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Cornell University Library
QD 5.W52
V.2
Watt's Dictionary of chemistry,
3 1924 002 980 575
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Library
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WATTS'
DICTIONARY of CHEMISTRY
VOL. IL
MUNIBD Br
SPOraiSWOODE, BALLANirNl! AND CX). LTD
lONBON, OOLCHKBTEB AKD ETON. EMGLAMO
WATTS'
DICTIONARY of CHEMISTRY
BEViaED AND ENTIRELY BEWBITTEN
BT
M. M. PATTISON MUIE, M.A.
FEI/LOW, AND FI^IiXOIOB IN GHEMISIBT, OF GONVILIiE AND CAIUS COIiIiEGE, CAMBBlDaS
AND
H. PQRSTEK MOELEY, M.A., D.Sc.
PEI/LOW OF UNIVEKSIXr-CaUiiHOB, LONDON, AND POBMEBLT PBOrBggOB OP OHEMIBTBT
. ^, dVBEN'l COI/IiEQX, LONDON
ASSISTED BY EMIS^NT CONTBIBUTOBS
IN POUE VOLUMKS *■
VOL. II.
NEW IMPRESSION
LONGMANS, GEEEN, AND CO.
89 PATEBNOSTER EOW, LONDON
POUBTH AVEN0E & 30th STEEBT, NEW YOBK
BOMBAY, CAIiCUTTA, AND MADRAS
1919
All T.ightt reserved
INTRODUCTION
TO THE ABTIOLES BELATING TO OBQANIO 0|p!MISTBY.
In the present volume the nomenclature is the same as tbftt adopted in the first
volume. It has been explained in the Introduction to that volw^e, pp. viii-xiv. Thus,
to take a single instance, the products of condensation between hydrazines and ketonio
compounds are still called hydrazides, although EmU Fischer has, since the publication
of the last volume, changed their name to hydrazones. Even supposing the latter
name to be preferable, its abrupt introduction would greatly confuse the nomenclature
by depriving it of uniformity.
Since the publication of the first volume I have been assisted in the work of .reading
and making abstracts of original memoirs by Drs. T. A. LawEon fmd Samuel Bideal,
Messrs. J. WUkie, ~5. T. Norman, V. H. Veley, G. N. Huntly, S. H. Collins, Dr. G. MoGowan,
and Mr, D. A. Louis. I have also been ably assisted by Mr. Arthur G. Green in the work
of revising the proof sheets. I have great pleasure in thanking tliese gentlemen for
the energetic and e£&cient manner in which they have carried out their share of
the work.
H. FOBSTEB MOBLET.
Xomenolatnre of Bing Formoles,
Hydrocwrbona.
0JH«<^^CH Indonaphthme.
CHj— CHj
CH,— CH,
TetramethyUne.
:,— CHj CH.
CH^^;g&> Pentamethylmt.
nitrogen ring eompound$.
CH-CH,^
A>NH Pyrrole 01 Pyrrol
H=CH^
CH>OH
I
-i.
Tetramtthenyl,
HN— CH^
I ^CH PyratoU.
N=CH^
H,C— N^
ICH MetapyraxoU.
HO=N'
CH— NH.
II >CH GlyoxaUint.
CH — "
CH<g^-^^N PynMM.
CH.^^g~^^CH Pyrimidine,
CH<^~(j2^CH Pyraeim.
K:CHv
I >
N:0H/
K:CHv HN.CH^
^NH or I ^N
CH=Nv
I ^NH Osotriazole.
CH— n/
N- N.
I >NH TetrazoU.
C,H.<^2^CH IndoU.
INTRODUCTION.
Nitrogen ring compounds — cont.
Triasole.
CHv
>NH Indazine.
^CHv
CjHj^'jjg^N Pseudo-indaHne.
0,HZ I ^C^4 Acridine.
Cfif<( I ^OjH, Phenazine.
N<^^2~^>CH TriazoKne.
N^~(]^CH OsotetrazoU.
c.h/
,CH=CH
CH
,CH=CH
C,
C.Hv
C.Hv
0,
CH=N
.N=CH
\n=ch
.CH=N
'\n = C!H
>CH=CH
i.HX I
■Qmnoxalitu, .
QmnazoUne,
CinnoUne,
CH=CH.
I ^0 Fii/rfu
CH=CH'
/
Oxygen ring compounds.
I ^N OxazoU.
ch=ch/
C.H,<^^^CH Coumarone.
„ XT /NHv.„ TT fPhenazoxine or. Di^henyU
^'^<<. O >C«H'\ oxazine.
CH=-CH.
I \S Thiophene.
CH=CH'^
CH=CHv
C — C ^ Thiophthene,
ch=ch/
CO<^-jjjj^ Carbizine. ,
Sulphur ring co/mpovmds.
I ^N ThiazoU.
ch=ch/
„„ f I)i-phenyl-thiazine {thiodi-
CjH4<^ g ^CbH, < phenylamine or Ivkdo-di-
L phenyl sulphide).
„ TT /Ns. „Vt f Methenyl-amido-phem/l-mer-
In many of the above formulae the exact structure is not Known ; alternative ways
of writing some of them will be found in vol. i. p. xiL
INITIALS OF SPEOIAL 00NTRIBUT0B8.
H.B. .
F.W. C.
I. P. .
A.G.G..
D. H. .
J. J. H. .
W. D. H.
F. B. J. .
G. M. .
P. W. B.
I. B. .
S.E. .
E.S. .
A.S. .
CO'S. .
J.J. T. ,
E. T. .
T. E. T. .
V.H.V..
HAEEY BAKEB, Esq., P.C.S,, Chemist to the Aluminivm Company, OUbury.
Contributes CnxsTAUiisATioN.
FBANK WIGGLESWOETH CLAEKE, Esq., B.Sc, Chief Chemist, United Statu
Oeological Swvey. Contributes Elements.
Miss IDA PEEUKD, Lecturer in Chemistry, Neivnham College, Cambridge, Con-
tributes Densities, belative.
AETHUE G. GEEEN, Esq., F.I.C., Research Chemist to the Atlas Works, EacJcney
Wick. Contributes Indioo.
DAVID HOWAED, Esq. Contributes Cinchona bark.
J. J. HOOD, Esq., D.So. Contributes Earths.
W. D. HALLIBUETON, M.D., B.Sc, Assistant Prof essor of Physiology at Umoersity
College, London. Contributes Hemoglobin.
FRANCIS E. JAPP, M.A., Ph.D., F.E.S., Assistant Professor of Chemistry at the
Normal School of Science, South Kensington. Contributes Gltoxalines, Hydba-
ziNES, and Eydbazones.
GEOEGE McGOWAN, Ph.D., F.E.S.E., Demonstrator in Chemistry at University
College of North Wales, Bangor. Contributes Cholesteein.
F. W. EXJDLEB, F.G.S., Curator of the Museum of Practical Geology, London.
Contributes Geoloqical chemistby.
lEA EEMSEN, Ph.D., Professor of Chemistry in Johns Hopkins University,
Baltimore. Contributes Equivaleiicy and Fobmul^.
SAMUEL EIDEAL, D.So., Lecturer on Chemistry at St. George's Sospital Medical
School. Contributes Febmentation.
Db. EDWAED SCHUNCK, Ph.D., F.E.S., Manchester. Contributes Chlobophymi.
ALFEED SENIEE, M.D., Ph.D. Contributes Cyanic acids.
0. O'SULLIVAN, F.E.S., Burton-on-Trent. Contributes Dexiein.
J. J. THOMSON, M.A., F.E.S., Professor of Experimental Physics in the University
of Cambridge. Contributes Equilibbicm, chemicaIi.
E. THEELPALL, M.A., Professor of Physics in the University of Sydney, N.S.W.
Contributes Dissociation and Explosion.
T. E. THOEPE, Ph.D., P.E.S., Professw of Chemistry at the Royal School of Mines.
Contributes Coubustion and Flame.
V. H. VELEY, M.A., PubUa Leei/wrer and Demonstrator in the University of Oxford,
Contributes Fobmio aoid.
Articles by Mr. MUIE are initialed M. M. P. M.
Unsigned Abticles are by Dr. MOELEZ.
ABBBBVIATI0N8
C7* Ct» 4
D. P. J.
Fr. . ,
Q.. . .
O.A.. .
H. . .
J. G. T. .
J.M. .
J. de Ph.
J. Ph. .
J.pr. .
J.Th. .
J.B.. .
3.Z.. .
L.T. .
M. . .
M.a.
MSm.
d'A.
S.
Iiiebig'a Annalen der Chemie.
Annales de la Sooiedad Cientifica Argentina.
Annales de Ghimie et de Physique.
Proceedings of the American Academy of Arts and Sciences.
American Chemical Journal.
Annales des Mines.
American Journal of Science.
Journal of the American Chemical Society.
American Cheihist.
American Journal of Pharmacy.
The Analyst.
Proceedings of the American Philosophical Society.
Archives nfierlandaises — The Hague.
MSmoires de I'Acad^mie des Sciences.
Archiv der Pharmacie.
Archives des Sciences phys. et nat.
Berichte der deutschen chemischen Gesellschaft.
Beports of the British Association.
Bulletin de la SociStS chimique de Paris.
Berliner Akademie-Berichte.
Biedermann's Centralblatt fiir Agricultur-Chemi*.
Berzelius' Jahresberichte.
Berliner Monatsberichte.
Memoirs ol the Chemical Society of London.
Journal of the Chemical Society of London.
Proceedings of the Chemical Society of London.
Chemical Newsi
Comptes-rendns hebdomadaires des Stances de I'Acad^mie des Sciences —
Paris.
Chemisches Central-Blatt.
Dingler's polytechnisches Journal.
Fresenius' Zeitschrift fiir analytische Chemie.
Oazzetta chimica itaUana.
Gilbert's Annalen der Physik und Chemie.
Hoppe-Seyler's Zeitschrift fiir physiologische Chemie.
Proceedings of the Boyal Irish Academy.
Jahresbericht iiber die Fortschritte der Chemie und verwandter Theile
anderer Wisseuschaften.
Jahresbericht fiir Chemische Technologic.
Jahrbuch fiir Mineralogie.
Journal de Physique et des Sciences accessoires.
Journal de Pharmacie et de Chimie.
Journal fiii praktische Chemie.
Jahresbericht iiber Thierohemie.
Journal of the Bnssian Chemical Society.
Jenaische Zeitschrift fiir Medioin und Naturwissenschaft.
Landwirthschaftliche Yersuchs-Stationen.
Monatshefte fiir Chemie und verwandte Theile anderer Wissenschaften.
Le Monitenr Scientifiqne.
M&aoires de la Soci6t6 d'ArcuoL
HSmoires oowonn^a par I'AcAd^iaie de Bru^eHed,
ABBREVIATIONS.
N'. . .
N.Ed.P.J.
N. J. P.
N. B. P.
N. J. T. .
P.M. .
P.. . .
P.B.. .
Pf. . .
Pr. E. .
Ph. . .
Ph. G. .
Pr. . .
P. R. I. .
P.Z. .
B.T.C..
B.P. .
Q. J. S. .
S.. . .
Scher. J.
S. G. I. .
Sits.W. .
T. or Tr.
T.E.. .
W. . .
W.J. .
Z. . .
Z.B. .
Z.f.d.g.
Natur-
wiss. .
Z.K.. .
Z. P. G.
Bn. . .
E. P. .
O.P. .
Gm. . .
Gm.-K. .
Girh. .
K.. . .
3.0. .
Stas.
Bech.
Stas.
Nouv. B.
Th. . .
Nature.
New Edinburgh Philosophical JoutnaL
Neaer Jahresbericht der Fharmacie.
Neues Bepertoiium fiir die Pharmacie.
Neues Journal von Tromms^orfC.
Philosophical Magazine.
PoggendorfE's Annalen der Physik und Chemie.
Beiblatter zu den Annalen der Physik und Chemie.
Pfluger's Archiv fur Physiologie.
Proceedings of the Royal Society jsf Edinbureh.
Pharmaceutical Journal and Transactions.
Pharmaceutisches Gentral-Blatt.
Proceedings of the Eoyal Society.
Proceedings of the Eoyal Institution of Great Britain.
Pharmaceutische Zeitschrift fjir Eussland.
Eecueil des travaux chimiques des Pays-Baa.
Bepertorium fiir die Pharmacie.
Quarterly Journal of Science.
Schweigger's Journal der Physik.
Scherer's Journal der Chemie.
Journal of the Society of Chemical Industry.
Sitzungsberichte der K. Akademie zu Wien.
Transactions of the Eoyal Society.
Transactions of the Eoyal Society of Edinburgh.
Wiedemann's Annalen der Physik und Chemie.
Wagner's Jahresbericht.
Zeitschrift fiir Chemie.
Zeitschrift fiir Biologic.
Zeitschrift fiir die gesammten Naturwissenschaften.
Zeitschrift fiir Erystallographie und Mineralogie.
Zeitschrift fiir physikalische Chemie.
Handbuch der organischen Chemie : von F. Beilstein, 2te Auflage.
English Patent.
German Patent.
Gmelin's Handbook of Chemistry — ^English Edition.
Gmelin-Eraut : Handbuch der anorganischen Chemie.
Traits de Chimie organique : par Charles Gerhardt.
Lehrbuch der organischen Chemie : von Aug. Kekulfi.
Graham-Otto : Lehrbuch der anorganischen Chemie [5th Ed.]
Stas' Eecherches, &o. "j
' Aionstein's German translation ia le-
Stas' Nouvelles Eecherches, &c. J f erred to as Chem. Proport.
Thomsen's Thermochemische Untersuchungen.
II. TeBMS and QnANIIIIES, &C., FBEQCENILT USED.
Aq,
aq.
A'
A"
A'"
B' B" etc,
cone.
dil.
g- •
mgm.
mm.
mol.
oil.
pp.
to ppt.
PPg-
ppd.
}
Water ; e.g. NaOHAq means an aqueous solution of caustic soda.
18 parts by weight of water.'
Eesidues of mono-, di-, and tri-basic acids. Thus, in describing the salts
of a monobasic acid NaA', CaA'j, AlA', may be written, HA' standing
for the acid. For a dibasic acid we should write NajA", CaA", AljA", &o.
Stand for bases of the ammonia type, in describing their salts. Thus the
hydrochloride would be B'HCl or B"2HC1, according as the baas ii
monacid or diacid, &o.
Concentrated,
Dilute,
gram,
milligram,
millimetre,
molecule.
liquid, nearly, or quite, insoluble in watn.
precipitate,
to precipitate,
precipitating,
precipitated.
ABBUEVIATIONS.
BOl. . .
insol. . .
V. e. sol. .
V. sol.
m. sol. .
si. sol. .
V. si. sol.
V. . . .
cf.. . .
0. . . .
["] • •
p • •
u* • . •
At. w. .
Mol.w.or
M. w.
D. . . .
cor. . .
UCCOT. .
i.V. . .
V.D. . .
S.G. . ,
S.G.V .
S.G. L» .
S.G.ia .
S.H. . .
S.H.V. .
S.H.p. .
H.G. . .
H.C. V.
H.C. p.
H.F.
H.F.T.
H.F.p.
H.V. .
T.C.
S.V.
S.V.S. .
E.C. . .
O.B. (10°
to 20°)
S.. . .
S. (alco-
hol)
/«fl. . .
B„
Boo
Ml,
Wj
soluble in.
insoluble in.
very easily i
very
moderately
slightly
very slightly i
soluble in.
compare.
about.
a melting-point.
a boiling-point.
Hardness (of minerals).
Atomic Weight.
Molecular weight.
Density.
corrected.
uncorrected.
in vapour.
vapour-density, i.e. density of a gas compared with hydrogen or air.
Specific gravity compared with water.
„ „ at 10-' compared with water at 0°.
l.'i° 4'
If *> II •'■*' II II II II * •■
„ I, „ 12° ; compared with water of which the temperatoie is
not given.
Specific heat.
„ „ of a gas at constant volume.
•I 11 II _ II II _ pressure.
Quantity of heat, in gram-units, produced during the complete com-
bustion of the mass of a solid or hquid body represented by its
formula, taken in grams.
Heat of combus'tion in gram-units of a gram-molecule of an element or
compound, when gaseous, under constant volume.
The same, under constant pressure.
Quantity of heat, in gram-units, produced during the formation of the
mass of a solid or liquid body represented by its formula, taken in
grams, from the masses of its constituent elements expressed by
their formulae, taken in grams.
Heat of formation of a gram-molecule of a gaseous compound from the
gram-molecules of its elements under constant volume.
The same, under constant pressure.
Heat of vaporisation of a liquid, i.e. gram-units of heat required to change
a gram-molecule of the liquid compound at B. P. into gas at same
temperature and pressure.
Thermal conductivity (unit to be stated).
Specific volume ; or the molecular weight of a gaseous compound divided
by the S.G. of the liquid compound at its boiling-point compared vdth
water at 4°.
Specific volume of a solid ; or the mass of the solid expressed by its
formula, taken in grams, divided by its S.G.
Electrical conductivity (the unit is stated in each case).
Coefficient df expansion (between 10° and 20°).
{of a gas = volume dissolved by 1 volume of water,
of a liquid or solid = number of grms. dissolved by
100 grms. of water. In both cases the temperature
is stated.
Index of refraction for hydrogen line P.
„ „ „ sodium „ p, &o.
Molecular refraction for sodium light, i.e. index of refraction for line d
minus one, multiplied by molecular weight, and divided by S.G. at 15°
compared with water at 0°.
The same ; S.G. being determined at 15°-20° and referred to water at 4°.
The same for line of infinite wave-length, index being determined by
Gauchy's formula (Briihl's Ba).
Specific rotation for sodium light.
„ ,, „ neutral tint, [o] = — x-. a = observed rotation tor
p a
100 mm. of liquid. d = S.Q.ol liquid. j)= no. of grammes of active
substance in 100 grammes of liquid.
XII
ABBREVIATIONS.
M. M.
m xa
Molecular maRnetio rotatory power = ^
where m = moleoulai
AO
Bz
Cy
Et
Me
Ph
Pr
Pr
B.B'
prim
tec
tert
n .
m,o,_
c .
i .
I
weight of the body ot S.G. = d, a = angle of rotation under magnetio
influence, a = angle of rotation of water under same influence, and
m' - molecular weight of water (18V.
Acetyl C.,n,0.
Benzoyl C,HjO.
Cyanogen CN.
Ethyl C,H,.
Methyl CH,.
Phenyl CA. Mn formula.
Normal Propyl CH,. CHj. CH,.
Isopropyl CH(CH,),.
&o- Alcohol radicles or alkyls.
primary,
secondary,
tertiary,
normal.
meta- ortho — para,
consecutive,
irregular.
Eymmetrical.
nnsymmetrical.
pseudo.
attached to nitrogen.
Employed to denote that the substituent is attached to a carbon atom
which is next, next but one, or next but two, respectively, to the
terminal carbon atom. The end to be reckoned from is determined
by the nature of the compound. Thus CH3.CHBr.C0.^H is a-bromo-
propionic acid,
denotes that the element or radicle which follows it is attached to a ter-
minal carbon atom.
a,/3,7,i!kc. indicate position in an open chain, only.
l,2,3,&c. indicate position ina ring only.
(a), {$), Used when a, B, &o. are employed in a sense different from the above,
&e. e.g. (a)-di-bromo-camphor.
Baeyer's Nomenclature : '
{B.) . . benzene ring.
{Py.) . , pyridine ring.
Thus (B. 1:3) dichloroquinoline, means a meta-dichloroquinoline in
which the chlorine atoms are both in the benzene ring.
While (Py. 1:3) dichloroquinoline, means a similar body, only the
chlorine atoms are in the pyridine ring. The numbers are counted
from two carbon atoms which are in different rings, but both united
to the same carbon atom.
{A.) . , denotes the central ring in the molecule of anthracene, acridines, and
azines.
eso- . . means that the element or radicle it precedes is in a closed ring,
*xo- . . ., „ „ „ „ not in a benzene ring.
alio- . . denotes isomerism that is not indicated by ordinary formuls ; thus maleio
acid may be called a22o-tumaric acid,
thio- . . denotes displacement of oxygen by sulphur,
sulpho- . „ the group SO,H, except in the word sulphocyanide.
Bulphydro- „ the group SH.
i Tribromonitrobenzene sulphonic acid [1:2:3:4:5] means that the three
I bromines occupy positions 1,2, and 3 ; the nitro- group the position 4,
and the eulpho- grcup the position 5. ~
" Denotes that the tcrmula to which it is affixed has not been determined by
analysis. >But it by no means lollcws that formulae without this mark are those of
analysed compounds.
All temperatures are given in degrees Centigrade unless when specially stated
otherwise.
Wave-lengths are given in 10"' mm.
Formulae, when used instead of names of substances, have a qualitative meaning
only.
Ihomsen's notation is used in thermochemical data.
DICTIONARY OF CHEMISTRY.
OHEMOCHOLIC ACID C^H^.O,. Formed by
boiling tauiochenocholic acid, from goose-bile,
with baryta-water (Heintz a. Wislioenus, P. 108,
647). Amorphous mass (from alcohol or ether),
insol. water. Gives Pettenkofer's reaction with
H2SO, and sugar. Insol. cold KOHAq, but dis-
solves on warming, forming a solution that is
ppd. by BaClj and CaCl^.— BaA', (dried).
CHEKOPODINE CbHisNO,. This base, which
occurs in white goosefoot {Chenopodi/um alhwm)
(Beinsch, N. J. P. 20, 268 ; 21, 132 ; 27, 193 ;
J. pr. [2] 22, 188), is probably leucine (G-orup-
Besanez, B. 7, 147).
CHICA. A red dye obtained from the leaves
of Bignonia Chica growing in South America.
The colouring-matter may be extracted by alco-
hol. It is insol. ether and NajCOgAq, but sol.
NaOHAq. Chromic acid oxidises it to anisic
acid (Erdmann, J.pr. 71, 198).
CHICOBY. The blue blossoms of Cichorium
Intyhus contain a glnccside CjjHa^Omi^aq
[215°-220°], which may be extracted by dilute
alcohol. It crystallises from water, in 'which it
is slightly soluble, in needles. Aqueous alkalis
and ajkaline carbonates form yellow solutions.
Boiling dilute acids split it up into glucose and
Ca,H„0, [250°-255°], which also occurs in the
blossoms. This forms needles, v. si. sol. boiling
water, coloured dark green by FejClj (Nietzki,
/. 1876, 851 ; Ar. Ph. [3] 8, 827).
CHICLE ALBAlf C,„H„0. [145"=]. S. (al-
cohol of S.G. -82) -66 at 14°. Obtained by
extracting chicle gum (Mexican rubber juice),
from Ohrysophylhim glycyplacum, with weak
alcohol (Frochazka a. Endemann, A. G. J. 1,
50). The mother liquor deposits chicle fluavil
CjoHajO (?) ; S. (alcohol of S.G. -82) 2-6 at lB-5''.
The residue of the gum, after extracting with
alcohol, contains two terpenes and arabin.
CHIN-. Substances beginning with Chin-
will be described under the alternative names
which begin with QuiN-. Thus Chinidine, Ohi-
none, and Chinoline are described as QniurDiNB,
QumoNE, and Quinoline.
CHIEATIN CjsHjjOis. Extracted by dilute
alcohol from the stalks of OpheUa cMrata
{Rohn, Ar. Ph. {2} 139, 213). Besinous mass,
decomposed by hot dilute HOI into ophelio acid
and morphous chiratogenin CuHjjO,.
CHITENIDINE C,,B^,Sfit- Formed by oxi-
dation of quinidine with KMnO^. Thin plates
(containing 2aq). Sol. alkalis and hot water, si.
sol. alcohol. — B"H2S04 3aq: white prisms. —
B"H201j^tCl, 3aq : large orange -red needles
(Forst a. Bohringer, B. 15, 1659).
CHITENINE OijHjjNjO,. Prepared by oxi-
dation of quinine with KMnO,. White prisms
Vol. 11.
(containing 4aq). Insol. alcohol and ether, si.
sol. water. Very weak base. — B„(HjS04), 15aq :
fine needles.— BHjCLPtOL 3aq (Skraup, B. 12,
1104).
CHITIIT V. Proteids, Append/ix C.
CHLOBAL CjHClaO i.e. CC1,.0H0. 2Vi-
chloro-acetic aldehyde. Mol. w. 147'5. [c. — 75°]
(Berthelot, Bl. [2] 29, 3). (98° cor.) (Perkin) ;
(97-2°) (Thorpe, G. J. 37, 191). V.D. 5-13.
S.G. 1 1-5292 (Perkin, O. J. 51, 808) ; ^ 1-5121
(Briihl, A. 203, 11) ; £ 1-5417 (Pa.). C.E.
(0°-10°) -001123; (0°-100°) -001295 (Laura
Passavant, C. J. 39, 53). /lo 1-4623. Boo 43-06.
M.M. 6-591 at 16° (Perkin). S.V. 107-4.
Formation. — 1. By the action of chlorine on
aqueous aldehyde (Pinner, B. 4, 256 ; Wurtz a.
Vogt, Z. 1871, 679).— 2. From tri-ohloro-acetal
and HjSO, at 150° (Patemo, A. 150, 256 ; Z. [2]
4,733). — 3. By distilling starch or sugar with
HCl and MnOj (Stadeler, A. 61, 101).— 4. By
distilling tetra-ohloro-ether, CClj.CHCl(OEt),
with H^SO, (W. a. V.).
Pj-eparaiiow.— Chlorinfi gas is passed into
absolute alcohol, which must be cooled at first,
but afterwards may be heated gradually to boil-
ing. The crystalline chloral alcoholate formed
is decomposed by shaking with H2SO4 and the
liquid chloral rectified (Liebig, A. 1, 189 ; Dumas,
A. Gh. [2] 56, 125 ; Miiller a. Paul, B. 2, 641 ;
Thomsen, Z. [2] 6, 156 ; Eoussin, Z. [2] 6, 96;
Personne, C. B. 69, 1363 ; Paul, Ph. [3] 1, 621 ;
C. J. "24, 134). By-products are ethylidene
chloride, ethylene chloride, and chloro-ethylene
chloride (116°). The ohlorination is promoted
by the presence of 6 p.o. Fe2Gl, (Page, D. P. J,
252, 343. V. also Chlobaii hydbate).
Theory of the process. — Chlorine oxidises
alcohol to aldehyde, this combines with alcohol
forming acetal CH3CH(0Et)2, which is then con-
verted into tri-chloro-acetal CGl,CH(0Et)2
which is saponified by the HOI formed in
the previous reactions : 0Cl3.CH(0Bt)j + HCl
= CCl,.CH(OH)(OEt)-HEtCl (Lieben, 0. S. 44,
1345 ; B. 3, 910). Wurtz (C. B. 74, 777) con-
siders that chloro-ether is first formed, thus:
0H,0H0 + HOEt + HOI = H^O + CHs.OHCl(OEt),
and this is then converted into tetra-chloro-ether
00l3.0HCl(0Et), which is converted by alcohol
into tri-chloro-acetal CCl30H(OEt)2, which is
then decomposed by HOI as above.
EstimaUon. — ^By shaking with standard
KaOH and determining the amount of al)iikli
neutralised.
ProperUes. — A liquid with odour resembling
aldehyde. It solidifies when shaken with a little
water, forming so-called chloral hydrate, but it
dissolves in much water. It reduces ammonia-
CHLORAL.
oal silver nitrate with formation of a mirror. It
Is not affected by distillation over quicklime or
BaO as long as the oxide is covered by the liquid.
It combines with NH,. When introduced into
the blood it is split up into chloroform and for-
mic acid (Liebreich ; Personne, G. B. 69, 979 ;
Byasson, O. B. 72, 742 ; Arloing, 0. B. 89, 245,
626; c/. Thomaszewicz, P/. 9, 35). Tanret sup-
posed that its physiological action was due to
the liberation of CO in the blood {J. Ph. [4] 20,
355). Some of the chloral passes into the urine
as urochloralic acid CgHjiGlsO,.
Beactions. — 1. Split up at once by NaOH
into chloroform and sodium formate, thus :
CCI3.CHO -1- NaOH = COljH + NaOHOj.
Alcoholic KOH andNaOEt act similarly, forming
formic ether and chloroform (Kek.ul&,A. 119, 187).
2. Zn and HCl reduce it to aldehyde (Personne,
A. 157, 118 ; C. B. 71, 227). Zino-dust and water
reduce it, on heating, to OH,, CH^Clj, and OH5CI
(Cotton, J3Z. [2] 42, 622) — 3. Fuming HNO3 oxi-
dises it to tri-chloro-acetic acid. CrO, or HgO
gives CO and COj. KMnOj gives CO^, chloroform,
oxygen, and chlorine (Cotton, Bl. [2] 43, 420). —
4. Chlorine in sunlight forms CC1„ hydric chlo-
ride, and COCI2 (Gautier, Bl. [2] 45, 86 ; 0. B.
101, 1161).— 5. Bromine forms CCl3CO.Br,
001,Br, CO, and HBr (Oglialoro, B. 7, 1461).—
6. PCI5 forms OOls.CCl^H (Paterno, G. 1, 590 ;
Z. [2] 5, 245).— 7. PCljBrj forms CCljCBr^H.-
8. H2SO4 forms chloralide crystals (g;. v.).
Fuming HjSO, forms a crystalline compound {v.
infra). — 9. KIAq forms iodine and chloroform.
- 10. AljClj forms paraohloral (240°) and C^Cl,
(Combes, A. Ch. [6] 12, 298).— 11. PjSs forms
CjHCl, (88°) (Paterno a. Oglialoro, &. 3, 538).
12. Aniline reacts violently forming tri-chloro-
ethylidene-di-phenyl-di-amine CCl3.CH(NHPh)2
[101°] (Wallaoh, B. 5, 251).— 13. AcetanUde com-
bines forming CCl3.CH(0H)(NHAc) (v. CHiiOBAi-
ammokia). — 14. Acetoniirile f ormsCCl3CH(NHAc)2
(Hubner, B. 6, 109 ; Z. 1871, 712 ; Hepp, B. 10,
1651) : needles (from HOAc). — 15. Heated with
syrupy lactic acid at 160° chloral forms tri-
chloro-ethylidene mono-laetate :
CH,.CH<'^^°>CH.CC1, [45°] (223°) (Wal-
laoh, A. 193, 36). This body may also be got
by dissolving chloral hydrate (1 pt.) in syrupy
lactic acid, and adding H2SO4 (1 pt.) (M.Nencki,
J.pr. 125, 239). In a similar way, tri-chloro-
lacUe acid heated with chloral forms chloralide
(g. V.) ; tri-bromo-lactic acid forms tri-ohloro-
ethylidene tri-bromo-lactate
CBr3.CH<^Q°>CH.CCl3 [132°-135°] ; tri-
ehloro-a-oxy-valeria acid forms
C,H401..CH<''°-°>CH.CCl3 [88°], (297°) ; gly-
collio acid forms CHj<;^°-°>CH.CCl3 [42°] ;
maUc acid forms tri-chloro-ethylidene malate
CO.H.CH..CH.Ov
I >CH.0C1, [140°] (Wallaoh, A.
co.o/
193, 37) ; tarta/ric acid gives
CCl3.CH<g (,o>CH.CH<° co>OH.CCl3 :
talicylic acid forms CjH,<^ q' ]]>CH.CC1,
[124°] ; while mandeU* add producea
C,H,.CH<*^Q°^CH.00l3 [82°]. — 16. When
mixed with benzene (1 mol.) and concentrated
sulphuric acid, di -phenyl- tri -chloro- ethane
CCl3.CH(CsHJj is formed (Goldschmiedt, B. 6,
985). Bromo- and ohloro-benzene and toluene
act similarly (Zeidler, B. 7, 1180 ; Fischer, B. 7,
1191). — 17. By acting on benzene with chloral in
the presence of aluminium chloride a liquid is
obtained having the formula CsHs.CCIj.COH.HOl
which by oxidation forms the acid
C5H5.CCI2.COOH (Combes, C. iJ.98, 678; Bl. [2]
41, 382). — 18. Zinc methide (1 mol.) followed by
water forms CC13.CH(0H).CB4. Excess of ZnMe,
followed by water forms (CH,)2CH.CMej.0H.—
19. Zi/no ethide followed by water forms tri-chloro-
ethyl alcohol COl3.CHj.OH. — 20. Hydroxylamine
forms ohloro-glyoxim CjHjClNjOj.
Combinations. — 1. With water v. Chloral
hydrate.
2. With alcohols v. Chloral hydrate.
3. With hydric sulphide: (CjCl3H0)2HjS.
[128°]. Formed by passing H^S into a solution -
of chloral (Hagemann, B. 5, 154 ; Wyss, B. 7, 2ll ;
Paterno a. Oglialoro, G. 3, 533). Bhombohedra
(from chloroform). Insol. water, sol. alcohol
and ether. Decomposed by heat. With PClj it
gives CCI3.CHCI2. Gives with AcCl a di-acetyl
derivative [78°].
4. With phosphuretted hydrogen :
(CCl3CHO)3PH,. [143°]. From chloral (3 g.) and
PH,! (2g.). Small prisms (from ether). Decom-
posed by cone. NaOH into formate, hypophos-
phite, and hydrogen (Girard, A. Ch. [6] 2, 43).
5. With mercaptan : CjCl3H0,HSEt. Crya-
talline.
6. With acetyl chloride : CCljCHC^OAo).
(c. 187°). S.G. iZ 1-476 (V. Meyer, B. 3, 445;
A. 171, 67 ; cf. Curie a. Millet, C. B. 83, 745).
7. With aceUc anhydride : CCl30H(OAo)2.
(222°). S.G. ii 1-422. Oil.
8. With ethylamim: CCl3.CH(0H)NHEt. On
distillation this forms CHCI3 and ethyl-form-
amide H.CO.NHEt.
9. With/Mmmgf sulphuric acid :
(CjCl3HO)3,SO„2HjSO,. [70°]. Chloral (1 pt.)
is mixed vrith fuming sulphuric acid (5 pts.).
The product is washed with cold water and crys-
tallised from ether (Grabowski, B. 6, 225, 1070).
A mixture of chloral with an equal volume of
fuming sulphuric acid forms large crystals of
(CC1,.CH0)4,H2SA.
10. With alkalme 'bisulphites :
OjClsHO.KHSOj (Stadeler, 4.106,253; Bathke,
A. 161, 154). This compound is also formed when
KjSO, is used, but if the solution be heated to
80° (S03K)2CH.CHO,EHS03 aq crystallises out,
while the mother-liquor contains 036230138,03, K,.
11. With hydrogen cyarUde: CClsCH(OH)CN.
Tri-chloro-lacto-nitrile. [61°]. (c.218°). Pre-
pared by the action of anhydrous prussic acid at
120° upon chloral (Hagemann, B. 5, 151) or by
boiling chloral with strong prussic acid (Bischoff
a. Pinner, B. 5, 113; A. 179, 77). Trimetrio
plates (from CSj). Saponified by HCl forming
tri-chloro-laotic acid. Saponified by KOH form-
ing potassic formate and cyanide and chloro-
form. With urea it forms CCl,CH(NH.CO.NHj).
(Pinner, B. 20, 2345). Acetyl derivative.—
CCl,CH(OAo),CN. [31°]. (208°). From acetic
anhydride and 4ibe above (Pinner a. I'uchs,
CHLOEAL.
B. 10, 1059). Bhombohedia. Insol. water,
sol. alcohol. Gone. H^SO, in the cold forms
CCla.CH(OAo).CO.NH2.
12. Another compound with hydrogen cyan-
ide: (001,.CHO),.ONH. [123°]. From cone,
solutions of chloral and of KCN (Ceoh, B. 9,
1020). Prisms (from ether or benzene). Insol.
water. Alcoholic potash (or even alcohol alone)
iorms di-chloro-acetic ether. On distillation it
splits up into chloral and chloralide (Wallach,
B. 6, 114). Alcoholic, or dilute aqueous, solu-
tions of EGN convert chloral into di-chloro-
acetic acid (or ether).
13. With cyarUc acid: (C2ClsH0)2CN0H
[c. 169°]. Formed by passing vapour of cyanic
acid into chloral, boiling the product with HCl
and crystallising the residue from ether. Small
prisms (Bischofi, B. 5, 86).
14. With both cycmic and prtissic acids,
CjCljHO, CNH, ONOH. [80°]. Prepared by
pouring a solution of GNOK upon a mixture of
solutions of chloral and KOy. Needles. Decom-
posed by hot water. Gonverted by ethylamine
into GGlj(NEtH)CHO. [45°] (Geoh, B. 8, 1174 ;
9, 1253 ; 10, 880).
15. With sodiwm acetate: GCl3GH(0Ac)(0Na).
Minute white crystals, decomposed by water and
alcohol (EebufEat, Q. 17, 406).
16. With carbamic ether :
CGlj.CH(OH).NH.GOjEt. [103°], Flaky mass
. (from ether-alcohol), formed by adding cone.
HGl to a solution of carbamic ether in chloral
(BischoS, B. 7, 631). Besolved into its compo-
nents by hot water or by heating at 100°.
17. With urea : GGl3.GH(0H).KH.G0.NHj.
[150°]. From chloral and a cone, aqueous solu-
tion of urea. Scales. Decomposed on melting
into chloral and cyanuric acid. The compound
(CGl3.CH(0H).NH),C0 [190°] is also formed, and
differs from the preceding in being nearly insol.
boiling water (Jacobsen, A. 157, 246).
18.. With benmnUdoxim:CsB,'Sfilfii. [135°].
White powder, insol. water, v. sol. alcohol and
ether. Besolved by boiling dilute H^SOj into its
constituents (Falck, B. 19, 1481).
19. With hexamidoxim: GjHisNjGlaOj. [130°].
White pearly plates. Formed by heating the
components together for a long time (Jacoby,
B. 19, 1505).
20. With thio-henzamide :
CC1,.CH(0H).NH.GS.G,H5. [104°]. Prom chloral
and thio-benzamide (Spica, G. 16, 182). Bhom-
boidal prisms of alliaceous odour, si. sol. water,
sol. alcohol and ether.
Chloral-ammonia GGl,.GH(OH).NHj. [64°].
Formed by passing NH, into a solution of
chloral in chloroform (Stadeler, A. 106, 253 ;
Schifi, B. 10, 167). Insol. cold water, decom-
posed by hot water into GEGI3 and ammonio
formate (Personne, A. 151 . 114). Boiling alco-
holic EON converts it into di-chloro-acetamide
(E. SchifE a. Speoiale, Q. 9, 338). With benzoic
aldehyde it gives GGl,.CH(OH).N:GHPh [130°],
which crystallises from benzene in white leaflets,
resolved by dilute acids into benzoic aldehyde,
chloral, and NH, (SchifE, Q. 9, 436).
Acetyl derivative. — CC\C'S.(aB)TSiB.ke.
Chhral-acetamide. [156°]. Formed by the
action of acetyl chloride or acetic anhydride on
the above; or from chloral and acetamide. Tri-
wetric plates (from water). Insol. ether. De-
composed by heat into chloral and acetamide.
Alcoholic EON forma CnHi.CljNjOs. [120"]
(S. a. S.).'
Di-aceiyl derivative.
OCl,.CH(OAo)(NHAo). [118°]. Formed by the
action of GlAc at 120° on the preceding^ De-
composed by warm water into the preceding and
acetic acid, the group (OAc) being unstable in
presence of so much chlorine.
Dichloracetyl derivative.
C0l3.0H(0H).NH.00.0H01j. [105°]. From chlo-
ral and di-chloro-acetamide (S. a. S-)- ^sxge
prisms (from water).
Benzoyl derivative.
CCli,.OH(OH).NHBz. [151°]. From benzamide
and chloral (Jacobsen, A. 157, 245) or bypassing
HOI into a mixture of chloral-hydrate and ben-
zonitrile (Pinner a. Elein, A 11, 10). Tables
(from alcohol). Alcoholic EON forms a com-
pound GjuHnOljN^O [131°J, which separates in
small crystaJs from ether (S. a. S.).
Chloral hydrate G^HjOlsOj i.e. 0Cl3.CH(0H)j.
Tri-chloro-acetic ortho-aldehyde. Mol.w. 165'5.
[57°]. (97°). S.G. ffi 1-6415 (Perkin, C. J. 51,
808) ; w 1-575 ; S.G. (soHd) 1-901. V.D. 2-8
(corresponding to a mixture of water and chloral).
S. (in OSj) 2 at 15° ; 20 at 46°. Ecp 47-94 (in
a 33-2 p.c. aqueous solution) (Kanonnikoff, J.pr.
[2] 81, 347). M.M. (fused) 7-151 at 54-6° ; (in
aqueous solution) 7-02 at 14°-
Formation. — ^By direct union of chloral with
water, absorption of heat taking place (Phipson,
O. N. 25, 267).
Preparation. — ^Alcohol (400g. of 97 per cent.)
is poured upon crystallised ferric chloride (5g.
of Fe^Ol, 12aq) and a large excess of chlorine is
passed in. The product is distilled. The distil-
late contains chloral and chloral hydrate but not
chloral alcoholate. After rectification the portion
boiling between 94° and 97° is converted by water
into chloral hydrate (525 g.) (Page, A. 225, 220 ;
cf. Detsenyl, C. 0. 1873, 7B7). Chloral hydrate
may also be purified by 'Crystallisation from GS^
(Fluckiger, Z. 6, 432).
Properties. — Monoclinio plates, v. sol. water
and alcohol. By shaking with cone. HjSO, it is
at once converted into chloral. In doses of more
than 5 g. it produces sleep (Liebreich, B. 2, 269).
It is antiseptic, preventing putrefaction of pro-
teids. The vapour of chloral hydrate is split up
by heat into chloral and water ; the dissociation
is complete at 100° at the ordinary pressure, and
even at 61° under a pressure of 9 mm. (Wurtz,
C. B. 89, 190 ; cf. Moitessier a. Engel, C. iJ.'86,
971 ; Troost, C. E. 84, 708 ; 85, 32, 400 ; 100,
834; A. Oh. [5] 13,411; 22, 155; Friedel, Bl. [2]
48, 56 ; C. B. 100, 891 ; Naumann, B. 9, 822).
The molecular magnetic rotation indicates
that chloral hydrate exists as such in its aqueous
solution. ' In amyl oxide solution it begins to
dissociate between 30° and 40°(Perkin, C. J. 51,
808). Ghloral hydrate differs from chloral in
''not exhibiting Schiff's test for aldehydes with
rosaniline and SOj (V. Meyer a. Caro, B. 13,
2343).
Detection. — Chloral hydrate may be extracted
by ether from its aqueous solution (e.g. urine)
and the following tests may then be applied:
{a) Warming with alcoholic EOH and aniline
gives (even with -OOOOlSg.) the disgusting odour
of phenyl carbamine. (6) Warming at 50° with
b2
CHLORAL.
oono. EOHAq and a little phenol gives a blue
colour (with -OOOOSg.). (c) After boiling with pot-
ash formic acid may be detected (with -OOOllg.).
(d) Lime-water and HjS give a pint colour (with
•00066g.) (Dragendorff a. Tiesenhausen, C. G.
1886, 636). The valuation of chloral hydrate
may be effected by decomposing it with ammonia,
EOEAq, or, better, with H^SOj (Versmann, Ph.
[3] 1, 701, 965 ; \Yood, Ph. [3] 1, 703 ; cf.
Miiller, Z. [2] 7, 66 ; 0. J. 24, 444 ; Paul, Ph. [3]
I, 621 ; 0. J. 24, 134).
BeacUons. — 1. With KCy it forms di-ohloro-
aoetio acid. — 2. Heated with glycerin it forms
chloroform, formic acid, and allyl formate (Byas-
Bon, C. B. 75, 1628). — 3. Boiled with ammonia
acetate it forms chloralimide, C0l3.CH:NH (Pin-
ner a. Fuchs, B. 10, 1068).— 4. Warmed with
aqueous KHS deposits Sulphur, and then crystals
of OiHjClsOjS [97°] (Michael, B. 9, 1267 ; cf.
Nicol, C. N. 43, 43). — 5. With aqueous ammonia
sulphide it forms a red powder OijHjjSuNjOs.
This dye separates from petroleum in lustrous
green crystals (E. Davy, P. M. [4], 68, 247;
Lerch, C. C. 1887, 299).— 6. Melted with KClOa
it reacts violently with production of tri-chloro-
acetio acid and decomposition products (Seubert,
B, 18, 3336). — 7. Boiled with zinc-dust it is de-
composed with formation of chloride and oxy-
chloride of zinc and liberation of hydrogen and
CH4(Cotton, Bl. [2] 42,622).— 8. HgO decomposes
chloral hydrate with formation of COCl^, carbonic
oxide, and 00^. — 9. KMnOj liberates chlorine,
OOj, and oxygen with formation of CHClj (Cotton,
Bl. [2], 43, 420).— 10. Heated with ammonic
sulphocyanide forms a white crystalhne body
CjHsOIbNjS, insol. water, sol. alcohol (Neneki a.
Schaffer, J.pr. 126, 430 ; Brodsky, M. 8, 27).—
II. Cam,phor forms an unstable compound (vol.i.
670).— 12. Acetyl chlorideioims CCl3.CHCl(OAo)
(Meyer a. Dulk, B. 4, 963).— 13. With di-methyl-
amimeandZnCl2itgivesCCl3.CH(OH).OsH4NMej
(Enoeffler a. Boessn^ok, B. 20, 3193).
Acetyl derivative CCls.CHfOAc)^. (222°
uncor.)._ S.G. " 1-422. Prom chloral and AcjO.
Liquid, insol. water, not attacked by cold KOHAq
(Geuther, A. 106, 249).
Ethyl ether CCl3.CH(0H)(0Et).
Chloral alcoholate. Mol. w. 193-5. [56°].
(Jacobsen) ; [46°J (Lieben, B. 3, 909). ' (115°)
(Martius a. Bartholdy, B. 3, 443). S.G. f 1-329.
V.D. (air = 1) : 3-49 at 200° (theory: 6-68). The
vapour-pressure has been examined by Eamsay
a. Young (C. J. 49, 686). Formed by the union
of chloral with alcohol (Personne, C. B. 69, 1863;
cf. EouBsin, 0. B. 69, 1144; Thomsen, B. 2,
597; Lieben, B. 3, 907; Jungfleisoh, Lebaigne
a. Boucher, J. Ph. [4] 9, 208). Its vapour is
dissociated by heat. Separated from aqueous
solution by CaClz. Decomposed by HjSO, with
liberation of chloral. With POI5 it gives tetra-
chloro-ether, CCl3.OHCl.OEt (Henry, C. J. 24,
255, 696 ; B. 4, 101, 435).
Ethyl-acetyl derivative
CCl3(OAo)(OEt). (198° unoor.). S.G. H 1-327.
Prom chloral alcoholate and AcCl. Also from
tetra-phloro-ether and AgOAc (Busch, B. 11, 447).
Methyl. ethyl ether 0Gl3(0Me)(0Et).
(193-4°). S.G. 2* 1-32. From tetra-chloro-ether
aiid MeOH (Magnanimi, G. 16, 830). Liquid,
imelliug like camphot.
Chloro-ethyl ether
CCl,.CH(OH)OCHj.CHjCl. Prom chloral ani
glycolic chlorhydrin. Converted by PCI5 into
CCl,.CHC1.0.CHj.CH2Cl (Henry, B. 7, 763). .
Jlfe<fe2/Ze4;ierCCl3.CH(OH)(OMe). Chlofal
methyl-alcoholate. [50°]. (106°) (Jacobsen, A.
157, 243) ; (98°) (Bartholdy a. Martius, B. 3,
443). Prom chloral and methyl alcohol.
Di-methyl ether CCl3.CH(0Me)j. (183°).
S.G. 1-28. From CCI3.CHCI.O.CH, and MeOH.
Liquid, smelling of camphor (Magnanimi, G. 16,
380).
Di-ethyl ether CCl3.CH(OEt)2. Tri-chloro-
acetal. (197°) (B.) ; (200°) (W.- a. V.) ; (205°
cor.) iF. a. P.). S.G. 2-281 (P. a. P.). S. -5.
Formed by passing chlorine into dilute (75 p.c.)
alcohol ; or by treating chloral alcoholate with
chlorine at 80° (Byasson, Bl. [2] 32, 304 ; O. B.
87, 26). Formed also by treating tetra-ohloro-
ethyl oxide CCls.CHCl.OEt with alcohol in sealed
tubds (Wurtz a. Vogt, C. B. 74, 777 ; Paterno a.
Pisati, G. 2, 333). Liquid, smelling like di-
chloro-acetal. Miscible with alcohol and ether.
By heating with water or H2SO4 it is resolved
into chloral and alcohol. Hot alkali has no
action. HNO3 gives tri-chloro-acetic acid. A
solid isomeride is described under CHLOBO-AOEiia
ALDEHYDE. "
Allyl ether CCl,.CH(OH)(OC3H5). Chloral
allyl-alcoholate. [21°]. (116°). From chloral
and allyl alcohol. Needles (Oglialoro, B. 7, 1462).
Acetyl derivative CCl3.CH(0Ac)(003Hs).
(106°) (Oliveri, G. 14, 13).
Isoamyl ether CClj.CH(0H)(005H„).
Chloral amyl-alcoholate. [56°]. (146°). S.G.
(liquid) SSi 1-234.
Cetyl e<;iflrCCl,.CH(0H)(C,3H3,). Chloral
eetyl-alcoholate. Very small needles.
Ethylene ether
CCl3.CH(0H).0CjH,0.CH(0H).CCl3. Chloral
glycolate. From chloral and glycol (Henry, B.
7, 762).
Isomeride of chloral hydrate. Chloral
mixed with glacial HO Ac and evaporated quickly
is converted into an isomeride of chloral hydrate
[80°], although the same solution when evapo-
rated slowly deposits ordinary chloral hydrate
[57°] (V. Meyer, B. 6, 449 ; A. 171, 74).
Heta-ohloral (02ClsH0)„. Formed by leav-
ing chloral to stand with H^SO,. Chloral that
has been freed from ^11 traces of H^SO, by dis-
tillation over BaO remains liquid for years
(Byasson, 0. B. 91, 1071). Amorphous soUd,
insol. water. HNO3 oxidises it to tri-chloro-
acetic acid. Alkalis form formate and chloro-
form. At 180° it is converted into ordinary
chloral (Kolbe, A. 54, 183). Trimethylamina
also polymerises chloral.
Paraohloral (C2Cl3H0)„. (240°). Formed,
together with tetra-chloro-ethylene, by treating
chloral with Al^Clj (Combes, A. Ch. [6] 12, 268).
Liquid; oxidised by HNOj to tri-ehloro-acetio
acid.
' Para-chloralide ' (CjjCl3H0)„. (182°). S.G.
i* 1'577. An isomeride of chloral said to be
formed by the action of chlorine on methyl
alcohol (Cloez, A. Ill, 178).
CHLOEAIIDE CsH^CljO,
i.e. CCl3.CH<;°-^0>CH.CCl,.
Tri-ehloro-ethylidene tri-chloro-lactate, [116»],
CHLOKHYDRIO ACID.
(273°). V.D. 11-3 at 300° (oalo. 11-2). Formed,
together with metachloral, by the action of
E2SO4 on chloral. Also by heating chloral vnth
' tri-ohloro lactic acid at 150° (Wallaoh, A. 193, 1 ;
B. 8, 1578).
Preparation. — Chloral hydrate (1 vol.) is
heated at 90° with a mixture ot cone. H^SO,
m vols.) and fuming H^SO, (1 J vols, of S.G. 1-85)
in a flask with inverted condenser until crystal-
lisation begins in the neck of the flask. The
contents are shaken till cold, and then poured
into water. The insoluble chloralide is washed
with water and recrystallised from ether or
chloroform (Otto, A. 239, 262 ; cf. Stadeler, A.
61, 104 ; Grabowsky, B. 8, 1433 ; Kekulfi, A. 105,
293).
Properties. — Monoolinio prisms (from ether).
Insol. water, si. sol. cold alcohol. Distils without
decomposition. Boiling KOH splits it up into
chloroform and formic acid. Alcohol at 150°
gives chloral alcoholate and ethyl tri-chloro-
lactate [67°]. Zn and HCl in alcoholic solution
reduce it to aldehyde and di-chlor'o-acrylic acid.
PCI5 forms an oil OsHCljOj. S.G. f 1-7436
(Anschiitz a. Haslam, A. 239, 300).
CHLORAITIL v. Tetba-chiiObo-quinone.
CHLOB-AKILIC ACID v. Di-ohlobo-di-oxy-
QUmONB.
CHLOBATES and FEBOHICBATES— SaZto
of chloric and perchlorio acids, v. Chiiobine,
OZY-AOIDS OT.
CttLOBHYDEIC ACID. HCl (Bydrochloric
acid. Hydrogen chloride. Muxiatic add gas).
Mol. w. 36-37. [-112-5°] (solidifies at -115-7°)
(Olszewski, M. 5, 127). V.D. 18-2. S.H.p.
(13°-100°) (equal mass of water = 1) -194
(Strecker, W. 17, 85) ; (27°-214°) -1867 (Eeg-
nault, Acad. 26, 1). S.H.v. (equal mass of
water = 1) -1304; (equal volume of air =1) -975
(Clausius, Mechan. WOrmetheorie, 1, 62 [1876].
g^gy (20°) 1-389; (100°) 1-4 (Strecker, W.
19, 85; experimentally determined). C.E.
(0°-33°) V, = V„ (l + at+bf), values of a for
HCl + 6-5H20 = -000446; for HCl + 50HjO =
-000 0625; values of 6 for HCl + 6-5H2O =
•000 000 43 ; for HCl + 50HjO = -000 008 71 ; for
HCl + 200HjO = -000 0153 ; for HCl + 200HjO =
•000 009 768 (Marignac, A. Sw^l. 8, 335). S at
760 mm. (0°) 503; (4°) 490; (10°) 470; (20°) 440;
(24°) 427; (36°) 396 :.(44°) 377 ; (48°) 367 ; (60°)
342. S. at 0° with varying pressure (60 mm.) 374 ;
(100 mm.) 400; (200 mm.) 431; (300 mm.) 450;
(400 mm.) 465; (600 mm.) 487; (800 mm.) 507;
(1000 mm.) 522 ; (1300 mm.) 545 (Bosooe a.
Dittmar,.^. 112, 328 ; v. also Deicke, P. 119, 156).
S. (alcohol, S.G. ^836) 327 (Pierre, A. Ch. [3]
81, 185). Vapour-pressure of liquid HCl ( - 73°)
1368 mm. ; ( - 51°) 3800 mm. ; ( - 30°) 8056 mm. ;
(0°) 19912 mm. (Faraday, T. 1845. 155). H.F.
[H, 01] = 22,000 ; [H, CI, Aq] = 39,315 (Th. 2, 20).
Critical point = 51^25° (AnsdeU, Pr. 30, 117).
S.G. liquid HCl (0°) -908, (7-6°) -873, (33°) -748,
(47-8°) -619 (A.). Coefficient of compressibility
(liquid HCl) for pressure from 62-8 to 208^19
Btmos. at 47° = -00166, at 33° = -00096, at
16-85° = -00062, at 6-7° =-000397 (A).
OcDwrrence. — In the gases of volcanoes, and
in streams issuing in volcanic districts (Bnnsen,
P. 83, 197). In the gastric juice of mammals
(Boedeker a. Troschel, B. B. 1854 486). An
aqueous solution of HCl has been known for
many centuries; the gas was first prepared
approximately pure by Priestley in 1774. The
acid was thought to be the oxide of an unknown
element, rnurmm,, until Davy proved in 1810
that it was a compound of H and CI.
Formation. — 1. By the action of diffused
sunlight on a mixture of equal volumes H and
CI. The mixture is best prepared by electro-
lysis of cone. HClAq, using carbon electrodes
(Boscoe, O. J. 8, 16). Combination occurs ex-
plosively in direct sunlight, or in electric, or
magnesium, light, or in the light produced by
burning NO in CSj vapour. Combination may
also be caused by heating to 150°, or by bring-
ing the gases into contact with Pt black, or by
absorbing them in charcoal. The gases do not
combine in the dark at ordinary temperature.
For details regarding the rate of combination by
exposure to light v. Chemical chaiige,vo1. i. p. 749.
2. By the action of CI on HjO in sunlight ; or
CI on HjS, HI, turpentine, and many other
organic compounds.— 3. By the action of
HjSOjAq or other acid on various metallic
chlorides. — 4. By the action of superheated
steam on MgClj, or on CaClj mixed with sand.
Preparation. — 1. By adding to 100 parts
pure NaCl, in a flask with an exit tube and
safety funnel, about 170 parts pure H2S04Aq,
prepared by diluting the cone, acid with | to I- its
weight of HjO and cooling, and gently warming.
The gas is passed through a little cone. HClAq,
and then dried by CaCI^; it is collected over
Hg, or by downward displacement of air. If
the materials react in the proportionsNaChH^SO,,
NaHS04 and HCl are formed at ordinary tem-
peratures ; then adding NaCl and strongly heat-
ing, NaHSOl and NaCl give Na^SOf and HCl.
If HClAq is to be prepared, the gas is led into
cold water, the exit tube passing only a little
way under the surface: the HClAq may be
purified by redistillation in contact with a little
Cu (to remove CI), after standing vrith pure
SnClj (to remove As), {v. Bettendorff, Z. [2]
5, 492 ; Zettnow, D. P. J. 205, 247 ; Hager, Fr.
1872. 306 ; Oster, Fr. 1872. 463 ; Houzeau,
A. Ch. [4] 7, 484 ; Eeinsch, J. pr. 24, 244 ; Otto,
B. 19, 1903).— 2. By dropping cone. HjSOjAq,
through a tube with glass stop-cock, into a flask
about one-third filled with commercial HClAq ;
the liquid gets warm and all the HCl except
about -82 p.c. is evolved (P. Hoffmann, B. 1, 272).
Liquid HCl may be prepared on a small scale
by placing a few pieces of NH4CI in the closed
end of a W shaped tube, running a little cone.
H2SO4 by means of a bent funnel tube into the
second bend of the tube, closing and thickening
the open end, and, after cooling, allowing the
acid to flow on to the NH4CI, and cooling the
other limb of the tube. After a little the limb
containing the reacting bodies is gently warmed
when liquid HCl collects in the cooled limb (Davy
a. Faraday, T. 1823. 164).
Properties. — HCl is a colourless gas with
most irritating, acrid odour ; it fumes in moist
air. The dry gas does not redden litmus paper.
At 10° under pressure of 40 atmospheres HCl
condenses to a colourless liquid (Faraday, T.
1845, 165). HCl is largely absorbed by water
with production of much heat; [ECl,Aq] =
B
CHLORHYDRIC ACID,
17,314 {Th. 2, 19). The solution is strongly acid ;
the affinity is taken by Ostwald as 100 (v.
AxvmiiY, vol. i. p. 75). When heated, cone.
HClAq gives ofi HOI and SjO; the tempera-
ture rises to 110° at mean barometric pressure
when a liquid S.G. l-l and containing 79'8 p.o.
HjO and 20-2 p.c. HGl distils over unchanged.
This composition corresponds with the formula
HOl.SHjO ; but it is not probable that the liquid
is a definite hydrate ; theB. P. and composition
of the liquid vary with the pressure. The follow-
ing numbers give the B. F. of BClAq, and the
composition of the liquid remaining in the retort,
at various pressures (Bosooe a. Dittmar, A. 112,
328 ; V. also Bineau, A. Ch, [3] 7, 257) :—
F.c. HCl in residual liquid.
22-8
22-1
21-7
20-9
20-2
19-1
18-1
B.P.
62»
76
84
97
110
Pressure in mm.
100
200
300
490
760
1520
2280
If dry air is passed into cone. HClAq the
liquid loses HCl ; the residual liquid has a con-
stant composition for a specified temperature.
The following numbers give the composition
of the HClAq remaining at t° after passage of
dry air until HCl ceases to come off (Boscoe a.
Dittmar, A. 112, 328) :—
Add of Sp.
Gr. 1-2.
p. ct.
1°
P.c. HOI.
1°
P.O. HOI.
f
P.O. HCl
0"
25-0
35°
23-9
70°
22-6
5
24-9
40
23-8
75
22-3
10
24-7
45
23-6
80
220
15
24-6
60
23-4
85
21-7
20
24-4
55
23-2
90
21-4
25
24-3
60
23-0
95
21-1
80
24-1
65
22-8
100
20-7
The following table (Boscoe a. Dittmar) shows
that the liquid obtained by passing air into
HClAq at a specified temperature has, in many
oases, the same composition as the liquid which
boils at that temperature under a certain pres-
Fres. in
iSM.
100
210
300
380
490
B.P.
P.C. HOL
Temp, with
air-stream.
61°-62
22-8
62°
76 -77
22-1
77
84 -85
21-7
85
91
21-3
91
97
20-9
98
P.O. HOL
22-9
22-2
21-7
21-4
21-1
The S.G. and composition of HClAq are given
in the following table (Ure). Temp. 15°.
Acid of Sp.
Gr. 1-2.
p.ct.
Specific
Gravity
Ohlorine p.o.
HCl P.O.
.100
1-2000
39-675
40-777
99
1-1982
39-278
40-369
98
1-1964
38-882
39-961
97
1-1946
38-485
39-554
96
1-1928
38-089
39-146
95
1-1910
37-692
38-738
94
1-1893
37-296
38-330
93
1-1875
36-900
37-923
92
1-1867
36-503
37-516
91
1-1846
36-107
37-108
90
1-1822
36-707
86-700
89
88
87
86
85
84
83
82
81
80
79
78
77
76
• 75
74
73
72
71
70
69
68
67
66
65
64
63
62
61
60
59
58
57
66
66
54
53
52
61
60
49
48
47
46
46
44
43
42
41
40
39
38
37
36
35
34
33
32
31
30
29
28
27
26
25
24
23
Speciflo
Gravity
1-1802
1-1782
1-1762
1-1741
1-1721
1-1701
1-1681
1-1661
1-1641
1-1620
1-1599
1-1578
1-1557
1-1536
1-1515
1-1494
1-1473
1-1452
1-1481
1-1410
1-1389
1-1369
1-1349
1-1328
1-1308
1-1287
1-1267
1-1247
1-1226
1-1206
1-1185
1-1164
1-1148
1-1123
1-1102
1-1082
1-1061
1-1041
1-1020
1-1000
1-0980
1-0960
1-0939
1-0919
1-0899
1-0879
1-0859
1-0838
1-0818
1-0798
1-0773
1-0758
1-0738
1-0718
1-0697
1-0677
1-0657
1-0637
1-0617
1-0597
1-0577
1-0557
1-0537
1-0517
1-0497
1-0477
1-0467
Chlorine p.o.
35-310
34-913
34-617
34-121
38-724
33-328
32-931
32-635
32-136
31-746
31-343
30-946
30-560
30153
29-767
29-361
28-964
28-567
28-171
27-772
27-376
26-979
26-583
26-186
25-789
25-392
24-996
24-599
24-202
23-805
28-408
28-012
22-615
22-218
21-822
21-425
21-028
20-682
20-235
19-837
19-440
19-044
18-647
18-250
17-854
17-457
17-060
16-664
16-267
15-870
15-474
16-077
14-680
14-284
13-887
13-490
13-094
12-697
12-300
11-908
11-506
11-109
10-712
10-316
9-919
9-522
9-126
HCl p.a.
36-292
35-884
36-476
35-068
34-660
34-262
33-846
33-437
33-029
32-621
32-213
31-806
31-398
30-990
30-582
30-174
29-767
29-359
28-961
28-544
28-136
27-728
27-821
26-913
26-505
26-098
25-690
25-282
24-874
24-466
24-058
23-050
23-242
22-834
22-426
22-019
21-611
21-203
20-796
20-888
19-980
19-572
19-165
18-757
18-869
17-941
17-534
17-126
16-718
16-310
15-902
15-494
15-087
14-679
14-271
13-863
13-456
13-049
12-641
12-233
11-825
11-418
11-010
10-602
10-194
9-786
9--37S
OHLOKHYDRIO ACID,
Aoid of Sp.
Gr. 1-2.
p. ot.
Speciflo
' Grarity
Chlorine p.o.
HCl p.o.
22
1-0437
8-729
9-971
21
1-0417
8-332
8-563
20
1-0397
7-935
8-155
19
1-0377
7-538
7-747
18
1-0357
7-141
7-340
17
1-0337
6-745 ,
7-932
16
1-0318
6-348
6-524
15
1-0298
5-951
6-116
14
1-0279
5-554
6-709 .
13
1-0259
5-158
5-301
12
1-0239
4-762
5-893
11
1-0220
4-365
4-486
10
1-0200
3-908
4-078
9
1-0180
3-571
4-670
8
1-0160
3-174
3-262
7
1-0140
2-778
3-854
6
1-0120
2-381
3-447
5
1-0100
1-984
2-039
i
1-0080
1-588
2-631
3
1-0060
1191
1-224
2
1-0040
0-795
1-816
1
1-0020
0-397
1-408
Kolb {D. P. J. 204, 322) gives the following
labia : —
P.O. HCl
atO°.
100 parts acid at 16° contain
SM.
Acid ol
Acid of
Acid of
HOI
20°
£eaum6
81° B.
32° B.
1-000
0-0
0-1
0-3
0-3
0-3
1-007
1-4
1-5
-4-7
4-4
4-2
1-014
2-7
2-9
9-0
8-6
8-1
1-022
4-2
4-5
14-1
13-3
12-6
1-039
5-5
6-8 .
18-1
17-1
16-2
1-036
6-9
7-3
22-8
21-6
20-4
1-044
8-4
8-9
27-8
26-2
24-9
1-052
9-9
10-4
32-6
30-7
29-1
1-060
11-4
120
37-6
35-4
33-6
1-067
12-7
13-4
41-9
39-5
37-5
1-075
14-2
15-0
46-9
44-2
42-0
1-083
15-7
16-5
51-6
48-7
46-2
1-091
17-2
18-1
66-7
53-4
50-7
1-100
18-9
19-9
62-3
58-7
55-7
1-108
20-4
21-5
67-3
63-4
60-2
1-116
21-9
23-1
72-3
68-1
64-7
1-125
23-6
24-8
77-6
73-2
69-4
1-134
25-2
26-6
83-3
78-5
74-5
1-143
27-0
28-4
88-9
83-8
79-6
1-152
28-7
30-2
94-5
89-0
84-6
1-167
29-7
31-2
97-7
92-0
87-4
1-161
30-4
32-0
100-0
94-4
89-6
1-166
31-4
330
103-3
97-3
92-4
1-171
32-3
33-9
106-1
100-0
94-9
1-175
33-0
34-7
108-6
102-4
97-2
1-180
34-1
35-7
111-7
105-3
1000
1-185
35-1
36-8
115-2
108-6
103-0
1-190
36-1
37-9
118-6
111-8
106-1
1-195
37-1
39-0
122-0
115-0
109-2
1-199
380
39-8
124-6
117-4
111-4
1-205
39-1
41-2
130-0
121-5
116-4
1-210
40-2
42-4
132-7
125-0
119-0
1-212
41-7
42-9
134-3
126-6
120-1
Eremers {P. 108, 115) gives a table by which
the S.G. Of HClAq can be found at a tempe-
rature other than 19-5° v/hich temperature is
taken as normal. (See table on next page.)
Thus, an acid containing 25-5 p.c. HCl has
S.G. = 1-101 at the normal temp. (W-6°), at 40°
the S.G. will be j^^^ = 1-092, at 100° the S.G.
will be i.noggiT = 1-06. Thbmsen, using the num-
bers in Ure's table, gives the S.G. of HClAq
100 /lOO- 1-0765 j;\|,
100 -p Vl00--726i) /
at 15° as S.G. =,
where p = p.o. of HOI (P. Jubelband, 144).
Eeactions. — 1. Decomposed by heat, at about
1500°, into H and CI, which combine again on
cooling. If a silver tube kept cold by running
water is placed inside a porcelain tube in a
wind furnace, and HCl is passed through the
latter tube, the free CI combines with the Ag, and H
remains (Deville, C. B. 60, 317). — 2. Moist, but not
dry, HCl is decomposed by oxygen in presence of
sunlight (Eichardson, G.J. 51,801).-^3. Electric
sparks very slightly decompose HCl. — 4. Many
metals decompose HCl when heated in it, giving
chlorides and H ; metalUc oxides form HjO and
01 ; many metalUc peroxides also set free 01. —
6. HCl is not combustible — 6. Mixed with air
and passed through a hot porcelain tube, or
over hot pumice, HjO and 01 are formed {comp.
Chlobine ; Formation, No. 3). — 7. By the action
otplalAm/wm black on a mixture of 1 vol. HCl
with i vol. O water is formed (Henry, T. 1800.
188).— 8. HCl is completely decomposed by
sodium amalgam at the ordinary temperature.
(This is applied as a lecture experiment for
demonstrating the composition of HCl, by
Hofmann ; v. Einleitung in die moderne Chemie
(6th ed.), 73). — 9. An aqueous solution of HCl
exposed to air and sunlight evolves a little
01. — 10. Cone. HOlAq evolves only H and 01 on
electrolysis ; diluted with 9 vols, or more HjO,
O is also evolved. Biche (G. B. 46, 348) says
that by electrolysis of HClAq, HOlO^Aq is
formed.— 11. Cone. HOlAq heated to 200° with
amorphous phosphorus produces PH, and
HgPOtAq. — 12. An aqueous solution, of HCl is
decomposed by many metals with formation of
chlorides and evolution of H. Let this decom-
position be expressed by the equation B, + 2HCLAq
^BOl^Aq-hH,; then considered thermally this
is composed of the parts (1) — [HS OP, Aq],
(2) -^ [E, CV, Aq]. a?he value of (1) is about
79,000, but is less the less the quantity of
water used ; for very cone, solutions it is equal to
about 69,000 : if then the value of [B, CP, Aq]
is greater than 79,000 we should expect the metal
E to decompose dilute HOlAq ; if [E, OP, Aq] is
greater than 69,000 we should expect E to
decompose cone. HClAq. [E, OP, Aq] is greater
than 79,000 when B==E2, or other allsali metal,
Ag2, Ca, Ba, Sr, Mg, Od, Zn, Mn, Fe, Oo, Ni, Sn.
[B, OP, Aq] is less than 79,000 when E = Tl2,
Pb, Ou, Hg, Pd, Pt, or ^ Au^ ; these metals do
not decompose dilute HCIAq. Now [Pb, OP, Aq]
= 75,970, which is > 69,000; Pb decomposes
cone. HOlAq. The following quantities of heat
are produced, per 2 grams of H formed, by the
action of certain metals on HOlAq; these
numbers afford approximate values of the
relative intensities of the actions : Mg = 108,300 ;
CHLORHYDRIC ACID.
1
Temp. o£ 19-5°
S.G. 1-0401
S.G. 1-0704
S.G. 1-101
S.G. 1-133
S.&. 1-1608
8-9 p.c. HOI
16-6 P.O. HCl
25-5 P.O. HCl
35-8 P.O. HOI
40-6 P.O. HOI
0
0-99557
0-99379
0-99221
0-99079
0-98982
19-5
1-00000
1-00000
1-00000
1-00000
1-00000
40
1-00707
1-00781
1-00877
1-00990
1-01063
60
1-01588
1-01665
1-01794
1-01969
1-02108
80
1-02639
1-02676
1-02791 •
1-02986
100
1-03855
1-03801
1-03867
1-04059
Al = 79,920; Mn = 49,370; Zn = 34,210; Fe
= 21,320; Co = 16,190; Ni = 15,070; Sn = 2,510.
(Data from Thomsen) .—13. When dilute HClAq is
added to a dilute solution of a chloride of an
alkali, alkaline earth, or magnesian, metal, little
or no thermal change occurs; but when a
solution of chloride of Au, Ft, Fd, Hg, or Sn is
used a considerable quantity of heat is produced :
thus, [Au'iCl'Aq, 2HClAq] = 9,060. Several
acids containing H, 01, and Au, Pt, Hg, or Fd",
have been prepared as solids ; e.g. BLjFtOlj.eHjO,
HAuCl,.4HjO &c. There can be little doubt that
solutions of AuCl,, &c. in HClAq contain definite
acids ; the heats of formation of these acids have
been calculated from experimental data hj
Thomsen (Th. 3, 536; v. also the various
metals) :
C. B. 89, 705).— 3. HClAq forms acids with the
chlorides of Au, Pt, Fd, and Sn {v. Beactions,
No. 13). According to Ditte {A. Oh. [5] 22, 551)
some metallic chlorides, e.g. HgCl,, dissolve
in HClAq to form definite compounds, e.g.
HgCl,.H01.7H20 ; SbCl,.3HCl, &o.— 4. With
water to form HC1.2HP ; prepared, as very un-
stable crystals decomposing quickly in air, by
passing HCl into HClAq at —22°; crystals
separate, and the temperature suddenly rises
to - 18° (Pierre a. Puohot, G. B. 82, 45, v. also
Berthelot, A. Ch. [S] 14, 368).
Thomsen has measured the heat of dilution of
HCl.jiH^O with mHjO. Assuming that when re = 1
the HjO is in combination with HCl forming the
hydrate HOl.H^O, then the heat of dilution of
HCLHjO is a continuous hyperboUo function of
R
[E, CIS 2HCIAq]
E
Sn
81,000
Sn
Hg
61,780
Fd
Fd
47,920
Pt
Ft
41,830
[E, CI*, 2HClAq]
156,920
72,940 (?)
84,620
E
Aa
[E, Cl», HOlAq]
31,800
The heats of neutralisation of these acids are the
same as that of H^Cl^Aq, viz. 2 x 13,740 {v. also
Gold, Mebc0ki,FaiiLabium, Platindm, Tin). — 14.
HClAq dissolves many metallic oxides; most
peroxides evolve CI; ca/rbcmates of the alkali and
alkaline earth metals, and of the heavy metals
except Ag, dissolve with evolution of CO^ ; most
metallic sulphides are decomposed and HjS pro-
duced.— 15. Heated with bromic or iodic acid,
H2O and BrCl or ICl are formed.— 16. With
chloric or hypochlorous acid, and the salts of
these acids, CI is evolved (v. further ohlobio
ACn> AND CKLOBATES, and HYPOCHIiOBOUS ACID AND
HYFOCBiiOBiTES, Under CbIiOBINE, ozy-acids of,
p. 15). — 17. When cone. HCIAq is mixed with
cone, aqtteous nitric acid a yellow liquid is
formed which dissolves Au, Ft, &c. metals
which are insoluble in either HCIAq or HNO,Aq.
This liquid is known as aqtia regia ; its solvent
action is due to the presence of 01 and NOCl ;
HNOaAq-f3HClAq = 2Hj,OAq + NO01 + Clj. By
the action of agiia regia on metals chlorides
are formed; e.g. 2HN03Aq + 6HCLAq + 3Cu
= SCuCljAq + 2N0 -1- 4H20Aq.
According to Gore (P.M[4] 29, 541) liquid HCl
does not (ict on metals, except Al which dissplves
with evolution of H ; it has also no action on
many oxides, sulphides, and carbonates, which
are decomposed by HCIAq.
Combinations. — 1. HCl and NHj combine
when mixed to form NH^OI ; [NH'.HCI] = 41,900
{Th. 2, 75).— 2. HOI and FHj combine to form
FHjOI, at 14° under pressure of 20 atmospheres,or
at —30 to -35° at the ordinary pressure (Ogier,
the quantity of 'H.jd added: the equation, heat of
dilution of HCl.jiHjO with mH,0 = (~- -i_ \
\n n + m,<
11,980, gives values which agree very closely
with the observed results, starting with to = 2-62,
and varying to from 49 to 200 ; the constant
11,980 is found from the experimental results.
The above formula gives the heat of dilution of
HOI with 300 HjO as 11,940, and the observed
value was 17,316; the difference, 5376, re-
presents the quantity of heat produced by the
union of HCl with HjO to form the hydrate
HCI.HjO. Thomsen's results do not indicate the
formation of any hydrate except HCl.HjO ; it is
fairly probable that the reactions of HCIAq with
hydroxides, metals, &e., are the reactions of the
compound HClHjO (? = Hj01.0H), and not of
HCl {Th. 3, 11-113; and 68-72) {v. further
Ohlobides). m. M. p. M.
CHLOiRIC ACID v. Chlobihe, oxy-aoids op.
CHLOBIDES. Binary compounds of CI with
more positive elements ; i.e. with any element
except F or 0. 01 forms compounds with all
elements except P; it combines directly vrith
all except F, 0, N, and C : much heat is usually
produced during the combination, thus FESCl^
= 211,220; [Ca,Cl''] = 169,820; [Zn,Cn = 97,210;
[FeSClT = 192,080 ; [Cu,OIT = 61,630 ; [Au,ClH
= 22,820 ; [H,01] = 22,000 ; [1,01] = 5,830 ;
[SS01»] = 14,260; [F,CI»] = 75,300,&o. (Thomsen))
Many metallic chlorides are produced by the
action of 01 on the oxides e.g. ZnCl„ PbClj,
MgOIj, BaCI,; lower oxides of metals which
CHLORIDES.
9
Jorm two oxides — e.g. FeO, Sb^O, — are usually
partly chlorinated and partly oxidised by CI, the
higher oxide being usually eventually changed
to chloride; all metallic oxides are converted
into chlorides when mixed with charcoal and
heated in a stream of CI, thus Cr^O, + 3C + 6C1
= SCO + Oracle- MetaUio chlorides are also
formed by the action of Cl on many bromides,
iodides, fluorides, and sulphides: they are
usually obtained by the action of ECllq on
metals, metaUio oxides, hydroxides, or carbon-
ates ; in some cases agua regia (v. CaLOBBTDKio
acid; Beactions, No. 17) is employed, e.g. to
form FtCl,. Non-metals, except C, N, O, and F,
combine directly with Cl. Nitrogen chloride,
NCI3, is extremely explosive, it is formed by
the action of Cl on various ammonium salts
in solution; CC1„ CjCl^, C^Clj, and OjCla, are
formed indirectly from various carbon com-
pounds; CljC is formed by the action of Cl on
HgO.ClOj by the action of HjSO^Aq on KCIO3 ;
no compound of Cl with F is known. Most
non-metallic chlorides are gaseous ; they are
decomposed by E^O forming acids and HCl, e.g.
PCI, -I- SHjO -I- Aq = H3P03Aq + SHClAq ;
SiCl, + 3HjO + Aq = H^SiOj + 4HClAq.
Most of the metallic chlorides are gasifiable
without decomposition; some yield lower chlor-
ides on heating, e.g. CuCl, gives Cu^Cl, and Cl ;
a few are completely decomposed into Cl and
metals, e.g. FdCl,. A few chlorides are in-
soluble or nearly insoluble in water — the chief
are AgCl, HgCl, Cu^Clj, PtClj, AuCl— the others
are soluble in water. Many metallic chlorides
are decomposed by water, forming oxychlorides
and HClAq, e.g. BiCl,, SbCl,; on evaporating
AICljAq, ZnOUAq, MgOljAq, and a few other
solutions of chlorides, decomposition into oxide
and HCl or into oxychloride, occurs. Heated in
superheated steam chlorides of alkali metals, Ba
and Hg, are undecomposed ; the others form
oxides and HCl (Eunheim, J. 1861. 149). Most
metallic chlorides are unchanged when heated
in dry air ; some, however, form oxychlorides,
e.g. FeCl,, CuCL, BiClj ; very many are de-
composed by heating in moist air. The chlorides
of the alkali, alkaline earth, and earth, metals
are not reduced by heating in H; ihe other
metallic chlorides are reduced ; some chlorides
not reduced by H, e.g'. AICI3, MgClj, are dechlor-
inated by heating with K or Na. Very many
chlorides are reduced to metal by CO. Some
ohloridesof heavy metals, e.g. AgCl, are partially
decomposed by digestion with aqueous solutions
of bromides of alkali, alkaline earth, or mag-
nesian, metals {v. Potilitzin, B. IS, 1522 ; also
Thorpe a.Bodger, C. J.Proc. 1887-88, 20). Many
metallic chlorides are partly decomposed when
heated with an equivalent quantity of Br to
270°-300'' {v. PotUitzin, B. 14, 1044 ; 15, 918 ;
16, 3051. For action of Br on AgCl in presence
of HjO, V. Humpidge, B. 17, 1838). Metallic
chlorides are decomposed, with evolution of Cl,
by heating with B^Og, SiOj, or P2O5, in presence
of steam. Aqueous acids decompose metallic
chlorides, forming HCl, or in the cases of easily
reducible acids — e.g. HNO3 — evolving Cl; Cl
is also evolved when cone. H^SOj is used in
presence of peroxide of Pb, Mn, Cr, &o. Heated
with KfixOt and cone. BijSO<, metallic chlor-
ides form CrOsCL,, which may bo easily con-
densed to a red liquid ; by the action of NH,Aq
on this liquid (NHJjCrOjAq is formed (this
reaction may be applied to detect chlorides in
presence of bromides).
Some metallic chlorides, especially those of
Hg, Au, Pt, Pd, and Sn, combine with HCl to form
acids (v. Celobhvdbic acid ; Beactiona, No. 13) ;
many form double salts with other metallic chlor-
ides, especially the chlorides of the less posi-
tive, with those of the very positive, metals ; e.g.
SnCIj.2KCl.H2O, HgCl3.2KOl.HjO, Pt01,.2NH^Cl,
&B. Many chlorides of the more negative metals,
e.gr. SbClj, BiCl,, SnCl^, &c., combine with oxides
of the same metals to form oxychlorides : some
metallic chlorides, e.g. HgCl,, combine with
sulphides of the same metals to form sulpho-
chlorides. Compounds are also known of
chlorides of some of the more negative metals
with non-metallic chlorides, e.g. SnCl4.PCl5,
SnCl,.2SCl4, &a. Many metallic chlorides, e.g.
CaCl„ AlCl,, AgCl, CoClj, CrCl,, HgOlj, PtClj,
combine with NH3 to form stable compounds
(v. AuMOHiuu ooMFoxnnJs ; and, in more detail,
the various metals, especially Chbouidu, CobaiiT,
Copper, Mercury, Plaukdm).
Thomsenhas considered the isomorphism of the
hydrated metallic chlorides (v. Th.i, 430). Many
chlorides produced by the action of HClAq on
metals or metallic oxides contain water of crystal-
lisation; they may be divided into the four groups :
(1) ECI3.2H2O; (2) BCL,.4H30; (3) EClj.eHjO;
(4) BCI3.8H2O ; when B= an atom of a divalent,
or two atoms of a monovalent, metal. The
members of group (1), where B = Ba, Cu, or
MnHg, crystallising in the trimetric system, are
isomorphous with many anhydrous sulphates,
formates, perchlorates, periodates, and perman-
ganates, e.g. BaSO,, PbSO,, Ba(CH02)2, KC10„
KIO4, KjMn^jOg, &o. The members of group (2),
where B = Na2, Mn, Di, Fe, crystallising in the
iuonoclinic system, are isomorphous with sul-
phates and formates containing 2H2O, e.g. with
CaSO,.2H30, Zn(CH02)j2H20. Group (3) com-
prises (a) monoclinio chlorides where B = Mg,
Ni, Co, or Mn, these are most probably iso-
morphous with Cu(CH02)j.4H20, MnS04.4Hj0,
and Ba(S03)2.4H20 ; and (&) hexagonal chlor-
ides where B = Ca or. Sr, and also the class
B"B''Cl3.6H20 which includes salts derived from
HjPtCl, and H2SnCl3, these are isomorphous
with many sulphites and double nitrates with
4H3O, e.g. Sr(S03),.4H30, CejMg,(N03)3.4H30,
LaNi(N03)2.4H20, &b. Group (4) contains
only one chloride, C0CI2.8H2O; it is isomor-
phous with the chlorates of Co, Cu, and Ni, and
with the hypophosphites of Co, Fe, Mg, Ni, and
Zn, containing 6H2O. Bach group of chlorides
is isomorphous with other salts containing
2H2O less than the chlorides. Thomsen con-
cludes that the 2H2O may be best regarded as
forming part of the acid radicle; he would
represent the four groups of chlorides as
(1)B(H2C10)2; (2) B(H2C10)2.2H20 ;
(3) E(H3C10)2.4H20; (4) E(H2C10)2.6H20: all
being derived from the acid H2CIOH, which
possibly exists in an aqueous solution of HCl
{v. Chlobhydeio acid ; Combinations, No. 4).
Armstrong {B. A. 1885 Meeting; Presidential
address to Section A.) suggests that the name
ohlorhydrio acid should be given to the acid
present in an aqueous solution of HCl, and that
10
CHLORIDES.
ECl itself should always be called hydrogen
chloride. M. M. P. M.
GHLOSIDE OF LVM.E— Bleaching powder,v.
HYPOOHLOEITES Under CHIiOEINE, OXT-ACLDS OF
(p. 17).
CHLOBISES, OBGAKIC v. Chlobo- com-
pounds.
GHLOBOE. CI. {Dejahlogisticated muriatic
acid gas.) At. w. 35-37. Mol. w. 70-74. (-33-6°
at 760 mm.) (Begnault). Solidifies at about
-102° (Olszewski, M. 5, 127). S.G. (liquid)
1-33 (Faraday, T. 1823, 160 a. 198). V.D. 35-8
(v. ProperUes,y. 11). S.H.p. (13° -202°) (equal
mass of H„0 = 1) -1241 (Begnault, Acad. 26,1).
S.H.v. (equal mass of H20 = l) -0928; (equal
volume of air = l) 1-35 (Clausius, Mechan.
Warmetheorie, [1876] 1, 62). ^^ (20° - 34°)
1-323 (Streoker, W. 13, 20; experimentally
determined). Vol. absorbed by 1 vol. HjO at
760 mm. = 3-0361 - -046 1964 + -000 llO 7<^(Sch6n-
field, A. 95, 1). ^lzI x At. w. = 10-6 (Gladstone,
a
T. 1870. 9). Emission-spectrum; principal lines
are a group of 4 about 6670, followed by 9 others
and then by one with wave-length 4130 (Salet,
A. Ch. [4] 28, 24). Absorption-spectrum marked
by many irregularly distributed lines ; the violet
is nearly wholly absorbed (Morren, C. B. 68,
376; Gernez, C. B. 74, 660).
Chlorine was discovered by Scheele in 1774
and supposed by him to be hydrochloric acid de-
prived of phlogiston. BerthoUet regarded it as
oxygenated hydrochloric acid; chlorine and hydro-
chloric acid were long supposed to be oxygen
compounds of an unknown element. In 1809
Gay-Lussac and Th^nard, showed that chlorine
behaves like an element ; in 1810 Davy estab-
lished the elementary character of the body and
gave it the name chlorine (x^oipiii = yellow-
green) (Scheele, Opusc. 1, 247 ; BerthoUet, 4cad.
1785. 286 ; Davy, T. 1810 ; Gay-Lussae a.
Thtoard, G. A. 35, 8; A. Ch. 91, 96).
Oceurrenoe. — Never free ; but in combination
with very many metals in various rooks ; in
sea-water as NaCl ; chlorides occur in plant-ash
and in many parts of animals.
FormaUon. — 1. By the action of cone.
HClAq on MnOj (Mn02 + 4H01Aq
= MnOljAq + 2HjO + Olj) ; or better by using
1 part MnOj, 2 parts HClAq (S.G. 1-14),
and 1 part cofto. H.,SO, diluted with its own
weight of water ' (MnOj + 2HClAq -i- H^SO^
= MnSO,Aq + 2HjO + Ol2). -y 2. By the action
of cone. H2SO4 on a, mixture of NaCl and
NaNOj ; the NOj produced is absorbed by
cone. HjSO, (2NaCl + 2NaN03 + 2H2S04
= 2NajS0, + 2N0j + 2H2O + CIJ (Dunlop,
D. P. J. 151, 48).— 3. By the action of a
porous substance, e.g. clay, on HCl mixed with
air. Deacon (C. N. 22, 157) soaks clay-bricks
in saturated CuSOjAq, and heats them to
370°— 400° in a stream of 5 vols, air and 4 vols.
HCl; CI is evolved {v. Deacon, C. J. [2] 10,
275). Probably CuCl^ is formed and decom-
posed to GU2CI2 and CI, and the Cu^Cl, is again
decomposed by the air to CuO and CI, the GuO
being changed to GuGl, by the HCl (Hengsen,
B. 9, 1674).
PreparaUon. — 1. 100 grams pyrolusite
(MnOj) free from carbonates are well mixed
with 130 grams NaOl, and placed in a capacious
flask ; a cold mixture of 125 o.c. cone. H^SO,
(S.G. 1-85) with 105 c.o. water is added. CI is
evolved ; after a time the flask is warmed in a
water bath ; about 80 grams of CI are obtain-
able from the above quantities. The CI carries
over with it a little HCl, and sometimes MnClj ;
it is passed through CuSOjAq (CuCljAq and
H2SO4 are formed) and then through water. If
dry CI is required the gas must be passed
through several tubes containing OaClj and'
through one or two long tubes filled with
pumice soaked in boiled H^SO,. The gas may
be collected by downward displacement, or
over warm water or saturated NaClAq. — 2.
Crystals of KfixJH, are acted on by cone.
HClAq in a capacious flask, the acid being
added little by little (14HClAq + K^CrjO,
= Cr^CljAq + 2KClAq + 7H2O + SQl^).— 3. Chlor-
ide of lime is decomposed by HClAq
(Ca(C10)2 + 4HClAq = CaOljAq + 2H.,0 + 2Cy.
Kammerer {B. 9, 1548) describes a lecture-
apparatus for the convenient preparation of
CI, based on this reaction. Dry chloride of
lime, intimately mixed with burnt gypsum,
is slightly moistened so that it can be rolled
with difficulty into balls between the fingers; ,
the mixture is powdered in an iron mortar
and then beaten into an iron frame 10-12 mm.
in height ; the frame is then covered with
oilcloth and very strongly compressed ; the com-
pressed plate is out into cubes, which are pre-
served in a stoppered bottle. When these cubes
are used in a Kipp's apparatus with HClAq of
S.G. 1-124 (free from H^SOJ diluted vdth its
own volume of water, a steady stream of chlorine
is obtained (Winkler, B. 20, 184).
Liquid Chlorine is prepared (Faraday, T.
1823. 160 & 198) by placing crystals of CUHjO,
thoroughly pressed between folds of paper
at 0°, in the closed end of a /\ tube, closing
the other end, placing the Cl.SHjO in water at
35°, and the other limb of the tube in a mix-
ture of snow and salt (v. also Biewend, /. pr.
15, 440). Mohr (A. 22, 162) places a mixture of
dry KHSO,, NaCl, and MuOj in the longer limb
of a A tube, and above this a layer of CaCl^;
the shorter limb is closed, and placed in a mix-
ture of snow and salt; the mixture in the
longer limb is then heated, and, when liquid CI
has collected in the other limb, is again cooled
to prevent re-absorption of the CI. The opera-
tion must be conducted in the dark, else HCl
andO are produced, and the tube is liable to be
broken. Liquid CI is solidified by surrounding
with liquid CjH, and lowering the pressure
(Olszewski, M. 5, 127).
Properties. — A greenish-yeUow gas, becoming
darker in colour when heated ; very irritating
odour ; liquefied at 15° under pressure of 4 atmo-
spheres (Faraday, T. 1823. 160&198); at 0° under
pressure of 6 atmospheres, and at 12-5° under
8J atmos. (Niemann). Liquid CI is dark yellow;
immiscible with water ; S.G. 1-33 ; B.P. - 33-6°
at 760 mm. ; non-conductor of electricity (Beg-
nault). Very poisonous ; even when mixed
with much air it attacks the mucous membranes
and causes irritation and even blood-spitting.
When working with CI, the nose and month
should be protected by a charcoal respirator, or
CHLORINE.
11
hj a oloth dipped in alcohol. Absorbed by
porous substances, e.g. charcoal, with production
of heat (d. Melseus, C. B. 76, 92) ; not combus-
tible in 0, but burns in E producing HCl. Dis-
solves in water with production of heat, [CP.Aq]
= 2600 {Th. 2, 400). Schonaeld gives these
data(A93„26; 95,8):—
1 vol. water absorbs x vols. CI at 760 mm.
t°
X
t°
X
t°
X
10
2-5852
21
2-1148
31
1-7104
11
2-5413
22
2-0734
32
1-6712
12
2-4977
23
2-0322
33
1-6322
13
2-4543
24
1-9912
34
1-5934
14
2-4111
25
1-9504
35
1-5550
15
2-3681
26
1-9099
36
1-5166
16
2-3253
27
1-8695
37
1-4785
17
2-2828
28
1-8295
38
1-4406
18
2-2406
29
1-7895
39
1-4029
19
2-1984
30
1-7499
40
1-3655
20
2-1565
Solubility is greatest at 10° ; chlorine-water is
therefore best prepared by leading CI into HjO
kept at about 10° and repeatedly shaking.
Solution of CI in H^O has smell of gaseous CI ;
it freezes at 0°, giving CI hydrate and ice {v. Com-
binations, No. 3) ; loses all CI on boiling (on loss
of CI from Cl-water at 100° in closed vessels, v.
' Pickering, G. 3. 37, 139) ; decomposes quickly
in direct sunlight into HCl and 0. The pre-
sence of HCl in Cl-water is detected by shaking
with Hg until the smell of CI is removed, filter-
ing, and testing' filtrate with blue litmus and
with AgKOjAq.
The atomic weight of CI has been determined
(1) by analyses, and determinations of V.D., of
many gaseous compounds, e.g. CIH, ClTl,
OljZn, ClaBi, C1,0, Cl^Ta, Cl^W, &o. ; (2) by
comparison of chlorides, &c., with isomorphous
bromides, iodides, &c. ; (3) by conversion of Ag
into AgCl by Berzelius (P. 8, 17) ; by conversion
of NaClOj and KClOj into NaCl and KCl by
Penny (K 129, 25) ; by conversion of KCIO, to
KCl, and KClOi to KOI, by Marignac {A. 44, 18) ;
by conversion of KClOj to KCl by heat, and by
decomposition of KCIO, by HCl, by Stas {fiecli.
118) ; by heating Ag in 01, by ppg. Ag solution
by gaseous HCl, also by HClAq, also by
NHjClAq, by Stas (Redh. 38, 42, 44) ; by reducing
AgClO, by SO.^q by Stas (2/ou«. iJ. 208).
The atom of CI is monovalent in gaseous
molecules. 01 acts as a very negative, acid-
forming, element; it appears to be positive to
0, and probably to F. Combines with all ele-
ments except F, directly with all except N, 0,
0, and F , with many elements combination
occurs at ordinary temperatures with production
of much heat [v. Celobides). Beplacement of
H in carbon compounds by CI is usually accom-
panied by production, or increase, of acidic
character; e.g. relative affinity of CHjCl.CO^H
is greater than that of CHa.CO^H («. Afi'initt,
vol. i. p. 83). Heats of formation, in solution,
of metallic chlorides are greater than those of
corresponding bromides or iodides; bromides are
wholly or partially decomposed, iodides are easily
decomposed, by 01. At least two oxides of 01 are
known as gases ; one oxy-acid, HCIO4, has been
obtained in separate and definite form {v.
Chlobises ; Halooen elements ; and HaiiOOEn
ELEMENISa BINABY COUPOtlNSS O?).
The S.G. of 01 gas at 200° was found by Lud-
wig to be 2-45 {air = l) [B. 1, 232). Many deter-
minations have been made by V. Meyer and his
pupils, using 01 prepared before and also during
the experiments ; the general result is that the
S.G. of 01 is very slightly, if at all, less at high
temperatures, 1000°-1400°, than at a red heat
(«. Langer a. Meyer, B. 15, 2769 ; also Crafts,
B. 16, 457) ; but that the S.G. of 01 formed in
the apparatus by heating PtClj at 1200°, is 2-05
(air = 1) in place of 2-45 calculated for 01^ (u.
V. Meyer, B. 13, 721). The determinations of
Jahn \B. 15, 1242) show that 01 does not attain
the S.G. calculated for 01, until it is heated to
about 240° above its B.P. ; the differences be-
tween the observed and calculated numbers are
however very small, much less than the differ-
ences in the case of Br (j. v.) (u. Halogen ele-
ments).
Beactions. — 1. 01 dissolves in water with pro-
duction of heat [CP.Aq] = 2,600 {Th. 2, 400) ; the
solution decoiQposes, rapidly in direct sunlight,
with formation of HCl and 0 ; according to
Popper (A. 227, 161) HOIO3 is also formed.
Chlorine water therefore acts as an oxidiser, e.g.
in bleaching (Poussaint, A. 137, 114). The
thermal value is, 2[H,C1, Aq] - [H^G] = 10,270
(Thomson). — 2. CI decomposes steam rapidly
when a mixture of the two is passed through a
red-hot tube. — 3. Aqueous solutions ot potash (or
soda) absorb 01, yielding KCl and KCIO in cold,
and KOI and KCIO3 in hot, solution : Ca(OH)j
absorbs 01 forming CaOCl.Cl. — 4. Aqueous am-
monia yields NH^Ol and N ; if 01 is in excess
chloride of N is formed. — 5. The more basie
metallic oxides are decomposed by 01, when dis-
solved or suspended in water, with formation
of metallic chloride and peroxide, or metallic
chloride and an oxygen compound of 01 (v.
Chlobtne, oxides op). Many metallic oxides
when heated in 01 give chlorides and 0 ; in
some cases, e.g. ALfl,, B^Oj, 0 is removed only
when 01 is passed over a hot mixture of the
oxide with carbon. — 6. All compounds of hydro-
gen, except HF, are decomposed by CI with
formation of HCl ; many at ordinary tempera-
tures ; e.g. HjP.HsAs, H^S, HI. — 7. All metallic
bromides, iodides, and sulphides are decomposed
either at ordinary or higher temperatures. —
8. Carbon compounds containing hydrogen are
usually easily decomposed by 01, with formation
of HCl, and frequently with separation of C;
turpentine e.g. burns in 01 with a deposit of
soot. Some vegetable colours are bleached by
01 by direct removal of H; in most cases, how-
ever, the action requires the presence of H^G
and is due to the 0 evolved in contact with the
colouring matter. (For the reactions of 01 with
Ag salts V. Krutwig, B. 14, 304.)— 9. An aqueous
solution of sodium thiosulphate is decom-
posed bv 01 ; the chief reactions are (1)
NaJSJ03Aq-^5H20■^8Cl
= Na^SO^Aq -I- 8HCLAq + H^SO^Aq ;
(2) Na,SAAq-)-2Cl + Hj0
= Na2S0,Aq-H2HClAq+ S; (3) 2Na AOjAq -f CI,
= Na2Sj0aAq + 2NaClAq. On dilution HjS is
evolved ; probably, 2Na2S203Aq
= Na^SjOjAq + Na^SAq ; and then
Na^SAq + 2HClAq (formed as in (1))
= 2Na01Aq + H,S (v. Lunge, B. 12, 404).— 10..
Many salis are decomposed by 01 with formation
12
CHLORINE.
cl aqueous solutious of HCIO : e.g.
Na2C03Aq + H20 + 2Cl2
=2NaClAq + 2HO0IAq + 00^;
CaCO, (suspended in H^O) + H^O + 201^
= CaCljAq + CO2 + 2H0ClAq : (o.Chlobinb, oxt-
AoiDs or). — 11. Iodine suspended in water is
converted into HIO3 : IjAq + 5C1, + 6H,0
=2HIO3Aq + 10HClAq.
CombmaUons. — 1. Directly with all elements
except 0, N, C, and F; indirectly also with
0, N, and C. In most oases much heat is produced
(v. ChiiObides). Dry Cl has no action on dry
Na (Wanklyn, C. N. 20, 271) ; K, Na, and Sb,
do not combine with liquid Cl at — 80° ; F and
As on the other hand combine readily (Donny a.
Mareska, A. 66, 160). The combination of Cl
and H takes place slowly in the dark, but very
rapidly and explosively in direct sunlight, in
electric light, in Mg light, or in the light pro-
duced by burning CS2 in NO; [H, Cl] = 22,000
(Thomsen). For more details regarding the com-
bination of Cl and H v. Chlobhydbio Acid, p. 5 ;
also Chkmioal uhanqe, vol. i. p. 749. — 2. Cl con-
densed in charcoal combines, without the aid of
beat or light, with sulphur dioxide to form SOjCl,
(Melsens, C. B. 76, 92).— 3. Cl combines with
water: when a saturated aqueous solution is
cooled to 0°, or when Cl is led into H^O kept
nearly at 0°, crystals of Cl.SHjO separate out
(Faraday, Q. J. S. 15, 71). This hydrate is
best prepared by passing Cl into a little water
in a flask surrounded by ice, tUI the water is
shanged to a thick yellowish magma ; and then
pressing strongly between thick layers of paper
kept at 0°. CLSHjO at -50° forms white tri-
metric octahedra, which may be sublimed (? with
partial decomposition) in a closed vessel filled
with Cl, the upper part being kept below 0°.
Cl.SH^O decomposes at ordinary temperatures
and pressures with evolution of Cland formation
of Cl water ; in a closed tube it separates into
Cl and HjO at about 35° ; on cooling to 15° or
80 the Cl.SH^O is re-formed (v. p. 10, Ligmd
chlorine) (compare Wohler, A. 85, 374).
Detection and Estimation. — Chlorine decom-
poses EIAq giving EClAq and lAq, the I is
detected by the blue colour it produces with
starch paste. Soluble chlorides ppt. Ag as white
AgCl from AgNOjAq. Solid chlorides when
heated with EjCr^O, and cone. E2SO4 produce
jaseous CrO^Clj which is easily condensed to a
reddish-brown liquid; bromides and iodides
under similar conditions give Br and I re-
spectively.
Chlorine in dilute aqueous solutions may be
estimated volumetrically (1) by determining the
mass of I (by means of standardised NajS^OgAq)
set free from EIAq by the Cl, or (2) by gently
warming in a closed vessel with excess of
NajSjOjAq — ^whereby part of the Na^S^Os is
changed to NaHSO^ — decomposing the remain-
ing NajSjOj by boilipg with HClAq, and esti-
mating the sulphate produced by the usual
methods. Chlorides, in solution, may be esti-
mated (1) by ppg. as AgOl, washing, drying,
slightly fusing, and weighing; or (2) volumetri-
cally by means of standardised AgNO^Aq, in
presence of a very little EjCrOjAq; the AgNQ,Aq
is added until the whole of the chlorine is ppd.
as AgCl, the completion of the reaction being,
determined by noticing the production of red |
AgjCrOi : the chloride ought to be present in
the liquid as alkali or alkaline-earth chloride ;
the liquid must be neutral to litmus. The re-
action of chlorides with EjCr^O, and cone.
HjSO, may also be. applied to the estimation
of 01 in presence of I and Br («. Dechan, C. /.
[2] 49, 682). M. M. P. M.
CHLOBINE, BROKIDE OF: better called
Bronxine chloride ; v. Bbouine.
CHLOBINE, CYANIDES OF: better called
Cyanogen chlorides ; v. Cyanooen.
CHLORINE, HYDEATE OF. C1.5HjO. Ob-
tained by passing Cl into HjO at 0° ; v. Chlo-
BiNE ; Combinations, No. 8.
CHLORINE, IODISES OF: ICl and ICl,:
better called Iodine chlorides ; v. Iodine.
CHLORINE, OXIDES OF. Chlorine and
oxygen do not combine directly. Two oxides of
Cl, CljO and CIO2, certainly exist ; a third is
usually described as Cl^O,, but it is probably a
mixture of ClO^ and Cl (v. Cblobine tbioxide).
They are all unstable bodies, easily decomposing
into their elements. Cl^O is the anhydride
of HCIO, but this acid is known only in dilute
aqueous solutions. The anhydride Cl^O cannot
be obtained from solutions of the acid; 01,0
is prepared by the action of CI on dry HgO.
The supposed CI2O3 is said to be obtained by
reducing HCIOjAq, generally by AS4OJ. ClOj is
not an anhydride of a definite acid ; it is obtained'
by the action of H^SO^Aq on EClO, ; on addition
of HjO, or EOHAq, it forms HClOaAq and
HClOsAq, or EClOjAq and EClOjAq. The hypo-
thetical anhydrides of HCIO, and HCIO4, viz.
CIjOj and Cl^O,, are unknown. The heat of
formation of CljO is negative ; [CP,0] = - 17,900
(Thomson). The heat of formation of the only
known oxide of I, viz. I^Oj, has a large positive
value [F,0'] = 45,000 (Thomson).
Berthelot discovered EClO, in 1786 ; it was
long known as oxidised potassium chloride.
Other compounds containing Cl and 0 were
prepared and examined by Chevenix (1802),
Stadion and Davy (1815), and by Balard (1834).
Millon in 1843 added much to the knowledge of
the oxy- compounds of Cl. In more recent times
Carius, Brandau, and Pebal have examined
these compounds. The body called by Davy
eu^hlorine, obtained by the action of HClAq on
ECIO9, and supposed by him to be an oxide of
Cl, has been proved to be a mixture of ClOj with
Cl. Millon's compounds CljO,, and CljO,, have
also been shown to be mixtures (H. Davy, T.
1815. 214; Gay-Lussac, A. Ch. 8, 408; Sou-
beiran, A. CK. 48, 113 ; J. Davy, N. Ed. P. J. 17,
49 ; MUlon, A. Ch. [3] 7, 298 ; Pebal, A. IT!, 1).
I. Chlobine monoxide. CljO. {Hypochloroua
anhydride.) Mol. w. 86-7. (5° at 738 mm.)
(GarzaroUi-Thumlackh, A. 230, 273). V.D.
43-5 at 10°. [Cl^O] = - 17,930 {Th. 2, 399). S.G.
2-977 (air = 1). Absorption-spectrum shows
bands in blue and violet (Gernez, C.B. 74, 803).
S. (0°) about 200.
Preparation. — Precipitated HgO is heated to
about 300° for some time, and cooled (Pelouze,
A. 46, 195) ; it is placed in a long tube sur-
rounded by water ; well washed and thoroughly
dried Cl is passed through the tube. The re-
action is HgO -H 2CI2 = HgClj + CljO ; the CljO is
passed into dry flasks; as each is filled it is
closed with a glass stopper which is then
CHLORINE, OXIDES OF.
IS
Dovered with paraffin. If liquid Cl^O is required
the tube containing EgO is connected with a Y
tube, the upper part of which is cooled to at
least —20°. Ladenburg (B. 17, 157) recommends
cooling by alcohol, the temperature of which is
reduced to —40^ by a smair ammonia-freezing
machine — dry test tubes surrounded by ice and
salt are placed under the Y tube, and a few
drops of CL;0 are collected in each tube. In
this way the principal reactions of liquid Clfi
may be demonstrated without danger (v. Laden-
burg, 2.C.). If crystalline HgO is used, no action
occurs between it and CI ; if ordinary ppd. HgO
is employed the action is too rapid, much heat
is evolved, and no GljO, but only 0, is obtained.
Properties. — Eeddish-yellow gas, with very
irritating odour : condenses at about - 20° to a
blood-red liquid which boils at about —17°
(Pelouze, A. Oh. [3] 7, 176). Both gas and
liquid are very easily decomposed, sometimes
with violent explosion, into CI and 0 ; pouring
the liquid from one glass vessel to another, or
contact with a scratch on the glass, may suffice
to bring about an explosion. Bise of tempera-
ture, or the action of electric sparks, causes the
gas to explode, with production of CI and 0
(Balard, A^ Ch. 57, 225; Gay-Lussac, C. B. 14,
927). The gas is said to decompose in sunlight
without explosion into CI and 0, the volumes of
these gases being as 2:1.
Beactimis and Combinations. — 1. Powdered
metals form chlorides and oxides, or oxychlor-
ides, frequently with explosion. — 2. Many me-
tallic oxides react with the gas to form chlorides
and higher oxides ; AgjO gives AgCl and 0. —
3. Phosphorus, Sulphwr, and Selenion, form
chlorides and oxides, with explosion. — 4. Hy-
drogen, in sunlight, decomposes the gas ex-
plosively, producing HCl and SjO. — S. Freshly
heated carbon, cooled under Hg, detonates in
CljO; CI, O, and a little COj are formed.— 6.
Hydrochloric acid gas forms H2O and CI. —
7. Acetic anhydHde, {C2HsO)20, absorbs the gas
forming the very unstable compound CjHsO.OOl
(Schiitzenberger, 0. B. 53, 538).— 8. The liquid
CljO sinks in water, and then slowly dissolves
forming HClOAq (g. v.). Water at 0° absorbs
more than 200 times its volume oi gaseous
C1,0 : the solution contains HCIO.
Method of Analysis. The gas was slowly
passed through a narrow glass tube with three
bidbs blown on it, the part of the tube before
the first bulb being heated ; by this means the
gas was decomposed, and the three bulbs were
filled with the products of this decomposition,
viz., CI and 0. The bulbs were sealed by the
blowpipe, and each was then opened under
EOHAq ; the CI was thus absorbed while the 0
remained. The volume of EOHAq was mea-
sured; the bulbs were filled with KOHAq and
the total volume was determined. The result
was that 2 vols. CI were found in each bulb with
1 vol. 0. The weights of CI and O formed
were calculated, and the weight of the volume
of the undecomposed gas which the bulb would
contaio when full was calculated from the
observed S.G-. of the gas. It was thus found
that 2 vols, of the gas are decomposed by heat
into 2 vols. CI and 1 vol. O. This calculation
assumes that the gas entering the small bulb
contains no free CI or O (Begnault).
jBe/erences.— BerthoUet, Statique CMmiqtte,
2, 183. Wagemann, G. A. 35, 115. Geiger,
B. P. 15, 40. Grouvelle, A. Oh. 17, 37. Ber-
zelius, P. 12, 529. Liebig, P. 15, 541. Sou-
beiran, A. Ch. 48, 113. Balard, A. Ch. 57, 225.
Martens, A. Ch. 61, 193. Gay-Lussac, C. B.
14, 927. Pelouze, A. Ch. [3] 7, 176. Kolb,
A. Ch. [4] 12,266.
II. OhiiObine peroxide. CIO2. {Chlorine
dioxide or tetroxide.) Mol. w. 67'29. V.D.
38-6 , 34-5 at 10-7° and 718 mm. (Pebal a.
Schaoherl, A. 213, 113). S.G. 2-315 (air = 1).
PreparatMm. — 1. About 100 grams pure
cone. llaSO, is placed in a platinum dish
surrounded by snow and salt; from 15 to 20
grams dry finely powdered KCIO, is added little
by little, with stirring with a glass rod after
each addition. When so much KCIO3 has been
added that the contents of the dish form a thick
oily liquid, this is carefully poured through a
funnel into a glass fiask, with the neck drawn
out, of a size such that it is not more than one-
third filled with the liquid. The greatest care
must be taken to keep the neck of the flask per-
fectly free from the oily liquid. The flask is
kept cold ; a piece of glass tubing of the sam<
diameter as the end of the drawn-out neck d.
the flask is pressed closely against the end 4
this neck, and the joint is made tight by caou
tchouc. The flask is then placed in a water batl:
and very slowly heated to 20°, and after somt'
time to 30°-40° ; the gas is collected, by down-
ward displacement, in small dry flasks, or it
may be liquefied by passing into small tubes
surrounded by snow and salt. The whole opera-
tion is best conducted by gas-light (Millon,
J. pr. 29, 401 ; Cohn, J. pr. 83, 54). If the
liquid is prepared each tube should not contain
more than 1 or 2 drops ; the liquid is frightfully
explosive. The gas prepared as above always
contains a little CI and O. — 2. According to
Jacquelain {A. Ch. 30, 339) fairly pure ClOj
may be obtamed by the action of a mixture of
equal volumes of cone. HjSO, and water on
pure ECIO3, in a flask with a long neck, placed
in water at 70° so that half the neck is im-
mersed,— 3. If a very intimate mixture of 3 pts.
finely powdered EClO, with 13 pts. finely pow-
dered crystallised oxalic acid is warmed in an
oil bath to 70° a mixture of CIO2 and COj is
evolved regularly and without danger; five-
sixths of the CI of the EClO, forms ClOj aai
one-sixth remains as ECl (Calvert a. Daviea
C. J. 11, 193; v. also Schacherl, A. 206, 75).
Properties. — ^Yellowish-green gas, condens-
ing (by snow and salt) to a red-brown liquid ,
and solidifying at about —59° (ether and solid
CO|j in vacuo) to hard, brittle crystals, resem-
bling EjCrjO, in appearance (Faraday, T. 1845.
155). Both gas and liquid are frightfully ex-
plosive ; explosions often occur without any
assignable cause. S.G. of liquid CIO, about 1-5.
B.P. about 9° (Pebal, A. 177, 1). In a vessel
wholly made of glass, liquid CIO, boils at 9-9°
under pressure of 730'9 mm. without explosion
(Schacherl, A. 204, 68). The gas has an irri-
tating odour, resembling that of NO, ; it does
not ^affect litmus paper ; it is unchanged in
the dark, but decomposes, usually explosively,
in sunlight.
Bea^Uons and Com'bmQ,imns^~X• Easily oxi-
14
CHLORINE, OXIDES OF.
dised bodies, e.g. P, or S, burn in ClOj, usually
with explosion. — 2. Mercu/ry absorbs the gas
and decomposes it with detonation. — 3. Hydro-
gen (8 Tols. H + 3 vols. OIO2) decomposes ClOj
explosively in presence of spongy Pt, or of elec-
tric sparks, forming HjO and HCl (Blundell, P.
2, 2X6; Stadion, G. A. 52, 197 a. 339).— 4. Ac-
cording to Kammerer (P. 138, 404) bromine and
iodine do not react with gaseous ClOj. — 5. Many
organic compownds cause explosion of ClO^ at
ordinary temperatures. — 6. Liquid CIO2 ex-
plodes when a piece ot potash is placed in it ; if
water is present, a mixture of equal equivalents
of KCIO3 and KC10.J is formed, much heat being
produced. — 7. Liquid ClO^ sints in water; on
shaking, much gas is given off, an explosion
usually takes place, and the water contains
HClOj and HClOj. If the Water is kept at 0°
yellow crystals are formed which cannot be
melted without evolution of considerable quan-
tities of gas (MUlon, A. Ch. [3] 7, 298). Water
at 4° absorbs about 20 times its own volume
of gaseous ClOj, with formation of HClO^Aq
and HClOjAq (Millon, l.c.) ; this solution de-
composes in sunlight, giving off CI and O, and
after a time only HCIO, remains in solution. —
8. Cono. sulphuric acid at — 18° absorbs about
20 times its own volume of gaseous ClOj, be-
coming yellow in colour; on removing the
acid from the freezing mixture the colour
changes to reddish ; at 10°-15° OlO^, C\fi, (?),
and a mixture of CI and 0 in the proportion of
2 vols, to 3 vols., are evolved ; when gas ceases
to come off, the residue contains HClOj (Sta-
tion, Q. A. 52, 197 a. 339 ; Millon, A. Ch. [3] 7,
298).
Method of Analysis. — (Pebal, A. m, 1 ;
213, 112). The gas was prepared by gently
warming H^SO^Aq (1 vol. cone, acid to 2 vols,
water) with a mixture, of oxalic acid and po-
tassium chlorate ; it was washed by passing
through a little water, dried by CaClj, and
liquefied in a small glass bulb with two glass
necks surrounded by CaCl, and snow. When
about 3 O.C. of the liquid were obtained, the
evolution of gas was stopped; one neck o{
the glass bulb was closed, and the other was
connected with a glass tube, furnished with
glass stop-cocks, placed in water. The freezing
mixture was removed, and gaseous CIO2 was
allowed to pass slowly through the glass tube
till all air was removed ; the stop-cocks of the
tube were then closed, and the temperature of
the water and the reading of the barometer were
determined. The glass tube fuU of ClO^was
surrounded by fine wire gauze (in case an explo-
sion should occur), and the water was gently
warmed uhtU decomposition of the gas oc-
curred ; the temperature of the water was then
allowed to come back to the first reading. The
mixed gases, or a portion of them, were then
transferred to a similar graduated glass tube,
fiUed with saturated NaClAq containing a little
GlAq and placed in a cylinder full of the same
solution; this solution absorbs hardly any CI
from a mixture of CI and 0. The volume of CI
in the known volume of the mixed gases was
determined by absorption by KIAq. The fol-
lowing results were obtained :
il) Volume - expansion on decomposition
a3-9;36-44= 2:3-06;
(2) Eatio of Cl-volume to 0-volume ll'l:23-2
= 1:209;
(3) Batio of 0-volume to expansion
24-65:12-54 = 1-96:1;
that is, 2 vols, chlorine peroxide yields 2 vols. 0
and 1 vol. CI. Then from the weights of 0 and
CI obtained, and the weight of chlorine peroxide
used (calculated from the observed S.G-. of the
three gases) the formula ClO^ is deduced. It is
possible that the gas at low temperatures, or
the liquid, may have the composition G[fi,.
CIO2 may also be analysed by allowing the
liquid to act on PeSO^Aq and determining the
Pe23S04 and the HCl produced ;
lOPeSOjAq + SHjSO^Aq + 2C10,
= 5Pe23S04Aq + 2HCLAq + 4H20 {v. Garzarolli-
Thurnlackh, A. 209, 205).
References.— atadion, O. A. 52, 197 a. 339.
Davy, T. 1813. 214. Gay-Lussac, A. Ch. 8, 408.
Soubeiran, A. Ch. 48, 113. J. Davy, N. Ed. P. J.
17, 49. Millon, A. Oh. [3] 7, 298. Calvert a.
Davies, O. J. 11, 193. Cohn, /. p^: 85, 53.
Faraday, T. 1845. 155. Blundell, P. 2, 216.
Kammerer, P. 138, 404. Pebal, A. 177, 1.
Garzarolh-Thnrnlackh, A. 209, 184.
III. ChiiOexne tkioxiue. CI2O3. (OfeZorowa
a/nhydmde.) The existence of this body is
very doubtful. The results obtained by Millon,
Carius, Schiel, &a. differed considerably: thus
Millon could not liquefy the gas he obtained;
Schiel and others obtained a dark reddish-brown
liquid by passing the gas into a tube in snow
and salt. Brandau determined the S.G. of the
gas to be 4-07 at 9°, 4-02 at 13°, and 3-17 at
16° ; Millon gave the S.G. as 2-63 and Schiel
as 2-6-2-73. (The calculated S.G. of CljO, is
4-109, air = l.) The gas was analysed by
MiUon by passing it over hot Cu and deter-
mining the CuClj formed ; Brandau dissolved in
water and titrated with KIAq, he also reduced
by HNOjAq and estimated the CI. The results
cannot be regarded as satisfactory. GarzaroUi-
Thurnlaokh (B. 14, 28 ; more fully, A. 209, 184)
in 1881 determined the relation between the
expansion of the gas on decomposing it by heat
and the volume of O thus obtained; he em-
ployed Pebal's method for analysis of ClOj
(2. V.) ; the gas .examined was prepared by the
action of (1) KGIO, and HNOsAq on ksfi,
(Millon's method), (2) KCIO3 and HjSOiAq on
C5H11 (Carius's method modified by Brandau),
(3) KClOs and HNO^q on sugar (Schiel's
method). In every case the volume of 0 ob-
tained was almost exactly double the total
expansion of the gas ; but it the gas were
CI2O3 the volume of 0 must be equal to the
total expansion, and this result would hold
good if free CI were mixed with the CljO,.
GarzaroUi-Thurnlaokh concludes that the gaa
supposed to be OljOs by MiUon and Brandau
was really a mixture of CIO2, with varying
quantities of CI, a little 0, and COj.
Preparation of compound said to be CljO,. —
1. Millon {A. Ch. [3] 7, 298) used 15 pts.
finely-powdered As^ and 20 pts. powdered
KCIO5 made into a thin cream with water ; to
this he added 60 pts. pure HNGjAq (free from
HCl and H^SOJ S.G. 1-33, diluted with 20 pts.
HjO ; the mixture was placed in a flask of a
size such that the liquid partly filled the neck,
an exit tube was attached, and the contents
CHLOKINE, OXY-ACIDS OF.
16
gradually warmed in a water-bath to about
25°. The gas may be dried by CaClj; it is
ooUected in dry flasks by downward displace-
ment. The flask should be covered with a
thick cloth in case of explosion. Slight ex-
plosions sometimes occur, but if the process
is conducted carefully it is unattended with
danger. — 2. Schiel {A. 109, B19) used a mixture
of 2 pts. KClOj, '6 to '8 pts. cane sugar, and
3 pts. HNOjAq, S.G. 1-3 diluted with 3-4 pts.
HjO ; the gas contained CO2. — 3. Carius (A.
140, 317 ; V. also Brandau, A. 151, 63) dissolved
10 pts. CjHj in 100 pts. cono. H^SO,, diluted with
100 pts. H,0, after cooling added 12 pts. pow-
dered KCIO,, and heated to about 50° on a
water-bath. The exit tube of the flask was
connected with a series of small bulbs contain-
ing water; from these the gas passed into a
tube kept at —18°; the liquefied oxide was
separated from crystals of hydrated chloric
acid (q. v.). About 5-7 o.c. liquid was obtained
from 54 grams KOIO, ; the liquid contained a
little water and traces of CIO, and HGIO3.
Properties of the supposed aompoimd. — The
properties said to belong to Cl^O, resemble those
which characterise CIO, ; the former is however
less explosive. It is described as a greenish-
yellow gas, condensing to a dark led-brown
liquid ; S.G. about 1*5 ; the liquid volatilises at
about 0°, the latter portions boiling at 8°-9°.
The gas is decomposed into CI and 0 at about
67° with slight explosion. In contact with
most non-metals, and with Te and As detonation
occurs. Fb, Cu, Sn, Sb, Ag, Zn, and Fe are
unchanged in the gas ; Hg absorbs it. One
volume H2O absorbs 8| vols, of the gas at 8° ;
the solution contains HCIO,, and after a time
also HOIO3. Brandau says that if the water is
at 0°, a solid hydrate of HCIO, containing from
50 to 67'5 p.o. HjO is produced.
References. — Millon, A. Ch. [3] 7, 298 ;
De Vrij, A 61, 248 ; Schiel, 4. 108, 128 ; 109,
317; 112, 73; 116, 115; Carius, A. 140,317;
142, 129; 143, 321; Brandau, A. 151, 340;
GarzaroUi-Thnmlaokh, B. 14, 28 ; A. 209, 184.
M. M. P. M.
CffLOEIHE, OXY-ACIDS OF.— Four com-
pounds are known, HCIO, HCIO,, HCIO3, and
HCIO,. The anhydride of HCIO, viz. 01,0, is
known ; the anhydride of HCIO,, viz. GI2O,, is
generally stated to be known, but the evidence
is not conclusive {v. Chlobtne tbioxide). Of
the acids, only HCIO4 has been obtained in
definite form apart from water. Aqueous solu-
tions of HCIO and HCIO, are easily decomposed
on heating, giving HClOgAq and HClAq ; the
most cone, solution of HClOgAq obtained
contains the acid and water in the ratio
'ELClOii^Kfi, this solution decomposes on
heating yielding HClO^Aq, CI, and 0 ; HClOjAq
is stable, it may be concentrated by distillation
until crystals of HCIO^.H^O are obtained; by
caretully heating these crystals the acid HCIO,
is formed, this aoid is very easily decomposed
with explosion. The following thermal data
are given by Thomsen (27s. 2, 400) : —
[H,Cl,Aq] = 39,315
DifE.= -9,885
[H,Cl,0,Aq] = 29,930
DifE.= -6,990
[H,Cl,0»,Aq] = 23,940
These numbers would lead us to expect that
neither HClOAq nor HClOjAq would be produced
by the direct addition of 0 to HClAq ; nor should
we expect to form KOlOjAq by adding 0 to KClAq,
for [KClAq,0»l= -15,370 (Thomsen) ; the pro-
duction of HClOAq by the direct combination of
01 and 0 in presence of H^O is also improbable,
considering that [CP,0,Aq] = -8,490 (Thomsen).
CI and 0 do not unite directly, but if a
moderately basic oxide, e.g. HgO or ZnO, is
acted on by CI and H^O, HClOAq is produced ;
if a strongly basic oxide, e.g. Kfi or NajO, ia
used, a salt of HCIO is formed in solution.
Odling {Ph. [2] 1, 469) says that HClOAq ia
formed when a current of air laden with HCl
is passed into a warm solution of KjMnjOg
containing H2S04. HClOAq is also said to
yield HClOjAq by the action of ozone. In the
ordinary processes whereby HClOsAq and
HClOjAq are obtained from HClOAq (or salts
of the higher acids from salts of HCIO) much
heat is produced in the decomposition of the
lower acid, or salt, and 0 is set free at the same
time ; under these conditions the higher acids,
or salts, are formed. When KClOAq is heated
KClAq and KClOgAq are produced ; when
KCIO3 is heated, 0 is evolved and ZCIO, and
ECl are produced ; on raising the temperature
EGl remains and all the 0 is evolved. Thom-
sen {Th. 2, 145) gives the following thermal
values for the possible reactions between CI and
K,0:-
, 78,935 if SKClOAq + 8KClAq
[Cl»,8K^0Aq] = 97,945 if KClOjAq + 5EClAq
1 113,315 if 30 + 6KClAq
are formed.
Chloric acid is as strong an acid, i.e. its affinity
is as great, as hydrochloric acid {v. Affinity,
vol. i. pp. 82, 83) {comp. Bhomine, Oxy -acids of.
V. also HaiiOqen elements).
Detection and Estimation of salts of HCIO,
HCIO2, HClOs, and HCIO,.
I. Salts of HCIO in solution react as oxi-
disers much in the same way as ClAq; on
adding a little extremely dilute HNOjAq and
distilling, a dilute solution of HClOAq is ob-
tained which (1) bleaches indigo at once, but
does not bleach if As^O^Aq is present, (2) gives
a brownish pp. of HgO.HgCl, when shaken with
Hg, (3) with SOjAq forms a solution containing
1 equivalent HCI to 2 equivalents HjSO,
(HClOAq -I- SOjAq -I- HjO = H^SO^Aq -i- HClAq).
Hypochlorites may be estimated by titration
with KIAq and NajS^OjAq. '
II. Salts of HCIO, in solution react very
much as mixtures of chlorates and chlorides;
they are decomposed by H^SOjAq (1 acid to
8-10 water) with formation of a yellow colour
probably due to CIO, and CI, whereas a mixture
of chloride and chlorate is not decomposed.
They bleach acidulated indigo at once even in
presence of As^O^Aq. With SOjAq a eolutioo.
is formed containing HCl and H^SO, in the
ratio HC1:2H,S04 (HClO^Aq -h 2S02Aq + 2H,0
= 2H2S04Aq + HClAq). Chlorites may be esti-
mated by allowing them to oxidise a standard-
ised acidulated solution of FeSO^, and determin-
ing the residual FeSO, by K,Mn,OBAq.
III. Salts of HCIO, in solution do not bleach
acidulated dilute indigo solution in the cold
until a little SOfAq is added (CI is. then set. free);;
16
CHLOKINE, OXY-AOIDS OF.
they do not separate I at once from EIAq.
They are decbmposed by digestion with warm
cone. EOlAq; salts of HGlOjarenot. Chlorates
may be estimatfid by reduction to chlorides, by
Zn and HjSOjAq, or by a Cu-Zn couple {v. Bo-
thamley and Thompson, C. J. 53, 159). They
may be separated from cblorites by conversion
into K salts, and repeated evaporation in vacuo
(v. CHLOBOUB ACID AND CHLOBITES). KGIO, iS
fairly soluble in water at 15° (S = 6), and KCIO,
is nearly insoluble (S = 1*6) ; KCIO, is insoluble
in alcohol containing alittleKCsHsO,; amethod
of separation of KCIO, and KGIO4 may be
based on these facts.
IV. Salts of HClOj are not decomposed by
digestion with cone. HClAq at 100° ; their solu-
tions do not bleach acidulated indigo even in
presence of SO^Aq, nor are they reduced by a
pu-Zn couple at ,100°. Perchlorates may be
estimated by converting them into KCIO, and
determining the 0 in them by heating, and the
E and CI in the residue by the usual methods.
I. HyPOOHLOKOFS ACID AND HyPOOHLOEIIES.
HClOAq; MClOAq. In 1788 BerthoUet ob-
tained a liquid with bleaching properties by
the action of chlorine on aqueous alkalis;
BerthoUet thought the liquid contained a com- ,
pound of the alkali and chlorine, the latter
being then regarded as oxidised hydrochloric
acid. Berzelius supposed that a mixture of
alkali chloride and chlorite was formed. In
1834 Balard proved that the bleaching liquid
contained a salt of a new acid (BerthoUet,
StaU^ue ChmdquB, 2, 183 ; Berzelius, P. 12,
529 ; Balard, A. Ch. 57, 225). The acid is
known only in aqueous solutions; one salt
Ca(C10)2.!i;H20 has been obtained as a solid.
Formation. — 1. By the action of CI on ZnO
in presence of water ; ZnCljAq is formed at the
same time. — 2. By the action of CI on (1) GaCO,
suspended in water; (CaCOj -l- HjO + Aq -^ 201,,
- CaCljAq + 2HC10Aq + CO,) :
(2) Na^COaAq ; (2Na2C03Aq + 2H2O + 201^
= SNaOlAq + 2HC10Aq + 2NaHC0,Aq ; then
2NaHC03Aq + 201j
= 2NaClAq + 2CO2 -h 2HC10Aq) :
(3) NajSO^Aq ; (Na^SOjAq + H^O + Clj
= NaHSOjAq + NaClAq + HClOAq).— 3. By the
action of 01 on AgCOj suspended in water ; AgCl
is also formed. — 4. By the action of 01 on
CaO^EjAq; CaOjCLj and OaClj are probably
formed (v. p. 17) ; when to an aqueous solution of
this product as much very dilute HNO,Aq is
added as suffices to convert less than th^ half
of the Oa into Ca2N03, and the liquid is dis-
tilled, dilute HOlOAq is obtained (Gay-Lussac,
A. 43, 153; Schorlemmer, B. 6, 1509; Kopfer,
0. J. [2] 13, 713).— 6. By passing 01^0 into RjO,
HClOAq is formed («. Chlobinb monoxide). — 6.
Addition of H^OjAq (containing 2-45 p.o. B..fl,)
to a large excess of ClAq produces HClOAq,
according to Fairley (B. A. 1874, 57); if much
H2O2 is added, the HClOAq is decomposed
forming HClAq, H^O, and evolving O. — 7.
According to Odling {J. 1860. 65) HClOAq is
formed by leading air laden with HCl into a
warm solution of E^Mn^O, containing H^SO^Aq,
or into a mixture of MnOj and HjSOjAq. — 8.
HClOAq is also formed, along with other salts,
by the action of CI on aqueous solutions of
Na,HPp„ FeSO,, ZnSO^, MnSO,, CuSO,,
Zn{Cja.fi^)i.—9. Alka^ salts of HCIO are
produced by electrolysis of NaClAq or EClAq
(Lidoff a. Tichomiroff, J. B. 1882. 212).
Preparation. — A flask of somewhat under
1000 o.c. capacity, with a good-fitting glass
stopper, is filled with air-free 01 in the dark ;
ppd. HgO, which has been heated to 300° and
cooled, suspended in a little H^O, is added, in
the proportion of 15 grams to 1 litre 01 ; the
flask is shaken for about 15 minutes, and the
hquid is poured off from the HgjOClj formed :
this solution contains from 2 to 3 p.o. of HCIO
(Carius, A. 126, 196). If the CI used contains
much air the reaction proceeds very slowly ; if
the HgO has not been heated to 300° much
Hg2C10, is formed. 2HgO -t- 2Clj -1- H^O h- Aq
= HgO.HgCl2-l- 2HC10Aq. The solution of
HClOAq is best kept in contact with a little HgO ;
any 01 set free is thus continually converted
into HCIO.
Properties. — An aqueous solution of HCIO
smells like CljO. It is very easily decomposed
into 01 and HClOjAq ; in sunlight this change
proceeds rapidly, the more cone, the solution the
more rapid is the decomposition, and traces of
HCIO, are also formed (Popper, A. 227, 161). A
dilute solution of HCIO may be distilled with
partial decomposition, the distillate is richer
in HCIO; Gay-Lussac found that, on distilling
a dilute solution to one-half, the distillate con-
tained five-sixths of the total HCIO (0. B..14,
927). HClOAq is a monobasic acid; added
to KOHAq or Ca(OH)jAq, EClOAq or
Ca(C10)jAq is formed. Thomson gives the heat
of neutralisation as [HClOAq, NaOHAq] = 9,980,
which is about | of the value of the heat of
neutralisation of one of the stabler monobasic
acids {e.g. HCl, HCIO3, HNO,), and is a little
greater than the value for HSHAq, viz., 7,740.
HClOAq does not dissolve bases insoluble in
water, nor does it decompose the carbonates of
these bases.
Bea^tidns. — 1. HClOAq acts generally as an
oxidiser^ it easily parts with 0 while HClAq
remains. Thus, As is rapidly oxidised with
evolution of light ; P, S, Se, Br, I are converted
to HsPOjAq, HjSOjAq, &c., even by dilute
HClOAq; lower oxides or salts are converted
into higher, e.g. SOjAq to H^SO^Aq, FeO to
Fe^Oa, As^OsAq to As^OsAq, PeSO,Aq to
Fe2(S0j3Aq, FcjCljAq, and FeA. MnSO^Aq to
MnOj; sulphides yield sulphates, e.g. H^SAq
gives HjSO,Aq and S ; NH3 gives N, HjO, and
NH^ClAq; HCl forms HjO and CI. The quantity
of the acid expressed by the formula HCIO
oxidises the same mass of an oxide &o. as can
be oxidised by Cl^ in presence of H^O ; thus
MnO + H,0+ { g^io = MnO,+ | 'i^}^H,0.
2. On many cor ion compoMJuJs HClOAq actspartly
as an oxidising, partly as a chlorinating, agent ;
e.g. HjCjOiM + HOlOAq = 200^ + HjO -l- HClAq.
Some organic compounds combine with the
acid : e.g. OsH, -1- 3HCI0Aq = C3H,Cl3(0H)„
CjHi + HOlOAq =C2H4C10H.— 3. Indigo solu-
tion, and various other vegetable colours, are
rapidly bleached by HClOAq; one formula-
weight of HCIO in solution exerts as great a
bleaching action as Clj (HClOAq =
HClAq + 0 ; CI, -^ HjO = 2HC1 + 0).— 3. HClOAq
CH1.0EINE, OXY-ACrospF.
IT
is BaicI to be ozi(1ised to HC104Aq by osone
(Fairley, B. A. 1874. 58).
HypochloriteB are yery easily decomposed ;
even in dilute solutions boiling suffices to con-
vert them iato chlorides and chlorates, in cone,
solutions boiling produces, chlorides and O.
Their solutions are also decomposed by heating
with OojO,, CuO, MnO, &o., O is evolved and
chlorides remain; «.<;. Ca(C10)2Aq-t-Co20,=:
OaCl^Aq + CojOj + O, (CoO, is perhaps formed
and again reduced to Co^Oswith evolution of O ;
Winkler, J. jar. 98, 340). As Oa(001)jAq is
formed by the action of Gl on GaOAq, it is easy
to obtain O by leading CI into strong warm milk
of lime containing a little Co203(Co.2N03 is
used). Solutions of EClO and NaClO, along with
ECl and KaCl, are obtained by leading CI into
cold dilate KOHAq or NaOHAq. Solutions of
hypochlorites bleach rapidly on addition of a
little HNOjAq, H^SOiAq, HClAq, or even COjAq ;
these solutions act as oxidisers towards P, S, I, &o.
As the hypochlorites are so easily decomposed
it is difficult to obtain them, even in solution,
free from chlorides. Eixigzett (C7. J. [2] 13, 404)
obtained crystals of nearly pure calpium hypo-
chlorite, CaO^Cl^-xH^O, by exhausting bleaching
powder with cold H^O, filtering, and placing
the filtrate m vacuo over cone. H^SO,. The
crystals very easily decomposed, even by drying
in vacuo, with evolution of CI. The greater
part of the CI was lost by heating the moist
crystals to 100°, the residue probably contained
chlorate, it also contained much carbonate. The
crystals dissolved in H^O; this solution was
decomposed by COj with evolution of most, but
not all, of the chlorine. That an aqueous solu-
tion of bleaching powder contains GaO^Clj has
been confirmed by 0'Shea.(0. J. 43, 422), who
proved that when such a solution is diffused
without a membrane the diSusate contains con-
siderably less active CI (i.e. CI which is so com-
bined with Ca and 0 that it is capable of bleach-
ing), and the residue considerably more active
CI than the original liquid, in proportion to the
CI or CaCl, ; that is, diffusion sufficed to render
the diitused liquid relatively poorer in active CI
and richer in chloride.
Bleaching powder. — 01 is absorbed by
slaked lime and the product possesses strong
bleaching properties. Oay-Lussac regarded
bleaching powder as containing CaCljO, and
CaCl, in the ratio CaCl^O.tCaCl^. Odling
{Manual of Ghem. 1, 56) suggested the com-
position Ca.OClCl, chiefly because bleaching
powder is not deliquescent nor is CaClj removed
from it by treatment with alcohol. Gopner
{J.pr. [2] 7, 441) asserted bleaching powder to
be a compound of CaO with CI, and to have the
composition CaO.Clj. Stahlschmidt (B. 8, 869)
suggested the composition Ca.OH.OCl. Bleaching
powder prepared by the action of pure dry CI on
pure dry Ca(0H)2 always containssome CaiOH), ;
but the quantity of this is variable and can be
much diminished by repeated treatment with
dry CI, the Ca(0H)2 is not therefore an essential
part of the bleaching compound {v. Kopfer,
C. J. [2] 13, 713 ; O'Shea, 0. J. 43, 422 ; Lunge a.
Schappi, D. P. J. 239, 63). That OaOlj is not
present as such in bleaching powder is shown
by the facts that it is not deliquescent, that
when treated with small successive quantities
Vol. U.
of water the first washings contain much less
CI than would be the case were CaCl^ present in
the liquid, and that in the presence of a little
moisture almost the whole of the CI can be re-
moved from bleaching powder by the action of
OOj (I)unge a. Schappi, D. P. J. 237, 63 ; v.
also Lunge a. Naef, B. 18, 840).
The composition CaO.Clj assigned by Gop-
ner to the bleaching compound in bleachiof;
powder was disproved by the experiments of
Eopfer (0. J. [2] 13, 718), who showed that
when an extremely dilute mineral acid (HCl,
HNO„ or HjSOj) is added to a solution of bleach-
ing powder, in quantity sufficient to saturate all
the lime and the Ga(OCl), present — calculated
on the assumption that the active (bleaching)
CI exists as Ca(0Cl)2— andthe liquid is distilled,
almost the theoretical quantity of HCIO is
obtained in the distillate. The formula
Ca.OH.OCl given to the bleaching compound by
Stahlschmidt assigns a limit to the amount of
active CI, i.e. CI available for bleaching, in the
powder : Stahlschmidt represents the formation
of the bleaching powder thus — 3Ca(0H)2 + 201,
= 2Ca.OH.OClH-CaCl2-t-2H20. The strongest
bleaching powder cannot therefore contain more
than about 33 p.a. of available 01 ; but Lunge a.
Schappi {D. P. J. 237, 63) prepared bleaching
powder containing 43-4 p.o. available 01. More-
over, according to Stahlschmidt's view, when
water acts on bleaching powder, the reaction is
2Ca.OH.OCl = Ca(OH)2 + Ca02CL:; therefore no
bleaching powder can be represented as con-
taining Ca020l2 and CaCl, in a greater ratio to
Ca(0H)2 than 1:1:1. Now O'Shea (C. J, 43, 422)
determined the ratio of Ca(OCl), (supposing all
available Gl to exist in this form): CaCLi:Ca(0H)2
in six samples of bleaching powder made from
pure Ca(0H)2 ; in 2 out of the 6 samples
the ratio was 3Ca02Cl2:3CaCl2:2Ca(0H)2. Finally
O'Shea removed any CaGl, present as such
from various samples.of bleaching powder, pre-
pared from pure Ca(0H)2 by repeated treatment
with alcohol, and determined the total CaOj the
total 01, and the available Gl, in the residue, i.e.
in the bleaching compound; the results in.
every case were — (1) CaO : total Cl = 1:2; (2)
available 01: total 01=1:2; (3) GaO : available
01=1:1.
Stahlschmidt's formula Ca.OH.OCl requires
for (1) the ratio 1:1 ; for (2) 1:1 ; for (3) 1:1.
Gay-Lussac's formula OaOsClj requires tor
(1) the ratio 1:2 ; for (2) 1:1 ; for (3) 1:2.
Odling'B formula Ca.0G1.01 requires for (1)
the ratio 1:2 ; for (2) 1:2 ; for (3) 1:1.
The experiments of Eingzett already referred
to (v. supra) showed that when water acts on
bleaching powder Ca02Cl2 is contained in the
solution. There can be little doubt that the
formula Ga.OCl.Gl better expresses the com-
position and properties of the bleaching com-
pound in bleaching powder than any other
formula yet suggested; and that the reaction
which occurs when water is added to this com-
pound is 2Ca.0Cl.Gl -h Aq = CaOsOljAq + GaCljAq.
II. Chloboqs Acin and Cbloriies. HGlOjAq ;
MClOj. Chlorous acid is known only in aqueous
solution ; it is indeed doubtful whether even a
solution of HGIO2 has been obtained free from
HCIO,. EGIO2 may be prepared b^ adding an
aqueous solution of CIO, of known strength to
0
i6
CHLORINE, OXY-ACmS OF.
the proper quantity of EOHAq, evaporating at
45''-60° m vacibo, separating from KOlOj which
crystallises out,, repeating the eTaporation and
separation of EClO,, then addihg alcohol to the
mother liquor, evaporating m vaauo, and col-
lecting the second crop of crystals which form
(Garzarolli-Thurnlackh a. J. Hayn, .1.209,203).
HClOjAq could not be obtained by the action of
acids on this salt. When the gas obtained by
acting on EClO, with HNOjAq and As,Og is led
into water, a yellowish-red acid solution is
obtained, which on warming, or on exposure to
sunlight, contains HCl and HOlO,. This solu-
tion when freshly prepared is generally supposed
to be HClOjAq ; but the experiments of Garza-
rolli-Thurnlackh (u. Chlobinb tbioxide) render
it almost certain that the gas obtained as above
is a mixture of CIO, and CI, and that the
solution contains both HCIO, and HCIO,.
The solution prepared as described reacts
with many metals; e.g. Hg forms an oxy-
chloride, Cu a mixture of CuCl, and Cu(C10,)2>
Zn and Fb form chlorides and probably chlorites,
and finally chlorates; with the lower salts of
Sn, Fe, Hg, &a., the solution reacts to form
higher salts of these metals ; As^OjAq is not
oxidised to ASjO^Aq ; HCl decomposes the
solution forming CI and H^O, HIAq gives HCl
and I ; HNO^Aq is oxidised to HNO,Aq ; SOjAq
is oxidised to H^SO^Aq. According to Brandau
(A. 161, 840) if the gas supposed to be Cl^O, is
led into H^O at 0° a solid hydrate of HCIO, is
obtained ; when pressed between paper the
hydrate is a lustrous mass remaining unmelted
at 10°, and volatilisable without residue. Two
specimens gave 50 and 67*5 p.c. water respec-
tively.
Chlorites. Very few of these salts have
been prepared. Potassium chlorite, EClO,,
prepared as above described, forms needles,
which deliquesce after standing soine time in
the air. The siVoer and lead salts, AgClO^ and
Fb(C102)2 are obtained by adding AgNO,Aq and
Pb{CjHj02)^q respectively, to KOlOjAq. AgClOj
crystallises from hot HjO in greenish-yellow
scales ; it is slowly decomposed in direct sunlight ;
SOjAq rapidly reduces to AgCl ; dilute H^SOjAq
evolves a gas the colour and smell of CIO,.
KCIOjAjj quickly oxidises FeSO^Aq; EClO,
mixed with S and rubbed ignites the S.
Pb{C102)2 after washing with hot H^O forms
'greenish-yellow scales; slightly soluble in hot
HjO; reactions similar to those of EClO,;
soluble in EOHAq. This solution is reduced by
SOjAq to PbSO, and PbCljAq (GarzarolU-
Thumlaokh a. J. Hayn, A. 209, 203). Millon
{A. Gh. [3] 7, 298) described Ba(C10s)j and
Sr(C102)j as very soluble salts; probably the
salts contained Ba and Sr(C103)2.
IH. Chlobic ACID Am] Chlobates. HClOgAq;
HCIO3. An aqueous solution of HCIO, is
formed when ClO^Aq is exposed, to sunlight, or
is heated. ECIO, and NaClO., are produced by
electrolysis of EClAq and NaClAq respectively :
ca;rbon electrodes are employed (LidofE a. Ticho-
miroff, J. B. 1882. 341).
Preparatitm. — 1. Ba(010,)j is obtained by
dissolving 3 pts. crystallised (NHj)i,S04 and 3
pts. EClO, in 15 pts. hot HjO, evaporating to a
thin syrup, digesting for a day at a gentle heat
with alcohol (80 p.c.), filtering from E^SO,,
adding BaOAq, evaporating, and crystallising
(Wittstein; v. also Bottger, A. 57, 138). A
weighed quantity of the crystals ol BalClOsJj is
dissolved in HjO ; a quantity of dilute H^SOjAq
exactly sufficient to pp. all the Ba as BaSO^ is
added, little by little ; the liquid is filtered— the
filtrate must give no pp. either with BaOAq or
H2S04Aq— and the filtrate is concentrated im,
vactio over HjSO^. — 2. Hot EClOjAq is decom-
posed by excess of H^SiFsAq ; after cooling, the
liquid is filtered from E;jSiF8 and evaporated
over H2SO4 and EOH in vactio ; the excess of
H^SiF, volatilises and HOlOjAq remains.
Properties. — By evaporation in vacuo of
dilute HOlOjAq, a somewhat oily, colourless,
strongly acid, liquid is obtained, with S.G. 1-282
at 14° ; according to Eammerer this liquid con-
tains HCIO3 'and HjO in the ratio HC103:7H2q ; ,
the same chemist says that if this liquid
remains longer in vacuo, sudden evolution of CI
and 0 occurs, and H010s.4^H20 remains (P.
138, 390). The strongest solution of HCIO,
does not solidify at -20°. HClOjAq reddens lit-
mus paper and then bleaches it ; paper or linen
soaked in fairly coi^c. acid and dried takes fire.
Heated to about 40° the solution decomposes
into HClO^Aq, CI, 0, and HjO (SeruUas, A. Ch.
45, 204 a. 270). Thomsen gives these thermal
values [H,01,0»,Aq] = 23,940, but [C1^0^Aq]
= -20,480; [HClO'Aq, EOHAq] = 13,760. .The
affinity of HC10,Aq is equal to that of the
strongest acids {v. Affihitt, vol. i. pp. 82, 83),
BeacUoits. — 1. Zinc and iron dissolve in
HCiP3Aq with evolution of H. — 2. Iodine ia
oxidised to HIOjAq. — 3. Oxidisable oxygen
compounds are converted into higher com-
pounds, e.g. SOjAq gives H^SOjAq, CI, and HjO;
HaPOjAq gives HjPOjAq. — 4- Ghlorhydric acid
forms HjO and CI.— 5. SuVph/wretted hydrogen
produces HjSO^Aq and S. — 6. Iodine gives
HIOjAq; bromine only traces of HBrO,Aq
(Eammerer, P. 138, 399). -7. By electrolysis
HC103Aq yields first HOlOjAq, and then 01
(Buff, A. 110, 257). — 8. Heated above 40°
HClOjAq decomposes into CI, 0, HjO, and
HClOjAq.
Chlorates. HC103Aq acts as a monobasic
acid. Normal chlorates are all soluble in water;
ECIO3 is less soluble than the others. Chlorates
may be prepared by acting on Ba(010,)2Aq with
the sulphate of the metal whose chlorate ia
required ; many are also obtained by the action
of the metallic oxide, or carbonate, on HC10,Aq.
Chlorates easily part with their Owhen heated;
they act therefore as oxidisers (v. Potassium
chlorate). Aqueous solutions are not, however,
very easily reduced (e.g. HjS has no action) ;
boiled with F, chlorides are formed (Slater,
J.pr. 60, 247); chlorates in solution are also
reduced by Zn and dilute H2S04Aq, and by a
Cu-Zn couple. Fusible chlorates detonate when
rubbed with easily cornbustible bodies, e.g. S or
SbjS, ; sometimes violent explosions occur.
HjSOjAq decomposes chlorates with evolution
of ClOj and CI; HClAq evolves euchZorine,
which is a mixture of CIO, and 01. Solutions
of chlorates do not bleach ; addition of a little
SOjAq liberates 01 and bleaching occurs.
Ammonium chlorate. NHj.OlOj. By adding
NHjAq, or (NHJ^COjAq, to HC10,Aq; or
(NHJj00,Aq to Ba(C10,)jAq and filtering; or
CHLORINE, OXY-ACIDS OF.
19
(NHJsSiPjAq to KClOsAq and filtering ; the so-
lution in each case is evapoiated, the salt sepa-
tates in needles. Solable in H2O, and alcohol ;
sublimes sqmewhat above 100° ; at higher tem-
perature decomposes to CI, TiJO, and H2O.
Bariwn chlorate. — By adding BaOAq, or
BaCO,, to HClOjAq. Thompson {P-¥- [3] 31,
510) mixes solutions, each in the mirn'mnm of
\rater, of 122 parts KCIO, and 167 parts
NH^.H.04H4O5,removesK.H.C4H,Os,adds alcohol,
filters, decomposes the NHi.ClOjAq by boiling
with freshly ppd. BaCO,, filters and orystalUses.
(v. also Bottger, A. 57, 138 ; Brandau, A. 151,
361; Bolly a. Merz, D. P.J. 153, 358). Crys-
tallises in 4-sided plates. S. (0°) 22-8 ; (40°)
52-1; (116°) 195; (135°) 287-4; (146°) 365-6 ;
(180°) 522-6 (Tilden a. Shenstone, T. 175, 23).
Calcium chlorate. Ca(0103)2. Prepared like
Ba(C10j)r Very deliquescent and difficult to
orystalUse.
Copper chlorate. Ou(C10s)2.6H20. By dis-
solving CnO in HClOjAq and evaporating. Green,
deliquescent, octahedra ; solable in alcohol ;
decomposed at 100° probably forming a basic
salt (Wiichter, A. 52, 233 ; v. also Casselmann,
Fr. 4, 24).
Lead chlorate. Fb(C10,)2. By saturating
HClOgAq -with FbO, and evaporating; hot
solutions deposit rhombohedral deliquescent
Pb(C10,)j.H20 (Waohter, 4. 52, 233).
Magnesium chlorate. Hg(010,)2. Obtained
as, and closely resembles, CaifClOjJij.
Mercury chlorates. (1) HgCIO,; columnar
crystals, soluble in SjO and alcohol; by dissolv-
ing HggO in EClO^Aq ; heated, gives HgCl, Hg,
and 0. (2) Hg(C10,)2 crystallises from solution
of HgO in warm HCIOjAq in needles. S. (about
15°) 25. Decomposed by heat to 0, HgCl,
HgClj, and a little HgO.
Potassium chlorate. EClO,. By passing CI
into warm milk of lime containing ECl, and
crystallising from the more soluble CaCl,;
purified by recrystallisation, or by rubbing
with water to a thick cream, and washing with
HjO until KCl is removed {v. Lunge, D. P. J.
189, 488; Hunt, B. 5, 229). White, pearly,
monoclinie plates. S.G. 2-35 (Eremers, P< 97, 1 ;
99, 25). S. (0°) 3-3; (15°) 6; (35°) 12; (50°)
19; (75°) 36; (104-8° = B.P.) CO. S. (120°)
73-7; (136°) 98-9; (160°) 148; (190°) 183
(Tilden a. Shenstone, T. 175, 23). S.G. of
EClOjAq at 19-5° (Eremers, P. 96, 62; Gorlaoh,
Fr.8, 290) 1 p,c. E010, = 1-007; 2 p.c. 1-014;
3 p.c. i-02 ; 4 p.c. 1026 ; 5 p.c. 1033 ; 6 p.c.
1039 ; 7 p.o. 1-045 ; 8 p.e. 1-052 ; 9 p.o. 1-059 ;
10 p.o. 1-066. S. (alcohol) as follows : Gerardin
[A. Oh. [4] 6, 129).
M.P. about 359° (Oa,melley, 0. J. [2] 18, 277).
Heated to about 400° evolution of O begins ; if
the temperature is not increased, evolution of O
ceases when EOl and EGlOj are formed (v. Peb-
CHLORio ACID ; Prepaiation,^. 20) ; if the tempe-
rature is increased the whole of the 0 is removed
and KCl remains ; when the temperature is lower
than that at which EOIO4 is decomposed the
reaction approximates to that represented by the ,
equation 8KC103 = 5K010<-t-3KCl-l-20j (Teed,
O. J. 51, 283; Frankland a. Dingwall, C. J. 51,
274). If I pt. ppd. MnOj, ¥eS>a, CuO, or spongy
Pt, is mixed with ECIO3, 0 is evolved at a much
lower temperature ; about 110°-120° with FbjO,,
200°-205° with MnO^, 230°-235° with PuO,
260°-270° with Pt black. The more finely divided
the CuO the lower is the temperature at which
evolution of 0 begins; the temperature is
lowered by so little as j^th part of very finely
divided CuO, MnO^, or FejOj, but the greater
the quantity of the foreign body the more rapid
is the evolution of O (MitsoherUoh, P. 55, 220 ;
Wiederhold, P. 116, 171 ; 118, 186 ; Baudrimont,
'J. Ph. [4] 14, 81 a. 161). EClOj is an energetic
oxidiser ; mixed with easily oxidised bodies, e.g.
S, P, Sb23„ and heated or rubbed, or sometimes^
even exposed to direct sunlight, explosions occur.
Charcoal, S, Sb, abjS,, finely divided Pe, As, very
fine Cu, &c. dropped on to molten EClOj, burn
with production of much light (BSttger, A. 57,
138). Cone. KClOjAq boiled with P produces
KClAq, KjHPOjAq, and KjHPOaAq: with As,
KOlAq and K^HAsO^Aq are formed (Slater, J.pr.
60, 247). For the action of acids on EOlOs v.
Chloiune, oxides of;' GhIiObine feboxide, and
ChIiOKIHE tbioxide.
Bubidxum chlorate. KbClOs. By decom-
posing EbjSOiAq by Ba(C105)jAq. Small tri-
metric crystals. S. (4-7°) 2-8; (13°) 3-9; (18-2°)
4-9 ; (19°) 5-1 (Eeissig, A. 127, 33).
SiVoer chlorate. AgClO,. A slow stream of
CI is passed into H^O containing Ag^O or AgjCO,
in suspension ; liquid is decanted from AgCl and
is again treated with CI; after standing for some
time at 60°, to eonvert any AgOlO into AgCIO,,
liquid is evaporated at 100° (Stas, Chem. Propert.
90). White, onaque, non-deliquescent, trimetrio,
crystals. S.G? 4-93 (Schneider, P. 106,226 ; 107,
113). S. (about 15°) 10; (about 80°-100°) 50:
insoluble in alcohol. Decomposed by CI to AgCl
while HCIO, remains in solution; gives AgCl
and O on heating ; mixed with S explodes more
easily than KGIO,. A double salt KC10s.A.gC10,
is formed by heating equivalent quantities of
KClOjAq and AgClOj to 200° in a closed tube
(Plaundler, O. C. 1862. 849).
Sodium chlorate. By action of CI on
warm NaOHAq ; better by EC10,Aq + NajSiFeAq.
S.O. of alcohol
■DilOi
S.O. -9793
aO. -9573
S.(J. -939
aa, -8967
8.0.-8439
a. at <°
4-9 13°
7-5 25
10-2 35
130 44
16-2 CO
S. at t9
3-2 14°
5-4 2G
7-9 38
12-2 51
17-5 63
S. at t°
1-9 13°
2-7 2b
4-3 36
7-9 55
10-5 63
S. at «°
1-1 14-5°
2-2 28
3-4 40
4-3 60
7-6 67
S. at f
■46 12°
1-28 31
1-95 43
8-10 58
S. at<»
•09 25
•12 34
•24 56
•32 64
o2
80
CHLORINE, OXT-ACIDS OF.
S. (0°) 82 ; (40O) 123-5 r(100'») 204 (Kremers, P.
97, 1 ; 99, 25). S. (alcohol, 83 p.o. 15°) 3. Be-
Bombles ECIO,.
Strontium chlorate. Sr(01O,)2.8H2O. Pre-
pared as Ba(CI0,)2. Deliquescent needles;
soluble in alcohol (Souchay, ^. 102, 381).
Zinc chlorate. Zn{010s)2. By dissolving
ZnCOj in HOlOjAq, or decomposing ZnSiFj by
KC10sA.q (Henry, J. Ph. 25, 265).
ThalUvm chlorate. By adding TlNOjAqto
EClOjAq ; the solution is decomposed by heat
and on evaporation TCIO, separates out (Crookes,
C. N. 8, 195). A chlorate of yttermwm was
obtained by Popp {A. 131, 179).
IV. PebohIiOBIo acid and Pebohlobateb.
HCIO4 ; MClOj. Mol. w. unknown for either the
acid or its salts.
Stadion ((?. A. 52, 197 a. 339) prepared
potassium perohlprate by the action of HjSOjAq
on KCIO, ; he obtained the acid by decomposihg
the new salt by HjSOiAq. Serullas (A. Ch. [2]
45, 270; 46, 294 a. 323), prepared the same
perchlorate by heating ECIO3 until the melted
mass becaqie semi-solid. The acid has been
investigated by Bosooe (A. 121, 346),
Formation. — 1. By heating HGlOjAq, 0 and
01 being also evolved (SeruUas, l.c.). — 2. By the
electrolysis of OlAq, or HClAq (Eiohe, 0. B. 46,
348).— 3. By electrolysis of KOlOaAq, iwith Pt
electrodes, ozone is evolved and ECIO4 and
traces of ECl are formed (Lidoff a. Tichomirofi
J. B. 1882. 341).— 4. By adding ozone to HClOAq
Fairly (B. A. 1874. 58).
Preparation. — 1. EClOjis prepared by fusing
ECIO3 until the liquid mass becomes pasty ;
2K010s = KClOi + KCl + Oj. Marignac (B.J.2i,
192) says that when 6^ litres 0 are evolved from
100 grams of KGIO, the residue contains 65-66p.c.
KGlOj. The fused mass is repeatedly digested
at 100° with cone. HClAq, to decompose ECIO3 ;
the residue is dissolved in the smallest quantity
of boiling H^O ; the crystals which separate on
sooling are again digested vrith HClAq at 100°,
and crystallisation is repeated from boiling
, water. Pure EC104 gives no yellow colour on
digestion with cone. HClAq. One part ECIO4
is distilled with 4 parts very cone, pure HjSO,
so long as the distillate solidifies in thereoeiver;
the crystalline distillate is melted, poured into
a small retort, and gradually heated to 110°
when yellowish fumes come o& and a brownish-
yellow distillate is formed. This distillate is
redistilled very slowly and cautiously, heating
being stopped whenever crystals begin to form
in the neck of the retort. The distillate is pre-
served in small sealed glass bulbs. — 2. 600 grams
EClOj are boiled with the H^SiPjAq prepared
from 1000 grams GaP,; after cooling, the
KjSiPj is filtered ofE ; the solution of HGlOgAq
is heated until white fumes of HCIO, appear ;
the liquid is then slowly distilled from a retort ;
the distillate is freed nrom HClAq and R^SO^Aq
by shaking with AgClO, and Ba(G10J<,, filtered,
and again distilled. Prom this HC10,Aq, the
^pure acid may be obtained by distilling with 4
volumes cone. H^SO^, and rectifying as described
in 1 (Boscoe, A. 121, 846).
The first product of the action of H2SO4 on
EClO. is nearly pure HGIO4 ; this is succeeded
by a liquid containing 72-4 p.c. HCIO4, when this
drops into the receiver crystals of EC104,H20
are formed. When these crystals are slowly
heated ECIO4 distils over, but after a time the
liquid containing 72-4 p.c. HCIO4 is formed in
the retort, and coming into contact with the
HCIO, forms crystals of HCIO4.H2O.
Properties. — ^HG104 is a colourless, oily, vola-
tile, liquid ; S.G. 1-782 at 15°. Pumes strongly
in moist air. Very easily undergoes decom-
position with explosion, even when kept in
glass bulbs in the dark. Cannot be distilled
without decomposition ; at 75? change begins ;
at 92° white clouds come ofi, and a yellow gaa
smelling like CIO2, also a few drops of a liquid
resembling Br ; at a higher temperature violent
explosion occurs ; the residue solidifies to white
crystals with 87-76 p.c. HGIO, (Eoscoe). HOIO4
is an Extremely powerful oxidiser ; one drop on
charcoal, paper, wood, &e., produces combustion
with violent explosions. A drop falling on to
the skin produces a severe wound. When the
hydrate HCIO4.H2O {v. Combinations, No. 1) is
distilled under ordinary pressure nearly pure
HCIO4 passes over at 110°. The temperature
then rises until 203? is reached, when it becomes
constant, and a heavy oily liquid, exactly re-
sembling cone. H2SO4, distils over; the same
liquid is obtained by distilling HClOjAq until
203° is reached. This liquid contains 72-1 p.c.
HCIO4, and does not correspond to a definite
hydrate (HOIO4.2H2O = 73-6, HG104.3H20 =
65-05, p.c. HjO) (Boscoe, 2.c.; v. also Weppen, A,
29, 318).
Beactioni and Combinations. — 1. ,H0104 /
combines with water with a hissing sound and
production of much heat; Berthelot gives
[HC104,Aq] = 20,300 (.4. Ch. [5] 27, 214). If water
is added little by little, crystals of the hydrate
HCIO4.H2O are obtained; these melt at about
50° ; S.G. (liquid) 1-81 at 50° ; decomposition
into HCIO, and HC104.a!H,0 begins at 110°.—
2. HClOjAq is not reduced by HjS, SOj, or
HNOjAq, nor by any known substance Record-
ing to Berthelot (Bl. [2] 38, 1).— 3. HGlOjAq
dissolves Zn and Pe with evolution of H.
Ferchlorates. — HCIO4 is a monobasic acid
forming one series of salts, MC104 or M«(0104)2;
a few basic salts are also known, e.g. BiO.ClO,.'
These salts arepreparedby the action of HC104Aq
on metals, oxides, or carbonates ; or by the de-
composition of Ba(C104)jAq by sulphates ; or by
the decomposition of chlorates by heat (v. Potas-
sium chlobate), or by~HjS04Aq, or by HNOjAq
> (Penny, A. 37, 203). The perchlorates are gene-
rally easily soluble in water ; ECIO4 is one o!
the least soluble of the salts. They are iso-
morphous with the permanganates. They are
decomposed by heat into chlorides and O, or
into oxides, CI, and 0, but at higher temperatures
than chlorates. When ECIO4 is heated so as to
evolve only a part of its 0, some EOIO3 isformed
(Prankland a. Dingwall, 0. J. 51, 278; Teed,
0. J. 51, 283). Cone. H^SO, forms HCIO, at
100° ; oono. HClAq does not act onperohlorates
at 100°. Solutions of perchlorates are verj!
slowly, if at all, reduced by reagents whicb
readily reduce chlorates.
The following perchlorates have been pre.
pared: NH4.C104 (Boscoe), isomorphous with
ECIO4; Ba(C104)2(Groth,i». 133,226; Potilitzin,
C. C. 1887. 1218); Cd(C104)„. very deliquescent
(SeruUas, A. Ch. [2] 45, 270; 46, 294 ». 323);
OHLORO-ACETIO ACID,
SI
Ga(GI04)2, very deliquescent (Seiullas, l.c.);
Ou(C10,)2, large, blue, deliquescent orystalB
(Serullas, Boscoe); I'e(C104)2, long oolourlesa
needles, stable in air (Serullas) ; Fe(G104)2.3H20,
greenish, very deliquescent, crystals (Boscoe) ;
Mn(C104)2, deliquescent, not obtained in crystals
(Serullas); HgClO,, non-deliquescent needles
(Serullas) ; HgClO^.l^HjO, very deliquescent
(Boscoe) ; Hg(C10,)2 (Serullas) ; KCIO, (v. liC10„
Preparation); S. (15°) 1"6, nearly insoluble in
alcohol ; AgOlO, (Serullas) ; NaClO, (Penny, A.
37, 203) ; TICIO, decomposes in moist air
(Crookes, O. N. 8, 195) ; Zn(010,)2 deliquescent
needles. M. M. F. M.
CHLOBINE, SULFHIDi: OF, better called
SnlphuT chloride ; v. Sulfhub.
CHLOBIIES — Salts of Chlorous aM, v.
Chlobine, oxz-aoidb of, p. 18.
' GHLOBO-. Use of this prefix applied to m-
orgatm compounds ; for Chloro- compounds and
Ghloro- salts v. the element the chloro- com-
pound of which is sought for, or the salts to the
names of which Chloro- is prefixed. Thus Chloro-
phosphide of nitrogen will be found under Ni-
iBoanN, and Cfihro-plaiinate of potassium under
Flatinates.
CHLOBO-ACETAL v. Cklobo-aceiio aldehyde
and ChiiOral.
CHLpBO-ACETAUIDE v. Gblobo-acbho aoid,
and AoETO-CHLOBO-AMiDE, vol. i. p. 6.
CHLOBO-ACEXAMIDO- v. ChiiObo-amido-.
CHLOBO-ACETAITILIDE v. Chlobo-aniline.
vChloro-acetanilide v. AhiiiIne, toI. i. p. 274.
CHLOBO-ACETENE. Is merely a mixture of
aldehyde, paraldehyde, and COClj (Eekule a.
Zinoke, A. 162, 141; c/. Harnitzky, ,4. Ill, 192).
CHLOEO - ACETIC ACID CjEaClO^ i.e.
CH,Cl.COjH. Mol.w. 94-5. [63°]. An unstable
modification [52°] (ToUens.B. 17, 664). (186°).
S.G. ft 1-366.
FormaUon. — 1. From ethylene and chlorine
peroxide (Fiirst, B. 11, 2188; A. 206, 78).— 2.
Together with AcCl by the action of chlorine on
acetic anhydride (Gal, 4. 122,374).— 3. By pass-
ing chlorine into acetyl chloride mixed with
iodine and decomposing the product with water
(Jazukowitsch, Z. 1868, 234).— 4. Chloro-acetyl
chloride is formed, together with di-chloro-acetyl
chloride, by boiling AcCl (40g.) with FOl, (200g.)
for some weeks (Michael, J. pr. [2] 35, 95).
Preparation. — 1. Dry chlorine is passed into
a retort containing acetic anhydride heated to
100°, dry acetic acid being simultaneously run
in. The acetyl chloride which is formed :
(CH3,CO)jO + Clj = CHjCLCOaH + CH3.CO.CI
is at once reconverted by the acetic acid into
anhydride, which is again attacked by the chlor-
ine, and so on, so that a small quantity of an-
hydride suffices for the chlorination of a large
quantity of acetic acid. When the absorption
of the chlorine slackens the mixture is fraction-
ally distilled (Hentschel, B. 17, 1286; cf. B.
Hoffmann, A. 102, 1). — 2. By passing chlorine
through a heated mixture of 50 g. iodine and
500 c.c. nearly glacial acetic acid S.G. 1-065.
The rectified product contains a little iodo-acetio
acid (Hugo MtiUer, C. J. 17, 398).
Properties. — ^Deliquescent trimetrio tablets or
needles. Blisters the skin; nearly inodorous.
V. sol. water, with absorption of heat.
B«Mtions. — 1. Water slowly converts it on
heating into glycollic acid (Buchanan, B. 4, 840,
868). CausUe potash acts similarly, while baryta
forms di-glycollic acid OfEJ)^ (KekuU, A. 105,
288 ; cf. Schwab, B. T. C. 2, 46).— 2. Ohloro-
aoetic acid (lOg.j boiled with PCI5 (88 g.) yields
tetra-chloro-ethylene and other bpdies (Michael,
Am. 9, 216).— 3. Sbdmm-a/nialga/nt partially re-
duces it to acetic acid. — 4. By heating with
dimethylaniUne it is broken up into iuetbyl
chloride and CO,; this decomposition is pro-
duced by the intermediate formation of the
body FhMejClN.CHj.COjH, which splits up into
COj, CHjCl, and dunethylaniline (Silberstein,
B. 17, 2661).
Salts. — KA' IJaq: laminsB, v. sol. water but
not deliquescent and not dehydrated at 100°, but
converted into glycollic acid at a higher tem-
perature. The same change takes place when
its aqueous solution is evaporated even below
100°. — EHA'ji small pearly crystals, si. sol.
water. — ^BaA'^aq : prisms. Decomposed but
slightly when its aqueous solution is evaporated,
and separates almost completely on cooling a
hot saturated solution. — AgA': pearly scales;
detonates at 110°-120°.
Methyl ehloro-acetate CHjCl.COjMe
(130°) (Schreiner, 4.197, 1). V.D. 3-71 (for 3-74).
S.G. i£ 1-22; 12 1.235 (Henry, C. B. 101, 260).
S.H. '389 (B. Sohiff, 0. 17, 286). Frepared by
passing HCl into a solution of chloro-acetic acid
in MeOH (Henry, B. 6, 743) or from CHjCl.CO.C/
and MeOH (P. J. Meyer, B. 8, 1152). InsoL
water. Converted by ammonia into chloro.,
acetamide.
Ghloro-methyl ether 0HsCl.C02.0Hj01.
(197°). S.G. Ill 1-822. From CHjCl.C0.Cl and
glycolic chlorhydrin (Henry, 0. B. 97, 1308). -
Ethyl ether CHjCLCOjEt. Mol. w. 122'j.
V.D. 4-24 (calc. 4-23). (143°) (Schreiner,'^. 197,
1); (144-5°) (Schifi, A. 220, 108). S.G. =,<■
1-1585 (Briihl, A. 203, 21). S.H. -401,
Mfl 1-428. Boo 43-51. S.V. 123-1.
Formed by ' mixing chloro-acetyl chloride
with alcohol in the cold (Willm, A. Ch. [3] 49,
97 ; A. 102, 109) ; or by heating chloro-acetic
acid (200 g.) with alcohol (120 g.) and H2SO4
(25 g.) for 6 hours at 100° (Conrad, A. 188, 218).
Oil with ethereal odour. With ammonia it
forms chloro-acetamide. It unites with Me^S
at 100° forming the hydrochloride of di-methyl-
thetine (Crum Brown a. Letts, Pr. E. 28, 583).
Chloro-acetic ether (2 mols.) heated with (1,
3, 4) tolylene-diamine (3 mols.) at 100° forms
oxy-toluquinoxaline dihydride thus :
80.H,Me(NH,).+20H,Ca.CO^t
=20.H.Me<^^;^^^+O.H.Me(NH,01).+3HOia.
When, however, chloro-acetic ether (2 mols.)
is heated with a smaller quantity (1 mol.)
of tolylene-diamine at 100° a compound
OiaHijNjOa [147°] is formed; it may be
OAMe<jj(0^:S&t)>CO (^""'^''S' ^■
237, 361). \
Chloro-ethyl ether CBjOl.C02.CS^.C^CiL
(198° uncor.). S.G. — 1-322. From chloro-
acetyl chloride and glycolic chlorhydrin (Henry,
C. B. 97, 1308). Also from ethylene and CljO
(Mulder a. Bremer, B. 11, 1958).
Propyl ether CHjCl.COjPr. (161°) (Schrei-
as
OHLORO-ACETIO ACID.
oer, A. 197, 1). S.G. « 1-11 (Henry, J.pr. [2] 31,
127). S.H. -422 (Sohifi, G. 17, 486).
n-Butyl ether CB.fil.COfi,B.,. (175°).
S.G. 2 1-103 ; is. 1-081. V.D. 5-1 (Gehring, Bl.
[2] 46, 146; 0.5.102,1399).
Isoamyl ether OHjCl.COjOsHnJ (190°).
S.G. 2 1-063 (Hugonnenq, Bl. [2] 45, 328).
see-Octyl ether CSfil.CO.fija.,,. (234°).
S.G. 12 -990. From ootyl alcohol of castor oil
(Gehring, 0. R. 104, 1000).
Phenyl ether CUfilCO^V^. [40°]. (230°-
235°). From phenol and chloro-aoetyl chloride.
Needles (Prevost, J.pr. [2] 4, 379).
Benzyl ether CIIjPhA'. (148°) at 9mm.
S.G.Jl-222.
Chloride V. Chlobo-aceiyii cblokide.
Amide CHjCl.CO.NH^. Chloro-acetaimde.
[119°] (Mensohutkin a. JermolajefE, Z. [2] 7, 5) ;
[116°] (Bauer, A. 229, 165). (225°). S. 10 at
24°.- S. (alcohol) 9-5 at 24°. Prom ohloro-acetio
ether and aqueous or gaseous NH„ or from
shloro-acetyl chloride and dry ammonia (Willm,
A. Ch. [3] 49, 99). Thick monoclinic prisms or
flat plates (from alcohol). Its aqueous solution
after treatment .with HgO deposits slender
needles of Hg(NH.CO.CH2Gl)2. Alcoholic KCy
forms 0„H,sClaN,03 (?) (SohifE a. Speoiale, G. 9,
335). Br and' KOHAq give ohloro-methyl-
ohloro-acetyl-urea OH.,Cl.NH.OO.NH.CO.OHjCl.
(Wallach, A. 184, 30).
Anilide CHjCl.CO.NPhH. [134°]. From
aniline and ethereal CH^CLCOCl (Wallach a.
Kamensky, A. 214, 221 ; Tommasi, Bl. 19, 400 ;
Cech, B. 10, 1376; Meyer, B. 8, 1152). Crys-
tallises from henzene. When treated with FCI5
it gives oS HGl and forms a base whose hydro-
chloride is insol. water, benzene or ether, but
crystallises from alcohol in long yellow silky
needles which appear to be CijHi^Cl^NjHCl.
p-Toluide CH^Cl.OONHOjHiMe. [162°]
(Meyer; Tommasi, 0. J. 26, 911; 27, 628)^
Nitrile CB.fi\.C^. (124°). S.G. S2 1-193.
V.D. 2-62. From the amide and VJO^. The
yield is 50 p.c. of the theoretical (Bissohopinck,
B. 6, 732 ; Engler, B. 6, 1003 ; Bauer, 4. 229, 165).
Di - chloro - acetic acid CjHjCljOj i.e.
0HC1,.C0.^. (190°). S.G. 15 1.522.
Formation. — 1. By the chlorinatiou of acetic
or of chloro-acetic acid (MaumenS, J52. [2] 1, 417).
9. By the action of aqueous ECy upon chloral
(Wallach, A. 173, 295).
Preparation. — By boiling chloral hydrate
(50 g.) with water (250 g.) and KjFeCy„ (84 g.) ;
the resulting potassium salt being extracted by
alcohol (WaUach, B. 9, 1212 ; 10, 1526).
PrqperWes.-r-Corrosive liquid; solidifies be-
low 0°.
Reactions. — 1. Converted into glyoxylic acid
by heating with moist AgjO. The same reaction
iis slowly effected by water at 100°, and by
alkalis (Beckurtsa. Otto, B. 14, 583).
Salts. — BA': laminaa (from alcohol). — AgA':
prisms, b1. sol. cold water; decomposes vio-
lently at 80°. — CaA'j 3 aq : needles (from alcohol).
— Na(UrO)2A', (Clarke a. Owens, B. 14, 35).
p-Toluidine di-chloro-acetate
CeH,Me.NH,0.C0.CH01,: [136°]; white needles
ffiuisberg, B. 18, 194). ,
' Methyl ether GKCi^.CO,Ue. (144°) (Wal-
lach, A. 173, S99). S.G. 12 1-381 (Henry, C. B.
101, 260). S.H. -322 (Sohiff, G. 17, 286).
E thyl ether OnCl^CO^t. (167°). S.G.w
1-2821 (Bruhl, A. 203, 22). fi^ 1-444. Ra> 62-19.
V.D. 5-38 (for 5-42). S.H. -338 (S.). S.V. 143-4.
Wormation.—l. Together with glyoxylic ether by
heating O^Cl, with NaOEt at 100°-150° for 13
hours. — 2. By adding chloral hydrate (1 mol.) to
potassium cyanide (1 mol.) in absolute alcohol :
CCls.CH(0H), + EtOH + KCN
- CH0ij.C0,Bt -f HON -H KCl + HjO. Or by gently
heating chloral cyanhydrin (1 mol.) with alcoholic
NaOEt (Wallach, B. 6, 114; 10, 1527, 2120).
Reactions.— 1. Boiling alcoholic KCy gives acetic
and oxaUc acids (Claus, B. 11, 496, 1044).—
2. Silver, or Na, converts it into maleic ether.
3. Alcoholic EOH gives glycollic acid (Claus,
B. 14, 1066).
Propyl ether CHClj,.COjPr. S.H. -352.
Isobutyl ether CHClj.CO^CHjPr. (183°).
s-Octyl ether GH,Gli.COAn„. (244°)(Geh.
ring, 0. R. 104, 1000).
Benzyl eifeer 0HClj.C08.0HjPh. (179°) at
60 mm. S.G. i 1-313 (Seubert, B. 21, 281).
Aviide CHCIJ.CONH2. [98°] (Hantzsoh a.
Zeckendorff, B. 20, 130'9). (234°). From the
ether and alcoholic NH„ or from chloral cyan-
hydrin CCls.CH(OH).CN and aqueous NH, (Pin-
ner a. Fuchs, B. 10, 1066). Monoclinic columns.
V. sol. hot water. It unites with chloral forming
CCl3.CH(0H).NH.C0.CHCl„ which crystallises
from water in prisms. PCI5 converts it into
CHCl2.CCl:N.P0Clj (Wallach, A. 184, 28).
Ethylamide CHCl^.CONHEt. [59°]. (226°).
Converted by PCX, into CHCl2.CClj.NEt.POCl,
(140° -150°) and CHClj.CCl:NEt (c. 163°).
^TOiZide CHOl2.CO.NHPh. [118°]. Forma-
tion.— 1. By the action of aniline on chloral in
presence of KCy or on chloral cyanhydrin (Cech,
B. 9, 837 ; 10, 1265).— 2. From aniline, di-chloro-
acetio acid, and P2O5 (C). — 3. By warming di-
chloro-acetamide with aniline (C). Properties.
Crystalline scales (from water); si. sol. hot water;
sol. KOHAq and reppd. by acids.
iVitj-iieCH01j.CN. (113°). V.D. 3-82. S.G.
11 1-374 (Bisschopinok, B. 6, 732). Formed by
distilling the amide with PjOj. Absorbs HCl
forming a crystalline compound which, when
heated in a sealed tube at 140°, splits up into
HCl and a polymeride of dichloro-acetonitrile
[70°] (Weddiga a. Korfier, /. pr. [2] 31, 176).
hi-chloro-ortho-acelic ether
CHCLj.C(OEt),. (205°). Formed together with
other bodies by heating Cfi\ with NaOEt at
100°-120°. Decomposed by water. Decomposed
by NaOEt into NaCl and di-ethyl-glyoxylio ether
(Geuther a. Brockhoft, J.pr. [2] 7, lOJ.).
Tri-chloro-acetio acid C^Glfi^Le. CCl,.COjH.
Mol. w. 163J. [55°]. (195°). S.G. ff 1-617. V.D.
5-3. Formation.-r-l. By the action of dry chlorine
(3 mols.) on glacial acetic acid (1 mol.) in sun-
shine (Dumas, A. Ch. [2] 73, 75).— 2. By the
oxidation of chloral with HCl and KCIO,, and of
chloral or metachloral with fuming HNOj (Kolbe,
A. 54, 182).— 3. Together with CjCl, by passing
chlorine into CjCl^ under water in sunlight (K.).
4. From CC1,.C0.C1, which is formed by chlorin-
ating ether (Malaguti, A. Ch. [3] 16, 10).
Prepm-ation.—l. Chloralhydrate(165Jpts.)is
just melted and fuming HNO, (63 pts.) is added.
The reaction proceeds without application of
heat, and after half an hour the liquid is frac-
tionally distilled (De Clermont, A, Ch. [6] 6, 135 ;
CHLORO-ACETIC AOID.
23
[6] 2, 401 ; C. R. 73, 112, 501 ; 74, 942 ; 76, 774 ;
81, 1270 ; cf. Tommasi a. Meldola, C. J. 27, 314 ;
Judson, Z. p] 7, 40).— 2. Chloral hydrate (165 g.)
is mixed with EClO, (37 J g.) ; as soon as the
mixtuie is melted a violent action sets in, with
evolution of gas, and potassium tii-ohloio-acetate
(120 g.) is formed (Seubert, B. 18, 3336, 3339).
Properties. — Deliquescent rhombohedral
scales. Y. sol. water. Blisters the skin. Its va-
pour is pungent. Markedly exhibits superf usion.
Beactions.^-l. Cone. HjSO, forms 00, COj,
and HCl. — 2. Both the acid and its salts are
decomposed by boiling with water or alkalis
into 00, and chloroform. Ammonia, dimethyl-
aniUne, and KCy also liberate chloroform (Sil-
berstein, B. 17; 2664 ; Bourgoin, Bl. 37, 403 ;
C. R. 94, 448). — 3. It is reduced to acetic acid by
fuming HI at 100° (Olermont), by electrolysis
(E.), or, in aqueous solution, by (f p.c.) potas-
sium amalgam (Melsens, A. Oh. [3] 10, 233). — 4.
KaOEt forms sodium chloride, carbonate, and
formate.— 5. KjSOsAq for OHO^SOjKjCOjKlJaq
(Bathke, A. 161, 149). — 6. Forms a compound
with aluminum chloride which is decomposed
by steam thus : (00l3.CO2)2Al2Cl, -1- pH^O
= 2CHCl3 4-2COj+4H01 + Al2(OH), (Elbs a.
Tolle, J. pr. [2] 32, 624).
Salt s. — EA' aq : long slender needles. Heated
with bromine it forms CO,, EBr, and CBrCl,
(Van 't Hoff, B. 10, 678).— EHA'j-. octahedra;
S. 26-1 at 0° ; 33-75 at 20° (Seubert).— NaA' 3aq.
On dry distillation it givesNaOl, CO, CO,, COCC
tri-chloro-acetyl chloride, tri-chloro-acetic acid
and its anhydride, and a little CjCl, (Henry, B.
12, 1844).— NH,A'2aq: [80°]; prisms. Boils
at 110°-115°, giving o£E chloroform and am-
monium bi-carbonate, and leaving NH^A', which
is soUd at 160°, but at a higher temperature
splits up into NHiOl, CO, and 0001, (M.).—
NH^HA', : octahedra — LiA'2aq: deliquescent
prisms— TlA'-TlHA'j—AgA': laminse, si. sol.
water ; explodes when heated, forming
AgCl, CO, CO,, and tri-chloro-acetic anhydride.
— CaA'jBaq: prismatic needles. — CaA'j3iaq. —
SrA'.6aq: radiate groups of prisms. — BaA^Baq :
very' thin laminaB. — MgA'j 4aq. — ZnA', 6aq :
laminffl.— CuA'j6aq (Judson, B. 3, 782).— HgA', :
prismatic needles, — Hg^',: small needles, sL
sol. water. — FbA'^aq: large prisms, v. sol. water,
b1. sol. alcohol.
Methyl ether CClj.COjMe. (154°) (Henry,
C. B. 101, 250). S.G. Ji? 1-489. S.H. -277
(Schiff, G. 17, 286). Obtained by distilling the
acid with methyl alcohol and H2SO4 ; or by the
action of methyl alcohol on the chloride or chlor-
inated aldehyde. Oil, smelling of peppermint.
Tri-chloro-methyl ether 001^.00.00013.
S.G. IS 1-705. (0.200°). Prom the preceding or
from inethyl acetate by. chlorine in sunshine.
Said to be identical with the penta-chloro-ethyl
Sther of chloro-formic acid CI.CO.O.CCI2.CCI3,
(180°-185°), S.G. i2 1-724 (Cahours, A. 64, 315).
Decomposed by moist air and by aqueous alkalis
into HCl, CO2, and tri-chloro-acetic acid. Bea^'-
Uons. — l.^TOBKmia gives tri-chloro-acetamide. —
2. jlZcok)Zgives tri-chloro-acetic ether and chloro-
formic ether; methyl alcohol acts similarly. —
3. Its vapour passed through a red-hot tube gives
COClj and tri-chloro-acetyl chloride.
Ethyl ether CClj.CO^Bt. (167°). S.G. f
»-3826(Bruhl). m/> 1-4667. Boo 60-57. S.H.-296.
V.D. 6-59 (for 6-61>. S.V. 163-8 (Schiff). Ob-
tained by distilling the acid with alcohol and a
little HjSO^ (Clermont, A. Ch. [6] 6, 241). Oil,
smelling of peppermint. , Heated with KCy
and absolute alcohol it yields CO2 and chloro-
form (Claus, A. 191, 58). POI5 at 150° forma
EtOl, POCI3, and OOI5.COOI (Michael, Am. 9,
213). Heated with KaOEt (containing NaOH)
it forms orthoformic ether, NaCl, and NaEtCO,
(Klien, J. 1876, 521). With EjSO, it forms
CHCl(S0aK)jC02K liaq (Bathke, A. 161, 166).
Penta-chloro-ethyl ethtr
CGl,.C0AClv (245°). S.G. ^ 1-79 (Malaguti,
A. Ch. [3] 16, 57; Oloez, A. Ch. [3] 17, 304).
Formed by passing chlorine through acetic
ethei:, finally in sunshine (Leblanc, A. Ch. [3]
10, 200). Liquid, gradually decomposed by
moist air into HOI and tri-chloro-acetic acid.
Reactions. — 1. Alcohol forms tri-ohloro-acetic
ether. — 2. Ammonia forms tri-chloro-acetamide.
8. Prolonged action of chhrime forms C^Cl,. —
4. Passage through a tube at 400° yields tri-
chloro-acetyl chloride.
Propyl ether CClj.COjPr. (187°) (Cler-
mont, C.R. 96, 437). S.H. -306.
Isobutyl ether C01,.OO^.CB^¥i.(188°){3.).
Isoamyl ether CC1,,C0,AH„. (217°) (C).
s-Octyl ether CC1,.C0,C,H„. (260°) (Geh-
ring, C. B. 104, 1001). Light oil.
Benzyl ether CHjPhA'. (179°) at 50° mm.
S.G. 1 1-389.
Anhydride (CCls.C0)j0. (224°). Formed
by treating the acid with PClj or CClj.COCl
(Buekney a. Thomsen, B. 10, 698 ; Clermont,
Bl. [2] 30, 505; C. B. 86, 337). Hygroscopic
liquid, rapidly converted into the acid by water. '
Chloride v. Tri-osLono-kcsTn, chloride.
Amide CCl,.OO.nSi. Mol. w. 162i. [136°].
(239°). Formed by the action of ammonia on
tri-chloro-acetyl chloride, on tri-chloro-acetio
ether, on perchlorinated acetic ether (v, supra),
and on perchlorinated formic, carbonic, oxalic,
and succinic ethers (Malaguti, A. 56, 286 ; Cloez,
A. 60, 261, A. Oh. [3] 19, 352 ; Gerhardt, Compt.
Ohim. 1848, 277). Preparation. — ^By mixing
NH, (1 pt.) dissolved in alcohol (10 pts.) with
trichloracetic ether (11 pts.) dissolved in alcohol
(16 pts.). The mixture is kept' cool. After 12
hours the reaction is complete (A. Weddige, J.pr
[2] 33, 78). Properties. — Monoclinio tables (from
water) ; sweetish taste. SI. sol. water, v. sol. al-
cohol and ether. Reactions. — 1. Amnionic^ forms
ammonium tri-chloro-acetate. — 2. F^O, gives the
nitrile.— 3. PCI, gives CC1,.CC1:N.P0C1, [c. 81°]
(0. 257°) (WaUach, A. 184, 23).
Chloro-amide CC1,.C0.NHC1. [121^.
Formed by the action of chlorine-water on tri-
chloracetamide (Cloez, A. Ch. [3] 17, 305).
Very volatile with steam. Large plates. Sol.'
alcohol, and ether, sl. sol. water. It dissolves in
NHjAq with re-formation of tri-ohlor-acetamide.
It is scarcely altered by boiling with alcoholic
EOH. By neutralising the alcoholic solution of
the chloro-amide with alcoholic EOH a well
crystallised potassium salt (CC1,.C0.KC1K) is
formed (Steiner, B. 15, 1606).
Methylamide OOl,.COTiiB.Me. [106°]. From
tri-chloro-acetic ether and inethylamine. Crys-
tals, sl. sol. water and ether, slowly attacked by
HNO3 (Pranchimonta.Klobbie,iJ.r. 0. 6, 234).
Di-methyl-amide COla.CONMe,. [0. 12°1.
u
Cm-ORO-AOETIO ACID.
(233°). S.O.iS 1-441. V.D. 6-68. Not attacked
by HNO, (S.G. 1-53) (F. a. K.).
Ethyl-amide OOl3.CO.NHBt. [74°]. (230°).
Qnadran^lar tables. Insol. cold water, v. sol.
alcohol, ether, or chloroform (Wallach a. Kamen-
sky, A. 214, 225). PCI5 appears to form the
imido-chloride COlsCOhNEt, but this gives no
basic condensation product.
Di-ethyl-amide COlj.CONEtj. [27°].
(F. a. K.) ; [90°] (Cloez). V.D. 7-23 (F. a. K.).
From hexa-ohloro-acetone and NEtjH (Oloez,
jun., A. Oh. [6] 9, 145). Crystals. Not attacked
by pure HNO, (S.0. 1-53) (P. a. K.).
Allyl-amide CG\.CO.niiC;B.y [45°].
(190°). From allylamine and hexa-chloro-ace-
tone (Cloez).
Anilide C01,.C0.NPhH. [94°]. Scales
(if om alcohol) ; gives no basic condensation pro-
dact with PCI,.
o.Toluide C01,.00.NH.C,H,Me. [G7°].
(215°). From hexa-chlorb-acetone and o-tolu-
idine (Cloez, jun., A. Ch. [6] 9, 145).
p-Toluide CCl,.C0.NH.0,H4Me. [80°].
(185°) (Cloez).
mtrile CC1,.0N. (84°). S.G. 12 1-439. V.D.
5-03. Formed by the action of chlorine on ace-
tbnitrile containing iodine (Beckurts, B. 9, 1594).
From the amide and PjO, ; the yield is 90 p.c.
(Dumas, Malaguti, a. Leblanc, C. B. 25, 442 ;
BisBchopinck, B. 6, 732; Bauer, A. 229, 165).
Pungent liquid, insol. water, sol. alcohol, ether,
and light petroleum. Forms ,a crystalline com-
pound with HBr which is decomposed by water.
Warmed with HCl changes to trichloro-aoetic
, acid. Polymerises when kept. NaOEt forms
ethyl derivatives of the nitriles of dichloro-gly-
colUo acid, and of ohloro-glyoxylio acid.
Paranitrile (CCI3.ON),. Per-chloro-tri-
methyl-cyanidine. [96°]. Formation. — 1. Cyauo-
formic ether, ON.OO.^Et, is distilled with PCI,,
and the liquid product, probably CN.COOl, is
heated in a sealed tube at 160° with PCI,. The
product is distilled with steam and crystallised
from alcohol. The yield is 6 per cent. (A. Wed-
dige, J. pr. [2] 28, 188 ; 33, 77).— 2. From ordi-
nary tri-chloro-acetonjtrile by saturating it with
HCl and exposing it, m sealed tubes, to sun-
light. In about a year the contents of the
tubes solidifies. The solid nitrUe is crystal-
lised from alcohol. Properties. — ^Large prisms
(from hot alcohol). Sol. alcohol, benzene, ether,
CSj, and chloroform. Hardly sol. water. Volatile
with steam. Beactums.—!. Decomposed by al-
coholic potash, thus :
(0C1,.CN), + 3K0H = 0,N3(0K), + SCHCl,,
forming chloroform and potassic cyanurate. —
2. Boiled with alcoholic ammonia it reacts thus :
C,N3(GC1,), -I- NH3 = HCCI3 + C3N3(CCl3),.Na.
The latter body forms flat prisms (from alcohol)
[166°]. It is sol. alcohol, ether, and benzene,
scarcely sol. water. It is not a base. — 3. When
heated with alcohplic NHj.in sealed tubes at
110° tri-chloro-acetic paranitrile reacts thus :
C3N.(CCl3), - 2NH, = 2CHC1, + C3N,(CCl3)(NH,),
The diamide crystallises from alcohol either in
long pyramids containing alcohol or in short
six-sided prisms without alcohol of crystallisa-
tion. It melts at [236°]. It is si. sol. ether and
benzene, hardly sol. cold water. It forms a salt,
C,N,(CCl3)(NH2)jHC12aq., crystallising in pearly
plates. This salt is decomposed by boiling water.
Boiled with NHjAq it forms ammeline, or an
isomeride C3N3(0H)(NH,)j.— 4. Heated with ,
NHjAq at 120°', or alcoholic NH, at 170° it
forms 03N3(OH) (NHJj u. Ammeline.— 5. Aqueous
or alcoholic methylamme at 20° forms
0,N3(CCl,)jNHMe. Small crystals [117°]. V.
sol. alcohol, sol. benzene. Is not a base.
With alcohoUo ammonia at 110° it gives rise to
C3Ns(CCl3){NH2)(NHMe). This body is also got
from C3N3(CCl3)j(NHj) and alcohoUc methyl-
amine. It forms colourless crystals [153°-165°].
6. Alcoholic methylamine at 110° in a sealed
tube forms C3Ns(CCl3)(NHMe)j. Small white
crystals [207°]. Sol. alcohol and benzene. Forms
salts. — 7. Aqueous methylamine at 120° forms
C,N3(0H)(NMeH)„. Slender needles. Forms a
piatino-chloride (B'HC^jPtCl, (Weddigej v. also
Hofmann, B. 18, 2770).
CHLOEO-ACETIC ALDEHYDE CHjCl.CHO.
(85°).
Formation. — 1. From vinyl chloride, HCIO,
and HgO (Glinsky, Z. 18G7, 678; 18G8, 617;,
1870, 647). — 2. From di-ohloro-ether and cone.
UJ80, (Jacobsen, B. 4, 216).
Preparation. — A mixture of ohloro-acetal
(1000 g.) and dry oxalic acid (590 g.) is distilled
at 100°-150° in an atmosphere of COj. The
residue consists chiefly of oxalic ether, the dis-
tillate contains formic ether, oxalic acid, and
chloro-acetic aldehyde. A portion (87°-91°) puri-
fied by fractional distillation 'is obtained in the
form of a crystalline hydrate either by use of a
freezing mixture or by means of NaHSOj. Water
of crystallisation is removed by distillation over
CaClj or CuSP,. The anhydrous aldehyde is,
however, best obtained by distilling its poly-
meride (Natterer, Jkf. 3, 442). ' >
Properties. — Colourless liquid which com-
bines with water, forming a crystalline hydrate,
CH2CI.CHO laq [43°-50°]. The V.D. (1-98) of
the hydrate shows that it dissociates. It forms
monoolinic crystals. Sol. water, alcohol, and
ether ; blisters the skin. Beduces ammoniacal
AgNOj, forming a mirror.
Beaetions. — 1. Oxidised by HNO, to chloro-
acetic acid. 2. Potassium, cyanide gives an oil
(CH3Cl.CH0)(CH,Cy.CH0) whence HCl forms
acetic and chloro-oxy -propionic acids. — 3. By
heating alone or with some H^SOj it is converted
into d7-di-ohloro-trotonio aldehyde. — 4. HCl
passed into a mixture of chloro-acetic aldehyde ,
and alcohol forms di-ohloro-ether.
Oombinaiioiis. — 1. With alcohol it forms an
alcoholate, CH2Cl.CH(0H)(0Et). (c. 94°). Also
formed from di-chloro-etb«r with water (7 vols.)
at 120° (Abeljanz, A. V , 217). Repeated dis-
tillation converts it into CgHisCL^O, (164°).—
2. With acmtyl chloride: CHjCl.CHCl(OAo).
(c. 147°). Formed also by reducing the corre-
sponding compound of chloral with acetyl
chloride by Zn and acetic acid (Curie a. Milliet,
B. 9, 1611).— 3. With bisulphite of soda:
C2H,010NaHS03 2aq: siX-sided tables (from
water). Separates from alcohol as a powder
(containing ^aq). Boiling Na2C03 decomposes
it without regenerating the- chloro-acetic alde-
hyde.—4. With calomel : 02H,CiOHg.i01j.
Chloro-acetic paraldehyde (CjHjClO),. [87°].
(140°) at 10 mm. S.G. 2-77. V.D. 8-25 (calo.8-31),
An amorphous porcelain-like mass into which
the aldelhyde slowly changes on keeping (pro-
CHLORO-ACETIO ALDEHYDE.
25
babl; when not perfectly pure). It also sepa-
rates from a solution of the hydrate in oonc.
HjSO^. Trimetrio crystals, a : 6 : c = 1'51:1: -941.
Insol. water, si. sol. cold alcohol, v. sol. ether.
M 245° it is reconverted into the ordinary modi-
fication. Not acted upon by iron and acetic acid,
by AgOAc and HOAo, by alcoholic HH„ by
KOHAq at 100", or by cold NaOEt (Natterer,
M. 6, 519).
Chloro-acetic orthaldehyde
''CHj01.CH(0H)2. Contrary to analogy, the
hydrate of ohloro-acetic aldehyde does not seem
to have the above formula, but appears to be
OH,C1.0H(OH).O.OH(OH).CH,C1 (v. supra). The
di-alkylated derivatives of ohloro-acetic ortho-
aldehyde are called acetals.
Ethyl etfcar 0H201.CH(0H)(0Bt). Chloro-
aldehyde ahoholate. {93°-95°). Formed by the
action of water at 120° on diohlorinated ethyl
oxide CHjCl.CHCl.OEt. On distillation it forms
an anhydride, (CH201.CH.OEt)jO, (les^-lGS"),
which is split up by oonc. H^SO, into ohloro-
acetic aldehyde and alcohol. This body is also
formed from di-ohloro-di-ethyl ether and potash.
Acetyl derivative of the ethyl ether
CHj01.CH{0Et)(0Ac). (170°). from di-chloro-
ethylether and silver acetate (Bauer,^. 134, 176).
Methyl ethyl ether 0H2Cl.CH(0Et)(0Me).
(137°). S.a. li 1-056. From di-ohloro-ethyl ether
and sodium methylate (Lieben, A. 146, 202).
Di-ethyl ether 0H201.CH(0Et)2. Ghloro-
acetal. (157°). S.d. a 1-042. V.D. 5-38 (oalc.
5-29). Formation. — 1. When chlorine is passed
into dilute alcohol (80 p.c.) for some time, on
adding water a heavy oil separates. By fractional
distillation this is found to consist chiefly of alde-
hyde, chloro-acetal, and di-chloro-acetal. The
fraction 120°-170° is digested for several days
with aqueous EOH and rectified (Lieben, A. Ch.
[3] 66, 313 ; Krey, Jena. Zeit. 10, 84).— 2. Prom
di-chloro-ethyl ether CH^Cl.CHCl.OEt and
NaOEt(Lieben,4. 146,193 ; Natterer, M. 3,444);
or by long boiling with alcohol (Paterno a. Maz-
zara, B. 6, 1202). — 3. From di-ohloro-ethylene
and aloohoUo NaOEt at 40°-50=' (Klien, J. 1876,
336).— 4. By warming chloro-acetic aldehyde
with alcohol (Natterer, M. 5, 497). Properties. —
Aromatic liquid, insol. water, sol. alcohol. Not
attacked by aqueous EOH. Does not pp.
AgNOj. — Beactions. — 1. NaOEt at 150=
gives CH.^(0Et).CH(0Et)2. — 2. Sodium forms
OH^rCH-OBt (WisUoenus, A. 192, 106).^3. Boil-
ing with powdered zinc gives EtCl and alcohol. —
4. Heating with oxalic acid gives chloro-acetic
aldehyde and oxalic ether. HOAc acts simi-
larly.— 5. HCl gives di-chloro-ethyl ether
OH2Ol.CHCl.OEt. — 6. Poured upon bleaching-
■powder, no action ensues, but upon heating over
a water bath a reaction takes place and a green-
ish liquid collects in the receiver. This distillate
presently decomposes, the products being chlor-
ine, HCl, undecomposed ohloro-aoetal, di- and
tri-chloro-acetals, chloroform, and an aldehyde
(Goldberg, J.pr. 132, 109).
D -chloro-acetic aldehyde, CHOlj.CHO.
Mol. w. 113. (89°).
Formation. — 1. By distilling di-chl6ro-acetal
with HjSO, (Grimaux a. Adam, Bl. 34, 29 ; Pa-
terno, Z. 1868, 667).— 2. By boiling CCl,:CH.OMe
with dilute H^SO, (Denaro, Q. 14, 119').— 3. By
distilling its hydrate obtained by ehlorination
of chloro-acetic paraldehyde (v. di-chloro-acetio
ortho-aldehyde) with H.SO4.
Properties. — ^Liquid, which, in presence of
some HCl, gradually changes to an amorphous
solid variety, which at 120° returns to the liquid
form.
Beactions. — 1. Oxidised by HNO, to dichloro-
acetio acid.— 2. PClj forms CHCL,.CHClj (147°)
(Paterno, Z. 1863, 667).
Si-ohloro-acetic paraldehyde
(CHCl2.CH0)a,. [130°]. S.G. 1-69, From di-
ohloro-acetic aldehyde (or di-chloro-acetal) in
presence of H^SO, in the cold (Jacobsen, B. 8,
87 ; cf. Kroy, J. 1876, 475). Hexagonal pyra-
mids (from alcohol). V. sol. hot alcohol. May
be sublimed, but at 240° in a sealed tube, or with
cone. HjSO, at 130°, it changes to liquid di-
chloro-acetic aldehyde.
Amorphous polymerlde (CHClj.CHO)„.
Formed spontaneously by the polymerisation of
(impure ?) di-chloro-aoetic aldehyde (Friedrich,
A.. 206, 252). Paraffin-like mass, insol. water,
m. sol. ether, si. sol. hot alcohol. Does not
melt below 200°. Converted by heat into ordi-
nary di-chloro-acetic aldehyde.
Dl-chloro-acetic orthaldehyde
CHCl2.CH(0H)j. Di-chloro-acetic aldehyde hy-
drate. [43°] (F.) ; [57°] (Denaro, <?. 14, 120)
(c. 120°). Formed as a by-product in the pre-
paration of tri-chloro-butyric aldehyde by the
action of chlorine upon paraldehyde (Friedrich,
il. 206, 251). Micaceous scales. T. sol. water and
ether. Oxidised by HNO3 to di-chloro-acetic acid.
Cone. H2SO4 converts it into di-chloro-acetic
aldehyde and its amorphous polymeride.
Di-ethyl ether CB.01i.CB.{0Mt)t. Di-chloro-
acetal. Mol. w. 187. (184°). V.D. 6-45 (calo.
6-44). S.G. " 1-138. Formed by chlorinating
alcohol (v. swpra) or aoetal (Lieben, A. 104, 114 ;
Pinner, B. 5, 148; Krey, J. 1876, 474). Also
fromtri-ohloro-ethyl ether CHClj.CHCl.OEt and
NaOEt, (Jacobsen, B. 4, 217).
Beactions. — 1. Zinc-ethyl at 140° gives pro-
pylene, ethylene, and other gases, leaving ether:
,(Paterno, C. B. 77, 458).— 2. PCI5 gives tri-
ohloro-ethyl ether CHCl2.CHOl.OEt.— 3. NaOEt
gives the tetra-ethyl derivative of ortho-glyoxal
CH(OEt)j.CH(OEt)j (Pinner, B.5, 151).— 4. Cone.
H2SO4 or HClAq converts it into di-ohloro-acetio
aldehyde. Fuming HjSO, forms a crystalline
compound O^fiXfi, [129°] (Grabowsky, B. 6,
1071). According to Pinner (A. 179, 34) di-chloro-
acetal is not converted into di-chloro-acetia
aldehyde by H2SO4, and does wof give di-chloro-
aoetio acid on oxidation by HHO,. '
Tri-chloro-acetic aldehyde v. Chlobal.
Tri-chloro-acetic orthaldehyde v. Chloual
hydrate.
Di-ethyl ether CCl3.CH(OEt)2 (v. p. 4).
An isomeride, possibly having the consti-
tution CHClj.CCl(OEt)j, [72°] (P.); [83°] (K.),
(230°), is formed as a secondary product in the
preparation of di-chloro-acetal by the ehlorina-
tion of 80 p.c. alcohol (Paterno, 0. B. 67, 765 ;"
Lieben, X. 104, 114; Kley, /. 1876, 475). Needles
(from ether). Volatile with steam. It is doubt-
ful whether it yields chloral on treatment with
H2SO4 ; snoh a reaction would indicate the same
formula as that ascribed to the liquid isomeride
(u. p. 4).
se
TRI-CHLOEO-AOETIC ANHYDRIDE.
TSI-CHLOBO-ACETIC ANHYSBIDE v. An-
hydride of Tri-OBLOBO-ICETIC ACID.
CHLORO-ACETO-ACETIC ETHER C„H,C10,
i.e. CHa.GO.CHCLCOjEt or CHjCl.CO.CH^CO^Et.
(194°). S.G.i±l-19. Formed, together with SOj
and HCl, by the action of SO2CI2 (1 mol.) or of
CI upon aceto-acetic ether (1 mol.) (Allihn, B. 11,
568 : Merves, A. 245, 58). Liquid. Alooholie
KOH liberates chloro-aoetio acid. (a)-Naphthyl-
amine forms C,gH,eNOjCl [75°] (Bender, B. 20,
2747). Fuming HNO, forms chloro-nitroso-
aceto-acetie ether CH3.CO.CCl(NO).C62Et (?)
(FrSpper, A. 222, 48). Phenyl-hydrazine in
ethereal solution forms C,jH„NjOj [51°], which
is probably CH3.e(N2Ph):0H.C02Bt, which may
be reduced to oxy-phenyl-methyl-pyrazole.
' MetalUc comjpownds. — Formed as precipitates
by shaking the ether with ammoniacal solutions
of the metallic salts.— (0|jHsO,Cl)jCu : green
" ' (OaHj03Cl)2Mg : white needles. —
IjNi : light - green powder. —
\fio: light-red powder (Hensgen, B.
12, i300)'.— CsHsOaClNa: crystalline powder,
V. sol. alcohol (Conrad a. Outhzeit, B. 16, 1554).
Di-chloro-aceto-acetic ether
CH3.CO.CCl2.COjBt or CH01j.CO.CH3.00jEt.
(206°). S.G.-i5| 1'293. Formed, together with
SOj and HCl, by the action of SOjClj (2 mols.)
on aceto-acetic ether (1 mol.) (Allihn, B. 11, 567).
Formed t^so by chlorinating aceto-acetic ether
(Conrad, A. 186, 232). Liquid. Decomposed by
dilute HCl at 180° into CO.^, alcohol, and di-
chloro-acetone. KOH gives i-ehloro-aoetic and
acetic acids. Decomposed by KCN into HCN,
acetic ether, and potassium di-chloro-acetate
(James, A. 240, 65 ; C. J. 51, 287). Di-chloro-
aceto-acetic acid does not form metallic salts,
nor does it react with aldehydes (difference from
di-bromo-aoeto-acetic ether).
Tri - cMoro - aceto - acetic ether OjHjCljOs
(223°). From aceto-acetic ether and CI in day-
light (Merves, A. 245, 70). With NaOEt it gives
di-chloro-acetic ether.
CHIiORO-AGETOIi v. Di-chlobo-pbofahe.
CHIQRO-AOEIONE CiH^CIO i.e.
CHs.CO.CHjCl. (118°). S.G. ia 1-158 (Cloez).
FormaUori. — 1. By electrolysis of a mixture
of acetone and HCl (Kiche, O. B. 49, 176).—
2. From acetone and HCIO (Mulder, B. 5, 1007).,
3. By passing chlorine (1 mol.) into well-cooled
acetone (M.).— 4. By dissolving di-ohloro-propyl-
ene CHjCl.CCliCHj in cone. HjSOi and distilling
the product with water (Henry, B. 5, 190, 965). —
6. From bromo- or chloro-propylene by the action
of hypochlorous acid and HgO (Linnemann, A.
138, 122). — 6. By oxidation of propylene ohlor-
hydrin (from propylene glycol) with KjCrjO,
and HjSO, (Morley a. Green, B. 18, 24).
Preipovratian. — By passing chlorine into ace-
tone at 15° (Cloez, A. Oh. [6] 9, 145).
Properties.— Pungent oil ; v. si. sol. water.
According to Cloez it is not pungent when quite
pure, and the pungency can be removed by
washing with very weak alkali. Volatile with
steam. It gives a splendid crimson colour with
solid KOH, or a strong aqueous solution of
KOH. With NaHSOj it forms orysfe^Hn«
C,HjCl(OH)(SOaNa) (Barbaglia, B. 6, 32 V
BeaeUom. — 1. Zn and HCl reduce it to
toetone.— 2. Moist Ag^O oxidises it to glyooIUo,
acetic, and formic acids. — 3. KjSOa gives
0H3.C0.CH..,S0,K.— 4. Potassium acetate forms
CHa.CO.CH2.t)Ao;— 5. Alcoholic KCN produces
CHJ.CO.CH2CN.— 6. 'FumingHNOj forms crystal-!
line nitroso-chloro-aoetone O3H4CINO2 P-IO*"]
(Glutz, X^jr. [2] 1,141).— 7. Alcoholic ffimmoMMWi
suVphoeyarMe gives the crystalline sulpho-
cyanide [114°] of imido-propyl sulphooyanide'
CH3.C(NH).CH2.SCN [42°] (Norton a. Toherniak,
Bl. [2] 33, 203). — 8. Barium ^uVphocyamAde forms
CHa.CO.CHjSCN which is an oil (Tcherniak a.
Hellon, B. 16, 349).— 9. Bromme at 100° forms
chloro-tri-bromo-acetone. — 10. Ammonia forms
a compound (CH3.CO.CH2NH2?) which gives
methylamine on distillation with potash (Cloez).
11. Chloro-acetone (2 mols.) added to an aqueous
solution of (1, 3, 4)-tolylene-diamine at 60° forms
N:CH
methyl-toluquinoxaline C3H3Me<' | ' [S4°]
(Hinsberg, A. 237, 368).— 12. Alcoholic KOBz
forms-CHs.CO.CHyOBz (245° at 380mm.) (van
Eomburgh, B. T. C. 1, 53).- IS. Cone. HCNAq
forms the cyanhydrin CH3.C(0H)(CN).CH3C1
which is the nitrile of ohloro-oxy-isobutyric acid
(ohloro-aoetonic acid) (C. Bisohoff, B. 5, 865).
Isomeride of chloro-acetone CgHjClO i.e.
0
CH3Cl.CH.CHj (?) Mpichlorhydrin (119°). S.Q.ii
1-194. Obtained from glycerin diohlorhydrin
CH3C1.CH(0H).CH3C1 and warm cone. KOH (Pre.
vest, P. [2] 12, 160). Liquid. Combines with
HCl, water, and HOAp forming derivatives of
di-ohlorhvdrin. With alcoholic NH, it forms
CjHijClNO, (Cloez, A.Ch. [6] 9,145).
u-Si-chloro-acetone CHCI2.CO.CH,. Mol. w.
127. (120°). S.G. iS 1-234.
Formatioij:. — By heating di-chloro-aceto-ace-
tic ether with water at 180° (Conrad, A. 186,
235) or by boiling it with HClAq for 5 hours
(V. Meyer, B. 15, 1165).
Preparation. — By the prolonged action of
chlorine upon well-cooled acetone (Fittig, A. 110,
40 ; 133, lie ; Mulder, B. 5, 1007 ; Cloez, A. Oh.
[6] 9, 145).
Properties. — Pungent liquid, si. sol. water.
Combines with bisulphite of soda forming
C3H,Cl3(OH)(S03Na)3aq. '
Beactions. — 1. ^mnumut forms the compound
CHj.Cb.CHC^NHj) which yields methylamine
when distilled with potash. — 2. FCI3 gives tetra-
chloro-propylene and a small quantity of pentu-
ohloro-propylene. — 3. KHS gives a yellow viscid
body CjHjSO, the alcoholic solution of which
gives with lead acetate a red pp. CaH^SOPbOaq
(Mulder, B. 6, 1008). — 4. Sydroxylamine forma
acetoximic acid CH3.C(N0H).CH(N0H) (v. voLi.
p. 38). — 5. Water at 200° gives lactic acid
(Linnemann a. Zotta, A. 159, 248). — 6. Potash
splits it up into acetic and formic acids. — 7. HCN
gives the cyanhydrin CH3.C(0H)(CN).CHC1,
or the nitrile of di-ohloro-oxy-isobutyrio acid
(Bischoff, B. 8, 1333).— 8. Aqueous KCN gives
crystalline tufts of (C3H,Clj0)2HCN (Glutz a.
Fischer, J. pr. [2] 4, 52).
Isomeride of di-culoro- acetone C3H,Cl20.
[44°]. (0. 168°). The entire product of the ac-
tion of chlorine on cooled acetone has the com-
position of di-chloro-acetone, although it boils
between 117° and 170°- This appears to be due
OHLOKO-ACETONE.
27
(0 the presence of this OTystalline iBomeride. It
only differs from s-di-chloro-acetone, derived
from diohlorhydrin, in yielding with bromine a
di-chloro-di-bromo-acetone identical with that
obtained from u-di-ohloro-acetone, and not with
that obtained from the said s-di-ohloro-acetone
(Barbaglia, B. 7, 4C8 ; Cloez). This compound
could not be obtained by Bischoff (B. 8, 1332).
O
Another isomeride A (?) Chlpro-
CHClj.CH:CH2
vpichlorhydrin (?) (170°), is formed by chlorin-
ating epiohlorhydrm (Cloez, A. Ch. [6] 9, 145).
With NHj it forms unstable CjHsCljNOj.
s-Bi-chloro-acetone CHjCl.CO.CH^Gl. [44°].
(173° cor.). V.D. 03-2.
Formaticm. — 1. By the oxidation of the
corresponding diohlorhydrin of glycerin
CHjCl.CH(OH).CHjCI with KjCr^O, and H^SO,.
Purified by means of its crystalline compound
with NaHSO, which is subsequently decomposed
by Na^CO,. The yield is very small (Glutz a.
Kscher, J. pr. [2] 4, 52 ; Hermann, B. 13, 1707 ;
MarkownikofE, A. 208, 349).— 2. By the union of
HCIO with o-chloro-allyl chloride (di-chloro-
propylene) CHjCl.CChCH^ and HCIO (Henry,
C^. 94, '1428). — 3. From s-di-iodo-acetone and
AgCl (Voelker, A. 192, 89).
Prop^Ues. — Long needles ortrimetrio tables.
Extremely pungent ; blisters the skin. M. sol.
water, v. sol. alcohol and ether. With bisulphite
of soda it forms long four-sided prisms of
C^.Cl2(0H)(S0,Na) 3aq.
Reactions. — 1. EI forms di-iodp-acetone
[61°].— 2. Dry KCN added to its ethereal solu-
tion forms crystalline tetra-chloro-di-ace-
tone oyanhydrin (OsHsCljOJHCN which
differs from the isomeric body obtained from
u-di-chloro-acetone in being insol. water (G.
a. F.).— 3. HCN forms (CH,Cl)jC(OH)CN, the
nitrile of di-chloro-oxy-isob'utyric (di-chJoro-aee-
tonic) acid. — 4. Oxidised by Xfirfi, and lijSO,
to chloro-acetic acid.
According to Cloez (A. Ch. [6] 9, 14'5) succes-
sive treatment with bromine and HgCl, gives
tetra-chloro-acetone, but the tetra-cbloro-acetone
prepared in this way from the di-chloro-acetone
obtained from diohlorhydrin is different from
that obtained from di-iodo-acetone. They also
give different penta-chloro-acetones when treated
with chlorine in sunlight. Cloez considers the
derivative from diohlorhydrin to be a pseudo-di-
O
chloro-acetone A It does not
CHjCl.CH:CHCl.
combine with EOAo, but reacts violently with
ECl, although the product, exposed over HjSO^,
is re-converted into i/f-di-ohloro-acetone.
Tri-chloro-acetone CGIj.CO.CHj. (180°)
(Combes).
Formaiicm. — Obtained in an impure state by
passing chlorine into acetone that is not kept
cool, especially if the chlorine be somewhat
moist, or the acetone be mixed with methyl
alcohol (crude wood spirit) (Bischofl, B. 8, 1331).
The crude product of the oxidation of isobutyl
alcohol with chromic mixture iuay also be used
(Kramer, B. 7, 252).
Fre^raUon. — ^1. Bj passing chlorine into an
aqueous solution of sodium citraconate at 100°
(Gottlieb a. Morawsky, J.pr. [2] 12, 3()9).— 2. By
the action of NaOH (1 mol.) upon hexa-u-chloro-
methylene dl- methyl diketone (hexa-chloro-
acetyl-acetone) (CG1,.C0)2CH2 (Combes, A. Qh.
[6] 12, 239).
Properties. — Liquid, heavier than water, with
fragrant odour. Converted by ammonia into
chloroform and acetamide. Does not unite
with NaHSO,; but with HCN it forms
CCl3.CMe(0H)CN (Bischoff). It unites readily
with water, forming a hydrate' C,H,Cl,0 2aq
[44°] crystallising in four-sided prisms, which is
resolved by distillation or by dry HOI into Its
constituents. The product of the chlorination
of acetone boils at 172°, and has S.G. 1-418.
According to Cloez it is a mixture ; for It solidi-
fies incompletely on cooling, when It deposits
needles [c. -^ 5°]. With aniline and KOH it gives
phenyl-carbamine, showing the presence of
CClj.CO.CHj. Successive treatment with am-
monia and KOH gives di-ohloro-methyl-amine,
indicating the presence of CHClj.CO.CHjCl;
Tri-chloro-acetone CHClj.CO.CHaCL (172°).
From M-dl-ohloro-aoetone by treating with bro-
mine and heating the resulting CHC^.CO.CHjBr
with HgCLjin presence of alcohol (Cloez). Gives
no chloroform with ammonia, nor phenyl-carba-
mlne with aniline and KOH.
u - Tetra -chloro-acetone 0Hj01.CO.CCl,.
(181°). S.G. iZ 1-482. Formed by saturating
acetone containing methyl alcohol or wood
spirit with chlorine in daylight, the tempera-
ture being allowed to rise (Bouis, A. Ch. [3] 21,
111). The fraction boiling at 1G0°-180° Is ex-
posed to a low temperature in contact with
water, whereupon the hydrate of tri-chloro-
acetone crystallises out first, then a compound
of this with tetra - chloro - acetone hydrate
(CjH3Cl30)(0,HjCl,0) 6aq [32°], and finaUy large
prisms of the hydrate of tetra-chloro-acetone
CsHjCljO 4aq [39°] (c. 179°), which may be re-
solved by dry HCl Into tetra-chloro-acetone and
water.
Properties. — Colourless hygroscopic liquid,
sol. water,.wlth pungent odour. Beadily volatile
with steam. Turned brown by air and light.
Partially decomposed by distillation. With
aniline and KOH it yields phenyl carbamine.
Aqueous ammonia at a low tenlperature forms
chloroform and chloro-acetamldo.
s - Tetra - chloro - acetone CHClj.CO.CHCLj.
(180°). S.G. 3i 1-48. Formed by treating M-dl-
chloro-acetone, or the s-di-ohloro-acetone derived
from s-di-iodo-acetone, with bromine and de-
composing the resulting CHCl|,.C0.CHBr2 with
HgCLj in alcoholic solution at 100°. Purified
by conversion Into its crystalline hydrate [48°] i
and subsequent dehydration by dry HCl (Cloez).
This tetra-chloro-acetone does not give the
chloroform and carbamine reactions. The di-
chloro-di-bromo- derivative obtained by the action
of bromine on dichlorhydrin yields with HgCLj
an oil which Is not attacked by ammonia. The
product of the oxidation of dichlorhydrin gives
with bromine CHClBr.CO.CHClBr (Markowni-
koff), whence HgOlj gives a fuming liquid (180°) ;
this liquid does not combine with NaHSO,, bi^t
yields with ammonia di-chloro-acetiimide, and
with anilme di-chloro-acetanllide, Cloez con-
28
OHLORO-AOETONB.
aiders that it is isomeiic, but not identical with
(■tetra-chloro-acetone ; thus it might bo
O
A
CHjCl.CH.OCl,.
Fenta-ehloro-acetone OCL.OO.CHCL. (192°).
S.G..W 1-576. S. 15.
FormaUon. — 1. By passing chlorine into a
strong solution of sodium citraconate (Planta-
mour, Gm. 11, 440).— 2. By the action of HOI
and'EClOg on various organic compounds, e.g.
quinio, citric, gallic, and salicylic acids, pyro-
gallol, quinone, indigo, tyrosine, and muscular
flesh (Stadeler, A. Ill, 277).— 3. By the action
of chlorine in sunlight upon commercial acetone
or on di-chloro-acetone (Cloez,sen.,.i. Ill, 180;
Cloez, jun., Bl. [2] 39, 637). Pure acetone gives
only di-chloro-aoetone when chlorinated at 100°
in sunlight (Fittig).
Preparation. — 1l solution of citric acid in
1^ pts. water is allowed to fall drop by drop down
a tube packed with pumice heated to 100", up
which a current of dry chlorine is passing
(Cloez; jun., A. Ch. [6] 9, 145).
Properties. — Colourless liquid, smelling (after
exposure to air) like chloral. With water at 4°
it forms a crystalline hydrate C3HCl504aq
[16°J, which, on fusion, separates into water and
penta - chloro - acetone. Penta - chloro - acetone
separates completely from its aqueous solution
at 60°. Penta-chloro-acetone dissolves a little
water, but on warming this separates as globules.
Beactions. — 1. Ammoma gives chloroform
and di-ohloro-acetamide [95°] (235°). — 2. Ani-
Une and KOH give phenyl-carbamine. — 3. KOH
gives di-chloro-acetic acid, KOI, and K^OO,.
laomeride of penta - chloro - acetone
O
A
CCl,.CH.CCl2(?). Tel/ra - chloro - epichlorhydrin.
{185°). S.G. 1 1-617. By the action of chlorine
m sunlight on the s-di-chloro-acetone from di-
ohlorhydrin (Cloez, jun., Bl. [2] 39, 639), Pun-
gent liquid. With ammonia it gives tri-chloro-
aoetamide [139°] (235°-240°) but no chloroform.
Another isomeride of penta-chloro-acetone
O
CHCL,.C01.CClj(?). (178°). From di-chloro-pro-
pylene oxide and chlorine (Oloez, jun., A. Ch.
[6] 9, 145). Fuming liquid. With ammonia it
gives di-chloro-acetamide, but no chloroform.
Heza-chloro-acetone CCl3.CO.CClj. [-2°].
(203°). S.G. ia 1-744. V.D. 9-62. Formed by
saturating a cone, aqueous solution of citric
acid with chloi-ine in sunshine (Plantamour,
B. J. 26, 428). The yield is 25 p.o. of'the weight
of citric acid. Formed also by the action of
chlorine on (commercial) acetone in sunlight.
On distilling the product a considerable quantity
of h'exa-chloro-benzene is usually formed.
Properties. — ^Limpid liquid, which has a feeble
odour in the cold, but becomes very pungent
when warmed. Solidifies when cooled in large
plates. SI. sol. water. Forms a crystalline hy-
drate CgClgO aq [1S°] almost insol. water.
Reactions.— 1. With aqueous ammoma it
forms chloroform and tri-chloro-acetamide. —
2. AniUne forms chloroform and tri-cbloro-acet-
aniUde. — 8. Water at 120° splits it up into
chloroform and tri-chloro-acetio acid.— 4. Potash
gives CO2 and tri-chloro-aoetic acid. — 5. With
o-toluidine it forms tri-chloro-aeetyl o-toluidine
OeH4Me.NH.CO.COl3 [67°] ; with p-toVuidine it
forms the Isomeric body [80°]. — 6. Diethylamme
gives NEtj.CO.OOlj [90°].— 7. Allylamime forms
NHCaHs.CO.CCl, [45°]. — 8. Ethylene-diamim
gives Nilj.CjHj.CO.CCl, [200°].— 9. Urea (Imol.)
at 150° forms 00(NH.OO.C01a)j.
Isomeride of heza - chloro - acetone
O ,
00l3.001.CClj(?) (0. 205°). This substance ap-
pears to be formed, together with heza-chloro-
benzene, by the action of chlorine on epichlor- '
hydrin in sunlight (Oloez, jun.).
CHLOBO-ACEIOITIC ACID v. Chlobo-ozx-
IBOBUTYIilC ACID.
CHLOBO - ACETONIIBILE v. Nitrile of
Chlobo-acetic acid.
Q>-CHLORO-ACETOFHENOir£
C,H5.C0.0Hj01. Phenacyl chloride. Phenyl
chloro-methyl ketone. [59°]. (245°). Formed,
together with di- and tri-chloro-acetophenone,
by passing chlorine into boiling acetophenoue.
The fraction (240''-250°) solidifies on cooling,
and is reciystallised from dilute alcohol (Grabe,
B. 4, 35 ; Stadel, B. 10, 1830 ; Gautier, C. B.
102, 1248). Colourless trimetiic plates ; a:b'.c=
-9957:1:-21S5 (Friedlander) ; v. e. sol. alcohol and
ether, insol. water. Its vapour is pungent.
Reactions. — 1. KOAc forms the acetyl deri-
vative of eo-oxy-acetophenone, CijHs.CO.CHjOAc.
2. POI5 forms di-chloro-styrene CsHs.OOhCHCl.-
3. Chromic acid oxidises it to benzoic acid. —
4. Ammonia passed into its ethereal solution
forms two isomerides OijHuClOj [117°] and
[155°]. Boiling aqueous ammonia forms (a)-
phenyl-amphinitrile or isoindole C,|,H„Nj [195"^,
which crystallises from alcohol in blue mono-
clinic needles (V. Meyer a. Treadwell, B. 16,
342). — 5. (1, 3, 4)-Tolylene-diamine gives pheiiyl-
toluquinoxaline C^HjMe^^i.Qpjj^ [135°]
(Hinsberg, .4. 237, 370).
jp-Chloro-acetophenone [4:1]C5H401.C0.0H,.
Chloro-phemjl methyl ketone. [20°]. (231°).
S.G. ^2 1-19. From chloro-benzene, acetyl chlor-
ide, and Alicia (Gautier, Bl. [2] 43, 602). V. si.
sol. water, miscible with alcohol and ether.
EMnO^ oxidises it to ^-chloro-benzoio acid.
Di-m-chloro-acetophenone CgHg.OO.OHClr
(248°). S.G. is 1-338. From di-chloro-acetyl
chloride, benzene, and AljCL (Gautier, C. B.
103, 812).
Trl-w- chloro -aeetophenone CsHr.CO.CCl,.
(249°). S.G. ia 1-427. From tri-chloro-aoetyl
chloride (60 g.), benzene (100 g.), and AljClj (Gau.
tier, C. R. 103, 812). Oil ; slowly oxidised by
EMnO, to benzoic acid.
TSI-u-CHLDSO-ACETOFHENOITE o-CABB-
OXYXIC ACID C01,.C0.0„H4.C0jH. [144°].
Formed by passing chlorine into a hot solution
of phthalyl-acetio acid in diluted HOAc (Michael
a. Gabriel, B. 10, 1556). Decomposed by alkalis
into chloroform and phthalio acid.
CHLOBO-ACEXOIHIENOKE v. Tbienti.
chlobotMethsii ketone.
CHLOEO-ACEXOXIM (CH3)jC:N001. Acet-
chloroxim. (134° uncor.) ; when quickly heated
it explodes with violence. V.D. 4-1 (for 3-7). '
Obtained by adding a solution of hypochlorous
OHLORO-ACRYLIO ACID.
29
•cid to an aqneouB Bolntion of aoetozim at 0° ;
the liquid that separates is washed with water,
and dried over CaCl,. Colourless mobile liquid
of pleasant odour, which solidifies in a freezing-
mixture of solid GO, and ether, to colourless
prisms. Y. sol. alcohol and ether, t. b1. sol.
water. Warmed with HCl or HI it sets free the
halogens (Mohlau a. Hoffmann, B. 20, 1505).
TKI-CHLORO-jS-ACETYL-ACBTLIC ACID v.
Ibi-chlobo-fhunomauc acid.
TBI-CHLOSO-ACEITL-BENZOIC ACID v.
TbI-CHLOBO-ACETOPHENONE CABBOX'SrLIO ACID.
CHLOEO-ACETTL BEOMIDE OHjCl.CO.Br.
(127°) (W.); (ISi") (G.). S.G. 2 1-913. Pre-
pared by adding bromine (160 g.) to chloro-acetio
acid (94 g.) and red phosphorus (15 g.) (De Wilde,
A. 130, 372; 132, 173; Gal, A. 132, 180).
Fuming liquid. With water it forms EBr and
chloro-acetio acid; alcohol gives EtBr and
chloro-acetic ether.
Tri-ohloro-acetyl bromide OCl3.CO.Br. (140°)
(H.); (143°) (G.). S.G. if 1-900. From PBr,
(2 mol.) and tri-chloro-acetio acid (3 mol.).
300 grms. of the acid give 200 grms. bromide
(Hofieriohter, /. pr. 128, 196 ; Gal, C. B. 76,
1019 ; Bl. [2] 20, 11). Water decomposes it
into HBr and tri-chloro-acetic acid ; alcohol
gives EtBr and tri-chloro-acetic^ ether.
CHLOSO-ACEITL CHLOSIDE CH^Gl.CO.Cl.
Mol. w. 113. (107°). S.G. 2 1-495. Formed by
the action of chlorine on acetyl chloride in sun-
light (Wurtz, A. 102, 93) ; or, together with di-
chloro-acetyl chloride by boiling acetyl chloride
with PCls (Michael, J. pr. [2] 35, 95). Formed
also by treating chloro-acetic acid with PCI,
(De Wilde, A. 130, 372). Liquid, converted by
water into HCl and chloro-acetic acid; and by
dry ammonia into ohloro-aoetamide.
Beactions. — 1. Successive treatment with zinc
methyl and water forms methyl-isopropyl-car-
binol (Bogomoletz, Bl. [2] 34, 330).— 2. With
o-anddo-phenol it forms 0^<(0H).NH.C0.0H2C1
[186°] (Aschan, B. 20, 1523). It reacts simi-
larly with other amido- compounds. — 3. Phosph/u-
retied hydrogen forms ohloro-acetyl-phosphide
CH2CI.CO.PH21 a white powder slowly decom-
posed by water into PH, and chloro-acetio acid
(Steiner, B. 8, 1178).
Di-chloro-acetyl chloride CHCL2.CO.CI. Mol.
w. 147^. (108°). Formed by the action of PCI,
on di-chloro-acetio acid (Otto a. Beckurts, B. 14,
1618) ; or, together with the preceding, by boiling
acetyl chloride with PCl^^ (M.). Pungent, fuming
liquid : decomposed at once by water. Successive
treatment with ZnMe, and water forms (6 p.c. of)
di-methyl-propyl-carbinol (B.).
Tri • cbloro - acetyl chloride CCl3.CO.Cl.
(117-9°) (Thorpe, 0. J. 37, 189). S.G. f 1-6564.
O.E. (0°-10°) -001095; (0°-100°) -0012013. S.Y.
125-51.
FwrmaUm.—l. From PCI, and COlj.COjH
(Gal, C. B. 76, 1019). The yield is very small.
2. By the protracted action of chlorine on ether,
the operation being conducted towards the end
in sunlight (Malaguti, A. Ch. [3] 16, 5). Also
by the distillation of penta-chloro-ethyl ether
(OgClJgO, or of perchlorinated acetic ether
CCIi-OOjOjCl,.— 3, Together with SO, from 0,01,
and SO, at 150° (Prudhomme, O. B. 70, 1137).
Also from C,C1, and SO,.
P/ojier^ies.— Liquid ; decomposed by water
into HCl and tri-cUoro-aoetio aoid; alcohol
gives tri-chloro-acetio ether.
Beactions. — 1. ^irusmot^iifefollowedbywater
gives the heptyl alcohol CMej.CMejOH (B.).— 2.
PH, gives CC1,.C0.PH, (Steiner, B. 8, 1178 ;
Cloez, A. Ch. [3] 17, 309).— 8. Tri-chloro-acetic
acid forms the anhydride (CC1,.C0)20 (Anschutz,
B. 10, 1881).
TBI-CHLOSO-ACEXTL CYAITIDE
CC1,.C0.CN. Tri-chloro-pyruvoniirile. (118")
(H.) ; (122°) (C. a. A.). S.G. i^ 1-559.
Preparation. — 1. By adding AgCy slowly to
cooled tri-chloro-acetyl bromide; the reaction
being finished by heating on a water-bath
(Hofferiflhter, J. pr. 128, 200).— 2. By boiling
tri-chloro-acetyl bromide with merourous cyanide
(Claisen a. Antweiler, B. 13, 1935),
Properties. — Pungent, hygroscopic liquid
smelling of prussic acid. Exposed to air it first
becomes crystalline (forming a hydrate?) then
deliquesces.
Beactions. — 1. Water decomposes it into tri-
chloro-acetic acid and prussic acid. — 2. HCl
(S.G. 1-16) at 50° converts it into tri-chloro-
pyruvic acid C01,.eO.C02H.
Polymeride (CCl,.C0.0N)x. [140°]. From
AgCy and tri-chloro-acetyl bromide at 150° (H.).
Dimetric tables (from ether-alcohol) ; insol. water.
CHLORO-ACETYLEWE CHiCOl. Formed by
boiling ;8-di-ohloro-acrylic acid CCl2:CH.C02H
with baryta-water (WaUach, A, 203, 87). Gas,
which explodes spontaneously, forming carbon
and HCl. It is stable when diluted with hydro-
gen, and then, when passed into bromine, forms
crystalline C^HClBr^. With ammoniacal cuprous
chloride it forms an orange pp., and in ammo-
niacal silver nitrate a white pp. These pps. ex-
plode violently when heated.
TBI-CHLOBO-ACEIYL IODIDE CC1,.C0.I.
io. 180°). From tri-chloro-acetio acid and PI,
Gal, a. B. 76, 1019).
CHLOBO-ACEIYL-FBOFIONIC ACID
CjHjClO,. Chloro-levulic acid.
Ethyl ether A'Et (225°-230°), S.G. f| l-196i
Prepared from j8 - acetyl - propionic ether
CH,.C0.CH..CHj.C02Et and chlorine. Colourless
pungent liquid (Conrad a. Guthgeit, J3. 17, 2286).
CHLOBO-ACETYL-UB EA
NHj.CO.NH.CO.CH,Cl. From urea and ohloro- ,
acetyl chloride (Tommasi, O. B. 76, 640). Thin
needles (from alcohol). SI. sol. boiling water.
With thio-ure'a it forms urea, HCl, and thio-
hydantoin.
Tri-cMoro-acetyl-nrea NH,.C0.NH.C0.CC1,. ,
[150°]. Formed by heating tri-chloro-acetyl
chloride with urea (Tommasi a. Meldola, C. J.
27, 404), or urea tri-chloro-aoetate with P,0, (De
Clermont, C. B. 78, 848). Needles or plates;
insol. cold water.
CHLOBO- ACIDS v. Chlobo- compounds.
a-CHLOBO-ACBYLIC ACID C,H,C10j ».«.
CH,:CC1.C0,H. [65°]. (0. 178°).
Formation. — 1. From a/3-di-chloro-propionia
acid CHjCLCHCLCO^H by treatment with baryta
or alcoholic KOH (Werigo, A. 170, 168 ; B. 10,
1499). — 2. From a-di-ohloro-propionic acid
CH,.CCl2.C02H and alcoholio EOH (Otto a.
Beckurts, B. 18, 239).
Properties.— Needles ; t. sol. water, but may
be extracted by ether. Faming HCl at 10Q°
forms BjS-di-ohloro-propionic a«id.
30
CHLORO-AORYLIO ACID.
Salt a. — ^AgA': white crystalline pp. — KA'aq:
needles. — BaA', 2aq : plates.
jS-Chloro-aorylic acid CHCl:CH.COjH. [84°].
Formation. — 1. From ethyl tri-ohloro-laetate
(or from chloralide), zinc, and HCl in alcoholic
solution (Pinner a. Bischoff, A. 179, 85 ; Wallach
a. Hunaeus, A. 193, 23). — 2. By combination of
propiolio acid with HCl (Bandrowsky, B. X$,
2702).
Preparation. — ^From chloralide (50 g.), alcohol
(150 g.), Zn (80 g.), HCl (80 g. of S.G. 1-24). The
reaction is moderated by cooling, and after 24
hours more HCl (20 g.) and Zn (15 g.) are added.
Aftei; 24 hours HCl (30 g.) is added. The alcohol
and by-products are evaporated off and the re-
maining solution is extracted with benzene. The
8-ohloro-aorylic acid which is dissolved is subse-
quently distilled with steam. 1,000 g. of chloral-
ide yield 12 g. of i8-chloro-acrylio acid (Otto a.
Promme, A. 239, 264).
Properties. — Flexible laminas, m. sol. chloro-
form, v. sol. water, v. e. sol. benzene. Above 15°
it separates from aqueous solution in oily drops.
Aqueous HCl at 80° gives CHClj.CH2.CO2H. Com-
bines with bromine (1 mol.).
Salt.— AgA'. '
Ethyl ether Mk'. (144°).
a/S-Si-chloro-acrylic acid CHChCCLCOsH.
[86°].
Formation. — 1. By the action of KOH on
mucochloric acid (Hill, Am. 3, 168 ; B. 12, 656).
2. By heating per-chloro-pyroooU octo-ohloride
or di-chloro-maleimide with water at 130° (Cia-
mioian a. Silber, B. 16, 2392).
Properties. — Monoolinic prisms ; a:b:c =
l-1865:l:-3637 (Hill a. MelviUe, P. Am. A. 17,
131). Volatilises rapidly in the air. Y. e. sol.
water, alcohol, and ether ; v. si. sol. benzene.
Salts.^AgA': slender needles. — KA': felted
needles. — BaA'^aq: trimetric plates. S. 6-6 at
18°. — CaA'2 3aq : soluble needles.
iS-Di-cMoro-acrylio acid CCl2:CH.C02H(?)
[77°] and [64°]. This acid may possibly be allo-
aj3-di-chloro-acrylic acid. Formed, together with
18-chloro-acrylic acid, by reducing chloralide in
alcoholic solution with Zn and HCl (Wallach, A.
193, 20 ; 203, 84). Slender needles or mono-
olinic 'prisms (from chloroform). Volatile in
air; but cannot be distilled. After heating to
120° it melts at 64°, but, on keeping, the melt-
ing-point rises to 77°. V. si. sol. water ; v. sol.
ether and chloroform. Does not combine directly
with Br. Not attacked by water at 200°. Boil-
ing baryta-water forms chloro-acetylene.
S alt s.— KA'.— AgA'.— CaA'22aq.— ZnA'22aq.
Ethyl ether'EW. (174°). Saponified by
oold KOHAq. Converted by treatment with
AgjO at 125° and saponification of the product
by Ca(0H)2 into malouio acid.
Chloride CCljiCH.COCl. (Above 145°).
Amide CCLjiCH.CONHj. [113°]. Needles.
Tri-chloro-acrylio acid CCl2:CCl.C02H. [76°].
S. 6 at 20°. From tri-chloro-bromo-propionio
acid and cold baryta-water (Mabery, Am. 9, 3).
Trimetric prisms, si. sol. water, m. sol. hot CS2,
V. Eol. alcohol, ether, and chloroform.
Salts. — EA': irregular plates, si. sol. cold
water.-^AgA' : slender needles, v. si. sol. cold
water. — Cak'^Z^iui : tu'ts of needles. -^
SaA', 3^a^ : brancbsa of pearly needle;.
CHLOBO-ALSEHYDE v. CHliOBo-ACETio udb.
HynE.
CHL0E0-ALD0XIM''CH3.CH:NOCl. Formed
by mixing solutions of aldoxim and hypochloroua
acid ; the liquid which separates being washed
with water and dried over CaClj., Colourless
liquid of powerful odour. Very unstable. De-
composes explosively on heating. Liberates
iodine from HI (Mohlau a. Hoffmann, B. 20,
1507).
CHLOBO-AXIZAIMN v. Chlobo-di-ozy-
ANTHBAQUINONE.
CHLOBO-SIALLYL v. Hexinyl CHLomDE.
a-CHIOBO-ALLYL ACETATE
CHjiCCLCHj-OAc. (145°). Formed in small
quantity, with other products, by the action of
KOAc on di-chloro-propylene CHgiCCl.CHjCl
(Henry, B. 5, 454).
j8-Chloro-aUyl acetate CHChCH-CKjOAo. (0.
158°). From di-chloro-propylene CHChCaCHjOl
and KOAc (Martinoff, B. 8, 1318). '
a-CHIOBO-ALLYL ALCOHOL 0^010 le.
CHjiCCLCHjOH. (136°) (H.) ; (c. 138° i.V.) (R.).
S.G. is 1-164. Formed by boiling di-chloro-
propylene CHatCCLCHjCl (95°) with a dilute
solution of EjCOj- for some hours (Henry, O. B.
95, 849). Formed also by the action of dilute
KOH or Ag20 upon o-chloro-allyl iodide
CH2:CC1.CH2X (Van Eomburgh, B. T. C. 1,
233).
Liquid with faint aromatic odour. Does not
attack the skin. M. sol. water ; gives a-chloro-
allyl acetate (145°) with Aefi. When distilled
with much water a-chloro-allyl alcohol yields
aoetyl-carbinol CHj.CO.CHjOH. HCIO gives
CH2CI.CO.CH2OH.
jS-chloro-allyl alcohol CHCljCH.CHjOH.
(153° cor.). S.G. ¥ 1'162. V.D. 3-3. Formed
by treating CHChCH.GHjCl with aqueous KOH '
at 100° (Eomburgh, Bl. [2] 36, 555). Pungent
liquid, si. sol. water. Blisters the skin. Com-
bines with bromine.
DI-C HLOEO-DI-ALLYl-AMINE CsH,CL,N i.e.
(CH2:CC1.0H2)2NH(?) (194°). Froms-tri-chloro-
propane and alcoholic ammonia by heating for
a few days at 140° (Bngler, Bl. [2] 9, 134 ; A.
142, 72). Heavy oil, si. sol. water.— B'HCl : de-
liquescent needles.— B'jHjPtCl,.
Tetra-chloro-di-allyl-amine OoHjCLN i.e.
(CH01:CC1.CH2)2NH. From CH2Cl.CCl2.CH,Cl
and alcoholic NHj at 120° (Fittig a. Pfefier, A.
135, 363). Alkaline liquid; cannot be distilled ;
volatile with steam; al. sol. water. — B'HCl:
needles.— B'H20204.
CHLOBO-ALLYI-BBOHIDEv.CaLOBO-BBOuo-
PROPANE.
CHLORO-AILYI-CHIOBIDE v. Di-ohloro-
PROPANE.
CHLOBO-AILYLENE o. Propabgyi, CHLORIDE.
CHIOBO-ALLYL ETHYL OXIDE v. Eihyi.
OHLORO-AliLYL OXIDE.
CHLOEO-ALLYL lOSIDE v. Chlobo-iodo.
PROPANE.
a-CHLOBO-ALLYL NITBATE C,H.01N0, t.«.
CH2:CCl.CH2.NOa. (140°). From B-ohloro-allyl
alcohol, HjSOj, and HNO, (Henry, C. B. 95, 849),
or from a-chloro-ai-iodo-propane CHj-.CCLCHjI
and AgNCj. Oil (Eomburgh, B. T. C. 1, 238).
a-CHLOBO-ALLYL THIO-CABBIMIDE
C^H^CINS i.e. CH2:CC1.CH2.NCS. (181°). From
CH^:CC1.CH,C1 and potassium sulphocyanida
OHLOEO-AMIDO-NAPHTHOIO LACTAM.
SI
(Henry, C. R. 95, 849 ; Bl. [2] 39, 526). Liquid,
smelling like mustard. Converted hj ammonia
into chloro-allyl thio-urea [91°].
CHLORO-AIiLYL TKH)-UEEA C,H,01NjS i.e.
0H2:CC1.CH..NH.CS.NH,. [91°]. Prepared as
above (Henry, B. 5, 188).
CHLOBO-AMIDES v. CHiiOKO-coMPonNDS.
DI-CHLOSO-AHISO-ACETIC ETHER
CACljNOj i.e. CCLj(NH2).C0.JEt. Di-chloro-
gtycocoll. Oxamethane chloride. From oxamic
ether and PCI, (Wallaoh, A. 184, 8). Unstable
crystals, splitting off HGl and leaving
NH:CCl.COjEt, and finally N:G.CO,Bt.
Beactions. — 1. Water forms Hdl and oxamio
ether. — 2. Butyl alcolwl forms butyl oxamate ;
other alcohols and phenols act similarly. —
3. POCl, forms NH(P0ClJ.CCl2.C0,Et [130°],
which may be crystallised from chloroform or
ligroin, but is decomposed by water or heat.
m-CHI.OBO-AMIDO-BENZENE(a).STrLFHO-
KIC ACID CsH,ClNSO,i.e. CjH3(Cl)(KHj)(S0,H)
[1:3:?]. Prepared by reducing m-chloro-nitro-
benzene (o)-sulphonic acid with ferrous hydrate.
Colourless soluble needles (Post a. Meyer, B. 14,
1607).
m-Chloro-amldo-benzene (i3)-8uIpIiomc add
C.H,(C1)(NH2)(S0,H) [1:3:?]. Prepared by re-
duction of m-chloro-nitro-benzene (/3)-3ulphonic
acid with ferrous hydrate. Plates, si. sol. water.
Salts. — NaA'2aq : colourless needles. —
BaA'27Jaq ; colourless thick needles, v. sol. water
and alcohol (Post a. Meyer, B. 14, 1607).
m-Chloro-amido-benzene (7)-aalplionic acid
CA(01)(NH2)(S03H) [1:3:?]. Prepared bysul-
phonation of m-chlor-aniline. Sparingly soluble
crystals.
Salts. — ^NaA'^aq: yellowish needles. —
KaA'2aq: colourless needles. — BaA'^aq: small
yellow needles, sol. alcohol. — SrA'^gaq: long
colourless needles, sol. alcohol and water (Post
a. Meyer, B. 14, 1607).
Di-chloro-amido-benzene snlphonic acid
C(HjCl2(NH2)(S0jH). From amido - benzene
m-sulphonio acid and chlorine (Beckurts, A. 181,
212). Slender needles (containing 2aq) : si. sol.
water.
CHLOBO-o-AMIDO-BENZOIC AOIS
C,H3Cl(NHj)(C0jH) [1:4:5]. ChUn-o-anthramUc
acid. [204°].
Formation. — From chloro-isatoio acid and
cone. HCl (Drosoh, J.pr. [2] 33, 50).
Properties. — ^Long white needles (from alco-
hol). V. sol. glacial acetic acid, acetone, and
alcohol, sol. ether, benzene, and water contain-
ing ECl, m. sol. chloroform, si. sol. water. Its
solutions have a yellowish colour and exhibit
violet fluorescence.
Amide 0,KfilCSS^).CO.nS^. [172°]. By
the action of hot NH,Aq upon ohloro-isatoio
acid. Flat needles (from alcohol or from water).
Sol. alcohol, acetone, and glacial acetio acid, less
sol. chloroform, ether, benzene, and water.
Chloro-o-amido-benzoic aoid
CAC1(NH,)(C0^) [1:2:3].
Chhro-anthramlio acid. [148°]. From
chloro-nitro-benzoio acid [136°] by reduction
(Cunze a. Hubner, j1. 135, 111 ; Hiibnera. Weias,
B. G, 175). Long needles, t. bI. sol. water. —
KA'2aq. — AgA'. — CaAUiaq. — BaA'-liaq. ~
PbAV
Chloro-m-amido-benzoic acid
C,H3Cl(NHj)C02H [1:2:4]. [212°]. Obtained
by reducing the nitro-acid [180°] (Beveill, A.
222, 184). Formed also by boiling the diazo-
imide of benzoic acid with HCl (Gfiess, B. 19,
315). Beduced by sodium amalgam to m-amido-
benzoic aoid. Salts. ~" "
HA'HjSO,.
Ghloro-m-amido-benzoic acid
CeH301(NHj)COjH[l:2:6].[185°].Formed together
with the [1:3:4] isomeride by boiling the TO-diazo-
imide of benzoio-acid OjHjNj.COjH with HCl
(Griess, B. 19, 315). White tables or small
prisms. V. sol. hot water.
Ghloro-m-amido-benzoic acid
C,HaCl(tej)C02H [1:4:6]. [212°]. From the
nitro- aoid [165°] by Sn and HCl (Wilkens a.
Back, A. 222, 198). Brownish needles (from
water); v. sol. water or alcohol. Beduced by
sodium amalgam to m-amido-benzoic acid.
Salt s.— PbA'j 1 1 aq.— (A'Cu)^^— HA'HOl.—
HA'H.SO,.— HATENOr
s-Chloro-m-amido-benzoic acid
CACl(NH2)00jH [1:3:5]. [216°]. From
CeH3Cl(N0„)C0jH [147°], Sn, and HOI (Hubner,
A. 222, 90). Long needles ; v. sol. alcohol or
ether, si. sol. water.
Salt s.-BaA's 4aq.— AgA'.— CuA'j.
Di-chloro-o-amido-benzoic acid
CeH2CL.(NH2)C0jH [1:2:4:5]. Di-chloro-an-
thranilio acid. i222°-224°]. Formed by boiling
di-chloro-isaioic acid with cone. HCl (Dorsch,
J.pr. [2] 33, 52). Needles. V. sol. ordinary
solvents, except water.
Amide C„H,Cl2(NH2)CO.NH,. [284°]. From
di-chloro-isatoio acid and aqueous ammonia.
Short thick needles (from alcohol-acetone). SI.
Bul. all solvents.
Tri-chloro-amido-benzoic acid
C„HC1,(NH,)(C02H) [1:8:5:2:4]. [210°]. From
tri-chloro-nitro-benzoic acid, tin, and HCl (Beil-
stein a. Kuhlberg, A. 152, 240). Small slender
needles (from water) ; si. sol. boiling water. Does
not unite with acids. — BaA'^ 3aq.
Tecra-chloro-amido-beuzoic acid
OeCl,(NHj).OOjH [1:2:3:4:5:6]. Tetra-chloro-
anthranilio acid. Obtained by reduction of
tetra-chloro-nitro-benzoio acid with tin and
HGl. Colourless amorphous solid. V. sol.
alcohol, nearly insol. water (Tust, B. 20, 2441).
DI-CHIOBO-o-AUIBO-BEirZGIC ALDEHYDE
C„H2Clj(NHj)CH0. [78°]. Obtained by reduction
of di-chloro-nitro-benzaldehyde with FeSO^
and NH3 (Gnehm, B. 17, 754). Yellow needles.
SI. sol. water.
CHLOBO-AUIDO-NAf HIHALENE v. Cblobo-
NAPHTHTIiAlUNB.
Chloro-di-amido-naphthalene v. Chlobo-
NAPHTHYI^EIIE-DIAIIIirE:.
GHLOBO-AIIID0-(a)-ITAPHTH0IC LACTAM
NH— CO
0„H,ClNOt.
-go
[270°]. Chloro-amido-
la)-naphthoid. Chhro-naphthostyril. Formed
by reduction of chloro-nitro-(a)-naphthoio aoid
[226°] with FcSO, and NH,. Yellow needles
(from »l9obol) (Kkstrand, B. 18, 2881).
OHLORO-AMIDO-NAPHTHOIC LACTAM.
[265°].
Si-cMoro-amido-naphthoio lactam
/CO
C„H.OL< I ZH-chloro-naphthoslyril,
Formed by ohiorination of the lactam of amido-
(a)-naplithoio acid. Also by heating nitTo-(a)-
naphthoic acid [215°] with excess of fuming HCl
for two hours at 140°-150°. Yellow needles (from
acetic acid). SI. sol. alcohol (Ekstrand, B. 19,
1132).
CHIOEO-o-AMIDO-PHENOL
0,H3C1{NH2)(0H) [1:3:4]. From oHoro-o-nitro-
phenol, tin, and HCl (Faust a. Saame, A. Suppl.
7, 193).— B'HCl: lamihm (from water).
Methyl ether C„H3Cl(NHj)(0Me). Chloro-
anisidine [52°]. (260°). From the nitro- com-
pound. White needles or prisms. Sol. alco-
hol, ether, and benzene. Salts. — ^B'HCl :
colourless soluble needles. — ^BjE^ClsFtCl^: soluble
yellow needles.
Picrate B'CeHj(NOj),OH : [about 200°];
yellow needles, sol. alcohol and ether, si. sol.
water.
Acetyl derivative [150°], (320°), glisten-
ing plates (Herold, B. 15, 1685).
Chloro .p. amido - phenol OsH3Cl(NH2)(OU)
[1:3:6]. [153°]. From ^-nitro-phenol by treat-
ment with KClOa and HCl and reducing the
product with tin and HCl (KoUrepp, A. 234, 6).
Unstable needles, t. sol. alcohol and ether.
Bleaching powder and HCl give chloro-quinone
chlorimide 0.H3C1(NC1)0. Salts. — B'HCl:
trimetrio plates. — B^H^SOj 2aq : scales. —
B'HjCASJaq: needles. — TartrateB'CjHjOj:
monoclinio crystals, insol. water.
Si-chloro-o-amido-pheuol
C.H301j(NH2)(0H) [1:3:5:6]. Prom di-chloro-
nitro-phenol [121°] by tin and HCl (Fischer, A.
Svppl. 7, 189). Unstable scales ; reduces
' AgNOj, forming a mirror. — B'HCl : ppd. by
HCl from solution.— B'jHjSO^.
I)i-chloro.^-amido-phenol
C3H2C1,(NH3)(0H) [1:3:5:2]. [167°]. From di-
chloro-nitro-phenol [125°] by tin and HOI
(Eollrepp, A. 234, 10; Seifart, A. Sifpl. 7, 202).
Needles (from water) ; may be sublimed. Oxi-
dation gives di-chloro-quinone. HCl and bleach-
ing powder give di- chloro -quinonimide. —
B'HCl. — B'HBr: hexagonal plates ; v. si. sol.
cold water.— B'jHjSO^ 3aq : needles.— B'HNOj :
[110°] ; plates.— B'HAO, : needles.
Di-chloro-2J-amido-pheuplOjH2Gla(NH2)(OH).
[173°]. Formed by passing HCl into an ethereal
solution of p-nitroso-phenol (Jaeger, B. 8, 895).
Needles ; may be sublimed. Is perhaps identi-
cal with the preceding.
Methyl ether C„H3Clj(NH,)(0Me). [72°].
Formed by passing HCl into a solution of
p-nitroso-phenol in MeOH (J.). Long slender
needles (from dilute alcohol).
Ethyl ether. C„HjClj(NHj)(OEt). [46°].
(276°).
Tri-chloro-m-amido-phenol
0„HC1,(NH,)(GH) [1:8:5:6:2]. [95°]. Formed
fromtri-chloro-nitro-phenolO,HCl3(NOj)(OH)by
reduction with tin atid HCl (Daccomo, B. 18,
1166). Colourless silky needles. V. sol. alcohol,
ether, benzene, and hot water ; Fej,Gl, gives a
splendid violet-red colouration.
Xri-chloroTp-amido-phencl
C^01,(N:^(0H). [159°J.
Formation. — 1. From y-amido-phenol by
ohiorination ; the by-products are tri- and
tetra- ohloro-hydro-quinone (Lampert, /. pr. [2]
33, 371).— 2. From quinone chloro-imide and
cone. HCl (Hirsch, B. 11, 1981 ; 13, 1907).
Preparation.— By passing chlorine gas into
cone. HCl in which ^-amido-phenol hydro-
chloride is suspended. The reaction is ended
as soon as a portion of the crystalline product
dissolves completely in water and gives, on add-
ing bleaohing-powder solution, flooculent tri-
chloro-quiuone ohloro-imide, while the super-
natant liquid shows no turbidity (which would
be duo to oily di-chloro-quinone ohloro-imide).
The base is precipitated by Na^OOj (E. Sohmitt
a. M. Andresen, J. pr. [2] 24, 42"6).
Properties. — Glittering needles (from alco-
hol). Is a weak base, its hydrochloride being
decomposed by boiling with water (Hirsch, B.
13,1903).
Beactions. — 1. NaOH solution and air convert,
it into tri-chloro-quinone. — 2. By diazo-reacOoi}
it yields tri-chloro-phenol [54°]. — 3. Bleaching-
powder and HCl give tri-chloro-quinone chlori-
mide. Salts.^B'HCl.— B'jHoSOj: smallneedles.
CHL0B0-2J-AIIIID0-FHEN0L i'-ST7LFH0iriC
ACID C„H3C1(0H)(NH.S03H) [1:2:5]. Formed
by adding cone, aqueous NaHSO, to mono- or
di-chloro-quinone chlorimide, air being excluded
(Eollrepp,.^. 234,21). Anhydrous needles (from
hot water), which change under water to trimetric
prisms (containing 2^aq). SI. sol. cold water,
insol. ether. Reduces boiling Fehling's solution.
Gives a silver mirror. Converted by nitrous
acid into the diazo- acid CgHjClN^SOj 3aq which
crystallises in prisms. Salts. — ZnA'^: trime-
tric prisms. — NiA'^. — CuA'ji minute yellowish-
brown needles, insol. cold water.
CHLOEO-o-AMIDO-DIPHENYL 0,jH,oClN
ue. C,jHaCl(NH2). [48°]. Formed by reducing
o-nitro-diphenyl with tin and HCl (Hiibner a.
Osten, A. 209, 349). Long needles (from dilute
alcohol) ; si. sol. water, v. e. sol. alcohol and
ether. Its salts are partially decomposed by
water.— B'HCl : laminse.- B'^HoPtCl, : orange
tables.— B'HN03.—B'jH,S0,.
Chloro-di-amido-diphenyl
0,H4(NH2).CsH,Cl.NH,. Formed by aUowing,an
alcoholic solution of beuzene-azo-^-chloro-ben-
zene mixed with SnClj and a couple of drops of
IIjSO, to stand in the cold. The base was not
isolated in a pure state. The hydrochlorides
B"H2Cl2 forms white concentric needles (Mentha
a. Heumann, B. 19, 2970).
Si-ohloro-di-amido-diphenyl
C3H3Cl(NH3).C„H3Cl(N5a). [60°]. Formed by
treating p-ohloro-benzene-azo-^-chloro-benzeno
C3H,Cl.Nj.CsH,01 with SnClj (Schultz, B. 17,
464)., Glittering lamina.— B'HjSO,. V-..
GHLOEO-SI-AMIDO-DI-FHENYI-AlHINErb-
CAEEOXYLIC ACID
C.HjCl(NH2)j.NH.0^,.C0jH. [c. 240°].- Formed
by reduction of chloro-di-nitro-di-phenyl-amine-
o-oarboxylio acid with tin and HCl (Jourdan, B.
18, 1455). Colourless felted needles. SI. sol.
hot water and ether, nearly insol. benzene and
ligroiin. FejClj gives a brownish-violet coloura-
tion.
DI - CHLOBO - TBI - AMIDO - TBI - PHENYl-
CABBINOL 0„H„CljN,0 i.e.
C(0H)(0„H,C1.NH,),(0,H4NH^. Di-cKUyro-parcr
OHLORO-AMTL-ALGOriOI,.
sa
rosanUine. Formed by hoating^-toluidine (21 g.),
D-chloro-toIuidine (50 g.), and aqueous arsenic
acid (106 g. of 75 p.o.) at 190° (Heumanu a.
Heidlberg, B, 19, 1989). Lustrous green mass.
Dyes a much bluer shade than ordinary rosani-
line.
CHLOBO-AIIIOO-FHENYLENE MEBCAF-
TAN C.H,01NSj i.e. C,HjCl(NH.)(SH)„ [3:5:2:1].
From the chloride of m-chloro-nitro-benzene
disulphinio acid by tin and HCl (Allert, B. 14,
1136). Does not react with formic acid.
CHLORO-AMISO-FHENYL-EIHYLENE v.
GHLOBO-AMISO-STYBEine:.
CHLOBO - AmiBO - FHEXTL ■ GLT0X7IIC
ACID V. IsAHN.
CHLOBO -AUISO-FHEITYL KEBCAFTAN
C.H,01(NH2)(SH). [130°]. From m-chloro-
nitro-benzene sulphonic acid, tin, and HCl
(Allert, B. 14, 1435).— B'HCl.
Exo - CHLOBO - esa-AMIDO - FEOFTL - FYRO-
CATECHIN Mono-methyl ether
03H.Cl.CsHj(NH,)(0Me)(0H) [1:5:3:4]. [97°].
From nitro-eugenol C3H5.CsHj(NOJ(OMe)(OH)
by tin and HCl (Weselsky a. Benedikt, M. 3,
389). Pearly plates (from alcohol).— B'HOlaq.
TBI-C{ILOBO-AMIDO-FYBISINE C^HjClsN,
probably N<;;q^}-^^j>C.NH2. [158°]. Formed
in small quantity, together with di-chloro-di-
oxy-amido-pyridine, tri-chloro-oxy-amido-pyri-
dine, and tetra-chloro-amido-pyridine, by heating
glutazine with FClj (6 to 7 pts.). Long felted
colourless needles. SubUmable. V. sol. alcohol,
e1. sol. hot water. Dissolves in aqueous acids,
but not in alkalis. Its bromo -derivative
forms flat colourless needles [228°] (Stokes a.
Pechmann, B. 19, 2710 ; Am. 8, 392).
Tetra-chloro-amido-pyridine C^H^NjCl, pro-
bably N<qq|qq|>C.NH,. [212°]. Formed,
together with an equal quantity of tri-ohloro-
oxy-amido-pyridine, and small quantities of di-
chloro-di-oxy-amido-pyridine and tri-chloco-
amido-pyridine, by heating glutazine with PCI,
(6 to 7 mols.). Thin colourless plates or cubical
crystals. Sublimable. Sol. hot benzene, m. sol.
hot alcohol, si. sol. cold alcohol, insol. water. It
does not dissolve in aqueous alkalis, and op.ly
slightly in cone. HCl. Alcoholic NaOBt forms
C5H,N,Cl3(0Et) [83°] and 0jH2NjCl3(0Et),
[98°] (Stokes a. Pechmann, B. 19, 2710 ; Am.-
' DI-CHLOEO-DI-AMIDO-aTTINONE
CaCl2(NH2)20j., Chloranilamide. Prepared by
adding crystallised tetra-ohloro-quinone rubbed
up with alcohol to a boiling alcoholic solution
of ammonia ; after the tetra-chloro-quinone has
dissolved, the compound separates in brown
needles (Laurent, Bev. Scient. 19, 141 ; A. 52,
347 -, Knapp a. Schultz, A. 210, 183), Dark lus-
trous needles, insol. water, alcohol, and ether;
readily sublimed. Its solution in alcoholic
KOH is violet. Boiling SnCl, forms unstable
CjCl3(NHj),(0H)j. Fuming HNOg forms chloro-
picrin and oxalic acid.
o-CHLOBO-o-AMIDO-STYBENE
CjH,(NH2).0H:CHC]. o-Amido-phemjla-chloro-
ethylene. White concentric prisms. V. sol.
alcohol and ether, t. sL sol. cold water. Formed
by reduction of ai-ohloro-o-nitro-styrene with tin
and HCl. By heating with sodium ethylate at
Vol. IL
about 170' it gives indole.— B'HCl : colourless
needles, v. sol. water and alcohol (Lipp, B. 17,
1071).
GHLOBO-ASIIBO-STJLFHO-BENZOIC AGIO
0,H,C1NS05 i.e. C„HjCl(NH,)(S05H)(C0,H)
[l:2:x:3]. From chloro-o-amido-benzoic acid and
fuming HjSO, (Cunze a. Hiibner, A. 135, 113).—
BaA" : clumps.
GHLOBO-AMIDO-THYMOL
C,HClMePr(NHj)(OH). [101°] (A.) ; [103'?] (S.).
Preparation.—!. By pouring 4 vols. oono. HCl
npon thymo-quinone-chloro-imide {g,-v.) ; the
liquid begins to boil and yellow crystals separate.
The liquid is shaken with ether, and the ether,
containing ohloro-thymo-quinones, is decanted ;
the residue, in which the ohloro-amido-thymol
hydrochloride is suspended, is then Altered and
decomposed by Na2C0j,. It dissolves in excess
of Na^COj giving the solution a green colour.
This must be avoided. — 2^ In a similar way
from chloro-thymo-quinone-chloro-imide {c[.v.).
3. From thymo-quinone-oxim (nitroso-thymol)
and cold fuming HClAq (Sutkowski, B. 19, 2315).
Prc^erties. — Glittering crystals (from water).
V. sol. alcohol and ether (Andresen, /. pr. [2] 23,
175). Bleaching-powder forms ohloro-thymoqui-
none chlorimide. Heating with chloranil in
HOAc produces a red dye CanHajClaNjOa [232°].
CHLOBO-AMIDO-IOLirENE v. Chlobo-iolui-
DINE.
CHLOBO-AHIOO-XYLENE v. CnLOBO-zyu-
DINE.
exo-Chloro-amido-o-xylene
ClCHa-CsHj-CHaNHj. Formed by the action of
HClAq at 200° on its phthalyl derivative (Strass-
mann, B. 21, 681).
Phthalyl derivative
[l-2]ClCH,C,Hj.CH2.N(CO)jCeH,[l-2]. Exo.
chloro-xyUne-phihalimide. [140°]. Formed by
the action of exo-di-chloro-o-xylene (1 mol.) on
potassium phthaUmide (1 mol.) at 200° (Strass-
mann, B. 21, 580). Prisms (from alcohol).
Heated with HClAq to 200° it is converted into
phthalio acid and exo-chloro-amido-xylene.
oi-CHLOBO-ISOAIKLYL ACETATE
CjHj.CHCi.OAo. (118°-128°).S.G. 1^-987. From
isovaleric aldehyde and AoCl (Maxwell Simpson,
Pr. 27, 120). Liquid ; slowly decomposed by
water.
Tri-chloTo-sec-amyl-acetate ,
CHMe(C,H4Cy.0Ac. (129°-134°) at 25 mm.j
(227°) at 726 mm. S.G. J-j| 1"305. From me-
thyl-tri-chloro-propyl carbinol and AcCl (Garza-
roUi-Thurnlackh, A. 223, 151).
CHLOBO-AMYL-ALCOHOL C,H„C10 i.e.
CfiifiHOK). Amyleneglycolehlorhydrin. (155°). '
From crude amylene and aqueous HCIO (Carius,
A. 126, 199 ; Eltekoff, /. B. 14, 360). V. sol.
water. Decomposed by potash with forination
of amylene oxide. NajSO, forms oxy-pentan'e
sulphonic acid (j. v.),
Tri-chloro-amyl alcohol CsHjCIjO i.e.
CH3.CHCl.CClj.CHMe.OH. [50-5°]. (109°) at
20mm.; (124°)at41mm. From tri-chloro-butyrio
aldehyde and ZnMe^ in ether, followed t>y whtei
(GarzaroUi-Thurnlaokh, A. 223, 149).
Properties. — Silky needles grouped inrosettes
(from ether). Smells of camphor. Volatile with
steam. Faintly soluble in water, v. sol. alcohol
and ether. Carbonised by cone. HiSO«.
m
CHLORO-AMTL-ALCOHOL.
Reactions. — 1. Warm fuming HNO, give3
COj and tri-ohloro-butyrio acid. — 2. HjSOj and
KjCrjO, give the ketone CjHjCla.CO.Me (191°-
193°).— 3. Finely divided iron and acetic acid
reduce it to oUoro-pentenyl alcohol (g. v.).
CHLOKO-AMYL-AHTHRACENE C,8H„C1 or
C,H,<^^[Jj«^")>C,Hj. [71°], Prepared by chlo-
rination of amyl-anthracene in OHCI3. Light
yellow needles with blue fluorescence.
Picric acid compound : red needles (Lie-
bermann a. Tobias, B. 14, 797). '
a-CHLOBO - n • AMYLENE C,H,C1 i.e.
CH3.CHj.CHj.CCl:CHj. (96°). S.G.5^'-872. From
amylene chloride and alcoholic KOH (Bruylants,
B. 8, 411).
a.-Chloro-iso-amylene (CH,)jCH.CH:CHCl.
(86°). FromisoamylidenedichlorideFrCHj.CHCIj
and alcoholic KOH (B.).
Chloro-amylene C5H5CI. VaUryhne hydro-
chloride. (100°). From valerylene and fuming
aqueous HCl at 100° (Beboul, Z. 1867, 173).
Isoprene hydrochloride OsH,Cl. (85°-91°).
S.G. 2 -885 (Bouchardat, C. B. 89, 1317).
Di-chloro-amylene CHa.CHiCCl.CHCl.CH,.
(142°-144°) at 736 mm. From ohloro-pentenyl
alcohol C,H,C1.CH(0H).CH3 by POl,. Partly
converted by boiling water into chloro-pentenyl
alcohol (Garzarollj-Thnrnlackh, A. 223, 160).
Di-chloro-amylene CsHjClj. (146°). Fromtri-
chloro-hexoic aldehyde and cone. KOHAq (Pin-
ner, A. 179, 35 ; B. 10, 1052). Gives with bro-
mine OsHjOljErj (230°-240°).
Tri-ohloro-amylene C,H,C1,. (200°). From
tetra-chloro-pentane (240°) and alcoholic KOH
(Bauer, C. B. 51, 572).
CHLOBO-AMYLENE SI-CABBAIkEIC ETHEB
0„Hj,01N,04 i.e. C^lI^Gl(THB..CO^t),. [130°].
From isovaleric aldehyde, carbamio ether, and
HCl (Bisohoff, B. 7, 633).
CHLOBO-DI-AmYL STTIf HONE
05H,„C1.S02.C5H„. (330°). Formed together
with di-chloro-di-amyl sulphone (0jH,gCl)2S02 by
treating di-amyl sulphone with ICl, at 130°
(Spring a. Winssinger, Bl. [2] 41, 307).
CHLOBO-ANETHOL C,ja:„C10. [6°]. (258°)
(Ladenburg); (229°) (Landolph). S.G. 2 1-115
(Lad.) ; ^a 1-191 (Lan.). Prepared by the action
of PCI5 on anethol (Ladenburg, A. Suppl. 8, 90).
By treatment with KOH it gives a mixture of two
liquids, the first of which, 0,^3^0,, boils at
(268°-270°),and the second can be converted into
the first by morn prolonged action of the KOH
(Landolph, B. 13, 148).
CHLOB0-AN6EL1C AOIS
CH3.CC1:CH.CH3.C0,H (?) [104°]. The ethyl
ether is formed by treating di-chloro-angelic acid
in alcoholic solution with zinc and HCl (Pinner
a. Klein, B. 11, 1498).
Ethyl ether l^tAf. Liquid.
Isomeride v. CHiiOso-TiaLic acid.
Di-chloro-angelic acid OsHgCLO^ i.e.
CH3.CC1:CH.CHC1.C02H(?). From ohloro-oxy-
angelic acid and PCI, (Pinner a. Klein, B. 11,
1498). Oil.
CHIOBANILIC ACID v. p-Di-asLOBO-p-m-
OSY-quiNONB.
0-CHLOEO-ANILINE CaHsClN ».e.
C„H^Cl(NHj) [1:2]. Mol. w. 127J. (207° i. V.).
S.G. S 1-2338.
Formation.— By reduction of o-ohloro-nitro-
benzene. May be separated from p-ohloro-ani-
line by distiUing the sulphates with steam, that
of o-chloro-aniline being decomposed (Beilstein
a. Kurbatoff, A. 176, 27).
Salts.— B'HCl: trimetrio plates: S. 12 at
13°.— B'HNOj: S. 10atl3-5°.— Picrate: v. si.
sol. cold water ; si. sol. alcohol.
Acetyl deri«a««8 0,H,01(NHAo). [88°].
Long flat needles (from dilute HOAc) (Beilstein
a. Kurbatoff, A. 182, 100).
m-Chloro-aniline O.H4Cl(NH,) [1:3]. (230°
i. v.). S.G. 2 1-243. From m-chloro-nitro-Denz-
one (B. a. K.). Its salts are hardly decomposed
by boiling water.— B'HCl.— B'HBr : long red
needles (Staedel, B. 16, 28).— B'HNO,.—
B',H„SO. : si. sol. cold water.
Acetyl derivative O^H^CUNHAc). [73°].
p-Chlord-aniUne 0„H^C1(NHJ [1:4]. [70°].
(231° i. v.).
Formation. — 1. By distilling ohloro-isatin
with KOH (Hofmann, A. 53, 1).— 2. By reducing
p-chloro-nitro-benzene with Snd:. — 3. From its
acetyl derivative obtained by chlorinating acet-
anilide (Mills, P. M. 49, 21).
Properiies. — Trimetrio prisms. Is a strong
Salts.— B'HCl.-B'2H3PtCl,.— B'HNO, : la-
minffl, S. 6-7 at 12-5°.- B'ijHjSO, : si. sol. cold
water.— B'HjOjO, ^aq.
Acetyl derivative OsB.fil.'S'HAo. [173°].
Thick needles (from dilute HOAc).
c-Di-chloro-aniUne C8H3Cl2(NHj) [1:2:3].
Mol. w. 162. [24°]. (252°). From nitro-benzene
by chlorination, in presence of SbClj and reduc-
tion (Beilstein a. Kurbatoff, A. 196, 214 ; B. 11,
1860). Needles (from ligroin).
Acetyl derivative CjHaCyNHAc), [157°].
c-Di-chloro-aniline ObH3C12(NHj) [3:1:2].
[39°]. From di - chloro - nitro - benzene [71°]
(B. a. K.). Needles, v. sol. ligroin.
Acetyl derivative CeHjC^NHAo). [175°].
s-Dl-ohloro-aniline C„H3Cl2(NH2) [1:3:5].
[50-5°]. (260° i. v.). From s-di-ohloro-nitro-
benzene (Witt, B, 8, 145 ; B'. a. E. ; Langer, A.
215, 120).
Acetyl derivative C„'H.,Cl2{'SKAo). [187°].
Di-chloro-anilineC,H30l2(NH2) [1:4:2]. [50°].
(251°). From di-chloro-nitro-benzene [55°]
(Jungrfeisoh, A. Ch. [4] 15, 252 ; B. a. K.). (251°).
Formed also* by chlorinating m-chloro-aniline
and by heating nitro-benzene with fuming HCl
at 245° (Baumhauer, A. Suppl. 7, 209). CrO,
gives di-chloro-quinone.
Acetyl dariuatioeCsHaCyNHAo). [132°].
Di-ehloro-aniline C5H,Clj(NH,) [1:3:4]. [63°].
(245°). From acetanilide (1 mol.) and chlorine
(2 m,ols.). Obtained also by chlorinating 0- ovp-
ohloro-aniline (Gricss, A. 121, 268; Beilstein,
A. 182, 95; Witt, B. 7, 1602).— B'HCl.—
B'jH^tCl,.
Acetyl derivative 08H3Cl2(NHAo). [143°l
Di-chloro-aniline CjHjCljINH^ [1:2:4].
[71-5°]. (272°). From di-ohloro-nitro-benzene
[43°], or by chlorinating m-chloro-aniline
(B. a. K.). Long needles ; strong base.
Acetyl derivative C.H,CUNHAa).
[120-5°].
c-Tri-ohloro-aniline CeH,Cl,(NHj) [1:2:3:4].
Mol. w, 196-6. [67-6°]. (292° i, V.).
CHLOllO-ANTHRACENE-OARBOXYLIC ACID,
35
Formation. — 1. From its acetyl deiiTative.
, 2. By reducing 0,H,(NOj)Cl, [1:2:3:4].
Acetyl derivativeCja..i(S'BAo)Cl,. [122°].
When chlorine is passed into a solution o£ acetyl
m-chloTo-aniline in strong (90 p.o.) acetic acid,
two aoetyl-trichloro-anilines are formed ; one of
these, CJH2Cl,(NHAc) [1:2:4:5] [185=] is hardly
soluble in dilute (50 p.c.) acetic acid, the other
[1:2:3:4] ia soluble (Beilstein a. KurbatofE, A.
192, 234).
Tri-chloro-aniline C8H,Cl3(NH2) [1:3:5:6].
[77-5°]. (262° i. V.). From aniline, p-ohloro-
aniline, or (1, 3, 4)-di-chloro-aniline in glacial
acetic acid by chlorine (Hofmann, A. 53, 35;
Beilstein a. Kurbatofl, '£. 11, 1862; Langer,
A. 215, 114). Also from aniline and S0,^G1,
(Wenghoffer, /. pr. [2] 16, 449). Long needles
(from ligroin). -
Acetyl derivativeO^C\,{SB^. [204°].
Tri-chloro-aniline C,Hj01a(NH3) [1:2:4:5].
[96°]. Prom CA(N0JCl3 [58°] (Lesimple,
A. 137, 125; BeiUtein a. KurbatofF, A. 192,
231). Obtained .also by chlorinating (2, 5, 1)-
or (3, 4, l)-di-chloro-ani]lne, or m-chloro-aniline.
Needles (from ligroin).
Acetyl derivative CgH2Cl,(NHAc).
[185°].
i - Tetra - ohloro - aniline CjH01,(NH2)
[1:2:3:5:6]. [88°]. Formed by chlorinating m-
chloro-aniline (B. a. E.). Gives, by eliminating
NHj, tetra-chloro-benzene [51°].
Acetyl derivative CjHCl,(NHAo) [174°].
s - Tetra - chloro - aniline C,HCl<(NHj)
[1:2:4:5:6]. [90°]. Prepared by reducing s-tetra-
ohloro-nitro-benzene (Lesimple, Z. 1868, 227).
c-Tetra-cMoro-aniline C„HC1,(NH2). [118°].
From c-tetra-chloro-nitro-benzene (Beilstein a.
Kurbatoff, B. 11, 1862).
4ce«y J ieriuo«ve [154°] (Tust,i5. 21,1533).
Penta- chloro -aniline OjOlsNHj [232°].
From 3-di-chloro-anUine by chlorinating it in
ethereal solution (Langer, A. 215, 120). Ob-
tained also by reducing penta - chloro - nitro -
benzene (Jungfleisch). Long white needles
(from alcohol). V. sol. alcohol and ether, m. sol.
benzoline. By further chlorination in acetic
acid solution it gives penta - chloro - phenyl
hypochlorite CjClsOGl.
CHLOBO-ANISIC-ACID v. Methyl derivative
of GbiiObo-oxt-benzoic acid.
CHLOBO - ANISISINE v. Methyl ether of
Cblobo-amiso-phienol.
CHLOEO-ANTHBACENE C„H,01. [103°].
Obtained by fusing anthracene dichloride (Fer-
kin, C. N. 34, 145). Golden-yellow needles, y. sol.
ether, alcohol, and benzene. The picric alcid
compound forms scarlet needles.
Di-(4).chloro-anthracene Cg'S,<^Qf^CJ3.i.
[209°]. Formed by the action of (2 mols. of)
chlorine upon anthracene-(4)-carboxylio acid or
upon {A. l)-chloro-anthracene-(il. 2)-carboxylic
acid (Behla, B. 20,704). Prepared by chlorinating
anthracene (Laurent, A. 34, 294 ; Perkin, C. J.
24, 14; Grcebe a. Liebermann, A. 160, 187;
Suppl. 7, 284). Long yellow needles ; v. sol. ben-
zene, b1. sol. alcohol and ether. Not affected by
boiling KOH. Gives anthraquinoue on oxidation.
Oi-cUoro-authracene C,
I.C1A<|^.
CcH,
[255°]. From tetra-chloro-anthraquinone by
^eating with zinc-dust and aqueous ammonia
(Kiroher, A. 238, 347 ; B. 17, 1169). Slender
needles. On oxidation it gives di- chloro- anthra-
quinone.
Tri-chloro-anthraoene C„H,Cla. [163°]. From
di-chloro-anthracene dichloride and alcoholic
KOH (Sohwarzer, B. 10, 378 ; cf. G. a. L.). Long
golden needles (from alcohol). The alcoholic
solution shows blue fluorescence.
Tetra-chloro-anthracone C,C1.< I >CaH,.
[149°]. From tetra-chloro-benzoyl-benzoic acid
(1 pt.), red phosphorus (^ pt.), and fuming HI
m pts.) at 215° (Kiroher, A. 238, 346). Slender
needles, sol. benzene and chloroform. CrO, gives
the corresponding tetra-chloro-anthraquinone.
Tetra-chloro-anthracene CnHjCl,. [152"].
Prepared by the action of boiling alcoholic KOH
on the di-chloro-anthracene tetrachloride [206°]
obtained from nitroso-anthrone and PCI, (Lieber-
mann a. Lindermann, B. 13, 1589). Tellow
needles, sol. hot acetic acid, si. sol. alcohol. On
oxidation with CrO, it gives crystalline dichlor-
anthraquinone.
Tetra-chloro-anthracene C,4H4Cl4. [164°]
(H.) ; [220°] (G. a. L.). Formed by the action
of alcoholic KOH upon pure di-chloro-anthra-
cene tetra-chloride [187°] (Hammerschlag, B. 19,
1108 ; Grisbe a. Liebermann, A. Suppl. 7, 283).
Golden yellow needles. SI. sol. nearly all sol-
vents. By CrO, and acetic acid it is oxidised to
di-chloro-anthraquinone [205°].
Hexa-chloro-anthraoene OnHjCl,. [320°-330°].
Yellow needles. Prepared by the action of SbCl,
on di-chloro-anthracene dichloride. Oxidation
with KfiT,fl, and H^SOt gives tetra-chloro-an-
thraquinone (Solas, C. N. 28, 167 ; Ciehl, B. 11,
17S).
Hepta-chloro-anthracene 0,4H,C1,. [above
350°]. Prepared by the prolonged action of
SbCl,on di-chloro-anthracene-dichlorideat 260°.
Sublimes in yellow needles (Diehl, B. 11, 176).
Octo-chloro-anthracene GifH^Cl,. [above
350°]. Feathery crystals. Prepared by the pro-
longed action of SbCl, at 280° on the lower chlo-
rinated anthracenes (Diehl, B. 11, 177). BuoS
{B. 9, 1488) could only obtain hesca-chloro-bena-
ene.
SI-CHLOEO-ANTHBACENE TETBA-SBO>
MIDE G,„H,GljBr,. [16C°](S.); [178°] (Hammer-
Bchlag, B. 19, 1106). Obtained by exposing di-
chloro-anthracene [209°] to bromine-vapour for
a considerable time (G. a. L. ; Schwarzer, B. 10,
376). Satiny needles (from benzene); si. sol.
alcohol and ether; v. sol. benzene and GHCl,.
At 180°-190°it is converted intodi-chloro-brorao-
anthracene [168°]. Boiling alcoholic KOH gives
di-chloro-di-bromo-anthracene.
{A. l)-CHL0B0-AITTHBAGENE-(i4. 2)-CABB-
OXYLIC ACID C,jH,OjCl i.e.
G.H,<g^^^>0.H4. [259°]. Obtained by
helating anthracene T^ith carbonyl chloride under
pressure at 240°-250° ; or by passing chlorine
(1 mol.) into a solution of anthracene-M)-oarb-
oxylic acid in GHGl,. Long yellow glistening
needles. Sublimes. Sol. alcohol, ether, and
acetic acid; al. sol. benzene, chloroform, and
xylene ; T. sL sol. water and ligroin. Its solu-
o2
88
OHLORO-ANTHRACENE-OARBOXrLIC AOID.
tions have a blue fluorescence. At its melting-
point it evolves CO^, leaving (^)-chloro-anthra-
cene. By CrO„ KMnO^, or dilute HNO3 it is
oxidised to anthraquinone. Alcoholic KOH at
160°-170° reduces it to anthraoene-{il)-oarboxy-
lio acid. Chlorine converts it into di-(jl)-chloro-
anthracene. Salts. — KA': very slender yellow
needles. — AgA' : minute yellow prisms. — BaA', :
thick yellowish glistening prisms (from water) or
/leedles (from alcohol).
Methyhether MeA': [123°]; yellow needles
or large six-sided tables ; sol. alcohol, ether, &a.,
with a blue fluorescence ; insol. water (Behla,
B. 20, 701).
BI-CHLOBO-ANTHBACENE I)I-CHLOBID£
C.H.<^^jp>O.H,. [150°]. Formed by passing
chlorine into anthracene dissolved in chloroform
(Schwarzer, B. 10, 377). Prisms (from chloro-
form) ; si. sol. alcohol and ether, v. sol. benzene.
At 170° it yields tri-chloro-anthracene [168°].
Boiling alcoholic KOH converts it into anthra-
quinone.
Di-cIiIoro-anthTaceuc-totra-chIorideC,,H,CL.
[187°] (H.) ; [145°] (D.). Thin white needles.
Prepared by passing chlorine for a long time
through a benzene solution of anthracene or di-
chlorauthraoene [209°]. By treatment with
alcoholic KOH it yields tetra-chloro-anthracene
[164°] (Hammerschlag, B. 19, 1107 ; cf. Diehl,
B. 11, 174).
Si-chloro-anthracene-tetrachloride
CnHgClj-Cl,. [205°-207°]. White needles. Does
not fluoresce. Prepared by heating nitroso-
anthrone with PCI5 to 180°. By boiling with
alcoholic KOH it gives tetra-chloro-anthracene
[152°]. (Liebermann a. Lindermann, B. 13,
1588).
DI-CHLORO-ANTHEACENE DISULPHOHIC
ACID C„H5C1,(S03H)2. Prom (1 pt.) di-chloro-
anthraoene [209°] and (5 pts.) fuming H^SO, at
100=' (Perkin, C. J. 24, 15). Orange needles ;
V. sol. water but ppd. by HCl or H^SOj. Dilute
solutions of the acid and its salts fluoresce blue.
On oxidation it gives anthraquinone disulphonic
acid.— Na2A"a! aq.— BaA".— SrA".
CHIOBO-ANTHKAHILIC ACID v. Chloro-
IMIDO-CENZOIC ACID.
m-CHLOSO-ANTIIRAftUIHOIJE C„H,C10,
i.e.C.H3Cl<;;^Q>C„H^. [204°]. Formed by heat-
ing TO-ohloro-benzoyl-benzoic acid with sul-
phuric acid at 160°-175°. Yellowish-grey
needles; v. sol. hot C^H,, si. sol. acetic acid
CSj, and hot alcohol. Sublimes without decom-
position (Grffibe a. E6e, G. J. 49, 531).
Di-chloro-anthraquinone C,H,(C2O,)0sHjCl2.
[205°]. Formed by oxidation of tetra-chloro-
anthracene [164°] with CrO, and acetic acid
(Hammerschlag, B. 19, 1109; cf. Graebo a.
Liebermann, A. Suppl. 7, 290). Formed also by
heating anthracene with SbCls at 100 ' (Diehl,
B. 11, 179). Glistening golden needles (from
acetic acid). By NaOH fusion it gives alizarin.
Di-chloro-anthraquinone C,CljH2(C202)CjH,.
[261°]., Formed by oxidising di-chloro-anthra-
oene [255°]. Needles (from ohloroform-ajcohol).
Gives alizarin when fused with potash (Eircher,
B. 17, 1169).
Tri-chlorc-anthraqninone CnHjOlaO^ [284°-
290°]. Got by heating anthraquinone with SbCl,
at 180° (Diehl, B. 11, 180). Yellow needles.
Tetra-chloro-antliTaquinone C,Gl4(C202)C,R,.
[191°]. From tetra-ohloro-o-benzoyl-benzoic acid
and HjSO, at 100° (Kircher, A. 238, 344 ; B. 17,
1167). Golden needles (from benzene-alcohol).
Oxidised by fuming HNO, at 140° giving totra-
chlorophthalio acid. Beduced by distillation
with zinc-dust to anthracene. Yields phthalic
acid on fusion with NaOH.
Di-sulphonic acid ''C„HjCl,02(S0,H)j.
Salts.— BaA".— CaA".
letra-chloro-anthraqninone C^HiGliO,,
[320°-330']. Prepared by long heating of di-
ohloro-anthraquinone with 6 pts. of SbCls at 200°
(Diehl, B. 11, 180). Yellow needles
PeAta-chloro-anthraquinone ChHjCIjOj.
Prepared by heating di-chloro-anthraquinoHa
with 8 pts. SbCls at 250° (D.). Sublimes with-
out melting. Insoluble in the ordinary solvents.
CHXOaO-ATBOPIO ACID C,H,C10j. [85°].
From tropic acid and PGlj. Needles (Laden-
burg, B. 12, 948).
CHI.OBO-AZO-BENZENE v. Benzene-azo-
ciiLOGo-BEitZENE, vol. i. p. 374.
Di-chloro-azo-beuzene v. CriiOho-benzene
AZO-CHLOnO-BENZENE, vol. i. p. 381.
CHLOBO-AZOPHENINE C^HjjClNj. [230°].
Formed by heating 2>-ohlorb-^-nitroso-di-phenyl-
amine with aniline and aniline hydrochloride at
100°. Very similar to azophenine, but more
sol. benzene (O. Fischer a. Hepp, B. 20, 2481).
Tri - chloro -azophenine C^uHjiClaN.
[246°1 (Fischer a. Hepp, B. 21, 676).
TBI-CHLOaO-AZO-PHEKOL v. Oxi-benzene-
Azo-PHENOL, vol. i. p. 388.
DI-CHLOKO-BABBIXUEIC ACID C,H;,CljNjO,
i. e. CC1j<;^q;^^C0. Formed by oxidising
di-chloro-oxy-methyl-uracil with fuming HNO,
(Behrend, A. 236, 64). Trimetrio crystals,
ffl:6:c = -777:1: -893. V. e. sol. alcohol and ether ;
sol. water.
CHLOBO - BENZALDEHTDE v. Cblobo -
BENZOIC ALDEHYDE.
CHLOBO-ISOBENZALFHTHALIMIDINE v.
CHLORO-OXY-PHENyL-ISOQUniOLINE.
CHLOBO-BENZAMIDE v. Amide of Chloeo-
BENZOIC ACID.
CHLOBO-BENZENE CbHsCI. Mol. w. 112i.
[-40°]. (132°). S.G. »,<> 1-1066. ^4- 1-5369. K<i •
60-67 (Bruhl). H.F.p.— 11,220. H.F.v,— 12,380
(Th.). S.H. (7°-64°) -326 (Schiff, G. 17, 486).
Vapour-pressure, Eamsay a. Young (O. J. 47,
654). S.V. 114-3 (Schiff, A. 220, 98); 114-5
(Ramsay). *
FormaUon, — 1. From phenol and PClj
(Laurent a. Gerhardt, A. 75, 79 ; Williamson a.
Scrugham, C.J. 7, 238} Eiche, A. 121, 357).—
2. By the action of chlorine on benzene in pre-
sence of iodine or other carriers (Hugo Muller,
C. J. 15, 41 ; Fittig, A. 133, 49).— 3. From benz-
ene and SO.Clj at 150° (Dumas, Z. 1866, 705).
4. From S^Clj and benzene at 250° (Schmidt,
B. 11, 1173).— 5. By heating benzene sulpho-
chloride with POlj at 210° (Barbaglia a. KekuU,
B. 5, 875). — 6. A solution of diazobenzene chlo-
ride, prepared from 30 grms. of aniline, and a
large excess of HCl is slowly run into a nearly
boiling solution of Cu^Cl^in HCl (150 grms. of a
10 p.o. solution of Cu^Cy. The bromo-benzene
is distilled ofE with steam (Sandmeyer, B. 17,
UHi^uitO-BENZENTE.
87
1633). — 7. By heating diazobenzene with a largo
exceBS of strong HCl; the yield is 40 p.c. of the
theoretical (Gasiorowski a. WaysB, £. 18, 1936).
Prc^erties. — Colourless liquid. When led-
throagh a red-hot tube it forms diphenyl, chloro-
diphenyl, di - chloro - diphenyl, and di - phenyl -
benzene (Kramers, A. 189, 135). Not affected by
boiling with Al^Clg. Converted by sodium into
diphenyl. MnO, and HjSO, give formic and
ii-chloro-benzoic acid (Carius, Z. [2] 4, 505 ; C.
Miiller, Z. [2] 5, 137). Cnloro-benzene passes out
of the system as ohloro-phenyl-mercapturio acid
0,^,jClNSO,.
o-Si-chloro-benzeue CgH^Cl, [1:2]. Mol. w.
147. (179° i. v.). S.G. 2 1-328 (B. a.K.); 1-325
(P. a. C).
Formation. — 1. In small quantity, by chlori-
nating benzene (Beilstein a. Kurbatoff, A. 176,
42 ; 182, 94 ; B. 7, 1398, 1739), Separated from
the greater part of the solid j>-di-ohloro-benzene
by pressure; it is then heated with fuming
HjSO, at 210° for 2 days ; this sulphonates only
o-di-chloro-benzene. The resulting sulphonic
acid is purified by crystallisation, and recon-
verted into di-chloro-benzene by hydrolysis (Frie-
del a. Crafts, A. Ch. [6] 10, 411).— 2. From o-
ohloro-phenol and FCl, (B. a. E.).
Properties. — Liquid. Gives a nitro- deriva-
tive [43°]. MeCl and Al^Cl, at 100° give chiefly
hexa-methyl-benzene and tri-chloro-mesitylene
(F. a. C).
»n-Di-oMoro-benzene CaH,Clj [1:3]. (168°
uncorr.) (S.) ; (172°) (K.). S.G « 1-307.
Formation. — 1. By running an aqueous solu-
tion of NaNOjinto a hot solution of jw-phenylene-
diamine and Cu^Cl^ in dilute HCl (Sandmeyer,
B. 17, 2652). — 2. From di-chloro-aniline by re-
moving NHj by the diazo- reaction (Korner, G.
4, 341 ; B. a,. K.). — 3. From m-di-nitro-benzene
vid m-nitro-aniline, m-chloro-nitro-benzene, and
TO-chloro-aniline (Griess, P. T. 1864 [3] 705). ,
Properties. — Liquid. HNO3 (S.G. 1-4) gives a
nitro-compound [38°].
^-Di-chloro-benzene C^HjCLj [1:4]. [55°].
(173°). S.G. !»? 1-458 ; S? 1-241 (Jungfleisch,
A. Ch. [4] 14, 186). S.V.S. 117-4 (Schifl).
Fonnation. — 1. By running a solution of
NaNO, into a hot solution of p-phenylene-
diamine and Cu^Cl^in dilute ECl (Sandmeyer, B.
17, 2652). — 2. The chief product of the action of
chlorine (2mols.) on benzene (1 mol.) in presence
Of iodine (Hugo MUller, C. J. 15, 41 ; Z. 1864,
401 ; Edmer, O. 4, 324) or in presence of M0CI5
(Aronheim, B. 8, 1400).— 3. By the action of
PClj on phenol p-snlphonio acid (Kekul^, B. 6,
944) or on ^-chloro-phenol (Beilstein a. Eurba-
toff, A. 176, 32; B. 7, 1395, 1759).
Properties. — Monoclinic laminie (from alco-
hol). Sublimes at ordinary temperatures. Fum-
ing HNO, gives a nitro- derivative [55°].
u-Tri •chloro-beuzene C,H,C1, [1:3:4]. Mol.
w. 181i. [IG^. (213° i. v.). S.G. (of liquid) 12
1-465.
Fonhalion. — 1. By ohlorination of benzene
in presence of iodine (Jungfleisch, A. Ch. [4] 15,
264).— 2. From di-ohloro-aniline, C8H3(NH2)Clj
[1:3:4] or [1:2:4] displacing NHj by CI by means
of the diazo- reaction.— 3. Fjom di-ohloro-phenol
[43»] and PClj (Beilstein a. Kurbatoff, A. 192,
230 ; B. 10, 270). — 4. From (;8)-benzene hexa-
chloride %ud alcoholic KOH.
Properties. — Gives on nitration a nitro- de-
rivative [58°].
c-Tri-chloro-benzene 0„H,C1, [1:2:3]. [54°].
(219^). By eliminating NH^ from C.Hj(NHj)Cl,
[1:2:3:4] by diazo- reaction (Beilstein a. Kurba-
toff, A. 192. 235). Also from (l,2,3)-di-chloro-
aniline by displacing NHj by CI. V. sol. CSj,
and benzene, si. sol. alcohol. Gives a nitro- deri-
vative [56°].
, s-Tri-ohloro-benzone C^HaCla [1:3:5]. [63-5°].
(208'5° i. v.). From ordinary tri-chloro-aniline,
by eliminating NK, by diazo- reaction (Korner).
Also from chloro-benzene tetra-chloride, and alco-
holic KOH (Jungfleisch). V. sol. ether, benzene,
CS2 and light petroleum. Sol. cold alcohol and
dilute (50 p.c.) acetic acid. Gives on nitration a
nitro- derivative [68°] (B. a. K.), or, when fuming
HNOjis used, a di-nitro- derivative [130°] (Jack-
son a. Wing, Am. 9, 348).
c-Tetra-cliloro-benzene CbHjCI, [1:2:3:4]. Mol.
w. 216. [46°]. (254° i. V.). From tri-chloro-
aniline CjH^CljfNHj) [1:2:3:4] or [1:3:6:2] by the
diazo- reaction (Beilstein a. Eurbatofi, A. 192,
238). Long needles (from alcohol). SI. sol.
alcohol, V. sol. ether, light petroleum, CS^, and
strong (90 per cent.) acetic acid. Gives a nitro-
derivative [65°].
i-Tetra-chloro-benzene CjH^Clj [1:3:4:5] [51°j
(B. a. E.) ; [35°] (L). (246° i.V.). From ordinary
tri-chloro-aniline displacing NH, by CI by the
diazo- reaction (Beilstein a. Eurbatofi, A. 192,
238). Obtained also by chlorinating benzene in
sunlight (Istrati, A. Ch. [6] 6, 383). . Colourless
needles (from alcohol). SI. sol. cold alcohol, sol.
benzene, v. sol. CS2 or light petroleum. HNOj
(S.G. 1-54) gives a nitro- derivative [30''] (Jung-
fleisch, A. Oh. [4] 15, 204), or [22°] (B. a. K.).
s-Tetra-chloro-benzene CjHoOlj [1:2:4:5].
[138°] (245° i. V.) (B.). S.G. " 1-734 ; i±2 1.399.
Formation. — 1. By ohlorination of benzene
(Jungfleisch).— 2. From OeHjCljINOJ [1:2:3:4]
by reduction followed by the diazo- reaction
(Beilstein a. Eurbatoff, A. 192, 236).— 3. In small
quantity by the action of chlorine on boiling
tri-chloro-toluene (Beilstein a. Euhlberg, A. 152,
247).— 4. By the action of Fe^Clj upon (2, 4, 6, 1)-
tri-chloro-phenol (Caccomo, B. 18, 1163).
Properties. — Crystallises best from benzene.
SI. sol. alcohol or light petroleum. Fuming
HNO3 forms, besides the nitro- compound [98°],
tetra-chloro-quinone. This is the only tetra-
chloro-benzene which gives chloranil under these
circu u^ s it fin c c s
Penta-chloro-benzene C5HCI5. [86°]. (276°)
(Ladenburg, ^. 172, 344). S.G. M 1-842. Formed
by chlorinating benzene (J.), di-phenyl sulphone
(Otto a. Ostrop, A. 141, 93 ; 154, 182) or tetra-
ohloro-benzyl chloride (Beilstein a. Euhlberg, A.
152, 247). Slender needles (from alcohol); v. si.
sol. cold alcohol, v. sol. ether and CSj. After
heating for a long time with cono. or fuming
HjSO,, on pouring the liquid into water a chest-
nut-brown pp. containing no sulphur and 36-8
p.c. chlorine is formed ; it is called ' franceine '
by Istrati (Bl. [2] 48, 35) ; it is a red dye, and
forms a red solution in alcohol.
Heza-chloro-benzene CgClg., Mol. w. 285.
[226°]. (326°), S.G. ^^a 1-669.
Formatimi. — 1. From methylene chloride and
ICl or ICl, (Holand, A. 240, 234).— 2. By passing
chloroform, CCl„ or CjCl, through a red hot
38
CHLORO-BENZENE.
tube (Jaliu ; Begnault, A. 30, 350 ; Basset, C. J.
20, 443 ; Berthelot a. Jungfieiscli, Z. [2] 4, 565).—
8. By oUorinating benzene in presence of SbCI,
(Hugo Muller, Z. 1864, 40).— 4. From tetra-
chloro-qninone (chloranil) and PClg (Grsbe, A.
146, 1). — 6. Is the ultimate product of the action
of SbCl, with chlorine on all chloro-toluenes
and chloro-xylenes (Beilstein a. Kuhlbcrg, Z. [2]
S, 183 ; A. 150, 309).— 6. By the action of chlorine
in presence of ICl upon all aromatic hydrocar-
bons, as well as upon aniline, phenol, thymol,
camphor (Buoff, B. 9, 1483; 10, 1234); sec-
hexyl iodide (Krafft, B. 9, 1085); and hexa-
chloro-acetone (Cloez, A. Ch. [6] 9, 145).
Properties. — Thin prisms (from alcohol-
benzene), V. si. sol. boiling alcohol, si. sol. ether,
m. sol. benzene. When heated with glycerin
and NaOH it gives penta-chloro-phenol.
CHLORO-BENZENE-AZO. v. Azo- compocnds^
CHLOBO-BENZENE HEXA-CHLOBISE
C^HjCl,. [267°]. From di-phenylsulphone and
chlorine in sunlight (Otto, A. 141, 101). Small
dimetric prisms (from alcohol) ; v. si. sol. ether,
si. sol. hot alcohol.
Si-oliloro-benzene hexa-chloride C^H^Cl,.
[above 250°]. From chloro-benzene and chlorine
in sunlight (JungSeisch, Z. [2] 4, 486). Prisms
(from chloroform) ; converted into penta-cbloro-
benzene by boiling alcoholic KOH.
Tri-chloro-benzene hexa-chloride ClgCgHjCl,
[1:2:4]. [96°]. Formed by chlorination of benz-
ene (Willgerodt, J. pr. [2] 35, 415). Smells of
rotten straw. Y. e. sol. ether, v. sol. alcohol.
Alcoholic KOH converts it into CsCL [226°].
CHLOBO-BENZENE STTLFHINIC ACID
C„H<Cl.SOjH. [90°]. From chloro-benzene
(^?)-sulpho-chloride and sodium-amalgam (Otto
a. Brummer, A. 143, 113 ; 145, 323 ; 146, 243).
Small needles or long thin columns ; si. sol. cold
water. Beduced by Zn and HjSO^ to chloro-
phenyl mercaptan, and by sodium-amalgam to
benzene sulphinic acid. Oxidation gives chloro-
benzene sulphonic acid.
Salts.— NaA'j2aq.—CaA'j.—BaA'j.—PbA'2.
Ethyl ether EtA'. [123°]. Needles.
' CHLOBO-BENZENE o-SUIFHONIC ACID
C^HjClSO, i.e. 0,H,01(S0,H) [1:2]. Fromamido-
benzene o-sulphonic acid by displacement of
NH; by CI by means of the diazo- reaction (Babl-
mann, il. 186, 325).
Chloride CeH,01.S0jCl [29=].
Amide 0,H,Cl.SOjNHj [188°].-
Chloro-benzene m-sulphonic acid
C,HjCl(S08H) [1:3]. Prepared similarly from
amido-benzene m-sulphonic acid (Kieselinsky,
A. 180, 108). , Deliquescent plates.— AgA'.—
KA'.— CaA'j.— BaA'j 2aq.— CuA'j 5aq.
i Chloride C,H<Cl(SOjCl). Oil.
il»iideC,H,Cl(S02NH,): [148°]; plates.
CliIoro-benzenejp-snlphonicacidO,H,Cl.S03H
[1:4]. Formed by sulphonating chloro-benzene
(Otto a. Brummer, A. 143, 102 ; Lindow a. Otto,
Z. [2] 4, 39 ; Glutz, A. 143, 184). Also by the
same method as the two preceding acids (Goslich,
A. 180, 106). Deliquescent needles ,or prisms.
Potash-fusion gives resorcin (Oppenheim a. Yogt,
A. Suppl. 6, 376). The Na salt fused with KCN
gives terephthalonitrile OsH4(CN)2.
Salts.— NaA'aq.—KA'.— AgA'.— CaA'jliaq.
— BaA'j 2aq.— PbA;^ 2aq.— CuA'j 6aq.
Chloride C^.Cl.SOjOl. [53°].
Bromide CjH.Cl.SOjBr. [58°].
Amide CeH.Ol.SO^NHj. [144°].
Anilide O^H^CLSO^NPhH. [104°]. Needles
(Wallach a. Huth, B. 9, 426).
Si-chloro-benzehe sulphonic acid
CjHjCySOsH) [l:2:a!]. Fromo-di-chloro-benzene
and fuming HjSO, at 210° (Beilstein a. Kurbatoff ,
A. 176,41; 182,94).-CaA'j2aq.— BaA'j2aq.—
PbA's 2aq.
Bi-chloro-benzene sulphonic acid
C,HjCl2(S03H) [l:3:a!]. From?»-di-ohloro-benzen8
and fuming HjSOjat235° (B. a. K.).— CaA'2 2aq.
— BaA'j aq.— PbA'j 3aq.
Bi-chloro-benzene sulphonic acid
CjHsCl2(S0jH) [l:4:a!j. Fromi»-di-chloro-benzene
and vapours of SO, (Lesimple, Z. [2] 4, 226).
Cone. HjSOj has no action even at 210° (B. a. K.).
Trimetric prisms (from water). — NHjA' aq ;
needles, m. sol.water. — KA.'aq. — AgA'. — NaA'aq :
six-sided tablets. — MgA'^eaq. — ^BaA'j: laminse.
— PbA'^ 3aq.
Iri-chloro-benzene sulphonio acid
C,H2Cl3(SO,H) [1:3:4:6?]. From M-tri-ohloro-
benzene and fuming H^SO, (Beilstein a. Kurba-
to£E, A. 192, 231).— OaA'j 2aq.— BaA'j 2aq.—
PbA'j 2aq.
CHLOBO-BENZENE THIO-STTLFHONIC
ACID. Chloro-phenyl ether OttEfil.^Sfi^
i.e. C,HiCl.S02.S.CaHjCl. [138°]. From chloro-
benzene sulphinic acid and water at 130° (Otto,
A. 145, 323). Small, four-sided, trimetric
columns (from alcohol). Beduced by zinc and
HjSOj to chloro-phenyl mercaptan.
DI-CHLOBO-BENZIDINE v, D1-CHI.0110-DI-
AMIDO-DIFHENYL.
CHLOBO-BENZIL or Benzil chloride v. Ben-
ziLic ACID, Beaclimi 5.
CHLOBO-BENZO-TBICHLOEIDE v. Tetra-
CHLOKO -TOLUENE.
0-CHLOKO-BENZOIC ACID CjHsClOj i.e.
CeH401(C0jH) [1:2]. Mol. w. 156J. [137°]. S.-114
at 0°. Electrical condiictwity : Ostwald (J. pr.
[2] 32, 349).
Formation. — 1. From salicylic acid (1 mol.)
and POI5 (2 mols.) ; the mixture is distilled and
the portion (above 258°) containing CjHiCl.COCl
is decomposed by water (Ohiozza, A. Ch. [3] 36,
102 ; Kolbea.Lautemann, A. 115, 184; Beilstein
a. Heichenbach, A. 132, 311 ; Hubner, Z. 1870,
293 ; A. 147, 26d ; Wilkins a. Back, A. 222, 192).
2. By boiling o-chloro-toluene with dilute
KMnO, (Bmmerling, B. 8, 880).— 8. By heating
TO-chloro-nitro-benzene with alcoholic KOy at
260° (Bichter, B. 4, 463).
Properties. — Large needles. Melts under
water. V. Bol. hot water, alcohol, and ether.
Gives a yellow pp. in neutral solutions with
FejCl,.
Beactions. — 1. Soda-fusion gives about equal
quantities of o- and m-oxy-benzoic acids (Ost,
J.pr. [2] 11, 385).— 2. In hot aqueous solution
it is reduced to benzoic acid by sodium-amalgam.
Benzoic acid so /prepared was called ' salylic '
acid until Beilstein a. Schlun {A. 133, 239)
showed it to be ordinary benzoic acid contami-
nated with a non-volatile substance which inter-
fered with its orystaUiBation. — 3. Fusion with
sodmm formate gives benzoic acid (V. Meyer.
B. 3, 363; 4,259).
Salts.— BaA'j 3aq.— BaA'j. S. 81 at 18-6°,—
CHLORO-BENZOIO ACID.
S9
CaA'i 2aq : t. sol. water ; v. b1. sol. alcohol. —
AgA' : ' scales (from boiling water).
Ethyl ether EtA'. (o. 240°) (Eekul£, B^.
ehim. pwre, 1861, 308).
Chloride CjH.Cl.COCl. (o. 237°).
Amide CjH,Cl.CONHj : [139°]; needles;
V. si. sol. cold water ; v. sol. alcohol and ether.
Anilide C,H,Cl.CONPhH : [114°] ; needles.
p-Nitro-aniUde C5HjG1.C0.NH.0,H^N0j :
[180°]^ from the anilide and HNOj (Wilkins a.
Back, A 222, 192).
p-Toluide C.H4C1.C0.NHC,H,(CH,): [131°];
colourless crystals; sol. alcohol, nearly insol.
water (Schreib, B. 13, 465).
m-Nitro-p-toluide
C^,Cl.CO.NHO„H3(CH3)(NOj):[139°]fyellowish
crystals ; sol. acetic acid, si. sol. alcohol, insol.
water. Prepared by nitration of the^-toluide.
Di-nitro-p-toluide
C,H^C1.C0.NH0„H2(CH3)(N0J2(?): [228°]; col-
ourless crystals. SI. sol. alcohol, y. sol. acetic
acid and chloroform. Prepared by further ni-
tration of the mono-nitro- compound.
Tri^nitro-p-toluide OitBsSfifil: [239°];
colourless crystals. Prepared by still further
nitration of thp above.
m-Amido-p-ioluide
C,H,01.00.NHCA{CH3)(NH2) : [153°] ; colour-
Jess crystals; sol. alcohol. .Prepared by reduc-
tion of the »»-mtro-j)-toluide.— B'HCl.— B'HNOj.
Bemoylamido-p-toluide
C^,Cl.CO.NHC5H,(CH3){NHBz) : [178°] ; colour-
less needles, si. sol. alcohol.
Nitrite CjHjCl.CN. o-Chloro-cyano-bem-
ene. [48°]. (232°). From the amide and PCI5
or F^Sj. Also from the amide or nitrile of sali-
cylic acid by the action of POI5 (Henry, JB. 2,
492). Long needles: si. sol. boUing water: m.
sol. alcohol and ether.
m-Chloro-benzoic acid CJB.fil.GOja. [1:3].
[153°]s S. -035 at 0°. Electrical cmductivity :
Ostwald, J.jpr. [2] 32, 349. ,
Formation. — 1. By chlorinating benzoic acid
by treatment with chlorine, with HCl and
EClO,, or with a boiling solution of bleaching
powder (Herzog, N. Br. Arch. 23, 15; Schar-
ling, A. 41, 49 ; 42, 268 ; Stenhouse, A. 55, 1 ;
Field, A. 65, 65; Otto, A. 122, 157; Hubner a.
Weiss, jB. 6, 175). — 2. From 9ra-amido-benzoio
acid by the diazo- reaction. — 3. By distilling m-
Bulpho-benzoic acid (1 mol.) with PCI, (2 mols.)
and treating the resulting m-ohloro-benzoyl
chloride with water (Limpricht a. Uslar, A. 102,
259). — 4. By oxidation of m-chloro-toluene with
chromic acid mixture (Wroblewsky, A. 168,
200). — 5. From j)-ohloro-nitro-benzene and KOy
, at 200° (Eichter, B. 4, 463).— 6. From s-chloro-
amido-benzoic acid by removing NH^ by the
diazo- reaction (Hubner, A. 222, 91).
Properties.— liong needles or small prisms.
Does not melt under water.
Beactions. — 1. Sodium amalgam reduces it
to benzoic acid (Beilsteina.Beichenbach,^. 132,
315). — 2. Poto«»-/Mstoregives m-oxy-benzoic acid
(Dembey, A. 148, 222).
Salts.— CaA'j 3aq: small needles. S. 1-21
at 12°.— BaA'j 4aq: small needles.— AgA'.
Ethyl ether CJifil.CO.-Et: (245°); liquid.
Chloride C^fiLCOCl: (225°); liquid.
Amide C,Mfil.OOTSB..: [133°]; needles.
Nitrile G,lifil.C^: [39°]. Formed by dis-
tilling OT-sulpho-benzamide with PCI5 (Limpricht
a. Uslar, A. 106, 35). Also from the nitrile of
jn-amido-benzoio acid by displacement of NH,
by CI (Griess, B. 2, 370). Needles ; insol. water.
Volatile with steam.
p-Chloro-benzoic acid CjHjCl.CO^H [1:4].
Chloro-dracylic acid. [236°]. S. -019. Electrical
conductivity: Ostwald, J.pr. [2] 32, 349.
Formation. — 1. From j)-amido-benzoic acid
by diazo- reaction (Wilbrand a. Beilstein, .4. 128,
257 ; Beilstein a. Sohlun, A. 133, 242).— 2. By
oxidation of iJ-ohloro-toluene with CrOj (Beil-
stein a. Geitner, A. 139, 336) or dilute KMnO,
(Emmerling, B. 8,880) — 3. Fromchloro-benzene,-
dilute HjSOi, and MnO^ (Carl Miiller, Z. [2] 5, 137).
Properties.— Needles (by sublimation) ; v. sL
sol. water, v. sol. alcohol and ether. ^Sodium
amalgam reduces it to benzoic acid (Hartmann,
/.^. [2] 12, 204).
Salts.— BaA'j 4aq.— CaA', 3aq.— AgA'.
Methyl ether UeX': [42°]; needles.
Chloride CaB.fil.C001. [222°].
Amide CsBfilCONKi: [170°]; needles.
Anilide CjH^Cl.CONPhH : [194°] ; needles.
Di-chloro-benzoio acid CjH3Cl2(C02H) [6:2:1].
Mol. w. 191. [126-5°]. Formed, together with
the two isomerides [156°] and [201°], by the ac-
tion of water on crude penta-chloro-toluene
C.H3CIJ.CCI, at 200° (Schultz, A. 187, 269).
Slender needles ; volatile with steam.
S a 1 1 s. — KA' 5aq.— NH,A' aq. - BaA'j 3 Jaq,
S. (of BaA'j in alcohol) 3-8 at 4°.— ZnA'j Uag.
Chloride CJIfiUCOGl: (244°); liquid.'
Amide C^Ufil^.Cb'SE.^: [166°]; needles.
Di-cMoro-benzoic acid CaHsCl-OO-^ [2:5:1].
[156°]. (801°). S. -0850 at 14°.
Formation. — 1. From chloro-nitro-benzoic
acid [164°] by reduction and displacement of
NH2 by CI by means of the diazo- reaction
(Wilkens a. Back, A. 222, 201).— 2. From crude
penta-chloro-toluene CjHjOlj.CCl,, together with
the acids [126-5°] , and [201°] (Schultz, A. 187,
268). — 3. By chlorinating o-chloro-benzoip acid
in presence of SbClj (Beilstein, A. 179, 286).
Occurs also among products of chlorination of
benzoic acid. — 4. By oxidising (6, 3, l)-di-chloro-
ethyl-benzene with chromic mixture (Istrati, A.
Ch. [6] 6,479).— 5. From CsH,MeClj [1:2:5] and
dUute HNO3 (Lellmann a. Klotz, A. 231, 319).
Needles (from water) ; sUghtly volatile with
steam. Heated with dilute H^SO, at 220° it gives
CO2 and p-diehloro-benzene. — ^BaA'jSaq. S. (of
BaA'j) 2-5 at 14-4°.— CaA'2 2aq. — PbA'^aq.—
CuA'j2aq (B.).— CuA'^ aq (I.).— FeA'„.— KA'2aq.
NH^A': slender needles. — AgA'.
Ethyl ether EtA'. (271° i. V.). S.G. s 1-328.
Amide CsSfih-CONB.^: [165°]; needles (B,).
Anilide: [240'-*] ; prisms (from benzene).
Di-chloro-benzoic acid C,H3Cl2(COjH) [3:2:1].
[156°] (C.) ; [166°] (S.). Formed, together with
the isomeride [201°], by chlorination of benzoic
acid (Glaus, B. 5, 658 ; 6, 721 ; 8, 948 ; 20,
1621). Formed also by oxidising c-di-chloro-
toluene with KMnO< (Seelig, A. 237, 162). Not
affected by dilute HjSO, at 220°. Distillation
over lime gives o-di-chloro-beuzene. Not decom-
posed by cone. H^SO, at 300°.— BaA'j 3aq. S. 8
at 28°.
Bi-chloro-benzoio acid CsHjCyCOaH) [4:2:1].
[158°]. From OaHjIVteClj [1:2:4] and dilute
HNO3 (Lellmann a. Elotz, A. 231, 315).
40
CHLORO-BENZOTC ACID.
Salt. -BaA'jSiaq.
Di-chloro-benzoio acid CsH3Cl2(C02H) [3:5:1].
[182°]. From C„H,MeClj and dilate HNO,
SLiellmann a. Elotz, A. 231, 324).. Needles (from
ilute alcohol). May be sublimed.
Si-chloro-benzolc acid CaH3(C02H)Cl, [4:8:1].
[201°].
FarmaVum. — 1. A product of the chlorination
of benzoic acid (Beilstein a. Euhlberg, A. 152,
232 ; 179, 291).— 2. Prom chloro-sulpho-benzoio
acid and PCls (Otto, A. 123, 226).— 3. By oxida-
tion of CbH,C12.CH3 or C„H3Cl2.CHjCl ; or by
heating C„HjCl2.CCl3 with water at 200- (B. a. K.).
4. From p-chloro-benzoic acid and SbClj at 200°
(B.). — 5. From chlorinated p-oxy-benzoie acid
and POl, (Losaner, J.pr. [2] 13, 433).— 6. From
CeHjMeClj [1:3:4] by dilute HNO, (LeUmann a.
Klotz, A. 231, 313).
PraperlAes. — Very slender needles (from
water) ; volatile with steam.
Salts .— CaA'o 3aq.— BaA'j 4aq. S. 1-1 at 18°.
Ethyl e<fe6rEtA':(263°); liquid.
Chloride Q,^^Q\.GOC\: (242°); liquid.
Avnide C^fi\SXmB.^: [133°]; needles.
Tri - chloro - benzoic acid C,H2Gla(C0.,H)
[6:3:2:1]. [o. 80-']. From the corresponding
aldehyde and KMnO< (Seeh'g, A. 237, 150).
Needles, v. sol. water.
Tri-ohloro-ljenzoic acid Cja,Cl3(C02H)
[4:3:2:1]. Mol. w. 225J. [129°]. Froto the
corresponding (4, 3, 2, l)-tri-chIoro-benzoic alde-
hyde by KMnO, (SeeUg, A. 237, 150). Needles ;
m. sol. water.
Tri - chloro - benzoic acid C5H2Cl3(C02H)
[5:4:2:1]. [163°]. From s-tri-chloro-toluene by
oxidation with chromic acid mixture (Jannasoh,
A. 142, 301). Formed also by boiling benzoic
acid with water and ble^iohing-powder for a long
time; and by heating OjHjCla.CCl, with water
at 260° (Beilstein a. Kuhlberg, A. 152, 284).
Slender needles (from water or by sublimation) ;
V. si. sol. cold water.
Salts.— NHiA'.—CaA'j2aq.— BaA'j7aq.—
SrA'2 4aq.
Ethyl ether EtA': [65°]; needles.
Chloride CsHjClj.COCl. [41°]. (272°).
Amide 0„H„C1,.C6nHj : [168°]; needles.
Tri - chloro - benzoic aeid CaH2Cls(C0„H)
[5:4:3:1]. [203°].
Formation. — 1. From di-nitro-p-amido-ben-
zoie acid and fuming HCl at 210° (Salkowski,
A. 163, 28). — 2. From crude hexa-chloro-toluene
OsH^Cls-CCl, and NaOH (Glaus a. Bucher, B. 20,
1626).
Properties. — Slender needles (from dilute al-
cohol or by sublimation).
Salts .— AgA'.— BaA'2 4aq.— CaA'„ 6aq.
Ethyl ether EtA': [86°]; slender needles
(S.).
Chloride C^HaClj.COCl. [36°] (S.).
Amide CsH^Cla.CONH.,. [176°] (S.).
c-Tetra'Chloro-benzoic acid CbHC1,(C02H).
[165°]. Formed by chlorination of the di-chloro-
benzoio acids melting at [201°] and [156°]
(Glaus) by heating with MnO^ and fuming HCl
at 190° (Glaus a. Bucher, B. 20, 1626). Also
from di-chloro-benzoio acid [156°] and SbClj at
230° (Beilstein, A. 179, 286).— BaA' 4aq (B.).—
BaA'j3Jaq (G.).
Tetra-chloro-benzoic acid C„HC1,(C02H)
[5:4:3:2:1]. [186°]. Prepared by heating tetra-
chloro-phthalic acid with acetic acid (2 or 3 pt».)
at 300° for 3 or 4 hours (Tust, B. 20, 2439 ;
21, 1532.) Long colourless needles. V. Bol.
alcohol and ether, v. si. sol. water.
Salts. — A'2Ca4aq: long colourless needles;
m. sol. hot water. — A'jCu 3^aq. — BaA'^ 3iaq.
Ethyl ether A'Et: [35°]; long colourless
needles.
Tetra-chloro-benzoic acid CjHGl4(C0.jH)
[6:4:3:2:1]? [186°]. From hepta-chloro-toluena
CHGlj.GGl, and water at 280° (BeUstein a. Kuhl-
berg, A. 152, 246).
Penta-chloro-benzoic acid C„Cl5(C0,H). [200°].
Formed by chlorination of the di-chloro-benzoio
acids [201°] and [156°] with MnO^ and HClAq
at 190° (0. a. B.).— BaA'j 4aq: stellate groups of
Niirile Gfil.,{C}<i). [210°]. Formed by ex-
haustive chlorination of benzonitrile with SbGl,
(Merz a. Weith, B. 16, 2885). Colourless needles.
Sublimable. V. sol. hot alcohol, chloroform,
and CSj, si. sol. cold alcohol and ether. It is
very stable towards HGl at high temperatures.
Alcoholic NaOH removes all its chlorine at 200°.
o-CHLOBO- BENZOIC ALDEHYS£ [2:1]
C„H,C1.CH0. (0. 215°). S.G. ^ 1-29. Formed
by heating tri-chloro-toluene CbH^CLCHCIj (from
salicylic aldehyde and PGI5) with water at 170°
or with {fg pt.) dry oxalic acid at 130° (Henry,
B. 2, 135; Anschutz, A. 226, 19). Oil, smelling
of almonds; volatile with steam. Forms a
crystalline compound with NaHSOj.
2)-Chloro-benzoio aldehyde [4:1] OaHjCl.CHO.
[48°]. (c. 212°). Obtained by boiling
CeHjGl.CHBr„ [48°] (10 pts.) with lead nitrate
(4 pts.) and water (100 pts.) for three days, in
presence of GO^ (Jackson a. White, Am. 3, 31 ;
N.Am. A. 15, 2)38; B. 11, 1042). Formed by
boiling GjHjGl.CHjCl with aqueous lead nitrate.
Formed also by passing chlorine into benzoic
aldehyde containing iodine (Beilstein a. Kuhl-
berg, A. 147, 339). Long needles ; may be sub-
limed. Sol. alcohol, ether, CS2, and HOAc, si.
sol. water. Absorbs oxygen from the air. Forms
a crystalline compound with KaHSO,.
Si-chloro-beuzoic aldehyde CsHsGlj.CHO
[5:2:1]. [58°]. (230°-233°). Preparation not
given. White crystals. On oxidation it gives
di-chloro-benzoic acid [162°] (Gnehm, B. 17,
752).
Si-chloro-bcnzoio aldehyde O5H3GI2.GHO
[6:2:1]. [08°]. Formed by heating
CSH2CI2.CHCIJ with water at 200° (Beilstein a.
Kuhlberg, A. 152, 224). Slender needles ; vola-
tile with steam ; si. sol. hot water. Attacks the
eyes. Combines with NaHSOj. Oxidises to
di-ehloro-benzoic aci4 [128°].
(i3)-Di-chIoro-benzoic aldehyde
G.H,Cl2.GH0 [4:2:1]. [71°]. (0. 233°). Formed
by the action of oono. HjSOj on O.HsClj.CHCU.
The aldehyde is separated by means of the
double compound with sodium bisulphite (See-
lig, A. 237, 167). White needles (from aloohol).
Oxidation with permanganate yields (i8)-diohloro-
benzoic acid [158°]. When heated with A0.JO
and NaOAc it forms ((3)-di-ohloro-cinnamie acid
[228°].
Tri-chloro-benzoio aldehyde CjHjClj.CHO
[113°]. Formed by heating C.HjCL.GHGl.
(281°) with water at 250' (B. a. K. ; SeeUg, B
18, 420; .A. 237, 148). Very dender needles 5
CHLORO-BENZYL CYANIDE.
41
Insot. boiling water, t. sol. alcohol ; Tolatile with
Bteam. Cono. H^SO^ and KNO, foritt tri-chloro-
nitro-benzoio aoid [222°] and an aldehyde [124°].
Tri-chloro-benzoio aldehyde OjHjO^.OHO
[4:3:2:1]. [90°]. Prom penta-chloro-toluene
C,H2Cl3.CH01j [84°] (Seelig). Gives on oxidation
tri-cbloro-benzoio acid [129°].
CHLOKO-BENZONITBILE v. KiiBixii ov
CnLOBo-B]i:Nzoic Acn>.
CHL0B0-BI!NZ0PHElI0irEC,H4Cl.CO.CsH5.
Phenyl chloro-phmyl ketone. [76°]. (above 300°).
Tom chloro-benzene, benzoic acid, and P^Oj
Eollarits a. Merz, JB. 6, 647). Mat needles
(from ether-alcohol) ; t. sol. ether, al. sol. cold
alcohol and ligroin.
CHLORO-o-BENZGTL-BENZOIC ACID
OHH,C10,i.e. C^5.C0.CeH301(00jH) [2:4or5:l].
Chloro-bemophenone carboxyUe acid, [171°].
From ohloro-phthalio anhydride [97°], benzene,
and Al^Gl, (Greebe a. B£e, C. J. 49, 531 ; ^.238,
239). Minute monoclinio prisms ; t. sol. ether
and alcohol, si. sol. CS,, v. si. sol. light petro-
leum. Cono.HjSOtConvertsitintochloro-anthra-
quinone [204°].
Di-chloro-o<benzoyl-benzoio acid
C^5.C0.C„H2Clj.C02H. [159°]. From (/3)-di-
cbloro-phthaiic anhydride [150°] , benzene, and
AIjCl, (Le Eoyer, /. 238, 356). Needles (from
dilute alcohol).
Tetra-chloro-o-benzoyl-benzoio aeid
C„H.C1A »•«• CeHs.C0.C.Cl4.C0jH. [200°].
From tetra-chloro-phthalio anhydride, benzene,
and Alicia (Kircher, A. 238, 338). White needles ;
si. sol. cold benzene, v. e. sol. alcohol, insol.
water. Cannot be distilled' or sublimed.
Beactions. — 1. Soda-ftisiongiyes benzoic acid.
2. H.^SO, and FCl^ give tetra-chloro-anthra-
quinone. — 3. HI gives tetra-chloro-benzyl-ben-
zoio acid.
Salts.— NaA'4aq. S. 1-7 at 20°.— KA' l^aq.
— CuA'j 2aq.— OuA'jOuO.
EtTiers: EtA' [90°].— MeA' [92°].
Chloride [183°]. Needles.
CHLOBO-BEirZOYL CHLOBIOE v. Chloride
of Chlobo-benzoic aoid.
CHLOBO-SIBENZTL v. CHLOBo-ni-PHE^tYL-
EIHANE.
jj-CHLOBO-BENZYL ACETAT£ C,H,C10,
i.e. [4:1] O.H,Cl.CHj.OAc. (240°). From
CgH^CLCHgCl and EOAc in boiling alcohol
(Beilstein a. Eohlberg, A. 147, 344).
Oi-chloro-benzyl acetate C^3Cl2.CH20Ac.
(259°). Similarly prepared from CtHsClj.CHjCl
(B. a. E.).
CHLOBO-BENZYL-ACEIO-ACETIC EIHEB
C„H,jC10, i.e. CH,.C0.CH(0HClPh).C02Et(?)
[41°]. Formed, together with an isomeride [72°]
possibly 0H,.C0.CCI(0H2Ph).C0jEt, by mixing
aceto-acetio ether with benzoic aldehyde and
saturating with HCl (v. vol. i. p. 24).
p-CHLOBO-BENZYL ALCOHOL C,H,C10 i.e.
C.H,C1.CH,0H. [66°] (B. a. K.) ; [71°] (J. a. F.).
Obtained by heating ^-chloro-benzyl acetate (v.
supra) with alcoholic NH, at 160'' (Beilstein a.
Kuhlberg, A. 147, 344 ; Neuhof, Z. [2] 8, 467).
>repared by boiling p-chloro-benzyl chloride
C„H^C1.CH,C1 with water (Jackson a. Field, Am.
2, 88 ; P. Am. A. 14, 56). Needles (by sublima-
tion or from water) : may be distUled. Sol. hot
water, alcohol, and ether. Chromic mixture
osidises it to 2>-chloro-ben^oic acid [233°].
Di-ohloro-bcnzyl alcohol OjHjClj.CHjOH.
[77°]. From the acetate (o. supra) by heating
with alcoholic ammonia at 180° (B. a. K.).
Needles ; v. si. sol. water.
Tri-ehloro-benzyl alcohol OsHjClj.CHjOH.
From tri-chloro-benzyl chloride CuHjCla.OHjCl
and alcoholio KOAo at 150°. Crystalline (Beil-
stein a. Euhlberg, A. 152, 241).
Tetra-chloro-benzyl alcohol C„HC1,.CH20H.
Prom OjHClj.CHjCl, alcohol, and KOAo at 180° ;
crystallised from water (B. a. K.).
Penta-chloro-benzyl alcohol OoCls-CHjOH.
[193°]. From C„01,.CHjCl, a,lcohol, and KOAc
at 200° (B. a. K.), 'White needles (from benzene-
alcohol) ; insol. water, si. sol. boiling alcohol.
2>-CHL0B0-BENZYLAMINE C,HjClN i.e.
[4:1] OjH4Cl.CHjNH2. ^-Chloro-benzyl chloride
(1 vol.) heated with alcoholio ammonia (2 vols.)
at 100° forms (OrfH^Cl.CHj)NHj, (0„H^C1.CH2)2NH
and (C,H4C1.0H2)3N. Their hydrochlorides may
be separated by crystallisation from alcohol
(Berlin, A. 151, 137 ; Jackson a. Field, Am. 2,
94 ; P. Am. A. 14, 50). Colourless oil; sol. ether.
Salts.- "BTECl : [241°]j narrow plates, sol.
water and alcohol. — B'jHJtClj : yellow needles..
"B'HBr: [230°]; decomposed by melting.—
"B'jHjCO, : [115°] ; plates (from water) or needles
(from alcohol).
Bi-^-chloro-di-benzyl-amine
(CeH,Cl.CHi)sNH. [29°]. From ohloro-benzyl
bromide and alcoholio NH, (Jackson a. Field,
Am. 2, 90; B. 11, 904). 'White blades; insol.
water, sol. alcohol, ether, benzene, and CS,.
Salts.— B'HCl: [288°]; plates, sol. water
and alcohol, insol. ether. — B'jHjPtClu: yellow
scales, si. sol. boiling water, insol. alcohol. —
B'HBr : [280°-290°], melting with decomposition.
Scales, si. sol. water, insol. ether.
(/3)-Di-chloro-di-benzyl-ainine
(CgH4Cl.CH2)2NH. This base occurs, together
with the two following, among the products of
the action of alcoholic NE, on crude chloro-benzy 1
chloride (Berlin, A. 151, 141).— B'HCl : [228°].
B'HBr : [224°].— B'HI : [215°].— B'HNO, : [204°].
. (7)-Bi-chIoro-di-beazyl-amine
(C^,01.CHj)jNH. Salts.— B'HCl: [220°].—
B'HBr: [212°].— B'HI: [187°]. — B'HNOj :
[193°].
(S)-I)i-chloro-di-benzyl-amine
(CsH.Cl.CHj,)2NH. Salts.— B'HCl : [222°].'^
B'HBr: [199°]. — B'HI: [218°]. — B'HNO, :
[179°].
Tri-^-chloro-tri-benzyl-amine
(05HiC1.0H,)aN. [79°]. From ^-ohloro-benzyl
bromide and alcoholic NH, (J. a. Fi). Needles;
sol. hot alcohol, ether, benzene, and CS,.
Salts.— B'HC12aq: [196°].— B' HjPtCl„: pale
orange plates, insol. water, jilcohol, and ether.
TETBA-CHLOEO-o-BENZYL-BEHZOIC ACID
C,H5.CH2.C8Cl4.C02H. Tetra-chloro-di-phenyl-
m,ethane eso-earboxyUe acid. [157°]. Prom
C8H5.CO.C5CI4.OO2H and cone. HI at 180° (Kir-
cher, A. 233, 343). Hair-like needles (from dilute
alcohol). Insol. water, v. sol. alcohol.
S a It s.— NaA' 4aq.— AgA'.
CHLOBO-BENZYL ^BOHIBE v. Chlobo-
BKOMO-TOLUENE.
CHLOBO-BENZYL CHLOBIDE v. Di-chlobo-
TOLUENE.
CHLOBO-BENZ'n. CYANIDE v. Nitrite at
CHLOBO-rBENTL-ACBIIO ACID.
OnLORO-BENZYL ETHYL OXIDE.
p-CHLOEO-BENZYIi ETHYL OXIDE
C«H,Cl.CHj.O.CA. (217°) (Sintenjs, A. 161,
335) ; (215°-225°) (Jackson a. White, Am. 2, 170) ;
(226°) (Errera, (?. 17, 206). Prom p-ohloro-
benzyl chloride (acetate or bromide) and alco-
holic KOH (Naquet, A. Suppl, 2, 251). Liquid, >
with fruity odour ; decomposed by heating above
its boiling-point into f-chloro-benzoic aldehyde
and ethane (E.).
a,.CHLOEO-BEirZYlIDENE.ANILINE
CjHj.NiCCl.CjHs Bensanilide - imide - chloride.
[41°]. Formed by isomeric change of the fir&t
formed oxim-chloride (CjH5)2C:NCl by the action
of PClj or POCI3 upon benzophenone-oxim
(CjH5)2C:NOH. Colourless rhombic tables (Beck-
mann, B. 19, 980).
GHXOBO-BEirZYLIDENE CHLOBIDE v. Tbi-
CHLOBO-TOLUENB.
0-CHLOBO-EENZYLIDENE-HALONIC ACID
C,„H,C10, i.e. C,HjCl.CH:CH(CO^)j. [192°].
Formed by heating malonio acid with o-chloro-
benzoic aldehyde and HOAc for some hours at
100° (Stuart, C. J. 53, 141). Decomposed on
melting into CO^ and ohloro-einnamio acid. Boil-
ing water splits it up into o-chloro-benzoic alde-
hyde and malonic acid.
u-CHLOEO-BENZYLlDENE-(a)-irAPHTHYI-
AMXNE C„H,CC1:N.C,„H,. [60°]. Frombenzoyl-
(a)-naphthylamine and PCI, (Just, B. 19, 979).
u-Chloro-benzyIideiie-(i3)-naphthylamine.
[68°]. Similarly prepared (J.). Leaflets ; slowly
converted into benzoyl-(;S)-naphthylamine on
exposure to the air,
CHL0B0-BENZYLISE17E-FHIHALI1SIIDINE
C,5H,„C1N0. [232°]. From benzylidene-phthal-
imidine and PCI, (Gabriel, B. 18, 1260). Keedles
(from alcohol).
B-CHLOEO-BENZYLIDENE-o-TOmiDINE
C,,H„C1N i.e. C,H4Me.N:CCl.C„H5 Bmzoyl-O'
toluidine-imide-chloride. Formed by the action
of PCI3 upon benzoyl-o-toluidiqe. Water regene-
rates benzoyl-jp-toluidine. The compound was
not obtained in a pure state. With sodio-malonio
ether it gives o-tolyl-;3-imido-benzyl-malonia
ether CsH5.C(N0,H,).CH(C0jEt), (Just, B. 19,
982).
m-Chloro-benzylidene-m-toluidiiie
C„H,jClN t.e. C8H,Me.N:CC1.08H5. Formed by
the action of PCI, upon benzoyl-m-toluidine. Not
obtained in a pure state. By the action of sodio-
malonic ether it yields m-tolyl-iS-imido-benzyl-
raalonic ether C.H5.C(N0,H,).CH(C0jEt)j (Just,
B. 19, 983).
oi-Chloro-benzylidene-f-tolaidine
C„H,Me.N:CCl.C,H,. [52°]. Formed by gently
warming benzoyl-^-toluidine with PCI5. Large
clear prismatic crystals. By boiling with water
or alcohol it is reconverted into the benzoyl-^-
toluidine. With p-toluidine it yields di-^-tolyl-
benzamidineC,Hi.C(NC,H,)NHC,H,.Withsodio-
malonie ether it gives ^-tolyl-j8-imido-benzyl.
malonio ether CaH,.C(NCjH,Me).CH(C0aEt)2
(Just, B. 19, 979).
CHLOKO-BENZYL-MALONIC ETHER
C,H,.CHj.CCl(CO,Et),. (305°). S.G. if 1-150.
Prepared by the action of benzyl chloride (26
pts.) on ohloro-malonic ether (38-8 pts.) and
NaOEt (from 4-6 pts. Na and 70 pts. alcohol)
(Conrad, A. 209, 243; B. 13, 2159). Liquid,
decomposed by EOH into alcohol, benzyl-tar-
tronic acid C,H,.Ca,.0(OH)(COjH)„ and a little
cinnamic acid, _ .
Amide C.H,C1(00.NHJ,. (0. 80°). White
needles. Sol. alcohol, insol. water. (BisohofE
a. Emmert, B: 15, 1112).
p-CHLOEO-BENZYL MEECAPTAN C,H,C1S
i.e. [4:1] C„H,Cl.CHj.SH. [20°] (J. a.W.). From
p - chloro - benzyl bromide (or chloride) and
alcoholic KHS (Eeilstein, A. 116, 347; 147,
346 ; Jackson a. White, Am. 2, 167 ; P. Am. A.
14, 312). Nauseous liquid or white crystals.
Mixes with alcohol, ether, benzene, and CS^. —
(OjH^ClSJjHg : from the mercaptan and ppd.
rigO ; needles ; insol. water, si. sol. ether and
alcohol.
DI-I3-CHL0E0-DI-BENZYL SULPHIDE
C„H,,CUS i.e. (C.H,C1.0a,)jS. [42°]. Fvomp-
ohloro-benzyl bromide and alcoholic Na^S (Jack-
son a. White, P. Am. A. 14, 312 ; Am. 2, 166 ;
B. 13, 1217). Thick needles, insol. water, v. sol.
alcohol, ether, benzene and CS^.
Di-p-chloro-di-benzyl disulphide CuHi^CliS:
i.e. (CXCl.CHi,)j8s. [59°]. From p-chloro-
benzyl bromide and alcoholic Na^S^ (J. a. W.).
Flat needles, with disagreeable smell. V. sol.
alcohol, HOAc, ligroin, either, benzene, and CSj.
^-CHLOEO-BENZYL SULPHOCYANIDE
C„H<Cl.CHjS.CN. [17°]. Prepared by boiling
an alcoholic solution of _p-ohloro-benzyl bromide
with KCNS (Jackson a. Field, Am. 2, 91).
White flat needles.
DI-p-CHLOEO-DI-BENZYL-SULPHONE
C„H,jCl,S02 i.e. (C,H,Cl.CHj)jSOj. [165°].
Formed, together with CfifiLCK^SO^'H., by the
action of E^SO, on p-chloro-benzyl chloride
(Henninger a. Vogt, A. 166, 374). Prepared by
oxidising ^-chloro-benzyl sulphide with CrO,
(Jackson a. White, Am. 2, 167 ; P. Am. A. 14,
312). Very small needles (from alcohol) ; insol.
water, sol. alcohol, ether, HOAc, and CSj.
leomerides [149°] and [185°] are formed when
crude chloro-benzyl chloride is used (H. a. V.).
CHLOSO-BEirZYL SULFHONIC ACID v.
CbiiOho-ioluene sulphonio acid,
DI-jp-CHLOEO-DI-BENZYL DI-SULPHOX-
IDE (CeH.Cl.CHJjSjO,. [120°]. Obtained by
oxidising di-j)-chloro-di-benzyl disulphide with
CrOj in HOAo (Jackson a. White, Am. 2, 169 ;
P. Am. A. 14, 315). Waxy solid, becoming
crystalline; insol. water, v. sol. alcohol and'
ether.
DI - CHLOEO - BETORCIN C„CL,Mej0H)j.
[142°]. Prepared by adding tetra-chloro-betor-
cin in small portions to boiling hydric iodide
il5 p.c). Crystallised from light petroleum
50 pts.) (Stenhouse a. Groves, O. J. 37, 395),
Colourless needles. Sol. CSo, benzene and ether.
Tetra-chloro-betorcin CaCl2Mej(0Cl)j. [109°].
Prepared by adding a solution of betorcin to a
slight excess of chlorine hydrate (ice and water
saturated with CI). The crystals which sepa-
rate after 12 hours are reorystallised from light,
petroleum. The yield is quantitative (Stenhouse
a. Groves, C. J. 37, 399).
Properties. — Large white prisms. V. soL
benzene and ether, insol. water.
CHLOEO-BROMAL v. Chlobo - Di - bbouo-
AOEIia ALDSBYDE.
CHLOEO-BEOMALIDE OsHjCl.BrjO,. [122°].
Colourless prisma. Formed by heating di-chloro*
OHLORO-BROMO-AOETONE.
43
bromo-acetio aldehyde with H^SO, (Jaoobsen a.
Neumeister, B. 15, 600).
CHLOBO-BBOKAinLIC ACID v. CmoRO-
BROMO- DI-OXT-QDINONE.
CHLOBO-BBOUO-ACETIC ACID
CHClBr.COJH. [201°]. Prepared by heating
chloTO-acetio acid (1 mol.) with bromine (1 mol.)
at 160° (Ceoh a. Steiher, B. 8, 1174). Pungent
liquid; attacks the skin. Its salts are t. sol.
Ethyl ether 'KiA.: (c. 162°). Smells like
peppermint; partially decomposed on boiling.
4mJdeCHCLBr.00NH,: [126°]; needles.
Chloro-di-bromo- acetic acid COlBrj.CO^H.
[89°]. (S33°). Formed by oxidation of the cor-
responding aldehyde with HNO, (Neumeister,
B. 15, 603). Trimetrio plates (from cone. HNO,) .
By alkalis it is split up into CO, and chloro-di-
bromo-methane.
Salts. — EA'2aq: glistening soluble prisms.
— FbA'^aq, sparingly soluble slender needles.
Ethyl ether A'Et : (203°); liquid. "■
Amide CClBr,.OONHj: [127°]; small trans-
parent dimetric tables ; y. sol. ether and chloro-
form, si. sol. benzene and CS2. Formed together
with CHClBrj by the action of dry NH, upon di-
chloro-tetra - bromo - acetone C015r2.C0.C0LBr2
dissolved in ether (Levy a. Jodlifika, B. 20,
2320).
Bi-cMoTO -bromo -acetic acid CCl2Br.C02H.
[64°]. (215°). Formed by oxidation of the cor-
responding aldehyde with HNO, (Neumeister,
B. 15, 602). Large prisms. Y. sol. water and
alcohol. By boiling with alkalis it is split up
into di-chloro-bromo-methane and CO^.
Salts. — KA'Saq: long trimetric prisms. —
NaA'Saq: large tables, sol. water, alcohol, and
ether. — "NHjA': long fine needles. — PbA'^aq:
sparingly soluble glistening prismsj
Ethyl ether A'Et: (189°); liquid.
Amide [139°]; (254°); tables. Sol. alcohol
and ether ; insol. chloroform.
CHLOBO-BI-BBOUO-ACETIC AIDEHYBE
CClBrj.CHO. Chlorobromal. (149°). S.G. "
2-2793. Prepared by the action of bromine on
chloro-acetal CH2Gl.GH(OBt)2. Liquid. By
treatment with KOH it gives ohloro-di-bromo-
methane (Jacobsen a. Neumeister, B. 15, 600).
Bydrate CClBrj.0H(0H)2. Chloro-di-
bromo-acetic orthaldehyde. [52°] ; small prisms.
Alcoholate CClBrj.CH(OH)(OEt): [46°];
long needles.
Combination with Acetamide [158°].
Di-chloro-bromo-acetic aldehyde CCljBr.OHO.
BromochU>ral. (126°). S.G. i5 1-9176. Pre-
pared by the action of bromine on di-chloro-
acetal CHClj.CH(OEt)j (Jaoobsen a. Neumeister,
B. 15, 600). Colourless pungent liquid.. On
heating with H^SO, it gives bromochloralide
C^HjCl^BrA [122°].
Hydrate CCljBr.CHfOH)^. Di-chloro-bromo-
acetic orthaldehyde. [51°]. Colourless trime-
trio plates. Sol. water, alcohol, and ether.
Alcoholate CCL^r.OH(OH)(OEt) : [43°];
slender needles.
CHLOKO-BBOMO-ACETO-ACETIC ETHEB
CjHjClBrO,. From chloro-aceto-acetio ether and
Br; or from bromo- aceto-acetic ether and CI
(Meives, .4. 245,62). Oil. NaOEt gives bromo-
Bcetic ether.
Chloro-di-bromo-aceto-acetic ether
CgHgClBrjO,. From di-bromo-aceto-acetio ether
and CI in diffused daylight (M.). NaOEt forms
chloro-bromo-acetic ether (162°).
Di-chlora-bromo-aceto-acetio ether
CjHjCljBrOj. Frombromo-aoeto-acetic ether and
CI (M.). NaOEt forms di-chloro-acetic ether.
Bi-chloro-di-bromo-aceto-acetic ether
CeH,CLBr,0, i.e. CHBrj.CO.CCl..COjEt(?)
S.G. ^ 1-956. Formed by bromination of di-
ohlorO-aoeto-acetic ether. Oil. On saponification
by heating with HCl it yields di-chloro-di-bromo-
acetone (Conrad a. Guthzeit, B. 16, 1551).
CHLOEO-BEOMO-ACETONE CAClBrO i.t.
0
0H2Cl.C0.CHj^r or CHjCl.CH.CHBr. [35°].
(c. 179°). Obtained from epichlorhydrin
O
CH2Cl.CH.CHj by treatment with HBr and oxi-
dation of the resulting CH2Cl.CH(OH).CH2Br
(Theegarten, B. 6, 897, 1276). Pungent crystals,
si. sol. water ; v. sol. alcohol and ether. Forms
a crystalline Compound with NaHSOj (Theegar-
ten; cf. Cloez, A. Ch. [6] 9, 145).
Chloro-tri-bromo-acetone CjHjBrjClO. [50°].
Prepared by heating dichloro-dibromo-acetone
with HBr ; or dichlorhydrin (1 mol.) with bro-
mine (3 mols.) and water at 110° (Claus a. Lind-
horst, B. 13, 1210). Trimetrio prisms : a:b:e
= •7124:1:2.
Chloro-tri-bromo-acetone CjHjClBraO. 2Vi-
bromo-epichlorhydHn. Prepared by treating epi-
chlorhydrin (1 mol.) with bromine (1 mol.) at
100°. Pungent liquid ; heavier than water ; can-
not be distilled even in vania. On shaking with
water it forms a hydrate CjHjClBrjO 4aq [55°]
(Grimaux a. Adam, Bl. [2] 33, 257 ; cf. Cloez,
A. Ch. [0] 9, 145).
Chloro-tri-bromo-acetone CgHjClBrgO i.«.
CBr,.C0.CH2Cl. (215°). S.G. 2-27. From chloro-
acetone and bromine at 100° (Cloez). Pungent
liquid. Forms hydratesC,H2ClBr30 4aq(from
water) and CjHjClBrgO aq (from alcohol). Cold
aqueous ammonia forms bromoform and chloro-
acetamide.
Bi-chloro-di-bromo-acetone C^H^Cl^BrjO i.e.
0
A
CHBrCl.CH.CBrCl or CHBrCl.CO.CHBrCl. [-8°].
(135°) at 40 mm. From di-ohloro-acetone (de-
rived from epichlorhydrin) and bromine (Cloez).
Does not combine with NaHSO,. With water
it forms long prisms of the hydrate
CjHjCljBraO 4aq [54°]. Does not give off a
chloro-bromo-mcthane when treated with am-
monia.
Bi-chloro-di-bromo-acetone CjHjCI^rjO i.e.
O
CBrjCl.CH.CHCl or CBrjCLCCCH^Cl (141°) at
20 mm. Prepared by heating dichlorhydrin
(1 mol.) with bromine (3 mols.) and J the volume
of water to 110° until the colour of the Br' has
gone ; the yield is theoretical (Claus a. Lindhorst,
B. 13, 1209 ; cf. Carius, A. 156, 38 ; Grimaux a.
Adam, Bl. [2] 32, 14 ; Cloez, loc. cit.). Forms a
hydrate CsHjCljEr^O 4aq, [56°], (140°-150°) at
20mm. Not identical with the freoeding (C).
£4
CHLORO-BROMO-ACETONE.
X)i-cliloro-di-1>romo-acetoii.eCHCl2.CO.CHBr2.
(120°) at 35 mm. Formed by the action of bro-
mine on ordinary di-chloio-acetone orBaibaglia's
di-chloTo-acetone (170°) (Gloez); It forms un-
stable hexagonal tables of GjH^Cl^Br^O 4aq. Am-
monia forms no chloro-bromo-methane. EgCl,
gives tetra-chloro-aeetone.
Si-chloro-di-bromo-acetone C^'SJSl^iJO or
CHClj.C0.CHBr2 (?) Formed by heating di-
chloro-di-bromo-aceto-acetic ether with HCl
(Conrad a. Outhzeit, B. 16, 1552). Colour-
less pungent liquid. Forms a hydrate
CjHjCljBrjO 4aq crystallising in large colourless
six-sided tables. Is perhaps identical with the
preceding.
Di-chloro-tetra-bromo-acetone
CCrBrj.CO.CClBrj. [79°]. Formed by the action
of bromine upon ^-di-ohloro-^-di-oxy-quinone
(chloranUio acid) CjCl2(0H)502. Transparent
monoclinic crystals (from acetic acid). Heated
with baryta-water it yields chloro-di-bromo-mo-
, thane CHClBrj. Dry NH, gas converts it into
chloro-di-bromo-acetamide CClBr.GOMH^ and
chloro-di-bromo-methane. With phenyl-hydra-
zine it gives a mixture of chloro- and bromo-
benzene (Levy a. Jedlidka, £. 20, 2319; c/.Steu-
house, A. Swpph 8, 17).
Tri-chloro-bromo-acetone CgR^CljBrO i.e.
CCl3.C0.CHsBr. (190°). Fromtri-chloro-acetone
and bromine at 100°- Very hygroscopip, forming
hexagonal tables of the hydrate CsH^GlgBrO 4aq
[48°]. With ammonia it forms chloroform and
bromo-acetamide (Cloez).
TEI-CHLOEO-a/S-DI-BEOMO-ACETYL-PKO-
PIONIC ACID O^HsCljBrjO, i.e.
CCls.CO.CHBr.CHBr.CO.,H. [98°]. From tri-
chloro-acetyl-acrylic acid and Br in chloroform
(Kekulfi a. 0. Strecker, A. 223, 188). Volatile
with steam ; may be sublimed ; insol. cold, water.
Boiling lime-water splits it up into chloroform
and inactive tartaric acid.
CHLOKO-BaOMO-ACBYLICACIDCsHjCIBrO
i.e. CBrCl:CH.C02H (?) [70°]. S. 6-75 at 20-.
Prepared by the action of HCl on bromo-propiolic
acid at 0° (Mabery a. Lloyd, Am. 3, 127 ; Hill,
B. 12, 660). Needles or prisms ; may be sub-
limed. V. sol. alcohol and ether. Chlorine
forms tri-chloro-bromo-propionic acid [84°] (Ma-
bery, Am. 9, 1).
Salts. — KA'. — ^BaA'2 2aq: flattened prisms.
8. 14-15 at 20°.— CaA',4aq: needles; y. e. sol.
hot water. — AgA'.
(a)-Chloro-di-bromo-aoryIic acid
OjClBrj.COsH i.e. CBrj:CCl.COjH (?) [104«]. S.
5-7 at 20°. Prepared by the action of ClBr in
chloroform on bromo-propioUc acid in the cold
(Mabery a. Lloyd, i4m. 6, 157). Triolinic prisms
(from CSa) ; v. sol. hot water, CSu, and chloro-
form.
Salt s.-^AgA' : trimetrio plates (from water) ;
not affected by light. — CaA'j 2|aq : branching
needles. — ^BaA'^ 3aq : flat prisms. S. 26 at 20°.
(;3)-Chloro-di-bromo-acrylic acid
CBrChCBr.CO^H. [99°]. S. 2-6 at 20°. From
chloro-tri-bromo-acrylio acid by adding baryta-
water in the cold till alkaline (M. a. L.). Prisms
(from CS2) ; y. sol. alcohol, ether, and hot
water. — BaA', 3aq : slender prisms. S. 35 at
20°. — CaA'2 4aq : branching needles.
Bi-chloro-bromo-aorylic acid Cfii<(Sii.CO^
i.t. CCLi:CBr.COjn(?) [78°-80°]. S. 6-9 at
20°. Obtained by the action of cold baryta-
water on di-chloro-di-bromo-propioni(j acid ob-
tained from o^S-di-bromo-aoryUc acid and
chlorine (Mabery, Am. 9, 8). Prisms; v. sol-
alcohol and ether : si. sol. cold CSj.
Salts. — KA' : slender needles. — AgA' ;
slender needles.— BaA'2 3aq : trimetric plates.—
CaA'j 4aq : pearly neecQes.
Dl-chloro-bromo-acrylic acid C2BrCl2.COjH
i.e. CClBr:CBr.COjH(?) [85°]. S. 2-6 at 20°.
Obtained by the action of cold baryta-water
(1 mol.) on di-ohloro-di-bromo-propionic acid
(1 mol.) that has been prepared from bromine
and n;8-di-chloro-aorylic acid (M.). Prisms ; v.
sol. alcohol and ether, m. sol.^ CSj.^ This aoid
is possibly identical with the preceding.
Salts.— KA': pearly needles.— AgA': slender
needles. — BaA'^ 3aq : trimetrio plates. —
CaA'2 4aq: jagged plates.
CHL0B0-BE09I0 -ALDEHYDE v. Chi«bo-
BEOMO-AOETIO ALDEHYDE.
<t- DI - 0HLOEO-7n-BBOMO - AMIDO - ACETO-
PHEWONE [5:2:1] CeH,Br(NHJ.C0.CHCl2.
[110°-120°]. Formed by boiling aiwm-tri-bromo-
araido-acetophenone with HCl (Baeyer a. Bloem,
B. 17, 967). Sublimable. Fine felted orange
needles or long flat prisms. V. sol. alcohol, si.
sol. water. By boiling with dilute NaOH and
exposure to the air it yields bromo-indigo.
CHLOEO-BEOMO-ANILIWE C,HsClBr(NHj)
[2:4:1]. [69°]. Formed, together with y-bromo-
aniline, by the action of tin and HCl on p-
bromo-nitro-benzene (Hijbner a. Alsberg, A.
156, 312 ; Fittig a. Biichner, A. 188, 14). Formed
also by chlorinating ^-bromo-aniline. Prisms ;
volatile with steam. — B'HCl.
Chloro - di - bromo - aniline OBHjClBrjjNHj)
[6:4:2:1]. [95°]. Formed by bromination of
o-chloro-aniline (Langer, B. 15, 1065 ; A. 215,
115). Long white needles (from benzoline) ;
V. sol. boiling alcohol and ether.
Chloro - di - bromo - aniline CjH2ClBr2(NH2)
Formed by bromiuating p-chloro-aniline (Hof-
mann, A. 53, 38). White prisms, which melt
in hot water; volatile with steam. Does not
form salts.
Chloro - tri - bromo - aniline CjHClBr3(NH,)
[3:2:4:6:1]. [124°]. Formed by bromination of
m-chloro-aniline by Br in dilute HCl (Langer,
B. 15, 1065 ; A. 215, 112). Thin white needles
(from alcohol) ; v. sol. boiling alcohol and
ligrom.
Di - chloro - bromo - aniline CjHjC13r(NHj)
[2:6:4:1]. [93-5°]. Formed by chlorinating
^-bromo-aniline (Fittig a. Biichner, A. 188, 22).
Does not unite with acids.
Di - chloro - tri-bromo-aniline CjCljBr3(NHa)
[3:5:2:4:6:1]. [219-5°]. From di-chloro-aniline
OsHs(NHj)Clj [1:3:5] in "dilute HCl by bromine-
water (Langer, A. 215, 122). White needles
(from alcohol). M. sol. boiling alcohol.
Tri - chloro-di -bromo - aniline C8Cl3Br.,(NH J
[2:4:6:3:5:1]. [238-5°]. From 0„H3(NH,)Br,
[1:3:5] in acetic acid by CI (Langer, A, 215,
118). White needles (from alcohol).
DI-CHLOEO-BEOmO-ANIHEACEirE
OnHjCljBr. [168°]. Formed by heating di-
chloro - anthracene tetra - bromide at 190° '
(Sohwarzer, B. 10, 376). Small greenish-yellow
lamime ; v. sol. benzene and chloroform.
OHLORO-BROMO-ETHANK.
45
Oi-chloTO-di-bromo-anthracene 0„HjGloBr2.
[252°]. From di-ohloro-anthraoene tetrabromide
and alooholio EOH (S.). Small yellow needles
(from benzene) ; si. sol. alcohol, y. sol. benzene.
Si-obloro-tetra-bromo-antliracene
CiiHtCl^Br,. Formed by the action of alcoholic
EOH upon di-ohloro-di-bromo-anthracene-tetra-
bromide (Hammerschlag, B. 19, 1107). Golden-
yellow needles. Solid at 380°- V. si. sol. all
solvents. By GrO, and acetic acid it is oxidised
to tetra-bromo-anthraquinone.
DI • CHLaRO - SI • BBOKO - ANTHBAGENE-
TETEA-BEOMIDE OuHjClJBrs. [212°]. Glisten-
ing white needles (from acetic acid). Formed
by combination of di-chloro-di-bromo-anthracene
with bromine vapour. By alcoholic EOH it is
converted into di-ohloro-tetra-bromo-anthracene
(Hammerschlag, B. 19, 1107).
m-CHLOBO-BBOMO-BENZENE 0,H,GLBr
[1:3]. From ^-ohloro-aniline by bromination
and elimination of NH, by the diazo- reaction
(Korner, J". 1875, 326; Q. 4, 305).
2) -Ghloro-bromo- benzene GgH^GlBr [1:4].
[67°]. (196°). From ^-bromo-aniline by dis-
placement of NHj by Gl; or from p-chloro-
aniline by displacing NH, by Br (Griess, Tr.
1864 [3] 702). Also by boiling p-chloro-benzene
with bromine (Eprner, O. 4, 342).
Chloro-tri-bromo-benzene CsH^CIBrs [1:2:4:6].
[80°] (S.) ; [82°] (L.). Fcynnation.—l. By heat-
ing the perbromide of tri-bromo-diazo-benzene
chloride (from tri-bromaniline) with glacial acetic
acid (Silberstein, J. pr. [2] 27, 113).— 2. From
C„H01Brs(NH,) [123-5°], alcohol, and amyl
nitrite at 100° (Langer, A. 215, 113; B. 15,
1065). Properties. — Long satiny needles. Insol.
water, si. sol. cold alcohol and glacial acetic
acid, V. sol. hot alcohol, hot glacial acetic acid,
ether, benzene and CHCl.,.
Si - chloro - di - bromo ■ benzene CjH^r^Gl,.
[67°] (Garzino, (?. 17, 502).
Bi-chloro-tri-bromo-benzene OoHGl^Br,
[1:3:2:4:6]. [121°]. From C6(NH„)Cl2Br, by
treatment with amyl nitrite and alcohol (Langer,
A. 216, 120 ; B. 16, 1332), Small thin needles
(from alcohol).
Tri-chloro-di-bromo-benzene CgHCi.Jiv,
[1:3:5:2:4]. [119°]. From G„(NHz)Cl,Brj and
amyl nitrite in alcohol (Langer, A. 215, 119).
Slender needles. Y. sol. boiling alcohol.
CHLOBO-BBOMO-BEJSrZOIC ACIB
C,H,ClBrO, i.e. OsH,ClBr.CO,H. [151°]. S.-26
at 21°. Formed- by adding bromine to a hot
solution of silver o-chloro-benzoate (but not of
the free acid) (Pfeifer, B. 5, 65G). Slender
needles (from water) ; may be sublimed. — KA'aq.
'— BaA'2 3aq.— GaA'j 2aq.
Cliloro-bromo7benzoic acid CuHaClBr.GOjH.
S. "09 at 21°. From «i-ehloro-benzoic acid and
bromine (P.). Slender needles. — BaA'j 2aq.
BI-CHLOBO-DI-BROMO-BUXANE
C,H.Gl,Br, i.e. CHj.GHBr.CHBr.CHCl,. From
Br and the di-chloro-butylene derived from cro-
tonio aldehyde (KekuU, A. 162, 98 ; Newbury,
Am. 5, 113). Decomposes above 100°. Con-
verted by boiUng dUute KjCO, into C^H^GlBrO
(115°-.120°).
CHLOBO-SI-BEOMO-BTJTYL ALCOHOL
C,H,GlBr,0. Obtained by the union of bromine
with chloro-butenyl (ohloro-crotyl) alcohol which
is itseli got by redaction of tri-imloro-butyl al-
cohol (GarzaroUi-Thurnlackh, A. 213, 378).
HNO, oxidises it to chloro-di-bromo-butyrio
acid.
CHLOBQ-SI-BBOMO-BVTYBIC ACIB
AHjGlBrjO, t. e. CHj.OHBr.OClBr.COjH (?)
[92°]. From a-chloro-crotonio acid and Bit
(SarnofE, A. 164, 105). Prisms, m. sol. cold, de-
composed by hot, water. Distillation, or treat-
ment with zinc and HGl, converts it into chloro-
Motonio acid. — PbA'j.— AgA'.
Chloro-tri-bromo-butyric acid C^HiClBrjO^.
[140°]. Formed by oxidising the corresponding
aldehyde with fuming HNO3 (Pinner, 'B. 8,
1324). Small plates.
CHLORO-BI-BEOHO-BUTYRIC ALSEHYBE
0,H5ClBrj.O i. e. CHj.CHBr.CClBr.CHO. From
Br and a-chloro-crotonic aldehyde in the cold
(Pinner, B. 8, 1322). Oil ; with water it slowly
forms a solid hydrate or orthaldehyde
CiH,ClBr,(OH),.
Ghloro-tri-bromo-bntyric aldehyde
CjHiCIBraO. Formed by warming o-chloro-
crotonic aldehyde with bromine (P.). Oil.
Forms a hydrate or orthaldehyde
C4H4ClBr,(OH)j [78°] crystallising in slender
needles.
Bi-chloro-di-bromo-batyrio aldehyde
CH^Ol.CHBr.CClBr.CHO. [o.-78°]. From 07-
di-ohloro-orotonic aldehyde and Br in the cold
(Natterer, M. 4, 540). Combines with NaHSO,.
It forms a crystalline hydrate or orthaldehyde
CH2Gl.GHBr.GGlBr.GH(OH)2 [72°].
, CHLOBO-BBOMO-CAMFHOB v. Gamfhob.
CHLOBO-BI-BEOMO-n-CUMEITE
CsHjCHBr.CHBrwCHjCl. [96-5°]. From styryl
chloride and Br. Tables (from ether).
TBI-CHLOBO-BEOMO-CYMENE
»CeCl,Br(CH3)(CsH,)(?) [65°]. From sodium
tri-chioro-cymene snlphonate and bromine-
water (Kelbe, B. 16, 619). Needles.
CHLOao -PEN r A - BEOMO - BECYLENE
C|„H„ClBr5. From Br and menthyl chloride
(Oppenheim, A. 130, 177).
5-CHLOKO-BROMO-ETHANE CHjCl.CH,,Br.
Ethylene chloro-bromide. (108'). S.G. 2 1-79 ;
12 1-70.
Formation. — 1. From s-chloro-iodo-ethane
and Br (Henry, A. 156, 14).— 2. From ethylene
di-bromide and HgClj (Montgolfier a. Giraud, Bl.
[2] 33, 12).— 3. From GHjCl.CHj.OH and Br at
130° (Demole, B. 9, 556). — i. From ethyl bro-
mine by ohlorination (LescoBur, Bl. [2] 29, 484).
Preparation.— 1. Bromine (500 g.) is dis-
solved in 700 CO. HGl mixed with 700 c.c.
water, cooled with ice, and treated with chlorine
as soon as the temperature of the liquid has
fallen to 2°. The chlorine is passed in, with
frequent shaking, until the colour of the bromine
has disappeared. Ethylene is then passed in,
and the oil washed, dried, and distilled. It
boils at 107°-109°. If it boils at 109°-111° it
contains ethylene bromide (M. Simpson, Pr. 27,
119 ; J. W. James, J.pr. [2] 26, 380 ; C. J. 43,
37).— 2. CjHjBr^ is gently warmed with SbClj,
the product poured into strong HGl, and the oil
washed with very dilute NaOH and distilled
(Lossner, J.pr. 121, 421 ; James, 0. /. 36, 806).
Reactions.— 1. Acts upon boiling alcoholic
EONS forming OACl(CNS).— 2. Alcoholic EOH
gives EBr and chloro-ethylene.
18
CHLORO-BROMO-ETHANE.
M-Chloro-bromo-ethane CHj.OHClBr. Elhyli-
dme-chloro-bromide. (82°) (B.) ; (83° i. V.) fS.).
8.G. ii 1-61 (B.) ; is 1-67.
Formaiion. — 1. From bromo-ethylene and
oono. HClAq at 100° (Eeboul, A. 155, 215).-2.
By brominatinK ethyl chloride in sunlight (Stae-
del, B. 11, 1739 ; Denzel, A. 195, 193).— 3. By
chlorinating ethyl bromide (Lescoeur, Bl. [2] 29,
483).
Pr(^erties. — Oil. Converted by alcoholic
KOH into £Br and bromo-ethylene. Ag^O gives
aldehyde.
Chloro-di-bromo-ethane CH,.CBr2Cl. (124°
i. v.). S.G. IS 2-134. A product of bromination
of ethyl chloride in sunlight (Staedol, B. 11,
1739 ; Denzel, A. 195, 196). Liquid. Converted
by alcoholic EOH into CH,:CClBr.
Chloro-di-bromo-ethane CH3r.CHClBr.
(163° i. v.). S.G. iS 2-268. From chloro-
ethylene and Br (Hugo Miiller, A. Suppl. 3, 287).
From chloro-bromo-iodo-ethane and Br (Henry,
Bl. [2] 42, 263). Also from EtCl and Br in sun-
light (S. ; D.). Oil. Alcoholic KOH gives
CHj:CClBr. With SbCl, it gives CH,Br.CHClr
ChIoro-di>bromo-ethane CH^CLCHBrj. From
crude chloro-bromo-iodo-ethane and Br (H.).
Alcoholic KOH gives CH^tCBrj (89°) and
CH,:CBrCl (63°).
Chloro-tri-bromo-ethane CHjBr.CClBr^. (201°
i. V.) at 735 mm. S.G. is 2-602. Formed by
the action of bromine on CHj.CClBrj, on ethyl
chloride, on CH.,Br.CHBrCl, or on CH^iCClBr
(S. -, D.; H.). Gives CHBr:CBrCl with alcoholic
KOH. SbCi, forms CHjBr.CCl,.
Chloro-tetra-bromo-ethane CHBr2.CBr2Cl.
Chhro-acetylene tetra-bromide. [33°]. (240°)
at 736 mm. S.G. " 3-366. From EtCl and Br
in sanlight (S. ; D.). From chloro-acetylene
and bromine (Wallach, A. 203, 89). Also from
chloro-di-bromo-ethylene and Br (Mabery, Ajn.
5, 255). Pungent crystals -, t. e. sol. alcohol and
ether.
Chloio-penta-bromo-ethane CjClBr,. [170°].
Prepared by the action of bromine on ohloro-
tribromo- and chloro-tetrabromo-ethane (Denzel,
B. 12, 2207).
Di-chloro-bromo-ethane CHj-CCl^r. (99°
i. v.). S.G. IS 1-752. Formed by brominating
ethylidene chloride in sunlight (S. ; D.). Liquid.
Di-chloro-bromo-ethane 0HCl2.CH.,Br. (138°).
S.G. 1-859. From CHClrCHjOH and PBr3(Laore,
C. B. 104, 1180). From CHBrj-CHaBr (Henry,
O. B. 97, 1491 ; Bl. [2] 42, 262), or CHClBr.CHjBr
and SbClj. Converted by alcoholic KOH into
CHjiCCl,.
Di-chloro-bromo-ethane CHClBr.CHjCl. (140°
cor.). S.G. if 1-8685; || 1-8542. M,M. 10-905
at 21*6°. Formed by gradually adding bromo-
ethylene to chloroform through which a current
of chlorine is passing (Ferkin, C. J. 45, 535).
According to Lescoeur {Bl. [2] 29, 485) three
isomeric di-ohloro-bromo-ethanes are formed by
chlorinating ethyl bromide, viz.: (1). (137°);
S.G. 2 1-88,— (2). (161°); S.G. s l-998,-(3). (o.
160°) ; S.G. 2 2-113.
Dl-chloro-fii-bromo-ethane CHCVCHBr,.
Acetylene di-ehloro-di-bronUde. (196°-200°).
S.G. ^ 2-391. From acetylene dibromide and
SbCljin-the cold (Sabanejefi, ii. 216, 256). Also
from acetylene, Br (31 g.), and (120 g.of) aqueons
HCIO. Beactions.—l. Converted bj Zn and
alcohol into chloro-bromo-ethylene (q. v.).— 2.
Boiled 6 hours with alcoholic KOAc it forms
CHBr:CCL, [114°-116°].
j-Di-chloro-di-bromo-ethaneCHClBr.CHClBr.
Acetylene di-chloro-di-bromide. (190°-195=).
From bromine and acetylene di-chloride ; or from
chlorine and acetylene di-bromide (Sa.).. Gives,
with zinc and alcohol, acetylene dichloride (50°-
60°).
Di-chloro-di-bromo-ethane CHjBr.CBrClj.
(177°). S.G. is 2-270. From CHj-CHCl^ and
Br in sunlight (S. ; D.).
Di-chloro-tri-bromo-ethane CHBr^.CBrCl.,.
(216°-220°). From CHj.CHClj and Br in sun-
light (S. ; D.).
Di-chloTO-tetra-bromo-etbane C^Cl^Br, i.e.
CBrj.CCljBr. [180°]. Colourless crystals. Pre-
pared by the action of bromine on CIIjBr.CCljBr
(Denzel, B. 12, 2207).
Tri-chloro-bromo-ethane CClj.OHjBr. (162°).
S.G. g 1-884. Formed by heating' tri-chloro-
ethane CCI3.CH3 with bromine at 160° ; or by
the action of SbClj on CCljBr.CKBr or
CClBr^CHiBr. Converted by alcoholic KOH
into CClj:CHBr (115°) (Henry, 0. B. 98, 370).
Tri-chloro-di-bromo-ethane CHBr^-CCl,.
(200°). S.G. s 2-317. From chloral and PCljBrj
(Paterno, /. 1871, 512 ; G. 1, 590).
Tetra-chloro-di-bromo-ethane CCljBr.CCl^Br.
Bromide of per-chloro-ethylene. S.G. -l 2-3.
From 0,014 and Br in sunshine (Malaguti, A. Ch.
[3] 16, 14). Tables (from alcohol). Begins to
volatilise at 100° but decomposes at 200° into
Br and C^Clj.
Tetra-chloro-di-bromo-ethane CCl,.CClBrj.
From penta-chloro-ethane and Br at 200° (Pa-
terno, G. 1, 593). Also from CHBrj.CHBrj and
chlorine (Bourgoin, Bl. [2] 23, 4). Prisms (from
alcohol) ; smells like camphor. May be sub-
limed, but decomposed by heat into chlorine and
CjCL^rj.
CHLOBO-BBOKO-ETHEB v. Chlobo-bbomo-
DI-EIHYL OXISE.
s-CHIOKO-BEOMO-ETHYLENE C^HjClBr i.e.
CHChCHBr. AcetylenecMoro-bromide. (82°). S.G.
s 1-8157 (P.) ; 1-779,(S.) ; as 1-747 (S.). Bromine
(2 mols.) is slowly added to acetylene chloro-
iodide under water. The liberated iodine is re-
moved by NajSjO,. The yield is small (Plimp-
ton, C. J. 41, 393). Formed also by treating
CHClj.CIIBrj with zinc and alcohol (Sabanejeff,
A. 216, 258). Liquid, does not polymerise. With
alcoholic KOH it gives oS an explosive gas, pro-
bably CjHCl.
Chloro-bromo-ethylene CHjtCClBr. (62°).
From chloro-ethylene bromide CHjBr.CHClBr
and KCy (Hugo MiiUer, C. J. 17, 420) or alco-
holio KOH (Denzel, A. 195, 206; Demole a.
Durr, B. 11, 1302). Also from chloro-bromo-
iodo-ethane (from CjHjBr and ICl) by alcoholic
KOH (Henry, Bl. [2] 42, 263). Pungent odour,
readily polymerises, becoming solid. Absorbs
dry oxygen forming chloro-acetyl bromide and
bromo-acetyl chloride.
Chloro - di - bromo - ethylene CHBr:CBrCl.
(142°) at 735 mm. S.G. is 2-275 (S.). From
chloro-tri-bromo-ethane CHjBr.CBrjCl and alco-
hoUc KOH (Staedel, B. 11, 1740). Formed also
by boiling chloro-tri-bromo-propionio acid with
baryta-water (Mabery, Am. 5, 256). Liquid.
OHLORO-BROMO-JIETFIANB
47
Chloro - tri - bromo - ethylene C^ClBr, i.e.
0Br,:CBr01. [34°]. (204°) at 730 mm. Pre-
pared by tbe action of alcoholio KOH on chloro-
tutra-bromo-ethane (Denzel, B. 12, 2208).
Di-ohloro-bromo-ethylene CHBrrOClj. [114°-
116°]. S.G. IS 1-906. Formed by the action of
alcoholic KOH on CH-Br-CBrClj (Denzel, A. 195,
206)j or on CCl,.OHjBr (Henry, 0. B. 98, 370).
Also from CHBr,.0HCl2 by alcoholio KOAo
(Sabanejeff, A. 216, 261).
Si - chloro - di - bromo - ethylene CCl^iCBr,.
(c. 194° 7). Prepared by the action of alcoholio
EOH on di - chloro - tri - bromo - ethane
OHBrj.CBrCl, (Staedel, B. 11, 1740). Also from
CClg.CClBr, by heating with aniline (Boargoin,
Bl. [2] 24, 116). Solidifies below 0°.
CHLOBO-DI-BKOUO-SI-ETHYL OXIDE
CHClBr.CHBr.OEt. (170°-180°). Prom ohloro-
vinyl ethyl oxide and Br (Godefroy, C. B. 102,
Tri-(
l-chloro-di-bromo-di-ethyl oxide
C.^fiiiBrjO i.e. OCl^Br.CClBr.OEt. [17°]. From
tri-chloro-vinyl ethyl oxide and Br(Busch, B. 11,
446). With AgOAo it gives OjCljBr(OAo)j.OEt
(180^-190°).
Eeza - chloro - tetra - bromo • di - ethyl oxide
C.Cl^riO. [90°]. Obtained by union of Br
with ohloroxethose C^H^O, a Substance formed
by the action of alcoholic E^S on perohlorinated
ether (Malaguti, A. Ch. [3] 16, 19).
DI-0HLOBO-I£TBA-BB0MO-FLUOBESCElir
C2.H,0501,Br, i.e. 0^01,(0,0,) (C„HBr20H),0.
Di-chloro-eosin. Formed by brominating di-
chloro-flnorescein (from resorcin and di-chloro-
phthalic anhydride). The alkaline solution has
a bluer shade than that of eosin (Le Boyer, A.
238, 358).
S al t.— Ca,H<K,04Ci;Br,.
CHLOBO-BBOUOf OBK v. Cblobo-di-bbomo-
CHIOBO-OI-BBOIUO-HEXAXE CHi-CUBr,.
(219°). From hexenyl chloride and Br in CCI4
(Destrem, A. Oh. [S] 27, 58).
Chloro-tetra-bromo-hexane CAGlBr^. From
Br and chloro-diallyl (Henry, 0. B. 87, 171).
CHLOBO-DI-BBOMO-EEXYL ALCOHOL
0,H„ClBrjO. (o. 254°). S.G. 15 1-99. From
ohloro-hezenyl alcohol (186°) and Br (Destrem,
A. Ch. [5] 27, 58).
CHLOBO-BBOUHYDBIir v. Chlobo-bbouo-
raOFTL AIiCOBOL.
CHLOBO-BBOUO-HTSBOClUIirOKE
0,H,ClBr(OH)j. [X72°}. Formed by saponifica-
tion of its di-acetyl-derivative produced by the
action of acetyl bromide on chloro-quinone
(Scholz, B. 15, 6S6). Formed also by the action
of cone. EBrAq on chloro-quinone (Levy a.
Schultz, A. 210, 160). Long needles. Sol. alco-
hol and ether, b1. boI. water. On oxidation
it gives chloro-bromo-qoinone [172°].
Di-acetyl-derivative GsH2CLBr(OAa)2
[146°]. Short needles. Sol. alcohol and benzene.
Di-chloro-di-bromo-hydroquinone
C,CljBr,(OH), [6:2:5:3:4:1]. [233°]. Formed by
reduction of the corresponding quinone by SnCl,
(Levy, B. 16, 1447 ; 18, 2369 ; Krause, B. 12, 54;
Hantsoh, B. 20, 2279). Monoclinic crystals:
o:6:c = 2-976:l:2-75; ^ = 77° 22'.
Di-acetyl derivative
C.Cl^r,(OAc),: [270°] (Levy, B. 18, 2369).
Tri-ohloro-bromo-hyaroqttlnoneOaBrCl3(OH),
[229°]. From tri-chloro-bromo-quinone, HI, and
phosphorus (Stenhouse, A. Suppl. 6, 219). Also
from tri-uhloro-quinone and cone. HBrAq (Levy
a. Schultz, A. 210, 161). Monoclinic needles,
ffl:6:c = 2-915:l:2-671; i8 = 77°40'. Insol. water,
sol. dilute alcohol.
CHLOBO - BEOUO-HYDBOTHYKOQTTINONE
0,Me{03H,)ClBr(0H)j [3:6:2:5:4:1]. [63°] or
[73°] (?). From chloro-thymoquinone
0„HMe(CjH,)01(0H)2 [3:6:2:4:1] and HBr; or
from bromo-thymoquinone
0„HMe(03H,)Br(0H)j [3:6:2:5:1] [45°] and HCl.
Obtained also by reducing chloro-bromo-thymo-
quiuone [87°] with hydroxylamine (Sohniter, B.
20,1318). Needles.
Chloro-bromo-hydrothymoqninone
0,Me(03H,)0IBr(OH)j [3:6:5:2:4:1]. [66^.
Formed by reducing chloro-bromo-thymoqui-
none [78°] with hydroxylamine (S.).
CHLOBO - BBOIIO - HyDBOIOLUQTJIirOirE
0„HMeClBr(OH)j. [123°] (anhy.). Formed by
the action of HBr upon ohloro-toluquinone.
Crystals (containing aq). V. sol. alcohol and
ether, m. sol. water and ligro'in, 3I. sol. benzene
and chloroform (Sohnitor, B. 20, 2286).
Cbloro-bromo-hydrotoluquinone
0„HMeClBr(0H)2. [121°] (anhy.). Formed by
the action of HCl upon bromo-tolaquinone,
Long needles, containing aq (from hot water).
Begins to sublime at 1.05° (Schniter, B. 20,
2287),
CHLOBO - BBOMO - lOBO • AOBYLIC ACID
02ClBrI.C0jH. [116°]. Formed by heating
bromo-propiolic acid with an ethereal solution
of 101 (Mabery a. Lloyd, Am. 4, 96 ; P. Am. A.
17, 99). Monoclinic prisms (from water) melt-
ing at 110° ; but at 116° when crystallised from
OS,; may be sublimed. — AgA'. — CaA', aq :
branching needles. — BaA'jS^aq: prisms; S.
25-4 at 20°.
Chloro-bromo-iodo-acrylic acid G,HClBrIOr
[129°]. Glistening colourless plates. V. sol.
water, alcohol, and ether. Formed by the action ,
of a chloroform solution of ClBr upon iodo-pro-
piolic acid (Stolz, B. 19, 539).
CHLOBO-BBOltlO-IOSO-ETHANE C,H,CLBrI.
(194°). S.G. 2 253. Slowly formed by union
of ICl with bromo-ethylene in the cold (Maxwell
Simpson, A. 136, 142; Henry, 0. B. 98, 680).
Oil. Converted by alcoholic KOH into KCl
(3pts.), KI (lpt.),bromo-iodo-ethylene CH,:CBrI,
and chloro-bromo-ethylene CH2:CClBr. Hence
the chloro-bromo-iodo-ethane must be a mixture
of isomerides.
CHIOBO-EBOmO-IODO-PBOFAIirE
CaHjClBrl. S.G. 2 2-325. From chloro-iodo-
propyl alcohol and PBr^ (Henry, B. 4, 702 ; c/.
3,351). Oil.
SI-CHLOBO-BBOUO-UESITYLEITE
C,H,BrClji.e.C,HjBr(CH3)(CHjCl)j. [76°]. From
bromo-di-<»-oxy-mesityIene by heating with cone.
HClAq (Colson, A. Ch. [6] 6, 101). Readily
gives oS HCl in the air.
CHLOBO - BBOMO - METHANE GH^ClBr.
(68°). S.G. {^ 1-991. V.D. 4-43. Formed by
the action of excess of bromine on CHjClI
(Henry, C. B. 101, 599). Oil; not decomposed
by light.
ChloTO-di-bromo-methane CHClBr^ GhlorO'
bromoform. (119°) at 730 mm. (L. a. J.) j (126=)
48
CHLORO-BROMO-METHANE.
(J, a. N.). S.G. IS 2-445. V.D. 7-37 (for 7-22),
Occurs in crude bromine (Dyson, C. J. 43, 36).
Formed by boiling di-chloro-tetra-bromo-aoetone
0CIBrj.CO.CClBrj with baryta-water. ' Prepared
also by the action of NaOH on chloro-di-bromo-
aoetio aldehyde (Jacobsen a. Neumeister, B. 15,
601). Colourless liquid, of Bweetish odour (Levy
a. JedUSka, B. 20, 2319).
Si-chloro-bromo-methane CHCljBr. (92°).
S.G. IS 1-9254. Bromochloroform. Colourless
Gquid. Prepared by the action of NaOH on di-
chloro-bromo-acetic aldehyde (Jacobsen a. Neu-
meister, B. 15, 601).
Tri-chloro-bromo-methane CBrCl,. (104°).
S.G. § 2-0550 (Thorpe, C. J. 37, 203). C.E.
(0°-10°) -001089; (0°-100°) -0012065. S.V.
108-48.
Formation. — 1. By heating CClj.BOjBr with
ftlcohol at 100° (Loew, Z. 1869, 624).— 2. By
bromination of chloroform (Paterno, O. 1, 593 ;
Priedel a. Silva, Bl. [2] 17, 538).— 3. By action
of bromine on potassic tri-chloro-acetate at 120°
(van "t Hoff, B. 10, 678).
Properties. — ^Liquid, smelling like carbon
tetrachloride.
CmOSO-BEOMO-METHAKE STJIPHONIC
ACID. Barium salt (CHClBr.S03)2Ba. Prom
ohioro-sulpho-acetate of barium and bromine
(Andreasoh, M. 7, 170). Satiny plates.
CHLOEO - BKOMO - METHYI, - ETHYL - BIY-
OXALINE OaHadlBrNj i.e. C3ClBr(0H3)(CjH5)Nj.
Chloro-bromo-oxal ethyline. From chloro-
methyl-ethyl glyoxaline by treatment with Br in
CS, followed by boiling water (Wallach, A. 214,
290 ; B. 10, 1193). Oil with narcotic odour.
Solidifies with difficulty. SI. sol. water. Not
volatile. With Br it forms CoHjClBrN^BrjHBr.
Salts.— B'HCl : prisms.-(B'HCl)jPtCl..—
B'^gNO,.
CHLOBO-BBOHO-NAFHTHALENE
C,oH.ClBr [1:4]. [115°]. From (o)-naphthyl-
aniine j)-sulphonic acid by conversion into
bromo-naphtiialene sulpbonio acid, and treat-
ment of the latter with PCI5 (CWve, Bl. [2] 26,
540).
Chloro-bromo-naphthalene C,„Hj01Br. [119°].
Formed, together with the following, by the ac-
tion of Br (1 mol.) on (a)-chloro-naphthalene
!1 mol.), or of Gl on (a) -bromo- naphthalene
Guareschi a. Biginelli, G. 16, 152 ; C. C. 1887,
618). Thin plates. Oxidised by CrOj to chloro-
phthalic acid [184°]. Possibly identical with
the pre6eding.
Chloro-bromo-naplithalene Cn^HjClBr. [67°].
(303° uncor.). Prepared as above. Needles (by
sublimation). CrO, in acetic acid gives chloro-
bromo-naphthoquinone [167°] and chloro-bromo-
phthalide.
Bi-chloro- bromo -naphthalene CgoH^Gl^Br.
[80°]. From di-phloro-naphthalene [38°] and
Br in the cold (Laurent). Slender needles.
The following chloro-bromo4iaphthalenes de-
scribed by LaQrent {A. Oh. 49, 218 ; 52, 275) are
insufficiently characterised: OjoHjCljBrj (two),
CjoHjClsBr (three), and CioHjClaBr^ (two).
The following compounds are probably mix-
tures or molecular compounds : (a) G2gH„Cl.,Br3.
[76°]. From di-chloro-naphthalene [38°] and Br
followed by alcoholic KOH (Faust a. Saame,
A. 160, 60). Needles (from ether-alcohol).
(6) Cj,H,Cl,Br3. [73°]. From di-chloro.naph-
thalene [68°] by successive treatment with B»
and alcoholic KOH (F. a. S.).
CHLO&O-BEOMO-NAPHTHAIEWE TETBA-
BEOMIDE 0,„H.ClBr,. [110°]. From ohloro-
naphthalene and Br (Laurent). Triclinio
columns.
CHIOBO - DI - BBOMO - NAPHTHALENE
TETBA-CHLOBIDE C,„H5ClBr.,Cl4. [150°]. From
di-bromo-naphthalene tetra-chloride and chlo-
rine. Triclinic columns, si. sol. ether.
CHLOBO-BBOMO-NAFHTHOQUINONE
C,„H,0IBrOs. [167°]. From ohloro-bromo-naph.
thalene [67°] by CrO, in HOAo (Guareschi, CO.
1887, 518).
CHLOBO-BBOMO-NITBO-ANILINE
CjE^ClBrN^Oj i.e. CeHjClBr(NOj)(NH,) [4:6:2:1]. '
[106°]. From chloro-nitro-aniline in HClAq
by bromine-vapour (Komer, J. 1875, 352 ; G. 4,
305). Orange-yellow needles.
CHLOBO-BBOmO-NIIBO-BENZENE
C„H,01Br(N0j) [1:3:5]. [82-5°]. From the pre-
ceding by diazo- reaction (Edmer, G. 4, 377).
LaminEB.
Chloro-bromo-nitro-benzene C^,ClBr(NOJ
[1:4:2]. [69°]. From ^ -chloro-bromo-bcnzene
and HNOs (K.).
Chloro-bromo-nitro-bcuzene 0^3ClBr(NO2)
[1:3:4]. [49-5°]. From chloro-nitro-aniline [123°]
by displacing NHj by Br (K.). With alcoholic
NH3 at 160° it regenerates the ohloro-nitro-
aniUne.
TBI-CHIOBO-BI-BBOMO-NITBO-ETHANE
CCljBr.CCIDr(N02). From C01j:CCl(NOj) and
Br at 150°. Crystalline (Hoch, J. pr. [2] 6, 95).
CHLOBO-BEOMO-SI-NITBO-UETHANE
001Br(N0j)j. Formed by passing chlorine into
an aqueous solution of potassio - bromo - di-
nitro-methane CKBr(N02) (Losanitsch, B. 17,
848). Oil. V. sol. alcohol, insol. water. By
caustic alkalis the Br atom is displaced by a
metallic atom.
Chloro-di-bromo-nitro-methane CClBr2(N0,).
S.G. ^ 2-421. Formed by simultaneous action
of bromine and potash on CC1H2(N02) (Tsoher-
niak, B. 8, 610). - An oil, insol. potash, volatile
with steam.
CHLOEO-BEOMO-NITEO-PHENOL
C„H3ClBr(N0j)0H [4:2:6:1]. [125°]. From
(4,6,l)-chloro-nitro-phenol [87°] and Br in HOAo
in the cold (Ling, G. J. 51, 787). Converted by
Br and water at 100° into tetra-bromo-quinone.
CsH,ClBrNO,K: dark red needles.— BaA'j aq.—
CaA'j2iaq.
Chloro-bromo-nitro-phenolCjH„ClBr(NO,)OH
[2:4:6:1]. [120°]. Formed by boiling (4,6,1)-
ohloro-nitro-phenol [87°] with Br and HOAo, an
isomeric change taking place (L.). Formed also
by chlorinating (4,6,l)-bromo-nitro-phenol [88°]i
When heated with Br and water it gives chloro-
tri-bromo-quinone. — CoHjClBrNOaK : red plates.
— CaA'2 7aq.
a> - TBI - CHLOEO - eso - SI - BEOUO - eso - 01-
NITEO-DI-PHENYL-ETSANE
CCl3.CH(C.H3Br.N0,),.
[170°]. From C01,.0H(C„H,Br), and fuming
HNO, (Zeidler, B. 7, 1180). Needles (from
alcohol).
' CHLOEO . BEOMO - DI - OXY.(o)-NAPHTHO.
ftUINONE DIHYDEIDE C,»H,ClBrO, i.e.
yCO.C(OH)j
C.HZ I . [105°]. From bromo-oxj.
CHLORO-BROMO-PRnPANE.
48
'a).naphthoquinone and CI in HOAc. Needlea.
Oxidation gives a body [141°] (Zincke a. Gerland,
B. 20, 3216).
SI • CHLOBO ■ 01 ■ BROHO - TETSA . OXY-
DIPHENYL 05HClBr(OH)2.CjH01Br(OH)j.
[265°]. From di-diloro-tri-bromo-resoroin by
Bucoessive treatment with NaHSOj and with
tin and HCl (Benedikt, ilf. 4, 227).
CHLOBO-B BOIIO-DI-OXT-QUINONE
0,01Br(OH)20j [6:3:5:2:4:1] (Hantzsch a. Sohni-
ter, B. 20, 2279). From OT-di-ohloro-TO-di-
bromo-quinone and aqueous EOH (Erause, B.
12, 54) or tri-qhloro-bromo-quinone (Levy, A.
210, 163; B. 16, 1444 ; B. 18, 2370). Red leaflets
(oontaining aq) ; may be sublimed — K2A"2aq. —
Na^"2aq.— AgjA".
CHIOAO-BI-BBOMO-OXY.VALEBIC ACID
CsHjOlBrjOa. [169°]. Prepared by the addition
ol Br to ohloro-oxy-angelio acid (Pinner a. Klein,
B. 11, 1497). Sol. ether, insol. benzene.
CHIOaO-DI-BBOMO-PElTTABrE 05H,ClBr,.
From isoprene hydrochloride CjH,HCl and Br
(Bonohardat, C. B. 89, 1217).
Di-chloro-di-bromo-pentane
CH5.CHBr.OBrCl.CHCl.CH,. (0. 143°) at 31 mm.
Prom di-ohloro-amylene CH3.0H:0Cl.CHCLCHs
and bromine (Thurnlaokh, A. 223, 161).
Si - chloro - di - bromo - pentane CsHgCl^Br,.
(230°-240°). From di-chloro-amylene (146°)
and Br (Pinner, A. 179, 35).
. SI-CHLOBO-BBOmO-FHENOL
0;H,Cl^r(OH). [68°]. (268°) (Garzino, O. C.
1887, 1546). From (4,2,l)-di-chloro-phenol and
Br. Tri-ehloro- bromo -phenol CeHCl,Br(OH).
Bromine converts tri-chloro-phenol [67°] into
OjEjClaBrO [99°]. This is perhaps 0„H),Cl3(0Br);
it is converted, by heating under water, into
an isomeride, which is probably CjHCl3Br(0H)
(Benedikt, M. 4, 235).
TBI - CHLOBO ■ SI - BBOMO - 01 . PHENYL-
ETHANE CClj.CH(C,H.,Br)j. [141°]. From
bromo-benzene (1 pt.), chloral (2 pts.), and
HjSO, (Zeidler, B. 7, 1180). Silky needles.
Oi-chloro-di-bTomo-di-phenyl-ethylene
CClj:C(0,H<Br)2. [120°]. Formed by the action
of alcoholic EOH upon the preceding body
(Zeidler, B. 7, 1180). Needles (from alcohol).
/3. CHLOBO - a -BBOMO - 0 -PHENYL. FBOPI-
ONIC ACIO C,Ps.CHCl.CHBr.COjH. [182°]. From
a-bromo-j3-ozy-j3-phenyl-propionic acid and cone.
HClAq at 100° (Glaser, A. 147, 92). Monoclinio
tables (from ohloroform). BoiUng water forms
HOI and bromo-oxy-phonyl-propionic acid, to-
gether with a little phenyl-acetic aldehyde and
w-bromo-styrene.
a-CUoro - /3 - bromo - J3 - phenyl - propionic acid
C^5.CHBr.CHCl.C0jH. [185°]. From o-chloro-
/9-oxy-;8-phenyl-propionio acid and cone. HBrAq
at 60° (G.). Monoclinic tables (from chloroform).
Boiling water gives m-ohloro-stjrrene and a little
ohloro-oxy-phenyl-propionio acid, and phenyl-
acetic aldehyde.
o-Chloro-oi8-di-bromo-j8.phenyI-propionicacid
O5H5.CHBr.CBrCl.COjH. [136°]. Fromo-ohloro-
/3-phenyl-propionio acid and Br (Forrer, B. 16,
855). Tables (from water).
CELOBO-BBOHO-PHIHALIOE
C,Hj01Bi<[q^>0. [179°]. Formed by oxi-
dation of ohloro-bromo-naphthalene [67°] with
CrO, (Guareschi, B- 19, 1164).
Vol. n.
CHLORO - BROMO - PICBIN v. Chlobo-m-
BBOMO-NITBO-METHANE.
ci-CHLOEO-o-BROMO-PBOPANE CjH„ClBr i.e.
CHa.CHBr.CHjOl. Propylene chloro -bromide.
(120°). Formed in small quantity, together with
CHjBr.OHg.CHXl by treating allyl chloride with
fuming HBr (Beboul, A. Oh. [5] 14, 487). Con-
verted by alcoholic KOH into HCl and bromo-
propylene.
a-CUoro-w-bromo-propane CHj.CHCl.CHjBr.
(120°). S.G. 2 1-585. V.D. 5-52 (oalc. 5-45).
From propylene bromide by boiling with HgCl,
(Friedel a. Silva, Bl. [2] 17, 532). Alcoholio
EOH converts it into chloro-propylene (25°-30°).
Chloro -bromo -propane CjHjOlBr, (119°).
From ClBr and CgHj (Maxwell Simpson, Pr. 27,
119). Probably a mixture of the two preceding
bodies.
B-CMoro-S-bromo-propaueCHjBr.CHj.CHjCl.
Tri^methylenechhro-bromide. (142°). S.G. s 1-63.
From tri-methylene bromide and HgClj. It is
also the chief product of the union of HBr with
allyl chloride (Eebonl). Boiling alcoholio KOH
gives ethyl-allyl oxide.
o-Chloro - o- bromo - propane CHj.CClBr.CH,.
Acetorie chloro-bromide. (0. 95°). S.G. 21 1-474. .
From a-ohloro-propylene CHa.CChCHj and cold
cone. HBrAq (Eeboul, A. Oh. [5] 14, 482). Alco-
holic EOH gives o-chloro-propylene and allylene.
u-Chloro-oi-bromo-prapane CHs.CHj.CHClBr.
(111°). S.G. ^ 1-59. From a-chloro-propylene
CHj.CH:CHCl and HBr (B.). AlcohoUo KOH
gives CH,.CH:CHC1.
Chloro-di-bromo-propane CaHjClBr^. (198°),
From allyl bromide and ClBr. They unite slowly
in the cold (Maxwell Simpson, Pr. 27, 119).
w-CbloTO-coa-di-bromo-propane
CHj.CHBr.CHClBr (177° , cor.). From
CH3.0H:CHC1 and Br (Beboul, Bl. [2] 26, 278).
a-Chloro-wa-di-bromo-propane
CH3.CClBr.CH^r. (170°). S.G. 2 2-064 (Friedel,
A. 112, 237). From CH^.CChOHj and Br (F. a. S. ;
E.). With alcoholic EOH it gives 0,H<ClBr
and ethyl-propargyl oxide CHJC.CHjO.Et (Oppen-
heim, A. Suppl. 6, 372).
ai-Chloro-a;3-di-broma-propane
CH^r.CHBr.CHjCl. (195°) (O.) ; (203°) (E,).
S.G. * 2-085 (E.). From allyl chloride and Br
(0.). Also from epichlorhydrin /\
^ ' ch:3.oh.ch,ci
and PBr, or PCljBrjj (Eeboul, A. Suppl. 1, 230;
Darmstadter, A. 152, 320). Solid KOH gives
CHj:CBr.CH2Cl. Alcoholio KOH gives rise to
CHiC.CHrOEt.
a-Chloro-u3-di-broma-propaiie
CH2Br.CHCl.CH.^r. (200°). From glycerin
dibromhydrin and PCI5 (Berthelot a. de Luoa, J.
pr. 72, 317).
Chloro-tri-bromo-prop^ne CsH^ClBr,. (238°).
S.G. 14 2-39. From chloro -bromo -propylene^
(from glyoide) and Br (Eeboul, A. Suppl. 1, 231).
Bi-chloro-bromo-propane C,HsCljBr. (180°-
187°). From allyl bromide and ClBr at 100°
(M. Simpson, Pr. 27, 119).
w^-Si-cWoro-o-bromo-propane
CHjCl.CHBr.OHjCl. (176°). From s-dichlorhy.
drin and PBr^ (Berthelot a. de Luoa, /. pr. 17,
50
GIILORO-BROMO-rKOP A NE.
aia-Di-cIiloTo-0-bramo-propane
CHjCl.CHCl.CHjBr.FromOHjC1.0H{OH).OHjBr
and PBrj.
Di-eliloro-bromo-propane CjHjOljBr. (156°-
160°). From bromo-propylene and chlorine
(Linuemanu, A. 138, 123).
oia-Si-chloro-a^-di-bTomo-propane
CHjCl.CCIBr.CH-Br. (205°). S.G.22-161. From
CHaOLOCliCHj and Br (Friedel a. Silva, O. B. 74,
805; 75,81; BZ. [2] 17, 386).
ud-Si-cbloroTaiS-di-bromo-propane '
CH,Cl.CHBr.CHClBr. (221°) (F. a-Sl); (212°)
(Hartenstein, J.'pr. [2] 7, 313). S.G. 2 2-19 '(F.
a. S.);!I15 2-083 (H.). From CHjCl.CH:CHCl
and Br (E. ; F. a. S. ; H.).
oia-Si-chloro-ua-di-bromo-propane
CH,.CClBr.CHC]Br. (189°). From allylene di-
chloride and Br (F. a. S. ; Pinner, A. 179, 44).
Alcoholic KOH gives OsHjOl^Br (143°).
Si - chloro - tri - bromo -propane CsHjCljBr,.
[207°]. From di-ohloro-bromo-propylene (143°)
and Br (P.). Alcoholic EOH re-converts it into
CHjCljBr.
i8-CHL0K0-a.BE0M0.PK0PI01TIC ACID
CHjCl.CHBr.CO2H. [37°]. (c. 218°). Formed
by the action of HNO, on the product of the
union of BrOH with allyl chloride (Henry, B. 7,
757).
a-CMoro-;3-bromo-propionic acid
CHjBr.CHCl.CO2H. [37°]. (0.213°). Formed
similarly by oxidising the product of the union
of ClOH with allyl bromide |H.).
Chlaro-tri-bramo-propionic acid
CjHClBr3.C02H. [103°]. From chloro-bromo-
acrylic acid [70°] and Br (1 mol.) by heating for
2 hours at 100° ; the yield is 70 p.c. (Mabery a.
Weber, Am. 4, 104; 5, 255; P. Am. A. 17, 106).
Triclinic prisms (from OS,) ; v. sol. alcohol and
ether. Boiling baryta- water forms C,HCLBrj;
cold baryta-water gives chloro-di-bromo-aorylic
acid.— KA'aq.— CaA'j.— BaA'j: S. 23 at 20°.
Si-chloro-di-biomo-propionic acid
C2HCI^rj.C0jH. [95°]. Prepared by the com-
bination of di-chloro-acrylio acid [86°] by heat-
ing vrith bromine at 100° for several hours (Hill
a. Mabery, P. Am. A. VI, 140 ; Am. 4, 267 ; B. 14,
1679). Triclinic prisms, ffl:6:c = l-023:l:l-052;
a = 91° ; 0 = 76° 31' ; 7 = 108° 5^'. V. sol. water,
alcohol, and ether, m. sol. OS, or benzene.
Salts . — ^A'Ag : flat needles.— A'jBa : long
easily soluble needles.
a;3-Di-cUoro-j33-di-bromo-propiouic acid
COlBr2.CHCl.COjH. [100°]. Prepaiied bypassing
chlorine into di-bromo-acrylic acid at 100° ; the
yield is 96 p.c. (Mabery a. Nicholson, Am.. 6, 166 ;
cf. Am. 4, 270 ; P. Am. A. 17, 140 ; B. 14, 1680).
Monoclinic prisms, v. e. sol. ether and alcohol,
sol. hot OHCl, and OS,, si. sol. water.
Salts .— CaA'2 l^aq.— KA' 2aq.
Iri-chloro-bromo-propionic acid
CjHCljBr.COjH. [84°]. Prepared by passing
chlorine into a cold chloroform solution of
chloro -bromo-acrylic acid in sunlight. The
yield is 90 p.c. (Mabery, Am. 9, 1). Trimetric
prisms ; si. sol. water, sol. ether, alcohol, and
CHCl,. Its salts are unstable. — KA' 2aq : tri-
metric plates. — GaA'2 : oblique prisms. — BaA', :
gummy.
Tetra-chloro-bromo-propionic acid
CBrCl2.CClj.COjH. [225°]. Prepared bypassing
^hlorine into a solution q( bromo-propiolic acid
in chloroform, till the product orystallises oul
(Mabery, Am. 6, 155). SI. sol. CSj and chloro-
form. Its salts are unstable.
o-CHL0E0-j3-BE0M0-PE0PyL AI.COHOL
C3H,ClBrOi.e.CH2Br.CHCl.CHjOH. (197°). S.O.
2 1-764. From allyl bromide and HOCl (Henry,
B. 7, 409, 758). Oxidation gives ohloro-bromo-
propionic acid (o. su^d).
;3-Chloro-o-bromo-propyl alcohol
CHjCl.CHBr.CHjOH. (197°). S.G. " 1-759.
From allyl chloride and HOBr (H.). Oxidised
by HNO3 to chloro-bromo-propionio acid [37°],
(215').
Nitrate CHj(N0,).0HBr.CH20H. From
the alcohol, HNO3 and H2S04. Oil.
a,-chloro-a2-bromo-isoprot)yl alcohol .
CH2Br.CH(OH).CH2Cl. G%laro - brQmhycMn.
(197°). S.G. i2 1-740. From epichlorhydrin and
HBr, or from epibromhydrin and HCl (Beboul,
A. Suppl. 1, 225). Cone. EOH splits it up into
HBr and epichlorhydrin. Oxidation gives chlora
bromo-acetone [85°] (Theegarten, B. 6, 1212).
Also from epichlorhydrin and Br at 100° (Gri-
maux a. Adam, Bl. [2] 33, 257).
Ethyl ether C,Ilfi\Bt.OEt. (187°). From
0
A
epichlorhydrin CHJ.CH.CH2CI and EtBr at 200°
(Beboul a. Lourenijo, A. 119, 238).
CHLOBO-SKOIIO-PEOFYL-BENZENE v.
CuLono-DROMO-CDMENE.
CHLOEO-BEOMO-PEOPYIiENE CjH.ClBr i.e.
ca„:CCl.CH2Br. (121°). From a-chloro-allyl
alcohol and PBr, (Henry, C. B. 95, 849).
Chloro-bromo-propylene CHBr:CH.CHjCl.
(120°). S.G. ii 108. From/3-bromo-allylaleo.
hoi and PClj (Henry, B. 5, 453).
Chloro - bromo - propylene 0H2:CBr.CHjCl.
(127°) (E.);' (120°) (H.). S.G. 141-69 (E.). From
CH2Br.CHBr.CH2Cl and solid KOH (Eeboul, A.
Suppl. 1, 230 ; Oppenheim, A. Suppl. 6, 374).
From j8-bromo-alIyl alcohol and PCI5 (H.).
Ghloro-broino-propyleue CHs.CChCHBr (?)
(105°). From CH,.CCIBr.CH2Br and alcoholic
KOH (Friedel, A. 112, 237).
Di-chloro-bromo-propylenc CH3.CCl:CClBr(?)
(143°). From allylene di-chloro-di-bromide and
alcoholic KOH (Pinner, A. 179, 45). Br gives
CjHiCljBr, [207°].
CHLOEO-BBOMO-QTTIHOlSrE C,HjClBrOj
[172^]^ Formed by oxidation of chloro-bromo-
hydroquinone (Schulz, B. 15, 656).
m-Bi-chloro-m-di-bromo-quinone C.01~Br„0,
[6:2:5:3:4:1]. [233°].
Formation. — 1. Formed by the action of Br
on di-chloro-phenylene di-imide (from bleaching-
powder andi)-phenylene-diamine hydrochloride)
(Krause, B. 12, 53).— 2. By bromination of m-di-
chloro-quinoue CjHjCljOj [6:2:4:1] (Levy, B. 16,
1447). — 3. By brominationof ^-di-chloro-quinona
CACljOj [6:3:4:1] (Levy, B. 18, 2367); in this
case one of the 01 atoms must undergo trans-
position from the p to the m-position. — 4. From
hydroquinone, cone. HCl and Br (Benedikt. M.
1, 347).
Properties. — Monoclinic golden-brown tables ■
a:h:c = 1-445:1:3-0286 ; j8 = 74° 31' (L.). SI. sol.
ether and alcohol, insol. water.
Beactions. — It is very readily reduced by
hydroxylamine hydrochloride to the correspond-
ing hydroquinone [234°], whose acetyl derivatir*
CHLORO-BUTANE.
51
melts at [270°] (Hantzsoh a. Schniter, B. 20,
t279). By boiling with aqueous alkalis it is
converted into a ohloro-bromo-di-oxy-quinone
C«CIBr(OH)jO..
Tri-chloro-bromo-qninone CjOljBrOj. From
tri-chloro-quinone and Br at 130° (Stenhouse,
A. Stvppl. 6, 219). Also from tri-ehloro-bromo-
hydroquinone and cono. HNOs (Levy a. Sohultz,
A. 210, 162). Golden monoolinio pyramids;
o:6:<! = l-48:l:2'95; i8 = 74° 41'. Sublimes at
160°- Dilute KOH gives ohloro-bromo-di-oxy-
quinone.
CHLOBO-SI-BBOKO-BESOBCIN
0,HBrjCl(OH)2. [105°]. Got by adding excess
ol bromine water to a solution of ohloro-resorcin
at 80°. . Crystallises from water in silky needles
(G. Beinhard, J.pr. [2] 17, 325).
CMoro-di-bromo-resorcin C|,HBr2C!l(0H).j.
[86°]. From C8HBr,Cl(0Cl)(0Br) and NaHSO,
(Benedikt, U. 4, 227).
Si-chloro-bromo-reisorcin CeHBrClj(OH)j.
[100°]. From Br and di-ohloro-resorcin. Silky
needles (from water) (B.).
' Di-chloro-tri-bromo-resorcin CsECl^BrgO, i.e.
C,HBr2Ca(0Cl)(0Br)(?) Formed by adding Br
(216 g.| dissolved in cone. HClAq (1,000 o.c.) to
a solution of resorcin (50 g.) in water (2,000 o. c.)
(B.). Yellow crystals. At 175° it gives crystal-
line Oi^CljBrjO, which is reduced by tin and
HCl to di-chloro-di-bromo-tetra-oxy-diphenyl.
Tri-chloro-di-bromo-resorciu 0^01,(051)^
[100°]. , Prepared by adding Br to tri-ohloro-re-
sorcin suspended in dilute HCl (B.). Small
golden crystals. Gives oS Br (1 mol.) on heat-
ing. Beduced by tin and HCl to tri-ohloro-
lesorcin.
HEXA-BBOMO-TEI-CHLOBO-DI-THIENYL-
ETHANE CCl,.CH(C^Br,S)j. [176°]. Formed
by bromination of di-thicnyl-tri-chloro-ethiine
(Peter, B. 17, 1343). White crystalline powder.
V. sol. ether and chloroform, si. sol. alcohol.
Does not give the indophenine reaction.
CHLOBO-BBGMO-THTUOQUINONE
CeMePrClBrOj [1:4:5:2:3:6]. [78°]. J'ormed
by bromination of m-cbloro-thymoquinone
C,IIMePrC102[l:4:5:8:6]. Yellowplates (Schniter,
B. 20, 1319).
Chloro-bromo-thymoqniuone CgMePrClBrOj
[1:4:2:5:3:6]. p -Chlpro- benzyl brormde. [87°].
Formation. — 1. By oxidation of the corresponding
hydroquinone with Fe^CIo. — 2. By bromination of
0-chloro-thymo-qninoneC,HMePrC10j[l:4:2:8:6].
Golden-yellow plates (Schniter, B. 20, 1318).
^-0HLOBO-<»-BBOMO-TOLUElirE C,HeClBr
i.e. C,H<Cl.CH^Br. [48-5°] (225°-230°). From
p-ohloro-tolnene and Br (Jackson a. Field, Am.
1,102). White needles (from alcohol); aromatic
odour ; volatile in the air.
ai-Chlaro-p-bramo-tolnene CsHfBr.CEjCl. &•
Brotno-bemyl chloride. Obtained, mixed with
an equivalent quantity of CjHjBr.CHjBr, by
brominating benzyl chloride (Errera, 0. 17, 193).
NaOBt converts it into CjH^Br.CHj.OEt (243°).
Di-chloro-bromo-toluene G,B.fil^r. (280°-
290°) (Jackson a. Field, B. 11, 905).
CHLOBO-BEOMO-TOLUQUINOIIE
CiHMeClBrO,. [111°]. From the hydroquinone
[123°], by oxidation. Thick needles. V. aoL
ether, benzene, and chloroform; scarcely sol.
Ifater (Schniter, B. 20. 2287).
Chloro-bromo-tolucLuinone C„HMeClBiOi.
[150°]. From the hydroquinone, [121°], by oxi-
dation. Glistening yellow plates (from' alcohol)
(Schniter, B. 20, 2287).
TBI - CHLOEO - DI - BBOMO - DI - TOLYL -
ETHANE C,,H„Cl^rj. [148°]. From tri-ohloro-
di-tolyl-ethane and fir in CS, (O. Fischer, B. 7.
1191).
DI-CHLOEO-BROMO-VINYL-BENZOICACID
C,H.CL,BrOj i.e. CCIBr:CCl.CeH4.C0jH. [174°].
From' CsH<<;^°j2^>CClBrand alcoholic NaOH
diluted with water (Zinoke a. Frohlich, B. 20,
2056). Needles.
Methyl ether MeA'. [82°].
CHLOBO-BTJTANE v. Butti, ohloridb.
oo-Di-obloro-butane CHs.CClj.ckj.CHj. (96°).
From methyl ethyl ketone and PCI5 (Bruylants,
B. 8, 412), Dry KOH gives CH:C.CH2.CH3. Al-
coholic KOH gives CHj-C-CCH^ (Favorsky, Bl.
[2] 45, 247).
ow-Si-chloro-isobatane (CH,)jCH.CHCl2.
Isobutylidene chloride. (104°). S.G. ^ 1-011.
V.D. 127 (H = 1) . From isobutyrio aldehyde and
PCI5 (Oeeonomides, C. R. 92, 884). Aqueous NH,
at 180° gives chloro-isobutylene (67°).
Bi-chloro-ieobntane C^HgCl^. (107°). From
chloro-isobutylene CH2:CMe.CH2Cl and , cone.
HCl (Ch^ohoukoff, Bl. [2] 43, 112).
Di-Bhloro-bntane O^H,Clj. (128°) (P.); (125?)
(Faraday). S.G. 2S 1-112. V.D. 4-43. Formed by
union of CI with the mixture of butylenes (3. v.)
obtained by treating isobutyl alcohol (25 pts.)
with H^SO, (25 pts.), CaSO, (40 pts.), and K^SO,
(10 pts.) (Puohot, A. Ch. [5] 28, 508 ; cf. Faraday,
2V. 1825, 440 ; Kolbe, A. 69, 269 ; 64, 339).
Di-obloro-butane O^HgClj. (106°). From tert-
butyl chloride and CI in daylight (D'Ottreppe de
Bouvette, Belg. Acad. Bull. [3] 4, 359).
Tetra-chloro-butaue G,Hfil^ i.e.
CH,.CCL,.CHCl.CHjCl. (85°) at 10 mm. From
tri-chloro-butyl alcohol by gradual addition of
PCI5 (Garzarolli-Thurnlaokh, A. 213, 372). Oil.
Tetra-chloro-butane
CHjCl.CHCl.CHCl.CHjCl. Butinene tetra-chlo-
ride. [73°]. From butinene and CI. Also from
erythrite and PCI5 (Henninger, Bl. [2] 34, 195).
Prisms.
Tetra-cMoro-iso-butane CClj.CMesCl. ZVt-
chloro-tri-methyl-carlmvyl chloride or chloro-
isobutyro-tri-chloride. (167°). Strong odour.
Formed, together with hexa-ohlpro-di-ferf-butyl
oxide (CCL.CMeJjO, by the action of PCI5 upon
acetone-chloroform (WUlgerodt a. Diirr, B. 20,
539).
Heza-chloro- butane G,H,Clg. (148°) at
50 mm. S.G. 12 1-67. A liquid formed by the
action of chlorine on isobutyl iodide (Prunier,
Bl. [2] 24, 24).
Hexa-cbloro-bntane C^HjCl,. Formed by
the action of chlorine on C4H8CI2 (from isobutyl
alcohol) in sunlight (Puchot, C. B. 85, 757).
Oil. Converted by KOH into 0,H,C1„ O.Olj,
and G4CI4.
Eeza-chloro-butane C^HjCl,. (c. 115°) in
vacuo. From tert-hutyl chloride and chlorine
in sunlight (d'O. de B.).
Hepta-chloro-bntane C4H3CI,. [36°]. (126'»-
135°) in vactm. From ter<-bntyl chloride and
CI in sunlight (d'O, de B.).
■ 9
62
CHLOKO-BUTANE.
Hepta-cHoro-butsne CjHaOl,. [42°]. (135°-
' 145°) in vacuo. Formed at the same time as
the preceding.
CHLOEO - BUTANE TETRA - CABBOXyilC
ACID CCl(C02H)2.C(CjE5)(C02H)2. Ethyl-cHloro-
acetyUne-tetra-carboxylic acid.
Tetra-ethyl-ether A'-Et,. S.G. |§ 1-076.
Formed by ohlorination of butane-tetra-oar-
boxylio ether. Oil {Bisohoff a. Each, B. 17,
2786).
CKLOBO-BUTENYL ALCOHOL OiH,C10.
Chloro-crotyl hOcohol. (158-3° i.V.) at 742-5 mm.
S.G. m 1-1312. V.D. 3-60 (for 3-68). From
tri-ehtoro-butyl alcohol by zino-dust and HOI
(GarzaroUi-Thurnlaokh, A. 213, 375). Crystal-
lises in a freezing mixture. Smells like allyl com-
pounds, M. sol. water, but separated by K^COj
or NaCl. Forms with Br in CHOlj chloro-di-
bromo-butyl alcohol, which is' very unstable.
If it be oxidised by HNOj it forms ohloro-di-
bromo-butyrio acid (not isolated), which is
reduced by zino-dust and HCl to ohloro-crotonic
acid [97°].
Acetate (168°-169°) iat 741mm. V.D.
S-23 (for 5-14). Colourless fruity liquid, heavier
than water. V. si. sol. water.
CHLOSd-BTITIlfENE CJisCl. (65°). From
di-chloro-butylene CHs.CHiCH.CHClj and alco-
holic KOH (KekuU, A. 162, 99).
Hexa-chloro-butinoue 0,Cls. [39°]. (284°).
From s-hexyl-iodide and ICl, at 100^-240°
(Krafft, B. 10, 803). Thin prisms (from
alcohol).
TBI -CHLOKO- BUTYL ACETATE
CACljOAc. (217-5°) at 733 mm. S.G. |°
1-344. From tri-chloro-butyl alcohol and AcCl
at 110° (GarzarolU-Thurnlaekh, A. 213, 373).
o-CHLOaO-ISOBTJTYL ALCOHOL C,H„CIO
i.«. (pHs)2CCl.CH20H Butylene-gVycol chlorlvy-
drin (137°). From isobutylene and HCIO (But-
lorow, A. 144, 25). SI. sol. water. Beduced by
sodium-amalgam to isobutyl alcohol. Oxidised
by HNO3 to chloro-isobutyric acid (Henry, B. 9,
1034).
ChloTO-£ec-bntyl alcohol. Ethyl ethe'r
CH3.CHj.CH(0Et).0H,Cl. (141°). S.G. 2 -9735.
From di-chloro-di-ethyl oxide and ZnEt^ (Lieben,
A. 123, 133).
Di-chloro-iert-butyl alcohol C^HsGl.O. (143-5°
i.V.). S.G. 2 1-0335. From (CHsljCrCHCl and
HOlO (Oecouomides, G. B. 92, 1235).
3^-chIoro-butyl alcohol
CH,.CCl2.GHCl.CH2.0H [62°]. (120°) at 45 mm.
From tri-chloro-butyric aldehyde (butyl chloral)
and ZnEtj, ZnPr^, or 2;n(CHjPr)j, followed
by water, thus: .C3H4Cl3CHO-i-Zn(C2Hs)a
= C^H^Gla.CH^OZnCjHs + CjH, (Garzarolli-
Thurnlaokh, A. 213, 370 ; 223, 166). Also from
urochloralic acid and ECl (Mcring, S. 4, 93).
Prisms (from ether). V. sol. alcohol or ether, si.
sol. hot water. Sol. warm cone. H^SO^, but de-
composed by heating the solution.
Reactions. — 1. PCI, has hardly any action.
2. Fuming HBr at 110° has no action 3. PCI5
gives tetra-chloro-butane.— 4. Fuming. HNO3
gives tri-chloro-butyric acid. — 5. Zinc-dust and
HCl reduce it to chloro-butenyl alcohol {q. v.).
Tri-chloro-tert- butyl -alcohol «. Acetoke-
CHIiPBOrOBV.
CHLOKO-ISO-BTrTYL-ISO-AMYL-GLYOXAI,.
INE (7) C,jH2,ClNj. CMoro-oxalamyUiie. (267°-
270°). Prepared from di-isoamyl-oxamide in
the same way as ohloro-oxalethyline from di-
ethyl-oxamide (Wallach a. Sohulze, B. 13, 516 ;
A. 214, 316).
Salt s.-(B'HCi;) jPtCl,.— B'HCl.
7-CHL0»0-n -BUTYL -BENZENE Ci„H„Cl
i.e. C,H,.CHC1.C,H,. From CeH,.CH(OH).CaH,
and HCl (Engler a. Bethge, B. 7, 1128). Liquid.
CHLOBO-ISO-BUTYLENE (CH,),C:CHCl. Iso-
hutmiyl chloride. Isocrotyl chloride, (c. 65°).
S.G: i^ -979. V.D. 89-7. From isobutylidene
chloride (CH3)jOH.CHCl2 and alcoholic KOH or
NH3. Formed together with (CH3)jCH.CHCV,
by treating isobutyric aldehyde with PCI5 (Oeco-
uomides, C. B. 92; 884, 1235 ;, Bl. [2] 35, 498).
Formed also by the action of chlorine on iso-
butylene, especially below 0° (Scheschuko^ J- B.
16, 493; Bl. [2] 41, 253; 43, 127). Converted
by water at 90° into isobutyric aldehyde.
Chloro-isobutylene CHj.C(CH2Cl):CH2. Bute-
nyl chloride, (c. 73°). S.G. 2 -955. Formed,
together with the preceding, by chlorinating iso-
butylene, especially above 0° (S.). Heated with
aqueous K^CO, it forms isobutenyl alcohol (113°).
HCl forms C^B^Ol^ (107°), whence KjCOa gives
C,H,(OH), (178°).
Di - phloro - n - butylene CHj.CHiCH.CHClj.
(126°). S.G. 32 i-iai. From orotonic aldehyde
and PCI5 (KekuK, A. 162, 98). Alcoholic KOH
gives C,H,C1 (65°) and C.HsCl.OEt (134°). Br
gives C^HjCl^rj whence aqueous K^CO, gives
0,H,ClBr(OH)j (0. 118°).
Tetra-chloro- butylene C^H^C1^. (200°).
From tri-ohloro-butyrio aldehyde and PCI,
(Judson, B. 3, 790). ,
Penta-chloro-butyleno C^HjCl,. (187°) at
460 mm. From teri-butyl alcohol and chlorine
(Lieben, B. 8, 1017).
TEI-CHLOE-BUTYLIDENE-IMIDE
CH3.CHCl.CCl2.GH:NH. [164°-165°]. (P. a.K.);
[170°] (S.). Prepared by the action of ammo-
nium acetate on tri-chloro-butyric ortho-alde-
hyde (hydrate of butyrochloral) (Pinner a. Klein,
B. 11, 1491). Also by heating tri-ohloro-butyrio
aldehyde-ammonia with benzoic aldehyde (E.
Schifl, Q. 9, 4^8). Sol. alcohol, ether, hot water
and hot benzene.
o- CHLOEO- ISOBUTYL -IIAIONIC ACID
CA.CCl:(OOjH)j. Di-ethyl-ether A"Et,.
(246°). B.G. ^ 1-091. Prepared by the action
of chlorine on isobutyl-malonic ether. Liquid. '
On saponification with KOH it gives iso-butyl-
oxy-malonio acid (Conrad a. Bisohoff, B. 13, 600;
A. 209, 237).
HEXA-CHLOEO-DI-TEET-BUTYL OXIDE
0,H,sCl„0 i.e. (CCls-CMeJ^O. 'Acetone-chloro-
form etJur.' (156°). Formed, together with
COls.CMeaOH, and its oily isomeride, by the
action of PCl, upon acetone-chloroform (Will-
gerodt a. Durr, B. 20, 539). Liquid. Volatile
with steam. Very pnngent.
o-CHLOBO-Ti-BUTYEIC ACID C.H.CIO, ».«.
CH3.CHj.CHCl.C0,H. From its chloride and
water. Thick liquid, v. sol. hot water.
Chloride OHj.CHj.CHCl.COCl. (c. 181°),
S.G. n 1.257. Formed by chlorinating butyiyl
chloride in presence of iodine (MarkownikoS.
4. 163, 241 ; cf. Z. [8] 4, 621),
OnLOEO-BUTYRIO ALDEHYDE.
S3
Ethyl ethit EtA'. (c. 158°). S.G. ^'
1-063 {if.).
/S-Chloro-tt-bntyrio add
CH,.0H01.0Hj.COsH.
Formation. — 1. By saponification of allyl
cyaniae by HCl (Pinner, B. 12, 2056).— 2. By
oxidation of the corresponding aldehyde (Earct-
nikoff, J. R. 11, 252).— 3. By treating the
hydrochloride of /3-chloro-butyric imido-ethcr
CH,.CHCl.CHj.C(NH)(OEt) with water ' (Pinner,
B. 17, 2008).
Eeactions. — Boiling baryta-water forms HCl
and orotonic acid.
Ethyl ether EtA'. Yo. 170°). S.G. s
1-072 (Ba.); f 10517 (Br.), ni, 1-4.S0. B.^,
S9'l. Obtained by chlorinating butyric acid
(Balbiano, B. 10, 1749; 11, 348; G. 10, 137).
Probably the same compound is got by satu-
rating an alcoholic solution of orotonic acid
with HCl (Briihl, A. 203, 28). Converted by
EOH into orotonic acid and i3-oxy-butyrio acid.
Heated with alcoholic NH, it gives jS-amido-
kutyramide.
7.Chloro-butyrio acid OHjCl.CHj.CHj.COaH.
[10°]. S.a 12 1-250. From the nitrile by HCl
(Henry, C. B. 101, 1158). Viscous liquid or thin
laminiB, si. sol. water. At 190° it splits up into
HCl and the lactone of y-oxy-butyric acid.
Methyl ether MeA. (174°). S.G. |g 1-891.
From the nitrile, MeOH, and HCl.
Ethyl ether EtA'. (184°). S.G. M 1-122.
Chloride CHjCl.CH,.CHj.COCl. (174°).
S.G. ig 1-268.
Amide CH.,01.0Hj.CH„.C0NHj. [90°].
Nitrile CHjCl.CHj.CHj.CN. (196°). S.G.
Jg 1-162. From CHjCl.CHj.CH,Br and KCy.
a-Chloro-isobutyric acid (CH3)2CC1.C02H.
From (CH,)jCCl.CHjOH by oxidation with HNO,
(Henry, £1. [2] 26, 24). Formed also by chlori-
nating isobutyrio acid (Balbiano, J?. 11, 1693).
Ethyl ether EtA'. (149° cor.). S.G. a 1-062.
Converted by alkalis into oxy-isobutyric, metha-
crylic, and * di-batyllactic ' (CaH„0,) acids (Testa,
6. 10, 377).
a;3-I)i-chloro-btttyric acid
CH,.CHCl.CHCl.COjH [63°]. Formed by com-
bining solid crotonio acid with chlorine, in CSj
solution. Large glistening colourless prisms.
By aqueous NaOH at the ordinary temperature
it is converted into a22o-a-chloro-crotonic acid
[66°]. If the solution is heated during the re-
action some ordinary a-chloro-crotonic acid is
formed simultaneously. On heating the neutral
alkaline salts in aqueous solution ai2o-a-chloro-
propylene is formed (Wislicenus, B. 20, 1008 ;
Michael a. Brown, Am. 9, 281 ; J.pr. [2] 36, 174 ;
ef. Friedrich, A. 219, 371).
Salts. — AgA'. — ^BaA'j! gummy.
Methyl ether MeA'. (84°) at 23mm.;
(177°). S.G. ? 1-2809 (Zeisel, M. 7, 368).
Ethyl ether EtA'. (96°) at 35mm. Con-
verted by alcoholic EOH into a-chloro-crotonic
acid [98°].
Chloride CH,.CHCl.CHCl.COCl. (164°).
From orotonic aldehyde and chlorine (Z.).
.iZ2o-a)3-di-chloro-butyric acid
CH3.CHCI.CHCI.CO2H. Liquid. Formed, to-
gether with some solid a;8-di-chloro-batyric acid
x[63°], by combination of liquid iso-crotonio acid
with 01. By excess of cold aqueous NaOE it is
converted into ordinary o-ohloro-crotonio acid'
[99°]. On heating the neutral aqueous solution
of the alkaline salts, ordinary a-chloro-propyjena
(80°) is formed (Wislicenus, B. 20, 1009).
A di-chloro-butyric, acid is formed by chlori-
nating n-butyrio acid in sunlight (Pelouze a.
G^lis, A. Oh. [3] 10, 434 ; Naumann, A. 119, 120).
ao-Di-chloro-butyric acid. Anilide.
CH,.CHj.CClj.O.NHPh. [200°]. From aniline
ethyl-malonate and PClj (Schramm, B. 21, 289).
Distillation with aqueous NajCOa converts it into
NPh:CH.O.C01Et.CO.NHPh which yields phenyl-
oarbamine when boiled with cone. EOBAq.
o-Toluide CH3.CHi.CClj.ONH0,H,. Pro-
pared in a similar way. la converted by aqueous
Na,CO, into NC,H,:CH.O.CClEt.CO.NHC,H,.
[107°].
Tri-cMoro-butyric acid CHj.CHCl.CCL.COjH.
[60°] (E.) ; [58°] (G.). (237°). S. 4. Formed
by oxidising tri-chloro-butyrio aldehyde (Erauier
a. Pinner, B. 3, 389 ;" Judson, B. 3, 785 ; Eahl-
baum, B. 12, 2337). From the alcohol and
fuming HNO3 (Garzarolli-Thurnlackh, A. 213,
374 ; 182, 185). The Silver salt when boiled with
water gives di-chloro-propylene (78°). — ^AgA'. —
CaA'.,.— PbA'j.
Ethyl ether EtA'. (212^).
Chloride CH,.CHCl.CClj.COCl. (0. 164°).
Amide CHj.CHCl.GHj.CONHj. [96°].
Tri-chloro-butyrie acid
CHjCl.CH2.CClj.COjH. [75°]. S. 5. From the
corresponding aldehyde and fuming HNO3 (Nat-
terer, M. 4, 539 ; 5, 251),
Tri-chloro-isobutyric acid C^HsClsOj. [50°].
Separates when chlorine is passed into an aqueous
solution of sodium ^itraconato (Gottlieb, J. pr.
[2] 12, 1). Prisms. Boiling alkalis convert it
into di-chloro-methacrylic acid. Zinc-dust and
HCl form chloro-methacrylic acid.
Salts.— NH^A'.—BaA'j.—PbA'j.— Aniline
salt NHjPhHA'. [164°] (Daocomo, J. 1884,
1385).— [4:l]CsH,Me.NH3A'. [154°] (D.).
Tetra-chloro-butyric acid C,HjCl,,Oj. [140°].
From n-butyric acid and CI in sunlight (Pelouze
a. G61is, A. Ch. [3] 10, 434).
/S-CHLOBO-n-BUTYRIC ALDEHYDE
C^HjClO i.e. CH3.CHCl.CHjCH0. [97°]. From
crotonio aldehyde and gaseous HCl (Eekuld, A.
162, 100). Needles (from dilute alcohol) ; insol.
water.
Tri-chloro-butyrie aldehyde
0H,.CHCl.CClj.CH0.
Butyl-chloral. Mol. w. 1751 (165°). S.G.
'j" 1-3956. 11^ 1-482. »„, 67-99 (Briihl, A. 203,
20).
Formation. — 1. By the action of chlorine on
aldehyde (Pinner, A. 179, 21 ; B. 3, 383 ; 8, 1561).
2. From chloro-acetic ortho-aldehyde by heating
with an equivalent quantity of aldehyde and a
trace of HCl ; the oily product (a-chloro-crotonic
aldehyde) being subsequently chlorinated (Lieben
a. Zeisel, M. 4, 531).
Properties. — Liquid; combines with water
forming a crystalline hydrate, whence it ia
liberated by ^stillation in a current of HCl.
Oxidation gives tri-chloro-butyrio acid. PCI,
gives C^H^Cl^ (200°).
Beactions. — 1 ZnMcj in ether followed, after
a time, by water gives tri-chlbro-amyl alcohol
(CsH^CyCHMeOH.— 2. ZnEtj (1 mol,) gives oft
bthylene, and the residue when treated with
64
CHLORO-BUTYRIO ALDEHYDE.
water forms tri-ohloro-butyl alcohol (QarzaroUi-
Thnrnlaokh, il.,213, 370).— 3. Tri-cUoro-lactio
acid at 130° gives C01j.CH<^q >CH.CsHiCl3
[107°] (Wallach, A. 193, 47).— 4. Lactic acid
gives CHa.CH<;°Q >CH.C3n^Cl, (201°). — 6.
Tri-chloro-ozy-valeric acid at 176° slowly forms
O.Cl,H,Cn<°Q^CH.C3Cl3H, [85°]i (300°-
310°) (W.).— 6. PHJ forms C^HijCl^POj [06°]
(Girard, A. Gh. [6] 2, 52). Split up by cone
NaOHAq into HCl, HsPO,, CjH,Clj, formic acid
and hydrogen.
Combinations. — 1. With • water : —
Tri - chloro - butyric ortho - aldehyde
OH,.CHCl.CCl2.CH{OH)2. Mol. w. 193A. [78°]
(K. a. P.) ; [75°] (L. a. Z.). V.D. 3-33 (oalc. 6-7)
(Moitesier, C. B. 90, 1075). Trimetric laminse ;
a:&:c = -65;l:l'2. Dissociated by heat. Be-
actions. — (a) Converted by boiling Na^COjAq
into di-chloro-propylene (77°) which on oxida-
tion with CrOj yields acetic acid.— (6) Zn and
HCl reduce it to chloro-crotonic and crotonic
aldehydes (Sarnow, A. 164, 108). — (c) Iron and
HOAo give butyric aldehyde, w-butyrio alcohol,
and butenyl alcohol (Liebena. Zeisel, Jf. 1,840).
— (d) After being taken into the system it is
excreted in urine as tri-chloro-butyl-gly-
curonio acid C,„H,5C1,0, (Mering, H. 6, 491;
Kiilz, J. Th. 1882, 95). This acid crSrstallises
in silky needles, is Issvorotatory, and split up
by boiling dilute acids into glycuronic acid and
tri-ohloro-butyl alcohol. — (e) Heated with dry
NH^OAo it forms C,H,C1,NH [165°] (Pinner, a.
Klein, B. 11, 1491) ; [170°] (Schiff, B. 11, 2167).
2. With hydrogen cyanide: —
Tri-ehloro-oxy-valeronitrile
CH,.CHCl.CClj.CH(OH).CN. [102°]. (c. 230°).
This is converted by alcoholic NH, into chloro-
crotouamide ; and by HjSO, into tri-chloro-oxy-
valeramide. Heated with urea it yields chloro-
orotonyl-urea CH,CH:CCl.CO.NH.CO.NHj as
chief product (about 60 p.c.) and butyro-
chloral-biuret
.'NH.COv
CH3.CHCl.CCL.CH<^g;^o>NH as a by-
product (about 6 p.c.) (Pinner a. Lifsohiitz, B.
20, 2347) .
3. With acetamide :— C4H5Cl3(OH)(NHAc).
[170°] (Pinner, A. 179, 40); [158°] (Schiff a.
Tassinari, B. 10, 1785). Tables; v. si. sol. water.
4.Withbenzamide:— C^H5Cl,(0H)(NHBz).
[150°] (Pinner, A. 179, 40) ; [133°] (Schiff a.
Tassinari, B. 10, 1785). Formed by melting
tri-chloro-butyric aldehyde with benzamide.
5. With carbamic ether: —
CjH,Cl3(OH)(NH.C02Et). [125°]. From tri-
chloro-butyrio aldehyde, carbamic ether, and
HCl (Bischofl, B. 7, 632). SmaU prisms.
6. With ammonia:— [62°] (S. a. T.).
7. With alcohol:-
CH,.CHCl.CClj.CH(OH)(OEt). Oil (P.).
8. With acetyl chloride: —
CH3.CH01.CH,.OH(OAo)Cl (220°).
Tri-obloro-butyric aldehyde
OH2CI.CH2.CCl,.CHO. [-78°]. From oy-di-ohloro-
crotonic aldehyde CHjCl.CH:CCl.CHO and HCl
(Natterer, M. 4, 551; 5, 253). Forms no
bydrate.
j8- CHLORO .BU1YB1MID0-ETS?I,-£THES
C3H„Cl.C(NH).0Et. Thehydrochlorideis formed
by passing HOI into a mixture of allyl cyanide
(1 mol.) and ethyl alcohol (1 mol.). The hydro-
chloride (B'HOl) crystallises in large colourlesa
prisms (Pinner, B. 17, 2007).
CHLOEO-CAFF£IN£ v. Caffeine.
CHLOBO-CAHFHOB v. Gampbob.
CHIOBO-CAFBOIC ACID v. CHi.oBO-HEZoia
Acm.
CHLOBO-TBICABBALLTLIC ACID. Methyl
ether CHj(C02Me).CCl(COjMe).CH2(COjMe).
From tri-methyl citrate and PCI, (Hun'ieus, B. 9,
1750). Oil ; split up by beat into HCl and tri-
methyl aconitate.
TBI-CHLOEO-CAEBAZOLE CuHjCljN. [180°].
Prepared by passing chlorine into acetic acid
containing carbazole in suspension until the mass
appears bright green (Grajbe, A. 202, 27).
Needles ; sol. benzene, ether, and alcohol. Its
solution in cono. H^SO, is bright green. Its
picric acid componnd [100°] forms red.
needles. '
Heza-chloro-carbazole CuHjCleN. [225°]..
Obtained by further chlorin^ation of the above..
Long needles; its solution in cone. H^SO^ is;
yellowish-green.
Octo-chloro-oarbazole CisHCljN, [275°]..
Formed by chlorinating the above in presence
of SbClj. Long needles, si. sol. alcohol. Further
chlorination in presence of SbCl^ at 160° gives:
hexa-chloro-benzene.
CHLOBO-CABBONIC ETHEE v. Chlobo-fob-
MIO BTHEK.
(3)-CHL0B0-CABB0STYBII CHjClNO i.e.
XH:C01
CjHjC^ I (Py. 3, Z)-Chloro-oxy-gmm»-
\n : C(OH)
lime. [242°]. Formed by heating di-chloro-quiaicr-
line [104°] with dilute HCl to 120°. By PCSj it
is converted back into the dichloro-quinoline
[104°] (Friedlander a,. Weinberg, B. 15, 336,
2679).
Ethyl ether C3HjCLN(0Et) : liquid, volatUe
with steam.
Chloro-carbostyril C„HjNOCl. [246°].
Formed by boiling a dilute HCl solution of
o-amido-phenyl-propiolio acid (Baeyer a. Bloem,
B. 15, 2148). Sublimable. Silky needles. SI.
sol. hot, insoL cold, wattr. May be identical
with the above.
Di-cMoro-carbostyril C.HsCljNO. [249°].
Formed by chlorination of carbostyril (Fried-
lander a. Weinberg, B. 15, 1425). Fine white-'
needles. PCI. converts it into tri-chloro-quino-
line [161°].
DOBECA-CHLOBO-CEBOTIC ACID
CjjHjoClijOj. From cerotio acid and ohlorine-'
(Brodie, A. 67, 190). Gummy mass. EtA'.
CH10BO-CETYLALCOH01C,JH3,010. (300°).
From oetene CuHjj and cold dilute HCIO"
(Carina, A. 126, 195). Liquid. KOH gives ■
C,„H3,0 [30°] (300°).
DI-CHLOBO-CHEIIDAMIC ACID v. Cheli-
DONIC AOIO.
HEPTA-CHLOEO-CHOLESTEEIN v. Choles-
lEBIN.
CHLOBO-CHBOMIC ACID. Name sometimes j
given to CrO„C\.„ v. Cmiotnmi, Oxy chlorides of. ..
CHLOEO-CHRYSEN £ v^ Chrysemb.
a-CHIOBO-CmirAUIC ACID
CHLORO- COMPOUNDS.
6&
0^s.CH:CCl.COjH. a-Chloro-&-plienyl.acryUo
add. [142°]. >
Formation. —1. By heating sodium ohlorp-
acetate with acetic anhydride and benzoic alde-
hyde (Ploohl, B. 15, 1945).— 2. By heating o-
ohloifo-/3.oxy-j3-phenyl-propionio aoid withNaOAc
and AcjO (Forrer, B. 16, 854).— 3. Together with
a small quantity of the $ isomeride by heating
O.H,.CHCl.CHCl.COjH with aloohoUo KOH
(Jutz, B. 16, 788).— 4. By digesting benzoyl-
acetic ether with PCI, and POCl, at 100° (Parkin,
G. J. 47, 240). In this reaction the $ acid might
have been anticipated. Needles. Volatile with
steam. V. si. sol. water, v. sol. alcohol and ether,
g1. sol. ligroin.
/3.Chloro-cinnamic acid CHj.CChCH.COjH.
? Allo-a-chlaro-dnnamic acid. [114°]. Formed
as above (Formation 3) and separated from the
a-acid by the smaller solubility of its potassium
salt in i^cohol. Trimetrio crystals (Haushofer,
Z. K. 8, 382, 389).
o-Chloro-cinnamic acid
[2:l]C^jCl.CH:CH.C0,H. [200^]. (G. a. H.) ;
[196°] (S.). Formed by boiling o-diazo-cinnamio
aoid with strong HCl (Gabriel a. Herzberg, B. 16,
2036). Also by heating o-chloro-benzylidene-
malonic acid to its melting-point (Stuart, C. J.
S3, 141). Sol. alcohol, ether, and acetic acid,
nearly insol. petroleum-ether and hot water,
»i-Chloro-cinnamic acid
[3:ljC„H.C1.0jH2.C02H. [167°]. Formed by
boiling m-diazo-cinnamic aoid with strong HCl
(G. a. H. B. 16, 2038). Needles. V. sol. hot
water, hot alcohol and ether, si. sol. benzene
and petroleum-ether.
^-Chloro-cinnamic acid
[4:l]CsH,Cl.C2H,.C02H. [242°]. Formed by
boiling ^-diazo-cinnamic acid with strong HCl
(Gabriel a. Herzberg, B. 16, 2039). V. sol.
alcohol, si. sol. cold water, benzene, and ether.
Di-chloro-cimiamic aoid CbHj.CIj.CHiCHCO^H
[1:3:6]. Formed by the action of Ao^O and
NaOAo on (/3)-dichloro-benzoic aldehyde (Seelig,
A. 237, 168). Fine needles (from dilute alco-
hol).
(a)-Tri-cliIoTO-cinnamic acid
6.HjCl,.CH:CH.C02H [113:4:6]; [201°]. Formed
by acting. on (a).trichloro-benzoic aldehyde with
acetic anhydride a,nd sodium acetate (Seelig, A.
237, 151).
(j3)-Tri-chloro-cinnamic acid
C„Hj.Cl,.OH:CH.CO,H [1:2:3:6]. [185°].
Formed by the action of acetic anhydride and
sodium acetate on (j3)-tri-ohloro-benzoio aldehyde
(SeeUg, A. 237, 151).
CHLOEO-CITEACONIC ACID C^HsOlO,. The
salts of this acid are formed from the anhydride.
The free acid, liberated by the addition of HjSOj
to the barium salt, splits up at onoe into water
and anhydride. Zn and HCl reduce it to pyrotar-
taric acid.
Salts. — CaA". — BaA"3iaq. — BaA" 4aq.—
PbA".— AgHA",— AgjA".
Anhydride C,H,C10,. [99°]. (212°).
Formed by distilling citra-di-chloro-pyrotartano
or chloro-citramalio acid (Gottlieb, /. pr. [2] 8,
73; Swarts, J. 1873, 582). Laminie ; may be
sublimed. SI. sol. water, v. sol. alcohol and ether.
CHLORO -CITBIC ACID C„H,C10,i From
aconitio acid and HOCl (PawoUeok, A. 178, 155).
Unstable syrup. Boiling with water or baryta-
water gives oxy-citrio aoid.
CHLOEO-CODEitSE v. Codeine. .
CHLORO- COMPOUNDS. See also Bbomo-
CoMPOTTNDS. In organic compounds chlorine can
displace hydrogen atom for atom, the resulting
compound possessing as a rule considerable
resemblance to the parent substance. This
observation in the hands of Laurent and Dumas
overthrew the electro-chemical theory of chemical
affinity which had been established by Berzelius
(c/. K. 1, 66). The hydrogen that is displaced
by chlorine is usually that attached to carbon.
Chlorination may be effected by a mixture of
KCIO3 and HCl, by PCl^, SbCl„ or AcCl, but it is
usually effected by the direct action of chlorine
gas. The chlorination of aromatic hydrocarbons
may beeffected by heating the hydrocarboiis with
the theoretical amount of PCI5 at 190° ; in this
case the PClj splits up into PCI, and chlorine, the
latter then attacking the aide chains ; the pro-
ducts are nearly pure (Colson a. Gantier, Bl. [3]
45, 6 ; G.B. 101, 1064). In the same way acetyl
chloride heated for several weeks with PCI5 in
an open flask is converted into chlorinated acetyl
chlorides (Michael, Am. 9, 215). Acetyl chloride
itself maybe used as a chlorinating agent ; thus
benzene-azo-benzene heated with AoCl at 170°
for 4 hours is converted into ^-ohloro-benzene-
azo-chloro- benzene and p-chloro-acetanilide
(Becker, B. 20, 2006). When free chlorine is
used the substitution is usually slow unless it is
aided by daylight, by sunlight, by heat, or by
carriers.
Sunlight enables chlorine to enter the side
chains of aromatic hydrocarbons even at 0°
(Schramm, B. 18, 1272), which it will otherwise
only do at a high temperature ; in the cold and
in the dark it only enters the benzene nucleus.
Chlorine enters the methyl group of acetophe-
none whether the action take place in daylight
or in the dark; the chlorination is, however,
much more rapid in daylight (Gautier, C. B. 104,
1714).
Carriers. Iodine greatly assists chlorina-
tion, probably forming ICI3, which reacts more
vigorously than chlorine alone (Hugo Miiller,
0. J. 15, 41). The chlorides of metals which
form two chlorides also act as carriers ; e.g.
SbClj (Hugo Miiller; Beilatein a. Geitner, A.
139, 334 ; Bnoff, B. 9, 1436), M0CI5 (Aronheuu,
B. 8, 1400 ; 9, 1788 ; Page, A. 225, 199), FejCL;
AljClj, TlCl, and the chlorides of Au, Sn, Bi, 8,
Te, Ga, Zr, Nb, In, Ta, and XJr. On ^he other
hand the chlorides of Na, K, Li, Ag, Cu, Ca, Ba,
Sr, Mg, Zn, Hg, B, P, As, Se, T, Ce, and Di, are
not carriers (Willgerodt, J. pr. [2] 34, 264 ; 35,
398). According to Page, however, the chlorides
of Sn, S, and Bi are not carriers, as is also the
case with the chlorides of Ti, Cr, W, Mn, Co, and
Ni. It is, however, not possible to draw an
absolute line of demarcatiori between carriers
and non-carriers ; the weaker carriers can only
attack substances prone to chlorination. The.
effect of various chlorides is modified by circum-
stances, such as their solubility in the substance
to be chlorinated, their stability ir presence of
watei:, and the temperature cI the reaction.
M0CI5 acts as a carrier of pLiorine to aromatic
bodies only and not to falcy compounds. It may
be supposed that these various carriers act by
ss
CHLORO- COMPOUNDS.
alternately giving up chlorine to the compound
and taking it up again:
C,H, + M0CI5 = C.H5CI + MoCl, + CIH
Mo01, + CL, = MoCl5.
This does not account for the fact that carriers
promote entrance into the benzene nucleus, nor
for the observation that no ferrous chloride is
formed when benzene is heated with FCjClj.
An alternative supposition is that in the case of
aromatic bodies a. molecular compound is first
formed, possibly aided by the somewhat un-
saturated condition of the benzene ring, and
that this molecular compound is subsequently
decomposed by chlorine.
Displacement of one halogen by another,
lodo- compounds may be converted into ohloro-
Bompounds by digestion with HgClj-, on the
other hand, chloro- compounds may be changed
to iodo- compounds by treatment with KI or,
better, OaljSjHjO. Even acetyl chloride may
be converted into acetyl iodide by heating with
crystallised calcium iodide, without being affected
by the water of crystallisation. In general, metals
with low atomic weights prefer the lighter halo-
gens. The following elements prefer chlorine to
bromine or iodine, and bromine to iodine ; viz.,
K, Mg, Ca, Sr, Ba, Al, Mu, Co.
On the other hand, Cu, Ag, Hg, Sn, Fb, As,
and Sb prefer iodine to bromine or chlorine, and
bromine to chlorine. P and Ti are indifferent.
The metals Zn, Cd, Tl, Bi, Fe, and Ni are vari-
able in their behaviour (Eohnlein, A. 225, 194).
Thus TO-propyl iodide is not acted on by MgClj,
SrCl,, or BaCl^ ; it is split up into gas and HI
by MnClj and TiCl, ; it is but slightly affected
by FeClj, CoClj, and NiCI^ ; but it is converted
into propyl chloride by ZnCl., CdCL, SnCL, SnCLj,
SbClj, and TlCl.
m-Propyl chloride is converted into propyl
iodide by Cal^, Srl^. Mnl„ and Ool^; is but
slightly afiected by Fel, and Nil, ; and is not
affected by SnI,.
The substitution of chlorine by iodine may
be effected by the use of EI in the case of cbloro-
lactic acid, chloro-acetone, di-chloro-acetone,
epichlorhydrin, and diohlorhydrin ; on the other
hand, EI does not act on dichlorinated ethyl
oxide, and decomposes chloral into chloroform
and CO.
The substitution of CI by I may be effected
by Aljlj in the case of CCl, and CH3.CHCI2 ; but
AIJ, does not act on 0,01, or on C^Clj, while it
splits up OjCl, into CjCli and Clj.
EBr converts di-chloro-acetone into di-bromo-
aeetone. AljBr,, converts CClj, CjClj, and CjOlo
into OBrj, O^^r^, and CjBr,, respectively.
The conversion of EtI into EtCl is not effected
by BaClj, CuOlj, or PbCl; at 72°, but is partially
brought about by BaClj at 140°, and is com-
pletely effected by CuCl.^ and PbCl, at 160°.
The observation of Henry (O. B. 96, 1062) that
silver nitrate converts ethylene chlorobroniide
CHjOl.CHjBr into chloro - ethyl nitrate
CH2CI.OH2O.NO2 is in accordance with the state-
ment made above, that silver prefers bromine to
chlorine. Chlorine may be displaced by iodine
by heating with cone. HIAq in sealed tubes, but
the resulting iodo- compound is, especially in the
case of aromatic compounds, liable to loss of
iodine in exchange for hydrogen; thus ohloro-
beuzenes are reduced to benzene by HI at 250°
without any iodo-benzenes being formed (Bei-
thelot, Bl. [2] 9, 30).
Chlorinated hydrocarbons.
Formatio7i.—1.' By chlorihation of hydror
carbons. Chlorine enters the a and a positions
in fatty hydrocarbons ; thus n-pentane gives
OH,.CHj.OH2.CH2.CHjCl
and CHj.CH2.OH2.CHCl.OH3. On further ohlori-
nation, the chlorine turns out hydrogen that is
attached to the same atom of carbon as the
chlorine atom already present. In the case of
aromatic hydrocarbons chlorine enters the side
chain only at a high temperature or in sunlight.
In presence of iodine or SbClj it enters the
benzene nucleus even at boiling temperature {v.
supra). The rules relating to substitution in the
benzene nucleus are given in the article Benzene.
The displacing action of chlorine is not confined
to hydrogen ; thus it can convert nitro-benzene
into C„C1, (Page, A. 225, 208).— 2. Mono-chlori-
nated hydrocarbons or alkyl chlorides are formed
by treating alcohols with HOI, P01„ PClj, or
pool,. The action of HCl on alcohols is pro-
moted by ZnOlj (Groves, C. J. 27, 686 ; A. 174,
372 ; Erilger, J. pr. [2] 14, 195), but in the case
&f the higher fatty alcohols the resulting chloride
is sometimes mixed with an isomeride derived
from the olefine formed by dehydration of the
alcohol (Schorlemmer, G.J. 28, 308; B.7, 1792).
The polyhydric alcohols will not exchange all
their hydroxyls for 01 by treatment with HCl but
require the use of PCI5. — 3. From olefines and
HCl ^ the chlorine attaching itself to the atom
of carbon that is combined with the fewer
hydrogen atoms. Di-chlorinated hydrocarbons
are formed by the union of 01 with olefines, or
of HOI with the hydrocarbons C„H,„-2. Al-
though chlorine combines with olefines in the
dark, its combination with benzene and acetylene
requires light (Romer, A. 233, 172). — 4. From
aldehydes or ketones and PCI5. — 5. From aro-
matic amines by the diazo- reaction (v. Di-Azo-
coMPODNDs and Amines). The conversion may
also be> effected by gradually adding HNO3 to a
hot solution of the amine in HCl (Losanitsch, B.
18, 39);
Beactions. — 1. Boiling water very slowly de-
composes chlorinated hydrocarbons ; the chlo-
rides of tertiary alkyls are the most readily
affected (Niederi?t, A. 183, 388). Presence of
Pb(OH)j or E^CO, in the water promotes the
conversion of chlorinated hydrocarbons into al-
cohols. If two chlorine atoms are attached to
the same carbon atom, the product is an alde-
hyde or ketone ; if three are attached to the same
carbon atom, the product is an acid. — 2. Am-
moma converts the alkyl chlolrides into amines.
3. Alcoholic potash removes HOI in two stages
from di-chlorinated hydrocarbons, the CI and H
being detached from neighbouring carbon atoms,
the hydrogen coming from the carbon atom to
which the less hydrogen is attached. — 4. Chlor-
ine may be displaced by hydrogen by treatment
with sodium-amalgam in presence of dilute alco-
hol ; with zinc-dust and HOAc ; or with cone.
HIAq. — 5. Dry oxalic acid displaces chlorine
by oxygen in the compounds BOHCl, and RCCl,
(Anschiitz, A. 226, 13).
Chlorinated acids.
Formation. — 1. By direct ohlorination ; chlor-
ine taking tlje a position if possible, especially
UHl^OKO-CllfiSOL.
ft?
il the temperature be not above 100° (Srlen-
meyer, B. 14, 131S).— 2. From salts of oxy- aoida
and Ppi„ the resulting oblorinated alkoyl chloride
being decomposed by water. — 3. By addition of
chlorine or of HCl to unsaturated acids ; HCl
aniting with acids of the form BGH:CH.C02H
gives rise chiefly to j8-ohloro- acids
BOHCl.OHj.COjH.
BeacUons. — 1. Boiling with water or alkalis
usually converts a-ohloro- acids into oxy- acids,
S-chloro- acids into unsaturated acids, and
y-chloro- acids into lactones. The j3-chloro-
Bcids also split up into HCl, COj, and an olefine
(Eittig, A. 195, 169 ; cf. Erlenmoyer, B. 14, 1318 ;
15, 49). EOEt converts a-chloro- acids into
ethoxy- acids, aa-di-chloro- acids are but slightly
affected by boiling water ; a0-di-chloro- acids give
the chloro-oxy- acid, and also split o£C CO,.
Alcoholic EOH converts acids of the form
BCH01.CH01.C0i,H chiefly into EOH:C01.00jH.
Acid chlorides.
Formation. — 1. By the action of PCI5, PCI3,
or POCI3 on the acid or on a dry salt of the acid
(Gerhardt, A. 87, 63 ; B£champ, C. B. 40, 944 ;
Eanonnilcoff, A. 175, 378). Although POl, does
not convert tri-chloro-methane-sulphonio acid
into its acid chloride, it acts upon methane sul-
phonic acid and chloro-methano salphonic acid
in the usual way. — 2. By the action of HCl on a
mixture of the acid and P^O, (Friedel, Z. 1869,
489).
Beactions. — 1. Quickly decomposed by juaier
into HOI and the corresponding acid, and even
more readily decomposed by alcohoU with for-
mation of ethers. — 2. Ammonia forms amides ;
primary ammas act similarly. — 3l ^alts of organic
acids form anhydrides. Dry oxalic acid also
converts them into anhydrides (Anschtitz, A.
226, 13 ; V. AsirrDiiiDES, Oboanic). — 4. Zinc ethyl
unites with them forming compounds such as
E.C(0ZnEt)Et01 which are converted by water
iiito ketones B.CO.Et; further action of sine
ethyl forms B. C(0ZnEt)Eto whence water forms
tertiary alcohols B.C(OH)e\. Thus COjEt.COOl
becomes C02Et.C(0H)Etj (Henry, B.5, 949).—
5. Aluminium chloride forms with acetyl chloride
diluted with CSj a white solid C,jH„0,A1j,01b
decomposed by water into CHj.OO.CHj.OO.CH3
with evolution of COj, and by alcohol into acetyl-
aceto-acetio ether. AljCl, acts similarly on
chlorides of other normal fatty acids (Combes,
A. Ch. [0] 12, 199).— 6. Chlorine acts by substi-
tution more vigorously upon acid chlorides than
upon the acids themselves (Jazukowitzsoh, Z.
1868, 234). — 7. Sodium amalgam added to a
mixture of an acid with its chloride reduces the
latter to the corresponding alcohol (Linnemann,
A. 161, 184 ; Baeyer, B. 2, 98).
Chloroamides and chloroimides B'.NHCl,
E',B*jNCl, B"NC1 where B', R'„ and B" are acid
radicles, and B'j acid or alcoholic.
These bodies are formed by adding a cone,
solution of chloride of lime to the solution of the
amide or imide acidifled with AcOH.
By treatment with alkalis, HCl, &c., their 01
atom is readily replaced by H (Bender, B, 19,
2272).
CHIOBO-GOiniNE v. OoKnNE.
(a)-CHLOEO-COUMASIN C^HjClOj. [123°].
From coumarin and POI5 at 200°. Also from
ooomarin dichloride and alcoholic KOH (Perkin,
C. J. 24, 43). Flat needles, m. sol. aleohoi, si.
sol. hot water. Converted by alcoholic KOH into
coumarilio acid.
(i8)-Chloro-coumarin CHjClOj. [162°]. From
AOoO and sodium ohloro-o-oxy-benzoio aldehyde
C„H,01(0Na)CH0 (Baseoke, A. 154, 85). Orys-
tals,_ si. sol. cold alcohol, v. e. sol. benzene.
Boiling KOHAq converts it into chloro-coumario:
acid.
Tetra-ohloro-conmarin CHjCljO,. [145°]..
Formed by passing chlorine into coumarin dis-
solved in 601, containing iodine (P.). Small l
needles (from alcohol).
CHLOHO-ij-CHESOL CsH3(0H,)01(0H) [1:3:4]!
(196°). S.G. M 1-2108. Formed by the actiom
of dry chlorine on sodium-^-cresol (Schall a. .
Dralle, B. 17, 2528), Liquid.
Methyl ether C^HsMeOUOMe). (214°),.
S.G. If 1-1493. Liquid.
Chloro-cresol C|^s(CHs)Cl(OH) or
0,Hj(0H;01)(0H). [56°]. (c. 240°). Formed by
chlorination of boiling crude cresol (Biedermann,.,
B. 6, 325). Needles ; v. sol. alcohol, ether, andl
benzene.
Chloro-cresol. Ethyl ether
0„H3MeCl(0Et). (c. 215°). S.G. i»l» 1-127..
From (a)-ohloro-nitro-toluene by reduction, diazo-
tisation, and treatment of the diazo- s'ulphate-
with boiling alcohol (Wroblewsky, A. 168, 209).
Chloro-cresol. Ethyl ether 0„H3MeCl(0£t),
(c. 215°). S.G. la 1-131. From (i3)-ohloro-nitro-
toluene in the same way as the preceding (W.).
Di-ohloro-jj-cresol CsHj(CH3)Cli,(0H)
[89° unoor.]. Formed by passing chlorine into
boiling ^-cresol (Glaus a. Eiemann, B. 16,
1598). Ijong prismatic needles. Sol. alcohol
and ether, si. sol. hot water. By CrO, in acetic
acid it is oxidised to di-ohloro-^-oxy-benzoio
acid [156° uncor.]. — A'NH,: long colourless
needles [125°], sublimable.
Di-chloro-m-cresol 0jH2(CH,)Clj,(0H) ; pro-
bably [1:4:6:3]. [46° uncor.]. Formed by chlo-
rinating m-cresol (Glaus a. Schweitzer, B. 19,
930). Colourless needles. Volatile with steam.
Y. e. sol. alcohol, ether, &c., sol. hot trater,
nearly insol. cold. It is oxidised by KjCrjO,
and dilute HjSO^ to di-chloro-toluquinone
[103°].
Di-chloro-o-oresol C„H2(OHs)Ol2(OH) -
[l:5:3or4:2] [54° uncor.]. Formed by chloi.
ination of o-cresol (0. a. E., B. 16, 1600).
Large colourless needles. Y. sol. alcohol, ether,
benzene, chloroform and CSj, sol. hot water, si.
sol. cold water. By OrO, and glacial acetic
acid it is oxidised to a mixture of di- and tri-
chloro-toluquinone. By KjOrjO, and dilute
HjSOj it is oxidised to mono-chloro-toluquinone
[90°] (Olaus a. Schweitzer, B. 19, 927).
JJao-Di-chloro-o-bresol C,Hj(OHCy(OH>
[1:2]. [82°]. From salicylic aldehyde (1 mol.)
and POI3 (1 mol.) (Henry, B. 2, 135). Prisms
(from ether) ; v. si. sol. cold alcohol.
Phosphoryl derivative
PO(O.C,H4.0HGl2)3. [78°]. From salicylic alde-
hyde and PCI5 (Stuart, 0. /. 53, 402). Needles
(from alcohol). Not affected by boiling dilute
NaOHAq.
Methyl ether C.Hj(CHOy(OMe). (231°).
From C8Hi(0Me)GH0 [1:2] and PCI5 (Stuart,
C. J. 53, 404). Oil. Decomposed in moist air.
a
OHLORO^RESOL.
Tri-chloro-cresol C,H(CH3)Cl3(OH). [96°].
(270°). One of the products of distillation of
crude penta-ohloro-thymol (Lallemand, J. 1856,
620). CiyatalB ; iusol. water, sol. alcohol and
fLlk&illS
Tetra-oMoro-cresol Cs(CH3)Cl4(OH). [150°].
Obtained by distilling pure penta-chloro-thymol
(L.). Needles. .
a-CHLOSO-CBOTONIC ACID
CH3.CH:CCl.C0aH. [97-5°]. (206°) (Kahlbaum.B.
12, 2335) J (212°) (Sarnow). S. 1-97 at 12°
(K.); 2-12 at 19° (Michael a. Brown, Am.
9, 283).
Formation. — 1. From tri-chloro-butyrio alde-
hyde by oxDlation and treatment of the resulting
tri-chloro-butyrio acid with zinc and HCl
(Kriimer a. Finner, A. 158,37) or with zinc-dust
and water (Sarnow, A. 164, 93 ; B. 4, 731 ;
6, 467). — 2. By boiling tri-chloro-butyrio alde-
hyde (29 g.) with K^FeOyo (42 g.) and water (500 g.)
(Wallach, B. 10, 1530).— 3. From solid crotonio
acid by addition of chlorine followed by heating
the product CHj.CHCl.CHCl.GOjH (Friedrich,
A. 219, 373).— 4. From chloro-butenyl alcohol
(q, v.) by oxidation. — 5. By the action of cold
aqueous NaOH upon the liquid aZTo-ajS-di-chloro-
butyric acid (the addition product of isocrotonio
acid and 01) (Wislioenus, B. 20, 1009).
Properties. — Small flat needles; may be
sublimed. Volatile with steam. Not attacked
by alkalis below 220°, at which temperature
acetic and oxalio acids are formed, together
with COj and a syrupy acid (F.). Seduced by
Bodium-amalgam to crotonic acid.
Salts. — ^A'K: pearly plates or tables (from
,80 p.c. alcohol) ; nearly insol. absolute alcohol. —
NH4A' ; lamina. — CaA'j. — ^BaA'j : lamina. —
PbA'j aq.— CuA'j : needles. — CuA'(OH) : amor-
phous.— AgA': needles.
Methyl ether Mek'. (161°). S.G. 4 1-0033
Its 1-4589 (Kahlbaum, B. 12, 344).
Ethyl elherEtA.'. (177'' uncor.). S.G. 15
1'129. From tri-chloro-butyrio aldehyde and
alcoholic KON (Wallach a. Bcihringer, A. 173,
301, cf. Glaus, A. 101, 63). Turns brown in
light.
lieactions. — 1. Treated with KCN (2 mol.)
and boiling alcohol it forms a product whence
boiling EOH produces tri-carballylic acid (Glaus,
A. 191, 64) and crotaconic acid, G,H,(C02H)2,
isomeric with itaconic acid. The tricarballylio
acid is formed through addition of HON to the
crotaconic acid. — 2. With KCN (2 mol.) and
dilute alcohol in the cold it forms potassic
cyano-crotonate (3. v.) only.
O&Zoride.— GH3.GH:C01.C0C1. (142°). (S.).
Amide CHa.CH:CCl.CO.NH2[112°] (P.a. K.);
[107°] (S.). (c. 235°) (S.). From the cyanhydrin
of tri-chloro-butyric aldehyde and alcoholic NH3
or dry ammonium carbonate (Pinner a. Klein,
B. 11, 1488). Also from the chloride and NH,
(S.). Laminm ; may be sublimed.
Nitrile CHj.CHtOCLCN. (136°). From the
amide and P^Oj (S.).
^2Zo-a-chIoro-crotonio acid GHj.CHtCCI.CO.H.
l67°]. S. 6-53 at 19°. Formed by the action of
an excess of aqueous NaOH upon ai8-di-chloro-
butyric acid [63°] at the ordinary temperature
(Wislicenus, B. 20, 1009 ; Michael a. Brown,
Am. 9, 283). Slender needles (from water).
More BO ublo in water than any of the other
chloro-orotonio acids ; si. sol. cold ligroln.—
A'K : concentric needles; v, sol. absolute alcohol
(diSerenoefrom the a-acid, whose K-salt is nearly
insoluble).— BaA'j Bjaq: crystals, si. sol. al-
cohol.— PbA'^aq: prisms, si. sol. water. — «AgA':
amorphous.
0-Chlora-crotonio acid CHj.GCltGH.CO^H.
[94-5°]. (c. 209°). S. 1-9 at 19° (Michael a.
Brown, Am. 9, 283) ; 2-25 at 12° (K.) ; 2-8 at
19° (G.).
Formation. — 1. The chloride of this acid is
formed together with that of aZZo-i3-chloro-
crotonic acid by the action of excess of PClj on
aceto-aoetic ether. The mixed chlorides are
saponified by water and the product distilled,
wiiereupon jS-chlo'rocrotonio acid passes over
first (Geuther, Z. 1871, 237).— 2. Prom tetrolio
acid and fuming HGl (Friedrich, A. 219, 370);
Properties. — Slender monoclinio needles ;
o:6:c = 1-2859:1: -6105 ;'fl = 73° 9'; volatile with
steam; maybe sublimed at 100°. At 160° it
Blowly changes into aZ!o-;3-chloto-crotonic aoid.
Beactions. — 1. Sodium amalgam gives cro-
tonic acid. — 2. Boiling aqueous potash (7 p.c.)
gives tetrolic aoid (K.).— Stronger potash (18p.o.)
gives chiefly acetone. — 3. Sodium ethylate gives
the same ethoxy-crotonio acid as is got from
aZ2o-3-ohloro-crotonic acid.
Salts. — NaA' -jaq: thin lamina, v. e. sol.
water. — ^BaA'j: trimetric octahedra'. S. 45 at 18°.
— OuA', aq.
Ethyl ether EtA'. (184° cor.). S. G. !??
Mil (G.).
^{{o-yS-chloro-crotonis add
CH,.CGi:CH.GO,H. [59-5°]. (195° cor.). S.M2
at 7°. Formed from aceto-acetlc ether as above
described (Geuther a. Frohlioh, Z. 1869, 270).
Formed also by heating the preceding acid fol
20 hours at 160° (Friedrich, A. 219, 363).
P»-qpar<ies.— Slender needles or prisms ; vola
tile with steam; sublimes even at 20°- Not
affected by boiling aqueous KOH.
Beactions. — 1. Alcoholic KOH converts it
into the ethyl derivative of fflZfc)-/3-oxy-orotonia
acid. — 2. Cone. KOHAq forms acetone and CO..,,
a small quantity of tetrolio aoid OJifi^ [75°-77°]
being also formed (Friedrich, A. 219, 341). Di-
lute KOH behaves similarly, but the tetrolic acid
is the chief product.
Salts. — NaA'^aq: satiny crystals, v. sol.
water. — KA' aq. — TIA' Jaq. — NH.HA'j aq. —
CaA'2 3aq. — BaA'2 2aq : four-sided prisms. —
MgA'jSaq.- ZnA'22laq.— PbA'34aq.— MnA'j2aq.
— CoA'jOaq.— NiA'2 6aq.— CuA'^ ijaq.— AgA'.
Methyl ether MeA'. (142° cor.). S.G.
15 1-143.
Ethyl ether EtA'. (161° cor.). S.G. 15
1-113. Boiling alcoholic KCN followed by KOH
converts it into tri-oarballylic aoid (Glaus a.
Lischke, B. 14, 1089).
Isomeride of ohloro-crotonio acid v. Chloro-
METHACRILIC ACID.
a3-Di-cMoro-cratoiiio acid
GH5.GCl:GGl.C0jH. From oafl-tri-chloro-butyrio
acid (1 mol.) and KOH (2 mols.) (GarzaroUi, B.
9, 1209).
a-CHLOBO-CBOTONIC ALSEHYSS
CH3.CH:G01.GH0. (148°). Formed, together
with tri-chloro-butyrio aldehyde, by chlorinating
aldehyde containing alcohol (Pinner, A. 179, 31).
Formed also by heating the Ijydrate of chloro-
CHLORO-ETHANE.
m
Mcetifl aldehyde with aldehyde and a drop ol
ituming HCl at 100° (Lieben a. Zeisel, M. 4, 531).
liiquid. Combines with chlorine forming tri-
ohloro-batyrio aldehyde. Br gives chloro-di-
bromo- and ohloro-tri-bromo- butyric aldehydes
<Pinner, D. 8, 1323).
a7-I)i-chlora-butyrio aldehyde
CH,C1.CH:C01.CH0. (86°) at 18 mm. Gradu-
ally separates as an oil when the hydrate of
chloro-acetie aldehyde is heated with a drop of
HjSOj at 100° (Natterer, M. 4, 589 ; 5, 507).
Oil; solidifies when cooled with solid CO,^.
Forms a crystalline compound with NaHSOj.
Beduces warm ammoniacal AgNO,. Beduced by
iron filings and acetic acid ton-butyl and butenyl
alcohols. Oxidised by HNO3 to oxalic and chloro-
acetie acids. Br forma ay-di-ohloro-a^S-di-bromo-
(butyric aldehyde. HCl gives tri-chloro-butyrio
aldehyde, ZnEtj followed by dilute HjSO, gives
a di-chloro-faexenyl alcohol CgH^Cl^O (c. 117°)
at 20 mm.
CHLOBO-CBOTONYL-TTBEA
CH,.CH:CCl.CO.NH.CO.NHj. [224°]. The chief
product of the reaction of the cyanhydrin of tri-
chloro-butyrio aldehyde with urea ; the yield is
about 60 p.o. Bhombic tables. Sol. alcohol, si.
80I. water. On heating it evolves HCl and is
converted into di-ozy-ethylidene-metapyrazole
CH3.CH:C.N^
I >C(OH) (Pinner a. Lifsohvitz, B.
(HO)C:N'^
20, 2347).
CHLOBO-CBOTYL u. Chloho-butenyl.
CHLOKO-.f'-CUMEirE C,H2(CH3),C1 [1:8:4:6].
[71°]. White plates. Formed by the action of
cuprous chloride upon diazo-pseudo-oumene
(Halle;, B. 18, 98) or by warming the piperidide
of diazo-peeudo-cumene with cone. HClAq (Wal-
lach a. Hejisler, A. 243, 232).
w-Chloro n-cumene C,H„C1 i.e.
C,Hf.CHo.CKj.CH2Cl. Chloro -propyl- benzene.
(219°). Prom C„H5.0H2.CH,.CH,OH and HCl
(Errera, (3. 16, 310). Oil. Not affected by fused
ZnClj nor by AgOAo. Alcoholic KOH gives
CA.CaH,.OEt (220°).
o-Chloro-»-cnmene CjHs.CHs,.CHCl.CH3. (c.
206°). From 0„Hs.CH,.CH(0H).CH3 and HCl
(E.). Formed also by chlorination of ra-propyl-
benzene (Errera, Gf. 14, 506). Partially detiom-
posed by distillation into HCl and allyl-benzene.
Alcoholic KOH also forms allyl-benzene, as does
ZnCl, likewise.
/S-Ohloro-ra-cnmeno CoHj.CHCl.CHo.CHs. (c.
203°). From the corresponding phenyl-propyl
alcohol and HCl (E.). Partially resolved by dis-
tillation, even in vacuo, into HCl and allyl-benz-
ene. AgOAc forms C„H5.CH(OAc).CH2.CH, (227°).
CHLOEO-CTJMINIC ACID C,„H„ClGj i.e.
CsH,.CsH,Cl.C02H [4:3:1]. 1123°]. Formed by
oxidation by HNO, of the chloro-oymene from
thymol and POI5 (Gerichten, B. 11, 365 ; Fileti
a. Crosa, Q. 16, 288). Long needles (from dilute
alcohol). Beduced to cuminio ac^id by sodium-
amalgam. — BaA'2 3aq : pearly plates.
CHLOBO-CUUOQUIirOLINE v. Chlobo-ibo-
PROPTL-QCnjOLINE.
CHLOBO-CYAITAIIIDE v. Auuelihe.
CHLOBO - CYANO - BENZENE v. Nitrite of
Ohlobo-bgnzoio acid.
CHLOBO-DI CYANO-NITEO-METHANE
CClCy,(NOj). Formed by warming chloropicrin
with alcoholic ECy (Basset, O. J. 19, 352).
Silver nitrate solution gives an orange pp. oi
(AgN0,),30ClCy,(N0,).
CHLOBO-CYMENE C,„H„C1 i.e. O^HsMePrCl
[1:4:2]. (210°). S.G. " 1-014. From carvaqrol
and PCI5 (KekuW a. Fleischer, B. 6, 1090).
Formed also by chlorination of cymene (from
camphor) in presence of iodine (v. Gerichten,
B. 10,1249). Oxidised by dilute HNO, to chloro-
toluio acid [196°].
CMoro-cymene C.HjMePrCl [1:4:3]. (213°).
From thymol (4 mols.) and PCI5 (1 mol.) ; the
yield being 85 p.c. (Carstanjen, J.pr.X2] 3, 64;
v. Gerichten, 2?. 10, 1250; 11, 365; Fileti a.
Crosa, O. 16, 287). Not affected by sodium
amalgam (F. a. C). Oxidation gives chloro-
cuminic [117°], chloro-toluio [149°], and chloro-
terephthalic, acids.
w-Chloro-cymene C„H,rr(CHjCl) [1:4]. Cwnyl
chloride. (0. 227°). Formed by passing chlorine
into boiling cymene (Errera, 0. 14, 277). De-
composed by long boiling with formation of
CjoHjj. Alcoholic KOH giveaO,|,H,sOEt. Sodium
amalgam reduces it to cymene. BoiUng aqueous
Pb(N0g)2 gives cuminic aldehyde.
Sffio-ohloro-oymene C„H4(CjHsCl)Me [1:4].
Two compounds of this nature are formed, to-
gether with the preceding body, on passing chlo-
rine into boiling cymene (derived from camphor).
One of them is not attacked by alcoholic KOH,
while the other is converted into allyl-toluene
CsHj(CsH,)Me (Errera, Q. 14, 283).
u-Chloro-jj-isooymene C8H,Pr(CHjCl) [1:4].
Cumyl chloride, (o. 230°). Foi;med, together with
cumyl carbamate, by passing cyanogen chloride
into cuminyl alcohol CgH^f r.CH^OH (Spica, O.
5, 394). Formed also by the action of HCl on
cuminyl 'alcohol (Paterno a. Spica, O. 9, 397;
B. 12, 2366).
ci>a)-Di-chloro-cymeiie08H4(0,H,).(CHCl2). Cu-
mylidene chloride, (c. 258°). From cuminic
aldehyde and PCI5 (Cahours, A. 70, 44 -tSuppl.
2, 311 ; Sieveking, A. 106, 258). Beconverted by
alcoholic KOH or by heating with water at 150°
into cuminic aldehyde.
letra-chloro-m-isocymene CgCl^PrMe [1:3].
[159°]. Formed by passing chlorine into a cold
saturated solution of tri-chloro-isocymeue sul-
phonio acid at 40° (Kelbe, B. 16, 617). Needles
(from alcohol) ; may be sublimed. Not oxidised
by HNO3 or chromic mixture.
TBI-CHLOEO-m-ISOCYMENE SULPHONIC
ACID CjCl3PrMe(S0|,H). From m-isocymene
sulphonio acid by passing CI into its aqueous
solution at 40° (Kelbe, B. 16, 618).— NaA':
laminie.
CHLORO-DECANE v. Deottl chloride. ■
CHIORO-DECYLENE C,„H„C1. (206° cor.).
From CI and boiling decanaphthene (Markowni-
koft a. Ogloblin, /. B. 16, 333). Alcoholic KOH
gives a mixture of deoinentes (155°-165°).
TErSA-CHLORO-DUBENE OsH2(CH2Cl),
[1:2:4:5]. [144°]. S.G. 1-479. Formed by heat-
ing durene with excess of PCI5 at 190° for 5 hours
(Colson a. Gautier, C. B. 102, 1076 ; Bl. [2] 46,
198).
DI - CHLOlRO - EOSIN v. Di-chlobo-ibiba.-
BBOMO-FUJOBESCEIN.
CHLORO-ETHANE v. Ethyl ohlobide.
Di-chloro-ethane v. EthyleiiB cblobide and
Etuylidenb ciilohide.
60
CHLORO-ETHANE.
Tn-cMoro-ethane CHaCl.CHClj. Ghloro-ethyl-
me chloride. (114°) (Schifl, A. 22^0, 97) ; (115°)
(Perkin, C. J. 45, 531). V.D. 4-66 (£or 4-60).
S.a. '-^ 1-4577 ; if 1-4553; IH-4430. M.M. 6-796
at 16-7°. C.B. (from 9° to 113°) -00121. H.F.p.
33980 (!^/^.). H.F.V. 32820. S.V. 102-77.
WormaUan. — 1. From chloro-ethylene (vinyl
chloride) and SbCl., (Eegnault, A. OA. [2] 69,
151 ; 71, 355).— 2. JFrom ethyl chloride and CI
(Kramer, B. 3, 261).— 3. By chlorinating ethyli-
dene chloride in presence of Al^Cl, (Tavildaroif,
B. 13, 2403).-4. From CHClj.CHjOH and PCI5
(de Lacre, C. B. 104, 1186).
Beactions. — 1. Aqueous or alcoholic ammonia
gives a theoretical yield of C^HoClj (37°) (Engel,
C. B. 104, 1621) ; alcoholic KOH forms the same
body.— 2. Sodium forms C„H„ CJl.fi\^, O^Hj,
and hydrogen (Briinuer a. Brandenburg, B. 10,
1496; 11,61).
Tri-chloro-ethane CH3.CCI3. (76°) (Perkin) f
(74-6°) (Geuther). V.D. 4-53. S.G. if 1-3247 ;
H 1-3114. M.M. 6-740 at 17-6° (Perkin) ; s 1-347
(Pierre, A. 80, 127). Formed by chlorinating
ethyl chloride (Eegnault, A. 83, 317 ; Geuther,
J. 1870, 435). Converted by NaOEt at 100° into
CH2:CCl(0Et), acetic acid, and ortho-acetic ether
CH,.C(0Et)3. Differs from its isomeride in
forming, when cooled, with aqueous HoS, a crys-
talline compound C2H3CI32H2S 23aq (Forcrand,
A. Ch. [6} 2S,25).
M-Tetra-chloro-ethauo CHoCl.CCla. (135°)
(Eegnault) ; 139° (Pierre, A. 80] 130) ; (1305° i.
V.) (Staedel, B. 15, 2563). . S.G. 2 1-6110 (P.).;
1* 1-576. Formed by chlorinating ethylene chlo-
ride (Laurent, A. 22, 292) or CHCl.CHClj (E.).
With NaOEt it gives CHCl:CCl(OEt) and
CHj(0Et).C02Na. H^S gives O^HfilfiS^S 23aq.
s-Tetra-ohloro-ethane CHCla.CHClj. Acetyl-
ene tetrachloride. (147° cor.). S.G. 2 1-614
(P. a;. P.) ; g 1-6897 (Kaconnikoli).
Formation. — 1. By passing acetylene into
SbClj, which slowly absorbs it and deposits
, . CjH^SbClj, the mixture of this body with SbClj
is then distilled (Berthelot a. Jungfleisch, G. B.
79, 542). — 2. By passing acetylene into PCI5 ;
I explosion often occurring (Sabanejeff, A. 21C,
262). — 3. By heating ethylene chloride with the
calculated quantity of PCI5 for ten hours at 190°
(Colson a. Ga,utier, 0. R. 102, 1075).— 4. From
di-chloro-acetic aldehyde and PCl^ (Paternd a.
Pisati, G. 1, 461 ; J. 1871, 508).
Pro2}erties. — Not affected by boiling water.
Slowly decomposed at 360° giving HCl and
hexa-'chloro-benzene.
Penta-cMoro-ethaue CHCLj.CClj. (158-9°)
(Thorpe). S.G. % 1-70893. C.E. (0°-10°)
-000949 ; (0°-100°) -0009944. S.V. 138-2.
Formation. — 1. From chlorine and EtCl
(Eegnault, 4. 33, 321).— 2. By chlorinating ethyl-
ene chloride (Pierre, A. 80, 130).
Preparation. — POI5 (190 g.) is gradually added
to chloral (113 g.), boiled with inverted condenser
and distilled. The portion distilling below 170°
is washed with water, dried with CaClj and recti-
fied. The yield is small (Patern6, C. B. 68,
450 ; Thorpe, 0. J. 37, 192).
Properties. — Liquid, solidifies below -18°.
Converted by alcoholic KOH into KCl and C2CIJ.
PCI, at 250° gives O^Cl,.
Hexa-chloro- ethane CClj.CClj. [179°]
(Geuther a.Brookhofl, J. pr. [2} 1,109); [185°
cor.) (Hahn, B. 11, 1735). (185° cor.) (H.). S.G.
2-0 (Schroder, B. 13, 1070). V.D. 816 (calo. 8-21).
Formation. — 1. J?rom OjOli and CI in daylight
or by heating (Faraday, 2'j-.1826, 47; Liebig, A. 1,
219).— 2. The ultunate product of the cblorina-
tion of ethyl chloride (Laurent, A. Oh. [2J 84,
328) or ethylene chloride (Faraday), and hence
formed in the chlorination of most ethyl com-
pounds in sunlight (Eegnault, A. Ch. [2] 69,
166; 81, 371; Ebclmen a. Bouquet, A. Ch. [3]
17, 66 ; Malaguti, A. Ch. [3] 16, 6, 14 ; Geuther
a. HoJaoker, A. 108, 61).— 3. By- passing CCl,
through a red-hot tube (Kolbe, A. 54,, 147) or
over finely divided copper at 120° (Eadziszewski,
B. 17, 834) or silver at 180° (Goldschmidt, B.
14, 9-28).- 4. From AcCl and PCI5 at 180"
(Hiibner a. MGller, Z. 1870, 328).— 5. Ultimate
product of the action of PClj on succinic acid. —
6. By heating propane, propyl chloride, or iso-
hutyl chloride and IClj at 200° (Krafft a. Merz,
B. 8, 1298). — 7. From propionic acid and ICl,
(Krafft, B. 9, 1085).— 8. By chlorination of boil,
ing butyric acid in sunshine (Naumann, A. 119,
120).— 9. Together with CbCI, and CCl, by heat-
ing ohrysene with PCI5 (Euoff, B. 10, 1234).
Properties. — Tables (from alcohol-ether) ;
smells like camphor. Trimorphous, crystallising
in the cubic, trimetric, and tricUnio systems
(Lehraann, J. 1882, 369 ; Z. K. 6, 580). Insol.
water, sol. alcohol and ether. When its vapour
is led through a red-hot tube C^Cl, is formed.
Beactions. — 1. Alcoholic potash at 100° con-
verts it into oxalic acid (Berthelot, A. 109, 118).
Solid potash at 200° does the same (Geuther; A.
Ill, 174). — 2. Boiling with NaOEt underpressure
gives CjClj, CCl,:CCl(OEt), CHCl.,.C(OEt)„ and
CHj(OEt).COjNa (Geuther a. Brockhofl). Zino
and dilute HjSO, do the same. — 3. Finely
divided silver at 280° also gives C^Cl,.— 4. SO, '
at 150° forms CCI3.COCI and COCl^ (Prudhomme,
A. 156, 342 ; Armstrong, Pr. 18, 502).— 5. Al^I,
forms C2CI4, Al^Cl^, and iodine (Gustavson, S. 9,
1607).
CHLORO-ETHAHE TSI-CAEBOXYLIC ACID.
tlthyl ether (CO.,Et)j.CCl.CH,(COjEt)
(2p5°-215°) at 160 mm. From ethane tri-oarbo-
xylia ether and chlorine (Bischoff) 4. 214, 46).
Beactions.— 1. Boiling aqueous HCl forms
fumario acid.— 2. KOH and dilute alcohol form
malic acid. — 3. KOH and 97 p.o. alcohol appear
to form (CO,Et)2.C(OEt).CH2.C02Et.
a-CHLGKO-ZTHANE STILPHONIC ACID
CHs.CHCLSOjH. Its sodium salt A'Na is formed
by heating pthylidene chloride with solution of
Na-jSOa at 140°. This salt forms plates, soL
alcohol (Bunte, A. 170, 317).
j3-Chlnro-ethano sulphonio acid
CH,Cl.CHj.S03H.
Formation.— 1, By the action of fuming
HNO3 on CH,Cl.CHj.SCy (James, J. pr. [2] 20,
353). — 2. By boiling its chloride with' water
(Dittrich, J. pr. [2j 18, 67 ; Kolbe, A. 122, 33).^
3. From (CH,Cl.CHj)jS., and HNO, (Spring a.
Lecrenier, Bl. [2] 48, 629).
Properties.-^-Verj deliquescent needles. Not
decomposed by boiling water. Heated with am-
monia in sealed tubes at 100° forms taurine,
CHj,(NH,)CH,SO,H.
Salts.- (E. Hiibner, A. 223, 213; James,
OHLORO-ETHTL ALCOTTOL.
fill
J.pr. [2] 26, 382 ; C. Jf. 43, 41).— NH,A'.— NaA' aq.
KA' : needles, insol. alcohol. — BaA'j aq (H.). —
BaA', 2aq : needles (J.).— PbA'j 2aq.— CuA'j 3aq
(H.).— CuA's 4aq : triclinio tablets (3.).— ZnA'„4aq
(H.).— ZnA'j6aq : plates (J.). — MgA'j 4aq.—
SrA', 2aq : needles. — ^MnA', 4aq.— PeA'j 4aq. —
NMeHjA' : plates (from alcohol).
CfcJorti«.-CH,Cl.CH,SO,Cl (200''-205°).
Prom potassic iaethionate and PCI, (Kolbe, A.
122, 38). Also from SO..Cl.CHj.CH,.SO,Cl and
PCl, (Konigs, B. 7, 1163)r It .is one of the pro-
ducts of the action of SO, on ethyl chloride
(Fargold, B. 6, 502). Oil, smelling lilcc mustard.
Does not give an amide with ammonia, or an
ether when heated with alcohol. FCI5 at 200°
gives ethylene chloride.
Si-chloro-ethane snlphonic acid
C2H,Cl2(S0aH). From ethane sulphonic acid
and ICl, (Spring a. Winssinger, B. 15, 446).
Converted by baryta into chloro-isetliionio acid
CjH3Cl(OH)(S03H), Ammonia at 100° gives
chlorinated taurine.
CHLOKO-ETHENTL-TBICAEEOXYIIC ACID
V. CHLOEO-ETnAKE-TBIOABBOXYLIC ACID.
CHLORO-ETHEB v. CiiiiOno-iiTHTL oxn>E.
CHLOEO-ETHULMIC ACID C„H,C10j. A brown
amorphous body formed by adding sodium to
chloroform containing alcohol (Hardy, A. Ch.
[3] 65, 340).
CHIOEO-ETHYL-ACETAMIDE v. Chloho-
ETBYLAMINE.
B-CHLOEO-ETHYX. ACETATE CH3.CHCl.OAc
V. AliDEHYSE.
a-Chlcro-ethyl acetate CH^Cl.CHj.OAc v.
ChLOBO-ETHTIi ALCOnOIi.
Other Chloro-ethyl acetates v. Acetyl deriva-
tives of the corresponding cnLono-EiHXL alco-
B01.8.
CHLORO-ETHYL-ACETO -ACETIC ETHER
C,H„CIO, i.e. CH,Cl.C0.CHEt.C05Et (192-6''
cor.). S.G. ^ 1-052. A product of action of
PCI5 on ethyl-aoeto-acetic ether (Isbert, A. 234,
187 ; cf. Conrad, A. 186, 241). Oil, smelling of
peppermint. Sol. alcohol or ether. With dilute
HCl at 180° it gives raono-chlorinated methyl
propyl ketone. With NaOEt (1 mol.) in alcohol,
it gives rise to ethoxy-ethyl-aceto-acetic ether
CHj(OEt).CO.CHEt.COjEt (210° cor.). S.G. ^
•957. Alcoholic KOH at 120° converts it into
EtO.CHj.CO.CH,Et.
Di-chloro-ethyl-aceto-acetic ether CgH^CIjO,.
(220°-225°). S.G. J^ 1-183. Formed at the same
time as the preceding.
CUoro-di-ethyl-aceto-acetic ether
CH.,Cl.CO.CEtj.COjEt. S.G.i^l-0C3. POI5 has
no aition on di-ethyl-aceto-acetio ether, even at
100°, but at a higher temperature HCl, EtCl,
cthyl-chloro-orotonic (chloro-hexenoio) ether, di-
elhyl-ohloro-Bceto-acetio ether, and di-ethyl-di-
ohloro-aceto-acetic ethers are formed. The pro-
duct is freed from PCI, by distillation, is then
poured into water and distilled with steam
(James, 0. J. 49, 50 ; A. 231, 235). Di-ethyl-
chloro-aceto-acctio ether is a liqui'd, which is
converted by treatment with sodium methylate
MeONa into CHj(OMe).CO.CEtj.COjEt and
CH2(0Me).C0.CHMeBt (131°). S.G. 22 -855.
Di-chloro-di-ethyl-aceto-acetic ether
CHClj.CO.CEtj.COjEt. S.G. 15 1-155. One of
the products of the action of PCI, on di-ethyl-
aceto-'acetic ether. Oil, with pleasant smell.
Miscible with alcohol and with ether. Converted
by NaOMe into CH(0Me)2.C0.CEtj.C0jEt (0.
195°) and CH(OMe),.CO.CHEtj (134°). S.G. ii
•886 (James, C. J. 49, 57).
co-CHLORO-ETHYL AiCOHOI CHa.CHCl.OH.
EthyUdene chlorhydrin. (25°) at 40mm. An un-
stable body formed by combination of aldehyde
with HCl in the cold. It changes spontaneously
into ' ethylidene oxy-chloride ' or di-chloro-di-
ethyl oxide (Hanriot, A. Ch. [5] 25, 219), v. Alde-
hyde, vol. i. p. 104.
Acetyl derivative CH3.CHCI.OA0. (121-5°
cor.). Formed by combination of aldehyde with
acetyl chloride; v. Aldehyde, vol. i. p. 105,
where other alkoyl derivatives are described.
Methyl derivative CH3.CHCl.OMe. (0.
74°). S.G. iZ -g'ge. Formed by passing HCl
into a well-cooled mixture of aldehyde (1 vol.)
and methyl alcohol (1^ vols.) (lliibencamp, A.
225, 209).
Ethyl derivative CH3.CHCl.bEt v.
Chloeo-di-ethyl oxide.
Chloro-etbyl alcohol CjHsClO i.e.
CH^ClCHjOH. Qhjcol chlorhydrin. Mol. w. 80*-
(128°-131°). S.G. 2 1-2233.
Formation. — 1. By repeatedly saturating
glycol with HCl and distilling the product
(Wurtz, A. 110, 125; cf. Schorlemmer, C. J. 39,
143). Besides the pure product (128,°) a fraction
boiling at 10C° is obtained ; this fraction may be
represented as (CjHsClOJjHCl 8aq, and has
S.G. 2,1-1926; by means of KOH (1 mol.) it
may be decomposed ■mth liberation of the pure
chlorhydrin (Bouchardat, C. B. 100, 452).— 2..By
heating glycol with SjClj at 100° and extracting
the product with moist ether (Carius, A. 124,
257) ; the yield is over 50 p.o. of the theoretical. —
3. From ethylene and ClOH (Carius, .4. 126,
197 ; cf. Butlorow, A. 144, 40).— 4. From ethyl-
ene oxide and HCl ; the union is attended with
disengagement of heat : (CaHjOiHCl) =36,000
(Berthelot, C. B. 93, 185).
Properties. — Liquid, miscible with water. A
mixture of glycol chlorhydrin (1 mol.) with water
(4 mols.) solidifies at — 17°.
Beactions. — 1. Oxidised by chromic mixture
to chloro-acetic acid (Kriwaxin, Z. 1871, 265).—
2. Reduced by sodium amalgam and water to
alcohol (Lourengo, A. 120,92).— 3. Converted by
votash into ethylene oxide. — 4. With COCl,, in
the cold, reacts thus: CH^CI.CH.OH-hCUCO
= HC1-I-0Hj01.CH;.0.C0C1, forming the chloro-
ethylio ether of cKloro-formio acid.— 6. Heated
with KjSO, and water at 180° it forms isethionic
acid CH20H.CH2S0,H.— 6. Ammonia forms
oxyethyl-amine CH^OH.CHjNH^ together with
CH,OH.CHrO.CH5.CH3NHj (Wurtz, A. 114, 51;,
121, 22G).— 7. Trimethylamime in aqueous solu-
tion forms neurine (Wurtz, A. Suppl. 6, 116,
197).— 8. Dimethylamine gives di-methyl-oxy-
ethyl-amine CHjOH.CHj.NMej (Ladenburg, B.
14, 2408), and CH,OH.CHj.O:CHj.OH2NMe2
(Morley, O. J. 37, 234).
Nitroxyl derivative CHjCl.CHj.O.NOj.
Chloro-ethyl nitrate. (150°). S.G. Zi 1-378.
From CHjCl.CH^OH, nitric acid, and HjSO„ or
from OH,Cl.CHjBr and alcoholic AgNO, (A. Ch,
[4] 27, 25'7 ; Henry, C. B. 96, 1062). Oil.
Acetyl derivative CHXl.CHjOAo. Olycol
chloracetim,. (145°). S.G. 2 l-i783. Formation.- -
1. From glycol, EOAc, and gag^ons HCl at 100°
63
CHLORO-ETHYL ALCOHOL.
(Simpson.il. 112, 147).^2. FroinCH,OH.CH20Ao
and HCl (Simpson, A. 113, 116).— 3. From glycol
and AcCl in the cold (Lourenfo, ^. Gh. [B] 67,
260 i 114, 126).— 4. From ohloro-ethyl aleohol
CH^CLCH^OH and AoCl (Henry, \B. 7* 70 ; De-
lacre, BJ. [2] 48, 707), orAcjO at 110° (Ladenburg
a. Demote, B. '6, 1024). T?rapeirtie&. — Liquid ;
Ronyerted'^by aqueons potash into ethylene oxide.
Chloro-aeetyl dirivative
CHjCl.CHj.0.C0.CH2Ca. (198"). From ehloro-
ethyl alcohol and chloro-acetyl chloride (Delacre,
m. [2] 48, 708), or from ethylene and C1,0
(Mulder a. Bremer, JB. 11, 1958).
Di-chloro-acetyl derivative
CH2Cl.CHj.0.C0.CHCl,. (211"). S.G.is 1-200 (D.).
^ri-chloro -acetyl derivative
CHjCl.CH2O.CO.CCl,. (217°). S.G. JS 1-251 (D.).
Sutyryl derivative CHjGl.CHjO.CO.Pr.
(190°). S.G. s 1-0854. From glycol, butyric
acid, and gaseous HCl (Simpson, A. 113, 119).
Benzoyl derivative CHjCLCHj.OBz.
(260°-270°)i. From glycol, benzoio , acid, and
HCl at 100° (S.).
ao-Di-ohloro-ethyl-alcohol CHjCl.CHCl.OH.
Acetyl derivative CHjCl.CHCl.OAo.
(o.l63°). From acetyl-ehloride and the hydrate ot
chloro-acetic aldehyde (Natterer, M. 3, 453). Oil.
An isomeride (147°) is formed by treating
CCl,.CHC1.0Ao with Zn and HOAc (Curie a.
Milliet, B. 9, 1611).
Di-chloro- ethyl alcohol CHClj.CHj.OH. .
(146° i.V.). S.G. is. 1-145. V.D. 3-93 (calc. 3-97)
(Delacre, C. R. 104, 1184). From di-chloro-
acetic aldehyde and ZnEt^, the product being
decomposed by water. Liquid, si. sol. water,
sol. alcohol and ether. Beduces a,mmoniacal
AgNOj. Does not dissolve CaClj. Fuming
HNOj giVes di-ohloro-aoetie acid. Converted by
PCI5 into CHClj-CH^Cl (115°), and by PBr, into
CHClj-CHjEr (138°).
li'itroxyl derivative CHCl'j.CH^.NOa.
JH-chloro-ethyl nitrate. (156° i.V.). V.D. 5-56
(oalo. 5-53) (De Lacre, C. B. 104, 1186). From
CHClj,CHjOH by HNO3 and H^SO,.
Acetyl derivative CHGl2.CH2.OAc. Di-
chloro-cthyl acetate. (167° i.V.). V.D. 5-74 (ealc.
5-42). S.G. l£ 1-104 (Delacre, C. B. 104, 1186).
Chloro-acetyl derivative
CI2CH.CH2O2C.CH2CI. (215° cor.). S.G. -'S 1-216.
Prepared by acting with mono-ohloro-aoetyl
chloride on di-chloro-ethyl alcohol on the water-
bjath until no more hydrio chloride is evolved
(Delacre, BZ. [2] 48,708).
Di-ehloro-acetyl derivative
CI2CH.CH2O2C.CHCI2. (223°). 8.0. " 1-25.
Formed by heating di-chloro-ethyl alcohol and
di-chloro-aoetyl-chloride together on the water-
bath (Delacre).
Tri-chloro-acetyl derivative
CI2CH.CH2O2O.CCI3. (230°). Formed by the ac-
tion of tri-chloro-acetyl chloride on di-ohloro-
eth'yl alcohol (Delacre). '
Tri-chloro-ethyl alcohol CCla.CHjOH. [18°].
(151°). S.G. 23 1-550.
The zinc salt (CClj.CHj.OJsZn is formed by
the action of ZnEt^ on chloral; it is decom-
posed by water into Zn(0H)2 and tri-a-chloro-
ethyl alcohol (GarzaroUi-Thurnlackh, A. 210, 63 ;
Delacre, Bl. [2] 48, 785). It is also formed, to-
gether with glycuronio acid CgH,oO„ by treating
urochloralic acid with dilute BCi (Kiilz, Z. j^.
20, 161). Hygroscopic trimetrio taMes ; gl. Bol.
water, v. sol. alcohol and ether. HNO3 forms
tri-chloro-acetic acid. Beduces hiit Fehling'a
solution.
Acetyl -derivative ClsC.CHjOAc. (170°).
S.G. isi-189. Formed by digesting at a gentle
heat acetyl chloride and triohloro-ethyl alcohol.
Chloro-aCetyl derivative
CljCCHjO^CCHjCl. (220° cor.). S.G. i£ 1-25.
From chloro-acetyl-ehloride and tri-chloro-ethyl
alcohol (Delacre, Bl. [2] 48, 710).
Di-chloro-acetyl derivative
CI3C.CH2O2C.CHCI2. (231°) at 767 mm, S.G.
^ 1-267. From di-chloro-acetyl chloride and
tri-chloro-ethyl alcohol.
Tri-chloro-acetyl derivative
CljC.CHjO.C.CCl,. [26°]. (236°). From tri-
chloro-acetyl chloride and tri-chloro-ethyl alco-
hol. ■
uaa-Iri-chloro-ethyl alcohol. Acetyl d»'
rivative _ CHCl2.CHOl.OAo. (185°). TSiom
AcCl and di-chloro-acetic aldehyde (Delacie, BU
[2] 48, 714).
SI - CHLOBO - ETHYLAISISO - ACETIC
ETHEE C,H„Cl2N02 i.e. NHEt.CCl2.C0„Et.
[above 60°]. From NHEt.CO.COjEt and PCI.
(Wallach, A. 184, 76). Needles or prisms.
Water regenerates NHEt.CO.QOjEt. Ammonia
forms ethyl-oxamide.
iJ-CHLOEO-TETEA-ETHYIi.ij.DI-AHIDO.
TEI-PHENYL-CAEBINOL
CeH,Cl.C(0H):(CeHi.NEt2V [lai"]. Large
glistening colourless tables. Formed by oxi-
dation of its lenco-basc, the condensation-pro-
duct of diethylaniline and^-chlorobenzaldehyde.
Its zinc double chloride is a bluish-green dye-
stuff (Kaeswurm, B. 19, 745).
TEI-CHLOEO-^-ETHYIi-AMIDO-PHENYL.
ETHYL ALCOHOL CCl,.CH(OH).C„H,.NHEt.
[98°]. From chloral hydrate and ethyl-aniline.
Crystals (from alcohol).— B'HCl.
Nitrosamine CCl3.CH(0H).CeH4.NEt.N0
[138°]. Crystals (Boessneck, B. 21, 783).
Tri-chloro-di-ethyl-amido-phenyl ethyl alco-
hoi CCl3.CH(0H).CsHi.NEt2. Yellow oil. Formed
by adding 10 gi-ms. of ZnClj to a cold mixture of
60 grms. of diethylaniline and 20 grms. of'
chloral hydrate, and allowing to stand for 2 days
at 40°. It is decomposed by alkalis into
chloroform and ^-di-ethjl-amid6-benzaldehyde.
—B'HCl: crystalline solid (Boessneck, B. 19,
367).
^-CHLOEO -TETEA-ETHTL.D.DI-AMIDO.
TEI-PHEHYL-METHAKE
CaH,Cl.CH(C,H,.NEt2)2. [110°]. Obtained by
heating together di-ethyl-aniline, ^-chloro-benz-
aldehyde, and ZnClj (Kaeswurm, B. 19, 744).
Small colourless needles. Sol. benzene, alcohol,
and ether, insol. water. On oxidation it gives a
bluish-green dyestuff.
CHLOEO-ETHYL-AMINE v. Ethyl-chloro-
amhie, described under Eihtl-amine.
;8-0hloro-ethyl.aniine C1.CH2.CH2.^H2. From
vinylamine and cone. HClAq. Formed also by
heating oxyethylphthalimide with cone. HCl to
200° (Gabriel, B. 21, 573, 1049).— Salts.—
B'HCl. y. e. sol. alcohol, ether, and water,
Piorate — B'CsH,N,0, iaq. Yellow needles.
[143° anhydrous]. B'jHjPtCl,. Orftnge plalies,
V. bqI. water, al. sol. alcohol.
CHLORO-ETHYL BENZENES.
fia
CHLOBO-ETHYL-AHILINE 0,H,„C1N ».«.
CjH5.NH.CHj.0H2Cl. Formed by the action of
fuming HOI at 170° on the compound CbHjNOj
derived' from phenyl-carbamia aoid {q.v.). —
B'HOl. [158°] (Nemirowsky, J. m. [2] 31, 175):
p-Chloro-ethyl-aniline [4:1] C„H^Cl.NHEt.
Fromp-ohloro-aniline and EtBr. Liquid (Hoi-
mann, A. 74, 143).
p-ChloTO-di-etliyl-aniUue [4:1] C,H,Cl.NKt,.
From the preceding and HBr (H.). Liquid. —
B'^^PtCl..
£!so-CHLOBO-ETHYL-B£KZENES .
ObH4G1.(02H,). The three eso-ohloro-ethyl-benz-
enea are obtained simultaneously by the action
of CjHj upon OaHjCl (500 g.), in presence of
ilLGle (100 gr.). The mixture is an oily liquid
(0.180°). S.a.ai-oes. V.D.4-77. Very vola-
tile, and of agreeable odour. Sol. ligroin (1 vol.),
OSj, CHC1„ and ether. Sol. CsH, (2 vols.) and
alcohol (3 vols.). The proportion of the three
isomerides ia roughly o:»re:j) = 7: 10:3. On
oxidation it gives a mixture of the three chloro-
benzoio acids. Heated with sulphuric acid it
gives sulphonic acids (Istrati, A. Ch. [6] 6, 402 ;
m. [2] 42, 114).
a-Chloro-ethyl-benzeae OHjCa.OHa.CaH3 (?).
(0. 202°). Formed by chlorinating boiling ethyl-
benzene (Fittig a. Eiesow, A. 156, 240 ; c/.
Schramm, M. 8, 105). Split up by boiling into
HGl and styrene. Converted by alcoholic KOy
into the nitrOeof |8-phenyl-propionic acid (?).
a-Chloro-ethyl-benzene CHa.CHCl.CeHs.
(194°). Formed by the action of chlorine on
ethyl-benzene in sunlight, and also on boiling
ethyl-benzene (Schramm, M. 8, 101). Formed
also by passing HCl into cold M-phenyl-ethyl
alcohol C„H,.OH(OH).OH., (Engler a. Bethge.B.
7, 1127). With benzene and AljOl, it gives s-di-
phenyl-ethane (Ansohiitz, A, 233, 829).
Cbloro-dl-ethyl-benzenes C^fi\(0^^.y A
mixture of ohloro-di-ethyl-benzenes is formed
by treating C0H5OI with CjH, in presence of
AljCl.. It ia a mobile liquid, with agreeable
odour. (0.218°). S.G.21-036. V.D.6-65. Sol.
ligroin (in all proportions), GS„ ether, and
CHCl,. Sol. benzene (3 vols,), alcohol (7 vols.).
On oxidation, it gives rise to two chloro-phthalie
acids, and chloro-ethylphenyl methyl ketone
(CjHJ.0,H3.Cl.C0.CH3 (Istrati).
Chloro-tri-ethyl-benzenes CeH-C^OaHJj. A
mixture of these substances is obtained by con-
tinuing the passage of ethylene into ohloro-
benzene in presence of AljClj. Mobile Uquid.
(248°). V.D. 6-87. Sol. (in all proportions)
ether, petroleum ether, CS^, and OHCI3. Sol.
benzene (3J vols.), and alcohol (30 vols.). On
oxidation with permanganate it gives a tri-car-
boxylio aoid, having an insol. Ba salt- (Istrati,
A. Ch. [6] 6, 426).
CWoro-tetra-etbyl-benzenes C,HC1(C2H5)<. A
mixture of iaomeridoa of thia composition is
formed by the further action of CjH^ upon
C.H-01 in presence of AljOl,. Liquid. S.G.
2 1022. (c. 27I). V.D. 7-17. V. sol. ether,
ligroin, CSj, and CHOI,. Sol. benzene (4 vols.)
and 90 p.e. alcohol (26 vols.) (Istrati).
Chloro - penta - ethyl - benzene C,01(CjHi),.
Formed by the prolonged action of CjH, upon
O.H,Cl in presence of AljOl,. The yield is not
good. Mobile Uquid. S.a. 2 1-065. (0. 292°).
VJ). 8-43. V. soL ether, ligroin, CS„ and CHOlj.
Sol. benzene (5 J- vols.) and 90 p.o. alcohol (32
vols.) (Istrati, A. Ch. [6] 6, 428).
Di-ohloro-ethyl-benzene 0^,01,(CjHJ [1:4:2].
S.G. 2-1.239. (213°). V.D. 6-24. Formed by
the action of O^H^ upon O^HjCl, [1:4] in pre-
sence of AljOlo, at 125°-150° (Istrati, A. Ch. [6]
6, 476). Liquid. Sol. benzene (3 vols.) and
90 p.o. alcohol (9 vols.). Yields a di-chloro-ben-
zoio acid on oxidation.
coai-Di-chloro-ethyl-benzene OgH^.OHa.OGlaH.
Phenyl-di-chloro-ethwne. Formed by the action
of PCI, on phenyl-acetic aldehyde (Forrer, B. 17,
982). Heavy colourless liquid. Volatile with
steam. By boiling with water it is converted
into w-chloro-styrene.
ao-Si-chloro-di-cthyl-benzene C,Hj.O0l2.OH,.
Aoetophenane chloride. From acetophenone and
PCI5 in the cold (Friedel, Bl. 1, 7 ; Ladenbur;;,
A. 217, 105). Beadily splits off HOI.
mn-Dl-ohloro-di-ethyl-benzene
CnHj.OHOl.OHiOl. Styrene diehloride. From
styrene and chlorine (Blyth a. Hofmann, A. 53,
309). Decomposed on distillation. Alcoholic KOH
gives 0„H30H:CH01.
Qi-chloro-di-ethyl-benzene C|iHjCL(02Hj)j. A
mixture of di-chloro-di-e'thyl-benzenes is obtained
by treating ^-di-ohlor-benzene with CjHj in pre-
sence of AljOl,. Liquid. S.G. 2 1-179. (c. 247°).
V.D. 7-17. Sol. benzene (4 vols.) and alcohol
(10 vols.) (Istrati, A. Ch. [6] 6, 482).
Bi-chlor-tri-ethyl-benzene C,H0l2(02Hj),
[1:4:3:5:6]. S.0. 2 II3I. (C. 273°). V.D. 8-77
(calo. 7-99). Formed by the action of CjH, upon
jp-di-ohlor-benzene in presence of Al^Clg (Istrati).
Ijiquid. Sol. benzene (5 vols.), alcohol (30 vols.).
HNO, gives C„(N0,)CU(0,,H5),, [20']. (312°).
JI,SO, gives 0„(S03H).CL.(0.,H,)3.
Si-chloro-tetra-ethyl-benzene C,Cl2(C2Hj)4
S.G. 2 1-129j (296°). V.D. 9-26 (calc. 8-96). Pre-
pared by the action of C.H, uponp-di-ohloro-ben-
zene in presence of AljOl,. Liquid. Sol. 90 p.c.
alcohol (46 vols.) and benzene (6 vols.) (Istrati,
A. Ch. [6] 6, 485).
Iri-chloro-ethyl-benzene CJIfil^^O^'ELi). A
mixture of these bodies is formed by treating
CbHjOI, [1:2:4] with C^Hj in presence of AljOl,
(Istrati, .4. 0/1. [6] 6, 490). Liquid. S.G. 2 1-389. '
(244°). V.D. 7-24. Sol. benzene (3| vols.) and
alcohol (17 vols.).
Tri-chloro-di-ethyl-benzone 0aHCla(C2Hj)j. A
mixture of these bodies is obtained by treating
CHsOla [1:2:4] with OjH, in presence of AljCl,.
Liquid, greases paper. S.G. 2 1-805. (269°). V.D.
8-37. Sol. benzene (5 vols.) and alcohol (26 vols.).
Tri-ohloro-tri-ethyl-beiizene CeCl,(C2H5),.
S.G. 2 1240. (291°). V.D. 8-42 (calo. 8-19).
Prepared by passing CjH, into a mixture of
AljCl, and C.H,C1, [1:2:4]. Oil. Sol. benzene
(5 vola.) and alcohol (41 vols.).
Tetra-ohloro-etliyl-benzene CjHC^CjH,).
S.G. 2 1-543. (3. 272°). V.D. 799 (calo. 8-47).
Formed by treating C.HjCl, [1:3:4:5] with C^H,
in presence of AljCl,. Yellowish liquid. SoL
benzene (5^ vols.) and 90 p.c. alcohol (16 vols.).
HNO, givea a nitro-derivative [30°] (Istrati,
A. Ch. [6] 6, 497).
aoMoj-Tetra-cMoro-ethyl-benzeae
CHClj.CCl2.CjH,. From di-chloro-styrene and
CI (Dyckerhoff, B. 10, 533). Liquid. On distit
lation it splits up into HCl and C01,:CC1.0,H,.
Bl
CHLOEO-RTHYI. BENZENES.
Tetra-chloro di-ethyl-benzeue C,Cl,(C2Hj)j
[1:3:4:5:2:GJ. S.G. is 1-431. [45°]. (290°). V.D.
8-44 (cale. 9"07). Formed by treating M-tetra-
chloro-benzene with ethylene and AljClj. Prisms
(from a mixture of alcohol and benzene). Sol.
benzene (7 vols.) and 90 p.o. alcohol (40 vols.)
(Istrati, i.Ofc. [6]6, 500).
Penta-ohloro-etliyl-benzeno 0,Clj(CjHj). [85°].
(,o. 297°). S.G. M 1-720. V.D. 9-57 (calc. 9-29).
Prepared by submitting CjHCl,, in presence of
CoHj, to the influence of AI2CI,. The yield is
Bmali. HCl gas facilitates the reaction and gives
a better yield. White crystals (from alcohol
with benzene). V. sol. ether, OHCl,, ligroin and
CSp Sol. benzene (9 vols.) and 90 p.c. alcohol
(108 vols.). Ou oxidation with permanganate
it gives OjCls.COjH, which immediately loses
COj forming CsHClj (Istrati, A. Ch. [6] 6, 502).
CHLORO-ETHYL-BEirZKirE SULPHONIC
ACID 0„H3C1(02H5).(S03H). Formed by heating
the mixture of ohloro-ethyl-benzenes with H2SO4
at 180°. The product appears to consist of
several isomerides (Istrati, A. Gh. [6] 6, 411).
J!so-CHL0EO-ETHYL-BENZ0IC ACID
C„H,(Ci,H5)Cl.C02H. [115°]. Formed by fusing
the ketone CjHsCl.(0jH5).C0.CH3 with KOH.
White solid ; insol. water ; begins to sublime at
100°. — BaA'j : small crystals ; insol. cold water
(Istrati, A. Ch. [6] 6, 424).
GHLOKO-ETflYL CABBAMATE
NHjCOAH,Cl. [115°] (G.) ; [76°] (N.). Formed
by the action of ohloro-ethyl-alcohol (glycol
chlorhydrin) on chloro-formamide (Gattermann,
A. 244, 41) J and of ClCHj.CHj.O.COCl on am-
monia (Nemirowsky, J. pr. [2] 31, 174). Colour-
less, strongly refractive plates. Insol. cold, m. sol.
hot water.
TETSA-CHLORO-DI-ETEYI. CAEBOHATE
(C^HjCy^CO,. Obtained by passing chlorine
into carbonic ether in diffused daylight, ulti-
mately at 80° (Oahours, A. Ch. [3] 9, 201).
Heavy oil, decomposed by heat.
Per-chloro-di-ethyl carbonate (CjCyjCOj.
[86°]. Formed by chlorinating the preceding in
direct sunshine (Malaguti, A. Ch. [8] 16, 30).
Mass of needles. Distils with partial decompo-
sition into GOj, CjOlj, and CCla-COCl. Solution
in alcohol converts it into carbonic and tri-chloro-
acetic ethers. Aqueous KOH gives potassium
formate, carbonate, and chloride. Gaseous or
aqueous ammonia forms tri-chloro-acetamide
(Gerhardt, Traiti, 1, 166) and a substance melt-
ing at 37°.
CHIORO-ETHYI-CEOTONIC ACID 0,H,C10j.
Chloro-hexenoie acid. [49-5°]. (215°). S. -2
at 1° ; -33 at 12°. Formed, together with ohloro-
and di-chloro-ethyl-aoeto-acetic ether by the
action of PCI, upon ethyl-aceto-acetic ether.
Keedles (from alcohol or ether). Unpleasant,
pungent odour (Isbert, A. 234, 183 j cf. Demarpay,
B. 10, 1177). Not reduced by sodium amalgam.
Salts. — NaA' deliquescent. — BaA'p —
CaA',2aq. S. 12 at 19°. Prisms.— AgA'.
Ethyl ether MA'. (185°).
^^ ^^
Chlobo-pbofionic acid.
CHLOEO-ETHYL CYAITIDl
NitriU of
CHLOEO-ETHYLENE CjHaCl i.e. CHjtCHCl.
chloride. (-16°). V.D. 2-17. H.F.p.
-1880 [Th.). H.F.V. -2460. Formed by
the action of alcoholic EOHon ethylene chloride
CH,C1.CH,CI (Begoanlt. A. 14, 28), or on ethyl-
idene chloride CIlj-CHClj (Wurtz a. FrapoIH, .A.
108, 224). It is a gas which polymerises in sun-
shine, changing to an amorphous mass, S.G.
1-41, which melts and turns black at 130° (Bau-
mann, A. 163, 817). Ammonia has no action
on chloro-ethylene below 100°, but at 160° it
forms ethylene diamine CH.NH,.OHjNH, (118°)
(Engel, Bl. [2] 48, 94). Chlorine unites with
CHjiCHCl in sunshine.
M-Di-ohloro-ethylene CHjiCCl™ (36°). S.G.
IS 1-250. V.D. 3-32 (oalo. 3-36). Formed by the
action of alcoholic KOH on CH^Cl.CHOl^ (Eeg-
nault, J. pr. 18, 80; Kramer, B. 8, 261), on"
CHjBr.CHClnOron di-chloro-iodo-ethane (Heitty,
C. B. 97, 1491 ; 98, 518). Liquid, with alliaceous
odour ; changes spontaneously into a crystalline
isomeride. Chlorine in daylight followed by
sunshine gives CjClj; direct siinshino gives C
and HCl. Does not react with KI.
s-Di-chloro-ethylene GHChCHCl. Acetylem
dichloride. Mol. w. 97. (55°). Formed by
passing acetylene into cool SbCl,, the resulting
crystalline compound OjHjSbCls being decom-
posed by water (Berthelot a. Jungfleisch, A. Ch.
[4] 26, 472 ; but cf. Sabanejeff, il. 216, 262). From
CHClBr.CHGlBr and zinc in alcoholic solution
(s.).
Tri-ohloro-ethylene CHChCClj. (88°). From
either tetra-chloro-ethane by treatment with aloo-
hplio KOH (Berthelot a. Jungfleisch, C. B. 79,
542 ; A. Swppl. 7, 255). From C^Cl,,, zinc, and
dilute H,SO, (B. Fischer, Z. 1864, 268). Also
from chloral and PjSj at 170° (Paternd a. Oglia-
loro, B. 7, 81). With alcoholic KOH it gives
CaHClrOEt. Aqueous or alcoholic NH, forms
CjHjClj (87°) (Engel, O. B. 104, 1621). Sodium
forms acetylene, ethylene, C2H2CI2, and hydro-
gen (Bronner a. Brandenburg, B. 10, 1496 ; 11,
61).
Tetra-cMoro-ethylene CjCl, i.fl. CCl^rCCl,.
(121°) (S.) ; (125°) (C). S.G. ~ 1-6312 (Sohifl,
A. 220, 97) ; =j° 1-6190. V.D. 5-82 (calo. 5-75).
C.E. (9-4° to 120°) -001147. it.^ 1-515. Bg, 49-66
(Bruhl), S.V. 114-18. H.F.p. -1150, (Th.).
H.F.V. -1730. Discovered by Faraday (27.
1821, 47) by subjecting C^Clg to a red heat either
' alone or in presence of E. Formed also by treat-
ing GjClg with alcoholic KHS (Begnault, A. Ch.
[2] 70, 104 ; 81, 372), with water and granulated
zinc (Geuther, A. 107, 212), with alcohol and
zinc filings, or with aniline (Bourgoin, Bl. [2]
23, 344). Formed also by the action of Al^Cl, on
chloral (Combes, A. Gh. [6] 12, 298). Obtained,
together withCGl,, by heating per-chloro-propane
at 300° (KrafEt a. Merz, B. 8, 1300).
BeacUoim. — 1. Bromme forms in sunshine
crystals of CjSifiT„. — 2. Dry chloritie combines
in sunshine fo'rming CjClg. — 3. Chlorine-water
gives tri-ohloro-acetic acid (Kolbe, A. 54, 181). — '
4. Dry oxygen has no action even at 120° (Demole
a. Dilrr, B. 11, 1302). — 5. Potash-fusion gives
potassium oxalate and hydrogen (Geuther, A, '
111, 174). — 6. NaOEt at 120° gives
CHClj.C(OEt)„ CH0l,.0O„Et, CH(OEt),.CO,Na,
and CGUGCLOEt (Geuther, J. 1864, 316 ; J.pf.
[2] 7, 108).— 7. SO, at 150° gives CCI,.C001.
CHIOEO-ETHYLENE OXIDE O^UfilO.
(89°-92°). Formed by heating chloro-iodo-ethyl.
ene CHC1:CHI, with water (60 vols.) at 150° tot
CHLORO-DI-ETIIYL OXIDE.
66
6 days (Sabanejefi, A. 216, 268). Liquid. SI.
sol. water.
CHLOEO-ETHYIEUE CHLOEIDE ». Tar-
OHLOBO-ETHANB.
CHI.OBO-EIHTL ETHES v. Chlobo-di-btuyl
OXIDS.
TEI-CHLOEO-ETHTLIDENE-ACETO-ACEXIO
EIHEE V. AOETO-AOBTIO ACID.
TEI-CHLOEO-ETHYLIDENE DIAMINE.
Acetyl derivative 001s.CH(NHAc)3.
Formed by heating chloral with aceto-nitrile
(Hubner, Z. 1871, 712; Hepp, B. 10, 1651),
the equation bemg: GClj.CHO + 2CH3CN + H^O
= C0^.0H(NH.C0.CH3)a. Needles (from glacial
aoetio acid). Sol. water and alcohol. Sublimes
without mejting.
Benzoyl deripative CCl3.CH(NHBz)2.
[257°]. From chloral, benzonitrile, and cone.
HjSO.. Needles; v. si. sol. ether.
CHLOEO-ETHYLISENE-ANIIIKE
OJECsNCl i.e. CHjCLCHiNOsH,. [136°].
Prepa/ration. — Di - ohloro - di - ethyl oxide
OHjOl.CHCl.OEt (1 mol.) is warmed with aniline
(2 mols.) in the presence of water. A white
powder [87°] is formed, which becomes red [136°]
when dried.
Properties. — Bed brown powder. Sol. aloor
hoi ; it may be a polymeride of the white com-
pound.
BeacHons. — 1. HNOj produces a yellowish
grey amorphous body which gives a blue colour
with phenol and cono. BLjSO,. — 2. Warmed with
anihne it forms phenylamido-ethylidene aniline
08H5N:CH.0Hj.NHG3H5 [104°] which yields in-
dole on heating (Berlinerblau a. Polikiev, if. 8,
187-189).
CHIOEO - ETHYLIDENE DI - CAEBAMIC
ETHEE CsH.sOlNA »•«• CH^Cl.CH(NH.C0jEt)2.
[147°]. Formed by the action of chlorine on a
strong solution of HON in alcohol ; and also by
adding cono. aqueous HOI to a solution of car-
bamic ether in chloro-acetal OH201.0H(OEt)2
(BlschofE,B.5,81; 7,630). Formed also by chlo-
rinating ethylidene di-carbamie ether (Schmid,
J. jpr. [2] 24, 122). Needles (from dilute alco-
hol). V. sol. ether and alcohol.
Di-cMoro-ethylidene di-carbamlc ether
CH0i,.0H(NH.C0^t)j. [122°]. Formed by
passing 01 into an alcoholic solution of HgCyj
(Stenhouse, A. 33, 92 ; Bisohoff, B. 5, 82). Also
by passing chlorine into carbamic ether at 90°
(Schmid, /. pr. [2] 24, 120). Long needles ; v.
sol. alcohol and ether.
TBI - CHLOEO-ETHYLIDENE-TEI-CHLORO-
LAOTATE V. Cei.oralide.
CHLOEO-ETHYLIDENE BIYCOL.derivativBS
of, V. Chloko-aldehtde.
TEI - CHLORO - ETHYIIDENE - MALONIC
ACID OOL.CH:0(002H),.
Ethyl ether Et^A". (160°-164°) at 23 mm.
From chloral, malonic ether and Aafi at 160°
(C. M. Thompson, 4. 218, 169).
TEI - CHLOEO - ETHYLIDENE-DI-PHENYL-
DIAMINE V. TKI-OHLOBO-M-PHBNyli-BIHTlilDENE-
DIAMINE.
TEI - CHIOEO-ETHTLIDEHE-aUIIIALDINE
V. [By. 3)-QrniOLTL-AOBYLO-TKI-CHLOEIDE.
CHLOEO - ETHYLIDENE -p - TOLUIDINE
C„H,„NC1 t.e. CH,.C„H,.N.CH.CH,C1. [58°].
Prepared by decomposing di - chloro - ether
CH2Ol.CHOl.OEt mth' water, and adding jp-
Voi,. IL
toluidiue. Sol. alcohol and ether; forms with
aniline or toluidine a compound free from chlor-
ine. Heated with aniline it yields indole (Ber-
linerblau a. Polikiev, M. 8, 190, 191).
DI-CHLOKO-ETHYLIDENE-DEEA
C0(NH)20H.0HCl2. From di-chloro-aoetio aide,
hyde and urea (Sohift, A. 151, 186). Needles.
Tri-chIoro.ethylideae-di-ureaC,H,Ol3N40ji.e.
CCl3.0H(NH.OO.NH2)i,. Is the.ohlef product of
the reaction of ohloral-cyanhydrin with urea.
White needles. Insol. ordinary solvents (Pinner a>
Lifsohiitz, B. 20, 2346).
CHLOSCETHYI-MALONIC ETHEE
02H5.CCl.(C02Bt)j. (228°). S.G. i^ 1-11. Liquid.
Prepared by passing 01 into ethyl-malonic ether
(Conrad, B. 14, 618). By saponification with
baryta-water it gives ethyl-tartronio acid,
DI-CHLOEO-ETHYL MESCAPTAN
0HjCl.CH3.S01(?). 8.0-. 13 1-408. Said to be
formed from ethylene and SOlj (Guthrie, A.
113, 275). ' Pungent oil, si. sol. ether.
CHLOEO-DI-ETHYL OXIDE 0^010 t.«.
CH3.CHCl.OEt. Aldehyde ethylo-chloride. Mol.
w. 108^. (98°).
Formation. — 1. The first product of the ac-
tion of chlorine on ether (Lieben, A. Ill, 121 ;
146,180; Abeljanz, 4. 164, 197 ; Jacobsen,JB. 4,
215). — 2. By the action of HCl on an alcoholic
solution of aldehyde (Wurtz a. FrapolU, A. 108,
226; Olaus a. Trainer, B. 19, 3004).— 3. By
the action of PCI5 (1 mol.) on di-ethyl-acetal (1
mol.) (Bachmann, A. 218, 39). — 4. By thei union
of aldehyde with EtCl.
Reactions. — 1. NaOEt gives acetal. — ^2. Cono.
HjSO^gives EtHSO,, aldehyde and HCL— 3. Cold
water forms aldehyde, alcohol, and HCl. Water
at 80° gives aldehyde (Laatsch, A. 218,36).
Alkalis act in the same way. Cold a,lcohol has
no action, but at 80° aldehyde and EtOl are
formed. — 4. Decomposes on keeping inio HGl
and a liquid boiling at 76°.
0). Chloro -di- ethyl oxide OHaCl.CHyOEt.
(108°). : S.G. 2 1-0572. V.D. 3-73 (calo. 3-74).
From iodo-di-ethyl oxide by the action of 01, of
SbClj, or of 101 in presence of water (Henry,
C.B. 100, 1007). It is not affected by light or
by water. ,
wa-Di-cMoro-di-ethyl oxide OHjOLCHOLOEt.
(c. 143°). S.G. 23 1-174. V.D. 493. Obtained
by the action of chlorine on ether below 30°
(Lieben, 4. Ill, 121; 123, 130; 133, 287; 141,
236 ; 146, 180 ; 150, 87 ; Abeljanz, A. 164, ,197 !
cf. D'Arcet, A. 28, 82 ; Begnault, A. Oh. [2] 71,
392 ; Malaguti, A. Oh. [2] 70, 338 ; [3] 16, 5, 19).
Formed also, together with the preceding, by
passing HCl into a mixture of aldehyde and al-
cohol (Natterer, M. 5, 496). Also from vinyl-
ethyl oxide CHj:OH.O.Et and 01.
BeacUms.—X. Water at 120° gives the com-
pound OHjCl.CH(OH) (OBt) , together with chloro-
acetic aldehyde, glyeollic aldehyde, alcohol and
HCl.— 2. Cone. i^SOj produces EtHSOj, ohloro-
acetic aldehyde, and HCl.— 3. With cone.
potash it forms ehloro-aldehyde alcoholate
and its anhydride, and also ' oxychldro-ether,'
CHaOH-CH^Cl-OEt (151°-155°)i This latter
body is split up by cone. HjSOi.inta HCl, alco-
hol and glyeollic aldehyde (?), tiHjOH.CHO.^
4. NaOEt gives chloro-acetal 0Hj01.0H(0Et),
and CH,(0Et).CH(0Et)2.— 5. AgOAo gives
0H.,01.GH'(0Et)(0Ac) (Bauer, A. 134, 176).—
CHLORO-DI-ETHYL OXIDE.
6. Dry metallio iinc acts vigorously, producing
HCl,.ZnClj, EtCl, alcohol, OHjCl.CHO, and a con-
densation product of the alcoholate of the latter,
CjH.eCLjO, (Wislioenus, A. 226, 271).— 7. Zme in
presence of water produces aldehyde, Et20,
alcohol and chloro-aldehyde, besides small
quantities of orotonic-aldehyde, chloro-acetal,
/S-oxy-ohloro- ether (OHjOH.OHCl.OEt) and
(CHj01.CH(OBt))jO (W.).— 8. In ethereal solu-
tion with ZnEtj it forms CHjOl.CHEt.OEt,
' ethyl chloro-ether ' (ethyl ohloro-butyl oxide).
9. Excess of ZnEtj gives ethyl hexyl-ether,
CH2Et.CHEt.OEt.— 10. With ZnMej it gives
CH2Cl.CHMe.OEt, i^. ethyl ohloro-isopropyl
ether. — 11. Di-chloro-di-ethyl oxide (25 g.)
heated with amilme (50 g.) and water forms
indole (Berlinerblau, M. 8, 180).— 12. Phenol
forms C2H,(C^40H), (Wislicenus a. Beinhardt,
'4- 243, 151). — 13. (a)-.NaphtholtoxTiis amorphous
C^,(G,oH,OH),. (;3)-naphthoI gives crystalline
plates of CjjHuClO [174°] (Wisliceuu* a. Zwan-
ziger, A. 243, 165).— 14. Mesorpin, Pyrocatechin,
and Sydroqumone form compounds of the form
C2H3(C,H,02H2)3 (Wislicenus a. Siegfried, 4. 243,
171).— 16. Thiourea forms thiazoUne (Hantsch
a. Traumann, B. 21, 938).
Si-ohloro-di-ethyl oxide (CH3.GHC1)20.
ElhyKdene oxychUmde. (117°). S.G. iil' 1-136.
V.D. 5-08 (calc. 4-95). From dry aldehyde
cpoled by a freezing mixture by passing dry HCl
into it. The product is dried with GaClj and
distilled (Lieben, C. B. 46, 662 ; Eessel, A. 175,
44 ; 176, 44 ; Geuther, A. 218, 16).
Beactions. — 1. Water on warming decom-
poses it into HCl and aldehyde. — 2. Alcohol forms
chloro-diethyl oxide (OHs.CHCljjO + 2H0Et
_=2CH,.CHCl(OEt)+H20.— 3. NaOBt converts
it (in ethereal solution) into aldehyde-resin,
acetal, and alcohol. — 4. Alcoholic sodiMm ethyl-
ate forms, besides the same products, a liquid
jCH,CH.0Et)20 (153° cor.) S.G. J* -891. Thjs
IS sparingly sol. water. It decomposes in a few
days into acetal and aldehyde: (CH,CH.0Et)20
= CH,.CH(0Bt)2-HCH,.CHO.— 5. Dry NaOEt
gives CH,.CH(0Et).0.CHCl.CH3 (146°), a liquid,
decomposed by hot water (Hauriot, A. Ch. [5]
25, 223).-^6. MeOH and NaOMe form similarly
(CH3CH.0Me)20 (126°-127°). S.G. HP -953.
This also has an aromatic smell and splits up
like the foregoing, though more slowly, into di-
methyl acetal and aldehyde. — 7. Sodium succi-
nate eivesO{GBiie.OCO)fi^H.t (Geuther, 4. 22G,
228). — 8. Zinc ethyl produces di-butyl oxide
(CH,.CHEt)20.
tri-chloro-di-ethyl oxide CHClj.CHCl.0Et.
(157°) (G.); (168°) (K.). From chloro- vinyl
ethyl oxide and CI (Godefroy, O. B. 102, 869).
Also from di-chloro-acetal and PCI, (Krey, /.
1876, 475). Occurs in the product of chlorina-
tion of ether. Fuming liquid ; with NaOBt it
gives CHCl2.CH(0Et) J. Cono. aqueous KOH gives
CClj:CH.OEt (145°).
Tetra-chloro-di-ethyl oxide CClj.CHCl.OEt.
Mol. w. 212. (190°) (P. a. P.) ; (0. 183°) (G.).
S.G. 2 1-437; 15 1-418.
Formation. — 1. From chlorine and ether at
90° in the dark. — 2. Froln chloral alcoholate
and PCI5 (Henry, B. 4, 101, 435 ; Patem6 a.
Pisati, J. 1872, 303; G. 2, 333).— 3. From di-
ohloro-vinyl ethyl oxide GCl2:CH.0Et and chlo-
rine (Godefroy, C. B. 102, 869).
Reactions.— 1. CoAc. HjSOj gives chloral,
HCl, and alcohol. — 2. Heated with alcolwl it
gives tri-ohloro-aoetal CCl3CH(OBt)2.— 3. With
dilute (10 p.o.) alcoholic potash it gives trichloro-
vinyl-ethyl oxide CCl2:CC1.0.Et.— 4. H2S gives
C^H^SjO [123°] and C^HjCljSO [72°] (Malaguti,
A 32 29). ^
Penta-chloro-di-ethyl oxide CCl,.CCl2.0Et.
(190°-210°). S.G. 1-65.
Formation. — 1. The final product of the action
of chlorine on ether in the dark (Jacobsen, B.
4, 217).- 2. From CCljiCCl.OEt and CI (Busoh,
B. 11, 445). It is partly decomposed on boiling.
Fenta-chloro-^-ethyl oxide
CCl3.CHC1.0.CHj.CHjCl. (235°). S.G. a : 1-577.
Prom PCls and C0l3.CH(OH).O.CH2.CH2Cl, a
compound of chloral and glycolio chlorhydrin
(Henry, B.7, 763).
Hexa-chloro-di-ethyl oxide (CHClyCHC^jO.
(250^). From PCI, and the hydrochloride of di-
chloro-aldehyde (Patern6 a. Pisati, G. 1, 461).
Octo-chloro-di-ethyl oxide C4H2CIBO. Formed
by the action of CI on aldehyde hydrochloride
in sunlight.
Crystals, smelling like camphor, may be sub
limed (Both, B. 8, 1017).
Per-chloro-di-ethyl oxide C,C1,„0. [69°]. S.G.
^ 1-900. Formed by the action of chlorine in sun-
light on ether (Begnault, A. 34, 27 ; Malaguti,
A. Ch. [3] 16, 4). Dimetrio octahedra (NickUs,
A. Ch. [3] 22, 28). Splits up on heating into
CjCl, and trichloro-acetyl chloride.
CHLOEO-ETHTL-OXY-TOLTIftTJXNOIIlSrE v.
CHLOBO-OXY-MEIHYIi-EIHYIi-QinNOLIIIE.
a . CHLOBO - DI - ETHYL - DI - PHENYL-
ETHANE CisHjiCl i.e. CH2Cl.CH(CaH,Et)2.
(c. 268°). From ethyl-benzene, CHjOl.CHCl.OEt,
and H2SO, (Hepp; B. 7, 14U). On distillation
it gives HCl and CuHj,,.
Bso-CHLOEO-ETHYL-PHEim METHYL
KETONE C„HsBt01.C0.CHj. Formed, together
with the two ohloro-phthalic acids, by oxidising
chloro-di-ethyl-benzene with chromic mixture
(Isirati, A. Ch. [6] 6, 421). Iiiquid ; not attacked
by boiling alcoholic KOH, but converted into
chloro-ethyl-benzoic acid by potash-fusion.
CHLOEO- TETEA-ETHYL- PH0SPHONHTM
CHLOEIDE (ClCHj.CHj)PEt3Cl. From Pfit, and
ethylene chloride in the cold (Hofmann, A.
Suppl. 1, 276). Needles. Moist AgjO converts
it intoanoxy-ethyl baseCH2(OH).CH2.PEt,OH.
Salt.— (OjH,Cl.PEt3Cl)2PtCl4. Orange needlfes.
CHLOEO-ETHYL-PEOPYL-OLYOXALINE
CbHijCINj., Chlor-oxal-propyVime (236° cor.).
V.D. = 6-65(obs.), S.G.iai.09. From di-propyl
oxamide by PCI5. Oil. V. si. sol. water, misc^ble
with alcohol, ether, or CHCI3. On reduction with
HI it gives ethyl-propyl-glyoxaline (Wallaoh a.
Sohulze, B. 13, 516 ; 14, 423 ; A. 214, 312).
Salts.— (B'HCl)jPtCl,,—B'HI.—B'jAgNO,:
needles.
(Py. 3, 2)-CHL0E0-ETHYL-ftUIS0LIlIE
.CH = C(CjH.)
0.,H„01N i.«. C.h/ I . [73°].
\n =CC1
Prepared by the action of PCI, on ethyl-hydro-
carbostyril (Baeyer a. Jaekson, B. 13, 120). Insbl.
water, v.soi. other solvents. Volatile vrith steam.
Weak base.— (B'H01)jPtCl4. V. sol. alcohol, de-
composed by water.
CHLOROFORM.
or
Chloro - eth7l(r) . isoquinoUne C„H,„N01.
[0. 80°]. Formed by boiling the di-ohloro- deriva-
tive [166°] witt HI and P, Colourless crystals.
By heating with HI and P to 200° it is com-
pletely deohlorinated (Gabriel, B. 20, 1206).
Di-ohloro.etliyl(?)-iaoquinoUae . C,,H„NCL
.0{4h.): COl " » »
probablyOjE,^ I [166°]. Pormedby
heating theimideof phenyl-di-methyl-oarboxylio
aoid C.HX | with POCl,; if the product
\00. NH
is a derivative of ethyl-iaoquinoline an isomeric
change must have occurred during the reaction.
Long colourless needles. By HI and P it is
first reduced to the mono-ohloro-derivative
[80°] and then to the ethyl(?).isoqninoline
[65°] (Gabriel, B. 20, 1206).
DI-CHLORO-DI-ETHyL SULPHIDE
(CE^C\Xm,).,S. (217°). Formed by the action
of PCI, on S(CHj.CHjOH)j obtained from glycol
chlorhydrin and KjS (V. Meyer, B. 19, 3259 ;
20, 1729). Oil. Very poisonous and violently
inflames the skin (difference from di-ethyl sul-
phide).
Tetra-chloro-di-ethyl sulphide (C^HjCUoS.
(167°-172°). S.G. 12 1-547. A yellow oil formed
bypassing chlorine into di-ethyl sulphide, which
is at first kept cool and in the shade (Biche, A.
92, 358). There appear also to be formed
(C,HjCl,),S (189°-.192°), (OjHCgj,S (217°-222°)
and (C,Cy,S (?).
Oi-chloro-di-ethyl di-snlphide
(CH,Cl.CHj),S2. S.G. 18 1-346. From ethylene
and CljSj at 100° (Guthrie, A. 119, 91 ; 121,
108). Pale yellow oil. Alcoholic KOH gives oily
(CH,OH.CHj)jS. HNO, forms CHjOl.OHj.SOjH
(Spring a. Lecrenier, Bl. [2] 48, 629).
Tetia-chloro-di-ethyl di-sulphid'e
(CjHjCyjSj. S.G. 11 1-599. Formed by passing
ethylene through boiling SjClj (G.). Oil.
CHLOEO-ETHYL SULPHOCYANIDE
Cl.CjH,.CNS. (203°). Formed by heating
CjHjBrj (100 g.), KCNS (66 g.) and alcohol
(250 c.c.) with inverted condenser. The product
is filtered, distilled to 150° and the residue
in the retort cooled in a freezing mixture.
C^,(CNS)2 now crystallises out. The liquid
portion is distilled (J. W. James, C. J. 35, 807,
J. pr. [2]" 20, 352 ; 31, 411). Formed in the
same way from ethylene ohloro-bromide (107°-
109°) (James, C. J. 43, 39 ; 47, 365).
Profpertiea. — Oil. Smells like mustard oiL
Bums with violet flame. Soluble in alcohol
and ether. Dissolves in hot water, but separates
again on cooling.
Beacticma. — 1. Fuming HNO, converts it into
chloro-ethane sulphonio acid, Cl.C^H^.SOjH.
Ammonia, of course, will convert this into
taurine. — 2. Alcoholic potassio sulphocyanide
converts it into OjH4(SCN)j— 3. With aqueous
Na^SO, in sunlight it forms CjH,(SCN)(SOsNa).
I)I-GHLOaO-(<<)-EIH7L-IHIOPHENE
04H(0jH.)Cl5S (236° cor.). A Uquid formed
by passing chlorine into cooled ' /3 '-ethyl-thio-
phene (Bonz, B. 18, 551).
DI-CHLORO-ETHYI-TOIUENE (?).
CsHijClj. (865°). Formed, together with propyl-
ene and chlorinated cresol by distillation of
penta-chloro-thymol (Lallemand, C, B. 43, 375).
DI-CHLOBO-EUXANTHIC ACID v. Edxan-
iHio Aam.
DI-OHLOEO-PLTJORENE q„H,OI,. [128°].
Formed by passing chlorine into fluorene (from
coal-tar) in chloroform (Hodgkinson a. Matthews,
O. J. 43, 170). Colourless plates. Oiddised by
chromic mixture to di-ohloro-di-phenylene
ketone [158°]. "^
Tri-chloro-fluoreae 0,3H,Cl3 [147°]. Formed
by leadmg chlorine into a CS^ solution of fluo-
rene for a long time (Holm, B. 16, 1082). White
plates. SI. sol. alcohol and ether.
Penta-ohloro-fluorene di-chloride CisHjCl,
[104°]. From di-ohloro-fluorene in chloroform
by chlorine (H. a. M.). Long needles. CrOj con.
verts it into a yellow ketone (?) [104°]. Al.
ooholio KOH converts it into a red bodj
(? CisHsCl,) which is insol. alcohol, but crystal-
lises from chloroform, petroleum or acetic acid
[c. 110°]. It is not attacked by HNO, or CrO,.
CHLOKO-PLUOEESCEIN
CO<ei?^^>C<gg!gi)>0. Formed by
heatmg chlpro-phthalic anhydride [97°] with
resoroin. V. al. sol. water and CHCI3. When
freshly prepared it is sol. alcohol and ether,
but it changes on keepinig into an insoluble crys-
talline form; v. sol. acetic acid ; insol. CbH„; sol.
aqueous KHO, and KjCOj forming a deep red
solution, which when diluted shows a fluorescence
like that of fluorescein (Graebe a. E6e, 0. J.
49, 530).
Di-chloro-fluorescein. Hydrate.
OaH2Clj:CA:(OeH3(OH),)j. Formed by heating ,
(^)-di-ehloro-phthalic anhydride [151°] with
resorcin at 200°. Loses aq when heated. Alkalis
form a red solution with green fluorescence (Le
Boyer, A. 238, 357).
Tetra-chloro-fluoreacein
Ofil,:G^O,:{0,Ufi^)fi. Formed by heating re-
sorcin with tetra-chloro-phthalio anhydride
(Graebe, A. 238, 333). Addition of acids to its
solution in NaOH pps. the hydrate or ortho- com-
pound, which at 180° is dehydrated. Insol. ether.
Diacetyl derivative
O.Cl,:CA:(OAOAc)A
Hydrate C.Cl4:CA:(0.H,(0a)J,. Ppd.by
adding acids to a solution of the fluorescein in
aqueous NaOH. Orange needles (from ether) ;
insol. water, si. sol. alcohol. Its alkaline solu-
tion is red with strong green fluorescence like
fluorescein. At 180° it gives oft H„0.
Chloride 0„Cl<:CA:(CaH,Cl)26. [259°].
CHLOEOFOBM CHCI3, Tn-Mm-o-methane.
Mol. w. 119^. [-70°] (Berthelot, Bl. [2] 29, 3).
(60-9°) at 754-3 mm. (Sohifl, 4. 220, 95); (61-4'^)
(Thorpe) ; (62°) (Perkin, C. J. 45, 530). S.G.'i?
1-6039 ; °5|? 1-4081 ; if 1-5009 ; |f 1-4849. O.E.
(11-8 to 60-9) -00138 (Schiff) ; (0°-10°) -001248
(Thorpe) ; (0°-50°) -0013368 (T.); see also Gri-
maldi, a. 17, 18. S. -987 at 0°; -775 at 55°
(Chancel a. Parmentier, C. B. 106, 577). V.D.
4-12 (for 4-12). H.F.p. 24110 (Th.). H.F.v.
23530. M.M. 5-559 at 15-3°. S.H. -233 (SohiiUer,
P. Suppl. 5, 116, 192). md 1-451 (Forbes, P. M.
[3] 35, 94). S.V. 84-6 (Schiff) ; 85-6 (Bamsay) ;
84-5 (Thorpe). Capilla/rity : Swan, 0, J. 1, 174 ;
P. M. [3] 33, 36. OompressibiUty : Grassi, A. Oh.
[3] 31, 437.
Formation. — 1. By the action of bleaching.
Jf2
68
CHLOROFORM.
pQwdeT on dilute aloohol (Soubeiran, A. Ch. [2]
48, 131 ; Soubeiran a. MialhS, A. 71, 225) or on
acetone (Liebig, A. 1, 198). — 2. By the action of
chlorine on marsh-gas m daylight, and ulti-
mately in sunlight (Begnault, A. Gh. [2] 71,
380). — 3. By passing a mixture of chlorine
and methyl chloride through animal charcoal
at 250°-3S0'" (Damoiseau, C. B. 92, 42).— 4. By
the action of aqueous potash on chloral (Lie-
big, A. 1, 199). — 5. By the action of nascent
hydrogen on 001,. — 6. By boiling tri-chloro-
acetic acid with aqueous alkalis (Dumas, A. Ch.
[2] 56, 115 ; A. 32, 113).— 7. From iodoform and
PCI5 (Gautier, Bl. [2] IB, 316).— 8. From CC1„
zinc, and dilute H^SO, (Geuther, A. 107, 212).
Preparation. — 1. By mixing chloral with di-
lute caustic soda. — 2. Bleaching powder (40pts.),
water (100 to 150 pts.), alcohol (4 to lOpts.), and
slaked lime (4 to 10 pts.) are distilled together.
The distillate separates into two layers, the lower
one being chloroform. This is freed iiom chlo-
rine by shating with potash, dried over CaClj
and rectified (Kessler, J. Ph. [3] 13, 162).
Theory of the process. — The bleaching powder
is supposed first to convert the alcohol into
chloral (3. v.), and the lime which is present (or
formed) would then split this up into calcic
formate and chloroform: SCaO.Olj + 2C2H1JO
= 2C,CljH0 + oCaCl, H- 3CaO + 5H,0 ,
= 2CCI5H + Ca(CH0;)2 + 50aClj + 2CaO + iH^O.
When alcohol of various strengths is poured
on bleaching powder the distillate, which some-
times explodes after shaking well with water, gives
an oil which can be separated by fractionating
into the following portions : —
1 pt. Bloohol miiecj with pts.
of water
I
9-8
12-3
21-0
50-6
4-2
1
3-4
12-4
31-6
27-5
24-9
3
'56-5
31-2
12-2
i
89-1
3-1
8
60°-70''
70°-80°
80°-100°
100°-160°
150^-160°
160°-180°
98-1
1-9
per-
centage
• compo-
sition of
oil.
The amount of chloro-acetal (150°-160°) is there-
fore greatly diminished by diluting the alcohol
(Goldberg, J. pr, 132, 111). The yield of chloro-
form is never more than equal in weight to the
weight of the alcohol used, this is less than one
molecule of chloroform from two molecules of
alcohol. Chloroform cannot be prepared from
pure methyl alcohol by means of bleaching pow-
der, although it is formed from commercial
methyl alcohol (Belohonbek, A. 165, 349). Chlo-
rinated compounds are formed by the action of
bleaching powder on isopropyl, isobutyl, and iso-
amyl alcohols ; so that the alcohol used to pre-
pare chloroform should not contain fousel oil
(J. Eegnault a. E. Hardy, J. Ph. [4] 30, 405).
ProperUes. — Characteristic odour and sweet
taste, almost insoluble in water. When pure it is
not turned brovm by H^SO^. Chloroform reduces
Fehling's solution, thus : CH01,-l-2CuO + 5KH0
= CUjO -I- 3K01 + KjCOj + 3H2O . (Baudrimont,
J. Ph. [4] 9, 410). It dissolves fats and resins.
A solution of iodiue in chloroform is violet, but
bromine forms a red solution. It is ansesthetic
(James Simpson, A. 65, 121) and antiseptio
(Rohm, C. B. 30, 62 ; Augendre, C. B. 31, 679).
When a mixture of chloroform and water is kept
at 0° for a long time with frequent shaking a
hydrate CHCl, 18aq separates in long lamins.
It is lighter than chloroform but heavier than
water, and melts at 1*6° (Chancel a. Farmentier,
C. B. 100, 27 ; cf. Sajohelyia. BaUo, B. 4, 160).
Detection. — Chloroform may be distinguished
from most other similar chlorinated hydrocar-
bons by boiling it with alcoholic potash and a
primary amine (e.g. aniline), when the character-
istic disgusting odour of the carbamines will be
noticed (Hofmanu, B. 3, 769). When the vapour
of chloroform is passed through a red-hot tube
chlorine is liberated, and will turn paper moistened
with starch and potassium iodide blue (Bagsky,
J.pr. 46, 170; Lnedeking, Am. 8, 358). Chloro-
form gives a reddish-purple colour (? rosolic acid)
when poured upon the hot residue obtained by
evaporating an alcoholic solution of phenol mixed
with caustic potash (Guareschi, O. 3, 401).
Impurities. — Chloroform that is to be nsed
f cr surgical operations should not give any brown
colour when shaken with H2SO4 (Gregory, Pr. E.
1850,391; c/.Vulpius,4r.Pfc.[3]13,37; 25,998).
The presence of alcohol causes opalescence when
chloroform is mixed vrith water (Mialh6, J. Chim.
Mid. [3] 4, 279), and a green colour with chromic
mixture (Cottell, J. Ph. [3] 13, 359). The reduc-
tion of potassium permanganate may also be
used as a rough index of the amount of alcohol,
aldehyde, and other oxidisable substances present
in chloroform (JoUes, Chcm. Zeit. 11, 786).
Estimation. — By treating a chloroform solu-
tion with alcoholicpotash thechlorine is obtained
as chloride. The conditions for getting a theo-
retical yield have been determined by De Saint-
Martin (0. B. 106, 492-4&6 ; of. Chancel a. Par-
mentier, C. B. 106, 577).
Beactions. — 1. CrO, mixture gives COClj. —
2. Zinc and dilute H^SO, convert it into C^jCl,
(Geuther, A. 107, 212 ; Kiohardson a. Williams,
C. N. 18, 60). — 3. Zinc-dust converts it in pre-
sence of ammonia into methane (Perkin, C. N.
18, 106). — 4. Boiled with alcoholic potash it
forms potassium chloride and formate, thus :
GHClj + 4KH0 = 3KC1 + CHOjK -h 2H,0. — 5.
With sodic ethylate it gives orthoformic ether,
CH(OEt)s (Williamson a. Kay, O. J. 7, 224).—
6. Mixed with ammonia and passed through a
red-hot tube it reacts thus: CHCIa-HNH,
= CNH-h3HC1. Aqueous ammonda at 220°
forms carbonic oxide, ammonium formate, and
ammonio chloride, thus : 2CHCL +'7NH, -1- 3H.,0
= C0-|-6NH,C1 + HC0,NH, (Andr6, O.B. 102,
553).— 7. Water at 220° forms CO, formic acid,
and HCl. — 8. Alcoholic KjS forms potassium
thioformate H.OO.SK (Nicol, Tr. E. 29, 531).—
9. Aniline at 190° gives di-phenyl-form-amidine
CeH5NH.CH:N.0„H, (Hofmann, Pr. 9, 229).-
10. Bromine at 200° gives CBrCl, (Patern6, G.
1, 593 ; Friedel a. Silva, Bl. [2] 17, 637).— 11.
With bromine (3 pts.) and iodine ( Ipt.) at 150°
it gives CBrjCl [70°] and CBr, [76°] (Bolas a.
Groves, O. J. 24, 779).— 12. HNOj containing
NOj forms at 100° a small quantity of chloro-
picrin (MiUs, C. J. 24, 641).— 13. Cone. HIAq
at 125° gives CHJj (Lieben, Z. [2] 4, 713).
PH.I and ZnO give CH,C1 (Hofmann, B. 6.
301).— 14. When passed ovsr red-hot copper
CHLORO-FORMIO AOTD.
some acetylene is formed (Berthelot, G. B. 50,
805). — 15. Potassizim amalgam, also forms
ftoetylene (Kletzinsky, ^. [2] 2, 127).— 16. KjSO,
at 170° forma OHj(SOsK)j and CH(S03K),
(Streoker, Z. [2] 4,, 214).— 17. Sodmm acting
on chloroform containing alcohol forms ohlor-
ethuhnio acid CoHjOlOj (Hardy, A. Ch. [3] 65,
840 ; O. B. 54, 470 ; ef. Kern, 0. N. 31, 121).—
18. The copper-ziric couple does not act on
pure chloroform ; in presence of alcohol at 60°
methane is evolved, together with a small
quantity of acetylene ; in presence of water me-
ttiane is evolved even at 12° (Gladstone a. Tribe,
C. J. 28, 508).— 19. SbCls at 100° forms CCl,
(Lossner, J.pr. [2] 13, 418). — 20. Electric sparks
decompose chloroform forming HCl and C^Olg ;
in presence of air GOGl, is formed (JT. Begnault,
J. Ph. [5] 6, 604).— 21. Potash added to a mix-
ture of acetone (1 mol.) and chloroform (1 mol.)
forms acetone-chloroform or oxy-isobutyro-tri-
chloride (CH3)2C(0H).CG1,. There is also formed
a liquid isomeride, possibly CHGLs.GMej.OGl,
(170°). It iB a strong poison and yields with
behzene and Al^Gl, ohloro-di-phenyl-tert-butyl
alcohol (239°) ; while with PCI5 it yields G^HaGl^O
(151') (Willgerodt a. Genieser, /. pr. [2] 37, 362).
Potash (8 mols.) acting on chloroform (1 mol.)
and acetone (2 mols.) forms GnHjgO, i.e.
CMe2(O.OMe2.G02E)2; an acid which, l&e ace-
tone-chloroform (a. v.'j, is converted into oxy-
isobutyrio acid by heatmg with water (Willgerodt,
B. 20, 2445; Bl. [2] 39, 157 ; Bngel, Bl. [2] 47,
499 ; C. B. 104, 688).— 22. With SO, it forms
carbonic oxide, ClSOgH and CljSjO, (Armstrong,
Z. 1870, 247).
Gombmation.—'^iih. aqueous H,S at 0° it
forms a crystalline compound GEG1,2H2S 23aq
(Loir, 0. B. 34,547; J. 1852, 560; Forcrand,
A. Ch. [6] 28, 12).
CHLORO-FOBMIC ACID "Cl.GO.OH.
Methyl ether. Gl.CO2.Me. (71° cor.).
S.G. 3^ 1-236 ffioese, A. 205, 228). Formed by
the action of COClj on methyl alcohol (Dumas,
A. 10, 277 ; A. Ch. 58, 52 ; Meyer a. Wurster,
B. 6, 965). Formed also by the action of chlor-
ine on gaseous methyl formate (Hentschel, /. pr,
[2] 36, 211). Preparation.— To avoid formation
of methyl carbonate proceed thus: Phosgene is
freed from chlorine by passing through a flask
full of pieces of antimony and powdered glass
and placed in the water bath. The gas is passed
into a few c.c. of cfaloro-f ormate of methyl at 0°.
Methyl alcohol is added in small portions at a
time, waiting each time until the phosgene goes
through unabsorbed. Altogether not more than
150 c.c. of methyl alcohol should be used (A.
Klepl, J. pr. [2] 26, 447). Properties. —Heavy
oil ; readily decomposed by boiling with water.
Gives the tri-chloro-methyl ether when chlorine
acts on it in sunlight. Intermediate compounds
are C^Kfilfit and 0,Hb01,0s. The compound
OjHiClsO, (109° cor.) is a very pungent oil, S.G.
II 1'4741 ; ^ 1-4786. It is decomposed by water
mto formic aldehyde. 2GO2, and GO; while
anilineform80,H,Cl3(NPhH)A[45°] ; andfusion
with NaOAc yields methylene diaoetate (166°).
The other compound, OsHjOl^Oj or OiB.fi\Os,
(181° cor.), S.G. 1-52, is a liquid, slowly decom-
posed by boiling water into CO, COj, HCl, and
tormie aldehyde (Hentschel, J.pr. [2] 36, 468).
Tri-chloro-methyl ether CClsk'. (128°
cor.). S.G. a 1-653. V.D. 94-3 (oalc. 99).
Formed by chlorinating methyl formate in sun-
light. Liquid ; inflames the skin. Above 300'
it changes into the isomeric COCl^; this change
takes place slowly even on boiling. At a dull
red heat it splits up into CCl^ and CO.. AljCl,
decomposes it in the same way (Hentschel, J.pr.
[2] 36, 99, 305). BeOcUons.—l. Like COClj, it
acts on NaOAo forming NaCl, COj, and AojO.—
2. MeOH forms an oil, possibly GCl3O.CO.OMe ;
it boils at 164° being split up into COClj and
Ol.COjMe. — 3. Dry and aqueous ammonia forms
urea but not tri-chloro-acetamide.— 4. Aniline
forms di-phenyl-nrea and phenyl cyanate.—
5. Benzene and AljCl,, give (G|^j)3CCl. — 6. Phenol
gives ObHsO.CO.CI.
Ethyl ether Cl.CO.;Et. Mol.w.lOSi. (94°).
S.G. 15 1-139. V.D. 3-82. Preparation.— Bj pass-
ing COCI2 into well-cooled alcohol (Dumas, A.
Ch. [2] 54, 226 ; Cloez, A. Ch. [3] 17, 303 ; Ca-
hours, A. Ch. [3] 19, 346 ; Klepl, J. pr. [2] 26,
448 ; Wihn a. Wisohin, A. 147, 150) ; or by
dropping alcohol into liquid GOCl^ standing in
a freezing-mixture (Hentschel, B. 18, 1177).
Properties. — Pungent liquid ; decomposed by h ot,
but not by cold, water. JReaotions. — 1. With
alcohol it forms carbonic ether, reacting thus :
ClCOjEt+HOEt = EtO.CO^t-l-HCl. — 2. With
sodium it reacts in this way: 2ClC02Bt -1- Na^
= 2NaGl -I- CO -1- COaBtj.— 3. With ZnMcj it reacts
in the following manner: 2ClC02Et -h ZnMcj
= ZnCl2-f200jH-2G2H4 + 2CH, (Butlerow, Z.
1863, 484). — 4. With ammonia it forms carbamic
ether, NHj.C02Et. — 5. AljClj splits it up into
COj and EtOl. — 6. Benzene and AljCl, give,
ethyl-benzene (Eennie, C. J. 41, 33).— 7. ZnClj
gives COj, EtCl, HCl, and ethylene (Ulsoh, A.
226, 281).— 8. Sodium amalgam, converts it into
formic acid (Geuther,^. 205, 225).— 9. NaOCsHa
gives (0„H50)CO(OEt) (Fatianoff, Z. 1864,77).—
10. NajS gives S(C0jEt)2 (V. Meyer; B. 2, 297).—
11. Potassium cyanate forms the following crys-
talline bodies : (a) C.^H.sNaO, or C,N30,,(COjEt)3
[119°]; (6) 0„H,3N30, or G3N303Et(CO,Et)j
[123°] ; (c) C,„H„N,O5or03N3O3Et,(CO,Efe) [107°] ;
(d) NH(COjBt)j [50°] ; and (e) GaNjOsEt, (Wurtz
a. Henninger, C. B. 100, 1419 ; Bl. [2] 44, 26).— '
12. With KNCS in presence of alcohol it forms
carbonic ether and allophanic ether (Wilm,
A. 192, 243) : 2Cl.CO,Bt-l-2KNCO-)-3HOEt
= 2KG1 -^ 2Et3C03 + GjHjSjOsEt.- 13. With thio-
urea it forms NK,.CS.NHCO,Et,HGl [117°]
(Pawlewski, B. 21, 401).— 14. With di-pUtiyl-
thio-wrea it forms di-phenyl-thio-allophanic
acid NHPh.CS.NPh.GOjBt.— 15. With phenyl-
tlm-urea it forms phenyl - allophanic acid
NHPh.CS.NH.OOaBt.— 16. With acetyl-phetvyl-
thio-vrea it forms' a-phenyl-thio-allophauio acid
NHjOS.NPh.COjBt.- 17. Cyanethine forms cyan-
ethine oarboxylic acid (E. v. Meyer a. Sohone,
J.pr. [2] 30, 123).— 18. Quinoline forms ethyl-
quinoline: G,H,N + ClCOjEt = CAEtNHCl + CO,
(M. a". S.).
Chloro-ethylic ether Cl.GO,.CHj.CHjCl.
(150°-160°). From glycolio chlorhydrin and
COClj in the cold (J. Nemirowsky, J. pr. [2] 31,
173). The product is mixed with KjCOj and
extracted with ether. Colourless, fuming, pun-
fent liquid, insol. water, sol. alcohol and ether.
leactions. — 1. Not decomposed by boiling water,
2. Converted by boiling iilvitepotash into glycol,
70
OHLOEO-FORMIO AOID.
potassium chloride, and potassium carbonate. —
3. Converted by anvmoma into the carbamate of
ohloro-ethyl,,as follows: Cl.CO.O.OjH4Cl + 2NHs
j=NH3,HCl + H,N.C0.O.CjHi01.— 4.WitliamZme
it reacts, forming the corresponding compound
NPhH-COjCaHjCl (phenyl-oarbamic acid).
Propyl ether GIGO^T. (115° cor.). S.G.
is 1-09. Liquid ; more stable than methyl ether
(Boese, A. 205, 229).
Isopropyl ether ClCO^Pr. , (95°). S.G.
4 1-144 (Spioa, G. 17, 168). Gives with NH,
isopropyl carbamate NHj.COjPr [37^].
Isobutyl ether ClCOjCjH,. (129° cor.).
S.G. i£ 1-053 (Eoese ; c/. Mylius, B. 5, 972).
, Ammonia converts it into isobutyl carbamate
NHj.COjCA [65°].
Amyl eifcer Cl.COjC,H„. (158°) (S.)-, (154°
cor.) (E.). S.G. iS 1-032. From COCl, and
amyl alcohol (Sohone, J. pr. [2J 32, 246).
Phenyl ether CLCOjCsHj. (187°). From
the tri-chloro-methyl ether and NaOFh (Hent-
schel, J.pr. [2] 36, 316).
Amide Cl.CO.NHj. [50°]. (62°). Formed by
passing dry 0001, into NH^Cl at 400° (Gatter-
mann a. Schmidt, B. 20, 858). Flat needles,
with unpleasant odour. Changes on keeping
into cyamelide with evolution of HCl. Decom-
posed by water into COj and NHjCl. With
toluene and AljClj it gives the amide of p-toluic
acid ; other aromatic hydrocarbons and phenol
ethers act similarly. Amines yield alkyl-ureas.
Aqueous NaOH forms cyanic acid. Alcohols in
small quantities form allophanic ethers, in excess
they give carbamic ethers.
Methylamide Ol.CO.NHMe ' Methyl-wrea-
chloride.' [90°]; (94°); colourless plates. Ob-
tained by passing carbonyl chloride COClj over
dry methylamine hydrochloride heated to 140°.
Distilled over lime it yields methyl cyanate
OC:NMe. Decomposed by water.
Ethylamide Cl.CO.NHEt • Ethyl-urea-
chloride.' (92°) ; colourless liquid. Obtained by
passing COCl, over dry ethylamine hydrochloride
-heated to 250°-270°. Distilled over lime it
yields ethyl cyanate OC:NEt. On conversion into
vapour it dissociates into ethyl cyanate and HCl,
which recombine on cooling. In most of its
reactions it gives the same products as ethyl
cyanate (Gattermaim a. Schmidt, B. 20, 118;
A. 244, 34).
Di-methyl-amide Cl.CO.NMe2. Colour-
less liquid. Sol. C^„ ether, and OS,. Prepared
by the action of carbonyl chloride (COCy on
dimethylamine. Is slowly decomposed by water
into CO2 and KHMe^HCl (Michlei a. Escherich,
B. 12, 1162).
CHLORO-FORMYI-TRICAEBOXYLld ACID
V. CHLOBO-METHANE-TniCAHBOXyLIO ACID.
CHLOEO-FUMAEIC ACID C.HCl(CO,a),.
[191°].
Pr^Mration. — 1^ Chlorine is passed to satu-
ration into succinyl chloride. Methyl alcohol is
added to the product as long as B!C1 escapes.
The liquid is then boiled. On cooling, methyl
ohloro-fumarate, [102°], separates. The filtrate
is poured into water, when a further quantity of
this body is thrown down. HCl at 140° decom-
poses the ether forming the acid (Kauder, /. pr.
[2] 81, 24).— 2. Tartaric acid (50 g.) and PCI,
(275 g.) are heated with inverted condenser.
The product is distilled to 130° and the residue
mixed with water. The solution is shaken with
ether and thd ether evaporated (Perkin a. Duppa,
A. 115, 105 ; 129, 373 ; 0. J. Proc. 4, 75).
Properties. — Clumps, from alcohol and benz-
ene. Vi sol. water, alcohol, and ether, si. sol.
benzene and ligroin. May be sublimed unaltered.
OonsUtuHon. — ^Perkin considers it tp be a
derivative of fumaric acid because it is very
soluble in water. The fact that it sublimes
without forming an anhydride would indicate
that it is a derivative of maleic acid (Kauder) J
Reactions. — 1. Sodium a/malgam, forms suc-
cinic acid (Perkin, A. 129, 375). — 2. Dissolved
in cold water and the equivalent of ardUne added
it gives a crystalline pp. of the acid aniline salt,
C02H.CH.CCl.C0jH.NHrPh. [178°]. An aqueous
solution may be kept for weeks without under-
going any change. On boiling the aqueous solu-
tion, it behaves like the corresponding bromo-
f umarate, although less readily (Michael, Am. 9,
180).
Salts. — EHA". Transparent prisms. —
BaA" 8aq. Clumps.— AgjA".
Methyl ether. Me^A". (224°).
Ethyl ether. Et^A". (245°). 8.0.22 1-178.
From tartaric ether and FCl, (Henry, A. 156,
178; Glaus, 4. 191, 80).
Amio ether CjHCl(C02Et)(C0NH2). [102°].
From chlorofumario ether and alcoholic NH,
(Claus a. Voeller^ B. 14, 150). Tables.
Imide C,HC10jNH. [131°]. Large colour-
less plates. Sol. water, alcohol and ether.
Formed by ohloriuation of suocinimide (Ciami-
ciau a. Silber, B. 16, 2394).
Ohloro-fumaric acid CjHC^COjHjj [178°].
(0. 190°). White pp. consisting of microscopic
needles. V. sol. alcohol, water, and ether.
Formed by the combination of acetylene-di-car-
boxylic acid with HCl.
Salts. — A"Kj: laige sparingly soluble
prisms. — A''Agj aq : fine crystalline pp. —
A'Tb 2aq : amorphpus pp. becoming crystalline
(Baudrowski, B. 15, 2695).
V. also ChiiOko-ualeio acid.
TETEACHIOEOGALIESX CjoHioOl^O,.
From tetra-chloro-phthalic anhydride and pyro-
gaUol at 200° (Graebe, A. 238, 837). At 180° it
gives off 2aq becoming 02„H,CliP,.
CHL0B06ENINE v. Amtondib.
jS-CHLOEOGLUTACONIC ACID
H02C.CH:CC1.CH,.C0,H. [129°]. Formed by the
action of PCI, (16 pts.) upon acetone-di-car-
boxylic ether C0(CH2C02Et)j (5 pts.) at 100°, and
.saponification of the ether with cono. HCl ; yield :
60-60 p.o. of the theoretical. The reaction is
probably due to the intermediate formation of
0Cl2(CH2C02Et)2. White needles (chloroform)
or plates (hot benzene). V. sol. water, alcohol,
and ether, less in chloroform, insol. cold ben-
zene. By zinc-dust and acetic acid it is reduced
to glutaconio acid [182°] ; by sodium amalgam
to glutario acid. By alcoholic KOH it is con-
verted into glutinio acid HO2O.OSC.CHj.CO8H
(Burton a. Peohmann, B. 20, 145).
DI-CHLOEO-GLUTAZIBrE v. Di-chlobo-di-
OXY-AMlDO-rYBIDnra.
TEI-CHLOBO-ISOGIYCEEIC ACID v. Tni-
OHIiOBO-PYBUVia ACID.
DI-CHL0E0-&LYC0C0L1D. Di-OHLOBo-AMiDO-
ACEIIO ACID.
CHLORO-HEPTENOIC AOID.
71
OI-CHLOSO-GLTCOLLIC ACID. The dialkyl
ethers C01j(OE').C0jR' of this aoid are the
primary products of the action of PClj upon
oxalio ethers. On distillation under ordinary
atmospheric pressure they split ofl alkyl chlorides,
and are converted into the chloro-glyoxylio ethers
Cl.C0.00jE' (Ansohiitz, B. 19, 2lS8).
Di-n-propyl ei/ier 001,(OPr).COiiPr: (111°
at 12mm.) ; colourless liquid. Formed by the
action of PCI, upon mono-propyl oxalate
OA(OH)(OPr).
Di-ispamyl eifcerCClj^OOjHiJ.COaCsH,,:
(152° at 13mm.) ; colourless liquid. Formed by
the action of FClj Upon mono-isoamyl oxalate
(Ansohiitz a. SohBnfeld, B. 19, 1443).
DI-GHLOKO-OLTCOLLO-SIIiaLE
0Cl2(0H).0N.
MelJvyl derivatme CClj(OMe)CN. (149°).
S.Q. 1'39. Prom di-chloro-aoetouitrile andNaOMe
(Bauer, A. 229, 168). Pleasant smelling liquid,
nearly insol. water, but slowly decomposed by
it. v. sol. alcohol, ether, and light petroleum.
Changes on keeping into a solid isomeride.
j;%Z deriuatiue CClj(OBt)ON. (161°). 8.0.
15? 1-339. "V.D. 153-24. Polymerises forming a
white solid. [171°].
Propyl Oerivatme CCl2(0Pr)CN. (183°). S.G.
!£5 1-238. V.D. 174.
Isobutyl derwative CCl2(OC4H8)ON. (196°).
S.G. }£P 1-123.
These bodies combine with FtCl^ forming
eompounds such as CCl2(OEt)CKPtCl4 (Bauer,
A. 229, 182).
They are acted upon by dry HBr with forma-
tion of tri-ohloro-aceto-nitrile, probably as a
result of these reactions :
(i.) OCl,(OMe)CN + HBr
= MeBr+CCl,(OH)CN.
(ii.) CGU6h)CN= HCl + C1.C0.cn.
(iii.) CClj(OH)CN + HCl=CCl,.CO.NHj
(Bauer, A. 229, 192).
So also dilute HjSO^ converts CClj(OMe)CN
into CClaCOoMe and CClj(OBt)CN into
CCl,,CO,Et.
CHLOKO-GIYOXIM CjHaClOjN, i.e.
CC1(N0H).CH(N0H). [151°]. Formed by the
action of hydroxylamine on ohloral-hydrate
(Nageli, Bi 16, 499). Glistening prismatic
needles. Sol. water and alcohol.
CHLOEO-GLYOXYLIC ETHEB Ol.Cb.COjEt.
Ethoxy-oxalyl chloride. (131°). S.G. " 1-216.
VJ). 4-68 (oalo. 4-71). Prepared by distilling
oxalic ether with PCI, (V.v. Eiohter, B. 10, 2228 ;
C. C. 1878, 446 ; ef. Henry, B. 4, 599).
Praperkes. — Fuming liquid ; decomposed by
water with formation of oxalic acid. Alcohol
gives oxalic ether. Alcoholic NH, gives oxamio
ether. Aniline forms COjBt.CO.NPhH.
Eeacticms. — 1. Zinc ethyl, followed by water,
forms oxy-hexoio ether CBt2(0H).C02Et (Henry,
B.5,949).— 2. With Mj-ea it gives ethyl oxalurate,
NH,.C0.NH.C0.C02Et (Henry, B. 4, 599 ; Salo-
mon, B. 9, 376).— 3, With HgPhj it gives
phenyl-glyoxylic aoid (Claisen a. Morley, B. 11,
1596).— 4. With di-methyl-ardUne it gives di-
methyl-amido-phenyl-glyoxylio aoid. — 5. With
cH-phemyl-thiMrea dissolved in benzene it reacts
vigorously, giving off CO^ and ethyl chloride and
forming aniline and a compound which is pro-
bably thio -carbanilido - thio - oxanilide
NPhH.CS.NPh.CO.CS.NPhH ^v. Stojentin, J.pr.
[2] 32, 2). This body melts at [231°]. It dissolves
m ether, sparingly in alcohol, not at all in water.
It' exhibits the following reacUom: (a) Warmed
with alcoholic AgNOj it forms AgjS and di-
<NPh-CO
I .
NPh-CO
(&) Forms a red solution in aniline, which when
warmed with dry alcohol and AgNOj forms oxalyl-
1 .NPh.CO
tri-phenyl-guanidine, 0(NPh)< I [230°1.
\NPh.CO
(c) Fuming HNO, forms a compound CsHgN^SOs.
It melts at [235°], is insol. ether, benzene, CS,
and light petroleum, and is readily decomposed
by aqueous NaOH, ^-nitraniline being formed.
(d) Alcoholic NHj converts it into OnHjsN^Oj, a
body which crystallises from alcohol in white
needles, [220°], and which is itself converted by
fuming HNOj into another body, C:^^^^^0„
sparingly soluble in water or alcohol, [235°].—
6. With phenyl thiurea, dissolved in boUing ben-
zene, it acts thus : 2NH, CS.NPhH + ClOO.CO^Et
= NH(CS.NPh)jCj02 + NH, + BtCl + H,0. The
product is oxalyl-di-phenyl-di-thio-
biuret. It forms slender needles (from alcohol)
[215°].— 7. JWhen warmed with phenyl-urea it
reacts as follows: NPhH.C0.NH2-hCl.C0.C02Et
= NPhH.CO.NH.COjEt + CO-i-HCl, and also in
the f oUowing way : NPhH.CO.NH2 + Cl.CO.CO^Et
=NPh<p^>NH + ClBt+H,0. The chief
products are, therefore, phenyl-allophanio
ether, which forms needles (from alcohol),
[120°], and phenyl-parabahic aoid, which
forms plates (from alcohol), [208°].— 8. Withii-
phenyl-urea it forms di-phenyl-parabanic
aoid, [204°]: NPhH.CO.NPhH + Cl.CQ.COjEt
-NPh<^Q>NPh-fEtCUH20.— 9. WithW-
phenyl-gtumidme it forms oarbonyl-tri-
phenyl -guanidine:
(NPhH)j:C:NPh + 201.CO.CO2Et
= NPh:C<^p^> C0,HC1 + HCl + CO + Et AO4.
The hydrochloride of this base forms concen-
tric needles (itam alcohol), [190°]; its nitrate,
B'jHNOj, forms ootahedra (from alcohol), [185°].
By means of fuming nitric acid white needles of
the formula C,sH,2N20„|aq, may be got (M. v
Stojentin, J.pr. [2] 32, i).
CHIOEO-GUAHIDIKE CHiClN,. From
guanidiUe carbonate and chlorine (Kamenski, B.
11, 1602)., Pale yellow crystalline powder. De
tonates about 147°.
CHLOBO-HEFTANE v. Hefi^tl oblobidk.
Bi-chloro-heptane C,H,4CL: i.e.
Pr.CHj.0Hj,.CH2.0HClj. SeptyUdene chloride.
(191° cor.). From oenanthol and PClsCLimpricht,
A. 103, 80). Converted by Na into heptylene.
Alcoholic EOH gives chloro-heptyleue.
Si-chloro-heptane C,B.ifil, *-e. Pr^CCl,.
(181°). From di-«-propyl ketone and POl,
(Tavildaroff, B. 9, 1442).
Si-chloro-heptane FrjCCl,. From di-isopropyl
ketone and PCI5 (Henry, B. 8, 400). Splits up
into HCl and C,H,3C1 on distillation. Alcoholic
KOH gives C,H,j (78°).
CHLOBO-HEFIENOIG ACID C,H„010r
From propyl-aceto-acetic ether and PClj (Do-
mar?ay, B. 10, 1178). Oil.
7.?
CHLORO-HEPTENOIO ACID.
Chlaro-lieptenoic acid C,H„C102, From iso-
propyl-aoeto-aoetic acid and PCI5 (D.). Oil.
CHLORO-HEPTYL ALCOHOL C,H„C10.
(207°). S.G. 2 1-014. From ootylene and HCIO
(De Clermont, Z. 1870, 411).
CHLOHO-HEXANE «. Hbxyl ohmmde.
Di-chloro-hexane C„H|201ii.e.
CH3.CHC1.CH2.CH,.CHC1.CH3. {170°-180=).
From diallyl and fuming HClAq (Wurtz, A. Oh,
[4] 3, 161).
Di-ohloro-hexane C„H,jCl,. {0. 182°). S.G. 22
1-087. From the hexaue of petrolemn by ohlori-
nation (Cahours, A. Ch. [4] 1, 5).
Di-chloro-hexane C„H,2Clj. (160°). Formed
by chlorination of diisopropyl (Sohorlemmer, A.
144, 187 ; Silva, B. 6, 38 ; 7, 953).
Si-chloro-hezane CjHi^Clj i.e.
(CH3)2.CCl.C01.(CH,)2.[160°].Frompinaconeand
POClj (Friedel a. Silva, B. 6, 3S). Crystalline.
Di-chloro-hexane (CH,)3C.CCl2.CH3. [151°].
From pinacoline and PClj (Favorsky, J. pr. [2]
37, 393). Very volatile crystals. Gives with
alcoholic potash CMe,.C:CH.
Dl-chloTO-hexane CsHijClj i.e.
OH3.CHCl.CHC1.0K,.CHj.CH3. (o.l64°). S.G. "
1-053. From ohloro-ethyl-propyl-oarbinol and
PCI5 (Henry, Bl. [2] 41, 363). Alcoholic KOH
gives C„H„01 (122°).
Tri-chloro-hexaneCsH„Clj. (o.217°). S.G.21
1-193. Formed by chlorinating M-hexane (Ca-
hours, J. 1863, 525).
Hexa-ohloro-hexane CbH,C1„. (0. 288°). S.G.
?2 1-598. From ra-hexane and CI (C).
CHLOBO-HEXENOIC ACID v. Chmbo-eihyl
CEOTONIO ACID.
Chloro-hexenoie acid CsHsClO^. [64°]. From
di-methyl-aoeto-aoetio ether andPClj (D.).
CHLOEO-HEXENYL ALCOHOL CbH„C10.
Allyl-chloro-propyl carbinol (0. 185°). S.G. 22
1-032. Boo 58-3. From epiohlorhydrin, (150 g.),
allyl iodide (273 g.), and zinc at 0° ; the product
being treated with water (Lopatkin, J.pr. [2]
30, 390). Oil. Oxidation gives chloro-oxy-valerio
acid.
Acetyl derivative C„H„C10Ao. (c.205°).
8.G. 2 1-065 ; 22 l.0d8. Ea, 75-1.
Chloro-hexenyl alcohol CsHnClO i.e.
CHj<;Q^g>CCl.CH,,OH (?). Chloj-o-viethyl.
tetra-methylene-ca/rbinol. (c. 167°). From the
following di-chloro-hexenyl alcohol by treatment
with iron and acetic acid (Natterer, If. 5, 579).
Liqviid, si. sol. water. Does not combine with
Br. Gives with PCI, a liquid C^HaCls (100° at
20 mm.).
Di-chloro-hexenyl alcohol C^HigCl^O i.e.
CH,<CH(CH,Cl)>''01-^^0^ (')• (°- 1"°)
at 20 mm. From ay-di-ohloro-crotonic aldehyde
by successive treatment with ZnEt^ and water
(Natterer, M. 5, 567). Thick liquid ; v. si. sol.
water. Does not combine with £r.
Acetyl derivative CsHjClaOAc. (123°)
at 20 mm. Converted by AgOAc at 110° into
C.H,Cl(OAc)j (140° at 20 mm.).
CHLOBO-HEXINENE V. Hexinyl chlobide.
letra-chloro-hexineue CgH^Cl^. Formed by
the action of FOl, on mannite or dulcite (Bell,
B. 12, 1273).
CHLOEO-HEXOIC ACID C,H„C10j ».e.
CEtiCl.COgH. Chloro-caproic acid.
Ethyl ether EtA'. From PCI5 and the ozy-
aoid (derived from oxalic ether) (Markownikoff,
B. 6, 1175). On distillation it gives HCl and
hexenoio ether ; sodium amalgam gives hexoio .
(di-eihyl-acetic) acid.
7-Chlaro-isohexoic acid
Me^CCLCH^-CHrCO^H.
Ethyl ether A'Et: (88" at 12mm.).
Formed by saturating an absolute alcoholic so-
lution of isocaprolaotone (the lactone of oxy-
hexoic acid) with HCl. On distillation jt evolves
HOI and yields pyroterebio ether (Bredt, B. 19,
614).
Tri-chloro-hexoio acid OsHjClaOa. [64°].
Formed by oxidation of the corresponding alde-
hyde by HNO, (Pinner, B. 10, 1052). Zinc and
HCl convert it into hexenoic acid.
TBI-CHLOaO-HEXOIG ALDEHYDE
CsHjCljO. Hexyl-chloral. (213°). Occurs among
the products of the chlorination of aldehyde
(Pinner, B. 10, 1052). Potash splits it up into
formic acid, CsHjClj, and HCl.
CHLORO-HEXTL ■ ALCOHOL CsHijClO i.e.
CH,.CH2.CHj.CHCl.CH(OH).CHs.ilfcft2/ZcHoro-
butyl carhinol. (170°). S.G. li 1-018. " From
hexylene and HOCl (Domao, M. 2, 319). Iron
and HOAc give sec-hexyl alcohol.
Chloro-hexyl alcohol CjHisClO i.e.
CH,.CHj.CHj.CH(OH).CHCl.CHa (?). Hexylene .
chlorhydrin. (171°). S.G. ii 1-014. From
hexylene oxide and HCl (Henry, 0. B. 97, 260).
Oil, with sweetish taste.
Acetyl derivative CaB.^iCl.OA.0. (189°).
S.G. s 1-04.
S-Ghloro-n-hezyl-alcohol
CH3.CHCl.CH2.CH2.CH,.CHj.0H (?). Hexylene
S-chlorhydrin. Formed by heating the glycol
with HCl (Lipp, B. 18, 3283). Colourless liquid
of peculiar smell. Heavier than water, in which
it is insoluble. By further heating with HCl it
is converted into the di-chloride.
Chloro-hexyl alcohol CjHisClO i.e.
CMejCl.CMe2.OH. [65°]. From CMe„:CMe2 and
HOCl (Eltekofl, J. B. 14, 390). Needles, smell-
ing of camphor. Aqueous KOH forms pinacone ;
solid KOH gives hexylene oxide.
Di-ohloro-hexyl alcohol C^HioCljO. (208°).
S.G. is 1-4. From hexenyl alcohol and chlorine
(Destrem, A. Ch. [5] 27, 58).
CHLOBO-HEXYLEH'E v. Hexenyl ohlomdb.
Di-chloro-haxylene C„H,„Cl2 i. e.
CH3.CCl2.CH2.CHj.CH:CH2. Allyl-chloracetol.
(150°). From methyl butenyl ketone and PCI5
(Henry, C. B. 87, 171). Heavy oil. Hot water
reconverts it into the ketone. Alcoholic KOH
gives CjHdOI.
Di-chloro-hexylene. CsH,„Clj. From mesityl
oxide and PCI5. Smells like turpentine and re-
sinifies'in the air. Distillation over lime con-
verts it into CXCl (130°) (Baeyer, A. 140, 298).
Penta-ohloro-hexyleneCeH,Cl5. [102°]. From
quercite by treatment with HOI. Needles
(Prunier, A. Ch. [5] 15, 1).
m-CHLORO-HIPPUKIC ACID C»H.C1N0,
i e. [3:1] C,H4Cl.C0.NH.CHj.CO2H. From hip-
purie acid, KCIO,, and HCl (Otto, A. 122, 129).
Found in the urine after taking m-chloro-ben-
zoic acid (Grtebe a. Sohultzen, A. 142, 346).
Viscid mass, sol. boiling water, mixes with
alcohol and ether. Its alkaline solution turns
OHLORO-m'BROQmNONI!:.
Ta
brown ia air. Boiling eono. HCl gives glycocoll
and m-ohloro-benzoio acid.
Salts.— NaHA'jiaq: stellate groups of
needles.— CaA'j : scales (from alcohol).— PbA'~
[100°].
Di-chloro-hippurio acid CeH,Cl,NO, i.e.
[1:2:4] C,H3Cl2.CO.NH.CIL,.CO.,H. Firmed to-
gether with the preceding by chlorinating hip-
purio acid with HOI, and KCIO, (0.). Soft,
semi-orystalline mass ; less sol. water than the
preceding acid. Cone. HCl, splits it up into
glycoooll and (1, 2, 4)-di-ohloro-benzoio acid.
Salts. — NaA'aq: soft warty crystals. —
CaA'j 6aq (from hot watnr). — CaA'^ 9aq
CaA'j lOaq (from -cold water). — BaA'j 3aq. —
Pb A', 4aq. — (PbA'JjPbO. - AgA' : cauliflower-
like masses (from hot water).
Ethyl ether'EtA.'. Oil.
CHLOEHYDRIN v. Gltoebin.
Dichlorhydrin v, Di-ohlobo-pkoptii AioonoL
and EPICHLOBHTDBIN.
Triehlorhydrin v. Tri-ohlobo-peopakb.
CHLOaO-HTDEACBYLIC ACID v. Chloho-
OXY-PROPIONIO ACID.
CHLOEO-HYDEO-ATEOPIC ACID v. Chlobo-
FBENVL-PBOPIOIIIO ACID.
CHLOEO - HYDEO - CINNAMIC ACID v.
CniiOBO-FHENYL-PBOFIONia ACID.
DI - CHLOEO - HYDEOCCEEULIGNOH v.
re<rai-me<%Z-M-0HiiOBO-HEXA-oxT-DiPHii;NYL.
CHLOKO -HYDEONAPHTHOQUINONE
0,i,H,C10, i. e. <3,„HjCl(OH)2 [117"]. From
oliloro-(/3)-naphthoquinone in acetic acid by
passing in SO3 (Zinoke, B. 19, 2498). Needles
(from water).
Di-chloro-hydronaphthoquinone C,oH,CljOj
i.e. C,„B.^ei^{OK).,. [125'']. From di-ohloro-
(j8) -naphthoquinone and SO2 (Zincke, B. 19,
2500). Slender needles.
Di-chloro-(a)-lLydronapb.thoqninone
C,^^Clj(OH)j. [135° uncof.]. Formed by shak-
ing an ethereal solution of di-chloror(a)-
naphthoquinone with aqueous SnCl, till de-
colourised. Long colourless needles. V. sol.
alcohol, ether, &c., insol. water. By air oxida-
tion it is converted into the quinhydrone
Cj„H,i,Cl,0„ which forms long violet-brown
needles [250° uncor.] (Glaus, S. 19, 1144 ; cf.
GrjBbe, A. 149, 6).
Di-acetyl derivative C,|,H.Clj(OAo)j.
[230°].
CHLOEO-HtDBOaUINONE Cs£L,Cl{On)^
[100°]. (263°). Prepared by boiling quinone with
HCl (Levy a. Sehultz, B. 13, 1427 ; A. 210, 137 ;
cf. Wohler, A. 51, 155; Wichelhaus, B. 12,
1504). Alsov from chloro-quinone and SOj
(Stiideler, A. 69, 307). Monoclinic crystals,
a:6:c = 2-77:l:2-31; |S==62° 3'. V. e. sol. water
and alcohol, si. sol. chloroform. On oxidation
it. gives chloroquinone. Heated with phthalic
anhydride it produces a chlorinated quinizarine
which is soluble in caustic soda with a blue
colour. Combines with aniline with formation
of 0„H,Cl(0H)j2NHjPh [92°] which crystallises
from hot water in glittering plates (Niemeyer,
A. 228, 322). With ^-toluidine it forms a com-
pound melting at 90°. These compounds are
not decomposed by crystallising from hot benz-
ene.
Di-acetyl derivative CjH^C^OAc),.
[72°] (L. a. S,); [99°] (Seheid, A. 218, 216).
Transparent prisms. Sol alcohol.
Di-benzoyl derivative CjH,Cl(0Bz)2.
[130°]. Long needles. Easily soluble in hot
alcohol, sparingly in cold.
(a)-Di-ohloro-hydroquinono C,H,C1,(0H),
[2:5:4:1]. [166°] (L. a. S.) ; [172°] (KrafTt, B. 10,
800). Prepared by boiling chloro-quinone with
HCl ; or by passing diy HCl into a solution of
chloroquinone in chloroform (Levy a. Sohultz,
B. 13, 1428 ; A. 210,148). Formed also by redu-
cing (a) -di-chloro- quinone [159°] with aqueous
SOj (Stadeler, A. 69, 312), Long needles (from
boiling water). May be sublimed. On oxidation
it gives (a)-dichloro-quinone. Combines with
aniline forming 0„H,Clj(0H),,2NHjPh [113°],
which crystallises in needles - (from water),
tables, or prisms (from benzene). The com-
pound with ^-toluidine melts at 115° (Niemeyer,
A. 228, 328).
Di-acetyl derivative 08HjCls(OAo)2.
[141°]. Formed by the action of acetyl chloride
on quinone or ohloro-quinone. Monoclinic
crystals (Sohulz, B. 15, 653; A. 210, 148)
a:b:c = 2-9:l:l-13 ; i8 = 72° 40'.
Di-benzoyl derivative CaHjOl2(OBz)2.
p.85°]. Woolly needles, sol. beiizene, insol.
water.
(;3)-Di.cliloro-hySro-qiiinone CjHjCl2(0H)j
[2:6:4:1]. [158°]. Formed by reduction of the
corresponding quinone [120°] (Faust, A. 149,
155). Yellowish laminie (from dilute alcohol).
Forms with ))-tolaidine a compound melting at
73°.
Di-acetyl derivative C,HjCl,(OAo),
[07°] ; fine needles.
Di-benzoyl derivative CgHjC^OBz),
[105°] ; colourless needles (Levy, B. 16, i445).
Di-methyl ether C„B..fil^{OidB)i. [126°].
Formed by chlorinating di-methyl-hydroquinone
(Habermann, B. 11, 1034). Small needles ; may
be sublimed.
Di-isobutyl ether C8HjClj(0CHjPr),
(Schubert, M. 3, 682).
Iri - chloro - hydroqninone
C„HC1,(0H),. [134°]. Prepared, together with
tetraohlorohydroquinone, by boiling (a)- or (|3)-
dichloroquinone with HCl, and separated from
tetra-chloro-hydroqninone by solution in water
(Levy a. Sehultz, B. 13, 1429 ; A. 210, 153).
Formed also by reducing tri-chloro-quinonewith
SO2 (StSdeler, A. 69, 321 ; Stenhouse, A. Suj^l.
6, 214 ; Grasbe, A. 146, 25), and by oxidising
benzene with KCIO, and HjSO, (Krafft, B. 10,
797; Carius, A. 142, 129). Flattened prisms.
Its alkaline solutions turn brown in the air,
ultimately forming di-chloro-di-oxy-quinone
fchloranilic acid). It forms two compounds vrith
aniline: CaHClj(0H)2, NH^Ph [60°], crystallising
in small needles, and C„HCl3(0H)2, 2NHiPh
[67°], crystallising in trimetrio tables. With
phthalic anhydride it does not produce chlor-
inated quinizarine.
Di-acetyl derivative C,HCl,(OAo)2.
[153°]. Needles.
Di-benzoyl derivative CeHCl,(OBz)y
[174°]. Needles.
Di-ethyl ether CsHCla(0Et)2. [68-5°].
Long needles.
Tetra-chloro-hydroquinone
CbC1,(0H)j. [232°] (Sutkowski, B. 19, 2316).
CIILORO-nYDRUQTTINONE,
Prepared by boiling (y8).diohloro-qninone or tri-
chloro-quinone with HCl (Levy a. Schultz, B.
13, 1429 ; A. 210, 255), or by passing HCl into
a solution of tri-chloro-quinone in acetic acid
(Niemeyer, A. 228, 324). Formed also by boil-
ing tetra-ohloro-quinone with SnClj, with HClAq,
with HBrAq, or with aqueous SOj. Monoclinic
pyramids ; a:b:e = 3-0:l:2-58 ; j3 = 76° 34'. May
be sublimed. Insol. water, v. si. sol. benzene,
T. sol. alcohol and ether. Beduoes silver solu-
tion. FCl, converts it into 0,01,. A cone,
solution in not potash deposits, on cooling,
prisms of CgClj^OK),. A solution of this
salt exposed to air forms Gfi\fi^{pK)^. Com-
bines with aniline, forming C,Cl,(pH)2XH2Fh
Di-acetyl derivative C.Cl.(0Ac)2.
[245°].
Di-bemoyl derivative C„Cl4(OBz)2.
[233°]. Sol. benzene, si. sol. alcohol.
Di-methyl ether C,Cl,(0Me)2. [154°].
From di-methyl-hydroqninone and CI (Haber-
mann, B. 11, 1035). Needles.
Di-ethyl ether C.Cl.lOEt)^. [112°]. From
tetra-ohloro-hydroquinone, KOH, EtI, and alco-
hol at 140^ (Graebe, A. 1'46, 19). Needles.
Methyl ethyl ether CjCl,(OMe)(OEt).
[101°]. From C.H,{OMe){OEt) and CI (Fiala, M.
6, 912).
Di-isohutyl ether C.CUOCHjFr): (Schu-
bert, M. 3, 682).
DI - jB - CHLOEO - HTDaOQTJINONE - DI-
CABBOXTLIC ETHER v. Dl-p-OHLOBO-Di-j)-
OZT-TEBEFHTHAIiIO BTHEB.
SI - CHLOBO - HySBOQUIHOKE SI-STTL-
FHONIC ACID
CjHjCljSjO, i.e. C„Cl2(OH)2(SOsH)j. From tetra-
chloro-quinone and aqueous KHSO, (Hesse, A.
114, 324; Greift, O. 0. 1863,, 1044). The free acid
is unstable. It gives an indigo-blue colour with
Fe^Clg. Alkaline solutions are oxidised by air
to euthiochronic acid — KjA" 2aq. — (NH,)jA"2aq.
. Tri - chloro - hydroqninone sulphonic acid
CjHjClsSO, i.e. C,Cl,(OH)jSOjH. Formed, to-
gether with euthioohroidio acid, by dissblving
tri-chloro-quinone in warm aqueous Ez^O,
(Grfflbe, A. 146, 55): Deliquescent needles.
FcjCl, gives a blue colour. — KA'aq. Alkaline
solutions are oxidised in air to
C„C1(0K),0„(S0,K).
CHlORO-HYDEO-THYMOaUINOirE
C,„H„C10j i.e. C„HC1(C,H,)(CH3)(0H),
[2:6:3:4:1]. [70°]. From thymoquinone and oono.
aqiieous HCl at 0° (Sobniter, B. 20, 1317).
Silky needles.
Di-acetyl derivative C,„H„Cl(0Ac)2.
[88°] . Formed by the action of acetyl chloride
on thymoquinone. Large crystals.
Di-henzoyl derivative [118°]. Colour-
less needles (Schulz, B. 15, 657).
Si-chloro-hydrothymoqninone
Di-bemoyl derivative GggHigCUOBz),.
[191°]. Formed bythaaotion of benzoyl chloride
on thymoquinone (Schulz,£.15,658). Sparingly
soluble white needles.
CHLOEO-HYDEOTOLTJaTimONE
C,ft(CH,)Cl(OH)j [l:3or4:2:5]. [116° unoor.].
Formed by reduction of chloro-toluquinone [90°]
with SOj. Long colourless needles. Sublim-
able and volatile with steam (Clans a Schweitzer,
B. 19. 929).
Chloro-hydro-toluqulnone 0|jH2MeCl(0H),.
[175°]. Obtained by the action of cold cono.
HCl upon toluquinone. White plates or needles.
V. sol. alcohol, ether, and hot water, si. sol.
ligroin (Schniter, B. 20, 2283).
Si - ohloro - hydro-tolnquinone
C.HMeCl2(0H)j. [121°]. Formed by the action
of HCl upon chloro-toluquinone. Not volatile
with steam (Sohniter, B. 20, 2288). Formed also
by reducing di-chloro-toluquinone obtained from
di-chlorinated o-oresol [54°] (Glaus a. Schweitzer,
B. 19, 937 ; c/. Southworth, 4. 168, 274). Feathery
crystals (from water). May be sublimed.
Bi-chloro-hydrotoluquinone
CeH(CH,)Clj(OH)j. [171° unoor.]. Formed by
reduction of di-ohloro -toluquinone [103"] (from
di-chloro-m-cresol) vrith SOj. Colourless needles.
V. e. sol. alcohol, ether, &o., sol.' hot water, si.
sol. cold (Claus a. Schweitzer, B. 19, 931).
Acetyl derivative C5HMeCl2(OAo)j,
[124°] (Southworth).
Tri-chloro-hydrotoluquinone CBMeCl3(0H)2.
[212°]. From tri-ohloro-toluquinone and aque-
ous SOj at 100° (Southworth ; Borgmann, A.
152, 251 ; Hayduok, A. 172, 211; Claus a. Eie-
mann, B. 16, 1608). Needles. Volatile with
steam. Turns green in moist air.
Di-acetyl derivative C,MeClj(OAo)2.
[114°].
Di-ethyl ether C,MeCl,(OBt)j. [107°].
Tetra - chloro - by drotolaqmnone C^^CltO^
From tetra-chloro-toluquinone and SO, (Braa-
ninger, A. 185, 353). Needles (by sublimation).
CHLOEO-HYSEOTOLUamNONE BI-STTL-
PHONIC ACIS CoMeCl(OH)j(S03H)j. From tri-
chloro-toluquinone and cone, aqueous KHSO,
(Borgmann, A. 152, 255). — ElA' : laminte.
CHLOEO-HySEOXYLOaUINONE
C3HClMej(OH)2 [a!:l:4:2:5]. [147°]. Formed,
together with the di-chloro- compound, by treat-
ing xyloquinone (phlorone) vrith cono. HCl
(Carstanjen, J.pr. [2] 23, 421). Needles. FCjCl,
colours its aqueous solution violet.
Bi-chloro-hydroxyloqninone Ofili'MeJO'S.)^
[180°]. Formed as above (0.) or by reducing
di-chloro-xyloqninone with aqueous SOj (Bad,
A. 151, 164). Coloured violet by ¥efi\. ■
BI-CHLORO-ICOSYLENE G^^,fil^. S.G. a
1-013. From C,,H„ and 01 (Lippmarm a. Haw-
liczek, B. 12, 69').
CHI,0E0IM:IB0-CAEB0NICACISC1N:C(OH)j.
Methyl ether ClN:C(OMe)2.'[20°]. Formed,
by leading chlorine into a cooled solution of
80 pts. NaOH and 80 pts. KCN (96-98 p.o.) in
150 pts. of methyl alcohol. White crystalline
solid. Its reactions are the same as those of
the ethyl ether.
Ethyl ether CW:G{0M)2. [39°]. Formed
by leading chlorine into a cooled solution of
80 pts. NaOH and 80 pts. KCN in 200 pts. of
ethyl alcohol ; the yield is 50 pts. of the pure pro-
duct. Large colourless prisms. V. sol. alcohol
and ether, insol. water. Eotates on water. De-
composes on distillation. Heated with aqueous
HjS it yields carbonic ether NH^Cl and S. By
dilute acids it is split up into carbonic ether,
chloride of nitrogen and NHj. From HI it
liberates iodine. By warming with a solution
of potassium arsenite it is reduced to imido-
carbonic ether HN:C(OEt)j (Sandmeyer, B. 19,
862).
CHM)RO-IOD0-OXY.BENZ0I0 ACID.
75
TETKA-CHLOBO-INDIOO 0„HeCl<N A- Very
analogous to ordinary indigo. Obtained by the
action of acetone and NaOH on di-ohloro-nitro-
benzoic aldehyde (Gnchm, B. 17, 762).
I)I-CHLOB-INI)OL£ 0,H,C1^ i.e.
e,Hj<^^C01. [104°]. Chlor . oxmdole-
chloride. From oxindole and PClj. Crystalline
mass smelling like fteces. Colourless laminsa
(from hot water), v. e. sol. alcohol, ether, and
benzene. Sol. alkalis. Can be methylated
(Baeyer, B. 12, 456 ; 15, 786).
OI-CHLOBO-IKDONAPHIHOQiriNONE
CA<cC>CClr [125°].
Formatum. — Tetrachloro - (j8) - naphthoqui-
none is dissolved in Na^COgAq, EOAo is. added
and afterwards HCl and chromic acid, the mix-
ture being gently warmed (Zincke, B. 21, 499).
ProperUes. — Plates (from dilute alcohol or
HOAc).
DI-CHLOSO-IOSHYDBIN v. Di-ceiiObo-iodo-
raoPANE.
a&. or go-CHLOEO-IODO-ACBYLIC ACID
CHI:CCl.COjHorCHCl:CI.COjja. [72°]. Formed
by boiling propiolio aoid with an ethereal solu-
tion of CU (Stolz, B. 19, 538). Pearly crystals.
Easily soluble in all solvents.
Cbloro-di-iodo-acrylic acid CsHO^GILi i.e.
Cl2:CCl.C0,H(?). [143°]. Formed by boiling
iodo-propiolic acid with an ethereal solution of
CU (Stolz, £:.19, 538). Colourless glistening
plates. Sparingly soluble in ligro'in and cold
water, more easily in alcohol and ether.
o-CHLOEO-IODO-BENZENE C^^CII [2:1].
(above 233°) (Korner); (230°) (B, a. K.). S.G.
— 1'928. From o-chloro-aniline by displacing
NH2 by I through the diazo- reaction (Korner,
Q. 4, 843 ; Beilstein a. Eurbatoff, A. 176, 83).
p-Chloro-iodo-benzene 0|,H,01I [4:1]. [56°].
(227°). From jp-ohloro-anffine by displacing
KH..2 by I; or from p-iodo-aniline by displacing
NH, by CI.
GHLOB-IOOO-BENZOIC ACID
CaHaClLCOaH [210°]. Formed by the action of
an alcoholic solution of iodine upon chloro-sali-
cylie acid [172°] (Smith a. Knerr, Am. 8, 95).
Curved needles. Sol. boiling water.
Salts. — BaA'j. Arborescent crystals.
CHLOEO - lODO - ETHANE Cja^ClI i.e.
CHjCLCHjI. Ethylene chloro-iodide. (140°)
(Thorpe, O. J. 37, 189). S.G. 2 2-151 (Simpson) ;
s 2*164 (Th.). Formed by the action of ICl on
ethylene or ethylene iodide (Maxwell' Simpson,
Pr. 11, 590; A. 125, 101 ; 127, 372; Suppl. 6,
254).
Beae^ons. — 1. Alcoholic KOH gives C^HjCl.
2. Moist Ag^O gives glycol. — 3. Zino and
HjSO, gives ethylene. — 4. Silver tovms ethylene
and ethylene chloride (Friedel a. Silva, Bl. [2]
17, 242).— 5. Cone. HI forms, on heating, C^^,
and OjHjIj.— 6. Ammonia forms ethylene-dia-
mine (Bngel, Bl. [2] 48, 96).
CMoro-iodo-etliane CH,.CHIC1. EtJvyUdena
ehloroiodAde. (118°). S.G. i2 2-054.
i'ormation.— Iodine (26 g.) is suspended in
Winter (120 g.) and saturated with chlorine in the
cold. The chloride of iodine is then shaken
with ethylidene iodide, the product washed with
dilute EOH and distilled.
Preparation.-- k\^, (8 g.) is dissolved in CSj
(24 g.) and slowly added to ethylidene chloride
(6g.) dissolved in CSj (6 g.) and kept at 0°, The
product is treated as above (Maxwell Simpson,
Pr. 27,424).
iji-'^hloro-iodo-ethane CjHjCy. (172°). S.G.
2 2-219. From CjH,Cl and ICl (Henry, C. B.
98, 518). Alcoholic KOH gives CH,:CC1, (37°).
CHLOBO-IODO-ETHYLENE OjHjICl. Acetyl-
ene chloro-iodide. (119° i. V.) (Plimpton) ; (115°)
(Sabanejefl). S.G. 2 2-230 (P.); 2 2-154 (S.) :
— 2-118 (S.). Formed by passing acetylene into
a solution of ICl in HCl (Plimpton, C. J. 4],
392) qr in ether (McGowan, Pr. E. 9, 589).
Prepa/ration. — Chlorine is passed into water
(6 pts.) containing iodine (1 pt.). The liquid is
poured off from undissolved iodine, and acetylene
is then passed ia (Sabanejefi, A. 216, 264).
Reactions. — 1. Zirui and alcohol gives off
acetylene.— 2. Alcoholic AgNO, forms needles of
a double compound. — 3. Heated with 50 vols, of
water at 150°, it is dissolved in 6 days the pro-
ducts being HI, C^HCl and chloro-ethylene oxide
CjHsClO (2. v.).—i. Alcoholic KOH gives off a
gas that decomposes in air (chloro- or iodo-
aoetylene).
Chloro-iodo-ethylene CH,:CC1I. (101°). S.G.
2 2-148. From chloro-bromo-iodo-ethane and
aloohoUc KOH (Henry, C. B. 98, 741). Oil;
turns purple in air and light, absorbing oxygen
DI:CHL0BO-TETBA-IODO-FLU0B£SCEIN.
Hydrate. C2,H,Cl2l.,Os. Formed by adding a
solution of iodine in dilute KOH to an alkaline
solution of di-chloro-fluoresce'in and acidifying
(Le Boyer, A. 238, 859). The alkaline salts are
used as dyes (' Bose Beugale ').
CHIOKO-IODO-METHANS CH,IC1. (100°).
S.G. 2» 2-49. From IHg.CH,Cl and Ij (Sakurai,
C. J. 41, 862).
Dl-chloro-iodo-metliane CHCljI. (131°). S.G.
2 2-454. Chloriodoform. A liquid formed 'by
the action of HgCl. or PClj en iodoform (SeruUas,
A. Ch. [2] 25, 314 ; 89, 225 ; Mitscherlioh, P.
11, 164 ; Bouchardat, A. 22, 229 ; Schlagden-
hauffen, J.Pfc. [3] 80, 401; Borodin, A. 126, 239).
Di-chloro-di-iodo-mathune CCl^I,. [85°].
From CHI, and HgClj (liorodin, A. 126, 239).
From CHjClj and IBr (BSland, A. 240, 234).
Glittering scales, with pungent odour. Turned
brown by light, alcohol, and ether.
GHIiOBO-IOOO-METHyL-FTBIDINE
C^HsClIN. [111°]. Chloro-iodo-picoUiie. From
chloro-(a)-piooline, [21°J, by digesting with I
and NaOH. I'rismE, apparently trimetric (Ost,
^.^r. [2] 27,257).
CHLOBO-IODO-mXBO-BENZENE
CAC1I(N0J [1:3:4]. [63°]. From the corre-
sponding chloro-nitro-aniline [123°] by displacing
NHj by i throDgh the diazo- reaction (Korner, O.
4, 381). Prisms (from ether-alcdiol); volatile
with steam ; si. so), cold alcohol.
Chloro - ioilo ■ nitro - benzene C8H,C1I(N02)
[1:4:3]. [63°]. From chloro-nitro-aniline [116°]
by the diaio- reaction (K.). Spherical groups
of needles (from hot alcohol).
CHLOBO-IODO-o-OXT-BElTZOIC ACID
0sH2(0H)CII(C02H) [2:a!:5:l]. Chlor-iodo-saU-
cyUcacid. [224°]. Prepared by heating chloro-
salioylic acid with iodine and HgO in alcoholic
solution (Smith a. Knerr, Avi. 8, 95). Colour-
ro
CIII.0RO-IODO-OXY-BENZOI0 ACID.
less needles ({roni dilute alcohol). Y. si. sol.
hot water. Gives a violet colour with Fe„Clj.
Salts.- BaA'j4iaq : pink needles; in. sol.
water. — NaA' 2aq,: flat needles. — : CaA', Caq :
pink needles ; sol. water.— MgA'j C^aq : pink
leaflets ; sol. hot water. — ZnA'j 3aq : white
needles ; v. sol. hot water.
Methyl ether MeA'. [130°]. Flat needles.
Ethyl ether EtA.'. White plates. V. sol.
hot alcohol.
TSI-qHIOKO-IODO-PHEHOI. OjHCljIfOH).
[80°]. Prom tri-chloro-amido-phenol by diazo-
reaetion (Lampert, J. pr. [2] 33, 391). White
needles (from alcohol).
Sthyl derivative O.HCl,I(OEt). [61°].
CHLORO-IODO-PEOPAira! CaHsClI i.e.
CH,.CHCl.CHjI. (149°). S.G. a 1-933 ; s^ 1-889.
From propylene and aqueous ICl (Maxwell Simp- "
son, Pr. 12, 278 ; Friedela. Silya, A. Ch. [2] 17,
535). Converted by HgCLj at 100° into propyl-
ene chloride. HI at 100° gives isopropyl iodide
and isppropyl chloride (Sorokin, B. 3, 626 ;
Silva, 0. B. 98, 739). Alcoholic KOH gives
CH,.CC1:GH,.
Chloro-iodo-propa&e CH,.CC1I.CH.,. Chloro-
iodo-acetol. (c. 120°) at 10 mm. S.G. a 1-824.
From CH3.0C1:CH2 and HI (Oppenheim, A.
Suppl. 6, 359). Decomposed by distillation
ahder atmospheric pressure. Moist Ag^O gives
acetone,
Di-chloro-iodo-pfopane CsHjCIj. Di-chloro-
iodhydrin. (o. 208°). From CjHsCl^OH) and
PCI5 (Henry, B. 4, 701).
CHLOBO-IOSO-PSOFTL ALCOHOL
C,H5CU(0H). Glycerin chloroiodhydrin. (226°).
S.G. 12 2-06. From epiiodhydrin and HOI -, or
from epichlorbydrin and HI (Beboul, A. Suppl.
1, 225). Cone. EOHAq gives epichlorbydrin.
CIILOBO-IODO-FBOPYLAUINE
CgHjClIIKHj). From allylamine hydrochloride
and ICl (Henry, B. 8, 399).— B'jHjPtClj.
CHLOSO-IOSO-PBOPYLESE 0,3. fill t.e.
CHj-.C01.CH,I. (0. 150°). S.G.15 1-913. From
di-chloro-propylene and Calj at 100° (v. Eom-
burgh, B. T. C. 1, 233). Combines with mer-
cury. Heated with EOH or Ag^O it yields a-
chloro-aUyl alcohol. AgNO, gives a-ohloro-allyl
nitrate.
Chloro-iodo-propylene CjHjCU i.e.
CHCl:CH.CH2l. (162°). S.G. is 1-97. Colourless
liquid, with ii;ritating odour and sharp taste. Fro-
pared by heating dry Calj with CHC1:CH.CH,C1
at 100°, or by heating dry KI or Cal, in excess
with aUylidene chloride at 100° for 24 hours.
Combines with Hg forming white plates, very
soluble in alcohol. With KOH it yields 0-chloro-
allyl alcohol (P. v. Eomburgh, B. T. C. 1, 233).
(o)-CHIORO.IODO-TOLTr£HE C,H,C1I.
(243°). S.G. i2 1-716. From (o)-chloro-nitro-
toluene by reduction and displacement of NH^ by
I through the diazo- reaction (Wroblewsky, Z.
[2} 6, 164 ; A. 168, 210). Liquid.
(5)-Cliloro.iodo-tolueneC,H,ClI. [10°]. (240°).
S.G.'2:' 1-770. From(;8)-chloro-nitro-toluene(W.).
Chloro-iodo-toluene CjHaClI. (240°). S.G. 42
1-702. From chlorinated o-toluidine (Beilstein
a. Kuhlberg, A. 156, 82).
CHLOBO-ISATIK v. Isatin.
CHLOBO - ISAIOIC ' ACID C,H,CmO. i.e.
C.H,C1<^°>C0^. [265°-268°]. Fromchloro-
isatin (10«.). OrOj (20 g.), and HOAo (120 g.)
(Dorsoh, /. 33?-. [2] 33, 49). Pearly plates (from
alcohol-acetone). Insol. water, ether, and benz-
ene. Boiling cone. HCl gives COj and chloro-o-
amido-benzoio acid. Ammonia gives COj and
chloro-benzamide.
Di-chloro-isatoio acid 0„H,C1.,<[|^°>C0.,H.
[256°]. From di-ohloro-isatin (10 g.), CrOa (15 g.),
and HOAo (60 g.) (D.). Yellow prisms (from
alcohol-acetone).
CHIOBO-LACIIC ACID v. Cblobo-oxt-fso-
PIONIC ACID.
CHLOBO-LEVULIC ACID v. Chlobo-aceiyl-
PBOPIONIC ACID.
GHLOBO-LtrilDINE v. Cblobo-di-ueiiiiyl-
PIBIDINE.
CHLOEO-MALEiC ACID C^ClHrCO^H),.
[172°]. The acid so called by Perkiu and Duppa
is probably ohloro-fumario acid {q. v.).
Formation. — ^Among the products of the ac-
tion of ClOH on benzene (Carius, A. 142, 139 ;
155, 217 ; c/. Kekulfi a. Streoker, A. 223, 183).
S alts .— KHA" aq.— BaA" 5aq. Crusts.
Anhydride CjClHiC^O,. [0°] and [34-5*].
Formed by heating a mixture of ohioro-fumaric
acid and its chloride (Perkia, C, J. Proc. 4, 76).
Dimorphous.
Di-chloro-maleic acid C2Cl2(C02H)2.
Preparation.— Ihe chloride OjClj^CjCl^O)
(see below) warmed with cone. HjSOj dissolves
with evolution of HCl. The crystals which se-
parate (anhydride) are dissolved in water (be-
coming nydrated), the solution is extracted with
ether, and the ethereal extract evaporated and
placed over HjSOi. Hygroscopic crystals of the
acid are formed. On sublimation they split up
into HjO and the anhydride, C201j(CO),0. The
acid may also be obtained by boiling its imide
with potash.
Properties. — ^Hygroscopic crystals. Changes
over HjSO,' into the anhydride. Also by boiling
with ligrom (40°), in -which the anhydride dis-
solves, but the acid does not.
Salt.— AgjA". Silky needles. Explodes
when heated.
Methyl ether.— Ue.,k". (225°).
Anhydride Gfi\JiGO).p. [120°]. Laminse;
may be sublimed. Slowly dissolves in watery
changing to the acid.
Tetraehlorinated derivative of the
anhydride C.OUCjOl.O),
(S) Solid: t4I'*] (209*
(Theory 277}. (? C,Clj(CCy,0)
). V.D. (H = l) 254
(a) Liquid: (194°-214°). V.D. (H = l) 236
(?CjCl2(CGl3)C0Cl).
Preparation. — By heating a mixture of POCl,
(24 g.), suooinyl chloride (8g.) and PClj (45 g.) in
sealed tubes at 230°. The product is distilled
and the fraction 125°-215° is treated with water.
The heavy oil which separates is distilled with
steam. It is chiefly liquid chloride. To get the
solid isomeride, the liquid is heated with PCI5 at
250°, the product poured into water and distilled
with steam. The oily distillate is dried over
CaClj and distilled. The distillate deposits plates
of the solid chloride, which may be recrystaUised
from alcohol of 90 per cent. (Kander, J.pr. [2]
31, 2, 7).
Reactions. — 1. Warm cone. HjSO, converts
both the solid and the liquid chloride into di>
TRI-OHLOEO-METHANE SULPHINTC AOID.
77
obbro-maleic anhydride. — 2. 'The vapour under-
goes dissociation when heated strongly, hence
the V.D. is rather low.— 3. Water and dilute
KaOH have hardly any action on the chlorides.
The liquid chloride is readily decomposed by al-
coholic NaOH, forming di-ohloro-maleio acid. —
4. Sodium amalgam reduces it in alcoholic so-
lution to succinio acid, di-chloro-maleic anhy-
dride being also formed.— 5. The liquid chloride
is violently attacked by ammonia. The solid
chloride is not attacked by alcoholic ammonia
below 130°. Ethylamine and aniline attack the
liquid, but not the solid chloride. — 6. Neither
chloride is attacked by 01 or Br.— 7. PClj at 250°
converts the liquid into the solid chloride, but
breaks both up thus :
CjCl,(0jCl40) + 3PCls = 2C.fi\ + 2PC1, + PCI3O.
Imide CfilfiJ^H.. Formed by chlorination
of Buocinimide at 150° ; or by boiling per-ohloro-
pyrocoll ortho-bromide with dilute acetic acid
(Ciamioiana.Silber,JS.lG,2393; 17,553; G.14,
31). Trimetric orystals,o:6:c = -9922 : 1 : 1-5934.
v. sol. hot water, alcohol, and ether. Heated
with POI5 at 200° for 24 hours it is converted
into the per-chloride CjCl^N, which is reduced
by zinc-dust and HCl to tetra-ohloro-pyrrol. By
heating with water it yields (a)-di-chloro-acrylia
acid, CO2, and NH,.
Perehlorinated imideO,Cl,N. [70°-73''].
(144° at 20 mm.). White wax-like solid. V. sol.
alcohol, ether, and acetic acid, nearly insol.
water. Formed by heating di-chloro-maleimido
with PCI, at 200° for 24 hours. Zinc-dust and
acetic or hydrochloric acid reduce it to tetra-
ohloro-pyrrol (Ciamician a. Silber, B. 17, 654).
Phinyl.imide Cfil^'^^'^NVh. [201°J.
Silvery plates. Got by action of PCI5 onphenyl-
Buccinimide (v. Sdooinimidb). HCl decomposes
it into aniline and di-chloro-maleic acid.
CHLOSOMALONIC ACID C3H3CIO, U.
CHCl:(COijH)j. [133°]. Formed by saponifica-
tion of the ether by cold alcoholic EOH (Conrad
a. Guthzeit, B. 15, 605). Prisms. Sol. water,
alcohol, and ether. Heated to 180° it loses CO3
and gives chloro-aeetic acid. — A'Ag: white crys-
talline pp.
Diethyl ether A"E%, (222°). S.G.ff. 1-185.
Prepared by the action of chlorine on malonic
ether. On saponification with KOH it gives
tartronio acid (Conrad a. Bisohoff, B. 13, 600 ;
A. 209, 218). The sodium derivative reacts
with [2:1] OgH,(OH2Br)2 with production of
O.H,(CH,.CCl(COjEt)2)j, whence alcoholic KOH
gives G.HiCH:CH.COjH), (Perkin, C. J. 63, 14).
Oroide CHC1(C0NH,),. [170°]. Tables, v.
Bol. hot water and alcohol.
CHLOBO-UECOITIC ACID v. Mscoiao acid.
CHLOEO-MECYLEKE v. Chloeo-pentinenb.
CHIOEO-TEIMESIC ACID C»HjCl(C0jH)3.
[278°]. From oxy-trimesio acid and PCI, (Ost,
J. pr. [2] 15, 308). Needles or tables (from
water) (containing aq).— BajA'", 7aci : m. sol.
hot water.
CHXOEO - MESITYIEUE CeHjCl(CH3)3.
(205°). Formed, together with di- and tri-
ohlorb-mesitylene by passing chlorine into cold
mesitylene (Fittig a. Hoogewei-ff, A. 150, 323 ;
Z. [2] 6, 168). Fuming HNO, forms a di-nitro-
derivative [177°!.
a-Chl oro-mesitylene C,H3(CH,),CH,C1. (216'-
220°). Obtained by chlorinating mesitylene at
216° (Eobinet, C. B. 96, 600). NaOAo gives
C,H3(CH3)jCH20Ac. (2420).
Di-ohloro-meaitylene CaHCyOH,),. [59°].
(244°). Formed by chlorinating cold mesitylene
(F. a. H.). Prisma (from alcohol). Volatile
with steam.
oo-Di-chloro-mesitylene C8H3(CHa)(CH2Cl),.
[41°]. (260°). Formed by chlorinating mesityl-
ene at 216° (B.). Needles.
Tri-ohloTo-mssitylene OoCl8(CHs),. [205°]
(F.a.H.); [208°] (Kurbatoff, J. B. 1883 [1] 129).
(280°). From cold mesitylene and excess of 01
(Kane, P. 44, 474 ; F. a. H.). From o-di-ohloro-
benzene, Al^Clg, and MeCl at 100° (Friedel a.
Crafts, A. Ch. [6] 10,411). Slender needles (from
alcohol). Not attacked by oxidising agents. HI
(S.G. 1-9) heated with it forms mesitylene.
u-Iri-chloro-mesitylene CeH3(0Hj01)j. (0.
280°). Prepared by heating the corresponding
alcohol with HCl and fractionating the crude
product in vacuo. Has not been obtained pure.
Heavy oil. Boiled with water and PbCO, it re-
generates C,H3(0H20H), (Colson, A. Oh. [6] 6,
97).
CHLOBO-MESIITLENIG ACID
CeH„Cl(CH,)„(00i,H) [4i3:5:l]. From chloro-
mesitylene and dilute HNO, (Fittig a- Hooge.
werfi, A. 150, 325). Honoclinic prisms (from
alcohol). Turns brown above 200° without melt-
ing. SL sol. boiling water. — BaA'2 4aq. —
CaA', 6aq : tufts of flattened needles. '
CHLOEO-METHACEYLIO ACID C.HsClO,.
[59°]. From tri-chloro-isobutyrio acid, HCl, and
zinc-dnst (Gottlieb, J. pr- [2] 12, 19). Formed
also by heating an aqueous solution of sodium
citra-di-chloro-pyrotartrate ; or by passing chlo-
rine into an aqueous solution of sodium citra-
conate (Swarts, J. 1873, 583 ; Morawski, J. pr.
[2] 12, 369; Siti. W. [2] 74,39). Needles, vola-
tile with steam.
S a 1 1 s. — KA' aq. — AgA'. — CaA', 3aq. —
BaA', 4aq.— PbA'j aq.— CuA'(OH).
Ethyl ether EtA'. (167°).
Di-chloro-meth acrylic acid C^HjCIjO,. [64°],
(216°). Formed by the action of aJkalis on tri-
chloro-isobutyrio acid (Gottlieb, J. pr. [2] 12, 8 ;
Morawski, C. C. 1877, 131). Slender prisms ;
may be sublimed. Attacks the skin. Sodium
amalgam forms isobutyrio acid. — NaA'aq.-^
KA'*aq.— AgA'.— CaA'j2aq.— PbA'jaq.[100°].—
CuA .
CHLOEO-METHANE v. Methyl celobide.
Di-chloro-methane v. Methylene ohlobidb,
Tri-«hloro-mettiane v, Chloboeobu.
letra-chloro-methane v. Cabbon-tetba-
OHLOBiDB, vol. i. p. 688.
CHLORO - METHANE . lEICABBOXTLIC
ETHEE CCl(OOjEt), (210°) at 140 mm. Pre-
pared by chlorination of methane-tricarboxylic
ether. By saponification it yields oxy-methane-
tricarboxylio acid (carboxytartronic acid) (Con-
rad, B. 14, 618).
TEI-CHLOEO-ICETHASfE SULPHINIC ACID
"OOI3.SO2H. From tri-ohloro-methane sulpho-
ohloride and alcoholic KCN or HjS (Low; Z.
1869, 82, 614 ; Bathke, A. 161, 149). Unstable
needles. — Salts. — KA'. Its solution gives with
Br a characteristic pp. of CCl3.S02Br. Boiling
water convertsit intoCHCl^(S03Kj. HJ^O,gi,aa
78
TRI-CHLORO-METHANE SULPHINIO AOID.
CCljSO^K'O,, a aolid, volatile with steam; re-
duced by Zn and HCl to methyl meroaptan. —
NH^A': from CCl,.S0j01 and cono. NHjAq
(McGowan, O. J. 61, 666).
CHLOBO-MEIHANE SULFHONIC ACID
CHjOl.SOjH. Formed by the action of zinc
and dilute E^SO, on trichloro-methane sul-
phonio acid (Kolbe, A. 54, 168). Acid Eyrup.
Sodium amalgam converts it into methane sul-
phonic aoid. EA': needles, insol. alcohol. — ^AgA'
crystalline.
Chloro-methane-disnlphonic acid
CHC^SOjH),. A by-product formed in the pre-
paration of chloro-Bulpho-acetic acid froQi chloro-
acetic acid and C1S0,H (Andreasch, M. 7, 172).
Very hygroscopic needles. Salts: EaA'2 4aq:
long thin shining needles. It is reduced by
sodium amalgam in HCl solution to the methane
disnlphonate. — AgA' : circular aggregates.
Si-chloro-methane sulphouic acid
"001^.80^
Formation.— Fiom CCls.SOjCl and SO, in
alcoholic solution (McGowan, J. pr. [2] 30, 297 ;
c/. Gerhaidt, Gompt. ehim. 1845, 197).
Prepwration. — 1. By action of Zn upon
CCljSOgH. The zinc is removed by K^CO,, and
the potassium salt crystallised from alcohol
(Kolbe). — 2. By heating chloroform with aqueous
KjSOa (Strecker, A., 148, 92).
Sail. — A'K: thin plates or long prisms. —
AgA'.
Chloride CCljH.SO^Cl. (o. 175°). S.G.
1*7. From FClj and the acid. An oU. Is Tiot
converted into CCljSO^Cl by chloride of iodine.
Amide CCL^.SOjNHj. Formed by the
action of dry NH, on the preceding. CrystaUised
from a mixture of benzene and alcohol.
Xri-chloro-methane sulphonio acid
CCl,.SOaH.
Pr^araiion. — Its chloride is digested with
aqueous baryta ; the barium is then removed
by HjSO, (McGowan, J.pr. [2] 30, 284).
Properties. — Small deliquescent prisms. Kot
volatile. Very acid.
BeactUma. — l.Does not attack spongy stiver;
dissolves iron forming a ferrous salt ; dissolves
zinc forming di-chloro-methane sulphonate of
zinc. — 2. FGl, reacts, but without forming tri-
chloromethane sulphochloride. FCl, does not
even attack potassiuni tri-chloro-methane sul-
phonate.— 3. Boiling cone. HNO„ aqueous CrO,,
and aqua regia have no action.
Salts.— KA' aq.— FeA'j 5aq.— PbA', 2aq.—
AgA'aq.
Chloride. CClaSOjCl. [ISS"]. (170°).
Formed by the action of chlorine and water on
CS-i (Berzelius a. Marcet, Schw. J. 9, 298). Pre-
pared by exposing a mixture of CSj, MnO,, aqueous
HCl and HNO3 to sunlight (Kolbe, A. 64, 145).
Crystallised from dry benzene. At 200° it splits
up into SO2, CCI4, COGL;, and CSCl, (Noeltiug,
Bl. [2] 37, 392). Eeactiom. — 1. Dissolves in
cone. EiNO,, but is reppd. by water unaltered. —
2. Boiling alcohol gives CCI4 and SO, (Carius, A.
Ill, 105). — 3. Aqueous or alcoholic KCN acts
thus : CCli-SO^Cl -1- KCN = CNCl + CCl,.SOjK
forming tri-chloro-methane sulphinate of potas-
sium. A secondary reaction also occurs, thus :
CC1,.S02K + KOH = KCl -h CCLj(OH)SOjK (Loew,
Z. 1868, 518; McGowan, J.pr. [2] 30, 288).—
4. Beduced by H,^ <>' S^i i" alcoholic solution
to the sulphinic acid, CCls.SOjH. — 6. NH,
forms tri-chloro-methane sulphinic acid and
nitrogen in this way: 8CClaSOjCl-t-8NH,
= 3CC1,.SO,NH4-hNs + 3NH4C1. This reaction
takes place whatever solvent is used.
^jjiHde.— CClaSOaNPhH. Needles. From
anilino and the chloride, dissolved in alcohol or
benzene, but not in ether.
Bromide. — CClj.SOjBr. From iri-ohloro
methane sulphinic acid and Br (Loew, Z. 18C9,
624). With alcohol at 100° it gives CCl,Br and
SO.,.
CHIOEO - METHENYL - AIUISO - NITPvO-
PHENYL-HEECAPTAN
C,H30jN,ClS or C.Hs(NO,,)/ *^CC1 [1:2]
\s/
[192°]. Needles. Has no basic properties.
Prepared by nitration of chloro-methenyl-amido-
phenyl-sulphydrate (Hofmanu, B. 13, 10).
CHLOBO - METHENYL - AMIBO - PQENYL.
MEECAPTAN CH^CINS or C,H,/ ^OCl [1:2]
[24°]. (248°). V.D. 82-4 (obs.). Prepared by
heating phenyl-thio-carbimide with PCI, (Hof-
mann,B. 12,1126; 13,8). Crystalline solid. Weak
base. The CI atom is very readily replaced. It
has none of the properties of a mustard oil and
is incapable of uniting with amines to form
thioureas.
CHLOBO-METHYL-ACETO-ACETIC ETHEB
C,H„C10,. (180°). S.G. IS 1-093. Formed, to-
gether with the di-chlcro-ether, by treating
methyl-aceto-acetic ether with PCI, (Isbert, A.
234, 188). With NaOEt (1 mol.) it gives
CHj(OEt).CO.eHMe.CO,Et (190°-195°). S.G.
S2 -976; whence alcoholic EOH gives
EtO.CH,.CO.CH2CH,.
Si-chloro-metbyl-aceto-acetic ether
C,H,.C1A- {210°-220°). S.G.i2 1-225. Formed
as above.
CHLOEO-MEIHYL-AMIDO-EENZOIC ACID
C,H3Cl(NHMe)C0,H [4:2:1] or [6:2:1]. [178°].
From the formyl derivative and alcoholic KOH.
Fine white needles. V. sol. alcohol with a blue
fluorescence, v. si. boI. water.
Formyl derivative
CeH,Cl(NMe.COH)COjH: [c. 202»]; fine white
plates or needles; si. sol. water, ether, and
chloroform, v. sol. hot alcohol. Formed, to-
gether with ohloro-methyl-isatin, by oxidation
of the methylo-chloride of (B. 1 or 3)-chloro-
quinoline with EMn04 (La Coste a. Bodewig, B.
18, 428).
j)-CHLOEO -TETEA - METHYIi-p-DI-AMIDO-
TBI-PHENYL-CAEBIN OL
C.H,Cl.C(OH):(C„H,.NMes),. [146°]. Colourless
crystals. Easily soluble in benzene and ether,
Formed by oxidation of the leuco-base the con-
densation-product of dimethylaniliue and p-
ohlorobenzaldehyde. The zinc double chloride
is a bluish-green dyestufE (Kaeswurm, B. 19
744).
TEI-CHLOEO-METHYL-p-AMlDO-PHENYL
ETHYI, - ALCOHOL Cl>C.CH(0H)C^4.NHMa
[112°]. Formed by the action of chloral hydrate
on methylaniUne (Boessneck, B. 21, 782). Crystals
(from alcohol).
Beactions. — 1. Sodium rvUHU added to a solu-
tion in HClAq forms a nitroso- compound
PER-OHLORO-TRl-METHYL-CYANIDINE.
r»
[116°] : needles, sol. alcohol, HOAo, and ether.
2. On heating with alkalis chloroform is split
oft, and methyl - amido • benzoic aldehyde is
formed.
Salt. — B'HCl: thick prisms, y. sol. hot, v.
si. sol. cold, water.
Tri - chloro - di - mathyl-^-amido - phenyl ethyl
alcohol CCl3.CH(0H).0,H,.NMe,.. [111°]. White
plates. Obtained by adding 5 pts. of powdered
ZnGl, to a cooled mixture of 10 pts. of ohloral
hydrate and 40 pts. of dimethylaniline, and al-
lowing the mixture to stand at about 50° for 24
hours ; yield 7 pts. By boUing with aqueous or
alcoholic EOH it is decomposed into chloroform
and di- methyl -^-amido-benzaldehyde [73°]. —
B'HCl. Sparingly soluble colourless needles
(Bcessneok, B. 18, 1616).
2)-CHL0B0-I£IBA-I[EIHYL ■ p ■ DI-AMIDO-
XBI-PHENYL-METHANE
C^.Cl.CH(0^,.NMe,,)j. [143°]. Obtained by
heating together di-methyl-aniline and p-chloro-
benzaldehyde in presence of ZnCl2 (Eaeswurm,
B. 19, 742). Small colourless concentric needles.
Sol. benzene, alcohol and ether, sparingly in
ligroin, insol. water. On oxidation it gives the
carbinol base which forms colourless crystals
[146°], easily Sol. benzene and ether, of which the
zinc double chloride is a bluish-green dyestufC.
Salts.— B"H201jPt01<: easily sol. . yellow
crystalline pp. The chloride and sulphate
are easily soluble colourless salts.
£79%)-I)i-chloro-di-methyl-di-amido-di-p1ieiiyl-
methane CCl2(08H4NMe2)2. Prom CS(CjH,NMe2)s
and BzGl in CSj (Baither, B. 20, 8289). Con-
verted by water into the ketone C0(C|,H4NMe2)j.
B-CHlORO-METHyL-o-AMIDO-STYEEHE
CsHi(NHMe).CH:CHCl. Formed by methylation
of ' ohloro-amido-styrehe (Lipp, B. 17, 2509).
Liquid, v. sol. alcohol and ether, nearly insol.
water. Volatile with steam. Heated with
sodium ethylate at 130°-140° it is converted
/CH^
into methyl-indole O^t'C. ^CH.
\NMe'^
K-DI-CHLOBO-UETHYL-AMINE v. Methtl-
CHLOBO-METHYL-ANIIINE C,H,C1N i.e.
CaH,Cl.NHMe. (240°). Formed by treating
NMe(CH0).CeH3Cl.CO2H with cone. HCl (La
Coste a. Bodewig, B. 18, 430). Liquid.—
B'HCl: [164°].
m-Ohloro-methyl-aniline [3:1] OjH.Ol.NHMe.
Aeetyi derivative C„H4Cl.NMeAc. [93°].
From wt-chloro-di -methyl- aniline and AoBr
(Staedel, B. 19, 1948). Tables, v. e. sol. benzene.
p-Chloro-methyl-aniline Nitrosamine.
C5HjOl.NMe.NO. [51°]. From i>-chloro-di-
methyl-aniline and nitrous acid (Eoch, B. 20,
2459).
o-Chloro-di-methyl-aiiilineCaHjCl(NMej)[l:2].
(206°). Formed by heating o-chloranUine
hydrobromide (1 mol.) with methyl alcohol
father more than 2 mols.) for 10 hours at 145°.
Colourlesa fluid. The hydrochloride forms
hygrosoopio needles, the ferrooyanide white
crystals, insol. water.— B'jHjCljPtOl, (Heidlberg,
B. 20, 149).
wi-Chloro-di-methyl-aniline [3:1] OaHjCLNMe...
(232°). From m-ohloro-aniline hydrobromide (a
little over 2 mols.) and MeOH (1 mol.) by heat-
ing for 8 hours at 145° (Baur s. Staedel, B. 16,
32). AoBr decomposes it in the cold, displacing
Ma by Ac, and forming OjHjClNMeAo (Staedel,
B. 19, 1948).— B'HBr: red plates.— B'HCl :
Blender needles.— B'jHjPtCl, : slender yellow
needles.
^-Chloro-di-methyl-aniline CoH<01.NMe2[l:4],
[36°]. (230°). Prepared by the action of CUjCl,
upon the diazo- compound of M-di-methyl-^-
phenylene diamine. Large flat glistening needles.
Sol. alcohol, ether, and benzene, insol. water.
The ferrocyanide forms microscopic prisms. —
B'^HjCLPtCL : golden-yellow prisms (Heidlberg,
J3. 20, 151). '
Bi-chloro-di-methyl-anillne OsHgOljNMe,^
(234°). From dimethylaniline and CI or SOjClj
(Krell, B. 5, 878 ; WenghofEer, J.pr. [2] 16, 462).
Liquid.— B'jHaPtOlo.
Tri-chloro-di-methyl-anillne OjH^CljNMej.
[32°]. (257°). From di-methyl-aniline and CI
(K.).— B'HCl.— B'^,PtCl,.
CHLORO-UETatL-BENZENE v. Chlobo-
lOLUENE.
Chloro-di-methyl-benzene v. OhiiObo-xyleiie.
Cl^loio-tri-metliyl-benzeae v. Chlobo-mesi-
TXIiEtlE and CHLOBO-;f'-OUMENE.
Ghloro-tetra-methyl-benzene 0. Chlobo-'
DUBENE.
Heza-chlor-heza-methyl-benzene O^H, ,01,.
[269°]. S.a. l£ 1-609. Probably 0.(CH2C1),.
Formed by the action of PCI5 upon (^^(CHa),.
I Colourless, flattened prisms ; commences to sub-
j lime at 269° ; v. si. sol. ether, or hot CHCl,. In
I contact with boiling water, made slightly alka-
I line, it very slowly loses all its chlorine, giving
a body of an aloohoho nature, [180°], v. sol.
acids ; which is sol. alcohol, si. sol. ether, t. si.
sol. water (Colson, Bl. [2] 46, 197).
I Heza-chlor-hexa-methyl benzene C^HijGls.
[147°]. 0^(CCl,)(CHjCl)3(CH3)2. Formed to-
gether with the preceding symmetrical isomeride
by the action of POI5 upon C5(CH3)e. Colourless
I crystals; sol. CHCI3. Boiling water, slightly
alkaline, removes its chlorine. The product is an
alcohol-acid, probably 0,(CH20H),(CH,)j(C02H)
(Colson, Bl. [2] 46, 198).
TBI - CHLOBO - TBI - IIETHTI - CARBINYI.
CHLOBISE V. Tetba-ohlobo-isobutane.
TEI-CHLOBO-DI-METHYL CAEBOITATE
C0(0Me)(00Cl3). (91°)at42mm. Formedbyaot-
ing on methyl alcohol with ClCOjCCl, (Hentschel,
J.iw. [2]36, 314).
Heza-chloro-di-metIiyl-oarbonateCO(OCCl3)2.
[79°]. Distils undecoinposed. Colourless crystals.
Prepared by the action of CI on methyl carbonate
(Oouncler, B. 13, 1698).
CHLOBO - METHYL -^sewtto- CAEBO-STYEIL
V. OHIiOBO-OXT-METHYL-QniNOLDJI!.
S-CHLOBO-a-METHYL CBOTONIC ACID
CH3.CCl:CMe.C03H. [69-5°]. Solidifies at 65°.
(210°). From methyl-aoeto-acetic ether and PCI5
(Isbert, A. 234, 188). LaminsB (from hot water).
Salts.— MgA'j 2aq.— ZnA'liaq.
Beaciicma.—l. NaOBt forms the ethyl deri-
vative of ;8-oxy-o-methyl-crotonio acid. — 2. Cono.
KOHAq forms methyl ethyl ketone and CO^:
chloro-butylene is not formed as 'Demar(jay
asserts.
Ethyl ether EtA.'. <173°).
PEB-CHLOBO - TBI - METHYL - CYANiniNE
V. ParanitriU of Tsi-cmMm-tSBXio ixna
80
CHLORO-TRIxMETHYLENE GLYCOL.
CmOEO-TBIMETHYLElTE GLYCOL v.
GliTOERIN {;8)-0HI.OBHYDKrN.
CHLOBO-METHTL ETHEK v. Chloro-di-
MBTHYIi OXIDE.
CHLOEO - METHYL - ETHYL - GLYOXALIITE
CsHjClNj. CMoro-oxal-ethyUne. (218°). S.G.is
1-142. From either di-ethyl-oxamide byPCl5(Wal-
laoh, il. 184, 37 ; 214, 261). Symmetrical di-ethyl-
ozamide gives a good yield, the nusymmetrical
a bad yield. , CONBtH.CONEtH gives, doubt-
less, NEt:CCl.CCl;NEt as intermediate product.
CONEtj.CONH, should give CCljNEt^.CN as in-
termediate product, but this then changes to
CClNEt.OClNEtbyintra-moleoularchange. This
view is supported by the production of chloro-
'cxal-ethyline by the action of PClj on di-ethyl-
cxamo-nitrile, NEtj.CO.CN.
- Properties. — Liquid, with narcotic odour, v.
e, sol. alcohol, ether, ligroin, and GHCl,. Changed
by frequent distillation into an isqmeric modifi-
cation (220°-224°), insol. ligroin. Water at
290° decomposes it, giving NH, and NH^Et.
Eeactums. — 1. Br in CS, or CHCl, forms
B'HBr, CoHgErClNjBrjHBr [113°], forming red
needles, and CsHsBrClNjBrj [133^. Both bodies
are unstable, and give, when boiled with water,
chloro - bromo - oxal- ethyline. — 2. KMnO, gives
oxalic acid.— 3. Dilute BLjSOj at 240° forms NH,
and NEtHj. — 4. Cone. HjSO, at 220° gives
acetic acid. -^ 5. Distilled over lime it forms
para-oxal-methyline. — 6. Na added to its solu-
tion in light petroleum forms di-oxal-ethyline,
C,jH,gN,.— 7. P and HI at 170° reduces it to
Salts .— B'jHjPtCl,.— B'HI aq.— B',H2ZnCl4.
B'HBr.— B'HClaq.—B'HgClj.—B'4HgClj.—B'£,
[110°].-B'AgNO..-B'H,C,O,.
Methylo-iodide B'Uel: [205°]; needles
(from alcohol).
CHLOBO-METHYL-TBI-ETHYL-PHOSPHO-
NIUM CHLOEIDE CH,Cl.PEt,Cl. From methyl-
ene chloride and PEt, (Hofmann, Pr. 11, 290) ;
CHi!(PBt3Cl)j being formed at the same time.
Formed also by the action of water on the com-
pound of PEt, and CCli.— (CHjCLPEtjO^jPtCl^.
Slightly soluble needles.
CHLOBO-METHYL-GLYOXALINE CHjClNj.
Chloro-oxalmethyline. (205°). V.D. 4-1 (obs.).
S.G. IS 1-247.
Preparation. — Pure di- methyl -oxamide
(10 pts.) is mixed with PClj (33 pts.) in the
cold. On warming HGl is evolved. The pro-
duct is distilled under diminished pressure, and
afterwards vrith steam, and is finally extracted
by shaking with GHCl, (WaUach, S. 14, 422;
A. 214, 308).
Properties. — Liquid ; reduced by HI to methyl-
glyoxaline.
Salts. — ^B'HI : needles, soL water and alco-
hol.-B',ftPtCle.
CHL0B0-IIETHYL-GL70XIS v. Chiabo-
ISO-NITR080-AOETONE OXIM.
SI-CHLOBO-MEXHYL-INDOLE
^'^*'^^n,)>^^ ^^^'^' I'°°«°«edle8. In-
sol. alkajia. Formed by methylation of ohloro-
oxindole-chloride (Baeyer, B. 15, 786).
CHLOBO.]«ETHYL.(PSEUDO)-ISATIN
C,H,Cl<^°jg>CO. [191°]. Long fine red
needles. Sublimable. Formed, together with
the formyl derivative of chloro-methyl-amida.
benzoic acid, by oxidation of the methylb-chlcrida
bf (B. lor3)-chloro-quinoUne with KMnO, (L*
Coste a. Bodewig, B. 18, 429).
TETBA - CHLOaO - BI - METHYL - DI - KE .
TONE (?) CHClj.CO.CO.CHCl,. [84°]. (202°).
A product of the action of EClO, and HGl on
chloranilio acid (Levy a. Jedlioka, B. 21, 318).
Large yellow tables (from ether). Pungent; sol.
water. Forms a phonyl-hydrazide [186°].
PEE-CHLOKO-METHYL-MEEOAPTAN
CCls.SC11(?). Tri-chloro-methyl-sulphur chloride. -
Thiocwrbonyl tetrachloride. (149° uncor.). S.G.
1-722 at 0° ; 1-7049 at 11° ; l-69o3 at 17i°/
Formation. — 1. From methyl sulphocyanide
and dry chlorine ; the yield is 83 p.c. of the
sulphocyanide (James, G. J. 51, 272). — 2. From
GSj and chlorine (Bathke, A. 167, 180).— 3. Prom
CSClj and CU.
Preparation. — By passing chlorine (5 mols.)
into cooled dry CS^ (1 mol.) containing a trace
of iodine ; the product is freed from chloride of
sulphur by treatment with water and distillaltion
with steam, and is Ihen fractionated in vacuo.
Properties. — Yellow oil, of very unpleasant
strong smell. By long heating to its boring-
point it slowly decomposes, probably into CCI4
and S.
Reactions. — 1. By treatment with chlorine in
presence of iodine it yields CCI4 and SgCl,. —
2. Alcohol forms an oil, possibly CS3CI,, and
orystaJs Of CjHbOj (126°).— 3. Water at 160°
splits it up into.COj, HCl, and S. Alkalis act in
the same way. — 4. By heating with suVphvv at
150°-160° it yields GS,, GGl4, GSClj, per-chloro-
methyl tri-sulphide (01013)28, and per-chloro-
methyl di-sulphide (CClj),^, ; but the latter ap-
pears to be the primary product : 2CCI,.SC1 + S^
= (CCl,)jSj + SjClj. Per-chloro-mcthyl-di-Bul-
phide is also formed by heating per-chloro-
methyl mercaptan with silver-powder, thus :
2CCl,.SCl-fAg2=(CCy„Sj + 2AgCl (Klason, B.
20, 2376).— 5. By SuCi^ it is reduced to CSOlj.—
6. HNO, (S.G. 1-2) oxidises it to GCls.SO.Gl.—
7. K2SO, gives C(SH)(S0aK)3.— 8. Anaine
(2 mols.) forms CCl,.S.NHPh ; an unstable oil
converted by excess ol aniline into di-amid-di-
phenyl sulphide, di-phenyl-thio-urea, and tri-
phenyl-guanidine ; and converted by alcoholic
KOH into CClj.S.NPh (?) [140°] (Eathke, 4. 167,
211; B. 19, 395). — 9. The analogous compound
CC1,.S.NHC„H4(CH,) is formed by adding
(2 mols. of) j>-toIuidlne to its ethereal solution.
This body is crystalline, and by boiling with
alcohol it is decomposed into p-toluidine, CO,
and HoS ; alcoholic KOH splits off HGl, giving a
body [i38°], which probably has the constitution
CGl2.S.N.GaHjMe (Eathke, B. 19, 395).
HEXA-CHLOBO-METHYL-METHYLENE DI.
KETONE (CCl,.CO)ipCH,; (258°). (0. 192°) at
20 mm. Is the final substitution product ob-
tained by the prolonged action of cmorine upon
acetyl-acetone at 120°-130°, and in direct sun-
light. Colourless liquid, decomposes when dis-
tilled under ordinary pressure. Treated with
NaOH (1 mol.) it gives tri-ohlor-acetone and
sodium tri-oblor-acetate (Combes, A. Oh. [6] 13.
238).
M-CHLOEO - (B) - METHYL - NAPHTHALEKB
C,.H,.CH,C1. [47°]. (168° at 20 mm.). VHiiiB
OHLORO-METHYL-QUINOLINE.
81
glisteniug plates. Formed by passing chlorine
into (j3)-metliyl-naplitlialene heated to about
250° (Sohulze, B. 17, 1529).
CHLORO-DI-MEXHYL OXIDE OjHjClO i.e.
Ca,C1.0.CH3. (60°). From di-methyl oxide and
CI in daylight (Friedel, Bl. [2] 24, 161 ; 28, 171 ;
C. R. 84, 247 ; Kleber, A. 246, 97). Decomposed
by water into HCl, MeOH, and formic paralde-
hyde (trioxymethylene). Ammonia forms hexa-
methyleneamine. KOAc gives CHj.O.CE^.OAc
(118°) ; Tyhioh is decomposed by water.
Di-ohloro-di-methyl oxide (CH^e^^O. (105°).
VJ>. 3-9 (oalo. 4-0). S.G. ^ 1-318. Frdm Me^O
and 01 in daylight (Begnault, A. 34, 31 ; A. Ch.
[2] 71, 396). Decomposed by boiling water into
HCl, formic acid, and formic paraldehyde (But-
lerow, Z. 1865, 618).
TetTa-chloro-di-methyl oxide (CHOy^O.
(130°). V.D. 6-4 (calo. 6-5). S.G. ^ 1-606.
From MojO and CI (Begnault, A. Ch. [2] 71,
396).
Eexa-ohloro-di-methyl oxide (CCyjO.
(100°). S.G. 1-597. From MCjO and 01 in sun-
Bhine (Begnault). Decomposed on vaporisation,
the V-D. being only 4-67.
2Vi - CHIORO - METHYL - PAKACONIC ACID
e, TBI-CHLOEO-OXT-ETHyL-SUOCniIC ACLD.
DI -CHlORO-DI-METHYL-^-PHENYIiENE.
DIAMINE O.HjClj(NMe,) (NH^) [5:2:4:1].
Formed, together with di-methyl-^-phenylene
diamine and di-ohloro-^-phenylene-diamine by
boiling nitroso-di-methyl-aniline with HCl (1-2
S.G.). By KjCrjO, and H^SO^ it is oxidised to
di-ohloro-quinone [159°]. By treatment with
FcjCl, in presence of H„S and ZnOlj it yields di-
chloro-methylene blue (Mohlau, B. 19, 2010).
CHLOEO-METHYL ISOPBOPYL KETONE
CsHbOIO i.e. 0HjC1.00.Pr. (o. 120°). From pe-
troleum pentane (?) or inactive amyl chloride by
treatment with CrOjCl^ followed by water (Etard,
C. R. 84, 127). Insol. water and aqueous KOH ;
reduces ammoniacal AgNOa. Does not combine
with NaHSO,.
TEI-CHLOKO-METHYI-PUEIN
■^r
N.CC1.C.N ^
C,(CH,)Cl3N, i.e. I II >01 (?) [174°].
CChN.C.NMe^
Small colourless crystals. Insol. alkalis.
Formed by heating di-chloro-oxy-methyl-purin
with POlj and POCl, at 160° for eight hours.
Heated with alcoholic NaOH it yields ohloro-di-
ethoxy-methyl-pnrin, which by HOI at 130° is
converted into methyl-uric acid (Fischer, B. 17,
331, 1787).
CHIOKO-a-METHYL-PYEIDIHE CsH,ClN.
Chloro-{a)-picoliMe. [21°]. (165° uncor.). S.G.
62 1-146. Formed by reducing the mixture of
penta- and hexa-chloro- picolines obtained by
heating comenamic acid with PCI5. The mixture
is heated at 210° with a solution of HI in
glacial acetic acid (Ost, J.pr. [2] 27, 278).
Properties. — Colourless prisms. Smells like
pyridine. Nearly insoluble in water, insoluble
in potash, soluble in alcohol and in ether.
Salts.-B',HC1. Prisms.-{B',HCl}2PtCl^.
Needles or prisms.
Chloro- methyl -pyridine CsH„ClN. (160 -
170°). From potassium methyl-pyrrol and
CHOI, (Ciamician a. Dennstedt, B. 14, 1162),—
B'jHjPtC]..
Vol. il.
Hexa-chloro-methyl-pyridine C5HCl3N(CClj).
[60°]. The chief product of _ the action of PCI,
(7 mols.) on comenamic (di-oxy-pyridine car-
boxylio) acid at 290° (Ost, J.pr. [2] 27, 277).
May be distilled with steam.
Properties. — Largo oblique prisma, or plates
(from alcohol). Insol. water, acids and bases.
Chloro-di-methyl-pyridine
MeC = N-CMe
I II . Chloro-lutidim. (178°). S.G.
HC:CC1 . CH
1-105 at 17°. Formed by heating oxy-di-methyl-
pyridine (leitidone) with PCI5 at 140° ; the yielii
i^ 50 p.o. Colourless oil. SI. sol. water.
Salts. — The hydrochloride forms slender
needles. — B'-,H2Cl.,PtCl4 : orange crystalline pp.
— "B'^HjCLjHgCO [155°], si. sol. water. Ohloro-
di-methyl-pyridine suspended in water gives
characteristic pps. with picric acid EjCr^O;,
CuSO<, and AgNOj (Conrad a. Epstein, B. 20,
104).
Tri • chloro - di - methyl - pyridine 0,Hs01jN.
Formed by chlorinating (B)-lutidine in presence
of iodine (Greville Williams, O. N. 44, 308).—
B'„H.,PtCle.
CHLOEO-DIMEXHYl-PYKIDINE CARBOXTr
Lie ACID
MeC = N-CMe
I II . Chloro-luiidine-di-ear-
H02C.C = CC1.C.002H
boxylic acid. [0. 224°]. Formed by the action
of PCI5 upon oxy-di-methyl-pyridine-di-carboxy.
lie acid (lutidone-di-carboxylio acid) at 140°.
White prisms. Sol. hot water (Conrad a. Ep-
stein, B. 20, 164).
Penta-chloro-tri-methyl-pyridinedi-carboxy-
lio ether. Di-chloride. [150°]. From hydro-
tri-methyl-pyridine di-carboxylic ether by ohlori-
nation (Hantzsoh, A. 215, 19). Woolly needles
(from alcohol).
IPy. 3)-CHL0S0-(Ptf. l)-METHYl-aUINO.
^ " ' CMe:CH
LINE 0,„H,NC1 w. O.HX I • [59°].
^ N :CCI
(296° cor.); From {Py. 3)-oxy-(Py. l)-methyj.
quinoline and PCI5 (Knorr, A. 236, 97). Mass of
slender needles (from dilute alcohol) ; v. si. sol.
water, v. sol; alcohol and ether ; volatile with
steam.— B'jHjPtClB 2aq. Eedueed by HI to
{Py. l).methyl-quinoline. Water at 160° has no
action : kt 200° it converts it into oxy-methyl-
quinoline.
(Pv. 2)-Cb.loTO-(Py. l)-methyl-quinoline
^ " ' ,CMe:CCl
C,H,MeClN ».«. 0.H.< | . [64°]. From
' ' \N : CH
skatole, chloroform, and alcoholio NaOH (Mag-
nanimi, Q. 17, 252). Delicate needles. Jts
picric acid compound melts at 208°, and
its anrochloride at 164°. _
Chloro-methyl-quinoline CAMeClN tx.
>CH:C01 ^ .V , , . ,
CHC I (^)- P^°]- Frommethyl-ketole,
" *\ ,N:OMe
chloroform, and alcoholic NaOH, thus s
C.HeMeN + 2NaOH -1- CHOI,
= CHsMeClN + 2NaCl + 2HjO
(Magnanimi, 0. 17, 249). White needles, insol.
water, sol. alcohol and ether. The picric acid
compound forms pale yellow needles [223°].
82
OHLORO-METHTL^UINOLINE.
(Py l)-Chloro-(Py. 3)-meth7l-qaiiialine
^CChCH
CH^MeCm i.e. 0^,< | . (y)-Chloro-
\ N:CMe
qumaldiTie. [43°]. (270°). From PCI, and oxy-
metbyl-quinoline, the product of condensation of
aceto-acetic ether with aniline (Goniad a. Lim-
pach, B. 20, 944). Water at 220° gives oxy-
methyl-quinoline. HI in HOAc at 260° gives
methyl-qninoline. The picric acid com-
ponnd melts at 178°.— B'^jPtOl,.— B'HBr.
(B. 4)-Chloio-(B. l)-methyl-quinoline
CH:eMe.O.GH:CH
OjEsMeOlN i.e. | || | . [49^.
CH:CC1.C.N:CH
From (6, 3, l)-chloro-ro-toluidine, nitro-benzene,
glycerin, and E^SO, (Gattermann a. Kaiser, B.
18, 2603). Needles ; v. sol. alcohol, ether, and
benzene. HI in HOAc converts it at 250° into
(B. l)-methyl-quinoline. The picric acid
compound melts at 172°.— B'HCl.HgClj.—
B'jH^tCI,.
{Py. 3)-Ghloro.(P^. 2,3)-di-methyl-qiunoline
.CMe:CMe
CJiX I . [131°]. From oxy-di-methyl-
\n = CCl
quinoline and POlj (Knorr, A. 245, 360). Crystals
(from alcohol). Water at 200° forms again the
di-melhyl-carbostyril. - B'jHjPtOlj 4aq.
{Py. l).Chloro-(Py. 3; B. 2-4).tri.methyl-
quinoline C,H,NClMe,. o-p-IH-meth^l-y-chloro-
qumaUme. [114°]. (298°). Formed by the
action of PCI, in presence of PdCl, on {Py. 1:3;
i}.2:4)-Ozy-tri-metbyl-quinoline (Conrad a.Lim-
pach, B. 21, 527). Flat prisms, .(from ether).
Sublimes easily. Almost insol. water, v. sol. dilute
acids, alcohol, ether, and benzene. On heating
with aniline the chlorine is replaced byNHPh. —
(B'HCl)2PtCl, : Needles ; t. si. sol. hot water.
Si-cliloro-(P^. 3)-iuethyl-qninoline
>CH:CH
CbHjOIjC I • Di-chloro-qmnaldme. [46°].
\ N:CMe
(300°). Obtained by heating di-chloro-o-amido-
benzaddehyde with sodium acetate and aqueous
NaOH (Gnehm, B. 17, 755).
I)i-chIoro-(J3. l)-methyl-qninoline
C;B,NMeCl,. [275°]. Formed by dissolving
(P.l)-methyl-quinoline in boric acid and treating
this with a solution of bleaching powder (Ein-
hom a. Lanch, A. 243, 361). Needles (from acetic
ether).
(Py.l:2:3)-Tri.chIoro-(B.4)-metliyl-qninoliiie
.CC1:CC1
0^{CB,)C I . Tri-ch}oro-toVuqmnolme.
^N : CCl
[112°]. Formed by heating {Py. 2:3:l)-di-ohloro-
oxy-(J5.4)-methyl-quinoline with PCI, at 125°.
Long colourless needles. Very volatile with
steam. Peculiar smell (Biigheimer a. Hoffmann,
B. 18, 2985).
(Py. 1:2:3) -Tri-cliIoro-fB. 2)-metIi7l-qiiinoline
^C1:0C1
0,H,(CH,K I • Tri^ehloro-toliiqimioUne.
Nn : CCl
[134°]. Formation.— 1. By the action of PCI,
npon malon-phenyl-amio acid. — 2. The acid
malonate of ^-toluidine (5 g.) is covered with
benzene (50 g.) and PCI5 (25 g.) slowly added;
after standing for some time the reaction is
corapleted by heating to boiling.
IS. — Long colourless needles. So),
alcohol, ether, benzene, &o., insol. water. Vola-
tile with steam. Peculiar smell. Weak base
(Rugheimer a. HoHmann, B. 17, 740 ; 18, 2975,
2979).
{Py. 2:4:1) - DI - CHLOEO - METHYL - ISO -
>OMe=CCl
ftTJINOLmrE CaH,< I . [102°]. Formed
NCCI =N
by the action of POCl, upon the imide of
phenyl - methyl - acetic - o - carboxylic acid
.0HMe.CO
CgH,^ [ . Long fiat needles (Gabriel,
\C0 - NH
B. 20, 2504)1
DI-CHLOBO-DI-lIETHYL-SUCCIinC ACID
C,H,CljO, t.e. C0;H:.CClMe.CClMe.002H. Di-
chloro-aMpic acid. [185°]. Formed, together
with pyrocinchonic acid, by the action of ' mo-
lecular ' silver upon a-di-chloro-propionic acid
in benzene solution (Otto a. Beckurts, B. 18,
847). Small crystals. Sublimable. ' V. sol.
water and alcohol, v. si. sol. benzene.
BeaciUms. — By further action of ' molecular '
silver it is converted into pyrocinchonic acid
C02H.CMe:CMe.C0jH. On reduction it gives
as chief product di - methyl - succinic acid
C0jH.CHMe.CHMe.00jH [194°]. By the ac
tion of alcoholic KOH, or by heating the silver
salt with water, chlorotiglic acid C^HgC^COjH)
is formed of melting-point [69°].
Salts.— A"Na2: plates.— A"K,2aq: plates.
— A"Ag2 : white crystalline pp.
FEB-CHLOKO-HETHTL-SI-STTLFHISE
(CCyjSj. (135° in vacuo). Obtained by the
action of silver-powder upon per-chloro-methyl-
mercaptan : 2 CCls.SCl + Agj = (CCy jSj + 2 AgCl.
Also formed by heating per-chloro-methyl-mer-
captan,with sulphur. Thick yellowish oU, of
slight turpentine-like smell. By distillation
at the ordinary pressure it decomposes into
CClj.SCl, CSClj, and other products. By heating
with sulphur at about 170° it yields per-chloro-
methyl tri-sulphide (CC^^S, (Elason, B. 20,
2379).
Per - chloro - methyl - tri - sulphide (CCl,) ^S,.
[57°]. (190° in vacuo). Formed by heating
per-chloro-metbyl di-sulphide with sulphur at
170° (Klason, B. 20, 2380) ; or by passing chlo-
rine into CS2 containing iodine (Bathke, A. 167,
209). Flat prisms ; v. e. sol. ether, CS,, and
warm alcohol. On distillation at the ordinary
temperature it decomposes into CCI3.SCI, CSClj,
S, and other products.
TBI - CHLOBO - METHYL-SULPHTTB - CHID-
BIBE V. PEB-CHLORO-METEYL-MEBCAf TAN.
CHLOBO-METHYI-TJBEA.
Acetyl derivative Ct'H.JC\'Sfi. i.e.
CHjCl.NH.CO.NH.CO.CHjCl. [180°]. From
ehloro-aoetamide, Br, and aqueous KOH (Hof-
mann, B. 18, 2735). Decomposed by acids and
alkalis into formic aldehyde and ohioro-acetio
acid.
CHLOBO-MTJCONIC ACID v. MuooNio acid.
(d)-CHLOBO-NAPHTHALENE C,„H,C1 i.«.
,CC1:CH
C.H.!
Z'
(251°) (P. a. S.) J (263°) (Atter-
'\CH:CH
berg, Bl. [2] 28, 509). S.G, •:* 1-20 (C).
i'ormatum. — 1. By heating (a)-diazonaphthal-
ene vrith a large excess of HCl ; the yield is
CHLORO-NAPHTHALENE.
83
88 p.o. of the theoretical (Gasiorowski a. Wajrsa,
B. 18, 1939).— 2. By boiling naphthalene diohlor-
ide 0„H,C1, with alcoholic KOH (Laurent, A. 8,
13 ; Faust a. Saame, A. 160, 68 ; Z. [2] 5, 705).—
3. By the action of PClj on (o)-nitro-naphthalene
(De Eoninok a. Marquart, B. 5, 11) or on naph-
thalene (a)-aulphoiiic acid (Carius, A. 114, 145).
4. From {a)-nitro-naphthalene and CI (Atter-
berg, B. 9, 317, 927).
Preparation. — By chlorinating naphthalene,
washing with alcoholic potash and fraction-
ating (Eoux, Bl. [2] 45, 515).
Prc^ertieis. — ^Liquid, not solid at -17°,
In CSi solution it is not much acted upon by
AljClj, but if (a)-chloro-naphthalene is warmed
with 20 p.o. of its weight of AI2CI5, some naphthal-
ene and tarry matters are produced together with
the (fl)- compound. In this reaction, therefore,
it behaves in a similar manner to (a)-bromo-
. naphthalene. Piorio acid compound [137°].
.CH:CC1
(;8)-Chloro-naphthalene C^Bj^ I [57°].
\OH:CH
(252°) ; (265° cor.). S.G. " 1-266 (E.).
Formation. — 1. By heating (fi)-diazonaph-
thalene with a large excess of HCl; the yield is
45 p.c. of the theoretical (Gasiorowski a. Wayss,
B. 18, 1940 ; cf. Liebermann a. Palm, A. 183,
270).— 2. By the action of PCI5 on ((8)-naphthol
or on naphthalene (/8) -sulphonic acid (Bimarenko,
B. 9, 663; CUve, Bl. [2] 25, 257).— 3. From
Hg(C,„H,)j and SOCl,, (Heumann a. Kochlin, B.
16, 1627). — 4. By intra-molecular change from
(a)-chloro-naphthalene {q. v.).
(l:2)-Di-cliloro-naphthalene C,„H,C1, [1:2]
[35°]. Formed by dropping a solution of potas-
sium nitrite (4 g.) in water (20 0.0.) into a boiling
solution of (a)-chloro-(;3)-naphthylamine hydro-
chloride (10 g.) and cuprous chloride (Sg.) in
hydrochloric acid; yield — 4g. Also from (a)-
ohloro-(;S)-naphthol and PCI, and from chloro-
(a)-naphthylamine (obtained by reduction of di-
chloro-a-naphthylamine) by replacing NH2 by
CI. Monosymmetrio tables, a:&:c = 1*5196:1:?,
fl = 76° 46' (CUve, B. 20, 1991). On nitration
it yields di-chloro-di-nitro-naphthalene [170°].
CrO, forms di-chloro-naphthoquinone [181°].
(11)- or (1, 3')-Di-ohloro-naphthalene C,„H„Cl2.
[48°]. From naphthalene (j3)-sulphonic acid by
nitration and treatment of the resulting {$)-
nitro-naphthalene (;3-) -sulphonic acid with FClj
(CUve, Bl. [2] 29, 499). Also from (/3).naphthyl-
amine (7)-sulphonic acid by exchanging NH,
for CI and treating the product with PCI, (Fors-
ling, B. 20, 2105). Also from (' P ')-naphthalene-
di-sulphonic acid and PCI, (Armstrong a. Wynne) ;
and synthetically from m-chloro-phenyl-isocro-
tonic acid (Erdmann a. Eirchhoff). Oxidation
by HNO, gives chloro-phthalic and nitro-phtha-
lic acids.
{B) or (l:3)-Di-chIoro-naphtIialene
C^.<^^'-^^>. [61° uncor.]. (286° uncor.).
Formation. — 1. From (5).nitro-naphthalene
(B).sulphonic acid and PCI, (C14ve, Bl. [2] 29,
415j. — 2. From di-ohloro-(o)-naphthylamino
[82°] by the diazo- reaction.
Properties. — Flat glistening plates, or slender
white needles ; may be sublimed, By HNOj it is
oxidised tc phthalic acid (ClSve, B. 20, 449).
The so-called ' a '-di-chloro-naphthalene [38°] is
a mixture of the fl and ' P '- isomerides. It gives
a Bulphochloride [148°].
, Dl-ohloro-naphthalene 0,„HaClj [1:2']. [64°].
Formation.—!. From ;8-chloro-naphthalene
sulphonic acid and PCI, (Arnell, Bl. [2] 45, 184 ;
Armstrong a. Wynne, 0. J. Proc. 4, 106).—
2. From (;8)-naphthol-('a') -Bulphonio acid
(Bayer's acid) by heating with PCJ, (Glaus a.
Volz, B. 18, 3157).— 3. From (;8)-naphthylamine-
(' o ')-sulphonio acid (Badische acid) (Forsling). —
4. From ohloro-jS-naphthol [101°] and PCI,
(C. a. v.). — 5. From p-chloro-phenyl-paraconio
acid (Erdmann a. Kirchhoff, A. 247, 379).
It gives a sulphochloride [119°].
('P') or (l,4)-Di-chloro-naphthaleno
,CC1:CH
C,.H,Clj t.«. C,H,< I . [68°J. (287°).
^CC1:CH
Formation.— 1. By distillation of naphthal-
ene tetrachloride (Erafft a. Becker, B. 9, 1089 ;
Faust a. Saame, A. 160, 70).— 2. From naphthal-
ene and CljO (Hermann, A. 151, 63).— 3. From
(o)-ohloro-naphthalene) in CHOI, and CI (Wid-
mann. Bra. II, 139). — 4.. By the action of PCI, on
(o)-nitro-(o)-naphthol (Atterberg, B. 9, 1189), on
bromo-naphthalene sulphonic acid (Jolin, Bl. [2]
28, 516), or on chloro-naphthalene sulphonic
acid, obtained from (a)-naphthylamine-^-sulpho-
nic acid (Cleve, Bl. [2] 26, 242).
Properties.— Needles (from alcohol). Boiling
dilute HNO, forms di-ohloro-phthalic acid. CrO,
in HOAc gives di-chloro-naphthoquinone [174°].
(0 or Pm-Si-chloro-naphthalene C,„H.CL,
CI CI
probably
rY^
(EkEtrand,B.18,2881). [83°].
Formed in smaiU quantity on distilling ' i8 '-di-
nitro-naphthalene with PCI, (Atterberg, B. 9,
1732). Formed also by nitratmg (7) -di-chloro-
naphthalene, reducing this to chloro-naphthyl-
amine [91°] and displacing NH, by CI (Atter-
berg, B. 10, 548). Prisms.
(K)-Di-chloro-naphthalene C„H,CL;. [94°
uncor.]. Formed by heating (a)-naphthoI sul-
phonic acid with PCI, (Claus a. Oeler, .B. 15,
314). On moderate oxidation it gives (a)-naphtho-
quinone and by further oxidation phtlialic acid.
(7)-Di-chloro-naphthalene C,„H,Cl2 [1:4']?
(Bkstrand, B. 18, 2881). [107°]. Formed by
the action of PCI, on (a)-nitro-naphthalene, or,
better, on (' a ')-di-nitro-naphthalene (Atterberg,
B. 9, 317, 1188, 1734), and on (a) -nitro-naphthal-
ene (a)-sulphonic acid (Cleve, Bl. [2] 24, 506).
Also from (a)-naphthylamine sulphonic acid
(Laurent's naphthalidinic acid) by diazotisation
and distillation of the resulting diazo-naphthal-
ene sulphonic acid with PCI, (Erdmann, B. 20,
3185). Formed synthetically from o-chloro-
phenyl-paraconic acid. Scales. Gives a nitro-
derivative [142°], and a di-nitro-derivative [246°].
Oxidation by HNO, gives chloro-nitro-phthalic
acid. CrO, in HOAc gives c-chloro-phthalic
acid [184°] (Guareschi, Q. 17, 119).
(8)-Di-chloro-naphthalene C,„H,Clj. [114°].
From naphthalene-(' a ')-di-sulphonia acid and
PCI, (CldVe, Bl. [2] 26, 244).' Large tables ; v.
sol. boiling alcohol. Dilute HNO„ gives chloro-
phthalic acid. It is perhaps Ci^HgCl, [2:2'].
(i)-Di-chloro-naplithalene G.^Kfil,. [120"].
Froiu naphthalene tetrachloride (4 pts.) and
64
CHLORO-NAPHTHALENE.
AfeO (3 pts.) at 200° (Leeds a. Everhart, Am.
2, 211). Formed, in very small quantity, when
Oji^jOl, is decomposed by alcoholic KOH (Wid-
mann, A 15,, 2162). Very thin lammEe; si. sol.
oold alcohol.
(e) or (2, 3')?-Di-chloro-naplithalene 0,„HeOl2.
ri36°]. (285° tmoor.).
Formation. — 1. By distilling (/3)-ohloro-naph-
thalene-sulphonic chloride -with FCl^; thechloro-
naphthalene-sulphonic acid being obtained either
by solphonation of (3)-chloro-naphth.aIene or by
the action of cuprous chloride upon the diazo-
compoundfrom tiie (/3)-naphthylamine sulphonic
acid obtained from (j3)-naphthol sulphonic acid
and NH, (Forsling, B. 20, 81 ; Arnell, Bl. [2]
45, 184). — 2. From naphthalene (* $ ')-disulpho-
nio acid, and from (3)-naphthol (a)-sulphonic
acid by distilling with POI5 (Olfive, Bl. [2] 25,
244; Armstrong a. Graham, C. J. 39, 142;
Glaus a. Zimmermann, B. 14, 1483). Needles
(by sublimation) or large monoclinic tables (from
alcohol). YolatUe. with steam. Sol. ether, chlo-
roform, and benzene, si. sol. alcohol. On oxida-
tion it gives chloro-phthalio acid CjHjC^COjHjj
■^4:2:1] and (' $ ')-di-chloro-(o)-naphthoquinone
il49°] (Glaus a. MiUler, B. 18, 3073).
(fl-Tri-cUoro-naphthalene C,„H5Cls. ' [56°].
Prepared by heating di-chloro-naphthalene (^)-
sulphonie chloride with PCI, (Widmann, B. 12,
962). Fine white needles. Insol. water, si. sol.
hot alcohol, v. sol. benzene.
(6)-Tri-ohloro-naphthalene CuHjCls. [65°].
From ))-di-chloro-naphthalene by nitration and
treatment of the resulting C,,H3Cl2(N02) with
PCI, (Cldve, Bl. [2] 29, 500). Needles, y. sol.
alcohol.
(e)-Tri.cMoro-iiaplithalene CjoHsClj. [76°].
From nitro-naphthalene (' a ')-di-sulphonic acid
and POI5 at 225° (A16n, Bn. II, 140). Small
needles (from HOAc). Y. sol. alcohol, m. sol.
boiling HOAc.
('o')-Xri-cliloro-naplitlialene C,„H5Glj. [82°].
Formation. — 1. By the action of alcoholic
KOH upon (a)-ehloro-naphthalene-tetra-ohloride
(Faust a. Saame, A. 160, 71). — 2. By heating
(n)-naphthol-di-sulphonio chloride with POI5
(3 mols.) at 170°-180° (Glaus a. Mielcke, B. 19,
1182).
Properties. — Colourless needles. V. sol.
chloroform, ether, and hot alcohol. HNO3 at
200° gives tri-chloro-nitro-phthalio acid (Wid-
mann, Bl. [2] 28, 511).
C"C1:C01
I
H:CCI
[90° nncor.]. (above 360°).
Formation. — 1. By heating di-ohIoro-(a).
naphthol [101°], or'sodium (a)-naphthol (;B)-sul-
phonatewith PGI5 at 130°-140° (Glaus a. Knyrim,
B. 18, 2926).— 2. By chlorinating (a) -nitro-naph-
thalene (Atterberg, B. 9, 926).
Properties. — Needles (from alcohol). Maybe
Bublimod. Insol. water, v. sol. other solvents.
Tii-cbloro-naphthalene CuPjCls. [90°].
Formed together with di-chloro-(;3) -naphthol
[125°], by heating sodium (3)-naphthol (j3)-di-
Bulphonate with 5 mols. of PCI5 at 210°.
Properties. — Fine white needles. Subli-
niatile. V. sol. ether, benzene, etc., and hot
ai<;ohol, si. sol. cold alcohol. Heated with nitric
seid (S.G. 1-16), at 210° it yields a syi-upy di-
chloro-phthalio acid. By CrO, it is oxidised to
the same di-chlbro-phthalic acid, together with
a tri-chloro-(ci)-naphthoquinoue which gives an
anilide C,„H8Clj(NHPh)03 which melts at [228°].
Hence it appears to be different from the tri-
ohloro-naphtha.lene of melting-point [90°]
already known (Clans a. Schmidt, B. 19, 3174).
(7)-Tri.chloro-naphthalene OioHsCl,. [103°].
Long white needles. Prepared by distillation of
dichIoro-naphthalene-(a)-sulphonic chloride with
PCI5 (Widmann, B. 12, 2230). Formed also by
chlorinating (o)-nitro-naphthalene (Atterberg, B.
9,317). Prisms. By heating to 170° with HNO,
(i'42) it gives di-nitro-di-chloro-phthalic acid.
(Tj)-Tri-cMoro-naphthalene OioHjClj. [113°].
From nitro-naphthalene (;3)-disulphonio chloride
and POli at 190° (Al&a, Bn. II, 140). Needles
(from HOAc). V. sol. warm alcohol ; v. e. sol.
benzene. Volatile with steam.
(S)-Tri.chloro-naphthalene C.oHjCl,. [131°].
Formed by the action of PCI,, on (' 0 ')-di-nitro-
naphthalene, nitro-(7)-di-ohloro-naphthalene,
('o') chloro-di-nitro-naphthalene [106°], ('3')-
ohloro-di-nitro-uaphthalene, and nitro-(' 0 ')-di-
ohloro-naphthalene (Atterberg, B. 9, 1187, 1733;
Widmann, £Z. [2] 28,511). Long needles. Oxida-
tion gives di-chloro-phthalic acid.
(' a ')-Tetra-chloro-iiaphthalene 0,„H,C1,.
[130°]. Formed by the action of alcoholic KOH
on the (' a ')-di-chloro-naphthalene (' o ')-tetra-
chloride, obtained by chlorinating naphthalene
(Faust a. Saame, A. 160, 72). Formed in the
same way from (' $ ')-di-ohloro-naphthalene tetra-
chloride, and from (' 0 ')-tri-chloro-naphthalene
dichloride (Widmann, Bl. [2] 28, 511). Long
needles. Oxidation gives di-chl6ro-phthalio
acid.
Tetra-chloro-naphthalene C,gH.Cl. i.».
>CC1:G01
CsHj< I (?). [140° nnoor.]. Formed by
NCChCCI
heating (a)-naphthoI-tri-gnlp]ionic chloride with
PGI5 (4 mols.) at 210°-250°. Sublimes in colour-
less feathery needles. Crystallises from toluene
in long thin needles. V. sol. hot alcohol, ether,
chloroform, &e., si. sol. cold alcohol, insol. water.
On oxidation with OrOj or HNO, it is converted
into di-chloro-(a)-naphthoqainone [189°],
XO.OCl
OjHjf^ ' II , together with chlorinated
^C0:CC1
phthalic acids (Glaus a. Mielcke, B. 19, 1184).
Tetra-chloro-naphtlialene OjoH^Cl,. [141°].
Formed by the action of alcoholic KOH on (7)-
di-chloro-naphthalene tetrachloride [85°], and
on tri-chloro-naphthalene di-chloride [93°J (At-
terberg a. Widmann, B. 10, 1842). Slender
needles ; si. sol. alcohol. May be identical with
the preceding.
(f) - Tetra - chloro - naphthalene C,„HjCl,.
[160-5°]. Formed by acting on (e)-di-chloro-di-
nitro-naphthalene with PClj (Al£n, Bl. [2] 36,
435). Interlacing needles.
(7) - Tetra - chloro - naphthalene C,|,H,C1,.
[176°]. Obtained by the action of alcoholic
KOH on, (' a ')-di-chloro-naphthalene (' a ')-tetra-
chloride got by chlorinating naphthalene (Wid-
mann, B. 10, 1724; Bl. [2] 28, 512). Flat needles,
si. sol. alcohol.
(e)-Tetra-chloro-naphthalcneC,„HjCl4.[180°].
From di-nitro-(7)-di-chlaro-naphtbalene by die-
CHLORO-NAPHTHALENE STJLPHONIO ACID.
tilling with POI5 (Atterberg a. Widmann, B. 10,
1843). Long needles ; si. sol. alcohol.
' (' j8 ')-Tetra-chloro-naphtlialene CioHjCl,.
[194°]. Formed by chlorinating nitro-naphthal-
ene (Atterberg, B. 9, 318).' Needles, v. si. sol.
alcohol.
Fenta-chloro-naphthalene G,.H,CL t.e.
^CH:OH
OfiU<C I • [169°]. (above 360°), Pre-
^CChCH
pared by heating di-chloro- (a) -naphthoquinone
with twice its weight of PCI, to 250° (Oraebe, A.
149, 8 ; Glaus a. Lippe, B. 16, 1016). Needles
(from alcohol). On oxidation with fuming HNO3
at 110° it gives tetra-chloro-naphthociuinone.
Dilute HNOj at 190° gives tetra-chloro-phthalio
acid.
(' fi ')-Fenta-cliIoro-uaphthaIene C,„HjClj.
[177°]. From nitro-(S)-tetra-chloro-naphthalcne
and PCI5 (Atterberg a. Widmann, B. 10, 1843).
Needles. Oxidises to tri-ohloro-phthalic acid.
Hexa-chloro-naphthaleue CggH^Clg. [143°].
Formed by chlorinating tri-ohloro-naphthalene
(Laurent). Six-sided columns; v. si. sol. alcohol,
m. sol. ether. May be oxidised to hexa-chloro-
aaphthoquinone.
.001:001
(/3)-Eepta-chloro-naphthalene 0,01,^ |
\CC1:CH
[194° oncor.]. Formed by heating tetra-chloro-
(a)-naphthoquinone (1 pt.) with POlj (2 pts.) for
6 or 8 his. at 250°. Small colourless needles.
Sablimable. By heating with HNO, (1-5 S.G.)
it is oxidised topenta-chloro-(a)-naphthoquinone
[217°], and , tetra-chloro-phthalic acid [250°]
(Claus a. Wenzlik, B. 19, 1165; c/. Glaus a.
Lippe, B. 16, 1019).
Fer-chloro-naphthalene OigCIg. [203° uncor.].
(403°). Formed by heating tetra-ohloro-oxy-
naphthoqninone [265°], penta-chloro-(a)-naph-
thoquinone [217°], or (a)-naphthol-tri-suiphonic
chloride, with POlj at 250°. Prepared by the
protracted chlorination of naphthalene in pre-
sence of SbOl, (Berthelot a. Jungfleisch, Bl. [2]
9, 446 ; A. Ch. [4] 15, 332). Colourless needles.
Sublimable (Clans a. Wenzlik, B. 19, 1169;
Claus a. Mielcke, B. 19, 1186). By heating with
SbClj at 290° it is split up into G„Hj, Cfil^, and
CCl, (BuofC, B. 9, 1048). It is partially converted
into naphthalene by passing with hydrogen
through a red-hot tube.
DI - CHIOEO - NAPHTHALENE TETEA -
^BOMIBE CioHaClaBr^. [c. 100°]. From di-
jhloro-naphthalene and Br.
(o).CHLOaO-NAPHTHAIENE TETSA-
CHLOBIBE 0,„H,0l5. [131°]. Formed by the
action of 01 on naphthalene ^aust a. Saame,.i.
160, 67) or on (o)-ohloro-naphthalene (Widmann,
B. 10, 1724; Bl. [2] 28, 605). Monoolinic
iprisms (from chloroform). Oxidation gives phtha-
lic acid. Alcoholic KOH forms (' a ')-tri-chloro-
naphthalene.
(/S)-Chloro-naphtlialene tetra-chloride
OijHjCls. From (/3)-chloro-naphthalene and CI
•(W.). Oil.
Di-chloro-naphthalene tetra-chloride
C,„HsGl,. [85°]. From (7)-di-ohloro-naphthalene
and CI (Atterberg a. Widmann, B. 10, 1841).
Prisms. Alcoholic KOH gives (5).tetra-ohloro-
naphthalene.
86
Si-chloro-naphthalrae tetra-chloride
,0,.HjCl„. [172°]. Formed by the action of CI
on (' a ') or (' $ ')-di-ohloro-naphthalene (Wid-
mann, Bl. [2] 28, 506). Monoolinic prisms (from
CHClj). V. e. sol. HOAo and benzene. Oxida-
tion gives di-chloro-phthalic acid. Alcoholic
KOH gives (' a ') tetra-ohloro-naphthalene.
Bi-chloro-naphthalene tetra-chloride
CioHjCl,. Formed, together with the preceding,
by the union of 01 with (' a ')-di-chloro-naphthal-
ene. Oil. Alcoholic KOH gives ('y)-tetra-chloro-
naphthalene.
(' o ') - Tri - chloro - naphthalene di - ohiorido
C.oHjClj. - [93°]. From (7)-di-ohloro-naphthal-
ene and 01 (Atterberg a. Widmann, B. 10, 1842).
Alcoholic KOH converts it into (5)-tetra-chloro-
naphthalene.
(' j8 ') - Tri - chloro - naphthalene di - chloride
0,„H,Cl5 [152°]. Formed, together with
GioHsClsHOAo [195°], by passing chlorine into a
solution of (a) - chloro - naphthalene in glacial
HOAc (Widmann, Bl. [2] 28,507). Short prisms,
si. sol. alcohol.
CHLOEO - NAPHTHALENE ~ SULPHINIC
ACID CjoHaCLSO^H. Formed by the action of
sodium amalgam on (o)-chloro-naphthalene sul-
phonic bromide (?) [115°] obtained from bromo-
naphthalene sulphonic acid by POl, (Qessnev, B.
9, 1504). Slender needles (from alcohol). —
BaA',l|aq.
(a)-CHLOBO -NAPHTHALENE (a)-StrLPHO -
NIC ACID G,„H,C1S0, i.e. C,„H,C1(S03H) [1:4-].
Obtained by heating (a)-diazo-(o)-naphthalene-
sulphonic acid with HCl. V. sol. colourless
tables (containing 2aq).
Salts. — A'K: silvery needles. — A'Na: thin
scales.— A'Ag : thin tablets, v. si. sol. cold water.
A'jBa aq : sparingly soluble powder.
Ethyl ether A'Et: [46°]; large monosym-
metrical prisms, a:6:c = l-6785:l:?, /8 = 68° 58'.
' Chloride C,„H,C1{S0,C1) : [95°]; large crys-
tals (from chloroform).
Amide C,„Ha01(S0aNHj) : [226°]; sparingly
soluble silvery scales (OlSve, B. 20, 72).
(ii)-Chloro-naphthaler6 (/3)wsulphanic acid
CpHjClSO, i.e. C,^fil{SO,m [1 i 2'or31. Ob-
tained by the action of CujGI, upon the diazo-
compound of the naphthylamine sulphonic
formed by reduction of the 'jS'-nitro-naphthal-
ene (i3) -sulphonic acid (sparingly soluble Ba salt),
which is one of the products of the nitration of
naphthalene (3)-suIphonic acid.
Properties. — V. sol. colourless rhombic tables.
When heated in a current of steam it yields (n)-
chloro-naphthalene.
Salts. — A'Ag: thin glistening tables, sol.
hot water, si. sol. cold. — A'jBa aq : sparingly sol.
crystalline powder.
Ethyl ether A'Et: [111°]; monosymme-
trical crystals, a:b:e = -4307:1:7, j8 = 86° 45' ; v. e.
sol. hot alcohol.
Chloride C,„HsCl(SOjCl) : [114°]; smaU
SCSilsS
Amide C,„H,Cl(SOjNHJ : [216°]; thin
plates (016ve, B. 20, 74).
(a) -Chloro -naphthalene j)-Bnlphonic acid
G,»H,CiS0, i.e. 0„H,C1(S0,H) [1:4].
Formation. — 1. By sulphonation of (a)-ohloro-
naphthalene (Zinin, J. pr. 33, 36).— 2. From
(a)-naphthylamine-27-suIphouic acid (naphthioni<<
8R
OHLORO-NAPHTHALENE SULPHONIC ACID.
acid) by the action of CuoClj upon its diazo- com-
pound.
Properties. — Silvery plates. Converted by Br
into ohloro-bronio-naphthalene [67°]. ,
Salts. — KA'. — BaA'r — , ZnA'j 6aq. —
CuA'2 7aq.— AgA' aq (Amell, Bn. ii. 153).
Ethyl ether EtA': [104°] ; large thin mono-
clinio tables, a:6:c = l-3281:l:l-1262, (3 = 80° 59'.
Chloride 0,;H.fil{80fi\) : [95°]; gives,
with PC1„ (' /3 'J-di-ehloro-naphthalene [68°]
(Arnell, Bl. [2] 39, 62).
Amide 0„H.01(S02NH,): [187°] (Cleve, JB.
20,73).
(a) - Chloro - naphthalene sulphonic acid
CioHeCLSOsH. Formed in small quantity, to-
gether with the preceding, by sulphonating ohloro-
naphthalene with Cl.SO^ (Armstrong a. Wil-'
Uamson, 0. J. Proc. 2, 234).
Chloride C„H5C1.S0,C1 : [127°]; short
thick prisms.
(0) - Chloro - naphthalene snlphonic acid
0,„H„C1(S05H). Sparingly sol. water.
Formation. — 1. By sulphonation of (3)-ohloro-
naphthalene by HjSO, or CISO3H (ArneU, Bl.
[2] 45, 184). It appears to be formed by isomeric
change from the preceding by heating to 150°
(Armstrong a. Wynne, C.J. Proc. 3, 22, 145).—
2. By the action of cuprous chloride upon di-
azotised (i3)-naphthylamine-sulphonic acid ob-
tained by treatment of (;9)-naphthol sulphonio
acid with NH,.
Salts.— BaA's.—KA' Jaq.'
Chloride C„H.Cl(SO,qi) : [110°] ; needles;
by distillation with PCI5 it gives (6)-di-ohloro-
naphthalene [136°].
Amide C,„H,Cl(SOjNHj) : [184°] ; needles
(Forsling, B. 20, 80).
(^)-Chloro-naphthaIene aulphonic acid
C,oH,Cl.SO,H[2:3']?
Formation. — 1. By heating (/3)-chloro-naph-
thalene with fuming H^SO^, and separated from
the preceding acid through the greater solubility
of its lead salt (ArneU, Bl. [2] 45, 184).— 2. By
diazotising (0)-naphthylamiue sulphonic acid,
and boiling with cone. HCl (Forsling, B. 19, 1715).
Properties. — Trimetric scales. — ^BaA', 4aq :
laminoi. — EA' aq : small scales.
Chloride [129°]. Converted by PCI5 into
di-chloro-naphthalene [61'5°].
Di-chloro-naphthalene (a)-Biilphonic acid
C,„H5Clj(S0,H). Prepared by boiling the tetra-
chloride of (a)-naphthalene-sulphonic chloride
with alcoholic KOH (Widmann, B. 12, 2228).
Long flat needles. H. sol. cold water.
Salts. — A'K 2aq : fine needles. — ^A'Na aq :
long flat prisms. — A'Ag 2aq : white needles. —
A'sCa 4aq : slightly soluble leaflets.
Chloride [145°]. Scales or needles. Sol.
benzene and hot acetic acid. By distUlation
with POlj it gives {7)-tri-chlor6-naphflialene.
Amide [about 250°]. Flat feathery
aystalg.
Si-chloro-naphthalene (;8)-sulphanic acid
0,oH^Cl2(SO,H). Prepared by boiling the tetra-
chloride of naphthalene- (^) -sulphonic chloride
(C,„H,(S02Cl)Cl4) with alcoholic KOH (Widmann,
B. 12, 959). Beadily sol. hot water, less in cold.
Strong acid.
Salts. — A'KSaq: very fine needles. S. 2-5
at 1&°.— A'E l^a^.— A'K 2^aq : small prisms.—
fine
A'Ag aq : crystalline powder. — A'-^Ba 4aq :
sparingly soluble needles. — A'jCa 2aq.
Chloride [133°]; fine white needles. Sol.
OjHs and CS^.
Amide [245°]; fine needles. Insol. water,
sol. alcohol.
Tri- and Tetra-ohloro-naphthalene sulphonic
acids have been described by Laurent {A. 72,
299), but not sufficiently characterised.
CHLOEO-NAPHTHAI.IC ACID v. Chlobo-
OXI-(a)-NAPHTH0(lUIII0NE.
CHLOSO - HAPHTHOHYDSOaUINONE v.
Chloro-htdbo-naphthoquinonb.
CHLOBO-(a).KAFHIHOIC ACID
CO.H
C,oH.Cl(COaH), probably
CO-
01
[245°].
Formation. — 1. By ohlorination of (o)-naph-
thoic acid in acetic acid solution. — 2. By the
action of cuprous chloride upon the diazo- com-
pound obtained from nitro-(a)-naphthoio acid
[239°].— 3. From the nitrile.
Properties. — Sublimes in white needles. By
fuming ENO, it is converted into chloro-nitro-
(a)-naphthoio acid [225°] and chloro-di-nitro-
naphthalene [175°] (Ekstrand, B. 17, 1604 ; 18,
2881).
Salt.— A'2Ca2aq: needles; S. -86.
Ethyl etfter A'Et: [42°]; quadratic tables.
Amide 0,„H.C1(C0NH,). [239°]. Formed
by boiling the nitrile with alcoholic KOH
(Ekstrand, Bn. ii. 925).
Nitrile C.ACl.ON [145°]. White needles.
Formed by ohlorination of (a)-naphthonitrile
(Ekstrand, B. 17, 1604).
Chloro-(/3)-naphthoic acid C„HaCl.COjH.
[261°]. From the nitrile and fuming HOI at
150° (Ekstrand, Bn. ii. 931). Needles (from
alcohol).
Ethyl ether 'Etk'. [45°]. Needles.
Nitrile O.j^sCl.CN. [138°]. From (;8).
naphthonitrile in HOAc by chlorinating in pre-
sence of iodine.
Di-chloro-(;3)-naphthoic acid C,„H5Cl2.C0jH
[291° uncor.]. Sublimable. Colourless needles.
Sparingly soluble in alcohol and in acetic acid.
Formed by ohlorination of (i3)-naphthoio acid.
Salts.— A'jCa 2|aq : small sparingly soluble
prisms.
Ethyl ether A'Et : [66°] ; long needles.
S. -03 (Ekstrand, B. 17, 1605).
(0,04) CHIOBO-NAPHTHOL C,„H.C1(0H)[1:4].
[57°]. Formed by the action of PClj on (o).
naphthol-sulphonic acid. Small felted needles.
On moderate oxidation, it gives (a) -naphtho-
quinone, and by further oxidation phthalic acid
(Clans a. Oehler, B. 15, 312).
Chloro-(a)-naphthol 0,oH.Cl(OH). [109°].
Formed by distUling the compound C,gH,(HOCl),
with aqueous HCl (Grimauz, Bl. [2] 18, 208).
(6)-Chloro-(a)-naphthol C,„H,C1(0H)[2:1] [0.
54°]. Is contained in the mother liquors ob-
tained by passing chlorine into a solution of
(a)-naphthol in HOAc (Cleve, B. 21, 894).
V. e. sol. most menstrua ; only orystallisable
from petroleum ether.
Chlorine forms di-chloro-napbthol [106°Ji
FCl, yields tri^sohloro-naphthalene [92°].
OHLOIlO-NAPHTUOQUmONE.
87
Chloro-(;8)-nap5ithol C,oH5Cl(OH)[l:2]. [68°]
(S.); [TO"] (0.). Formed by the action o£
chlorine on (;3)-naphthol sodium suspended in
CSj (Sohall, B. 16, 1901), or dissolved in HOAo
(Cleve, B. 31, 895).
Needles or monoolinio plates (from chloro-
form); o:6:e = l-96:l:l-956;/3 = 66°54'. Volatile
with steam. Gonveited by PCI, into chloro-
naphthyl phosphate (OjaHsClJsPO, [152°] or, at
a higher temperature, into (1, 2)-di-ohloro-
naphthalene [34°].
.OH:C(OH)
(2:3)-Chloro-(3)-naphthol CaH,< I
\CH:CC1
[101° nncor.]. (308°). Formed by heating
sodium (/3)-naphtuol (/3)-snlphonate (Bumpf's
acid) (1 mol.) with PCI, (2 mols.) at 150°-160°.
Fine colourless needles, v. e. sol. alcohol, ether,
etc., si. sol' water. Volatile with steam. By fur-
ther action of FGl, it yields di-ohloro-naphthalene
[61°] (Glaus a. Volz, B. 18, 3157).
Chloro-(;8)-naplithol G„H„01.0H. [115° un-
eor.]. Formed, together with (c)-di-chloro-
naphthalene, by heating potassium (i8)-naphthol-
sulphonate with PCI, (8 mols.) to 170° (Glaus a.
Zimmermann, B. 14, 1484). Fine needles or
prisms. Sol. alcohol, ether, and hot water. Kot
volatile with steam.
.C(0H):GC1
Di-chloro-(a)-naphthol ^e^■^\ I •
^GH ;GC1
[101° nncor.]. Formed by heating sodium (a).
naphthol-(jS)-sulphonate (1 mol.) with PCI,
(2-2i mols.) at 100°-120°. Sublimes in white
needles. V. sol. ordinary solvents. By further
treatment with PCI, it is converted into tri-
chloro-naphthalene [90°]. By dilute HNO, at
200° it is oxidised to phthalic acid. By boiling
with an acetic solution of CrO, it is oxidised to di-
.CO.GGl
ohloro-(a)-naphthoqainoneGJS.C^ II [189°].
\C0.CG1
(Glaus a. Enyrim, B. 18, 2926).
lli-chloro-(a)-naphtliol C,oH,Clj(OH) [1:3:4].
[106°] (C.) ; [108°] (Zinoke, B. 21, 1027). Formed
by passing chlorine into a cold solution of (m)-
naphtholin HOAc (Cleve, B. 21, 891). Needles.
Sol. alcohol, chloroform, benzene. Crystallises
from HOAc as G,jH5Cl20H + HOAo losing HOAo
at 40°-50°.
BeaeU<ms. — 1. Yields on heating a substance
Cj,H„Cl20j (?).— 2. Dilute HNO, forms yellow
needles of a quinone-like substance and phthalic
acid. — 8. Oxidation with chromic acid forms
chloro-naphthoquinone [116°], which on heat-
ing with aniline forms the anilide [203°] (c/.
Knapp and Schultz, 4.210, 189).— 4. PCI, forms
(1,8,4) tri-chloro-naphthalene.
Acetyl derivative O.oHsCLjOAo. [76°].
Di-chloro-(;8)-naphthol C,aB.fili{OE). [125°
uncor.]. Formed, together with tri-chloro-
naphthalene [90°], by heating sodium (j3)-
naphthol-(/3)-di-snlphonate with PCI, at 210°.
Colourless felted needles. Sublimable. V. sol.
alcohol, ether, etc., si. sol. hot water (Glaus a.
Schmidt, B. 19, 8174).
Tri-cliloro-(o)-iiaphthol C,„H4Cl3(OH)[4:8:2:l].
[160°]. From tri-ohloro-naphthol dichloride
and NaHSO, (Zincke, B. 21, 1027). Silky
needles (from HOAo). CrO, oxidises it to di-
chloro-(a)-naphthoquinone.
C.H,<
Acetyl derivative 0,oH,Cl,OAc. [124°].
< GO. CGI J
I 0'
COlrCH
!Pruehloro-{a)-'ketonaphthalene.
/
'\gc1j.ch'
[121°]. From (o).naphthol in HOAc by ohlorina-
tion (Z.). Flat monoclinic prisms; v. e. sol.
benzene. Boiling dilute alcohol converts it into
chloro-(a)-naphthoquinone. Hydroxylamine hy-
drochloride appears to form an oxim [c. 148°],
a compound OuH,Cl,(NO), and a third body
[205°].
xaccij
Tetra-chloro-(a)-napIitIioI 0,B.jC I
/CO. CGI \gC1:CCI
or CjH^^ II . Tetra-chloro-{a)-ketonaph-
^GGlj.CCl
thalene. Two modifications, corresponding
perhaps to the above tormuls, are formed by
chlorinating tri-ohloro-(a)-naphthol (Z.), viz.
rhombohedra [105°] and prisms [94°]. Boiling
dilute alcohol or dilute HOAc convert both into
di-cliloro-(a)-naphthoqainone. Dilute alcoholic
KOH forms chloro-oxy-naphthoquinone. EOH
in absolute alcohol appears to form
00 CO
CjaZ I . [149^.
\C(OBt):CCl
'IIlI-GHLOKO-(a)-irAFHTHOI. SICHLOBISE
C.H,(
GCCCli,
[157°]. From Gl and (a)
•GGL,.CH01
naphthol in cold HOAc (Zincke, B. 21, 1027).
Monoclinic plates (from benzene). NaHSO, in
presence of HOAo reduces it to tri-chloro-(a)-
naphthol. Dilute alcohol or dilute HOAc ' ai
130° form di-chloro-(a)-naphthoquinone. Alco-
<C0 G(NPhH)
II
C(NPh).CCl
[157°] whence B'jHjPtGl..
, Ietra-cblaro-(a)-iiaphthol dichloride
.CO . CClj
CtUt<(^ I . [130°]. From tetra-chloro-
^GGIj.CCIq
(ct)-naphthol, MnO^, and HCl (Z.). V. sol.
benzene and hot alcohol, si. sol. ether. Does
not react with aniline. May be reduced to tri-
chloro - (a) - naphthol. Alcoholic EOH forms
CCls:CCl.CO.GeH,.GOjH [128°].
CHL0B0-(a)-KAFHXH0aUIN0N3: 0,^,010,
jCO CCl
i.e.0.H,< 'll [111T(P.); [116°] (GUve,
\go.cci
B. 21, 891); [118°] (Zinoke, B. 21, 1027). A
by-product in the preparation of di-chloro-(a)-
naphthoquinone [189°] by treating di-nitro-(a)-
n'aphthol with KCIO, and HOl (Plagemann, B.
15, 485).
The following amides are formed by treating
di-chloro-(o)-naphthoquinone with the corre-
sponding amine in'alcoholic solution (P.) :
Methylamide G,„H^C10,NMeH. [150°].
Orange needles, v. sol. alcohol.
Di-methyl-amide C,„H,C10jNMe,. [85°].
Scarlet needles, v. sol. alcohol.
Ethylamide GioHiGlOjNEtH. [110°].
Brownish-red needles, v. sol. alcohol.
Anilide C„H4C10j.NHC„H, [208°] (P.);
[202°] (E. a. S.; G.). Bed metallic needles.. SoL
88
OHLOEO-NAPHTHOQUINONE.
Metic acid and alkalis, e1. sol. alcohol. Its
Bolution in cone. H2SO4 is of a magenta colonr.
SnCl, redaeas it to, a dihydride [170°] (Knapp a.
Schultz, A. 210, 189).
mbroaamim C,(,H,C10jN(N0)C.H5 : [126°];
yellow needles or plates, sol. benzene, si. sol.
iigioin ; formed by passing nitrous acid into the
anilide suspended in acetic acid (Flagemann, B.
16, 895).
p-Bromo-anilide OipHiClOj.NHC^HjBr.
[262°]. Formed by bromination of ohloro-naph-
thoqninone-anilide; or by the action ofp-brom-
aniline on di-chloro-naphthoquinone. Sol. in
NaOH to a red solution, si. sol. alcohol and acetic
acid.
»t-ir»«ro-oratZ«ieO,„H,0102.NHCjH,(NOj).
[245°]. Formed by the action of TO-nitraniline
on di-ohloro-naphthoquinone. Yellowish-red
sparingly soluble needles.
jp-J^itro-oni2iieC,„HjC10j.NH.OaH,(N02).
[282°]. Formed by the action of ^-nitraniline
-oh di-chloro-naphthoquiuone ; or by nitration
of chloro-naphthoquinone-anilide. Bed felted
needles. SI. sol. alcohol and acetic acid, sol.
alkalis to a violet solution. Nitrosaminc
0,„H^C102N(NO)0,H,(NOj). [126°].
o - To luide , C„H,0102.NHC,Hs(CH3)H.
[152°]. Bed metallic crystals. Formed by the
action of o-toluidine on di-ohloro-naphthoqui-
none. ,
2>-roZM»ieO„H.C10j.NHC,H,(CH3). [196°].
Formed by the action of j>-toluidine on di-chloro-
naphthoquinqne. Metl^c red crystals. Sol.
acetic acid, si. sol. alcohol. Dissolves in NaOH
to a violet solution.
Bromo-o-toluide
C,.H,C10,.NHC,H3(CH,)Br. [212°]. Formed by
bromuiation of chloro-naphthoquinone-o-toluide.
SI. sol. alcohol and acetic acid.
BTomo-p-toluide
C,„H,C10;.NHCsH3(CH3)Br. [185°]. Formed by
bromination of chloro-naphthoquinone-p-tdluide.
Bed needles. SI. sol. alcohol, dissolves in NaOH
to a violet solution.
Nitro-o-toluide
0,„H,C!0j.NH.CeH3(CH,)(N0j). [230°]. Formed
by nitrating the o-toluide (P.).
Nitro-p-toluide
C,„H4C10j.NHC3H3(CH3) (NO^. [236°-240°].
Formed by nitration of ohloro-naphthoquinone-,
p-toluide. Bed felted needles. SI. sol. alcohol
and acetic acid. Dissolves in NaOH to a violet
Bolution.
<CO.CO
I
CH:CC1
[172°]. Obtained by passing chlorine gas into
(;3)-naphthoquinone suspended in ten times its
weight of acetic acid^ Bed needles. Sol. hot
alcohol, acetic acid, benzene, and chloroform.
Dissolves in dilute caustic alkalis with a reddish-
brown colour forming chloro-oxy-(a)-naphthoqui-
none. With alcoholic NH, or aniline it yields
respectively the imide or anilide of chloro-oxy-
(a)-naphthoquinone (Zincke, B. 19, 2497).
/CO.CO
Dichloride CJiX | . [128°].
NCHCl.CClj
Formed by passing chlorine into a solution of
(;8)-naphthoquinone in EOAo (Zincke, B. 20,
2S0Q). 'Xhin. needles (containing 2aq). ,In the
hydrated condition it melts at 112°. Methyl-
<CQ.C(OH)
<i%5 [200°].
C(NMe).CCl
Di-cMoro-(o)-naphtlioqTiinone CioHjCljOj i.e.
,00.001
0.h/ II [189°].
\co.cci
Formation. — 1. From chloro - naphthalene
tetrachloride C,„H,C1, and boiling HNO, (Lau-
rent, A. Oh. [2] 74, 35 ; Bev. Soient. 13, 591).—
2. From di-nitro-naphthol, KClOj and HCl
(Graebe, A. 149, 3). — 3. From naphthalene Ji
HOAo and OrOjClj (Carstanjen, B. 2, 633).—
4. Together with chlorinated phthahc acids by
ozidatioh of tetra-chloro-naphthalene [140°]
(from (a)-naphthol-tri-sulphonic chloride and
PCI5) with CrOj or HNO3.
Properties. — Sublimes in yellow needles.
Insol. water, si. sol. oold alcohol and ether. By
alkalis it is converted into ohloro-oxy- (a) -naph-
thoquinone which forms yellow needles [215°].
With aniline it yields 0,„H4Cl(NHPh)0j, splen-
did violet-red crystals [208° uncor.] (Glaus a. ■
llieloke, B. 19, 1184). Oxidation gives phthalio
acid. PCI, forms penta-chloro-naphthalene.
Di-chloride CioHjCliOj. [117° uncor.].
Formed by heating di-chloro-(o)-naphthoquinone
(10 pts.) with HOI of S.G. 1-2 (48pts.) and MnOj
(10 pts.) for 10 hours at 230°. Large colourless
prisms. Sublimes unaltered. By SnOl, or other
reducing agent it is re-converted into di-chloro-
(a) -naphthoquinone (Clans, B. 19, 1142).
(■ P ')-I)i-chloro-(a)-naphthoquinone
/CO.CCl
CioHjCLjOa probably OjHjOSr || [149° un,
^CO.CH
cor.]. Formed, together with ohloro-phthalio
acid CsH3Cl(C02H)j [4:2:1], by oxidation of (e)-
di-chloro-naphthalene in acetic acid solution by
CrOj. Yellow needles. Sublimable without
decomposition. Dissolyes in aqueous KOH
with a red colour. By boiling with alkalis it is
converted into ('j8')-ehloro-oxy-naphthoqui-
none C,jH4Cl(0H)0j. (Clans a. MMler, B. 18,
3073).
Di-chloro - (a) - naphthoquinone CuKfilfif.
[153°]. Formed, together with the isomeride
[189°] by chlorinating di-nitro-najlhthol (P.).
2)-Di-cliloro-(a)-naphthoquittone CijH4Clj0j.
[174°]. Formed, together with di-ohloro-phthal-
ide, by oxidation of di-chloro-naphthalene [68°]
with CrOj and glacial acetic acid. Long yellow
needles. Subhmable. Sol. alcohol and ether,
nearly insol. water. By NaOH it is converted
into chloro - oxy - (o) - naphthoquinone. With
aniline it forms C,„HjCl(NHPh)02, garnet red
needles, [185°] (Guaresohi, B. 19, 1155).
C' OO.CO
I
ChCCl'
[184°]. Formed by the action of chlorine upon
(/3) -naphthoquinone, or better (a)-amido-(;8)-
naphthol in acetic acid. Bed plates, long flat
needles, thick rhombic or monoclinic tables.
Sol. chloroform,, si. sol. alcohol. Sublimable.
With alcoholic NHj or aniline it yields the imide
or anilide of chloro-oxy-(o)-naphthoquinone. It
dissolves in cold dilute NaOH to a colourless
solution forming an acid CjoHsCljO, which pos-
DI-CHLOKO-NAPHTHYLENE-DIAMINE.
/C(0H).00jH
aibly has the constitution O.H.< "^ .
N001.C01
(Zincke, B. 19, 2499). This acid crystallises in
slender needles (containing aq) [100°] ; it forms
a methyl-ether C,„H,0l2(0H).00oMe [138°] and
aaacetyl-in(ithyletherO,^fil2(OA.c)OO.Jile[16°2.
Iri-chloro-^a).napIithoqniiione CsHsGlsOg.
Formed by oxidation of tri-chloro-naphthalene
[90°] (from (;3)-naplitho^-(i3)-di-salphoniO' acid
and FClg) with CrO, and acetic acid. It was not
isolated, but by treatment with aniline was con-
verted into the anilide C,„H30l2(NHPh)Oa, which
formed reddish-violet plates [228°] uucor.,
Bublimable (Clans a. Schmidt, B. 19, 3177).
Xetra-chloro-(a)-naphthoc|.iiuiouei
yCO.CH
CiCl»< II [160° nncor.]. Long yellow
XiO.OH
needles. Sublimable. Prepared by oxidation of
penta-chloro-naphthaJene with fuming HNO, at
110°. PClj converts it into hepta-chloro-naph-
thalene (Clans a. Lippe, B. 16, 1018).
Feata-chloro-(a)-naphthoqmnone
yCacci
CbCI4< II [217° uncor.]. Formed together
\CO.CH
with tetra-chloro-phthalic acid, by oxidation of
hepta-chloro-naphthalene [194°] with HNO^
(1-5 S.G.) at 100°. Glistening golden plates
(from chloroform). Sublimes in long glistening
needles. By alkaUs it is converted into
salts of tetra-chloro-ozy-naphthoquinone
,C(OH)
I . With aniline it yields
CH
XO.C
C.C1<- I
X!O.C
^•<c,
.CO.C(NHC.HJ
II
0.0H
which crystallises from
alcohol -or acetic acid in glistening red plates
[240° unoor.]. By heating with PCI5 at 250° it
is converted into per-ohloro-naphthalene [203°]
(Claus a. Wenzlik, B. 19, 1166).
SI . CHLOEO - (0) - NAPHIHOQUIKOITE DI ■
. CO.CO
CHLOEIDE CjH.< | [91°]. Formed
\CCLj.CClj
by passing chlorine into a solution of (1, 2)-
amido-naphthol in HOAo (Zincke, B. 21, 495).
Yellowish crystals (from ether) ; v. sol. ether,
EOAc, and petroleum ether.
DI-CHLOEO-(a)-NAPHTHOQTJmrON? STTL-
PHONIC ACID 0,A0l20j(S0aH)[2:3:l:4:3'].
From sodium di-nitro-(a)-naphthol sulphonate
{la)^naphthol yellow), KCIO3 and HCl (Claus,
J.pr. [2] 37, 181). Light yellow plates, v. sol.
water and alcohol, insol. ether. Converted by
potash-fusion into (/8)-oxy-phthalio acid. Aniline
forms 0,JH,Ol(NPhH)O2(SO3H) [190°], a colour-
ing matter crystallising in dark-red plates.
S.alts. — NaA': yellow crystalline powder
(from water) or yellow plates (from alcohol). —
CaAV— BaAV
DI-CHIOEO-HAPHTHOSTYEIL v. Di-
CHLOBO-AUmO-NAPHTHOIO LACTAM.
TETEA-CHLOEO-(j8;3).DINAPHTHYL
CjjHioCl,. Amorphous (Smith a. Poynting, C. J.
27, 854).
Eeza-chloro- (ao) -dinaphthyl CjoHjCli.
Ajnorphous (Losseu, A. 144, 77).
CHLORO-(a).KAPHTHYI.-AMIirE C,„H,aN
.C(NH,):Ca .C(NH,):CC1
t.e.O.HZ I or C.HZ; | .
\ CH=C01 \ CH=CH
[56°]. Obtained by reduction of di-chloro-(o)-
naphthylamine [82°] with tin and HCl. Thin
white needles. Very unpleasant smell. SI. sol.
hot water. Very volatile with steam. Its salts
are decomposed by water.
Salts. — B'HClaq: silky needles. —
B'HClSnClj: thin glistening plates.— B'HjSO^aa:
slender white needles (CUve^ B. 20, 460).
Chloro-(ii).naphtliylamine C,„Hj01(NH2).
[86°]. From chloro-nitro-naphthalene by re-
duction (Atterberg, B. 10, 548).— B'HCl.
Chloro-(a)-naphthylamine OioH^C^KH,).
[94°]. Formed by reducing (7)-di-chloro-nitro-
naphthalene (Atterberg, B. 9, 1730). FcjOl,
gives a greyish-green coloration. ■ Displacement
of NHj by CI forms (Q-di-chloro-naphthalene
(Atterberg, B. 10, 648).-B'H01aq.— B'HSnCl,.
— B'H^SO,.
Chloro-(a)-napht!iylamine C,oH,Cl(NH,).
[98°]. Formed by the alow action of SnOli on
a solution of (a)-naphthylamine hydrochloride
exposed to air (Seidler, B. 11, 1201).
Acetyi derivative C,„H801(NHAc). [184°].
(o)-Chloro-(j3)-naphtliylamine CioHjCLNH,
[1:2]. [59°]. From the acetyl derivative and
HCl. Elimination of NHg gives (a)-ohloro-
naphthalene. — ^B'HCl aq.
Acetyl derivative 0,oHsCl.NHAo. [147°].
Formed by passing chlorine into a solution of
acetyl (;8)-naphthylamiue in dilute HOAo (ClSve,
B. 20, 1989).
Dl-chIoro-(a)-iiaphthylamine 0,oEgCl2(NH2).
[104°]. Formed by reducing (• /S ')-di-chloro-
nitro-naphthalene [68°]. Needles (from alcohol).
B'HCl.— B'HSnCl3.—B'2HjPtC1.2aq.—B'H2SO,.
(7i)-Di-chloro-naphthylamine C,oHjCl2(NHj).
[94° ?]. Formed by reducing (i))-di-chloro-nitro-
naphthalene {Cl6ve, Bl. [2] 29, 500).— B'HCl.
Di-chloro-(a)-nap]itliylamine C,|^,C1,N pro-
.C(NHs):CCl
bablyCjH,^^ ■ | . [82°]. Obtained by
\ C!H=0C1
saponifying its acetyl derivative, which is formed
by passing chlorine (2 mols.) into an acetic acid
solution of aeetyl-(a)-naphthylamine (1 mol.).
Crystalline solid, of disagreeable odour. V. e.
sol. alcohol. Volatile with steam. Non-basic.
By BnStOa it is oxidised- to phthalio acid. By
elimination of the NH, group by the diazo-re-
aotion, di-ohloro-naphthalene [61°] is formed.
By 'tin and HCl it is reduced to mono-chloro-(a)-
naphthylamine [56°].
Acetyl derivativeC,„nfih.'SBAo:[2Wy,
long thin white needles ; sol', acetic acid, alcohol
and chloroform; sublimable (CUve, B. 20, 448).
DI-CHL0E0-DI.(;3)-NAPHTHYL-AMINE
(C,„H.Cl)oNH.
Bemoylderivative(C,„-afil),-!!lBz. [203°
nncor.] ; small white needles ; sol. alcohol,
benzene, and chloroform. Formed by the action
of PCij on the benzoyl derivative of di-(i8)-naph-
thylamine (Claus a. Eiohter, B. 17, 1590).
DI - CHLOEO - NAPHXHYLENE - DIAMINE
C,„H,Clj(NHj)2. [205°]. Formed by reduction
of di-ohloro-di-nitro-naphthalene [253°] by tin,'
HOI, and HOAo (Alto, BL [2] 36, 435),
90
DI-CHLORO-DINAPHTHYLENE-OXIDE.
DI-CHLORO(o)-DINAPHTHYLENE.OXIDE
C2„H,„CljO. [1B1°). Prepared by the action of
PCI5 on (o)-dinaphthylene-pxide (Knecht a. Un-
zeitig, B. 13, 1725). Sublimes and crystallises
in yellow needles. V. sol. benzene and acetic
acid, si. sol. alcohol, ether, and chloi:oform.
iDi-c]iloro-(/3)-dinaphthylene-ozideC2oH„Cl2(X
[245°]. Prepared by the action of PCI5 on (3)-
dinaphthylene-ozide (K. a. U.). Yellow glisten-
ing needles (from benzene).
TSI-CHIOBO- (a) and (;3) .DI-NAFHIHTL-
ETHANE CCl3.CH(C,„H,)2. Formed together
by the action of H2SO4 on a mixture of naphthal-
ene and chloral, thus : GC1,.CH.0 + 2C„H,
= CCl,.CH(C,A)s + H,0.
Preparation. — 6 pts. of H^SO, mixed with
dnpta. of fuming H^SO, are added to a mixture
of 3 pts. of chloral, 8 pts. of naphthalene, and
6 pts. of chloroform (Grabowski, B. 11, 298).
{$)-modifi cation [156°]. Crystals. Insol.
. cold, si. sol. hot, alcohol and ether. Separated
from the (a) -modification by its sparing solu-
bility in alcohol. On distillation it loses HCl
forming dichloro-(j8)-dinaphthyl-ethylene.
Tetra-niUro-dervBatmie [258°]. Yellow pow-
der. Insol. alcohol, ether, C,H„ &o.
{a)jmodification. Kot isolated in the pure
state. V. sol. alcohol.
DI.CHLOKO-(a)-DI-NAPHTHYI-ETHTIENE
CCls:CH(C,„H,)2. [150°]. SI. sol. cold, v. sol.
hot, alcohol. Long colourless needles. Less
stable than the (j3) -modification. Prepared by
distilling crude trichloro-(a)-di-naphthyl-ethane
with 20 p.c. of lime (Orabowski, B. 11, 299).
Tetra^mtro-derivative. [214°].
I)i-chloro-(;8)-di-naphtliyl-ethylene
CClj:CH{C,„H,)s. [219°]. (above 360°). Distils
without decomposition. Short prismatic pillars.
SI. sol. alcohol. Prepared by the distillation of
tri-chloro-(i8)-di-naphthyl-ethane.
Tetra-nitro-derivaii/ue. [293°] (Grabowski,
B. 11,299).
CHLOBO - (j3) ■ ITAPHXB7L-FH0SFH0BIC
ACID C,„H,01.0P0(0H)2. [205° uncor.].
Formed as a by-product in the action of PCI,
(2 mols.) on potassium (j3)-naphthol-sulphonate
(1 mol.) at 150° (Claus a. Zimmermann, B. 14,
1483). Small plates. By boiling alkalis it is
decomposed into chloro-(;3)-uaphthol and phos-
phate.
CHLOEO-NICOTIIIIC ACID v. Chlgbo-ptki-
DINE-OABBOXTLIC ACID.
w-DI-CHLOBO-0-lTITBO-ACETOFHENONE.
0^,(NOj).CO.CHClj. , [73°]. Nitro-pJienyl di-
ehlm-o-ntethyl ketone. Formed by chlorination
of C,H4(N0j).C0.Me (Gevekoht, A. 221, 328).
Plates (from benzoline).
CHLOKO-mTBO-AUIDO-FHENOL
OaHjOlNjO, i.e. C.ELjCl(N0j)(NH2)(0H) [2:4:6:1].
[160°]. Formed by reducing chloro-di-nitro-
phenol [110°] with ammonium sulphide (Griess
a. Eolbe, A. 109, 286; Faust a- Miller, A.ns,
315 ; Z. 1871, 339 ; Armstrong, O. J. 25, 14).
Slender brass-yellow needles (containing ^ aq)
(from hot water). When dried at 100° it is scar-
let. Elimination of NH^ gives chloro-nitro-
phenol [110°].— B'HCl : yelloiyish needles.—
B',H,SO,.— NH4(0,H,CmA).-
Ba(C,H4ClN209)2 4aq : slender black needles.
Chloro-nitro-amido-phenol. Methyl ether
0^(Cl)(NOj)(OMe)(NHJ. CUaro-nitro-anisi-
dine. Acetyl derivative [185°], yellow
needles, sol. alcohol and ether, insol. cold water
(Herold, B. 15, 1686).
Chloro-di-nitro-amido-phenol. Methyl
ether G.H(Gl)(NOJj(OMe)(NH,). Acetyl de-
rivative [165°], yellow needles (H.).
Chloro - tri - nitro - amide - phenol. Me thy I
ether 0.(Cl)(N02),(0Me)(NHj). Acetyl de-
rivative [198°], orange-yellow needles (H.).
CHLOBO ■ NITBO - AMIDO - DI - PHENYL -
AUINE V. CHLOBNITBOPHISNTIi-PHEirZUeiNE-DT-
AMINE..
CHLOBO-iriTBO-AlilLINE ]
C„H3Cl(N0J(NHj) [4:3:1]. [103° nncor.].
Formation. — 1. By nitration of j7-ohloro-
aniline dissolved in 10 pts. of EjSO, ; the yield
is 50 p.c. of the ohloraniline. — 2. Together with
a much larger quantity of the (6:3:l)-iso-
meride by redaction of ohloro-di-nitro-benzene
C„HgCl(N02)2 [4:3:1] in alcoholic solution with
SnCl^ and HCl.
Properties. — Small yellow glistening needles
(from hot petroleum-ether), or long thin needles
(from boiling water). V. sol. alcohol, ether and
chloroform, m. sol. hot water, nearly insol. cold
water. Weak base. By elimination of the NH,
group it gives o-ohloro-nitro-benzene [33°]. By
replacement of the NH, group by CI, di-cbloro-
nitro-benzene [55°] is formed.
Acetyl derivative CeH3CI(N02)(NHAc)
[100°] ; small yellow needles (Claus a. Stiebel
B. 20, 1379).
Chloro - nitro - aniline GsH3Cl(N0J(NHj)
[2:4:1]. [105°]. Prepared by heating (1, 2, 4)-
di-chloro-nitro-benzene [43°] with ammonia at
210° (Beilstein a. Kurbatoff, A. 182, 98). Ap-
pears also to be formed in small quantity by
nitrating acetyl-o-chloro- aniline. Light yellow
needles. Elimination of NH^ gives m-chloro-
nitro-benzene.
Acetyl derivative CaH.Cl(NOj)(NHAc).
[139°].
Chloro - nitro - aniline C5H5C1(N0„)(NH,)
[4:2:1]. [115°]. (B. a. K.) ; [116°] (K.). From
(l,4,2)-di-chloro-nitro-benzene and alcoholic
NH3 at 165°. Formed also by nitrating acetyl
^-chloro-aniline (Korner, O. 4, 373; Beilstein a.
Kurbatoff, B. 9, 633 ; A. 182, 94). Orange-
yellow needles (from water) or spherical groups
of brick-red needles (from alcohol). Elimination
of NHj gives m-ohloro-nitro-benzene. Bedue-
tion to chloro-phenylene-diamine followed by
treatment with sodium-amalgam gives o-phenyl-
ene-diamine (Eorner).
Chloro - nitro - aniline CaH,Cl(NO,) (NH,)
[6:3:1]. [117°].
Formation. — 1. Together with a smaller
quantity of the (4:3:1) -isomeride by reduction of
ehloro-di-nitro-benzene C,H3Cl(N0j)j [4:3:1] in
alcoholic solution with SnClj (Claus a. Stiebel,
B. 20, 1379).— 2. By nitration of acetyl-o-ohloro-
aniline (B. a. K.).
Properties. — Yellow needles. Elimination of
NH2 gives j)-chloro-nitro-benzene.
Acetyl derivative CjH,Cl(NO,)(NHAo).
[154°]. '
Chloro - nitro - aniline OsH,Cl(NO,) (NH.,)
[3:6:1]. [125°]. '^ "
Formation, — 1. By heating (3,6,l)-di-ohloro-
nitro-benzene [33°] with alcoholic NH, for
10 hours at 160° (K6rner, Q. 4, 373).— 2. From
OHLOEO-NITRO-BENZENE.
81
ohioro-di-nitio-benzene [39°] and NH, (Iiauben-
heimer, B. 9, 1826). — 3. By nitrating acetyl
m-chloro-aniline (B. a. K.).
Properties. — Thin yellow lamines (from alco-
hol). Elimination o{ NH, gives p-ohloro-nitro-
benzene. Seduction by tin and EOl gives-
chloro-phenylene-diamine whence sodium-amal-
gam produces o-phenylene-diamine (Korner).
Acetyl derivative C.H,Cl(N02}(XHAo).
[115°].
Chloro - nitro - aniline 0„Hs01(N0s){NHj)
[3:4:1]. [157°]. Formed, together with the
preceding, by nitrating acetyl m-chloro-aniline
(B. a. E.). Yellow laminis (from benzene).
Eliminatidn ot NH, gives o-ohloro-nitro-benz-
ene [32-5°].
Acetyl derivative [142°].
Chloro - di-nitro - aniline C„H2Ca{N02)2(NHj)
[4:2:6:1]. [145°]. From di- chloro -di- nitro-
benzene [104°] and alcoholic NH,. Formed
also by chlorinating di-nitro-aniline [138°] and
by treating the methyl ether of chloro-di-nitro-
phenol [65°] with NH, (Korner). Orange needles.
AlcohoUo KOH converts it into chloro-di-nitro-
phenol.
Di-chloro,nitro-aniline CaH2CLj(N02) (NH^)
[3:6:2:1]. [68°]. From its acetyl derivative,
which is formed, together with the (3,6,4,l)-iso-
meride [153°], by the nitration of CjH30l2(NHAe)
[3:6:1] (Beilstein a. Kurbatow,, A, 192, 232).
Also from (3,6,2,l)-di-chloro-di-nitro-benzene
and alcoholic NH, (Korner). Yellow needles.
Displacement of NH^ by 01 gives (3,6,l,2)-tri-
chloro-nitro-benzene [89°].
Acetyl derivative 0,Hj01j{N02)(NHAo).
[205°].
Di-chloro-nitro-aniline C,B^Ol2(S0i)(TSiB..,)
[3:5:6:1]. [79°]. Prepared together with the
(3,5,4,l)-isomeride [171°] by nitration of acetyl-
(l,3,5)-di-chloro-aniiine. Yellow needles. Con-
verted by elimination of NH^ into di-ohloro-
nitro-benzene [33°].
Acetyl derivative [139°]. Sol. OS,
(Beilstein a. Kurbatow, B. 11, 1979).
Di-chloro-nitro-aniline OjH2Cl2(NOj) (NH^)
[4:3:2:1]. [96°]. Prepared together with the
(4,3,6,l)-i«omeride [175°] by nitration of acetyl-
(4(3,l)-di-chloro-aniline. Yellow needles.
Acetyl derivative [153°] (Beilstein a.
Knrbatow, B. 11, 1978).
Di-chloro-o-nitro-aniline CeH2Cl2(N02) (NH^)
[2:4:6:1]. [99°]. Formed by passing chlorine
into a solution of o-nitraniline in cone. HCl
(Langer, A. 215, 111). Formed also by nitration
of a«etyl-(4,2,l)-di-chloi:o-aniline, or by ohlorina-
tion of acetyl-(4,2,l)-chloro-nitro-aniline, and
decomposition of the resulting acetyl derivative
by HCl (Witt, B. 7, 1603; 8, 820). Slender
orange needles (from benzoline). V. sol. alcohol,
ether, or benzoline. Elimination of NHj gives
di-chloro-nitro-benzene [65°] ,
Acetyl derivative C.HjCL,(N0,)(NHAc).
ri88°i
Di-cMoro-nitro-anillne CjH2CLj(N02) (NHj)
[3:6:4:1]. [153°]. Prepared, together with the
(3,6,2,l)-isomeride [68°], by nitration of aoetyl-
(,3,6,l)-di-ohloro-aniline. Yellow needles.
Acetyl derivative [146°] (Beilstein a.
Kurbatow, B. 11, 1978 ; A. 196, 235).
Di-chloro-nitro-aniline 04H201,(N02)(NHj)
[3:2:6:1]. [163°]. Formed by heatingC,HjClj(NOa)
[^6°] with alcoholic NH, at 210° (Beilstein a.
Kurbatow, A. 192, 235). By elimination of KU,
it gives di-ohloro-nitro-benzene [43°].
Di-ohloro-nitro-anilino C„H.,Clj(N0j) (NH,,)
[3:5:4:1]. [171°]. Large yellow "needles. Pre-
pared, together with the ^3,5,6,1) -isomeride [79°],
by nitration of acetyl-(S,3,l)-di-ohlor6-aniline.
Elimination of NH, gives di-chloro-nitro-benzene
[71°].
Acetyl derivative. [222°]. Insol.inCS,
(Beilstein a. Kurbatow, A. 196, 227; B. 11,
1979).
Si-oUoro-nitro-anillne C^jCkf^O^) (^^z)
[3:4:6:1]. [175°]. Prepared by the action of
alcoholic NH, on trichloronitrobenzene [5S°] or,
together with the (4,3,2,l)-isomeride [96°], by
the nitration of acetyl-(4,3,l)-di-chloro-aniline. .
Yellow needles. Displacement of NH, by 01
gives tri-chloro-nitro-benzene*[58°].
Acetyl derivative [124°]. Less sol. .
alcohol than the isomeride (1;4,5;6) (Beilstein a:
Kurbatow, A. 196, 225; B. 11, 1978).
Di-chloro-nitro-aniline CeHjCl2(N0.J (NHJ
[2:6:4:1]. [188°]. Formed by ohlorination of
^-nitro-aniline (Korner, 0. 4, 276 ; Witt, JB. 8,
143). Lemon-yellow needles. Elimination of
NH, gives di-chloro-nitro-benzene [65°].
Acetyl derivative CaH2CLj(N0J(NHAc).
[210°].
Di-cMoro-di-nitro-aniline C,HCl,(N0s)2(NH,)
[3:4:2:6:1]. [128°]. Formed by nitrating acetyl-
(4,3,l)-di-chloro-aniline, and eliminating Ac by
HjSO,, (Beilstein a. Kurbatow, A. 196, 235 ;
B. 11, 1978). Large red needles.
Acetyl derivative C,HCl,(N0J,(;NHAc)
[246°].
Tri-chloTO-m-nitro-aniline
CeH01,(N0,)(NH,) [5:4:2:3:1]. [98°]. From
?re-nitraniline (1 pt.), cone. HCl (25 pts.) and
water (20 pts.), by passage of a mixture of air
and .chlorine (Langer, A. 215, 110). Long,
broad yellow needles (from light petroleum).
Tri-chloro-nitro-aniline 05HCls(N02)(NHi)
[2:4:5:6:1]. [124°]. Prepared by nitration of
acetyl-tri-chloro-aniline [185°], and elimination
of Ac by HCl. Yellow needles.
Acetyl derivative CeHCl,(NO,)(NHAc).
[193°] (Beilstein a. Kurbatow, A. 196, 235;
B. 11, 1980).
CHLORO -NITEO- ANISIDINE v. Methyl
ether of CHLORO-NITEO-AMIDO-rHENOIi.
CHLOBO-NXTBO-ANISOL v. Methyl ether of
Chloro-nitbo-phenol.
0-CHLOEO-NITEO-BENZENE C.H,C1(N0,)
[1:2]. Mol. w.l67i. [32-5°]. (243°). a.Gr.^
1-368.
JV^naiMMi.— l.Togetherwiththej)-isomende,
by nitrating chloro-benzene (Jungfleisoh, A. Ch.
[4] 15, 186; Laubenheimer, B. 7, 1765 ; 8,1621;
SoltolofE, Z. 1866, 621 ; Lesimple, Z. [2] 4, 225).
2. From chloro-nitro-aniline [157°] by elimina-
tion of NHj through the diazo- reaction (Beilstein
a. Kurbatoff, B. 9, 633 ; A. 182, 107).— 3. In
small quantity by the action of PCI5 on o-nitro-
phenol (Engelhardt a. LatschinofE, Z. [2] 6, 225).
Properties. — Needles ; converted by aqueous
NaOH at 130° into o-nitro-phenol. Not attacked
by alcoholic KCy.
M-Chloro-nitro-benMne C,H,C1(N0J [1:3].
[45°]. (236° cor.).
FormaUon. — 1. By ohlorination of nitro-
m
CHLOEO-NITEO-BENZENE.
benzene in presence of iodine (Laubenheimer,
B. 7, 1765) or SbCl, (Beilstein a. Kurbatoff, A.
182, 102). — 2. From m-nitro-aniline by displace-
ment of NH, by CI through the diazo- reaction
(Griess, Pr. 13, 381).
Pr^aration. — 1. Fromnitro-benzene (500 g.)
and FejGlg (10 g.) by ohlorination (Yarnholt,
J.pr. [2] 36, 25).— 2. By running a solution of
NaNO, into a hot solution of m-nitro-aniline
and CUjOI, in dilute fiCl (Sandmeyei;, B. 17,
Properlies. — Trimetrio crystals ; a:b:c =
•661:1: -498. Sublimes in flat needles. V. sol.
ether, benzene, chloroform, CS,, HOAc, and hot
alcohol.
Reactioni. — 1. IfitraUon forms ObHjC^NOj)^
[39»].— 2. Alcohoho KOH gives (C^H^CliiNjO.
[97°]. — 3. Alcoholic KCy gives o-ohloro-benzo-
nitrilB (Bichter, B. 6, 1418).
j)-Chloro •nitre •benzene C,H«C1(K02) [1:4].
[83°]. (242°). S.a.a»l-38.
FormaMon. — 1. Together with the o-iso-
meride, by nitration of chloro-benzene (Biche,
A. 121, 367 ; Jungfleisch, A. Ch. [4] 15, 186).—
2. From ^-nitro-aniline by displacement of NHj
by CI (Griess, Pr. 13, 381).— 3. From ^-nitro-
phenol and FGl, (Engelhardt a. Latschinoif , Z.
1870, 230). — 4. From (3,6,1) -ohloro-nitro-aniline
by eliasdnation of KH, (Beilstein a. Kurbatoff,
A. 182, 105).
Prcyperties. — Trimetrio plates.
Reactions, — 1. Heating with aquebus NajCO,
and KaOH at 130° slowly forms ^-nitro-phenol.
2. Alcoholic KOH gives (CjHjG^jNjO and, at
180°, CsH,Cl.Nj,.CsH,Cl. If the alcohol be dilute
OeH^CLOEt is formed.— 3. Alcoholic KCy gives
m-cbloro-benzonitrile.
Chloro-di-nitro-benzeneC,H3Cl(N02)j [1:3:4?].
Mol. w. 202 1. According to Laubenheimer {B.
9, 760, 768) the chloro-di-nitro-benzene formed
by nitrating m-chloro-benzene, exists in four
modifications, viz. :
(a). [36°]. Thick monoclinic prisms: a:b:c
- 1-887:1: -981 ; /3 = 114° 14'. Gradually passes
into the (7) modification.
(P). [37°]. Monoclinic prisms, a:b:c
= ■625:1: -560; /S = 91° 27'. Gradually passes
into the (7) modification.
(7). [39°]. Thin trimetrio needles.
(S). Liquid.
BeacUcms.^-1, Aqueous NaOH forms chloro-
'nitro - phenol [39°]. — 2. Aniline forms
C,HaCl(N02)(NPhH).— 3. Tin and HCl reduce
it to ohloro-phenylene-diamine [72°].— 4. Boiled
with a solution of sodium sulphite it gives
chloro-nitro-benzene-Bulphonic acid and KaHO,
(Laubenheimer, B. 15, 597). — 5. Phenyl-hydra-
zine forms C,H»Cl(N0,).NjH2Ph [140°] (Willge-
rodt, J.iir. [2]37, 355).
Chloro-di-nitro-benzene C,H3Cl(N0j)j [1:2:4].
[68-5°]. (315°). S.G. i2 1-697.
Formation, — 1. By nitration of o- or p-
ohloro-nitro-benzene (Jnhgfleisch, 4. Ch. [4] 15,
186); — 2. From di-nitro-phenol and FClg (Clemm,
Z. 1870, 274).
Properties, — ^Trimetrio crystals; v. si. sol.
cold alcohol, T. sol. boiling alcohol and ether.
Jungfleisch describes a physical isomeride [42°].
BaacUans, — 1. Tin and HCl form chloro-
nitro-aniline [89°]. — 2. Strong aqueous KOH
forms di-nitro-phenol.— 3. Alcoholic KH, at
110° forms di-nitro -aniline [175°]. — i. Alcoholic
NMe, forms C„H3(N02),(NMe2) [78°].-5. Di-
mefhyl-amiline gives C8H3(N0j)2(NPhMe) [167"*]
(Leymann, B. 15, 1233).— 6. By the action of
KOH dissolved in an alcohol, it gives the ether
of the di-nitro-phenol corresponding to the alcohol
used (Willgerodt, B, 12, 762).— 7. Phenyl-hy-
drazine in the cold forms C^a^^O^i^^^h.
[120°] crystallising in red plates and converted
by boiling HOAc into C„H3(N0)2.NjPh [247°]
(Willgerodt, J.pr, [2] 37, 347, 449).
Chloro - tri - nitro - benzene G^Cl^^O^,,
[1:2:4:6]. Picryl chloride. Mol. w. 247^. [83°].
From tri-nitro-phenol (picric acid) and PCI,
(Pisani, A. 92, 326 ; Clemm, J, pr. [2] 1, 145 ;
Z. [2] 6, 444). Amber-yellow monoclinic tables
(from ether) or nearly colourless needles (from 1
alcohol). V, sol. boiling alcohol, si. sol. ether:
Combines with benzene and other aromatic hy-
drocarbons (Liebermann a. Fahn, B. 8, 378).
Reactions. — 1. Water or aqueous Na^CO,
converts it into tri-nitro-phenol.^ — 2. Ammorda
forms tri-nitro-aniline. — 3. Alcoholic KOH forms
C5H2(N02)30Et. — 4. Ethyl -hydrazine forms
i 0„H2(N0,)aNjH2Et [200°] (Fischer, A. 199,
299).'— 6. Phenyl-hydrazine forms CuH-NjO,
[225°] (238°) (Willgerodt, J. pr. [2] 37, 357).—
6. Alcoholic Si - methyl - amine gives rise to
C3Hj(N0j)3NMe2 [114°] (Van Eomburgh, R. T, C.
2, 105).
Di-chloro-nitro-benzene 0bH3C12(N0j) [1:3:4],
[33°]. Formed by nitrating TO-di-chloro-benz-
eue (Korner, G. 4, 305 ; J. 1875, 323 ; Beilstein a.
Kurbatoff, A. 182, 97). Long needles (from
alcohol). Converted by alcoholic NH, at 210°
into CaH,Cl(NHJ(NOJ [1:3:4] [125°]. Aqueous
Ka^CO, has no action even at 290°. Alcoholic
NaOH readily forms C3H3Cl(OEt)(NOJ.
Di-chloro-nitro-benzene C„H,Cl2(N0j) [1:2:4].
[43?]. From Ci,H2Clj(N02)(NHj) [1:2:4:3] and
[0:2:4:3] by displacement of NH^ by H (Beilstein
a. Kurbatoff, A. 192, 235). Formed also by
nitration of o-di-chloro-benzene (B. a. K., A.
176, 41). Long needles (from alcohol). Con-
verted by alcoholic ammonia at 210° into
C„H3C1(NH2)(N02) [105°].
Di-chloro-nitro-benzene C.H.01,(N0J [1:4:6].
[55°]. (266°). S.G. 22 1.669.
Formation. — 1. By passing chlorine into
cold nitro-benzene (75 g.) containing FojCl,
(11-5 g.) (B. a. K.; Page, 4. 225, 208).— 2. By
nitration of p-di-chloro-benzene (Jungfleisch). —
3. From 0,H3Cl(N02)(NHj) [4:3:1] by the action
of CU2CI2 upon the diazo- compound (Claus a.
Stiebel, B. 20, 1381).
Prqpsr&s.— Triolinic crystals (from CSj).
Volatile with steam. Alcoholic KOH converts
it. into C3H3(0H)C1(N02) [1:4:6] [86°], together
with (C„H3Clj)jN,0 and di-chloro-aniline [50°]
(Laubenheimer, B. 7, 1600). By alcoholic NH,
at 200° it ia converted into chloro-nitro-aniline
[115°].
Di-chloro-nitro-benzene C3H3Cl2(N0j) [1:3:5].
[65°]. From the di - chloro - nitro - anUinea
C,H2(NHj)Cl,(N0j) [1:2:4:6] and [1:2:6:4] by
eliminating NK, (Korner, G. 4, 376 ; Witt, B. 7,
1604; B. 8, 144). Long thin laminse (from al-
cohol). Volatile with steam. Alcoholic NH, does
not act upon it.
Di - chloro - dl - nitro-benzene C„Hj0l2(NOj),,
[103°]. Formed by nitrating m-di- chloro.
OHLORO-NITRO-BENZOIC ACID.
93
benzene (Korner, G. 4, 305 ; J. 1875, 323). Yel-
lowish prisms. Converted by aqueous KOH into
a chloro-di-nitro-phenol.
Di - chloro - di - nitro - benzene Gg'EL^Clii'S'iO,)^
[1:4:2:6]. [87°] (J.); [104°] (Bngelhardt a.
Latsohinofi). (312^). S.G. i£ 1-710. Formed, to-
gether with the following, by nitrating p-di-
chloro-benzene (Jungfleisch). Small monoclinio
plates. Boiling aqueous NSjCO, converts it into
di-ohloro-phenol [80°].
Di - chloro - di - nitro - benzene CuHjCljfNO,) j
[1:4:2:3 or 5] [107°] (J.); [101°] (B.a.L.). (318°).
S.G. — 1*695. Formed as above. Monoolinic
needles. Boiling aqueous NajCOg converts it
into ohloro-di-nitro-phenol [70°]. Alcoholic
NH, at 160° forms 0,HsClj(NHj)(NO,) [66°]
(Korner, G. 4, 860).
Iri- chloro -nitro •benzene C^Clg(N02)
[1:2:4:5]. [57°]. (288°). 8.0.221-790. Formed
by nitrating 0,HsCls [1:2:4] (Lesimple, Bl. [2]
6, 161; A. 137, 123). Sulphur-yellow mono-
clinic prisms {tiom OS2). Converted by NH,
into C„H,(NHj)CL,(NOj) [1:3:4:6].
Tri-chloro-nitro-benzene
OJEi:,Cl,(NOj) [1:2:8:4]. [56°]. From c-tri-
chloro-benzene and fuming HNO3 (Beilstein a.
Eurbatow, A. 192, 235). Colourless silky needles
(from alcohol). V. sol. ether and CSj, m. sol.
dilute (50 per cent.) acetic acid, si. sol. alcohol.
May be reduced to tri-chloro-aniline [68°].
Alcoholic NH,forms C5H„CLj(NHj)(N0j) [1:2:3:4]
[168°].
Tri-ehloro-nitro-benzene
CeHjCl3(N0,) [1:3:5:2]. [68°]. From s-tri-chloro-
benzene and fuming HNO, (Beilstein a. Eur-
batoff, A. 192, 233). Long needles (from alco-
hol). V. sol. CSj and light petroleum. Am-
monia at 230° forms C.Hj(NHJ,Cl(NOs) [1:3:5:2].
Tri-chloro-nitro-benzene
CeH,Cl,(N02) [1:3:8:2]. [89°]. Formed from
C.Hj01j(NH,)(N02) [3:6:1:2] by diazo-reaction
(B. a. E.). Colourless needles (from light petro-
leum). V. sol. alcohol, less sol. light petroleum.
Tri-chloro-di-nitro-benzene C8HClj(N02)j.
[103-5°]. (335°). S.G. 2£ 1-85. Formed by
nitration of tt-tri-ohloro-benzene (Jungfleisch).
Light yellow six-sided prisms. Insol. cold alco-
hol, sol. hot alcohol and ether.
Tri - chloro - di - nitro - benzene CaHCl,(N02),j.
[1:3:5:2:4]. [130°]. Formed by nitrating s-tri-
chloro-benzene (Jackson a. Wing, .4m. 9, 353).
Thick white prisms (from alcohol). Sol. cold
alcohol and ether; T. sol. benzene, CS„ and
chloroform.
Tri -chloro -tri -nitro -benzene C5Cl3(N02),
[1:3:5:2:4:6]. [187°]. Foi?ned by nitrating the
preceding (Jackson a. Wing, Am. 9, 354).
Thick white needles (from alcohol). V. si. sol.
water, soL alcohol, ▼. sol. ether, benzene, and
CSj.
Tetra-chloro-nitro-benzene
CeH(NOj)Gl, [1:2:3:4:6]. [22°]. From M-tetra-
chloro-benzone and fuming HNO, (Beilstein a.
EurbatofE, A. 192, 238). Colourless needles.
v. sol. benzene, CSj, and hot alcohoL
Tetra-chloro-nitro-benzene
CsHCl,(NOj) [1:2:3:4:5]. [64-6°]. From c-tetra-
ohloro-benzene and fuming HNO, (Beilstein a.
Eurbatoff, A. 198, 239). Small needles, sL eol.
ftloohol.
Tetra-chloro-nitro-benzene
C.H(N0,)C1, [1:2:3:6:6]; [99°]. (304"). S.G. »-i
1-744. From s-CjHjCl^ and fuming HNO,. Some
ohloranil is also formed, but Ught petroleum
dissolves the CgH(N0j)01, only (Beilstein a.
Eurbatow, A. 192, 236; ef. Jungfleisch, loc. cU.).
Formed also by passing chlorine at 100° into
nitro-benzene containing FcjCl, (Page, A. 225,
208). Needles (from alcohol).
Fenta - chloro - nitro - benzene C|jCl5(N0j).
[146°]. (328°). S.G. 2= 1-718. Formed by heat
ing penta-ohloro-benzene with fuming HNO,
(Jungfleisch). Slender needles (from alcohol)
or monoclinio tables (from CSj). V. sol. boiling
alcohol, CSj, and chloroform.
CHLOBO - NITBO- BENZENE - SULFHONIC
ACID OeH3(Cn(NOJSO,H [1:4:3]. Formed by
boiling. (l:3:4)-chloro-di-nitro-benzene with a
solution of Eodio sulphite. — NaA'2aq: glistening
prisms or needles, sol. water a!nd alcohol.
Amida [159°]. Plates or needles. Sol.
alcohol, si. sol. water (Laubenheimer,J3. 15, 597).
m-Chlor-nitro-benzene snlphonio acid
C,H,(01)(N0j)(S0,H) [l:3:a!]. Prepared by sul-
phonation of m-chloro-nitro-benzene. On re-
duction it gives a chloro-amido-phenyl-mer.
captan which does not form anhydro- compounds.
Salts. — A'jBa" : white sparingly soluble
needles. — A'^Pb" : soluble needles. — A'K: white
soluble needles (AUert, B. 14, 1434).
(a)-Chloro-nitro-beiizene-sulphonlc acid
C,H3(01)(NOJS03H [1:3:?]. Formed together
with an isomeric (i3]-acid by sulphonation of
m-chloro-nitro-benzene.
Salts. — ^A'E : needles or plates, sol. alcohol.
A'Na 2|aq : yellow needles. — ^A'^Ba 2aq : small
brown needles or plates, v. pol. alcohol. —
A'^Srfaq: thick brown plates, sol, alcohol
(Post a. Meyer, B. 14, 1606).
(;3)-Chloro-nitro-benzene-Bnlphonic acid
OsH3(Cl)(NO,)S03H [1:3:?]. Formed together
with the preceding by sulphonation of m-chloro-
nitro-benzene.
Salts. — A'K|aq: light yellow prismS. —
A'jBa^aq : small yellow needles, insol. alcohol.— r
A'jSr: yellow crystalline powder (Post a. Meyer,
B. 14, 1606).
m-Chloro-nitro-benzene di-sulphonic acid
C3H2{Cl)(N02)(S03H)j [1:3:?:?]. Prepared by
siilphonating m-chloro-nitro-benzene with boil-
ing HjS0i.—A"K2 : pearly scales (Allert, iJ. 14,
1436).
CHIOBO-NITBO-BENZOIC ACID
C„H3Cl(N0j)(C0jH) [2:4:1]. [137°]. Formed by
oxidising chloro-nitiro-toluene [65°] by alkaline
KMnO, (Waohendorff, A. 185, 275 ; Lellmann,
B. 17, 634).
Chloro-nitro-benzoio acid
C3H,C1(N0J(00,H) [3:2:1]. [137°]. Formed by
the action of HjSO, and HNO, on the di-ohloro-
benzoio acid [156*] obtained by direct chloriha-
tion of benzoic acid (Clans a. Biicher, B. 20,
1624). Either this or the following acid ought
to be identical with the isomerido [235°].
Chloro-nitro-benzoio acid
0,H,01(N02)(C02H) [3:4:1]. [136°]. Obtained
by the action of HjSO, and HNO3 on the di.
chloro-benzoio acid [201°] formed by ohlorina-
tion of benzoic acid (G. a.B.).— BaA',4aq (B. a. E.).
(j3)-Cbloro-nitro-benzoic acid
0A01(NOJ(C0jH) [3t6:l]. [138°]. One of the
94
OHLOKO-NITRO-BENZOIC ACID.
products of the nitration of m-chloro-benzoio
acid(Ulrich,il.222, 97).
Salts. -BaA'j.— CaA'aafj.— PbA V—
KA' 2iaq.
Ethyl ether 'Etk'. [282°] (Ounzoa.Hiibner,
A. 135, 113).
Anilide C,H.a(NOj)(CONPhH) : [164°];
needles.
Chloro-ziitro-benzoic aci^
C,HaCl(N02)C02H [4:2:1]. [139°]. Prom
CaHjClfNOJMe [4:2:1] by oxidation with
HNO, (S.G. 1-1) (Varnholt, J.pr. [2] 36, 30).
Formed also by saponifying its nitrile with dilute
H2SO4. Long needles ; si. sol. cold water and
OSg, m. sol. chloroform.
Nitrile C,H,Cl(NOj)CN. [98°]. From the
corresponding ohloro-nitro-aniline by Sand-
hieyer's reaction (Olaus, J. pr. [2] 37, 197).
Keedles, v. sol. ether and alcohol, m. sol. cold
water.
Chloro-nitro-benzoic acid
C5H3Cl(N02)COjH [1:3:5]. [147°]. From
0jH,(NHj)(N0j)002H, cone. HCl, and nitrous
acid gas (Hiibner, A. 222, 89). Small needles.
V. sol. alcohol, ether and glacial acetic acid.
Salts.— BaA', 4aq.— PbA',.
Chloro-nitro-beilzoic acid OjHjC^NOzJCOjH
[2:5:1]. [164°]. S. -361 at 15°. Formed by
nitration of o-chloro-benzoio acid (Wilkens a.
Back, A. 222, 195; ef. EokuU, A. 117, 153).
Formed also by the action of FOl, on nitro-o-ozy-
benzoic acid (Hiibner, Z. [2] 2, 614). Long thin
monoclinio needles (from dilute HCl). V. sol.
hot water, si. sol. cold water, v. e. sol. alcohol,
ether and benzene.
Salts. — NH,A'. — NaA'. — BaA'^Saq. —
SrA'j4iaq.— CaA',2aq.— ZnA'j5iaq.— CdA'jSaq.
— PbA'..
Ethyl ether EtA'. [29°].
Nitrile C.H,C1(N02)CN. [106°]. Formed
by nitrating the nitrile of o-ohloro-benzoic acid
(Henry, B. 2, 493).
Chloro-nitro-benzoio acid C,H,Cl(N02)C0oH
[4:3:1]. [180°]. Formed by nitration of ^J-chloro-
benzoic acid (Beveill, A. 222, 182). Formed »lso
by oxidising the corresponding ohloro-nitro-
toluene (Hubner, Z. [2] 2, 614).
Salts.— BaA'j4aq.^^CaA'j5Jaq. — MgA'2 5aq.
Ethyl ether EtA'. [59°].
Anilide C,H,Cl(NOj)CO.NPhH. [131°].
Nitrile CjH,Cl(NO,)CN. [101°]. From
the corresponding chloro-nitro-aniline by Sand-
meyer's reaction with cuprous cyanide (Claus,
J.pr. [2] 37, 197). Keedles, si. sol. cold water.
Chloro-nitro-benzoic acid C,Hs01(NOj)002H
[8:4:1]. [186°]. From the nitrile by saponifica-
tion with dilute H^SO, (Claus, J.pr. [2] 37, 200).
White needles. V. sol. hot water, alcohol, ether,
chloroform, si. sol. cold water, OS,. — Salts. —
BaA'2 2aq. — CaA'j2aq. — AgA': needles (from
water).
J^i^riZo C.H,Cl(NOj)CN. [87°]. From the
corresponding chloro-nitro-aniline by displace-
ment of NHj by Cy. Colourless needles, d. sol.
cold, v. aol. hot, water.
(a)-Cliloro-nitro-benzoic acid
C,H3Cl(N02)(C0jH) [3:2:1]. [235°]. From m-
chloro-benzoic acid and fuming HNO,. Separated
by water from the more soluble (/3)-isomeride
il37°] (Ulrich, A. 222, 95). Long thin needles.
or six-sided tables. V. si. sol. water, t. boI.
ether.
Salt s. -BaA'j 4aq.— CaA', 3aq.
Anilide C,H3Cl(N0j)(C0"NPhH). [186°].
Chloro-di-nitro-benzoic acid
C<,H,Cl(N02)jC0jH [2:(3or)5:3?:l]. [238°].- By
nitration of o-ohloro-benzoic acid (Wilkens a.
Back, A. 222, 201). Small colourless needles
(from petroleum). V. sol. water, alcohol, ether,
or petroleum, si. sol. benzene.
Bi-chloro-nitro-benzoic acid
C.H,Cl2(N02)(C02H) [4:3:a!:l]. [160°]. Obtained
by nitration of (4,3,l)-di-chloio-benzoio acid
[201'], which is formed by direct chlorination of
benzoic acid (Claus a. Biicher, B. 20, 1621).
Small needles. , Sol. water.
Si-chloro-nitro-benzoic acid
C„H.,Clj(NOJ(COjH) [3:2:a!:l]. [215^. Prepared
by nitrating (3,2,l)-di-chloro-benzoio acid [156°],
'which is got by chlorinating benzoic acid (Claus
a. Bucher, B. 20, 1621). SI. sol. boiling water.—
BaA'2 4aq : lens-shaped aggregates of small
needles.
Tri-chloro-nitro-benzoic acid
C„HCl3(NO,)(C02H) [2:4:6:3:1], [220°]. From
CsHCljiCOaH) [2:4:6:1] by nitration (Beilstein a.
Knhlberg, A. 152, 239). Small needles (from
water). V. si. sol. boiling waier. — CaA', IJaq. —
BaA'2 2aq : crystalline powder.
Xetra-chloro-nitro-benzoic acid
C„Cl,(NO.JCOjH [5:4:3:2:6:1]. Formed by nitra-
tion of tetra-chloro-benzoio acid [5:4:3:2:1], by a
mixture of fuming HNO3 and cone. K^SO,.
Silvery plates. Sol. water. By tin and HCl it
is reduced to tetra-ohloro-amido-beuzoio acid..
Salts. — A',Ba2^aq: v. sol. water, small
colourless needles. — A'.^Ca: easily soluble glisten-
ing plates (Tust, B. 20, 2441).
CHLORO-NITEO-BEMZOIC ALDEHYDE
C„H3C1(N02)CH0 [3:4:1]. [62°]. From [3,4,1]-
chloro-nitro-toluene by chlorinating and treating
the resulting C,H3Cl(N0j).CHjCl with lead or
copper nitrate solution (Landsberg, D. P, J. 262,
139). White needles (from water).
Di-chlcro-o-nitro-benzoic aldehyde
C„H.,Clj(NO.JCHO. [138°]. Obtained by nitra-
tion of di-chloi'o-benzoic aldehyde with a mixture
of HNO, and H.,SO^ (Gnehm, B. 17, 753). Pearly
plates or needles. By treatment with acetonq
and NaOH it yields tetra-chloro-indigo.i
CHLORO-N ITKO-CAMPHOB v. Camphok,
o-CHLOEO-^j-NITEO-CINNAMIC ACID
0„H,(NOj).CH:CCl.COjH. [224°]. From a-ohloro-
p-nitro-/3-oxy-i8-phenyl-propionio acid and HCl
(S.G. 1-1) at 180° (Lipp, B. 19, 2646). Prisms
(from alcohol).
CHLORO-DI-WITKO-CYMENE
C,HC1(N02)5(CH,)(C,H,) [2:?:?:1:4]. [109°]. Mo-
noclinio prisms. Prepared by nitration of chloro-
oymene [214°] (Geriohten, B. 11, 1091).
Chloro-di-nitro-cymene
C.HC1(N02),(CH,)(C,H,) [3:?:?:1:4]. [lOl"].
From di-nitro-thymol and PCI, (Ladenburg a.
Engelbrecht, B. 10, 1220). Light yellow prisms.
u-Di-chloro-nitro-cymene
C,H,(CH0L,)(N0J(C,H,) [1:8:4]. From nitro-
cuminio aldehyde O.H,(CHO)(NOJ(C,H,) and
PCls (Widmann, B. 15, 167). Oil.
CHL0R0-DI-NITE0-ETHANEC2H,Cl(NO,)j?
A liquid formed when ethylidene chloride is
CHLORO-NITRO-DI-METHYL-ANILINE.
9fi
heated in a sealed tube with HNO3 at 100°
(Lauterbach, B. 12, 677).
Tetra - chloro - di - nitro - ethane CjCl^NjO,.
Formed by direct union of tetra-ohloro-ethylene
with nitric peroxide (Hoch a. Kolbe, J. pr. [2] 4,
60). Feathery needles (from alcohol) ; insol.
water. Volatile with steam. Decomposes at
140°. Alcoholic KOH forms long prisma of
C,Cl3(N0,),(0K).
CHLOBO-iriTIlO-ETHTt.-ANILINE
C,H,01NA»-e.0JHjCl(N02).NHBt [5:2:1]. [84*].
From chloro-di-nitro-benzene and an alcoholic
solution of ethyl-aniline (Laubenheimer, B. 11,
1156). Golden needles ; si. sol. cold alcohol.
SI-OHLOBO-SrilBO-EIIIYL-BENZENE
C,H,.CHCl.CHCl.NOj. [30°]? Formed by the
union of CI with CsH5CH:CH.N02 (Priebs, A.
22.5,344). Usually an oil. Volatile with steam.
Aqueous NaOH forms C,H5.C01:CH.NOj.
Di-chloro-nitro-ethyl-benzeneCjHjCl^lNOJEt
[l:4:x:2]. [175°]. Formed by boiling di-chloro-
^thyl-benzene with HNO, and HjSO, for 50
hours (Istrati, Bl. [2] 48, 41). Crystalline plates,
sol. hot water. Gives a yellowish-white pp.
with FejOlj.
Oi-chloro-tri-nitro-ethyl-henzene
CsClj(NOj)sEt. [195°]. Formed at the same
time as the preceding (Istrati). Groups ot
small crystals; insol. water, t. boI. alcohol.
FcjOl, pps. its alcoholic solution.
letra-chloro-nitro-ethyl-benzene
CbCI,(N02)(CjHJ [1:3:4:5:2:6]. [30^. Formed
by passing C^H, into a mixture of AI2GI, and
C;aCl,(NOj) (Istrati, 4. Ch. [6] 6,498). Gelatin-
ous solid, V. sol. ether and CHCl,. Decomposes
on distillation, giving tetra-chloro-di-ethyl-
benzene.
TEI-CHL0RO-IIITE0-ETHYI.ENECjCl,NOj(?)
Formed by adding C2GI4 to a cooled mixture ot
nSO^ and fuming HNO, (5och, J.pr. [2] 6, 95).
Pungent yellow oil ; decomposed by water and
alkalis. Br at 150° converts it into C20l3Br2(NOj)
[c. 120°]. Liquid nitric peroxide at 115° forms
feathery crystals of an unstable compound
C,Cl,(NOj),.
CHLOEO-NITEO-MESITTLENE C,H,oClNOj
i.e. C.H01(N02)Me, [2:4:1:3:5]. [57°]. Formed
by nitrating ohloro-mesitylene (Fittig a. Hooge-
werff, A. 150, 324 ; Z. [2] 6, 168). Pale yeUow
spicular crystals, v. sol. alcohol.
Cbloro-di-nitro-mesitylene CgCl(N02)2Me,.
[179°]. The chief product of the action of
fuming HNOj on ohloro-mesitylene (P. a. H.).
Long colourless needles (from alcohol). SI. sol.
cold alcohol. May be sublimed.
CHLOBO-NITEO-HEIHANE OH2C1(N02).
(123°). S.G. ^ 1'466. Formed by the action
of chlorine - water on sodium nitro - methane :
CHjNa(NOj) + Cl,=NaCl-l-OH2Cl(NOs). Thepre-
sence of CI and the chlorous nitroxyl (NO2)
render the hydrogen displaceable by sodium:
hence the liquid dissolves in alkali.
Chloro-di-nitro-metliane C01H(NO2)2.
Potassinm salt CKC1(N02)2 : large yellow
crystals, soL water, explodes at 145° (Losanitsch,
B. 17, 849).
Oi-cUoro-di-mtro-methane CCLiCSO-Ji,
(above 100°). S.O. ^ 1-685 (M.). Formed by
passing chlorine into an aqueous solution of
CKCl(N0j)2 (Losanitsch, B. 17, 848).
Pr^araiion. — Crud^ naphttialeuo tetrachlor-
ide (200 grms.) is treated with fuming HNO,
(400 c.c.) in a large retort ; when the reaction
is over, the mixture is distilled as long as the
residue in the retort froths strongly. The distil-
late is diluted with twice its bulk of water and
the di-chloro-di-nitro-methane distilled oft vrithi
steam; the yield is 4 p.o. of the naphthalene
tetrachloride (Marignao, A, 38, 16 ; Baschig; B.
18, 3326).
Properties. — Pungent oil; volatile with
steam. On reduction with SnOli it yields
hydroxylamine.
Tri-chloro-nitro-methane C01,(N02). Chloro-
picrim. Nitro-chloroform. Mol. w. 164k (112°
cor.). S.G. S 1-6928 (Thorpe). O.E. (0°-10°)
■001106; (0°-100°) -0012256. S. (alcohol of
80-5 p.c.) -743 (Oossa, O. 2, 181). S.V. 110-49.
II., 1-4679 (Gladstone, C. /. 23, 101).
Formation. — 1. By distilling picric acid and
other nitro- compounds with bleaching-powder
(Stenhonse, A. 66, 241 ; P. M. [3] 33, 53 ; Ger-
hardt a. Cahours, Compt. chim. 1849, 34, 170). —
2. By distilling chloral with cone. HNO, (Ke-
kul6, A. 106, 144). — 3. From chloroform and
HNO, (Mills, C. J. 24, 641).— 4. By distiUing
alcohol with sodic chloride, KNO, and H^SO,
(Kekul6, A. 101, 212).
Preparation. — A saturated (at 30°) solution
of picric acid (Ipt.) is mixed with bleaching
powder (10 pts.) previously made into paste with
water, and the mixture distilled (Hofmann, A.
139, 111).-
Properties. — Pungent liquid. V. si. sol.
water, v. sol. alcohol and ether. ^
Reactions.— 1. May be redticed by iron and
acetic acid to methylamine (Geisse, A. 109, 282).
2. Fuming HI at 100° forms NH„ HCl, and 00,
(Mills, C. J. 17, 153).— 3. NaOEt in absolute
alcohol give^ orthocarbonio ether G(OEt),
(Bassett, 0. J. 17, 198).— 4. KCy and dilute
alcohol forms chloro - nitro - malonitrile
C(N0^)ClCy2, an unstable compound which gives
with aqueous lead acetate app. C(N02)ClCy23PbO
and with silver nitrate(C(N02)ClCy2),(AgNO,),8aq
(Bassett, C. J. 19, 352). — 5. Alcoholic ammonia
forms guanidine C(NH)(NH2)„ (Hofmann, C. J.
19, 249).— 6. Alcoholic KOH gives KOI and
KNO2 (S.).— 7. Alcoholic KOAc at 100? gives
KCl, KjCO,, and KNOj (Bassett, O. J. 18, 31).—
8. K2SO3 forms CH(N02)(S03K), (Eathke, A.
161, 149). — 9. With benzene in presence of
AI2CL it yields tri-phonyl-carbinol and tri-
phenyl-methane (Elbs, B. 16, 1274).— 10. With
phenol and Al2Cle the chief product is aurin
(tri-oxy-tri-phenyl-carbinol) (E.). — 11. With
naphthalene and Al^Cl, it yields tri-naphthyl-
caibinol (&.).
DI-CHLOED-NITEO-TETEA-METHYL-DI-
AMIDO-TEX-PHENYL-METHANE
C,,H23N,Cl20, i.«. 0,H,(N02).CH(0,H,01.NMe2),.
[208°]. From «i- chloro -di- methyl -anilino,
p-nitro-benzoic aldehyde, ZnCl,, and HGl (Kock,
B. 20, 1562). Lemon-yellow scales (from ben-
zene). May be reduced to CjsHaN.Ol, [181°].
P i 0 r a t e CjHjjN.Oi.Clj. [189°].
CHLOKO-NITEO-DI-MEIhYL-ANILIH'II
C„n,Cl(N02)(NMe,) [4:3:1]. [56°]. Formed to-
gether with other products by the action ot
nitrous acid upon ^-chloro-di-methyl aniline
(Kooh, B. 20, 2459 ; c/. Heidlberg, B. 30, 149)^
96
CHLORO-NITRO-NAPHTHALENE.,
CHLOBO-NITEO-NAPHTHALENE
C,oH„01(NOj) [1:4]. [85°]. From (o)-ohloro-
naphthalene and cold HNO3 (S.G. 1-4). Ex-
tremely slender, light yellow concentric needles.
PCI5 gives (' P ')-di-ohlpro naphthalene. Tin and
HCl reduce it to (a)-naphthylamine (Atterberg,
B. 9, 927).
(' a ')-CIiloro-di-nitro-naphthaIene
C„H,Cl{NO„)j [1:4:1']. [106°]. Formed, together
vith the foregoing by treating (a)-chlorp-uaph-
thalene mth warm HNO, (S.G. 1-4) (A. ; Faust
a. Saame, A. 160, 68). Long yellow pliable
needles, v. sol. hot alcohol. PGlj converts it
into (i)-tri-chloro-naphthalene.
(' j8 ')-Chloio-di-iiitra-naphtIialene probably
NO, NO,
[180°] (A.) ; [175°] (B.). Obtained
<X)
by the action of hot faming ENO, on (a)-ohloro-
naphthalene (Atterberg). Formed by the action
of ENO, upon chlorp-nitro-(a)-naphtJaoio acid
[225°] (Ekstrand, B. 18, 2881). GUstening
yellow needles (from alcohol). SI. sol. boiling
alcohol.
(■ J3 ')-Dl-cUoro-mtro-naphthalene
C,oH,Cl,(NO,) [1:4:11, [92°]. From ('$')-di.
ohloro-naphthalene and HNO, (S.G. 1-45) (Wid-
mann, Bl. [2] 28, 509). With POI5 it gives (5)-tri-
chloro-naphthalene.
Di-chloro-nitro-naphthalene C,oHsCl2(N02).
[95°?]. Formed, together with an isomeride
[142°], by the action of cold cone. HNO3 on (5)-
di-ohloro-naphthalene (AUn, Bl. [2] 36, 433).
Si-chloro-nitro-naphthalene G,oHsCl2(N02).
[0. 114°]. From (c)-di-chloro-naphthalene and
cold fuming HNO, (AUn, Bl. [2] 36, 435). Yel-
lowish needles.
(ii)-])i-chIoio-nitro-naphthalene
0,„H5C1,(N0,). [119°]. Formed by adding
fuming HNOg to a solution of (7)-di-chloro-naph-
thalene in HOAo (Cl^ve, Bl. [2] 29, 499). Golden-
yeUow needles; m. sol. boiling alcohol. FOl,
forms (e)-tri-chloro-naphthalene.
Oi-culoro-nitro-naphthalene .C,oH3Cl2(N02).
[139°]. Formed, together with the isomeride
[114°], by treating (e)-di-chloro-naphthalene
with cold fuming HNO, (Alen, Bl. [2] 36,' 435).
Needles, turning brownish-violet in the air.
Si-chloro-nitro-naphthaleue C„H5Cl2(N02).
[142°]. From (S)-di-chloro-naphthalene and cold
cone. HNO, (AUn, Bl. [2] 36, 433). Needles,
turning green in the air.
(7)-I)i-chloro-mtro-uaphthalene
C„HsCUNOs). [142°]. From (7).di-ohloro-
naphthalene and cold HNO, (S.G. 1-4) (Atter-
berg, B. 9, 928). Short sulphur-yeUow brittle
prisms (from HOAc). PCI, gives (S)-tri-ohloro-
naphthalene.
(■ $ ').I)i-cIiloro-di-nitro-naphthaIen8
C„H4Cl2(NO,)j. [158°]. Formed by adding
HNO, (S.G. 1-48) to a solution of ('3 ')-di-ohloro-
naph&alene in HOAc (Widmann, Bl. [2] 28,
610). Long yellow needles : si. sol. alcohol.
(7)-I>i-cMoro-di-nitro-iiaphthaIene
CK^^CliNOj),. [246°]. From(7)-di-chloro-nitro-
naphthalene [142°] and HNO, mixed with
H^SO, (Atterberg, B. 9, 1730). Light yellow
brittle prismatic needles ; v. si. sol. ^11 solvents.
PCI, gives (ej-tetra-chloio-naphthaleue.
(S)-I)i-chIoro-di-nitro-naphthalene
C,„H,Cl2(N02)2. [246°]. Formed by adding
fuming HNO, to a solution of (5).di-ohloro-
naphthalene in HOAc (Alto, Bl. [2] 36, 434).
Pale yellow prisms, turning green in aif.
(E):I)i-cliloro-di-mtro-iiaphthalene
G,„H,Clj(N0j)2. [253°]. Formed by acting on
(c)-di-clLloro-naphthalene dissolved in glacial
acetic acid with fuming HNO, (AUn, Bl. [2] 36,
435 ; Glaus a. Dehne, B. 15, 320). Pale yell6w
needles, turning red in air. POl, gives (f )-tri-
ohloro-naphthalene. Alcoholic KOH forms
C,.H,(OEt)2(N02)2.
Di-chloro-tri-nitro-naputnalene
0,»H,Gl2(N0j),. [178°]. From ('o')-ai-ohloro-
naphthalene, HjSO,, and HNO, (S.G. 1-48)
(Widmann, Bl. [2] 28, 505). Brittle yellow
prisms (from HOAc); sL sol. alcohol, t. sol.
chloroform.
(e)-Di-chIoro-tri-mtro-naphthalene
0,^01^(^0^),. [200°]. Formed by boiling (t).
di-chloro-naphthalene with fuming HNO, (AUn,
£2. [2] 36, 435). Pale yellow needles. POl, gives
(i))-tetra-chloro-naphthalene [160°].
i)i-cliloTO-tri-nitro-naphthalene
C,„HsGlj(N0j)3. [201°]. Formed by^ acting on
(S) -di-chloro-naphthalene with fuming HNO, at
100° (Alto, Bl. [2] 36, 434). Pale yellow needles,
turning greenish in the air.
Tetra-chloro-nitro-naphthalene
0,oH,Gl4(NOj). [155°]. From (S)-tetra-chloro-
naphthalene and cone. HNO, (Atterberg a. Wid-
mann, B. 10, 1841). Ijarge pale-yeUow trimetrio
prisms (from alcohol-toluene). PCI, gives (' J3 ')•
penta-chloro-naphthalene.
CHLOBO-HITaO-(a).irAPETHOIC ACID
NO, CO,H
C,„H,G1(N0J(C0,H) probably
CO
[225°|.
Formed by nitration of oUoro- (a) -naphthoic acid
[245°]. Prismatic needles.
Ethyl ether A'Et: [121T; tables (from
alcohol) (Ekstrand, B. 18, 2881).
TEI-CHI0E0-TETEA.NITE0-DI.(3).1TAPH.
THYL - ETHANE C„H„(N0,),G1,. [258°].
From tri - chloro - di - (iS) - naphthyl - ethane
(0,„H,),GH.0Cl3 and HNO, (Grabowski, B. 11,
298). GrystaUme. powder, insol. alcohol, etheii
and HOAc.
SI - CHLOEO ■ TETBA - NITEO- I>I.(a).irAFH.
THYL-ETHYIEHE 0„H,„(N03).Clj. [214°].
From di - ohloto - di - (a) - naphthyl - ethylene
(G„H,)2G:CC1, and fuming HNO, (Grabowski, B.
11, 299).
I)l-chloro-tetra.Bitro-di-(j3)-naphthyl-ethyl-
ene Oj2H,„(NO,)4Cl, [293°]. Formed by nitra-
ting di-chloro-di-(j3)-naphthyl-ethylene (<>.).
CHLOEO-NITBO-o-OXY-BEKZOIC ACID
C.H3(Cl)(N02)(OH)CO,H [5:?:2:1]. [163°]. Pre-
pared by nitration of m-ohloro-salioylio acid
(Smith a. Feiroe, B. 13, 34; Am. 1, 176). Short
needles.
Salt s — A'K : soluble yellow needles.— A'^Ba :
sparingly soluble orange needles. — A'Ag : inscL
pp.
Ethyl ether ATEit: [89°]; colourless flat
needles.
Amide [199°]. SI. sol. water, t. sol. alcohcL
OHLORO-NITEO-PHENOL.
97
ChloTo-di-nitro-o-ozy>benzoio acid
C5HCl(N0j)j(0H).C05H. [78°]. Prom ohloro-
salioylio acid and fuming HNO, (Hasse, B. 10,
2191). Long yellow needles (from water).
{Py. l:2).DI.CHL0a0-(B. 1 : 3or4)-DI-NITEO.
{Py.3)-0XY-(B. 2).lIETHYI.-QTrar01INE
^001:001
C,AN»C1,0. ».«. O.H(CH3)(NOJ.< I
^N : C(OH)
lii<ihl(m)-d%^tro-tolucw'bos1yril. [186°].
Formed by nitration of (Py. l:2:3)-di-ohloro-oxy-
(£.2)-metbyl-quinoline in cold H^SOj solution
by means of NjO,. Long yellow needles with
greenish reflex (Biigheimer a. Hoffmann, B. 18,
e.CHI0B0.o-NITE0-a.0XY-i8.PHE»YL.
PHOPIONIC ACID CAOINO5 i.e.
[2:l]C,H,(N0J.CHCl.CH(0H).00jH. [126°].
From o-nitro-a-oxy-cinnamio acid and fuming
HCl (Lipp, B. 19, 2649). Needles (from ether-
ligroin). Alcoholic EOH le-oonverts it into o-
nitro-a-oxy-cihnamio acid.
;3-ChloTO-p-nitro-a-ozy-jS-phenyl-propionlc
acid [4:l]q,H,(NO,).CHCl.CH(OH).C02H. [168°].
From p-nitro-a-ozy-oinnamic acid and fuming
HCl (L.). Small glittering needles ; si. sol. cold
water. The Ba salt is spht up by boiling water
into 0O„ BaCl,, and ^-nitro-phenyl-acetic alde-
hyde. AlcoboUo EOH gives ^-nitro-a-oxy-cin-
namio acid.
a-Chloro.o-nitro-;S-ox7-;8-phenyl-propionie
acid [2:l]O.H4(NO,).CH(OH).CHC1.002H. [120°].
Formed by passing chlorine into a solution of o-
nitro-cinnamio acid in dilute aqueous NaOH
(Baeyer, B. 13, 2261). Crystalline mass (from
benzene-ligroin). Sol. ether. Converted by NaOH
and FeSOf into indole. Alcoholic EOH gives 0-
nitro-0-oxy-oinnamic acid.
a-Chloro-2]-nitrO'i3-oxy-phenyl-propionic acid
[4:l]0»H,(N0j).0H(0H).CHCl.C0,H. [165°]. Pre-
pared in the same way from ^ -nitro-cinnamio
acid jBeilstein a. Euhlberg, A. 163, 142). Tri-
metric plates (from water). HCl (S.Cr. 1*1) at
150° gives chloro-nitro-cinnamic acid. Na2C0,Aq
gives, on warming, 2>.nitro-/3-oxy-cinnamic acid.
CHlOEO-o-NITBO-PHENOL C,H,01N0, i.e.
0,H,C1(NOJ(QH) [3:6:1]. Mol. w. 173^. [39°]
{L.). [40° and 32^°] (U.).
FormaMon^-l. By boiling (3,6,l)-ohloro-di-
nitro-benzene with aqueous NaOH (Lauben-
heimer, B. 9, 768). — 2. By nitrating m-chloro-
phenol (Uhlemann, B. 11, 1161).
Properties. — ^Lemon-yellow needles or prisms
(from water).
Salts.— C,H,Cl(NOj)(ONa) : scarlet prisms,
m. sol. cold water.— BaA', aq : slender scarlet
needles.— AgA'.
Methyl ether O.H,Cl(N02)(OMe). [70-5°].
Needles.
Chloro-o-nitro-phenol 0,H3Cl(N0j)(0H)
[6:2:1]. [70°]. Formed, together with the iso-
meride [111°], by treating o-ohloro-phenol with
nitric acid (S.O. 1*36) diluted with an equal
weight of water (Faust a. Miiller, A. 173, 309).
Flat yellow needles (from chloroformj. Volatile
with steam. HNO, gives chl<^ro-di-nitro-phenol
[111°].
Salts.— <3,HsCl(N0s)(0E) : long dark-red
needles, v. Bol. water.— CaA', aq : reddish-brown
prisms, m. sol. water.— BaA', aq : short copper^
Yoi-U,
brown platas, si. sol. water.— AgA' : carmine-red
scales, si. sol. water.
Ohloro-o-nitro-phenol 0,H,C1(N0,)(0H)
[4:2:1]. [87°].
Formation. — 1. The sole product of the action
o(_dilute HNO3 on p-ohloro-phenol (Faust, B. 6,
132 ; A. 173, 317 ; Suppl. 7, 190 ; Z. [2] 5, 450).
2. By ohlorination of o-nitro-phenol (Armstrong
a. Frevost,£. 7, 922).-~3. One of the products of
the action of alcoholic EOH on (4,2,1) -chloro-di-
nitro-benzene (Laubenheimer, B, 7, 1601).
Properties. — Light yellow monoolinio prisms
(from CHOI3). y. si. sol. water, m. sol. alcohol.
Volatile with steam. Br and water at 100° give
ohloro-bromo-nitro-phenol [125°] (Ling, 0. J. 61,
786). But Br in HOAc gives an isomeric ohloro-
bromo-hitro-phenol [120°]. •
S alt B.— C,H301(N0,)(0NHj) : orange-red
needles.^NaA' aq : red prisms. — BaA', 4aq :
short red prisms. — AgA'.
Ethyleth6r0,B.,a(S0,)(OEt). [62°]. From
AgA' and EtI. Formed also by nitrating the
ethyl ether of 2>-chloro-phenol (Hallock, Am. 2,
258; B. 14,37).
Ghloro-^-nitro-phenoI C,H3C1(N02)(0H)
[2:4:1]. [111°].
Formation. — 1. By chlorinating p-nitro-phe-
nol (Armstrong, O. J. 25, 12 ; Faust a. Miiller,
A. 173, 309 ; Eollrepp, A. 234, 4).— 2. Together
with the isomeride [70°],' by treating o-ehloro-
phenol with dilute HNO, (F. a. M.).— 3, From
ohloro-di-nitro-phenol [111°] by reduction to
chloro-nitro-amido-phenol followed by displace-
ment of NH2 by 01 through the diazo- reaction
(Faust, Z. 1871, 339).
Properties. — White silky needles, m. sol. boil-
ing water, v. sol. alcohol, ether, and chloroform^
Very slightly volatile with steam. HNO, con-
verts it into ohloro-di-nitro-phenol [111°].
Salts.- C8H3Cl(NOj)(OE)aq: brown needles,
V. sol. water. — OaA'^ 4aq : tufts of canary-yellow
needles, v. sol. water. — BaA'2 7aq: long dark-
yellow needles. — ^AgA': copper-brown flattened
needles, si. sol. water.
Methyl ether CaH,Cl(N03)(OMo). From
the methyl ether of nitro-o-amido-phenol by dis-
placement of NH, by 01. Needles.
Ethyl ether C.H,01(NO,)(OEt). Chloro-
mtro-phenetol. [78°]. Formed by chlorinating the
ethyl ether of ;-nitro-phenol by HCl and EClO,
(Hallock, B. 14, 37 ; Am. 3, 21).
Ghloro-nitro-phenol. Methyl ether
0,H,Cl(N02)(0Me) [2:a!:l]. Chloro-nitro-anisol.
[94°]. Prepared by nitration of the methyl ether
of o-chloro-phenol (Fischli, B. 11, 1461). Colour-
less spikes.
Chloro-di-nitro-phenol 0,H,Cl(NOj)3(0H)
[4:2:6:1]. [81°].
FormaUon. — 1. From p-chloro-phenol and
HNO, (S.0. 1-4) (Dubois, Z. 1867, 205).— 2. By
nitration of p-chloro-phenol snlphonic acid
(Petersen a. Praderi, A. 167, 150).— 3. By nitra-
ting chloro-nitro-phenol [87°] (Faust a. Saame).—
4. From di-chloro-di-nitro-benzene [104°] and
boiling aqueous NaOH (Engelhardt a. Lat-
schmofl, Z. 1870, 234; Earner, O. 4, 395).—
6. By chlorinating (' $ ')-di-nitro-phenol (Arm-
strong, B. 6, 649).— 6. In small quantity, together
with the isomeride [111°], b^ the action of ICl
on tri-nitro-phenol (picric acid) (Petersen, B, 6,
369 J Armstrong, he. ci«.).— 7. By boiling chloro-
H
98
CHLORO-NITTlO-PnENOL.
di-nitro-aniline [145°] with aqueous KOH (Kor-
ner). — 8. By dissolving ohloro-o-oxy-benzoic acid
in fuming HNOa (Smith a. Peiroe, A. Ph. S. 17,
707; 4m. 1,176; B. 18, 35).
Properties. — Yellow monoclinio prisms (from
chloroform). SI. sol. hot water, v. sol.
alcohol. CombincB with aniline, forming
CeH,Cm ANHjCA [187°] (S. a. P.) ; decom-
posed by boiling water.
Salts.— 0^201(X02)2(OE): long red needles
with green lustre; t. sol. hot, t. si. sol. cold
water. — NH,A': deep orange needles. — NaA'Saq :
scarlet moss-like forms. — BaA'^aq : pale, saffron-
yellow needles, v. si. sol. hot water. — GuA', 2aq :
saffron-yellow needles. — ^FbA',aq: yellow needles.
AgA' : red needles.
Methyl ether C.HjCl(N02) (OMe) : [66°].
, Ethyl ether OeHsCl(NOj)j(OBt) : [55°].
Chloro-di-nitro-phenol G^G1(N02)2(0H).
[80°]. Formed, together with the preceding,
with which it is perhaps identical, by nitrating
chloro-o-oxy-benzoio acid (Smith a. Feircej
A. Ph. S- 17, 707). Solidifies at 25°, whereas
the preceding solidifies at 69°. — EA' l^aq : orange
needles, much more soluble in water than the E
salt of the preceding. — AgA' : bronzed needles.
OUoro-di-nitro-phenol G,H2C1(N02)2(0H)
[2:4:6:1]. [111°] (F. a. S.) ; [96°] (Zehenter, M.
6,527). S. -052 8110°.
Formation. — 1. From o-ohloro-phenol and
cone. HKO, (GriesB, A. 109, 286; Armstrong,
e. J. 26, 96 ; Faust a. Miiller, A. 173, 312).—
2. From o- or ^-nitro-phenol by successive
ohlorination and nitration (Faust a. Saame, A.
Suppl. 7, 195; Seifart, A. Swppl. 7, 198).—
3. The chief product of the action of ICl on
picric acid (Petersen, B. 6, 368). — 4. By chlori-
nating di-nitro-phenol [114°] (Armstrong, C. J.
25, 12 ; Faust, Z. 1871, 339).— 5. By nitrating
(2,4,l)-ohloro-nitro-phenol (Armstrong; F. a. M.).
6. By nitrating (2,6,l)-ohloro-nitro-phenol (F.
a.M.). — 7. From di-nitro-amido-phenol (picramic
acid), by displacing NH, by Gl through the diazo-
reaction (F.). — 8. By the action of HNO, on di-
chloro-phenolf -sulphonio acid (Armstrong, C. J.
24, 1112). — 9. From di-ohloro-j>-nitro-phenol and
HNO, (A.). — 10. By nitrating o-chloro-phenol
Eulphonic acid (Armstrong a. Prevost, JB. 7, 405).
Properties. — Yellowish laminse (from alcohol)
or irregular six-sided tables (from GHOl,). SI.
sol. hot water, m. sol. alcohol and ether. Tastes
bitter.
Salts.— O.H,Cl(NO,),(OE)aq: short slender
yellow needles. — ^NaA' liaq : short yellow needles.
— NH,A' liaq.-NH4A' (a.).-NH,A'aq (F. a. S.).
— BaA',9aq (F. a. S.).— BaA', lOaq (F. a. M.).—
OaA'2 7aq: flat golden needles.- MgA', 7aq. —
MgA', lOaq.— CuA', 8aq : gteenish-yellow hair-
like needles.— AgA' aq.
ChloTo-di-nitro-phenol OJBijBlQSO^i(OB.),
[70°]. From di-ohlon^di-niteo-benzene and
aqueons NaOH (Engelhardt a. Latschinoff, Z.
1870, 234 ; E5mer, 0. 4, 896). Long needles.—
BaA'^Saq: yeUow needles.
Si-chloro-nitro-phenol 0A01<(K0,)(0H)
[2:4:6:1]. [122°]. , ,
FormatUm. — 1. By nitrating di-chloro-phenol
[43°] (Fischer, A. Sivppl. 7, 185 ; Ghandelon, B.
16, 1752) or its sulphonic acid (Armstrong, 0. J.
24, 1119 ; 26, 93).— 2. By passing chlorine into
an aqueons BolutioQof o-nitro-phenolji-Bulpbonio
acid (Schmitt a. Olutz, B. 2, 52).— S. By chlori-
nating oliloro-nitro-phenol [87°] (Faust a. Saame,
A. Suppl. 7, 195). — 4. From o-chloro-phenol by
successive nitration, and ohlorination (A.). —
6. By chlorinating chloro-nitro-phenol sulphonic
acid (A.). — 6. From di-chloro-o-oxy-benzoio acid
by dissolving in HOAc and treating with HNO,
(Smith a. Enerr, Am. 8, 95).
Properties. — ^TeUow laminae (from alcohol).
SI. sol. water, forming a deep yellow solution,
v., sol. alcohol and ether. Volatile with steam.
Explodes when heated suddenly. HNO, forma
chloro-di-nitro-pheuol [81°]. Bromine and water
at 100° form chloro-tri-bromo-quinone (Ling,
C. J. 61, 781).
Salts. — C,H,Cl!(NOj)(ONH,) : orange
needles; may be sublimed. — NaA': nodular
groups of orange-red needles. — EA' : needles of
the colour of CrO,.- EA'aq (Faust, A. 173, 317).
BaA'2 2aq: orange needles, v. si. sol. water. —
MgA', 2aq.— PbA'(OH).— ZnA', 2aq.
Ethyl ether O.H,Cl,(NO,)(OEt). [29°].
Pearly prisms.
Acetyl derivative 0,H2Cl2(N02)(OAc).
[77°]. From NaA' and AcCl.
Si - chlor 0 - nitro - phenol C,H2CL(N0,) (OB)
[6:2:4:1]. [125°].
Formation. — 1. By chlorinating j)-nitnt>
phenol (Seifart, A. Suppl. 7, 198 ; Eollrepp, A.
284, 8). — 2. By nitrating di-chloro-phenol sul-
phonic acid (Armstrong, C. J. 24, 1112 ; 'Faust,
Z. 1871, 338).
Properties. — Slightly yellowish prisms or
tables (from ether), or colourless needles (from
chloroform). Y. si. sol. hot water ; not volatile
with steam. Converted by heat into di-chloro-
quinone, NO, and N (Armstrong a. Brown, B. 7,
926). HNO, (S.a. 1-45) forms chloro-di-nitrq-
phenol [111°]. Bromine and water at 100° form
di-ohloro-di-bromo-quinone (Ling, C. J. 51, 786).
Salts.— C,HjOl2(NO,)(ONHJ aq : shining
yellow needles, becoming anhydrous and colour-
less over HjSOi NaA' 5aq : yellow needles. —
EA'aq : orange needles.- BaA'j 3|aq : red needles
(Ling, C.J. 61, 786).— BaA'j4aq (S.) : brown-
red laminffi or red needles. — BaA'j 8aq : yellow
needles (F. a. M. ; A. 173, 311).- CaA'j9aq:
golden needles or laminee, v. sol. water.—
CdA'j3Jaq. — PbA'j4iaq. — CuA'^ 5aq. —
MgA'j lOaq : rosettes of yellow needles.— AgA' :
colourless needles.
Ethyl ether O.H,Cl,(NO,)(OEt) [36°].
Di-chloro-nitro-phenol C,H2Clj,(N0J(0H).
Formed in small quantity by nitrating di-chloro-
phenol with ClSOaH (Armstrong, Z. 1871, 679).
Short yellow needles (from water).
Tri-chloro-nitro-phenol
CeHCl3(N9,){OH) [6:4:2:3:1]. [69^. Obtained
by saponifying its nitro-benzoyl derivatives,
which are pbtained by nitrating benzoyl-tri-
chloro-phenol (Daccomo, B. 18, 1164). Glisten-
ing colourless needles. V. sol. alcohol, ether,
and benzene, si. sol. water. Fe,Cl, gives a
violet-blue colouration.
Salts.— A'NH, : small yellow needles.—
A'E aq.— A'Ag : small yellow needles.— A'^Ba aq •
yellow plates.
o-Nitro-benzoyl derivative
C,HCl,(NO,).OCO.G«H,(Nb,) : [106° cor.] ; col-
ourlesB glistening scales ; soL l^cohol and ether.
OHLOBO-NITRO-PHTHALIO ACID.
09
m-Niiro-bemoyl derivative
0^Ca,(NOj).OC0.CeH,(NO,): [146° oor.]; large
eoloarlesa tables ; Bol. alcohol and ether, insol.
water.
Ethyl ether (V) [54°]. Prom tri-chloro-
phenetol and cold H-SO, and HNO. (Faast, A.
149, 152).
Tri - ohloro - nitro - phenol 08H01,(N0j)(OH)
[2:3:5:4:1]. [146°]. Prom tri-ohloro-phenol[64°]
and HKO,. White needles. Beducea to tri-
ohloro-j)-amido-pbenol (Lampert, J. pr. [2] 33,
Et]}yl ether 08H01,(NO,)(OEt). [69°].
Tri-ohloro-di-nitro-phenol. . Ethyl ether
0.01,(N0j)j{0Et). [100°]. Prom tri-chloro-
pbenetol and warm HXO, mixed with H^^^^i
(Panst, A. 149, 152).
GHLOKO-KIIBO-FHEITOL STTIFHONIC ACID
0,Hj01(N0,)(0H)(S0,H) [2:6:1:4]. Prom di-
ohloro-phenol Bolphonio aoid and cold HNO,
(Armstrong, C. J. 24, 1117). Pormed also by
nitrating o-ohloro-pbenol sulphonio aoid (Arm-
strong a. Frevost, B. 7, 404). An isomeric
acid is formed by chlorinating nitro-phenol
snlpbonic acid (Armstrong a. Brown, 0. J. 25,
872). HNO, converts it into chloro-dl-nitro-
pbenol [111°]. Chlorine forms di-chloro-nitro-
pbenol [121°].
Salt s.— CAClNSOgK, : orange-red six-sided
plates, V. e. sol. hot water. — OgH,ClNSOaK^aq :
yellow needles.
SX-CHLOBO-SI-inTBO-BIFHENYL
C^,(N0s)01.0jH,(N02)01. [140°]. Prepared
by the nitration of di-chloro-diphenyl. [4:1]
C.H.C1.0,H,C1 [1:4] (Schmidt a. Sohultz, B. 12,
494). Small needles or long prisms. SL sol.
cold, V. sol. hot, alcohol, and GgHg.
CHLOBO-NIIBO-DI-FHENTL-AinNE
C,ja,01NA »•«• 0,H,.NH.CsH301(N0i,). [109°].
Slowly formed,' together with benzene-azo-
aniline (amido - azo - benzene) by mixing
(l,3,4)-ohloro-di-mtro-benzene [39°] (Imol.) with
anOine (3 mols.) (Laubenheimer, B. 9, 771).
Long red needles (from alcohol). Does not com-
bine with acids.
NitrosamiM C.H..N(NO).C.H,Cl(NOj).
[111°]. Tellow, aiz-sided laminas, m. sol. cold
uoohoL
CHXOBO-DI-KITBO-DI.FH£inn..AlIINE-
o-CAaBOXTLIC ACID
C.H,(NOJjCl.NH.O,H,.COJH [256°]. Formed by
mixing alcoholic solutions of di-cbloro-di-nitro-
benzene OeHjOl!(NO,)2[l:4:2:6] and anthranilio
acid 0,H,(NH,)CO,H[1:2] and adding NH, (Jour-
dan, B. 18, 1454). Qlistening red prisms. Sol.
hot alcohol and acetic acid, insol. water.
CUoro-dl-nitro-di-phenyl>amine-o-carboxylio
aoid 0,H,(NOj)j.NH.OsH,Cl.CO^. [282° nncor.].
Obtained by mixing alcoholic solutions of chloro-
di-nitro-benzene C,BLjCl(N08)2[l:2:4] and chloro-
ftmido-benzoio acid C,H,G1(NH2)C0;^[1:4:6], and
adding NH, (Jonrdan, B. 18, 1450). Pine orange
needles. V. si. SoL cold alcohol and acetic aoid,
insoL water, benzene, and ligioin. A',Ca : si. sol.
water.
TBI - OHtOBO - BI - HITBO - DI - PHENYL -
BUTANE 0„H„01,(N0j),. Prom tri-chloro-di-
phenyl-butane and fuming HNO, (Hepp, B. 7,
1420). Small yellowish tables (from alooboQt
81. wd. CS« T. BoL ether.
CHLOBO - NITBO - FHENYLENE • OI&UINE
CeHjCl(NO,)(NH2)2[l:4:3:5]. [192°-194]. Prom
0,Hj01,(N02)[l:3:5:2] and alcoholic NH, at 200='
for several days (Beilstein a. KurbatoS, A. 192,
233). Bed needles. V. sol. alcohol, sol. dilute
(50 per cent.) acetic acid or benzene, si. sol. light
petroleum.
DI-CHLOBO-NITBO-PHENYIi-ETHANE v.
Dl-CHLOBO-nrmo-ETB'ni-BEIIZBIIJE.
Penta-ohlora-di-uitro-di-plienyl-etbane
C„H,01.N,0, i.e. CC1,.CH(CA01.N02),. [143°].
Prom 001,.0H(08H^Cl)j and fuming HNO,
(Zeidler, B, 7, 1181). Needles (from alcohol).
CHLOBO -NITBO -PHENYL HEBCAFTAN
0„HiClNSO,i.e. 0,H,C1(N02)(SH) [3:6:1]. [171°].
Prom (3,6,l)-chloro-di-nitro-benzGne and alcoho-
lic ESH (Beilstein a. Kurbatoff, A. 197, 82).
Yellow needles, t. sol. chloroform, y. si. sol. alco-
hol.
ChloTO-nitro-phenyl mercaptan
0„H,01(N0j)(SH) [4:2:1]. [213°]. Prom (1,4,3).
di-chloro-nitro-benzene and alcoholic KSH (Beil-
stein a. Kurbatoff, A. 197, 79). Yellow tables
(from HOAc). SI. sol. alcohol. Alcoholic am-
monium sulphide converts it into CigHgCl^NjS,
[147°], which crystallises in yellow nfsedles, and
is converted by HNO, into C,H,01NjS [104°].
CHLOBO-NITBO-FHENYL-m-FHENYLENE-
DUMINE NHj.O,H,.NH.C,H,a(NOj). [151°].
Bed needles. SI. sol. cold alcohol. Prepared by
warming an alcoholic solution of m-pheuylene-
diamine and (1,3,4) - chloro - di - nitro - benzene.
Forms with acids unstable yellow salts (Lauben-
heimer, B. 11, 1158).
(Py. 4:1:2) -CHLOBO - NITBO - PHENYL - ISO-
>0(NO,):CPh
QUINOLnTE 0,.H,C10^,»A 0,Hi< |
>001=N
[156°]. Pormed by heating nitro-qzy-phenyl-
isoquinoline (nitro - iso - benzal • phtnalimidine)
with POOl, (Gabriel, B. 19, 834). Small yeUow
needles or prisms. T- sol. hot acetic acid, benz-
ene, chloroform, ether, and GS, ; si. sol. alcohol,
T. si. soU Ugroin. By HI and P it is reduced to
amido-phenyl-isoquinoline. Heated with alco-
holic sodium ethylate it yields the ethyl-ether of
nitro-oxy-phenyl-isoquinoline.
DI-CHLOBO - DI- NITBO -DI-FHENYL-B1TL.
PHIDE (GeH,01.N0,)jS. [150°]. Yellow needles.
Almost insol. alcohol, si. sol. acetic acid. Pre-
pared by the action of alcoholic EjS on (1, 4, 6)-
di-chloro-nitro-benzene (Beilstein a. Eurbatow,
J3. 11, 2056; 4.197,79).
CHLOBO-NITBO-PHENYL-p-TOLYl-AMINE
G.H,Me.NH.G.H,Cl(NOj). [124°]. Small red
needles. SI. sol. cold alcohol. Prepared by the
action of a cold alcoholic solntion of p-toluidine
on (1, 3, 4)-chloro-di-mtro-benzene (Laubenhei-
mer, B. 11, 1157).
DI - CHLOBO-DI-NITBO-DI-FHENYL - TTBE A
C„H,C1,NA i*. CI0(NH.0,H,G1.N0,),. [210°].
Prom di-chloro-di-phenyl-guanidine and HNO,
(Losanitsoh, Bl. [2] 32, 170). Yellow tables, in-
sol. water, si. sol. alcohol.
CHtOEO-NITBO-FHTHALIC ACID
0,H,ClNO.i.«. CA01(N0,)(00^),. Prom (7)-
di-chloro-naphthalene and HNO, (Atterberg, B.
10, 647).— KjA" : crystals; eii)lodes above 300°.
Di-ohloro-nitro-phthalie aoid. Prom (C)-tri-
chloro-naphthalene and HNO, (S.G. 1-2) at 150°
(Widmann, B. 12, 9§0),
100
CHLOKO-NITRO-PHTHALIO AOID.
Iri-chloro-nitro-plitlialio aoid CsH^CI,NO,.
From {'a 'j-tri-ebloro-naplithalene and EHO3
(Atterberg a. Widmann, B. 10, 1844).
DI-CHLOBO-SI-iniflO-f&OFAirE
C3H4Cl2(NO,), (?). From di-ohloro-propylene
(from tri-ohioro-butyrio aldehyde) and fuming
iraO, (Pinner, A. 179, 49). OU; converted by
tin and HCl into C,H.C1, (19°), C,H,01,(NHj),
and tri-chloTo-nitro-propane
Tri-cMoro-nitrOrpropaue C,H«C1,(N0J. (c.
193°). Formed as above.
DI-CHLORO-NITRO-FBOFTLENE
OjH,CL,(NQJ. (0. 159°). Formed by the action
of aqueous NaOH upon di-ohloro-di-nitro-pro-
,pane and upon tri-chloro-nitro-propane (Pinner,
A. 179, 67).
CHL0EO-lHTRO.QirXKOi:.INE C„H.Cl(NOj)N
[120°-123°]. Formed, together with the isomer-
ide [186"^, by nitration of {B. 1 or 3)-chloro-
quinoline (La Coste a. Bodewig, B. 17, 927).
V. sol. hot alcohol, si. sol. water.
Chlcro-nitro-qTmioline CjHsC^NOJN. [186°].
Formed, together with the preceding, by nitra-
tion of {B. 1 or 3)-chloro-quinoline (La Coste a.
Bodewig, B. 17, 927). Long colourless needles.
SI. sol. alcohol.
CHLOBO-NITBO-QTTIirONE Anilide
CeHCa(N0J(NHPh)02 [6 or 2:3:2 or 6:4:1]. [208°].
Small red trimetric tables. Formed by the action
of aniline in alcoholic solution upon di-chloro-
nitro-quinone C^Clj(N0s)0j [6:2:3:4:1] (Guarea-
chi a. Daccomo, B. 18, 1172).
Si - chloro • nitre - qninone CsHCl2(N02)02
[6:2:3:4:1]. [220°]. Formed by the action of a
mixture of HNO, and H2SO4 upon the propionyl
derivative of tri-chloro-phenol (Guareschi a.
Daccomo, B. 18, 1171). Small yellow needles.
Sol. cold alcohol, el. sol. ether and CS,, v. si. sol.
hot water.'
CHIOBO-ISO-NITSOSO-ACETIC ETHEB
N(OH):CGl.COjEt(?). Chloro - oximido - acetic
ether. [80°]. From chloro-aoeto-acetic ether
(v. Allihn, B. 11, 567) and fuming HNO3 (Prop-
per, A. 222, 60). Glittering columns (from
ether). V. e. sol. alcohol and ether. Boiling
water splits it up into hydroxylamine, oxalic
acid, and alcohol.
CHLOBCISO-irXTBOSO-ACEIONE
CH,.00.CC1(N0H). Mono-oxim of o-ehloro-
pynwic aldehyde. [110°]. Formed in small
quantity by treating chloro-acetone with fuming
HNO, (Glutz, Z. 1870, 629; Barbagha, B. 6,
321). Formed also by heating the product of
the action of nitrous acid gas upon acetone
((CH,)jC(ONOj).C(NOH).CO.CH,(?)), with dilute
HCl ; acetone and HNO, are formed at the same
time (Sandmeyer,£. 20, 640). Prisms or tables ;
v. sol. water, alcohol, and ether.
Oxim CH,.C(NOH).Ca(NOH). Di-oximof
a-chloro-pyruvie aldehyde. Chloro-methyl-gly-
oxim. [171°]. Small white needles.
a-CHtOBO-o-NIIBO-STTBENE C,H.ClN02t.«.
C,H,(NO,).CCl:CHr NUro-phenylohloro-ethyl-
ene. From o-nitro - acetophenone and PCI,
(Gevekoht, il. 221, 329). Oil.
a-CUoro-p-nitro-styreiie OaH,(N02).CCl:CH,
[64°]. From ^-nitro-acetophenone and PCI,
(DrewBon, A. 212, 162). Concentric groups of
slender needles (from benzoline).
a.ChlOFO-ai.nitro-st7rene Ph.CCl:CH.NO,
[49°]. From FhOHGl.CHCl.NO, and aqueous
NaOH (Priebs, A. 225, 345). Golden platei
(from light petroleum). Insol. water, soluble,
when finely divided, in alkalis.
<»-0hloro-o-nitrQ-styreneCaH4(NO2).CH:CHCl.
[59°]. Formed as a by-product in the pre-
paration of chloro-o-nitro-oxy-phenyl-prOpionio
aoid by the action of hypoohlorous acid on o-
nitro-cinnamio acid (Lipp, B. 17, 1070). Glisten-
ing needles or prisms. V. sol. ether and hot
alcohol, si. sol. hot water, insol. cold water.
TBI-CHLOEO-NITBO-THIOPHENE
C4S01,(N02). [86°] Formed by nitration of
tri-ohloro-thiophene. Eeddish-yellow felted
needles. V. sol. benzene and ether, less in al-
cohol (Eosenberg, B. 12, 652).
GHLOBO-NIXBO-TOLVENE
C,H3(CH3)C1(N0J [1:4:3] : [9°]. (260° i. V.).
S.G. II 1-297.
FomuiM(m.—l. Together with the (1:2:4)-
isomeride by iiitration of ^-ohloro-toluene (10
pts.) with a cold mixture of cone. HNO3 (12 pts.)
and cone. H^SO, (17 pts.) (Engelbrecht, B. 7,
797; Goldsohmidt a. Honig).— 2. Fromwi-nitro-
jp-toluidine C3H,(CH3)(N04(NHj) [1:3:4] by the
action of CujCl, upon the diazo- compound (Gat-
termann a. £aiser, B. 18, 2599).
Beaction. — On reduction it gives p-ohloro-»t-
toluidine [28°] (Goldsohmidt a. Hdnig, B, 19,
2438).
(o)-CMoro-iiitro-toluene CsH3(CH,)Cl(NOs)
[1:2:3!]. (250°). Oil. Formed by nitration of
0-chloro-toluene. On redaction it gives a chloro-
toluidine [83°] (Goldsohmidt a. Honig, B. 19,
2443; cf. Wroblewsky, A. 168, 200).
Chloro-nltro-tolueneG,H3(CH,)Cl(NOJ[l:4:2].
[38°]. (240° at 718 mm.).
Formation,.— 1. Together with the [1:3:4]
isomeride, by nitration of ^-ohloro-toluene (10
pts.) with a cold mixture of cone. HNO, (12 pts.)
and cone. H^SO, (17 pts.) (Engelbrecht, B. 7,
797 ; Goldsohmidt a. Honig, B. 19, 2438).- 2.
From o-nitro-j>-toluidine by the action of Cu^Gl,
upon the diazo- compound (Beilstein a. Euhlberg,
A. 158, 336).
ProperUes. — ^Needles; si. sol. cold alcohol,
volatile with steam. On reduction it gives 2>-
chloi-o-o-toluidine [22°] (Goldsohmidt a. Honig,
B. 19, 2438).
Chloro-nitro-tolnene CeH,MeCl(N02) [1:2:5]
[44°]. (248°) at 711 mm. Obtained by the
action of Cu2Cl2upon diazotisednitro-o-toluidiite
C.H3Me(NH2)(N02) [1:2:5]. Needles (from ether)
(Goldsohmidt a. Honig, B. 20, 199).
Chloro-nitro-tolneneG,H,(CH3)Cl(N02) [1:3:6].
[55°], Formed from m-nitro-m-toluidine-
CgH3Me(N02)NH2 [1:3:6] by the action of cuprous
chloride upon the diazo- compound. Yellow
needles (from alcohol). Volatile with steam
(Honig, B. 20, 2419).
Chloro-nitro-tolnene CsH3(CH3) (CI) (NO^)
[1:2:4]. [65|°]. Formed by the action of PCI,
on p-nitro-toluene (Lellmann, B. 17, 534 ; ef.
WaohendorS, A. 185, 273). Colourless crystals.
V. sol. alcohol. Volatile with steam. On re-
duction it gives ohloro-f -toluidine [26°] (238°).
Chloro-di-nitro-toluene C^(CH3)C1(N02),
[1:4:3:6]. [48°]. Formed by nitration of ohloro-
nitro-toluene C,|H5(CH,)Cl(N0j) [1:4:3]. Long
white needles (Honig, B. 20, 2420).
Chloro-di-nitro-toluene 0,H,(CH3)(N02)2C1
[1:3?:67:4]. [76°]. Small yellow needles (from
CHLORO-OXETHOSE
ether). Formed by nitration of p-ohloro-toluene
with fuming HNO, (Goldsohmidt a. Honig, B.
19, 2439).
CUoro-di-nitro-tolnene C,Hj(CH,)Ca(NOj)j
[1:4:2:6]. [101°]. Formed by nitration of
p-ohloro-o-nitro-tolneneC„Hj(OHs)(N02)Cl[l:2:4J.
Long white needles (H5nig, B. 20, 2420).
Di-cWoro-nitro-toluene OaH2(OH,)CL(NO„).
[-U*]. (274°). S.G.iZ 1-455. From di-chloro-
toluene and fuming HNO, (Wroblewsky, A. 168,
212). Oil.
(iS)-I)i>chloro-nitro- toluene
C,Hj(CH,)Cl2(N0J [1:2:4:?]. [53°]. Formed by
the action of cono. HNO, on (a)-diohlorotoluene
(Seelig, A. 237, 163). Long needles (from methyl
alcohol).
(a) -Dl-chloro-di-nitro-tolnene
C^(CH,)Cl,(N02)j [1:2:3:?:?]. [122°]. Formed
by the action of HNO, (2 pts.) and H^SO,
(1 pt.) on (a)-di-chloro-toluene (10 pts.) (Seelig,
A. 237, 163). Needles (from methyl alcohol).
Yields on redaction a diamine which is appa-
rently meta.
(/3) -Di-chloro-di-nitro-tolnene
C,H(0H3)C1,.(N0J, [1:2:4:5:6]. [102°]. Formed
by the action of a mixture of HNO, (2 pts.) and
H2SO4 (1 pt.) on (J3)-chloro-toluene (10 pts.)
(SeeUg, A. 237, 163). Needles.
(a).Tri-clLloro-nitro-tolaene
0^(CH,)0l3(N0,). [92°]. S. (alcohol) 4-5 at
20° (Sohultz, A. 187, 277). Formed by dissolving
(a)-trichlorotoluene in cone. HNO, (Seelig, A.
237, 139 ; B. 18, 422 ; Beilstein a. Kuhlberg, A.
152, 240). Colourless plates (from alcohol).
(jS) -^-chloro-nitro-toluene
C.H(CHJCl,(NOj). [60°]. Formed by dissolving
(;8)-brichlorotoluene in. cone. HNO, (Seelig, A.
237, 140). Long yellow needles.
(a-) Iri-ohloro-di-nitro-toluene
C,(CH3)Cl3(N02)2. [227°]. Formed by warming
(a)-trichlorotoluene with a mixture of cone.
HNO, and H,S0, (Sohultz, A. 187, 280 ; Seelig,
A. 237, 140 ; B. 18, 422). White plates or needles ;
V. si. sol. alcohol. Beduced by tin and HCl to
tri-chloro-tolylene-p-diamine.
(;3-) Xri-chloro-di-nitro-toluene
0,(CH,)Ca,(N02)ij. [141°]. Formed by warming
(j3)-trichlorotoluene with a mixture of cono.
HNO, and HjSO, (Seelig, A. 237, 140; B. 18,
422). Light yellow needles, si. sol. alcohol.
Alcoholic NH, at 100° gives tri-chloro-nitro-
tolnidine [191°].
CHLOBO - NITBO . lOLTTENE SULFHONIC
ACID C^,ClNSOst.«. CA(CH,)01(N0,)(S0,H).
From Uquid (a)-chloro-nitro-toluene and. fuming
Bolphnrio acid (Wroblewsky, A. 168, 204).—
BaA', 4aq: needles, si. sol. water.
(a).TBI-GHLOBO-NIIBO-IOLTriDINE
C.(CH,)(NOj)Cl,(NHJ. [191°]. Formpdbythe
action of alcoholic NH, upon tri-chloro-di-nitro-
toluene [227°] (Seelig, B. 18, 423 ; A. 237, 140).
Orange-yellow needles (from alcohol).
(3)-Tri-chloro-nitro-toliiidine
C,(CH,)(NO,)Cl,mHj). [192°]. Formed by the
action of alcoholic NH, upon tri-ohloro-di-nitro-
toluene [141°] (Seelig, B. 18, 423). Orange-red
needles (from alcohol).
TBI • CHIOBO • DI - NITBO - DI - TOLTL-
ETHABTE OiA3<».(NO,),. [122°]. From
tri-cbloio-di-tolyl-etbane (C,H,),CH.CC1, and
101
Short
fuming HNO, (O. Fischer, B. 7, 1191).
yellowish prisms.
DI-<»-CHLOEO-liriTEO.XYLENE .
0,H,(NOs)(CHjCl)j. [45°]. From di-a-chloro-
p-xylene and fuming HNO, (Grimaux, Z. 1871,
598). Small plates. V. sol. ether.
Di-chloro-di-nitro-xylene Cj(OH,)jCl,(NOj)r
[225°]. Formed by nitrating di-chloro-j>-xylene
(Kluge, B. 18, 2098). Needles.
CHLOBO-OCTAIfE «. Ooitl ohlobidb.
Bi-chloro-ootane 0,H„Clji.e. C,H„.C0l2.Cn„
(c. 195°). From methyl hexyl ketone and PCI.
(Daohaner, A. 106, 271).
Di-chloro-ootane CaH„Cl,. (0. 199°). From
CI and the octylene from castor oil (D. ; c/.
Bfihal, Bl. [2] 47, 33).
Di-ohloro-octane CgHisClj. (0. 235°). Formed
by the action of CI on a mixture of octylene and
octane derived from paraffin (Thorpe a. Young,
A 165, 16).
CHLOEO-OCIYL ALCOHOL 0,H„C10. S.G.
2 1-003 ; Si -987, From octylene and very dilute
(I p.c.) aqueous HOCl (De Clermont, Z. 1870,
411). Oil.
CHLOBO-OOTYL-BENZENE 0,H4(C,H„)01i
(270°-27S°). Formed by chlorination of octyl-
benzene in presence of a trace of iodine. Oil.
y. sol. alcohol and ether, insol. water (Ahrens,
B. 19, 2719).
CHLOBO-OFIANIC ACID v. Opuma acid.
TEI-CHLOBO-OECIN (?) C,H,Cl,6j ».«.
C,(0H,)01,(0H)2. [59°]. From orcin and CI
(Sohunok, A. 54, 271) or HOI and KCIO, (De
Luynes, A. 130, 34). Slender needles.
Tri-chloro-orcin C,(CH,)Cl3(0H)j. [123°].
From the pentachloride, HI, and phosphorus
(Stenhouse, Tr. 1848, 88; Pr. 20, 72). Needles
(from water) or plates (from HOAc), m. sol. CS^,
m. sol. benzene, v. e. sol, alcohol and ether.
Volatile with steam. HIAq and phosphorus at
180° convert it into orcin. EjFeCy, oxidises it
to di-chloro-oxy-toluquinone [157°].
Fenta ■ oUoro -' orcin C,(CH3)C1,(0C1)2 or
CB(CH,)01(CyA- [120-5°]. According to Sten-
house, this, and not tri-chloro-orcin, is formed by
treating orcin with EClO, and HCl. Prisms
(from CS2). M. sol. CS^ and benzene, v. sol.
ether. Boiling water or alcohol decompose it
with formation of tri-chloro-orcin. Liberates
iodine from KI, and gives a pp. of AgCl with
AgNO, (Liebermann a. Dittler, A. 160, 265).
Compound C,(CH,)C1,(0C1)2HC10. [140-5°].
From orcin, calcium hypochlorite, and HOI.
Prisms (from benzene). V. sol. ether, sl. sol.
CSj. Converted by NH, into C.H5C1,N0 [187°]
(Stenhouse, B. 6, 575).
CHLOBO-OSUVLAIIYLINE v. Chlobo-ibo-
BPIYIi-ISOAMYL-OLTOXALIKE.
CHLOBO-OXALETHYLINE
V. ChIiOBO-ME-
THXIi-BTHTL-QIiTOXAMNE.
GHLOBO-OXALMEIHYLINE v. Chlobo.
MBrHYL-OLtOXAIilNE.
CHLOBO-OXALFBOFYIrllTE «. Chlobo-
«THTL-PB0PXI,-OLT0XAIilNB.
CHLOBO-OXETHOSE C,01,0. (210°). S.G.
u 1-652. Formed from alcoholic E2S and per-
chlorinated ether :
C<C1,„0 + ilS^S = 4KCU Sj + 0^01,0
(Malagnti, A- Oh. [3] 16, 19). Oil ; smells like
meadow-sweet. Has a sweet taste.
Beactims.—'i. Li sunlight it te-combinea
109
OHLORO-OXETHOSB,
Tfith chlorine 0,01,0 + 2Clj = C,Cl,„0.^2. Chlor-
ine water forms trichloracetic acid.
CHIOBO - OXIUIDO ■ ACETIC £THEB v.
COLOBO-ISOinTBOSO-AOEIIO BIHEB.
OHLOBO-OXIIfSOLE v. Oziin>oi.s.
CMoriMizindole oUoride v, Di-ohlobo-in-
ixos.
OHLOBO-DI-OXY-ACEIIC ACID Chlaro-gVy-
oxylie acid.
Diethyl derivative of the Nitrile
ClC(0Et)2GN. (o. 160°). Obtained, impure,
from CCl2(0Et)0N and NaOEt (Bauer, A. 229,
176). Polymerises.
Dipropyl derivative of the Nitrile
C10(0Pr),CN. (e. 201°). From C0l2(0Pr)CN
and NaOFr. Polymerises.
TETBA-CHLOBO - TEIBA. OXY • ADIFIC
ETHEK. Anhydride OioHigOl^O, t.0.
Et020.CClj.OO.OO.CClj.002Et.Oa»Z2/i-di-cfcZoro-
aeetic ether. [93°]. Formed by the action of
chlorine upon di-oxy-quinone-di-carboxylic ether.
Slightly greenish prisms. By hot alcoholic NH,
it is split up into 1 mol. of oxamide and 2 mols.
of di-ohloro-acetamide (Hantzsch a. Lcewy, B.
19, 26, 2386 ; Hantzsch a. Zeckendorf, B. 20,
1308).
OI-CHLOBO-SI-OXY-SI-AKISO-BENZEKE
V. Dl-CHi;.OBO-DI-AMII>0-BXI>BOQUINONE.
SI-CHLOBO - SI- OXY-AUIDO • FYBIDINE
C.H.C1AN, probably N<gjg^j=g°}>O.NH,..
IX-chloro-glutazine. [242°]. Formed in small
quantity, together with tri-chloro-oxy-amido-
pyridine, tri-chloro-amido-pyridine, and tetra-
chloro-amido-pyridine, by heating glutazine with
FClj (6 or 7 pts.). Short flat colourless needles.
SI. sol. hot water and alcohol. Dissolves readily
in aqueous acids and alkalis. Combines with
bromine (Stokes a. Peohmann, B. 19, 2710;
Am. 8, 391).
IH-ethyl derivative N<^|^g*|;^Q^OJ?a,:
[98°]. Long colonrless needles. Beadily sub-
lime. Volatile with steam. V. sol. alcohol and
ether, insol. water. Formed together with the
mono-ethyl derivative by heating tetra-chloro-
amido-pyridine with an excess of sodium ethyl-
ale at 190° for B or 4 hours.
Mono-ethyl derivatioe
^<ci0Et):C0^°-N^' [162°]. Flat needles.
Sublimable. Not volatile with steam. V. sol.
alcohol and ether, sL sol. hot water. Dissolves
in alkalis, bat not in dilute acids. It is also
formed by heating tri-chloro-oxy-amido-pyridine
with sodium ethylate.— A'Na : glistening rhom-
bic tables (Stokes a. Pechmann, B. 19, 2710;
Am. 8, 896).
TBI - OHLOBO ■ OXT - AUIDO • FYBIDINE
OACMI^ probably N^gg^^gg^OJJH,
[282°]. Formed, together with an equal quan-
tity of tetra-chloro-amido-pyridine and small
quantities of di-ohloro-di-oxy-amido-pyridine
and tri-ohloro-amido-pyridine, by heating gluta-
zine with PCI, (6 to 7 pts.). Flat colourless
needles, Sublimable. V. sol. hot water, nearly
insol. oold, m. aol. hot alcohol, si. sol. cold, si.
sol. ether and benzene, insol. ligroin. Mono-
basic acid, decomposes soluble carbonates. Dig-
solves in oone. HCS or cone. H,SO„ but is re-
precipitated on dilution. — A'Ha scaq : needles, a.
sol. oold water.
Ethyl derivative N<gg^)=gg}>O.NH,:
[82°]. Colourlessueedles. Very volatile with steam.
Peculiar odour. V. sol. alcohol, ether, etc.
Formed by ethylation of the above, or by heat-
ing tetra-chloro-amido-pyridine with sodium
ethylate (Stokes a. Peohmann, B. 19, 2710 ; Am.
8 892).
' 7-CHI0B0-a-0XY-AIir6ELIC ACID 0,H,010,
t.e.OHj.0Cl:0H.CH(OH).CO,H. [116°]. From
tri-ohloro-oxy-valeric acid, zinc, and HCl (Pin-
ner a. Bischoff, A. 179, 100 ; Pinner a. Elein, B.
11, 1496). V. sol. water, alcohol, and ether,
si. sol. OS2. Combines with Br. PCl^ gives
0H3.0C1:CH.0H01.C0C1. — ZnA'y — OuA'^ —
AgA' : needles, m. sol. cold water.
Ethyl ether mA!. (230°).
Isobutyl ether OHJ^lA.'. (0. 238°).
CHLOBO-DI-OXY-AKTHBAaTriNONE
0„H,0104. Chloro-aKzarim. [244°-248°]. Pre-
pared by the action of 01 on a cold solution of
alizarin in OS, (Diehl, B. 11, 187). Sublimes in
red needles. Sol. boiling, si. sol. cold, wa1;er.
Di-ohloro-di-ozy-anthraqninone OifEtgOl^O,.
Di-chloro-aKzarin. [20S°-210°]. Prepared by
the action of SbOl, on alizarin (Diehl, B. 11, 188).
Sublimes in beautiful orange-red spikes. Com-
bines with mordants readily, the colours resem-
bling those produced by nitro-alizarin.
Tetra-chloro-di-ozy-anthraquinone
C,4H^^OH)2C1^0^. Tetra-chhro-alizarm. [0.
260°]. Prepared by the action of SbCl, on
alizarin (Diehl, B. 11, 189). Further action of
SbOlj forms 0,C1„ CjCl„ 001,, and COj. Reddish-
brown crystalline powder. Does not combine
with mordants.
CHIOBO-OXY-BENZAUIDE v. Amidb or
CBL0B0-OS7-BENZ0IC AOID.
DI-CHLOBO-TEIBA-OXY-BEirZEir£
0,Gl2(0H)4. SydrochloraniliB acid. From di-
ohloro-di-oxy-quiuone by reduction with aqueous
SO2 at 100°, or with tin and HCl (Koch, Z. 1868,
203; Oraebe, A. 146, 32). Needles. Y. sol.
water, alcohol, and ether. Oxidised by moist air
into di-ohloro-di-oxyquinone (ohloranilic acid).
Tetra-aeetyl derivative C.CUOAc),.
[235°].
CHLOBO-o-OXY-BENZOIC ACID C,H,C10,
i^. CAC!1(0H).C02H [5:2:1]. CKIaro-taUcyUe
add. Mol. w. 175^. [172-5°] (H. a. B.); [168°]
(V.). S. -09 at 20° ; 1-25 at 100°.
Fopnation.—!. By passing the calculated
quantity of chlorine into salicylic acid dissolved
in a large quantity of CSj (Hubner a. Brenken,
B. 6, 174 ; cf. Oahours, A. Ch. [3] 13, 106), or in
HOAo (Smith, B. 11, 1226 ; MarahaU, A. Ph. S.
17, 476).— 2. From (6,2,l)-chloro-amido-benzoio
acid by displacement of NH, by OH through the
diazo- reaction (Hiibner a. Weiss, B. 6, 176). —
8. From (2,5,l)-oxy-amido-benzoio acid by dis-
placement of NH, by 01 (Schmitt, Z. 1864, 321 ;
Beilstein, B. 8, 816).— 4. Fromp-ohloro-phenol,
CCI4, and alcoholic EOH (Hasse, B. 16, 2196).—
6. From C.H,Cl(ONa) [1:4] and 00, at ISO"
(Vamholt, J. pr. [2] 36, 20).
JPtoperties. — Needles (from water). V. sol.
alcohol, ether, and benzene. Fe^Ol, colours its
aqueous solution red.
CHLORO-OXY-BUTYRIO AOID.
103
Baits. -NaA'.— LLA. 2aci.— KA'.— BaA's3aq.
CaA's 3aq.— PbA'j.— CnAV— AgA'.
Methyl ether MeA'. [48°]. (249°). Needles.
Ethyl ether EtA'. [110°]. Needles.
Acetyl derivativa CaH,CI(OAo).CO^
[149°].
Amide OACl(OH)(CONHj) [223"].
Chloro-ozy-beiuoio acid 0,H301(0H).002H
[3:2:1]. [178°]. S. -08 at 3-5°. From [2:1]
CeH^OHONa) and CO^ at 150° (Vamholt, J.pr.
[2] 36, 22). Long needles, volatile with steam,
maybe sublimed. Y. sol. alcohol and chloro-
form. Fe,Cl, gives a violet colour. — NaA'.—
BaA', Baq.
Methyl ether MeA'. [83°]. (260°). Needles.
Chloro-ozy-benzoio acid C«H,C1(0H).C02H
[4:2:1]. [207°]. From CeH,01(0Na) [1:3] by
treatment with CO, and heating the product,
C,H4Ca(0.C0^a) at 150° (Vamholt, J. pr. [2]
36,28). Also from 0,H,(C0jH)(N0,)01 [1:2:4] by
reduction, diazotisation, and boiling with water.
Small needles, volatile with steam, may be sub-
limed. Y. sol. alcohol and chloroform, si. sol.
water. Fe,Cl, gives a violet colour.
Chloro-p-ozy-benzoic acid CsB3Cl(0H)C02H
[8:4:1]. [188°] (P.) ; [170°] (L.). 8. -37 at o. 15°.
Formation. — 1. From silver p-oxy-benzoate
and CI (Peltzer, A. 146, 284; Z. [2] 5, 225).—
2. Fromjv-oxy-benzoio acid and SbCl, (Lossner,
J. pr. [^ 13, 432).— 3. Prom o-chlorophenol,
EOH, CCI4 and alcohol at 130° (Basse, B. 10,
8192).
Properties. — Silky needles ; v. Bol. hot water,
T. e. sol. alcohol and ether. May be sublimed.
Fejyi, gives a reddish-brown pp. in neutral
solutions.
• Salt.— BaA'^eaq.
Methyl derivative 0,H,Cl(OMe).CO^.
Chloro-amisic acid. [215°]. White glistening
scales. Formed by oxidation of the methyl-
ether of ohloro-2)-oresol. — A'Ag; sparingly
soluble pointed plates.— A'jBa 3|aq : thin rect-
angular tables, soluble in hot water (Sohall a.
DraUe, J5. 17, 2529).
Chloro-p-oxy-benzoic acid. Methyl deri-
vative OaH,Cl(OMe)C02H. Ghloro-amisie acid.
[176°] (0.) ; [180°] (L.). From anisic acid and
CI (Laurent, B. J. 23, 421;- Cahoura, A. 56,
812). Prisms or needles. May be sublimed.
Insol. water, v. sol. alcohol and ether. Probably
identical with the preceding.
I)i-chloro-OM>xy-beszoic aeid
0ACli(OH)(CO2H). Di-ehloro-saUeyUe add.
[214°]. Prepared by leading CI into an acetic
acid solution of salicylic acid (Smith, B. 11,
1225 ; A. Ph. 8. 17, 486 ; cf. Cahours, A. Ch.
[3] 13, 106). Formed also by heating salicylic
acid (1 moL) with SbCl, (8J mols.) (Lossner,
J.pr. [2] 13, 429). Smiul prisms (from dilute
alcohol). SL sol. hot water. May be sublimed.
Salts.— A'gBa 3aq. Long needles, insol. cold
water.— A'K: soluble needles.— AUa : large
soluble needles.— A'^g: small soluble oiystals.
A'aPb. Lisolublepp.
Methyl ether: [142°]; needlei.
Ethyl ether: [47°]; needles.
Iso-butyl ether: [188°]; small needles.
Amide: [209°] ; needles.
Methyl derivative C,HjCls(OMe)00^
n04°]. From metbyl-salicylio acid and CI
(Procter, J. Ph. [3] 3, 275 ; Cahours, A. Ch. [3]
10,343). Needles.
Ethyl derivative CeH2C140Et)C02H.
Needles (Cahours, A. Ch. [3] 27, 461). .
Di-chloro-p-oz7-benzoio acid
0,Hj01j(0H).C0^ [156° unoor.]. Formed by
oxidation of di-ohloro-^-cresol with CrO, in
acetic acid (Clans a. Biemann, B. 16, 1600).
Sublimable. Long white needles. Sol. alcohol,
ether, and hot water, nearly insol. cold water.-^
A'Na" : small needles, sol. water and alcohol.
Di-cUoro-p-ozy-benzoic acid. Methyl deri-
vative C,H2Cl2(OMe).C02H. Di-chloro-anisie
add [196°]. Formed, together with tetra-ohloro-
quinone, by treating anisic acid with HCl and
ECIO3 (Beinecke, Bl. [2] 7, 177). Large needles
(from alcohol) ; insol. water.
CHLOEO-o-OXY-BENZOIC ALDEHYDE
CjHsClOj *.«. CaH3Cl(0H).CH0. From salicylic
aldehyde and CI (Pina, A. 30, 169 ; Ldwig, B. J.
20, 811). Tables (from alcohol). Insol. water.
Combines with NaHSO, (Bertagnini, A. 85, 196).
Ba(0.C,H3Cl.CH0)j : powder. With NH, it
forms yellow needles of (C,HaCl(0H).CH)3N,
(Piria, A. Ch. [2] 69, 309).
Chloro-p-oxy-benzoic aldehyde
CeH3Cl(0H).0H0. [149°]. Fromp-oxy-benzoio
aldehyde and dry chlorine (Herzfeld, B. 10,
2196). Silky needles; v. sol. water, alcohol,
and ether. Absorbs NU, (2 mols.). Fe^Cl, gives
a violet colour.
CHLORO-OXT-BENZYL ALCOHOL
0,H,C10j i.e. C,H,Gl(OH).CHjOH, Ohloro.
saUgemn. From chloro-salicin by hydrolysis by
emulsin (Piria, A. 56, '60). Trimetrio plates
(from water). Turned blue by FcjOl,.
a-CHLOEO-0-OXY-B1TIYBIO ACID
CH,.CH(OH).CH01.COjH. [63°]. Prepared by
addition of hypochlorous aoid (ClOH) to (a)-
crotonio aoid (Melikoff, B. 16, 1270; Bl. [2] 41,
311; 47, 167; PavolofE,BZ. [2] 43, 115). Needles.
Y. sol. water.
Beaetions. — 1. By the action of alcoholic
EOH it gives propylene-ozide-carboxylio {{ff)-
methyl-glycidio) aoid /\ [84°]
CH3.CH.CH.COjH
whence HCl forms the following acid. — 2. Heat-
ing with HjSO, givM a.ehloro-crotonio aoid
whence zino and HjSO, produce orotonic acid.-^
3. Heating with HCl gives OHa.CHCl.CHCl.COiH
[69°] (?) whence alcoholic EOH gives rise to
CH3.CH:CCLC02H [98°].
Salts.— A'jZn: extremely soluble tables. —
A'oCa: easily soluble amorphous powder. ;
Chloro-oxy-butyrio acid 03H.C1(0H).C0,H.
Formation. — 1. By the addition of hypo-
chlorous aoid (ClOH) to iso-crotonic acid.— 2.
By the addition of HOI to propylene oxide
oarboxylio acid.
Properties. — ^Long prisms. V. sol. water,
alcohol and ether. By the action of alcoholie
EOH it gives bntyro-glycidic aoid.
Salts.— A':Ca4aq: easily soluble micro-
Mopio crystals. — A'sZn 2aq : trimetrio crystals,
si. sol. oold water (Melikofi, B. 16, 1268).
dUoro-ozy-bntyric acid
0H2C1.CH(0H).CH2.C0,H. Formed at the same
time as the 'preceding by the onion of HOCl
Irith iaocrotonio aoid (Melikofi, /. B. 16, 541).
104
OHLORO-OXY-BOTYRIO ACID.
Liqnid. Converted by alcoholic KOH into
propylene oxide carbozylic ((7)-methyl-glycidic)
add /\
CH, . OH.CHrCOjH
CIiloro-oxy-iBobutyric acid
CH,Cl.CMe(OH).GO^. Ghloro-aeetonie acid.
[107°]. (c.233°).
Formation. — 1. From ohlpro-aoetone by
treatment with HON and saponification of the
resulting nitrile (Bisohoff, B. S, 865).— 2. From
methaorylic acid and EOCI (Melikoff, Bl. [2]
41, 311; 43, 116).— 3. From propylene oxide
oorboxyUo acid ((a)- methyl -glycidio acid)
O
^«^^ and cono. HCl (M.).
C!HrC(CO^.CH,
Properties. — ^Long prisms (from ether) ; v.
80L water. Converted by alcoholic KOH into
propylene-oxide carbozylic acid.
Salts.— CaA', 2aq.— ZnA',.
Nitrile CHjCl.CMe(OH).CN. Fromchloro-
acetone, by boiling with alcohol and cone,
aqueons HCN (B^. Oil. Split up by distilla-
tion into HCy and! C,'BfihO.
Cbloro-ozy-bntyric acid. Nitrile
C,H,C1N0,. From epichlorhydrin and anhy-
drous HCy at 140° (Hormaim, B. 12, 23).
Liquid, ▼. sol. water. Dilute HCI forms a liquid
chloro-ozy-hntyrio acid.
Di-chloro-oxy-isobatyric acid
CHClj.CMe(OH).COJH. [83°]. From its nitrile
and HClAq at 100° (BischoS, B. 8. 1334).
Prisms. — AgA'.
Ethyl ether BtA.'. (c. 212°).
Nitrile CHCl,.CMe(OH).CN. From di-
cbloro-acetone and cone, aqueous HCy (B.).
Liquid. Split up by distillation or by alkalis
into HCy and di-ohloro-acetone. Aqueous KGy
forms crystalline (C,H«C1,0)2HCN (Glutz a.
Fischer, J. pr. [2] 4, 52).
Oi-chloro-oxy-isobutyrio acid
(CH,Cl),C(OH).COiH. [92^.
Obtained by boiling its nitrile for 12 hours with
cone. HClAq (Orimaux a. Adam, Bl. [2] 3G, 20).
Deliquescent tables, t. boL alcohol and ether.
KCN converts it into a nitrile of citric acid
(OH,CN)jC(OH).CO^
Ethyl ether EtA'. (c. 228°). From a-
di-ohloruydrin, chloroformic ether, and sodium
amalgam (Kelly, B. 11, 2222). Cone. KOH
produces glycerin.
. Nitrile (CHjCl)jC(OH).CN. From «-di-
chloro-acetone (50 g.) by digesting with HCy
(20 g.), a little water, and alcohol 8 o.c.
Tn-chloro-ozy-isobutyric acid
CCl,.CMe(0H).C02H. From tri-chloro-acetone
by successive treatment with HCy and HCl
(BischoS, B. 8, 1339). Syrup.
TBI-CHLOSO-DI-OZY-SI-CTKYL-ETHANE
OsjHbCIsO, ie. CCl,.CH(C,„H,sOH)y [194°].
From thymol (2 mol.), ohldral (1 mol.) and
cono. H,SO« diluted with HOAc (Jaeger, B. 7,
1197 ; O. J. 31, 262). Monoclinic needles (con-
taining HOEt). Insol. water. Alcohol and
zinc -dust form CH,CH(OuH,20H)2 and
CH,:C(0,ja,jOH),.
CHIOBO -OXY-ETHTL.AHIDO ■ PHENYL-
ETHAKE CCl,.CH(0H).C^4NHEt. [98°]. From
chloral hydrate and ethyl-aniline (Boessneck, B,
91, 783).
Nitrosamine C,„H„C1,N(N0) [138°].
(Fy. S:l:2)-CHL0E0-0XY-ETHYL.ftUIN0L.
,C(OH):CBt
INE GMjC I . [248°]. Formed by
\k=^6ci
the action of FCl, upon aniline ethyl-malonate
under benzene. Colourless needles. M. soL
alcohol (Kiliani, B. 20, 1235).
TBI-CHLOBO-OXY-ETHyi.-STrCCINIC ACID
Lactone. CC1,.CH.CH(C0,H).CH2.C0.0. Tri-
chloro-methyl-paraconic acid. [97°]. From
chloral, sodium succinate and AcjO (Fittig, B.
20, 3179). Converted by baryta into barium
isocitrate.
DI-CHLOEO-DI-OXY-HEXANE C.H.^CljOj
i.e. CH,01.CH{0H).CH2.CH2.CH(0H).CH2C1. (?)
S.G. Z 1-4. From diallyl and aqueous HOCl in
the cold (Henry, B. 7, 415 ; Z. [2] 6, 479). Oil.
Potash converts it into diallyl dioxide whence
baryta-water produces the anhydride of tetra-
oxy-hexane C^H, A (Przibytek, Bl. [2] 45, 248).
Si-cbloro-tetra-ozy-hezane v. Mannitis.
SI-CHLOBO-SI-OXY-HEXINOIC ACID
6„H„01A t.e.
CH,Cl.C(OH):CCl.C(OH):CH.COjH (7). Di-
chloro-di-oxy-amemyl carboxylie acid. [177°].
From the following by sodium amalgam
(Hantzsch, B. 20, 2789). Lustrous prisms.
Cono. aqueous NaOH forms CaHjClOiNaj 6aq
which crystallises in canary- yellow needles and
is converted by HCl into CsHiClOj [97°], which
forms a salt NaA' 3aq.— NH,A'. [185°].
Acetyl derivative [134°].
Tri-chloro-di-ozy-hezinoic acid CgHjCljO,
t.e, CH,CI.C(OH):0Cl.C(0H):CCl.COjH (?)
[177°]. Formed, together with tri-ohloro-phe-
nol, by passing chlorine into an alkaline solu-
tion of phenol (Hantzsch, B. 20, 2789). The
yield is 60 p.o. Needles (from water) ; or monq-
olinio crystals (containing 4aq). Decomposed
by cone, aqueous KOH. — NH,A' 2aq : trimetrio
prisms, si. sol. water.
Methyl ether MeA'. [126°].
Hi - acetyl derivative CgHjAc^CliO^
[188°-192°].
CHLOBO-SI-OXY-INSONAPHTHENE
,C(OH). „o
CaH,<^ I ^CO or C^^<^^^C(OH). Phe.
nyUne-chloro-oxy-aeetylene^ketone. [114°].
Formed by the action of acids or alkalis upon
/
C(OH)
\.r
the amides C.H,C I >C:NR or
\(JC1 /
CbH4<^„^0:NHR, which are obtained by the
action of amines upon di-chloro-oxy-indonaph>
thene (j. v.), C»Hj.<'j,qj^CC1. It is reconverted
into these amides'by the action of amines (Zincke,
B. 20, 1271). Whiteglistening plates (from dilute
alcohol), or small compact crystals (from petro-
leum-spirit). Dissolves in aqueous alkalis with
a red colour. By PCI,. it is converted into the
,OClv
compound CJi^^ | \C0.
CHLORO>]>I-OXY-METHTL>PURIN.
{In. 3:l:2)-Si-oUoro-ozy-indonap1ithena
.OClv
C.H,<M \aO. [125"]. Formed by the BOtion
ol PCI, upon ohloro-di-ozy-indonaphthene
C.H,<;;^^^)>CO. OUstoning plateg (from di-
lute alcohol) (Zinoke, B. 20, 1272).
{In. 3:2:l)-I)i-oUoro-ozy-indonaphthene
O^t^QQ^Od. Phenylene-di-chloro-aceiyUne-
ketone. [90°]. Formed by oxidation of the car-
/0(OH).COjH
bozylio acid OfiX \ (from di-chloro-
\CC1:CC1
. (i3)-naphthoqmnone) with CrO,. Small yellow or
long glistening golden needles. Very volatile
with steam. It has some of the characteristics
of a qninone. With aromatic bases it forms
colonred compounds. Beaots with hydroxyl-
amine and with phenylhydrazine. With halogens
it yields colourless addition-products. It is not
affected by SnCL, or by PCI,. *
Methyl. amide C;B,<QQ^C.NHMe or
/C(OH).
C^,< I >C:NMe : [195^; long dark-red
\CC1 /
needles, sol. hot iJcohol.and acetio acid, si. soL
benzene.
Di-methyl-amide CaH4:03C10.KMe2 :
[140°]; long red needles or thick tables. —
B'jHjCljPtCl, : yellow crystalline pp.
Anilide CaH^rCjClCNHPh : [204'*]; slender
deep-red needles; dissolved in warm dilute al-
kalis without decomposition.
Oxim CeHi<;Q|^°^)^C01 : [120°]; long
yellow needles ; t. sol. warm alcohol and acetio
acid (Zinoke, B. 20, 1265).
Di-chloride C.H,<;^Qj^CClp [108°].
Converted by aqueous NaOH into tri-ohloro-
vinyl-benzoic acid [163°] (Zincke a FrShlich, B.
20, 2053).
Di-bromide C^,<cQjB,>CClBr. [114°],
and, when rapidly heated, [c. 128*^. Converted
by aqueous NaOH into di-chloro-bromo-vinyl-
benzoio acid CClBr:CC1.0,Hj.C0jH [174°].
Chloro-ozy-indonaphthalene dichloride
C„H,<°!^Qj>CClr 169°]- From the dihydride
of tri-chloro-di-ozy-indonaphthene carbozylio
acid and dilute CrO,Aq (Zincke, B. 20, 2890).
Thick needles (from alcohol). Converted by al-
kalis into di-chloro-vinyl-benzoio acid.
OI-CHLOBO-SI-OXY-INSONAPHXBENE
C(0H)C02H
CABBOXTUO ACID OJBi^fiCi, [139°].
CO
Formed by dissolving the hydrate of tetra-ohloro-
(0) -naphthoquinone in dilute NajCOjAq and ppg.
with an acid (Zinoke, B. 21, 497). Thick needles
(containing aq) (from water). V. sol. alcohol,
benzene, and HOAc. CrO, gives C.H,<;pQ>CCl,
[124°].
Methyl ether MeA' [124°] large obhque
•rystals.
106
[126°].
Acetyl derivative Oii^ikoCljOf
Prisms.
Tri-chloro-ozy-indonaphtliene earbozylia
acid. Dihydride 0,M,ClLO.i^.
/ C(OH).CO^
\Q^(;iy>0(Slv From the dihydride of di-
, CO.CO
ohloro-(0)-naphthoquinoneC,H4^ I and
CHCl.CClj
dilute NaOH (Zinoke a. Frdhliob, B. 20, 2894).
Liquid.
Methyl ether Me\'. [160°].
Acetyl derivative of the methyl ether
OioHsMeAcGljO,. [116°J.
SI-CHLOBO-OXY-UEIHANE SUIfEimC
ACID CCL,(0H)S02H. Unstable deliquescent
needles.
Salt.— A'E. Trimetrio plates. From ECy
and aqueous or alcoholic trichloro-methane sul-
phochloride {a. v.) : CCI3.SO0CI + KCy + H,0
= 0y01 + HCUC01s(0H).S0,K. Boiled with
potash it forms EGl and E^SO, (Loew, Z. 1868,
618 ; MoGowan, J.pr. [2] 30, 288).
DI-CHLOBO-OXY-MEIHAHE SULFHONIC
ACID.
CAZortdt.— ■CCl2(OH)SO,CLFromFGl^and
CClj(OH)SO,E (MoGowan, J.pr. [2] 30, 289).
Anilide.— CC\i(OB.)aO,TH'BhB.. Rhombo-
hedra. From aniline and the above chloride.
TBI -01 - CHLOBO - a-OXY- 1IETH7I.-A1IID0-
PHENYL - ETHANE CCl,.CH(OH)C,H<NHMe.
[112°]. From chloral hydrate and methyl-ani-
line (Boessneck, B. 21, 782).
Nitrosamine CCl,.CH(OH).C,H,NMeNO.
[118°]. Needles.
Tri-n-chloro-a-ozy-di-methyl-amido-benzene
CCl3.CH(0H).C,H«NMe,. Fotined by condensa-
tion of chloral hydrate with di-methyl-aniline in
presence of ZnCIj (EnSfler a. Boessneck, B. 20,
3193).
{Py. 3:1)-CHL0B0-0XY.(B. 4)-1IIETHYIh
{Py. 2)-EIHYL-(l1TIN0LINE
X!(0H) = CEt
O^Me< I
•^ \N===CC1-
a-Chloro-p.ethyl.y.oiiy.o-tol'uquinolme.
[225°]. Formed by the action of PCI, upon a-
toluidine ethyl-malonate under benzene. Silky
needles (from ^cohol) (Eiliani, B. 20, 1233).
CHLOBO-DI-OXY-MEXHYI-PUBIN.
Methyl ethyl derivative
C5N,(CH,)(0Me)(0Et)Cl (7) Ethoxy-chloro-oxy-
di-methyl-pwrin. [160°]. Granular crystals.
Formed by the action of a solution of KaOH in
60 pji. alcohol on di-chloro-methozy-methyl-
purin.' By HCl at 130° it is converted into tri-
oxy-di-methyl-pnrin (di-methyl-urio acid). By
HI it is reduced to di-ozy-di-methyl-purin
(Fischer.JS. 17, 335).
Di-ethyl derivative C,(CH3)(OEt)2ClN4.
Formed by heating tri-chloro-methyl-purin with
alcoholic NaOH (Fischer, JB. 17, 332). Fine
felted needles. Heated with HCl at 130° it
gives methyl-uric acid (tri-oxy-methyl-purin).
Di-chloro-ozy-methyl-pniin C,H,0N,Cl2 i.e.
N=CC1
C.(CHJ(OH)CljN, probably OIC C— NH
N=C— NMi
Nco
lOfl
CnLORO-DI-OXY-METHYL-PURIN.
[274°]. Obtained by beating methyl-urie acid
with POl, and POClj at 130° (Fischer, B. 17, 330,
1786). Fine white needles. Very stable body,
volatilising without decomposition and not being
attacked by HNO, or by KCIO, and HCl. By
HI it is reduced to ozy-methyl-purin.
Oi'-obloro-ozy-di-methyl-parin CHgOGl^N,
N=CC1
A-,
010 0— NMev or C,N,(CH,)(OMe)Clj
II II >co
N— C-NMe^
tl83°]. Di-chUrro-methoxy-mefhyl-pwrin. Formed
by heating the lead compound of di-chloro-ozy-
methyl-purin ^vith methyl iodide (Fischer, B.
17, 334, 1787). Fine colourless needles. Insol.
alkalis. By HI it is reduced to methozy-methyl-
pnrin.
(Py. 4, 3) ■ CHLOBO-OXT - IB. 2) . METHYL-
QiriNOLIIfE C,H,CH,N0C1 Lt.
CMe:CH.G.CH:CH
I II I • Ohloro- methyl -pseudocar-
CH : CH.C:N01.C0
bostyril. [121°]. Formed by treating a solu-
tion of (B. 2) methylquinoline in borie acid with
bleaching powder solution (Emhom a. Lauch,
A. 243, 3S8). White needles (from acetic ether).
BeactUms.—l. Boiled with NaOHAq {B. 2)-
methyl-carbostyril [228°] is obtained. — 2. Yields
an isomeride [281°] on boiling with alcohol.
(Pv. l,3,4)-Cliloro-oxy-]iiethyl-qmnoline
y OChCH
0«H/v I [117-6°]. From (7)-ohloro-oar-
>NMe.CO
bostyril, Mel, and alcoholio NaOH (Friedliinder
a. Miiller, B. 20, 2009). Hair-like needles (from
MeOH).
(Py.)-Chloro-di-ox7.(£. 2)-methyl-quinoline
Di-ethyl derivative C,H,(€H,)NC,Cl(0Et)2.
[71°]. Formed by heating {Py. l:2:3)-tri-chloro-
(B. 2)-methyl-quinoIinewith a solution of sodium
in absolute alcohol at 100°-130°. Long colourless
needles (Biigheimer a. Hoffmann, B. 18, 2982).
{Py. 2:3:1) -Chloro-di-oz7-(3. 4) -methyl -
quinoline 0,,HgNCl,0 tA
.C(OH):OC1
CA(CH,)< I or
N N = C(OH)
.C(0H):CC1
OJB.,{CS,)^ I . Ohloro-oxy-tolucarbo-
\ NH— CO
stynl. [277"]. Formed by heating {Py. 2:3:1)-
di-chloro-ozy-(£. 4)- methyl -quinoliJae with
dilute HCl at 160°. Large plates or tables. Y.
sol. acetic acid, si. sol. alcohol, insol. water.
Dissolves in acids and alkalis (Biigheimer a.
Hoffmann, B. 18, 2986).
{Py. l)-Chloro-(£. 2)-ozy-methyi-qainoUne.
Methyl derivative C(OMe):GH.C.CCl.CH
I II I
CH=CH.O.N.CMe
[100°]. (o. 298°). From the corresponding
C^«Me(OH)(OMe)N by FOCI, (Conrad a. Lim-
pach, B. 21, 1649). Silky prisms.
{Py. 1:2:8) - Oi - chloro ■ ozy - {B. 2) - methyl -
quinoline C„^,NCLO (.e.
'CC1:CC1 .CC1:601
C.H.(CH.)< I orC.H3(CH,)<; [ .
-'\n=c(oh) \nh.co
Di-cKloro-toluearhostyril. [292°]. Obtained by
beating (Py.l;2;3)-tri-ohloro-(£.2)-methyl-quino-
line with dilute HCl at 180°. Small oryatals. Sol.
benzene and acetic acid, si. sol. alcohol and ether,
insol. water. Has both weak basic and weak acid
propWties (Biigheioiet a. Hoffmann, B. 18,
{Py. 1:2:8)- Di - chloro • oxy - {B. 4) - metliyl •
>CC1:CC1
quinoline C,H,(CH,)< | . iM-cfcJoro-
NN : C(OH)
toVucarbostyril. [288°]. Formed by heating
{Py. l:2:3)-tri-chloro-(B. 4)-methyl-quinoline
with dilute HCl at 180°. Small white needles
(from acetic acid). Sublimes in needles. SI.
sol. alcohol, insol. water (Bugheimer a. Hoff-
mann, £. 18, 2985).
{Py. 2:3:1) -Di - chloro - ozy - {B. 4) - methyl-
.C(0H):CC1
quinoline O.H,(CH.)< | . [245°].
\n=^^oi
Formed by the action of PCI, upon the acid
malonate of o-toluidine in presence of cold
benzene. Needles. SI. sol. alcohol and acetic
acid, nearly ^nsol. water. Decomposes alka-
line carbonates (Bugheimer a. Hoffmann, B. 18,
2983).
(P^.2:4:3) - CHLGBO-OXY-KETHYL-ISO-
.CH:CC1
QUINOIINE OiAClNO i.e. C,H4< | .
^CO.NMe
[112°]. Formed by methylation of {Py. 2:4)-
chloro-oxy-isoquinoline [220°]. Long needles.
Y. sol. ether, benzene, chloroform, and hot alco-
hol (Gabriel, B. 19, 2361).
{Py. 4:2:l)-ChIoro-ozy-methyl-iBoqninoIine
nM^.nir\TT\ xCHMe.CO
c.H<ca;r^^'»o.<cci=ilf-^'''°^'
Needles (from acetic acid). Sol. aqueous alkali*.
Formed as a by-product of the reaction of
POCl, upon the imide of phenyl-methyl-acetic-o-
,CHMe— CO
carbozylic aoid OMJ^ \ (Gabriel, J3.
\C0 — NH
20, 2504).
CHL0B0-OXY-(a)-NAPHTH0QUINON£
CuHjClOa i.e. C|„H,01(0H)0j. CMoro-naph^
thaUc acid, [above 200°]. Formed by boiling
chloro-naphthalene tetrachloride with HNO,
(Laurent, A. 35, 298). Formed also by boiling
di-chloro-naphthoquinone with alcoholic EOH
(Graebe, A. 149, 14 ; P. a. E. Depouilly, Bl. [2]
4, 10) ; and by boiling the alkylamides of
chloro-(a)-naphthoquinone with acids or aqueous
EOH. Yellow needles ; may be sublimed. Insol.
water, m. sol. alcohol and ether. HNO, oxidises
it to phthalio and oxalic acids. Turned red by
alkalis. Distillation with PCI, gives penta-
chloro-naphthalene.
Salts. — ECjgHjClO^zaq: crimson needles. —
BaA'2 aq : silky orange needles.
>C0 . C(OH)
Imide C,H«< II . [0. 260°].
\C(NH).CC1
Formed by the action of alcoholio NH, upon a
hot alcoholic solution of ohloro-(^)-naphtho-
quinone. Dark metallic plates. SI. sol. alcohol
and acetic aoid. Dissolves in dilute NaOH with
a_ dark- violet colour. Long boiling with HCl
yields chloro-ozy-(a)-naphthoquino&e (Zincke,
£.19,2499).
CHLORO-OXT-PHENYL-CARBAMIC AOID.
107
00 0(0H)
Anilide O.H,<; || . [2580].
^0(NPh).CCl
Dark metallic plates. Formed by the action of
aniline upon a hot alcoholic solution of ohloro-
(;3)-naphthoquinone /Zinoke, B. 19, 2499).
(■ 0 ')-Chloro-ox7-(a)-naphtho4ainone
0,^Cl(OH)Oj. [205" unoor.]. Formed by
boiling (* j3 ') - di - ohloro - (a) - naphthoquinone
O.H,Ca<^o!cH ^^ alkalis. Felted yellow
needles. V. sol. alcohol, ether, &c., si. soL
water. Sublimable. The alkali-salts are t. sol.
water with a deep red colour; the Oa and Ba
salts are sparingly soluble. — A'^Cu : insoluble
red pp. — ^A'^b : yellowish red pp.
Anili'de OtJ}fil{T!(B.Ph)0^: [155° unoor.].
Formed by boiling an alcoholic solution of
(' $ ')-di-ohloro-naphthoquinone with aniline.
Dark violet orystals. Y. sol. acetic acid, si. sol.
alcohoL
o-roIaidaCi^jOipSHOjHJO: [175° un-
oor.].
p.Toluide C,„H4C1(NHC,H,)0, : [164° un-
WTj (Claus a. Muller, B. 18, 3074).
(lluora-ozy-(/3)-naphthoquinone. Ethyl de-
JOO— 00
rivativt Ofi£ \ . [149°]. From
3(0Et):CCl
OO.CCl,
teira-ohloro-(a)-naphthol 0J3.,<C | and al
ACC1:C01
cohoUo KOH (Zincke, B. 21, 1027). Orange
Propyl derivative 0„H<C10j(0Pr). [190°].
Formed in like manner, using propyl alcohol.
Tri:-chloro-ozy-(a)-naplithociuinone
C,„HjCl,(OH)Oj. [235° oncor.]. Formed by
boiling tetra-chloro-(o)-naphthoquinone with
alcoholic KOH. Yellow needles. Sublimable.
V. sol. alcohol, ether, &a., si. sol. water. Its
Bsdts are deep red. By treatment with aniline it
gives an anilide [180° uncor.], which forms
coppery iieedles. Sol. hot alcohol, acietic acid,
and ether, si. sol. oold alcohol, insol. water.
The corresponding o- and j)-toluidine deriva-
tJTes melt at [205°] and [203°] unoor. respec-
tively (Clans, B. 19, 1141).
Tetra-oliloro-oz7-(a)-naphtho4ninone
<CO.C(OH)
II , [265° uncor.]. Formed by
DO.Ci(OH)
dissolving pehta-ohloro-(a)-naphthoquinone m
alcoholic KOH, and precipitating the acid by
HOI. Sublimes in yellow needles. The alkaline
salts are v. sol. water, the Ajg, Pb, Ou, &o. Salts
■re red pps. (Claus a. Wenzlik, B. 19, 1168).
DI-CHLOBO-SI-OXT - (a) -NAPHTHOCITJI-
r./
,OO.C(OH),
[105°].
HONE DIHTSBIDE CJiX I
From ohloro - amido - naphthoquinone and 01
(Zincke a. Gerland, B. 20, 3216). Thick needles.
Converted by alkalis into a compound [129°]
which may be oxidised to another [125°].
CHLOKO-OXY-NAPHTHOftTIIKOlIE SUl-
PHONIC ACID (?) 0,,H,C1S0. t.e.
C,^,C10j(0H)(S03H). From naphthalene,
EClO,, and HjSO, (Hermann, A. 151, 63; Z.
[2] 4, 661). Amorphous mass, m. sol. water, v. sol.
klcohol and ether. When boiled with water it
exchanges CI for OH. The K Bait is a red
dye.
(2, 8 ?)-Chloro-ozy-(a) -naphthoquinone (S*).
Bulphonio acid 0,„H3C10j(OH)(S03H). [211°].
From di-ohloro-naphthoquinone sulphonic acid
by displacing 01 by OH (Claus, J. pr. [2] 37,
184). Crystals ; t. sol. water, si. sol. alcohol,
insol. ether.
Salts. — The normal salts are yellowish-red,
the basic salts are dark red. — Na2A"2aq. —
BaA" 2aq.— PbA".— AgjA"aq.
Phenyl derivative
C„H3(S03H)01(OPh)Oj. [121°]. Formed by
the addition of phenol and a small quantify
of potash to a hot solution of the sodium salt.
0,„H3(S0sNa)01(0Ph)0j(Ph0H).— BaA'j2PhOH.
Small needles (from water). — AgA'PhOH.
Needles. V. sol. hot, si. sol. cold, water.
Acetyl derivativeO,fi^(SO^)0\(Oko)Oi.
Salt B. — NaA' : bright yellow needles. The Agi
Fb and Ba salts form double salts with the pre-
cipitant.
CHLORO-OXY-NICOTIKIC ACID «. Cni.0B0-
OXY-PYBIDINI! CABBOXYLIC kCTD.
OI-CHLOBO-DI-OXY-OCTANE
0aH„CU0H)2. Formed by the action of OlOH
on CHj:0Me.0HyCHj.0Me:CH2 (Przybitek, B. 20,
8239).
DI-CHLOEO-OXY-OCTOIC ACID CjHi.CljO,
i.e. (0sH8Cl)jC(0H).C0jH. Formed by the
union of HCl with (C3H5)20(0H).00jH obtained
from oxalic ether and zinc allyl (Sohatzky,
J. R. 17, 73). Syrup.
DI-CHLOBO-HEXA-OXY-DIPHEITYL.
Tetra-methyl ether, O^HigOljO, i.e.
0,2H2Cl2(OH)j(OMe),. Di-chlaro-hyAroccwu-
ligium. [220°]. From its acetyl derivative and
alcoholic KOH (Hayduck, B. 9, 929). Small
plates (from alcohol). M. sol. hot alcohol. —
CieH.jK^ClA : needles.-BaA".
Di-acetyl-derivative
0,2HjCl2(0Ac)j(0Me),. [172°]. From di-acetyl-
coerulignon and FClj. Small prisms.
Hexa-methyl ether CijHjCyOMe),.
From C,sH,(OMe)„and 01 (Ewald, B. 11, 1624).
Keedles (from alcohol).
Tetra-chloro-di-ozy-diphenyl Ci^gCl^O,
».e. C,HjCl,(OH).C,HjClj(OH). [233° uncor.].
From di-oxy-diphenyl in HOAo and 01 (Ma-
gatti, B. 13, 227). Needles (from dilute alcohol).
Fuming HNO, gives dark red insoluble scales of
0,H,Glj.O
O.H,01^0
Ooto-chloro-di-oxy-diphenyl 0,jCl8(0H)j.
Per-chloro-ddphenol. [234°]. Prepared by heat-
ing per-ohloro-diphenyl with alcoholic NaOH
at 150" (Weber a. SSUsoher, B. 16, 883). Quad-
ratio tables. Sol. benzene and alkalis.
Di-methyl ether 0,jCl,(OMe), : [226°];
long white needles.
Di-acetyl derivative C,20l3(OAo), :
[194°] ; pointed crystals.
CHLOEO-OXY-PHENYL-CAEBAMIC ACID.
Anhydride C3H301<™>00. CarbonyU
ehloro-anvido-phenol. [193°]. Formed by boil-
ing with alcohol the product
(0,H,C1<;'^Q ^^CO) of the action of bleaching.
108
CHLORO-OXY-PHENTL-CARBAMIC AOID.
powder on CsH^<^-^(^>CO (Jaooby, /. jpr. [2]
37, 32). Plates (from water, HOAo, and benz-
ene). SI. sol. hot water. May be sublimed.
£io.i>.di-o]iIoro-ozy-phenyl-carbainio acid.
Anhydride 0,H.01<;^^';>00. (o)-Car-
bonyl chloro-phenol chlorimide. [119°]. From
the preceding and chlorine- water (Jacoby, J. pr.
[2] 37, 40). Plates; m. sol. chloroform and
benzene. Converted by heat into the following
isomeride. Converted into the preceding body
by boiling with alcohol, ether, water, aniline,
di-methyl-aniline, and phenyl-hydrazine.
Bi-ehloTo-ozy-phenyl-carbamic acid. Anhy-
dride 0,H,C1,<^>C0. («) - Carbonyl - da -
chloro-amAdo-phenol. [270°]. The chief product
of the action of heat on the preceding, the fol-
lowing isomeride being also formed (J.). Prisms
(from alcohol). May be sublimed.
Si-chloro-ozy-phenyl-carbamio acid. An-
hydride OjHjClj^^^CO. {P)-Ca/rbonyU
di-ehloro-evmido-phenol. [214°]. Formed as
above. Needles; t. e. sol. alcohol, ether, and
HOAo; m. sol. water. Sublimes in needles.
Tri-cUoro-ozy-phenyl-carbamio acid. An-
hydride OjH2C1j<^^q'>CO. {a)-Carhmyl-di-
chloro-phenol chlorimide. [o. 147°]. Prom
CaHjCK^ Q ]>C0 and a solution of bleaching-
powder (Jacoby, J.pr. [2] 37, 46).
Tri-cnloro-ozy-phenyl-carbamic acid. An-
hydride C.H,C1,<^^^>C0. [89°]. {P)-Ca^-
hanyl-di-chloro- phenol ehlorhmde. From
CaHaClj^^^^CO in HOAo by adding a solu-
tion of bleaching-powder (J.). Needles; sol.
water.
Tri-chloro-ozy-plienyl-carbamio acid. An-
hydride CfiCl,<^^yc6. Carbonyl - tri-
chloro-amido-phenol. [262°]. Formed from
C,H4<^^]>C0 in HOAo by chlorination and
subsequent decomposition . of the product by
boiling alcohol (J.). Needles, si. sol. alcohol,
HOAc, and water. Sublimes in plates.
letra-ohlbro-ozy-phenyl-carbamic acid.
Anhydride C,C1<<^>C0. Carbmvyl-
tetra-chloro-amido-phenol. [o. 229°]. Formed
by heating Cja;Cl,<;^Q'>CO which is ob-
tained by treating a solution of the preceding in
HOAo with bleaching-powder (Jacoby, J. pr. [2]
87, 48). White crystalline sublimate; A. sol.
water; m. sol. alcohol and HOAc; v. sol. ether
and benzene. Converted by bleaching-powder
solution into 0,C1,<^ q ^CO whence it is re-
generated by boiling with alcohol.
TBI ■ CHLOBO ■ BI - OXY - SI - PHENYL -
ETHAKE 0„H„C1,04 i.e. C01,.0H(C.H40H)j.
[202°]. From phenol, chloral, H^SO^, and
HOAo at 0° (ter Meer, B. 7, 1201). Small crys-
tals; T. sol. alcohol and ether. Alcohol and
lino-duBt give CH2:C(C^tOE),.
Di-acetyl derivative
CCls.OH(OaHiOAc)j. [188']. Needles.
DI - CHLOBO - OXY - PHENYL - UETHYIi •
PYEAZOLE C,„HsNjOCL, i.e.
Ph.N<^rcM|>- [61°]- Obtained by pass.
ing chlorine into oxy-phenyl-methyl-pyrazole
dissoli^ed in chloroform (Knorr, A. 238, 178).
CrystaUiHe mass, volatile with steam, insol.
water and alkalis, sol. alcohol and ether. Be-
dnced by Sn and HCl to oxy-phenyl-methyl-
pyrazole.
;3.CHL0B0-(o)-0XY - PHENYL - PROPIONIC
ACID CsHjClO, i.e. Ph.CH(OH).CHCl.CO,H
[104°]. From sodio cinnamate, sodic carbonate
and chlorine (Glaser, A. 147, 80 ; 219, 183) or
better, from potassio cinnamate and HCIO
(Erlenmeyer a. Lipp, A. 219, 184). Slender
six-sided lamina (containing aq). Melts, in
the hydrated condition, at 80°. M. sol. cold
water.
Reqetions. — 1. AlkaKs form so-called iS-oxy-
phenyl-cinnamic acid which is probably the
anhydride of ofl-di-oxy-phenyl-propionio acid
O
/\ (Erlenmeyer, B. 20, 2465),
C5H5.CH . CH.COjH
and o;3-di-oxy-phenyl-propionio acid. — 2. So-
dium amalgam, forms j3-oxy-phenyl-propionio
acid. — 3. Fuming HCl produces a;3-di-(diloro-
phenyl-propionic acid. — 4. Boiling with AO2O
gives a-chloro-cinnamic acid.
Sal t.^AgA': crystalline powder.
a-ChIoro-;8-ozy-phenyl-propiasic acid
CA.CH(OH).CHCl.COjH. From a;8.di-oxy.
phenyl-propionic acid and HCl (Leschhoni,
Dissert. Wurzburg, 1884). Formed also by the
O
action of HCl on CgHj.CH.CH.CO2H, which is
obtained by treating the preceding acid with
alkalis (Erlenmeyer, jun., B. 20, 2466).
Chloro-ozy-a-phenyl-propionic acid 0,^010,.
Chloro-tropic acid. [130°]. From atropic acid
and aqueous ClOH (Ladenburg, A. 217, 110).
Crystals ; v. e. sol. water. Zinc-dust and iron
fiUngs in HOAc convert it into tropic acid.
{Py. 1:4:2) -CHLOBO - OXY -PHENYL -ISO -
aumOLlNE C,5H,„C1N0 ».e.
>CCl:CPh .CCl : CPh
0.H,< I orC^,<; I .
\CO.NH \C(OH):N
Chloro4sobemalphthaUrmdm,e. [212°]. Formed
by heating chloro-methoxy-phenyl-isoquinol-
ine [76°] with fuming HCl at 100°. Silky
needles. T. sol. benzene, chloroform, and acetic
acid, m. sol. cold alcohol and ether (Gabriel, S.
19, 2358).
Methyl derivative CHi-NOCl i.e.
.CCl : CPh
0«Hj<; I . [76°]. Formed by heating
\C(OMe):N
di-chloro-phenyl-isoquinoline with a solution of
sodium in methyl alcohol at 100°. Colourless
needles. V. sol. ether, chloroform, benzene, and
acetic acid. Yery weak base. By heating with
fuming HCl at 100° it yields ohloro-oxy-phenyl-
isoquinoline (chloro-isobenzalphthalimidine) and
methyl chloride (Gabriel, B. 19, 2357).
TRI-CHLORO-OXY-PROPYL-ACRIDmE.
lOQ
TETSA . GHLORO - DI - OXY - DI - PHENYL
B'JLPHONE C,JI„C1,S0, i.e. S0^(GJEifll^.01i)^.
[289°]. S.G.ia 1-777. From SOj(0,H^.OH)„
EClO,, and HCl {Annaheim, A. 172, 38 ; B. 9,
1150). Needles or prisms. Insol. water, v. si.
Eol. cold alcohol.
DI - CHLOEO - DI - OXY - DI - PHENYL -
THIOXrSEA. Di-methyl ether
SC(NH.C.H,Cl(OMe))r [153?]. From ohloro-
anisidine, aloonol, and CS,. White needles, sol.
alcohol and ether (Herold, B. 15, 1687).
CHLOSO-OXY-PICOLINIC ACID v. Chlobo-
OXT-FIBIDIIIB CABBOXYLIO ACID.
CHLOBO-OXY-FBOFANE SULPHONIC ACID
CsHjClSO, i.e. CH,Cl.CH(0H).CHj.S03H. From
epichlorhydrin and NajSO, at 100° (Darmstadter,
A. 148, 126). Syrup. — NaA'2aq: monoclinic
crystals. — NaA'aq: trimetrio tables.— NaA'^aq
(Pazsohke, J.pr.l2] 1, 94).— CaA'j6aq.- BaA'jaq.
PbA'j 2aq.— AgA' 3aq.
0.CHLOBO-a-OXY.PBOPIONIC AaO
CH,C1.CH{0H)C02H. Chloro-lactic add. [78°].
Formation. — 1. From chloro-acetio aldehyde
by treatment with HON and HCl (Glinsky, Z.
1870, 615 ; Frank, A. 206, 344).— 2. Together
with its isomeride by the union of HOCl with
acrylic acid in aqueous solution at 0° (MelikofE,
B. 13, 2153).
PreparaUon. — Epiohlorhydrin (5 g.) is heated
with (20 g. of) nitric acid (S.Cr. 1'38) on a water
bath mitil the odour of chloropicrin is perceived.
The product is poured into water and extracted
with ether. On evaporation this leaves an oil
that solidifies over HjSO^ (v. Eiohter, J.pr. 128,
193).
Properties. — Flat, deliquescent prisms. Y.
sol. water, alcohol, and ether. Cannot be dis-
tilled. Moist Ag20 converts it into glyceric acid.
When heated with water it splits up into alde-
hyde, COj, and HCl (Erlenmeyer, B. 13, 309).
Salts.— CaA'j3aq.— ZnA'j3aq.—MnA'j3aq.
CuA',.-AgA'.
Methyl ether MeA': (186°); Uquid,
Ethyl ether EtA'. [37°]. (205°).
a-Chloro-j3-ozy-propionic acid
CH,OH.CHCl.COaH.
Formation. — 1. From glyceric acid and HCl
(Werigo a. Melikoff, B. 12, 178). —2. From
acrylic acid and HOCl.— 3. By tbe action of
water on a/3-di-chloro-propionio acid (MelikoS,
B. 12, 2227); — i. From ozy-acryUo acid and HCl
(Melikoff, B. 13, 273).
Properties. — Syrup. V. sol. water, alcohol,
and ether. Converted by moist AgjO into gly-
ceric acid, and by alooholio EOH into oxy-acryllo
acid. Cone. HCl forms, at 100°, a^-di-chloro-
propionio acid [50°]. Zino and dilute H^SO^
reduce it to bydracrylio acid (Melikoff, J. B. 13,
164).
Salt. — ZnA', : hygroscopic gummy mass.
Di-chloro-ozy-propionic acid
CHCl,.CH(OH).COjH. [77°]. From di-chloro-
acetio aldehyde, HCN, and HCl (Grimanz a.
Adam, B. 10, 903 ; Bl. [2] 34, 29). Deliquescent
tables; v. e. sol. water, alcohol, and ether.
Beduces ammoniacal AgNO,.
Ethyl ether EtA'. (220f). From the acid.
Also from tri-chloro-oxy -propionic ether in alco-
holic solution, by treatment vrith zino, and HCl
^nner a. Bisohoff, A. 179, 88).
Tri-dhloro-oxy-propionic acid
CCla.CH(OH).CO.jH. Tri'chloro-lacUc acid.
[105°-H0°]. From its nitrile by HCl (Pinner.
A. 179, 79 ; B. 17, 1997). Prisms,; sol. ether.
Split up by alkalis into chloral and formic acid.
Beactions. — 1. With strong aqueous NH, it
gives glyoosine. — 2. With hydroxylamine it
yields glyoxim. — 3. With phenyl-hydrazine it
yields glyozal-di-phenyl-hydrazide. — 4. With
urea and a little water it gives acetylene-urea
>NH.CH.NHv
CjHjNA t.«. 00< I >C0 (Pinner, B.
^NH.CH.NH'^
17, 1997). — 5. Fusion with wrea forms some uric
acid (Horbaczewski, M. 8, 584).
Salts.— NH,A'.—KA': prisms.
Ethyl ether EtA'. [67°]. (o.235°). Formed
by heating ohloralide with alcohol (WaUach, A.
193, 8).
Preparatiow.— Chloral-hydrate is converted
into its cyanhydrin by mixing with strong HCN,
and after 24 hrs. standing the mixture is digested
on the water-bath for 4-6 hrs. and evaporated.
The crystalline cyanhydrin is dissolved in one-
third its weight of alcohol and HCl gas led into
the boiling solution. When the reaction is com-
plete the ether is precipitated by water, and
solidifies on cooling ; the yield is 90 p.c. of the
theoretical (Pinner, B. 18, 754).
Properties, t— Insol. water. Converted by
alkalis into tartronic acid. Zino and HCl reduce
it, in alcoholic solution, to di-chloro-oxy-propionio
acid.
Acetyl derivative CCl,.CH(0Ac).C02H.
[65°].
Tri-ehloro-ethylidene ether v. Cblo-
BALIOB.
Tri-brpmo-ethylidene ether
CBr3.CH<^-°'^>CH.CCl,. [149°] (Wallach, A.
193, 1).
Amide CC1,.CH(0H).C0NH,. [96°]. From
the nitrile, HOAc, and H^SO, (Pinnet a. Fuohs,
B. 10, 1061). Slender needles ; v. sol. cold water.
Acetyl derivative CCl,.CH(OAo).CO.NH,.
[95°].
Nitrile CC1,.CH(0H).CN. [61°]. (o. 218°).
From chloral and HCN (Hagemann, B. 5, 151 ;
Pinner a. Bischoff, A. 179; 77; 17, 1997). Tri-
metrio tables (from CSj). V. sol. water, alcohol,
and ether. Beactions. — 1. Alkalis split it up into
chloroform, HCy, and formic acid. — 2. Ammonia
forms di-chloro-aoetamide. — 3. Heated with
urea it yiejds tri-chloro-ethyUdene-di-ureide
CCls.CH(NH.CO.NHJj, as chief product, and
biuret as a by-product (Pinner a. Lifschiitz, B.
20, 2345).
Acetyl derivative CCI,.C(OAo).CN. [31°].
(208°).
a,-TBI.CHL0B0-j3-0XY.(4.).P50PYL-ACBID.
INE C,.H„0NC1, Cfit
».e. N— C:OH,.CH(OH).CCla(?).
0,H,
Methyl-acridine chloral. Formed by warmmg
(^.)-methyl-acridine (60g.) suspended in benzene
(600 g.) with anhydrous chloral (70 g.) ; at 70°-
75° tbe product separates as a sandy pp.; the
yield is nearly theoretical. Yellow needles or
prisms. Above 200° it is again resolved into
110
TRI-GHLORO-OXY-PROPYL-AORIDINE.
methyl-aciidine and ohloral. SI. sol. all ordi-
nary solvents. Its basic properties are very slight.
The Bolntion in cone. H^SO, has a splendid
greenish-yellow fluorescence. By alkaUs it is
partially resolved into methyl-aoridine and chlo-
ral, and partly converted into acridyl-acrylic acid
C„H,N.CH:CH.C02H whence EMnO, produces
.Oij-CHO
»oridino.(ii.).aldehyde 0,HX | \C,H, [140°]
(Bemthsen a. Mnhlert, B. 20, 1542).
DI-CHLOBO-OXT-FYBIDINE G,H2(OH)Gl2N
n78°]. Formed by heating the ethyl ether with
HGl (KoenigB a. Geigy, B. 17, 1834). Colourless
crystals. V. sol. hot water.
Ethyl ether 05H,(0Et)Cl2N : [81°]; white
eiystals; formed by heating tri-ohloro-pyridine
with so^nm ethylate.
CHXOBO-(y)-OXT-FTBII)INE CABBOXYLIC
ACID 0sHjC1N(0H)(C0jH). Chloro-oxy-picoUnia
acid. a. 4 at 100°.
Preparaiion. — Comenamioacid(2.«.)isheated
with FCl, (5 equivalents) in a sealed tube at
220°. The product is poured into water at 0°.
The oil that separates is extracted with hot
water and the extract evaporated to crystallisa-
tion. The crystals are dissolved in a Uitle hot
water and NH, is added : ammonio comenate se-
parates and ci^aia chloride is then added to the
filtrate. Calcic ohloro-oxy -methyl pyridine car-
boxylate orystaUises out slowly (Belbnann, J.pr.
[2] 29, 3).
Propertiei. — ^Pointed needles (containing aq).
Insol. oold water, ether, chloroform, and benz-
ene. Sol. alcohol and acids.
R»acti<ms.—\. FejCl, gives a brown pp. sol.
excess. — 2. AgNO, gives a bulky white pp. soon
becoming granular. — %. Beduced by Sn and HOI
to (7)-oxy-pyridine carboxylic acid {('y)-oxy-pico-
linic acid).
S alts. — B'HCl. Very soluble pointed needles.
CaA', aq. Oot by adding CaCl, to a solution of
the acid nearly neutralised by NH,. M. sol.
water.— 0,Hj01N<[QQ>Ca ^aq. Got by adding
CaCl, to a solution of the acid quite neutralised
byNH,.
Chloro-oxy-pyridlne carbozyllc acid
0,H2C1N(OH)CO^. Ohloro-(xcy-picolime add.
[o. 257°]. Obtained by heating penta-ohloro-
methyl-pyridine CjH^Cl^N.CCl, withH^SO, (Ost,
J. pr. [2] 27, 257). Thick needles (containing
aq). Beduced by HI in acetic acid to (j3)-oxy-
picolinio acid.
Salt.— GaA':4aq.
CUoro-oxy-pyridine carbozyllc acid
C,H2ClN(0H).C0jH. Chloro-oxy-picoUnicaeid.
Obtained by the action of H2SO4 on penta-chloro-
methyl-pyridine obtained by treating picolinio
acid with PCI, (Seyfferth, /. pr. [2] 84, 254).
Clusters of needles. Does not melt below 315°.
SI. sol. cold water. Does not combine with EOl.
Chloro-ozy-pyridine carbozyllc acid
OsH,ClN(OH)C02H. Chloro-oxy^mcoUnic acid.
[802°]. From nicotinic acid by successive treat-
ment with PCI, and HjSO^. Monoclinic prisma
(S.).
Di-cUoro-ozy-pyridine earbozylic acid
OiHCl^(OH)CO,H. Di-eKloro-oxy-pieoUiUe
goid. [c.382°].
PrgMTitionf-Bj be«tiiit; bexa-chloro-me-
thyl-pyridine CsHOljN.CCl, with (80 p.c.) H^SO,
(Ost, J.pr. [2] 27,257).
Properties. — Felt-work of fine needles (con.
taining aq) (from water), or else as small hard
prisms. Decomposes about 282°. Not attacked
by Sn and HCl or by aqueous HI. Beduced by
HI in glacial acetic acid to (a)-oxy-pioolinic acid.
Salts. — Mostly soluble, except the calcium
salt, CaA'2, which is but slightly soluble, although
it is more soluble than the acid. Separates by
spontaneous evaporation as silvery stars.
CRIOBO-OXY-FYBOTAXIABIC ACIB
CjH,C10,. Ohhro-citramalie acid. [100°].
Formation. — 1. From oitraconates and HCIO
(Carins, A. 126, 204). — 2. From citra- or mesa-
di-chloro-pyrotartarie aoid by warming with
water (Gottlieb, A. 160, 101 ; Uorawski, J. pir.
[2] 10, 68; 11, 466).— 3. By passing chlorine
into an aqueous solution of sodium mesaconate
(Morawski, J.-pr. [2] 12, 392).
Properties. — Trimetric crystals. Water at
120° converts it into di-oxy-pyrotartoric acid
and acetone.
Salts. — ^BaA''4aq: monoclinic tables, t. sL
sol. cold water. — PbA"4aq. — AgjA".
Chloro - ozy - pyrotartaric acid CjH,C10,,
S.ydro-ehloro-oxy-ciix'aeoma acid. [162°]. From
oxy-citraconic acid and fuming HCl at 120° (Mo-
rawski, X ^. [2] 11, 443). Plates. Split up by
bases into HGl and oxy-oitraconic acid. Sodium
amalgam reduces it to oxy-pyrotartaric acid g.v.
CHLOBO-OXY-QTrmOLUIS 0^,N0C1 i«.
.CH:CH
C^X^ I . [112°]. Formed by the action
^ N :C0C1
of bleaching powder solution on the borate of
quinoline (Einhom a. Lanoh, A. 248, 343).
White prismatic needles. Sol. hot water, acetic
ether, HOAo.
Reactions. — 1. Boiled in an alkaline solution
carbostyril is formed. — 2. PCI, forms {Py. 3)
ohloro-quinoline. — 8. Boiled with alcohol p-
chloro-carbostyril [263°] is formed.
(B. 2)-Clhloro.(Py. 3)-oxy-quinaUne
CG1:CH.C.CH:CH
J n I . p-CMoro-ear6os^n{. [263°].
CH:GH.C.N:C(OHJ
Formed by treating the following body with
alkalis, and, by intramolecular change, from the
preceding body. When its iJkaline solution
mixed with KaOCl is treated with CO, the fol-
lowing body is ppd. EMnO, gives p-chloro-
isatin [248°].
{B. 2, Py. 3)-Bi-cUoro-(Py. 8)-ozy-qmaoline
CC1:CH.C.GH:CH
I II I . [116°] and [145°]. From
CH:CH.C.N:C0C1
(B. 2)-chloro-quinoline and bleaching powder
^inhom a. Laudh, A. 243, 353). Plates (from
HOAc) or needles (from EtOAo). Dimorphous.
BoUing alkalis give chloro-carbostyril [263°].
Chloro-ozy-qvinoline v. CaLOBO-OAKBosiYBiii.
Tri-ohloro-ozy-quinoline CgHjClgON. [200°]. -
Prepared by passing chlorine for 6 hours into a
solution of quinoline in dilute acetic aoid. The
prodnot is orystaUised from alcohol. The yield
is 15p.c., most of the quinoline being recovered.
Thin matted needles, sol. benzene, ehloroform,
and alcohol. Beduced by HI at 250° to oxy-
qninoline, which is found to be (Py. 3)>ozy'
quinoline (J. Botheit, J.pr. [2] 29, 300).
CHLORO-OXY-TOLUOARBOSTYRIL.
Ill
^PV. 3:4)-CHI0B0-0XT-IS0QUIN0LIIT£
. CH : CCl XH:CC1
C»H,ClNOt.«.CAC I orO^-C | .
\0(OH):N \C0.NH
[220°]. Fine needles. V. sol. ordinary solvents.
Dissolves in dilute NaOH. Formed as a by-
product in the action of alcoholic EOH upon di-
chloro-isoquinoline. Obtained by the action of
diy HCl gas at o. 150° upon (Py. 2:4)-ohloro-
methozy-isoquinoline CgH,(
/"
CH-
=C01
On
'\c(OMe):S
methylation with Mel and methyl alcoholic EOH,
it is converted into (Py. 2:4:3)-ehloTO-oxy-me-
i!H:CCa
thyl-isoqninoline C^,^ I , isomeric with
^CO.NMe
the above chloro-methozy-isoquinoline (Gabriel,
B. 19, 2360).
X!H=C(31
Mtthyl derivative 0,H,^ |
N3(0Me):N
[74°]. Formed by heating di-chloro-isoquinoline
with a solution of sodium in methyl alcohol, at
100°. Thick needles. V. sol. alcohol, ether, &o.
By digestion with fuming HCl at 100° it is con-
verted into the imide of phenyl-acetio-o-oarboxy-
/CHj.CO
lie acid CMjC \ (di-oxy-isoqninoline). By
\ CO.NH
dry HCl at 1S0° it is converted into ohloro-oxy-
isoqninoline (Gabriel, B. 19, 2359).
<OH==C01
I .
C(OEt):N
[37°]. Formed by heating di-ohloro-isoqumoune
with alcoholic sodium ethylate at 100°. Long
needles. V. sol. ordinary solvents (Qabriel, B.
19, 2368).
(Py, 4:2)-Chloro-oxy-isoqninoIine GgHgClNO
>CH: 0(0H) iOHj.CO
W.O.HX I orO.H4<; I [197°].
\CC1:N \C01:N
Formed as a by-product in the preparation of
di-chloro-isoquinoline by the action of FOCI, at
150'-170° upon Uie imide of phenyl-aoetic-o-
.CH,.CO
Mtboxylio acid 0^4< I (di-oxy-isoquino-
line). Long thick needles, or oolonrless plates.
U. sol. hot alcohol, si. sol. ether, cold acetic acid,
hot benzene, and chloroform.
Methyl derivative C„Hs(OH,)NO : [67°].
Small white crystals ; v. sol. alcohol, ether, Ac,
insol. alkalis. Formed by heating chloro-oxy-
isoqninoline with Mel and methyl - alcoholic
KbH (Gabriel, B. 19,2355).
Di-cUoro-ozy-isoqninoline (?)
.CO.CHCa
C^jCljNO probably 0^4^ I .Formed by
heating hippniio add with POl^ By further
action of PCI, it is converted into a body
0,H,NCls, [184°] (Rugheimer, B. 19, 1169; e/.
Bchwanert, A. 112, 69). ^„„„„,
DI-p-CHMKO-DI-OXY OTIHOKE
C.C1,(0H) A[l:*:2:6:3:6]. ChloraniUe aetd
(Hantzsoh, S. 20; 1303, 2279). .
FormatUm.—l. By dissolving tetra-ohloro-
oninone (ohloranil) in dilnte aqueous KOH
(Etdnuuin, /. gr. 22, 281; </. Stenhonse, JL.
Swppl. 8, 14).— 2. By the action of potash on
tri-chloro-quinone (Graebe, A. 146, 24).
Properties.— Glittering red plates (containing
aq). May be partially sublimed. Its aqueous
solution ii violet, but decolourised by HCl or
HjSO,, by which it is ppd.
Beacti<ms.—1. Reduced by tin and HCl to
di - chloro - tetra - ozy - benzene. — 2. POI5 forms
tetra-chloro-quinone. — 3. By treatment with bro-
mine it is converted into di-chloro-tetra-bromo-
aoetoneCBr2Cl.CO.CBrjCl[79°] (Levy a. Jedlidka,
B. 20, 2318; cf. Stenhouse, A. Suppl. 8, 17).-^
4. HCl and EClO, form tetra-chloro-acetone
CHCIJ.CO.CHCI2, which crystallises with 4aq
[49°] (Levy a. Jedlifika, B. 21, 318).— 5. Am-
moma forms 0,Cl202(KH2)(0H) 3aq crystal-
lising in black needles and forming the salts
0,Cl,0j(NHi)(0NH,) 4aq and C,ClA(NHj)(0Ag).
6. A small quantity of SO, forms tetra-chloro-
tetra-oxy-quinhydrone C^HsCl^O,, crystallising
in black needles.
Salts.— KjOgCIsOjaq: purple prisms, form*
ing a purple solution in water or alcohol, —
Na^"4aq: dark crimson needles (Hesse, A.
114, 30i).— BaA"3aq: red-brown scales.— Ag^":
red pp.
Di- ethyl ether EtJCaClJOt. Bed prisms
(from alcohol).
CHLOBO-DI-OXY-QTTINONE S1TLFH0NI0
ACID C,HsClSO, i.e. 0,C1(OH)A(SO,H).
Potassium salt C,Cl(OE)A(SOsE) 2aq.
From tri-chloro-hydroquinone sulphonic acid
and EOH (Grssbe, A. 146, 66). Bed needles;
V. sol. water, insol. alcohol. With HCl it gives
yeUowlaminee otC,CI(OH),0,(503E), decolourised
by tin ana HCl.
01.^. CHLOBO-BI-p-OXT-TEBEFHTHALIO
ACID C,Cl2(0H),(C0^), [1:4:2:5:3:6]. From the
colourless ether (v. infra) and cone, aqueous
KaOH at 100°. . Greenish-yeUow needles (con-
taining 2aq). Stable in the air, but effloresces
over H2SO4 into the white anhydrous pseudo>
form (di-chloro-quinone di-hydro-di-carboxylio
acid) which is reconverted into the unstable form
by heating with aqueous NaOH.
Ethyl ether. IH-chloro-hydroquinone-di-
earboxyUc ether. [123°]. Formed by reduction
of di - chloro - quinone - di - carboxylic ether
CgGl,02(C02Et)2 with zinc-dust and acetic acid.
Long thin colourless needles. V. sol. ethef.
By melting and quick cooling it is converted
into yeUowish-green dichroic tables, which are
probably the pseudo-farm G^Lf^fijf^O^l)^
(di-chloro-quinpne-di-hydro-di-carboxylic ether) ;
this is unstable, and by a gentle warming is con-
verted back into the colourless needles of the
stable form (Hantzsch a. Zeckendorf, B. 20,
1812).
CHLOBO-OXT-THTMOaTTIirONE
0,„H,.(0H)C10, i.t. C.C1(0H,)(C.H,)02(0H).
[122°]. From di-nitro-thymol by treatment with
PClj, thechloro-di-nitro-thymol so formed being
reduced by tin and HCl and the resulting
amido- compound oxidised by CrO, (Ladenburg
a. Engelbrecht, B, 10, 1218). Lemon-yellow
prisms (from alcohol). Beadily sul}limes. Its
alkaline solutions are violet. Boiling with EOH
converts it into di-oxy-thymoquinone.
CELOBO - OXY - TOLTJCABBOSrnUX ft
CBIiOBO-VI-OZT-IIETByL-QIJINOIitia.
112
0HLOR()-UXY-TOLU0,tnNOLINE.
CHlOEO-OXY-TOlTIftUIlfOIINE v. Chloro-
OST-HBTHni-QVINOLTNE.
I>I-CHL0B0-SI.0XY-T0LUQT7IN0II£ (?)
C,H.CljO, i.e. C,Cl,Me(OH)Oj. [157°]. From
tri-ohloro-orcin and alkaline K,FeC}re (Stenhouse
B. Groves, B. 13, 1306). Deep yellow scales
(from water). SI. sol. water, v. sol. alcohol.
Beduoed by SO, to oolonrless CjH^CljO,, which
on oxidation gives purplish-brown crystals of a
qninhydrone. A di-chloro-di-oxy-toluquinone
has been described by Brauninger {A. 185, 339)
as obtained from beech-wood creosote by treat-
ment with KOlO, and HCl ; the resulting tetra-
ohloio-toluquinone being reduced by SO, to the
tetia-chloro-hydrotoluquinone, whence dilute
EOHf orms di-chloro-di-oxy-toluquinone, a brick-
red orystalline powder.
I>I-CHLOBO-DI-OXY-SI.o-TOLTL-FYB&.
c,H,.N-cca.co
ZIKE III. [201°]. Fromdi-oxy-
C0.CC1.N.C,H,
di-tolyl-pyrazine dihydride and PCI, (Abenius a.
Widmann, B. 21, 1662).
CHLOBO-OXT-VALSBIC ACIO
C,H4Ca(0H).CH,.C0jH. Obtained by oxidising
ohloro-allyl-propyl alcohol by chromic mixture
(Lopatkin, /. pr. [2] 30, 396). Orystalline.
S a It s .— BaA', 8aq.— KaA' aq.
7-CliloTO-7-oxy-valeric acid
Lactone. C,H,0,C1 »•«• CH3.CC1.CH2.CH,.C0.0
(80°-82°) At 10 mm. Got by passing HCl into
(a)-angelioo-Iaotone. Decomposed by water into
HCl and levnlic acid. On distillation it splits
up into HOI and (j3)-angelico-lactone. Bromine
converts the lactone into brominated bodies,
whence water forms a great deal of di-bromo-
levnlic acid and some bromo-levulic acid (Wolff,
A. 229, 249).
Chloro-ozy-valeiic acid C^HgClO, i.e.
eH,.CHCl.CMe(OH).00,H. [75°]. Formed,
together with its isomeride, by the union of
tiglio acid with HOCl (Melikoff, A. 234, 225 ;
Bl. [2] 47, 166). Needles, sol. water, alcohol,
and ether. Alcoholic EOH converts it into butyl-
ene oxide carboxylio (di-methyl-glycidio) acid
O
/\
CH,.CH.CMe.CO,H [62°], whence HCl repro-
duces the origin^ acid [75°].
Salts.— ZnA'j. — CaA', : prisms.
Chloro-oxy-valeric acid
CH,.CH(OH).CMeCl.CO,H. [112°]. Formed,
together with the preceding, by the union of
HOCl with tiglio acid (M.). Prisms; v. sol.
water, alcohol, and ether. Alcoholic EOH con-
verts it into the same butylene oxide carboxylic
acid as the preceding.
Salts . — These are gummy masses. — ZnA',. —
CaA'j.— BaA',.
Tri-chloro-ozy-Taleric acid
CH,.CHC1.0Clj.CH(OH).CO,H. [140°]. Pre-
pared by boiling with HOI the compound of tri-
chloro-bntyrio aldehyde with HON (Pinner a.
Klein, B. 11, 1492 ; A. 179, 99). Trimetric tables,
V. sol. alcohol, ether, and hot water.
Salts.— NaA'aq: crystals.— PbA', ^ amor-
phous pp.
Ethyl ether EtA'. [40°]. (255°). Long
Vrisms. AloohoUoNH,coiiver(Bitinto C,H,C1N,0
(? amide of ohloro-imido-angelio acid) [118°]
whence boiling alcohol produces OjHgClKO,.
Acetyl derivative OiK^eOyOaaq. [84°].
Slender needles.
Tri-chloro-ethylidene ether
CCl3CH<3 Qo>OH-CCl,.CHC1.0H3. [87°].
(297°). From the acid and chloral at 175°
(WaUach, A. 193,37). Thick crystals (from
chloroform) ; explodes when struck.
A mide 0H3.CHC1.0Cli,.CH(0H).C0.KH,
[119°]. SI. sol. water and OuHj, v. sol. alcohol
and ether. Prepared by the action of strong
H2SO4 on the nitrile (Pinner a. Elein, B. 11,
1490).
Nitrile CH,.CHC1.CC1,.CH(0H).0N. Butyl-
chloral cyanhydrin. , [102°]. (c. 230°). From
tri-chloro-butyric orthaldehyde, alcohol, and
cone. HCyAq. Leaflets (from dilute HClAq) ;
m. sol. cold water, v. sol. alcohol. Converted by
alcoholic NHj into the amide of (i3)-chloro-cro-
tonio acid. XTrea gives chloro-crotonyl-urea
CjHjCl.CONH.CO.NH2 and butyro-chloral biuret.
Acetyl derivative of the nitrile
CH3.CHCl.CCl,.0H(OAc).CN. (240°-252°). From
the nitrile and AcCl. Yellowish oil.
TETEA-CH10a0-<»-DI-0XY-XYLENiE. An
hydride 0,H,C1,0 i.e. C.CI^^q^'^O- P18°].
From tetra-chloro-phthalic acid (7*7 g.), cone.
HI (3-5 CO.) and red phosphorus (2 g.) at 230°
(Graebe, ^.238, 331). Needles (from toluene).
SI. sol. hot alcohol, m. sol. hot benzene or HOAc.
Insol. boiling alkalis.
CHLOBO-PENTANE v. Amyi. chioride.
J)i-eb.loro--penta,neCs'B.,„Cl2.Amylenechloride.
(145°). S.G. 2 1-22 ; a 1-058. From crude amyl-
ene and POl, (Guthrie, C. J. 14, 128 ; A. 121,
115) or CI, the temperature being first at —15°,
afterwards boiling (Bauer, Z. [2] 4, 380, 667 ; cf.
KondakofE, C. C. 1887, 979).
Di - chloro - pentane (CH,)2CH.CH,.CH0l2.
Isoa,myUdme chloride. (130°). S.G. '^ 1-05.
From isovaleric aldehyde and PCI5 (Ebersbaeh,
A. 106, 265). EOH gives (GB.,)fiB..CB.:CH.Gl
(86°) and (CH,),CH.C:CH (Bruylants, JB. 8,413).
oo.Di-cMoro-pentaneCH3.CH,.CH2.CClj.CH3.
From methyl propyl ketone and PCI, (Bruylants,
B. 8, 411). Liquid; decomposed by distilla-
tion. Dry EOH forms CH,.CH3.CH2.C:CH. Al-
coholic EOH forms 0H3.Cia:,.CH,.CCl:CH2 (96°)
and CHj.CiCCjHs (Favorsky, Bl. [2] 45, 247).
Di-chloro-pentane CsH.oCl,. (155°-160°).
S.G. » 1-19. Formed by chlorination of ordinary
amyl chloride (BufE, A. 148, 350).
Di-chloro-pentane CjH,„Cl,. (151°). From
valerylene and HCl at 100° (Eeboul, Z. 1867,
173). Heavy oil.
Tri-ohloro-pentane CjHjCl,. (185°-190°).
S.G. ^ 1'33. , By chlorination of ordinary amyl
chloride (Buff, A. 148, 350). A crystalline tri-
chloro-pentane is formed (160°-190°) by chlori-
nating crude amylene (Bauer, J. pr. 100, 42).
Tetra-chloro-pontane CsHsCl,. (240°). S.G.
2 1-429. From amylene and CI (Bauer, J. pr.
100,43). \ > r
Fenta- and Heza-cMoro-pantanes haye been
obtained by Spring a. Lecrenier {Bl. [2] 48, 623)
by chlorinating isoamyl mercaptan.
cmOBO-ISO-PENTANE SULPHONIC ACID
C,H„C1.S0,H. From isopentane sulphouic acid
OHLOflO-PHENOL.
IIS
and CI in sunshine or, in presence of iodine, at
130" (Spring a. Winssinger, B. 17, 537 ; Bl. m
41,301).— BaAV • . lj
CHEOaO-PENTENOIC ACID t>. OmpBO-ANan-
Lio ACID and CHiiOBo-TiaLio Acn>.
CHLOBO-FENTENTL AICOHOI.
CH3.CH:CCa.CHMe.0H. Methyl-chloro-allyl
ca/rbinol. (159°) at 725 mm. S.G. {J-} 1-0882.
V.D. 4-09 (Theory 4-17). From tri-ohloro-amyl-
aloohol C,H,as.CHMe.OH, finely divided iron,
and acetio acid (Garzarolli-Thumlaokh, A. 223,
164), or zino-dust and dilate HCl. Cioloarless
mobile liquid with pungent smell, faintly soluble
in -water, soluble in ether, CSj, and chloroform.
Combines with bromine. Acetio acid is among
the products of oxidation by chromic mixture.
Acetyl derivative CsHjAcClO. (173°) at
735 mm. V.D. 5'73 (for 5-66). Does not com-
bine with bromine.
PEE-CHLOBO-PENnNENE C,C1,. Per-
ehZoro-meeylene. [89"]. From oomenic acid and
pa, at 280° (Ost, J.pr. [2] 27, 293). Prisms
(from alcohol); smells like camphor. Begins
to distil with decomposition at 270°.
CHLOEO-PHENANTHBENE v. Phenan-
THBENE. «
CHLOBO-PHENETOL v. Ethyl ethtr of
ChLOBO-PHENOIi.
o-CHlOBO-PHElf OL CaH<Cl(OH) [2:1]. [7°].
(176° i.V.).
Formation. — 1. From o-amido-phenol by
displacing NH, by CI by the diazo- reaction
(Sohmitt a. Cook, B. 1, 67 ; Faust a. Miiller, B.
5, 777). Solution of NaNO, is run into a hot
solution of o-amido-phenol and CUjCl, in dilute
HCl (Sandmeyer, B. 17, 2651).— 2. Together
with the f -isomeride by passing chlorine into
phenol (F. a. M. ; Kramers, A. 173, 331)
3. From o-chloro-aniline by displacing NH, by
OH through the diazo- reaction (Beilstein a.
Eurbatoff, A. 176, 39).— 4. Formed by neutralis-
ing with acid a mixture of sodium hypochlorite
and phenol (Chandelon, B. 16, 1749).
Properties. — Colourless liquid ; si. sol. water,
V. sol. ^cohol and ether. Potash-fusion converts
it into pyrocatechin (Petersen, B. 6, 368). HNO,
gives two chloro-nitro-phenols [111°] and [70°].
FCl, gives o-di-chloro-benzene (179°).
Methyl ether C^^C^OMe). o-Chloro-
anisol. (203°). Prepared from o - anisidine
C,H4(NH2)(OMe) by Sandmeyer's reaction (Wal-
laoh a. Hensler, A. 243, 237; ef. Fischli, B. 11,
1463).
Ethyl ether C^4CI(0Et). o-Chloro-phe-
netol. (208°).
Benzoyl derivative C,H4C1.0Bz. (314°).
Phthalyl derivative 0,B.fitOi(00,B.fil)^
[98°] (Mosso, C. C. 1887, 1396).
TO-Chloro-phenol CeH,Cl(0H)[3:l]. [28-5°].
(214° i.,V.). From jre-ohloro-aniline by displacing
NH, by OH through the diazo- reaction (Beilstein
a. Kurbatoff, A. 176, 45 ; Uhlemann, B. 11, 1161;
Vamholt, J.pr. [2] 36, 26). White needles.
BetiBoyl. derivative 0,H.Cl(OBz). [86°].
Phthalyl derivative [108°] (Mosso).
j»-Chloro-phenol C,H,C1(0H)[4:1]. [37°].
(217°).
Simnation. — 1. From phenol and SO^Cl,
(Dubois, Z. [2] 2, 705; 8, 205).-2. Together
with the o-isomeride by passing chlorine into
Vol. H. '
cold phenol (D.; Petersen a. Bahr-Praderi, A
157, 123). — 3. From p-amido-phenol by displa-
cing NH; by CI through the diazo- reaction
(Sohmitt, B. 1, 67).— 4. From p-ohloro-aniline
by displacing NH, by OH through the diazo-
reaotion (Beilstein a. Kurbatofi, A. 176, 30 ; B.
7, 1395).
Pj-oper*ies.— Crystalline ; v. si. sol. water,
y. e. sol. alcohol and ether. Insol. aqueous
NajCO,. Potash-fusion converts it into hydro-
quinone and resorcin (Petersen, B. 6, 1399 ; 7,
61; cf. Faust, B. 6, 1022). PCI, gives ^j-di-
ohloro-benzene [53°]. HNO, forms ohloro-nitro-
phenol [87°].
Salt.— C,H,Cl(ONa) (Vamholt, J.pr. [2] 36,
Methyl ether C,H,Cl(OMe). (o. 200°);
S.G. a 1-182 (Henry, Z. [2] 6, 247).
Ethyl ether 0,H,Cl(OEt). [21°]. (211°).
Benzoyl derivative C,H,Cl(OBz). [93°].
Phthalyl derivative C,H4(C02C,H,01),.
[11°] (Mosso).
(4:2:l)-Di-ohloro.phenol 0,H,CU0H)[4:2:1]
[42°]. (210°).
Formation.— 1. By chlorinating phenol (Lau-
rent, A. Oh. [2] 63, 27 ; [3; 3, 210 ; F. Fischer, Z.
[2] 4, 386; A. Suppl. 7, 180). -2. By adding
HCl to a mixture of phenol (1 moL) and aodium
hypochlorite (2 mols.), the (6:2:l)-isomeride is
formed simultaneously (Chandelon, B. 16, 1751).
Properties. — White needles. Sol. alcohol and
ether, nearly insol. water. Expels CO, from
boiling aqueous Ka^CO,, but in the cold it is ppd.
from its salts by CO,. PCI, gives tri-chloro-
benzene [16°].
Salts.— NHjO.CbH^CI: needles (from hot
NH,Aq). — KA' Jaq : decomposed by water at 70°,
giving oft ^-chloro-phenol. — HOPbA'. — AgA'.
Ethyl ether CaH^C^OEt). (237°).
Acetyl derivative C,H4Cl(0Ac). (245°).
Benzoyl derivative C,H,CljOBz. [97°].
Phthalyl derivative C,Hj(CO,C(|H,Cyj.
[108°] (Mosso, Ann. ChAm. Farm. 87, 184).
(6:2:l)-Di-chloro-plienol C.H,CL(OH)[6:2:ll
[63°]. (218°).
Formation.— rl. Together with the (4:2:1)
isomeride by adding HCl to a mixture of phenol
(1 mol.) and sodium hypochlorite (2 mol^.)
(Chandelon, B. 16, 1752).— 2. From di-chloro-
j)-amido-phenol by displacing NH, by CI through
the diazo- reaction (Seifart, A. Suppl. 1, 303 ; Z.
[2] 6, 450).
Properties.— 'Seedlea, Sol. alcohol and ether,
nearly insoL water.
Tri - chloro ■ phenol OACl3(OH)[6:4:2:l].
[68°]. : (244°). S. -051 at 11° ; -243 at 96°,-
Formation.— 1. By ohlorination of phenol '
(Laurent, A. Ch. [2] 68, 27 ; [3] 8. 497), of sali
genin (the product being distilled with cone.
H2SO4, Piria, A. 56, 47), of aniline (Hofmann,
A. 53, 8), of indigo (Erdmann, J. pr. 19, 332 ;
22, 276; 26, 472), of phenol snlphonio acid
(Vogel, Z, 1865, 629), or of phenyl benzyl oxide
C,H,0.CH2Ph (Sintenis, A. 161, 838).— 2. By the
action of NaOCl npon (2, 6, l)-di-chloro-phenol
[65°], and upon (2, 4, l)-di-ohloro-phenol [43°]
(Chandelon, Bl. [2] 38, 123).
Properties. — Needles or prisms. Acid to
litmns.
Reactions. — 1. HNO, forms di-chloro-quinona
[120°]; alcohol and N,0, produce the same
114
OTILORO-PHENOL.
body. — 2. PCI, or FojCl, from tetra-ohloro-benz-
•ne. — 3. HCl and EClO, give tetra-chloro-qain-
one. CrO, and HOAo produce the same body
(Levy a. Sohultz, A. 210, 160) 4. KjSO, at 170°
gives obloTO-phenol disulphonio acid and di-
chloro-phenol sulphonic acid (Armstrong a. Ear-
row, G. J. 29, 474).— 6. Br gives O^OjOBr
[99°] (Benedikt, JIT. 4, 236).
Salts.— NH,0,HjCl,0: needles; ▼. d. sol.
cold water. — KA' |aq. — MgA', 2aq. — BaA'. 4aq:
radiate groups of laminse. — PbA'^ — (PbA'JjPbO.
AgA' : yellow amorphous pp.
Ethyl ether Cja,Cl,(OEt) : [44°]. (240°'
(Faust, A. 149, 162 ; Lamport, J. pr. [2] 33, 381;
Acetyl derivative C,H,CII,(OAo). (26"
Propionyl derivative
C,HjClj.O(CO.OjHJ (263° anoor.), colourless
heavy liquid.
,Butyryl derivative OAC1,.0(CO.C,H,) :
(274° unoor.).
Valeryl derivative CAG1,.0(C0.C,H,) :
(283° unoor.).
Benzoyl derivative C.H^Cls.OBz : [70°];
colourless needles ; sol. alcohol and ether, insol.
water.
Phthalyl derivative
C;H,C1..0<g3>C.H,: [194°]; t. sol. chloro-
form, si. sol. alcohol and ether, insol. water
(Daccomo, B. 18, 1168).
Tri-chloro-phenol C.H,Ca,(OH). [64°]. (263°
nncor.). From tri-chloro-j>-amido-phenol (Lam-
pert, J.pr. [2] 33, 378). Also from phenol and
NaOCI (Chandelon, Bl. [2] 38, 119). Silky
needles (from dilute alcohol). Volatile with
steam. HNO, gives no quinone, but a nitro-
derivative [146°]. PCI, giVes 0,HC1,.
Ethyl ether CjHsCl,(OEt) ; (246° nncor.).
Acetyl derivative C.H,Cl,(OAc) ; (269°
nncor.).
Tetra-oUoro-phenol 0,H2Cls(0Cl) [6:4:2:1]
or C„H2C1,(CL;)0. ' jM-chloro-phenol chloride.'
[119°]. Formed by passing CI into tri-chloro-
phenol suspended in fuming aqueous ECl (Bene-
dikt, M. 4, 233). Trimetric pyramids; a:b:c
= 1:-61:-61. May be distilled. Cone. EOHAq
turns the crystals blue, and on boiling forms tri-
chloro-phenol. Hot cone. H^SOj gives tri-chloro-
phenol and tetra-chloro-quinone.
Penta-chloro-phenol C,C1,(0H) [188°].
JPormation. — 1. By the action at chlorine on
an alcoholic solution 6f tri-chloro-phenol, chloro-
isatin, or di-chloro-isatin (Erdmann, J. pr. 22,
272; Laurent, A. Oh. [3] 3, 497).— 2. From
phenol and chloride of iodine (SchUtzenberger,
Bl. [2] 4, 102). — 3. By passing chlorine into a
mixture of phenol or tri-chloro-phenol and
SbCl, at 200° (Merz a. Weith, B. 6, 458 ; Bene-
dikt a. Schmidt, M. 4, 606).— 4. Obtained by
heating heza-ohloro-benzene with a glycerin solu-
tion of NaOH at 250°-280°. Properties.— Sub-
limes in long white needles. ENO, forms tetra-
chloro-quinone. PCI, gives C,C1,.
S al tg.-C,01,0Na.-KA'.— AgA'.
Methyl ether C,Cl,(OMe): [108T; long
white needles ; v. sol. alcohol ; snblimable.
Acetyl derivative C,Cls(OAc): [148°];
fine white needles; v. sol. alcohol; sublimable
(Weber a. Wolff, B. 18, 336).
Bichloride C,Cl,(OE).Clj [78i°-^0^.
formed in the cblpnpatiQP 91 ff»-eblpro-aoetani}<
ide in acetic acid (Beilstein, B. 11,2182). Large
colourless pillars. Difficultly soluble in 50 p.o.
acetic acid, easily in C,H„ CHCl,, CS,, alcohol,
&o. Alkalis decompose it entirely. On heating
with alcohol per-chloro-phenol is formed.
Heza-chloro-phenol C.C1,0. [46°]. Formed
by passing CI into a solution of penta-ohloro-
phenol in dilute HCl (Benedikt a. Schmidt, M. 4,
607). Golden-yellow crystals ; gives oS chlorine
on heating. Tin and HCl re-convert it into
penta-chloro-phenol.
Diohloride 0,01,0. [102°]. Formed by
chlorinating penta-chloro-phenol in acetic acid
solution (B. a. S.). Prisms (from ligroin).
Eeza-chloro-phenol C,C1,0. [106°]. From
penta-chloro-aniUne by chlorination in acetic
acid solution (Langer, A. 216, 122). Tellowish
prisms (froni ligroin).
Fer-chloro-diphenol «. Ooto-ohlobo-di-ozt-
SIPHENYIi.
o-CHLOBO-FHEKOL (Y)-81TLFH0inC ACID
CjEjClSO, i.e. 0,H3C1(0H)S0,E. Fromo-chloro-
phenol and fuming EjSO, (Kramers, A. 173,331).
Small colourless plates or cubes (containing aq).
V. e. sol. water and alcohol. It begins to de-
compose at 80°. Fe^Cl, colours its solutions
violet. ENO, forms chloro-di-nitio-phenol
[111°].
Salts.— KA'iaq: S. (of KA') 14 at 9°.—
KjCgEjClSO, 3|aq : deliquescent lamina. —
NaA'aq. — NajC,H,ClSO, 3aq. — CaA'^aq.— ■
CaC,E,ClS04 3|aq: efflorescent crystalline
aggregates ; S. 38 at 12°.— BaA', l|aq : granu-
lar aggregates of crystals. — PbA'j 4aq. '—
PbC,H,ClSO, aq.— CuA'24aq : bluish-green tri-
metric prisms.
0-ChIoro.pnenol (8)-Bnlphonie acid
O,H,Cl(0H)S0,H. Formed, together with the
preceding, when the sulphonation is effected in
the cold by faming HjSO, (1 pt.) mixed with
cone. HjSO, (1) pts.) (E.).— KA' : small platen
CaC,E,ClSO, 2aq : small needles; S. 2-26 al
11°.
o-Chloro-phenol (/3)-snlplionic acid
C,E,C1(0E)S0,E. Obtained, in small quantity,
in Bulphonating impure n-chloro-phenol (Peter-
sen a. Baehr-Praderi, A. 157, 129). Potash-
fusion gives pyrogallol. Fe,Cl, colours iti
neutral solutions violet. EKO, gives chloro-di-
nitro-phenol [81°].— KA': stellate groups of
short prisms; less soluble than potassiom
j>-chloro-phenol sulphonate.
jp-Chloro-phenol (a)-Bulplionia acid
O.E,Cl(OE)(SO,H). [76°]. From p-oUoro-
phenol and fuming H2SO4 at 100° (Petersen a.
Baehr-Praderi, A. 167, 121). Glittering plates
(containing aq). Begins to decompose at 100°.
Gives a bluish-violet colour with Fe^Cl,. Pot-
ash-fusion gives pyrogallol and a trace of hydro-
quinone. HNO, forms chloro-nitro-phenol sul-
phonic acid (Armstrong, B. 7, 404) and chloro-
di-nitro-phenol [81°].
Salts. — EA'2aq: flat monoclinio prisms;
S. 10-8 at 20°; 44-3 at 100°.— KA' aq.— KA'
(from alcohol) : needles. — NaA' : groups oi
needles LiA' aq.— NH,A': [230°].— BaA',.—
BaC,H,aSO, 2aq.— CaA', 2aq : easily soluble
needles. — MgA'^Oaq: small flat plates or
needles. — CuA', 6aq : greenish-white needles, t.
e. sol. water.
Kihyl rferivff<»«« C.E,Cl(OEt)SO^
OHLORO-PHENYL-AOETIO AOID.
Ilfi
Salt. — KA' : stellate groups ot needles.
Chloro-phenol disulphonie aoid
0,H,01(OH)(SOjH), [4:1:6:2]. Formed, together
with di-ohloro-phenol sulphonio acid, by heating
tri-ohloro-phenol with EjSO, at 170° (Armstrong
a. Harrow, C. J. 29, 474). The same aoid
appears to be formed by sulphonating p-ohloro-
phenol at 100° (Petersen a. Baehr-Praderi, A.
157, 163). Gono. HKO, forms chloro-di-nitro-
phenol [81°].
Di-chloro-phenol snlphonie add
C.HjCl,(0H)(S03H) [4:2:1:6]. From (4,2,l)-di.
chloro-phenol and CISO3H [43°] (Armstrong,
C. J. 26, 93). Formed also by ohlorinating
phenol o-Bulphonic acid; and by heating tri-
chloro-phenol with EjSO, at 170° (Armstrong a.
Harrow). HNO, (S.a. 1-36) forms di-ohloro-
nitro-phenol [121°].
Di-chloro-phenol snlphonie acid
CjaL,CLi(OH)(SO,H) [2:6:1:4]. Formed by chlo-
rinating phenol j>-sulphonio acid (Eolbe a.
Gaohe, A. 147, 76) and by snlphonating (2,6,1)-
di-chloro-phsnol. Deliquescent trimetrio tables
or prisms. HNO, forms di-chloro-nitro-phenol
and ohloro-di-nitro-phenol [111°] (Faust, Zm
1871, 338; Armstrong, C. J. 24, 1112).—
BaA',2aq (dried at 100°).
Tri-chloro-phenol snlphonie acid
C,HCa3(0H)(S0aH). From tri-ohloro-phenol
and C1S0,H (Armstrong, C. J. 2S, 97 ; cf. Ke-
kul6, K. 3, 233). Its aqueous solutions decom-
pose with deposition of tri-chloro-phenol.
TSI-CHLOSO-FHENOUALIC ACID
CHjCljO, ».«. CCl,.CO.CH:CH.COjH oc
CH.C(OH).GC!l,
jl >0 (Anschutz,^.239,176). 2Vt-c%Zoro-
CH.CO
aeetyl-acrylie acid. [132°]. From benzene (80g.),
HjSO, (1,200 g.) and water (600 g.), to which
KCIO, (120 g.) is slowly (in 5 days) added with
gentle shaking. The benzene is then separated
and eyaporated, the residue is extracted with
water and the acid (6 g.) extracted from the
water by ether (Carius, A. 140, 317 ; 142, 131 ;
KekuU a. O. Strecker, A. 223, 179). Qumone
may be gnbstituted for benzene.
Properties. — Glittering plates (from water).
May be sublimed. Is volatile with steam.
Reactions. — 1. Warmed with baryta it gives
chloroform and bario mtileate. — 2. Combines
with bromine in chloroform with formation of
CC!l,.CO.CHBr.CHBr.CO^ [97-5°]. This is si.
sol. water, v. sol. alcohol, ether, and chloroform.
Boiled with lime water, it gives chloroform and
inactive calcic tartrate.
Theory of Formation. — Kekul6 supposes
that it is produced from chloro-quinone, and if
this is written 00<g2:QQ>CO the conversion
of it into CO<QgQQ >C!0 does not appear
very di£Sonlt to understand.
CHLOBO-FHENOZT-ACETIC ACID
C,H,C10,».«. C,H401.0.CH,.C0jH. [162°]. From
phenoxy-acetio aoid by successive treatment
with PCI. and water (Michael, J.pr. [2] 85, 96).
Trimetric prisms (from watei).
o-CHIOSO-SIPHEirTL O^fiJOL i.e.
0,H..C,H,C1 [2:1]. [34°]. (267°). Formed, to-
gether with the p-isomeride, bypassing chlorine
into diphenyl mixed with SbCl, (KrSmers, 4-
189, 142). Monoclinic crystals ; v. sol. ligroln.
CrOj gives o-ohloro-benzoic aoid.
TO-Chloro-diphenyl C,H5.0,H,01 [3:1] 7 [89°].
Formed by heating 0,B.fiK with calcium
ra-chloro-benzoic aoid (Pfannkuch, J.pr. [2] 6,
j»-Chloro-diphenyl O.H..O,H,Cl [4:1]. [76°].
(282°). Formed by chlorinating diphenyl («.
supra) or by treating jp-oxy-diphenyl with POl,
{Ot. Schultz, B. 7, 52). Thin plates (from
ligroiin). Smells like oranges. May be oxidised
top-cmoro-benzoio aoid.
Di-i)-chloro-diphenyl[4:l]O.H,C1.0,H.CI[l:4].
[148°]. (o. 317° oor.).
Formation. — 1. Amongst the products of the
action of PCI, on di-^i-oxy-diphenyl (Schmidt a.
Schultz, B. 12, 494; A. 207, 339).— 2. From
di-amido-diphenyl (benzidine) by displacement
of NH2 by Gl through the diazo- reaction (Oriess,
Tr. 1864, iii. 730) ; e.g. by heating tetrazo-di-
phenyl with a large excess of HGl; the yield
being 16 p.a. of the theoretical (Gasiorowski a.
Wayss, B. 18, 1941).— 8. By ohlorinating di-
phenyl (Kramers, A. 189, 138, 145).— 4. By
passing chloro-benzene through a red-hot tube.
Prcfperties. — Prisms or needles ; insol. water,
si. sol. alcohol, T. sol. ether. CrO, gives 2>-chloro-
benzoic acid.
Penta - chloro - diphenyl (CuHjClj. [179°].
Formed together with other products by , the
action of PCI. on di-p-oxy-diphenyl (Schmidt a.
Schultz, B. 12, 495 ; cf. Doebner, B. 9, 130).
Long needles. Sublimable.
Fer-chloro-diphenyl O^Cl,,. Prepared by
exhaustive chlorination of diphenyl in presence
of SbOl, or iodine (Buoff, B. 9, 1491 ; Weber a.
Sollscher, B. 16, 882 ; Merz a. Weith, B. 16,
2881). Formed also by exhaustive chlorination
of ditolyl (Merz a. Weith, B. 12, 677), benzidine,
carbazole (Zetter, B. 10, 1233), and phenanthra-
quinone (Merz a. Weith, B, 1ft, 2871). Iiong
tables or prisms. Does not melt below 270°.
V. si. sol. alcohol or ether. Not attacked by
SbCl, even at 350°. Alooholio NaOH at IbT
gives 0,jGl,(OH)j.
o-CHLOBO-PHENYL-ACETIC ACID C,H,C10,
i.e. 0^j.CHCl.CO:,H. [78°].
Formation. — 1. From mandelic acid
C.H,.CH(OH).CO^ and HCl at 140° (Badzis-
zewski, B. 2, 208). — 2. From benzoic aldehyde
by conversion into PhCH(OH)GN by EGN and
HCl, the mandelo-nitrile being then treated with
HCl (Spiegel, B. 14,'235; B. Meyer, A. 220,41).
3. From C9H,.GH:CH.N0, and fuming HCl at
100° (Priebs, A. 225, 337).
Properties. — Trimetrio tables; sL sol. cold
water and ligroln, t. e. aol. alcohol and ether.
Sodium amalgam oonverts it into phenyl-acetio
aoid. Boiling aqneona EOH forms mandelic
aoid. Phenyl-hydrazine forms benzylidene-
phenyl-hydrazine C,H,CH:N2HPh (Beissert, B.
17, 1452). The salts are unstable.
Methyl ether MeA' (248° oor.). Oil (Meyer
a. Boner, B. 14, 2392).
j)-Chloro-phenylacetio acid OriH,ClCHg.C02H.
[104°]. Prepared by saponification of the nitrile
(Nenhof , A. 147, 346 ; Jackson a. Field, P. Am. A,
14, 68). Also by treating phenyl-acetio acid
with CI in sunshine (Badziszewski, B. 2, 208)
Long needles (from w^ter). V. sol. bpnzene,
116
OHI^ORO-PHENTI^AOETIO ACID.
water, alcohol, and ether. — AgA' : cuidy mass. —
CaA'jaq.
4mtd« C;H,C1.0H,.C0NHj. [176°]. Tables
(from aloohol). V. sol. alcohol and ether, si. sol.
hot water.
Nitrile CjH,Cl.CH2.CN. [29°]. From p-
ehloro-benzyl bromide by heating with alcoholic
KCy (Jackson a. Field, Am. 2, 88). Prisms ;
Bol. alcohol and ether.
Oi-a-chloro-phenyl-acetio acid
C^s.CClj.COjH. [68°]. Prepared by the action
of PCI5 on phenyl-glyoxylio ether and subsequent
saponification (Glaisen, B. 12, 630). Small tables.
V. sol. water, alcohol, and ether.
Ethyl ether A'Et. (263°-266°)l
Nitrile CfiyCClfON. (224°). From benzoyl
cyanide and PCa, (C).
SLa-CHLOBO-FHENTL-ACETIC ALDEHYDE
C^s.CCl,.GHO. (295°). From chloral, benzene,
and AIiGlg at 70°. The product is treated with
water and fractionally distilled in vacuo, y^hen
the compound 0,Hj.CC!l2-GHCl(0H) passes over
at 180°. By the action of EOH it is converted
into the aldehyde by removal of HCl (Combes,
0. B. 98, 678). Liquid. Beduces Fehling's
solution and combines with NaHSO,, although
with di£Sculty. Benzene and Al^Cl, convert the
aldehyde into tri-phenyl-methane.
CHLOBO - PHENYL • ACBYLIC ACID v.
Chlobo-cinkamic acid.
CHLOBO-FHENYL-AMIDO-CHLOBO-ITAFH-
THOQTTIKOD'E v. Chloko - naphthoquinone -
CHLOBO-ANILIDE.
CHLOKO-PHENYL-AMIDO-HYDBONAPH-
THOQTIINOlfE C„H,jClNOj i.e.
C,„H,01(0H)2(NHPh). [171°]. From ohloro-
naphthoquinone anilide and cone, aqueous SnOlj
(Knapp a. Sohultz, A. 210, 190).
■ Acetyl derivative [169°].
CHLOBO ■ DI- PHENYL-DI-AIIIDO -HYDBO-
auiNOHE C„H, jClN Ai-e- C,HCl(OH)j(NHPh) j.
From ohloro-di-phenyl-di-amido-quinone, cone.
SnCljAq, and alcohol (Knapp a. Schultz, A. 210,
181). Slender needles. Decomposes about
223°. Beadily oxidised to the corresponding
quinone.
Di-chloro-dl- phenyl- di - amido-hydroqninone
C„H,,GL,NA »•«• C,Glj,(NHPh)2(0H)j. Formed
by boiling dt-chloro-di-phenyl-di-amido-quinone
C,Clj(NPhH)202 with cone, aqueous SnGl^
(Enapp a. Schultz, A.210, 181). Slender needles,
V. sol. water. Oxidation gives C,Cl,(NPhH)202.
Boiling Ac^O gives long needles of O.M^Ji,
[235°].
j>CHLOBO-DI-PHEirYL-DI-27-AUIDO-TBI-
PHENYL-METHANE C.H4Cl.CH(C,H,.NHPh)j.
Not isolated in a pure state. Formed by heating
together diphenylamine and p -chloro-benzalde-
byde in presence of ZnCl^ On oxidation it gives
a green dye-stuff (Eaeswurm, B. 19, 745).
TEX - CHLOBO - TBI - PHENYL -TBI. AMIDO-
Li-FHENYL-IOLYL-CABBINOL v. TBt-CHi,oBo-
Tni-PnENYI.-BOSANILniB.
CHLOBO -FHSNYL-AIOIDO-QTriNONES «.
AKiiiiDES of Cblobo-quinoniis.
p-CHLOBO-DI-FHENYL-AMINE
PhNHCjH,a. [74°]. Formed by treatmg diazo-
tised p-amido-di-phenyl-amine with cuprous
chloride (Ikuta, A. 248, 286). Long prisms.
T. si. lol. water, v. sol. ether, aloohol, benzene.
petrolenm ether. Yields a nitrosamine
PhN(NO)CBH,Gl [88°], v. sol. alcohol and ether,
which on standing with alcoholia HGl is con-
verted into the isomeric ^-nitroso-ohloro-di-
phenyl-amine C,H,(N0)NH0,H,01 [159°] green
plates (from benzene).
Dl ■ chloro - di -phenyl - amine NH(0,H4C1),.
[80°]. From the benzoyl derivative and alco-
holic EOH at 160° (Glaus a. Sohaare, B. IS,
1286). Needles.
Benzoyl derivative'S'Bz{0,B.Sil)i. [153°].
From benzoyl-di-phenyl-amine by chlorination
(G. a. S. ; cf. Glaus, B. 14, 2368). Needles (from
aloohol).
Tetra-chloro-di-phenyl-amine NH(CeH,CI,)2.
[134°]. Formed by passing CI into a solution of
di-phenyl-amine in EOAc (Gnehm, B. 8, 1040).
Prisms or needles.
Per-chloro-tri-phenyl-amine N(CjCl5)3. From
tri-phenyl-amine by exhaustive chlorination
(Buofi, B. 9, 1494). Needles (from benzene-alco-
hol).
DI-CHLOBO-FHENYL-ANTHBANOL
/G(G,H,C1).
0„B.,,Clja i.e. C.H/ I >0.H,C1. [170°].
\C(OH) - /
From C0<q''2*(,i>G(0H).CsH,C1 (phenol-
phthalidein chloride), acetic acid, and zinc-dust
(Baeyer, A. 202, 95). Needles (from aloohol).
Y. si. sol. alcohol; m. sol. acetone and ether,
with bluish-green fluorescence.
Dihydride O.H,<^gg«^^.Cl)^c.H3Cl.
Hydrophenolphthalidin chloride. [56°]. From
the preceding by heating in alcoholic solution
with sodium amalgam (B.). Long needles (from
CSJ.
FEB-CHLOBO-DI-PHENYL-BENZENE
G,jGl,4. Formed by exhaustive chlorination of
di-phenyl-benzene by means of SbCl, (Merz a.
Weith, B. 16, 2884). Colourless needles. V.
sol. hot nitrobenzene, si. sol. alcohol, ether, and
acetic acid.
Per - chloro - tri - phenyl - benzene Cj,Cl„.
Formed by exhaustive chlorination of tri-phenyl-
benzene by means of SbCl, (Merz a. Weith, B.
16, 2883). Colourless needles. V. sol. hot
nitrobenzene, si. sol. ether, benzene, and alcohol.
It is only slightly attacked by HNO, at 350°.
CHLOBO-FHENYL BENZYL OXIDE
C8H,C1.0.CHjPh. [71°]. From phenyl benzyl
oxide and Gl in presence of HgO (Sintenis, A.
161, 338). Long needles (from alcohol).
V TBI-CHLOBO-DI-PHENYL-BUTANE
0,8H,sCl, i.e. CH3.GHGl.CGlj.CHPhj. [80°]. S.
(ether) 50; (alcohol) 2. From tri-chloro-butyric
aldehyde, benzene, and HjSO, (Hepp, B. 7, 1420).
Monoclinic prisms (from ether-alcohol).
TBI-CHLOBO-DI-PHENYL-BUTANE DISUL-
PHONIC ACID C,.H„G1,(S0,H),. From 0,<,H,.C1,
and fuming HjSO, (Hepp, B. 7, 1420).— BaA".
CHLOBO-DI-PHENYL-«er<-BUTYL ALCOHOL
CClPhj.CMejOH. (239°). From Uquid acetone-
chloroform, benzene, and ALCl, (Willgerodt,
J.pr. [2] 37, 362).
Di-chlora-phenyl-<er^'batyl aloohol
CCljPh.GMejOH. (217°). From acetone-chlo-
roform, benzene, and A1,C1, (Willgerodt a. Oe-
nieser, /.pr. [2]87, 367). Liquid,
CULLORO-DI-PHENYL-ETHYLENE.
117
CHLOBO-o-FHENTLENE-SIAiaNE
C<P,C1N, i.e. C,H,Cl(NH2)j [4:2:1]. [72°]. Prom
ehloro-di-nitro-benzene [39°] by leduction with
tin and HCl (Laubenheimer, B. 9, 773). Laminee.
VejBi, gives a red colour and a brown pp.
Chloro-m-phenylene-diaiuine CgHaCllNH^),
[4:3:1]. [86°]. From ohloro-di-nitro-benzene
[50°], tin, and HCl (Beilstein a. Kurbatoff, A.
197, 76). Keedles (from ligroin).
Chloro-p-phenylene-diamine CaH3Cl(NH2)2
[2:4:1]. [123-5°]. From di-ohloro-nitro-aniline
[188°], tin, and HOI (Witt, B. B, 145). Flat
needles. — B'HCl : long needles.
Oi-chloro-o-plienylene-diamine C^fi\.JJXB^)i
{6:3:2:1]. [60-5°]. From di-ohloro-nitro-aniline
[100°], tin and HCl (Witt, B. 7, 1604). Long
flexible needles (from alcohol).
Bi-ehloro-p-phenylene-diamineCgE^Cl^fNHj):
[5:2:4:1]. [164°]. Formed, togethe* with di-
methyl-j}-phenylene-diamine and di-chloro-di-
methyl-j)-phenylene-diamine, by boiling nitroso-
di-methyl-aniline with HCl (S.G. 1-2) (Mohlau,
B. 19, 2010). Colourless glistening prisms. By
EjCr^O, and H^SO, it is oxidised to di-chloro-
quinone [159°]. The dilute HCl solution on
treatment with chloride of lime yields di-chloro-
quinone-di-cblorimide [134°].
Tetra-chIoro-j)-phenylene diamine
C,0l4(NE[j)r [218°]. Formed by boiling quinone
dichlorimide with HCl (S.G. 1-2) (Krause, B. 12,
51). Bed needles (from dilate alcohol).
DI-CHLOBO-BI-PHENYLEKE EEIONE
C„H,CljO. [158°]. From di-chloro-fluorene by
CrO, (Hodgkinson a. Matthews, C. J. 43, 170).
DI-a-CHLOBO- PHENYLENE - SI - U£THYL-
DI-MAIONIC ETHEB CjH,(CHjCCl(COJEt),i);.
V. Exo-di-chloro-xylylene-malonic ether.
TEIBA-GHLOBO-FHEXYLENE-DI-METHTL
OXIDE C,C1,<qJ^0. [218°]. V.D. 8-6 (oalo.
8-9). From tetra-chloro-phthalic acid, HI, and P
at 230° (Grsebe, A. 238, 831). Needles (from
Octo-chloro-phenylene-di-methyl oxide
0,CI^<^^^0. [140°]. From tetraohloro-
phthalio anhydride and PCI5 at 200° (G.)
DI-CHIOBO-PHEinrLEHE-(a)-NAPHTHYI.
EHE-OXIDE C„H,C1,0. [245°]. Prepared by
the action of PCI, on phenylene-(o)-naphthylene-
oxide (Arx, B. 13, 1727). Fine white needles.
V. sol. alcohol and ether, si. sol. benzene.
TETBA-GHLOBO-FHEKYLENE OXIDE
C,C1,0 (?) [320°]. (above 360°). Formed by
distillingpotassiumpenta-chloro-phenolCgClsOK
(Merz a. Weith, B. 5, 461). Flat needles. V. si.
sol. alcohol and ether. Not affected by PCI, at
250° or by sodium-amalgam.
CHLOBO • PHENYL - ETHANE v. Chlobo -
ETH^L-BENZENi:,
Chloro - di - phenyl - ethane C,«H„C1 i.e.
CHsCl.CHPhj. From di-ohloro-di-ethyl oxide
OHjCl.CHCl.OEt, benzene, and HjSO^ (Hepp, B.
6, 1439). Liquid. Splits up on distillation or
treatment with alcoholic KOH into HCl and
CnH|2.
Di-p-chloro-di-phenyl-ethane
C8H4Cl.CH,.CH2.CsH,Cl. JH-chloro-dAhmzyl.
[112°]. Formed by passing chlorine over a solid
«ake of dibenzyl (150 pts.) and iodme (1 pt.) till
■the cake liquefies. This is distilled and the pro-
duct crystallised from alcohol (Kade, J.pr. [2]
19, 462). Glittering plates which feel greasy.
Sol. alcohol, ether, and chloroform. Chromic
mixture oxidises it to j}-chloro-benzoio acid.
(a)-Di-exo-cMoro-s-di-phenyl ethane
C,H5.CHC1.CHC1.C,H5. Stilhem (o)-cAZorii«.
[193°]. Formed, together with the (/SJ-isomeride,
by the action of PCI, on hydrobenzoin (Zincke,
A. 198, 129) and by the union of 01 with s-di-
phenyl-ethylene (Laurent, B.J. 25, 620). Formed
also from isohydrobenzoin and PCI5 (Ammann,
A. 168, 67). Perhaps identical with the com-
pound [180°] which is formed by heating benzyl-
idene chloride with copper-powder at 100° (Onu-
frowicz, JB. 17, 835).
Prcfperties. — Silky needles (from alcohol),
prisms (from toluene), or plates (0.). SI. sol.
boiling alcohol. May be sublimed. Alcoholio
EOH forms s-di- phenyl -acetylene (tolane),
AgOAo followed by KOH gives isohydrobenzoin.
(;3)-Di-exo-chloro-s-dl-phenyl-ethane
C,H5.CHCl.CHC1.0„Hi. SHlbene {0)-chloride.
[94°]. Formed as above. Thick tables. At
200° it is partially converted into the (a)-iso<
merlde.
Tri - chloro - s - dl - phenyl - ethane 0,4E„C1,.
[85°]. From s-di -phenyl -ethylene and CI
(Laurent).
Tri-chloro-u-di-phenyl-ethane CCl,.CHFh,.
[64°]. From chloral, benzene, and HjSO^
(Baeyer, B. 5, 1098). Small thin plates. Alco-
holic KOH gives CPhj:COl,.
Tri-chloro-u-di-phenyl-ethane
CH2Cl.CH(CsH,Cl)j. From di-chloro-di-ethjl.
oxide CH^CLCHCLOEt, chloro-benzene, and
HjSO, (Hepp, B. 7, 1419). On distillation it
gives CBL,:C(C^,C1)2.
Tetra-chloro-s-di-phenyl-ethane
Ci,'E.yCClpCCli.OfiyToUineteira-chloride.p.eS°}.
FormaUon. — 1. Frombenzil and PCl5(Ziuin,
Z. 1868, 718).— 2. A by-product in the pre-
paration of benzotrichloride by chlorinating
toluene (Liebermann a. Homeyer, B. 12, 1971).
3. By heating benzotrichloride with copper-'
powder at 100° (Onufrowicz, B. 17, 833).— 4.
By heating benzotrichloride with benzene and
copper-powder (Hanhart, .B. 15, 901).
Properties. — Trimetrio crystals;, sol. benz-
ene, hot alcohol, and ether. Gives a violet dye
with dimethylaniline and ZnCl^. Alcohol and
zinc-dust gives (o) and (;8) di-chloro-di-phenyl-
ethylene.
Penta-chloro-M-di-phenyl-ethane
C0l3.CH(CsH,Cl)j. [105°]. S. (95 p.o. alcohol)
10. From chloral, chlorobenzene, and HjSO,
(Zeidler, B. 7, H81). Felted needles (from
ether-alcohol). Alcoholic KOH gives CuHgCl,.
CHLOBO-DI-PHENYL-ETHYLENE
CsH5.CCl:CH.C„Hj. Chloro-stilbene. Fromstil-
bene di-chloride and alcoholic KOH (Zinin, A.
149,375). OU.
(a)-Di,-chloro-«-di-phenyl-ethylene
C„H,.CCl:CCl.CeH5. Tolaiie - (o) - 3i - chloride.
[143°]. Formed, together with the (3)-modifi-
cation, by the action of powdered zinc on an
alcoholic solution of tetra- chloro -di- phenyl
ethane (Liebermann a. Homeyer, B. 12, 1973 ;
c/. Zinin, B. 4, 289) ; or of iron powder on an
acetic acid solution of the same body (Lacho-
wicz, B. 17, 1165). Formed also by passing 01
into a solution of s-di-phenyl-ethyleue in chloro-
118
OHLORO-DI-PHENYL-ETIIYLENE.
form. Both modifioationa are also formed by
heating benzo-tricbloride with oopper-powder
(Hanhart, B. 15, 899), and by heating s-di-
phenyl-ethylene mth PGl, at 180° (Limprioht
a. Schwanert, B. 4, 379). Trimetrio tables or
prisms. SI. sol. alcohol. Alcoholic EOH at
180° giveB *-di-phenyl-acetylene (tolane).
(jB)>Di-ohloro-s-di-phenyl-ethylene
0,H,.CC1:C01.G,H,. Tolane - (/3) ■ dt - chloride.
[63°]. Formed as above. Long needles. Mora
soluble in alcohol than the (a) -modification.
The (a) and {$) modifications can be partially
ohanged into one another by distillation.
Si-cbloro-u-di-phenyl-ethylene CCl^iCPh,.
[80°]. Formed by passing CI into u-di-phenyl-
ethylene and distilling the resulting CCl^.OClFh,
(Hepp). Formed also from GCls-CHPh, by
boiling with alcoholic EOH (Baeyer, B. 6, 223).
Monoolinic prisms (from alcohol).
Si-chloro-di-phenyl-ethylene
C,H,G1.CH:0H.C„H<C1. [170°]. Formed by pass-
ing CI in excess into melted dibenzyl (Eade,
J. pr. [2] 19, 466). Needles or plates (from
alcohol).
Si-cnlorO'»-di-phenyl-ethylene
JH,:C(C,H,C1)2. (283°). Formed by distiUing
CHjCl.CH(O.H,Gl), (Hepp, B. 7, 1419).
Iri - ohioro-t-di - phenyl - ethylene C^HgCl,.
Two modifications are formed by treating s-di-
phenyl-acetylene (tolane) with PGlj (Limpricht
a. Schwanert, B. 4, 379).
(a)-Modifieation: [137°-145°]; needles.
(i3)-Moditiaation: [150°]; prisms.
Tetra-chloro-di-phenyl-ethylene
CClj:G(G,H,a)j. [89°]. From GC1,.GH(G,H,G1),
and alcoholic KOH (Zeidler, B. 1, 1181).
<.-IBI-CHLOBO-])I-FH£NTL-£IHYLII)Eir£
DIAMINE C,.H„NjCl, i.e. GGl,.GH(NHG.HJj.
[101°]. Formed by the action of aniline on
chloral (Wallaoh, B. 5, 251; A. 173, 277).
Tabular crystals (from alcohol). Insol. water.
Decomposes at 150°. Boiling with alkalis forms
phenyl carbamine. — B'^RjPtGl, (Amato, B. 9,
198).
DI-CHLOaO-DI-FHENTL-GUANISIirE
0„H„G1,N, lA NH:C(NH.C,^4Cl)j. From
aqueous di-phonyl-guanidine hydrochloride and
Gl (Hofmann, A. 67, 147). Lamina: (from aloo-
hol).— B'jHjPtCl,. <
Di-ohloro-di-phenyl-gnanidine
NH:C(NH.CeH,01)j. [141°]. From di-ohloro-
di-phenyl-thio-urea, PbO, and NH, (Losanitsch,
Bl. [2] 32, 170). Needles. Perhaps identical
with the preceding.
Tri-p-chloro-tri-phenyl-guanidine
C„H„Cl,N,i.e. C.H,Cl.N.C(NH.C.H,Cl)j. Formed
by adding iodine to an alcoholic solution of di-
ohloro - di - phenyl -thio - urea CS(NH.G,H,C1)2
(Beilstein a. Kurbatofi, A. 176, 51). Slender
needles (from GSJ.— B'HCl.— B'HI : [255°].—
B'jHjSO,.
CHLOBO-SI-FHENTL-KETONE v. Chloro-
BBNZOFBENOm.
CHLORO-FHENTL IIEBCAFTAN
0,H,C1.SH. [64°]. From ohloro-benzene sul-
phonic chloride, zinc, and dilate H^SO, (Otto,
A. 143, 109). Four-sided trimetric tables (from
alcohol).— (08H<Cl.S)2Pb : yellow pp.
. p-CHLOSO-FBENyl. MEBCAFIUBIC ACID
C„H,jClNSOji.e.
CH,.CO.NH.CMe(S.G.H,Cl).CO,H. [164°].
Found in the urine of a dog after it had taken
ohloro-benzene (Jaf[6, B. 12, 1092). Goloarlesg
leaflets or tables. V. al. sol. ether, t. soL
alcohol.
;3 ■ CHLOBO ■ J3 ■ FHEKTL - UETHACBTLIO
ACID 0,„H,C10,t.«.O.H5.CGl:CMe.COjH. [116°].
From methyl-benzoyl-acetic ether, POGI,, and
PCI, (Ferkiu, jun., a. Caiman, G. J. 49, 159).
Needles, t. sol. alcohol, ether, benzene, and
HOAo, m. sol. cold light petroleum. — ^AgA'.
' CHLOBO-DI-FHENTL-METHANE
(CgHJ^GHGl. Di'phemyl-eavhmyl chloride.
[14°]. From di-phenyl-carbinol and HCl (Engler
a. Bethge, B. 7, 1128). Decomposed Iby heat
into HCl, tetra- phenyl- ethylene, and tetra-
phenyl-ethane (Anschiitz, A, 236, 220).
Dl-ohloro-di-phenyl-methane (C,Hi),CCIy
Bemophmoneehloride. (305° i.V.). S.O. — 1'235.
From benzophenone and PClg (Behr, B. 3, 752). ,
Liquid. Decomposed by distillation. Warm
water reconverts it into benzophenone. EH3
gives (CgHJ,^CS. Heating with silver forma
PhjCCPhj. Aniline forms PhsC:NPh. Di.
methyl-aniline gives Ph^CH-GgH^NMe, (Fauly,
A. 187, 198).
Chloro-tri-phenyl-methane (CsHs),GCl. Tri-
phenyl ca/rbiwyl chloride. [105°-11S°]. From
tri-phenyl-carbinol and PCI, (Hemilian, B. 7,
1207). Formed also by the action of benzene on
CCI4 in presence of Al^Cl, (Friedel a. Grafts,
A. Ch. [6] 1, 602). At 250° it gives HCl, tri. ,
O.H.V
phenyl-methane, and I ^CH.C,H,(Hemilian,
■B, 11, 837). Hot water forms tri-phenyl-car-
binol.
DI-CHIOBO - TBI . FHENIL ■ METHANE
CABBOXYLIC ACID (C,H,Cl),CH.G„H,.GOjH.
[206°]. From di-chloro-di-phenyl-phthalide and
boiling alcoholic NaOH ; the resulting
(C,H<Cl)jC(OH).C.H,.COsH being reduced with
zinc-dust and aqueous NaOH (Baeyer, A. 202,
84). Six-sided tables (from alcohol). CrO,
gives di-ohloro-phenyl-ozanthranol.
Tetra-chloro-di-phenyl-methane oarbozylio
acid V. TslBA-CHLOIIO-O-BENZYL-BENZOia ACID.
DI-CHLOBO-DI-FHENYt-METHANE STTL-
PHONIC CHLOBIDB C„li,Sfifil, ».«.
CCL,(C5H,S0sCl)r [129°]. From C0(C.H<S0,G1),
and PClg (Becknuum, B. 8, 992). Amorphous;
si. sol. alcohol.
T£IBA - CHLOBO- 01 - PHENYL - METHYL.
AMINE G„H,NC1, i.e. (C.H,Clj),NMe. [97°].
Formed by passing CI into a solution of NPhjMe
in HOAc (Gnehm, B. 8, 1040). Prisms.
CHLOBO- PHENYL -METHYL -KETONE v.
CHIiOBO-AaEIOFHENOIIB.
BI-CHLORO-FHENYL-OXAStIC ACID
0,HaCl,.NH.CO.COja. [122°]. S. -124 at 25°.
Prepared by boiling tetra-chloro-oxanilide (4 gr.),
alcohol (125 co.) and EHO (6 gr.) for 10 minutes
(Dyer a. Mixter, Am. 8, 854). White fibres.
Sol. alcohol and ether. EHO solution gives di.
chloro-anUine [63°].
Salts.— £A': white hair-like fibres.
TETBA-CHLOBO-DI.FHENYL-OXAMIDE
CA(NH.C„H,Cl,)j [1:2:4]. Tetra-chloro-oxaniU
ide. [0. 265°]. From oxanilide by chlorinatioa
in HOAo (Dyer a. Mixter, Am. 8, 349). White
fibres.
CnLORO-DI-PHENYL SULrnONB.
119
M-CHIOBO-PHENTl-OXANTHBANOL
Ca^H,,ClA t.e. CO<g«j|»Qj>C(OH).O.S,C!l.
Phenol-phthalide'Cn-cHlorike. [156°]. From di-
oxy-phenyl-oxanthranol (pMnol - phthalidein)
and PCa, at 130° (Baeyer, A. 202, 100). Silky
Aeedles ({rom alcohol).
jCHLOBO-FHENYL-FHOSPHOBIC ACID
0,H,ClPO,t.e.C,H«CaO.P0(0H)j. [81°J. Formed
together with p-di-ohloro-benzene by treatment
of phenol p-salphonio acid and PCI, ; the result-
ing CjH,Cll.O.POCLj being deoompoaed by water
(Kekulfi, B. 5, 877 ; 6, 944).— BaA".
Chloride C„H,Ca.O.POCl,. (265°).
f -CHLOBOPHEina FHTHALIUISX
0-0
0.h/No [194°-195° nncor.]. Pre-
C=N.C,H,d
pared by heating f-ohloro-aniline with phthalio
anhydride (Gabriel, B. 11, 2260). Long fine
needles. Sol. hot alcohol, CgH,, and acetic
acid.
a-CHLOBO-o-FHENVL-FBOFIONIC ACID
CsH,aO, t.«. CH3.CClPh.CO2H. Chloro-hydro-
atropie aoid [73°}. From atrolactio acid and
HCl in the cold (Merling, A. 209, 19). Small
prisms, m. sol. hot water, si. sol. cold water.
Volatile with steam. Attacks the mucous mem-
brane. Decomposes at 110°. Boiling alkaline
carbonates form no styrene.
/3-Chloro-a-phenyl-propio&ic acid
CHsOl.CHPh.CO2H. Chloro-hydratropie acid.
[89°]. Possibly identical with the preceding.
Prepared by the action of HCl on the cyan-
hydrin obtained from acetophenone and HCN
(Spiegel, B. 14, 236). From tropic acid andPCl^
foUowed by water (Ladenburg, A. 217, 77).
Formed also by the union of atropio acid with
fuming HCl at 100° (Merling, A. 209, 3). Colour-
less prisms. Sol. alcohol, ether, and benzene,
■1. sol. water and ligroin. On boiling with
aqueous NaOH it gives atropio aoid. On heat-
ing with NajCO, solution to 130° tropic acid is
formed. Boiling aqueous NajCO, forma tropic
aoid and a little styrene.
o-ChIoro-;3-phenyl-propionio acid
C^fS^Xj^tSjOfi^o-Chloro-hydrocimM'micacid.
[97°]. Needles or plates. Formed by reduc-
tion of o-ohloro-oimiamio aoid with HI and P
(Qabriel a. Herzberg, B. 16, 2037).
m-Chloro-/3-phenyl-propionio acid
CjH,Cl.C,H,.COjH. m - Chloro - hyd/rodrmamic
acid. [78°]. White easily soluble plates. Formed
by redootion of wt-ehloro-cinnamic aoid with HI
and P (G. a. H.).
ji-CliIoro-phenyl-propionie acid
0,H,Ca.C2H,.COjH.^-Cfctoro-Aydroci»WMW»«! acid
[124°]. Formed by ledaotion of ji-chloro-oiu-
namio acid (G. a. H.).
3-Chloro-;3-phenyl-propionie acid
C,H5.CHC1.CH2.C0:^. [126°]. From P-orj-P-
phenyl-propionic aoid and fuming HCl (Glaser,
A. 147, 95). Very slowly formed by combina-
tion of cinnamio aoid with HCl in cone, aque-
ous solution (Erlenmeyer, B. 14, 1867). Laminie.
Split up by heat into HCl and cinnamic aoid ;
and by aqueous NajCO, into CO^, HCl, and
styrene.
a^-Di-chlorO-iS-phenyl-propioiiifi acid
C»H,-CHCl.CHCl.COjH. [164°]. White plates.
Formed by leading 01 into a CS, solution of cin-
namic acid. With aqueous Na,CO, it gives «.
ohloro-styrene (Erlenmeyer, B. 14, 1867).
{py. i)-0Ei.0B0-(Py. 2)-PH£inri.-isoQTriir-
. ^001:0Ph
OMNE 0„H,.C1N «A Oja^ \ . [70°].
Obtained by reduction of {Py. l:4)-^-ohloro-(P^.
2)-phenyl-i8oquinoline with HI and P. Glisten-
ing pillars. Salts ^B'HCl : small thick crys-
tals.—B'jHjCljPtCl, : orange yellow needles (Ga-
briel, B. 18, 8475).
(Py. 4)- Chloro- (Py. 2) ■ phenyl -isoqninoline
I . [78°]. Prepared
C1:N
by boiling {Py. A)-oxy-{Py. 2)-phenyl.isoquinoline
(isobenzalphthalimidine) with POCl, (2 pts.). It
is also formed by heating the same compound
with PClj at 100°- 130°. Plat pointed needles.^
Sol. alcohol, V. sol. benzene, ether, petroleum-
spirit, chloroform, and CS^, insol. water. Heated
with HI and P at 170° it is reduced to phenyl-
isoquinoline (Gabriel, B. 18, 3473).
{Py. l:4)-I)i-oliloro-(P^. 2)-phenyl-i3oquinol-
yCa:CPh
ine C„H,0ySf i.e. 0,H.< | [163°]. Ob-
\CC1:N
tained by heating {Py. 4)-oxy-(Py. 2)-phenyl-iso-
quinoline (isobenzalphthalimidine) with POl, at
100°. By boiling with HI and P it is reduced to
{Py. l)-ehloro-(^. 2)-phenyl-iBoquinoline [70°]
(Gabriel, B. 18, 3473).
TBI - CHLOBO-IBI-FHENYL - BOSANILINE
C.H,Cl.NH.C,HjMe.C(0H)(CsH,.NH.C,H,Cl)2.
The 0-, i»- and2>-compounds are formed by heating
rosaniUne with o-, m-, or p-chloraniline in pre-
sence of benzoic acid. They dye silk various
shades of bluish violet (Heumann a. Heidlberg,
B. 19, 1992).
SI-CHLOBO-DI-FHENYL SULFmDE
(CeH,Cl)jS. [89°]. From ' thio-aniline '
S(C„H4NHj), by displacement of NH, by CI
through the diazo- reaction (Krafit, B. 7, 1165).
Di-chloro-di-phenyl di-snlphide (0<H.C1)~S-.
[71°]. From C.H,01.SH and HNO, (S.G. 1-12)
(Otto, A. 148, 111). Tables. Zinc and dilute
HjSO, reconvert it into chloro-phenyl mercaptan.
CHLOBO-DI-FHENYL SULFHONE
ObHs.SOj,.CoH,01. [92°], (889°). From benzene
sulphonio chloride, benzene, and AI^Cl, ; the
yield is 87 p.c. of the theoretical (Beckurts a.
Otto, B. 11, 2067 ; 19, 2418). Leaflets. Insol.
water ; v. sol. hot alcohol.
Si-o-chloro-di-pheuyl sulphone (CeH4Cl),S02.
[174°]. (860°); Formed in sulphonating,o-di-
chloro-benzene (Friedel a. Crafts, A. Ch. [6] 10,
414). Crystals.
Di-chloro-di-phenyl-snlphone 0,JB.,C[jiOi.
(above 300°). Formed by chlorinating di-phenyl-
sulphone in diffused daylight at 100° in presence
of iodine (Otto a. Gruber, A. 149, 180). Oil.
Si-jj-chloTo-di-phenyl-salphone (C,H4C1)2S02.
[141°] (O.) ; [147°] (B. a. O.). From ohloro-
benzene and SO, (Otto, A. 145, 28). Also from
ohloro-benzene and CISO3H- (Beckurts a. Otto,
B. 11, 2065). Plates. HjSO^ at 150° gives
chloro-benzene sulphonic acid. Sodium amal-
gam in alcoholic solution gives benzene, chloro-
benzene* sulphonio acid, and benzene sulphonio
acid.
ISO
CHLORO-PHENYL-THIO-OAHBAMIO ETHER.
CHLOBO-PHENTL-THIO-CABBAUIC EXHES
C,H<Cl.NH0a.OEt. [103°]. Formed by adding
iodina to an alcoholio solution of di-ohloro-
di-phenyl-thio-nrea (Beilstein a. KurbatofF, A.
176, S2). Needles.
o-CHLOBO-PHEITTL-THIO-CASBIMIDE
C.H,(C1).NCS [1:2]. [45"]. (250°). Crystalline
solid. Prepared by the action of PJO^ on the
corresponding urea derived from o-chloro-nitro-
benzene (Hofmann, B. 13, 14). An isomeride is
chloro-methenyl-amido-pbenyl-mercaptan
c.H,<g>oca.
fn-Chloro-phenyl-t1iiocarbiimdeOiH,(Cl).NCS
[1:3]. (250°). Prepared by the action of PA
on the corresponding urea [122°] obtained from
f»-ohloro-aniline and CS, (Hofmann, B. 13, 13).
Liquid.
f-CUoro-pIien7l-thio-carbimideCsH4(Cl).NCS
[1:4]. [45°]. (250°). Crystalline solid. Pre-
pared by the action of GS, on j>-chloro-aniline
and decomposition of the resulting di-chloro-
phenyl-nrea (Hofmann, B. 13, 13 ; BeUsteiu a.
Eurbatoff, A. 176, 61 ; Losanitsch, B. 6, 156).
DI-o-CHLOBO-BI-PHENYL-IHIO-nBEA
C„H,„CljN,S i.e. CS(NH.C.H,Cl)j. [146°]. From
o-chloro-aniline and CS2 (Hofmann, B. 13, 14).
Oi-Tn-chloro-dl.plieuyl-thio-urea [122°] (H.).
Bi-p-chloro-di-phenyl-thio-nrea [168°]. S.
(In CSj) -0264 at 13-7° (Beilstein, A. 176, 47).
From p-chloro-aniline, CSj,^ and alcohol (Losa-
nitsch, B. 5, 156; Bl. [2] 32, 170). Iodine acting
on its alcoholic solution forms di-chloro-di-
phenyl - urea, tri - chloro - tri - phenyl - guanidine,
ohloro-phenyl thio-carbimide, and chloro-phenyl-
carbamic ether.
TBI - CHLOBO -PHENTL- lOLYL.ETHANE
CABBOXTIC ACID Cifi„Cl,Oti.e.
CH,.C,H,.CH(CCy.C.H4.C0jH. [174°]. From
(CHj.CgHJ^CH.CCl, and chromic mixture (O.
Fischer, B. 7, 1192). Tables (from alcohol).
Alkalis give CH,.C,H^C(C0y.C.Hj.CO,H.
DI - CHLaBO - FH£K YL - TOLYL ■ KETONE
CABBOXTLIC ACID v. Di-cmoito-TOLCYL-BKN-
zoio Acm.
u-CHLOBO-PHENYL-TOLYL-UETHANE
CH2Cl.CgH4.CH2.CeHs. A mixture of the o- and
p- varieties of this body is one of the products of
the action of benzyl chloride on water at a high
temperature, the reaction being as follows :
2CeH5.CH2Cl = HCl + CHjCl.CeH4.CH2.C„H5. The
mixture on oxidation gives o- and j>-benzoyl-
benzoic acid (Senff, .i. 220, 249).
DI-p-CHLOBO-DI-FHENYL-UBEA .
(C,H4C1.NH)2C0. A secondary product in the
preparation of p-chloro-phenyl thiocarbimide by
the action of P^O, or of iodine on the corre-
sponding thio-urea (Beilstein a. Eurbatoff, A.
176, 46). Long needles (from HOAc). Volati-
lises at 270°.
TBI-qHLOBO-PHlOBOGLUCIN C.H3CI3O3.
[129°]. Formed b;^ passing chlorine into a solu-
tion of phloroglucin in HOAc until the liquid
ceases to give a. red colour with wood (Webster,
C. J. 47, 423 ; Hazura a. Benedikt, M. 6, 706).
Blender needles (containing,3aq^. Dilute HNO,
gives oxalic acid. Chlorine, in presence of CCl,,
{ives chlorinated acetic aldehyde and tri-ohloro-
icetic acid. 'When chlorine is passed into an
Aqueous solution of phloroglucin there is formed
dl-chloro-acetic acid.
Sexa-Bydride C^C1,0,. [123°]. From
hexa-bromo-phloirogluoin dibromide, tin, and
HCl (H. a. B.). Needles (containing 3aq).
CHLOBO-PHLOBONE v. CHLOBo-XTLogvi-
KONE.
u-CHLGBO-PHTHALIC ACID C^^ao^ t.«.
CeHjCUCOaH), [4:2:1]. [148°] (0. a. D.; G.a.
.B.; 0.a.M.); [130°] (I.); [0. 134°] (E.).
Formation. — 1. By oxidation of (e)-di-chloro-
naphthalene [135°] (AWn, Bl. [2] 36, 434), of
chloro-(/S)-naphthol (Claus a. Dehne, B. 15, 320),
of the two chloro-toluic acids [130°] and [166°]
(Eruger, B. 18, 1758), of (' 3 ')-di-ohlorb-(«).
naphthoquinone (Clans a. MiiUer, B. 18, 3076),
and of chloro-di-ethyl-benzene (Istrati, A. Oh.
[6] 6, 413). — 2. By saponifying the chloride
which may be formed by the action of PCI, on
the tri-chloride of sulpho-phthiilic acid
0<^Q 2>C,H,.S02C1 (Bfie, A. 233, 236).
Properties. — Small needles. V. sol. water and
alcohol ; m. sol. dilute HCl, chloroform, and CSj,
si. sol. benzene, insol. ligroin. With resorcin it
gives a chloro-fluorescem.
Salts. — EjA":' large needles, v. sol. water.:—
BaA" : amorphous ; si. sol. water. — ^BaH^A";, :
small needles, si. sol. water. — CaA" : scalqs, si.
sol. water. — AgjA" : white pp.'
Anhydride CjH,C1<^^q>0. [95°] (0. a.
D.) ; [97°] (G. a. E. ; E.) ; [114°] (I.). Formed
by heating the acid. Triclinic needles (by sub-
linlation).
Methyl etherUe^k". [37°]. Needles.
Ethyl ether Et^". [-20°]. (c. 303°)
(Graebe a..B£e, C. J. 49, 528).
Chloride C^lB.,C!i<^''yO. (276°uncor.).
Liquid.
Imide C.H,C1<^°>NH. [211°]. From
the anhydride and NH3 (E6e, A. 233, 236).
c-Cbloro-phthalic acid C.HjCllCO.^)^ [3:2:1].
[184°] (G.) ; [181°] (K.). S. 2-16 at 14°.
Formation. — 1. By oxidation of chloro-tolnio
acid [154°] with EMuO, (Eruger, B. 18, 1758).^
2. By oxidation of (7)-di-chloro-uaphthalene
[107°] with CrO, in HOAo (Guareschi, Q. 17, 121 ;
B. 19, 134).
ProperUei. — Long needles ; si. sol. cold, v.
sol. hot, water ; ▼. sol. alcohol and ether. Gives
the anhydride on melting. Heated with phenol
and cone. HaSO^ it gives a phthaleiu which dis-
solves^ alkalis forming a violet solution..
Salts. — ^BaA"aq : long silky needles, v. sol.
cold, si. sol. hot, water. By boiling with water
it is converted into an insoluble crystalline pow-
der BaA" aq. — ^AgjA" : crystalline pp.
Anhydride C.H3C1<;^^>0. [123°].
Needles (by sublimation). By chlorination of
phthalic acid Auerbach (J. 1880, 862) obtained
an (impure ?) phthalic acid [150°] whose anhy-
dride melted at l43°.
Di- chloro- phthalic acid C„HjClj(COjH)r
Formed by oxidation of the tri-chloro-naphthal-
ene [90°] (from (3)-naphthol-(j3)-di-snlphonate
and PCy, by heating with dilute HNO,, (S.G.
1-16) at 210". Syrup. Could not be obtained
crystallised although apparently pure.
Salts. — The Na and E salts are excessively
DI-OHLORO-PHTHALIMIDINE.
121
8ol. water. — ^A"Ba : ▼. Bol. amorphous solid. —
A"Ag, : -white pp., nearly insol. oold water.--
A,"Fb : insol. white pp. (dlaoB a. Schmidt, B. 19,
3176).
(fl)-Di.oUoro-phthaUo aoid 0,01sH2(C02H)j.
[118°]. Formed by oxidation of a ohl«rinated
naphthalene (Qraebe a. Le Boyer, A. 238, 360).
V. e. sol. hot water, m. sol. cold water or alcohol.
Salts.— (NHJjA". — Ag^", — CaA" 4aq —
BaA" 2aQ
Ethers.— EtjA" [60°].— EtHA"[76''-86<n.—
Et(NH,)A".
Anhydride 0,01^0,0,- [c 161°]. (340°).
Chloride O.CljHjCAOls. [below 60°]. (c.
814°).
Tetrachloride Ofil^OfiCl^ [117°].
(above 300°).
Imide O.COAOANH. [191°]. Beduced
by Zn and HCl to diohlorophthalimidine [210°].
Bi-chloro-phthalic acid - OACSlzi^^Oa^):-
[183°]. Eormed by oxidation of the di-chloro-
o-zylene [4°] by dilute HNO3 (Glaus a. Kautz,
B. 18, 1370). formed also by oxidation of (' ;3 ')-
di-chloro-naphthalene (Atterberg, B. 10, 547) ;
and by boiling di-chloro-uaphthalene tetra-
chloride witn HNO3 (Fausl, A. 160, 64). Prisms ;
T. sol. hot water, alcohol, and ether.
Salts. — ^BaA"aq. — CaA"4aq : prisms, si. sol.
water.
Anhydride C„H,C1,0A- [187°].
Tri-chloro-pbthalic acid C,HC1,(C02H).^.
Formed by oxidation of tri-ohloro-o-xylene [93°]
by dilute HNO, (Glaus a. Kautz, B. 18, 1370).
Formed also by the action of cone. HNO, on (p)-
■ penta-chloro-naphthalene (Atterberg a. Wid-
mann, B. 10, 1841). Yellowish-white mass; con-
verted by heat into the anhydride.
Anhydride [157°]. Needles.
Tetra-cMoro-phthalio acid CsCl,(G02H)2.
[250°]. S. -57 at 14° ; 8-03 at 99°.
Formatum. — 1. From (o)-penta-chloro-naph-
thalene and dilute HNO, at 190° (Graebe, A.
149, 18). — 2. Together with penta-chloro-(o)-
naphthoquinone, by oxidation of hepta-chloro-
naphthalene [194°] with HNO, (1'5 S.Q.) at 100°
(Glaus a. Wenzlik, B. 19, 1166).
PrepwratUm. — ^Phthalio anhydride (5 kilos.)
is heated with SbCl, (30 kilos.) at 200°, and
chlorine is passed in for 10 hours. The product
is distilled (Gnehm, A. 238, 319).
ProperUes. — Plates (from water). V. sol. al-
cohol and ether, si. sol. benzene and chloroform.
Beaciitms. — 1. Converted by heat into H^O
and its anhydride. — 2. Galcinm salt gives octo-
chloro-anthraquinone (in small quantity) when
distilled (Kircher, B. 17, 1170).— 3. Sodium
amalgam reduces it in dilute alcoholic solution
to phthalio aoid (Glaus a. Spruck, B. 15, 1401) ;
the reduction is better performed in aqueous so-
lution, but hydrophthalic acid and other products
are also formed (Graebe, A. 238, 323).-4. HI
and P at 230° give tetra-ohloro-s-phenylene-di-
methyl oxide, C,Cli<cg'>0, and sometetra-
chloro-phthalide C,Cl,<c^>0. The latter
body is also produced by the action of zinc-dust
»nd glacial acetic acid.— 5. PCI5 forms
C.Cl.<^S''>0andC.Cl.<^C1^0.
Salts. — KjA".— BaA 2iaq. — BaA'j S^aq
(Tust, B. 21, 1532).— GuA"2aq.-Ag2A".
EtheiB.- EtjA". [60-6°].— EtHA". [95°].—
MejA". [92°].
Anhydride 0,Ca,<^3>0- ^246°].
Chloride O.Ca,<^^^«>0. [118°]. (336°)
at 733 mm. From the anhydride and PCI, at
220°.
Tetrachloride C.Cl4<co}«>0. [140°],
Imide C,C1,0,02^H. From NH, and the
anhydride.
J7)-CHL0E0.IS0.PHTHALI0 ACID
oX01(COjH)j. [278°]. S. -026 at 16°.
Prepwratiim. — ^A solution of amido-iso-
phthalio acid in HCl is mixed at 0° with NaNOj,
and the pp. of the hydrochloride of diazo- iso-
phthalio acid is gently warmed with HCl.
Crystallised from water (Beyer, J. pr. 133, 506).
Properties. — Slender needles (from water).
When dried over S^SO, they contain water
(^aq). Y. si. sol. hot water.
Salts.— The neutral potassium salt gives
no pp. with solutions of salts of Ca, Sr, Ba,
Mg, Zn, Hn, Go, Ni, nor with HgCl,. It gives,
with CdSO,, bulky white pp.; Fe,Cl, light
brown pp.; Pb(0Ac)2 and AgNO,, white pps.
soluble in hot water. CuSO,, blue pp.;
Hg2(N0,)2, white gelatinous pp. A"E, : needles
arranged like ferns. — ^A"Na2. — A"Mg 7aq. —
A"Ca2aq. S. 3-54 at 16°.-A"Sraq. S. -929 at
15°.— A"Ba 2aq. S. 1-41 at 15°.— A"0d. S. -303
at 15°. — ^A"Ag2. Gelatinous pp. Crystallises in
small needles (from hot water).
Ethyl ether A"Et, [46°]. Short prisma
(from ether). -
Chloro - tere - phthalio acid «. Ohlobo-
TEBEFHTHAUC AOID.
SI-CHLOBO-PHTHALIDE
0JHjClj<^QQ ^>0 . [122°]. From the chloride
of di-ohloro-phthaUc aoid 0,HjC1,<qq^> O by
reducing with Zn and HCl (Le Boyer, A. 238,
355). Also from nitroso-di-ohloro-phthalimid-
ine and alkalis. Crystals (from alcohol).
Di-ohloro-phthalide C,HjC1j<qq»>0
[1:4:5:6]. [163°]. Formed, together with di-
chloro- (a) -naphthoquinone by oxidation of di-
chloro-naphthalene [68°] with CrO, and glacial
acetic acid. Short prisms or flat needles. Sol.
alcohol and ether, v. si. sol. water. Sublimable.
It does not react with hydroxylamine (Guar-
eschi, B. 19, 1165).
Tetra-chloro-phthaUde C,6l4<(^^>0.
[208-5°]. From tetrachlorophthalie anhydride,
glacial HOAc and zinc-dust (Graebe, A, 238,
330). v. si. sol. cold alcohol ; insol. NajGOjAq ;
sol. boiling NaOH and reppd. by acids un-
altered.
CHLOBO-PHTHALIKIDE V. Imide o/Chlobo-
PHTHALIO ACID.
DI-CHLOBO-PHTHALIMIDINE
C,H,,C1,<^Q*>NH. [210°]. From di-ohloro-
phthalimide, tin, and HCl (Boyer, A. 238, 336),
132
DI-OHLOEO-PHTHATJMIDINE.
Crystals (from oUoroform). Gives a nitroao-
deiivative.
TEIBACHLOBO-BIFHTHALTL C^HtOlA
yO 0 .
i.e. C.01Z yo o<^ nX^*^*' ^"'^"^^^''y
the condensation of tetra-ohloro-phthalide and
pbthalic anhydride without the use of sodium
acetate (Graebe a. Guye, A. 233, 245). Brownish
yellow powdei; insoL alcohol, glacial acetic
acid and toluene ; soL chloroform, aniline and
phenol.
CHLOSOFHYLL— the peculiar substanoe to
which the green colour of leaves and other
parts of plants is due — ^was first examined by
Pelletier and Caventou, who called it chloro-
pkyll. From the chemist's point of view it is
simply an organic colouring matter, like indigo
or alizarin.
It is important to bear this in mind, since
much confusion and misunderstanding have
arisen from the term chlorophyll having been
applied to distinct things. Some chemists under-
stand by chlorophyll the sum of the coloured con-
stituents of leaves insoluble in water, and it has
accordingly been proposed to call that consti-
tuent the colour of which inclines more to blue,
Kyanophyll, while that constituent or group of
constituents which gives solutions of a yeUow
or greenish-yellow tint should be named Xam-
thc^hyll. In works on vegetable physiology the
term chlorophyll is sometimes applied to the
complex of substances contained in living green
cells, which take part in the process of assimi-
lation and of which the colouring matter con-
stitutes a portion, and chemists, following this
example in giving a name to the whole which
should have been confined to one part, have
been led to ascribe to chlorophyll properties
which no mere chemical substance can possibly
possess. In order to avoid confusion it should
therefore be understood that in using the term
chlorophyll we mean simply the substance — or
it may be mixture of substances — to which
the pure green colour of ordinary healthy leaves
and of other vegetable organs, such as unripe
fruit, is due. The appearance in leaves of any
colour other than green, such as red, yellow, or
purple, would indicate the presence of some sub-
stance accompanying the chlorophyll and dis-
guising its colour or even replacing it entirely.
Chlorophyll is invariably present in vege-
table cells in which the process of assimilation,
t.e. the formation of organic matter from CO,
and HjO with elimination of 0, is going on.
Parasitic and other plants, such as fungi, which
obtain their nutriment ready-formed from -other
organisms or from decaying organic matter, and
do not decompose CO, in the same way as the
majority of plants, contain no chlorophyll.
Plants or shoots grown in the dark from seeds
or tubers are also devoid of chlorophyll ; they
grow at the expense of the matter stored up in
the seed or tuber, and when this is exhausted
they die. The appearance of chlorophyll in
etiolated plants on exposure to light indicates
the commencement of assimilation. It is cer-
tain, therefore, that chlorophyll plays some part
in the process of assimilation, and that its
pre:ience is essential, but how it acts in assist-
ing the process is unknown, its physical and
chemical properties, so far as they are known
to us, affording no certain due to the solution
of the problem. In the green cells of plants
the chlorophyll is found associated with the'
protoplasmic constituent from which it may
be easily separated by treatment with alcohol
or ether. The green corpuscles seen in vegetable
cells are in fact masses of albuminoid and other
matters, permeated and tinged by chlorophyll,
which is probably contained in a state of solu-
tion in the cell and not as a solid.
Physical and chendcal properties of chloro-
phyll.— Considering the great importance of
chlorophyll in relation to the process of assimi-
lation in plants, it can hardly be a matter for
surprise that it should very frequently have
been examined. The literature of chlorophyll
is very extensive, and comprises memoirs by
physicists, chemists, and physiologists, some of
them men of great eminence in their respective
branches of science. Nevertheless, our know-
ledge' of its properties, physical and chemical,
is very scanty. The imperfect state of oui
knowledge of the subject is due to several causes.
In the first place the (quantity of chlorophyll con-
tained in an extract of leaves, though the latter
may be intensely coloured, is extremely small ;
secondly, chlorophyll is associated in the plant
with large quantities of other substances, colour-
ing matters, resins, fats, &c., which accompany
it on extraction with ordinary solvents, and
from which it cannot easily be separated ;
thirdly, it is a substance which is very apt to
undergo change, so that during any process of
purification to which it may be submitted, it
will almost certainly be more or less altered ;
fourthly, chlorophyll, like most substances which
play an important part in the vegetable or
animal economy, is certainly amorphous, and
the freedom from impurity of any specimen
must therefore always be more or less doubtfuL
Some observers have described bodies which
they have held to be crystallised chlorophyll,
but the writer is of opinion that these were in
all cases products of decomposition derived
from chlorophyll. Chlorophyll contains nitro-
gen in addition to carbon, hydrogen and oxygen,
but the percentage is certainly not large. It
has been supposed to contain iron like the
haemoglobin of blood; after incineration a minute
quantity of ferric oxide is indeed always found
in the ash, but whether this is derived from
chlorophyy, or from some substanoe or sub-
stances accompanying it, is uncertain. The
ash also contains calcium and magnesium
phosphates, but of these again it cannot with
certainty be said that they are constituents of
chlorophyll itself. Chlorophyll may be de-
scribed as a neutral body, like indigo, having
the properties neither of an acid nor a base ;
in constitution it may resemble the fats or the
lecithins, as suggested by Hoppe-Seyler. Though
not itself a gluooside, it is always found asso-
ciated with a body having the characteristics
peculiar to that class, as was first pointed out
by the writer.
Chlorophyll is insoluble in water, but soluble
in alcohol, ether, carbon disulphide and ethereal
oils.
These solutions show a lively green colour
of great intensity, accompanied by a marked
CHLOROPHYLL.
12S
red flooreaoenoe. The soIationB show an ab-
lorption apeotrum which is quite oharacteriatio,
and muat therefore be shortly described. A. solu-
tion o{ chlorophyll made by extracting fresh green
leaves with alcohol or ether ie found, when very
lark, to absorb nearly the whole spectrum, only
a narrow atrip of light at the extreme red end
being visible. When the aolution is made paler
by the addition of more solvent, the green of
the spectrum begins to appear, a faint absorption
band showing itself about the middle. On still
further diluting, other bands make their appear-
ance in sncceasion. When an average depth of
eolour is reached the following absorption bands
are seen : — A very dark band beginning close
to the line B and extending over C, followed by
a second band between C and D which is much
lighter, after which comes a third still paler
one beyond D and close to the latter, lastly, a
fourth band is seen partly on E which is usually
the faintest of all, but is sometimes as dark as,
and even darker than the third (see Fig. i.).
Total obscuration begins about the line F. The
lour bands just described are usually marked
with the numerals I.-IV. in accordance with
the notation employed by AngstrSm, and are
seen so constantly and invariably, when proper
precautions are taken to have a solution of un-
changed chlorophyll of average strength, as to
constitute a certain test for chlorophyll, which
may accordingly be defined as the substance
which in solution shows this particular absorp-
tion spectrum. It should be mentioned that
there is a considtsrable amount of obscuration
throughout the whole spectrum of chlorophyll
solutions, excepting only at the extreme red, so
that the parts usually represented as white are
in reality more or less darkened, and also that
the bands, with the exception of band I., are not
so sharply defined as the ordinary representa-
tions would lead one to suppose in consequence
of the edges gradually shading off. Opinions
differ as to whether the same absorption spec-
trum is seen when a green leaf is placed before
the slit of a spectroscope, some observers main-
taining that only band I. is discernible, while
others say that all four bands can be made out,
the only difference being that the bands are all
shifted towards the red end, from which it has
been inferred that in the plant chlorophyll
exists in a state of solution, the solvent having
a density greater than that of alcohol or ether.
Beturning to, the solution of chlorophyll showing
the spectrum just described, let us now see what
takes place on further dilution. A beam of
sunlight having been thrown on the slit of the
spectroscope the solution is to be considerably
diluted until it becomes quite pale. It will then
be found that band I. having become narrower
and paler has left the line C altogether and
taken its place near B ; band II. has become
much narrower and paler, but remained in the
same place, while bauds III. and IV. have
entirely disappeared. At the other end of the
spectrum, however, two pale, ill-defined bauds
have made their appearance, one being situated
between F and G, the other on G (see Fig. ii.).
These bands are numbered V. and VI. Whether
they belong to chlorophyll itself or to some
other colouring matter accompanying it is un-
certain, no one having as yet succeeded in
obtaining a aolution of chlorophyll in which
they are not seen, provided the solution is
sufficiently dilute and is observed in sun-lighk
The writer is of opinion that the two bands
belong to a yellow colouring matter (xantho-
phyll 7) always accompanying chlorophyll, from
which the latter cannot be separated. It is
certain that all leaves contain a colouring
matter, the ohrysophyll of Hartaen ^Bougarel's
erythrophyll), which may be obtained m lustrous,
orange-coloured crystals, and givea yellow solu-
tions, showing two distinct absorption bands at
the blue end — not exactly in the same position
as those just referred to — but no trace of any
band in the other parts of the spectrum ; the
bands V. and VI. may belong to a nearly allied
substance.
The absorption bands of chlorophyll solu-
tions were first described by Sir D. Brewster,
who was also the first to observe the red fluor-
escence of these solutions. The bands were
next examined by Stokes and XngstrSm, by the
latter of whom they were also correctly figured.
Many other observers have worked on the same
field; among these the following may be named:
Askenasy, Gerland and Bawenhoff, Hagenbaoh,
Harting, Kraus, L. Liebermann, Lommel,,A.
Meyer, Mioheli, Morot, Pringsheim, Bussell and
Lapraik, Sacchse, Simmler, Sorby and Wiesner.
The memoirs of Hagenbaoh, Kraus, Lommel,
Pringsheim, BusselL and Sorby on the subject
are especially worthy of study. It should be
mentioned that aome of the abaorption spectra
figured in memoirs on chlorophyll really belong
to derivatives of the latter. Whenever in such
figures band IV. appears rather dark and is
followed by another dark band nearer the blue
end, we may conclude that the observer has
worked with a specimen of chlorophyll that has
undergone some change.
Products of decomposition of chlorophyll. —
A solution of chlorophyll inclosed in a sealed
tube and kept in the dark retains ita colour for
any length of time, but in an open vessel, espe-
cially when exposed to light, the colour dis-
appears rapidly, only a faint yellow tinge re-
maining; what is formed during this change,
which is doubtless due to oxidation, is not
known.
By the action of acids chlorophyll under-
goes a marked change, which no one who has
worked with the substance can have failed to
observe. When to an alcoholic solution of chloro-
phyll a small quantity of sulphuric or hydro-
chloric acid is added, the colour of the aolution
changes at once from a bright green to a dull
yellowish-green or olive. Examined in the
usual manner the spectrum will be found en-
tirely altered; bands I. and II. have become
more distinct from the clearing up of the space
between the two, band III. appears much paler,
and band IV. much darker, than before. After
the solution has stood for aome time band IV.
wiU be found to have greatly increased in in-
tensity, while another dark band has made its
appearance near the line F just in front of the
part where total obscuration begins. This is
what has, not very appropriately, been called
the absorption spectrum of acid 'chlorophyll,
and is due to the formation of products derived
from chlorophyll by a process the nature of
124
CHLOROPHYLL.
which ia not understood. That this process is
not snoh a one as might admit of explanation
by sapposing chlorophyll to have the constitu-
tion of a salt, its acid constituent b«ing expelled
by the addition of a stronger acid, is proved by
the fact that if alcoholic potash or soda be
added in excess to a solution of chlorophyll
which has been acted on by acids, the original
bright green colour is not restored. To those
conversant with the decomposition of complex
organic substances, another explanation may
Buggest itself, viz. that the change is due to
hydrolysis in presence of an acid, accompanied
perhaps by a splitting up of the same kind as
that which glucosides undergo when acted on
by acids or ferments. Bussell and Lapraik are
of opinion that the change is a molecular, not a
chemical one. Weak acids produce the same
change as strong ones, but only after some time.
On the addition of a comparatively large quan-
tity of acetic acid to an alcoholic solution of
chlorophyll, no change of colour is perceived at
first, nor is the spectrum in any way altered, but
on standing the colour slowly passes over to yel-
lowish-green, and the same bands make their
appearance as when a strong acid is employed.
The same change frequently takes place when
a solution of chlorophyll is left to stand in a
loosely-stoppered bottle kept in the dark; in
this case the effect is probably due to the pre-
sence of some substance, an ethereal oil for
instance, which by oxidation yields an acid of
some kind. Some leaves, such as those of the
vine and Virginian creeper, naturally contain
much free acid which, on extraction of the
leaves with alcohol, accompanies the chloro-
phyll and changes it after a short time.
In order to obtain the products derived from
chlorophyll by the action of acids, fresh green
leaves are extracted with boiling spirits of wine;
the liquor after straining is allowed to stand,
BO that a portion of the fatty matter contained
in it may be deposited, after which it is filtered
and a current of hydrochloric acid gas is passed
through it; By the action of the acid a dark
brownish-green flocculent precipitate is formed,
which after standing is filtered off and washed
with alcohol. This precipitate contains two
peculiar colouring matters, which Fremy named
phyllocyamn and phylloxanthin, along with im-
purities of a fatty nature. The two colouring
matters are separated by Fremy's method ; the
mixture is dissolved in ether, and the solution
is shaken up with about a quarter its volume of
concentrated CIH, Vhereupon it separates into
two layers, an upper yellowish-green one con-
taining phylloxanthin, and a lower bright-blue
one containing phyllocyanin.
The phylloxanthin of the upper stratum is
largely contaminated by fatty matter, from
which it cannot easily be separated, but the
phyllocyanin from the lower stratum can be
purified and is obtained in microscopic crystals,
which are generally opaque, but when very
thin appear olive-coloured by transmitted light.
The general properties of phyllocyanin have
been described by the writer, but a few only of
these can here be mentioned. Phyllocyanin is
a body entirely sui generis, resembling no other
natural colouring matter. It is insoluble in
water and ligroJin, but soluble in alcohol, ether.
acetic acid, chloroform, benzene, and carbon bi-
sulphide. The solutions show an absorption
spectrum with five bands (see Fig. iii.). It
dissolves in concentrated CIH and SH^O^ giving
solutions of a bright blue colour, and is repre-
cipitated unchanged by water. It dissolves in
alkaline lyes, but is entirely changed by the
action of the alkali. Its most interesting pro-
perty is that of yielding by the combined action
of acids, chiefly organic acids, and metallic
oxides, such as cupric, ferrous and zinc oxides,
compounds, the solutions of which are bright
green and closely resemble solutions of chloro-
phyll not only in colour but in other respects
also.
Phyllocyanin is remarkable for its great
stability ; its solutions remain for a long time-
unchanged whan exposed to light and air,
whereas solutions of chlorophyll are rapidly
bleached under the same circumstances. Phyl-
locyanin yields with alkalis and reducing agents
products which show absorption spectra of
great variety and beauty (see Figs. v. and vi.).
Phylloxanthin resembles phyUocjanin in many
of its properties, but is a less interesting sub-
stance. Its absorption spectrum shows only
four bands (see Fig. iv.). It wiU be seen that
when the two substances are present together
in solution, the bands of phylloxanthin will be
concealed by those of phyllocyanin.
On reading some of the older memoirs on
chlorophyll, such as those of Berzelius, Mulder,
and Fremy, it will be evident that the authors
worked not with chlorophyll itself, but with
products due to the action of acids on the latter.
It is probable that the chlorophyllan of Hoppe-
Seyler and the hypochlorin of Pringsheim are
products belonging to the same class as phyllo-
cyanin and phylloxanthin. According toTschirch
chlorophyllan is the first product of the action
of acids on chlorophyll, and splits up into
phyllocyanin and phylloxanthin when the ac-
tion of acid is prolonged, This short account
may serve to show that our knowledge of the
derivatives of chlorophyll is still very defective.
VhloropJiA/U in relation to plant life. — There
can be no doubt that the presence of chloro-
phyll is necessary during the process of assimi-
lation by plants, but what part it plays in the
process is unknown. It was at first supposed,
considering how powerfully the more refrangible
end of the spectrum is absorbed by solutions of
chlorophyll, that it was especially the blue rays
that effected the decomposition of COj and HjO
within the cells. This idea was soon abandoned
in favour of another theory, according to which
it is the red rays that are more active than the
others in promoting assimilation, they being
also strongly absorbed by chlorophyll. The
latest investigations make it probable that the
yellow rays, which are the least absorbed of any,
produce a more abundant evolution of 0, and
consequently a greater amount of decomposition
of CO2 and HjO than either the red or blue
rays. Pringsheim is of opinion that chloro-
phyll acts simply as a screen which absorbing
the less refrangible rays.moderates the energetic
heating and oxidising action of the latter during
the process of assimilation. All that can be
positively asserted with regard to this part of:
the subject is that the colour, i.e. th« alsorp-
OHLORO-PROPANK.
12«
tiTO power of chlorophyll has something to do
with its mode of action.
It has heen thought, and we often find it
stated in books, that chlorophyll has itself the
power of absorbing CO^ and evolving 0; at-
tempts have even been made to prove that this
takes place in oi ^nary solutions of chlorophyll.
This is, however, erroneous ; it is certain that the
complex which physiologists call the chloro-
phyll corpuscle, or simply chlorophyll, has the
power of decomposing CO, and HjO with evolu-
tion of O, but tiiat any such power resides in
the colouring matter when dissociated from the
other constituents of the complex must be in-
correct, since it is opposed to all that we know
of the chemical properties of organic substances.
List of the most important memoirs and
works on chlorophyll : —
Angstrom, Ueb. d. grttne Farbe d. Pflanzen,
P. 93, 475 ; Askenasy, Bot. Ztg., 1867, 225 ;
phyllfarUtoffe, Stuttgart, 1872; Kromeyer,
ZerUgtmg des Chlorophylls in emem bUmen
und einem gelben Fa/rbstoff, Ar. Ph. 155, 104 ;
Ij. Liebermann, Sitz. 17.72,599; Lommel, Ueb.
d. Verhalten d. Chlorophylls mm Licht,P. 143,
568; Meyer, Das Chlorophyllkom, Leipzig,
1883 ; Micheli, Arch. d. Sc. de la bibl. unw. d.
GetUve, Mai 1867 ; Morot, Arm. des Sc. Nat.
3rd ser. 13, 160 ; Mulder, Ueber d. Chlorophyll, -
J. pr. 33, 478 ; Pelletier et Caventou, Sur la
mahire verle des feuilles, A. Ch. 9, 194;
Pfaundler, A. 115, 37 ; Pringsheim, Untersuch-
ungen Ub. Lichtwirkvng u. Ghlorophyllfunction
in d. Pflanzen, Leipzig, 1881 ; BusseU 'and
Lapraik, A Spectroscopic Study of Chlorophyll,
C. J. 41, 334 ; Saohsse, Die Chem. u. Physiol
d. Farbstoffe, Leipzig, 1877; Schunck, Con-
tributions to the Chemistry of Chlorophyll, Pr.
39, 348, 42, 184 ; Simmler, P. 115, 603 ; Sorby,
Comparative Vegetable Chromatology, Pr. 21, •
Explanation op Cut.
Fid. 1. — Absorption spectrum of cfaloropbyll, strong aolntlon.
» 1^ » » « »' weak „
„ 111. „ » » phyllooyanin.
,, iv. „ HI* pbylloxanthin.
p T. H » H B phyllooyanin derivative.
„ vi. n » » ethyl compound of the preceding;.
BerzeliuB, XJntersuchung d. Blattgrilns, A. 27,
296; Brewster, On the Colours of Natwral
Bodies, T. E. 12, 538 ; Chautard, Examen spec-
t/roscopique de la chlorophylle, C. B. 76, 103,
670, 1031, 1066, 1273 ; Klhol, C. B. 61, 371 ;
66, 1218; 79,612; Premy, Sur la matiire colo-
rante verte des feuilles, C. B. 50, 405 ; 61, 188 ;
Oautier, Sjw la chhrophylle, G. B. 89, 862;
Gerland and Bawenhoff, Becherches sur la
ehlorophylle, Ar. N. 6, 97 ; Hagenbaoh, Unter.
suchungen lib. d. opHschen Eigenschaften d,
Elattgrms,p. 141, 245; Harting, P. 96, 543;
Hansen, ' Der Chlorophyllfarbstoff,' Arb. d. hot.
Inst, in W'Orzburg, 3, 1; Hartsen, O. O. 1872,
624, 1875, 618 ; Hoppe-Seyler, TJeber d. Chloro-
phyll d. Pflanten, H. 3, 1879, 339; 4, 1880, 193,
5, 1881, 76 ; EiauB, Zwr Kermmias d. Chloro-
452 ; Stokes, On the supposed identity of Bili-
verdin with Chlorophyll, with retnarks on the
Constitution of Chlorophyll, Pr. 13, 144;
Tschirch, Untersuchungen ilb. d. Chlorophyll^
Berlin, 1884 ; Verdeil, Becherches s. la mat. col.
verte des feuilles, C. B. 33, 689 ; Wiesner,
Bemerkungen Ub. d. aikgebl. Bestandtheile d.
Chlorophylls, Flora, 1874, 278. E. S.
CHLOBO-FICOLIIfE v. CRLOBO-MBTHyL-PT-
BtDINE.
CHIOBO-FIGOLIHIC ACID v. Cbloro-pxbi-
DINE CABBOXYLia AOID.
CHLOBOPICBIN V. TKi-OHiK>i!0-NiTno-iis-
THANE.
CHLOBOPLAIINATES v. putinatbb under
Flaitinuu.
CHLOBO-FBOFANE v. timfOi Cbi>obide.
126
CHLORO-PROPANE.
oia-Di-chloro-pTopane CjHaCl, m.
CH,.CHCl.CHjCl. PropyUm chloride. Mol. w.
113. (97°oor.). S.G.2 1-584; i4 1-155(F.a.S.);
14 1-166 (Linnemann, A. 161, 62).
Formation. — 1. From chlorine and propylene
(Cahonrg, A. 76, 283 ; Keynolda, A. 77, 124).—
2. From ohloro-iodo-propane and CI (Friedel a.
Sflva, C. B. 76, 1596).— 3. From propane and
CI (Sohorlemmer, Pr. 17,372; A. 150. 214).—
4. Together with CHj.CClj.CH,, by chlorinating
CHa.CflCl.CH, in sunshine (Friedel a. Silva, Bl.
[2] 16, 3). — 6. From isopropyl chloride and ICl
(Friedel s. Bilva, C. B. 73, 1380).— 6. From
allyl chloride and cone. HCl at 100° (Beboul,
A. Ch. [6] 14, 453).
Beaetums. — 1. Alcoholic KOH gives a-chloro-
propylene CH,.CC1:CH, (Friedel a. Silva, A. Ch.
[4]16, 349).— 2. Water (20 vols.) at 220" gives
propionic aldehyde and acetone. Water and
FbO at 160° give propylene glycol (Eltekoff, B.
6, 658).— 3. Cone. HI at 160° gives isopropyl
«hloride.
oiwDi-ehloio-propane GH3.CH2.CHCI2. Pro-
pyUdene chloride. (86°). 8.0.12 1-143. Formed,
together with ohioro-propylene GH3.CH:0HC1,
by the action of FCl, on propionic aldehyde
(Beboal, A. Ch. [6] 14, 458). Alcoholic KOH
gives CH,.CH:CHC1 (34°).
aa-Di-nhloro-propane CH,.CCl2.CH3. Chlor-
acetol. Methylchloracetol. (70°). S.G.i|l-09G6;
II 1-0848 (Perkin, C. /. 45, 529) -, la 1-827 (Linne-
mann, A. 161, 67). E.F.p. 42080. H.F.V.
40340 (Th.).
FoTTnation. — 1. From acetone and PGlj (Frie-
del, A, 112, 236). — 2. From isopropyl chloride
and CI (Friedel a. Silva, Z. 1871, 489).— 3. From
' allylene and fuming ECl in the cold (Beboul,
A. Ch. [5] 14, 453).
Beactions. — 1. Alcoholic KOH forms a-chloro-
propylene CHa.CChCHj (24°).- 2. AgOBz gives
{CH.,)fi(0Bz)i.—3. Water (8 vols.) at 170° gives
acetone (Oppenheim, B. 2, 213).
oijS- Si - chloro - propane CH^Cl.CH^.CHjCl.
Tnmefhyhne chloride. (119°), S.G. is 1-201 (B.);
!p 1-1896 (F.). From the corresponding dibrom-
ide and HgCl, at 180° (Beboul, A. Ch. [5] 14,
453). Formed also from trimethylene glycol
CHjOH.CH2.CHjOHandHCl(Freund,ir.2,638).
Alcoholic EOH gives allyl chloride..
oid^-Tri-cliloro-propane CjHjCl, t.«.
CHjCLOHCLCHjCl. Trichlorhydrin. Olyeeryl
chloride. Allyl trichloride. (158°). S.G. i|
1-3984; if 1-3878 (Perkin, O. /. 45, 632); 9 1-41
(O.). M.M. 7-897 at 21-6°.
Formation. — 1. From glycerin dichlorhydrin
(di-chloro-propyl alcohol) and FCl, (Berthelot a.
De Luca, A. Ch. [3] 48, 304 ; 62, 483 ; Fittig, A.
135, 369). — 2. By passing CI into allyl iodide
under water (Oppenheim, Bl. [2] 2, 97).— 3. One
of the products of chlorination of propylene
chloride (Belohoubek, B. 9, 924), or of propane (7)
(Berthelot, A, 165, 105). — 4. From propylene
chloride and ICl at 160° (Friedel a. Silva, Z.
1871, 683).
Beactions. — 1. Tra<(!r(20Tol8.) by heating at
160° for 24 hours foims glycerin.— 2. EOH
gives CH2-.CC1.CH,C1 (101°) and a little
CHC1:CH.CH,CL— 8. Alcoholic ESH gives
C,S.(SE),.— 4.AlooholioNH,fonna(C,H,CI),NH.
6. AlJs gives allyl iodide (Gastavson, O. 0.
1877, 19).
oiiuffi-Tri'Oliloro-prdpane CH,.CH2.CC1, (146°-
150°). From Pr^S and dry CI in daylight
(Spring a. Ijecrenier, Bl. [2] 48, 623). Ag^O
converts it into propionic acid.
uuia-Tri-chloro-propane 0H,.CHCl.CH01r
a-Chloro-propylidene chloride. (140°). S.G.^
1-402; aa 1.372. Formed by chlorination of pro-
pylene or propylidene chloride in sunshine. Also,
together with the preceding, by heating pro-
pylene chloride with 101 at 160° (Friedel a.
Silva, C. B. 74, 805). Formed by union of
CHj.CCliOHj with 01 (Berthelot, A. 155, 106).
cDaa . Iri - chloro - propane CHt.GCls.CH^CL
(123°). S.G. a 1-360 ; ^ 1-318.
Formation,.— 1. From CH5.OClj.OH3 by 01 in
sunshine, or by ICl (F. a. S.). — 2. From pro-
pylene chloride and 01 (Belohoubek, B. 9, 924).
3. From chloro -acetone and POlj. — 4. From
CHs-CCliCHj and 01 at 0° in sunshine.
Beaationa. — 1. Water at high temperatures
forms CHj.C0.0H0 (?).— 2. Alcoholic KOH gives
two di-chloro-propylenes (75°) and (94°) (Friedel
a. Silva, C. B. 74, 808).
Tri-chloro-propane CHj01.CHj.CHCl,.
P-Chloro-propyUdene chloride. (147°). S.G. «
1-362. V.D. 4-95. Formed by the action of
POI5 on 18-chloro-propionic aldehyde or on aoro-
le'in (Geuther, Z. 1865, 29 ; van Bomburgh, Bl,
[2] 37, 98). Alcoholic EOH gives di-chloro-pro-
pylene CHj:OH.CHClj.
Tetra-chloro-propane CH3.OOIJ.OHOI2. (153°).
S.G. i3 1.47. From di-chloro-acetone and POl,
(Borsche a. Fittig, A. 133, 114). Also from
allylene dichloride (Pinner, A. 179, 47). Appa-
rently the same body is formed as a by-product
in the preparation of tri-chloro-butyric aldehyde
by chlorinating aldehyde (Pinner, B. 10, 1057).
Alcoholic EOH gives OaH,Cls (116°).
Tetra-chloro-propane 0,H,0l4 i.e.
CHjCl.CH3.CH3? [178°J. (203°). From propana
and CI in sunshine (Schorlemmer, Pr. 18, 29).
Stellate groups of needles (from alcohol). Smells
like camphor.
Tetra-chloro-propane CH3Cl.CCls.0HjCl. Iso-
allylene tetrachloride. (164°). S.G. i^ 1-496.
From OHjCLCOliCH, (95°) and CI or HOCl
(Fittig a. Pfeffer, A. 135, 360 ; Henry, 0. B. 94,
1428). Also from CHj.COliCHj and 01 (Ber-
thelot, A. 155, 105). Alcoholic KOH gives 0,HsCl.
Alcohohc NH, gives (CjH.Cy^H. Sodium
gives allylene.
Tetra-chloro-propane C,H.01. ifl.
CH3.CHOI.CCI,. [145°]. (0.185°). Fromiso.
propyl iodide and CL Beaembles camphor (B.).
Xetra-chloro-propane 03H,C1,. (0. 198°).
S.G. 1-65. From propylene chloride and 01
(Cahours, A. 76, 283). Probably identical with
the preceding or, possibly, with the following.
Tetra-chloro-propane CH,Cl.CH01.CH01r
Tetra-chloro-glyeide. AltyUden* tetrachloride.
(180°). S.G. V 1-621. V.D. 6-3. From
CH3.COI-.CH3CI and 01 (Hartenstein, /. or. [3]
7, 313). From OHjtCH.CHCl, and CI (van Bom-
burgh, Bl.l2\ 36, 653).
Fenta-chloro-propane C,H,01, {.e.
CH3a.CCl3.CHCl,. (194°). Prom di-ehlon>-
aoetone and PCI, (BorSohe a. Fittig, A. 138, 116).
Alcoholic KOH gives C,H,C1, (166°).
OHLORO-PROPIONIO ACID.
197
Peata-oMoTO-propane CiHjCl, t.«.
CH,.0Cas.C01,? From CH,.C01j.0HCl, and 01
(B. a. F.). Prisms.
fenta-ohloro-propane G,H,Cls. (o. 223°).
From propylene chloride and CI (Gahours, A.
76, 283).
Heza-ohloro-propane C,H,C1, %.e.
CClrCH,.C01,? (250°). Formed by chlorina-
ting propane in the brightest sunshine (Sohor-
lemmer, Pr. 18, 29)> Liquid, smelling like
•amphor.
Heza-ohloro-propaaa CJBjSH, i*.
CC1,.CHCLCH01,? (0,243°). S.0. 1-63. Prom
propylene chloride and 01 (0ahour8,il. 76, 283).
Hepta-ohloro>propane C^Cl,. |260°). S.G.
X'73. From propylene chloride and 01 (Oahours).
Fer-ehloro-propane 0,01,. [160°]. (269°).
From CH,01.0H01.0H,01 and 101, at 200°.
Formed also, together with COI4, by heating iso-
butane with 101, at 240° (EraSt a. Merz, B. 8,
1045) ; and, together with 0,01, and 001, by the
action of 101, on isobutyrio acid (Erafft, B. 9,
1085). Crystalline mass; t. e. sol. alcohol,
ether and ligroin. At 250° it splits up into
0,01, and CCI4.
CHLOBO-FBOFANE SULFHONIC ACID
CaHgOl.SOaH. From the product of the action
of 101, on propane sulphonio acid at 160° the
salts (0,H,ClSO,),Ba(0,H,SO,);^a aq and
(0A01S0,),Ba3(0,H,S0,),Ba may be isolated
(Spring a. Winssmger, B. 16, 828).
a-CHLOBO-FBOFlOiriC ACID C,H,010, U.
0H,.CH01.00,H. Mol.w.l08i. (186°). S.G. 21-28.
Pr^araticm. — Calcic lactate (17 g.) is shaken
with PCI, (40 g.) and distilled from a bath of
H2SO,. The distillate is mixed in the cold with
the requisite quantity of cold water. The yield
is 60 per cent. (J. M. Lov6n, J. pr. [2] 29, 366 ;
c/. Wurtz, A. 107, 192; Ulrioh, A. 109, 271;
Lippmann, A. 129, 81 ; Buchanan, Z. [2] 4, 523;
Briihl, B. 9, 35 ; Mazzara, <?. 12, 261).
Properties. — Liquid, miscible with water;
blisters the skin.
Beactums.—l. Zme and HCl convert it into
propionic acid. — 2. The solutions of the Ba and
Ag salts change to lactate on boiling. — 3. With
cone, solution of EHS (2mols.) it gives thiolactate
and thiodilactylate of potassium.
SaltB.— AgA'.— BaA',.
Methyl ether MeA'. (182^°). S.G. *
1'075. lin 1-423 (Kahlbaum, B. 12, 344).
Bthyl ether ^ik: (147°). S.G. "f 1-0869.
M 1-4237. Ba, 61-12 (Briihl, A. 203, 24),
Reactions. — 1. When heated with thiurea 6
hours at 100° it gives the hydrochloride
of lactylthio-nrea : CS<^|;g'^'.-2. With
potassic sulphocyanide 5 hours at 150° it gives
CH,.CH(SCN).CO,Et (Freytag, /. pr. 128, 380).
a. NaOEt gives CH,.OH(OBt).OO^t.
Amide CH,.CHC1.00NHr [80°]. Scales;
T. 80I. water (Beokurts a. Otto,B. 9, 1692).
Chloride OH,.CH01.00C1. (110°). y.D.
4-88. S.0. 2? 1-239 (Henry, C. B. 100, 114).
Nitrilt 0H,.CH01.CN. (122°). Pungent
liquid.
B-Chlon-propionic acid CH,01.0H,00,H.
[41°]. (B.a.O.); [38°] (H.). (204°).
S'omialum.—l. By heating hydracrylic aoid
with fuming HOI at 120° (Beokurts a. Otto, B.
18, 226). — 2. From its chloride, which is formed
by the union of ethylene with GOOl, (Lippmann,
A. 129, 81 ; Henry, C. B. 100, 114).— 3. From
acrylic acid and HOI (Linnemann, A. 163, 95). —
4. From ;3-iodo-propionic aoid and chlorine-
water (Biohter, Z. 1868, 451).
Properties. — White plates; v. e. sol. water
and alcohol. Does not blister the skin.
Methyl ether UeA.'. (156°).
Ethyl ether EtA'. (163°). V.D. 4-94.
S.G. a 1-116.
Ghloro-ethyl ether CH^Cl.CHsA'.
(c. 213°). S.G. s 1-282. From the acid and
CH20H.CH,01 (EL).
Chloride 0Hj01.CH,.0OCl. (144°). VJ).
4-42. S.G. M 1-331.
aa-Di-ehloro-propionio aoid 0H,.001,.C0,H.
(0. 188°).
Formation. — 1. From pyruvic aoid and PCI,
(Klimenko, B. 3, 465 ; 5, 477 ; Beckurts a. Otto,
B. 11, 386).— 2. The nitrile is formed by chlori-
nating propionitrile (Otto, A. 132, 181; B. 9,
1877).
Properties. — ^Liquid; v. sol. water; insoL
cone. HOI. Solidified by cold. Converted by
zinc and HGl into propionic acid. Water at
140° gives pyruvic acid. Boiling alcoholic
KOH gives o-ohloro-aorylic acid. Beduced
silver forms GO,H.OMe:CMe.CO,H and 00,H;
OMeOl.OMeOl.OO2H.
Salts.— NHjA'. — KA'6aq. — BaA',aq.—
GaA',aq. — OaA'2 3aq. — ZnA'2aq: easily soluble
flat needles. — AgA'. — On heating with water it
decomposes into pyruvic acid, diohloropropionic
acid, and AgCl. On heating the dry salt it
yields pyruvio-dichloropropionic anhydride
Ch' Cci .C0>° "°^ ^'^^^ (Beckurts a. Otto,
B. 18, 227).
Methyl ether UeAf. (144°).
Ethyl ether EtA'. (157°) (B. a. C);
(160°) (K.). S.G. £ 1-249.
Isobutyl ether CHjFrA'. (184°).
Allyl ether CjajJ. (177°).
Chloride CH,.001j.G001 (c. 110°).
Anhydride (GH,.G01,.C0),0. (191°).
Amide CH,.CCl2.C0NH2. [116°]. Mono-
clinic lamince (Haushofer, Z. K. 7, 267). —
(CH,.CGL.C0NH),Hg aq : needles.
Nitrile CH,.0G1,.CN. (105°). S.G. 15 1-431.
Poraref triie (0H,00y,C,N,(?). [74°]. S.
(alcohol) 14 at 20°. Chlorine acting upon pro-
pionitrile forms a liquid di-bhloro-propionitrile
(104°-107°) and a solid isomeride [74°] ; the for-
mation of the latter is promoted by aJow tem- ,
perature. Both give the same di-chloro-propi-
onio acid on saponification, hence the solid form
is probably a polymeride of the liquid. The
liquid form sometimes changes spontaneously
into the solid form (Otto a. Voigt, J. pr. [2] 36,
79). Beactiona of the parcmitrile. — 1. HjSO,
(1 vol.) mixed with water (1 vol.) at 180° gives
a-di-ohloropropionio acid.— 2. Alcoholic NH,
gives di-chloro-propionamide. — 3. Zine and
aeetie acid reduce it to (0,H5),0,N, (195°).—
4. Zine acting on a solution in dilute alcohol
forms a base 0,H„N„ [111°], (0. 273°), crys-
tallising from petroleum ether in needles ot
plates, V. sol. ether and alcohol, v. si. soL
water. It forms salts : B'HOl.— B'jH^Ol,—
AgO,H„N,iaq.
139
CHLORO-PEOPIONIO ACID
cf/B-Di-chloro-propionic acid
CH,Cl.bHCl.CO,H. [50°]. (210°).
Formation. — 1. Prom glyceiio acid and HCl
(Werigo, J5. 12, 178 ; cf. A. 170, 163) 2. From di-
ohloro-propyl alcohol CHjOLCHCLCH^OH by
oxidation (Henry, B. 7, 414 ; Werigo a. Melikoff,
B. 10, 1500). — 3. From a-chloro-acrylic acid and
HOI at 180° (W. a. M.).— 4. Formed from
CHi,(0H).0H01.C0jH and fuming HCl at 100°
(Melikoff, 3. B. 13, 163 ; C. C. 1881, 354).
ProperUes. — Small needles. Alcoholic KOH
gives a-chloro-aorylio acid. — HO.PbA'.
Ethyl ether Mk: (184°). S-G.'," 1-2461.
Itg 1-4538. Ba, 59-76 (Briihl, A. 203, 25). Suc-
cessive treatment with alcoholic ECy and EOH
gives funaric and inactive malio acids (Werigo
a. Tanatar, A. 174, 867).
iSjS-Si-chloro-propionic acid CH0L:.CH2.C02H.
[66°], From /S-chloro-acryUo acid and aqueous
HCl at 80° (Otto a. Fromme, A. 239, 268).
Prisma, t. sol. alcohol, ether, benzene, chloro-
form, and water. Converted by alcoholic EOH
into OHCl:CH.COjH.
Ether M&.'. (171°- 175°).
Amide CHClj.CH,.OO.NH,. [140°]: needles.
Tri-chloro-propionio acid (?) C3H3CI3OJ (?).
[60°]. From per-chloro-succinic ether and oono.
KOHAq(Malaguti,il.Cfc. [3] 16, 67, 72,82).—
AgA'.
jS-CHLOBO-PKOPIONIC AISEHTSE
CjHjOlO i.e. CHjCl.CH2.CHO. Acrolein Jij/dro-.
chloride, (c. 46°) at 10 mm. (130°-170°). Formed,
together with the paraldehyde, by passing gase-
ous HCl into acrolein (Geuther a. Cartmell, A.
112, 3 ; Erestownikoff, J. E. 11, 249 ; Grimaux
a. Adam, C. B. 92, 800). Liquid. Beduces
Fehling'B solution. Bapidly changes to the
solid paraldehyde. HNO, forms /3-chIoro-pro-
pionic acid.
j8-Chloro-propionioparaiaeliyde(C3HsC10)a(?).
[33-5°]. (170°-175°) at 15 mm. Formed by
spontaneous polymerisation of the preceding,
into which it is reconverted by distillation under
ordinary pressure. Needles. Insol. water. It
does not reduce Fehling's solution. Not acted
upon by water or baryta at 100°, nor by AgOAo
or Pb(OAc)j at 120°. Water at 120° gives HCl
and metacrolein. Distillation over solid EOH
also forms some metacrolein.
aj3-Si-chloro-propionic aldehyde
CH,C3.CHC1.CH0. From acrolein and CI (Aron-
Btein, A. Suppl. 3, 190). Oil. Itsalcoholate
CH,01.CHC1.0H(0H)(0Bt) boils at 160°-l65°.
^.CHLOBO-PBOFix ALCOHOL 0,H,C10 i.e.
CH^CLCAfCHjOiB. Trimethylene chhrhydrin.
(161° cor.). S.G. iZ 1-132. S. fiO. From tri-
methylene glycol CH2OH.CH2.OH2OH and HCl
at 100° (Beboul, A. Ch. [5] 14, 491).
a-Chloro-iBopropyl aloQhol
CH,.0H(0H).CH,C1. PrqpyUm ehlorhydrin.
(128°). S.G.2 1-130.
Formation. — 1. From propylene glycol and
HOI (Oser, A. Svppl. 1, 254) or SjOlj (Morley, B.
13, 1805).— 2. From allyl chloride (1 pt.) and
cone. HjSOf (3 pts.) at 100°; the product being
distilled with water (10 pts.) (Oppenheim, A.
Suppl. 6, 867). — 3. From propylene and HOCl
(MarkownikoS, Z. 1870. 423).
Properties. — Iiiqnid,soL water. May probably
•ontain CE^.CHC1.0H,0H.
Beaetionit—l. P,0, gives allyl obloride and
ohloro-propylene (Henry, ^. 1871,600).— 3. The
ehlorhydrin obtained by the action of SjClj upfm
propylene glycol gives chloro-aoetone on oxida-
tion with EjCrjO, and H^SO^, or with HNO,
(Morley a. Green, B. 18, 24 ; C. J. 47, 132). The
ehlorhydrin obtained from propylene and HOC!
is oxidised (by chromic mixture) to chloro-aoet-
one according to Markowuikofl, or (by HNO3) to.
a-chloro-propionic acid according to Henry (B.
7, 1649, 1790). — 3. HNO, gives chloro-acetio acid
(Henry, Bl. [2] 25, 389).— 4. Heating with ZuO
or FbO gives propionic aldehyde and acetone
(EltekofE, J. B. 10, 222).
Benzoyl derivative CjHsOlOBz. (269°
cor.). S.G. i2 1-172; ±5 1-149. From the alco-
hol and BzCl. Oil. Alkalis form propylene
oxide. ZnBtj gives propylene ethyl phenyl ke-
tate C5Hj<[Q>CEt.O„H5 (Morley a. Green, C.I.
47, 134 ; J3. 17, 3015).
Ethyl ether CH3.CH(0Et).CH,Cl. (118°).
S.G. a -984. From di-chloro-di-ethyl oxide and
ZnMe3»(Lieben, A. 146, 225 ; 178, 14).
ajS-Di-chloro-propyl alcohol
CHjCLOHCLOHjOH. Dichloride of allyl alcohol.
(182°). S.G. s. 1-380 (T.) ; IL' 1-355 (G.).
Formation. — 1. From allyl alcohol and CI
(ToUens, A. 156, 164 ; Hubner a. MMler, A. 159,
168).— 2. From allyl chloride and HOCl (v.
Geyerfeldt, A. 154, 247 ; B. .6, 720 ; Henry, B.
3, 352 ; 7, 414). —3. Together with its isomeride,,
by passing dry HCl into glycerin (Fauconnier a.
Sanson, J52. [2] 48, 236). According to Markow-
nikoS {A. 208, 349) passing HCl into a mixture
of glycerin and aqueous HCl only produces
CH2C1.0H(0H).CHjCl {cf. ToUens, Z. 1869, 174).
Properties. — Viscid oil, si. sol. water, sol.
alcohol. Aqueous NaOH gives epichlorhydrin
(119°]. HNO3 gives ni8-di-chloro-propionicacid.
Di-chloro-isopropyl alcohol GgHuGljO i.e.
CH2Cl.CH(0H).CHjCl. QVycerin dichldrhydriii.
Mol. w. 129. (176° i.V.). S.G. 2 1-383 ; 12 1-367
(Markownikoft, A. 208, 349). S. 11 at 19°.
Formation. — 1. From glycerin and HCl (Ber-
thelot, A. 92, 302 ; Hubner a. C; Muller, Z. [2]
6, 344; Watt, B. 5, 257).— 2. From glycerin and
S3CI2 (Carius, A. 122, 73 ; aaus, A. 168, 42).—
3. From epichlorhydriii and fuming HOI (Beboul,
A. Swppl. 1, 225). — 4. l^ogether with its isomer-
ide, by the anion of HOCl with allyl chloride
(Henry, B. 3, 352).
Beactions. — 1. Chromic acid mixture o^d^eea
it to s-di-chloro-acetone [43°] and chloro-acetio
acid. — 2. Sodmm amalgam converts it intoiso-
propyl alcohol (Buff, A. Suppl. 5, 250).— 3. So-
dium added to its ethereal solution forms allyl
alcohol (H. a. M.; Tom6e, B. 21, 1282).— 4.
Alcoholic (4p.c.) NH, (2}mols.) forms amorphous
'chlorhydrinimide' C,jHj,N301j04. Weaker alco-
holic NH, (1 p.c.) forms hydrochlorides of ' di-
amido-hydrin ' CjHioNjO, and of ' glycidamine '
C3H,N0 (Claus, A. 168, 29 ; B. 8, 244).— 5. AniU
ime forms C,HsONPh.— 6. Solid NaOH gives
epichlorhydrin CaHsClO.— 7. Br at 100° gives di-
chloro-di-bromo-acetone CBrjCl.CO.CHjCl and
chloro-tri-bromo-acetone (Grimaux a. Adatu, Bl.
[2] 32, 18).— 8. PjO, aotsirigoroualy, forming di-
chloro-propylene.
Formyl derivative
CH,01.CH(0CH0).0HjCl. (0. 152°) at 22 mm.
Formed by heating the alcohol with nitro^
CHLORO-PROPYLENE.
129
methane at 220° (Pfungst, J. pr. [2] 34, 28).
The nitro-methane may perhaps first form
hydroxylamine and lormio acid: dHjNOj + HjO
"OHjOa + NHjO; but no hydrozylamine oould
be found.
Acetyl derivative CKfil.OB.lOko).G^fil.
(204°) (B. a. L.; T.); (195°) (H.); (o. 142° at
, 25 mm.) (P.). S.G. ii 1-283 (T.) ; a 1-274 (H.).
Formation. — 1. From glycerin and AoCL —
2. By passing EGl at 100° into a mixture of
glycerin andEOAo (Berthelot a. Delinaa,, A.Gh.
[3] 62, 459).— 2. Prom CHjCl.CH(0H).CH201 and
AoOl (Henry, B. 4, 704).— 3. Prom epiohlor-
hydrin and AoCl (Truchot, A. 188, 297). — 4. Prom
the fonnyl derivatiye and AgOAc (Pfungst, J. pr.
[2] 34, 28).
Butyryl derivative
(CH,Ca),CH.O.CO.C,H,. (227°). S.Q.U 1-194 (T.).
Isovaleryl derivative
(CH,0I),.CH.O.C0.04H,. (245°) at 737 mm. S.G.
U 1'149 (Truohot, A. 138, 297).
Benzoyl derivative (CH2Cl)2CH.0Bz.
(222^) at 40 mm. S.G. a 1-441. Prom epichlor-
hydrin and BzCl at 180° (I.). Also from the
formyl deriyative and BzGl (P.).
1^-chloro-isopropyl alconol
CC!1,.CH(0H).CH,. [49°]. (150°-160°). Prom
chloral by suaoessive treatment \rith ZnMei, and
I water (Garzarolli-Thnrnlackh,i4.210,77). Small
deliquescent needles (from ether). May be sub-
limed. Smells like camphor.
TEI-CHLOKO-PEOPYLAMINE C3H,Gl,.NHj.
Formed by the action of Sn and HGl on dinitro-
aUylene-diohloride G3HjGlj(N0j)2 (Pinner, A. 179,
55). Oil ; may be distUled.
/S-CBXCEO-o-PEOPYL-CINirAlltlC ACID
O.H,.C01:0(03H,).GOjH. [121°]. Prom its ether,
which is formed by treating propyl-benzoyl-apetio
ether with Pd, (W. H. Perkin, jnn., O. J. 49,
163). Tricljnio prisma; a:6:c= -797:1: -740;
rt = 122° 33' ; ^ = 106° 21' ; 7 = 69° 25' (Haushof er).
May be sublimed. V. Bol. alcohol, ether, benzene,
chloroform, and HO Ac ; m. sol. ligroin.'
Ethyl ether EtA'. (248°) at 300 mm. OiL
iS-CHLOBO-PBOPTLEirE GH2:GH.CH2C1 v.
AliLTL OHLOBIDX.
ai-CUoro-propylene CHG1:CH.CH,. Propenyl
chloride. (36°). Formed, together with some of
the following isomeride, by treating propylene
chloride with alcoholic EOH (Gahours, G. B. 31,
291). Obtained by heating propylidene chloride
CH,.CH2.CHCn2 with alcoholic KOH (Eeboul,
A. Ch. [6] 14, 462). Formed also by heating the
neutral solution of the alkaline salts of the
liquid o;8-di-ohloro-bntyric acid (Wislicenus, B.
20, 1010). Liquid. Br at 15° forms CH^GIBrj
(177°), Alcoholic KOH gives allylene. HBr
gives 0H3.CH,.GHGlBr (110°) and a small quan-
tity of CH,.OHBr.GHjGl (121°).
.iito-a-chloro-propylene 0H01:CH.0H3. (33°).
Formed by heating the neutral solution of the
alkaline salts of aj8-di-chloro-butyrie acid [63°]
(Wislicenus, B. 20, 1010).
o-Chloro-propylene OH2:GC1.0H3. (23°) (O.;
L.); (25-5°) (P.). S.Q.2-9307(P.); 2-931(0.).
V.D. 2-83 (calo, 2-65). The chief product of the
action of alcoholic KOH on propylene chloride.
Formed also by treating OHj.GGl^.CH, (from
acetone and PCU with alcoholic KOH, with
NH3, or with AgOAc.
Beaetunu.—!. HjSO, followed by water gives
Vol. n.
acetone (Oppenheim, C. B. 65, 854 ; A. Suppl,
6, 357).— 2. Wat&r at 160° also forms acetone.—
3. Br gives CHjBr.GOlBr.CHa (c. 173°) (Friedel,
A. Ch. [4] 16, 343).— 4. Alcoholic KOH at 120°
gives allylene (Priedel, O. B. 59, 294).~5. HI at
100° gives OHa.CGU.OH,.— 6. 01 in sunshine
forms OH2Gl.CGlj.OH3 (127°). In the dark Gl forma
0Hj:G01.0H2Gl.— 7. HBr gives GH3.GBrOl.GH,
(93°). — 8. HGIO gives cUoro-aoetone (Linne-
mann, A. 138, 122).
oj8-Di.chloro.propylene GHj:GCl.GH2Gl. (a).
Epidichlorhydrvn. (a)-Chloro-allyl chloride.
(94°). S.G. fi 1-236 ;ai 1.204.
Formation. — 1. Together with the following,
by the action of 01 on GHj.GGhGHj in the shade
(Priedel a. Silva, C. B. 73, 957; 74, 806; 75, 81;
Pittig, A. 135, 359), or of KOH or NBt. on
GH2GI.GHGI.GH2GI (Eeboul, A. Swapl. 1, 229;
a. B. 95, 993).— 2. Prom GH3.G01,.CH,01 and
alcoholic KOH (F. a. S.).
BeaciAom.—!. Br forms G3H,CltBrj (205°).—
2. Fuming HOI at 100° gives OHa.CGlrGHjOL—
3. HjSOj followed by water gives chlororacetone
(Henry, B. 5, 186).— 4. Alcoholic KOH gives
0H2:G01.GH,0Et (110°) 6. GIOH gives s-di-
chloro-acetone [42°] andOH,ai.G01,.CH2Gl (164°)
(Henry, 0. B. 94, 1428).— 6. NBt, at 100° forms
GH2:GGl.CH,NBt,Gl (Eeboul, O. B. 95, 993).—
7. Sodium gives allylene and propylene. —
8. Alcoholic KCy followed by KOH gives trioar-
ballylic acid and a little ozy-orotonio acid (Claus,
A. 170, 126).
(»j3 . Si - chloro - propylene OHOhCH.GH^GL .
P-EpidAcMorhydrm. $-Ohloro-aUyl chloride.
(106°) (P. a. S.) ; (110° cor.) (B.). S.G. V 1-226
(R.) ; 2 1-250 (P. a. S.). V.D. 3-83.
Formation. — 1. Together with the preceding,
by the action of solid KOH on GH2C1.GHG1.GB^G1
(P. a. S.). — 2. In the pure state by treating
GH201.0H(0H).0H2G1 with PA (Hartenstein,
J. pr. [2] 7, 310).— 3. A by-product in the action
of PGl, on acrolein (Geuther, Z. 1865, 25;
y. Boihbargh, Bl. [2] 36, 549).
BeacUons.—!. CI gives CHjCl.CHCl.CHGl,
(180°).— 2. Does not unite with HGl 3. Alco-
holic KOH gives GH01:CH.GHjOEt (123°).—
4. Aqueous KOH gives /S-ohloro-aUyl alcohol. —
6. Sodium forms isoaUylene GH2:C:GH2 (Harten-
atein).- 6. Br gives GHClBr.OHBr.CHsCl (212°).
aa-Tii- chloro - propylene GH,.GGI:0HG1.
Allylme Chloride. (75°) (P. a. S.) ; (78°) (P.
a. K.).
Formation. — 1. Prom GH3.CC12.CH2G1 by
treatment with alcoholic KOH (Priedel a. Silva,
Bl. [2] 17, 386;, J. 1872, 322).— 2. Prom tri-
chloro-butyrio aldehyde and aqueous KOH (Pin-
ner a. Kramer, A. 158, 47 ; 179, 44).
Beactions.—!. Br forms GH,.CCIBr.GHClBi
(188°).— 2. Sodvum forms allylene OH,.C:OH.
Sl-ohloro-propylene GHjrCH.GHCl,. AlVyl-
idene chloride. Acrolein chloride. (85° cor.).
S.G. 'i2 M70. V.D. 3-83. Formed, together
with CH01:OH.GH2G1 and OHC1:CH.GH,OH, by
the action of PGl, on acrolein (Geuther, A. 114,
36; Z. 1865, 25; v. Eomburgh, Bl. [2] 36,
649).
BeaoMons.~l. 01 forms CHjCl.OHGl.GHOl,
(180°).— 2. KI or Calj at 100° gives 0,HjClI
(162°) (v.Bomburgh, B. T. C. 1, 233).— 3. Potas-
sium acetate gives C,H,(OAo), (0. 130°). —
K
130
CHLORO-PROPYLENE.
4. Sodium has no action. — 6. Alcoholic KOH
gives 0Hj:0H.CH01(OBt) (o. 118").— 6. NaOBt
gives CH2:0H.CH{OEt)j (Aronstein, A. Suppl. 3,
181). 7. Cone. HClAq at 100° changes it to the
^isomeric 0Hj01.CH:CHCl.— 8. NH, at 100° forms
aorol^b-ammonia.
Tri - chloro - propylene 0H2C1.C01:CH,C1.
(142°). S.G. as 1.414. From CHjCl.COlj.CHjCl
and alcoholic KOH (Pfeffer a. Pittig, A. 135,
861).
Tri-cUoro-propylene OHa.CChCClj. (113°).
S.G. i4 1-387. From CH3.C01j.0HClj and alco-
holic KOH (Bprsche a. Fittig, A. 138, 117). 01
forms solid CjHsCl,.
Tri-chloro-propylene CHsdj. (139°). From
the crude product of the chlorination of alde-
hyde (tri-chloro-bntyrio aldehyde) and aqueous
NaOH (Pinner, JB. 6, 207). Alcoholic KOH oon-
Tcrts it into CsH^Gl^.
Tetra-chloro-propyleneOsHjCl,. (166°). From
C3H3CI, (derived from acetone) and alcoholic
KOH (B. a. P.,
CHLOBO-PEOPTLENE GLYCOL v. Glycekin
cMorJiydrin.
CHLOBO-FBOFTLISENE CELOBIDE v. Tbi-
CHIjOBO-PBOPANE.
CHLOBO-DI-ISOFBOFYL-KETONE
PaH,.C0.03H,Cl. (142°). Prepared by passing
CI into di-iao-propyl-ketone at 0° (Barbaglia a.
Gucci, B. 13, 1670 ; G. 11, 92). Liquid.
Bi-chloro-di-iaopropyl-ketone C,H,2Cl2:CO.
(176°). Prepared by passing chlorine into di-
isopropyl-ketoue at the ordinary temperature
(B. a. G.). Colourless liquid. Tnrpentine-like
odour.
Iii-cIiloro-di-isopTopyl-ketone CjHuCljiCO.
(about 229°). Prepared by passing 01 into boil-
ing di-isopropyl-ketone (B. a. G.). Liquid with
pungent turpentine-like odour.
CHLOBO-ISOFBOFYL NITBATE
CH3.0H(N0,).CHjCl. (158°). S.G. la 1-28.
From chloro-isopropyl ^cohol HNO3, and HjSO,
(Henry, A. Ch. [4] 27, 263).
ad-Si-chloro-propyl nitrate
CH3CI.CHCI.CHJNO8. (180°). S.G. ^ 1-3. From
CHjCLCHOLCHjOH and HNO, (Henry, B. 7,
409).
Si-cUoro-isopropyl nitrate (0H201)2CH.N0s.
(180°-190°). S.G. 12 1.465. Formed from
CH„Cl.CH(OH).CHjCl, HNOs.andHjSO, (Henry,
A. 165, 167).
(Py. 3)-CHL0E0-(B. 3)-IS0FE0PYL axrmOL-
<OH:CH
I Chloro-immogmnol-
N:CC1
me. Formed by heating isopropyl-carbostyril
with PCI5 (Widmann, B. 19, 265). Yellowish
oil. Heavier than water. V. sol. alcohol, ether,
benzene, &o., nearly insol. water. Sparingly
volatile with steam. Weak base. — B'sECjCl^tCl, :
[138°] ; yellow monoclinic prisms.
CHLOBa-FYBENE v. PyssNB.
CHLOEO - PYBIDINE CsH^ClN Le.
N<^g:°^CH. (148°). V.D. 67 (obs.).
FormaiUm. — 1. By heating potassium pyrrol
with chloroform in presence of ether ; the resi-
due after evaporation of the ether is boiled with
dilute HCl to resinify the unaltered pyrrol, and.
after making alkaline with KOH, the chloro-
pyridine is distilled over with steam (Ciamician
0. Dennstedt, 0. 11, 224, 300 ; ^5. 14, 1153).—
2. By the action of CCl,, chloral, or tri-chloro-
acetic ether on pyrrol-potassium (Ciamician a.
Dennstedt, B. 16, 1179). — 3. From oxy-pyridine
and PCI, (Lieben a. Haitinger, U. 6, 316).
Properties. — Pungent ^kaline liquid; m.
sol. water.
Reactions. — 1. HI at 145° gives iodo-pyrid
ine ; at 200° it forms pyridine (L. a. H.) — 2. Br
and I form additive compounds. — 3. Sodium
amalga/m forms chloro-piperidine OjH,gClN.
Salts. — B'HCl : deliquescent crystals. —
B'jHjPtClaaq : monoclinic needles; a:h\o ••
1-197:1:1-172; 5 = 109° 48' (0. a. D.); o:6:c =
l-04:l:l-25; j8 = 72° 42' (L. a. H.). Converted by
heat into B'^PtCl,.
Hexahydride 0,H,,C1N. Chloropiperidine.
From chloro-pyridene by reduotion-with sodium
amalgam or with Zn and HOI. — ^B'jajPtCljaq :
monoclinic needles; a:&:c = 1'209:1:1'094; $ =
113° 35'.
Di-chloro-pyridine C5H3CI2N. [67°]. Formed
by heating barium pyridine-di-sidphonate with
PCI5 (Koenigs a. Geigy, B. 17, 1833). Volatile
with steam. Glistening plates. Y. sol. alcohol,
si. sol. water. Hgdj added to the aqueous or
alcoholic solution precipitates a double salt
which forms long fine needles [18^°]. —
B'jHjOlaPtCl, 2aq : fine yellow needles.
Di-Dhloro-pyridine C^HsClsN. [72°]. Formed,
together with other products, by the action of
dry chlorine upon dry pyridine. Slender white
needles; sol. pyridine and alcohol, insol. water.
Has an agreeable aromatic odour (Keiser, Am.
8, 308).
Tri-oliloro-pyridine05H2Cl,N. [50°]. Formed,
together with di-chloro-pyridine [67°] by heating
barium pyridine - di - si^phonate with PCI,
(Koenigs a. Geigy, B. 17, 1832). Volatile with
steam. Long flat needles. Sol. alcohol, nearly
insol. water. '
Tri-chloro-pyridine (?) , CsHjClaN. [66°].
Formed, along with omoro-ozy-pyridine car-
bozylio aoid (g. v.) by treating nicotinic acid with
PCI5, and warming the product with H^SO,
(80 P.O.) (Seyfferth, J. pr. [2] 34, 261). Long
needles (by sublimation) ; v. si. sol. water, sol.
alcohol, «ther, and benzene.
CHLOBO-FYBIDmE-CABBOXYLIC ACID
Os'B.tGWOi i.e. CjHjClN.OOjH. Ohhro-pieolmic
acid. [180°]. From picolinic acid by treatment
with POlj, the resulting chloro-picolines, in-
cluding O5H3CINOCI,, 'being warmed with HjSOj
(80 p.c.) (Seyflerth, J.pr. [2] 34, 249).
Pr(^ertm. — Dendritic needles or prisms, sl.
sol. cold water ; extracted by ether from aqueous
solution.
Salts. — CaA'j aq.
Beaction. — I. HI reduces it to picolinic acid;
in presence of phosphorus, picoline is also formed.
Chloro-pyrldine carbozylic acid
CsHsNOLCOaH. [168°]. Chlm-o-picoUnic aeid.
From di-chloro-pyridine carboxylic acid, HOAc,
and HI at 150° (Oat, J. pr. [2] 27, 284). NeedJes
or prisms (containing aq). — ^BaA', 2aq.
Chloro-pyridine-oarboxylic aeid
«C01.0H:CH
03H3NC1.00jH i.«. Nf / . Chloro.
\ OH:C(CO,H)
nicoUnic acid. [199°]. Formed by the action of
P01( on ozy-pyridine-oarbozylio acid [303°]
OHLORO-PYROTARTAEIC ACIDS.
181
, (Peohmann a. Welsh, B. 17, 2392 ; C. J. in,
145). Sublimable. Glistening plates. Sol. water,
alcohol, ether, and aoetio acid, si. sol. benzene.
By tin and HGl it is reduced to nicotinic acid.
Dl-ohloro-pyridiue carbozylic acid
C5HjNClj.C02H. Di-ehloro-nicotmio acid. [138°].
One of the products of the action of warm HjSO,
(80 p.o.) on the oily product got from nicotinic
acid and PCI5 (Seyfferth, J. pr. [2] 34, 262).
Clumps of needles (from water).
Ethyl ether EtA'. [50°].
Si-chloro-pyridine carboxylio acid
CjHjOljN.CO^. Di^Moro-picoUmc acid. [180°].
Preparation. — The mixture of penta- and
heza-ohloro-picolines obtained by boiling (10 g.)
comenamic acid with (20 g.) dilute (80 p.c.)
H2SO4 tor an hour contains diohloro-, dionloroxy-,
and chloroxy-pioolinio acids. The first acid is
extracted by chloroform, the other two are sepa-
rated by means of their lime salts, the calcic
chloroxy-pioolinate being the more soluble (Ost,
J.pr. [2] 27, 281). Properties. — Slender needles.
(containing aq) ; si. sol. cold water, v. sol. hot
water and chloroform. Gives no odour with
Fe^CI,. Seduced by HI in glacial acetic acid to
picolinio acid.
Salts. — NaA'. Trapezoidal plates. — KA'.
Triangular and trapezoidal plates, often twins.
Tetra-hydride OjHjOlN.CO^H. [0.268°].
From the above by tin and HCl. Iiamina (from
water).— B'HCl.
Oi-chloro-pyridine-carboxylic acid
C,H,N(C1),(C0,H) U. ^(^^^CCO^ (?).
[210°]. Formed by heating citrazinio acid with
PCI5 (Behrmann a. Hofmann, B. 17, 2694).
Colourless plates. Sol. alcohol, v. e. sol. ether,
b1. sol. water. — A'Ag: colourless needles.
TETEA-CHLOEO-PYBIMIDINE C^NjCl^ t.fl.
CC1=CC1— OCl
I II . [68°]. Formed by heating
N = C01 — N
alloxan (1 pt.) with POl, (6 pts.) and POCI3
(5 pts.) for 8 hrs. at 120°-130°. Colourless
pearly plates, of oamphor-like smell. Volatile
with steam (Ciamician a. Magnaghi, Q. 16, 173 ;
B. 18, 3445).
TETEA-CHLOEO-PTEOCATECHIN
C.Ca4(0H), [1:2:3:4:5:6]. [174°]. Obtained by
passing chlorine into a hot, strong solution of
pyiocatechin in aoetio acid. Colourless needles
or thick plates. On oxidation it gives tetra-
chloro-o-qninone CjClA (Zincke, B. 20, 1779).
PEE-CHLOaO-PYEOCOLI. CoNjOjOIs. [above
320°]. Formed, together with the tetra-chloride,
by heating pyrocoll (1 g.) with PCI5 (12 g.) at
220° for 6 hrs. (Ciamician a. Danesi, G. 12, 81).
Scales. Insol. cold HOAo. Changed by long
boiling into tri-ohloro-pyrrol carboxyUc acid.
Tetra-chloride CioNAClw Formed as
above (C. a. D.). Pearly triolinio prisms (from
HOAo). SI. sol. oold HOAc.
Octo-ohloride C,„NAC1m- [147°]. From
per^shloro-pyroooll and PCI5 at 250°. Subhmes
a little above 100°- Smells like camphor. By
redaction with zino-dust and acetic acid it yields
tetra-ohloro-pyrrol. Heated with water at about
130° it decomposes into (a)-di-ohloro-aorylioaoid
r86»], NH„ COj, and HCl. By boiling with di-
lota Boetio acid it ifl resolved into di-ohloro-
maleimide, CO, and HOI (Ciamician a. Silber,
(?. 13, 320; JB. 16, 2389).
TEX - CHLOEO - PYEOaALIOL 0„Cl3(0H),.
Tri-chloro-pyrogallic acid. [o. 185°] (H. a. S.).
A mixture of pyrogallol (5g.) and acetic acid
J12-0 c.c. of 60 p.o.) is kept cool and dry chlorine
is passed in. In half-an-hour tri-chloro-pyro-
gaUol crystallises out (Webster, C. J. 45, 205). '
Properties. — Fine needles (containing 3aq).
Kesemblestri-bromo-pyrogallol, notably in giving
a deep blue colour when baryta is added to its
ethereal solution. When anhydrous it melts
about 177° {W^ ; when hydrated it melts at 115°
(W.) or 75° (H. a. S.). Sol. water, but slowly
decomposed by it. Sol. acetic acid, benzene,
chloroform, CSj, and CCI4. V. sol. alcohol and
ether. Beduces ammoniacal AgNO, to a mirror.
Beactions. — 1. Sodium sulphite gives a fugi-
tive red colour. — 2. Cone. HNO, decomposes it.
3. Treated with chloroform saturated with chlor-
ine, it turns wine-red, then effervesces and be-
comes yellow. On evaporation, crystals of ' leu-
cogallol,' C,sHs01jO,2 2aq (Stenhouse a. Groves,
C. J. 28, 704), separate. Hence pyrogallol
added to chloroform saturated with chlorine is
converted into ' leucogallol,' the intermediate
tri-chlorinated body being found to very small
extent.
Salts. — Ba3(C,Cl,0,)2 6aq (Hantzsch a.
Schniter, B. 20, 2033).— Cu,(CsCl30s)j 6aq.
Acetyl derivative d,Cl,(OAc),. [122°].
^Y-Di-CHLOEO-PYHOSmCIO ACID CaH^OljO^
[169°]. Obtained by the action of cone, alcoholic
KOH upon pyromucic - ether - tetra - chloride
(formed by combination with chlorine in the
oold) (Denaro, O. 16, 333 ; Hill a. Jackson, B.
20, 252). Felted needles. Sol. hot water, v. sol.
alcohol and ether, m. sol. boiling benzene or
chloroform, si. sol. cold benzene or chloroform.
Warmed with excess of bromine-water it is con-
verted into mucochlorio acid with evolution of
COj. By boiling with dilute HNO3 (1:2) it yields
mucochlorio acid and di-chloro-maleic acid.
Salts. — A'2Ba3aq: fine needles, si. sol. cold
water. — A'sCa 4aq : long needles, si. sol. oold
water. — A'K: rather sparingly soluble small
prisms. — ^A'Ag : fine needles.
Ethyl ether A'Et: [64°], slender needles.
Amide O1HCljO.CO.NH2: [176°], felted
needles. '
CHLOKO-PYEOTAETAEIC ACIDS.
Ita - chloro - pyrotartaric acid CsH^OlOt.
[140°-145°]. (0. 230°). From itaconio acid and
cone. HCl at 130 (Swarts, Z. 1866, 721). In a
current of dry air at 150° it forms an anhydride.
Boiling water or alkalis form paraconio acid,
CjHjO^, which rapidly changes to itamalic acid,
CsH^O,.
Diethyl ether Et^A". (251°).
Citra- chloro -pyrotartaric acid CsH,010,.
[129°]. From oitraeonio anhydride and cold
fuming HCl. Formed also by the union of mesa-
conio acid with HCl (Fittig, A. 188, 61).
Tables. Boiling water splits it up into HCl and
mesaconio acid.. Boiling alkalis form meth-
acrylic acid.
Ita-di-chloro-pyrotartario acid CjH,C]jO,.
(S.).
Citra-di-chloro-pyrotartaric acid C5H3C1204.
From citiaconio acid and CI (Swarts, J, 1873,
k2
.182
OHLORO-PTBOTARTARIO AOIDS.
582 ; Bull. Acad. Boy. Belg. [2] 33, No. 1). On
distillation it gives HCl and oitraoonic anhydride.
Boiling water oonverta it into chloro-citramalio
acid CjHjClOs. The Ha salt when boiled in
aqueons solution gives chloro-methacrylio acid.
TETEA-CHLORO-PYEEOL aCl.NH. [110°].
(261°) at 754 mm.
FormalAcm. — 1. Together with di-chloro-
maleiG acid and NH,, by treating pyrrol with
NaOGl. — 2. By reduction of per - chloro-
pyrocoU-ooto-chloride with zinc-dust and acetic
acid. — 3. By heating di-chloro-maleimide with
PCI5 at 160°.— 4. By reducing with zinc-dust
and HCl the per-ohloride GjCljX which is ob-
tained by heating di-chloro-malelmide with FCl,
at 2U0° (Ciamician a. Silber, B. 16,2390; 17,
554, 1743; G. 14, 356). Very volatile. Long
silky plates. V, sol. alcohol and ether, si. sol.
water. Dissolves in alkalis. The ammoniacal
solution gives a white pp. with AgNO,. It dis-
solves in strong E2SO4 with an intense reddish-
brown colour ; on adding a few drops of water
this changes to violet, and by further addition
of water gives a green pp. which dissolves in
EOH with an intense orange colour.
(«) - TEI - CHLOEO-PYESOL-CAEBOXYLIC
ACID C5Cl,HjN0s i.e. C^HOljN.COjH.
Prepared by heating per-ohloro-pyrocoll with
caustic potash.
OjoCljNjO, + 2K0H = 2C4Cl3HNOOjK
(Ciamician a. Banesi, O. 12, 34). Long silky
needles (containing aq). V. sol. alcohol and
etfier, si. sol. water ; its solutions give with lead
acetate a white pp., and with ferric chloride an
intense red colouration. It decomposes with
violence at 150°. BaA'j aq : scales, m. sol. al-
cohol, si. sol. water.
TEI-CHLORO-PYRTTVIC ACID Hydrate
CC1,.C(0H)2.C02H. ' Tri-chloro-isogVyaric acid.
[102°]. Prepared by saponification of tri-ohloro-
acetyl cyanide with HCl (Claisen a. Antweiler,
B. 18, 1937). Formed also, together with tri-
oarbaUylic acid, by treating gallic acid, salicylic
acid, or phenol with HCl and KCIO, (Schreder,
A. 177, 282). Colourless prisms. V. sol. water,
alcohol, ether, acetic acid, and acetone ; m. sol.
C,He and CSj ; insol. petroleum ether. Beduces
FehUng's solution and ammoniacal AgNOg.
farmed with an alkali it readUy splits up into
chloroform and an oxalate. — A'TBa : small soluble
prisms. — KaA'xaq (HoSerichter, J. pr. [2] 20,
198).
Amidt CCl5.C(0H)j.C0NH,. [127°]. Pre-
pared by the action of cold aqueous HCl on tri-
chloro-aoetyl cyanide. Colourless crystals. Sol.
water, alcohol, ether, and acetone ; si. sol.
CS2, CgH,, and CHCl.. On heating it loses HjO
and is converted into a compound of the formula
CgClgOjHjN, which forms small plates or needles
of melting-point [218°], which are gublimable
and sol. ether, si. sol. water.
Nitrile v. Tbi-ohlobo-acettd cTAmDE.
a-CHLOEO-FYETTVIC AIJ)EHYB£
CH,.C0.C010.
Omm CH,.C0.CC1(N0H) : v. Chlobo-
ISOmiBOBO-AOEIONE.
CHIOEO-QUAETEimJC ACID v. Celobo-
CBOIOMIO ACID.
DI-CELOEO-QTTIKAIDINE v.
{Py, 3) -MEIHtL-QDIKOblNB.
DZ-OHLOBO-
(£.l)-CHLOEO-(lUIITOLIirE C,H,G1K U.
CH:C01.C.CH:CH
I r I
CH:OH.C.N = CH
[32°]. (268°). Formed together with the (B. 3) -iso-
meride by heating m-ohloro-aniline with glycerin,
nitrobenzene, and H^SOj (La Coste,£. 18, 2940).
Formed also from the corresponding amido-
qiiinoline by Sandmeyer's reaction (Freydl, M,
8, 583). Needles or thick glistening prisms.
The bichromate forms long yellow needles,
[165°] ; sol. hot water, si. sol. cold.
(B. 3)-Chloro-quinoline
CH:CH.C.CH:CH
I II I
CC1:CH.C.N : CH
(0. 257°). Formed, together with the (B. !)•
isomeride, by heating m-chloro-aniline with
glycerine, nitrobenzene, and HjSO,. Liquid;
solidifies in a freezing mixture. Volatile with
steam. V. soL alcohol, ether, and benzene;
nearly insol. water. Is probably not quite pure
(La Coste, B. 18, 2940).
Salts. — B'HCl : colourless tables.
B'2H2Cl2PtCl4 2aq : orange silky needles.
B'jHaOrjO,: [119°] fine yellow silky needles;
S. -25.
Methylo -iodide B'Mel : [232°]; long
yellow needles. On oxidation with KMnO, it
gives the formyl-derivative of ohloro-methyl-
amido-benzoic acid, and chloro-methyl-isatin
(La Coste a. Bodewig, B. 17, 926 ; 18, 428).
(B, 2)-ChloFO-quinoIine
CChCH.C.CH:OH
I II I
OH:CH.O,N : OH
(256°). Prepared by heating |>-chloraniline with
glycerine, lutro-bepzene, and H-SOi ; the yield
is 100 p.0. (La Coste, B. 15, 560). Colourless
liquid.
Salts. — BHCl: soluble colourless needles.
(BHCl)jPt01,2aq : yeUow crystalline pp.
Meihylo-iodide B'Mel: soluble crystalline
solid.— (BMe01)jPtCl4 : orange crystalline pp.
{Py. 3)-Chloro-quinoline C,H,NC1. [38°].
(267°). Formed by the actionof PClsOncarbostyril
or oxy-carbostyrU (Friedlander a. Ostermayer, B.
15, 33p). Volatile with steam. Long needles.
V. sol. alcohol, ether, benzene and ligroin, nearly
insol. water. On heating with water to 120° it
gives carbostyrU.
Chloro-quiuoline CjHjClN. Formed by heat-
ing oynurin with PCI. and POOL (Kretsohy, M.
2, 77).— B'H^tCl. 2aq.
(Py. 1,3) - Di - ohloro - quinoline, called (7),
" 'CH *
[67^. (281°). Formed by the
action of POl, on (Py. l,3).di-oiy-quinoUne
(Friedlander a. Weinberg, B. 15, 2683) or on
(7)-chloro-carbostyril (Baeyer a. Bloem, B. 15,
2150). Slender needles ; sol. alcohol, ether, and
benzene, nearly insol. water.
(B. l:4)-Di-cMoro-qiiinoUne
CH:CC1.0.CH:CH
I II I • [93°]. Prepared hy heating
CH:CaO.N = CH ' «
(3:6:l)-di-chloro-aniline with glycerin, nitro-ben-
zene, and H2SO, (La Coste, B. 15, 661). Volatila
nndecomposed. CblonrlesBneedlwqrti^l)!^^ ggi.
alcohol and ether.
>CC1:C
^N :C
aHlOEO-QUINONE.
133
(B. a:4)-Di-cUoro-qnbiaIin«
CC1:OH:,O.OH:OH
I II I . [104°]. Prepared by heating
CH:CC1.C.N : CH
(4:2:l)-di-ohloro-aniline with glycerin, nitro-ben-
zene, and HjSO, (La Ooste, B. 15, 561), Long
fine colourless needles. SI. sol. alcohol.
(Py. 2,3)J)i-ohloTO-CLninoline C,H,CljN t.e.
^CHiCCa
^^t\ i • [105°]. Weak base. Prepared
^ N:CC1
by treating hydro-carbostyril with POl, and dis-
tilling the product with steam ; the yield is 20-30
p.o. (Baeyer, JB. 12, 1320). Insol. water, sol. al-
cohol, ether, and CjH,. On reduction with HI
it gives qninoline.
Tri-chloro-qninoline OjH^CajN. [108° unoor.].
Formed by heating phenyl-malonamio acid
(malonanilidio acid) CO2H.GE2.CO.NHFh with
benzene and PCI, (Bugheimer, B. 17, 736). Long>
colourless needles. Volatile with steam. Sol.
alcohol, benzene, and Ugroin. By heating with
an acetic acid solution of HI at 240° it is reduced
to quinoline.
Tri-cUoro-qninoIine C^,CljN. [161°]. From
di-chloro-earbostyril and PCI5 (Friedlander a.
Weinberg, B, 15, 1426). Slender needles (from
alcohol) ; slightly volatile with steam. '
Tri-ohloro-quinoline OgH^CljN. [211°].
Formed by acting on the borate ol{B. 4)-chloro-
quinoline with bleaching powder solution (Em-
horn and Lauch, A, 243, 361). Keedles (from
acetic ether).
{Py. 2)-CHLOS0-IS0aTniroLIKE CsH^ClK
.CH:CC1
M.CM.JC I (?). [45°-48°]. (280°) at 753
NCH:N
mm. Formed by heating the di-chloro-deriva-
tive [123°] with HI and P at 170°. By more pro-
longed action at 200° it is completely di-chlori-
nated to isoquinoline. Long colourless needles.
Weak base (Gabriel, B. 19, 1655, 2356).
> (Py. 2:4)-I)i-ohIoio-iBoquiiioIine CsHjClgN i.e.
xcacci
C^.< I . [123°]. (306°). Formed by
X!a:N
heating the imide of phenyl-acetio-o-oarbozylio
^Hj.CO
acid C.H.< I with POCl, (3 pts.) at 150°-
\C0. NH
170°. Very long flat needles (from alcohol). ' V.
Sol. chloroform, benzene, ether, and hot alcohol.
Slowly volatilises with steam. By HI and P it
is first reduced to the mono-chloro-derivative
and finally to isoquinoline (Oabriel, B. 19, 1655,
2355).
CHIOEO-aTriNOHi: CjEgClOp [57°].
Formation. — 1. By distilling onprio quinate
(25 g.) with NaCl (60g.), MnOj (40 g.), H^SO,
(100 g.), and water (170 g.) (Stadeler, A. 69, 300).
2. By oxidation of chloro-hydroquinone with
CrO, (Levy a. Schultz, A. 210, 144 ; B. 13, 1428).
3. By adding aqueous KjCrO^ to a slightly acid
solution of chloro-amido-phenol Bolphate (Koll-
tepp, A. 234, 14).
ProperUes. — ^Long yellow trimetric needles;
o:5:c = ■47:1:1-71; v. sol. ether, m. sol. alcohol,
HO Ac, and hot water. Turns the skin purple.
Reduced by SO2 to ohloro-hydroquinone.
ReacUms. — 1. When mixed with m-rdtro-
aniline in benzene solution, dark green crystals
of 0,n,Cl(0)j(NHyC»H,.NO,), separate. This
breaks np into'its constituents even on recrystal-
lising from benzene (Niemeyer, A. 228, 322).
2. p-Toluidine forms, in the same way, white
plates [90°] (" 0,H,C1(0H)2(C,H,N)2?)
(o).Di-chloro-quinone C^HjCljOj [5:2:4:1].
[159°].
Formation. — 1. One of the products of the
distillation of cupric quinate with MnO,, NaCl,
and HjSO, (Stadeler, A. 69, 300).— 2. From
benzene and CI^O (Carina, A. 143, 315).— 3. Toge-
ther with chloro-benzene and tri-ohloro-pheno-
malic acid, by dissolving benzene (48 g.) in'
HjSOi (300g.), diluting with water (150 g.), and,
after cooling, adding more benzene (100 g.) and
KClOa (150 g.). The mixture is left to itself for
a week (C.).^ — 4. By the oxidation of (a)-di-
chloro-hydroquinone.with cone. HNO3 (Levy a.
Schultz, B. 13, 1428 ; A. 210, 150>.— 5. By oxi-
dation of di-chloro-^-phenylene-diamine [164°]
with KjCr^O, and H^SO, (Mohlau, JB. 19, 2010). —
6. By oxidation of ^-di-chloro-anUine with
KjCrjO, and HjSO,. — 7. From quinone by two
alternate treatments with HCl and with Fe^Cl,
(Levy, B. 18, 2366).— 8. By adding KjCrO, to
a solution of di-chloro-amido-pheuol sulphate
(EoUrepp, A. 234, 15).
ProperUes. — yellow monoolinio crystals ;
a:6:c;=l-15:l:2-21; 3 = 66° 26' (Grunling) ; a:b:c
= l-09:l:l-84; /3 = 89° 11' (Fock, Z. K. 7,40).
Sol. ether and chloroform, nearly insol. alcohol,
insol. water. Volatile with steam. SO2 reduces
it to di-ohloro-hydroquinone [172°].
Beactions. — 1. AnMne in acetic acid solu-
tion, in presence of some HCl, forms blue plates
of the anilide .CsHCljOafNPhH) [5:2:4:1:3]
[180°], which dissolves in cone. H2SO4 giving a
deep-blue liquid (Niemeyer, A. 228, 332).— 2. If,
after warming with aniline, the hot solution is
treated with HOAc, lustrous brown plates of the
di-anilide OaCl202(NPhH)2 [290°] are formed.
This is the so-called ' chloranil-aniUde ' obtained
from tetra-chloro-quinone and aniline. — 3. m-
Nitro-aniUne forms dark green crystals of
C,HjCl2Q2(NH2.CeH,.N02)2 [110°] which may be
crystallised from hot benzene (Niemeyer, A,
228, 322).— 4. p-Toltddme forma a crystalline
compound [115°] ('<C.H2Cl202(C,H,N)2?).
(i3)-I)i-chIoTO-quiiione C^^CljO, [2:6:1:4].
[120°].
Formation. — 1. By oxidation of triohloro-
phenol with HNO,, or a mixture of HNO, and
HjSO, (Faust, Z. 1867, 727; Weselsky, B. 3,
646 ; Levy a. Schultz, JB. 13, 1428 ; Guareschi
a. Daccomo, B. 18, 1170). — 2. In small quan-
tity by treating di-chloro-nitro-phenol [125°]
with HNO, and H2SO4 (Armstrong, Z. 1871,
521). — 3. By oxidation of di-chloro^-phenylene-
diamine with CrOj (Levy, B. 16, 1445). Yellow
trimetric crystals, o:6:c = •7127:1:2-027. V. sol.
boiling alcohol, v. si. sol. hot water. Turns the
skin brown. Beadily sublimes. Volatile with
steam. SO2 forms (/3)-di-chlorQ-hydroquinone
[158°].
Beactions. — 1. ArUUne (Imol.) in alcoholic
solution containing a little HCl, forms bluish-
violet needles or plates of the anilide
C8HCl202(NPhH) [154°]. This is sol. alcohol
and ether, and gives a violet-blue solution in
cone. HjSO, (Niemeyer, .4. 228, 332).— 2. Excess
of aniline added to an alcoholic or acetic acid
134
CHLORO-QUINONE.
Bolution forms CaHClOafNPhH)^ [2:1:4:6:3]
[262°]. This forms lustrous brown plates, si.
sol. alooholand benzene, m. sol. hotHOAc (N.). —
8. m-Nitro-amline forms glittering dark greein
prisms of CsHjCl202(NHj.C6Hi.NOjj [112°].— 4.
p-Toluidme forms, m the same way, slender
needles [73°] (''0^fi^OB.)jO,^H,m).
Tri-oMoro-quinone OjHOlsOy [163°].
Formation. — 1. By chlorinating quinone
(Woskresensky, J. pr. 18, 419). — 2. By boiling
quinio acid with MnOj and HCl (Stiideler, A. 69,
318). — 3. Together with tetraehloroquinone, by
treating phenol with KClOj and aqueous HOI
(Graebe, A. 146, 9 ; Stenhouse, 0. J. 21, 141).—
4. From benzene and CrOjClj (Carstanjen, B. 2,
633). — 5. By dropping sodium hypobromite solu-
- tion slowly into a solution of the hydro-chloride
of tri-chloro-p-amido-phenol ; the pp. is re-
crystalUsed from alcohol (M. Andresen, J. pr.
[2] 28, 422).— 6. From ^i-amido-phenol (g. v.)
tnd bleaching powder (Schmitt a. Andresen,
/.jw. [2] 23,436).,
Properties. — YeUow prisms. May readily be
sublimed. Does not colour the sMn. Insol.
wateri sol. hot alcohol, v. sol. ether. DUute
aqueous EOH dissolves it, forming di-ohloro-di-
ozy-quinone (chloranilic acid).
Reactions. — 1. With alcoholic solution of
aniline it gives glittering plates of di-chloro-
quiuone - di - anilide : 2CJHCI3O, +.3PhNH2 =
C5(NPhH)jCljO, + C,HC1,(0H)2 +' PhNH^HCl.
This substance crystallises from benzene in
tablets which have a bluish lustre (M. Andresen,
J. pr. [2] 28, 423).— 2. Aniline (1 mol.) forms
lustrous leaflets of CeHC10„(NPhH)2. This forms
a blue solution in cone. H^SO, (Schultz, B. 10,
1792 ; A. 210, 180).— 3. AniUne treated with
excess of the quinone forms blue plates of
CsCljOjINPhH) (Niemeyer, A. 228, 332).— 4. m-
Nitro-aniUne forms lustrous dark-green prisflas
of C^Cl,Oj{NH2.C5H4.N02)j [108°] (N.).— 5.
pels at 190° gives CsClj.- 6. AcCl gives the di-
aoAyl derivative of tetra-ohloro-hydroquinone. —
7. Boiling cone, aqueous ECl forms tetra-
chloro-hydroquinone.
letra-chloroquiuone CJCI4O2.
Formation. — 1. By the action of a mixture
of EOIO3 and HCl on quinone, aniline, phenol,
tri-ohloro-phenol, di-nitro-phenol; tri-nitro-
phenol, salicin, salicylic acid, isatin, quiuic
acid, tyrosine, m-amido-benzoic acid, &o. (Hof-
mann, A. 52, 65 ; Hesse, A. 114, 303 ; Staedeler,
i4.69,326; 116,99; Stenhouse,^. 78,4; A.Stippl.
6,209 ; Erlenmeyer, J.1861,404 ; N.Jahr.Pha/rm.
xvi. 292). — 2, By passing chlorine into an alco-
holic solution of chloro-isatin (Erdmann, A. 48,
309).— 3. From penta-ohloro-phenol and faming
HNOs (Merz a. Weith, B. 5, 460).— 4. Prepared
by oxidation of tetraohlorohydroquinone (Levy a.
Schultz, B. 13, 1429).— 5. By heating trichloro-
quinone (6 g.) for 12 hours with fuming HCl
(100 O.C.). The product is oxidised by strong
HKO, and recryst^sed from alcohol (Aiidresen,
J.pr. [2] 28, 425). — 6. From s-tetra-chloro-benz-
ene [137°] and faming HHO, (Beilstein a. Eur-
batofF, A. 192, 236).— 7. From phenol and chlo-
ride of iodine (Stenhouse, O, J. 23, 6). — 8. From
' di-chloro-di-oxy-quinone and PCI5.
Properties. — Pale yellow lustrous scales.
Monoclinio; a:&:c= l-52:l:3-00; i3 = 73°58'(Fork,
Z. K. 7, 40). VTien heated gently it sublimes
without melting. Insol. water, v. si. sol. cold
alcohol, m. sol. ether. Npt attacked by HNO„
by HCl, or by boiling cone. H^SO,. SO, reduces
it to tetra-chloro-hydroquinone. Boiling HCl or
HBr also reduce it to the same body.
Reactions. — l.Conc. aqueous KHSOjforms 'po-
tassium thiochronate ' Co(OH)02(SO*K)(SOjK)2.
Dilute KHSO, gives OsCl2(OH)j(SO,K)j.—
2. Aqueous EOH forms a purple solution con-
taining CsClj(OE) A'—S. AoCl at 170° gives CI
and C,Cl4(0Ac)j (Graebe, A. 146, 12).-4. PCI,
at 180° gives OgClj. — 6. Aqueous NH, gives
Cb01j(NH2)(0H)0j (Erdmann, J. pr. 22, 287;
.Laurent, A. Ch. [3] 3, 493).— 6. Alcoholic NH,
forms CaCl2(NH2)202. — 7. An alcoholic solution
of amline reacts thus: CaCl402-i-4NPhHj
= CBCl2(NPhH) A + 2NPhH;j,HCl (Andresen,
J.pr. [2] 28, 426). — 8. m-Nitro-amline forms
almost black crystals of C„C140j(NHj.CbH,.0H)j
(Niemeyer, A. 228, 322). — 9. A hot aqueous so-
lution of NaNOj converts it into nitranilic acid
(Nef, B. 20, 2027).— 10. By warming an acqtic
acid solution of ^-amido-xylenol (4 pts.) with
chloranil (1 pt.) there is formed a colouring
matter C2,H2sN203. Sol. alcohol, ether, benz-
ene, and acetone, insol. water. Dissolves in
alkalis with a blue colour, in cone. EEj.S'^t ^^^^
a greenish-blue. By CrO, it is oxidised to p-
xyloquiuone (Sutkowski, B. 20, 980).
Tetra-chloro-o-quinoue C5CI4O2 [1:2:3:4:5:6],
[132°]. Obtained by oxidation of tetra-chloro-
pyrooatechin with HNOj, or directly by passing
chlorine into a hot acetic acid solution of pyro-
catechin until it assumes a deep reddish-yellow
colour. Dark-red crystals. Y. sol. acetic acid
(Zincke, B. 20, 1779).
p-DI-CHLOBO-ftTIIKONE.DI - CAEBOXYLIC-
ET^yL-ETHES 05Cl202(C02Bt)2 [1:4:2:5:3:6].
[195°]., Formed by the action of chlorine
upon quinone-di-hydro-di-carboxylic ether (di-
oxy-terephthalic ether) or upon succinyl-suo-
cinio ether, suspended in alcohol. Greenish-
yellow nee^es. Sol. acetic acid and chloroform,
si. sol. alcohol and ether. The CI atoms are ex-
tremely mobile : thus by very dilute NaOH it is
dissolved with formation of di-oxy-quinone-di-
oarboxylio ether; by NH, or' amines it is readily
converted into di-amido-quinone-di-earboxylio
ether or its alkyl-derivatives. It is reduced by
zinc-dust and acetic aoid to the colourless di-
chloro-hydroqoinone-di-oarboxylic ether (di>'
chloro-di-oxy-terephthalio ether, q.v.) (Hantzsoh
a. Zeokendorf, B. 20, 1310).
Dihydride C8H2020l2(C02Et)2.^ The colour-
less di-chloro-di-oxy-terephthalic ether becomes
intense greenish-yeUow when melted, changing
to the tautomeric dihydride of tetra-chloro-qui-
none di-carboxylio ether. The colourless body
dissolves in benzene, chloroform, and cone.
S04H2 with an intense greenish-yellow colour,
whereas the solution in alcohol is colourless ;
the formation of an alcoholate (with 2H0Et)
appears in the latter case to hinder the tauto-
meric change. This alcoholate can be dissociated
by adding benzene to the colourless alcoholio
solution when it turns yellow (Hantzsoh •.
Herrmann, B. 21, 1757).
CHLORO-QTJINON^E-CHLOIIIMIDE
OaHjCl^'l [2 1]. Formed by adding bleach.
OHLOEO-RESOROIN.
186
!ng powder to a aolntion of the hydro-ohloride
of ohloro-p-amido-phenol at 0° ^ollrepp, A.
234, 16). Yellow needles (from alcohol or
HOAo).
Si-chloro-quinone-ohlorimide
C^jCl,/) [6:2:J]. [67"]. Prom di-ohloro^
amido-phenol hydrochloride by treatment in the
eold with bleaching powder (EoUrepp, A. 234,
19). Tellow needles ; sol. alcohol ; decomposes
at 170°.
Di-chloro-qniaone di-cMorimide
.NCI
CaH«\ I • Prepared by the action of chloride
^NCl
of lime on an acid solution of ^-phenylene-di-
amine (Erause, £. 12, 47). White needles. Insol.
cold water, sol. hot water, alcohol ether, CgEs &o.
Neutral body. On reduction it gives ^i-phenyl-
ene-diamine. By boiling with HGl it gives
tetrachloropheuylene diamine. Bromine in
acetic acid solution converts it into di-chloro-di-
bromo-quinone.
Tri-chloro-qninone eUorlmide
C^C!l,<Oci>. [118"].
Pr^aration. — ^By stirring a slightly acid
solution of tri-ohloro-p-amido-phenol (j. v.) with
a Solution of bleaching powder (Schmitt a. An-
dresen, J.pr. [2] 23, 438 ; 28, 427).
Properties. — ^Long yellowish needles, with
rough ends. V. sol. hot alcohol, ether and benz-
ene, less sol. cold water. When melted it forms
a light-brown liquid, which boils at 18S° with
decomposition.
BeaeUons. — 1. AniKne (3 equivalents) forms
di-chloro-quinone dianilide :
OeCl,H<^£jj> + SPhNH, + H.0
= 0BClj(NPhH)2<Q> + PhNH2,HCl + NH^Cl.
But when excess of aniline (5 mols.) is added to
saturated alcoholic solution of the chloro-imide
at 60° a violent reaction occurs, and the crystals
which ultimately separate contain another body
also. TbiB IB di-^heiiiyl-M-amido-eKloro-qumoTie-
cKUyro-phmyUmide, C,Cl(NPhH)jH<^Q^> ,
[195°]. It forms long elastic needles(fromalcohol).
It is sol. ether, benzene, glacial acetic acid and
CS,. (a) Nitrous acid passed into its alcoholic
solution produces an unstable nitroso-derivative.
(Vj It is not affected by boiling aqueous potash,
but is converted by alcoholic potash into glitter-
ing red needles of C,CI(NPhH)»H(ONa)(NPhNa).
But this compound is so unstable that alcohol
reconverts it into the original body with simul-
taneous formation of NaOEt. (e) Fuming HCl
mixed with alcohol reacts thus :
OeCl(NPhH)jH<^^^> + H,0 + HOI
= C,C!l{NPhH)^<Q> + PhNH2,HCa (Andre-
sen, J.pr. [2] 28, 427).— 2. The ethyl derivative
of o-amido-phenol (08H4(OEt)NHj) acts upon
tri-chloro-quinone-cWorimide in a similar way,
forming di-ethbxy-di-phenyl-di-chloro-quinone :
C,Cl2(NH.0BH,.0Bt)A- This body melts about
[200^, crystallises from alcohol in glittering
brown prisms, and is thrown down as a grass-
green pp. when water is added to its alcoholic
solution. It is not dissolved by alkalis, but
forms a deep-blue solution with HjSO,. —
3. Di-methiyl<i,ri,iU7i6 in warm alcohoho solution
acts thus: O.ClsHC I -h2PhNMe,-
\NC1
O.ClsB
\n.o,h^.
,NMe,
+ O.H,NMe„HOL Trl-
ohloro-quinone-di-methyl-amido-phenyl-imide is
almost insoluble in water. It crystallises from
alcohol in golden-green needles which have a
blue streak (when scratched) and are very tough.
It is V. sol. ether, benzene, and chloroform. It
is reduced by SO, to di-methyl-amido-plhenyl- '
tri - chloro - phenol, C.0l3H(OH).NH.CeH4NMe2.
This latter is insoluble in water, readily soluble
in ether, benzene and chloroform. Becrystallised
from alcohol, it melts at [139°], but its alcoholic
solution is readily oxidised by the air to the pre-
ceding imide. Salt. — B'HOl. The suVpJumio
acid of this base 050l3(SOsH)(OH).NH.C5H,NMe2
is formed along with the base itself by the action
of SO, on tri-chloro-quinone-di-methyl-amido-
phenyl-imide. It crystallises in pearly plates
when HCl is added to its solution in KHg. It
is insoluble in water, alcohol, ether and benz-
ene. BaClj added to a solution of the acid in
an alkali gives a pp. which may be recrystaUised
from hot water (Schmitt a. Andresen, J. pr. 132,
426).--4. Aqueous HCL acts upon tri-chloro-
quinone-chloro-imide as follows :
O.Cl3H<^*^^> -H H,0 + 2HC1
=C8Cl3H<^^ + NH4CUCl2. HBr acts simi-
larly (Andresen, J. pr. [2] 28, 435).
Si-chloro-quinone-di-chloriiuide
>N01
CeHjClj^[ [6:2:4:1]. [135°]. Formed by
treatment of a dilute HCl solution of di-chloro-
^-phenylene diamine [164°] with chloride of Ume
(Mdhlau, B. 19, 2011). Colourless prisms (from
ether). Sublimable.
CHLOSO-BESOKCIN C^HaC^OH),. [89°].
(256°).
Preparaiion — Sulphoyl chloride (li pts.) is
added gradually to a solution of resorom (1 pt.)
in dry ether (3 pts.). C;ai(OH)j + SOjCl,
= HCl + SOj + CeH3Cl(OH)2.
Properties. — Sol. water, alcohol, ether, benz-
ene, and OSa- Crystallises with difficulty. Its
aqueous solution is feebly acid to litmus. Am-
monia turns its aqueous solution first yellow,
then green; acids decolourise this liquid. JPe^Cl,
gives a bluish-violet colour. Ammoniacal silver
solution is reduced on boiling (G. Beinhard,
J.pr. 125, 322). Bronnne gives ohloro-di-bromo-
resorcin (q. v.).
Beneoyl derivative CsHjCHOBz),.
[98°]. Hexagonal crystals (from alcohol). In-
Bol wflitsr
'Di-m'ethyl ether C.H.Cl(OMe)p [118°],
From di-methyl resorcin in HOAc and CI
(Honig, B. 11, 1039). Long needles (from
alcohol). Insol. cold HOAo, v. sol. ether.
Di-ehloro-resoroin OjHjCL,(OH)j. [77°].
(249°). Formed by stirring, and finally melting,
a mixture of aulphuryl chloride (2^ pts.) with
13S
CHLOKO-RESORCIN.
resoroin (1 pt.). Fniified by snblimation. The
yield is 80 p.o. (O. Beinhard, 3.^. [2] 17, 328).
Praperima.—y . sol. water, alcohol, ether,
benzene, and OSj. Aqueous solutions are feebly
acid to litmus, reduce boiling ammoniaoal silver
nitrate, and give a bluish-red ooloui with Fe^Ol,.
Beactions. — 1. With bromme-water it gives
di-chloro-bromo-resorcin (g. v.). — 2. With CISO3H
it forms a crystalline insoluble powdei
CjjH^CltSgO,, probably the anhydride of di-chloro-
resoroin sulphonic acid (CsHCl2(B0,H)OH)2O.
Benzoyl derivativeCfiC^OBz)^ [127°].
Di-methyl ether OjBLjClj(OMe)j. Prom
di-inethyl-resoroin in HO Ac byCl(H5nig, B. 11,
1039). Oil ; decomposed at 140°. /
Sulphonic acid C^0U0B.)j30aK. A
white powder, sol. water and alcohol. Formed
by dissolving its anhydride (see above) in K^COj,
acidifying, evaporating, and extracting with
alcohol. Salt,— BaA'^.
Tri-chloTO-resorcia CsHCl,(OH)r [83°] and
[73?].
Preparations.-^!. By digesting resorcin with
Bulphuryl chloride (6 pts.) for 3 hours at 100°.
Crystallised from water. The yield is 30 p.c. —
2. Besorcin (20 g.) dissolved in water (80 g.) is
kept cool and treated with chlorine gas until the
red colour, which first appears, is nearly gone.
The Uquid is heated to 70°, filtered from resin
and allowed to deposit crystals. — 3. By chlori-
nating a solution of resorcin (100 g.) in HOAo
(250 g.) (Benedikt, M. i, 224).
Properties. — Silky needles, si. sol. cold water,
y. sol. hot water, alcohol, and ether. When
purified by sublimation it is yellow and melts at
[73°]. Its solutions resemble those of chloro-
resorcin in behaviour towards Utmus and AgNO,.
With Fe^Cl, it gives a wine-red colour on
warming (Beinhard, J.pr. [2] 17, 336). Oxidised
by KjFeCy, to CjHjOijO, [60°] (Stenhouse a.
Groves, B. 13, 1307).
Benzoyl derivative C,HClj(0Bz)2. [133°].
Glittering prisms (from alcohol).
Tri-chloro-resorcin CeHCl3(OH)2. [69°].
Formed by the action of KHSO3 on penta-chloro-
t resorcin (Claassen, B. 11, 1441). White needles.
V. sol. alcohol, ether, and hot water. May be
identical with the preceding.
Tetra-chloro-resorcin. Di-propyl ether
C,Cl4_(OC^H,)2. From di-propyl-resoroin and CI
(Eariof, B. 13, 1678). Liquid; decomposed at
100°. Sol. alcohol and EOAc ; si. sol. water.
Fenta-chloro-resorcin CeCl4(0H)(0Cl) or
C.C1,(C1,)0(0H). [92-6°]. Formed by adding
alternately m small portions KCIO, (5 pts.) and
a solution of resorcin (2 pts.) in HCl (8 pts.) to
cooled HCl (40 pts. of S.G. 1-17) (Stenhouse, Pr.
20, 78). Plates or flat prisms (from CS^). V.
sol. CSj, and benzene, v. e. sol. alcohol and ether.
Changes in the air into a modification melting
at 65° (Liebermann a. Dittler, A. 169, 265).
Hot water effects the same change.
Beactiona. — 1. Dissolves in a cold solution of
potassium bisulphite with evolution of heat and
formation of tri-chloro-resorcin [69°] (Claassen,
B. 11, 1441). EI appears also to form tri-chloro-
resorcin (Stenhouse, O. N. 23, 230).^2. Unlike
penta-bromo-resorcin, it is not affected by alde-
hyde and formic acid.
CHLO£0-B£I£N£ v. BuiEin.
CHLOBO-BOSANILIITE v. Di-ohik)bo-tiu-
AMICO-TBI-PHENTL-OABBmOL.
CHLOBO-SAIIGIN v. Samoin.
CHLOBO-SALIGTLIC ACID v. Chlobo-o-ozz-
BBNZOIO AOm. '
CHLOBO-SAIIOTIOL v. Cblobo-o-oxt-bex-
ZOIO AliDEHYDE.
CHLOBO-SAIICrEmiT v. Chlobo-oxt-benztIi
AIiCOHOIi.
PEB-CHIOSO-SEBACIC ACID C„Cl,„Hj0,.
Per-chloro-butyl ether C,„Clu{OfiQflt.
[172°]. (200°). From butyl sebacate and CI in
Bunshijie (Gehring, C.B. 104, 1624). Hexagonal
prisms.
Per-chloro-isoamyl ether ^
C,oCl,8(05Cl„)jO,- [179°]. From isoamyl seba.
oate and CI in sunshine (G.). Tough trimetric
prisms (by snblimation) ; volatile with steam.
Insol. water, si. sol. alcohol, v. sol. ether, benz-
ene, chloroform, and Ugroin.
CHLOEO-STEAEIO ACID
stearic acid and CI at 100° (Hardwick, C. J. 2,
232).
CHLOBO-SIILBEITB v. Chlobo-di-phentl-
ETHYLENE.
CHLOEO-STEYCHNraE v. Stbyohninb.
(u.).CHIOEO-STYEENE C,H5.CH:CH01,
(196°) at 716 mm.
Formation. — 1. By distilling styrene di-
chloride CjH5.CHCl.CH2Cl either alone or over
CaO (Byth a. Hofmann, A. 53, 310).— 2. By
heating CjHs.CHj.CHOlj with alcoholic KOH at
120° (Forrer, B. 17, 983).
Properties. — Liquid, with pungent odour.
Cone, alcoholic EOH followed by distillation
with water gives phenyl-acetio aldehyde. KCy
gives the nitrile of phenyl-succinic acid (Biig-
heimer, B. 14, 428).
(o)-Chloro-styrene C^H^-CChCH,. (199°).
S.G. 23 1-112.
Formation. — 1. By treating cinnamio acid
with EOCl or with HCl and potassium chlorate
(Stenhouse, A. 55, 1; 57, 79). — 2. By heating
C8H,.0HCl.CH(0H).C0jH with water at 210°
(Glaser, A. 154, 166).— 3. From C,H5.CClj.CH,
and alcoholic KOH (Friedel, O. B. 67, 1192;
Erlenmeyer, B. 12, 1609).- — 4. By neutralising a
solution of CsHj.CHCl.CHCl.COj^ (Erlenmeyer,
B. 14, 1867}.
Properties. — Liquid, with the odour of hya-
cinths. Does not so readily give up its CI as
the precediag. Bat by heating with water
acetophenone may be formed (Erlenmeyer, B.
14, 323).
Bo-Di-chloro-styrene C,H5.CC1:CH01. (221°).
From 0,H5.CO.OH2Cl and PCI. (Dyckerhoff, B.
10, 120, 533).
CHLOaO-SUBEEANE CABEOXTIIC ACID
CiHi^CLCO^H. From the corresponding oxy-
acid and HCl. Oil; sol. alcohol and ether.
KOH gives suberene carboxylic acid C,H,20,
(Dale a. Schorlemmer, O. J. 39, 539).
CHLOEO-SUBEEIC ACID CsHuClO^. From
suberic acid and CI (Bauer a. Qroger, M. 1,
610 ; 4, 341). Syrup, sol. water, v. e. sol. ether.
CHLOEO-STIBEBONIC ACID 0,H,sC10j.
From oxy-Buberio acid and cone. HCl at 180°
(Spiegel, A. 211, 119). Oil ; v. sol. alcohol and
ether. Converted by sodium amalgam into
Buberouio acid. Boiling NaOHAq forma C,H„0,.
CHLORO-THIENYL METHYL KETONE.
137
CHLOBO-SirCCIlflC ACID
COiiH.CHj.OHCa.COjH. [152°], Prepared by
heating f umaric acid with a solution of HCl in
glacial acetic acid (Ansohiitz a. Bennert, B. 16,
642). Crystalline solid. Sol. water and acetic
acid, si. sol. chloroform.
CHC1.C0
Anhydride I >0. [41°]. (130° at
CHj . CO
16 nun.). Prepared by heating the acid with
acetyl onloride. Formed as a by-product, when
malelo anhydride is produced by heating f umaric
acid with AoCl for 8 hrs. at 140° (Ferkin, 0. J.
41, 269). Crystalline ' solid. Sol. chloroform.
On heating it decomposes into maleic anhydride
and HCL
Di-chloro-snccinic acid CjHjC^COjH),. Two
acids of this constitution are formed by the
anion of CI with fumaric and maleic acids re-
spectively. They differ in melting-point and
solubility (Petrieff, Bl. [2] 41, 309).
letra-chloro-Buccinic acid. Per-chloro-
ethyl ether C,0l,(C0jCpCl5)j. [116°-120°].
From succinic ether and CI in sunshine (Cahours,
A. 47, 294). Small needles. Decomposed by
solution in alcohol, and by alcoholic KOH, tri-
chloro-acetic acid being among the products.
Ammonia forms tri-ohloro-acetamide and other
products (cf. Malaguti, A. Ch. [3] 16, 72).
CHLOBO-SirLFHO-ACEIIC ACID
CHCl{S05H).C0jH. From chloro-acetio acid and
CISO^. Formed' also by oxidation of thio-
hydantoin by KCIO3 and HCl (Andreasch, M. 7,
159).— BaA"aq: S. 2-5 at 17°.— KjA"4aq.—
(NHJjA": needles, v. sol. water.— Ag^A" |a,q :
prisms.
CHL0B0-S1TLFH0-SEKZ0IC ACID
O^sClSO. U. O.H,Cl(SO,H)(COjH) [l:3or5:2].
From o-chlpro-toluene sulphonic acid by oxida-
tion with chromic mixture (Hiibner a. Majert,
B. 6, 792),-KHA"aq.— BaA"2aq.— PbA"2aq.
Chloro-sulpho-benzoic acid
CsH5Cl(S0,H)(C0jH) [1:3?:5]. Jrom j»-chloro-
bonzoic acid and SO3. (Otto, A. 123, 216).
Needles (containing a;aq); v. sol. water, alcohol,
and ether. With PCI5 it gives di-chloro-benzoie
chloride.— KHA"liaq.—KjA"3aq.—BaA"2aq.—
BaH,A"j 4aq,— CaHjA", 3aq.— PbA" 3aq.
Amide C^U,Cl{S0^1SllEQ{C0nB^ : crystals.
Chloro-snlpho-benzoic acid
CaH„Cl(S03H)(C0,^) [1:2:4]. From jj-chloro-
benzoio acid and fuming H2SO4 at 130° (OoUen,
A. 191, 29; B. 9, 758, 1248). Long needles
(from water). ^1. sol. alcohol and ether.
Salts.— NaHA"2aq.—AgjA"aq.—BaA"3aq.
MgA" 6aq.— ZnA" 4aq.— CuA" 6aq.— PbA" 4aq.
Chloride C.H,Cl(S0,Cl)C0jH. [140°-
150°]. Needles (from ether).
(a)-CHLOBO-IEE£BlC ACID C,H,C104 i.e.
(CB^),C.CH(00jH).CH,.C0.0? (Frost, A. 226,
3G3), [191°]. From terebic acid (1 mol.) and
PCI5 (8 mols.) (WiUiams, B. 6, 1097 ; Eoser, A.
220, 265). The (;8)-isomeride is formed at the
same time. V. sol. hot water, alcohol, or ether.
At 150° it begins to sublime.
BeacUon.—!. Splits off HCl, forming terebi-
lenio acid C^HgO, [q.v.), when heated to 200°, or
with water at 140°, or by boiling with NaOEt
fW, Boser, A. 220, 261).— 2. Boiled with water
md CaCO, it forms oxy-terebic acid.— 3. With
POj at ia0°-140° forms ehloro-terebilenic
acid.
S alt s.— CaA" 2aq.— AgHA".— PbA" 3aq.
Ji3)-Chloro-tereMc acid OjHjClO^ i.e.
(CH3)j.C.CBr(COjH).CH2.CO.O(?) [168°]. Formed
by the action of CI on teracohic acid in presence
of water in the cold. Colourless, transparent, tri-
metrio crystals ; a:6:c = 0-9827:l:0-7137. Easily
decomposed by boiling water into HCl and tere-
biUc acid : C^HgOj (Frost, A. 226, 363).
CHLOHO-TEREBILEHIC ACID G,n,C10,i.e.
MejO.C(CO,H):CCl.CO.O (?) [200°-203°]. Prom
chloro-terebic acid [191°] and PCI5 at 140° (W.
Boser, A. 220, 265). Small prisms. Y. sol.
water. Not affected by boiling water, hardly
even by boiling with moist Ag^O.
Salts.— CaA'j2aq.—AgA'.
CHLOBO-TEREFHTHAI.IC ACID
CjHs.Cl(COjH)j' [1:2:5], [123"]. Formed by
oxidising CjHjCliC^Hjj with bichromate mix-
ture and separating the two isomeric acids
formed by boiling water. White crystals ; insol.
boUing aq ; sol. ammonia, reppd. by HCl as a
curdy pp. resembling AgCl ; si. sol. warm alco-
hol ; sol. benzene, CHCl,, CS, and ether ; sol. hot
ligroin. Sublimes at 100°. It distils without
forming any anhydride (Istrati, A. Ch, [6] 6,
418).
Chloro-terephthalic acid CgHaC^CO^H),
[2:1:4]. [above 300°]. Obtained by the action of
cuprous chloride upon the diazo- compound from
amido-terephthalio acid. Colourless crystals.
Y. sol. alcohol and ether, si. sol. hot water.^
AgjA" : white pp.
Di-methyl ether A"Mej: [60°]; silky
plates ; v. sol. alcohol and ether, si. sol. water.
Chloride C^fi\{COG\)t: (Ci300°); orys.
talline.
4»»ideCBHsCl(C0NHj)j: [above 300°]; white
crystalline crusts ; si. sol. water (Ahrens, B. 19,
1638).
Di-chloTo-terephthalic acid C,H2Cl2(C02H)2
[5:2:4:1]. From the dihydride and dilute HNO,.
Hair-like needles ; does not melt at 300°.
Methyl ether Me^X". [132°J.
Dihydride 0,B.fiUCOja.),. [c.274°]. From
succinyl-succinic ether (1 molt) and PClj (4 mols.)
(Levy a. Andreocci, B. 21, 1463). Scales (from
water), Y. sol. alcohol and ether, si. sol. benz-
ene, CHGl,, and CS,.— BaA"3aq.— OaA"4aq.—
NaHA" 3aq.— AgjA".- McjA". [110°].— Bt^A",
[71°].
TBI-CHI0R0-DI-THIE1IYI.-EXHANE
CCl3.CH(C<HaS)s. [76°]. Obtained by adding
HjSO, to a mixture of thiophene and chloral
dissolved in acetic acid (Peter, B. 17, 1341).
Colourless tables. Y. sol. ether, petroleum-
ether, CSj, and hot alcohol, si. sol. cold Alcohol.
Heated with isatin and H2SO4 it gives a violet-
red colour.
DI-CHLOBO-DI-THIEIIYL-ETHYLENE
CClj:C(C,H,S)j. Formed by boiling tri-chloro-
di-thi8nyl-ethane with alcoholic EOH, or, better,
KCN (Peter, B. 17, 1343). Colourless oil. Yola-
tile with steam. With isatin and H^SO^ it gives
a violet-blue colour.
CHLOBO-THIENYL UETETL KETONE
C,SH,C1.C0,CH,. Chloro-acetothlencme. [52°],
138
cjhloro-thiEnyl methyl ketone.
Formed by the action of acetyl ohioiide upon
ohloro-thiophene in presence of AJ^Olj. Large
oolouiless tables (from alcohol or ether). ^ Very
'Tolatile with steam. By alkaline EMnO^ it is
oxidised to chloro-thiophene-oarbozylia acid
[140°].
Phenyl-hydragide
C,SHjCl,C(NjHPh).CH,: [108°]; yellow tables ;
sol. hot alcohol (Oattermann a. Bomer, B. 19,
693).
Isomeride ; THiENXti ohlobo-mbthyl ketone.
CHLOBO-THIO-ACETIC ACID CHjOl.OS.OH.
Ethyl ether A'Bt. (167°). Prepared by
heating chloro-acetio ether with P^Sj at 140°
(Meyer, B. 14, 1508). Liquid.
Si-chloro-thio-acetic acid CHCI2.CS.OH.
Ethyl ether A'Et. (178°). Prepared by
heating di-ohloro-acetic ether with P^Sj at 180°
(Meyer, B. l4, 1507). Oil.
p-CHIOEO-DX-THIO-BENZOIC ACID
C5H4C1.CS2H. Prom Cb1£,C1.CC1, and alcoholic
potassium sulphide (Engelhardt a. Latschinoti,
Z. 1868, 459). — HgA'2 : greenish-golden laminas
(from alcohol). — PbA'j : brick-red pp.
CHLOEO-THIO-CABBONYL CHLOBIDE v.
THio-OABBONYL cHiiOiiiDE, Tol. i. p. 695. See also
Peb-ohlobo-metbti. mebcaptan,
CHLOBO - THIO - CABBONTL SULFHUB-
CHLOBIDE CSC1.SC1. (140= in vacuo). Oil.
Formed by heating CSClj with sulphur at 130°-
150°. By chlorine it is converted into per-
chloro-methyl-mercaptan and sulphur chloride,
as foUows : 2CSC1.B01 + 3Clj = 2CC1,.SC1 + SjCl^.
Heated with sulphur at about 160° it yields GSj
and SjCl, (Klason, B. 20, 2381).
CHL0B0-XHI0-70B1IIC ACID C1.C0.S.H.
Amyl ether CI.CO.S.C4H,,. (193°). S.G.
»1» 1-078. /tn 1-4766.
Preparatim. — ^By saturating amyl meroaptan
with COCl,, and, after a few days, fractionally
distilling the product (H. Schone, J. pr. [2] 32,
243).
Properties. — h. liquid of unpleasant odour,
between that of amyl alcohol and that of mer-
captan. It does not fume in the air.
Reactions. — 1. Converted by NaSMe into
C0(SC5H„)(SMe).— 2. Converted by NaOEt
into C0(SC5H„)(0Et).— 3. Dry NH, forms
C0(SCjH„)(NH2).— 4. With aniUne it forms
CO(S.CsH„)NPhH (v. Phenyl thio-oabbamic
acid). — 5. It reacts with urea forming
NH2.CO.NH.CO.SC5Hi, («. Thio-auiOphanic Acm).
6. With phenyl - thib - urea it gives rise to
NPhH.CS.NH.C0.S.05Hj, {v. Pheotl-di-ihio-
AUiOPHANio acid). — 7. With diphenyl-thio-urea it
forms KPhH.CS.NPh.CO.S.CsH„ {v. Di-phektl-
DI-IHIO-AU^OFHADIO AOId).
Ethyl ether Cl.CO.SEt. (136°). S.G. is
1-84. From COClj and mercaptan (Salomon,
J. pr. [2] 7, 262). Oil. Converted by NH, into
NH,.CO.SEt.
Chloro-thio-foimic acid Cl.CS.OH.
Ethyl ether CLCS.OEt. (136°). Formed
in small quantity by the action of alcohol on
CSClj (Klason, B. 20, 2384). Converted by NH,
into xanthogenamide NHj.OS.OBt.
Chloro-di-thio-formic ether Cl.CS.SEt. (100°)
in vacuo. S.G. IS 1-141. From OSClj and EtSH.
I'dlow oil, smelling like garlic (K.).
CHIOEO-THIOPHEITE C^HjClS. (130°).
Obtained, together with di-chloro-thiophene, by
passing chlorine into crude thiophene (Weitz, S.
17i 794). Strongly refractive colourless oil.
Gives the indophenine reaction.
Di-ohloro-thiophene pjHjCljS. (170°). Ob-
tained, together with themono-chloro-thiophene,
by passing chlorine into crude thiophene (Weitz,
B. 17, 794). Heavy oil. Gives the indophenine
reaction.
Tri-cMoro-thiophone C4SHCI,. (206° uncor.).
A by-product in the preparation of tetra-chloro-
thiophene (Eosenberg, B. 19, 6S0). Heavy oil. ,
Gives the indophenine reaction.
Tetra-chloro-thiophene OjCl^S. [36°]. (245°).
Obtained by passing chlorine into di-bromo-
thiophene (Weitz, B. 17, 792). Long white
needles.
CHLOBO-THIOPHEWE-CABBOXYLIC ACID
CiSHjC^COjH). Ghloro-thAophemo add. [140°J.
Formed by oxidation of chloro-thienyl methyl
ketone with alkaline KMnO^. Colourless needles
(from hot water). Sublimes in spikes. SI. sol.
water (Gattermann a. Eomer, B. 19, 694).
TETBA - CHLOBO - THIOPHENE TETBA -
CHLOBIDE C.ClsS. [215°].
Preparation. — Chlorine is passed into a solu-
tion of iodo-thiophene in CHOI,. The liquid is
shaken with aqueous NaOH, the chloroform
evaporated, the residue extracted with alcohol
and crystallised from chloroform.
Properties. — Thick prisms, resembling urea.
A pungent, bat not unpleasant odour. V. sol.
chlorpform, ether, benzene, CS:, glacial acetic
acid, and alcohol (0. WiUgerodt, J.pr. [2] 33,
160).
TBI - CHLOBO - THIOPHENE - STJLPHONIC
ACID C<SCl3.S03H. Formed by boiling the an-
hydride with water or alkalis.
Anhydride (OiSClj.SOj)^ Formed bytha
action of pyrosulphuric acid upon tri-oUoro-
thiophene. White glistening crystals. Sol.
benzene, nearly insol. water, alcohol, and ether
(Rosenberg, B. 19, 651).
CHLOBO -THYMOHYDBOftTIINOllE «.
ChIiOEO-HYDEO-THYMOQDINONE.
TBI . CHLOBO - THYMOL C,„H„01sO i.e.
C„Ol3(C3H,)(GHs)(OH). [61°]. From thymol and
CI in daylight (Lallemand, A. Ch. [3] 49, 148).
Lemon-yeUow mouoolinic prisms. Decomposes
at about 180°. Gone. H^SO, at 100° converts it
into a crystalline body [45°] (250°).
Penta-cMoro-thymol Ci^aCljO. [98°]. From
thymol and CI in bright daylight (L.). Hard
crystals. At 200° it splits up into propylene,
HCl, and tri-chloro-cresol.
o-CHLOEO-THYMOQTJINONE CaHMePrClOj
[1:4:2:3:6]. Formed by oxidation of the corre-
sponding hydroquiuone with FejCl„. Yellowish
mobUe oil. BasUy volatile with steam. " V. sol.
alcohol and ether (Schniter, B. 20, 1317).
m - Chloro - thymoquinone CjHMePrClOj
[1:4:6:3:6]. Formed from m-bromo-thymoquinone
by treatment with chlorine, the Br being re-
placed by 01. Oil (Schniter, J3. 20, 1319).
Di - chloro - thymoquinone CaCl2MePr<^
[99°]. The ethereal extract from the product of
the action of HCl on thymo-quinone-chlor-
imide (q. v.) is evaporated and distilled with
steam. It crystallises in the receiver.
Properties. — Trimetric tablets (from alcohol).
CHLORO-TOLIIENJE,
Turned brown by light. Not reduced by SO,
(Andresen, J.pr. [2] 23, 176).
CHIOBO - THYMO - aTTIKOmE! CHLOB -
IMIDE C.H01MePr<^Qj. An oU prepared by
adding a solntion of bleaohing powder, to the
hydrochloride of ohloro-amido-thymol, exactly
as described under thymo-quinone-chlorimide.
Reactions. — Cone. HCl acts upon it exactly
as it does upon thymo-qninone-chlor-imide,
fonuing ohloro-amido-thymol, ohloro-thymo-
quinone, and di-ohlorothymoquinone (a. v.) (An--
dresen, J.^ir. 131, 187).
CHLOEO-TIGIIC ACID CiHsOLCO^H. [69°].
(210°). Formed by the action of alcoholic
EOH upon (o)-di-ohloro-di-methyl-succinic acid
CO,H.CClMe.CClMe.COjH, or by heati^ig tte
silver-salt with water (Otto a. Becknrts, B. 18,
853). Formed also by treating methyl-aceto-
acetic ether with PCI5 followed by water (Biicker,
4.201, 64; Demar(fay, B. 10, 1177). Glistening
plates, or small needles. Sublimable and easily
volatile with steam. V. sol. alcohol and ether,
si. sol. oold water. Decomposed by aqueous
EOH at 160° into 00, and methyl ethyl ketone
(Priedrioh, A. 219, 359).— BaA',.— ZnA'j IJaq.—
AgA'.
Ethyl ether-&tM. (174°) (B.); (179°) p.).
Oil.
SI-CHXOBO-IOITrCAItBGSITBIL v. Dl-
OHLOEO-OXI-METHYIi-QtllNOIiDIE.
o-CHLOEO-TOIUENE 0,H,C1 is.
0^,(CH,)a [1:2]. M0I.W. 126i. (164° unoor.).
FormaU(m.—X. In small quantity, together
with the j;-modification, by chlorinating toluene
in presence of iodine (Hubner a. Majert, B. 6,
790). — 2. By running a solution of NaNO, into a
hot solntion of o-toluidine, and Cu^Cl, in dilute
HCl (Sandmeyer, B. 17, 2651 ; of. Beilsteiu a.
Kuhlberg, A. 156,. 79). — ^3. By heating o-diazo-
toluene with a large excess of strong HCl ; the
yield is 40 p.c. of the theoretical (Gasiorowski a.
Wayss, B. 18, 1939).— 4. By decomposing with
superheated steam the sulphonic acid obtained
by acting on commercial mono-chloro-toluene
with' sulphuric acid. The o- compound is much
more easily snlphonated than the p- compound,
and the Ca and Na salts of the resulting acid are
much less soluble. The separation is, however,
not a perfect one (Seelig, A. 237, 151, 165).
Propertiea. — Idquid. Converted by oxidation
into o-chloro-benzoic acid (Wroblewsky, Z. [2]
6, 460). On nitration it gives a mixture of
C,H,(CH,)Cl(NOj) [1:2:6] and [1:2:6] (Honig, B.
20, 2417).
OT-Chloro-toluene C.H<(CH3)C1 [1:3]. (166°).
From m-toluidine by displacement of NHz by CI
through the diazo- reaction. Formed also by
eliminating NHj from ohloro-^-toluidine. (Wro-
blewsky, A. 168, 199). Oxidised by CrOj to m-
chloro-benzoio acid.
l).Chloro-tolueno C^4(CH,)C1 [1:4]. [6-5°].
(160°). S.V. 134-91 (B. Sohiff, A. 220, 99).
S.G. " 1-080.
Formation. — l.'By chlorinating toluene in
presence of iodine, M0CI5, or other carriers
(Deville, A. Ch. [3] 3, 178 ; Beilstein a. Geitner,
A. 139, 331 ; Bl. [2] 1, 251; Aronheim a. Dietrich,
B. 8, 1402).— 2. By running a solution of NaNOj
into a hot solution of ^-toluidine and CujCl, in
dUute HCl (Sandmeyer, B. 17, 2651; c/. Hubner
139
a. Majert, B. 6, 794).— 3. By healing p-diazo-
toluene with a large excess of HCl ; the yield is
40 p.c. of the theoretical (Gasiorowski a. Wayss,
B. 18, 1939).
PrqperWes.— Liquid. Not attacked by water
at 200°, nor by alcoholic NHj at 100° or alcoholic
NajS, NaHS, or NaOBt at 150°. Chromic mixture
gives o-chloro-benzoio acid. On nitration it gives
(4:2;1) ohloro-nitro-toluene [38°], and (4:3:1)
chloro-nitro-toluene [9°] (Goldschmidt a. Honie.
£.19,2438).
w-chloro -toluene v. Benztl chloride.
(fl)-Di-oliloro.toluene C.H,(CH,)cL[l:2:4].
(197°) (S.). S.G. §2 1-2460 (L. a. K.). Frim
C,H3MeCl(NOJ[l:2:4] vid C„H,MeCl(NH2) (Lell-
mann a. Klotz, A. 231, 314). 'Formed also by
chlorinating p-ohloro-toluene (Seelig, A. 237,
167). ' Oil. Gives di-chloro-benzoic acid [158°].
Di-chloro-tolueue C,H8{CHJCl2[l:2:5]. [5°]
(194° uncor.) at 745 mm. S.G. |a 1-2535. From
C5HsMe(NH2)Cl[l:2:5] by diazo- reaction (LeU-
mann a. Klotz, A. 231, 318). Gives di-chloro-
benzoio acid [156°].
Dl-chloro-toluene C5Hj(CH3)Clj[l:3:5]. [26°].
(195° uncor.) at 729 mm. Prepared from
C^jMe(NH2)CL,[l:4:3:5] by diazo- reaction (Lell-
mann a. Elotz, A. 231, 323). Gives di-chloro-
benzoio acid [182°].
(a^Di-chloro-tolnene 05Hs(CH3)Clj[l:2:3].
(197°). Formed by the action of chlorine on
toluene in presence of ferric chloride or other
carriers (Seelig, A. 237, 167). Yields a nitro-
derivative [51°] or a dinitro- derivative [122°].
On oxidation with alkaline permanganate it gives
di-chloro-benzoio acid [166°].
Di-cMoro-toluene 08Hs(CH5)Cl2 [1:3:4]. (200"
unoor.) at 740 mm. S.G. |g 1-2612.
Formation.—!. From C(,H3MeCl(NHj) [1:3:4]
by diazo- reaction (Lellmann a. Elotz, 4. 231, 311).
2. A product of the chlorination of toluene in
presence of carriers (Beilstein a. Geitner, A. 189,
341 ; Beilstein a. Euhlberg, A. 150, 313 ; Aron-
heim a. Dietrich, B. 8, 1401 ; Nenhof, Z. [2] 2,
653 ; Schultz, A. 187, 263).— 3. From chloro-p-
cresol and POI5 (SchaU a. Dralle, B. 17, 2535).
Properties. — Oil. Gives on oxidation di-
ohloro-benzoic acid [201°].
wp-Di-ehloro-toluene [4:1] GgHfilOSJCjl. p-
Chloro-benzyl chloride. [29°]. (213°).
Formation. — 1. By chlorinating jj-chloro-
toluene at 160° (Neuhof, A. 146, 320; Jackson a.
Field, Am. 2, 85 ; P. Am. A. 14, 54 ; B. 11, 904).
2. By chlorinating cold benzyl chloride in pre-
sence of iodine (N.).
Properties. — Needles or prisms ; insol. water,
sol. alcohol and ether. Powerfully attacks the
mucous membrane. Very volatile. Oxidation
gives ^-ohloro-benzoic acid. Boiling water forms
jp-chloro-benzyl alcohol. Boiling aqueous Pb (NOJj
gives ^-chloro-benzoic aldehyde. Alcoholic KOy
forms phenyl-acetonitrile.
uo) . Si - chloro • toluene v. Benzxlidene
CBLOBIDE.
(o)-Tri-ehloro-toluene C„H2(CH3)Cl3 [1:2:4:5].
[82°]. (230°). Is foi-med, together with the {$)-
derivative, by passing chlorine into toluene in
presence of FejOlj or other carriers (Liinpricht,
A. 139, 303 ; Aronheim a. Dietrich, B. 8, 1401 ;
Schultz, A. 187, 274 ; Seelig, A. 237, 133). Long,
needles, sol. alcohol. Forms a sulphonic acid,
which is decomposed by superheated steam at
140
CHLORO-TOLUENE.
160°. Chromic miztnie oxidises it to tri-chloro-
benzoio acid [163°] (Janasoh, A. 142, 301).
(;a).Tri.oliloro-toluene OePj,(CH3)0^ [1:2:3:4].
[41°]. (232°). Is formed together with the (a)
isomeride by passing chlorine into toluene in
presence of Fe^Cl, (Seelig, A. 237, 133). Forms
a sulphonate, which is decomposed by super-
heated steam at about 210°. Gi-roB tri-chloro-
, benzoic acid [129°].
v-exo-Tri-chloro-tolnene O^OLfCBjCiL
(240°). S.a.1-44. A product of the chlorination
of toluene and of benzyl chloride (Naquet, A.
Sui^l. 2, 248 ; EekulS, K. 2, 661). Formed also
by chlorinating boiling di-ohloro-toluene (Beil-
stein a. Euhlberg, A. 146, 317). Liquid. Alco-
holic EOAo gives 0,H;,Cl2.CH20Ao.
aiuo-Iri-chloro-toluene [2:1] CgB.jCl.CH.CLp
o-Chloro-bemyKdene chloride, (c. 230°). From
salicylic aldehyde and FCl, (Henry, B. 2, 135 ;
Z. [2] 5, 371). Formed also, together with the
following, by chlorinating benzyUdene chloride
,in presence of iodine (B. a. K.). Water at 170°
converts it into chloro-benzoic aldehyde. Chromic
mixture forms o-chloro-benzoic acid. Distillation
with dry oxalic acid forms o-chloro-benzoic alde-
hyde (Anschutz, A. 226, 19).
««p-Tri-chloro-tolnen,e [4:1] C^iCl.CHClj.
p-ChCoro-bemylidene chloride. (234°). Formed
as above (B. a. E.). Besembles the preceding in
its reactions.
cc»a)-Tri-chlora-toluene v. Benzotbichlobidi!.
Tetra-chloro-tolnene CjHCl^.CHj. [96°] (L.) ;
[91°] (B. a. E.). (276° cor.). Among the pro-
ducts of chlorinating toluene in presence of SbClg
(Limpricht, A. 139, 327). Slender needles (from
alcohol).
Tetra-chloro-tolnene Cfifil,, (280°-290°).
' From di-ohloro-toluene tetrachloride and alco-
holic EOH (Fieper, ^.142, 305).
Tetra-chloro-tolnene CeHjCl,.CHjCl. 2W-
ehloro-bemyl chloride. (273°). S.G. 2S 1-547.
From C^Cl3.CH, and Gl at high temperatures
(Beilstein a. Euhlberg, A. 160, 286).
Tetra-chloro-toluene 0,HjClj.CHCL, [4:3:1].
{a)-I>i-chloro-benzyUdene chloride. (257°). S.G.
22 1-518. From CI and boiling (4,3,l)-di-chbro.
toluene (B. a. E.). Water at 220° gives di-chloro-
benzoic aldehyde.
Tetra-chloro-tolnene CHjGlj.CHOlj [1:3:6].
{$)-Di-cKloro-bensyUdene chlorMi. (c. 260°)
Formed by passing chlorine into (j3)-di-chloro-to-
luene heated at 230° (Seelig, A. 237, 167). Is
converted into dichlorobenzoic aldehyde on
treating with cone. H2SO4.
Tetra-chlord^toluene [2:1] CsH,Gl.CCl,. a-
ChJoro-benzolriehloride. [30°]. (260°). From
o-oxy-benzoic acid by distilling with FClg (Eolbe
a. Lautemann, ii. 116, 196) . Water at 160° gives
o-chloro-benzoic acid.
Tetra-chloro-toluene [8:1] C,H4Cl.CCl3. m-
Chloro-benzotriehloride. , (235°). From m-sul-
pho-benzoic acid and FGlj (Canus a. Eammerer,
A. 131, 158).
Tetra-chloro-toluene [4:1] C,H,C1.CC1,. -p-
Chloro-beneoirichloride. (246°).
Formation. — 1. From benzotrichloride and
CI in presence of carriers (Beilstein a. Euhlberg,
A. 146, 317).— 2. From benzoyl chloride and FClj
(Limprioht, A. 134, 67). — 3. From j>-oxy-benzide
C,HZ I and PCI,, The product is freed from
'•Q
FOCI, by distillation, and the residue shaken
with dUute NaOH (KlepI, /.jw. [2] 28, 204).
Properties. — Oil. Converted by warm cono.
HjSO, or by water at 200° into jp-ohloro-benzoio
acid.
Fenta-chloro-toluene 0,CI,.CH,. [218°].
(301°). Formed by chlorinating toluene in pre-
sence of iodine (B. a. E.). Needles (from benzene).
Penta-chloro-toluene CsHCl,.CHjCI. Tetra-
ohloro-benzyl chloride (296°). S.G. ^ 1-634.
From boiling tetra-chloro-toluene and CI (B, a.
E.). Further chlorination gives CgCl, and CCI4
(Beilstein a. Euhlberg, Z. [2] 5, 527).
Penta-chloro-toluene CaHjClp.CHClj [2:4:5:1].
{a)-Tri-chloro-ben3ylidene chloride. (281°). S.G.
22 1-607. From CI and boiling tri-ohloro-toluene
(B. a. K.). Needles (below 0°). Water at 250°
or cold fuming H2SO4 gives tri-chloro-benzoio
aldehyde.
Penta-chloro-toluene CjHjClj.CHCl^ [4:3:2:1].
(ffj-Tri-chloro-bemylidene chloride. [84°]. (0.
280°). Formed by passing chlorine, through
boiling (j3}-tri-chloro-t61uene (Seelig, j1. 237, 146).
OU solidifying to a crystalline mass. Sol. petro-
leum ether. Treated with fuming sulphuric acid
it forms (/3).tri-chloro-benzoic aldehyde.
Penta-chloro-toluene CbHjC12.CC13. Di-
chloro-benzofrichloride. (273°). S.G. 21 1-587.
From crude di-chloro-toluene and CI (B. a. E.).
Water at 200° gives a mixture of di-chloro-ben-
zoic acids.
Hexa-chloro-toltiene CjHjOl, i.e. C,CI,.CHjCl.
Penta-chloro-benzyl chloride. [103^. (326°).
From benzyl chloride and CI in presence ol
SbClj. Formed also by chlorinating boiling
penta-chloro-toluene (B. a. E. ; cf. Deyille, A.
44, 304). Slender needles; si. sol. alcohol; v.
sol. benzene. Alcoholic EOAc at 200° gives
OSCI5.CH2OH.
Hexa-chloro-toluene CsHCIj.CHClg. Tetra-
chloro-benzyUdene chloride. (306°). S.G. 2«
1-704. From CI and boiling tetra-chloro-toluene
CjHCl^.CHs (B. a.E.). Water at 280° gives tetra-
ohloro-benzoic aldehyde.
Hexa-chloro-toluene CaHClj.CClai Tri-chloro-
benzotrichloride. [82°]. (308°). From CI and
boiling CsHClj.CHs (Beilstein a. Euhlberg,^. 150,
305). Slender needles (from alcohol). Water at
260° gives tri-chloro-benzoic acid.
Hepta-chloro-toluene CaCIj.CHClj. Fenta-
chloro-benzyUdene chloride. [110°]. (334°).
Formed by chlorinating benzylidene chloride
with the aid of carriers (B. a. E.). Flat lamime
(from alcohol). SI. sol. cold aJcohol, v. sol. boil-
ing alcohol. Water at 300° does not act upon it.
Hepta-chloro-toluene OjHClj.CClj. [104°].
(316°). From CI and boiling C.HG14.CH, (B. a.
E.). Short needles (from alcohol) ; m. sol. hot
alcohol. Water at 270° gives tetra-chloro-benzoic
acid.
CHLOSO - TGinEITE - AZOXY • CHLOBO •
TOLUENE V. AzoxY- coMPonin>s.
DI-CHIOEO-TOLITENE TETBACHIORIDE
C,HsCl. i.e. OeH,Cle.CH3. [150°]. From toluene
and CI (Pieper,. 4. 142, 304). Prisms (from CSj).
Alcoholic NaOH at 110° gives di-chloro-benzoic
acid [203°] and tetra-chloro-toluene (c. 285°).
j7-CHLOKO-TOLUENE-(0).STJLPHONICACII>
CbHsMbC^SOjH) [1:4:2]. From 2)-ohloro-toluene
and HjSOj (Vogt a. Henninger, A. 165, 362).
Also from the corresponding ^ -toluidine o-Bol-
OHLORO-TOLUIDINE.
141
phonio acid by displacement of NH, hj CI
(JenBaen, A. 17*2, 239).
Salts.— BaA'^l^aq: S.1-9 at 16°.— BaA'^aq
(Hiibnei a. Majeit, B. 6, 790). — EA' aq. —
CaA'j 6aq.— PbA'j 8aq.— CuA', 7aq.
Amide O^aOl.Me.SOjNHj [138°]. From
0,H,(NH2)Me.SOjNHj by HCl and nitrons acid
gas (Heffter, A. 281, 209).
j)-Chloro-tolnene (a)-8nIpbonic acid
C ,]CMe01(SO,H) [1:4:3]. Formed, together with
the preceding, by sulphonating 2>'-chloro-tolaene
(Vogta.Henninger,il.C;i. [4] 27, 129). Converted
by potash-fusion into orcin.
Salts. — KA'^aq: lamina. — NaA'5aq. —
BaA', 2aq : S. 6-71 at 16-5° (V.a. H.).— BaA'^ iaq :
S. 14 at 14-5° (Hiibner a. Majert, B. 6, 790).—
BaA'j aq (V. a. H.).— BaA'j 7aq (Bngelbrecht, B.
7, 796).— OdA',2aq.— PbA', 6aq.— CuA'^ lOaq.
o-Chloro-tolnene sulphonic acid
C,H,MeCl(SO,H) [l:2:3or5]. From o-ohloro-
tolnene and HjSO, (Hubner a. Maiert,B.6, 790).
Sodinm amalgam gives toluene nt-sulphonio acid.
Oxidation forms ohloro-sulpho-benzoio acid. —
NH,A' aq. — KA' |aq.— NaA'teq.— BaA'j 2aq.—
CaA'j2aq.— PbA'j 2aq.— OuA'^ ^aq.
Chloro-toluene sulphonic acid
C|5B^MeCl(S05H) [1:2:4]. From the amide and
HCl at 150°. Salts.— BaA'j.—KA'.
Chloride CHjClMe.SOjCl. Oil.
Amide' CsHjMeOl.SOjNH,. [135°]. From
C,H,Me(S6jNBy.Nj.NH.CjH,Me.S0sNHs and
HCl (Paysan, 4.221,212). ^
j)-Chloro-tolaene a-snlphonic acid
[4:l]CgH4Cl.CH2.SOsH. Chlorobmzyl sulphomo
acid. [108°] (?). From C^^CLCHjOl and
aqueous KjSO, (B6hler, A. 154, 56 ; Vogt a.
Henninger, A. Ch. [4] 27, 129 ; Jackson a. White,
Am. 2, 159 ; P. Am. A. 14, 312 ; B. 13, 1217).
Potash-fusion gives p-oxy-benzoic acid.
Salts.— KA'(B.-, J.a.W.)-KA'aq(V.a.H.) :
sol. boiling alcohoL— NaA' : flat crystals (from
water) orpearly scalesHrom alcohol).— BaA'jaq.—
BaA'j2aq (J. a. W.): Needles.— CaA'j 2aq.—
CaA'j7aq (J. a. W.); trimetrio crystals.—
CuA'j2aq: pale green needles.— PbA'j aq (J. a.
W.) : long needles. — ATbOHaq. — A'jPb,OjS
TJAflnlflH
Chloride 0,Ufil.CBt.SOfiL [85-6°] : flat
crystals, v. sol. ether.
CHIOBO-0-TOI.TJIC ACID CA(0H,)01.COjH
r3:4:l]. [130°]. Formed, together with the [6:3:1]
isomeride [166°], by oxidation of ohloro-o-xylene
CA(CH,)2C1 [1:2:4] with HNO3 (Kriiger, B. 18,
1757). Fine needles or thick prisms. By further
oxidation by means of KMnO^ both acids yield
ohloro-phthaUo acid [130°-134°]. By KOH
fusion it is converted into oxy-o-toluip acid
C^(CH,)<OH)GOjH [2:4:1].— CftA'jSaq.
Chloro-p-tolnio acid C,H,(CH,)Cl(COjH)
[4:2:1]. [150°]. Formed by the action of boiling
dilute HNO, on ohloro-cymene (derived from
thymol and PCIJ . Slightly volatile with steam.
(Fileti a. Crosa, G. 16, 290).
* Ohloro.o-tol^c8cidC.H3(CH,)aCO^[2:3:l].
ri54°l Formed by oxidation of chloro-o-xylene
OA(CH.),0l [1:2:3] by HNO, (piiger, B. 18.
1758) Needles. V. sol. alcohoL By further
oxidation by means of KMnO^it yields cWoro-
phthalic acid [181°].— A',0»2aq: sparmgly
soluble long prisms.
Chloro-o-tolaicacidO,H,(CH,)C1.002H[6:3:l].
[166°], Formed, together with the isomefide
(2:4:1), by oxidation of ohloro • o - xylene
0„H,(CH,)j01 [l:2:4],with HNO, (Kruger, B. 18.
1757). Needles. Sol. alcohol, v. si. sol. water.
By further oxidation by means of EMnOj both
acids yield chloro-phthalic acid [130°-134°].
By KOH fusion it yields oxy-o-toluic acid [173°].
— A'jCa 2aq : sparingly soluble short prisms.
CWoro-p-toluio acid CjH,(CH,)Cl(CO,H)
[4:3:1]. [196°]. Formed by the action of boiling
dilute HNO, on the chlbro-cymene that is ob-
tained from carvacrol and FCl, (Fleischer a.
Eekul£, B. 6, 1090 ; v. Oerichten, B. 10, 1249 ;
11, 366). Laminee. — CaA', 3aq. — ^BaA', 4aq.
Chloro-m-toluic acid C,H,(CH,)C1C0^
[3:4:1]. [203°] (V.); [210° cor.] (J.); [204°
cor.] (B. a. K.).
Formation. — 1. By oxidation of chloro-m-
xylene CjH,(CH3)2Gl [1:3:4] with K,0rj0, and
HoSO, (VoUratb, Bl. [2] 7, 342; Jaoobaen, B.
18, 1761). — 2. From 0,H3(0H,)(N0j)(C0,H)
[3:4:1] by displacement of NO, by CI (BeUstein
a. Erensler, A. 144, 182; Bemsen a. Euhara,
Am. 3, iSl). !
Properties. — Needles (from alcohol). By
KOH fusion it gives oxy-m-toluic acid [173°].
Salts. — BaA'gSaq: slender needles (V.). —
CaA'2 3aq.
Ethyl ether EtA'. (263°).
w-Chloro-o-tolnio acid Amide [2:1]
CH2C1.0,Hi.C0NH,. [c.l80°]. From the nitrile
and HjSO, at 90°, followed by water (Oabriel,
B. 20, 2234). Slender needles (from alcohol).
Boiling water converts it into phthalide. At
160° it changes to oily 'pseudophthaUmidine'
0,H,NO.
Nitrile CHjCl.CjH4.CN. o-Cytmo-bemyl
chloride. [61°]. (252°)., Formed by passing
CI into the boiling nitrile of o-toluic acid (Ga-
briel a. Otto, B. 20, 2223). Monoclinic crystals;
a:bus = -778:1: -294 ; ;8 = 60° 2'. Sol. hot water.
Pi-chloro-toluio acid 0,H,(CH,)C1,(C0,H).
[161°]. Prom crude di-ohloro-xylene (222°) and
chromic mixture (Hollemann, A. 144, 269). —
CaA',9aq.— AgA'.
Di-ai-chloro-toluic acid. Nitrile
CHCl,.CeH4.CN. Cyano-bemyUdene chloride.
(260°). Formed by the action of chlorine on the
boiling nitrile of o-toluic acid (Gabriel a. Weise,
B. 20, 3197). Fuming HOI at 170° gives
0,H,(CHO)(00^). [97°].
Tri-u-chloro-o-toluic acid. Nitrile
OCl3.CsH1.CN. Cyano-benayl trichloride. [95°].
(c. 280°). From boiling o-toluio nitrile and 01
(G. a. W.). Monoelinio crystals (from alcohol) ;
a:6:c = l-546:l:l-106; /3 = 73° 63'.
o-CHLOEO-o-TOLTJIDINE C,H,(CH,)C1(NH,)
[1:2:6]. Formed by reduction of the correspond-
ing nitro- compound (the nitration-product of 0-
oMoro-toluene). Liquid.
Acetyl derivative C,HsCl.NHAo: [136°];
white needles (H6nig, B. 20, 2417)
s-CUoro-tolnidine C,H,(CH,)01(NH,) [1:3:5].
(242°) at 730 mm. Formed by reduction of the
corresponding nitro- compound. Liquid. Vola-
tile with steam.- B'HNO, : [198°], colourless
Acetyl derivative C,H,Cl(NHAc) : [198°];
colourless needles (Honig, B. 20, 2419).
143
OHLORO-TOLTJIDINE,
CMoro-p-toluidine OeH3(CH,)Cl(NH,) [1:3:4].
[7°]. (219° nnoor.). Got by boiling its acetyl
derivative with HCl. Elimination ol NH, gives
tra-ohloro-toluene.— B'HCl.— B'HNOj. S. 2-59 at
19°.— B-HjSO,.— B'HAO,.
Acetyl derivative GeH3MeCl(NHAc)
[1:3:4]. [115°]. Formed by ehlorination of ^-
acet-toluide. Bad yield (Iiellmann a. Klotz, A.
831, 309; cf. Wroblewsky, A. 168, 196).
p - Chloro . o • toluidiue aeH3(CHs)Cl(NH2)
[1:4:2]. [22°]. (237° at 722 mm.). Colourless
liquid or white oryataUine solid. Formed by
teduotion of (4:2:l)-ohloro-nitro-toluene [38°].
Salts. — B'HCl: colourless needles. —
B'i(H2CljPtCli2aq: fine yellow , needles.
Acetyl derivative 08H3(CHs)Cl.NHAc :
[131°]; long slender colourless needles, v. sol.
not water, ^cohol and ether, si. sol. cold water
(Goldschmidt a. Honig, B. 19, 2440 ; cf. Bngel-
brecbt, B. 7, 797; and Beilstein a. Kuhlberg,
A. 158, 336).
Chloro - p . toluidine C,H,(CH3) (01) (Nttj)
[1:2:4]. [26°]. (238°). Formed by reduction
of chloro-nitro-toluene [65°] (LeUmann, B. 17,
635). Colourless crystalline solid. V. sol. all
solvents except water. By diazotisation and
treatment with alcohol it yields o-chloro-toluene.
Salts. — B'HCl: broad colourless needles. —
B'jHaSO,: small colourless plates.— B'jHjPtCls.
Acetyl derivative OsH3MeCl(NHAc).
[105°]. From C,H3M;e(NHAc).N2.NC5Hi„ and
boiling HClAq (WaUach, A. 235, 254).
p. Chloro -m- toluidine 03H,(CHs)Cl(NH2)
[1:4:3]. [28°] (G.8.H.); [30°] (G.a.K.). (230°).
Formed by reduction of (4:3:1) -chloro-nitro-
toluene [9°]. White crystalline solid. The
base and its salts are extremely soluble. —
B'HCl : colourless tables.
Acetyl derivative C8Hs(CH3)Cl.NHAo:
[97°] ; long silky needles, m. sol. water (Gold-
schmidt a. Honig, B. 19, 2442 ; cf. Engelbrecht,
B. 7, 797 ; and Gattermann a. Kaiser, B. 18,
2^99K
Chloro-o-toluidiue C3H8(CH3)Cl(NHj) [1:5:2].
[30°]. (237° nnoor.) at 730 mm. Prom its
acetyl derivative (L. a. K.). The same com-
pound ([30°], (241°)) appears to be a by-product
in the reduction of o-nitro-toluene by tin and
HCl (Beilstein a. Euhlberg, A. 156, 81).
Salt.— B'HCl: si. sol. water.
Acetyl derivative C„H3Me(NHAc)Cl.
[140°]. Got by chlorination of acetylated
o-toluidine (LeUmann a. Klotz, A. 231, 317).
o-Chloro-m-toluidine CsH3MeCl(NH2) [1:2:5].
[83^. (239°) at 215 nun. Obtained by reduc-
tion of the corresponding nitro- compound [44°]
(Goldschmidt a. H8nig, B. 19, 2443 ; 20, 199 ;
Wroblewsky, A. 168, 200 ; Henry a. Eadziszew-
sky, B. 2, 308, 699). Formed also as a by-
product in the reduction of m-nitro-toluene by
zinc-dust and HCl (Kock, B. 20, 1567). Glisten-
ing colonrless needles of characteristic odour.
Salts. — B'HCl: long slender needles. —
B'HNO,: [164°], broad colonrless needles. S.
601 (W.).— B'jHjSO,.
Acetyl derivative CaH,MeCl(NHAo) :
[89°] ; coloorlesB plates.
Di- chloro ^-tolnidjae 0,Hj(CH3)CLi(NH,)
[1:8:5:4]. [60°]. Needles (from dilute alcohol).
v. sol. alcohol and ether. Weak base. May be
BubUmed.
Acetyl derivative 08HjMe(NHAo)Cl,
[1:4:3:5]. [201°]. From C,H3Me(NHAc)01 [1:4:3]
by chlorination (LeUmann a. Klotz, A. 231, 322).
White needles (from alcohol). V. sol. alcohol,
insol. water, sol. ether and glacial acetic acid.
May be sublimed.
(,8) - Di- chloro - toluidine C,H2(CH3)Clj(NKj).
[1:2:4: ?]. [87°]. (259°). Formed by reducing
(i8)-di-chloro-nitro-toluene [53°] (Seelig, A. 287,
163). Plates (from methyl alcohol).
Di - chloro - toluidine CeH(CH,)Cl2(NH2)
[1:2:4:6]. [88°]. (259°). Obtained by reducing
di-chloro-nitro-toluene [-14°] (Wroblewsky, A.
168, 213). Does not combine with acids.
Tri - chloro - toluidine C5H(CH3)C1,(NH3)
[1:2:4:6:3] or [1:2:4:5:6]. [91°] (Sohultz, A. 187,
278); [95°] (Seelig, B. 18, 423). From tri-
chloro-nitro-toluene [89°], tin and HCl. Needles
(from alcohol).
Acetyl derivative 03H(CH,)Cl,(NHAa).
[191°].
Benzoyl derivative C8H(CH3)Clj(NHBz).
[213°].
Tri - chloro - toluidine C8H(CHg)Cl3(NHj)
[105°]. From (S)-tri-chloro-mtro-toluene, SnCl^,
and HCl (Seelig, B. 18, 423). Needles.
CHLOEO-TOLTJdTmiOLIHE v. Chloiio-(B.).
METHTL-QTJINOIiINE.
CHLOEO - TOLTJQTJINONE CeH2(CH3)010j.
[l:4or3:2:5]. [90° uncor.]. Formed by oxida-
tion of di-chloro-o-cresol with K^Cr^O, and dilute
HjSO,. Long yeUow needles. Volatile with
steam, and sublimable. Y. sol: alcohol, ether,
&a., sol. hot water, si. sol. cold. Dissolves in
alkalis with a dark-red colour. By SO^ it is re-
duced to chloro-hydrotoluquinone [115°] (Claus
a. Sweitzer, B. 19, 929).
Chloro-tolnqninone C3H2(CH3)C102. [105°].
From chloro-hydro-toluqoinone [175°] by dis-
tillation wiQi aqneouB Fe,Cls (Schniter, B. 20,
Di - chloro - tolue[uinone CjH(CH3)Cl20j
[1:2:4:3:6]. [103° nncor.]. Glistening yeUow
plates. VolatUe with steam. Formed by oxida-
tion of di-chloro-m-cresol with KjCr^O, and
H2SO4. Also from m-cresol, HCl, and KCIO,
(Southworth, A. 168, 270). Yellow tables (from
alcohol). The corresponding di-chloro-hydro-
toluquinone melts at [171°] (Clans a. Schweitzer,
B. 19, 931).
Di - chloro - tolaqninone CjH(CH,)CljOj
[1:?:?:2:5]. Prom, o-cresol, KCIO3, and HCl
(South worth, A. 168, 274). Not obtained pure.
Beduced by SO, to di-chloro-hydrotoluquinone
[121°].
Tri-chloro-toluquinone C,(CH3)Cl,0j. [232°].
From o-cresol, HCl, and KCIO3 (Grsebe a. Borg-
mann, A. 152, 248; Southworth, A. 168, 273;
Knapp a. Schultz, A. 210, 176). Formed also by
treating o-toluidihe sulphonio acid with KGIO,
and HCl (Hayduok, A. 172, 209). YeUow plates ;
si. sol. cold aloohol, t. soL ether. VolatUe with
steam.
Tetra-chloro-tolnqninone CH^CI.CgCliO^. Oc-
curs among the products of the action of HCl
and EClOg on beech-wood creosote (Gorup-
Besanez, A. 143, 159 ; Brauninger, A. 186, 339).
Golden scales. May be sublimed. SI. sol. cold
aloohoh
Dl-OHLOBO-YDTYL-BENZOIO AOID.
143
GHIOBO-TOLITQTriirOXALINrE Dihydride.
^NH.OH,
CANjCl i.e. C.H3(0H,)< | . [77°].
\n=cci
Formed by heating oxy-di-hydro-toluquinoxaline
witliPGlj. Long colourless needles. Insol. water,
T. e. sol. other solvents. Volatile with steam
(Leuokart a. Hermann, B. 20, 29).
Si-cliloro-tolaquinozalme OA^sO^ *-^-
O.H,Me<^:g°}> . [115°].
From di-ozy-tolnquinoxaline (1 mol.) and FClj
(2 mols.) at 170° (Hinsberg, A. 237, 350).
Needles (bom obloroform and petroleum-ether).
Insol. water.
SI-CHLOBO-TOLTrTI.-BENZOIC ACID
CHs.08H,.00.0„H,01j.OO^. Di-cUoro-phmyl
tolyl ketone carbosyyUe aeid. From (3)-diohloro-
phfhalio anhydride, toluene, and A1,C1, (Le
Boyer, A. 238, 357).
CHLOBO-(a)-IOLTITLIC ACID v. Chlobo-
PBENTL-ACETIO AOID.
DI-CHLORO-BITOLTL
[3:4:l]05H3MeCa.O,H,MeCl[l:3:4]. [51°]. From
di-amido-ditolyl by Sandmeyer's reaction (StoUe,
B. 21, 1096). Lamina (from alcohol). CrO,
gives ohloro-toluio acid [205°].
CHIOBO-DI-TOLYL-fert-BTTTYL ALCOHOL
CCl(C.H4Me)j.CMejOH. (o. 265°). From ace-
tone-chloroform, toluene, and Al^Clj (Willgerodt
a. Genieser, J.pr. [2] 37, 369).
Di-chloro-tolyl-tert-bntyl alcohol ■
CCaj(0<p,Me).CMejOH. (o. 245°). From ace-
tone-chloroform, toluene, and AljOlj (W. a. G.).
CHLOaO-TOLYIENE-m-DIAMINE
0,H2(CH,)C1(NK,)2 [1:4:3:5]. [111°]. Formed by
reduction of ohloro-di-nitro-toluene [48°]. Gives
the chrysoidine and Bismarck-brown reactions
(Honig, B. 20, 2420).
(j3)J)i-chloro-tolylene-diamine
C^(CH,)Ol2(NHJj[l:2:4:5:6]. [110°]. Formed
by reducing (j8)-di-chloro-di-nitro-tolnene [102°]
(Seelig, A. 237, 164). Plates (from ligroinj. On
boiling with HOAc for twenty-five hours the
anhydro- base is formed [170°] ; browniab needles
(from alcohol).
(o)-Tri-chloro-tolylene-aian»ine
C,(0H,)01,(NByj. [196°]. Formed by reduction
of tri-ohloro-di-nitro-tolueno [227°] (Seelig, B.
18, 422 ; A. 237, 143). White needles (from
alcohol). CrO, oxidises it to a quinone.
Acetyl dtrivative C,(CH,)Cl,(NAc2)2.
[220°].
(;8)-Tri-chloro-toIylene-dianiine
C8(CHs)Cla(NHs)2. [207°]. Formed by reducing
tri-chloro-di-nitro-toluene [141°] with stannous
chloride in alcohoh'o solution (Seelig, A. 237,
143). Needles (from petroleum ether). On
boiling with EOAc an anhydro- base is formed,
hence the substance is an orthodiamine.
«-CHLOEO.DI-TOLYL-ETHANE
CHj01.CH(C«H,.CH3)s. From CHjCl.CHCa.OEt
(di-chloro-ether), toluene, and HjSO, (Hepp, B.
7, 1413). Alooholio KOH gives CH,:C(C«H,Me)p
Xri-M-chloro-di-tolyl-ethane
C01,.0H(0,H,.CH3)r [89°]. S. (ether) 50; (alco-
hoi) 2-5. From chloral, toluene, and H,SO« (O.
Fischer, B. 7, 1191).
d;-CHL0B0-DI-T01YL-ETHYIENE
001,:C(0,H4.CByr P2°]. S. (ether) 60 ; (bIoo-
hoi) 2-9. From the preceding body and alcoholic
KOH (0. Fischer, B. 7, 1191). Needles.
DI-CHLOEO-DI-TOLYL-METHANE
CHj(08Hj.0H201)j. [108°]. From benzyl ohlor-
ide, methylal CHJOMe),, and H^SO,. LaminiB
(Weiler, B. 7, 1181).
o-CHLOaO-m-TOLYL-PHENYL-THIO-UEEA
0„H..NH.CS.NH.0„H3Me01 [5:1:2]. [109°]. White
granules. Prom CaH3MeCl(NHa)[l:2:5] and
phenyl-thiocarbimide (Goldschmidt a. Honig, B.
20, 201).
CHLOEO-TEOPIC ACID C,H,C10a i.e.
C,H5.001(C0.^).CH30H. [125°-130°]. From
atropio acid and HCIO (Ladenburg a. Biigheimer,
A. 217, 109). V. e. sol. water, si. sol. benzene.
Beduced by zinc-dust, iron filings, and EOH to
tropic acid.
CHLOBOITS. Adjective sometimes used as
synonymous with negative or acidic; generally
applied to radicles which combine with basylom
radicles to form salts, e.g. the radicles SO^N^O,,'
CIO, are called aMarous, as distinguished from
E2O, CaO, &c., which are basylous. The term
chlorous is also sometimes applied to the more
negative elements, especially to those which, like
chlorine, do not displace the H of acids to form
salts. The correlative term is basylous.
M. M. P. M.
CHLOEOUS ACID HClOj; «. Ohlobini, oxy-
ACIDS 07, p. 17.
a-CHLOEO-ISOVAIEEIC ACID bsHjClOj Le.
(CH3)2CH.CHCl.COjH. From sodium isovalerate
and aqueous HOCl (Sohlebusch, A. 141, 322).
Oil ; decomposed by heat.
Tri- and tetra-chloro-isovaleric acids were
obtained by Dumas a. Stas by chlorinating iso-
valeric acid' in the dark. They decompose be-
tween 110° and 150°, giving off HCl.
CHLOEO-ISOVALEEIC ALDEHYiDE C^OIO.
(135°). S.G.i^ 1-108. From isovaleric aldehyde
and CI at - 18° (SchrOder, B. 4, 402). Combines
with NaHSO,.
Di-chloro-isovaleric aldehyde CsH^Cl^O
(147°). From isovaleric aldehyde and CI at 15°.
Oombines with NaHSOj (Kiindig, A. 114, 1).
TEI-CHLOEO-VALEEOLACTIO ACID v. Tbi-
CHLOBO-OXT-VAIiEBIC ACID.
CHLORO-VALERO-LACTONE v. CmoBo-oxT-
VAiiBEio AOID, Anhydride of.
DI-CHLOEO-VALEEYLENE CJS.fil, i.e.
CHj:CCl.CHj.CCl:CH2. Di-chloro-di-vinyUne-
thane. (145°). Formed by the action of POI5
upon aoetyl-icetone. Liquid ; boils without de-
composition. Beadily takes up Br, forming
CsHjCljBr,. Heated with alcohoUo KOH it gives
CH:C.CHj.O(OCjH,):CH, (Combes, A. Ch. [6]
12 222)
'lI-CHL0E0-o-VINY1-SENZ0IC ACID
Cj,H01j.C^4.C0jH. [121°]. From tri-rfiloro-oxy-
indonaphthene C,H4<^(jg-Qj>COL5 by solution
in aqueous alkalis (Zincke, B. 20, 2890). Slender
needles (from dilute alcohol). ^ Sodium amalgam
converts it into o-ethyl-benzoic acid [68°].
Methyl ethef MeA'. [47°].
o-£izo-tri-ohloro-vinyl-benzoic acid
C.H4(C01:C0yCO2H[l:2]. [161°].
Pormation. — 1. By the action of NaOHAq
on tetra-ohloro-oxy-indonaphthene
C,H,<^,>COI, (Zincke, B, 20, 8055).—
144
DI-CHLOKO-VINYL-BENZOIO AOID.
2. Tetraohloro-(/3}.iiaphtho-qninone is dissolved
in KaOHAq, HOAo added, and the mixture oxi-
dised \rith ohiomio acid (Zincke, B. 21, 499).
Properties. — Needles or plates. V. sol. alco-
hol and HOAc. Sodium amalgam yields o-ethyl
benzoic acid.
Methyl ether ATile. .[75°J.
CHLOBO-VIim ETHYL OXIBS 0,H,C10
».e. 0Hj:CC1.0Et, (123°). S.G. sa 1-02 (Geuther) ;
12 1'036 (Godefroy). V.D.3-52. From tri-ohloro-
ethane CH,.CC1, and NaOEt at 120° (Genther,
Z. 1871, 128). Formed also by the action of
zinc-dust or the ziuo-copper couple on the oom-
poond C^ijGl^O, obtained by passing chlorine
throagh a mixture of alcohol and 'Kfivj^i (Gode-
froy, C. B. 102, 869).
Beoctions.— 1. Br forms CHjBr.CClBr.OBt
(170°-180°), whence CI forma CHjCl.C01j.0Et.—
2. HCl forms CH2Ol.CHCl.OEt.— 8. HNO3 gives
acetic and chloro-acetic acids. — 4. Beduoes am-
moniacal AgNO,, forming a mirror. — 5. Exposed
to the air it rapidly changes to a vitreous mass
(C4H,CI0),aq.
Si-chloro-vinyl ethyl oxide CHCI:0C1.0Et.
(128° cor.). S.G. ISIO8. Formed by the action
of NaOEt upon CH^CLCHCl, (Geuther a Brock-
hoff, J.pr. [2] 7, 112) or CClH:OCLj (Patem6 a.
Oglialoro, B. 7, 81). Water at 180° forms gly-
OoUic acid.
Di-chloro-vinyl ethyl oxide GCl2:CH.0Et.
(145°). From CHCVCHCl.OEt and cone, aqueous
EOH (Godefroy). Sweet-smelling oil. Beducea
ammoniacal AgNOj, forming a minor. Greedily
combines with Br.
Tri-chloro-vinyl ethyl oxide CCV.OCl.OEt.
(155°) (B.) ; (0.160°) (G.). S.G. s 1-373 ; 122 1-235
(P. a. P.); 12 1-332 (G.).
Formation,.— 1. From CCljiCClj and NaOEt
at 110° (Geuther a. Fischer, J. 1864, 316).—
2. From CCl,.CHC1.0Et and cone, aqueous EOH
(Patern6 a. Piaati, Q. 2, 333 ; Godefroy, 0. R.
102, 869 ; Buach, B. 11, 446). Smells like mint.
Br forma CCLjBr.CCIBr.OEt [17°]. CI gives
CjOIrO.CA-
CELOBO - DI - VIKYL • METHANE v. Di •
CBLOBO-VAIiEBTCGNE.
HEXA-CHLOBO-DI-VINTL OXIDE 0,01,0
tA {CCV.001)sO. Ohloroxethose. (210°). S.G. si
1'652. Prom (OjCl5)jO and alcoholic K,S (Mala-
guti, A. Oh. [3] 16, 19). Br forms O^ClsBr.O
[96°].
CHLOBOX- V, CmoBo-ox-.
CHLOBOXAL- «. Chlobo-oxaii-.
CHLOBOXETHOSE v. HuxA-OHLOBO-sx-Tiirei.
OXIDE.
CHIOEOXY- V. Chmbo-oxy-.
CHLOBO-o-XYLENE 0,H,(CH,)jCl, [1:2:8%
Mol.w.l40^. (190° cor.). Fluid at -10°. Formed,
together with 'the (l:2:4)-isomeride, by chlorina-
tibn of o-xylene in presence of 5 p.c. of iodine.
By dilute ENO, it is oxidised to .chloro-toluic
acid [164°], which by KMnO, ia further oxidised
to chloro-phthalio acid [181°] (Eriiger, B. 18,
1756).
CMoro-o-xylene C.H,(C^)2C1 [1:2:4]. (192°
cor.). Fluid at -20°. S.G. ft 10692. Formed,
together with the (l:2:3)-isomeride, by chlorina-
tion of o-xylene in presence of 6 p.o. of iodine.
By dilute HNO, it is oxidised to two isomeric
efalsro-toluio acids [166<^ and [130°], which by
further oxidation with EMnO, yield ohloro-
phthaUc acid [130°-134°] (Eruger, B. 18, 1755).
tlhloro-o-xylene CeHs(CHa)jCl. .(205° uncor.).
S.G. 12 1-0863. Colourless, strongly refractive
liquid. According to Olaus a. Eautz (B. 18,
1367) this is the only ohloro-o-xyleue formed by
chlorination of o-xylene in the cold in presence
of iodine. It is readily oxidised by dilute HNO,
to chloro-phthalio acid.
Chloro-TO-xylene CjH3(CH,)j01 [1:3:4]. (186°
cor.). S.G. §2 1.0598, Fluid at -20°. Formed
by chlorination of tn-xylene in presence of 5 p.c.
of iodine. By EjCo^O, and H^SO, it is oxidised
to ohloro-m-toluio acid CjH3(OH3)01.COiiH [3:4:1]
of melting-point [210°] (Jacobsen, B, IS, 1760;
cf. Vollrath, Z. 1866, 488).
Chloro-p-xylene 03H3(CH3)jCl [1:4:2], [-^2°].
(186° cor. at 767 mm.). Formed by chlorination
of ^-xylene in presence of I (Eluge, B. 18, 2099).
a-Chloro-o-xylene CsH,(CH3)(CHsCl) [1:2].
(198°),
FormaUon. — 1. By chlorinating boiling o-
xylene (Eeyman, Bl. [2] 26, 534).— 2. By heating
CeHj(CH3)(CH30H) [1:2] with cono. HCl. If
cannot, however, be obtained pure in this way
(Colson, A. Oh. [6] 6, 117),
Reaction. — Boiling aqueous Pb(NO,), gives
o-toluic aldehyde.
u-Chloro-nt-xylene CjS4(0H3)(CH2Cl) [1:3].
So-called m-roZj/ZoMoWde, (196°). S.G. 21-079.
FormaUon. — 1, From 01 and boilingTTi-xylene
(Vollrath; Lanth a. Grimaux, Bl. [2] 7, 233;
A. 145, 115 ; Gundelach, C, B. 82, 1444).— 2, By
the action Of HCl upon CaH4(CH,),(CHjjOH) [1:3]
(Colson, A. Oh. [6] 6, 118).
<o-Chloro-p-xylene C,H4(CH3)(0H3C1) [1:4],
(192°). From 01 and boiUng^-xylene (L. a. G.),
Di.cMoro-o.xyleneCaHj(CH3)Cls. [3°]. (227°).
Colourless atrongly refractive liquid. Formed by
chlorination of o-xylene in the cold in presenot
of iodine. It is readily oxidised by dilute HNO,
to di-chloro-phthalic acid [183°] (Clans a. Eautz,
B. 18, 1367).
Di-chloro-m-xylene 0sH3(0H3),CIj. (222°),
From m-xylene and 01 in presence of iodine
(HoUemann, Z. 1865, 554 ; A. 144, 268). White '
laminsa ; melts by the heat of the hand.
Di-chloro-p-xylene C,H,(CH3),0L [1:4:2:5],
[71°], (221° i.V,),
Formation. — 1, By chlorination of j>-xylene.
2. From chloro-jp-xylidine [92°] by diazotisation
and treatment with CujClj (Eluge, B. 18, 2098).
Plates or flat needles. V. soL hot alcohol and
ether, si. sol. cold alcohol.
<o(u-Di-cMoro-o-zyleue ' (1.2)C.H.(CH,C1)~
[55°]. (240°). S.G.21-393. S.H. (15° to 40°) -283.
FormaUon. — 1. By the action of HCl on ojw-
di-oxy-o-xylene (Hessert, B. 12, 648 ; Colson, Bl.
[2] 43, 7).— 2. By heating o-xylene (10 c.o.) with
POl, (35 g.) at 180°-200° (Colson a. Gautier, Bl.
[2] 45, 6 ; C. iJ, 101, 1064 ; 104, 428 ; Strassmann,
B. 21, 578).
Properties. — White crystals; v, sol, ether,
alcohol, ligroln, and chloroform. Converted by
heating with water into 0,H,(CHjOH), [62°]»
Potassium phthalimide reacts with formation of
CH.,01.C„H,.CH,.N:0,H,0, [140°] (Strassmann,
B, 21, 576)..
Di - chloro- 0 - xylene C^,(CH3)(0H01,)(?).
[103°]. (225°). From 01 and boiling o-zylene
(Beyman, Bl. [2] 26, 534)
OHLORO-XYLOQUINONE.
141
■-M-cMoro-jw-xylene OjHJCHjOl) Jl:3]. [34°].
(253=). S.G. 22 1-302. S.H. (15° to 40°) -295.
m3rmaU(m.—l. From 0„Hj(CH20H)j [1:8]
and HOI (Colson, Bl. [2] 43, 7). By heating m-
xylene at 180° with the equivalent amount of
PClj. The yield is not so good as with the o- and
p-oompounds, and to obtain it pure it is necessary
to saponify the crude product and treat the glycol
Bo produced with HOI (Colson a. Gautier, Bl.
[2] 45, 6 ; A. Ch. [6] 6, 114).
Di-u-chloro-p-xylene CeH,(0H2Cl)j [1:4].
[100°]. (240°-250°). S.G.21-417. S.H. (15° to
40°) -282.
Formaticm. — 1. From 01 andboilingp-xylene
(Lauth a. Grimaux, A. 145, 115). — 2. From
0eH,(0H2OH)j [1:4] and HCl.— 3. By heating p-
xylene at 180° with the equivalent amount of
PCI5 (Oolson a. Gautier, Bl. [2] 45, 6).
Froperties. — Tables (from alcohol). Heated
with water it gives the glycol G^tlfjE^OB.)^.
[113°] (Grimaux, O. B. 70, 1363).
Tri-chloro-o-xylene CaH(0Hj)2Clj. [93°].
(265° nncor.). Formed by ohlorination of o-
xylene in the cold in presence of iodine (Claus
a. Kautz, B. 18, 1367). Long colourless glisten-
ing needles. V. sol. ether, benzene, hot acetic
acid, and hot alcohol, v. si. sol. cold alcohol. It
is readily oxidised by dilute HNO, to tri-chloro-
phthalic acid, the anhydride of which melts at
[167°].
Tri-cMoro-TO-xylene a,H(0H3)jCl3. [150°].
(255°). From m-xylene and 01 in presence of
iodine (Hollemann, A. 144, 270). Silky needles :
T. sol. not, si. sol. cold, alcohol.
Tetra-chloro-o-xylene Os(CH3)jOl4. [215° un-
cor.]. Formed by ohlorination of o-xylene in the
qold in presence of iodine (Claus a. Kaijtz, B. 18,
1367). Sublimable. Long colourless needles.
Not volatile with steam. Sol. ether, benzene, hot
acetic acid, and hot alcohol, si. sol. cold alcohol.
It is not oxidised by heating with HNO,.
Tetra-a-cMoro-o-xylene CjH4(CHCl2)j [1:2].
[86°](0.a.G.); [89°] (H.). (274°). S.G. £ 1-601.
S. (ether) 50 at 15° ; 100 at 35°. S.H. (15°-60°)
■24.
Wormatvm. — 1. From 01 and boiling o-xylene
(Hjelt, B. 18, 2879).— 2. From PClj and o-xylene
at 150° (Oolson a. Gautier, Bl. [2] 45, 10).
Properties. — Triolinic crystals (from ether)
o:6:c = -972:1: -741; a = 54° 38'; j8 = 54° 20';
7 = 58° 24'. Its solubility in petroleum ether ia
double thatofthep-compound. Sol. O5H5, CHOI,,
and alcohoL Water at 170° converts it into
phthalide.
Tetra-oi-chloro-M-xylene C5H4(0H0l2)2.
(273°). S.G. 1-536 (Oolson a. Gautier, Bl, [2]
45, 509).
Tetra-»-cMoro-^.xyle'ne C^tiCaCli^ [1:4].
[93°]. S.G. 2 1-606. S.H. (15° to 60°) -242. S.
(ether) 50 at 35°; S. (ligroiin) 7. Formed by
heating p-xylene (5| 0.0.) and pure PCI5 (40 g.)
at 195°, and crystallising the product from ether
(Colson a. Gautier, Bl. [2] 45, 9). Saponified
by boiling with water gives terephthalio aldehyde
0^,(COH), [1:4]. [114°].
Penta-«-chloro.o-xylene CsH4(CCl3) (CHOl^)
[1:2]. [54°]. From o-xylene (3-2 o.C) and PCI5
(40 g.) at 200° (Gautier a. Colson, O. B. 102,
689). Converted by boiling water into
C,I-I,(CO.,H)(CHO). [97°].
Yoi. II.
Hexa-cMoro-M-xyleno OjHiCl, [1:3]. (0. 286°),
From OT-xylene and POl, (Oolson a. Gautier,
O. B. 102, 689). Converted by alkaUs into a
chlorinated acid.
Hexa-B-chloro-p-xylene 0^4(0013), [1:4].
[111°]. Formed by heating ^-xylene (1 mol.)
with PCI3 (6-5 mol.) for 10 hours at 200°. Trans-
parent crystals. Sol. ether. Heated with a
solution of NaHO, it loses all its chlorine, form-
ing terephthalio acid (Colson a. Gautier, Bl. [2]
45, 507).
CHLOEO-o-XYLEHE-STJIPHONIC ACID
C„H.(CH3)j01.S03H [1:2:4:5]. Formed by sul-
phonation of chloro-o-xylene (1:2:4) (Kniger, B.
18, 1756). On reduction with sodium amalgam
it gives o-xylene-sulphonic acid (1:2:4).
Salts. — A'Na5aq: glistening needles or
large flat prisms. — A'E : short needles. —
A'2Ba4aq: long needles, sol. hot water, more
sparingly in cold.
Amide CjHjMejCl.SOjNHj : [207°]; long
felted needles, sol. hot, si. sol. cold, alcohol, v. si.
sol. water.
Chloro-o-xylene-sulplionic acid
C„H2(CH3)2C1.S03H [1:2:3:6]. Formed by sul-
phonation of ohloro-o-xylene (1:2:3) (Eriiger, B.
18, 1756).
Salt s. — A'Na aq : large pearly plates. — A'K :
plates. — ^A'jBa aq : thin glistening plates.
Amide OuHjMejOl.SO^NH, : [199°]; fine
silky needles or long prisms, sol. hot alcohol, si.
sol. water.
Ohloro-m-xylene-sulplionio acid
05H2(CH3)jCl.S03H [1:3:4:6]. Formed by sul-
phonation of ohloro-m-xylene, OgHj(OHj)2Cl
[1:3:4] (Gundelach, Bl. [2] 28, 343 ; Jacobsen, B.
18, 1761).
Salts. — AITaaq: long fine needles, si. sol.
cold water. — ^A'K aq : needles, v. e. sol. water. —
A'jBa very sparingly soluble small tables.
Amide OeHj(CHs)j01.S02NHj. [195°].
Prisms (from alcohol).
Clilora-j7-xylene-saIplionic acid
ObH2(CH3)201.S03H. Formed by sulphonation
of chloro-^-xylene.
Salts. — A'Naaq; easily soluble prisms.^
A'2Ba aq : sparingly soluble needles (Eluge, B.
18, 2099).
CHL0E0.»»-XY1IDINE C,H,o01N. [89°].
From (2,3,l)-nitro-jre-xylene, tin, and HOI
(TavildarofE, Z. 1870, 419). Crystalline.
Cbloro-p-xylidine C^B.^(CE.,)fi\.^n^ [1:4:2:5].
[92°]. Formed by the action of tin and HCl upon
nitro-^-xylene (Jannasoh, A. 176, 55). Laminsa
(from water). By diazotising and treatment
with cuprous chloride it yields di-chloro-f-
xylene [71°].
Salts. — B'H012aq. — B'^S04 2aq. —
B'jHjOA.
Acetyl derivative CjHjMejCl.NHAo —
[171°], colourless needles (Huge, B. 18, 2098).
CHLORO-XYLO-HYOBOQUINONE v. Chlobo-
HYDEO-XYIiOQUINONB.
CHLOEO - XYLOariKONE 0,HClMe,0.
[a!:l:4:2:5]. Chloro-phlorone. [48°]. Gone. HCl
dissolves xyloquinone, but immediately a brown
crystalline mass separates. This is a mixture
of mono- and di-chloro-hydro-xyloquinones. If
it be oxidised by CrOj or HNO3 a mixture of
mono- and di-chloro-xyloquinones is got. From
alcohol the former crystallises in needles, the
146
CHLORO-XYLOQUINONE.
latter in plates (Carstanjen, J. pr. [2] 23, 430 ;
cf. V. Bad, A. 151, 158). Chloro-xyloquinone is
converted by boiling with HCl into di-chloro-
hydro-xyloquinone.
Di-cMoro-xyloquinone G,G\.^ejd^. [175°].
Prepared as above. Not afiected by boiling HOI.
a - SI - CHLOBO-0-XYLYLENE-SI - HALONIO
ETHER OjH4[CH2.0Cl(OOjEt)Jj. Prom sodium
chloro-malonio ether and [l:2]G^,(CH2Br)2
(Baeyer a. Perkin, B. 17, 452 ; C. /. 63, 14).
Liquid. AloohoUo EOH gives o-phenylene-di-
acrylic acid.
Si-chloro-m-xylylene-dl-malonio ether
CeH4(CH2.0Cl(C02Et)j)j. Formed by the action
of chloro-malonio ethyl ether and sodium ethylate
on m-xylylene dibromide (Kipping, C.J. S3, 26).
Thick yellowish oil.
Dl-chloro-jp-xylylene-di-malonic ether
C,H4[0Hj.CCl(C0jEt) J,. [87°]. Formed by
acting with ethyl chloromalonate and sodium
ethylate on ^-xylylene dibromide (Kipping,
C. J. 53, 35). Colourless six-sided plates. Insol.
water, v. sol. alcohol, ether, petroleum ether,
and HOAc.
CHLOBO-DI-XYLYI-ETHANE C,gH2,Cl i.e.
CHjC1.0H(C8H3Me2)j. From di-chlorinated ether
CH2Ol.CHCl.OEt, xylene, and H^SO, (Hepp, B.
7, 1416). On distUlation it splits up into HOI
and CHj:0(C,HsMe2)2.
CHOLAliIG ACID v. Cholio acid.
CHOLANIC ACID CjaHj^O, ^aq. [285°] (L.).
8. '025 at 100°; -Oil at 20° (L.; cf. Kutscheroff,
B. 14, 1492) ; S. (alcohol of 98-5 p.c. at 18°) 1-37.
[o]d = 53° (T.); 88° (Kutscheroff). Formed by
oxidation, with KjCr^O, and HjSO,, of eholeic
acid CjsHijjOj, of dehydrooholeio acid C^sHjgOj,
and also (according to L.) of desoxycholic acid
(Tappeiner, .d. 194, 231; Latschinoff, B. 13,
1052; 18, 3045; 19, 474, 1521; 20, 1044; Bl.
[2] 46, 818). Large tables or flat prisms. Tribasio
acid. Dextro-rotatory. On further oxidation by
boiling with HNO, (1-28 S.G.), it gives choloid-
anic aoid and pseudo-choloidanio acid.
Salts. — ^A"'2Baa6aq: tables or plates; S.
(at 18°) 4-12; [o]^ =+ 49-37°.
Mono-methyl ether ^'"BJKe: [207°];
very slender needles; v. sol. alcohol, less sol.
ether ; the Na, E, Ca, and Ba salts are v. sol.
water and alcohol. — A"'MeBa.
' Mono-ethyl ether A"'HjEt: [190°]; the
properties are the same as those of the mono-
methyl ether.— A"'EtBa.—A"'EtPb.
■ " ether A"'HMe8: [176°];
A"'HEtj: [131°].—
Di-methyl
needles.
Di-ethyl ether
A"'^tjBa.— A"'2Et,Pb.
Tri-methyl ether k'"^^^: [121°]; needles.
Tri-ethyl ether A"'Bts: [76°]; needles.
Jso-cholBnio acid C^r^ssOA^) [248°].
[o]d = 73'3°. S. -022; S. (alcohol) 9-1 ; S. (ether)
•018. Formed in small quantity, together with
oholanio aoid, by oxidation of ohbleio acid, with
KjCrjO, and H2SO4 (Latschinoff, B. 15, 713;
19, 1529). The cholanio aoid described by Tap-
peinei appears to be contaminated with a small
quantity of this isomeric aoid. Pearly plates.
Fenta-basic acid.
Salts. — A'Kj: soluble hair-like needles. —
A'KjHj : fine needles.— A'^Baj lOaq? : sparingly
soluble amorphous powder. — A'Ba.jH. —
A'jPbj 6aq : amorphous pp., insol. water and
alcohol. — A'Ags : insoluble amorphous pp. -^
A'2Cu50u404 lOaq : amorphous blue pp.
Methyl ether Cjai,fi,M.e,: [136°]; plates.
From the lead salt and Mel.
Ethyl ether OaHaO^Etj: [43°-50°]; flat
CHOLECAMFHOSIC ACID v. Choloicanic
ACID.
CHOLElC ACID Oj5H4j04(?). [185°-190°].
S. (water at 20°) -0045 ; (75 p.c. alcohol at 20°)4 ;
(absol. alcohol at 20°) 7"1 ; (absol. ether at 20°)
■133. With 300 mm. of a 6-06 p.o. solution in
absol. alcohol at 20°, [<j]o = 66°40'. From alco-
hol or acetic acid it crystallises in heniihedral
rhombic needles, a:b:c = 1: '5057: 1*8598. Occurs
in saponified ox-gall together with oholic and
desoxycholic acids. It gives Pettenkofer's test
for bile acids (Mylius,' H. 11, 492). On gentle
oxidation with CrO, and acetio acid it is con-
verted into dehydrooholeio aoid OjbHjjO,, by more
vigorous oxidation, with 'S^Giji, and H2SO4,
into oholanio acid (but no biliauic aoid). Ac-
cording to Latschinoff by boiling with glacial
acetio acid it is converted into desoxyohoho
acid (called by him ' hydrated choleio aoid ') ;
Mylius, however, was unable to confirm this
statement.
Salts. — A'Ag. — A'^Ba: microscopic plates,
insol. strong alcohol and water, v. sol. dilute
alcohol forming the hydrated salt. — A'jBa 6aq :
needles, v. sol. dilute alcohol, S. (water at 20°)
•083 (Latschinoff, Bl. [2] 46, 817 ; B. 18, 3039 ;
19, 1140; 20, 1043, 1053 ; Mylius, B. 19, 369;
20, 1968).
Dehydrocholeic acid C2jH3g04(?) according
to L. [183° uncor.]. Obtained by slowly adding
a 10 p.c. solution of CrO, (3 pts.) in acetic acid
to a 10 p.c. solution of eholeic acid (4 pts.) in
acetic acid ; the yield is 60 to 70 p.o. Accord-
ing to L. it is also formed by similar treatment
from desoxycholic acid. SUky tables. Less
soluble in water and alcohol than dehydrocholio
aoid. By further oxidation, with K^OrjO, and
H2SP4 it yields oholanio acid. — A"Ba i^aq :
needles, v. sol. alcohol, si. sol. water (Latsohinolf,
B. 18, 3045 ; 20, 1044).
CHOLESTEHIN JArUmal cholesterin)
C25H440,aq, or O^sH^jO.aq, or Cj-H^jOaq. [146°,
Hesse] [147*5°, or cor. = 148-5°, Beinitzer]
[usually given at 145° to 146°].' [«]„ for
anhydrous cholesterin from gallstones in chloro-
form = (-36-61 -H 0-249 p.) (0. Hesse). This
rotation depends to some extent on the strength
of the solution. S.G. |- 1-046 (Mehu, J. Ph.
[4] 20, 175); 1-067 (Hoppe-Seyler, Omelin's
Handb., 18, 118) ; 1-03 after fusion (Hein., ibid.).
Occurrence. — This substance was first ob-
tained by Gonradi in 1755 from human gall-
stones, of which it sometimes constitutes nearly
the entire substance. It has been found in
human bile (Chevreul, A. Gh. 95, 5 ; 96, 166) ;
in the blood (Lecanu, A. Gh. 67, 54 ; Boudet,
ibid. 336; Denis, J. Chim. Med. [2] 4, 161;
Becquerel a.Bodier, Oaz. Med. 47) ; together with
protagon as an essential constituent of the
nervous tissue, of the yo^k of egg, of the
seminal fluid, and of the red and white cor-
puscles of the blood (Hoppe-Seyler, Med. Ghem.
' When cholesterin is mixed with iso-cUoleBteiin, the
melting point I9 loweied.
OHOLESTERIN.
147
Vnters. 1, 140; /. 1866, 7i4) ; in the biain
(Couerbe, 4. Ch. 56, 281; Fremy. i5W. [3] 11,
486; Beneke, Bied.Centr. 1881, 568)— the brain
of a boy 16 years old was found to contain 26-92 g.
oholesterin- 2-34 P.O., that of a woman 19 years
old, 26-79 g. = 2-12 p.o. (Beneke) ; in the yolk of
egg (Lecanu, /. Ph. 15, 1; Onblej.ibid. [B] 12,
12— four hen's eggs yielded 0-592 g., and four
newly hatched chickens 0'41 g. ffieneke); in
oxen bile (Hufner, J.pr. [2] 19, 305); in human
mUk to the amount of 0-0318 p.o. (Tolmatschefi,
Med.-Ghem. Unters. 1, 272); in cow's mUk
(Schmidt a. Miilheim, ArcMv f. d. ges. Physiol.
25, 384) ; in the spleen, and abundantly in the
excrements of the orocodUe (Marcet, A. Ch. [8]
59, 91) ; in guano (Hoppe-Seyler, J. 1863, 654);
in the corpus luteum of the cow (Lieben, Z.
4, 646); along with paracholesterin in the proto-
plasm of ethaMwm septicum (Beinke a. Bode-
wald, A. 207, 228) ; along with iso-eholesterin in
the grease of sheep's wool (Hartmann, Inatig.
Dissert. QotUngm, 1868 ; B. Schulze, Z. [2] 6,
453) ; and in certain morbid products of the
animal economy, ■ such as cerebral concretions,
scirrhous matter of the mesocolon, hydropic
liquid of the abdomen, ovaries, testicles, <&o. (Las-
saigne, A. Ch. 9, 324 ; O. Henry, J. CJdm. Med.
1, 280 ; Caventou, J. Ph. 11, 462 ; Lehmann,
Lehrb. d. Physiol. Chem. 2te Aufl. 1, 286).
The first exact analysis of cholesterin was
made by Chevreul, who assigned to it the for-
mula C2SH44O. Its metamorphoses have been
studied by Marchand {J. pr. 16, 37) ; Bedten-
bacher (A. 57, 145) ; Meissner a. Schwendler
(ibid. 59, 107, also J,pr. 39, 247); Zwenger {A.
66, 5 ; 69, 347) ; Heintz (P. 79, 524) ; Berthelot
(A. Ch. [3] 56, 61) ; andf by others, who will be
referred to in the course of this article.
Prepa/raticm. — 1. By crystallising biliary
calculi from boUing alcohol, to which a little
potash is added to dissolve any fatty acids that
may be present. — 2. By extracting brain sub-
stance with ether, and boiling the evaporated
extract with alcoholic potash. — 3.' From the
grease of sheep's wool by saponifying for 20
hours at 100° with alcoholic potash in a closed
stoneware bottle, evaporating the alcohol, taking
up with water and shaking with ether. The
residue from the evaporation of the ether con-
' sists of a mixture of cholesterin, iso-cholesterin,
and a nearly-related amorphous alcohol poorer
in carbon,' and these are best separated from
one another by conversion into their benzoic
ethers, by fusing the mixture of alcohols (2
parts) with benzoic anhydride (1 part) to abbut
180° for 48 hours. The resulting mass is rubbed
up with a little alcohol in a mortar, treated first
with a cold solution of N%CO„ and then with
warm water to extract the benzoic acid formed
^ This amorphous alcohol, which is poorer in carbon
than cholesterin, is v. sol. cold alcohol, ether, and acetone,
but it has not yet been obtained pure, in fact there is as
yet no guarantee that it is a chemically simple substanpe.
It has a weak, aromatic odour, and melts at a gentle heat.
It appears to be present in the fat, partly free and partly
combined with acids, chiefly oleic. The greater portion
of wool-fat consists of compound ethers, but a portion of
the alcohols — at least of the oholesterins — and also some-
times a portion of the acids are present in the free state.
The formation of potash soaps tu wool-fat is now readily
explained by the presence of free fatty acids on which the
KjCO, can act ; a portion of the compound ethers may,
however, be decomposed also (Schulse a. Vtieh,J.pr.li}
and the excess of anhydride, and then dried.
To_ the mixture cold ether is now added, in
which the benzoate of the amorphous alcohol is
readily soluble, those of cholesterin and iso-
cholesterin dissolving only slightly. The two
latter may then be separated by slow recrystal-
lisation from ether and elutriation, oholesterin
benzoate crystallising in plates, and iso-eholes-
terin benzoate in needles. The benzoates are
then separately saponified for their respective
cholesterins, which are reorystallised for further
purification (E. Schulze, J.pr. 7, 163). — 4. On
adding ether and HCl to fresh oxen bile, the
cholesterin is obtained in the ethereal layer
(Hiifner, J. pr. [2] 19, 305).
Properties.-^Monaiomia aleihol. Laminated
transparent crystals of CasHjiCaq (from a mix-
ture of alcohol (2 vols.) and ether (1 vol.)), which
give off their water at 100°. Plates (containing
aq) (from alcohol and ether). Anhydrous needles
(from chloroform). Tasteless and inodorous. In-
sol. water, v. s61. hot, si. sol. cold, alcohol, v. sol.
ether, chloroform, carbon bisulphide, oil of tur-
pentine, Boap water, and neutral fats, &a.
BeacUons. — (a) Sublimes at 200°, but decom-
poses at a higher temperature, (b) Besists the
action of cone, alkaline solutions, even at the
boiling temperature, but is decomposed by lime
at about &50°, with evolution of hydrogen and for-
mation of an amorphous body nearly insoluble in
alcohol, (c) For the action of halogens v. De-
rivatives, (d) Yields with cone. H2SO4 a. b. and
0. Cholestenlins (1). these) (Zwenger). (e) Yields
with cone. H3PO4 (o) and (;8) Cholesterones (3. v.).
CharaclerisUe tests. — (a) When a few
centigrammes are dissolved in chloroform and
the solution is shaken up with an equal volume
of KjSO^ (best of 1-76 S.G.), the chloroform
layer, at first yellow-brown, soon becomes blood-
red, and then cherry-red or purple, the colour
remaining for some hours if the solution is in a
closed bottle, i.e. if air be not admitted ; it then
becomes blue, green, and finally yeUow. The
sulphuric acid at the same time shows a fine
green fluorescence (Hesse, A. 211, 283 ; Beinke a.'
Bodewald, A. 207, 229 ; Salkowski, C. 0. 1873).
(b) When a small quantity is evaporated at a
gentle heat with a drop of nitric acid, a yellow
spot is left, which turns red when touched with
a drop of ammonia, and the red colour thus pro-
duced is hot essentially altered by subsequent
addition of fixed alkali, thus distinguishing this
from the corresponding reaction with uric acid
(SchiiJE, A. 115, 113). (c) When slowly evapo-
rated to dryness with 3 volsv cone. HCl or
H2SO4 and 1 vol. 'Befil^ solution, the particles re-
maining undissolved assume a violet-red colour,
changing to bluish-violet at a somewhat higher,
and dull-grey at a still higher, temperature.
This reaction, which is likewise produced with
AuClj, PtCl,, or KjCr^Oj + HCl, is not exhibited
by the colouring matter or any other constituent
of the bile (SohifE).
AppUcaUons. — Cholesterin possesses the pro-
perty of absorbing more than 100 p.c. of water
(Liebrich, of. C. S- I. 5, 578), a, point of great
therapeutic moment. The grease of sheep's
wool is now therefore being, purified in quantity,
and the manufactured product, which is termed
' lanolin,' used as a basis for ointments, &o.
l2
148
OHOLESTEKW.
Cholestoryl cMortde, OMH,sCa. [97°, Wa-
litzky]. [96°, Baymann]. Prepared by the action
of PGl, on cholesterin or its acetate. Small
scales, si. sol. alcohol,'y. sol. ether. Not decom-
posed by aqueous, but by boiling alcoholic potash
(Planer, A. 118, 25 ; Lindeumeyer, J. pr. 90,
321 ; Eayman, Bl. [2] 47, 898).
Cholesterin dibromide CjuH^OBrj. Prepared
by the action of bromine on cholesterin,- both
dissolved in CS^. White needles (from ether-
alcohol), si. sol. alcohol, T. sol. ether. Is recon-
T«rted to cholesterin by Ka amalgam (Wishcenus
a. Moldenhauer, A. 146, 175).
Cholesteryl chloro-dibromide Gj^HjsCl.IBrj,.
[128°]. Prepared by gradually adding Br to an
ethereal solution of cholesteryl chloride. White
powder or large colourless crystals (from CSj).
Sul. carbon bisulphide, chloroform, and ligroin
(B^yman).
Kitro-cholesterin [94°]. Bed-yellow mass,
insol. water, sol. NHjAq and K(Na)OHAq, v. sol.
alcohol, ether, chloroform, &e. (Beinitzer, M. 9,
. 421).
Di-nitro-cholesterin C2jH,2(NOj)20 or
CjsHjJNOj)^©. [121°]. Colourless needles (from
alcohol). V. sol. hot alcohol and ether (Preis a.
Bayman, B. 12, 224).
Hitro-cholesteryl chloride CjsH,j(NOj)Cl or
Cj5H„(NOj)01. [149°]. Colourless needles (from
alcohol) (P. a. B.).
Cholesteryl acetate CjjHjjO.CjHaO or
C2,H„O.C2H30. [92°, Lobisoh, B.5, 513] ; [113°,
Baymann, Bl. 47] [111°-112° uncor. (chol. from
gallstones), Jacobsen] ; [114'5° cor.] (from gall-
stones) (Beinitzer, M. 9, 428).
Preparation.— By heating cholesterin, also
sodium cholesterate, with acetic anhydride, or
with acetic acid or acetyl chloride. Needles
(from benzene). Trimorphous, the first modi-
fication being monosymmetric crystals, and the
second monosymmetric plates with rhombic
edges, while the third form has not yet been de-
fined. Shows curious changes of colour on soli-
difying after fusion, which changes are not yet
explained, but are apparently closely connected
with the separation — during fusion — and re-
solution of a substance whose nature is not
known (Leymann v. Beinitzer, loc. cit.).
Bromo-cholesteryl acetate C^^B^^Br^.C^'SsO^.
[118° cor. and 116° cor.] (Beinitzer, M. 9, 424).
Long glancing tables (from ether-alcohol).
Dimorphous, the first modification being mono-
symmetric tables [118°], and the second asym-
metric tables [116°]. Somewhat decomposed by
light (Beinitzer).
Cholesteryl butyxate CjjH„O.CiH,0. M. sol.
hot alcohol.
Chale8terylstearateC2gH„O.C,sH,sO.Needles,
b1. sol. cold ether, almost insol. alcohol (Ber-
thelot).
Cholesteryl benzoate O^sH^O.CjHsO or
C„H„0.C,H50. [150°-151° Schulze; 146-6° cor.
Beinitzer].
Preparation. — See separation of cholesterin
and isocholesterin (Schulze, J. pr.). Better, by
heating anhydrous cholesterin (10 pts.) with
benzoic anhydride (12 pts.) in an open flask to
150°-160° for H hours (Beinitzer, M. 9). Beau-
tiful small glancing tables (from ether) ; m. sol.
ether, si. sol. boiling alcohol (Berthelot, Schulze).
TrimorphouB, the first modification being tetra-
gonal crystals, the second forming rhombic
needles or small plates, and the third crystallisiu/:^
in thin broad plates. Exhibits on fusion colour
phenomena similar to those shown by the acetate,
but not quite the same (Beinitzer, foe. cit.).
Sodium cholesterate Cj^H^NaO. [150°].
Formation. — ^By the action of Na on a satu-
rated solution of cholesterin in petroleum. Silky
needles (from petroleum or chloroform). Slowly
decomposed by water, more quickly by alcohol
(Lindenmeyer, /. pr. 90, 321).
Cholesterylamine CajH^NH^. [104°] (Henry).
Small plates.
Cholesteryl-aniline CaHji.CjHsNH. [187°].
Preparation. — By heating cholesterin chlo-
ride and aniline to 180° for 6-12 hours ( Walitzky,
Chem. Sect. d. Euss.phys.-chem. Oes., Oct. 1878 ;
B. 11, 1937). Long rectangular plates (from
CSj) ; m. sol. ether and boiling alcohol, t. sol.
carbon bisulphide. Ppd. from ethereal sojlution
by mineral acids.
Salts.— The HjSO,, HNO„ and HCl salts
are crystalline.
Cholesteryl-jp-tolnidine OjsH4,NHC,H,. [172°].
Prepared at 150°-180°. Bectangular tables
(from ether). Sol. alcohol, ether, and carbon bi-
sulphide. Weak base (Walitzky).
Salts. — TheHNOj salt is much more stable
than those of HCl or BLjSO,.
Tri-oxy-cholesterin Cj^H^Oj. ■
' Preparation. — (a) By saponifying the di-
acetin (see below) with alcoholic potash, dissolv-
ing the residue in water and ppg. by an acid
(L^tschinoff, Chem. Sect. d. Buss, phys.-chem.
Ges., Oct. 1878 ; B.'ll, 1941).
(6) By oxidising a solution of cholesterin in
HOAc by KMnO,; this latteir method does not
yield it quite pure.
Properties. — Yellowish powder. Sol. alcohol,
ether, and KOHAq. Mol. w. not yet determined.
Besembles phenol in behaviour.
Di-acetyl derivative C^iKifiiCfifiX-
[77°].
Preparation. — Cholesterin acetate is oxidised
by KMnO, and the di-aoetin dissolved out of the
resulting mass by ether (Latschinoff).
Properties. — White hard powder, indistinctly
crystalline, obtained on adding water to the HOAo
solution. V. sol. glacial acetic acid, alcohol,
ether, benzene, &c., but not crystaUisable from
any one of these.
Cholesteriline a, b, and c C.^,™ or C^sH^
(Zwenger, A. 66, 5 ; 69, 347).
Preparation.— Bj acting with cone. H^SO, on
a slightly heated mixture of cholesterin and
dilute sulphuric acid.
Properties. — (a) [240°]. Amorphous. Insol.
water, almost insol. alcohol, v. si. sol. ether. (6)
[265°] shining scales. Insol. water, m. sol. hot
ether, (c) [127°]. Besinous. Insol. water, sol.
hot ether.
Walitzky's Cholestene Oj„H,j, obtained by
heating cholesterin with sodium to 150°-155°,
appears to be identical with c, also with the com-
pound obtained by acting on cholesterin with
HI (S.G. 1*5), or by heating it with soda-lime up
to 250°. Cholestene and the two last give, with
excess of Br, the same compound C5.H,,Br,
(Walitzky, C. iJ. 92, 195).
T. Weyl {Archiv f. Anat. wnd Physiol. 1,
182) has studied these compounds anew, and
CHOLESTERm.
149
considers that they agree with the formnla
(CjHsj.HjO. B'or the relations between oholes-
terin, cholalio acid, and the terpenes, see Lat-
sobinoff, Walitzky, and Weyl.
Cholesterones 0„H„ or CjsH„. When oholes-
terinis boiled with excess of cone, phosphoric acid
it forms two ooinpounda, a- and /3-cholesterone,
isomeric with each other, but differing in physi-
cal properties (Zwenger, A. 69, 347).
a-Chloresterone. [68°]. Eeotangular
prisms, y. sol. alcohol and ether, and distilling
without decomposition.
P-Oholesterone [175°]. Small silky
needles, almost insol. alcohol, si. sol. ether.
Cholesterio acid C,2H,gO,.
Formation, — By the oxidation of oholic acid
0MH„O,or(0aH„Oj)a;, byK,Cr.p, (10 parts) and
H2SO4 (16 partsj. The acid must ^e diluted with
at least three times its volume of water before
the oxidation, and the latter interrupted as soon
as the cholesteric acid is formed, otherwise it is
obtained mixed with pyro-cholesteric acid (see
below). Bedtenbaoher's cholesteric acid GieHjgOg
{A. 57, 160) is such a mixture. The filtered
solution must be concentrated at a low tempera-
ture, unless the H^SO^ is first neutralised. The
cholesterio acid crystallises, and is purified either
by washing with a little cold water or by recrys-
tallisation from ether (Tappeiner, A. 194, 211 ;
B. 12, 1627 ; LatsohinofE, B. 12, 1518).
Properties. — Tribasio acid. Needles (from
water and alcohol), long prisms (from ether con-
taining some water). V. sol. hot water. Not
volatile with steam. Slightly dextro-rotatory in
alcoholic solution. Gives no colouration with
sugar and E2SO4, and has not the toxic action
of cholic acid. Its power of crystallisation is
greatly diminished by the presence of small
quantities of the pyro-acid.
Salts. — The Ca and Ba salts are less sol.
hot than cold water. At 100° they generally go
into salts of pyro-cholesteric acid (Tappeiner).
A"'jBa„ A"'Ag3, A"'H;,Ag.
Fyro-cholesteric acid C„H,sOs. [108°].
Prt^aration. — (a) Best by heating a solution
of cholesteric acid in glycerin for 5 to 8 days at
198°, saponifying the glycerates, distilling off
small quantities of volatile acids, such as pro-
pionic, and extracting with ether (Tappeiner).
,(6) Also by boiling with EjSO, diluted with
3 vols, water, but in this case the decomposition
goes further.
Properties. — Gummy mass, sol. water.alcohol,
and ether.
Iso-cholesterin CjjHj.O. [138°-138-5°]. [o]i, in
ethereal solution + 60° (Schulze, J.pr. [2] 7, 163 ;
Schulze a. Urieh, J. Pr. [2] 9, 321 ; Schulze,
B. 12, 249).
Occurrence, — ^In the fat of sheep's wooL
For Preparation and separation from choles-
terin, see the latter.
Properties. — Flocks (from dilute alcoholic
solution), a jelly (from concentrated alcoholic
solution), fine transparent needles (from ether
or acetone). SI. sol. cold, v. soL hot, alcohol,
ether, and acetone, i.e. solubiUty is very much
the same as that of cholesterin. A mixture of
cholesterin and iso-cholesterin melts at a lower
temperature than either separately.
Beactums.—(a) The OHOlj and HjSO, test
gives only a very feeble colouration (Schulze,
J. pr. [2] 7, 163). (6) The HNO, and NH, test
gives the same colouration as cholesterin.
Iso-cholesterin derivatives.
Iso-eholesteryl chloride 0J3.tfi\.
Prepared by the action of PCI5 on iso-cholesterin.
Amorphous. V. sol. ether, si. sol. alcohol.
Acetyl derivative [below 100°]. Amor-
phous ; si. sol. alcohol.
Stearyl derivative [72°]. Fine white
needles (from ether). V. si. sol. alcohol.
Benzoyl derivative G,^Ji.C,'B.fi.
[190°-191°]. Fine needles (from ether). SI. sol.
alcoholj m. sol. acetone, v. sol. ether.
Phytosterin Cj.H„0,aq. [132-133°] (Hesse,
A. 192) ; [133°] (v. Lippmann, B. 20, 3201) ;
[133°] Paschkis.H. 8, 356; [132°], [135°], [133°],
and [136°], Jacobsen; [136-137°], Beneke;
[136-137°] Schulze a. Barbieri (from lupines),
J. pr. [2] 25, 159. [o]d (anhydrous in CHOI,)
= -34-2° (Hesse)
= -33-7° and -35-1° {v. Lippmann)
from -30-4 to -33-4 (Jacobsen)
-32-7° (Paschkis)
- 32-5° in ether (Lindenmeyer)
-36-4° (Schulze a. Barbieri).
Those who first isolated phytosterin considered
it to be cholesterin. The name phytosterin was
given to it by Hesse.
Occurrence.^ — In peas and olive oil (Beneke,
A. 122, 249; Knop, C. C. 1862,819); calabar
beans (Hesse, A. 192, 176) ; in the seeds and
cotyledons of the shoots of the yellow lupine,
* Lupinus luteus ' (Schulze a. Barbieri, J. pr. [2]
25, 159) ; in almonds; mustard seed ; Bockshorn
seed; in numerous fungi, e.g. Polyponis offici-
nalis (Schmieder, C. C. 86, 774) ; in , the seed
oil of rape, lentils, almond, cotton, earth nut or
pea nut, poppy, and cocoa (Salkowski, Z. f.
Anal. Ohem. 26, 557) ; together with cholesterin
in butter and cod-Uver oil (Salkowski) ; in hog's
beans and vetches (Jacobsen) ; in the juice oi
beet (v. Iiippmann, B. 20, 3201) ; in wheat gluten
(Bittnausen, J. pr. 85, 212 ; 88, 145) ; in maize
grains (Hoppe-Seyler, Krit. Zeit. 10, 32); in
barley fat (Stellwaag, Zeitschr. f. d. g. Bratiwes.
1886, 176 ; Chein. Zt., Chem. Bepert. 10, No. 23) ;
in the fat of meadow hay and of oat straw
(Eonig, Iiandw. Versuchstationen, 17, 3, 11);
in colchicum seeds (Paschkis, H. 8, 356) ; in the
oil of the seeds of Chaulmoogra {Gynocardia
odorata, Boxb.), of J^qairity (Abrus precatorvui.
Lam.), and in the fat of the leaves of Ery-
throxylwm hyperificifolmm Lam. (Heckel a.
Schlagdenhauffen, O. B. 102, 1037) ; probably
also in the animal body, possibly together with
cholesterin, as maybe deduced from older ob-
servations (Gmelin, JSandh. 4, 2092).
Preparation. — (o) From peas (Benek^, toe.
cit?).
(6) From calabar beans. These are extracted
with petroleum ether. When this is evaporated,
a fatty oil is left, out of which phytosterin crys-
tallises. It is separated from the oil by pressure,
purified by dissolving in ether with bone black,~
and recrystallised from alcohol (Hesse, il. 192,
176),
(c) From beans. The powdered beans are
extracted with alcohol, the alcohol distilled, and
the residue extracted with ether. This extract
* It is poBslble that in some of the oases here men*
tioned » oholesterin other than phjtosteiin is present.
X60
CHOLESTERIN.
18 saponified mtli 25 p.c. NaOH, and the layer
of fat separated froiti the deep-coloured motner
liquor. The fat, purified from glycerin, is then
extracted with ether, and the phytosterin ob-
tained from this ether extract (Jacobsen, IncMig.
Dissert. Konigsberg in Preussen, 1887).
(d) From the powdered seeds and shoots of
the yellow lupine (Schulze a. Barbieri, J. pr. [2]
25, 159). The finely powdered seeds and shoots
are extracted with ether, the extract distilled,
and the residule boiled for several hours with
alcoholic potash, using a reflux condenser. The
solution thus obtained is evaporated, the residue
rubbed up with water and shaken with ether
several times. The ether is then distilled ofi,
and the residue dissolved in the least possible
quantity of hot alcohol. On cooling, the phyto-
sterin crystallises out. It may then be purified
by conversion into the benzoate, re-saponifica-
tion of this with alcoholic potash, and re-crystal-
lisation from alcohol.
(e) Beinitzer recommends the following
method for the separation of cholesterin from
fats {M:. 7, 597). The juice — e.g. of carrots— is
ppd. with PbACj, the pp. dried, and — together
with the pressed vegetable — extracted by carbon
bisulphide. The residue after distillation of the
bisulphide is saponified vtith alcohoUc potash,
the alcohol, evaporated, the mass taken up with
water and ppd. by BaClj, and the washed and
vacuum-dried pp. extracted by acetone.
Properties. — Glittering plates of CajH^jOaq
(from alcohol), silky needles of O^jH^O (fromchlo-
rof orm, ether, and petroleum ether). Insol. water
or EOHAq, v. sol. hot alcohol, ether, and chloro-
form. A mixture of phytosterin (from lupines)
and cholesterin crystallises from alcohol in a
mass of small needles, i.e. in a form different
from that of either separately.
BeacU(ms.—(a) The CHOI, and H^SO^ test
gives exactly the same results as with cholesterin
and quebrachol (Hesse, A. 211, 283).
(6) Cautiously evaporatted with HCl and
FejCls, it gives a violet colour like ordinary cho-
lesterin.
Acetyl derivative C^aO(CjB.30) or
Ci,5H„0(C2H30). [120°, Hesse]. [126°, 120°,
118°, and 125° uncor., Jacobsen], Glancing
plates (from alcohol) (Hesse). Eesembles in its
properties the acetates of cupreol and quebra-
cho! (H.). Prismatic needles (from alcohol)
(Jacobsen). SI. sol. alcohol, v. sol. ether and
chloroform.
Benzoyl derivative [145-5°, 147°, 146°,
and 145° uncor., Jacobsen]. Thin glancing
rectangular plates (from ether), si. sol. alcohol,
m. sol. ether and chloroform. Gives the colour
reactions with OHClsandHjSOj and with FojClj,
but not with HNOj and NH, (Jacobsen).
Hydrocarotin OjaH^Oaq? [136-5°] [o]d (in
CHCy -36° (Amaud, C. B. 102, 1319; also
100, 751). [138-2°]. [o]„ (in CHOI.) -37-4 (Bei-
nitzer, M. 7, 579). This substance is probably
phytosterin, although Beinitzer considers that it
more nearly resembles liiebermann's cholestol
(oiyquinoterpene) 0„H„Oj? [139°], which latter,
in its turn, Hesse looks on as being probably
almost pure cinchol.
Occurrence and preparation. — In and from
carrots.
Properties.— S^&ien (containing aq) (from
alcohol), anhydrous needles (from the other sol-
vents). Insol. water, si. sol. cold, v. sol. hot
alcohol, ether, chloroform, Ac. Frohde (J.pr.
102,424) declared hydrocarotin to be cholesterin,
which Husemann repudiated. Amaud, how-
ever, finds that Husemann's hydrocarotin (A.
117, 200) is phytosterin mixed with some caro-
tene.
Beactiom.— Gives the cholesterin reactions
with
(a) CHClj and HjSO,
■■■ HNO, andNH,
HOI and FejOlj
Liebermann's with (Ao)20 and HjSO, (B.
18, 1803).
Acetyl derivatives. [128-2°]. Colourless
crystalline scales (from ether-alcohol). SI. sol.
hot alcohol.
Benzoyl derivative^ [145°]. Dimetrio
glancing tables, when slowly crystallised from
ether. V. sol. ether. {Of. phytosterin.)
Para-cholesterin CjjHMOaq. [134°-134-5°
uncor., B. a. E.]. [o]b (in CHOla) -28-88 and
-27-24 for different strengths (B. a. B.).
Occurrence. — In the protoplasm of EthaUum
Prepa/ration. — EthaU/u/msepticum is digested
with alcohol and the whole mass evaporated to
dryness and extracted with ether. From this
the p-oholesterin crystallises out, and is purified
by crystallisation from hot alcohol, the chole-
sterin which is also present remaining in the
alcoholic mother liquor (Beinke a. Bodewald, A.
207, 229^).
Properties. — Plates (containing aq) (from
alcohol), silky glancing needles (from ether and
chloroform). V. sol. hot alcohol, ether, and
chloroform, m. sol. cold alcohol. Gives up its
water over HjSO,. In general properties it
agrees with cholesterin, iso-cholesterin, and
Beneke's cholesterin from peas, in chemical
properties it resembles Hesse's phytosterin.
Beactions. — The CHCla and HjSOj test gives
much the same colouration as Schulze's iso-cho-
lesterin. At first both the chloroform and sul-
phuric acid layers are coloured yellowish-brown,
the latter with green fluorescence. On prolonged
standing the cMorof orm becomes blue and then
violet, while the acid becomes a deeper brown
and the fluorescence increases (B. a. B.).
Benzoyl derivative. [127°-128° un-
cor.]. Thin glancing rectangular plates (from
ether). V. sol. ether and chloroform, m. sol.
hot, si. sol. cold, alcohol (B. a. B.).
Cauloste'rin CjsH„Oaq. [158°-159°]. [o]d (in
chloroform) -49-6°.
Occurrence and preparation. — In the root
and growing parts (radicles) of the shoots of the
yellow lupine, ' lupinus luteus,' from which it is
extracted in the same way as the phytosterin
from the seeds (Schulze a. Barbieri, J.pr. [2]
25, 159].
Beaction.—a. With CHOlj and H^SOj it be-
haves in the same way as cholesterin and phy-
tosterin.
Benzoyl derwaU/ae. — Thin glancing plates
(from ether).
It will be seen from the foregoing description
of the cholestering that much investigation ia
OHOLIO ACID.
181
still required to determine irhether they are
homologues or isomerides.
1. The various animal oholesterins (from
biliary caloali, brains, &a.) have hitherto been
considered to be one and the same substance,
since preparations from many different sources
have been found to possess the same melting-
point, and also because of the homogeneity of
the benzoic ether (Sohulze a. Barbieri) ; but the
point still requires further proof (Eeinitzer, if. 9).
It is not impossible that different cholesterins
should occur in different animal organs, just as
different varieties were found by Schulze and
Barbieri in different parts of the yellow lupine
(c/. Hesse, A. 192). For the probable relation
of the cholesterins to the terpenes and camphors
V. WaUtzky (B. 9, 1310), Latschinoff (B. 12,
1518), Liebermann (B. 17, 871; 18, 1803), and
Weyl (ArchAo f. Anat. u. Physiol. 1, 182, B.
19, Bef. 618). The analogy of cholesterin to
camphor is confirmed by the absence of any
action when it is treated with hydrozylamine
(Baymau, Bl. 47).
2. Iso-cholesterin is apparently a simple
substance.
3. Para-cholesterin differs little from phyto-
sterin, excepting in specific rotatory power, and
requires to be further examined.
4. With regard to vegetable cholesterins,
Hoppe-Seyler (Handb. d. physiol. u. pathol.
Chem. Analyse, 4te Aufl. p. 110) surmised that
cholesterin was probably a constant constituent
of meristematio plant cells. Since they are so
widely distributed among plants the cholesterins,
according to Sohulze and Barbieri, are to be
looked upon as invariable constituents of the
protoplasm. These last-named authors found
oholesterins in very considerable quantity in the
etiolated shoots, but only in very small quantity
in the green plants of the yellow lupine, and
hence they concluded that vegetable cholesterins,
especially caulosterin, are decomposition pro-
ducts of albuminous compounds in the life
process of the cells, a point already suggested
by Hoppe-Seyler {Handb. 1, 81). Hesse considers
that, because normal cholesterin possesses a
stronger rotatory power than phytosterin, the
former compound must be the next homologue
to CjgH^O i.e. O25H42O, the formula proposed by
Walitzky, and also at one time by Bertheloi
{(imelin,Handb.d. Org. Chem. 4, 2093), although
the latter returned later on to the one usually
accepted, viz. CjsH^O; Beinke and Bod'ewald,
however, think this insufficient to overthrow
the theory of the isomerism of the cholesterins.
Cupreol, oinchol, and quebraohol (all of them
C2,H,40,H20), and also Liebermann's cholestol
(which is believed by Hesse to be nearly pure
cinchol), aU belong to this class of cholesterins.
Beinitzer is of opinion that cynancocerin, cynan-
chin, echicerin, and echitine (Hesse, A. 192, 182),
aspidol (Baccomo, Ceniralbl. 87, 1357), ambrain,
castorin, &e., must also be included, and that
the cholesterins will ultimately be found to be
divisible into two homologous- groups, dextro-
and Ifflvo-rotatory. For the latest discussion on
this point, v. Beinitzer (M. 9). G. M.
CHOLESISOFHANE v. Di-methyl-PsniBiisiio
Law.
CHOLIC ACID OmH^Os i.e.
Ci»,H„(CH.OH)(CHj.OH)j,COi,H (?). Cholalie
acid. [195°]. S. (of anhydrous crystals) 133
at 100° ; -025 at 15°.
FormaUon. — By the hydrolytia action of
alkalis on glycooholio and taurooholic acids,
which occur in the bile (Demarpay, A. Oh. [2]
67, 177 ; Theyer a. Schlosser, A. 48, 77 ; 50,
285; Strecker,.^. 65,'9; 67,1; 70,161,166).
Preparation. — Glycooholio acid (50 grms.) ia
boiled for 16 hours with water (6 litres) and
baryta (200 grms.). The liquid is filtered hot
and, when cold, HOI added. A sandy pp. of
oholic acid falls. Crystallised from alcohol.
The yield is 80 p.o. (Hartmann, J, pr. [2] 19,
307 ; cf. Tappeiner, A. 194, 213).
Properties. — Crystallises from hot water in
anhydrous microscopic crystals, from cold solu-
tions, e.g. very dilute acetic acid, in trimetric
tables (containing aq). The acid combines with
methyl-, ethyl-, propyl-, and ethylene-aloohols
and with mustard oils, but not with acetone.
The hydrated and anhydrous acid and its
various alooholates aU crystallise in the tri-
metric system, the axis-ratio a:c remains con-
stant whilst bie varies in the different alooho-
lates. Gives a blood-red colour with cane sugar
and H2SO4 (Fettenkofer's test, v. Biue).
Beactions. — 1. By gentle oxidation with
acetic acid and CrO, it yields dehydrocholic
acid CjjHjjO,, probably Cj„H„(CO)(CHO)jCOjH;
by more vigorous oxidation with KjCr^O, and
H2SO4, bilianic acid CjtHg^Og is formed (but no
oholanic acid) {of. Destrem, C. B. 87, 880 ; Cldve,
0. B. 91, 1073). — 2. By putrefactive fermenta-
tion it is reduced to desoxycholic acid O^tH^gO,.
The latter acid probably accompanies oholic
and choleic acids in saponified oz-gaU. — 3. Com-
bines with iodine and HI or other metallic
iodides to form unstable blue compounds
(A'H)4MIs which greatly resemble iodide of
starch in properties. — (A'H)4Hl5 icaq : formed by
adding iodine and HI to an alcoholic solution of
choUo acid. — (A'H)4Kl5 x&q : formed by adding
iodine and KI to an alcoholic solution of cholic
acid. Small bronzy needles, which suspended
in water form an indigo-blue liquid. Beadily
decomposed into its constituents by heat, great
dilution with water, alkalis, &o. — (A'H)sBaI,„ a;aq:
like the preceding compounds (Mylius, B. 20,
683).
Mono-aeetyl derivative Cj4Hs8(OAo)04;
formed by passing HCl gas through an acetic
aoid solution of cholic acid. Amorphous powder.'
V. e. sol. alcohol, ether, benzene, &o.
Di-acetyl derivative Oj4H5j(OAo)20j :
formed by allowing cholic aoid to stand with
cold acetic anhydride till it dissolves. White '
granular crystalline powder. V. sol. alcohol,
ether, benzene, &a., insol. water. Bitter taste.
Its Ba salt is insol. water (Latschinoff, Bl. [2]
33, 297 ; B. 18, 3039 ; 20, 1043; Mylius, B. 19,
369, 2000; 20, 1968). Schotten (H. 11, 268)
denies the existence of acetyl derivatives of
cholic acid.
Amide G^^^fii^'B.^. Formed by heating
the acid with alcoholic NH3 at 250°. Small
crystals (containing 3aq). SI. sol. water. The
hydrated compound melts at [125°-130°]. The
anhydrous compound melts slowly from [130°-
140°], again solidifies at about 180° to a colour-
less crystalline mass, which again melts at
[c. 228°^; if this crystaUiue mass ia cr^atftllisecl
163
OHOLIO Aom.
from alcohol, nothing ia obtained but the ordi-
nary amide.
Di-methyl-amide CiHH„0,.NMej. [171°].
Formed by heating the acid with aqaeons di-
methylamine at 250°.
Anhydrides, — ^By heating cholio acid under
various conditions mixtures of various anhy-
drides have been obtained, none of which have
been isolated in a pure state (MyUas, B. 20,
1968).
Ethyl ether O^iU^^tO^. [147°].
Preparation. — Gholio acid (20 pts.) is dis-
solved in dilute (90 p.c.) alcohol (140 'pts.). and
the solution saturated, in the cold, with dry
ECl. An equal volume of alcohol is at once
added and every 100 c.c. of the Uqoid poured in
a thin stream into a litre of water. After a few
days, needles of the ether appear (Tappeiner ;
Eartmann).
Lehydrocholio acid OjjEj^Oj probably
Oj„B„(CO)(CEO)jOOsB. [232°] (M.). [228° un-
oor.] (L.). Formed by slowly adding a 10 p.c.
solution of CrO, (9 pts.) in acetic acid, to a 10 p.c.
solution of oholio acid (10 pts.) in acetic acid.
Anhydrous needles. By further oxidation with
K^Cr^O, and EjSO, it is converted into biliauic
acid 0„E„Os i.e. C,„E3,(C0)2(C0jB),. It does
not give Pettenkofer's bile reaction.
2'ri-oa;i»jtC24Es4(NOE)j02: formed by the
action of a cold solution of hydroxylamine upon
sodium dehydrocholate. Colourless 'microscopic
tables. SI. sol. hot alcohol, nearly insol. water
and ether. Stable in alkaline solution, but
resolved into its components by acids (Latschi-
noff, B. 18, 3045; Mylius, B. 19, 2005; 20,
1979).
Phenyl - mercaptide 02,H3404(SCaE5)2 :
[o. 220°] ; colourless glistening needles ; si. sol.
water. Formed by passing HCl through a cold
solution of the acid in phenyl-mercaptan. The
sodium salt forma fine needles, insol. water.
Phenyl-mercaptide-phenyl-hydr aside
C23H,a(SCsE5)2(NjECsHs)jCOjH : separates in
colourless needles on warming an acetic acid
solution of the phenyl-meircaptide with phenyl-
hydrazine (Mylius, B. 20, 1979).
Desozy-choUc acid (probably identical with
the so-called ' hyd/rated choleic acid' of Latschi-
nofl) 0«E„04(M.) or Cj^E^AHaq (L.). [135°-
140°] (L.) ; [160°-170°] (M.). Large dimetrio
crystals, a:a:c = 1:1:2-4828 (L.). White needles,
V. sol. alcohol, si. sol. acetic acid (M.), Occurs,
together with cholic and choleic acids, in sapo-
nified ox-gall (L.). Formed by putrefactive
fermentation of cholio acid (M.). According to
L. it is formed in small quantity by boiling
choleic acid with acetic acid, but M. was unable
tp effect this conversion. By gentle oxidation
with CrOg and acetic acid it is converted into
dehydrocholeic acid; by more vigorous oxidation
with K,CrjO, and EjSO, into cholanio acid (L.)
(LatBchinofl, B. 18, 3041 ; 20, 1043 ; Mylius, B.
19, 373 ; 20, 1968).
The observations marked (Ii.) refer to Lat-
schinoff's hydrated choleic acid, those marked
(M.) relate to the desoxycholio acid of Mylius.
CHOLIN£ V. Neukine.
CHOLOlBAinC ACID C^^E^O,, i.e.
C2„B8jO(OOjB)j (?). Cholecampkoric acid. S.
•015 at 18°; -18 at 100°. [o]d57°56'. Formed,
together with pseudo-choloidamo acid, by boil-
ing cholanio acid (1 g.) with HNO, (30 o.e. oi
S.&. 1'28) for several hours. Formed also by
the action of ENO, on bile (Theyer a. Schlosser,
A. 50, 243) or ohoUc ^cid (Bedtenbacher, A. 57,
145; Tappeiner, A. 194, 239; OlSve, Bl. [2] 38,
135).
Salts . — ^A'Agj 4aq : gelatinous pp. — A'^jPb, :
amorphous pp. — ^A'2Ba5 20aq: thick prismatic
crystals, S. (at 18°) about 20 (LatschinofE, B.
13, 1052; 19, 1521).
PseMio-choloidanic acid 05pH„02,(?). Formed,
together with choloidanic acid, by boiling oho-
lanic acid (1 g.) with HNOj (30 c.c. of S.G. 1-28)
for several hours. Microscopic needles.
Salts. — A"»B4Ba2 20aq: flat needles.—
A'^'Agj : amorphous pp.
Ethyl derivative Os„E,„(0-iE5)402,: [247°].
Obtained by the action of EtI upon the lead
salt. Needles. Y. sol. alcohol, less in ether. —
C,gHet|Ft402iBa2 2aq : prisms.
Methyl derivative ''0j„Ej|,(CB3)402, 1
[194°-196°]; needles.
Neutral methyl ether C5i|H|;5(CBj)502, :
[128°]. Obtained by the action of ethyl iodide
upon the silver salt. Flat needles (from alcohol)
(Latschinoff, B. 19, 1521; cf. Cldve, Bl. [2] 38,
135).
CHOITDBIIir V. Pboteidb, appendix G.
CHBOUATES, Salts of GhromAo- Add; v.
Chbomiom, Acms as, p. 154.
CHBOMS AIiTTM
Gr23S04.Kj[or(NB4)JS04.24B20 v. Alums, also
Sulphates of Chrommm under SuiiFeates.
CHBOMIC AGIS BjGrOt; v. Ghbomiuu,
ACIDS OP, p. 154.
CHBOMIC ANHTSBIOE CrO,; v. Chromium,
OXIDES OF, p. 164.
CHEOMITES, Salts of the form MCCrjO,;
V. Ghbomium, acids or, p. 158.
CHEOMITIM Or. At. w. 52-45., Mol. w.
unknown. [Above M. P. of Pt which is about
2500°] (Deville, A.Ch. [3] 46, 182). S.G. 6-5-6-8
(Wohler, A. Ill, 230 ; Loughlin, Am. 8. [2]
45, 131 ; Bammelsberg, Handbuch d. krystal-
log. u. physikal. Chemie, part 1 [1881]). S.B.
(22°-50°) -0998 (uncertain) (Kopp, T. 155, 71).
S.V.S. about 7-8.
Occurrence. — Never free : chiefly as oxide in
combination with FeO as chrome-ironstone,
FeO.CrjOa, with CrgO, more or less replaced by
FcjOg and Mfi,, and FeO by MgO. Also as basic
chromate of lead, as chromic oxide, <fec. The
ores of Or are not very widely distributed. Chro-
mium was discovered by Vauquelin in 1797 ;
the name was given (xpSjua) because of the num-
ber of compounds of different colours obtained
from the metal.
Preparation. — Chrome ironstone is separated
from gangue, finely powdered, washed, mixed
with CaO and KBO, dried at 150°, and heated
to bright redness in contact with air, the mass
being constantly stirred ; after cooling, the
KjOrO, formed is dissolved out in a little warm
E2O, enough oouc. E2SO4 to convert all the
K2CrO, into KfiijO, is added, and the K2Cr20,
which separates is re-crystallised from hot BjO.
The KjCrjO, is heated with S, or starch, or
NB4CI, and the product washed with BjO, in
which the CrjO, formed remains undissolved
{v. Chromic oxide, p. 164). CrjOj is then mixed
with rather less charcoal than ia theoretically
OHKOMIUM.
163
required for oomplete rednotion, and heated to a
very high temperature in a lime oruoible. Or,
OtjOj is mixed with charcoal, and heated in 01
whereby CrCl, (q.v.) is obtained; the OrOlj is
then heated to bright redness, and H carrying
with it Ha vapour is passed over it; monometrio
crystals of Or are thus obtained (Fremy, C. B.
44, 632). Wohler {A. Ill, 230) mixes 1 part
violet OrCl, with 2 parts of a fused and powdered
mixture of 7 parts NaCl and 9 parts KCl, presses
the mixture firmly into a oruoible, and places
2 parts granulated Zn over it, and more NaCl
and EGl over this again; he gradually heats
until the mass is melted. As soon as the Zn boils,
and the flame of burning Zn is seen on removing
the crucible, the temperature is decreased, and
the mass is kept just melted for 10 minutes.
The whole is then allowed to cool, the crucible
being shaken once or twice ; the crucible is
broken, the zino regulus dissolved in dilute
HNOjAq, the metallic Cr then boiled once with
HNOjAq, washed, and dried. Zettnow prepares
CrCl, solution by reducing K^CrjO, in HOlAq by
G^HgO, adds KOI, evaporates to dryness, and re-
duces by Zn as already described (P. 143, 477).
According to Bunsen (P. 91, 619) Or may be ob-
tained in lustrous plates by electrolysing an acid
solution of OrClj containing OrOl,. Vincent
(P. M. [4] 24, 328) and Eoussin (J. Ph. [4] 3,
413) form an amalgam of Or, by acting oh solu-
tion of a chromic salt by Na amalgam, and heat
this in H or vapour of rock-oil.
Properties. — Descriptions of properties of Cr
vary considerably. The metal obtained by re-
ducing CrOl, by Na vapour, or by reducing
OrA by 0, is described (Fremy, O. B. 44, 632)
as unchanged by heating in air, in aqua regia or
KFAq, or by fusing with KOH or ENO,. The
metal obtained by electrolysis (Bunsen, P. 91,
619), or by reducing CrOlj by Zn (Wohler, A.
Ill, 230), is oxidised by molten KNOj or KOlO,,
and is dissolved in hot dilute HOlAq or H^SOtAq.
Berzelius {A. 49, 247) supposed that Or existed in
two distinct forms. The metal insoluble in aqua
r^ia probably contained Si derived from the
vessels. According to Bunsen and Wohler, Oris
a greyish-white powder, consisting of small, lus-
trous, very hard, brittle, rhombohedral crystals
(diMetric octahedra, Bolley, G. J. 13, 333) ; only
superficially oxidised, unless in very fine powder,
by heating in air; slowly oxidised by heating
to redness in steam ; burns brightly when heated
in an alcohol flame fed with O; oxidised by
molten EOlO, or END,, but not by molten
NajCOs ; dilute HOlAq, or hot dilute HjSOiAq,
dissolves it readily with evolution of H; scarcely
acted on by hot cone. HKO,Aq ; bums in 01 gas
forming violet CrOl,. Cr is less fusible than Pt
(Deville, A. Oh. [3] 46, 182). It is not magnetic
(Wohler, A. Ill, 230) ; slightly magnetic (Fara-
day).
The atomic weight of Cr has been determined
(1) by analysing and determining V.D. of OrOjOL,
and OrCla; (2) by measuring the S.H. of Or;
(3) by analyses, and comparison with other analo-
gous compounds, of OrCl, (PSligot, A. Ch. [3] 12,
530) ; AgjOrO, and AgjOrjO, (Berlin, 4. 56, 207) ;
Cr,(NH,)j(SOj4.24H20 (Moberg, J.yr. 43, 114) ;
CrCl, (Siewert, J. 1861. 241) ; by synthesis of
BaOrO, from BaOlz (Wildenstein, J.pr. 59, 27) ;
by oxidising FeClgAq by EaCrA and by EClO,,
and by oxidising As^OaAq by E^CrjO, (Eessler,
P. 95, 210) ; (4) by comparing ohromates with
isomorphous manganates and tellurates. The
atom of Cr is trivalent in the gaseous jnolecule
CrOlj (Scott, Pr. E. 14, 410) (v. Chromium hexa-
FLUOMDE, under CnaoMinM, PLtroniDBS ov, p. 162).
Chromium is both metallic and non-me-
tallic; Cr replaces the H of most acids form-
ing two series of salts, the simplest f ormulee for
which are CrXj and CrX„ respectively, where
X= a, &c., NO, &o.,^&o., ^« &c.; the
chromous salts, OrX,, are very unstable, and are
easily oxidised to chromic salts, CrX,. Many
basic chromic salts are known. The oxide CrjO,
is basic towards acids, and at the same time ex-
hibits feebly acidic properties ; OrOj seems to be
a neutral oxide and not to form salts either by
the action of acids or alkalis ; CrO, is distinctly
an anhydride. CrOjAq behaves as a dibasic acid,
forming a series of salts MjCrO,, the acid HjCrO,
has also been obtained. Although no salts of
the form MHOrO, are known as definite solids,
yet the thermal reactions of CrO.,Aq point to the
formation of these salts ; thus (Th. 1, 254)
w [CrO'Aq, n NaOHAq]
1 13,134
2 24,720
4 25,164.
By the action of acids on M.fivO„ dichromates,
MjCrjO,, are formed : a few tri- and tetra- ohro-
mates, M20r,0„ and M20r4O,„ are known. CrO,
also reacts with strong acids to form chroniio
salts and O ; it combines directly with a few an-
hydrides, e.g. with SO,. Chromic oxide, CrjO,,
reacts towards acids as a salt-forming oxide, but
at the same time it combines with some of the
more positive metallic oxides, e.g. with OaO,
MnO, ZnO. Several hydroxides of Cr, or perhaps
rather hydrated oxides, are known, derived from
the oxide Or^O,, and the lower oxide CrO which
has not itself been obtained free from Cr^O, ;
these hydrates are salt-forming in their reactions
with acids. The pps. produced by adding
EOHAq or NaOHAq to solutions of chromio
salts always contain potash or soda which can-
not be removed by washing with hot water.
CrjS, exhibits slight salt-forming properties in
its reactions towards sulphides of more positive
metals ; no hydrosulphide of Or is known. Chro-
mium is closely related to Mo, W, and U ; less
closely to S, Se, and Te ; it also shows distinct
relations to Al, Mn, and Fe (v. Chbomiies;
Cebomium oboup op elements ; also Chromium,
SAI.IS ov ; Ohbomates ; and the arts, on Htdboz-
IDES, Oxides, Chlorides, &c. oe Chbomium).
BeacUons. — 1. Decomposes steam at bright
red heat. — 2. Dissolves in hydrochlorie and suU
phurio adds, forming salts and H. — ^3. Oxidised
by molten potassium nitrate or chlorate,— i.
Bums when heated in chlorine, forming CrOI,.
5. Is oxidised by strongly heating in oxygen. — 6.
Forms OrN by heating in nitrogen, and CrjS, by
heating with sulphur.
GombinaUcms. — Most of the compounds of Cr
are obtained directly or indirectly from the oxides.
The metal combines directly with 01, N, 0, and
S. Compounds of Cr with each of the non-
metals, except H, B, Si, and Te, are known;
alloys with Al, Fe, and Hg, have been prepare^
154
OHEOMTOM, ACIDS OF.
{v. the various binary oomponudai oi Cr, also
Chromium, aujots or).
Estimation. — Chiomium may be estimated
in the form of oxide Cr^O,, after ppn. by
NH3Aq from a warm solution. Cliromates are
usually estimated as BaOrO,, or tbey may be
ppd. by HgNOjAq, and the HgjCrO^ heated
until only Cr^Oa remains ; or the ohromate may
be reduced, by alcohol, to a chromic salt, and
■ the Cr determined by ppn. with NHjAq &o. Cr
may be separated fiom many heavy metals by
ppg. these metals as sulphides, by H^S ; Ba and
gr are best separated by ppn. with H^SOfAq;
separation from Ca, Mg, and Fe, is effected by
ppg. Orfi,.xH.jO by NHjAq, collecting, drying,
and fusing with KNO, and KjCOj until all the
Cr ezists as KfizO,, dissolving in water and
ppg. as HgjCrO, or BaCrO^. If alumina is pre-
sent, it is ppd. from the solution containing
K^OrOj by digesting with ammonium carbonate.
Cr^OjicHjO is ppd. by digesting solutions of
chromic salts witii excess of BaCO, ; under the
same conditions salts of Ni, Co, Mn, and Zn, are
not ppd.
Chroniium, acids of, and their salts (comp.
arts. Acids; Aoids, basicity of; Hydboxides),
Chromic acid HjOrO, is said to have been ob-
tained in definite form, by the action of HjO
on the anhydride CrOj (v. infra, Chkomio acid).
This acid forms a series of chromates, M2Cr04,
isom,orphous with M^SO,. H^CrOiAq reacts as
a dibasic acid (v. imfra, Chbomio acid); no
salts of the form MHCrO,, but only the salts
MjCrOj, have been obtained by neutrahsing
the acid by alkalis ; when acids react with
chromates of monovalent metals MjCrO,, two
formula-weights of the chromate usually re-
act with one formula- weight of a dibasic acid
{e.g. HjSb^), half of M is removed, and a di-
ch^omate, MJCifl, — similar to the disulphates
MjSjO, — is produced. Several trich/romates
MjCrjOjo, and tetrachromates MfiTfli,, are also
known ; these salts are probably best regarded
as derived from MjCrjO, and MjCrO^, and from
2MjCr20„ respectively, by the removal of half
the total M and condensation of the residues.
The following formula express this view of
the constitution of the di-, tri-, and tetra-,
chromates :
(1) Ghronde add, Cr02(OH)2 ;
(2) Chromates, GiO^iOU)^;
(3) Dioha-omates, OM.OrOj.O.CrOj.OM ;
(A) Triohromates, OM.CrOj.O.CrOj.O.Cr02.0M ;
(6) Tetrachromates,
OM.CrOj.0.CrO2.6.0rOj.O.CrO2.OM.
These various series of salts may also be regarded
as direct compounds of metallic oxide with CrO,
(MjO.CrO,; Mj0.2CrO,; MjO.SCrOj; Mj0.4CrOs).
Besides these salts, several basic chromates are
known (v. mfra). Chromic acid, H^CrO,, being
dibasic, and forming M^CrO^ analogous with
MjSO^is probably a dihydroxyl acid, CiO^iOE)^.
If this is so we should expect that each OH
would be replaceable by CI ; the first compound
thus produced, CrO2.Cl.OH, ought to be a mono-
basic acid (analogous with SO2.CI.OH); this
compound is not itself known, but several
salts derived from it have been prepared, e.^.
CrO2.Cl.OK {v. imfra, under Chromates). Fluo-,
bromo-, and iodo-, chromates, Cr02.X.0M (where
X = F, &e., and M = alkali metal), are also mown.
Salts of the hypothetical amido-chromie acid
(CrOj.NHj.OM) are known; and it is probable
th&t nitro-derwaiives of KjCr^O, alfid KjCrjOij,, re-
spectively, have been obtained, viz. Cr20j,N02.0K
and CrjOj.NOj.OK (v. Potassmm dichromate,
under Siohromates). Cxjd, reacts towards acids
as a salt-forming or positive oxide ; no acid
corresponding to this oxide is known ; the oxide
is itself insoluble in HjO. Salts MCCr^Oa,
where M= Zn, Mn, Pe, Ac, have, however, been
prepared, by fusing MO and Cr^O, with BjOj, &o. ;
these maybe regarded as derivatives of the hypo-
thetical chromous acid H2Cr204 (v. Chromitea,
p. 158). The sulphide Cr^Sa, corresponding
to Cr^O,, also reacts as a feebly salt-forming
compound towards more positive sulphides (v.
CHROMinM, THIOAOID OF, p. 168).
Ckromic acid HjCrO,. Said to be obtained
as small red crystals by adding a little H^O to
excess of pure OrOj, keeping the solution for
some hours at 90°, decanting and cooling to 0°
(Moissan, A. Ch. [6] 6, 568). But Miss Field has
shown that the crystals thus obtained are CrO, ;
the solution, however, probably contains HjCrOj
and HjOrjO, (O. J. 61, 405 [1892]). The
thermal values of the reaction between NaOHAq
and HjCrOfAq show that this acid is dibasic;
salts of the form MHCrO^ appear not to exist as
solids ; if enough alkali is added to saturate
half the H2Cr04 in solution, and the liquid is
evaporated, the salt M2Cr20, is obtained — pro-
bably 2MHCr04 is formed and decomposed to
MjCrjO, and Hfi. If HjCrOjAq is added to
solution of MjCrO^, Hfitfi, is obtained on
evaporation. The thermal data (Th. 1, 255)
show (1) the dibasicity of the acid, and (2) the
action of excess of acid on the normal salts :
the corresponding data for H2S04Aq are given ;
addition of HjSOjAq to KjSO^Aq produces
KHSO^Aq :— 1
n [wNaOHAq, CrO'Aq] m [wiCrO^Aq, 2NaOHAq]
1 13,134 i 12,582
2 24,720 1 24,720
4 25,164 2 , 26,268
re[reNaOHAq,SO'Aq] m [mSO'Aq, 2NaOHAq]
1 14,754 I 15,689
2 31,378 1 31,378
4 31,368 2 29,508
Chromates. (Di-,tri-,tetra-,chromates.)
MjCrOf or M'iCr04 ; also basic and double salts.
Chromates are mostly yellow or red ; the salts
of the alkali metals, and of Ca, Mg, and Sr, are
e. sol. water, the others are generally insol. or
b1. sol. They are formed by the action of bases
on H2Cr04Aq; by fusing Cr^Os with alkali in
presence of air; or by double decomposition
from the alkali salts. Neutral MjCrOjAq
(M = alkali metal) goes red on addition of a
mineral acid from formation of M2Cr20,Aq, on
adding alkali the yellow colour returns. Chro-
mates are easily reduced to 0120, or salts of this
oxide,; e.g. boiling HClAq produces CrCljAq,
and chloride of the metal, H2S04Aq produces
Cr23S04Aq. Chromates of the less positive
metals give OrjOj when strongly heated; MjCrjO,
(M = alkali metal) give Cr20j, O, and M2CrO,.
Insoluble chromates yield alkali chromates by '
fusion with KOH or NaOH. Heated with NaCl
and cone. HjSO,, chromates give CrO^Glj. Solu-
tions of chromates have a metallic taste, and are
poisonous.
0HROMATE8.
16S
Almninium, chromate. — The basic salt
Al,3CrO,.2AlA-21HjO( = AlA.CrO<.7H20) is a
floceulentyellowpp.obtained by adding KjCrO^Aq
to alum solution, or by evaporating Alfi,.xBifi
in CrOsAq (Fairrie, C. /. 4, 300 ; Mans, P. 11, 81 ;
Elliot a. Storer, P. Am. A. 5, 192).
Ammonium chromate. — (NHJjCrO,. Citron-
yellow needles ; e. sol. water ; gives off NHj in
air; on heating leaves CrjOj. Obtained by
slowly adding CrOjOlj to excess of NH,Aq, and
evaporating below 60°; also by BaCrO.
+ {NHJjSOjAq, and by CrOjAq + NH,Aq (Darly,
A. 65, 2041) (o. Di-, Tri-, and Hexa-ohromates).
Baritim chromate BaCrO,. Yellow, crys-
talline powder ; obtained by KjCrO^Aq + BaCljAq ;
S.a. 3-9 ; also by fusing 1 pt. KjCrO, with 1 pt.
NajCrO, and 2 pts. BaOl^, and cooling slowly ;
S.G. 4-6 (Bourgeois, Bl. [2] 31, 243). . Insol.
HjO; sol. HClAq, or HNOjAq, and reppd. by
KH,Aq. Decomposed by alkali carbonates and
sulphates (Bose, P. 95, 426) (v. Bichromates).
Beryllmm chromate. — ^Basio salt
Be0rO,.13Be0.23H2O ; yeUow pp., insol.' HjO
(Crenzburg, D. P. J. 163, 449).
Bismuth chromates (Lowe, J.pr. 67, 288 a.
463 ; Pearson, P. M. [4] 11, 204 ; Pattison Muir,
O. J. li] 15, 12 ; [2] 16, 24 a. 645). Normal
chromate, Bi23Gr04, has not been prepared.
The following basic salts are known : —
2(Bij3Cr04).7BijOj. by PPg- Bi3N03 in small-
est excess of HNOjAq by K^CrOjAq ;
2(Bi23Cr04).Bi20j, by ppg. a more acid solu-
tion of BiSNOj in HNOjAq by KjCrOjAq;
(Bij3CrO,).2Bi203, by boiling the preceding
salt with dilute SOTOjAq or with alkali ;
3(Bij3CrO,)iBi,03, by prolonged heating
2 Bij3Cr0j.Bi^0s with dilute HNOjAq ;
7(Bi23CrOJ.feBij03, by treating (Bi28CrO,).2Bi20s
first vrith cone, then with dilute, HN03Aq. These
salts are aU yellow to red, heavy, crystalline
powders ; insol. water, and slowly- decomposed
by hot acids (v. also Sichromates).
Cadmivm, chromate. — ^Basic salt
CdCrO4.CdO.HjO ; by reaction of CdSO^Aq with
large excess of EjOrO^Aq (Freese, B. 2, 476;
Sarzeau a. Malaguti, A. Oh. [3] 9, 431).
Galcivm, chromate CaCr04.2HjO ; by dissolv-
ing CaC03 in CrOjAq and evaporating. Yellow
prisms ; S.'(14°) "41 ; insoluble in alcohol ; loses
its KjO at 200° (Siewert, Z. f. d. g. Natimviss.
19, 11) (v. Sichromates).
Cerium chromate Ce(0r0j)2 ; yellow powder,
by dissolving Ce(CrOs)2 in CrOjAq and evaporat-
ing (Beringer, A. 42. 143).
Chromium chromate (Crj3CrO,).2Cr303. This
name and composition is sometimes assigned to
CrO, {v. ChboitIiuu dioxide under CHBOnavM,
OXIDES OF, p. 164.)
Cobalt chromates. — ^Basio cobaltoas salt
CoCrO,.Co0.2H20 (Freese, B. 2, 4^6);
CoCrO,.2Co0.4H20 (Sarzeau a. Malaguti, A. Ch.
[3] 9, 431). Clear red-brown pp. by
Co2N03Aq -h KjCrO^Aq. Cobaltic chromate
Co23Cr04 is ^own in combination with KH,
and NH4CI; the salts (COj3CrO4).10NH5,
(Coj3CrOJ.12NH,.5HjO, and
(COj3Cr04).2NH,.2NH4Gl, are described by
Braun (A. 125, 153 a. 197), Gibbs a. Genth {A.
104, 150 a. 295), and Gibbs {B. 4, 790) («. also
CHBOuinu, AiiMoiao-sAi.is or).
Capper chromates. — ^Basic salts:
CuCrO4.2CuO.2H2O, yellowish-brown pp., by/
KjCrOjAq + CuS04Aq, and by
CuSOjAq + KfiifijAq and adding enough KOH
to produce KjCrOjAq (Freese, P. 140, 87 ; Eosen-
feld, B. 13, 1469). Loses its H2O at 260° and
takes it up again in moist air. Two salts,
2(CuCr04).5Cu0.5H20, and CuCrO4.6CuO.5H2O,
are described by EoseHfeld (Z.c.); obtained by
adding CuSOjAq to KjCrjO^Aq with excess of
KOHAq. The salt CuCrO4.2CuO.2H2O dissolves
in NHjAq at 0°; dark-green crystals of
2(CuCrO4)CuO.10NH3.2H2O separate (Sarzeau
a. Malaguti, j1. Ch. [3] 9, 431; Viefhaus, .7. ^jr,
88, 431 ; Slater, /. pr. 60, 247) («. also Potas-
sium chromate). .
Iron chromate. — Basic ferric salt
(Fe23Cr04).2Fe203 ; brown pp. by K2CrO;Aq
acting on iron-alum solution ; decomposed by
HjO to PejO, and CrOjAq. An acid salt,
Fe23Cr04.Cr03, is said to be formed by digesting ,
CrOsAq with FeJOgSg, and evaporating (Klet-
zinsty, D. P. J. 207, 83; Elliot a. Storer, P.
Am. A. 5, 192),
Lead chromate PljCr04. Occurs native as
red-lead ore, in yellow, translucent, monoolinic
prisms, S.G. 5-2 to 6'1, Obtained as yellow pp.
by KjCrOjAq or KjCrjOjAq acting on neutral so-
lution of a Pb salt; also in crystals by strongly
heating KjCrO, with PbOl2, S.G. of crystals 6-12
(Manross, A. 82, 348; Drevermann, A. 87, 120).
S.H. -09 (Kopp, A. Suppl. 3, 1). Insol. in HjO,
sol. inHNOjAq or KOHAq ; melts without change,
but at higher temperature gives O, 'Cr203, and a
basic salt (PbCrP4J'b0). Acts as an oxidiser,
hence used in organic analysis (v. Vohl, A. 106,
127).
Basic salt PbCrO,.PbO ; red crystals, ob-
tained by throwing PbCrOj in small quantities
into molten KNO„ cooling somewhat, pouring off
stiU liquid part, and quickly washing residue vrith
H2O ; also by digesting PbCrO, with cold KOHAq,
or with hot K2Cr04Aq. Lisol. in E.fi ; sol. in
KOHAq ; acids vrithdraw PbO (Wohler a. Liebig,
P. 21, 580). Another basic salt, 2(]^bCr04).PbO,
occurs native as Ifelanochroite, and is said to be
formed by diffusing K2Cr04Aq and Pb2N03Aq
(Drevermann, A. 87, 120). Lead chromates are
used as pigments.
Lithium chromate Li2Cr04.H20; red trime-
tric crystals, easily sol. in HgO. A double salt,
Li.NH4.CrO4.2H2O, is obtained by saturating
Li2Cr20,Aq with NHgAq (Bammelsberg, B. B.
1865. 629) (v. Sichromates).
Magneswm chromate 'M.gptOi.l'&jti. Citron-
yellow soluble crystals; isomorphous with
MgS04.7H20 ; S.G. 1-66-1-75 ; by dissolving MgO
in CrOjAq and evaporating (Kopp, A. 4Si, 100 ;
Grailich, W. B. 27, 174).
The double salt MgOr04.NH4Cr046H20 crys-
tallises from a solution of its constituents ;
yellow monoclinic crystals, isomorphous with
corresponding double sulphates (Grailich, Z.c.).
V. also Potassium chromate.
Mangamese chromate. — Basic manganous salt ;
MnCrO4.MnO.2H2O, brown pp. by reaction of
boiling MnS04Aq and K2Cr04Aq (Fairrie, C. J.
4, 300; Freese, P. 140, 87; Warington, P. M.
[3] 21, 380 ; Beinsoh, P. 55, 97).
Mercwry chromates. — Mercurous onromate
HgjCtOt; red crystalline powder; by reaction of
166
CHROMATES.
HgNOsAq and KjCrO^Aq or KjCrjO^q (H.Eose,
P. 53, 124; Freese, Z. [2] 6, 30). Decomposed
by heat to Hg, 0, and CrjO, (Darly, A. 65, 204;
Freese, P. 140, 87). By action ot alkalis a black
basic salt, Eg2CrO{.2Hg20, is obtained (Bichter,
JB. 16, 1489).
Meicuiic chiomate HgCiO, ; dark, garnet-red,
trimetric prisms; obtained by evaporating equal
parts of yellow HgO and CrO, in H^O. Decom-
posed by EgO to CrOjAq and EgCrO^.aHgO.
Decomposed by acids (Geuther, A. 106, 247;
Millon, A. Ch. [3] 18, 365).
The basic salt HgCr04.2HgO is a brick-red
powder, obtained by boiling EgO with EjCrO^Aq,
or by reaction of Eg2N0,Aq and KjCrjOjAq
(Mmon,.i. Oh. [3] 18, 365; Freese, Z. [2] 6,
30).
A double salt 2(HgCr04).HgS is obtained by
digesting freshly ppd. HgS with solution of
freshly ppd. HgO in CrOgAq, and drying at 30° ;
easily explodes when rubbed (Fahn, J. 1862.
221) (v. also Ammmdiim dichromaie).
■ Nickel ch/romate. — ^Basic salt
NiCrO4.2NiO.6HjO; brown pp. by reaction be-
tween NiSOjAq and KjCrO,Aq. Loses its H„0
above 300° (Freese, P. 140, 87). Other basic
nickel chromates are described by Schmidt (A.
166, 19). A double compound, NiPrOj.eNHj, is
obtained in yellow dichroic crystals by addition
of alcohol to a solution of the basic salt in pre-
sence of NHjAq ; the crystals lose NH, in the
air (Schmidt, l.c,),
JPotaasium ch/romate EjCrO,. S.G. - 2-71.
S.H. '189 (Kopp, A. Sv^l. 3, 1). O.E. (0°-100°)
•01134 (Joule a. Playfair, C.J. 1, 121 ; Sohiff, A.
107,64). S. (0°)'58-9; (20°) 62-94; (60°) 71-02;
(100°) 79-1 : boiling-point of saturated Bolutiou
= 104-2° (Michel a. Kraft, A. Ch. [3] 41, 471;
Schiff, A. 108, 326; v. Hauer, X^ir. 108, 114).
Fre6zing-point of saturated solution = - 12-5°
(Budorfl, P. 122, 337). S.G. i21° 38-44 p.c. solu-
tion =1-3787; 17-09 p.c. solution = 1-1476; 8-54
p.c. solution = 1'0703; 4-27 p.c. solution = 10349
(Michel a. Kraft, A. Ch. [3] 41, 417 ; Alluard,
C. B. 59, 500).
Preparation.-^!. By heating 5 parts KjCrjO,
with 4 parts KNO, or K^GO, until the whole fuses
quietly, dissolving in water, and crystallising.—
2. By neutralising KjCrjOjAq with KjCOj, eva-
porating and crystallising.— 3. By fusing Gi.fi,
with K2OO, and KNOg, dissolving in water aind
orystfJlising.— 4. By fusing chrome-ironstone
with KjCO, and CaO^Hj, lixiviating with HjO,
boiling down, and crystallising.
Properties. — Pale lemon-yellow, double six-
sided trimetric pyramids; isomorphous with
K2SO4. Melts without change. Insol. alcohol.
Solution in H^O is alkaline, with metallic taste,
and is poisonous ; on evaporation, this solution
gives crysjtals of K^Cr^O,, and mother liquor
gives crystals of KgCrO,.
Beactions. — 1. Acida, even CO^Aq, produce
KjCrjO, (Schweitzer, N. B. P. 3, 212 ; Margue-
ritte, J. pr. 64, 502 ; Mohr, Fr. 1872. 278).— 2.
Seduced by H,S or KjSAq, with formation of
Ctfii.xHfi, and by SO^Aq with production of
Crj3S0,Aq.— 3. With HOI gas, KCfl, H^O, and
KjCr,0, are formed, and then the Kfizfi, is re-
duced to CrCl, and CrO^ (Thomas, C.J. 33, 371).
ComlmiaUom. — 1. With varions chromates to
form double salts. K2Cr04.(NH4)jCr04 crystal-
lises from oonc. KjOr^O^Aq saturated with NH,
(Berthier, A. Ch. [3] 7, 77 ; Johnson, J.pr. 62,
261). K2CrO4.CaCrO4.2HjO crystallises from
KjOrjOjAq neutralised by CaOjHjAq.
E^Cr04.5CaCr04 obtained by slowly evapora-
ting a mixture of CaCl^Aq and K^CrOjAq (Bahr,
J. pr. 60, 60j Duncan, J. pr. 60, £4 ; Bammels-
berg, P. 98, 507). K2OrO4.2CuCrO4.CuO.2H2O,
obtained by reaction between cold CuS04Aq and
K2Cr04Aq, or by adding KOHAq to n)ixture of
KjCrjOjAq and OuS04Aq (Freese, P. 140, 87).
K2CrO4.Fe23CrO4.4H2O, by reaction between
oonc. Fe2Cl8Aq and K2Cr04Aq, dissolving
pp. in HdAq, cooling, and washing rapidly
with cold H2O (Hengson, B. 12, 1300 a. 1656).
K2CrO4.MgCrO4.2H2O ; by evaporating cone.
K2Cr20,Aq after neutralising by MgO or MgCO,
(Hauer, J.pr. 80, 222 ; Schweitzer, A. 64, 276).
K2CrO4.2ZnCrO4.2ZnO.3H2O ; byprolongedaction
of cold ZnSOjAq on excess of KjCrOjAq (Freese,
B. 2, 476 ; Prussen a. PhUippona, A. 149, 92).—
2. With merctmc chloride and cyanide, to form
K2Cr04.2HgCl2, and 2K2Cr04.3Hg(CN)2, respec
tively (Darly, A. 65, 204 ; Eammelsberg, A. 28,
217; 84, 281) {v. also Di-, Tri-, and Totra-
chromates; also Bromo-, CMoro-, Flue-, lodo-,
Chromates).
Bubidium chromate Eb2Cr04. YeUow tri-
metric crystals, isomorphous with K2Cr04 and
K2SO4 (Piooard, J.pr. 86,449; Grandeau, A. Ch.
[3] 67, 155).
Silver chromate Ag2Cr04. Dark-red crys-
tals; byreaction between K2Cr04AqandAgNOsAq,
or by digesting moist Ag20 with KjCrOjAq.
Insol. HjO; sol. adds, NH,Aq, and alkali chrom-
ates ; KOHAq withdraws all CrOj. Under H2O
is slowly reduced by Zn, Cd, Sn, Ac. (Freese, P.
140, 87; Fischer, P. 8, 488). Combines with
NH, to form Ag2Cr04.4NHs ; produced in yellow
crystals, isomorphous with corresponding sul-
phate and selenate, by dissolving Ag2Cr04 in hot
NHjAq and crystallising (MitscherUch, P. 12,
141 ; Wohler a. Eantenberg, A. 114, 119).
Sodium chromate Na2CrO4.10H2O ; yeUow,
deliquescent crystals, isomorphous with
Na2SO4.10H2O. Trepared similarly to K2Cr04
(Johnson, J. pr. 62, 261 ; Kopp, A. 42, 100) (v.
also Sichromates).
ThalUwm chromate Tl2Cr04. Yellow pp.
obtained by reaction between KjCrOjAq and
neutral solution of a thallous salt (Carstanjen,
J.pr. 102, 65 a. 129; Hebberling, A. 134, 11;
Strecker, A. 135, 207 ; Crookes, C. N. 8, 255)
(v. also Si-, and Iri-chromates).
Thorium, chromate Th2Cr04.8H20 ; crys-
tallises by evaporating a solution of Th-O, in
CrOsAq (Chydenius, P. 119, 43).
Zimc chromates.— \aAovia basic salts are
obtained by the reactions between ZnS04Aq
and K2Cr04Aq: the most marked seems to be
ZnCrO4.ZnO.2H2O (Sarzeau a. Malaguti. A. Ch.
[3] 9, 431 ; Thomson, J', M. 3, 81 ; Prussen a.
Philippona, A. 149, 92). By dissolving this
salt in a little NHjAq, and adding alcohol,
ZnCrO4.4NH8.3H2O is obtained (Sarzeau a.
Malaguti, l.c. ; Bieler, A. 151, 223) («. also
Potassitmi chromate).
Chromates of In (Meyer, A. 150, 137); Mo;
Sr; Sn (Leykauf, J. pr. 19, 127); U; and Yb
(Popp, A. 131, 179) seem to exist, but very
CHROMATES.
in
little is known concerning them, nor have their
compositions been satisfactorily determined.
Flno-, Bromo-, CMoro-, and lodo-chromatea ;
also Amido-chromates (v. supra beginning of this
art., p. 154). Salt? derived from the hypo-
thetical acids, fluoohromic CrOj.F.OH, bromo-
chromio OrO2.Br.OH, &c., and amidochromic
Cr02.NH,.0E. These acids are not themselves
known.
Potassmm ftiwchromate CrOj.F.OK. Euby
red, semitransparent, crystals; efSorescent in
air; melts when heated; acts on glass. Prepared
by heating powdered Kfkjd, in a Ft dish with
excess of cone. HPAq (Streng, A. 129, 225;
Heintze, J. pr. [2] 4, 225 ; Varenne, C. R. 89,
358; 91,389).
Potassium bromochromate CrOj^r.OK.
Dark-brown crystals ; gives up Br in an exsicca-
tor ; decomposed by H^O. Obtained by satura-
ting cone. KjGtfljA.q with fuming EBrAq, and
crystallising from HBrAq (Heintze, J, pr. [2] i,
225).
Potassium ehlorochromate CrO2.Cl.OK. Ob-
tained by heating for a short time 3 parts
E20r20, with i parts cone. HCIAq and a little
H3O, and cooling; or by adding Cr02Cl2 to
KClAq, or to K2Cr04Aq sligh(!ly acidified with
acetic acid :
KjCrjO, + 2HClAq = 2Ci:02.Ca.0K + H^OAq ;
CrOjCL, + KClAq + Sfi = Cr02.a.0K -1- 2HClAq;
CrOja, + KjCrO^Aq = 2CrO2.Ol.OK + Aq
(Pffigot, A. Ch. 52, 267; Geuther, A. 106, 240)-
This salt is also produced, along with CrjO,,
when violet CrCl, reacts with molten KjCr^O,
(Geuther, A. 118, 68). Large red prisms;
S.G.— 2-497; C.E. (0°-100°) -0159 (Playfair a.
Joule, G. J. 1, ' 121). May be crystallised un-
changed from H2O containing a little acid ;
crystals of KjOrjO, separate from an aqueous
solution, d is evolved at 100°- Decomposed
by cone. H2S04 with formation of OrOjClj and
CrjOsClj (2. V.) ; with NOj gives NO2CI (Heintze,
J. pr. [2] 4, 211). By reaction with cone.
KCNAq, CNCl is formed. By the action of dry
NH3, salt having the composition K^CrjOg
(7CrO2.OK.CrOz.OK.CrO2) is formed, along with
KCl and NH4& ; if the chlorpchromate is sus-
pended in (C2H5)20 and NH3 is passed in, crys-
tals of potassium amidochromate CrOj-NHj-OE
. (o. V.) are formed (Heintze, J. pr. [2]. 4, 211).
Chlorochromates of Na— CrO2.Ol.ONa.2H2O ;
of NH4— Cr02.C1.0NH,;'of Ca, Sr, Ba, Mg, Ni,
Co, and Zn— (Cr02.C1.0)2M.a;H20 ; have also
been prepared, by adding CrOzClj to fairly oono.
solution of • the metallic carbonates in CrOjAq.
When M = Mg. Ni, Co, or Zn, the salts crystallise
with 9H2O; when M = Ca, with SHjO; when
M = Sr, with ABLfl; and when M =Ba, with Kfi
(Pfligot, A. Ch. 52, 267 ; Prffitorius, A. 201, 1).
Potassium iodoehromate CrOj.I.OK. Ob-
tained, as garnet-red, easily decomposed, crystals,
by gently heating cone, colourless HIAq with
finely powdered KjCr,©, (Guyot, C. B. 73, 46).
Potassium amidochromate CrO2.NH2.OK.
Finely powdered CrOj.Cl.OK is slowly added to
water and ether (free from alcohol), the liquid is
simultaneously saturated with NHs ; after stand-
ing 24 hours, the ether is poured oS, the residue
is gently warmed to get rid of adhering ether, and
is then treated with water; the liquid is evapo-
rated at a low temperature, and allowed to orys-
taUise. The salt is recrystallised from H,0,
and the crystals are dried at 100°. Garnet-red ,
unchanged by cold H,0, or cold NaOHAq; de-
composed by HjO, or NaOHAq, at 100'', giving
CrO2.OK.ONH,, and CrO2.OK.ONa, respectively;
decomposed by nitrous acid to K2Cr20„ N, and
H2O. CrO2.NH2.OK is changed by dry NH3 to a
dark-brown powder, from which HjO removes
NH4CI and leaves a crystalline salt, Cr,0,(0K)2:
the corresponding NH, salt is obtained by. acting
on CrOjOlj dissolved in CHOlj with NH3, and
reacting with H2O (Heintze, J. pr. [2] 4, 214).
Dichromates M2Cr20, and MCr20,. Most of
these salts are soluble in water ; many of them
are decomposed by water. The greater number
are salts of monovalent metals. They are ob-
tained by the action of acids on M2Cr04.
Ammoniwmdichromate{'!^'H.^)fiifi,. Orange
coloured, monoclinio, crystals ; S.G. 2-367 ; de-
composed by heat to Crfi,, S.jO, and N. Pre-
pared by neutralising CrOgAq with NHjAq,
adding an equal quantity of CrO,Aq, and evapo-
rating (Biohmond a. Abel, 0. J. 3, 199 ; Siewert,
Z.f. a. g. Natwwiss. 19, 11; Sohabus, P. 116,
420 ; Weiss, SUz. W. 37, 373; Bammelsberg,P.
118, 158 ; SchiS, A. 107, 64). Two double com-
pounds with HgClj, viz. (NH4)2Cr20,.HgCl2.H20,
and 8(NH4)2Cr20,.HgCl2, exist (Darly, A. 65, 204 ;
Zepharovich, Sitz. W, 39, 17 ; Clarke a. Stern,
Am. 3, 351).
Barium dichromate BaCr20,.2H20 ; yellow
needles, obtained by dissolving BaCrO, in cone.
CrOjAq, evaporating, crystaUising, and drying at
100°. Decomposed by HjO to BaCr04 and
CrOjAq (Bahr, ~J. pr. 60, 30 ; Zettnow, P. 144,
167 ; Preis a. Eayman, B. 13, 340).
Bismuth dichromate.— The salt '
2(Bi23Cr04)3i20„ obtained by ppg. BiSNO, in
HNOjAq by KjCrOtAq, described as a basic bis-
muth chromate (p. 155), may perhaps be better
regarded as Jbasio bismuth dichromate
(BiO)2Cr20,.
Calcium dichromate CaCrjOj.SHjO ; deli-
quescent, red, crystals ; obtained by dissolving
CaCrO, in GrO,Aq and evaporating (Bahr, J. pr.
60, 60).
Copper dichromate CuCr20,.2H20 ; brown-
black, deliquescent, crystals; e. sol. in HjO or
alcohol; decomposed by hot HjO with separa-
tion of CuCr04.2CuO ; obtained by dissolving
CUO2H2 in cone. CrOjAq, and evaporating
(Droege, A. 101, 39).
Lead dichromate PhCi^O,. Brick red, cry s.
talline, powder ; by action of CrOjAq on PbCrOj
(Preis a. Bayman, B. 13, 340).
Lithium dichromate lAjCtJO, ; black-brown,
deliquescent, crystals (Bammelsberg, B. B. 1865.
629).
Potassium dichromate KJOrfi,. S.G. £
2-692 (Joule a. Playfair, C. /. 1, 121 ; SchifE, A.
107, 64). M.P. about 400° (Tilden a. Shenstone,
T. 1884. 34). S.H. -186 (Kopp, A. Su^l. 3,
1 a. 289). O.E. (0°-100°) -0122 (Joule a. Play-
fair, C. J. 1, 121). S. (0°) 4-9 ; (10°) 8-4 ; (40°)
29-2 ; (80°) 73 ; (100°) 102 ; (117°) 128-3 ; (129°)
153-8.; (148°) 200-6 ; (180°) 262-7. S.G. of solu-
tion 6-08 parts in 100 water = 1-0405 at 19-5°,
of 13-1 parts in 100 water = 1-0847 ; saturated
solution boils at 104° ; insol. alcohol (EroiAers,
P. 92, 497 ; 96, 110 ; 96, 39 ; Alluard, 0 B. 59,
158
CHROMATES.
600; Michel a. Eraft, A. Ch. [3] 41, 471 ; la-
den a. Sheustoae, T. 175, 23).
Prepa/ration. — Chiome-ironstone is heated,
powdered, and mixed with E^CO, and CaO ; the
mixture is heated to 150° until quite dry, then
to bright redness, in presence of air, with frequent
stirring. The fused mass is allowed to cool, and
is then treated with a small quantity of boiling
water; if the solution contains CaCrO, it is de-
composed by adding KjCO, and filtering from
CaCO,. Sufficient acid to change the E2CrO, to
E.CrjO, is added, the liquid is evaporated and
allowed to crystallise. The crystals are purified
by reorystaUisation from water.
Properties. — Large, red, triolinic, crystals ;
unchanged in air. Solution in water is acid to
litmus, has a metallic taste, and is poisonous. Is
rapidly changed by light in presence of organic
matter; hence used in photography (Schwann,
Z>. P. J. 199, 130). Decomposed at white heat to
EjCrO,, 0, and CrjOj-
Beactions. — Beduoed by heating with 0, S, or
NH,C1; or with solid HjCjOj (Bothamley, C. J.
51, 159 ; Werner, 0. J. 53, 602) ; KJDxfi,Aq is
reduced by SO^Aq to Cr^SSOjAq, and by HjS to
CrjO, and S ; NO is absorbed and after a time
CrOj is ppd. (Vogel, J. pr. 77, 482). Heated
with cone. HjSO,, EjSO,, Cr23SO„ HjO, and O
are produced; addition of 2 formula-weights
H2SO4 to a boiling solution of one formula-
weight Kfirfi, produces pp. of orange-red
HESO,.E2Cr20„ which is decomposed by H2O
(Schwarz, D. P. J. 186, 31). Solution of E^CrjO,
in cone. EGLAq gives CrOj.Cl.OE {q. v.) on cool-
ing. From a hot solution of the salt in 12 parts
HNOjAq, carmine-red crystals of CrjOj.NOj.OK
(?OE.CrOj.O.CrOj.NOj) separate on cooling; by
re-crystalUsing this salt from ENOjAq, the salt
CrA-NOj.OE (70E.CrOj.O.Cr02.0.Cr02.N02) is
obtained (Darmstadter, B. 4, 117). A double
compound Kfiifij.lELgCl^ is obtained by evapo-
rating a mixture of its constituents (Darly, A.
65, 204; Hahn, Ar. Ph. [2] 99, 147).
BubidMmi dichromate BbjCr^O, ; and SodUrni
dichromate, MjCrjO, ; closely resemble E^Cr^O,
(Picoard, J. pr. 86, 449 ; Grandeau, A. Ch. [3]
67, 155).
Silver dichromate Ag^CrjO,. By ppg.
KjCr^OjAq by AgKO,, or digesting moist Ag^O
with KjCrjOjAq; somewhat soluble in HjO,
crystallising in red, triclinio, crystals; decom-
posed by boiling water; when strongly heated
gives GrjO, and Ag(Freese,P. 140, 87; Waring-
ton, P. M. 11, 489; Tesohemaoher, P. M. 1,
345 ; Nason, A. 104, 126).
ThalUum dichromate Tifitj^,. Bed, crystal-
line, powder; insol. in HjO; decomposed by
oonc. acid to TljCraO,, (2, v. infra). Obtained
hy rtootion of thallous salis with E:Cr20,Aq.
Iri-, i'dtra-, and Eeza-ChrQmates : M'^CrjOig,
M'sCr^O,,, and M'jCrjO,^ Very few of these salts
are known. (NHJjCrjO.o, EjCr,0,„, and TljCrsO,.
are obtained by crystallising solutions of the di-
ohromates in HNOgAq (Siewert, Z. f. d. g. Na-
turwiss. 19, 11 ; Bothe, J. pr. 46, 184 ; Hauer,
Site. W. 39, 439; Willm, A. Oh. [4] 5, 5).
EjCr^O,, is obtained by long-continued digestion
of, EjCrjOio in cone. HNOjAq (Siewert, i.c.).
(NH4)2Cr„O,g.l0H2O was obtained by Bammels-
beig (P. 94, 507) from a solution of QHU^ffiifir.
Chromites. Compounds of Cr/), with more
positwe metalUo oxides. A compound2CaO.Cr20,
is obtained, according to Chancel (C. B. 43, 97),
by the reaction between KHjAqanil chrome-alum
solution mixed with OaCl,. By mixing solutions
in EOHAq of Cxfi, and PbO or ZnO, pps. are
obtained of the composition MO.Cr^Oj (Pelouze,
A. Oh. [3] 33, 6). Compounds of the form
MO.CrjOj, where M = Mn, or Zn, are also pro-
duced by fusing together the component oxides
with BjO, at a white heat ; the compounds
crystallise out on cooling; ZnO.Cr20, forms dark
green ootahedra, S.G. 5-309; MnO.Cr^Oj, hard
iron-grey ootahedra, S.G. 4-87 (Ebelmen, A. Ch.
[3] 83, 34). These compounds may be regarded
as chromites, MCr^Ot, i.e. salts of the hypo-
thetical chromous acid H2Cr.204. Certain me-
tallic o^des which are insoluble in EOHAq
become soluble therein when mixed with
Cr^Og.xH^O ; e.g. a mixture of Cr^Og.xH^O with
40 p.o. FejO,, 12-5 p.o. MnO, 20 p.o. CoO, or
25 p.c. NiO, is completely soluble in EOHAq ;
on the other band Cr^O, is completely ppd. by
EOHAq in presence of 80 p.c. J^efi,, 60 p.c.
MnO, or 50 p.o. CoO or NiO (Church, Ph. 0.
1853. 391).
Chromium, alloys of. An alloy of Or with
Al is described by Wohler (A. 106, 118) as very
fusible, tin- white, crystals; becoming brittle
after fusion ; S.G. 4-9. Fremy (O. B. 44, 632)
obtained an alloy with Fe by reducing chrome-
ironstone with C, or by the action of Fe on
Cr^O, at a very high temperature ; long needles,
harder than steel. By the action of Na amal-
gam on CrOlgAq an amalgam of Cr with Hg is
produced (Vincent, P. M. [4] 24, 328 ; Schon-
bein, P. 112, 445).
Chromium, ammonio- salts of ; or Chrom-am-
monium salts. Freshly ppd. CrjOs.a!H20 dis-
solves in cone. NHjCLAq containing NHjAq ;
on standing in air a reddish- violet pov^der is
deposited; when this is dissolved in ooldHClAq
and excess of cone. HClAq is added, a rose-red
crystalline powder is produced having the
composition Cr2Cla.8NH3.2H2O. By treating
this salt with cold cone. H^SO^, a new com-
pound Cr2Cl2(SOj2.8NH3.2H20 is produced;
by the action of BaljAq on this, the salt
Cr2Cl2I4.8NH3.2H2O is formed; and from this,
Cr2Cl2Brj.8NH3.2H2O may be obtained by the
action of cone. HBrAq. Various othet deri-
vatives are known of the general form
Cr2M2.X4.8NH3.a!H20, in which M = a,Br, or I,
and X= negative radicle, 01, Br, I, NOj, ?^'
&o. The reactions of this series of compounds
forbid us to regard them as ordinary double com-
pounds of Cr2M5 with asNHj ; they are usually
looked on as compounds of the hypothetical
groups, chloroch/rom-, bromochrom-, iodoahrom-
ietrammomum, with ^negative radicles CI4,
(N0,)4, &a. On this supposition the formula
N4H8(NH4)4.(Cr2MJ.X4 would represent the com-
pounds in question ; the names chloro- (bromo-,
iodo-,) ch/romtetrmnmomum chloride, bromide,
&o., are nsed. The less hypothetical formula
Mj.Crj.SNHj.Xi is also frequently employed to
represent the ohloro(&c.)chromtetrammonium
compounds.
Six other series of ohromanuuonio-com.
OHROM-AMMONIUM SALTS.
159
pounds are known. They may all be repre-
sented by the general form Orj.xNH3.X8, where
a! = 10 or 12, and X = negative radicle; in some
of these part of the X, is easily replaced by other
radicles and part is not ; in others the whole of
the Xb is easily replaced. If M represent the
radicle which is replaced with difficulty, and X
the radicle which is easily replaced, we get the
developed general formula for the seven series
of compounds Mj;.Crj.8(10 or IZJNHs.Xs ; whore
iB = l, or 2, and a = 4, 6, or 6. The second to
seventh series may also be regarded as derived
from the first (i.e. from the ohlorp(&c.)ohrom-
tetrammonium salts, by replacing H in
N^H,(NHj4.(CrjMj).X, by the radicle NH,. The
following formulsB represent the seven series of
compounds :—
(1) Mj.0r,.8NH,.X, or N,H3fNH,),.(Cr,Mj).X,
Ch/romtetrammonium salts.
(2) M,.Crj.lONH3.X, or N,H,(NH,),(0r3Mj).X,
Pti/rpureochrom salts.
(3) Crj.lONH3.X, or N4H.(NH,)3.Crj.X.
Boseochrom salts.
(i) M,.Crj.lONH,.X, or N,H,(NH,)3(CrjMj.)X,
Xanthochrom salts ; (M^ = 2NO2).
(5) Or,.12NH3.X, or N,H,(NH,)3.Crj.X.
Luteoehrom salts.
(6) & (7) M.Cr,.10NH3.X3 or N,H,(NHj5(Cr2M).X5
Bhodoohrom and Erythrochrom salts ; (M = OH).
The purpureo- and roseo- salts are isomeric,
using the term in a rather wider sense than is
given to it in organic chemistry as the molecu-
lar weights of none of these salts are known ;
AgNOsAq pps. I of the 01 from purpureochro-
mium chloride in the cold, but all the 01 fr9m
roseochromium chloride ; HNOjAq, HBrAq, &c.,
also removes | of the 01 from the former salts ;
boiling HIAq, however, produces I2.Or2.lONH3.I4
{iodopmyureoehromium iocUde) ; and by acting
on this with dilute HOlAq, I2.Or3.lONH3.Ol, {iodo-
purpiinreochroimum chloride) is obtained. Pur-
pureo- compounds, in which M2 and X, are
the same radicle (e.g. Br2.Or2.10NH,.Br4, or
Cl2.0r2.10NH,.Ol4) easily change to roseo- com-
pounds by standing in the air, or by heating.
Xanthochromium chloride is obtained by the
action of NaN02Aq and dilute HN03Aq on
Cl2.Cr2.10NH,.Ol4, or on Or2.lONH3.Bre. The
three series, purpureo- luteo- and rhodo- salts,
are obtained by more or less slowly oxidising
CrjOlj in NH401Aq in presence of NHjAq ; the
purpureo- and rhodo- salts are obtained by oxi-
diMng in presence of air, the luteo- salts in ab-
sence of air (v. mfra). The roseo- and erythro-
salts are obtained froni the purpureo- and rhodo-
respectively (v. infra). The rhodo- and erythro-
salts are isomeric; the former change to the
latter by standing in air {v. infra).
In the nomenclature of the chromtetram-
monium and purpnreochromium salts it is neces-
sary to use prefixes, ohloro-, bromo-, &a., to ex-
press the nature of the radicles M. ; thus chloro-
purpureochromium chloride, and bromopurpureo-
chromium' nitrate, are Cl2.Or2.lONH3.Ol4, and
Br2.Or2.10NH3.(NO3)4, respectively. In the other
series prefixes are unnecessary.
It will suffice here to describe the chief com-
pounds in each series. The principal references
are Fremy, A. Ch. [i] 9, 431 ; ClSve, J.pr. 76, 47,
Am. S. [2] 49, 251 ; Jdrgensen, J. pr. [3] 20,
105 ; 25, 83 ; 25. 321 ; 30, 1 ; Christensen, /. pr.
[2] 23, 26 ; 24, 74 ; 25, 398.
I. Cbbomietbammonitiii Seiuhs
M2.0r2.8NH3.X4.a;H20. Chloroohromtetrammo-
nmm chloride Cl2.Cr2.8NH3.Cl4.2H2O. Deep-red,
very lustrous, almost opaque, trimetrio crystals.
Obtained by digesting freshly ppd. chromium
hydroxide in a closed fiask with oono. NH4CI in
NHjAq, until the hydroxide dissolves: the deep-
red liquid is allowed to stand in the air, the dark-
violet powder which separates is dissolved ia
cold HOlAq, excess of oono. HClAq is added, the
rose-red crystalline powder which separates out
is washed with cone. HOlAq, then with strong
alcohol, and is crystallised from warm H^O con-
taining a little HCl. This compound begins to
decompose at 120-' ; when strongly heated NH„
NHjCl, and HjO, are given off, and CTjOb re-
mains ; heated in air-free H, or in OO2, OrjOCl,
remains. The salt is soluble in water, but on
boiling Cr203.a!H20 and NH, are produced.
Treated with H2O' and moist AgjO, a liquid is
obtained probably containing Oly Crj.SNH,. (OH),;
it soon decomposes with evolution of NH3.
The sulphate Cl2.0r2.8NH3.(S04)2.2H20 is ob-
tained by treating the chloride with cold cone.
H2SO4, and then-with HjO ; from this the iodfide
(X, = I,) is produced by the action of BaljAq, and
by the action of fuming HBrAq on this, the
6romiie {X4= Br,) is produced.
If freshly ppd. Cr203.a!H26 is treated with
NH,Br in NH,Aq, bromochromtetram,momwn
bromide, Br2.Cr2.8NH3.Br,.2H20 is produced ; an
aqueous solution of this salt dropped into cone.
HClAq gives the bromo-chloride (M2=Br2,
X4 = Cl4).
II. PuBFUBEOCBiiOIIIDM SERIES
M2.Cr2.lONH3.X4. Chloropiwpureochromium
chloride. Ol2.Or2.lONH3.Ol,. Prepared by re-
ducing K20r20,by alcohol and very cone. HClAq,
so that 12 g. KjCiJJ, give SOc.c. OrCl, solu-
tion, pouring the liquid (from KCl) through a
separating funnel into a cylinder fitted with a
reversed U-tnbe and an exit tube, and contain-
ing sticks of Zn, and adding a little HClAq ; when
the liquid is the colour of 0uS0,Aq (which in-
dicates reduction to CrOL,), forcing it through
the U-tube into a solution of 600 g. NH4OI in
1,000 c.c. NHjAq, S.G. '9; and repeating this
operation untU 50 g. K2Cr20, have been reduced,
and the CrCl, solution further reduced to OrClj
and driven into the ammoniacal NH,GlAq. The
blue liquid is then oxidised, by long-continued
passage of air, until it becomes deep carmine-
rod; 2i litres of cone. HCIAq are added, the
liquid IS boiled for a few minutes, when the
chloride separates out as a oarmine-red crystal
line powder. This liquid is allowed to cool, and
poured off, the residue is washed free from
NH4CI by cone. HOlAq -1- an equal volume of HjQ,
collected on a filter and again washed with the
same HClAq, dissolved in H2O slightly acidified
with HjSOi, and re-ppd. by cono. HClAq ; the pp.
is boiled with a little cone. HClAq, washed with
the same strength of HClAq as before, then with
90 p.c. alcohpl, and dried at about 18''-20°.
Chloropurpureo-chromium chloride crystal-
lises in small carmine-red octahedia : S.(>. ^
160
CHROM-AMMONIUM SALTS.
1-687; S. (16°) -65 ; insoL cone. HClAq; on
boiling an aqueous solution Toseoohromium
chloride is obtained; decomposed hj heat, giving
CrA-
Bromo-bronUde (Mj = Br2, X4 = Br,) is pre-
pared similarly to the chloro-chloride, nsing
NH^Br in place of KH,G1, &e. By treatment
mth excess of HCIAq it yields bromo-chloride
(Mj = Br„ X4 = Cl<). By treating ohloro-chloride
with boiling oono. HIAq iodo-iodide (M2=l2,
X,^!,) is formed. By the action of dilute
BITO^q, H.^SOfAq, &o., on chloro-chloride,
chhro-nitrate, chloro-suVphate, &o., are obtained
(H2 = CL„ X4:==4NO„ 2SO4, &o.); the action of
E2Cr04Aq produces chloro-chromate (M, = C!lj,
X4 = 2CrOJ. Besides these the following com-
pounds have been prepared : —
M, X, M, X4 , M, X4
CI, 2SiI', Br, 2PtBr, L, Q,
Br, 4N0, I, 4N0,
Br, 2CrO, I, 2PtCIe
in. BoEEOOHBOMIUM SEBtES Cr2.10NH,.Xe.
Roseochrom^um chloride, Cr2.10NH,.C!l,. Ob-
tained by rubbing 5 g. dry chloropurpureo-
chloride mth the moist Ag^O from 20 g. AgNO,
for a few minutes in a mortar, filtering, neutral-
ising the alkaline liquid with HCIAq, filtering
from AgCl, evaporating in a rapid air-stream,
pressing pp. between paper, washing once with
a little E2O, and drying in air out of direct sun-
light. Orange-yellow crystals; v. sol. HjO;
insol. alcohol ; very unstable, giving off NH, ;
changed, as are all roseo- salts, by heating with
oono. HCIAq, to purpureo- salt. AgNOgAq pps.
all the CI in the cold.
The other roseo- salts are formed by neutral-
ising the solution obtained by action of moist
AgjO on purpureo-chloride by various acids ; the
solution in question probably contains roseo -
hydroxide [X, = (OH),]. The chief roseo- salts
are X,=Br„ I„ 380,, 6NO3, Br2(PtBr.)2,
(SO,m01.,Br2(CrO4)2.
Iv. Xahthoohbomium series
(NOj)2.Cr,.10NH3.X4. Xanthoch^omium chloride,
(NO,),.Cr2.10NHj.a4. To 20 g. chloropurpureo-
ehloride 300 c.c. warm water and about 20 drops
dilute HKOgAq are added, the liquid is slowly
heated to boiling, then cooled, and filtered ; the
insoluble purpureo-chloride is again treated in
the same way ; 40-50 g. pure NaNO, and 25 c.c.
HCIAq (12 p.c.) are added to the total liquid ;
the y^low crystalline salt which separates out
is washed with water, then with alcohol, dissolved
in water, and ppd. by fairly cone. NH4ClAq.
Xantho-chloride is a yellow crystalline powder ;
fairly sol. H2O; insol. alcohol; easily decom-
posed by acids with production of HNO, ; treated
with HCIAq, chloropurpureo-chloride is formed;
fairly stable towards alkalis ; forms doable salts
with 2PtCl4 and 4HgOl2.
The other most important zantho- salts are :
X4 = Br4, I„ 2SO4, 2S2O,, 4N0„ 2C0„ 2Cr04;
the hy&oxide, X4= (OH),, is known in aqueous
solution, it is fairly stable, and has a strongly
alkaline reaction.
V. LuTEOOHBOMnm sebies Cr2.12NHs.X,.
Luteochrommm nitrate, Cr,.12NH,.(NO,)o. 80 g.
E2Cr20, are reduced to CrCl, by the method
described under chloropnrpureoohrominm chlor-
ide ; the solution is forced by H pressure into
a flask containing 700 g. KH4CI in 760 0.0. NHjAq
(S.G. -gi) ; the flask, which must be entirely
filled with the liquid, is closed by a cork carrying
an exit tube opening under water, and is sur-
rounded by cold water ; after about 24 hrs. evo-
lution of H ceases ; the liquid is poured off from
ppd. luteo-chloride and NH4CI, and is ppd. by
alcohol ; the crude luteo-chloride is washed with
alcohol, dried, dissolved in warm water, and the
solution is filtered into HNOjAq (S.G. 1-39) ; the
crystals of luteo-nitrate are washed with dilute
HNOaAq (1 vol. cono. HNO,Aq to 2 vols. TELfi);
and then with alcohol. The pp. of mixed
NH4CI and luteo-chloride formed in the process
may be dissolved by repeated treatment with
H2O, and iuteo-nitrate obtained by ppn. with
HNOjAq. Luteo-nitrate crystallises in orange-
yeUow, lustrous plates ; S. (abt. 15°) 2*5 ; insoL
alcohol; nearly insol. dilute HNO,Aq.
The luteo-chromium salts form many double
compounds with acid radicles, and also with
some negative metallic radicles ; the more im-
portant salts are : —X, = 2NO,.2S04, 2NOs.2Pt01„,
Cl„, Br„ I,. Cl4.H,PtGl„ Cl2.2Pt01., 3PtCl„
3PtBr„ I2.2SO,, 3S0., 2S0,.PtCl„ 30fi„
2NaP20„ E'e2(CN),2, Co2{CN),2, Cr2(CN)„ (Jor-
gensen, J.pr. [2], 30, 1).
VI. Bhodochbomium sebies
OH.Cr2.10NH,.X,. Bhodochromium bromide,
OH.Cr2.lONH3.Brj.H2O. Ctfi,.xBijO, equal to
10 g. Cr20„ is dissolved in 100 o.c. cone. HBrAq ;
the green solution is poured on to Zn in a cylinder
arranged with a reversed U-tube, i&c., as described
under purpureochloride; 30 c.c. ^Br Aq(l vol. oono.
solution -I- 1 vol. H2O) are added ; when the liquid
is blue (after about 10 min.) 30 0.0. of the same
HBrAq are added, and the H pressure is caused
to force the liquid into 150 g. NHjBr in 750 0.0.
cono. NH,Aq ; the blue solution is oxidised by a
stream of air, after aU particles of Zn have been
removed; the liquid is quickly decanted from
the blue pp. (basio rhodo-bromide), which is
treated with excess of HBrAq (1 vol. cono. solu-
tion 4 3 vols. HjO), whereby red rhodo-bromide is
formed ; the salt is washed with dilute HBrAq
and then with water, it is then dissolved in cold
water and the liquid is poured into moderately
dUute HBrAq ; the crystals which separate ara
washed with dilute HBrAq and then with alco-
hol, and are dried in the air. Dried for some
days over H2SO4 they lose their HjO. Ehodo-
bromide is a ptde oarmine-red crystalline pow-
der; slowly loses its H2O over cono. E2SO4;
si. sol. cold HjO; on warming, the solution
goes bine- violet ; on boiling, NH, comes off, and
Cr203.!);H20 pps.; insol. dilute HBrAq and
NHfBrAq; boiled with very dilute HBrAq it i^
changed to roseochromium bromide ; boiled with
cone. HBrAq it gives brompurpureo-bromide ;
with AgNO, aU the Br is ppd. ; dilute NaOHAq
or NH^Aq removes i Br, and a basio rhodo- salt
remains; dilate acids form the respective rhodo-
salts.
The ohief rhodo- salts known are: — ^Xj=CI.,
I3. 5N0,. 2iC0„ 2JS0., 2^820., 01,.2AuCl4,
Cl,.PtCl„ C1.2PtCl, ; and the basio salts :—
X5 = 0H3r4, OaCl,!,, 0H.2S20, (J8rgensen,
J.jw. [2]26,321).
VU, EByiHBocmtouinu sebies
OH.Or2.lONHs.X5. Erythroch/romium nitrate,
OH.Or2.lONHj.5NO3.H2O. Ehodo-chloride is
prepared by filtering a Solution of rhodo-bromide
CHROMIUM. CHLORIDES Oif.
161
into HCI&q (1 vol. cono. solution + 1 vol. H^O) ;
it is washed with alcohol, 5 g, rhodo-dhloride are
dissolved in 50 o.o. H^O + 35 o.o. dilute NHjAq;
when the blue solution has beoome red by stand-
ing in air 4-5 vols, of dilute HNOjAq are added;
the pp. is repeatedly treated with dilute HNOjAq,
dissolved in HjO, reppd. by HNOjAq, washed with
alcohol, and driedin the dark. Brythroohromium
nitrate is a crimson powder composed of mioro-
Boopic octahedra ; it decomposes slowly even
in the dark ; when strongly heated N oxides are
evolved and Cvfi, remains ; fairly sol. cold water ;
insol. alcohol; aqueous solution decomposes
when boiled with separation of CroOj.KHjO;
aqueous solution boUed with a few drops of
HNOjAq gives roseoohromium nitrate ; solid
erythronitrate boiled with dilute HClAq gives
chlorpurpureo-chloride.
Other salts are obtained by the action of
acids on the bromide or chloride ; the principal
are:^-X3=Br5, OII4, 2^80^; and the basic salts
X5 = 0H.Brj, OH.4NO3, OH.2S20a (Jorgensen,
J. pr. [2] 25, 398),
Chromiom, arsenates of. — Existence uncer-
tain (v. AiisisNAiES, under Absenio, acids os ;
vol. i. p. 308).
Chromium, bromides of. — Two are known ;
as neither has been gasified the formula CrBrj
and CrBr, may or may not represent the com-
position of the gaseous molecules ; judging from
the analogy of CrOl, it is probable that the
formulae CrBr^ and OrBrj are molecular. These
compounds resemble the chlorides (g;. v.) in their
properties. '
I. CHEOMons BBOMiDE CrBr^ or OrjBr,. Ob-
tained as white crystals by heating OrBrj in H,
by leading HBr over heated Or, or by the action
of N saturated with Br vapour on Cr a;t a red
heat (Moissan, A. 0%. [5] 25, 401). Unchanged
in dry air, but oxidises in presence of traces of
moisture ; dissolves in H^O forming blue liquid,
which dissolves large quantities of violet CrClj.
II. Chbomio bromtdb CrBr, or Or^Brj. SmaU
cylinders formed of Cr„03, C, and starch paste,
are dried and heated to redness in a covered cru-
cible; they are then heated in a tube of hard
glass in dry Br vapour ; crystals of CrBr, sub-
lime, and some remain mixed with, but easily
separable from, Cr^O,. Dark, metal-hke, lus-
trous, hexagonal crystals; olive-green by trans-
mitted light, slightly diohrbio in red light (Woh-
fer, A. Ill, 382). Heated in air Cr^O, is formed ;
KOHAq or NaOHAq decomposes CrBr, into
Cr^O, and KBrAq or NaBrAq. Insol. in H^O,
but dissolves in presence of a little CrBr2. A
green solution containing CrBr, is obtained by
the action of HBrAq on CrjOsHa.
Chromium, chlorides of. — Two exist, CrClj
and OrOV Chromic chloride has been gasified
(at 1200°-1500°) and, the observed V.D. corre-
sponds with the formula CrOlj ; it is probable,
but not certain, that the molecular formula of
ohromous chloride is CrClj.
CrCl,, like several other compounds of Cr,
exists in two forms ; one sol., the other insol.
in HjO. CrOLjAq is an energetic reducer. Solu-
tions of CrOj and CrOs in cold cone. HClAqmay
contain CrCl, and OrClj respectively ; these solu-
tions are brown, they evolve 01 when heated, and
CrCl, remains.
Vol. n.
I. GHBoMons CHLoitiDE CrClj or CrjCl^. MoL
w. unknown. '
Formation. — 1. By the action of dry HCl on
Cr at a red heat (Ufer, A. 112, 302 ; Moissan,
A. 0;j. [5]-25, 401).— 2. By heating CrClj with
KH4CI to a very high temperature (Moissan, l.o.),
' Preparation. — Violet, sublimed OrClj ia
heated in a stream of perfectly dry,H, frpe froiii
every trace of 0, to a very low red heat ; the re-
duction takes place very slowly, but the tempe-
rature must not be raised, else some Cr will ba
formed (Moberg, J. pr. 29, 175 ; 43, 125 ; 44, 322 ;
P61igot, A. an. [3] 12, 528). The H psed should
be passed through a solution of SnCl^in EOHAq,
then through cone, H^SOj, then over red hot Cu,
and lastly through boiled HjSOj and over CaClj.
Properties. — White lustrous crystals ; sol. in
HjO, with production of heat, forming a blue
liqiiid, which rapidly absorbs 0 turning green.
F6Ugot determined the quantity of 0 absorbed ;
it corresponded with formation of CrjCl^O.
Loewel {A. Ch. [3] 40, 42), by the prolonged
action of granulated Zn on a solution of
CrClj.GHjO in 3-5 parts H^O in a flask nearly
filled with the Zn, obtained a colourless solution
of CrClj (containing Zn), which acted as a strong
reducer ; e.g. KoOrO^Aq was reduced to CrOj,
HgOljAq to HgOi, CuSOjAq to CujCl^ and Cu^O,
and solutions of Au and Sn salts to An and Sn.
Beactions. — CrCljAq protected from air gives
the following reactions : — 1. Withpotask or soda,
brownish-yellow CrO^H^, which quickly becomes
CrOjHj with evolution of H. — 2. Potassium sul-
phide pps. black OrjSa. — 3. Sodivmi acetate forms
a red liquid from which red lustrous crystals of
Cr(02H302)2.H20 separate after a time.
Oombinations. — 1. With water, to form
2CrCl2.BH20 (Moissan, A. Ch. [5] 25, 401).—
2. With dry kl/drochloric acid, to form an easily
decomposed compound 6Crqi2.4HC1.26H:26 (Ee-
coura, a. B. 100, 1227).
II. Chbomio chlobide CrCl,. Mol. w. 15S'55.
V.D. 77-45 (Scott, Pr. E. 14, 410).
Formation.— Bj heating CrjSjin dry CI (Bei-
zeUus, P. 50, 79 ; Brunner, D. P. J. 159, 356).
Preparation. — An intimate mixture of Cr^O,
and lampblack is made into little pellets with
starch paste ; tlie pellets are dried and heated in
a covered crucible, they are then placed in a Hes-
sian crucible, through the bottom of which is
fitted a porcelain tube about 6 inches long ; the
upper end of this tube, which passes a very little
way into the crucible, is loosely covered with a
very small crucible to prevent the pellets falling
into the tube ; into the mouth of the Hessian
crucible is fitted a smaller crucible, inverted, and
pierced by a hole. The crucibles are arranged
in a furnace, so that the lower one may be heated
very highly and the upper kept comparatively
cool. The porcelain tube is connected with a
supply of dry 01. The pellets are now heated in a
rapid stream of 01 ; OrClj sublimes into the upper
crucible ; the whole is allowed to cool in 01, else
OrjOj may be formed. The sublimate is washed
with cold HjO to remove Al^Clj formed from the
crucible (Wohler, A. Ill, 230 ; Ufer, A: 112, 281).
Properties. — Lustrous, peach - blossom
coloured plates. S.G. 3-03 (Schafarik, J.'pr. 90,
12). Decomposed at high temperature without
fusion with evolution of 01 (OarneUey a. Williams,
O. /. 37, 126). Insol. in water, unacted on by
M
162
CHROMIUM, CHLORIDES OF.
acids, ev^n by a^ua regia, CrOl, may be obtained
in soft violet-coloured plates, t. sol. in 'B.JO, by
dissolving green CrO,H, in HClAq, evaporating
slowly nntil crystals of CrGl,.6H20 separate,
and heating these in HCl or CI not above 250°
(Moberg, J.pr. 44, 325 ; P61igot,. X pr. 37, 475).
CrCl, thus prepared dissolves very easily in
H^O, forming a green solution ; heated above
250° the salt sublimes to crystals of the peach-
blossom coloured, insoluble variety. The latter
crystals when powdered and boiled with water
for some time go into solution with production
of a green liquid ^Jacquelin, 0. B. 24, 679).
A violet solution of CrCl, is produced by de-
composing violet Gr^SSOfAq by an equivalent
quantity of BaCl^Aq. When this solution is
boiled it becomes green.
The green solutions evaporated at 100° give
crystals of CrClg.icH^O (v. Combinations, No. 1) ;
the same green hydrates of CrOl, are obtained
by dissolving green CrOjH, in HOlAq, or the
insoluble CrCl, in H2O containing a trace of
CrCl^, or PbCrO^ in cone. HClAq and reducing
by alcohol, and evaporating at about 100° ;
evaporated at higher temperatures, oxy-chlor-
ides (q. v.) are obtained. These green solutions
probably therefore contain CrCl,.' But only
two-thirds of the total CI is ppd. from them in
the cold by AgNOjAq ; on boiling for some time
the rest of the CI also forms AgCl. On the other
hand, AgNOjAq pps. all the 01 frodi the violet-
coloured solution of CrClg obtained by the action
of BaCljAq on violet Or^BSOiAq. Moreover,
green-coloured double chlorides, MCl.CrClg,
where M = alkali metal, are not obtained, whereas
several violet double chlorides are known {v.
Combinations, No. 2). Pfiligot {J.pr. 37, 475)
supposed that a green solution of OrOl, contains
CrOCl and HCl; Eerzelius {P. 60, 79) supposed
that on adding AgNO, a double compound of
AgCl and CrCl, is formed and that this is
decomposed only on boiling.
Beactions. — 1. Finely powdered CrCl, boiled
for some time with water slowly dissolves, form-
ing a green solution (Jacquelin, G. B. 24, 679).
If the water contains j^ to jig of its weight of
CrClj, or a little SnCl^ or CujCl^, the CrCl,
quickly dissolves with production of much heat,
forming a green liquid with the same reactions
as that obtained by dissolving CrOjH, in HClAq
(P^ligot, J.pr. 36, 150; Loewel, J.pr. 87, 150;
Pelouze, P. 24, 233 ; Moberg, A. 109, 82 ; Bar-
reswill, A. Ch. 12, 528) {v. Combinations, No. 1 ;
also Chbomium, oxyohlomdes or). — 2. Boiled with
potash or soda CrCl, is slowly decomposed with
formation of CrjO,. — 3. Fused with nitre and an
alkaU or alkaline carbonate chromate and chlor-
ide of the alkali metal are formed.— 4. Molten
potassiumdichromate forms CrOj.Cl.OK (Geuther,
. A. 118, 61). — 5. Heated with cliromic anhydride
Cr,Os and CrOjClj are produced. — 6. Heated in
air CrjO, results. — 7. Heated in dry hydrogen
CrClj, and then Or, is formed. — 8. Zincovpotas-
si/um reduces CrCl, to Or when heated with it. —
9. Heated in ammoJiiaCrN is formed. — 10. Heated
in phosphoretted hydrogen CrP results. — 11.
Heated insulphuretted hydrogen or with sulphur
the product is Cr^Sg.
Combinations. — 1. With water, to form vari-
ous green, crystalline, easily soluble hydrates : —
2CrCl3.9HjO, by evaporating CrOjH, in HClAq
in dry air at 100° (Moberg, J. pr. 29, 17S) ;
CrCl,.6H;0, by evaporating (1) violet CrCl, in
H2O containing a trace of GrCl, in dry air, or (2)
solution obtained by action of cone. HClAq and
alcohol on PbCrO, (Pfiligot, J. pr. 37, 475 ; Mo-
berg, Xfr. 44, 326). Godefroy {Bl. [2] 43, 229)
describes also CrClg.lOH^O, and GrCl3.4H20, as
green crystals. One or other of these hydrates
is probably formed when violet CrClj dissolves
in HjO containing a trace of CrCl,; Loewel
(/. pr. 37, 150) supposes that the CrCl, is re-
duced to CrCl, by the action of the CrCl, pre-
sent, and that the CrCl, thus formed combines
with H2O and dissolves as CrClg.xH^O, and that
more CrCl, is reduced by the freshly formed
CrCl,, and so on (v. also Becoura, G. B. 102,
921). According to Eecoura (C. B. 102, 513 a.
548) the hydrate 2CrCl3.13H,0 exists in two
varieties : (1) green crystals, produced by pass-
ing HOI into a saturated solution of green CrCl,
(or by passing air into cooled CrCl,Aq containing
much HCl, and then passing in HOI ; C. B. 102,
921) ; (2) greyish blue crystals, produced by heat-
ing a solution of 1 pt. of the green crystals in
1 pt. water, and then saturating with HOI. The
green crystals dissolve in water (S. = 130) with-
out production of heat ; the greyish blue crystals
dissolve very readily in water with production of
much heat [2CrCR13H''0, Aq] = 24,000. — 2.
With alkali chlorides to form double salts
MCl.CrOl,, the properties of which are little
known; prepared by treating' MjOr,©, (M = K,
Na, or NH4) with HClAq and alcohol, and
evaporating at 100° until the residue is violet.
On adding H,0 solution occurs, the liquid is
yellow-red, but soon becomes green. Godefroy
(Bl. [2] 42, 194) says that various double metaUio
chlorides containing CrOl, may be obtained by
passing 01 into a mixture of metallic chromate
and alcohol, and washing the products with
HOlAq ; these double salts are decomposed by
H2O, but are unchanged in HClAq containing
32J p.c. HCl. — 3. With phosphoric chloride to
form 20rCl,.2PCl5 ; obtained by heating the con-
stituent chlorides in a sealed tube, and then to
140°-150° in an open vessel (Crouander, B. 6,
1466). — 4. With ammonia to form several com-
pounds (v. ObBOUIUM, AMUONIO-SAIiTS OF).
Chromium, cyanides of, and their derivative!
V. Cyanides,
Chromium, fluorides of. Only one is known
with fair certainty. CrP, is described by De-
ville (C. B. 43, 970) as forming lustrous, mono-
metric, octahedra; obtained by dissolving dry
CrOjH,, which has not been strongly heated,
in HFAq, evaporating in a Pt dish, and heating
the green mass to a very high temperature. The
double salts OrF,.2MF.H20, where M = Na, K,
or NH„ are described by Wagner (B. 19, 896).
Unverdorben (P. 7, 311) obtained a red gas by
heating fluorspar and PbCrO, with cone. H^SOj.
Dumas {A. Ch. [2] 31, 435) prepared the com-
pound as a deep red liquid, by warming 4 pts.
dry PbCrOj, 3 pts. dry pure CaF,, and 5-7 pts.
very cone. H2SO4, in a retort of Pt or Pb, and
leading the gas through a well-cooled tube of Pt
and Pb into a Pt receiver. The liquid is vola-
tile ; the vapour acts on the mucous membranes
and produces violent coughing ; it is at once de-
composed in ordinary air, or by HjO, to HF and
CrO,; it acts rapidly on glass, forming SiF,,
CHROMIUM, NITRIDE OF.
103
The fonaula OtF, was given from estimations
of the quantities of CrO^ and HP produced by
leading the gas into water. Bose (P. 27, 665)
found more i" than agreed with CrPo. Oliveri
(G. 16, 218) recently examined this supposed
fluoride ; according to him it is an oxyfluoride
CrOjFj analogous to CrOjClj.
Chromium, hydrated oxides of, v. Chuomium,
EYSnOXIDEB OF.
Chromium, hydroxides of. Several com-
pounds of Cr with H and O are known. They
react rather as hydrated oxides than as
hydroxides {v. art. HyoBoxiDEs). Chromous
hydroxide, or hydrated chromous oxide,
CrOjHj(OrO".HjO) is very easily oxidised ; it be-
haves towards acids as a salt-forming compound.
At least three hydrates of Cr^Oj are known : —
Cr2O,-7HjO(Cr,06H,.4H,O),
CrA.4H,0(CrAH„.H,0),
and CTfi^.lLfl{Gi.fi^.0.iBL^ ; these compounds
are all salt-forming in their reactions with acids,
V but at j;he same time they exhibit feebly acidic
functions. The hydrate CrO,.H20{Cr02.0jH2) is
a strongly marked acid.
The hydrates of Cr are more or less easily
separated into oxide and E2O by the action of
heat ; the oxide Cr^O, does not directly combine
with water; CrO, readily combines with H^O,
but the solution is separated into CrO, and H^O
by boiling ; the action of CrO towards H^O is
not known as the oxide has not been prepared.
I. Chbomous HTDEoxiDE. CrOjHj Or CrO.HjO.
It is doubtful whether this compound has been
obtained quite free from Cr20,.!EH20. A solution
of CrCl, in air-free water, and protected from
air, gives a yellowish-brown pp. with KOH dis-
solved in air-free H^O (Moberg, J. pr. 43, 114 a.
125). The hydroxide quickly absorbs O and be-
comes dark brown ; it rapidly decomposes HjO,
and combines with part of the 0 evolved. CrO^H,
is slowly dissolved by acids with separation of
Cr and formation of chromous sallts CrX,, e.g.
CrSO<.7HjO, Cr(CjH30j)2.H20, &c. ; these salts
are unstable, and readily oxidise to chromic salts
CrX, (Moberg, J. pr, 41, 330; F^got, A. 62,
247) (v. CmtouinM, salts oip, p. 167).
n. Cheomio hidboxides. Preparation. — A
dear blue pp. of Cr203.!>;H20 is obtained by the
action of KH,Aq on GrCljAq at the ordinary
temperature. The CrCl,Aq must be perfectly
tree from any fixed alkali; it is prepared by dis-
solving Cr in HClAq, or CrCl, in H^O contain-
ing a trace of CrCl,, or by reducing CrO, by
EClAq. When the pp. is thoroughly washed
and dried over sulphuric acid the compound
CrjO,.7H:jO(Crj08H,.4H20) is obtained; when
dried in vacuo Cxfi3A'B^0(CTJd^s^'^) remains ;
and when dried at 200°-220° in H,the compound
Cr,03-HjO(CrjOj-(OH)2) is produced (Siewert, Z.
f. d. ges. Natwrwisi. 18, 244). .
For accounts of the earlier experin^ents on
composition of the various CrjOj.ii!HjO v. Lefort,
/. pi: 61, 261 ; Hertwig, A. 45, 298 ; Schaflner,
A. 51, 168; Premy, O. B. 47, 883; Ordway,
Am. S. [2] 26, 197; Mitscherlich, Lehrb. d.
Chem. [4th ed.] 2, 751 ; Vincent, P. M. [4] 18,
191).
The pp. obtained by the action of EOHAq
or NaO£U.q on CrCl,Aq, or on solutions of other
chromic salts, contains alkali which cannot be
removed by hot water.
Graham (2'. 1861. 183), by long-continued
dialysis of solution of freshly ppd. CrjOs.ffiHjO
in CrCljAq, obtained a liquid containing 1-5 pts.
HOI to 98-5 Crj03( = HCl:31-2CrA:a;H!0)5 ^^
solution, which may be taken as nearly pure
Cr^Oj-irHjO dissolved in water, was unchanged
on dilution or boiling, but was coagulated by
addition of traces of salts, with separation of
Cifi^.xE.fi.
A green hydrate — approximately pure
Crj03.2H20 —known as GuigUet's green, is ob-
tained by heating 10 pts. K^Cr^O, and 18 pts.
crystallised boric acid to low rediiess, and treat-
ing with H«0. It is scarcely soluble in boiling
HOlAq («. Scheurer-Kestner, Bl 1865. 23 ; Sal-
v6tat, O. B. 48, 295).
Properties and Beactions. — Any of the hy-
drates Crj03.a;H20 heated to 200° in air takes
up O, forming a black powder, which reacts
with HClAq evolving CI, and from which HjO
dissolves out CrO, (Siewert, I.e. ; Kruger, A. 52,
249). The three hydrates where a; = 7, 4, or 1,
are hygroscopic ; CrjOj-HjO is insol. in boiling
dilute HClAq, the two others dissolve in acids
forming chromic salts, CrX, (v. Chbomium, saiiIS
op). The hydrates are sol. in KOHAq, but on
standing or boiling they are reppd., and the pps.
contain alkali; they are si. sol. in NHjAq, but are
reppd. on boiling.
. The hydrates Cr203.a;H20 react towards acids
as salt-forming hydroxides ; but they also exhibit
slightly acidic functions. Thus, the pps. obtained
by adding EOHAq to solutions of chromic salts
cannot be washed free from alkali even by hot
water. Also, NH,Aq added to solution of a
chromic salt mixed vrith a salt of Ca or Zn, i&c
forms a pp. containing Cr^O, and CaO or ZnO,
&c. (Pelouze, A. Ch. [3] 33, 5). Solution of PbO
or ZnO in KOHAq, mixed with solution o<
CrjOj-EHoO in KOHAq, yields a pp. of MO.CrjO,
(Chancel, O. B. 43, 927). By long digestion ol
Cr203.a;H20 in cone. NHjAq a dark-blue com-
pound of Cr^Oj with NH, is produced, insol.
in water, but sol. in HClAq (v. Chbomites ; and
Chbomiujii, ammonio-balxs of).
Chromium, iodides of. Very little is knowil
regarding these compounds. None seems to have
been definitely isolated (v. Walz, C. N. 26, 245).
Moissan [A. Ch. [6] 25, 401) describes Crl,, or
Cr,!^, as a white salt, sol. in water with forma-
tion of blue liquid; obtained by the action of
HI, or I vapour, on heated Cr.
Chromium, nitride of, CrN. Mol. w. un-
known.
Preparation. — 1. Finely powdered Cr isheated
to whiteness in N ; the metal is again powdered
and heated in N, and this process is repeated
several times. Unchanged Cr is dissolved out
by cone. HClAq (Briegleb a. Geuther, A. 123,
228). — 2. CrCl, dried at about 120° is strongly
heated in dry NHj, the process being repeated
several times ; the residual CrCl, is removed by
long digestion in cone. HClAq in contact with
Sn (CrCl, is formed and dissolved) ; the product
is washed, and dried at 100°-120° (TJfer, A, 112,
281; i>. also Liebig, P. 21, 359; Schr6tter, A.
37, 148 ; Gmelin, Gm. 4, 139).
Properties and Beaetions. — Heavy, black,
amorphous powder. Heated to about 1500° in
absence of air, it is decomposed to Cr and N
(Ufer, A. 112, 281). It is unacted on by EOHAq.
u2
164
CHROMIUM, NITRIDE OF.
by dilute acid^, by cono. HClAq or HNO3, by H,
by steam, or by molten NiijCOj ; aqika, regia dis-
Bolves it slowly; cold cono. HjSO, dissolves it
with form^ation of Cr2(NH,)2(S04)4.24H20, and
' without evolution of N. Heated in HCl gas,
CrClj and NH,C1 are formed. Slowly sol. in solu-
tions of alkaline hypochlorites, with formation
of alkahne chromates and N ; decomposed by
molten KNO3, or KCIO3, with formation of
KjCrO, and N (Ufer, I.e.) i decomposes NH3 to
N and H at red heat ; unacted on by CI in the
cold, but when heated slight explosions occur,
and CrCl,, and N are produced.
Chromium, oxides of. Three oxides of
Cr are known, "CrjOj, CrO^, and CrO., ; CrjO^,
Cr^Oj, and perhaps an oxide higher than CrO^,
probably exist. Gr^Oj acts as a salt-forming
oxide towards acids, and also shows feebly acidic
properties ; CrO, is distinctly an anhydride, it
reacts with water to form the acid H^CrOj ; with
av-ids jt forms chromic salts, CrXj, and 0 ; no
salts corresponding to CrO^ have been prepared,
this oxide is said to evolve CI by the action of
HClAq. Chromous oxide, CrO, is not known,
but approximately pure CrO.H„0 (j;. CHEOMinM,
HYDKOxiDES 01") has been prepared. Crft, is said
to combine directly with 0 to form Cr02 ; it is
readily oxidised in presence of alkali to ohromate
MjOrOj, from which CrOj is obtained. CrjO.,
and CrjOp, if they exist, may be regarded as
CrO.Cr^Oa and 2Crj03.Cr03, respectively; CrO^
is sometimes regarded as Cr^Oj.CrO, (v. Chbo-
MIUM, ACIDS of).
I. Chkomio oxide CijOj {green oxide of
cTvronwum). Mol. w. unknown as compound has
not been gasified. S.G. 4'91 to 5'01 (Playfair a.
Joule, C. S. Mem. 3, 57; Schroder, P. 106, 226).
Schiff (A. 106, 114) gives S.G. 6-2 for crystallised
CrjOj. Crystallises in hexagonal forms ; a;c
=£1:1'3682. S.H. (21°-62°) -177 (Kopp, T. 155,
71).
Occurrence. — As ch/rome-ochre ; in combina-
tion with I'eO in chrome-ironstone.
Formation. — 1. By heating chromic hydrox-
ide (q. v.). — 2. By heating finely divided Cr in 0.
3. ByheatingCr03.— 4. By heating {NH<)2Cr20,
or Hg^CrO,. — 5. By heating CrClj in air.' ,
PreparaUon. — 1. A mixture of 5 pts. finely
,powdered, dry, KjCr^O,, and 1 pt. S, is heated
to redness in a crucible, and the product is
washed with HjO until all E2SO4 and K^S
are dissolved out (Lassaigne, A. Ch. [3] 14, 299 ;
Dietrich, W. J. 1866. 273).— 2. Equal parts of
dry, powdered, K^Cr^O,, and NH^Cl, are mixed
With a little Na2C03, strongly heated so long as
any gas (N) comes off, and the residue is washed
free from KCl (Wohler, P. 10, .46; Bottger, A.
47, 339).— 3. Crystallme Cr^Oj may be prepared
by passing vapour of CrOjCl^ through a glass
tubs heated to low redness (Wohler, P. 33, 341-) ;
or 'by heating to bright redness, in a Hessian cru-
cible, a mixture of equal parts of dry, powdered,
K2Cr20, and NaCl, covered with a layer of NaCl,
and washing the residue free fromEOl and NaCl
(SchifE, A. 106, 114 ; 108, 30). The crystalline
oxide is also obtained by strongly heating the
amorphous oxide in O (Sidot, C. B. 69, 201) ; or
by fusing the amorphous oxide -with CaCO, and
B,0, (Bbehnen, A. Ch. [3] 22, 211). Blake
(Am. S. [2] 10, 352) found crystalline Cr^Oa in
a furnace used for making K2Cr04 from chrome-
ironstone. (For other methods of preparing amor-
phous Cr^Oa V. Bariau, A. 40, 203; Berthier,
A. Ch. [2] 17, 56 ;, Bottger, J.pr. 103, 314. Foi
other methods of preparing crystalline CrjO, v.
Gentele, J. jar. 54, 187; Fremy, A. 49, 274; Miil-
ler, P. 127, 404 ; Otto, A. 142, 102.)
Properties :i,nd Beactions. — Amorphous Cr^O,
is a green powder, more or less dark, according
to the method of preparation. Crystalline Cr^Oj
forms very dark green, lustrous, hexagonal crys-
tals ; as hard as corundum ; isomorphous with
Fe^O, and AI2O3. Crj03 which has been strongly
heated, or crystalline Cr203, is insol. acids ; fused
with KNO3, or KHSO4, KjCrOj is formed and
dissolves in HjO. Amorphous Cr^Oa, if not
strongly heated, dissolves in most acids to form
chromic salts CrX3. Cr^Oj is not reduced by H,
and by C only when intimately mixed and
strongly heated. Heated in CI, CrO^Cl^ is formed ;
if the oxide is jierfectly dry, a little CrClj is pro- .
dueed (Moissan, Bl. [&] 34, 70) ; heated to about
440° in air, Cr02 is produced (Moissan, Z.c.) ;
heated in H^S, CrjS, results (Moissan, Z.fe.). .
Combinations. — 1. With water, indirectly,
to form CrjOj.icHljO; v. CIhbomium, hydhoxtdes
or. — 2. With, several metalUc oxides to form
compounds MCCr^O, ; v. Chbomiies ; under
CHBOMinM, ACIDS OF, p. 158.
II. Chuomium DIOXIDE CrOj. {Chrormum
tetroxide.' Brown oxide of chromium. Chromdte
of civromium.) Mol. w. unknown. This oxide
is a product (1) of the oxidation of Cr^Os, (2) of
the reduction of CrO,.
Formation. — 1. By heating Cr^Oj in air, or
0, to about 400° (Moissan, 4. Ch. [5] 21, 243).—
2. By heating Cvfia.x'Efi in air to about 250°
(Kriiger, P. 61, 219).— 3. By the action of
cone. Cr23S04Aq, or> CrCljAq, on KjCrOjAq
(? 5K2Cr04 Aq -F Cr23S04 Aq
= 3KjS04Aq-)-2K2Cr20,Aq-i-8Cr02) (Maus, P. 9,
127 ; Bensch, P. 55, 98).— 4. By the action of
NajSjOjAq on KjCr^OiAq
(? 2K2Cr20,Aq -I- NajSaOjAq
= E2Cr04Aq -i- K2S04Aq -i- Na2S03Aq-(- 3Cr02)
(Popp, A. 156, 90). (For other methods v. Kopp,
0. N. 11, 16 ; Vogel, J. pr. 77, 482 ; Siewert, Z.
f. d. ges. Nattmoiss. 18, 285 ; Schiff, A. 120,
207 ; Traube, A. 66, 106 ; Eammelsberg, A. 60,
203; Braun, J.pr. 90, 356; Oppenheim, Bl. [3]
1, 165).
Preparation. — NO is passed into warm dilnte
KjCrjO, Aq; CrOjis slowlyppd.: the solution must
not become concentrated (?2K2Cr20,Aq-l-2NO
= 2KN0sAq-fE2Cr04Aq-f3Cr02). The pp. is
wasljed with HjO, then with alcohol, and dried
at 250° for a long time untU the weight is con-
stant (Schweizer, /. pr. 39, 269 ; Hintz, A. 169,
367).
Properties and Beactions. — Dark grey, almost
black, powder ; very hygroscopic. Loses 0 at
300° ; heated in CI to 250° a little CrjOsClj is
formeS ; heated with HClAq, or with mixture of
HClAq and H2S04Aq, evolves CI (Moissan, ,
A. Ch. [5] 21, 243) ; heated with KOHAq, out
of contact with air, forms K2Cr04Aq and OrjOj
(Moissan, l.c.) ; not acted on by PCI, (Hintz, A.
169, 367).
III. Chbomtdm tbioxidb OiOa. (Chromic
anhydride. Bed oxide of cTvrommm.) Mol. w.
unknown. S.G. 2'67-2-82 (Playfair a: Joule,
C. S. Mem. 8, 67 ; Sohafarik, Sitz. W. 47 [2nd
CHROMIUM, OXIDES OF.
166
part], 256). CrystaUises in trimetrio prisms ;
0:6:0 = •7246:1: -6285. [About 190°] (Zettnow, P.
143, 468). S. (26°) 165 (Zettnow, Z.c.).
Occurrence.— In oombihatiouwithPbO, CuO,
&c., in a few minerals.'
S'armaUon. — Chromates, MjOrOj, are pro-
duced by heating Gtfi^ with alkaline oxidisers,
t.g. KOH,KNOs, KCIO3; or by the action of
oxidisers— e.5f. CI, KjMn^OsAq— on Cj:.fi,.xBJ)
in EOE!Aq. CrOs is obtained from chromates
by the action of strong acids.
Freparatum. — 300grams commercial K^Cr^O,
are warmed with 500 0.0. H^O and 420 0.0. cono.
HjSOi until dissolved; after 10-12 hours the
mother liquor is poured off from the crystals of
KHSO4 ; the solution is kept at 80°-90°, 150 c.c.
cono. BLjSOj are added, and then HjO drop by
drop till the pp. of CrOj has just dissolved ; the
liquid is evaporated until crystallisation begins.
After 10-12 hours the liquid is separated from
crystals of CrO, by pouring through a fuimel in
which is placed a little filter of thin Ft pierced
with smaU holes. The mother liquor yields a
second and third crop of CrOj crystals, by eva-
poration. The crystals of CrOj are spread out
on a porous plate, after 24 hours they are re-
moved, 50 o.c.pureHNOgAq (S.G.1'46) are added,
and the whole is placed on another porous plate;
if after 12 hours the CrO, still gives reactions
for H2SO4 and K, 25 o.c. BNO,Aq are added and
exposure on a porous plate is repeated. The
HNO3 is now removed by warming the crystals
in a basin, at first very slightly, then to a rather
higher temperature (60°-80), until the crystals.
appear perfectly dry and fumes of HNO3 are no
longer evolved. About 84 p.c. of pure CrO, is
obtained (Zettnow, P. 143, 468; modification of
methods of BoUey, A. 56, 113, and Bunsen, A.
148, 289). CrOj may also be prepared from
PbCrO^ by the action of cone. HjSOj (Sohrotter,
P. 59, 616) ; or by the action of HNOjAq (Du-
villier, C. B. 75, 711) ; also from BaCrO, (Duvil-
lier, Ijc.) ; also by the action of moisture on a
fluoride of Cr (? oxyfluoride ; v. Chromium fluob-
IDE, p. 163) obtained by decomposing PbCrO,
and CaFj by cono. HjSOj (Unverdorben, N. J. P.
9, 26 ; Berzelius, Leh/rbuch [5th ed.], 2, 319).
Properties. — Carmine-red, very lustrous, tri-
metrio prisms (Nordenskjold, P. 114, 612) ; or
loose, red, flakes. When melted at about 190°
and solidified, appears as very dark red, metal-
like, crystalline mass. Veiy sol., in H^O;
[OrO', Aq] = 1,900 (Sabatier, O. B. 103, 267);
S.G. of solution containing x p.c. CrOa at tempe-
rature t (Zettnow, P. 143, 474) :—
X,
t.
S.O.
8-25
16°
1-0606
12-34
19-6
1-0957
19-33
19
1-1569
31-83
20-1
1-2026
37-77
22
1-3441
62-23
22
1-7028
Sol. in pure ether and in cold dilute alcohol
(Zettnow, l.c.}. Solution in water is acid and
reacts with metallic oxides, &a., to form salts
MzCrOi {v. Chbomio acid). CfO, is easily de-
oxidised ; by action of acids it yields chromic
salts CrX„ and gives up 0.
BeacUms.—CiO, is very easily reduced.
1. CrOjAq is reduced by hydrogen pjudwig, A,
162, 47). — 2. Amorphous phosphorus heated to
200° forms CrO^ ; P dissolves in OrOsAq forming
an acid phosphate of Cr (Oppenheim, 5Z. [2] 1,
165). — 3. Potossmm or soaMtm reduces CrOj on
heating, probably to ' Cr.— 4. Sulphur forms
Cr^S,, and SO, (Moissan, A. Ch. [6] 5, 668).—
5. Heated with sulphydric acid, Cr^S,, HjO, and
S are fortaed (Harten, A. 37, 350).— 6. With
haloid aqueous aeids, halogen is evolved and
CrXj formed. — 7. Sulphurous anhydride has no
action at 100° ; at 180° CrO, and SO, are formed
(Traube, A. 66, 103) ; SOjAq and OrOjAq form
at first.HjSOjAq and CrO,, and then CroSSOjAq.
8. Nitric oxyie reduces CrOj to Cr^Os (Beinsoh,
J. pr. 28, 391; Wohler, A. 34, 236).— 9. Ar-
senious oxide forms Cr^Oj and HjAsO^Aq with
CrOjAq. — 10. Ammonia forms Cr^Oj, HjO, and
N ; light is produced. — 11. Phosphoric chloride
forms CrOjCl, and POCl, (Schiff, A. 106, 116).—
12. Ferric chloride heated with CrO, forma
Fe^O, and CrO^Clj (Geuther, A. 106, 239).—
13. Heated with violet chromic chloride CrOjClj
and CrjOj are formed (Geuther, A. 118, >69). —
14. CrOjAq is reduced to Cr^Oa by stannous
chloride,SnClf and SnOj being formed. — 15. Cold
cone, sulphuric acid dissolves CrO, (it is said to
be quite insoluble in very cone, acid with 16-17
p.c. HjO added) ; a compound Cr03.H2SO, is
probably formed {v. Combinations, No. 2), but
on heating, Cr^SSO,, or a basic Cr sulphate
(4Cr20s-6S03.7H2SOi according to Cross a. Hig-
gins, C. J. 41, 113), is formed, with evolution of
0. — 16. CtO, Aq is reduced by electrolysis to
Cri Cvfia, and 0 ; 30,225 gram-units of heat are
produced (Favre, O. B. 73, 890 a. 936; Geuther,
A. 99, 314 ; Buff, A. 110, 257).— 17- Iodine dis.
solves in cono. GrOsAq; the products are un
certain (Walz, G. N. 26, 245).— 18. Oxygen,
ozone, or pure dry chlorine, has no action on
CrOj (Moissan, A. Ch. [6] 5, 568).— 19. Heated
with carbon disulphide to 180° a Uttle COS is
formed (Armstrong, B. 2, 713). — 20. Very many
carbon compounds, e.g. Cfi^, CjHj, C^HjO,
CjHjO,, C5H5.CH3, &B., are oxidised by CrOjAq :
a mixture of K^Cr^O,, HjSO„ and HjO is gene-
rally employed.
Combinations.— 1. With water to form HjCrO^
(Moissan, A. Ch. [6] 5, 568; v. Chbomio acid,
under Cheomium, Aoms op). — 2. According to
Bolley {A. 56, 113) CrOj combines with sul-
phuric acid to form CrOj-HzSO; (?H2CrS0,)-,
it is prepared by addii^g crystallised CrO, to
cone. HjSO,, little by little, until no more is
dissolved, and after some days collecting the
brown solid matter and drying on a porous plate.
3. Schroder describes a compound with sulphuric
anhydride Cr03.3S03 (P. 69, 616 ; v. also Gay-
Lussac, S. 32, 447 ; Fritzsche, J. pr. 27, 252).
4. Moissan (O. B. 97, 96) says that the body pro-
duced by the action of H^OjAq on CrOjAq, usually
regarded as a higher oxide than CrOj, is rea,lly
a compound of CrO, and HjOj, viz. Cr03.HjOj
{v. infra).
IV. OlHEB OXIDES OP OHBOMICM.
(i) The oxide Or304 — corresponding to FejO^
NiaOi, and C03O4— is said to be produced by the
action of air-free KOHAq on CrCljAq, immediate
washing the pp. with boiling water and drying in
vacuo ; it is scarcely soluble in acids ; when
heated it fakes up O forming CrjOj (Pfligot,
A. Ch. [3] 12, 539). By electrolysing CrCljAq,
106
CHEOMIUM, OXIDES OF.
containing CrCl,, nndei special aondition8,Bunsen
obtained a black, amorphous, po'wder, insol. acids,
oxidised by heating in air to CijOg (P. 91, 619).
This powder seems to have been either a mixture
or a compound of CfO and Cr^Os (but v. Geuther,
A. 118, 66).
(ii) When CrO, is heated in air, or O, to a
little over 200° (Geuther a. Merz, A. 118, 62],
or -when a rapid stream of CrOjClz vapour is
passed through a tube heated to above 200°,
but not to redness (Wohler, A. Ill, 117), small,
lustrous, dark- violet, trimetrio prisms, S.O. about
4, sjiB obtained. According to Wohler the com-
position is CrgOj ; according io Geuther Cr^Og.
These crystals are distinctly magnetic, but lose
their luagnetism by heating in air ; when strongly
heated Gr^Og is formed. Insoluble in aU acids
including aqtM rcgia ; slowly acted on by cono.
boiling KOHAq ; decomposed by molten KOH to
CrA and KjCrO,.
Traube (A. 66, 108) describes two oxides
CrgO,, and Cr^O,:; but the existence of these as
definite compounds is doubtful.
(iii) When H^OjAq is added to CrOsAq, or when
a dilute, strongly acid, solution of BaO^in HClAq
is addedto 'Kfirfi^kxi, a deep-blue colour is pro-
duced in the solution (Barreswill, A. Ch. [3] 20,
SQi) ; this Colour quickly disappears, 0 being
.evolved (Schonbein, P. 108, 471). The blue
compound is more stable in ethereal than aque-
ous solution. paOj is added to HOlAq, ether
(free from alcohol) is then added, and then
KjDrjO,Aq drop by drop with constant shaking ;
the ether becomes deep azure blue, it is free from
HOI and H^SO,. The ethereal solution evolves
O when evaporated, and CrOj remains (Aschoff,
J. pr. 81, 401 a. 487). Ferrous salts are oxidised
by the blue ethereal liquid ; alkalis decompose
it to alkali chromates and 0 ; it is also decom-
posed by P2O5, CaCl„ MnOj, PbaO„HgO, Na, and
by acids and bases (Moissan, C. B. 97, 96; v.
alsoMartinon, jB2. [2] 45, 862). Certain alkaloids,
e.g>. strychnine and quinine, seem to form com-
pounds with the blue-coloured body ; these com-
pounds are, however, unstable. According to
Aschoff {J.pr. 81, 401 a. 471), for the formation
and complete decomposition of the blue-coloured
compound HjOj reacts with EjOrjO, in the ratio
6H202:K2Gr20, : assuming the blue compound to
be an oxide of Cr with the composition Cr^O,,
the reaction in question might be represented as
(1) KjCrjO,Aq + H20jAqH-2HCLA.q=
2KGlAq + 2H:jOAq + Gr^OjAq ;
(2) CrAAq + 6HClAq-)-4H20jAq =
Cr^GlsAq + 7H20Aq -1- 80. Pairley (C. N. 33, 237)
supposes that the blue compound is GrOe.3H20.
Moissan (C B. 97, 96) obtained an ethereal solu-
tion of the dark-blue compound containing 5 p.c.
Cr; at —20° in vacuo deep indigo blue, oily,
drops were' produced ; by the action of Na, H was
evolved, and by gently warming O was evolved ;
the volumes of these gases obtained corresponded
with those required by the formula Cr03.H20j.
The blue compound cannot be obtained by the
action of ozone on CrOjAq ; it is formed during
electrolysis only when HjO^ is also produced
(Moissan, Z.c).
Chrominm, oxychlorides of. Various oxy-
ohlorides, or perhaps compounds of Cr^Og and
CrCL, are obtained by evapor,ating CrCljAq at dif.
fercut temperatures (p. 167). Of the compounds
theoretically derivable from erOj(OH)j by re-
placing OH by 01, viz. OrO^OHGl and CrOjClj,
the second only is known ; the first would react
as an acid, the E salt of this aloid^is known (v.
Chloro-chromatesxxniei Ghbouiuu, acids oir,
p. 157). CrOgCl, easily parts with 0 and CI;
heated in a closed tube CrgOgGl, is produced.
I. Chbouyl ohlobidb CrO^Glj {Ohlorochromio
acid. Chlorochromicanhydnde). Mol.w. 155-06,
(115-9°) (Thorpe, C. J. 37, 3|62). S.G. J 1-961T
(Thorpe, l.c.). V.D. 78.
Formation.— 1. Equal parts CrOj and FeClj
are heated together in a retort (Geuther, A. 106,
239). — 2. CrOj and GrGlj are heated together in
the ratio 2CrGla:3Cr03 (Geuther, A. 118, 69).-3.
1 part CrO, and 2 parts PGl, are heated together
(Schifl, A.106, 116).^-4. EOl is passed into con<x
H2SO4 containing GrO, in suspension {B. 10,
1041). — 5. HGl is passed over OrO, (Moissan,
A. Ch. [6] 5, 568).
Preparation. — 10 parts NaGl are fused with
12^ parts KjCr^O, ; the fused mass in fair-sized
pieces is placed in a retort connected with a well-
cooled condenser, and 25 parts fuming E2SO4
are added. The reaction proceeds without heat-
ing (Thomson, T. 1827. 159 ; Berzelius, B. J. 6,
131 ; Wohler,' P. 33, 343 ; Etard, A. Ch. [5] 22,
218). About 70 p.c. of the theoretical yield of
GrOjOlj is obtained; part of the CrO^Gl, is de-
composed by the acid to GrO,, Gl, and Gr^SSOj
(Etard, Z.c). The distillate is redistilled several
times in CO^.
Properties. — ^A dark-red, mobile, liquid;
fumes much in the air ; dissolves CI and I in
large quantities. The vapour absorbs all the
light from a luminous flame except a narrow
band in the red (Stoney a. Eeynolds, P. M. [4]
41„291). If the vapour is mixed with O and
passed into a Buuseu lamp a violet flame is pro-
duced, showing lines in the violet, green, yellow,
orange, and red, part of the spectrum (Gott-
schalk a. Dreohsel, J. ^. 89,473). CrOjGlj is
best kept in sealed glass tubes.
Bea^tions. — 1. Easily parts with 0 and Gl;
acts as an energetic oxidiser and chlorinating
agent,, e.g. oxidises P, S, Hg, alcohol, tur-
pentine, &e., oxidises and chlorinates GgH,
(forming C„HCl302),C,oHa (forming O.oH^CljOJ
&c. (v. Liebig, P. 31, 359; Sohrotter, , 4. 37,
148 ; Heintze, J. pr. [2] 4, 211 ; Carstanjen, J.
pr. [2] 2, 61).— 2. Heated with POI3, POGl,, or
PCI5, OrClg and GrjOj are formed with evolution
of Gl (Gasselmann, A. 98, 213 ; Schiff, A. 102,
111 ; Weber, P. 107, 375 ; Gronander, B. 6,
1466).— 3. With water, CrOgAq and HGlAq are
formed with production of much heat. — 4. De-
composed, giving crystalline CrO,, when passed
through a warmtiibe (Wohler, P. 33, 331). —
5. Heated in a closed tube to 180°, CrjOjGlj and
01 are formed {Thorpe, C. J. [2] 8, 31).— 6.
Iodine dissolves in GrO^Glj; on heating GrgOjClj
and ICl are formed (Macivor, 0. N. 28, 138). —
7. Eeacts with KGlAq to form GrOj.OKCl (g. v.
under Chuomates) and HGlAq (Pfiligot, A. Ch.
52, 267).— 8. With K20r04Aq combines to form
GrO2.OK.Cl (Geuther, A. 106, 24Q).— 9. Burns in
dry NHj to form NH,01 and CrO, (Eideal, O. J.
49, 367).
II. Tbicebouyii chlobidi: Cr,OgCLi (Chro-
miiMn chromato-chloride). Mol. w. unknown.
Formation. — 1. Potassium chlorochromate,
CHEOMIUM, SALTS OF.
107
OrO,OK.Cl. is heated with oono. HjS04; CrO.Caj
and CraOjClj are produced together (Zettnow, P.
143, 328).— 2. I is dissolved in CrOjOlj, and the
product is distilled (Macivor, O. N. 28, 138).
Preparation.— CrOfil, is heated in a closed
tube for several hours to 180°, and the residue
is heated in dry OOj to 120° to remove unchanged
CrOjClj (Thorpe, O. J. [2] 8, 31).
Properties and Reactions. — ^A. black, amor-
phous, very deliquescent powder ; heated in air,
O, CI, and Cr^Os are formed ; easily reduced by
H to CrgOj with evolution of 0 and 01 ; dissolves
in HCL&.q, 01 is evolved, and OrOljAq remains ;
aqueous solution also gives oS 01 on heating.
III. OxYCHLOKiDEs from OrCljAq (Moberg,
J. pr. 29, 175 ; Loewel, /. pr. 37, 38 ; Paigot,
J. pr. 37, 475 ; Sohiff, A. 124, 157 ; Ordway,
Am. S. [2] 26, 197 ; Btehamp, A. Ch. [3] 56, 306 ;
57, 296). By evaporating CrOlaAq at 120° a
reddish residue, soluble in H^O, agreeing with
composition Or20,.80rCl3.24H20, was obtained;
this heated to 150° left a reddish-grey powder,
Orj03-4CrCl,.9H20( = Orj001«.3HjO) ; when more
strongly heated, and water added, a residue
rema;ined, 20rjC)a.2CrCl3( = OrOCl) (Moberg).
CrjOGl, was also obtained by heating CrClj-xE^O
to 150°-260°, and by long-continued digestion of
Cr203.a;H20 with cold dilute HClAq (Loewel ;
P^ligot).
CrOC1.3HjO was obtained by addingBaO^HjAq
to CrOljAq until the pp. no longer dissolved,
evaporating, treating the residue with alcohol
(BaCL; remained), evaporating to dryness at 100°
and ^Ting at 120° (Pffigot) ; the same com-
pound was obtained by boiling' OrOljAq with
Or^Oj-'KHjO (B6ohamp).
Chromium, oxyfluoride of, OrO^F,. Said to
be obtained by reaction between PbCrO,, CaPj,
and HaSO, (v. OUveri, 0. 16, 218).
Chromium, phosphide of, CrP. Mol. w. un-
known. S.G. 4-68.
Formation. — 1. By strongly heating OrPO,
with 0 (H. Bose, P. 34, 333)-^2. By passing
PHj over hot OrCL, (H. Kose, Z.c).
Preparation. — Pieces of P are placed in the
closed end of a tube of very infusible glass ; dry
EjCrOf is placed at a little distance from the P.
The SjOrO, is heated to redness ; the P is then
heated so that the vapour passes over the
KjOrOj; much heat and light are produced
during the reaction. The product is treated
with HjO, which dissolves out K phosphates and
leaves the CrP (Martius, A. 109, 82).
Properties and Beactions. — ^A grey-black,
crystalline, metal-like powder ; insoluble in all
acids ; heated in O, burns to CrPO, ; heated in
CI, forms POlj and CrOlj,; oxidised by molten
KOH with evolution of H, and by molten KOIO3
with evolution of 01.
Chromium, salts of. Compounds obtained
by replacing H of acids by Or. Two series of Or
salts exist; chromous salts OrX,, and chromic
salts CrX3, where X = C1 &o., SO, &o., PPj &a.
2 8
The v. D. of two compounds of Or, viz. CrOjClj
and CrOlj, have been determined; from this,
and the S.H. of Or, the value for the atomic
weight of the element is found to be 52-4 : the
simplest formulsa that can be given to the salts
of Or (Cr = 52-4) are CrX^ and CrX,, but these
formula do not necessarily represent the com-
position of gaseous molecules.
Chromous chloride, CrOLj, is the starting-
point for preparing most of the chroinous salts ;
these salts !are red or blue, and soluble in water ;
they very quickly absorb 0, becoming ohromio
salts ; they also absorb NO, and also OjHj (Ber-
thelot, A. Oh. [4] 9, 385). The most stabU ,
chromous salts at present known are the sulphate
CrS04.7H20, blue crystals isomorphous with
FeS0,7H.fi ; the acetate 0r(C2H3Oj)j,HjO, red
trimetrio prisms ; and the oxalate CrOjO,, yellow
crystalline powder, more stable than any other
chromous salt. (Por more details of individual
salts V. Acetates, Cabbonates, Bobates, Oxaii-
ATES, Phosphates, Sulphates, Svlfhiies; also
Ohbomous bbomide, Ohlobide, Etsboxide, Snii-
PHIDE.)
The normal chromic salts, CrX„ are obtained
by dissolving 0r203.a;H20 in acids, or by double
decomposition £;om soluble chromic salts ob-
tained in this way; these salts may be regarded
as derived from the hydroxide CrjOgHj. Ku-
merous basic saltsialsq exist, many derived from
the hydroxide Cr20.04Hj (v. Chbomic hydboxides).
The starting-point in the preparation of chromic
salts is usually K2Cr20, ; a solution of this salt
is heated with HClAq, or HjSOjAq, and a re-
ducing agent (commonly alcohol or SOjAq);
OrOljAq or CrjSSOfAq is thus obtained ; addi-
tion of NHjAq pps. CrjOj-icHjO, from which the
chromic salts are obtained by the action of acids.
Very many chromic salts exist in two forms, one
violet to red, the other green. In some cases
both varieties are known in the solid form and
with the same composition, e.g. red and green
CroSSO,; in other cases only a violet salt is
known in crystals, but a green solution is obtain-
able from this. Aqueous solutions of most of
the violet salts when boiled become green ;
many of these solutions become red or violet
again on cooling, sometimes only after standing
a long time. Only the violet, or red, solutions
yield crystalline salts ; the green solutions give
aiyorphous, gummy solids on evaporation. Vari-
ous hypotheses have been suggested to account
for these colour-changes. The change does not
seem to be due to hydration and dehydration
(Schrottpr, P. 53, 613), as dehydrating agents
do not effect the change from red to green
(Doyer van Oleeff, J. pr. [2] 23, 58). The experi-
ments of Kriiger (P. 61, 218), Siewert (A. 126,
94), and Boyer van Oleeff {J.pr. [2] 23, 68) seem
to show that in some cases at any rate, e.g.
chrome-alum, tlie normal violet salt is partially
decomposed, on boiling, into basic salt and acid,
and that on cooling the normal (violet) salt is
re-formed. Van Oleeff dialysed a green solution
of chrome-alum, and found the dialysate to con-
tain free H2SO4, and the liquid in the dialyser
excess ot Ci-fia ; he also dialysed a violet solu-
tion of chrome-alum, and found the same com-
position in the liquid, both inside and outside
the dialyser. The same chemist also found that
the violet solution became green on addition of
a little KOH, NaOH, HH3, or alkaline oarhon&ie ;
and that a little acid sufficed to reproduce the
violet colour. For details of individual salts v.
the arts. Cabbonates, Bobates, Kitbaies, SuIi-
fhates, &o. &o.
168
CHROMIUM, SELENIDES OF.
Chromium, selenides of, CrSe and Or^Se,.
Moi&sau (C. JR. 90, 817) describes these com-
pounds as black powders ; OrjSe j obtained by heat-
ing CrjO, in Se vapour, or OrOlj in HjSe ; CrSe ob-
tained by heating Cr^Se, in H, or OrClj in HjSe.
Chromium, sulphides of, Cr and S combine
when heated together to form Or^S, ; the same
sulphide is produced by heating CrjO,, CrCl,,
CrOj, &c., in HjS. No sulphide of Cr, but only
CrjOj.ajBtjO, is produced by. the action of H,,S,
alkali sulphides, &o., on solutions of Cr salts.
CrjS'j is reduced by H to CrS. The sulphide
OrjS, has also been obtained. Phipson (C. N. 4,
125) stated that a heptasulphide Cr^S, exists ;
but this has been disproved (v. Bender, B. 20,
756). Compounds of Cr^S, with ZnS, MnS, PeS,
&c., are obtained indirectly, e.g. ZuS-Cr^S, ;
CrjSa therefore resembles Cr^O, inasmuch as it
acts as a feebly salt-forming sulphide towards
more positive sulphides.
I. Chbomio sulphide CroSj. Mol. w. un-
known. S.G. 3-77 (Schafarik, J. 1863. 225).
Preparation, Dry HjS is passed over Gr^Oj
heated to about 440° ; the product is powdered
and agElin heated in H^S, and finally washed
with HjO, and dried at 100° (Moissan, 0. B. 90,
817). CrjSs is also obtained by the action of
HjS on hot CrClj (Liebig, P. 21, 359) ; or on
CrjBS04 (Traube, A. 66, 87); or by strongly
heating Cr^O, in CS^ (H. Eose) ; or KjCr^O, in
CSj (Schafarik, J. pr. 90, 9 ; Miiller, P. 127, 404);
or by heating CrjOa.aHjO with S, in absence of
air (Berzelius).
Properties and Reactions. — Brown-black,
lustrous powder, steel-grey if fused; not attacked
by acids, except HNOjAq and agua regia, which
dissolve it. Heated in air, gives SO^ and Cr^O, ;
in CI, gives SjOLj and CrCl, ; with molten
KNOj, EjCrO, and Ej^O, are formed; heated in
H, gives off HjS and S, and CrS remains (Mois-
san, CB. 90, 817).
Combinations. — Cr^S, is not acted on by
KOHAq or K^SAq ; but by heating KjCrOj with
K^COj and S, and washing with water, greenish-
black crystals (S.G. 2-79) are obtained, which
are easily soluble in HNOjAq ; these are proba-
bly a compound of K^S and Crj^, (Kopp, C. B.
19,1156; Schafarik, /.;?)»■. 90, 9). By heating
CrjO,.a!H20, MO.icHjO (or M^Os.ajH^O), and S,
in S vapour, and then in COj until no more S is
given off, Groger (Sitz. W. 81 [2nd part], 631)
obtained compounds of the form MS.Cr^Sj;
M = Zn, Fe, Mn. (v. Chromium, thioaoid or).
II. Ohbomous sulphidk CrS. ' Mol. w. un-
known. A black powder, produced by heating
CrjSa in H, or by heating CrCl, in H^S at 440°
(Moissan, C.B. 90, 817). Unchanged by heating
in absence of air ; heated in air CrjO, and 80^
are formed ; heated in CI, gives CrCl, ; scarcely
acted on by acids.
III. Chromium tetkasulphide CrjSj. Mol. w.
unknown. A greyish-black powder; insoluble
in H^O ; slightly soluble in cone. HClAq, easily
in cone. HNOjAq. , Prepared by heating dry CrjO.,
thoroughly mixed with excess of well-powdered,
S in H until no more S is given off, again mix-
ing with S and again heating in H (Groger, Sitz.
W. 81 [2nd part], 531).
Chromium, sulphooyanides of, and derivatives
of these compounds, v. SuLPHOCYAmnES, under
Cyanides.
Chromium, thioacld of. No thioaoid of Cr
is known; but Cr^Sj behaves towards some more
positive metallic sulphides as a salt-forming
sulphide ; in this respect it may be regarded as
the thioanhydride of hypothetical thiochromous
acid, H^Cr^Sj. Groger (Sitz. W. 81 [2nd part],
531) obtained the thioohromites ZnCr^S^,
i'eCr.^S,, and MnCrjSj, by heating mixtures of Cr
hydroxide and hydroxide of Zn, Fe, or Mn, with
8, for some time, then powdering and heating
in S vapour for several hours, and finally heating
in CO.^ until S was no longer given off. These
thiochromites are dark-brown or black powdesrs,
insoluble in H^O and HClAq, soluble in HNOjAq
and aqua regia. M. M. P. M.
CHBOMItJM GROTIP OF EIEMEHTS Chro-
mium, Molybdenum,Tungsten, Uranium. — These
four metals were discovered towards the end of
the eighteenth century. None of them is found
in the free state in nature, and the minerals in
which their salts occur are all comparatively
r.are. Chromium was obtained in 1797 by
Vauquelin from a mineral now known to con-
sist chiefly of lead chromate; in 1782 Hjelm
prepared molybdenum from an" acid earth-like
compound, which Scheele had obtained four
years earlier from molybdenum-glance, a sub-
stance until then supposed to be the same as
galena ; three years after the preparation of
molybdenum a new metal was obtained by the
brothers d'Elhuyar, by deoxidising an acid which
they had prepared from the mineral wolframite.
This acid was shown to be identical with that
which Scheele had made in 1781 from the
Swedish mineral tungstein, hence the new metal
was called tungsten, or by some chemists wolf-
ram. Uranium was the name given by Klaproth
to a new metal obtained by him 1789 from
pitchblende.
Chromium, molybdenum, and tungsten are
obtained by reducing the oxides of these metals
by carbon at a high temperature ; uranium is
prepared by removing chlorine from the chloride
by means of sodium. These metals are very hard
and very infusible ; uranium is fairly malleable ;
the others are brittle. The table on p. 169 pre-
sents the prominent physical and chemical pro-
perties of the chromium metals.
General formulce and character of salts.
MO, M2O3, MOj, MO., ; MS, M^Sj, MS,, MS.,, MS^ ;
MCI2, MCI3, MG1„, MCI5, MClj; -H^MO,, tIm^O,,
&c. The lowest oxides, MO, are scarcely known ;
hydrates of these oxides, when M = Cr or Mo, ap- ■
pear to , exist ; a few chromous salts, e.g,
CrSOj?!!^©, exist, but are unstable, and easily
become chromic salts. Sesquioxides, M^Oj, of
Cr and Mo are known ; the former dissolves in
acids with production of well-marked salts, the
chromic salts, Cr^SSO,, Cr26NOs,. Crj2P04, &o. ;
the latter is easily oxidised to MoOj, when moist
it dissolves in acids, but no definite salts have
been obtained from such solutions. Dioxides,
MOj, of all the metals of the group have been
prepared : of these, CrO^ is the least stable to-
wards heat or the action of acids, it parts with
oxygen at 30Q°, and dissolves in acids apparently
without deoxidation, but without producing defi-
nite salts ; M0O2 and WO^ also dissolve in acids
and produce salts, which, however, have scarcely
been obtained in definite crystalline form; the
CHROMTOM GROUP OF ELEMENTS.
169
fiolntiong of MoO, readily take up oxygen from
the air ; both oxides, when heated, are oxidised
to MOj ; TJOj dissolves in aoida to form a series of
nranous salts, e.g. V{SOi),, which are fairly easily
oxidised to uranyl salts, e.g. UOjSO, ; when this
oxide is heated it becomes UaOs. The oxides MO,
are all anhydrides; the mono-liydrated oxides
M0,H2O( = HjMO,) act as dibasic acids, forming
salts X2MO4 ; several series of salts derived from
more complex hydrates of MO, are also known,
e.!/. X2M2O,, XjMjOio, XMfljg, &o., in the case of
each metal except Cr these di- tri- or tetra-salts
are more distinctly marked than the salts XjMOi.
The anhydride OrOj eombifies with some normal
salts, e.g. K2Cr04Cr03, and also with a few anhy-
drides, e.g. CrOj.SSOa ; when dissolved in warm
acids it forms chromic salts (Cr^SSO,, &o.) with
evolution of oxygen. The anhydrides MoO, and
WO, form a series of complex compounds witb
anhydrides and water ; e.g.
PA-20M:oO,.38H2O ; SiOj.l2MoO,.26HjO ;
PA-24W03.6H,0; PA-22WO,.6H30, &o. &a.;
MoO, also combines with SO, to form M0O3SO,
(?MoOjS04). The anhydride UO, dissolves in acids
to form uranyl salts, e.g. UO^SO^, U02(N03)2, &o.,
which are more stable than the uranous salts
derived fromUO,. The metals of the chromium
group form several other oxides intermediate be-
tween those briefly described, e.g.Gtfi, interme-
diate between Cr^O, and CrOj, WjO, and WjO,,
between WOj and W0„ UjO, and UaO, between
UO3 and UO, : there are also indications of the
existence of a more oxidised oxide than CrO,
Atomic
Weights.
Chbomiuii.
62-4.
UOLYliDENnM.
95'9.
TuKaSTEN.
183-6.
TJRASITIM.
239.
One or more compounds of each element ' have been gasifidd ; specific heats have
been directly determined. Molecular weights unknown.
Spec. grav.
(approx.).
Specific heats.
Atom, weight,
Spec. grav.
(approx.).
Occurrence
and
jfreparation.
Physical
Above m.p. of Pt
(which is 2000°-
2500°).
6-5-6-8,
0-10 (? too low).
7-T.
Occurs chiefly as
chrome - iron-
stone, PeO-Cr^O,,
in which PeO is
more or less re-
placed by MgO
&a., and Cr^O, by
AI0O3 &o.; ^so as
lead chromate,
&c.; not widely
diffused ; ob-
tained by deoxi-
dising Cr,Os by G,
or xemoving 01
from CrCl, by
means of K or Zn,
or by electrolys-
ing a solution of
CrClj containing
CrCl,.
Very hard ; brittle ;
crystalline pow-
der composed of
small, brilliant,
tin-white crys-
tals (? rhombo-
hedra); descrip-
tions of proper-
ties differ consi-
derably, probably
the metal has not
been obtained in
approximate pu-
rity.
full
Infusible at
white heat.
8-5-3-6.
00C6
11-3.
Occurs in small
quantities as ox-
ide and sulphide,
also as lead or
cobalt molyb-
date ; obtained
by reducing the
oxide or chloride
by H, or the ox-
ide by C or by
KCN.
Ashen-grey powder,
or, when com-
> pressed, a silver-
like,, lustrous,
hard, brittle, in-
fusible metal.
Softens and agglo-
merates at white
heat.
18-2-19-2.
00334.
9-7.
Occurs very spar-
ingly as tung-
state of Ca, of
Pe and Mn, and
of Pb, also as
oxide ; obtained
by reducing the
oxide or chloride
in hydrogen.
Eesembles iron in
colour andlustre;
very hard, and
brittle; also ob-
tained as a brown
amorphous pow-
der; forms a very
hard durable
alloy with iron.
A full red-heat.
18-4-18-7.
0-028.
12-9.
Sparingly distri-
buted as oxide in
pitchblende, as
uranite of Ca and
of Cu, as carbon-
ate of U and Ca
&c.; obtained by
reducing the
chloride by
m^ansof sodium.
White, Instrona ;
hard, softer than
steel; somewhat
malleable, but
cannot be beaten
into thin plates ;
also obtained as
a grey - black
powder.
170
CHROMIUM GROUP. OF ELEMENTS.
Table — cont.
Chemical
OHROMnjM.
Burns in stream of
0 ; somewhat
more stable in
air than iron;
heated in air be-
comes covered
with very thin
film of oxide ;
oxidised by mol-
ten KNOa or
KC10s,butnotby
molten Na^CO, ;
easily dissolved
by dilute HClAq
or HjSOjAq, but
not attacked by
hot concentrated
HNOjAq ; com-
bines easily with
CI and I when
heated ; decom-
poses steam
slightly at a red
heat ; forms ' a
well-marked cy-
anide CrCy,.
Beplaces H of
acids forming
two series of
salts ; trioxide
acts as an anhy-
dride, forming
chromic acid
HjCrO,, from
which many salts
are obtained ;
Or^O, also forms
salts (chrotoites)
by heating with
ZnO, &o. Atom
of Cr is trivalent
in CrOl,.
MOLTBDKXUU,
Not oxidised in air
at Ordinary tem-
perature, but
burns at low red
heat; unacted on
by HCa, HF, or
dilute HjSOjAq;
dissolves in
cone. HjSO, ;
oxidised to HoO,
byHNOsAq; oxi-
dised by molten
KOH, but not
attacked by hot
KOHAq ; com-
bines with CI to
form M0CI5 when
heated ; also
with Br to form
MoBr^ and
MoBr^, but not
with I; forms a
nitride (?MosN2)
when MoCl, is
strongly heated
in NH,. Salts
in which H of
,acid is replaced
by Mo scarcely
known ; MoO,
acts as anhy-
dride of HjMoOj,
from which acid
several series of
salts are ob-
tained ; MoOj
also combines
with acid radi-
cles, e.g. SO,,
PjOs.&o. Formis
many oxyhaloid
salts. Atom of
Mo pentavalent.
TUNOSTEN.
Unchanged in or-
dinary air, but
burns in air at
red heat; com-
bines with CI
only at a high'
temperature, to
form WClj; dis-
solves iii boiling
cone. KOHAq to
form E tungstate
with production
of H ; oxidised
to WOa by hot
HNOaAq,
H,,SO,Aq, or
HGlAq ; forms a
nitridamide,
WaNa.W2NH2,by
heating WCI5 in
NH3. Does not
appear to form
salts by replacing
Hof acids; WO,
is the anhydride
of the acid
HjWOj, which
yields several
series of salts ;
WOj also com-
bines with acid
radicles, e.g. SO3,
Si02, &o. Forms
many oxyhaloid
salts. Atom of
W penta- and
hexa-valent.
UBAJfllTH.
Slowly tarnishes in
air ; oxidised at
150°-200° in air,
with evolution of
light and sparks;
combines with CI
or Br when
heated to form
VG\ and UBr< ;
very slightly at-
tacked by iodine
vapour ; heated
in S vapour
forms US2 ; dis-
solves in warm
dilute HjSO^Aq,
with evolution of
H, easily in
HClAq, also in
HNOsAq (when
melted and
cooled it is
nearly insoluble
in HNOs); does
not decompose
water; a nitride
(?UsNJ formed
by heating tJCl,
mixed with
NH.,C1 in NH,.
Forms two series
of salts, uranous,
e.g. 11(804)2, and
uranyl, salts, e.g.
U0,(S0J; UO,
is the anhydride
of HjUO,, from
which several
salts are derived,
the most marked
being M2U2OJ.
Atom of U tetra-
valent.
(I Ctfl,), and the oxide UO, is said to have been
obtained in the- hydrated state.
The sulphides MS3-(M = Mo, W) are acidic ;
sulpho-salts of the form HjMS, are known.
Of the haloid compounds of these metals the
following have been obtained as gases : CrCl,,
MoCl,, WCls, \VC1„ UCl,, UBr< ; the formulae of
these compounds represent the relative masses
of their molecules. It is said that CrF, has also
been prepared in the state of gas, but the evi-
dence is very doubtful ; the oxychloride CrOjClj
is an easily gasifiable body. Of the haloid com-
pounds, CrCl, and UCl, are obtained by heating
a mixture of Ci^aO, and C, or of UO^ and C, in a
stream of CI gas ; the former compound is very
stable, the latter is reduced by strongly heating
to UC1„ which is again reduced to UCl, by heat-
ing in hydrogen. When Mo or W is heated in
chlorine, in the one case M0CI5 and the other case
W Cl„ is produced, the other chlorides are ob-
tained by heating these in H or in CO,. All the
metals of this group readily form oxyhaloid salts.
Chromic chloride is a particularly interesting
compound; it exists in two varieties, one (green)
soluble in water and scarcely crystallisable, the
other (violet) obtainable in well-formed crystals,
but with difficulty soluble in water ; some other
chromic salts seem also to exist in two varieties,
e.g. the sulphate CrjSSOj (v. Chbomium, cklob-
IDES of, p. 162). At least seven series of double
compounds exist containing chromium, am-
monia, and acid radicle (Chbomiuu, aumonio-
SALTS OF, p. 158).
Of the four elements under consideration
only Cr and U form well-marked salts by re-
placing the hydrogen of acids ; these salts are
not, however, analogous in composition or pro-
perties. The chromic salts are for the most
part isomorphous with the salts of aluminium
and the persalts of iron ; the composition of these
three groups of salts is also similar, e.g. MuSSOj
where M = Cr, Al, or Fe. The uranyl salts —
UO2SO4, &c. — to a certain extent stand by them-
selves, although we know of many so-called
OHKYSANISIC AOID.
171
basio Baits of chromium, iron, copper, Ac, which
resemble the uraiiyl salts in containing ozygen
as well as metal and acid radicle.
Of the trioxides, M0„ it may certainly be
said that the most acidic in character is GrO,,
and the least acidic is 170, ; this is in accord-
ance with the general rule that the higher oxides
of the elements in the same growp (as group is
used in the nomenclature 'of the periodic law)
become less acid in character as the group is
ascended.
The four elements all show distinct analo-
gies with S, Se, and Te, which occur in the same
group but in odd series ; e.g. existence of acids
MO^IOH),, and of anhydrides BIO3, &c. ; but
^hese three elements are more distinctly non-
metallic in their properties than Or, Mo, W, or U.
The elements of the chromium group, as well as
the three elements S, Se, and Te, show analogies
with that element which is the first odd series
member of the group, vis., oxygen (v. Classifi-
cation, p. 207 ; also Oxyoen Gbotip or Bub-
MBNTS. For detailed accounts of the proper-
ties of the elements of this group and their
chief compounds v. Chboioiuim, MoiiTBDENtru,
Tdnosten, Ueanium, and for the other salts of
these metals, v. Cabbonates, Nitrates, Sul-
phates, &o. M. M. P. M.
CHBOICYL CELOBISE CrO^Cl, v.CEBOMniu,
OXYCHLOBIBES OP, p. 166.
CHEUSOCBEATHTINE C5H5N2O. A feebly
alkaline substance said to occur in muscular
tissue (Grautier, El. [2] 48, 18). Its solutions
are ppd. by HgClj, by ZnOl^, by iodine dissolved
in aqueous KI, and by sodium phosphomolybdate.
It forms a deliquescent hydrochloride and a
crystalline platinochloride.
CHBYSAMMISIC AOID v. TEiBA-mTBO-ox;-
iUIDO-ANTHBAQUINONE.
CHBYSAHUIC ACID v. Tetba-niibo-di-oxs-
ANTHBAQUIKOIIB.
CHBTSANILIITE C„H,sN, i.e.
ato-
Di-anUdo-phenyl-acridine.
[2C7°-270°]. A by-product in the manufacture
of rosaniline. Discovered by E. 0. Nicholson
and investigated by Hofmann (O.B. 55, 817; B.2,
379), who prepared methyl ethyl and phenyl
derivatives.
Preparation. — Commercial ' phosphine,'
which is chrysaniline nitrate,"is dissolved in hot
.vater, cooled, and slowly added to dilute NaOH.
The base separates as a bright yellow flocculent pp.
It is dried at 100° and crystallised from benzene,
which retains homologues in the mother liquid
(O.Pischer a. G. Komer, A. 226, 177 ; B. 17, 203).
Synthesis. — Byoxidisingq?)p-tri-amido-triphe-
nyl-methane[2:l]NH,.C8H,.CH(CsH^.NH2[4:l])a
which is obtained by reduction of the product of
condensation of o-nitro-benzoic aldehyde with
aniline.
ProperWes.— Golden plates (from benzene)
C,bH,5N8,C„H„. The benzene of crystallisation
is easily expelled. Golden needles of C,gH,jN,2aq
(from alcohol). Much less soluble in alcohol
than its homologues. When pure it does not
clot together when heated with NaOH. In small
quantities it may be distilled without decompo-
sition. It dyes wool and silk yellow.
Reactions. — 1. Heated with cone. HCl
(8 vols.) at 170°, NHj is exchanged for OH and,
on cooling, large red prisms of the hydrochloride
of chrysophenol separate. These dissolve in
NaOHAq, but on exactly neutralising, chryso-
phenol GggHi^N^O, separates as an orange pp.,
si. sol. water, ether, or benzene, but v. sol. alco-
hol. From dilute alcohol it crystallises with
2aq. It is a yellow dye and a strong base, form-
ing acid and neutral salts. It is insol. aqueous
NaaCOa, but sol. aqueous NaOH (0. Fischer a.
G. Komer, A. 220, 181).— 2. By diazotisation
and treatment with alcohol it is converted into
phenyl-acridine. Chrysaniline (10 g.) dissolved
in H,S04 (50 g.) and water (4 g.) is well cooled
and treated with nitrous acid gas in excess. The
product (containing the diazo-sulphate) is slowly
poured into boiling alcohol (600 g.). The alcohol
is distilled ofi and the residue mixed with water
and distilled with' steam at 200°-250°. Phenyl-
acridine [181°] passes over. 3g. pure chrys-
aniline gave 1 g. phenyl-acridine, or 40 p.c. of
the theoretical yield. — 3. McI gives C^gHisMegNjI,,
which separates from water in red needles. NH,
converts it into CjoHuMcaNjI, whebce AgjO
forms CjjHijMejNj, a brown amorphous powder.
EtI acts in the same way.
Wormation in, the rosamline melt : This can
be explained by two hypotheses: (1) That in
the condensation of jp-toluidine (1 mol.) with
2' mols. of aniline, together with the ordinary
para-condensation producing rosaniline, a con-
densation simultaneously takes place which is
partly ortho and produces o-di-^-tri-amido-
methane, which by further oxidation yields
chrysaniline —
0
1— NHj /NnHj
NH,
OK)^-^
NH,
(2) That o-di-^-tri-amido-methane is produced
by condensation of 1 mol. of o-toluidine with 2
mols. of aniline. This latter hypothesis is the
most probable and is supported by the above-men-
tioned synthesis (Fischer a. Komer, B. 17, 203).
Salts. — B'2H01.—B'2HC1 aq.—B'HCl.—
B'HNOj.- B'2HN0,.
Picric acid compound
B'(CeHj(N0j)30H)j aq (at 100°). Bed needles.
ii-acet2/Z-<Zerti;afi«eC,jH„N(NHAc),. —
Microscopic needles, dissolves in alcohol with a
blue fluorescence, nearly insol. water. It ie
nearly as strong a base as chrysaniline itself
and forms salts which greatly resemble, the
corresponding salts of chrysaniline.— B'HCl :
soluble yellow microsoojpic ' needles, dyes wool
and silk yellow. — B'HNOs : sparingly soluble
crystalline pp. (Anschiitz, B. 17, 433).
GHBYSANISIC ACID v. Di-nitbo-amido-
BEHZOIO AOID.
172
CHEYSAROBIN.
CHUTSAROBIN C^UJ), i.«.
C.H.(OH)<gg(0^)>CA(OH,)(OH)
O [170°-178°1.
C.H,(OH)<^g(OHj>0,H,(CH,)(OH)
Occurs in Goa powder (also called arrarobo
powder) to the extent of about 70 p. c, from whiob
it is extracted with C^g. Small yellowleaflets, m.
Bol. benzene, CHCI3, and a,cetic acid, si. sol. alcohol
or ether, insol. water. Insol. NHjAq (difference
from chrysophanic acid). By leading air into the
solution in KOH, ohrysophanic acid is formed :
Cs„Hj,,0,+ 20j= 2C,5H,„04 + 3B.fi. By distilla-
tion with zinc dust it yields methylanthracene.
Di- acetyl derivative. Light yellow
leaflets.
Tetra- acetyl derivative [228°-230°].
Yellowish prisms ; si. sol. alcohol with a blue
fluorescence. By oxidation with^CrOj it gives
di - acetyl - chrysophanic acid (Liebermann a.
Seidler, S. 11, 1603; A. 212, 29; cf. De SUva,
Ph. [3] 5, 723; Holmes, P;i. [B] 5, 801).
CHEYSATIC ACID a,H,,N,0,5 (Mulder,
J.pr. 48, 16 ; A. 72, 289) or C.oH.^NA (Schunok,
A. 65, 240). An acid obtained by heating chrys-
ammic acid with aqueous KOH. Sol. water.
CHEYSATEOPIC ACID G,jai,fi,. [202°].
S. (hot water) 1-3. An acid extracted by ether
from an acidified infusion of the root or leaves
otAtropa belladonna (Kunz, Ar. Ph. [3] 23, 722).
Pale yeUow trimetrio prisms ; may be sublimed.
SI. sol. cold water. Its alcoholic solutions ex-
hibit green fluorescence.
CHEYSAZIN V. Dl-OXY-ANIHEAQUINONE.
CHEYSAZOL v. Di-oxt-anihuaceke.
CJioHcCH
CHEYSENE C„H,j i.e. \ \ . Mol. w.
C„H,.CH
228. [250°]. (above 360°). S. (alcohol) -037 at 16°;
•17 at 78° ; S. (toluene) -24 at 18° ; 5-39 at 100°
(Bechi, B. 12, 1978). V.D. 7-95 (calc. 7-89).
Ocowrrence. — In coal-tar, in petroleum, and
in the product of the dry distillation of fats, fir-
wood, amber, and resins (Laurent, A. Ch. [2] 66,
136; Berthelot, Bl. [2] 7, 30; J. 1867, 605;
PeUetier a. Walter, A. 48, 345; Williams, J.pr.
67, 248; Adler,B.12, 1891; Prunier, A. Ch. [5]
X7, 6). I
Fomumon. — 1. By passmg naphthyl-phenyl-
ethane through a red-hot tube (Graebe a. Bun-
gener, B. 12, 1079).— 2. The statement that
chrysene is among the products of the passage
of benzene through a red-hot tube has been con-
tradicted (Berttelot, J. 1867, 605 ; Bl. [2] 7, 30 ;
22, 437; G. Schultz, B. 6, 415).— 3. Among the
products obtained by passing benzene-azo-benz-
ene through a red-hot tube (Olaua a. Suckert, B.
8, 37). •
Properties. — Colourless Scales or , flat tri-
metric octahedra (from benzene) ; a:b:c =
1:1-376: 2-490 ; v. si. sol. alcohol, si. sol. ether
and cold CS,, m. sol. boiling benzene and HO Ac.
The solutions as well as the crystals exhibit deep
reddish-violet fluorescence. Hot couc. H^SO^
forms a blue solution (Liebermann,^. 158, 299).
CrOj in HOAc gives ohiysoquinoue (i^.v.). By ex-
haustive chlorination with SbClj it yields GC1„
CjClg and pei-chloro-benzene (Meiz a.Weitb,£.
16, 2881).
' Pioiio acid compound '
CisHiAHaiNOJaOH. Beddish-brown needles
(from crude xylene) (Galletly, O. N. 10, 243).
Deooriiposed by alcohol.
Di-nitro-anthroquinone oompou,nd
C„H,jCnH„(N02)„02. [294°]. Formed by dissolv-
ing greenish-yellow commercial anthracene [208°]
(50g.) in alcohol (5 litres) and adding HNO,
(30g. of S.G. 1-4), and boiling. Bed needles;
v. si. sol. alcohol, ether, and benzene. Tin and
HGl reduce the di-nitro-anthraquinone, setting
free pure chrysene, which may conveniently be
prepared in this way.
Di-chloro-blirysene C,sH,„Cl2. [267°]. From
chrysene and 01. Soft white needles (from
benzene) ; v. si. sol. alcohol ; may be, sublimed.
Tri-chloro-chrysene CuHjCla. [above 300°].
Slender needles (from benzene). From chrysene
and 01 at 170° (Schmidt, J.pr. [2] 9, 270). "
Di-bromo-chrysene C,8H,„Br2. [273°]. From
Br and chrysene in CSj. White needles (from
benzene) ; y. si. sol. all menstrua. Kot attacked
by alcoholic KOH below 180°. KjCrjO, and
HjSO., oxidise it to ohrysoquinone.
Hitro-chrysene CigHjiNOz. From chrysene
and HNO3 (S.G. 1-25) at 100°. [209°]. Thick
prisms, grouped in stars (from benzene). May
b^ sublimed ; v. si. sol. alcohol, ether, and CSj.
Di-nitro-ohrysene C,sH,„(N02)2. [above 300°],
From chrysene and boiling HNO3 (S.G. 1-3).
Slender yellow needles (from HOAc). V. si. sol.
alcohol, ether, and benzene.
Tetra-nitro-ohrysene 0,8Hi,(N0j)j. [above
300°]. From the preceding and fuming HNO3.
Yellow needles (from HOAc). Detonates above
300P.
Tri-bromo-di-nitro-chrysene C,jH,(N02)2Br3.
Yellowish-red needles. Sol. hot alcohol, less in
0,Hj and ether. Prepared by the action of
bromine on tetra-nitro-ohrysene (Adler, B. 12
1894).
Isomeride of chrysene C,8H,j. [196]. A
by-product in the preparation of diphenyl by
action of sodium on bromo-benzene (Schultz, A.
174, 229). Long needles (from alcohol). Is per-
haps triphenylene (Schmidt a. Schultz, A. 203,
135).
Isomeiide of chrysene (1) 0,sHij. [186°].
A product of the action of Al^Clj on a mixture
of naphthalene and phthalic anhydride (Ador a.
Crafts, C. B. 88, 1855). Laminse (from ether-
alcohol). Its bromo-derivative melts at 112°.
CHBYSETTDIENE. A hydrocarbon, obtained
in small quantity in the distillation of aluminum
(;3)-naphthol (Gladstone a. Tribe, C. J. 41, 16).
CHEYSIN CisH,„0,. Gh/rysmic acid. [275°].
S. (cold alcohol) -66 ; (hot alcohol) 2. Occurs in,
the buds of Fopulus nigra, P.pyramidaUs, and
P. balsamifera (Piccard, B. 6, 884 ; 7, 888 ; 10,
176). The alcoholic extract, after successive
treatment with lead acetate and H^S, is evapo-
rated, and the residue reorystaUised from spirit
and washed with alcohol, ether, CS^, boiling
water, and boiling benzene. The residue is
heated to 275°, and crystallised from spirit.
Bright yeUow plates. Insol. water, nearly insol.
benzene, CSj, and chloroform. Aqueous alkalis
form a yellow solution, but on boiling they split
it up into phloroglucin, acetophenoue, benzoic
acid, and acetic acid. Lead acetate gives, in
alooholio Bolutions, a pp. soluble in excess.
CHRYSOQUINONE.
178
FejCl, gives a violet colour in alooholio solu-
tion.
Di-bromo-chrysin CisHsBrjO,. Formed by
adding Br to an aloohoUo solution of ohrysin.
Felted mass of silky needles.
Di-cJiloro-chrysin. Needles.
Di-iodo-ohryBin G,,B.J..ft^. Formed by add-
ing iodine and iodic acid to an alcoholic solution
of chrysin.
Di-nitro-ohrysin C,^B^(S02)fit. ^^o^ ohry-
sin and HNOj. Large crystals (from hot HOAo
or aniline). Forms an orange-red basic ammo-
nium salt and a yellow acid ammonium salt.
Methyl derivative C,5HaMe04. Tecto-
chrysin. [164°]. From chrysin, Mel, and KOH
dissolved in MeOH. Exists in poplar-buds toge-
ther with ohrysin, from which it may be sepa-
rated by means of its much greater solubility in
benzene and chloroform. It is much less solu-
ble in alcohol than ohrysin. Large sulphur-
yellow monoclinic prisms (from alcohol) ; a:h:c
= l-54:l:l-86 ; .;8 = 53°. Insol. alkalis. It forms
a di-brbmo-derivative.
Ethyl derivative G^^^^iOi- [146°].
Iso-amyl derivative C^^Jfj^^^O^.
[125°]. Its di-bromo- derivative crystallises in
needles.
CHRYSOFLUOEENE C„H,j i.e. |° 'NcH^
[188°]. Silvery glistening tables. V. e. sol.
ether, chloroform, and benzene, less sol. cold
alcohol. Formed by heating chrysoketone with
HI and P at lo0°-160° (Bamberger a. Kranzfeld,
B. 18, 1934).
Chrysofluorene alcohol | ^OH(OH).
[167°]. Formed by reduction of chrysoketone
with .zino and HCl (B. a. K.). White silky
needles or glistening plates. Sublimable. V.
sol. alcohol, ether, and benzene, si. sol. ligroin.
Its alcoholic solution is turned blue by addition
of H2SO4. Strong H2SO4 dissolves it with a
reddish-violet colour.
CHBYSOGEN C. 94-3 to 95 p.o. ; H 5-7 to 5
p.c. [280°-290°]. S. (cold befizene) -04; (boil-
ing benzene) "2 ; S. (boiling HOAc) 'Oo ; (cold
HOAc) -01. An orange-coloured hydrocarbon
contained in smaU quantity in crude anthracene,
and separated therefrom by repeated crystallisa-
tion from benzene (Fritzsche, G. B. 64, 910 ; Bl.
[2] 6, 474 ; Prunier, Bl. [2] 31, 293). Orange
tables with green lustre ; may be sublimed.
Cono. H2SO4 dissolves it without change. Small
quantities colour white hydrocarbons yellow.
Its solution, is bleached by sunlight. It forms,
with di-nitro-anthraquinone, a compound ciys-
tallising in olive needles with golden lustre.
CHEYSOGLYCOILIC ACID
1" >0{OH).COjH. White powder. Formed
c,„h/
by boiling freshly precipitated amorphous chryso-
quinone with alkalis (Bamberger a. Kranzfeld,
B. 18, 1933).
CHBYSOIDJNE v. Bemene-i^o-m-phenylene
diamine.
CHEYSOKETONE |° *\cO. [130°], Glis-
tening red needles. Scarcely volatile with
steam. V. sol. the ordinary solvents. Formed
by the oxidation of ohrysoglycoUio acid
I " ' \c(OH).00,H with K^CrjO, and HjSO,
(Bamberger a. Kranzfeld, B. 18, 1933).
CHRYSO-NAPHTHAZINE C^sHi^N, ».«.
CisHioC I ^C,„Hj. Formed by mixing a solu-
tion of chrysoquinone in aqueous-alooholio
NaHSOj with an aqueous solution of naphthyl-
ene-o-diamine hydrochloride, sodium acetate,
and acetic acid. Yellow microorystalline pow-
der (Liebermann a. Witt, B, 20, 2443).
CHRYSOPHANIC ACID v. Di-oxy-methil-
AHIHBAQmNONE.
CHEYSOPHANIN. A white amorphous flub-
stance said to be contained in the aqueous
decoction of senna leaves (Bourgoin, 0. B. 73,
1449).
CHEYSOPHEUOL C^HisNA Oxy-amMo'
plumyl-acridiiie. Formed by heating ehrysani-
line with HCl under pressure at 180°, NH, being
replaced by OH (Fischer a. Korner, B. 17, 205).
Small yellowish-red needles (containing aq). SI.
sol. water, benzene, and ether, v. sol. alcohol and
caustic alkalis. The hydrochloride and sul-
phate form sparingly soluble yellow crystals.
CHEYSOaTriNCWE C.sH.oOj i.e. C,,H,-CO
I I
C^H,— CO
C H C O
or I '° ° II I . Mol. w. 258. [235°]. . Occurs
o<;h4.c.o
in American pletrolenm to which, according to
Prunier (Bl. [2] 31, 293), it imparts the blue
fluorescence. Obtained by oxidising chrysene
with CrO, in HOAc (Liebermann, A. 158, 309 ;
Graebe, B. 7, 782 ; B. Schmidt, J. pr. [2] 9, 250,
270). Orange plates (from alcohol) ; m. sol.
benzene and HOAc, si. sol. ether and CS^. May
be sublimed. Cone. H2SO4 forms a deep-blue
solution whence it is ppd. unaltered by water.
KaHSO, forms a crystalline compound, decom-
posed by much water.
Beactions. — 1. KMnOj gives phthahc acid
(Anschiitz a. Japp, B. 11, 211).— 2. Distillation
over zinc-dust forms chrysene.— 3. Aqueous SOj
at 100° forms hydro-chrysoquinone. This
body is also formed by the action of zinc-dust
and aqueous KOH. It is an amorphous white
powder, re-oxidised by air at 200°, or by shaking
its solution in H2SO4 with air. — 4. PCI5 and
POClj at 200° form di-chloro-chrysoquinone and
deca-ehloro-chrysene. — 5. Distillation with soiia-
Ume gives a hydrocarbon C,sH,j (? phenyl-naph-
thalene). — 6. Heated with benzoic aldehyde and
aqueous NHj in sealed tubes at 100° it forms a
product which, if boiled first with alcohol and
then with benzene, yields to the latter a body
CjsHijNO crystallising in silky needles [259°-
265°] which may be sublimed. The reaction is
analogous to that of benzoic aldehyde and am-
monia on phenanthraquinone (a. v.), hence this
.C-0
body should be 0,8H,„< || >C.Ph (Japp a.
NO— N'*^
Streatfeild, 0. J. 41, 167).
174
OHRYSbQUINONE.
Di-chloro-cIiryBoquinone CisHgCljOj. From
ohrysene POClj and PCI, (2 mols.) at 200°; a
yellow flocoulent pp. is then obtained by adding
alcohol (L.).
Di-bromo-chrysotiuinoiie CgHsBrjOj. Bed
leaflets. [160°-165°]. Prepared by bromination
of ohrysoquinone (Adler, B. 12, 1893).
Di-nitro-ohryBoquinone C^^^i^O^fi^. [230°].
From ohrysoquinone and HNO3 (S.d. 1'4) (A.).
Bed needles.
Tetra-nitro-chrysoquinone C,sH8(N02)40j.
From chryaoquinone and cold cone. HNO3.
Oratige powder (L.).
Chrysoquinone di-sulphonio acid
C,.H,(SOaH),Oi.-BaA" (A.).
Di-ozy-chrysoquiuone 0,i,Hj(0H)j02. Chrys-
ezarin. [above 300°]. Said to j have been ex-
tracted from crude artificial alizarin (Claus, B.
8, 1S7). Dark brown needles with bronze lustre
(from HOAc). Insol. cold water, sol. alcohol,
ether, and alkalis.
CHEYSO-TOLTJ-AZINE C^^^^'i.e.
/^\
CisHijC I >C5H3(CH3). Prepared by mixing a
solution of chrysoquinone in aqueous-alcoholic
NaHSO,, with an aqueous solution of tolylene-o-
diamiue hydrochloride, sodium acetate, and
acetic acid. Small golden needles. Sublimable.
Dissolves in ovanc. H^SO, with a blackish-violet
colour (Liebermann a. Witt, B. 20, 2443).
CHBYSOTOLTIIDIITE OjiHjiN, (?). Found
among the by-products in the preparation of
rosaniline (DeLaire, Girard, a. Chapoteaut, C. B.
68, 964).
CICTJTA OIL. The oil from the seeds of
Cicuta virosa is of the same nature as Boman
oil of chamomile (g. v.) (Trapp, J. pr. 74, 428).
CICUTENE C,„H,„. (160°). A dextrorotatory
terpene in the essential oil obtained from the
root of the water -hemlock, Cicuta virosa (An-
kum, Z. 1869, 248). The same plant is said to
contain an alkaloid, Cicutine (Polex, Ar. Ph.
18, 174 ; Wittstein, Buchner's Bejaert. 18, 19).
CmiCIC ACID C,5HjA- Mol. w. 240. [44°].
Occurrence. — In the foetid oil ejected by a
kind of bug BhapMgaster punctipenrds when
irritated. The insects are washed with alcohol,
and the residue extracted with ether (Carius, A.
114, 147). Occurs also in spider's web (Yaleute,
<?. 12,567).
Properties. — Prisms (from ether), lighter than
water. Insol. water, v. si. sol. alcohol, v. sol.
ether. Has a rancid odour.
Salts. — NaA'. — KA': amorphous.
Chloride C,sH„OCl : [0. 44°].
Sthyl ether BtA'. Oil.
CIMICIC ALDEHYDE OuH^sO. [72°]. Occurs
in spider's web (Valente, G. 12, 557). Beduoes
Fehling's solution and ammoniacal AgKOg.
CIKCHAUIDHiTE v. Cinchona bases.
CINCHENE G,^,„Nj. Cinchomdene. [125°].
Formed by treatment of cinchonine or cinchon-
idine with PCI5, and boiling the resulting cin-
ctonihe-chloride CigHjiOl or cinchonidine chlor-
ide with alcoholic KOH. Trimetric tables a:b:a
= •6017:l:-5022. By heating with HCl at 220°-
230° it is converted into apocinchene G,3H„N0,
MeCl and KB, being split off and E^O taken up
(Comstock a. KBnigs, B. 14, 1854; 17, 1989).
Methylo4odMe BTVIel: [186°]; monosym-
metrioal tables, a:&:c = l-5838:l:-9114; t. sol.
alcohol, si. sol. water, scarcely sol. ether (Com-
stock a. Koenigs, .5. 18, 1219).
(a)-Cinchene-di-broinide GiJ3^t^s. [113°].
Formed, together with about an equal quantity
of (i3)-cinohene-di-bromide, by the addition of
bromine to cinchene (Comstock a. Konigs, B. 19,
2858 ; 20, 2512). Monosymmetrical crystals^
a\h:o = -9570:1: -8686, ;8 = 65° 62'. Converted by
boilingwith alcoholic EOHinto dehydrocinchene.
The hydrobromide forms concentric needles ; the
nitrate small colourless crystals, si. sol. dilute
HNO3 ; the zinc-double chloride colourless
needles [c. 250°].
(;S).Cinehene-di-bromide Ci.HjjNjBrj [134°].
Formed, together with (a)-cinchene-di-bromide
[118°], and in about equal quantity, by the addi-
tion of bromine to cinchene. Bhombic sphen-
oidal hemihedral crystals, a:&:c = '6552:1:1'2017.
Somewhat less sol. alcohol and ether than the (a)-
isomeride. Like the (a)-isomeride it is converted
by boiling with alcoholic EOH into dehydrocin-
chene. The hydrobromide forms granular crys-
tals more soluble than the (a)-hydrobromide(sepa-
ration). The zinc-double chloride forms colour-
less needles [c. 250°]. The nitrate separates in
the form of a jelly, si. sol. dilute HNO3 (C.a.K.).
Cinchene-bromo-hydride CuHjiBrNj. Hydro-
bromcinchene. [10S°-116°]. Formed by dis-
solving cinchene in cooled HBr and allowing to
stand for two days. Monoclinic crystals,
a:5:c = -8541:1: -8280, 3 = 63° 7'; isomorphoua
with cinchene-di-bromide. V. sol. alcohol, ether,
benzene, chloroform, and acetic ether, si. sol,
ligroin (Comstock a. Konigs, B. 20, 2522).
Dehydrocinchene 0,„H,bNj. [0. 60° hydr.]. Ob-
tained by boiling dehydrocinchonine chloride
OibHidN^CI or (o)- or (/3)-cinchene-di-bromide
OijHjjBr^Nj with alcoholic EOH. Iiong colour-
less needles (with 3aq). — B'^jBrj! very soluble
small prisms. — ^B"HjCl2ptCl, : very sparingly
soluble red tables (Comstock a. Ednigs, B. 19,
2857).
Apocinchene C,„H„NO. [209°]. Formed by
heating' cinchene with HCl at 220°-.iJ30° (Com-
stock a. Konigs, B. 14, 1854 ; 17, 1986 ; 18,
2379; 20, 2674). Colourless needles. Sol.
alcohol, acids, and alkalis. The compounds
which it forms with acids and with bases are
dissociated by water.
ReacUons. — By fusion with KOH or NaOH it
gives oxy-apocinchene C^H^NO,. Its ethers
are oxidised by CrOj to cinchonic acid ; on oxi '
dation with ^ute HKO, they yield alkyl-apo
cinchenio acids C„H,s(OB)N.COjH.
Salts.— B'HBr. [c. 256°]: yellow needles
(from alcoholic HBr).-^B'HI. — B'jH^tCl„.
[0. 235°]. The Ag salt is a nearly insoluble pp.'
Acetyl derivative Gyt'B.^f^kaSlO. [119°].
Methyl ether Ci,H,j(OMe)N : oil; v. sol.
alcohol, ether, &a., nearly insol. water.
B'HCliaq: [c. 198°], crystalline solid.
Ethyl ei;terC„H,8(OEt)N:[71°]; colour-
less prisms.
Bromo-apocinchene 0„H,i>BrNO. [188°].
From apocinchene hydrobromide in chloroform
and HOAc by adding Br. Crystalline, v. sol.
aqueous alkalis, benzene, and chloroform, less
sol. alcohol and ether. CrO, oxidises it to
bromoform and cinohonio acid. Boiling alco-
holic NaOH does not attack it.
CINCHONA BARK.
17£
Ai-bromo-apocinclieiie. Ethyl ether
C,^,eBrj{OEt)N. [118°]. From ethyl-apooin-
chone (10 g.) and Br (15 o.o.)
Oxy-apocinchene 0,sH,„NOj. [217°]. Formed
by fusing apocinchene 0,5H,s(0H)N with KOH
or NaOH (Gomstook a. Koenigs, B. 18, 2385).
Colourless crystals. V. sol. caustio alkalis, si.
Bol. cold alcohol and pure ether, nearly insol.
water and dilute acids.
Acetyl derivative PisH,jAoNOj. [203°].
Hethyl-apocinchenic acid
C„H,3(0Me)N.C08H. [234°]. Formed by oxida-
tion of the methyl ether of apocinchene with
dilute HNO3 (Gomstook a. Koenigs, B. 18, 2383).
Colourless crystals. V. sol. alcohol, acids and
alkalis, nearly insol. water.
Ethyl-apotfinchenic acid 0„H,j(OEt)N.COjH.
Formed by oxidation of the ethyl ether of apo-
cinchene G,jH,a(OBt)N with dilute HNOj (Corn-
stock a. Koenigs, B. 18, 2384 ; 20, 2674). Crys-
tallises from absolute alcohol in yellowish anhy-
drous needles [162 ] ; from dilute alcohol in
crystals (containing aq) [126°]. By heating with
HCl at 130° it is split up into CO,, EtCl, and
homo-apooinchene C„H,5N0a!aq [185°].
The hy drobromide of homoapocinohene B'HBr aq
crystallises in yellow needles or prisms [222°]
si. sol. water. Homo-apociuchene on fusion with
potash gives an acid [230^] split up by heat into
CO2 and another acid C„E[„NO., (?) [223°].
Salts. -The Ag, Ga, Ba, Pb, Zn, and Cu
salts are sparingly soluble. — AgA'. —
(HA')APtOl,.
CINCHOL OjoHajO. [139° water-free]. Is
found in all true cinchona barks but not in G.
Ouprea; in largest amount (up to 0-03 p.c),
along with gome quebraohol, in 0. Oalisaya Var.
Ledgeriana. Found also along with oupreol.
Helms' ' Cinchocerotine ' (Ar. Ph. [3] 21, 279)
was probably wholly or partly cinchol. Further,
Liebermann's ' Oxy-ohino-terpene ' {S. 17,871)
is cinchol (Hesse).
Preparation. — From crude cupreol, the
acetate being separated by repeated crystallisa-
tions from alcohol from the acetates of quebra-
ohol and cupreol (0. Hesse, A. 228, 288 ; 234, 375).
Properties. Plates (containing aq) from
alcohol. LsBvorotatory in chloroform solution ;
[o]„= -34-3° (in a 6 p.Cj solution). Its proper-
ties are similar to those of cupreol.
Acetyl derivative Ca,H330(CjH90).
[124°]. White needles from alcohol. M. sol.
alcohol, V. sol. ether and chloroform. Ltevo-
rotatory (in chloroform); [a]n=— 41-7° (in a
i p.c. solution).
Propionyl derivative C2,H,jO(C3H50).
[110°]. Microscopic plates.
CINCHOCEEOTIN Gj,H„0,- [130°]. Pro-
bably identical with the preceding. Deposited
in tubes through which an alcoholic extract of
South American oalisaya- bark and lime is
passed (Hehns, Ar. Ph. [3] 21, 279). Chromic
acid gives acetic acid, butyric acid, and oincho-
oerotio acid 0,„HbOj [72°].
CINCHOLEPIDINE v. (Py. 1) MBiHYL-gcDJo-
LINE.
CItrCHOIiINE. strongly basic oil. Volatile
with steam. Occurs in the mother liquors from
quinine. V. sol. alcohol and ether, less sol.
vrater. The hydrochloride forms colourless
quadratic plates. The oxalate is sparingly
soluble in water (Hesse, B. 15, 858).
CUrCHOMEBONIC ACIO and iso-cinchome-
ronio acid v. Ptbidine di-oabboxylio aoid.
CINCHONA BARK. Cortex OvnclwncB and
Chinee, Cortex Peruvianus, Peruviati Bark,
Ecorce de Qwmquina,China rimde. — This name is
given to the bark of various species of Cinahoiia,
which, with about thirty other allied genera,
constitute the tribe CinchoneeB of the order
BubiacecB {v. Pharmacographia, f. 338). They
have been long known for their antifebrile pro-
perties, which are chiefly due to the contained
alkaloids, which are absent in all the allied
genera, with the exception of Bemigia, some
species of which contain them.
These medicinal barks were first introduced
into Europe from Peru about the year 1638, by
the Countess of Ghihohon, wife of the Viceroy
of Peru (in whose honour the name cinchona
was given to the genus by LinnsBus), and being
afterwards sent over by the Jesuits, acquired
great celebrity for the cure of intermittent fevers,
being known by the names of Pulvis Gomitessie,
Jesuiticus, Patrum, &o. The cinchonas are
natives of the mountain regions of South
America, on the eastern slope of the Cordillera
of the Andes and on the mountain ranges of
Ecuador and New Granada, growing at eleva-
tions from 3,000 to 11,000 feet, no species being
known to inhabit the low aUuvial plains.
In 1853 an attempt was made by the Dutch
Government to introduce the cultivation of cin-
chona into Java, but at first great difficulty
was found in obtaining seeds or plants of good
qualities, oWing to the extreme jealousy of the
natives.
In 1860 Mr. Clements Markham was sent by
the Government of India to South America to
collect seeds and plants, and after great difficul-
ties be and his coadjutors succeeded in intro-
ducing the most valuable species of cinchona
into India, and Mr. G. Ledger, who was then re-
siding on the west coast of America, also suc-
ceeded in obtaining a supply of seed of the'' finest
variety of the Galisaya bark.
The cultivation of the cinchonas thus intro-
duced into the East Indies has increased to such
an extent that much the greater proportion of
the bark is now supplied from Ceylon, Java, and
India,from whence upwards of 14,000,000 lbs. of
bark were imported in 1885.
This cultivation has also been successfully
introduced into Jamaica and elsewhere, in tropi-
cal regions where high mountains give the re-,
quisite elevation, and in the natural home of the
genus there are ndw large plantations of culti-
vated cinchonas of the finest qualities.
In collecting the bark in tiie native forests,
the trees are invariably out down, and the bark,
when stripped off, dried either in the sun or on
hurdles arranged over a fire in a hut.
In the plantations of cultivated bark, the
system of cutting down the trees is adopted to
some extent, but a far more economical method
of harvesting the bark is by the pn)cess of ' re-
newing,' introduced by the late W. G. Molvor,
by which a succession of crops of burk can be
obtained from the same tree. For this purpose
longitudinal incisions are made into the bark
and about half the bark removed in alternate
17G
CINCHONA BARK.
strips, leaving the remaining bark intact, and the
stem is then covered viith moss. A fresh layer
of bark is then formed from the cambium with
Eurprisingrapidity, and in a few months it attains
the thickness of the original bark when several
years old.
It is remarkable that the renewed bark is not
only in most oases richer in total alkaloids than
the natural bark but contains a far higher pro-
portion of quinine, which appears to take the
place of the less valuable alkaloids. Another
more imperfect process adopted •for renewing
barks is to cut off the external layers with a
spokeshave, but the results are rarely so good
as in the former process, as it is essential that
the liber layers of the bark should be cut
through without injuring the cambium beneath,
which is more difficult to do in this manner than
in the other system.
Between thirty and forty species of cinchona
have been described, but most of them are of no
practical value. Those used in pharmacy and
in the manufacture of quinine are as follows.
I. Yellow or Calisaya Bark. This is the
most valuable of all the species of cinchona. It'
is'found in commerce in quills formed by the
contraction of the bark when drying, which are
covered with a rough epidermis. It was for-
merly found also in flattened pieces, from which
the epidermis had been removed, and which
have been dried under pressure, and was then
known as fiat yeUow bark.
II. Crovm bark. Pale bark. Loxa bark
yielded by O. officinalis and the allied species,
found in quills, with a rough blackish-brown or
dark grey surface. This was formerly the chief
bark used in medicine imder the name of Peru-
vian bark. It is largely cultivated and approaches
the Calisaya in richness.
III. Bed bark, Cinchona Rubra and Succi-
rubra, so called from the red colour of the sap
and of the mature bark. Owing to the vigorous
growth of this species, it has been, cultivated in
India to a very large extent, and has been adopted
in the British Pharmacopoeia for use in galenical
preparation. It is less suited for the preparation
of quinine, owing to the great proportion of cin-
obonidine that it contains.
IV. Soft bark. Columbian and Carthagena
ha/tk, yielded by C. Lucumifolia and Lancifolia,
imported inquills or broken pieces, with a whitish
shining epidermis, which scales off easily. They
vary greatly in the quantity and quality of the
alkaloids.
V. PitoAjo harks, yielded by O. Fitayensis,
are imported in short curly pieces of a brownish
colour, either bare or with a rugged whitish epi-
dermis. They are rich in alkaloids, especially
quinine and quinidine.
VI. Cuprea bark, yielded by Remigia Pe-
dunculata. Although not a true cinchona bark,
tUs may convenieijtly be included here as the
only known species of any other genus that has
yielded the cinchona alkaloids. It is imported
in short quiUs and broken pieces of a deep red
colour. The bark is of a very compact texture,
of much higher specific gravity than the true
cinchonas. It gives with ammonia a purple
solution of considerable tinctorial power. It
contains quinine, quinidine, cinehonine, but no
cinchouidine, and an alkaloid, cupreine, dis-
covered by Paul and Oownley, which exists itt
the bark in a combination with quinine, pre-
viously taken for a distinct alkaloid, and desig
nated homoquinine, an allied species. B. Pur-
dieana yields no quinine, but a new alkaloid
called by the discoverer, M. Arnaud, Cinohon-
amine.
Along with these principal species are found
in commerce the bark of a great number of
species of Cinchona, most of which contain
little or no valuable silkaloid, and also barks of
allied genera, especially of Ladenbergia and
Exostemma. These barks contain none of the
cinchona alkaloids..
The organic constituents of cinchona bark
are quinine, quinidine, cinehonine and ciu-
chonidine, and some isomeric modifications
of these bases, quinamine, uncrystaUisable
alkaloids, in some species aricine, paricine,
and their congeners ; quinic acid, quinovin and
cinchotannic acid, cinchona red, colouring matter,
wax, and fatty matter, a small quantity of vola-
tile oil, along with starch, gum, and woody fibre.
The barks of some of the allied genera also
contain quinovin, cinchotannic acid, and quinic
acid. The ash of cinchona bark consists chiefiy
of calcic and potassic carbonate, containing also,
besides iron, a notable quantity of manganese.
For detailed analysis vide Carles, Ph. [3] 3, 723.
The first chemical examination of cinchona
bark appears to have been made in 1785 by
Hermbstadt, who obtained from it calcium
quinate, which he designated as essential salt of
quinine. Schneider in 1807, and Vauquelin in
1808, separated quinic acid from the calcium
salt. Quiuotannio acid was discovered by Deyeux
in 1793, and obtained in a more definite form by
S^guin in 1797. Cinchona bitter and cinchona
red were obtained from red cinchona bark by
Beuss in 1810. The first discovery of the alka-
loids was made by Gomes of Lisbon in 1811, who
appears to have obtained cinehonine in an im-
pure state ; but its true nature was not dis-
covered till 1820, when Houtou-Labillardifiro
drew attention to its alkaline reaction, and com-
municated his observations to Pelletier and
Caventou, who in the same year succeeded in
isolating first cinehonine, and afterwards qui-
nine, and proved them to be true vegetable
alkaloids. The isomeric modifications of these
alkaloids were afterwards discovered and vari-
ously named. Pasteur (O. B. 36, 26 ; 37, 110) re-
duced those then known to four, quinine and its
isomeride, quinidine, and cinehonine and its iso-
meride, cinchonidine, and also investigated the
isomeric modifications of these alkaloids pro-
duced by the action of heat in strong acid solu-
tion, viz. quinicine and cinohonicine. Hesse
has now investigated the whole subject, and has
described various alkaloids which, however, with
the exception of a modification of cinchonidine
named by him ' homo-cinchonidine,' and the
recently discovered hydroquiniue, h.o not seem
to have been isolated by other observers.
Cinchona barks are employed medicinally in
the form of tinctures, fluid extracts, and infu-
sions, and were thus used long before the dis-
covery of the alkaloids, and, although it is to
these bodies that the medicinal value is chiefiy
due, the cinchotannic acid and other ingredients
appear also to be of medicinal value.
CINCHONA BAEK.
177
Beaction» of Cinchona bark. — Most salts of
the ciuohona alkaloids give a puiple tar when
strongly heated in a test-tube, especially if they
are mixed with cellulose. The same reaction is
observed when a bark containing them is heated,
and is very oharaoteristio. The test was pro-
posed by Grahe, of Kasau, in 1858. Water ex-
tracts a portion only of the alkaloidal contents
of cinchona bark, and the cinohotannates of the
alkaloids being more soluble in hot than in cold
water, a hot infusion becomes turbid on cooling.
The solution obtained by treatment with acidu-
lated water gives the following reactions : — The
alkaloids give a whitish precipitate with excess
of caustic alkali, and with tannic acid, and a
yellow crystalline precipitate with platinic
chloride, if these precipitates are submitted to
dry distillation, the characteristic odour of quinol-
ine is observed. Of the acid constituents quino-
tannic acid gives precipitates white with solution
of gelatin, green with ferric salts, dirty white
with tartar emetic. Quinovio acid gives, with
sulphate of copper, first a green colour and then
a precipitate which, when washed, has a bitter
metallic taste. Quinic acid ^stilled with sul-
phuric acid and manganese peroxide yields a
distillate of quinone ; this test is proposed by
Stenhouse (Mem. Ohem. Soc. ii. 22t)) to distin-
guish true cinchona bark.
For the qnantitative analysis of cinchona
bark, various processeshavebeen proposed, many
of which give good results in practised hands,
but in all of which success largely depends on
details of manipulation only to be acquired by
practice. The earlier processes depended on dis-
solving out the alkaloids with hydrochloric acid,
precipitating the alkaloids by caustic alkali. A
great excess of acid is required for the extrac-
tion of the whole alkaloid, and a great excess of
alkali for the complete separation of the alkaloids
from the cinohotannio acid which precipitates
along with them by exact neutraUsation. Better
methods are those in which the salts of the
alkaloids are decomposed in the bark by treat-
ment with alkaU, and the alkaloids then ex-
tracted by suitable solvents. De Vrij (Phar-
mctcographia, p. 365, and Ph. [3] 4, 241) recom-
mends to mix 20 g. of powdered bark with milk
of lime (5 g. lime to 50 c.c. water), dry the mixture
slowly, stirring frequently. Then boil the dry
powder with 200 c.c. alcohol of S.G-. 0'830, pour
off and filter the solution, and boil a^gain with
100 c.c. alcohol, throw the whole on the filter, and
wash further with 100 o.c. alcohol, acidulate with
dilute sulphuric acid, filter, and distil, but not
to dryness (water must be added if necessary),
when all the spirit is separated the aqueous solu-
tion is filtered. The filtrate and washings are
reduced to 50 c.c, and while still warm treated
with caustic soda in excess. After cooling, the
solution is decanted ofi and water added before
throwing it on the filter. It is then washed with
the smallest possible quantity of water, pressed
between folds of blotting paper, dried, and
weighed. The weight is that of the total alka-
loids in the bark.
The process given in the British Pharma-
copceia, f. Ill, is also a good one, it is as fol-
lows : — Mix 200 grams of the bark in fiaie powder
with 60 grams of hydrate of calcium ; moisten
the powders with half an ounce of water, mis
Voi. U.
the whole intimately ; allow it to stand for an
hour or two, it will then present the character!
of a moist dark-brown powder, in which there
should be no lumps or visible white particles.
Transfer the powder to a fiask, boil for half an
hour with three fluid ounces of a mixture ot
three volumes of benzene and one of amylio
alcohol, decant and filter the solution, leaving
the bark in the flask, boil again with the same
solvent and decant as before ; repeat the third
time, and finally throw the bark on the filter and
wash with the solvent. The filtrates are then
shaken repeatedly with water acidulated with
hydrochloric acid tiU the alkaloids are all re-
moved, the acid washings concentrated, and if
, the process given below for the separation of
the alkaloids is adopted, the alkaloids are pre-
cipitated by excess of alkali.
The process given in the German Pharma-
copceia is also efficient. /
The separation of the oinohona alkaloids
depends on their relative solubihties in various
reagents, but in most cases these do not differ
so widely as to give a perfectly satisfactory sepa-
ration, and the separation is made more ^ffioult
by the tendency of the alkaloids and their salts
to form more or less definite compounds with
one another.
A convenient process giving fairly aooarate
results is as follows : — Treat the powdered mass
of mixed alkaloids with ten times its weight of
ether ; this will dissolve the quinine and amor-
phous alkaloid, and small quantities only of the
other alkaloids ; wash the alkaloids out of this
ethereal solution by excess of dilute sulphurio
acid, and neutraUse after heating to boiling with
dilute ammonia, using no more water than is
necessary; the quinine will then, on coohng,
crystallise out almost entirely as sulphate, which
saJt is almost insoluble in a cold solution con-
taining ammonic sulphate. The crystals after
filtration and washing with a small quantity of
water are pressed between blotting paper and
dried at 100°. 73-4 pts. of the anhydrous salt
equal 100 of the hydrated crystals. The salt
should be tested for cinchonidine, which may be
present in small quantity. The alkaloids con-
tained in the mother liquor are then precipitated
by alkalis, converted into neutral acetates, and a
solution of potassium iodide and a small quantity
of alcohol is then added ; on standing quinidine
iodide wiU crystallise out if present. Of this
salt 100 pts. equal 71*8 of the alkaloid. A solu-
tion of potassio-tartrate of sodium is then added
to the mother liquor, and on agitation and stand-
ing, tartrate of cinchonidine will crystallise out
if any of that alkaloid has been dissolved by the
ether ; 100 pts. of this salt equal 80-4 of the
alkaloid. The mother liquor now contains amor-
phous alkaU, which may be precipitated by a
solution of sodic hydrate and weighed. The
portion insoluble in ether must be also converted
into neutral acetates, and the solution tested for
quinidine by potassic iodide, a few drops of spirit
being added, and for cinchonidine by potassio-
tartrate of sodium as above. If a considerable
proportion of this alkaloid is present it will pro-
bably contain a notable quantity of quinine, as
ether fails to give a complete separation. After
removal of any quinidine and cinchonidine present
by those reagentSi the solation contains the oia-
178
CINCHONA BARK.
ohonine, whioli may be precipitated by caustic
alkali and weighed. Dr. de Vrij recommends
that the quinine should be precipitated from the
solution of alkaloids soluble in ether, as iodo-
sjilphate {Ph. [3] 6, 461) ; in skilful hands this
inethod of analysis gives accurate results. In-
stead of commencing the separation of the alka-
loids by ether, Dr. Moens recommends that the
neutral aqueous solution of the mixed alkaloids
be treated with excess of solution of sodic potas-
sio-tartrate, which throws down the whole of
the quinine and cinchonidine as tartrates. The
tartrate is then decomposed by alkali, and the
quinine and cinchonidine separated by ether,
the alkaloid dissolved in the ether being either
weighed directly as quinine or preferably con-
verted into sulphate and weighed as such. Great
care must be taken in this case to decompose the
tartrate entirely, to avoid underestimating the
quinine.
The method of estimating the relative pro-
po]?tions of quinine andjjinchonidine in the pre-
cipitated tartrates by determination of the specific
rotation of the polarised ray has been recom-
mended by Drs. De Vrij and Oudemans, but no
published process for bark analysis gives the
tartrate obtained direct from the crude mixed
alkaloids in a sufSeient state of purity to give
really trustworthy results by this method.
The distribution of the alkaloids in the
bark has been the subject of careful observation.
It was first observed by Carles (Ph. [3] 3, 643)
that though quinine exists in all portions of the
bark, it is contained in much larger proportion
in the external and cortical layers than. in the
internal .liber layers, and his observation has
been confirmed by other observers.
On the other hand, the corky epidermis found
in some barks, specially in certain varieties of
officinalis, such as the knotty bark of Jussieu
does not contain alkaloid.
Alkaloids begin to form in the bark even when
very young, and increase in quantity until the
bark is mature, the maximum yield being at-
tained at ages varying with the species and cir-
cumstances of growth — from five to fifteen years,
or even later. The relative proportion of the
different alkaloids also varies greatly in the same
tree.
The increase of the dextrogyrate alkaloids,
qninidine and cinchonine, in the root barks is
remarkable. This is specially the case in stunted
or unhealthy trees in which the root bark is often
exceptionally rich in alkaloid. As a rule a
luxuriant growth of the plant is required to give
the maximum of alkaloid, and therefore it is
natural that manures should have a beneficial
effect. Wluable experiments on this subject
have been carried out by Mr. Broughton at the
Government Plantation at Ootacamund {Ph. [3]
3, 521). He found that a great improvement in
the yield of quinine was caused by the use of
guano, a greater by the use of ammonia salts,
but most of all by the use of farmyard manure.
A series of experiments on renewed bark of
C. succirubra in Ceylon, on the other hand,
showed a maximum of improvement from the
use of bones ; ammonia and cattle Inanure pro-
ducing less improvement, the different result
being, no doubt, owing to a different condition
pf the soil. In some soils a very great improve-
ment is caused by dressings of lime. , This ques-
tion is one deserving of much more investigation
than it has yet received. D. H.
CIKCHONA BASES Quinine, Cinchonine,
Cinchonidine, and Arioine are described in
separate' articles. The existence of many of the
following bases, requires confirmation. In the
names of these alkaloids guis used before i, and
ch before any other vowel.
Chairamine Cj^H^eN^O, aq. [140°]. [233°
when dry] [o]d = ibout -i- 100°. In the bark of
Bemijia Pturdieana (Hesse, A. 225, 243). Named
from xaipm, because Hesse ' rejoiced ' at dis-
covering it. Slender needles (containing aq)
(from dilute alcohol). Sol. ether and chloroform.
Its alcoholic solution is alkaline to litmus.
H2SO4, with or without M0O3, forms a colourless
solution, turning dark green.
Salts.— B'HGlaq. Needles.— B'sH^SOj 8aq. ,
— (B'HCl)2PtCl,2aq.
ConchairamineC^jHajNaOiaqBtOH. [82''-86°] ;
B'aq [c. 110°] ; B' [c. 120°] [o]d (for B') = -I- 68-4
in 2 p.e. alcoholic solution. In the bark of Be-
myia PurcUeana (Hesse, A. 225, 246). It has
three melting-points according as it is dry, with
water of crystallisation, or with alcohol of crys-
tallisation also. Colourless prisms (containing
aqEtOH) (from alcohol). Sol. ether and chloro-
form. Cone. HjSOj, with or without M0O3,
forms a brown solution turning green.
Salts. — B'HCl. — (B'HCl)2PtOl4 5aq. —
B'HI aq.— B'HSNG aq.— B'^H^SO^gaq.
Methylo-iodide. — ^B'Melaq. Bed crystals.
B'Mel 3aq. Colourless crystals.
Methylo-chloride.—'B'MeOl 2aq. Pla-
tino-ohloride.— {B'MeCl)3HCl(PtCy2l4aq.
Chairamidine C^^H^jd^ aq. [0. 128° when
dry]. [oJd = -F 7*3° in 3 p.o. alcoholip solution.
In the bark of Bemijia PwfcUeana (Hesse, A.
225, 253). Amorphous powder, insol. waiter, sol.
ether, alcohol, benzene, and chloroform ; solu-
tion in cone. H^SO^ slowly turns green. Animal
charcoal removes it from solution in acetic acid.
Salts.— (B'H01)jPtCl4 5aq.— Sulphate is
gelatinous.
Conchairamidine G^^B^jdf aq. [115° when
dry]. [a]D = — 60° in a B p.o. alcoholic solution.
In the bark of Bemijia Purdieana (0. Hesse, A.
225, 256). Crystalline. V. sol. ether, aloohoi*
chloroform, benzene, and acetone. Its alcoholic
solution is neutral to litmus. In cone. HjSO,,
with or without MoO,, the solution is dark
green.
Salts. — Well crystallised. — B'HCl 3aq. —
(B'HCl)jPtCl, 5aq.-B'jH2SO, 14aq.
Cinchamidine G^U^TAfi. [230°]. [o]b =
— 98'4. Occurs in the mother-liquors from
homocinchonidine (Hesse, B. 14, 1683 ; cf. Porst
a. Bohringer, B. 14, 1270 ; 15, 520). Colour-
less plates, needles, or prisms. Sol. alcohol and
chloroform, si. sol. ether, insol. water. Has an
alkaline reaction.
Salts. — B'HCl 2aq: trimetrio prisms. —
(B'HCyjPtCl, 3aq: yellow amorphous pp. —
B'HjCl^PtCl, : orange plates. — Tartrate
B'jCjHjO, 2aq : colourless prisms, si. sol. cold
water.
Cinchonamine C„HjiNjO. [194°] (A.);
[185°1(H.). [o]„= -i-121°(lpt.basein50pts.
of 97 p.o. alcohol at 15°).
Occurrenoe, — In Cinchona Pwdieana {Itit'
CINCHONA BASES.
179
naud, O. S. 93, 593; 97, 174; Hesse, A. 225,
218 ; Planohon, /. Ph. [5] 5, 352).
Properties. — Colourless hexagonal prisms
(Friedel, C. B. 105, 985). Sol. alcohol, ether,
chloroform, CSj and benzene ; si. sol. petroleum
or water. Highly poisonous. Its alcoholic so-
lution is alkaline and gives no colour with Fefi\
or CI and NHj. In oono. HjSO, forms reddish-
yellow solution, in oono. HNO3 a bright yellow
solution. In HCl it is insoluble, and on heating
at 150° it gives no MeCl.
Salts.— B'HCl.—B'HClaq.—{B'HCl),PtCl,.
— B'HBr.— B'HI.— B'HSCN.— B'HNOs. S. -2 at
15°.— B'3H,S04. [«]d = 4- 36-7° at 15° in 2 p.o.
solution (H.) ; = + 43-5 at 15° (A.). V. sol. water.
B'HjSOj Mo = 34-6°. — B'H^SA-— Tartrate
B'jH„0^0„. S. 1-I5atl5°.— MalateB'O.HAaq:
S. 1 at 15°.— Citrate : prisms. S. 1-95 at 16°.
Acetyl derivative OuHaAoNjO. [80°-
90°]. Amorphous. Sol. acetic acid, ether, alco-
hol, and chloroform, sparingly so in dilute HCl.
In cone. H2SO4 it forms a purple solution, turned
yellow by heat. Kot saponified by alcoholio
potash.
Si-nltro-cinchouamine CtsB^J^OJl^^O.
[118°]. Formed by treatment with HNO, of
SlGr. 1-06. Explosive. Ploooulent pp., sol. acetic
acid, ether, chloroform, and alcohol, and in
dHute HCl.— (C,gH2j(NOj)2NjOHCl)2PtCl4.
Methylo-iddide B'Melaci.
MethylocMorideWMeOh—lfi'MeGVj^VtGl,.
ThehydrateB'MeOHgivesmethyl-oinchonamine
on boiling with water.
Methyl-cinohonamine OjaHjaMeN^O. [139°].
Amorphous powder, v. sol. alcohol, ether, and
chloroform, insol. water. Sulphomolybdio acid
is slowly turned dark blue by it. Porms a floo-
culeut platino-chloride
(0,»H23MeNjOHCl)2PtCl, 4aq.
Ethylo-iodideB'iitl. Insol. water. When
treated with AgCl and PtCl4 successively it gives
(B'EtCl)2PtCl4 2aii. And with Ag^SOj it gives
(E'Et)jS04. When an alcoholic solution of B'Etl
is boiled with addition of a little NaOH, ethyl-
cinchonamine is formed.
Ethyl-ciuehonamine CuHjsBtNjO.aq. [75°-
78°] ; when dry it melts at [c. 140°]. Amorphous,
resembling methyl-cinchonamine. Platino-chlor-
ide: (0„Hj3EtNjOHCl)2FtCl4 3aq.
Cincholine. An oily &lk^oid which accom-
panies quinine {Hosse, B. 15, 858).
Hydrocinchonidiue OisHs^NaO. [229°-230°]
[a]„ = 98-4 (in 97 p.o. alcohol, p = 2) (Forst a.
BShringer, B. 14, 1270 ; 15, 520 ; O. Hesse, B.
14, 1893 ; A. 214, 1). Found in the mother-
liquors from which cinchonidine sulphate or
homo-cinch onidine sulphate has crystallised.
Six-sided plates (from hot dilute alcohol) or
short prisms (from strong alcohol). Less sol.
alcohol than cinchonidine or homo-cinchonidine.
v. si. sol. chloroform, ether, or water. Freshly
ppd. si. sol. ether, quickly separating again in
six-sided plates. Alcoholic solution is alkaline
and bitter.
SeacUons. — 1. Its sulphate does not at once
bleach KMnO, and shows no fluorescence.- 2.
Ammonda gives, in solutions of its salts, a floc-
oulent pp. becoming crystalline; in very dilute
solutions a orystaUme pp. after some time.— 3.,
Chlorine and NH3 give no oolour.-r4. Cone.
H^SOt dissolves it without colour.- 5, Insoluile
in KOH, baryta or lime.— 6. HCl (S.G. 1-125) at
160° has no action.
Salts.— (Hesse.) B'HCl 2aq.— B'CNSH.—
B'jH^PtCle 3aq.— B'HjPtCls.— B'C,H,jOe (quin-
ate). — B'jHAOi. — B',C.,H,0„ (tartrate), —
B'jHjSjO, aq.— B'HjSO, 4aq.- B'^H^SO^ 7aq. S,
1-75 at 10°. [a]D= -75-2° (in water, i) = 2);
- 93-8° (in 97 p.c. alcohol).—
B'jC„H,(OH)SOsH 5aq.
Acetyl derivative C^H^jAoNjO. [42°].
[o]d = - 29-5° (in 97 p.o. alcohol, p = 2);-50-9°
(in water with 3HC1, p = 2). Amorphous hygro-
scopic mass. V. sol. alcohol. Saponified by
alcoholic KOH. Soluble in acids forming salts,
e.g. C„Hj3AcNjOH.,PtCl5 2aq.
Amorphous hydro cinchonidine [oQd —
- 12° (in water with 3HC1, p = 2). Is formed by
fusing the sulphate at ,140°, and adding aqueous
NaOH to the product. It is a brownish amor-
phous base, isomeric with hydrocinchonid;ne.
It is V. sol. ether, alcohol, chloroform, or acids.
Its salts are amorphous, e.g. B'HjPtClj 2aq.
Di-cinchonine CjgHjjN^O,. [40°]. [ct]n= -1-66°.
Occurs in the bark of Cinchona rosulenta and
of G. succi/rubra especially. Not present in the
bark of 0. Calisaya, va/r. Boliviana, and var.
Ledgeriana, C. Tucujensis or C. Pelletierana,
or of Bemijia pedunculata or B. Purdieana
(0. Hesse, A. 227, 153). '
Properties. — Yellowish amorphous base. V.
sol. ether, acetone, alcohol, chloroform, and
benzene, less sol. water and light petroleum,
insol. in aqueous NaOH. Its alcoholic solution
is strongly alkaline and tastes bitter, gives no
colour with CI and NHj, and is dextrorotatory.
Salts. — The base dissolves in dilute acids
and is reppd. by NH3 or NaOH as a resinous
pp.— B"2HC1.— B"2H01.PtCl4.
BeacHon.—'S.Gi. at 160° converts it into dl-
apocinohonine, which is also formed from cin-
chonine under similar conditions.
Hydrocinehonine CuHjiNjO. [256°]. Occurs
in C. cuprea (Hesse, B. 16, 855).— B"H2PtCls 2aq.
Cinchotine C.bHjjNjO. [277° cor.]. S. '07
at 20° ; S. (ether) '19 at 20°. Occurs in crude
cinchonine sulphate (Willm a. Caventou, A.
Sitppl. 7, 248;.Forst a. Bohringer, B. 14, 436;
1267; 15, 519; Skraup, A. 197, 352; 0. 0.
1877,629). Slender prisms and scales. Dextro-
rotatory. On oxidation it gives oinehonic acid.
Salts. — B'jHjSO^ 12aq : fine needles or
prisms. S. 3-28 at 13°.— B'HNO, aq: tables.—
B'HCl 2aq : fine needles.— BH.,Cl2.—B'HCI 2aq ;
S. 2-12 at0°.— B'HBr2aq.— B'H^Br.;: prisms.—
B'HIaq.— Sulph-ocyanide B'CNSH: long
needles, si. sol. water. — Oxalate B'^HjCjO^aq:
needles; S. 1-16 at 10^ — Tartrates
B'CjHjOa 4aq : needles, sol. hot water. —
B'jCjHjOs 2aq : prisms.— B e n z o a t e B'C,H„Oa :
needles, si. sol. cold water.
ftuinamine CigHj^NjO^. [172°]. Mb = 93-5°
(in a 2 p.c. chloroform solution), [o]d = 104-5°
(in a 2 p.c. alcoholic solution). S. •064 at 16°.
S. (ether) 2 at 16°- Occurs in the bark of Cin-
chona sitcci/rubra, and of many other species ol
cinchona (Hesse, A. 166, 266 ; 182, 163 ; 199,
335 ; 207, 288 ; Da Vrij, Ph. [3] 4, 609 ; /. 1874,
874). Obtained from the mother-liquor after
quinine and .cinchonine have been ppd. as tar-
trates. Long prisms (from dilute alcohol). Dex-
trorotatory. Its alcoholic solution is alkaline to
180
CINCHONA BASES.
litmns. AtiCl, gives a yellowish pp. which soon
tarns purple. , ,Paper moistened with an acid
solution of the sulphate is turned green, and
finally blue, by OljO^.
Salt s.— B'HCl aq : prisms.— B'HjPtClj 2aq.
— B'HClOj.— B'HBr aq.— B'HI. S. 1-4 at 16°.—
B'HNOs.
ftuinamidine CjbHj^NjOj. [93°]. , [o]d = 4-5°
(in a 2 p.c. alcohoUc solution), formed by the
action of acids upon quinamine (Hesse, A. 207,
299). Nodules ; v. e. sol. alcohol. Not ppd. by
NH, from acid solutions, but ppd. by NaOH.
AuCl, gives a purple colour in solutions of its
hydrochloride. — B'HCl aq. — B'jHjPtCIs 6aq. —
B'HBraq.— Oxalate B'oHjCA 4aq.
Quinamicine CiaHjiNjOa. [109°!. [a]D = 3-8°
(in a 2 p.c. alcoholic solution). i?ormed by heat-
ing quinamine with dilute acids at 130° (Hesse,
A. 207, 303). Amorphous, but gradually becomes
crystalline. V. e. sol. alcohol. Dextrorotatory. —
B'jHjPtCleSaq.
Frotoquinamiclue C^H^uNjO.,. Formed by
heating dry quinamine acid sulphate , at 130°
(Hesse, A. 207, 305). Amorphous brown base. —
B'jHjPtCI,,
Apaqninamine CggH^jN^O. [114°]. Formed
by boiUng quinamine with excess of HCl (S.G.
1-125) for 3 minutes (Hesse, A. 207, 294). The
alcoholic solution is inactive and neutral to
litmus: the hydrochloride is Isevorotatory. —
B'HCl iaq.— B'jHjPtCl, 2aq. — B'HNO^. — 0 X a -
late B'jHjCaOiaq.— Tartrate B'^C^HjOb a;aq.
Acetyl derivative CiJBjiAcN^O. Amor-
phous;-^B'5H2ptCl, 2aq.
Conqninamine C.jHmNA- [123°]. [o]d = 205°
(in a 2 p.o. alcoholic solution). S. (91 p.c. alco-
hol) 13-5 at 19°; S. (ether) 13-5 at 15°; S.
(benzene) 24-4 at 18° ; S. (CS^) 6-05 at 18°.
Occurs in the bark of C. stiecirubra and rosu-
Icnta. It is best separated from quinamine
through the greater solubility of its salts (Oude-
mans, A. 209, 38 ; Hesse, A. 209, 62).
Properties. — ^Long prisms or pyramids. It
resembles quinamine in its reactions with HjSOj
and HNO3. Gold chloride gives a golden pp.
followed by a purple colouration. Heating with
HCl forms apoquinamine CuHjjNj.
Salts. — B'HCl: ootahedra, m. sol. water;
[a]D = 205°.— B'ttjPtCl, 3aq (0.).— B'H JtCl, aq
(H.).— B'HCIO,.— B'HCIO^.- B'HBr.— B'HI. S.
9-4 at 16°.— B'HNOs.— B'jHjSD^.— Formate
B'CHjOj : monoclinic crystals. — Acetate
B'HOAc : dimetrio crystals. — Oxalate
B'^A04 3aq. — Quinate B'CjHiaOj 2aq :
prisms.
Qninldiue G^fi^^fip Conqwmme. [168°].
[a]„ = 236*8 — 32? (in a p p.c. alcoholic solution).
S. -05 at 15° ; S. (ether) 3 at 10°. Occurs in the
bark of Cinchona CaUsayq:, G. pita^ensis, and
other species of Cinchona (van Heijningen, A.
72, 302; Pasteur, C. B. 36, 26; Stenhonse, A.
129, 16; Hesse, .4. 146, 357; 166, 232; 174,
338 ; 176, 225 ; 182, 168 ; B. 10, 2154; 12, 425 ;
Oudemans, A. 182, 53). By adding NaOH to
the mother-liquors from which quinine sulphate
has separated crude quinidine is ppd. Pure
quinidine may be isolated from this by means
of its iodide. Prisms (containing 2|aq) (ivom
alcohol), rhombohedra (containing 2aq) (from
ether), or lamina (containing l|aq) (from water).
Its solution is dilute HjSO, fluoresces blue.
Chlorine-water and NHj give a green colonr.
Dilute HjSO, at 100° changes it to quinioine.
Cone. HCl converts it on heating into apoquin-
idine and apoquinidine chlorohydride. It is a
febrifuge. It crystallises in trimetrio forms with
various alcohols : B'MeOH; B'EtOH; B'PrOH;
B'CsHjOH ; and S'fi,B.^(OB.), (MyUus, J5. 19,
1773).
Salts.— B'HCl aq. S. 1-6 at 10°; [a]a
= 212-2-56 p (in ap p.o. alcohoUo solution). —
B'H^Cl^aq: [a],, = 250° in a 2 p.o. aqueous solu-
tion.—B'HjZnClj.—B'sHjZnCl^.—B'jHjHgCl,.—
B'HjPtCl, aq. — B'^H^PtClj 3aq.— B'HjAuOls.-.-
B'HBr. S. -S at 14° (de Vrij, /. Ph. [3] 32, 328).—
B'HI. S. -08 at 15°.— B'HJj 3aq. S. 1-1 at
15°. — B'HNO,. S. 1-2 at 15°. — B'AgNO,.—
B'2H2S04 2aq. S.latl6°. [«]„ = 184° in a 3 p.o.
solution in chloroform. — B'i^SO, 4aq. S. 11-5
at 10°.— B'^jSOjHjIj (Jorgensen, J. pr. [2] 14,
356; 15, 67).— B',(H2S04),By,„.— B'jHjSeO,HjI„.
— B',(H:jSe04)4H3l„.— B'jHjSA2aq.— B'H,PO..
— B'jHjCrOj 6aq : large yellow plates (Hesse, A. •
243, 144).— Oxalate B'jHjCAaq- S. -66 at
15°.— Succinate B'„CjHj04 2aq.— Tartrate
B'jCjHjOs aq- S-2-6 at 15°.— Acid tartrate
B'C^fi, 3aq. S. -25 at 10°.— B'C,H5(SbO)Oe 4aq.
S. -18 at 10°.
Acetyl derivative CjjHjjAoNjOj. [o]„
= 128° in a 2 p.c. alcoholic solution at 15°.
Amorphous.— B'HjPtClj Saq.- B'HjAu^Olj 2aq.
Methylo-iodide C^^^^jd^el: needles
(Stahlschmidt, A. 90, 221).— B'Mel, [165°] (Jor-
gensen, J.pr. [2] 3, 153).
Ethylo-iodide CjjHjjNjOjEtl (Stenhonse,
A. 129; 20).— B'Btlaq (Howard, C.J. 26, 1183).
— B'BtClaq.— B'BtHPtCls.- B'jEtjIjHjSO,.
Quinidine chloride CjoH^gNjOCl. Conqmrline
chloride. [132°]. Formed by the action of
PCI5 upon the hydrochloride of quinidine (con-
quinine) (Comstock a. Eonigs, B. 18, 1223).
Colourless crystal^. Y. sol. alcohol, benzene,
and chloroform, si. sol. ligroin and dry ether.
By boiling with alcoholic KOH it is converted
into quiniene C2jH„NjO.
Apoquinidine C^HjjNjOo. Apoconqwmne.
[137°]. [a]D = 155° (in a 2 p.c. alcoholic solu-
tion). Formed, together with MeCl, by heating
quinidine with cone. HCl. White, amorphous
powder (containing 2aq). Sol. alcohol and ether,
[o]d = 153-3^=2, i = 15° in 97 p.o. alcohol. The
solution in dilute H2SO4 does not fluoresce, and
gives no green colour with CI and NH, (Hesse,
A. 205, 326).
Hydrochloride: acicular crystals, t. sol.
water. — ^B'HjPtClj 3aq : yellow flocculentpp.
Diacetyl derivative C„Hj|,Ao«NjOj.
[o]„ = 40-4° in a 2 p.o. solution in 97 p.o." alco-
hol at 15°. Its sulphate fluoresces blue, and
gives a green colour with CI and' NH,. —
B'HjPtClg 2aq : golden crystalline pp.
Apoquinidine chlorohydride C„Hj,ClN20j.
Formed by heating quinidine or apoquinidine
with fuming HCl at 150°- Crystalline (with 2aq)
or amorphous when anhydrous [164°]. Sol. ether
and alcohol. [o]d = 203-7° (p = 2, « = 15-97 v. p.o.
alcohol). Does not give a green colonr with CI
and NH3.— B'2H01.— B'HjPtCl, 4aq.
Diacetyl derivative CigHjiAojClNjOj.
[168°]. Gives no green colour with CI and NH,^
[aj„ = 95° in a 2 p.c. solution in dilute HOI, —
B'HjPtCl, 3aq,
CINCHONA BASES.
Iffl
fco-quinidine OJBU^S/i^ Formed by dis-
solving qmnidine in cono. HjSO, (Hesse, A. 243,
149). Long needles (from ether). — B'jHjSO, 8aq :
needles — ^B'HjPtOli, 3aq: yellow flocoulent pp.
Quiniene OjoHjjNjO. Qumem. [81°]. Formed
by treatment of quinine or quinidine ^1111 PCI5
followed by alcoholio KOH (Comstook a. Konigg,
B. 17, 1989 ; 18, 1223). Trimetrio crystals (con-
taining aaq), a:b:o = -5322:1: -6642. The solution
in dilute HjSOj shows a greenish-blue fluo-
rescence. By heating with HBr (or HCl) it is
converted into apoquiniene CuH^NOj.
S alts. — B"H2Cl2ZnCl2 2aq : trimetric prisms,
a:&:c = -3424:l: -4964.— The tartrate is si. sol.
cold water, and well crystallised.
Dibromide OjoHjjBrjNjO. Obtained by
addition of bromine to quiniene. By boiling
with alcoholic KOH it is converted into dehydro-
quiniene O^a'B.JS^O. The hydrobromide
B"HjBr2 2aq forms yellow crystals, si. sol. alco-
hol, aqueous HBr, or cold water (Comstock a.
Konigs, B. 20, 2516). '
Dehydroquiniene CjjHjjNjO. Formed by
boiling quiniene-di-bromide with alcoholic EOH.
Colourless crystals (with 3aq). V. sol. alcohol
and ether, nearly insol. water. Dissolves in very
dilute H2SO4 with a strong green-blue fluores-
cence. Gives the quinine reaction with chlorine
and ammonia (Oomstock a. Eonigs, B.2Q, 2517).
ftuinicine OjjHjjNA- [60°]. [o]d = 44° (in
a 2 p.c. chloroform solution). Occurs in cin-
chona bark (Howard, C. J. 24, 61 ; 25, 101).
Formed by heating the sulphate of qulniue >or
quinidine with HjSOi at 130° (Pasteur, O. B. 37,
110 ; Hesse, A. 178, 245). Formed also by heat-
ing quinine or quinidine with glycerin at 200°
(Hesse, A. 166, 277). Oil, which slowly solidifies.
SI. sol. water, v. sol. alcohol and ether. Its alco-
holic solution is alkaline to litmus. CI and NH,
give a green colour. Its solution in dilute
H2SO4 is not fluorescent.
Salts.— B'HjPtCl, 2aq. — B'HI aq. —
B'jHjSO^ 3aq.— Oxalate B'^HjCA 9aq. S. -4
at 16°.— Acid tartrate B'C.HjO^ 6aq. [100°].
Snlphocyanide B'HSCy,^aq.
Apoqniniene OjjHirNOj. Apoconquinme. [246°].
Formed by heating quiniene with aqueous HBr
(S.G. 1-5) at about 180° (Comstook a. Konigs, B.
18, 1226). Colourless crystals. V. sol. alcohol,
bL sol. water, ether, and benzene. It dissolves in
aqueous acids and alkalis, forming yellow solu-
tions. The sulphate is sparingly soluble. The
hydrobromide forms small yellow crystals.
Cupreine C.jHjjNA- [198°]. (Paul a.
Cownley, Ph. [3] 15, 221 ; Hesse, A. 230, 55).
Occurs in cuprea bark. The crude quinine sul-
phate from such bark is dissolved in aqueous
HjjSO,, excess of NaOH is added, and the ppd.
quinine shaken out with ether. The aqueous
Uquid is warmed and neutralised with 62804.
Cupreine sulphate then separates (Hesse, A.
226,240; 230,57).
Properties. — Concentric prisms, containing
2aq (from ether). From alcohol it separates in
the dry form. V. si. sol. ether or chloroform,
more sol. alcohol. The alcoholic solution is
alkaline to litmus, gives a dark reddish brown
colour withFejClj, and a deep green with chlorine
water, followed by ammonia. The solution in
dilute HjSOj does not fluoresce, but gives with
NH, a pp. slightly soluble in excess of KH„
and easily soluble in NaOH. Ether extracts the
base from the ammoniacal solution, but not from
the solution in NaOH. It rotates light to the
right almost as strongly as quinine. Its neutral
salts form yellow solutions; its acid salts are
colourless. HCl (S.G. 1-135) at 140° converts
cupreine into apoquinine, no MeCl being evolved.
Salt s.— (Hesse, 4. 230, 59.1 B"2H2S04 6aq.
B"H2S04 aq. — B"HC1 aq. — B"(HCl)j. —
(B"HGl)2PtCl4 4aq. — B'^HC^^PtCl, aq. —
B"2H,C„0e 2aq. The base combines with NaOH
and KOH (1 mol.), but not with NH3. It also
forms calcium, lead, and silver compounds.
Diacetyl derivative CuHjjAojNjOj
[88°]. Salt.— C,8H2^o,N202H2PtC1.3aq.
Mono-methylo- compounds. — B"MeI. la
thrown dowfi on adding Mel to alcoholio cupreine
solution. Colourless needles, very sparingly solu-
ble in alcohol or water, insoluble in ether. Very
soluble both in acids and alkalis. — B"MeCl. —
B"Me01.HCl.PtCl, 2aq.— (B"Me)2S0,. On adding
baryta to a solution of the methylo-sulphate,
and evaporating the filtrate, the hydroxide,
(B"Me)OH, remains as a yelloy amorphous
residue. It has a bitter taste, is insoluble in
ether, but very soluble in water. ' With a little
bleaching-powdei: and ammonia it gives a green
colour; if more bleaching-powder is used the
colour is red.
Di-methylo- compounds B"2MeI 5aq
forms orange plates (from water), soluble in
acids, alkalis, and alcohol (though not in water).
The corresponding hydroxide is only known in
solution.
Hydrocupreine C,„H24N202. [169°]. Formed
by heating hydroquinine sulphate with HClAq
(S.G. 1-125) (Hesse, A. 241, 279). Miorocrys-
talline powder (containing 2aq). Alkaline
to litmus. A solution of its sulphate does not
fluoresce — B'jH2S04 : small needles, v. si. sol.
water and alcohol. — B'jCjHjOo 2aq. — B'HjCL, aq.
— B'HjPtOV
Homoquininc!. This substance, obtained from
CMnacvprea (the bark ot Ber/Mjia pedwnculata) ,
(Howard a.Hodgkin, C. <7'.41,66),iB also formed
by addmg sodium cupreine to quinine hydro-
chloride (Hesse, A. 230, 70). It is therefore a
molecular compound of quinine and cupreine,
C2i;E2,N202,C,sH22N202, 4aq.
CuBcamiue. [218°]. An alkaloid in the bark
of Cinchona Pelletierana (Resse, A. 200, 304).
Prisms ; v. sol. ether, m. sol. alcohol.
Cusconine C23H2„N204 2aq. [110°]. S. (ether)
3 at 18°. [o]i> = -54° (in a 2 p.c. alcoholic solu-
tion). Occurs together with aricine in the bark
of C. cuprea (Hesse, .4. 185, 320 ; Paul a. Cownley,
Ph. [3] 12, 497). Plates (containing 2 aq) (from
ether). Its acid solutions do not fluoresce.
Laivorotatory. Cone. HNO3 turns it dark green.
B'HHgCl32aq. — B'2HjPtCls5aq: amorphous.—
B'2Hj,S04a;aq.— B'HSCy 2aq : yellow, powder.
Concusconine CjaHj^NjO^aq. [144°]. When
dry [c. 208°]. [0]],= -l-40'8° at 15° in 2 per cent,
alcoholic solution. In bark of BemijiaPua-dieana
(cuprea bark) (0.Hesse,.4. 225,234). Monoclinio
crystals (containing aq). SI. sol. alcohol, but
ppd. by water from that solution. Y. sol. benzene,
ether, and chloroform; si. sol. petroleum. Its
alcoholio solution is neutral to litmus. At 150°
it partly changes to an amorphous variety. It
forms no acetyl derivative with- Ac,0. Cono.
189
CINCHONA BASES.
HNO3 added to its solution in aeetie acid or HCl
gives a splendid dark -green colour. Cono. HoSOj
forms a blue-green solution, turned olive-green
on warming. ^ '
Salts .—Mostly gelatinous.— (B'HCl)^?!©,
5aq.— B'jHAQ,.B'i,HjSOj. Prisms.
{a.)-Meihylo-i'odide B'Mel. Crystalline
powder : hardly sol. alcohol, sol. boiling water.
iProm it may be obtained : B'MeCl, needles ;
(B'M6Cl),PtOl4, amorphous; (B'Me)jSOj; and
B'MeOH, which when dry melts at [202°].
($)-Methylo-iodide B'Mel. Gelatinous.
V. sol. alcohol. From it may be obtained :
B'MeCl, amorphous ; (B'MeC^jPtCljSaq, amor-
phous; (B'MeJjSO,; and B'MeOH SJaq.
Cnsconidine. An amorphous alkaloid in
CuBco bark (Hesse, A. 200, 303).
ConcuBConidine CjsHjsNjO,. [124°]. A
slightly dextrorotatory amorphous alkaloid, said
to occur in cuprea bark (Hesse, B. 16, 62). —
B"jHjPtCle.
Hydroquinine C,„'S,s1i!fi^. [168°]. [a]n
= -142-2° (p = 2-4 in 95 p.c. alcohol at 20°, but
[o]„ = - 227-1° in dil. HCl. Discovered by Hesse
\B. 15, 856) in mother-liquors o£ quinine sulphate.
Preparation (Hesse, A. 241, 255). — The
mother-liquor from quinine monosulphate is
treated with successive quantities of sullphuric
acid until a neutral salt is obtained containing
over 30 p.c. of hydroquinine sulphate. The
quinine is then removed with KMnO^, and after
neutralisation with NaOHAq the hydroquinine
is extracted with ether, benzene, or chloroform.
Properties.— Can be obtained by neutralising
the, solution in dilute acid with NaOHAq
as an amorphous pp. having the composition
CjoHjjNjOj 2aq. Crystallises from . chloroform
in concentric grouped needles. V. sol. alcohol,
chloroform, ether, benzene, and CSj, m. sol.
ammonia, si. sol. water, insol. NaOHAq. Solu-
tion in dilute H2SO4 shows blue fluorescence,
and gives the same reactions as quinine with
CI and ammonia, but decolourises KMnOj very
slowly. Alkaline reaction, bitter taste. Heated
with HCl it yields hydrocupreine.
Salts. — B'2H2S04 6aq: short white prisms;
v. sol. alcohol and hot water, si. sol. cold water,
'insol. ether. S. -287 at 15°. [a]D= - 193-4°.—
B'HjSO, 3aq : long thin needles ; v. sol. water
and alcohol, m. sol. acetone. Heated to 120°
it gives off water, and to 140° yields hydroquin-
icin sulphate.— B'2HjS2022aq.—B'HC12aq : long
flat prisms; v. sol. water and alcohol, insol.
ether. — ^B'sPtClnH^ 3aq : yellow amorphous pp.;
V. si. sol. water and alcohol. — ^B'PtCljHj 2aq. —
B'2AuCl.|H 2aq(?) : yellow amorphous pp. —
B'2HClHgCl2 : small colourless flat needles. —
B'BrH,2aq.— B'(BrH)j3aq: B'lH: oil, becoming
solid but not crystallising. — B'(IH)2 4aq: shining
yellow needles. — B'HjI, a;aq : metallic, dichroic
flat needles. — B'HCNS: a resin; m. sol. water. —
B'Cj,H4026aq. [100°]: small colourless needles ;
V. sol. water and alcohol. — B e n z o a t e B'CjHjOj :
small needles ; v. sol. alcohol, si. sol. water. —
Salicylate E'C^HjOs: small colourless needles;
T. si. sol. cold water, m. sol. hot water, v. sol.
alcohol. — Piperonylate B'CjHj04. —
B'jOj04H2 6aq: long sjiining needles; insoL ether,
V. sol. hot, si. sol. cold, water, v. sol. alcohol.
S. -213 at 15°.— B'jCHjO, 2aq : thick colourless
prisms ; m, sol. hot water, alcohol, v. sol. chloro-
form-alcohol, si. sol. water. S. "183 at 17".
[a]D=-176-35° {cf. Ph. IS] 16, 1025)!- Citrate
B'sCsHsOjlOaq : small white needles; v.' sol.
boiling, si. sol. cold, water.— B'jP04Hs7aq : small
white needles; si. sol. water. — B'3(AsO4H3)jl0aq:
long white needles.— B'jCrO^Hjeaq: long golden
needles; m. sol. hot, si. sol. cold, water, v. si. sol.
chloroform.
Combinations. — 1. With oupre!ne
C2„H2jN20j.C,jH22Nj022aq; long shining needles
grouped concentrically. — 2. With quinidine
C2„H2jN202.C2„H2iN20j 2|aq ; white needles.— s;
With anethol (C2|,H2jN202)2C,„H,20 2aq. Large
shining dimetric prisms, V. sol. hot alcohol;
ether ; si. sol. cold alcohol ; insol. water. De-
composes at 120° into hydroquinine, anethol,
and water. — 4. Also forms compounds with
hydroquinidine, cinchonidine, hydrocinohon-
idine, and homocinohonidine, but not with cin-
chonine or hydrocinchonine.
Methylo- compounds B'MelEtOH. Pale
yellow prisms. [218°]. V. ,sol. hot, m. sol.
cold alcohol, insol. water.— B'MeCl 2aq [168°].
— B'MeHPtClj 2aq : brange-red needles. —
B'^Me^PtClji pale-yellow needles; m. sol. alco-
hol and water. — ^B'MeOH : resin ; insol. ether
and chloroform ; v. sol. alcohol and water. Ab-
sorbs CO2.
Acetyl derivative OjjHjsNjOjAc. [c. 40°].
Y. sol. ether, alcohol, benzene, acetone, and
acids; si. sol. water, and NH3. [a]i, = — 73"9°.
in 3 . molecules HClAq p = 3, t = 15°. —
(C.aH25AcN202)PtCl8H„2aq: powdery pp.; si. sol.
dil. HCl and water.— (CjoHjsAcNjOjjSOjHj 9aq :
long needles ; v. sol. hot water, alcohol, si. sol.
cold water, insol. ether.
Sutphonic acid. — Strong H2SO4 at
ordinary temperatures forms hydroquinine sul-
phonic acid CjjHjsNjOj.SOaH aq [239°] ; insol.
ether, chloroform ; si. soli NHj and NaOHA«q.^^ '
(02„H25NsO2.SOsH)PtClBH2 8aq : pale - yellow
needles.
Hydroquinicine CjoHjuNjO^. Formed by
fusing hydroquinine sulphate at 140° (Hesse,
A. 241, 273). Yellow resin. V. sol. ether,
alcohol, chloroform and dilute acids. Solution
in dilute H2SO4 is intensely yellow, addition of
chlorine-water and ammonia gives a yellowish
green colouration. More easily acted on by
KMn04 than hydroquinine. — S alts . — N e u t r a 1
sulphate ; white needles, v. e. sol. alcohol and
water. — B'PtCljHjaq : pale yellow flocculent pp.
changing to orange-coloured crystals insol. water,
si. sol. dilute HCl.
Hydroquinidine CjdHjjNjOj. Hyd/rocmgwm-
me. [167°]. Occurs in crude quinidine, and
obtained therefrom by treatment in acid solution
with KMnOj which does not attack- hydroquin-
idine (Forst a. Bohringer, JB. 14, 1954 ; 15, 519,
1656 ; Hesse, B. 15, 854). Needles or tables.
M. sol. ether, y. sol. alcohol and chloroform.
The alcoholic solution is alkaline to litmus. Its
solution in dilute H^SOj shows blue fluorescence.
It is dextrorotatory. Chlorine-water and NH,
give a green colour. Chromic mixture forms
quinic acid.
Salts. — B'HCl: soluble prismatic tables. —
B'HBr : plates, si. sol. cold water.— B'HjPtClo '^aq-
B'„H2S04l2aq.-B'HI.— B'HJjSaq: large brange
soluble crystals. — Tartrate B'.2CjH50j 2aq :
glistening soluble prisms. — Aoid tartrate
CINCHONIDINE.
18S
B'CjHbOj 3aq : ^thin white needles, si. sol. cold
water. — Benzoate B'0,HbOj,: colourless tables.
—Salicylate B'CjHjOj : six-sided tables.
Hydrocinchonidine. Identical with Cinohami-
DiNE (v. Cinchona basbs).
Homooinclionidine OuH^NjO. [206°]. S.
(alcohol) 4-9 at 13°; S. (ether) -46 at 15°.
Md= —107° in a 2 p.o. alcoholic solution at 5°.
Occurs in very small quantity in many cinchona
barks, especially that of C. rosulenta (Hesse, B.
U, 46, 1891; A. 205, 203; 207, 310; cf. Skraup,
A. 199, 365). Obtained by reorystallisation of
crude oinohonidine sulphate. Prisms'or plates.
Iissvorotatory. Its alcoholic solution is alkaline
to litmus. Its solution in H2SO4 does not
fluoresce. It gives no green colour with CI' and
NH3. Cone. HCl at 150° gives apocinchonidine
and apocinchonidine ohlorohydride. KMn04
forms lormio acid and oinchotenidine.
Salts.— B'HClaq.—B'HC12aq. [a]„= -139".
— B'HjPtCl, aq.— B'jH2PtClB2aq.— B'HNO, aq.—
B'H^S^Oa 2aq. S. -5 at 13°.— B'^H^SO, 6aq. S.
1'45 at 22°. [a]D= — 138° in an 8 p.o. aqueous
solution.— B'HSOy. — Tartrate E'C^HuOe 2aq.
S. -075 at 10°.— Quinate B'OjHijOs.— Phenyl
sulphate B'^HSO^Ph 5aq.
Acetyl derivative CigHjiAcNjO. [ajj,
— — 34° in a 2 p.e. alcoholic solution at 15°. —
B'HjPtCla 2aq.— B'(HAuCl4)2 aq.
Cinchotenidine CibH^oNjOs. [256° cor.]. S.
(alcohol) '13 at 78°. Formed by oxidation of
nomocinchonidine or cinchonidine (Skraup a.
Vortmann, A. 197, 235 ; Hesse, B. 14, 1892).
Needles or prisms (containing 3aq). Its solution
in dilute H^SO, does not fluoresce. Its solution
in HClAq. is leevoi-otatory. [b]d 201°.—
B'sfH^PtCls.- B'jH2S04 2|aq; v. e. sol. water.
Siconquinine CjjHjsNjOj. An amorphous
alkaloid occurring in most cinchona barks
(Hesse, B. 10, 2155). Is the chief constituent
of commercial 'quinoidine.' Dextrorotatory.
Gives a green colour with 01 and NII3. The
solution in dilute H^SO, is fluorescent. Its
salts are amorphous.
Paricine CisH^NjO. [130°]. Found by
Winkler {B. J. 27, 338) in a false cinchona bark.
Occurs in the bark of C. lutea, and O. siLccvrubra,
of Darjeeling (Hesse, A. 166, 263 ; Ph. [3] 9, 889).
The aqueous solution of the mixed sulphates of
quinine, oinchonine, paricine, &a. is treated
with cone. HNO3 which throws down paricine
nitrate. Paricine may also be ppd. from the
mixed sulphates by adding NajOOj to feeble
alkaline reaction. Yellow powder. V. e. sol.
alcohol and ether. The alcoholic solution is
alkaline to litmus and is inactive. —
B'jHjjPtCla 4aq.
Javanine. Occurs in the bark of 0. Calisaya
javamka (Hesse, B. 10, 2162). Plates (from
water). Its solution in dilute H^SOj is intensely
yellow.
CIKCHONIC ACID v. Quinolinb-(P2/. 1)-cab-
BOXTLIO ACID.
CINCHONIDINE C.jH^^NjO. [200°] (H.);
[210° cor.] (S. a. V.). S. -06 at 10°. S. (ether)
•53 at 15°; S. (97 p.o. alcohol) 6-1 at 13°.
[a]o=— 70° in a 4 p.c. solution in alcohol-
chloroform. Discovered by Winkler (Bepert.
Phann. [2] 48, 384 ; 49, 1) and occurs in" most
cinchona barks (Leers, A. 82, 147 ; Pasteur,
C. B. 37, 110; a. J. 6, 276; Bussy a. Guibourt,
J. Ph. [3] 22, 401; Hesse, 4. 135, 333; 166,
240 ; 176, 203 ; 181, 50 ; 182, 160 ; 205, 196 ;
207, 310 ; Skraup a. Vortmann, A. 197, 226).
Separated from quinine and other bases by re-
peated extraction with ether. It is then Con-
verted into the hydrochloride and ppd. by hydro-
sodio tartrate. The base, liberated from the
tartrate, is then crystallised from alcohol.
Properties. — Gives no> green colour' wi1;h
chlorine water and ammonia. Its solution in
dilute H2SO4 does not fluoresce.
Reactions. — 1. HNiOj gives the same products
as with cinohonine. CrOj doe^ the same. — 2.
H2SO, at 130° or glycerin at 200° converts it
into oinohonicine. — 3. Heating with HCl gives
apocinchonidine, (;3) -cinchonidine, and apocin-
chonidine chloro-hydride. — 4. Oxidised by KMnO,
to pyridine tri-carboxylio acid. [257°] (Eamsay
a. Dobbie, C. J. 35, 189).— 5. PCI5 converts it
into oinchonidine-chloride CuHjiN^Ol, which by
boiling with alcoholic KOH gives oinohene
CjoHjoNj, and this by heating with HCl at 220°
is converted into apocinchene C,aH„NO (Corn-
stock a. Konigs, B. 17, 1986).
Salts. — ^B'HOlaq: monoolinic crystals. S.
3-3 at 10°. S. (ether) -3 at 10°. Lmvorotatory.
[o]d varies from —24° (in chloroform) to —152°
(in dilute HClAq).— B'HC12aq: prisms.—
B'HjGlj, aq.— B'HjHgCl, : scales.- B'HjPtOls aq.
B'H^PtClj 2aq. — B'H,AuCla. — B'HJ^aq. —
B'HNOaaq. S. 1-4 at 10°.— B'^H^SO^ 6aq. S.l
at 12°; 1-5 at 22°: prisms. [o]d = - 111° ' (in
water). — B'HjSOjSaq: striated prisms, v. sol.
water and alcohol. — B'(H2S04)2 2aq : short
prisms, si. sol. cold water. — B'ELjSjOj 2aq. S.
•45 at 10°.— B',2(H2S04)9Hjl5j 8aq : golden plates
(Herapath, O. J. 9, 130 ; Jorgensen, J. pr. [2] 14,
371).— B',(H2S04)2H3ls4aq.^',(HjS04)5H<,I„6aq.
B'2H2S04HI,aq. — B',2(RjSe04),Hj32 8aq. —
B'jH2Se04Hl5aq. — B'jCHjPO,), 12aq.—
B'2(H3P04)2Hl3.— B'2(H3As04)2.-B'HSCy. ,S. -5
at20°. Acetate B'HOAoaq. — Benzoate
B'C,HjOj. S.^3 at 10°.— Oxalate B'jH^CjOjeaq.
S. -i at 10°. [a]B = - 99°. — B'^B.fiJO^^„. —
Succinate B'jCjHjOj 2aq. S. -17 at 10°.
Tartrate B'204H50s2aq: crystalline pp.; in-
sol. aqueous sodio-potassium tartrate.' S. '04
at 10° (tartrate of cinchonine is far more
soluble). — B'2C4HaOsHl3. — Acid tartrate
B'(C4H508)23aq. — Salicylate B'C,Hj03. S.
•13 at 18°.
Combinations with Phenol. — B'^HOPh;
Prisms. Forme^ by mixing alcohoHo solutions
of phenol and' cinchonidine. — ^B'j(H0Ph)3: un-
stable crystals. — B'HGlHOPhaq: crystalline
grains, formed by adding phenol to an aqueous
solution of cinchonidine hydrochloride. —
B'2S03H0Ph 5aq. Formed by mixing hot aque-
ous solutions of phenol and cinchonidine suli
phate. Prisms. S. -235 at 15°.
Acetyl derivative OinH^iAoNjO. [42°].
[o]i>= —38° in a 2 p.o. alcoholic solution at 15°;
= — 81° in a solution in dilute HCl. Brittle
mass.— B'HjPtClj 2aq.— B'(HAuCl4)j aq.
Methyl-oinohonidine CisH^MeNjO. [76°].
From the iodide by treatment with aqueous
KOH (Stahlsohmidt, A. 90, 218 ; Claus a. Bock,
B. 13, 2191; Hesse, B. 14, 45). Needles or
tables (containing aq). Its salts are mostly
deliquescent. Iodide C,„H„,MeN,OHI. [248°J,
From cinchonidine and Mel. Slender needles.—'
184
CINCHONINE.
Chloride BBOl. [158°]. Slender needles
(containing aq). — ^B'E^PtCl, 3ac[k
Methylo -iodide CigHjiMeNjO.Mel 2aq :
crystals.
Methylo-di-iodide C,8H2,MeNjO.HI.MeI :
large prisms.
Ethyl - cinchonidine OjjHjjNsO. [90°].
Colourless needles. V. sol. alcohol and ether,
insol. water. Prepared by the action of aqueous
SOH on thd iodide (Glaus a. Dannenbanm, B.
13, 2189).
Salts. — ^B'EClSaq: cubes; v. sol. water
and alcohol (Howard, O. J. 26, 1181 ; Glaus, B.
14, 1922). LsBVorotatory.— B'HBr aq.— B'HI.
[261°]c I'rom cinchonidine and EtI. Needles.
B'HI,.— B'HGy. [140°]. Slender needles, v.
sol. water (Glaus a. Merck, B. 16, 2745). —
B"HjClsPtCl4 aq : brystaUine pp.
Methylo-iodide BMel. Colourless needles.
Decomposes at 257°.
Ethylo-iodide BEtl. Besembles the
methylo-iodide; on treatment with KOH it
gives a di-ethyl-cinchonidlue.
Ethylo-di-iodide CigHaiEtNaOHEtljaq.
[255°]., Golden crystals.
Isoamyl - cinchonidine C,9H2,(C5H„)N20.
Eesin.— B'HjPtCl,a;aq (Glaus a. Weller, B. 14,
1922).
Si-bromo-cinchonidine Ci^'H.^^x^/)/ From
cinchonidine in GS^ and Br (Skalweit, A. 172,
103). — ^B'SLjBr,: needles, t. sol. alcohol.
Si-ozy-cinchonidine 0,9Hj„(OH)2N20. From
the preceding by long boiUng with alcoholic
KOH (S.). Bamified orystals.^B'2H2S042aq:
plates.— BTHjSO^.—B'HjPtCl,.
Apooinchonidine CisH^jNjO. [225°]. [o]n
= —129° in a # p.o. alcoholic solution at 15°.
Foraned by heatmg cinchonidine with HGl (Opts.
of S.G. 1-105) at 150° (Hesse, A. 205, 327).
Small plates (from alcohol). LEevorotatory. Its
acid solutions do not fluoresce.— B'H2FtCl£2aq.
Acetyl derivative CigH^iAoNjO. [a]D
= —62° in a 2 p.c. alcoholic solution at 15°. —
B'HjPtCle2aq.— B'(HAuGy 2 aq.
Apooinchonidine ohlorohydride GuH^aClNjO.
[200°]. [o]d = - 142° in a 2 p.c. solution of dilute
HCl (containing 3HC1). From apooinchonidine
and fuming HCl at 150° (Zorn, J.jpj-. [2] 8, 283 ;
Hesse, A. 205, 346). Plates (from alcohol).
IiBBVorotatory.— B'HjCLj.— B'H2PtCls2aq.
Acetyl derivative CigHjjAcGlN^O. [150°].
Prisms (from ether). LcBvorotatory. —
B'HPtC1.2aq.
(3).Cinchonidine Gj,'S^^fi. [207°]. [a]D
= —181° in a l^- p.o. solution in dilute HCl at
15°. Formed, together with apocinchonidine,
by heating cinchonidine with HCl (S.G. 1-105)
at 140°. Separated from apocinchonidine
through the insolubility of its tartrate (Hesse, A.
205,327). Short prisms or plates. liSTorotatory.
The neutral tartrate is v. si. sol. water. By
heating with HCl for a long time it' changes to
apooinchonidine. — ^B'EjPtCls aq.
Iso-oinchonidine C^fi^fi. [235°]. Formed
by dissolving cinchonidine in cone. H^SO,
(Hesse, A. 243, 149). Colourless plates. V. si.
sol. ether, v. sol. alcohol and chloroform.
CINCHONINE 0,»HaN,0. [236°] (when
slowly heated); [248°-252°] (when quickly
heated) (Hesse); [260°] (Skraup). [a]n = 226° in
«t 1 p.o, alcoholic solution ; = 255° in dilute
HjSO^; =268° inalOp.e. solution containing
1 mol. H^SP, at 15° (Hesse ; c/; Oudemans, Ar.
Nierl. 10, 193). S. -262 at 10°; S.~ (alcohol of
S.G. -852) -71 at 10°; S. (ether) -27 at 10°; S.
(CHGlj) -28. Occurs, together with quinine, in
most of the true cinchona barks (Fourcroy, Ann.
CMm. 8, 113 ; 9, 7; VauqueUn, Ann. CMm. 59,
30, 148; Gomez, Edinb. Med.and Surg. Jbitmal,
1811, 420 ; PfafE, Schu). J. 10, 365 ; Pelletier a.
Caventou, A. Oh. 15, 291, 337; PoUetier a.
Dumas, A. Ch.'2i, 169 ; Gerhardt, Bevue scient.
10, 886 ; Traitd, 4, 105 ; Laurent, A. Ch. [3] 19,
363 ; Eegnault, A. Ch. 68, 113 ; A. 26, 15 ;
Liebig, A. 26, 49 ; Hlasiwetz, A. 77, 49 ; Weidel,
A 173, 76; Hesse, 4. 122, 226; 135,326; 166,
217 ; 205, 211 ; Skraup, A. 197, 353 ; Oudemans
A. 182, 44).
Preparation, — The bark is extracted with
dilute acid. The alkaloids are ppd. by lime,
NajCOg, or NaOH, and crystallised from alcohol
(85 p.c.). Cinchonine crystallises out before
quinine, unless the quantity of the latter present
be relatively large, in which case a portion of
the quinine is first removed by crystallisation of
the sulphates. Quinine may be separated from
cinchonine by ether, which dissolves quinine
most readily.
Properties. — Prisms (from alcohol). When
ppd. by ammonia from aqueous solutions of its
salts it is amorphous, but rapidly becomes crys-
talline. Tastes bitter. Its solutions are alka-
line to litmus and dextro-rotatory. Its solution
in dilute HjSO, does not fluoresce. It does not
give a green colour with chlorine- water and
ammonia. It gives a yeUow pp. with chloride
of iodine.
Beactions. — 1. Oxidised by EMnOj to pyri-
dine tri-carboxylic acid (Dobbie a. Bamsay, C. J.
35, .189). 10 g. cinchonine dissolved in 4-5 g.
H2SO4, diluted with water to 100 c.c, and treated
gradually with 285 o.c. of a 5 p.c. solution of,
KMnO, gives oinohotine, cinohotenine, and
quinoline oarboxylic acid (Skraup, j4. 201, 294).
In the syrupy oxidation products of cinchonine -
are a monobasic acid CjHijNOj, a base CsH^NOz,
yielding an ethyl-pyridiue identical with that of
Wyschuegradsky, CsH^NO, identical with Schmi-
deberg a. Kretsohy's base kyuurine, and an amor-
phous product CjjHisNOj (Skraup, M. 7, 517,
518). AlkaUne KMnO, gives off 41 p.c. of the
nitrogen as NH3 (Hoogewerff a. Van Dorp, A.
204, 90).— 2. HjSOi and PbO^ give a red sub-
stance', cinchonetin (Marchand, J. CMm. Med.
10, 362).— 3. Boiling HNO3 (S.G. 1-4) forms
quinoline oarboxylic (cinchonio) aoid, quinolio
acid CjHjNjOs, pyridine dicarboxylio (cincho-
meronic) acid, pyridine tri-carboxylio acid and
a base C„H,jNA CV^eidel, A. 173, 76).— 4. CrO,
gives quinoline oarboxylic acid and some formic
acid, which perhaps indicates a methoxyl group
(Skraup, A. 201, 294).— 5. PCI5 converts it into
ci^chonine-chloridb CijHjiN^Cl [52°], which by
boiling with alcoholic KOH gives cinchene
CipHjpNj, and this by heating with HCl at 220°-
230° is converted into apocinchene C,gH,jNO by
splitting off MeCl and NH, and taking up H2O
(Comstock a. KSnigs, B. 17, 1984).— 6. Treat
ment -with CuO and KOH gives quinoline and
a resin wnence oxidation produce? pyridine di-
carboxylio aoid (Wysohnegradsky, B. 13, 2318).
7. Distillation with solid potof^ yields methyl-
OINCHONINE.
185
amine, {a) and {fi) di-methyl-pyridine, (o) and
(3) tri-methyl-pyridine, quiaoline, and quinbline
tetrahydride (Oechsner de Coninck, A. Oh. [5]
27, 453 ; C. B. 94, 87).— 8. Aqueous KOH gives
4uinoIine and a solid body (Butlerow, J. B. 10,
244) ; in presence of superheated steam KOH
forms also methyl-quinoline (Krakau, Bl. [2] 45,
248).— 9. HjSO< and a little water at 130° forms
the isomerio oinchonicine ; this body is also
formed by fusing the aoid sulphate of cinchonine.
Aoeording to Jungfleisoh a. L6ger (C. B. 105,
1255) pure sulphate of cinehoniue dissolved in
a mixture of equal parts of water and pure H2SO4
yields a colourless liquid, which when heated for
some time to 120° and then rendered alkaline
yields a pp. of six bases: cinchonibine
(oi, = + 175'8"' in a I p.o. alcoholic solution), oin-
chonifine jod = + 195°), cinchonigine (od = — 60°),
einchoniline (bd= +53°), aU having the for-
mula CggH^^NjOj, and the two oxyoinchonines
(au= +182-56° and o„= + 187-14°) of the formula
OagHjjNjO,. Fuming HjSOi forms cinchonine
Bulphonic acid. — 10. HCl at 150° forms suooes-
sively apocinchonine, diapooinchonine, and
finally apocinchonine ohlorohydride. — 11. The
product of the action of sodiwn ethylate- on.
cinchonine, after distilling with steam, yields
CjjHjsNj, a heavy reddish yellow viscous oil
smelling like quinoUne. The constitution of this
base is probably C,8H2,Nj(C2H5) (Michael, Am.7,
182). — 12. Gone. HBrAq forms apocinchonine
bromohydride CigHosBrN^O and the hydrobro-
mide of that body OuHjsBrNjOHjBrj (Skraup,
A. 201, 324).
Salts.— B'H012aq. S. 4-2 at 10° ; S. (alco-
hol) 77 at 16°; S. (ether) -35. [o]d = 163° in a
1 p.o. aqueous solution ; = 212° in presence of
2 mol. HCl (Hesse; cf. Sohwabe, J. Ph. [8] 38,
389).— B'HjClj.— B'HCl. — B'H^Pj ^aq (Elder-
horst, A. 74, 80).— B'HjHgCli : formed by mix-
ing alcoholic solutions of cinchonine hydrochlor-
ide and of HgCla (Hinterberger, A. 77, 201).
Needles. — B'HjZnCli aq. — B'^HsZuClj 3aq. —
B'jHsZnClj aq.— B'HjSnCl,.— B'HjPtClo : amor-
phous pp. — B'HjPtCl, aq. — B'HjPtCl, 2aq. —
B'H^AuOls.- BTaClO, : bulky crystaUine tufts
(Serullas, A. Ch. [2] 45, 278).— B'(HC104)o aq
(Bodecker, A. 71, 59; Dauber, A. 71, 66).—
B'HaBr,.- B'HI aq.— BTLjI^ aq.— E'EI, (Bauer,
Ar. Ph. [3] 5, 289 ; cf. Pelletier, A. Ch. [2] 63,
181).— B'HIj aq [92°]; trimetrio brown tables
(from alcohol) (JSrgensen, /. pr. [2] 3, 145 ; 15,
82).— B'HClHaL [97°].— B'HjHgl4(Caillbt,B. J.
10, 193).-B',(HjSO.).H^,<,2aq. [140°-145°]
(Jorgensen, J. pr. [2] 14, 356; cf. Herapath,
C. Ji 9, 151).— B'4(H2S0JsH4l,,.— B'jHjSO^HjI,.
B'„H,SeO,HjI,. — B'CajO fit) jai,lu. — B'HIO,.
Explodes at 120°.— B'HiFeCya 2aq : formed by
mixing alcoholic solutions of cinchonine and
HjPeOyj ; lemon-yellow pp. ; v. si. sol. alcohol
(DoUfus, A. 65, 224).— B'HaFeCyj 2aq : orange
pp., formed by adding aqueous EjFeCye to
aqueous cinchonine hydrochloride — ^B'HSOy. —
B'HNOjaq: prisms, v. sol. water. [o]d = 172°
Bouohardat).— B'jHiS04 2aq. Hard prisms. S.
1-5 at 13°. [a]D = 169° in a 1 p.o. aqueous solu-
tion ; = 193° in a 1 p.c. alcoholic solution (Hesse).
[a]n4-[B]o = l-2C8 (Grimbert, J. Ph. [5] 16, 295).
B'H,SO, 3aq : trimetric ootahedra (Baup, A. Ch.
[-2] 27, 323).-B'H,,SO, imi.—WM,S..O, 2aq.—
B'jHjSA aq. — B'jH„Cr„0,. — B'^H^O, 12aq.-
B'jHjAsO^ 12aq.— Oxalate B'HAO, 2aq. S. 1
at 10° Suooinate B'C,H,0,l^aq. —
B'O^HjO, aq.— Tartrate B',0,B.fi,2a.q. S. 3
at 16°. — Aoid tartrate B'OiH.O, 4aq. S. 1
at 16° (Pasteur, J. 1853, 419). — Laevotar-
trate B'CiHjOjaq. S. (alcohol) -3 at 19°;
v. si. sol. water.— Citrate B'jOjHsO, 4aq. S.
2-1 at 12°. Acid citrate B'jC,HsO,4aq. S.
1-8 at 15°.— Urate B'C,,H,NA 4aq.— Piorate
B'j(0,Hj(N02)3(0H))3.— B e n z o a t e B'HOBz. S.
•6 at 15°.
Acetyl derivative OuHjiAcNjO. [«]d
= 114° in a 2 p.c. alcoholic solution. Amor-
phous; V. sol. alcohol and ether.— B'HjPtCI„aq.
B'(HAu01<)2aq.
Benzoyl derivative OjbHjiBzNjO..
Amorphous (Schutzenberger, A. 108, 351).-^-
B'HjPtCls icaq.
Metiyl-cinolionine CuHjiMeN^O. [74°]..
From cinchonine by successive treatment with.
MeBr and aqueous KOH (Glaus, B, 13, 2286;;
cf. Stahlschmidt, A. 90, 218). Tables (fromi
ether). B'HBraq. Ginchomine methylo-bromide..
[248°]. From cinchonine and MeBr. Said not:
to be identical with the compound of methyl-
cinchonine with HBr.— B'HI [254°].— B'HIj,
[162°].— B'HjPtCljaq.— B'HMeBrj [235°]. FrouL
cinchonine (1 mol.) and MeBr (2 mols.) at 160°.
B'Mel. [201°] ; needles.— B'Me^I,. [235°].
Ethyl-cinchonine O^JS^^TSfi. [50°]. Crystal-
line solid. Prepared by the action of alcoholic -
KOH on cinchonine-ethylo-iodide (Glaus a.
Kemperdick, B. 13, 2286 ; ef. Howard, C. J. 26,
1183).
Salts.— B'HI. [260°]. Cinchmme ethylo-
iodide. White needles. From cinchonine and
EtI.— B'HCl aq.— B'HBr.— B'HIa [142°] (Jdrgen-
sen, J".^. [2] 3, 152).— B'H,Cl^tGl4 2aq: yellow
pp. The gold double chloride forms small
yellow plates.
Ethylo-iodide B'Etl. [242°], From
ethyl-cinchonine and EtI. Fine white needles.
With KOH it gives di-ethyl-cinehonine. B'HBt^.
Cinchonine dl-ethylo4odide: B'Et^Ijaq. [264°].
Yellow prisms sol. water.
' Benzyl-cinchonine O^B.,^Ti^fi. [117°]. Colour-
less needles. Prepared by the action of KOH on
cinchonine-benzylo-chloride (Glaus a. Treupel,
B. 13, 2294).— B'HGl. Cinchonine benzylo-chlor-
ide. [248°]. From cinchonine and C,H,G1 in
alcohol. Needles, sol. hot water and alcohol.
AgjO converts it into C,,H2,(0,H,)N20 aq said
not to be identical with the isomeride got by the
action of KOH (Glaus).— Carbonate [116°].—
B'HjCLiPtClj 2aq : yellow crystalline pp.
Benzyla-chloride B'G,H,C1: [255°] ;co.
loarless needles.
Si-chloro-cinchonine CigHjoCljN^O. The hy-
drochloride is ppd. by passing chlorine into a
cone, solution of cinchonine hydrochloride
(Laurent, A. Ch. [S] 24, 302). Crystalline.-
B'HjOlj. S. (alcohol) 2. — B'HuPtOl, aq. —
B'HjBrj.
Bromo-cinchonine'CigHjiBrNjO. Formed by
adding Br to an alcoholic solution of cinchonine
(Laurent, A. Ch. [3] 24, 302i ; A. Kopp, Ar. Ph.
[3] 9, 34). Boiling alcoholic KOH gives ' oxy-
oinchonine ' [205°].— B'H^Cl,.
Di-bromo-cinchonine GijHjoBrjN^O. Formed
by bromination of cinchonine (Comstock a.
Konigs, B. 17, 1995 ; cf. Laurent, Cornet, chim.
186
CnsrOHONINE.
1849, 311). Colourless crystals containing aq.
SI. Bol. alcohol, insol. water. Alcoholic KOH fs
said by H. Streoker (A. 123, 380) to convert it
in^o an oxyciuchonine which crystallises from
alcohol in plates.
Cinchouine - (a) - di ■ bromide Gi^^T'f^r/).
Formed by the action of bromine upon oin-
chonine dissolved in a mixture of chloroform
and spirit. Crystallises with aq. Boiled with
alcoholic KOH it is converted into dehydro-
einchonine 0,„Hj,N.,0.,— C,„Hj2N2Br.,0,H^r2
(Comstock a. Konigs, B. 19, 2854 ; 20, 2510).
Cinchonine - (,8) - di - bromide OigH^N^BrjO.
Formed at the same time as the preceding, from
which it differs in crystallising in an anhydrous
condition.
Cinchonine - di - bromide ■ sulphnric acid.
Formed by several hours' standing at the ordi-
nary temperature of a solution of oinchonine-di-
bromide in 7-8 parts of cone. H.SO,. Crystal-
line solid. SI. sol. cold water, v. sol. aqueous
alkalis, an excess of which precipitates the
alkaline salts of the acid. By heating with
dilute HBr at c. 130° it is split up again into
oinchonine-di-bromide and HjSOj (Comstock
a. Konigs, B. 19, 2855).
Cinchonine-chloro7hydTide CuHjsClNjO. Hy-
ArocMorcinchonme. [218°]. Formed by allow-
ing a solution of cinchonine in fuming ECl
(saturated at —17°) to stand at the ordinary
temperature for several weeks. Colourless crys-
tals (from alcohol). By boiling with alcoholic
KOH it yields isocinchonine and a little cin-
chonine. The hydrochloride 0,„H2sClN„0, HjClz
crystallises in prisms (Comstock a. Konigs, B.
20, 2519).
Cincbonine-bromo-hydride CuH^jBrNjO. By-
irohromcinchoivme. 'Bromcmchonide ' of Skraup.
Formed by the action of fuming HBr (saturated
at — 17°) upon cinchonine at the ordinary tem-
perature or at 100°. Boiled with alcoholic KOH
it gives a mixture of cinchonine and isocin-
chonine. — C,„H23BrN20,H2Br2 (Comstock a.
Konigs, B. 20, 2520).
einchonine - chloride CuHjiNjCl. [72°].
Formed by heating the hydrochloride of cincho-
nine with POCI3 and PCI5. Trimetric prisms.
By boiling with alcoholio'.KOH it yields cinohene
C,sHj,„lf 2 (Comstock a. Konigs, B. 14, 1854 ; 17,
1984). , ■
Behydro - oincbonine OjjHjjN^O. [203°].
Formed by heating oinchonine-di-bromide with
alcoholic KOH. Colourless needles. Sublimable.
v. sol. alcohol, acetone, and chloroform, m. sol.
ether and hot benzene, v. si. sol. ligroin and
water. — B'HBr : colourless prisms. — "B'HCl:
very soluble long silky needles (Comstock a.
Konigs, B. 19, 2856).
Sehydro-cinchonine-bromo-bydride
CijHsiBrNjO. Hydrobromdehydrocinchonine.
Bromo-cinchonine. [c. 235°]. Crystalline.
Formed by allowing a solution of dehydro-
oinchonine in very cone. HBr to stand for 8 days
at the ordinary temperature (Comstock a. Konigs,
B. 20, 2524).
' Debydrocincbonine - chloride ' C|„H„NjCl.
[149°]. Formed by the action of PCI5 upon de-
hydrpcinohonine. Colourless crystals. V. sol.
alcohol, ether, acetone, chloroform, and benzene,
nearly insol. ligroin. By boiling with alcoholic
KOH it is converted into dehydrticinchene
0„H„Nj (Cdmstook a. Konigs, B. 19, 2857).
Di-bydrd-di-cincbonine (C„Hj|,N„0)2. [258°].
Formed by treating an acid solution of cinchonine
with sodium-amalgaip or with zinc and H.SO,
(Zorn, J.pr. [2] 8, 293 ; Howard, C. J. 26, li79 ;
Skraup, B. 11, 812). Scales (from alcohol). —
B'HjSO...
Hydrocincbonine CigHj^NjO. Formed at the
same time as tlie above. Aifaorphous. When
CI is passed into an aqueous solution of its
chloride there is formed hexa-chloro-hydro-
oinchonine CuHigCljNjO and tetra - chloro -
dispoliue CuHjCliN^ HNO3 converts hydrocin-
chonine into amorphous tetra-nitro-hydropiri-
chonine C,aH2„(N02)4N20.
Ciucbonibine C^Hj^N^O. [259°]. [o]d=176°
(in alcohol) ; = 220° (in HClAq). Insol. water
and ether. Alkaline to litmus, but not to
phenol-phthaleiin. — B'Mel. — B'MejI, l^aq. —
B'Etl.— B'EtjIj (Jungfleisch a. L^ger, C. B. 106,
1410).
Cinchonigine CisHjjNjO. [128°]. [o]d=-60°.
The bases formed from cinchonine by heating
with sulphuric acid oa^u be separated by ether.
From the ethereal extract HCl pps. cinchouigine
hydrochloride and the mother-Uquor on concen-
tration, addition of soda and re-extraction with
ether gives with HI oinchoniline hydro-iodide.
The bases insoluble in ether are 4 in number,
and are separated by weak alcohol, in which cin-
ohonibine and cinchonifine are insoluble, while
(o) and ifi) oxycinchonine dissolve (Jungfleisch
a. Leger, 0. B. 106, 68, 857).
Properties. — Colourless prisms, volatile, dis-
tils under reduced pressure, sol. alcohol and di-
lute HCl. SI. sol. water ; v. sol. chloroform, benz-
ene, and acetone^ less sol. dry ether. Pro-
bably identical with the base obtainefl by Caven-
tou a. Girard (0. B. 106, 71) by heating cincho-
nine with oxalic acid and.HjSO,.
Salts.— B'HClaq ; [213°].— B'2HC1 aq.—
B'HBr aq. — B'HI aq.— B'2HI aq. — B'^C^H^O, ;
needles.— B'P^HjOe 8|aq.— B'Mel [253°] ; colour-
less needles. — B'Etlaq [232°]; large prisms from
alcohol.— B'EtBr aq.— B'H^PtCls aq (Jungfleisch
a. Leger, 0. B. 106, 857).
CinobonilineCigHj^NjO. [130°]. [o]d = + 53-22°
in alcohol. Prepared as above. Ehombic prisms,
dextrorotatory. SI. sol. water, v. sol. most sol-
vents. Its aqueous solution is turned blue by
litmus and red by phenol-phthalein. Eeduoed
in the cold by KMuOj. Yields the same products
as cinchonine on heating.
Salts.— B'HC18aq [226°]; v. sol. water [o]d
= +5°.-^B'2HClPtCl,aq; yellow prisms.—
B'2HClAuCl3 ^aq ; prisms.— B'HBr 3aq ; prisms,'
less soluble than the chloride.— B'HI aq ; B'2HI ;
B'HCNS aq.
Methyl amd ethyl compounds B'Mel
[235°] ; B'Etl ; B'EtBr are all three v. sol. most
solvents (Jungfleisch a. Leger, C. B. 106, 657).
Ciucbotenine CuHjoNjO,. [198°]. [a]„ = 135°
in a 2 p.c. alcoholic solution. The chief product
of the action of KMnO, on cinchonine dissolved
in dilute H^SO^ (Skraup, B. 11, 311 ; A. 197,
376). Needles or plates (containing 3aq); Dex-
trorotatory. Not attacked by coldiKMuO,. —
B'HjPtCln; prisms.— B;(HAuC1,)2 ; needles.
Ciucbotenioine CuHjoNjOs. [153°]. The sul-
phate is formed by fusing cinchotenine sulphate
CINEOL.
187
It is feebly dextrorotatory, and forms an amor-
phous platinoohloride.
Cinohonioiue CuHjjNjO. (a)D = 4C-5° in a 2
p.o. solution in chloroform. Formed by heating
the acid sulphate of oinchonine or oinohonidine
(Pasteur, C. R. 37, 110; Hesse, A. 178, 253).
Formed also by heating the tartrate or acid tar-
trate of oinchonine, and by heating oinchonine,
oinckonidine, or oinchonine sulphate with glyce-
rin (Howard, C. J. 25, 102 ; Hesse, A. 147, 242 ;
166,. 277). Slightly yellowish viscid mass, ■which
becomes a mobUe liquid at 50°. Y. sol. alcohol
and ether. Its alcoholic solution tastes bitter
and is alkaUne to litmus. CI and NH, give no
green colour. Bleaohing-powder gives a white
pp. in a solution of its hydrochloride (difference
from oinchonine and cinchonidine). Dextro-
rotatory.
Salts. — ^B'HI : prisms, m. sol. cold water. —
B',H3Cls(PtClJ,4aq (?).— BH^PtCljaq. - Oxa-
late B'jHjCjO, 4aq : slender prisms. — Acid tar-
trate B'CjH„Oj aq.
Apocinchonine CuHj^NjO. [209°]. [o]d = 160°
in a 1 p.o. alcoholic solution at 16° (H^sse, A.
205, 380 ; Oudemans, B. T. C. 1, 173). Formed,
together with diapooinohonine, by heating oin-
chonine with HCl (S.G. 1-125) at 150°. The pro-
duct is nearly neutralised with ammonia, alcohol
is added, and the solution heated to boiling ; ex-
cess of NHj nowpps. apooinchonine. Prisms, si.
sol. ether, insol. water.
Salts. — The salts are dextrorotatory, for the
neutral salt Wd varies from 180° to 215° ; for
the basic salts from 164° to 176°.— B'HC12aq.—
B'HjPtCls 2aq. — B'HBr aq. — B'HI aq. —
B',H5,SO,2aq(H.).— B'jHjS0,3aq(0.).— B'HClOa.
B'HCIO, aq.— B'aHjO^O^ 2aq.
Acetyl derivativeC,,'H^i&.a!>(fi. [a]D = 71°
in a 2 p.o. alcoholic solution at 15°. —
B'HjPtCls2aq.
Apocinchonine chlorohydride CggHsjClN^O.
[197°J. [o]d = 211° (Oudemans), = 205° (Hesse)
in a ^ p.o. alcoholic solution at 16°. Formed by
heating oinchonine or apocinchonine with satu-
rated HCLAq at 150° (Zorn, J. jar. [2] 8, 280;
Hesse, A. 205, 348). Needles; v. si. sol. water ;
si. Bol. ether and alcohol. Dextrorotatory. In
the case of the neutral salts [o]p varies from 215°
to 229° ; for the basic salts it lies between 192-5°
and 195° (0.).— B'H,C1,.— B'HCl aq.— B'H,Br,.—
B'HjPtClj2aq. — B'jH,S0<3aq. — B'HNO,. —
B'HClOa.- B'HCIO, xnq.—B'Hfifit xaq.
Acetyl derivative OidHj^AoCINjO. [oJd
= 108° in a 2 p.o. alcoholic solution at 15°. Amor-
phous ; V. sol. alcohol and ether.
Apocinchonine bromohydride OigHjsBrNjO.
From oinchonine and cone. HBrAq at 100°
(Skraup, A. 201, 324). Scales (from alcohol).—
B'HjBrj,: crystals.
Apoclnchonicine CjgHj^NjO. A resinous base,
formed by heating apocinchonine acid sulphate
at 140°. Inactive ; v. sol. alcohol and ether. —
B'HjPtCls 2aq.
Si-apocinchonine (CijHjjNjO)^. [a]D = 20°
in a 2 p.c. alcoholic solution at 15°. Formed
by the prolonged action of HCl on apooinchonine.
Amorphous powder, v. sol. alcohol and ether.
Dextrorotatory.— B'HjPtClj 4aq : amorphous.
Acetyl derivative CagHj^Ao^NiOj. [ajo
= 26° in a 2 p.c. alcoholic solution. Yellow
amorphous mass. — ^B'H2PtClo4aq; amorphous
pp.— B'(HAuCl,),2aq.
Iso-oinohonine CigHjjNjO. [127°].
Crystalline. Formed together with oinchonine
by boiling oinchonine-ohloro- or bromo-hydride'
(CisHaClNjO or C„Hi,sBrNjO) with alcoholic
KQH. V. e. sol. alcohol, ether, benzene, chloro-
form, acetic ether, andCSj, si. sol. ligroin, nearly
insol. water. It forms easily soluble salts. The
zinc double chloride C,aH22Ni,0, ZnClj, HjClj
forms small needles (Comstock a. Eonigs, B. 20,
2521). A substance called isocinchonine has also
been obtained by Hesse (A. 243, 149) among the
products of the action of cone. H^SO^ on oincho-
nine.
CINCHOTENICINE v. Cinohoninb.
CINCHOTENIDINE v. Cinchoninb.
CIHCHOTESINE v. Cinohoninb.
CINCHOTINE V. Cinchona babes.
CINCHOVATINE v. Abicine.
CINENE 0,„H,B. Cynim. (181°-182°). S.Gr.
IS -854 (Wallaoh a. Brass, A. 225, 309).
Formation. — 1. By passing HCl into boiling
oleum cinse (worm-seed oil) or oineol (c/. VSlckel,
A. 89, 358).^2. From cineol andBzCl.- 3. From
CjoHijIj (got from cineol and HI) and aniline. —
4. Among the products of the distillation of
caoutchouc (when it is called caoutohin). — 5. By
heating isoprene at 260°- ,
Properties. — Oil, with pleasant odour of lemon.
Beactions. — 1. JBromine added to its cold so-
lution in alcohol or ether forms the tetrabromide
Cj^.sBr, [125°].— 2. Cone. HjSOi converts it
into cymene, giving off SO2. PjSj behaves
similarly. (V. also Tekpbnbs.)
Dihydrochloride C.oHisClj. [50°].
Dihydrohromide C,„Hi8Brj. [64°]. White
silky plates. Formed by the action of HBr gas
upon worm-seed oil. It is slowly decomposed
on standing in contact with alcohol. On heat-
ing or by boiling with water or dilute alkalis it
loses HBr giving cinene. It decomposes on
keeping in the course of several weeks (Hell a.
Bitter, B. 17, 2609).
Dihydroiodide C,„H,jl2 [77°]. White
felted needles. Formed by the action of gaseous
HI upon worm-seed oil. It decomposes on keep-
ing in the course of a few days, and quickly in
contact with alcohol. By ziflo-dust and water
it is reduced to eynene-di-hydride C,„Hij (Hell
a. Bitter, B. 17, 2611).
DihydrideG^^,,. (166°). V.D. = 5 (obs.).
Colourless liquid, of ethereal odour. Formed
by boiling cinene-di-hydroohloride or cinene-di-
hydroiodide with zinc-dust and water (Hell a.
Bitter, B. 17, 2612).
CINEOL C„H„0. (176°). S.G. S2 .927.
/tD = l'458. V.D. 5-12 (Wallach a. Brass, A. 225,
295 ; 245, 195 ; Gladstone, 0. J. 49, 621). The
6hief constituent of oleum cinsB and of oil of
eaj^put;, occurs also in oil of rosemary (Weber,
238, 89). Liquid, smelling like camphor, in-
active. Boiling HNO3 (S.G. 1-15) forms oxalic
acid only.
Beactions. — 1. HCl passed into its solution
in ligroin forms crystals of (C,„H,„0)2HCI, a
body which is decomposed by water, reproducing
cineol, biit when heated alone produces cinene :
(C,„H„O)jHCl = 2H2O-fHCl-H0i„H„. -r 2. HI
passed into oleum cina ultimately converts it
into a crystalline mass of CuHi.Ij. Crystallised
188
OINEOL.
from light petroleum, this forms trimetrio
tablets: a:6:c = -7588:1: -7074 [TS-S"!. Alcoholio
KOH conTerts it into cinene. — 3. Excess of
Broimme added at 0° to a solution of cineol in
light petroleum forms red crystals of G,gH„0Br2.
These crystals decompose on keeping, forming
cinene tetrabromide and water: 2C,gH„0BT2
= 0,„H„Br4 + 2HsO + 0„H„. When a smaller
quantity of Br is added to a solution of cineol in
light pettoleam, needles of (C,gH,,0)2Br2 are
formed (Wallach, A. 230, 228).— 4. Cineol also
combines with iodine forming crystals of
.Co»s<i£u<ici».^-Sodium, FCljiu the cold, and
BzCl at 120° do not act on cineol. Hence it
appears not to contain hydroxyl. At 150° BzCl
removes HjO. Hydroxylamine and phenyl-
hydrazine do not act on cineol. Brdhl
(B. 21, 461) gives cineol the constitution
Pr
O I ^ since it is optically inactive and on
passing HCl through it it is converted into opti-
ClPr
cally inactive I .
ClMe .
Iscmerides of Cineol are described under Bor-
MEol; v.alsoCAMPHOB3,vol.i.p.672. The matter
will be less complicated if we can assume the
existence of only two compounds of the formula
C,„H„OH with rotatory power +38= and -38°
respectively, the others being mixtures of these
in varying proportions. Thus the IsBvorotatory
camphols ([«]!)=— 38°) derived from BUi/mea
hahamifera (N'gai camphor and also, from the
same tree. Bang Phito), Martico camphor, the
camphor from oil of valerian, and that from
madder, are in all respects identical (Haller,
C. i2. 103, 64, 151). Ordinary bomeol is a cineol
of rotatory power + 38°. Camphol from amber
appears to be partly of the racemic character
(i.e. an inactive compound of camphols of rotatory
power +38° and —38°) and partly of dextro-
rotatory bomeol (Haller, C. B. 104, 66). By dis-
solving a camphol (50 g.) in toluene (150 g.),
heating with sodium (6 g.) and passing in cya-
nogen a product is got whence water extracts a
camphyl carbamate C,|,H„.O.CO.NHj. Thepro-
.dnct derived from dextrorotatory camphol is
described (vol. i. p. 523) as bornyl carbamate. It
is dextrorotatory and forms dextro-hemihedral
crystals. Ltevorotatory camphol forms an
isomeride [127°] which is Isevorotatory ([a]i,
= - 29*90°), and crystaUises in lasvo-hemihedral
forms. In each preparation, camphyl carbonate
(C,gH,,)2C0, is a by-product; the carbonate
from borneol is dextrorotatory while that from
Iffivorotatory camphol is Iffivorotatory. Both
melt at 215° (Haller, C. fl. 98, 578).
CINNAUElIT V, Benzyl ether of Cinnamic
ACID.
cnrNAKENE V. Stybene.
CINITAUEirYL COMPOUNDS
C,Hi.CH:CH-X V. Sixsn ooufoundi.
CINN AMENTL - AUISO - PHENYL - MEB ■
CAPTAN C.sHiiNS i.e.
0„H,<|^C.CH:CH.O„H. [111°]. Prepared by
the action of cinnamic acid on amido-phenyl-
mercaptan (Hofmann, B. 13, 1235). Colourless
prisms. Sol. alcohol. Weak base. On fusion
with EOH it is split up into cinnamic acid (which
is further converted into benzoic acid) and
amido-phenyl-meroaptan.
Salts.^B'HCl: unstable salt.—
(B'HCl)2PtCl4 : yellow needles.
CINNAMIC ACID C„H,Oji.e.
CjH5.0H:CH.C0jH. Phervyl-acryUcacid. Benzyl-
idene aceUa acid. Mol. w. 148. [133°] (Kraut,
A. 133, 93 ; 147, 112). (300°). S.G. * 1-248
(Schroder, B. 12, 1612). S. -03 at 17° ; S. (alco-
hol) 2-3 at 20°; S. (CHCy 6 at 15°; S. (CS^) -9
at 15°. Electrical condimtmity: Ostwald, J. ^.
[2] 32, 365.
Occimrenoe.— 1. In oil of cinnamon (Dumas
a. Paigot, A. Oh. 57, 311 ; Herzog, Ar. Ph. 17,
72 ; 20, 159). — 2. In liquid storax which contains
styrene, cinnamic acid, and styryl cinnamate
(styracin) (E. Simon, A. 31, 265 ; D. Howard,
C. J. 13, 135 ; Beilstein a. Kuhlberg, Z. [2] 7,
489). — 3. In balsam of Peru, which contains
benzyl cinnamate, benzoic acid, and cinnamic
acid (E. Kopp, Compt. cUm. 1847, 198 ; 1849,
146 ; 1850, 140 ; Eraut, B. 2, 180 ; Delafontaine,
Z. 1869, 156). — 4. In balsam of Tolu, which is
similar in composition to that of Peru (Fr^my,
A. 30, 338 ; Devilles A. 44, 304 ; B. Eopp, A.
60, 269 ; Busse, B. 9, 830).— 5. In gum benzoin
from Sumatra (Eolbe a. Lautemann, A. 119, 136).
6. In the leaves and stalks of Globularia vulgaris
(Heckel a. Sohlagdenhauffen, A. Ch. [5] 28, 69).
7. In the leaves of Eukianthus japonicus (Byk-
man, B. T. C. 5, 297).
Formation. — 1. By heating benzoic aldehyde
with AcCl for 24 hrs. at 125° (Bertagnini, Ci-
mento, 4, 46 ; A. 100, 126).— 2. By heating ben-
zoic aldehyde with HOAo and ZnCl, at 160°
(Schiff, B. 3, 412 ; Z. [2] 6, 700).— 3. By heating
benzoic aldehyde (2 pts.), Ac^O (8 pts.), and
NaOAc (1 pt.) at 145° (Perkin, C. J. 31, 389 ;
Slocum, A. 227, 58). This reaction, commonly
known as Perkin's synthesis, is discussed under
AiiDEHiDES (vol. i. p. 108). — 4. By the action
of benzoic aldehyde on sodium malonate in pre-
sence of AcjO in the cold, COj being evolved :
Ph.CHO + CH,(COjH), = PhCH:C(OOjH)j + H,0
= PhCH:CH.C02H + 00^ + HjO (Stuart, C. J. 43.
404). — 5. By heating benzoic aldehyde with ma-
lonio acid at 130° (Michael, Am. 5, 205).— 6. By
the action of KOH on benzyl-chloro-malonio
ether (Conrad, B. 13, 2160).
Properties. — Monoclinioprisms (from alcohol)
(Schabus, Sitz. W. 1850, ii. 206). When quickly
distilled it is but little decomposed, but when
slowly distilled it splits up into COj and styrene
(Howard, O. J. 13, 135). Volatile with steam.
V. si. sol. water, v. sol. alcohol, v. e. sol. ether ;
V. si. sol. cold ligroi'n.
JBeaciiojM.^-l. Distillation with lime gives
styrene and benzene. — 2. Potash-fusion gives
potassium acetate and benzoate (Chiozza, A. Ch.
[3] 39, 439 ; Kraut, A. 147, 113). Fusion with
NaOH gives COj and benzene (50 p.c. of theo-
retical) (Birth a. Schreder, B. 12, 1257).— 3. SO,
forms sulphobenzoio acid. Boiling with H^SO^
CINNAMIO AOTB.
189
diluted with 1 to IJ vols, water forms an oil,
consisting of distyrene 0,5H,a and distyrenio aoid
G„K,flp — 4. Gone. HNOj gives nitro-benzoio
acid, but a more dilute aoid gives benzoio alde-
hyde.— 5. Boiling with PbOjin aqueous solution
forms benzoic aldehyde and lead benzoate (Sten-
house. A, 65, 1 ; 57, 79). — 6. Chromic mixture
also forms benzoio aldehyde (Simon).' KMnO^
in feebly alkaUne solution acts in the same way
(A. Bauer, A. 220, 37). KMnO, in very dilute
neutral solution at 0° oxidises cinnamic acid to
PhCH(OH).CH(OH).COoH (Pittig, B.21, 919).—
7. Br gives di-bromo-phenyl-propionio acid (A.
Sohmitt, 4. 127, 319).— 8. Fuming HBr gives
bromo - phenyl - propionic acid. HI acts in a
similar way. — 9. Sodium amalgam reduces it to
phenyl-propionic acid (Erlenmeyer.jl. 137, 327).
Gone. HIAq does the same (Popoff, Z. [2] 1, 111).
10. HCIO gives ehloro-oxy-phenyl-prbpionio acid
(Glaser, A. U7, 78 ; Z. [2] 3, 65 ; 4, 131).— 11.
Boiling aqueous K^SO, gives sulpho-phenyl-pro-
pionic acid. — 12. Chlorine acts on aqueous sodio
cinnamate in two ways, viz. :
(1) Ph.CH:CH.002Na + Gl,
= Ph.CHCl.CHCl.C02Na
- Ph.GH.CHCl.G0.0 + NaCl
= Ph.GH:CHCl + 00^ + NaCl
(2) Ph.CH:GH.COjNa + 0l2 + H2O
= Ph.CH:CH.C02H + HCIO + NaCl
= Ph.CH{0H).CHCl.C02H + NaCl
producing a-ohloro-styrene and chloro-oxy-phe-
nyl-propionio acid (Erlenmeyer a. Lipp, A. 219,
184). — 13. Diphervylamine and ZnCLat 250° form
phenyl-acridine (Bernthsen, B. 20,,1552). — 14. m-
Oasy-bemoic acid and H2SO4 form a body CuH^O,
„ „ > G'^P^-9?>0 [260°] (Kostanecki, B.
or ObH,^ qq > UjUj^
20, 3137). It forms a diaeetyl derivative [260°].
15. s-Di-oxy-bemoio acid and H2SO4 give the
oxy-derivative of the preceding [325°] which
forms a crystalline acetyl derivative 0,bH,Ac04
[255T (K.).— 16. Gallic acid and HjSO, at 50°
form, in the same way, ' styrogallol,' a dioxy-
derivative of the above CjgB.gO^, which crystal-
lises in minuteyeUowneedles, melting above 350°
(Jacobsen a. Julius, .B. 20, 2588). Its di-acetyl
derivative melts at 260°.
Salts (Herzog, J. pr. 29, 51 ; E. Kopp, C. JR.
63, 634).— NH^A' Jaq : si. sol. cold water.—
KA' §aq : monoolinic crystals ; v. sol. water, m.
sol. alcohol. — NaA'iaq: needles (from dilute
NaOHAq).— NaHA'j (Perkin, G. J. 31, 388).—
AgA'': curdy pp. insol.' boiling water..^BaA'2 aq
(Herzog).— BaA'j 2aq : pearly plates (Kopp).—
BaA'2 3aq : iridescent leaflets or striated prisms
(Eebuffat, Q. 11, 166).— OaA', 2aq (H.; E.).—
OaA'jSaq (K.). S. -16 at 17°. — SrA'j4aq:
nacreous needles. — MgA'j 3aq : white needles.^
CuA'2(Cu02ll2)a;: greenish - blue pp. — PbA'jt
crystalline powder or flattened needles. —
CdA'2 2aq. — MIM^.': 2aq. — ZnA', 2aq : prismatic
needles (from hot water).
Methyl ether UeA'. [34°], (263° i.V.).
S.G. %• 1-0415. Formed by the action of the
ethyl ether on methyl alcohol in presence of
NaOMe (Purdie, C. J. 61, 628; cf. E. Kopp,
C.JR.21, 1376; Anschutz a. Kinnioutt, B. 11,
1220; Weger, A. 221, 74). With Br it forms
O.H5.0HBr.OHBr.COi,Me [117°].
Ethyl ether EtA'. [12°] (Friedlander, .i.
221, 76). (266°) at 741 mm. (Briihl, A. 235, 19).
(271° i. V.)(A. a. K.). S.G. "j" 1-0490. fiD 1-560
(B.). PreparaUom. — Ginnamic acid (500 g.) is dis-
solved in dry alcohol (1 litre) and HGl is passed
in to saturation. After 3 hrs. the product 13
poured into ice-cold water. The oil is washed,
dissolved in ether, and shaken with aqueous
sodic carbonate, dried over GaCl,, and the ether
evaporated (Perkin, Jun., C. J. 45, 17.^ ; cf.
Herzog, Ar. Pk, [2] 17, 72 ; Marchand, A. 32,
269 ; E. Kopp, J.pr.Pharm. [3] 11, 72; Planta-
mour, A. 30, 345). BeacUons. — 1. With broTnime
it forms CoHj.CHBr.CHBr.COjEt [69°].— 2. So-
di/um-aceto-acetic ether in presence of alcohol at
100° forms an aoid 0,5H,e04 [140°]. Its silver
salt, AgA', forms radiating prisms, insol. water
(Michael, J. pr. [2] 35, 354).— 3. With sodkim
malonic ether at 100° in presence of alcohol it
forms an oil G,i,Hj<0„ (305°-310°) or (215° at
15 mm.). Ph.CH:CH.COjBt + NaHOloOjEt), ,
Ph.CH.OHNa.COjEt
I +HjO
OOjEt-CH-OOjEt
Ph.GH.CHj.COjEt
°> I + NaOE. On saponify-
CH(COjEt)j
ing and heating the resulting acid CO, is evolved,
and there results phenyl-glutario acid
Ph.CH.CHj.COja
I [138°]. Its silver salt, AgA',
CH.CO2H
is amorphous (Michael, J. pr. [2] 36, 349 ; Am,
9, 118).
n-Propyl ether PrA'. (283°-284° i.V.)
(A. a. K.). S.G. 2 1-0435 (Weger, A. 221, 76).
Benzyl ether GjH5.GH:CH.CO.OOHsOjHj.
Cinnwrnetn. [39°]^ Discovered by Plantamour
(A. 27, 329 ; 30, 341) in balsam of Peru (FrSiny,
A. Gh. 70, 184 ; E. Kopp, Compt. chim. 1S50,
140 ; ScharUng, A. 74, 230 ; 97, 184 ; Kraut, A.
107, 208 ; Grimaux, Z. [2] 6, 157). Formed also
by boiling dry sodium cinnamate with alcohol
and benzyl chloride for some hours. Short
prisms (from alcohol).
Phenyl ether CjHi.OjHj.COjC^s : [73°];
(206") at 15 mm. Formed by the action' of
cirmamoyl chloride upon phenol. By slow dis-
tillation it loses carbonic acid, giving stilbene
CeH5.G^.C5H5 (Anschutz, B. 18, 1945; C. J.
47, 898).
p-Tolyl ether CeHs.CjHj.COAH,: [101°];
(230°) at 15 mm. (A.). By dow distillation it
yields s-phenyl-tolyl-ethylene (A.).
Phenylpr.opyl ether
05Hs.0^,.G0j.GHj.CHj.CH2.0eH5. Occurs in
storax (Miller, A. 189, 353), and is also_ formed
by treating styraoin bromide with zinc and
HjS04.
Thy my I ether 0^,.0A.C020„H„: [70°];
(240°) at 15 mm. (A.).
(ffl-Naphthyl ether CA-OjHj.COjCjoH,:
[102°]. By distillation CO, is split ofl with
formation of s-phenyl-naphthyl-ethylene (A.).
Cinnamyl ether
C-H5.CH:CH.C0.0.CHj.CH:CH.CA- Styracin.
[44°]. S. (ether) 33 ; S. (alcohol of S.G. -826)
33 at 78°; 6 at 16°. Occnis in liquid storax
(Bonastre, J. Ph. 1831, 338 ; E. Simon, A. 31,
265 ; E. Eopp, Compt. oMm. 1860, 140 ; Toel,
A. 70, 1; Stieoker, A. 70. 10; 74, 112; WqIS,
190
OWNAMIO AOID.
A. IS, 297 ; Plantamour, A. 27, 329 ; 30, 341 ;
GoBSniann,^. 99, 376 ; Soharlin^, A. 97, 90, 174 ;
W. V. MiUer, N. Bep. Pharm. 24, 1 ; A. 188, 200 ;
189, 344). Needles or prisms (from alooliol).
Chlorine forms a viscid tetra-chloro- derivative
CijHijClA- Br forms C^sB^fiLfi^ [151°] and
0,„H,„Br,Or
Chloride C„H5.CH:CH.C0.C1. [36°]. (170°)
at 58 mm. Prisms (Cahours, A. Ch. [B] 23, 341;
Eostoski, A. 178, 214 (Olaisen a. Antweiler, B.
13, 2123),
Cyanide OeHs.CHrCH.CO.CN. [115°].
Prisms. Sol. ether, CHCls, C„Hs, and CS^ ; v.
si. sol. water. Prepared from the chloride By
the action of silver cyanide. On saponification
it gives oinnamoyl-formio acid.
Anhydride (CjH^.CHiCH.CO)^^ [127°].
{GerhaTdt, A. Ch. [3] 37, 285 ; A. 87, 76).
Crystalline.
Amide C„H5.CH:CH.C0.NH,. [142°]. (v.
Eossum, ^.1866, 362).-(C,H,.C^2.CO.NH)2Hg.
Anilide CsH5.CH:CH.c6.NPhH (Cahours,
A. 70, 43). Slender needles.
Diphenylamide OjHs.CttCH.CO.NPhj.
[153°] (Bernthsen, B. 20, 1554). Needles.
Nitrile CsHj.CHiCH.CN. [11°]. (255°).
From the amide and PCI5. Also from oinnamio
acid and lead sulphocyanide at 190° (Kriiss, B.
17; 1768).
Cinnamic acid dihromide v. Di-bbomo-fhentii-
FEOPIONIO ACID.
Cinnamic acid hydrohromide v. Bbomo-
PHENYL-PBOKONIO AOID.
Cinnamlc-acid-di-nitrite
C|,H5.C2Hj(N02)2.C02H. Phenyl-di-nitro-propio-^
•mc dad. Colourless crystals. Formed by direct
combination of cinnamic acid with NjG,. Very
, unstable. By treatment with water or alcohol
it evolves COj and yields phenyl-nitro-ethylene
C.H5.CH:CH(N0j,) (Gabriel, B. 18, 2438).
p-Aldehydo-cinnamic acid
C,H,(CH0)(CH:CH.C02H). [247°]. From tere-
phthalic aldehyde, NaOAc, and Ac^O by Perkiu's
reaction (Low, A. 231, 374). Flat prisms or
needles. SI. sol. hot water, ether, or chloroform,
more sol. glacial acetic acid. When sublimed
it forms large plates. Salt. — AgA.
Ethyl ether EtA'. Seduces ammoniacal
AgNOj. Gives by Perkin's reaction
C„H,(CH:CH.COjH) (CH:CH.CO^Et)
(•». Phentiienb-w-aoeylid acid). Reactions. —
1. Eeduces ammoniacal AgNO, with difficulty. —
2. Does not react with NaOAc and ACjO. — 3. On
nitration gives nitro-aldebydo-cinnamic acid
- Dz-oromide
C,H,(CHO).CHBr.CHBr.COJH. [176°] (with de-
composition). Prisms (from methyl alcohol).
Insol. water; v. sol. ether, chloroform, and
alcohol.
^-Carbozy-cinnamic acid
C„H,(00jH) (CHiCH-CO^H) [1:4]. Got by sapo-
nifying its ether. Powder, will not melt, but
may be sublimed. Nearly insoluble in solvents.
Does not combine with bromine in the cold.
Forms a nitro- derivative.
Dibromide
C,H,(CO,H)(CHBr.CHBr.COjH). Di-lromo-
ca/rboxy-phenyl-propionic acid. Formed at 100°.
WiU not melt. Sol. methyl alcohol, from which
it may be crystallised.
Mono-ethyl ether
C„Hj(CO.^t)(OH:CH.CO^H) [220°]; From p-
aldehydo-tefephthalio ether, NaOAc, and kafi
by Perkin's reaction (L6w, A. 231, 369). Prisma
(from ether).
Other derivatives of cinnamic acid are de-
scribed as AMroo-,BEOMO-, Chlobo-, Hydeazido-,
N1XEO-, SULPHIDO-, SCLPHYDEO-, and SULPHO-
cinnamic ACID. Oxy-cinnamio atjid is described
as COUMAEIC ACID.
CINNAMIC ALDEHYDE C^HjO i.e.
C5H5.C.,H,.CHO. Mol. w. 132. (i29°). S.G. "^
1-0497" (Briihl, A. 235, 18). /»„ = 1-619.
M, = 1-683.
Occurrence. — In oil of cassia and oil of cinna-
mon, whence it raay be extracted by shaking
with NaHSOj and distilling the resulting crys-
talline compound with aqueous Na2C0j (Perkin,
a. J. 31, 403; ef. Mulder, A. 34, 147; Berta-
gnini, A. 85, 271).
Formation. — 1. By oxidising cinnamyl alco-
hol with the aid of platinum black (Strecker, A.
93, 370). — 2. By distilling calcium formate with
calcium cinnamate (Piri?,, A. 100, 105).
Preparation. — A mixture of benzoic aldehyde
(10 pts.), acetic aldehyde (15 pts.), 10 pts. of
lOp.c. aqueous NaOH, and 900 pts. of water is
allowed to stand for 8 or 10 days with frequent
shaking at about 30°, the cinnamic aldehyde
being' finally extracted with ether (Chiozza, A.
97, 350 ; Peine, B. 17, 2109).
Properties. — Oil. Forms crystalline com-
pounds with HCl, HNOs, NaHSO,, KHSOj, and
NHjHSOj (Dumas a. Pffigot, A. 14, 65).
Beactions. — With alcoholic NHj it gives
hydrocinnamide OjjHjjNj [106°]. With HCN it
yields the nitrile of o-oxy-phenyl-crotonio acid.
With resoroin and dilute HOI it giyes a resin in
the cold (Michael a. Eyder, Am. 9, 134). HCl
passed into a mixture of cinnamic aldehyde with
phenyl meroaptan forms OjH5C„H2CH(SPh)2
[81°] (Baumann, B. 18, 885). With carba-
mio ether it forms Ph.C,H2.0H(NH.CO^t)2
[135°-.143°] (Bischoff, B. 7, 1079).
Phenyl hydrazide
C,H5.C2H2.CH:N2HCjH5: [168°], yellow plates
(Fischer, B. 17^ 575).
Anilide C^,.CJ3.^.CBi:1^G,n^: [109°],
yellow glistening plSites. Very stable towards
HOI. Forms orystallisable salts with acids
(Doebner a. Miller, B. 16, 1665 ; Peine, B. 17,
2109).
Di-methyl-amido-anilide
C„H5.C2Hj.CH:N.C„H,(NMe^ : [141°] ; yeUow
needles ; sol. alcohol, si. sol. cold ether (Nuth,
B. 18, 574).
Ethylene-di- amide
(C,H5.C,H,.CH:N),CjH, : [110°] ; tables, m. sol.
ether (Mason, B. 20, 267).
Di-bromide v, o;8-Di-bbomo-phenyl-pbo-
PIOKIO ALDEHYDE.
CINNAMIC AIDOXIM
CsH5.CH:CH.CH:N0H. Phenyl-acryUc aldo^im.
[136°]. Fine silky needles. V. sol. alcohol,
ether, acids, and alkalis, nearly insol. cold water
and ligroin.
Benzoyl derivativeO^^.O^.G'E.CSiO'Bz.
[125°]. White needles ; si. sol. cold alcohol and
benzene, insol. water and ligroin (Bornemann.
ii. 19, 1512).
OITRACONIO ACID.
19}
OHfarAMIC-CARBOXYLIC ACID v. Can-boxy.
eiNNAMIO AOID.
CINNAMIDOXIM 0,H,„N,0 i.e.
0,S.^.GR:Gn.C(^OB.)lS-B.^Phenyl.allmyl.aniM.
oxim. [93°]. Formed by direct combination
of cinnamo-nitrile with hydroxylamine. Kod-
like prisma. Sol. hot, less sol. cold water, v. sol.
alcohol, ether, and benzene, si. sol. ligroin. De-
composed by long boiling with water.
Salts.— B'HCl: [155°], flat concentric
prisms.— B'jHjCyPtClj : concentric needles, sol.
alcohol.
Methyl ether CsHj.qNHJNOMe : [98°];
prisms ; volatile with steam ; v. sol. alcohol,
ether, &o., nearly insol. cold water, more readily
in hot.
Ethyl ether C8H,.0(NHj)N0Et : [83°];
like the preceding.
Benzoyl derivative CgH.,.C(IHB^)'SOBz :
[160°]; fine needles; v. sol. alcohol, more
sparingly sol. benzene, chloroform, and ether,
insol. cold water. On boiling with water it loses
1 mol. HjO, giving phenyl-aUenyl-azoxim-benz-
enyl (Wolff, B. 19, 1507).
CINKAMO-LACTONE v. Cotjmaein.
CINNAMOITE v. Di-benzylidene-acetonb.
CINWAMOYL-ACETO-ACETIC ETHEB
C.^H.jO, i.e. Ph.CH:CH.C0.CHAc.C02Et. [40°].
From sodium aoeto-acetio ether and oinnamoyl
chloride (Fischer a. Knzel, B. 16, 166). Crys-
talline grains (from ligroin).
o-CINNAMOYIi-BUlYEIC ETHER v. Bemyl-
idene-ethyl-icsTo-Acsiic etheb, vol. i. p. 24.
CINNAMOYL-FOKMIC ACID v. Sixkyl-gly-
OXYIiIO ACID.
CINNAMYL AICOHOI OsH,„0 i.e.
C^s.CH:CH.CH,OH. Slyrone. Mol. w. 134.
[33°]. (254°) at 747 mm. S.G. "j" 1-0440. /!„ 1-582
at 20° (Briihl, A. 235, 16). E^ 69-7 (in a 9 p.c.
alcoholic solution) (Kanonnikoff ; Nasini a. Bern-
heimer, O. 14, 158). Obtained by distilling
styraein (cinnamyl cinnamate) with aqueous
potash (Simon, A. 31, 274 ; Eamdohr, Z. Pharm.
1858, 113; J. 1858, 446; T61, A. 70, 3). Long
thin needles, smelling like hyacinths. SI. sol.
oold water, v. e. sol. alcohol and ether.
Beactions. — 1. Oxidised by air and platinum
black to cinnamic aldehyde; and by chroinio
acid mixture to cinnamic acid and benzoic alde-
hyde.— 2. Boiling with aqueous KOH and PbOj
gives benzoic aldehyde. — 3. Eedueed by sodium
amalgam in presence of much water to phenyl-
propyl alcohol (Eiigheimer, A. 172, 122). Ee-
dueed by (15 p.c.) sodium amalgam by heating
with a little water for 3 days at 100° it forms
styrene CjHs and methyl alcohol, as foUows :
PhCH:CH.CH20H + H2= Ph.OH:CHj + CH3OH
(Hatton a. Hodgkinson, C. J. 39, 319). — 4. Aque-
ous HI {S.G. 1-96) at 190° gives toluene and
allyl-benzene (Tiemann, J3. 11, 671). — 5. Fuming
H.,SOi forms CgHnSOsH (?) (Jaoobsen, A. 146,
90). — 6. B2O3 forma cinnamyl oxide (CaHjjjO, a
heavy oil.
Acetyl derivative CfKaOAxi. (245°).
CINWAMYLAMINE CgH„N i.e.
C,H5.CH:CH.CH2.NHj. (100°). From cinnamyl
chloride and alcoholic NH, at 100° (Eamdohr,
Z. Phamn. 1858, 113 ; J. 1858, 448). According
to Malbot (O. R. 105, 574) the chief product is
di-oinnamyl-amine. — B'HCl : stellate groups of
Brystals.- B'jHjPtCla : si. sol. cold water.
CINNAMYL CHLORIDE C,,H„01 i.»,
CsH5.CH:GH.CH2Cl. Ahquid, obtained bypassing
HOI into cinnamyl alcohol. NaOEt converts it
into oUy C,H„OEt (Eamdohr, Z. Pharm. 1858,
113 ; J. 1858, 448). K^S forms oily (C^HJ^S.
CINNAMYLIDEHE - DIACETONAMiNE v.
vol. i. p. 28.
CINNAMYLIDENE - DI - THIO - GLYCOLLIC
ACID Ph.CH:CH.CH:(SCH2C0,,H)j. [143°].
Formed by the action of cinnamic aldehyde on
thio-glycollic acid (Bongartz, B. 21, 481). White
plates (from hot water). By the action of zinc-
dust in an alkaline solution cinnamyl thio-gly-
collic acid is formed.
CINNAMYL IODIDE Q,H,I. From cinnamyl
alcohol and PIj. Oil. Converted by alcoholic
KCy into oily C„H,Cy.
DI-CINNAMYL KETONE v. Di-benzymdbnb-
AOETONE.
CINNAMYL-METHYl KETONE v. Benzyl-
rDENE ACETONE.
CINNAMYL-PHENYL-KETOHE v. PhenyIt
OINNAMYIi-KETONB.
CINNAMYL-THIO-GLYCOLLIC ACID
Ph.0H:CH.CHrS.CH,.C02H. [77^"]. The com-
pound obtained by the action of cinnamic alde-
hyde on thioglycollic acid when treated with
zinc-dust in an alkaline solution yields this sub-
stance ' (Bongartz, B, 21, 481). White plates
(from dilute alcohol).
CH:CH
CINNOLIHE C^B.^J.e.C^i
/"
Thia
\n:N
base has not been isolated. The first of its de-
rivatives prepared was oxy-cinnoline carboxylic
>C(OH):C.COjH
acid GJS.t'C I
\N = N
obtained by warming
o-diazo-phenyl-propiolic acid with water (Eioh-
ter, B. 16, 677 ; v. also Widman, B. 17, 722).
CINNYL, A name sometimes applied to the
radicle cinnamyl Ph.CH:CH.CH.,.
CIRCULAR POLAEISATIOif v. Physical
METHODS.
CITRACETIC ACID C^fls- An acid said to
be formed, together with aoeconitio acid, by
treating bromo-acetic ether with sodium (Baeyer,
A. 135, 306).— Ba3A"'5,2aq : gummy. -PbjA'''^ 2aq.
CITRA-DI-BROMO-PYROTABTARIC ACID1;.
Dl-BKOMO-PYEOIABTAEIO ACID.
CITRA - CHLORO - PYEOTAETARIC ACID
V. CH]X>BO-PYROTABTAKia ACID.
CITRACONANIL v. PhenyUmide of Citba-
COKIO ACID.
CITEACONIC ACID Cfifi,- Mol. w. 130.
[80°]. S.G. 1-6. S. 238. B,^ 44-68 (in a 7 p.c.
aqueous solution) (Kanonnikoff, J. pr. [2] 32, ,
497). H.C. 477867 (Louguinine; O. E. 106,
1291). Beat of solution: 2793 (Gal a. Werner,
Bl. [2] 47, 159). Heat ofneutralisaticm: 27082
(G. a. W.).
Formation. — 1. The anhydride is the chief
portion of the distillate obtained by heating
citric acid. It rapidly combines with water
(Lassaigne, A. Ch. [2] 21, 100; Eobiquet,.4. Ch.
75, 78 ; Liebig, A. 26, 119, 152 ; Gottlieb, A. 77,
265 ; Baup, A. Ch. [3] 33, 192 ; Kammerer, A.
170, 191 ; Wilm, A. 141, 28).— 2. By the distil-
lation of itaconic acid (Crasso, A. 34, 68), of
lactic acid (Engelhardt, A. 70, 246), of citramalio
109
CTTKAOONIO ACID.
aoid (Caritia, A. 129, 160), and of ozypyrotaTtaric
acid (Demarpay, G. B. 82, 1337).
Properties. — Monoolinio four-aided piisms.
Deliqnesoenl;. V. sol. water, alcohol, and ether.
Volatile with steam. By dry distillation it is
partially resolved into its anhydride.
BeacHons. — 1. Sodium amalgam in presence
of water reduces it to pyrotartario aoid. — 2.
Bromine unites with it in the cold, forming
oitra-di-bromo-pyrotartaric acid (Eekul6, /. 1S62,
313).— 3. Faming hydria bromide unites with it
even in the cold, forming citra-bromo-pyrotar-
taric acid. — 4. Electrolysis of the potassium salt
forms allylene CH^.O-OH.— 5. Water at 120°
changes it to the isomeric itaconic acid. — 6.
Boiling dilate HNO3 forms mesaconic acid. —
7. Chlorine acting on sodium oitraconate in
aqueous solution forms chloro-citramalic, chloro-
methacrylio, and tfi-chloro-isobutyrio acids and
tri-chloro-aoetone (Gottlieb, J. pr. [2] 12, 1 ;
Morawski, J. pr. [2] 12, 369).
Salts .— NH^HA".— CaA" aq.— CaHjA,", 3aq.
CaA"5aq (Kammerer, A. 148, 326). —
SrHjA", 3aq. — BaHjA'', aq : silky needles. —
BaA" 2iaq (Kammerer, A. 170, 191 ; Petri; B.
14, 1634). — PbHjA'V — PbA". — PbA" 2aq. —
PbA"PbO.— AgHA".--AgjA".— AgjA." aq : hexa-
gonal crystals.
The acid aniline salt HA"NH3Ph loses HjO
when its aqueous solution is allowed to stand for
a few days, and deposits crystals of the acid
aniHde OOjH.O3H1.CO.NPhH.
The neutral aniline salt when boiled with
water gives the phenyl-imide 0,H4(0202)NPh.
The ethyl-aniline andmethyl-aniline
, salts do not give anilides when heated. The same
is the case with GjHs.NMej and CeH3.NEt2 salts.
The ethyl derivatives of^-toluidine behave
exactly like the corresponding aniline com-
pounds.
Di-phenyl-amine citraconate is only
formed at 100°, since the Ph^KH separates com-
pletely on cooling (Michael, Am. 9, 194).
MefhylefherMaJ^'. (212° i. Y.). S. Sat
15°. S.a. if 1-1168; |g 1-1050. mb 1-4442;
/Uh 1-4721 at 15-5°. From citraconic acid, methyl
alcohol, and HOI (Perkin, G. J. 39, 655). From
silver oitraconate and Mel. OU; pleasant odour.
Mthyl ether Et^A". (232° i. V.). S.G. »
1-051; |g 1-038. M.M. 10-499 fPerkin, O. J.
Proa. 3, 99). /^d 1-4397; Mh 1-4659 at 16-5°
(Gladstone). An alcoholic solution with sodium-
aceto-acetic ether at 100° forms an oil C^H^O,
(174°) at 26 mm. (Michael, J. pr. [2] 35, 354 ;
Am. 9, 118).
Ghloride OjH4(COCl)j. (95°) at 17-5 mm.
S.G.iw 1-408. From the aoid and PCI5 (Strecker,
B. 15, 1640).
Anhydride 0,nfi fi,. [7°]. (214° 1. V.).
S.G. 14 1-241 (Anschiitz, B. 13, 1542 ; 14, 2788).
Partially converted by distillation into xeronic
anhydride (Fittig, A. 188, 64). Thiourea at 130°
converts it into NHj.OS.NH.OO.O3Hj.OO2H [223°]
(Pike, B. 6, 1106).
Amide CjHjOjfNHJj. Thin colourless
tables, sol. water, decomposes at about 186°
(Strecker, B. 16, 1640).
Imide Ofiflt(SS). [110°]. Formed by
distilling acid ammonium oitraconate (Gottlieb,
A. 77, 274; Ciamioian a. Dennstedt, 0.12, 601).
Needles (from water). Br forms C,H,Br02(NH)
[0.181°] and 05H,BrjO3(NH) [o.l44»]. OjHjOjNAg
(Mendini, (?. 15, 184).
Anilide CsHiOj(NHPh)j : [176°], long flat
needles, sol. alcohol and ether, slightly in water
(Strecker, B. 15, 1639).
Acid anilide COjH.O3H4.CO.NHPh.
Gitraconamlic acid. Formed spontaneously by
allowing the aqueous solution of the acid anUins
salt to stand for a few days. Large trimetHo
prisms or long needles.
Phenylimide G,'3.,<^f,Q'^'S'Ph. Citracon-
anil: ,[98°], formed by boiling aniline and
citraconic acid in aqueous solution (Michael a.
Pabner, B. 19, 1375 ; Am. 9, 180).
p-Ghloro-phenylimide
C3H4:Cj02:N0sH4Cl. [114°]. From the preced-
ing and 01 (Morawski a. Haudy, M. 8, 399).
Bromo-phenylimide "GjHjOj.N.OjHjBr,
[118°]. From the phenylimide and Br (M. a.
K.).
Di-nitro -phenylimide
C3H,:OjOj:N.C5H3(NOj)j. [120°]. Prom the
preceding, HNO, and HjSO, (Gottlieb, A. 85,
21).
Acid toluide ''C0jH.03H4.00.NHC,H,
[166°]. Formed by warming an aqueous solu-
tion of acid j7-toluidine citraconate.
p-Tolylimide C3H,:02O2:N08H4Me. [115°].
{aS-Naphthylimide CsH^OjNC.oH,. [142°].
(360°). YeUow plates, sol. most solvents, insol.
cone. HClAq (Morawski a. Glaser, M. 9, 286).
{ffj-Naphthylimide 0,5H„0jN. [110°].
From citraconic aoid and ()3)-naphthylamine at
175° (M. a. G.). Pale yellow needles.
m-Garboxy -phenylimide
03Hj<^°>N.0,H4.C0jH. [218°]. Formed by
boiling ni-amido-benzoic acid with an aqueous
solution of citraconic acid. Prismatic needles,
sol. hot alcohol an4 water, sol. dilute alkalis.
Phenyl-hydrazide 03H,<^^q> NjHPh.
[160°]. Bright yellow needles; si. sol. cold, y.
sol. hot, water.
Isomerides of Citraconic Acid v. Itaconic
Acn>, Mesaoonio aoid, Cboiaoonio acid, and
FTHYLIDEIIE-IIALOIIia ACID.
GonsUtution of Gitraconic acid. — Citraconic
aoid stands to mesaconic acid in the same rela-
tion that maleic acid does to fumario aoid. The
formation of allylene by the electrolysis of citra-
conic and mesaconic acids indicates the presence
of a methyl group, so that citraconic acid is
methyl-maleio acid, while mesaconic aoid is
methyl-fumario aoid. On the other hand, itaconic
acid is said to give isoaUylene CHjiCzCHj on
electrolysis.
Citraconic knd maleic aoids differ from the
aZZo-isomerides in combining vigorously with
halogens and HBr. The ethers of citraconic
and maleic acids have higher boiling-points than
those of mesaconic and fumario acids, the differ-
ence being much greater between the methyl
than the ethyl ethers.
On the o&er hand, (a)-ooumaric ethers have
lower boiling-points than (;3)-coumaric ethers.
Citraconic acid with PCI, gives mesaconyl
chloride, (o)-coumaric aoid with POI5 gives (fi)-
coumaryl chloride (Petri, B. 14, 1634).
The indices of refraction of the oitraoonifl
CITRIC ACID.
103
and mesaconio ethers are neatly the same for the
ted end of the speotrum, but the mesaoonic
ethers refract the violet raya more powerfully.
The ethers of oitraconio, maleio, and (a)-
eoumario acids contract in volume on changing
to the more stable isomerides. The acid aniline
salts of citraoonic and maleic acids readily
change, especially when their solution is eva-
porated at 100°, into phenylimides ; the corre-
sponding salts of mesaconio and fumario acids
are not affected (Ferkin, C. J. 39, S61).
The initial velocity of etheriflcation is 29-3
for itaoonio acid, 37'9 for mesaoonic acid, and
47-4 for citraconio acid (Menschutkin, tT'. B, 13,
627 ; B. 14, 2680).
CITBAKALIC ACID v. Oxy-pyboiabiabio
USID.
CIIBANILIC ACID v. Phenylimide of Cmbio
ACID.
CITBAIABTABIC ACID v. Ci-ozy-pybotab-
TABIC ACID.
CITBAZIC ACID v. Di-ozs-pybidine-oabbo-
XYLIC ACID.
CITBENE V. Tbrpenes.
CITBIC ACID CsHjO, i.e.
COjH.CHj.C(OH){0OjH).CHj.C0jH. [147^
(Grimaux a. Adam). S.G. 1-54. S. 125 at 15° ;
200 at 100°- S. (of OsHjO, aq in 80 p.o. alcohol)
87 at 15° ; S. (of C^fi, in absolute alcohol)
75-9 at 15°; S. (of O^Ufi, in ether) 2-26 (Bour-
join, Bl. [2] 29, 244) ; S. (of 0,HA in ether)
9-1 (Lippmann, B. 12, 1650). HJ". 354,000 (v.
Bechenberg).
Oceurrence. — Inlemons, oranges, cranberries,
cowberries, and sundew {Drosera intermedia) ;
together with malic acid in red currants, goose-
berries, whortleberries, raspberries, and cloud-
berries (Buhus ChamcBmorus) ; together with
both malic and tartaric acids in tamarinds and
mountain ash berries (Scheele, Opvscula, 2, 181 ;
Berzelius, A. Ch. 94, 171 ; [2] 52, 424, 432 ; 67,
303; 70, 215; Bobiquet, A. Gh. [2] 65, 68;
Liebig, A. 5, 134 i 26, 119, 152 ; 44, 57 ; Mar-
chand, J. pr. 23, 60; Cahours, A. Ch. [3] 19,
488 ; PebaJ, A. 82, 78 ; 98, 67 ; Tilley, J. Ph. 13,
305 ; Ferret, Bl. [2] 5, 42 ; Warrington, C. J. 28,
925 ; Stein, B. 12, 1603 ; Eossovic, C. C. 1887,
1157). Occurs also in certain plants, e.^. celan-
idine (Haitinger, M. 2, 485), leaves of the wild
cherry (Bochleder, Z. [2] 6, 176), Lwpitms luteus,
Vicia saUva(y etch), Vicia Faba, Pisumsatwum
(peas) and white beans [Phaseolus) (Bitthausen,
J.pr. [2] 29, 357). Occurs as Ume and potash
salt in tobacco, and in the juice of lettuce. Oc-
curs in the root and leaves of madder (Boch-
leder, A. 80, 322 ; WiUigk, A. 82, 343), in beet-
root (Michaelis, J. 1851, 394 ; J. pr. 54, 184 ;
Schrader, A. 121, 370), and in young vines
(Wittstein, J. .1857, 620 ; Vier. pr. Pharm. 6,
192).
Synthesis. — s - Di - ohloro-acetone combines
withhy(fcogencyanideforming(CH2Cl)2C(OH).CN
which is converted by saponification into
(0H201)2C(OH).CO^, whence KCy readily forms
(CN.CHyjC(OH).COjH which is converted by
treatment with HCl into citric acid (Grimaux a.
Adam, A. Ch. [5] 23, 356 ; O. B. 90, 1252).
Preparation. — Lemon juice is allowed to
undergo incipient fermentation, and is then
boUed with chalk and lime. The ppd. calcium
Vol. U.
citrate is decomposed by an equivalent quantity
of H,SO,.
Properties. — Usually crystallises in efflores-
cent trimetric prisms (containing aq) a:b:e
= 'BOeS:!: '4106. Different specimens of crys-
tallised citric acid when powdered and left over
HjSOj lose water at very different rates (Gros-
jean, O. J. 43, 331). From boiling solutions
citric acid separates in anhydrous crystals
(Sarandinaki, B. 5, 1101). Crystals containing
2aq may sometimes be obtained (Cloez). Lime
water produces little or no pp. in the cold, but
calcium citrate is ppd. oh boiling. Calcium
citrate is insoluble in KOH ; it dissolves inNH,01,
but is reppd. on boiling. Citric acid differs also
from tartaric acid in not forming an insoluble
acid potassium salt. Boiling, strongly alkaline,
permanganate is reduced by citric acid to man-
ganate only, the liquid becoming green, whereas
in the case of tartaric acid the reduction pro-
ceeds further, the liquid becoming brown (Chap-
man a. Smith, Laboratory, 1, 89 ; cf. Wimmel,
Z. [2] 5, 286). PeCl, gives a light yeUow pp.
in a hot solution of an alkaline citrate ; the
pp. dissolves in excess of the citrate (Eiimmerer,
Fr. 8, 298). Silver citrate dissolves in hot water
without blackening. Cone. KjOrjOjAq is
blackened in the cold by tartaric acid but not by
citric acid.
Estimation (in lemon juice). — The juice is
neutralised with Na^CO,, CaCL, is added, and the
liquid boUed. The pp. is collected and washed.
The filtrate and washings are treated with I^H,
and evaporated to a small bulk. Some more
calcic citrate then separates (Grosjean, C, J. 43,
332; cf. Fleischer, Ar. Ph. [3] 6, 97; Allen,
O. N. 32, 277 ; Creuse, Ph. [3] 2, 547). A second
concentration may then be effected, when a third
quantity sometimes separates. Turmeric is better
tiian litmus as an indicator in alkalimetric ex-
periments with citric acid (F. Watts, S. C. I. 6,
214).
Beaotions.—1. By heat it is split up at 176°
into HjO and aconitio acid CgHgO,, which on
dry distillation again splits up into CO, itaconio
acid OsHjOi, citraconic anhydride 05^40,, and
acetone. — 2. By heating with water (10 pts.) at
160° it is split up into itaconio acid and CO,
(Markownikofla. Furgold, ^.[2] 3,264).— 3. Cit-
ric acid (100 g.) heated with water (60 g.) and
sulphuric acid (100 g.) for 5 hours gives aconitio
acid which separates on cooling (Hentschel,
J. pr. [2] 35, 206). 100 g. citric acid heated
with 100 g. water and 5g. HjSO, at 170° give
aconitio and itaconio acids (Pawolleck, A. 178,
152).— 4. Cone. HjSO, at 40° gives off CO, CO,,
and acetone, and forms an acid whose acid
barium salt is (05H,S0j)2Ba, and is converted by
baryta-water into (CaHsSOJjBa (Wilde, A. 127,
170). —5. On dry distillation with glycerin, it gives,
besides acetone, acrolein, CO, and CO2, a distil-
late containing the pyruvic ether of glycide
CH„.CH.CH~O.CO.CO.CH,. [82°]. (241°)
\y
O
(De Clermont a. Chautard, 0. B. 106, 520).— 6.
Cone. HOlAq at 160° gives aconitic acid ;'at200°
it also forms diconic acid G^,gOs, and gives oft
CO and CO^ (Hergt^ J. pr. [2] 8, 373).— 7. An
aqueous solution mixed with yeast and chalk
and exposed to the air at 25° forms acetic and
O
794
CITRIC ACID.
butyric acids (How, C. /. 5, J , Peisonne, C. B.
36, 197). — 8. GMorme acting on a cone, aque-
ous solution of soditun citrate forms hexa-chloro-
acetone and chloroform. Br acts in the same
way (Cloeia, 0. B. 53, 1120).— 9. Potash-fusion
gives oxalic and acetic acids (Liebig, A. 26, 158).
10. Acetone is formed by distilling sodium
citrate with lime (Preidl, M. 4, 151). — 11. An-
hydrous citric acid is converted by a mixture of
fuming HNOs (1 P*-) and HjSO, (2pts.) into the
nitrate Oan^{ONOi){OOJB.), erroneously eaUed
nitro-oitric acid. It is insol. ether, and forms
insoluble salts BasA'''^ and PbjA'''^ (Champion
a. PeUet, Bl. [2] 24, 448).— 12. Citric acid (1
mol.) heated with glycerin (1 mol.) at 100°
forms glyceryl citrate G^^.G^fi, a glassy
mass, insol. water (Bemmelen, J. pr. 69, 84).
Excess of glycerin at 170° givfes so-called
citrp-diglycerin C,2H,gO,„(?). — 13. Citric
acid (1 mol.) heated with mannite (1 mol.)
at 140° forms oitromannitan 0,jH„Oj
(Bemmelen, J. 1858, 435). Excess of citric acid
(2 mols.) heated with mannite at 150° forms
dicitromannitan C,9H2oO„. Both bodies are
amorphous.
Salts. — NHjHjA'" : triclinio crystals. —
(NHJjHA". S.G. \» 1-479 (Clarke, 4to. 2, 174).—
(NH4)jA"'aq: deliquescent. Eerric and alumi-
nium oxides, fresUy precipitated, dissolve in a
solution of ammonium citrate, and from the solu-
tions when evaporated salts of the general type
CeH3O,H(NH02(OAO,(NH,)j3M2H,O crystal-
lise out. Sunilarly magnesium, manganese, nickel,
cobalt, zinc, copper, and mercuric oxides dissolve
in ammonium citrate to form salts of general
type [CjHsOjfNHJJjM generally with 1 mol.
H2O. Solutions of these salts are not precipi-
tated by ammonia, the alkaline hydroxides and
carbonates, but completely precipitated by H^S
or anmionium sulphide. The oxides and carbo-
nates of Ba, Sr, and Ca decompose boiling solu-
tions of ammonium citrate forming insoluble
pps. of the corresponding salts CajA'^ &c. (Lan-
drin, A. Ch. [5] 25, 233; C. B. 86, 1336).—
fNHJsHsA'", (Heusser, P. 88, 121).— LijA'" (?)
(Thomson, Ph. [3] 13, 783).— NaHjA'" aq.—
NazHA"'aq: needles.— NajA'" 5iaq. S.G. 2?
1-858 (Clarke, Am. 2, 174 ; Kammerer, A. 148,
294; 170, 176). Trimetric prisms or groups of
silky needles. — NajA'" 2aq (Heldt, A. 47,
157). — KHjA'" 2aq. — K,HA"'. — K,A"' aq.—
K,(NHJ2HA"V-K2(NH,)A"'. - K,Na,A"'26iaq.
KjNa8A"'j llaq.— TI3A'" (Kuhlmann, C. B. 55,
607). — Ba8A"'27aq:amorphouspp. — ^BaaA"'j5aq:
groups of minute needles, formed by boiling
the above with water. — ^Ba,A"'j 3Jaq : minute
monoclinio prisms, formed by treating either
of the two preceding salts with ammonia. —
Sr3A"'2 5aq: minute silky needles. — Sr3A"'j2aq.
SrjHjfCeH^O,), llaq. — Sr,H2(C,H,0,), 2iaq.—
CajA" 2 laq. From NajA'" and OaClj : pp. changed
in water at 100° into minute transparent needles.
CajA'''^ 7aq.— CaHjA"'j aq.— Mg,H3(C,H,0,), 8aq.
Mg,A"'2 9aq. — MgaA'", 6^aq. — MgaA'", 7aq. —
Mg„Hj(C3H,0,), 13aq. — Mg,Hi(C„H,0,)s 3aq. —
MgjA "j 14aq.— Mg(NH,)4A"'j 2aq (Landrin, C.B.
86, 1336). — Zn,A"'j2aq. — Zn,H,(C3H.0,)5. —
ZnsHjA'", 2aq. — Zn(NH J ,A"V — Cd,A"'s faq. —
CdjA'", lOaq.— Cd,Hj(C,H40,)5 18aq : needles.—
CdgHj(C„H,0,)5 27aq, — Cu,OeH.0, 2iaq : green
crystalline precipitate which is obtained by bo3.
ing a solution of cupric carbonate in citric acid. —
CusHjfCjHjO,), 15aq : greenish pp. got by adding
alcohol to the above solution. — Cu(NH4)4A"'2 aq
(Landrin, O.B. 86, 1336) Pb3A"'2 3aq: crystal-
line pp. from lead nitrate and Na,A"'. —
PbjCsHjO, 2aq : amorphous ; got by heating the
preceding with ammonia. — PbjA'", aq : amor-
phous pp. from alcoholic Pb(0Ac)2 and citric
acid. — PbHA'" : crystals, v. sol. water. —
PbjA"' PbjOj3aq (at 100°) (Otto, A. 127. 176).—
Fb,A."'^hfl,. - Hg(NHJ,A"'r — C03A'", 14aq :
amorphous.— Co(NH<),A'"j 4aq. — Ni,A"', 14aq :
amorphous. — Ni(NH4)4A"'j4aq.—MnsA"'j2aq:
crystalline powder formed by boiling citric acid
with MnCO, (Heldt) ; the following salts are
formed at the same time (E.). Sodium citrate
does not precipitate salts of manganese. —
MnHA'" aq. — MujA'", 9aq : trimetric prisms. —
Mn5Hj(0,H,0,)s 15aq.— Mn,H,(C8H40,)4 18aq.—
Mn(NHj4A"'j.— FeHA^aq : crystalline powder
formed by boiling iron with aqueous citric acid. —
EeNaA'": app;ie-green scales (Bother, P%. [3] 13,
629). — ^Pe(0H)Na2A"' : amorphous grass-green
powder. — FeNaaHjA'",. — PelS%Hj(PO,)A"'.—
EeA'" Ifaq : got by dissolving Pe(OH), in citric
acid. Light brown film.— Ee(0H)HA"'2aq
(Schiff, A. 125, 147).— Fe(NHJiA"',: greenish-
yellow mass.^Ee(NH4),HA"'j.— Ee(NHJH,A"V
(FeO)j(NH4)A"' 4aq. — FeA"'(NH,), Saq* —
Eej(NH4)3(03H,0,)j3aq (M6hn, J. 1873, 570).—
Ee(OH)(NHj4A"'j2aq. — Al(OH)(NHJjA"'s. —
SmA'" 6aq : amorphous pp. sol. ammonia. The
ammoniacal solution does not become turbid on
heating (ddve, Bl. [2] 43, 172).— Y»A"', 14aq.—
LaA'" 3iaq (Czudnowicz, J. 1860, 128 ; J. mr.
80, 31). — CeA"'3iaq. — K3SbA"'2 2iaq: hard
prisms grouped in tnifts. — ^BiA'": granular pp.
obtained ,by boiling bismuth nitrate with citric
acid (Bother, Ph. [3] 6, 764; Cavazzi, <?. 14, 289).
— {BiO)(NHJjA"': obtained, together with the
following body, by boiling the preceding with
ammonia.— (BiO)(NH0HA"'.—BiA"'4Bi(OH)3:
gelatinouspp.— BiA"'(NH3)3aq(Bartlett,O.JV.ll,
28).— FeA"'BiA"'(NH3)3 3aq.— AgjA'" : powder;
crystallises from water in needles. — AgjHA'"
(Eonnefahrt, J. 1876, 562).— Ag3A"'(NH5) IJaq
(Wohler, A. 97, 18).— Ag^A'" (?) (W.): got by
heating AgsA'" at 100° in a current of hydro-
gen. — Ag2CaO,H40,. — Telluro - citrate.
E2A"'2TeOH2 aq : leaflets, v. sol. water ; formed
by adding citric acid to a solution of potassium
tellurite and evaporating (Elein, C.B. 102, 47). —
Boro-oitrat'es. Boro-oitric acid HjA^BtBOj at
80° is formed by dissolving boric acid (1 mol.) in a
solution of citric acid (2 mols.). It is a deli-
quescent mass. The boro-citrates are formed by
dissolving boric acid in solutions of the citrates.
The magnesium borocitrates do not crystallise. —
Na3A"'3HBOj.— Na2BLA"'2HB02.—
NaH2A"'HB02. — KjHA"'2HB0,. — K3A"'3HBO,.
KH3A"'HB0j.— KH^A^jSHBOj.-
LiH2A"'HB02.— LijHA"'2HB0-.— Li3A"'3HBO-
MgH4A"'3HBOj.— Mg2H2A"'24HB02.—
Mg3A"'j6HBOs (Scheibe, Ph. [3] 11, 389).—
Aniline salt NPhH,OsHgO,. Needles (Pebal,
A. 82, 91). At 145° it changes to the phenyl-
imide. i^-Oumidiue salt CsH,Me,NHjH,A"'
[133°] (Schneider, B.21, 660).
Methyl ether MeHA'" (Demondesir, A,
80. 302).
CITRIC ACID.
195
Di-methyl ether UeMA!" (St. Evre, A
80 325). ^
Tri-methyl ether MesA'". [79°]. (c.
285°); (176° at 16 mm.). Penned, together with
the two preceding bodies, by passing HOI into a
solution of citric acid in MeOH (St. Evre, 0. B.
21, 1441). Triclinio crystals. Partly split up
on distillation into HjO and tri-methyl aoonitate
(271°). PCI, gives oily 0,Ufil(OO^e)^.
Acetyl-trimethyl ether
C,H,(OAo){CO,Me),. (281°); (171° at 15 mm.).
Mono-ethyl ether EtHaA'". Formed by
the action of sodium amalgam upon wet EtjA'"
(Glaus a. Boennefahrt, B. 8, 866). Formed also
by boiling citric acid with acetic ether (Ereitmair,
B. 8, 737). Thin prisms ; v. sol. water, alcohol,
and ether.— NajEtA'" (at 100°); prisms.—
Ag,EtA"'.
Di-ethyl ether M^A.'". (218°) at 60 mm.
Formed, together with the preceding, by the
action of sodium amalgam on wet citric ether. —
NaEtjA'" : deliquescent. FormaUon. — (Conen,
B. 12, 1658 ; Euhemann, O. J. 51, 404).
Tri-ethyl ether EtsA'". (218° at 60 mm.)
pjuhemann, B. 20, 799 ; C. J. 51, 404) ; (213° at
85 mm.); (263° at 300 mm.) (Conen, B. 12,
1653). S-G.^i" 1-137(0.). ;«^ 1-4513. Bo, 10509
(Briiiil). Formed by heating citric acid with
alcohol and H^SO,, or, better, by saturating an
aleohoUc solution of citric acid with HOI (Th6-
nard, Mdm. d'Arcueil, 2, 12 ; Malaguti, A. Oh.
63, 197 ; Dumas, O. B. 8, 528 ; Marchand, J. pr.
20, 318 ; Heldt, A. 47, 167 ; Demondesir, O. B.
33, 227; Pebal, A. 98, 67; Claus, B. 8, 867),
Oil ; 7. sol. alcohol and ether. It boils with de-
composition at 280°.
Acetyl- tri-ethyl-ether
C,H4(OAc)(004Et)3: (288°) ; (229° at 100 mm.),
(214° at 40 mm.) ; S.G. ^ 1-1459. By the action
of strong aqueous NH, it is converted into the
amide of di-oxy-pyridine-carboxylic acid (citraz-
/0(OH):OHv
iniide)N^- — ■■ ^C-CONHj (Buhemann, B.
\0(OH);OH'^
20, 799; C.J. 61, 404; cf. WisUcenus, .4. 129,
176). yields a phenyl-hydrazide [128°].
Tetra- ethyl ether 03H4(OEt)(COjEt)j.
S.G. =j° 1-1022. Hf, 1-4548. Bo, 119-97 (Briihl).
Thick liquid. Bitter taste. (238° at 150 mm.,
and about 290° at 760 mm.). With POl, it gives
aeonitic ether (Conen, B. 12, 1653).
Tri-n-propyl ether C3H,(OH)(00,J'r)s.
(198°) at 13 mm.
Acetyl-tri-n-propyl ether
C3H,(0Ac)(C0203H,),. (205° at 13 mm.). When
heated to 250°-280° the acetyl ethers readily-spUt
oS acetic acid, yielding the corresponding ethers
of aeonitic acid (Aiischutz a. Klingemann, B. 18,
1953).
Mono-isoamyl ether GsHnHjA'" (Breun-
lin, A. 91, 318). — (NHJj(C5H„)A"'. —
NaH(C,H„)A"'.-KH(0,H„)A"'.-Pb,(0„H„0,),
0aHj(05H„)2A"', xaq : laminae.
Ethyl isoamyl ether CsHnEtHA'". Oil.
Tri-phenyl ether CaH50(C02Ph),. [125°].
From citric acid, phenol and FOCI, (Seifert,
/,l»r. [2]31,470).
Mono-amide OjHsO(0O^jCONHj. Citro-
mon-andc add. [138°]. Colourless crystals ; ex-
tremely sol. water, less sol. alcohol, insol. ether
ftnd ligroin. Formed as a by-product iu the
preparation of the tri-amide. By boiling with
HOI, pi by heating with 75 p.o. H^SO,, it is con-
verted into citrazinic acid C^jNO,. — Salt.
CsHjOeNAgj: white pp.
Di-amide 03H50(002H)(CONH,)j: citro-
di-armc-acid: [158°] ; white plates ; v. sol. water^
nearly insol. alcohol and ether. Formed as a
by-product in, the preparation of the tri-amide.
By boning with HCl, or by heating with 75 p.c.
HjSO,, it is converted into citrazinic acid. —
CjHjOsNjAg : crystalline pp.
Tri-amide OsHsO(CONH,), : [210°-215°];
colourless crystals; S. (at 18°) = 2-7; (at 100°)
= 33-3 ; insol. alcohol, ether, &o. Prepared by
the action of strong aqueous NH, (-88) in the
cold upon the tri-methyl ether of citric acid.
By heating with HCl or with 75 p.c. H^SO^ it is
converted into citrazinic acid (Behrmann a. Hof •
mann, B. 17, 2682).
Tri-methyl-amide
C3Hi(0H)(00.NHMe),: [124°]; white prisms, v
sol. cold water.
Phenylimide 0,H4(0H)(C0jH)(0ANPh).
CitramiUc acid. Formed by heating citric acid
(1 mol.) with aniline (1 mol.) at 150° (Pebal, A.
82, 92). Crystalline spherules (from water). —
Ag0,ja,„N0,.— NPhH,0,^„NO,.
Dianilide CsH,(OH)(COjH)(OONPhH)j.
[150°]. Formed by boiling the di-phenylnamide-
imide with ammonia. Concentric groups of
silky needles (from aJcohol).
Bi-phenyl-amide-imide
OjH,(OH){CONPhH)(OANPh). Formed by
heating m6 aniline salt of the phenylimide.
Hexagonal plates ; sol. alcohol.
Tri-anilide C3H«(0H)(00NPhH)s.
Formed by heating normal aniline citrate.
Prisms (from alcohol). InsoL alkalis.
p-Tolyl-imide
C,H,(0H)(C0^)<^3>NC,H,: [173°]; smaU
white crystals; v. sol. alcohol, ether, and hot
water, si. sol. cold water. Formed by heating
mono-j>-toluidine citrate at 160°-170°.
Di-p-tolyl-amide-imide
C,H,(OH){OO.NHC,H,)<gO>NC^, : [205°] ;
small granular crystals; m. sol. alcohol and
ether, insol. water. Formed by heating 1 mol.
of citric acid and 2 mols. of 2>-toluidine for three
hours at 160°-170°.
Di-p-tolyl-di-amide
C,Hj(OH)(CO.NHC,H,)j(COjH) : [161°]; smaU
needles; sol. alcohol and ether, insol. water.
Formed by heating the preceding compoimd with
aqueous NH,.
Tri-p-tolyl-tri-amide
0,H,(OH)(CO.NHC,H,),: [189°]; silky white
microscopic needles; si. sol. alcohol, insol.
water. Formed by heating 1 mol. of citric acid
and 3 mols. of ^-tolnidine at 140°-145° (Gill, B.
19, 2352).
Bi-'^-cumyl-amide-imide
C,H^(OH)(CO.NHO^jMe,)(OANO,H,Me,).
[173°]. The chief product of the action of
iji-cumidine (2 mols.) on citric acid (1 mol.) at 160°
(Schneider, B. 21, 660). Prisms; v. sol. alcohol.
Di-f^-cumidide
C,H4(0H)(COja)(C0.NH.C.H,Me,)r [194°].
Formed by treating the preceding with alkalis. — .
NaA'. [236°].
09
196
CITRIC ACID.
Tri-yji-cumidide
CsH.(0H){C0.NH.0,H,Me3),: [185°]; white
powder, si. sol. alcohol. Formed by heating
citric acid (1 mol.) with ilf-cumidine (3 mols.).
Bemidide
XO-NH-CbH^
OjHitomfCOjHK I . From benzidine
\OO.NH.CeH^
and citric acid at 150°. Carbonises above 300°.
Crystalline powder.
Tolylene- diamide
C3H,(0H)<^»°^^>0,H,Me. [187°]. From
citric acid and tolylene-diamine. [99°] at 130°.
Minute crystals.
Tri-nitro-anilide
03H4(OH)(CO.NH.CeH,NOj),. [108°]. Formed
by nitrating the anilide.
Di.{0)-naphthyl-ainide-imide
C3H,(0H)(C0.NH0,„H,)<;g°>NC,„H, : [233°].
Formed by heating 1 mol. of citric acid with
2 mols. of ()3)-naphthylamine at 140°-150°.
White Biz-sided plates. SI. sol. alcohol, insol.
water.
Di-(0)-nap'hthyl-di-amide
0,H4(0H)|00jH)(C0.NHC,„H,)j: [172°]. Formed
by digesting the preceding body with cone,
aqueous N^ at 170°- Microscopic concentric
needles, Insol. water. Weak acid reaction to
litmus. — ^/L'Ag.
> Tri-(p)-naphthyl-tri-amide
C,H^(OH)(CO.'NHC,oH,),: [215°]. Formed by
heating the di-naphthyl-amide-imide with (j8)-
naphthylamine (1 mol.) at 150°-170°. Micro-
scopic prisms. V. sol. alcohol, insol. water.
Di-{a)-naphthyl-amide-imide
C3H.(OH)(CO.NHO,oH,)<^°>NO,.H, : [194°].
Formed by heating 1 mol. of citric acid with
2 mols. of (o)-naphthylamine at 140°-150°. Six-
sided plates (from benzene). V. sol. alcohol,
ether, &o., insol. EClAq.
Di-(a)-naphthyl-di-amide
C»H,(OH)(COjH)(C0.NH0^<,H,)j: [149°]. Formed
by heating tine preceding body with aqueous
NH, at 150°-160°. Small needles (from alcohol).
A'Ag.
Tri-{a)-naphthyl-tri-amide
C3H,(0H)(CQ.NHC,„H,)3 [129°]. Formed by
heating the di-(o)-naphthyl-aTOide-imide with
(i8)-naphthylamine (1 mol.) at 150^-170°. Micro-
scopic rhombic prisms (Hecht, B. 19, 2614).
ISOUEBISE OF CITBIC ACID v. Oxy-ibi-
CABBA£Lyi/IO ACID.
CITSIDIC ACID V. AcoNiTio acid.
CITaONEIIOI C,„H,80 (Gladstone, C. J. 25,
47) or C„H,30 (Wright, 0. J. 12, 318). (210°-
220°). The chief constituent of the oil of
citronella {Andropogon Ncwdvs or Schcenanthus) ,
a grass cultivated in Ceylon. PjSj appears to
form a mixture of terpenes and their polymerides.
It combines with Br, forming a dibromide, which
is split up by heat into HjO, cymene, and HBr.
CLADONIC ACID. {^)-Usmc acid. [175°].
Occurs in Cladoma ramgiferma (Stenhouse, A.
155, 50 ; Hesse, A. 117, 346). Yields betorcin
on dry distillation. Cladonic acid is probably a
mixture of usnic and barbatic acids (Paterno, O.
6, 113; 12, 231 ; Stenhouse, A. 203,285).
CLASSIFICATIOIT. CHEMICAL.— In the fol-
lowing article nothing more is attempted than to
sketch the outlines of the methods by the em-
ployment of which a fairly satisfactory scheme
of chemical classification may be attained. 'By
the classification of any series of objects ia
meant the actual or ideal arrangement together
of those which are like and the separation of
those which are unlike; the purpose of this
arrangement being primarily to disclose the
correlations or laws of union of properties or
circumstances, and secondarily to facilitate
the operations of the mind in clearly con-
ceiving and retaining in the memory the
characters of the objects in question.' '
The importance of classificatidn in chemistry
can scarcely be too much insisted upon. The
fundamental object is to arrange the various kinds
of matter with which chemistry is concerned in
classes, so that the connexions between the pro-
perties and the composition of these kinds of
matter shall be 'made apparent. Inasmuch as
our knowledge of the connexions between the
composition and the properties of different kinds
of matter is being modified from day to day, it is
evident that no system of chemical classification
can be regarded at present as a final system.
That we may draw the outlines of a scheme of
chemical classification, it is necessary first of all
to inquire what the objects are which the scheme
is to include.
Chemistry concerns itself vrith the connexions
between the properties and the composition of
homogeneous kinds of matter; a homogeneous
kind of matter being such that all the portions,
however small, into which it can be divided, are
possessed of the same properties as belong to
the mass. But the properties of homogeneous
kinds of matter are of two kinds; on the one
hand, there are those properties which belong
to, or which may be acquired by, the specified
kind of matter considered apart from other
kinds of matter; on the other hand, there are
the properties which are exhibited by the spe-
cified kind of matter when it acts on, and is
acted on by, other kinds of matter. Chemistry
concerns itself more especially with the latter
kind of properties. Another classification of the
properties of homogeneous kinds of matter may
be njade ; we may pay regard to those properties
which are the sums of the properties of the parts
of the specified mass of matter ; or we may look
to those properties which are dependent on the
configurations of these parts. Any mass of
matter may be conceived to be made up of a
vast but finite number of minute particles, which,
for the purposes of the investigation in hand,
may be regarded as indivisible. These particles
may or may not be possessed of the properties
which distinguish the mass of matter imder
consideration ; the properties of the mass may
be the sum of the properties of the particles, or
they may differ from the sum of these properties.
In the latter case we assume that the properties
of the mass depend, among other conditions,
on the relative arrangement of the particles.
The weight of any mass of matter, i.e., the force
with which the matter is attracted towards the
* Stanley Jevons (in Ptinciples of Science^ ii. 348, Isl
ed.) modifying Huxley's definition given in Lectureton ttm
JElemerUt itf Comparative Anatomy (1864), p. 1.
CLASSIFICATION, CHEMICAL,
197
earth's centre, is absolutely independent of the
arrangement of the particles, and is equal to the
sum of the weights of these particles. The volumes
occupied by specified masses of homogeneous
gases, on the other hand, are entirely dependent
on the relative arrangement of the particles, and
are not the sums of the volumes occupied by
these particles when separated from each other.
Most of the chemical properties of any homo-
geneous kinds of matter are not the sums of
the properties of the particles of such kinds of
matter.
Such then being, very broadly, the kind
of properties considered in chemistry, we have
next to inquire as to the meaning of the term
composition. This inquiry at once carries us
back to properties. Experiment shows that from
certain kinds of homogeneous matter there can
be obtained two or more different kinds of ho-
mogeneous matter, which new kinds of matter
are wholly unlike the original in properties, and
the mass of each of which is less than the mass
of the original ; the sum of the masses of the
new kinds of matter being, however, always
equal to the mass of the original matter. Ex-
periment also shows that from certain kinds of
homogeneous matter new kinds of matter can be
obtained only by adding on to (or combining
with) the original matter one or more different
kinds of matter, and that in these oases the mass
of the new kind (or kinds) of matter produced
is greater than the mass of any one of the kinds
of matter which have united to produce it, but
is equal to the sum of the masses of all these
kinds of matter. Experiment thus enables us to
arrange all known kinds of homogeneous matter
in two classes ; those kinds belonging to the first
class, i.e., those from which can be obtained two
or more different kinds each unlike, and weigh-
ing less than, the original, are called com-
pounds ; those belonging to the second class,
i.e., those which can be changed only by adding
on to them some other kind of matter, are called
elements. A compound may of course be changed
by adding on to it a new kind of matter in the
same way as an element may be changed ; but
an element can be changed in this way and in
this way only. So far as exact knowledge goes,
elements may be said to be completely homo-
geneous ; not only are we unable to separate a
specified mass of an element into particles un-
like each other, by grinding, or cutting, or
dividing the mass in any way, but we have
every reason to suppose that the extremely
minute particles of matter, by the union of which
we are obliged to regard the mass as built up,
are themselves completely identical in proper-
ties. Although by grinding, or cutting, or
dividing by a machine, we cannot separate a
specified mass of a compound into particles un-
like each other, yet we are certain that the ex-
tremely minute particles of matter, by the union
of which we are obliged to regard the mass as
built up, are themselves built up of yet smaller
particles, some of which are wholly unlike some
others. But notwithstanding this distinction,
which may perhaps be removed as more knowledge
is gained, we are justified in applying the term
homogeneous kind of matter to elements and
sompounds alike.
Chemistry then concerns itself with the con-
nexions between the properties and the composi-
tion of elements and cotnpounds. By the com-
position of an element is meant, at present,
simply a statement of the name of the element ;
the element is composed of itself. By the com-
position of a compound is meant, at present, a
statement of the elements by the union of which
the compound is produced, and of the mass of
each element which goes to produce a specified
mass of the compound. But the word composi-
tion, as we shall see hereafter, has a fuller
meaning than this.
Let us then regard the composition and pro-
perties of compounds with the view of placing
together those which are like and separating those
which are unlike. The moment we attempt to do
this, we find that our classification of compounds
must include elements also. A series of com-
pounds may be formed by the union of one ele-
ment with other elements; the properties of
these compounds present some points of simi-
larity ; the presence in all of them of the speci-
fied element is accompanied by certain more or
less marked similarities of properties. We wish
to connect properties of compounds with com-
position,; therefore we must learn the properties
of the elements which by their union produce
these compounds ; but this involves the study
of these elements both as they are in themselves,
that is, as they aire when unacted, on- by other
elements, and also as their properties are modi-
fied when the elements combine vrith others.
We cannot then classify compounds without
studying the properties of elements, and we
cannot classify elements without studying the
properties of compounds.
Compounds may be classified in accordance
with (1) the number of elements in each;
(2) the qualitative properties of the elements in
each ; (3) the quantity of the elements in each ;
(4) the quality and quantity of the elements in
each ; (5) ths functions performed by each ;
(6) the qualitative and quantitative elementary
composition and at the same time the function
performed by each.
Making the number of elements in each com-
pound the class-mark, we should have a division of
compounds into binary, ternary, quaternary, &c.;
but this arrangement would tell very little about
the compounds in each class; many compounds
may be binary compounds, and yet the differ-
ences between them be very great. K the quali-
tative properties of the elements in a number
of compounds are made the cl&ss-mark, we
should have a division into compounds of oxy-
gen, compounds of chlorine, compounds of iron,
and so on; but not only would this arrange-,
ment convey little information regarding the
compounds classified, but it would involve an
immense number of classes, and the classes
would overlap each other ; e.^. the chlorides of
iron would be placed both in the class of chlorides
and also in that of compounds of iron. Nor can
the quantity of the elements in compounds by
itself be made the characteristic mark of a class ;
else we should have vast numbers of quantita-
tive analyses as the sole basis of classification.
More hopeful is it to attempt a classification of
compounds based on the functions which they
perform under stated conditions; this scheme
leads to the placing together e.g. of acids, basic
198
CLASSIFICATION, CHEMICAL.
compounds, metallic oompounds, peroxides, an-
hydrides, &o., &e. ; but unless we connect the
composition of the iicids,. the basic compounds,
the anhydrides, &o., with the functions of each
of these groups, our classification must at the
best be one-sided and subject to continual modi-
fication. The characteristic mark of a class
should be some property or circumstance, or a
conjunction of properties or circumstances,
which is easily detected, and which belongs to
all the members of the class and to no others.
The property which we propose to employ as a
class-mark is power of performing a stated action
under stated conditions, and with this property
we shall endeavour to connect a certain com-
position. The term composition must be inter-
preted as meaning not only a statement of the ele-
ments, and of the masses of these elements, which
produce a specified mass of any given compound,
but also a statement of the number of atoms of
each element in the atomic complex or reacting
chemical unit of the compound in question ; or,
in the case of gaseous compounds, of the number
of elementary atoms in the molecule of the com-
pound. We shall assume the molecular theory
of the structure of matter, and the atomic theory
of chemistry (v. Atomic and moleouiiAs
WEIGHTS, vol. i. p. 336). We shall also assume
L AlkaU-forming oxides.
LijO, Na^O, K2O, EbjO,
Cs20;TljO;MgO,CaO,
SrO,BaO;(?AgjO?PbO)
II. Acid-forming oxides.
BA; CO, CO2; NjO, NjOj, NjO,,
NA; SiOj; PA. PjOs; SOj,
SO3; CI2O, CIA; SeO^; TeOj,
TeOj ; lA 1 3,nd the following
oxides of metals, viz. VjO,, VjOj ;
AsjO,, ASjOj-, SbjOj, SbA;
NbA; TaA; (?Bi,0,); (IDlfl,);
CrOs; MoOj; WO^; AuA; IrA;
OSO3 ; PtO, PtOj ; PbOjj ; MnO, ;
SnO, SnOj,; TiOj,; ZrOj.
evolution of carbon dioxide, and react with
many metals to produce compounds composed
of the metal and a portion of the elementary
constituents of the acid, this action being fre-
quently accompanied by evolution of hydrogen.
Oxides which react in this way are, generally
speaking, but not always, oxides of non-metallic
elements. Other oxides again exist which either
do not dissolve in water, or dissolve only in re-
latively very large quantities of water, and
which do not thus produce either alkalis or acids,
but react with aqueous solutions of acids to form
salts and water. Such oxides are for the most
part oxides of well-marked metallic elements.
Finally a few oxides exist which do not belong
to any one of the three classes already con-
sidered; omitting these, the three classes of
oxides may be named (1) alkali-forming or
alkaline oxides ; (2) acid-forming oxides or an-
hydrides ; (3) salt-forming or basic oxides. The
alkaline oxides' are all oxides of metals, the
acid-forming oxides are generally oxides of non-
metals, and the salt-forming oxides are oxides of
elements most of which are usually classed with
the metals. The following list will serve as
data on which a comparison of the properties
with the composition of each of these classes of
oxides may be based :
that the reader is familiar with chemical fot-
mulse and notation.
A number of compounds exist which dis-
solve in water to produce more or less alkaline
liquids, that is to say, liquids which exert a
corroding action on organic fibres, change the
tint of various vegetable colouring-matters, neu-
tralise acids without evolution of any gas, pre-
cipitate the hydroxides of most heavy metals
from solutions of salts of these metals, have a
peculiar, soap-like action on the skin, and sapo-
nify fats. The compounds which thus dissolve
in water to produce alkaline liquids are found
on analysis to be binary oompounds of oxygen ;
the element present in combination with oxygen
is in each case a metal. Other oxides exist
which dissolve in water to produce more or less
acidic liquids, or which can be obtained from
acids, that is to say, compounds aqueous solu-
tions of which, like alkalis, exert a corroding
action on organic fibres and change the tint of
various vegetable colouring-matters, which neu-
tralise alkalis with the production of water and
salts but without the evolution of any gas, neu-
tralise carbonates of the alkaU-metals with
III. Salt-forming oxides.
Host of the oxides not placed in
groupsLandll.; the chief exceptions
being HjO, H^Oj, NO, and some of
the oxides of Or, Mo, W, and U. The
oxides (MjO) of Li, Na, K, Bb, Cs
and Tl, and the oxides (MO) of Mg,
Ga, Sr, and Ba.being already classed
as alkali-forming, may be omitted
from this group, although they re-
act with acids to form salts ; some
metallic oxides containing rela-
tively much oxygen, e.g. NajOj,
K2O4, BaO^, BiAi <^°-> form salts
by the action of acids but at the
same time evolve oxygen.
The alkali-forming oxides are oxides of
strongly marked positive elements ; if more than
one oxide of such an element exists, that with
the less oxygen is alkali-forming. The acid-
forming oxides are either oxides of the mora
negative elements (non-metals), or they are the
higher oxides of the less positive metals ; many
of the anhydrides belonging to the latter class
do not form acids when acted on by water, but
are-obtained by removing water (usually by the
action of heat) from the hydrated oxides which
are themselves feebly acidic in character. By a
body of a feebly acidic character is meant a
compound which, as a rule, is insoluble or nearly
insoluble in water, does not react with aqueous
solutions of alkalis to form salts, but gives rise
to the production of salts when it is fused with
an alkali ; the salts thus produced are unstable
and are easily separated into their constituent
oxides. The salt-forming oxides which are
neither alkaline nor acid-forming constitute by
far the greater number of the well-marked me-
tallic oxides. The physical properties of the
oxides'placed in the same class are not neces-
sarily similar; thus CO, CO^, NAi SOj, and
CLASSIFICATION, OHEMIOAL.
199
some other anhydrides, are gaseous under ordi-
uary conditions of temperature and pressure, but
the metallic oxides belonging to this class are
solids, many of which melt, if at aU, only at
high temperatures^
The division of oxides into three classes, an
outline of which has now been given, is based to
a great extent on the properties of compounds
which are produced by the interactions of these
oxides with water on the one hand, and with
acids on the other hand. In order then more
completely to grasp the olaasification of oxides it
is necessary to consider the properties and the
classification of alkalis, &cids, and salts.
The term alkali was originally applied to the
ashes of sea-plants; but it was soon extended
to include substances which, Uke the ash of sea-
weed, easUy dissolved in water to form solutions
having a soap-like action on the skin, affecting
the colour of many vegetable matters, and re-
acting with acids with effervescence and the pro-
duction of new substances wherein neither the
properties of the alkali nor the acid were promi-
nent. About the middle of the eighteenth cen-
tury Black proved by quantitative experiments
that the efiervesoenoe which occurs during the
interaction of an aoid and an alkali is caused by
the outrush of a gas which existed in the alkali
in combination with the other constituents of
that body. That the same gas may also be ob-
tained from the alkali by the action of heat was
also proved by Black. From this time it became
customary to distinguish mild or carbonated al-
kali from burnt or caustic alkah, the former being
regarded as a combination of the caustic alkali
with carbonic acid gas. Both carbonated and
caustic alkali reacted with acids to produce the
same substance, in which the properties of alkali
and acid were lost, or rather merged into a new
set of properties ; the action was attended in the
case of carbonated alkali with evolution of car-
bonic acid gas, but in the case of caustic alkali
no gas was produced. Continued examination
of alkali showed that the composition of the sub-
stance thus named was not always the same ; this
led to the recognition of more than one kind of
matter exhibiting the characteristic properties of
alkalis. Lavoisier adduced reasons for regarding
the various alkalis as compounds of imknown
metals with oxygen, but he did not succeed in
actually demonstrating their composition. In
1807 Davy decomposed two alkalis, potash and
soda, each into oxygen and a metal, by passing
an electric current through them when molten,
and a year later by the same agency he separated
the three earthy bodies, lime, strontia, and baryta
— bodies which to a great extent resemble alkahs
in their properties — into oxygen, and in each case
a metal. The composition of the various bodies
having the properties already summarised as
characteristic of alkali was now settled; these
bodies were oxides of metals. But further in-
vestigation showed that aqueous solutions of these
metallic oxides did not contain the oxides, but
rather compounds of metal, oxygen, and hydro-
gen, and that these compounds, these hydrox-
ides, were obtained as definite weU-marked solid
bodies by boiling off the water from the solutions
in question. Now as the characteristic properties
of alkah belonged to aqueous solutions of the me-
tallic oxides under consideration it was better to
apply the name alkali to the hydroxides rather
than to the oxides of certain metals. The com-
position of alkalis is represented by the formula
MOH, where M = Li, Na, K, Bb, Cs, or the com-
pound radicle NH^ ; each of these compounds,
except NHjOH, is known as a definite solid body.
An aqueous solution of ammonia, KH,, reacts
towards vegetable colouring-matters, towards
acids, towards solutions of the salts of iron, cop-
per, bismuth, tin, and many other heavy metals,
in a manner very similar to that in which aque-
ous solutions of the five alkaline hydroxides,
MOH, react towards these classes of substances.
The salts formed by the action of acids on the
hydroxides in question are generally isomorphous
with, and in other properties similar to, the salts
formed by the action of the same acids on an
aqueous solution of ammonia. For these and a
few other reasons the composition of an aqueous '
solution of ammonia, NH„ is supposed to be
similar to that of aqueous solutions of the solid
alkalis ; but the compositions of the latter solu-
tions are represented by the symbols LiOitfAq,
NaOHAq, &o., therefore the composition of the
former solution is represented by the symbol
NH^OHAq. As we have hydroxides of the metals
hthium, sodium, potassium, &o., so we have a
hydroxide of the compound radicle ammonium
(NH4); the former hydroxides are stable solid
bodies, the latter exists only in aqueous solu-
tion (u. Ammonium oompocnds, vol. i. p. 200). The
hydroxides MO^Hj where M is Mg, Ca, gr, or Ba,
all more or less resemble the alkahs ; these hy-
droxides are white sohds, which require for solu-
tion much larger relative quantities of water
than are needed to dissolve equal masses of the
alkalis, but which thus produce solutions capable
of neutrahsing acids without effervescence, of
changing vegetable colouring-matter in the same
way as solutions of the alkalis, of precipitating
oxides or hydrated oxides of many heavy metals
from solutions of the salts of these metals, of
corroding organic fibres to some extent, of sapo-
nifying fats, and of quickly combining with car-
bonic acid to produce carbonates. As all the
alkaUs and the four compounds of Mg, Ca, Sr,
and Ba, just mentioned are compounds each of
oxygen, hydrogen, and a metal, and as many
other metallic hy^oxides, e.g. CuO^H,, FcjOgHg,
&o. &o., do not exhibit alkaline properties, it
seems probable that the alkaline qualities of the
hydroxides of Li, Na, K, Eb, Cs, Mg, Ca, Sr, and
Ba, are to be associated with the properties of
the metals, Li, Na, K, . . . Ba.
Thus in our attempts to classify oxides we are
obliged to have regard, first, to the properties of
alkalis, and then to the properties of the elements
of which these alkalis are composed. What,
then, are the properties of the metals Li, Na, K,
Eb, Cs, Mg, Ca, Sr, and Ba?
The metals Li, Na, E, Eb, and Cs, are silver-
white solids, with low melting-points, and very
small specific gravities (Li, Na, and E, being
lighter than water); the metals are extremely
easily oxidised, the process of oxidatioii being
attended with production of much heat; they
rapidly decompose cold water with evolution of
half the hydrogen of the water decomposed and
production of hydroxides MOH which remain in
solution ; during this process much heat is pro-
duced. The metals easily and rapidly combine
200
CLASSIFICATION, CHEMICAL.
with the halogens and with sulphur; they are
eleetro-positiveto all other metals, and the most
electro-positive metal of the group is that with
the largest atomic weight (Cs). The composi-
tions of the chief compounds of these metals
are represented by the symbols M^O, MOH,
M,S, MSH, MX {X = C1, Br, I, F, ON), M^SO,,
MHSO,, MNO3, M.fiOs, MHCO3, &c., where
M = Li, Na, K, Eb, or Os. These compounds are for
the most part white and easily soluble in water ;
many of them are not chemically changed by the
iction of heat alone ; all compounds of similar
composition, e.g. all M^SO^ or aU MCI, are as a
rule isomorphous; the sulphates M2SO4 form
alums by combination with sulphates of the
composition M^SSOi where M = Fe, Al, Or, In, or
Ga. The properties of the hydroxides MOH have
already been detailed.
The metals Ca, Sr, and Ba are whitish-
yellow solids, the melting-points of'whioh have
not been accurately determined, but are some-
■trhere about a red heat ; the specific gravities
of these metals are represented by small values,
which are, however, decidedly greater than those
that represent the specific gravities of the
metals Li . . . to Cs ; these metals are harder
than the alkali metals, but, compared with the
group of metals as a whole, they are soft ; they
quickly oxidise in air or oxygen, and decompose
cold water with production of much heat, evolu-
tion of half the hydrogen of the water decom-
posed, and formation of solutions of the hydrox-
ides MO2H2. In the cases of Li . . . Cs one atom
•of metal reacts with one molecule of water evolv-
ing one atom of hydrogen, in the cases of Ca
. . . Ba one atom of metal reacts with two mole-
cules of water evolving two atoms of hydrogen ;
the Inetals, so far as exact experiment goes, seem
to combine easily and rapidly with the halogens
and with sulphur ; they are electro-negative to
the metals Li . . . Cs, but positive -to aU other
metals. The compositions of the chief com-
pounds of these metals are represented by the
symbols MO, MOj,H„ MS, MSA, MX^ (X = C1,
Br, I, F, CN), MSO,, M2NO3, MCO3, &c., where
H = Ca, Sr, or Ba. Most of these compounds are
white ; the oxides and hydroxides are not very
soluble, the sulphates and carbonates are nearly
insoluble, the chlorides and nitrates are easily
soluble, in water ; the hydroxides, nitrates, and
carbonates are decomposed by the action of heat
alone ; almost all similar compounds are isomor-
phous ; the sulphates do not form alums, nor do
the compounds generally exhibit any marked
tendency to form double or basic salts. The
properties of the hydroxides have already been
detailed. ;
The metal magnesium is a silver- white solid,
the melting-point of which is about 500='-700°
(not accurately determined), and the specific
gravity is a little greater than that of calcium ;
the metal is much more malleable and ductile
than Li . . . Cs or Ca . . . Ba ; it is scarcely oxid-
ised by exposure to air or oxygen at ordinary
temperatures, but when rapid oxidation is begun
by heating the metal in air or oxygen it proceeds
with production of much , heat and light. Mag-
nesium decomposes water at 100° very slowly
with formation of MgOjHj; it does not act ehemi-
oally on cold water; it does not combine with the
halogens or with sulphur at ordinary tempera-
tures. The comppsitions of the chief compounds
of this metal are represented by the symbols
MgO, MgO,H„ MgS, MgX,(X = Cl,Br,I,F, CN),
MgSO„ Mg2N03, MgCOj, &e. Most of the com-
pounds are white ; the oxide and hydroxide are
only very slightly soluble in water ; the oxide
conibines with water to form MgO^Hj, but much
less heat is produced during this process than
when CaO, SrO, or BaO, combines with water to
form the hydroxide. The hydroxide is easily de-
composed by heat alone into oxide and water ;
the sulphate, nitrate, and haloid salts are easily
soluble in water, the carbonate is nearly insoluble
in water ; many compounds of magnesium salts
virith those of the alkali metals, &o., are known ;
some of the magnesium compounds are isomor-
phous with the similar compounds of Ca, Sr, and
Ba, but the isomorphism pf the two series of salts
is very far from' being complete. (For more de-
taOs of 'the properties of the three classes of
metals v. AiiEAlis, metals of the, vol. i. p. 114 ;
ALKALrNE EABTHS, METAIiS OP THE, Vol. i. p. 112 ;
and MAONEsniM meials.)
These facts concerning the metals whose
hydroxides are the alkalis, and concerning those
whose hydroxides more nearly approach the
alkalis than do the hydroxides of any other ele-
ments, show that the property of forming an
alkaline hydroxide is accompanied by the follow-
ing properties on the part of an element : low
specific gravity, not very high melting-point,
small malleability and ductility, softness, occu-
pation of a very positive position in the electrical
series of elements, power of rapidly decomposing
water with evolution of part of the hydrogen
thereof, power of forming salts which are not
easily decomposed by heat alone, and many of
which are easily soluble in water, great readiness
to combine with oxygen and with the halogens.
Of all the metals whose properties we have con-
sidered in detail, magnesium difiers most from
the ideal 'alkali-forming metal ; but the hydrox-
ide of magnesium is decidedly less markedly
alkaline than the hydroxide of any other metal
in the two groups from Li to Sr.
When a given element exhibits a fair num-
ber of the properties given above as charac-
teristic of the alkali-forming elements we may
conclude that the hydroxide of that element
will be more or less alkaline in its properties.
There is a certain element characterised by
the following properties : specific gravity large
(11'9), melting-point moderately low (290°), very-
soft, malleability and ductility moderate, oxid-
ises rather rapidly in air but action soon stops
because of formation of film of oxide, burns
rapidly in oxygen at about 300°, does not de-
compose water untU a red-heat is reached ; less
positive than zinc, which is again less positive
than Ca, Sr, or Ba; combines readily with the
halogens and with sulphur; most of the salts
of this -metal are white and easily soluble in
water, some of them are isomorphous with, and
of similar composition to, salts of potassium.
In many respects then this metal approaches
the ideal alkali-formmg element ; but in others,
notably its high specific gravity and compara-
tively negative position in the electrical series, it
departs from the alkali-forming type. We should
efpect the oxide and hydroxide of this metal to
present fairly close resemblances to the corra-
CLASSIFICATION, CHEMICAL.
201
sponding compounds of the lithium group of
metals, but at the same time to show consider-
able differences from these compounds. As a
matter of fact, the metal forms two oxides and
two hydroxides ; one pair of these compounds
shows close analogies with the corresponding
compounds of the alkali metals ; the other pair
shows fairly marked analogies with the corre-
sponding compounds of aluminium. The metal
in question, which is thallium, belongs to two
groups of elements ; it forms an alkaline oxide
and hydroxide T1,0 and TIOH, and another
oxide and hydroxid'e TI2O3 andTlO.OH.
Hajpng thus learnt something regarding the
properties and compositions of alkalis, let us
turn to the second group of compounds which it
is necessary to consider before we can complete
the classification of oxides ; let us briefly consi-
der the group of acids. The name oxygen per-
petuates the Lavoisierian conception of the com-
position of acids : this element was for Lavoisier
emphatically the acid-producer. The products
of the combustion in oxygen of sulphur, phos-
phorus, carbon, boron, nitrogen, selenion, and a
few other elements, dissolve in water to form so-
lutions which have * acid reactions,' that is to
say, have a sour taste, corrode organic fibres,
change, the tint of many vegetable colouring-
matters, neutralise alkalis with production of
salts and water, and dissolve many metals with
evolution of gas (generally hydrogen). By re-
moving water from these solutions, at least one
definite compound can in most cases be ob-
tained, composed of the element which had been
burnt in oxygen, combined with oxygen and hy-
drogen ; when this compound is again dissolved
in water the original acid liquid is reproduced.
Very many other compounds are known which
form aqueous solutions characterised by acidic
reactions as above enumerated; most of these
compounds are composed of oxygen, hydrogen,
and a third element. On the other hand, very
many compounds formed by the union of oxygen,
hydrogen, and a third element do not form acidic
solutions when dissolved in water ; and, finally,
a few compounds are known, aqueous solutions
of which are most definitely acidic, but which do
not themselves contain oxygen. Oxygen is there-
fore not the sole acid-producing element; but
I the fact remains that by far the greater number
of acids are composed of oxygen united with
other elements.
Putting into one class all those compounds
which dissolve in water with formation of solu-
tions having acidic properties, as these have
been already enumerated, and then tabulating
the composition of these compounds, it becomes
evident that they are all compounds of hydrogen
with one or more other elements. Hydrogen
then, rather than oxygen, would seem to be the
acid-producing element. But further exalmina-
tion of the compounds of hydrogen shows that
very many of these are not possessed of any of
the characteristics of acids.
Is it possible then to trace any definite con-
nexion between the composition of compounds
and the possession or non-possession by them
of acidic properties? In attempting to answer
this question we are confronted with the great
difficulty of chemical classification. We cannot
define the class acids, just as we could not de-
fine the class alkalis : an ideal acid or alkali
may be defined, but it is necessary to place in
one or other of these classes many bodies which
possess some of the properties of the ideal type,
but in other properties diverge more or ' less
widely from that type. Chemical classification,
based on the notion of connecting properties
with composition, is at best a typical classifica-
tion, and such a system cannot be regarded as
final in an exact science. The mark of a class
should be some property or circumstance, or
conjunction of th^se, which is clear and definite,
and which belongs to all the members of the
class and to no other bodies. But we cannot
predicate any one property of acids which is
perfectly clear and definite, and the possession
or non-possession of which shall determine
whether a specified compound is or is not to be
admitted to this class. The reaction which
occurs between an acid and a metallic hydroxide,
or hydrated oxide, more nearly approaches to a
good class characteristic than any other single ,
property of acids. The products of the action in
question are water and a compound formed of
the metal of the hydroxide employed, and the
elements of the acid excepting the whole or a
part of the hydrogen; such a compound is called
a sait. The following equations, representing
the distribution of the elements of the reacting
compounds before and after the mutual actions
of various acids and metallic hydroxides, will
illustrate, more clearly. than can be done in
words, the characteristic reaction of an acid :—
(the symbol Aq is used to denote that the com-
pound which it follows is dissolved in water)
1. HOUq + NaOHAq = NaClAq.+ H^OAq.
2. HNOsAq + TlOHAq = TlNOjAq + H^OAq.
3. H,SO,Aq + KOHAq = KHSO^Aq + H,,0 Aq.
4. HjSO^Aq + 2K0HAq = K^SOiAq + 2B.flA.(i.
5. HjSO^Aq + CuOjHj = CuSOiAq + 2H30Aq.
6. 2H,Cj0^q + PbO A = Pb(afifi^), + SH^OAq.
7. KfijO^kq + NaOHAq = NaMfifiM + H^OAq.
8. HsPO^Aq + TlOHAq = TlHjPO.Aq + H^OAq.
9. 2H3P04Aq + Fe AH» = 2FeP0, + 6H,,0Aq.
10. HjCjO^Aq + CaOjHjAq = CaOA + 2Hj0Aq.
An acid, then, may be provisionally defined
as a compound of hydrogen with another ele-
ment, or other elements, which, when dissolved
in water, reacts with metallic hydroxides to pro-
duce water and a salt ; a salt being a compound
formed by the union of the elements of the acid,
excepting the whole or a part of the hydrogep,
with the metal of the metalho hydroxide. This
definitionis more commonly put into the shorter
form, an acid is a compound containing replace-
able hydrogen; but unless a definite meaning is
given to the expression replaceable hydrogen,
the definition of acid means nothing : the mean-
ing of the words replaceable hydrogen is given
in the longer definition of acid stated above. _ It
is found that most cpmpounds which are acids,
in accordance with the provisional definition we
have adopted, when dissolved in water form more
or less corrosive liquids, which affect vegetable
colouring matters, have a sour taste, and dis-
solve many metals with forination of salts and
evolution of gas, which is usually hydrogen. But,
on the other hand, some compounds which are
possessed of many of the properties just detailed
do not react with metallic hydroxides to form
209
CLASSIFICATION, CHEMICAL.
Baits ; and, further, some compounds which are
pot possessed of any of the properties detailed
do react with metallic hydroxides to form salts
{v. Acids, vol. i. p. 47).
Looking at the composition of compounds
which undoubtedly come under the definition of
acid, and which at the same time are charac-
terised by. the other four properties enumerated,
we find that the elements, or some of the ele-
ments, which by their union with hydrogen form
che acid, are strongly negative in character ; in
other words, the element or elements other than
hydrogen more or less resemble oxygen in their
general chemical characteristics. As a whole,
the elements whichiare classed as non-metallic
are those which by union with hydrogen, and
generally with hydrogen and oxygen, produce
acids. When an acid is a compound of a metal
united with hydrogen and another element or
elements, for no binary metallic compound is
acidic, that other element is always very nega-
tive. The following list exhibits most of the
well-marked metallic acids which have been ob-
tained in approximate purity: —
Acids containing metals,
HaAsO, HjSnO, HjSnSj
HAsO, — —
H.ASjO, (?HjPbO,) (?HjAsS4)
HsSbO, HjCrOi
HjSbOj —
HSbO, pH^Mnfi,)
H4Fe(CN),
H3Fe(GN),
&o.
(?H,PtOU
(?HAuBrj
(?HAuClj
H^SbaO, HjMoOi
HVO, HaWO,
H,Ta,0, /?HjMaO, I whereM= Mo,W,\
- ^?H,M,0,„f or U. /
/'?HjTiOA
VH^TiO,/ HjPtOj
The element which is generally combined with
hydrogen and a metal in these acids is oxygen :
in a few acids sulphur, in (?) three acids chlorine
or bromine, and in a few acids the negative group
ON is combined with hydrogen and a metal.
It is also to be remarked that the metals which
form well-marked acids by union with oxygen
and hydrogen are those which, compared with
the majority of the metals, are negative.
The general conclusion to be drawn from the
facts now reviewed concerning the connexions
between the properties and the composition of
acids is, that those compounds which are de-
cidedly acidic in properties, as the term acidic pro-
perties has been defined, are formed by the union
of hydrogen with one or more decidedly negative
elements. Acids are seen to be strongly con-
trasted with alkalis, both in properties and com-
position.
Oxides were divided {«.p.l98) into three groups :
alkali-forming, acid-forming, and salt-forming,
oxides. We can now understand in a general way
what is meant by an alkali-forming oxide, or by
an acid-forming oxide; it remains to consider
the meaning of the term salt-forming as applied
to oxides. At the outset, let us remark that a
salt-forming oxide may also be acid-formimg,
and that an alkali-forming oxide also is salt-
forming. In considering the meaning of the
term salt-forming oxide, it will therefore be
necessary to study those typical compounds
which possess the property in question to a
marked extent. A salt has been already stated
to be one of the products of the mutual ac-
tion of an acid and a metallic hydroxide or
hydrated oxide, and to be composed of the
elements of the acid, excepting the whole or
part of the hydrogen, united with the metal of
the metaUio hydroxide. It is impossible to
generalise the properties of salts ; manypf them
are soluble in water, some are insoluble j aqueous
solutions of many exhibit acidic reactions, aque-
ous solutions of others exhibit alkaUne reactions,
and aqueous solutions of very many are neutral,
i.e. exert no corroding action on organic fibres,
have no sour or soap-like taste, do not affect
vegetable colouring-matter, do not saponify fats,
do not dissolve metals, or react with metallic
hydroxides, &o. We must be content to look at
the composition and the conditions of formation
of salts. The composition of salts, regarding
them as derivatives of acids, has already been
stated. But salts are formed in other ways ;
they are sometimes produced by the mutual action
of an acid-forming oxide and an oxide containing
much oxygen, called a peroxide — e.gf. Ba02 + SO,
= BaS04; sometimes by the action of a salt-
forming oxide on an aqueous solution of another-
oxide from which an acid has not actually been
obtained, thus K2O + C0,Aq = K20OsAq; some-
times by fusing together a metalUo and a non-
metallic oxide, e.j. CaO-l-Si02 = CaSi03; some-
times by dissolving the sulphide of a less positive
metal in a solution of the sulphide of a very
positive metal, thus ASjS, + KjSAq = 2KAsSjAq,
or WS3-^KJSAq = KJWS4Aq; and sometimes in
other ways. The products of such actions as
these are called salts, either because they can
also be directly obtained by the mutual actions
of acids and metallic hydroxides, or because they
are composed of positive elements (metals) com-
bined with negative elements, of which oxygen
is usually one, and which negative elements are
known to form acids by union with hydrogen,
although the special acid of which any one of
these specified salts is theoretically a metalUc
derivative may not have been prepared. All
oxides are in a sense salt-forming ; an alkaline
oxide reacts with water to form an alkali, and
the alkali reacts with an acid to form a salt ; an
anhydride reacts with water to form an acid,
and by the mutual action of this acid and an
alkali a salt is produced. But placing on either
side those oxides which have been already
classed as alkali-forming, and those which have
been classed as acid-forming, there remain a
great many oxides which are emphatically salt-
forming oxides. As a class, these oxides form
salts by reacting either with acids or with solu-
tion of oxides which act as if they contained
acids, although no acid may actually be obtained
when the dissolving water is removed, or, lastly,
by reacting in the liquid state (not in solution)
with the oxides of non-metals or of the more
negative metals ; examples of these three types
of action are exhibited by the following pro-
cesses : —
CLASSIHOATION, CHEMICAL.
203
(1) CuO + H,SO,Aq = CuSOAq + H,OAq,
(2) BaO + COjAq = BaCO, + Aq,
(3) K,0 + TaA(fusea) = 2KTaO,.
Borne salt -forming oxides also produce salts,
either by dissolving in oonoentrated solutions
of alkalis, or by combining with alkalis when
melted in contact with them; thus freshly
ppd. aluminium oxide dissolves in solution of
acids to form salts, and also in a oonoentrated
aqueous solution of potash to form a salt ; the
two actions may be represented thus :
(1) AljO, + 6HClAq = Al^Cl^Aq + 3H,OAq,
(2) Al5,03 + 2KOHAq=Alj04K,Aq + HjO.
Again, moist SnCj dissolves in concentrated
aqueous potash to form a solution of potassium
stannate K^SnO,, but the same oxide dissolves
in hydrochloric acid to form stannic chloride,
SnCl,;_ inasmuch as the acid H^SnOa, of which
SnOj is the anhydride, is known, we have in
stannic oxide, SnO^, an example of a compound
which is at once an acid-forming and a salt-
forming oxide. The oxide MnO^ dissolves in
molten KOH to form the salt potassium man-
ganate, K^MuOj ; the same oxide, when produced
in a concentrated solution of lime, combines
with the lime to form a series of salts, of which
CaMnO, may be taken as a representative ; and,
lastly, the same oxide, when hydrated, dissolves
in strong sulphuric acid to form a sulphate of
manganese Mn02.2S09. This oxide, HnO^, thus
exhibits some of the properties of two of the
three classes into which we have divided
oxides.
We began by proposing to arrange oxides in
three classes in accordance with certain promi-
nent reactions of these oxides; that we ^ might
attach to the reactions in question such definite
meanings as should suffice for classificatory
purposes, we were obliged to consider the mean-
ing of the terms which summarise the reactions
and composition of three other groups of com-
pounds— acids, alkalis, and salts ; that we might
grasp the significance of these terms, we had to
turn from compounds to elements, and roughly
to classify these in accordance with their acid-
forming or alkali-forming functions; but we
found all this scheme of classification to be
based at once on the composition and the
functions of the bodies- classified, and the word
function we were obliged to interpret as implying
the notion of mutual action and reaction between
at least two kinds of matter. We arrived at no
perfectly clear definition of any one of the
classes of compounds under examination ; we
did succeed in conceiving the properties and
the composition of a typical acid-forming, alkali-
forming, and salt-forming, oxide ; but when we
applied this conception, gained, it is to be re-
marked, from tiie study of actual acid-, alkali-,
and salt-forming oxides, to individual compounds,
we found that very few of these exhibited all
the characteristics which we had laid down as
marking off the typical acid-forming from the
typical alkali-forming, or both from the typical
salt-forming, oxide.
Looking back for a moment at the classifica-
tion of oxides, and considering what it implies,
one thing stands clearly out, namely, that this
classification of oxides carries in itself a classi-
fication of elements. Those elements which
form markedly alkaline oxides fall into one
class, those which form oxides which ore dis-
tinctly anhydrides fall into a second class, and
a third class includes those elements the best-
marked oxides of which are neither , alkali-
forming nor acid-forming, but salt-forming. Or,
putting the matter in even more general terms,
the classification of oxides suggests a means of
classifying the elements. Let us put into one
class all the elements which, under similar con-
ditions, form compounds similar in composition
and function. Let us then examine the elements
in si class with the view of finding whether they
do or do not exhibit similarities in physical
properties. If the result is fairly successful,
let us examine more closely into the composition
of the compounds belonging to specified classes,
and endeavour to learn something of the struc-
ture of these compounds in the light which is
thrown on structure by the molecular and atomic
theory. Finally, let tbe knowledge which may
thus be gained of structure react on that pre-
viously amassed concerning function, that by
the help of both some advance may be made in
finding a solution for the fundamental problem
of chemistry, which is, to trace the connexions
between changes of composition and changes of
properties in homogeneous kinds of matter.
Instead of following the course of this inves-
tigation step by step, it will be more advantageous
to begin with the leading principle, which has
been gained after much laborious inquiry. In
the article Atomic and uolecitlaii weiohib a
sketch was given of the periodic law. The
substance of that sketch it would be needless to
repeat here ; let us rather apply it to the point
in hand, namely, the classification of the ele-
ments, remembering always that a good classifi-
cation of elements implies and carries with it a
good classification of compounds also.
The classification founded on the periodic
law arranges the elements in groups and series
(u. vol. i. p. 351) ; the members of the same
group more or less closely resemble each other ;
the properties of the members of a series vary
from member to member so that the last, that is
the element with the largest atomic weight, is
more unlike the first than any other member of
the series. Each series to some extent repeats the
charaoteristics of that which precedes it. The
properties of an individual element are chiefly
conditioned by (1) the group, (2). the series, to
which it belongs, (3) its position in the group
and in the series, (4) its relations to elements
situated similarly to itself in other groups and
series, and (5) the relations of the group and of
the series to other groups and series. As regards
thecharacteristicsof individual groups and series,
and the relations between various groups and
series, it should be remarked, (1) that each group
is made up of elements belonging to even series
and elements belonging to odd series; (2) that
an odd and an even series together comprise 14
elements, and that in the cases of series 4 and 5,
6 and 7, and 10 and 11, there is a group of three
elements (Group VIII.) forming what is called
by MendelejeflE a 'transition-period' from the
even to the odd series ; (3) that there is cer-
tainly no such ' transition-period ' connecting
series 2 and 3, but that very probably such
a period of three elements will be discovered
between soriep 8 and 9 ; (4) that the elements in
S04
CLASSIFICATION, CHEMICAL.
the even series, or in the odd series, of any group
are more like one another than elements in the
eyeh are like those in the odd series ; (5) that,
omitting series 2 and 3, the passage from an even
td an odd series is accomplished by a gradual
change of properties, but the passage from an odd
to an even series by a more sudden change of
properties; (6) that the distinctly non-metallic
elements occur in odd series, except in the
case of series 2; (7) that, omitting series 2,
easily gasified organo-metallio compounds, so
far as data go at present, are formed only by
elements which occur in odd series ; (8) that
the properties of hydrogen are so marked, and
are typical of such diverse elements, that it is
placed in a series [series 1] by itself ; (9) that
all the members of series 2 [liitoF], and at least
the first member of series 3 [Ka], are to a great
extent marked by peculiar properties, and that
the relations of these elements to those in
series 4, and in the case of sodium to series 5,
are rather markedly different from the normal
relations of an odd series to the next odd series,
or of an even series to the next even series.
The elements Li to Na have been called by Men-
delejeff ' typical elements.' The following table
(copied with a few changes from one given by
Mendelejefi) exhibits the arrangement of the ele-
ments in groups and in odd and even series (at.
wts. in round numbers) :—r
The even series elements in this group are be-
ryUimn, calcium, strontium, and barium. The
three metals, Ca,-Sr, and Ba, are yellowish -white,
rather soft, solids, with comparatively small
specific gravities ; their characteristic properties
have aJready been detailed in the present article
{v. p. 200). The metal beryllium differs con-
siderably from the other even series members of
the group ; unlike these metals, it cannot be ob-
tained by electrolysing the chloride ; the method
by which beryllium is obtained is very similar
to that whereby magnesium is prepared, viz. by
heating the chloride vrith metallic sodium. Be-
ryllium appears to be a silver-white, hard, solid ;
its specific gravity is small (approximately 1-7),
melting-point high, not accurately determined,
but certainly above 600°; the specific heat of
this metal increases rapidly as temperature rises,
and approaches a constant value between 400°
and 500°. The spectrum of beryllium more nearly
resembles that of lithium than of any other ele-
ment, in the number, relative position, and inten-
sity, of the lines ; but the character of the lines
of greatest intensity in the beryllium-spectrum
closely resembles that of two pairs of lines in
the spectrum of calcium. This metal does not
oxidise in air at ordinary temperatures, and even
when heated in oxygen it is only superficially
oxidised ; it combines with chlorine and iodine
only at high temperatures; when heated with
Series
ffroiiM
1
2
4
- 6
8
10
12 '
I.
■S
f Li= 7
K=39
Eb=86
Os=133
—
_
II.
Be= 9
Oa=40
Sr=87
Ba=137
_
_
in.
B
B=n
Sa=ii
Tt=89
La=139
Tb=lTJ
IT.
1-
0=12 ,
Ti=48
Zr=90
Oe=U0
—
Tli=232
T.
K=14
T=B1
Nb=94
Di=]44
Ta=183
—
VI.
0=16
Or=62
Mo =96
. —
WalSi
r=240
VII.
•H
F=19
Mn=55
—
—
-^
.—
VIII.
s
Pe=66 Ni=68-B,
Ell=104 Eu=104-S
_ ^
Os=191 lr=192-6
— ,^
fi
^ Na=23
Co=69 Ou=63
Pd=106 Ag=108
—
Pt=194-6 Au=197
_
I.
H=l
Cu=63
Ag=108
. —
Au=197
._
II.
M:g=24
Zn=65
Cd=112
—
Hg=200
^
III.
Al=27
Ga=69
In =114
—
Tl=204
_
rv.
SI=28
Ge=72
Su=118
—
Pb=207
—
v.
P=S1
As=76
Sb=120
Br=166
Bi=208
..
VI.
S=32 .
01=36-6
Se=79
Te=126
—
— .
_-
vn.
Br=80
1=127
_
—
1
3
5
7
9
11
13
SsEiBa
As regards the mutual relations of groups and
series, it should be further remarked that, calling
the even series members of a group a family, and
the odd series members a family, in groups 1
and 7 the family-character is more marked than
the group-character, in groups 3, 4, and 5 the
group-character preponderates over the family-
character, and in groups 2 and 6 the two charac-
ters are about balanced, so that these two groups
present, perhaps, the best examples for the de-
tailed study of the application of the periodic
law to the classification of elements. Grroup II.
contains the following elements: —
Group II.
Even series :
2 4 6 8
Be = 9 Ca = 40 Sr = 87 Ba = 137
Odd series :
3 5 7 9 11
Mg = 24 Zn=06 Cd = 112 — Eg = 200
sulphur, no sulphide of beryllium is formed ; it
very readily combines with silicon. Beryllium
does not decompose water even at a red heat ; it
dissolves in an aqueous solution of potash with
formation of beryllium oxide and evolution of
hydrogen ; it is easily soluble in dilute hydro-
chloric or sulphuric acid, but has little or no
action on nitric acid. The compositions of the
salts of beryllium are represented by the same
formnlsB as express those of the salts of Ca, Sr,
and Ba ; the oxide BeO does not combine with
water, but the hydroxide, BeO^H,, can be pre-
pared indirectly; this hydroxide is easily decom-
posed by heat alone, it resembles the hydroxides of
zinc and of aluminium in being soluble both in
acids and in aqueous potash, it coiabines with
carbon dioxide to produce BeOOj ; the oxide
crystallises in the same (hexagonal) form as
aluminium oxide ; under certain conditions zinc
oxide can also be obtained in this form ; beryl-
Uam oxide usually occurs in combination with
CLASSIFICATION, CHEMICAL,
208
alumina and silica, as beryl. Most of the salts
of beryllium are white; the nitrate, sulphate,
and chloride are solu^)le, the carbonate and phos-
phate are insoluble, in water. Beryllium sul-
phate does not form an alum, but does combine
with potassium sulphate to form a double salt
having the composition BeSOj.KjSO4.2H2O : the
chloride does not form double salts with the
alkali chlorides ; the carbonate is fairly stable
towards heat, but easUy forms basic, aua also
double, salts ; the sulphate, which also readily
produces basic salts, is completely decomposed
into oxide and oxide of sulphur by the action of
heat alone. The chloride and bromide of beryl-
lium have been gasified ; an ethide, Be(C2Ej)2>
is known ; it is a fuming liquid which takes fire
when gently warmed in air.
The odd series members of the group we are
considering are magnesium, zinc, cadnuum, and
mercury. The properties of the metal magne-
sium have already been stated in this article
(v. p. 200) ; of the remaining metals, zinc and
cadmium are yery similar, while mercury differs
in many respects from any other member of
the group. Zino and cadmium occur together
in minerals, chiefly as sulphides ; both are ob-
tained by deoxidising the oxides by hot carbon ;
both are heavy, moderately hard, tin-white
solids (S.G. Zn = 7-2, S.G. Od = 8-6); both melt
at fairly high temperatures (M.P. Zn = 420°,
M.P. Od = 320°), and both can be volatUised at
temperatures somewhat under 1000°. Cadmium
is ductile and malleable, the ductility and mal-
leability of zinc vary considerably with varia-
tions of temperature ; both are easily soluble in
the ordinary mineral acids, zinc ^ssolves in
concentrated warm aqueous solutions of potash
or soda, with evolution of hydrogen find produc-
tion of an unstable zincate of the alkali metal
{xZnO.yMfi) ; both are nearly unacted on by air
or oxygen at ordinary temperatures, but are
rapidly burnt to oxides when heated in oxygen ;
both readily combine with the halogens and with
sulphur. The formulae which represent the com-
positions of the chief compounds of Be, Ca, Sr,
Ba, and Mg, also represent those of the chief
compounds of Zn and Cd; almost all similar
salts of Zn and Cd are isomorphous. The
oxides, MO, do not combine with water to form
hydroxides ; the hydroxides, MO^H,, are qxute
insoluble in water, and are readily decomposed
by heat alone into oxides and water ; ZnO^EL, is
soluble, CdOjHj is insoluble, in aqueous potash.
The (^oride, sulphate, and nitrate of either
metal is soluble, the phosphate and carbonate
ere nearly, if not altogether, insoluble, in water ;
these salts show great readiness to form double
salts, especially .with the alkali metals and with
ammonia, and also to form basic salts, but the
zino salts are more ready to undergo the latter
changes than the salts of cadmium. Mercury
differs from aU. other metals in being liquid at
temperatures above —39°. This metal occurs
chiefly as sulphide, from which it may be ob-
tained by heating with iron, and in other ways ;
it is a silver-white, heavy liquid (S.G. about
13-5) ; it boils at 350°, and is very easily vola-
tilised ; it is unacted on by oxygen until a tem-
perature near 350° is reached, when it slowly
combines with oxygen to form HgO. Mercury
readily combines with the halogens and with
sulphur; it is without action on water ; dilute
nitric acid quickly dissolves mercury, and it ia
also soluble in hot concentrated sulphuric acid,
but neither boiling hydrochloric, nor boiling
dilute sulphuric, acid acts upon it. Mercury
forms two series of salts, mercurous salts repre-
sented by HgjO, HgjCl,, HgjSO„ HgNO,, &c.,
and mercuric salts represented by EgO, HgCl,,
HgSOj, Eg2N0„ &c.; the latter, as a class, are
more soluble in water, and are much more stable,
than the former. No hydroxides of mercury are
kuown ; EgO is said to be very slightly soluble
in water, and also in molten potash. The salts of
mercury, especially the mercuric salts, form a
great many double compounds, chiefly with the
salts of the alkali metals ; they also readily form
many basic salts ; a very large number of com-
pounds of mercury salts with ammonia, and de-
rivatives of aiomonia, is known.
The following data present some of the
measurements which have been made (chiefly
by Thomsen) of the quantities of heat produced
during similar changes undergone by the ele-
ments, or by compounds of the elements, in the
group we are now considering : — *
Ca 187,600
Sr 195,700
Ba 196,300
Mg 186,900
Zn 112,800
Cd 96,800
Eg 53,200^
Hgj 62,600«
[M,Br"^q] [M,P,Aq]
165,800 135,300
173,800 143,400
174,400 144,000
165,000 134,600
90,900 60,500
74,400 44,000
41,480« 24,300'
50,950' 28,400*
[M,0,N»0'Aq] [M,0]
177,160 130,930
185,410 128,440
187,000 124,240
176,480 146,000
102,510
86,000
37,070
47,990
85,400
65,600
30,670
42,200
M
Zn
Cd
[M,Cy»^KC!yAq]
62,230
44,750
27,780
So far as these data warrant us in drawing /
general conclusions, it appears that the quantity
of heat produced during the occurrence of a
similar chemical change increases as the atomic
weight of the metal increases in the cases of
even series members of Group II., but that the
quantity of heat produced decreases as the atomic
weight of the metals in odd series of the group
increases. Further, it seems that the increase
in the even series members is much less for
equal increments of atomic weights than the de-
crease in the odd series members. And lastly it
is seen that the value for magnesium, which is
the first odd series member of the group, is gene-
rally nearly the same as the value for calcium,
which is the first even series member for which
thermal data have been observed. Unfortunately
hardly any thermal measurements have yet been
made for compounds of beryllium ; the follow-
' The Bquare bracket denotes that the thermal value of
the chemical change which occurs between the bodies
within the bracket is measured ; the comma means that
chemical action occurs between the bodies the symbols of
which are separated by this comma ; the symbols at ele-
ments and compounds are to be read in grams ; the figures
represent gram-units of heat produced ; the symbol Aq is
used to denote so large a mass of water that an increase
in this mass would not affect the thermal value of the
change. Thus [Oa,Cl',Aq] = 187,600 means that 187,600
gram-units of heat are produced when 40 grams of calcium
and 71 grams of chlorine combine, in presenoa of much
water, to produce 111 grams of calcium chloride.
' These figures represent the heats of formation of
tolU HgCl. Hg.Olv HgBr, Eg,Br„ Hgl„ and Hg^t, re-
spectirely.
206
OLASSIFIOATION, CHEMICAL.
ing numbers, taken from Thomsea's work, show
that the beat of neutralisation of beryllium
hydroxide is very much less than that of the
other even series members of the group, or of
magnesium, and approaches the values for
sine, cadmium, and mercury : —
Q [Q,2H01Aq]
BeOjHj 16,100
CaOjHj 27,900
SrOjHj 27,630
BaOjHj 27,780
MgOjHj 27,690
I ZnOjHj 19,880
CdOjHj 20,290
HgO 18,920
Looking at these thermal measurements as a
whole it' is clear that, thermally considered, mag-
nesium is very analogous to the three metals Ca,
Sr, and Ba ; that the three metals Zn, Cd, and
Hg form a second class, mdrked ofC from the
Mg...Ba class; and that, if one may draw any
conclusions from the meagre data, beryllium
seems to belong to the zinc rather than to the
magnesium class, A consideration of the ther-
mal values of the reactions of the metals in
Group II. with acids shows that mercury is
more widely separated from the other members
of the group than these other members are from
one another. Thus, take the values of the
differences (1) between the heats of formation of
the chlorides of the metals and that of gaseous
hydrochloric acid, and (2) between the heats of
formation of aqueous solutions of the nitrates of
the metals and that of aqueous nitric acid ;
these differences give comparative representa-
tions of the quantities of heat produced, or which
disappear, when equivalent masses of the metals
react (1) with the same (equivalent) mass of
gaseous hydrochloric acid, and (2) with the same
(equivalent) mass of nitric acid dissolved in
much water : —
M [M,0P]-[H",01"] M [M,O,lsr»0"Aq]-[lf»O',Aq]
Ca 125,820 Ca 117,520
Sr 140,550 Sr 125,770
Ba 150,740 Ba 127,380
Mg 107,010 Mg 116,840
Zn 53,210 Zn 42,870
Cd 49,240 Cd 26,360
Hgj 18,600 Hgj -11,650 (used)
Hg 9,200 Hg -22,570 (used)
As a general rule, such thermal data as are
given here and elsewhere in this article repre-
sent differences between the quantities of energy
degraded from more chemically available to less
chemically available forms, during similar reac-
tions. Of two systems producible from the
same initial system, that one will be the more
stable the production of which is attended with
the running down of the greater quantity of
energy. It is most important to trace con-
nexions between the compositions of chemical
systems and the quantities of energy degraded
during the production of these systems; but
such thermal data as are given here can only
be regarded as affording bases for very rough
comparisons of the stabilities of the various
systems produced by the diiBerent chemical
operations formulated (v. further Equimbbium,
OHEMioAii ; and Physical heihods).
Further data on which comparisons of the
compounds of the elements in Oroup 11. may be
based are furnished by (1) the melting-points,
and (2) the so-called specific volumes, of similar
compounds. The specido volume of a compound
is defined as the quotient obtained by dividing
the formula-weight by the specific gravity of
the solid compound ; it represents the volume,
in cubic centimetres, occupied by the mass of
the solid compound, in grams, represented by
the formula of the Compound. The difference
between the specific volume of a binary com-
pound and that of one of the elements contained
in one formula-weight of the compound may be
taken as representing the specific volume of the
other element in one formula-weight of the com-
pound; these differences afford useful data for
comparing similar compounds of elements in the
same or different groups : —
Melting-points of chlorides and bromides (approz.),
BeClj 600° BeBrj 600°
CaClj 720 CaBrj 080
SrClj 825 SrBrj 630
BaClj 800 BaBrj 810
MgClj 700 MgBr, 700
ZnCla 260 ZnBrj 400
CdCl^ 540 CdBrj 670
HgCLj 280 HgBrj 240
Spec. vols, of solid oxides MO.
round difEer-
numbers euces
BeO 8
CaO 18
SrO 22
BaO 28
10
4
6
MgO 12
ZnO 14
CdO 16
HgO 19
Spec. vols, of MO— spec, vols, of M.
(=bypotIietic!tl spec. vols, of 0 in MO)
In BeO +2-7
'„ CaO -7-2
„ SrO -12-9
„ BaO -8-5
„ MgO -1-8
„ ZnO -^5•l
„ CdO +6'3
„ HgO +4-7
As regards the meltir>pointa of chlorides
and bromides, we see that the five metals Be,
Ca, Sr, Ba, and Mg, are closely related to each
other, while the three remaining metals of the
group, viz. Zn, Cd, and Hg, form a class by them-
selves. As regards the specific volumes of oxides,
we notice that the values increase from BeO to
BaO, then fall to MgO, and again increase from
MgO to HgO ; the great difference between the
value for CaO and that for BeO (10), and the
smaller difference between the value for BeO and
MgO (4), suggest that BeO is more allied to the
group MgO HgO than to the group CaO,
SrO, BaO. An analogy between BeO and the
oxides of Zn, Od, and Hg, is also pointed to by
the value for the speciflo volume of O in th»
oxides MO.
Finally, let us tabulate the differences be-
tween the values of the atomic weights of pairs
of consecutive metals in the group we are con.
sidering : —
CLASSIFIOA.TTON, CHEMICAL.
Ba-Srl ^„ 50 + 47
137-
a.-Sr\ _-.
7_87J-=50;
= 48-5.
OM series f,Zm-^l ^.tl^^"
2^|:?i'2}=88 = ax.; 111^1 = 44.
47 + 50+41 + 47 + 44 ^ ^g.g_
5
Omitting the difference Ca-Be, it is eeen that the
diSerence between the atomio weights of a pair
of consecative elements approaches the value 45 ;
and that the difference is rather larger in the
cases of the elements belonging to even series
than in those of elements belonging to odd series.
But the difference Ca— Be is only 31: in this
respect beryllimn stands marked ofE from the
other elements of the group. If the differences
between the values of the atomic weights of the
first and second even series members of Groups I.
to YII. are tabulated, it is found that this differ-
ence varies from 32 (K— Li) to ,36 (Mn— P), and
has a mean value of 34 ; but 34 is considerably
less than 45, which is about the mean difference
between any two elements (omitting the elements
from Li to Ka) in the same group and in con-
secutive even, or consecutive odd, series.
Looking back at the properties of the ele-
ments in Group II., it appears that beryllium is
distinctly marked oS from the other elements of
the group ; that calcium, strontium, and barium
are more closely related to each other than they
are related to any other elements of the group ;
that the relations between zinc and cadmium are
most marked ; and that mercury is to some ex-
tent separated from the other members of the
group. Beryllium approaches magnesium in the
method of its preparation ; in its high melting-
point ; in the unreadiness with which it oxidises ;
in the ease with which its hydroxide is decom-
posed by heat ; in the solubility of its sulphate ;
in the specific volume of its oxide ; and in some
other properties. Beryllium approaches calcium,
among other respects, in the nature of its spec-
trum; and in the readiness with which its
hydroxide combines with carbon dioxide. In
the melting-point of its chloride and bromide,
beryllium approaches the three metals calcium,
strontium, and barium. The analogies between
beryllium and zinc are marked by the following
among other properties : action on water ; solu-
bility in aqueous potash ; crystalline form of the
oxides. The solubility of beryllium sulphate in
water ; the readiness with which basic salts, and
also double salts, of beryUium are produced ; the
existence of gasi&able chloride, bromide, ethide,
and propide, of beryllium ; the specific volume of
oxygen in beryllium oxide; and the thermal
value of the neutralisation, by aqueous hydro-
chloric acid, of beryUium hydroxide; these pro-
perties indicate the analogy between beryllium
and the three odd series members of the group,
zinc, cadmium, and mercury. Calcium, stron-
tium, and barium certainly stand byihemselves ;
but in the specific volume of the oxygen in its
oxide, And more especially in the thermal values
of similar reactions, the odd series metal mag-
nesium is dosely related to these three even
series metals. Mercury is marked off from the
other elements of the group by the fact that it
forms two series of salts, and by the thermal
values of the reactions between it and hydro-
chloric and nitric acids; but in the general
character of its persalts, in the melting-points
of its chloride and bromide, in the specific volume
of its oxide and of the oxygen therein, mercury
is clearly related to zinc and cadmium; and in
the solubility of its oxide in molten potash, the
relationship of mercury more especially to zinc
and beryllium is rendered evident. An element
has yet to be discovered which shall have an
atomio weight equal to about 158, and which
shall form a link between cadmium and zinc on
one side and mercury on the other.
Putting together all we have learned of the
elements and the compounds of the elements in
Group II., we see that the group contains certain
sub-groups or families, but that the special
characteristics of these families are balanced by
the strength of the group-character which im-
presses itself on all the members of the group.
Group VI. comprises the following ele- '
meuts : —
Even series
2 4 6 8
0 = 16 Cr=52 Mo=96 —
10 12
W = 184 U = 240
Odd series
3 6 7 9 11
S = 32 Se = 79 Te=125 — —
We have here two families : the even series
members O, Cr, Mo, W, and U; and the odd
series members S, Se, and Te. But in many
respects the first member of the even series
family, oxygen, more resembles the odd series
family than it resembles the other members of
its own family. There is a distinct line of sepa-
ration between oxygen on one side' and Cr, Mo,
W, and U on the other side. The four members
of the even series family Cr . . . . U may be
divided into two sub-fanulies, Cr and Mo, and
W and U ; but there are well-marked analogies
between Cr and U on the one hand, and between
Mo and W on the other hand. Finally, some of
the members of the even series ' family, besides
oxygen, show very distinct relations to members
of the odd series family ; e.g. Cr and S, and U
and Te, are more or less closely related.
Let us consider these relationships very
briefly. The compositions of the binary oom-
poTinds of O, S, Se, and Te; emphasise the rela-
tions between the four elements : we have MH,,
MCl^, MKj, MCa, M(C»H2„+i)2, Ac, where M = 0,
S, Se, or Te. The properties of these compounds
are also very similar. No hydrides of the other
even series members (Cr . . . . TJ) are known, the
best-marked chlorides of the^e elements are not
MCI,, nor do these elements form compounds
with K, Ca, or the radicles C„H2n+i. There is a
less-marked gap between the physical properties
of O on one hand, and ' S, Se, and Te on the
other, than between the former element and Cr,
Mo, W, and U: thus, the melting-points of S,
Se, and Te all lie under 550°, whereas Cr, Mo,
and W, are scarcely fusible at the highest at-
tainable temperatures, and XT melts only at a
full red heat. The specnfic gravities also of S
and Se are less than 5, whereas the values of
this quantity for Cr . . . . U vary from 6'7 (Or)
to 19 (W). The specific gravity of Te is about
CLASSIFICATION, CHEMICAL.
6*2. The elements S, Se, and Te, are distinctly
non-metaUioand negative; their oxides areaoid-
forming ; these elements do not replace the hy-
drogen of acids with formation of salts; in these
respects they approach closely to oxygen, which
is the typical non-metallic acid-forming element.
Tellurium, however, is to some extent separated
from selenion and sulphur ; it is a white, brittle
solid; its haloid compounds are much more
stable than those of S or Se ; its oxides are not
strongly acid-forming; the acids HjTeO, and
H^TeO, are easily separated into water and
anhydride, they are only slightly soluble in
water, and are feeble acids (this statement may
be made although the relaiwe affimties of these
acids have not yet been determined). Thomsen's
measurements of the relative affinities of sul-
phuric and selenic acids (H^SO^ and B.JSeO,),
and the confirmation of these results by Ostwald's
study of the electrical conductivities of aqueous
solutions of these acids with varying masses of
water (v. Apfinitt, vol. i. pp. 75, 81, 83), show
that these two acids are most closely related in
their powers of combining with bases. The heat
of formation of aqueous solutions of the oxides
MO3, however, point to a closer relation between
Se and Te on one hand, than between either of
these elements and S on the other hand : thus,
142,410 when M = S
[M, 0',Aq] = . 76,660 „ M = Se
98,380 „ M=Te.
Notwithstanding these resemblances we must
admit that oxygen is distinctly cut off from the
other members of the group, whether they be
even series, or odd series, elements. Thus the
thermal values of the formation of hydrides re-
veal a great gap between 0 and S : [H', O]
= 68,360, but [ff, S] =4,740 (unfortunately
values for [H^ Se] and [H'^ Te] have not yet
been determined). Oxygen, like beryllium in
Oroup II., is a so-called 'typical' element; the
relations of this element to the odd series family
of its group — S, Se, and Te — are not unlike the
relations of the typical Be to the members of its
group which belong to odd series — Mg, Zn, Cd,
Oxygen is distinctly cutoff from the even family
Cr . . . . TJ by its physical properties ; by the
composition of compounds with the same ele-
ments, e.g.00l2, 0,Cl,CrCl3, MOCl,, WCls, UCl, ;
by the properties of many of these compounds,
e.g. OGI2 boils at -18°, MOCI5 and WClsmelt
between 200° and 300°, the heat of formation of
OCI2 has a large negative value, the heats of
formation of chlorides of the other elements
have not been determined, but from established
analogies there can be no doubt that the numbers
representing these heats of formation have large
positive values ; further the elements Cr, Mo,
W, U, act both as acid-forming and salt-forming
elements, whereas oxygen is in the most marked
way the typical acid-forming element.
The even family Or .... U may be broadly
divided into two sub-families, Cr and Mo, and
W and U, Thus the specific gravities of Cr and
Mo are, respectively, 6-7 and 8'5, of W and U 19
and 18-5; the specific volumes (i.e. atomic
weight-s-S.G. of solid) are 7*7 and 11-3, and 9-7
and 12-9. Some of th? oxides of chromium, e.g.
CrjOj, are distinctly salt-forming, but CrO., is the
anhydride of a well-marked acid, HjCrO,, from
which is derived a large series of well-marked
salts, for the most part isomorphous with simi-
lar sulphates and manganates. The oxides of
Mo can scarcely be (dassed as salt-forming,
although M0O2 is said to dissolve in acids with-
out evolution of oxygen ; M0O3 is the anhydride
of an acid H2M0O4; two classes of chromium
salts exist, chromous salts represented by
CrS047H20, and the more stable chromic salts
represented by CrjSSO,, CrjONOj, &c. ; hydrated
oxides of the composition MO^jH^O, both of Cr
and Mo, seem to exist, but they are easily oxi-
dised to compounds of the form Mfi^Sfi.
The relations of W to U are similar to those of
Mo to Cr; few, if any, distinct salts are known
obtained by the replacement of the hydrogen of
acids by W, but U forms two well-marked series
of salts, represented by USO4 and UOjSO^ re-
spectively ; the oxides WO, and UO, are both
anhydrides of acids HjW(U)04. The oxide WO,
resembles M0O2 in that it dissolves in acids
without evolution of oxygen; WO, and MoO,
also form double compounds with various anhy-
drides, e.g. with PjOj, SO5, &o. The salt-form-
ing character of the oxides of the family Cr,
Mo, W, U, decreases from Cr to Mo, and again
increases from W to U, but at the same time
the extremes of the family (Cr and U) produce
more distinctly marked acid-forming oxides
(MO9) than either of the means (Mo and W).
Finally, the highest members of the odd and
even series of Group VI., Te and U, are, on the
whole, more positive (although XJ produces a
well-marked acid-forming oxide) than the other
members of either family ; and the first member
of the even family, viz. Or (excepting oxygen,
which belongs both to the odd and the even
families), shows fairly marked analogies with
the first member of the odd family, viz. S.
Summing up the characteristics of Group VI.,
and comparing them with those of Group II., we
see that the former group, as a whole, is non-
metaUic ; its members are comparatively nega-
tive, and their best-marked oxides, as a class,
are acid-forming ; but we find in it two families,
one of which, Cr . . . U, is more metallic and
salt-forming, and the other, S . . . Te, is more
non-metallic and acid-forming. Similarly we
find in Group II. two families, one more dis-
tinctly metallic than the other; but, on the ojiher
hand, the whole character of Group II. is me-
tallic, and the oxides of the members of the
group are salt-forming. In each group we have
found a ' typical ' element : in Group VI. oxygen,
in Group II. beryllium ; the properties of this
element to some extent summarise theprOperties
of all the members of the group. The difference
between the value of the atomic weight of oxygen
and that of the next even series member of
Group VI., viz. Cr, is 36 ; the difference between
the atomic weight of beryllium and that of the
next even series member of Group II., viz. Ca,
is 31 ; the mean difference between any two con-
secutive even or odd members of either group ia
about 45 ; oxygen perhaps rather more closely
approaches the properties of the odd family of
its group than beryllium approaches the pro-
perties of the family of Group II. the members
of which belong to odd series.
Let us now turn for a moment to those groups
in which the family-character preponderates over
the group-character. Groups I. and VII., and to
CLASSIFIOATION, OHBMIOAL.
209
those in which the group-oharaoter is much more
marked than the family-oharaoter, Groups III.,
Group I.
Sven Series —
2 4 6 8
Li = 7 K = 39 Rb = 85 Cs = 133
Odd Series —
3 5 7 9 11
Na = 23Cn = 63Ag = 108 — Au = 197
The very marked similarity between Li, Na,
K, Kb, and Os.both as regards the metals them-
selves and their compounds, quite overshadows
the much more feebly marked similarities which
exist between Ou, Ag, and An. But the thermal
values of the reactions between lithium and
water, between Id and 0, Li and CI, or Li and
Br in presence of water, &o., the comparative
insolubility of LiOH, LijCOj, LijPOi, the non-
formation of an alum containing Li, the non-
formation of double salts containing LiCl, the
comparatively less ready oxidation of Li, and
some other properties, show that lithium is to
some extent separated from the metals Na . . . Os.
The properties of those salts of copper of
which the chloride CujCl, is a representative,
exhibit some analogies with those of the com-
pounds of lithium. Silver approaches the even
famUy of Group I. in the composition of aU its
well-marked salts, in the distinct alkaUnity of
its oxide, and in the fact that silver sulphate
forms an alum. Although gold is distinctly
marked off from the other members of the group,
yet in the softness of the metal, in the facts
that compounds of the form MjO are known,
that the auric haloid compounds very easily
form double salts with the haloid compounds of
Na . . . Cs, that Au^O and Au^S are sol. in
water, and in a few other respects, this metal
exhibits some analogies with the even family
of the group and with sodium.
Group VII.
2 4
P = 19 Mn = 65
Odd Series —
3 5 7
01 = 35-5 Br = 80 1 = 127
Here thp family-character of the odd series
members impresses itself on the whote group ;
fluorine exhibits definite relations to the odd
family, but the two facts that it forms no com-
pounds with oxygen, and that its compounds
with hydrogen and the alkali metals exhibit the
greatest readiness to form double salts, suffice
to cut it ofl to some extent from CI, Br, and
I. The heat of nentraUsation of HF is consider-
ably larger than the heat of nentraUsation of
HCl or HBr; [HMAq, NaOHAq] = 13,740 when
M = C1 or Br, but =16,250 when M=I', but
the relaUve affinity of HP is very small ; it is
approximately equal to 5 when that of HCl = 100,
and that of i£Bi = 95 or so. The thermal values
of some similar reactions of CI, Br, and I, show
that these elements are not so closely related to
each other as a consideration of the outstanding
chemical properties of their compounds would
lead one to suppose ; thus, [H, CI] = 22,000 ;
[H, Br] = 8,040 ; [H, I] = - 6,040 (absorbed). The
Vol. II.
differences between the properties of perchloric
and periodic acids also emphasise the differenced
between chlorine and iodine. The isomor-
phism of permanganates and perchlorates, the
markedly acid-forming character of MnOj, and
the existence of permanganic acid, establish a
connection, feeble though it be, between man-
ganese and the other members of Group VIL
In studying the relations of the members of this
group it should not be forgotten that no repre-
sentative of series 6, 8, 9, 10, 11, 12 or 13, is at
present known.
Group III.
Even Series — >
2 4 6 8 Iff
B = ll So = 44 T = 89 La = 139 Tb = 173
Odd Series —
3 5 7 9 11
Al = 27 Ga = 69 In = 114 — Tl = 204
The group-character is here impressed on
aU the elements ; Al and Ga form a family to
which In is allied and Tl shows analogies in one
class of compounds ; Sc is not without analogies
to Al and Ga, it is also distinctly related to B ;
of the other metals too little is known to enable
us clearly to see their analogies. The last mem-
ber of the group, thaUium, astonishes us by the
marked way in which in the thaUous salts
(TLjO, TljSO,, &c.) it approaches the even series
members of Group I.; viz. Li . . . Cs. The
typical element, boron, while showing analogies
with all the other members of the group, and
with other elements, e.g. with 0 and Si, is yet
different from any of them; it is a good repre-
sentative of the want of family likeness between
the even series members or the odd series mem-
bers of this group, and at the same time of the
distinctly group character which is impressed on
all the elements in the group.
Group IV.
Even' Series —
2 4 6 8 10 12
C = 12 Ti = 28 Zr = 90 Ce = 140 — Th = 232
Odd Series —
3 5 7 9 11
Si = 28 Ge = 72 Sn = 118 — Pb = 207
Here again the even series members do not
form a family marked off from the odd series
members. Certain minor families are, it is true,
to be found in the group, but on the whole, the
group-character much preponderates. Carbon
stands by itself ; it is marked off from all other
elements by the immense number and com-
plexity of the compounds which it forms with
H, O, N, S, and the halogens. Most nearly re-
lated to carbon we have the first odd series
member of the group, silicon ; the silico-organio
compounds, the existence of allotropio varieties
of silicon, the relations between the specific heat
of silicon and temperature, the thermal values
of similar reactions of carbon and silicon, ex-
hibit the analogy between these elements (v.
Cabbon oboup 07 ELEMBNis). The physical
properties of Ti and Zr, the stabili'.y, and acid-
forming character, of their oxides MO^, the
volatility of their chlorides MCl,, 'the iso-
morphism of some titanates and zirconates with
silicates, these points emphasise the connectioua
210
CLASSIFICATION, CHEMICAL.
between Ti, Zr, Sii and C. But the formation
•of the sulphate ^(SOJj, ,of various salts of
zirconium, e.g. Zr(S04)2, Zr(N03)4, &o., show that
these elements incline also towards Ce and Th
which follow them in the even series, and to-
wards Sn and Fb which belong to odd series of
the same group. Cerium forms salts analogous
to those of zirconium, e.g. Ce(S0,)2, but its most
marked compounds are represented by the per-
oxide GeOj. Thorium again approaches more
closely to Ti and Zr than Ce does; the existence
of ThOj, Th(S04)2, KjThF,, ThF^, marks this
analogy. Tin and lead resemble each other
physically mpre "than they resemble other
members of the group ; they exhibit the group-
character in their oxides MO and MO,, in their
chlorides (or ethides) MCI4, in their salts E2MO.,;
tin further exhibits this character in its stannic
salts Sn(S04)2, Sn(N03)„ &o. ; but each of these
elements produces compounds which have no
analogies among those of the other members of
the group.
Group V.
Even Series —
2 4 6 8 10
N = 14 V = 61 Nb = 94 Di = 144 Ta = 182
Odd Series —
3 S 7 9 11
P = 31 As = 75Sb = 120Er = 166 Bi=208
The group-character is so impressed upon the
whole of these elements that we may almost say
there are no families ; and yet the group falls
into two subdivisions, each of which nearly re-
peats the characteristics of the other. From N
to Ta we pass from a most markedly non-
metallic, aoid-forming, element to an element
which, on the whole, is more metallic than
non-metallic ; from F to Bi we repeat the same
gradation,, only here the starting-point is an
elenlent rather less negative in its functions than
nitrogen, and the last member of the series is
decidedly more positive than tantalum. The
less prominently acid -forming character of
phosphorus as compared with that of nitrogen
is exhibited, among other ways, by the relative
affimiUes of nitric and phosphoric acids; the
former being taken as 100, the latter is approxi-
mately equal to 20. The balance of metallic and
non-metallic properties in tantalum is well
shewn by the action of acids on aqueous solu-
tions of potassium tantalate. Acids whose rela-
tive aflSnity is large, e.g. sulphuric or hydro-
chloric acids (affinity = (approx.) 70 and 100),
decompose this salt and pp. tantalio acid
(HjTaOg) in combination with a portion of the
acid used; acids with a smaller affinity, e.g.
sulphurous acid (affinity. not determined, but,
from Ostwald's electrical experiments, it must
be considerably less than HL^SO,), completely
pp. pure tantaUc acid; acids with yet smaller
affinities, e.g. H3FO4 (affinity about 20), pp. po-
tassium tantalate ; and, lastly, acids vrith very
small affinities, e.g. acetic or succinic acid (affi-
nities 6 and 7 respectively^, cause no pp. when
added to solutionsof potassium tantalate. That
the last member of the odd series family, viz.
bismuth, is more metallic than the last member
of the even series family, viz. tantalum, is
shown by the fact that in all its well-established
compounds bismuth is positive to the other ele-
ments with which it is combined, and that if
hydrated bismuthio oxide, Bifi^wKfi, acts as
an acid it forms salts which can scarcely be
obtained in definite form, and which are cer-
tainly at least partly decomposed by the action
of hot water.
We have thus endeavoured to draw the out-
lines of a scheme of classification of the elements
and their oompounds based on the comparison
of those which are similar in physical and
chemical properties, and by similar chemical
properties we have implied similarity of function
and similarity of composition. It yet remains,
however, to examine somewhat more closely into
the composition of the compounds classified,
with the view of finding whether anything can
be learnt of the structure of these bodies in the
sense which is given to the word structure by
the molecular and atomic theory. The composi-
tions of the highest oxides, and of some of the
other compounds of the elements, appear to vary
periodically with variations in the atomic weights
of the elements. If B represent the mass of an
element expressed by its atomic weight, and if
X represent the masses of F, CI, Br, or I, ex-
pressed by the respective atomic weights of these
elements, or the masses of the groups OH, KOg,
CIO,, &o., expressed by these formulse, or the
masses of the elements or groups of elements
expressed by Jialves of the formula O, &, SO,,
Cr04, &b., then we may say that the compositions
of the oxides
BjO, BO, Ej0„ BOj, EjOj,
are expressed by the symbols
BX, BX2, BX3', BX4, EX5.
We may also say that the compositions of the
EjSO,; E(N0,)2; B(N0,)„ EOCl, B2(S0J„
BONO,; EOCl,,
are expressed by the symbols
EX ; BX^; BX„ EXj, EX,, BX3 ; BX,.
In this way it becomes possible to give general
expressions for the forms of the highest stable
oxides characteristic of each group, and also for
the forms of the highest well-marked salts of the
elements of each group. It is generally found
that the greater the value of X in the oxide-
form the smaller is the value of X in the salt-
form. The following symbols are given by
Brauner (Sitz. W. IMath.-naturwiss. Classe'], 84,
1165) :—
Groups .
Oxide forms
Salt forms
. I.
. EX
. EX,
II.
BX2
EX.
TTT,
EX,
EX,
IV.
EX,
EX,
Groups .
Oxide forms
Salt forms
. V.
• EX,
. EX,
VI.
EX,
EXj
VII.
EX,
BX
VIII,
EX,
E2X
The characteristic oxides of most of the ele-
ments belonging to Group I., Li ... . Au, are
represented by the general symbol E2O ; putting
X = — , the ratio of metal to O in these oxides
is expressed by the symbol BX. Similarly the
composition of the characteristic oxides of the
elements of Group II., Be ... , Hg, is repre-
sented by BO; but, as 0 = X2, the symbol BX,
expresses the same composition as the symbol
BO, The salt-forms, EX, .... BX, are inter-
OLASSIFIOATION, CHEMIOAL.
211
meted in the same way as the oxide-forms.
Thus Na forms a bydiated hydroxide of the
composition Na.0H.3H(0H); now, if X = H = OH,
this compound belongs to the general form RX,;
similarly, the salt SjOl^ (Group VI.) belongs to
the general form BX. These symbols must be
' interpreted only in a wide and general way.
For instance, the highest oxide of a metal of
Qroup I. is E2O4, and this belongs to the form
SX,, but the most characteristic oxides (MjO)
of the majority of the metals of this group
belong to the form BX ; the most characteristic
oxide of copper, however, is CuO, and of gold is
AujO, ; these oxides belong, respectively, to the
forms BX2 and BX,. But Cu and Au are classed
both in Groups I. and VIII.; the oxide form of
Group VIII. is BX„,and the salt form is BjX;
but no well-marked oxide or salt of either Gu or
An belongs to either of these forms. So again.
Group V. has assigned to it the oxide form BX,
and the salt form EX3; the oxides NjOj ....
BijOs certainly belong to the form EX,; the
salts N02(0H),P0j(0H), &o., belong to the form
EX,; but the salts PO(OH)„ Sb,0,(OH)„ &c.,
belong to the form EX,, and the saltBi20,H(0H)
to the form EX5. The symbols given must then
be interpreted as representing the limits between
which the compositions of most of the com-
pounds of each group vary; that with the
greater value of X represents the composition
of the highest compounds, and that with the
smaller value of X represents the composition
of the lowest compounds of the elements in
any specified group. The expressions ' salt-
forms ' and ' oxide-forms ' are not to be recom-
mended ; it would be better to summarise the
facts of composition in some such way as
this : —
Limiting forms between which the composition of compounds varies.
Groups.
L n. ni. IV. V. VI. VII. viii.
EX, to BX BX, to BXj BX, to EX, BX^ EX, to EX, BX, to EXj BX, to EX BX, to EjX
In Groups I. to III. the lower form usually
represents the composition of what may be called
the typical group oxides ; in Groups V. to VIII.
the higher form usually represents the composi-
tion of the typical group oxides. The ' typical
group oxides ' are not always the most stable
oxides; e.9. Bi20,(BX,) is less stable than
BijO,(EX,) (Group V.), Pb02(EXj) is less stable
than PbO(EX2) (Group IV.). Sometimes these
' typical group oxides ' are scarcely known to
exist ; e.g. no oxide of the form BX, has certainly
been obtained where B is an element of Grou^
VII. ; but the composition of the highest, and
speaking broadly the most stable, acids (? acids
with largest aifinities) of this group of acid-
forming elements is represented by the symbol
HMO, (where M = C1, 1, or Mn), and the hypo-
thetical anhydrides of these acids have the com-
position MjO,, that is, are represented by the
symbol EX,. Of the 11 elements which ought
to find places in Group VII., only 5 are actually
known ; when the remaining 6 have been pre-
pared and their compounds examined some of
them may be found to form oxides belonging to
the form EX,. Concerning Group VIII., it is
difficult to say which oxides of the members of
this group are to be taken as the typical group
oxides ; for Ni, Co, and Ou, one would be inclined
to adopt the oxides MO(EXJ, for Fe and Au the
oxides M,0,(BX,), for silver the oxide Ag,^0(EX),
and for Os and Bu the oxides M0,(BX,). The
compositions of these vary between the limiting
forms EX, and EX; there is probably a sub-
oxide of silver (Ag^O) belonging to the form
EjX.
When we deal with compounds other than
oxides, the application of the Umiting forms be-
comes yet more difficult. If the term salt be
taken to mean (1) acids, in the cases of markedly
negative elements, or (2) metallic derivatives of
acids, in the cases of markedly positive elements,
then the characteristic salts of the elements of
Group I. are represented by Li2S04, and they
belong to the form BX ; the characteristic salts
of Group II. are represented by BeSO^, and they
belong to the form BXj. Tabulating in this way
the characteristic salts and their general symbols
for the groups, we have the following result : —
Groups
Salt .
Form .
Group
Salt .
Form ,
I.
LijSO^
BX
Group
Salt .
Form ,
Group
Salt
Form
II.
BeSO,
EX,
III.
IV.
Al^aSO,, B(OH),
CC1„ Sn(SO,),
EX,
EX,
V.
NO,(OH), BiSNO,-) ^^^ J'PO(OH)„ SbCl,
EX, / \ BX,
VI.
C'^fO^and (^^\^^°*>»} and {^^I" f^^^^'
VII.
. . . MnSOa ^jj^ rMnO,(OH), C10,(0H)
• • • BX2 / \ BX,
Group
VIII.
l:i : ^1?'} -^ r'''\C'^'^y} .nd {^ii;} and {OsO(O^K)H(OH)}
and /PtClS02(0H), PtPCl,, PtO,2H(OH)
I EX,
pa
812
CLASSIFICATION, CHEmCAL.
U the term salt is nsed to include all com-
pounds of a given element, whether these be
classed as double salts, basic salts, hydroxides,
<Sso., &e., then it is easy to find representatives
of most forms, intermediate between the limiting
group forms, for the members of any group.
For instance, salts higher than EX and up to
B?, belonging to Group I. are represented by
KI, (EX,), KA,uC!l, and KAuBr, (EX^), and
Na{0H).3H(0H) (EX,) ; salts of the form EX^
belonging to Group HI. are represented by BOGI3,
AlKOl,, and AIKI, ; salts belonging to Group H.,
of the form EX,, are represented by MgNaP, and
BeKPs, and of the form EX, by BeK^,, ZnKjF,,
Bud Ba02H(0E). It has been sought to trace
special relations between the forms of hydrides
and hydrated oxides in each group ; thus, Men-
delejeff gives the following symbols : —
Groups
{Sydrideform . .
Example . . .
{Hydrated oxide form
1
them and other groups, or single atoms. The
way was thus prepared for regarding all chemical
phenomena as essentially the results of mutual
actions and reactions between elements or com-
pounds, and for the conception of chemistry as
the study, not so much of this kind of homo-
geneous matter, or that, as of the connections
between the changes of composition and the
changes of properties which these kinds of mat-
ters exhibit when they mutually act and react
under defined conditions. The conception ol
radicles went hand in hand with that of types.
The meaning of a typical classification of ele-
ments and compounds has been illustrated in
the present article {v. also Badicles and Types).
The most complete outcome of this method is
the classification based upon the periodic law ;
and the use of typical forms to express the com-
Oronps
{Sydrideform . , <
Example . . ,
{Hydrated oxide form ,
Example
The limiting forms of compounds which the
periodic law supplies as an aid in classifying
elements and compounds are undoubtedly useful
if employed with caution. The search for such
limiting forms has always been carried on in
chemistry. , Dalton and Berzelius made it the
main business of their lives, as chemists, to seek
for formulsa which should express the maximum
numbers of atoms of each element capable of
combining together. Berzelius developed his all-
embracing system of dualism on the conception
that every compoimd is built up of two parts,
themselves either simple or complex, one of
which is electrically positive towards the other
{v. DuaIiISIi). This conception at once led to
that of radicles, or groups of atoms which re-
main so closely united throughout various
chemical changes that the functions performed
by them in these changes are, to all intents,
the functions of single atoms. The conception
of the radicle brought with it into chemistry a
mode of reasoning which has been of much im-
portance in the advances made within recent
years. The group of atoms named a radicle was
not known, as a rule, except as it manifested
itself in the reactions of compounds supposed to
be formed by the union of the radicle with other
radicles or with elements. The arguments for
or against an explanation of a chemical occur-
rence wherein radicles were regarded as taking
part were necessarily based on experimental
evidence which failed to bring into court the
actual complex of atoms asserted to be an essen-
tial part of the mechanism of the change. Che-
mists became accustomed to think of certain
collocations of atoms as necessary factors in this
or that operation; but they attributed actual
existence to these atomic groups only when
mutual action and reaction was occurring between
I.
n.
III.
•
EH,
EH,
BH5
•
•
EH,0,
BH,0,
BH5O,
. NaOH.3HOH
Ca{OH)22HOH
AljOsSHjO
2
IV.
V.
VI.
VII.
EH,
CH,
EH^O,
Si(OH),
EH,
PH3
BH,0,
PO(OH),
BHj
OH,
EH,0,
SO,(dH),
EH
CIH
EHO,
CIO,(OH)
positions of oxides, and other compounds, of each
group of elements, is one of the points whereiu
the periodic law emphasises the continuity of
chemical science.
The great objection to the use of these typi-
cal or limiting forms seems to be that they are
based too exclusively on the notion of showing
the composition of compounds, and that their
employment tends to hide the importance of
combining the study of composition with that of
properties. The purely empirical compositions
of the salts KAuOl, and NaOH-SHjO are cer-
tainly represented /by the symbols EX5 and BX„,
as illustrations of the existence of which forms
in Group I. the salts in question are brought
forward ; but a comparison of the properties of
these salts with those of such compounds as
AujO, and Na20 at once shows that there is a
great difference between the two classes of com-
pounds. The mere fact that platinum forms a
compoundwhioh, by the dexterous use of symbols,
may be represented as belonging to the type EXj,
can be of little assistance in developing a ra-
tional scheme of classification. One of the pla-
tinum compounds of this type is PtClSOj(OH) ;
why should not this compound be used to prove
that sulphur forms compounds of the type BX„
or that chlorine forms compounds of the type
EXj? Why is the compound BeK^F, {i;e.
Be£'2.2KE') to be adduced as an example of the
existence of compounds of the form EX, in
Group II., and not as an example of the existence
of compounds of the form BX, in Group I., or
of the form EX in Group VII. ? If empirical
composition is everything, it is only necessary to
write this double fluoride as KjBeF,, to prove that
it belongs to the (EjXjX, that is) EX, form of Group
I. ; or as P,BeKj, to prove that it is an example
of the (E,XjXj that is) EX form in Group VII.
CLASSIFICATION, CHEMICAL.
213
The history ol the olassifioations which at
different times have been founded on the notion
of types conclusively proves that unless attention
is constantly paid to the functions, as well as to
the compositions, of the bodies classified, the
systems do little to further > chemical advance,
and the conception on which they are founded
is shorn of most of its value as a science-pro-
ducing idea. It is most certainly true that the
classification presented by the periodic law is
based on the study at once of the compositions
and the functions of the bodies classified ; it is
this, indeed, which gives the method so marked
an advantage over all others; but just because
of this fact should we be ever on our guard
against placing too much trust in any single part
of the method, unless that part is used in con-
junction with the other parts, all of which
together constitute the complete method.
The forms assigned to many salts, especially
to the double and basic salts, almost wholly de-
pend on the values given to the different ele-
mentary atoms. Why do we begin by asserting
thatX = F,Cl,Br,I,N0„C103, ^O*. £2l, 0,
&c. ? How is the equivalency assumed to exist
between these atoms and groups of atoms actually
proved to exist? In writing the equations
P=01=Br = N0, = ^ = ^S and in applying
these to the study of typical forms of salts, we are
making many far-reaching assumptions. The
chief assumptions are two. In the first place,
the molecular theory is carried over from gases
and applied without modification to liquids and
solids. In the second place the tentative hypo-
theses which chemists have framed to help them
to group together what they have learned from
the study of gaseous compounds regarding the
equivalency of atoms are applied to solid and
liquid compounds. Both assumptions are made
without acknowledging the great differences be-
tween the phenomena on which a theory of the
structure of liquids and solids must rest, and
the phenomena from which the prevailing theory
of the structure of gases has been developed.
The very word molecule is defined only in terms
of gaseous phenomena. It is the study of
gaseous phenomena that has obliged chemists
to recognise two orders of small particles, the
molecule and the atom ; and it is from the study
of the mutual actions of gases that a working
hypothesis of the structure of molecules has been
developed. In the article Aiomo and MoiiEcn-
lAB WEIGHTS (vol. i.p. 349), an attempt has been
made to show that tiie reacting chemical unit of
a compound should at present be regarded as a
collocation of atoms, which, under definite con-
ditions, takes part in chemical changes as an
individual existence. Admitting the existence
of such collocations of atoms, it follows almost
necessarilyfrom every-day chemical facts thatthe
groups have definite configurations, which remain
unchanged throughout considerable changes of
conditions ; for all the facts of chemical change
force us to regard most chemical properties as
dependent on the relative arrangement, as well
as on the nature and number, of the atoms which
form the reacting units of compounds._ There
are few, if any, properties of bodies which, like
weight, are the sums of the properties of the
atoms, and, like the volumes occupied by gaseous
compounds on the other hand, are dependent
only on the state of combination of the atoms.
But while we admit that the chemical proper-
ties of liquid and solid compounds are partly
conditioned by the configuration of the atoms
which constitute their reacting units, we cannot
admit, on present evidence, that these configu-
rations do not undergo considerable changes
under the influence of other kinds of matter,
or of physical agencies. We rather assert that
what we know of these collocations of atoms
(and what we know is as nothing compared
with what we do not know) favours the view
tl)at their structure is easily changed, and that
in this respect they present gradations from
those which are so chemically mobile as scarcely
to be recognised as definite chemical individuals,
to those which are so chemically stable as
almost to merit the name of molecules. If then
we refuse to speculate regarding the structure
of the atomic groups which seem to form the
reacting units of liquid and solid compounds ;
and if, as a consequence of this, we also refuse
to admit the validity of any arrangement of the
atoms of solid and liquid compounds in order of
strict equivalency — for equivalency means equal .
value in exchange, and the chemical equiva-
lency of atoms can only be known when we
know the functions performed by the various'
atoms in molecules of similar structure — can
we hope to learn anything definite regarding
the equivalencies of the atoms which constitute
the molecules of gaseous compounds ?
The subject of the equivalency of atoms goes
hand in hand with that of the structure of
molecules. The subject is too large to be dis-
cussed in an article on classification ; but it is
necessary to sketch the outlines of it as sharply as
possible. All gaseous molecules formed by the
union of atoms of hydrogen, fluorine, chlorine,
bromine, and iodine are formed of two atoms ;
the molecules in .question are these: Hj, Cl^,
Br^, Ij, HF, Hpi, HBr, HI (at very high tem-
peratures the molecule of iodine is mon-
atomic).
Those atoms which combine each with a
single other atom to form a gaseous molecule
are called monovalent atoms ; the standard
monovalent atoms are H, F, CI, Br, and I. If the
gaseous molecules formed by the union of atoms
of H, F, CI, Br, or I, with other atoms are tabu-
lated, and the other atoms are then arranged in
classes according as they are each found to
combine with one, two, <Sio. atoms of H,- F, CI,
Br, or I, the following arrangement results {v.
next page). The atoms in column I. are mono-
valent ; the atoms in column II. are called diva-
lent, those in column III. trivalent, and so on.
Atoms whose valencies are greater than one may
be classed together as polyvalent. Of the 89.
elements (exclusive of the 5 standard mono-
valent atoms) in these six columns, at least five
occur each in two columns, viz. Hg, In, P, Sn,
W (In probably occurs in three columns); tlie
atoms of Ga, Cr, and Fe are probably also botli
divalent and trivalent.
The valency or equivalency (or quanti valence)
of an elementary atom may be defined as tlie
number which exjpresses the maximwrn number of
814
CLASSIFICATION, OHEmOAL,
monovalent atoms E, 7, CI, Br, I.
Atoms whioh produce compound gaseous molecules by union each with
II.
one monovalent two monovalent
atom
K,Eb,Cs,Hg,
A«.Tl,(?In).
atoms
0, S, Se, Te,
Be, Cd, Zn,
Hg, Sn, Pb, r
Mn,In,(?Ga,
Or, Fe).
III.
three mo7iovalent four monovalent five monovalent
atoms
B, N, P, As,
Sb, Bi, In, Cr,
Fe, Al, Ga.
IV.
monovalent atoms (i.e. atoms o/H, F, CI, Br, or I)
with which the given atom is foimd to combine to
form a gaseous molecule. When bismuth com-
bines with chlorine to form bismuthous chloride,
one atom of the metal combines with three
atoms of the halogen, and the molecule BiCl, is
produced. When hydrogen combines with
chlorine to form hydrochloric acid, one atom of
hydrogen combines with one atom of the halo-
gen and the molecule ECl is produced. As a
single atom of Bi combines with three times as
many atoms of chlorine as an atom of hydrogen
combines with, an atom of bismuth is said
to be equivalent to three atoms of hydrogen.
In the molecule formed by the union of atoms
of H and Gl, viz. HGl, there must be direct mu-
tual action and reaction between the two atoms ;
in the molecule formed by the union of atoms
of Bi and CI, viz. BiCl,, there may or may not
be direct mutual action between the Bi atom
and each of the CI atoms. But the atom of
chlorine is monovalent (i.e. combines with a
single other atom to form a molecule), by defi-
nition, and by reason of the facts on which the
definition is based; the hypothesis most in
keeping with the monovalency of the chlorine
atom is that each atom of chlorine in the mole-
cule BiCl, directly acts on, and is acted on by,
the altom of bismuth. Similarly, because of the
existence of the molecule SbCl,, the atom of Sb is
said to be equivalent to three atoms of hydrogen ;
and, further, one atom of Sb is said to be equi-
valent to one atom of Bi. The conception of
equivalency is here evidently that of equal value
in exchange. One atom of Bi can be exchanged
for one atom of Sb ; one atom of 0 can be ex-
changed for one atom of Se ; one atom of C can
be exchanged for one atom of Si ; one atom of
Mo can be exchanged for one atom of W ; and
in each case the other parts of the molecules
between which the exchange is effected remain
unchanged. (The molecules in question are:
BiCls and SbClj; OHj andSeHj; CCl^andSiCl^;
M0CI5 and WClj.) The molecules concerned in
the various transactions may be said, without
putting too great a strain on the words, to have
similar structures. But the notion of equivalency
is carried further ; an atom of N cannot be ex-
changed for an atom of In, but the molecules
NH, and InCl, exist; assuming that 3 atoms
of CI are strictly equivalent to 3 atoms of H,
it follows that an atom of N is equivalent to an
atom of In. An atom of S cannot be exchanged
for an atom of O in the molecule OClj ; but the
molecule SH, exists, therefore, on the assump-
tion that H2 is strictly equivalent to Clj ; it fol-
lows that S is equivalent to O. This conclusion
is upheld by the direct exchange of S f or O in
the molecules SH, and OK,. The coniQeption of
aUms
C, Si, Ti, Ge,
Zr, V, Sn,
Th,U.
V.
atoms
P, Nb,Ta, Mo,
W.
VI.
monovalerA
atoms
W.
equivalency is evidently stretched a little beyond
its strict meaning when we say for instance
that, because of the existence of the molecules
OH2 and TiOl,, an atom of Ti is equivalent to two
atoms of 0. But notwithstanding this, the
definition of the valency of an atom which has
been given may be applied to considerations
regarding the structure of molecules. So far as
data go, we seem justified in widening the de-
finition of the valency of an atom, and in assert-
ing that this number expresses the maximum
number of other atoms, be they monovalent or
polyvalent, with which the given atom combines
to form a gaseous molecule. Underlying the
word combines is the conception of direct inter-
action in the molecule. It is not necessary to
venture on any hypothesis as to the states of
motion of the atoms which form the molecule, or
as to the nature of the mutual actions which
occur between them; it is only necessary to
distinguish direct from indirect action.
The prevailing notions regarding the structure
of molecules are based on that of the valencies
of atoms ; and this carries with it the conception
of each atom being able to act (fa, and be acted
on by, a limited number of other atoms. These
conceptions are indicated more or less clearly
in the ordinary notation. Thus the so-called
H^C-C=:H,
structural formulas (1) | and
OH
(2) H3=C— O— C^Hj imply, that each carbon
atom in either molecule acts directly on, and is
directly acted upon by, 4 other atoms (the C atom
is tetravalent), that each oxygen atom acts
directly on, and is directly acted on by, 2 other
atoms (the 0 atom is divalent), and that each
hydrogen atom acts directly on, and is directly
acted on by, a single other atom ( the H atom is
monovalent). But the distribution of the inter-
atomic reactions is represented as being different
in each molecule. In the first, 5 atoms of H
are represented as in direct union with (i.e. as
directly interacting with) atoms of carbon ; the
sixth atom of E is represented as in indirect
union (through an atom of O) with a carbon
atom ; the atom of 0 is represented as in direct
union with one carbon and one hydrogen atom.
In the second molecule, all the H atoms are re-
presented as in direct union with C atoms, and
there is also direct action and reaction between
the atom of O and each C atom. These for-
mulae are arrived at after a careful study of the
reactions of the compounds; they summarise
these properties in the language of a special
outcome of the molecular and atomic theory.
It would be out of place to pursue the subject of
structural formulsB here (v. FoRMULai); these
f ormulss are supposed to rest on the fundamental
CLASSIFICATION. CHEMICAL.
216
eonoeption of the valency of the atom of each
element. This conception at once limits the
number of atoms with which any specified atom
can be directly combined in gaseous molecules ;
and it enables us to bring together under cer-
tain fairly definite expressions (which are, how-
ever, very easily misunderstood) regarding the
composition of compounds, as composition is
viewed by the molecular theory, many facts re-
garding the functions of compounds gained by the
careful study of the behaviour of these compounds
nnder different conditions {v. EgnivAiiBiiCT).
We have already somewhat fuUy discussed
the meaning to be given to the term acid ; we
have learnt that those compounds which contain
replaceable hydrogen also contain negative ele-
ments. Many gaseous acids are known ; the
application to these of the conception of struc-
ture which springs from that of the equivalency
of atoms leads to the view that in the molecule
of an acid there is always direct mutual action
between those atoms of hydrogen whose function
is shortly expressed by the qualifying term re-
placeable, and one or more negative atolns or
groups of atoms. Thus, in the molecules HCl,
fJBr, HI, HP, H(ON), there must be mutual
action and reaction between the positive H atom
and the negative 01, Br, I, or F atom, or the
negative group of atoms (CN). Again, the reac-
tions of the molecule C^H^O^ oblige us to admit
that direct mutual action occurs between the
atom of replaceable hydrogen and an atom of
the negative element oxygen, and that the three
atoms of hydrogen which do not act as acidic
hydrogen are in direct union with carbon atoms
only: (H,=C-C<gH).
A system of (■lassification of compounds may
be developed on the lines of the structure of the
molecules of these compounds. If this classifi-
cation is to be of much permanent value it must
be limited to compounds to which the funda-
mental conceptions of the system can be ap-
pUed. We have tried to show that this is
equivalent to saying that the system must at
present be limited to gaseous compounds. But
the vast majority of chemical compounds, other
than those of carbon, have not been gasified,
and most of them appear to be incapable of
existing in the gaseous state. Hence a system
founded on the conception of molecular struc-
ture cannot be strictly applied at present to the
bodies which come within the province of in-
organic chemistry. Some of the subsidiary con-
ceptions gained as the applications of the sys-
tem to carbon compounds axe developed may,
however, be used as aids in classifying non-
gasifiable bodies, provided always care be taken
not to overstep the limits imposed by the condi-
tions of the inquiry. Thus, arguing from the
similarities of properties exhibited by acids as a
class, and from what the hypothesis of molecular
structure helps us to understand of the connec-
tions between the functions of particular atoms
and the arrangement of all the atoms in the
molecules of gaseous acids, we may conclude that,
in the collocations of atoms which (by hypothesis)
form the reacting units of non-gasiflable acids,
there is more direct mutual action between the
atoms of replaceable hydrogen and some nega-
tive atoms or groups of atoms, than between those
atoms of replaceable hydrogen and the more
positive atoms of the reacting atomic complexes
Again, when we have learned from the study of
the gaseous compounds of phosphorus that an
atom of this element appears to be capable of
directly acting on, and being acted on by, not
more than five other atoms in a moleome, we
may conclude that in the collocations of atoms
which (by hypothesis) form the reacting units of
the non-gasifiable compounds of phosphorus,
each atom of this element is probably in direct
union with not more than five other atoms.
This tentative conclusion may then be appUed to
the development of limiting forms for phosphorus
Compounds ; the compositions of these com-
pounds may be represented so that they shall
all come under the limiting form BX^. But it ia
easy to forget the limits within which such
a method as this is of any real help. It ii easy
to forget that the notion of the equivalency of
atoms, on which such a conclusion as that just
reached regarding the limiting forms of phosphorus
compounds is really based, is a notion which, some-
whatvague in itself, becomesvaguer the moment an
attempt is made to apply it to discussions about
solid and liquid bodies, for which only the outlines
of a molecular theory have yet been drawn.
A system of classification, even of gaseous
compounds, cannot be reared on the conception
of atomic valency pure and simple. If one
atom can directly interact with, say, four other
atoms, the existence of a vast number of mole-
cules buUt up by the union of this atom with
those of two or three other elements becomes
possible. Why do not all these molecules exist 7
Because, replies the hypothesis of molecular
structure, the properties, and hence the possible
existence, of a molecule, depend not only on
the nature, number, and actual valencies, of
the constituent atoms, but also on the manner
in which the mutual interatomic reactions are
distributed in the molecule. Besides the valen-
cies of the atoms, it is necessary to consider the
distributions of the interactions of these atoms.
But how can we frame a working hypothesis re-
garding the distributions of the interatomic
reactions which shall help us to understand the
structure of the collocations of atoms with which
it seems we have to deal in hquid and solid
compounds ? These interatomic actions may be
distributed now in this way, now in that; the
effect of this or that reagent may be to cause
changes in the distributions of these reactions.
We have as yet no soUd basis of facts, or even
of intelligible hypothesis, on which to build.
Compounds of about fifty-six elements (exclud-
ing carbon) have been gasified ; as a rule, not
more than six or eight compounds of each ele-
ment are known in the gaseous state ; about sixty
of these compounds are available as data on
which to base arguments regarding the valencies
of perhaps forty-five elementary atoms. Sup-
posing, then, that a system of classification of
compounds is to be based strictly on the valencies
of the atoms in the molecules of these coul-
pounds, the system must be restricted to 200 or
300 compounds, formed by the combinations of
about fifty-six elements.
As regards the connections between atomic
valencies and atomic weights, it appears that
the valencies of the elementary atoms in certain
216
CLASSIFICATION, CHEMICAL.
series of elements vary from a minimum value
for the first member of the series to a maximum
tor the middle member, and back again to the
minimum value for the last member of the series.
Thus take series 2— Li, Be, B, 0, N, 0, F— the
following are the valencies of the atoms of the
members of this series so far as these valencies
have been established on reasonably satisfactory
data (the valency is in each case represented by
a Boman numeral placed above the symbol of
the element) : —
Qrov/pa.
I. II. in. IV. V. VI. vii.
Series 2— Li' Be" B™ C" N"' 0" F'
It is possible that the valencies of the elemen-
tary atoms vary periodically with variations in the
atomic weights of the elements. Should it be
established that this is so, we shall have another
illustration of the wide application and useful-
ness of the periodic law. But the classification
which is founded on the periodic law rests on this
generalisation as a whole, and not on any single
property of either elements or compounds. The
periodic law insists on the paramount importance
of the comparative study of aU the properties of
elements and compounds ; element must be com-
pared with element, compound with compound.
Thus, and thus alone, can we hope to gain a final
system of chemical classification. Thus, and
thus alone, can we expect to trace the fundamen-
tal relations which undoubtedly exist between
the properties and the composition, and between
the changes of properties and changes of com-
position, of homogeneous kinds of matter. On
the basis of the periodic law a scheme of classi-
fication of the chemical elements and compounds
may be raised, which exhibits (1) the composi-
tion of the compounds in so far as this can be
shown in the present state of chemical know-
ledge ; (2) the functions of the compounds, that
is to say the reactions in which they take part ;
and (8) the connections between the compositions
and the functions of the compounds ; and in thus
classifying the compounds of the different ele-
ments the method at the same time classifies the
elements themselves. M. M. P. M.
In connection with the subject-matter of this
article the following articles should be read : —
Atomic and ugleculab weiqhis; Chkuicmj
CEANOE ; EQUnilBBinM, CHEMICAIi ; EqUIVAIiENCT ;
FoBMUL^ ; MoiiECtTLAB STBUCIUSE OF MAITEB,
THEOBIES BEQABDINa; FeBIODIO LAW; FhVSICAIi
METHODS OP INQTIIBT USED IN OHEMISTET. Further
details of the properties of the various families of
elements and their chief compounds are given in
the following articles : — ^Ai/Kaline earths, metals
or THE (Ca Sr Ba) ; Alkalis, metals op the (Li
Na K Bb Cs, NH, — Tl) ; Boeon ; Oaebon geoup of
ELEMENTS (0 Si — Ti Zx Sn Ce Pb Th) ; Chbomium
OBOUP (Cr Mo WTJ) ; Coppee oboup (Cu Ag, An) ;
Eaethb, metals op the (A1 Ga In, Sc Y La Yb —
Tl) ; Halooens, the (F 01 Br I, ON— Mn) ; Hs-
dbooen ; Ieon oeoup (Fe Ni Co — Mn) ; Lead ;
MAGNESinM OEOTTP (Be, Mg Zn Od, Hg) ; Nitbooen
OEOUP (N P As V Nb Sb Di Er Bi) ; Noble metals
(Au, Bh Bu Pd, Os Ir Pt) ; Oxyqen geoup (0 S
Se Te— Cr Mo W U) ; Tin geoup (Sn Ge Pb);
Titanium gboup (Ti Zr Ce Tb).
The following memoirs and books may be con-
sulted by those who wish to trace the develop-
ment of the various schemes of chemical classi-
fication which have from time to time prevailed
in the science :—
Lavoisibe (Compound radicles), TraMi Hi-
mmtcm-e de CUrme (edit. 1789), 1, 197, 209.
Dumas and Boullas (Compound ethers), A.
Ch. 27, 15 (1828).
WoHLEB and LiEBia (Benzoyl compounds),
A. 3, 249 (1832).
Beezelius (Badicle of thebenzoic compounds),
A. 8, 282.
Bebzelius (Badicles of alcohol and its deri-
vatives), J". 1833. 189 ; P. 28, 617.
Liebiq (Ethyl), HandwHrterb. d. Chemie {1"
Auflage), article ' ^ther ';A.9,1.
LiEBiG (Acetyl, constitution of acetic acid,
&c.), A. 14, 133.
Dumas (Substitution), A. Ch. 56, 143 (1835) ;
TraAti de GMmie appliguie aiuc Arts, 6, 99.
LiuBENT (Nucleus theory), A. Ch. 61, 125
(1836).
Gbbhabdt (Conjugated compounds), iUd. 72,
184 (1888).
Dumas (Substitution), C. B. 10, 149.
Gbbhabdt (Atomic weights of oxygen, carbon,
&o.), A. Ch. [3] 7, 129 ; 8, 238 ; Pricis de Chimie
orgamgue (1844), 1, 47).
Gebhaedt (Homology), Pricis, 2, 489.
Laueent (Law of even numbers of atoms ;
nature of the elements in the free state ; monads
and dyads), A. Ch. [3] 18, 266 (1846) ; Chemical
Method, 46-96, et passim.
WuBTZ (Compound ammonias), 0. B, 28, 233,
323 (1849) ; 29, 169; C. J. 8, 90.
HopMANN (Compound ammonias), T. 1850. 93 ;
C. J. 3, 279.
Williamson (Mixed ethers, etherifioation),
C. J. 4, 106, 229 (1851).
WiLLiiMsoN (Constitution of salts), 0. J. 9,
350 (1851).
Gebeabdt and Chancel (Constitution of or-
ganic compounds), Compt. chim. (1851) 7, 65.
Gebhabdt (Basicity of acids), Compt, chim.
(1851) 7, 129.
Gebhabdt (Anhydrous organic acids ; olassi
fication by types), 0. B. 84, 755, 902 (1852) ;
0. J. 5, 127, 226 ; more fully A. Ch. [3] 37,285 ;
Dumas's Beport, C. B. 86, 505.
Bebthelot (Synthesis of fats ; nature of gly-
cerine), A. Ch. 61, 216 (1853-54).
Odling (Constitution of salts; polyatomic
radicles), 0. J. 7, 1 (1854).
WuETZ (Theory of glycerine-compounds;
polyatomic radicles), A. Ch. [3j 43, 493 (lS55).
WuBiz (Mixed radicles), ibid. 44, 275.
Gebhabdt and Chiozza (Amides), ibid. 46,
129 (1855-56).
H. L. Bupp (Polyatomic radicles), Pr. 8, 188
(1856).
WuBiz (Dihydrio alcohols), A. 100, 110; more
fuUy, A. Ch. [3] 55, 400 ^1856-59).
Kexule (Mixed types, radicles, &a.)', A. 104,
129 (1857);
Kekulb (Ditto ; tetravalent character of car-
bon atom), Ubid. 106, 129 (1858).
CouPEB (Valency of carbon and oxygen),
A. Ch. [3] 68, 504 (1858) ; A. 110, 46 (here fol-
lowed by critique by Buttlerow, 1859).
EoLBE (Constitution of lactic acid), A.
109, 257 (1859) ; same subject, ibid. 118, 22a
(1860).
COBALT.
217
Foster (Nature of radicles and types), B. A.
1859, 1.
WuBTz (Basioity of acids), A. Oh. [3] 51, 842
(1859).
Cahoubs (Oombining capacity of the elements ;
limits of combination), A. Ch. [3] 68, 5 (1860).
FiuNEiiAND (same subject), O. J. 13, 177
(1860).
WuBiz (Constitution of lactic acid), A. Ch.
[S] 69, 161 (1860).
Cahoubs (same subject), A. Ch. [3] 62, 257
(1861).
BuTiLEBow (Valencies of the elements), Z. 4,
649(1861).
EbiiEnmb^bb ^same subject), i&i<2. 6,18 (1862).
EoLBB (Classification of organic bodies), A.
113, 293 (1860); Critical Bemarks by Wurtz,
B^p. CUm. Pwe, 2, 364.
LossEN (Critical discussion of valency), A.
204, 265 (1883).
Lehmakn (Physical isomerism), Z. K. 1, 97.
MEin>Ei.EjEFT (Periodic law), G. Nj40and 41.
Papers on the applications of the periodic law
are numerous ; v. especially CarneUey, P. M. [5]
8,315; 18,1; 20, 259, &c.
LAtrsENT, Mithode de Ohrnnie, 1864 ; CaveU'
dish Society's translation, 1856.
Gebhabdt, TraiU de CMmie orgamigue,^ vols.
1853-56 ; especiaUy 1, 121-142 ; 4, 661-808.
Eekuii^, Lehrbuch der orga/wischen, Ohemie,
vol. 1 (1859-61).
OnLma, Mamial of Chemisiry, pt. 1 (1861).
BL0ii8TBAin>, IHe Ohemie des JeUteeit (1869).
Ii. Meyeb, Lke modemen Theorien der GhemAe
[4th ed. 1883; EngUsh ed. 1888].
OsiwAU], Iieh/rbueh der allgemeinen Ghertm.
(1885-87).
Patxison Muib, Treatise on the Primcvples of
Chemisiry (1884 ; 2nd edit. 1889).
Teousen, Thermochemische CFntersiuslmngen
[4 vols. 1882-86]. Condensed accounts of the
bearings of thermochemical investigation on che-
mical classification will be found in Jahn's Die
Orvmdsatze der Thermochemie (1882), and in
Pattison Muir's Blements of Thermal Chemistry
(1886).
CLOVES, OIL OF. Contains eugenol
C,oH,jOj. and a terpens OijHj,, (264° cor.) ; V.D.
7-7 ffittling, A. 9, 68 ; Brunlng, A. 104, 205 ;
Williams, A. 107, 242 ; Chnrchr G. J. 28, 113).
The terpene is converted by Br into G^^B^
(250°-260°)(Bec]£ett a. Wright, C. J. 29, 1).
CKICIK C,2H„0,5 (?). Occurs in the leaves
of Centa/uirea ben^dicta or Onictis benedictus and
bitter plants of the order GompositcB sub-order
Cynaroeephala (Morin, J, Ghmt,. Mid. 8, 105 ;
Scribe, G. R. 16, 803). Silky needles, with
bitter taste ; v. soL alcohol, v. si. sol. ether ; si.
sol. hot water. Dextro-rotatory, [o] = 131°
(Bouohardat). Its solution is rendered turbid
by long boiling. HjSO^ forms a blood-red solu-
tion. Cone. HClAq becomes green, and deposits
a resin on warming.
COAL TAB. The oily product of the distil-
lation of coal contains benzene, toluene, o-, m-,
and j)-, xylene, naphthalene, anthracene, phenol,
0-, m-, and j>-, cresol, and ammonia. _ The minor
constituents are water, hydrogen, nitrogen, car-
bonic oxide, COS, cyanogen, CSj, HjS, HON,
COj, methane, ethylene, acetylene, propylene,
■llylene, butylene, orotonylene, amylene, hexyl-
ene, hexinene, ennane, decane, styrene, mesi-
tylene, ^-cumene, terpenes, naphthalene dihy-
&ide, methyl-naphthalene, di-methyl-naphthal-
ene, diphenyl, acenaphthene, fluorene, phenan-
threne, fiuoranthene, ifi-phenanthiene, methyl-
anthracene, pyrene, ohrysene, picene, acetic
acid, acetonitrUe, tfaiophene, methyl-thiophene,
di-methyl-thiophene, phenyl thiocarbimide,
pyrocreosols, carbazole, phenyl-naphthyl-oarb-
azole (phenylene-naphthylene-imide), xylenol,
benzoic acid, (a)- and (^)-naphthol, pyridine,
pyrrole, methyl-pyridine, di-methyl-pyridine,
tri-metbyl-pyridine, aniline, qninoline, methyl- .
quinoline,| parvohne, coridine, mbidine, viridine,
lepidine, cryptidine, and acridinc (e/. Schultz,
Die Ghemie des Steinkohlentheers). Many of
the hydrocarbons present in coal tar are probably
formed from phenols by splitting off water, and
reduction (Schulze, A. 227, 162). Others are
formed by the action of heat on simpler hydro-
carbons. Thns marsh gas is converted by
passage through a red-hot tube into benzene,
propylene, and naphthalene ; ethane gives CjH,
, and hydrogen ; ethylene gives ethane and acetyl-
ene ; acetylene gives hydrogen, ethane, ethylene,
benzene, styrene, and naphthalene; benzene
gives diphenyl and hydrogen; whUe a mixture
of benzene and ethylene gives anthracene (Ber-
thelot, A. 142, 254 ; Schultz, A. 174, 203 ; 203,
118). Most of the bases are probably formed
either by the action of ammonia on the phenols,
or by the condensation of bases so formed with
themselves, with other bases, with phenols, or
with unsaturated hydrocarbons.
COBALT Co. At. w. 58-8. Mol. w. unknown
as element has not been gasified, [c. 1500°]
(Pictet, O. B. 88, 1317). S.G. 8-5-8-7 («. Play-
fair a. Joule, C. S. Mem. 3, 57). S.G. 8-96
(Bammelsberg, P. 78, 93). S.H. -107 (Begnault,
A. Gh. [3] 68, 5). V, = Vo (1 + 3 X •00001236<),
« = 40° (Fizeau, 0. B. 68, 1126).. E.G. at 0°
(Hg at 0° = 1) 9-685 (Matthiesen a. Vogt, P. M.
[4] 26, 242). T.O. (Ag=100) 17-2 (Barrett, J.
1878.131). S.V.S.c.6-84. H.C. [Oo^O',3ff O]
= 149,880 (T/i. 3, 306).
Occwrrence. — The metal is found in small
quantities (1 p.c.) in some meteorites. Chiefly
as smaliine, CoAs, in which Co is more or less
replaced by Ni and Fe ; and cobaU-glance, CoAsS
with Co partially replaced by Fe and Ni, Co
compounds also occur as oxide, sulphate,
arsenate, &o., chiefly with compounds of Ni, Fe,
and Mn. Compotmds of Co were used for pro-
ducing blue glasses in ancient times. ' Smalt '
was prepared in Saxony in the 16th century.
Cobalt was first recognised as an element by
Brandt in 1736. The name is said to be derived
from ' Kobold ' ( = sprite or goblin) a term applied
by miners in the middle ages to minerals which
were employed in the arts, but from which no
useful metal could be extracted.
Formation. — The ore is roasted to partly re-
move arsenic and sulphur ; the residue is dis-
solved in ECIAq with a little HNO, ; Fe is ppd.
by CaOjH, ; Gn, Bi, &c. are ppd. by H2S ; ad-
dition of bleaching powder then pps. Co^Os-zH^O ;
this is heated, and the 00,0^ formed is reduced
by beating with charcoal.
Prepa/ratum. — 1. The chief impurities to be
removed are As and other metals ppd. by
HgS, Fe, and NL Ihe roasted ore freed front
S18
COBALT.
gangue may be fused with nitre, tieated with
water to dissolve K arsenate, the residue dis-
BoWed in aqua regia, evaporated, diluted, satu-
rated with H2S, and filtered; the filtrate may
then be mixed with so much of a ferric salt that
a brown pp. (ferric arsenite and 'FejO^B.^) forms
on partial neutralisation, E2C03Aq is then added
BO long as the pp. is brown, and until a few drops
of the filtrate give a reddish pp. (showing ppn.
of Ni) with alkali ; almost every trace of As is
thus removed; the filtrate may be acidulated
with HOI and reppd. by H^S. To the filtrate
(which should be only slightly acid) solution of
bleaching powder or NaClO is added, so long as
the pp. is black (C03OJ, a reddish-brown colour
indicates ppn. of Ni oxides ; the pp. is washed,
and dissolved in nitric acid, the liquid is con-
centrated and neutralised by KOH, mixed with
ENOjAq, strongly acidified by acetic acid, and
allowed to stand for a few days ; the pp. of
E-Co nitrite is washed; dried, and strongly
heated ; K is removed by washing with water ;
the residual Co oxide is dissolved in oxalic acid,
and the Co oxalate is reduced by strongly heat-
ing in a closed crucible (Hermbstadt, J. pr. '61,
105; Patera, J.pr. 67, 14).— 2. The oxide, pre-
pared as described in 1, is reduced in a stream
of H at temp, above 320° (Muller, P. 136, 51).—
3. The oxide is dissolved in HClA.q and the solu-
tion is evaporated to crystallisation, the crystals
of C0CI2.6H2O are dried and heated in a stream
of CI ; and the CoCl^ thus obtained is reduced
by heating in H (Peligot, G. B. 19, 670).— 4. A
solution of the oxide is saturated with NH,
oxalate, and the liquid is warmed, a little BoUd
NHj oxalate is dissolved in the hot liquid which
is then electrolysed, using a Ft basin as negative,
and a piece of Ft foil as positive, electrode
(Classen a. Yon Beis, B. 14, 1622).
Properties. — Steel-grey, lustrous, crystalline
plates ; nearly white when polished ; hard ;
somewhat malleable ; very ductile at red heat
and upwards; slightly magnetic, even at fuU
red heat (Fouillet). The compact metal does
not oxidise in air at ordinary temperatures, but
when heated it forms CO3O4 ; the finely divided
metal obtained by reducing the oxide or chloride
in H at moderate temperatures is pyrophoric.
Combines directly with CI. Oxidised superfi-
cially by HgOjAq. Decomposes steam at red heat,
and NBC, to N and H. Dissolves in mineral
acids forming cobaltous salts. Cobalt wire
heated till superficially oxidised, and at once
plunged into fuming nitric acid, does not dis-
solve; it shows 'passivity' (NickWa, C. B.'SS,
284) due either to the formation of a protecting
layer of N oxides, or to a layer of cobalt oxide
(cf. passivity of iron, under Ikon). Co in thin
leaves is said to absorb H much as Fd does
(Bettcher, /. 1874. 295).
Cobalt is distinctly metallic in its chemical
behaviour ; CoO forms a series of weU-marked
normal salts, many basic salts are also known ;
CojO, dissolves in acids probably forming salts,
but these are very soon decomposed to cobaltous
salts ; double cobaltic salts are, however, stable,
«.g'.Co(NOj)3.3KN02('B.alsoCoBALTAMiNEs). When
CoO is added to molten EOH, the compound
(Cb,Oj),.E,0 is said to be produced, in which Co
forms part of the acid radicle (v. CobaiiTaies).
The Bidphides of Co show no acidic character.
The atomic weight of Co has been deter-
mined (1) from analyses of the sulphate and
chloride (Mariguao, Ar. So. 1, 373) ; (2) b|y reduc-
tion of CoO in H (Eusaell, C. J. [2] 1, 61) ;
(3) by reduction of NH,-Co cyanide and phenyl-
ammonium cobalt cyanide (Weselsky, B. 2, 592) ;
(4) by reduction (by heat) of strychnine- and
bruoine-cobalt cyanide (Lee, O. N. 24, 234) ; (5)
by reducing CoO in H (Zimmermann, A. 232,
324). Determinations of the S.H. have shown
that 58'8 and not a multiple of this number is
to be adopted. This result has been confirmed
by the isomorphism of several Co salts with the
corresponding salts of Ni and Fe.
Cobalt is very closely related in its chemical
properties to Ni, it is classed with this metal and
Fe, and it also shows analogies with Hn ; v. Ibon
QBOUF OF ELEMENTS.
Reactions anA. Combinations. — l.WithsfeoOT
at red heat forms CoO and H. — 2. Strongly
heated in air burns to Co,0,. — 8. Decomposes
ammonia at red heat to N and H. — 4. Dissolves
in mineral acids with formation of salts ; with
H2SO4 evolves SOj, and with HNO, gives N
oxides. Thomsen (Th. 3, 306) gives these
thermal data; [Co,ffSO*Aq] = 19,710 giving
CoSO, -H Hj- [Co,ffCl'Aq] = 16,190.— 5. Combines
with chlorine, bromme, and iodine, by heating
in contact with these elements, forming GoCl,,
CoBrj, and Colj, respectively. [Co,Cl^ = 76,480;
[Co,OP,Aq] = 94,820 ; [Co,Br^Aq] = 72,940 ;
[Co,P,Aq] = 42,520 {Th.3, 306).— 6. Heated with
sulptmr forms CoS and Co,S,. — 7. Combines
with selenion to form CoSe, by heating the two
elements together (v. Cobam, selekidb or). —
8. Combines with a/rsenia (v. Cobalt, absenides
of). — 9 Absorbs (? combines with) small quan-
tities of carbon when strongly heated with it,
forming a hard grey mass resembling steel. —
10. Forms alloys with several metals, especially
Sb, Bi, Au, Fe, Fb, Ft, Ag, Sn, and Zn ; little is
known of these bodies.
Detection a/nd estimation. — Co compounds
give a clear blue colour with a bead of borax or
m,icrocosniic salt in both blowpipe flames. Black
CoS is ppd, by alkaline sulphides, but not by
H2S in acid solutions. Ammmtia pps. blue basio
salts, soluble in Excess to a reddish liquid which
absorbs 0 from the air and becomes brownish ;
EOHAq pps. part of the Co as hydrated oxide
from this solution. Traces of Co are detected
by adding excess of NHjAq, andthenEaFeCyjAq,
when a dark yellowish red colour is produced
(Skey, 0. N. 15, 111) ; or by adding excess of
ECNAq followed by NH4 sulphide, when a blood-
red colour is formed which slowly disappears
(Tattersall, 0. N. 39, 66 ; Fapasogli, B. 12, 297).
Co may be estimated by ppn. as oxalate, which
is then decomposed by heat to metal. The Co
may be separated from Ni by evaporating an
acid solution to a small bulk, adding slight
excess of EOHAq, acidifying with acetic acid,
adding excess of a cone, solution of ENOj
strongly acidified by acetic acid, allowing to
stand for 24 hours in a warm place, and washing
the ppd. Coj(N02)s.6EN02 with solution of 1
part K acetate in 9 parts HjO. The pp. is dis-
solved in HClAq ; liquid is evaporated until very
cone, and all free acid is removed, KjCjOjAq is
added drop by drop until the pp. which forms ia
dissolved, a Uttle water is added, the liquid ii
COBALT.
219
heated to boiling, and rather more than an
equal volume of 80 p.o. aoetio aoid is added very
tUnoVy ; after standiiig 6 hours at about 50° the
ppd. Go oxalate is filtered of[, washed with a
mixture of equal yolumes of cono. aoetio acid,
alcohol, and water, and dried ; it is heated in a
closed crucible, then strongly in the air (to
oxidise C), and the oxide is reduced by strongly
heating in H. After weighing, the Co should
be washed in hot water and again heated
in H (Classen, Fr. 18, 189). Classen recom-
mends the electrolytic estunation of Co by
depositing the metal from a solution in excess
of warm KsCjO^Aq (v. Classen's Quantitative
Analyse duroh Electrolyse, Berlin, 1886. A
description of the apparatus will be found in
Dittmar's Exercises in Quantitative Chemical
Analysis, Glasgow, 1887). WoUE (Fr. 18, 38)
proposes to determine minute quantities of Co
fay a spectroscopic method based on the absorp-
tion-spectrum of very dilute solutions of Co to
which excess of NHjAq and a little NH^SCy
have been added.
Technical appKcatUms. — ^By adding a fraction
of a per cent, of Hg to Go an easUy worked
metal is obtained, which is very compact and
lustrous, and resists the action of the air (Fleit-
mann, B. 12, 454 ; Biedermann's Ohem.-techn.
Jahrber. 1884^5. 25). Many metals may be
covered with a thin deposit of Co by electrolysing
a fairly cone, solution of Co01j.NH,Gl (Bottoher,
W. J. 1876. 219 ; Gaifie, O. B. 87, 100) (v. Co-
BAIiT COLOUBINO JUTTEBS, p. 229.)
Beferences. — ^Besides tiiose in the text the
following are of importance : (1) Begarding the
metallurgy and preparation of Co ; Manh^s {B.
17, 622), Wohler (P. 6, 227), Liebig(P.18, 164),
Langier {A. Oh. 9, 267), Stromeyer (A. 96, 218).
(2) Begarding the properties of Co ; DeviUe (I).
P. J. 140, 428), Barrett (/. 1873, 131). (3) Be-
garding technical applications of Go; Wiggin
(W. J. 1881. 69 ; v. also W. J. 1883. 149). (4)
Begarding separation and estimation of Go;
Kscher (P. 74, US), Braun (Fr. 7, 313), Liebig
{A. 65, 244; 87, 128), Fleischer (J.pr. 1870, 2,
48), Donath {B. 12, 1868).
Cobalt, alloys of. Little is known of these
bodies ; Co seems to form alloys with Sb, Bi,
Au, Pe, Pb, Pt, Ag, Sn, and Zn.
Cobalt, ammonia compounds of v. Gobali-
AUINES, p. 222.
Cobalt, antimonate of. Co(Sb03)2.!cE20
(Heflter, P. 86, 418 ; cf. vol. i. p. 285).
Cobalt, arsenates of. GoH,(As04)2 and
Co,(AsO<)j.8HjO; v. vol. i. p. 308.
Cobalt, arsenides of. Co and As are said to,
form a grey-black, porous, mass, when heated
together in the ratio of 2 parts Co to 3 parts As.
The mineral smalOne is more or less pure Co
arsenide, GoAsj: aniskutteruditeianeaxlj-pum
CoAs,.
Cobalt, arsenite of. GoaH|i(AsO,)4.H20; v.
vol. i. p. 306.
Cobalt, borate of. Probably
2C6Bfl,.Co0^.3njO (H. Eose, P. 88, 299).
Cobalt, bromide of. CoBr^. Mol. w. unknown.
[Co,Br=,Aq] = 72,940 (Th. 3, 306). A green, deli-
quescent, lustrous solid; prepared either by
heating Co in Br vapour (Bammelsberg, P. 55,
244) ; or by warming Co in contact with Br and
B»0, evaporating over HjSOi, drying the crystals
of CoBrj.6H,0, and heating to o. 130° (Hartley,
O. J. [2] 12, 214). The crystals of CoBrj.6H20
melt at 100°, giving the purple-grey hydrate
GoBrj.2HjO (Hartley). CoBrj absorbs NH, form-
ing OoBr,.6KH„ from which all NH, can be
removed by heat (v. GobaiiTAuinbb). GoBrjAq
and PtBr^Aq evaporated yield carmine, rhom-
bohedral, very deliquescent, crystals of
CoBrjrPtBr,.12HsO ; S.G. 2-763 (Topsoe, J. 1868.
276).
Cobalt bromide, hydrated ; v. Cobalt, bbomidb
OP.
Cobalt, carbides of. Co absorbs G when
heated with charcoal, forming a hard, grey, steel-
like solid. It is not known whether definite car-
bides are formed or not.
Cobalt, chloride of, GoCl^. Mol. w. unknown.
[Co,Cl»] = 76,480; [CoCP.Aq] = 18,340 {Th. 3,
306). Absorption-spectrum, v. Eussell, Pr. 32,
258.
Preparation. — 1. CoO, or CoCO,, is dissolved
in dUute HClAq, the solution is evaporated until
a blue-green solid separates, which is sublimed
in a stream of dry 01 or dry HGl. — 2. Finely di-
vided Co or CoS is heated in a stream of 01. —
3. G0OI2.6H2O, obtained by crystaUising solution
of CoO in H01A.q, is heated to 120° ; traces of
oxyohloride are always formed thus (Potilitzin,
£.17,276).
Properties and BeacUons. — Blue crystalline
scales : easUy soluble in water forming reddish
liquid, also in absolute alcohol. CoOljAq of dif-
ferent S.G. contains as follows (Franz, J. pr. [2]
5, 274) :-
S.G. OoQ, P.O. 3.Q. OoCl, p.a.
1-0496 6 1-2245 20
1-0997 10 1-3002 25
1-1579 15 1-3613 saturated at 17-5°.
A saturated alcoholic solution contains 23*6 p.o
CoOlj, appears blue by reflected light and almost
black by transmitted light, becomes colourless
when dUuted so that one part CoGli is contained
in 10,000 parts of solution, but blue colourreturns
on warming; S.G. of this solution is 1-0107. Ad-
dition of water to the blue alcoholic solution pro-
duces violet and then red colour ; a method of
determining water in alcohol or in organic com-
pounds miscible with alcohol has been founded
on this reaction (Winkler, J. pr. 91, 209). An
aqueous solution of CoCI^ becomes blue on addi-
tion of cone. HClAq, H2SO4, or other dehydrating
agent ; also on heating, the temperature of change
being the lowerthe more cone, is the solution, thus
a 50 p.c. solution changes colour at 60°-100°, a 25
p.c. solution at 85°-135°, and a 10 p.c. solution
at 180°-207° (Tiohborne, J. 1872. 27). Addition
of HOI to cono. CoGl^Aq pps. crystals containing
from 1 to li HjO (Ditte, A. Ch. [5] 22, 551).
The change of colour of solution of OoClj from
blue to red is accompanied by hydration (Poti-
litzin, B. 17, 276) ; it is not an isomeric change
as supposed by Bersoh {W. A, B. 56, 724).
CombinaUons. — 1. With water to form va-
rious hydrates (v. PotUitzin, B. 17, 276). The
hexahydrate, GoCl2.6H20, separates by care-
fully evaporating a red solution of CoO or OoOD,
in HClAq; dark red monoolinic crystals; S.G.
= 1-84 ; lose water at 30°-35°, and at 45°-50° form
the dihydrate ; slowly lose water over HjSO,
forming the dihydrate; [CoC1^6ffOJ= 21,190 J
230
COBALT.
[CoCa'.BH'O.Aq] = - 2850 (Th. 3, 306). The di-
hydrate, C0CIJ.2H2O, forms a rose-red finely
crystaUine powder ; prepared as described above ;
absorbs water from the air forming the hexahy-
drate. The monohydrate, Co01,.HjO, is ob-
tained by heating the dihydrate to 0. 100°, or by
slowly evaporating a solution in absolute alcohol
of theheza- or di-hydrate, the temperature being
gradually raised to 95°. Lustrous, violet-blue,
c^staUine needles : dehydrated at 110°-120°. —
2. WithommoniatoformthecompoundsM.eNHj,
M.4NH,, and M.2NH, where M = CoCl, («. Oo-
BAiiTAMiNEs). — 3. With a/mmonmm chloride to
form C0G4NH4CI.6H2O ; prepared by evapo-
rating a mixture of solution of CoO in 2 parts
HCl&q and NH, in 1 part EGlAq (Hantz, A.
66, 284); not obtained from mixed solutions
of CoOl, and NH,01 (Merrick, J. 1876. 251) ;
forms ruby-red, deliquescent crystals. — 4.
With a/nMme,]paratolvAidme, and xylidme. The
aniline compounds are GoCl2.(CsHs.NE2)2 and
Co01j(0,H5.NHj)j.20jH,0 ; the former, lustrous
blue crystals, is obtained by dissolving C0CI2
in hot aniline and crystalUsing from abso-
Inte alcohol; the latter, rose-red leaflets, by
adding aniline to an alcoholic solution of
OoCl,; at 100° alcohol is completely removed.
The toluidine and zylidine compounds, ob-
tained similarly to tite aniline compound,
are blue needles: CoGl2.(C^,.GH,.NH2)2 and
CoGl2.(GA(CH,)2.KH2)2(Lippmanna.yortmann,
B. 11, 1069 ; 12, 79).— 6. With cadmium chlo-
ride, gold chloride, and einc chloride to form
CoGl2.2GdGlj.l2HjO, G6Glj.2AuGls.8H2O, and
CoCl2.ZnGl2.6H2O, respectively ; by evaporating
mixed solutions of the constituent chlorides. —
6. With cobaltotis oxide; when dilute NHjAq^
is added drop by drop to boiling CoGljAq a blue
pp. is formed, which turns peach-red ; this pp.
when dried probably has the composition
2G0GI2.6C0O.7H2O (Habermann, M. 5, 442).
Cobalt chloride, hydrated ; v. CobaiiT, ohlo-
BtDB or ; OombinaUons, No. 1.
Cobalt, ohromates of ; v. Chbomates.
Cobalt, cyanides of, also Cobalto- and Cobaltl-
eyanides ; v. Cyanides.
Cobalt, fluoride of, C0PJ.2H2O. Mol. w. un-
known. Bose-red crystals ; by dissolvitig CoO in
excess of HEAq ; soluble in Aq containing HF,
or in a little cold water ; decomp.3Bed by much
hot water to oxyfluoride Go20F2.H20 (Berze-
lius). Combines with potassium fluoride, sodium
fluoride, and armiuym/wm fluoride, to form double
salts; CoPyKP-HjO, OoP2.lfaP.H2O, and
CoP,.2NH4P.2H20 (Berzelius ; Wagner, B. 19,
897).
Cobalt, haloid compounds of. — These com-
pounds all belong to the form GoX,; X^^p, Gl,
Br, or I. None has been gasified, and therefore
the molecular weight of none is baown'with cer-
tainty. These compounds are greenish-blue
solids; all form hydrates, which are reddish.
All are soluble in water, and all seem to form
double compounds with alkali haloid compounds.
A very few oxyhaloid compounds have been pre-
pared.
Cobalt, hydrated oxides of; «. Gobalt, oxides
AND BYDBOXIDES OF.
Cobalt, hydroxides of; v. Cobalt, oxides and
■ncBOSSDSB ov.
Cobalt, iodide of. Col,. Mol. w. unknown. A
black, graphite-like, solid ; obtained by digesting
Go with water and iodine, filtering, evaporating
the red liquid till it gets thickish, cooling over
H2SO,, and heating the crystals to 130° (Hartley,
C.J. [2] 12, 502). The liquid prepared as described
yields green crystals of G0I2.2H2O ; these are ex-
ceedingly deliquescent. When the same solution
is kept at 16° or so for some days red crystals of
C0I2.6H2O separate (Hartley ; Erdmann, J. pr.
7, 354 ; Eammelsberg, P. 48, 155). Col, com- :
bines with NH, to form G0I2.4NH3 (Bammels-
berg, P. 55, 245).
Cobalt, oxides and hydroxides of. — Cobalt
forms three well-marked oxides: CoO, Co,04,
and C02O3 ; four other oxides are known, which
are usually regarded as compounds of the first
and third of these, viz. CojOs.2CoO, C02O3.3C0O,
Co20s.40oO, and Oo20a.60oO. The monoxide
CoO is distinctly basic ; the sesquioxide C02O,
dissolves in acids, probably with formation of
salts, but very few salts corresponding to this
oxide have been obtained as they are very easily
reduced to salts of CoO ; the other oxides do not
form corresponding salts. The monoxide is
stable when heated to a moderate temperature,
but at full redness it is oxidised to CosO, ; CojOg
is deoxidised by heating strongly with formation
of CogOj. Several hydrates of the various oxides
are known.
I. GoBAiiTous oxiDB CoO. {Cobalt monoxide,
cobalt oxide.) Mol. w. unknown. A greenish-
brown powder, slightly hygroscopic. S.Q-. 5-59
to 5-75 (Playfair a. Joule, 0. S. Mem. 3, 57).
Prepared by heating CoCQ, or Co(OH)2 (q. v.) in
complete absence of air (Beetz, P. 61, 473) ; or
by heating CoGl, in steam (Schwarzenberg, A.
97, 211) ; or by heating C03O4 in a stream of CO,
(Bussell, C. J. 16, 61). CoO is unchanged in air,
but when strongly heated it is oxidised to C03O4 ;
it is reduced to Co by heating in H or CO, or with
G ; it is quickly changed to CoS by heating in
H2S.
CoBALTons BYDBoxiDE Go(OH)2. {Cobalt hy-
d/rate. Hydrated cobaltous oxide.) [Co,0,H'0]
= 63,400 (Th. 3, 806). Obtained by adding
potash to solution of a cobaltous salt in absence
of air ; the pp. is a blue basic salt, which slowly
changes to the rose-red hydrate ; the change is
quickened by heating (Winkelblech, A. 13, 148,
253 ; Beetz, P. 61, 478). If potash is added to
a boiling solution the pp. contains alkali and
some basic salt (Premy, A. 80, 277 ; 83, 227,
289). A rose-red powder ; absorbs O from air
turning brown ; heated in absence of air gives
CoO. Cobaltous oxide and hydroxide dissolve
in acids forming stable cobaltous salts (v. Cobalt,
SALTS ov, p. 221). [GoO"H^H2SO'Aq] = 24,670;
[CoO'H^H^CPAq] = 21,140 (Th. 3, 307).
II. CoBALTio OXIDE CojO,. (Cobalt sdsquioxide.
Cobalt peroxide.) Mol. w. unknown. A steel-
grey, lustrous solid. Heated in air gives GogO,.
Dissolves in cone, acids, but very few salts have
been obtained corresponding to the oxide ; solu-
tion in cone, cold acetic acid gives brown pp. of
C02O3.3HJO with an alkali ; some double salts
are known, e.g. Co2(NO,)„.6KN02 («. Cobalt, salts
or, p. 221). Prepared by gently-heated Co2NO,
80 long as reddish vapours are evolved, powder-
ing finely and again gently heating ; or by heaU
ing 00208.3H20 to 600°-700°.
COBALT.
SJTi
CoBAiiTia HYDBoxiDBS. The oompound
Coj(OH), or CojOa.SHjO is obtained by expos-
ing a solution of a cobaltous salt, with excess of
NHjAq added, to ihb air until brown, and ppg.
by KOHAq ; or' by ppg. a oobaltoas salt solu-
tion by a hypoohlorite in presence of alkali ; or
by passing Gl into, or adding BrAq to, Co(OH)2
or CoCOj suspended in water ; the pp. is dried
by pressing between paper. A dark-brown powder
[Co^0^3ffO] - 149,380 ; pCoQ-H^Cff 0] =
22,580 {Th. 3, 306). By drying at 100°, or by
prolonged exposure over HjSO,, the hydrate
C0JO3.2H2O [?CojO(OH)J is obtained. The
same hydrate is formed as a black lustrous
deposit on the positive pole, when a slightly
alkaline solution of cobaltous-potassium tartrate
is electrolysed, using Pt electrodes (Wernicke, P.
141, 119) ; S.a. as thus obtained =2-483. The
hydrate 3Co20,.2H20 is obtained by heating
GoOlj and Co2(NH,),g01, in the ratio 2:1 mols.,
with water in a open vessel (MiUs, P.M. [4] 35,
257). .
The cobaltic hydrates lose water when gently
heated, giving CojOj ; when strongly heated they
yield C03O4. They dissolve in cold cone, acids,
forming brown solutions ; these solutions are
decomposed on warming and thus give cobalt-
ous salts ; the solution in cone, acetic acid is
{airly stable ; potash pps. Co^Oj-SH^O from
this solution. Freshly ppd. Co^Os.SHjO dis-
solves in neutral (NHjjSOjAq forming a solu-
tion of CojO3-10NH3.6SO2 (Geuther, A. 128,
157).
III. CoBALio-coBAiiTia OXIDE G03O,. (Block
oxide of Cohalt.) Mol. w. unknown. Obtained
by strongly heating in air, or in 0, GoO, Go(OH)2,
CojO, or any of its hydrates, GoCOj, Go(NOj)2, or
CoCjO,. A black amorphous powder which slowly
absorbs water from the air. S.G. 5-833-6-296
(Bammelsberg, J. 2, 282). Obtained as lustrous,
metal-like, greyish-black lulcroscopic octahedra,
by strongly heating a mixture of GoOl, and
NH4CI in a stream of air or 0, or a mixture of
006204 and NHjGl in 0, and treating the residue
with hot cone. HGlAq. The crystals are unacted
on by many cone, acids, but dissolve slowly in
cone. HoSOj (Schwarzenberg, A. Wl, 211) ; they
are non-magnetic.
Hydeates of coBAiiTO-ooBAiiTio OXIDE. Three
have been described. G0JO4.2H2O, obtained by
exposing to ordinary air Co,0, prepared by heat-
ing O0GO3 ; Go304.3H,;0, obtained by boiUng a
solution of roseo-cobaltio sulphate (Genth a.
Gibbs, Am. S. 23, 257) ; Go304.7H20, obtained by
allowing Go{OH)2 ppd. by adding excess of
alkali to a cobaltous solution to stand in the air
(Fremy).
IV. OtHBE OOBALIO-COBALTIO OXIDES. (I.)
Ob208.2CoO ; a black powder, obtained by heat-
ing dried GoGO, to 100°-150° in a closed crucible,
or by heating luteo- or purpureo-oobalt chloride
with 30-40 parts water to 70°-100° in a sealed
tube (MiUs, P. M. [4] 35, 257). (u.) Go20,.3CoO ;
obtained by beating purpureo-cobalt chloride
with 2 mols. GoCL, and some water to 100° in a
sealed tube (Mills, I.e.). (iii.) Go^03,4GoO; a
black powder, unchanged by boiling with HNO3
or HjSO,, obtained by strongly heating cobalt-
ous salts in air. (iv.) CojOs-eCoO ; obtained
with 6H2O by adding NHjAq to Co(N03)2Aq and
allowing to stand in air tUl pp. is yellow. _
Cobalt, ozyhaloid compounds of. Very few
of these compounds have been prepared.
2CoOLj.6OoO.7H2O, V. GOBALT, OmOEIDB OF;
CombmaUons, No. 6. G0F2.G0O.H2O, v. CobalIj
FLUOBIDB OP.
Cobalt, ozysulphide of, OojOS. ( = GoO.GoS).
Dark-grey powder ; by heating G0SO4 in H.
Pilute acids dissolve GoO; cono. acids also
evolve H2S ; heated, gives GoO and SO,.
Cobalt, phosphide of, C03F,. Black powder ;
obtained by ppg. GoOljAq by NajHPO^Aq and
heating the ppd. phosphate in a stream of H;
also by heating GoCl^ in PH,. Insoluble in
cono. HGlAq; easUy soluble in HNOaAq. Go
and P combine, by heating Go with a mixture ol
P2O5 and charcoal.
Cobalt, salts of. Compounds obtamed by
replacing the B of acids by Co. Many of these
salts are known ; most of them belong to the
class of cobaltotis salts GoX, where X=G1, NO,,
§2<> IPO4, &a. ; a few double cobaltic salts GoX,
are known. The Go salts are generally obtained
by dissolving GoO or C0O.H2O in acids, or by
double decomposition from other Co salts.
Cobaltous haloid salts, sulphate, nitrate, and
some others, are soluble in water ; the carbonate
and phosphate, &o., are insoluble. Co forms
many basic salts. Aqueous solutions of cobaltous
salts are generally pink ; when very cone, they
usually become blue to blue-green ; this colour-
change is accompanied by dehydration and
rehydration (c/. Gobalt, chloeidb or ; Properties
and Reactions). For some account of the resem-
blances between Fe,Ni, and Gov. Ibon Gbouf oi*
MktaiiS. Cobaltous salts closely resemble Xi
salts ; many of them are also very similar to,
and isomorphous with, ferrous salts. Cobaltic
hydrate Co20,.3H20 dissolves in cone, cold acids
probably forming cobaltic salts ; on warming,
these solutions are generally quickly decom-
posed with production of cobaltous salts ; a
solution in acetic acid is fairly stable. When
ENO2 is added to an acetic acid solution of a
cobaltous salt a pp. of the double cobaltic
salt Go(N02),.3KN02 is obtained. As no com-
pound of Co has been gasified the formulse of
the Co salts are not necessarily molecular. The
chief salts of oxyacids are the carbonates, ni^
irates, phosphates, and sulphates ; chlorate,
bromate, iodate, nitrite, phosphite, sulphite, and
a few others, are also known (v. Cabbokates,
HiTBATES, &B.). A great many double com-
pounds of Co salts with ammonia are known
\v. CobaiiIAuines, p. 222).
Cobalt, seleiride of. OoSe. Go and Se com-
bine when heated together, forming a metal-like,
lustrous, greyish mass, which is fusible at red
heat (Berzelius). The oompound GoSe is ob-
tained by passing vapour of Se over hot Co in
an atmosphere of H ; S.G. 7-65 ; when melted
under borax it forms a yellow, crystalline, metal-
like soUd (Little, A. 112, 211).
Cobalt, sulphides of. Go and S combine
directly in difEerent proportions. Sulphides are
also formed by ad£ng alkali sulphides to co-
baltous salts, and by passing HjS into an acetio
acid solution of C02O3, orCoO,and in various other
ways. The following sulphides are known :
Co^S,, OoS, Go,S,, Co,S„ CoSji these ^e th?
232
COBALT.
simplest formolse that oan be given, but they
are not necessarily molecular. The sulphides
of Co are basic ; GoS combines with AS2S3 and
SbjSj.
I. CoBAiiTona suiiPHTDE OoS. {Cobalt mono-
suTpMde.) Oean.TBTia,tvrea.s Syejpoorite. Prepared
by heating Co with S, or CoO with S, or C0SO4
with BaS and excess of NaCl; forms bronze-
coloured, lustrous needles, soluble in acids.
Also obtained as a black amorphous powder by
adding NH4 sulphide to an aqueous solution of
a cobaltous salt, or by passing HjS into a dilute
acetic acid solution of GoO, or into water hold-
ing Ge(0H)2 in suspension; the black pp. is
soluble in dilute mineral acids, but not in acetic
acid; insoluble in alkali sulphides; when moist
it oxidises rapidly in air to C0SO4. Non-
magnetic (Hjordtdahl, C. B. 65, 75). Com-
pounds of GoS with As and Sb sulphides,
M2S3.2C0S, are obtained by adding Go solutions
to Na thio-arsenite, &o.
II. GoBAIiTIO SULPHIDE GOjS,. (Coholt SBS-
gmaulpkide.) Occurs native as Cobalt-pyrites in
octahedra. Prepared by heating GoS or Go(OH)2
in a stream of H^S, or by strongly heating a
mixture of CoO, S, and EOH, and washing with
water ; forms a graphite-like crystalline powder.
Also obtained as an amorphous black pp. by
passing H^S into a solution of GOjO, in acetic
acid, or by adding NH4 sulphide to the solution
of a roseo- or purpureo-cobalt salt. Insoluble in
KGNAq, thus differing from NiS.
III. Cobalt bisulphide GoSj. {Cobalt per-
sulpMde.) Cobalt-glance is approximately pure
G0S2.G0AS2. Obtained by moderately heating a
mixture of 1 part dry GoO with 3 parts S, or of
1 part CoCO, with 1^ parts S, until excess of S
has been removed (Setterberg, P. 7, 40). A black
lustrous powder ; heated in absence of air to red-
ness forms GoS ; unacted on by acids except
cone. HKO3 and aqua regia.
IV. GOBALIO-OOBALTIO SULPHIDB COjS,.
Occurs native as Lmneeite. Formed, as a
greenish-black powder, by heating GoCljAq with
E polysulphide solution to 160° (S^narmont,
A. Ch. [3] 30, 137).
Y. The sulphide Co^S, is said to be obtained
by heating C0SO4 to whiteness in a carbon
crucible, or by strongly heating Go vrith S, or
CoO with HjS (Hjortdahl, 0. B. 65, 75). A grey
metal-like, lustrous mass, soluble in hot HOlAq
with evolution of H2S.
Cobalt, Bulphooyanide of, Co(SOy)2; v. Sul-
PHOOYANiDES, Under Cyanides.
Cobalt, borotnngBtate of; v. BosoTniiasTATEB,
nnder Tdnosten. M. M. P. M.
COBALTAMINES. {Cobaltammormm, com-
pounds. Cobalt-ammuyrda, compounds. Ammo-
mo-cob'alt salts. Ammomacal cobalt bases.)
Compounds of anunonia, cobalt, and negative
ladicles, formed either by combination of NH,
with cobaltous salts in absence of air, or by re-
actions between cobaltous salts and ammonia in
presence of air.
Bergmann noticed the solubility of cobalt
salts in ammonia: Tassaert {A. Ch. [1] 28, 95,
[1799]) noted that colour-changes occur when
these solutions stand in the air. Th^nard {A. Ch.
[1] 42, 211 [1803]) and Proust {A. Ch. [1] 60, 264
[1806]) explained these changes as caused by
absorption of oxygen from the air. Quantitative
measurements of the changes in question werf
made by L. GmeUn (S. 36, 236' PfaH (S. 35, 486),
Dingier {B. J. 10, 139), Hess (P. 26, 547), and
Winkelblech {A. 13, 259). Beetz (P. 61, 489 ;
B. J. 23, 169) and H. Eose (P. 20, 147) carried
further the investigation of the compounds pro-
duced. In 1850-60 Gibbs (P. Am. A. ; v. post)
began his investigations of the compounds formed
when ammoniacal solutions of cobalt salts are
exposed to air ; these researches form the basis
of our knowledge of the subject. The chemists
who have chiefly contributed to the elucidation
of the subject of ammonio-cobalt salts, besides
Gibbs, are Fremy, Claudet, Gen^h, Braun, MiUs,
Vortmann, F. Bose, and Jorgensen (references
will be given to original memoirs by these
and other chemists under the individual com-
pounds).
Some cobaltous salts combine with ammonia
in absence of air, forming salts which crystallise
from ammoniacal solutions but are decomposed
by water ; these a/mmMi/io-cobaltous salts, or
cobalto-anvines, generally belong to the form
M.6NH, where M = a cobaltous compound, e.g,
G0CI2 or C0SO4. Many cobaltous salts in solu-
tion react with ammonia in presence of air to
form compounds of the type GojXj.asNHj where
X = an acidic radicle. These ammondo-eobaltic-
salts, or cobalti-amines, may be classified, pri-
marily, according to the value of a; in the general
formula Go2Xg.xNH3, and secondarily according
to the nature and relation to the rest of the salt
of the acidic radicl« X.
Becent researches have shown that when
ammonia is added to a cobaltous salt solution in
presence of air, the cobaltous compound probably
oxidises, and at the same time combines with
ammonia, and that the various ammonio-cobaltio
compounds subsequently produced are derived
from these oxidised compounds by removal of
oxygen and ammonia, followed in some cases by
recombination with more ammonia. The final
production of this or that ammonio- compound
seems to depend chiefly on the relative masses
of the cobaltous salt and ammonia or ammonium
compound originally present.
The oobaltamines form compounds with many
acids and with metallic salts. The mutual rela-
tions of the various classes of oobaltamines, and
the constitution of each class, are not yet
thoroughly elucidated. The following classifica-
tion is a fairly satisfactory scheme of arrange-
ment, and is generally adopted : —
I. COBALTO-AMINES or AMMONIO-GO-
BALTOUS SALTS. Formed by the reaction of
cobaltous salts in solution with ammonia in
absence of air. These compounds belong to the
form M.ieNH, where H = a cobaltous compound
and X is generally = 6.
II. OXY-COBALTAMINES or AMMONIO-
OXTCOBALTIC SALTS. Formed by prolonged
oxidation of ammoniacal solutions of cobalt salts
by a stream of air. Most of these compounds
may be represented as belonging to one or
other of the series Co2(NH,),oB,.OH.O.OH and
Go2(NSC,),gBs.O.OH, where B=> an acidio radicle
01, Br, I, ?^|PO„4o.
in. COBALTI-AMINES or AMMONIO-GO-
BALTIC SAXiIb. Formed by exposing ammo
C0BALTA5IINES,
niacal solutions of cobaltons salts to the air, and
adding an aoid or a salt. These compounds may
be divided into four main series : —
(i.) Hexauines or Hi:xAMiiomo-ooBAi.Tia salts ;
Co,(NH,).Ki. e.g. Oo,(NH3).(SOj3.6H,0. These
salts are also called dichrocobalHo salts.
(ii.) OCTAMINES or OOTAMMONIO-OOBALTia BALIS ;
0Oj(NH,),E% e.g. Coj(NH3),01r2H,O.
(iii.) Decamhies or Deoammonio - cobaiiIic
baits; Oo,(NH3),^',e.j. Coj(NH3),„(OH)8.
(iy.) DOSECAMINES or DoDECAMMONIO-OOEAIiTIO
SALTS ; 0oj(NH3),jais e.g. Coj(NH3),j(CO,)3.7H,0.
The fourth series is also called the series of
Vuteo - eobaltarmmes or luteo - ammomo - cobaltio
salts.
The octammes and decammes are generally
divided each into three divisions : —
OCIAMINES.
(a) Praseo-eobaltio salts; normal salts,
e.j.Coj(NH3)3(SO,)3.4HjO.'
(&) Pusco-cohaltic salts; basic salts, e.gr.
Co,(NH3)8Cl<(OH),.2H,0.
(c) Groceo-cohaltic salts, also called
mtrammes of the octamme series; derived from
praseo-salts by replacing | of B by NO^ e.g.
Oo,(NH3).SO,{NO,),.
Decamineb.
(a) Boseo-cobaltic salts; \ „,' tfnt^
CoiNH,),.Cl,2H,0 ^°-*^*y
(b) Purpureo-cobaltic salts; .1 '
(3o,(NH3),.01.. j J^^.^_
(e) Xantho-eobaltic salts, also called
tiitrammes of the deca/rmne series ; derived from
purpureo- or roseo-salts by replacing § of E by
NO, e.g. Co,(NH3),„Cl,(NO,),.2H,0.
Many cobaltamines of different classes com-
bine with acids and with metallic salts to form
double compounds.
The empirical formulae given to the cobalt-
amines do not sufficiently represent the proper-
ties of these compounds. It is sometimes neces-
sary to distinguish between the functions of
different radicles in the same compound ; and
isomerism is exhibited by some of these bodies.
Thus, in the ootamine series, two octamine chlo-
rides exist, Co2(NHa)sCl5.2H20 ; one is green, it
loses all its water at 100^, its aqueous solution
is easily decomposed giving a pp. of CojOj.SHjO ;
when the solution of this salt is treated with
fairly cone. HOlAq a violet salt crystallises out,
having the same composition as the green salt ;
this violet salt does not begin to lose water at
120°, it is considerably more stable than the green
salt. These two salts are representatives of two
subdivisions of the division jpraseo-saZfs ; the
subdivisions are known as oatamine-praseo-salts
ani oetamme.pwrpureo-saUs respectively. Again,
iu the decamine series; the chloride Coj(NH,),„Cl,
is a violet-red solid which dissolves in water,
and when digested with dilute HClAq yields a
red diohroio powder having the composition
Ooj{NH,),„01s.2HjO ; this salt is very unstable,
it is changed to the violet-red compound on
warming or on solution in water ; a solution of
this salt is not ppd. by Na^PjO^Aq, while a solu-
tion of the violet-red salt is ppd. by this reagent.
These two salts are representatives of two divi-
tions of the decamine si:iiiEB,.viz. the purpurea'
and roseo-deeamines. Some of the pnrpnreo-
salts crystalUse with xRfi, e.g.
00j(NH8)„(SO4),.HjO ; but such salts lose water
without undergoing essential change, hence the
water is water of crystallisation, whereas in the
roseo- salts the water seems to be rather water of
constitution. Again, there is a compound of the
purpureo - division of the decamine series,
Co2(NHj),„(Sb,)j(NOj)j, which is isomeric with
another compound of the same division, and
both are isomeric with a roseo-salt of the deca-
mine series. So also in one of the series of oxy-
cobaltamines, viz. the series Co2(NE3),gB3.0.0H,
f of the radicle E are more firmly held to the
rest of the salt than the remaining one-fifth.
It is generally possible to give formulie to
each series, or division, which shall more or less
satisfactorily represent the typical reactions of
the compounds as connected with the arrange-^
ment of the different radicles, and ammonia,
relatively to the cobalt atoms ; but, considering
the present state of knowledge of the constitu-
tion of complex mineral compounds, such for-
mulsa have Uttle permanent vi^ue.
In this article accounts will be given of the
leading properties of each class, series, and divi-
sion, of the ammonio-cobalt compounds, and
descriptions will be added of the methods of
preparation of one or two of the best-known
members of each group; the less-known com-
pounds will merely be recorded. For details
concerning individual compounds other than
those described, reference must be made to the
original memoirs. (A good account of the
cobaltamines will be found in the article ' Ko-
balt ' in Ladenburg's Hamckotlrterbuch der Che-
mie, 5, 601 et seq.) •
Class I.— COBALTO-AMINES or AMMO-
NIO-COBAIiTOUS SALTS, M.a!NH3; M = co-
baltous salt, a; generally =: 6. These salts were
first examined by H. Eose (P. 20, 147). They
are produced by combination of NH, with dry
cobaltous salts, or adding cone. KHjAq to cone,
solutions of cobaltous salts in absence of air ;
they are decomposed by heat with loss of NH3 ;
their aqueous solutions also undergo decomposi.
tion, especially on warming.
Ammonio-cobaltous chloride G0CI2.6KH3 ;
obtained by adding cone. NH,Aq to cone' CoCl^Aq
until the blue pp. which forms is dissolved, in
absence of air, and allowing to crystallise. Bed
octahedra; unchanged in a closed vessel; in
the air, or over HjSO^, or by warming with Aq,
NH, is separated. Soluble, without change, in
dilute NHjAq, scarcely sol. in cone. NHjAq, in sol.
alcohol. The compound C0CI2.4NH3 is formed
when NH, is absorbed by dry CoCl,; and
CoCaj.2NH, is produced by heating CoClj.GNH,
to 120° (H. Eose, P. 20, 147).
Ammonio-cobaltons nitrate
Co(NO,)8.6NH3.2HjO; obtained similarly to the
chloride. Bed crystals, which quickly turn
brown; decomposed by water with removal of
NH, (Fremy, A. Ch. [3] 35, 257).
Ammonio-cobaltous sulphate G0SO4.6NH,;
obtained by adding alcohol to an ammoniacal
solution of CoSO, (Fremy), or by combination of
dry CoSO, with NH, (Eose).
The compounds CoBrj.GNH,, CoIj.eNHj, and
C0I2.4NH, are aJso known (Bammelsberg, P. 56,
245; 48,155).
OOBALTAMINES.
Class n.— OXY-COBALTAMINES or AM-
MONIOOXYCOBALTIO SALTS, or OXYOO-
BALTIAO SALTS, Ooj(NH3),;BVOH.O.OH, and
Ooj(NH,),„Bis.O.OH, where Ei = monovalent
acidic radicle. These salts are obtained by' the
combined action of NH, and air on cobaltous
salts ; when a stream of air is passed into an
ammoniacal solution of a cobaltous salt, the
colour of the liquid changes to brown, and if the
solution is sufficiently cono. the oxycobaltamine
frequently separates ; in some cases the salt is
obtained by adding a salt or an acid to the solu-
tion obtained as described. The oxycobaltamines
generally partially decompose when heated alone
or in NHgAq, giving off oxygen and forming
salts of the octamine (fusco-) series, which, by
combination with NH,, form salts of decamine
and dodecamine series. The oxycobaltamines
are decomposed by warm water with ppn. of
Co20,.3H20 or a basic cobaltous salt and
tvolution of oxygen. Dilute acids partially
decompose the oxycobaltamines of the form
Coj(NHj),i,K4.0H.O.OH with production of green
salts and separation of water. The green salts
thus formed are regarded by Vortmann (M.
6, 404) as amhydro-oseycobaltammes ; e.g. oxy-
cobaltamine chloride Co2(NHs),o01<.OH.O.OH
with conc.HClAq gives anhydro-oxycobaltamine
chloride Co2(NH3)„Cl4.C1.0.0H, thus
Co2(NH,),„01,.OH.O.OH + HOI
= Co2(NH,),„Cl,.C1.0.0H + HjO. The oxycobalt-
amines were formerly represented as containing
the group CojOj; and the anhydro-oxycobalt-
amines were regarded as acid salts derived from
the oxycobaltamines (Maquenne, O. B. 96, 344) :
the change from the chloride to the anhydro-
ohloride, for instance, was formulated thus : —
OoA(NH3)„Cl,.H,0 + HCl
= CoA(NH3)„0l4.0IH + H2O. But Vortmann's
observation thatsolutions of the oxycobaltamines
reduce EMnOjAq and KiCr^O^Aq points to the
presence of the group O.OE ; and the formation
of octamine salts with evolution of ammonia and
oxygen by heating ammoniacal solutions of oxy-
cobaltamines confirms this supposition; thus
Co,(NH,),„(NO,)4.0H.O.OH.H,0
= 0Oj(NH,)a(NO3),(0H)j + 2NH, + H^O + 0.
Whether the green salts obtained by the reaction
of acids with the oxycobaltamines are regarded
as acid salts of the oxycobaltamines (Maquenne),
or as anhydro-oxycobaltamines (Vortmann),
in either case f of the acid radicle is repre-
sented as related to the rest of the salt dif-
ferently from the other , four-flftha ; thus the
nitrate is either Co3(NHj)„(N03)4.N03.0.0H or
GoA(NH3)„.(N0,)i.N0,H. _ If Vortmann's
formula for the oxycobaltamines is adopted, it is
better to regard the green salts as anhydro-oxy-
cobaltamines. One-fifth of the acid radicle is
regarded by Vortmann as directly associated with
the Co atom. The existence of acid salts of the
oxycobaltamines, differing in properties from the
anhydro-ozycobaltaminea, and very probably
belonging to the same type as the oxycobalt-
amines (e.g. Co2(NH3),„(NOj)4.0H.O.OH.HN03),
tends to show that the green salts are better
regarded as anhydro-oxycobaltamines than as
acid salts of oxycobaltamines.
Series I. Oxs-oobaijIiac saiiIs; or Amuokio-
o^T-coBtfiTio SMiTS, Co,(NH,),^4.0{[.O.OH.
Ozy-cobaltamina iodide
Co,(NH,)„I,.OH.O.OH (Vortmann, M. 6, 404) j
obtained by adding cold cone. EIAqto an oxidised
ammoniacal solution of CoCl,. Green needles ;
unchanged in air; decomposed by much H^O
with evolution of O. DUnte acids separate I and
evolve O; hot cone. HNO, forms luteo-cobalt
nitrate Coj(NH3),j(NO,)3.
Oxy-cobaltamine chloride
Coj(NH3),oCl4.0H.O.OH (Vortmann, M. 6, 404) ;
obtained by dissolving crystals of CoClj in 2|
parts NH,Aq S.Q-. '913, with gentle warming,
passing air into the cold solution until the pp. of
CoGl,.a;NH„ which forms, redissolves, saturating
with NH,C1, and adding alcohol ; ppn. is aided
by rubbing with a glass rod. Greenish-brown
powder ; very unstable, easily giving off 0, and
then passing into fusco-cobalt chloride
Coj(NH3),.Cl4(OH)j (c/. Fremy, A. Ch. [3] 35,
257).
Oxy-cobaltamine nitrate
Coj(NH,),„(N03),.OH.O.OH (Fremy, Lc; Vort-
mann, Z.c. ; Gibbs, P. Am. A. 10 [1875] 1 ; 11,
1); obtained by leading air into saturated
Co2N03Aq, to which saturated NHjNOsAq, and
5 parts of NHjAq S.G. -938, have been added.
Dark brown prismatic crystals. Very unstable ;
loses water and a little NH, in dry air ; when
heated appears to form fusco-cobalt nitrate
Oo,(NH,)3(N03),{OH)3.
Oxy-cobaltamine sulphate
Oo2(NH3),„(S04)j.OH.O.OH (Fremy ; Vortmann);
obtained similarly to, but more easily than, the
nitrate. Dark brown crystals ; more stable than
the nitrate ; heated to 110°-120° it loses H^O,
NH„ and 0, and forms fusco-cobalt sulphate
C03(NH3)3(S0,),(0H),.
Ozy - cobaltamine acid nitrate, sulphate,
Bulphato-chloride, &c. These salts are obtained
by dissolving the nitrate or sulphate in cone.
HNOj or H2SO4 respectively, or by dissolving
the sulphate or nitrate in cone. HCLAq. Their
compositions are expressed by the formula
Co3(NH,),„(NO3)4.OH.O.OH.HN03,
CoJnH,L S0,)j.0H.0.0H.2HjS0„
CojJnHj),, SOJCI3.OH.O.OH.4HCI,
Co2(NH,),„(N03)jClj.OH.O.OH.4HCl,
and Ooj(NH,),„(SO,) (N03)j.OH.O.OH.4HN03.
These salts are all very easily decomposed by
heat, giving green salts, the change probably
consisting in removal of the excess of acid.
Series II. Anhtdbo-oxyoobaliuo salts,
or Anhidbo-oxy-oobaltamines,
Coj(NH3),3VB'-O.OH (Vortmann, M. 6, 404).
Anhydro-oxy-cobaltamiue chloride
Co2(NH3),„01,.01.O.OH.HjO ; obtained by digest-
ing freshly prepared oxy-cobaltamine chloride in
cold cone. HClAq until the colour is green, and
crystallising from warm dilute HClAq. Small
green needles; stable in air; loses NH3 and
H2O on warming; e. sol. water, the solution
rapidly decomposes ; when a solution in HClAq
is boUed, purpureo-chloride, Coj(NH,),„01„, is^
formed ; heated with NH3Aq, purpureo-chloride
is formed, along with luteo-chloride
Co,(NH,),2Cls. Forms double salts with
2PtCl4.5Hj,0, and 3Hg0l2.
Anhydro-ozy-cobaltamlne nitrate
Co2(NH,),„(NO,)^N03.0.0H.Hi,0 ; obtained by
adding oxy-cobaltamine nitrate to a mixture of
equal vols, cone. HKO, and H,0, digesting in the
CX)BALTAMINES:
225
cold and then warming until all is dissolved ;
on cooling a blue-green finely oryatalline pp.
forms. SI. sol. water, solution rapidly decom-
poses; solution in dilute acids may be boiled
without change.
The other important salts of the amhydro-oxy-
cobaltarmne series are the following : —
Sulphate (Co,(NH,)„.O.OH)j(SO,),.8HjO.
Bichromate (COj(NH3),o.O.OH)2(CrjO,)j.8HjO.
Ghloro nitrates
Co2(NH,),o(NO,),01j.C1.0.0H.HjO, and
Co,(NH,),o(NO,),C1.0.0H.H,0.
Add sulphates
(0oj(NHj),„.O.OH)j(SOJ5.!bH2S0j.wHjO ; » = !
and 2, and n=2 and 3.
Acid nitrate-sulphate
Cos(NH,),o(SOj2(NO.).O.OH.H,SO,.H,0.
Class III.— COBALTI-AMINES, or AMMO-
NIO-COBALTIC SALTS Oo2(NH,) JEli, ; a; = 6,
8, 10, 12. This class comprises by far the
greater number of the ammonio-cobalt salts.
It is divided into four series, and some of these
are again subdivided. The series are:
(i.) Hexmnines Co.j{KB.3)^g.
(ii.) Octanwnes Co2(NH3)sB„.
(iii.) Decwmmes Co2(NH3),|,E,.
(iv.) Dodecwrmnes Coj^H^y^p
Series I. Hexamines, or Eexammonio-
conAiiTio SALTS Co2(NH3)eB',. Also called
dichro-cobalUc salts. These salts are very un-
stable ; they are readily decomposed by potash.
Hezamine chloride Co2(NH,),Cls.H20 (Di-
chrocobaltic-chloride). Octamine cobalt car-
bonate, OojfNHjjjICOs),, is obtained by dissolv-
ing CoCOj in NHjAq in presence of (NHJ^COj,
exposing to air for some time, evaporating on
water-bath to a small volume, adding (NH,)2C03
and evaporating again; this salt is dissolved
in NHjAq, (NHJ^COa is added, and the solution
is evaporated to dryness on the water-bath;
evaporation after addition of a little water and
(NHJjCO, is repeated two or three times ; the
crude carbonate thus obtained is treated with
dilute HClA.q ; the turbid liquid is heated nearly
to boiling, and then quickly cooled, when the
hexamine chloride separates as small green
crystals (Vortmann, B. 10, 1451; 15, 1890). Crys-
tallises from neutral solution in green crystals,
appearing almost black when large ; crystallises
from acidified solution in red-brown tables.
Dichroism is best seen by evaporating a drop of
solution of salt on an object-glass, and examin-
ing under microscope. Water is not completely
removed at 120°. Fairly soluble in water ; on
warming solution becomes violet, and contains
octamine purpureo-chloride Coj(NHj)sOl5.2H20
which may be ppd. by HCl ; solution in HGUiq
on warming gives pp. of decamine purpureo-
chloride Coj(NHj),„01a. Forms a double salt
with HgClj.
The chief salts of the heosamme series,
besides the chloride, ore the following :
M = 002(NH,),.
Basic carbonate M.(OH)j(CO,)2.3H20.
Nitrates M.(NO,),.8H20 ; and
M.(N03)3(OE),.yH,0.
Sulphate M.(SO,),.6HjO.
Witrii^ M.(NOj), (Erdmann, J.pr. 97, 405).
Series II. Ociauines, or Octaumonio-
poBALTic SALTS Coj(NH,)8E'„. The salts of this
Vol. XL
series are arranged in three divisions, the ptaseo-,
the fuseo; and the croceo- eobaltic salts.
Division I. Praseo-cobaltie salts.
Fraseo-oobaltic chloride Co2{'SB.,)ifi\.Z'H^O
(Vortmann, B. 10, 1451; 15, 1890; F. Eose,
Untersucfmmgen Uber ammomakaUsche Kobalt-
verbindungen [Heidelberg, 1871]). This salt
exists in two modifications generally known-
as praseo-cobaltie chloride and octamine-pu/r-
pureo-cobalt chloride, respectively. Fraseo-
chloride forms green lustrous crystals; e. sol.
water, the solution readily decomposes, turning
violet, and HCl then pps. deoamine-purpureo-
chloride Coj(NH3)i„Cl3.2HjO ; dried at 100°
this salt becomes anhydrous. Ootamine-
purpureo-chloride forms deep violet octa-
hedxa ; does not lose any H,0 at 120°.
The praseo-salt is generally found in the
mother-liquor when any cobalt salt is exposed
to air in presence of ammonia, and the solution
is ppd. by HCl ; it is separated from such liquid
by addition of NH^Cl.' The pp. is separated
•from admixed decamine-purpureo-ohloride by
washing with alcohol, drying, dissolving in cone.
HzSO,, and carefully ppg. by HClA.q added drop
by drop ; it is then dissolved in ice-cold water,
and at once ppd. by a little HClAq.
The purpureo-salt is obtained by oxidis-
ing an ammoniacal cobalt chloride solution in
the air, evaporating to a small bulk after addi-
tion of (NH4)jC03, filtering from ppd. luteo-
chloride (Co2(NH,)„Clg) and allowing to stand.
When a praseo-chloride solution is warmed
with fairly dilute HClAq, a violet liquid is ob-
tained, from which octamine-purpureo-ohloride
separates on cooling. When cone. H^SO, is
added to an aqueous solution of the purpureo-
chloride crystals of the praseo-salt gradually
separate.
Praseo-chloride forms two double salts
with HgClj, viz., M.Hg0l4 and M.2HgClj. Pur-
pureo-chloride forms the double salts
M.6Hg01j.2HjO and M.3HgClj.HjO ; where M =
Co2(NH3)gCl3. When a solution of octamine
carbonate, formed as described under hexamine
chloride {v. supra), is ppd. by coW HClA.q, small
red crystals are obtained ; these have the com-
position Coj(NH3),Cl3.2H20.2HjO; at 120° the
crystals lose 2H2O, becoming octamine pur-
pureo-chloride. This salt is usually known as
octamine roseo-cobalt chloride; it forms
a double salt 00j(NH3)3Cl,.2H,0.6HgCL,.3H,0.
The two salts, praseo-cobalt chloride and
octamine-purpureo-chloride, are isomeric ; in
the second the two molecules of water are more
firmly held to the rest of the salt than in the
praseo- compound. The ros&o-chloride differs
from the two others by containing two molecules
of water loosely held to the rest of the salt.
Each of these salts is the representative of a
subdivision of praseo-cobaltie salts ; the
praseo-salts proper, the octamine pwrpureo-salts,
and the octamine roseo-salts. The chief salts
in these subdivisions are the following : —
M = Co,(NH,)3.
Fraseo-cobalt ohromato-chloride
M.Cl^,Cr20,.H,0.
Fraseo-cobalt nitrate-chloride
M.Cl,.(N0s),.2H,0.
Octamine purpureo-cobalt (hromate
M.(CrOj3.2H30.2H,0.
Q
320
OOBALTAMINES.
Octamine-purpnreo-oo'balt snlphate
M.(SO,),.2H,0.2HsO.
Octamine roseo-cobalt snlphate
M.(S04)a.2a,0.4HoO. 1
Octamine cobalt carbonateB M.(CQ,),.3H20';
and M.(C03),.HjCO,.2HjO.
Octamine cobalt Bulphato-carbonate
M.(COs)jS04.aHjO.
Octamine cobalt nitrate M.(NO,)g.2H20.
Division II. Fusco-cobaltic salts
(Fremy, A. Oh. [3] 35, 257). These compounds,
which are basic salts of the octamine series, are
obtained from the brown liquids formed by
allowing ammoniacal cobalt solutions to stand
for a long time in air ; they are also formed by
decomposing ozy-cobaltamines by water. They
are non-crystallisable ; alcohol, or passage of an
ammonia-stream, pps. them from their solutions.
Boiled with water, especially if alkali is present,
they are decomposed with separation of
Co^Oj.SHjO. The chief salts are the loUowing :
M = Co,(NH,),(OH)j.
Fusco-cobalt chloride M.CI4.2H2O.
Fnsco-cobalt nitrate H.(NOs)4.2H20.
Fusco-cobalt sulphate M.(S0,)2.2H20.
Siyision III. Croceo-cotaltie salts.
These compounds, which are tetra-nitro-deriva-
tives of the praseo-salts, are produced by the
action of ammonia and nitrous acid (or ammo-
nium or potassium nitrite) on solution of
C02NO3 or C0SO4 ; dark-coloured solutions are
thus formed, from which thecroceo-salts separate
in yellow crystals mixed with Go(OH)2.
Croceo-cobaltic sulphate
Co2(NB3),(N02),.S04. Preparedby adding NHjAq
and (NHJnOj to CoS04Aq, and reorystallising
from hot dilute HjSOiAq. Yellow lustrous
tables ; large wine-red crystals from dilute solu-
tions. SI. sol. hot or cold water. The other
important croceo-salts are represented by the
following formulas, where M = Co2(NH3),{N02)4 :
Chloride M.Clj ; forms double salts M.Clj.PtCl,
and M.Cl2.2Au01j ; Bromide M-Br^ ; Ch/romate
M.CrO,; DichrrnnateHL.CiiO,-, Niirate'H.I^O^i;
Periodide M.Ij.I,.
Series III. Decamines, or CEOAMMomo-
coBALTio SAiiTS, C02(NH3)„Bi,. This series
contains very many compounds; these com-
WithPtOl,, roseo-ehloride gives M.Clj.2PtCl,.6H20;
AuOl, „ „ M.01j.2AuCl3.2HjO;
(NHJ2CA..
M.(0204)„6H20 ;
M= C02(NH,),..
1 the roseo-salts; they are changed to the latter
by long-continued warming in presence of water,
by long-continued digestion with dilate acids at
the ordinary temperature, or generally by pro-
cesses which result in hydration, but not merely
by solution in water and crystallisation. The
xantho-salts bear a somewhat similar relation
to the purpureo-salts that the croceo-componnda
of the octamine series bear to the praseo-com-
pounds of the same series ; the zantbo-salts are
dinitro-derivatives of the purpureo-salts, the
croceo-salts are tetra-nitro-derivatives of the
praseo-salts.
Diy^sion I. Boseo-eobaltio salt$.
These salts are obtained as products of the de-
composition of the oxy-oobaltamines, from
aqueous solutions of which they are ppd. by
acids in the cold. They are obtained from pur-
pureo-salts by long-continued digestion with
dilute acids, or, more readily, by treating these
salts with lilkajis, e.g. dilute solution of KH, or
NaOH, AgjO and water, or BaCOj — and subse-
quent saturation with acids. The roseo-salts
form red to peach-coloured crystals, which ex-
hibit dichroism ; they are fairly easily soluble in
water; their ammoniacal solutions are decom-
posed on boUing with ppn. of COjOg.SHjO.
These salts lose water by treatment with cone,
acids, and form purpureo-salts. Boseo-salts in
solution give a pp. of roseo-pyrophosphate on
addition of sodium pyrophosphate; potassium
ferrocyanide also gives a pp. with these salts;
these reactions serve to distinguish roseo- from
purpureo-salts (Jorgensen, J. pr. [2] 31, 49).
The roseo-salts show many analogies — e.g. in
crystalline form, methods of formation, and
general reactions — with the dodecammonio- (or
luteo-) salts Co2(NH,),jE',. Jorgensen (J. pr,
[2] 31, 49) regards the roseo-decamlnes as luteo-
salts in which 2NH, is replaced by 2H2O. Boseo-
chloride, nitrate, oxalate, &o., in aqueous solutions
react with BaCl2Aq and Ba(NO,);^q to give only
roseo-salts. Boseo-ohloride is soluble in 4*8 pts.
water at 10°, while purpureo-chloride requires
287 pts. water for solution at 10°. Aqueous so-
lutions of the two chlorides often give difierent
compounds by reacting with the same re-agents,
aai purpureo-ehloride gives M.Cl,.2PtCl4.
„ „ „ M.Cle.2AuClr
M.Cl2(C20J,
pounds are well-marked and stable bodies, fre-
quently obtained from cobaltamines by decom-
posing these by acids. The series is arranged in
three divisions: the roseo-, the purpureo-,
and the xantho-salts. The following are
typical representatives of these divisions : roseo-
cobalHc chloride Co2(NHj),jCl,(H20)2 ; purpwreo-
cobaltie chloride Co2(NH,),gCle ; xamtho-cobaltic
chloride Co2(NHj),„('N02)20l4. The roseo- and
purpureo-salts differ in the quantities of water
they contain, the purpureo-salts are generally
anhydrous, the roseo-salts usuallyoontain 2H2O ;
inasmuch as these salts form very distinct com-
pounds with different properties, it seems neces-
sary to conclude that the SHjP of the roseo-salts
is not water of crystallisation, but forms an inte-
gral pari of the molecule of each of these salts.
The purpureo-salts areless soluble in water than
Boseo-cobaltio chloride Co2(NHj)„(H20)2C!l,
(Jorgensen, X pr. [2] 18, 209; 31, 49; Gibbs a.
Genth, Researches on the Ammonia-cobalt bases
[Washington, 1856] ; Mills, P. M. [4] 35, 245;
Geuther, Lehrbuch der Chemie, 442). Obtained
from an ammoniacal solution of CoCl, by oxidis-
ing in air, or by KMnO,Aq (Mills), and ppg.
by HCl, avoiding rise of temperature ; also by
digesting purpureo-chloride (q. v.j with dilute
EClAq, or by dissolving the same salt in NH^Aq
and ppg. by HCl in the cold (Jorgensen, l,e.;
Geuther, l.c.). A red, dichroic powder, appearing
crystalline under the microscope. Loses 2H2O
at 100°, giving purpureo-chloride. Soluble in
4-8 pts. water at 10°. Very unstable, easily going
to purpureo-chloride. Forms agoldsalt,M.2Au01„
by reaction with AuCljNaCl : forms three Pt salts ;
M.PtCl4.2H20, M.2PtCl4,H20, and M.3PtCl2.6B^O
OOBALTAMnSTES.
227
(Wrgensen, l.c.) : fonns two Hg salts ; M.2HgCl.
and M.6HgCl,.2H20 (Jorgeusen, I.e.),
[M= C0;(NH3),.{0H,),Cl,.l
Gibbs {l.c.) describes a yellow form of rosea-
eWorWfl obtained by dpoomposing the yellow
form of roseo-sulphate (j. ■».) by BaCl^Aci; this
form does not yield purpureo-ohloride by reaction
with HClAq.
Boseo-cobaltic sulphate
Coj(NH,)„(H,0)2(SO,)3.3H,0 (Fremy, A. Ch. [3]
35, 257 ; Gibbs a. Genth, Besearohes on the Am-
monia-cobalt bases [Washington, 1856] ; Gibbs,
P. Am. A. 10, 1 ; 11, 1 ; Braun, A. 138, 109 ;
142, 50; Jorgensen, J. pr. [2] 31, 49 ; 35,417).
Obtained by adding the proper quantity of
H^SOjAq to a solution of roseo-oarbonate, and
evaporating over H^SO,, or ppg. by alcohol ; the
roseo-carbonate solution is prepared by decom-
posing purpureo-chloride or bromide by AgjCOg
(Genth, A. 80, 275 ; Claudet, P. M. [4] 2, 253 ;
Jorgensen, /. pr. [2] 18, 209 ; 19, 49). Boseo-
Bulphate forms reddish crystals ; soluble in
94-6 pts. water at 17°, and in 58 pts. water
at 27°. Two other forms of the sulphate are
described by Gibbs a. Genth (P. Am. A.10,1;
11, 1) ; they differ chiefly in solubility from
the ordinary form. An acid roseo-sulpfuite
Coj(NHJ,„(OHL(SO,),.2H2S0j.H2O is described
by Fremy (Z.c.) (v. also Jorgensen, l.c.). The
normal sulphate forms a gold and also a Pt salt :
M.(S0JjCL,.2AuCl, and M.(SOJjOl2.PtCl< (Jor-
gensen, Ix.) [M= Coj(NH,),„(OH2)J.
The chief salts of the roseo- mvision besides
the chloride and Eiulphate are represented by the
f oUowing formulas, where fij = Co2(NHs),„(Hj,0)2: —
DicM-omate, M.(Cr20,)3.3HjO (Gibbs). Bromide,
M.Br„ forming Pt salts with 2PtBr,.2H20, and
3FtBr4.4H20 (Jorgensen). Iodide, M.Ig (Jorgen-
sen). Nitrate, ^.(NOa),, (Gibbs; Jorgensen);
forming a Pt salt, M(NO,)20l4.2PtOl4.2H20.
Nitrato-suVphate, lll.l^O,)Ji_s6^2 (J.). Oxalate,
M.{C204)3.4H20. SuVphato-osialate,
M.(CjOJ.,(SOJ.SO,.2HjO (Gibbs a. Genth).
Ordurphosphates, U.I^O^^'H^VOi.^B.fi ;
M.(OH),,(P04H)j.2HjO (J.). Pyrophosphates,
Mj.(PjO,)3.12H20 ; M.(P20,H), (J.); also
M.(P20,Na)2.23H;,0 (Gibbs, Braun, Porumbarn,
C. B. 91, 933 ; 93, 342). Brcmo-sulphate,
M.Br2(S0 jj; forms a gold salt M.Br2(SOj2.2AuBrs
(J.). lodosulphate, 'iS.,lj^^0^2{Kxdk.,ActaUrwoers.
Lund. 1870). Sulphite, M.(SO,)j.3HjO (Gibbs) ;
forming a double salt M.(S03)3.Co2(S03)3.9H20
(Kiinzel, J. jpr. 72, 209; Geuther, l.c.).
Division II. Purpureo-cobaltic salts.
Co2(NH3),„B'8- These salts are the most stable
of all the cobaltamines. They are formed from
the roseo-salts by heating with cone, acids, or
sometimes by continued digestion with cone,
acids in the cold ; also by the action of acids on
fusco- and zantho-cobaltio salts. The purpureo-
salts are generally anhydrous ; they are less
soluble in water than the roseo-salts, into which
salts they are changed by prolonged digestion
with dilute acids. Solutions of purpureo-salts
are decomposed by boiling with alkalis, giving
pps. of CojOj.SHLjO. These salts probably con-
tain two acidic radicles more closely asso-
ciated with the rest of the salt than the other
four radicles; e.g. they form xantho-salts
C0j(NH3)„(N0j)2B'j ; again, chloro-purpureo-sul-
jphate Co2(NH,),„01,(S04), does not give HCl
with oonc. H^SO^, nor is it pj^d. by AgNOjAq
even on warming (JSrgensen). It is convenient
to consider the purpureo-salts in four main sec-
tions: the ehloropurpweo-salta Coj(NH3),„Ol2.B'„
the bromopurpzM'eo-salts Co2(NH,),„Brj.B'4, the
nitrato-piirpwreo-salts Oo2(NH,),„(N03)j.B'4, and
the sulphato-purpureo-salts Co2(NHa),j(SO j.EV
Chloro-purpareo-cobaltic chloride
Co2(NH3),<,Cl2.0l4 (Mills, P. H^. [4] 35, 245;
Porumbaru, C. B. 91, 933 ; 93, 342 ; Genth, A.
80, 275; Claudet, P. M. [4] 2, 253; Terreil,
G. B. 62, 139; Braun, A. 138, 109; 142, 50).
This salt is formed when an ammoniacal solu-
tion of C0GI2 is allowed to oxidise in the air;
boiling with excess of HClAq pps. the salt as a
carmine-red powder. The reaction of HCLAq or
NHjClAq with very many cobaltamines pro-
duces this salt. Instead of oxidising OoClj in
NHjAq in air, which process takes a long time
to accomplish, it is advisable to use EMnO^Aq
(Terreil), bleaching powder (Mills), or ozonised
turpentine or indigo-blue (Braun). Chloro-
purpureo-ohloride is a carmine-red crystalline
powder ; in larger crystals it appears carmine-
red to black; these crystals are tetragonal
pyramids, isomorphous with roseo - chloride ;
they are diohroio ; S.G. ^ 1-802 ; sol. 287 pts.'
water at 10-2°, 255 pts. at 11-5°, and 244 pts. at
15*5° (F. Bose) ; insot. alcohol according to
Fremy {A. Ch. [3] 35, 257). An aqueous or
alkaline, but not an acid, solution, pps.
C02O3.3H2O on boiling. Heated in air CoCl,
and Co are obtained ; at a higher temperature
with free access of air C03O4 is produced. Many
double salts of chloropurpureo- chloride are
known, e.g. M.Cl4.2PtCl4- ; M.OI4.2AUOI, ;
M.Cl,.6HgOl2; M(SiF,)2 [M = Co2(NH3),.Oy.
The other chief salts of the chloropitrpwreo-
section of purpureo-cobaltic salts are the fol
lowing : —
M = C02(NH3),„Cl2.
Bromide,'M..Bi,; doublesalts, M.Br4.2PtBr.,
(M.Brj2.9HgBr2.
Iodide, M.I,; double salts, M.I,.4S[gl2,
M.I,.2Hgl2.
Carbonates, M.(C03)2.9H20 ; M.(C0a)j.H20.
Chromate, M.(CrOj2 (Jorgensen, J. |)r. [2] 18,
209).
Diehrmnate, M.(Cr20,)2 (Jorgensen),
Nitrate, U.QHO^t (J.).
Oxalate, M.(C204)2 (J-)-
Pyrophosphates, M.(¥J!3,)jcSfi ;
M.(P20,).HjP20, (J.) ; double salts,
M.(2P04H.5Mo03), M.(2P04NH4.5IIJoO,) (J.).
SulphaUs, M.(S0J2.4H20; M.(SOJ,;
M2.(S04).(HSOJ, (J.).
Dithionate, M.(S205)2 (J.).
Thiosulphate, M.(S208)2 (J.).
Tartrate, U.(C,B.fi,),.5HJ0 (J.J.
Bromo-purpureo-cobaltic bromide
Co2(NH3),oBr2.Br4 (Jorgensen, J.pr.l2] 19,49).
Obtained by oxidising ammoniacal CoBrjAq and
heating with HBrAq; or by heating roseo-
sulphate with cone. HBrAq, and in other ways.
Blue-violet, dichroic, microscopic octahedra;
from solutions in very dilute HJBrAq separates
as large black octahedra. S.G. V = 2'483. Less
sol. water than the chloride ; 1 pt. dissolves in
530 water at 16°; insol. HBrAq, KBrAq, and
alcohol, but si. sol. in warm water acidulated
with HBr, long digestion with this liquid pro-
q2
228
COBALTAMINRS.
duces roseq-bromide ; decomposed to bromo- |
purpureo-chloride by digestion with excess of
AgCl ; AgjO or AgjCOj produces solutions of roseo-
.lydroxide and carbonate respectively. Forms
double salts, e.g. M.Br,.6HgBrj ; M.(SiPJj;
M.Br,.2PtBr, [M = Co2(NH,)„BrJ.
The following are the chief salts of the
bromopurpureo- section of purpureo-cobaltic
compounds :
M = Co,(NH,)„Brj.
OWori(ie,M.Clj; double salts, M.Cl4.2PtCl4,
M.Cl,.6HgCl, (J.).
Chromate, M.(Cr04), (J.).
Nitrate, M.(N03)i (J.).
Oxalate, M.ICjOJj (J.).
Sulphate, M.(SOj)j (J.).
Dithionate, M.(S.A)2 (J-)-
Nitrato-pnrpureo-cobaltic nitrate
Co,(NH3),„(N03)2.(N03), (Genth, A. 80, 275;
Fremy, A. Ch. [3] 35, 257 ; Gibbs, Researches,
&o.; also P. Am. A. lO, 1 ; 11, 1). Obtained by
dissolving CoCOj in the minimum of warm
dilute HNOjAq, adding twice the volume of
cone. NHjAq, boiling with addition of 127 pis. X
for every 59 pts. Oo used, filtering after I is all
dissolved (from ppd. Inteo-salt), and warming
the filtrate with HNOjAq, whereby I is changed
to HIO, and the nitrato-salt separates out (Jor-
gensen, J. pr. [2] 23, 227). Bed powder with
shade of violet ; 1 pt. dissolves in 273 pts. water
at 16° ; decomposed by boiling with water, giving
OojOj.SHjO. The nitrato-salts are more easily
changed by hot water to roseo-salts than are
the chloro- and bromo-purpureo salts. Basic
nitrates are known; Co2(NH3),„(OH)2(N03)j.6BLjO
(Gibbs); and Co2(NH3),„(OH)(N03)5 (Kiinzel,
J.i)r.72, 209).
The following mtx'ato-compounds form the
mere important members of the section :
M = Co„(NH3),„(NO,)„.
Chloride,'iS..C\i-i double saIts,M.Cl4.2PtCl4,
M.C1^.2HgClj (J.).
Bromide, M.Br, (J.).
Ghroniaie, M.(Cr04),.
Bichromate, M.(Cr20,)2.2HjO (J.).
Oxalate, M.(C~OJ, (J.).
Sulphate, M.(SOJj.2H20 (J.).
mthionate, M.(S203)2.2HjO (J.).
Diarmm-cobalt n/itrite M.2[Co2(NH3),(N02)8]
(J.).
Snlphato-purpureo-cobaltic sulphate
Co,(NH5),„(S04).(SO.,)2.HjO (Gibbs, P. Am. A.
10, 1 ; 11, 1 ; Jorgensen, J. pr. [2] 31, 262).
Obtained by adding alcohol to aii oxidised
ammoniacal solution of O0SO4 (Gibbs), or to a
2^p.o. aqueous solution of the acid sulphate
Cb,(NH3),„(S04).(SO,[S04H]J.4H:20 (J.). Violet-
red, microscopic, dichroic needles ; v. sol.
water, from which solution roseo - sulphate
separates on evaporation. Forms a Ft salt,
Co,(NH3),„(SO,).SO,.Clj.PtCl4.2HjO. The chief
suiphato-salts are the following :
M = Coj(NH3),„(SOJ.
Bromide, M.(S04)Brj (J.).
Nitrate, M.(SO,)(NOs), (J.)
A few other purpureo-cobaltio salts are known
besides those belonging to the four sections
already described ; the chief are
Purpureo-cobaltic iodide,
Co,(NH3),„I,.l4 (J., J. pr. [2] 31, 262).
Purpureo-cobaltic chromate and di-
chromate, Co,(NH3),„(OH)2(Cr04)3, and
Co,{NH3)„(CrA)s-H,0 (Gibbs).
Division III. Xantho-cobaltic salti.
These salts are derived from the purpnreo-
compounds by replacing one-third of the acidic
radicle by the group KO, ; they may be called
nitro-pitrpureo- salts, CoJTS'H.,)i^,.{NO.^„ These
salts are produced by the action of nitrous acid
or nitrites on ammoniacal solutions of cobaltous
salts, or on neutral or acid solutions of purpureo-
or roseo-cobaltic salts. The xantho-salts are
yellow or brownish yellow; they are more soluble
in water, and more easily decomposed by water,
than the other salts of the decamine series. By
reacting with mineral acids they form purpureo-
salts. The following are the chief xantho-
salts : —
(Gibbs a. Genth, Besearclies on the Ammonia-
cobalt bases [Washington, 1856]).
M = Co,(NH,)„(N03),
Chloride, M.C[f; double saltsj
M.Cl4.2AuCl3.2H;,0 ; M.Ca,.2PtCl4.2BL,0 ;
M.Cl4.4HgClj.2H20.
Iodide, M.I4.
Chromate, M.(Cr04)j.2H,0.
Dichromaie, M.(CrjOj)j.
Oxalate, M.(C204)2.
Sulphate, M.(S0,)j.
lodo-sulphate, M.l2(S04).
Nit/rate, U.<;^O^t.
Chloro-mitrate, M.CL,(N03)2; double salts,
M.Cl2(N03)2.2AnCl, ; M.Cl2(N03)3.PtCl4.
Bromo-rdirate, M.Br2(N0,)2.
Niinte, M.{^SiiO^)^.iH^O■, double salt,
M.(NO,)4.2(Co.(NO,),).
Series IV. Dodscauines, or Dodecam-
MONIO-COBAIillO SALTS, Or LuTEO-COBAIiTIC SALTS,
Co^CNH,),,^',. These salts are formed, along
with other oobaltamines, by the oxidation of
ammoniacal solutions of cobaltous compounds,
especially in presence of much salammoniac;
they are also produced by treating fusco-cobaltic
salts with dilute acids, and by boiling roseo- or
purpureo-cobaltic salts with ammonia. The
Inteo-salts are yellow to bronze-yellow in colour;
easily crystallisable ; generally more soluble in
water than the corresponding roseo-salts. Acid
solutions of these salts are stable ; aqueous and
alkaline solutions are decomposed . on boiling
with ppn. of C02O3.3H2O. Those luteo-salts
which contain water of crystallisation e£Boresce
in air or oyer H2SO4 im vacua. The luteo-salta
are closely analogous to the roseo-salts of the
decamine series, Co2(NH,),e(0H2)2Bs; the crys-
talline forms of many luteo- and roseo-salts are
the ' same ; the solubilities are similar ; both
series of salts give similar pps. with K4Fe(CN)„Aq
and Na4F20,Aq ; haloid salts of both series are
decomposed by Ag salts giving up the whole of
their halogen. Ammonia reacts differently with
the two series ; the roseo-salts are dissolved
with formation of basic compounds, while the
luteo-salts are unchanged. Jorgensen (J. pr. [2]
31, 49) regards the luteo-salts as roseo- com-
pounds in which 2H2O has leen replaced by
2NH,. •
Luteo-cobaltio chloride Coj(NH3),jClj (Mills,
P. M. [4] 35, 245; Gtenth, A. 80, 275; Braun,
A. 138, 109 ; 142, 50 ; J8rgenBen, J. pr. [2] 35,
417). Obtained by heating an ammoniacal
solution of C0CI2 in presence of NH4CI and an
COBRA POISON.
oxidiser Bach aa PbO., MnO„or EMnO,; also by
digesting purpureo chloride with NH,Aq to
60°-60° in a closed tubn, and in other ways.
Bed-yellow, diohroio, monoclinio crystals ; S.6.
r7016 at 20° ; when dry it is unchanged in
air at 130° ; soluble in 16-8 parts water at 11-4°
(F. Bose) ; crystallises from hot water On cooling;
aqueous solution is ppd. by alkali chlorides,
mineral acids and alcohol ; unchanged by heat-
ing with cono. HClAq at 100° in a closed tube ;
slowly decomposed by heating with KH,Aq,
more rapidly by KOHAq. Forms various double
salts of which the chief are :— M.2Au01,
(Jbrgensen), M.2PtCl,.H20, M.PtC1^.2H20,
M.3PtCl,.6H20, M.3PtCl4.4H20, M.2HgCl„
M-SHgClpSH^O, M-SSnCl^-lOH^O (J.; also Braun)
[M = Co,(NH,),2ClJ.
luteo-cobaltic snlphate
Co2(^H,),2(SO,),.5H20. Obtained by passing air
for some days into an ammoniacal solution of
CoSO, and CoCl, mixed with NH^Cl, treating the
yellow pp. of luteo-ohloride and sulphate which
forms with hot water, adding Ag^SO^ and a few
drops of KjSOjAq to the solution, and crystal-
lising by eTaporation (Gibbs a. Genth, Besearches,
&c.). Also by rubbmg together luteo-chloride
and AgjO with water, filtering, acidulating the
filtrate with H^SO,, and evaporating (JSrgensen,
J. pr. [2] 35, 417). TeUow, rhombic, dichroic,
crystals ; slightly soluble in cold, more soluble
in hot, water ; loses 4H2O over H^SO, ; aqueous
solution is only slowly decomposed on boiling ;
not ppd. by acids from aqueous solution. Forms
double salts with sulphates of Ce and La;
M.BLaSOj.Hj,0, M.SGeSO^.H^O, M.Ce.,(S04)3.a,O
(Wing, Am. 8. 49, 303). [M = Co2(NH3),,,(SO,)J.
The chief luteo-salts besides the chloride and
sulphate are the following :— M = Co2(NH3),2.
Carbonate, M.(COa),.TE.fl (Gibbs a. Genth,
Besearches, &c.).
Chrcyrnates, U.(CrO^,.5Bj:i (G. a. G.).
DicJwomate, M.(CrjO,)3.xHjO.
Bromide, WiBr^; double salt,
M.Br..2PtBr4.2HjO (J5rgensen).
JocMe, M.Ij (J. ; G. a. G.).
Nitrate, H.(NO,)s; double salt,
M.(NO,)j.01,.2PtCl,.2HjO (J.; also Vxemy,A.Ch.
[3] 35, 257).
Nitrato-su^]iate, M.{N03)j.(S04)s (J.).
Oxalate, M.(CA)»-4HjO ; double salt,
M.(Cj04)j.Clj.2AuOl3.4HjO (G. a. G.).
Phosphates, M.(P04)j.8H30 (J.); '
M.(P04H)3.4Hi,0 (J.); M.(PjO,Na)j.23HjjO (J.);
M.(PA)3-20H3O; M.(P20,H), (J.).
Chloro-sulphate, M.(S04)2.Clj ; double
salts, M.(S04)2.Cl2.2AuCl3, M.(S04)2.Cl2.2HgC!l,
(J.; G. a. G.; Sehiff, A. 123, 1; 121, 124;
Krok, Acta Uidv. Lund, 1870).
Bramo-sulphate, M.(S04)2Brj (J.); double
■alt, M.(S04)j.Br2.2AuCl,.
lodo-sulpliate, M.(S04)jIi, (Krok).
Double salts of nitrite, sulphite, and di-
thionate, M.(N0j),.Coj(N02), (Sadtleir, Am.
S.49, 198); Sl.(SO,),.COj(SO,),.2H30(Geuther,
A. 128, 158; Kiinzel, J.pr. 72, 209) ;
M.(SO,)3.2Co2(S03),.l6H20 (Geuther, Kunzel);
2[M.(SjOJ,.(OH)J.COi,(SjOJ».(OH)2 (G.; also K.).
COBALTAMINES NOT INCLUDED IN ANT
OF THE FOEEGOING CLASSES.
Erdmann's salt Co,(NH,)4(NOj)9Kj (Erd-
mann, J. pr. 97, 405). Brown, Instrous, pnsms,
separating from a solution of CoGL, in presence
of much NH4CI on addition of EXO,. Solutions
of this salt give pps. of analogous compositions
with solutions of many metallio salts, e.g. of
Pb, Hg, Ag, Tl (Gibbs, P. Am. A. 10, 1 ; 11, 1).
Melano-oobaltio chloride
Co2(NH:,),.NH2C1.0l4 (F. Rose; Vortmann, B. 10,
1451; 15, 1890). Greyish violet, very hygro-
scopic, crystals; obtained by oxidising an am-
moniacal solution of a cobaltons salt, adding
HGlAq, filtering after an hour or so from pur-
pureo-chloride, and dropping the filtrate into an
equal volume of ice-cold fuming HClAq. This
compound forms double salts, and derivatives,
especially M.Cli.PtCl,, M.(0H)j.01j.PtCl4,
M.(OH)j.Cl2.3HgClj.H20 (Vortmann).
[M = C02(NH3),.NH,C1.].
Ammonio-cobaltic oxychloride
Co,(NH3)jO,Clj.5HjO (Fremy,4.0fe. [3] 85,257).
Black crystals ; obtained by exposing ammo-
niacal CoCLjAq to the air for some months,
boiling with NHjAq, filtering from purpureo-
chloride, and boiling again. M. M. P. M.
COBAITATES. When ' CoO, Co(OH)2, or
CoCO, is dropped into 6-8 parts molten potash,
a blue colour is formed which after a time
changes to brown ; if fusion is continued until
dark-coloured crystals begin to form, the
mass is then allowed to cool and treated with
water, thin, black, lustrous, six-sided tablets
remain. These crystals have the composition
(Co30s)a.E20.a;H20; according to Schwarzenberg
a; = 3, or if the crystals are dried at 200° x=i
{A. 97, 212; also Mayer, A. 101, 266). Von
Pebal {A. 100, 257) says that all water is re-
moved at 100°. The crystals of potassium,
cobaltate are insoluble in water; they are de-,
composed at a little over 200°, water then dis-
solves out KjO and Co,04 remains. Mayer (l.c.)
says that long-continued washing or boiling
with water removes potash from the originiJ
crystals, and that dilute HGlAq removes Co
(c/. alsoEussell, Pr. 32, 258). M. M. P. M.
C0BALTI-CYA2TID£S and COBALTO-CYAN.
IBES V. Ctanides.
COBALT COLOTTSING MATIESS. Addi-
tion of a Co salt to potash glass produces a deep
blue colour. Boasted Co ore is fused with
pearl-ash and quartz-sand, the molten mass is
poured into water, and then finely powdered ; it
is used as a colouring matter under the name
of Smalt. Smalt is essentially a double silicate
of Co and £ approaching the composition
CoO.Kj,0(SiOj),. Cobalt-ultrcmwrvne or Thi-
nard^s blue, and Oceruleum, are essentially salts
of Co chiefiy phosphates and arsenates. Cobalt-
green or Binman's green contains Co and Zn
oxides, and sometimes a little As^O, ; it is pre-
pared by evaporating mixed solutions of Co and
Zn salts and strongly heating the residue. (For
details of these colouring matters v. Dictiomabt
on TECHNICAIi OHBMISTBT.) M. M. P. M.
COBBA POISON (A. Pedler, Pr. 27, 17;
Blyth, Analyst, i. 204 ; Warden, C. N. 64, 197).
Two-thirds of the organic matter in the poison
of Naja trijmdians ia of albuminous character.
280
COBRA POISON.
being ppd. by alcohol, the poisonous substance
is soluble in alcohol. NH, is not an antidote,
but HCl retards the physiological action, while
HCl and platinio chloride form a salt,
(0„Hj,N40„HCl)jPtCl4(?),whiohisnotpoisonous.
AuClj and EMnOj mixed with the poison before
injection prevent death; but after the poison
has been injected, the subsequent injection of
these liquids will not prevent death (T.L. Brun-
ton a. Sir J. Fayrer, Pr. 27, 465). A poisonous
crystalline substance may be obtained by dia-
lysing the poison.
COCAINE CijHjiNO,. Bemoyl-methyl-
ecgonine. [98°]. S. -14 at 12°.
Occurrence.— In the leaves of Erythroxylon
Coca of South America' (Niemann, Ar. Ph. [2]
103, 120, 291 ; A. 114, 213). These leaves are
chewed by the inhabitants.
Formation. — In small quantity by heating
together ecgonine, benzoic anhydride and
methyl-Iodide at 100° for 10 hours (Merck, B.
18, 2952).
Preparations. — 1. Coca leaves are digested
with ether; the ether is evaporated and the
residue extracted with boiling water ; the solu-
tion is mixed with magnesia and evaporated and
the ' cocaine extracted by amyl alcohol (Tru-
pheme, G. G. 1881, 447).— 2. The leaves are
extracted with alcohol, colouring matter is ppd.
by lime, and the filtrate evaporated to a small
bulk and mixed with water. The alkaloid is
then ppd. by KjCOj and dissolved in ether and
decolorised by animal charcoal (Schull, Ph. [3]
10, 408).
Prqperfes.— Small monoclinic prisms ; a:b:c
■= l-186:l:l-223 ; /3 = 73° 50' (Tscherniak, Sitz.
W. 48, i. 34) ; v. si. sol. water, v. sol. hot alcohol
and ether. Cone. HjSO, dissolves it without
colour. It produces insensibility to pain in the
tongue, eye, or other part touched by it. Taken
internally it acts somewhat like opium (Ken-
nedy, Ph. [3] 10, 65 ; J. Grasset, O. B. 99, 983,
1122; 100,364; Richard, O. iJ. 100, 1409 ; Laf-
font, C. B. 105, 1278 ; Sighicelli, 0. G. 1887,1150).
An injection of cocaine acts as a cerebro-spinal
stimulant or anti-narcotic (Mosso, 4r. Ph. [3] 26,
179). Solutions of salts of cocaine are ppd. by
KOH,NHj, andNajCOj; the pp. is soluble only
in a large excess of EOH, but insol. NH,. Am-
monium carbonate gives a pp. sol. excess. Picric
acid, tannin and HCl, potassio-mercuric iodide,
iodine solution, SnClj, AuOlj, and PtClj also give
pps. By heating with cone. HCl cocaine is split
up into ecgonine CjHuNOj, methyl alcohol, and
benzoic acid (Lessen, A. 133, 351). Cocaine,
freshly ppd. by NH, and left under water, slowly
decomposes forming MeOH and benzoyl-ecgonine
(Paul, Ph. [3] 18, 783). The specific rotation in
chloroform' solution at 20° is given by the
formula: [«f]D= -(15-827 + -00585 q), where
q = weight of chloroform in 100 pts. by weight of
tiie solution, and the tube is 100 mm. long. If
q = 0 then [o]„= -15-827.
Salts. — ^BBCl: the melting-point varies
in different preparations between [181°] and
[185°]. For its medicinal employment its abso-
lute purity is essential, and this is best deter-
mined by taking its specific rotation. In dilute
alcoholic solution at 20°, with a tube 100
mm. long, the specific rotation is given by
the formaUi: i«]o= -{52-18 -h -1688 q), and
[a]n=- (67-982 -'158270), where q= weight of
dilute alcohol of S.G. ?i-9353 (mixture of 6 pts.
by weight of absol. alcohol to 9 pts. by weight of
water) in 100 pts. by weight of the solution, and
c = weight of cocaine hydrochloride in 100 pts.
by vol. of the solution. Whan q = 0, then
[o]d = 52-2! when q = 100, then [o]d = 68-0 (An-
triok. B. 20, 310).— B'^H^PtCl..— B'HAuCl,.—
WB^CPi : feathery crystals.
Amorphous coca'ine. An amorphous alka-
loid accompanies cocaine in coca-leaves. It is
V. sol. alcohol and ether. Its hydrochloride is
amorphous, and its solution partially decom-
poses on evaporation, becoming acid (Paul, Ph.
[3] 18, 784). According to Hesse (Ph. [3] 18,
71) this base is isomeric vrith cocaine (c/. Stock-
man, Ph. [3] 17, 861; Howard, Ph. [B] 18, 71;
Bender, G. G. 1885, 490. V. also Ecqonine).
COCATANNIC ACID C„H„08. [189°]. Occurs
in coca leaves (Warden, Ph. [3] 18, 985). Gives
a red colour with KOH. PeSO^ and Vejul^ give
a dark-green colour. Pb(OAo)j gives a rose-red
pp. It reduces alkaline silver solution, but not
Fehling's solution. Potash-fusion gives butyric
and traces x>i benzoic acids.
COCCEKIC ACID CjiHjA- [93°]- Pormed,
together with eocceryl alcohol, by saponification
of ooccerin, the wax of cochineal. White crys-
talline powder. Sol. hot alcohol, ether, benzene,
&c., si. sol. the cold solvents. On oxidation
with CrO, and acetic acid it gives pentadecoic
acid, the same product as from eocceryl alcohol
(Liebermann a. Bergami, B. 20, 964). — A',Oa
and A'jBa : flocculent pps.
Ethyl ether A'Bi. [c. 70°] (Liebermann,
B. 18, 1980).
COCCERIK C3„H5„(0.03iH5,Oj)2. Goccerylcoe-
cerate. [106°]. Occurs in cochineal in quantity
varying from 1 p.o. to 4 p.o. and is obtained by
extraction with benzene. The cocoons of the
cochineal insect consist of coccerin to the extent
of I of their weight (Liebermann, B. 19, 328).
Thin glistening plates. SI. sol. all cold sol-
vents, nearly insol. alcohol and ether. On
saponification with alcoholic EOH it gives eoc-
ceryl alcohol C3oH5„(OH)2 and cocoerio acid
Ca.Hs^O, (Liebermann, B. 18, 1975).
COCCERYl ALCOHOL Cs„,H„<,(OH)j. [101°-
104°]. Formed, together with oocceric acid, by
saponification of coccerin, the wax of cochineal
(Liebermann, B. 18, 1975). White crystalline
powder. On oxidation with CrOj and acetic acid
it gives pentadecoic acid OisHjjOj and probably
also an acid CjjHsjOj.
Acetyl derivative C3„H|i(|(OAo)j : [50°];
crystalline solid ; v. sol. ether, warm alcohol,
and acetic acid ; v. si. sol. acetone.
Benzoyl derivative OaoH|i„(OBz)j : [62°];
crystalline solid; v. sol. ether, warm alcohol,
and acetic acid, v. si. sol. acetone (Liebermann
a. Bergami, B. 20, 959).
COCCINIBT V. Caeminio Aom.
COCCOGNIN CjoHbO,. A crystalline sub-
stance occurring in the seeds of Daphne Meze-
rev/m. SI. sol. water, v. sol. alcohol and ether.
May be sublimed, when it emits an odour like
coumarin. Boiling dilute H2SO4 forms no glu-
cose from it (Casselmann, Z. [2] 6, 681).
C0CCiri.ni C,„HaO„. Occurs in coconlui
indicus. Found in small quantities in the pre-
CODEINE.
281
patation ot piorotoxln {§. v.i, from which it can
be Beparated by means of absolute alcohol, and
leorystailised from hot water acidulated with
HGl. Cone. HsSO, colours it pale yellow, dis-
appearing on stirring (LSwenhardt, A. 222, 353).
COCETHTLINE O.sHjjNO,. [109°]. Ob-
tained by heating benzoyl-eogonine with ethyl
iodide for, 8 hours at 100°. Splendid glistening
prisms. Has an anaesthetic action. FtCl, gives
with very dilute solutions of the hydrochloride a
yellow pp. of the platino-chloride B'ljHjOljPtCl,,
which crystallises from a large quantity of hot
water in glittering yellow rhombic plates. AuGl,
gives a very sparingly soluble yellow pp. HgCl,
forms a white pp., v. sol. hot water (Merck, B.
18, 2954).
COOHLEAHIA OIL. The essential oil of
scurvy-grass {CochUaria officinalis) is isobntyl
thiocarbimide (Hofmann, B. 7, 508).
COCOA HUT OIL or cocoa butter. The fol-
lowing acids have been described as present in
the product of saponification of this fatty oil :
hezoio, octoic, deooio, laurio Oj^^fii, an iso-
meride of laurio [58°], tridecoic 0^,'B.^O,, myris-
tic, palmitic, stearic, oleic, and arachic acids.
Eingzett (C J. 33, 38) also found an acid
0„H,j,Oj [72°] (Bromeis, A. 35, 86 ; FehUng, A.
63, 399; Goergey, A. 66, 290; Oudemans, J.pr.
81, 367 ; Carr Bobinson, 2V. E. 28, 277 ; Traub,
Ar. Ph. [3] 21, 19).
CODAMIKE OjoH^jNO,. [126°] (from benz-
ene) ; [121°] (from alcohol or ether). An alkaloid
occurring in the aqueous extract of opium (Hesse,
A. 153, 56 ; Suppl. 8, 280). Six-sided prisms
(from ether) ; m. sol. boiling water, v. sol. benz-
ene, alcohol, chloroform, and ether. Cone. HNO,
• gives a green solution. Fe^Cl^q gives a green
colour. Cone. H^SO^ gives a blue colour, changing
to green, and to dark violet on warming. NH,
and EOH give pps. sol. excess. — B'2H2PtCl, 2aq.
B'HI l|aq.
CODEiNE OisHjiNO,. Methyl-morphme.
Codeia. [150°]. S.G. 1-32. S. 1-26 at 15?,
6-88 at 100°. [o]d=-134° (in alcohol). S.
(amyl alcohol) 15-68; S. (benzene) 9-60 (Eubly,
J. 1866, 823).
SyntJiesis. — ^By gently heating morphine
(1 mol.) with NaOH (1 mol.) and Mel (1 mol.)
dissolved in alcohol (Grimaux, C. B. 92, 1140,
122S ; Hesse, A. 222, 210). The yield is small,
but by doubling the quantity of Mel a good yield
of codeine methylo-iodide may be obtained.
The codeine so prepared is Iffivorotatory; [«]„ =>
-130°.
Prepa/raUcm. — Aqueous extract of opium is
freed from meconic acid by ppg. with CaClj,
and the filtrate evaporated to crystallisation.
The mixed hydrochlorides of morphine and
codeine are dissolved in water and ppd. by am-
monia; morphine is ppd. but codeine remains
in solution. On evaporating the filtrate codeine
hydrochloride crystallises out (Eobiquet, A. Oh.
[2] 51, 259; A. 5, 106; Gregory, A. 7, 263;
Anderson, A. 77, 341; Ed. Phil. Trans. 20,
57 ; cf. Couerbe, A. Oh. [2] 59, 158 ; Begnanlt,
A. Oh. [2] 68, 136; Gerhardt, Bev. Sdent. 10,
203 ; Winekler, B^p. Phwrm. 44, 459 ; Merck,
A. 11, 279 ; Plugge, Ar. Ph. [3] 25, 343).
Properties. — Trimetrio crystals (containing
aq). From CS, it separates in anhydrous tri-
metric crystals a:&:c = ■930:1:-S09 (Aizruni, Z. K.
1, 302). Lffivorotatory ; [a], (in alooha;) = - 136° ;
(in CHOy= -112° (Hesse, A. 176, 191; c/.
Grimbert, J. Ph. [5] 16, 295). The rotatory
power is much a&cted by the presence and
amount of acid in solution (Hesse ; ^ Tykoci-
mer, B. T. O. 1, 144). It is a strong base,
reddens litmus, and pps. salts of Fb, Fe, Cu,
(fee. Sol. ether. Codeine is insoluble in aque-
ous KOH and hardly more soluble in aqueous
NH, than in pure water. Its physiological ac-
tion resembles that of morphine.
Oolov/r reactions. — 1. H^SO, forms a greenish
solution which, after a week, becomes indigo
blue. — 2. FcjCl, gives no colour. — 3. H^SO^ and
Fe^Cl, gives an intense blue (Lindo, O. N. 37,
158). — 4, Chloride of iodine gives a yellowish
pp. in solutions of salts of codeine. — 5. EjCrO,
gives the chromate. — 6. KjFeCy, gives no pp.
(Plugge, Ar. Ph. [3] 25, 793).
Beactions. — 1. Hot H^SOf decomposes it, and
after diluting, Na^CO, pps. ' amorphous codeine '
as a grey powder [100°], v. sol. alcohol, but ppd,
therefrom by ether. — 2. Heating with KOH gives
off trimethylamine. — 3. Heating with a large
excess of cone. HClAq forms ' chlorocodide '
C,gHj„ClNOj, apomorphine, and MeCl. — 4. HBr
gives ' bromoeodide ' C^H^gBrNO,, ' deoxy-eo-
deine ' C„Hj,N02 (sol. ether), and ' bromo-tetra-
codeine ' O^jHggBrN^O,, (insol. ether) (Matthies-
sen a. Wright, Pr. 17, 460 ; 18, 83 ; Wright, Pr.
19, 371, 504).— 5. HI and P at 100^ to 130°
forms some amorphous substances (Wright, Pr.
20, 8). — 6. Codeine (1 pt.) evaporated with
HPO, (3 pts.) and water (5 pts.) is partly con-
verted into dicodeine C^gH^jK^O, and tetraco-
deine CjjHgjNiO,, (Matthiessen a. Wright, Pr.
18, 87).— 7. Alkaline KMnO, expels half the
nitrogen as NH^fWanklyn a. Gamgee, O.J. 21,
25).— 8: PCI5 forms two bases OigHjoOlNOj and
CijHisCLjNOj (v. Geriohten, A. 210, 107).— 9.
Cyanogen, passed into a cone, alcoholic solution
of codeine, forms crystals of CuHjiNOjCy,.
Salts. — B'HC12aq; radiategroups of prisms.
S. 5 at 15-6° [o]j=-108°.— B'jH2PtCl,4aq:
light yellow powder, gradually becoming crys-
talline.— B'HI aq : long thin needles. S. 1'3. —
B'HI, : red crystals vrith violet reflex. — B'HI^. —
B'HNO, : small prisms, v. sol. hot water. —
B'^HjCgO, 3aq : prisms or scales. 8. 3*3 at 15-5° ;
200 at 100°.— B'HsPO, l|aq : scales or prisms.—
B'jHjSO, 5aq : trimetrio prisms. S. 3*3 in the
cold [o]j = - 101° at 20°.— B'HjSA 5aq : prisms;
S. 5-5.— B'HSCy ^aq. [100°]. Eadiating
needles. Ohloro-aoetate B'CjClHjOj [154°].-
Di-chloro-acetate E'CjCl^H^Oj [156°].-
Tri-ohloro-acetate B'C^ClsHOj. [93°].—
Chloro-crotonate B'C^HgClOj. [171°].—
Tri-ehloro-butyrate B'OACIA [173°].—
Di-bromo-pyruvate B'CsHjBrjO, [70°]
(Daccomo, J. 1884, 1385). , 1
Acetyl derivative CigH^gAcNOg. [135°].
From codeine and AojO (Wright, G. J. 27, 1031 ;
Hesse, A. 222, 212).— B'HCl 2aq.— B'jHjPtOl,.
Propionyl derivative
C,8Hj,(C^50)N03. Prom codeine and pro-
pionic anhydride. Y. sol. alcohol, ether, and
benzene. Gone. H2SO4 gives a blue colour.
Forms well-crystallised salts. — B'HC12aq. —
B'ja JtOl,.— B'HI aq.— B'HjOA 3aq (Hesse, A.
222, 212).
Butyryl derivative CuHjo(CiH,0)NO,.
232
CODEINE.
Amorphous (Beckett a. Wright, C. J. 28, 15). —
BHCl 3aq.— B'jHjPtOI,.
Benzoyl derivative C,bH2|,(C,H50)NO,.
Crystallises from ether.— B'HCl aq.— B'jHjPtOls.
Succinoxyl. derivative
C,sHj„N03{CO.CH2.CHj.COja) 5aq. Formed by
heating codeine (Ipt.) with succinic acid (2 pts.)
at 180° (Beckett a. Wright, 0. J. 28, 689).
Insol. water, ether, and benzene. — B'HCl aq. —
B'^PtOle.
Gamphoryl derivative
C,8H2,K03(G„H,jO,). From codeine and cam-
phoric acid at 180°. Crystalline.— B'HCl 3aq.—
B'jHiPtCl,.
Methylo -iodide CigH^iNOjMel. Prepared
from codeine and methyl iodide, or from mor-
phine, methyl iodide and sodium in presence of
alcohol. Pine needles when hydrated: hard
voluminous crystals when anhydrous. With
moist silver oxide yields a hydroxyl derivative
converted by dehydration into methyl codeine
(g. V.) (Grimaui, A. Ch. [5] 27, 276 ; 0. B. 93,
691). By successive treatment with AcjO and
AgOAc it is converted into C^HnOa [131°] which
crystallises from alcohol in needles (Fischer, B.
19, 794).
Ethylo-iodide CigHaiNOjBtl. Formed by
heating codeine with EtI and alcohol at 100°
(How, 0. J. 6, 125). Cryslialline mass, v. sol.
water. Not decomposed by KOH but converted
by AgjO into a very alkaline hydroxide. The
hydroxide changes, when its alkaline solution is
evaporated, into ethyl-codeine. Acetyl deri-
vative C,8H2„AcN03EtIiaq: crystals, v. si.
sol. cold alcohol (Beckett a. Wright, C. J. 28,
318). . Gives rise to OisHjjAcNOsEtCl and
(C,8Hs„AcNO,EtCl).PtCl4. Butyryl deriva-
tive 0,sHa,(d,H,0)N03EtIiaq.
Chloride CuHjoClNOj. Codeyl chloride.
[147°]. Formed by treating codeine with PCI5
mixed with POCI3. Colourless leaflets ; insol.
water, sol. alcohol and ether (v. Gerichten, A.
210, 105).-B'jH>PtCle.
Chloro-codide OisH^ClNOj. Formed by
prolonged heating of codeine (1 pt.) with cone.
HCl (12 pts.) at 100° (Matthiessen a. Wright, Pr.
17,460 ; 18, 83 ; A. Suppl. 7, 364). Amorphous ;
V. sol. alcohol and ether. Water at 140° gives
HCl and codeine. Cone. HCl at 140° gives
MeCl and apomorphine. — B'HCl : amorphous. —
B'jHjPtCl..
Bromo-codide 0,jH2„BrN02. From codeine
and HBrAq (S.G. 1-5) at 100° (Wright, Pr. 19,
371). Unstable.— B'HBr : gummy.
Chloro-codeline C„Hj„ClN03 l^aq. [170°].
From codeine, KCIO3, and HCl. Crystalline
powder : si. sol. ether and hot water, v. e. sol.
NHjAq.— B'jHjSO, 4aq : prisms.- B'^H^PtCle.
Chloride CiaHijCljNOj. ChLoro -codeyl
chloride. [196°]. Formed by heating codeine
a mol.) with PCI3 ^^ mols.) and POCl, at 70°
(v. Gerichten, A. 210, 105). Trimetric prisms;
insol. water, V. sol. alcohol, ether, and benzene.
Its hydrochloride crystallises in grouped
needles.— B'jHjPtCls.
Bromo-codeine CuHjjBrNOs. [162°]. From
codeine and bromine-water. Needles (containing
4 aq or IJ aq). V. si. sol. water, v. e. sol.
NHjAq.-B'sH^tClj.— B'HBr aq: prisms.
Ethylo-hydrate B'EtOH. Deoompoaes
on evaporation of its aqueous solution forming
bromo-ethyl-oodeine (JB. 15, 1485).
Chloride C,sH„BrClNOj. [131°]. From
bromo-codeine and FCl,. Prisms; sol. alcohol
and ether.
Iri-bromo-codeine , CigH,^r,N02. From
bromo-codeine and bromine-water (Anderson).
Amorphous powder.— B'jSHBr.-B'aH^PtClj.
Oi-iodo-codeine CiaHioIjNOa (?). From
codeine hydrochloride and ICl. Crystals (from
alcohol). Insol. water. — B'sH^PtClj aq.
Nitro-codeme C,8H2„(NOj)NO,. Fromcodeine
and hot dilute HNO3 (S.G. 1-06). Silky laminse
(from alcohol). SI. sol. boiling water (Ander-
son).—B'2H2Pt01e4aq.—B'^S042aq (at 100°) :
radiating needles.
Sicade'ine (CigHsiNOg).^ 2aq. Formed by heat-
ing codeine with dilute HjSOj.with PjOj, or with
oxalic acid (Anderson, Ed. Phil. Trans. 20 [1] 57 ;
Armstrong, C. J. 24, 56 ; Wright, 0. J. 25, 506 ;
28, 312, 696). Amorphous powder. Insol. water,
sol. alcohol and ether. Immediately ppd. from
its salts by Na^COj (codeine comes down only
after some time). FejClj gives no colour.
HNO3 gives a pale orange tint. Hot cone. HCl
converts it into Cj^HjaClNjOuHjClj. HI and
phosphorus at 120° form CujHissINsOaiHals (?).
Salt.— B"H2CLj6aq.
Acetyl derivative (C^jHjnAcNOsJj. From
dicodeine and kojd (Beckett a. Wright, G. J, 28,
15). Amorphous; v. sol. ether. — B"H2Cl2 5aq:
crystalline.— B"H2PtClj.
Tricodeine (C,aH2,N03)3. A product of the
action of H^SO, or of ZnClj on codeine (Wright,
O. J. 25, 507 ; 27, 101 ; Pr. 20, 203). Amor-
phous. Sol. alcohol and ether. Its hydro-
chloride is amorphous and extremely deliques-
cent. Cone. HCl converts it on heating into
apocodeine. Fe^Cl, gives no colour at first, but
afterwards a reddish -purple. HNO3 gives a blood-
red colour. Na^COj immediately pps. it from
solutions of its salts (difference from codeine).
Hot concentrated hydrochloric acid forms
CioBHn4NaO,jH,Cl8.
Tetracodeine (OisHjjNOj),. From codeine
and PjOj. Formed also by boiling codeine with
benzene and NaOEt (Wright, O. J. 27, 107 ; 28,
324). Amorphous ; sol. alcohol ; insol. ether.
Its hydrochloride is amorphous and deliquescent.
Fe2Cla gives inmiediately a reddish-purple colour.
HHO3 gives a blood-red colour. Kfitfi, and
H2SO4 gives an evanescent red colour (this re-
action is given also by tricodeine, but no colour
is got with codeine or dicodeine). KajCO, im-
mediately pps. tetracodeine from its salts.
Boiling aqueous HCl has no action. Boiling
HI a,nd phosphorus form CujHijjIjNjOjjHjIj (?).
Acetyl derivative (CggHsgAcNOg),. From
tetracodeine and AcjO at 120°. Amorphous. —
B"APtCla,
Bromo-tetracodeme C,2Hj3BrN40,2. From
codeine and HBr. HCl forms O^HsjClNjO, jH,Cl,.
Hydric broniide forms bromo-tetramor-
phine OjsH^BrNjOu.
Salt.— C^HjjBrN.CjH^Br^.
Deozycodeiue CigHjiNOj. From codeine and
HBr. Insol. water, sol. alcohol and ether.
Turns brown in air. — B'HBr : small crystals.
Apocodeine CuH^NOj. Formed by heating
codeine hydrochloride with a cone, solution of
ZnClj foi 16 minutes (Matthiessen a. Buruside,
OCEEttLtGNOIft!.
m
Pr. 19, 71). Gummy mass ; insol. water, sol.
alcohol and ether. Gives a blood-ied colour
with HNOj — B'HOl : amorphous. Aots as a
mild emetic.
Methyl-coaoJine 0,8Hj,N0,. Di-rmthyl-
morphAne. [119°]. Prepared by evaporating the
product of the action of silver oxide, or of KOH,
on codeine methylo-iodide. The substance sepa-
rates oat as an oil, which solidifies on desiccation.
Hard, brilliant lamince. It appears to possess
all the properties of a tertiary base and to be
formed by the dehydration of methyl codeine
hydroxide. With sulphuric acid it gives a
brown colouration, turning violet on addition of
water (Grimaux,^. Oh. [5] 27, 283).
Ethyl-codeine Oij^jEtNO,. Formed by
evaporation of a solution of codeine ethylo-
hydroxide.
Methy lo -iodide CisHaBtNOsMel. Eeadily
formed by the union of Mel with ethyl-codeine.
Methylo-hydroxide B'MeOH. Formed
by the action of moist -AgjO on the methylo-
lodide. On heating to 130° it decomposes into
methyl-ethyl-propyl-amine and a body C,5H,„0j
(Geriohten a. Schrotter, B. 15, 1486). The
compound G,5H,„02 [65°] is converted into
phenanthrene by distUlation with zinc-dust.
According to Grimaux (O. B. 93, 591), a crystal-
line tertiary base (? melnyl-ethyl-codeine) [132°]
is formed by heating ethyl-codeine methylo-
iodide with moist Ag^D or KOH.
Bromo-ethyl-codeine CijHjjEtBrNOs. Long
white needles. Sol. acids and strong NHj.
Tertiary base. Formed by evaporation of a
solution of the elhylo-hydrate of bromo-codeine.
Ethylo-hydrateWyLeOiR. Formed by the
action of moist Ag^O on the methylo-iodide. On
evaporating the solution to dryness it decom-
poses into methyl-ethyl-propyl-amine and a
body CjsHgBrOj (Gerichten a. Schrotter, B. 15,
1485). This compound 0,sH;,Br02 [122°] is
converted by CrO, into a substance which is
apparently a quinone.
PICODETHime v.Ethylme-mosBnmv.
CODETHYLENE v. Mhyl-movsm^x.
CffiEULEIN CaiHgO, M.
O
<C C,Hj ^Q
co> ^^{^W "
Formation. — 1. By heating gallein with con-
centrated sulphuric acid at 190°-200°, an olive-
brown solution is formed, from which the coeru-
lein is precipitated by water. — 2. By oxidation
of coeruUn,
Properties. — ^Dark-blue, metallic glistening
crystals, si. sol, water, alcohol and ether.
When heated with zinc-dust phenyl-anthracene
is produced.
Triacetyl derivative Ca,HjOj(OAo)j,
red needles, sol. alcohol, acetone and chloro-
form, readily decomposed with separation of
ccerulein (Buchka, A. 209, 272).
C(EEULIlirC2„H,A»-«-
C.H.<^Ofij>c':.Hffl'>0- Fo-^dbythe
action of concentrated sulphuric acid on gallin ;
formed also by I'eductiou of ccerulein with am-
monia andzino-duBt (Baeyer, B. 4, 656, 663) : the
solution is acidified and agitated with ether, on
evaporation of which oosrulin ia left as a red
substance, sol. alcohol, ether and acetic acid
with golden-green fluorescence. It is readily
oxidised to ccerulein.
Tetra-acetyl derivative
05,„HsOj(OAo)4. [256°], Cannot be prepared
directly from coernlin, but indirectly from cceru-
lein, acetic anhydride and zinc-dust; yellow
needles sol, alcohol, chloroform and benzene,
converted on oxidation into tri-acetyl-ooerulein.
OonstiUtUon. — Ocerulin bears to gallin (g. v.)
the same relation that phenol-phthalidin bears
to phenol-phthalin, as shown by its analogous
method of formation (Buchka, A. 209, 274).
CiERTTLIGMOL G.^uO^i.e. C,H„(OMe)(OH).
Blue-oil. (241° cor.). S.G. is 1-06. Obtained
first by Beichenbach among the higher boiling
portions of beech-tar oil, and characterised by
giving a blue colouration with baryta water. Is
best separated by boihng 4he oil for some time
with acetic acid just strong enough to dissolve
it. On pouring the solution into water the
compound separates out. Colourless oil, of crea-
sote-like odour, m. sol. hot water, alcohol, ether
and acetic acid. From its reaction with nitro-
benzene and strong sulphuric acid it appears to
be a homologue of pyrocatechin, probably of
guaiacol (Pastrovich, M. 4, 188). It gives a blue
colouration with baryta water or bleaching pow-
der ; with ferric chloride in alcoholic solutioh,
a green, but in aqueous solution, a carmine-red
colouration. Heated with hydrochloric acid it
forms a substance C^Hg^Oj i.e. CJB.,„{0T3.)2
crystallising in prisms [56°]. On melting it
evolves methyl chloride.
Acetyl derivative C,(,H„Ac02 (265°);
viscid, colourless oil, once obtained in fan-
shaped crystals.
Nitro-derivative C,oH,,NOA [124°],
obtained together with oxalic acid, the principal-
product, by the action of nitric acid (S.G. 1-12)
on coerulignol. Light yellow crystals, sol. water
and alcohol.
CffiRXriIGNONE CijHi.Os i,e, 0,C8Hj(0M:e),
O.CjH2(OMe)j
Tetra/methyl-ether of ietra-oxy-diphenylene-
gv/inone. Oed/ri/ret. One of the products ob-
tained by Beicheubach from beechwood tar
{J.pr. 1, 1). The crude acetic acid prepared
from wood is treated with KjCr^O, which oxi-
dises the di-methyl-ether of pyrogallol that is
present (Liebermann, B. 5, 746; 6, 381 ; A. 169,
281; Hofmann, B. 11, 335). It is purified by
solution in phenol and ppn. by alcohol or ether.
Small dark steel-blue needles. Insol. ordinary
solvents ; cannot be distilled. Dissolves in cone.
HjSO, with blue colour, but is decomposed
thereby with elimination of one or two methyl
groups. Heated with aqueous KOH it forms a
green solution, quickly becoming yellow. Potash-
fusion gives an intense but fugitive violet colour.
Beducing agents convert it into hydrocoeruMgnoue
CjjHijOe [190°] which is the tetra-methyl-ether
of HBXA-OXY-DrPHENTL (g. «.).
Coernlignoue of the ethyl series
CeHj(OEt)j.O
I I . Greenish-golden glistening
C,H,(0Et)^6
prisms. Prepared by the oxidation of diethyl,
pyrogallol with chromic acid in acetic acid4
234
CCERULTGNONE.
May be reduced to the hydro - derivative
C,Hj(0Et),(0H).0<,H2(0Et),,(0H) [175°] which
crystallises in long white needles (Hofmann, B.
11, 801).
Si-bramo-hydrociBmliguane v. Hzxa-ozx-
DirHENYIi.
COFFEE V. Oatfbini: and Cati'ioii.
COLCHICIlfE CjjHmNO. t.e.
C,5H„(OMe),{NHAo)(COjMe) (?). Methyl ether
of colcHceHn [145°]. Occurs in all parts of the
meadow-saffron {Colchicum cmtv/mnale), espe-
cially in the seeds (Pelletier a. Caventou, A. Oh.
[2] 14, 69 ; Geiger a. Hesse, A. 7, 274 ; Hubsch-
mann, Ar. Ph. [2] 92, 330 ; Asohoff, Ar. Ph.
[2] 89, 4 ; Bley, Ar. Ph. [2] 89, 18 ; Hubler,
O. G. 1865, 536 ; Fliickiger, Ph. [3] 7, 372 ;
Hertel, 0. C. 1881, 501 ; Ph. [3] 12, 498 ; Eosen-
wasser, Ph. [3] 8, 507 ; Houd&s, C.B. 98, 1442 ;
Zeisel, O. B. 98, 1587 ; M. 4, 162 ; 7, 557 ; 9, 1).
Preparation. — The whole seeds are extracted
with hot 90,p.c. alcohol, and the residue digested
with water. The aqueous solution is shaken with
CHCI3. On evaporation the chloroform leaves
a syrupy residue, which after some days begins
to crystallise. It is recrystallised repeatedly
from alcohol and chloroform, and finally from
water (Zeisel).
Properties. — Telloyriflh-white powder. Sol.
water and alcohol; insol. ether; darkens when
exposed to the light. It is leevorotatory. Mineral
acids colour the solution yellow. Weak alkalis
also give a yellow colour; concentrated acids
yield a yellow resinous pp. Cone. HNO, gives a
violet colour. Cone. HjS04 with a trace of nitrate
gives a yellow green. Br water a yellow pp.
Iodine in KI a brown pp. Fefil^ no colour ex-
cept on warming, when a green colour is pro-
duced. HgClj in neutral solutions gives a slight
turbidity, when acid a yellow pp. AuCl, yellow
needles, Cdlj, potassium bismuth iodide, potas-
sium mercuric chloride, phosphotungstic and
phosphomolybdic acids, and chromates give
yellow pps. Tannic acid in acid and neutral solu-
tion a white pp. It forms an addition compound
with CHCI3 of the formula C2jH5,5N05.2CHCl3
with evolution of heat. Yellow needles decom-
posed by water. Phenol gives a milkiness, and
finally a yellow resin. Colchicine acts as a
diuretic, purgative, and irritant poison (Mairet
a. Combemale, O. B. 104, 439, 515).
Salts. — Colchicine is a weak base, most of
its salts being decomposed by water. The aoro-
ohloride B'HAuClj is stable.
Colchicem CjiH^jNOa i.e.
C„H,.(OMe)3(NHAo)(COjH). TH-methyl-acetyl-
eolchicinic acid [c. 166°].
Preparation. — By warming an aqueous solu-
tion of pure colchicine with 2 p.c. HjSOj or 1 p.e.
HCl. Separates in white needles. There are
also formed methyl alcohol, an acid substance,
and a new or possibly two new bases.
Properties. — Shining white needles (contain-
ing I aq) ; becomes anhydrous at 140°-150°.
LiEvorotatory. V. e. sol. alcohol and chloroform,
insol. ether and benzene. Sol. mineral acids giv-
ing a yellow solution, in the case of HCl with rise
of temperature. Alkalis also dissolve it, yield-
ing yellow solutions. Cone. HjSO, and HNO,
behave with it as with colchicine. Br water, phos-
phomolybdic acid and aqueous phenol yield slight
pps. in the aqueous solution, bat not other le-
In HCl solution it behaves like colchi
cine with most reagents. From cone. HCl eola-
tion AuCl, ppts. an orange-gold compound, which
can be subsequently crystallised in needles. Lead
and copper acetates give pps. HCl converts it
into the hydrochloride of tri-methyl-colchicinic
acid G„H2,N0jHCl which forms a Ft salt
(0,BH2,NO,H01)jPtOl4 2aq. The dimethyl-col.
chicinio acid and colchicinio acid are also pro-
duced.
Salts.— B'HAu01j.—(02,HaN0JjCu 5aq
(Zeisel, M. 7, 585 ; 9, 8).
Amide of eolchice'in
CjiHjjNA i.e. 0,sH,(0Me)s(NHAc)(00NHj) (?).
Formed when colchicine and alcoholic NH, are
heated together in a sealed tube. After evapo-
rating the alcohol a yeUow crystalline mass is
left, which is recrystallised from alcohol. Two
kinds of crystals separate. Those which efSoresce
contain ^ mol. alcohol.
ProperHes. — ^Heated with NaHO it forms eol-
chicoin and NH,. It behaves as a base, being sol,
HCl, insol. water. Fe^Cl, gives a brown coloura-
tion, and in HCl solution ENO, gives a violet
colour, and the alkaloidal reagents give pre-
cipitates. Cone. H2SO4 dissolves it, giving a
yeUow-red colouration (Zeisel, M. 9, 26).
COLCHICIHIC ACID ChH.sNOs t.e.
C„H,(0H)3(NH,)(C0,H)(?).
Prqaa/ration. — The hydrochloride remains in
the mother-liquor after separating the dimethyl-
aud trimethyl-derivatives formed from colchicein
by heating with HCl. After drying at 109° the
colchicinio acid is obtained as a yellow powder.
Properties. — HCl solution is ppd. by Br water,
KI, HgClj, Pt01„ AuClj, CdL, and by the usual
alkaloidal reagents. Phenol gives no pp. Cone.
Hj,SO,. gives a brown colouration ; if a nitrate bo
present, and then excess of NH3 added, a red
colour is produced. FcjCl, gives a red-brown
colouration (Zeisel, M. 9, 22).
Dimethyl-derivative C„H,s,N05. [142°].
The hydrochloride is formed with the trimethyl-
dsrivative. It crystallises from hot water as
B'HCl aq, from which the free acid is obtained
in yellow microscopic prisms by the addition of
weak NaHO. These prisms contain 4|aq. A
solutiongivesthe usual alkaloid reactions (Zeisel,
M. 9, 17).
Trimethyl derivative C[9Hj,N0j i.e.
C,jH„(0Me)3(NHj)(C0jH) ? [150°]; From the
hydrochloride formed from colchicein (f.v.).
Microscopic prisms (containing 2 aq). It forms
a Pt salt (B'HCl)jPtCl,2aq.
COLEiN C,gH,„0, (7) A brittle red resin,
which may be extracted by acidulated alcohol
from the leaves of Ooleus VersehaffeltU (Church,
C. J. 31, 253).
COLLAGEN v. Pboteids, Appendix 0.
COLLISINE V. Tm-MEiHTii-ciBiDiiii: and
MeTHIIi-KIHYL-PTEIDINE.
COLLINIC ACID obtained by FrShde (J.pr.
80, 344) by oxidising gelatin with CrO, is Bekzoio
Aon>.
OOLLODION V. CELLni.osE.
COLLOIDS. Name given by Graham to those
substances which do not difiuse through porous
membranes. Colloids are contrasted with Crys-
talloids. V. Diffusion, and PetsioaIi methods.
OOIXOTUSINE V. LoiuBiNE.
COMBINATION, CHEMICAL, LAWS OF.
236
COLOCTNTHIN C^^sAii (?) S. (cold) 5 ; (hot)
6'3. The bitter principle occurring in the pulp
of the fruit of Oitrulliis ColocyntMs (Vauquelin,
J.P}i/ys.8i, 338 ; Braconnot, J. Ph. 10, 415 ; Her-
berger, Buchner's Beperi. 35, 368 ; Baatiok, Ph.
10, 239 ; Walz, Ar. Ph. [2] 96, 141 ; 99, 338 ; Le-
bourdais, A. Ch. [8] 24, 58 ; Henke, Ar. Ph. [3]
21, 200).
Preparation. — The fruit ia extracted with
alcohol, the alcohol is evaporated, and the resi-
due taken up by cold water ; lead acetate is added,
and in the filtrate, after removing the excess of
lead by H^SO,, the colocynthin is ppd. by tannin.
The compound with tannin is then decomposed
by lead carbonate.
Properties. — Yellowish prisms or powder. Sol.
water and alcohol, insol. ether, OS^, benzene,
chloroform, and ligroin. Gone. HjSOj gives a red
colouration. It easily reduces Fehling's solution.
Boiling aqueous ECl gives a dark green greasy
pp., and the solution stiU reduces Fehling's
solution. According to Walz, colocynthin is split
up by boiling dilute H^SO, into glucose (2 mols.)
and a resin oolooynthein OiiHjjO,,.
COLOMBIIT V. OOLDMBIN.
COI,OFH£N£. This name is applied by Ann-
strong and TUden to the viscid yellow oU left
after distilling all that is volatile in steam from
the crude product of the action of H^SOj on the
terpenes. It is probably a mixture of polymer-
ides of these hydrocarbons (C. J. 35, 748). De-
viUe {A. Ch. [2] 75, 66 ; [3] 27, 85) applied the
name to the portion of the product of the action
of H2SO4 on French turpentine that boils a little
above 300°- This might be called dicamphene,
CsgHgj. A similar product occurs among the
products of the distillation of colophony, but it
differs from DeviUe's colophene in forming a
grease when rubbed with slaked lime. V. also
Tbbfenes.
COLOPHONY V. Tebpenes and Tvefeniine.
COXiUUBIC ACID CjiH^jOsaq? An acid
which may be extracted by lime-water from Oo-
lumbo root (Bodecker, A. 69, 47). Amofphous,
nearly insol. water, v. sol. alcohol, si. sol. cold
ether.— Pb2A'4Pb(OH)2aq ?.
COLUMBIA OjiH^jO,. [182°]. S. (alcohol)
3 at 78°. Occurs in the Columboroot (&om Me-
mspermum palmatin, together with berberin and
a substance [220°] which crystallises from HO Ac
in prisms. Prepared by extracting the root with
ether. On evaporation a crystalline residue, to-
gether with a fatty substance, separates out ; the
latter is removed by washing with ether, and the
former crystallised from alcohol (Wittstock, P.
19, 298; Liebig, P. 21, 30; B5se, P. 19, 441;
BSdecker, A. 69, 39 ; Patemo and Oglialoro, Q.
9, 66 ; Alessandri, Ph. [3] 12, 995). Tastes very
bitter. V. si. sol. cold water, alcohol, and ether.
COMANIC ACID OjH302.COi,H i.e.
c^'^cao^^-co^^ (') P^'>°J-
Pr^a/raHok. — 1. Comenio acid (g.v.) is
treated with PCI5 and the di-chloro-comanio
acid produced is reduced by HI (b.p. 127°) (Ost,
J.pr. [2] 29, 62).— 2. Ohelidonio acid is heated
in vacuo at 230° (Haitinger a. Lieben, M. 6,
279).
ProperUea. — Oblique prisms. SI. sol. water.
Gives no colour with Fe-CL.
Beactiom. — 1. Decomposed by excess of
baryta with precipitation, of the salt of an acid
which gives a brown colour with FCjClj. On
warming the pp. with excess of baryta it changes
to baric oxalate, acetone being evolved (compare
chelidonio acid).— 2. Heated by itself it splits
up into CO, and C,H,02, pyrocomane, a neutral
substance, insol. water, [32°] (c. 213°).—
3. Warmed with cone. NH, it reacts thus (com-
pare the behaviour of comenic and of oxy-
comenic acids) : CsH,0, H- NH, = CoHsNO, + HjO.
The product is oxy-pyridine carboxylic (i8-oxy-
picolinic) acid 05H3N{OH)(002H).— 4. When
comanio acid (10 g.), hydroxylarmne h/ydro-
chloride (6 g.), Na^COj (4-5 g.) and water (100 g.)
are warmed together, the sparingly soluble
oximido- acid separates C5H30(NOH).C02H.
Crystallised from water, it forms crystals which
decompose at 200°. With fuming HOI at 200°
this forms CgH^NO:, a crystalline body that is
very soluble in water. The oximido- acid
is reduced by Zn and HCl to oxy-pyridine
carboxylic acid. From this it would appear
that the oximido- acid is di-oxy-pyridine car-
boxylic (di-oxy-picolinio) acid (H. Ost, J. pr,
[2] 29, 378) 5. Eth/ylamme converts oomanic '
acid into oxy-ethyl-pyridine-carboxyHo (oxy-
ethyl-pioolinic) acid, C5HjN(0H)(C0jH)Et. This
acid splits up at 160° into COj and (?) oxy-ethyl-
pyridine.
Salts . — BaA'j aq : v. sol. water. — ^BaA'j 3aq.
AgA'.
Mthyl ether EtA.'. [103°]. Prisms; not
acted upon by AcCl.
Chloro-comanic acid CjHsClOi. [247°].
Formed, together with the following, from co-
menio acid by successive treatment with PCI5
and wat^r. Needles.
Di-oMoro-comanic acid C,HjClj04. [217°].
Needles (from alcohol). HI converts it into
comanic acid.
COHBINATIOIT, CHEMICAL, LAWS OF.—
Chemistry concerns itself with the changes of
composition and properties which certain defi-
nite kinds of matter undergo. Those kinds of
matter which are studied in chemistry are
divided into two classes, elements and com-
pounds. Elements are those Jdnds of matter
which undergo chemical change only by com-
bining with other elements or compounds. Com-
pounds may combine with other compounds or
with elements, or they may be separated into
two or more elements or compounds each unlike
the others, and each weighing less than the ori-
ginal quantity of the compound used.
The expression 'homogeneous bodies' has
sometimes been employed to denote elements
and compounds, and to distinguish these from
mixtures which palpably consist of unlike
portions.
The law of the conservation of matter holds
good in all chemical, as in all physical, changes.
This law may be stated as f oUows as regards chemi-
cal occurrences : — When hwnogeneotis bodies in-
teract to produce new bodies, the sirni of the
masses of the bodies produced is equal to the stmt
of the masses of those which have interacted to
produce them.
The proof of this law is found in the whole
body of chemical and physical science. A few
numbers are here given, taken from the re-
sm
COMBINATION, CHEMICAL, LAWS OR
searches of Stas, which were conducted with
very great care and accuracy.
(1) Silver iodide is the sole product of the
combination of iodine and silver ; if the law of
the conservation of mass holds good, the mass
of silver iodide formed should be exactly equal
to the sum of the masses of silver and iodine
used.
silver
iodide DifCerencea.
Iodine
used.
32-4665
46-8282
44-7599
Silver Sum o{ Sliver
used and Iodine.
27-6223
39-8405
38-0795
160-2752 136-8548
96-7964 82-3631
60-0888
86-6687
82-8394
296-6300 296-624
179-1595 179-159
formed.
60-086
86-6653
82-8375
-•0028
-•0034
-•0019
-■0060
-•0005
The mass of silver' iodide formed was in every
case slightly less than the sum of the masses of
silver and iodine used ; but this is accounted for
by the fact that it .is impossible to collect abso-
lutely the whole of the silver iodide formed. The
differences amount to about ^^ of the total
weight, and fall within the limits of necessary
experimental errors.
(2) In another series of experiments Stas
heated silver iodate, and so decomposed it into
silver iodide and oxygen; the diilferences between
the mass of iodate used and the sum of the
masses of iodide and oxygen obtained amounted
to about j^ of the total weight. Here are a
few of the results : —
Silver Sliver
iodate iodide
98-2681 81-5880
156-7859 130-1755
Oxygen
16-6815
26-6085
Sum Difference
98-2695 + -0014
156-7840 --0019.
Homogeneoits bodies interact to produce new
homogeneous todies in certcum definite and fixed
raUos ; there is a constant ratio between the
masses of the interacting bodies, and also be-
tween the mass of each interacting body a/nd the
■mass of the product, or of each of theprodu^ts, of
the change.
The validity of this statement is assumed in
all chemical investigations. Stas carried out a
series of elaborate researches in order to deter-
mine whether the statement is or is not abso-
lutely accurate. The following numbers taken
from Stas' memoirs are illustrations of his
results.
(1) Potassium chloride was caused to react
with nitric acid to form potassium nitrate ; the
masses of potassium chloride and of potassium
nitrate were determined.
Potassium
Potassium
Potassium nitrate
DiHerence
chloride
nitrate
from 100 parts
from
taken
formed
of chloride
mean
60-7165
68-6938
' 185-643
--002
80-2610
108-8665
185-638
-•007
72-1022
99-8050
135-647
-^•002
50^2175
68-1200
135-649
■f-004
48-9274
63-3675
135-645
•000
69-8836
94-7900
135-640
-•005
14-2578
19^3415
185-655
+ •010
Mean 135-646
The divergences from the mean are very small
and are wholly accounted for by necessary ex-
perimental errors.
(2) A solution of silver was added to a solu-
tion of potassium bromide until the whole of
the bromine was precipitated as silver bromide,
and from the results was calculated the mass of
potassium bromide which reacted with 100 parts
by weight of silver. The numbers obtained
established the absolute identity of the ratio of
silver to potassium bromide in every experiment.
Thus five experiments gave the following re-
sults : —
Potassium
bromide
9-20526
20-12315
15-8310
11-0613
16-3032
surer
8-34305
18-23665
14-3451
10-0253
14-77495
Potassium bro-
mide reacting
with 100 parts of
silver
110-332
110-343
110-357
110-334
110-335
Mean 110^840
Difference
from
mean
-•008
H--003
-f-017
-■006
-•005
The relations between the masses of interacting
homogeneous bodies are expressed in the three
laws of chemical combination, usually known as
the law of fixity of composition, or the law of
constant proportions ; the law of multiple pro-
portions ; and the law of reciprocal proportions,
or the law of combining weights. These laws
may be stated in various forms of words ; the
following are fairly satisfactory.
Law of constant proportions. The masses of
the constituent elements of every compound stand
in an unalterable ratio to each other, and also to
the mass of the compound formed.
Law of multiple proportions. When two ele-
ments combine to form more than one compound,
the masses of one of the elements which combine
with a constant mass of the other element bear a
simple relaUon to each other.
Law of reciprocal proportions; or law of com-
bining weights. The masses of different elements
which severally combine with one and the same
mass of another element are also the masses of
these different elements which combine with each
other, or they bear a simple relation to these
When gaseous homogeneous bodies react to
produce new gaseous bodies, the relations be-
tween the volumes of the interacting bodies and
the volume of the product, or the volumes of the
products, are expressed in the law of volumes or
the law of Gay-Lussac.
Law of volames. When gaseous elements or
compoimds interact, the volu/mes of the interact-
ing bodies bear a simple relation to each other,
amd also to the volumes of the gaseous products
of the reaction.
The law of constant proportions asserts the
absolute invariability of the composition of every
chemical compound. This law was finally gained
as one result of the long controversy waged be-
tween Berthollet and Proust throughout the years
1801 to 1808. Many of the older chemists re-
garded every chemical compound as of fixed
composition; the investigations of Bergmann
COMBINATION, CHEMICAL, LAWS OF.
287
and Lavoisier, for instance, implicitly assumed
the validity of this law of fixity of oomposition.
Indeed, even so far back as the middle of the
17th century Van Helmont spoke of the satura-
tion-point which is reached when a definite
quantity of an acid is added to a specified quan-
tity of a base. The experiments of Hiohter in
the last years of the 18th century rendered it
probable that the masses of two acids, which
severally neutralise one and the same mass of a
given base, bear a constant ratio to each other
independently of the nature of the base with
which they react.
BerthoUet, in his EssaidestaUguecMmic[iie,
published in 1803, stated the fundamental law
of chemical action, to the effect that the amount
of a chemical change is dependent on the affi-
nities and the masses of the reacting bodies.
One of the conclusions which he drew from this
generalisation was, that the composition of the-
products of a chemical reaction may vary within
certain limits, which are determined by the re-
lative masses of the interacting bodies, and by
the physical states of these bodies, and of those
produced in the change. Proust opposed this
notion of variability of composition. He analysed
with great care many series of compounds, chiefly
metaUio oxides and sulphides, and as a final re-
sult he estabUshed the law of fixity of composi-
tion, or of constant proportion, on a firm basis of
experimentally determined facts.
Proust admitted that two elements might
combine in more than one ratio. Indeed he
analysed various pairs of oxides and sulphides
of the same metal; for instance, he gave the
following analyses of oxides of copper and of
tin: —
Copper oxides Tin oxides
(1) (2) (1) (2)
Copper =86-2 80 Tin =87 78-4
Oxygen = 13-8 20 Oxygen = 13 21-6
Proust contented himself with stating the
results of his analyses of compounds in percent-
ages of the constituent elements. Had he calcu-
lated the masses of oxygen which were com-
bined with the same mass of copper, or the same
mass of tin, he might perhaps have forestalled
Oalton and announced the law of multiple pro-
portions. For Proust's analyses quoted above, if
thus treated, give these results : —
Copper oxides Tin, oxides
(1) (2) (1) (2)
Copper =86-2 86-2 Tin =87 87
Oxygen = 13-8 21-5 Oxygen = 13 24
Dalton analysed two compounds of carbon
and hydrogen, and found that the ratio of carbon
to hydrogen in one compound was twice that of
carbon to hydrogen in the other ; in other words,
he found that a fixed mass of hydrogen com-
bined with a definite mass of carbon to form one
compound, and with twice that mass of carbon
to form another compound. Dalton did not
conduct the experiments which led to this result
solely with the view of finding the quantitative
laws of chemical combination, but rather with
the object of rendering clear the atomic concep-
tion of chemical change which at this time was
occupying his attention. While determining
(he composition of series of compounds, he had
always in his mind the conception of chemical
combination as consisting in the union of ex-
tremely minute portions of the combining bodies.
These minute portions, or atoms, of an element,
he pictured to himself as chemically indivisible,
and as all of the same mass ; hence, he argued,
if two elements combine to form more than, one
compound, the masses of one of these elements
which combine with a fixed mass of the other
element must bear a very simple relation to each
other, one must be a whole multiple of the other,
because portions of atoms cannot combine, and all
the atoms of thesame element have thesamemass.
The law of multiple proportions was a neces-
sary consequence of the Daltonian atomic theory.
As a matter of fact, the law was deduced from
experimental data by reasoning directed by the
mechanical conceptions of this theory (v. Aiomio
AND Moi^ouiiAB WEIGHTS, vol. i. pp. 336-7). Dal-
ton's analyses were not very accurate. There can
be little doubt that it was not the analytical results
which led him to the discovery of the law of
multiple proportions, but that the law was ten-
tatively deduced from the atomic conception t^e
had formed of chemical processes, and was then
confirmed by the results of his analyses of com-
pounds.
The announcement of the law of multiple
proportions at once threw a flood of light on the
empirical data already amassed regarding chemi-
cal composition ; and it also led to more careful
analyses of numerous compounds, by showing
the importance of these analyses, and by inter-
preting their results in terms capable of general
application.
After the publication of Dalton's New System
of Chemical Philosophy in 1808, chemists every-
where busied themselves with making accurate
analyses of compounds. Some chemists accepted
the atomic theory of Dalton, others preferred to
speak of combining proportions, or equivalents,
rather than of atoms, of elements ; but whether
accepting or rejecting his theory, all were influ-
enced by Dalton's teaching. The development
of the^tomio theory and the verification of the
laws of chemical combination are indissolubly
bound together.
If the atomic theory were granted, not only
the law of multiple proportions, but also that of
reciprocal proportions, followed as a necessary
consequence. For the masses of two or more
elements which combine with each other must
be the masses, or whole multiples, or sub-
multiples, of the masses, of those elements which
severally combine with a fixed mass of some
other specified element ; because combination
occurs between atoms, and atoms are chemically
indivisible, and all the atoms of any element are
of the same mass.
The outcome of the researches of Berzelius
and his followers into the composition of com-
pounds was to establish the laws of chemical
combination on a firm basis ; but so intimately
were those investigations connected with the
development of the atomic theory, and with the
controversies which attended that development,
that many chemists who demurred to the theory
were inclined to deny the absolute validity of the
laws as expressions of fact, and to think that
these iaws must stand or fall with the theory
which had first given them importance.
238
COMBINATION, CHEMICAL, LAWS OF.
The results of the laborious researches of
Stas ' have shown that the laws of chemical com-
bination by mass are perfectly accurate state-
ments of facts which hold good in all chemical
processes.
Some of the results obtained by Stas have
been already given (p. 236). The following
analyses of silver chloride, and of ammonium
chloride, prepared by different methods, serve to
show that the composition of each of these two
compounds at any rate is absolutely fixed : —
Glrams of silver
Method of chloride obtained
preparation of silver chloride from 100 of silver
, 1. Ag burnt in CI gas . . 132-842
2. Ag dissolved in HNOjAq,
and ppd. by HOI gas . 132-847
3. Ag dissolved in HNO^Aq,
and ppd. by HClAq . 132-848
4. Ag dissolved in HNOjAq,
and ppd. by NH^ClAq . 132-842
The ammonium chloride analysed was pre-
pared in four different ways : —
(1) Commercial salammoniac was dissolved
in water and boiled with nitric acid to destroy
organic matter ; the Uquid was decomposed by
pure lime ; the ammonia produced was led into
water and then neutralised by hydrochlorioacid;
the ammonium chloride was sublimed in a stream
of ammonia.
(2) Commercial sulphate of ammonia was
heated with sulphuric acid, then boiled with
nitric acid ; the solution was treated in the same
way as described in (1).
(3) A solution of potassium nitrite was mixed
with potash, zinc-dust was added, and the liquid
warmed; the nitrite was thus reduced to am-
monia, which was led into water, and then
neutralised by hydrochloric acid, the ammonium
chloride was sublimed in an ammonia-stream.
(4) A part of the ammonium chloride pre-
pared in (3) was sublimed in vacuo.
Weighed quantities of the different prepara-
tions were dissolved in water, and the quantity
of silver required for the precipitation of all the
chlorine was very accurately determined ; ex-
periments were conducted at different tempera-
tures. A selection is given from the results : —
Qnans
used
Silver
used
Grams
NH,01 de-
composed
by 100'
grams
silver
Speci- Ut 20°
men (1) | at 100°
, > at 20°
" ^^> at 100°
,„> /at 20°
" W\at 20°
,.>/at 20°
" Wlat 20°
11-79643
39-62130
11-80844
13-40631
6-25216
10-71756
13-5129
6-2250
23-7843
79-88613
23-8086
27-0277
12-60716
21-6093
27-2429
12-5523
Mean
49-598
49-5974
49-597
49-602
49-693
49-597
49-598
49-592
49-5968
* Recherchea stir la rapportt ridproques cles poidt ato-
miquet [1860]. Noumllesrechereliet sur let lots desproportioTU
chimigueat sur les poids atomigues et leurs rapports mvivels
[1866], A. German translation of both memoirs was pub-
Ushed in 1867, with the title UntersvdntngmiiberdieQesetze
der chemisdien ProporUonm, Uber die AlomgemiMai tout
Uf« gegensettinen TerMUviue.
One of the forms in which the law of r«ci-
procal proportions may be stated is as follows :
The elements combine m the ratios of their com-
bining weights, or in ratios which bear a simple
relation to these. By the combining weight of
an element is here understood the smallest mass
of that element which combines with unit mass
of a standard element (v. Oousininq weiohis of
eiiEUENIb). Suppose the standard element were
oxygen ; then if the combining weight of an
element were determined from analyses of dif-
ferent compounds of that element, all of which
compounds contained oxygen, the law asserts
either that the same value for the combining
weight should be deduced from all the analyses,
or that the different values found should bear a
simple relation to each other. Stas proved the
absolute accuracy of the law as regards silver,
by determining the mass of this element com-
bined with 16 parts by weight of oxygen in
various compounds. The compounds chosen
were, silver iodate, bromate, chlorate, and sul-
phate. Stas reduced these compounds to silver
iodide, bromide, chloride, and sulphide, respec-
tively, and then determined the amount of silver
in these salts.
The following values were obtained for the
mass of silver combined with iodine, &o., and ,16
parts by weight of oxygen : (1) From analyses
of iodide prepared by reducing iodate 107 928;
(2) from analyses of bromide prepared by re-
ducing bromate 107-921; (3) from analyses of
chlorate prepared by reducing chloride 107-937 ;
(4) from analyses of sulphide prepared by re-
ducing sulphate 107-920. Stas further reduced
potassiuin chlorate tg chloride and then deter-
mined the mass of silver needed tb precipitate
the chlorine which was combined with 16 parts
of oxygen.in the original chlorate ; he thus in-
directly obtained a value for the combining weight
of silver, meaning thereby the mass of this
element which combines with that mass of
chlorine which enters into union with 16 parts
by weight of oxygen; the number found was
107-930. Another method which Stas used for
testing the accuracy of the law of reciprocal pro-
portions consisted in finding the ratio of the
masses in which two elements united to form a
binary compound, and also the ratio of the
masses in which the same pair of elements were
united in a compound formed by the addition of
a third element to the first binary compound.
Stas determined the ratio of silver to iodine in
silver iodide and iodate, of silver to chlorine in
silver chloride and chlorate, and of silver to
bromine in silver bromide and bromate. The
results proved the absolute accuracy of the law.
There can be no doubt as to the accuracy of
the laws of chemical combination by weight.
These laws are perfectly accurate statements of
facts, and they bold good in every chemical
change.
The law of combination of gaseous elements
and compounds by volume, enunciated by 6ay-
Iiussac, has not yet been subjected to so rigorous
an examination as that which the laws of com-
bination by weight have undergone.
The ratio of the volumes in which hydrogen
and oxygen combine to form water was deter-
mined by Lavoisier, in 1783, to be 1-91:1. Other
ohemists stated the ratio to be approximately
COMBINING WEIGHTS OF THE ELEMENTS.
>:1. In 1805 Gay-Lussao and Hamboldt an-
noniioed that the ratio was exactly 2:1, and in
1808 Gay-Lussac made the generalisation, which
he based on numeroas experiments, that the
volumes ot gaseous elements or compounds
which combine to form gaseous products can be
expressed by small whole numbers, and that the
Tolnme of the gaseous product of such combina-
tions is either the smn of the volumes of the con-
stituents or it bears a very simple relation (J, J,
i, &a.) to this sum. Qay-Lussac's experiments
showed, for instance, that 1 volume of nitrogen
combines with 3 volumes of hydrogen to form
2 volumes of ammonia, and with 2 volumes of
oxygen to form 2 volumes of nitrogen dioxide,
Ac.
Investigations have recently been made by
Scott regarding the volumetric ratio in which
hydrogen and oxygen combine to form water.
The results {v. Scott, Pr. 1887. 398 ; B.A. 1887.
668 ; iV. 87, 439) do not finally settle the ratio
but they all tend to show that it is slightly less
than 2:1, the most probable value being 1-997:1.
The laws of chemical combination are all
included in the two statements :
1. The elements combine in the ratios
of their combining weights, or in
ratios which bear a simple relation to
these.
S. The gaseous elements combine in the
ratios of their combining volumes, or
in ratios which bear a simple relation
to these.
By combining weight is here meant the
smallest mass of an element which combines
with unit mass of some specified element taken
as a standard; and by eombining volume is
meant the smallest volume of a gaseous element
which combines with unit volume of some
specified gaseous element taken as a standard.
The first statement has been amply verified
by accurate experiments ; the second does not
yet stand on so firm an experimental basis.
In connexion with this article v. the articles
Atouic and molecvlab weiohts; CoMBiNma
WEIGHTS of elements; Coufosiiion, ohemical;
Equivalents ; Fokmul^. M, M. F. M.
GOUBINING WEIGHTS OF THE ELE-
KENTS.- The laws of chemical combination by
mass are expressed in the statement, theehmenh
combine in the ratios of their combinimg weights,
or in ratios which bewr a simple relation to these.
The term combinmg weight is here taken to
mean the smallest mass of an element which
combines with unit mass of a standard element.
Hydrogen is adopted as the standard element ;
hence the practical definition ot combining
weight, as here understood, is the smallest
mass of an element that combines with 1 part
by weight of hydrogen. But many elements do
not combine with hydrogen ; it is therefore often
necessary to make use of some element other
than hydrogen as a standard.
All the element? except fluorine and bromine
form oxides, and most of the elements combine
with chlorine. These two elements, oxygen and
chlorine, are therefore frequently used as stan-
dards of ref ei;ence in determinations of combining
weights.
Oxygen combines with hydrogen in two
ratios (by weight), 8:1 and 16:1 ; bat chlorine
and hydrogen combine only in the ratio 35*5:1
(these values are given in round numbers). In
accordance with the definition given above, the
combining weight of oxygen is said to be 8, and
the combining weight of bhlorine to be 35-5.
The combining weight of an element may then
be taken to be the smallest mass of it which
combines with 1 part by weight of hydrogen, or
8 parts by weight of oxygen, or 35-5 parts by
wdght of chlorine.
The same value is found for the combining
weights of some elements which form both
oxides and chlorides, whether the value is deter-
mined from analyses of the compounds with
oxygen or with chlorine. Sodium and silicon
are cases in point. But in some cases, one value
is found for the combining weight of an element
from analyses of its oxide, and another value
from analyses of its chloride. Thus -^ is the
smallest mass of iodine that combines with 35'5
parts by weight of chlorine, but ifi parts by
weight of iodine combine with 8 parts of oxygen,
and if the combining weight of iodine is deduced
solely from analyses of its hydride, the value
found is 127. So also, the smallest mass of
nitrogen that combines with 1 part by weight of
hydrogen is 4*66, but a compound of nitrogen
and oxygen is known which is composed of
2*8 parts of nitrogen in union with 8 parts of
oxygen.
Different values, then, are frequently ob-
tained for the combining weight of an element
according as the combining weight is determined
in reference to hydrogen, chlorine, or okygen, as
the standard element. But the different values
always bear a simple relation to each other.
The following table presents the values found
for the combining weights of a few elements;
the ratios of the numbers are stated in the last
column. Bound numbers are given : —
Combining weights
Batlo ol
referred to
values
H = l 0 = 8 Cl = 3B-5
Nitrogen .
. 4-6 2-8 4-6
6:3:5
Potassium .
. — 9-75 39
1:4
Copper
. 63-2 31-6 31-6
2:1:1
Arsenic . .
. 25 15 25
5:3:5
If, then, we define combining weight solely
in terms of hydrogen as unity, we can determine
the combining weights only of a minority of the
elements ; if we admit the employment of oxy-
gen and chlorine as standards of reference, we
frequently arrive at different values for the com-
bining weight of the same element. One primary
object in determining combining weights is to
find a basis for a system which shall represent
the composition of compounds in formulas, by
showing the number of combining weights of
each element which are combined to form that
quantity of a specified compound which is repre-
sented by its formula. In order to frame a satis-
factory system of notation, some compromise
must be come to as to the meaning to be given'to
the term combining weight. The di£Scnlty may
be partly overcome by adopting as the com-
bining weight of an element the least comnjon
multiple of the numbers which express the
masses of the element that severally combine
with 1 part by weight of hydrogen, 8 parts of
oxygen, and 35*6 parts of chlorine. For instance,
240
COMBINING WEIGHTS OF THE ELEMENTS.
In the case of nitrogen, the L.C.M. of 2-8 and
4*66 is 14 ; and in the case of arsenio, the L.C.M.
of 25 and 15 is 75.
The values thus obtained are usually adopted
when it is desired to frame a fairly satisfactory
definition for the term combining weight. These
values are either the same as the atomic weights
of the elements, or the latter are whole multiples
of the former numbers. If a satisfactory and
consistent system of notation is to be based on
the combining weights of the elements, it is better
to adopt for the combining weights values which
are always identical with the atomic weights.
The term combining weight of an element must
then be taken to mefln either the smallest whole
number, or a whole multiple of the smallest whole
number, divisible without remainder by each of
the numbers that express the masses of the
element which combine with 1 part by weight of
hydrogen, 8 parts of oxygen, and 35-5 parts of
chlorine, respectively. The following table ex-
hibits the smallest masses of each element that
combine with 1 part by weight of hydrogen, 8
parts of oxygen, and 35-5 parts of chlorine ; it
also shows the L.C.M. of these numbers, and
the last column contains the whole number by
which each L.C.M. must be multiplied in
order to get the value used as the combining
weight of the specified element in the ordinary
chemical notation, which value is identical with
the atomic weight of the element. (The values
in the table in the next column are given in
round numbers.)
The combining weight of an element is some-
times said to be the smallest mass of that element
which enters into chemical combination with
other elements, the smallest mass of hydrogen
which combines chemically being taken as unity.
But in order to give an exact meaning to the
phrase, ' smaUest relative mass of an element
which enters into chemical combination with
other elements,' it is necessary to add, ' to form'
a chemically reacting unit of a compound,' or
some such expression as this. Now, the only
conception of 'the chemically reacting unit of a
compound ' which has been put into an exact
form capable of presentment in quantitative
terms and of general application is that which
arises from the application of the molecular and
atomic theory to chemical occurrences ; it is in-
deed the conception of the molecule. The defi-
nition of combining weight as ' the smallest rela-
tive mass of an element which enters into
chemical combination vrith other elements ' is
essentially an atomic and molecular definition,
although it 'is not couched in atomic and mole-
cular language. For many years attempts were
made to base a system of representing the com-
position of compounds on the combining weights
of the elements without the help of the concep-
tions of atom and molecule. That mass of an
element which combined with 1 part by weight
of hydrogen, or 8 parts of oxygen, was sometimes
taken as the combining weight of the element,
and sometimes a multiple of this mass was pro-
posed. But it was only when the atomic and
molecular theory led the way that a satisfactory
ana consistent scheme of representing chemical
composition was gained. The atomic weight of
an element is always equal to, or is a whole mul-
tiple of, the least common multiple of the nxaa-
'
Smallest mass of
, :<
element that combines
with
L.O.M.
L.O.X.
"SlemtnA
of these =at.
numbers vrt.x»
jDiiaiuoiiw
1 part
bywt
ofH
35-6
parts of
Gl
8 parts
of 0
Alnmlnlnm . .
9
9
9
Antimony . .
40
24
24
120
Arsenio . •
25
26
16
75
Barium .
68-5
34-35
68-5
Beryllium .
—
4-5
4-6
4-6
Bismuth
«
69-33
41-6
208
Boron . • ,
—
3'G6
3-66
3-66
Bromine .
SO
80
—
80
Oadmlnm .
fi6
28
66
OsBsium • •
—
133
133
133
Oiiloium .
—.
20
20
20
Carbon « •
3
3
3
3
Corium .
36
36
36
Chlorine .
35-6
— .
8-876
36-5
Chromium • •
—
17-4
17-4
17-4
Cobalt .
29'S
W-66
69
Copper . .
63'2
31-6
31-6
63-2
Didyminm ,
—
48
28-8
144
Erbium • . •
...
65-33
66-33
56-33
^ 3
Fluorine • .
19
19
19
Gallium . .
23-3
23-3
23-3
Germaulnm.
—
18-05
18-06
18-06
Gold . . .
_
68-66
65-66
65-66
Hydrogen .
_
1
1
1
Indium .
—.
3r-8
37-8
37-8
Iodine . • •
127
42-33
25-4
127
Iridium
_
48-15
32-1
96-3
Iron . . .
—
18-66
18-66
18-66
lianthanum
^
46-66
46-66
46-66
Lead . . .
m^
103-6
61-76
103-6
Lithium . .
..
7
7
7
Magnesium • .
^
12
12
12
Manganese .
^
27-6
13-76
52
Mercury . •
^ '
100
200
200
Molybdenum
—
19-2
16
96
Nickel . . .
_
29-3
29-3
29-3
Niobium . .
__
18-8
18-8
18-8
Nitrogen .
4-66
4-66
2-8
14
Osmium
47-76
23-776
47-76
Oxygen
8
8
8
Palladium .
—
2e-6
26-6
26-5
Phosphorus.
10-33
6-2
6-2
31
Platinum .
__
48-S
48-6
48-6
Potassium . .
—
39
39
39
Bhodiiun .
_
26
17-33
104
Bnbidium • •
85-4
85-4
85'4
Ruthenium .
26-15
26-16
26-16
Scandium •
__
14-66
14-66
14-68
Seleniou m
39'6
19-76
13-33
80
Silicon . M -.
7
7
7
7
Silver . , .
108
108
108
Sodium
23
23
23
Strontium • •
-_
43-6
43-5
43-6
Sulphur .
16
8
6-33
16
Tantalum .
_
36-4
36-4
36-4
Tellm-ium .
62-5
31-26
20-83
62-6
Terbium , .
49-33
49-33
49-33
Thallium ,
•M,
68
68
68
Thorium .
_
68
68
68
Tin . . .
—^
29-6
29-6
29-6
Titanium ., .
_^
12
12
12
Tungsten . ' .
..
30-66
30-66
30-66
Uranium • 4
._
48
60
240
Vanadium • •
__
12'8
10-24
61-2
Ytterbium .
—
67-66
67-66
67-66
Tttrium ■ •
_
29-66
29-66
29-66
Zinc . . .
«
32-6
32-6
32-6
Zirconium . .
—
22-8
22-5
22-6
bers that express the smallest masses of the
element which combine with 1 part by weight of
hydrogen, 8 parts of oxygen, and 35'6 parts of
chlorine, respectively ; the principles which guide
chemists in their choice of the multiple are set
forth in the article Atomio and MOLEcmiAB
WEiQHia. If accurate values are to be found for
the atomic weights of the elements, it is evident
that the combining weights must be determine^
with the greatest care.
COMBUST [ON.
S4!
The exact definition to be given to the term
eombining weight is not a matter of paramount
importance, for it is evident that whether we call
the combining weight of an element the smallest
mass of it which combines with 1 part by weight
of hydrogen, or 8 parts of oxygen, or 35'5 parts
of chlorine, or whether we say that the combin-
ing weight is the Ii.C.M. of these numbers, or
whether we take the expression to mean a whole
multiple of this L.C.M., in any case the law
holds good that the elements combine in the
ratios of their combining weights or in ratios
which bear a simple relation to these. What is
required to be determined with the greatest care
and accuracy is the ratio between the combining
masses of every element and hydrogen, oxygen,
chlorine, orother standard element ; because this
ratio, taken in conjunction with the definitions
of atom and molecule, determines the value of
the atomic weight of the element, and on this
value depend many of the chemical properties of
the element. In connexion with this article v.
the arts. Atomic and uoi<ecuiiAB weiohis ; Gom-
BiNATioN, CKBBnoAii, iiAws OS ; 'Eas.watjM ; Nota-
tion. M. M. P. M.
COMBTTSTION.— Any manifestation of chemi-
cal energy attended by combination and accom-
panied by production of much heat is, strictly
speaking, an instance of combustion. As com-
monly used, however, the texm carries with it
the idea of incandescsnce ; that is, the reacting
bodies are not merely mcalBscent, but have
their temperature raised to a point at which they
einit light, or become self-luminous. This defi-
nition includes that of inflammation, which is,
however, best restricted to instances of combus-
tion in which the incandescent substances are
gaseous. Such cases of combnstioh wUl be con-
sidered under FiiAme.
All phenomena of burning are instances of
combustion, and in the great majority of cases
they consist in the union of the oxygen of the
air with the substance which is being burnt,
the visible signs of combustion, i.e., the heat and
light, being the result immediate or proximate
of the chemical energy so expended.
It has been frequently observed that primi-
tive communities regard as sacred all things that
contribute to their existence or promote their
well-being, and hence it is intelligible that a
phenomenon so mysterious in its origin and
process as fire, and at the same time so neces-
sary to the welfare of mankind, should have
been looked upon from the earliest times with
particular reverence and awe. The evidence of
fire worship is to be found probably in every
religion. And it would be easy to show on
strictly evolutionary principles how the idea of
sanctity associated with the phenomenon of
burning ramified and became interwoven into
theories of the origin of life, of generation, and
the nature of the soul and mind, and how it
passed into the art of healing, and thence into
the sciences which have sprung out of, or have
been grafted on to, that art. The idea, but Uttlo
shorn of its transcendental and spiritual attri-
butes, is to be found in the earliest theories of
chemistry. Fire plays such an important part
in the operations of chemistry, the changes
which it induces are so profound and extraordi-
nary, burning and the evolution of heat by in-
voL. n.
trinsic agencies are so constantly witnessed ati
the result of chemical operations, that it ia
hardly surprising that the earlier chemists
should have regarded combustion, as the essen-
tial phenomenon of chemistry. A theory of
combustion was to them also a theory ol
chemistry. Minds so sharply contrasted as
those of Bacon and Boyle clearly apprehendedthe
importance of a comprehensive theory of com-
bustion from this point of view, but Bacon made
no attempt to construct such a theory, and Boyle,
in spite of his habitual caution, weiit singularly
wrong in his efforts to explain the essential
nature of fire and the phenomena we now recog-
nise as due to oxidation. John Joachim Becher
(1635-1682) has the credit of having first at-
tempted to group aU the facts of chemistry then
known in such manner that they could be de-
duced from one general or universal principle.
George Ernest Stahl (1660-1734) eagerly adopted
Beoher's fundamental idea, and amplified and
worked it into a comprehensive system, capable
of wide generalisation and fruitful of fresh lines
of investigation. The theory of Becher and
Stahl was essentially one of combustion. As it
has exercised a very powerful infiuenqe on the
development of chemistry, it may be desirable to
sketch its main features with some degree of
detail.
The theory as elaborated by Stahl is to be
found in his Fundamenta Ohymia, published in
1720, when its author was resident at Berlin as
physician to the King of Prussia. It is not im-
probable that it was taught publicly at Halle
between 1694 and 1716 when Stahl was Pro-
fessor of Medicine at that University. Stahl de-
fines chemistry as the art of resolving com-
pounds into their constituents, and of recom-
bining these constituents to again form the
original or other compounds. According to
Becher and Stahl, all combustible bodies are
compounds, and in the act of burning they part
with a constituent which is common to them all.
This common principle was termed by Stahl
phlogiston (it>\oyurr6s = burnt). Bodies are com-
bustible in proportion as they contain phlogiston ;
phosphorus, sulphur, charcoal, alcohol, sugdr,
the oils, resin, &e., are pre-eminently endowed
with it. The metals also contain it, but in vary-
ing amount. When certain of the metals are
strongly heated they are gradually converted
into an earthy powder, termed a calx. The
change which the metal had undergone was con-
sidered by Stahl as akin to ordinary combustion,
and metals were regarded as compounds of calces,
which were recognised as intrinsically dissimilar
bodies, in union with the common principle,
phlogiston, which was dissipated by the action
of heat upon the metal. The re-conversion of
the calx into the metal by processes which we
now term reduction, that is by the action at a
sufficiently high temperature of bodies like char>
coal, coal, or by combustible gases, &c., was ex-
plained by Stahl as being due to the union of
the phlogiston of the charcoal, &o., with the
calx of the metal. It was noticed that many
substances like phosphorus and sulphur on being
burnt formed acids which when treated with
a highly phlogisticated body such as charcoal
gave rise to the original substances. Thus,
phosphoric aoid on being heated to a high tem^
242
COMBUSTION.
perature with charcoal formed phosphorus again.
Hence phosphorus was considered to be a com-
pound of phosphoric acid and phlogiston; in
the act of burning the phlogiston was disen-
gaged and the acid left; on restoring phlogiston
to the acid the phosphorus was regenerated.
Stahl sought to demonstrate the identity of the
combustible principle in aU substances by point-
ing to the fact that the calx of lead, for example,
could be conyerted into the metal by the em-
ployment of phlogisticated bodies of such widely
different properties as charcoal, sulphur, flour,
sugar, iron, &e. As only one substance, viz.,
lead, was formed by the action of each of these
bodies, it seemed to follow that they must aU
contain a common principle. In the same way
it was pointed out that phosphoric acid could
be changed into phosphorus by the action of a
great variety of combustible bodies, such as
lamp-black, resin, sugar, or even the metals.
Of course it was known that many substances
existed which were incombustible and were not
sensibly changed by the action of fire, as, for
example, lime, clay, rocks, &o. ; such bodies were
regarded as dephlogisticated by the action of pre-
vious heat, or as being incapable of combining
with phlogiston. As the doctrine of phlogiston
extended, the ideas of the phlogistic school re-
specting its essential nature became more and
more vague. There seems to be no doubt, how-
ever, that Stahl and his immediate followers,
Neumann, Pott, and Margraaf, in Germany, and
BSaumur, Duhamel, and Macquer, in Frince, re-
garded phlogiston as a definite substance pos-
sessing all the essential attributes of matter.
Stahl himself appears to have considered that
phlogiston, when isolated, would turn out to be
a solid earthy body insoluble in water like char-
coal, sulphur, phosphorus, bitumen, and the
metals. Indeed, as so many highly phlogisticated
bodies were insoluble in water, while their de-
phlogisticated constituents, e.g., phosphoric and
sulphuric acids, were readily soluble, the pro-
perty of solubility came to be regarded as depen-
dent on or related to the presence or relative
amount of phlogiston. Its presence or absence
in fact affected all the properties of bodies, and
caused all the changes they were capable of ex-
periencing, as, for example, their relative sta-
bility, their capacity for union with other bodies,
their acid or canstio characters, their colour,
odour, and taste, and even their physiological
and therapeutic activity. Many other natural
phenomena, such as fermentation and decay,
the growth of plants, and the processes of animal
life, were also capable of explanation by the aid
of the same general principle.
The doctrine of phlogiston was of incalcu-
lable service to chemistry. Indeed, it is not too
much to say that Stahl's generalisation first
raised chemistry to the dignity of a science. It
not only served to present a simple and intelli-
gible explanation of a mass of hitherto uncon-
nected facts, but it pre-eminently fulfilled the
function of every fruitful hypothesis by stimu-
lating fresh inquiry and suggesting new lines of
thought. Men like Black and Cavendish, whom
we commonly reckon as phlogistians, were, how-
ever, not unmindful of its weaknesses, and Black
certainly recognised its inadequacy to explain
facts which he knew to be incontrovertible, such,
for example, as the results obtained by Boyle on
the calcination of metals. Boyle himself was
doubtless aware of the doctrine in the form in
which it was presented in Becher's Physica
Subterranea, but it had probably no influence
on his labours. Indeed he failed to perceive
that much of his work was in direct opposition
to Becher's teaching. His experiments on the
calcination of lead and tin were interpreted by
him as proving the tnateriality of heat, and it
was reserved for Lavoisier and the so-called anti-
phlogistic school of French chemists to point
out their real significance.
The doctrine of phlogiston was paramount
in cliemistry for upwards of half a century : the
discovery of nitrogen by Butherfordin 1772, and
of oxygen by Priestley in 1774, and the fuller
recognition of the functions of these bodies in
the air, by paving the way towards a clearer
apprehension of the nature of combustion,
brought about the downfall of Stahl's generalisa-
tion. Geber, upwards of ten centuries ago, had
supplied chemistry with facts respecting the
nature of calcination which the long subsequent
labours of Sulzbaoh, Cardan, Bey, and Boyle had
confirmed and strengthened. Hooke, in the
MicrograpMa, and Mayow, in his Ojpera Oninia
Medicophysica, pointed out that combustion con.
sists in the union of something with the body
which is being burnt, and Mayow, both by ex-
periment and inference, demonstrated in the
clearest Way the analogy between respiration
and combustion, and showed that in both pro-
cesses one constituent only of the air is con-
cerned ; he distinctly stated that not only is there
increase of weight attending the calcination of
metals but that this increase is due to the ab-
sorption of the same spiritus from the air that
is necessary to respiration and combustion.
Mayow's experiments are so precise, and his
facts so incontestable, that, as Chevreul has said,
one is surprised that the truth was not fuUy re-
cognised until a century after his researches.
This recognition was forced upon the world by
the experimental labours and writings of La-
voisier and his immediate followers in France.
By repeating and extending the observations of
Mayow, Black, Butherford, and Priestley, La-
voisier proved that respiration, combustion, and
calcination are essentially identical processes, in
that they are primarily due to the action of oxy-
gen— Priestley's dephlogisticated air — on the
body undergoing change, and that the heat which
is manifested is the result of the chemical change
of which all these processes are examples. La-
voisier's experiments were so well devised and
so admirably executed, his reasoning was so
perspicuous and his proofs so irrefragable, that
his conclusions seemed irresistible so far as the
theory of combustion was concerned.
As Lavoisier's explanation of the true nature
of combustion effected a complete revolution in
the theory of oheriustry, it may be desirable to
trace the steps by which he was led to formu-
late it.
Lavoisier published in all some sixty me-
moirs, about half of which were concerned with
the subject of combustion and of matters which
immediately grew out of it. These appeared
in different memoirs of the Academy between
1774 and 1788. It appears from bis collected
COMBUSTION.
243
memoirs, published after his death in 1794,
that his earliest experiments on the cause of
the augmentation of weight which bodies ex-
perience during combustion and caloiiiation
were -made in 1772.
In a memoir published in 1774 Lavoisier de-
scribed a repetition of Boyle's experiments oh
the calcination of tin, in which he showed that
during the formation of the calx a portion of the
air disappears, and that the tin increases in
weight in amount equal to the loss of weight
experienced by the air. Hence he concluded that
a portion of air had unitedwiththe tin, and that
the calx of tin is composed of tin and air.
There is nothing in this memoir nor in the
note of 1772 to indicate that Lavoisier had any
idea of the compound nature of air. StiU it is
evident that he had advanced beyond the posi-
tion of Boyle and Eey. Boyle inferred that his
experiments proved the materiality of heat, while
Eey appears to have imagined that the absorbed
air was merely entangled with the metal.
In the autumn of 1774 Priestley exhibited to
Lavoisier his method of making oxygen gas from
the calx of mercury. In the following year ap-
peared Lavoisier's memoir On the nature of the
principle which combines with the metals dwring
their calcination and which augmenis their
weight. Starting from the fact that many of
the metaUio calces can be reduced by charcoal
with the production of a! gas which is identical
with that produced by burning charcoal in the
air, Lavoisier concluded that carbonic acid gas
contains an elastic principle which is common
to the air and the metallic calx. In the case of
the calx of mercury he could obtain this elastic
principle by heat alone. The gas so obtained
was identical vrith Priestley's dephlogisticated
air. Lavoisier surmised that this gas, which he,
like Priestley, found to be pre-eminently a sup-
porter of combustion and respiration, was pro-
bably contained in nitre, inasmuch as this salt
when heated with charcoal forms large quantities
of carbonic acid gas. Mayow, on other grounds,
had -already made the same supposition. This
memoir was followed in 1777 by that On the
combtisUon of phosphorus and the nature of
the acid which results from that combustion, in
which Lavoisier first distinctly recognised that
the air was composed of two distinct substances,
one of which was absorbed by the burning phos-
phorus to the extent of one-fifth of the original
volume of air, while the other, originally termed
by him mouffette atmosph4rigue, was incapable
of supporting combustion or animal life, and was
not absorbable b> laetals when heated, and hence
was not concerned in the process of calcination.
In the same year he published a paper On the
combustion of candles in atmospherical oAr, and
in air eminently respvrable, in which he demon-
strates that the mouffette aimosph^rigue, or azote
as it is now called, plays no part in the burning
of the candle, but that the combustion is entirely
due to the dephlogisticated air or oxygen. Al-
though Lavoisier's theory of combustion and of
calcination was now practically complete, and
was fully developed by him in his memoir On
combustion in general in 1778, it made com-
paratively little impression even in Franoe,^nd
gained no converts of note until 1785, when Ber-
Ulpllei m^ I'puioio^ ^ave |n th@it fuU?9si9i> to
the new doctrine. The death-blow to phlogiston
really came from the discovery of the compound
nature of water. It was only after Cavendish's
experiments on the combustion of hydrogen that
Lavoisier was able to combat the generally re-
ceived opinion as to the nature of the process of
solution of metals in acids. It was observed
that when certain metals were dissolved in acids,
hydrogen was evolved, and the metals were cori-
verted into calces which could be again trans-
formed into the metals by heating in hydrogen.
These facts were accounted for by the Stahlian
hypothesis on the assumption that the gas
evolved on the solution of the metal was actually
phlogiston, and that on heating the calx with
the gas the phlogiston again combined with it
to regenerate the metal. In 1783 Lavoisier was
informed by Blagden, who at that time acted as
Cavendish's assistant, of the experiments of the
latter, made in 1781, on the production of,^watel:
by the combustion of hydrogen. The importance
of the discovery of the true chemical nature of
water was at once perceived by Lavoisier. He
and Laplace repeated Cavendish's experiment in
presence of Le Boi and Blagden, and found that
water was composed of 1 vol. of oxygen and
1-91 vol. of hydrogen. Further evidence of the
compound nature of water was obtained by
passing steam over red-hot iron contained in a
porcelain tube, when free hydrogen was formed
together with a calx of iron. Lavoisier was now
able to explain the origin of the hydrogen in
the act of solution of a metal in a dilute acid,
on the assumption that in the process water was
decomposed, and that the oxygen united with the
metal to form the calx, wMle the hydrogen
escaped in the free state. This view is further
developed in the memoir On the solution of the
metals in acids, published in 1785. Mnally, iu
an elaborate paper On Phlogiston, Lavoisier con-
nects together his various observations, elaborates
his own theory of combustion, and confutes the
phlogistic hypothesis.
' Whatever may be thought of Lavoisier's
clainis to be considered the discoverer of oxy-
gen, and of the true nature of air and water,
there can be no question as to his merit in being
the first to recognise the relation of these dis-
coveries to the theory of combustion. As far
back as 1772 he seems to have been fully per-
suaded of the insufficiency of the Stahlian hypo-
thesis, and for upwards of a dozen years he '
laboured, practically alone, to demonstrate its
insufficiency. His triumph was complete in
1785, and La Chimie Fran^aise, as the new
doctrine was termed by Fourcroy, was embraced
in Prance with all the fervour of revolution.
Nor did national prejudice long delay its adop-
tion in Germany and Great Britain. The Berlin
Academy pronounced against phlogiston in 1792,
Black early became a convert, but both Caven-
dish and Priestley, in spite of the fact that their
discoveries had contributed so largely to its
downfall, remained faithful to Stahl's doctrine
to the end — an exemplification of the truth pi
Priestley's- words that ' We may take a maxim
so strongly for granted, that the plainest evidence
of sense will not entirely change, and often
hardly modify, our persuasions ; and the more
ingenious a man is, the mpre effectually he is
entangled iq his errors, his ingenuity only help-
244
COMBUSTION.
ing him to deoeive himself by evading the force
of truth.'
T. E. T.
In connexion with Combustion v. OxroAiiou
and Dboxidaxion.
COMENAHIC ACID v. Di-oxy-pyeiddie oab-
boxytjIg acid.
OXY-COMENAMIC ACID u. Tbi-oxy-ptbidikb
CAKDOXYLIO ACm.
COMENIC ACID Cja.fi,. S. above 6 at 100°.
Got by boiling meconio acid C,H,0, with HCl,
COj coming off. Purified by crystallising the
difficultly soluble ammonium salt from water
(How, A. 80, 65 ; Ed. Phil. Trans. 20 [2] 225 ;
cf. Bobiquet, A. Ch. [2] 51, 326 ; S3, 423 ; Liebig,
A. 7, 237; 26, 116; Steuhouse, P. M. [3] 25,
196). Comenic acid is thrown down as a white
powder when HCl is added to a solution of its
ammonium salt.
Properties. — ^Prisms, laminae, or grannies;
Bol. boiling water, insol. alcohol. At 260° it
splits up into COj and pyromecouic acid. Fe^Cl,
gives a red colour. Does not react with hy-
droxylamine (Odernheimer, B. 17, 2081).
Beactions. — 1. Sodiivm-amalgajA reduces it
to syrupy hydrocomenio acid CuHjOj, which
forms a salt AefiJB.fi, (v. Korff, A. 138, 191).—
2. If comenic acid is boiled with PCI, (4 equiva-
lents) and POCl, until no more HCl comes off,
and the liquid distilled till the thermometer
reaches 150°, an oU remains in the retort which
is converted by boiling water into di-chloro-
comanic acid, C5HCLJO2.GO2H (yield, 20 p.c). It
crystallises from alcohol in needles, [217°].
Some chloro-comanic acid, CSH2CIO2.CO2H,
[247°] is formed at the same time. Both acids
are reduced by boiling cone. HI to comanio acid,
CiHjOj.COjH {q.v.). When comanic acid is
boiled with aqueous KH, it is converted into
(i8)-oxy-picolinic (oxy-pyridine oarboxylic) acid.
3. Heated with PClj at 280° it gives Cfil, or
* perchloro-mecylene,' and hexachloro-ethane.
Perchloro-mecylene crystallises from alco-
hol in compact oblique prisms, melting at
[39°] (Ost, J. pr. [2] 27, 294).-4. Ethylamme
gives di-oxy-ethyl-pyridine carboxylio acid,
C5HEtN(0H)2C02H.— 5. AniUne gives similarly
di-oxy-phenyl-pyridine carboxylio acid (H. Ost,
J.pr. [2] 29, 380).
Salts. — NH^HA" aq : four-sided prisms ;
reddens litmus. V. sol. boiling water. — KjA" :
b1. sol. water. — KHA" : short square needles ;
reddens litmus. — NaHA" : four-sided prisms
(from hot water). -BaA"aq(atl21°).—BaA"5aq:
inpol. boiling water. — BaHjA", 6aq : sol. water. —
CaA"aq (at 121°). — CaA"6iaq: prisms, insol.
water. — CaA"3Jaq. — OaH2A"j7aq: crystals, v.
sol. hot water. — MgA"5^aq: crystalline
grains. — MgHjA"j8aq. — CuA"aq (at 100°).—
Fe(OH)HjA", 2aq (at 100°).— PbA"aq.— AgHA":
granular pp. — AgjA" : thick yellow pp.
Ethyl ether C,H;jO,(OH).COJKt. [135°]
(How) ; [127°] (Eeibstein). From an alcoholic
solution of the acid and HCl. Formed also by
heating meconio acid with EtI and alcohol at
100°. Needles, v. sol. hot water. May be sub-
limed, FejCl„ gives a red colour. Very readily
saponified. By successive treatment with so-
dium-amalgam and chloroformic ether a com-
pound C„H,20, [87°] may be got (Drechsel,
J.pr. [2] 17, 164),
Acetyl derivative of the ether
CJS.fijfik.a){COJ&i). [104°]. From the abov«
and AcjO at 150° (Eeibstein, J.pr. [2] 24, 277).
Ethyl derivative 0,HjOi,(OBt)COjH.
[240°]. Obtained by fusing the ethyl derivative
of meconic acid (<;. v.) by itself. Crystallised
from water, animal charcoal being used, it forms
long white needles (Mennel, J. pr. [2] 26, 458).
Salt. — AgA'2|aq: white needles.
Amide C5Hj02(0H)(C0.NHj). Formed by
passing NH, into an ethereal solution of ethyl
comenate. A pp. of C5Hj02(0NHJC0jEt is first
formed, but this is then slowly converted into
C5H20j(0NH,)C0.NHj, whence HCl liberates the
amide. White plates (from water). Not aSected
by boiUng water. BoiUng NaOH converts it into
Eodio comenate. Its aqueous solutions give a
red colour with FojCl,.
Salt.— C5H;,0j(0K)(C0.NH,)aq. Insol. al-
cohol.
Chloro-comenic acid
C5HC10j(C0jH)(0H) liaq. Formed by passing
CI into water in which powdered comenic acid
is suspended (How, Ed. Phil. Trans. 20 [2]
225). Four-sided prisms (from water). More
soluble in water than comenic acid, v. e. sol.
warm alcohol.— Ag^A" (at 100°).— AgHA" iaq.
Bromo-comenic acid C5HBrOj(COj5H)OH.
Formed by the action of bromine-water on co-
menic or meconic acids. Four-sided prisms;
less soluble than the preceding body. Boiling
baryta-water gives oxy-comenic acid. — AgTTA"
(at 100°).— AgHA" iaq.
Ethyl ether EtA'. [141°]. From silver
bromo-comenate and EtI. Glittering needles
(Mennel, J.pr. [2] 26, 472).
Di-bromo-comenic acid
C5HBr0j(0Br)(C0jH) (?).
Formation. — From Br and bromo-comenic
acid.
Preparation. — Meconio acid (10 g.) is sus-
pended in water (80 g.) and bromine (18 g.) is
added. The product separates at once as crys-
talline plates (containing 3aq).
Properties. — Its solution gives no colour with
Fe^Cl, in the cold, a red colour appears on heat-
ing, bromo-comenic acid being formed. At 105°
the crystals give ofi Br (2 mols.) and Hfi. An
aqueous solution of the acid gives no pp. with
BaClg, but on adding NH, a red colour and an
orange pp. are got. Zn and HCl reduce it to
bromo-comenic acid.
Constitution. — This acid is not a true di-
bromo-comenic acid, nor a compound of comenic
or bromo-comenic acid vidth HBrO, hence it
probably contains bromine in hydroxy!, although
this is very unusual (Mennel, J. pr. [2] 26, 466)r
Ethyl ether C5HBrOj(OBr)(CO;^t). From
mono-ethylic meconate (10 g.), water (80 g.) and
bromine (18 g.). Small yellowish tablets (con-
taining 2aq). Sol. water, alcohol, and ether.
Beadily decomposes. When heated with water
or with SO2 it changes to white needles of bromo-
comenate of ethyl [141°] (v. supra).
Nitro-comenio ether CjH(NOa)(OH)COjEt.
[147°]. From HNO, (S.G. 1-5) and comenic
ether in the cold. Better by passing NjO, into
an ethereal solution of ethyl comenate (B.). SoL
hot water, alcohol, and ether. Its aqueous so-
lutions give with Fe,Clj a red colouration.
COMPOUND RADICLES.
246
Salts.— OsH(NO,){ONa)CO^t. Yellow
needles. Explodes when heated. —
{0,H(NO,)COjJ!t}jO»Ba. Explodes when heated.
Silver salt blackens even when cold.
Amido-oomenio acid C5H(NHj)02(0H)C0jH.
Foimed by reduction of nitro-comenic ether by
Sn and HGl (B.). Slender silky needles (con-
taining aq) (from^ water). SI. sol. alcohol and
ether. Its aqueous solutions give a blue colour
with a little Fefil„ more PejCl„ turns the Uquid
red.
Salt.— C5H(NHj)Oj(OH)COjH,HCl,3aq.
Glittering scales, formed by adding cone. HCl to
the above. Decomposed by water, losing HCl.
Oxy-comenic acid C,HOj(HO)2C02H. From
bromo-comenic acid by boiUng baryta, or with
HCl (B.). Also from comenamio acid, KMnO,,
and dilate HjSOj. CryBtalUses from water in long
needles (with 3aq) or in short prisms (with aq).
y. sol. water and alcohol, si. sol. ether. In its
aqueous solution Fefilg gives a blue colour turned
red by excess. NH, at 100° gives tri-oxy-pyri-
dine carboxylic acid.
Salts.— C5HOs(HO)2COjNH,.— ,
{C5HOj(OH)jCOj}jBa,2aq.— 05HOj(OK)jOO,K.
Ethyl ether C^OJJB.O)fi0^t. [204°].
Small prisms (from alcohol).
Di-acetyl derivative of the ether
C5H0(0Ac)jC0jEt. 175°]. Small needles (from
alcohol).
COMFOSITIOIT, CEEUICAL. By the chemi-
cal composition of a compound is meant, pri-
marily, a statement of the masses of the elements
by the combination of which a specified mass —
say 100 parts — of the body has been produced,
or into which a specified mass of the body may
be resolved. So long as nothing more than the
percentage elementary composition of com-
pounds was determined, chemistry remained a
collection of unclassified facts. The establish-
ment of the law of multiple proportions, and the
development of this law, and also that of com-
bining weights, led to the possibility of assign-
ing to each compound a certain number which
expressed the smallest relative mass of it that
entered into chemical reactions with other com-
pounds ; but no generally applicable method for
determining the values of these chemically re-
acting masses was found until the help of the
atomic and molecular theory had been sought
(v. Combination, ceemical, Li.ws of ; and Com-
BiNiNO WEioHTS OF ELEUENTs). The Composi-
tion of the smallest chemically reacting mass is
expressed by the focmula of the compound,
which tells the number of combining weights of
each elementary constituent which have com-
bined to form the mass in question. This wider
meaning of chemical composition rests on, and.
arises from, the laws of chemical combination ;
but it became definite only when supplemented
by atomic and molecular conceptions.
The atomic weights of all the elements have
been determined with more or less accuracy;
when the molecular weight of a compound is
known, the chemical composition of that com-
pound is expressed in a formula which states
the number of atoms of each element that have
combined to form a molecule of the compound
{v. Atomic and hoiiECDIiAB weiohts). In this
further widening of tbe conception of chemical
composition, the properties of a compound are
represented as determined by the nature and
number of the atoms which form the molecule
of the compound. This conception rests on, and
arises from, the molecular and atomic theory.
It frequently happens, especially among com-
pounds of carbon, that two or more compounds
have the same composition and the same mole-
cular weight, and yet differ in properties ; such
compounds are said to be isomeric. These
differences in properties are generally regarded
as associated with differences in the arrangement
or configuration of the atoms which form the
molecules of the compounds in question. More
or less conventional methods are used for ex-
pressing the supposed relations between the
properties of isomeric compounds and the struc-
tures of their molecules. These methods are
based on the hypothesis of atomic valency which
has arisen from the application of the molecular
and atomic theory to the study of isomerism
(«. Equivaminoy ; EoBMuiia: ; Isomehism).
The term chemical constitution (q. v.) is often
used to express that conception of chemical com-
position which includes an attempt to ^exhibit
the properties of a compound as determined not
only by the nature and number, but also by the
relative arrangement, of the atoms which form
the molecule of the compound.
In the preceding paragraphs it has been
assumed that the composition of every element
is always the same. As a matter of fact many
bodies which were once regarded as elements
have been proved to be compounds ; and recent
researches show that this process is likely to be
repeated on some of those kinds of matter which
are now classed among the elements. Be this
however as it may, it is certain that some ele-
ments exhibit different properties when they are
obtained from their compounds under different
conditions. Phosphorus, carbon, oxygen, sul-
phur, and several other elements, exist in more
than one form ; they exhibit the phenomenon
of aUotropy. What we have learned of the
connexions between properties and composition
shows that these differences in properties are to
be regarded as associated with differences in
composition. The only consistent conception
which can be formed at present of variations in
the composition of elements is that which is
furnished by the molecular and atomic theory
According to this conception, the properties of
an element depend not only on the nature of its
atoms, but also on the numbers of these atoms
which are combined to form a molecule, and on
the relative arrangement of the atoms in the
molecule [v. Ailoikopy, vol. i. p. 12S).
M. M. P. M.
COMPOTIIID RADICLES. The study of che-
mical composition and properties has led to the
conception that certain groups or collocations of
atoms in the molecules of various compounds
remain so closely associated throughout chemi-
cal changes which the molecules undergo, that
the functions performed by those- groups of
atoms in these reactions are practically identical
with the functions performed by elementary
atoms. Such groups of atoms are called com-
pound radioles in distinction to the atom of «.n
element which may be called a simple radir.la.
When two elements combine we may say t)iat
the compound is formed of two simple radicleu ;
248
COMPOUND RADICLES.
e.g. NaCl is formed of the radicles Na and CI ;
when two compounds combine to form what is
generally called a double compound or a double
salt, which double compound is easily resolved
into the compounds by whose union it was
formed, we may say that the double compound
is formed of two compound radicles, each of
which can be isolated. Similarly, when a com-
pound goes through a series of reactions with
the production of new compounds, all of which
contain certain elements of the original com-
pound, we may suppose that these certain ele-
ments were in some way closely associated in
the original compound, and although we cannot
isolate this group of elements, yet we may
advantageously regard the original compound
and those produced from it as formed by the
union of this collocation of elementary atoms,
or this compound radicle, with other atoms.
The conception of the compound radicle is only
a widening of the conception of the element ;
it is closely associated with the subjects of
chemical classification and chemical constitu-
tion (q.v.). In connection with ^thjs subject v.
Badiole and Types, vol. iv.
M. M. P. M.
CONCHIOLIN V. Pkoteids, Appendix C.
CONCUSCONIDINE v. Cinohona babes.
CONCTTSCONINE v. CraoHOUA babes.,
COKESSINE C,,H„„N. [121i°]. Probably
identical with wrightine (Stenhouse, Ph. [2] 6,
493 ; Haines, Ph. [2] 6, 432 ; Warneoke, Ar. Ph.
[3] 26, 248, 281), which occurs in the bark and
seeds of WrighHa anUdysenterica, called conessi
bark ; occurs in the bark of Eola/nhena africcuna
(P. a. 3.), and (though in much smaller quantity)
in the East-Indian S. antidysenterica (Polstorff ,
B. 19, 1682). White silky needles. V. sol.
alcohol, ether, benzene, and chloroform, v. si.
sol. water. Very bitter taste. Scarcely volatile
with steam. Tertiary base. H2SO4 and dilute
KIO3 form oxy-oonessine CjoHiojNjOj (?), a base
which is coloured rose-red by cone. H„SO. at
100° (W.).
Salts . — B'HCl aq : small very soluble needles.
B'HNO, : needles.— B'HCl.— B'jHjCljPtCl^iaq:
very sparingly soluble yellowish-red needles. —
B'HClAuCl, IJ aq : long yellow needles, v. sol.
alcohol, nearly insol. water. — B'HCl,Au01s 3iaq :
golden-yeUow needles. — ^B'HClHgClj : needles,
b1. sol. water.
Picrate B''CeH2(N02)30H aq : very slightly
soluble glistening golden needles.
Methylo-iodide OuH^oNMellJaq: tables.
V. e. sol. hot water.
Ethylo-iodide C^HgiNEtl^aq: glisten-
ing tables.
Methylo-hydroxide C,jH2i,NMe(0H) :
strongly alkaUne base fcrmed by the action of
Ag^O upon the iodide. It readily absorbs COj
forming the carbonate (C,2H„|,NMeO)jC04aq,
which crystallines in long needles. On heating
to c. 150° it splits up into conessine and MeOH
(Polstorff a. Schirmer, B. 19, 76).
COWGLTTTIH v. PnoiEins.
COB'GO-IIED V. Amido-sulpho-naphthalene-
azo-diphenyl-azo-naphthylamint sulphomc acM,
Tol. i. p. 416.
CONHTDSIN V. Conhne.
CONICEiiDlKE V. Coniin*.
CONICElillE V. CoHUNli.
CONIFEHIN C,„Hi,A- [185°]. S. (cold) -Bl.
[a]B= -66-9 at 20° (B. 18, 1600).
Occivrrence. — 1. In the cambium of coni-
ferous trees (Kub'el, J. pr. 97, 243). — 2. In small
quantity in beet-root, and hence it gives rise to
traces of vanillin sometimes found in beet-sugar
(Lippmann, B. 16, 44). — 3. In asparagus {B. 18,
3335).
Preparation. — The juice of the cambial cells
of fir trees is boiled, filtered, and evaporated to
crystallisation.
Properties. — Satiny needles (containing 2aq).
Efflorescent in dry air. V. sol. hot water, si.
sol. alcohol, insol. ether. Lsevorotatory. Some-
what bitter. Its aqueous solution is not ppd. by
metallic salts. Boiling dilute H^SO, splits it up
into glucose and a resin. Cone. H2SO4 gives a
dark violet colour, and, on adding water, an
indigo-blue pp. It is hydrolysed by emulsin
into glucose and conif eryl alcohol. Phenol and
H^SOj give a blue colour, especially in sunlight.
A dilute alcoholic solution of thymol and KCIO,
turns coniferin moistened with H^SOj blue
(Molisch, .0. C. 1887, 366). Chromic mixture
oxidises it to vanillin, giving the odour of
vanilla (Tiemann). In weak alkaline solution
sodium amalgam reduces it to eugenol (L.
Chiozza, G. G. 1888, 443).
Tetra-acetyl derivative C|eH,gA0i0j.
[126°]. From coniferin and ACjO (Tiemann a.
Nagai, JB. 8, 1140). Crystalline. Insol. cold
water, m". sol. cold alcohol and ether.
CONIFEBYL ALCOHOL C,„H,jO, i.e.
C,H,(bH)(OMe)(C,H,OH). [4:3:1]. [74°].
Fornied by subjecting an aqueous solution of
coniferin to the action of emulsin at 25° :
C„H,20, + H2O = CeH, A + C,„H„03 (Tiemann a.
Haarmann, B. 7, 611). Prisms. SI. sol. hot
water, m. sol. alcohol, v. sol. ether. Sol. alkalis
and reppd. by acids in an amorphous condition,
which softens at 160° and is v. si. sol. alcohol
and ether. This amorphous form is coloured
red by cone. H^SO,, and afterwards dissolved
with a red colour. Chromic acid mixture pro-
duces vanillin', which may be recognised by its
characteristic odour ; the other products of oxi-
dation are HOAc and aldehyde. Potash-fusion
gives protocatechuic acid. Sodium amalgam
reduces it to eugenol C^HijO,.
CONIINE CaHijN i.e. C.H„PrN or
CHj
A
HjC CH,
II . Dextro-{t^- propyl -pvperidin*.
V
KH
Mol. w. 127. (169°). S.G. li» -846 (Petit, B. 10,
896) ; -886 (Sohorm). S. (cold) 1-11. S. (ether)
17. [a]„ = 13-8.
Occurrence. — In all parts of the hemlock
[Conium maculatum) (Giesecke, Brando's Ar.
Ph. 20, 97 ; Geiger, Mag. Pharm. 35, 72, 259 ;
36, 159 ; V. Planta a. Kekul6, A. 89, 129).
Synthesis. — (a)-Allyl-pyridine (from (o)-pico-
line and paraldehyde) on reduction with sodium
and alcohol gives (o)-propyl-pyridine hexabj-
dride ; this (a)-propyl-piperidine is identical ip
all its properties with coniine, except that it is
optically inactive, but by means of the acid tar-
trate it can be sef aiated into a destro- and ■
OONUNE.
24}
Ibto- base, the former of which is identical with
natural coniiue (Ladenburg, B. 19, 2579).
Formation. — 1. By heating oonhydrine with
HI and phosphorus, and treating the resulting
hydriodide of iodo-coniine with tin and HGl
(Hofmann, B. 18, 5).— 2. By reducing (o)-ooni-
ceine with HI and P (Hofmann).
Preparation.— 100 kilos, of hemlock seeds,
after soaking in hot water till swollen, are mixed
with a solution of 4 kilos, of Na^CO, in 4 litres
of water, and the mixture distilled with steam of
about 3 atmospheres. The aqueous distillate is
neutralised with HCU eyaporated, NaOH added
and extracted with ether. The residue after dis-
tilling off the ether is fractionated. Another
method consists in extracting the ground seeds
in vacuo with dilute acetic acid, evaporating the
solution to a syrup in vacuo, adding magnesia,
and extracting with ether (Sohorm, B. 14, 1765 ;
cf. Wertheim, A. 100, 328 ; 123, 157).
Properties. — Oil, smelling like mice. Is a
violent paralytic poison which acts on the
motor nerves (Hofmann, B. 14, 705 ; cf. Christi-
Bon, J. Ph. 22, 413; J. Chim. Med. 12, 461;
Kuhlmann, N. Br. Arch. 23, 38). 'Sot white
mice the lethal dose is -0758 g. per kilo., whilst
'0750 g. does not produce death (Ladenburg).
Its aqueous solution becomes turbid on warming.
Volatile with steam. Alkaline to moist test-
papers. Coniine (100 pts.) dissolves water (25
to 80 pts.) and the solution when heated be-
comes turbid from separation of water. V. sol.
alcohol, ether, chloroform, benzene, amyl alcohol,
and acetone; si. sol. OS,. Goniine dissolves S
but not P. Coniine gives a yellow pp. with
phosphomolybdic acid, a cheesy pp. with po-
tassio-mercurio iodide, and an orange pp. with
potassio-bismuthio iodide. If coniine is dropped
into a solution of alloxan, an intense-purple red
colour is gradually developed, while white
needles separate, which dissolve in cold KOHAq
forming a purple solution (Schwarzenbach, cf.
W. Blyth, Poisons, 1884, p. 251). Chloride of
iodine gives a dark yellow pp. Coniine does
not dissolve CaCl,.
Estimation. — Cripps, Ph. [3] 18, 511.
Reactions. — 1. Oxidises readily in the air,
becoming brown. — 2. Boiling chromic ndxture
evolves w-butyric acid (Blyth; Griinzweig, A.
162, 193). — 3. Alcoholic solution ot iodine touaa
a dark brown pp. which afterwards disappears,
the liquid becoming colourless. — 4. Bromine
forms a mass of needles [c. 100°] ; if too much
bromine is used a gummy mass is formed
jBlyth). — 5. Chlorine gas produces a turbidity
m moist coniine. — 6. Nitrous acid gas produces
' azoeonhydrine ' CjHuNjO (Wertheim, A. 123,
157).— 7. By prolonged treatment with HI
coniine is reduced to octane and NH, (Hofmann,
B. 18, 5). — 8. By distillation with zino-dMst it
loses hydrogen and is converted into propyl-
pyridine (conyrine) (Hofmann, B. 17, 825). — 9.
By the action of hromme m alkaline solution it
gives a very unstable bromo- derivative which
probably has the formula GgHuNBr. If this
bromo- derivative is treated with H2SO4 it yields
(a)-eonioeme CjHisN with splitting off of HBr.
If however the elimination of HBr from the
bromo- derivative is produced by treating it with
alkalis (7)-coniceine is obtained (Hofmann, B.
18, 109) 10. Beacts with aldehydes thus :
20,H,„NH + CH3.OHO = (CjH,eN),OH.0Ha + H^O
&c. (Sohifl, B. 6, 143).— 11. ChloroformAc ether
forms C,H,„N.C0JBlt (245°). This is an oil,
lighter than water, and very stable (Pohotten,,
JB. 15, 1947). — 12. Phenyl cyanate forms the
anilide of the same coniine iz-carboxylic acid
C8H,„N.C0.NHPh, which is v. sol. alcohol, ether,
and benzene (Oebhardt, B. 17, 3041).— 13.
Phenyl thiocarbimide forms OgH,jN.CS.NHPh
[88°] (G.). — 14. PhthaUc anhydmde forms
C02H.C„Hi.CO.N.G8H,8 [155°] the coniine salt of
which when heated at 210° gives amorphous
C.H,:CA:(N08H„)j (Piutti, Q. 13, 558; A. 227,
181).
Salts.— B'HOl: [218°]. Colourless deli-
quescent laminie. Dry HOI is said to colour dry
coniine blue.— B'jHjPtOlo: orango crystalline
powder.— B'HBr : [100°] (Mourrut, Ph. [3] 7, 23).
Trimetrio needles; a:6:c = -8876:1: -4218.— B'HI:
flat monoclinio prisms; a:6:c = l-2112:l:l'1532
(Sohorm, JB. 14, 1765).— B'HI,: octahedra
(Baur, 4r. PA. [3] 5, 214).— O X a 1 a t e B'^HjC A :
small crystals. — Tartrate B'C^HjO, 2aq : large
trimetrio crystals ; a:6:c= -7766:1: -5859.
Combinaiicm. — B'2HgCl2 : lemon-yellow pp.
(Blyth).— B'HjS (7). Unstable (Schmidt, B. 7,
1525).
Benzoyl derivative CsH,gNBz. Thick
oil. On oxidation with EMnOf it yields the
benzoyl - derivative of homo - coniic acid —
0,H,5NBzC0jH (Schotten a. Baum, B, 17,
2548).
Nitroaamine CgH„N.NO. Azoeonhydrine.
(150°-160°). Prom coniine by treatment with
nitrous acid gas, followed by water (Wertheim,
A. 123, 157; 130, 269). Yellow oU. V. sol.
alcohol and ether. HCl passed into its ethereal
solution reproduces coniine, giving off N and NO ;
zinc and HCl do the same.
Uethyl-coniine CgHjaNMe. Prom coniine
and Mel. Formed also, together with C^H, and
H2O, by distilling its ethylohydroxide (Kekul6 a.
Flanta, A. 89, 143). Liquid.
E thy lo 'hydroxide CsH^NMeEtOH.
From the preceding by successive treatment
with EtI and inoist Ag^O (K. a. P.). Strongly
alkaline base. — CgH,gNMeEtI : crystalline pow-
der, not affected by aqueous KOH. —
CsH,eNMeBt013Hg01j.— (CsH,gNMeEtGl)^tCl,:
yellow octahedra. — CgHuNMeEtAuCl,. '
Methylo-hydroxideC^B^^MejiyB.. From
coniiue by treatment with excess of Mel, the
resulting iodide being decomposed by moist
AgjO.
Di-methyl-coniine (C,H,5Me)NMe. (182°),
Prepared by the dry distillation of the methylo-
hydroxide of methyl-coniine. Liquid. —
(B'HCl)2PtCl4 : sparingly soluble needles.
Methylo-iodide CsH,jMeNMe2l : crystal-
line solid.
Methylo-hydroxide CgHuMeNMe^OH :
on dry distillation it splits up into H^O, CHgOH,
NMe,, di-methyl-coniine, and cpnylene (C,H,J
(Hofmann, B. 14, 708).
Ethyl-coniine C,H,gNEt. From coniine and
EtI, the resulting 0,H,gKEtHI being decom-
posed by KOH (K. a. P.). Oil, smelling like
rdioe.— (CgH,gNEt)2H2Pt01„ : yellow crystalline
powder.
Ethylo-iodide CgH,gNEt.,I. Crystallin«
mass. Gives (C,H,gNEtj01)J'tCl^
248
rONIINE.
Oxy-ethyl coniine C,H,„N.CHj.CH,OH.
(241°). The hydrochloride is formed by the
action of glycol ohlorhydrin on coniine.
Benzoyl derivative
C,H,jN.CH2.CH2.0Bz. From BzOI and the
aboVe.— B'HI : small pearly plates. — B'HCl :
very soluble crystals (Ladenburg, B. 14, 2409 ;
15, 1144).
Tri-bromo-oxy-coniine CjEtuBrjON. Obtained
as a by-product in the preparation of (7)-coni-
ceine by treatment of coniine with bromine and
alkali. Formed by the, action oi bromine and
alkali upon (7)-coniceiine (Hofmann, B. 18, 121).
Heavy oil. Very unstable. The free base quickly
decomposes spontaneously into the hydrobrom-
ide and di-bromo-oxy-coniceine 2C5H„Br30N
= CsH,4Br30N,HBr + CaH,sBr20N. On reduction
with tin and HCl it gives coniine and (7)-coni-
ceine.
Salts.— B'HBr: needles.— B'HNO "3 : very
sparingly soluble. — B'JSfil^tGl,: nearly insol.
yellow crystalline pp. — B'HClAuCls : crystalline
solid.
Di-methyl-oxy-coniine CsH^MeJON. (226°).
Formed by the dry-distiUation of the hydrozide
of the ammonium-base CgH,jMeON,MeOH, the
iodide of which was obtained- by digesting
(7)-ooniceine with methyl iodide and alcoholic
NaOH (Hofmann, B. 18, 117). Colourless liquid.
SI. sol. water. Strongly alkaline. — B'HCl,AuClp :
sparingly soluble crystals.
Eomo-coniic acid C,H„02N i.e.
CH,.CH,.GHj.CH(NHj).CH,.CH2.CH2.C02H (?).
[158°]. Obtained by saponification of the benzoyl
derivative (Baum, B. 19, 502). White crystals ;
y. sol. water and alcohol. The aqueous solution
reacts neutral. Optically inactive. Is not
poisonous. It readily loses H2O, and is con-
verted into the inner-anhydride. When treated
with nitrous acid it evolves nitrogen.
Benzoyl derivative CiHjjNBz.COjH.
[143°]. Formed by oxidation of benzoyl-coniine
with KMnOj (Schotten a. Baum, B. 17, 2549).
Needles or prisms ; sol. alcohol, nearly insol.
water and ether.— vA'Ag : nearly insoluble white
amorphous pp. — ^A'^Cu : blue amorphous pp. ;
b1. sol. hot water, insol. alcohol.
Ethyl ether CjH.sNBz.CO^Et. [95°].
Iiong white flat prisms; v. sol. alcohol, ether,
&c., nearly insol.' water and petroleum-ether
(Baum, B. 19, 600).
Inner anhydride C,H„ON. [85°].
Eeadily formed by. splitting off H^O from the
acid by heating it to its melting-point, treating
itwith absolute alcohol, (Sic. (B.). White crystals.
V. sol. water, alcohol, ether, and chloroform ;
m. sol. petroleum-ether. Sublimable. It is re-
converted into the acid by boiling with baryta-
water and ppg. the Ba with COj.
(a)-Conioeine C,H,5N. [c.-16°]. (158°).
V.D. = 4-31 (obs.). S.G. ii -893.
Formaticm.— l. Together with (;8)-ooniceine,
by heating conhydrine CsHpON with P^Oj. — 2.
Together with the (5)-coniceine, by heating
conhydrine with HCl. — 8. By the action of
H2SO4 on the bromo- derivative C|,H,„NBr ob-
tained by treating coniine with bromine and
NaOH. The yield is 40 p.b. of the coniine — 4.
Together with (;3)-coniceiLne, by heating iodo-
coniine C|,H,„IN.
Properties.— Colourless liquid. SI. sol. water.
Its odour is extremely like that of coniine.
Tertiary base of strongly alkaline reaction. Its
physiological action resembles that of coniine,
but it is about five or six times as poisonous.
By HI and P it is reduced to coniine.
Salts. — B'HCl : six-sided tables.—
B'^jCyPtCl, : large yellow trimetrio prisms.—
B'HClAuCla : yellow needles. — Piorato
B'C,Hj(NOj)aOH [225°] : yeUow needles ; si. sol.
cold alcohol, nearly insol. water,
Methylo-iodide B'Mel: crystalline solid;
very sol. water and alcohol. — (B'Me01)jPt01j :
yellow pp. (Hofmann, B. 18, 5).
(;8)-Conioeine OsHijN. [41°]. (168°). Formed
together with (ct)-conioeine (1) by heating conhy-
drine CjHjjON with P2O5, (2) by heating conhy-
drine with fuming HCl, (3) by heating iodo-
coniine CjH,jIN above 100°. Colourless needles.
Very volatile. Coniine-like odour. Secondary
base of strongly alkaline reaction. Weaker poi-
son than the (a)-coniceine.
Salts. — ^B'HCl : colourless, very soluble
prisms.— B'HClAuCls.
(7)-Coniceine O^^JS. (173°). Obtained by
the action of aqueous alkali upon the bromo-
derivative CgHuNBr formed by treatment of
coniine with bromine in alkaline solution; the
yield is 30 p.o. of the coniine. Colourless liquid.
Not solid at — 50°. Volatile with steam. About
12 times more poisonous than coniine. SI. sol.
water. Strongly alkaline. Lighter than water.
Secondary base. By further treatment with
bromine and alkali it is converted into tri-bromo-
oxy-coniine OsHnBrjON. By digesting with
methyl-iodide and alcoholic NaOH it yields the
methylo - iodide of oxy - di - methylo - coniine
CsHisMe^ONMel.
Salts.— B'jHjCljPtOl,: large crystals; S (at
20°)2-4.— B'HClAuCla: sparingly soluble crys-
tals.— B'JB^CljSnClj : large crystals, the most
characteristic salt of the base.
Acetyl derivative CsH„NAo (252°-255°) ;
oil (Hofmann, B. 18, 111).
Oxy-coniceine CbHi^ON (210°-220°). Formed
by reduction of di-bromo-oxy-coniceine with tin
and HCl (Hofmann, B. 18, 125). Colourless
fluid. Volatile with steam. By digestion with
alcoholic KOH it loses HjO and is converted into
ooniceidine CijHjgNj.
Salts. — B'HCl: colourless needles. —
B'HClAuClg : easily soluble thick needles. The
stannic double chloride is sparingly soluble.
Di-bromo-oxy-oouioeme CjHijBrjON. Formed
by spontaneous decomposition of tri-bromo-oxy-
coniine, thus : 2CsH„BrsON = CgHHBraON.HBr +
OgHijBrjON. Prepared by shaking the tri-
bromo-oxy-coniine hydrobromide with aqueous
NaOH and ether. By tin and HCl it is reduced
to oxy-coniceiine (Hofmann, B. 18, 124).
Ooniceidine C.jHjjNj. [56°]. (above 300°).
Colourless needles. Sol. alcohol and ether.
Formed by elimination of HjO from oxy-coni-
ceine by digesting it with alcoholic KOH.
Salts. — B'HCl: small sparingly soluble
tables.— B"H2CljPtCl4: nearly insoluble needles
(Hofmann, B. 18, 126).
Conhydrine CaH„NO. Oxy-conUne. [121°].
(225°) at 720 mm. Accompanies coniine in hem-
lock seeds (Wertheim, Sitz. W. 47 [2] 299). Glit-
tering plates (from ether). M. sol. water, v. goU
OOPAIBA BALSAM.
L'-SU
alcolio] and ether. Alkaline. Does not react
with nitrous acid. Is a weak narootio poison.
Beaations. — 1. By the action of PjOj it is not
converted, as Wertheim {A. 127, 76) supposed,
into coniine, but into a mixture of , (a)- and (;8).
ooniceine OgHuN. These products are also
formed by heating oonhydrine with strong HCl
(Hofmann, J5. 18, 5).— a. By heating with HI
and P it is converted into an iodo-coniine
CsHiijIN, which on heating above 100°is converted
into the hydroiodides of (o)- and (6)-coniceine,
and is reduced by tin and HCl to coniine. — 3.
PBr, converts it into a bromo-ooniine 0,H,aBrN.
Salt.— B'jHjPtCl,: red crystals. The sul-
p hate is also crystalline.
Ethyl-ooahydrine OaHuBtNO. Formed by
the action of KOH on the crystalline compound
of oonhydrine with EtI. Oil.
Ethylo-iodide CsHuBtNOEtl. Trime-
trio crystals ; a:6:c = -8823:1: -105 (Zepharovich,
SiU. W. 47 [1] 275). Converted by Ag^O into a
caustic ethylo-hydroxide, whence HCl and PtCl,
give (CaH,sEtNOEt01)jPtOl4 : dimetrio crystals ;
arc =1: -870.
Faraconiceine CjHjjN. Paracormne. Mol.
w. 125. (169°). S.G. a-913; aa -842.
Formation. — 1. By heating butyric alde-
hyde with alcoholic NH^ and totilling the re-
sulting dibutyraldine (Sohiff, A. 157, 352 ; 166,
88; B. 6, 42).— 2. Prom butylidene chloride
CE^.CH2.CH2.CHCl2 (or bromide) and alcoholic
N^ at 180° (Michael a. Gundelach, Am. 2, 172 ;
B. 14, 2105).
Properties. — Yellow liquid, smelling like
coniine. Y. sol. alcohol and ether; si. sol.
water. The aqueous solution becomes turbid
when warmed. Inactive. As poisonous as
coniine. Chlorine water produces in the aqueous
solution a white pp., sol. HOI. The hydro-
chloride, when evaporated, becomes violet.
Iodine dissolved in EI gives a brown pp. Is a
tertiary base. — ^B'JEjPtClj : orange crystals. ■
' ParadiconUne ' 0,8Hj„N. , (210°). S.G-. is -915.
Formed, together with paraoonioeine, by the pro-
longed action of alcoholic NHj on butyric alde-
hyde. Its salts are amorphous.
CONIMENE CisH.,!. (264°). An essential
oil obtained by steam-distillation from conima
or incense-resin (called also Gam Hyawa), the
produceof Jci(!a^_p^%'^'^ (Stenhouse a. Gtroves,
a. J. 29, 175).
COIT^'ITINrAllIINS V. Cincuoka bases.
CON'^TTINEN'E v. Cinchona bases.
COITQTTIITIN'E v. Cinchona bases.
CONSTITUTION, CHEMICAL (c/. Composi-
tion, chemical). — The conception of chemical
constitution is a development of that of chemi-
cal combination. All our present notions on
the subject of constitution are essentially mole-
cular and atomic. We cannot, indeed, express
our conceptions of chemical constitution without
using the language of the molecular theory.
The chemical molecule is regarded as a definite
structure built up of atoms, or groups of atoms,
which are related to one another in a definite,
although as yet unknown, way. The properties
of the molecule are regarded as conditioned by
the nature and number of the atoms, and also
by the relations between the atoms, which form
the molecule. Our only method of expressing
the relations which undoubtedly exist between
the parts of molecules is based on supposing
these relations to be essentially space-relations.
We try to picture the molecule as a configura-
tion of parts, each of which bears a definite
space-;relation to each other, while all are capa-
ble of performing regulated motions without the
disruption of the molecule.
This conception of the molecule as a struc-
ture is developed in the hypothesis of valency,
and attempts are made to give consistent repre-
sentations of it, with the help of certain conven-
tions, in constitutional or structural formulie
(v. Equivalency ; EoKMnLJB ; Isomebism).
M. M. P. M.
CONTACT ACTION v. Chemical change.
CONVALLAMABIN C^K^fln- Occurs, toge-
ther with oonvaUarin, in the lily of the valley
(Gonvallaria majalis) from which plant it may
be extracted by alcohol (Walz, JV. Jahrb. Pharm.
1858, 10, 145 ; Langelbert, J. Ph. [5] 10, 26 ;
G. J. 48, 271). Powder, with bitter taste, y. sol.
water and alcohol, v. si. aol. ether. Decomposed
by boiling dilute H^SO^ into glucose and oou'
vallamaretiu, which separates in crystalline
spangles, and becomes resinous in boiling
water.
Convallarin. Eeotangular columns. Insol.
water and ether, v. sol. ether. Resolved by boil-
ing dilute acids into glucose and convaUarin.
CONVICm V. VioiN.
CONVOLVULIN C,,nji^^. [150°]. Occurs
in tuberose or officinal jalap root (from Ocmvol-
vulus Sahiedanus), and may be extracted from
jalap resin by washing with ether, then exhaust-
ing with alcohol, and evaporating the alcoholic
extract (Mayer, A. 95, 161 ; A. P. Stevenson,
Ph. [3] 10, 644). A hard resin. Odourless,
tasteless. Sol. chloroform, and hydro-chloric
acid; insol. water, ether, light petroleum, CSj,
benzene, and oil of turpentine. After being taken
internally it is not secreted unaltered (Dragen-
dorff, C. C. 1886, 589). Dissolves in H^SO^ to
a bright red colour. Potassium chromate, per-
manganate, nitrate, or chlorate give an odour
of rancid butter and an olive green colour.
Cone. HNO3 gives oxalic acid and ipomio acid
CioHjsOv
Convolvulic acid CsiHs^O,, (?) [100''-120°].
Formed by boiling convolvalin with baryta-
water (Kayser, A. 51, 81 ; Mayer, A. 83, 126 ;
95, 162). White hygroscopic substance ; sol.
water and alcohol, insol. ether.
Salts.— EA'^aq: [100°-110°]; amorphous.—
BaA'j.— PbAV
Convolvulinolic acid C2^H„0|,aq. [39°].
Formed, together with glucose, by the action of
emulsin or of dilute acids on convolvulic acid.
Minute needles : v. si. soL water, v. e. sol. alco-
hol, m. sol. ether. Tastes bitter. Cone. H^SO,
turns it red. Cono. HNO3 gives oxalic and ipomic
acids. The same body, or an isomeride, is formed
by fusing convolvulin or convolvulic acid with
moist NaOH. It forms salts : BaA'^aq (at
100°).— PbA'^.— CuA'., Jaq (at 100=').
CONYLENE v. Ooiinene.
CONYLENE BKOMIDE v. Di-bkomo-octiti,-
ENE.
CONYLENE GLYCOL ■w.'Di-oxy-ooiylene.
CONYRINE is (a)-PiioPTL-i'YKiDiNE (q. v.).
COPAIBA BALSAM. Exudes frominoisions in
the stemsof various species of Copaifera. Diuretic.
250
COPAIBA BALSAM.
Itconlains alcevorotatory terpene(Co'Daiba oil)
Cj„H,j (250°-260'') ; S.G. ■Q ; V.D. 9^5. The ter-
pene from ordinary copaiba balsam yields a crys-
talline hydrochloride Cj„H324HCl [77°], but those
from Maraoaibo balsam do not (Bonastre, J. Ph.
n, 529 ; Ader, J. Ph. 15, 95 ; Gerber, Brande's
Arch. 30, 157; Blanchet, j4. 7,156; Soubeiran
a. Capitaine, J. Ph. 26, 70 ; A. 34, 321 ; Posselt,
^. 69, 67 ; Lowe, Ph. 14, 65 ; Strauss, A. 148, 151).
The terpene from Maraoaibo balsam yields
terephthalio acid on oxidation (Brix, M. 2, 507).
Moist copaiba oil distilled over sodium gives a
dark blue hydrate CajHsjiaq (252° -260°). The
difierent varieties of copaiba balsam also con-
tain resins and resinous acids (Stoltze, Jahrb.y.
Pharm. 27, 179 ; Oberdorfer, Ar. Ph. [2] 44,
172 ; Ulek, Ar. Ph. 122, 14 ; Stockhardt, Ar.
Ph. 38, 12 ; Procter, Ph. 10, 603 ; Eoussin, J.
Ph. [4] 1, 321 ; Sohweizer, P. 17, 784; 21, 172 ;
Eose, P. 38, 83 ; Hess, A. 29, 140 ; Fehling, A.
40, 110 ; Wayne, Am. Joum. Pharm. [4] 3, 826 ;
Siebold, Ph. [3] 8, 250 ; Bowman, Ph. [3] 8,
330 ; Martin a. Vigne, J. Ph. 1842, 52). On
oxidation with KuCr^O, and HjSOj copaiba balsam
yields M-di-methyl-suocinic acid [140°] (Levy,
B. 18, 3206).
Copaivic acid C2„Hjj02(?) Extracted by
alkalis from copaiba balsam (Bose, A. 13, 177 ;
40, 310 ; Pluokiger, J.pr. 101, 235 ; Eush.Pfc. [3]
10, 5). Crystalline.— CaAV—PbAV—AgA'.
Metacopaivic acid C^fisflt- [206°]. -Ex-
tracted by alkalis from Maraoaibo balsam ob-
tained from Columbia (Strauss, A. 148, 153).
Plates. Insol. water, v. sol. alcohol and ether. —
CuA"aq. - Ag2A"aq.
Oxycopaivic acid O^oB^fi,. [o. 120°]. Found
in a balsam from Para (ITehling, A. 40, 110).
Crystals. Forms an amorphous hydrjtteCjjHjjO,.
PbAV— AgA'.
COPAL. This name is given to a variety of
resins which exude from different trees, e.g.
Rhus copalUna, Eleocarpus copaUfer, Hymenoea
verrucosa, Dammara austraUs. They contain
many resins, and often yield terpenes on distil-
lation (FiUiol, A. 44, 823 ; Thomson,^. 47,351;
Sohibler, A. 113, 389 ; Unverdorben, B. J. 11,
265 ; Violette, C. B. 63,461 ; Muir, G. J. 27, 733 ;
Eennie, G. J. 39, 240). A similar substance
(copalin) is found fossilised at Highgate (John-
ston, P. M. [3] 14, 87).
COFKIiLIDHrE V. Tbi - methyl - pybidinb
HEXAHTDEIDB.
COPPER GSOUP OF ELEMENTS. Copper,
SiLVBB, Gold. These metals occur native ; they
have been known and used from very early
times. They show a general resemblance to
each other in their physical and chemical pro-
perties, but there are differences between them.
The table in the next column presents some of
their properties.
The three metals are hard, lustrous, malleable,
tenacious, and ductile ; they are good conduc-
tors of electricity ; they crystallise in forms be-
longing to the regular system. Cu is oxidised
by treating in air ; Ag combines very slowly with
O at extremely high temperatures ; Au does not
directly combine with 0. Cu and Ag interact
with acid to foum salts ; Au is acted on by aqua
regia, hut not by HClAq or HNO, separately.
Cu decomposes steam at a red heat ; Ag and Au
are without action on steam.
Copper
surer
Gold
Atomic weight .
63-3
107-66
197
Holeculu weights are unknown.
MeUing-polnt . .
Spenifle gruvity
<appro3dmate) .
Atmde might .
c. 1100°
7'2
■096
0. 1000°
10-6
10'3
■067
C.1200*
19-S
10^1
■0324
Specific gravity .
Specific heat . ,
Heats of formation of various com
pounds (Thomsen),
[M»,On , . . 66,750 68,760
[M»,0] . . . 40,810 6,900
[M',8] . . . 20,270 6,340
11,620
Heats of neutralisation of oxides (Tbomsen).
[M-'0,2H01Aq] . 49,300 42,680
[AuO»H»,3HOliei]
=18,440 ,
General formulcB and character of convpounds.
— Oxides, MO and MjO, also Au^O,. Sul-
phides, MS (except Ag), M,^. Haloid com-
pounds, MX, (except Ag), MX or M^X,, AuX,.
Salts, Cu2X,Ag2X, andafewAujX; CuX; afew
AujSX; (X = S04,2N03,C03,fPO„SA.&o.). The
oxides CujO and AujO are produced by reducing
cupric and auric salts, e.g. CuSOjAq and AuClgAq,
in presence of an alkali; Ag^O is obtained by
adding alkali to an argentous salt, e.g. AgNO,Aq.
Addition of alkali to a cupric salt, e.g. CuSOjAq,
ppts. CuO-HjO, which loses water on heating to
dull redness ; addition of alkali to an auric salt,
e.g. AuCljAq, ppts. AU2O3.3H2O, which lo :s
water at 100°, and at a higher temperature be-
comes AuO ; argentic oxide AgO is formed by
the action of ozone on Ag^O. Of the oxides of
Cu, CuO is the more stable ; it dissolves in acids
and forms a large series of well-marked salts ;
Cu^O forms a few salts by directly interacting
■mill acids, but generally it reacts to form salts
of CuO with separation of Cu. Of the oxides of
Ag, AgjO is much the more stable ; it reacts with
acids to form argentous salts ; AgO acts towards
acids as a basic peroxide, forming argentous salts
and evolving 0. None of the oxides of Au is
stable ; a few salts corresponding to each are
known, e.g. Au^SjO, derived from Au^O, AuSO,
from AuO, and AuCl, from AujO,. The oxides
of Cu and Ag are distinctly basic ; moist Ag^O
acts like a weak alkali, although a hydroxide has
not been certainly isolated. Au^O and AuO are
feebly basic ; Au^O, is also feebly basic, but it
likewise dissolves in KOHAq to produce a salt,
KAuO,, in which Au forms part of the negative
radicle.
The sulphides Cu^S and Au^S are produced
by the combined action of H^S and reducing
agents on cupric and auric salts ; e.g. a cupric
salt heated in H^S and then in H gives Cu^S ;
AUCI3 dissolved in KCNAq and ppd. by HjS
giyes AujS. Argentous salts give Ag^S on addi-
tion of H^S. The sulphides CuS and AuS are
formed by reactions between H^S and cupric or
auric salts. Both sulphides of Cu, and sulphide
of Ag, are stable ; Cn^S being the more stable of
the Cu sulphides. These sulphides are basic,
forming some compounds with the sulphides of
less positive elements, e.g. Cu^S.SbjSa ; OujS also
forms some double compounds in which it
appears to be negative to the other constituent,
e.g. KaS.3CU2S.2CuS. AUjS when freshly ppd.
dissolves in water ; both this sulphide and AuS
COPPER.
251
drasolvB in alkali snlphidea to form sulpho-salta,
e.g. NaAuS, KAuS.^.
The salts of Cu belong to two series ; e.g.
OujCl.^ representative of cuprous salts, and CuSO,
representative of ouprio salts ; the cuprio- salts
are the more stable. Silver forms but one series
of saluS, the argentous salts, e.g. AgNOj, AgjSO^.
Few gold salts are known ; AuoSjOj is a repre-
sentative of the aurous salts, AuSOj represents
the auro-aurio salts, and AuClg belongs to the
auric series. Auric chloride and bromide AuOl,
and AuBr, combine with HCl and HBr respec-
tively, forming the monobasic acids HAuCl, and
HAuBrj. Gold is distinctly the most negative
of the three elements Cu, Ag, Au ; the non-me-
tallic character of Au is shown in the formation
of aurates, e.g. KAuOj, derived from AujO,, of
Bulpho-aurates, e.g. NaAuS and EAuS^, derived
from AuS, of the acids HAuCl^ and HAuBr^, and
in the instability of the salts of Au. Silver is
distinctly metallic in all its chemical relations.
Cu is also metallic, but the formation of such
compounds as K2S.3Cu2S.2CuS shows a tendency
of Cu to react as a feebly non-metaUic element.
The position of the elements Cu, Ag, Au in
the scheme of classification based on the periodic
law is peculiar {v. CiiAssifioation, p. 204). These
elements are placed in Group I. ; this group com-
prises Li, Na, K, Eb, and Cs, which are the most
positive, and chemically the most metallic, of all
the elements ; but Cu finds a place in the long
period containing the metals Fe, Ni, and Co ;
Ag comes in the long period which contains Eh,
Bu, and Fd; and Au follows Os, Ir, and Ft. The
three sections of Group VIII., viz. (1) Fe, Ni, Co,
(2) Eh, Eu, Fd, (3) Os, Ir, Ft, appear to impress
their own properties on the elements immedi-
ately preceding and succeeding them. Cu, Ag,
and Au exhibit analogies at once with the other
members of the group to which they belong, and
with those metals of Group VIII. which form
part of the long periods including Cu, Ag, and
Au respectivelyi The analogies with the metals
of Group VIII. are shown in the physical pro-
perties of Cu, Ag, and Au, and also to some ex-
tent in their general chemical characters. The
analogies between the alkali metals and the ele-
ments of the Cu group are shown in the com-
position of the alkali salts and the cuprous salts,
the argentous salts, and the few aurous salts
which have been isolated ; also in the basic
character of cuprous, argentous, and aurous
oxides. The existence of AgO and CuO,^, and
the . fact that these behave as peroxides, esta-
blishes an analogy between Cu and Ag on one
side, and Na or K on the other ; Ag also forms
an alum, Ag2S04.Ali(S04)3i24HjO; moist AgjO
reacts as a weak alkali ; the non-existence of any
salts of Ag except those of the type AgX
(X = ^--11N08, Ac.) establishes another resem-
blance between Ag and the alkali metals. It
should be noted here that the molecular formula
of cuprous chloride is Cu.fi\^, while that of silver
chloride is AgOl ; in this point Ag resembles the
aUcali metals, as the molecular forimulte KCl and
CsCl have been established. Au differs more
than either Cu or Ag from the alkali metals ; this
difference is emphasised in the acidic characters
of AUjOj, AujS, and AuS, in the formation of
HAuOl,, &o., and in the gi'eat instability of the
salts of Au ; on the other hand, the solubility in
water of AU2O and AU2S suggests the solubility
in water of the oxides and sulphides of the alkaii
metals. The methods of 'formation of Au.O and
AuaS suggest the processes by which CvJO and
CujS are formed. (For more details about the
metals of the copper group, v. Coppeb, Silver,
Gold ; v. also Noble metals.) M. M. F. M.
COPPER. Cu. At. w. 63-2. Mol. w. unknown
(c. 1100° ; for various determinations v. Camel-
ley's Melting and Boiling Points). S.G. varies
from 8-36 for finely divided Cu to 8-95 for ham-
mered Cu (v. Playfair a. Joule, C. S. Mem. 3, 57;
Dick, P. M. [4] 11, 409 ; Baudrimont, J. pr. 7,
287; Hampe, G. 0. 6, 379 ; Marohand a. Scheerer,
J. pr. 27, 193, &c.). S.H. (15°-100°) -0938 ;
(16°-172°)-0948; (17°-247°) -0968 (B^de, Aftira.
B. 27 [1855-56]. O.E. (Unear 0°-100°) -00001066
(Matthiessen, Pr. 15, 220). C.E. (cubical) V, = Va
(1 + •00004443* + -0000000555*2) (Matthiessen,
1.0.). T.O. (Ag = 100) 73-6 (Wiedemann a. Franz,
P. M. [4] 7, 33). E.G. at 0. 19° (Ag wire = 100),
93 (Matthiessen, Tr. 1860 ; Pr. 11, 126). E.G.
at 0° (Hg at 0° = 100) 0. 52-54 (Siemens, P. M.
[4] 21, 24). E.G. is much decreased by small
quantities of P, As, Zn, Fe, Sn, &o. (v. Matthies-,
sen, I.C.). Emission-spectrum characterised by
lines in the green 5217, 5153, and 5105 (Thal^n)
Hartley (Tr. 1884. 105) gives the following as
prominent lines of high refrangibility : 3273-2
3246-9, 2544-6, 2370-1, 2248-2, 2247-7, 2244,
2243-5. Crystallises in regular ootahedra. S.V.S.
c. 7-1.
Occurrence. — ^Very abundantly; as metal,
oxide, sulphide, chloride, arseqate, carbonate,
phosphate, sulphate, silicate, and vanadate.
Small quantities of salts of Cu are found in sea-
weed (Malaguti, A. Oh. [3] 28, 129) ; in sea- water
(Dieulafait, A. Ch. [5], 18, 349) ; in the blood of
various animals (v. Harless, Ohem. Gazette, 1848'.
214; Genth, P. 95, 60; J. 1848. 871,874; 1849.
530 ; Ulex, J. pr. 94, 376 ; Wioke, W. J. 1866.
73) ; in flour, eggs, &c. (Odling a. I)upr6, Ouy's
Hospital Beports, October 1858) ; in aU plants
that live on primary rocks or on soil derived from
these rocks (Dieulafait,^. Ch. [5] 19, 550). In
many mineral waters. Copper has been known
and used for making tools from very early times.
Formation. — 1. From native oxides and car-
bonates by melting with silica in presence of
lime and charcoal ; silicate of calcium is formed
and the charcoal reduces the oxide of copper. —
2. From native sulphides, and sulphides of Cu
with Fe, &o., by roasting and then melting ; CuO
is first formed, and then reacts with FeS in the
ores to form OuS and Fe205, the greater part of
the iron passes into the slag ; by repeating this
process approximately pure CuS is obtained ; this
is roasted so as to convert a part of it into OuO,
the mixture of CuO and CuS is melted in closed
apparatus when SO.^ and Cu are produced
(2CuO -I- CuS = 3Cu + SO2) ; the impure copper is
refined by poling, a process consisting in stirring
the melted metal, covered with a layer of anthra-
cite, with a green pole of birch or oak, the heated
wood evolves reducing gases (CO, Bi.fi, hydro-
carbons).— 3. From oxide, or from roasted native
sulphides, by treatment with heated cone. NaClAq
whereby OuClj is formed and dissolved, followed
bj ppn. by means of scrap iron. — i. From oxide,
2)2
COPPER.
or from roasted native sulphides.by treatment with
hot NaOJAq and FeSO^Aq mixed with CaCl„ and
subsequent ppn. by scrap iron ; the chief reaction is
30uO + 2FeCljA.q = Fe^O, + CujCl^Aq + CuCI^Aq.
6. By electrolysis of solution of Cu salts.
Preparation. — 1. Commercial copper is dis-
solved in fairly cone. H^SOjAq ; PbSO^ is ppd. by
diluting largely with water ; the liquid is filtered
and poured on to Zn or Fe (sifted Zn powder is
best), and digested until nearly but not quite
colourless; the pp. is freed from Zn or Fe by
treatment with warm dilute HClAq ; it is then
washed, dried, and fused under borax ; or the pp.
of Cu after digestion with acid is washed, dried
quickly at 75°, and heated in a stream of fi
(Bottger, A. 39, 172). [For impurities in com-
mercial copper V. Abel a. Field, C. J. 14, 280.] —
2. CuSO.Aq is mixed with KC^HjO^Aq, arid
HjPOjAq is added ; Cu ppts. quickly (Wohler, A.
79, 128). — 3. Commercial copper is dissolved in
equal parts of H^SO^ and water ; the solution is
boiled with a little HNO, (to oxidise Fe salts) and
crystallised, the crystals are recrystallised from
water, dissolved and electrolysed (Millon a. Com-
maiUe, 0. B. 56, 1249).— 4. Hampe (Fr. 1874.
352) adds KOHAq to CuS04Aq until a pp. of
basic salt is formed (this pp. contains any Bi
which might have been present in the CuSOJ ;
the filtered solution is evaporated and crystallised ;
the crystals are dissolved in the smallest possible
quantity of water ; 20 cc. cone. HNOjAq are
added to every 500 cc. solution ; an electric cur-
rent is passed through this liquid using cone-
shaped Ft electrodes, the current being stopped
before the whole of the Cu is ppd., whereby Fe,
Zn, and other metals remain in solution ; the
ppd. Cu is washed and dissolved in pure HNOjAq,
the solution is evaporated to dryness, and the
Cu('N03)2 obtained is decomposed by heating ; the
CuO is reduced by heating in pure H. The Cu
thus obtained is dissolved in HjSO^Aq ; crystals
of CnSO, are obtained, and the foregoing process
of electrolysis is repeated. The metal obtained
by the second electrolysis is boiled in water, to
remove traces of undecomposed CuSO,. The Cu
thus obtained is heated to a very high tempera-
ture in a porcelain tube in a current of pure
COj (about 50 grams Cu at a time) until melted.
H is then passed over the molten metal for a
time, and finally it is allowed to cool in CO.^. —
5. Finely divided Cu may be obtained (a) by re-
ducing CuO in H, stream of H ; (6) by strongly
heating a mixture of 5 parts CuzClj with 6 parts
dry NajCO,, and some NHjCl, and washing the
product (Liebig a. Wohler, P. 21, 582) ; (c) by
digesting CuSO^Aq with sifted zinc powder,
pouring ofl the liquid before quite colourless,
washing the residue with dilute HClAq, pressing
betwteen paper, and drying at about 75°.
Properties. — A reddish-yellow solid. The red
colour of ordinary Cu is due to a film of Cu^O.
Crystallises from molten state, or by slow elec-
trolytic deposition, or by ppn. by means of P, in
cubes and bctahedra belonging to the regular
system. Melts at high temperature, about 1100° ;
expands on solidifying ; very ductile, malleable,
hard, and elastic ; fairly tenacious ; very good
conductor of heat and electricity ; may be highly
polished; sonorous. Copper melted in air as-
sumes a vesicular structure on cooling owing to
escape of bubbles of gas, either CO formed when
the Cu is melted under charcoal, or 80.^ formed
by action of traces of S in the Cu on traces of
CuO present (Dick, P. M. [4] 11, 409 ; Matthies-
sen a. Eussell, P. M. [4] 23, 81). Finely divided
Cu may readily be hammered and pressed into
masses. Cu is slightly volatile when very strongly
heated (Eiemsdyk, G. N. 20, 32) ; in the OH
flame it boils and partially volatilises ; Despretz
(C. iJ. 48, 362) volatilised Cu in a H stream by
passing a current through it from 600 Bunsen-
cells. Molten Cu absorbs various gases (Hampe,
Zeitschr. f. d. preuss. BergSUtten und Salinen
Wesen, 1874 a. 1875 ; Graham, P. M. [4J 32,
503 ; Lucas, A. Ch. 12, 402 ; Marchand a. Schee-
rer, V. pr. 27, 195; Dick, P. M. [4] 11, 409;
Matthiessen a. Bussell, P. M. [4] 23, 81 ; Lenz,
J. pr. 108, 438). H is absorbed in considerable
quantity (finely divided Cu absorbs -6 volsi of H,
Graham) ; the whole of the H is not given out on
cooling, or on heating to 160° (Lietzemnayer, B.
11, 306) ; but if the Cu is heated to 250° it is
slightly oxidised, and if it is then heated to red-
ness in a nearly closed tube a little H^O is formed,
and the CuO is reduced (L., Ix.). Cu prepared
by reducing CuO in H retains a little H, which ,
may be removed by the method described; or
by heating in a stream of formic acid vapour
(Wegl, B. 15, 1139). SO^ and CO are also absorbed
by molten Cu ; C0._, and N are not absorbed. Cu
in masses is unchanged in dry air; when gently
heated it is superficially oxidised to Cu^O, at a
higher temperature CujO and CuO are formed ;
finely divided Cu burns to CuO in air considerably
under a red heat. In moist air containing CO^,
Cu becomes covered with a film of greenish basic
carbonate ; after a considerable time the interior
of such Cu contains crystals of Cu^O (D. P. J.
206, 200). Finely divided Cu, obtained by re-
ducing CuO under red heat, is changed by ordi-
nary air to Cu^O. Cu in mass decomposes HjO
at a full red heat, and then only slowly. Cu is
slowly acted on by many dilute organic acids in
the air ; eatables should not, therefore, be allowed
to remain in Cu vessels exposed to air, although
they may be boiled with water in such vessels, as
then the escaping steam removes the air. Cu is
slightly dissolved by HClAq or HjSOjAq in pre-
sence of air ; cone, hot H^SO, forms CuSO, and
GuS with evolution of SOj ; cone, hot HIAq forms
Cujij and H ; HNOjAq readily dissolves the metal
with evolution of N oxides ; SO^Aq' slowly forms
OuSOs and HjSOjAq. NHjAq, in presence of 0,
acts on Cu, forming Cu-NH, nitrate ; heated in
KHs, Cu nitride is formed. NH, salts, and some
other metaUio salts, in solution dissolve appre-
ciable quantities of Cu. Cu combines directly
with CI, Br, S, P, Si, As, Sb, and many metala
(v. Copper, AUiOTs or).
The atomic weight of Cu has been determined
(1) by reducing CuO in H (Berzelius, P. 8, 1H2 ;
Erdmann a. Marchand, J.pr. 31, 391 ; Millon a.
Commaille, C. B. 67, 147 ; Hampe, Fr. IS, ."iS-i) ;
(2) by electrolysing CuSOjAq and weighing tlie
Cu (Hampe, Fr. 13, 367; Shaw, P. M. [5J •^i,
138) ; (3) by reducing AgNOjAq by pure Cu and
weighing the Ag (Biohards, P. Am. A. 22 ; 23,
177). The number 63-2 is confirmed by the S.H.
of Cu, and by comparison of the crystalline forms
of Cu compounds with some ferrous compounds,
and also with compounds of Co andNi, and with
some compounds of Ag.
COPPER.
253
Copper is distinctly a metallic element; it
foims salts by replacing the H of most acids ;
most of these salts belong to the series GuX,
SO
where X = CI, NOj, -—J, &o. ; but several cuprous
2
salts, GU2X2, are also known. There are indica-
tions of the existence of compounds of Gu with
strongly positive metals and 0, in which the Cu
forms part of the negative radicle of the salts,
but such salts have not been isolated (v. Cofpeb,
OXIDES or). Copper is analogous in its chemical
relations on one hand to Ag, and on the other
to Fe, Ni, and Co ; it also shows similarities with
Au and with the alkali metals. In the periodic
classification of the elements Cu is generally
placed both in Group VIII., which comprises Fe,
Ki, Co, and the Pt metals, and also in Group I.,
which includes H, the alkaU metals, Ag, and Au
{v. CopPEB GKOUP OP EiiEMENTs). The valeucy of
the atom of Cu has not been determined with
certainty ; the only compound whose molecular
weight in the gaseous state has been determined
is CUjClj, the atom of Cu is most probably di-
valent in this molecule.
Allotropic form of copper. Schutzen-
berger (0. B. 86, 1265) described a bronze-co-
loured solid, obtained by electrolysing a solution of
Cu acetate containing some basic acetate (produced
by boiling) ; the negative electrode consisted of a
plate of Pt, and the positive of a somewhat larger
Cu plate; 2 Bunsen- or 3 Daniell-ceUs were
used ; the electrodes were placed 3 or 4 centims.
apart, r The bronze-coloured body was deposited
on the face of the Pt electrode turned towards
the Cu plate. The deposit was lustrous ; very
brittle ; S.G. o. 8 to 8-2 ; it contained 5 to 10 p.o.
CuO; it was oxidised readily in moist air; cold
HNO^q (10 p.c.) dissolved it readily with evolu-
tion of nearly pure NjO. This substance was
changed to ordinary Cu by heat. No H vfas
evolved by heating to 100° in COj. Wiedemann
{W. 6, 81) says that the substance obtained by
electrolysing Cu acetate as described is ordinary
Cu containing CuO sometimes amounting to 35
p.c; Schutzenberger {Bl. [2] 31, 291) asserts
that his allotropic copper is changed to ordinary
copper without change of mass {v. also Mackin-
tosh, C. N. 44, 279).
Beactions. — 1. Cu decomposes water slowly
at a fuU red heat (Eegnault, A. Oh. 62, 364).—
2. In dry air Cu is unchanged ; but in ordinary
moist air it becomes covered with a film of a
basic carbonate (U. P. J. 206, 200), and crys-
tals of CujO are formed in the interior of the
mass. — 3. Heatedin oxygen CuO is formed; very
finely divided Cu is said to form CujO in oxygen
without heating. — 4. Not acted on by weak acids
in absence of adr, but slowly dissolved by dilute
H01A.q, &c., in presence of air. Thomson gives
these thermal data (Th. 3, 320):-[Cu, 0', SC^
= 111,490; [Cu, 0', 2N0S 6H=0] = 96,950 ;
[On, O, H«SO^Aq]= 55,960; [Cu, 0,-2HN0»AcG
= 52,410. — 5. In very cone, niiric add Cu is
passive, because of formation of layer either of
NO or CuO (c/. Passivity of Iron, under Ikon).
Dissolves rapidly in less cone, nitric acid giving
ofE NO and NjO.— 6. Cone, hydrochloric acid in
presence of air dissolves finely divided Cu, form-
ing Cu,CLi and evolving H (Odling, G. J. 9, 291) ;
less COM. HCUq slowly dissolves Cu when
heated with it in presence of air. — 7. Dilute
sulphti/rio acid in presence of oxygen slowly dis-
solves Cu (forming E^Oj according to Traube,
B. 18, 1887). Cone. H^SOj acts on Cu even at
20°, forming CujS, and CuSO,; at higher
temperatures SOj is evolved, until at 270° the
action is represented by the equation
Cu + 2H2S04 = OUSO4 + SO2 -t- 2HzO (Pickering,
C. J. [2j 18, 112).— 8. Sulphii/rous acid alowly
acts, forming sulphite and H^SO^Aq ; if large ex-
cess of HjSOaAq is used, CuS is formed along with
S (Causse, Bl. [2] 45, 3). — 9. Conc.hydriodio acid
attacks Cu forming CuJ, and H. — 10. Aqueous
solutions of many metalUc salts slowly dissolve
Cu ; chlorides and nitrates, especially of ammo-
nium, are the most active {v. Pattison Muir,
C. N. 34, 223, 234 ; Carnelley, 0. J. [2] 15, 1).
According to Traube (B. 18, 1887) Cu dissolves
in (NH4)2COjAq with production of HjOjAq. —
11. Ammonia solution slowly dissolves Cu with
previous formation of CuO; Schonbein (B. B.
1856. 580) says that Cu-NH, nitrite is pro-
duced. Heated in ammonia to full redness, Cu
becomes brittle and now contains N, a nitride is
probably formed (Warren, G. N. 55, 155). —
12. Sulphuretted hydrogen forms CuS. — 13. Many
fatty oils, e.g. olive, rape, linseed, &c., dissolve
considerable quantities of Cu (Thomson, 0. N.
34, 176, 200, 213). ,
Gombinations. — Copper combines directly with
the following non-metallic elements either at
the ordinary or higher temperatures: chlorine,
bromine, iodime, oxygen, sulphur, selevAon, phos-
phorus, silicon, a/rsenAc, antimony (for details v.
OOPPBE, OHLOEIDE OP ; BBOMIDB OF, (fcc). It IS
not quite certain whether Cu combines directly
with nitrogen or not ; Blondlot (C. B. 102, 210)
got indications of combination when discs of
Cu and Pt were strongly heated in an atmo-
sphere of N (c/. COPPEB, NITBIDE OP).
Detection and Estimation. — Cu salts in solu-
tion give a deep-blue colour with excess of
NHjAq ; a mahogany-coloured pp. of ferro-
eyanide of Cu in very dilute Ikiuids. Minute
traces of Cu may be detected by immersing u
small couple of Zn and Pt wires in the
liquid, and then exposing the Pt wire to the
vapour given off by adding cone. H^SOj to KBr ;
if a trace of Cu has been deposited on the Pt a
deep-violet colour is produced, due to formation
of a compound of CuBrj.aiHjO with HBr (Cresti, ,
(?. 7, 220). Copper is often estimated by ppn.
with KOHAq, heating, and weighing as CuO ;
also by ppn. as metal by means of Zn and Pt.
Yolumetrio methods of estimation are based on
the reaction of ammoniacal Cu solutions With
KCNAq to form colourless Cn(CN)j.2NH4CN ;
on the reaction of Cu solutions with EIAq to form
Cu^j, and I; on the reaction of CujO with
FejCljAq to form CuCljAq and FeOljAq ; and on
other reactions. Cu may also be estimated by
electrolysis (v. Classen, Quantitative Analyse
durch Electrolyse [Berlin, 1886]). For details
of methods a Manual of Analysis must be con-
sulted.
Copper, Alloys of. — Many alloys of Cu are
much used in manufactures because of their
malleability, hardness, and durability, and in
some cases sonorousness. Only'a brief account
of the chief classes of these alloys is given here ;
for details of those alloys which are of especial
264
COPPER.
technical importance reference must be made to
the Dictionary of Technical Ohemisiry.
1. With altmiinmm. Alumina and CuO are
strongly heated with carbon in about the ratio
Al:9CuO:9C. The alloy which results has the
composition Cu,Al ; it has the colour o£ gold, is
very tenacious and malleable, very hard, and
takes a high polish. This alloy, or an alloy con-
taining from 5 to 10 p.o. Al, is generally known
as alumimium-hronze (v. Debray, C. B. 43,
925).
2. With antimony. Cu and Sb alloy in al-
most all proportions. Compounds SbCUj and
SbOUi probably exist (v. Ball, C. J. 53, 167).
These alloys are brittle. Sb is present in many
varieties of bronzes and in alloys for making
parts of locomotives. For action of acids on
alloys of Sb and Cu v. Calvert a. Johnson, T.
1858. 349.
3. With arsenic ; v. Copper, absenidbs op.
4. With bismuth ; various alloys are formed
by heating the metals together ; an alloy of 2
parts £i with 1 part Cu expands after solidifica-
tion (Marx, S. 58, 470).
5. With gold v. Boberts, A. Ch. [5] 13, 133.
6. With iron. Cu is alloyed with iron by
fusion. (For description of alloys v. Mushet,
P. M. (3) 6, 81.)
7. With lead. Cu and Pb melted together
at a red heat form alloys ; biit the fused mass
tends to separate into two layers; the upper con-
taining much Cu and httle Pb, and the lower
much Pb and little Cu ; separation is partly
prevented by rapid cooling. Pb is found in
many clock-metals and bronzes.
8. With nickel. Alloys of Cu and Ni, with
about lOCu and 4Nj, are nearly white ; alloys
containing Cu, Ni, and Zn are largely used under
the names of German silver, Packfong, &a.
9. 'With, silver ; Cu and Ag alloy in very varied
proportions (for detaUg v. Eoberts, A. Ch. (5) 13,
111).
10. With tin. The various bronzes, gun-
metals, and bell-metals, are alloys of Cu and Sn;
these alloys are formed by fusing the two metals
together. Many bronzes contain Pb, and some
contain small quantities of Fe and Sb. For de-
tails of the manufacture and properties of the
copper-tin alloys v. Dictionary of Technical
Chemistry. Two compounds of ,Cu and Sn ap-
pear to exist, CUjSn and CUjSn; the evidence
is based on the variations in the specific gravi-
ties, electrical conductivities, and other physical
properties, of the alloys of Cu and Sn (v. Mat-
thiessen, T. 1860. 161; Riche, 0. B. 55,
1862 ; Lodge, P. M. (5) 8, 554 ; Calvert a. John-
son, T. 1858. 349; Eoberts, P. ilf.(5)8, 58, 551;
Laurie, C. J. 53, 104 ; Ball, C. J. 53, 167).
11. With zinc Ordinary brass is an alloy
of about 2 parts Cu to 1 part Zn ; many alloys
of the two metals in various proportions areused
in manufactures under the names of Pinchbeck,
Mosaic gold, &o. Modern bronze is generally
an alloy of Cu with zinc and tin. These alloys
are formed either by fusing the metals together,
or by heating Cu with ZnO and charcoal. In
some cases one metal is ppd. on the other from
solution. For details regarding the manufac-
ture, properties, and uses of the various brasses,
&c., V. Dictionary of Techmcdl Cherrmtry.
There are indications of the formation of a com-
pound of Cu and Zn, viz. CuZn^ (v. Laurie, C. St,
S3, 104). For action of acids on Cu-Zn alloys
V. Calvert a. Johnson, G. J. [2] 4, 435; also
Matthiessen, C. J. [2] 4, 502.
Copper, Antimonate of. Cu(Sb03)j.5II,0
(Fremy, A. Ch. [3] 12, 499 ; Hefiter, P. 86, 418).
Copper, Antimonides of {v. Cofpeb, aliioyb
of).
Copper, Arsenates of. Cu5H2(AsO,)4.2H20,
and Cu5(A304)2 {v. Absenio, aoids op, vol. i. 308).
Copper, Arsenides of. The compounds
CujAs, GUijAs, and Cu^As, occur native as
Domeykite, Algodonite, and Darwinite, respec-
tively. According to Lippert {J.pr. 81, 168) the
grey deposit obtained by heating Cu in an HCl
solution of As^Oa in Cu^As, ; when this is heated
in H, CujAs remains.
Copper, Arsenites of. CuHAsO,, and
Cu(As02)2; V. Arsenic, acids or, vol. i. 306.
Copper, Borlde of. When amorphous B is
heated with Cu in a crucible for some hours,
above the M.P. of Cu, a yellow, very hard, brittle,
mass is obtained, S.G. 8'116 ; this is CUgBj ac-
cording to Marsden (O. J. 37, 672).
Copper, Boroflnoride of. Cu (BF^),, v. under
Copper, fluorides of.
Copper, Bromides of. Two bromides are
known, CuBr^, and CujBr^ (or OuBr). The mole-
cular weight of neither in the gaseous state has^
been determined ; but judging from the chlorides
the formula given are probably molecular.
Thomsen gives the thermal values [Cu^Br"]
= 49,970; [Cu,Br^ = 32,580 ; [Ou'Br',Br'^
= 15,190; [Cu,Br^AcLl = 40,830 (r^i. 3,319).
L CuPRio bromide, CuBr,. {Copper dibrom-
ide^ Prepared by dissolving CuJOH)^ in HBrAq,
or digesting Cu turnings with excess of BrAq, or
adding EBrAq to CuSiPjAq ; the green solution
turns brown on evaporation ; when the residue
is gently heated, CuBr, remains as a graphite-
coloured fusible mass. If the green solution is
evaporated m vaciu> over H2SO4, CuBrj is ob-
tained in lustrous iodine-coloured crystals (Bam-
melsberg, P. 55, 246). By evaporating in air,
Berthemot (A. Ch. 44, 385 ; v. also Lowig, P.
14, 485) obtained greenish-brown crystals of
CuBrj.SHjO. CuBr, is deliquescent and very
soluble in water ; when heated it gives CuBr and
Br. This bromide combines with ammonia to
form CuBrj.SNH, and CuBrj.SNH, ; the former
is a blue powder obtained by passing NH, over
CuBrj; the latter forms dark-green crystals, ob-
tained by adding alcohol to CiiBr^Aq saturated
with NHj (Eammelsberg, P. 55, 246). These
double compounds dissolve in water ; on dilution
Cu(OH)j is ppd.; when heated they give off
KE, and NE^Br and leave a mixture of CuBr,
and CuO.
' II. CuPEOTJS BROMIDE. Cxi^T^ (Copper mono-
bromide.) Prepared by heating CuBr,, by pass,
ing Br over heated Cu, or by reaction between
Cu and CuBrjAq mixed with FeBr,Aq (Benault,
C. B. 59, 319). A white powder, insoluble in
water. S.G. 4-72; M.P. = 604°; B.P. between
861° and 954° (Carnelley a. WilUams, C. J. 37,
125). Not decomposed by cone. H^SO,, but by
HNOjAq (Berthemot, A. Ch. [2] 44, 385; Lowig,
P. 14, 486). Turns bluish in sunlight and is
then less soluble than before in KaClAq 01
NajSjO^q (Renault, 0. B., 69, 319),
COPPER. CHLORIDES OF.
255
Copper, Chlorides of. Two chlorides of cop-
per are known, CuClj and CuCl or Cu^Olj. Many
experiments have been made on the Y.D. of
cuprous chloride ; it is very probable that the
molecular formula of this salt is CujClj. Thom-
sen gives the thermal data [Ou'-'.CH'] = 65,750 ;
[Cu.Ol'^ = 51,630 ; [Ou, CP,2H^0] = 58,500 ;
[CuC1^2ffO] = 6,870; [Cu.Ol^Aq] = 62,710 (Th.
3, 319).
I. CuFBia CHLOBiDB. CuGl,. (Coppgr di-
ehloride.)
Preparation. — 1. By burning Cain 01 gas, or
by passing 01 over heated OuOl. — 2. By dis-
solving Ou in aqua regia, or in boiling cone.
HOlAq in presence of air, or by dissolving CuO
or OuOO, in hot HOlAq; the green solutions
thus obtained are evaporated and the crystals of
CuCLj-aHjO which form are heated to 100°.-^
3. By mixing NaClAq with OuSOiAq, evaporating,
filtering from Ka^SO,, evaporating, and heating
the GaOl2.2H20 obtained.
Properties and Reactions. — ^A brownish-yellow,
deliquescent, solid ; melts at red heat and gives
CuGl and 01. Easily soluble in water, solution
in a very little water is dark-green (Solly, P. M.,
1843. 367) ; on addition of more water it becomes
green, colour of very dilute solutions is greyish-
blue (Gladstone, C. J. 8, 211, says that
OuOl2.2CuO.4H2Q is formed) ; addition of cone.
HOlAq or better H^SO, produces a yellow colour
in a green solution of OuOl^. JPranz (J. pr. [2]
6, 274) gives the following data showing the com-
position and S.Q-. of OnCLiAq : —
P.c.0u01, S.G. P.e. OuCl, S.G.
5 1-0455 25 1-2918
10 1-092 30 1-3618
15 1-1565 35 1-44 i7
20 1-2223 40 1-5284
CuOl, is soluble in alcohol and in ether ; alco-
holic solutions burn with green flame. CuCljAq
ppd. by KOHAq yields various oxyohloridea (v.
CoPFEB, oxYHUiOiD COMPOUNDS op). Fot rcactions
of OuOlj with metallic sulphides, v. Bammels-
berg (C. J. 39, 374), and Baschig {A. 228, 1).
Combinations. — 1. With water to form
CnOl2.2H20 ; obtained by evaporating solutions
of Oudl, and crystallising (v. swpra) ; rhombic
prisms a:6:c = -9179:1: -4627 {Gfm.-K. [6th ed.] 3,
642) ; lose 2HjO at 100°, or over HjSO, (c/. Vogel,
D. P. J. 136, 239, with Graham, A. 29, 31).—
2. With amnumia to form M.2NHa, M.4NH3.HjO,
and M.6NH, [M = CnCU (Kane, A. Ch. 72, 273;
Bose, P. 20, 155). Cu01j.6NH3 is formed by
passing KH, over OnCl, as long as absorption
continues ; when heated to 149°, NH, is evolved
and CaClj.2NH, remains. When NH, is passed
into hot cone. CaCL,Aq until the pp. which
forms has re-dissolved, and the liquid is allowed
to cool, Cn01j.4NHj.HjO separates in dark-
green octahedra which lose NH, on drying.—
3. With ammonia and salammoniae to form
Ou01j.2NH,.2NH4Cl ; obtained by boiling Ou
turnings with cone. NH^OlAq till a deep-blue
liquid is obtained, filtering from Cn2Clj.2NH,
which separates, allowing the filtrate to oxidise
in the air until it becomes greenish, and cooling
Saitthausen, J.pr. 60, 376). Dark-green tablets,
ecomposed by water. — 4. With cuprous chloride
and ammonia to form 0u01j.0ujClj.4NH3.H,0
(Eitthausen, X pr 60, 374); obtained by dis-
solving CujOlj in NH^q, allowing the solution
to become deep blue by exposure to air, and
crystallising; or by the prolonged action of
NHjClAq on Ou turnings at the ordinary tem-
perature. Blue prisms; decomposed by water
and alcohol ; al)s6rb 0 from air and lose KH, ;
when heated leave On^Olj; soluble in hot
HClAq from which solution 0uCl2.2NH.,01.2H,O
crystallises out. — 5. With ammonium chlor-
ide, to form (a) OuCl2.2NH4Ol.2H2O, and (b)
CuCl2.NHj01,2H2O. The former is obtained by
crystallising a mixed solution of the two sajts
(Mitscherlich, J.pr. 19, 449; Graham, A. 29,
132) ; or by concentrating a mixed solution of
OuSO, and NH^Cl (Vogel, J. pr. 2, 194) ; or
saturating OuCljAq with NH3 (Cap a. Henry,
J.pr. 13, 184). Light-blue rhombic tables, or
octahedra; loses all HjO at 110°-120°; S.G.
1-96 to 1-97. The salt CuCL.NH,01.2H20 was
obtained by Hantz (A. 66, 280), as blue-green
crystals, by neutralising 1 part HClAq by NH,
and 2 parts of the same HOlAq by CuCO,, mix-
ing the solutions, and crystallising.— 6. With
potassium chloride to form CuCl2.2KCl.2H2O ;
obtained by evaporating a mixed solution of th^
two salts. S.G. 2-4.
n. CnPBOus OhiiObide. CujOIj. {Proto-
cMoride of copper.) Mol. w. 197-14. V.©. (c.
1560°) 6-8. Formula found to be OU2CIJ and not
CuCl from results of V.D. determinations by V.
and 0. Meyer, at 0. 1560° (B. 12, 1112, 1283).
[0u^ 01'=] = 65,750; [OtfCl^ CP] = 37,510 (Th.
3, 319).
Formation. — 1, Cu is heated in 01, keeping
the Ou in excess.^2. Ou is heated to duU red-
ness in a stream of HCl (Wohler, A. 105, 360).—
3. By heating together OuCl, and Cu in HClAq.—
4. By heating together Cu and Fe20l5Aq. — 5. By
heating OuClj.— 6. By reducing CuCl2Aq or
CuSOjAq by SnCl2, or SOj.— 7. By heating 2 parts
HgCLj with 1 part Cu turnings. — 8. By heating
OUSO4 with NaH^POj in a little water (Cavazzi,
G. 16, 167).
Preparation. — 1, Sulphur dioxide is passed
into a mixture of 1 part NaCl and 2^ parts
OUSO4.5H2O dissolved in water ; the white pp.
is washed with SOjAq, then with glacial acetic
acid, pressed between paper, and dried at 100°
(Wohler, A. 130, 373; Bosenfeld, B. 12, 954).
pCuCljAq H- H2SO, + HjO
= OU2OIJ + HjSOjAq + 2HClAq].— 2. An intimate
mixture of 14-2 parts powdered CuO with 7 parts
zinc powder is thrown, little by little with con-
stant shaking, into cone. HClAq, until a white
pp. of OU2OI2 begins to form ; more acid is added,
and then a little more of the mixture, and so on
until the whol^ of the mixture has been used.
The liquid is then poured into boiled water in a
flask so that the flask is filled; the flask is
closed ; the Cu^OIj, which separates as a shining
white solid, is washed with distilled water,
and dried in the dark (Heumann, B. 7, 720).
[2CuO+Zn + 4H01Aq
= 00201, + ZnOLjAq + 2H2O].
Properties. — Snow-white crystalline powder ;
insoluble in water, alcohol, dilute HNO, or
HjSO^Aq ; soluble in hot HCLAq, separating on
cooling in tetrahedra ; soluble in NH,Aq ; solu-
ble, on heating, in KGlAq, NaClAq, Fe2Cl5Aq,
ZnCljAq, and many other metallic chlorides;
soluble in Na,S203Aq when the two salts are in
the ratio CujOl2:NaaSjO, (Winkler, /. pr. 88,
256
COPPEE, CHLORIDES OF.
428). S.G. 3-7. Melts below rod heat, and boils
between 95-1° and 1032" (Canielley a. Williams,
C. J. 37, 126). Solution in HClAq acts as an
energetic reducer, converting HgOL, to HgCl,
AuClj to Au, decolourising Prussian blue, &o. ;
this solution rapidly absorbs CO (v. Hempel, B.
21, 898 ; cf. Drehsohmidt, B. 21, 2158), colour-
less crystals of Ca2Cl2.00.2H^O separate from a
saturated solution of 00 in CujCl^ (Berthelot,
A. Oh. [3] 46, 488), on warming the solution CO
escapes. This solution also absorbs various
gases, e.g. C^H^ and PHj (Biban, B. 12, 1208;
Bose,P. 4, 110; 6,205).
MeacHons. — 1. Moist CU2CI2 changes in sun-
light and air to yellow, violet, and then blue-
black; an oxychloride is formed (CuOl^-SCuO,
according to Vogel, D. P. J. 136, 238) [concern-
ing the action of sunlight on CujCl^ v. Carle-
mann, J. jpr. 63, 475]. — 2. Heated in oxygen or
in wafer-vapour, CuO is formed. — 3. By repeated
washing with water CuClj and CujO are pro-
duced.— 4. Reduced to Cu by hydrogen, or by
digestion under water with iron filings. — 5.
Scarcely acted on by sulphuric acid, even when
cone, and hot (Eoseufeld, B. 12, 954). — 6. Eeaets
with many metallic sulphides to produce Cu^S
{v. Easchig, A. 228, 1).
CombitmtionSi — 1. With ammonia to form
CU2CI2.2NH3. By dissolving CUaClj in NHjAq ;
or better by boiling Cu turnings with cone.
NH,ClAq until rapid evolution of NH3 begins,
filtering the boiling liquid into ^ its volume of
water, and repeatedly filtering from C\i.jP.xn.JO,
allowing to cool, repeatedly washing the solid
which separates with alcohol and quickly press-
ing between paper (Eitthausen, J. pr. 59, 369,
Millon a. Commaille, 0. B. 56, 309); Colourless
rhombic dodecahedra, becoming violet in air;
decomposed by water into its constituents on
heating ; solution in water reduces ammoniacal
silver solutions (M. a. C), it absorbs 0 from the
air forming CU2Cl2.OuCl2.4NH3.H2O (g.i). under
OupBiooHiiOinDB, CombinaUons, No. 4). — 2. With
salcmimoniac to form Cu20l2.4NHj01. Obtained
by dissolving OU2CI2.2NHS in HGlAq, or by add-
ing a little NHgAq to CajOI; in HClAq ; white
crystals, becoming brown in air, and giving
CujClj and NH4CI when heated (Eitthausen,
J.pr. 5.9, 369).-^3. With potassium chloride io
form OujCl2.4K01; large octahedra; prepared
by dissolving CUjOLj in boiling KClAq, and al-
lowing to cool in a closed vessel (Mitscherlich,
A. Ch. 73, 384). A compound with NaCl is also
known ; it is very soluble and difficult to crys-
tallise.—4. "With phosphorus hydride, to form
OU3CI2.2PH,. Obtained, as long colourless
needles, by passing PH3 into CujOL, in HClAq
until crystals form ; when heated gives Cu phos-
phide, PHj, and HCl; water forms PHj and
CujPj (Eiban, Bl. [2] 31, 385).
Copper, Fluorides of. Two fluorides have
been isolated, CuPj and CujFj (Berzelius, P. 1,
28).
I. Cdpkio rLTJOEiDE, CuPj.2H20. Best ob-
tained by dissolving CuCOj in HPAq, and adding
alcohol of 95 p.e. (Balbiano, 0. 14, 74). Pale-
blue orystalline powder; sparingly soluble in
water, very easily decomposed to oxyfluoride
CuF2.0u{0H)j[=0aP.0H] {v. Oxyfluoride under
Copper, oxyhaloid oompocnds op). Decomposes
on keeping for four or five days -with evolution of
HP. Combines with KB" to form very soluble
0uB'2-2KP. Absorbs NH, with formation of
CuI'3.0u(OH)3.4NH3.2NH,P.2H20 (palbiano, l.c.),
Gupria horofluoride
0u(BPi)2[= CuPj.ZBFa] is obtained by mixing
Ba(BB'j)3 and OuSO^Aq.
Oupric siliaofluoride OuSiPj.6H20 is
produced by dissolving CuO in HjSiJE'iiAq and
evaporating.
II. OuPBons FLUORIDE, CujF^- A. red powder
obtained by treating CUjO.sHjO with HPAq;
washing with water, pressing, and drying in
vacuo ; decomposed by moist air to Ou(OH)2.0uP2
(BerzeUus, l.c.).
Copper, Hydride of. A compound of Cu and
H is said to be produced by the following re-
actions:— 1. 1 pt. Ba(H2P02)2 is dissolved in
water, the Ba is exactly ppd. by HjSO^Aq, the
filtrate is added to "8 parts OuS04.5Bi20 in rather
dUute solution, at the ordinary temperature, ppn.
is allowed to proceed slowly ; the pp. is washed
with air-free water in an atmosphere of OOj,
and dried by pressure between paper (Wurtz,
A. Oh. [3] 11, 250; C. B. 89, 1066; 90, 22).—
2. NaHSQjAq is added in excess to 0uS04Aq;
if the CUSO4 is in excess the pp. contains some
Cu (Sohutzenberger, 0. B. 69, 196).— 3. Zinc is
placed in CuSOiAq acidulated with H^SO,
(Sohoor, Ar. N. 12,96; [J. 1877. 273]).— 4. A
moderately strong current is passed through
very dilute slightly acidulated CuSOjAq; the
compound forms at the negative pole but begins
to decompose, with evolution of H, as soon as
the current is stopped (PoggendorfE, P. 75, 337).
Copper hydride is described as a reddish-brown
powder, having the composition CujHj ; it de-
composes at 60° into Cu and H; in HClAq it
gives. Cu,Cl2 and H; it takes fire in CI. (0/. Ber-
thelot [Cf. B. 89, 1005, 1097], who says that the
so-called copper hydride always contains 0, H,0,
and P ; but Wurtz [O. B. 90, 22] gives further
details and analyses, showing that the prepara-
tion is apt to contain Cu phosphate, but the pre-
sence of more than a mere trace of this may be
avoided by ppg. the CujHj very slowly in cold
solutions.)
Copper, Hydroxides of, v. Htdrated oubes
OP Copper, under Copper, oxides op.
Copper, Iodides of. Only one iodide of copper
has been isolated; this is the cuprous com-
pound, Ca2l2. Whrai KIAq is added to the
solution of a oupric salt, a pp. of OuJ.^ mixed
with free I is obtained; e.g. 2CaS04Aq + 4KIAq
= Gn2l2 + ti + 2K2SO,, Aq. CUjIj dissolves in alco-
holic solution of I; the liquid is not ppd. by
water, but on heating and adding alcoholic solu-
tion of KI, CU2I2 is ppd. along with KIj. Solu-
tions containing about 3 gram CUI2 per 100 c.c.
have been obtained ; compounds are known
which probably contain Culj {v. infra).
Cuprous iodide, CujI,. S.G. 4-41 (Schiff).
B.P. between 759° and 772° (Carnelley a. Wil-
liams, O. J. 37, 126). Mol. w. not determined,
but from analogy of Oifil^ it is probably CujI.
= 379-46. [CuMT = 35,200 {Th. 3, 319).
JB'ormaUon.—l. Pinely divided Cu heated
with I forms CU2I2; a plate of Cu exposed to the
vapour of I becomes covered with crystals of
Cu,l2 (Eenault, 0. B. 59, 319).— 2. Cu is dis-
solved in cone. HIAq, on standing in air (or
better on adding a trace of HjS) Cujlj ppts. in
COPPER. OXIDES OF.
257
crystals (Eose, P. 4, 110).— 3. Cu^S is dissolved
in oono. HIA.q (Mensel, B. 3, 123).— 4. KIAq is
added to ,OuSO,Aq; Cujij is ppd. along with I.
Preparation.—OaSOikq is saturated with
SOj, or a mixture of 1 pt. CuSOj.SHjO and 2| pts.
FeSOj.THjO is dissolved in wMer, KIAq is added,
the pp. is washed and dried (Duflos, A. 39, 258 ;
Soubeiran, J. Ph. 13, 427).
Properties and Reactions. — A white, or
brownish-white, crystalline powder; insoluble
' in water, alcohol, and dilute acids; soluble in
EIAq, and in NHjAq in presence of air. Soluble
in hot cone. HOlAq and reppd. on addition of
water. Decomposed by cone. HNO3 or HjSO,.
Heated with MnO, or KOIO3, CuO is formed ;
reduced to Cu by boiling with water and Zn, Sn,
or Fe (Berthemot, J. Ph. 15, 445). When Co,!,
is dissolved in NH,Aq by heating in an open
vessel, colourless crystals of OU2X2.4NH3 separate
on cooling, and the mother liquor on addi-
tion of alcohol deposits a dark-blue compound
OuIj.4NH3.HjO (Kammelsberg, P. 48, 162; v.
also Berthemot, J. Ph. 15, 445 ; and Saglier,
O. B. 102, 1552). Oujij dissolves in alcoholic I ;
when this liquid is heated to 30°, and mixed
with alcoholic NH, at 80°, crystals separate in
a few hours having the composition OuI2.4NH3.I2
(Jorgensen, Jipr. [2] 2, 353).
GomMnations. — 1. With tj/mmonia to form
CU2I2.4NH3 (Kammelsberg, P. 48, 162). Obtained
by passing NH, over OujI,; white, lustrous
crystals ; decomposed by heat to Oujij and NH,.
The same compound is formed by mixing KIAq
with an ammoniacal solution of a cuprous salt
in absence of *air ; as thus obtained the compound
caimot be dried without losing NH, (Levol,
N. J. P. 4, 328). — 2. With ammmdwrn iodMe ;
the compound Ca2I2.2NHJ.H2O is obtained, as
white needles, by dissolving 100 gs. NHjI in
1,000 gs. water, adding 10-15 gs. Ou{OH)2, heat-
ing until all is dissolved, boiling with a large
excess of On untU the liquid is colourless, and
allowing to cool. The mother liquor in air de-
posits black crystals of OU2I2.2NH4I.2NH3.4H2O.
These crystals are very unstable (Saglier, G. B.
104, 1440). — 3. With ammoma and czi{pric iodide;
when 100 gs. of an ammoniacal solution of OuO,
containing 7-8 p.c. CuO, is mixed with an equal
mass of 10 p.c. alcoholic I solution, warmed
until the pp. of NI3 dissolves, heated in the
water bath for an hour, and allowed to cool,
brilliant green crystals are deposited of the com-
position Cual4.4NHj, probably = Cu2X2.CuI2.4NHj
(Sagher, C. B. 102, 1552).— 4. With siloer iodMe
to form a series of bodies resembling alloys;
Cujlj.iEAgl, X varying fi;om 1 to 12 ; for physical
constants of these bodies v. Eodweli,Pr. 33, 143 ;
Bellati a. Eomanese, Pj-.,34, 104. According to
Guyard (Bl. [2] 41, 12) a double iodide of Cu
and N is produced when an alkaline di-iodide is
added to an ammoniacal Cu solution.
II. CnpKio IODIDE. Cuprio iodide, CUI2, has
not been isolated. A solution of OU2I2 in alco-
holic I is not ppd. by water, but on heating and
adding alcoholic KI, OujIj is reppd. along with
KIj, the solution may perhaps contain a periodide
of Cn (Jorgensen, /. pr. [2] 2, 347). CUjIj in
presence of I dissolves in much water ; this solu-
tion probably contains CuL, (Traube, B. 17, 1064).
Carnegie {priv. comm.) has obtained aqueous
solutions of cuprio iodide containing e. '3 g.
Vol. II, ■
Culj in 100 CO., by digesting CujI^ with I in
water at 80° for a tew minutes, cooling, shaking
for a short time with Cu foil or CSj to remove ex-
cess of I. Solution of Culj containing c. '9 g,
CUI2 with excess of I is very easily decomposed,
almost anything that removes the I at the same
time decomposes the Culj to Cul and I, e.g.
starch or Ag leaf ; the solution partially decom-
poses when boiled out of contact with air, also
when' a current of air, N, or other indifferent
gas, is passed through it, and even when kept
m vacuo at the ordinary temperature. Solutions
of OUI2 are also obtained by digesting CuOjHj, 01
CuCO,, with fairly cono. HIAq saturated with I,
and filtering from excess of CUO2H2, or CuCOj,
Potassium iodide withdraws I from solutions of
Culj, ppg. Oul ; when KI interacts with a cuprio
salt in molecular proportions, Culjis almost cer-
tainly produced, but as the change is not com-
plete the residual KI interacts with the Culj in
solution to produce Cul and KI.kI. Thomsen
gives [Cu,F,Aq] =10,410 (Th. 3, 820).
Various compounds areknown , one constituent
of each of which is probably Culj. The forma-
tion of the compounds Cul2.4NH,.H20, and,
OuI2.CU2I2.4NH3 has been described {v. Oupkods
IODIDE, BeacUons, also Gomhinations, No. 3).
The compound CuI2.4NH3.I4 was obtained by
Jorgensen (J.pr. [2] 2, 853) as blue orystalB,v
by mixing solutions of I in KI and Cu-NHj
nitrate, at 50°, and filtering hot into water at
50° (v. also Saglier, C. B. 102, 1552). Saglier
(C. B. 104, 1440) describes the compounds
CuI2.2NH4I.2NH3.2H2O, and Oul2.4NH,.H20,pro-
duced by boiling NHjIAq with Ou(OH)2; he
also describes a compound with (NH4)l2, viz.
OuI2.2NH4I2.2NH3.6H2O, obtained by dissolving
Ou(OH)2 in hot NH4l^q.
Carnegie (priv. comm.) has obtained the
compound CuO.2OuI2.4H2O by partially immers-
ing slips of Cu in BaljAq ; black crystals slowly
form on the sides of tiie vessel ; they are easily
decomposed by washing with water ; they may
be washed with alcohol and dried over CaCl2.
Copper, ITitride of. OU3N. When finely
divided OuO, ppd. from hot CuSOjAq by KQH,
is heated in a tube to 250° and dry NH, is passed
over it, greenish -black copper nitride is formed ;
if the solid is powdered &om time to time and
the passage of NH3 is continued, the whole of
the CuO may be changed to nitride. Copper
nitride decomposes by heating to about 300°,
giving Cu and N ; in 01 it gives CUCI2 and N ;
in HClAq, OUOI2, and NH4OI are formed ; it is
oxidised rapidly by HNOjAq, and decomposed to
On and N by H2S04Aq (Schrotter, A. 37, 136 ;
V. also Warren, G. N. 55, 155). By heating to
bright redness discs of Cu and Pt placed 3-4 mm.
apart in an atmosphere of N, Blondlot got indi-
cations of the formation of a compound of Cu
and N ; but he did not isolate the compound
(C. B. 102, 210). According to Schrotter (l.c.i
Cu and N do not directly combine.
Copper, Oxides of. Copper forms four oxides ;
OU4O, OojO, CuO, and OuOj. There are indica-
tions of the existence of other oxides, but none
has been certainly isolated. The best-studied
are OU2O and CuO ; both are basic, and each
forms a series of corresponding salts, those
corresponding to OuO being the more stable.
The oxide Cu.O reacts with acids to form Cu and
S
268
COPPER, OXIDES OF.
a .?.iU, in some cases a cuprous, and in other
cases a oupric, salt. The oxide OuO^ reacts with
acids as a basic peroxide, forming cupric salts
and oxygen. Any oxide other than CuO is
changed into CuO by heating in air or oxygen.
By adding solution of bleaching powder to
Cu2N03Aq, a pp. is obtained which soon decom-
poses with evolution of O ; this pp. is possibly a
salt the acidic radicle of which is composed of
Cu and 0 (v. p. 260). No oxide of Cu has been
gasified, hence the formulse given are not neces-
sarily molecular.
I. CoppBB SUBOXIDE CujO. {Quadroxide of
copper) (Bose, P. 120, 1). An olive-green powder;
stable under water in absence of 0, but rapidly
oxidised in air to Cu^O and then to CuO ; decom-
posed by dilute HGlAq to GU2GI2 and Gu, and by
dilute HjSOjAq to CuSO^ and Cu ; insoluble in
KHjAq, and in a mixture of NHjAq and
(NHJjOOjAq. Prepared by reaction between
CuSOjAq and SnClj in presence of EQH ;
Cu(0H)2 is first precipitated and then reduced
with simultaneous formation of K stannate :
4Cu(OH)2 + 12K0HAq + SSnCljAq
= Gu,O-h6KGlAq + 3K2SnO8Aq + 10H2O. To
prepare this oxide, Bose directs to make 300 o.c.
CuSO,Aq ' containing 10 g. Cu; to add this to
1,000 0.0. of a solution of 50 g. SnCL, in KOHAq,
and to shake in a weU-closed vessel which is
completely filled with the liquid, keeping cool
by water ; to filter after twenty-four hours in an
atmosphere of H, and wash the pp. with water
containing KOH, then with water, then with
very dilute NHjAq, and finally with water. It
is difficult to obtain Gu^O free from the other
oxides. (For precautions v. Bose, l.c.)
II. CopBous OXIDE GujO. {Semi-oxide of
copper. Protoxide of copper. Bed oxide of cop-
per.) S.G.J2 5-749 (native), 5-345-5-375 (arti-
ficial). H.F. [CuSO] =40,810 (Th. 3, 320). Occurs
native as Cvprite, in lustrous, red, octahedra.
Formation. — 1. By heating Cu in air; the
outer film thus formed is GuO, beneath this is a
film of CujO. Finely divided Gu (obtained by
reducing CuO in H at a moderate temperature) '
oxidises in air to Cu^O (Berzelius, A. 61, 1 ; v.
also Mitscherlich, J.pr.l^, 450 ; and Marchand,
J. pr. 20, 505). — 2. By hea,ting Cu turnings with
CuO (Berzelius), or with dehydrated GuSOj
(Dllgren, P. 55, 527), or with CuSO, and NaoCOj
(Malaguti, J.pr. 2, 167).— 3. By heating CijCl^
with NajCO, (Wohler a. Liebig, P. 21, 581).— 4.
By the reaction of Cu with Cu2NOs and a little
CuO, in absence of aii (Becquerel, A.Ch. 41,
223). — 5. By the prolonged action of NHjAq on
a mixture of CuSOjAq and FeSOjAq in presence
of Fe2(OH)5 (Wibel, Reduction von Eupferoxyd-
sahen [Hamburg, 1864], 2).
Preparation. — 1. 5 pts. CujClj are heated
with 3 pts. dehydrated NajCO,, the resultant ^lass
is washed with water (W. a. L., P. 21, 581).— 2.
A mixture of 1 pt. OuS045H20, IJ pts. cream of
tartar, 2 pts. grape sugar, in 12 pts. water, is
heated in a basin ; 1^ pts. NaOH are added, and
the whole, is boiled until the supernatant liquid
is colourless ; the pp. is washed with water, then
with alcohol, and dried (Bottger, i). P. J. 171,
77).— 3. An intimate mixture of equal parts GuO
and (NHJ2CO3 is heated over a Bunseu-burner
till the smell of NH, is no longer apparent (Sohiff,
W. J. 1864. 274).
Properties. — ^A carmine-red crystalline pow-
der. Melts at full red heat and oxidises to
GuO. Soluble in NHjAq, forming a oolourlegs
liquid which becomes blue in the air, and reacts
as a strong reducing agent.
Reactions. — 1. Hyd/rochlorioaddioTnii OujCIj,
soluble in exbess of the acid [Cu'0,2HClA^
= 14,660 (Th. 3, 320).— 2. DiVwte acids, e.g.
HjSOjAq, HNOsAq, HjPOiAq, H.HjGjOyAq, pro- ■
duce Cu and cupric salts. — 3. Gone, nitric acid
forms CU2NO3. — 4. Bromime water forms CuBr,
and CuO. — 5. Eeduced to Gu by hydrogen, po-
tassium, or carbon. — 6. Sulphur forms CujS. —
7. Many metalUc chlorides in solution, e.g.
MgCl^Aq, ZnClj,Aq, form soluble double salts
and also ppt. hydrated oxides of the metals. —
8. Ferrio chloride solution produces FejO,, Cu,
and CujClj. — 9. From neutral silver solution
CujO ppts. a mixture of Ag and a basic cupric
salt.
Hydbated cnpEous oxide ?40u20.H20. Pro-
duced, as a yellowish powder, by adding an alkali
or alkaline carbonate to the solution of 'a cuprous
salt,(Fremy, A. Ch. [3] 23, 391). Also formed by
heating to boiling moist Gu(0H)2 with milk sugar
and some Na^COjAq. According to Mitscherlich
(/. pr. 19, 450) the hydrate loses its water at
360°- Oxidises in air to Cu(OH)j {v. also Qm.-K.
[6th ed.] a, 595 ; Millon a. GommaiUe, 0. R. 57,
145 ; Field, 0. J. [2] 1, 28 ; P. de Saint-Gilles,
A. Oh. [3] 42, 36). Dissolves in dilute acids to
form cuprous salts, very few of which have been
isolated.
III. Cupbio oxide CuO. {Black oxide of
copper. Copper oxide.) S.G-. 6'1 to 6*4 (Boullay,
A. Ch. [2] 43, 266 ; Playfair a. Joule, O. S. Mem.
3, 57). H.F. [Cu,0] =37,160 {Th. 3, 320). Oc-
curs native in North America as MelaJcomte.
Crystallises in monoclinic forms; a:b:e
= l-49:l:l-36 (Maskelyne, B.A. 1865).
Formation. — 1. By heating Cu in air or 0,
removing the scales which form, and strongly
heating in air. — 2. By heating Cu2N0„ Cu(0H)2,
CuCOs, or very strongly heating CuSOi-
Preparation. — 1. Pure Cu, prepared by elec-
trolysis, is dissolved in HNO,Aq, to one-half of
the solution NHjAq is added until the pp. which
forms has just dissolved, the other half of the
liquid is then added, the whole is evaporated to
dryness, and the Cu nitrate thus obtained is
strongly heated ; the oxide thus formed is well
washed, and again heated in a Pt dish (Bei-
schauer, .T. 1863. 274; Erdmann a. Marchand,
eT. pr. 31, 389). The oxide must not be too
strongly heated else it partially fuses and con-
tains CujO ; according to Thudichum a. Kingzett
{0. J. [2] 15, 363) the oxide should be heated
in vactio to remove traces of CO,. — ^2. A so-
lution of equivalent masses of CUSO4.5H2O and
NajCO, is evaporated to dryness and the residue
is heated strongly in a crucible and then well
washed ; moist air is then passed over the heated
oxide to remove traces of chlorides (Stanford,
O. N. 7, 81 ; Erlenmeyer, Z. 1863. 157). The
oxide as thus prepared is specially adapted for
use in organic analysis.r-3. The oxide is obtained
in cryst^s by dropping CujClj in small succes-
sive quantities into a red hot Pt crucible (Schulze,
J.pr. [2] 21, 413) ; Becquerel {A.Ch. 51, 122) ob-
tained crystals of GuO by heating to dull reduesa
COPPEB, OXIDES OF.
259
6 grams amorphous CuO with 2-3 grams pure
KOH, washing with water, and separating the
crystals by shaking.
Properties. — Brown-black amorphous powder;
or metal-like, lustrous, monoclinic crystals. Hy-
groscopic (u.Bentzsch, J.pr. [2j 21,413). Slightly
volatile in a porcelain-oven (Eisner, J. 1866. 35).
Said to lose 0 when strongly heated giving
Cu0.2CujO (Pavre a. Maumenfi, G. B. 18, 658).
According to Eeisohauer (J. 1859. 216) CujO is
formed by very strongly heating CuO ; this is
confirmed by Debray and Joannis (C. B. 99,
583) provided the heating is conducted in vacuo.
According to Joannis (0. B. 102, 1157) OuO pre-
pared at a high temperature develops leas heat
when dissolved in HClAq than specimens pre-
pared at a low temperature. CuO is a basic
oxide reacting with acids to form cuprio salts
CnX2[X = N0„^» &o.]; it dissolves in much,
KOHAq, and perhaps forma salts in which CuO
ftcts as an acidic radicle.
Beactions. — 1. Easily reduced to Cu by heat-
ing in hydrogen or carbon monoxide, . or with
carbon or carbon compounds [hence its use in
organic analysis] (for temperatures at which re-
duction in H and CO begins v. Wright a. LufE,
C. J. 33, 1). — 2. Heated with copper forms
OUjO.— 3. Heated with pJwsphortis, phosphide
and phosphate of Cu are formed.— 4. Heated
with sulphuretted hydrogen, or with sulphur in
a stream of hydrogen, Cn^S is formed (Rose, P.
110, 120). — 5. Heated with sulphur alone gives
CujS and SO, if S is in excess, or Cu^O and
CuSOj if CuO is in excess (Jordan, J. pr. 28,
222). — 6. Heated with salammoniac CxijOl^ and
a little CuClj are f ormed.^7. Heating with ferric
chloride produces Ee^Oj with GuClij and CujOlj
(Hunt, 0. B. 69, 1357).— 8. Beaots with zvne-
chloride solution to produce a green powder
Znfiufil,.eHfi (Andr6, C. B. 106, 854).— 9. So-
li^ble in ammonia, also in molten potash. — 10.
Acids dissolve CuO with formation of cnpric
salts: Thomson gives the following thermal
data (M = CuO) ; [M,2HC1Acl1 = 15,270 ;
[M,H'SO'Aq] = 18,800 ; [M,2HN0'Aq] = 15,250 ;
[M,2HC10»Ac|] = 15,910; [M,2C^H*0'Aq] = 13,180;
[M,SO'] = 42,170 ; [Cu,0,H''SO«Aq] = 55,960 ;
[Cu,0,2HN0'Aq] = 52,410.
Combinations. — 1. With water to form
CUO.H2O, produced indirectly, v.infra. — 2. With
water and amrnonia to form xGuO.yJiS^ji^O.
CuO dissolves inNH^Aqin presence of air, especi-
ally if a small quantity of an ^H, salt is present
(BerzeUus). Kane {A. Ch. [2] 72, 283) obtained the
compound 3Cu0.4NH,.6HjO by adding NHjAct
to CuCljAq. Halaguti a. Sargeau {A, Ch. [3] 9,
438) obtained CuO.4NH3.4H2O by treating with
NH, the mother-liquor from the preparation of
Cu-KHj chromate. A solution of CuO in NH,Aq
dissolves cellulose ; the solution is conveniently
prepared either by digesting Cu spirals with
NHjAq in air, or by ppg. CuSOiAq by the calcu-
lated quantity of NaOHAq, washing ihe pp. of
Cu(0H)2 and dissolving it in NH,Aq (Schweizer,
J. pr. 72, 109). Ammoniaoal solutions of CuO
are reduced with ppn. of Cu, by P, Zn.Co, &o. —
4. With a few metallic oxides to toira compounds
of the type 0aO.xMjO, ; e.g. CuCEe^Os, formed
by heating together the two oxides (List, B. 11,
1516), or by the rea,ctiQu of CaO with Ee,ClaAq,
or by ppg. by KOHAq a solution of equivalent
masses of a Cu and a ferric salt. The compound
SCuCMnA is obtained by adding NaOH to an
ammoniacal solution of CuO, and then MnCl^Aq
drop by drop with jonstant stirring (Schneider,
Am. 9, 269). The compound CuO.CrjOj is de-
scribed by Persoz (A. Oh. [3] 25, 283).
Hydbated cupeio oxide or Coppbb hydeoxidh
CuO.H,0 = Cu(OH)j.
, Preparaiioji.— Obtained by adding dilute
NaOHAq or KOHAq in slight excess to
OuSOjAq ; or preferably by adding CuS04Aq
to NaOHAq, keeping the latter in excess
(Oglialoro, J. 1876. 217); washing very many
tipies, and drying at alow temperature: Bottger
(J.pr. 73, 491) recommends to drop NHjAq into
boiling CuSOjAq until the pp., which at first
is greenish, becomes blue, to wash this pp.
thoroughly, and then to addf airly cone. NaOHAq,
keeping the temperature about 20°-40° (1). also
Lowe, D. P. J. 149, 270 ; Peligot, C. B. 63, 209).
Properties. — A blue solid, sometimes crystal-
line, very easily dehydrated. Heated in presence
of water it turns black, the change occurring
more readily if KOH or NaOH is present ; the
black compound is 3CuO.HjO according to Harms
(/. 1857. 246), 6CuO.H,0 according to Eose (P.
84, 480). When heated to 100° it loses water,
but it is not fully dehydrated even at 200°-300°
according to Eose (l.c.; cf. SchafEner, A. 51,
168). The hydrate is soluble in acids, also in
NHjAq, and in solutions of NH4 salts ; also in
Na^S^OaAq (Eield, C. J. [2] 1, 28).
Beactiwns. — 1. With ferrous hydroxide ■^to-
ducesFejOsHa and CujO-sH^O (Levol, A. Ch. 65,
320). — 2. With ferrous sulphate solution pro-
duces CujCieH^O and basic ferric sulphate
(Braun, J. 1867. 301).— 3. Dissolves in acids to
form cupric salts. — 4. Dissolves in 4 to 6 parts
molten potash; on adding water CuO is formed,
but some of the Cu remains in solution, and on
adding a large excess of KOHAq all dissolves.^
5. Dissolves in large excess of potash solution to
a blue liquid ; according to Chodnew («7". pr. 28,
217) this liquid remains blue on boiling or on
adding much water, but on standing in air for a
long time a part of the Cu in solution is ppd. as
CuO.HjO ; addition of HClAq to the blue liquid
until nearly neutral ppts. Cn(0H)2, but a little
Cu remains in solution. Chodnew {l.c.) also
states that addition of a large excess of KOHAq
to CuS04Aq or Cu(N05)2Aq causes some of the
Cu(0H)2 to dissolve ; the solutions must be cold
and dilute ; the whole of the Cu is not ppd. on
boUing. The hydrate dissolves in NaOHAq
(70 p.c), and gives a blue pp. on long standing,
containing CuO and Na,0 according to Low (Fr,
9, 463). ' '
IV. CoppEB PBROXIDB. — The oxide CuO, has
not been obtained, but a hydrate CuOj-H^O ia
known. This hydrate is prepared (1) by digest-
ing finely-divided CuO, or Cu(0H)2, with HjOjAq
for several days at 0° (ThSnard ; Kriiss, B. 17, ,
?593) ; (2) by shaking very dilute CuSOiAq with
excess of Mu02.a;H20 or PbO,, keeping cold
(Schmid, J.pr. 98, 136); (3) by adding HjOjAq
to a solution of CU-NH4 sulphate (Weltzien,
A. 140, 207). CUO2.H2O is very easily decom-
posed with evolution of 0 ; decomposition of the
moist hydrate in presence of water begins at 6°
(Eriiss, 2.C.). When quickly washed with cold
82
260
COFFEE, OXIDBS OF.
water, piessed between paper, and then dried m
vacuo, it is obtained pure. This hydrate forms
an olive-^een powder; it reacts with acids to
give ouprio salts and HjOj; dilute HOlAq is
said to produce a little 0.
Oxides of copper other than C\i,0,
CU2O, CuO, and CuOj. Different chemists have
asserted the existence of oxides of the form
xCxiO.yCnfi intermediate between CuO and
CuOj, obtained either by strongly heating CuO,
or by the action of hypochlorites on cupric salts
in solution {v. Kriiger, P. 62, 445 ; Crum, A. 55,
218; Fremy, A. Ch. [3] 12, 457; Kriiss, B. 17,
2593). But according to Osborne [Am. S. [3]
32, 333) these bodies are all mixtures of GuO
and CU2O ; this result is confirmed by the ex-
periments of Debray and Joannis on the dissocia-
tion of these mixtures (C B. 99, 583), and by
the thermal measurements made by Joannis
(C. B. 100, 999).
Copper, oxybromide of, v. Coppeb, oxthaioid
coMPonNDS of.
Copper, oxychlorides of, v. Coppeb, oxthaiiOiii
OOMPOtJITDB OF.
Copper, oxyfluoride of, v. Coppeb, oxyhalois
COUFOCNDS OF.
Copper, oxyhaloid compounds of. — Several
oxychlorides of the form CuxCl^O^ are known ;
an oxyfluoride CuF2.Cu(OH)2, and an oxyiodide
2CuI2.CuO.4H2O, are also known ; an oxybrom-
ide probably exists, but it has not been isolated.
CoppBB OXYBBOMIDE. — When a little NHjAq
is added to CuBrjAq, a pale-green pp. is obtained,
which becomes grey on heating ; both of these
bodies are oxybromides according to Liiwig (P.
14, 485).
CoppEK OXTCHIOBIDES. — Various compounds
of CuO with CuClj are obtained by digesting
CuClj with Cu(OH)j, also by the incomplete ppn.
of CuClj by alkalis, and also by the action of O
on moist CuClj. The following are the chief
oxychlorides : —
I. CuOl2.2CuO.4H2O ; blue-green pp. by adding
to CuClj enough KOH to decompose a of the
OuClj; ; or by diluting CuCljAq until the liquid is
blue (Gladstone, G. J. 8, 211). This oxychloride
loses 3H2O at 140°, leaving a chocolate-coloured
monohydrate (Kane, A. Ch. 72, 277).
n. 2(CuCl2.3CuO).7H20 ; green pp. by adding
excess of NaC2Hs02Aq to boiling CuCljAq, or by
the action of NaClAq on Cu(C2H302)2 (Cassel-
mann, Fr. 4, 24). Also obtained by adding
NH,Aq, insufficient for complete decomposition,
to a mixture of CuS04Aq with excess of NaCl
(Eeindel, J.pr. 106, 378).
ni. CuOl2.3CuO.4H2O ; occurs native as
Ataca/mite; used in the arts »,a Brunswick green.
Prepared by the action of air on copper plates
covered with HClAq or NHjClAq ; or by digest-
ing in air a mixture of NaCl, Cu turnings, and
CUSO45H2O with enough water to form a thick
magma, or by exposing moist CUjCl, to the air
(Vogel, D. P. J. 136, 238; v. also Field, P. If.
[4] 24, 123 ; Debray, Bl. [2] 7, 104).
Coppeb oxYPLnoBXOE CuP2'Cu(OH)2
[=CuF.OH] (Balbiano, &. 14, 74). A greenish-
white solid obtained by adding to HFAq, CuO or
CuCOj in quantity not sufficient to saturate the
acid ; or by mixing CuSO^Aq and KFAq.
Cop PSB oxYiomcE 2Cul2.Cu0.4H,0 ; prepared
by the action of Ca on BaljAq in presence ol
air (v. supra, Cupbio lonroE).
Copper, oxysnlphides of, a;CuS.^CaO. When
KajSAq is dropped into an ammoniacal solution
of CUSO4 at 70°-80° tin the blue colour dis-
appears, a pp. of SCuS.CuO is formed; at higher
temperatures the pp. contains more CuO, and at
ordmary temperatures CuS is the product (Po-
louze, A. Ch. [3] 17, 393). According to Mau-
menfi (A. Ch. [3] 18, 311) various bxysulphides
are formed during the action of cone. HjSO,
with Cu, but this is negatived by the experiments
of Pickering (0. J. [2] 18, 112).
Copper, phosphides of. — Two phosphides of
copper are known, CujPj and CUjPj; another,
CU2P2, probably exists. The moleciilar weight
of none of these compounds is known with
certainty. Cu and P may be melted together in
all proportions.
I. Tbi-ooppbe phosphibe CujPj. Obtained by
passing PH, over warm CUCI2, or by passing
PH3 into CuSOjAq (H. Eose, P. 14, 188; 24, 328).
According to Bottger (/. 1857. 107) the pp. pro-
duced by boiling P with CuSO^Aq, and washing
with K2Cr20,Aq acidulated with H^SO, (to re-
move basic Cu phosphate), has the composition
CUsPj. Prepared by the reaction of PHj with
CuCl:, the phosphide is a black solid, insol.
HOlAq, and loses half its P when strongly
heated in H. Prepared by passing PH, into
CuSOjAq, the phosphide is sol. HClAq with
evolution of inflammable PH3. Prepared by
Bottger's method the phosphide is an easily
oxidised powder, slowly dissolved by HClAq
with evolution of non-inflammable PE, (v. also
Sidot, O. B. 84, 1454).
II. Hexacoppeb PHOSPHIDE CugPj. Obtained
by leading PH, over heated CU2CI2 or CU2S
(H. Eose, P. 6, 209; 24, 328); by strongly
heating CusP, in H (Eose, l.e.) ; by passing
P vapour over Cu heated to dull redness (Abel,
G. J. [2] 3, 249). Grey-blaok solid, e. sol.
HNOjAq, insol. HClAq.
A Di-ooppEE PHOSPHIDE, CujPj, 13 described
as a grey powder obtained by heating CuHPO,
in a stream of H (H. Eose, P. 14, 188 ; 24, 328).
Also produced by heating P with Cu turnings,
and then carefully heating the product with
amorphous P (Berzelius ; but cf. Abel, 0. J. [2]
3, 249). A phosphide, having the composition '.
CujPj, was obtained by Cross a. Higgins (0. J.
35, 424) by heating CUjCl^Aq with amorphous.P
to 160° for many hours.
Copper, salts of. Compounds obtained by
replacing H of acids by Cu. Copper forms two
classes of salts, the cuprous CujXj [X = 01, Br, I,
SON, ^, &c.], and the ciupric CviX^ [X = CI, NO,,
SO CO
-g-J, -^, &c.]. Few cuprous salts except those
derived from haloid acids are known; a few
double salts of this class have been prepared, e.g.
Cn2S03.(NHj2SO„ and some cupro-cupric salts
are known, e.g. CU2SO3.CuSO3.5H2O. The cuprous
salts are generally insol. water, while the normal
cupric salts as a class dissolve in water. The
cuprous salts are less stable than the cupric;
but cuprous iodide is no much more stable than
cupric iodide, that the latter has not beenisolated,
reactions which might be expected to yield Cul,
COPPER,, SULPHIDES OF.
201
(e.g. KIAq + CuSOjAq) produce Cu^Ij and iodine.
Many basic cupric salts are known. The cuprous
salts are not generally obtained by reacting on
CujO with acids, but by reduction of cupric salts
(v. e.g. CuPKous ohlokide). Cupric salts are
usually obtained by reactions between acids and
CuO or CuCOa. A great many cupric salts have
been prepared (v. Caebonates, Niteates, Sui.-
PHATBS,&o.) ; thefollowingaretheohief salts of this
class : — bromate, carbonates, chlorate (and salts
of other chlorine oxyacids), iodate aai periodate,
molybdates, nitrates a,ni nitrites, phosphate (and
salts of other phosphorus oxyacids), selenates
and sehtdte, silicates, sulphates and sulphites,
tungstates, wranates, vanadates.
Copper, selenides of. I. Cvpnons selenide
CujSe. A steel-grey mass, obtained by heating
Cu turnings with Se. Occurs native as BerzeUa-
nite. II. CupBio seienide OuSe. A greenish-
black soUd, obtained by passing Se vapour over
copper plates (Little, A. 112, 211) ; S.G. 6-66.
Also formed by passing HjSe into a solution of a
cupric salt (Berzelius).
Copper, silicide of. No definite compound
has been isolated. Bodies more or less resembling
alloys, of Cu and Si are obtained by heating
KjSiFs with Na and Cu (v. Deville a. Carbn, C. B.
45, 163; Winkler, J.pr. 91, 193).
Copper, silicofluoride of, CuSlPs.6HjO. Blue
crystals, obtained by dissolving CuOin HjSiFjAq;
deliquescent ; heated to 60° gives CuSiPs.4H20
(Berzelius ; Stolba, J. pr. 102, 7). Decomposed
at 130°-140° giving CuF.OH, SiP,, dnd HP ;
absorbs NH^ giving CuF.OH.2NH3, NH^P, and
SiOj (Balbiano, G. 14, 74).
Copper, sulphides of. Two sulphides of copper
are known, CUjS and CuS. As neither has been
gasified the molecular formulae are not known
with certainty; Pickering (C. J. 39, 401) says
that CuS heated in H at 260° gives Cu^S, and at
c. 650° it yields Cu ; because of this reaction he
thinks that the formula of cupric sulphide ought
to be CU2S2 E^nd not CuS. Cuprous sulphide,
GUjS, is the more stable of the two sulphides ;
both are distinctly basic, forming the basic
radicles of various sulpho-salts ; but CuS also
combines with Ka^S &c., forming compounds in
which CuS acts as the negative radicle {v. Cv-
PBous, and Cupbic, sulphide ; Combinations).
Compounds are also known which probably con-
tain the radicle CuS^ (v. p. 262).
I. CuPEOus SULPHIDE Cu^S. Occurs native
as Copper-glance; S.G. 5-97 (Karsten, S. 65, 820,
394). CrystaUises in' rhombic forms a:b:c
= •582:1: -973; and also in regular octahedra;
isomorphous in both forms with AgjS. Porms
compounds with some less positive sulphides {p.
Combinations).
FormaKon. — 1. By heating a mixture of 4
parts finely divided Cn with 1 ps^rt S (Winkel-
blech, A. 21, 34). Spirals of Cu burnin S vapour
to CUjS. CUjS is also formed by repeatedly and
strongly pressing together a mixture of Cu and
S (Spring, B. 16, 999).— 2. By the action of
NH^SHAq on Cu (Heumann, B. 6, 748).— 3. By
heating CuSO, with carbon.
Preparation.— 1. By heating eleotrolytieally
deposited copper with cone. H2S0, for a short
time at c. 124° (Pickering, C.J. 39,402).— 2. By
heating pure CuS in a stream of H to c. 265° so
long as HjS is evolved (P., Ix.). — 3. By passing
HjS into solution of a Cu salt in presence of
NaHOOjat 200° (de Senarmont, .i. 0/s. [3] 32,
116). — 4. By heating CuSO,, or other Cu salt, in
dry HoS and then in H (Carnot, Bl. [2] 32, 163).
Properties and Reactions. — (S.G. v. supra.)
Greyish-bljie solid, fusible at moderate tempera-
ture.—!; Generally said to be unchanged when
heated in hydrogen,hut according to Pickering it
is reduced to Cu by heating in H stream at 0.
650° (C. J. 39, 404).— 2. Eeducedto Cu by heat-
ing to white heat in water vapour (Eegnault,
A..Ch. 62, 387).— 3. Chlorine slowly acts on hot
CujS. — 4. Heated in air gives CuSO^ and CuO. —
5. Heated with cupric oxide forms SOj and Cu
or Cuj,0.— 6. Heated with Ufharge, SOj, a little
CujO, PbO, and Pb are formed.— 7. Phospho-
retted hydrogen forms Cu phosphide. — 8. AlkaU
carbonate does not react with CUuS when the
two are heated together, but in presence of
carbon.or caustic alkali a part of, the CUjS is
reduced to Cu. — 9. Heated with rdtre, K^SO,
and Cu are formed. — 10. Silver nitrate reacts in
accordance with the equation Cu^S -h 4AgN0, =
2Cu(N03)2 + Ag^S -I- 2Ag (Heumann, B. 6, 751 ; 8,
534 ; Schneider, P. 152, 471 ; 154, 295).— 11.
Boiling cone, hydrochloric acid slowly forms
CujClj, ; cold nitric acid forms CuS and Cu(N0j)2 ;
hot nitric acid forms Cu(N0X and separates g. —
12. Heated in carbon dioxide to about 250°-300°
Cu is formed (Pickering,, O. J. 39,405).
Combinatums. — 1. With non-metallic sul-
phides (i.) Cu^S.PjSj, and 2CU2S.P2S ; produced,
the former by adding PjS to ammoniacal OujCljAq,
the latter by heating the first to redness in a re-'
tort (Berzelius, P. 7, 29). (ii.) 2OU2S.P2S3 ; the
pp. from ammoniacal CujCljAq by alkaline poly-
sulphides is heated with P^S (Berzelius). (iii.)
3CU2S.2AS2S3, occurs native as Binmite;
3OU2S.AS2S5 occurs native as Enargite. (iv.) '
Cu2S.Sb2S3 occurs native as Copper-antimon/y
glance ; 3Cu2S.Sb2S5 is formed by heating
2Cu2S.CuS.Sb2S5 which is produced by pre-
cipitating CuSO^Aq by NajSbSi.- 2. With ms-
talUc sulphides. Cu2S.Pe2S3, 3Cu2S.Pe2S„ and
Cu2S.2PeS.Fe2Ss occur as minerals. — 3. With
non - metalUo and metallic sulphides. (i.)
4:{Ciig^e)S.AaJS3^TermamUte; 3Cu2S.3PeS.As2S5
= Epigenite. (ii.) Cri28.2Ph8.8h283 = Boumonite.
II. CuPEio SULPHIDB CuS (or OU2S2, V. begin-
ning of CoPFEB, sulphides of) occurs native as
CovelUte; S.G. 4-59 to 4-64 (Karsten, 8. 65, 320,
394). A green-black solid ; by compressing
at 6500 atmos. appears as dark-blue metal-like
mass (Spring, B. 16, 1142). ' Acts as a basic sul-
phide, forming compounds with less positive
sulphides; but also forms compounds with NaJS
&o., in which CuS forms the negative part of the
salt.
Colloidal form of CuS (Spring a. De
Boeck, Bl. [2] 48, 165). An aqueous solution of
CuS is obtained by ppg. a Cu salt solution by
HjS, or preferably by NHjHSAq, and* prolonged
washing by deoantation with dilute HjSOjAq,
then dissolving in water and boiling for a few
moments to expel HjS. The aqueous solution
of CuS is dark-coloured, with slight greenish
fluorescence ; the CuS is ppd. by addition of
various salts, e.g. alum, AljSSO,, &c.
Formation. — By adding an alkaline sulphide
to solution of a Cu salt ; Thomsen {B. 11, 2043)
says that the pp. formed by adding Na2SAq to
COtPER. SULPHIDES OF.
CuSO^Aq lias the composition Cu^Sa'. By pass-
ing HjS into solution of a Cu salt.
'Preparation. — 1. CuSOjAq, prepared from
pure electrolytic Cu, is ppd. by H^S, and the
pp. is dried at a low temperature in a current of
HjS. — 2. Pure electrolytic Cu is heated with
cone. H2SO4 to about 180° for some little time,
the residue is washed, and heated for a short
time in a rapid current of H at c. 160° (Picker-
ing, O. 3. 39, 401).— 3. Pure finely-divided Ou^S
is treated with cold cone, nitric acid, the residue
is thoroughly washed. — 4. 2| parts finely di-
vided Cu (ppd. by Zn) are gently heated with
\\ part flowers of S, so thdt the excess of S sub-
limes ; any residual S may be removed by wash-
ing with KOHAq.
Profgerties and BeacUons. — 1. Moist CuS
readily oxidises in oij- to CuSO^. — 2. Heated to
c. 330" for some hours, Cu^S is formed (Picker-
ing, O. J. 39, 406). — 3. Heated in carbon dioxide
to c. 180° CUjS is formed, and at o. 350° Cu is
produced ; heated in hydrogen to o. 200° reduc-
tion begins, and at c. 265° CujS is formed, and
at 0. 620° Cu is produced jPiokering, 0. J. 39,
403). — 4. Dissolved by mtric acid with separa-
tion of S ; hot cone, hydrochloric acid slowly
forms CuuClj. — 5. Dissolved hy potassium cyanide
solution, also by solution of alkali hiccurhonates.
6. Insoluble in alkali sulphides. — 7. Not at-
tacked by H^SOjAq containing | of its volume
of HjSO, (Hofmann, A. 115, 286).
ComHnaticms. — 1. The following compounds
of CuS vrith sulphide of arsenic and antimony
• are described by BerzeUus, obtained by reac-
tions between Cu salts and sulpharsenates and
Bulphantimonates (P. 7, 29) ; 2CuS.As2S5 ;
120uS.ASjS, ; 2CuS.AsjSs ; SCuS.SbjSs.— 2.
Berzelius also describes the compounds with
phosphorus sulphides, CuS.PjS; 2OUS.P2S5. —
3. With sulphides of the alkali metals. Schnei-
der (P. 138, 311) obtained KjS.3CujS.2CuS
( = KjCubS8) by heating together 1 part finely-
divided Cu, 6 parts EjCO,, and 6 parts S ; when
the same proportions of Cu, NajCO,, and S were
used, the compound Ha2S.Cu2S.CuS( = Na2Cu3S3)
was produced. Schneider also describes the
compounds K^FeCugS, and NajFeCu^Sj, obtained
by heating ¥e, S, and E^CO, or NajCO,.
III. CoMPOOTinS OF HTPOIHETlCAIi OOPPBK TBI-
SDLPniDE (CuS,). When CuSOjAq to which
excess of NHjAqhas been added is dropped into
(NH4)2SAq until a pp. forms, the liquid is filtered
and allowed to stand in absence of air, a salt
Cu2(NH,)2S, [? = (NH,)2S.2CuS3] is formed in red
needles. This compound is decomposed on ex-
posure to air, or by addition of warm water. A
corresponding K salt was obtained by Priwoznik
{B. 6, 1291) by the action of alkali polysulphides
on CujO, OuO, or Cu^S. (For more details v.
Priwoznik, l.c. ; Peltzer, A. 128, 184 ; Gescher,
A. 141, 350; 143, 375; Bloiam.C J. [2] 3, 94;
Vphl, J.pr. 102, 32 ; Berzelius, P. 7, ,29).
Copper, telluride of. By boiling a solution
of Cu acetate in presence of ppd. Te, Parkman
{J. 1861. 126) obtained CuaTe, as a black powder.
If the solution is cold and SO, is added, the pp.
isCuTe. M. M.P.M.
COPPEE-AMMONIUM COMPOTTNLS. (Cm-
prammoniwm compounds. Owpra/mines). Many
of the bodies which are formed by the combina-
tion of KHs with the haloid and other com-
pounds of Cu may bo regarded as compounds of
various hypothetical radicles supposed to be de-
rived from NH„ NjHj, NjH,,, Ac, by replacing
Hj by Cuj or du. Thus' the compounds
CUCI2.2NH3 and Cu2CL,.2NH3 may be formulated
as NjH„(Cu)Gl2 and N2Hj(0Uj)0l2 respectively.
From these compounds others may be derived
by assuming that part of the E is substituted by
NH4; thus the compound GuCl^.lNH, may be
formulated as N2H,(NHj)2(Cu)Clj, Compounds
supposed to be derived from the hypothetical
radicle N2He(Cu2) are sometimes called cupro-
ammonium compounds ; examples of these
are ciipro-am/mordum chloride N2H8(Cu2)Cl2,
diammonium - cupro - ammonium iodide
K2H4(NH4)2(Cu2)l2. Compounds supposed to be
derived from the hypothetical radicle N2H,(Cu)
are sometimes called cupri-ammonium com-
pounds ; examples of these are c«pri-amTO(wmin
chloride N2H8(Cu)Cl2, diammamum-cupri-dm-
monium oxide N2H4(NH4)2(0u)0. It is, however,
very doubtful whether anything is gained at pre-
sent by this extremely hypothetical way of for-
mulating the double compounds of NH, and Cu
salts. M. M. P. M.
GOFBINE. A name given by Niemikowicz
{M. 7, 241) to the methylo-hydro'xide of Di-
MBTHYL-AMinO-ACEIONB (?.«.).
COFTIN£. An alkaloid contained, together
with berberine, in Coptis trifolia (Gross, N. Bep.
Pharm. 23, 53 ; Schultz, Ph. [3] 14, 973 ; J. Ph.
14, 273).
COBALIIIT V. Bosouo acis and anhydride of
Tm-oxy-di-phenyl-toltl-cabbinol.
COSIAMYETIN Cs„H3,0,„. [220°]. S. 1-44
at 22°. S. (alcohol) 2 at 22°. [o] = 24-5 at 20°.
The active principle of Coria/ria myrtifoUa, 'a
purgative and poisonous plant growing in South-
ern Europe (Eiban, Bl. 1864, i, 87 ; 1867, i, 79),
formerly used for the production of a black dye.
Prisms (from alcohol). Dextrorotatory HI forma
a black pp. which gives an alcoholic solution,
which is turned crimson by NaOH. Baryta
forms BaC3„H„0,a(?). Br gives C3„H34Br20,„,
which crystallises in needles (from alcohol).
Hexa-acetyl derivative C3gH,iA<!gO,o3aq
[below 100°]. Transparent brittle mass.
C0EIANDEB0ILC,„H,,OH. [a]D= -92-55° at
15°. The volatile oil of Coriander seeds (Tromms-
dorff, Ar. Ph. [2] 2, 114 ; Kawalier, J.pr. 58, 226).
Decomposed by distillation forming C^^fl
(165°-170°). P2O5 forms a terpene C,„H,3. On
treatment with iodine it gives cymene. It forms
a solid sodium derivative C,gH„ONaand various
ethers. On oxidation with neutral KMnO^ it
gives a ketone C,„H,bO (186°), S.G. -897, which
combines with NaHSOj, and is converted by fur-
ther oxidation into COj, acetic acid, and di-
methyl-succinic acid. Alkaline EMnO^ oxidises
it to GO2, acetic, and oxalic acids (Grosser, B.
14, 2485). HCl forms C,„H„C1, S.G. -963, while
HI gives C,„H„I, which explodes below 100°.
COEIDINE C,oHjbN. (211°). S.G. ^ -974.
A base of the pyridine series occurring in coal
tar (Thenius, C. G. 1862, 53) . Turns litmus paper
blue. SI. sol. water, v. sol. other ordinary men-
strua. The hydrochloric acid solution gives a
pp. with HgClj, which melts at 28°, but may be
obtained as white needles. Colours acidified
pine wood yellowish red. — B'2H2PtCl, : orange pp.
CO£K V. CELLULOSE, vol. i. p. 721.
OOTO BARK.
263
COBNEIN' v. PnoTEiDg, Appendiai 0.
CORNICULAKIC ACID OpHijOj or
Ph.0(0O2H):CH.0O.CH2.Ph. [115°]. Longcolour-
less ueedlea or tables. Formed as a by-product
in the reduction of pulvio acid to di-hydro-corni-
cularic acid. This latter acid is also formed by
reduction of cornicularicaoid with zinc-dust and
NaOH (Spiegel, B. 15, 1546; A. 219, 23).
ComicTilar-lactone C^K^fi^ oi
00 0
Ph.d:OH.(J:OH.Ph. |141<»]. Yellow needles.
Insol. in caustic alkalis even on boiling. ,
Di - hydro - cornlcularic acid C^Hi^Og i.e.
(0bH5)j0,H4(OH).0O2H. Di-phen/yl-oxy-angelio
oAd. [134°]. Colourless needles. Sol., alcohol,
ether, benzene, and acetic acid, si. kol. CSj, insol.
ligroin. Prepared by reduction of pulvic acid
with zinc-dust and NHj, COj being evolved. On
further reduction with sodium amalgam it gives
tetra-hydro-corniculario acid. Oh fusion with
KOH it is resolved into phenyl-succinic acid and
toluene. Distillation with quiok-lime gives
C,H5.CH2.0H2.C0.CH,.CbH5. AojO forms a com-
pound C,;H,40jHOAo [99°].
Salts. — A'Ag and A'^Pb: amorphous white
pps.
Methyl ether AfMe: colourless monoolinio
prisms [68°], formed by reduction of pulvio ether
or from silver dihydrooomioularate and EtI.
Lactone C^HijOj. [117°]. Colourless
needles. Sol. ether, benzene, acetic acid, hot
alcohol, and OS2, slightly in ligroin. Prepared
by heating the acid (Spiegel, B. 14, 1690).
Tetra-hydro-cornicularic acid C„H,gO, or
CbH5.CHj.CH(0H).0H2CH(C5HJ.C0,H(?). Di-
•phenyl-oxy-valeria acid. Thick colourless oil.
Formed by reduction of di-hydro-corniculario acid
with sodium amalgam (Spiegel, B. 14, 1692).
Lactone C^HisOj. [71°]. Plat colour-
less needles. Sol. alcohol, ether, and benzene,
si. sol. ligroiin, insol. water. Formed by boiling
the acid with water (Spiegel, B. 14, 1692).
Jso-Si-hydro-cornicular-Iactone C^Hi^O:.
[0. 105°]. Colourless needles. Formed as a by-
product in the reduction of pulvic acid (Spiegel,
B. 15, 1546).
COBITIIT. A crystalline bitter substance
which may be extracted by water from the root
of Oonmsflmda (Geiger, A. 14, 206). Ppd. by
lead subacetate.
COBTICIC ACID CjjHioOs? An amorphous
acid said to exist in cork (Siewert, Z. 1868, 383).
COBYDALINE OisH.jNO,. [130°]. Occurs
in the roots of CorydaUs bulbosa, O.fabacea, and
Aristohchda cava (Wackenroder, Kasfn. Arch.
(1826); Pesohier, Trommsd. N. J. 17, 80;
Winckler, Phcmn. Cenir. 1832, 38 ; A. 87, 225 ;
Euiekholdt; A. 64, 869 ; Miiller, Viertetjahr. pr.
Pharm. 8, 526 ; Wicke, A. 137,274). The alka-
loid is extracted by dilute acid, and may be iso-
lated after ppn. by sodium phosphotungstate.
Short prisms (from strong solutions) or slender
needles (from-dilute solutions) ; insol. water, sol.
ordinary solvents. Tastes bitter. Ppd_. by NaOH
from its solution in aoids, the pp. being sol. ex-
cess, Ppd. by the usual reagents for alkaloids.
— B'HC15aa: tuftsofneedles.—B'jH^PtOl,: yel-
low crystalline pp.— B'HjSOi: needles, si. sol.
water.
Ethylo-iodide BCEitl. Ciystalline, si. sol.
water. Not decomposed by aqueous NaOH, but
converted by moist Ag^O into an alkaline hy-
droxide.— (B'Bt01)2PtOl4 : amorphous pp.
COTABNAMIC ACID v. Nakcotine.
COTAENIC ACID 1;. Nabootinb.
COTAENINE v. Nabcotine.
COTO BAEK. Two kinds of ooto bark are
exported from Bolivia, one from the interior of
the country called oinchona-coto or genuine,
ooto, derived probably from some plant belong-
ing to the Lauraoe£B or Terebinthaoew, rather
than to the BubiaoesB. It is used in cases of
diarrhoea and colic, as also for neuralgia, rheu-
matism and gout. The other kind of coto-
bark or paraooto-bark (Jobst a. Hesse), from the
banks of the river Mapiri, resembles the former
in appearance, though its physiological action is
much weaker. True coto bark contains cotoin
and diootoin ; the other bark contains paracotoin,
hydroootone, and its dibenzoyl derivative, leuco-
tin, and oxyleucotin; piperonylio acid is present
in both (Harz, Ar. Ph. [3] 7, 214 ; Gietl, ibid.
231 ; Wittstein, ibid. 219 ; Burkart, Med. Corres.
Arts. Vere^n Wilrtembwrg, 1876 ; ISalz, Central-
blatt Med. Wiss. 1878 ; Jobst a. Hesse, A. 199,
17). The physiological action of cotoin and
paracotoin has been studied by Albertoni (J. 1883,
1353, 1488).
Cotoin OmHisO,. [130°].
PrvparaUon. — The finely-powdered ooto-bark
is exhausted with ether, the extract evaporated
to one-tenth, and the residue mixed with warm
petroleum; on cooling a black resinous mass
separates, the liquid from which on evaporation
deposits crystals of cotoin. From the resin the
compound is also obtained by boiling with lime,
and the solution acidified with acetic aoid ;
from this liquid cotoin is deposited in leaflets or
pale golden needles. It is finally purified by
charcoal.
Properties. — Prisms or tabular crystals, v.
sol. alcohol, chloroform, and benzene, si. sol.
water and petroleum; sol. alkalis and their
carbonates, but reprecipitated on acidification.
Neutral to litmus. Inactive.
ReactAons. — 1. With rdtric acid it gives a
blood-red colouration. — 2. Rediices gold a;nd silver
salts and Fehling's solution when warmed. —
3. With amimowia and Pb(OAo)j it gives a
yellow flocoulent pp. C22H,2Pb30B. — 4. Heated
with concentrated acids or alkaUs it yields
benzoic acid.
Triaoetyl derivative C^JB^^^kofig. [94°].
Prisms, sol. CHOlj and water.
Xri-bromo-coto'in. [114°]. Yellow prisms,
insol. cold water, decomposed by hot water, sol.
alcohol, chloroform, and ether.
Dicotoiu p^HjiO,,. Anhydride of coto'ini
[74°-77°]. When crude cotoin is treated with
boiling water, crystals of cotoin at first separate,
then leaflets of dicotoin, which are separated
by a sieve. Pale-yellow glistening leaflets, sol.
alcohol, acetone, ether, and alkalis. By potash
it is converted into cotoin ; and by AcjO into
tri-acetyl-cotoin (Jobst a. Hesse, A. 199, 29).
Paracotoin C,„H,20a. [152°].
Preparation. — Finely divided para-ooto bark
is extracted with ether, and from the residue
left on evaporation a crystalline mass of para-
cotoin, oxyleucotin, leucotin, and its di-benzoyi
derivative separates out. This is fractionally
264
GOTO BARK.
erystallised from alcohol, when the paraootoin
separates out first.
ProperUes. — Pale yellow leaflets, sol. ether
and chloroform ; of neutral reaction ; does not
react with Ao^O.
Reactions. — 1. Sol. nitric acid forming a
yellow nitro- product. — 2. Br gives an unstable
bromo- derivative. — 3. On fusion with potash it
yields formic and protocatechuic acids, but
when boiled with a solution of potash paraeu-
marhydrin is formed thus C,bH,20s + 2H2O
= 2CgH803 + CO2 together with paraootoio acid.
Hydrdcotoin CisHnO,. [98°]. Occurs in
para-coto bark. Extracted by dilute soda from
the resinous mass obtained after separation of
the paracotoin, leucotin, and oxyleucotin. Large
pale yellow prisms, sol. hot water and alcohol,
V. sol. chlorofdrm and acetone. With ferric
chloride and sulphuric acid it gives a dark-
brown colouration; with bromine it gives a
bromo- derivative 0,5H,jBr04, crystallising in
monoclinic prisms [147°], sol. ether, chloroform,
and alcohol. Further bromination gives a di-
bromo- derivative, C,5H,2Br204, crystallising in
prisms [95°]. On fusion with potash it yields
hydrocotone and benzoic acid (Jobst a. Hesse, A.
199, 57).
Acetyl derivative CisHiACOAo). [83°].
White prisms. V. sol. hot water. Forma a
bromo- derivative CisHijBrAcOj, [166°], crys-
tallising in white prisms, sol. chloroform and
boiling alcohol.
Hydrocotone CigHjA- [49°]- (243°). V.D.
II'IB. Formed by fusion of leucotin with
potash; white prisms, sol. ether, acetone, and
chloroform. Heated with concentrated nitric
acid it yields di-nitro-cotone 0,gH2i,(N02)205,
which crystallises in brown leaflets of metallic
lustre ; when heated it explodes, emitting violet
vapours.
Di-benzoyl- derivative C^H^^zfig.
[113°]. Occurs in the para-coto bark; white
prisms, sol. alcohol, ether, and acetone, si. sol.
hot water. Concentrated nitric acid forms with
it a bluish-green resin. Sulphuric acid gives a
dark-yellow colouration. On fusion with potash
it yields hydrocotone and benzoic acid. It is
nnaltered by acetic anhydride. With hromvne it
yields a di-bromo- derivative Cj^Hji^BrjOa
[147°], crystallising in white prisms, sol. alcohol
and acetone, as well as a tetra-bromo- deri-
vative OajHajBriOs [84°], orystalUsing in oota-
hedra, sol. alcohol and chloroform.
Paracnmarhydrin 0,^.^0,. [83°]. Formed
by boiling paraootoin with aqueous KOH. La-
minsB; smelling like coumarin; si. sol. oold
water, v. e. sol. alcohol.
Leucotin G^fi^flp [97°]. The chief con-
stituent of theextract of para-coto bark. Separates
from the alcoholic mother-liquor in the prepara-
tion of para-cotom. Small prisms. SI. sol. boiling
water, v. sol. alcohol and ether. Inactive. Not
attacked by AcjO. HNO, gives a bluish-green
resin and solution. Potash-fusion gives benzoic,
formic, and protocatechuic acids, protocatechuic
aldehyde, cotogenin, and hydrocotoin. Br gives
a di-broitio- derivative Cj^HjoBrjOj [187°],
and a tri-bromo- derivative CjjHjgBr^Oj
[157°].
Cotogenin C^HhOs. [210°]. Obtained by
(using leucotin with EOH. May be crystallised
from HOAc. Gives off pyrocateohin when
strongly heated. V. si. sol. cold alcohol and
ether. Dissolves in alkalis, forming solutiolis
which turn brown in the air. Fe^Clj colours its
alcohoho solution green.
Paracotoic acid C„H„0,. [108°]. Formed
by boiUng jiaracotoin with dilute alkalis
C,5H,20j + H20 = C,gHnOj. Yellow amorphous
powder, sol. alcohol and ether, insol. water.
The Ba, Pb, and Ca salts (MA',) are yellow
amorphous pps.
Oxyleucotin CjiHjjO,^. [134°]. Occurs in
paraooto bark. Prisms (from alcohol). V. e.
sol. alcohol and HOAc, m. sol. ether. By heat-
ing with cone. HNO3 it is converted into a
bluish-green resin and a bluish-green solution.
Inactive. It is not coloured by FOjCIb. Gone.
HOI at 140° gives protocatechuic acid. Potash-
fusion gives protocatechuic acid and aldehyde,
benzoic acid, formic acid, and cotogenin. Br
gives a di-bromo- derivative Cs^HjjBrjOu
[192°], and a tetra-bromo- derivative
G^^BJ&r: fin [159°].
Paraooto oil. Prepared from the para-coto
bark by distillation with superheated steam.
Light mobile- liquid. S.G. is -93, a= -2-12;
separated by fractional distillation into (a) and
(;3) paraootene, (a), (0) and (7) paracotole.
(o) Paraootene C.^H,,. V.D. 5-17. (160°).
S.G. i£ -87. [ix]d = + 9-34. Strongly refractive
oU of aromatic odour.
(0) Paraootene C„H,5. (171°). V.D. 4-83.
S.G. iS-88. [a]D = --63. Oil, of faint aromatic
odour.
(a) Paracotole C.^Hj^O. (221°). V.D. 6-17.
S.G. IS -93. [a]D = -11-87, isomeric with the
oil of cubebs, w^oh it resembles in many re-
spects.
(j8) Paracotole C^B.,fi^ (236°). V.D. 12-8.
S.G. 14-95. [a]D = -5-98. Oil of faint aromatia
odour.
(7) Paracotole C^sH^O^. (240"). S.G. «
-97. [o]i, = — -52. Turns yellow on exposure from
absorption of oxygen (Jobst a. Hesse, A. 199, 75).
COTTON V. Cellulose.
COUMALIC ACID Gfifi^ i.e.
0_CH = C(C02H)
I I . Cumalic acid. [207°]
OC-CH=CH
Prepared by heating malic acid with HjSO, or
ZnClj, and precipitating the melt in water ; the
yield is nearly theoretical. The reaction probably
consists in the splitting oS of formic acid with
production of the semi-aldehyde of malonio
acid CHj<^j-jQ^, which then undergoes further
condensation, forming coumalic acid (Pechmann,
B. 17, 936). Sublimable. Small colourless
prisms. V. sol. alcohol and acetic acid, si. sol.
cold, more sol. hot, water. It reduces ammonia-'
cal silver and copper solutions on boiUng. Its
aqueous solution is decomposed on boiling. On
oxidation it gives fnmaric acid. NHj forms, in
the oold, oxy-pyridine earboxylio acid.
Methyl ether A'Me: [74°]; (0. 260°),
long, colourless needles or plates.
Conmal-anilidic acid
C02H.CH:CH.C(C0jH):CH.NHPh. (?)
Mono-methyl ether
COi^.CH:0H.C(C02Me) :CH.NHPh. [140°].
COUMARIO ACrO.
265
Poi'med by the action of aniline on an aleoholio
solution of the methyl-ether of coumalio acid
(Pechmann a. Welsh, B. 17, 2392 ; 0. 7.47, 145).
Yellow needles, v. sol. hot alcohol, chloroform,
and benzene, si. sol. ether, insol. water. By
boiling with aqueous NaOH it is converted into
the phenyl derivative of oxy-niootinio acid —
OjH,N(OPh)COjH[l:2:5].
Bromocoamalic acid v. vol. i. p. 565.
PARACOTTMAEHYDBIN v. OoTO bark.
o-COUMABIG ACID CgHjOj. o-Oxy-citma-
mic acid. o-Oxy-phenyl-acrylic acid, Mol. w.
164. [208°], V.D. 6-6 (calc. 6-66).
Occurrence. — In melilot {Melilotus officinalis)
and in the leaves otAngrcBcumfragrans (Z wenger,
A. Suppl. 8, 30).
Fcmnation. — Fromo-amido-oinnamic acid by
the diazo- reaction (Fischer, B. 14, 479 ; A. 221,
274).
Prepa/raiaAm. — Comnarin (10 g.) is added to a
solution of sodium (3-5 g.) in dry alcohol (65 c.c),
and the mixture heated for 1^ hours. The pro-
duct is diluted and evaporated to a small bulk.
The coumario acid is ppd. by HCl. The pp. is
dissolved in NaljCOjAq, freed from unaltered
coumarin by shaking with ether, the acid is
reppd. by HCl and crystallised from water
(Ebert, A. 226, 347 ; cf. Delalande, A. Oh. [3] 6,
343 ; A. 45, 338 ; Bleibtreu, A. 59, 183).
Properties. — Long needles, v. si. sol. cold
water and ether, v. sol. alcohol, insol. CHCl, and
CS,. Not volatile with steam. Decomposed on
distillation with formation of phenol. Its solu-
tion in alkalis is yellow with green fluorescence.
Gone. HBrAq slowly 'changes it in the cold into
its anhydride, coumarin.
Beactions. — 1. Potash-fusion gives acetic and
o-oxy-benzoio acids. — 2. Sodium cvmalgam gives
o-oxy-phenyl-propionic acid (Tiemann a. Herz-
feld, B. 10, 286).— 3. Bromine (1 mol.) added to
its solution in CSj gives a white crystalline
substance [o. 111°] (? di-bromp-o-oxy-phenyl-
propionic acid), which, when exposed to the air,
' gives off HBr, and yields (j3)-di-bromo-eouaiarin
[177°].
Salts. — BaA'jaq: nodules, v. sol. water. —
PbA'2 : crystalline pp. — ZnA', : needles, si. sol.
cold water. — AgA'.
ConatitutAon. — Like cinnamic, fumaric, and
citraconic acids, coumaric acid is a symmetrical
derivative of ethylene, so that it might be ex-
pected to exist in two modifications. These two
modifications are found in its alkyl derivatives.
The existence of two modifications might also be
accounted for by ascribing to one of them the
/CH:OH
formula OjH.<^ | (Anschutz, A. 239,
\0. 0(0H),
161 ; 240, 133). Except as regards boiling-point,
the physical properties of the (o) -coumario ethers
stand to those of their (/3)-isomerides exactly as
those of citraconic and maleic ethers stand to
those of mesaconic and fumaric ethers respec-
tively (Perkin, O. J. 39, 559).
(a), (or Alio-) Methyl derivative
C„Hj(0Me).CH:CH.C02H. [89°]. Formed by
heating coumarin with KaOH (2 mols.) and Mel
(1 mol.) at 150° (Perkin, 0. J. 39, 409). Mono-
clinic crystals (from OSs). a:6:c= •677:1:1'122 ;
B = 87° 12'. V. e. sol. alcohol, m. sol. ligroin.
Uhauges into the (/3)-iBomeride en boiling, or
even by exposing a concentrated alcoholic solu-
tion to sunlight. Sodium amalgam reduces it,
as well as its (i8)-isomeride, to the methyl deriva-
tive of oxy-phenyl-propionio acid. Br in CSj
gives the methyl ether of (a)-di-bromo-o-oxy-
(3)-phenyl-propionic acid (v. vol. i. p. 603).
Undiluted bromine forms the methyl-ether of
tri-bromo- oxy-phenyl-propionio acid. HNO,
gives the same di-nitro- derivative as with its
(/3)-isomeride. Fuming HI unites in the, cold,
and on adding KajCO, there is formed
CsH,(0Me)CH:0H2. KMnO< oxidises it to [2:1]
0„H,(OMe)COjH. — BaA'j. — Methyl ether
[2:l]C8H4(OMe).OH:CH.COjMe. (276°). S.G. if
1-140 ; |g 1-278. Formed by heating coumarin,
MeOH, and Mel for 3 hours at 100°. Converted
by NHj at 150° into the amide of the (;8)-iso-
meride.
(&)-Methyl derivative
[2:l]OaH,(OMe).CH:CH.0O2H. [183°]. Formed
by heating [2:l]CBH^(0Me).CH0 (2 pts.) with
NaOAc (1 pt.) and AcjO (3 pts.), at 175° (Perkin,
G. J. 31, 414). Formed also by heating its
(a)-isomerid6. Small monoolinic prisms (from
xylene) a:6:c = •441-1: -807; /3 = 64°41'. M. sol.
alcohol. Br in OSj gives the methyl derivative of
(/3)-di-bromo-oxy-phenyl-propionio acid (v. vol. i.
p. 603). Undiluted broriiine forms the methyl
ether of tri-bromo-oxy-phenyl-propionio acid.
KMnO, gives G^Jifi^%).COJEi. (Tiemann a. Will,
B. 15, 2078). Potash-fusion gives salicylic acid.
HNO3 forms a di - nitro - derivative [193°].—
Methyl ether C,H,(0Me).CH:CH.C02Me.
[293°]. S.G. if 1-1486; |2 1-1362. V.D. 6-5
(calc. 6-6). M.M. 2-389. /*„ 1-5905 at 10°. Ob-
tained by means of PCI5 and HOMe. Formed
also by heating its (o)-isomeride. With Br in CSo
it gives C„H<(0M6).CHBrCHBr.C0.,Me [68°] and
an isomeride [125°].
Amide C„Hi(OMe).OH:CH.OONHj. [192°].
Small needles (from alcobol).
(o)- (qx Alio-) Ethyl derivative
[2:l]C„H,{0Et)CH:CH.00.,H. [102°] (P. a. E.) ;
[104°] (P.). From alcohol, sodium (3-2 g.), cou-
marin (10 g.) and EtI (12 g.) (Fittig a. Ebert, A.
216, 142 ; Perkin, O. 3. 39, 412). White plates
(from water), or tables (from dilute alcohol).
V. si. sol. cold water, si. sol. hot water, v. sol,,
alcohol and ether. Sparingly volatile with steam.
Beactions. — 1. On distillation an oil is got,
whence NajCO, extracts the (;8)-isomeride ; the
yield is 30 p.c. — 2. KMnO, gives ethyl-salicylic
aldehyde and acid. — 3. Sodium amalgam forms
the ethyl derivative of oxy-phenyl-propionio
acid.— 4. Br forms adibromide [155°]. Salts. —
(0„H„03),Ba 2aq.— CaA'j, 2aq. S. 2-11 at 21°.
Ethyl ether CsH,(OBt).CH:CH.COjEt.
(291°). S.G, « 1-084 ;fg 1-074, /*d = 1:558. From
coumarin (I45 g.), NaOH (8 g.) and water, by eva-
porating to a small bulk and heating the residue
with alcohol and EtI (32 g.) at 100°.
(fi)-Ethyl derivative
C,H,(0Bt)0H:CH.COjH. [133°] (E.a.F.); [135°]
(P.). Formed, together with the (a) -isomeride,
by treating o-coumarTc acid with NaOEt and EtI.
Formed also from the (o).isomeride by distilla-
tion, or by long heating to a high tetaperature
(Fittig a, Ebert, A. 216, 144). Obtained by heat-
ing C„H4(0Et)CH0 with NaOAo and acetic an-
hydride at 160° (Perkin, 0. J. 39, 413). Needles
(from water), or prisms (from alcohol). V. bL
268
OOUMARIO ACID.
sol. cold water, si. sol. hot water. V. e. sol.
alcohol or ether. The Na salt is oxidised by
KMnOj to ethyl -salicylic aldehyde and ethyl-
salicylic acid. Sodium amalgam forms the ethyl
derivative of oxy-phenyl propionic acid. Br forms
a dibromide [155°]. S alt s.— (C„H„Oj)jOa 2aq.
S. -43 at 21=.— BaA'j 4aq. Ethyl ether
CsH4(0Et).GH:CH.C0iEt. (303°). S.G.^1-09.
Formed by treating the preceding mth PCI5, fol-
lowed by alcohol. Formed also by boiling the
(a)-isomeride for some time.
Acetyl derivative
C„H,(OAo).CH:CH.COjH. [146°]. Formed by
gently heating salicylic aldehyde (3 pts.) with
KaOAc (4 pts.) and AcjO (5 pts.) (Tiemann a.
Herzfeld, B. 10, 284). Needles (from water).
V. sol. hot water, alcohol, and ether. Converted
by dilute KOHAq into coumaric acid ; and by
heating above 150° into HOAc and coumarin.
C arboxy-methyl derivative
C02H.CHj.0.08H,.CH:CH.C02H. o-Oourmr-oxy-
acetic acid. [190°]. Formed by heating o-alde-
hydo-phenozy-acetic acid (1 pt.) with acetic an-
liydride (5 pts.) and sodium acetate (3 pts.) to
boilingJoir 1 or 2 hours (Bossing, B. 17, 2997).
Yellow needles. V. sol.^ alcohol, ether, and
hot water, si. sol. benzene, chloroform, and cold
water. Sublimable.
•n; i,v„r„5^<. p Ti /CHBr.CHBr.OOjH
Di-bromide C,H,<q ^^^ ^,^^2 ^.
[220°]. White needles ; si. sol. benzene, chloro-
form, and water, v. sol. alcohol and ether.
Anhydride C,H,<g5^^c^0>0. [176°].
Crystalline soM. Y. sol. alcohol and ether,
b1. sol. water. Formed by heating the acid with
phosphoric acid.
^CHBr.CHBr.CO
Di-bromide CsSt< \ ' . [o.213°].
\O.CHj.CO -O
Orange-yellow needles ; v; sol. alcohol and ether,
(il. sol. water and benzene (Bossing, B. 17, 3001).
Bromo-coumaric acid v. vol. i. p. 564.
m-Conmaric acid
[3:1]C5H4(0H).CH:CH.C02H. [191°]. Formed
by heating ra-oxy-benzaldehyde with acetic an-
hydride and sodimn acetate ; or by boiling di-
azocinnamic acid with water (Tiemann a. Ludwig,
B. 15, 2048). White prisms. Sol. alcohol, ether,
benzene, and hot water.
Acetyl derivative
CsH4(0Ac).CH:CH.C0jH. [151°]. White needles,
eol. alcohol, ether, and hot water.
Met^hyl derivative
C,Hi(OMe).CH:CH.COJE. [115°]. Long white
needles, sol. alcohol, ether, and benzeiie, si. sol.
hot water (Tiemann a. Ludwig, B. 15, 2048).
Garboxy -methyl derivativeO,y'H.jfi^i.e.
C„H4(O.CH2.CO^).CH:CH.COjH [1:3]. m-Phen-
oxy-acetic-acryUc acid. m-Omna/r(xey-a,cetic acid.
Phev/yl-gVycollic-m-acryUc acid. [219°]. Pre-
pared by heating TO-aldehydo-phenoxy-acetic
acid with sodium acetate and acetic anhydride.
White needles (from hot water). V.sol. alcohol,
ether, and acetic acid, si. Sol. cold water. The
Ag, Pb, Cu, and Fe salts are sparingly soluble pps.
(Elkan, B. 19, 3047).
^-Coumaric acid CjH4(0H).CH:CH.C02H.
p-Oxy-cinncundc add. p-Oxy-phenyl-acryUc
acid. Naringenic acid. [206°].
Preparation. — 1. 2^ kilos, of ^loes aie boiled
for two hours with 5 litres of water and 400 g.
cone. HjSO,; after cooling the liquor is decanted
and the residue again boiled with 2 litres of
water, the combined extracts are evaporated to
^, and when cold extracted with ether. The c^ude
^-coumaric acid (yield : 1-5 to I'S p.c.) left on
evaporating the ether is purified by conversion
into the barium salt (Hlasiwetz, A. 136, 31 ;
Eigel, B. 20, 2527).— 2. ^-Oxy-benzaldehyde
(5 pts.) is heated at 175° with dehydrated sodium
acetate (8 pts.) and acetio anhydride (10 pts.) ;
the yield is 70 p.c. of the oxy-benzaldehyde
(Tiemann a. Herzfeld, B. 10, 63, 283 ; Eigel).
3. By heating p-diazo-cinnamic acid with water ;
small yield (Gabriel, 5. 15, 2301).— 4. Together
with phloroglucin by boiling naringenin with
cone, aqueous NaOH (Will, B. 20, 299).
Pr(^erties. — Thick warts (anhy.) or long
needles (with aiaq). Y. si. sol. cold water, v. sol.
hot water, v. e. sol. alcohol and ether, si. sol.
benzene, insol. ligroin. Fe^Cl, colours the alco-
holic solution brown. Sodium-amalgam gives
p - oxy - phenyl - propionic acid. Potash -fusion
forms ^-Oxy-benzoic acid (Barth, B. 12, 1259).
Salts. — NHjA'aq: monoclinic tables. —
CdA'jSaq.— CuA'j 6aq.— AgA'.
Methyl derivative
CsHi(OMe).OH:CH.COjH. [169°] (E.); [171°]
(P.). Formed by heating anisic aldehyde with
acetic anhydride and sodium acetate at 180°
(yield : 70 p.c. of the anisic aldehyde), or by
saponification with KOH of the di-methyl-ether
CeH4(OMe).CH:CH.C02Me formed by heatingthe
acid with methyl iodide and KOH. Occurs
among the products of the action of KOH and
Mel upon tyrosine (Komer a. Menozzi, G. 11,
549). Formed also by oxidising the methyl de-
rivative of methyl oxy-styryl ketone with NaOCl
(Einhorn a. Grabfield, A. 243, 363). Yellow
needles, m. sol. alcohol, hot water, and HOAc;
si. sol. cold water and chloroform (Perkin).
Gives when heated the methyl derivative of
vinyl-phenol CH^rCH.CjHiOMe. This body is
also formed by successive treatment with HI
and NajCOj (Perkin, C. J. 33, 214).— A'Na.—
AgA' (Eigel, B. 20, 2527).
Methyl ether C,H,(OMe).CH:CH.OOs,Me:i
[89°]. (308°). Lamina. In chloroform solu-.
tion it takes up bromine, with production of
CeH4(0Me)CHBr.CHBr.C02Me [118°] (Yalentini,
Gf, 16, 424; Perkin, C. J. 39, 439).
Chloride C5H,(0Me).CH:CH.C0Cl. [50°].
Amide C,H,(OMe),CH:CH.CONHj. [186°].
Acetyl derivative
CeH4(0Ac).CH:CH.00jH. [0. 195°]." Formed
by heating sodium ^-oxy-benzoio aldehyde
C„H,(0Na).CH0 with NaOAo and Ac^O (Tie-
mann a. Herzfeld, B. 10, 65). Pelted groups of
slender nfiedles (from hot water). Sublimes
readily. Sol. boiling water, alcohol, ether, and
HOAc, V. si. sol. cold water, benzene, and CHCl,.
Garboxy -methyl derivative C„H,gO(
i.e. 0jH,(0.CHj.00»H).CH:CH.C02H [1:4]. jp-C«-
maroxy-acetie acid. Phenyl-glycolUc-p-acryUc
acid. [225°]. Prepared by boiling a mixtureof
^-aldehydo-phenoxy-aoetic acid (1 pt.), sodium
acetate (1 pt.), and acetic anhydride (3 pts.) for
5 hours. Warty crystals. Sol. benzene and
benzoline, v. sol. alcohol, ether, and acetic acid,
si. sol. cold water. The Ag, Pb, Cu, and Fe salts
are sparingly soluble pps. (Elkan, B. 19, 3046).
OOTJMARm.
267
9i-1)romide of oonmarlc acid v. Di-beomo-oxt-
rHENTIi-PEOPIONlO AOID.
Hydro-coumario acid v. Oxt-phenyl-peo-
FIONIO ACID.
other derlTatlTes are described as Nitko-
ooTJUAiiia ACID, Ci-oxY-cdKAMia AOID, and OxT-
AMIDO-OIKKAMIO AOID.
0-COTJMABIC ALDEHYDE
CjH,(OH).CH:0H.0OH. Oxy-cimnamic aldehyde.
[133°]. Long slender needles. Y. sol. alcohol
and ether, si. sol. water. PejClj gives a red pp.
Formed by the decomposition of its gluooside
under the influence of emulsin (Tiemann a. Kees,
B. 18, 1962).
aiueoside [2:l]0,H4(OC8H„O5).C2Hj,COH.
Olueo-coumaric aldehyde. [199°]. Formed by
adding a few drops of dilute NaOH to a mixture
of helicin [2:l]OsH4(OC5H„05).COH and acetic
aldehyde. This condensation even takes place
in dilute aqueous solution and at a low tempera-
ture (Tiemann a. Kees, B. 18, 1958). Fine white
needles (containing aq). V. sol. hot water and
alcohol, insol. ether and chloroform. Leevorota-
tory. By emulsin it is split up into coumario
aldehyde and glucose. So^um amalgam reduces
it to glnco-coumaryl alcohol
CeH,(OCeH„0.).CA.CH,(OH).
Phenyl hydrazide of the glucoside
C5H4(OCeH„05).C2H2.CH:NjHPh: [132°]; sol.
alcohol and hot water, nearly insol. cold water.
Oxim of the gVucoside
C^4(OCsH„05).Ojft.CH:NOH : [230°]; long
white needles (containing 2aq) ; v. sol. hot water,
less sol. alcohbl, insol. ether.
TO-Coumaric aldehyde
[3:1] CsH4(0H)CH:CH.CH0. [100°]. From m-
aldehydo-phenoxy-'"">tio acid, aldehyde, and
dilute NaOHAq (Elkan, .S. 19, 3048).
p-Coumaric aldehyde
[4:1] C^i(OH)CH:CH.CHO. [182°]. Fromp-
aldehydo-phenoxy-acetic acid in the same way.
COUMAEILIC ACID CgHeOa i.e.
C,H,(0H).C:0.C02H or C„H^<'^^^C.CO,H.
o-Oxy-phenyl-propioUe acid. [191°] {¥.);
[193°] (P.). (c. 312°). Formed by treating (o).
bromo-ooumarin with hot alcoholic KOH (Per-
kin, C. J. 24, 45 ; Fittig, A. 216, 162). Long
needles (from water) ; v. e. sol. alcohol, m. sol.
water, si. sol. chloroform and CS,. Kot at-
tacked by Br or cone. HBr. Potash-fusion gives
salicylic and acetic acids. KMnOj forms only
CO^. Sodium amalgam reduces it to hydrocou-
marilic acid CgEgOg.
S alt s. — AgA'. — CaA'j 3aq. — BaA'j 4aq.
Ethyl ether BtA': [27°]; (274° at 720mm.)
(Hantzsoh, B. 19, 2401).
Methyl derivative C,H4(OMe).C:C.C02H.
[126°]. From the methyl -derivative of exo-
bromo-conmaric acid and dilute KOH (Perkin,
C. J. 39, 423). Needles (from CS^).
Dromo-conmarHic acid
C,PaBr<;°^O.COjH. [250°]. From (o)-di-
bromo-coumarin and alcoholic KOH (Perkin,
C. J. 24, 45). Needles, si. sol. water, v. sol.
^cohol.
Methyl derivative
0sHaBr(OMe).C!C.CO2P, [168°]. Prepared from
C«H3Br(0Me).C2H;fBrj.C02H and aqueous KOH
(Perkin, C. J. 39, 419). Small needles (from
benzene). ,
p-Oxy-eumarilio acid Methyl derivative
C5H,(0Me)<:^*^^C.0O2H[4:2.1]. [196°]. Formed
by boiling bromo-umbelliferon-methyl ether
CH:CBr
CaHJOMeX' / with cone, alcoholic KOH.
0.00
Long white needles. V. sol. alcohol and ether,
scarcely sol. cold water, more readily in hot.
Slightly volatile with steam. — BaA'2 4aq : white
crystalline solid (Will a. Beok, B. 19, 1783).
Ethyl derivative C„H,|,04 i.e.
C,H3(0BtX^^C.C0,H [4:2:1]. [163°],
Formed by boiling bromo-umbelliferon-ethyl
CH:CBr
ether CeH3(0Et)<f I with cone, alcoholic
^ o.co
KOH. Long felted needles (Will a. Beok, B. 19,
1785).
Hydro-coumarilic acid CgHgO, i.e.
C,H,<^^2>CH.C02H. [117°]. (299°).,
Formed by treating coumarilio acid with sodium
amalgam, and extracted by ether from the acidi-
fied product (Fittig, A. 216, 166). Pearly plates
(from water) ; very ^volatile with steam. V. sol.
alcohol and ether, m. sol. water. Partially de-
bomposed on distillation, yielding a phenol.
Gives phenol on distillation with lime.
Salt s. — AgA'. — CaA'2 2aq. — BaA'^ 2aq.
Ethyl ether EtA'. [23°]. (273°).
^-Oxy-hydrocoumarilic acHMethyl deriva-
tive C,„H,„04 i.e. C,S^(OMe)<;^Q^yCS.CO;H.
[4:2:1]. [114°]. Formed by reduction of the
methyl derivative of oxy-coumariHo acid
OeH3(OMe)<^^^C.G02H with sodium-amal-
gam. Hard prisms. V. sol. ordinary solvents.
Volatile with steam (Will a. Beck, B. 19, 1783).
Ethyl derivative C,,H,204 i.e,
C„H3(0Et)<;^^''>CH.C02H [4:2:1]. ' [119°].
Formed by reduction of ethoxy-coumarilic acid
C5H3(OEt)<;*^^C.C02H with sodium amal-
gam. Hard white needles (Will a. Beck^ B. 19,
1785).
Di-oxy-coumarilic acid Di-ei/ij/Meriva-
«we C„H2(0Et)j<°2.>C.C0^. [195°]. From
bromo-sesouletic ether C„H2(0Et)2<^Q WBv^^^
and alcohoUc KOH (Will, B. 16, 2119)! Slender
needles. '
V. also Mbthtii-ooumabilio acid. ■ '
.CH:OH
COUMABm CjHjOj i.e. CeH^i
/^
Mol.
'\o , CO
w. 146. [67°]. (290°).
Occvrrence. — In Tonka heans, the fruit of
Coumaruma odorata, or Dvpteryx odorata, as
small white crystals between the seed coating
and the kerilel; found in woodruff (Asperula
odorata), in MeUlotus officinalis (as melilotate
CjjHijOj [128°]), in the flowers of sweet-scented '
vernal grass {Anthoxanthum odoratvm), in the
leaves of F^ham (Angrcecum fragrans), of an-
208
COTTMARIN.
other orchid, Orchis fusca, and of Lidtris odo-
ratissvma (Guibonrt, Histoire des Drogues Sim-
ples ; BouUaJr a. Boutron-Chaillard, X Ph. 9,
480 ; Delalande, A. Gh. [3] 6, 343 ; Bleibtreu,
A. 59, 177 ; Procter, Bip. chim. App. 1861, 143 ;
Fontana, B. J. 14, 311 ; Guillemette, A. 14, 328 ;
Kossmann, A. 52, 387 ; Gobley, A. 76, 354).
FormaUon. — 1. By boiling Balioylio aldehyde
with AcjO and NaOAo (Perkin, C. J. 21, 53, 181 ;
cf. vol. i. p. 158).— 2. Together with HOAo by
heating acet^^l-coumaiic acid (Tiemann a. Herz-
feld, B. 10, 287).— 3. By the action of Br at
170° on the anhydride of o-oxy-phenyl-propionio
aoid (Hochstetter, A. 226, 360).— 4. By heating
phenol with malic acid and E^SO, or ZnOlj.
The reaction probably takes place in the follow-
ing stages : (1) By splitting oS formic acid the
semi-aldehyde of malonic apid is formed.
CH(0H).C02H CHO
I = I +H,dO,
CHj.COjH CH,.COjH
' (2) By condensation of this aldehyde with
the phenol an oxy-phenyl-laciio acid is pro-
duced—
CHO
CeH..OH + I .
CH2.CO2H
= C„H<g^{OH).CH,CO,H
(3) By splitting two mols. of water from this
body a cumarin is formed :
Qjg. ^CH(OH).CH2.C02H
CH:CH
= C,H,< I + 2H,0
0-CO
(Peohmann, B. 17, 929).
Properties. — Triclinio crystals, ia:h:c
= -8833:1: -3696 (Seacohi, G. 14, 568). Peculiar
odour. M. sol. hot water, v. e. sol. alcohol, insol.
cold aqueous baryta, but dissolves on boiling.
Ether will not extract it from the solution, but
acids, even CO,, re-ppt. it. It appears, however,
to have formed the barium salt of an oz^- acid,
which is not o-coumario acid, unless the boiling is
prolonged after the coumarin is dissolved (Ebert,
^.216, 139). Coumarin dissolves in boiling aque-
ous E^COg without evolution of COj, apparently
fornling a compound with it. BaCO, has no
action on coumarin.
Beactions. — 1. Boiling cone, aqueous KOH
gives o-coumaric acid. — 2. Potash^fusion forms
acetic and salicylic acids.— 3. Gaseous HBr
passed into its solution forms large transparent
crystals [c. 45°] of what is probably an addition-
product. Exposed to th^ air, these crystals
quickly lose SDBr, leaving pure coumarin (Ebert,
A. 226, 347). — 4. Sodium amalgam reduces it tO/
oxy-phenyl-propionic acid. In alcoholic solu-
tion sodium amalgam forms di-hydro-di-couma-
ric acid OjsHisOj, which is si. sol. cold water,
forms the salts NajA"10aq, CaA" 2aq, PbA",
CuA"2aq, and AgjA", and an anhydride
CjjHisOs [222°] (Zwenger, A. Svppl. 8, 32).
Conibmations with bases. — Cj,H,022KOH. —
CsHsOjSNaOH. Obtained by boiling coumarin
(1 mol.) with aqueous NaOH (2 mols.) for a few
minutes. Deliquescent; at 160° it becomes
C,HANa,0.— C,H.02Ba(0H)j.— CsHAaPbO.-
CsHjOjAgjO: yellow t>p. Formed by adding
AgNO, to the yellow solution of coumarin in
aqueous KOH (Perlun, C. J. 22, 192 ; William-
son, C. J. 28, 850).
Oxim C„H^<°=^=>C(NOH) : [ISl"].
Formed by the action of hydroxylamine upon
thiocoumarin in alcoholic solution. Long white
needles. Y. sol. alcohol, ether, and benzene ; sol.
hot water, nearly insol. cold. It is very stable
to alkalis and acids, but by long heating with
HCl it is split up into coumarin and H^NOH.
Ethyl-oximO,B.t'<Cp^»yC{1^0M) : [50°].
Formed by ethylation of the oxim. Colourless
plates. Y. sol. alcohol, ether, and benzene, in-
sol. water.
Phenyl-hydrazide
CsH,<;^»^>C(NjHPh) : [144°]. Formed by
heating thiocoumarin with phenyl-hydrazine in
alcoholic solution. Long yellow needles. Y. sol.
benzene and ether, sol. hot alcohol, si. sol. cold
alcohol, insol. water. Dissolves in H^SO, with a
green colour (Tiemann.JS. 19, 1662).
Coumarin bromide G^fi.fii^. [105°]. From
coumarin (7 pts.) and Br (8 pts.) in CSj (Perkin,
C. J. 17, 368; 9, 37). Oblique prisms (from
alcohol) ; v. sol. alcohol, but decomposed by
boiling therewith. Gives oft Br a little above
its melting-point. Alcoholic KOH converts it
into (a)-bromo-coumarin {v. vol. i. p. 564).
Chloro-conmarin v. p. 57.
Di-coumarin C,gH,g04 i.e.
°«H*<S^o>°-°<co.o>^«H' ? t"''""'
330°]. From salicylic aldehyde, sodium succinate,
and ACjO at 100° (Dyson, G. J. 51, 62). Insol.
ether, alcohol, and benzene, si. sol. chloroform,
and HOAc. Slowly dissol vpp -n boiling NaOHAq,
but is reppd. unchangeil oy acids. Beduced in
alkaline solution by sodium amalgam to hydro-
di-coumaric acid C,sH,,05, which is insol. water,
sol. CHCI3 and benzene. It forms the salts
BaA'^daq and AgA'. At 133° hydrodicoumario
acid splits up into water and its anhydride
hydrodicoumarin CjjHi^O, [256°]. It is recon-
verted into the acid by long heating with cone.
NaOHAq or with HOAc. Bromine acting on
hydrodicoumarin in CHCl, forms C,8H,,BrOj.
Hydro-dicoumaric acid is perhaps
Beduced in aqueous alkaline solution by sodium
amalgam it gives the diuydro-dicoumario acid
C„H,Aor
™-""YoS>^H.CH<«W,OH
not identical with Zwenger's acid. Its salts are
CaA'jBaq. — AgjA". It forms an anhydride
0,gH„0, [224°].
Homologues of coumarin. Obtained by the
action of fatty anhydrides upon sodium o-oxy-
benzoic aldehyde (Perkin, 0. J. 28, 10). They
are described as anhydrides of the correspond-
ing oxyr acids.
Ozy-coumarins. Described as anhydrides of
Dl-oxY-ciNNAMio ACID, &c. The di-oxy-benzenes
and their homologues may be converted by treat-
ment with maUc aoid and H2SO4 into oxy-
coumarins, and by aceto-acetic ether and a de-
hydrating agent into oxy-methyl-ooumarins.
When excess of aceto-acetio ether is used, small
CREATINE.
269
quantities of polyooumarins are also formed
(Peohmann, B. 17, 929, 2191 ; 20, 1328).
Thus from resoroin may be prepared umbelli-
feron [4 U C.H3(0H)< | [224°],
^ \0 . CO
(/3)-metliyl-umbelliferon
/CMe:OH
U I] C.H,(OH)< I [248°],
^ -' ^O . CO
and di-methyl-di-ooumarin
OH:CMev ,CMe:CH
CO . C^ NO .
Orcin gives rise to
>CH:CH
00
C,H,Me(OH)
/^
I [248°] and
\o. CO
XMe:Cq;
C,HjMe(OH)< I >[250°].
\o . CO
Pyrogallol forms daphnetin
CH'CH
f 4:3:1] CjH2(0H)/ '| [255°], and
*- -■ N) . CO
(^)-methyl-daphnetin
.CMe:CH
[ 4:3:1] CA(OH),<;^
Fhloroglucin gives
CO
,/
.CMe:CH
C^j(OH),< I [284°], and
\o . CO
:).
* tri-methyl-tri-coumarin '
kCMe:CH
^ 0 . CO
NH
A
.CH.CH
Imido-dihydro-conmarin C^H,^ I
\0 .CO
NBz
A
/CH.CH
Benzoyl derivativeCM,( I [171°].
\0 .CO
Fine white needles ; sol. warm ether, alcohol,
benzene and acetic acid; insol. water. Formed by
boiling an acetic acid solution of the benzoyl de-
rivative of o-oxy-phenyl-o/3-imido-propionic an-
hydride |0sHj(0H).0jHj(NBz).C0l 0. By
treatment with concentrated aqueous NaOH it
is converted into o-oxy-phenyl-glycidio acid
O
C8H<(0H).CH.CH.C0jH
(PlooM a. Wolfrum, B. 18, 1184 ; cf. Eebuflat, G.
15, 527).
O
.CH.O&
Camarin ozide C.HX I
N) .CO
Inner cmh/ydride of o-oxy-phenyl-glycidio acid.
[153°]. Long needles or prisms. V. sol. ether
and warm alcohol. Formed by boUiug o-oxy-
phenyl-glycidio acid with dilute HjSO,,. By
boiling with water it is partly converted back
again into piy-phenyl-glycidio acid (PlSohl a.
Wolfrum, B. 18, 1187).
COtrilABIIir ■ OABBOXYLIC ACID
OjH,.
/'
O-CO
[187°].
\CH:C.COOH
Formed by heating salicylic aldehyde, malonio
acid, and glacial HOAc at ,100° (Stuart, 0. /.
49, 366). White needles (from water). It is
not decomposed by boiling with water or on
melting, but on heating above 190° it evolves
CO2, leaving coumarin.
Salts. — BaA'2 and AgA' are white pps.
COTTHABIN DIHYDSIBE v. Anhydride of
OXY-PHENYL-PEOPIONIC ACID.
COUMARONE C»H,0 i.e.
C,H,^gH^CH.
(169°). Formed by heating coumarilic acid
with lime, CO, being split off (Fittig a. Ebert, A.
216, 168 ; 226, 347). Formed also by boiling
o-aldehydo-phenoxy-acetio acid with AojO and
NaOAc (Enssing, B. 17, 3000). Heavy oil ;
volatile with steam. Not attacked by sodium
amalgam. Converted by a drop of H^SO, into a
reddish-white amorphous mass.
Dibromide CgHjOBry [86°]. Prisms (from
CS2). Converted by boiling with water into
coumarone and other products.
Bromo-coumarone CgH^BrO. [36°]r From
coumarone dibromide^ and alcoholic KOH.
Needles (from dilute alcohol). V. e. sol. alcohol
and ether, insol. water and alkalis.
jp-Methoxy-coomaroue CgHgO, i.c.
C5H3(OMe) <*^^CH [4:2:1]. (179°). Formed
by dry-distillation of the silver salt of methoxy-
ooumarilic acid CjHs(OMe)<^^^^C.COjH in a
stream of CO,. Colourless oil, having a strong
odour of flowers. Somewhat heavier than water.
Very volatile with steam (WiU a. Beck, B. 19,
1784).
Ozy-methyl-conmarone CgHgO, i.e.
[4 1]C,K,(0H)<'^^^>CH. [97°]. Formed, by
loss of CO,, by distiUatiou of oxy-methyl-cou-
marilicaoid C5Hs(0HX*^q^0.C0,H. White
needles. Sol. benzene and hot water, v. e. sol.
alcohol and ether. Dissolves in alkalis without
alteration. Sparingly volatile with steam.
Sublimes slowly at the ordinary temperature.
Gives a violet colouration on warming with
cone. HjSOj (Hantzsch, B. 19, 2929).
Gonmarone-a-carbozylic acids are identical
with CociTABiLia acids (j. v.).
o-COUMABYL-ALGOHOL. Glucoside.
CeB.f{OG^B.^fis).Oja.2.CKjOS. Gltiao-coumcwyl
alcohol. [116°]. Fine white needles (containing
aq). v. sol. alcohol, insol. ether. Formed by
reduction of glaco-o-ooumario aldehyde with
sodium amalgam. By emulsin it is split up
into coumaryl alcohol (which is an oil) and
glucose (Tiemann a. Eees, B. 18, 1962).
CKEATINE C^HgNjO, i.e.
NH,.C(NH).NMe.CH,.CO,H. Mol. w.131. Kethyl
guanido-aeetic acid. S.G. 1-35. S. 1-3 at 18°.
S. (alcohol) -016.
Occii/rrence. — In the muscular flesh of mam-
malia, birds, ampbibi^,^ a,nd, fis.h«s (Chevreul,
S70
CREATINE.
/. Pfe. 21, 234 ; Pettenkofer, A. 52, 97 ; Liebig,
A. 62, 282; 108, 354; Heiutz, P. 62, 602; 70,
460; 73,596; 74,125; O.iJ. 24, 500; Gregory,
C. J. 1, 25 ; Dessaignes, C. B. 38, 889 ; 41,
1258 ; J. Ph. [3] 32, 41 ; A. 97, 389 ; Schloss-
berger, A. 49, 344 ; 66, 80 ; Price, G. J. 3, 229 ;
Stadeler, J. pr. 72, 256). Occurs also in urine,
blood, and brains (Verdeil a. Mareet, J. Ph. [3]
20, 89; Miiller,4. 103, 142; Voit, J. 1867, 791).
In some cases where creatine has been found it
may have been formed from pre-existent crea-
tinin by the proceB8| pf extraction. Oreatinin
does not, however, appear to exist in flesh
(Neubauer, Fr. 2, 22 ; Nawrboki, Pr. 4, 330).
Synthesis. — By the direct union of cyan-
amide with methyl-amido-acetic acid (saroosine)
in aqueous or alcoholic solution (Volhard, Z.
[2] 5, 819; Strecker, J. 1868, 686). ■
PreparaUm. — Finely-chopped meat (250 g.)
is heated with water (250 o.c.) at 60° for 10
minutes, the liquid is squeezed out and heated
till the albumen is coagulated. The filtrate is
treated with lead sub-acetate as long- as ppn.
occurs, is filtered, and freed from excess of lead
by IljS. The filtrate from PbS is evaporated
to a syrup, from which creatine slowly separates ;
a further quantity may be ppd. by adding alco-
hol (2 or 3 vols.) (Neubauer, Fr. 2, 22 ; Mulder
a. Monthaan, Z. [2] 5, 341).
Properties!. — Monoclinio prisms (containing
nq). SI. sol. water, v. si. sol. alcohol, insol. ether.
The aqueous solution is neutral to litmus. Con-
verted into its anhydride creatinin by heating
with aqueous HOI, with ZnClj, with H^SOj, Or
even (although slowly) with water at 100°.
Gaseous HCl passed over creatine at 100° also
forms creatinin hydrochloride. If 5 or 6 drops
of a ^0 p.c. solution of AgNO, are added to 2 o.c.
of a cold saturated solution of creatine, and a
solution of EOH is added so as just to redissolve
the white pp. which is first formed, the liquid
presently solidifies to a transparent jelly ; re-
duction of silver takes place on heating (Bngel,
C. B. 78, 1707).
BeacHons. — 1. Boiling baryta-water splits it
up into urea (or COj and NHj) and methyl-
amido-acetic acid. Methyl-hydantoin is also
formed.— 2. Nitroiis acid decomposes it, giving
ofl half its nitrogen in the free state. — 3. Alka-
line NaOBr gives off two-thirds of the nitrogen
as such (Httfner, J. pr. [2] 1, 7). — 4. Boiling
with water and HgO gives methyl-gnanidine
and oxalic aoid.^^5. When heated with soda-
lime it gives off methylamine.
Salts.— -B'jHjSOj : slender prisms.— B'HCl.
' — B'HNOj: short thick prisms. — B'CdCl2 2aq:
large crystals.— B'ZnClj: small crystals, resolved
bylhot water into creatine and ZnCl^ (Neubauer,
A. 137, 298).— HgOjHjNsO^iaq: white pp. from
creatine, HgCl^, and KOH (Engel, C. B. 80, 885 ;
B. 8, 546).
Ampbicreatine CgH,gN,Oj. A base occurring
In muscular tissue (Gautier, Bl. [2] 48, 19).
Yellow crystals ; not ppd. by Cu(0Ae)2 or HgClj
but ppd. by sodium phosphomolybdate. Its
hydrochloride is crystalline but not deli-
quescent. Itsplatinochloride forms soluble
tables.
Isomeride of creatine v. Alacbeaiine, vol. i.
p. 93.
C2EATININE C,H,N,0 i.«.
.NMe.CH.
HN:C< I .
\nh . CO
Mol. w. 113. S. 9 at 16«.
S. (alcohol) 1 at 16° (Liebig) ; -3 at 16° (Johnson).
Occurrence. — In human urine to the extent
of -5 p.c. (Pettenkofer, A. 52, 97 ; Heintz, P. 62,
602 ; 73, 595; 74, 125 ; Liebig, A. 62, 298, 324;
Neubauer, A. 119, 39). Occurs also in urine of
horses, calves, and dogs (Heintz ; Voit, C: C. 1867,
504; Socoloff, A. 78, 243; 80, 114; Maly, A.
159, 279) and in the flesh of some fish (Kruken-
berg, J. Th. 1881, 344).
Formation. — From creatine by the action of
mineral acids or of dehydrating agents.
Preparation.-^l. Fresh human urine is neu-
tralised with milk of lime ; chloride of calcium
added as long ais a pp. of phosphate of calcium
continues to form ; the filtrate evaporated till
the salts crystaUise out ; 32 pts. of the mother-
liquor mixed with 1 pt. of chloride of zinc dis-
solved in the smallest possible quantity of water ;
the mixture set aside for four days ; and the zinc-
compound, which separates in nodules, washed
with cold water. The zinc-compound is then
decomposed by boiling with Pb(0H)2, the filtrate
is evaporated, and the mixture of creatine and
creatinine digested ;with cold absolute alcohol,
which dissolves the creatinine only (Liebig ;
Dessaignes, J. Ph. [3] 32, 42 ; Heintz ; Loebe, -
/. pr. 82, 170 ; B6p. chim. pwre, 1861, 25 ;
Neubauer, A. 119, 27; Socoloff, A. 78, 243;
Grocco, C. C. 1887, 17).^2. From urine, after
adding ^ vol. saturated aqueous NaOAc, by
fractional ppn. with HgCl^. A spherical salt
(0jH5HgN3OHCl)^8HgCl2 2aq is obtained, which
is suspended in water and decomposed by HjS.
The filtrate on evaporation deposits creatinine
hydrochloride, whence Pb(OH)j hberates crea-
tinine (Johnson, Pr. 42,, 365 ; 43, 493).
Pr(^erties. — Monoclinio prisms (anhydrous)
or efflorescent prisms (containing 2 aq). Neutral
to litmus (SaJkowski, n. 12, 211). V. sol. hot
water, m. sol. hot alcohol. According to John-
son (Pr. 43, 493) there are two varieties of crea-
tinine, differing in reducing power, solubihty, and
character of their gold salts. Each exists in
efflorescent and in tabular form. 1 part of
tabular creatinine from urine dissolves in 10'78
pts. water at 17°, and in 362 pts. alcohol at 17°,
and its Pt salt dissolves in 14'1 pts. water at 15° ;
on the other hand, 1 pt. of tabular creatinine
froipi creatine dissolves in 10'68 pts. water at
16-5°, and in 324 pts. alcohol at 18-5°, while its
Pt salt requires 24-4 pts. water at 15°. According
to Liebig, 1 pt. creatinine dissolves in 11-5 pts.
water at 16°, and in 102 pts. alcohol at 16°.
Beactions. — 1. In alkaline solutions it is
slowly converted by taking up water into crea-
tine (Dessaignes, J. Ph. [3] 32, 41).— 2. Boiling
with water and HgO gives methyl-guanidine. —
3. Baryta-water at 100° gives NH3 and methyl-
hydantoiin (Neubauer, A. 137, 289).— 4. KMnO,
gives oxalic acid and methyl-guanidine.
DetecUan. — 1. A small quantity of Fehling'a
solution at 60° gives a white flocculent pp., con-
sisting of a compound of creatinine with cuprous
oxide. 1 mol. creatinine can reduce about | mol,
OuO (Worm-Miiller, J. Th. 1881, 76 ; Maschke,
Fr. 17, 134). According to Johnson {Pr. 42,
365 ; 43, 493) the creatinine obtained from crea-
CREOSOTE.
271
tine has not the ^ame reducing power as that
from .urine, the reducing effect of 2 mols. glucose
being equal to that of 5 mols. of the former, but
oalj 4 mols. of the latter. — 2. If a dilute solution
of sodium nitroprnsside is added to a solution of
creatinine and dilute NaOH slowly dropped in, a
ruby-red colouratibn is produced. By this test
the presence of creatinine in urine can be demon-
strated. With creatine no colour is produced,
unless it is previously converted into creatinine
by boiling with a dilute acid ; in this way the
presence of creatine in milk can be proved (Weyl,
B. 11, 2175). On acidifying and warming Prus-
sian blue is formed (Salkowski, S. i, 133 ; Co-
lasanti, O. 17, 129). According to Guareschi
(C. C. 1887, 580) this reaction is given also by
thio-hydantoin, methyl-hydantom, and other
compounds containing the group N.CHj.GO.N.
Salts. — B'HCl : prisms (from alcohol) or
laminae (from water). — ^B'HA.uCl,. According to
Johnson this salt when prepared from creatinine
derived from creatine is decomposed by ether,
but when prepared from urinary creatinine it is
not affected by ether. — B'jHjPtOlj 2aq : orange
prisms. Solubility: v. supra. — ^B'HI: large
crystals (from water). — ^B'jHjSO,: dimetric tables
(from dilute alcohol). — ^B'^ZnCl,: monoolinic
prisma (Schmidt, A. 6l, 332). Insol. absolute
alcohol. S. 1-86 at 15° ; 3-65 at 100°. S. (98 p.o.
alcohol) -0108 at o. 18°; S. (87 p.o. alcohol) -0174
(Neubauer). — B'jHjZnCli : large crystals, v. sol.
water and alcohol (Dessaignes, J. Ph. [3] 32, 43).
NaOAc added to its solution pps. B'jZnClj (Neu-
bauer, A. 120, 267).— B'jCdClj : more soluble in
water than B'^ZnCl^.— B'2Hg(N03)2HgO : crys-
talline pp. formed by adding aqueous-mercuric
nitrate to a cone, solution of creatinine. —
(B'AgN03)2AgjO : delicate white needles (from
wa|er).
(a)-Witroso-creatinine (?) C^HgNiOj. [210°].
Formed, together with its isomeride, by passing
nitrous acid gas into a cone, solution of creati-
nine. It is much less soluble in water than its
(;3) -isomeride (Dessaignes, C. B. 41, 1258 ; A.
97, 339; Marcker, A. 133, 305). CrystaUme
powder, si. sol. cold water, v. si. sol. alcohol.
HCl at 100° converts it into methyl-parabanio
acid, NHj, and oxalic acid (Streoker, A. 118, 151).
Br forms OiHjBrNjOj (?), a neutral crystalling
substance, v. sol. water. EtI at 160° followed by
AgjO gives extremely soluble needles of OjHaNO^
• [152°]. Salts. — B'HClaq. — B'jjHjPtOla. —
B'HNO,. >,
(/3)-B'itroso-creatinine OiHsNjOj. [195°].
Formed as above. Nodules, v. sol. water.
Salts.— B'HOl: laminae, v. e. sol. cold water. —
B'^^PtCl,.
Etbyl-creatinine CjHjEtNjO. From creatm-
ine and EtI at 100°f the resulting hydroiodide
being decomposed by moist AgjO (Neubauer, A.
119, 50 ; 120, 257). Needles (containing |aq).
v. e. sol. alcohol, insol. ether. — ^BCHCl : needles,
V. e. sol. alcohol and water, insol. ether. —
B'jHjPtCl,.— B'm : needles.
Zantho-creatinine CeH„N,0. _
Occwrrence. — In muscular tissue (Gautier,
Bl. [2] 48, 18) and in human urine, ■ especially
during fatigue (Monari, 0. 16, 588).
Properfes.— Sulphur-coloured crystals, hav-
ing a slightly bitter taste. On warming it smells
like acetamide. It has a double action on litmus,
turning blue litmus red, and sensibly blueing red
litmus.
BeacUmis. — ZnGl2givesa similar pp. to crea-
tine, B'jZnClj. AgNO,, a flocculent pp., sol. hot
water, crystallising in needles. Ppd. after some
time by sodium phosphomolybdate. Itshydro-
chloride forms feathery crystals ;itsplatino-
chloride crystallises in long soluble bundles.
Chrnsocreatinine v. p. 171.
CEENIC ACID (xpiiyr,). . Said by Berzelius (P.
13, 84 ; 29, 3, 238) to occur in vegetable mould
and in the oohreous deposits of ferruginous
waters. The deposit is boiled with potash, and '
the filtrate treated vnth EOAc and cuprio acetate
as long as a dark-brown pp. continues to form.
This pp. contains apoorenioacid. The filtrate
is neutralised with ammonium Carbonate, more
cuprio acetate is added, and the liquid heated to
80° ; oupric crenate is then ppd. Crenic acid is
pale yellow and uncrystallisable ; apocrenic acid
is brown and si. sol. water. According to Mulder
{A. 36, 243) crenio acid is Ci^Hj^O,, while apo-
crenic acid is C^fHi^O,,. Orenic acid dissolves
ferrous carbonate (Boutigny, G. E. 58, 247).
CREOSOL 0,H,„Oj i.e. C,H,Me(OMe)(OH)
[1:3:4]. Mol. w. 138. (220°). S.G. ^ 1;0894.
Occurs among the products of the distillation of
beech wood and of gum guaiacum (Hlasiwetz, A.
106, 339). Formed also by distilling homova-
nilhc acid C,H,(0Me)(0H).CHj.C02H with lime
(liemanu a. Nagai, B. 10, 206). Aromatic hquid,
b1. sol. water, miscible with alcohol, ether, and
benzene. FcjCl, gives a green colour. HI or
potash-fusion convert it into C5H3Me(OH)j (Tie-
mann a. Koppe, B. 14, 2025). PCI5 gives
C,H3Me(0Me)Cl (?) (185°) S.G. 1-028 which gives
a green colour with FejOlj and a pp. of AgCl
with AgNOs (Bieohele, A. 151, 115).
Salts.— K0,H90j2aq: needles, v. sol. water
and alcohol. — KEfA'jaq: thin prisms; decom-
posed by water into KA' and creosol. — BaA'^ 3aq :
SI]Q.3ill SCSil63
Methyl ether C^TcL,Me{OMe)^. (218°). Oc-
curs in beech wood creosote (Tiemann a. Men-
delsohn, B. 8, 1137). Formed by fusing papa-
verine with KOH (Goldschmiedt, M. 4, 705). Also
from creosol, KOH, and Mel. Gives no colour
with FejCl,.
Ethyl ether CjH,Me(OMe)(OEt). Oil. 1
Acetyl derivativeCeB.sM.e(OM.6){OA,o).
(247°). Oil (Tiemann, B. 9, 418 ; 10, 58). '
CBEOSOL SUIFHONIO ACID
0^2Me(0Me)(0H)(SO,H). From creosol and
cone. HjSO, at 60° (Bieohele, A. 151, 109 ; Tie-
mann a. Koppe, B. 14, 2026). Hygroscopic
syrup. — KA' : needles ; its aqueous solution is
coloured blue by Fe^Cls.- BaA^- PbA'j.
CBEOSOL CABBOXYLIC ACID v. Methyl de-
rivatme of Di-oxx-ioiinio acid.
CBEOBOTE {Kpeas (rd^etv). — A mixture of sub-
stances of a phenolic character, which, may be
extracted by alkalis from the tar obtained by the
dry distillation of wood. Ehenish beech tar
creosote contains phenol, cresols, guaiacol,
phlorol, and creosol (Beichenbach, Schw. J. 66,
801, 345 ; 67, 1, 67 ; 68, 352^ Ettling, A. 6, 20.9 ;
Laurent, C.B. 11, 124 ; 19, 574 ; Deville, A. Oh.
[3] 12, 228; Gorup-Besanez, A. 78, 231; 86,
223 ; 143, 129 ; Z. [2] 4, 3S3 ; Voelckel, A. 86,
93; -87, 306; Hlasiwetz, 4. 106, 389 ; Shnon.P.
32, 129 ; Hubschmann, A^ 11, 40 ; Eone, A. 16,
sr?
OREOSOTR.
63 ; FJiokiger, Ph. [3] 2, 1008 ; Euot, SI. [2] 8,
875 ; H. Miiller, Z. 1864, 40 ; Marasse, B. 1, 99 ;
2, 11;, Z. [2] 4, 502; 5, 348; Friseh, J.pr. 100,
223; J. Williams, C. G. 1878, 167; Hofmann,
B. 8, 66 ; Tiemaun a. Mendelsohn, B. 8, 1136 ;
Clark, Ph. [3] 3, 1057 ; Watzel, Ar. Ph. [8] 10,
130).
CBESA1TBIN v. Anhydride of tbi-oxy-tei-
lOIiTIi-CABBINOL.
CEESOLS C,H,0 i.e. CsH,Me(OH). Mol. w.
108. Oxy-tohienes. Methyl pJienols. — The three
cresols occur in the tar obtained by the destruc-
tive distillation of coal, beech wood, and pine
wood (Schotten a. Tiemann, £. 11,783; Schulze,
B. 20, 410; DucloB, A. 109, 136; Marasse, A.
162, 64). They are best obtained in a state of
purity from the corresponding toluidines by the
diazo- reaction, or from the toluene snlphonic
acids by potash-fusion. A cresol is formed by
oxidising toluene in presence of Alfil^ (Friedel
a. Crafts, C. B. 86, 884). Acid sulphates of the
three cresols occur in horse's urine, and cresols
are converted into such acids when given to
animals in their food (Banmann a. Herter, B. 9,
1389) . The three cresols, by heating with ammo-
niacal ZnBr, and NH^Br, or with ammoniacal
ZnClj and NH^Cl, are converted into the corre-
sponding toluidines and di-tolyl-amines in vari-
able proportion (Merz a. Miiller, JB. 20, 544). _.
Aeo- compounds of the three cresols. — ^-Cresol
combines with diazo- compounds as easily as
phenols not substituted in the ^-position, the
diazo- residue entering the o-position to the OH.
Disazo- compounds of ^-cresol cannot be ob-
tained. In the azo- compounds of o- and
m-cresol the diazo- residue takes the p- position
to the OH. Both readily yield disazo- compounds,
in which the two azo- residues stand in the j)- and
0- position to the hydroxyl, and hence are meta to
each other, o- and m-Cresol readily give nitroso-
derivatives, but ^-cresol does not (Nolting a.
Kohn, B 17, 351). .
o-Cresol 0,H4Me(OH)[2:l]. [30°]. (190-8°).
S.G. 5516 1-0053; g 1-0578. C.B. (0°-10°) -00072
(Pinette, A. 248, 37). H. F. 50,992 (liquid) ;
-3250 (solid) (Stohmann, J.pr. [2] 34, 311).
Formation. — 1. By fusing toluene o-sulphonic
acid with EOH (Engelhardt a. Latschinoff, Z.
1869, 620).— 2. Prom o-toluidine.— 3. By distil-
ling (1, 2, a!)-oxy-tolnio acids with lime. — 4. By
heating carvacrol with PjOj, and fusing the re-
sulting o-tolyl phosphate with KOH (EekulS, B.
7, 1006). — 5. By treating camphor with ZnCl,
(Eeuter, B. 16, 624).
Properties. — Crystalline. Convertedby potash-
fusion into salicylic acid. EClO, and HCl give
di- and tri- chlorotoluquinone (Southworth, A.
168, 278). Br gives C5HjBrjMe(0H) [S7°] (Wer-
ner, Bl. [2] 46, 278). Excess of Br gives
C.H^r3(0Br).
Salt. — (C,H,MeO)jAl. From o-cresoI, Al, and
a little iodine (Gladstone a. Tribe, O. J. 49, 26).
Black, vitreous mass, forming a dark-green solu-
tion in benzene, decomposed by water and by
alcohol. On distillation it yields di-o-tolyl oxide
(b,^fili.a)fi (o. 275°), o-oresol, and a compound
biB^lnO, crystallising in colourless plates.
Benzoyl derivative C,H,OBz. Oil.
Methyl ether 08HiMe(0Me). (171-3°).
S.G. % -9967. S.V. 1461. C.E. (0°-10°) -00084
(Pinette, A. 243. 37 } cf. Korner, Z. [2] 4, 327).
E thy t ether C;B.^Ue(OEi)i (184-^°). S.G. §
•9679. S.V. 170-9. C.E. (0°-10°) -0009 (Pinetto,
A. 243, 38). From alcohol, EtBr and potassium
cresol by boiling (Staedel, A. 217, 41). The yield
is 67 p.c. Also from diazo-toluene sulphate and
absolute alcohol (Bemsen a. OrndorS, Am. 9,
394). HNOs converts it into G,Hj(NOj)jMe(OEt)
[51°] and a little C^n^{T^0,)^6(aB) [82°].
Ethylene ether (0,^,0)^^^ [79°].
White plates, si. sol. cold alcohol.
Propyl e«fc«rCAMe(OPr). (204-1°). S.G.
a -9517. S.V. 195. C.E. (0='-10°) -00087 (Pinette).
Butyl ether 0,HjMe(0C4H,). (223°).
S.G. 2 -9437. S.V. 218-4. C.E. (0°-10°) -00092.
Beptyl ether C,H4Me(OC,H,5). (277-5°).
S.G. % -9243. S.V. 292-95. C.B. (0°-10°) -00083.
Octyl ether 0,H4Me(0C»H„). (292-9°).
S.G. -9281. S.V. 317-9. C.E. (0°-10°) -00084.
Bensyl ether v. vol. i. p. 490.
m-CresoI C„H,Me(OH). [4°]. (202-8°). S.G.
2 1-0498. S.V. 128-2. C.E. (0°-10°) -00078
(Pinette, A. 248, 40). Ma 1-5816 at 25°- H.P.
53,044 (Stohmann, J. pr. [2] 84, 311). Occurs ,
in coal-tar cresol, together with its m- and p-
isomerides (Schulze, B. 20, 409 ; cf. Ihle, J. pr.
[2] 14, 442). From thymol (100 g.) and PA
(40 g.) ; propylene being given off ; the resulting
m-tolyl-phosphorio acid being fused with KOH.
The yield is 51 p.c. (Staedel, A. 217, 46; cf.
Engelhardt a. Latsohinoff, Z. 1869, 621 ; South-
worth, A. 168, 268; Tiemanu a. Schotten, B.ll,
769). Formed also bydistillingm-oxy-uvitic acid
with lime (Oppenheim a. Pfaff, B. 8, 886), and
by distilling aluminium thymol (Gladstone a.
Tribe, G. J. 41, 12). Formed also by the action
of dry oxygen upon toluene in presence of -
AljCl, (Friedel a. Crafts, A. Oh. [6] 14, 436).
Properties. — ^Liquid. Can be solidified by
throwing a crystal of phenol into the liquid
cooled in a freezing-mixture (Staedel, B. 18,
3448). Its aqueous solution is coloured bluish-
violet by Fe20l5. Fusion with KOH gives m-oxy-
benzoio acid. HCl and KCIO, from di-chloro-
toluquinone Br (8 mols.) gives CjHBrjMe(OH)
[82°]; excess of Br forms C„HBr3M6(0Br)
which liberates iodine from KI (Werner, Bl. [2]
46, 276).
Benzoyl derivative C,H,OBz. [38°].
(o. 293°).
Methyl ether CsH,Me.(OMe). (177-2°)
S.G. § -9891. S.V. 147-45. C.E. (0-10°) -00092
(Pinette, A. 248, 40). H.F.p. 39,748 (0,08= 94;
112,0 = 69) (Stohmann, J.pr. [2] 35, 24).
Ethyl etJierC^t^e{0^t). (192°). S.G.
g-965. S.V. 172. C.E. (0°-10°) -0009 (Pinette,
A. 243, 41). From m-diazo-toluene sulphate and
alcohol (Bemsen a. OmdorfC, Am. 9, 894).
Propyl ether CsB.tUe{OPi). (210-6°). S.G.
g -9484. S.V. 196-2. C.E. (0°-10°) -0009.
Butyl eiherG^,Me{OCtn,). (229-2°). S.G.
g -9407. S.V. 220-45. C.E. (0°-10°) -00092.
Heptyl ether C„H4Me(OC,H,5). (283-2°).
S.G. g -9202. S.V. 296-7. C.E. (0°-10°) -00084.
Octyl ether C,H4Me(OC8H„). (298-9°).
S.G. S -9194. S.V. 321-95. C.E. (0°-10°) -00086
(Pinette, A. 243, 43).
Benzyl ether v. vol. i. p. 490.
m-Gresyl ether «. Di-to-tolyl oxron.
i)-Cresol 0„H,Me(OH). [36°]. (201-8°). S.G.
•5:5 -9962 s g 1-0522. S.V. 123-45. C.E. (0°-10^)
cresoi^-phthaleIn.
273
•00086 (Pinette, A. 243, 43). H.F, 51,100 (soUa) ;
-2459 (liquid) (Stohmann, J.pr. [2] 34,'311).
Occurrence. — In coal-tar (H. Buff, B. 4, 378).
As p-tolyl Bnlphuiio acid in urine of horses, of
cows, and sometimes qf men (Brieger, H. 4,
204).
Formation. — 1. By fusing its sulphonate with
KOH (Vurtz, A. 144, 121; 156, 258). If the
mixture of sulphonio acids of crude cresol is
treated with excess of baryta, basic barium p-
oresol-sulphonate is ppd. (Armstrong a. Field,
C. N. 29, 282 ; Banmann, B. 6, 185).— 2. From
j)-t61uidine. — 3. Got by putrefaction of ox-brain
at 40° (F. StacHy, J.pr. [2] 24, 17). Found also
among the products of putrefaction of horses'
liver, tyrosine, ^-oxy-phenyl-acetio acid, and^-
oxy-phenyl-propionic acid (Banmann a. Brieger,
B. 3, 149; 4, 304; Weyl, E. 3, 812).— 4. To-
gether with carpene' by the dry distillation of
podocarpio acid or its Ca salt (Oudemans, A. 170,
259). — 5. By heating j)-oxy-phenyl-acetio acid
with CaO (Salkowski, B. 12, 1440).
FreparaUon. — From ^-toluidine by diazoti-
satibn in presence of excess of H^SO^.
Prqperiies.-^Prisms. Its aquebus solution is
coloured blue by FejOlj. Potash-fusion converts
it into p-oxy-benzoic acid. HCl and KClOj give
no chlorinated toluquinone (Sonthworth, A. 168,
271). Br (2mols.) gives a pp. of C„H2BrjMe(0H)
[49°], but a larger quantity of Br (3 mols.) gives
0,HjBr2Me(0Br), while a large excess forms
C,]^r,(OH) (Werner, Bi. [2] 46, 278). Chloral
forms OiHjOCjHCljO [52°-56°] (Mazzara, G. 13,
272).
Salt.— (CaH,MeO)3Al. On distillation it
gives a small quantity of dx-p-toljX oxide and a
ketone C.^HnO [168°] (307°). S. (alcohol) -4 at
20° ; 2-5 at 78°. S. (benzene) 3-3 at 21°. V.D.
209-1 (Gladstone, C. J. 41, 8).
Acetyl derivative C;H,OAo. (o. 210°).
OU (Fuchs, B. 2, 626).
Benzoyl derivative 0,H,OBz. [70-6°].
H.F. 69,010 (Stohmann, J. pr. [2] 36, 8 ; cf.
Guareschi, A. 171, 142).
Lauryl derivative G^'B-fi-C^^i^O. [28°].
(220°) at 15 mm. (Kraft a. Burger, 3. 17, 1378).
Myristyl derivative C,H,0.0,4Hj,0.
[39°]. (240°) at 15 mm. (K. a. B.).
Palmityl derivative 0,H,0.0,jH3iO.
[47°]. (258°) at 15 mm.
Stearyl derivative 0,H,0.C,sHs50. [54°].
(276°) at 15 mm. (K. a. B.).
Methyl ether CeH,Me(OMe). (175°). S.G.
g-9868. S.V. 147-7. O.E. (0-l0°) -00084 (Pinette,
A. 243, 44 ; Earner, Bull. Acad. Belg. [2] 24,
154).
Ethyl ether 0,H,Me(OEt). (189-9°).
S.G. g -9662. S.V. 172-1. C.B. (0°-10°) -00086
(Pinette, A. 243, 44). H.P.p. 46,880 (Stohmann,
J.pr. [2] 35, 24). Formed (llj p.c), together
with aldehyde and toluene (18 p.c), by decom-
posing ^-diazo-toluene sulphate with alcohol
(Eemsen a. Orndorff, Am. 9, 394). HNO3 (S.G.
1-5) converts it into di-nitro-j)-oresol [84°] and
its ether [75°] (Staedel, B. 14, 898). KjCrjO,
and HOAc form [4:1] C8H^(0Et)C0jH.
Ethylene ether (C^M^O)j:i^i. [135°].
(297°) (Fuehs, B. 2, 624).
Fropyl ether C5H,Me(0Pr). (210-4°).
S.G. 2 -9497. S.V. 196. C.B. (0°-10°) -00089
(Pinette, A. 243, 45).
Vol. II.
Butyl ether C,H^Me(00,H,). (229-5°).
S.G. ° -9419. S.V. 220-8. O.E. (0'-10°) -00092.
Heptyl ether C„H^Me(0C,H,5). (283-3°).
S.G. g -9228. S.V. 297,-7. O.E. (0°-10°) -0009.
Octyl ether C^n^Ue(OC;B.^X (298°).
S.G. 2 -9199. S.V. 322-4. C.E. (0°-10°) -00088.
Benzyl ether v. vol. i. p. 490.
Nitro-hemyl ether v. jj-Tolyl niibo-
BENZYL OXIDE.
p-Gresyl ether v. "Di-p-roviTi ozins.
Serivatives of cresols v. Auido-obesol,
Bbomo-cbesol, Ghlobo-cbesoIi, Iodo-cbesol, Ni-
IBO-OBESOIi.
CKESOL SICABBOXYLIC AOISS v. OxY-
nviTio, OxY-METHYii-iso-piiTHALio, and 0X7-
METHYl-TEBEPHTHALIO ACIDS.
0-CKESOL-PHTHALElN G^^fii »•«•
(0„H,MeOH)2C<^^^>CO. [214°].
Preparation. — By heating o-cresol (2 pts.),
phthalic anhydride (3 pts.), and stannic chloride
(2 pts.) at 120°-125°. From the fused mass thus
obtained the undecomposed cresol is separated
by steam-distillation ; and the phthalein is
purified by reorystallisation from alcohol (Baeyer
a. Fraude, A. 202, 153).
Properties. — Flesh-red crystals, v. sol. alcohol
and ether, m. sol. hot water ; sol. caustic alkalis
with violet colouration, showing a broad absorp-
tion band in the red.
Ecactions. — 1. With bromine it forms a di-
bromo-derivative together with a bromo-oxy-to-
luyl-benzoio acid CO2H.0,H4.CO.C„HjMeBr(OH) *
[228°]. — 2. With rdfyic add it gives a di-nitro-
derivative. — 3. Zinc-dust forms the correspond-
ing phthalin. — 4. Phtlmlic anhydride and. cone.
sulphtiria acid give oxy-methyl-anthraqninone.
Di-acetyl derivative C^ie^iOf. [75°]:
white amorphous mass.
Di-bemoyl derivative CjjHuBzjO,.
[196°].
Di-bromo-derivative02^,^ViO,.\255°].
Crystalline. Sol. alkalis with blue, and in cone,
sulphuric acid with rose-red, colouration. Con-
verted by phthalic anhydride and sulphuric acid
to bromo-oxy-methyl-anthraquinone.
Di-nitro- derivative Ci^^^{^O^fi^
[248°]: yellow crystals. Sol. Na,COjAq with
red-brown colouration.
o-Cresol-phthalin CjjHjoOi i.e.
(C„HaMe.0H).,CH.C„H,.C02H. [218°]. Prepared
by reduction of o-cresol phthalein with zinc-dust
and KOH (Fraude, A. 202, 168 ; B. 12, 243).
Small concentrically grouped needles ; sol. water
and alcohol, slowly oxidised to o-cresol-phthalein
by exposure to air. By the action of H^SO^ it
gives o-cresol phthalidin.
Di-acetyl derivativeG2^^t^cfi^. [139°].
Crystalline powder. Sol. acetone. Converted
by cone. HjSOj into the phthalidin.
Di - 6 rojra 0 - d er I'D OS <i«e CjjHisBrjO,. [236°].
^-Cresol-phthaleiu anhydride G^^fi^ i.e.
0<c£m:>K%''*>CO- t246°]. From
^-cresol, phthalic anhydride and HjSO, at 160°.
Excess of p-oxeso\ is removed by steam, and the
residue washed with boiling dilute KHO (Drew-
sen, A. 212, 340). Plates or prisms (from alco-
hol). Sol. alcohol, ether, and benzene ; v. sol.
CHOI, ; insol. ligroin, KHO and weak acids.
Conc.H^SOjgives a green fluorescence. Sublimeg
T
27^
ORESOL-PHTHALEIN.
unohangfed. Eeduoed by zino-dngt and AoOH
to the phthalin anhydride. , Fused with KHO it
yields di-oxy-di-methyl benzophenone. [105°].
Heating withoono. H2SO4 yields methyl-er^i/tro-
oxy-anthraquinone. ,
5)-CreBol phthalin anhydride C^^B.,fis i.e.
0<Q=2^^3>CH.0.H,.C0,H. [210°]. From
the preceding by reduction with zino-dust and
AcOH ; crystallises from CHCI3. V. sol. alcohol,
benzene, ether, and acetic a9id. Sol. cone.
HjSO, forming a brown solution (Drewsen, A.
212, 340).
' o-CEESOL STILPHOHIC ACID C,HbS04 i.e.
CsH3Me(OH)(S03H) [1:2:4]. From o-toluidine
sulphonio acid by displacing NH^ by OH through
the diazo- reaction (Hayduck, A. 172, 204 ; 174,
345). Formed also in small quantity by sul-
phonating o-cresol in the cold. At high tem-
peratures it is the only product of this sulpho-
nation (Engelhardt a. Latschinofi, Z. 1869,
621 ; Hantke, B. 20, 3209). Does not crystallise.
Potash-fusion converts it into salicylic acid, to-
gethfer with small quantities of (l,2,4)-di-oiy-
benzoic acid.
Salts. — BaA'jlJaq: extremely soluble ag-
gregates , of monoclinic prisms (Hayduck). —
BaA'2aq(E.a.L.). — ^BaA'^: amorphous (Hantke).
-r-KA'^aq: short needles (from dilute alcohol).
Methyl derivative
CsHsMe(OMe)(SO,H). Formed by boiling D-diazo-
tpluene sulphonic acid with MeOH. Syrup. —
' BaA'2 2aq : small laminse.
Ethyl derivative CjHsMe(OEt)SOsH.
Formed by boUiug p-diazo-toluene sulphonio
acid with alcohol (Paysan, 4.-221, 214, 363;
Hayduck, A. 172, 215).— KA'aq.— BaA'2 2aq (P.).
.^BaA'jSaq (H.).— PbA'jSaq, The amide
C8H,Me(OBt).SOjNH2 crystailises in lamina
[137°] ; the chloride is an oil.
o-Cresol sulphonic acid CBHsMe(0H).S03H
[1:2:5]. From the corresponding toluidine sul-
phonic acid by boiling the diazo- salt with water
(Nevile a. Winther, C. J. 37, 631). The chief
product of thejSulphonation of o-cresol in the
ooM (Hantke, B. 20, 3209). Very deliquescent
needles.
BeacUons. — 1. At 140° it is split up by water
into o-cresol and H^SOj. — 2. HNO3 (1 part) with
wa-ter (2 or 3 parts) converts it into di-nitro-
o-cresol, [86°]. — 3. Potash-fusion gives salicyHo
acid and very small quantities of a di-oxy-ben-
zoio acid which is turned blue by Fe^Olj.
Salts.— BaA'j2iaq(Gerver, A. 169, 386).
Needles (from dilute alcohol). Gives a violet
colour with FcjCl,. — BaA',: large sparingly
soluble plates (Hantke).— KA' : very soluble
pearly plates (H,). — OuA'jSaq: tables. —
PbAj2Jaq <G.). Small needles.
Ethyl derivative C3H3Me(0Et)(S03H)
[1:2:5].— From 03H3Me(NH2)SO,H, by heatmg
its diazo- derivative wil^ alcohol (Foth, A. 230,
306).— BaA'j4aq. ^
m-Cresol Bulphonic acid C,H,Me(0H)(S03H)
[1:3:6]. [118°]. From m-cresol and H^SOj at
110° (Olaus a. Krauss, B. 20, 3089 ; cf. Engel-
hardt a. LatsohinofE, Z. 1869, 622 ; Nolting a.
Salis, B. 15, 1862). Plates (containing 2aq) [75°]
(from dilute HjSOJ or (containing IJaq) [96°]
(from cone. H^SOJ. v. sol. water, alcohol,
ether, and benzene. Gives a violet colour with
t'eoClj. CrOa gives toluqninone.— KA'SJaq!
stellate group of needles with fatty lustre. —
CuA'^Saq: tufts of pale-green prisms. — ^BaA'jaq:
nodules.— BaC,H3S0j2aq.
^-Cresol sulphonic acid Q„H3Me(0H)(S03H)
[l:4:2]i [188°]. From ^-toluidine sulphonio
aciid by the diazo- reaction (Jenssen, A. 172, 237).
Long needles (containing 6aq) [99°]. V. sol.
water, alcohol, and ether. Hydrolysed by passing
steam through its solution in dilute HjSO^ boil-'
ing above 120° (Armstrong a. Miller, C. J. 45,
148). — BaA'2 : amorphous, v. e. sol. water. Its
solution is coloured violet by FejClj.
Methyl derivative 0„H3Me(OMe)S03H.
From the diazo- derivative of toluidine sul-
phinic acid by gently, warming with methyl
alcohol (Limpricht a. Heftter, A. 221, 352). Its.
amide crystallises in prisms [150°] ; its chlor-
ide is an oil.^BaA'2.— KA'.
Ethyl derivative C3H3Me(OI|t)(SO,H).
Prepared as above, using ethyl alcohol.
Formed also by warming diazo-toluene sul-
phonic acid with alcohol (Bemsen a. Palmer,
Am. 8, 245).— BaA'j 3iaq.— KA'. The amide
CsH^Me(0Et)S03NH3 [136°] (L. a. H.) ; [144°]
(B. a. P.) crystallises in needles. The chloride
is an oil.
^-Cresol sulphonic acid 0,H,Me(0H)(S03H)
[1:4:3]. From ^-cresol and fuming HjSO,. Also
from the corresponding ^-toluidine sulphonio
acid by the diazo- reaction (Engelhardt a. Lat-
schinoff, Z. 1869, 619 ; Pechmann, A. 173, 203).
Syrup. Fefilg colours its solution blue. Potash^
fusion gives p-oxy-benzoio acid. — KA'2aq:
laminaa. — BaA'j : tables. S. 7 at 17° (Baumann,
S. 4, 813).— BaO,H3S042aq. V. si. sol. water.—
PbA'23aq. — PbA'^l^aq : laminas (from alcohol).
Cresol sulphonic acid OjH3Me(OH)(S03H)
[l:?2:a;]. Formed by fusing toluene di-sulphonio
acid with KOH (Brunner, Sits. W. [2] 78, 665).
Feathery groups of crystals (containing ^aq at
100°) [81°]. Hygroscopic. V. sol. alcohol and
ether. — NaA'22aq. — KA'2aq ; prisms [0. 228°], —
BaA'jaq. Its solution is turned blue by FcgClg. —
CaA'24aq.— PbA'23aq.— CuA'28aq.— ZnA'jlO^aq.
Cresol sulphonic acids have been obtained
by sulphonating cresols by Duclos {A. 109, 138),
and by Armstrong a. Field (B. 6, 974), but not
sufficiently characterised.
p-Cresoleso-solphonic acid
CeH40H).CH,S03H [1:4]. From
CjH^fNHjj.CHjSOsH by diazo- reaction (Mohr,
A. 221, 221). Deliquescent needles; v. sol. ^
alcohol. The aqueous solution is turned bluish-
violet by FejOlj.—KA'.^aq.— BaA'2 7^aq.
Ethyl derivative CjH4(OEt).CH2.S03H.
Prepared' by decomposing the dia20- derivative
of C3]^.,(NH2).CH2.S03Hby boiUng with alcohol.
— BaA'2 2aq.
o-CresoldiBulphonicaeidCjH2Me(OH)(S03H),
[1:2:3:5]. From o-toluidine disnlphonio acid by
diazo- reaction (Limpricht, B. 18, 2176; H,
Hasse, il. 230, 293). Tables or needles. V. sol
water and alcohol. — KjA"l^aq: very solubU
needles. — BaA" 3.Jaq : smaU needles.
Ethyl derivat'^ve C3H2Me(OEt)(SO,H),
From the diazo- derivative of o-toluidine disul-
phonic acid by boiling with alcohol under an
extra pressure of 400 mm.— BaA"2Jaq.
m-Cresol disnlphonic acid
C„H2Me(0H)(S03H)2. From m-oresol (1 pt.) and
CKOCONIO AOID,
276
HjSOj (5 pts.) at 130° (Claus a. KrauBs, B. 20,
3089). V. sol. water and alcohol, m. sol. ether
and benzene.— KA' 3aq : plates.— BaA'aJaq.
^-Cresol disulphonio acid
C.H^e(0H)(SQ3H)j [l:4:3:2or6]. Promp-tolui-
dine di-sulphonio aoid by diazo- reaction (Lim-
prioht. B. 18, 2178 ; E. Eiohter, A. 230, 322).
Needles. V. e. sol. water and alcohol.— BaA" 4aq :
needles.- KjA" Jaq ? : tables.— PbA" 3aq : v. sol.
water.
p-Cresol disnlphonic acid
CsHjMe(OH)(SOaH)j [1:4:3:51. From ^j-oresol
Bulphomo aoid and faming H2SO4 (Engelhardt
a. Latsohinofl, Z. 1869, 620).— KjA'* 3aq : crys-
tals, V. e. sol. water. — BaA''2^aq: needles, si.
sol. water.
m-Cresol trisnlphonic acid
C,HMe(OH)(SOjH:)s. From m-cresol, fuming
HjSO,, and Ffi^ at 180° (Claus a. Krauss, B. 20,
3089). The Ba salt is v. sol. water.
CBESOBCELLIO ACID v. (5:3:2:1)-Di-ozy-o-
lOLUIC AOID.
CEESOSCIN V. Dr-OXT-TOLBENE.
CEESOBCIN-CAEBOXYLIC ACID v. Di-oxt-
TOLUIO AOID.
CEESOTIC ACID v. Oxy-toluio acid.
CBESS OIL. The volatile oil of garden-cress
{Le^i3iMm sativum) consists to the extent of 75
p.c. of phehyl-acetonitrile (benzyl cyanide) (Hof-
mann, B. 7, 1293). " The volatile oil of water-
cress (NAst'wrtmm officinaUs) consists of phenyl-
propionitrile (Hofmann, B.'j, 520).
CBESYL COUFOirNDS v. Toltl compounds.
CBOCETIN OsiH^Oj. Formed by the action
of dilute acids on crocin, a sugar (crocose) being
the correlative product (Eayser, B. 17, 2231).
Bed powder. V. soli alcohol and ether, nearly
insol. water. Dissolves in alkalis with a yellow
colour. lake crocin it dissolves in H2SO4 with
a blue colour, which slowly becomes violet, red,
and finally brown. StuSs mordanted with
stannous chloride acquire, by boiling in a solu-
tion of crocetin (from Gardenia), a dingy greenish-
yellow colour, which by treatment with ammoni-
acal water is converted into a brilliant yellow
colour, unaltered by light and air. The yellow
robes of the Chinese mandarins are dyed with
the fruit of the Oardenia.
CBOCIN {the eolovHng matter of saffron)
C,JB.,„0^. Appears to be identical with the
colouring matter of Chinese yeUow pods {Oar-
denia grandiflora) (Boehleder, J. pr. 56, 68).
Yellow powder. V. sol. water and dilute alcohol,
si. sol. absolute alcohol, nearly insol. ether.
Preparation. — The saffron, which has been
previously extracted with ether, is soaked in cold
water, the colouring-matter is removed from the
aqueous solution by animal charcoal, and after
drying is extracted fiom the charcoal by means
of 90 p.c. alcphol.
BeacOons.— It dissolves in HjSO, with a deep
blue colour, which gradually becomes violet, then
ted, and finally brown. HNOj also produces a
blue colouration, which almost instantaneously
passes into brown. By dilute acids it is split up
into crocetin OajHuOo and a sugar (crocose)
C„H,„0, (Kayser, B. 17, 2228).
CitOCONAMIC ACID CjHaNO, i.e.
C,03(OH)(NH2),ormoreprot)ablyC50,(NH)(OH)_j.
ImUo-croGoma aoO.—'Sixa ammonium salt u
formed by heating the di-anilide of oroconie
acid with aqueous NH,. Mono-basic acid.
Salts. — A'NH4: red prisms with bluish reflex.
A'Ag icaq : yellow needles.— A'^Ba 3aq : sparingly
soluble sm^l yellow needles. — BaC5HNOj4aq:
sparingly soluble yellow plates (Nietzki a.
Benckiser, B. 19, 773 ; 21, 1856).
CBOOOWIC ACID C.H-0. or
<C(OH).CO
I I (?)•
C(OH).CIO
FormaUon. — 1. From the black-residues ob-
tained in the preparation of potassium byBrun-
ner's method (Gmelin, P. 4, 37; A 37, 58;
Liebig, A. 11, 182 ; P. 33, 90; Heller, J.pr. 12,
280; A. 24, 1; 34, 232; Will, A. 118, 177).
When CO is passed over melted potassium and
the product is treated with water, a red salty
potassium rhodizonate, is formed. A so-
lution of this salt changes on standing exposed
to air to potassium oroconate. Excess of alkali
converts rhodizonic aoid into croeonic acid dihy-
dride, which appears to be an intermediate /body
in the formation of croeonic acid from rhodi-
zopic acid (Nietzki, B. 20, 1617). — 2. By heating
benzene-tri-quinone C^Osto 100°, or by boiling
it with water, COj being evolved. — 3. By exposing
an alkaline solution of tetra-oxy-quinone
Ca(OH)402 to the air, oxalic acid being formed
simultaneously. — 4. By evaporating hexa-oxy-
benzene Cg(OH)„ with dilute KOH in an open,
dish (Nietzki a. Benckiser, B. 18, 509).
PreparaHon. — ^By boiling the hydrochloride
of djiamidotetraoxybenzene Ce(NH2)2(0H)4 (1 pt.)
with EjCO, (4 pts.) precipitated MnOj (3 pts.)
and water (60 pts.) for ^ hour ; on adding BaCl,
to the filtrate acidified with HCl the sparingly
soluble barium croconate separates in golden-
yellow plates ; the yield is 70 p.c. of the theore-
tical (Nietzki a. Benckiser, B. 19, 293).
Properties. — Sulphur-yeUow plates or grains
(containing 3aq). V. sol. water, sol. dilute alco-
hol. Di-basic acid. Forms a sparingly soluble
red crystalline anilide. Heated with NH, it
gives the tri-imide of leuconio acid. With hy-
droxylamine it gives the penta-oxim of leuconio
acid Cs(NOH)j. By H^S it is. converted into
thio-oroconio aoid CgH^OjS. It is reduced by
SnCl,, SO2, or zinc-dust to the colourless hydro-
croconic acid CsH^O,, which is readily reoxidised
to croeonic >acid. By heating potassium cro-
conate with HI it is reduced to ' croconic-acid-
hydride' (OioHjOij ?), whose salts are deep
coloured; by further reduction it gives a colour-
less substance which is readily reoxidised to
the hydride. Croeonic acid is oxidised by HNO,
to leuconio acid C5O5.
Salts. — KjA": long dark-yellow needles (N.
a.B.).— K2A"2a'q: orange needles (G.).— HKA":
brownish-yellow needles with violet reflex. —
NaKA"a;aq : yellow rhombic plates, become red
on drying. — CaA"3aq: yellow powder (W.). —
BaA"lJaq : lemon-yellow powder, insol. water,
V. si. sol. HClAq. — PbA"2aq: lemon-yellow pp.,
insol. water. — CuA" 3aq : sparingly soluble
orange needles with blue reflex. — AgjA" : orange
PP-
Aniline salt A"(NH3Fh)2: yellow plates^
m. sol. water.
Bi-anilide Cj(HO)ijO(NPh)2 : slender red
needles. Formed by heating the aniline salt with
t2
276
CROCONIC ACID.
alcohol. V. si. Bol. all solvents but aniline. Dis-
solves in aqueous alkalis, and on heating the
solution orbconio acid and aniline are regene-
rated. Heated with aqueous NH, it is converted
into croconamio acid CjHsNO^ (Xietzki a.
Benckiser, B. 19, 772).
Mono-phenylhydrazide
C5(0H)A(NsHPh) : [above 300°] ; yellow
needles ; v. sol. alcohol, insol. water. Di-basic
aoid. — KjA": nearly black coppery needles, v.
Eol. water with a brown colour.
Tolylene-o-diamide v. Cboconic-di-iolu-
OUINOXAIINE.
< Croconic-acid-hydride ' O5H4O5 or 0,„HsO,„
yC(OH).CO
i.e. CH(OH)^l I (?). The'hydrocroconic
\C(OH).CO
acM' Of Lerch (A. 124, 20). Formed by heating
potassium croconate with HI. Its salts are dark-
coloured. By further reduction it is converted
into a colourless substance, which is readily
reoxidised to the hydride. — 05H205Ba2aq or
C,jH20,„Ba2 4aq: deep orange crystalline powder
or amorphous flocoulent pp. — PbCsHjOj: red
pp. (Nietzki a. Benckiser, B. 19, 297).
CBOCONIC-TOLUftUINOXALlNE O.jHsNjO.,
t.e. 0,Ha^ I ^C50(0H)2. Croconic-acid-tolylene-
o-diamide. Formed by mixing a cold aqueous
solution of croconic acid with a salt of tolylene-
, o-diamine. Fine needles, with green reflex. Sol.
alcohol with a brown colour, insol. water. Di-
basic acid. — A"E2 : black metallic needles
(Nietzki a. Benckiser, B. 19, 776).
CBOCOSE (saffron-sugar) CbH.^Os. Trimetrio
crystals. Sweet taste. Dextrorotatory. Its
reducing power is half that of dextrose. Formed,
together with crocetin, by the action of dilute
acids on crooin (Ea^ser, B. 17, 2232 ; cf. Boch-
leder a. Mayer, J. 1858, 476 ; Sits. W. 29, 3).
CBOSSOFIEBINE. An amorphous alkaloid
in the bark of Crossopterix Kotschydna (Hesse,
B. 11, 1646).
CBOTACOHIC ACID C3H<(C0jH)j. [119°].
Solidifies at 90°. From oyano-orotonio acid
which changes spontaneously into acid ammonic
crotaconate (Claus, A. 191, 74;,B. 10, 822).
ProperUes. — Crystals. iBol. water, alcohol,
and ether. At 140° it decomposes, giving off
CO2 (difference from itaconic, citraconic, &o.).
Combines with HBr forming an acid
C3H,Br(C0jH), [141°].
Salts.— (NHJHA". — KHA" 2aq.^KjA"aq.
— PbA".— AgjA".
Dimethyl ether Ue^A.". S.G.i^l-U. Sol.
alcohol and ether.
Isomerides : Oiteaconio, Itaconic, Mesa-
coKic, and Ethyuseke-malonic, Acros.
CBOTONIC ACID O.HjOj i.e.
CH,.0H:CH.C08H. Mol. w. 86. [72°]. (185°
cor.). S. 8 at 19°. B-o) 35-71 in a 4-12 p.c.
aqueous solution (Kanonnikofi).
Occurrence. — in crude wood vinegar (Kramer
a. Grodzki, B. 11, 1369). ' Its name is derived
from croton oil, from which it was erroneously
supposed to be formed by saponification (Pelletier
a. Caventon, J. Ph. 4, 289 ; 11, 110 ; Schlippe,
A. 105, 1 ; Geuther, Z. [2] 5, 270).
Preparaticm. — 1. By oxidation of crotonio
Aldehyde (from acetic aldehyde) in the air or
by moist Ag^O (Kekulfi, B. 3, 604; Z. [2] 6.
705). — 2. From aUyl cyanide (v. vol. i. p. 136)
obtained from mustard oil (Will a. Eorner, A.
125, 273).— 3. By distillation of (/3)-oxy-butyrio
acid (WislicenuB, Z. 1869, 325).— 4. By boiling
o-bromo-butyrio ether with alcoholic KOH (Hell
a. Lauber, B. 7, 560). — 5. From isoerotonic aoid
by intramolecular change brought about by heat-
ing to 175° (Hemilian, A. 174, 322).— 6. From
malonic acid (1 mol.), paraldehyde (1 mol.), and
excess of glacial acetic acid at 100° (Eomnenos,
A. 218, 149). The yield is good (50 p.c.).— 7. By
heating pyruvic «cid (1 p,t.) with Ac^O (5 pts.)
and NaOAc (5 pts.) at 170° (Homolka, JB. 18,
987). — 8. By reduction of aceto-acetio ether
with sodium-amalgam (BeUstein a. Wiegand, B.
18, 482).
Properties. — ^Trimetricplates (bysublimation)
or monoolinio crystals (from water) ; a:b:o
= 1 : 1-8066 : 1-5125 ; j8 = 131°. M. sol. hot Ugrom.
Beactions. — 1. Potash-fusion forms only
acetic acid.— 2. Not reduced to butyric aoid by
sodium amalgam (Korner, J. 1866, 318 ; A. 137,
233; c/.3ulk, A. 139, 62).— 3. Br gives OiS-di-
bromo-butyric aoid. — 4. Cone. HBr at 100° gives
a- and a little /3- bromo-butyrio aoid. — 5. HOOl
gives chloro-oxy-butyric acid.^6. Cone. HNO,,
gives acetic and oxalic acids. — 7. Chromic acid
mixtwre gives aldehyde and acetic acid (Kekul^,
A. 162, 315).— 8. Aqueous ammonia forma'
o-amido-butyric acid (Engel, O. B. 106, 1677).
Salts. — KA' : deliquescent needles. — KHA', :
plates (from alcohol) (Pinner, B. 17, 2008).—
NaA'. S. (alcohol) 1-4 at 14°.— BaA',: easily
soluble plates. — CaA', : v. sol. cold, si. sol. hot,
water (BeUstein a. Wiegand, J5. 18, 482). —
PbA'2: stellate groups of needles.— ZnA'j 2aq
(Albert!, B. 9, 1194).— AgA': curdy pp.
Methyl etherUeA;. (121°). 8.0,4-9806.
liD = 1-4138 (Kahlbaum, B. 12, 344).
Ethyl ether :EU.'. (139°cor.). /»d = 1-424.
Boo 50-45 (Briihl, A. 235, 8 ; B. 14,' 2798). S.G.
If -9268 ; §1 -9186. M.M. 7-589 at 24-4° (Perkin,
C. J. 45, 537).
Amide. Syrnp; v. sol. water (B. a.W.). A
ciystalline amide [0. 151°] was obtained by
Pinner (J5. 17, 2008) by exposing to the air
the hydrochloride of j3-chloro-butyrimido-ether
CHs.CHCl.CHj.C(0Et).NH2Cl.
Iso-crotonic acid CfSfi^ i.e.
CH2:CH.0Hj.C0jH (?). .QuartenyUc acid. (172°
cor.). S.G. ^ 1-018. Occurs in crude wood
vinegar (Grodzki a. Kramer, B. 11, 1359).
Prepa/ratioii. — Aceto-acetic ether is treated
with POI5 and the product poured into water.
The two chloro-orotonio acids formed are dis-
tilled with steam. The chloro-iso-crotonio acid
alone passes over. It is reduced by sodium
amalgam, and the iso-crotonic aoid i? extracted
by ether. On evaporation this leaves iso-crotonic
acid as a syrup.
ProperUes. — ^Liquid, smelling like butyric
acid; miscible with water. At 175° it changes
to the preceding isomeride (Hemilian, A. 174,
322).
Beactions. — 1. Bromine acting on a solution
of iso-crotonic acid dissolved in CSj produces the
dibromide of ordinary solid crotonic acid {v. Di-
BKOMO-BUTYRio aoid) (Kolbe, J. pr. [2] 25, 397). —
2. Potash-fusion gives only acetic acid.^-3. So-
dium amalgam has no action.
CRYFTOPINE.
277
Salts. — CaA'i^aq; very soluble needles. —
BaA'22aq: small crystals, v. e. sol. water. —
PbA'jaq. [68°].— AgA.'.
Ethyl ether EtA. (136°). S.G. 12 -927
(Geuther, Z. 1871, 243).
Isomerlde of crotonic aeid 0,HjOj. [19°].
(181°). Prom vinaconic acid (q.v.) by distillation
(Eoder, A. 227, 24).
S alts.— CaA'2 6aq.— BaA'22aq.— AgA'.
Constitution. — From its formation, from
0Hj:CH.0H(C02H)jit should bevinyl-aoeticacid,
CH.,:CH.CHj.OOjH, a formula, attributed, with-
out sufficient reason, to isocrotonio acid.
Another isomeride of crotonio acid v. Meth-
ACBYLIC ACID.
Sibromide of ciotonic acid v. Di-bbomo-buty-
BIO ACID.
Derivatives of crotonic acid v. Bbomo-cboto-
Nic ACIDS and Celobo-cbotonio acids.
CROTOKIC ALDEHYDE O^Ufi i.e.
CH,.CH:CH.CHO. Mol. w. 70. (105°). S.G.a
1033.
Formation. — 1. By heating aldehyde with
ZnCLj and a little water to 100°, aldol being first
formed : 2CH,.CH0 = CH3.0H(0H).CHi.CH0
= CHs.CH:CH.CHO-i-HjO. Other dehydrating
agents may be used (Lieben, A. Suppl. 1, 117 ;
Kekulfi, Z. [2] 6,572 ; A. 162, 92 ; Bauer, A. 117,
141 ; Lieben a. Zeisel, M. 1, 820). Hence it
occurs in crude spirit (Kramer a. Pinner, B. 3,
75).— 2. By the distillation of aldol (Wurtz, C.
B. 87, 45). — 3. From vinyl bromide by succes-
sive treatment with H2SO4 and water (Zeisel, A.
191, 371). — 4. Prom acetylene by successive
treatment with HjSO, and water (Lagermarck a.
Eltekoff, B. 10, 687).
Prepanration. — Paraldehyde (1 pt.), water
(1 pt.), and cone. HClAq (2 pts.) are kept at 25°
for 5 days. The liquid is then, neutralised with
Na^COg, the ppd. dialdane is filtered ofi, and the
filtrate extracted with ether. The ethereal ex-
tract is distilled under reduced pressure, and the
crude aldol (Jpt.) (85° to 120° at 200 mm.) is split
up into water and crotonio aldehyde (| pt.) by
distillation under ordinary pressure (Newbury,
C. B. 92, 196 ; Am. 5, 113).
Properties. — Pungent Uquid; m. sol. water.
Oxidised in the air or by AgjO to crotonic acid.
It forms a crystalline combination with NaHSQj,
m. sol. water, whence NajCO, does not liberate
the aldehyde (Lieben a. Zeisel, M. 1, 818).
Beactions.—l. POlj gives di-ohloro-butylene
(126°).— 2. By saturation with HCl in the cold
it is converted into /3-chloro-butyric. aldehyde
[97°]. — 3. Br gives oUy o;8-di-bromo- butyric
aldehyde (L. a. Z.). — 4. 01 forms a;8-di-chloro-
butyric aldehyde, and finally o;8-di-ehloro-butyryl
chloride (Zeisel, M. 7, 359). — 5. Iron and acitic
acid reduce it to butyric aldehyde, butenyl alco-'
hoi, and re-butyl alcohol (L. a. Z.). — 6. Ac^O
gives the di-acetyl derivative of crotonic orthal-
dehyde CH,.CH:CH.CH(OAo)2 (205°-210°). S.G.
14 1-05 (Lagermarck a. BltekofE, J. B. 11, 79).—
7. Dilute HCl at 0° forms, by hydration, a little
aldol, paraldol, and dialdane (Wurtz, O. B. 97,
1169). — 8. Ammonia forms tri-orotonylene-
amine OijH^jNi. At -20° ammonia passed into
an ethereal solution of the aldehyde forms
C,H,5N.O (Gombes, C.B. 96,1862).— 9. Crotonic
aldehyde (1 pt.) treated with aldehyde (2 pts.)
and ZnCljat 100° forms an aldehyde CaH,0
(172°)- KekulS, A. 162, 105).— 10. By heating
with HON and saponifying the product penti-
noic acid OHjtOH.OHiOH.OOjH is formed
(Lobry de Brnyn, Bl. [2] 42, 159).
Derivative 0H3.0H:CH.CH01(0Et).
(184°). From di-chloro-butylene and alcoholic
KOH (KekuU, A. 162, 99).
CItOIONIIIlILE V. Allyl OTAmoB.
CBOTON OIL. A fatty oil contained to the
amount of 50 p.c.in the seeds of Croton TiglAum,
a euphorbiaceous plant. It is purgative, and
inflames the skin (Schlippe, A. 105, 1 ; Mayer,
N. Jahr. pr. Pha/nn. 10, 318 ; Geuther a. Pr5h-
lich, Z. [2] 6, 26, 549). It contains glyoerides
of formic, acetic, isobutyric, isovaleric (isobutyl-
formic) and tiglic acids (E. Schmidt a. J.Beren-
des, A. 191, 94; B. 10, 835; Ar. Ph. [3] 13,
213). The nature of the purgative principle has
not been satisfactorily made out (Senier, Ph.
[3] 14, 446 ; Kobert, Chem. Zeit. 11, 416).
CBOTOKTTL ALCOHOL v. Buiekyii aloohol,
vol. i. p. 639. '
CEOTON YLENE v. BninraNB.
TEI-CEOTONYLENE-AMINE C.jHjjN^. (0.
190°) at 40 mm. Formed by heating aldol with
excess of aqueous NHj at 160° ; or from cro-
tonio aldehyde and NH3 at 100° (Wurtz, 0. B.
88, 1154). Efflorescent prisms (containing Saq) ;
si. sol. cold water, v. sol. alcohol. HOI at 150°
resiuifies it.
Salts. — Crystallise readily from acid solu-
tions.—B'SHCl : hexagonal prisms.— B'SHNO, :
hexagonal prisms. — B'HaCl3(PtClJj. —
B'2H,01a(PtCl,),.— B'H^Cl^AuOla.—
B'HsCljAuCl, 2aq.— B'jH,0l8(Au01,),.
CBOTONYLEITE GLYCOL v. Ebtthbiib and
Di-oxt-butylekb.
OEOTYL ALCOHOL v. Butenyi. alcohol.
CEOTYLAMINE 0,H,NHj. (75°-80°). Pre-
pai^d by the action of alcoholic KH, on iso-
butylene bromide. Liquid (Hofmann, B. 7,
514 ; 12, 992).— (B'HCl)jPt0l4. YeUow scales.
ISO-CEOTYL BROHIDE v. Bbouo-buiylene.
ISO-CEOTYL CHLOBIDE v. Chlobo-isobuiyl-
ENE. ' ,
CEOTYL IODIDE v. Iodo-butyiene.
CEOTYL THIOCASBIMIDE C,H,N.CS.
(179°). From crotylaitiine (Hofmann, B. 7,
516). Pungent liquid.
CEOTYL-THIO-TJEEA 0,H,NH.CS.NHj.
[85°]. Prom the preceding and NHs(H). Crys-
talline.
CEYPTIDINE C„H„N. (274°). A homo-
logue of quinoline ^occurring in coal tar (Gre-
ville WUliams, Chem. Qaz. 1856, 283).
Cryptidine Cj,H„N. (270°). Prepa]?ed by
the dry distillation of xylldine-acrolran (Leeds,
A. C. J. 5, 2). Eeddish-yellow oil. Disagree-
able odour. Bitter taste. — B'HCl: fine thin
tabular crystals.— B'HjPtCla : fine yellow crys-
tals. Sol. water, insol. alcohol.
CEYPTOPHANIC ACID CsH^NOa. An acid
said to occur in normal human urine (Thudi-
chnm, C. J. 23, 116 ; 34, 81). The urine ia
evaporated to one-fourth of its bulk and Fe^Ol,
added. The pp.' contains the iron salts of
cryptophanic, paraphanic, hippuric, and benzoic
acids. It may be decomposed by baryta. Amor-
phous gum, V. e. sol. water. — PbA". — CaA".
CEYPXOPINE OaiHjsNOs. [217°]. S. (alco-
hol) -08 (Smith). S-G. 1-35 (Schroder B. 13.
278
CRYPTOPINE.
1075). A base oeourring in very small quantity
in opium (T. a. H. Smith, Ph. [2] 8, 595, 716 ;
Hesse, A. Suppl. 8, 299 ; A. 176, 200 ; Kauder,
Ph. [3] 18, 250). Ppd. by adding NaOH to the
mother-liquor, from which codeine, naroe'ine,^
thebaine, and papaverine have been separated.
Six-sided prisms (from alcohol) ; when freshly
ppd. it is soluble in ether, but it slowly separates
from the solution. SI. sol. boiling alcohol, v. si.
sol, benzene and ligroin, m. sol. chloroform.
Dissolves in excess of KQHAq. Inactive to
light. Cone, (impure) HjSO, gives a blue colour
turned orange by KNO3. FejClj gives no colour.
Not decolnposed by HCl.
Salts. — Separate from aqueous solution as
jellies, but subsequently become crystalline. —
B'HOl 6aq : soft mass of crystals (from alcohol). —
B'HCl 5aq. — B'jHjPtCl, 6aq. — B'^HjCrjO,. —
B'B.jCS>i- S. -3 at 12°.— B'C.HsOe 4aq. S. -15
at 10°.— B'C8Hj(NOj)30H aq.
Meconate B'gCjHjO, lOaq : si. sol. boiling
water.
Nitro-cryptopine C2,Ha(NOj)N05. [185°].
From oryptopine and HNOj (S.G. J.-06) at 55°.
Dark-yellow crystalline powder. Insol. water
and EOEAq. Cone. H^SO^ dissolves it with
blood-red colour.— B'HCl 3aq B'^H^PtCl, lOaq.
— B'HNO,.— OxalatesB'jHjCA 12aq. S.6-8 at
16° and B'HjCA 3aq.
CEYSTALLIN v. Peoteids.
CBYSTALLISATION.— The examination of
a crystal and the determination of its form and
properties may serve as a means of recognising
and defining any given body. But besides this
practical application, the examination may help
to find an answer to the question : What is the
connexion between the chemical constitution
and the cryst^ine form of bodies ?
^ The complete examination of the form and
properties of a crystalline substance may de-
mand a thorough knowledge of crystallography,
and also skill in the use of complicated and
costly instruments ; but a general knowledge of
the principles of the subject, and of the use of
a geological mic:;oscope, such as ought to be
found in every laboratory, will very often enable
the chemist approximately to determine the
form of a substance, the identity or non-identity
of two samples, or the homogeneous character of
his preparations. The following account may
serve as a general view of the subject, or as an
introduction to a more complete study; it is
necessarily incomplete, and for further details
special books must be consulted, such as Groth's
PhysikaUsche Ki'ystallograplm; current litera-
ture being found in the Zeitschrift fil/r Krysial-
lograpMe, and the different mineralogical
journals.
A crystal may be described as a solid homo-
geneous body bounded by planp faces that are
arranged around the body in a certain regular
manner, which is constant for each chemical
compound. Neither the number of faces that
bound a crystal, nor the shapes of these faces,
are constant and characteristic, since both
may vary considerably with very slight altera-
tions of external conditions at the time of
crystallisation ; but the regularity, or the sym-
metry which aU the faces bear to each other,
and the manner in which the faces occur in
groups or sets or 'forms' is constant and
characteristic.
Single or Simple crystalline form.— ThaA all
the faces of a crystal do not belong to the same
form is often strikingly evident by a difference
in colour, as in many of the platinocyanides, or
in the condition of the faces, some of which are
smooth and lustrous, while others are dull or
streaked with numerous fine lines, or are rough
with little pittings, or appear to be made up of
numerous scales, and then show a pearly lustre ;
such differences are to be noticed on crystals of
magnesium sulphate, quartz, salt, alum, potas-
sium ferrocyanide, potassium chlorate, gypsum,
copper sulphate, &o. The same fact is often
also to be noticed in another way, viz. by the
appearance of splits or cleavage planes that run
parallel to certain faces but not to others, as in
calcite and potassium ferrocyanide; often where
such are not manifest the crystal may be easily
split or cleaved parallel to certain faces but not
to others, as with gypsum, cane sugar, magne-
sium sulphate, &e. Differences in the forms of
the faces of crystals are often shown by the way in
which the crystal during its growth has inclosed
foreign substances, as bubbles of liquid or gas,
or fragments of solid substances that were sus-
pended in the solution, viz. the inclosures are
distributed in lines or planes parallel to certain
edges or planes of the crystal, but not to others.
In examining a crystal all such observations are
of the greatest service, as they at once give a
means of classifying |^e may-be numerous faces
into their proper sets or forms.
A crystal may be completely bounded by
only one set of faces, e.g. a cube of rock salt ;
but there are several crystalline forms that are
not capable of inclosing space, as the various
prisms and pinacoids, or basal planes, and such
forms necessarily never occur alone. The mini-
mum number of crystalline forms that may
occur on a crystal is limited only by the con-
dition that they must completely inclose the
crystal; the maximum number is unlimited;
but however many there may be, all are cor-
related by an empirical law, known as the
rationality of indices, and the symmetry of
faces constituting each individual form is the
same.
This last statement, though strictly true,
is apparently not so in several cases, as certain
forms show externally a geometrical symmetry
apparently other than that which belongs to
their internal structure ; thus both salt and iron
pyrites crystals often exhibit no other form than
the cube, and therefore are apparently possessed
of the same kind and amount of symmetry, yet
other forms that occur in these two substances
show that iron pyrites is really possessed of a
lower degree of symmetry than sodium chloride
[v. Hemihedral forms, p. 283).
Symmetry of crystalline forms. — A solid
figure may be symmetrical about a point, or
about a plane, or a number of planes. A
solid figure is symmal/rical about a point when
any number of particles on the surface being
joined to the central point by straight lines,
these being produced to equal distances on the
other side of the centre shall exactly coincide
with a series of similar particles. This kind of
symmetry only demands that to every face there
CRYSTALLISATION.
279
be a second and parallel one ; it is only met
with in the asymmetric {i.e. without symmetry)
crystals, as, for instance, copper sulphate and
potassium anhydrochromate.
A solid figure is symmetrical about a plane
when from any numher of particles on the sur-
face perpendiculars being drawn to the plane
and produced equal distances on the other side
of the plane, the points so found shaU exactly
coincide with a series of similar particles ; in
other words, the one half is the mirrored image
of the other, the mirror being the plane ^ of
symmetry. Thns a cube is symmetrical about
the plane ac g e. A line perpendicular to the
plane of symmetry is called an axis of symmetry,
and about a central point in this axis the figure
is also symmetrical. Thus (fig. 1), starting with
acge&B B, plane of s^nmetry, and abfe as any
given plane, the existence of ad he and dcgh
necessarily follows, as the former is the image
mirrored in the plane of symmetry, and the
latter is the plane symmetrical to the first with
regard to the central point; the existence of
bcgf follows similarly from either or both of
the last two faces.
Fio. 1.
Besides the above-mentioned plane a c g e
there are five others that divide the cube in
exactly the same fashion, viz. the planes b d hf,
b a h g, cfed, afgd, and b e he, and these
make therefore a set of six planes of symmetry ;
and the corresponding six axes of symmetijy
are the lines m n, op, g r, s t, u v, and w x,
joining the centres of the opposite edges (fig. 2).
A plane that is at right angles to two planes
of symmetry contains two axes of symmetry, and
metry are the lines A B, CD, and E P (fig. 3).
As a plane of principal symmetry contains two,
and in the hexagonal system three, exactly
similar axes of symmetry, the appearance and
Fia. 2.
must therefore itseU be a plane of symmetry ;
and if, as in the case now considered, the two
contained axes of symmetry are similar, then
the symmetry of the new plane is of a higher
order than that ql the two others. The above
six planes may be taken two at a time in three
different ways, and thus a set of three new
planes of a higher order are found ; they are
called planes of principal symmetry as dis-
tinguished from planes of ordina/ry. symmetry;
they are qsrt, wuxv, and ompn (fig. 2),
juid the corresponding axes of principal sym-
M
n--,-:^-
Pia. 3.
actual position of a crystal is not changed by
rotating it about the axis of principal symmetry
such that first one and then another of the
similar axes of ordinary symmetry come to
occupy the same position. In this way a plane
of principal symmetry may be most readily dis-
tinguished from a plane of ordinary symmetry.
Division of crystalsinto classes. — Aorystaloan
only be possessed of a set of three exactly similar
axes of principal symmetry, or of one such axis, or
it must be devoid of any such ; and aU crystals m ay
accordingly be divided into three great classes :
(1) Crystals possessed of three axes of principal
symmetry must necessarily contain also a set of
six axes of ordinary symmetry (as explained
above in the case of the cube), and all such
are said to belong to the Regular system.
(2) Crystals possessing one axis of principal
symmetry must necessarily contain axes of
ordinary symmetry at right angles to the first.
The number of these axes of ordinary symmetry
may be either (1) a set of three inclined to each
other at one-third of four right angles, with, as
a necessary consequence, a second set of three,
also inclined to each other at one-third of four
right angles, but removed from the first set by
one-sixth of four right angles, or (2) a set of two
at right angles to each other, with, as a neces-
sary consequence, a second set of two also at
right angles to each other, but removed from the
first set by half a right angle. Crystals satisfy-
ing the first set of conditions are said to belong to
the Hexagonal system, and those satisfying
the second set to the'Quadratic system. (3)
Crystals destitute of any axis of principal Sym-
metry may yet contain axes of ordinary syni.
metry, and the possible cases are (i) three sets
of one axis each, i.e. three dissimilar axes,
whida must of necessity be at right angles to
each other, (ii) one single axis, and (iii) no axis
of symmetry at alC Crystals satisfying these
three conditions are said to belong to the
Rhombic system,to the Monosymmetric
(formerly called the monoolinic) system, and
to the Asymmetric (formerly called the tri*
clinic) system.
Thus all crystals may be divided geometri-
cally into the above six systems ; and it is a very
important fact that exactly the same division is
effected by a consideration of all the physical
properties, more especially the optical and me-
chanical ones, viz. tensional strength, the ther-
mal and electrical properties being difficult of
investigation, and also by a mathematical dis-
cussion of the possible ways of arranging a
number of . points in space. Crystals of th«
280
CRYSTALLISATION,
legulai system behave optically like amorphous
bodies, they are singly refractive and are there-
fore said to be isotropic. All other crystals are
doubly refractive and are called amsotropic ;
they are divided into two classes according as
they contain one direction or no direction afong
which a beam of light may travel and then
emerge from the crystal without suffering double
refraction ; those possessed of this axis of single
refraction are termed optically wniamal. The
hexagonal and quadratic crystals are both
uniaxial, and optically they are undistinguish-
able; in both cases the tensional strength in
the plane of principal symmetry varies with the
direction in which it is determined, but while
hexagonal crystals shpw three directions of mini-
mum and of maximum strength, quadratic crys-
tals show only two. Anisotropic crystals that
are not uniaxial have been caUed optically bi-
axial, though they have not two directions that
are truly void of the power of doubly reftaoting
light as above defined. When a properly-cut
section of a biaxial crystal is examined in
' convergent polarised light ' the two optical axes
are seen surrounded by dark and light rings
gradually shading into each other, and as the
' interference figure ' is not the same for light
of any two colours, so the rings, merging more
or less completely into each other, are fringed
with colour, and by a careful examination of
the coloured fringes it can be determined to
which of the last three systems the crystal be-
longs ; viz. if rhombic, the figure is symmetrical
about both diameters A B and C D, and con-
sequently also about the central point E ; if
monosymmetrio, the figure is symmetrical about
one or other of the diameters or about the cen-
tral point, according to circumstances ; if asym-
metric, the figure is void of symmetry (fig. 4).
Fio. 4 (diagrammatic).
In studying the geometrical properties of
crystals, certain lines must be taken within the
crystal, to which all the faces may be referred ;
these Unes, of which there must be three, are
called the orystallographical axes, and they are
represented by the letters a, 6, o, while the in-
elmations which they make with each other are
represented where necessary by the letters a,P,y,
viz. a:6 = 7; a:c = P; and 6:o = a. In each sys-
tem the crystallographic axes are chosen in such
a way that the different forms may be most
simply expressed. By this is to be understood
that each of the different faces that together
make a single crystalline form is to be related
to the axes in exactly the same numerical way,
or in other words the geometrical symbol for
each of the faces of a form is exactly the same
if the signs be omitted that denote a face to be
at the top, front, right hand, &o. In the regular
system the three axes of principal Eynunetryare
chosen, and as these are all exactly similar and
equal, the expression a, b, o becomes a, a, a, and
as 'a' stands thus alone it may itself be con-
sidered as unity, and the axial expression thus
becomes o=(i=ai = lorfl5 = l; the expression for
the axial angles is always o=;8 = 7 = 90°. In
the hexagonal system one set of three axes of
ordinary symmetry (two of these three axes
would be sufficient, biit for the sake at com
pleteness it is convenient to include the third,
this is also not without its advantages), and the
axis of principal symmetry, are chosen ; as the
first three are exactly alike, but are independent
of the last, the expression for the axes a, 6, c
becomes a,a,a,c; one of these may te made
equal to unity, most conveniently a, and the
orystallographical axes are expressed a:c = l:e.
The axial angles are in all cases a:c = 90° an
a:a = 120°. Here notice that any and every
crystal of the regular system has its axes repre-
sented by ffl = 6=c = l and a=j8=7 = 90°, and
these facts do not therefore need to be re-
peatedly stated, for they are comprehended in
the expression 'regular system.' Thd same
holds good with the axial angles of any and
every hexagonal crystal, viz. a:a:ffl=120° and
a:c = 90°; but with the relative lengths of the
axes it is otherwise, the ratio of a:e is not the
same for any two substances, and in describing
a hexagonal crystal -the crystallograpJmal con-
sta/nt, the axial ratio a:c, must be accurately
measured and given ; thus for example in lead
dithionate it is as 1:1'5160, while in strontium
dithionate, which has almost exactly the same
form and is therefore said to be isomorphous,
it is as 1:1-5024.
These crystaUographical axes are not to be
considered as definite lines,, having definite
lengths, but as directioiisj determined by the
symmetry of the crystal, and consequently en-
dowed with certain properties — i.e. like axes
must be cut by the like number of faces at the
like angles — and upon which the relative lengths
of the intercepts cut off by the various faces
maybe calculated trigonometrically from the
measurements of the interfacial angles. These
angles are always measured by means of a re-
flecting goniometer, above th^ centre of whose
graduated circle the edge, over which the angle
is to be measured, is exactly placed by means
of adjusting screws. About the same centre
the crystal and a collimator or telescope may be
made to revolve ; the position of ,a beam of
light incident upon the crystal, and the positions
of the reflected beams from the two lustrous
crystal faces, are thus measured, and the inter-
facial angle determined. The method of calcu-
lation may be exemplified by reference to a
beryl crystal. Here there are four sets of faces,
each of which, of course, outs the axes differ-
ently, and one of these manners of cutting
must be chosen as the standard (fig. 5); The
basal faces (0001) cut only the vertical axis,
the prismatic faces ^(1010) cut only the hori-
CRYSTALLISATION.
281
Eontal axes, and henco neither of these forms
alone allows a determination of the ratio a:c.
Pio. 6.
But the faces of each of the two pyramids (1011)
and (2lll) out both horizontal and vertical axes ;
for the sake of simplicity the faces (1011) are
chosen as those of the primary pyramid, and
the three horizontal axes are thus fixed as being
parallel to AA.', BB' and CO'. The angle
1011:0001 having been measured and found
I
I
FiQ. 6.
150° 3' 20", a:e is easily calculated thus;
tan (180= -150° 3' 20") =—, but if oa = unity,
OTO
then
OTO = ^, hence 01! = -^ tan (180° -150° 3' 20")
= 0-4989; that is, a:o = 1:0-4989 (see fig. 6).
If, however, the angle of the pyramid over
a terminal edge, i.e. (10il):(0111) had been
measured and found equal to 151° 5' 40", then
by describing from the" point a a spherical
triangle cutting the face of the crystal in AB
(fig. 7), the plane of principal symmetry in AC,
and the plane of ordinary symmetry in CB, the
side a can be found from the known data,
B = i(151° 5! 40"), 6 = 60°, and 0 = 90° ;
thus Bin c ■■
sin b
, hence c= 63° 25' 20",
sin B
then tan iffl = tan W-^i^npZ^
tan 1° 42' 40" x sin 82° 46' 25".
" sin 7° 13' 35"
hence \a, = 13° 15' 25", and a = 26° 30' 50";
end lastly °^'^ g = tan of 26° 30' 60", from
axis a
which the value for the vertical axis c = 0-4989
is aRiiiii touiil.
lur any given crystal the axial ratios are
thus exactly determinable, biit where any
arbitrary choice has been made, as in this
instance, then the same is adopted by all sub-
sequent observers unless good reasons are found
for making an alteration.
In the quadratic system one of the two sets of
two axes of ordinary symmetry, and the axis of
principal symmetry, are chosen ; the axial
angles are in all cases 90° ; the expression a, b,
0, thus becomes a, a,o, and, as in the hexagonal
system, the axial ratio a:o has to be actually
determined in every individual case. In the
rhombic system the three axes of ordinary sym-
metry are chosen ; the axial angles are in aU
cases 90° ; as these three axes are not similar, the
expression a, b, c, remains as such; making
one equal to unity, the other two constants have
to be determined in every individual case. In
themonosymmetric system the axis of symmetry
is chosen as one crystaUographical axis ; the
other two axes must lie in the plane of symmetry,
but otherwise their positions are perfectly arbi-
trary; for simplicity's sake, they are chosen
parallel to two well-defined edges or faces on
the crystal; in this system a, b, c, are quite
independent and have to be determined, b is
generally the axis of symmetry and is made
equal to unity ; the inclinations of b:a and b:e
are in all cases 90°, but the inclination of a:c
(axial angle 0) is variable and must be deter-
mined. In the asymmetric system the crystallo-
graphic axes are chosen quite arbitrarily ; gene-
rally however they are chosen parallel to three
prominent edges of the crystal ; they are quite
independent of each other, therefore of unequal
lengths, and moreover no two of them are in-
clined at right angles to each other ; for asym-
metric crystals there are thus five constants to
be determined.
Relation of faces to axes. BaHonaUty of
-When a number of sets of faces on a
crystal are referred to the axes whose relative
lengths have been found as just explained, it is
noticed that the intercepts cut oS can in all
cases be expressed as some simple multiple or
sub-multiple of the fundamental axial lengths.
This is known as the rationality of the indices.
Thus in the case of the beryl crystal (fig. 5),
while the faces of the primary pyramid cut the
axes a:a:a:c at the distances l:oo :l:0-4989, those
of the faces (2111) cut at 1:2:2:0-9973; here
1 is 1 X 1, 2 is 2 X 1, and 0-9978 is 2 x 0-4989,
and the numbers 1, 2, 2, 2 are here indices. The
indices are generally expressed by very simple
numbers, as 1, 2, 3, 4, 6, 6, ^, |, |, &c., but in
some cases the ratios are not so simple.
The indices of a face may be measured in
two ways — the one known as Neumann's system,
and the other as Miller's. Let the relative
lengths of any set of primary axes be expressed
by the letters a, b, c, and let there be another
face on the crystal, which cuts the axes at some
other distances, say 2a, 36, 4c, from their centre.
According to Neumann the indices of this face
are —, 55.. ^ i.e. 2, 3, 4 ; following Miller,
a be
however, the indices are the reciprocals of
those of Neumann, viz. --, — , — -, 1.0.^,^,^,
la do 4c
or, simplifying, the expression becomes G, 4, 3,'
232
CRYSTALLISATION.
Of course there will be more than one face hav-
ing this symbol, the number depending on the
symmetry of the crystal, but the relative posi-
tions of any of these may be exactly denoted by
the following device. In all the systems the
extremities of the axes forming the front upper
right comer are called positive, and are simply
written a, h, e, &b., while the opposite extremities
are called negative, and are written u, B, c, &c.
Thus taking the pyramid of the beryl crystal,
and using Miller's symbols, we have the axes
and faces numbered as in figs. 8 and 9.
Fio. 9.
The axial ratios once determined, it is pos-
sible from them and the symmetry to say at
once what forms ,are possible, and to calculate
their interfacial angles, &c. ; but what forms
will actually occur, under any conditions, can-
not be predicted; their existence depends on
external conditions, as presence of imparities in
the solution, nature of the solvent, temperature,
and speed of growth. Mineralogists and crystal-
lographers often pay too much attention to the
finding of new or numerous forms upon speci-
mens without attempting to determine what
were the conditions necessary for the production
of these forms, which is the only point of real
interest.
The following may serve as an example of
the way in which the symmetry of a crystal
determines the number and position of the faces
of a form. In fig. 10 the three similar crystal-
Pio. 10.
lographio axes of the beryl crystal (fig. 6) are
represented by the lines a„ a„ and a^, while the
principal axis c is perpendicular to the plane of
the paper. Suppose a face of the hexagonal
pyramid to be present in the front, upper, middle
segment, i.e. 1011, then this demands the exist-
ence of a face 1101, because the plane passing
through axis a, and the vertical axis c is a plane
of symmetry ; the_ presence of llOl demands
the existence of 0111, because the plane con-
taining ^2 and c is a plane of symmetry ; further,
these-three faces demand the existence of other
three, viz. 0111, 1 101, 1011, because the plane a^c
is a plane of symmetry ; and lastly, these six
planes demand the presence of other six on the
under part of_the crystal, viz. 1011, 0111, 1101,
iOli, Oill, 1101, because the plane containing
axes OS,, Oj, a, is a plane of symmetry. And with
these twelve faces the form is complete, foi the
other three planes of symmetry belonging to thlil
system are already satisfied.
It would be very tedious and redundant to
denote this or any other form by writing the
symbols of all its faces, and it is therefore
customary to write the symbols of only one,
generally one in the front, upper, right corner,
and to inclose it in brackets thus (lOll) for -the
pyramid in question. The general shape of a
form is not essentially altered by varying the
indices within certain limits ; thus JB031) and
(1013) (figs. 11 and 12) as well as (1011) (fig. 8),
Fig. H.
represent hexagonal pyramids, though the form
(3031) is very high and pointed, whUe the form
(10i3) is proportionally low and flat-looking.
These may all be expressed by one general
Pia. 12.
symbol (mOml) (where m has any value between
0 and CO ), and are said to be particular forms
of one general form (mOnil) ; thus fig. 12 repre-
sents the particular form for a crystal of beryl
when m=3, for 1013 is the same as ^0|, i.e,
mOml.
But if the index m has the value of 0, then
the six upper faces of the pyramid fall together
into one plane, and so also do the six lower
faces, so that the form (0001) consists only of
two faces psirallel to each other and also to the
plane of principal symmetry; if m has the
value of 00 , then each of the upper six faces
becomes coincident with the subjacent bottom
face, and the form_(oD 000*1), or, as it is more
usually vrritten, (1010), consists of six faces, all
parallel to the axis of principal symmetry, and
consequently not limited towards either end ;
these two forms (0001) the basal plane, and (1010)
the prism, may be- called open forms, and can
never occur alone on a crystal. They contain
no variable quantity, and may therefore be
called ^a;e<i!/orms, while the pyramid is, a van-
able form.
These two forms, the basal plane and the
prism, though derivable from the pyramid and
related to it in position, are obviously quite dis-
tinct forms, and all are so far independent of each
other that any one may or may not occur on a
crystal in conjunction with the others. By
varying the indices in every possible manner, as
just indicated, it ia easy to determine the shapeg
CRYSTALLISATION.
288
and number of aU suoh fundamental or geneial
forms for every system ; and indeed it is only
possible to grasp the relationships existing be-
tween them by regarding them as being derived
from one perfectly general form (mnl). ■ The
number of individual forms is very limited; the
following is a complete list of their symbols and
names.
Regular system.— (mnl), (mml), {mnO),
{mmO), (111), (001), (110), oaUed respectively
hexakis octahedron, triakis octahedron, tetrakis
hexahedron, trapezohedron, octahedron, cube or
hexahedron, and dodekahedron; the last three
are fixed forms.
Hexagonal sy stem.— {mpnl),{Note:int'he
symbols for aU hexagonal forms m + »+jp = 0).
{mpnO), in both these cases the ratio ^ varies
n
onlj between 1 and 2; (mOjal), (1010), {2mmml),
(2ll0), and (0001), called respectively the di-
hexagonal pyramid and prism, the hexagonal
pyramids and prisms of the first order, and of
the second order, and the basal plane.
Quadratic system. — (mnl) and (mwO),
where the ratio — varies between 1 and oo;
(mml), (mmO), (mOl),' (mOO), and 001; the
forms are called the diguadratic pyramid
and prism, the guad/ratlc pyramid and prisms
of the first order, and of the second order, and the
basal plane.
Rhombic system. — {mnl), (mnff), (001),
called respectively pyramids prisms or domes,
aadi'basal plane or pinacoids.
Monoclinic system. — The sameforms exist
as in the rhombic system, but here, owing to low
order of symmetry, all the pyramids and some
of the domes are composed of independent halves,
which are distinguished as + or — , or by more
fully denoting _Qie position of the face ; thus
(mnl) and (mnl).
Asymmetric system. — The same forma
exist as in the rhombic system, but here, owing to
the lack of symmetry, aU the pyramids are com-
posed of independent quarters, thus (mnl),
(nml), (mnl), and (mnl), and all the prisms
and domes are composed of independent halves,
thus (mnO) and (mnO).
The forms just described are collectively
called holohedral or whole or complete-faced
forms, to distinguish them from other forms
known as hemihedral or half -faced, and tetarto-
hedral or quarter-faced.
Hemihedral forms may be considered as
derived from the holohedral forms by re-
solving these by a set or sets of planes of sym-
metry into a number of equal segments, when
the faces contained in any one segment belong
to the one hemihedral form, whUe those con-
tained in the adjacent segment or segments
belong to the other hemihedral form, and so on
all round the crystal.
The hemihedral forms of the hexagonal sys-
tem being very important yrUl be taken by way
of example. Any holohedral hexagonal form
may be divided into segments in three different
ways : —
Firstly, by the plane of principal symmetry
and one of the two sets of three planes of
ordinary symmetry ; making then the adjacent
faces independent, the rhombohedral hemihedral
forms are produoed. Numbering the faces of
the most general form, the dihexagonal prism, as
in fig. 13 it is seen that the faces are divided
thus:
2 9 4 5 6 ? » 9 10 U i3
2346678^10 11 12
en
Fio. 13. .
The two forms
12. .56. .9 10. .
. . 3 4 . . 7 8 . . 11 12
and
. . 34 . . 78 . . 1113
12. .56. .9 10. .
are known as the + and — scalenohedrons (figs.
14 and 15), which differ from each other in posi-
Pio. 14.
Fio. 15,
tion and in physical properties. Just as in the
holohedral division, so here, the indices of only
one face is written within brackets to denote
the whole form, but to distinguish it from the
symbol of the original pyramid the prefix k is
added; thus the symbols for the two scaleno-
hedrons are K(mpnl) and K(pnml). By
varying the values of these indices m,n,p in
every possible way, or by dividing aU the other
holohedral forms into segments in the same
fashion, it is found that there are produced two
other new forms, the + and — rhombohedrona
K(mOml) and k(OtotoI), figs. 16 and 17 ;
while the following forms already mentioned in
the holohedral division appear again without
apparent alteration, viz. (mpnO), (lOlO),
(2mmml). (2110), and (0001). But the con-
284
CRYSTALLISATION.
Btancy of these latter forms in both divisions is
not real, as the physical properties are different ;
this is especially to be seen in the manner
in which they yield to the action of solvents,
whereby little pittings or etch-figures are pro-
duced which vary in their symmetry according
as the fdrms are holohedral or hcmihedral. It
Fio. 16.
IB to be understood that practically the holo-
hedral and hemihedral forms are perfectly dis-
tinct, that is, a given substance shows the forms
of only one of the two classes, never those of the
other. For example, oalcite frequently occurs
in the form of the scalenohedron (3i21), fig. 14,
and is therefore obviously hemimorphous, but it
also frequently occurs in the form of fig. 18, and
^ ^^
Fio. 17.
Fia. 18.
this may be either a holohedral or a hemihedral
crystal, but the fact that such crystals cleave
with the utmost readiness parallel to the faces
of the positive rhombohedron k (toOtoI) at
once removes it from the class of holohedral
crystals ; its hemimorphous nature is also proved
by other physical properties.
A holohedral hexagonal form may be divided
into segments, secondly, by means of the two
sets of three planes of ordinary symmetry,
whereby the pyramidal hemiJiedral forms are
produced ; for example : —
12S4"S6'?89 10 1112
12a466?89 10 1il2
- The uncrossed faces ^{pnml) are represented
on a cryslal of apatite by figure 19 where
r{pnml) = 7r(2l3l}. AU other forms are exter-
'fxsPWV
10 1 Q
vA__^
Fio. 19.
nally the same as in the holohedral division,
with the exception of 7r(pram0). These two new
forms are called the pyramid and prism of the
third order.
Thirdly, by means of the two sets of three
planes of ordinary symmetry and the plane of
principal symmetry, whereby the trapezohedral
hemihedral forms are produced ; for example ; —
i234g6789 10ill2
1234567 8 Oie 11 Ifl.
These forms are distinguished by the prefix
T, the crossed faces being T{mphl) ; such forma
have not been actually observed.
The tetartoliedral forms before referred to
may be considered as being produced by the
superposition of two dilferent hemihedr^ upon
the same crystal. As there are in the hexagonal
system three classes of hemihedrie, there can be
obtained two or perhaps three different classes
of tetartohedrie. In the following schemes the
faces suppressed by the rhombohedral, pyra-
midal, and trapezqhedral, hemihedrte are re-
spectively crossed /, — , or \.
First, the rhombohedral tetartohedrie is pro-
duced thus : —
^;Z34^0?-8^KI1112
i2^^, S6?^dl0ill2.
The faces of a dihexagonal pyramid remaining
uncrossed, viz. 2Vio"'i form a rhombohedron of
the third order, written ior(m?lpl), which is ex-
hibited in fig. 20 of a copper silicate _ (dia-
spore) crystal, where the indices are Kir(14.l3.1.6).
Fig. 20.
Fig. 21.
Secondly, the trapezohedral tetartohedrie is
produced thus : —
j;J{3^^jii71^?M1118,
the form KT(npml) consisting of the six un-
crossed faces '^j",'",! being known as the trigonal
trapezohedron, and in the figure representing a
quartz crystal the faces of such a form, viz.
kt(5161) are shown (fig. 21).
Thirdly, the scheme
!^2!^4^6^8$1Q}4 12
shows a form bounded by six faces meeting the
vertical axis above, but no face meeting it below.
It is doubtful whether this tetartohedrie has
been observed ; for exactly the same form would
be produced by making either of the forma
ir(mpral) or T(m§nl) hemimorphous or haJf-
sided.
Hemimorphism may be described as the di-
viding of the faces of a cry stalline form into two
independent halves, the one half cutting the one
extremity of an axis of symmetry, and the other
half the other extremity of the same axis. Hemi-
morphism is to be found in the first five systemsin
CRYSTALLISATION.
385
holohedral, hemihedial, and tetartohedral, divi-
sions alike; it is supposed to be due to. asymmetry
of the atoms in the molecule, and the solutions of
the substances showing this phenomenon, as, tar-
taric acid, milk, sugar, <feo., are generally optically
active. It is to be noticed that some divisions
of crystals are necessarily hemimorphous. Thus
the hexagonal trapezohedral tetartohedral forms
are hemimorphous to the axes of ordinary sym-
metry.
The hexagonal crystals are thus divided into
the following six or seven distinct classes:
{a) holohedral ; (b) hemihedral, and that of three
kinds, rhombohedral, pyramidal, and trapezo-
hedral ; and (c) tetartohedral, and that of at least
two kinds, rhombohedral and trapezohedral, and
possibly another ; and lastly to each of these six
classes there may or may not be assimilated also
hemimorphism, making in all twelve or possibly
thirteen divisions of hexagonal crystals, in only
one of which can any substance ever crystallise.
These six or seven classes are to be considered
as being due to the different arrangements of the
molecules in the crystal, but among these dif-
ferent molecular arrangements there are certain
regularities common which group them all to-
gether into one general system. It is to be noted
that all hemihedral and tetartohedral divisions
are invariably possessed of fewer planes of sym-
metry or of planes of a lower degree of symmetry
than are the holohedral forms ; thus the trape-
zohedral hemihedral forms and all tetartohedral
forms of the hexagonal system are possessed of
no plane of symmetry whatever, i.e. as defined
at the commencement of this article ; but such
forms do not, therefore, belong to the asymmetric
system, for in the first pl^ce they show a perfect
regularity in the recurrence of equal faces and
angles in sets of three or of six, which an asym-
metric crystal can never do, and secondly they
show none of the physical properties of these
crystals, but properties that are either identical
with those of the hexagonal holohedral crystals,
or are in the main of the same kind, difiering
only just so much as might be expected from
the lower degree of symmetry they possess.
Just as hexagonal crystals are divided into a
number of distinct classes, so also are the crys-
tals of the other systems as far as their varying
symmetry allows. Thus regular crystals are
either (a) holohedral, (6) hemihedral, and that of
three kinds, viz. tetrahedral, pentagonal, or pla-
gihedral, or (c) tetartohedral of one kind only ;
the quadratic crystals are subdivided exactly like
the hexagonal ones; the rhombic crystals are
either (a) holohedral or (6) hemihedral ; and the
monosymmetrio and asymmetric crystals can
show neither hemihedrie nor tetartohedrie.
There still remains another regularity met
with in the forms of crystals, viz. the symmetri-
cal growth of two or more crystals as one indi-
vidual. Such a complex is called a twin or tril-
Ung, and in such the component individuals are
definitely related as regards position, viz. the one
crystal generally occupies such a position that
were it rotated through 180° about a particular
line, called the twin axis, aU its faces &o. would
then be exactly parallel to those of other crys-
tals. The plane at right angles to the twin axis
is called the twin plane, and in many instances
the two individuals meet in this plane, and it is
then also termed the contact plane ; but in other
instances the two individuals penetrate each
other in a perfectly irregular manner, and there
is then no definite contact-plane. The formation
of a twin crystal is probably explained by ex.
treme viscosity of the solvent, or of an insufficient
lapse of time between the separation of two
molecules from a solution and their approximation
to form a single solid particle, and for either of
which reasons the molecules would not be able
to become exactly parallel, which must be the
most stable position, but would take up the next
most stable position by reason of the molecule
being originally more nearly in that position. As
a plane of symmetry for the external form is also
a plane of symmetry of the intermolecular force,
which varies with the direction in which it is
exercised, so a plane of symmetry can never be
a twin plane, else the two individuals would be
exactly parallel ; that is, they would be identi-
cal: further, as the arrangement of the mole-
cules, and consequently the external form, de-
pends on this same intermolecular force, so the
twin plane and axis are invariably connected with
the external form; generally the twin plane is a
possible crystalline face, and often one that is
expressed by a very simple symbol. Twin or
complex crystals are often characterised by re-
entering angles, but these are frequently eithei^
BO small as to be unnoticeable or are not present,
and the crystal then affects a symmetry that it
does not really possess.
The following figs, represent rhombic arago-
nite crystals ; fig. 22, a simple crystal, and fig. 23,
^^
Ol"
oil
^
<5
\oji /
/
\
11°
J'
i m I
p
^ on \
N
s|
X-
Pio. 23.
a twin, showing re-entering angles, the twin plane
being the prism face ; and lastly, fig. 24 represents
^
i
ni ^
:^
fij
Fio. 24.
a trilling, showing only the forms (110) and (001),
which externally appears very like a hexagonal
cjrystal, except that two of the vertical faces are
a little nicked because the angle of the prism
(110) is not exactly 120°. The real nature of
such compound crystals is most easily' detected
by their optical properties, a section cut parallel
to the base at once resolving itself in a parallel
beam of polarised light into a number of seg-
ments distinguished from each other by differ-
ence of colouV or luminosity, and whose relative
positions can readily be determined by opticai
examination.
286
ORTSTALLTSATION.
Eesides representing tKe form of crystals by
parallel projections, as in the various figures,-
these forms are often also represented in a totally
different manner, viz. by spherical projection.
From a central point within a crystal, imagine
a sphere of any radius described, and from its
centre a line let fall perpendicularly on to every
crystalline face and produced until it cuts the
surface of the sphere. The positions of the
faces are thus recorded by as many points upon
the surface of the sphere, and their positions
may very conveniently be represented upon a flat
surface by making a diametral section of the
sphere bringing the recording plane and one ex-
tremity of the diameter at right angles to that
plane into the point of view, whereby great labour
in drawing and calculating is saved, as all great
circles on the sphere appear in the projection as
straight lines or as arcs of circles. In the regu-
lar, hexagonal, and quadratic, systems the dia-
metral section is always drawn parallel to the
plane of principal symmetry, in the rhombic
system to the basal plane, in the monosymmetrio
and asymmetric systems it is drawn perpen-
dicular to the faces of the prisms. Thus the
beryl crystal, fig. 5, as far as the sphere lies in
the plane of this paper, appears as in /fig. 25,
and the position of the three faces, when drawn
upon the plane of principal symmetry, as in
fig. 26 ; the one straight line joining the three
Fios. 25 and 26.
points shows that they are in the same zone,
that is, are all parallel to one conmion direction,
and therefore their intersecting edges are paral-
lel, and this fact is very easily noticed or tested
when the crystal is mounted on the goniometer
for measuring. The completed projection ap-
pears as in fig. 27, where zones are all in^-
cated by the various lines circular or straight.
This method of projection also allows of the
positions of optical axes, cleavage planes, &c.,
being shown.
It now only remains to mention a few points
concerning the growth and actual appearance of
the faces of a crystal, beyond those mentioned
on p. 278. A crystal once formed in a solution
and continuing to increase in size, every face, or
at least every face of any set of faces, would re-
ceive a deposit of the same thickness, and an
ideally perfect crystal as represented in the
figures would result, were it not that the li(iuid
.1100
010
■y^\ '/
V^^Tx
oTio^
'\/S^'i
/
\^\Trtt>*
^JrSTr^-'^v'A
\otHirV
^^k?^ \
"s
^^TbijX I
\
^^^, ^t^Nl y
uoi^
/\y °
o\^
L-%
1010
Fia. 27.
in depositing the solid substance altered its
specific gravity, and currents being thus gene-
rated difierent par;ts of the crystal are thus sub-
jected to different conditions, and the several
faces receive unequal deposits of new material.
In consequence, the intersections of the similar
faces and their superficial extent are often very
dissimilar, though every face always remains
exactly parallel to its original position, and
the interfacial angles are constant. This so-
called distortion is often brought about or in-
creased by the crystal becoming attached by an
end or side to other crystals, or to the contain-
ing vessel. Thus fig. 28 represents an alum
crystal that has lain on the flat bottom of the
containing vessel, and fig. 29 represents the ideal
Fig. 28.
Fia. 29.
form such as may be obtained by constantly
changing the position of the growing crystal.
When new material is very quickly presented
to a growing crystal, it is often noticed that the
acuter solid angles grow extremely rapidly, shoot-
ing out into long needle-like points, and often
other acicular points will start from along the
first, and thus fern-like forms are produced; all
such growths are termed crystallme skeletons ;
when the rate of deposit becomes less the needles
almost cease to grow in the direction of their
length, bat increase continually in breadth and
thickness until they touch each other, and the
crystal returns to its original appearance, though
almost invariably it will contain a great number
of larger or smaller cavities, filled with the
mother-liquor, and, as already mentioned, these
cavities exhibit an arrangement or a form that
corresponds with the general symmetry of the
crystal. Some substances, as ammoniam chloride,
CRYSTALLISATION.
287
metallic silver, &o., are very prone to form such
dendritic forms, while with other Bubetanoes, as
platinum-potassium chloride, if existing crystals
were not able to take up the new material, a
multitude of minute crystals would at once
lorm. The direction of these skeleton arms is
always coincident with some orystallographio
direction, and they are in reality made up of
numerous crystals, in exactly parallel position.
It has been mentioned that the faces of crystals
are often striated; thestriis consist of numerous
alternating faces of one or more forms ; thus
nitre crystals are vertically striated on the prism
and pinacoid faces by reason of these faces being
repeated alternately very many times.
Finally it may be useful briefly to describe
such a microscope as is used for the examination
of minute or growing crystals, or for the exami-
nation of rook sections. In this connexion
reference should be made to the papers of
Behrens (Boyal Micros. Soc. Joum., 1882) and
others, on the microchemical reactions by which
minute fragments of minerals &c. may be ana-
lysed qualitatively by converting their consti-
tuents into crystalline precipitates that may be
recognised under the microscope. The essential
parts of the microscope are the same as in every
other instrument, the parts specially concerned
in crystaUographic work being the following.
The stage can be rotated freely about the optical
centre of the instrument, and is brought exactly
into that position by a couple of adjusting
screws; the circumference is graduated into
degrees, and fractions can be read by a vernier.
The eye-pieces contain crossed (rectangular)
threads, and these always occupy a fixed position
by reason of a pin in the eye-piece and a notch
in the outer tube. Plane angles of crystals that
lie suitably, the angles between the lines of inclo-
sures &o., are easUy measured by the rotating
stage and the cross of the eye-piece. The fine
adjustment-screw for focussing is of known pitch,
and is provided with a head divided on its circum-
ference. By using a high power and a rather thick
specimen it is easy to determine the refractive
index not only of solids but of liquids (Sorby).
In the eye-piece can be fitted a micrometer scale,
and by using this and the micrometer screw the
interfacial angles of minute crystals can be
measure,d> though the method is one that would
only be used if the goniometric measurement
were not possible. During the cutting or grind-
ing of sections, especially rock sections, the
crystals often cleave, and the positions of the
planes of cleavage are at once determined from
the fine parallel hair-like cracks in the specimen.
Underneath the stage a polarising prism is
quickly put into position so that its polarising
plane is parallel to one of the cross threads in
the eye-piece ; crystals may then be examined
for dichroism. Above the stage, and most con-
veniently over the eye-piece, a second polarising
prism may be placed or rapiiUy removed; it may
be rotated about the central axis, and t^e amount
of rotation is approximately shown on a smaU
divided circle.. When the two prisms are crossed,
isotropic and anisotropic crystals are at once dis-
tinguished, unless the crystalline.plate is at right
angles to the optical axis, but in this caBe the
interference figure can be obtained as described
below ; further, if the crystal be anisotropic,
twinning is generally at once recognised, and, with
the help of the rotating stage, the relationships
of the different parts are determined, by com-
paring the depolarising directions among them- '
selves and with the edges of the crystal ; simi-
larly in a simple anisotropic crystal the angles
between the depolarising directions and the edges
may be measured, and the system of crystallisa-
tion thus determined when the examination of
the external form alone would not have been
conclusive ; and even when the external form has
been destroyed, or when it has been lost by
veason of the crystal growing until it filled the
whole space that happened to be at its disposal,
the examination of the cleavage cracks, lines of
inclosures, and depolarising directions, is often
sufficient to determine the crystalline system.
The relationship between depolarising directions
and edges may be used for discriminating bet ween
different substances crystallising in the mono-
symmetric or asymmetric systems, as the various
felspars. Finally anisotropic crystals lying in
suitable positions can be examined for their
interference figures by removing the eye-piece,
but retaining both polarising prisms, placing a
small, very short, focus-lens above the lower
prism and directly below, but quite close to, the
crystal, and lastly using a short focus objective
and bringing it down rather close to the speci-
men. The interference figures thus observed are
certainly very small, and an extra lens is some-
times inserted above the objective to magnify
them, but the angle of vie w is thereby diminished.
Uniaxial and biaxial crystals are thus at once
distinguished, and if the former show any marked
amount of circular polarisation, or the latter any
marked amount of dispersion for the various
colours, these phenomena can also be noticed,
especially if use is made of red and blue glasses
to simplify the phenomena; such glasses are
also used in the measurement of the angles be-
tween depolarising directions and crystalline
edges. H. B.
CUBEBS ^The fruit of Piper Cubeba, a na-
tive of Java. It contains a volatile qil (from
which ' camphor of cubebs ' may be separated),
a crystalline substance cubebin, an acid resin
cubebic acid, and an indifferent resin (Monheim,
J. chim. Mid. 11, 352 ; Blanchet a. Sell, A. 6,
294 ; Miiller, A. 2, 90 ; Winckler, A. 8, 203 ;
Soubeiran a. Capitaine, A. 31, 190; 84, 311;
J. Ph. 26, 75 ; Aubergier, Bev. Seient. 4, 220 ;
Schmidt, Ar. Ph. [2] 191, 1 ; Schaer a. Wyss,
Ar. Ph. [3] 6, 316; OgUaloro, 0. 5, 467).
Oil of Cubebs. Contains dipentinene, the
hydrochloride of which C,„H,s2H01 melts at
49°, but consists chiefly of hydrocarbons boiling
between 250° and 270°, amongst which is a
sesquiterpene C.sHj, (275°). V.D. 6-73 (oalc.
7'05), whose hydrochloride 0,5H242HC1 melts at
[118°] (Wallaeh, A. 238, 80) or [131°] (S. a. C).
Camphor of Cubebs O.sHjeO. [67°]. (148°).
Occurs only in old cubebs. Trimetric crystals
(from alcohol-ether). Lsevorotatory. At 230°
it is split up into water and cubebene 0,5!!^,
(Schmidt, B. 10, 189 ; tf. Berthelot, Bl. [2] 11, 3). .
Cubebin 0,„H,„Oa
i.e. gx]CH,<°>C„H,(03H,0)? [125°]. S.
(alcohol) 1-31 at 12°. S. (ether) 3-75. Extracted
by alcohol from cubebs after removal of the
288
OUBEBS.
essential oil by steam distillation (Schuck, N.
Beperi. Fiumn. 1, 213 ; ' Steer, A. 36, 331 ;
Weidel, Sitz. W. 74 [2] 377 ; SchSr, Ar. Ph. [3]
25, 531),
Prc^erties. — Small needles (from alcohol);
V. si. sol. water. Cone. H^SO, colours it crimson.
ECl and HI have no action on it.
Reactions. — 1. KMnO^ on warming oxidises it
to oxalic acid and a resin, from which, after ex-
tracting with CHCI3, a crystalline residue of
piperonyUo acid CgHjOj [228°] is obtained. —
2. When heated with acetic anhydride and sociivm
acetate to 140° C. it yields OjoHjgOs [78°], which
can be obtained pure by crystallisation frdm
alcohol (Pomeranz, M. 8, 466). — 3. Potash-ftision
gives OO2, HOAc, and protocatechuic acid. —
4. HNO, gives oxalic and picric acids. —
5. Nitrotis acid giVes yeUow crystals of nitro-
oubeTjin C,|,H8(N02)Os, which dissolves in
aqueous KOH, forming a violet solution. — 6. Br,
added to a solution of cubebin in chloroform,
gives CioHjBraO^, which separates from boiling
xylene in white crystals.
Benzoyl derivative OuHoBzOa. [147°]
(Pomeranz, M. 9, 323).
Cubebic acid C^HieO, (Schulze, Ar. Ph. [3]
2, 888); C„B., fi, (Schmidt, Ar. Ph. [2] 191, 1).
A resinous acid extracted from cubeba by ether,
freed from volatile oil by steam-distillation, and
purified by re-orystaUisation of its Ba salt (Ber-
nazik, C. C. 1864, 191). Amorphous, insol.
water and acids, v. sol. alcohol, ether, and al-
kalis.
CUDBEAB. A name given to a variety of
archil, being al&o prepared from lichens, chiefly
of the genus Lecanora.
CUMALIC ACID v. Couiulio acid.
CimABHYSBIN v. Coio babe.
.((-CTrMENEC„Hs(CH3)s [1:3:4]. i-TrUnethyl.
benzene. Mol. w. 120. (169J° i.V.) (Jacobsen,
B. 19, 2513). S.G. 2 -8048 ; as -8580. H.F.p.
1310. H.P.V. -1590 (TA.). Dielectric constant
2-431 at 14° (Negreano, C. R. 104, 423). j»d
1-484. Occurs in aU kinds of petroleum (Ameri-
can, Bussian, &e.) (Engler,. B. 18, 2234 ; ef.
Mansfield, C. J.l, 244; A. 69, 179; Bitthausen,
J.pr. 61, 79 ; Beilstein a. Kogler, A. 187, 317).
Formation. — 1. From bromo-m-xylene and
bromo-iP-xylene by treatment with Mel and
sodium (Fittig, A. 139, 187; 151, 257, 286).—
2. From di-bromo-toluene, Mel, and sodium
YJannasch, A. 176, 286).— 3. From phorone
(derived from acetone) by treatment with PjOj
(Jacobsen, B. ID, 855).— 4. From toluene, MeCl,
and AljCl, (Friedel a. Crafts, A. Oh. [6] 1, 461).
5. By boiling pseudo-cumyl- hydrazine vrith
aqueous CuSO^ (Haller, B. 18, 92).
Preparatimi. — The mixture of t)i-cnmene and
mesitylene obtained by the distillation of coal tar
is snlphonated by agitationwith cold cone. BL,SO,;
on adding water a portion of the <)'-oumene sul-
phonic acid is ppd., the remaining acids are con-
verted successively into their Ba salts, chlorides,
and amides, and the latter are separated by crys-
tallisation from alcohol, in which the amide of
tfi-cumene sulphonic acid is sparingly soluble.
The sulphamide is then converted into i/f-cumene
by heating with fumiing aqueous HCl at 175°
(Jacobsen, B. 9, 256). The sulphonic acids of
^(-cumene and mesitylene may also be sepa-
rated by heating with HClAq at 100° for one
hour, when the latter only undergoes hydrolysii
(Armstrong, B. 11, 1697). <(i-Cumene sulphonio
acid is decomposed by distillation with dilute
H2SO4 in a current of steam, hydrolysis begin-
ning at 115° (Armstrong a. Miller, C. J. 45, 148) .
Reactions. — 1. Beadily attacked by halogens.
In the dark 1 mol. of bromine produces mono-
(eso)-bromo-pseudo-oumene CgHjMegBr [73°] ;
further bromination yields di- and tri-(eso)-
bromp-pseudo-cumene (GgHMegBr and C,Me,Br3)
of melting-points [61°] and [226°] respectively.
Direct simshme acts like heat, causing the sub-
stituiion to take place in the CH, groups ; 1 mol.
Br produces a liquid a>-bromo-(pseudo)-cumene
(pseudo-cumyl bromide) GjHs(CH3)2.CH2Br ; 2
mols. bromine produce w,-w2-di-bromo-pseudo-
oumene 0jH3(CH3)(CHjBr)2 which melts at 97°
(Schramm, B. 19, 216).— 2. Converted by boil-
ing with AljClg into toluene, m-xyleue, a little p-
xylene, mesitylene, durene, and isodurene (An-
Bchutz, A. 235,186). — 3. Methylene chloride ani
AlgClg give durene, tetra-methyl-anthracene [c.
163°], hexa-methyl-anthracene [c. 220'^] and
C„H„ [c. 290°] (Friedel a. Crafts, A. Oh. [6j 11,
263).— 4. Gives a tri-nitro- derivative [185°]. —
6. Dilute HNO3 gives two di-methyl-benzoio
acids and a little CsH,Me(C0^)2.
t(>-Cumene hezahydride CgH„. (137°). S.O.
g -7812; "^ -7667. From ifi-cumene, HI, and P.
HNO3 gives tri-nitro-i)'-cumene. Br and AljBr,
give tri-bromo-ili-cumene (Konovalo6, CO. 1887,
1183). Probably identical with nonaphthene.
Cumone C,H,2 i.e. CgH^Pr. Isopropyl-he/nz-
ene. Mol. w. 120. (153° i.V.). S.G. a -8776 ; ^
•8577 (Silva, Bl. [2] 43, 317) ; 2 -8798 ; ^ -8587
(Patern6 a. Pisati, Q. 3, 574).
Formation. — 1. By distilling cuminio acid
with baryta or lime (Gerhardt a. Cahours, A.
Ch. [3] 1, 87, 372; 14, 107; A. 38, 88; cf. A.
220, 27). — 2. From isopropyl bromide, benzene,
and Al^Br, (Gustavson, B. 11, 1251; B. Meyer,
J:pr. [2] 34, 98). In the same way from »-pro-
pyl bromide, inasmuch as ?i-propyl bromide i8
converted by heating with Al^rg into isopropyl-
bromide (Kekul6 a. Schrotter, B. 12, 2280).—
3. By acting with isopropyl chloride or ra-propyl
chloride on benzene in presence of alimiinium
chloride (Silva ; Glaus a. Schulte, B. 19, 3012). -
4. As a by-product by the action of allyl chloride
on benzene in presence of Al^dlj. — 5. By the
action of di-chloro-acetone in presence of ALCl,
on benzene as a by-product (Silva). — 6. From
benzylidene chloride and ZnMe, (Liebmann, B.
13, 45). — 7. From iso-propyl iodide, bromo-
benzene, and sodium (Jacobsen, B. 8, 1260).
Reactions. — 1,, Chrondc mixture gives benz-
oic acid. — 2. Br and Al^Br, give CjBrj, isopropyl
bromide, and tri-bromo-propane (c. 218°).
Cumene tetrahydiide GgH,3, (155°). Occurs
in small quantity in oil of resin (Benard, A. Ch.
[6] 1,239).
Cumene hesabydride GgH,,. (0. 149°). S.G.
^ -787. Occurs in oil of resin (Benard, A. Ch.
[6] 1, 229 ; cf. PeUetier.a. Walter, A. Ch. [2] 67,
99).
n - Cumene CjHaPr. n - Propyl - benzene.
(158-5°). S.G.a-88(Spioa,<?.8, 408); |? -8703
SohifE). C.E. (9-8 to 158-5) -001184. V.D.4-14
(for 4-14). S.y. 161-8 (Schiff, A. 220, 93).
Formation. — 1. From »- propyl bromide,
CUMENE^ULPHONIC ACID.
280
'hromo-benzene, and spdium (Fittig, Sohafler a.
Kdnig, A. 149,'324).— 2. From benzyl chloride
and ?5nBtj (Patern6a. Spioa, G. 7, 21).— 3. From
ALCij, benzene and allyl chloride (Wispek a.
Zuber, A. 218, 378) ; according to Silva (Bl. [2]-
43, 318) the product is isopropyl-benzene. —
i. A product of the action of ethylidene chloride
on tolaeue in presence of Al^Clg (Ansohutz a.
Eomig, B. 18, 665).
BeaotUms. — 1. In CS, solution it combines
with CrOgOl,, forming a chocolate pp.
PhPraCrOjClj converted by water into phenyl-
propionic aldehyde (Etard, A. Ch. [5] 22, 252).
2. Cho'ormc mixture gives benzoic acid.— -3. By
the action of bromine (1 mol.) in the dark or in
presence of 8 p.c. of iodine in diffused daylight,
a mixture of o- and p-bromo-propyl-benzene
C5H4Br(08H,) is obtained. By the action of
bromine (1 or 2 mols.) in direct sunshine, the
' side chain is substituted in the ;3-position giving
0,H5.CHBr.CH.,.CH3 or CsH5.GBr2.CH2.CH3. If
the ^-mono-bromo-propyl-benzene is treated
at 100^ in the dark with another mol. of bro-
mine, o3-di-bromo-propyl-benzeue is produced
Cs.H5.CECBr.CHBr.OH, [65-5°] (Schramm, B. 18,
1274).
Seferences. — ^BiioMO-cnMENE,CEiiOBO-ccMEm:,
NiTRo-ouMENB, &0. V. also Azo- and Hydbazo-
OOMPODNDS.
ijf-CUMENE CABBOXYLIC ACID v. Cu-
IHNIO AOID.
ifz-CUUENE-SUIiFHONIC ACID
C„H2Me3(SOaH) [1:3:4:2]. Obtained by debromi-
nation of di-bromo-pseudo-oumene-sulphonio
acid CsMe3Brj(S0sH) [1:3:4:5:6:2] by the action
of zinc-dust and aqueous NHj upon the sodium
salt. It is formed, together with the isomeride
(1:3:4:5) and other products,, by the prolonged
action of cone. HjSOj upon durene (q.v.) or its
mono-sulphonio acid. — ^NaA': very soluble small
flat needles or plates.
Amide 0,njlAe,(SOiT<iSt): [113°]; small
flat needles or plates ; v. e. sol. alcohol (Jacob-
sen, B. 19, 1222). ,
ij,-Cumene-sulphonio acid C5H2Mes(S03H)
[1:3:4:5]. Obtained by debromiiiation of bromo-
pseudocumene-sulphonio acid by the action of
zinc-dust and aqueous NH, upon the sodium
Bait (Jacobsen, B. 19, 1218), or by sodium-
amalgam (Kelbe a. Pathe, B. 19, 1556). It is
formed, togetber with the isomeride [1:3:4:2] and
other products, by the prolonged action of cone.
H2SO4 upon durene (g. v.) or its mono-sulphonio
acid.
Salts.— NaA'aq: needles, v. sol. hot water.—
KA'aq: similar to the preceding. — AgA' aq :
sparingly soluble white plates.— BaA' aq : plates,
sparingly sol. cold water (K. a. P.). — BaA'j : thin
prisms; sol. hot water, si. sol. cold (J.).
Amide CnMBsiSO^Nn^): [172°] (J.);
[179°] (K. a. P.) ; needles or very small pnsms ;
v. sol. alcohol.
if^-Cumene sulphonie acid OsHjMesSOsH
[1:2:4:5]. [112°]. Formed by dissolving <li-
cumene in cone. HjSO, at 80°, and crystallised
from dilute H^SOj (Jacobsen, A. 184, 199).
Cubes, si. sol. dilute H^SO^. Converted by
potash-fusion into C.HjMej(OH)COjH, whence,
by distillation with lime, m-xylenol CjHjMejCOH)
[l'3-4] is got. Fusion of the K salt with sodium
formate gives C,-E^Me,.CO^K (Eeuter,B. 11,29).
Vol.. II.
By the action of bromine upon the aqueous
solution 76 p.o. is converted into bromo-pseutlo-
oumene GJi,Ue,'BT [1:2:4:5], the remainder
.yielding bromo-pseudo-oumene-sulphonio aoM
CsHHejBr.SOsH [1:2:4:3:5] (Kelbe a. Paths, B.
19,1546). , -
Salts. — NaA' 5aq : transparent plates, loses
4aq in the air.— NaA'aq: white plates (from
cone! solution). — KA' aq : sparingly soluble
prisms.-^AgA' aq : sparingly soluble needles. —
BaAV S. 4-5 at 11-5° (J.).— BaA'j aq (Fittig a.
Ernst, A. 139, 188).
Chloride CjHjMejSOjCl. [61°]. Mono-
clinic prisms (from ether).
Amide CsHjMe,SOjNHj. [176°] (K.a.P.);
[181°] (Jacobsen, B. 19, 2513). S. -014 at 0° ;
■26 at 100°. Large prisms, sol. hot, si. sol. cold
alcohol. Cone. HOI at 176° splits it up into
NH„ H^SOj, and ij'-cumene. Potassium perman-
ganate gives CsHj(C0jH)Me2(S0jNHj) [1:2:4:5],
CsHj(C0jH).,Me(S0jNH2) [1:4:2:5], and finally
CsH2(COjH)3(S02NH2) (Jacobsen a. H. Meyer, B.
16, 190). By heating with a small quantity of
HCl there is formed (CjHjMejSOjjjNH [177°],
which is soluble in alkalis.
Gumene-(a)-salphonic acid 0,H,(03H,).S03H.
Isopropyl-benzene sulphomc acid. Formed in
largest quantity by sulphonating cumene in the
cold. By warming to 100°, or by several weeks'
standing with the excess of H^SO^ it isin great
part converted into the (i3)-aoid (Claus a. Tonn,
B. 18, 1239). Small deliquescent scales. Potas-
sium permanganate in presence of KOH forms
(CH,)2C(0H).0sH4.S0iH(E. Meyer, A. 219, 300)
Salts. — KA'. — BaA'^aq: lamins. S. 4-6 at
16°, 5-6 at 60°, 50 at 100°.— PbA'j aq : pearly
scales.— OaA'j 2aq.—SrA'j 2aq. S. 100. On
heating the solution saturated in the cold to
100° a crystalline pp. of SrA', is formed. —
MgA'j 7aq.— AgA'.
Amide OsH^Pr.SOjNHj. [108°] (M.; Spica,
a. 9, 433) ; [112°] (0. a. T.). Converted into
p-oxy-benzoic acid by treatment with KMnO,
and fusion of the product with potash.
Cumene-(i3)-sulphanic acid C,H4(C3H,)SO,H.
Formed, together with a smaller quantity of the
(ci) -sulphonie acid, by heating cumene with an
excess of ordinary H^SO, on the water-bath (Claus
a. Tonn, B. 18, 1289 ; Spica, (?. 9, 433). Small
needles. V. sol. water. By fusion with sodium
formate it is converted into a cuminic acid which
gives phthalic acid on oxidation (Claus a. Schulte, '
B. 19, 8012).
Salts. — ^A'2Ba3|aq : small needles; S. 20 at
16° ; more soluble than the Ba salt of the preced-
ing acid.- A'jPb 2aq : easily soluble microscopio
needles. — A'jMg 8aq : soluble pearly plates. —
A'2Zn7aq: easily soluble glistening needles.—
A'jCu 8aq : easily soluble large green needles.
Chloride C,H„.SOjCl: yellow oil.
Amide C,H„.S02NH,: [127° unoor.] (0. a.
T.); [96°] (S.); ''glistening needles.
»-Cumene snlphonlc acid Cs£[,,Pr.SO,H. ,
From w-oumene and H^SO,. According to P^-
tern6 a. Spica (0. 8, 408) both the 0 andp acids
are formed.
Salts.— KA'^aq (from alcohol).— CaA',—
BaA'j (Fittig, A. 149, 830).
Amide 0,H,Pr.SOjNH,. [110°]. Scales
(from water) (B. Meyer, A. 219, 29f ). •
290
CUMENOL.
t^-CTTMEBrOI C,Hj{CH,),OH[5:4:2:l]. [72°].
(235°). H.F. p. 68,540 {Stohmanh, J. or. [2] 34,
318)..
FormaUon. — 1. Formed by diazqtising rfi-on-
midine f62°] and boiling the diazo- compound
with water (Liebermann a. Kostanecki, B. 17,
885 ; Auwers, B. 17, 2976 ; Krohn, B. 21, 884).
2. By fusing i^-cumene sulphonici acid with KOH
(Beuter, B. 11, 29).
Properties. — Slender flexible needles, very
volatile with steam. Insol. cold water. FejClu
does not colour its solutions. Gives a bronio-
derivative [32°] and a di-bromo-deriv-ative [150°].
Benzoyl derivativeOgB.2Me3{OBz). [63°].
H.P. 87,240 (Stohmann, J. pr. [2] 36, 8).
Methyl ether C,H2(CH3),OMe. (214°)
(H.) ; (211°) (Auwers, B. 18, 2657) ; colourless
liquid. Formed by heating sulphate of diazo-
pseudo-cumene with methyl-aleohol (Hofmaun,
B. 17, 1918).
Ethyl ether C^'EiiCashOEi- (224°); co-
lourless liquid. Formed by heating sulphate of
diazo-pseudo-cumene with ethyl-aloohol.
Isoamyl e^^ier CbH2(CH,),OC5H:„ : (265°).
Sulphate CsB^UeaiOSOtB.). From i)/-cu-
menol and HjSO, (Eeuter, B. 11, 29). Small
crystals; decomposed by water into if-oumenol
and H,SO, even in the cold.. — BaA'j: slightly
EolubW leaflets.— KA'.—ZnA'j.
iJ-.Cumenol C,H2Me,(OH)[l:8:4:2]. [62°].
(233°). Formed from pseudo-oumene-sulphonic
acid (1:3:4:2) by KOH fusion (Jacobsen, B. 19,
1223). Long needles (from ether). FejClj gives
no colouration.
;|/-CumeD0lC„H2Me,(OH). [95°]. (231° i.V.).
From the corresponding oamidine [36°] bydiazo-
reaetion (Edler, B. 18, 630). Formed also by
fusing the corresponding sulphonio acid with
potash (Jacobsen, B. 19, 1219). Long prisms.
Gives no colour with Fe^Clj. It gives a di-bromo-
derivative [152°].
if'-Cumenol C,H2Me3(0H). (217°). From the
xliazo- compound of <(/-oumidiue (224°) by boiling
with dilute H^SO, (Engel, B. 18, 2230).' Oil.
Gives no colouration with FejCl,.
■ o-Cumenol OjH^Pr.OH. o-Isopropyl-pheru>l.
[15°]. (212^1. v.). S.G. 2 1-0124. From o-onmi-
dine by displacing NH2 by OH through the
diazo- reaction (Fileti, 0. 16, 113). Formed also
by potash-fusion from cumene o-sulphonio acid
(Spica, G. 9, 433). Its aqueous solution is
coloured violet by FejClj. It gives a bromo- and
a tri-nitro- derivative. Sodium an^ CO^ gives
cumenol carboxylic acid and di-oxy-di-isopropyl-
diphenyl-oarboxylio acid. FBr, gives bromo-
cumene and (CBH4PrO)gPO (0. 378 at 280 mm.),
whence alcoholic KOH forms (G,B.^xO)i{E.O)^0.
Acetyl derivative OsH^PrOAo. (229°).
S.G. 1-03. Liquid, decomposed by prolonged
boiling with water.
Methyl ether C„H4?rOMe. (199° cor.).
Ethyl ether OeH^PrOEt. (209° cor.).
S.G. 2 -9444.
p-Cumenol C5H,Pr(0H) [1:4]. [61°]. (229°
cor^. From cumene ^-sulphonio acid by potash-
fusion (Patern6 a. Spica, G. 6, 535). Formed
also by heating C„H3(C0.,H)?r(0H) [1:3:6] with
cone. HCl at 180° (Jesurun, B. 19, 1416).
Fe^Cls colours the alcoholic solution green.
Acetyl derivative C,H,?rOAo. (244°
wr.). S.G, 2 1-026.
Methyl ether C,H,5r.0Me. (213° oor.).
S.G. 2 -962.
Ethyl ether G^n^.G&i. (215°). 8.0.9
1'026. V
o-w-Cnmenol CjH4Pr(0H)[l:2]. o-Propyl-phe-
not (c. 225° cor.). S.G. 2 1-015. From allyl iodide
and phenol in presence of zinc and aluminium
foil (P. F. Frankland a. T. Turner, C. J. 43,
358) : C8H,OH + CsH5l = HI + C,H5.0„H,OHand
OsHs-CoHjOH + 2Hi = C,H,.0eH,OH -1- 13. Formed
also by fusing the corresponding sulphonic acid
with potash (Spica, G. 8, 418). Liquid; its
aqueous splution is turned violet by FejOl,. CO,
acting on its sodium derivative at 140° gives o-
oxy-propyl-benzoio acid.
Methyl ether CBH^Pr.OMo. (208° cor.),
S.G. a -9694.
??i-TC-Cumenol C8H4Pr(OH)[l:3]. [26°]. (228°
i.V.). From oxy-m-cuminic acid and cono.
HClAq at 190° (Jacobsen, B. 11, 1062). Crystals,
V. si. sol. water. Fe^Olg colours its alcohoUo so-
lution green.
i)-»i-Cumenol OaH4Pr(OH)[l:4]. (231° cor.).
S.G. 2 1-009. Formed by fusing the correspond-
ing M-cumene sulphonic acid with potash (Spica,
G. 8, 411). Formed also by diazotising amidq-
propyl-benzene and boiling the product with
water (Louis, B. 16, 109). ,Oil. SI. sol. cold
water, v. sol. alcohol and ether. FOjClj gives at
first a violet and then a permanent green coloura-
tion. CO2 on the Na derivative gives ^-oxy-»i-
cuminic acid.
Acetyl derivative C5H4Pr(OAo). (243°
cor.). S.G. 2 1-029 ; 122 -942.
Methyl ether C3H4Pr(OMe). (215° cor.).
S.G. 2 -964; 122 -912. Tields anisic acid on oxi-
datioh.
The same ether appears to be formed, to-
gether with anisole, by the action of boron-fluor-
ide on anethol (Landolph, B. 13, 145).
Isomerides of camenol v. Mesitoii and Hbmi-
MEIiLIIHOIi.
Berivatives of cnmenol v. AiiiDo-cnMBiioi^
Bbomo-cumenol, NiiBo-cnMENOL, &a.
Si-cumenol v. Di-oxY-Di-oDMii..
CUMEITOL-CAKBOXYLIC ACID v. OxY-oo-
MINIC ACID.
CTJMENOL SULPHOIflC ACID
CsH3Pr(OH)(S03H). From cumenol and H^SO,
(Jacobsen, B. 11, 1062). The Ba salt forms crys-
talline crusts. Its solution is coloured violet by
Fe,Cl,.
CUHENTIi. A name sometimes applied to
the radicle cumyl C,H„.
CTJMENYI-ACEYLXC ACID v. CtrMYi,-AOBYiio
Acn>.
CTTMIC V. CuMiNic.
CTJMIDIC AOID V. Xylekb dioakboxtuo acid.
o-CUmiDINE CjHijN i.e. C^B.^?TQS^^\l■.i].
(215°). Formed by distUling amido-ouminio
acid with baryta (Fileti, G. 13, 379). Formed
also, together with the following, by nitrating
cumene and reducing the product (Constam a.
Goldsohmidt, B. 21, 1157). Converted by passing
over red-hot PbO into indole.
Salts .— B'HCl : large prisms.— B'SjOjOj aq:
[173 ] ; long prisms.
Acetyl derivative C,H„NHAo. [72°].
Tufts of needles.
p-Cumidine C„H,Pr(NH,)[l:4]. (225°) (N.);
(219°) (0. a. G.). S.G. -953. Formed by reducing
CUMINIC ACID.
291
nitro-ouiaene (from ouminio acid) (Nioholson,
A. 65, S8). Fiom aniline, isopropyl alcohol,
and ZnOla at 270° (Louis, B. 16, 111). May be
solidified by cold. — B'HOl. — B'jH^PtCl,. —
B'HNOa.— B'jH^SO,.— B'jOjNj : long needles
(Hofmann, A. 66, 145). Ox alate B'2HA04 2aq:
[159°] (Oonstam a. Goidsohmidt, B. 21, 1157).
Acetyl derivative C|,H,,NHAo [102°].
<|i.Cuinidine 0^2Me3(NHj[l:3:4:5]. [36°].
Formed by reduction of nitro-(pseudo)-oumene
[20°] (Edler, B. 18, 630). Colourless crystals.
BasUy volatile with steam.
Salts.— BUClifine felted needles.— B'HNOa!
small glistening plates. The oxalate and sul-
phate are sparingly soluble in cold water.
Acetyl derivative \194l°]; long prisms;
nearly insol. ether.
i(<-Cuniidine C,HjMe3(NHj)[l:2:4:5]. [68°]
(Auwers, B. 18, 2661) ; [63°] (H.). (235°). Crys-
talline solid.
FormaUon. — 1. Occurs in the crude cumidine
obtained by heating xylidine hydrochloride with
methyl alcohol at a high temperature under
pressure (Hofmann a. Martins, B. 4, 747 ; 13,
1730 ; Hofmann, B. 15, 2895 ; cf. Nolting a.
Forel, B. 18, 2680). — 2. By nitration and reduc-
tion of pseudooumene (Schaper, Z. 1867, 13).
Large prisms. Nitrous acid converts it into
CsK,Me3.N2.0jHMe3(NH,), whence may be ob-
tained CaH2Me,.N2.0eHMe3N,^r3 [124°],
C3H,Me3.N,.C„HMe3.N. [91°],
C3H3Me3N<;|[>C3HMe3 [85°] and
C3HjMe3.Ns.CeHMe,.N2H [153°] (Zinoke a.
Jaencke, B. 21, 546).
Salts. — ^B'HCl: thick prisms, sol. water, si.
sol. dilute HCl.— B'.^HjCljPtOl4 : fine needles,
' decomposed by boiling water (De Coninok, Bl.
[2] 45, 181).— B'jHjSnCl^ : laminae.- B'H3P04
(Lewy, B. 19, 2729).
Acetyl deriudiiiJeCjHjMej.NHAc: [164°];
(360°) ; thick white needles ; v. sol. alcohol and
acetic acid, insol. water (Auwers, B. 18, 2661 ;
cf. Nolting a. Baumann, B. 18, 1146).
Formyl derivative CaH2Me3.NH.COH:
[121°] ; colourless prisms ; v. sol. alcohol and
ether, nearly insol. water.
Thioformyl derivative
0,H2Mej.NH.CSH. Formed by heating the for-
myl derivative with PjSs (Senior, B. 18, 2296).
t|'-Cumidine CjH^Mea.NHj. (224°).
Preparatiim. — The solid hydrochloride ob-
tained by adding cone. HCl to crude ooml. cumi-
dine is basifled with NaOH and fractionated.
The fraction 0. 225°-227° is boiled with acetic
acid for twelve hours, and the product crystal-
lised from alcohol ; a small quantity of acetyl-
mesidine crystallises out, and the mother-liquors
contain the acetyl derivative of the new cumi-
dine, which is obtained pure by several crystal-
lisations from water, and finally converted into
the base by saponification with solid KOH.
Salts.— B'HCl : white needles ; v. sol, water,
nearly insol. cone. HCl. The platino-ohloride is
insol. water, si. sol. alcohol. The nitrate is less
soluble than the sulphate.
Acetyl derivative CgH^Mog.NHAc :
[112°] ; crystalline solid (Engel, B. 18, 2229).
Cumidine C3HjMe3(NHj)[l:2:3:4] ? J3emi-
melUthidine ? Amido-c-tri-methyl-henzene.
(240?). From o-xylidine hydrochloride aad
MeOH at 310° (Nolting a. Forel, B. 18, 2680).
Liquid.
Acetyl derivative C,H2Me3(NHAc).
[above 180°].
■(--Cumidine 03H2Mea.NHj[l:3:4:2]. (236° un-
oor.). Liquid at — 15°. Obtained from nitro-if'-
cumidine (from tri-nitro-i|'-oumene) by elimina-
tion of the NHj group by the diazo- reaction
and reduction of the nitro-if'-cumene [30°], which
is obtained with SnCl^ (Mayer, B. 20, 971).
Probably identical with the i|/-cumidine obtained
by Nelting and Forel (B. 18, 2680) by nucleal
methylation of the o-xylidine OeH,Me2NH2[^:3:l].
Acetyl derivative CeH2Me3(NHAc).
[186°].
ro-Cumidine v. Amido-fhenyl-fbopane, vol. i.
p. 179.
Isomeride of cumidine v. Pebnyl-fbofyl-
A.MINE.
CUMILIC ACID CjoHj^O, i.e.
(C,Hi(C,H,))2C(0H).C0jH? [120°]. Prepared
by fusion of cuminil with KOH ; yield 70 p.o.
(Bosler, B. 14, 326). Fine white needles. Sol.
alcohol, ether, and benzene, si. sol. water.
CUffllNAI-ACEIONE v. Methyl pbofyi.-
SIYEYL KETONE.
Si-cuminal-acetpne v. Di-PBOPYn-si-siYBYL
ketone.
cumindigo v. dl-isofkofyl-indigo.
CUHIHIC ALCOHOL v. CumNYL alcoroi..
o-TC-CUMINIC ACID C,„H,A ie.
CBHjPr(C02H) [1:2]. o-n-Propyl-Unzoie acid.
Mol. w. 164. [58°]. From phthalyl-propionio
acid, cone. HIAq (lOpts.), and red phosphorus
(Ipt.) (Gabriel a. Michael, B. 11, 1014). Slen-
der leaflets.
^-w-Cuminic acid CBH4.Pr(C02H) [1:4]. p-n-
Propyl-benzoic acid [140°].
Formation. — 1. From ^-bromo-«-propyl-
benzene, sodium, and COj (R. Meyer, J. pr. [2]
34, 102).— 2. From CeH^PrJr by oxidation (Pa-
tern6 a. Spica, B. 10, 1746).— 3. From C„H<Pr,.
and dilute HNO3 (H. KSrner, A. 216, 228).
Properties. — Lamina (from water) or needles
(from dilute alcohol). SI- sol. boiling water.
Volatile with steam. EMn04 gives terephthalio
acid.
Salts . — CaA'j 3aq : slender satiny needles. —
SrA'22laq.— BaA'j 2aq.— PbA'^ 2aq.— AgA'.'
Nitrite C,B.tBx.CN. [227°]. From ^-propyl-
phenyl thiocarbimide and copper powder at 220°
(Francksen, B. 17, 1229). Liquid. Saponified
by cone. HClAq at 200°.
o-Cuminic acid CsHjPr.COjH [1:2]. Formed
by fusing a salt of cumene-(^)-sulphouio acid
with an excess of sodium formate ; the yield is
10 p.o. Sublimable. Volatile with steam. V.
sol. alcohol, ether, &o., insol. cold wate^. Oxi-
dation with KMnO, gives o-phthalio acid. Its
alkaline salts are excessively soluble. — A'Ag:
insoluble white pp. — A'2Ca2aq: small soluble
needles. — A'jBa2aq:solubleneedles. — ^A'jMgeaq:
very solubleneedles.— A'jPbaq,: very sparingly
soluble white powder.— A'jCu 2iaq : very spar-
ingly soluble blue-green amorphous pp.
Chloride CjHjPr.COCl: yellowish oil, v.
sol. ether and chloroform.
Amide CjHjfr.CO.NHj : [124° unoor.];
small needles ; v. sol. alcohol and ether, v. si.
sol. water (Claus a. Schulte im Hof, B. 19,
8013).
u2
292
OUMINIC AOID.
X)-Iso-cumiiiio acid CjH,Pr{COJa) [1:4].
[117°] (M.). H.C.V. 1,239,000 (Berthelot a. Lou-
guinine, A. Oh. [6] 13, 383).
Formation. — 1. Frombromo-iso-propyl-benz-
ene, Na, and COj (E. Meyer, J.pr. [2] 34, 100).—
2. By the oxidation of ouminic aldehyde or oil
of cumin (Gerhardt a. Cahonrs, A. Ch. [3] 1, 70 ;
Beilstein a. Kupfler, B. 6^ 1184 ; A. 170, 302 ;
Lippmann a. Lange, B. 13, 1660; Meyer, A.
219, 244). — 3. Cymene when taken internally
passes into the urine as cuminic acid (Nencki a.
Ziegler, B. S, 749 ; cf. Hofmann, A. 74, 342).
Properties. — From water (3 pts.) and alco-
hol (1 pt.) it separates in triclinic needles:
b:6:c = -6742:1: -8072 J 0=86° 55', j8 = 101'' 12',
, y=ip6° 55' (Groth; cf. Panebianoo, Gf. 10, 81).
v. b1. sol. cold water, v. sol. alcohol and ether.
Converted into cumene by distillation over lime.
Chromic mixture oxidises it to terephthalic acid.
EMnOj forms, as an intermediate product, oxy-
propyl-benzoio acid (CH3)jC(OH).OsH,.C02H
(Meyer).
Salts. — BaA'22aq: lanunse. S. -996 at
20-5°.— CaA'j5aq: needles. S. -81 at 20-5°.—
MgA'j6aq: laminffl. S. -825 at 20-5°.— AgA'.
Ethyl ether -EtA.'. (240°). V.D. 6-65.
Phenyl ether FhA'. [58°]. Frompotas-
siam-phenol and the chloride of the aoid (Wil-
liamson a. Scrugbam, Pr. 7, 18): Also formed
by distilling cuminyl-salicylic acid (Kraut, J.
1858, 406 ; Ar. Ph. [2] 96, 271).
Eugenyl etherCfi,(C,'B^){OKe)A'. Tables
(Cahours, A. 108, 323 ; A. Ch. [3] 41, 491).
Anhydride (C5HjPr.CO)jO. Oil (Gerhardt,
A. 87, 77; A. Ch. [3] 37,304).
Peroxide (CsHj^r.CO)^- Needles (from
ether). Explodes when heated (Brodie, P. 121,
372; Pr. 12, 655).
Chloride C^K^i.COCl. (257°). S.G.151-07.
Liquid (Cahours, ^..70, 45 ; A. Ch. [3] 23, 347).
Amide OeH.Pr.CONHj. [154°] (F.); [c.
157°] (G.). Formation. — 1. By heating ammo-
nium ourainate (Field, A. 65, 49). — 2. From the
nitrile and alcoholic KOH. — d. From the anhy-
dride and NH, (Gerhardt, A. 87, 167).— 4. By
heating cuminic acid (164 g.) with potassium sul-
phooyanide (50 g.) for 5 hours with inverted con-
denser at 240°, and then for 1 hour at 800°. The
nitrile is formed at the same time (Fileti, 0. 16,
281). — 6. By the action of chloroformamide
0C(NH2)C1 upon cumene in presence of AljCl,
(Gattermann a. Schmidt, A. 244, 64; B. 20,
860). Properties. — Biaxial crystals, insol. cold
water, si. sol. ether, v. sol. alcohol and hot benz-
ene. When boiled with water and yellow HgO
it forms (OeH4Pr.CONH)2Hgljaq, which crys-
tallises in needles [190°].
Anilide CjHjfr.CONHPh. Long satiny
needles (from alcohbl). SI. sol. alcohol (Cahours,
A. Ch. [3] 23, 349).
Benzene sulphamide
C„H,?r.C0.NH.S02Ph. [161°]. From onminyl
chloride and the amide of benzene sulphonio
acid (Gerhardt a. Chiozza, A. Ch. [3] 46, 161).
Prisms. AgKO, and a little NH, give needles
of C,H,5r.C0.NAg.S0jPh, which forms a crys-
talline compound with NH, ' (1 mol.). The
benzoyl derivative OjH^Pr.CO.NBz.SO^h
is formed as a crystalline mass by treating
AgKBz.SO,Ph with cuminyl chloride.
o-Oxy-bemamide
0,H4?r.CO.NH.CO.C8H4.OH. From salicylamide
and cuminyl chloride. Needles.
Nitrile C,H,?r.CN. (244° i.V.). S.G. "
■765. Formed by heating the amide (Field,
Mem. Chem. Soc. S, 408 ; A. 65, 51), or by heat-
ing cuminic acid (2 mols.) with ECyS (1 mol.)
(Letts, B. 5, 674 ; Fileti, Gf. 16, 282). Formed
also by treating potassium cuminate with CyBr
(Cahours, A. Ch. [3] 52, 201; A. 108, 326).
Liquid, si. sol. water, v. e. sol. alcohol and ether.
<f'-Camimc acid C,H2Me,(C02H) [1:2:4:5].
Durylie acid. Tri-methyl-bemoic acid. [149°].
Formation. — 1. By boiling durene with dilute
ENO, (Jannasch, Z. 1870, 449) or with the cal-
culated quantity of CrO, in HOAc (Gissmann, A.
216, 205). — 2. By fusing potassium iff-cumene
sulphohate with sodium formate (Beuter, B. 11,
31).-^3. From the nitrUe (Nef, A. 237, 3).—
4. By hydrolysis of its amide (v. infra).
Preparation. — Durene is boiled for 3 or 4
hours with dilute HNO, (1 vol. of HNO, (1-4 S.G.)
to 3 vols, water). The product is fUtered off,
extracted with NajCO,, and the solution precipi-
tated with HCl. The crude acid is filtered off,
treated with tin and ECl to remove nitro- com-
pounds, and distilled with steam. The yield is
40-50 p.c. of the durene (Nef, B. 18, 2801).
Properties. — Needles (from benzene). V. si.
sol. boUing water, v. e. sol. alcohol and ether.
Volatile with steam.
Salts. — CaA'j 2aq.— BaA'2 7aq : prisms.
Amide CsHjMej.CONBL,. [201°]. From i^-
cumene and chloroformamide Cl.CONE, in pre-
sence of AljCl, (Gattermann, A. 244, 54). Needles
(from dUute alcohol).
Nitrile [58°]. (250°). Formed by the ac-
tion of GuSO, and KCN upon diazo-pseudo-
cumene (Haller, B. 18, 93). Long colourless
needles. V. sol. alcohol, ether, benzene, and
ligroin, insol. water.
((i)-Ciiininic acid C,H2Mea(C02H) [1:2:3:5].
[216°]. (a)-Isodtirylie acid. Formed together
with the (18) and (7) isomerides by oxidation of
isodurene with HNO,. Distillation witK lima
yields hemimeUithol. — A'jBa 4aq: long fine
needles. — A'Ca5aq (Jacobsen, B. 16, 1855;
Bielefeldt, A. 198, 384).
(/3)-Caminic acid C,HjMe3(C0jH) [1:3:5:2].
{ff)-Isodwrylic acid. MesityUne carboxyUe acid.
[151°]. Formed together with the (a) and (7)
isomerides by oxidation of iso-durene with
HNO, (Jacobsen, B. 15, 1855). Distils without
decomposition. Thick glistening prisms. On
distillation with lime it gives mesitylene.
CaA'2 2aq : microscopic needles.
(7)-Cnnunic acid CjH3Me3(COjH) [1:2:4:6].
ffi-Cimiene carboxyUc add. (y)-IsoduryUc acid.
[86°]. Formed' together with the (a)- and (B)-
isomerides by oxidation of isodurene with HNO,
(Jacobsen, B. 15, 1855). Distils without decom-
position. Volatile with steam. Needles. Sol.
alcohol, ether, and hot water, nearly insol. cold
water. On distillation with lime it gives pseudo-
cumene.
Salts. — k'K": extremely soluble amorphous
solid. — A'^Ba" : oncrystallisable. — A',Ca 2aq :
microscopic needles.
c-Onminic acid C^Meg(COjH)[l:2:3:4]. 2Vt.
methyl-benzoic add. [168°]. Formed by oxida-
tion of the conseontiTe tetra-methyl-benzeiM
CUMINURIC ACID.
(prehnitene) by boiling for 12 hours with dilute
HNO,. Long glistening prisms. V. e. sol. hot
alcohol. Volatile with steam. By distillation
with lime it yields the consecutive tri-methyl
benzene (hemimellithene) (Jacobsen, B. 19, 1214).
Beferences. — AMiDO-cnMimo Aom, Bromo-
cnunno acid, NirBo-onMiuio acid, Ojct-cuminio
ACID.
CUHINIC ALDEaYI)EC,oH,20i.e.
CeH,(OaH,).OHO [1:4]. Curmnol. Isopropyl-
henzoio aldehyde. Mol. w. 148. (287'5° cor.)
(Schiff) ; (222" cor.) (Lippmann a. Streokor, Sitz.
W. [2] 78, 570). S.G. 2 -9832 ; 13i -9727. V.D.
6-24 (oalc. 5*13). Occurs, together 'with cymene,
in oil of cumin (from Cuminum Gyminwm), and
in the volatile oil from the seeds of the water-
hemlock {Cicuta virosa). It is separated from
these oils by EHSO, (Gerhardt a. Cahours,
A. Oh. [3] 1, 60 ; Bertagnini, A. 85, 275 ; Kraut,
A. 98, 866; Trapp, A. 108, 386). Formed by
boiling OiHj.CgH^.CHjGl with lead nitrate and
water (Errera, G. 14, 278). Formed also by
treating cymene (1 mol.) with CxOju\ (3 mols.)
in CSg, without cooling, and decomposing the
product with water (Etard, O. i2.,90, 634). The
cuminic aldehyde (220°) so formed is perhaps
identical with ordinary cuminic aldehyde. On
oxidation it gives a cuminic acid [129°], whence
potash-fusion gives f-toluic acid.
Properties. — Oil, smelling like oil of cumin.
Oxidises in the air, becoming resinous.
Beactums. — 1. Cold fuming HNO, gives j>-
iso-cnminio acid. Hot HNO, forms nitro-iso-
cuminio acid. — 2. Chromic acid mixture gives
^-iso-cuminio and finally terephthalic acid. — 3.
01 and Br act by substitution. — 4. NH, forms
hydroonmin-amide a thick liquid (Gerhardt
a. Cahours; Borodin, B. 6, 1253). According
to Uebel [A. 245, 303) it is a stellate mass [65°]
which may be reduced by sodium amalgam to
cuminyl-amine and di-cuminyl-amine, and is
converted by dilute acids into NH, and cuminic
aldehyde. Sieveking {A. 106, 357) could not
obtain it. Aqueous NH, at 130° forms an isome-
ric base CjuHjjNj [205°] which forms a sparingly
soluble sulphate [192°]. — 5. Ammonium sulphMe
forms (G,„H,^S)x. — 6. Boiling fflgM«cwts and alco-
holic potash form cuminyl alcohol and ;-iso-
ouminic acid. — 7. Potash-fusion gives ;p-iso-cu-
minic acid and cymene. — 8. Heating with potas-
sium forms C,„H„OK(?) (Chiozza, A. 87, 302;
ef. Church, P. M. [4] 25, 622).— 9'. In ethereal
solution it is partly converted by treatment with
sodium amalgam into the sodium derivative of
hydrocuminoinC„HjPr.OH(OH).CH(OH).CeH4Pr
[135°] (M. Wallaeh, A. 226, 78; ef. Claus,
A. 137, 104).— 10. Acetamide at 175° gives
C.Hj(C3H,)CH(NHAc)j [212°] (Raab, B. 8,
1150). — 11. Bemam^ide gives in the same way
C.H,(C,H,}CH(NHBz)j [224°] which crystallises
from alcohol' in needles, insol. water (R.). —
12. 'Ethylene - diamine at 120° gives
(0,H,.d,H,.CH:N)AH4 [64°] (Mason, B. 20,
267). — 13. Hydrogen cyanide and HCl give
C.H4(0,H,).CH(OH).00jH.— 14. Distillation over
ZnCl, gives cymene (Iiouguinine, Z. 1867, 351).
16. With butyric aldehyde and butyric anhydride
it gives C3H,.CeH,.CH:CEt.C02H (Perkin).
Ooj»6i«otMm.— 0,jH,j(OH)(SOaNa) aq :
needles, sol. water, insol. cold alcohol, ether,
and aqueous NaHSO,.
Di-methyl-amido-anilide
C^,(03H,).CH:N.CjHj(NMe2) : [99°] ; small glis-
tening crystals (from alcohol) (Nuth; B. 18,
573).
Oxim C,„H,j.NOH. [52°]. Formed by the
action of hydroxylamine on cummio aldehyde
(Westenberger, B. 16, 2994). SI. sol. water.
Derivatives of cnmiuic orthaldehyde.
Diacetyl derivative OsH4(CjH,)CH(OAo)2.
Obtained by the action of silver acetate on
OsH4(C3H,)CHOl2 (from cuminolandPOlj). Crys-
tals (Sieveking, A. 106, 258).
Di-benzoyl derivative
CeH4(C,H,).CH(0Bz)j. [88°]. Needles (Tutt-
schefi, A. 109, 368).
Di-thymyl derivative
C,H,(C3H,).0H(00,„H,3),. [157°]. From
C„Hi(CsH,).CHCla, thymol, and KOH (Engel-
hardt a. LatschinofE, Z. 1869, 43). Tables.
Cnminoin Cj„Hj,02 i.e.
C„H,(0,H,).C(0H)H.C0.C,H,(C3H,). [101°]. Pre-
pared by boiling cuminic aldehyde with alcoholic
KCN ; the yield is about 45 p.c. (Bosler, B. 14,
823). Slender white needles; sol. alcohol,
ether, and benzene, si. sol. water and ligroin.
It reduces Fehling's solution in the cold. Alco-
holic KOH gives a violet colouration.
Acetyl derivative C2„H230(0Ac) : [75°];
' tables or prisms (Widmann, B. 14, 609).
Hydrocuminoln
C,H,.CsH^.CH(OH).CH(0H).CaH4.CsH,. [135°].
Formation. — 1. From cuminoin and sodium
amalgam. — 2. From cuminic aldehyde by treat-
ing its ethereal solution with sodium amalgam
or with alcoholic HCl and zinc (Claus, A. 137,
104 ; Eaab, B. 10, 64).— 3. Its di-acetyl deriva-
tive is formed by heating cuminic aldehyde with
NaOAc and AcjO at 160° (Widmann, B. 19, 266).
Properties. — Small needles (from dilute alco-
hol). Insol. water. Oxidised by cone. HNO3 to
cuminoin. Pentachloride of phosphorus gives
C3H,.C.H,.CHC1.0HC1.C3H4.C3H, [186°].
Di-acetyl derivative OjoHjjAojOj. [144°].
Beozy-cnminoin
C3H,.CeH,.CHj.C0.C3H4.C,H,. [68°]. From cu-
minic aldehyde by treatment with zinc and alco-
holic HCl (B.). Slender laminss (from dilute
alcohol) ; v. si. sol. water.
Cuminil CjoHijOj i.a.
C3H,(C3H,).CO.CO.C3H,(0,H,). [84°]. Yellow
prisms. Sol. alcohol, ether, and benzene, v. si.
sol. water. ■ Distils undecomposed. Prepared by-
oxidation of cuminoin with chlorine. On fusion
with caustic potash it gives rise to cumUic acid
(C3H,.0,H,)jC(0H).00jjH [120°] (Bdsler, B. 14,
325).
Isocumiiiio aldehyde 0,„H,20. [80°]. (220°).
Formed together with the liquid aldehyde
by the action of water upon the compound
C,^n2Cr02Cl2, obtained from cymene derived
from turpentine (Etard, A. Ch. [5] 22, 269). Solid
resembling camphor. Oxidised by the air to a
cuminic acid [61°].
CITMINOL V. CcMnno aldbhyde.
CUMINTJEIO ACID O.JBE.sNO, i.e.
[4:l]C3H4(C,H,).CO.NH.CHj.COjH. [168°]. Oo.
curs in the urine of animals who have been given
doses of cymene (Jacobsen, B. 12, 1612). Pre-
pared by the action of cuminyl chloride on gly-
coobl-silver (Cahours, .^. Ch. [3] 63, 356). Glisten-
ing scales or large plates. Insol. cold water, v.
294
CUMINURIO ACID.
Eol. hot water and alcohol. On heating with
BCl to 120° it deoomposes into glycocol and
cuminio acid [117°].
Salts. — BaA'jaq; leaflets or flat needles,
S. '45 at 6°. — CaA'j 3aq : fine needles, si. sol.
cold water. — KA' and NaA' : very soluble fine
needles.
DI-CUMINYL CjoHjB i.e.
C3H,.C„H4.CH2.CH2.C,H4.C3H,. (above 360°).
From ouminyl chloride and sodium (Cannizzaro
a. Bossi, A. 121, 251). Plates.
CUMINYL ALCOHOL C,„H„0 i.e.
CjHjJJr.CH^OH [4^:1]. Mol. w. 150. (247° cor.).
S.G. -- '978. Formed, together with cuminic
acid, by boiling cuminic aldehyde with alcoholic
potash (Kraut, A. 92, 66 ; 192, 224 ; Fileti, <?.
14, 498). Liquid, miscible with alcohol and ether.
Boiling with zinc-dust converts it into Ji-oymene,
the ?r changing to Pr. Boiling alcoholic KOH
forms cuminic acid and cymene. Boiling with
small quantities of dehydrating agents converts
it into di-cuminyl oxide.
CUMimrL-AMIBO-FHENOL
H0.CaH,.NH,CHa.C5HiPr. Oxy-phenyl-cuminyl-
amine. [108°]. Formed by reducing with sodium
amalgam the product obtained by the action of
cuminol on amidophenol (Uebel, A. 245, 297).
Greyish white plates. V. e. sol. alcohol, ether.
, Salts.— C,BH„NH(ONa). V. sol. water, giv-
ing a red solution. — B'HOl. White plates. V. sol.
alcohol, hot water, m. sol. cold water.
Nitrosamine C,jH,;OHN.NO. Yellowish
brown crystalline substance. V. sol. alcohol,
ether.
CUMINYL-AMINE C„H,5N i.e.
C5Hj(C3Hj).CH2.NH2[l:4]. JSxo-amido-cumene.
Jaqpropyl-bemyl-amine. (226° at 724 mm.).
Prepared by reduction of the oxim of cuminio
aldehyde, C„H4(C3H,).CH:NOH (5 pts.), with so-
dium amalgam (150 pts.) and acetic acid (12 pts.)
in alcohoUc solution at 40°-50° ; the yield is
good (Goldschmidt a. Gessner, B. 20, 2413).
Formed also, together with di- and tri-cuminyl-
amine, by heating cuminyl chloride with alco-
holic NHj at 100° (Eossi, C. B. 51, 570;
' A. Suppl. 1, 141). Also from thio-cuminic amide
C3H,.C5H4.0S.NHj, zinc and alcoholic HCl
(CzumpeUk, B. 2, 185). Colourless liquid, of
basic smell. Nearly insol. water. Absorbs COj
from the air, and solidifies to a crystalline car-
bamate.
Salts. — B'HOl : glistening colourless plates,
V. sol. water and alcohol. — B'jHjCl^PtOl^ : nearly
insoluble yellow pp.
Acetyl derivative C,„H|s(NHAc) : [65°];
pearly plates ; v. sol. alcohol, ether, and benzene,
si. sol. hot water and hot ligroln.
Di-cuminyl-amine (OsHj.OjHJjNH. [168°].
(o. 290° at 100 mm.). Formed as above (E.).
Formed also by the action of sodium amalgam
on the product of the action of dry NH3 on cu-
minic aldehyde (Uebel, A. 245, 309). Crystals,
insol. water, v. sol: alcohol and ether. Forms
a crystalline nitrosamine.
Salts. — ^B'HCl: plates (from alcohol); v.
d. sol. cold, m. sol. hdt, water, v. e. sol. alcohol.
— B'jHjPtClj ; yellow needles.
Tri-ouminyl-amine (03H,.OeH4)jN. [82°].
Formed as above (B.). Its hydrochloride forms
needles, insol. water.
CUUXNYL-CABBAMATE
NH2.CO2.CHj.CjHj.OsH,. [89°]. Formed, to-
gether with w-chloro-cymene, by passing cyano-
gen chloride into cuminyl alcohol (Spica, O. 5,
394). Prisms, not volatile with steam. SI. sol.
cold, V, sol. hot, water.
CUKIITYL CHLOSISE v. w-Ohlobo-cxuene.
CITMINYL-ETHYL OXIDE CsHjPr.O.Et.
(227°). From , u-ohloro-cymene and alcoholic
KOH (Errera, 0. 14, 282).
CUBIIITYLISENE.ACETONE
CH3.C0.0H:CH.CeH,Pr. (181° at 23 mm.). From
acetone (20 pts.), cuminic aldehyde (20 pts.),
water (300 pts.), alcohol (170 pts.), and NaOH
(2 pts.) in the cold (Claisen a. Ponder, A. 223,
147). Thick yellowish oil.
Di-ciiminylidene-acetone(08HjPr.OH:CH)2CO.
[107°]. From cuminic aldehyde (20 pts.), ace-
tone (4 pts.), water (300 pts.), alcohol (250 pts.),
and NaOH (2 pts.), m the cold (0. a. P.). Long
light-yellow prisms (from alcohol).
CUmiNYLIDEKE-AMIDO-PHElTOL
HO.C,H,N:CH.CeH,Pr. [183°]. Formed by the
action of amidophenol on an alcoholic solution
of cuminol (Uebel, A. 245, 296). Green pris-
matic needles (from alcohol). Is converted by
sodium amalgam into cuminyl amido-phenol.
CUMINYLIDENE CHLOBISE v. uvu-Hi.
CHLOKO-CYMENE.
DI-CUMINYLIDENE-ETHYLEWE-DIAMINE
C^H2,N2i.e. 02H4(N:CH.C,H,Pr)2. Di-isopropyl-
bemylidene-eth/ylene diamine. [64°]. Formed
by heating ethylene diamine (1 mol.), with
cuminic aldehyde (2 mols.) to 120°. Long white
needles. Easily soluble in alcohol, benzene,
chloroform, and petroleum-ether. Decomposed
into its constituents by acids or by heating with
water (Mason, B. 20, 270).
CUMIN YLIDENE -DI-METHYL-p-PHENYL-
ENE DIAMINE Pr.C.H.CHiNCsHjNMej. [100°].
Formed by the action of Pr.CjHj.CHO on di-
methylaniline (Uebel, A. 245, 299). Lemon-
yellow ntedles. V. sol. alcohol and ether, insol.
water. Is decomposed by acids or alkalis into
its components.
CUMINYL -DI - METHYL-^ -PHENYLENE
DIAMINE Pr.CaH,.CH2.NH.0sH4.NMe2. [39°].
Formed by reducing cuminylidene-di-methJyl-jp-
phenylene-diamine with sodium amalgam in an
alcoholic solution (Uebel, A. 245, 300). Colour-
less prismatic plates. V. e. sol. alcohol and ether.
Gives a nitroso- derivative [87°], crystallising in
yellow needles. The hydrochloride is v. sol.
water, v. e. sol. alcohol, and si. sol. ether.
DI-CUMINYL OXIDE C2„H„„0 i.e.
(C„H,?r.CH2)20. (350°).
Formation. — 1. From OsHjPr.CHjONa and
OjHjPr.CHjCl (Fileti, 0. 14, 496).— 2. By distil-
ling cuminyl alcohol with dilute H2SO4. — 3. One
of the products of the action of alcoholic potash
on cuminic aldehyde.
Properties.— Oil. Boils at 350° with partial
decomposition into cuminic aldehyde and cymene.
CUMINYL-PHENOL 0,„H,gO i.e.
C3H,.C„Hj.CH2.C„H40H. (300°) at 60 mm.
Formed by treating a mixture of phenol and
ouminyl alcohol with HOAc and HjSO, (Paternd
a. Fileti, O. 5, 383).
CUMINYL THIOCABBIMIDE
C^,Pr.CH,NCS. (245°-270°). From di-oumi.
nyl-thio-urea and PgO, (Baab, B. 10, 52).
CUMYL PEOPYL-BENZYL KETONE.
296
CTTMINYL-THIO-TTREA
C^H,(C3H,).CH,.NH.CS.NH.j[l:4].Prop2/Z-6«»iz3/Z-
thio-urea. [o. 110°]. Formed by mixing solutions
of ammonium sulphocyanide and oumyl-amine
hydrochloride, and evaporating to dryness. Co-
lourless plates (Goldschmidt a. Gessner, B. 20,
2416).
Si-cnminyl-thio-xirea
{0,H„{C3H,).CH2.NH}„GS[1:4]. Di-jp-propyl-di-
hemyl-thio-ureat [128°]. Formed by the action
of alcoholic sulphide of carbon upon oumylamine
C„Hj(C3H,).CHj.NH,. Glistening needles (Eaab,
B. 10, 53 ; Goldschmidt a. Gessner, B. 20, 2415).
CUMINYL-liKEA 0„H,50Nji.e.
CBHj(CaH,).CHj.NH.Cb.Nn, [1:4]. Propyl-ben-
zyl-urea. [135°]. Formed by warming a solu-
tion of oumylamine hydrochloride with potassium
cyanate. Slender white needles (from hot water)
(Eaab, B. 8, 1151; 'Goldschmidt a. Gessner, B.
20, 2414).
Di-cuminyl-urea (03H,.CsH,.CH2.NH)2CO.
[122°]. From cuminyl cyanate and cuminyl
amine (Eaab, B. 10, 52). Small needles.
CTJMONITKILE v. Nitrile of ouMiNid Aom.
CTJMOPHEITOL v. Cumenol.
CU MOQUIlTOLIirE v. (iso)-PKOPYii-QniNoi,iNB.
;(/-CUMOftTIINOi!JE C^BMefi^ [2:3:5:4:1].
[11°]. Formed by oxidising isoduridine
CsHM;e4(NHj) [2:3:5:4:1]. Needles (from water).
Liquid above 11°. Eeduoed by SO^ to hydro-
eumoquinone CjHMe3(0H)j [169°] (Nolting a.
Baumann, B. 18, 1152).
il'-CTTMOQUIITOITE CASBOXYLIC ACID
C5Me30j.C02H (1:3:4:2:5:6). [128°]. Formed
by oxidising an aqueous solution of the chloride
of di-amido-tri-methyl-benzoio acid with FejClj
(Nef, A. 237, 11). Golden yellow needles. V.
sol. alcohol, ether, chloroform, m. sol. petroleum
ether.
BeacUons. — Liberates COj from carbonates ;
Bol. alkalis and ammonia with yellow colour.
Hydroxylamine 'yields an unstable quiuone oxim.
HNO3 (1,4) yields nitro-tri-methyl-quinone. Ee-
duced by zino-dust and aqueous NaOH to di-oxy-
tri-methyl-benzoio acid. The Ag, Pb, Ba, and
Cu salts are all yellow.
Ethyl ether Gfi^UesCO^M. [51°]. Yellow
needles. V. sol. alcohol and ether, m. sol. ligroiin.
CTJMOSTiEIL v. {Py. S)-Oxy-{B. 3)-isopbo-
PTL-QtlNOLlNE. ,
CUMYL. This name is sometimes given to
the radicles cuminyl C9H„.0H2 and ouminoyl
CgH„.CO, but it is used in this dictionary to de-
note the radicle OjH,, ; cumyl being propyl-
phenyl, while il^-cumyl is ■a-tri-methyl-phenyl.
CTJMYL-ACRYLIC ACID 0,jH„Oj i.e.
CeH,(G3H,)CH:CH.C0^ [4:1]. Isopropyl-cin-
namic acid. [158°]. From ouminic aldehyde,
NaOAo, and Ac^G (Perkin, G. J". 31,388; Wid-
mann, B. 19, 255). Needles (from alcohol). V.
sol. alcohol and HOAo, si. sol. boiling water.
Split up by heat into 00^ and isopropyl-styrene.
Aqueous CrOg gives cuminic aldehyde.- Sodium
amalgam gives 5-w-onmyl-propionio acid.
Salts.-^''NHjA': asbestos-like crystals, m.
sol. water. — OaA'.^ : needles, si. sol. water ; ab-
sorbs oxygen at 100°. — SrA'j 2aq.— AgA' ; bulky
PP-
Chloride CeH4Pr.CH:CH.C0Cl. [0. 25=].
Amide C,HjPr.CH:CH.CONHj. [186°].
SeTivatives «. Amido-,Nitbo-, andOxY-CDMiii-
AORYLIO ACID. ■ '
Di-bromide 03H<(03H,).CHBr.CHBr.C02H.
[190°].. Small white balls. Sparingly sol. in
hot benzene (Widmann, B. 19, 258).
if'-CUMYL-AMIDO-CEOTOlinC ACID
Me3C3H2NH.C(Me):CHC02Et. Formed by the
action of acetoaoetic ether on CjHjMe3(NHj)
[1:2:4:5] (Conrad a. Limpach, B. 21, 528). Vis-
cous mass. Yields on distillation di-oumyl-urea
and a quinoline derivative.
Methyl ether MeA'. [60°]. Formed by
the action of methyl aoetoacetate on ;|'-oumidine
(Conrad a. Limpach, B. 21, 528). White crystals
(from alcohol). Yields a quinoline derivative on
distillation.
OUMYL-AWBELIC ACID O^^n^fi, i.e.
C8Hi(C3H,)CH:CEt.C02H. [123°]. From ouminic
aldehyde, butyric anhydride, and sodium buty-
rate (Perkin, 0. J. 31, 403). Needles (from al-
cohol). Forms a crystalline dibromide.
CTTMYIi BBOffllDE v. Bboho-oumbne.
CUMYL CHLOBIDE v. Chlobo-cumens!.
CUMYL-CEOTOHIC ACID CigHuO^ *.«.
0sH,(CsH,).0H:CMe.C02H. [91°]. Fromcuminio
aldehyde, propionic anhydride, and NaOAc (Per-
kin, G. J. 31, 403; 35, 137). Nodules (from al-
cohol) or prisms (from light petroleum). — AgA' :
bulky pp.
Di-6romi£ZeCeH4(C3H,)CHBr.CMeBr.COj,H.
[140°-150°]. Prisms. Converted by KOH into
allyl-isopropyl-benzene.
if^-CUMYLENE-m-DIAMINE CoHMes(NH2)j
[1:3:4:2:6]. [84°]. Formed by reduction Of nitro-
ij'-oumidine (from tri-nitro-if'-oumene) or of the
corresponding nitro-t('-cumidine sulphonio acid.
Long thick needles. Fe^Cl,, gives a dark red
colouration. Gives the Bismarck-brown and
chrysoidine reactions. The hydrochloride forms
white plates (Mayer, B. 20, 970).
Isomerides v. Di-AMiDO-cnMENE.
CUMYLENE BROMIDE v. Di-bbomo-oumene.
DI-iff-CUMYL-ETHYLENE-DI-KETONE
[5:4:2:1]. C3Hj,Me3.CO.CH2.CHj.CO.C,H2Me,
[1:2:4:5]. [120°]. Formed by the action of suc-
cinyl-chloride upon ilf-cumene (over 2 mols.) in
presence of AljOlj. On oxidation it gives tri-
methyl-benzoic acid [150°] (Glaus, B. 20, 1378).
i(<-CUMYL-ETHYL.KETONE-iB-CAEBOXYLIC
ACID C,HjMe,.CO.CH2.CH2.COjH [5:4:2:1].
[105° uneor.]. its chloride is formed by the
action of sucoinyl chloride (1 mol.) upon >)/-cnmene
(1 mol.) in presence of Al^Clj. Small colourless
crystals (Claus, B. 20, 1378).
i('-CUMYL-HYDEAZINEC„H,(CH,),.NH.NHj
[1:3:4:6]. [120°]. Formed by reduction of the
sulphite of ■ diazo-pseudo-cumene with zino-dust
and acetic acid, and heating the sulphite which
is formed with dilute HCl (Haller, B. 18, 91).
Colourless needles, v. sol. alcohol and ether,
nearly insol. water. By boiling with aqueous
CuSO^ it is converted into pseudo-oumene.
CUMYLIDENE - ETHYLENE - ANILINE v.
Dl - PHENYL - l(i-OCMYL - METAPYBAZOIi - TBTEA-
HYDEIDE.
CUMYLIZIN - ACETO - ACETIC ETHEE v.
ACETO-AOETIO-ETHBK-CUMYL-HYDBAZIDE.
DI-CUMYL DI-KETONE is Cumfml v. Ou-
minic ALDEHYDE.
CUMYL PEOPYL-BENZYL KETONE is De-
oxy-cwmm&in v. Cuminic aldehysb.
293
OTJMYL MERCAPTAN.
i(<. CTJ3ITI,' MEBCAPTAII CsH,„S i.e.
C^ajMej^SH) [1:2:4:5]. [87°]. (23o°'). Formed
by reduction of ilf-cumene sulphonic chloride
<Beilstein a. KBgler, A. 137, 322). Laminae
(from alcohol). — (C,HjMejS)sHg : needles (from
alcohol) (RadlofE, B. 11, 32):
OUMYL METHYL KETONE CjH.^r.CO.CH^.
(253° i.V.). S.G. 15 -976. From- oumene, AcCl,
and AljClj (Widmann, B. 21, 2225).
OiEim C„H4Pr.C(N0H).CH,. [71°]. Trime-
tric tables (from ligroin).
i)-CUMYI-PROFIONIC ACID C.jH.A i.e.
CiH,(C,H,).CH,.CHrC02H. [76°]. From cumyl-
acrylic acid and sodium-amalgam or HI (Perkin,
0. /. 31, 388 ; Widmann, B. 19, 2773). LaminsB
(from ligroin). — AgA'.
^ - CUMYL BISULPHIDE (C.H.MeJjSj.
[115°]. From ifi-oumyl meroaptan and i)(-oumene
sulphonic acid in alcohol (Badloff, B. 11, 32).
DI-if^-CUMYL-THIO-UREA
SC(NH.C,H2Mes)j. [146°]. Formed by heating
if'-cumidine (224°) with CSj. Prismatic crystals.
Sol. hot alcohol, si. sol. ether, insol. wateir
(Engel, B. 18, 2233).
^ - CUMYL-UEEA O.HjMea.NH.CO.NHj.
Formed by mixing aqueous solution of ^a')-cumi-
dine hydrochloride and potassium oy anate. White
needles. Sol. hot alcohol, si. sol. ether, insol.
water. Decomposes at c. 227° without melting,
evolving NHj andgivingdi-(tf)-oumyl-urea (Engel,
B. 18, 2232).
o-Cnmyl-urea [2:1] CaH<Pr.NH.C0,NH2.
[134°]. Small needles (Constam a. Goldschmidt,
ii. 21, 1157).
ij-Cumyl-urea [4:1] C„Hj?r.NH.C0.NH2.
[152°]. Slender needles (C. a. G.).
Dl- ^ - cumyl - urea OC{NH:.C„H2Me3)j;.
[above 290°]. White silky needles. Sublimable.
SI. sol. alcohol. Formed by heating the mono-
'oumyl-urea, NH, being evolved (Engel, B. 18,
2233).
Di-t((-cumyl-urea
Me3GeH2NH.C0.NH.C„H;,Mes [above 300°]. Is
a pioduct of the distillation of the ethyl or
methyl ether of i((-cumyl-amido-orotonic acid
C„H2Mes.NH.CMe:0H.C02H (Conrad a. Lim-
pach, JB. 21, 528). White needles, insol. ordinary
solvents.
CUPBElNE V. Cinchona bases.
CUPEONINE V. Naecotine.
CURARIWE CijHjsN (?) Occurs as sulphate
in curara -Or urari, a resinous arrow-poison used
by the South American Indians, and said to be
obtained by boiling a climbing plant of the genus
Strychnos with water. Deliquescent prisms;
V. sol. water and alcohol, m. sol. chloroform,
insol. ether. It is coloured red by cone.
HaSO,. HNO3 gives a purple-red colour. K„SOj
and H2SO4 give a violet colour like that from
strychnine. — B'jHjPtCls: yellowish white pp.
— Pier ate B'G,Hj(N02)aOH : yellow pp.
(Eonlin a. Boussingault, A. Oh. [2] 39, 24 ;
A. von Humboldt, A. Ch. [2] 39, 30 ; Pelletier a.
P6tr6z, A. Ch. [2J 40, 213 ; Pelouze a. CI. Ber-
nard, C. B. 31, 553 ; 40, 1327 ; Reynoso, C. B.
89, 697 ; Pelikan, C. B. 44, 507 ; Milleroux, C. B.
47, 973 ; Preyer, Bl. [2] 4, 238 ; Dragendorff, Z.
[2] 3, 28; Bert, G. C. 1865,958; Schnetzler,
N. Arch. ph. mat. 24, 318 ; Fliiokiger, N. Bepert.
PUarm. 22, 65; Koch, C. 0. 1871,219; Salomon,
Fr. 10, 454 ; Bcehm, C. C. 1887, 520 ; Sachs. A.
191, 254 ; Villiers, J. Ph. [6] 11, 053).
CURCUMIN C„H„0,. [178"]. The colour-
ing matter of turmeric root, from which it
may be obtained by extracting with ether
after removing an oil by ligroin (Vogel, Schu). J.
18, 212 ; Pelletier a. Vogel, J. Ph. 1815, 259 ;
Vogel, jun., A. 44, 297 ; Daube, B. 3, 609 ;
Sehiitzenberger, Bl. [2] 5, 194 ; Jackson a.
Meuke, Am. 4, 79; 6, 77; P. Am. A. 17, 110).
Stout needles (from alcohol) ; nearly insoL water,
benzene, CSj, and ligroin ; sol. HOAc, alcohol,
and ether. Its ethereal solution exhibits green
fluorescence. Its alkaline solutions are brown,
but it is reppd. unaltered by acids. Salts of Ba,
Ca, and Pb give brown pps. in the alkaline
solution. Paper stained with curcumin and
moistened with boracic acid becomes, according
to Daube,' orange after drying ; turmeric paper
bscomes crimson under these conditions ; in
either case the colour is turned bluish-blafck by
alkalis. Treatment with boracic acid and cono.
HjS04 gives 'rosocyanin,' of which the solu-
tions are magenta and the metallic salts blue.
Chromic acid mixture oxidises curcumin to tere-
phthalic acid (Gajevsky, B. 6, 196). According to
Eachler {B. 3, 713) distillation over zinc-dust
yields anthracene.
Metallic derivatives C,4H,3KO,: very
dark crimson amorphous body, sol. water and
alcohol. — CuH.jKjO,: orange-red needles, sol.
water, insol. ether. Long boUing with EtI forms
a di-ethyl derivative.
Acetyl derivative CijHijAcO,. Brown
mass, sol. alcohol and HOAc, si. sol. ether and
benzene, insol. CSj.
Diacetyl derivative GnHi^AojO^. [154°].
Formed by heating curcumin with Ac^O and
NaOAo. Yellow trimetric plates. Cone. HjSO,
forms a blood-red solution with green reflex.
p-Bromo-bensyl derivative
C,4H„(C^3BrMe)04. [78°]. From potassium
curcumin and ^-bromo-benzyl bromide in alco-
hoi. Yellow crystals, sol. alcohol and HOAo.
Oxidised by KMnO, to vanillin.
CUSCAMIITE V. Cinchona bases.
CUSCONIDINE V. Cinohona bases.
CUSCONINE v. Cinchona bases and Abicine.
CUSPARINE CigH^NOj. [92°]. An alka-
loid present in the Angustura bark (from Cus-
paria febrifuga). An ethereal solution of this
bark yields with oxalic or sulphuric acids
pps. of the corresponding salts as yellow crys-
talline substances, which yield on decompo-
sition the alkaloid. Long colourless needles, sol.
petroleum. Decomposed by potash into an
aromatic acid, and another alkaloid [250] (Kiir-
ner a. Bohringer, Gf. 13, 363 ; cf. Saladin,
J. civim. med. 1833, 9, 388 ; Herzog, Ar. Ph. [2]
93, 146).
Salts. — The sulphate, hydrochloride,
and oxalate are sparingly soluble, the tar-
trate is readily soluble in water. The platino-
chloride is an orange yellow pp.
CYAMELIDE v. Cyanic acid.
CYAMELURIC ACID v. Cyanic acid.
CYAMIDO- = Cyanamido-.
CYANAMIDE v. Cyanio acid.
Di-cyan-diamide v. Cyanic acid.
CYANAMIDE-CARBOXYLIC ACID
" Cy.NH.COgE. Only some salts of this dibasic
OTANATES (METALLIC).
297
ao^ are known (G. Meyer, J'.pr, 12^, 419). The
acid, when liberated, spli,ts up into GO, and
oyanamide.
Salts. — CyNNa.COjNa. Formed by passing
carbonic acid into a boiling aloohoUc solu-
tion ol sodium oyanamide: 20yNNaH + 00j
_= CyNHj + OyNNa.CO,Na. Amorphous powder,
insoluble in alcohol, soluble in water. May be
obtained in groups of microscopic needles by
dropping its aqueous solution into alcohol. Con-
verted by fusion into the isomeric sodio cyan-
ate.— OyNKOOjE. Got by passing COj into boil-
ing alcoholic potassio cyanamide. Besembles the
foregoing sodium salt.— {CyN(C0,)}Ca,5ac[. In
a similar way from calcium cyanamide, by pass-
ing OOj into its alcoholic solution. Thin white
needles, slightly soluble in water. Its aqueous
solution is decompose^ by heat into GaCO,. and
oyanamide. — {CyN(062)}Sr, 2iaq. Gritty crys-
talline powder, resemblmg the caloimn salt. —
{OyN(COj)}Ba, l^aq. Eesembles the strontium
salt.
JReotcHans. — A solution of the potassium salt
gives : — 1. With silver nitrate a pp. of silver
oyanamide and evolution of COj. — 2. With basic
lead acetate a white pp. of lead carbonate, cyan-
amide being in solution.
Ethyl ether CN.NH.COjEt. From cyan-
amide di-carboxylio ether and alcoholic EOH
(Bassler, J. pr. [2] 16, 146). Syrup. Eeadily
polymerises. — B"2HC1 : crystalline powder, v.
sol. water ; converted by boiling water into allo-
phauic ether.— CN.NNa.002Bt [241°] : needles ;
spUt up by heat into NaOyO and EtN.OO. —
CN.NK.COjEt. .[199°]. Converted by EtI at
150° into CN.NEt.COjEt (213°).—
HO.Cu.NOy.COjEt.— CN.NAg.OO,Et.
Cyanamide di-carbozylic ether
CN.N(C0.,Et)2. [33°]. Prom sodium cyanamide
and CLCdjEt (Bassler, J.pr. [2] 16, 134). Prisms.
Insol. water. Boiling water decomposes it into
CO2, alcohol, and cyanamide oarbbzylic ether.
CYANAKIDO-BENZOIC ACID
CN.NH.C,H,.GO^ [1:8]. [above 200°]. Hat
pearly needles (containing i aq). Sol. hot water,
alcohol and ether, nearly insol. cold water and
benzene. Formed by the action of cyanogen
chloride on an alcoholic solution of m-amido-
benzoio acid.
Beactions. — Heated with baryta-water to
140° it decomposes into m-amido-benzoic acid
OO2, and NHj. It is not altered by boiling with
water, and only slowly with NaOH. Heated to
140° alone it evolves cyanic acid lisaving a white
amorphous insoluble substance. BoUed with
dilute HOI it is converted into w-uramido-
benzoio acid. With ammonium sulphide it gives
m-thio-uramido-benzoic acid. On heating the
barinm-salt polymeric substances are formed.
It combines with aniline to form a di-phenyl-
guanidiue-carboxylio acid.
Salts.— The salts of the alkalis, alkaline
earths, and of Zn, Hg, Ni and Co are easily
soluble. EejOlj gives a yellow amorphous pp.
AgNO, gives' a white gelatinous pp. and CuSO,
gives a brown floooulent pp. (Traube, B. 15,
2113).
DICYANAMIDO-BENZOYL v. vol. i. p. 155.
p-CYANAMIDO-PHENTL-ACETIC ACID
GN.NH.G,H,.CH3.C0,H. [134°]. Formed by the
action of cyanogen chloride onf -amido-phenyl-
acetic acid in alooholio solution (Traube, B. 16,
2121). Colourless plates or tables. Y. sol.
water, alcohol and ether.' It is very unstable.
Dilute HCl converts it into jj-uramido-phenyl-
aoetic acid. CuSO, gives a brown pp. soluble
in alcohol.
CYANANILINE {Gfi,SS^}fi^^
Formation. — ^By the action of aniline upon
oximido-ether :
EtO.O(NH).C(NH).OBt+ 2PhNH,
= PhNH.C(NH).0(NH).HNPh + 2H0Et (Sent,
J-.^jr. [2] 35,514).
Preparation. — 1. Aiuline (1 pt.) is dissolved
in alcohol (5 pts.) and cyanogen is passed in
;Hofmann, A. 66, 129; 73, 180).— 2. Aniline
lOg.) is dissolved in alcohol (30g.) and water
60g.) is then added. On passing cyanogen gas
into the solution cyananiline separates; it is
purified by solution in dilute H2SO4 and reppn.
by NHj (Senf, J.pr. [2] 35, 514).
Beactions. — 1. Dry nitrous acid gas passed
into ether containing cyananiline in suspension
forms the nitrate B"2HN03. Nitrous acid gas
passed into a solution of cyananiline in 65^ p.c.
acetic acid forms ozanilide, (1, 3, 4)-di-nitro-
phenol, and phenyl-carbamine. Nitrous acid
gas passed into' a solution of cyananiline in
glacial HOAc forms the same products, and
also di-^-nitro-oxanilide.— 2. Sodium amalgam
forms NHj, aniline, and formic acid. — 3. Bro-
mine in .chloroform solution at 0° forms un-
stable amorphous 0,fi,<,'SfBi., which is prob-
ably(CjH,Br.NH.O(NH).Ci(NH).NH.C,H^Br)HBr,
being reduced by SO^Aqto di-bromo-cyananiline.
Bromine in boiling glacial HOAc forms di-^-
broino-oyananUine. Bromine-water forms tri-
bromo-aniline. — 4. Mel at 120° gives dimethyl-
anUine. — 5. PhthaUo anhydride gives phthal-
anil, 0,H^(CjO,)NPh (Senf, J.pr. [2] 85, 527).
Salts.— B"2HN03: [192°]; decomposed on
melting, with evolution of phenyl-carbamine. —
B"HjCl2.— B"H,PtGl„.— B"2HAuCl4.— B'H^Brj.
Di-p-bromo-cyananiliue OnHj^NaBr^ i.e.
CeH<Br.NH.C(NH).C(NH).NH.C„H<Br. [245°].
From cyananiline and bromine ; or by the union
of ^-bromo-aailine and cyanogen (Senf, J. pr.
[2] 35, 53|)). White plates (from alcohol), v
GYANAIBS (METALLIC). Cyanie acid has
the composition HCNO ; several isomerides of
this composition may exist (v. Ctanic acid). The
metallic cyahates are probably salts of the acid
NC.OH. A polymeride of cyanic acid, HaOjNjOj,
exists; this acid is known as cyarvwric acid.
Isomerides of this composition are possible;
cyamuric acid very probably has the constitution
(CN)3(OH)3 («. p. 810), and the metallic cyan-
urates are Salts of this, acid (v. Ctanueates).
Another polymeride of cyanic acid is also
known, Cyamelide (v. Cyanic acid).
Cyanates. Metallic cyanates are most pro-
bably all salts of the acid CN.OH. They are
produced in the following among other reactions :
(1) by passing cyanogen into solution of an
alkali or alkaline earth ; (2) by heating alkaline
carbonates to low redness in cyanogen, or with
mercuric cyanide ; (3) by fusing alkaline cyan-
ides or ferrocyanides with an easily reduced
oxide, such as PbO^, or with a nitrate ; (4) by
electrolysis of KCNAq; some cyanates are ob-
tained from KCNOAq by double decomposition.
Most metallic cyanates are soluble in water, the
2fl8
CYANATES' (METALI^IC).
oyauates of Gu, Pb, Hg, and Ag are only slightly
Bbluble. Alkali cyanates are not decomposed
by heating to dull redness in dry air ; in moist
air they give carbonates of NH4 and the alkali.
Gyanates of the alkaline earths, and , of most
heavy' metals, are decomposed by heat to CQ2
and cyanide of the metal {v. Dreohsel, /. pr. [2]
16, 201). Acids decompose cyanates, forming
CO2 and NH3, sometimes with a little un-
changed cyanic acid ; some acids ppt. solid K
oyanurate f rom KCNOAq.
Ammonium cyanate (NHJCNO. Obtained
by passing NH, into an ethereal solution of
HCNO, or by bringing together dry NH3 and
HCNO vapour. Very soluble in water. Easily
changed into its isomeride urea (Liobig a.
Wohler, P. 20, 369, 395 ; A. 59, 291).
Potassium oyanate KCNO. S.G. 2-05. H.F.
[K, C, N, 0] = 102,800; [KCN, 01 = 72,000;
[KCNO, Aq] = -5,200 (Berthelot; O. B. 91, 82).
Formation. — 1. By heating KCN in air, or in
presence of an easily reduced oxide. — 2. By
passing cyanogen into KOHAq, or over heated
K2GO3 (Wohler, 0. A. 73, 157).— B. By electro-
lysing KCNAq (Kolbe, A. 64, 236).— 4. By defla-
gi-ating KNO3 with KiFe(CN)8, or Hg(CN)2, or
nitrogenous charcoal (W., O. A. 73, 157).
Preparation. — 4 parts dry pulverised
K4E'e(CN)|, are mixed with 3 parts drypulverised
KjCrjOj ; a little of the mixture is placed in a
porc&lain or iron dish, which is heated consider-
ably below redness until the mixture becomes
like tinder and blackens ; the rest of the mix-
ture is then thrown in little by little, each quan-
tity being allowed to blacken before the next is
added (complete oxidation of KCN to KCNO is
thus ensured). After cooling, the contents of
the dish are added to successive quantities of
boiling alcohol, as much being added to each
quantity of alcohol as suffices to saturate the
latter ; the alcoholic solution is cooled, and the
crystals of KCNO are dried between paper, and
then in vacuo over H^SO^. The yield is about
42 p.c. of the KjI'e(CN)5 used ; if carefully con-
ducted the KCNO contains about 1 p.c. impuri-
ties (Bell, G. N. 32, 99 ; modification of method
of Liebig a. Wohler, A. 88, 108 ; 41, 289 ; v. also
Clemm, A. 66, 382).
Properties.- — Small colourless odourless
laminffi, resembling KClOa ; fuses below redness
to a colourless liquid, soluble in water, fairly
soluble in boiling hydrated alcohol; insoluble
in absolute alcohol.
Reactions. — 1. Unchanged by heat; but if
water is present the salt is decomposed to KjCOj
and NH5.. — 2. Eeduced to KCN by heating in
hydrogen,, or with potassium, iron, or ca/rhon. —
3. Melted with siAphwr gives K^S, KSCN, and
KjSO,. — 4. Sulphuric' acid iorms KjS and
KSCN with some NH, sulphide. — 5. -Heated in
hydrochloric acid gas, KCl and NH4CI are formed.
6. Sodium amalgam, reacts with a neutral solu-
tion to produce formamide (HCO.NH2).
The other cyanates have not been much
studied. Insoluble cyanates, e.g. of Pb or Ag,
may be obtained by proceeding as directed for
preparation of KCNO, but exhausting the heated'
mass with very cold water, removing KjCrO^ by
Ba(N03)2Aqf and ppg. by solution of a nitrate
of the metal. The following cyanates have been
isolated.
I ^ Barium cyanate Ba{0NO)j (Wohler, A.
45, 357). By adding alcohol to a mixture of
ECNOAq aiid Ba acetate ; crystalline.
Calcium cyanate has not been crystallised ;
obtained by passing HCNO vapour into milk of
lime.
Cobalt-potassium cyanate Co(CN0),j'.2KCN0
(Blomstrand, /. pr. [2] 3, 207). Dark blue
qiiadratic crystals ; obtained by adding KCNOAq
to Co acetate solution.
Copper cyanate, not crystallised ; by mixing
solution of Cu acetate and Ba cyanate.
Lead cyanate Pb(CN0)2 (Wohler, 0. A. 73,
157 ; Williams, J. pr. 104, 255). Crystalline,
nearly insoluble in hot water.
.Silver cyanate AgCNO (W., 6. 4. 73, 157).
By adding AgNOjAq to KCNOAq; S.G. 4-0;
somewhat soluble in boiling water ; dissolved
and decomposed by dilute HNOaAq; decom-
posed by heating, to Ag mixed with C and some
N. Soluble in NHjAq, giving a double com-
pound which loses NH3 in the air.
Sodium cyanate NaONO. Eesembles KCNO ;
crystalline.
Thallium cyanate TICNO ; tablets, sol. water,
insol. alcohol (Kuhlmann, A. 126, 78).
M. M.P. M.
CYANBENZINE v. PararUtrile of Phenhi.
ACETIO AOID.
CYAKTBUTINE v. Pao'anitrile of Valeeio
iOID.
CYANCONIINE C,B.,,^,. (205°). S.G. -93.
Cyanethine heated with HCl gives 'oxy-cyan-
coniine ' (v. infra), whence PCl^ forms ' chloro-
cyanooniine,' which is reduced to cyan-coniine.
This name is given to the base by E. v. Meyer \
{J. pr. [2] 22, 286), although it is not formed in
any way from coniinci
Properties. — This base dissolve somewhat
in water, forming an alkaline liquid, but it sepa-
rates again if the solution is warme'd. It is a
colourless liquid of narcotic odotir. It boils at
205°. It is volatile with steam. It is poisonous,
and its physiological effects resemble those due
to coniine. Its aqueous solution gives vrith silver
chloride crystalline needles of a double salt:
B'HgClj) Jaq. [c. 90°].
Combinations. — 1. With ethyl iodide at 100°
forms a compound, whence by AgCl' and PtCl^
sharp yellow prisms of (B'EtO^jPtOl, maybe
got.— 2. With acetyl chloride it gives unstable
needles, probably BApCl.
Beactions. — Eeduced by Zn and HCl to a
new base OuHjjN,, vAieh forms a zinc double
salt (E. V. Meyer, JT.pr. [2] 2^, 340).
Oxy-cyanconiine CgHnNjO. [157°]. S. -75
at 25°. S. (alcohol of 90 p.c.) 8 at 18°.
Preparation. — 1. This base is got by heating
(20 g. of) cyanethine {q. v.) with cone. HCl
(30 CO.) for 3 hrs. at 190°. The product is eva-
porated, mixed with ammonia, and the pp. crys-
tallised from water. — 2. It may also be got by
passing NjO, into a solution of cyanethine
in glacial acetic acid (v. Meyer, J. pr. [2] 26,
Properties. — Bunches of glittering needles
(from water), long striated prisms (from alcohol),
or dendritic aggregates (by precipitation). May
be sublimed. SoIj chloroform, benzene, and
ether.
Reactions. — 1'. Heated with, ethyl iodide it
CYANETHINE.
299
foims a syrup, whence by successive treatment
witli AgiO, HOI, and PtCI,, trimetrio crystals of
(B'EtC!l)jPtCl4 are formed. Henoe it is a tertiary
base. — 2. With acetyl chloride forms a peculiar
compound B'AcCl, not decomposed by ammonia
(M.). — 3. Not aSEeoted by heating with Aop at
180°.— 4. With PCli at 140° it gives ofE HCl.
Product shaken with solution of NaOH and
extracted with ether, is found to be an oil
CgHiaNjCl. This reaction looks as if the base
contains hydroxyl. It is converted by NHj at
220° into oyanethine: CaHisN^Ol + 2NH3
= NH^Ol + 0„H,3Nj.NHj. AlcohoUo potash
rapidly removes its chlorine forming a new base :
C,H,aNjCl_ + KOBt = KCl + OjHisN^.OEt. The
new base is an oil smelling of herbs and boiling
at 230°. Its platinum salt crystallises in ocia-
hedra (B'HCljjPtOl,. Heating with fuming HCl
at 210° it is converted into the original oxy-oyan-
coniine : 0,H„N.,OEt + HCl = EtCl + CgH.iNjO.
These various reactions point to the presence of
hydroxyl in oxy-cyanooniine and of amidogen in
oyanethine. The chlorinated base CgH,jClNj
may be reduced by Zn and HCl. The zinc
double salt ,of a new base is thus got :
ZnClj,C,8H5„N42HCl. If this salt be treated
with solution of NaOH and shaken with ether,
the ether leaves, on evaporating, cyanconiine
CgHg^N,, in the form of an oil. The base
C„]^N4, which is first formed in the reduction
of chloro-cyanconiine, is readily oxidised by
Ag^O to cyanconiine. — 5. With OlCOjEt pxy-
cyanconiine forms a liquid carboxylic ether,
which is decomposed by cone, mineral acids
into the oxy-base COj and alcohol (E. v. Meyer,
J.iw. [2]30, 121).
Salts. — Sol. water. Solutions acid to lit-
mus.—B'HCl (at 110°). — (B'HOljjPtCl,. —
B'HNO,.— B'HAO,. Prisms.
Oxy-cyanconiine can occasionally act as an
acid, for it forms a silver salt CgHisAgNjO, sol.
HNO, and NH^.
Methyl derivative CsH^MeNaO. [77°].
(276°). S. 8 at 18°. Mel (5 pts.) is heated with
oxy-cyanconiine (2 pts.) at 150°. Crystals of
C„H„MeN20,HI are got. NaOH sets the base
free. It forms white needles. Insol. potash.
Salts. i-fBTaC^^PtCl,: yellow trimetric
prisms. — HgCl2B',^a(i : needles grouped in
stars.
Ethyl derivative C„H„EtNjO. [43°].
(208°).
Salts.— (B'HCnjPtCl,: tablets.—
HgCl^',iaq.
Ethylene derivative G^tip^i^fi)^.
[164°]. S. -01 at 24°. From ethylene bromide
(7 pts.) and the base (2 pts.) at 170^
Salt.— B"(H01)jPtCl,: prisms.
Constitution. — Since methyl-, ethyl-, and
ethylene-oxy-cyanconiine are insoh strong potash,
it would appear that the alkyls have entered an
hydroxyl (E. v. Meyer, J". j)r. [2] 26, 352). But
this is not the hydroxyl corresponding to the CI
of chlorc-cyanconiine, because the product of
the action of EOEt upon it is a different body
to the ethyl-oxy-cyanooniine here described.
Nevertheless, EtI and Mel acting upon oxy-
cyanconiine in presence of alcoholic potash form
the above ethyl- and methyl-oxy-cyanconiines.
The isomeric methozy-oyanconiine from MeOE
And chloro-cyanconiine boils at 225°. Tho
ethoxy-base boils at 230°. E. v. Meyer thinks
the isomerism can be explained thus :
ethoxy-cyanooniine 0,H,5N2(OBt)
ethyl-oxy-cyanconiine CjH,.,N(NEt)(OH).
CYANETHIIIE CgH.jN,. [190°]. S. -073 at
17°. S. (alcohol of 90p.c.) 5-8. , According- to
E. V. Meyer (J, pr. [2] 35, 84) cyanethine is
not the paranitrUe of propionic acid CjNjEtj,
since this body, obtained by reducing a-di-chloro- ,
propionic nitrile, has quite other properties.
PreparaUon. — Propionitrile (240 g.) is added
gradually to sodium (30 g.), in a flask full of
carbonic acid. A violent reaction occurs a few
minutes after the addition of each pqrtion. The
excess of propionitrile is distilled off. The re-
tort is broken up and the contents treated with
water. The insoluble cyanethine is crystal-
lised from 90 p.c. alcohol. The yield is 50 p.c.
(Fraukland a. Kolbe, C. J. 1, 69 ; E. v. Meyer,
J. pr. [2] 22, 262). One third of the sodium be-
comes Bodio cyanide ; for every molecule of
sodic cyanide formed one molecule of ethane is
given off. If ether be used as a diluent, there
is formed an interinediate product Me.CHNa.CN,
which on being treated with water yields an
oil which gradually crystallises, and has the
same percentage composition as cyanethine; but
is polymeric with it [48-"] (258°). The compound
Me.CHNa.CN, heated with propionitrile to 150°,
yields cyanethine (E. v. Meyer, J. pr. [2] 37, 412).
Properties. — Monoolinic crystals (from
alcohol).
Beactions. — 1. With ethyl iodide at 160°
forms B'Etl, a syrup, whence by moist Ag^O an
alkaline Uquid may be got, and on adding HCl
and PtCl, a well crystallised double salt
(B'EtO^jPtCl, is obtained. But if the iodide be
treated with Ag^O, and the resulting alkaline
solution be shaken with ether, the latter is found
to contain ethyl-cyanethine CjHjjEtN,. [45°].
(260°). — 2. Excess of strong hydrochUrria acid
converts it into cyanconiine CgHijNs + H^O + HCl
= HjNCl + CgHnONj. It is precipitated by am-
monia.^3. This same body is formed by passing
a.fls into a solution of cyanethine in glacial
acetic acid. — i. With ClCOjEt it forms cyanethine
carboxylic ether CgH,3NjNH(C02Et). This is a
solid which melts at a low temperature and
boils at (247°). It is converted by boiling
alkaU into cyanethine, alcohol, and CO^. Its
aqueous solution gives, with AgNO^, a pp.
CgH,jN2NAg(C0ijEt), aq. Cyanethine carboxylic
ether is decomposed by aniUne with formation
of an anilide CgHuNrNH.CO.NHPh [184°]. This
is a very stable body, not decomposed by hot
alcoholic potash, but when heated in a current
of HCl it gives off phenyl cyanate, becoming
cyanethine
C,H„Nj.NH.CO.NHPh = CgH.jN^.NHj-l- CO.NPh
(E. V. Meyer a. Biess, J. pr. [2] 30, 115),—
5. Combines at 100° with phenyl cyanate
C,H,jN2.NHj + CONPh = CgH„N2.NH.C0.NHPh.
Salts.— B'HCl aq.—B'Xi'tCllj.—B'HNOi,:
large prisms, neutral to litmus.
Combination. — B'jAgNOj (at 120°) : crystal-
line pp.
Mono-aceiyl derivative CjHuAcN,
[59°].
Tri-chloro-cyanethine CjHuCljNa. [110°]
Obtained by passing CI into a solution of cyan-
ethine in chloroform. Besembles tri-bromg.
soo
CYANETHINE.
cyanethine in its properties. N^O, passed into
its solution in glacial acetic acid forms tri-
chloro-oxy-oyanconiine 0,H,„(0H)01sN2 [132°].
This latter may be reduced by EI to the ozy-
cyanconiine.
Bromo-cyanethine CoHi^BrN,. [153°].
Pregaralium. — Oyanethine (30 g.) is dissolved
in EBr and an equivalent of Br (30 g.) is added.
A perbromide of bydrobromide of cyanethine
separates as an oil, which soon solidifies. The
whole is heated in sealed tubes at 100° for
6 hours. On cooling, crystals of the bydrobrom-
ide of bromocyanethine separate. The base is
got by adding NE, to an aqueous solution of
these crystals (C. Eiess, 3. ^r. [2] 30, 146).
ProperHes. — Needles. Penetrating odour;
T. si. sol. water.
S alts.— B'HNO,. Trimetric— (B'HCa)jPtCa,.
— B'HClAuCl,.— B'HBr.
Beaciions. — 1. Boiled with alcoholic NaOEt
it forms ethoxy-cyanethine (g. v.). — 2. Fuming
HCl at 200° displaces amidogen by hydroxyl,
the product being 0„H,jBrNj(OH), [171°]. The
salts of this bromo-oxy-cyanconiine are decom-
posed by water. — 3. With aniUne at 200° it
forms 0,H„(NPhH)N3, phenyl-amido-oyanethine.
This is insol. water, but crystallises from alcohol
in plates, [125°].— 4. Zimc and EGl reduce it to
cyanethine. — 5. N^Og passed into its solution in
glacial HOA.C forms bromo - oxy - cyanconiine
[172°] (B. V. Meyer, J.pr. [2] 26, 358).
Tri-bromo-cyanethine CfHi^BraNj. [126°].
This is formed when brorcine acts on cyanethine
dissolved in chloroform. It forms pearly plates
insol. water, sol. alcohol, ether, and chloroform.
It dissolves in strong acids, but is reppd. by
water. By passing K2O3 into a solution of the
base in glacial acetic acid, the corresponding
' tri-bromo-oxy-cyanooniine ' may be formed :
C,H,„(OH)Br,N„ [149°].
lodo-cyanethine CbHuINj. [152°].
Preparation. — Iodine simply combines with
cyanethine, forming a per-iodide. Substitution
takes place in presence of HNOg, as follows :
cyanethine (1 pt.) is dissolved in excess of dilute
HjSOj, iodine (I5 pt.) is added, and then the
liquid is digested on the water-bath while cone.
HNO, is run in until all the iodine has dis-
appeared. From the filtrate NaOH throws down
iodo-cyanethine.
Properties. — Sol. acids and dilute alkalis.
Decomposed by boiling NaOH.
SaZt.— B',HCl,AuC]s.
Beactions. — 1. Iodine added to its acid solu-
tions throws down glittering green plates of a
periodide. — 2. Unlike the chloro- and bromo-
derivatives, it is not affected by passing N2O3
into its solution in glacial acetic acid. — 3. Never-
theless fuming HNO„ acting upon its solution
in glacial acetic acid, does produce iodo-oxy-
oyanconiine: CjH,2lNj(0H). This maybe crys-
tallised from alcohol. It melts at [157°]. —
4. Dilute HNO3 or cone, HCl (at 180°) con-
vert iodo-cyanethine into oxy-cyanconiine,
CsH,3(0H)Nj, [156°] pjiess, J.pr. [2] 30, 168).
Methyl-cyanethine C8H„MeN,. [74°] (0.
257°). From oyanethine and Mel at 160° (E. v.
Meyer, J. pr. [2] 26, 343). V. sol. water, form-
ing an alkaline solution from which it may be
extracted by ether. It separates as an oil when
its solution, saturated in the cold, is warmed.
Cyanethine itself is very slightly soluble. Methyl-
cyanethine affects the brain-cells, producing
muscular contraction. Chloral, chloroform, and
morphia are antidotes.
Combinations. — B'2,AgN03. Pp. sol. hot
water, separating as plates. — B',(HCl)2PtCl4.
Beacticm. — 1. Heated with HCl at 180° it
splits up into methylamine and oxy-cyanconiine :
C,H,3N,(NHMe) + H,0 = C|,H,3Nj(0H) + NHjMe.
Uethoxy • cyanethine CgH,4(0Me)N„aq.
[130°]. Besembles ethoxy-cyanethme in prepa-
ration, properties, and salts. It also exchanges
NH2 for OH when acted on by N2O,, the product
being the mono-methyl derivative of di-oxy-
cyanconiine CgH,2(MeO)N2(OH). This forms
the salts: B',HCl,Au01,.— C,H„Ag{MeO)Nj(OH)
(C. Eiess, J.pr. [2] 30, 153).
Ethoxy-oyanethine CoHn(OEt)Nj. [116°].
PreparaUon. — From sodic ethylate and
bromo-cyanethine (Biess, J.pr. [2] 30, 148).
Properties. — Trimetric plates. Sublimes at
100°. More soluble in cold than in hot water.
Its solution is alkaline to test-paper. Separated
by KOH from its aqueous solution, Sol. alcohol,
ether, chloroform, and acids.
Beaciions. — 1. An aqueous solution of the.
free base precipitates the hydrates of copper and
lead from their salts. — 2. N2O3 passed into a
solution of the base in glacial acetic acid forms
the corresponding ethyl derivative of di-oxy-
cyanconiine: CgH,2(OEt)N20H. This melts at
[51°] and forms a silver derivative,
C|,H„Ag(0Et)N20H.— 3. Heated with cone. HCl
at 200°, it appears to form di-oxy-cyanconiine :
C!,H,„(0H)3N2 [151°], a silver salt,
C„H„Ag{0H)2Nj," being analysed.
Salts.— (B',H01)jPtCl,.—(B',HCl)AuCl,.
. Combinations.— B'r^NOi,
CYAN£THOLINE v. supposed Ethyl ether ol
Normal Cyanic acid.
CYANHYSBIC ACID HON. (Hydrocyanic
acid. Prussic acid. Formmtitrile.) Mol. w.
26-98. [ — 15°]. (For melting-points of mixtures
of HON and H,0 v. Gautier, A. Ch. [4] 17, 120).
(26-5°). S.G. (Liquid) at 7° = -7058, at 18° -6969.
V.D. -966 at 40°, -942 at 77°, -936 at 96°, -924 at
158°, -903 at 198° (Gautier, A. Ch. [4] 17, 119).
M" = 1-263 at 17° (BuBsy a. Buignet, A. Ch. [4]
3, 231). /It, for mixture of HON and HjO
(17°) (B. a. B., Z.C.); ratio 2HCN:H,0= 1-282,
2HCN:2H30 = 1-297; 2HCN:3H;0 = 1-306,
2HCN:4H20 = 1-308. H.F. [C, N, H]= -27,480;
[CW,H2] = 10,740; H.C. [CNH,0§] = 158,620
{Th. 2, 389). Heat of neutralisation [HCNAq,
Na0HAq] = 2,770 [Th. 1, 295). H.V. = 5,700
(Berthelot, A. Ch. [4] 6, 432). HCy is an ex-
tremely weak acid; the affinity is so small that
the compound can scarcely be classed as an acid
fv. Ostwald's Lehrbttch der allgemeinen Oiemie,
2, 849). Contraction of volume occurs on mixing
with water; v = vol. of HON, v' = vol. of H/),
t" = vol. of mixture ; then (B. a. B., 2.c.).
Ratio o£ HCNiH,0 t+t'-t"
T+V
2:1
-0328
2:1-6
•0541
2:2
-0603
2:2-5
-0611
2:3
■0623
2:3-6
•0536
3:4
-0468
CYANHYDRTC ACID.
301
Lowering of temperature occurs on mixing
frith water (B. a. £., Us.),
HONiH/)
lUl of temp,
o
3:1
8-6
3:1-6
9
2:3
9-25
2:3-6
9-25
2:3
9-75
2:38
8-25
2:4
7-75
Maximum contraction and maximum fall of
temperature occur when the acid and water are
mixed in the ratio 2HCN:3H:0.
Yapour-pressure of liquid HCN at 13-25°
-472 mm. (B.a. B., Z.C.).
Prussio acid was discovered by Soheele in
1782 ; it was examined by Berthollet, Froust, and
others ; the pure acid was prepared by Gay-Lussac
in 1821 {A. Oh. 77, 128 ; 95, 136).
Occurrence, — In tobacco-smoke (Yogel a.
Beischauer, D. P. J. 148, 231 ; Yohl a. Euren-
berg,\^. 147, 130). Among the products of oxi-
dation of many carbon compounds by ENO,
(Gill a. Mensel, Z. 1869. 65). As a product of
the action of EHnO^Aq on thialdine and analo-
gous compounds, also of boiling NaOHAq on aro-
matic nitro- compounds (Guareschi, B. 12, 1699 ;
Post a. Hubner, B. 5, 408). As a product of the
distillation with water of parts of plants contain-
ing amygdaUn (3. v. vol. i. p. 205).
Formation. — 1, By subjecting cyanogen and
hydrogen to the electric discharge (Boillot, C. B.
76, 1132) ; or by heating the mixture to 500°-550°
(Berthelot, J5Z.33, 2) ; or by dissolving cyanogen
in water and allowing to stand (Wphler, P. 16,
627 ; D.also Ctanooen). — 2. By the action of the
induction-spark on a mixture of acetylene and ni-
trogen (Berthelot, 0. B. 67, 1141 ; Dewar, Pr.
29, 188 ; 30, 85), or on a mixture of N with hy-
drocarbons which yield OjHj (Berthelot, l.c.;
Perkin, C. N. 21, 66).— 3. By rapidly heating
NH4 formate or formamide withP^Oj (Lorin, A.
132, 255 ; Handl, W. A. B.' 32, 252 ; 42, 747 ;
Hofmann, /. pr. 91, 61).— 4. By burning moist
methylamine (Tollen?, Z. 1866. 516).— 5. By
passing CHClj vapour with NH3 through a hot
tube, or by heating GHCl, and alcoholic NE, to
180°-190° (Heintz, A. 100, 369) ; or by mixing
CHCl, with KOHAq and NHjAq (Hofmann, A.
144, 116).— 6. By decomposing Hg(CN)2 by
HClAq or HjSOjAq, preferably in presence of
NHjCl, and purifying by passing through CuCOj
and CaClj (Gay-Lussae; Bussy a. Buignet, A. Ch.
[4] 3, 250).— 7. By decomposing Hg(CN)j by H^S,
or by shaking with HjSO.Aq and Fe filings. —
8. By decomposing AgCN by HClAq.
Prepa/ration. — 1. A cold mixture of 12 parts
water with 9 parts HjSO, is poured on to 8 parts
coarsely powdered K,Fe(CN), in a capacious
flask ; the flask is connected with two bottles
containing calcium chloride placed in a bath of
oold water ; the exit tube f ilom the bottles passes
into a dry flask surrounded by snow and salt.
The mixture is warmed, and HON passes into the
CaCLj-bottles ; after about ^ hour the water sur-
rounding the CaClj-bottles is warmed to 30° or
80, when dry HON passes into the flask in the
freezing mixture, and is there liquefied (Pessina,
Traiti de Pharmacie de Soubeiran, 2, 337 ; q^.
Wohler, A. 73, 218). C^reat care must be taken,/
as EON is frightfully poisonous ; the CaCl,
used should be dissolved (after use) in a large
quantity of water, HCK is evolved during solu-
tion. If HCNAq is to be prepared, 10 parts
E4l'e(CN), may be distilled with about 4 parts
E2SO4 and a convenient quantity of water ill a
flask with very good condenser; the distillate
may be rectified by distilling over MgO, — 2. A
solution of HON of determined strength can be
prepared by mixing KON and tartaric acid in the
ratio K0N:H2.04H40s with a measured volume of
water; HONAq and KH.O4H4O, are formed, al-
most the whole of the latter is ppd. If 4 parts
pure EON are added to 9 parts tartaric acid in
60 parts water, and shaken in a stoppered bottle
nearly filled by the liquid, and then allowed to
stand for 12 hours, the liquid contains 3*6 p.c.
HON (Olarke, A. 1, 44 ; cf. Liebig, A. 41, 288).
Properties. — ^A mobile, colourless liquid, hav-_
ing a peculiar and very penetrating odour ; does
not redden litmus ; intensely poisonous ; one drop
of the anhydrous acid is instantly fatal if swal-
lowed. Inhalation of minute quantities of va-
pour suffices to kill, even when mixed with air the
vapour is e:^tremely poisonous ; soluble in water,
alcohol, and ether (for temperature and volume
changes on dissolving in water, «. ante). Evapo-
ration in air suffices to freeze part of the acid,
crystals thus formed are transparent orthorhom-
bic prisms. HON or HCNAq is unstable; brown,
hnmus-Iike products are formed (v. also BeacMons
No. 2) ; addition of traces of formic acid or a
mineral acid serves to prevent this decomposi-
tion. Burns in air with blue flame. HCNAq is
a very weak acid ; its affinity is almost not^iing ;
cyanides are generally very easily decomposed
by acids.
Beaetions, — 1. Passed through a tube heated
to dull redness, H, ON, 0, and N are formed (De-
ville a. Troost, J. 1863. 307) ; heated to about
100° HON forms a black mass, which at a higher
temperature gives NH, and NH,.CN (Girard,
C. B. 83, 344) ; passed over red hot iron HON is
decomposed into H,0, andN (Gay-Lussac, A. Ch.
95, 200).— 2. Even m the cold HON or HCNAq
easily undergoes change ; brownish, humus-like
bodies are formed ; according to Gautier {A. Ch.
[4] 17, 119) perfectly pure HON does not undergo
change, but if a trace of NH3 is present decom-
position proceeds with formation of azuhnic add
(q. v. vol. i. p. 429). Traces of alkali hasten the
decomposition of HON (hence if the OaOL, used
for drying contain OaO the acid produced soon
begins to chatige), traces of acids retard the
change ; among the products is the polymeride
HjOjN, (v. TBIOTAHHyDBIO ACID, p. 302). In
presence of water NH4 formate is produced. —
3. A series of electric sparks passed through
HON causes partial decompositipn to N and
CjHj with separation of a little C, after a time
the OjHj and N begin to recombine. An electmc
current passed through HCNAq evolves H at the
negative electrode with formation of cyanide of
the metal forming the positive electrode ; if the
HONAq is cone, and mixed with H,S04, COj and
NH, are produced (Schlagdenhauffen, J. 1863.
305).— 4. Mixed with oxygen, and brought to a
flame, violent explosion occurs vrith ppduction
of OOj, HjO, N, and traces of HNO,. — 5. Potas-
svum permcmganate in alkaline solution oxidise)
302
CYANHYDRIO ACID.
HCNAq to HONOAq (Pfiam de Saint-GiUes, A.Ch.
[3] 55, 374).— 6. Chlorine reacts with HON in
daylight to form C3N3CI3 ; with HCNAq it forms
CNCl and HCl (BisohoS, B. 5, 80). Aooording
to Wurtz {A. 79, 280) CI also forma CjNjCl^.CNH ;
if the HCN is in alcoholic solution a crystalline
'Compound CaHuClNjO, is said to be produced
(cf. Wurtz, Z.C. and Bischoff, l.c.). — 7. Bromine
forms CNBr and HBr.— 8. Iodine with HCNAq
gives CN and HIAq. — 9. Hydrogen (nascent)
forms CH3NH2 ; the same compound is produced
by passing HCN vapour and H over hot spongy
Pt (Menduis, A. 121, 129 ; Linnemann, A. 145,
38; Debus, id. 128, 200).— 10. Potassium Taeatei
with HCN gives KON and H. — 11. Eeaction with
water, v. beginning of this article.— 12. Heated
vfith hydviodic acid, NHj and CH, are produced
(Berthelot, J. 1867. 347).— 13. Cone, mineral
acids form formic acid and NH, ; boiling solu-
tions of alkalis react similarly ; very cone. HClAq
in the cold produces f ormamide (Claisen a. Mat-
thews, B. 16, 308) ; with HCl and alcohols, alkyl
salts of formic acid are produced (Volhard, A.
176, 135). — 14. With alhaUs in solution, alkali
cyanide is formed ; on heating alkali formate
and NH3 are produced. — 15. Some metallic ox-
ides form cyanides and H^O, e.g. ZnO, HgO;
others give oxy-oyauides, e.g. PbO, CdO ; some
evolve cyanogen, e.g. PbOj (Liebig, A. 35, 3). —
16. Some metallic salts are decomposed by
HCNAq giving cyanides, e.g. many acetates, some
salts of Ag and Cu, some alkaline carbonates. —
17. Alkali polysulpMdes form sulphocyanides.
Com,binations. — 1. With water hydrates are
perhaps formed, but none has been isolated ; the
contraction and lowering of temperature (v.
beginning of this art.) point to formation of
2HCN.3H2O ; the change of M. P. on addition of
water seems perhaps ' to indicate a hydrate
HCN.H3O (Gautier, A. Ch. [4] 17, 120).— 2. With
hydrogen peroxide to form bxamide, CjOj{NH2)2
(Attfield,G.J.[2]l,94).— 3.With%dra5re»itoform
-CH3NH2 {v. Beactions, No. 9). — 4. With the haloid
acids : HCN saturated with HCl gas at - 10°,
and then heated to 35°-40° forms crystals of
NCH.HCl, insol. ether, sol. water, alcohol, and
acetic acid ; the dry compound dissociates in
vacuo (Gautier, C. B. 65, 410) ; dry HCl passed
into a mixture of HCN and CjHjO.OC^Hj at
— 10° to — 15° forms white prismatic crystals of
SNCH.3HC1, insol. ether, CHCI3, and acetic
acid, sol. water with decomposition (Claisen a.
Matthews, B. 16, 308). The compound
2NCH.3HiBr is produced similarly to the hydro-
chloride (Gal, C. B. 61, 643 ; Gautier, A. Oh.
[4] 17, 141 ; C. a. M., Z.C.). When HI gas is passed
into HCN the compound NCH.HI is formed,
crystallises from alcohol in rhombohedra, sub-
limes at 300°-400° with but slight decom-
position ; insol. ether, sol. cold water ; soon
changes to HI and NH4 formate (Gautier, C. B.
61, 380 ; Gal, C. B. 61, 643).— 6. With metalUc
, chlorides : anhydrous HCN combines with several
metallic chlorides with production of much heat ;
the compounds are decomposed by water; the
following have been obtained : (1) TiCl,.2NCH
(Wohler, A. 73, 226) ; (2) SnCl,.2NCH (Klein,.!.
74, 85); (3) Sb0l5.3N0H (Klein, l.e.) ; (4)
Fe,Cl„.4NCH (Klein, I.e.). BCI3 seems to form a
compound with HCN (v. Martins, A. 109, 81).
6. tfCN combines directly with very many
aldehydes, e.g. with acetic aldehyde it forma
OjHjO.NCH («. the different aldehydes).
Detection and Estimation.— \. Addition of
KOHAq followed by FeSO,Aq containing some
ferric salt ppts. Prussian blue mixed with
Fe(6H)j and FefOH), ; addition of HCl dis-
solves the Fe hydroxides and leaves Prussian
blue. If there be very little HCN or cyanide
present, a blue-green liquid is formed, wMoh on
standing deposits bluish flocks. This test will
detect fis grain of HCN in a very dilute liquid
(Taylor, A. 65, 263).— 2. To the liquid to be
tested are added a few drops of yellow NH,
sulphide, the liquid is evaporated on the steam-
bath, (NHJSCy is thus formed ; a few drops of
water are added and a drop of FcjClgAq, when
blood-red Fe(SCy)3 is iormed. This test will
detect
grain HCN in a very dilute liquid
(Taylor, i.c.).— 3. AgNOjAq pps. white AgCN,
e. sol. NHjAq, nnblackened by light, sol. cone,
boiling HNO, with evolution of CO,. Other
tests axe founded on (1) the insolubility of
Cuj(CN)j in dilute HClAq (Lassaigne, A. Ch. 27,
200) ; (2) the production of a blood-red colooi
on heating KCNAq with picric acid (Braun, Fr.
1864. 464 ; Vogel, G. C. 1866. 400 ; (3) the blue
colour produced by Cu salts with tincture of
guiacum in presence of HCN (Schonbein, £>.
1869. 67 ; Yogel, l.c. ; Eckmann, Fr. 1870. 429 ;
Link a. Mockel, Fr. 1878. .455). Insoluble
cyanides may be fused with dry NajSjOj,
dissolved in water, and tested with FojClaAq
(Frohde, C. G. 1863. 698). In cases of suspected
poisoning, HCN is separated by distUlation after
acidifying the matter with tartaric acid. (For
details, a manual of analysis must be consulted.)
HCN may be estimated by ppg. as AgCN,
from solutions slightly acidulated by HNO„ by
addition of AgNO, ; haloid acids must be absent;
the pp. is washed, dried at 100°, and weighed.
Liebig's volumetric method may be used when
haloid acids are present (A. 77, 102) ; the solu-
tion is made strongly alkaline by KOHAq, and
standardised AgN03Aq is added until a permanent
turbidity is produced ; the compound AgK(CN),
is produced but remains dissolved until addition
of excess of silver forms insoluble AgCN. 1 c.o.
of decinormal silver solution (10-8 grams Ag per
litre) = -0054 gram HCN.
Constitutwn. — Cyanhydric acid may be
(1) HCN or (2) HNC; formula (1) represents
the atom of H as directly associated with the C
atom, while formula (2) represents the atoms of
H and N as directly associated. The reactions
of this acid vriih alkalis show that the H atom
is acidic ; the fact that the acid combines
directly with the haloid acids favours the for-
mula N.CH, which suggests the properties of a
derivative of NHj. The formation of the acid
by the reaction of CHClj with KOHAq is in
keeping with the formula N.CH; this formula
also suggests the production of CH3NH2 by the
reaction of hydrogen with N.CH ; the production
of H.CC^NH, when cyanhydrio acid reacts with
H2O cannot decide between the formula N.CH
and G.NH. On the whole cyanhydric acid is best
regarded as the nitrile of formic acid; the for-
mula is written N.CH.
POLYMERIDE OP OTANHYBRIO AOTD. Tricyan-
hydric acid. HjCjN,. Produced by spontaneous
polymerisation of HCN, or of cone. HCNAq, in
CYANIC, niOYANIC, AND TRICYANIO ACIDS.
303
presence of alkalis, also from KCN (Lange, B. 6,
99 ; Wippermaun, B. 7, 767 ; Lesooeur a. Bigault,
C. B. 89, 310). Prepared by treating tiie brown
Bubstanoe produced when HON is allowed to
cbange in air, with much ether, crystallising, dis-
solving in ether, shaking with animal char,
crystallising, and re-crystallising from hot water.
Triclinio crystals ; v. sol. alcohol, less sol. ether.
Solubility in water -55 at 34°, 5-5-5 at 100°.
Begins to decompose at 140°, melts at about
180°, and deflagrates at a higher temperature.
When slowly heated with water forms HON
and the products of decomposition of this acid
(H.COjH, NH„ &c.). He^ated with BaOAq, with
HOlAq, or HIAq, produces XJOj, NHj, and glycocoU
fWippermann, B. 7, 767) ; hence tricyanhydrio
acid appears to be the nitrile of amido-malonio
acid, CN.CH(NH2).CN (c/.Bieyer, A. 131, 297).
M. M. P. M.
DICYANHTDEIH v. Di-oyAuo-PKopyi, al-
cohol.
CYANIC (SULPHO) ACID. SULPHOCYANIC
ACID AND POLYHEEIDES. (Thioayanio acid.
Eydro-sulphocyanic acid. Sulphocyanhydric
'acid. Sulphocarbimide.) Only one isomeride
of the composition HCNS is known,' and it is
probably normal sulphooyauic acid HS.CN ; the
acid HN.CS has not been isolated although
ethereal salts derived from it are known. A
polymeride pt sulphooyanic acid, viz. H^S^N^Cj, is
known, and the methylic salt of trisulphocyanio
acid (H5C:,N.,S;,) is also known (cf. Cyanic acid).
The metallic salts of the form MS.CN are
described as sulphocyanides in the article
Cyanidhs.
Preparation. — 1. Dilute solutions of HS.CN
are obtained by distilling excess of a sulpho-
cyauide with dilute H^SOjAq ; more cone, solu-
tions are obtained by distilling KS.GN with cone.
•H3P04Aq, or by the reaction of HjS with
Hg{SCN),, or Pb(SCN)., (Hermes, J. pr. 97, 465;
Zimmermann, A. 199, 1). -2. Sulphooyanic
acid is obtained by gently heating a small quan-
tity of Hg(SCN)j in a stream of dry H,S (Wohler,
O. A. 69, 271) ; explosions may occur if large
quantities are used (Hermes, i.e.).
Properties. -A colourless, strongly smelling,
liquid ; crystallises when surrounded by snow
and salt. An aqueous solution containing 12-7
p.e. of the acid has S.G. 1-04 at 17° (Hermes,
l'.c.). HSCy is a very strong acid ; the affinity
is nearly equal to that of HCl (v. Ostwald's
Lehrbuch der allgemeinen Chemie, 2, 849).
Reactions. — 1. Decomposed by heat to HON
and persulphocyanio acid (H2C2N2S3). Stable
in dilute aqueous solution (about 5 p.c.) ; the
anhydrous acid polymerises on standing, On
distilling the aqueous acid the greater part is
vapourised unchanged.— 2. Heated with mineral
acids, is decomposed to HON and H^C^N^Sa, or
to CO,, NH„ and CSj or H^S ; the products of
decomposition vary with the concentration of the
solution of HS.CN used {cf. Volckel, A. 43, 74).
8. Decomposed by sulphydric acid (3.^8) to
CS2 and NH3 (Volckel, J.c.).— 4. Oxidisers, e.g.
KMnOjAq, produce HON andH^SG, (P6an, CB.
46, 626).— 6. With zinc and sulphwric acid, re-
acts to form HjS, NH„ NH2(CH,), and (CHJ^S,
(Hofmann, B. 1. 179).— 6. Heated with fairly
cone. suVphv/ric acid, COS and NH, are pro-
duced (Than, A. Swppl. 6, 236). — 7. Orgamc
acids react to form COS and amides, or
sometimes nitriles, e.g. HS.CN + CjHjO.OH
= COS + 0aH,0.NH2 (Letts, B. 5, 669; Kekul6,
B. 6, 113).
The metallic salts of sulphooyanic acid are
described as Sulphocyanides under Cyanides.
The ethereal salts of normal sulphooyanic acid,
of the type Et.S.Cy, are described as Ethyl, <feo.,
suiPHooYANiDE ; the ethereal salts derived from
isosulphboyanio acid, of the type Et.N.CS, are
described as Ethyl, &o., thio-oabbimide.
PoLYMEBIDES OE SULPHOOYANIC ACID.
I. Disulphocyanic acid HjSaCjNj (Fleischer,
A. 179, 204). Prepared by adding alcoholic so-
lution of KOH to persulpliooyanic a,oid (HjCaN^Sj;
obtained by adding 3 vols. H^SOiAq, S.G. 1'34,
to cone. NH^.SCNAq, and crystallising the crys-
tals which separate from hot water) ; the crystals
which separate are K2C2NJS2, they are collected
and decomposed by dilute H^SOjAq ; the acid
separates as a wax-like yellow mass, which
hardens after a time. Sol. alcohol, nearly insol.
water; when the solution is heated HSCN is
formed.
II. Trisulphoeyanic acid ; this acid is not
known, but its methylic salt, MejSjCaNj, is ob-
tained' along with methyl thiocarbimide
[Me.N.CS (q. v.)}, by heating Me.S.Cy to 180°
(Hofmann, B. 13, 1349). '
For metallic salts of disulphocyanic acid v,
Cyanueates and Sulphocyanubates, p. 360.
M. M. P. M.
CYANIC, DICYANIC, AND TRICYANIO
ACIDS and their derivatives. — HistokioalInteo-
DUOTioN. — Very soon after his inquiry into the
constitution of Prussian Blue, an investigation
which had enriched science with the discovery of
Prussic Acid, Soheele (1786, Opuscula 2, 76) con-
ducted a series of experiments with a view to
determine the nature of a specimen of urinary
calculus. The calculus happened to be of the
I acid variety. The outcome of this work was the
I discovery of Uric and Cyanurfc or Pyro-urio
acids. This is the earliest record of an oxygen
compound of cyanogen. ^ Soheele, however, did
not realise that he had in his hands a hitherto
unknown chemical compound. Distilling some
of the calculus he obtained among other products
a brown sublimate, which admitted of purifica-
tion by resublimation. The properties of this
sublimate are those now known to belong to
cyanuric acid. Moreover, oyanuric acid may be
obtained by the mode of procedure described. To
Scheele the sublimate appeared to resemble suc-
cinic acid. Pearson (1798, Tr. 34) repeated these
experiments, and observed in addition most of
the characters of cyanuric acid known at the
present day, but, like Soheele, this observer did
not recognise the sublimate as a new substance,
and was content to note its similarity to benzoic
acid. Henry (1818, Thomson's Systim'e de
Chemie, 2, 198) was the first to point out the
independent nature of the acid, and the earliest
analysis was made by Chevallier and Lassaigne
(1820, A.Ch. 13, 155).
At the same time that the oyanuric acid of
Soheele was being studied; the first observations
were made of three important classes of com-
pounds —the fulminates, the cyanates, and thii
thiocyahates. Brugnatelli (1798, A. Ch. 27, 331)
prepared ' Fulminating Silver,' which, however,
804
OYANIC, DICYANIO, AND TRICTANIC ACIDS.
he 'regarded as oxalate, and Howard (1800, Tr.
201) about the same time described the manufac-
ture and properties of ' Fulminating Mercury'.'
That sulphur is capable of combining directly
with potassium cyanide, forming ' Thiocyanate,'
was first distinctly observed by Porret (1814, Tr.
527), the reaction having been studied previously
by Buchholz (1798, BeitragzvirErweiterungund
Berichtigung der Chemie, 1, 88). The predic-
tion of Gay-Lusaac of a class of cyanates was
verified by Vauquelin (1818, A. Ch. 9, 115, 22,
134), who found Ammonium Cyanate among the
prodnots of the spontaneous decomposition of
cyanogen in water.
The discovery of the first compound of cyanic
acid was soon followed by that of other cyanates
and of the acid itself. Wohler (1822-24, G. A.
71, 95 ; 73, 157 ; P. 1, 117) analysed many of
these, including the silver salt, from which he
derived the formula of the acid. A little later,
when heating some cyanuric acid, this chemist
noticed that a gas was given off, having
a pe/suliar pungent odour. This proved to be
free Cyanic Acid, and by a suitable cooling ap-
paratus Wohler succeeded in liquefying it. The
free cyanic acid thus obtained was examined in
an important memoir by Liebig and Wohler
(1830,P. 20, 369), and its constitution established
so far as the exigencies of the time required,
liiebig reverts to this question again in 1838 (A.
26, 122), pointing out that cyanic acid does not
form double salts and is monobasic.
In the meantime a study of the fulminating
mercury of Howard had furnished Liebig with
some interesting results. These were published
in 1823 (Gf. A. 75, 393) and in conjunction with
Gay-Lussao in Paris in 1824 {A. Ch. 25, 285).
From the silver salt, which was obtained in a
condition sufficiently pure, the composition,
molecular weight, and basicity of fulininic acid
were ascertained. The free acid was, however,
, not isolated. Later (1838, A. 26, 122) Liebig
points out the relation of fulminic acid to its
isomerides, cyanic and cyanuric acids. It is
shown to form double salts and to be dibasic.
In the hands of Berthollet (1787, A. Ch. 1,
35) and Gay-Lussac (1815, A. Oh. 90, 200) chlo-
rine had been made to act upon prussic acid with
the formation of gaseous Cyanogen Chloride.
Serullas (1828, A. Ch. 38, 390), now employing
the same agents in the presence of sunlight, ob-
tained a crystalline solid now known to be Cyan-
nric Chloride. By the prolonged action of water
this compound was found to decompose, forming
hydrochloric acid and a new solid, named by
Serullas Cyanic Acid. This cyanic acid was
perceived to be quite distinct from the cyanic
acid of Wohler, but Serullas does not seem to
have compared it with the pyro-uric acid of
Scheele. Nevertheless, the properties noted by
Serullas agree in all respects with those given by
Pearson for Scheele's acid. The analysis made
by Serullas, though not inaccurate for the time,
entirely overlooked the hydrogen.
Wohler made the next step forward by the
. discovery Of a new compound, Cyanuric Acid,
among the products' of the action of heat on
urea (1829, P. 15, 622). This cyanuric acid was
at OQce compared both with the pyro-urio acid of
Scheele and with the cyanic acid of Serullas.
Its properties were found to agree with both of
the earlier known substances, and when careful
analyses were made of all three they proved tu
be identical. The Subject is finally discussed
by Liebig and Wohler (1830, P. 20, 369), where
it is suggested that the term cyanuric acid should
be adopted for the single compound whether ob-
tained by the distillation of uric acid (Scheele),
the action of water on cyanuric chloride (Serullas),
or the action of heat on urea (Wohler), and that
the name cyanic acid should be retained for the
pungent liquid which Wijhler had found as a
decomposition product of cyanuric acid, and of
which Vauquelin had previously prepared 'the
ammonium salt.
The question of the constitution of cyanic
acid and its isomerides is the subjecf of another
memoir by Liebig (1838,4.26, 145). The basicity
of cyanuric acid, which had been a matter of
controversy between Wohler and Liebig, is finally
decided by the discovery of a triargentic salt, and
it is shown to have the formula B. fig's gO^iSfi.
The analogy is pointed out between the acids of
phosphorus as elucidated by Graham (1833, Tr.
253) and the three isomerides : — monobasic
cyanic acidHCNO,dlb&sic fulminic acid H22CNO,
and tribasic cyanuric acid H33CNO.
The Thiocyanic Acid, of which Porret pre-
pared the potassium salt, was isolated by Wohler
in 1829 (C. A. 69, 271), a,nd in the same year
Liebig (P. 15, 563) came across a solid substance
among the products of the action of water on
cyanuric chloride which, in conjunction with
Wohler, he found again (1830, P. 20, 386) as a
product of the decomposition of cyanic acid with
, water. This compound isomeric with cyanuric
acid, but insoluble, was called ' insoluble cyanuric
acid ' or, later, Cyamelide.
About this time, too, Liebig (1834, A. 10, 10)
by acting on ammonium thiocyanate by heat
produced a substance called Melam, and from
this, by the action of dilute soda, a base was
formed richer in the elements of ammonia. This
base was regarded by Liebig as the amide of
cyanuric acid, and was called from its parent
substance Melamin^ (1834, A. 10, 18). Another
base nearly related to these, Mellone, was ob-
tained by the action of heat on melam, and from
mellone, by treatment with nitric acid Liebig
(1834, A. 10, 34) prepared an acid, Cyanilio Acid,
which proved to be an isomeride of cyanuric acid,
distinguished from the latter acid chiefly by its
crystalline form and solubility.
The thirty-five years following 1840 were very
largely devoted to the discovery of ethereal deri-
vatives of cyanic and cyanuric acids, and to a
study of their structure with a view to rendering
intelligible the very remarkable metameric series
of compounds which were brought to light. But
aside from this main current of research there
are many other discoveries of scarcely less im*
portance. Two of these call for attention at
once — ^the study of the action of heat on nitrate
of urea by Pelouze (1842, A. 44, 106) and Wiede-
mann (1848, A. 68, 324), and the interesting re-
action between cyanic acid and aldehyde whereby
Liebig and Wohler (1846, A. 69, 296) prepared
the compound known as Trigenio Acid.
Three important series of alkyl derivatives
were discovered during the years 1847-48;
the cyanic and cyanuric ethers of Wurtz, and
the thiocyanic ethers of Cahours. By acting
OYANIO, DICYANIC. AND TRIOYANIO ACIDS.
805
on alkyl pot&ssium sulphate with a salt of cyanic
acid, Wurtz (1848, O. B. 26, 368 ; 27, 241) ob-
tained Alkyl Cyanates,, and using a cyanurate
instead of a cyanate he suooeeded in preparing
a series of Alkyl Cyanurates. Both these classes
of ethers when decomposed by water, in presence
of dilute acids or alkalis, give amines and carbon
dioxide, showing that they have a similar struc-
ture. The discovery of the ethers of Wurtz was
partly anticipated by Cahours (1847, A. Ch. 18,
261), who by the analogous reaction of alkyl
calcium sulphate with potassium thiocyanate
obtained Alkylthiooyanates. The thiooyanic
ethers do not admit of their constitution being
studied by decomposition with water, but the
same end is attained if they be subjected to the
reducing action of nascent hydrogen. The thio-
others of Cahours give by this treatment mer-
captan and hydrocyanic acid, showing that the
^yl radicle is attached to the sulphur and not
to the nitrogen.
The study of ethereal derivatives must now
give way to tiie consideration of several new re-
actions which were -brought to light at this time.
Debus (1849,, A. 72, 18) in his work on ethyl
thiocarbamate or xanthogenamide NH^.CS.OEt
orNHj.CO.SEt was led to the discovery of a re-
action by which this compound breaks down
into mercaptan andcyanurio acid. If the consti-
tution of xanthogenamide were better known, an
iinportant insight might thus be obtained into
that of oyanurio acid. Notwithstanding the
attempts of Bineau (1839, A.Oh. 70, 251) to pre-
pare an amide of cyanic acid homologous with
the cyanuramide or melamine of Liebig, no such
compound was isolated until Cloez and Can-
nizzaro instituted their inquiry in 1851 (O. B.
32, 62). These chemists obtained Cyanamide
by acting upon cyanogen chloride with am-
monia. A very remarkable property of the
cyanamide thus obtained is the ease with which
it undergoes polymerisation. The result of this
intramolecular rearrangement, as shown by
Bailstein and Geuther (1868, A. 108, 99; 123,
341) is the formation of the dieyanogen homo-
Ijgue Dicyandiamide. An isomeric series of
tomologous amides is thus completed corre-
sponding to the three classes of mono-, di-, and
tri- cyanogen compounds. Employing amines
instead of ammonia in the reaction of Cloez and
Cannizzaro, the alkyl cyanamides were prepared
by Cahours and Clpez (1854, 0. B. 38, 354).
Another instance of polymerisation was an-
nounced at this time by Liebig (1855, A. 95, 282).
When fulminating mercury is allowed to stand
in presence of water it gradually changes its
colour and other properties. These changes
were found to correspond to an entire rearrange-
ment of the molecule, the dicyanic fulminic
acid having polymerised to trioyanio Pulminurio
Acid. The new acid is metameric with oyanuric
acid, but in its basicity and in other respects it
is quite distinct from that compound. Puhnin-
urio acid was discovered independently by
Schisohkow (A. 97, 53 ; 101, 213), whose atten-
tion was also directed to the constitution of the
isomeric fulminic acid from which it is, derived.
Mercuric fulminate, according to Sohischkow
(J. B. 16, 276), is Hg(CN)2.02(N03)j.Hg, and ful-
minic acid (H0N)j.0A2NOj. On the other
hand Kekul6 (A. 101, 200 j 105, 279), in view of
Vol. U.
other reactions, regarded fulminic acid as nitre-
aeetonitril GHaNO^CN.
Eeturning once more to the ethers, a reaction
must be noticed that was first studied by Cloez
(1857, 0. B. 44, 482), which in the hands of
Hofmann and other later investigators has done
much to give order to the knowledge of cyanic
derivatives. Cloez caused cyanogen chloride to
act on sodium ethylate,.and obtained a oompound-
whioh he called OyanethoUne and which has
sometimes • been regarded as consisting of Bp
cyanic ether isomeric with that of Wurtz. Gal
(1866, G. B. 61, 527), who observed its decom-
position products, correctly so regarded it, and
moreover judged that it was related to the cyanic
ethers of WurtZ- in the same manner that the
nitriles are related to the isonitriles.
Still another reaction was announced at this
time for the preparation of ethers. Habioh a.
Limpricht (1859, A. 109, 111) discovered that
silver cyanurate and alkyl iodides react, forming
cyanuric ethers identical with those of Wurtz.
The Cloez reaction was now, in 1870, the
subject of an important investigation by Hof-
mann and Olshausen (B. 3, 269). No cyanic
ether was found,^ but, instead, these observers
succeeded in preparingaseries of Cyanuric Ethers
metameric with those of- Wurtz. The niethyl
analogue of the cyanetholine of Cloez and Gal
proves to be a mixture containing cyanuric ether
and an amido- derivative. Cyanic ethers homo-
logous with these cyanuric ethers and metameric
with the cyanic ethers of Wurtz have never been
isolated. Hofmann and Olshausen were led to
predict the formation of a series of cyanuric ethers
in this reaction from its analogy to that of Cloez
and Cannizzaro for cyanamide and Cahours and
Cloez for alkyl cyanamides, thus : —
01]0N + (NH)H|H (Cloez and Cannizzaro)
Cl|CN-H(NH)EtiH (Cahours and Cloez)
ClfON + OEtJH (Hofmann and Olshausen).
Now in the second reaction the alkyl cyanamide
was known to polymerise readily at the moment
of its formation to alkyl melamine. Just in the
same manner, thought Hofmann and Olshausen,
might the product of the third reaction, which
differs only in containing oxygen for imidogen,
polymerise at the moment of its formation to a
cyanuric ether. This hypothesis was confirmed
by experiment.
The cyanuric ethers thus obtained when
submitted to the action of water in presence of
dilute acids or alkalis give cyanuric acid and
alcohol, showing that the alkyl radicle is at-
tached to the oxygen and not to the nitrogen,
as it would seem to be in the case of the Wurtz
ethers. It would thus appear that the Wurtz
ethers are substituted imide compounds, while
those of Hofmann and Olshausen are substituted
hydroxyl derivatives. The reaction of both
with water then becomes clear, thus :—
Hofxnann and Olsbausen.
OaNsSOE'
03H3H3
~(0N),30H|3B'03" SOOjISNHjR'"
■Wurtz.
CjOaNsB',
> O^H,,
sm
CYANIC, DICYANIC, AND TRICYANIO ACIDS.
The difference between these two classes of
ethers may be represented by the formulas : —
(CN),^OE'
\0E'
(00)/^KE'
01 better still by the use of ring formulae, a de-
vice which" is especially useful when more com-
plex reactions have to be studied. The ether
correeponding to the hydroxy! acid is of course
the normal ox ortho-ether, while the imide sub-
stituted ether is the iso-ether : —
Iso-ether ol Wurtz.
CO
>NE'
Normal ether of Hofmann and
Olshausen.
COE'
JnoR'
E'OO'i ^COR'
N
una
oc
CO
In the same manner the normal cyanic ether
which in the Cloez reaction is probably formed
in the first instance, but which has not been iso-
lated, may be supposed to be related to the
cyanic ether of Wurtz : —
(CN).OE'
Hypothetical nohnal cyanlo
ether.
(CO):NE'
Isocyanlc ether of
Wurtz.
And the decomposition by water of the two
ethers may be represented : —
CNOE'
HOH
CONE'
OH,
(0N)OH|E'OH COj|NajB'
Decomposition of hypothetical Decomposition of
normal ether. iso-ether.
A very interesting instance of intramolecular
change was announced by Hofmann andOlshau-
sen in this same memoir. It was noticed that
the melting-point of trimethyl normal oyanurate
changed on continued heating. In the &:st place
it melts at 132°, but after heating for some time
the melting-point rises and remains constant at
175°. Metastasis was suspected, and it was found
that, while before the application of heat the
cyanurate gave when decomposed with water
alcohol and cyanuric acid, after that operation
its decomposition products were carbon dioxide
and amine. The normal ether had changed into
the corresponding iso-ether of Wurtz. Such in-
stances of intramolecular migration from nor-
mal to iso- in the case of alkyl derivatives of
cyanogen compounds are now known to be of
frequent occurrence.
Of the thio-analogues of these isomeric ethers,
one series had been discovered by Cahours. On
reduction with nascent hydrogen they gave mer-
captan and hydrocyanic acid. These were the
analogues of the hypothetical normal cyanic
ethers. The series of isomeric thiocyanates
corresponding to the cyanic ethers of Wurtz
were syntbesised by Hofmann (1868, B. 1, 25 a.
169 ; 2, 452 ; 7, 814; 8, 106), and constitute the
'mustard oils' of which ordinary mustard oil is
a member. When the mercury salt of mono-
alkyldithiocarbamic acid is distilled it loses
mercuric sulphide, and sulphuretted hydrogen
and alkyl thio-isocyanate passes over. The
thio-isocyanio ethers give on treatment with
nascent hydrogen not mercaptan and hydro-
cyanic acid but amines and thio-aldehyde. The
two reactions may be seen thus : —
Normal thio-ether of Cahours. Isothio-ether of Hofmana.
CN.SE' CS:NE'
li JB. S2 Mj
CNH I E'SH HCHS | NH^R'
The following discoveries also belong to this
period : — The production of isocyanic ethers from
isonitriles by direct oxidation accomplished by
Gautier (1869, C. B. 67, 804). The discovery of
Dicyanio Ethers and Alkyl Melamines by Hof-
mann (1861, A. Suppl. 1, 51 ; B. 3, 765 ; 1869, B.
2, 602 ; 3, 264). The former by polymerisation
of phenyWsocyanate in presence of triethyl-
phosphine, and the latter by desulphurisation
of monoalkylthio-urea in which case alkyl cyan-
amide is doubtless first formed and then changed
into the polymeric melamine. Finally, the ex-
periment of Beilstein (1860, A. 116, 357), which
showed that cyanuric acid treated with phos-
phorus pentaohloride gives cyanuric chloride.
Cyanuric chloride is thus seen to be related to
cyanuric acid precisely in the same way aa
acetyl chloride for example is related to apetio
acid. It may be obtained from the acid by
substitution of its hydroxyl by chlorine when
treated with phosphorus pentaohloride, and, as
Serullas was the first to show, the chloride by
treatment with water loses its chlorine and again
assumes hydroxyl in its place, becoming cyanuric
acid.
A period is now reached, commencing about
the year 1875 and extending to the present day,
during which the activity of investigators in this
subject has been directed in the main to the
question of the constitution of cyanic and cyau-
np:ic acids. To these must be added melamine,
for just as the acids give rise each to two parallel
series of metameric ethers, so, as it will appear,
does melamine. This isomerism has not yet been
found among the alkyl cyanamides or dicyanic
diamides. It will be seen that in the case of
the parent hydrogen compounds no reactions
have been discovered which permit, as in the
case of their alkyl derivatives, the assertion
that the one is normal or of the hydroxyl type,
and the other iso- or of the imide type.
The discussion was inaugurated by Nencki
(1876, B. 9, 232), who, working on the compound
aceto-guanidine, found that by a series of reactions
it is converted finally into cyanuric acid. In a
second communication (B. 9, 244) he suggested
an explanation of these reactions assuming the
imide nature of cyanic acid. This procedure led
of course to the view that cyanuric acid is iso-
or imide in its constitution. Further evidence in
favour of the imide structure of both cyanic and
cyanuric acids is found according to Fleischer
{JB. 9, 486) in the desulphurisation of ammonium
thiocarbamate NH^.CO.SNH, by which reaction
either urea or iso-cyanate should result : experi-
ment showed that ordinary ammonium cyanate /
was formed. Weith (B, 9, 454) then joined the
controversy, and proposed an altogether new set
of formulas for the compounds obtained by Nencki
from aceto-guanidine. Nevertheless, whilepoint-
ing out that the imide nature of the acids waa
not proven, he considered the weight of evidence
to be in favour of that view. Hichler(B. 9, 716)
advanced another reaction to support the iso-
CYANIC, DICYANIO, AND TRIOYANIC ACIDS.'
307
theory, the distillation of M-dlphenylur6a, which
yields cyanic acid and diphenylamine. This
teaction has, however, no' more value as proof
than the action of heat on nrea itself.
So far the evidence had been very largely in
favour of the iso- hypothesis. Glaus (B. 9, 721)
now joined issue with the preceding observers.
He questioned the value of the little understood
guanidine reactions of Nenoki as proof of con-
stitution, and showed, as Weith had indeed al-
ready done, that with equally probable assump-
tions the ehaugfes observed by Nencki might be
explained so as to support the opposite view.
Similarly he contended againstMeischer that the
formula for ammonium thidcarbamate is by
no means established, and if the alternative
hydroxyl formula, NHj.CS.ONHj, be used, the
reaction supports the normal hypothesis. To
these criticisms both Nenoki and Fleischer re-
plied, Fleischer (B. 9, 988) defending the for-
mula which he had employed for thiocarbamio
acid, and Nencki (B. 9, 1008) considering at
length the evidence for and against the two con-
tending theories. The leading points are as fol-
lows : For the imide or iso- formula. — 1. The
easy breaking down of cyanic acid by the action
of water into ammonia and obrbon dioxide
C0NH + 0Hj=C0j + NH3.— 2. The conversion
of cyanic acid into formamide by the action of
nascent hydrogen C0:NH + H2 = H.C0.NHj.—
3. The reaction of Wurtz in which cyanates
and cyanurates yield iso- and not normal ethers
(CONjK + KE'SO^^CONE' + K^SO^. For the
hydroxyl or normal formula.— 1. If in order to
explain all the reactions of these bodies it is
found necessary to assume an intra-molecular
change, it is easier to imagine it taking place
from the normal to the isd- than from the iso-
to the normal atomic arrangements, since it is
known with what ease normal cyanic and cyan-
uric derivatives change to the iso- condition, and
thus to suppose that in the Wurtz reaction normal
ether is at first formed and that it immedi-
ately changes to iso-ether. — 2. Finally, Beilstein
had shown that cyaniiric chloride, the normal
structure of which does not admit of question, is
the chloride corresponding to cyanurio acid.
Nencki admits that the acetoguanidine reactions
tell equally for both theories. Nenoki concludes,
however, with Weith that the weight of evidence
is in favour of the imide structure. The discus-
sion was continued by Glaus {B. 9, 1165), Flei-
scher (B. 9, 1459), and Nencki (B. 9, 1552), but
little further advance was made.
The fundamental distinction between mono-,
di-, and tri-cyanic acids which Liebig so clearly
pointed out has been confirmed, and its value
appreciated more and more. It may be that
fulminic acid is not the dicyanic acid homo-
logous with cyanic and cyanuric acids, and that
this has yet to be discovered. Indeed, there may
be many such mono-, di-, and tri-cyanogen series
to which the numerous isomerides of cyanic acid
of which the constitution is at present so little
known will contribute members.
By the help of this conception a place is
ready for the Thiodicyanio Acid discovered in
1876 by Fleischer {A. 179, 204), and perhaps
for several new isomerides of cyanic acid which
have now to be noticed. It was just at this
time that Herzig {B. 12, 170) announced the
discovery of o- and jS-Oyanuric Aoids. These
new acids were said to be obtained by the action
' of hexabromaoetone on urea. It has, however,
recently been shown (Senior, 0. J. 49, 693 ; 49,
748) that both these acids are merely ordinary
cyanuric acid disguised by traces of impurities.
The isomerism of the cyanamido-oarbonio acid
discovered by J. Meyer (1878, /. pr. 18, 419)
is merely coincidental, that compound having
nothing further in common with cyanuric deri-
vatives. Four isomerides, however, remain to be
noted, aU derived from fulminic acid. The first
is Isofulminurio Acid. It was prepared by Bhren-
berg (1884, J.pr. 30, 38) by acting on an ethereal
solution of free fuhninic acid with ammonia.
The remaining three isomerides were discovered
by Scholvien (1885, J.pr. 32, 461), and all arise
out of the action of dilute sul^huno acid on ful-
minates. They are Meta-fulminurio Acid, /3-Iso-
fnlminurio Acid, and Iso-oyanilic Acid. Metallic
salts of each were described, but no alkyl or
other derivatives.
In the present state of their history it would
be premature to speculate as to the constitution
of this remarkable group of isomerides. It may,
however, be worth while to bear in mind that the
possible metamerides of cyanurio acid are very
great, especially when mixed types are con-
sidered, as, for instance, the two conceivable inr
termediate acids between normal and iso-oyan-
uric acid (c/. Senior, Inaug. Dissert., Berlin,
[1887] 28).
A further study of these fulminuric acids
may help to olear up the constitution of fulminic
acid itself, for like the latter acid some of th^m
evolve hydroxylamine when decomposed by
water in presence of hydrochloric acid. It was
on this account that Steiner (1883, B. 16, 1484)
suggested the following isonitroso- formula for
0=NOH
fulminic acid |{ . , whereas he had pre-
C=NOH
viously (1876, B. 9, 782) been an adherent of
KekuU (1857, A. 101, 200 ; 105, 279), who re-
garded it as nitroacetonitrile. The recent work of
Divers ([1886] C. J. 47, 79) has led to another
N=CH
formula 0<' | . According to Armstrong,
N=GOH
the essential facts are best represented for the
«C— OH
present by one of the following, N? |
\0=N.OH
N=GH <
or I I (O.X47,79).
0-C=N.OH
In the next place two announcements call for
notice which have an interesting bearing on the
constitution of cyanuric acid. The first is the
production of melanurenic acid, a derivative of
cyanuric acid, by Bamberger^ by the action of
water on dicyandiamide (Inaug. Dissert., Berlin
1880 ; B 16, 1074 ; 16, 1459 ; 16, 1703). Bam-
berger ascribes to dicyandiamide the formula
G:NH.NH2:NHGN as preferable to Baumann's
formula (1873, B. 6, 1375), (CNH)<;^j^(ONH).
The second is the study of the absorption spec
trum of cyanuric acid which led Hartley (1882,
G.J.il, 48) to the conclusion that it has a ring
formula and doubly-linked atoms. This is of
x2
308
CYANIC, DICYANIC, AND TRIOYANIC ACIDS.
course quite in accord with the normal' or hy-
droxyl theory.
There remain to be considered the important
researches of Hofmann, Elason, Fonomareff,
Mulder, and Bathke. These investigations are
for the most part contemporaneous. They also
largely supplement one another ; and although
they do not explicitly support the same hypo-
thesis, they do not take the form of a discussion.
Only an outline of the more important features
of this work can be attempted here.
Commencing with Mulder in the year 1882 :
the Cloez reaction was the first to engage the
attention of this observer (ii. 1, il, 191 ; 2, 133;
3, 2S7). ' The results in the ethyl series were
similar and parallel to those in the methyl series
of Hofmann and Olshausen, The most interest-
ing observation is that normal cyanic and cyan-
uric ethers give bromine addition compounds,
while the isocyanio and cyanurio ethers form no
such combinations. This, according to Mulder,
becomes a test by which the one structure can be
distinguished from the other. Now cyanurio
acid does not combine with bromine, and hence
it is regarded as iso- in constitution. The com-
pound with cyanuric ethyl ether has the formula
OgNjOgEtsBr,. By the use of this test Mulder
was led in 1885 to recognise the diethyl cyanurio
ether of Habich and Limpricht as an iso- com-
pound (B. 4, 91). Subsequent observation has,
^however, not confirmed the value of this reaction
as a test in all cases.
Many attempts have been made to discover
among the metallic cyanates and cyanurates
isomeric differences like those found among the
others. An investigation of Gahuels in 1884
{0. E. 99, 239) would seem to show that metallic
cyanides analogous to the nitriles andcarbamines
edst, but hitherto no one has found evidence of
a similar isomerism among the metallic cyanates
or cyanurates. The experiments of Mulder in
1882 {B. 15, 69) with this object proved as
fruitless as those of Bannow (1871, B. 4, 254 ;
13, 2201) had been.
Mulder suggested new formulee for bromide
and chloride of cyanogen K33CBr and NjSCCl,
and in a series of communications in 1885-6 (i2.
4,47; 4,151; 5, 65; 5, 84; 5,99) studied the
properties of the bromide. The curious fact was
noted that pure cyanogen bromide does not
polymerise, but that this change takes place
readily in presence of a trace of free bromine.
Two curious addition products of cyanogen
brfflnide with ethyl cyanurate are described
C3N,OsBt32BrCN and C.NjOaEtjBlrCN (cf. Senior,
Itumg. IHssert., Berlin, 1887, 34).
As in the case of Mulder, so the work of
PonomareS commenced with a study of the
cy^netholine of Clo€z. This chemist in 1882
(B. 15, 613) arrived at results in accordance with
those of Hofmann and Olshausen, and proposed
the use of mercuric chloride to distinguish iso-
f rom normal cyanuric compounds. This reagent
gives crystalline addition compounds with nor-
mal derivatives, that in the case of normal
ethyl cyanurate being (CN)j30Et,Hg01j. Unfor-
tunately, like the corresponding bromine test of
Mulder, this mercuric chloride test has been
shown to be inapplicable to all cases (Hofmann,
1885-6, B. 18, 2796.; 19, 2093).
The study of the formation of cyanurio ethers
and the preparation of alkoyl derivatives in the
hands of Ponomareff threw additional light on
their structure. Hofmann and Olshausen had
prepared the cyanuric ethers by the Cloez reac-
tion, using cyanogen chloride. The method was
simplified by Ponomareff in 1885 {B. 18, 3261),
who employed the already polymerised cyanurio
chloride. By this means he obtained normal
cyanurio ethers which gave cyanuric chloride
again when treated with phosphorus pentachlor-
ide, and gave melamine by the action of am-
monia. In the next place this observer studied
the reaction of Habich and Limpricht, by which
only isocyanurio ethers had been obtained. By
allowing the alkyl iodide to act on silver cyan-
urate at a low temperature there was always
formed together vnth the isocyanurate some
ether that gave a crystalline compound with
mercuric chloride, and hence was judged by Po-
nomareff to be normal ether. The experiment
was afterwards repeated by Hofmann and the
crystalline mercuric chloride compound examined
(1886, B. 19, 2093), but it was proved that the
mercuric chloride was combined not with normal
but with iso- ether. In the same memoir Pono-
mareff described the first alkoyl derivative, of
cyanurio acid, triacetyl cyanurate. The corre-
sponding tribenzoyl cyanurate was obtained soon
afterwards by Senior (1886, C. J. 49,813).
The reaction between dicyandiamide and
carbon dioxide already pointed out as giving
rise to a mixed cyanurio acid and mela-
mine, melanurenio acid, ^was made the basis
of an interesting communication froin Bathke
in 1885 (B. 18, 3102). This inquirer noted that
when such compounds as H^O or I^, or QO^,
which can divide into two divalent radicles, for
instance H, + 0, H^ -I- NH, and O + CO, combine
to form addition compounds with cyanogen deri-
vatives, they do so in accordance with a general
law, the one residue joining the carbon and
the other the nitrogen. Thus nitriles take up
the residues of water or sulphuretted hydrogen,
giving acid amides or thio-amides, or they take
up ammonia or amines forming amidines. To
this class of reactions belongs, according to
Bathke, the conversion of dicyandiamide into
melanurenio acid, and also the parallel reaction
announced for the first time between dicyandi-
amide and thiocyanic acid, where combination
to thioammeline takes place. Using Bamberger's
formula for dicyandiamide^ the reactions may be
lepresented thus : —
C S C3
hnAjj
HN
y\
^NH
HNcl + CI
H-
HNO
. JcNH
NHH
Dioyan- Thio-
diamide cyanio sold
Thio-
ammeline
C 0
CO
HN A N
hn/N
NH
HNci + '^O -
HNct ,
00
NHH
Dicyan- Cat
diamide dio
boa
xide
Mela
nure
wld
nio
The bearing of these reactions on the oonsti*
tution of cyanurio acid and melamine is evident
CYANIC, DICYANIO, AND TRICYANIO ACIDS.
309
Anuneline and melanurenic acids are amido-
acids between melamine and oyanurio acid, and
if the above expressions be the true ones, both
the acid and melamine are imido- or iso- and not
normal compounds. The following formuls
showing cyanuric acid and Inelamine both as
normal and iso- compounds wUl assist in making
this clear : —
COH
Iformftl
ONH,
hoc!
CNH,
HN
According to Hofmann the weight of eyidence
is in favour of the view that both these com-
pounds are normal in constitution. Bathke
pointed out that these two reactions must be
considered, and whether/ the formula of Bam-
berger be employed or the alternative one of
Baumann, they both lead to the conclusion that
thio-ammeline and melanurenic acid are iso-
compounds, and indirectly to the iso- nature of
cyanuric add and melamine. One class of re-
actions requires the one formula, another class of
reactions the other. In Bathke's view it is im-
possible to find a formula to account for both
classes of reactions. It seems that the position
of the hydrogen atoms, unlike that of the alkyl
radicles^ is not stable, and that indeed both for-
mulas may be employed side by side. In the
same manner Kathke recommends the use of two
formulsa for hydrocyanic acid, acetacetic ether,
the lactam and lactim groups, thio-urea, and
other similar cases.
In another communication (1887, S. 20, 1056)
this standpoint was developed further, and in
view of the discovery of several triphenyhuela-
mines Bathke suggested the addition of a third
imide type for alkyl melamines, thus : —
ONHR'
EBNOli JONHR'
Noimol
CNH CNB'
ETSr^NB' Hn/NnH
HNCl jONH
E'NCvJCNB'
NH ,
Slid iso-.
The radicles attached directly to th^ ring as in
the first iso- form are said to be in the eso- posi-
tion, while those attached to side chains as in
the second iso- form are termed exo-. This sys-
tem was suggested in order to account for the
iutanoes of complex isomerism in the case of
phenylmelamines, which Hofmann was the first
to point out. In the communications following,
Bathke ([1887-8], B. 20, 1065 ; 21,867 ; 21, 874)
announced several new complex derivatives, the
constitution of -^hich he studied by means of
this hypothesis. These are Phenyl Thiamme-
line, Triphenyl Ammeline, Honophenyl Iso-cy-
anuric acid, Diphenyl Melamine, and Triphenyl
Melamine.
No inquirer in this department of chemical
research has been more unwearied, and none
has been more successful, than Hofmann. As
early as 1857, in conjunction with Cahours {A.
102, 293), he discovered allyl cyanata, and from
that time to this he has reverted to the subject
again and again. The earlier communicationB
have been already noticed, but there remain a
series of exhaustive critical memoirs which have
appeared during the last few years of which only
the barest outUne can be given. They are an
attempt to settle the question of the constitution
chiefly of cyanuric acid and melamine, but they
bring into their service numerous new reactions
and classes of compounds.
In oneof the firstof these, in 1881 (B. 14, 2728),
Hofmann described a new reaction in which iso-
ethers are among the products. It is the action
of heat on alkyl acetyl urea. Together with
isocyanic ether di- and tri-alkyl isocyanurate are
formed. In another paper in 1880 {B. 13, 1349)
some interesting instances of intramolecular
change are described. Just as the cyanic methyl
ether at first formed in the CloSz reaction was
found by Hofmann and Olshausen to polymerise
to methyl cyanurate, so the same change is now
effected in the case of methyl thiocyanate, which
is converted into methyl thiocyanurate, and also
(1885, B. 18, 765) in that ^of phenyl isooyanate,
which becomes phenyl isocyanurate. The general
tendency of the normal to pass over into the mora
stable iso- atomic arrangement finds another
example here, for together with the tnmethyl-
thiocyanurate some of the iso- compound is
always formed. Hofmann called attention to
the fact that pure methyl-thiocyanate does not
polymerise by heat alone, but does so in presence
of a little hydrochloric acid. It wiU be remem-
bered that in the same manner Mulder found
that cyanogen bromide only admitted of poly-
merisation when mixed with some other sub>
stance, as, for instance, with free bromine. The
action of such agents as hydrochloric acid and
free bromine in these instances, and the still
more remarkable action of triethylphosphine or
pyridine (Snape, 1886, C. J. 49, 254); which con-
vert phenyl isocyanate only into dioyanate, while
if certain dry salts are substituted, sodium ace-
tate, sodium formate, or sodium carbonate, the
intramolecular re-arrangement goes as f ai; as the
production of cyanurate ; these are facts of
which chemistry in its present state of develop-
ment offers no explanation.
Prom methyl-thiooyanurate thus obtained
Hofmann isolated in 1885 for the first time free
Thiocyanurio Acid (B. 18, 2196). The methyl
ether, by treatment with sodium sulphide, is
converted into the sodium salt, methyl mercap-
tan being formed at the same time, and the
sodium salt, when treated with hydrochloric acid,
has its sodium replaced in three stages, forming
two intermediate acid sodium thio-oyannrates,
810
CYANIC, DIOYANIO, AND TRICYANIO ACIDS.
and finally free thio-cyanurio acid. The sodium
Bait of thiooyanuricacid maybe also prepared from
cyanuric chloride by the action of sodium mer-
captide.
Pursuing the inquiry still further into the
behaviour of this thio- analogue of cyanuric
acid, the action of ammonia and amines on the
trimethyl ether was investigated in 1885 {B.
18, 2755). Water decomposes the ether in ac-
cordance with the general reaction into cyanuric
acid and mercaptan, and it was thought that
ammonia might similarly give mercaptan and
melamine, thus : —
(CN)33SMe + 3H(HO) =(CN)s30H +3MeSH
(CN)a3SMe + 3H(NHj) = (CNJsSNHj + 3MeSH-
Experiment proved this to be the case. Mela-
mine is thus advantageously prepared. The
reaction takes place, however, iu_ three stages,
two, intermediate compounds being formed —
mono-amido- and di-amido- ether — thus : —
/SMe
/NH,
.-NH,
/NH,
yame yi^a^ /J^-f-z vJ^I-Hz
CAr-SMe CaNj^SMe CsNj^NH, C.Njf-NH,
\SMe \SMe \SMe \kHj
ether intermediate compounds melamine.
The action of substituted ammonias was now
tried, aud corresponding alkyl melamines and
intermediate alkyl amido- ethers resulted.
Melamine and alkyl melamines are also
produced, as was expected, from cyanuric chlor-
ide, and ammonia or amines, and in this case,
too, a series of intermediate amido- and alkyl
amido- cyanuric chlorides was ,obtained, thus :
/CI /NH, /NH, /NH,
(CN),(-C1 (CNJsf CI (CN),f NH, (CN),^NH,
\C1 \C1 \C1 \nHj
cyanuric intermediate compounds melamine.
chloride
The second of these intermediate compounds
was identified as Liebig's ohlorcyanamide (1834,
.^.10,43), and its phenylamido- analogue as the
compound described by Laurent (1848, A. Cli.
[3] 22, 97) under the name chlorcyanilide.
The al^yl melamines obtained by these re-
actions were at once compared with those which
Hofmann had himself prepared sixteen years
b^ore by desulphurisation of substituted thio-
ureas, and were found to be metamerides. Here,
then, were two metamerio series of alkyl mela-
mines just as there are two series of alkyl
cyanates and cyauuraies and their thio- ana-
logues. One might be normal and the other iso-, .
corresponding to the normal and iso- cyanates
or oyanurates. Their constitution was now to
be solved. It was feared that the action of
water would give no clue to the structure of
these compounds, because on the assumption of
either constitution cyanuric acid and amine
would probably be produced. Thus :
(CN)s3NHMe + 3HjO = (CN)8aOH + SNH^Me
alkyl-71-uielamine cyanuric acid amine
(ONMe)33NH + 3H,0 = {C0)33NH + SNH^Me
alkyl-iso-melamine cyanuric acid amine.
It is true that in the one case the acid at first
formed ought to be normal and in the other iso-,
but all experience had shown that, whatever
might be the constitution of the acid in the first
moment of its existence, it was always found i
when examined to be one and the same cyanuric
acid. Experiment confirmed this expectatioa,
and it became necessary to seek some other
method.
This was found by Hofmann in 1885 (jB. 18,
2781) in a reaction between cyanuric chloride
and secondary amines. In this reaction neither
melamine nor its primary alkyl derivatives, but
secondary alkyl melamines were produced —
Hexa-alkyl Melamines. These were prepared,
and it was seen that an examination of the
decomposition products when acted upon by
water would decide whether they were normal or
iso- compounds. Thus :
(CN)33NMe2 + 3HjO = (CN)330H + 3NHMe,
alkyl-n-melamine cyanuric acid secondary
amine ,
(CNMe)s3NMe + SRfi = (C0)s3NMe + 3NH,Me
alkyl-iso-melamine metbyl-iso- monamine.
cyanurate
Here was a distinction that could be observed,
and experiment showed that the first equation
represents the reaction which takes place. The
new alkyl melamines are to be regarded, then,
as normal derivatives, and the iso- structure is
reserved for the metameric compounds derived
from substituted ureas. •
What, then, is the constitution of melamine
itself? When the close analogy existing between
the reactions by which the normal alkyl mela-
mines are produced, and that by which melamine
itself may be obtained is perceived, there cannot
remain much doubt as to its normal constitution,
thus : —
(CN)3Cl3 + 3H(NMe3) = (CN)33NMe2 + 3HC1
(CN)3Cls H- 3H(NHMe) = (CN)33NHMe + 3HC1
(CN)3C1, + 3H(NH3) = (CN)33NHj + 3HC1.
Moreover the normal constitution of cyanurio
chloride must not be forgotten. From it ace
derived only normal ethers, and from normal
ethers, as Hofmann himself -shows, cyanurio
chloride may be reproduced by the action of
phosphorus pentachloride. Two subsequent mo.
moirs (B. 18, 3217 ; 19, 2061) contain a desorip-
tion of many new derivatives of normal and iso-
cyanuric acid and melamine. Besidues in the
position which Bathke afterwards proposed to
designate by the denomination eso are shown to
exist in some of these complex derived com-
pounds. This is notably the case with the
triphenylmelamine which Hofmann designates
unsymmetrical, and which Eathke would term
diesotriphenylmelamine. It has the formula
0 NHPh
/^
PhN. N
I I
HNC CNH
\/
NPh,
and is composed of two iso-melamine and one
normal melamine group. The cyanurid ethers
were submitted to a careful re-examination in the
first of these papers, and their melting-points
and boiling-points re-determined and corrected,
and in most cases their crystalline form sub-
mitted to exact measurements.
The question of the constitution of cyanuric
acid was considered by Hofmann mainly in one of
the memoirs already referred to (B. 18, 2791).
It was pointed out in the first place that the con*
OlANIO, DICYANIC, AND TIllOYANIO ACIDS.
311
Btitation of the normal and iso- series of alkyl
derivatives is establishedbeyond question by the
perfectly distinct products which they give when
subjected to the decomposing action of water.
The normal ethers break down into oyanurio acid
and alcohol, the iso- ethers into carbon dioxide
and amine. So far, then, as the decomposition
of the ethers is evidence, oyanuric acid is a nor-
mal compound. But, on the other hand, no one
has succeeded in preparing normal ethers from
oyanuric acid. Iso- ethers, as in the methods of
Wurtz and Habioh and Limprioht, are always
obtained. So far, then, as the formation of the
ethers is evidence, cyanurio acid is an iso-com-
pound. Consideration of these reactions leaves
the question an open one. Other reactions must
be studied. It is argued that cyanuric acid is
iso- because of its formation from urea and cer-
tain allied compounds ; but this assumes a con-
Btitution for urea which is by no means finally
established ; and which, indeed, as Hofmann
points out, has been directly questioned. Again
to cyanuric acid is assigned, the iso- structure,
because of its homology with cyanic acid, which is
assumed to be iso-. If cyanic acid were really
iso- this argument would have great weight ; but
Hofmann showed, especially by means of its
close analogy to normal thio-cyanic acid, that
cyanic acid is probably normal in constitution.
It is admitted, however, by Hofmann that in
order to explain all the reactions, whichever view
be accepted, an intra-molecular rearrangement
has sometimes to be assumed. For instance,
maintaining the normal hypothesis such a change
has to be supposed in the case of the reactions of
Wurtz andHabich and Limpricht. It is shown,
however, that instances of this change from nor-
mal to iso- are of frequent occurrence, whereas
there is scarcely a case on record — only one
which Hofmanil himself in alatermemoirpointed
out— of the opposite change. This then is an
argument in favour of the normal hypothesis.
But perhaps the strongest of all arguments in
support of the normal view is the relation of
cyanuric acid to cyanuric chloride. This chlo-
ride is, for reasons already given, unquestionably
a normal compound. Now phosphorus penta-
chloride behaves towards normal cyanuric ethers
in a manner precisely parallel to its action, as
shown by Beilstein, on cyanuric acid itself. In
both cases cyanuric chloride results. Again, from
cyanurio chloride and alcohol (Sodium ethylate)
normal ether is obtained, and in the parallel
reaction between cyanuric chloride and water
(sodium hydroxide) cyanuric acid results. Thus : —
(CN),30B' + 3PCI5 = (CN)3Cl3 -t- 3POCI3 + SR'Ol
(CNJjSOH + 3POI5 = (CN)3Cls + 3POOI3 + 3HC1
and
(CN)3C1, + 3R'0H = (CNjjBOR' + 3HC1
(0N)3Cl3 + 3H0H = (CNJaSOH + 3HC1.
This analogy receives important support from
the corresponding thio- derivatives. It is scarcely
conceivable that intramolecular change takes
place in one series of these reactions and not
in the other, and indeed the composition of the
chloride of iso-cyanurio acid is probably such
that it would be impossible for it by metastasis
to be converted into oyanurio chloride; at all
events Hofmann shows that the action of phos-
phorus pentachloride on iso- ether leads to the
formation of a chloride having an altogether
different composition. In another memoir in
18S6 (J5. 19, 2084) Hofmann continues this dis-
cussion. Klason in the meantime had offered
another explanation of Bathke's dicyandikmide
and thiocyanic acid reaction, which led to the
normal and not the iso- structure for thio-aiame-
line. Hofmann adopted this. With regard to
the use of more than one formula as suggested
by Bathke, Hofmann can only admit this prac-
tice if it be meant to imply that a compound
behaves in one reaction as if it had one consti-
tution, and in another reaction as if its consti-
tution were a different one. The identity of a
substance requires that in its quiescent state it
be regarded as one and the same thing. The
only way out of the difficulty with regard to the
constitution of cyanurio acid is to adopt that
formula which explains the most reactions, and
to assume in the others that metastasis takes
place. Hofmann therefore adopts the view that
cyanuric acid is a normal orhydroxyl compound.
There now remain to be considered a series
of important communications from the Swedish '
chemist, P. Elason (or Glaesson, as it is vrritten
in the Swedish memoirs). The field indepen-
dently worked out by this observer is covered
very largely by that of Hofmann, and has already
been noticed. This is true also with regard to
the view to be taken of the constitution of cyanic
and cyanurio acids and melamine. The leading
points which remain must now be briefly
stated.
In an early communication in 1885 {B. 18,
496 B.) some important improvements were sug-
gested in the preparation of cyanuric chloride,'
and the discovery of Cyanuric Iodide was an-
nounced. A series of normal melamines was
described a little later (£. 18, 497 B.), and it
was shown that thio-ammeline was normal and
not iso-, as Bathke had maintained. Klason
proved this by its synthesis from Liebig's chlor-
cyanamide (normal diamido-cyanuric chloride),
by the action of sodium sulphydrate. The fact
that oyanamide by polymerisation gives ordinary
normal melamine leads to the view that it also
is normal {B. 18, 499 B.). On the other hand
Klason considered the only known series of 'alkyl
oyanamides to be iso- compounds because they
polymerise to alkyl iso- melamines. Maintaining
the normal structure for cyanic and cyanuric
acids Klason (1886, J. pr. 38, 126) submitted the
reasoning of Nencki and the more recent argu-
ments of Bathke to a detailed criticism. It was
shown that another formula can be ascribed
equally well to acetoguanidine, and that this
leads to the normal formula for cyanuric acid.
This is the case also with Bathke's reaction
between dicyandiamide and thiocyanic acid, for
Klason maintained that the diamide is a normal
and not an iso- compound. The case of Bam-
berger's reaction is admittedly different. In
order to explain that reaction, metastasis has
undoubtedly to be assumed. Subsequent exami-
nation of the melam compounds by Klason (1886,
J. pr. 33, 285) showed that ordinary melam is ,a
mixture of true melam and a new compound
melem, and that ordinary ammelide is a mixture
of melanurenic acid and ammeline. It was there-
fore proposed to apply the name ammelide to
melanurenic acid, in which case the compoundi
312
CYANIO, DICYANIC, AND TRIOY^VNIO ACIDS.
between oyanurie aoid on the one hand and
melamine on the other would be as follows : —
,/
OH
■NH,
y
■NH,
(0N)3^OH (ON),^OH (CN),^NH3(CN)3f KH,
\0H \0H \0H XnHj
cyannric acid ammelide ammeline melamine.
MONOCTANOGEN GEOUP.
Normal cyanic acid CNOH %.&. (C:N).OH.
F,onnatUm. — 1. By the action of heat on
oyanurio aoid (Wohler, 0. A. 71, 95 ; 73, 15? ;
P. 1,117; Liebig a,. Wohler, P. 20, 369).— 2.
In place of cyauuric acid a mixture of F^Os and
urea may be employed (Weltzien, A. 107, 219)
or a mixture of uric aoid with llnOj or H^SO,
(Dobereirier, O.A.7i, 121), or mercuric urate
may be heated alone. — 3. Cyanic acid is also
formed when ethyl thiocarbamate is subjeoted
to distillatibn. OO.NH^.SEt = CNOH + BtSH
.(Debus, 4. 72, 1; 75, 127; 82, 253).
Cyanic acid cannot be isolated by treatment
of its metaUio or alkyl salts with hydrous acids or
water, for the moment it is liberated it takes up
the elements of water and appears as NH, and
COj.
Preparation. — Anhydrous oyanurio acid is
heated nearly to redness in a current of COj.
This is conveniently accomplished in a tube
bent at right angles, the charged arm of which
can be placed in a combustion furnace. The
vapour of cyanic acid is led into a suitable con-
denser surrounded by a freezing mixture. More
or less polymeric cyamelide is always formed
and condenses as a snow-white solid in the
cooler parts of the tube (Wohler) (Baeyer, A.
114, 156).
Properties. — A thin colourless liquid which
reddens litmus and has an extremely pungent
odour suggestive of glacial acetic acid. The
vapour causes a copious flow of tears and the
liquid applied to the skin quickly raises a blister.
S.G. (2) 1-140; (-2a) 1-156 (Troofet a. Haute-
feuille, J. 1868, 314). V.D. 1-50 (oalc. =1-49)
(T. a. H.). H.C. 98,470 (T. a. H.). Cyanic acid
changes readUy into the isomeric cyamelide or
' insoluble oyanurio acid.' At 0° this transforma-
tion takes place quietly in the course of an
hour, but at higher temperatures the action be-
comes explosive. The heat , evolved by this
atomic rearrangement is 17,630 gram-units
(T. a. H., J. 1869, 99). In ice-water cyanic aoid
dissolves without decomposition until a certain
degree of concentration is attained.
Beactions. — 1. In presence of triethyl phos-
pMne it polymerises to cyanuric acid (Hofmann,
- O. 8. Mem. 13, 322).— 2. Acted on by water it
immediately splits into NH, and COj. — 8. Alco-
hol reacts on cyanic acid forming allophanio
ether 2CN0H + EtOH = C0.NH2.NH.C00Et.—
4. With epichlorhydrin OjHjOOl it combines
to form ohloroxypropyl carbamic anhydride
/NH
C0< \
\0— CjHsCl (Thomsen, B. 11,2136).— 5. By
the action of aldehyde trigenic aoid is produced
2CNOH + CH,GHO=C,H,N,02 + COj (Liebig a.
Wohler, A. 59, 296; Herzig, Jf. 2, 398).— 6. So-
dium ainalgam reacts on CNOK, producing
formamide (Basarow, B. 4, 409).— 7. When dry
HCl is passed over CNOK or better CNOAg
cyamelide is formed and a liquid cyanic acid
hydrochloride CNOH, HCl distils over (W6hler,
A. 45, 357). — 8. With ehloral cyanic acid
vapour combines to form cyanic aoid chloral
(OCl,CHO)jCNOH, and with chloral hydrocy-
anide it also combines to form the compound
(CCl3CH0,HCN)CN0H' (Bischoff, B. 5, 86;
Cech, B. 8, 1174; 9, 1253; 10, 880; Wallach,
B. 8, 1327).
Halogen demvaxives.
Cyanogen chloride CNCl i.e. (C:N).C1.
Formation. — By the action of CI on aqueous
hydrocyanic acid (BerthoUet, A. Ch. 1, 35 ; Gay- / /
Lussao, A.' Oh. 90, 200), or on certain metaUie
cyanides in presence of water (Serullaa, A. Oh.
[2] 35, 291, 387 ; of. Wohler, A. 73, 219 ; Cahours / /
a. Cloez, A. 90, 97 ; Cloez, A. 102, 854 ; Klein, I.
A. 74, 85 ; Martius, A. 109, 79 ; Langlois, A. Oh.
[3] 61, 481). '
Preparation. — About 15 gramsof Hg(CN)jare
placed in a 3-litre bottle and partly covered with
water. CI is then led in till the whole of the
air is displaced, and the bottle is set aside in a
dark place for 24 hours. The colour of the CI
gradually disappears, its place being taken by
colourless gaseous cyanogen chloride. Several
such bottles may be charged and set aside at the
same time, Por most purposes the gas thus
prepared may be at once made use of. If, how-
ever, it is desired to isolate the pure chloride the
bottle must be placed in a freezing mixture, when
crystals of CNCl form, and these by a series of
operations are separated in a pure state (SeruUas)
(Wohler). Explosions haying sometimes occurred
by the above method (Weith, B. 7, 1745), the re-
action between aqueous HCN kept in a freezing
mixture and Gl is preferred by some chemists . ■
(Gautier, A. 141, 122). In any case the greatest
care is requisite, on account of the extremely
poisonous nature of this gas, to prevent its escape
into the atmosphere of the laboratory.
Properties. — ^At ordinary temperatures it is a
colourless gas with a pungent odour and irrita-
ting action on the eyes. Exceedingly poisonous.
At — 12° to — 15°, or at 0° under a pressure of 4
atmospheres, it condenses tq a colourless liquid,
and at — 18° it crystallises in prismsi V.D.
=2-124 (oalo.=2-128) (Salet, 4. 136, 144; cf.
Wurtz, A. 79, 284 ; Eegnault,. J. 1868, 65, 67,
70). CH. (Berthelot, J. 1871, 79; 1874, 114).
Polymerises spontaneously but gradually into
(CN)30l3. S. 25 ; 50 (ether), 100 (alcohol). The , ,
aqueous solution does not redden litmus; and ' '
gives no pp. with AgNOj.
Beactions. — 1. Potassium heated in CNCl gas
gives KCN and KCl, and antimony in a similar
manner forms a chloride aijd liberates cyanogen.
2. With aqueous KHO it is converted into
CNOK and KCl.— 3. Aleofiols dissolve CNCl,
and on standing a reaction gradually takes place
with the formation, among other products, of
carbonic and carbamic ethers (Wurtz). — 4. With
sodmrni alkylate CNCl reacts, forming, in the
first instance,^ normal cyanic ethers, whicii, how-
ever, immediately polymerise to the correspond- '
ing cyanuric compounds (Cloez, G. B. 44, 482 ;
Hofmann a. Olshausen, B. 3, 271).- 5. With
armnonAa cyanamide and NH4CI are formed,
and in the same manner aZ/cj/Z armnoniaa iona
alkyl cyanamides (Cloez a. Cannizzaro, A. 78,
I 229 ; 90, 95).
CYANIC, DICYaNIO, AND TKIOYANIO ACIDS.
313
Combinations. — 1. With other halogen com-
pounds: SbCljGNCl (Klein, A. 74, 87); BCl,
CNCl (Martins, A. 109, 79) ; Fe^Olj 2CNC1 (K.) ;
TiOljCMCl (Wohler, A. 73, 220) ; EtCNCNCl
(Henke, 4.106, 286) ; the oompound (CNpi)sHCN
(Wurtz, A. 79, 281) is said not to exist (Yogt,
A. 1S5, 170).— 2. With NHjOH, HCl, PH,HI,
CO2NH2, <S;o. (Traube, B. 18, 462).
Cyanogen bromide ONBr i.e. (0:N).Br.
Formation.— Bj the action of Br on Hg(CN)ji
(Sernllas, A. Ch. {2] 34, 100 ; 35, 294 a. 315) or
on HONAg (LSwig, Das Brom uncL seine che-
mischen VerhUltmsse, Heidelberg, 1829, 69), or
on a cold solution of KGN (Ijanglois, A. Ch. [3]
61, 482). ^
Pr^aration. — When 1 part of Br is allowed
to flow gradually on 2 parts of Hg(CN)j in a
retort surrounded with ice CNBr and HgBrj are
formed with great evolution of heat. The CNBr
sublimes in needles, contaminated at first with
free Br, but ultimately the Br flows back and
enters completely into combination. Gentle heat
is then applied, and the CHBr subUmed into a
receiver surrounded with ice (SeruUas).
Properties. — CNBr subhmes in colourless
needles, which afterwards change to cubes (S.).
[+4°] (Lawig) ; [above 16°] (S.) ; [not even' at
40°] (Bineau, A. Ch. [2] 68, 425) ; [48°] (Senier,
priv.com.); [52°] (Mulder, iJ. 4, 151). (61°) (750
ram.) (M.). H.F. (Berthelot, J. I871, 80).
Vapour pungent and irritating, resembhng
CNCl. V. sol. KjO and alcohol. Forms a
crystalline hydrate less fusible than the anhy-
drous compound.
Reactions. — 1. Heated in a closed tube from
130°-140° it is, converted into (CN),Br,.— 2. With
KHOAq it forms KBr, KCN, and KBr03(S.)(L.).
3. Ammonia gas reacts with the formation of
CNNH^ and NH^Ol.
Cyanogen iodide CNI i.e. (C!N).I.
Formation.— Bj the action of I on mercuric,
silver, or other metaUio cyanides (Davy, G. A.
54, 384 ; Wohler, G. A. 69, 281 ; SeruUas, A. Ch.
[2] 27, 184; 29, 184; 34, 100 ; 35, 293 a. 344 ;
Van Dyk, B. P. 21, 223). CNI sometimes occurs
as an impurity in commercial iodine (Scanlan,
C. S. Mem. 3, 321; F. Meyer, 4r. Ph. [2] 51, 29;
Klobach, Ar. Ph. [2] 60, 34).
Preparation. — 1. Iodine is dissolved in a
warm cone, solution of KCN until the liquid, on
cooling, solidifies to a crystalline mass. On
gently heating the CNI sublimes, and it may be
purified by reorystallisation from alcohol or ether
(Liebig, Chim. Org. 1, 180).— 2. 2 pts. of iodine
dissolved in ether are added to 1 pt. of Hg(CN)2,
Beaction takes place, and the CNI goes into
solution in the ether, from which it may be
obtained by evaporation (Linnemann, A. 120,
36).
Properties. — ^Long, delicate, colourless needles,
or from its solution in alcohol or ether in four-
sided laminffi (Herzog, Ar. Ph. [2] 61, 129). It
has a pungent, penetrating odour and acrid
taste. It is very poisonous. Sol. water, more
sol. alcohol, still mdro sol. ether and volatile
oils. No one has hitherto succeeded in converting
it iato the polymeric (CN)3l,. H.F. (Berthelot,
J. 1871, 79 ; 1874, lU) {of. B. Meyer, J.pr. [2]
36, 292).
ReaotUms.—l. KHO reacts, forming KCN,
KI, and KIOj (SeruUas).— 2. NHj cbnverts it
into CNNH, and NH.I.- 3. With ZnB'., or AIR',
aJkyl nitriles and metaUio iodides are formed
(Calmels, Bl. 43, 82).— 4. It dissolves in alkaline
sulphites with the formation of HI, HCN, and
alkaline sulphates (Strecker, A. 148, 95).
CmiMnations. — When 4 pts. of I are dis-
solved in a solution of 1 pt. of KCN in 2 pts. of
water long oolohrless crystals separate, which
after recrystalUsation from ether have the com-
pbsition KI,4CNI,4aq. [120°-130°] (Langloia,
A. Ch. [3] 60, 220).
METAUiio DEErvAirvES V. Oyanaies, p. 297.
AiiKYi. DEEiVATivEs. Normol cyanic ethers.
Normal cyanic ethers have never been isolated.
The reaction between sodium alcoholate and
cyanogen chloride (Cloez, 0. JR. 44, 482), which
was supposed to yield normal cyanic ethers,
proved when further investigated, both in the
methyl series (Hofmann a. Olshausen, B. 3, 271)
and in the ethyl series (Mulder, B. 2, 133),
to give no cyanic ether, but instead a mixture
of alkyl cyanurate and amido- derivatives.
There is not much doubt that in this reaction
normal cyanic ethers are formed in the first
instance, but they polymerise almost imme-
diately to their cyanuric homologues (c/. Pono-
mareff, B. 15, 515 ; Mulder, B. 1, 210 ; 3, 306).
AlKOYL DEKIVAirVES.
Acetyl cyanate CjHjNOj i.e. (C-N).OA».
Silver cyanurate acts upon acetyl chloride,
forming what is probably a polymeric form of
this compound. When this is subjected tc> dis-
tillation liquid acetyl cyanate or cyanogen
acetate is obtained, together with acetonitrile
and cyanogen. Water decomposes it into
acetamide and CO.^ (Sohutzenbergor, A. 123, 271).
Normal thipcyanic acid v. Thiocyahic acid.
Normal cyanamide CH^Nj i.e. (C:N).NHj.
Formation. — ^1. By the action of CNCl, CNBr,
or CNI on NH,. CNCl + 2NH3 = CNNHj + NH,01
(Bineau, 4. Ch. [2] 67, 368; 70, 251; Cloez a.
Cannizzaro, A. 78, 229).— 2. CNNNa., is the end
product of the reaction between NHjNa and CO2,
"a) NH2Na-HC02 = NH„.C0.0Na,
'6) NH2.CO.ONa = CNdNa + H20,
>) CNONa-)-NH2Na = CNNNa2 + HjO
(Beilstein a. Geuther, A. 108, 93; Drechsel,
J.pr. [2] 16, 203). — 3. By the action of sodium
on urea, ammonium carbamate, or ammonium
carbonate CO(NHJj+ Na = CNNH^ + H + NaHO
(Fenton, C. J. 41, 262). -4. By desulphurisation
of thio-urea by means of HgO. CS(NHJj-HjS
= CNNH2 ( Volhard, J. pr. [2] 9, 25 ; Baumann,
B. 6, 1371; Mulder a. Smit, B. 7, 1636).
Preparation.— Moist freshly ppd- mercuric
oxide, which has been purified by boiling with
NaHOAq and then with water, is added in small
portions at a time to an unsaturated cold solu-
tion of thio-urea in water. Excess of HgO is
avoided, otherwise insoluble mercuric cyanamide
is fbrmed (Engel, Bl. 24, 273). The operation is
continued untU all the thio-urea is desulphurised,
which may be ascertained by the liquid ceasing
to give a black pp. when a drop of it is tested
with NHjAgNOj. The sulphide pp. is then fil-
tered off and the filtrate concentrated as quickly
as possible by evaporation, the latter part of the
process being co,aduoted in a vacuum over
H2SOJ. From the residue, ether extracts cyan-
amide and leaves dicyandiamide, which is also
formed, undissolved (Volhard; Drechsel, J.pr.
314
OYANIO, DICYANIO, AND TRIG YilNIO ACIDS.
[2] 11, 298 ; 21, 79). Another method employs
an alcoholio instead of an aqueous solution of
thio-urea (Baumann, B. 6, 1376 ; Pratorius, J.pr.
[2] 21, 131). It is noteworthy that pure thio-
urea does not admit of complete desulphnrisation
in this reaction, the presence of traces of such
a substance as CNSNH.,, however, renders the
action of the HgO perfectly easy (Traube, B. 18,
461).
Properties. — Cyanamide is a white crystalline
compound [40°]. When melted, however, it may
be cooled far below 40° without solidification
taking place. This, however, is at once effected
by contact with a pointed solid body. V. sol.
water, alcohol, and ether ; si. sol. CSj, CHCI3, and
benzene. Heated above 40° it passes into the
homologous ra-di-cyandiamide (0N)22NH2, and at
about 150° it soUdifies with evolution of heat,
forming w-tii-oyantriamide or melamine, together
with other products (Drechsel, J.pr. [2] 13, 331).
Cyanamide suffers this intramolecular condensa-
tion with great readiness. Thechange takes place
at once when a solution containing ammonia is
evaporated, or, again, when an alcoholic solution
is heated together with phenol. In these cases
the dioyanogen homologue results. More slowly
cyanamide pblymerises into dicyandiamide
simply by standing.
Reactions. — 1. CNNH^ is reduced by nascent
II'{Zn and HOI), with the formation of NH, and
MoNHj. (a) ' CNNHj + H^ = CNH + NH,,
(b) ONH + H, = MeNHj (Drechsel).— 2. Heated
with KNOnAg^ a violent reaction takes place with
evolution of nitrogen and production of carbon
dioxide and di-cyandiamide 4ONNH2 + 4KNO2
= 2K2COS + HjO + 8N + (CiSr)22NH2 (Drechsel).—
3. The addition of HNOj'to an ethereal solution
causes it to combine with a molecule of water,
forming urea, which, being insoluble in the ether,
ppts. Sulphuric, phosphoric, salicylic and lactic
acids behave in a similar manner (Baumann, B.
6, 1373; Pratorius). — 4. With feaZoii ac«?s direct
addition compounds are formed. — 5. With HjS,
or better with yellow ammonwwm sulphide, cyan-
amide conibines to form thio-urea. — 6. AgNOj
reacts on CNNH2 forming AgCN and a yellow
fiocculent pp. CNNAg^. SCNNH^ + 4AgN02
= CNNAgj -I- AgCN + AgNO, + CO^ -i- 6N + BHjO.
7. With glycocoll CNNHj yields glycooyamine
(Strecker, Hcmdio. d. Chem. [2] 3, 286), and withj
methyl-glycoooU CH2(NHMe)C00H it forms'
creatine. — 8. CNNHj dissolves in aldehydei and.
after standing the mixture becomes resinous,
and contains the compound (CN)33NC2Hj, aq
triethylidene melamine (Enop, A. 131, 253). —
9. Heated with oxalic ether formomelamine
(CN)3(NHj)2NHCHO results.— 10. At high tem-
peratures it combines with NHjCl, forming
guanidine hydrochloride C(NH)2NH2,HC1> and
with NHjOHCl forming ox'yguanidine hydro-
chloride C(N0H)2NH2,HC1. In the same man-
ner, with (CNjSNHj guanidine thiocyanate
C(NH)2NH2,HSCS is obtained. — 11. CNNH^
combines Erectly with CN, forming a yellow
powder (Hofmann, /. 1861, 630).— 12. With
CNOK. cyanamide combines to form mono-
potassium amidodioyanate (CN)j.NH2.0K. —
13. Alloxanthin reacts on cyanamide, forming
iso-urie acid (Mulder, B. 6, 1236).— 14. With
guaftMin it combines to form diguanid.
Combinations. — With lialoid acids (Drechsel,
X pr. [2] 11, 315; Mulder, B. 7, 1634).
CNNH22HCI is producedas a orystaUinepp. when
anhydrous HOI is conducted into an ethereal
solution of cyanamide. V. sol. water, sol. alco-
hol, insol. ether. If to the alcoholio solution of
this compound HgO be added, and the clear so-
lution evaporated, crystals of CNNHjHgOljSaq
are obtained. They are v. sol. water. The cor-
responding HBr compound exists, CNNH22HBr
(D.). — With chloral. The two compounds com-
bine directly, to form' chloral cyanamide,
001,0H0,CNNHj (E. SchifC a. Fileti, B. 10,
426).
MeTATiTiTC dekivatives.
Formation. — MonometalUc salts. Aqueous
or alcoholic solutions of alkalis or earttis or
alkyl alkalis, act on cyanamide, giving mono-
derivatives NaOEt + CNNHj = CNNHNa + EtOH
(Drechsel, J. pr. [2] 11, 307; 16, 205; 21, 81),
Di-metallic saMs. — 1. By the action of heat on
earthy and other metallic cyanates, Oa(CNO)2
= ONNOa + COj (Drechsel).— 2. By heating pure
Ba(0N)2 in a current of N. Ba(ON)j + N
= CNNBa + CN (Drechsel).— 8. ONNK^ is among
the products of the heating of EON or CNOK
with NaHO.
2K0N + 4NaH0 = CNNK,, -1- Na^CO, H-Na^O -h H,
(Drechsel). — 4. By heating together NH^Na and
ONONa.
CNONa + NHjNa = ONNNa, -1- H„0 (Drechsel)
Properties. — Sodium salt CN.NHNa. Fine
crystalline powder. V. e. sol. water, sol. alcohol,
insol. ether. It absorbs oxygen and OOj with
avidity. With CO, it forms a salt of cyanamido-
carboxylic acid CO<(^qj^ , an isomeride of
cyanic acid, With ethyl chloroformate OlOOOEt
sodium cyanamide combines to form oyanamido-
dicarboxylic ether CN.N(C00Bt)2. Isoeyanio
and isothiocyanio ethers combine with ONNHNa
with the production of amido-dicyanic deriva-
tives ONNHNa + OONEt = CN.(NNa).C0.NHEt.
Calcium salt (0N.NH)2Ca. This may be pre- '
pared by acting on CNNH, with Ca(HO)jAq.
From an aqueous solution crystals of the salt
CNN(0a0H)2 6aq have been obtained (G. Meyer,
J.pr. [2] 18,425).
Disodium salt CN-NNaj. Heated With char-
coal it gives NaCN. Sodium potassium salt
ON.NKNa (Drechsel). Calcium salt CN.NOa.
Decomposed by water with formation of mono-
salt (Drechsel ; G. Meyer). Mereurio salt
CN.NHg" (Engel, Bl. [2] 24, 273). Lead salt
CN.NPb. Ammoniaoal solution of ON'NHj gives
a lemon-yellow pp. of this compound with
Pb(02H30)2. CopiJersffiZi ON .NCu (Engel). Silver
salt CN.NAg^. An amorphous yellow pp. V. e.
sol. HNO3, insol. dil. ammonia. Explodes quietly
when heated (Drechsel; Beilstein a. Geuther,
A. 108, 99).
Alkoyl beeivativbs.
Acetyl cyanamide CsH,N~0 i.e.
(C.-N).NHAo.
Formation. — 1. By the action of acetyl
chloride on cyanamide in ethereal solution
(Drechsel, J.pr. [2] 11, 344).— 2. Sodium acetyl
cyanamide is formed by treatment of sodium
cyanamide with acetic anhydride. This is con-
verted into the silver salt from which the silver
is removed by HjS (Mertens, J. pr. [2] 17, 7).
Properties.— A. syrupy acid liquid. V. soL
CYANIO, DIOYANIO, AND TRICYANIC ACIDS.
316
water, alcohol, ether, and chloroform, insol.
benzene. When heated the liquid undergoes a
violent reaction and is converted into a solid
(polymeric 7) mass (Mortens).
Combinaticms with metals. — Sodium salt
(CN)NAoNa. A hygroscopic crystalline powder.
Sol. alcohol, insol. ether. Heated it splits into
acetonitrile and sodium cyanate. Silver salt
(CN)NAoAg. Prepared by precipitating
(CN)NAcNa,Aq mth AgNOj. A white crystal-
line powder. Insol. water, v. sol. ammonia.
Heated it evolves acetonitrile.
Diacetyl cyanamide OsHuNjO, i.e.
(O-Nj.NAcg. Bhombic plates decomposing at
65°. Insol. water, v. si. sol. alcohol, sol. ether.
Obtained by acting upon CNNHAo in ethereal
solution with AcCl (Mertens).
Butyryl cyanamide CsHgNjO i.6.
(C:N)NH(0,H,0). The sodium salt is formed
by acting on (ON)NHNa with (04H,0)20 in
ethereal solution. This salt is insol. ether, but
sol. water. From the aqueous solution AgNO,
ppts. the silver salt, which is sol. ammonia, and
from which the free cyanamide maybe obtained.
Isovaleryl cyanamide CsHjoNjO i.e.
(CiN)NH(05H,0). Formed in a similar way to
aoetyl-oyanamide. An acid syrup, sol. water,
alcohol, and ether. Converted by heat, with a
violent reaction, into a solid (polymeric ?) mass.
Sihier saUiGS)N(Cja^O)A.g.
Benzoyl cyanamide CgHgN.O t.e.
(C;N)NHBz.
Formation. — By the action of benzoyl chlor-
ide BzCl on sodium cyanamide (CN)NHNa in
ethereal solution.
Properties. — Unstable. Decomposes into
COj, (ON)NH, and BzON. Digested in ethereal
solution it polymerises to tribenzoyl normal mel-
amine (Gerlich, J.pr. [2] 13, 272).
Lactocyanamjide v. Lactic Acm.
Succincyanimic acid\
Sucoincyanimide [v. Succinic acid.
Succincyamide '
CABBOXTIilC DEBIVATIVISS.
Oyanamidocarbonic acid v. Ctanami-
DOCABBOXyiilO Acm.
Cyanamidodicarbonic acid v, Cyan-
AMIDOnCCABBOXYLia ACID.
Condensed cyanamide compounds.
Cyanogen cyanamide CjHN, i.e.
(C!N),NH.(C:N). Not known in a free state.
CN.NK.cn is formed by the action of KHO on
GNCl or paracyanogen, or by fusing paracyano-
gen with KCN. Needles. CN.NAg.CN is ppd.
when AgNOj is added to an aqueous solution of
CN.NK.cn (Bannow, B. 4, 254).
Isocyanic acid CHNO i.e. (C:0):NH. Iso-
cyanic acid has not hitherto been isolated, neither
are halogen or metallic derivatives known.
Alkyii DEEivATivES. Isooyatdc ethers.
Formation.— 1. By distilling alkyl sulphate
of potassium with potassium cyanate. Part of
the isocyanic ether formed polymerises to iso-
oyanurate (Wurtz, A. Oh. [3] 42, 43).— 2. From
carbamines by oxidation with HgO (Gautier, A.
149, 313).— 3. By the action of alkyl iodides on
silver cyanate (Brauner, B. 12, 1874).— 4. By
distilling alkyl-ohloroformamides with lime
(Gattermann, A. 244, 36).
Properties.— Low-boiling pungent irritating
liquids.
Beac«ions.— (Wurtz.) 1. Polymerise gradually
on standing into the corresponding isocyanurio
ethers. — 2. SyAvlysis when heated, mth dilute
KHOAq, they break down into CO,j and amines
CONEt + HjO = COj + NHjEt. When treated with
water alone the reaction does not go so far, COj
and s-dialkyl urea being formed, 2CONEt + H20
= C0s, + C0(NHEt)2. — 3. With alcohols they
combine to form alkyl-carbamio ethers, thus:
CONEt + EtHO = NHEt.CO.OEt. — 4. Organie
acids react giving acid amides and carbonic
acid CONEt + AcOH = COj + AoNHEt. — 5. An-
hydrides yield tertiary amides and carbonic acid '
CONEt + AcjO = CO2 + AOjNEt. — 6. NH3 and
prim, and sec. amines combine to form substi-,
tuted ureas CONEt + NHEtj= NEt.,.CO.NHEt.—
7. The oxygen may be replaced by sulpliur by
treatment with PjSj, mustard oils or isothio-
cyanic ethers being formed.
Methyl isocyanate C^HjNO i.e.
(C:0):NMe. (37°)(Gattermann) : (44°) (Wurtz;
Gautier).
Fihyl isocyanate C3H5NO i.e. (C:0):NEt.
(60°). S.G. 0-898 (Wurtz). The pure ether does
not polymerise on standing, but the presence of
NaOEt quickly transforms it into isocyanurate
(Hofmann, J. 1861, 515 ; A. 103, 358; 115, 275).
In the same manner NEt^, with which it does
not combine, determines its polymerisation
(Hofmann, J. 1862, 335). Hydrochloride
C0NEt,HCl is formed by acting directly on the
ether with HCl gas, or by distillation of
C0(NHEt)„HCl (Habich a. Limprioht, A. 109,
107). Highly pungent irritating liquid (95°) (H.
a. L.). (108°-112°) (Gal, Bl. 6, 435). Water
decomposes it with violence into NH,EtHCl and_
COj. Hydrobrcmide CONEt.HBr (118°-122°)
(Gal).
Isopropyl isocyanate C^H^NO i.e.
(C:0):N(C3HJ. (67°) (Hofmann, B. 15, 756).
Isobutyl isocyanate CjHgNO i.e.
(C:0):N(C4Hj). (110°) (Brauner, B. 12, 1877).
Tertiary butyl isocyanate CjHgNO i.e.
(C:0):N(CMes). The action of isobutyl chloride
on silver cyanate gives small quantities of iso-
butyl isecyanate together with tertbutyl isocyan-
ate, a polymeric butyl isocyanate, isobutylene,
cyanic, and oyanurio acids. The polymeric iso-
butyl isocyanate remains behind after ieributyl
isocyanate is distilled off, and may be separated
from the other products by solution in ether
(Brauner, B. 12,1874). Aromatic pungent liquid.
(85'5° cor.). S.G. 2 08676. Does not solidify
at -25°.
Isoamyl isocyanate CjH„NOi.e.-
(C:0):N(C5H„). (100°) (Wurtz, J, 1849,428);
(134°-135°) (Custer, B. 12, 1330). Insol. and
lighter than water. Solution of PEtj in ether
polymerises it to isocyanurate (Custer).
JSexyl isocyanate C,H,sN0 i.e.
(C:0):N(C8H,3). (above 100°) (Cahours, a. Pe-
louze, J. 1863, 526).
Allyl isocyanate C4H5NO i.e.
(C:0):N(08H5). (82°) (Cahours a. Hofmann, A.
102, 297).
Benzyl isocyanate v. Benzyl cyanate.
Phenyl isocyanate CjHjNO i.e.
(C:0):NPh (Hofmann, A. 74, 9 a. 33; J. 1858,
348; B. 3, 655; 18,764).
316
OYAOTC, DIOYANIC, AND TRIOYANIO- ACIDS.
FormaUcm. — 1. By the distillation of melan-
-NPhCO
oximide (C:NH)^ | .—2. By distilling oxa-
\NPhCO
nilide CA(NHPh)j with PA-— 3- By the ac-
tion of P2O5 on di-phenyl-urea. — 4. By dis-
tilling alkyl oarbanilate NHPh.CO.OEt with
PjOs-— 5- By acting on melted C0(NHPh)2 or
NH,Ph,HCl with COClj (Hentschel, B. 17, 1284).
, , Properties. — Highly pungent irritating liquid
(1CG° at 769 mm.). S.G. 1-092 at 15°- T.D.'4-09
(calo. 4-13).
Beactions. — 1. In presence of PEtj, or O5H5N
(Snape, C.J. 49, 254), it polymerises to diphenyl-
isodicyanate (C:0)2(NPh)2. — 2. Heated with cer-
tain dry salts, CH3COOK, HCOOK, or NafiO, it
polymerises to isocyanurate. — 3. It forms addi-
tion compounds with 01 and Br. — 4. Water im-
mediately converts it into carbanilide and
COj, thus: 2CONPh + H20 = COj + CO{NHPh)s.
5. Alcohols find jahenols combine with phenyl-
isocyanate to form aU:yl phenylcarbamates
CONPh + EtHO = CO<Qgj^^
6. Ammonia
amines and a/mides form with it substituted
ureas.: — 7. Aniline is produced when it is heated
with zinc-dust. — 8. Heated with AojO'; acet-
aniUde and CO2 are among the products. — 9. In
presence of AlOl, it combines with C„H, and
its homologues to form benzanilide, &o.
CONPh + PhE = BzNHPh (Leuckart, B. 18, 875).
In the same manner it combines with phenolic
ethers (Leuckart a. Schmidt, B. 18, 2338).
GomlnrMUons. — C0NPh,Cl2: unstable crys-
tals (Gumpert, J. pr. [2] 32, 294).— CONPh,Brj
(G.).— C0NPh,H01. : crystalline [45°] (Hentschel,
B. 18, 1178).
p-Bromophenyl isocyanate
CONC^H^Br. [39°]. (226°). Sol. ether (Donn-
Btedt, B. 13, 228).
o-Tolyl isocyanate OjHjNO i.e.
(C:0):N(0,H,).
Formation. — By acting on ethyltolylcarba-
mate CO<|Qgj^'^' with P^ (Girard, B. 6,
445).
Properties. — Liquid. (186°). Powerful pun-
gent odour. Polymerises into a solid modifica-
tion by the action of PEtj (Nevile a. Winther,
B. 12, 2324).
p-Tolyl isocyanate CgH,NO i.e.
(C:0):N(C,H,). Similar to o-ether. Formed also
from ^-toluidine and COCl^ (Kiihn a. Henschel,
B. 21, 505). (185°). Water decomposes it into
di-f)-tolyl-urea and COj (Hofmann, B. 3, 656).
Mksiiyl isocyanate C,„H,,NO i.e.
(C:0):N(Cj,H„). Disagreeable smelling liquid.
(218°-220'=) (Eisenberg, B. 15, 1017).
Oumyl isocyanate 0„H,3N0 i.e.
(C:0):N(C,„h:,3) (Eaab, B. 8, 1151).
{<i)-Naphthyl isocyanate C„H,N0 i.e.
(C:0)N(C,„H,). Pungent irritating liquid. (269°-
270'') (Hpfmannj B. 3, 658).
Diphenyl isocyanate CisHjNO
(C:0):N(C,jHa) (Zimmermann, B. 13, 1965).
Diphenylene diisocyanate
CO:N.C^<.0<,H..N:CO [122°] (Snape, 0. J. 49,
255).
Thioisocyanio acid derivatives v. Tnioiso-
OYANIO ACID.
Isocyanamide (G:NH):NH. This compound
has not been isolated, but its alkyl derivativeg
exist.
Aleyl debivaiives.
Formation. — 1. By the action of ONCl on
primary amines (Oloez a. Oannizzaro, A. 90, 95).
2. By the desulphurisatiou of alkyl thio-ureas
NH,.CS.NHMe - HjS = (CNMe)NH. '
Properties. — Neutral syrupy liquids. By re-
peated evaporation of their aqueous solutions,
polymerisation to the corresponding isomela-
mines takes place (Baumann, B. 6, 1372 ; Ela-
Boa, Bihamg till K. Svenska Vet. Ahad. Samd,
1885, [10] No. 7).
Methylisocyanamide CjH4N2i.e.
(0:NMe):NH (Baumann, B. 6, 1372).
Diethylisocyanamide CjH,gN2i.«.
(C:NEt):NEt.
Formation. — 1. (0NEt)NH breaks down when
distilled into (ONEt)NEt and a crystalline base,
possibly ethyldicyandiamide (Gloez a. Oanniz-
zaro). —2. By the action of (ON)NAgj on Btl
(E. SchifE a. Eileti, B. 10, 428).
Prope»-«ies.— Liquid, (186°) (S. a. P.) ; (190°)
(0. a. 0.). By treatment with HCl it yields C0„
NHj, and NHEtj.
Allylisocyanamide O^B.^'S^i.e.
(0:N0,H5):NH.
Formation. — (Will, A. 52, 15; Bobiqnet a.
Bussy, J.pr. 19, 234 ; Audreasoh, M. 2, 780).
Prc^erties. — A thick syrupy liquid which
gradually crystallises in monoolinic four-sided
prisms with jaq. [100°]. Sol. water, alcohol,
and ether. Strong alkaline reaction. Precipi-
tates metallic oxides from solution of their salts
and liberates ammonia from its combination
with acids. The oxalate is difficultly crystal-
lisable. Its solution gives precipitates with
HgClj and PtCl, :— C:N03Hs:NH,HgCl, and
(0:NC,H5:NH)jPtCl4.
Allylethylisocyanamide CgHigNj ix.
(OrNEQiNOjHs.
Properties. — Needles. [100°]. Insol. water,
sol. alcohol and ether. Beaction alkaline. Taste
bitter. Compounds with HgOl, and PtOl^: —
(C:NEt:NC3H5)23HgClj and (0:NEt:NOaH,)jPtCl,
(Hinterberger, A. 83, 346).
Bemylisocyanamide v. Bwnzaojm-
AMIDE.
Dibenzylisocyanamide v. DiBENZiif
CYANAMIBE.
Phenylisocyanamide C,H.N2i.e.
(C:NPh):NH.
Formation. — (CloBz a. Oannizzaro; Hot
mann, B. 3, 266 ; 18, 3220 ; Berger, M. 5, 219 a.
458 ; Bathke, B. 12, 773).
Properties. — Syrup gradually crystallising in
presence of alcohol in needles (Feuerlein, B. 12,
1602). [47°] (Hofmann). V. si. sol. water ; sol.
alcohol and ether. When water is added to the
alcoholic solution phenyl-urea, C0.NHPh.NH2,is
precipitated. In the same manner in a benzene
solution HjS gives phenyl-thio-nrea (Weith,B.9,
820). Silver salt : C:NPh:NAg (Hofmann ;
Feuerlein ; Berlinerblau, J. pr. [2] 30, 114).
Platinum chloride salts: (0,HsNjHCl)2Pt01.
(Peuerlein); (C,H„N22HCl)2Pt01, (Hofmann).
With acetamide, among other products, two bases,
CjgHasNipand OlsHijNs, are formed (Berger).
Diphenyl-isocyanamide OijHijNj i.e.
(C:NPh):NPh. Formed by the action of ONCl
OYANIO, DICYANIO, AND TRIOIANIO AOIDS.
317
on dipbenylamine (Weith, B. 7, 848). Ehombo-
hedxa. [292°]. Heated with oono. HCl it gives
NH,, NHPhj, and COj.
DICYANOGEN GROUP.
Fnlminic acid CJEL^^^O^. This dibasic acid
has not been isolated. A solution in ether is,
however, probably obtained when dry HCl is
conducted into a mixture of fulminating mer-
cury with that solvent. It forms acid neutral
and double salts, all of which are explosive
compounds. The mercury and silver com-
pounds have long been known and employed
for the filling of percussion caps. The ethereal
solution treated with NaHO evolves NH,, but
no amine. When it is shaken with NH, isof ul-
minuric acid, fulminuramide, and other products
are formed (Ehrenberg, J. pr. [2] 30, 55). DEute
H.SOj also sets free fulminio acid in presence of
ether, but in this case the products of its decom-
position give rise to another series of isomeric
modifications (Scholvien, J. pr. [2] 82, 481).
Only metaUio derivatives of fulminio acid are
known.
TMetallio deeivatives.
Disodium fulminate Na2C„N20j 2aq.
Formed from mercuric fulminate suspended in
water by the action of sodium amalgam. The
liquid concentrated over HjSOj or CaO deposits
prismatic crystals of the disodium salt. Ex-
plodes when rubbed or heated. HjO, decomposes
it with formation of NH3, COj, and HON (Ehren-
berg, J. jw. [2] 32, 231).
itisilver fulminate AgjOjNjOj.
Preparation. — 1 pt. of silver is dissolved in
10 pts. of HNO3 (S.G. 1-36), and the solution
poured into 20 pts. of spirits of wine (85-90 p.c.)
(Brugnatelli, A. Ph. 1798, 27, 331; Gerhardt,
Traitide Chvm. Org. 2, 348). The salt separates
in fine needles.
Properties.—^. 36 at 100° (Liebig, B. J. 4,
111) ; V. si. sol. cold water ; v. sol. ammonia.
More explosive than the mercury salt.
Reactions. — 1. Half of the metal is replaced
by treatment with allcaline chlorides (Gay-Lussao
a. Liebig, A. Ch. [2] 25, 285).— 2. Hydrochloric
acid separates all the silver, but with breaking
Dp of the molecule of the acid (Gay-L. a, L.).
When furuing HCl is employed three-quarters of
the molecule breaks down into hydroxylaniine
and formic acid, the other products being CO^,
NH3, and HON. With dUute acid more NH3OH
and formic acid are formed, and only traces of
NHj (Divers a. Kawakita, C. J. 45, 15 ; 47, 69).
Silver sodium fulminate NaAgCgNjO^.
Small crystalline plates.
Silver potassium fulminate
KAgCjNjOj. Colourless plates. S. 8 at 100°
(Liebig). ■
Silver hydrogen fulminate HAg02N20j.
Falls as a pulverulent pp. when cone. HNO, is
added to an aqueous solution of AgKCjNjOj (Lie-
big)-
Zinc fulminate ZnO^NjOj (E. Davy, B. J.
12, 120).
Zinc hydrogen fulminate ZnHj2C2N202
(E. Davy ; Fehling, A. 27, 130).
Copper fulminate CuCjNjOj (Gladstone,
A. 66, 1).
Mercuric ftilminate 'Hg"C^'Sfia.
Preparation.— 3 pts. of mercury are dis-
solved in 36 pts. pf HKOj (S.G. X-345) in a largo
fiask without the application of heat. The solu-
tion is poured into 17 pts. of spirits of wine
(90-92 p.c.) and the mixture returned to the
large flask. After a time a violent reaction com-
mences, which is moderated by the addition of
more spirits of wine to the extent of another
17 pts. Mercuric fulminate gradually deposits,
and is collected and reorystallised from water.
It may be also purified by solution in KCN and
reprecipitation by means of dilute acids (Howard,
Tr. 1800; Liebig, it. 95, 284 ; Steiner, B. 9, 787).
Properties. — Mercuric fulminate crystallises
from alcohol in minute octahedra, from water in
needles containing |aq (Schischkow, A. 97, 54).
S.G. (anhydroiis) 4-42 (BertJielot a. Vieille,
A. Ch., [5] 21,569). Y. si. sol. cold, more , sol.
hot water. Explodes by heat, friction or per-
cussion, or by treatment with H2SO4. The pro-
ducts of deconiposition are Hg, N, and CO. H.O.
(Berthelot a. Vieille).
Beactions.—l. Zn and H^SO,, or Sn and
HCl, or zinc dust and ammonia, break down the
molecule into Hg, COj, and NH3.— 2. Sodium
amalgam converts it into the Na salt. The by-
products of this reaction, by treatment with
ferrous and ferric oxides yield among other com-
pounds nitroprussides. — 3. Heated with water
containing Cu or Zn, these metals displace the
mercury. — 4. Chlorine conducted into the salt ,
mixed with water reacts, forming HgCl^, ONOl,
and ohloropicriu 0(N02)Cl3 (Kekul6,4. 101, 206).
5. Bromine in the same manner forms dibro-
monitroaoetonitril OBrjNOjCN (Schischkow). —
6. Heated for 8 hours with water alone, or for a
shorter time in presence of NaCl or NHiCl, it
polymerises to the corresponding fulminurate
(Schischkow ; Liebig).— 7. Mixed with ether it
reacts with dry HjS forming HgS, nitrothio-
acetamide CH2(NOj)CSNH2, oxalio acid and
ammonium thiooyanate. In presence of water
the products are HgS, ammonium thiooyanate,
and CO2 (Kekul6).— 8. Mixed with KHOAq and
heated, a pp. of HgO falls.— 9. Ammonia dis-
solves mercuric fulminate, but when the solu-
tion is heated to 60°-70° a reaction takes place
with the production of urea, ,guanidin, and the
compound called fuhnitriguanarate. Heated in
closed tubes to 70° with alcoholic ammonia the
compound fulmitetraguanarate is also formed
(Steiner, B. 8, 520, 1177 ; 9, 781).— 10. Coric-
HOl or HBr react, evolving COj, precipitating
HgCl and 2 mol. of NH^OH going into solution.
Traces of HCN also occur, but no NH3 (Steiner,
B. 16, 1484 a. 2419 ; Car'stanjen a. Ehrenberg,
J. pr. [2] 25, 232).— 11. Dilute HCl in the c6ld
yields formic acid, hy^roxylamine and HgClj
(Ehrenberg, J.pr. [2] 30, 41).— 12. H^SO, (1 in
5) reacts on warming, forming COj, NH,,
NHjOH, HgSOj, and HgAO, (?) (Ehrenberg a.
Carstanjen ; Divers a. Kawakita). — 18. Cono.
HCN dissolves the fulminate, but When the
solution is diluted Hg(CN)2 precipitates. — 14.
Aqueous CNSH reacts, forming COj, Hg(SCN)2
and NH^SCN. With NH,SCN polymerisation to
fulminurate takes place (Ehrenberg, J. pr. [2]
80, 62).
OoTO&MiffliMms. -With KI: (HgCjNjOj)^^
(Schischkow). — With KCN : HgC^NA.KCN
(Steiner, B. 9, 786). — With KSCN it forma
Hg02lSrjO„KSCN(Schischkow).— WithNaANA:
HgCAOa. NaANjOj. a^ (Ehrenberg).
318
CYANIC, DIOYANIC, AND TRICYANIC ACIDS.
Compound C^HjHgjN^Og.
Formation.-^T!his substance, the nature of
which is little known, is formed when a cold
solution of Hg(N0,)2 free from fumes of HNO,
is thrown into alcohol (Cowper, 0. /. 39, 242).
Properties. — Minute hexagonal plates. De-
composes quickly when gently heated, but if the
temperature be suddenly raised to about 130° it
explodes. Insol. water, alcohol, and ether. Sol.
HCl with decomposition. Sol. and maybe re-
orystallised from dilute H^SO,.
Beactions. — 1. With ILjSAq the compound
yields HgS and mercaptan. — 2. Digestedi with
caustic alkalis nitric acid is removed, and the
compound C2H2(HgO)„H20 remains. — 3. Heated
with alcohol and HNO3 it is converted into mer-
curic fulminate. <
Normal amidodicy^nic acid CjHgNaO i.e.
(H0)C^^^C(NH2). Semi-amide of normal
dicyanic acid.
fformatton. — 1. By heating dicyandiamide
with baryta water one of the amido- groups is
replaced by hy(h:oxyl (HaUwachs, A. 153, 295).
2. By allowing a. solution of CNOK to stand to-
gether with eyanamide, when direct combination
takes place, NH.2(CN)20K being formed (HaU-
wachs). f
Properties. — Needles. Monobasic acid. De-
composes carbonates. Heated alone or together
with dilute H2SO4, it takes up the elements of
water, forming biuret, thus :
(0N)2(NH,)0H + HjO = NH2.CO.NH.CO.NHj. In
the same manner with (NHJjS thiobiuret is ob-
tained (Baumann, B. 8, 709).
MeTATiTiIO dekivatives.
(CN)2NHjOK.— NaA'.— BaA'j 3aq. — CuA'j 4aq.
Large blue crystals. Y. si. sol. cold water.
Aqueous solution,iwhen boiled, deposits a dark
green pp. insol. water, and v. si. sol. (iold acetic
acid. This pp. has the composition C^NjCuHO i.e.
(?) ,tCN)2<^^>Cu.— (CN)2{NH2)OAg. Amor-
phous powder, or from ammoniacal solution in
needles. Insol. water.
AlE7L debitaiives.
Ethyl amidodicyanate OjHjNjOj i.e,
7 NH2C<^^^*>C0. The sodium salt of this
compound is formed by direct combination of
ethyl isocyanate and normal sodium eyanamide.
The free acid decomposes when liberated with
formation of eyanamide and other products.
Salts.— (0N00):NEt.NHNa.—AgA' (Wun-
derlich, B. 19, 449).
Slthiodicyanic acid v. Diieiodictanic aoid.
Normal dicyandiamide OjH^N^ i.e.
(NHj)C'^S^C(NHj). Di-andde of normal di-
cyanic acid.
Formation. — Cyanamide polymerises to di-
cyandiamide by long continued evaporation of
its aqueous solution (Beilstein a. Geuther, A.
108, 99 ; 128, 241). This change is more readily
effected if a little NH, is present (Haag, A. 122,
22), or dilute alkalis, or even in the cold when
concentrated alkalis are employed (Baumann,
B. 6, 1373).
Properties. — ^Broad laminis [205°] (Haag).
Sol. water and alcohol. Insol. ether (cyanamide
is sol. ether),
Beactions. — 1. Seated alone one part poly-
merises to normal melamine, another loses NH,
and forms melam (Dr^chsel, J. pr. [2] 13, 331). —
2. Heated with water polymerisation takes place,
and at the same time two amidogen groups are
replaced by hydroxyl, forming melanurenic acid
(CN)3(NHj)(0H)2 and NH,. This aoid is also
formed by heating dicyandiamide to 120° with
a solution of (NH,)2G0,. — 3. Heated with dilute
acids it assumes the elements of water, forming
NTT
guanylurea C0<[j;j2^(j/jj-g-j-^-g- . Similarly with
BLjS gnanylthiourea is produced. — 4. With HO
and zinc melamine and NH, are formed (c/. Bam-
berger, B. 16, 1462). — 5. Guanidiu hydrochloride,
together with CO., and NH„ are formed by heat-
ing it with NH,Ci at 150° (Eathke, B. 18, 3107).
6. Heating with Ba(0H)2Aq one amido group is
replaced by hydroxyl, leaving amidodicyanio
acid. — 7. It combines with CNSH to form thio-
ammeline (CNj^NH^ (Eathke, B. 18, 3102).
Metallic debivaiives.
Sodium, dicyandiamide C^H^NtNa - i.e.
(CN)j(NH2)NHNa. A soluble crystalline pp. ob-
tained by mixing together alcoholic solutions of
dicyandiamide and sodium ethylate (Bamberger,
B. 16, 1461).
Dicyandiamido siVoernitrate (C2H,N4)AgN0,.
Precipitated in minute needles on adding AgNO,
to an aqueous solution of dicyandiamide (Haag).
Silver dicyandiamide C^HjNjAg i.e.
(CN)2(NH2)NHAg. Formed by treating an aque-
ous solution of dicyandiamido silver nitrate with
ammonia.
Aleyl derivatives.
Ethyl dicyandiamide C^HgNi i.e.
(CN)2(NH2)NHEt. A weak base formed by dis-
tilling ethyl cyanamide (Cloez a. Cannizzaro, A.
90, 96). Distils unchanged at 300°. Gives a
yellow insoluble platinochloride salt.
AlKOYL DERIVATIVES.
Dibemoyl dicyandiamide CuiHijNjO,
ix. (CN)2(NHBz)2. Formed by heating triben-
zoylmelamine in a current of hydrogen. Crystals.
[112'=]. V. sol. alcohol, less sol. etiier, v. si. sol.
water (Gerlich, J.pr. [2] 13, 272).
Isodicyanic acid C2H2N202i.e. (0:0)2(NH)2 or
C0<[]jjTT^C0. Alkyl derivatives correspond-
ing to this hypothetical acid have been prepared.
Alktl deeivatives.
(?) Dimethyl isodicyanate OtK^JO^i.e.
CO^jjjjr^CO. Methyl isocyanate polymerises
in presence of PEtj to a solid compound [98°]
(Hofmann, B. 3, 765), which is not identical
with either methyl isooyanurate [176°-6°] or
methyl cyanurate [185°], and which possibly
has the above constitution.
Diphenyl isodicyanate O^HigNjO, i.e.
co<]^Ph>co.
Fonnation. — By polymerisation of phenyl
isocyanate in presence of PFt, (Hofmann, A.
Suppl. 1, 57 ; B. 4, 246) or pyridine (Snape, O, J.
49, 254).
PrcrperHes. — ^Square tables from alcohol
[175°] Insol. water or ether, v. si. sol. alcohol.
OYANIO, DIOYANTO, AND TRIOYANIO ACIDS.
819
Beaotions. — 1. Heated it evolves phenyl iso-
cyanate. — 2. Heated with alcohols it forms alkyl
diphenylallophanates CO.NHPh.NPhCOOEt.—
3. With phenol phenyl-carbanilate is formed
NHPh.CO.OPh. — 4. Alooholio ammonia reacts
with the formation of 3-di-phenyl-biuret
NHPh.0O.NPh.CO.NHa.— 5. With amiUne tri-
phenyl-biuret results.
Derivative. — Di-p-bromo-phenyl isodioyana te
(CO)2(NOaH^Br)2 is formed by polymerisation of
p-bromo-phenyl isooyanate with PEtj. Laminse.
[199°] (Dennstedt, B. 13, 228).
Di-p-tolyl dicyanate C^fiJO^)^.
[185°] (Frentzel, B. 21, ,411). Converted by
alcohol into di-p-tolyl allophanio ether [111°].
TBIOTANOGEN GEQUP.
Normal cyauuric acid CiEJS.O, i.e.
COH
•OH N N
(C!N)/-OH i.e. il 1. . Tricyamcacid.
\0H HOC COH
\//
N
FormaKon.—X. Htj distillation of uric acid
(Soheele, Opuscula, 2, 76). — 2. By the action of
water on (0N),Cl3 (SeruUas, A. Ch. 38, 390).—
3. By the action of heat on urea (Wohler, P. 15,
622). Instead of urea itself the salts of urea
may be employed (Pelouze, A. 44, 106 ; De Vrij,
A. 61, 249 ; Wiedemann, A. 68, 324).— 4. By
heating oyamehde with cone. HjSOj (Weltzien,
A. 132, 222). — 5. Cyauurio acid is one of the
products of me action of COClj on NH.,. — 6. The
action of heat on xauthogenamide 3CS(NH2)OEt
= (CN)3(0H),-HEtHS (Debus, 4.72, lH).-7. By
the action of HCl on such compounds as mslam,
melen, melon, melonic hydride, melamhie, am-
meline, ammelide, psetadothiooyanogen , andthio-
prussides.-=-8. From guanamide by oxidation with
PNO3 (Nencki, B. 9, 235).— 9. From cyanic acid
by spontaneous polymerisation together with
qyamelide. This may be effected by adding HCl
to CNOKAq in presence of ether and agitating.
The cyauuric acid is taken up by the ether
(Klason, J. pr. [2] 33, 129).
Prepa/ration. — 1. Urea is heated till it ceases
to give off ammonia, the residue is dissolved in
boiling water, and the filtrate left to crystallise
on cooling. The crystals so obtained are ptirified
by dissolving them in hot H2SO4 and dropping in
HNO3 until the solution is colourless and efiEer-
, vesoence has ceased. After cooling the solution
is diluted with water when the cyauuric acid falls
as a snow-white powder (Wohler a. Liebig). —
2. Dry chlorine gas is passed into melting urea,
whereupon the mass swells up strongly, gives off
fumes of NHjCl, together with HOI and N, and
is converted into cyauuric acid (Wurtz, A. 64,
307). -3. De Vrij (A. 61, 248) uses HCl instead
of 01. peruUas prepares the acid from oyanuric
chloride, and Merz a. Weith (B. 16, 2896) simi-
larly employ cyanurio bromide.
Prqpertes.— Colourless oblique rhombic
prisms (jErom water) containing 2aq, or aiihydrous
octaheora. Measurements (Kef erstein a. Sohabus,
P. 99, 275). Crystals effloresce. By heating to
100°-120°, or by crystallisation from cone. HCl
or H2SO4, the acid becomes anhydrous (Wohler,
B. J. 1-0, 83 ; Voit, A. 132, 222). S.G. s 1-768;
M 2-5Q0; ^ ?-228; ^ l-fio (Troo?t a, Haiite-
feuille, J. 1869, 99 ; of. Schroder, B. 13, 1072).
H.C. 250,260 (T. a. H.). S. 2-5 cold, more sol.
liot water. S. (alcohol) 21°-24°, 0-1 (Senier,
0. J. 49, 695). Sol. hot HOI, HNO,, or H^SO^,
without decomposition unless the heat be pro-
longed for a considerable time. Absorption ,
spectrum (Hartley, 0. J. 41, 48). By treatment
with PCI5 cyanurio chloride is formed (Beilstein,
A. 116, 357).
Test Reactions. — 1. Heated in a. small tube
closed at one end it evolves cyanic acid, the pun-
gent odour of which may be detected even in the
case of very minute quantities (Wohler). — 2. A
fragment of the acid is dissolved in dilute am-
monia and a drop of ammonio-sulphate of copper
solution added. On stirring a beautiful pink
copper salt ia precipitated (Wohler). — 3. A satu-
rated solution of the acid in cold cone. ^NaflOAq
becomes thick vrith suspended crystals of the tri- ,
sodium salt on heating (Hofmann, B. 3, 770).
BaIiOOEN sebivatives.
,/:
Cl
Cyanurio chloride O3N.CI3 i.e, (0N)3^01.
-\oi
FormaUon. — 1. By the action of anhydrous
01 on anhydrous HON in presence of sunlight
(SeruUas, 4. Oh. [2] 35,, 291 a. 337; Liebig, P.
20, 369 ; 34, 604).— 2. By treatment of cyanurio
acid with PCl^ (Beilstein, A. 116, 857).,
Preparation. — The employment of the method
of SeruUas has given rise to several improve-
ments, chiefly with the view of preventing the
formation of persistent double compounds of
HGl and HON. The HON is dissolve-d in anhy-
drous ether, into which the 01 is led (Gautieri^.
141, 122), or the ether may be advantageously
replaced by chloroform, in which Cl is more
soluble, for an excess of this agent leads to a
better result. 70 p.o. of the theoretical yield was
thus obtained by Klason (Bihwng till K. Svenska
Vet. Akad. Handl. 1885, 10, No. ,5). Another
plan to attain this end is to ensure excess of 01
from the commencement. The chloroform sur-
rounded by a freezing mixture is first saturated
with chlorine, and then a mixture of 01 and HON
is passed slowly in until after some 24 hours the
evolution of HCl ceases, and the whole of the
HON is converted into chloride. A portion of
the cyauuric chloride in most instances sepa-
rates from the CHOI3 during the operation in
beautiful crystals. The remainder is obtained by
distii;iing ofE the chloroforin (Fries, C. J. 49, 739).
Properties. — Colourless crystals. Measure-
ments (Hofmann (Fock), B. 19, 2063). [146°]
(Hofmann). a90°) (SeruUas). V.D. 6-35 (calc.
6-39) (Bineau, A. Ch. [2] 68, 424). Odour re-
sembling mice. Exceedingly irritating to the
eyes. Very poisonous.
Reactions. — 1. Cold wflsier has little or no ac-
tion on (0N),Cl3. By long boUing with water
or quickly in presence of alkalis it is converted
into cyanurio acid (SeruUas). — 2. Alcohols and
phenol behave similarly to water, cyanurio acid
and alkyl chlorides being formed (Klason). — 3:
KHS in the same manner gives trithibcyanurio
acid (Hofmann, B. 18, 2201). — i, AmmoMa or
amines react successively, forming liormal mono-
and di-amide- chlorides, and finally normal me-
lamines (Hofmann, B. 18, 2774 ; Klason, /. pr.
[2] 33, 294).— 5. Cyanurip chloyide reacts on ti)e
820
OYANIO, DIOYANIC, AND TRICYANIO ACIDS.
anhydrous soduim salts of organic acids giving
acid dhlorides and sodium cyanurate (Senior, C. J.
49, 312). — 6. BenzamMe is converted by oyanurio
chloride into benzonitrile, and the water thus
liberated acts on the chloride forming oyanurio
acid and HGl (Senier).
/Br
Cyanuric bromide C^'^^i^i.e. (CN)3^Br.
XBr
Formation. — 1. By the action of bromine on
anhydrous HON (SeruUas, P. 14, 446; Ponoma-
reff, B. 18, 3261 ; Merz a. Weith, B. 16, 2894).—
2. By heating an ethereal solution of CNBr to
130°-140° (Eghis, B. 2, 159). Pure CNBr does
not polymerise. Polymerisation may, however, be
effected by passing SCBr through an ethereal
solution of CNBr when the less soluble polymer-
ide comes out in crystals (Ponomareff).
Properiies.^— Amorphous white powder. At
300° it melts with decomposition. Insol. cold
water, cold alcohol, ether, and benzene. Heated
with water or alcohol it is converted into cyan-
uric acid. With acetic acid it yields oyanurio
acid and acetyl bromide (Ponomareff).
A
Cyanuric iodideO^T^'J^i.e. (CTS)^^!. Ob-
\l
tained by double decomposition between (CN)30l3,
and HI In the cold {Kinson, Bihang till K. Svenska
Vet. Akad. Bandl. 1885, 10, No. 5). A dark
brown insoluble powder which at 200° decom-
poses into paracyanogen and iodine. Heated
with water at 125° it splits into HI and cyanuric
acid.
Cyanuric chloro iodide OjNjIjGI i.e.
A
(CN),^I. An intermediate product between
\ci
cyanuric chloride and iodide, also formed in the
preparation of the latter (Elason).
Metallic debivatxves v. Oyahubates.
Alkyl derivatives.
Formation. — ^By the action of ONCl on so-
dium alcoholates, in which case normal cyanic
ether is probably first formed and then polymer-
ised (Hofmann a. Olshausen, B. 3, 271). CNBr
or (CN)8Br,' is conveniently substituted for CNCl
in this reaction (Ponomareff, B. 18, 3264 ; Ela-
son, J.pr. [2] 33,131).
Beactioi}s. — 1. By distillation they are con-
verted into the corresponding iso- ethers (Hof-
mann a. Olshausen). — 2. Heated with dilute al-
kalis they assume the elements of water, and
break down into alcohols and pyanurio acid.
Trimethyl cyanurate OjHjNaOj i.e.
yOMe
(ON),^OMe. Needles. Measurements (Hof-
\OMe
mann (Fock), B. 19, 2065). [135°]. (265°) (Hof-
mann). SI. sol. cold, v. sol. hot water (Hofmann
a. Olshausen). PCI5 reacts forming (CN)3Cl3
(Hofmann, B. 18, 2799). With HgClj it gives
08HjNsOj,HgCl2 (Ponomareff, B. 18, 3266).
Diethyl-cyanurio acid C,H„N,0, i.e.
/OEt
(CNjs^OBt. Formed by the action of Ba(H0)2Aq
\0H
or dilute NaHOAq on the triethyl ether (Ponoma-
reff, B. 18, 3267 ; Hofmann, B. 19, 2077 ; Mul-
der, R. 4, 91). Crystalline powder [100-180]
(Hofmann). Sublimes above 200° with decom-
position. SI. sol. cold water or alcohol, insol.
ether. Warmed with acids oyanurio acid is set
free. The barium salt crystalUses with 3aq from
concentrated or with 12aq 'rom dilute solutions.
Y. sol. water. The lead salt is insol. water.
Triethyl cyanurate CgH^NjO, ij».
/OBt
(CN)3^0Et.
NOBt
Properties. — An oily liquid crystallising at
0° (Mulder, B. 15, 70 ; B. 1, 195 ; 2, 133 ; 4, 91 ;
Ponomareff, B. 15, 513). [29°-30°] (Hofmann, B.
19, 2074). (275°) (Elason, J. pr. [2] 33, 131).
S. 0-7 in cold water. V. sol. alcohol, ether, CHCl,,
and CS,. The aqueous solution at 0° deposits a
crystalline hydrate containing 12aq (Mulder).
With HgClj it forms the crystalline double salt
C5H,5N303,HgCl2 (Ponomareff), and with Br the
compound C3H,5N3P3,Br, (Mulder).
Beactions.—l. Heated to 180°-200° it is con-
verted into triethyl isocyanurate. — 2. Cone. HCl
sets free cyanuric acid. — 8. Dilute NaHO or
Ba(H0)2 removes one of the Bt radicles form-
ing diethyl-oyanuric acid. — 4. PCI5 reacts with
formation of (CN),Cl3. — 5. Heated with cone.
NHjAq to 170°-180° amidogen replaces ethoxyl
groups, ammeline and melamine being formed.
Tri-iso-amyl cyanurate C,8H„N,0, i.e.
yOC,H„
(CN),^0C5H„. Syrupy liquid. Undergoes in-
\0C,H„
tramolecular change above 360°. (Elason).
Triphenyl cyanurate 02,H,5N30, t.e.
yOPh
(0N)3^0Ph. Needles. [224°]. Distils un-
\OPh
changed. Insol. water and ether, sol. benzene.
Cone. HCl at 180° causes it to combine with the
elements of water and break down into phenol
and cyanuric acid (Hofmann a. Olshausen ; Hof-
mann, B. 18, 765 ; 19, 2083 ; Elason, Bihang
till K. Svenska Vet. Akad. Handl. 1885, 10,
No. 7).
Tri-p-nitrophenyl cyanurate
/OCeH^NO,
CjiHijNA i.e. (CN)3^0C„H,N0jj. Pale yeUow
NOCsH^NO,
tables. [194°] (Otto, B. 20, 2236).
Tri-tolyl cyanurates CsJ3^'S,0, m.
/0C,H, ■
(CN)/-OC,H,.
\00,H,
cyami/rate. Pale yellow needles.
Tri-o-
[152°] (Otto)
^Ri-m-tolyl
scopio needles.
Tri-p-tolyl
cyanurate. Coloui;less mioro-
[225°] (Otto).
cyaniM'ate. Silky colourless '
[207°] (Otto) ; [265°] (Brentzel, B. 21,
OasHjaNaO, i.e.
needles,
411).
Tri-eugenyl cyanurate
xO(C,.H„0)
(CN),fOfC,.H„0).
\0(0,„H„0)
Pale yellow microscopic laminee. [122°] (Otto).
Tri-thymyl cyanurate CagHagNaO, i.e,
/0(C,„H,a)
(CN)3f 0 C„H,a .
Pale yeUow crystalline powder. [161°] (OttO).
OYANIC, DIGYANIO. AND TRIOYANIO A0ID3.
521
Tri-naphthyl c^a>iMj-a<esCjsHj,N,Osi.e.
\00,„H,
Tri-{a)'nap'hthyl cyanurafe. Greenish yellow
powder, atv^-iposing when heated without hav-
ing a distinct melting-point.
Tn-ipynaphthyl cyanv/rate. Light green
powder (Otto).
AlKOYL DEMVAirVES.
Formatwn.—'Sj the action of alkoyl chlor-
ides on silver cyanurate (Ponomareft, B. 18,
3273 ; Senier, O. J. 49, 313).
Tri-acetyl cyanurate OjHjN^Oi, i.e.
/OAc
(ON)AOAo.
\OAo
Acetyl chloride and silver cyanurate are
brought together in presence of ether, the mix-
ture is afterwards evaporated, and the residue
crystallised from chloroform. Minute crystals.
[170°] with decomposition. Insol. ether; si. sol.
CHCI3. Sol. warm water with decomposition
into acetic and cyann;dc acids (Fonomarefi). A
very similar compound to this was obtained by
the action of AcCl on CNOAg in the preparation
of cyanogen acetate or acetyl cyauate (Schittzen-
berger, A. 123, 271).
Tri-benzoyl cyanurate OjjHuNjOj i.6.
/OBz
(CN)3fOBz.
\OBz
Benzoyl chloride and silver cyanurate are
heated together in closed tubes at 100°. The
contents are extracted with CHCI3, which on
evaporation deposits tribenzoyl cyanurate in
needles. On heating it decomposes. SI. sol.
CHCI3 ; insol. ether. Warmed with water it de-
composes into cyanuric and benzoic acids (Senier).
Normal thiocyanuric acid v. Thioovasubio
ACID.
IToTmal amido-cyannric acid. Ammelide.
Melan/wrerdc acid (v. Ammelide).
Normal diamido-cyauuric acid. ArmneUne
, (v. Ammeline).
Halogen DEKiVAirvES v. Ammelinb.
AliKT[h DEBIVATIVES.
Di-methyl-di-amido cyanuric acid.
Dimethyl ammeline CsHjNjO i.e.
/NHMe
(CN)3^NHMe. Dimethyl amide ofcyamuricacid.
\0H
Formed by heating di-methyl di-amido cyanuric
chloride with dilute acids or by heating it with
water at 200° (Hofmann, B. 18, 2770), or by
heating tri - chloroacetonitril with aqueous
methylamine at 120° (Weddige, J.pr. [2] 33, 89).
Crystalline pp. Heated it decomposes without
melting. V. si. sol. boiling water; insol. alco-
hol and ether ; sol. NaHOAq. Possesses acid
and basic properties. (C5HBN5O,H01)2PtCl4.
Ethyl diamido - cyanurate v. Amme-
line.
Ethyl ethylamido-amido-cyanurate.
/NH,
Dlethyl-ammeline GjH,3N50 i.e. (CN)3^NHEt.
\OBt
Obtained by acting on (0N)3Cl3 with NH.,Et
and treatment of the resulting compound with
HCl (Hoftaann, B. 18, 2776).— Platinochlor-
ide (0,H„N30,HCl)2Pt01,.
Vol. II.
Ethyl di-ethy I -di-amido- cyanurate.
/NHBt
Tri-ethyl-ammeline CoHijNjO i.e. (CN)3^NHBt
\OEt .
Formed by heating tri-ethyl-melamine with
HCl (Hofmann, B. 2, 604). Syrupy liquid. Pt.
salt :— (C,H„Ni,0,HCl)2PtCl4.
Di-methyl -di-amido -cyanuric chlor-
ide C3H3N5CI i.e. (CN)3^NHMe. Pre-
\C1
pared by the action of (0N)3Cl3 on a solu-
tion of methylamine in methyl alcohol (Hof-
mann, B. 18, 2766 ; Klason, Bihang till K.
Svenska Vet. Akad. Bandl. 1885, 10, No. 7).
Needles. [241°]. Insol. water, alcohol, and ether.
Soluble with partial decomposition in glacial ace-
tic acid. Eeaots with water, forming dimethyl-
ammeline. Ammonia converts' it into dimethyl-
melamine; methylamine turns it into trimethyl
melamine,
Methylamido ■ methoxy- cyanuric
chloride CjHjNjOCl i.e.
/NHMe
(CN)3f OMe .
\C1
Formed in the same reaction with the last-
mentioned compound (Hofmann, B. 18, 2771).
Needles. [155°]. Sol. alcohol and ether.
Phenyl diamidocyanurate. Phenyl
y
•NH,
Insoluble
ammeline CgHjNjO i.e. (CN)3^N'H2.
\OPh
white ctystalline powder. [245°] (Otto, B. 20,
2240).
o-Tolyl diamidocyanurate. Tolyl
/NH,
ammeline C,|,H„N50 t.e. (CN)3^NH2
\0(C,H,)
White crystalline solid. [225°] (Otto).
AlKOTL DERIVATIVES V. BENZOYL AMMELINE.
Normal cyanuramide. Normal Melamme.
/NH,
C3H3N3 i.e. (0N)3^NH,.
Xnh^
Eormation. — 1. Is one of the by-products in
the preparation of melam by the action of heat
on ammonium thiocyanate (Liebig, A. 10, 18,
53, 342 ; Volhard, J.pr. [2] 9, 29 ; Glaus, 4. 179,
121 ; B. 9, 1915 ; Jaeger, B. 9, 1554).— 2. By the
action of aqueous ammonia at 100° on (CN)3Gl3
(Hofmann, B. 18, 2765 ; Klason, Bihang till K.
Svenska Vet. Akad. Handl. 1885,' 10, No. 7).—
3. From trimethyl thiocyanurate by the action of
concentrated ammonia at 180° (Hofmann, B. 18,
2759). — 4. Gyanamide polymerises by the action
of heat to dicyanamide, and then passing to the
trimolecular grouping, part forms melamine, and
part with evolution of ammonia condenses to
melam (Drechsel, J.pr. [2] 13, 331). — 5. Melamine
thiocyanate is formed when strong ammonia is
made to act on pseudo-cyanogen sulphide at
160° (Ponomareff, J. B. 8, 215).— 6. By the ac-
tion of heat onguanidine carbonate in presence of
phenol (Nencki, J. pr. [2] 17, 235).— 7. Cyan-
melamidine breaks down when heated with HGl
into melamine and HCN (Byk, J.pr. [2] 20, 346),
Preparation. — Trimethyl thiocyanurate is
inclosed in a tube with an excess of concentrated
solution of ammonia, and heated at a temperature
of 180° for several hours. The temperature must
not vary much, for if 200° or so is attained
Y
322
CYANIC, DICYANIC, AND TRIOYANIO ACIDS.
hydroxyl compounds are formed, and if it falls
much below lbO° the reaction is incomplete, and
the melamine will be found to contain sulphur,
rendering a second treatment with ammonia
necessary. When the operation is successful
the tube on cooling will contain an upper layer
of methyl mercaptan, while below in the aqueous
portion large colourless crystals of melamine
will haye made their appearance. It may be
further purified by reorystallisatiqn from water
(Hofmann).
Properties. — MonocUnio prisms (WeibuU,
/. pr. [2] 33, 292). Heated gently it sublimes.
V. si. sol. cold, V. sol. hot water. V. si. sol. hot
alcohol, sol. hot glycerin. Powerful base form-
ing salts and decomposing many metallic salts.
Beactions. — 1. Seated to low redness two
molecules combine with evolution of 3NH, to
formmeUon (CN)3:{NH)3:(CN),.— 2. Heated with
dilute HNOj the amidogen groups are succes-
sively replaced by hydroxyl giving ammeline,
ammelide, and finally cyanurio acid (Knapp, A.
21, 256). — 3. Fused with KHO potassium mellon
and potassium cyanate are formed. — 4. (CN)3Cl3,
AcCl, and Ao^O are without action on melamine
(Senier, ^. 19, 312).
dombinaUons. — B',HC1 l^aq : needles (Lie-
big, A. 26, 187; Byk, J. pr. [2] 20, 345).
— (B'H01)j,PtCl4 2aq (Hofmann, B. 18, 2760 ;
Klason, J. pr. [2] 33, 298).— B'2H3S04 2aq also
with l^aq and 3aq. V. si. sol. cold water. Test
for melamine (Dreohsel, J.pr. [2] 13, 332 ; Byk ;
Jaeger, B. 9, 1555).— BSHjSOj. Short rhombic
prisms. Decomposed by water (Nencki, J. pr.
[2] 17, 237).— B'jHjC^Oj. V. si. sol. water.
— B'HSCN : prismatic crystals. V. si. sol. cold
water (Olaus, B. 9, 1915 ; Ponomarefl, J. B. 8,
215). — ^B'AgN03. Crystalline pp. sol. hot water
and ammonia (Liebig; Byk). , — B'ZAgNOj:
needles (Zimmermann).
MeTAUiIO debtvatives.
By treating (CN)5(NH2)52AgN03 with ammo-
nia a compound said to be diargentomelamitie
yNHAg
(CN)5^NHAg is obtained (Zimmermann).
\NH3
Aleyii debivatives.
Formation. — 1. By the final action of amines
on (CN)3Cl3 (Hofmann; Klason).— 2. By the
action of secondary amines on (CN)3Cl3 (Hof-
mann, B. 18, 2773). — 3. By the action of amines
on trialkyl thiocyanurates (Hofmann).
BeacUons. — 1. Water (dilute acids) decom-
poses alkyl-melamines into cyanurio acid and
amines.
(CN)3(NHEt)3 + 3H0H = (CN)3(0H)3 + 3NHjBt
and
(CN)s(NEtj), + 3H0H = (CN)3(OH)3 + SNHEtj
(Hofmann, B. 18, 2773).
Dimethyleyanuramide. Dirmthylmela-
/NHMe
mme. OsHuN, i.e. (CN)3^NHMe. From dia-
\NH2_
mido-cyanurio chloride by the action of ammonia.
Crystalline base. Sol. water, si. sol. alcohol and
ether (Hofmann, B. 18, 2768).
Trimethyleyanuramidi.
Base.
Kelamine CeHijN, i.e. (CN)3^NHMe.
\NHMe
[115°]. V. sol. water and alcohol.— (B'H01)^tCli.
Liquid.
Prisms. — B'(HCl).^,PtCl4 : long needles (Hofmann,
B. 18, 2763 a. 2767 ; Klason, J. pr. [2] 33,
293).
Sexamethylcyanuraviide. Sexame-
thylmelwmme CjHjgNj i.e. (CN)j^NMe2. Base.
NNMe
Needles. [171°-172°].— (B'HCl)JtCl,: long
needles. SI. sol. water ; sol. alcohol (Hofmann).
Triethylcy anur amide . TrietKylmela-
/NHEt
rrmie C,13.„^^ i.e. (CN)3(-NHEt. Base. Needlea
NNHEt
(from water) or prisms (from alcohol). [73°-
74°]. SI. sol. boiling water. Sol. alcohol, ether,
and benzene.— (B'HC^jPtCl, : insoluble needles.
— B',(H01)2PtCl,.— B'jAgN03 (Hofmann, JB. 18,
2775; Klason, J.pr. [2] 33, 294).
Semaethy ley anur amide.
/NEt,
melamine OijHsjNa i.e. (0N)3^NEt2.
\NEtj
Sol. alcohol , and hydrochloric acid. Base.
(B'HCljjPtCl,. CrystaUine. Sol. alcohol, si. sol.
water. — BTICljAuClj : needles. V. si. sol. water
and alcohol (Hofmann, B. 18, 2778).
Tripiperidyl-cyanuramide. Tripipe-
/NC3H,,
ridylmelarmne CigHjnNs i.e. (CN)3^NC5H,|,. Base.
Xnc^h,,
Needles. [213°].— (B'HC^^PtCl,. Heated with
HCl at 150° it is decomposed into piperidiae
and cyanuric acid (Hofmann, B. 18, 2780).
Triethylidencyanuramide. Tri-
/NC^,
ethyUdermielamine CjHjjNe i.e. (CN)3^NC2H4.
\NO,H,
Formed by the action of CH,CHO on CNNH^.
Sol. alcohol ; insol. water, CS,, CHCI3, benzene,
and aniline (Knop, A. 131, 253).
Cyanuramido acetic acid. Melamyl
/NH,
acetic add. C,'B.s!!ifiJ.e.{CN),(-NB.2
\nH.CH3C00H.
Formation. — By the action of chloro-acetio
acid in presence of sodium ethylate on cyan-
amide (Dreohsel, J.pr. [2] 11, 332).
Properties. — Crystalline powder. Decomposes
without melting when heated. V. si. sol. water,
insol. alcohol and ether. Sol. alkaline solutions.
Combines with bases, acids, and salts.
Combinations.— K salt : sol. water. Com-
bines readily with CO,. — B'HCl : needles ; v. si.
sol. water; insol. hydrochloric acid. — B'HNO^aq:
laminEB. — B'AgNGj aq : needles. — B'^H^SOi :
large prisms. ' .
Phenylcy anur amide. PhenyVmela/mirie
Formed by heating
/NHPh
0,H„N3 i.e. (CN)3^NH, .
NNH^
diamidocyanuric chloride with aniline at 150°.
Prisms. [284°]. Sol. alcohol. (B'HCl),PtCl,
(Klason, J. •jpr. [2] 33, 295).
Triphenylayanuramide. Triphenyl-
melamine
/:
■NHPh
0„H,3N3i.e.(CN)3^NHPh.
NNHPh
Needles.
[228°]. . (360° sublimes). Insol. usual solvents.
81. sol. glacial acetic acid (Hofmann, B. 18,
3218; Elason).
CYANIC, DICYANIC, AND TRIOYAlNlC ACIDS.
323
Pseudotripheny ley anur amide. Tn-
plienylmelamine CjHjPhjN,. Formed by the
destructive distillation of tribenzoyl-melamine.
ifellow crystalline insoluble powder. Sol. hot
, phenol, [c. 3(>0°] (Gerlich, J. pr. [2] 13, 286 ;
Drechsel, B. 21, 1549).
Tetraphenylcyanur amide. Tetraphe-
/NPh,
nylmelamine CjjHjjNs i.e. (CN),,^NPh2.
■\nh,
Formation. — 1. By heating diphenylguani-
dine to 170°-180° (Hofmaun, B. 7, 1737).— 2.
By the action of CNCl on aniline at 170°-180°
(Weith a. Ebert, B. 8, 912).
Properties. — Needles. [217°]. Insol. water ;
T. b1. sol. ether. Mono-acid base. Heated alone
it decomposes into NH,, mono-, and di-phenyl-
amine and HON ; with HCl or KHO the products
are 00.^, NH,, and aniline. Hydrochloride: —
B'HCl. Pt salt :— (B'HCl),PtCl,.
Sexaphenylcyanuramide. Sexaphe-
/NPh,
nylmelamine OjjHjjNa i.e. (0N)5^NPh2. Ehom-
XNPh^
bic tables (from nitrobenzene), [above 800°]. In-
sol. usual solvents. Does not combine with HCl.
At 200° HCl decomposes it into diphenylamine
and oyanurio acid (Hofmann, B. 18, 3219).
Tri-p-toly ley anur amide. Tri-p-tolyl-
melamine C^iHjjNj i.«. (ON)j^NHC,H,. Indif-
\nhc,h,
ferent. Insoluble. Needles. [283°] (Klason, J.pr.
[2] 33, 294).
Triamido-tritolyl cyanuramide. Tri-
toluidylmelamine C^iHj.Ns, i.e.
/NHC,H,NHJ
(CN)s^NHC,HjNHj. Formed by the action of
\nHO,HjNHj
tolylene-diamine on cyanuric chloride (Fries,
0. J. 49, 314 a. 739). The two intermediate
compounds mono- and di-tolylene-amido-
cyanuric chloride are also formed in this
reaction (Fries).
Trinaphthyl - cyanuramide. Tri-
/NHC,.H,
napMhylmelamine CjjHjjNii i.«. (CN)j^NHC,„H,
\niic,.h,
Formedby the action of (a) and (|8) naphthylamine
on (0N),0l3 {a)-trinapMhyl-melamine [223°] and
(SytrinapMhyl-melamine [209°] together with
the (o) and (/3) mono- and dinaphthylamido-
cyanvHe chlorides are formed (Fries).
Triphenyl- tri - amido - cyanuramide.
Trianilylmelarrmie G^^K^, i.e.
/NHJitH.Ph
(CN)3f-NH.NH.Ph. Obtained together with the
\NH.NH.Ph
mono- and dvphenylhydrazine-cya,rvwric chloride
by the action of phenylhydrazine on (CN)3Cl3
(Fries).
AlKOYL DEIilVATIVES.
Formyl - cyanuramide. Formyl-mela-
/NH(CHO)
miree C,H.N|,0'i.e. (ON)s^NHj . Prepared
\nh,
by the action of oxalic ether on oyanamide
(Mulder, B. 7, 1631). Insol. water. Decomposed
by acids or long boiling with water.
Tribenioy I -cyanuramide. Tribenzoyl-
/NHBz
melamine C2,H„N„0, i.e. (CN)3^NHBz. Formed
\nHBz
by polymerisation of benzoyl-cyanamide. Yellow
powder. [275°]. Insol. water, alcohol, and ether.
Heated the products are COj, HCN, benzonitrile,
dibenzoyldicyanamide, and pseudotriphenyl-me-
lamine (Gerlich, J. pr. [2] 13, 272).
Condelised cyannramido- compoandB.
Melam 0|,HgN„ i.e.
(CN)3f NH3 H^-^{CN),.
\ — NH — /
Preparation. — Crude melam is obtained by
the action of heat on ammonium thiocyanate
leCNSNHj = 2GeH3N„ ■¥ 5(NH,),S h- 4CS, + SH^S.
A strong heat should be applied, best by means
of a metal bath, rising quickly to 300°, and
continued till the evolution of gas ceases (Liebig,
A. 10, 10 ; Glaus, A. 179, 118). The product
consists of melam thiocyanate and melem. It
is washed by boiling with water and afterwards
with cold dilute potash. Then it is dissolved in
hot dilute HCl and reppd. by KHO (Klason,
J. pr. [2] 33, 286).
Properties. — An indifferent insoluble powder.
Slightly sol. acids and hot alkalis. Heated
alone it yields NH3 and meUon ; with dilute
acids or alkalis it gives NH, and ammeline ; with
cone. HNO3 cyanuric acid.
Melem G|iH„N,5 i.e.
/NHj HjN\
(CNJaf NH ^(CN)3 (?). Prepared by di-
\ — NH — /
gesting 1 pt. of crude melam with 4 pts. KHO
and 80 pts. of water for 24 hrs. at 100°, Melem
remains unacted upon, while melam is converted
into ammeline. By heating with cone. KHO
melem forms ammelide and NH, (Klason, /. pr.
[2] 38, 287).
/NH\
Mellon C„H3N, i.e. (CN)3f-NH-^(CN)3 (?).
\NH/
This compound, which is the homologous tri-
moleoular modification of cyanogen cyanamide
(CN).NH.(CN), of which metallic derivatives are
known (Bannow), is formed among the products
of the action of heat on numerous cyanogen
derivatives — ^pseudothiocyanogen, mercuric thio-
cyanate, ammonium thiocyanate, melem, mela-
mine, ammeline, ammelide, diamido-cyanuric
chloride, oyanamide, &o. (Liebig, A. 10, 4 ; 50,
342 ; Laurent a. Gerhardt, A. Oh. [2] 19, 85 ;
VoBlckel, P. 61, 375). A light yellow powder.
Insol. water, acids, and alkalis.. Heated alone
it breaks down into N, CjN^, and HCN ; with
KHO, into NH3 and mellonpotassium, and with
HNO3 into cyanilic acid and NH3.
Mellonhydride CjHjNia i.e.
/(CN)3 = NH
N^ CN)3=NH (?).
\(CN)3 = NH
Preparation. — The potassium salt of mellon-
hydride is formed either by heating a mixture
of mellon and KHOAq in presence of cyanogen,
or by melting potassium thiocyanate together
with melam, mellon, or SbCl, (Liebig, A. 95, 271 ;
Volhard, J. pr. [2] 9,- 29 ; Klason, J.pr. [2] 33,
289). The potassium salt is converted into a
s2
S34
CYANIC, DICYANIC, AND TRIOYANIC ACIDS.
copper compound, and this decomposed by H^S
gjves an aqueous solution of the free hydride.
Properties. — A strongly acid solution. De-
composes carbonates. AH attempts to isolate
the free hydride have been unsuccessful. It
forms primary, secondary, and tertiary salts.
Salts. — KH„C„N,s. — K^HCjN,, 3aq. —
KjCjNiaSaq. Needles. Bitter. S. 2-7 in cold
water. — Ca3{C|,N,3)2 4aq. — Ba3(CaNi3)2 6aq. —
Cu3(C9N,3)2 5aq.— AgsCjNij.
Cyameluric acid CbH3N,0325HjO i.e.
NH H0\
(CN), O (CN)3 (?), or possibly
/OH H0\
(ON),/ H0-)(CN)3.
Formation. — By the long-continued digestion
of potassium mellon with KHO and liberation
of the free acid from the salt so obtained by
HCl (Henneberg, A. 73, 235 ; Volhard, J.pr. [2]
9, 30).
Properties. — Powerful tribasio acid. White
powder.' V. si. sol. water. Heated alone it yields
cyanic and oyanuric acids and mellon.
Salts. — KjA^Saq: needles. Sol. water
with strong alkaline reaction (Liebig, A. 95,
281).— KHjA'" 2aq.— Ba3A"'j aq— AgjA'".
^NH
Isocvanuric acid (C0)5=NH. The hypo-
^NH
thetical acid corresponding to the isocyanurio
ethers.
Alktl dekivatives.
Formation. — 1. By the distillation of a mix-
ture of potassium cyanurate and alkyl sodium
sulphate (Wurtz, A. Ch. [3] 42, 57).— 2. By the
action of heat on alkylacetylurea alkyl iso-
cyanurates are formed, together with acetamide
and other products (Hofmann, B. 14, 2728). —
B. From dialkylureas by heating (Wurtz, J.
1856, 700).— 4. By the action of alkyl iodides
on silver or potassium cyanurate (Habich a.
Lirapricht, .4. 109, 112; Ponomareff, B. 18,
3270). — 5. By polymerisation of isocyanio ethers
or the intramolecular change of normal cyanuric
ethers (Hofmann a. Olshausen, B. 3, 271).
Reactions. — 1. The action of water (heating
with dilute acids) causes the isocyanurio ethers
to break down like the isocyanic ethers into COj
and amines (Wurtz).— 2. With PCI3 isocyanurio
ethers do not give oyanuric chloride, but chloro-
alkyl substitution compounds (Hofmann, B, 18,
2800).
Dimethylisocyanurie acid C^Hj^fi,
^NMe
i.e. (C0)3=NJIe. Needles. Crystal measure-
^NH
ments (Hofmann, B. 19, 2071). [222=]. Its salts
are not very stable. Ammoniacal solution gives
with CuSOj a violet Cu salt. Silver salt v. si.
sol. water (Hofmann, B. 14, 2728 ; 19, 2069) ,
Trimethylisocyanurate CuHjNjOj i.e.
^NMe
(C0)3==NMe. Prisms. Crystals measured (Hof-
%NMe
mann, 5.19, 2067). [175°-176°]. (274°). Insol.
cold, si. sol. hot water. Sol. alcohol. Treated
with PCI3 the compound (CN)3(0CHjCl), is
formed.— B'HgClj crystals (Wurtz ; Hofmann a.
Olshausen ; Ponomareff, B. 18, 3271 ; Hofmann,
B. 18, 280Q ; 19, 2093).
Combinations with formamide (Gautier, A.
149, 313) (CN)3(NMe)s,HC0NH2. Obtained by
the oxidation of acetonitrile. [175° with partial
sublimation] (CN)3(NMe)3,(HCO)jNH. [163°].
(168°).
Diethylisocyanuric acid CjH„Nj03 ix,
y^NEt
(C0)3=NEt. Hexagonal prisms. Measurements
^NH
(Hofmann, B. 19, 2078). [173°]. SI. sol. cold,
sol. hot, water. Sol. alcohol, ether, ammonia,
and alkalis. — B'^Ba aq : sol. water. — B'Ag :
needles, ppd. by ammoniacal AgNOj. Copper
salt rose-coloured (Habich a. Limprioht, A. 109,
112 ; Wurtz, /. 1856, 700 ; Ponomareff, B. 18,
3270).
Triethyl-isocyanurate CsHijNsOj i.e.
^NEt
(CO)a=NEt. Ehombio prisms (Hofmann, B. 19,
^NEt
2076). [95°]. (276°). Distils with steam. Sol.
hot water, alcohol, and acids. PCI, has no
action, and KHO decomposes the ether with
difficulty. Heated with Ba(OH).Aq it yields CO,
and triethylbiuret, and similarly with sodium
alcoholate ethylene, ethylamine, triethylguani-
dine, and triethylbiuret are formed (Hofmann,
J. 1861, 516). Chlorine forms substitution
derivatives (Wurtz ; Habich a. Limpricht ;
Ponotnareff ; Gal, A. 137, 127).
Tetrachlorotriethyl isocyanurate
CjHiiCljNjOa. Crystals. Insol. water ; sol. al-
cohol. Not ppd. by AgNOj. Compounds con-
taining less CI are obtained by the action of
alcoholic potash (Habich a. Iiimpricht, A. 109,
109).
Tribenzyl isocyanurate v. Benzyl-
CYANUEATE.
Triphenyl isocyanurate CjiHisNjOi
^NPh
i.e. (C0)3C=NPh.
%NPh
Fonjiation. — 1. The NH groups of triphenyl- '
isomelamine are replaced by oxygen by treatment
with alcohol and HCl. — 2. Phenyl isooyanate is
polymerised to isocyanurate by heating for 3hrs.
at 100° with dry potassium acetate (Hofmann,
£.3,268; 18, 765 a. 3225).
Properties.— Prisms. [274°-275°]. Distils
mostly unchanged. Insol. water ; sol. hot
alcohol.
Cakboxylio derivatives.
By the action of ethyl chloroformate
ClCOOEt on potassium cyanate, besides carbox-
ethyl-carbamio ether, three carboxethyl deriva-
tives of isocyanurio acid have been obtained.
These are triethyl isocyanurcarboxylate, and two
derivatives intermediate between that compound
and isocyanurio ether. By distillation they lose
CO: ^n<} s,re converted into isocyanurates (Wurtz
a. Henninger, Bl. 44, 26).
Triethyl isocyanurcarboxylate
/NCOOEt
C.jH.jNsO, i.6. (C0)3^NC00Et. Crystals.
\NC00Et
[118°- 119°].
CYANIC, DICYANIC, AND TRICYANIC ACIDS.
325
Diearboxethyl ethylisocyanurate
/NCOOEt
C„H,5N,0, i.e. (C0)3f-NC00Et . Crystals.
\NEt
[123°].
Garboxethyl diethylisocyanurate
/NCOOEt
C,.H,5NsOj i.e. (COJs^NEt . Needles.
NNEt
[107°].
Isoammelide (hypothetical)
CNH
hn,/\nh
o^Uco
NH
Aleyl derivatives.
Trimethylisoammelide CjHijNjO^ i.e.
CNH
MeNl/'^NMe
. Formed by the action of HCl
J CO
y
OC
on the platinnm salt of trimethyliaomelamine. —
UHCl : needles ; sol. alcohol, insol. ether. —
B'HCl.AuClj : needles ; v. si. sol. water (Hof mann,
2i. 18, 2786).
Triethylisoammelide CaH^NiOj i.e.
CNH
EtN,/\NEt
. Obtained by treatment of tri-
^CO
OG
NEt
Plhvl isomelamine with HCl. — (B'HCl)2PtCl,
(llo'fmann, B. 18, 2789). '
Triphenylisoammelide CjiHuN^Oj i.e.
CNH
PhN
00
Q
NPh
CO '
From triphenyl isomelamine
NPh
by heating with HCl. Needles. [272°].—
(HHCl)2PtClj: amorphous (Hofraann, B. 18,
B'225).
CNH
hn.-^Nnh
ocl Jcnh"
NH
Isoammeline (hypothetical)
C^H^NjO i.e.
00
AliKTL DEBIVATIVES.
Trietkylisoammeline
CNH
EtNf^NNEt
. Formed by the action of HCl
^sJCNH
NEt
on triethylisomelamine (Hofmann, B. 18, 2789).
Triphenylisoammeline C^i^^Nfi i.e,
CNH
^NNPh
. This and the corresponding iso-
JCNH
ammelide derivative represent the two possible
intermediate compounds between alkylisomela-
niine arid alkyliso-oyanurate. Both are prepared
by treatment of triphenylisomelamine with HCl,
the isoammeline being first formed (Hofmann,
B. 18, 3224).
Isomelamine (hypothetical) (CNH)j3NH ie.
CNH
/\
HN NH
HNC CNH
\/
NH
AlKYL DEBIVATIVES.
Formation.^— By heating solntions of alkyl-
eyanamides, whereby polymerisation takes place
(Hofmann, B. 2, 602).
lieacticms. — Heated with dilute acids the
alkyl isomelamines yield NH,, and become
converted into isocyannrates (Hofmann).
Trimethylisomelamine CjH|2N„3aq i.e.
(CNMe)s(NH)s 3aq. Needles. [179°]. Commences
to sublime above 100°. Sol. water and alcohol,
insol. ether. Beaction alkaline. HCl acts in the
first instance, forming trimethylisoammelide and
then trimethylisocyauurate. — B"(H01)2,PtCl4.
LaminsB. Y. si. sol. water and alcohol. —
B"(HCl)j,,AuCl,,. Needles (Hofmann, B. 3, 264 ;
18, 2784 ; Baumann, B. 6, 1372).
Trieihylisomelamine 09H,sN„4aq i.e.
(CNEt)3(NH)3 4aq. Crystals. [92°]. V. sol. water
and alcohol. Beaction alkaline. HCl reacts form-
ing successively triethyl-isoammeline, triethyl-
isoammelide, and triethyl isocyanurate. — Sal t s :
E"(HCl),„PtCl,. Sol. water.— B'(HCIAuCl3)2.
Needles. SI. sol. water and alcohol (Hofmann,
B. 2, 602 ; 3, 266 ; 18, 2788).
Tribemy I -isomelamine G^^ELu'Sg i.e.
(CNCjH,)3(NH).,. LaminsB [higher than benzyl-
oyanamide]. — B"(HC1)2. Needles. SI. sol. water
(Strakosoh, B. 5, 694).
Triphenyl -isomelamine C^iHigNj i.e.
(CNPh)33NH. Needles. [185°]. V. si. sol. hot
water, sol. alcohol and ether. HCl reacts forming
successively triphenyl-isoammeline, triphenyl-
isoammelide, and triphenyl-isooyanurate. —
B3(HCl)„PtClj. Needles (Hofmann, B. 3, 267 ,'
18, 3223").
Normal-iso Cyanuric acids (hypothetical).
ALKyii DEBIVATIVES.
Phenyliso-dinormal cyanuric a'cid,
Monophev/ylisocy anuria acid
COH
PhN,/^,N
CgHjNsOs i.e. . Formed by the
OCL JCOH
N
action of cone. HCl on Bathke's triphenyl-am-
meline. Flat needles. [285°-289°]. V. sol. hot,
V. si. sol. cold water (Bathke, B. 20, 1070 ; 21,
868).
Diphenyliso -normal cyanuric acid
COH
PhN/^,N
CjjHiiNsOa or . Prepared by heat-
OClv ico
NPh
ing M-triphenyl-melamine with cone. HCl at
150°. The phenylamido group is thus replaced
CYANIC, DIOYANIC, AND TRIOYANIC AOIDS.
by hydroxyl and the imido- groups by oxygen.
Needles or laminsa. [261°]. Insol. water, sol.
alcohol, V. si. sol. ether. With cone. HCl at
280° it breaks down into COj, NHj, and aniline.
I CjsHijAgNsOs crystalline pp. formed on addition
of AgNOj to a solution of the sodium salt (Hof-
mann, B. 18, 3230).
Kormal-iso ammelines (hypothetical).
Aleyii debivatives.
Phenylnbrmalamido - diphenyliso-
amido-cy anuria acid. Priphewyl a/mmeline
COH
PhN/'^^.N
OjiHjjNjO i.e. . Obtained
PhNCL JONHPh
N
by treatment of ethyltriphenylthioammeline hy-
drobromide, a compound prepared by the action
of ethyl bromide on triphenyl-thioammeline, with
alcoholic potash. Colourless laminae. [275°].
V. si. sol. alcohol, si. sol. chloroform. Cone.
HCl at 160' converts it into phenyliso-dinormal-
oyanuric acid (Eathke, B. 20, 1069; 21, 868).
Phenylnormalamido-phenyliso-
amido'phenylisocyanurate. Tri/phenyl-
CNHPh
PhN/^|N
ommeKweCjiHjjNjOi.e. . Pre-
OCt JCNH
NPh
pared by acting on Hofmann's u-triphenylmela-
mine with HCl at 100°. Crystals. [265°].
Heated further with HCl it is converted into di-
phenyl iso-normal-oyanuric acid (Hofmann, B.
18, 8229).
Normal-iso melamiues (hypothetical).
AliKYI. DERIVATIVES.
Phenylnormal - diphenyliso - mela -
mine. u-Triphenyl-melwmvne
CNH^
PhN /"**|N
C„H,sN, i.e. I
PhNC I. JCNH
NPh
Formation. — By the desulphurisation of
monophenylthiourea by HgO in alcoholic solution.
Properties. — Needles. [217°]. Insol. water,
b1. sol. ether, sol. chloroform, sol. dilute acids
and reprecipitated by alkalis.
Reactions. — By the action of HCl it is con-
verted at 100° into Hofmann's isonormal tri-
phenylammeline,andat 150°-200° into diphenyl-
isonormal cyanuric acid (Hofmann, B. 18, 3226),
Diphenyl -melamine C.sHuNj. A by-
product in the preparation of Eathke's triphenyl-
melamine. Formed together with anihue when
in that process the further action of alcoholic
ammonia causes the isonormal triphenylmela-
mine to change into the normal isomeride. It
may possibly prove to be a normal compound.
[202°-204°]. (B'HCl)jPtCl4 (Bathke, B. 21, 872).
Triphenylmelamine. (?) Diphenylnor-
mal phenyUsomela/mine
CNHj
PhN |/'*^,N
C„H„N^i.e. (?)
PhNC
N
CNHPh
CNH
PhN NH
PhNC CNPh
\/
NH
Formation. — ^By the action oJ alcoholic am^
monia on ethyl triphenyl-thio-ammeline hydro-
bromide, the reaction being : CjNjHPhjSEt -i- NH,
= CjNjHPh jNHj -I- EtSH. Diphenylammeline,
aniline, and normal triphenylmelamine are
formed in the same reaction (Bathke, B. 20, 1071;
21, 868).
Properties. — Prisms. [221°]. Sol. hot al-
cohol. Base. The hydrochloride and sulphate
are soluble, the nitrate is si. sol. water.
Reactions.— 1. Heated with alcohol and am-
monia it changes to normal triphenylmelamine.
2. Heated with cone, HCl at 125° it is converted
into Bathke's triphenylammeline, and at higher
temperatures into phenyl iso-dinormal-cyanurio
acid.
Other isomerides of cyanuric acid.
The members of this division of trimolecular
compounds are so little known that it would be
premature to attempt to assign to them struc-
tural formulse.
The (o) and (/3) Cyamiric acids (Herzig, B. 12,
170) are not included, recent investigation having
shown that when purified they are in all respects
identical with each other and with ordinary
cyanuric acid (Senier, O. J. 49, 693 a. 743),
Gyamelide (C'SOB.)^.
Formation. — 1. Liquid cyanic acid poly-
merises slowly at 0°, and instantly at higher
temperatures with evolution of heat forming
cyamehde. This reaction takes place when cya-
nates are treated with anhydrous acids (Liebig
a. Wohlei:, P. 15, 661; 20, 384; Troost a.Haute-
feuille, J. 1869, 99; Weltzien, A. 132, 222).— 2,
Is formed, together with cyanuric acid, by the
action of (CN)3Cl3 on water (Liebig, P. 15, 563).
Cf. Mulder (R. 6, 199).
FroperUes. — Tasteless.inodorous solid. Insol.
water, alcohol, ether, and dilute acid, sol.
KHOAq or NHjHOAq, cyanurate being formed
on evaporation. Heated alone it evolves cyanic
acid. Heated with HjSOj it is converted into
ordinary cyanuric acid. Cyamelide may possibly
prove to be free isocyanuric acid (Klason, /. pr.
[2] 33, 129).
Oyanilic acidG^^O^^i'B.fi,
This compound is so nearly related to cyan-
uric acid that when further studied it may prove
to be identical with it. Mellon is heated to-
gether with HNO,, and the product extracted
with water. Becrystallised from water it con-
sists of pearly laminss, or from HNO, of four-
sided prisms. By solution in H„SO, it is con-
verted into cyanuric acid, which faUs on the ad-
dition of water. It has the same proportion of
water of crystallisation, and the crystals effloresce
just in the same manner as cyanuric acid. With
AgNOj it forms a salt AgHjC2H,02, correspond-
ing to a similar cyanurate. its solubility in
water was, however, found to be greater than
that of cyanuric acid, and its crystalline form to
be difierent (Liebig, A. 10. 34).
CYANIDES.
827
Pulminuric aeid HOjHoN.O. m.
C:NOH
/\
O O
HN:C-
-t
:NH.
Formation. — By heating fulminating mer-
cury (not fulminating silver) with an aqueous
solution of alkaline chlorides or iodides (Liebig,
A. 95, 282 ; Sohisohkow, A. 97, 53 ; 101, 213),
or with water (Bhrenberg, J. pr. [2] 32, 98), or
in tubes with alooholio ammonia (Steiuer, B. 9,
781). The potassium or ammonium salt thus
obtained is converted into the lead or silver com-
pound which suspended in water ip treated with
HgS. The aqueous solution which results depo-
sits the free f ulminuric acid as an indistinct crys-
talline powder on spontaneous evaporation.
PropertAes. — Small anhydrous colourless
prisms, from alcohol. Sol. water, alcohol, and
ether. Solutions have an acid reaction, and
give a characteristic ,deep blue pp. with am-
mouio copper sulphate.
Reactions. — 1. Heated it explodes at 145°. —
2. Heated with dilute acids or alkalis NH,,
CO2 and HAO, are formed (Steiner, B. 5, 381).
3. The silver salt heated with cone. HCl sepa-
rates one of its N atoms as NHjOH (Ehrenberg).
4. Two atoms of N are evolved as ammonia by
heating with soda lime. — 5. With chloride of
lime it forms OpSTOJCla.— 6. With H^SO, nitro-
acetonitrile is formed, and in presence of HNO3
tri-nitroacetonitrile.
Halogen derivatives. — Chlorofulminuric
aoid CaHjClNaOj. Salts AgCaHClNjOj. —
AgoCjClNjOj. Bromof ulminuric acid
CaH^BrNsOa (Ehrenberg, J.pr. [2] 32, 111).
Metallic derivaUves. — NH4A' : prisms, sol.
water, insol. alcohol (Liebig).
(NH,A')j(Hg2SCN), [150°] (Ehrenberg, J. pr.
[2] 30, 64). — NH,A',HgSCN [161°]. —
(NH,A'),2Hg(S0N), [156°]. — KA' : prisms, sol.
water, insol. alcohol. Explodes at 225° (Schisch-
kow). — MgA'j,5aq:needles(Steiner). — BaA'22aq:
prisms (Liebig). — ZnA'2,5aq: needles (Steiner). —
HgA'j! crystalline powder (Steiner). — HgA'^jHgO
(Steiner). — PbA'j, 2aq : needles (Steiner). —
CuA'2,' 4aq : emerald green rhombs. CuA'2,4KH3 :
characteristic deep blue pp. Prisms. Insol. water,
, V. si. sol. ammonia. — AgA' (Liebig).
Alhyl derivatives. — An unstable oil CaHnNOj
is obtained by passing HCl into a mixture of
potassium fulminurate and alcohol. It combines
with NH, and amines— C5H„N05,NH, [152°].
C„H„N05,NH2Ph : needles. [81°] (Ehrenberg,
J.pr. [2] 32, 106 ; Schischkow, A. 97, 61).
Isofulminuric aeid CgH^NsO,.
Formation. — Together with other products
by the action of aqueous ammonia on an ethereal
solution of fulminic acid obtained by leading
HCl at 0° into a mixture of fulminating mercury
and ether. The aqueous solution on sponta-
neous evaporation deposits fulminuramide, and
from the solution by further treatment isoful-
minuric acid is obtained.
Properties. — Pulverulent. Chars without
melting when heated. V. sol. water and alcohol.
Gives no pp. with ammonio-cupric sulphate.
Salts.— NHjA'.—BaAV— AgA' : amorphous
pp., insol. cold water (Ehrenberg, cA^. [2] 30,48).
FuZminMramiia.— C3H2NH2N3O2 : long mi-
nute needles.— (B'),Cu02NH3 : light blue pp.—
B'j,AgN03 : needles (Ehrenberg).
Metaf ulminuric acid C3H3N303,3HjO.
Formation.— Ey the action of dilute HjSO,
on sodium fulminate. The product is extracted
vrith ether which evaporated in a current of air
below 30° deposits the metafulminurio acid in
needles. The solution contains isooyanilic acid
which is formed in the same reaction.
Properties. — [81°]. Anhydrous acid explodes
at 106°. Tribasio acid. V. sol. alcohol and
benzene, less so in water and ether. Decomposes
gradually with evolution of HCN.
Reactions. — 1. KHO or water at 130° breaks
it down into CO^ and NHj. — 2. Heated with
cone. HCl, NHjOH is formed.— 3. Gradually
changes into (3)-isofulminuric acid on standing.
Salt s.— NH^HjA'".- (NH4)jHA"'.—
H3A"'(NH2Me)2 : yellow needles. — K5A'". —
PbHA"'aq: lemon-yellow insol. pp. — Ag2HA"'aq.
On adding AgN03 to the aqueous solution the
sUver salt falls as a characteristic cinnabar red,
at first gelatinous, precipitate. Explodes when
dry at 86° (Scholvien, J. pr. [2] 32, 464).
{$)-Isofulminuric acid C3H3K30g2|H20.
Metaf ulminuric acid changes gradually on stand-
ing, being converted into this metaineric modifi-
cation. Needles, from water. [188°]. [196°
anhydrous, with decomposition]. Sol. water and
alcohol.
Salts.— NH,A'.—BaA'j.— AgA' insol. pp.,
crystallises in needles (Scholvien, J. pr. [2] 32,
474).
Isooyanilic acid (CNOH)^:.
Formation. — To the ethereal mother-liquor
from which metafulminuric acid has be^sn sepa-
rated, water is added and the evaporation con-
tinued, when isooyanilic acid comes out in needles.
It may be reorystallised from water.
Properties. — Does not explode on heating.
Sol. hot water, alcohol, and ether. Gives no pp. in
aqueous-solution on adding AgNO, or Pb(C2H.,Oj)2
or CuSO,. Heated vrith cone. KHO the solution
is coloured deep red violet, and on the addition
of alcohol a salt of the same colour is ppd. This
red violet compound in aqueous solution gives
vfith Pb(C2H302)a a bright red violet explosive
lead salt PbjCsH^NiOj (Scholvien, J. pr. [2] 32,
476). A. S.
CYANIDES (including sulphootanides and
SEiiENOcxANiDEs). Binary compounds of cyano-
gen. In this article only metallic cyanides are
described. Alkyl cyanides are described as
nitriles ; e.g. for description of CH3.CN v. Aoeto-
NIIBILE.
Cyanogen forms binary compounds with
above 30 metals ; most of these cyanides form
several, some form very many, double cyanides ;
some of the double cyanides are best regarded
as metallic derivatives of acids composed of H
combined with metals and the atomic group CN
{v. post). Cyanogen also forms binary com-
pounds vrith the non-metals Br, CI, I, F, Se, and
S. Of these compounds, CNBr, CNCl, and CNI
are described under Cyanic Acin (p. 312, 313) ; the
others are described under Ctasoqen as Cyano-
gen phospMde, &o.
The simple cyanides may be regarded as de-
rived from cyanhydric acid NCH, by replacing
H by metals; the general formuln expressing
828
CTANIDES.
their compositions are NC.M, (NC),M",
(NC)3M.>", &o.
Alkali cyanides are formed by the direct
union of cyanogen with alkali metals, by reac-
tions between HCNAq and alkali oxides, by
strongly heating nitrogenous organic matter
with alkali carbonate. Many other cyanides
are obtainable from alkali cyanides by double
decomposition.
Alkali and alkaline earth cyanides are soluble
in water ; the other simple cyanides, with the
exception of HgCy^, are insoluble in water, but
may dissolve in solutions of alkali cyanides with
production of double cyanides.
Alkali cyanides are very easily decomposed
with evolution of HON, passage of a current of
air free from CO^ sufBces to effect this change.
Some of the insoluble cyanides are readily de-
composed by dilute acids, e.g. PbCy^ and ZnCyj;
others are very stable towards acids, e.g. cyanides
of Au, Hg, and Ag. Hot cone. H^SO^ decomposes
all cyanides, some easily, others slowly ; the pro-
ducts are sulphate and HON or CO and NHj.
Alkali cyanides are unchanged by heat alone ;
cyanides of the heavy metals are decomposed by
heat, generally forming metal and Cy , sometimes
N is evolved and C deposited on the metal, or a
carbide of the metal is formed. Water decom-
poses cyanides at high temperatures (250°-
300°), giving {NH4)jC0a and HCOj.NH, with
metallic oxide, or sometimes metal and
(NHJ2CO3. Chlorine decomposes most cyanides
generally forming metallic chloride and CyCl.
Boiling with water and excess of HgO decom-
poses all cyanides, except platino-cyanides, with
formation of HgCy, and oxide of the metal of
the cyanide.
Many cyanides form double salts, generally
with haloid metallic compounds.
Very many cyanides combine with other cya-
nides to form double cyanides. These double
cyanides are divisible into two classes, according
as they are, or are not, decomposed by solutions
of mineral acids with evolution of HON. Silver
potassium cyanide, AgKCy^, for instance, reacts
with dilute HNO^Aq to givei AgCy, KNO,, and
HON, and with dilute HClAq it gives AgCl, EOl,
and HON ; potassium ferrocyanide, K^PeCyj, on
the other hand, reacts with HClAq to give ferf 0-
cyanic acid HjFeCyj. The members of the second
class of double cyahides are generally regarded
as metallic derivatives of acids which are them-
Eclves composed of H united with a metal and
the radicle cyanogen, the metal and cyanogen
together forming the negative radicle of the acid ;
thus, ferrocyamc acid HjFeOyj (better called
ferrocyanhydric acid) forms a, series of well-
marked stable metallic derivatives which are ob-
tainable from the acid by reactions similar to
those whereby salts are produced from HNO3,
H,SO.„ HjPO^, &c.
Mangdnocyanic acid (ormanganooyanhydric
acid) HjMnCyg, cohalUcyamc acid (or cobalti-
cyanhydrio acid) HjCoCye, aimcyanic acid (or
auridyanhydric acid) HAuCy,, platincyanic acid
(or platincyanhydrio acid) H^tCyj, and some
other acids the negative radicles of which are
composed of metal combined with cyanogen,
have been isolated. Some of these metallic-
cyanogen acids form derivatives in which part
«f the negative radicle is replaced by a negative
group, e.g. H^.FeCyjNO. A few metallie-halogeti
acids are known, more or less analogous to the
metallic-cyanogen acids, e.g. H.AuClj, Ho.HgCl,,
Hj.PtCl,; but the metallic-cyanogen acids are
more numerous, and form many more stable
salts, than the metallic-halogen acids. The nega-
tive character of the radicle CN is well seen in
the production of the nui^erous ferrooyanidea,
manganocyanides, platinocyanides, &a. The affi-
nities of a few metallic-cyanogen acids have been
determined {v., e.g., p. 333); they seem to be
very strong acids ; on the other hand cyanhydrio
acid N.CH is an extremely weak acid (v. Cvan-
HYDKio ACID, p. 301) ; but sulphocyanic acid,
N.CSH, has a very large affinity (v. Sulpho-
cyanic ACID, p. 303).
It would be possible, and for some reasons
advantageous, to divide the metallic cyanides
into two main classes ; class I. would include
those cyanides which are decomposed by dilute
mineral acids with evolution of HCN, and are
therefore to be regarded as derivatives of HCN,
and also those which although not yielding HCN
by reactions with dUute acids must nevertheless,
on account of their composition and modes of
preparation, be regarded as derived from HCN
{e.g. HgCyj) ; class 11. would include those cyan-
ides which yield metallic-cyanogen acids or are
derived from such acids. The first class would
contain all the simple, and many double, cyan-
ides. Some double cyanides would hardly fall
into either class ; HgCy,^.2KCy for instance re-
acts with solutions of salts of Zn, Cd, Pb, &o., to
form salts of the general form HgCy^-MCyj
(M = 2;n, Pb, Cd, &c.), hence HgCy2.2KCy seems ■
to be the K salt of the hypothetical aoidH^HgCy,.
The metallic-cyanogen acids which have been
isolated are H4CrCyii (salts of HjCrCyj are also
known), H^CoCye, HjCoCy., HAuCy^, H,IrCye,
H,FeCye, HsFeOye, H^MnCy^, H.OsCy,, salts of
H^PtCy^, ^[jPtCyjCla (or Br^), salts of HaEhCyj,
HjEuCyj ; salts of the hypothetical S^iCy^ are
also known, but they react more like double
cyanides. No nickelo- or nickeli-cyanides are
known corresponding to MjCoCyj and M^CoCy^ ;
Ni double cyanides are easily decomposed by
dilute acids with evolution of HCy, and are
therefore to be classed with the leas stable double
cyanides.
Those cyanides, simple or double, which are
readily decomposed by dilute acids with form-
ation of HCy are poisonous ; the stable salts
of metallic-cyanogen acids, e.g. KiFeCy,, are not
poisonous.
In this article the cyanides will be described
in alphabetical order; the descriptions of the
various compounds will show to which of the
two main classes of cyanides they belong.
This article also includes descriptions of the
sulphocyanides and the selenocyamdes. '
SbIiEnocyanides. These compounds are de-
rived from selenocyanh/ydmc acid HSeCN. The
aoid itself is only known in aqueous solution ; it
is very easily decomposed to HCN and Se ; the
K salt is obtained by dissolving Se in KCNAq.
(For individual selen'ocyanides, v. p. 348).
Sulphocyanides. Metallic derivaUves of
sulphocya/nic (or thiooyanic) acid. Sulphocyanic
acid almost certainly has the constitutionHS.GN ;
while the replaceable H of cyanic acid is pro-
bably in direct union with N. The metallic snl-
CYANIDES,
329
pliocyanides are not strictly comparable with the
metallic oyanatos ; for this reason it seems better
to use the name sulphocyanides rather than sul-
pha- (or thio-) cyanates. Cyanhydrie acid is an
extremely weak acid, but the affinity of sulpho-
oyanio acid is nearly equal to that of hydrochloric
{v. Ostwald's Le}trbuch der allgemeinen Chemie,
2, 849).
The general formula expressing the compo-
sition of sulphocyanides are NCS.M, (NCS)aM",
(NCS)sM^"^ &c. These salts are sometimes called
rhodanides, a name first given to them by Ber-
zelius because of the red colour which they give
with ferric salts (^6Sov).
Sulphooyamde of K is formed by direct ad-
dition of S to KCN ; Na.SCN is produced by
passing CSj over heated NaNHj (NaNH^-fCSa
= NCS.Na-(-H2S); NH^.SCN may be obtained
by adding (NHJ^Sj to NCHAq, or by heating CS^
with alcohoUc NH^ (CS2 + 4NH3
= NCS.NH^-^(NHJ2S); the sulphocyanides of
the heavy metals are usually formed by double
decomposition from the alkali sulphocyanides.
Most sulphocyanides are soluble in water;
the salts of Cu, Pb, Hg, and Ag are insoluble.
Dry alkali sulphocyanides may be heated in ab-
sence of air without change ; in presence of air
SO2 is evolved and sulphate and oyanate are
produced. Sulphocyanides of the heavy metals
are decomposed by heat, generally giving S, CSj,
metallic sulphide, and mellon {q. v. p.. 323),
on strongly heating the mellon yields Cy and N.
The insoluble sulphocyanides are completely de-
composed by HjS. Sulphocyanides of P and Si,
P(SCy)3, and Si(S0y)4 respectively, are described
under Phosphoeus and Silicon.
Many double sulphocyanides are known ;
most of these react as double salts, but some as
metallic derivatives of acids composed of H
united with a negative radicle which is itself
composed of metal and sulphocyanogen (SON).
For instance chromsuVphoeyania (or chrom-
Bulphoeyanhydrio) acid H3Cr(SCN)3 is known in
aqueous solution, and many salts of this acid
have been isolated. The acid H2Pt(SCN)4 is
also known in aqueous solution. (For individual
sulphocyanides v. p. 348 et seq-)
Analysis of cyanides and suVphocyamdes.
I. Alkali cyanides are estimated by. ppn.
with AgNOjAq, or by Liebig's volumetric method
{v. Cyanhydbic acid).
II. Many cyanides, including the double
compounds of NCK with OuCyj, NiOyj, and
ZnCy^, may be estimated by heating for some
time with AgNOj, then adding HNOjAq, and
heating again ; the AgCN formed is collected
and weighed. According to Weith (Fr. 9, 879)
KjFeOys, KgOoCys, and Prussian blue, may be
wholly decomposed by heating for several hours
in a cfosed tube with ammoniacal AgNO,; oxide
of the heavy metal is ppd. while NH^Cy goes
into solution ; filtering and adding HNOaAq ppts.
AgCy.
III. Mercuric cyanide may be analysed by
heating with ammoniacal Zn(N03)g, whereby
ZnCy^ is formed (v. Bose a. Finkener, Fr. 1, 288).
IV. Many cyanides may be analysed by long
boiling with HgO and water, filtering and deter-
mining Oy by boiling with ammoniacal Zn(NOj)j.
V. The metal in most cyanides may be' deter-
mined by continued heating vrith cone. HjSO,,
vapourising excess of acid, and estimating the
metal in the remaining sulphate by one of the
usual methods.
VI. Soluble sulphocyanides may be analysed
volumetrically by means of standard Ag solution
in the same way as chlorides (Volhard, Fr. 1874
242).
CYANIDES.
Aluminium cyanide. Not isolated. A double
Al-Fe cyanide is described by Tissier (J. Ph. 35,
88) as obtained by boiling K^FeCyjAq with excess
of an acid solution of a salt of Al ; the compo-
sition of the pp. is approximatelySFeCy^.SAljClij.
Ammonium cyanide NH4.CN. Formed by
passing NH3 over red-hot coal (Kuhlman, A.
38, 62 ; Clouet, A. Ch. 11, 30 ; Langlois, A. 38,
64) ; also by passing CO and NH5 over heated Pt
black (K., Z.C.). Prepared by heating together
3 parts dry K^FeCy^ with 2 parts NH^Cl at 100"
and leading the vapour into a well-cooled re-
ceiver (Bineau, A. Ch. 70, 263). Crystallises in
cubes ; volatilises at c. 36° with dissociation
into HON + NHj (Bineau, I.e. ; Deville a. Troost,
C. B. 56, 891). Vapour is inflammable in the
air. Very poisonous. Easily decomposes in the
air to a brownish mass. Easily soluble in water
and alcohol. Berthelot (C. B. 91, 82) gives the
following thermal data:— [C, N^ H<] = 3,200
(formation of solid NH ,.CN) ; [N,<3N, H*] = 40,500
(solid NH4.CN); [HCN, NH»] = 20,500 (solid
NH4.ON from gaseous materials) ; [HCNAq,
NH»Aq] = 1,300 ; [NH'.CN, Aq] = -4,400.
Barium cyanide Ba(CN)2. Prepared by
heating BajFe(0N)5, and extracting, with water
(Sohulz, J.pr. 68, 257). The hydrate Ba(CN)2.H20
may be prepared by bringing HCN gas into con-
tact with hydrated BaO (for details v. Joannis,
A. Oh. [5] 27, 489). It is also formed when air
is passed over a red-hot mixture of BaO and C
(Margueritte a. Sourdeval, O. B. 50, 1100). Crys
talline ; quickly absorbs CO2 from air ; si. s61. in
water; heated to 300° in steam evolves NH,.
When HCN is passed into BaO in CH3.OH, a
crystalline powder is formed of the composition
Ba.CN.OCH3 + CH3.OH, and when this is strongly
heated barium oxycyanide BaCy2.BaO is formed
(Dreohsel a. Kriiger, /. pr. [2] 21, 77). Joannis
(I.e.) gives the following thermal data : —
[BaOAq, 2HCNAq] = 6,340 ; [BaOy«, Aq] = 1,780.
Weselsky (Z. [2] 7,61) prepares various double
cyanides containing barium cyanide by
passing HCy gas into a mixture of BaCO, with
a salt of the other metal ; e.g. using PtCljAq
and BaCOj, the double cyanide BaCyj.PtCy^ is
obtained. The following double cyanides were
produced : [M = BaOyJ 2M.3CdCy2.10HjO ;
M.CujCyj.H,0; M.NiCy2.3H20 ; M.PdCy2.4HjO ;
M.2AgCy.H20 ; M.ZnCy2.2HjO.
Cadmium cyanide CdCy,. Obtained by dis-
solving freshly ppd. CdO.MjO in HCyAq, filter-
ing from oxycyanide, and crystallising (Bam-
melsberg, P. 38, 364). Small white crystals;
unchanged in air; decomposes above 200° in
air. S. c. 1-7 in cold water. H.F. [Cd, Cy', Aq]
= 33,960; [CdO^ff, 2HCyAq] = 13,700 {Th. 3,
474).
Cadmium oxycyanide. By digesting CdO.M^O
in HCyAq : the residue insol. in the acid is said
to have the composition CdCyg.CdO.SHiO
(Joannis, O. B. 93, 271).
Double cyanides containing cad.
880
CYANIDES.
mium cyanide. The salt CdCy2.2KCy is pro-
duced by adding ECyAq'to solution of Cd ace-
tate, evaporating, and crystallising. White oc-
tahedra; v. sol. water; unchanged in air at
c. 200°. H.F, [Cd, Cy2, 2KCyAq] = 44,750 ;
[OdCy^'Aq, 2KCyAq] = 10,790 (Th. 3, 474). Solu-
tion gives pps. with various metallic salts, e.g.
with solution of salts of Ca, Ba, Cu, Mn, Sr, Zn
(Rammelsberg, P. 38, 364). The double salt
20dCy2.Cu2Cy2 is said to be formed by dissolving
CdOjHj along with CuCOj in HCyAq, and evapo-
rating (Schuler, A. 87, 48). By dissolving
CdOjHj and CuOjHj in HCyAq and allowing
the liquid to evaporate in the air, the salt
2CdOy2.CuCyjis obtained (Schuler, l.c.). Various
other double salts are described by Schuler {I.e.).
, Calcium cyanide Ca(CN)2. By heating
CajFeCyj (Schulz, J. pr. 68, 257). A solution of
CaOyj is obtained by adding HCNAq to OaCOg ;
the solution soon decomposes ; if cone., crystals
of an oxycyanide separate, 8CaO.CaCy2,15H20
(Joannis, C. B. 92, 1338, 1417). H.P.
[CaOAq,2HCyAq] = 6,440 ; [Ca,OySAq] = 115,340
(Joannis, A. Ch. [5] 27, 489).
Cerium cyanide, not isolated. KCyAq added
to salts of Ce ppts. a white solid which at once
decomposes with evolution of HON, leaving Ce
oxide (Beringer, A. 42, 139).
Chromium cyanides. Simple cyanides have
not been isolated ; the pps. obtained by adding
KCyAq to CrCljAq and GrCljAq soon decom-
pose.
Potassium chromocyanide KfirCjg.
CrCOa (obtained by adding KjCOjAq to CrCljAq
saturated with CO,, air being excluded) is mixed
with KCyAq until the solid has partially dis-
solved, the yellow liquid is filtered and evapo-
rated (Moissan, A. Ch. [6] 4, 136). Long yellow
needles ; S.G. 1-71 ; S. (20°) 3233 ; insol. alco-
hol, ether, benzene, and chloroform. Unchanged
in air at ordinary temperature. Non-poisonous.
Aqueous solution partially decomposed on boil-
ing. Oxidising agents form chromicyanide,
KaCrCy,, ; with PeSOjAq gives red colouration,
•i^a part of the salt in a solution may be thus
detected (Moissan, l.c.). Gives pps. with metallic
salts {v. also Ohristensen, J.pr. [2] 31, 163).
Potassium chromicyanide K^CrCy,.
Prepared by oxidising KfirCj^; or by heating
KCyAq with Cr alum, or with Cr-K chloride,
or by dissolving freshly ppd. CrjOgHj in acetic
acid, evaporating to dryness, dissolving in water,
and adding the liquid to hot KCyAq (Kaiser, A.
Sv^lbd. 8, 163 ; Stridsberg, J. 1864. 304 ; Des-
camps, A. Ch. [5] 24, 178 ; Christensen, J. pr.
[2] 31, 163). Yellow monoolinic crystals ; sol.
water, insol. absolute alcohol ; easily decomposed
by dilute acids. Gives pps. with most metallic
salts (v. Christensen, J. jpr. [2] 23, 52).
Ammonium chromicyanide
(NH4)sCrCy„ (Kaiser, A. Sujaplbd. 3, 163).
Chromocyanhydric acidB.fixCjf{chro-
mocyanic acid). Small white crystals, obtained
by decomposing the K salt by dilute HjSOiAq ;
sol. water, solution rapidly decomposes in air
(Moissan, A. Ch. [6] 4, 136).
According to Descamps {A. Ch. [5] 24, 178)
salts analogous to nitroprussides (q. v. p. 340)
are produced by passing NO into chromooyan-
ides.
Cobalt , cyanides. One simple cyanide,
CoCyj, is known; two series of salts derived
from cobalto-oyanhydric acid and cobalti-oyan-
hydric acid have been prepared ; the cobalto-
oyanides are very unstable, while the oobalti-
oyanides are stably salts.
Cobaltous cyanide Co(CN)j. Buff.oo-
loured pp. by adding KCy to Co salts, or HCNAq
to Co acetate (Wohler, Oehlen's Joum. 6, 234).
The pp. contains 2H2O which it does not lose
till c. 280° (Zwenger, A. 62, 157). Dissolves in
KCyAq to form KjOoOyj, which quickly changes
to KjCoCyj.
Cohaltocyanhydric acid H,CoCy, (Co-
baltocyanic acid). Very unstable pp. obtained
by decomposing Pb cobaltocyanide by HjS, fil-
tering, and adding alcohol (Descamps, Bl. [21
31,49).,
Potassium cobaltocyanide K^CoCy^
Amethyst-coloured, deliquescent needles; ob-
tained by adding alcohql to a cold solution of
CoCy, in a slight exoesa of cone. KCyAq. Very
unstable: easily changes to KjCoCyg. Insol.
alcohol and ether. Solution gives pps. with many
metallic salts ; these are probably cobaltocyan-
ides (Descamps, l.c.). According to Descamps
(A. Ch. [5] 24, 178) salts analogous to the nitro
prussides (g. v. p. 340) are obtained by passing
NO into cobaltocyanides.
Cobalticyanhydric acid 'SfioOjg.xH.jO
(Cobalticyamc acid). Obtained by evaporating
the K salt in solution with cone. HjSO,, and ex-
tracting the residue with alcohol (Zwenger, A.
62, 157) ; or by decomposing the Cu salt by
HjS. Colourless needles ; v. e. sol. in water
and alcohol ; insol. dry ether. Very acid taste.
Not decomposed by heating with cone. HClAq
or HNOjAq, but slowly by hot cone. H^SO,,
giving sulphates of NH, and Co, and evolving
SO2, CO, and COj.
Potassium cobalticyanide KjCoCy^
Obtained by dissolving CoCy^ or COjO, in KCyAq,
evaporating, and crystallising (Zwenger, A. 62,
157). KCy and K2CO3 may he removed by de-
composing by acetic acid and ppg. by alcohoL
Slightly yellow, transparent, rhombic crystals ;
isomorphou? with K.,FeCyu. E. sol. water, insol.
alcohol. S.G. 1-906. Decomposed by strong
acids with separation of cobalticyanhydric acid
HaCoCyg ; not decomposed at ordinary tempera-
tures by HClAq or HNOjAq. Eeduced by Ba-
amalgam to KfioOy,.
Cobalticyanides.t Besides the K saltthe
following have been isolated (X = CoCy8) : —
(NHJaX-H^O (Zwenger, A. 62, 157).
[N(CH,)J,X (Claus a. Merck, B. 16, 2737).
Ba.,2X.22H20 (Z., l.c.) ; BaNH^.X.H^O ;
Bak.X.llH20 ; BaLi.X.15H20 ; Ba32X.Ba02Hj;
Ba32X.BaCl2.16H20 (Weselsky, B. 2, 588).
CaNH4.X.10H2O ; 0aK.X.9Hj0 (W.,Z.c.).
CrX-SNEj-liHaO (Christensen, J. pr. [2] 23,
52) ; CrX.eNH, (Braun, A. 125, 153, 197).
C032X.I4H2O (Z., l.c.) ; C0.X.5NH3.IJH2O (Gibbs
a. Genth, A. 104, 150, 295 ; Braun, Z.c.) ;
C0X.6NH3.IH2O (G. a. G.,l.c.). CU32X.7H2O;
Cua2X.4NH3.10H2O (Z., I.e.). Pb32X.7H20 (Z.,
l.c.) ; Pb32X.6PbO.3H2O (Z., l.e.) ;
Pb32X.3Pb02H2.11H20 ; Pb32X.Pb(N03)2.12H20-,
PbKX.3H20; Pb(NH,)X.3H20 (Schuler, W.A.B.
1879 [n]. 302) ; Ni32X.12H20 ;
Ni32X.4H2O.7H2O (Z., Ix.). Na3X.2H„0(Z.,Z.c.);
CYANIDES.
831
Na(NH4).X (Weselsky, B. 2, 588). Ag,.X ;
Ag3.X NH,.iajO (Z., l.e.). Srs2X.20H2O ;
Sr(NHJ.X.10HjO ; SrKX.gnjO (W., l.c.). TI3X
(Fron-Miiller, B. 11, 91). YX.2H.0 (Clceve a.
Hoeglund, Bl. [2] 18, 197).
A fairly general method of preparing oobalti-
syanides consists in first preparing the barium
salt Ba,(CoGye)2.a;E20, decomposing a solution
of this by the sulphates of other metals, filter-
ing, and crystallising ; the Ba salt is most easily
produced by passing HCy gas into a mixture of
C0SO4 and BaCO,, filtering, and crystallising
(Weselsky, W. A. B. 60, 261). Cobalticyanides
containing two metals, e.g. (NHJNa.CoCyj,
BaE.CoGy3, are obtained by mixing solutions
of the cobalticyanides, evaporating, and crystal-
lising; these salts generally crystallise well
(Weselsky, l.c.). Cobaltous cobalticyanide
Cos{CoCy5)2.14H20 corresponds in composition
to ferrous ferricyanide Fes(FeCyj)2 (g;. «. p. 338)
or TwmbulVa blue ; it is a pale red amorphous
solid ; obtained either by adding KaCoCyjAq to
CoSOjAq and washing thoroughly with water, or
by heating HjCoCyj with cone. H^SOj, and add-
ing water before decomposition is complete.
This salt loses part of its water at 100°, and
turns blue. It is insol. water ; decomposed by
EOHAq with separation of CoO.aiHjO. Dry
Co3(CoCy8)2is blue ; it combines with water with
production of much heat (Zwengler, A. 62, 172).
Copper cyanides. , Three cyanides of On are
known, cuprous cyanide, cupric cyanide, and
cupro-oupric cyanide ; the first-named is the
most stable ; double compounds of each, espe-
cially with NH3, have been isolated.
Cuprous cyanide CujCyj. Formed by
adding KCyAq to Cu^Cl^ dissolved in HClAq, or
to CuSO^Aq reduced' by SOj ; also by the action
of HCNAq on freshly ppd. Cu(0H)2 (Eammels-
berg, P. 42, 131; 85, 145). Prepared, as small
lustrous monoolinio crystals, by decomposing
Cu2Cy2.PbCy2 suspended in water by H^S, filter-
ing, and allowing the filtrate (which probably
contains HjCu^CyJ to evaporate (Dauber, A. 74,
206; Wohler,4.78, 370) ; the salt Cu2Cy2.PbCy2
is obtained by adding a Pb salt to the solution of
COjCyj.ECy, formed by dissolving Cu(OH)j in
KCyAq. Insol. water ; sol. HClAq, NHjAq, and
solutions of NHj salts (Pagensteoher, N. J. T. [3]
1, 451) ; ppd. by HjO from solution in HClAq ;
decomposed by cone. HNOjAq, not by dilute
HjSOjAq. Dissolves in alkali cyanides to form
double salts, from which it is ppd. by HClAq.
Double cyanides containing cuprous
cyanide (sometimes caUei ouprosocyanides) : —
1. With NH^CN, forming monoolinic prisms,
insol. HjO— Cu2Cyj.NH4Cy (Lallemand, O. B.
60, 1142); Guj,Cy2.2NHiCy (Dufau, G. R.
36, 1099).— 2. With KCN— Cn2Cyj.KCN.H2O
(SchiiEE a. Becchi, A. 138, 24) ; Cu2Cy2.2K0N ;
CujCyj-eXCN (Eammelsberg, P. 42, 114 ; 106,
491) ; 3Cu2Cy2.4KCN (Eammelsberg, P. 73,117).
The salt CujCys.KCN.HjO is insol. in H^O, the
others are soluble ; the soluble salts give pps.
with salts of the heavy metals ; e.g. with salts
of Fe, Pb, Mn. The pps. thus obtained may be
regarded as cuprosocyanides of iron, &o. Many
of the double cyanides containing Oufiji are
sometimes called owprosocyamdes, and are re-
garded as salts of the hypothetical cuprosocyan-
hydrio acid HjCujCy^: e.g. Cafijj.2NB.fiy is
often formulated as (NHJjCUjCy^, and is 9alled
ammonium cuprosocyamde. The chief objection
to this view is that the so-called cuprosocyanides
are easily decomposed by dilute acids with pre-
cipitation of Cufijj and evolution of HCy ; hence
it seems better to class them with the double
cyanides (e.g. of Ni) than with the salts of acids
the negative radicles of which are composed of'
metal and cyanogen. — 8. With other cyanides —
OujCy2.BaCy2.HjO (Meillet, J. Ph. [3] 3, 413 ;
Weselsky, B. 2, 688) ; Cu2Cy2.2CdCyj (Schiiler,
A. 87, 46) ; compounds with NaCN also exist,
but their composition has not been accurately
determined {v. Meillet, J. Ph. [3] 3, 413).
Cupric cyanide OuCyj. This is probably
the composition of the yellow pp. obtained by
adding KCyAq to solutions of Cu salts ; very un-
stable, decomposing at ordinary temperatures to
Cy and Cu2Cy2.CuCyj (Eammelsberg, P. 42, 131 ;
85, 145 ; LaUemand, C. B. 58, 750).
The double cyanide CuCv2.2CdCyj is de-
scribed by Schiiler {A. 87, 46).
Cupro-cupria cyanide
CuCys.CU2Cyj.5HjO. Obtained by adding KCyAq
to a Cu salt solution and allowing the pp. to re-
main exposed to the air, or by adding a solution
of one of the K cuprous cyanides to a Cu salt
(Hadow, O. J". 13, 106). Green lustrous crys-
tals, decomposing at 100° to Cufij^ with evolu-
tion of H2O and Cy. Acids evolve HCy, ppg.
CujCyj, and leaving a cupric salt in solution.
The fact that this salt may be obtained by add-
ing 2KCy.Cu2Cy2(K2Cu2Cy4) to solution of a Cu
salt suggests that CuCy2.Cu2Cy2 may be the
cupric salt of the hypothetical cuprosocyan-
hydrio acid HjCUjCy, ; if this view is adopted
the salt in question would be formulated as
Cu.CUjCy, and called cupric cuprosocya/nide.
The compounds CuCyj.CUjCyj.HjO and
CuCyj.2CujCy2.H2O have been described (Dufau,
C. B. 36, 1099 ; Lallemand, C. B. 58, 750).
Double compounds of cupro-cupric
cyanide with ammonia. The following
have been isolated (X = CuCy2.Cu2Cyj) : —
X.2NH3.H2O; X.4NH3; X.6NH3 (Dufau, C.B.
36, 1099). X.3NH3 (Mills, Z. 1862. 545). Also
CuCy2.2CU2Cyj.4NH3.2HjO (Hilkenkamp, A. 97,
218). These ammoniacal compounds are some-
times looked on as salts of the hypothetical
cuprosooyanhydric acid HjCujCyj ; they are sup-
posed to be obtained by replacing H by complex
radicles containing Cu derived from aNHj. On
this view the compounds in question may be
formulated and named as follows : —
(NjHsCu) .Ou2Cy4, cuprodiammonio-cuprosocyan-
ide ( = CuCy2.CujCy2.2NH3).
(N2Hi(NH4)2Cu).CujCy4, cuprotetrammonio-cu-
prosocyanide ( = CuOy2.C1l2Cy2.4NH3).
(N2H2(NH4)4Cu).CujCyi, cuprohexammonio-cu-
prosocyanide ( = CuOyj.CU2Cy2.6NH3).
Gold cyanides. Aureus cyanide AuCy, and
several double cyanides of AuCy are known ;
also auricyanhydrie acid HAuCy4 and its salts.
A urous cyanide AuCy. Prepared by eva-
porating AuCy.KCy with HClAq, and washing
the residue with water ; AuCy.KCy is obtaiaed
by dissolving finely divided Au or AujO in KCyAq,
AuCy is also obtained by heating Au20.iEH20
with HCNAq (Himly, A. 42, 157, 337). Citron,
yellow crystalline powder; insol. water, alcohol,
or ether. Heated it gives Au and Cy. Not
332
CYANIDES.
acted on by hot HClAq, HNOaAq, or HjSO.Aq ;
slowly deoompoBed by agua regia ; not acted on
by HjS ; sol. (NHJ^SjAq, from which solution
acids ppt. AUjS. Decomposed by hot KOHAq
to Au and a solution of AuCy.KCy. Sol. hot
NHgAq, and in alkali thiosulphates.
Double cyanides containing aurous
cyanide: AuCy.KCy; obtained by dissolving
AnCy, Aufi, or finely divided Au, in KCyAq, and
evaporating (Himly, A. 42, 157, 337 ; Bagration,
J. pr. 31, 367 ; Eisner, J. pr. 37, 333). Colour-
less, transparent, rhombic ootahedra. E. sol.
^ater, si. sol. alcohol, insol. ether (Glassford a.
Napier, P. M. [3] 25, 71). Decomposed by
warming with acids, giving pp. of AuCy, Iodine
dissolves in AuCy. KCyAq, when excess of I is
added and the liquid cooled dark brownish violet
crystals separate of AuCy.KCy.Ij ; analogous
compounds are obtained by adding excess of: Br
or CI to AuCy.KCy Aq. These compounds may
be regarded as K salts of the hypothetical iodo-,
bromo-, and ohloro - aurioyanhydrio acids
HAuCy^Xj (X = I, Br, or CI) (v. Lindbom, B. 10,
1725 ; Blomstrand, J. pr. [2] 3, 213). The fol-
lowing double cyanides are also known ; most of
them combine with l„ Br^, and Clj ; AuCy.NH4Cy
(Himly, A. 42, 157, 337 ; Lindbom, B. 10, 1725) ;
2AuCy.BaCy2.2H2O ; 2AuCy.CaCy,.BH20 ;
2AuCy.CdCy2.; 2AuCy.CQCy2 ; AuCy.NaCy ;
2AuCy.SrCyj.3H2O; 2AuCy.ZnCy2 (Lindbom, B.
10, 1725). A number of other double cyanides of
Au are described by Lindbom {Bl. [2] 29, 416).
Auricyanhydric acid HAuCyj.SH^O.
Large white tablets ; obtained by ppg. KAuCy,
by AgNOjAq, and decomposing the pp. by less
than an equivalent quantity of cold HGlAq. Sol.
water, alcohol, and ether. Melts at 50°, decom-
posing at a higher temperature to AuCy and
HCy, and then to Au and Cy. Solution gives
AuCy on heating (v. Lindbom, B. 10, 1726).
Aurioyanides (Himly, A. 42, 157, 337;
Lindbom, Z.C.). NH,.AuCy,.H20. KAuCy^.liHjO ;
formed by adding perfectly neutral AuCljAq to
warm cone. KCyAq ; colourless tablets, v. sol. hot
water, insol. absolute alcohol : loses all H2O at
200°, and at the same time decomposes to
AuCy.KCy and Cy. AgAuCy j ; yellow pp. formed
by adding AgNOjAq to KAuCy4Aq ; insol.
HNOjAq; sol. NHjAq. Co(AuCy4)2.
Indium cyanide. Pp. obtained by adding
KCyAq to an In salt solution ; sol. excess of
KCyAq; on evaporating this liquid all In is
ppd. as hydroxide (Meyer, J. 1868. 244).
Iridium cyanides. The cyanide IrCy, is
known ; also iridium cyanhydrio acid HjIrCyj and
its salts {v. Martins, A. 117, 357 ; Claus, J.
1855. 444 ; Wohler a. Booth, P. 31, 161 ; Eam-
melsberg, P. 42, 140).
Iridium cyanide IrCy^. Green powder,
obtained by decomposing HjliCyjAq by HClAq.
Iridium cyanhydric acid HjIrCyj.
Obtained by decomposing the Ba salt (g. v.) by
H2S04Aq, filtering and adding ether. Crystal-
lises from ether in white crystalline crust ; e.
sol. alcohol and water. Decomposes at 300°,
evolving HCN. Decomposed by HClAq giving
pp. of IrCys.
Iridicyanides KjIrCyj; obtained by fusing
IrCl4.2NH,Cl with IJ pts. KCy for 10-15 miu.,
treating fused mass with water, filtering, and
crystallising. Very stable salt; crystallines in
orthorhombic prisms ; insol. alcohol (W. a. B.).
Ba,(IrCy5)2.18H,0 ; obtained by fusing
IrCl4.2NH,Cl with i^ pts. KCy ; allowing to cool,
dissolving in water, adding HClAq, ppg. by addi-
tion of CuSO^Aq, washing pp. and digesting it
with excess of BaOjH,, passing CO^ through the
liquid, filtering and crystallising ; the first crop
of crystals generally contains Ba platinocyanide,
the second crop is free from this salt. Crystal-
lises in prisms, which effloresce in air, losing
I2H2O ; very stable salt.
A solution of HjIrCyj gives pps. with salts of
many heavy metals.
Iron cyanides. No simple cyanide of Fe has
been isolated with certainty. Addition of
KCyAq to solution of a ferrous salt produces a
yellow-red to brown-red pp., which is pro-
bably EeCy2, but always contains K (Fresenins,
A. 106, 210) ; when the ferrous salt is in slight
excess the composition of the pp. approximates
to KPeCys (Stadeler, .4. 151, 1). KCyAq added to
solution of a ferric salt ppts. EejOgH, (Haidlen
a. Eresenius, A. 42, 130). If iron cyanides exist
they are very unstable. Very many compound
cyanides of iron with other metals have been
prepared ; these belong to the class of stable
compound cyanides which are not resolved by
acids into their constituent cyanides ; as a rule
their reactions are similar to those of ordinary
■salts, e.g. cf. the reaction of K^PeCyjAq with
CuSOjAq, giving CuFeCyj and ILSO^Aq, with
that of BaCljAq and Na2S04Aq, giving BaSO,
and NaClAq. The compound cyanides of iron
are generally more stable than their constituent
cyanides. This is shown, among other ways, by
looking at the thermal changes which accompany
the production of these double cyanides. Thus,
the heat of formation of solid KjFeCy,, from
4K + Ee + 6Cy is 0. 367,000 (Berthelot, C. B. 91,
82), the heat of formation of 4KCy (soUd) from
4K + 4Cy is c. 270,000. We have then
[KSFe,CyT = 367,000
[K<,Cy'] = 270,000
hence [4KCy, Ee, Cy^ = 97,000
Now the heat of formation of a ferrous salt is
generally somewhat less than that of the corre-
sponding Zn salt ; but [Zn, Cy^] = c. 53,000 (solid
ZnCyj), therefore we may provisionally ooncluda
that [Ee,Cy'Q = 0.50,000.
Now if [4KCy, Fe, Cy''] = 97,000 and [Fe, Cf]
= 50,000, it follows that [4KCy, EeCy'^
= 47,000 : that is the combination of 4KCy with
FeCy2 to produce K^EeCyj is accompanied by the
production of a quantity of heat roughly equal
to 47,000 gram-units. This quantity of heat is
much larger than that generally produced in the
formation of double salts ; e.g. [KCy, AgCy]
= 11,200, [HgCyAq, 2KCyAq] = 12,000, [Hgl^
2KI] = 3,000, [ZnSOS K^SO '] = 4,000. Hence on
the thermal evidence alone we might provision-
ally conclude that K^EeCyj does not belong to
the class of double salts.
In considering the compound cyanides of
iron, it is advantageous to begin with the two
typical salts, potassium ferrooyanide KiFeCy,,
and potassium ferricyanide KsFeCyj. K,FeOy,
is produced by the action of oxidisers onKjFeCy,,
and reducing agents change KjFeCysto KjFeCy,.
To each of these salts there corresponds an acid,
CYANIDES.
338
HiFeCy, and HjFeCys respectively. These
Bcids have heen isolated, and from each has
been obtained a great many salts and double
salts. Some of these salts form derivatives, e.g.
the nitrorymssides ; and finally there are a few
compound iron cyanides not belonging to either
of the two main classes.
We shall consider first ferrocyanhydric acid
HjPeCyj, and its salts, the ferrocyanides; then
fbrricyanhydric acid, HaFeCyj, and its salts, the
ferricyamdes ; then the nitroprussides ; and
finally the perferrocyamdes.
The ferro- and ferri- cyanides are described
in alphabetical order; double salts are also
described in alphabetical order, thus barium
potassium f errocyauide is described under barium
ferrocyanides, but strontium-potassium ferro-
oyanide under potassium ferrocyanides.
IFEiaiocyANHyDiiic acid and Fekbocyanides.
S'errocyanhydrioacidH.,FeCjg. {Ferro-
cyanicadd. Hydroferrocyamcacid. Ferroprussic
acid. Hydrogen ferrocyanide.) Discovered by
Porret in 1814 {T. 1814. 527).
Formation. — 1. BajFeCysisdecomposedby an
equivalent of H^SO^Aq (Porret, Z.c.).— 2. Cu^FeCyj
or PbjFeCys is decomposed by H^S (Berzelius, S.
30, 44). — 3. Prussian blue is decomposed by cone.
HClAq, the solutionis separated from FejOj, and
evaporated (Bobiquet).
Preparation. — To a cold cone, aqueous solu-
tion of KfFeOje, which has been boiled to expel
air, is added a slight excess of cold cone, air-free
HClAq ; ether is then added, whereby from 96
to 100 p.c. of the HjFeCyj produced is ppd. ; the
pp. is washed with HClAq and then with ether ;
it may be recrystaUised by dissolving in alcohol
and adding ether ; all operations should be con-
ducted as far as possible in absence of 0 (Fos-
selt, A. 42, 163; v. also Liebig, A. 87, 127;
DoUus, A. 65, 224).
Properties and Reactions. — ^White crystalline
powder ; becomes blue in moist air, with evolu-
tion of HON and production of Prussian blue,
Fe,Cy,, (Eeimann a. Carius, A. 113, 39). Un-
changed in sunlight in an atmosphere of H.
Soluble in water ; solution is strongly acid to
litmus ; it decomposes carbonates, acetates, tar-
trates, and oxalates. H^FeCy,; is a strong acid ;
relative affinity not very much less than that of
HCl (v. Ostwald's Lehrbuch, 2, 851). When
boiled with water is decomposed to HON and
white FeH2(Feqye) (E. a. C, i.e.). Berthelot
(0. R. 91, 82) gives H.i'. of the acid in solution
as [H*,Fe,40N,Aq] = 107,200 ; and the heat of
neutraUsation (C. R. 78, 1085) as [H'FeCy"Aq,
4K0HAq] = 54,000. Ferrocyanhydric acid is
tetrabasic, forming salts M'lFeCys, M^'^FeCy,,,
M«MVFeCys, &c.
Ferrocyanides (Ferroprussiates). Salts
of ferrocyanJiydric acid H^FeCy,. These salts
are not to be regarded as double cyanides ; v.
remarks supra. Many ferrocyanides are co-
loured ; the production of one of these salts by
adding K^FeCy, to a metaUie salt solution is
often used as a test for different metals. The
soluble alkali ferrocyanides are not poisonous.
Those ferrocyanides which are completely dehy-
drated by heat without decomposition are decom-
posed at higher temperatures into N and Pe car-
bidey and either a cyanide of the other metal,
e.g. KjFeCy„, or N and metallic carbide, e.g.
PbFeCy„, or Cy and metal, e.g. Ag.FeCys. Those
ferrocyanides which cannot be completely dehy.
drated without decomposition are resolved at a
high temperature into HON, C02,NH5, and either
a mixture or compound of each of the metals
with C. When aqueous solutions of the alkali
ferrocyanides are electrolysed alkali separates at
the negative pole, and HON and Prussian blue
at the positive pole ; if the positive pole is Cu,
CuCyj is formed. Heated with cone. ILSO, fer-
rocyanides give SO2, CO, CO2, and N, and form
sulphates of NHj, Fe, and the other metal of the
original salt. Some ferrocyanides are decom-
posed by HjS giving metallic sulphides and fer-
rocyanhydric acid, e.g. Pb2FeCy5. Ferrocyanides
of heavy metals are generally decomposed by
aqueous alkali, giving alkali ferrocyanides and a
pp. of the hydrated oxide of the heavy metal.
Aluminiu7n ferrocyanide
Al4(FeCys),.a;H,0 (Wyrubow, A. Oh. [5] 8, 444 ;
Tissier, C. R. 45, 232). By mixing cone, solu-
tions of alum and KjFeCyj ; many reactions have
been tried to give an Al salt, but there is doubt
as to the isolation of a definite salt.
Ammonium ferrocyanide
(NH,)jFeCy„.6HjO. Produced by action of NHjAq
on Prussian blue (Scheele), or by adding
(NHJ2CO3 to Pbj^eCys (Berzelius). Best pre-
pared by neutralising HiFeCyjAq by NHjAq, and
adding alcohol (Bette, A. 28, 120 ; v. also Bun-
sen, P. 36, 404). White crystals, isomorphous
with K4FeCy5 ; sol. in water, insol. in alcohol.
Double salts (NHJ,FeCy,.2NH,C1.3H20,
and (NH,)4FeCy„.2NH,Br.3HjO ; obtained by mix-
ing solutions of the constituent salts and cooling
(Bunsen, P. 36, 404 ; Himly a. Bunsen, P. 38,
208 : crystalline forms are given).
Double ferrocyanides of ammonium
(NHJ^CuJeCy, (Schulz, J. pr. 68, 257).
(NHj2Li2.FeCys.3H,0 (Wyrubow, A. Oh. [4] 21,
271). (NHj)K3.FeCyB.3H20 ; obtained by acting
on KgFeCyjAq in presence of NH., by lactose or
glucose until the solution is yellow, and then
adding alcohol (Eeiudel, J. pr. 65, 450).
(NH,)2K2.FeCy5.3H,0 ; by decomposing
BaKj.FeCys {v. Bariwrn ferrocyanide) by
(NHJjSOjAq, or by treating FeK,.FeCys with
NHjAq (Eeindel, J. pr. 76, 342 ; 100, 6 ; Play-
fair, J". ^.69, 287).
Antimony ferrocyanide
Sb4(FeCys),,.25H20 (Atterberg, Bl. [2] 24, 355).
Yellow pp. by adding SbClj to KjFeCyjAq.
Bariuin ferrocyanide Ba2FeCyi,.6H20
(Berzelius, Lehrh. 4, 400 [4th ed.] ; Wyrubo\v,
A. Ch. [4] 16, 280). Formed bypassing air over
a heated niixture'of C and BaCOj, and then act-
ing with FeSOj ; by boiUng Prussian blue with
BaOAq, filtering, and orystalUsing by cooling ;
or by boiling K^FeCy^Aq with an equivalent
quantity of BaClj, filtering, and cooling. Yellow
monoolinio prisms ; sol. in 1,000 parts water at
.15°, and in 100 parts at 75°.
Double ferrocyanides of barium
BaK2.FeCys.3H2O (Bunsen, P. 36, 404 ; Eeindel,
J.pr. 76, 342; Mosander, P.25, 890; Duflos, S.
65, 238). Crystallises with SH^O according to
Wyrubow (.4. Ch. [4] 21, 271). By mixing cone,
solutions of BaClj and K^FeOyj, the latter in ex-
cess. Eeacts with soluble sulphates giving
BaSO^ and double ferrocyanides, of the form
1M"K .FeCy„ (Eeindel, I.e.).
8S4
CYANIDES.
Beryllium ferrocyanide
Be2FeCy„.4BeO,H2.7H20 (Atterberg, Bl. [2] 19,
497; c/.Toozynsky, 2. 1871.276). By the action
of BeSOiAq on Pb jeCyj in presence of NHj.
Bismuth ferrocyanides. Bi((PeOyi5)5; al-
most colourless salt obtained by adding solution
of BiSNOj in smallest excess of air-free HNOjAq
to air-free K^FeCyjAq, in cooled flask, washing
with air-free water in atmosphere of COj and
drying over H2SO4 in. vacuo (Pattison Muif , O. J.
[2] 16, 651 ; 17, 40). Salt soon decomposes when
moist, giving off HON and forming Prussian blue.
Decomposed by CI or Br in presence of alkali.
Changed by CI or dilute HNOjAq in the cold to
ferrioyanide Bi.,(FeCy5)s. Wyrubow {A. Ch. [5]
8, 444) says that BijFeCyj.SH^O is produced by
action of BiSNOj with H^PeCyj; but the data
are meagre.
Double ferrocyanide of bismuth. Ac-
cording to Wyrubow (l.c.) addition of K^FeCyj
to Bi(N03)3 in HNOsAq ppts. BiK.PeCy„.4H20 ;
the existence of this salt wants confirmation.
Cadmium ferrocyanides. None iso-
lated.
Double ferrocyanides of cadmium
CdK,.FeCys.H20 (Hermann, A. 145, 235); or
Cd,K,(FeOys)^.llHjO (?) (Wyrubow, A. Ch. [5]
8, 444). By adding KjFeCyjAq to solution of a
Cd salt.
Calcium ferrocyanide Ca2(FeCyij).12H20.
Triclinic crystals ; Bol. in 2 parts of water at
90° ; by decomposing Prussian blue by CaO Aq,
filtering, exposing to the air, filtering from CaCOj,
and evaporating (Wyrubow, A. Ch. [4] 16, 280 ;
Berzelius, S. 30, 12).
Double ferrocyanides of calcium
CaK2.FeCyB.3H2O (Mosander, P. 25, 390 ; Mar-
ohand, J. Chim. Mid. 20, 558) ; by ppg. a Ca
salt by excess of K4FeCy5Aq. CaNa5(PeCyi,.)2
(Wyrubow, A. Ch. [4] 21, 271). CaSrFeCy^.lOHjO
(W., I.C.).
Cerium ferrocyanide Cej(FeCys),,.30H2O
(Wyrubow, A. Ch. [5] 8, 444). Double ferrocyan-
ides of Ce and K are also said to exist ; but
none of the salts has been thoroughly examined
(v. Jolin, Bl. [2] 21, 535).
Chromium ferrocyanides. Addition
of KjFeCyjAq to CrCl2Aq gives a yellow pp.
probably CrjFeCyj (Stridsberg, J. 1864. 304;
c/. Kaiser, A. Swpplbd. 3, 163).
Cobalt ferrocyanides. K^FeCy^Aq
added to a Co salt solution produces a blue pp.
which soon changes in air to reddish ; this
Vp. is a ferrocyanide of Co, but the exact com-
position has not been accurately determined.
Wyrubow (A. Ch. [5] 8, 444) gives the
formulffl C02FeCy„.7H.,0, Co,(FeCy„)j.22H20,
CoKo-FeOye, and Co3K5{FeCy„)„ to the pp. ob-
tained under different conditions. Compounds
of Co ferrocyanides with NHj are described by
Curda (Z. 1869. 369), and by Gintl (Z. 1868.
525) ; the formulae CO2FeCye.i2NH3.9H2O, and
Co2FeCyij.8NH3.10H2O are given ; a salt having
the composition Co2FeCyj(NO2)2.10NH3.7H2O is
described by Gibbs a. Genth (A. 104, 150, 295 ;
cf. Braun, A. 132, 33).
Copper ferrocyanides. The brown-red
pp. obtained by adding K^FeCyj to a Cu salt
solution is more or less pure CujFeCy,; ; it is
better prepared by using H,FeOyBAq, as the pp.
obtained by K4FeCy, is mixed with Cu-K ferro-
cyanides (u. Williamson, A. 57,225). The pp.
dried over H2SO4 is said to contain 7H2O (Earn..
melsberg, P. 74, 65), or 9H2O (Mouthiers, A. 64,
297), or lOHjO (Wyrubow, A. Ch. [5] 8, 444).
If an excess of KjFeCyj is used as pptant., double
Cu-K ferrocyanides are obtained; the formula
CaK2-E'eOyii.H20, and Cn3K2(FeCys)j.l2H20, are
given (Bammelsberg, P. 74, 65 ; Sohulz, J. pr.
68, 257 ; Wyrubow, A. Ch. [5] 8, 444 ; Eeindel,
J. pr. .103, 166). The salt CuNaoFeOy, is de-
scribed by Sohulz (I.e.).
Double compounds of cuprio ferro-
cyanide. By ppg. an ammoniacal solution of
CuO by KiteCys, the salt 0u2FeCye.4NHs.H.0
is formed (Bunsen, P. 34, 134 ; Mouthiers, A.
64, 297). By digesting CUjPeCye with NH^Aq
crystalline CuJ'eCyB.8NH3.H,0 is formed (Mou-
thiers, l.c. ; Guyard, Bl. [2] S'l, 438).
Cuprous ferrocyanide. This salt is said
to be formed by adding K^FeCyjAq to CujOlj
in HOlAq ; it probably has the composition
Cu.,FeCy5 (Proust). The following double
cuprous-potassium (and sodium) ferro-
cyanides have been obtaioed : —
Cu2K2.FeCy„.liH20 ; CujNaj.FeCyj (Schulz, J. pr.
68, 257); CuK3.FeCy8.!cH20 (BoUey, A. 106,
228 ; Wonfor, C. J. 15, 357).
Didymium and Erbium ferrocyan-
ides. The double ferrocyanides
DiK.FeOys.4H2O, and ErK.FeCys.4H2O are
said to be produced by adding KjFeCyjAq to
salts of Di and Er respectively (Cl^ve, Bl. [2] 21,
196 ; Clfeve a.Hoeglund, Bl. [2] 18, 197).
Iron ferrocyanides. Ferrous ferro-
cyanide, Fej.FeCys; and ferric ferrocyanide,
Fe4(FeCy3)3, are both knovm; also derivatives
of both. In connexion vrith these compounds
cf. Ikon ferkioyanidbs, p. 388.
Ferrous ferrocyanide Fej.FeCys. Ob-
tained by ppg. ferrous salts by HjFeCyj; if
KjFeCy, is used the pp. always contains K.
Also formed when Prussian blue reacts with ,
H2S. It is obtained pure by boiling H4FeCy,Aq
in absence of air (Asohoii, Ar. Ph. [2] 106,
257). [3H4FeCy„=Fe2.FeCya-i-12HCN.] White
amorphous pp. soon oxidised in air with
production of blue-coloured compounds; reac-
tion may perhaps be 3(Fe2.FeCy„) + 30 + 3H2O
= Fe2(0H)s + Fe4(Fe0ys)3 (Erlenmeyer, Lehr-
buch der organ. Chemie [1867], 148 et seq.).
Double ferrocyanide derived from
ferrous ferrocyanide.
Potassium - ferrous ferrocyanide
K2Fe.FeCyi,. (Everitt's salt.) Obtained by de-
composing KjPeCyj vrith hot dilute H2S04Aq, •
in making HON pKiFeCyjAq + 3H2S04Aq
= 6HCN + 3K2S04Aq + KjFe.FeCyJ (William-
son, A. 57, 225; Everitt, P.^T. [3].6, 97). White
mierosoopio quadratic crystals, becoming blue in
air; oxidisers produce potassium-ferrous ferri-
oyanide, PeK.FeCyj. Also produced by boiling
H,FeCy,Aq with KjSO, (Asohoff, Ar. Ph. [2]
106, 257) ; probably always present in the white-
blue pp. obtained by adding KjPeCyjAqto ferrous
salts (Aschoff, I.C.). ,
Ferric ferrocyanide Pe4(FeOyj)a.
{Prussian blue.) This body was accidentally
discovered in 1704 by Diesbach, a colour-maker
in Berlin. It was afterwards found that the blue
compound could be prepared by calcining blood
with potash and then adding sulphate of iron.
CYANIDES.
S.%
In 1724 Woodward of London prepared the
Bolouring matter by deflagrating cream of tar-
tar with nitre, calcining the residue with ox-
blood, dissolving in water, and ppg. by alum and
sulphate of iron ; he thus obtained a greenish
pp. which turned blue when treated with hydro-
chloric acid. More or less pure ferric ferro-
oyanido is obtained commercially by mixing
■KjFeCyjAq with partially oxidised ferrous sul-
phate, and oxidising the light-blue pp. thus
formed by exposure to air or by the action
o£ CI, HNOjAq, aqua regia, or alkaline hypo-
chlorites; the blue body thus formed, known
commercially as Pnissian blue, is a mixture
of ferric ferrooyanide, Fe.,(FeCyj)3, with fer-
rous ferro-cyanide Fej.FeCyj, ferrous ferri-
cyanide 'Pe,{FeGjg)2 (known commercially as
TumbulVs bVue), and probably one or more
of the K-Fe ferro- or ferri-cyanides (u. ■post).
The simultaneous production of iron ferro-
cyanide (Prussian blue) and iron ferrioyanide
(Turnbull's blue) is probably explained by the
fact that both ferrous and ferric salts are pre-
sent, and that ferric salts oxidise ferro- to ferri-
cyanides, while ferrous salts reduce ferri- to
ferro- cyanides (v. Skraup, W. A. B., 74 (2nd
part) ' Juniheft, 1876). The blue pp. obtained by
adding KiFeCyjAq to excess of a ferric salt
solution is nearly pure ferric ferrocyanide,
Fe4(FeCy5)3 ; as thus prepared the substance is
known commercially as Paris blue. The name
Prussicm blvs is often extended to all the blue
pps. obtained by adding iron salts to K ferro- or
ferri-cyanide. For an account of the manu-
facture of Prussian blues v. Dioiionaey of
lEOHNIOAIi CHEMISTRY.
Formation. — 1. By the reaction of ferric
salts with KiFeCyjAq (v. sv^-a) ; if the ferric
salt is kept in excess, approximately pure
Fej(FeCys)3 is obtained; if the K^FeOy, is in,
excess the pp. always contains K-Fe ferro-
cyanide, KjFe.FeCy,.— 2. By adding a ferrous
and a ferric salt to KCyAq, or to HCyAq with
excess of KOH added, and then adding acid
to dissolve the Fe(0H)2 and Fe(OH)s ppd. by
the KOH or the KCy. [ISKCyAq + SFeSOiAq
= SK^FeCyjAq + SKjSOjAq ;
3K,FeCy,Aq + 4FeClsAq
= 12KClAq + Fe^(FeCy,)3.]— 3. The action of
air, or other oxidiser, on H^FeCy„, or on ferrous
ferrooyanide, Fej.FeCy,, forms Fej(FeOyj)3.
PreparaUon. — K4FeCy8Aq is added to
FeCl3Aq keeping the latter in excess ; the pp.
is digested with FeCl3Aq, to remove any
K4Pe.FeCyj, thoroughly washed and dried. Or
HjFeOys is used in place of K^FeCyj ; in this
case the pp. is pure Fe4(FeCye)a.
PraperHes. — Dark-blue amorphous solid
with lustre resembling that of copper. Obtained
in lustrous crystals by spontaneous evaporation
of solution in cone. HOlAq (Gintl, D. P. J. 235,
248). Does not become perfectly dehydrated
until heated to c. 250° ; complete dehydration is
accompanied by partial decomposition, with
evolution of NHiCy and (NHJaCO, (v. Eeimann
a. Carius, A. 113, 39 ; Skraup, A. 186, 371 ; Eam-
melsberg,.4. 64, 298). Strongly heated it glows
and is burnt to FojO,. Insoluble in water,
alcohol, ether, oils, and dilute acids ; sol. in
cone. HClAq, addition of water ppts. the original
compound ; sol. in HjOjOiAq, also in (NHJ tar-
trate solution ; is entirely ppd. from solution in
H2C.,04Aq by exposure to sunlight (Schoras, B.
3, 12).
BeacUojis. — 1. Heat alone decomposes
Fe,,(FeCy,)„ evolving CO,, CO, NH,Cy, HON,
and (NHiJ^CO,. — 2. Seated m ow it is burnt to
FOjOa, NHjCy, and CO2. — 3. Decomposed by
alkalis (including MgO) to FCjOj and KjFeCyjAq;
similar change is effected by KjCOjAq, and by
excess of NHjAq. — 4. Boiled with mercuric oxide
and water, Fe^Oj and HgCyj are formed. —
5. With lead oxide, Fe^Oj, PbjFeCyj, and
K3FeCy8 are produced. — 6. Eeduced 6y suT/phwr-
etted hydrogen, also by iron or zinc, to white
ferrous ferrocyanide Fe2.FeCy„. For account of
Soluble Prussian blue v. Potassium-ferrous
ferricyanideundiex Ferrous ferricyanide.
Double ferrocyanide derived from
ferrip ferrocyanide.
Ammonio-ferric ferrocyanide
Fe;.(FeCy5)5.6NH3.9HjO (Mouthiers, J. Ph. 9,
262). When excess of NH3Aq is added to
FeCl^Aq and the liquid is filtered into
KjFeCyjAq, a white pp. forms which soon be-
comes blue in the air ; this blue solid when heated
with NHj tartrate solution at 60°-80° for some
hours to dissolve FejOjHj leaves blue am-
monio-ferric ferrooyanide, which is washed with
water, and dried beloW 100°. The compound
evolves HON at 100° ; no NH, is evolved below
160°. The same compound is the first product
of the action of NHjAq on Fe4(FeCyj)3 (Mouthiers,
I.C.). Because of the stability of this compound
it may perhaps be regarded as ferric-ferric-
armmornum ferrocyanide (FCj-NoHigFej) (FeCy5)3.
Lanthanum ferrocyanide. — None has
been isolated, but the double salt LaK.FeCyg.4H2O
is described by CMve (Bl. [2] 21, 196; v. also
Wyrubow, A. Oh. [5] 8, 444).
Lead ferrocyanide Vh^^Cja-SKfi.
White pp. formed by adding K^FeCyjAq to
Pb(N03)2Aq and washing repeatedly with water
(Berzelius; Wyrubow, A. Oh. [5] 8, 444). Loses
all HjO at moderate temperature. Dehydrated
salt heated in air evolves N and leaves mixture
of carbides of Fe and Pb.
Lithium ferrocyanide Li,.F^Cyj.9H20 ;
very soluble salt ; deliquescent crystals (Wyru-
bow, A. Oh. [4] 16, 280). The double salt
Li2K2.FeCye.3H2O is described by Wyrubow
{A. Oh. [4] 21, 271).
Magnesium ferrocyanide
Mg2.FeCy5.12H20. ' By dissolving MgCO, in
HiFeCyjAq and evaporating ; pale yeUow crys-
tals ; sol. 3 pts. cold water ; unchanged in air
(Bette, .4. 22, 148; 23, 115). The double salt
MgKj.Fe0y8 is described by Berzelius (Lehrb. 4,
400 [4th ed.]).
Manganese ferrocyanide
Mn2FeCys.7H20 ; white pp. by adding K,FeCyjAq
to solution "of a manganous salt (Wyrubow,
A. Oh. [0] 8, 444 ; Mosander, P. 25, 390).
'errocy
MnK2.FeCyj (Berzelius ; Wyrufeow, l.c.).
Mercury ferrocyanides. Mercurous and
mercuric salts give pps. with KiFeOyj, but the
composition of the pps. was not accurately de-
termined. Bunsen (P. 34, 134) obtained a com-
pound of ammonia with mercwric ferrocyamde
Hg„FeCy8.2NH3.H20 by mixing cooled solutions
of Hg(N0a)2Aq, NHjAq, and NH,NO,Aq.
336
CYANIDES,
MolybdentLm ferrocyanides
Mo2FeCys.8H,0 ; MOjFeCyj.liHaO ;
Mo4FeOyj.20H2O ; and the double salt
MoiKjPeCyj.20H2O (?) (Wyrubow, A. Oh. [5] 8,
444 ; cf. Atterberg, Bl. [2] 24, 355). These salts
are said to be formed by reactions between
KjFeCyijAq and salts of Mo, or in some oases
NH, molybdate ; their composition is doubtful.
Nickel ferrocyanides. According to
Wyrubow (.4. Oh. [5] 8, 444) K.PeCy,, added to
a salt of Ni, ppts. NiKj.FeCyj.SHjO : if excess of
ferrocyanide is used the salt is said to have the
composition Ni3K2.FeCyij.65H20. By using
HjFeCyjAq in place of the K salt, salts are
obtained which Wyrubow formulates as
Ni,(FeCye), and Ni2PeCy„.ll{or 14)H,0. By
adding KjFeCyjAq to a Ni salt solution contain-
ing KH, various salts are formed, and from
these again others are obtained by treatment
with NHjAq; the following are described: —
Ni2FeCys.iONH3.4HjO ; Ni2FeOy5.4NH3.HjO
(Eeynoso, A. Ch. [3] 30, 252) ;
Ni2FeCy5.2NH3.4(&9)HjO ; NiJB'eCys.8NH3.4H20;
Ni2FeOye.i2NHs.9H2O (Gintl, Z. 1868. 525).
Niobium ferrocyanides. — Nonecertainly
isolated. Several double salts are described
(Wyrubow, A. Ch. [5] 8, 444; Atterberg, BZ. [2]
24, 356) ; they are said to be formed by adding
KjFeCyjAq to niobic acid in presence of KHCjO, :
Nb,3K(FeCy,)2.67H20 (?); Nb,2K2.FeCy3.39H20 (?);
(NbO)3K.(FeCye)„.10H2O(?).
Potassium ferrocyanide K^FeOy^.
{Yellow prussiate of potash. Ferroprussiate of
potash.) Discovered about 1750 by Macquer;
obtained by him by boiling Prussian blue with
potash. BerthoUet showed that the iron in it
was an essential part of the salt. H.F.
[K*,Fe,Cy»] = 367,200; [K*FeOy',Aq] = 5,400
(Berthelot, C. B. 91, 82).
Formation. — 1. By fusing nitirogenous animal
matter (horn, feathers, dried blood, leather-
clippings, &c.) with KjCO, and scrap iron,
lixiviating with water, filtering, and crystallising ;
EOy is formed, and on addition of water this
reacts with the iron to produce KjFeCyj (Liebig,
A. 38, 20 ; NoUner, A. 108, 8 ; Hoffmann,
D. P. J. 151, 63). [2Fe + 12KCNAq + iSfi
= 2KiFe0yeAq+4K0HAq + 2H2; or in presence
of air 2Fe + 12KCNAq + 2B..fl + O2
= 2K,Pe0ysAq -I- 4K0HAq]. — 2. By heating
NHj.SON with scrap iron to dull redness, and
dissolving out with water (G61is, W. J. 1862. 283 ;
1863. 321; Fleck, W. J. 1863. 323; Alander,
D. P. J. 226, 318 ; Tscherniak a. Giinsburg, J.
1878. 1123).— 3. By the action of KCNAq on
Fe(0H)3, FeCOj, or FeS, &a. (Fresenius a.
Haidlen, A. 43, 132 ; Liebig, A. 38, 20).— 4. By
reaction between KOHAq and various ferro-
cyanides.
Prepa/raUon. — Pmto Prussian blueFe4(FeCyj)3
is added to boiling KOHAq so long as the blue
colour changes to brown, the solution is filtered,
evaporated, and the salt is recrystallised from
water. Impure KiFeCyj (prepared from com-
mei;ial Prussian blue) generally contains KjCO,,
S^SO,, (fee, and sometimes Prussian green; it
may be purified, according to Berzelius, by heat-
ing until it effloresces, and then to its melting-
point, dissolving in water, filtering from 0 and
Fe carbide, adding acetic acid to convert K2CO,
and KCy into acetate, adding Ba acetate ittle by
little to pp. sulphates, filtering, evaporating, ppg.
EjFeCyg by alcohol, and reorystallising twice
from water. -
ProperUes. — Eeddish-yeUow quadratic pyra-
mids (Bunsen, P. 36, 404) ; crystallises with
3H2O. S.G. 1-86 {W. J. 1875. 503). Not
poisonous. Loses all H2O at 60°-80° ; un-
changed at ordinary temperatures. Sol. 0. 4 pts.
cold H2O and in c. 2 pts. at 100° ; insol. alcohol ;
1,000 0.0. K^FeC^sAq saturated at 15° has S.G.
1-144, and contains 258'77 g. salt and 885-34 g.
water (Michel a. Kraft, A. Ch. [3] 41, 471).
Solution decomposed in sunlight with ppn. of
Prussian blue and evolution of HON.
Beactions. — 1. Heated in closed vessel melts at
little above red heat, evolves N, and leaves mix-
ture of EOy and Fe carbide; if salt is not de-
hydrated it gives off OO2, NHs, HON, and N.—
-2. Heated to redness in aAr gives KOyO ; same
product formed by heating with reducible metal-
lic oxides. — 3. Changed slowly by ozone into
KjFeCy,; not, however, acted on by oxygen. —
4. KjFeCyjAq electrolysed forms KjFeCyj at posi-
tive, and KOHAq and H at negative, pole (Schlag-
denhauffen,J'.1863.305).— 5.K4FeOy,Aqischanged
to KjFeCyjAq by oxidisers, e.g. KMnOjAq, PbOzi
Mnbj (Brodie, P. 120, 302; Weltzien, A. 138,
129; Eeindel, J.iJr. 76, 342; Bottger, /. ^. 76,
238 ; Braun, J.pr. 90, 356).— 6. Ghlonne forms
KCl and KjFeOyj ; bromine reacts similarly to
CI. — 7. Iodine dissolves in warm K^FeCy, to
form an olive-green liquid, from which crystals
of a double compound , of KI and KjFeCyj
(KI.KjFeCyj) separate on cooling (Mohr, A. 105,
57 ; Blomstrand, J.pr. [2] 3, 207 ; Preuss, A. 29,
323). — 8. Fairly cone, nitric acid forms nitro-
prussic acid (g^.v. p. 341) ; very cone, nitric acid
decomposes the salt entirely, forming N, Oy,
NO, OO2, KNO3, and FCjOa.- 9. Dilute sulphuric
acid forms HiFeCy^Aq if cold, if the H2S04Aq is
warm HCy is evolved (2K4FeCy8Aq + SH^SO^Aq
= 6HCyAq + FeK2(FeOyB) + SK^SO^Aq ; Witt-
stein, Vierteljahr. Pharm. 4, 515 ; Asohoff, Ar,
Ph. [2] 106, 257). Heated with cone. HjSO,
almost pure CO is evolved (Fownes, P. M.
[3] 24, 21) [K,FeCy3 + &B..,BO^ + 6H,0
= W..,^0, + 3(NHJ2S0,, + FeSOi -1- 6C0].— 10. De-
composed by boiling with mercuric oxide and
water, Hg0y2 and Fe2(0H)s being formed (Weilh,
Z. 1869. 381). — 11. Boiled with salamvmomac
NHjOy is volatilised (Wyrubow, A. Oh. [4] 16,
280). — 12. Ammomacal silver nitrate forma
Fe(0H)3 and AgOy.KOy.— 13. KjPeCy, boiled
with a very little ferric chloride solution forma
some KjFeCye (Williamson, A. 57, 238).—
14. K^FeCyijAq reacts with most metallic salts
to give pps. ot ferrocyanides (g.v.).
Double ferrocyanides derived from
potassium ferrocyanide. (Those only are
mentioned hero which contain potassium, and
another metal the first letter of the name of
which follows P in alphabetical order ; the other
double ferrocyanides containingK are mentioned
under the headings of the metal other than K).
Na3K.FeCy5.9H,0 (Wyrubow, A. Ch. [4] 16,
280).
Na2K2.FeOys.8H2O (Eeindel, J. pr. 100, 6).
NaKs.FeOy8.3H2O (Eeindel, J. pr. 65, 450).
K2Sr.FeOys.3H,0 (Wyrubow, A. Ch. [4] 21,
271).
cyANlDES.
8a7
, K.Wj.KeCys.7HjO ; K^W ,ieeCy,.201IjO (?)
(Wyrubow, A. Gh. [5] 8, 444).
K,U3.FeCy..6HjO (?) ; K,3UOj.(FeCye),.6H,0 ;
K.5UO2(Fe0ye)4.12H2O (W., I.e. ; Atterberg, Bl.
[2] 241, 355).
K,.V.(E'eCy.),(??) (W., Z.c.) ;
Ke{VO)5(PeCy,)^.60H,O (?) (A., l.e.).
KY.PeOye (OWve a. Hoeglund, Bl. [2J 18, 197).
Double salts containing potassium
ferrooyanide.
K,,PeCye.2KN03.2NaN03 (Martiua, Z. 1866.
319 ; cf. Wyrubow, A. Ch. [4] 16, 280).
K^FeCy,.3HgCyj.4H20 (Kane, A. 35, 357 ;
Lowe, J. 1857. 273).
Osmium ferrooyanide OS;jFeCya (Mar-
tins, A. 117, 357).
Buhidiumferrocyanide'&h^eQiyi^.^IL^O.
Yellow triolinio crystals. Obtained by dissolving
IlbjCO, in HjFeCyjAq, and evaporating (Piocard,
/.^w. 86, 449). - .
Silver ferrooyanide Ag,FeCyi, (Glass-
ford a. Napier, P. M. [3] 25, 71) ; with 2H,0,
according to Wyrubow (A. Gh. [5] 8, 444).
White pp. turning blue in the air by adding
EfFeCyeAq to solution of a Ag salt. Sol. in
ECyAq, Combines with NH, to form
Ag,FeCy..2NH3.6H,0
(Gintl, W. A. B. 59, 554 ; 60,470). Decomposed
by warm NHjAq to PeO.ffiH^O and solution of
AgCy and NH^Oy (Weith, Z. [2] 5, 381).
Sodium ferrooyanide Na4FeCy„.12H20
(Berzelius), or 9H.jO when ppd. by addition of
alcohol to its hot solution (Weith, A. 147, 329).
Obtained by boiling Prussian blue with NaOHAq,
filtering, and cooling. Monoclinio, pale-yellow
crystals, which effloresce in air (Beindel, J. pr.
102, 42).
Strontium ferrooyanide
Sr2FeCy,.15HjO ; easily soluble, yellow mono-
oUnic crystals. Obtained by dissolvirig SrCOj
in H4PeOy,Aq, evaporating, and recrysiallising
the crystals which separate (Bette, A. 22, 148).
Wyrubow {A. Gh. [4] 16, 280) obtained crystals
with 8HjO.
Thallium ferrooyanideTl\^%Cji,.2'B.^O ;
small, lustrous, yellow tricUnio crystals. Formed
by crystallising a mixed solutioii of cone.
KiFeOyj with cone. TljCOjAq (Lamy a. Des-
oloiseaux, A. Gh. [4] 17, 310 ; Wyrubow, A. Gh.
[4] 16, 280).
Tin ferrooyarhides. Stannous ferrooy-
anide Sn2FeCy8.4H20 ; white pp. by adding
K,FeCy„ to SnClj solution (Wyrubow, A. Gh. [5]
8, 444). Stannic ferrooyanide SnFeCyB.4H20 ;
brownish pp. by adding K^FeCyjAq to SnOl^
solution (W., I.O.). Wyrubow describes other
ferrocyanides of tin, but their composition is
doubtful.
Titanium ferrooyanides. According to
Wyrubow {A. Gh. [5] 8, 444) various Ti ferro-
cyanides are obtained by adding E4FeCyjAq to
solutions of Ti salts ; the composition of these
compounds is doubtful .{of. Atterberg, Bl. [2]
24, 355).
Thorium ferrooyanide Th2FeCy5.4Hj0
(ClSve, Bl. [2] 21, 119).
Uranium /erroc yijsraitZeUFeCyij.lOHjO;
U,KjFe0y,.20H2O (Wyrubow, A. Gh. [5] 8, 444).
Vanadium ferrooyanide. The salt
(VO)2FeCye.llHjO is said to be formed by ppg.
voj>. n.
V salts by KjFeCy„Aq (Atterberg, Bl. [2] 24,
355).
Yttrium ferrooyanide. The salt Y^FeOy,
is said to be produced by boiling yttria with
Prussian blue, filtering and evaporating slowly
(Popp, 4. 131, 179). For double K-Y salt v.
Potassium ferrooyanide.
Zinc ferrooyanide ZnjFeCys.SIJjO
(Schindler, Magaz. Pharm. 35, 71), or with
4H,0 (Wyrubow, A. Gh. [5] 8, 444). White pp.
by adding excess of ZnSOjAq to KjFeCyjAq ; or,
better, by using HiFeOyj. If the ZnSOiAq con-
tains NHj, a double salt, Zn2FeOy,.3NH3.H20, is
produced (Bunsen, P. 34, 134 ; Mouthiers, A. 64,
297).-
Feekictanhydeio acid and febbioyanldes.
Ferricyanhydric acidSfPeGy^. (Werri-
cyanic acid. Sydroferricyanic acid. Ferri-
prussio acid. Hydrogen ferricyanide.) Pre-
pared by decomposing Pbs(FeCy()2 by dilute
H^SO^Aq (Gmelin) ; or, preferably, by adding
to cold cone. KjFeCysAq two or three times its
volume of very cone. HClAq, and colWoting the
acid which separates on a porous plate, and dry-
ing m vacuo (Sohafarik, W. A. B. 47, 262),
Forms lustrous brownish-green needles ; very
sol. in water and alcohol, insol. in ether ; de-
composed in air with evolution of HON and pro-
duction of blue-coloured residue (Posselt, A. 42,
163). Joannis (C. B. 94, 449, 541, 725) ex-
amined the thermal data for HjFeCyaAq; the
solution was prepared by the action of Br on
H^FeOysAq :—
[ffFeCy«Aq, 3K0HAq] = 43,500 ; [H', Fe, Cy«,
Aq] = 77,400 (gaseous Cy) ; [HTeCy»Aq, H] =
29,200 (production of solution of H,FeOy, from
solution of HsFeCyj).
Ferricyanides (Perriprussiates). Salts of
ferricyanhydrio acid. These salts are produced
by the action of oxidising agents on the ferro-
cyanides ; the action consists in the withdrawal
of I of the metal of the ferrooyanide ; MjPeCys - M
= MjFeOyj. Alkali ferricyanides are soluble ih
water ; most of the other ferricyanides are insolu-
ble, and may be formed by ppn. Alkali ferricyanides
give pps. with salts of many different metals.
Ammonium ferricyanide
(NHJaFeOyj.SHjO. Chlorine is passed into NH,
ferrooyanide solution until the liquid ceases to
give a blue pp. or colour with FeOljAq (free from
FeClj) ; the liquid is evaporated slowly, then
cooled ; the crystals of (NHJ^FeCyj are separated
from those of NH^Cl formed in the reaction, and
are recrystallised from water. Cannot be wholly
dehydrated without partial decomposition, HCN
being evolved and some Prussian blue produced
(Jacquemin, Bl. [2] 1, 349 ; Bette, A. 23, 115). ■ ^ ■
By boiling K^FeCyjAq with (NHJjSOjAq
Schaller {Bl. [2] 1, 275 ; 2, 93) obtained crystals
otihe double salt (NH4)jK.FeOyB. Schuler (W.
A. B. 77, 692) obtained the double salt
NH4Pb.FeCys.3H2O.
Barium ferricyanide Baj(FeCy8)220H2O
(Sohuler, W. A. B. 77, 692). By passing CI into
a solution of BaKj.FeOy,, (obtained by mixing
cone. BaCl2Aq with excess of cone. K^FeCy^Aq),
warming to remove excess of CI, adding alcohol,
and cooling, the double salt BaE.FeCy8.3H2O
was obtained (Bette, A. 23, 115).
Beryllium ferricyanide (Joozynsky, ^.
1871, 276). Composition undecided.
Z
3S8
CYANIDES.
V Bismuth ferricyanide Bi3(FeCys)s.
Brownish red pp. produced by adding KsFeCyjAq
to Bi(N03)3 dissolved in very little HNOjAq,
washing with cold water, and drying in vacuo
over H2SO,. Decomposed by boiling water with
evolution of HON. 01, in presence ot hot water,
forms BijOj, Prussian blue, and HON ; Br and
NaOHAq gives BijO, and 'Ee.fi,. Beduced by
Na-amalgam to BijIFeCyJj.
Also obtained by reaction of dilute HNOjAq
with Bi4(FeCyj)5 fe. v.) (Pattison Muir, O. J. [2]
16, 654 ; 17, 40).
Cadmium ferricyanide. Yellow pp. ob-
tained by adding EgFeOy^Aq to solution of a
Cd salt ; composition undecided. This pp.
dissolves in NHjAq ; if little NHjAq is
used the double salt Cd3(FeCys)26NH,.3H20
is formed; if much NHjAq is added the salt
Cd3(FeCye)2.4NH3.2H20 is produced after a time
(Wyrubow, A. Ch. [5] 10, 413).
Calcium, ferricyanide
Ca3(FeCyB)2.ia(or 12)H20 (Berzelius, S. 30, 12 ;
Bette, A. 23, 115). Formed by the action of CI
on CajFeCyjAq. Fine, red, deliquescent needles.
The double salt CaK.FeCy, is described by Mo-
sander (P. 25, 390).
Cerium ferricyanide CeFeCyB.4H20
(Jolin, Bl [2] 21, 535). By adding alcohol to a
mixture of Ge nitrate with KsFeOy^Aq.
Chromium ferricyanide. Compound ob-
tained by adding KjFeCyj to a Cr salt. Compo-
sition undecided {v. Stridsberg, J. 1864. 304).
Christensen (iT. pr. [2] 23, 49) describes the
double compound CrFeCyj.5NH3.l5H20.
Cobalt ferricyanide Co,{FeCy3)j. Eed-
brown pp. obtained by adding KjFeCygAq to a
Co salt (Gm. 7, 497). When Co3(FeCyj)j is kept
in contact with NHjAq for a long time the
double compound Co3{FeCyB)2.2NH3.6HjO is pro-
duced (Braun, A. 125, 153, 197).
Copper ferricyanides; Cuprous ferri-
cyanide Cu3(FeCy5) ; brownish red pp. formed by
adding CujClj in HClAq to KjFeCypAq. Sol. in
NHjAq, but not in NH4 salt solution. Cupria
ferricyanide CUjIFeCyj)^; yellowish pp. formed
when a onprio salt solution is ppd. by KsFeCy,, ;
said always to contain excess of K3FeCyj, pos-
sibly in combination ; sol. NH,Aq, also in solu-
tions of NHj salts (Wittstein, B. P. 63, 314 ;
Williamson, A. 57, 225).
Iron ferricyanides. Turnbull's blue,
FejCy,,, is probably ferrous ferricyanide
Fe3(Fe0yj)2. Soluble Prussian blue, KPojCyj,
is probably potassium-ferrous ferricyanide,
FeK.FeCyj : there is also a corresponding NH^
salt. Pelouse's green (or Prussian green),
FCijCyas, may be regarded as ferroso-ferric ferri-
cyanide, Fe"3.Fei«4{FeCy,)8.
Addition of FeCl3Aq to K^FeCyjAq produces
soluble Prussian blue, which is generally regarded
as a ferricyanide ; the same compound is pro-
duced by adding FeS04Aq to KsFeCyjAq. The
formation of a ferricyanide from the reaction
between a ferrous salt and a ferricyanide, and
. also from that between a ferric salt and a ferro-
cyanide, is explained by Skraup's observation,
that ferrous salts reduce ferricyanides to ferro-
cyanides, while ferric salts oxidise ferro- to
:'erri- cyanides (W.A. B. [Juniheft, 1876] vol. 74,
part 2). When soluble Prussian blue is treated
with FeSO,Aq Turnbull's blue, Fe3(FeCy„)j, is
formed ; when ferric sulphate is u^ed the product
is Prussian blue, which is ferric ferrocyanid*
Fe4(FeCyj)3. Ferrous f errocyanide Fe2.FeCy, {q.v.
p. 334),. when partially oxidised, produces ferrous
ferricyanide (Turnbull's blue), and when more
fully oxidised ferric ferrocyanide (Prussian blue)
is formed. These reactions suffice to show how
easy is the passage from ferrooyanides of iron
(both ferrous and ferric salts) to ferricyanides,
and vice versd.
Ferrous ferricyanide Fe3(FeCyj2.
{Tu/mbull's blue). Obtained by adding KjFeCyjAq
to an excess of a ferrous salt, digesting the pp. for
some time with the ferrous solution, and washing
with hot water ; also obtained by partial oxida-
tion of ferrous ferrocyanide Fej.FeOy3, which is
the pp. formed by adding H4FeGy„Aq to a ferrous
salt. Best prepared by ppg. excess of a ferrous
salt by H3FeCy3Aq (2. «.). When dried in air
retains about 28 p.c. water (Williamson, A. 57,
225) ; cannot be completely dehydrated without
partial decomposition, giving Fe^Oj and Prussian
blue, Fej(FeCy5)3. Oxidised when moist by ex-
posure to air to ferric ferrocyanide (Prussian
blue). Deep-blue powder, with tinge of oopper-
led; insol. water, alcohol, and dilute mineral
acids ; sol. H^CjOjAq. Decomposed by KOHAq
or KjCOjAq, giving KjFeCyjAq and FCjO,;
Prussian blue gives Fe^O, and jK4l'eCyjAq.
Ferroso-ferric ferricyanide
Fe™4.Fe«s(FeOy3)5 = Fe,3Cy3e. (Prussian green.
Pelouse's green) (Pelouze, A. Ch. [2] 69, 40;
Erlenmeyer', Lehrb. der organ. Chemie [1867],
p. 48 et seq. ; Williamson, A. 57, 225). Green
pp. obtained by passing excess of 01 into KjFeCy,
or K3FeCyi|, boiling the liquid, washing the pp.
with cone, boiling HClAq (to remove Fe^Og and
Prussian blue) so long as the liquid is turned
blue on addition of water, washing with water, .
and drying. Also produced by prolonged con-
tact of KjFeCyj with aqueous acids ; and by
boiling soluble Prussian blue (E-ferrous ferric
cyanide, FeK-FeCyJ with HNOsAq. Changed to
Prussian blue, Fej(FeCy5)3, by prolonged contact
with air. Heated to 180^ gives off Oy and HCy.
Decomposed by KOHAq, giving FcjOjHj and
KiFeCyaAq and K3FeCyji.
Another cyanide of iron, which is probably a
ferroso-ferric ferricyanide, viz. FcjCu
= Fej"Fe.i«(FeOyj)4, is described by Eeynolds
(C. J. Trans. 1888. 767) as a black solid, formed
by heating to boiling 40 parts of bromine with
20 parts of KjFeCyj in saturated solution in a
flask with a reversed condenser for 5 or 6 hours,
washing with dilute HClAq, then thoroughly with
cold water, and drying over H^SO, in vacuo. The
substance is hygroscopic ; potash decomposes it
to FeOsHj, EjFeCy,, and KjFeCys ; it dissolves
in cone. HClAq after long digestion, giving FeClj
and FeClj ; when moist it is changed in air to
Prussian blue.
Double ferricyanides derived from
ferrous ferricyanides.
Ammonium-ferrous ferricyanid»
NH4Fe.FeCy„.liHjO (Wyrubow, A. Ch. [5] 8,
444). Corresponds with, and prepared in man-
ner similar to, the E salt (v. post), but more
stable than that salt; may be dried without
decomposition ; not ppd. from solutions by alga-
bol,
CYANIDES.
S39
Potassium-ferrous ferricyanide
KFe".FeCye. {Soluble Prussian, him.) This
salt may perhaps be better regarded as potassium-
ferric ferrooyanide KFein-PeOyj. It is obtained
by mixing FeClaAq and K^PeOyjAq in the ratio
FeCljtKjPeOyo ; solutions of known strength of
the reacting salts are poured simultaneously
into the same vessel with constant stirring, the
pp. is at once washed with cold water, and
dried over H^SOj in vacuo (Skraup, W. A. B.
[Juniheft, 1876] 74, 2nd part). It is also
formed by dissolving about 80 g. KjFeCyj in
water, and adding about 3g. FeSO,.7H20, free
from ferric salt, dissolved in water ; the pp. is
washed with air-free water containing a little
KCl, and then with pure water (Skraup, I.e.).
Dried in vacuo the salt has the composition
2(KFe.FeOys).3iH20 (Skraup, I.e.). (For pre-
paration V. also Briicke, J. 1866. 288 ; Reindel,
D. P. /. 190, 396).
A blue solid, sol. cold water, solution is de-
composed by boiling with formation of yellowish
pp. Addition of salts, mineral acids, or alcohol,
to the aqueous solution of this compound pro-
duces a blue pp. After continued washing with
alcohol, soluble blue becomes insol. in water
(Skraup, A. 186, 371). From an aqueous solu-
tion of soluble blue, containing a little alkali,
ferric salts ppt. Prussian blue, Fej(FeCy„).|, and
ferrous salts ppt. Turnbull's blue Fe,(FeCyij)j
(Skraup, I.e.). Alkalis, NHjAq, and alkali car-
bonates ppt. Fe^O^s, and form a solution of
ferrocyanide. Digested with K^FeCyjAq,
KsFeCyj, and potassium ferrous ferrocyanide
(KjEe-FeCys) are produced.
The tlue compound obtained by Williamson
{A. 57, 225) by heating potassium ferrous ferro-
ejanide, KjFe".FeCy8, with dilute HNOjAq ap-
pears to be identical with soluble Prussian blue.
This body was prepared by digesting 1 pt. white
KjFe^.FeOys with 1 pt. cone, acid and 20 pts.
water ; when the liquid was nearly boiling NO
escaped, and the lamp was removed ; treatment
with HNOjAq was continued until a samplis of
the blue compound produced gave pure FefiJiL^,
unmixed with FejO^, when decomposed by
KOHAq.
Lead ferricyanide. Grmelin gives the
formula Pb,(FeCy„)j; Schuler {W. A. B. 77,
692) gave Pb,(FeCyj)2.4H20 ; v. Zepharovioh
(W. A. B. 59 [2nd part], 800) Pb3(FeCye)2.16HjO.
According to Wyrubow (A. Gh. [5] 10, 413) the
salt with I6H2O is obtained by mixing hot solu-
tions of equivalent weights of Pb(N03)2 and
K^PeCyu, and allowing to cool. Small dark-
reddish crystals ; not e. sol. water. Double salts ;
PbK.FeCys.3H2O (Wyrubow, l.c.). The mother-
liquor from Pbs(FeCyi;)2 deposits this salt on
cooling. Red, six-sided triclinio plates ; a:b:c
= l-7205:l:-9309. Decomposes on exposure to
air. Pb,(FeCy„).,.3Pb02H2.11H,0 ;
Pb3(FeCyj)2.Pb(N0,)2.12H20 (Schuler, W. A. B.
77,692). ■
Magnesium ferricyanide Mg3(FeCy5)j;
reddish brown, non-orystallisable ; obtained by
treating Mg^FeCyj (j. v.) with 01 (Bette, A. 23,
115). Eeindel (/. pr. 103, 166) obtained the
double salt MgE-FeCyg.
Manganese ferricyanide Mn,{FeCys)2;
brownish pp. by adding KjFeCyjAq to solution
of a Mn salt (Wittstein, B, P. 63, 314), s
Nickel ferricyanide; pp. formed by add-
ing KaFeCy^Aq to solution of a Ni salt is prob-
ably Nis(Fe0y„)2 (0m. 7, 500). According to
Eeyrioso (A. Ch. [3] 30, 252) addition of
KsFeCy^Aq to an ammoniacal solution of a Ni
salt produces a yellow pp. of the double salt
Ni3(FeCy„)2.4NH3.H20.
Potassium ferricyanide K^eCj^. (Bed
prussiate of potash).
formation. — 1. By adding PbO, to
E^FeCygAq, and neutralising the KOH produced
by an acid (Seuberlich, D. P. J. 238, 484).— 2. By
adding BrAq to KjFeCyuAq until FeCljAq ceases
to give blue pp. — 3. By passing ozonised O into
K,FeCyeAq. — 4. By electrolysing E^FeOysAq
(Sohlagdenhauflen, J. 1863. 305).
Preparation.— 1. K^FeCycAq is digested with
potassium-ferrous ferrocyanide, K2Fe.PeCyg
{q.v. p. 334) the liquid is filtered and crystallised
(Williamson, A. 57, 225).— 2. Well washed 01 is
passed into cold K^FeCyjAq, with constant agita-
tion, until a few drops of the liquid give a brown-
red colour, but no pp., with FeOl3Aq ; the liquid
is evaporated, and the crystals are repeatedly
reorystallised from water [KiFeCy„Aq -)- 01
= K01Aq + K3FeCy8Aq] (Gmelin, S. 34, 325;
Zimmermann, D. P. /.,127, 211). If the passage
of 01 is continued too long some Prtissian green
is formed {v. Ferroso-ferric ferricyanide, p. 338) ;
to remove this, Posselt (A. 42, 170) evaporates
to the crystallising point, then adds 2 or 3 drops
of KOHAq (not more), filters from FCjOAi ^.nd
allows the liquid to crystallise. — 3. Ehien
(D. P. J. 206, 151) recommends to mix HClAq
with cold KjFeCysAq in the ratio 2K<FeCyj:H01,
and then to add a cold filtered solution of bleach-
ing powder until Fe0l3Aq gives no blue pp. ;
any excess of acid is then neutralised by OaOOj,
and the solution is evaporated to the crystallising
point. The first crop of crystals is pure, the
subsequent crops contain traces of lime which
may be removed by re-orystallisation.
Properties. — ^Large red prismatic crystals;
monoolinic,a:6:c = ■7457:1"5985 (Kopp,Zrj/stoZZo-
graphie, 311) ; according to Schabus ( W. A. E.
1850. 582) the crystals are trimetric with the
ratio of axes ffl:6:c = l-2418:l-6706:l. S.G. 1-8-
1-85 (Schabus, l.c. ; Wallace, 0. J. 7, 77). S.
33 at 4-5°, 36-6 at 10°, 89-4 at 15-5°, 58-7 at 38=,
77-5 at 100°, 81-9 at 104° ( = B.P. of saturated
solution) (WaUaoe, l.c.). S.G. of KaFeOyjAq
saturated at 15-5° = 1-178 (Schift, A. 113, 199).
Nearly insol. alcohol. H.F. [K», Fe, CyT
= 278,700 ; data obtained by oxidising K^FeOyjAq
by 01 and Br, also H^FeCyjAq by Br, and re-
ducing Zn3(FeOyj)2 by HIAq (Joannis, C. B. 94,
449, 541, 725).
Beacttons. — 1. Seated in a closed vessel, de-
crepitates, evolves Oy and a little N, residue con-
sists of K0y,K4p'eCyj, Fei(FeCy5)3, C, Fe, and prob-
ably paraoyanogen. Heated in air, Oy is evolved
and Fe203 and KOy remain. — 2. KjFeOyeAq is
reduced to K^FeCyjAq by the action of sunlight
(not by yellow light) (Vogel, B. 4, 90 ; Schon-
bein, P. 67, 87) ; also reduced by HjS (William-
son, A. 57, 225) ; by alkali sulphide (Liesching,
D. P. /. 128, 206) ; by thiosulphates (Diehl,
J. pr. 79, 430; of. Lowe, /. 1857. 273) ; by HI
(Lenssen, A. 91, 240) ; by reduced Ag, Zn, Fe,
Bi, &c. (Eder, /. pr. [2] 16, 211 ; Bottger, 0. 0.
1872. 708) ; by ferrous salts when hot (Skraup
z2
340
CYANIDES.
A. 186, 371) ; by Hj,Oj,Aq in alkaline solution
■(Weltzien, .4. 138, 129) ; also by SO^Aci, phos-
phites and hypophosphites ; also by many or-
ganic reducing agents, e.g. formic acid (Sohon-
bein, ' P. 67, 87). — 3. Alkaline solution of
Kjl^eCyj acts as an oxidiser, e.g.; towards sugar,
starch, alcohol, oxalic acid (WaUaoe, C. J. 7,
77), indigo (Mercer, P. M. [3] 81, 126) ; NO is
oxidised to HNOj, P to HjPO.,; and S is said to
be oxidised to H^SOjAq (Wallace, I.e.). — 4. Am-
moma reacts with EaFeCyjAq to form KjPeCyj,
(NHj)^FeCyj, and N (Mouthiers, J. Ph. [3] 11,
254). — 5. Potash when boiled down with cone.
KsFeCyjAq produces KjFeCyj and KCy, evolv-
ing Cy and ppg. Fefi, (Boudault, J. Ph. [3] 7,
437). — 6. Some oxidisable metallic oxides, e.g.
PbO, CrjO,, MnO, SnO, when boiled with
KaFeCysAq in presence of KOH, form K^FeCyjAq,
and a higher oxide of the metal ; OoO and NiO
are not thus oxidised ; salts of Ag and Au pro-
duce Fe^Oj with solution of KiFeCyj and double
cyanide of K and Ag, or K arid Au. — 7. When
mercuric oxide is boiled with EsFeCyjAq,
HgCy^Aq is formed, and the whole of the Fe is
ppd. as Fe^Oj (Gmelin).— 8. KaFeCyjAq is decom-
posed by excess of chlorine with production of
HCy and CyCl ; on boiling, or on addition of
alkali, the liquid deposits ferroso-ferric ferri-
cyanide Fe,™.Fe3«(FeCyj)5 (g. v. p. 338). Bro-
mine, in excess, and with prolonged action, pro-
duces Prussian blue ; when the action is con-
tinued for a shorter time a black cyanide of
Fe, FejCy,,,, probably a ferroso-ferric compound
Fe3"Fe2"i(FeCye)4, is formed (v. p. 338) ; when
the ferrioyanide is in excess TurnbuU's blue is
produced (Eeynolds, C. J. Trans. 1888. 767).—
9. Nitric acid produces nitroprusside of potas-
sium {q. V. p. 341) and nitre (Playfair, P. M. [.3]
26, 197, 271, 348).— 10. Hydrochloric acid when
boiled with KaFeCy^ forms KCl.FeGlj, and Turn-
bull's blue, FejfKeGyB)^. — 11. Nitric oxide pro-
duces K nitroprusside (Bunge, Z. 1866. 82).
Combination. — With potassium iodide to
form KjFeCyj.KI ; very unstable salt (Preuss, A.
29, 323 ; Mohr, A. 105, 57 ; Blomstrand, J. pr.
[2] 3, 207 ; cf. Kern, C. N. 33, 184).
The double salts KNa^FeCyj, KjNa3(FeCyj)2,
KjKaFeCyg, have been isolated (■». Eeindel, /. pr.
102, 43 ; ibid. Z. 1870. 147 ; Laurent, 3. 1849.
291; Wyrubow, Bl. [2] 12, 98; 14, 145).
Silver f err icy anide AgjFeCyj. Orange
yellow salt obtained by adding KjFeCyjAq to
AgNOjAq. When freshly ppd. AgsFeOyj is treated
■ with NH3Aq, or when KjFeOyjAq is added to
AgNOjAq with enough NH^Aq to form a clear
liquid, a reddish pp. of the double salt
2Ag3FeCyo.3NH3.^H20 is produced (Gintl, W.A.B.
59, 554). This compound dissolves in excess of
NHjAq, and on heating decomposes, giving
(NHJ,FeCy„Aq, NHjAq, Ag,|FeCye, and N.
Sodium ferricyanide NajFeCyj.H^O.
Euby-coloured deliquescent prisms ; obtained by
oxidising Na^FeCyjAq by CI and evaporating.
S. 16-9 cold water, 80 at 100° (Bette, A. 23, 115;
Eeindel, J. pr. 102, 43 ; Kramer, J. Ph. 15, 98).
Tin ferricyanides ; stannousferricyanide
Sn3(FeCyj)2, gelatinous pp. by adding EjFeCyjAq
to SnClj solution. Wyrubow {A.Ch. [5] 8, 444)
gives the formula Sn,(FeCyj)4.25H20. i
Ferrieyamdes of wra/m/um, vanadium, and
sine probably exist, but there is little accurate
knowledge regarding them.
NiTKOPKTjssiDES (Nitrovrussiates. Niiro-
ferrieyamdes.) Salts of nitroprussic acid
HjFeOsNjO (probably H^FeCyj.NO). These salt?
were discovered by Playfair in 1850 (P. M. [3]
36, 197, 271, 348). They have been studied by
Gerhardt, Hadow, Eoussin, and others, but their
constitution cannot be regarded as finally deter-
mined. The nitroprussides are formed by reac-
tions between nitric acid and tihe alkali ferro- or
ferri-oyanides, or between ferro- or ferri-cyanhy-
drio acid and nitric oxide, or by adding KNO,
and a dilute acid to a ferrocyanide. The first
products of the reaction between KjFeCyjAq and
HNO3 are KjFeCyj and NC( ; these then react
to produce K nitroprusside with evolution of HCy,
N, and CO^. According to Jensen (/. Ph. [5] 11,
315) continued electrolysis of KjFeCyj produces
a liquid which gives the reactions of K nitro-
prusside. By boiling a mixture of FeCl,Aq and
KCy, to which KNOj has been added, K nitro-
prusside is formed ; according to Eoussin {A.Oh,
[3] 52, 285) this process is analogous to that
whereby iron rdtrosulphide (g. v. under Iboh) is
produced, K2S being used in place of KCy.
Alkali nitroprussides are soluble in water ; the
insoluble salts, e.g. of Cu, Fe, Zn, are obtained
from these by double decomposition ; the Fe or
Cu salt decomposed by NHjAq, GaOAq, or
BaOAq, gives a solution of the NHj, Ca, or Ba
nitroprusside. The nitroprussides are generally
coloured and crystallise well. A solution of a
nitroprusside gives a deep brilliant purple colour
with an alkali sulphide ; the colour soon fades ;
this reaction is used as a very delicate test for
nitroprussides. The nitroprussides are decom-
posed by boiling with alkalis, giving Fej03, N,
alkali ferrocyanide, and probably alkali nitrite.
With HjS they give Fe^Os, Prussian blue, S, a
ferrocyanide, and a nitrosulphide of Fe ; they
are not usually changed by SOj, sulphites, or
thiosulphates, but are decomposed by hot cone,
E2SO4. Some of these salts are stable ; others
undergo change in solution with ppn. of Prus-
sian blue or Fe.ft,.
The constitution assigned by Gerhardt to the
nitroprussides (Traiti, 1, 344) was M.^FeCy5.N0
[M = K, — , &c.] which represents the com-
2
pounds as salts of a dibasic acid containing
the groups NO and Cy in combination with Fe.
The reaction between ferricyanhydric acid and
nitric oxide is represented thus : HjFeCy„ + NO
= H2FeCy5.NO + HCy. Hadow (0. J. [2] 4. 341)
supposed that the nitroprussides contained the
group N2O3, because NO2 does not change
KjFeCyjAq acidulated with HjSOj, whereas
nitroprusside is formed by passing the gas
evolved by heating starch with nitric acid into
KjFeCyjAq. Stadeler (Z. 5, 559) represents the
preparation of K nitroprusside by the action of
nitric acid on KjFeCyj (Playfair's method) by
the following equations (supposing that HjFeCy,
is first formed) (1) 2H,FeCy„Aq + HNO,
= 2H3FeCy3Aq + HNOjAq + HjO j
(2)2H3FeCy,rAq + 2HN02
= 2H23?eCy.j(NO) + 2H2O + Cyj.
Eegarding constitution of nitroprussides v, Kyd
(4. 74, 340), Weith (if. [2] 4, 104).
OXANIDES.
341
Nitroprussic acid SJ^60^TSfi.B..fi ; pro-
bably HjFeCyj.NO.HjO {Nitroferricyanic acid.
Nitroferricyanhydric acid.) Obtained by decom-
posing the Ag salt by an equivalent quantity of
HClAq, or the Ba salt by an equi|falent of
H^SOjAq, filtering, and evaporating in vacuo.
Dark red deliquescent crystals ; very easily de-
composed in solution with formation of HGy and
Fe,Ps (Playfair, l.c.).
Ammonium nitroprusside
(NHj)2FeC5NjO. Obtained by decomposing the
Pe salt by NHjAq, filtering and evaporating
gently. Very unstable ; solution deposits Prus-
sian blue when boiled (Playfair).
Bariumnitroprusside'Ba.FeC^liifi.SiLp.
Obtained similarly to the NHj salt. Dark red,
very soluble, quadratic crystals ; give off most of
their Hfl at 100° (P.).
Calcium nitroprusside
CaFeC5Nj0.4H20; very soluble, easily decom-
posed, crystals (P.). _
Copper nitroprusside CuFeC5N|,0.2H20 ;
greenish pp. becoming grey on exposure to light;
produced by adding solution of the K or Na salt
to Eolation of a Cu salt (P.).
Iron nitroprusside (ferrous). Yellowish
pink pp. by adding KjFeCsNsOAq to a ferrous
salt ; ferric salts give no pp. Decomposed by
alkalis. Probably Fe.FeC^N.O (P.).
Potassium nitroprusside
K,FeCjN,0.2H,,0 (P.; also Enz, Vierteljahr.
Plmrm. 2, 239). Prepared similarly to the so-
dium salt (q. v.). Dark red monoclinic crystals.
S. c. 100 at 16° ; sol. alcohol. Very deliquescent ;
solution slowly deposits Prussian blue. The
basic salt 'K.;SeC,)ifi.'Kf).B.fi is obtained by
mixing a solution of the normal salt with twice
its volume of alcohol, and then adding potash.
Jensen (J. Ph. [5] 11, 315) prepared the salt by
reacting on KjFeCyj with Ca hypochlorite solu-
tion.
Silver nitroprusside kg^eC^fi. Flesh-
coloured pp. obtained from the Na or K salt by
adding AgNOjAq ; insol. water, alcohol, or
HNO^Aq (P.).
Sodium nitroprusside
NaiFeC,,Nj0.2H20. The other nitroprussides
are made from this salt.
Preparation.— Vawc parts powdered K^FeCy,
are mixed with e. 5| parts nitric acid S.G. 1'36,
the cone, acid being diluted with its own volume
of water. The acid is poured on to the salt in one
quantity ; the lowering of temperature is sufficient
to moderate the reaction. The salt dissolves
forming a cofiee-coloured liquid, and evolving
COj, N, Cy, and HCy ; the liquid is placed in a
large flask, and warmed on the water-bath so
long as gases are evolved, and until the liquid
gives a dark green or slate-colonred pp., instead
of a blue pp., with a ferrous salt ; on cooling,
crystals of ENO, mixed with a little oxamide are
deposited; the mother-liquor is neutralised by
Na^COa (if K^CO, is used, K nitroprusside is ob-
tained) and boiled ; it is then filtered, and
evaporated at c. 40°, or better in vacuo, until
crystallisation begins on cooling ; the KNO, sepa-
rates, and the mother-liquor yields the_ nitro-
prusside which is purified by recrystallisatjoii
from water, the prismatic crystals which forai
being removed from the hot liquid, dissolved in
a little hot water, and allowed to crystallise by
cooling (in this way the KNOj is separa^ted) (P.;
cf. Weith, A. 147, 312; Overbeok, Ar. Ph. [2] 72,
270; Boussin, J. 1852.438; Schafarik, W.A.B.
47, 262).
Pro2>erties amd Reactions.— haige rubj-red
triclinic prisms ; non-deliquescent. S. c. 40 at
15°- Does not lose water at 100° (P. ; also
Eammelsberg, P. 87, 107). 1. Aqueous solution
decomposes rapidly in sunlight or on heating
with ppn. of Prussian blue (Eoussin, J. 1863.
309). — 2. Electrolysis also produces Prussian blue
(Sohlagdenhaufien, J. 1863. 305 ; Weith, A. 147,
312).^3. An alkaline solution acts as an ener-
getic oxidiser (Stadelei-, A. 151, 1). — 4. Boiled
with alkalis FejOjH, is ppd., N evolved, and the
solution contains a nitrite and a ferrooyanide.—
5. Sulphuretted hydrogen ppts. S and Prussian
blue, and NajFeCyj remains in solution. — 6. So-
diwm amalgam, in presence of acetic acid, pro-
duces a yellow colour, and alcohol causes a pp.
in this liquid (for details v. Weith, A. 147, 312).
7. Oxidised to NaNO, and Na^FeCyj hy potassium
permanganate in alkaline solution (Weith, l.c.).
8. Decomposed by chlorine when heated with it,
or when exposed to sunlight (Davy, G. N. 38,
105). — 9. Decomposed by bromine at tempera-
tures above 100° (Weith, I.e.). — 10. Easily decom-
posed by cone, sulphuric acid. — 11. With soluble
metallic stilphides, including NH, sulphide, a
deep purple colour is produced ; the liquid soon
becomes turbid, and ppts. S and Fe.^03, while
NaN02, Na,FeCyj, and NaSCy remain in solution.
If an alcoholic solution is used the coloured
body separates in oily drops, which give a green
powder when dried in vacuo (Playfair).
Zinc nitroprusside ZnFeCsNjO. Yellow-
rose pp. by adding K^FeCsNaOAq to solution of a
Zn salt.
Pebfekkooyanldes. — When K^FeCyuAq is
heated with I a greenish-brown liquid is formed,
from which alcohol ppts. a crystalline salt ; this
salt dissolves in water forming a dark reddish
violet liquid (Stiid^ler, A. 151, 1). The salt is
better prepared by mixing powdered KjFeCyj
with KCIO3, adding HClAq, heating very gently,
neutralising by Na^CO, after disengagement of
gas has ceased, evaporating, ppg. by alcohol, and
again dissolving in water and ppg. by alcohol
(Bong, Bl. [2J 24, 268 ; Skraup, A. 189, 368).
The salt is nearly black ; it dissolves in water,
is deep violet ; the compound is very unstable,
soon giving off Cy ; even in the dark it changes
colour to greenish black, and then dissolves to
form a green solution. Boiled with water ij
forms KjFeCyiiAq and Fe2(0H)s. -An aqueous
solution of this salt gives green pps. with many
metallic salts ; it acts as an energetic oxidiser.
Nitric acid forma K nitroprusside, KjFeCsNjO.
The salt probably has the composition K^EeCy^ ;
if this is established the relation of potassium
perferricyanide to potassium ferricyanide ia
similar to that of the ferri- to the ferro-cyanide
(K^FeCy,, K,FeCy„ K,FeCy„).
Lanthanum cyanide, LaCy^ (Frerichs a. Smith ,
ji. 191, 365). A gelatinous pp., formed by adding
solution of La2(S04)a to KCyAq; forms double
cyanides, e.g. 2LaCy3.3PtCy2.18H20.
Lead cyanides. No cyanide of Pb has been
isolated. Pb salts are not ppd. by HCNAq ; but
if NHj is present a white pp. of lead oxycyanlde
PbCy2.2Pb0 is obtained (Erleifmeyer, J. pr. 48,
342
CYANIDES.
356; Sutler. A. 06, 63). KCyAq added to Pb
salts gives a pp. insoluble in excess of KCy.
Joannis (C. B. 93, 271) gives the thermal data
[Pb, Gm\ 2PbO, ffO] =17,800 (formation of
solid PbOy2.2PbO.H2O from gaseous Cy^ and
other materials as solids). Bammelsberg (P. 42,
114) says that addition of ZnCy2.2KC!yAq to solu-
tion of a lead salt ppts. PbCyj.ZnCyj. The ohloro-
oyanide 2Pb0y2.PbCl2 is described by Thorp
(Am. 10, 229) as obtained by digesting PbOlj with
KCyAq.
Magnesium cyanide. Not isolated; solution
of MgO in HCNAq soon decomposes with evolu-
tion of HON (v. Sohulz, J.pr. 68, 257).
Manganese cyanides. No simple cyanide of
Mn has been certainly isolated (Eaton a. Fitti^,
A. 145, 157). Several compounds are known
which are best regarded as salts of mangano-
cyanhydric acid H^MnCyj, which acid has itself
been isolated, and manganicycmhydric acid
HaMnOye-
Manganocyanhydric acid H^MnCyj.
Obtained by decomposing the Pb salt by H^S,
filterinjf, and evaporating in vacuo over H2SO4 ;
insol. in ether, si. sol. in alcohol (Desoamps,
A. Ch. [5] 24, 178). The Pb salt is obtained by
adding Pb(C2H,02)2Aq to a freshly-prepared
solution of KiMnCyj, which is itself formed by
adding 10 grams manganous acetate to 40-45
grams KCy in 100 c.c. almost boiling water, and
then adding 15-20 grams KCy, and dissolving
the crystals of K^MnCyj (which separate on
cooling) in water (Christensen, J'.jpr. [2] 31, 163).
Manganocyanides. KjMnCyj.CHjO (for
preparation v. supra); deep -blue quadratic
crystals; lose 6H2O over H2SO4; may be crystal-
lised unchanged from a little KCyAq (Eaton a.
Fittig, A. 145, 157 ; Desoamps, A. Ch. [5] 24,
178). IFreshly-prepared solution of this salt gives
pps. with most metallic salts ; the following are
soluble in water and orystallisable :— BajMnCyj;
BaKjMnCys ; OajMnCys ; Na4MnCy,16H20 ;
SrjMnCys (E. a. F., l.c. ; D., l.c.). Addition of I
to K^MnCyjAq ppts. aU Mn as hydroxide (Beil-
stein a. Jawein, B. 12, 1528). According to
Desocmps (A. Ch. [5] 24, 178) passage of NO
into manganocyanides produces salts analogous
to mtroprussides (q. v. p. 340).
Mfinganicyanides. KjMnCyj is obtained
by allowing solution of K^MnCy, in KCyAq to
oxidise in air (Eaton a. Fittig, A. 145, 157) ; or
by adding manganous acetate to warm KCyAq
until the liquid is deep-red, filtering, and cool-
ing (Christensen, J.pr. [2] 31, 163). Reddish-
brown needles, isomorphous with KjPeCyB (Ram-
melsberg, P. 42, 112 ; Handl, W. A. B. 32, 246).
By long boiling with water all Mn is ppd. as hy-
droxide. Other manganicyanides described are
Bas(MnCys)„ Caa(MnCyj)j, and NajMnCy,.2H20
(Baton a. Fittig, A. 145, 157). The manganicy-
anides are reduced to manganocyanides by Na-
amalgam (Desoamps, A. Ch, [5] 24, 178).
Mercury cyanides. Only one cyanide of Hg
is known, HgCyj; it forms very many double
cyanides, and also combines with many other
salts to form double compounds. When Hg^O is
heated with HCNAq, HgCy^ and Hg are formed.
Mercuric cyanide HgCyj. Prepared by
boiUng Prussian blue with HgO and water ; or
by boiling 1 part K |FeCy„ with 2 parts HgSOj
und 8 parts water ; or by dissolving ligO in sliglit
excess of HCNAq and crystallising. Whit*
quadr.atic prisms (De la Provostaye, A. Gh. [3]
6, 159; Kopp, EinUitung in d. Krystallog. p.
163). S.G. 4-0 (Schroder, B. 13, 1070). Very
poisonous. Sol. in about 8 parts water at ordinary
temperature, much more sol. in hot water, insol.
in absolute alcohol. When heated gives Hg, Cy,
and paracyanogen (Johnston, A. 22, 280 ; Troost
a. Hautefeuille, O. B. 66, 735, 795). Solution not
ppd. by alkalis ; but readily decomposed by HjS,
also by HClAq; very slightly decomposed by
other dilute acids in the cold (Plugge, Fr. 1879.
408). Decomposed by heating with cone. HjSO,;
decomposed by 01, Br, and I, giving HgClj', &c.,
and CyCl, <fcc., action of 01 is attended with ex-
plosions (Bonis, A. 56, 267 ; 64, 305 ; Weith, B.
6, 1705 ; Serullas, A. Ch. 35, 293 ; Steuhouse,
^.33,92). H.F. [Hg,Cy^] = 18,950; [HgCyUqJ
= -2,970 {Th. 3, 512).
Merc%(,ric oxycyanide HgCyj.HgO.
Small needles, formed by dissolving HgO in
warm HgCyjAq, and crystallising. Very slightly
sol. in water ; explodes when heated (Johnston,
T. 1839. 113 ; Schlieper, A. 59, 10 ; Clarke, B.
11, 1504). Joannis (0. B. 93, 271) gives the
thermal data [HgCy^HgO] = 2,400.
Double cyanides containing mer-
curic cyanide: — HgCy2.2KCy; obtained as
transparent octahedra, unchanged in air, by dis-
solving HgCy2in hot KCyAq and crystallising, or
byheatingHg0y2withHCyAqandK20O3(Genthcr, ,
A. 106, 341). H.F. [Hg,Cy^2KCyAq]- 27,780;
[HgCyS2K0yAq] = 8,830 ; [HgCy»Aq,2KCyAq]
= 11,800 {Th. 3, 472). Dissolves in c. 4 parts
cold water ; solution gives pps. with soluble salts
of Zn,Pb,&o., these pps.being double cyanides of
Hg and the other metal ; the following have been
isolated :— SHgCyj.aCdCy^ (SchiUer, A. 87, 46) ;
Hg0y2.HgO.7AgCy (Bloxam, B. 16, 2669) ;
HgCy2.N(CHj)4Cy (Claus a. Merck, B. 16, 2737).
Double compounds of mercuric
cyanide with metallic salts (Desfosses,
J. Ghim. Mid. 6, 261 ; Geuther, A. 106, 241 ;
Dexter, C. G. 1862. 597 ; Brett, P. M. [3] 12,
235 ; Poggiale, C. B. 23, 762 ; Liebig, S.49, 253;
Weeren, P. 93, 461 ; Clarke, B. 11, 1504 ; Ahlen,
Bl. [2] 27, 365 ; Caillot, A. Ch. [3] 12, 235 ; 19,
220; Berthemot, P. 22, 620; Kletzinsky, Z. 1866.
127 ; Nylander, J. pr. 79, 879 ; Wohler, P. 1,
231 ; Kessler, P. 74, 274 ; Caillot a. Podevin, /,
Ph. 11, 246 ; Bammelsberg, P. 42, 131 ; 85, 145 ;
Darby, A. 65, 204 ; Kane, A. 35, 356 ; Bookmann,
A. 22, 153 ; Philipp, P. 131, 86 ; Winckler,
Btcchner's Bepert. 31, 459 ; Claus a. Merck, B.
16, 2737 ; Custer, A. 68, 323 ; Apjohn, P. M. 9,
401).
I. With chlorides : with NH^Cl, BaClj, CaClj,
MgCl2, SrClj, NaOl, UnC\„ ZnClj (Brett^ Poggiale);
with KCl (Defosses, Geuther, Dexter) ; with CoCl,,
FeCls, NiOlj, SnOl, (Poggiale, Dexter) ; with
HgClj (Poggiale, Liebig, Weeren, Clarke) ; with
chlorides of Ce, Di, Sr, La, and Y (Ahl^n).
II. With bromides : with BaBrj, SrBr,, NaBr
(Caillot) ; with CaBr2 (Custer) ; with KBr' (Brett,
CaiUot, Berthemot).
III. With iodides : with Cal2 (Poggiale) ; with
Balj, Srl2, Nal (Custer) ; with KI (Apjohn,
Caillot, Geuther, Kletzinsky).
IV. With other metallic salts : with KCIO,
(Poggiale) ; with nitrates of Cd, Co, Cu, Fe, Mn,
Ni, Zn (Nylander); with AgNOj (Wohler, Qea-
CYANIDES.
S43
ther) ; with HgNO^ (Geuther) ; with K^S^Oj
(Eessler) ; with KfijOt and kgfifif (Caillot a.
Podevin, Eammelsberg, Darby) ; with K^FeCyB
^ane) ; with sulphooyanides of Ba, Ca, Mg, K
(Bookmann, PhUipp) ; with H.CO jNH4 (Poggiale) ;
with H.COjK (Winokler) ; with Na-O^HaOa (Ous-
ter).
V. With organic ammonium derivatives and
alkaloids. HgCy, reacts with N(CHj)4l to
form two isomeric compounds : a white salt
HgCy2.N(CH3)4l, and a yellow salt
HgCyI.N(CH3)4Cy (Glaus a. Merck). HgOy^
forms double compounds with aniline cyanhy-
dride, with iodq-ethyl quinine, iodo-ethyl cin-
chonidine, and iodo-ethyl strychnine (Glaus a.
Merck).
Nickel cyanides. Only one cyanide of Ni is
known, NiCy,; it forms several double cyanides;
neither nickelo-cyanides nor nickeli-cyanides cor-
responding to the cobalto- and cobalti-cyanides
have been isolated.
Niekelous cyanide NiCyj.aiBLjO. Apple-
green pp. obtained by adding KOyAq to solution
of a Ni salt, or HCNAq to Ni acetate solution.
Loses all water at c. 200° ; at higher temperatures
decomposes, evolving Cy and N, and leaving Ni
and a carbide of Ni. Soluble in excess of KOyAq
to fohn NiGyj.2KCy (Wohler, Oehlen's Joum. 6,
234 ; Bammelsberg, P. 42, 114).
Double cyanides containing niekel-
ous cyanide. NiCy2.2KCy.H2O; obtained by
. adding excess of KCyAq to solution of a Ni salt,
evaporating, and crystallising. Bed-yellow mono-
clinic prisms ; S.G. 1'875 at 11°. Loses all water
at 100°. Solution decomposes slowly on heating
(Balard, G. E. 19, 909 ; Eammelsberg, P. 42,
114 ; 90, 35 ; Clarke, J. 1877. 43). The following
double cyanides have also been isolated:
NiCy2.2NH,0y (Wohler, Oehlen's Joum. 6, 234) ;
NiOy2.BaCy2.3H2O (Wohler, l.c. ; Weselsky, B. 2,
688 ; Mouthiers, A. 64, 297) ; NiCy2.Ca0y2.a;H2O
(Wohler, l.c.) ; NiCy2.2NaOy.3HjO (Wohler, i.e. ;
Eammelsberg, P. 42, 114) ; Ni0y2.SrOy2.a;H2O
(Handl, W. A. B. 32, 246). Solutions of these
double cyanides are decomposed by dilute acids
with ppn. of NiOyj, and evolution of HOy ; HgO
decomposes them ppg. NiOy2 and NiO; CI or
Br ppts. NijOj.
Niobium cyanide. No cyanide of Nb has been
isolated. When NbjOs is strongly heated vrith
Na200, and charcoal in a current of air, a metal-
like solid is formed resembling the compound of
Ti with Cy and N ; this solid is possibly analogous
in composition to the Ti compound {v. Titanium
cyanides) (Joly, C. B. 82, 1195).
Osmium cyanides. One cyanide of Os, OsCy2,
and osmoeyanhydric acid H^OsCyj and some of
its salts, have been prepared.
Osmous cyanide 0s0y2. Dark violet soUd
obtained by continued boiling H^OsOy,, with
HClAq (Martins, A. 117, 357).
Osmoeyanhydric acid HjOsCyj. Ob-
tained by adding cone. HOlAq toK^OsCyjAq
{q.v.), collecting the pp. which forms, washing
it with cone. HOlAq, and crystallising from al-
cohol by adding a few drops of ether. White
hexagonal prisms ; unchanged in dry air ; in
moist air decomposes to OsOyj and HON ; sol.
in water and alcohol, ppd. by a little ether (Mar-
tius, A. 117, 857).
OsnlocyanideS. Kj03Cy..3HjO ; prepared
by ditisolving 1 part osmic acid in KOHAq until
the liquid remains feebly alkaline, adding 1);
parts KGy, evaporating to dryness, heating in a
closed vessel, dissolving in water, and crystal-
Jising once or twice (Martins, 4. 117,357; Glaus,
Beitmge jj. Chemie d. PlaOmnetalle [Dorpat,
1854], or /. 1855. 444; Claus, J. pr. 85,129),
Tellow-white plates isomorphous with KiFeCyj
(Glaus, J.pr. 85, 129). The following osmooyan-
ides have also been described: Ba20s0y5.6H2O
(Martins, A. 117, 357) ; BaKjOsCyj.SBLjO (Mar-
tins, Z.C.). K^OsOyjAq §ives ppa. with many
metaUio salts.
Palladium cyanides. Two cyanides of Pd,
PdCy^ and PdOy^, are known. Several double
cyanides of PdOyj have been prepared. They
may be regarded as derivatives of the hypothe-
tical palladium-cyanhydric acid HjPdCy,; this
acid has not been isolated, but the analogies in
crystalline form and general properties between
the double cyanides of PdCy, and those of PtOy,
point to the Fd salts as being derived from
H2PdCy4 ; the acid H2PtGy4 is known.
Palladpus cyanide PdOy2. Tellow-white
pp. obtained by adding HgOy^Aq to neutral PdOlj
solution. Decomposed by heat to Fd and Gy ;
not decomposed by ordinary acids nor by HgO ;
soluble in NH,Aq, from which solution the com-
pound FdOy^.^NHj separates in white needles ;
soluble in KOyAq forming PdCy^. 2KGy (Berzelius,
P. 18, 460; Fehling, A. 39, 119; Bossier, Z.
1866. 175). Joannis (0. B. 95, 295) gives some
thermal data: [Pd,Oy^ = 23,600 (solid PdOyj
from gaseous Cy and solid Fd) ; [PdO,2HCyAq]
= 44,800 (giving solid PdCy2).
Palladia cyanide FdGy,. Beddish pp.
easily decomposing with evolution of HCN ; ob<
tained by shaking HgCy^Aq with FdCV2K01.
Double cyanides of palladous cyan-
ide, or pallado-cyanides. FdOy2.2NH4Cy
(or (NHJjPdCyj) ; obtained by adding HgCyjAq
to an ammoniacal solution of a palladous salt ;
said to be ppd. by adding HCNAq to
FdGl2.2NH4Gl (Croft, J.pr. 104, 64 ; v. alsoBossler,
^.1866. 175). PdCy2.BaCy2(orBaPdCy,).4H20;
large greenish monoclinic prisms; formed by
adding HCNAq to a mixture of PdCy2 and BaOO,
(Bossier, Z. 1866. 175; Weselsky, B. 2, 588).
FdCy2.2KCy (or KjPdCyj ; obtained by dissolving
FdCy2 or Pd black in KOyAq, and crystallising.
Crystallises with 3H2O in white monoclinic crys-
tals, or with H2O in lustrous tablets (Bossier, Z,
1866.175). The following double cyanides are also
described by Bossier (l.c.) ; FdCy2.GaCy2.4HjO ;
PdCyj-CuCyj; PdCy2.FbCy2; PdOy2.MgCy2.4H2O,
this compound forma the complex cyanide
MgFdOy4.MgPtCy4.14H20 (Bossier) ;
FdCy2.HgOy2; PdCy2.2AgCy; ■ FdCy2.2NaCy.
Most of these double cyanides are isomorphous
with the corresponding platinooyanides which
are derivatives of the acid HgPtCyi. Solutions
of the Pd double cyanides are decomposed, slowly
in air, more quickly by acids, with separation of
FdCy2 ; HjS ppts. FdS ; Zn ppts. Fd.
Platinum cyanides. Platinum cyanide PtCyg
is known ; also platincyanhydrio acid H2FtCy4,
and many salts derived therefrom ; there are also
several compounds which may be regarded as
additive compounds of the platinocyanides with
halogens, or better as derivatives of perchloro-
{bromo- or iodo-) plaUncyanhydi-ic acid
344
CYANIDES.
fljX^PtCyj; and finally there are some com-
pounds of doubtful composition.
Platinous cyanide PtCyj. Obtained by
heating PtCy2.2KCy (prepared by heating KCyAq
•with cone. PtCLjAq, or by warming PtCl4.2NH,Cl
with KCy and a little KOH) with HgCl^; or by
heating' PtCy2.HgCy2 (prepared by adding
HgCljAq to PtOyi,.2KCyAq) (Dobereiner, A. 17,
250; Quadrat, A. 63, 164). Also formed by
heating PtCy2.2NH,Cy to 300° (Schafarik, J. pr.
66 385); also by heating PtCy2.2K0y with oouo.
H2SO4 (Enop a. Sohnedennann, J. pr. 37, 461) ;
also by ppg. neutral PtCljAq by HgCy^Aq (Boss-
ier, Z. 1866. 175) ; also, along with other pro-
ducts, by heating H^PtCys with HNOjAq (Scha-
farik, I.e.). Sulphur-coloured solid; insol. in
water, acids, and alkalis ; when heated gives Cy
and Pt ; dissolves in alkali cyanides forming
platinocyanides ; when freshly ppd. dissolves in
NHjAq.
Platinocyanhydric acid H^PtCyj. HCN
is passed into a mixture of 1 part PtCl^ with 1^
parts BaCOj suspended in 5 parts water kept
nearly boiling ; the passage of HON is continued
so long as COj is evolved ; BaPtCyj.iHjO crys-
tallises out on cooling ; this salt is dissolved in
water (1 part dissolves in 33 parts water at 16°),
and an equivalent quantity of H^SOjAq is added ;
the filtrate from the ppd. BaS04 is evaporated
at a gentle heat and crystallised (Weselsky, J. pr.
69, 276). Or CuPtCy^ is prepared by adding
PtCy2;2ECyAq to Cu(N03)2Aq, and the Cu salt is
decomposed by H^S (Quadrat, A. 63, 164). Crys-
tallises with 5H2O in cinnabar-red prisms with
blue sheen on surface, or with more than SH^O
in yellow-green, metal-like crystals, or in blue-
black needles. Deliquescent. Very sol. in water
and alcohol. Heated, decomposes above 140° to
HON and PtCyj. Carbonates are decomposed
by H^PtOy,.
Platiuocyailides. These salts generally
form very beautiful dichroio crystals; the soluble
salts may be prepared by decomposing BaPtCyi
by the various metallic sulphates ; the insoluble
platinocyanides may be formed by adding the
various metallic salts to KjPtCyjAq.
AmmQnium platinocyanide
(NHj2PtCy,.H20. White, translucent needles;
crystallises with 2H2O as yellow prisms ; both
with blue reflection. V. sol. water (Schafarik,
J. pr. 66, 385 ; Quadrat, A. 63, 164 ; Knop a.
Schnedermann, J.pr. 37, 461). An hydroxyl-
ammonium salt (NHjO)2PtCyi.2H20 is known;
and also the double salt
(NH,.NHjO)PtCy,.3|H20 (Scholz, M. 1, 900).
Barium platinocyanide BaPtC!y.,.4H20.
Prepared by passing HON into 5 parts almost'
boiling water holding 1 part PtCl^ and 1^ parts
BaCO, in suspension, until CO2 ceases to be
evolved, and crystallising (Weselsky, J. pr. 69,
276) ; PtCli may be used in place of PtCl2, in
which case 0 is evolved (PtCl, -H 3BaC03 -i- 4HCN
= BaPtCy, + 2BaCl2 + 2H2O + 3CO2 -h 0 ; Wesel-
sky, J. pr. 103, 566). Monoolinio prisms. S.G.
3-054 (Schabus, W. A. B. 1850. 582). Crystals
appear green in direction of principal aiiis, and
sulphur yellow with blue- violet sheen in direction
at right angles to this. Soluble in 33 parts water
at 16°, considerably more sol. at 100°. Loses
all water at 180°, and begins to decompose.
Forms double compounds, BaPtCy^.KjPtCy,,
(Martins, A. 117, 357), and BaPlCy4.BbjPtCy,
(Ditsoheiner, W. A. B. 50, 373).
Magnesium platinocyanide
MgPtCy4.7H20. Prepared by adding MgSOjAq
to BaPtCy^Aq, filtering, evaporating to ^yness.
dissolving in a boiling mixture of alcohol and
ether, and crystallising. Bed quadratic prisma,
showing greenish on the surfaces near the middle
of the crystals and' blue near the extremities
(Haidinger, P. 77, 89 ; Werther, /. pr. 76, 18C ;
Greiss, P. 106, 645). At 40° loses water, turning
yellow. The yellow salt may be obtained in fine
crystals by evaporating an alcoholic solution of
the salts with 7HjO over H^SO^; the crystals
contain SH^O (Werther, J. pr. 76, 186). Becomes
colourless at c. 100° ; at 150° still contains 2H2O ;
dehydrated at 200°-230°, becoming orange yeiiow
(Werther, l.c.). (For more details v. Schafarik,
/. pr. 66, 385 ; Quadrat, A. 63, 164 ; 70, 300 ;
Weselsky, J.pr. 69, 276.)
Mercuric platinocyanide HgPtCy,.
White pp. obtained by adding HgCljAq to
KjPtCyjAq (Schafarik, J. pr. 66, 385).
Platino-ammonium platinocyanide
PtPtCy4.4NH3. {Platino-cyano-dAplatoso-am-
moniimi. Ammoniwn-platinammonium platino-
cyarUde.) White pp. obtained by adding KCyAq
to ammoniaoal PtOlj solution. With AgNOjAq
forms Ag2PtCy4 and Pt(N03)2.4NH3 (Knop a.
Schnedermann, J. pr. 37, 461 ; Backton, A. 78,
328).
Potassium pldtinocyani-de
K^PtCyj-SHjO. Clear yellow rhombic prisms,
with blue appearance in direction of principal
axis. S.G. 2-4548 at 16° (Clarke, J. 1877. 43).
Effloresces in air, becoming nearly white with
slight orange tint. Does not decompose at c. 600°.
SI. sol. cold, V. sol. hot, water. Decomposed by
HjSOjAq in the cold, giving PtCy, and CO.. Solu-
tion gives white pp. with mercurous salts with
Hg not in excess, and a blue pp. with excess
of Hg salts ; this reaction characterises pla-
tinocyanides. The salt may be obtained by dis-
solving PtCl4.2NH,Cl with a little KOH in a
cone, boiling solution of KCy, and crystallising
from water (Martins, A. 117, 357). It is also
produced by boiling Pt black with cone. KCyAq
(Deville a. Debray, G. B. 82, 241) ; also by heating
a mixture of Pt black and KjiPeOyj nearly to red-
ness, treating with water, filtering, evaporating,
and recrystallising from water the crystals which
separate.
Silver platinocyanide AgjPtCy,. White
pp. b.y adding AgNOjAq to KjPtCyjAq. Com-
bines with NH3 to form AgjPtCy4.2NHs (Knop a.
Schnedermann, /. pr. 37, 46l) ; prepared by
adding KoPtCyjAq to .ammoniacal AgNOjAq, or
to a solution of AgCO, in (NHjjjCOjAq. Sol.
dilute NHjAq, not in water.
Besides the preceding platinocyanides, the
following have been isolated: — CaPtCy4.5H,0;
and CaPtCy4.K2PtCy4 (Dobereiner, A. 17, 250;
Martins, A. 117, 357; Quadrat, A. 70, 300).
CdPtCy4; CdPtCy4.2NH3.H2O; andPbPtCy4.a;H20
(Martius, i.e.). CuPtCy4.a!H20 ;
CuPtCy4.2NH,.H20 ; Na2PtCy4.3H20 ;
NaK.Pt0y4.3H,0 ; SrPtCy4.5H,0 (Schafarik, J.pr.
66, 385; Quadrat, A. 63, 164; Martius, I.e.).
Ce2(PtCy.|)3.18H.,0 ; La2(PtCy4)3.18H20 (Czudno-
wicz, J. pr. 80, 16). CoPtCy4.2NH3 ;
NiPtCy,.2NH,.H20; ZnPtCy4.2NH3.H,0 (Knop
CYANIDES.
845
a. Sohnedermann, J. pr. 37, 461).
Di,(rtCy,)3.18H20 (Cldve, Bl. [2] 21, 246).
Er,(PlCy4),.21H20 ; Y,(PtOy,)3.21H20 (CUve a.
Hoeglund, Bl. [2] 18, 197). Li J'tCy,.a;HoO ;
Li(NH^O)PtOy..3H20 (Soholz, M. 1, 900).
Eb.;PtCy4.a;HjO (Ditsoheiner, W. A. B. 50, 373).
TL^tCy^; TljPtCyi.Tl^OO, (PrisweU, A. 159, 383 ;
F. a. Greenaway.S. 10, 1858). Th{PtCyJ,.16H20
(CkV'e, BZ. [2] 21,116).
The salts (NHjMej^PtCy,, (NH3Et)2PtCy4,
(NHjEy^PtCyj, and (NHEt3)ji'tCyj, have been
isola,ted (Debus, A. 128, 200 ; Soholz, M. 1, 900).
EtjPtCy, is described by Than (A. 107, 31S) ;
aisc salts at aniline, paratoluidine, and a-naph-
thylamine (Soholz, l.c.). Salts of alkaloids are
also known (v. Schwarzenbach, Vierte^ah/r.
Pham. 6, 422 ; Delfs, Fr. 3, 152).
Halogen addition products of pla-
tinocyanides, or salts of perchloro-,
perbromo-, andperiodo-platinocyanhy-
dric aoid. These salts have the general form
Bn Ph Ni Al
MiPtCy,.X,whereM = E, Na,:^, ^, -^, ^, &o.,
and X = CI, Br, or I. They were first obtained
by Hadow /C. J. 13, 106), and have been
examined also by Blomstrand {J. pr. [2] 8, 207),
and by Hoist (Bl. [2] 22, 347). Alkalis, or
AgNOjAq, withdraw halogen from -these salts
re-producing the platiuOcyanides. These salts
give white pps. with excess of HgNOjAq, whereas
platinocyanides give bluj pps. under same con-
ditions. When cone, solutions of the perhaloid-
platinocyanides are mixed with cone, solutions of
platinocyanides, double compounds of the form
SMjPtCyj.MjPtCyiXj are ppd. {v. Chiobo- &o.
PLATINOCYANIDES, infra). Those salts bleach in
presence of alkalis ; the chloro- and bromo- salts
decompose EI.
Potassium perchloroplatinocyanide
KjPtCy4.Cl2.2H2O (Knop a. Sohnedermann, J. pr.
37, 461). This salt was formerly regarded as
PtCy4.2KCl, i.e. as a double compound of KCl
with the hypothetical PtCy, ; but the researches
of Hadow show that it is rather to be looked on
as the final product of the reaction of CI with
KjPtCyj, the intermediate product being the
salt (described below) 5K2PtCy,.K3PtCy4.Cl2, which
is called by Hadow potassium-chloroplatino-
eycmide. Potassium perchloroplatinocyanide is
prepared by dissolving K-ohloroplatinooyanide
(q. V.) in nearly boiling ag^ua regia and crystal-
lising (K. a. S.), or by oxidising the same salt by
KMnOj in presence of HCl, evaporating at 100°,
and crystallising. Large rhomboidal triolinio
plates ; v. sol. water and alcohol ; very efflor-
escent ; heated gives off Cy, leaving ICCl and
K-^tCy,, and at a higher temperature gives KCl
and Pt. Partially reduced by Zn and NHjAq, or
by SO Aq, to mixture of K^PtOy, and eKaPtCy^-Glj
(K-chloroplatinooyanide). When cone, solution
of KJPtCyj.Clj and K-PtCyj are mixed crystals of
the chloroplatinocyaiiide (SKjPtCyi-^i^I'tCyj.CL)
are deposited.
The following perchloroplatinocyan-
ideshave been isolated, besides the Ksalt: —
(NHJ„X.2H20 ; BaX.SHjO ; OaX ; MgX.a!Hp,;
MnX.^HjO (Hoist, Bl. [2] 22, 347) [X = PtCyj.Cl J.
Perchloro -platinocyanhydric aoid
H.,PtCy,.Cl2.4H20 (Hoist, Z.c). Obtained by de-
ooinpoaing the Ba salt (itself produced by passing
CI into BaPtCy^Aq) by HaSO^Aq, filtering and
crystallising. White crystals; very soluble in
water and alcohol.
Perbromo-platinocyanhydric acid
H2PtCy4.Br2.a;H20 (Hoist, l.c.) is obtained by
adding Br to BaPtCy^Aq and crystallising; it
forms white crystals very sol. in alcohol and
ether.
Several per bromo -platinocyanides and
some periodoplatinocyanides have been
isolated ; they are produced by the action of lir
or I on the platinocyanides; the salts of tlie
alkalis and alkaline earths are very soluble in
water and may generally be easily crystallised ;
most of the salts of the heavy metals are insol.
or only si. sol. in water. Hoist (l.c.) describes
the following :-[X = PtCy4.Br2] AI2.3X.22H2O •
(NHJjX; BaX.SHjO; BeX; CdX.aiH^O;
C0X.5H2O; PbX.2H,0;' LijX; UgX.xHjO;
mX.xB.fi; KjX; NajX; SrX.7H20; ZnX.SH^O.
The periodo- salts described by Hoist are
BaPtCy4.l2a!H20, and K2Pt0y4.l2.
Double compounds of platinocyan-
ides with perhaloid platinocyanides;
or chloro-&c. platinocyanides, or chloro-
&c. platinidplatinocyanides. These salts
were formerly supposed to be double compounds
of KCl ifcc. with the hypothetical PtCy,, of the
form M2PtCy5 = PtCy3.2MCy. They are pro-
duced by the reaction of CI, Br, HNO,, and other
oxidisers, with the platinocyanides M.^PtCy,. The
change was supposed to be somewhat analogous
to that which occurs when a ferrocyanide
(MjEeCyJ is oxidised to a ferrioyanide (MjEeCy,;);
thus 2K4FeCy„ + 0 = 2K,FeCys + Kfi, and
3K2PtCy4 + 0 = 2K2PtGy5-HPtCy2-fK20. In ac-
cordance with this conception, the compounds
were called platimeyamMes (and sometipies
plaUnosesguicyanides when their composition,
was indicated by the formula Pt2Cye.4MCy).
Hadow (O. /. 13, 106), however, showed that
the salt of this series obtained by the limited
action of CI on K^PtOy^ contained 01; his
analyses and methods of synthesis of the salt
led him to give it the formula (K2PtCy4)jCl2, and
to indicate its formation by the reaction
6KfPtCy4 + Cl2 = 6(K2PtCyJCli. The synthesis
of the same salt by mixing cone, solution of K
perchloroplatinocyanide (KjPtCyj.Clj) and K
platinocyanide (K2PtCy4) shows that the for-
mula 6(K2PtGy4)Cl2 is better written so as to
indicate that the salt is a double compound,
viz. 5K2PtCy4.K2PtCy,.Cl2 ; this formula is con-
firmed by the fact that reducing agents (e.g.
SOaAq, or Zn and NH,Aq) decompose the salt
to a mixture of K2PtOy4.Cl2 and K2PtCy4 ; more-
over, the salt in question reacts with excess of
CI to form K2PtCy4.Cl2, and with excess of I or
Br to form K2PtGyj.l2 or K2PtCy4.Br2, respec-
tively. Hoist (B. 8, 124) got results which show
that although the composition of the chloro- &c.
platinocyanides is always to be represented by
the formula a;M2PtCy4.2/M2PtCy4.X2 yet the ratio
of x:y is not always 5:1.
Potassium chloroplatinocyanide, or
Potassium chloroplatinidplatinocyan-
ide, 5K2PtCy4.K2PtCy4.Cl2.21H20 (Hadow, C. /.
13, 106 ; Knop, A. 43, 111). CI is passed into
warm K2PtCy4Aq so cone, that crystals are depo-
sited on cooling ; the crystals are dried between
paper and recrystallised from water acidulated
8i6
CYANIDES.
with nci (Enop). Hadow divides a solution of
KjPtCy, into 6 parts ; into ^ be passes CI until
the liquid is saturated (KjPtCyj.Clj is thus
formed), he then adds the remaining | and eva-
porates. Green prismatic crystals, with red
metal-like surface colour by reflected light. Sol.
in water giving colourless solution, insol. in
alcohol. Gives off part of 'Kfl over H^SOj,
becoming black ; loses ISH^O at 100° and the
rest at c. 180° ; when strongly heated gives off
Cy.
Hoist {B. 8, 124) obtained the salt
10SrPtOy4.SrPtCy^.Ij.a;H,,O.
Weselsky (J. pr. 69, 276) describes some salts
obtained by the action of HNOjAq on platino-
cyanides ; he regards these as platiuocyanides
or platinum sesquicyanides (Pt2Cyii.4MCy) ; but
it is very probable that they are analogous to
Hadow's double compounds of platinocyanides
with perchloro- &o. platinocyanides, only that
the halogen is replaced either by NOj or NO, (c/.
Hadow, G. J. 13, 106; also v. Martius, A. 117,
357, for reaction of PhPtCy^ with HNOj whereby
a;PbPtCy4.2/PbPtCy4(NOj) seems to be produced).
The compound obtained by Hadow by the
action of PbO^ on KjPtCyi in HjSOj solution
seems also to belong to this class and to have
the halogen atoms replaced by the radicle SOj.
Potassium cyanide KCy. S.G. ia° 1-52
(Bodeker). [E, ON] = 65,350 ; [K,N,OJ = 32,500;
[KCy, Aq]= -3,010 {Th. 3, 23.5); [KOHAq,
HCNAq] = 2,770 (Th. 1, 160).
Occurrence, — In blast furnaces.
Formation. — 1. By fusing K in Cy or in
HON gas.— 2. By fusing KjCOj with nitro-
genous carbon. — 3. By passing N over a strongly
heated mixture of C and KOH or KjCOj. —
4. By deflagrating KNOj with K acetate, tar-
trate, &c., especially by heating a mixture of
KNO2, K2CO3, and KC2H3O2 (Desfosses, A. Ch.
38, 158; Fownes, J. pr. 26, 412; Delbriick, A.
64, ,296 ; Bunsen a. Playfair, J. pr. 42, 397 ;
Eeiken, A. 79, 77; Lauglois, A. Oh. [3] 52,
326 ; Koussin, O. R. 47, 875).— 5. By passing
NHj over a heated mixture of 0 and KjCOj or
KOH (Kuhlmann, A. 38, 62).
Preparation. — 1. Ordinary commercial KCN
(containing KCNO) is prepared by fusing
dry KjFeCye with B:jCO,[2K,FeCy8 + 2K2CO3
= 10KCN + 2KCNO-H2]?e + 2COj]; the fused
mass is poured off from the iron. — 2. HON
gas is passed into alcoholic solution of KOH
^1 part KOH in 3 parts alcohol) (Wiggers, A.
29, 65). An aqueous solution of pure KCN is
obtained by passing HON into KOHAq. —
3. Nearly pure KCN is prepared by fusing
dry KjFeCys in absence of air, and treating
with 50 p.c. hot alcohol (Geiger, A. 1, 46) ;
pKjFeCyj = 8KCN -1- 2FeC., + 2Nj].
Properties. — Crystallises from alcohol, or by
slowly cooling the fused salts, in white cubes, or
octahedra, v. sol. in water; deliquescent; si.
sol. in strong alcohol. Very poisonous. Melts
easily, and volatilises unchanged (in absence of
moisture) at full red heat.
Reactions. — 1. Aqueoiis soZMiioji decomposes
in air, slowly at ordinary temperature, rapidly at
100°, giving HCOjK and NH,.— 2. Melted in
nir forms KCNO. — 3. Heated with metallic
orides gives KCNO and metal ; thus acts as an
energetic reducer, e.g. reduces oxides of Pb, Fe,
Sb, Sn, Ac, &c., when heated with them. —
4. Heated with potassium chlorate or nitrate,
detonates violentiy. — 5. Beduces alkaline sul-
piiates to sulphides by heating with them. —
6. With sohition of potassium permanganate,
KCN forms CO.,, HNO3, HNO.„ HAO« H^OOj,
and CO2NH2 (Schlagdenhauffen, J. 1863. 305),
7. With alkali poVysuVphldes, KCNAq forme
KCNSAq. — 8. With iodme in cone, solution
KCN forms KI and Oyl. — 9. With sodium thio-
sulphate forms NaCNS. — 10. With potash pro-
duces NH, and HCO^K ; heated to redness with
KOH, K2CO3 Is formed and H evolved.
Oombmation. — 1. KCNAq dissolves many me-
tallic cyamdes forming double cyanides, e.g,
HgCyj, AuCy, PtCy^, OUjCyj, &a. (v. various me-
tallic cyanides). — 2. When sulphur dioxide is
passed into cold cone. KCNAq, two compounds
are formed, CNK.SOj.H^O and CNK.SO,KH.SOj;
they maybe crystallised (Btard, C. R. 88, 649).
Testing KCN for common impurities. — The
chief impurities in ordinary KCN are KCNO,
K.,CO„ K,S, KNCS, KHCO„ K^FeCy^, K^SO,,, and
KCl. K^CO jis detected by treating with alcohol
at 80° and examining the insoluble portion by
the ordinary tests. K^S ; Pb salts give a black
pp., in absence of KjS a white pp. is formed.
KCNS ; HClAq is added and the HCN is removed
by wanning ; a few drops of FeCl,Aq are added,
when a deep-red colour shows KNCS. KCNO ;
alcohol at 80° is added and the solution is acid-
ulated, effervescence shows KCNO. KHCO2 ; a
current of CO^ is passed through until HCN is
removed, the liquid is evaporated to dryness,
the residue is distilled with HjSO^Aq, and to the
distillate are applied the ordinary tests for
formic acid. K^FeCy,; pure FeCljAq gives
blue pp. or blue colouration. K2SO4; HCN is
removed by warming with HClAq, and Ba2N0,Aq
is added. KCl ; the specimen is heated with
2 parts KNO, and 10 parts Na^CO,, the fused
mass is heated with water, and AgNO, and
HNOjAq added to the aqueous solution to pp.
AgCl.
Bhodium cyanides. Bh^Cye, and a rbodi-
oyanide KjEhCyj, are known.
Rhodium ses^uicyanide Eh^Cyu. Car-
mine-red powder, obtained by adding hot cone,
acetic acid to KsEhCyj (Martius, A. 117, 357).
Dissolves in KCNAq with re-formation of
K,EhCy».
Potassium rhodicyanide K,EhCy,. Mo-
noclinic crystals : easily decomposed by acids ;
formed by fusing EhCl4.2NH4Cl with KCN (Claus,
J. 1855. 444).
Suthenium cyamdes. No simple cyanide has
been isolated; HjEuCy, and some of its salts
are known.
Rutheno-cyanhydric acid HjEuCy,
(Claus, 7.1855.444). Obtained by adding HClAq
and ether to the K salt (q. v.) ; lustrous, irides-
cent tablets ; e. sol. alcohol and water ; heated
with HClAq, HCN is evolved.
Potassium rutheno-cyanide
K4EuCy5.3Hp (Claus, Z.c). Obtained by heating
KCN withEuCl(.2NH4Cl; small, white, quadratic
tablets, isomorphous with KjFeCy„. The solu-
tion of this salt gives coloured pps. with salts of
Cu, Fe, Pb, and Zn.
Silver cyanide AgCy. Only one cyanide of
Ag is known ; it forms various double salts.
CYANIDES.
347
White, curdy pp. obtained by adding HCNAq or
KCNAqto solution of a salt of Ag ; excess of KCN
must be avoided, as AgCy is sol. KCyAq ; the pp.
is dried at a temperature under 126". S.Gr. o. 3"9S
(Schroder, JS. 13, 1074). H.P.[Ag, Cy] = 1,395;
[Ag, C, N] = -81,455 ; [2HCyAg, Ag^O] =42,310
(ppd. AgjO ; formation of solid AgOy) (Th. 3, 382).
Not blackened by exposure to light. Sol. NHjAq ;
b1. sol. boiling HNOi^Aq ; sol. KCNAq.
Beactions. — 1. Heated, is decomposed to Ag
and Cy.— 2. Water at 280° forms NH,.Ag.C03
(Eeynoso, A. Ch. [3] 45, 111).— 3. Chlorine
forms AgCl and CyCl. — 4. Sulphur heated with
AgCy forms AgNOS. — 5. Ammonia dissolves
AgCN, forming AgCN.NH,. — 6. Potassium cyan-
ide dissolves AgOy, forming AgCy.KCy. — 7. De-
composed by sulphuric acid or hydrochloric aoid,
with evolution of HCN.^8. Decomposed by sul-
phuretted h/yd/rogen, also by sulphivr chloride
(Schneider, J. pr. 104, 83).
Combinations. — 1. With ammonia to form
AgCy.NHj ; monoclinic tablets, which give oif
NHj in the air ; obtained by heating AgCy in
NH3 (Weith, Z. 1869. 380 ; Liebig a. Eedten-
bacher, A. 38, 129). — 2. With silver nitrate to
form AgCy.AgNO, (or ? 2AgCy.AgNOs) (Bloxam,
C. N. 48, 154 ; Wohler, P. 1, 231) ; obtained by
dissolving AgCy in hot couc. AgNO^Aq.
Double cyanides containing silver
cyanide. The alkali salts are obtained by dis-
solving AgCy in solution of the alkali cyanide
and evaporating ; the salts of the heavy metals
are generally obtained by adding AgCy.KCyAq
to solutions of these metals.
Silver-potassium cyanide AgCy.ECy.
Begular octahedra ; sol. 4 parts water at 20°,
and in 25 parts alcohol (85 p.c). Decomposed
by acids with separation of AgCy. H2S ppts.
AgzS, except from solutions in much KCNAq
(Glassford a. Napier,P. M. 15, 66 ; Eammelsberg,
P. 38, 376; Baup, A. Ch. [3] 53, 462; B^ohamp,
J. pr. 60, 64). H.F. rAg-Cy^2KCyAq] = 12,980 ;
[Ag^Cy^2KCyAq] = 15,780 {Th. 3, 470). The
other important silver double cyanides are : —
AgCy.NaCy; 3AgCy.2KCy.NaCy (Baup, l.c.);
AgCy.TlCy(Fronmiiller,P.ll,91) ; AgCy.NMe4Cy
(Thompson, B. 16, 2338; Glaus a. Merck, S. 16,
2737); 2Ag0y.HgCyj.HgSO,.H2O (Geuther, A.
106, 241).
Sodinm cyanide NaCy. Prepared by pass-
ing HGN gas into an alcohoUo solution of NaOH
mitil NaCy pps. Obtained also by methods simi-
lar to those whereby KCy is formed (v. Potas-
Sinn CYANIDE, p. 346). NaCy crystallises with
diiEculty. According to Joannis (A. Ch. [5]
27, 482) two hydrates are obtained by crystal-
lising from alcohol at different temperatures;
2NaCy.HjO, and NaCy.2HjO. Joannis (Z.c.)
gives some thermal data: — [Na, Cy] = 60,400
(solid NaCy formed); [NaCy, Aq]= -500;
[HCyAq, NaOHAq] = 2,900.
Strontium cyanide SrCy^. Prepared, simi-
larly to BaCyj, by heating SrFeCy,; ; or prefer-
ably by passing HCN vapour into crystals of
SrOjHj. Unstable salt. Crystallises from solu-
tion with 4H20 ; the crystals are v. deliquescent
and absorb COj from the air (Joannis, A. Ch.
[6] 27, 482 ; Schulz, J. pr. 68, 257). Joannis
(I.e.) gives the thermal data : — [SrOAq, 2HCyAq]
-e,260.
Thallium cyanides. Two cyanides of Tl are
known, TlCy and TlCy.TlCy.,.
Thallous cyanide TlCy. Obtained by
adding excess of cone. HCNAqto a cone, solution
of a thallous salt, and then adding much alcohol
and ether. Heavy white pp., e. sol. water, crys-
tallising in lustrous tablets from the hot solu-
tion. Decomposed by heating (Fronmiiller, B.
6, 1178).
Thallo-thallie cyanide TlCy.TlCy,
( = Tl2CyJ. Formed by evaporating m vacuo a
solution of TI2O, in HCNAq. Large, white,
rhombic plates ; e. sol. water ; decomposed at
125°-130°withrapidevolution of Cy (Fronmiiller,
B. 11, 91).
Double cyanides containing thallous
cyanide. — TlCyAq dissolves the cyanides of
Hg, Ag, andZn; when the solutions are crys-
tallised the following salts are obtained: —
2TlCy.HgCy2; TlCy. AgCy; 2TiGy.ZnCy2 (Fron-
muller, B. 11, 91). No double cyanides of TljCy,
are known.
Titanium cyanides. No cyanide of Ti is
known, but the compound TijCN^ exists ; this
body is almost certainly a double compound of
Ti cyanide vrith Ti nitride TiCyj.3TisNj.
TitanHkm cyano-nitride TiCy2.3Ti3N.,
This compound is formed in smelting titanifer-
ous iron-stones in the blast furnace (WShler, A.
73, 34; 74, 212). It may be obtained by very
strongly heating K^FeCyj with TiOj, (Wohler,
I.e.), by heating KCN in vapour of TiCl,, and by
passing N over a mixture of C and TiO^ heated
to the M.P. of Pt (Wohler a. Deville, A. 103,
230). Metal-like, reddish octahedra, resembling
metallic Cu. S.G. 5"28. Volatile at very high
temperature. Not acted on by boiling HNOjAq
orHjSOj. Sol. HNOsAq containing HF. Heated
in water-gas is decomposed thus : TijCNj + lOH^O
= CNH-)- STiOj + 3NH3 + SHj. Decomposed when
heated with CI, giving TiClj, and probably a
compound of TiClj with CyCl. Heated with
KOHAq forms K titanate and NH,. CuO, PbO,
and HgO are reduced to metals when heated
vrithTisCN^.
Uranium cyanide. None has been certainly
isolated. The oxides of U do not dissolve in
HCNAq; addition of KCNAq to solution of U
chloride ppts. an oxide of U (Bammelsberg, P.
59, 2). According to Wittstein (B. P. 63, 214),
when KCNAq is added to a uranie salt solution
a yellow pp. is obtained, sol. in excess of KCNAq,
not ppd. again by acids.
Vanadium cyanide. None has been isolated.
Berzelius made some observations on the reac-
tions between vanadic acid and HCN (P. 22, 26).
Yttrium cyanide. No cyanide has been cer-
tainly isolated. Eydrated YjOj is said to dissolve
in HCNAq, and white nodules to be formed on
evaporation (Berlin).
Zinc cyanides. ZnCy^ is known, and also
several double cyanides.
Zinc cyanide ZnCyj. Obtained by adding
KCNAq (free from K2CO3) to solution of a Zn
salt, or by adding HCNAq to Zn acetate solu-
tion. Special precautions are needed to insure
production of pure ZnOy, (v. Wohler, B. J. 20,
152 ; Oppermann, /. 1860. 226 ; Joannis, 0. E.
92, 1388, 1417; Eammelsberg, P. 42, 114).
ZnCvjis obtained in crystals by covering a layer
of cone. Zn(C2H302)2Aq with * Uttle water, and
S48
CYANIDES.
very tarefuUy pouring on to this dilute HCNAq;
the crystals form slowly. Crystallises in ortho-
rhombic prisms. The pp. by KCN and HON is
white with a tinge of yellow. Decomposed by
strongly heating, giving off Cy (Eammelsberg).
Insol. water and alcohol ; e. sol. alkalis and
KCNAq ; si. sol. in cone, solutions of Zn salts
(Joannis). With hot KOHAq it forms K„O.ZnO
and ZnCy,.2KCy. H.P. [Zn,Cy-l = 58,600;
[ZnO,2HCyAq] = 13,400 (Joannis).
Double cyanides containing ZnCyj. —
These compounds are obtained by dissolving
ZnCyj in a solution of the other cyanide and
crystallising : —
ZnCy.,.2NHjCy (Corriol a. Berthemot, J. Ph.
16, 444).
Zn0y2.BaCy2.2H.p (Weselsky, B. 2, 588).
Zn0y2.Ca0y2.a;H20(Schindler,lfa3a3.PfeM'm.
36, 70).
' ZnOy2.2KCy (Gmelin ; Fresenius a. Haidleu,
A. 43, 132). [Zn,0y^2KCyAq] = 62,230 {Th.i,
475).
ZnCy2.2NaCy.5H20(Eammelsberg,P.42,112).
ZnCy2.HgCy.i.HgCl2.6H20 (Varet, 0. R. 106,
1080).
ZnCyj.HgCy2.HgCl,.6NHs (Varet, I.e.).
SELENOCYANIDES. Salts of seUiwcyan-
hydric acid HSeCy. Also called selenocyanatcs.
Discovered by Berzelius in 1820 [S. 31, 60);
more fully examined by Crookes (C. J. 4, 12).
Selenocyanhydric acid HSeCyAq. (Seleno-,
or selenio-cyanic acid. Hydrogen selenio- or
seleno-cya/nate. HydroseUnocyanic acid.) Known
only in solution; prepared by passing a rapid
stream of HjS through hot Pb(SeCy)2Aq con-
taining Pb(SeCy)2 in suspension, filtering from
PbS, heating the filtrate nearly to boiling, and
filtering again (if necessary) from ppd. Se. This
solution, which is markedly acid, is decomposed
on boiling; it cannot be concentrated without
change even over HjSOj in vacuo. It is decom-
posed by acids into HOy and Se. The solution
dissolves Zn and Fe with evolution of H
(Crookes, C. /. 4, 12).
Ammonium selenooyanide NH,.SeCy. By
neutralising HSeCyAq by NH^Aq and evaporat-
ing. Soluble, deliquescent, crystallises in minute
needles (Crookes, Z.c).
Barium, Calcium, and Strontium eeleno-
cyanides M(SeCy)2 [M = Ba, Ca, or Sr]. By dis-
solving MCO3 in HSeCyAq and concentrating in
vaciu) (Crookes).
Copper selenooyanide. Brown pp. by adding
KSeCyAq to OuSO,Aq ; very soon decomposes
to HSeCyAq and CuSe (C).
Gold selenooyanide. Not isolated. When an
alcoholic solution of KSeCy is added to AuCl^Aq,
Se is ppd., and the filtrate on evaporation yields
small dark-red prisms of the double salt
AnK(SeCy)j (Clarke, B. 11, 1326).
Iron selenooyanide. Not isolated. Crookes
{l.c.) mentions various reactions which do not
yield a definite salt.
lead selenooyanide Pb(SeCy)2. By adding
ESeCyAq to Pb acetate solution, dissolving the
pp. in boiling water, filtering (if necessary), and
crystallising. Lemon-coloured needles ; insol.
alcohol ; not changed at 100° (C).
Magnesium seleuocyanide. By dissolving
MgCO^ in HSeCyAq and evaporating ; a gummy
non-crystallisable mass; composition und^oiJetl.
Mercury selenocyanide. Two salts have been
isolated, Hg(SeCy)2 and HgSeCy (Cameron a.
Davy, Tr. Irish Acad. 27, 148).
Mercuric selenocyanide Hg(SeCy)j; a
greyish white salt obtained by adding KSeCyAq
to Hg(02H5O2) jAt[. Soluble in HgCl2Aq, forming
Hg(SeCy)2.HgCl2. Not obtained by using HgCl,
in place of Hg(02H302) (Crookes).
Mercurous selenocyanide HgSeCy;
olive green, amorphous ; by ppg. HgNOjAq by
KSeCyAq.
Platinum selenocyanide. Not isolated. Ad-
dition of PtCljAq to an alcoholic solution of
ESeCy forms a reddish pp. ; when this is treated
with boiling water part of it dissolves, and the
filtrate gives crystals on cooling ; these crystals
are dissolved in alcohol and re-crystallised ;
they are the double salt KJPi{SeOy)g ; 8.Q. 3-377
at 10-2°, 3-378 at 12-5° (Clarke, Am. 8. 16, 119).
Potassium selenocyanide KSeCy. Prepared
by dissolving red Se (ppd. in the cold) in KCyAq
and evaporating (Sohiellerup, A. 109, 125). Also
by fusing 1 part Se with 3 parts dry KjFeCy, in
a small retort, digesting with absolute alcohol,
passing COj through the liquid to decompose
KCy and KNCO and ppt. KHOO,, distilling oft'
the alcohol, dissolving in water, filtering, and
crystallising in vacuo over H2SO4 (C). White,
needle-shaped deliquescent crystals ; melt with-
out change, if out of contact with air (Berzelius) ;
in air decomposes a little above 100° (C).
KSeCy jAq is alkaline to litmus ; decomposed by
acids with evolution of HCy and ppn. of Se. CI
produces CyCl and Se (c/. Kypke a. Neger, A.
115, 207). Several double compounds are de-
scribed by Cameron a. Davy {Tr. Irish Acad.
27, 151) ; X.HgCy„ X.HgBr„ X.Hgl,, X.HgCl„
X.Hg(SCy),.
Silver selenocyanide AgSeCy. Ppd. on
adding AgNOjAq to KSeCyAq; if NHjAq is
present pp. separates in small shining crystals.
Blackens in light; insol. in water; sparingly
sol. in cold dilute acids; decomposed by hot
cone, acids (C).
Sodium selenocyanide NaSeCy. Small crys-
tals ; by neutralising HSeCyAq by NajCOj, and
evaporating in vacuo (C).
Zinc selenooyanide. Non-deliquescent crys-
tals [?Zn(SeCy2) J ; by dissolving Zn or ZnO in
HSeCyAq and evaporating (C).
SCLPHOCYANIDES. {Bhodanides. Sul-
phocyanates. Thiocyamates.) Salts of sulpho-
cyanic acid HSCN. For an account of sulpho-
oyanio acid v. Cyanic (suipho) acid, p. 303;
and for general properties of sulphocyanides v.
p. 328. Disulphoeyanides (salts of H.jC2N,,S3)
are described in the art. Cyanueates (metallic)
and Sdlphoctantieates, p. 360.
Aluminium sulpliocyanide AljOj.isHjO dis-
solves slowly in HSCyAq ; when the solution is
evaporated over HjSOi a gummy mass is ob-
tained, which ma'y be the neutral salt ; if the
solution is evaporated at 100° HjS and HOy are
evolved and yellow flakes (? basic salt) separate
(Meitzendorff, P. 56, 63).
Ammonium sulphocyanide NH^SCy. H.F.
[N, H', S, Cy] = 59,100 (Joannis, A. Ch. [5] 20,
540). Produced by decomposing Cu(SCy)j by
NHjHSAq, filtering, and evaporating; also by
evaporation of NH^Aq mixed with alcoholic
. solution of CSa (Milloii, Z. 1861. 64 ; Zeise, A.
CYANIDES.
S4f)
47, 36; Glaus, A. 179, 112). Prepared by digest-
ing the HCNAq from 6 parts K^FeOyj (by dis-
tilling with 3 parts oono. HjSOj mixed with
1^ parts water) with the NH^ polysulphide solu-
tion obtained by saturating 2 parts NHjAq,
S.G. -95, with HjS, and adding 2 parts of the
same NHjAq and 2 parts S. ; the liquid is boiled
till aU NH, sulphide is decomposed with separa-
tion of S, filtered, evaporated, and crystallised
(about lA to If parts NH^SCy are obtained)
(Liebig, A. 61, 126). Large, white, deliquescent
Iilates. S.G. 1-3075 at 13° (Clarke, J. 1877. 43).
V. sol. water and alcohol ; melts at 159° (Eey-
noso, A. 150, 255) ; and at higher temperature
(i80°-190°) evolves CS^, HjS, and NH3, and
leaves guanidin sulphooyanide (Volhard, B. 7,
92 ; Delitsoh, J. pr. [2] 8, 240 ; 9, 1) ; at 230°-
250° thioprussiamic acids are formed (Glaus a.
Seippel, B. 7, 92) ; at stUl higher temperature
mellam is formed, and finally mellone (Volhard,
J.pr. [2] 9, 28). Heated for some time nearly
to its M.P., thio-urea, CS(NHj)2 (isomeric with
NH,SCy), is produced (Volhard, B. 7, 92; Eey-
noso, A. 150, 255). S. 122-1 at 0°, 162-2 at 20° ;
much heat disappears during solution (Eiidorff,
B. 2, 68 ; Glowes, Z. 1866. 190 ; Joannis, A. Ch.
[5] 26, 482). Several metallic oxides, e.g. HgO,
ZnO, AgjO, dissolve in NHj.SGyAq and form
double sulphocyanides (Fleischer, A. 179, 225).
Combines with HgCyu to form the double com-
pound NH,SGy.HgCy2 (Cl^ve, Bl. [2] 23, 71).
Arsenic snlphocyanide As(SCy)3. Produced in
very small quantity by heating together AsClj
and Pb(SCy)2 ; volatile at c. 400° forming oily
drops which solidify to crystals; insol. in all
ordinary menstrua; decomposed by water to
AsAM and HSCy (Miguel, A: Ch. [5] 11, 341).
Barium Bulphocyanide Ba(SCy)2.2H20.
Formed by neutralising HSCyAq by BaCO,,
evaporating at 100°, and then over H^SOj (Meitz-
endorff, P. 56, 63). Long, lustrous, deliquescent
needles ; v. sol. alcohol and water. From warm
solution of this salt mixed with warm HgCy^q
the double compound Ba(SCy)2.HgCy2.4HjO sepa-
rates on cooling (Cldve, Bl. [2] 23, 71; cf. Storok
a. Strobel, D. P. J. 235, 156).
Beryllium sulphocyanide [?Be(SCy)J. Pre-
pared by adding BeSO, to Ba(SCy)2Aq (Toc-
aynsky, Z. 1871. 276) ; or by dissolving BeCOjiu
HSCyAq and crystallising (Hermes, J", pr. 97.
465).
Bismuth sulphocyanide Bi(SCy)3. By dis-
solving Bi203.a;H20 in HSCyAq, evaporating,
filtering from the yellow basic salt which sepa-
rates, and evaporating again ; dark orange red
powder (Meitzendorff, P. 56, 63).
Cadmium sulphocyanide Cd(SCy)2. White
crystals ; sp. sol. water ; by dissolving CdCOj in
HSCyAq and evaporating (Meitzendorff, P.
56, 63). By dissolvihg this salt in NHjAq,
and evaporating with frequent addition of
KHjAq, the double eompoimd Cd(SCy)2.2NH3
is formed (M.). The double compound
Cd(SCy)j.2HgOy2.4H20 is described by CWve {Bl.
[2] 23, 71).
Calcium sulphocyanide Oa(SCy)2.8HjO. Pre-
pared like the Ba salt. Crystallises badly; sol.
water (Meitzendorff, P. 56, 63). From hot solu-
tions of this salt and HgCy.^ the double compotmd
Ca(SCy)j.2HgCy;j.8Hj,0 crystallises on cooling
(CWve, Bl. f2J 23, U: Bockmsnn, A. 22, 153),
Cerium sulphocyanide Ce(SCy)3.7HjO; double
compownd Ce(SCy)3.3HgCy.,.12H„0 (JoUa, Bl. [2]
21, 585).
Chromium sulphocyanides. Beniiei chrMnic
sulphocyamde, the acid chromisulphocya/nhydric,
H30r(SOy)3, is known in aqueous solution, and a
series of salts, chromisulphocyanides, is derived
from it; there are also several c?wom-amwio?im»«
sulphoeyanides known.
Chromic sulphocyanide Cr(SCy)j.
Dark-green, amorphous, deliquescent mass, ob-
tained by dissolving CrjOj-aH^O in HSCyAq, and
evaporating over H^SO, in vacuo (Clasen, J. pr.
96, 349).
Chrom,isulphocyanhydric acid, or
chromisuVphocyania acid, H3Cr(SCy)3Aq; known
only in aqueous solution, which is obtained by
decomposing the Pb or Ag salt by H,S. The
solution is dark wine-red and distinctly acid ; ' it
decomposes on evaporation to HSCyAq and
Cr(SCy)3 (Eosler, A. 141, 185).
Potassium chromisulphocyanide
K3Cr(SCy)3.4H20. Prepared by heating for
about 2 hours a fairly cone, solution of 6 parts
KSCy and 5 parts chrome-alum, ppg. by alcohol,
filtering, and crystallising from alcohol. Forms
almost black crystals, which appear ruby red
by transmitted light; loses all H^O at 110°.
Solution of this salt is not ppd. by alkali car-
bonates or by NHjHS ; it is ppd. by NaOHAq
only on heating; evaporated with HClAq, KCl
and 0rCl3 are produced (Eosler, A. 141, 185).
Besides the K salt the following are described
by Eosler (l.c.) : —
(NH,)3Cr(SCy3).8H,0 ; Ba32Cr(SCy)3.16H,0 ;
Pb320r(SCy)3.4Pb(OH)j.8H20 ; Ag3Cr(SCy)3 ;
Na3Cr(SCy),.7H30.
Chrom-ammonium sulphocyanides.
The composition of these salts may be expressed
by the formula 2Cr(SCy)a.4NH3.M"(SCy)2 where
M = 2NH4, K2, Ag, Cuj, or Hg ; these salts do not
seem to be double compounds, but rather salts
of the complex acid H2(SCy)s(N4H,„Cr2). The
acid itself is known in aqueous solution ; it is
obtained by decomposing the Hg salt by HjS ;
the solution is deep-red, by careful evaporation
a red amorphous mass is obtained (Beinecke, A.
126, 113).
The ammonium salt
(NH,)2(SCy)a(NiH,„Crj,) is obtained by adding
powdered K^CrjO, to molten NH^SCy until the
mass becomes solid, treating with hot water,
and adding pieces of NH^Cl to the deep-red
liquid, when the salt separates in reddish crys-
tals. V. sol. alcohol and ether; by prolonged
treatment with water it forms NHjSCy, Cr(SCy)3,
and Cr^Os ; easily decomposed by dilute acids or
alkalis (Eeinecke, A. 126, 113 ; cf. Morland, /.
1860. 162).
The potassium salt K2(SCy),(N4H,3Cr2)
is obtained by reacting on the NH, salt by cone.
KOHAq, and re-crystallising the compound
which separates from hot water.
The sodium salt is obtained by a similar
process, using NaOHAq. The soluble salts give
pps. with salts of -many heavy metals ; the fol-
lowing have been isolated: —
Cn,(SCy)3(N,H,„Cr,), Hg(SCy),(N,H,„Or,),
Ag2(SCy)3(N4H,„Crj).
Cobalt sulphocyanide Co(SCy)2 (Glaus, A.
99, 48). Obtained by dissolving CoO.xH^O i^
3G0
CYANIDES.
HSOyAq, and evaporating. According to Meitz-
endor'fl (P. 56, 63) the salt crystallises with
iHjO. Solution in water is rose-red, beoonaing
deep blue by concentration. Alcoholic or ethe-
real solution becomes blue on dilution ; this re-
action has been applied for the optical determi-
nation of Co (Wolff, ¥r. 1879. 38). The doubU
compound Co(SCy)2.Hg(SCy)2 is known (Cldve,
J.pr. 91, 227 ; Skey, J. 1874. 300).
Copper sulphocyanides. Cuprous sulpho-
cyanide Cuj(SCy)2 (Meitzendorff, P. 56, 63).
Formed by adding KSCyAq to CuSO,Aq reduced
by FeSO, or SOj. White powder, insol. water
and dilute acids ; sol. NHjAq. May be used in
quantitative estimation of Cu"(Eivot, C. B. 38,
868; Busse, Fr. 1878. 55). Gupric sulpho-
cyanide Cu(SCy)2 (Meitzendorff, Z.c. ; Hull, 4.
76, 93). Black crystaUiue powder ; by adding
ESCyAq to fairly air-free couo. CuSOjAq con-
taining a little H2SO4; decomposed by water,
quickly when hot, to Cnj(SCy)j, HSCy, HCy, and
H2SO4. Dissolves in NHjAq, and gives the double
salt Cu(SCy)2.2NH3 (Meitzendorff, Z.c).
Didymium sulphocyanide I)i(SCy)j.6HaO
(CWve, Bl. [2] 21, 248).
Erbium sulphocyanide Er(S0y)j.6H2O (C14ve
a. Hoeglund, Bl. [2] 18, 197). Double compound
Er(SCy)3.3HgCy2.12H20 (ClAve, Bl. [2] 21, 344).
Gold sulphocyanides; known only in combi-
nation.
Aurous - potassium sulphocyanide
AuSCy.ESCy. AuCljAq is added drop by drop
to KSCyAq at 80° as long as the pp. dissolves,
the liquid is evaporated and crystallised. Straw-
yellow prisms ; melts at 100° ; decomposed by
heat to S, CS2, Au, and KSCy. Solution blackens
in light ; it gives pps. with salts of many heavy
metals (CUve, J.pr. 94, 14). Addition of NHjAq
pps. the double compound AuSCy.NHj.
Auric-potassium sulphocyanide
Au(SCy)3.KSCy. AuCljAq is added to excess of
KSCyAq in the cold (OWve, J.pr. 94, 14). Crys-
tallises from warm water in orange-red needles ;
sol. alcohol and ether. Forms dotible compowids
(Skey, J. 1874. 300).
Auric -sodium sulphocyanide
Au(SCy)3.NaS0y (Kern, J. 1876. 319).
Iron sulphocyanide. Ferric sulphocyan-
ide Fe(SCy)3.l|H20; by KSCyAq to FeCl.,Aq
and evaporating. Small blackish-red crystals ;
V. sol. water, alcohol, and ether. Solution is
decolourised by NaHCOj'with ppn. of all Fe ; not
decolourised by HClAq (Cleve, J.pr. 91, 227 ; cf.
Skey, /. 1874. 300). Ferrous sulphocyan-
ide Fe(SCy)2.1iH20. Greenish prisms, by
adding KSCyAq to FeSOjAq ; v. sol. water, alco-
hol, and ether ; unstable (Claus, A. 99, 48).
Forms a double compound Fe(SCy)2.Hg(SCy)2
(Cl^ve, J.pr. 91, 227).
lanthanum sulphocyanide La(SCy)3.7H20.
Double compound La(SCy)a.3HgCy2.12H20
(Clfive, Bl. [2] 21, 196).
Lead sulphocyanide Pb(SCy)2. Yellow lus-
trous monoelinio crystals; by ppg. neutral
Pb{CjH,02)Aq by KSCyAq. S.G. 3-82 (Sohabus,
W. A. B. 1850. 108). Decomposed by hot water
to the basic salt PbOH.SCy, which is also ob-
tained by adding basic Pb acetate to KSCyAq
(Liebig, P. 25, 546). H.F. [Pb, S, Cy] = 23,000
(Joannis, A. Gh. [5] 26, 540). The double
mlts Pb(SCy)2.PbBrj, Pb(SCy)s.8Pb?r.. i^nd
3Pb(SCy)a.PbIj. are described by Thorp {Am. 10,
229).
Lithium sulphocyanide LiSCy (Hcrmea,
jr. pr. 97, 465). ,
Magnesium sulphocyanide Mg(SCy),.4H20.
White deliquescent crystals; by ^ssolving
MgCOs in HSCyAq and evaporating (Meitzen-
dorff, P. 56, 63). Forms the double compound
Mg(SCy)2.2HgCy2.4H20 by mixing warm solutions
of the two salts and allowing to cool (Cl^ve, Bl.
[2] 23, 71).
Manganese sulphocyanide Mn(SCy)2.3H20
(Meitzendorff, P. 56, 63). By dissolving MnCO,
in HSCyAq and evaporating. Loses 3H2O at
160°-170°.
Mercury sulphocyanides. Merourous sul-
phocyanide HgSCy (Wohler, O. A. 69, 271).
H. F. [Hg, S, Cy] = 18,000 (Joannis, A. Gh. [5]
26, 540). White pp. by adding dUute KSCyAq
to a large excess of very dilute HgNOjAq with a
little HNOj added ; if the solutions are not di-
lute the pp. is grey and contains Hg (Claus, J.pr.
15, 401H Hermes, J. pr. 97, 465). Sol. in hot
HClAq, also in KSCyAq, with separation of Hg
(Philipp, P. 131, .86). Mercuric sulphocy-
anide Hg(SCy)2. White pp. by mixing HgCljAq
orHg(N05)2Aq and KSCyAq; sol. excess of either
salt ; V. si. sol. water, m. sol. alcohol; soluble
with decomposition in splutions of chlorides.
When Hg(SCy)2 is heated it swells up, giving ofl
Hg vapour, N, and CSj, and leaving a grey mass
like graphite, and at a higher temperature form-
ing meUon. This salt is sold under the name of
'■PharaoWs serpents.' (Hermes, J.pr. 97, 465 j
Philipp, P. 131, 86.) Hg(SCy)2 dissolves in some
other sulphocyanides forming double sulpho-
cyamides ; the following have been isolated : —
Hg(SCy)2.2KH,SCy (Fleischer, A. 179, 225);
Hg(SCy)2.2KSCy (Hermes, J. pr. 97, 465);
Hg(SCy)2.Zn(SCy)2 (ClAve, J. pr. 91, 227). Be-
sides these double sulphocyanides Hg(SCy)2
forms several double compov/nds with other salts ;
Hg(SCy)2.3NH,.H20 (Fleischer, A. 179, 225) ;
Hg.SCy.NH2.HgO (Claus, J.pr. 15, 401 ; Philipp,
P. 131, 86; Fleischer, l.c.); Hg(SCy)2.3HgO
(Fleischer, l.c.) ; Hg.SCy.CjHjOa (Byk, J.pr. [2]
20, 328); Hg(SCy)2.KCy.2H20 (Bockmann, A.
22, 153 ; Claus, l.c. ; Philipp, 2.C.).
Molybdenum sulphocyanide. Pp. formed by
adding cone. KSCyAq to a Mo salt is probably
Mo(SOy)3 (?). Sol. in water or ether with in-
tense dark carmine red colour (Braun, Fr. 1863.
36; 1867.86). Said to form a double compound
with Hg(SCy)2 (Skey, C. N. 30, 25).
Nickel sulphocyanide Ni(SCy)2.^H20 ; yellow
crystalline powder ; obtained by evaporating so-
lution of NiO in HSCyAq (Meitzendorff, _P. 66,
63). Dissolves in NHjAq, and solution evapo-
rated on water-bath gives blue efflorescent crys-
tals of the double compound Ni(SCy)2.4NHs;
decomposed by water to NHjAq and NiO (Meitz-
endorff, I.C.). Also forms a double compound
with Hg(S0y)2, viz. Ni(SCy)2.Hg(S0y)2.2H2O
(Cldve, J.pr. n, 227).
Palladium sulphocyanides. None certainly
isolated ; if a simple sulphocyanide of Pd exists
it is very soluble in water (v. Porrett, T. 1814.
527). By dissolving Pd0l2.2KCl and KSCy in
water and crystallising, a double sulphocyanide
of Fd and K is obtained; other double palladium
sulphocyanides ^re alsp Paid to be formed by re-
CYANIDES.
S51
actions similar to those whereby sulphooyano-
plaiinum compounds are produced ; the oompo-
Bition of these salts is not yet finally decided, the
data are meagre (v. Croft, C. N. 16, 53).
Phosphorus sulphocyanide P(SCy)3 v. Phos-
rHOBUS.
Platinum sulphocyanides. The reddish-brown
Bolid obtained in the reaction between some of
the double Pt sulphocyanides, e.g. KjPt(SOy)j
and CI or HNOjAq, is-piob&blj ptatinous sulpho-
cyamde,Ft{S0y)2 (Buckton, O. J. 7, 22). PlaHnic
sulplwcyamde has not been isolated. Many
double compounds of Pt(SCy)2 and Pt(SCy)4 are
known, but they are better regarded as salts of
the aoids HjPt(SCy), and HaPt(SGy)„, both of
which are known in aqueous solution ; the salts
in question are generally called sulphocyano-pla-
tinites and sulphocyano-platinates, or sometimes
platmoso- and platino- sulphocycmides. The K
salts are formed by reaction between KSCy and
PtOljAq or PtCljAq; the salts of the heavy
metals are formed from the E salts by double
decomposition. Both series of salts are decom-
posed by CI or HNOjAq with formation of HCy,
H2S0j(HCl), K2S04(KN03), and separation of a
brownish-red solid which is probably Pt(SCy)jj.
NHjAq reacts with salts of both series to form
pikbiioscmanonium sulphocyanide (N2H5Pt).2SCy
(j. v.). The sulphooyano-platinum compounds
have been chiefly investigated by Buckton (O. J.
7, 22).
Sulphocyanoplatinous acid
H2Pt(SCy)4Aq. {Platijwso-sulphocyanio acid.
Platinoso-sulphocyanhydrie acid.) Known only
in aqueous solution, which is obtained by care-
fully adding dilute HjSO^Aq to the Ba salt ; the
solution soon decomposes even by evaporation
in vacuo, giving HSCyAq and a pp. containing
Pt.
Ammonio-platinous sulphocyano-
platinite or platinoso-sulphocyanide
(NjH,2Pt).Pt(SCy)i. (Diammomo-platosammo-
mum sulphocyano-plaUnite,
(N2H4[NHJjPt).Pt(SCy)4.) Obtained by adding
KSCyAq to diplatosammonium chloride,
NJH4[NHJjjPt2.01j ; buff pp. ; insol. in water and
alcohol, sol. in dilute HClAq ; when heated it is
decomposed, burning like tinder, and leaves Pt.
This salt seems to be polymeric vrithplatosammo-
nUim sulphocyamde, (NjH8Pt).2SCy (q. v.).
Potassium sulphocyanoplatinitc or
platinoso-sulphocyanide Kj,Pt(SCy)4. Pre-
pared by dissolving equal parts of PtClj andKSCy
in as small a quantity as possible of hot water,
and crystallising from alcohol the salt which
separates. Also by adding PtOl2.2ECl in small
successive quantities to cone. KSCyAq, crystal-
lising from alcohol, pressing between paper, and
re-orystaUising from water. Bed microscopic
crystals; six-sided prisms; S. 40 at 16-5°; v.
sol. in alcohol. Non-deliquescent ; not changed
at 100° if aiy; decomposed by NHjAq to
(NjHePt).2SCy and KSCyAq.
Silver sulphocyano-platinite or pla-
tinoso-sulphocyanide Ag2Pt(SCy)4. White
curdy pp. by adding AgNOjAq to solution of the
K salt. Partly soluble in NHjAq with decompo-
iiition ; sol. in KSCyAq.
Sulpho-oyanoplatinic acid ox platino-
suiphocyanio acid {PlaUno-sidphocyamhy-
iriQ acid) HjPt(SCy),Aq. Knqwn only in a^iie- ;
ous solution, which is obtained by decomposing
the Pb salt by HaS ; decomposes when evapo-
rated, even in vacuo ; dark-red liquid with acidic
taste ; decomposes carbonates and dissolves Zn
evolving H.
Ammonium sulphocyanoplatinate or
platino-sulphoc^anide (NH4)2Pt(SOy)i5.
Carmine-red six-sided tables ; formed by boiling
1 part (NH4)jS04 with IJ parts KjPt(SCy)e in
oono. solution, separating (NHj)2S04 and KjS04
by adding alcohol, and re-crystallising the salt
jErom warm water. Aqueous solution is decom-
posed by boiling, giving off HSOy.
Barium sulphocyanoplatinate or
platino-sulphocyanide BaPt(SCy)5. Bed
needles ; sol. in water and alcohol ; by reaction
between excess of BaCljAq and KjPt(SCy)e, eva-
porating and dissolving in alcohol.
Cuprio sulphocyanoplatinate or
platino-Sulphocyanide; green pp. by add-
ing KjPt(SOy)sAq to CuS04Aq, probably
CuPt(SCy)j; becomes black when liquid is
boiled ; sol. in NHjAq, reppd. by HClAq.
Iron sulphocyanoplatinates or pla-
tino-sulphocyanides. The ferrous salt
FePt(SCy), is a black crystalline pp., insol. in
water and alcohol, obtained by adding slightly
acidulated FeSOjAq to cone. KjPt(SCy)sAq. The
ferric salt is prepared by using FeCl,Aq in place
of PeSOjAq and boiling ; probably Pe32Pt(SCy),.
Lead sulphocy anoplatinate or pla-
tino-sulphocyanide PbPt(SCy)B; golden-
yellow hexagonal plates, obtained by mixing
cone. Pb(CjH302)2Aq and cone. K2Pt(SCy)j, wash-^
ing with cold water, and crystallising from al-
cohol ; decomposed by hot water. The basic
salt PbPt(SCy)s.PbO is formed as a red pp. by
ppg. basic Pb acetate solution with cone.
K2Pt(SCy),Aq.
Mercurous sulphocyanoplatinate or
platino -sulphocy anide'B%^i(SGj)^,j^oyi
pp. by adding HgNOsAq to Ks,Pt(SCy)sAq.
Potassium sulphocyanoplatinate or
platino-sulphocyanide K^Pt^SOy),. Pre-
pared by adding 2 pts. E^PtClu to a warm solu-
tion of 2^ pts. KSCy, heating nearly to boiling,
filtering, and allowing to crystallise ; the crystals
are dissolved in boiling alcohol (to separate
KCl), and the liquid is passed through a filter
which is kept warm. Also produced by adding
PtCljAq to cone. KSCyAq at 70°- 80°, and allow-
ing to cool. Deep carmine-red, six-sided prisms ;
permanent in air at ordinary temperatures;
S. c. 8^ at 60°, S. much greater at 100°. Crys-
tallises with 2H2O according to Gmelin (c/. Wyru-
bow, Bl. [2] 33, 402). Heated to redness gives
KSCy, Pt, and gase'^us products. Decomposed by
hot H2SO4 or HClAq. With HNOjAq or CI pro-
bably gives Pt(SCy)». Reacts with NH^Aq or
{NH4)2COsAq to form KjS04, KSCy, NH4Cy,
NH,SOy, and ppt. yellow needles of platosam-
monium sulphocyanide (NjHjPt).2SCy (g. v.).
Silver sulphocyanoplatinate or
platino - sulphocyanide Ag2Pt(SCy)8.
Orange-yeUow pp. by mixing AgNOjAq with
K2Pt(SCy)5Aq. Forms a double salt
Ag,Pt(SCy)„.2KSCy.
Sodium sulphocyanoplatinate oi
platino - sulphocyanide NajPt(SGy)3.
Garaet-cgloured tablets ; obtained by de^ompos-
362
CYANIDES.
ing the Pb salt by NajSOjAq; sol. water and
alcohol.
FlatoBammosinm sulphocyauide
(N5,HsPt).2SCy. This salt is obtained by de-
composing potassium platiuo-sulphooyanide
EjPt(SCy)j (v. supra) by NHjAq or (NHJ^dOsAq,
collecting the crystals which separate, washing
them with cold water, and reorystallising from
alcohol. It is also produced when NHjAq re-
acts with potassium platinoso-sulphocyanide
ICPt(SOy)„ or by mixing 1 pt. KSCy with 1-6 pts.
platosammonium chloride NaH^PtCl^ in aqueous
solution, heating nearly to boiling, adding an
equal volume of alcohol, filtering hot, and allow-
ing to cool. Straw-yellow needles ; melts at
100°-110° ; decomposes at c. 180°, giving off
NHj and HCy, and also SOj if in air, and leaving
Pt. Sparingly sol. cold water, more sol. alcohol.
Not acted on by dilute HClAq or HjSO^Aq.
Aqueous solution is decomposed on boiling, evolv-
ing NHj (Buckton, 0. J. 7, 22). The salt de-
scribed as ammonio-platinoits platinoso-sulpho-
cyanide (N2H4[NHj2Pt).Pt(SCy)4 (v. p. 351) is
probably polymeric with platosammonium
sulphocyanide.
PotasBium sulphocyanide ESCy. H.F.
[K,S,Cy] = 87,800 (Joannis, A. Ch. [5] 26, 482).
Formation. — 1. By fusing 1 pt. dry K4FeCys
with 3 pts. KjSA (Frohde, P. 119, 317).—
2. By heating NHjSCy with KOHAq, or
(NH^),CS, with KjSAq (G61is).— 3. By adding a
mixture of S, C, and (NH4)2S04 to a molten mix-
ture of KOH and S (Fleck, D. P. J. 169, 209)
[(NH4),S04 + C + S = NH^.SCy + SOj + 2B.fi ; and
2NH,SCy + KjS = 2KSCy + (NHJ^S].— 4. An
aqueous solution of ECy (65 pts.) is digested
with S (32 pts.) until S is all dissolved (Wiggers,
A. 29, 819).
Preparation, — A mixture of 32 pts. S with
17 pts. KjCOj is heated until it melts, 46 pts. dry
KjFeCy, are added, and heating is continued
until the mass fuses quietly and a little taken
out does not give the reactions of ferrocyanide ;
temperature is then raised for a little to change
any K^SjOa into E^SO, ; the cold mass is ex-
tracted with water, and the liquid is neutralised
by HjSOiAq; the liquor is evaporated to dry-
ness, the residue is boiled with alcohol, the
alcoholic solution is filtered and crystallised
(Henneberg, A. 73, 230 ; c/. Liebig, A. 50, 345 ;
61, 288; Babcock, Z. 1866. 666; Frohde, P.
119, 317).
Properlnes. — Long, white, striated prisms,
resembling nitre. S.G. 1-886-1-906 (Bodeker,
J. 1860. 17). S. 177-2 at 0°, 217 at 20° (Eiidorff,
B. 2, 68). By dissolving 150 pts. of the salt
in 100 pts. water at 10'8°, temperature falls
to -23-7° (Evidorff, B. 2, 68). Joannis {A. Ch.
[5] 26, 482) gives the heat of solution [KSCy,Aq]
= -6100. Melts at 161-2° (Pohl, J. 1851. 59).
The molten salt becomes brown, then green,
finally indigo blue, but on cooling it again goes
white (Nolluer, P. 98, 189). Non-poisonous
(Wohler a. Freriohs, A. 65, 342 ; Hermes, J. pr.
97, 465). According to Berzelius {S. 31, 42),
when KSCy is heated in moist air it evolves
CO2 and NH3 and KjS remains. KSCyAq slowly
decomposes, quickly on boiling, evolving NHj
<Yogel, S. 23, 15).
Heactions. — 1. Chlorine passed into melted
f^^Cj forms S^jCl, aad CyjCl, (Liebig, P. 16, 648;
34, 676). CI passed into fairly cone. KSCyAq
forms pseudosulpliocyanogen C3N3HS3: with
excess of CI, NH„ H.,SOj, HOI, and COj are pro-
duced (Liebig, A. S9, 215 ; 50, 337 ; Volckel, A.
43, 97 ; Paruell, P. M. 17, 249).— 2. Cone, nitric
acid ppts. OjNjHSa (Liebig ; Volckel). — 3. Potas-
sium permanganate, manganese dioxide, or lead
peroxide oxidises the S of KSCy to H2S04 (Hadow,
a. J. 11, 174).— 4. Molten KSCy reacts violently
with hydrochloric acid gas, forming HCy, CS„
and NH4CI (Liebig, l.c.). — 5. Heated gently with
phosphorus pentachloride CyCl, KCl, and PSOl,
are produced ; at a higher temperature the pro-
ducts vary (Schiff, A. 106, 116).— 6. Heated with
iron FeS, KjS, and K^FeCy^ are formed (G61is,
P.ep. Chl/m. App. 1862. 370).— 7. KSCyAq electro-
lysed gives H,,SO„ SO2, HCy and S (Sohlagden-
hauffen, J. Ph. [3] 49, 100).
Combinations. — With merctiric cyanide and
iodide to form KSCy.HgCyj.2H2O (Bockmann,
A. 22, 153; ClAve, Bl. [2] 23, 71; Philipp, P.
131, 86) : 2KSCy.HgI2.2HjO (Philipp, I.C.).
Silicon sulphocyanide Si(SCy)4 v. Silioon.
Silver sulphocyanide AgSCy. H.F. [Ag,S,Cy]
= 16,500 (Joannis, 4. Ofe. [5] 26, 540). While
curdy pp. by adding KSCyAq to AgNOjAq.
Blackens in light. Insol. water and dilute acids;
sol. NH,Aq and alkali sulphecyanides, also in
HgNOjAq (Wackeuroder, A. 41, 317). Addition
of NHjAq to a solution of AgSCy in NHiSCy
ppts. shining tablets of the dotiile compoumd
AgSCy .NHj ; loses all NH, by treatment with
w^ter (Gintl, W. A. B. 60, 474 ; Weith, Z. 1869.
310; c/. Gossmann, A. 100, 76). Solution of
AgSCy in hot KSCyAq on cooling deposits the
double salt AgSCy.KSCy ; decomposed by water
(Hull, A. 76, 93). The double salt AgSCy.NH.SOy
is also known (Gossmann, 4. 100, 76; Fleischer,
A. 179, 225).
Sodium sulphooyanide NaSCy. H.F. [Na,S,Cy]
= 77,100 (Joannis, A. Ch. [5] 26, 540). Prepared
by neutralising HSOyAq by NajCO,, evaporating,
and crystallising from alcohol. Also by heating
1 pt. KjFeCys with 3J pts. dry NajS.jOj, and dis-
solving out with hot alcohol (Frohde, P. 119,
317; Meitzendorff, P. 56, 63). Very deliquescent
rhombic plates ; e. sol. alcohol. Forms the
double compound NaSCy.HgCy, (Cl^ve, Bl. [2]
23, 71).
Scrontium sulphocyanide . Sr(SCy)2.3H20.
Prepared by neutralising HSCyAq with SrCOa,
and evaporating at 100°, and then over HjSO,
(Meitzendorff, P. 56, 63). Gives off SH^O at 100°,
and begins to decompose at 160°-170°. Forms
the double compoimd Sr(SCy).,i2HgCy2.4H20
(ClAve, Bl. [2] 23, 71).
ThallouB sulphocyanide TlSCy. Small
shining needles ; by mixing TljCOjAq with
KSCyAq (Kuhlmann, J. pr. 88, 175 ; Hermes,
J.pr. 97, 465). For crystalline form «. Miller
(Pr. 14, 455). Forms a double salt with KSCy
(Carstanjen, J. pr. 102, 129).
Tin sulphocyanide. The stannous salt
Su(SCy)2 is obtained by heating freshly ppd.
SnO.aiBLjO in HSCyAq, filtering, boiling, filtering
again from SnO, and evaporating. Citron-yellow
crystals ; sol. water and alcohol ; aqueous solu-
tion reflects blue light (Olasen, J. pr. 96, 349).
Stannic hydrate scarcely dissolves in HSCyAq.
Uranium sulphocyanide U(SCy)2. Daik
greeii mass, by dissolving uranoua hydrate iff
OYANO-AOETIO ACID.
369
HSOyAq and evaporating (Eammelsberg, A. 43,
235). Existence of uranic sulphooyanide is
doubtful (v. Porret, 2". 1814. 527).
Tttrium sulphocyanide Y(SGy)3.6H20 (014ve
%. Hoeglund, Bl. [2] 18, 197). Forms the double
compmifid T(SCy)j.3HgCyj.l2HjO {CUve, J.pr.
91, 227).
Zinc Bolpliocyanide Zn(S0y)2. White crystals;
obtained by dissolving freshly ppd. ZnCOj in
HSCyAq, evaporating, and crystallising from
alcohol (Meitzeudorfl, P. 56, 63). Dissolves in
NH,Ac[, rhombic prisms separate of the double
aympound Zn(SCy)2.2NHj ; these are decomposed
by water to ZnO and NH^SCy (Meitzendorff,
I.C.; Fleischer, A. 179, 225). Also forms the
double compounds Zn(SCy)j.2HgGy2.4H20, and
Zn(SCy),.2HgOyj.BNH, (Cldve, Bl. [2] 23, 71).
TBLLUEOCTANIDBS. — A potassium
tellurooyanide is probably momentarily formed
when Te and EGy or E^FeCyg are melted
together, but if so it is quickly decomposed on
treatment with water with ppn. of To (Berzelius,
S. 31, 60). M. M. P. M.
CYANIDIKE, a name proposed by Pinner
(B. 18, 760) for derivatives of CaNjH, in which
H, is displaced by hydrocarbon radicles, e.g.
CjNjMej would be tri-methyl-oyanidine. These
compounds are mostly described as paranitriles
of the corresponding acids. See also Cyane-
XBiNii, Ctanmbthethine, and Oyahmethine.
CYAKIXiIC ACID v. Cyanic acids.
CTAirilSrE or QTJINOLIHE BLUE v. Qdino-
2-7 at 20°.
•Pi'eparaftion. — Sodium (1 pt.) is added to a
mixture of propionitrile (6-6 pts.) and aceto-
nitrile (3-3 pts.). The sodium dissolves with
evolution of gas^ The product is freed from excess
of nitriles by distillation, washed with water and
fractionally crystallised from alcohol and benz-
ene. Cyanethine is first obtained, but the chief
portion is cyan-meth-ethine, formed thus :
iC^B.fiT!( + OBi,aS = C,U,^, (0. Riess a. E. v.
Meyer,,r.iW. [2]31, 112J.
Properties. — Trimetric plates (from benzene).
Begins to sublime below 100°.
Salts.— B',HGl,AnCl3. Plates.—
(E'lHCy^PtClj. Clustered needles.
nombvnaUori,. — ^B'j,AgN03.
Meactions. — 1. Bromine warmed with a solu-
tion of the hydrobromide forms a colourless
solution, out of which NH, throws down bromo-
cyanmethethine, OgH,jBrNs. This is soluble in
hot water, alcohol, ether, and benzene, and forms
trimetric crystals [155°].— 2. HCl at 180° forms
an ' oxy-base ' [150°].
CYANMETHINE CsH,Ns. [181°]. S. 156 at
18°. S. (alcohol) 19 at 18°-
.;.' Preparation. — ^From aoetonitrile (methyl cy-
anide) (6 pts.) and sodium (1 pt.) (Baeyer, B. 2,
319 ; KeUer, J. pr. [2] 31, 366). Marsh gas is
evolved, not ethane.
Properties. — Very similar to cyanethine, but
2,140 times more soluble in water. It may be
crystallised from alcohol. Its aqueous solutions
give pps. with AgNOa, Pb(OAc)j, HgGlj, and BaGl^
(B. V. Meyer, J.pr. [2] 27, 152).
Com6iMa<ions.-(0„H„N3)jAgNO,. Ehombo-
bedra (from hot water).
Reactions.— 1, 'S.ft,, passed into a solution
Vot. II.
of oyanmethine in glacial acetic acid, forms an
oxy-base, 0„H,N2(0H) ; the nitrate of this base,
C8H9NjO,HNOs, separates as tufts of needles
from the cold solution. The free base, CuHjNjO,
melts at [193°], and crystallises from alcohol in
needles. This base is also formed by heating
oyanmethine with HCl at 180° (WoUner, J. pr.
[2] 29, 131). The nitrate of the oxy-base gives
with AgNOs, on neutralising with NHj, a pp. of
CjHjAgN.20. — 2. Bromine gives, even in the
cold, a bromo-cyan-methineil4S°']. Decom-
posed by boiling water, with formation of NH^Bn
Nitrous aoid gas, passed into a solution of
bromo-cyanmethiiie in glacial acetic aoid, gives
white needles of the nitrate of the bromo-'oxy-
base': C„H,BrNjO,HNO, [158°]. This com-
pound forms a silver derivative : G^HsAgBrNjO.
Bromo-cyan-methine retains its bromine much
more strongly than bromo-cyanethine. It is
converted by phenyl cyanate into a urea :
GABrN2.NH.GO.NPhH [186° -206°]. Bromine
converts this into a tri-brominated urea,
probably 0,H,BrN2.NH.CO.NH.C„H3Brj [257°].
3. Chlorine forms a dichloride of ohloro-cyan-
methine, whence aqueous NH, liberates chloro-
cyan-methine GaHjClN,. (Cyan-ethine forms
a tri-ohloro-. derivative.) N^O, converts the di-
chloride, G,H9GlN„Gl2, dissolved in glacial acetic
acid, into the nitrate of the chloro-' oxy-base,'
CbH,G1N20,HNOs. [153°].— 4. Phenyl cyanate
(6 g.), warmed with oyanmethine (5g.) dissolved
in benzene, forms crystals of a complicated
urea: GjH,N2.NH.C0.NPhH. This melts at
[225°]. Bromine added to its solution in HGI
forms a di-bromo- derivative [238°].
Salts.— B'HCl: needles. — B'.,H,PtGls. —
B'HI. — B'lo. — B'HIj. — B'HIj. — B'HNO,. —
B'jH,SO,.— B'(H,SO ,),.-B',H AO4 2aq.
Constitution. — The presence of amidogen in
cyan-methine is shown by the action of phenyl
cyanate and of N^O, upon it. Other reactions
indicate, however, that it is differently consti-
tuted to cyanethine.
CYANO-ACEXIC ACID OsHjNO^i.e.
CN.GHj.COjH. Semi-nitrile of malonia acid.
Mol. w. 85. [55°] (Van 't Hoff, Ar. N. 10, 274).
Formed by boiling ohloro-aoetio ether (250 g.)
with KGy (300 g.) and water (1,200 g.) (Hugo
MuUer, A. 131, 350; Moves, A. 143, 201).
Properties. — Crystalline ; decomposed by
heat into CO.^ and aoetonitrile.
Beactions. — 1. Boiling aqueous KOH gives
malonic acid. — 2. Br gives di-bromo-aoetonitrile,
bromoform', and COj (Van 't Hoff, B. 7. 1383,
1571). — 8. Electrolysis gives ethylene cyanide
[38°] (Moore, Am. S. [3] 3, 177).
Salt s. — KA' : deliquescent. — ZnA'^ 2aq. —
HgA'22HgO.-PbA'jaq.— MnA'2 2aq (Bngel, Bl.
[2] 44, 424) : beautiful crystals. — GuA'j.— AgA'.
Ethyl ether BtA'. " (207°).
Dissolves sodium, forming CN.CHNa.GO^Et
as a white, very hygroscopic, and easily fusible
powder. This sodium derivative is easily acted
on by alkyl iodides, thus CH3I gives rise to
CN.CH(CH,).CO,Et (194°). V.D. 4-34; C^HJ
gives CN.dH(G,H3).C0,Bt (204°). V.D. 4-63;
0,nj. gives CN.GH(G3H5).C02Et (215°-220»).
ClCO.OEt acts easily upon the Na derivative^
giving GN.GH.(C02Et)2. The mono-chlor- and
mono-bromo-derivatives are formed with remark-
able neatness. CN.CHCl.CO^Bt is a colourless
AA
S64
CYANO-AUETIC ACID.
liquid, with a pungent odour (190°). V.D. 5-11
(Henry, O, B. 104, 1618; Haller, Bl. [2] 48, 27).
The following ethers have been obtained by
the action of Na and ethyl or methyl oyanacetate
upon the corresponding diazo-chloridea : —
Methyl bemene-aeo-cyanaoetate
C,H5.Nj.0H(CN).C0,Me. [86°].
Ethyl bemene-azo-cyanacetate
06H5.N2.CH(CN).COjEt. [125°].
Methyl o-toluene-aao-cyanacetAte
CeH,Me.N2.CH(CN).C0jMe. [167°].
Methyl p-tolioene-azo-cyanacetate
C8H4Me.Nj.CH(CN).C02Me. [133°].
Ethyl o-toluene-azo-cyanacetate
C8HjMe.Nj.CH(CN).C02Et. [126°].
Ethyl p-toluene-azo-cyanacetate
C,3:,Me.Nj.CH(CN).002Bt. [74°] (Haller, C. B.
106, 1171-1174).
Amide CN.CHj.CONHj. [118°]. Formed
by dissolving cyano-aoetie ether in aqueous am-
monia, and allowing the solution to evaporate
spontaneously. Crystallises from alcohol in
small needles (Henry, 0. B. 104, 1618).
Acetyl-cyano-acetic acid
CH3.C0.CH{CN).C0jH.
Methyl ether MeA'. [47°]. From
CHj.OO.CHNa.COjMe and cyanogen chloride in
MeOH (Haller a. Held, O. B. 106, 210). Also
from CN.CHNa.COzMe and acetyl chloride. —
Ca(C5H(N03)2 6aq : efflorescent crystals.
Ethyl ether EtA'. Formed similarly; v.
Cyano-aceto-aoe*ic ethek.
Propionyl-cyano-acetio ether
CH,.0Hj.C0.CH(CN).C02Et. (160°) at 50 mm.
— Ca(0,H,„N03),2aq.
TC-Butyryl-oyano-aeetic ether
PrC0.CH(CN).002Et. (171°) at 66 mm. —
CaA'jjSaq.— BaA'jSiaq (HaUer, G. B. 106,
1085).
Isobutyryl-cyano-acetic ether
¥r.CO.CH(CN).CO,Et. (173°) at 85 mm. —
CaA'jSaq.
Senzoyl-cyano-acetic ether v. Cyakobenz-
OYii agetio acid.
o-Toluyl-cyano-acetic ether
C,H4Me.C0.CH(CN).C0jEt. [35°]. Prisms
(Haller, G. B. 107, 104).— CaA'24aq.
Fhenyl-acetyl-cyano-acetic ether
CH2Ph.0O.GH(ON).COjEt. Oil.
Cinnamyl-cyano-acetie ether. [104°].
Di-oinnamyl-cyano-aoetio ether
(PhCH:CH.CO).C(CN).COjEt. Silky needles.
CYABTO-ACETIC ALDEHYDE CH,(CN).CHO.
(72°). S.G.15-881. V.D. 2-33. Formed by the
action of AgCN as an alcoholic solution of
iodo-acetio-aldehyde. Colourless mobile liquid.
Misclble with most solvents. It does not solidify
at —20°. It reduces Fehling's solution, forms
a compound with NaHSOj, and is resiuified
by NaHO and HCl. HNO3 oxidises it to cyano-
acetic acid. It forms with aniline a base ril3°l
(Chautard, G. B. 106, 1167-1169).
CyANO-ACETO-ACETIC ETHEE
CH3.CO.CH{CN),C02Et, [27°]. (119°) _ at
20 mm. Formed by the action of potassium
cyanide on ohloro-aceto-aoetic ether; the salt
CN.CHj.C(OK):CH.COjEt being also formed in
small quantity (James, A. 240, 61 ; C. J. 51,
287 ; 0. J. Proc. 3, 25). Formed also by treat-
ing sodium aceto-aoetio ether with cyanogen
ebloride, and frpm cyano-acetic ether and AcCl
(Haller a. Held, Bl. [2] 47, 888 ; C. B. 96, 235;
104, 1627 ; 105, 115).
Properties. — Silky needles, cannot be dis-
tilled. Insol. water, sol. alcohol and ether.
Gives a characteristic red colouration with
FojCls. Decomposed by boiling alkalis into
acetic acid, CO^, and ammonia.
Salts.— NaCjHsNOj : crystals (from alcohol).
EA' : needles (from alcohol) ; insol. ether and
benzene.— CaA'j Baq : monoclinio crystals (from
alcohol).
CYANO-AOETONE C4H5NO i.e.
CH,.CO.CHjCN. _ (0. 123°). Prom chloro-
acetone and KCy in dilute alcohol (Matthews a.
Hodgkinson, B. 15, 2679). Converted by alco-
hol and HCl into aoeto-acetic ether.
Isomeride. [166°]. From chloro-aoetone and
aqueous KCN (Glutz, J. pr. [2] 1, 141; cf. Ben-
der, B. 4, 518). Very volatile crystals. Forma
a crystalline compound with HI.
M-CYAWd-ACETOPHENONE v. Benzoti,-
ACETONITKILE.
jp-Cyano-acetophenone
[4:1]C5H,(CN).C0.CH3. [61°].' From p-amido.
aoetophenone by displacing NH^ by Cy (Ahrens,"
B. 20, 2955). Needles (from dilute alcohol).
Boiling alcoholic EOH converts it into aceto-
phenone p-carboxylic acid (q.v.).
Oxim. C3H4(CN).C(NOH).CH3, [160"].
CYANO-ACETYI. BROMIDE CHi(CN).COBr.
Appears to be formed, together with the isomeric
bromo-acetyl cyanide, by heating AgCN with
bromo-acetic acid and chloroform (Hiibner, A.
124, 315; 131, 66). Needles (from ether or
chloroform). Converted by EOH into cyano-
acetic and malonic acids.
CYANO-ACETYL-DI-METHYL-TJEEA
NHMe.CO.NMe.CO.CR,.CN. [above 260°]. Pre-
pared by the action of cyano-acetyl chloride on
dimethylurea (Mulder, B. 12, 466).
CYANO-ACETYL-UBEa.
NH2.CO.NH.CO.CHj.ON. [200°_210°]. SI. sol.
water and alcohol. Prepared by the action of
cyano-aoetyl chloride on urea (Mulder, B. 12, 465 ;
Bl. [2] 29, 531).
CYANO-AITGELIC ETHEB
C,H5.CH(CN).C02Et. (0. 218°). From sodium
cyano-acetio ether and allyl iodide (Henry, 0. B.
104, 1618).
DI-CYANO-BENZENES v. Nitnles 0/
isoPHTHALio and Tekephthalio acids.
o-CYANO-BENZOIC ACID C3H3NOJ i.e.
CjH4(CN).C0jH. Semi-mtrile of phthalic add.
Appears to be formed from o-amido-benzoic acid
by the diazo- reaction, but changes spontaneously
into the isomeric phthalimide (Sandmeyer, B.
18, 1499).
Ethyl e«;ierA'Et: [70°]; needles; v. sol.
alcohol, ether, &a., si. sol. hot water. Obtained
from anthranilic ether by diazotisation and treat-
ment with Cu2(CN)j (Miiller, B. 19, 1498).
TO-Cyano-benzoic acid C8H,(CN)00jH [1:3].
[217°].
Formation. — By the action of a hot solution
of cuprous potassium cyanide upon m-diazo-
benzoic chloride (Sandmeyer, B. 18, 1498).
Properties. — Mibroscopio needles. V. e. sol.
ether, alcohol, and hot water. Gives isophthalio
acid on saponification. By distillation of the Ca
salt with lime benzonitrile is formed. By HNO, it
ig oxidised to isophthalic acid. By alcoholic H|S
CYANO-BUTYRIO ACID.
S55
it is converted into th e acid OfjHuOiNjS probably
CA(COjH).0(NH).S.C(NH).C,H,{CO,H) [199'^]
whence tin and HCl pive a>-imido-m-di-toluio
acid. By treatmejit with fuming sulphuric
acid and pouring the mixture into water it
yields 0|sH,„0jN2 probably
0„H,(GO,H).0(NH).O.C(NH).C,H,(COjH).
[above 300°].
Salts.— OjH4(CN).C02A.g: insoluble pp.—
A'jCa 3aq : crystals, sol. hot water. — A'^Ba S^aq :
soluble crystals. — A'^Zn : white pp.
Methyl ether A'Me : [65°]; crystals; v.
b1. sol. water, v. sol. alcohol, ether, &o.
Ethyl ether A'Et: [56°] ; crystals; nearly
insol. water.
Amide CsHi(CN).C0NH2 : [above 300°];
V. Bol. alcohol and ether, insol. water.
Amidoxim C„U,(GO^B.}C{NB.^):^OIi :
[198°] ; crystalline. Formed by the action of
hydroxylamine upon m - cyano - benzoic acid
(Bromme, B. 20, 524; cf. Miiller, B. 19, 1494).
y-Cyano-benzoic acid C,JI,(CN)C02H [1:4].
Formed by the action of a hot aqueous solution
of cuprous potassium cyanide upon p-diazo-ben-
zoio chloride (Sandmeyer, B. 18, 1496). Quickly
changes into terephthalamic acid.
Ethyl eifeer A'Et : [54°] ; needles; v. sol.
alcohol and ether (Maier, B. 18, 2485).
ISO-CTANO-BENZOFHENONE
CjH5.C0.CsH,NC. [119°]. FromjB-amido-benzo-
phenone, chloroform, and alcoholic KOH (Doebner,
B. 14, 1838). Silky needles, when hot it smells
unpleasant. HCl splits it up into formic acid
and amido-acetophenone.
]]i.^.cyauo-benzophenone
C.H^(CN).CO.CeH,(CN). [205°]. Formed by dry
distillation of calcium ^-cyano-benzoate. Warty
crystals. Sublimable. V. sol. alcohol, ether,
and benzene, slightly sol. petroleum -ether and hot
water. With phenyl-hydrazine it yields the oom-
C^^O(NH^:N,HPh
pound \C:NjHPh . The latter body
^«^*\C(NHj):N2HPh
forms warty crystals [212°]; v. sol. alcohol,
ether, benzene, and CS2 (Bromme, B. 20, 521),.
Isocyauo-benzophenone v. BsiizosL-FUEiiyL-
OABBAMINE.
CYANO-BENZOYL-ACETIC ACID.
. Methyl ether CBzHCy.CO^Me. [74°].
From methyl cyano-acetate and BzCl (Barthe,
C. B. 106, 1416). Long prisms, sol. ether and
alcohol. Gives a red colour with FeClj, _ Its
alcoholic solution has an acid reaction. Boiling
waterspHtsitupintoC02andPh.CO.CHjCy[82°].
Its sodium derivative Oy.CBzNa.COjMe
forms hard crystals, decomposing at 123°- Its
barium salt Ba(CBzCy.COjMe)j aq is also crys-
talline.
Ethyl ether C|„H,NOj i.e.
C,H;,,.CO.CH(CN).COjEt. [41°]. From benzoyl-
aoetic ether, NaOEt, and CyCl. Also from
CN.CHNa,COjEt, and BzCl (Haller, C. B. 101,
1270 ; 105, 130). Prisms ; sol. alcohol, aqueous
alkalis, «nd NajCOjAq. Gives an intense red
colouration with Fe^Clj. Boiling water forms
cyano-aoetophenone and COj. AlcohoUo HCl
gives CO2 and acetic and benzoic ethers.
o-CYANO-BENZYI-AMINE
C^^(CN).CHj.NHj. Formed, together with
phthalic acid, by digesting phthal-o-cyano-
benzylJmide with fuming HCl. The solution of
its hydrochloride is converted by nitrous acid
into nitroBo-phthalimidjne. — B',HC1 aq ; glisten-
ingneedles. PiorateB'0|jHj(NOJ,OH: sparingly
soluble yellow crystalline pp. (Gabriel, B. 20,
2232).
o-CYANO-BEHZTL CHLOEIDE
CjH<(CN).CH2Cl[l:2]. [61°]. (252° at 758 mm.).
Monosymmetrical colourless crystals a:b:i
= -7775 : 1 : -2939, J3 = 60° 2'. Prepared bj leading
chlorine into nearly boiling o-cyano-toluene till
its weight has increased by 30 p.c. (Gabriel a.
Otto, B. 20, 2222).
o-CYANO-BENZYL-CYANIDE
CeH,(CN).CH2.CN [1:2]. o-Cymio-phenyl-aceto-
rdtrile. [81°] .
Prejparation. — o-Cyano-benzyl chloride (30
pts.) is added to a solution of 15 pts. of potas-
sium cyanide (96-98 p.c. KCN) in 60 o.c. of water
and 300 c.c. of alcohol. After cohobating tor
I hour, § of the alcohol is distilled off and the
residue poured into water (about f litre) ; the
crystals which separate are recrystallised from
alcohol (yield : 25 pts.) (Gabriel a. Otto, B. 20,
2224, 2502).
Properiiest — Colourless plates. V. sol. ordi-
nary solvents. By warming with alcoholic so-
dium ethylate and Mel or EtI it is converted
into CeHj(CN).CHMe.CN or C,H,(CN).CHEt.CN.
By heating with cone. H^SO, at 80°, and pouring
the product into water it is converted into the
imide pf phenyl-acetic-o-carboxylic acid
.CH..CO
C.H /
\ CO.NH
a-CYANO-BENZYUDEHE-PHTHALIDE
C = C(CN).C,H5
CjH^/^O [165°]. Fine yellowish needles.
CO
Formed by heating phthalic anhydride with
benzyl cyanide, best with addition of dry sodium
acetate (Gabriel, B. 18, 1264).
o-C YANO-BENZYL-P HTHALIMIDE
C = N.CH,.C„H<(ON)
C.^H.jNjOj i.e. C„H,/No. Phthal - 0 ■ cyano ■
CO
bimyl-imide. [182°]. Prepared by heating
phthalimide-potassium (9 pts.) with o-oyano-
benzyl chloride (7 pts.) slowly from 100° to 120°.
Large prisms. By boiling with fuming HCl it
is split up intophthalic acid and o-cyano-benzyl-
amine (Gabriel, B. 20, 2231).
eao-CYANO-BENZYL-UEEA v. Phenyl-
DBAMIDO-AGETOIIITBILE.
CYANO-BOBNEOL. Has been shown by
Haller to be bornyl carbamate (q.v.). 7. also
GmEOL.
^-CYAKO-ISOBUTYL-BENZENE v. Nitrite
o/^-(iso)-BurrL-BENzoio acid.
o-CYANO-BTJTYB,IC ACID
CH,.CHj.CH(CN).CO,H.
Ethyl ether EtA'. (209° cor.). S.G. 2
1*009. From o-bromo-butyrio ether, alcohol,
and HgCy^KjCyj at 180° (Markownikoff, A. 182,
330). Also from sodium oyano-acetic ether and
EtI (Henry, C. B. 104, 1618).
Amide CH,.CHj.CH(CN).qONHj. [113°].
Pearly scales (from alcohol).
aa2
356
OYANO-BUTYRO-ACETIO ETHER.
CYANO-BTTTYRO-ACETIC ETHEB
CH,Me.CHj.C0.CHGy.C02Et. (o. 172°) under
66 mm. From sodium cyano-acetic ether and
butyryl chloride (Haller, C. B. 106, 1083).—
CaA'j 2aq. — ^BaA', 3aq.
Cyano-iso-bntyro-acetlc ether
CHMe„CO.CHCyCOjEt. (174°) at 85 mm. Formed
asabovefromisobntyrylohloride(H.).^-0aA',2aq.
CYANO-CAMPHOE v. Camphor.
CYANO-CAKBIMIOAUIDO-BENZOIC ACID
«. vol. i. p. 157.
CYANO-CARBONIC ACID v. Oianofobmio
ACID.
CYANO-CAEBOXAMIDO-BEITZOJC ACID v.
vol. i. p. 157.
CYANO-TBI-CABBALLYLIC ETHER
C„H,i,NOs i.e. 0(0N)(CO2Et)(CHjC0jEt)j.
[4i°]. {197°). Formed in small quantities in
the preparation of cyano-suooinio ether {q. v.).
It is also formed from cyano-succinic ether by
Ha and chloro-acetic ether. Colourless. Sol.
alcohol and ether; insol. water and alkalis
(Haller a. Barthe, G. B. 106, 1414).
M-CYANO-CIlIlIAMYI.-irEEA v. NitriU of
PHENYL-a-UEAMlDO-CROTONIO ACID,
CYANO - CROTONIC ACID CjH^(CN)02H.
When liberated from its salts by an acid, it
changes to acid ammonic crotaconate.
Salt. — KA'. From o-ohloro-crotonic acid,
cold dilute alcohol and KCy (Clans a. v. Waso-
wicz, A. 191, 69). Boiled with KOH it forms
crotaconio acid (g. «.). — AgA'.
/S-Cyano-crotonic ether CH3.C(0N) iCH.COjEt.
[71°]. From aoeto-acetio ether, formamidine
hydrochloride, and dilute aqueous Na^COj (Pin-
ner, B. 18, 2846). Needles (from ether).
CYANO-ETHYL-ACETO-ACETIC ETHER
CH3.C0.C(CN)Et.C0jEt. (108°) at 18 mm.
S.G. — "976. From sodium aceto-acetio ether
and CyCl, followed by water (Held, C. B. 98, 522).
Oil ; insol. aqueous alkalis. Boiling aqueous
EOH gives acetic and butyric acids, NH,, and
CO,.
CYANOrORM CHOyj. From chloroform
and alcoholic KCy at 130° (Fairley, G. J. 11,
362; Pfankuch, J.pr. [2] 4, 38 ; 6, 97. Accord-
ing to Claus, A. 191, 35, cyanoform does not
exist). Small needles. Decomposed by HCl
into NH3 and methane tricarboxylic acid
CH(00,H),.
Gompound.—VfWa meroivtic iodide •
3Hgl2,{CHCy3)j, crystalline needles got by heat-
ing iodoform with alcoholic HgCy^ at 120°.
CYANO-FOBMIC ACID CN.00,H. Gyamo-
carbonic acid. Semi-nitriU of oxaUo acid.
Methyl ether CN-OG^Me. (101°). From
methyl oxamate NH^CO-CO^Me and P.,Os
(Weddige, J.pr. [2] 6, 117; 10, 193). Pungent
oil. Quickly decomposed by water into HOy,
methyl alcohol, and GO,. Combines with H^S,
forming NHj.CS.COjMe.
Ethyl ether CN-COjEt. (116°). Formed
by distilling oxamio ether with PjOj. Formed
also by distilliflg NHj.CCl^.CO^Et, the product
of the action of PCI5 on oxamic ether (Wallach,
A. 184, 12; B. 8, 299). Oil, lighter than water.
Slowly decomposed by cold water into CO,,
alcohol, and HCy. Cone. HCl gives oxalic acid.
Ammonia forms NHjCy and carbamic ether;
alkylamines act similarly. HI reduces it to
amido-acetio ether.
Isohutyl ether CN.CO^CHjPr. (146°).
Allyl ether CN.COjCjHj. _ (135°). From
di-cyano-propyl alcohol (dicyanide of allyl alco-
hol) and fuming HCl (Wagner a. ToUens, B. 5,
1045). ,
4»iii« CN.CONHj. [60°]. Formed, together
with oxamide, by passing cyanogen into 96 p.o.
acetic acid and, after a few hours, heating to
100° (Beketofi, J.B. 7,99). Tables, v. sol. water,
alcohol, and ether. Split up at 120° into HCy
and cyaniiric acid.
Di-ethyl amide ON.CO.NBtj. (220°)
From u-di-ethyl-oxamide and P^Oj (Wallach, B,
14, 737). Oil; volatile with steam; si. sol.
water. . IJighter than water. PCI, gives ' chlor-
oxalethyline.'
Pora-cyano-formic acid (CN.COjH)„. From
its ethers by treatment with cold aqueous EOH ;
the acid is then ppd. by HCl as a bulky mass,
insol. alcohol and ether, v. si. sol. water. Boiling
water converts it into oxalic acid and NH,.
Salts. — K„(C2N0j)„: long needles (from
water). — Ag„(CjNOj)„: yellow pp., insol. HNO,.
Methyl ether Me„(COCN).. [154°]. Ob-
tained by polymerisation from methyl cyano-
formate under the influence of HCl. Also from
the silver salt and Mel. Small needles.
Ethyl ether Et„(COCN)„. {165°]. Formed
by saturating oyano-formic ether with HCl and
heating the liquid to 100° for several hours, or
leaving it to itself in the cold for a few weeks
(Weddige). Six-sided prisms, v. si. sol. cold, si.
sol. hot, sucohol. Cannot be distilled. Boiling
alkalis give oxalic acid, NH,, and alcohol.
Isohutyl ether (PrCHj)„(COCN).. [158°].
Amide (CN.CO.NHj)^. Amorphous.
Methylamide (CN.CO.NHMe).. [250°].
276 G diss
Anilide (ON.CO.NHPh).. Needles.
CYANOGEN CN. Mol. formula C^N,. MoL
w. 52-96. [-34-4°] (Faraday, A. 56, 158 ; Loir a.
Drion, J. 1860. 41). (0. -20°) (Bunsen, P. 46,
101). S.G. -866 at 17° (Faraday). V.D. 1-805.
S. (gas) at 20° = 4J; S. (gas) in alcohol at 20°
= 23; S. (gas) in ether at 20° = 5. Vapour-
pressure in atmos. at — 17-7° = 1-25, at — 9-4''
= 1-72, at -5° = 2, at0° = 2-37, at +6-9° = 3, at
17-2°= 4, at 25°= 5, at 31-3°= 6, at 37-4° = 7
(Faraday, l.c.), /to = 1-000804, /jl,, = 1-000834,
j«o= 1-000895 (Croulleboi3,4.CA.[4] 20, 185; v.
also Chappuis a. Eivi^re, O. B. 103, 37). H.F.
[C^N21 = -65,700; H.C. [C'N^O^ = 259,620 {Th.
2, 388). For spectrum v. Wiillner (P. 144, 517),
and Ciamician (W. A. B. 79 [2nd part], 8) ; dis-
persion V. Croullebois {A. Gh. [4] 20, 185), and
Maacart (0. B. 71, 617, 679). For transpiration-
coefficient V. Meyer (P. 143, 14).
Cyanogen was first prepared by Gay-Lussao
in 1815 ; he compared cyanogen with chlorine,
and the compounds of one with those of the
other, hence arose the conception of the com-
pound radicle CN replacing the simple radicle
CI. The name cyanogen (from "Kiavos) was sug-
gested by the colour of Prussian blue, which was
the earliest known compound of cyanogen.
The formula Cy is often used to denote
cyanogen.
Occwrrence. — In the gas from coke-ovens
(Bunsen a. Playfair, J. pr. 42, 143).
Formation. — 1. By passing induction-sparks
between carbon poles in an atmosphere of N
CYANOGEN.
367
(Morren, C. R. 48, 342). — 2. By heating
(NH<)jC.,0, or OACNHjjj, either alone or with
dehydrating agents (Dumas, A. 10, 295 ; Berta-
gnini, A. 104, 176).— 3. By heating AgCN (Del-
bruok, A. 64, 296) or AuCON). (Himly, A. 42,
157, 337).
Preparation. — Perfectly dry mercuric cyanide
is heated in a dry flask or small retort with a
long exit tube dipping under mercury in an in-
verted tube; the cyanide is decomposed to
cyanogen' and mercury, which condenses in the
exit tube.
Properties. — A colourless gas, with penetra-
ting odour resembling that of HON. Very
poisonous. Burns with purple flame. Liquefied
by cold and pressure; at —20*7° at ordinary
pressure ; liquefaction may be eflected by heat-
ing Hg(CN)2 or porous charcoal saturated with
cyanogen (Melsens, C. B. 77, 781) in a Faraday-
tube (c/. also Hofmann, B. 3, 663). At very low
temperatures freezes to a crystalline, ice-like
mass. Liquid cyanogen is a colourless, mobile
liquid; non-conductor of electricity; dissolves
P, I, camphor, and various other bodies (v. Gore,
C. if. 24, 303). Cyanogen gas is absorbed by
Hg at c. 100° (Amagat, C. B. 68, 1170) ; it is
also largely absorbed by porous charcoal (Hunter,
C. J. [2] 9, 76; 10, 642). Cyanogen combines
with several non-metals, e.g. with CI, Br, I, S,
P; it also forms compounds with most of the
metals ; in its chemical relations it shows analo-
gies with the halogens, e.g. in the composition
and properties of the acids HM and HMO,
where M = C1, Br, or CN, and in the composi-
tion of many cyanides. The hydraoid HON is
much weaker than the corresponding halogen
acids. Substitution of H in aromatic hydro-
carbons by the group CN generally results in the
production of compounds one or more H atoms
in which are acidic (v. Meyer, B. 20, 2944;
Schneidewind, B. 21, 1323; Papoke,B.21,1331;
Enoevenagel, B. 21, 1344). The modes of pre-
paration of cyanogen, e.g. from (NH4)2C204, and
its reaction with Hfi to -form C202(NH2)2i show
that it is the nitrile of ozaUc acid.
BeacUons.—l. Heated to o. 500° paraoyano-
gen is slowly formed (Troost a. Hautefeuille,
C. B. 66, 735, 795 ; v. also Pabacyanoqen), at
c. 1200° N is liberated (Meyer a. Goldschmidt,
B. 15, 1161). Heated in presence of iron or pla-
tinum C and N are formed.— 2. Decomposed to
C and N by a series of electric sparks, but after
a time re-formation of Cy begins (Bufi a. Hof-
mann, A. 113, 129; Andrews a. Tait, Pr. 10,
427).— 3. TTaicr dissolves Cy, the solution slowly
decomposes, except an acid be present (GianeUi,
J. 1856. 435), with separation of brown flocks of
azulmic acid (Pelouze a. Bichardson, A. 26, 63),
and formation of NH4 oxalate and carbonate
(Vauquelin, A. Ch. 9, 113 ; 22, 132), and also
HCN and OO.2NH2 (Wohler, P. 15, 627).— 4. 42-
colwlic and ethereal solutions decompose simi-
larly to aqueous solutions (Buff a. Hofmann, A.
113, 129 ; Marchand, J.pr. 18, 104).— 5. Water
in presence of aldehyde produces oxamide. —
6. With sulphwretted hydrogen either cyan-thio-
formamide (ON.CS.NH,) (2.11.) or dithio-oxamide
(NH,.0S.CS.NH2) (q. v.) is formed, according as
the Cy or the H^S is in excess. — 7. Chlorine re-
acts only in presence of moisture and sunlight,
CNCl and (CN),Cl3 are formed (SeruUas, A. Oh.
[2] 35, 291, m).—i. Sydvogen at 600°-550°
forms HCN (Berthelot, Bl. [2] 33, 2) ; HCN is also
produced when electric sparks are passed through
a mixture of Cy and H (Boillot, C. B. 76, 1132).
Nascent hydrogen (Zn and HClAq) produces
ethylene-dmmine {q. v.) (Fairley, A. Suppl. 3,
371). — 9. Potassium and sodium heated in Cy
form cyanides. — 10. Strongly heated iron decom-
poses Cy with formation of C and N. — 11. Zinc
forms cyanide, rapidly at 100°; cadmium, copper,
and lead, at high temperatures, form small quan-
tities of cyanides ; mercury and silver do not re-
act (Berthelot, Bl. [2] 33, 2).— 12. When a mix-
ture of Cy and oxygen is submitted to a powerful
electric spark, explosion occurs with production
of CO and CO, ; with a weak spark no explosion
occurs ; the explosion is not dependent on the
dryness of the gases ; slow combustion occurs in
presence of strongly heated Pt (Dixon, 0. J. 49,
384). — 13. Cone, cold li/ydrochlorie acid produces
oxamide (Schmidt a. Glutz, B. 1, 66) ; HCl in
absolute alcohol forms oxalic ether (Volhard, A.
158, 118 ; Pinner a. Klein, B. 11, 1481).— 14. Cone.
hydriodicacid when cold forms oxamide (Schmidt
a. Glutz, B. 1, 66) ; when hot forms glycouoll
(EmmerUng, B. 6, 1352) ; at 280° forms NH,
and CjH^ (Berthelot, J. 1867. 347).— 15. With
potash, cyanide and cyanate are formed. —
16. With dry ammonia, hydrazulmin, CjHjNj
(g. V. vol. i. p. 429), is formed ; when Cy is passed
into very cone. NHjAq, azulmic acid, GtSiJSfi
{g. V. vol. i. p. 429) , isprodnced ; with dilute NHjAq
oxamide is formed along with NH,, oxalate, and
oxamate.
Combinations. — 1. With hydrogen to form
HCN (v. BeacUons, No. 8). — 2. With water in
presence of aldehyde to form oxamide. — ;3. With
sulphuretted hydrogen to form cyan-thio-form-
amide or dithio-oxamide (v. Beactums, No. 6). —
4. With ammonia to form hydrazulmin, &o. (v,
Beactions, No. 16). — 5. With some metals to
form cyanides {v. Beactions, Nos. 9, 10, 11).
PoLYMERmE OF CYANOGEN. Paraoyanogen
a;CN. When HgCy, or AgCy is heated, a part is
changed to a loose, brownish-black solid, having
the composition scCN ; the value of x is unknown ;
MaumenS thinks it may be 4 (Bl. 35, 597).
Liquid cyanogen is slowly polymerised by heat-
ing (at 350°-S00°, Troost a. Hautefeuille, O. B.
66, 735, 795). Paraoyanogen is prepared by
heating dry HgCy, to 440° in a closed tube for
24 hours, and then passing cyanogen into the
tube at the same temperature to volatilise and
remove the Hg (T. a. H., l.c.). The quantity of
paracyanogen formed depends on the temperature
and pressure. Heated to 800° in a closed tube,
or heated in a stream of CO^ or N, paracyanogen
is changed to cyanogen. At each temperature
equilibrium results between the cyanogen and
paracyanogen when a definite pressure is at-
tained ; T. a. H. give the following data : —
Temp. Equilibrium-pressure
602° 34 mm.
506 60 „
659 123 „
675 129 „
587 157 „
599 275 „
601 318 „
629 8fi8 „
640 131U „
S58
CYANOGEN.
Heated in H paraeyanogen forms HCN, NH„
and C (Delbruok, J.pr. 41, 161). With molten
KOH it forms KCN and KCNO ; boiled with
cone. KOHAq it is slowly dissolved with evolu-
tion of NH,; by prolonged boiling with oono.
BNOjAq it forms a yellow solution.
Cyanogen bromides. Two are known, CXBr
and aiCNBr, x probably = 3. Mol. w. of the poly-
meride is not known with certainty, analogy with
CjNjClj points to formula GjNjBr,. For prepara-
tion, &c., V. Gyanoqek bbouide and Cyanubio
BBOMiDE, under Cyanic acid, p. 813.
Cyanogen chlorides. Two are known, CKCl
and CgNsCl, v. under Cyanic acid, p. 312.
Cyanogen iodides. Two are known, CNI and
a polymeride which is probably (CN),I, ; v. under
Cyanic acid, p. 313.
Cyanogen phosphide (CNjjP. (Phosphorus
cyanide.) Mol. w. not determined. White
needles; very easily decomposed in contact with
moist air to P, HjPOj, and HON. Melts at 200°-
203°, and boils a few degrees higher. Takes
fire when slightly heated in air. SI. sol. ether,
CS2, and PCI3. With alcohol forms ethylio
phosphite and HCN. Prepared by moistening
AgCy with PCI3 at a low temperature, closing
the tube, and heating to 130°-140° for 6 hours,
warming (after opening the tube) to remove ex-
cess of PC1„ and heating residue to 130°-140° in
a stream of dry CO, tiU the P(CN), sublimes
(Hubner a. Wehrhane, A. 127, 254 ; 132, 277).
Cyanogen selenide ?(CN)2Se (Schneider, P.
129, 634). Colourless plates ; obtained in small
quantity by adding dry AgCy to a solution of
Se^Br, in CSj, and crystallising from CS,. De-
composed by hot water to Se, HjSeOs, and
HCN.
Cyanogen sulphides (CN)2S, and (CN)2S3.
Mol. w. of neither has been determined.
I. Cyanoqen sulphide. (Sulphur cyanide.
Sulphocyamo anhydride.) (GN).iS. Produced
by reaction between SI2 and AgCy, SCI, and
HgCyj, and Cyl and AgjS. Prepared by mixing
ethereal solution of Cyl with an equivalent
quantity of AgNCS, evaporating with constant
stirring, and allowing to stand in a small closed
vessel ; the residue is treated with boiling CS.^
which dissolves the Cy^S, leaving Agl ; the Uquid
is cooled to 0°, and the crystals are dried in
vacuo over H2SO4. Forms rhombic plates melt-
ing at c. 60° ; decomposed by heating in moist
air ; sol. ether, alcohol, and water ; decomposed
by Bi,BOtA.q, HClAq, or HNOjAq ; with NH,
forms NHjCyS i with H^S forms HCN, HCNS,
and S (Linnemann, A. 120, 36).
II. Cyanoqen febsulphide (CN)2Ss. Ob-
tained along with (CN)2S in reaction between
AgCy and SCI,. Exists in two forms : (1) colour-
less crystalline mass, sol. CSj ; (2) dark-yellow
powder, formed by spontaneous change of (1), in-
Eol. alcohol, ether, water, or CS,, becomes elec-
trical when rubbed (Schneider, /. pr. [2] 82, 187).
III. The compound OsNsHS, is sometimes
called PsEUDOOTANOOEN SULPHIDE. This body is
produced by the action of oxidisers on HSCN or
on soluble sulphooyanides. Obtained by passing
CI into ESCNAq, or gently warming a solution
of 1 pt. KSCN in 3 pts. water with ^ its weight
of cone. HNOjAq ; the yellow pp. is repeatedly
washed with hot water (H^CjNsS, is dissolved
out, Jamieson, A. 69, 339), then with CS, (which
removes S, Linnemann, A. 120, 36), it is then
dissolved in cone. HjSOj, re-ppd. by water,
dried, boUed with absolute alcohol and again
dried (Volckel, A. 89, 126; Letnii, B. 8,707;
Laurent a. Gerhardt, A. Gh. [3] 19, 98 ; Liebig,
P. 15, 546 ; Wohler, O. A. 09, 271). Insol. in
water, alcohol, and ether; sol. without change
in cone. HjSO^ and in dilute alkalis ; si. sol. in
NHjAq. Decomposed by molten KOH to KSCy
and KCyO; heated with cone. NHjAq to 100°
NH,SCy and CjHsNjS (thio-ammelin) are formed.
Heated with POI5 reacts thus CaSjNjH + 3PC1,
= CjNaCl, -H 2POI3 + PSCI3 + S^CL, -^ HCl (Pono-
mareff, C. M. 79, 1335). Heated alone, gives
CS„ S, and mellone (C^NjHs) (Liebig, P. 15, 546).
Heated with CI, forms CyCl, SjClj, and mellone.
Cone. HClAq at 130°-140° produces CS^, S, and
cyanuric acid. Not acted on by nascent H, nor
by HIAq (Glutz, A. 154, 39, 44, 48).
M. M. P. M.
CYANOGEN HYDROXIDE v. Cyanic acid.
CYANO-MALONIC ETHEB CN.CH.(C02Et),.
Formed by acting on sodium malonate with
cyanogen chloride. Formed also from sodium
cyano-acetic ether and ClCOjEt (Haller, Bl. [2]
39, 262 ; C. B. 95, 143 ; 105, 169). Strong acid,
forming crystalline lead and calcium salts.
Boiling alkalis give malonic acid.
Salts.— NaCCy(C02Et)j: slender needles. —
CaA'2 2.^aq: triclinio prisms. — PbA'^aq. [88°],
CYANO-MELAMIDINE v. Guanidine.
CYANO-UETHYL-ACEIO-ACETIC ETHER
CH,.CO.CMe(CN).CO^t. (c. 93°) at 20 mm.
S.G. ^ -996. From methyl-aoeto-acetic ether,
NaOEt, and CyCl (Held, C. B. 98, 522 ; Bl. [2]
41, 330). Oil; insol. alkalis. Boiling alkalis
form acetic and butyric acids.
CYANO - NAPHTHALENE v. NiMU of
Naphthoic acid.
CYANO-NAPHTHOPHENAZINE C„H,CyNj
[237°]. From sodium naphthophenazine snl-
phonate by distilling with ECy and KjFeCy,
(Brunner a. Witt, B. 20, 2660). Alcoholic KOH
gives naphthophenazine carboxylic acid [above
360°J.
a-CYANO-(o)-NAPHTHYI.a-AMIDO-PRO.
PICNIC ACID 0H3.C(CN)(NHC,„H,).C02H.
Ethyl ether A'Et. [134°]. Formed by
digesting a-cyano-a-oxy-propionic ether with (a)-
naphthylamiue. Small white plates; sol. not
water, sparingly cold, v. sol. alcohol and benzene
(Gerson, B. 19, 2968).
a-Cyano-(;3)-naphch7l-a-anudo-propianic acid
CH3.C(CN)(NHC,„HJ.C0j,H.
Ethyl ether A'Et. Formed by heating a-
oyano-o-oxy-propionic ether with (;8)-naphthyl-
amine. Small rosettes ; sol. benzene and hot
alcohol, nearly- insol. water and cold alcohol
(Gerson, B. 19, 2969).
a-CYANO-o-OXY-PROPIONIC ACID
CH3.C(0H)(CN).C02H. Pyruvic-add-cyanhy-
drin. Crystals (containingEtOH) ; [151°]. Formed
by slowly adding pyruvic acid to KCN suspended
in boiling alcohol (Gerson, B. 19, 2963).
CYANO-PHENOL v. Nitrile of Oxy-benzoio
ACID. \
0-OYANO-PHENYL-ACETO-NITRILE v. 0-
CyANO-BENZYL CYANIDE.
(8 - C YANO - PHENYL - ;8 - AMIDO - BUTYRIC
ETHER CH,.0(CN)(NHPh).CH,.CO,Et. Formed
OYANO-TOLYLAMIDO-PKOPIONIO ETHEU.
S59
by the action of aniline upon the oyanhydrin of
acetoacetio ether (Schiller- Wechsler,B.18, lObO).
a - CTANO -o-PHENYL - AMIDO - PROPIONIC
ETHEE CH3.C(ON)(NHPh).002Et. [102°].
Formed by digesting an alcoholic solution of
o-oyano-a-oxy-propionio ether with aniline for
21 hrs. at 80^ Large trimetric crystals, a:b:c
-•7902:l-0:l-56366 {Gerson, B. 19, 2963).
o-CYANO-PHENYl-BTrTYRONITEILE
0„H4(0N).0HEt.CN. a-EthyUhomo-o-^hthalo-
nitrile. , [40°]. (294°). Formed by warming
o-oyano-benzyl-cyanide CsH,(CN).CH2.CN with
alcoholic NaOEt and EtI. Short thick prisms.
By heating with cone. H2SO4 and pouring into
water it is converted into the imide of phenyl-
/CHEt.CO
ethyl-acetic-o-carboxylio acid C^^ I
\C0 — NH
(Gabriel, B. 20, 2605).
DI-CYANO-DI-PHENYL.EIHANE
CN.CHPh.CHPh.CN. [218°]. Crystalline solid.
Formation. — 1. By reduction of di-cyano-di-
phenyl-ethylene with sodium-amalgam. — 2. To-
eether with di-cyano-di-phenyl-ethylene by boil-
mg phenyl-bromo-acetonitrile with an excess of
alcoheUc KCN (Beimer, B. 14, 1799).
DI-CYAKO-DI-PHEtt YI-ETHYLENE
CN.CPh:CPh.ON. Di - cyano - stilbme [158°].
Colourless plates. Insol. water, sol. hot alcohol,
benzene, acetic acid, and CS^. Prepared by the
action of bromine on benzyl cyanide, or from
phenyl-bromo-acetonitrile by heating to 170°,
or, better, by boiling with alcoholic KCN
(Beimer, B. 13, 742 ; 14, 1798). By boiling with
alcoholic EOH it gives diphenyl-f umaric anhy-
dride. By reduction with zinc and HCl it gives
a compound of the constitution C,„H„N2 which
forms small needles melting at [208°] ; insol.
water,- sol. alcohol.
CYANO-PHENYL-METHYL-TEIAZOLE
N— NPh
0,oH.N, probably y/ \ [109°],
MeO— N=C(CN)
Formed by the action of acetic anhydride upon
di-cyan-phenyl-hydrazine. Also by warming
di-cyan-phenyl-hydrazine with pyruvic acid in
alcohol : Ph.N(NH,).C(CN):NH + CHj.CO.CO.H
= 0,„H,N, + HCOjH + HjO. By alcoholic KOH
it is converted into phenyl-methyl-triazole-car-
boxylio acid [170°] (Bladen, B. 19, 2598).
o-CYANO-PHENYI-PEOPIO-NITEILE
CaH,(CN),CHMe.CN. a-Methyl-homo-o-phthalo-
nitrile.. [87"]. (285°). Large trimetric crys-
tals; o:5:c= •9449:1:1-0809; «=97°2',/3 = 103°13',
7=87° ir. Prepared by warming an alcoholic
solution of o-cyano-benzyl-cyanide (o-cyano-
phenyl-aceto-nitrile) with KOH and methyl
iodide. V. sol. ordinary solvents, si. sol. ligroin.
By heating with cone. HjSO, at c. 130° and
pouring into water it yields the imide of phenyl.
yCHMcCO
methyl-acetic-carboxylic acid C^H^
■^CO — NH
(Gabriel, B. 20, 2503).
CYAKO-PHEKYI-TETEAZOLE
»
„N=N.C.H.
Formed by the action of nitrous
\n=c,cn
acid upon di- cyano -phenyl -hydrazine. On
saponification it gives phenyl -tetrazole-car-
Jwxylic acid (Bladin, B. 18, 2907).
o-OYANO-PEOPIONIC ACID
CH3.CH(CN).C0jH.
Ethyl ether EtA'. (194"). V.D, 4-34.
From sodium cyano-acetic ether and CyCl
(Henry, C. B. 104, 1618). Heavy oil.
i3-Gyano-pTopionic acid. Amide
CN.CH2.CHJ.CONH2. Formed, together with
ethylene cyanide, by digesting ethylene bromide
with alcoholic KCy (Pinner, B. 16, 360). Prisma
(from water).
Cyano-propionioacid(?)04H5NOj. Preparedhy
dissolving wool (1 pt.) in water by means of KOjH
(3.pts.), and oxidising by KMnO., (2pts.) (Wanfe-
lyn a. Cooper, P. M. [5] 7, 356). Amorphous,
pale yellow, brittle solid (containing Ig aq).
Softens at 100°. V. sol. water and alcohol.
When strongly heated it gives off aoetonitrile.
Potash-fusion gives ethylamine and oxalic
acid.
Salts.— Sol. water, but not in alcohol.-^
KA'aq. — KA' 4aq. — KA' 5aq. — CaA'„ 4aq (at
100°). — BaA'jSaq (at 100°).— Ba3A'<0 7aq.^
PbA^aq (at 100°).— MgA'^ 3aq.— AgA'^aq (at
100°).— Ag3A'j(0H) aq (at 100°).
CYANO-PEOPIONYl-ACETIO ETHEE
CHjMe.CO.CHCy.CO^Bt. (160°) at 50mm. From
sodium cyano-acetic ether and propionyl chloride
(Haller, G. B. 106, 1083).— CaA'j2aq: long
needles, v. sol. water.
DI-CYANO-PBOPYL ALCOHOL
CH,Cy.CHCy.CH20H. (151°). From allyl al-
cohol and cyanogen (ToUens, B. 5, 621).
CYANO-PYEIDINE v. NitriU of Pyeidisb
OABBOXYIilO ACID.
CYANO-auiNOLINE v. JViWie 0/ Quinolinb
CABBOXYLIO ACID.
CYANO-SUCCINIC ETHEE C^H.^NOj i.e.
CH(CN)(C02Et).CHj.C0,Et. (158°) at 14 mm.
Formed, together with oyauo-tricarballylio ether,
by the action of sodium on oyanoaoetic ether
dissolved in alcohol, the product being decom-
posed with chloro-acetio ether. Oil. Sol. alco-
hol, ether, and alkalis (Haller a. Barthe, C. R.
106, 1413).— CjH.jNaNO^.
CYANO-TEEEPHTHALIC ACID
CsH3(CN)(C02H)2. From amido - terephthalio
acid by cuprous cyanide and nitrous acid
(Ahrens, B. 19, 1635). Amorphous yellow mass.
Decomposed by boiling alkalis into trimoUitio
acid.
a-CYANO-o-TOLUIC ACID C^H^NOj i.«.
CN.CHj.C3Hj.CO2H. [116°]. From phthalide
and alcoholic KCy (W. Wislicenus, A. 233, 102),
Crystalline powder (from HOAc). Aqueous
KOH gives COjH.CH^.C.H^.CCH.-CaA'jaaq.
3 - CYANO - J3 -o-TOLYLAMIDO - BTTTYEIO
ETHEE CH3.C(CN) (NHC,H,).CHr CO^Et.
Formed by heating the oyanhydrin of aceto-
acetio ether with o-toluidine (SohUler-Wechsler,
B. 18, 1050).
a - CYANO - o - 0 - TOLYLAMIDO - PEOPIONIC
ETHEE CH3.C(CN)(NHC,H,).C02Et. [93°].
Formed by digesting a-oyano-o-oxy-propionic
ether with o-toluidine in alcoholic solution.
Small white needles ; v. sol. benzene and warm
alcohol, si. sol. cold alcohol, insol. water (Gerson,
B. 19, 2966).
o - Cyano -a-p- tolylamido - propionic ether
CH3.C(CN)(NHC,H,).0P2Et: [81°]; glistering
spangles ; sol. alcohol and benzene, al. sol. wat>)r
360
CYANO-TOLYLAMIDO-PROPIONIC ETHER.
Formed by digesting a-eyano-o-oxy-propionio
ether in alcoholic solution with jj-toluidine
(Gerson, B. 19, 2967).
7.CYANO-VALEBIC ACID CsHsCyOj i.e.
CiHjCy.COjH. [95°]. Formed by heating valero-
, lactone to 290° with KCN. Prisms. Sol. water,
CHCI3, and CgH,. G^ives, on saponification,
a-methyl-glutaric acid (W. Wislicenus, A. 233,
114).
C'iA'SFK^'SIS'E V. Cyaphenine.
CYANPEOPINE C.jHj.N,. [115°]. S. -063
at 23°. Formed by the action of sodium on
butyronitrile under an extra pressure of about
20 cm. of mercury (B. v. Meyer, J. pr. [2] 37,
■ 397). White prisms (from ether).
Beactions. — 1. Is converted by heating with
cone. HCl to 180° into C^H^oNjO, [97°], S. -067
at 23°. — 2. Gives with bromine in an acid solu-
tion the hydrobromide of bromocyanpropine from
which ammonia liberates the base [80°].
Salt.— (B'HCl)jPtCl4. [97°]. Eeddish-yel-
low prisms.
CYANTJEATES (metaUio) ; and SULPHO-
CYANTTBATES (metallic). Cyanuric acid is a
polymeride of cyanic acid HNCO ; it probably
Las the constitution (CK)3(OH)3,
Ctanubates. Cyanuric acid is tribasic ; with
most bases, however, it forms acid salts. Cyan-
urates of the alkalis and alkaline earths are
80I. water, the others are insol., or only si. sol. ;
the alkali cyanurates are decomposed by heat to
HNCO, (NHj)NCO, CO^, N, and cyanate of the
metal ; the cyanurates are decomposed by
HjSOjAq or HNOjAq, giving HjNjCaO,.
Ammonium cyanurate
(NH,)H2.N3C,0,.H20 ; white lustrous prisms,
which effloresce in air.
Barium, cyanurates.
(1) Ba(Hj.N,0303)2.2H20 ; obtained by adding
BaOAq to boiling HjNjC^OjAq till slight per-
manent pp. is formed; loses 2H3O at 280°.
(2) Ba2(HN,Cs03)2.3H20 ; crystalline pp. by
adding boiling H3N3C30,Aq to ammoniacal
BaCljAq (Wohler. A. 62, 241).
Calcium cyanurate. Not obtained in
definite form (Chevallier a. Lassaigne, A. Ch.
[3] 13, 155).
Copper cyanurates. The normal salt
Cu3(C3N303)2.HjO is obtained by mixing acid Mg
cyanurate with CuSOjAq ; when NajCjNgOjAq is
used the salt CuHCjNjOy.SH^O is obtained (Claus
a. Putensen, J. pr. [2]" 38, 208). C. a. P. also
obtained the basic salt (CuOH)tC3N30,.3H20.
The following ammonio-copper cyarmraies are
described: Cu(HN3C30„).2NH3.H,0 (W., I.e.);
Cu(H.;N,CsOa)j.2NH3 (Wiedemann, P. 74, 73) ;
Cu(H2N,C303).!bNH3 where a; = 3 and 4, and the
add salt Cu(HsN,C,0,).H3N3C303.NH3.HjO (C. a.
P., Z.C.).
Lead cyanurate FblKT^fisOs)^^.^; pp.
obtained in microscopic prisms by dropping ex-
cess of basic Pb acetate into boiling HjNjCjO, Aq ;
decomposed to (NHJCN, C0(NH2)j, and Pb by
heating in H (W., l.c.).
Potassium cyanurates. (1) KH2N3C3O3
by adding HClAq to crude K oyanate solution
difficultly sol. water (Liebig a. Wohler, P. 20, 369
Campbell, 4. 28, 52). (2) KjENsCjOs ; by adding
alcohol to solution of the first salt, in presence
of KOH ; decomposed by water to KOH and the
dih^drogen salt (Ij. a. W.» 2.C.).
Silver cyanurates. (1) Ag^HNjCjOg; pp.
obtained by adding cyanuric acid to silver acetate
in acetic acid (W., I.e.). (2) Agfi,'Sfi,; by add-
ing hot AgNOjAq to hot HgNjCjOj in NH3Aq,
and drying pp. at 800° (Liebig, A. 26, 123 ; De-
bus, A. 72, 20; cf. Wohler, A. 62, 241).
Silver-ammonium, cyanurates.
(1) Ag.,HN3C303.2NH3 ; formed by digesting the
first Ag salt with NHjAq ; loses allNH, on heat-
ing. (2) Another salt is described by Liebig
{A. 26, 123 ; cf. Wohler, A. 62, 241), probably
Ag,C3N,03.(NH,)3C3N303.H,0.
Silver-potassium and silver-lead cy-
anurates. By boiling triargentio cyanurate with
KOHAq a salt is formed, probably Ag^KCjNjOj
(W., Z.C.). By boiling Pb cyanurate with excess
of AgNOjAq, the salt AgiPb(CsN303)2.2H20 is
produced (W., l.e.).
Sodium cyanurate NajCjNsOj; fine
needles; separates on adding excess of hot
NaOHAq to cone. HjCjNjOsAq (Hofmann, B. 3,
770).
SuLPHocYANUBATRS (Hofmann, B. 18, 2X96).
'Salts of sulphocyanurio add, H3CaN3S3. For
an account of sulphocyanuric add v. Cyanio
(suLPHo) Acm and Polymebides, p. 303.
Sodium sulphocyanurate
NaHjOaNjSs; large crystals, e. sol. water;
formed by digesting Na^S with methyl sulpho-
cyanurate. Sulphocyanurates of Gu, Pb, Li, K,
and Ag are described.
DisuLPHooYANiDEs (Fleischcr, A. 179, 204).
Salts of disulphocyamc add H^SjCjNj (g. v.
p. 303, under Ctahio (sulpho) acid and polymer-
ises).
Potassium disulphocyanide
KjSjCjN^.H^O ; obtained by adding an alcoholio
solution of KOH to persulphocyanio acid,
HjC^NjSj, and pressing the crystals which sepa-
rate. Yellow monoclinic prisms ; insol. absolute
alcohol ; v. sol. water ; solution in water changes,
quickly when heated, to E sulphocyanide. The
other salts described by Fleischer (2.c.) are
BaS2C2N2.2H20 ; v. soluble, white rhombic
prisms; CuSjC^Nj, brown-red pp. insol. dilate
acids; PbS^CjN,, citron-yellow pp. not acted
on by dilute acids; Ag2S2C2N2, green pp.;
AgKSjCjNj, yellow, crystalline.
M. M. P. M.
CYANTTEIC ACID v. p. 319.
CYANUEIC BBOlfflDE v. p. 320.
CYANUEIC CHLOEIiE v. p. 319.
CYANTJROMALIC ACID CaH^NjOj. An un-
stable crystalline body formed by dissolving the
cyanide of barbituric acid (g. v.) in aqueous KOH
(Neneki, B. 5, 887).
CYAPHEHINE (CjHjN), i.e. CyjPh,. [230°].
(above 350°).
Formation. — 1. By heating benzoyl chloride
with KNCO (Cloez, A. 116, 27).— 2. By heating
benzonitrile bromide alone or with lime (Engler,
A. 133, 146). — 3. From benzonitrile and Na
(Hofmann, B. 1, 194). — 4. Traces are got front
benzamide and COClj (E. Schmidt, J. pr. [2] 5,
35). 5. From benzonitrile and ZnEtj, the pro-
duct being treated with alcohol and then with HCt
(Pranklaud a. Evans, C. J. 37, 564).— 6. From
Cy,Cla, bromo-benzene dissolved in ether, andi
sodium (Klason, J.pr. [2] 35, 82), CyjClPhj [136°]
being the chief product.
Preparation. — 10 g. of benzonitrile are addodi.
CYMENE.
361
p-Bdually to 50 g. of slightly fuming H^SOj, kept
cold. After 48 hours the liquid is slowly poured
into 300 00. water. The ppd. cyaphenine, after
washing with water and alcohol, weighs !•! g.
(A. Pinner, J.pr. [2] 30, 126 ; B. 11, 764).
Properties. — White branching crystals. Inaol.
water, v. el. sol. alcohol and ether. Not affected
by boiling KOH or HCl.
BeacHons. — Heated in a sealed tube at 250°
with oono. HCl it is entirely converted into
benzoic acid and NH, (F. a. B.).
CYCLAMIN C,„H3„0„(?) [236°]. [a]„
--11° 40' (in alcohol) (Miohaud, G. 0. 1887,
1397); =-15°10' (Sachsse). Occurs in the
roots of Cyclamen europmum and perhaps also of
cowslips ('Primulin') (De Luoa, Cimento nuovo,
6, 225 ; 8, 182 ; G. 2, 556 ; Martins, Buchner's
N. Bepert. 8, 388; Mutschler, A. 185, 214;
Fliiokiger, Ph. [3] 8, 488). White amorphous
substance (from alcohol). Irritates the throat.
v. sol. boiling alcohol, insol. ether, chloroform,
CSj, and alkalis. Absorbs water from moist
air, swelling up ; slowly dissolves in water. The
aqueous solution froths like soap, and is coagu-
lated by heating. In contact with water it
slowly decomposes forming glucose and mannite
(De Luoa, C. B. 87, 297). Aqueous HCl coagu-
lates it and, at 80°, forms sugar. HOAc dis-
solves it and does not coagulate it on heating.
It gives a white pp. with Fehling's solution, but
does not reduce it even when hot. Cone. H^SO^
forms a red solution ; on diluting with water
glucose remains in solution, and there is ppd.
white amorphous oyclamiretin Qi^tH^fii [198°].
Chlorine water forms 'oyclamicacid' 035H5jO,j(?)
HKOs forms ' ohrysolin ' C.sHjiNOs.
CYCIOPIC ACID OjHgO,. Occurs in the
leaves of Cyclopia VogeUi (Cape Tea). The
aqueous decoction is digested with Pb(0H)2, the
lead compound suspended in dilute (50 p.o.) al-
cohol, and decomposed by H^S. The filtrate is
concentrated and mixed with alcohol and ether.
Cyclopin is ppd.; oyolopic acid is obtained by
evaporating the filtrate (Church, C. N. 22, 2 ;
Ph. [3] 11, 693; Greenish, Ph. [3] 11, 569).
Tellow needles, sol. water, insol. alcohol, ether,
and CSj. Aqueous alkalis form a yellow solution
with green fluorescence. FeCl, gives a green
colour, becoming brown on heating. Cupric ace-
tate gives a grey pp. KjCr^O, and HCl give a
dark brownish-red colour.
Cyclopin C^sH^gOigaq. Obtained as above.
Bed substance, v. sol. water, insol. benzene, CS^,
ether, CHCl,, and ligroin. Its aqueous solution
decomposes on standing into glucose and cyolo-
pin-red. KOH gives a brownish-red solution
with green fluorescence. FeClj gives an olive-
green colour turned yellow by HCl and brown
by NH,. Ppts. salts of Cu, Pb, and Ag.
Cyclopin-red 0,8HjjO|„. Formed as above.
SI. sol. water, ether, and benzene, v. sol. alcohol
• (when freshly ppd.). Alkalis dissolve it, forming
red solutions. FeCl, gives a brown colour.
CaClj or alum followed byNH, gives a violet pp.
CYCIOTHRAUSXIC ACID OpHi^NA i.e.
[2:l]CO,H.C„H..NH.CO.C,H„N[P3/. 3]. [252°].
Formatim. — o-Diquinoline is oxidised by
EMnO, in presence of hot oono. AcOH. The
pp. is filtered and digested with SOj until all the
MnOj is converted into sulphate. ' After filtering
again and well washing with hot water, the acid
is dissolved in KOH. The K-salt is decomposqd
with weak HjSO,, washed, dried, recrystallised
from boiling xylene, and decolourised with
animal charcoal.
Preparation.— By heating dry anthranilio
and quinaldinio acids together to 180° (Weidel
a. Wilhelm, M. 8, 197).
Properties. — White woolly needles; insol.
water, v. si. sol. hot EtHO, Et^O, CHCI3, CjH„
and xylene ; v. sol. hot AcOH iand HCl.
Salts.— A'jCa4aq : yellow flakes. — A'^a aq.
Beactions. — 1. With Ac^O it forms an anhy-
dride C„H,„N202 [196°], crystallising in long
colourless needles.— 2. KMnO, in alkaline solu-
tion oxidises it to 'pyridanthrilic acid' 0,5H,„N,0„
in acetic acid solution .quinaldinic, a-oxyisocin-
chomeronio, and anthranilio acids are formed
(Weidel a. Strache, M. 7, 285).
CYMEN JE C,„H„ i.e. C„HjMePr[l:4]. p-Pro-
pyl-toVuene. Mol. w. 134. (175°)». V.D. 4-63
(calc. 4-65). S.G. ^ -864 (Sohiff, A. 220, 94) ;
f -8569 (Briihl, A. 235, 19). C.E. (9-8 to
175-4°) -001159 (S.). li. 1-494 (B.). /t„ 1-484
(Gladstone, O. J. 49, 623). H.O. 1401609
(C, 0^ = 94; H„ 0 = 69) (Stohmann, J. pr. [2]
35, 41). S.V. 184-5 (Schiff) ; 181-62 (Kamsay).
Occurrence. — In the volatile oil of cumin
(from Cuminum Cynwmim) ; in the seeds of the
water-hemlock (Cicuta vwosa); in the oil of
thyme; in oil of Ptychotis Ajowan; in Euca-
lyptus oil ; and (to the extent of 6 p.c.) in oil of
lemons (Gerhardt a. Cahours, A. Oh. [3] 1, 102,
372; A 38, 101,345; Trapp, 4. 108, 386 ; Lalle-
mand, A. Ch. [3] 49, 156 ; Haines, 0. J. 8, 289 ;
H. Miiller, B. 2, 130; Faust a. Homeyer, B. 7,
1429 ; Ar. Ph. [3] 5, 385 ; Beilstein a. Kupffer,
B. 6, 1181 ; A. 170, 282 ; Fittica, A. 172, 303 ;
Tilden, Ph. [3] 9, 654).
Formation. — 1. By the dehydration of cam-
phor by means of PjO^, ZnOlj, PjSj, or PCI,
(Gerhardt, A. 48, 234 ; Delalande, A. 38, 342 ;
Pott, B. 2, 121 ; Fittig, Kobrioh, a. Jilke, A.
145, 129 ; Wright, C. J. 26, 686 ; Beckett a.
Wright, C. J. 29, 1).— 2. By heating dibromides
of terpenes CuHiaBrj with aniline (Oppenheim,,
B. 5, 94, 628).— 3. By distilUng crystallised
terpin hydrate with Br (Barbier, C. B. 74, 194).
4. From thymol and PjSj. — 5. From oil of tur-
pentine and iodine (Eekuld a. Bruylants, B. 6,
437) or chlorine. (Naudin, Bl. [2] 37, 111).—
6. From oil of turpentine and H.SO^ or Et^SO,
(Riban, Bl. [2] 20, 100, 244 ; Wright, 0. J. 26,
700 ; 0. N. 29, 41 ; Patern6, <?. 4, 113 ; Bruto,
C. B. 90, 1428 ; Eichter, B. 6, 1257).— 7. From
absinthol and PjSj (Faust a. Homeyer, B. 7,
1427 ; Graebe, B. 5, 680 ; Beilstein a. Kupffer,
A. 170, 282).— 8. From menthene C,„H,|, and Br
(Wright, C. J. 29, 1). — 9. By boiling cuminic
alcohol with zinc-dust (Kraut, A. 192, 224). —
10. From j)-bromo-toluene, Ji-propyl-bromide,
and sodium (Fittig, Schaffer, a. Konig, A. 149,
334; Fittica, A. 172, 320; Jacobsen, B. 11,
2049).— 11. According to Bouchardat (0. B. 90,
1560), cymene may be obtained from valerylene
(derived from amyl alcohol) by heating it to 250°
and treating the resulting divalerylene C,„H|j
with Br in CS2. — 12. By passing steam into
cymene-sulphonio acid'dissolvod in diluted H.^SO,
hydrolysis begins at 130° (Armstrong a. Miller,
C. J. 43, 14a;.
383
CYMENE.
Spectrum. — Absorption bands in ultra-violet,
a narrow one at cadmium-line 17, and a broad
band between Cd 17 and Cd 18. The first baud
enables the presence of cymene in essential oils
to be detected and estimated, for it is visible
when diluted with 20,000 volumes of alcohol, and
examined in a column 15 mm. long (Hartley,
C. J. 37, 676).
Reactions. '-I. H^SO^and KjCrjO, give tere-
phthalic acid.— 2. Oxidised by air, in presence
of aqueous NaOH, to cuminic acid. In this re-
action Pr changes to 3Pr. — 3. The urine of animals
who have been given doses of cymene contains
cuminuric acid, together with small quantities
of cuminic acid (Jacobsen, B. 12, 1512 ; c/.
Nencki a. Ziegler, B. 5, 749). Here, also, »-pro-
pyl becomes isopropyl. — 4. KMnO, gives oxy-
isopropyl-benzoic acid [c. 153°], as well as tere-
phthalic acid (Bemsen a. Emerson, Am. 8, 267).
5. HNO, forms^-tolyl methyl ketone and ji-toluic
acid. HNO, containing nitrous fumes forms
' m-nitrocymene ' CiaHuNjOi [125°] (HoUeman,
JS. T. C. 6, 60).— 6. Converted by AljCl, at 150°
into toluene and other products (Anschiitz, A.
235, 191). Liquid compounds (C,gH,4)3Alj,01„ aqd
(0,oH„)3Al2Bre may be prepared (Gustavson, J.
R. 11, 81). Al2Bre, in presence of Br, ultimately
formspenta-bromo-tolueneandisopropyl bromide
(Gustavson, B. 10, 1101). In this reaction the
PrBr first formed is changed by the AljEr^ into
¥zBv. — 7. By the action of CrOjClj, and treat-
ment of the compound with water, it gives p-
tolyl-propionic aldehyde (Bichter a. Schiichncr,
B. 17, 1931 ; of. Etard, B. 16, 2921 ; A. Ch. [5]
22, 258).
Cymene hexahydride CijHjj. (172°).
S.G. J^ -Sia. Occurs in oil of resin (Eenard,
A. Ch. [6] 1, 230).
o-Cymene GeHjPrMe[l:2]. o-Propyl-tolmne.
(182° uncor.). From »i-propyl bromide, o-bromo-
toluene, and sodium (Claus a. Hansen, B. 13,
897).
m-Cymene CBHjPrMe[l:3]. m-Propyl toluene.
(177°). S.G. iS -863. From w-bromo-toluene,
w-propyl bromide, and sodium (Claus a. Stiisser,
B. 13, 899).
w-Isocymene CeH^MePr [1:3]. (175°). S.G.
•865. Occurs in the essential oU obtained by
distilling resin of fir trees (Kelbe, A. 210, 1 ;
Eenard, A. Ch. [6] 1, 249). Formed from
toluene, isopropyl iodide and Al^Clj (Kelbe, A.
210, 1). Formed also, together with ordinary
cymene, by the dehydration of camphor (Spioa,
O. 12,543 ; Armstrong a. Miller, B. 16, 22S8).
Preparation. — Essence of resin is washed
with aqueous NaOH (to remove phenols), distilled
with steam, shaken with dilute and afterwards
with cone. H^SOj in the cold, washed again with
NaOH and distUled with steam. It is then
Bulphonated with a mixture of H2SO4 (4 pts.),
and fuming HjSO, (1 pt.) at 90°. The sodium
salt of the iso-cymene sulphonic acid is decom-
posed by heating with cone. HCl for two days at
185°, and the liberated cymene distilled over
with steam (Kelbe a. Warth, A. 221, 158).
Reactions. — 1. Oxidised by chromic acid or
perm3.nganate to isophthalic acid (Zeigler a.
Kelbe, B. 13, 1399).— 2. Dilute HNO, forms
m-toluio acid or aldehyde. Fuming HNO3 forms
a tri-nitro- derivative [72°].- 3. CrOjCl, forms a,
chocolate-brown powder whence water liberates
m-toluio acid.
^-Isooymene CjHjMePr [1:4]. (173°). S.G. 9
•86!); ss-y62. From ^-bromo-cumene, Mel, and
sodium (Jacobsen, B. 12,429 ; B. Meyer, A. 220,
27), or from isopropyl chloride, toluene, and
AljCl^ (Silva, Bl. [2] 43, 321).
CYMEKE-AZO-CYMEN'E v. Azo- coMPonxDa,
CYMENE-CARBOXYLIC ACID ,
C^HsMePrCOjH. [63°]. Prepared by fusing the
amide with potash, or preferably by heating it
with concentrated hydrochloric acid at 180°.
Crystallises in slender needles isomeric with
Eossi's homo-cuminio acid (Patern6 a. Spica,
G.9,400).
4miie C,ftMePr.C0NH2. [139°]. Formed
from potassium cymene sulphonate by fusing
with KCy and treating the resulting crude nitrile
with alcoholic KOH (Patern6 a. Fileti, O. 5, 30).
Needles, si. sol. cold water, v. sol. alcohol and
ether.
m-Cymene carboxylic acid C„HjMePr(COaH)
[2:5:1]. [75°]. From the nitrile which is formed
from tri-carvacryl phosphate and KCy (Kreysler,
B. 18, 1714). Needles (from dilute alcohol). V.
si. sol. cold water. — AgA'.
Nitrile CJIjaePrCN. (245°).
CYMENE SllLPHINIC ACID
CsH3MePr(S0jH) [1:4:2]. From cymene Bul-
phonic chloride, water, and zinc-dust. Sy-rnp
(Berger, B. 10, 977).— KA'Slaq.— AgA'.
CYMENE (o)-SULPHONIC ACID
CeH3MePr(S0sH) [1:4:2]. Formed, together with
the (;3)-isomeride, by shaking cymene with cone.
HjSO^ or CISO3H at 90^ (Gerhardt a. Cahours,
A. Ch. [3] 1, 106 ; Delalande, A. Ch. [3] 1, 368 ;
H. Miiller, B. 2, 130; Jacobsen, B. 11, lOCO;
Claus a. Cratz, B. 13, 901 ; 1-1, 2141 ; Spioa, G.
11, 201 ; B. 14, 652 ; Sievekii.g, A. 106, 260 ;
Beilstein, A. 170, 287 ; Paterno. B. 7, 591 ; G.
3, 544; Kraut, A. 192, 226; Biiar, A. 220, 18).
Also formed by debromination of bromo-cymene
sulphonic acid obtained from cymidine (Wid-
mann, B. 19, 249).
Tables (from dilute HjSO,). The crystals
contain 2aq and melt at 51° (S.) or 79° (C.) ;
when anhydrous they melt at 220° (C.). The
K salt is oxidised by KMnO, to oxy-isopropyl-sul-
pho-benzoic acid C3H3(CO.,H)(SOsH).CMej(OH).
HNO3 forms sulpho-^-toluic acid. Potash-fusion
forms carvacrol. By treatment in aqueous solu-
tion with bromine it yields bromo-oymena
CjnjPrMeBr[4:l:2] and bromo-cymene-sulphonio
acid C„H,PrMeBr(S03H)[4:l:5:2] (Kelbe a. Kosch-
nitzsky, B. 19, 1730).
Salts.— KA'aq.—NaA'Saq (Patern6, O. 8,
291).— NaA' 5aq.— BaA'2 3aq. S.. (of BaA'j) 2'5
at 12° (S.). Pointed leaflets, crystallising readily ;
m. sol. 90 p.c. alcohol. — CaA'2 2aq: monoclinic
crystals, a:6:c = l-374:l:l-124 ; )3 = 95° 13' (Jero-
fejeff, A. 170, 297).-PbA'2 3aq. S. (of PbA',) 1-3
tol^9.— NiA',5aq.
Amide C,H3MePr(S0,NHJ. [112°] (J.):
[116°] (Kelbe, B. 19, 1969).—
CsH,MePr(SO,NHAg) (Berger, B. 10, 976).
Bemoyl-amide CoHaMePrJSO-NHBz).
[153°] (Wolkoff, B. 5, 142).
Cymene (;e)-Bulphonic acid GsH3MePr(S0jH)
[1:4:3]. [131°]. Formed, in small quantity, in
the sulpbonation of cymene (Claus a. Cratz, B,
13, 901 ; 14, 2141). Formed also by debromin*-
CYMIDINE-STTLPHONIC ACID,
363
tion of bromoeymene sulphonio acid (Bemsen
a. Day, Am. 5, 154 ; v. also Kelbe a. Kosohnitzky,
B. 19, 1730 ; Glaus a. Christ, S. 19, 2165). Gra-
nules ; extremely sol. water, sol. alcohol, insol.
ether.
Salts.— NaA'aq. — liA'aq. — CaA'jcaq. —
BaA'jSaq (over H^SOj). Gelatinous; v. e. sol.
water, sol. alcohol. — PbA'j 3aq : amorphous, v. e.
sol. water. — CuA'jaq.
Amide CoHaMePr.SO^NHj. [148°].
o-Cymene (o) -sulphonio acid CjHjMePrfSOsH)
[1:2:2]. Formed, together with the following, by
Bulphonating o-cymene, especially at low tempe-
ratures (Glaus a. Hansen, B. 13, 897).— KA'^aq.
BaA' aq : stellate groups of laminae. — GuA', 4aq.
o-Cymene (i8)-sulphonic acid CjH3MePr(S03H)
[l:2:a;]. Formed as above. — BaA'j xaq : gelati-
nous mass, V. e. sol. water.
Amide. Very slender needles (from water).
m-Cymene (a)-Bulphonic acid
C,HjMePr(SO,H) [l:3:x]. Formed .together with
the (fl)-iBomeride, by warming m-oymene with
cone. H-iSO, (Glaus a. Stusser, B. 13, 899).—
KA'. — GaA'22aq. — BaA'^aq: laminse. S. (of BaA'J
■43 at 17°.— PbA'jSaq.— GuA'j4aq.
m-Cymene (/3) -sulphonio acid
C,H,MePr(SOjH) [l:3:a!]. Formed as above.—
BaA', aq : needles. S. (Of BaA',) 3-83 at 16°.
m-Isocymene (a)-sulphonic acid
C,H,MePr(SO,H) [1:3:6]. [89°]. Formed, to-
gether with the (/3)-isomeride, by treating iso-
cymene with cone. H^SO, (Kelbe, A. 210, 30 ; B.
15, 39; Spica, 0. 12, 487, 546). Deliquescent
micaceous leaflets. Br in the cold gives bromo-
isocymene sulphonic acid, but at 40° it forms
(6,l,3)-bromo-isooymene. KOH and KMuOj gives
oxy-isopropyl-sulpho-benzoic acid.
Salt 8. — NaA' aq. — ^KA' 3aq. — KA' (Armstrong
a. Miller, B. 16, 2258).— BaA'„ aq : pearly plates,
V. si. sol. cold, si. sol. hot, water. S. "37 (Spioa).
BaA'j: plates (Boner, A. 220, 33).— PbA', aq.
S. 1-3 at 22° (Spica).— CuA'j 2aq.— GuA', 4aq.—
NiA', 5aq.
Amide GjHsMePr.SOjNHj. [73°] (K.) ; [75°]
(S.). Laminaj, si. sol. boiling water.
m-Isocymeue (;S) -sulphonic acid
C;H[,MePr(SO,H) [1:8:4].
Formaticm. — 1. By sulphonation of isocy-
mene. — 2. By sulphonation of (o)-bromo-isocy-
mene and removal of the Br by sodium amalgam
(Kelbe a. Gzarnomski, B. 17, 1746 ; A. 235, 285).
Salts. — ^NaA' 3aq.— BaA', Saq : laminiE, v. e.
Bol. water.— CaA', 5 J aq.— CuA', 3|aq.— PbA'jSaq.
Amide C,„H,s(SO,NH,) [162°].
p-Iso-cymene (a)-snlphonlc acid
C,HsMePr(SOsH) [1:4:2]. From iso-cymene and
HjSOj, together with the (/3)-isomeride (Jaoobsen,
B. 12, 431). KOH and potassium permanganate
converts it into oxy-propyl-sulpho-benzoio acid
C.H,(CO.^)(G(OH)Me,)SO,H (B. Meyer a. H.
Boner, A. 220, 30). Potash-fusion gives oxy-
terephthalic acid and oxy-cuminic acid [88°].
Salts. — BaA', aq : slender needles. S. 4-28
at 0°.— CuA',4aq: blue leaflets.
Amide G„H3MePr(S0,NH,)._ [98°],
^-Isocymene (;3) -sulphonic acid
C,H3MePr(S03H). Formed as above. Its Ba
Bait is extremely soluble in water.
Amide C„ri3MePr(SO,NH3). [80°-90°].
Cymene disulphonic acid C,H2MePr(S0jH),.
JCrom cymene and funiing H,SOj (Kraut, 4. 192,
226).— BaA" aq : v. e. sol. water (Glaus, B. 14,
2140).
m-tso-CYMENOL 08H,?rMe(0H) [4:2:1].
Methyl-isopropyl-pheriol tn-isocymophenol.
(231°). Bqq 1'62. From! m-isocymene sulphonio
acid (Ipt.) by fusion with KOH (6pts.) (Kelbe,
A. 210, 40). Liquid, smelling like thymol.
Gives a violet colour with FeClj. By KOH
fusion it is converted into o-oxy-isophthalio acid
andp-ouminol-carboxylic acid CgH,Fr(OH)GO,H
[4:1:2]. .
Benzoyl derivative CgH3frMe(0Bz).
[73°]. Monoclinio crystals; ffl:6:c='52:l:-82;
i8 = 82°17'.
Methyl ether 03H3PrMe(OMe) : (217°).
Ethyl ether G3H3PrMe(OBt) : (224°).
Tri-hromo- derivative G8Br3PrMe(OH) :
[222°]; plates (Jesurun, B. 19, 1413).
Isomerides: Cabvacboii and Thymol.
' TO-iso-CTMENOL-CAEBOXYLIC ACID
OjH,?rMe(OH)CO,H [1:3:4:5]. Cymenotic acid.
[147°]. Formed by the action of GO, upon
sodium m-iso-cymenol (m-isopropyl-phenol).
Long slender needles (from hot water). Si- sol.
hot water, nearly insol. cold water. FcjCl, pro-
duces a bluish- violet colouration.
Salts. — AgA': small needles, m. sol. hot
water. — BaA',4aq: needles, v. sol. alcohol.
Methyl ether X'Me: [148°] : short needles
(from alcohol) (Jesurun, B. 19, 1414).
Isomerides: CAKVACBOiia and Thyuoiio
ACIDS.
CYMIDINE C.H3(C3H,)(CH3)NH, [4:1:3].
Preparation. ■ — Nitro - cymylene - dichloride
C„H3(GjH,)(N0,)(GHGl2), obtained by the action
of PCI5 on nitrocuminio aldehyde, is reduced with
zinc and HCl.
Properties. — Golonrless oil. Volatile with
steam. Sol. alcohol and ether. Stable towards
oxidising agents. By nitrous acid it is converted
into thymol.
Salts.— B'HGl: fine needles.— (B'HGl),Pt01,:
sparingly soluble yellow needles. — B',BLjS04 2^aq :
small white needles, si. sol. cold water.
Acetyl derivative, [about 112°]. White
needles (Widman, JB. 15, 167 ; 21, 2126 ; cf. Bar-
low, A. 98, 248 ; P. M. [4] 10, 454).
Cymidine G,H3PrMe(NH„) [4:1:2]. From
(2,4,l)-nitro-cymeue (Loderbaum, B. 21, 2127).
— B'HCl.— B',H,SO, aq.
m-Isocymidiue CBHjFrMefNH,) [3:1:5 or 6].
(233°). From nitro-iso-cymene (Kelbe a. Warth
A. 221, 163). Yellowish oil. V. si. sol. water,
V. sol. alcohol, light petroleum, or benzene.
Salts.— B',H,SO^. SI. sol. water.— B'H,G,04.
Acetyl, derivative CsHaPrMeNHAa
[118°].
Benzoyl derivative CjHjPrMeNHBz,
[165°].
Phthalyl derivative
G.H,G,0,NG3H33?rMe. [145°].
(?ra)-CYMIDINE-STTLPH01TIC' ACID
C3H,Me(G3H,)(NHJS03H [1:4:3:6]. Formed by
heating cymidine with fuming H,SO,. Thin
glistening colourless plates or prismatic needles.
V. b1. Bol. cold water. Insol. alcohol. Is pro-
bably a »-propyl-derivative, since by treat-
ment of the diazo- compound with HBr and
debromination it gives rise to the sulpho-
nio acid of n-cymene. The oorresponding
304
CYMIDINE-SULPHONIC ACID.
/SO,
Diazo- compound C|,HjMePr<^ I forma
small white needles, v. e. sol. water, si. sol.
alcohol, insol. ether. By warming with absolute
alcohol it is conTerted into the sulphonic acid of
the ethyl-ether of thymol (Widmann.B. 19, 246)
Isocymidine sulphonic acid
OjHjMe?r(NHj) (SOaH). From amido-iso-cymeije
and fuming H^SO^ (Kelbe a. Warth, A. 221, 177).
Salt.— BaA.V
CYMINYL. Also called Cymyi, (g. «.).
CYUOFHENOL v. Ctmenol.
CYMOFHENONE v. Phenyl oymyl ketone.
CTMYL. The radicle CjH3Me(C,H,). .Its
derivatives are described below ; see also Cahva-
CBYL and IhymyIi compounds. Cuminyl
C5H4(CjH,)CHj is isomeric with cymyl.
CTIIYLAMINE v. Thyuylamine and Cabva-
CBYIiAMINE.
ISOCYMYI-CABBAMIC ETHEK
CsH3¥rMeNH.C02Bt. [229°]. From ClCO^Et
and amido-iso-cymene. Slender needles (from,
alcohol).
ISOCYMYl CAHBAMINE C^HaPrMeNC.
From amido-iso-cymene, KOH, CHClj, and al-
cohol (Kelbe a. Warth, A. 221, 170). Oil of very
nasty odour, nearly insol. water, sol. alcohol,
ether, and benzene. Oan be distilled with steam,
but not alone at ordinary pressure.
DI-CYMYL ETHYLENE DIKETONE
(C„H,MePr.C0)jC2H,. (o. 320°). From oymene,
Buccinyl chloride, and AlCl, (Claus, B. 20,
1378).
ISOCYMYL ETHYL GTTANIDINE
0sH3l^rMeNH.C(NH).NHEt.
From CeHsPrMeNH.CS.NHEt, alcoholic NHj,
and FbO (K. a. W.). Gummy mass.
Trihemoyl derivative
CaHjPrMeNBzC.(NBz)JiIBzEt. [165°]. Needles
(from alcohol).
CYMYL ETHYL KETONE CAEBOXYLIC
ACID 0,H3(C.,H,)Me.CO.CH2.CH2.C02H. From
cymene, succinyl chloride, CS^, and Al2CIe (Claus,
B. 20, 1378).— PbA'j.
ISOCYMYL ETHYL THIO-UEEA
CeH,PrMeNH.CS.NHEt. Methyl-iso-propyl-
phen/yl-thio-ethyl-tirea. Formed by heating
amido-iso-cymene with ethyl-mustard oil. An
amorphous gummy mass (K. a. W.).
CYMYL METHYL KETONE
CH3.00.CeH3MePr [1:2:5]. (248°). From cymene,
AcOl, and AICI3 (Glaus, B. 19, 232).
SI-ISOCYMYL THIO-UaEA
(CsHaPrMeNH)2CS. [160°]. From amido-iso-
cymene and CS2 in a sealed tube at 100°
(K. a. W.). Slender needles (from alcohol).
ISOCYMYL - TJEEA NHj.CO.NH.CjHaPrMe.
Eso-methyl-eso-iso-propyl-phem/l-urea. [17G°].
From ENCO and amido-iso-cymene sulphate
(Eelbe a. Warth, A. 221, 171). Matted glittering
needles (from water).
Di-isocymyl-nrea C0(NH.C8H3PrMe)a. From
COCI2 and amido-iso-cymene in ether. Slender
needles (from alcohol).
CYNANCHOL. A crystalline substance ex-
tracted by Butlerow (A. 180, 349) from Cyndn-
chum acutum, a creeping plant growing near
the Oxus, and said to poison camels. According
to Hesse {A. 182, 163) it is a mixture of cynan-
ohocerin [146°] and cynanchin [149°].
CYNAFINE. Areddish -yellow oil with power,
f ul odour, contained in the seeds of fool's parsley
(^thusa Cynapium), ■whenae it may be extracted
by distilling with milk of lime. Strongly alkaline
in reaction (Fioinus, Mag. Pliarm. 20, 357 ; Bern-
hardt, Ar. Ph. [3] 16, 117).
CYNENE V. CiNENE.
CYNEOL V. CiNEOi..
CYNITEENIC ACID is Oxy-qtoioune cab-
BOXYLIC ACID (g. V.).
CYNUEIC ACID CsHjNOj i.e.
CO2H.CeHj.CO.CO2H. OoMloxyl-o-amiio-hewsoio
acid. [189°]. S. 1-12 at 10°. Formed by oxi-
dising cynurenio acid, acetyl-quinoline tetra-
hydride, or carbostyril by alkaline KMnO,
(Kretschy, M. 4, 157 ; Friedlander a. Ostermaier,
B. 15, 332). Formed also by heating dry oxalic
acid with o-amido-benzoic acid at 130° (Kretschy
M. 5, 21). Needles (from ether). FejClj colours
its aqueous solution crimson. Boiling acids and
alkalis split it up into oxalic and o-amido-
benzoic acids.
S alt s.— KHA"iaq.— (NH,)jA".— BaH2A"2aq.
BaA" aq.— OaA" 2iaq. -CusA"sO 4aq.— Ag^A".
Ethyl ether EtA'. [181°]. From indoxylio
ether and chromic mixture (Baeyer, B. 15, 778).
Needles (from alcohol).
CYSTEIN O3H.NSO2 t.e.
CHs.C(NH2)(SH).C02H. Prepared by adding
tin to a solution of cystin in hydrochloric acid
(Baumann, S. 8, 299). Crystalline powder, sol.
water, ammonia, and acids. The aqueous solu-
tion is oxidised to cystin even by the air.
CYSTIN C^H.jNjSjOj i.e. S(CMe(NH2).C0.,H)2.
[o]„= -206° in 11 p.c. HClAq (Mauthner, H. 7,
225) ; [a]j = -142° in NH^Aq (Knlz, Z.B.20,1).
Occasionally occurs as urinary calculus or sedi-
ment (Wollaston, P. T.ISIO, 223 ; GoldingBird,
Treatise on Urinary Concretions % Toel, A. 96,
247 ; Lassaigne, A. Ch. [2] 23, 328 ; Baudrimont
a. Malaguti, /. Ph. 24, 633 ; Thaulow, A. 27,
197 ; Marchand, J. pr. 16, 254 ; Eobert, J. Ph.
7, 165 ; 0. Henry, J. Ph. 23, 11 ; Taylor, P. M.
[3] 12, 337; Niemann, 4. 187, 101; Udranszky
a. Baumann, jB. 21, 2744). Found also in the
kidneys of the ox (Cloetta, A. 99, 299) and in the
liver of a drunkard who died of typhus fever
(Soberer, N. Jahrb. Pharm. 7, 306). In very
small quantities it is a normal constituent in
urine (Goldmann a. Baumann, B[. 12, 254).
Properties. — Neutral and tasteless. ' Crystal-
line mass. Insol. water and alcohol ; sol. aqueous
ammonia (difference from uric acid) and potash,
and reppd. as six-sided laminea by HOAc. Sol.
HClAq. Separates from an ammoniacal solu-
tion as colourless laminae. Cold ammoniacal
AgNOa followed by HNO, gives a canary yellow
pp., but hot ammoniacal AgNO, ppts. Ag^S
(I)uwar a. Gamgee, Ph. [3] 1, 385). Baryta-water
at 150° gives barium sulphide and sulphite.
Nitrous acid forms pyruvic acid (Dewar a. Gam-
gee, Ph. [3] 3, 144 ; H. 6, 329). Boiling aqueous
NaOH converts part of its S into HjS.
Benzoyl derivative CeH,gBz2N2S20,.
[158°]. Its Na derivative is ppd. by adding BzCl
to a solution of cystin in aqueous NaOH. Slender
needles. Strong acid, insol. water, si. sol. ether,
m. sol. alcohol (G. a. B.).
CYTISINE CjoHj^NjO. [155° cor.]. An al-
kaloid occurring in the unripe seeds of the labu7-
n\xm,Cytisiis Ldbwrmim (Chevallier a. Lassaigne,
DAPHNETIN.
S65
/. Ph. 4, 340 ; 7, 235 ; Pesohier, J. Chim.
6, 65 ; Husemann a. Marmfi, Z. [2] 1, 161 ; 6,
677). Crystalline mass (from alcohol) or thin
needles and lamina (by sublimation). V. e. sol.
water and alcohol, neai^ly insol. ether, benzene,
and chloroform. Expels KH, from its salts,
even in the cold. Poisonous. Does not reduce
Fehling's solution. Fotassio-merouric iodide
gives a white flocculent pp. becoming crystal-
line. I in EI gives an amorphous red pp.
changing to prisms. Bromine-water gives an
•range pp. even in very dilute (1:15000) solu-
tions. Sodium phosphomolybdate gives a yellow
pp. Tannin forms a pp. only after neutralisa-
tion with NaOH. Picric acid gives a yellow pp.
soon becoming crystalline.
Colour tests.— Cone. HjSO, gives no colour.
Sulphomolybdic acid reaction gives no colour.
HjSO, and KjCrjO, a yellow turning brown.
HNOj an orange-yellow.
Salts B'(HN03)2 Saq : prisms, with bitter
taste.— B'H,01, xaq. — B'H JtOl,.— B'H.Pt01,.—
B'(HAuOgj.— B'HgjOl,.
D
DAMALTTEIC ACID C,H,„Oj. [63°]. An acid
said to have been obtained from cows' urine
(Stiideler, A. 77, 27 ; Werner, Z. [2] 4, 418).
DAMBONITE Cfi,fi^. [190°]. Dumethyl-
dambosB. Di-methyl-inosite. Occurs in a pecu-
liar kind of caontchono. Exported from Gaboon
in West Africa (Girard, C. B. 67, 820). Six-
sided prisms (from alcohol), oblique prisms (con-
taining 3aq) (from water), or slender needles
(by sublimation). Not afiected by dilute acids
or alkalis, by Fehling's solution, or by fermen-
tation. HI gives Mel and damboae, identical
with inosite. EI forms crystals of C,E,,0,EI.
HNO, and H^SOf form an explosive nitrate
(Champion, O.'B. 73, 114).
Acetyl derivative C^HijAo^Og. [193°].
(337°). Needles (Maquenne, A. Oh. [6] 12, 566 ;
C. B. 104, 1853).
Benzoyl derivative CgHijEzjOo. [250°].
Minute pale-yellow needles (M.).
LAMBOSE CjH,sOj. [218°]. Obtained by
heating dambonite with aqueous EI at 120°
(Girard, O. B. 67, 820 ; 73, 426 ; 77, 995). Ac-
cording to Maquenne (C. B. 104, 1853) it is
identical with inosite {v. Inosiie and Suqabs).
Six-sided prisms (from dilute alcohol) ; mono-
clinic prisms (containing 2aq) (from water). In-
active. V. e. sol. water, insol. absolute alcohol.
Not prone to fermentation.
Sexa-acetyl derivative C^Jiofl^
[211°].
Methyl ether G^^^UeO^. Bomesite. [175°].
In caoutchouc from Borneo (Girard, Z. [2] 7,
335).
Di-methyl ether v. Damboniib.
DAMKABA BESIN. New Zealand Eauri
gum, the gum-resin from Dammara atistralis
contains a slightly Itevorotatory terpene dam-
marole C,oH„ (158°) S.G.iS-863 (Eennie, C.J.
39, 240; ef. Thomson, A. Ch. [3] 9, 499 ; Muir,
C. J. 27, 733). Dammar-Puti or East Indian
dammara resin may be separated, according to
Dulk {J. pr. 14, 16), by successive treatment with
weak alcohol, absolate alcohol, and ether into
hydrated dammarylic acid OjiH^O, [60°],
anhydrous dammarylic acid C„H„03
[60°],and dammaryl 0«H„ [190°], the residue
being CjoH,„0 [215°]. Franchimont obtained an
acid CjaHjA- See also Sohrotter, P. 59, 37.
OANAIN CnHijO,. Said to occur in the root
of Danaia fragrant, and to give by hydrolysis a
sugar and resinous danaidin (Schlagdenhauffen,
J. 1886, 1815).
(3:4) y{l) CH:CH
DAPHNETIN C;3U(0B.)jC I • -D*-
N(2) O— CO
oxy-coumarin. [256°]. Prepared by hydrolysis
of daphnin, a gluooside occurring in the bark of
Daphne alpina and Daphne Mezereum (Zwenger,
A. 115, 8; Stunkel, B. 12, 109).
Synthesis. — By heating molecular proportions
of pyrogallol and malic acid with H2SO4 (twice
the weight of the former), and precipitating the
melt in cold water (Pechmann, B. 17, 938).
Properties. — Needles or prisms. Sol. hot
water, si. sol. ether, nearly insol. chloroform;
benzene, and CS,. Dissolves in alkalis with a
reddish-yellow colour.
Beactions. — Fe2Cl, gives a green colouration
which changes to red on adding NajCO,. Po-
tassic ferricyanide and NH, gives a reddish-yel-
low colour. HNO, gives an intense red. It re-
duces AgNO, and Fehling's solution in the cold.
Baryta water, Zn(OAo)2, and Pb(OAo)2 give yel-
low pps. After boiling with NaHSO,, Fe^Cl,
gives an intense blue colour.
Di-acetyl derivative C,H402(OAc)2 :
[129°] ; colourless needles, insol. water, sol.
other solvents.
Di-benzoyl derivative C,H<02(0Bz)j :
[152°]; fine needles, insol. water and ether,
sparingly soluble in alcohol (Pechmann, B. 17,
933).
Mono-ethyl ether CjHA(OEt) : [155°];
colourless glistening plates, v. sol. alcohol, ether,
benzene, and aqueous alkalis, si. sol. water.
Di-ethyl ether CjH402(0Et)2 : [72°]; co-
lourless needles. Y. sol. alcohol, ether, and
benzene, insol. water and aqueous alkalis (Will
a. Jung, B. 17, 1081).
Bromo-daphnetin C^fitO^.
Di-ethyl ether 0„HjBrO2(OEt)2 : [116°];
colourless feathery crystals. Sol. hot alcohol,
ether, and benzene, si. sol. cold alcohol, insol.
aqueous alkalis. Formed by bromination of the
di-ethyl ether of daphnetin. By boiling with
alcoholic KOH it is converted into the di-ethyl-
derivative of daphnetilic acid (Will a. Jung, B.
17, 1084).
Tetra-bromo-daphnetin. Acetyl deriva-
tive C^HBr^AoO^. [0. 290°]. From aoetyl-
daphnetin and Br at 100° (Stiinkel).
sen
DAPHNETIN.
p.lS. ehyl-daphnetin
<4:3) /(I) 0(CH,):CH
C,Hj(OH)j< I . Formed by the
\(2) O CO
action of H^SO, on a mixtuie of aceto-acetic
ether and pyrogallol. By boiling with sodium
bisulphite till dissolved and then adding FejClj
a blue colouration is produced (Fechmann a.
Cohen, B. 17, 2188').
Daphnetic acid CjHj(0H)3.CH:CH.C02H.
Tri-oxy-cinnamio add.
Tri-ethyl derivative
CsHj(OEt)s.Cj]3:2.C02H; [193°]; colourless crys-
tals. V. sol. hot alcohol, ether, and benzene,
insol. water and CSj. Obtained by evaporating
the di-e]thyl-ether of daphnetin with aqueous
NaOH, and heating the residue with -^ethyl
iodide. On oxidation with KMnO, it gives tri-
ethoxy-benzoic aldehyde and acid (Will a. Jung,
B. 17, 1086).
Daphnetilic acid C„H30(0H)„.00jH.
Di-ethyl derivative C„H3b(OEt)2.COjH.
[154°]. Fine felted needles. Formed by boiling
the di-ethyl ether of bromo-daphnetin with alco-
holic KOH (Will a. Jung, B. 17, 1085).
DAPHNIN CisH.eO,. [c.200°]. Aglucoside
occurring in the bark of certain species of
Daphne (Vauquelin, A. Ch. 84, 173 ; Gmelin a.
Baer, Seh. J. 35, 1 ; Zwenger, A. 115, 1). Beet-
angular prisms (containing 2aq) (from water).
SI. sol. cold water, v. sol. boiling alcohol, insol.
ether. Alkalis and alkaline carbonates dissolve
it, foribing a yellow solution, which turns brown
in air. FejOl, colours its aqueous solution
bluish. It slowly reduces boiling Fehling's solu-
tion. Hot solutions are ppd. by basic lead acetate.
Emulsin or dilute acids split it up into glucose
and daphnetin.
DATISCIH Cj,H,,0,j. [180°]. A glucoside
occurring in the leaves and roots of Datisca
cannabina, which are used to dye silk yellow
(Braconnot, A. Ch. [2] 3, 277 ; Stenhouse, Chem.
Oaz. 1856, No. 318 ; A. 98, 166). Silky needles,
b1. sol. cold water, v. sol. alcohol, v. si. sol.
ether. Tastes bitter. Eesolved by dilute acids
into glucose and datiscetin. Bases dissolve it
with deep-yellow colour. Lead acetate, Fe^Clg,
CUSO4, and SnCl, ppt. its solution.
Datiscetin C,5H,„Oo. Formed as above.
Tasteless needles, nearly insol. water, v. c. sol.
ether.— 0,sH,PbO,.
SATirBINE is identical with ATBOfiKi: (q.v.).
DAVYTTU. According to Kern, some speci-
mens of Russian platinum ores contain a metal
which is not Ir, Os, Pd, Pt, Eh, nor Eu [C. N.
36, 114). The mother-liquor remaining after
separation of Eh and Ir by Bunsen's method
{P. M. [4] 36, 253) was heated with excess of
NH,C1 and KH,NOg ; the dark-red pp. thus ob-
tained was strongly heated, whereby the new
metal was obtained as a spongy mass, which
fused in the 0-H flame to a silver-white button.
The ore contained about -045 p.c. of the new
metal, to which Kern gave the name Da/uyum.
The metal is described as hard, but malleable
when heated ; e. sol. aqua regia, v. si. sol. boil-
ing H,,SO<. S.G. 9-389. At. w. about 154.
Several salts of this metal are described by Eern.
The whole subject requires re-investigation.
M. M. P. M.
DECACBYLIC ACID v. Dboenoic aoid.
DECANAPHTHENE v. Decylenb.
n-DECANE C.oHjj. (169°-170°) at 742 mm.;
(107°) at 100 mm. S.G. ? -745 ; « -734 ; i^
-069. S. (glacial acetic acid) 8 at c. 15° -, 20 at
60°. From n-ootyl bromide, EtBr and Na '
(Lachowicz, A. 220, 179). Formed also from
methyl ennyl ketone by treatment with POI5 and
reduction of the product by HI and P ; and by
reducing ootoic acid with HI and P (KrafEt, B.
15, 1695). Has hardly any smell and no taste.
Not attacked by cono. H^SO^. Attacked by Br
only when heated.
Secane C,„H22. Inactive di-isoamyl. (158-8°
cor.) at 782-8 mm. S.G. ^ -7216 (Lachowicz, A.
220, 172). V.D. 72 (for 71). S. (in glacial acetic
acid) 8 at c. 15° ; 20 at 65°. S.V. 231-3 (Schift, A.
220, 88). From isoamyl iodide and zinc (Frank-
land, C. J. 3. 32). From isoamyl bromide or
iodide and sodium (Wurtz, A. Ch. [3] 44, 275 ;
Grimshaw, B. 10, 1602 ; 0. J. 32, 260, 687).
Formed also by the electrolysis of sodium hexoate
(Brazier a. Gossleth, C. J. 3, 221). Tasteless,
with faint odour. Flashing-point 53°. Not at-
tacked by HNO5 or cone. HjSO,. Gives with
bromine decyl bromide, which on distillation
splits up into deoylene and HBr.
Decane CHMeEt.CHa.CH^.CHMeEt. AcUve
diamyl: (160°). V.D. 4-82 (for 4-91). S.G. ^
-7463. [o]d = 6-49° for 100 mm. at 22°. From
active amyl iodide and sodium (Just, A. 220, 155).
Decane (152°-153°). S.G. 21 .7187. V.D.
69-4 (for 71). In Galician petroleum (Lachowicz,
A. 220, 195).
Another decane from same source: (162°-
163°). 8.0.22-7324.
Decane C,^^. (160°) (Pelouze a. Cahours.
A. Ch. [4] 1, 5) ; (156°) (Wurtz, Bl. 1863, 300;
Lemoine, Bl. [2] 41, 165). S.G. is -757 (P. a. C.) ;
a -764 (L.). V.D. 4-95. Occurs in American
■petroleum.
Decane. (171°). S.G. i5 -756. In coal tar
(Jacobsen, A. 184, 202).
DECARBDSHIC ACID v. Usnetic acid.
DECENE V. Dectlene.
DECENOIC ACID O.oH.sOj i.e.
C,H„.CH:CH.CH2.C0jH. [10°]. Formed by
distilling the lactone of j3-oxy-heptyl-succinic acid
(3. v.). Oil, hardly soluble in, and lighter than,
water. Volatile with steam. Combines with
HBr (Schneegans, A. 227, 91).
Salts.— BaAV—CaA'j. '_
Decenoic aeidC|„H,j02. Amenyl-valeric acid.
(269°). S.G. i^ -961. From sodium isoamylate
andCOatl65° (Frohlich a. Geuther, A. 202, 297).
OU. The Na salt is deliquescent.
Decenoic acid CuHigO^. Amydecylemc acid.
(242° cor.). S.G.2-9096. Formed by oxidation
of the corresponding aldehyde (Borodin, B. 5,
481 ; Hell a. Schoop, B. 12, 193). Oil. Oxidised
by chromic mixture to acetic and isovaleric acid
(Gaess, B. 10, 455). The E salt is deliquescent.
CaA'2 -jaq : needles (from alcohol).
Decenoic acid C„H„02. Decacrylic acid.
[86^]. S. (cold alcohol) -08; (hot alcohol) 2.
Occurs in cork. Amorphous. Acid to litmus
(Siewert, Z. 18S8, 383).
DECENOIC ALDEHYDE C„H„0. Diisova-
leric aldehyde, (c. 189°). S.G. 2 -861. Formed
from isovaleric aldehyde by heating with zinc
filings, or by treating with Na, KOH, K.^CO„ o'.'
HCl (Borodin, B. 2, 552 ; 5, 481 ; 6, 983 ; Eiban,
DECOIO ALDEHYDE.
8W
Bl. [2] 18, 64 ; KekuW, B. 3, 135 ; ,Gaess a. Hell,
B. 8, 371). Oil. Does not combine with NaHSO,.
Btduces amtnoanical AgNO,.
DECENYL ALCOHOL O.oH^oO 'i.e.
CH,:OH.CHj.CPrj.OH. AUyl-di-propyl-carUnol.
(192° i.V.). S.G-. a -8602 ; f -8427. C.E. (15°-
29°) -00101. H.0. 1,544,900 (Louguinine, Bl. [2]
86, 663). From di -propyl-ketone, zinc, and allyl
iod de (SaytzefE, A. 196, 109). Oil, smelling like
turpentine. Chromic mixture oxidises it to di-
propyl-ketone, butyric aoid, and propionic acid.
Aqueous KMnO, gives COjH.CH^.CPrs.OH.
Acetyl derivative 0,„H„OAo. (210° i.V.).
B.6. » -890 ; "i -8733.
Secenyl alcohol C,„Hj„0 i.e.
CH.iCH.CELj.OPrj.OH. ' Allyl-di-isopropyl-car-
Unol. (170°). S.G. a -8671 ; '5* -8477. C.E.
(0°-24°) -00095. From di-isopropyl-ketone, allyl
iodide, and zinc (Lebedinsky, /. pr. [2] 23, 22).
Oil, smelling like turpentine. KMnO^ gives
COjH.CH2.CPrj.OH and isobntyrio acid. Forms
a liquid dibromide.
Docenyl alcohol C,„Hjj0. (0. 194°). From
acetone (75 g.), allyl iodide (205 g.), isobutyl
iodide (230 g.), and granulated zinc (Schatzky,
J.^ir. [2] 80,216). Oil.
DECEWYLENE v. Deoinene.
DECENTLEKE TETBABBOUIDE v. Tetba-
BBOUO-DEOANE.
DECINENE C,„H,s. DecenyUne. (c. 158°).
S.G. g -787; « -774; « -770. Bo, 77-1 to
78-8 (theory 75-8). Formed by heating
allyl-di-propyl-carbinol (decenyl alcohol) with
H,SOj (1 pt.) and water (1 pt.) at 130°. The oily
product is distilled, and the portion boiUng at
150°-170° is distilled over sodium in an atmo-
sphere of COj. Absorbs oxygen from the air.
Combines with bromine forming C,„H,jBr4. Oxi-
dised by chromic mixture gives acetic, propionic
and butyric acids (S. Beformatsky, /. pr. [2] 27,
389 ; Bl. [2] 40, 185).
Secinene C,(,H,j. Butylene. (150°). From
diamylene bromide and alcoholic KOH (Bauer,
A. 135, 344).
Deoinene C,„H,g. Sebacin. [55°]. (above
300°). Formed by distilling calcium sebacate
(Petersen, A. 103, 184).
Deoinene C,„H,8. (165°). Formed by the
action of alcoholic potash on di-bromo-deoane
derived from petroleum (Beboul a. Truchot, A.
144, 248).
Deoinene C|„H,j. Sydrocamphsne. [120°].
(160°). A product of the action of sodium on
the solid hydrochloride C,„H,eHCl derived from
turpentine (Montgolfier, A. Ch. [5] 19, 145). In-
active.
Deoinene C,|,H|g. Eydrocamphene.^ [140°
nncor.]. Prepared by the action of sodium and
gaseous HCl on a benzene solution of bornyl
chloride (C,„H,.C1), or of oamphor-diohloride
(C„H,5Clj) (Kachler a. Spitzer, B. 13, 615 ; M.
1, 589). White crystalline solid. V. sol. ether,
less sol. alcohol and acetic acid. Does not com-
bine with HCl. Very stable towards oxidising
agfents. Probably identical with the preceding.
Deoinene (?)C,„H,s. CampUm. (0. 169°).
S.G. 25 -827. Formed by distilling camphor
with iodine or HI (Glaus, J. pr. 25, 264 ; Weyl,
Si. I, 96). Br acta upon it by substitution.
DECINOIC ACID 0,„H,„Oj. [525"']. (307°)
Formed by the action of sodi.tm on butyrio
ether (Briiggemann, .4.246, 132).- Long needles.
DECINYL ALCOHOL C,„H„0 i.e.
(CHj:CH.CHj)jCPr.OH.Di.aZZj/Z:pro^Z-cor6MtoZ.
(194°). S.G. a -9707. O.B. (0°-20°). -00082.
Boo 78-7. From w-butyrio ether, allyl iodide,
and zinc ; the product being poured into water
and distilled (Saytzeff, A. 193, 362). Oil, smell-
ing like turpentine.
Decinyl alcohol C,jH,jO i.e.
(CHj:OH.CHj)jCPr.OH. Di-allyl-isopropyl-car.
Unol. (183° i.V.). S.G. 2 -8647'-, \° -8512.
From isobntyrio ether, allyl iodide, and zino
(Biabinin a. Saytzefl, A. 197, 70; Bl. [2] 31,
199). Oxidised by the air.
Deeiuyl alcohol (?)C,„H„0. (176°). From
valerylene and diluted HjSO, (Beboul, A. 143,
378). Oil.
Decinyl alcohol (?)C|,H„0. (c. 211°). A
product of the action of allyl iodide and zinc on
acetic ether (SohestakofE, /. pr. [2] 30, 215).
DECIFFITJU. According to Delafontaine
(O. B. 87, 632 ; 93, 63 ; O. N. 88, 223 ; 44, 67)
Sama/rskite from Korth Carolina, and Sipylite
from Virginia, contain an element belonging to
the group of the earths, but differing from all the
other metals of this class. To this element De-
lafontaine gave the name Decippium. The
double sulphate of Dp and E is insoluble in satu-
rated KjSO^Aq ; on this fact is based a method
of separating from terbium. Further researches
are required before the existence of decippium
can be regarded as established {cf. Eauths ; and
Eaeths, metals of the). M. M. P. M.
DECOIC ACID C,„Hj„Oj. Gapricaoid. Mol.w.
172. [30°]. (269°). S.G. 21 -930.
Occurrence. — 1. As glyceryl ether in butter
(Chevreul, Becherches sur Us corps gras) and in
cocoa-nut oil(G6rgey, A. 66, 295). — 2. As iso-
amyl ether in fusel oil from grapes (Fischer, A.
118, 307 ; Grimm, A. 157, 264), and in fusel oil
from Scotch whiskey (Bowney, A. 79, 236). — 3.
In Limburg cheese (Iljenko, A. 55, 85). — 4. To
the extent of 5 p.c. in the fatty mass deposited
by the water used to extract yolk {suint) from
wool (Buisine, C. B. 105, 614).
Formation. — 1. By the distillation of oleio
acid (Gottlieb, A. 57, 63).— 2, By oxidation of
oleic acid by HNO3 (Bedtenbacher, A. 59, 54). —
3. From octyl-aceto-acetio acid (Guthzeit, A.
204, 5).
Properties. — Slender needles, hardly sol.
water, of faint rancid odour. Sol. alcohol and
ether.
Salts. — AgA'. Needles from boiling water.
SI. sol. water.— BaA'j. Plates from boiling
water. SI. sol. water, sol. alcohol.— CaA'r —
MgA'j.— CuA'j.— NaA'. Sol. water.
Methyl ether MeA'. (224°).
£)thyl ether EtA'. (244°). S.G. -862.
Iso-amyl ether (275°-290°). In fusel oil
from grapes.
Chloride C,„H,50C1. (0. 210°) (Grimm, A.
157, 272).
Amide C,„H„0NHj. [98°]. Prepared by
digesting ammonio decoate at 230'' under
pressure ; the yield is 75 p.c. (Hofmann, B. 16,
984).
DECOIC ALDEHYDE C,,H,,.C0H (c. 106°)
at 15 mm. Formed by distilling a mixture of
368
DECOIC ALDEHYDE.
barinm decoate (caprate) and barium formate.
Liquid. On reduction with zinc-dust and acetio
acid it gives n-prim-decyl alooliol (Erafft, S.
16, 1716).
Isodecoic aldehyde C.oH^jO. (169° oor.J.
S.G. 2 -828. Formed by oxidation of iso-oapryl
alcohol. Oil. Does not combine with NaHSOj
(Borodin, J. 1870, 680).
SEOOmPOSITION, CHEMICAIt. The break-
ing down of one definite kind of matter into
simpler kinds is called chemical decomposition.
By a definite kind of matter is meant, in chemis-
try, an element or a compound. The term de-
composition can be applied in strictness only to
one class of changes undergone by compounds.
The products of the decomposition of a com-
pound are either elements or compounds ; the
mass of each is different from the mass of the
compound decomposed, and the properties of
each are different from those of the original com-
pound. The simplest cases of chemical decom-
position are those brought about by the action
of an external agency such as heat, light, or
electricity on a compound ; water, for instance,
is decomposed by the electric current into hydro-
gen and oxygen ; salammoniac is decomposed by
heat into ammonia and hydrogen chloride. By
a slight extension, the term chemical decomposi-
tion is used to include cases of chemical inter-
action between two or more bodies resulting in
the formation of new bodies, some at least of
which are simpler than the original substances.
Thus when water and potassium interact potash
and hydrogen are produced ; the water is often
said to be decomposed by the potassium, inas-
much as one of the products of the interaction
is the element hydrogen, which was formerly
combined with oxygen forming water. So when
acetic acid and phosphorus pentachloride react
to produce acetyl chloride, phosphorus oxy-
ohloride, and hydrochloric acid, each of the re-
acting bodies may be said to be decomposed by
the other. This example shows that the term
chemical decomposition is used as covering the
greater number of reactions known as chemical
changes. The combination of two elements, or
of one element and compound, or of two (or
more) compounds, would not generally be called
a decomposition ; nor would the term be custom-
arily employed with reference to an isomerae or
allotropic change, such as that of ammonium
cyanate into urea, or of one form of crystalline
arsenious oxide into the other form ; but with
these exceptions the terms chemical decomposi-
tion and chemical change have practically the
same connotation.
When a chemical change between two or
more bodies is called a decomposition, the term
is generally used with the object of concentrat-
ing attention chiefly on one of the changing sub-
stances. Thus the change which occurs when
potash solution reacts with chlorine to form
potassium chloride and chlorate is a decomposi-
tion of the potash, but a combination of the
chlorine with other elements. Again, when it is
said that common salt is decomposed by sul-
phuric acid with production of hydrogen chloride,
only one part of the chemical change is brought
prominently forward ; it might be necessary some-
times to say that sulphui-ic acid is decomposed
by common salt with production of sodium sul-
phate ; neither statement is a full account of the
occurrence.
Among chemical decompositions, in a nar-
rower sense of the term, processes of dissociation
take a prominent place. In these processes one
definite compound is resolved, by the action of
heat, into two or more elements or compounds
differing from itself, and each weighing less than
the original compound; thus hydrogen iodide is
dissociated into hydrogen and iodine, ammonium
carbamate is dissociated into ammonia and car-
bon dioxide, and so on.
Chemical decompositions ar.e special cases of
chemical change; the laws whith state the con-
ditions and course of chemical changes apply to
chemical decomposition. These laws are stated
and discussed in other articles; v. especially
Affinity, vol. i. p. 67 ; Chemical change, vol. i.
p. 731 ; Combination;, Chemical, Laws of ; Com-
position, Chemical. M. M. F. M.
BECO^ENE C,.H,.. (o. 148°). Prom di-
bromo-decylene (rutylene bromide) and alco-
holic potash (Bauer a. Verson, A. 151, 52;
Tugolesoff, J. B. 13, 447). Oil, smelling like
turpentine. Its bromide C,„H,|jBr2 gives no
cymene when heated with aniline. HCl gives
(C,.H,J,HC1.
Isomerides v. Tebfenes.
DECONOIC ACID C,<,H,,Oj. Tri-etUenyl.
butyric acid (?) (o. 255-'). Formed by heating
NaOEt and NaOAo in a current of GO at 205°
(Geuther a. Prohlich, A. 202, 309).
TC-prim-DECYL-ALCOHOL C,„H.„.OH i.«.
CH,(CHj),CHjOH. Mol. w. 158. [7°]. (119°) at
15 min. S.G. (liquid) I -8389 ; =," -8297 ; f -7734.
Large rectangular prisms or a thick sweet-smell-
ing highly-refractive liquid.
Formation. — Capric aldehyde (obtained by
distilling barium caprate with barium formiate)
is reduced with zinc-dust and acetic acid.
Acetyl derivative C„,HiiOAc (125° at 15
mm.). Mobile peculiar-smelling liquid. Solidifies
at a low temperature (Kr.ifft, B. 16, 171H).
Deoyl alcohol C„H„CHPr.OH. Propiil-heTiil.
earhinol. (211°). S.G. 2 -839 ; ^J" -826. Fioin
cenanthol and ZnPr.^ followed by water (Wagner,
Bl. [2] 42, 330 ; J. B. 16, 329). OU.
Decyl alcohol C,„H„OH. (200°). S.G. !??
•858. From the decane of petroleum vid docyl
chloride (Lemoine, Bl. [2] 41, 165 ; cf. Polouze
a. Cahours, J. 1863, 529 ; A. Ch. [4] 1, 5).
Deoyl alcohol C,|,H.;,OH. Isocajjric alcohol.
(203°). S.G. 2 -857. From isovaleric aldehyde
and sodium (Borodin, Z. 1870, 415).
Acetyl derivative CuH^iOAo. (220°).
S.G. 2 -883.
Benzoyl derivative C,„H.,,OBz. (above
280°).
Deoyl alcohol 0,„Hj,OH. (c. 230°). S.G. -84.
From isoamyl isovalerate and sodium (Lourenpo
a. Aguiar, Z. 1870, 404).
Acetyl derivative C,„H2,0Ac. (o. 232°). ^
Deeyl alcohol CuH^iOH. Diisoamyl alcohol.
(203°). Formed, together with an isomeride
(212°), from di-isoamyl (decane), by chlorination
and displacement of CI by OH (Grimshaw, £.10,
1602).
DEOYL BBOUIDE CgH^iBr. From di-iao-
amyl. Splits up on distillation into EBr and
decylene.
DEHYDKACETIO ACID.
S6A
UECYX CHLOaiDK 0„Hj,Cl. (200°). From
ai-isoamyl and CI (Schorlemmer, A. 129, 24G).
Decyl chloride O.oHj.Cl. (o. 202°) (Pelouze
s. Cahours, A. Ch. [4] 1, 5). S.G. la -908 (Le-
moine, Si. [2] 41, 165). From decane of petro-
leum and chlorine.
Decyl chloride C|„H2,CI. (o. 195°) (Wurtz,
Bl. [2] 5, 315). Prom CI and the decane from
di-bromo-deoane (diamylene bromide).
Decyl chloride C,„H2,C1. (o. 180"). From
decyl alcohol (isocapryl alcohol) (Borodin, /.
18ti4, 338).
DECYLENE 0,„Hj,. Di-amyUne. (156°-
156-3°) at 757-4 mm. ; S.G. w -7789 ; C.E. (10°-
156°) -00121 ; V.D. 4-86 (for 4-84) ; S.V. 211-3
(Schiff, A. 220, 90).
Formation. — 1. From isoamyl alcohol by
treatment with PjO, or ZnCl, (Cahours, A. 30,
295; Balard, A. 52, 316).— 2. From amylene
(tri-methyl-ethylene) and ZnCl, or cone. H..SO4
(Bauer, SiU. W. 44 [2] 87; Wysohnegradsky,
J. B. 7, 165 ; Berthelot, A. 128, 311 ; Lebedeff,
J. B. 7, 246 ; Erlenmeyer, Z. 1865, 362 ;
Schneider, A. 157, 207).
Properties. — Oil. Yields, among the products
of its oxidation, amethenic acid C^Hj^Oj.
Dedylene 0„H.,,. (163-7° cor.) at 744 mm.
S.G. S2 -7387. V.b. 70 (ealo. 70). From di-iso-
amyl by treatment with Br and distillation of the
resulting bromo-di-isoamyl (Lachowicz, A. 220,
178). Formed also by distilling deiyl acetate
(from decyl bromide and NaOAc). Aromatic
liquid. Soluble in dilute H2SO4 (1:1). Combines
readily with Br, but some HBr also comes off.
The product is decomposed by distillation.
Decylene C„H,„. (0. 159°). S.G. i* -855.
From petroleum decane (Lemoine, Bl. [2] 41,
165).
Decylene C,„Hj„. Decanaphthene. (161°). S.G.
S -795. Eqo 77-2. Occurs in petroleum from
Baku (Markownikoff a. Ogloblin, J. B. 15, 332).
Decylene 0,„Hj„. (171°). Among the products
obtained by strongly heated paraffin (Thorpe a.
Young, A. 165, 22).
Decylene C,„Hj„. (175°). S.G. 2 -791. From
blubber by saponification and distillation of the
lime salts of the resulting acids (Warren a. Storer,
Z 1868, 231).
Decylene C,oH,„. (176°). S.G. s -823. From
petroleum from Burmah (Warren a. Storer, Z.
1868, 231).
Isomerides v. Tetrahydrides of Teepenes.
DECYLENE GLYCOL v. Di-oxT -decane.
DECYLENE OXIDE C,„H2„0. Diamylene
oxide. (170°-180°). From C,„Hj„(0Ac)j and splid
E0H(Bauer, Site. TF. 45 [2] 276). Oil. Beduoes
ammoniacal AgNOj.
Decylene oxide C,„Hj„0. (c. 201°). V.D.
6-3 (calo. 5-4). Formed by the action of cone.
KOHAq on the product of the action of, crude
amylene on BzjO^ at 110° (Lippmann, M. 5, 563).
Does not reduce ammoniacal AgNOj nor combine
with NaHSO,.
DEHYDRACETIC ACID CsH,Oi t.«.
CMe.O.CMe
Ij II (?). [109°]. (270° cor.). S. 1
CH.CO.C.CO,H
at0°.
Formation. — 1. By passing the vapour of
aceto-acetie ether through a glass tube filled
with, pumice and heated to redness (Genther, Z.
Vol. II.
[2] 4, 655 ; Perkiu, jun., C. J. 47, 240 ; 51, 489).—
2. By the action of pyridine or picoUne upon
acetyl chloride ; these bases probably only act
by removing HCl, for they are found unaltered
at the end of the reaction (Dennstedt a. Zimmer-
mann, B. 19, 75).
ProperUea. — Needles or trimetrio tables (froic
water), Y. sol. hot water, hot alcohol, and
ether. Fe^Cl, colours its solution orange.
Beactions. — 1. Boiling cone. NaOHAq splits
it up into CO2, acetic acid, and acetone. Alco-
holic KOH forms, as intermediate products,
aceto-acetio ether and acetic acid. — 2. Ammonia
forms oxy-di-methyl-pyridine (Perkin, B. 18, 682 ;
Haitinger, M. 6, 105). — 3. Zn and HCl forms an
acid [187°] (Oppenheim a. Preoht, B. 9, 1101).—
4. PClj forms C,H„OjClj [101°], reconverted by
water at 200° into dehydracetic acid.
S a 1 1 s . — NaA' 2aq. — BaA'j 2ac[. — CaA',. —
ZnA'j 2aq. -AgA'.
Methyl ether A'Me : [91°]; prisms; v.
sol. water. Has distinct acid properties, forming
C,H„(Na)04Me (Perkin, B. 18, 218).
Ethyl ether EtA'. [92°].
Amide CgB^O^mi^. [209°]. From the acid
and aqueous KH, (0. a. P.).
Anilide C,H,0,NHPh. [115°],
Oxim C,H,0aC(N0H) : [173°]; colourless
crystals, sol. alcohol. Formed by the action of
hydroxylamine on potassium dehydracetate.
Fe^Cl, gives a purple-red colouration.
Phenyl ■ hydraeide 0,HgO,C(N.NHPh) ;
[c. 207°]; glistening yellow tables (from alcohol).
Formed by the action of phenyl-hydrazine on
potassium dehydracetate (Perkin a. Bernhart,
B. 17, 1522).
Chloro-dehydracetic acid C,H,C104. [93°].
From dehydracetic acid and CI (0. a. P.). Small
needles.
Bromo - dehydracetic acid C„H,BrO, i.e.
CBr.co.o.co.;a
II II (?)■ [137°].
CMe.O.CMe
Preparation. — Dehydracetic acid (5 g.) is dis-
solved in chloroform (50 g.), a slight excess of
bromine and a little iodiAe are then added, and
the whole warmed on the water-bath at about
50°. The reaction once started continues by
itself and is finished in about 12 hrs. (Perkin,
0. J". 51, 490).
Properties. — Plates and prisms. V. sol. hot
alcohol, chloroform, benzene, and petroleum-
ether, si. sol. cold alcohol.
Ozy-dehydracetic acid C,n,03 i.e.
COaH-O— CO— C.0H
II II (?). [c.253°].
Me.C — O-C.Me
Preparation. — Bromodehydraoetio acid is
dissolved in a little alcoholic potash, excess of
the latter is then added, and the whole allowed
to stand for several days at about 40° (Perkin,
C. /. 51, 491).
Properties. — Four-sided crystals. M. sol.
hot alcohol, almost insol. cold water, chloroform,
petroleum-ether, benzene, and acetone. Is readily
sol. alkalis. Sublimes with slight decomposi-
tion.
Salt.-C,HAAg2 (?).
Acetyl derivative C,H,04(0Ac). [167°].
Bhomboidal plates. V. sol. hot alcohol, m. soL
benzene, chloroform, ether, and CS,.
BB
S70
DEHYDRACETIC ACID.
Isodehydracetic acid v. Carbo-aceto-acetio
ether, vol. i, p. 20.
DEHYDEODlACETONAMINE v. Aceion-
AMINE.
DEHYDEACETONE-BEKZIL v. Acetone-
BENZIL.
DEHYDEACETONE - PHENANTHRAQUI-
NONE V. Agetone-phenanthraqdinone.
SEHYDEACETOPHENOITE-ACEIO-ACETIG-
ACID V. Aci:tofhenone-aceio-acetio acid.
SEHYBBACEIOFHENONE ■ ACETONE v.
ACETOFHENONE -ACETONE.
DEHYDEACETOPHENONE-BENZIL v. AcE-
lOFHENONE-BENZIL.
S£HYSEO-B£NZOYL-AGETIC ACID
CH.OO.C.COjH
C,.H„0^ i.e. II II (?). [172°]. Pre-
CPh.O.CPh
pared by heating benzoyl-aoetic ether for 7 or 8
minutes at its boiling-point, alcohol being split
off (Baeyer a. Perkin, jun., B. 17, 64 ; C. J. 47,
262; Am. 8, 101). Long yellow needles. V.
sol. ether and chloroform, m. sol. alcohol, si.
8ol. ligroin.
Beactioiis. — 1. By standing with cold alco-
holic EOH it is reconverted into benzoyl-acetic
BOid. — 2. It dissolves in cold HjSO, with an
olive-green colour, and on heating becomes a
splendid violet, the spectrum of which exhibits
the indigo bands; on dilution with water the
colour vanishes. — 3. Sodium amalgam reduces
it to an acid C,sH,20j [112°], and an acid
0,gH„04 [145°-150°].— 4. PcjClj colours the hot
alcoholic solution orange-red. — 5. Does not com-
bine with Br. — 6. Does not react with ACjO.
7. Eed-hot soda-lime gives acetophenone. —
8. Phenyl-hydrazine forms a yellow compound.
9. PCI, gives C„H„C10, [151°].
Salts. — FeSO, gives a blackish- violet amor-
phous pp., and Fe^Clg gives a deep scarlet pp. in
neutral solutions (Baeyer a. Perkin, B. 17, 64).
A'Ag : white floeculent pp.
Ethyl ether EtA'. , [159°]. Needles. M.
Bol. alcohol, benzene, and CS,, si. sol. ether and
light petroleum. FejClj colours its alcoholic
solution reddish-brown. NaOEt added to its
ethereal solution forms a sodium derivative.
Derived aci
C : CH.O.COjH
II II (?). [112°]. , Formed as above
CPh.O. CPh
(Reaction 3). Tables. V. sol. alcohol, ether,
benzene, CS^, and chloroform, almost insol.
light petroleum. Does not decolourise Br, in CSj
solution. Gone. H^SOj gives an intense orange
solution which on warming becomes first colour-
less and then greenish-brown.
Derived acid CnHnO, i.e.
CH.CH(GH).C.C02H
II II {?). [145°-150°]. Found in
CPb — 0 — CPh
the mother-liquor from which the above has sepa-
rated. Yellow needles (from alcohol-petroleum).
V. sol. most solvents, si. sol. light petroleum and
CSj. Gives off CO.^ on fusion. The CS^ solution
does not decolourise Br in the cold ; on warming
HBr is given off. Cone. H.^SO, forms a yellow
solution which becomes brownish-red on warm-
ing. Boiling Ao,;0 forms CJliflt [145°-150°]
which crystallises from 80 p.c. acetic acid in
yellow needles ; it is v. sol. hot ftlgoboli benaene,
and chloroform, but si. sol. ether ; and its alao
holic solution is turned scarlet by Fe^Cl,.
DEHYDBOBENZYXIDENEDIACETOACETIO
ETHEE V. BenztijIdiine-diacetoaceiio etheb.
DEHYDBO-CHOLEiC ACID v. Chole'io
ACID.
DEHYDEO-CHOLIC ACID v. Cholic acid.
DEHYDEO-CINCHENE v. Cinchene.
DEHYDEO-CINCHONINE v. Cinchonine.
DEHYDEO - CONatrilTINE v. Cinchona
DEHYDEO-MirCIC ACID v. Mucic acid.
DEHYDB0-DIFE0T0CATECH1TIC ACID v.
Tbtba-oxi-di-phenMi di-oaeboxylic acid.
DELPHININE Cj^H^NO.. [119°] (Blyth).
S. -02 at 20° ; S. (alcohol) 5 at 20° ; S. (ether) 9
at 20°; S. (chloroform) 6-3 at 20 \ An alkaloid
occurring, in the seeds of staveSacre, or Del-
phinium staphisagria (Lassaigne a. Feneuille,
A. Ch. 12, 358; Brandes, Schw. J. 25, 369 1
O. Henry, J. Ph. 18, 661 ; Couerbe, A. Ch: [2]
62, 352 ; J.. 9, 101 ; Erdmann, Ar. Ph. [2] 117,
43 ; Marquis, Bms. Zeit. Phamn. 16, 449, 481,
613). Trimetric crystals (from ether) ; a:bx
= •637:1: -804. Decomposes at 120°. Inactive ;
has a slightly alkaline reaction. Tastes somewhat
bitter. Cone. HjSO, gradually forms a faintly
brown solution changing to reddish-violet. A
mixture of delphine (1 pt.) and malic acid (1 pt.)
is coloured orange by H^SO^, the colour changing
through deep rose to blue (TattersaU, C N.
41, 63).
Salts.— B'2HCl.—B'HAuCl..—B 32HNO, (?).
-B',2H,S0,(?).-B'HHgI,.
Delphinoidina C^H^jN^O,. [110°-120°] (?).
S. •017; S. (ether) 33. Separates from the
ethereal solution out of which delphinine has
olystallised (Marquis). Miscible with alcohol.
Inactive. Tastes bitter. Has an alkaline re-
action. With sugar and H^SOj it becomes first
brown, then green (c/. Schneider, Fr. 12, 219).
HjSOj and bromine water give a violet colour.
Salts.-B'2HC1. — B'HjAujCL. — B'HjSO,.
— B'2HN0,.— B'2H0Ac.
Delphisine CjjH^NjO, '(?). Once found in the
mother-liquors, from which delphinine had
separated. Less soluble than delphinoidine
which it resembles.
Staphisagrine Cj^HjjNOs. [c. 90°]. S. -5;
S. (ether) ^117. Also occurs in stavesacre. Amor-
phous. Differs from the preceding alkaloids in
being much less sol. ether. Soluble in all pro-
portions in alcohol and chloroform. Optically
inactive. Has an alkaline reaction. Cone. H^SO,
gives a cherry-red or violet colour. Does not
give a green with sugar and H^SO,, or violet
with H^SO, and Br. HNO, colours it orange.
Salts. — B'HOl. — B'HNO,. — B'HOAo. —
B'HAuCl,.— B'Hgl, (?). -B'jH„SOj.
DENSITIES, BELATIVE, of soUdi, Uqnids,
and gases. — The subject of densities, absolute
densities, relative densities, and specific gravities,
deals with the following points : —
1. The mass contained in a definite volume
of any one substance, or, knowing that weights
are proportional to masses, the weights of defi-
nite volumes of different substances.
2. The ratio between the mass contained in
any volume of a substance and the mass con-
tained in an equal volume of a substance chosen
as the standard, or, expressing this somewhat
DENSITIES, RELATIVE.
371
differently, the ratio between the weight of a
certain volume of any substance and the weight
of an equal volume of the standard substance.
The terms in which these different ideas are
embodied are density, absolute density, reUiHve
■ density, and speeifle gravity. Unfortunately
there still exists a great deal of confusion as to
the use of these terms, and even the standard
text-books do not show agreement on this point.
It is, therefore, necessary to give definitions of
these terms showing the meanings which will
be given to them in this article, and then to
indicate wherein there is want of scientific pre-
cision in the ordinary use of the terms, and also
wherein the meanings given to them in the
text-books difier.
1. The density, or the absolute density, of
any substance at any temperature is the mass
of unit volume of that substance at that
temperature.
Thus, if D| stands for the absolute density
of the substance at temperature t, M., for the
mass of the substance at temperature t, Vt for
the volume of the substance at temperature t,
we have the relation D,= — ^; the numerical
value for the absolute density will depend on
the units of mass arid length employed.
Making use of the notation of dimensional
equations as introduced by Maxwell we get
m [L]' '■■"■•'
that is, we find the unit of density to be of one
dimension in mass, and of minus three dimen-
sions in length.
2. The specific gravity, or the relalmie density,
of a substance at any temperature is the ratio of
the mass of any volume of the substance to that
of an equal volume of some standard substance.
The standard substance generally chosen is
water at the temperature of its maximum
density.
The above definitions show that relative
density may be found by comparing the masses
of any volume ; we may choose the masses of
unit volume, but inasmuch as we have given
the name of density or of absolute density to
the mass of unit volume, we shall thus get a
new definition for specific gravity or relative
density, namely.
The specific gravity or the relative density of
a substance at any temperature is the ratio of
its absolute density to the absolute density of the
' standard substance.
Putting S for the relative density, we get
Mj
where M, and Mj stand for the masses of volumes
V and V
It is evident from the above formula that,
inasmuch as S is the ratio between two masses,
its value is independent of the unit chosen for
mass. Hence the number expressing the rela-
tive density or specific gravity is a pure number,
and has no dimensions.
On referring back to the two definitions given
above, we find density and absolute density,
relative density and specific gramity, used as
synonymous terms. It does not matter which
of them we employ, but it is better to make
a definite choice at the outset and to abide by
it. Absolute density goes with relative density,
and density with specific gravity. The terms
absolute density and relative density will be
used in this article. Unfortunately the terms
density and apedfie gravity are often used as
synonymous, specific gravity being applied to
solids and liquids and density to gases. To
give the same meaning to two terms which
express entirely distinct ideas is quite unpardon-
able. Attention has been drawn to this un-
scientific use of scientific terms in some of the
more recent standard text-books, but there is still
a difference of opinion as to the advisability of
using the term specific gravity in preference to
relative density, or vice versd. Agreement on
this point would be desirable.'
We have found that the numerical value for
the absolute density depends on the system of
units employed, while that of the relative density
is the same whatever the system of units. If
we use the C.G.S. system of units, as is now
done in scientific work, we find that there is a
definite relation between the unit of mass and
the unit of volume, the unit of mass being the
mass of unit volume of water at the tempera-
ture of its maximum absolute density. There-
fore the maximum absolute density of water is
equal to unity, and the irelative density of any
substance when referred to water at its maxi-
mum absolute density as standard is expressed
by a number which is identical with that of
its absolute density. Thus, taking the case of
gold, its absolute density in the C.G-.S. system
of units is 19-2 grams, i.e. 1 c.c. of gold weighs
19'2 grams ; the relative density of gold is also
19'2, that is, the mass contained in any volume
of it is 19'2 times as great as that contained in
an equal volume of water.
There are evidently two main methods for
experimentally determining the relative density
of any substance.
1. Determine its absolute density, that of the
standard being known.
2. Determine the ratio of the mass of the
substance to that of an equal volume of the stan-
dard.
A short account of the principles underlying
the most important methods for determining
relative densities is all that can be given here.
For detailed accounts of the relative values of
the various methods and for the necessary ex-
perimental precautions books on practical phy-
sics must be consulted. (The article Dichte in
Ladenburg's SandwSrterbuch der Chende, 3,
231-280, is particularly complete.)
I. Eelativb densities of solids. — The stan-
dard substance is water at the temperature of
its maximum density. It is not easy to produce
this temperature and maintain it constant ; how-
ever, we know accurately the density of water
' The German equivalents of density (DlchligteU) and
Bpeoiflo gravity (,Spec{IUchet GewieM) are used in exactly
the same sense as in English. There seems to exist a
great deal of ambiguity about the use ot the French terms
denslti ani pMs tpidflgm. The two are nsed as synony-
mous, or, lia difference is made, this consists in defining
demili as the matJ contained in unit volume, and poUU
tpid/iqut as the weight of unit volume (». Ditto, Exfosi i»
gutlqiui proprUtii ginirala del corps).
B B A
373
DENSITIES, EELATIVE.
at various temperatures, so that we can always
calculate what the mass of water at the tempe-
rature of the experiment would become at the
temperature of maximum density.
1. Experimental processes based on
Ihe first method, that is, on determining
the absolute density, that of water being
known. — Using the C.G.S. system of units
we find the absolute and the relative density to
be numerically the same. From the formula
M
D = ^ we see that the experimental work con-
sists in determining (a) a mass, that is practi-
cally a weight, (b) a volume. The following
methods are used in practice.
(i.) The body is weighed in air and then
thrown into a graduated vessel partly filled with
liquid. The difference in readings before and
after introduction of the solid gives its volume.
The weight in grams divided by the volume in
cubic centimetres gives the absolute density
which is numerically equal to the relative den-
sity.
(ii.) By means of the stereometer or volu-
menometei: The use of this apparatus is based
on the assumption of the truth of Boyle's law,
according to which pressure x volume = constant,
when temperature is constant. (For a descrip-
tion of the instrument reference must be made
to a manual of practical physics.)
2. Experimental processes based on
the second method, that is, on determining
the ratio between the mass of the substance and
the mass of an equal volume of the standard
substance.
(i.) The specific gramty bottle. — The form
and capacity of this instrument vary widely, ac-
cording to the special purpose for which it is
used, (generally it is a small fiask of thin glass
which will hold a definite volume of liquid. The
amount of liquid is adjusted either by filling the
flask up to a mark on the neck or by filling it
coQipletely and inserting a perforated stopper
through which excess of liquid flows out. The
obscrvatioils necessary are :
(a) The weight of the flask filled with dis-
tilled water
(6) The weight of the solid in air
w.
(c) The weight of the flask into which the
solid has been introduced filled with water up
to the mark or completely as before
W„.
Then we know that owing to the introduc-
tion of the solid into the flask a volume of
water has been expelled which is equal to that
of the solid introduced, the weight of this vo-
lume of water is (W;-1-'W)-Wy,, therefore the
relative density of the solid is
weight of solid
S =
W
weight of equal volume of water
W, + W-W„
The following methods for determining rela-
tive densities of solids are based on the principle
of Archimedes, according to which a body when
immersed in a liquid experiences a loss of weight
equal to the weight of the volume of liquid dis-
placed.
(ii.) The hydrostatic baUmce.—Tha solid is
weighed in air ; eall this weight W ; it is then
suspended by means of a fine thread from one
of the scale pans and weighed again ; call this
W, ; it is then suspended as before, immersed
in water and weighed ; call this W„. Then, by
the principle enunciated above, the weight of
water displaced by the solid — that is, the weight
of a volume of water equal to the volume of the
solid immersed — is W„ — W„ and the relative
W
density of the solid is S=.== — ==■.
W„-»Wf
(iii.) Jolly's balance. — The principle is the
same as that of the hydrostatic balance.
(iv.) Nicholson's hydrometer. — This instru-
ment belongs to the class of hydrometers in which
the volume immersed is kept constant while the
weight is changed. It consists of two cups
connected by a fine stem on which is placed the
mark of constant immersion. The instrument
is placed in a vessel of distilled water of suitable-
size and the following observations are made : —
(a) Weights, W, are placed in the upper cup
till the instrument sinks to the mark.
(6) The solid, together with sufficient weights,
W,, to produce the same result, are placed in the
upper cup.
(c) The solid is placed in the lower cup, and
weights, W^y, in the upper cup till the instru-
ment sinks to the mark again. From these data
w w
we find the relative density S = j= — =J-.
W,-W„
All the methods mentioned must be modified
for
1. Porous substances. In order to determine
what is termed the qppwremt density, that is, the
weight of the apparent volume including air
spaces, porous substances pervious to water must
be covered with varnish before immersion.
2. Substances soluble in water. It is neces-
sary to substitute for water some liquid of known
relative density, p„ in which the solid will not dis-
solve. Then if p is the relative density of the
solid when referred to the liquid of density p, as
standard, its relative density referred to water is
3. Solids lighter than water, (a) A liquid of
known density in which the solid will sink is sub-
stituted for water. The calculation is the same
as above in 2. (2>) The solid may be attached
to one of known weight, w, and known relative
density, p„ and of such a volume that the two
together will sink. The heavy solid is called a
linker ; the form it takes must vary according
to the light solid, the relative density of which
is required. The calculation is simple. Let the
weight of the solid in air be W ; the total loss of
weight on immersing sinker plus solid =W,;
then weight of water displaced by sinker = -
Pil
therefore, loss of weight on immersion due to
light solid =y{,—w,
iP,
and relative density of light solid = S ="
W
Wj-tfl'
Pi
(c) The solid may be prevented mechanically
from rising; this might be done by having a
wire cage attached to the lower pans in a Jolly's
balance or in a Nicholson's hydrometer.
DENSITIES, RELATIVE.
373
II. BbIiAtive dekhiiies of liquids. — The
standard is water at the temperature of its
maximum density.
1. Experimental processes based on
the determination of the absolute
density are not numerous. Specifio gravity
bottles which when filled up to a mark in the
neck contain a definite volume, generally marked
outside, are much in use. The difference be-
tween ^e weight of the bottle when filled with
liquid and when empty gives the weight of a
known volume of liquid, from which the absolute
density, i.e. the weight of unit volume, can be
calculated.
2. Experimental processes based on
determining the ratio between a speci-
fied mass of the liquid and that of an
equal volume of water,
(i.) The hydrostatic balance. — A glass rod is
weighed first in air, then immersed in the liquid,
and finally immersed in water. If W and W, are
the losses of weight on immersion in the liquid
and in water respectively, then these are the
weights of equal volumes, as both are the weight
of a volume of liquid equal to the volume of the
rod. Hence the relative density of the liquid
isS = ^
W,.
(ii.) Tlie specifio gravity bottle. — A glass
vessel of suitable size and form is weighed when
empty in air — ^let this be W ; it is then weighed
when filled with woter — let this be W, ; it is
again weighed when filled with the liquid— let
this be W„; the relative density is given by
the formula S=Sii^
w, — w.
(iii.) Method based on the fact that when
two columns of Uguid are in eguiUbriv/m with
each other their heights are inversely propor-
tional to their densities. — A tube of the shape
A- -S
^a
shown in the figure is very suitable. There
is air between A and B, water between B and F,
and the liquid under examination between A and
B. The vertical distances A E and B ¥ are
measured — let these be h and h'; then /)h = p,h,
where p and p, are the absolute densities of fbe
■ two liquids, but p, = 1 and p = i-'.
(iv.) Bydrometers.— These are of various
kinds.
A. The volume immersed is kept constant,
and is indicated by a mark on the stem.
The relative density is given by S = „— -,X.
G + W/
where G is the weight of the hydrometei-, W ia
the weight necessary to make it sink to the
mark when immersed in the liquid, and W, ia
the weight required to cause it to sink to tha
same mark when immersed in water. Nichol-
son's and Fahrenheit's hydrometers belong to
this class.
B. The weight of the hydrometer is kept con ■
stant, and the volume immersed varies. A scale
is attached to the stem ; this is divided differently
in different types of instruments.
a. It is divided into equal parts; to find the
relative density it is necessary to consult' a table
in which these arbitrary units are expressed in
terms of densities. BeaumS's hydrometer is an
instrument belonging to this class.
/3, The scale-readings give directly the relative
densities sought. In order that this may be done
the volumes immersed must decrease in har-
monical progression as the densities increase in
arithmetical progression. Twaddle's hydrometer,
belongs to this class. A difference in relative
density of 0-005 is taken as one degree, so that
there are 200° for a range of relative density
between 1 and 2. Hence for a reading of n
Twaddle, the relative density 3 = 1 + ^
(v.) Specific gravity balls. — These are sets
of small glass baXia with the number indicating
a relative density marked on each. The ex-
perimental work consists in ascertaining which
ball will just float in the liquid. The number
on the ball gives directly the relative density of
the liquid.
The nature of the liquid, the quantity of it
at our disposal, and the degree of accuracy re-
quired, must decide to which of the above
methods the preference is to be given. For very
rapid and only approximate work it is best to
use a hydrometer, while the specifio gravity
bottle, which can be made very small and so as
to present a minute surface for evaporation, is
best for accurate work as well as for cases in
which we have to deal with only a small quantity
of liquid or with a very volatile liquid.
III. Bel^tivb densities of gases and
VAPOUBS. — The standard is air at 0° and a pres-
sure of 7G0 mm. Eelative densities are found
by determining the absolute density at a known
temperature and pressure, and then calculating
what that density would be at 0° and 760 mm.
pressure, on the assumption of the rigorous
truth of Boyle's and Charles's laws. The ab-
solute density of the standard, that is of air, ia
supposed known ; Begnault's value, 0-001293, is
generally accepted. It is to be regretted that
the word density 'is almost universally used
when the relative density or the specific gravity
of a gas or vapour is meant.
A. Relative densities of gases, that
is, of substance^ which are gaseous at the ordi-
nary temperature.
1. Begnault's method. — The method first
used by Biot a. Arago' was wonderfully im-
proved by Begnault.' A large glass balloon ia
■ Blot a. Arago, 'Determination da poids da litre
d'aii,' Mimoira de I' Acad. 1808.
■ Begnault, ' D6tcrmiiiation de la deasltd des ga^'
iUmoira de I'lnitUut, XXI.
874
DENSITIES, RELATIVE.
filled with the ,gas at pressure H, and the tern-
perature of melting ice. In order to avoid the
very uncertain correction for buoyancy in air,
which is of the greatest importance in weighing
quantities of gas, which are often lighter than
&e air displaced, the balloon is weighed when
counterbalanced by one of the same volume and
made of the same glass. It is then exhausted
to pressure h, the temperature being kept at
zero, and weighed again. The difference, W,
between the two weights gives the weight of the
gas filling the balloon at pressure B.-h, from
which that at normal pressure is deduced to be
=W„ = W.^. The volume of the balloon
being known or determined, we possess all the
necessary data for calculating the absolute den-
sity of the gas. The utmost has been done from
the physical side to secure accuracy in these de-
terminations ; the great difficulty at present is to
obtain the gases used in a state of sufficient
chemical purity.
2. Bunsen's method.'' — This is based on the
law that the velocity of effusion of gases through
fine tubes is inversely proportional to the square
roots of their relative densities. This method is
applicable when only small quantities of gases
are at our disposal, and when only approximate
values are required.
B. Relative densities of vapours, that
is, of substances which must be raised to a tem-
perature above that of the atmosphere, in order
to change them into gases.
Here, again, it is the absolute density which
is determined directly, and which is referred to
that of air. The experimental processes consist
either in determining the weight of a known
volume of gas (Dumas's method), or in determin-
ing the volume occupied by a known weight'
(Gay-Lussao'a, Hofmann's, Meyer's method).
Let W be the weight of any volume, v, of any
vapour at temperature t and pressure p ; let W
be the weight of an equal volume of air at the'
same temperature and pressure ; then the lela-
W
tive density of the vapour <2 = 7iv but
W-=''»TT7r
■P. .
760"
W 760
vS
-^(l + of)
where S is the weight of 1 o.c. of air at 0° and
760 mm. According to this formula, in which 8
and a are constants, four magnitudes, v, t, p, and
W, must be determined in order to give us d.
Dumas's method. — The weight w of a thin
glass balloon ending in a long fine neck, when
' full of dry air at temperature T and pressure P,
is determined. Excess of the substance to be
v^pourised is introduced into the balloon,
which is then heated in a bath to a suitable tem-
perature. When vapour ceases to escape from
the neck of the balloon, the end of the neck is
sealed by melting in the blowpipe ; the tempe-
rature, t, of the bath, and the atmospheric pres-
sure, p, being noted. The weight, w,, of the
balloon full of vapour is thus determined. By
breaking the point of the neck under water or
mercury, the balloon is completely filled with
one of these liquids, and the diflerence between
■ Bunsen, Qaiometrische Methoden.
■ <lfi ANAI.T8IB, vol. L pp. 327-323.
the weight of it when tilled and when empty
gives the weight of liquid filling it; the ab-
solute density of this liquid being known, we
have the data required for calculating the volume
of the balloon. We have now obtained v, t, and
p by direct observations. We must find the
weight, W, of vapour filling the balloon at temp,
t, and pressure p.
W='w, —weight of glass
= w, —{w — air filling balloon at temp. T and
pressure P)
= w, —w+w,,
where «„ = «S. j^^ . ^^.
Oay-Lussac's method. — A tube of about half
the barometric height, divided into cubic centi-
metres, and completely filled with mercury, dips
into a trough of mercury and is surrounded by a
vessel of water. The whole apparatus can be
heated to the required temperature. A known
weight of the substance contained in a small
glass bulb is allowed to rise in the tube filled
with mercury. On heating the apparatus the bulb
breaks, and the substance is changed to vapour.
The four data necessary for substitution in the
above formula are obtained, in the following
way:—
W = the weight of substance, is obtained by
direct weighing ;
t) = the volume, is obtained by reading the
volume occupied by the vapour in the
tube in terms of scale-divisions ;
t = the temperature of the surrounding water ;
p is given by the difference (reduced to 0°)
between the height of the barometer
and the height of the mercury column
in the tube.
Sofmann's method. — ^This method is a modifi-
cation of that of (ray-Lussac, a tube longer than
the barometric height being used. The observa-
tions and calculations are the same as in Gay-
Lussac's method. This method has the advantage
that the substances are volatilised at tempera-
tures lower than their ordinary boiling-points.
V. Meyer's method. — A known weight, W, of
substance is dropped into a glass vessel of the
form shown in the figure. The bulb
of the apparatus is kept at a tempera-
ture higher than the boiling-point of
the substance. The volume, v, of the
air which escapes through the side
tube, and whose place in the tube is
taken by an equal volume of vapour,
is collected and measured at temp, t
and pressure p. We have so ob-
tained all the data necessary. This
method is very rapid, and it possesses
the additional advantage of not re-
quiring a determination of the tempera-
ture of the vapour itself, a process which
is always attended with great uncerr
tainties.
Corrections to be applied in
determinations of relative den-
sities. The relative density being
the ratio of two absolute densities,
we have to consider the circumstances
which produce a change in the absolute
density, and how we can introduce
suitable corrections. The absolute density being
got by dividing the weight by the volume, it ii
DENSITIES, RELATIVE.
875
best to consider the corrections to be applied
to each of these two quantities separately.
1. The weight. — ^In order to eliminate errors
due to the balance we must in all accurate work
use the method ot double weighing. This gives
the true weight in air ; the true weight in vacuo
is given approximately by
W = w(l — +^)' where w = true weight in air.
A = relative density of air at the moment of
weighing. This will depend on, and entail
a knowledge of, the temperature, pressure,
and hygroscopic condition, ot the air.
(Tn relative density of substance weighed. The
approximate value for this obtained by
using the uncorrected weight may be used.
f- relative density of the weights. •
2. The volume. — The volume changes with
the temperature and with the pressure.
a. Influence of temperature. — In nearly
all cases the volume increases as the tempera-
ture is raised. Hence the absolute density,
which varies inversely as the volume, decreases.
If the volume V,, at temperature 0° changes^ to
V, at temperature t, where V( = V(l + to), a
being the coefficient of cubical expansion, the
density D,, changes to ^^a'
It is therefore necessary in all accurate density
determinations to state the exact temperature at
the time of the experiment, .and to record the
result as relative density at temperature f , or if
the determination has to be reduced to normal
temperature, that is, to the temperature of the
standard (4° when water, 0° when air), it is neces-
sary to calculate what the absolute density at
that temperature would be from the above
formula, knowing the value for o.
6. Influence of pressure. — The change in
volump owing to change in atmospheric pressure
is imperceptible in the case of liquids and solids,
but it is very large in the case of gases and
vapours. Boyle's law gives us the means of
calculating what the volume would be at normal
pressure, that at any other pressure being known.
The volume being inversely proportional to the
pressure, the absolute density is directly propor-
tional to the pressure.
Lord Bayleigh has pointed out {Pr. 43, 356)
that the glass balloon used in Begnault's method
for determining the relative densities of gases
when exhausted is sensibly compressed by the
pressure of the air ; hence the tare of the balloon
is too large because of the lessened buoyancy of
the atmosphere, and therefore the weight of the
gas when the balloon is filled is too small. A
correction must therefore be experimentally made
for each balloon used (for method v. Lord Bay-
leigh Z.C., also Cooke and Bichards, P. Am. A.
24, 184).>
' Dumas' method lor determining the relative densities
of gases is described in A. Ch. [2] 33, 337 ; Gay-Lussao's In
Biot's TraM de Phgi. 1, 291 ; Hofmann's in S. I, 198 ; and
Victor Meyer's in S. 11, 1868 and 2263. For oritioiams on,
and modifloationa ol, Meyer's method v. B. 12, 609, and
1112 ; 13, 401, 861, 991, 1079, 1186, and 2019 ; 14, 1727 ; and
16, 137, 1161, and 2776 (in the last paper by V. Meyer (A
16, 2776) vpill be found an interesting and valuable criti-
cism of the various methods for finding the rel. densities
of gases) ; ». also B. 16, 1051 ; 19, 1R61 ; also C. J. Tram.
for 1880,491. Modlflcutionsof Dumas's method are de-
scribed by Bunsen, c. GiKomelilm-he i/eihodeii. 2iid ed. 1877,
p. 172 ; also by Pettersson and Ukstraud, Jl. 13, 1191 ; and
It remains now to indicate in how far the de-
termination of the density, that is, of one of the
physical constants, of various kinds of matter is
of importance in those investigations into the
constitution and the decompositions of matter
with which the chemist is concerned. In these
investigations it is often found more convenient
to deal with the reciprocal of the density -^
a
to which the name of specific volume has been
given.
Let us first consider those cases in which we
are concerned only with the constitution of sub-
stances in the state of chemical equiUbrium, and
not with chemical change.
1. The density being a well-defined physical
constant, a determination of its value tells us in
many oases whether the substance under exami-
nation is or is not approximately pure. It must,
however, be borne in mind that in the case of
many metallic elements the value of the relative
density will depend on the previous treatment
the substance has undergone, such as whether
it has been hammered or drawninto wire, whether
it has been tempered, &o.
2. Many tables have been compiled, in which
the percentage of acid or of alkali contained in
an aqueous solution of definite relative density
is given. By the help of such tables the deter-
mination of the relative density enables us at .
once to estimate quantitatively the acid or alkali
present in a known volume of the solution.
3. How the determination of the relative den-
sity of a gas or of a vapour gives us the means
of calculating its molecular weight will be found
described in the article Atomic and uoleculah
wBioHTs (vol. i. p. 336).
4. Those elements which exist in allotropie
modifications, and those compounds which show
polymorphism, differ, though often only slightly,
in density. Thus we have
Sulphur
Octahedral .... 2'05
Prismatic .... 1-98
Amorphous insoluble 1'95
Cai-bon
Diamond .... 3-55
Graphite .... 2-3
Gas carbon .... 1-885
Phosphorus
White . . 1-82
Bed . . 2-2
Arsenious oxide
Amorphous
vitreous 3-7385
Octahedral 3-695
Bhombio . 3-85
Calcium carbonate
Arragonite 2-94
Calcite . 2-72
Titanic acid
Entile 4-24
Brookite 4-15
Anatase 3'9
especially by Pawlewski, B. 16, 1293. Thorpe (C. J. Tram.
for 1880, 147-160) has described a very complete method
based on Hofmann's process. V. Meyer {B. 9, 1260, and 10,
2U68) has described a method based on the displacement of
mercury. In W. A. 22, 466 and 493, von Klobukow de-
scribes two processes for determining vapour densities with
great aSsouracy ; one is adapted tor bodies with low boiling-
points, the other for bodies which boil at high tempera-
tures. La Coste (B. 18, 2122) describes a modification of
V. Meyer's apparatus whereby the vapour densities of
easily decomposable compounds may be determined at low
temperatures and under very small pressures. A modifi-
cation of T. Meyer's apparatus, by which a vapour density
and the exact temperature of observation can be simulta-
neously determined, is described by Nilson and Pettei-sson
in J. pr. [2] 33, 1 ; «. also Soball, B. 20, 1433. Malfatti and
Schoop (,Z. P. C. 1, 169) describe an apparaVis for deter-
mining vapour densities under small pressures. '
876
DENSITIES, RELATIVE.
Silica
Quartz . . . 2-G5
Tridymite . . 2-3
(e/. AiiLoiBOFY, vol. i. p. 128). Little has been
done as yet in tracing the connexions be-
tween these differences in density and the other
physical and chemical properties of these sub- ,
stances, but some interesting facts have been
brought to light. Thus we know that long-con-
tinued heating changes the relative density of
anatase, 3-9, and of brookite, 4*15, to 4-24,
which is the relative density of rutile ; in the
case of silica, and in that of calcium carbonate,
the relative density of the heavier variety is
changed into that of the lighter variety, by the
action of heat. It has also been noticed that in
a great many cases the higher relative density
belongs to that allotropic modification which con-
tains the less potential energy in so far as there
has been production of heat in the change from
the less dense to the more dense modification.
Thus 80 gram units of heat are produced in the
change of 82 grams of prismatic sulphur (rel.
dens. 1-98) into octahedral sulphur (rel. denis.
2-05) ; the change of white phosphorus (rel. dens.
1-82) to red phosphorus (rel. dens. 2-2) is aooom-
panied by the production of about 25,000 thermal
units per 31 grams phosphorus changed. How-
ever, the case of the change of ai-ragomte (rel.
dens. 2-94) to calcite (rel. dens. 2-72), which is
accompanied by the production of 4,000 heat
units per 100 grams material changed, as well
as other similar cases, prove that this rule is by
no means general.'
6. It has been observed that on bringing to-
gether quantities a and <t' of two substances of
relative density d and d', the resulting density is
. . , . a+a'
not given by A = •,
a a ; that is the resulting vo-
lume is not the sum of the volumes of the con-
stituents. The following cases have been inves-
tigated : —
I. Solution of a salt in water. — Contraction
generally takes place. From measurements of
the amount of contraction, and of the specific
heat of the solution, and the coefiicient of expan-.
sion, Deville has calculated the amount of heat
due to the contraction, and has tried to show
that in most cases this is sufficient to account
for all the thermal phenomena of solution.
It has been observed further that the amount
of contraction increases with the quantity of the
solvent, approaching a maximum. Also the
amount of contraction for the same amount of
solvent decreases as the temperature at which
solution is effected is raised. The most interest-
ing researches in connexion with this subject
are those of Valsou,^ who has endeavoured to show
that the contraction produced on dissolving a
salt in water is made up of two parts, one of
which is a characteristic constant of the basic
radicle, and the other is a characteristic con-
stant oi the acidic radicle.
II. Mixture of two liquids. — A contraction
always takes place which varies in magnitude
■ St. Claire Deville, Sur la Contiaction et la Chaleur de
Ctmiftietion (C. R. 60).
' \'nlsrti), Propri^/i.i moSuhtiivt des solufiona KtUrma au
foiiit dii fuf ilifs d..'tuitis ^C. li. ^'i).
with the relative quantities of the two liquidg
used. Here again Deville has tried to explain
the thermal effect produced on mixing the two
liquids by means of this contraction. The vo<
lume-change on mixing alcohol and water is the
one which has been most thoroughly studied.
III. Chemical action between two solutions.—
The cases studied deal mainly with neutralisa-
tion-phenomena. It has been established that
the volume-change is expansion if the bases are
KOH and NaOH, and contraction if the base is
NH4.OH. Here also the volume-change decreases
as the temperature is raised. Ostwald, who in-
vestigated the density- changes attendant on the
neutralisation of dilute aqueous solutions, has
arrived at a law the same as that found by Val-
son for solution. He found the volume-change
due to chemical change to be the sum of two
constants which belong individually to each of
the components, and which do not depend on
the substance with which each component com-
bines.
6. A knowledge of the relative density of an
element or of a compound is necessary for the
determination of the constants ;
atomic volume = ( atomic weight x
\relative density/ '
and imlecuUr volume = f molecular weights
\ relative density /
A description of how the atpmic volume, regarded
as a periodic function of the atomic weight, assists
in classifying the elements will be found in the
articles Classification, cheuicai., and Febiodio
LAW. The generalisations arrived at with regard
to molecular volumes of solids, and especially of
liquids, will be dealt with in the article, Specii-io
VOLDMES, in vol. iv.
7. Another physical constant which entails a
knowledge of the relative density of a body, and
which has led to some valuable generalisations
as to the interdependence of chemical constitu-
tion and physical properties, is the refraction
egvmalent. This constant is defined as ^iZ.^
a
where ft is the refractive index, M the molecular
weight, and d the relative density, of the sub-
stance under examination. On this subject v.
Physical methods used in ohemistky.
The cases in which a knowledge of the rela-
tive density has been employed in the soljation
of problems belonging to chemical kinetics are
but few.
1. The change in the relative density of va-
pours and gases (calculated to normal tempera-
ture and pressure) under different temperatures-
and pressures has been utilised to trace the rate
of decomposition relatively to the change of tem-
perature or pressure (v. Dissociation).
2. From a knowledge of the volume-change
produced on neutralising a base A by an acid B,
and on neutralising A by another acid C, as well
as from knowing the specific volume of a solu-
tion containing A, B, and C, in equivalent quan-
tities, Ostwald deduced the chemical composi-
tion of this solution, that is, he determined the
ratio between the quantities present of AB and
AC. The knowledge of this ratio enabled him
to calculate the coefficients of relative affinity
of the acids B and C (v. Affinity, vol. i. p. 75).
DESMOTHOPY.
^77
S. In his researches on the velocity of chemi-
cal change as dependent on the varying conditions
of the experiment, van 't Hoff ' investigated the
velocity of the change of rhombic sulphur into
monosymmetrio by observing the increase in
^ volume at fixed intervals of time. The increase
in volume being due to the change of rhombo-
hedral sulphur of relative density 2-05 into
obUque sulphur of relative density 1'98. I. P.
SEOXIDATIOK. This term was originaUy
used to denote any process wherein oxygen was
removed, wholly or in part, from a compound.
Thus the formation of KCIO, by heating KCIO^,
several classes of compounds to produce less
oxidised bodies is called a daoxidismg agent or
reducing agent ; while any element or compound
which generally reacts to form bodies more
oxidised than the original substances is called
an oxidising agent or oxidiser. Probably every
element and compound takes part in some
chemical changes in which it acts either as an
oxidiser or a deoxidiser; but these terms are
generally confined to such elements and com-
pounds as frequently react in the way indicated
by the names. The following equations exhibit
some common oases of deoxidation : —
Original element or
compound
o,
(in this case the
a,
o.
2C1,
ci;
2HN0,
2KC10,
FeA
CuO
BeClj
i'e,(S0,)3Aq
2FeCl,Aq
2HgCljAq
HgCL^q
SAgNOjAq + HjO
KjMn.,OsAq
I'eClaAq
Deoxidiser Deoxidised product Oxidised product
+ 2Hj = 2H2O + (2H2O)
water may be regarded as produced either by the oxidation ot
hydrogen or by the reduction of oxygen)
+ H, = 2H01 + (2HC1)
+ Hg = O, + r -
(in this case the ozone is reduced to oxygen)
2HgO
=
Hg,OCl,
+
K,FeOy.
=
KCl
+
Sn
=
NA
+
3G
IS
2KC1
+
3H,
=
2Fe
+
CO
=
Cu
+
Na
=
Be
+
SO,
=
2FeS0,Aq
+
Zn
=
2FeCl2Aq
+
HNOAq
=
■H,0
+
SnCl^q
=
2HgCl
+
SnCLAq
=
Hg
+
C,H^O
=
2Ag
+
3B.fi.flM
=
K20Aq + 2MnO„
+
KIAq
=
FeCljAq + i
+
as well as that of KGl by heating KGIO,, are
alike deoxidations ; similarly the production of
CrA from CrO, by the action ot alcohol, and
the formation of Cr by heating CrA '^^^
carbon, are deoxidations. But as the term
oxidation {q. v.) has been widened to include
those chemical reactions wherein the negative
or acidic radicle of a compound is increased
relatively to the rest of the body, and also those
wherein an element combines with a more nega-
tive element, or with a radicle more negative than
itself, so has the term deoxidation been extended
ontil it is now generally applied to all processes
which result in the withdrawal of the whole or
a part of the negative radicle of a compound.
The terms deoxidation and redtiction are
practically synonymous ; the latter is more com-
monly used than the former.
As thus employed the terms deoxidation and
oxidation are correlative; the deoxidation of one
body is accompanied by the oxidation of another.
Thus, to take a very simple case, when hydrogen
is burnt in oxygen with production of water, the
hydrogen is oxidised and the oxygen may be said
to be deoxidised. If the reaction is represented
in molecular formula the processes of oxidation
and deoxidation are made apparent ; 2EH -)■ 00
= 2HA Similarly, when hydrogen and chlorine
combine, HH-hC1C1 = 2H01, the hydrogen is
oxidised while the chlorine is deoxidised or
reduced.
Any element or compound which reacts with
< .Sluda de l>iinamiqae Chlmique,
01,0
K/PeCy.
SnO^ + K-ja
3C0j
3HjO
COj
2NaCl
2S0^q
ZnCljAq
HNOgAq
SnCl,Aq
SnCl,Aq
CjH.Oj + 2HX0jAq
3H,0 + 6CO,
KClAq
Among the substances commonly used in the
laboratory to accompUsh deoxidations, hydrogen,
carbon, carbon monoxide, sulphur dioxide, ni-
trous acid or a nitrite, stannous chloride, and
aldehyde are prominent. The conditions under
which deoxidations occur vary much : thus,
HgCljAq is almost instantly reduced by SnClj at
the ordinary temperature; to reduce FcjiSOJjAq
completely to FeSOi by SO^ the gas must be
passed into the liquid for a long time, even when
the liquid is kept hot ; KjMn AM i^ reduced by
HjOjOjAq rapidly if the liquid is warm and con-
tains sufficient H^SOf to dissolve the MnO, pro-
duced ; to effect the complete reduction of
PeCljAq by KI the iquid must be slightly aci4,
and the reaction should proceed for some time
at a fairly high temperature and under increased
pressure; FeA i^ deoxidised by E when a
stream of the gas is passed over the heated
oxide ; to reduce BeOL, by Na the chloride must
be kept molten (cf. articles Combustion, Oxida-
tion, Eedtjoiion). M. M. p. M.
DEOXY- V. Desoxy-.
SEOXTBENZOIIT v. Fbehttl benzyl ketonb.
DEOXY-BENZOIIf -ACETIC AaD v.Phenyl-
BBNZOYL-PBOPIONIO AOID.
DEOXY-BEKZOlN' CABB0X7LIC ACID «.
Phenyl benzyl ketone cabboxylic acid.
Anhydride v. Benzylidene-puthalide.
DESMOTROPY. A term given to the break-
ing up of the 'double bonds' in the benzene
ring. Thus phloroglucin forms a penta-ethyl
derivative in which the five ethyl groups are
S78
DESMOTEOPY.
directly united to ring carbon atoms. The con-
■titntion of this body, according to Herzig a.
OEt:C(OH).OEtj
Zeisel (Jir. 9, 217), must be f , | .
CO.OEtj.CO
SESOXALIC ACID C AO, i.e.
COjH.CH(OH).C(OH)(COjH)j.-Oar6oa!3/-racem«!
aei4. Its ether is formed, together with a syrupy
isomende (Brnnner, B. 12, 542) and other pro-
ducts, by the action of 3 p.c. sodium-amalgam
on cold oxalic ether. After saponification by
EOH the free acid is obtained by exactly neu-
tralising the Ba salt by HjSO, and evaporating
at 46° (L8wig, J. pr. 79, 455 ; 83, 139 ; 84, 1;
Klein,/.i)r. [2]20, 146).
PmperUes. — ^Hygroscopic crystalline mass
(containing aq). V. e. sol. water and alcohol.
Decomposed by heat. Its solution evolves CO,
on evaporating above 60°, leaving racemic acid.
Salts.— Na3A"'.—K,HA"'. S. 6-2 at 16°:
erystalline crusts. — KjA'": gummy. — Ba3A"'j2aq.
— Ca,A"'j 3aq.— Pb^"'jO,.— Ag,A"'.
Ethyl ether EtjA'": [85°]. S. 10 at 16°.
Triclinic crystals, a:6:c = -422:1: -757; a = 84° 27',
(8=90° 32', 7 = 90° 6'.
Acetyl derivatives C^HsAcO, and
OsH^ACjOg are non-hygroscopic oils, not decom-
posed at 120°.
Benzoyl derivatives C^H^BzO, and
CjH^Bz^Og are oils, not decomposed at 140°.
Amide. Amorphous (Brunner).
SESOXT-AMALIC ACID v. Amalic acid.
SESOXT-BENZOIIT v. Fhenxl benzyi. ze-
TOME.
SESOXT-CHOLIC ACID v. Cholio acid.
SESOXT-CODEINE v. Codeini!.
SESOXT-CXrMINOlN v. Cumdioin.
SETTTEBO-ALBirUOSE v. Fboieibs.
DEXTEANE C.H,„05 (at 130°). [b]d = 223°.
A guiomy substance occurring in unripe beet-
root (Scheibler, J. T. C. 1875, 790). Formed
also in the lactic fermentation of sugar (Tieg-
hem, Jahres. d. Agriculturchemie, 1879, 544).
Amorphous ; v. sol. water, forming a sticky li-
quid. Insipid taste. Its cone, aqueous solution
is ppd. by lead subacetate, and gives with Feh-
ling's solution a light-blue sticky pp., no reduc-
tion taking place. Boiling dilute H2SO4 con-
verts it into glucose. EKO, gives oxalic acid
only. Iodine gives no colouration.
Animal dextrane O^HioOj. [a]o = 157°. Se-
creted by ScM^onewra larmginosa, a louse that
forms galls on elm trees. Amorphous. SI. sol.
cold, more sol. boiling, water, insol. alcohol and
ether. Fehling's solution gives a gelatinous
coagulum, without reduction. Iodine gives no
colour. Boiling dilute E^SO, gives a substance
that reduces Fehling's solution (L. Liebermann,
Ff. 40, 454).
SEXIRIK nCjjH^gO,,. Although this term
has been in use for a long time, and a correct
percentage composition stated for the body it
represents, it is ohly recently that its characters
have been more accurately defined, and a place
given to it among chemical compounds. Most
of tiie substances to which the term has hitherto
been given have many properties in common
with dextrin.'but it is evident that many of these
hold no relation to it, and many more of them
are impure conditions of it.
Occwtttnee.-^ia) Dextrin is said to be present
in the sap of plants and in most seeds. Tha
evidence of this is, however, altogether unsatis-
factory, other bodies possessing some of its pro-
perties being in most cases mistaken for* it. —
(6) It is a constituent of the juice of horse-flesh
(Limprioht, /. 1865, 673), and it is probable,
though not proved, that the body therein found
is true dextrin. — (c) Keiohardt {Ar. Ph. [3] 5,
502) states that the urine of diabetic patients,
under certain conditions, contains dextrin ; but
from his description it is impossible to say
whether the body he had under observation was
dextrin or not. — [d) Dried starch, heated to
210° and maintained at that temperature for
some time, yields a product known as British
gum or commercial dextrin. — (e) By moistening
the starch with dilute nitric acid, and drying
before heating, this conversion is expedited. —
(/) Digestion with dilute acids, inorganic and
organic, converts starch into dextrin and other
bodies. The commercial products from these
sources contain dextrin or dextrine, but there
are no analyses of them to show what dextrins
they contain. For the action of heat and acids
on starch see Biot and Persoz, A. Ch. [2] 52, 72 ;
Payen, ibid. 55, 225 ; 61, 372 ; 65, 235, 334 ;
Gu6rin-Varray, ib^d. 60, 68 ; Jaoquelain, ibid.
[3] 8, 225 ; B^ohamp, O. B. 51, 256 ; Anthon,
D.P.J. 218, 182; 219,, 457; 0 ' Sullivan, 0. /.
25, 581. — (g) When starch paste is submitted
to the action of the unorganised ferment found
in germinated grain, and known as diastase,
dextrins, among other substances, are produced.
It is one of the bodies derived from this source
upon which we shall look as a chemical entity,
and describe as dextrin ; and it is only in as far as
the bodies hitherto called dextrin, and obtained
from the various sources above mentioned, agree
in properties with those we shaU find this to
possess that we can consider them dextrin. — (h)
Dextrin is found in beer, and is probably present
in bread, being the product of the action of diastase
on starch. — (i) Cellulose is converted into dextrin
by the action of sulphuric acid (Branomot, A. Ch.
12, 172), but the identity of the body thus pro-
duced is not established. — (j) Dextrose is said
to be converted into dextrin (Musoulus, Bl. [2]
18, 66) by submitting the sulpho-glucosic acid
to the action of spirit containing 95 p.c. alcohol.
This, from its optical activity, is not pure dextrin. '
Preparation.— 100 grams of carefully purified
potato starch (any other starch would answer,
but this is most easily manipulated) are stirred
up with 200 c.c. of water at 55''-60°, and as soon
as the granules are thoroughly dispersed through
the liquid 400 to 500 c.c. of boiling water are
added with continual stirring. In this way an
almost transparent and perfectly homogeneous
paste is obtained. This is cooled to 62°, and a
solution containing, in 50 0.0., 1 to 1'5 grams
diastase,' or, its equivalent in cold malt-extract
added to it, and the mixture maintained at
60°-63° until the filtrate from a portion cooled
no longer gives a colouration with iodine, and it is
' It is impossible to state an exact quantity of the pre-
paration of diastase or of cold malt-extract, because the
activity of tlie extract from a definite quantity of malt,
and of the preparation of diastase, varies very consider-
ably. A few experimcn^jy will, however, be sufficient to
determine the quantity of either necessary to transform
starch paste into products having on optical activity
[a]j=l"?°.
DEXTRIN.
379
touod that the optical activity of the solid matter
in solution (v. Sacohammetby) is [a]] = 176'6°
(O'SuUivan, J. C. [2] 17, 125), 166-7° (Brown a.
Morris, ibid. 47, 527). I£ the diastase is fairly
active, and the proportion above given employed,
this point is reached in five minutes' digestion or
less ; but inasmuch as, if the diastase is not
very active, no further conversion to any extent
takes place in a moderate time, the digestion
may be continued for 15 or 30 minutes without
any injurious effect. The solution is then cooled
and filtered, to remove a slight turbidity due to
a little flocculent matter from the diastase and
impurity from the starch or undissolved, because
ungelatinised, starch. The filtrate is then quickly
boiled and evaporated, best under diminished
pressure in a vacuum vessel, to about 200 o.c,
and alcohol (S.G. -83) added until a precipitate
begins to form ; a little more alcohol is added,
and the mixture allowed to stand until the syrupy
layer collects at the bottom. The clear super-
natant liquid is decanted off, and the syrup
washed with alcohol. This is dextrin more or
less contaminated with maltose and a constituent
of the diastase ; the former can be completely,
but with difficulty, separated by repeatedly dis-
solving in water, and carefully precipitating with
alcohol in the least possible excess, until a
portion of the precipitate, dissolved in water,
no longer gives a reaction when boiled for three
or four minutes with Fehling's solution. The
diastase bodies are separated also with difficulty :
the precipitate, freed from maltose, is dissolved
in a little water and alcohol gradually added,
until 5 to 10 p.o. of the whole is precipitated,
pure dextrin remains in the supernatant liquid,
and is precipitated from it by strong alcohol. To
obtain it in the dry state the precipitate is
treated with absolute alcohol, which extracts
water from it, and renders it capable of being
rubbed down to a white hygroscopic powder.
The dextrin thus dried retains Alcohol with much
pertinacity, and if it be required to obtain a pre-
paration absolutely free from that body, the
powder must be dissolved in a little water, and
boiled in a vacuum vessel until all alcohol is
eliminated, and the solution reduced to a thick
syrup. It is then transferred, in small quanti-
ties at a time, to an evaporating dish, and, while
hot, placed under the beU glass of an air-pump
over sulphuric acid and the air pumped out. If
the syrup was sufficiently thick it swells up and
blows out from loss of water. When this cools
it becomes a porous, brittle, glassy mass, which
can be rubbed down to a white powder if allowed
to stand over sulphuric acid for a day or two, or
in a few hours if the temperature of the dish be
maintained by a steam coil in the air-pump re-
ceiver. Brown and Morris, acting on a suggestion
of Wiley (C. N. 46, 175), propose to remove the
lust traces of maltose by treating a solution of
the impure dextrin with a slight excess of a
solution containing equal weights of mercuric
cyanide and caustic soda until no further re-
duction takes place. This product would have
to be purified from the materials employed,
from the decomposition products, &o. ' This
CO aid probably be accomplished by neutralising
with hydrochloric acid, evaporating to a_ syrup
in a vacuum vessel, and submitting to dialysis,
precipitating the dextrin in the concentrated
solution with alcohol, and further purifying by
partial precipitation with some reagent until the
optical activity of the chief product becomes
constant. '
Properties. — Dextrin is uncry stallisable ; dried
as described above, it is a glassy, colourless
body, capable of being rubbed down to a white
powder. It is without marked taste, and is
colourless. Its solutions are neutral. It is easily
soluble in water, and solutions containing as
much as 80 p.c. of the body, although syrupy,
are thin-fluid. It is slightly soluble in dilute
spirit, but insoluble in spirit containing 60 p.o.
alcohol. It is not coloured by iodine. Exposed
to moist air, and then allowed to stand over
sulphuric acid, its weight becomes constant,
when it contains from 9*5 to 10 p.c. water. This
is almost completely lost in a vacuum over sul-
phuric acid, and completely in a current of dry
air at 100°. The quantity of water corresponds
to the formula n{C,JS.^0,„20B^), and the amount
of carbon and hydrogen yielded by the dry body
agree well with the formula Cj^H^gOio. It is not
precipitated by lime or baryta water, but it forms
compounds with those earths which are insoluble
in alcohol. It is precipitated by ammoniacal
lead acetate, but not by the neutral or basic salt
alone. Dilute sulphuric acid converts dextrin
into maltose, and thence into dextrose, according
to the equations Cj^H^gOig-i-OHj'^Oi^H^^O,, and
CijHjjO,, + 0H2 = 2CjH,208. The phases of this
reaction have as yet not been fully worked out.
Diastase converts it slowly into maltose. Nitric
acid converts dextrin into saccharic and oxalic
acids. With a mixture of nitric and sulphuric
acids it yields a nitrate, GsH,(N02)20,, dinitrate
according to B^champ. By dissolving dextrin
in acetic anhydride, and heating to 160°, tri-
acetyl dextrin is produced (Schutzenberger a.
Naudin, C. B. 68, 814), but these substitution pro-
ducts require further investigation. A solution of
10 grams dry dextrin in 100 c.o. — a vessel holding
exactly 100 grams water at 15-5— has a S.G. 1-0396,
and its apparent optical activity is [a]j==222,
= [a]u = 200-4. These are good working factors ;
but a careful and accurate determination of
them is yet required. Under the influence
of ordinary saccharomyces it is not converted
into alcohol (fermented) in a moderate time ; in
presence of active diastase and this organism it
ferments easily. Besides the dextrin here de-
scribed, there are other dextrins to be found '
amongst the products of the action of diastase
and of acids upon starch {v. Stabch), but experi-
menters with these bodies are not yet agreed as
to their number or properties. Most of the pro-
perties just described are common to all the
dextrins; but the distinguishing character of
the dextrin of which we write is the action of
diastase upon it. When a solution containing
dextrin and diastase, in the proportion of 1 of
the latter to 100 of the former, is digested at
60°-63° no more maltose is formed in the first
five minutes than in the second five, in propor-
tion to the amount of dextrin in solution, the
conversion being a very slow and gradual process.
It may be fairly said that the opinions of
Bondoneau (0. B. 81, 972, 1210) and those of
Musculus and Gruber {Bl. 30, 54) have been
shown to be untenable. The former describes
three dextrins with different optical activities
380
DEXTRIN.
and powers of reducing copper oxide ; the latter
mentions three not coloured by iodine, of different
optical activity, two having the same reducing
power, and the third a higher power. O'Sullivan
{CJ. 35, 770) isolated and described three, ftnd
indicated the existence of a fourth dextrin, all
possessing the same optical activity as that
given above, and being without reducing action
on alkaline copper solution. Brown and Heron
(0. J. 35, 696) and Brown and Morris {ib. 47, 527)
maintain the evidence of eight dextrins without
isolating any of them, but confirm O'Snllivan's
observations that all the dextrins have the same
optical activity qj = 222, and that they are with-
out action on alkaline copper solution. The
i3-dextrin-iii of O'Sullivan, and the final dextrin
of Brown and Morris, agree in properties ; it is
the dextrin described. All the dextrins are white,
glassy, friable bodies, v. sol. water, and insol.
strong alcohol. O'Sullivan characterises the
dextrins as follows : — a-dextrin, coloured by
iodine reddish-brown, unacted , upon, or but
slightly, by diastase at 69°- 70°; at 66°-67°,
17'4p.c., on transformed products, of maltose is
prpduced in four to ten minutes, there being no
increase in the next two hours if the diastase ia
not in excess and the temperature maintained ;
at 65°-66°, 34-5 p.c. maltose is formed ; at 63 °-64°,
51'2 P.O.; and below 62°, 67-8 p.c. This would
indicate the molecule of this dextrin to be at
least C„H,2gO„. 0-dextrm, not coloured by
iodine. jS-dextrin-i is not acted upon, or but
slightly, by diastase at 66° ; at 63°-64° it yields
in five or ten minutes 34*6 p.c. maltose ; at
61°-62° the same quantity is observed, and at
58°-59° there is no increase in the yield ; this
would indicate the formula CsjHjjOs,, for j3-dex-
trin-i, if the formula of ;3-dextrin-iii be taken as
C^f'B.ffi^ According to Brown and Morris (2.c.)
there are eight dextrins,beginningwithC,gsH,„Ogg,
each differing from the one below it by the group
CigHjoOjg.butthey do not appear to have prepared
any one of the bodies in a pure state. They deter-
mine the position in the series of an unknown
one of them by the amount of maltose that it is
capable of yielding when acted upon by diastase
at 60° (O. J. i1, 548). All the high dextrins are
acted upon in a fermenting solution, and yield
maltose, and thence alcohol, the lowest dextrin
being left. Although the researches referred to
herein have thrown much light on the nature
and character of the dextrin bodies, much still
remains to be done before we can cdusider our
knowledge complete.
EatmwMon. — In substances from which dex-
trin has not hitherto been isolated, and in which
its presence is suspected from the optical acti-
vity of their solution, or the nature of their
source, before any attempt at estimation is
made, it would be necessary to prove its presence
by eliminating the bodies with which it may be
accompanied by processes indicated above, and
comparing the properties of the body isolated
with those herein given for dextrin. The esti-
mation may then be effected after the manner
indicated below, attention being given to the
nature of the bodies with which it may be
accompanied. In products in which the presence
of dextrin is well established, viz. the various
commercial sugars obtained by the action of
acids on starch, inalt-^xtract, beer, and such
products, dextrin is estimated as follows : — In
the commercial starch sugars a known weight of
the sugar (15 g. or thereabouts is a suitable
quantity) is dissolved in a small quantity of
boiling water, the solution cooled and then made
up to 100 c.c. This is submitted to fermentation
with 0'5 g. yeast, and the fermentation pushed
as far as possible. The alcohol is eliminated
by distillation, the residue filtered and made up
to 100 cc. with the washings ; of this an optical
activity is taken and E determined (v. Sac-
CHAiiiuETBY) ; if the latter indicates more than
15 p.c. calculated on the solid matter unfer-
mented, the solution must again be submitted
to fermentation, and the amount of reducing
sugar further diminished ; if less, the reducing
body may be taken as maltose, and. the calcula-
tion made accordingly.
Exa/mple. — 15 g. glucose symp dissolved to
100 c.c, submitted to fermentation with 0'5 g.
yeast, yielded 100 cc. of residue of S.G. 1-0012
= about 3"038 g. solid matter per 100 c.c. 18-57 g.
of this solution yielded 0-087 g. CuO ; this corre-
sponds to -087 X -7256 ' = -0631 g. maltose, and
to a total amount of maltose in the 100 cc. of
l"»-12x-0631..3402g., or to -087 x -4535
1857
-0394 g. dextrose, giving a total amount of
dextrose in the 100 c.c. of
100-12 X -0394
18-57
= -2124g.
This is less than 15 p.c on the solid matter in
solution, hence the reduction found above ia
taken as maltose. The optical activity of the
solution was 26-5 divisions of a Soleil-Ventzke-
Scheibler saccharimeter ; this corresponds to
26-5 --34 X 8-02 ^2.143 dextrin, and as the soUd
11-56
matter was found to be 82-0 p.c. of the syrup the
dextrin is 17-4 p.c. of the solid matter. In
beer the estimation is made in the same way,
only, as a rule, in a beer of any age the
cupric oxide reduced may be calculated as mal-
tose without further consideration, a correction
of -0008 g. being subtracted from the weight of
CuO for every gram of beer taken for the reduc-
tion. In malt-extract the estimation is effected
in the same manner as described for sugar syrup
above, the procedure after fermentation being
the same as followed in the case of beer. Should
active diastase be present in the malt-extract,
as is usually the case in the best preparations,
the solution should be boiled before fermentation.
According to Wiley (C. N. 46, 175) dextriii can be
estimated in the starch products by eliminating
the reducing bodies by alkahne solution of mer-
cury dicyanide. He proceeds as follows : — The
mercury solution is made by dissolving 120 g.
HgCy, and 120 g. NaOH in water, and making
up to 1 litre. 1 g. of the sugar to be examined
is dissolved in 10 cc ; this is boiled for two or
three minutes with an excess of the mercury
solution, of which 25 c.c. will as a rule be found
sufficient. The solution is cooled, neutralised
vrith EOl, and the bulk made up to 50 c.c An
observation of the optical activity of this solu-
tion gives the dextrin. For example, the
optical activity of a solution, prepared as
described, and observed in a 200 mm. tube,
was found to bo 2-3 divisions of a S.Y.S.
- CuOxO'7S66=maltose corrCB^ODdtcg to CuO.
DICHEOlNS.
881
' Baooharimeter— 2-3 -4- 11-56 = 20 g. dextrin in
100 c.c, i.e. •! g. in 50 o.o. 1 g. sugar yields
•1 g. dextrin or 10 p.o. (Further on this subject
V. Sacchabimeibs.) If any of the higher dextrins
should be present the quantity could be approxi-
mately estimated by the action of malt-extract
at the various temperatures indicated above,
and the position and approximate quantity of
the dextrin inferred from the amount of maltose
formed in five to ten minutes. 0. O'S.
DEXTSO-. Compounds'beginning with this
prefix, indicating a right-handed rotatory effect
on light, are described under the remaining part
of the name ; e.^. dextro-tartaric acid under
Tabtabio acid.
DEXmONIC ACID «. Gluoonio acid.
SEXIBOSEv. SuoABS.
DI-. When this prefix is used in a numerical
sense it is entirely left out of account in deter-
mining the alphabetical position assigned to a
compound in this dictionary.
DIALTJEIC ACID C^H^NjO, i.e.
CO<^g;^Q>CH.OH. Tartrmyl-urea. Mol.
w. 144.
Formation. — 1. By passing HjS through a
boiling aqueous solution of alloxan (Liebig a.
Wohler, A. 26, 276).— 2. By treating alloxan
■with zinc and HCl. — 3. By dissolving uric acid
in dilute HNO, and adding ammonium sulphide.
4. By treating an aqueous solution of alloxan
with ammonium or {lotassium cyanide (Strecker,
A. 113, 49). — 5. By treating alloxantin with
sodium amalgam (Baeyer, A. 127, 12). — 6. By
treating di-bromo-barbiturio acid with HjS
(Baeyer, A. 130, 133).
Properties. — Needles, si. sol. water, acid to
litmus. Oxidised by moist air to alloxantin.
Combines with alloxan forming alloxantin.
Heated with glycerin at 100° it forms hydurilic
acid.
Salts. — NHjA' : sillty needles; converted
at 100° into blood -red murexide.— KA' (cf. Men-
Bchutkin, A. 182, 70). Urea dialurate
CONjH^C^HiNjO, : stellate crystals (Mulder, B.
6, 1010).
NH— C(OH)
^COH.
"NH— CO
Iso-tartronyl urea. Formed by the action of
bromine water on isobarbituric acid, amido-
nracil, or hydroxanthine (Behrend a. Eoosen,
5. 21, 1000). Prisms (containing 2aq). V. sol.
water. Stable towards oxidising agents. Is
converted by warming with urea and cone.
HjSOj into what is believed to be uric acid.
DIALYSIS. The separation of certain sub-
stances by liquid diffusion; v. Ditfusion and
Physicaii methods, vol. iv. p. 172.
DIAMOND V. Caebon, vol. i. pp. 686, 686,
687.
DIASTASE C 44-33, H 6-98, N 8-92, S 1-07,
O 32-91, ash 4-79. The substance that enables
malt to convert starch into dextrin and sugar.
Green barley malt is digested with dilute alcohol
(20 p.c.) for 24 hours ; the extract is ppd. with
24 vols, absolute alcohol, and the pp. washed
with alcohol and ether (O'SuUivan, O. J. 45, 2 ;
Lintner, J.pr. [2] 34, 386 ; 36, 481).'
Purificati<m.^Ca,nnot be purified by ppg.
Iso - dialnric acid CO'
<.
with basic lead acetate (L.) ; purified by repeated
solution in water and ppn. with alcohol ; the
ash can be reduced by dialysis to less than 5 p.o.'
consisting of calcium phosphate.
Properties. — Amorphous; has not been ob-
tained pure. Its action on starch is prevented
by strong acids or alkalis, by salts of Cn, Hg, and
Ag, by alum, and by Fe^Olj, but not by phenol.
Hydroxylamine, formic aldehyde, and nitrous
acid at 40° render diastase inactive (Loe\ir,J.pr.
[2] 37, 101). Presence of CO, accelerates the
power of diastase to eonvert starch into sugar
(Baswitz, B. 11, 1443). Above 63° the ferment-
ing power is weakened.
Betictions. — 1. Does not reduce Fehling's'
solution even after boiling with HCl. — 2. Does
not give a violet colour with CuSO, and KOH. —
3. Ppd. by boiling. — 4. HCl gives a pp., sol.
NaOH.— 6. HO Ac a pp. sol. excess. — 6. HgCl2a
pp. — 7. Basic lead acetate a pp. — 8. HOAc and
KjFeCys a pp.— 9. Millon's reagent gives albu-
men reaction. — 10. Warmed with fuming HOI a
violet colour. — 11. Guaiacum tincture mixed with
a little HjOj gives a blue colour.
Beferences. — Payen a. Persoz, A. Ch. [2] 53,
73; 56, 237; 60, 441; 61, 351; Gufirin-Varry,
A. Ch. 57, 108; 60, 22 ; 61, 22 ; Bouchardat,.4.
Ch. [3] 14, 61 ; Fankhauser, Bied. Centr. 1888,
205 ; Defresne, C. B. 89, 1070 ; Brasse, C. B.
100, 454 ; H. Muller, Ann. Agronom. 12, 481 ;
Bourquelot, C. B. 104, 576 ; Kjeldahl, O. J. 38,
502 ; Zulkowski a. Eenner, 0. J. 38, 661 ; B. C;
1879, 929 ; Sohartler, Ci C. 1887, 634 ; Huppe,
O. J: 44, 101 ; Schneider, O. J. 46, 1366 ; Herz^
field, B. C. 10, 203 ; Stutzer a. Isbert, S. 12, 72).
V. also FEimnNiATioti, Dexibin, Siabch, and
SUQABS.
Diastase of K6ji. Kdji is used in Japan to
make beer. It is fo^ed by steaming rice-grains
and leaving them till a fungus grows on them.
An aqueous infusion of this Edji acts somewhat
like malt-extract, for it inverts cane-sugar and
hydrates maltose and dextrin, and it liquefies
starch paste, forming first maltose and dextrin^
then glucose and dextrin (E. W. Atkinson, Pr,
31, 523 ; 32, 299). The diastase-like ferment is
obtained from the albuminous matters in the
rice through changes produced by the growth
of the fungus.
DIATESEBIC ACID v. Tebebic acid.
DIAIEBEBILENIC ACID v. Tebebilenio
ACID.
DIATEBFENYLIC ACID v. Tebfenylio Acn>.
DICHBOitNS. A name given by Brunner and
Chuit (B. 21, 249) to the fluorescent colouring
matters obtained in Liebermann's reaction by
treatment of phenols with cone. H2SO4 and
nitrous acid. They are obtained by the action
of H2SO4 saturated with nitrous acid on para-
nitrosophenols ; but only those polyhydrip
phenols having the hydroxyl-groups in the meta-
positions to one another yield dichroi'ns. The
dichroinsare divided into (a) -dichroins containing
the complex C|,.N:(0.0j)2, and (3)-diahroins with
the group C8.N<^q^08. The colouring matters
CigHisNO from phenol, 0,jH,.,NO„andOaeH2„NjO„
from resoroin, and CaHjiNOj from orcin belong
to the (o)-group, whilst the (;8)-group includes
C„H„N03 from orcin, azoresorcin, azoresorufiu,
and azoresorufin ether; the last three are re-
382
DICHEOtNS,
epectiyely (S)-rcsorcin-, dir(^)-resorcm-, and
tetra-(;3)-resorcin-dichroui (H. Brunner and
P. dhuit, B. 21, 2479).
Chroms. — Chroins are colouring matters re-
salting from the action of H^SO, containing ni-
trous acid on hitroso-phenola, 'which are analogous
to the qainoneozimes, and they appear to con-
tain the (0,),:N— 0— N:(Cj),.
Ozycuroins. — Oxychroius are bodies bearing
a similar relation to nitro-phenols as dichroins
do to nitroso-phenols. They are obtained in
most reactions along vith the dichroins during
the preparation of the latter. They are richer
in oxygen than dichroins and do not fluoresce.
SICHBOIsm. The property exhibited by
many doubly refracting crystals of showing dif-
ferent colours when examined in different direc-
tions.
SICHBOUATSS. Salts of the hypothetical
acid H^Cr^O, v. Chromium, acids of, p. 154, 157.
DICONIC ACID CJB.,„0,. [200°]. Formed
by heating citric acid with cone. HClA.q at 200°
(Hergt, J. pr. [2] 8, 372) ; aconitio acid seems to
be an intermediate body. Small crystals, v. spl.
water, alcohol, and ether. Beddens litmus.
Salts.— KjA" : deliquescent. — (NH,)»ft." :
[95°] ; deliquescent crystalline mass. — BaA"lf aq;
more sol. cold than hot water. — BaHjA. j. —
SrA"6aq.— 70aA"aq. — MgA"6aq: hard crystal-
line crusts, V. sol. water.— Fe{OH)sHA" (?).—
MnA"5aq: plates. — OoA"6aq: rose-coloured
monoclinio plates. — NiA."6aq. — ZnA"6aq: mo-
nocUnic plates. — ZnHjA"j7aq. — CuA"3aq :
bluish-green prisms. — SnA"Sn04aq: insoluble
PP-
Diethyl ether M^A.". Oil.
SISyMIim Di. At. w. 143 (exact value
doubtful). Mol. w. unknown. S.G. 6-544. S.H.
■04563 (Hillebiand, P. 158, 71). Melts above
Ce and La. In 1842 Mo^ander separated a new
metal from the mineral Cerite (P. 56, SOS) ; as
the metals Ce and La had already been found
in this mineral, the name didymium was given
to the new metal to suggest its close relationship
to lanthanum (SfSv/ios = two-fold). Becent inves-
tigation has succeeded in obtaining from certain
Di salts what seem to be two classes of com-
pounds distinguished by their absorption-spectra
and colour ; these compounds in all probability
are salts of two distinct elements (v. infra) ; the
name didymium is therefore a singularly happy
one. In the present state of knowledge of the
rarer elements it seems well to describe the body
regarded until recently as a single element, and
the compounds of this body.
Occi(/rrence. — As silicate in various Scandi-
navian and Siberian minerals, Cerite, OadoU-
ti/Ue, Orthite, &e., accompanying Ce and La.
PrepwraUon. — The mixed oxides of Ce, La,
and Di are separated from Cerite by treatment
with H2SO4, &c., as described under CEimiM (vol. i.
p. 723) ; Ce is then separated as basic nitrate
by one of the methods described under Cesium.
The solution of Di and La nitrates may then be
treated in different ways: Bunsen a. Jegel (P.
155, 377) recommend ppn. of the hydrated oxides
of Di and La by NH,Aq, solution in H^SOjAq,
evaporation, and crystallisation of the sulphates ;
the sulphates are then dried and powdered,
1 part is dissolved in small successive portions
in 6 parts water at 2°-3°, the solution-is heated
to c. 40°, when La^SSOj separates, the mother- .
liquor is slowly evaporated by standing in a
warm place, when rose-coloured rhombohedru
of DijSSO, separate ; thin violet plates generally
also form on the sides of the dish, these are a
mixture of the two sulphates, thoy are easily
distinguishable from the DijSSO^ crystals; the
rose-coloured crystals are picked out, and puri-
fied by re-crystallisation (Mosander, P. 56, 503,
or P. M. 28, 241). The crystals thus obtained
usually contain a little La^SSO, ; Hermann
{J.jpr.Si, 385) evaporates the solution of Di^SSO,
containing some La.^SSO, to dryness at about
18°-20°, adds a little cold water to the residue
which dissolves DijSSOj with very little La^SSO,,
evaporates to dryness at 18°-20°, treats with
cold water, &o., and repeats these operations so
long as there is any residue not quickly sol. in
a little cold water. To complete the separation,
Hermann (Z.c.) dissolves the DLjSSO^, which may
contain traces of La,^3S04, in water, divides the
solution into two parts, ppts. one part by NHjAq,
washes the pp. thoroughly^ mixes it while moist
with the other part of the solution, and allows
the whole to remain at a moderate temperature
for some days ; basic La sulphate thus dissolves
completely and basic Di sulphate separates ;
after a few days the crystals which separate
are collected, washed, dissolved in HjSO^Aq, and
again crystallised (v. also Erk, Z. [2] 7, 104).
Other methods for separating Di salts from
La salts are based on the relative solubilities of
the oxalates and nitrates of the two metals ;
V. Marignac, A. Ch. [3] 27, 226; Holzmann,
Zeitsch/r. fUr Chem. vind Pharm. 1862. 66a;
Zschiesohe, J. pr. 107, 65 ; Freriohs a. Smith,
A. 191, 331. Frerichs (B. 7, 798) describes a
method of separation founded on the reaction
between DiCl, and LaOCl, whereby DijO, and
LaCl, are produced.
According to Cleve (C. J. 43, 362) the DijSSO,
prepared as described may still contain gamarium
salts; samarium oxide is separated by long con-
tinued fractional ppn. with cold dUute NHgAq,
the earlier fractions are rich in samaria, the
later are chiefly didymia; by solution of the
later portions in HKO,Aq and repeated fractional
ppn. by dilute NH^Aq, didymia is at last ob-
tained free from samaria. (Cleve's paper con-
tains a description of a method for the approxi-
mate separation of the rare earths, which he
says is very convenient.)
The 01,3804 purified ^^ described is dissolved
in water, and NH,Aq is added in excess, the
ppd. hydrate is washed, and dissolved in HClAq,
the liquid is evaporated after addition of KH4CI,
and the residue is heated; nearly pure DiCl,
containing a little DiOCl is obtained. The DiCl,
may be reduced by heating with Kin a porcelain
tube ; on washing with water small particles of
Di are obtained (Marignac, A. Ch. [3] 38, 148) ;
the reduction is better effected by mixing with
NaCl, melting, and electrolysing (Hillebrand a.
Norton, P. 155, 633).
Properties and Beactions. — White metal,
malleable and ductile, harder than Ce. Oxidises
in air ; when finely divided it burns in a flame
with production of much light ; dissolves readily
in dilute HClAq, HNO,Aq, and HjS04Aq ; de-
composes cold water slowly and hot via.tex
rapidly.
DIDYMIUM.
883
Tlie atomfo weight of Di has been determined
(1) by analysing the sulphate (Marignao, A. Oh.
[3] 27, 231 ; Brk, Z. [2] 7, 106) ; (2) by analys-
ing the chloride (Marignao, A. Oh. [3] 38, 153) ;
(3) by transforming the oxide into sulphate, or
vice versd (Hermann, /. pr. 82, 387 ; Erk, Z.
[2] 7, 106 ; Ksohiesohe, J. pr. 107, 65 ; Cleve,
Bl. [2] 21, 246; 39, 289; O.J. 43, 362 ; Brau-
ner, O. J. 41, 68, and (later) W. A. B. 8, 141,
499) ; (4) by determining S.H. of Di, Hillebrand
a. Norton (P. 158, 71). The numbers obtained
for the atomic weight of Di vary from o. 145 to
o. 142 ; Oleve thinks that the value 142-124 iz
■0326 may be accepted; Brauner thinks that
Di = 145-2 to 145-4 (O. J. 43, 288).
Separation of didymvum into different con-
stituents.— ^La-NH, nitrate is more sol. HNO^Aq
than Di-NHj nitrate; when a long process of
fractional crystallisation is conducted with a
mixture of these salts, the La salt may be com-
pletely removed, and at the same time the Di
salt separated, according to v. Welsbach, into
two perfectly distinct compounds (Sitz. W. 92
[2nd part], 317). A large quantity of the mixed
nitrates of La and Di obtained from cerite after
separating basic Ce nitrate (v. vol. i. p. 723) is
mixed with the necessary quantity of NH^NOg,
about ^th part cone. HNO,Aq is added, and the
liquid is evaporated until small crystals appear
on the surface, a little water is added, and crys-
tallisation is allowed to proceed for about 24
hours ; the crystals are drained and washed with
a little HNOjAq which is added to the mother-
liquor; the inother-Uquor is evaporated and
crystallised ; the liquor from this is again eva-
porated, and so on until 6-8 fractions have been
obtained ; these fractions are then systemati-
cally refractionated by crystallisation from
HNOjAq several thousand times. Two nitrates
are finally obtained, one forming a pale-green
solution, the other forming a rose-coloured solu-
tion ; these solutions give difierent emission-
and absorption-spectra, the sum of the two
spectra is the same as the spectrum of didymium
nitrate. From each solution salts are obtain-
able, one series is green, the other is rose-co-
loured ; by decomposing the green nitrate by
heat a brownish-black oxide is obtained, and by
decomposing the rose-red nitrate a blue-grey
oxide is produced ; analyses of the oxides and
salts are not given in the original paper. For
the element which forms green salts v. Wels-
bach proposes the name praseodymium, and for
that which gives rose-coloured salts he proposes
the name neodymium ; he assigns the atomic
weight 143-6 to praseodymium, and the atomic
weight 140-8 to neodymium, the oxides having
the composition M2O3. When a salt of praseo-
dymium is mixed in certain proportions with
a salt of neodymium, the spectrum of the mix-
ture is the same as that of didymium.
Beequerel (C. B. 104, 1691; 777) has ex-
amined the absorption-spectra of Di salts, and
concludes that these salts are mixtures of at
least two substances. Brauner (O. J. 43, 281)
got indications of the complex nature of Di by
careful fractional ppn. of Di3N05 solution by
NHjAq. Crookes {N:3i, 266) did not succeed
in separating v. Welsbach's praseo- and neo-
dymium from didymium ; he thinks that these
names may represent two different groups of
molecules into which what is called didymium
is separated by one particular method of frac-
tionation.
Ohemicalrelations of Didymium. — If the body
called didymium is an elementary substamse, it
must be placed in Group V. with'N, P,...and Bi.
Di forms the oxide DijOj, and probably 01,0,, but
only one class of salts Di23X where X = S04,2NO|,
(fee. ; one class of haloid salts is known, DiX„
where X = F, 01, Br ; the oxyohlorlde DiOCl has
been prepared. Di is more closely analogous to
Bi than to any other element of Group Y.
Bidymium arsenate v. vol. i. p. 308.
Didymium bromide DiBr,.6HjO. 'Violet,
deliquescent crystals; S.G. 2-81 (Cleve, Bl.
[2] 89, 289); obtained by dissolving Di^O, in
HBrAq and evaporating over HjBO,. Forms
double salts (Frerichs a. Smith, A. 191, 342) :
2DiBr,.3KiBrj.l8H,0 ; 2DiBr,.3ZnBr,.36HjO
(24HaO according to Cleve, Bl. [2] 39, 289), very
deliquescent ; DiBr,.AuBr,.10H,O (Cleve, Z.C.).
Didymium chloride DiCl,.6H20. Violet, de-
liquescent, monoclinic crystals; very soluble in
water or alcohol ; S.G. 2-286 (Cleve, l.e.). Ob-
tained by dissolving Di^O, in EClAq, evapora-
ting, and crystallising ; when the solution is
evaporated to dryness after addition of NH,C1
and the residue is heated, or when the residue
obtained by evaporating Di20, in HClAq to dry-
ness is heated in a stream of HCl, nearly pure
DiClg, containing a little DiOCl, is obtained.
Double salts.— 2Di01,.8AuCl3.2H20: bril-
liant yellow deliquescei;t plates, by evaporating
a solution of the mixed chlorides (Frerichs a.
Smith, A. 191, 340); 2DiCl,.9HgClj.24HjO ;
2DiCl,.3Pta4.24H,0 (F. a. S.) ;
DiCl3.PtCl4.10|H:jO, deliquescent prisms ; S.G.
2-689 (Cleve, Bl. [2] 39, 289) ; DiCl,.SnCl,.10!H,O
(Cleve, Bl. [2] 31, 196).
Didyminm fluoride 2DiF,.H20; reddish pp.
by adding EFAq to solution of Di acetate
(Cleve). According to Frerichs a. Smith (A.
191, 343) the pp. formed by adding HFAq to
Dij3S04Aq is 2DiF,.3HF ; this is denied by Cleve
{B. 11, 910).
Double salts. — Obtained by treating Di,0,
with KP.HP (Brauner, C. J. 41, 68) ;
2DiF5.3HF.H2O; 3DiF,.3KF.HsO ; 4DiF,.3KF.
Didymium hydroxides v. Distmium, oxides
AND BTDIUTED OXIDES OF.
Didymium iodide. Not isolated. Frerichs a.
Smith (A. 191, 343) obtained the double salt
2DiI,.3Znl2.24H20 as deliquescent yellow plates.
Didymium, oxides aad hydrated oxides of.
Di forms the oxide Di^O, ; another oxide Di,0,,
and another intermediate between these, Di^O. or
Di,0„ probably exists. The hydrated oxide
Di20s.3H20 seems not to have been obtained in
a state of purity ; Di20s.3HjO has probably been
isolated. The oxides and hydrated oxides of Di
are basic; the higher oxides react with acids
as peroxides, forming salts of the series Di^SX
(X = N03,^«,&c.).
DiDYMinu OXIDE Di^O,. S.G. 7*18 (Clever Bl.
[2] 39, 289) ; S.H. -081 (Nilson a. Pettersson, B.
13, 1459). Obtained by ppg.DiCl,Aq by EOHAq,
and strongly heating the hydrated oxide thus
formed ; also by strongly heating Di(NO,)„
Di,(C,OJ„ or Di,(CO,),; it is advantageous to
884
DIDYMIUM.
complete the decomposition in a stream of H to
deoxidise any higher oxide formed. Greyish-
blue solid (Cleve, Bl.[2] 39, 289) ; white without
any blue tinge according to Hermann {I. pr. 82,
885). Unchanged by heating in H; probably
combines with 0 when heated in that gas {v.
infra). Emits white light when very strongly
heated, the lines in the spectrum of the light
emitted are the same as the dark lines in the
absorption-spectrum of dilute Di salt solutions.
Dissolves in acids to form salts BLSX where
SO
' '— Insoluble in water, but in
X = NO„
&o.
hot water foritns a hydrate probably DlfiySHJi).
In ordinary air forms DijSCOj ; decomposes hot
solutions of NHj salts, evolving NH,.
HVDnATED DIDYMIUM OXIDE 7pi.jO3.3H.jO
(=Di(0H)3). The pp. obtained by adding
EOHAq or NaOHAq to solutions of Di salts is
gelatinous, pale rose-red, insoluble in excess of
the pptnt. ; it always contains a little carbonate.
NHjAq ppts. basic salts from solutions of Di
salts. Thomsen gives the heat of neutralisation
of didymium hydrate [Di-0».a;ffO,3H^SO'Aq]
= 77,160 {Th. 1, 375).
Oxides or didymium other than DljO,. Ac-
cording to Frerichs a. Smith {A. 191, 344), Di^Oj
prepared by gently heating Di(N03)3 absorbs 0
when heated in that gas, forming a chestnut-
coloured powder approximating to the composi-
tion Di^Oj. The same chemists also obtained
DijOj by heating l>i.,{C.JOf), in a stream of 0.
Hermann {J.pr. 82, 385), by heating Di^Oj inO,
obtained a product with only c. -8 p.c. more 0
than DljO, ; Cleve (B. 11, 910) states positively
that Di^Og cannot be obtained as described by
Frerichs a. Smith. Brauner (C. J. 41, 68) says
that the oxide obtained by carefully heating
basic Di nitrate to dull redness in a stream of 0
has the composition Difl^; he describes this
oxide as an amorphous chocolate-brown powder,
soluble in dilute HNOjAq or dilute HjSOjAq
without evolution of gas, but soluble in more
cone, acids with evolution of 0, insoluble in
EFAq, depomposed when strongly heated with
production of 0 ; reduced in H at low red heat ;
S.G. at 13° = 5-.368; reacts with acids to form
salts Di.j3X, and must therefore be classed as a
basic peroxide. Brauner (I.e.) ppd. a solution of
DiSNOj, containing H^O,;, by dilute KOHAq and
dried in vacuo, he thus obtained a light red
powder to which he assigns the formula
DijOs.3H.p. It is still uncertain whether Brau-
ner's peroxide can be obtained from a specimen
of DiSNO, perfectly free from samarium.
Sidyminm. oxyhaloid compounds of. The
only one of these compounds definitely knovra
is the oxychloride, DiOCl; it is a greyish powder,
S.G. 5-751 (Cleve, Bl. [2] 39, 151), obtained by
heating DiCIg.CH^O and treating the residue with
water (Marignao, A. Ch. [3] 38, 148), or, accord-
ing to Frerichs a. Smith {A. 191, 341), by heating
DijOa in 01 at 200°.
Didymium ozysnlphide. Marignao {A. Ch.
[3] 38, 148) describes a greyish powder, insoluble
in water, obtained by heating DioO, with S and
NaOH ; he gives it the formula DijOjS.
Bidyjninm, salts of. Di forms one class of
salts, Dij3X, where 'S. = '^0„^* . fPO« &e. ;
many of them are soluble in water, forming rose-
red liquids ; several double salts, but yeiy few
basic salts, are known. The chief salts are
borate, bromate, carbonate, chlorate, iodate,
molybdate, nitrate,'oxalate, phosphates, selenace
aiid selenite, sulphate and sulphite, tungstate,
vanadate; v. Gabbonates, Niiiiaies, Sulphates,
&o.
Didymium sulphido Di.jSji A brownish-
green powder ; obtained by heating Di^O, in H
charged with CSj vapour. Decomposed easily
by acids with evolution of HjS ; decomposed by
heat to Di^O, and basic Di sulphates (Marignac,
A. Ch. [3] 38, 148 ; Frerichs a. Smith, A. 191,
345).
Didymium snlphocyanide v. Sulphocyanides
under Cyanides, p. 350. M. M. P. M.
DIFFUSION. The mixing or mutual inter-
penetration, by reason of the movements of the
minute particles of the fluids, of gases or liquids
which do not chemically interact, is called dif-
fusion, whether the fluids are in immediate con-
tact or are separated by porous partitions. When
a liquid passes through a membrane into another
liquid the process is generally . called osmotic
diffusion or simply osmose ; when the difEusion
of a liquid is accompanied by a separation,
partial or complete, into two or inore chemically
different bodies, the process is generally known
as dialysis. Substances which when in solution
pass freely through it porous membrane, or
readily diffuse into another liquid in contact
with them, are generally called crystalloids,
while those substances, solutions of which do
not diffuse, or diffuse very slowly, ave usually
called colloids. For an account of diffusion and
the applications of this process to chemical
questions v. Fhysicaii methods, vol. iv. p. 172.
M. M. P. M.
DIGITAIIH 0 58-2 p.c; H 37 p.c.
S (cold 90 p.c. alcohol) 8i ; (boiling 90 p.c. al-
cohol) 17. Occurs in the leaves of the common
foxglove (Digitalis purpurea). It may be ex-
tracted from the leaves by dilute (50 p.c.) alcohol ;
the solution treated with basic lead acetate, and
the flUrate, freed from excess of lead by
Na.jCO„ ppd. by tannin. The digitalin tannate
is then decomposed by lead oxide and the
liberated digitalin crystallised fi-om alcohol
(Lefert, J. Ph. [5] 6, 424; cf. Nativelle, /. Ph.
[4] 9, 255; 20, 81; Ph. [3] 2, 865; Le Boyer,
Bibl. Uniu. 26, 102 ; Lancelot, A. 12, 251 ;
Trommsdorff, A. 24, 240 ; Ar. Ph. 10, 113 ;
HomoUe, J. Ph. [3] 7, 57 ; O. Henry, J. Ph. [3]
7, 460 ; HomoUe a. Quevenne, Mimoires sur la
Digitaline, Paris, 1851 ; Bipert. Pharm. [3] 9, 2 ;
Walz, Jahrb. pr. Pharm. 14, 20 ; 21, 29 ; 24, 80 ;
26, 296 ; Oerh. 4, 286 ; N. Jahrb. Pharm. 8, 332 ;
9, 802 ; 10, 319 ; J. 1847, 645 ; 1851, 567 ; 1852,
679; 1853, 568; 1857, 520; 1858, 528; Delffs,
N. Jahrb. Pharm. 9, 26 ; J. 1858, 528 ; Koss-
mann, J. Ph. [3] 38, 5 ; [4] 20, 427 ; C. J. 28,
650 ; Fluckiger, N. Jahrb. Pharm. 39, 129 ; 0. C.
1873, 371; Goerz, J. 1873, 815; Schmiedeberg,
Ph. [3] 5, 741 ; Morin, J. Ph. [3] 7, 294).
Properties. — Slender needles grouped around
a common axis (Nativelle) or small minute plates
(Fluckiger). Insol. water and dilute alkali, v. si.
sol. ether, v. sol. chloroform, chloroform-alcohol,'
and acetic acid. Hydrochloric acid dissolves it,
forming a yellowish solution, slowly becoming
DISSOCIATION.
386
emorald-gieen. Cono. HjSO, and H3PO1 also give
green colours. Digitalin lias no smell but a bitter
taate. It is poisonous, acting on the heart. Split
up by boiling dilute acids into glucose, digitaliretin
(0. 66 p.o. ; H. 4-6 p.o.), and other bodies (Koss-
mann). Treatment with H^SO, (1 pt.) and alco-
hol (1 pt.) containing a few drops of aqueous
Pe^Cl, gives a greenish-blue solution (Lafon, Bl.
[3] 44, 18). Digitalin, being a glliooside, colours
a hot mixture of bile and H^SO, red (Petten-
kofer's reaction ; ef. Brunner, B. 6, 96).
Digitalein 0 53-2 ; H 8-1 p.o. An amorph-
ous substance occurring in the leaves of Digitalis
purpv/rea and D. lutea. V. sol. water and cold
alcohol, si. sol. chloroform, insol. ether. Fpd.
from its aqueous solution by tannin or lead sub-
acetate. Split up by dilute acids into glucose
and digitaliretin. Narcotic poison.
Digitin (CjHjOj)^? Occurs in foxglove
leaves. Stellate groups of needles, insol. water,
chloroform, and benzene, v. sol. ether and al-
kaUs (Goerz, J. 1873, 814).
Sigitoniu C 53*4 p.c. ; H 7'5 p.o. A white
amorphous substance occurring in foxgloves.
Besembles saponin and melanthin. Y. sol.
water, forming a solution that froths on
shaking. Ppd. from its aqueous solution by
alcohol, baryta-water, or lead subacetate. Gives
a red colour when boiling with dilute acids
(Greenish, Ph. [3] 10, 909 ; 1018).
Bigitozin C 63-6 p.o. ; H 8-1 p.o. Occurs in
the leaves of the foxglove. Needles or tables,
insol. water and benzene, si. sol. ether, v. sol.
alcohol and chloroform. Boiling dilute acids
convert it into amorphous soluble toxiresin.
Both digitoxin and toxiresin are very poisonous.
Accordmg to Kopp digitoxin is eight times as
poisonous as digitalin.
OILITTBIC ACID v. Niteo-baebitdbio aoid.
DHL OIL. S.G. -9. (0.190°). The volatile
oil of Apium (or Anethum) graveolens. It con-
tains carvene and oarvol (Wallach, A. 227, 292;
cf. Nietzki, Ar. Ph. [3] 4, 317 ; Gladstone, O. J.
17,1; 25,1).
DIMOKPHISMandTEIMOEPHISM. These
terms are used to denote the existence of the
same chemical substance, elementary or com-
pound, in different crystalline forms. The two
kinds of crystals of u dimorphous body, or the
three kinds of crystals of a trimorphous body,
may belong to different systeins, e.g. carbon orys-
tallises in the regular system as diamond and in
hexagonal forms as graphite ; nickel sulphate
crystallises in trimetrio prisms, in dimetric octa-
hfidra, and in monocUnio prisms ; or the different
crystals of the same body may belong to the
same system, and yet so differ in their corre-
sponding angles that they cannot bef reduoedto
the same form ; mono-sodium phosphate, for in-
■'stance, NaH2P04.a!HjO, crystallises in two differ-
ent trimetrio forma. Di- and tri- morphism is
usually accompanied by differences of S.G.,
colour, hardness, or other properties (v. Cbtstal-
lisauon and Isomobphism). M. M. P. M.
DIOSMIN C 53 p.o. ; H 6-1 p.c. [243°].
Ocowrrmce. — ^In the leaves of Bwrosma ere-
nata and hetuUna (Cape of Good Hope).
Preparaiiow.— The leaves are first extracted
with petroleum to remove the essential oils to-
gether with chlorophyll, a wax and a resin ; then
they are extracted with cold, and finally with
Voi. n.
hot, alcohol (80-85 p.o.). The diosmin is obtained
by heating with ammonium carbonate, and
finally washing with alcohol and ether (P. Spica,
a. 18, 1).
Properties. — White or yellowish- white crys-
tals, insol. most solvents, but sol. hot alcohol
(80-85 p.c). In composition it ig practically
identical with hesperidin (Patem6 a. Briosi, Q.
6, 169). Beduces Fehling's solution. Dissolves
in concentrated acids and alkalis, but is reppd.
on neutralisation. Heated with conoentrated
mineral acid it is decomposed into a glucose and
an orange-yellow crystalline substance [145°],
Shimoyama (Arehvo der Pharm. 1887) considers
the similar glucoside hesperidin to be present
in the leaves of various species of the Barosma.
DIOSPHENOl 0,„H,30j. [82°]. (c. 220°).
The stearoptene in oil from buohu leaves (Spica,
Gf. 15, 195 ; Shimoyana, Ar. Ph. [3] 26, 403). .
Monoclinio crystals (by sublimation) ; v. sol.
alcohol, si. sol. ether, insol. water. Smells like
camphor. FeCl, gives a green colour.
Reactions.— 1. Alcoholic KOH partly con-
verts it into diolio aoid CggH^Ojaq, which
forms the following salts : BaA', 5aq. S. I'f at
17-5°; 5 at 100°.— AgA'.— 2. Beductionin alco-
holic solution by sodium a/malgam forms C„H,,0,
[159°].— 3. Bromine gives 0,„H„BrjOj [43°].
Methyl derivative 0,„H,5MeOj. (234°).
S.G. ^ -985. From diosphenol, EOH, and Mel.
Ethyl derivative CjoHijEtOj. (271°).
S.G. i5 •967.
Acetyl derivative C,oH,5AoOj. (270°).
S.G. 22 -1032.
DIFPEL'S OIL. An oil obtained by rectify-
ing the oUy product of the destructive distillation
of bones or other animal matter. Becommended.
as a medicine by Dippel, an apothecary of the
seventeenth century ; , v. Bone-oil, vol. i. p. 522.
SISACBTL V. AoBoidEsiN.
DISPOLINE C„H„N. (282°-304°). An al-
kaloid homologons with quinoline found among
the products obtained by distilling 'oinchonine
with potash (Greviile-Williams, Laboratory, p.
109; .^. 1867,428). Oil.— B'^H^PtCl,. Not de-
composed by boiling water (De Coninck, Bl. [2]
40, 271).
DISSOCIAHON. A term proposed by Devillo
for the purpose of particularising a certain class
of reactions chiefly studied by himself and by
those whom he inspired.
Many facts now studied by the method of the
theory of dissociation have been known from early
days. The observations of Gay-Lussac on the
decomposition of chalk by heat, and of Avogadro
in 1811, and Ampere in 1814, on the abnormal
vapour densities of gases may be me;ntioned. The
starting-point of the modern doctrine is Grove's
Bakerian Lecture (T. 1847), in which the decom-
position of gases by heat,, and especially the de-
composition of water by fused platinum, is an-
nounced and explained. The following extracts
■mH show that the theory of the decomposition of
water was correctly stated by_ Grove, though the
terms in which he expresses it are now obsolete.
After describing the action of a hot platinum wire
on dry and wet carbonic oxide respectively, he
continues : —
■ I tbonght mnch upon this erperlment ; it appeared to
me ultimately that the ignited platinum had no specific
effect in producing either oomposition ordecompositionot
C 0
383
DISSOCIATION.
water, but tliat it simply rendered the ohemlcal eqnillbrinm
unstable, and that the gases then restored themselYoa to a
stable equilibrium according to the ciroumstances in which
they werQ placed with regard to surrounding affinities ;
that if the state of mixed oxygen and hydrogen gas were,
at a certain temperature, more .stable than that of water,
ignited platinum wire would decompose water as it does
ammonia.* ' It now appeared to me that it was possible to
effect the decomposition of water by Ignited platinum ;
that, supposing the atmosphere of steam in the immediate
vicinity of ignited platinum were decomposed, or the affi-
nities of its constituents loosened, if there were any means
of suddenly remoying this atmosphere I might get the
mixed gases ; pr secondly, if, as appeared by the last two
experiments, quantity had any influence, that it might be
poisible so to diride the mixed gases by a quantity of neu-
tral ingredient as to obtain them by subsequent separation
'(or as it were filtration) from the neutral substance. Both
these were realised."
He then relates how on heating platinum in
steam he got a small bubble of gas, which deto-
nated when all was cold ; and then says : —
*The experiment was then repeated, continuing the
ignition for a longer time, but the gas could not be in-
creased beyond a very limited quantity ; indeed, it was
not to be expected, as, supposing it to be a mixed gas, re-
combination of the excess would have taken place.*
The matter was taken up by Deyille in 1857,
who repeated Grove's experiments on a large
scale. Advantage was taken of an old observa-
tion of Begnault concerning the action of molten
silver on steam, and an equivalent method, in
which silver is replaced by fused litharge, was
described.
This ia the first of the many ingenious
methods invented by DevUle for the study of
dissociation-phenomena, and to him and his
pupils we owe much of our knowledge on the
subject. The appended bibliography (v. end of
this article) will indicate the further history of
the matter, as well as the more important
memoirs which have appeared on the subject.
Before defining the meaning of the term
dissocia1A(m it will be well to become in some
measure acquainted with the simpler facts and
arguments of the subject. Let ab be a tube
n.adQ of some material capable of resisting a
high temperature, such as glazed porcelain. Let
0 be a porous septum, e.g. a plate of porous
earthenware, fitted into the tube ab, so as to
be air-tight in the ordinary signification of the
term. Let there be means of placing the end b
of the tube in connexion with an air-pump and
gas-knalysis apparatus. The end a can be
closed by a non-porous stopper, and the tube is
to be so placed that it can be raised to any
desired temperature. The space oa can be
flUed with any gas or vapour, and the stopper
at a famished with such arrangements as to
allow the pressure of the vapour in oa to be
kept constant, whatever the temperature may
h«. Though' such a combination oi appari^ns
as this has never been put together, and though
it would be exceedingly inconvenient in prac-
tice, it is easy to understand, and will serve to
establish the main principles of dissociation.
The part of the tube o a is supposed to be
filled with saturated water- vapour, and is placed
on the heating apparatus, b c is kept vacuous,
or as nearly so as possible, by means of the air-
pump. In now studying the changes produced
in the water- vapour by the action of heat, let us
direct our attention solely to the part of the
tube 0 A. Then we know that, as the tempera-
ture increases from 100°, the dry steam inoA
will expand at almost exactly the same rate as a
permanent gas. In fact, if we made two air-
thermometers at constant pressure, and filled
one with dry air and one with unsaturated
steam, they would keep together approximately
tm a very high temperature is attained —say, up
to a red heat. After that we should observe
that the expansion of the steam becomes greater
than the expansion of air, and continues tft
increase, at all events up to the highest-tem-
perature we can reach experimentally. If we
replaced the steam by the vapour of acetic acid
the same phenomena would be observed, except
that we should finally be able to reach a point
where the coefficient of expansion of the acetic
acid vapour attained a maximum ; and it would
decrease from that point till it again became
the same as for air. The apparatus with the
porous plate will enable us to give an explana-
tion of the change in the coefficient of expansion
of dry steam. We know that when we mix two
volumes of hydrogen and one volume of oxygen
and keep the mixture at a temperature a little
over 100°, and then explode the gases by means
of an electric spark, so that they may form
water-vapour, and finally allow the.temperature
to become the same after explosion as it was
before explosion, then the three volumes will
become reduced to two volumes. In other words,
oxygen and hydrogen when combined together
only occupy two-thirds of the space they occupy
before combination.
Now, suppose that we heat the water-vapour,
and let us assume that the heating in some way
undoes the combination of the hydrogen and
oxygen, so that we no longer have pure water-
vapour, but a mixture of water- vapour, oxygen,
and hydrogen. If we further assume that the
ratio of the weight of the uncombined gases to
the weight of the steam increases as &e tem-
perature rises, we shall have a hypothetical
explanation of the change in the coefficient of
expansion. This hypo'thetical explanation may
be converted into a real explanation by experi-
ments performed with the apparatus described.
The raU of diffusion of difierent gases through
porous septa is very nearly inversely proper
tional to the square roots of the densities of the
gases. Hydrogen, therefore, passes through
porous septa four thnes as fast as oxygen and
three times as fast as steam. If, therefore, the
steam in the part of the tube a c be really de-
composed, we shall be able to detect the decom-
position by means of an analysis of the gases
diffused into the part b c. In order to make
the proof complete we must still show that no
other change takes place in the steam in a o ; this
would be very difficult lio do directly, especially
DISSOCIATION.
887
for steam which only decomposes at very high
temperatures, and therefore we must adopt a
rather different method. If we can show that
the change in the ooeffloient of expansion is
proportional to the amount of steam decomposed
at aU temperatures, then we can deduce that
the most important part of the change at all
events is to be traced to the decomposition, or,
as we shall say for the future, to the dissociation,
of the steam. This may be done by means of
our apparatus. Since the pressure in ao is
kept constant, the ' partial pressure ' produced
by the hydrogen and oxygen wiU be proportional
to the ratio of the weights of the uncombined
gases to the weight of steam per unit volume.
We know from experiment that the weights of
gases diffused per unit time, under otherwise con-
stant conditions, are proportional to the pres-
sures, within the limit that the pressure is above
some very small value depending on the kind of
gas and the size of the pores in the septum.
In all ordinary experiments the pressure is well
above the hmit. In order to simplify matters
we will arrange our furnace so as to keep b a at
the same temperature as ac, and let the air-
pump work so fast that, however much gas
comes through the plate, the vacuum is not
perceptibly impaired. For a reason to be given
further on, we will also aUow the gas coming
from BO to cool slowly, so that the hydrogen
and oxygen may reoombine. This will leave us
with a mixture of water-vapour and hydrogen
in our analysis apparatus. We have therefore
to keep our diffusion-tube at different constant
temperatures, allow the diffusion to go on slowly,
and measure the amounts of, hydrogen coming
through per unit time. From what has been
said, tiiese quantities will be proportional to the
dissociation at the temperature considered ; and
we have only to compare them with the oo-
ef&cients of expansion at those temperatures to
test our theory.
In no particular case does the evidence in
favour of the hypothesis stated above amount
to a complete demonstration. Thus in the case
of bodies like sal-ammoniac, which decompose
into substances chemically different from them-
selves, and therefore recognisable by chemical
methods, no experiments have been made to
show that the abnormal vaponi density is efiy
tirely accounted for by the dissociation. Again,
in the case of substances like nitrogen tetroxide
and acetic acid^ where the vapour-density is a
function of the temperature, experiments have
indeed shown that the quantities of heat absorbed
at different temperatures, less the quantities of
heat required to raise similar supposed less de-
composable gases through the same range, are
proportional to the rate at which the coefScient
of expansion deviates from the normal. Unfortu-
nately, in both these cases (the only ones specially
studied as to this point) we have no chemical
means of testing whether the supposed molecular
decomposition takes place or not. In fact, some
chemists consider it does not, but that we have
in these cases merely a change comparable with
that from the liquid to the gaseous state, and
which does not take place at a definite tem-
perature, but goes on gradually even though
the liquid as such may have disappeared
tv. Berthelot a. Ogier, A. Ch. [5] 36, 382). In
other words, these chemists are inclined to at-
tribute the change which takes place in the co-
efBeient of expansion merely to the molecules
of the gas increasing their mean distance from
each other faster in these oases than in the
standard oases. This view, however, woald lead
to a very serious modification of all our views
as to the physical signification of the gaseous
state. Avogadro's law would have to be aban-
doned amongst other things. On the other hand,
if we consider that nitrogen tetroxide and acetic '
acid vapour suffer molecular decomposition,
then we must allow that all other gases which
are formed from their elements, with condensa-
tion— like nitrous oxide, for instance — may also
undergo a molecular decomposition, since their
specific heats have smaU positive temperature-
ooeflScients (Eeguault). There is nothing sur-
prising in this, in fact it is in complete accord-
ance with the views of Olausius and Williamson
and physicists generally on the meaning of the
deflmte composition of gases. Eamsay and
Young {G. J. 49, 790) have shown that the
specific gravity of acetic acid vapour decreases
as temperature rises, whether the pressure be
large or small, and that the specific gravity also
decreases as pressure falls, whether the tem-
perature be high or low, but that the specific
gravity of a normal) vapour, such as that of
alcohol or ether, increases as temperature falls
until a limit is reached, after which the specific
gravity remains unchanged.
The hypothesis of dissociation sketched above
will therefore be adopted in what follows, for
not only is it in complete harmony with eyery
experimental fact observed, but it serves to co-
ordinate and bring into the same field of view a
very great number of experimental results, at first
sight very unlike each other and inexplioabla
separately. It will be noticed that we have aa
yet said nothing as to the mechanism by which
dissociation takes place ; this is a very obscure
subject, and indeed very often seems to depend,
amongst other things, on the form and material
of the containing vessel (Menschutkin a.Eanona-
low).
The effect of porous surfaces, however, pre-
sents little difSculty to the kinetic, and still le'ss
to the vortex-ring, theory of gases. Practically
it may be taken to mean that an experimenter
attempting to reproduce any of the experiments
described below will most probably fail to repro-
duce the numerical results unless he carefully
copies the original experimenter's apparatus.
Particular instances wUl be found in their proper
places.
There is no reason to suppose that dissocia-
tion is limited to gases, or that a rise of tempe-
rature is the only physical condition capable of
bringing it about. It is a matter of common
experience that chalk, when heated, decomposes
into quicklime and carbonic acid; and if the
operation be conducted in a closed chamber so
that the carbonic acid cannot escape, it is found
that the decomposition of the chalk is never com-
plete, and that recombination occurs, to a certain
extent, when the temperature falls. There are
many other substances which behave like chalk
as far as their decomposition by heat is con-
cerned ; that is, their degree of decomposition
in closed vessels is almost entirely a function of
002
388
DISSOCIATION.
the temperature, and is reversible. ' The consti-
tation of solutions of many salts in water or in
other solvents also appears to be dependent on
the temperature. AU these phenomena are col-
lected together as cases of tJiennolysiSjOt de-
composition by heat alone, and their study
forms the larger part of the subject of dissocia-
tion, which also embraces cases of decomposi-
tion by other physical processes, such as expo-
sure to light or electrical discharges.
There are many substances which undergo
a complete and non-reversible chemical change
nnder the action of heat ; these decompositions
may be regarded as cases of unlimited dissocia-
tion, and are generally called decompositions
simply. Such unlimited changes are, however,
best studied by themselves, and will not be
dwelt upon in this article. For convenience of
treatment we may define dissociation as fol-
lows : —
Let there be a chemical system consisting of
atoms of kinds. A, B, C, &o., capable of combi-
ning together in any way ; and let their actual
state of combination at any instant depend par-
tially on the physical conditions to which the
system is exposed at the instant considered;
and let the state of combination be called the
state y when the physical conditions are denoted
by a. Then if y changes when x changes, in
such a way that y always returns to its original
value when a returns to its original value,
the system is called a dissociable system. In
fact the value of a; must be independent of
the ' previous history ' of the system ; this neces-
sarily implies that in dissociable systems the
change of state of combination must be rever-
sible. Dissociation, therefore, is the doctrine
of reversible chemical reactions. Dissociation-
processes are but special cases coming under
the general laws of chemical equilibrium ;
as such they will be considered in the article
KQUHilBItinil, CHEMICAL.
The changes which take place in the energy
of the system as its chemical constitution varies
must necessarily exert a very great influence on
the readiness with which such variation can
occur. It is obvious, for instance, that the state
of combination cannot change by itself from a
condition of less to a condition of greater energy
unless that energy be supplied from without.
A supply of energy has therefore to be provided
in order that many dissociation reactions may
take place. In consequence of this, the thermal
changes taking place during some cases of dis-
sociation have been carefully studied (Berthelot) ;
and much valuable information has been drawn,
in other cases, from a consideration of the avail-
able energy of the electric field (J. J. Thomson).
Before treating special cases in detail it will
be well to form a simple working hypothesis
of dissociation, in order to shorten/' as much as
possible, the treatment of the experimental re-
sults. Such an hypothesis is ready to hand if
we translate the results of i say, our experiments
on steam, into the language of the kinetic theory
of gases, and the ordinary molecular and atomic
theory of chemistry. Taking the case of steam,
we may sum up the results arrived at by saying
that as the temperature rises the kinetic energy
oi the molecules increases, and in consequence
the number of molecular collisions per second,
as well as the violence of these collisions, must
also increase. When the atoms of oxygen and
hydrogen are uncombined they will be called
free atoms ; when combined they will be called
' paired ' atoms. The ' mean time ' during which
the atoms are free is called the ' mean free
time,' and the time during which they are paired
is called the ' mean paired time.' If in the case
of a system of oxygen and hydrogen where W9
may have molecules of oxygen, hydrogen, and
steam, as well as atoms of the two former, the
actual state of combination at any instant will
depend on the ratio of the paired to the free
time. If the time during which the atoms of
oxygen and hydrogen are paired together is long
compared with the time during which they are
free, or paired with atoms of the same kind as
themselves, then we are considering what is
equivalent to a volume of steam. If, however,
the paired time is comparatively short, then the
state of the system approximates more to that
of a mixture of oxygen and hydrogen. If we
assume that the ratio is altered by a variation
of the frequency of collisions, or of their vio-
lence, or by any other variation produced by a
rise of temperature, then we shall have increased
decomposition if the ratio of paired time to free
time decreases as the temperature increases.
When the temperature falls, on the other hand,
we shall get recombination.
We can, therefore, form a mental image of
a purely mechanical character as to the way in
which dissociation may take place. We should
expect that the effects would be modified at the
boundaries of the gaseous system; and that
some of the phenomena observed might be
traced to the influence of the state of the walls
of the containing vessel ; and so, in fact, it is.
The presence of porous bodies in particular
seems to exercise a profound influence on the
chemical state of gaseous systems exposed to
their action. The above hypothesis of the me-
chanics of dissociation is at present to be re-
garded as a mere hypothesis of the most arbi-
trary character : if we can justify it afterwards
by cumulative evidence that is another matter.
It vrill also be convenient to take advantage
of a very simple method of regarding the phe-
nomena of lUssociation first put forward by
Pfaundler in 1867. We are to regard a system
in which dissociation is taking place as a field
in which two tendencies are at work ; on the
one hand a source of energy from without the
system is tending to produce decomposition;
and on the other the ' chemical nature ' of the
component parts of the system is tending to pro-
duce recombination. Without committing oui-
selves to explain in any way the modus operandi
of these tendencies, we can see that it is possible
for the system to attain a state such that the
amount of decomposition and recombination
per unit time is the same. When this state is
reached the ' limit of the reaction ' is said to be
attained. If by raising the temperature of the
system, or by any other means, we alter the
potency of one of the tendencies, we shall have
a new equilibrium or limit. The idea is that
for every given set of conditions we shall have
a definite equilibrium, which will alter when the
conditions alter, and which is therefore called a
' mobile equilibrinm.'
DISSOCIATION.
389
The ratio of the weight of the unoombined
part of the system to the weight of the whole
system which is capable of combination is called
the 'fraction of dissociation,' and is a very con-
Tenient quantity in discussing dissociation phe-
nomena. Thus in a system of hydriodio acid,
weighing say 10 grama before dissociation takes
place, we might arrive at a temperature such
that 1 gram became decomposed; then the frac-
tion of dissociation would be denoted by A, and
would be expressed by the same number whether
we added iodine or hydrogen in excess, or, in-
deed, any inert gas.
If the external conditions change, then a
period of time, short or long, is required for a
new equilibrium to be established. Different
writers have adopted different methods of ex-
pression for the rate at which the new equi-
librium tends to become established, and various
arbitrary rules have been given for finding the
velocity of the reaction, depending of course on
special definitions of the expression ' velocity of
reaction.' In some case^ the velocity of the re-
action has been defined as the weight of sub-
stances combined or decomposed per unit time
in a system of arbitrarily chosen weight. The
most exact method would be to define
' velocity ' as the rate at which the fraction of
dissociation changes. The particular definition
which we may happen to adopt is not of any
very great importance, since it is from a com-
parison of velocities, and not from their abso-
lute value, that useful information is most readily
obtained.
The object of experiment is to determine the
relation existing between the fraction of disso-
ciation, when the limit is attained, and the other
quantities involved. The most important of
these are temperature, pressure, and proportion
of reacting substances. The velocities of the
reactions must also be studied experimentally.
We follow Lemoine in his distinction between
the reactions which take place in homogeneous
systems, and those which occur in non-homo-
geneous systems. If we start with a homo-
geneous system and by dissociation convert it
into a system which is not homogeneous, we
should expect a corresponding modification in
the reaction, and such is the case. The most
valuable results will be obtained when the ex-
perimental conditions are as simple as possible;
and therefore more attention ought to have been,
devoted to the dissociation of systems which
remain homogeneous than to those which are
non-homogeneous to start with, or which be-
come so by dissociation. Unfortunately, how-
ever, it is diflicult to experiment on homogeneous
systems.
Qualitative experiments whereby the exist-
ence of the dissociation of compounds was
established. — Eegnault describes some experi-
ments under the article ' Chaux ' {Course iU-
inentawe de CMmie [1854], 2, 2,3,5) which show
that some solid bodies, decomposable by heat
into one or more solids and a gas, give ofi the
gas more freely when in presence of a foreign
gas than when exposed to the products of their
own decomposition. Chalk loses its carbonic
acid more freely in ordinary air than in an at-
mosphere of carbonic acid. Eydrated salts lose
cheir water of hydration more readily in an
atmosphere of dry air than in one of water
vapour. Grove, as we have seen, demonstrated
the decomposition of steam by heat, and pointed
out that the condition that the decomposition
shall be sensible is that the products of decom-
position must be rapidly cooled, or in some
other suitable way removed from the sphere of
action before recombination can take place.
Prom a theoretical point of view it is immaterial
whether we hinder recombination by preventing
the atoms from getting to one another through
admixture with an inert gas, or whether we
lower the temperature so rapidly that it falls
below the combination point before all the atoms
are recombined.
Deville first laid down these principles with
great clearness, and practically invented all the
apparatus requisite for the realisation in prac-
tice and on a large scale of the necessary con-
ditions. His apparatus is of three kinds.
I. For raising gases to a high temperature,
and removing, at that temperature, the pro-
ducts of dissociation, by tdking advantage of the
laws of gaseous diffusion.
II. For raising gases to a high temperature
and preventing recombination by admixture with
an inert gas.
III. For raising gases to a high temperature
and preventing recombination by sudden dool-
ing. This apparatus took two forms : —
a The hot and cold tube.
/3 Apparatus for sucking the hot gases into a
tube through which water is circu-
lating.
Exact information may be obtained from
DeviUe's papers {v. Bibliography) ; and espe-
cially, from his Legons sur la Dissociation pro-
fessie en 1864 devant la Sociiti Chimigue.
I. A glazed porcelain tube is fitted with good
corks at each end ; through these corks, and
concentric with the axis of the porcelain tube,
another tube of unglazed earthenware is passed.
The porcelain tube can be heated, by means of
a suitable furnace, to a very high teinperature.
The gas to be decomposed is made to circulate
through the annular space between the two
tubes. A current of an inert gas continually
passes through the tube of unglazed earthen-
ware and sweeps away with it the products of
diffusion (v. fig. 1).
DeviUe decomposed steam by means of this
apparatus, using carbon dioxide as the inert
gas ; the carbon dioxide was subsequently ab-
sorbed by potash, leaving a mixture of oxygen
and hydrogen.
II. A porcelain tube is filled with pieces of
porcelain in order to expose a large surface.
The gas to be decomposed is mixed with a much
larger volume of some inert gas and passed
through the tube which is heated as before. This
apparatus is not so powerful as the one last de-
scribed. In an experiment in which a mixture
of steam and carbon dioxide was passed through
the apparatus, the yield of explosive mixture of
oxygen and hydrogen was much smaller than
when the porous tube was used; though of
course in that case the mixture was chiefiy hy-
drogen. This method is less applicable to quan-
titative experiments because of the complication
introduced by the action of the large extent of
porcelain surface exposed.
390
DISSOCIATION.
Illo. The hot and cold tube : this was used
first for demonstrating the decomposition of
carbonic oxide into carbon and carbon dioxide.
If resembles form I. with the modification that
the porous central tube is replaced by a tube of
silver through which a stream of cold water is
kept constantly flowing. The decomposition of
the carbonic oxide gas was proved by thfe depo-
sition of carbon on the silvered tube, and by the
presence of carbon dioxide in the stream pf gas
which passed through the tube.
ni^. An apparatus of the same kind as the
last, but with the important modification that a
small hole of "2 mm. diameter is bored in the
side of the metal tube. The result is that when
a stream of water is allowed to flow through the
tube, air is sucked in at the small hole after the
manner of a velocity pump. This apparatus
was employed by Deville to examine the con^
stitution of the gases in the middle of a candle
flame ; and was afterwards employed by CaiUetet
for extracting the gases from a blast furnace
(C.iJ. 62, 891).
By means of these various forms of ap-
paratus the dissociation of the following gases
was demonstrated : —
an accidental phenomenon connected with the
rapid heating and cooling of portions of the gas.
J. J. Thomson (P. M., June 1883) has, however,
given good reason for believing that decomposi-
tion is a necessary condition for the passage of
electrical discharges ; that in fact a spark can
no more pass through an atmosphere of water-
vapour without resolving it partially into oxygen
and hydrogen than an electric current can pass
through copper sulphate solution without de.
composing it into copper and sulphuric acid.
Whether Faraday's law of electrolysis extends
to gases is still an open question ; the pro-
bability is that it does not. However the de-
composition is produced, there will probably be
a certain amount of recombination as soon as
the gases cool sufficiently. Since the products
of decomposition are in general diluted with a,
large proportion of undecomposed gas, the tem-
perature of the decomposed portions will often
fall below the minimum temperature of com-
bination before complete recombination has had
time to take place. This will leave a balance of
decomposition at each spark. As soon, how-
ever, as the products of decomposition have
accumulated to a small extent, they, as well as
Fia. 1.
Water vapour by I. and II. — Carbon dioxide
by II. — Carbonic oxide by III. ; carbon deposited
on the tube. — Sulphur dioxide by III. ; tube
blackened, and deposit of sulphur trioxide on
it. — Hydrochloric acid by III. ; surface of tube
being previously amalgamated, and chloride of
mercury and silver formed by the dissociation.
It will also be convenient to notice here the
dissociation of gases produced by electrical dis-
charge. There is no real difference between the
spark discharge and the so-called silent dis-
charge. The silent discharge is merely a spark
discharge in which the sparks are very numerous
and very small. In the cases where a limit has
not been observed, the explanation is to be found
in the fact that one or more of the products of
decomposition is either liquid or solid, and is so
removed from the sphere of action. This is
notoriously the case with acetylene and hydro-
carbons generally. Where a limit is attained, the
reaction may generally be made complete by in-
troducing a substance capable of absorbing at
least one of the products of decomposition. It
was formerly believed that the decomposition of
gases by electric sparks was, so to speak, merely
the undecomposed gas, will be acted on by the
spark, and a certain amount of recombination
will take place. It must be noted, however, that
the decomposition produced by each spark is
very small, since the energy of the electric field
is in general small compared with the amount
of energy required to produce even a small de-
composition. After a certain length of time the
decompositions and recombinations will become
equal, and the limit of the reaction will be at-
tained. The production of a limit in the experi-
ment of ozonising oxygen is well known, and the
production of ozone at all shows that oxygen
molecules must be previously electrolysed into
oxygen atoms. This is also proved by an ex-
periment of De la Bue and MiUler, repeated and
modified by Thomson and Threlfall, whereby a
large increase of volume is observed to take place
in a tube through which a spark passes, and
which is much greater than can be accounted
for by the expansion due to heating. In oxygen,
if the sparks are very small so that the heating
is insignificant, a diminution of volume is ob-
served to take place owing to the production of
ozone. The action of the spark on gases seems
DISSOCIATION.
391
to be dependent on the nature of the spark, and
this in turn depends to a gr^at extent on the
pressure of the gas. Much work still requires to
be done in this direction. At present the fol-
lowing list of gases which have been decom-
posed will suffice : Oxygen, nitrogen (?), carbon
dioxide, methane, ether, acetylene, ammonia,
acetic acid, phosphoretted hydrogen, carbonic
oxide, hydrocarbons generally, sulphuretted hy-
drogen, seleniuretted hydrogen, cyanogen, &o. De-
composition of the fluorides of boron and silicon
and chlorine has not yet been observed, but
there is little doubt thatthe decomposition of these
bodies will ultimately be demonstrated. Most of
the above observations have been made by P. and
A. TMnard (0. B.) andi by Berthelot . An ac-
count of the extremely valuable researches of
Berthelot and Yieille on dissociation during ex-
plosion, as well as of the observations of Dixon,
will be found in the article Explosion.
tures have to be made, and these are subject to
the almost unavoidable experimental uncertainty
attendant on that very difficult operation. A
judgment as to the trustworthiness of the re-
sults obtained can in general be formed only
from astudy of the observer's own account of
his experiments.
The methods of thermal chemistry have been
applied by Berthelot to the solution of many in-
teresting questions. '
Dissociation in non-homogeneona
systems. — ^We shall consider first the allotro-
pic change produced by heat in ordinary phos-
phorus. When yellow phosphorus is heated
in a closed space it is partially changed into red
phosphorus; and when red phosphorus is
heated it is partially converted into yellow phos-
phorus. It is found that neither reaction is
complete, but that the same limit is attained
whether we start from red or from yellow pho8»
Owve r^esemUng the pressures of ordina,ry phosphorus which Umit the alloiropie
transformation of the phosphorus at Afferent temperatures.
■i
jam.
60-
60
40
■g-g
I"!
s3
20
10
^^ a.
260
300
500
550
too
Scales
3S0 400 450
Temperatnres.
1 mm. for 1 nmi. of vapour-pressure, and 0-2 mm. lor 1 degree ot temceratnrei
FlQ. 2.
Quantitative Experiments on Dissoeiatiou.^ —
It is now our business to discuss the quantitative
experiments which have been made on particular
cases of dissociation. Prom a theoretical point
of view these experiments fall into two classes :
(a) Those made on the determmation of the
Umit, and its dependence on pressure, tempera-
inure, dc.
(0) Those rtferrmg to the velocity of the
reaction.
Prom an experimental point of view very
different methods have to be adopted in different
oases. In one class of experiments the obser-
vations take the form of determinations Of va-
jpour density at different temperatures and pres-
sures. Experiments on velocity usually depend
on the ordinary methods of analysis; and of
course involve observations by the chronometer.
In many cases observations of high tempera-
phorus. If we start with yellow phosphorus, and
heat it to a definite temperature in a closed
vessel in connexion with a manometer, a
transformation into red phosphorus will take
place. Tellow phosphorus has a considerable
vapour-pressure ; the transformation vriU go on
tiU the pressure inside the vessel reaches a cer-
tain value; this value will be less than the
maximum vapour-pressure of red phosphorus
corresponding to the temperature, and is called
the ' limiting pressure.' If, on the other hand,
we start with red phosphorus, the vapour-
pressure will diminish from the maximum to
the limiting pressure. This pressure is found
to be the same in both cases, provided the tem-
perature is the same. Analysis of the residue
gives the proportions of red and yellow phos-
phorus. Each temperature has its definite
limiting pressure. If we start with a small
392
DISSOCIATION.
Ordinary phos-
phorns intrc^ Quantities of ordinary phosphonu
quantity of yellow phosphorus, and heat it in
a vessel so large that it is not able to produce
the limiting pressure corresponding to the tem-
perature, no red phosphorus wiU be formed.
The phenomenon is, therefore, quite analogous
to the yapourisation of a liquid according to the
two cases when the conditions are such that the
vapour is (a) saturated, or (;3) unsaturated.
The accompanying curves (figs. 2, 3, 4) and
numbers will give the results obtained. (The
tesults are ohielSy taken from Lemoine'a J&Uides
aur Us ^mlibres Chimigues.)
Ctirves representing the weights of ordinary phosphorus rernaJinmg at the end of different t/i/mes,for
a simMa/r weight P of ardi/na/ry phosphorus introduced (Lemoine).
space ot one
litre.
Grams.
2-9 (Lemoine)
S-g a.
16-0 id.
24-0 f Hittorf)
30-5 (Lemoine)
6m.
gr.
15-5
Jh. 2h.
€r. gr.
ll-l 70
— 6-4
8h.
gr.
2-g
S'S
60
4-4
4-0
17h.
gr.
3'r
241i.
gr.
si
32h.
gr.
4'9
4lfi.
gr.
47
The common limit Is 36 grm.
F=6-9 gx. ot ordinary
phospboras per litre.
3^ma»
\
'P=ii gr. of ordinary
phosphorus per litre.
V
F— 30 gr, ot ordinary
phosphorus per litre.
2 8 V
Scales : 2} mm, for 1 hour, and 2} mm. tor 1 gram.
Fia. 3.
SShoon,
1-8 gr. of red phosphonu per litre. I/tT
a 3
32
4'9 gr. of red phosphorus per litre.
U gr. of red phosphonu per litre.
SO gr. of red phosphorus per litre.
2 S
Scales : 2} mm. for 1 hour, and 2 mm, tor 1 gram.
Fia. 4.
DISSOCIATION.
893
We may account tor these same differences
by calculating, according to the preceding data,
the mean quantity of red phosphoma produced
in one hour : —
Ordinary phosplio.
ms inteoducedper
litre.
Bed phosphorus formed in grams
iu one hour at 440°.
Time.
from 0 to 2h.from 2 to 8h Jrom 8 to 32h.
grma,
SO'O
Red phospho-
rus employed
per litre.
■«— 0'075 -*. 0-016
18-30 • 0-233 0016
Temperature 440°.
Quantities of ordinary phosphorus
in grams produced at the end of :
1-8
4-9
16
30
100
1000
ih.
— 0-80 1-33 —
— 1-62
— 3-67
8h. 23h. 32h. 39h. 47h. 83h.
1-7 — —
2-9 — — 3-3 — 3-32
4-6 — 4-0 _ _ —
4-54 4-75 4-4 3-9 3-74 — 3-72 —
_ _ 3-6? ———-.—
It will be noticed that in some of the velo-
city experiments, starting from red phosphorus,
the vapour-pressure at first produced is higher
than the pressure of the limit ; this is explained
by the previous history of the red phosphorus,
of which it appears there are several allotropio
modifications depending on the temperature at
which they have been produced. This has been
studied by Troost and Hautefeuille and com-
pletely explained.
Cyanogen is slowly transformed into para-
cyanogen on heating. The velocity is very small,
but appears to be greatest at about 500°. The in-
verse reaction has a comparatively great velocity.
There is a limiting pressure of transformation
just as in the case of phosphorus. Observations
are complicated by a continual slow decomposi-
tion of the cyanogen into nitrogen and carbon.
An analysis has, therefore, to be made of the
residue before the correct limiting pressure can
be obtained. The following are the numbers of
Troost and Eautef emlle :
Temperaturea
502°
54
506
56
559
123*
575
129»
587
157
599
275*
601
318
629
868*
640
1310
The immbers with asterisks have heen obtained with
paracyaiiogen prepared from cyanide of aUrer. The others
have been furnished by paracyanogen prepared from
cyanide of mercury, and perfectly freed from the metal.
Cyanio acid, is converted into cyamelide and
vice versd. The velocity depends on the tempe-
rature ; and it is by no means the same for the
two reactions. A complication is introduced,
because above 150° gaseous cyanic acid is trans-
formed into solid cyanic acid ; and below 150°
cyamelide is produced. The production of a
maximum vapour-pressure limiting the decom-
positions ia perfectly clear and definite. The
numbers are —
Temperatures
160' 170 180 195 215 227 251 330 350
Transformation-pressures
66mm. 68 94 125 157 180 285 740 1200
Allotropio transformations of homo-
geneous systems. Acetic acid. The vapour
of acetic acid has long been known to possess
a vapour density greater than the theoretical
density. This diminishes, however, as the tem-
perature rises, or, in other words, the coeflcient
of expansion of acetic acid vapour between cer-
tain temperatures is greater than it is for most
gases. A discussion of the explanations ad-
vanced to account for this has been already
given. The data for the dissociation of acetic
acid are given on p. 394 (Ramsay a. Young, C. J.
49, 790).
■ Nitrogen tetroxide (DeviUe and Troost, O. B.
64, 237). The relation between the vapour-
density and temperature of nitrogen tetroxide
under ordinary pressures shows &at at about
150° the change of tetroxide into a gas of the
molecular formula HO, ia complete. The num-
bers are as follows : —
Dissociation of nitrogen tetroxide K^O,. Sp.
gr. of NjO,=3'18; of NOj + N02=l-59; (air=l).
Temp.
26-7°
35-4'»
39-8°
49-6°
60-2°
70°
80-6°
90°
100-1°
111-3°
121-5°
135°
154°
Mean increase in per-
Sp. gr. of Percentage centage dissociation
gas dissociation for 10° rise of tem-
perature
2-65
2-53
2-46.
2-27
2-08
1-92
1-80
1-72
1-68
1-65
1-62
1-60
1-58
19-96
25-65
29-23
40-04
52-84
65-57
76-61
84-83
89-23
92-67
96-23
98-69
100
6-5
8-1
H-0
12-1
13
10-4
8-8
4-4
3-1
3-5
1-8
Troost, continuing the experiments in 1878
at very low pressures, finds that at temperatures
as low as 27° complete dissociation may take
place.
Naumann gives a large series of numbers, aa
in the case of acetic acid vapoui, between tem-
peratures of —6° and +22*5° and pressures of
84 to 801 mm. Another determination of the
density of nitrogen tetroxide vapour has been
made with extreme core by E. and L. Natanson
(W. A. 1886. 164).
Aa baa been already stated, Berthelot and
Ogier have measured the specific heat of acetic
acid and nitrogen tetroxide vapoura. The method
adopted was Begnault's ; care was taken in the
case of nitrogen tetroxide to have all the apparatus
made of glass. The specific heats were of course
measured under constant pressure. Through the'
range of temperature over which it undergoes
change, the specific heat is enormously greater
than the mean specific heat of permanent gasea
formed from their elementa with condensation.
For the latter Begnault gives, for nitrous oxide,
for instance ;
Molecular specific heat 8-76 -^ ■0055<
And for carbon dioxide 8-23 + ■01177<,
while for gases formed without condensation we
have practically the same value without a tem-
perature-coefficient, at least up to 200°. For
some organic substances the specific heats are
much greater. Wiedemann gives as follows :—
394
DISSOCIATION.
Ethyl bromide .
Acetic ether . .
Benzene . . .
Molecular speoiflo heat
. 14-76 + -0388*
. 24-1 +-0765i
. 17-45 + -0798J,
while for acetic acid and nitrogen tetroxide the
specific heat rises above 50°, and the tempera-
ture-coefficient is itself a function of the tempe-
rature. The following numbers will make the
results of Berthelot and Ogier clear: —
Temperature interval
Total heat
absorhed by
1 gram-
molecule of
NjO. ex-
pressed in
gram-
degrees
Mean mole-
cular specific
heat for
the range
specified
27° to 67° (40 degrees;
67° „ 103° (36 „ )
103° „ 150° (47 „ )
150'> „198°(48 „ )
198° „ 253<* (55 „ )
253° „ 289° (36 „
2988-0
2050-8
1271-1
436-1
463-4
594-2
74-7
57-0
27t0
9-1
8-9
12-9
This table shows that the heat absorbed is
very great, even at 27°, and the specific heat di-
minishes till the temperature of 150° is reached.
From there it remains fairly constant till the
temperature rises to 253°, and above that it in-
creases. Berthelot subtracts from the values
given above, the heat which would be taken to
raise the temperature of a non-dissociable gas
through the same ranges, adopting Eegnault's
f ormida, molec.sp. heat = 8-76 -I- -OOSSt. The re-
maining heat is probably taken np in dissocia-
tion-work ; assuming this to be the case, Berthe-
lot calculates the amount of dissociation which
should take place, and compares the result with
the numbers obtained by Naumanu and Salet as
deduced from observations on the vapour density.
It wiU be seen that the numbers agree as well as
could possibly be expected, bearing in mind
the unavoidable experimental errors of such a
difficult operation as a determination of the
specific heat of a gas.
Decomposition between
different temperatures as
deduced from heat absorbed
Decomposition between
different temperatures de>
duood by Naumann and
Salet from vapour density
observation
Bange of tem-
perature
Decompo-
sition in
percen-
tages of
total
Bange of tem-
perature
Dccompo-
sition in
percen-
tages of
total
27° to 67°
67° „ 103°
103° „ 150°
40
26-3
13-2
Below 26°
26° to 70°
70° „ 100°
100° „ 136°
20
35-6
, 23-6
9-5
79-5
68-7
The agreement will be better seen from the
curve (fig. 5). In order to compare the two
effects the ordinates are proportional to the
quantities of heat absorbed for one curve, and
proportional to the decomposition in the other.
The abscisses give the temperatures. It will be
seen that the agreement is very close ; if it were
complete the curves would coincide. It is still
closer, however, for acetic acid vapour, for which
Berthelot and Ogier have made similar experi-
ments and calculations. The curves will explain
this; for the actual numbers v. the origii>al
paper. An extension of Gibbs' thermo-dynamic
theory has been made to embrace these variations
of specific heat by Duhem (/. dePh., July 1886).
The calculated and observed variations seem to
agree fairly well.
lodme. — The vapour-density of iodine varies
with temperature and pressure. A very full and
complete study by Crafts and Meier has been
made of the vapour of iodine {v. curves, fig. 6),
The results may be summarised by saying that
from 300° to 700° iodine vapour behaves like a
perfect gas; at 700° the relative density of the
vapour begins to diminish under all pressures,
and this continues till the temperature reaches
a value of about 1,500°, when the vapour again
conforms to the gaseous laws. The two states,
below c. 700° and above 1,500°, correspond to the
Acetic acid. Theoretical vapour-density (H=l) 29-92.
Pressure in mm.
t
£0
40
100
300
iOO
1000
2000
BOOO
10000
16000
20000
21000
40°
' 54-22
50°
50-62
53-61
60°
47-04
50-38
70°
43-55
47-12
51-21
80°
40-45
48-86
48-08
100°
35-63
37-92
41-81
48-50
120°
32-75
34-01
36-50
42-79
46-71
140°
31-32
32-12
33-72
38-05
41-42
46-81
160°
32-10
34-77
36-88
41-80
47-81
180°
31-17
32-66
34-01
37-39
42-58
200°
38-64
47-99
220°
85-82
42-39
240°
34-00
38-79
47-60
260°
32-89
36-39
42-80
53-00
2S0°
32-21
34-66
39-10
45-45
51-34
60-70
DISSOCIATION.
396
lormulffl Ij and I respeotively. Considering the
rate of dissociation and its relation to pressure
we may say that the rate o£ dissociation per
degree of temperature becomes greater as the
pressure diminishes. These changes are accom-
panied by a change of the absorption-spectrum
(Salet, Bl. 1873. 674).
DisBooiation of compounds.
I. Systems that are not homogeneous.
Carbonate of calcmrn.
BibUograpKy.—Debraj (O. B. 64, 603) ; Wein-
hold (P. 149 ; J. 1874. 119) ; Eaoult (0. B. 1881.
189); Birnbaum and Maher {Bl. 1880. 88);
Wiedemann (P. Jubelbd. 1874. 474 ; J. pr. [2] 9,
838).
Debray made the first research on this sub-
ject. His method consisted in heating Iceland
Debray found it, and that the variations of pres-
sure are never regular. Baoult finds that, start-
ing with quicklime and COj, combination takes
place with incandescence at about 550°. The
compound formed has, however, the formula
(OaO)2C02. This compound is capable of ab-
sorbing more_ carbon dioxide, though the velocity
of the reaction is very small ; in twelve hours
after a continual passage of a stream of GO,
over the compound, analysis shows that a body
of the composition 4Ca0.3C02 is produced,
and an extremely slow absorption still goes on.
Baoult also finds that the amount of carbon di-
oxide absorbed depends on the previous history
of the quicklime and that it is much less ab-
sorbent if it has been previously heated to a
high temperature. Wiedemann finds that much
100
-,5''"'
i^^
^
go
4,
^
.^"^
uu
A
S
r
70
'f-
4
^o'
60
-1y
t/f.
u
r
40
^
K
30
/
If
M
/J
<-\
1
/]
V
%
,
10
30
40
SO
60 ro
80
90 ino 110 120
130
140 150
?or the acetic add cuxres tlie teinperature scale Is
snpposed to be Increased by 100°. The heat abscrbcd
between 120° and 260° is divided into 100 parts, as is the
change ol vapour-density.
For the nitrogen tetroxlde the amount of heat absorbed
between 127° to 198° is divided into 100 pai-ta, as is the
disso'jiaMon as given by Naumann and Salet.
FXQ. 5.
spar in a vessel connected with a manometer
and air-pump ; an arrangement providing for the
introduction of carbon deoxide was also attached
to the apparatus. Decomposition of the calcium
carbonate begins at 440°, the crystals becoming
opaque owing to changes atthe surface. Above
this point the phenomenon of limiting pressure
depending on the temperature is observed. Ac-
cording to Debray the limit is the same whether
we start from calcium carbonate in a vacuum, or
from quicUime in an atmosphere of carbon di-
oxide. If in any case the pressure is kept below
the limiting pressure corresponding to the tem-
perature, the Iceland spar will be completely
decomposed.
Vapour-pressure at 860°= 85 mm. of mercury.
„ 1040° = 520 mm.
Weinhold, repeating these experiments, finds
that the pressure of CO, is always greater than
depends on the crystals of Iceland spar selected
being previously carefully dried. Debray is
probably substantially correct in his general de-
ductions, but not in his experiments.
Hydrated salts. — Efflorescence (Debray, C. B.
1868. 194). In general, the same phenomena
are observed in heating hydrated salts as in
heating calcium carbonate. There is a definite
limiting pressure for every temperature ; this is
the same whether the water-vapour exists by ■
itself or in presence of air. In fact the hydrated'
salts act very much like liquids in their appre-
ciation of ' partial pressures.' The phenomena
are modified in accordance with the fact that
each salt is generally capable of forming more
than one definite hydrate.
The numbers observed by Debray for crys-
tallised sodium hydrogen phosphate will
serve as examples. (NajHPO, -H 24HjO) and
SOB
DISSOCIATION,
(Na^HPO, + I4H2O). / ia maximum vapour-
pressuie of the salt, F is pressure of water-
vapour at same temperature : —
Temperotoiea
Phosphate at Phosphate of
Bodiam con- sodium contain-
tainioglrom ing a little less
14to24H,0
than 14H,0
^ 4
f i
0
mUHmetres
miUimetra
12-3
7-4 0-694
4-8 0-452
16-3
9-9 0-717
6-9 0-500
20-7
14-1 0-776
9-4 0-517
24-9
18-2 0-777
12-9 0-551
81-5
30-2 0-819
21-3 0-618
36-4 (the ealt melted)
39-5 0-877
80-5 0-678
400
50-0 0-901
41-2 0-750
Wiedemann has observed the relation be-
tween limiting pressure and temperature for the
following salts :—
MgS0^.7H20
emp.
Pressures
Temp,
Pressures
0
mm.
0
mm.
24-3
17-8
50
75-7
35
35-6
60
122-5
40
47-2
70-4
190-3
40-2
46-3
80
276
ZtiRO
,7KjO
(The crystalB
melt at 70-5°)
emp.
Pressures
Temp.
Pressures
0
mm.
0
mm.
16-5
113-9
60
116-6
30
20-3
70
170-8
40
44-2
75
221-2
40
43-6
85-6
376-4
50
731
90
427
60
74-5
Temp.
D
22-1
35
35
45
45
65
Temp.
o
25
35
35
45
56
Pressures
mm.
115-9
34-6
35-6
62-3
65
106
CoSO<,7H,0
Temp,
o
65
75
75
85
90
Pressures
mm.
19-3
36-4
38-4
• 63-7
105-6
NiSO,.7H20
Temp,
o
65
65
75
8a
Pressures
mm,
168-2
252-6
254-7
377-4
447-9
Pressures
mm.
163-8
165-9
251-6
342-5
Sulphate of iron E'eSOi,7HjO
(The crystals melt at about 90°)
Semp,
o
20
30
40-2
50
55-2
60
Pressures
mm.
10-9
20-3
40-1
74-8
103-5
131-3
Temp.
o
65
65
75
86
93-5
Pressures
mm.
163-4
160-9
263-9
897-7
648-9
Naumann has studied the efflorescence of
sulphate of copper very carefully, and it is
chiefly through his researches that the influence
of previous history and the precautions neces-
sary in observing the equiUbrium of slow velocity
changes have been brought to light. These ex-
periments show very clearly how the velocity
depends on the state of the salt with respect to
the size of its particles. In the case of crystals
a slow progressive change goes on as the inner
portions become dehydrated, and it is only when
Curve repreaenVng the density of iodine vcvpowr at different temperatimes and at different pregiwres
according to the experiments of Crafts and Meier (licmoine).
9-0
8-8
8-0
=S '"0
60
6-0-
4-4-
r —
100
— I —
400
— I—
BOO
— I
eoo
700
800 900 1000 UOO
Temperatures.
1300 1300 1400 lEOO
Scales : 8 mm. to 100 degrees, 13-26 mm. to 1-0 of variation ol denait;,
Fm. 6.
DISSOCIATION.
397
the composition of the crystals is uniform
throughout that the equilibrium is obtained.
Carbonates of manganese and silver (Joulin,
/. Ch. 1873. 276).— The velocity of the reaction is
very slow; and the influence of the previous
history is even more marked than in the case of
carbonate of lime, so much so that the author
considers that allptropio modifications of the
salts exist, and that these have different vapour
pressures. Carbonate of silver appears to be
even more irregular in its behaviour than car-
bonate of manganese. Lemoine has summed
up these experiments as follows. After laying
down the simple principles as deduced from ex-
periments on carbonate of lime hesays : ' Mais
Oxide of iridium (H. St. C. Deville and
Debray, C. B. 1878. 441).— A clear example of
dissociation. Limit at 823° is 5 mm., and at
1139°, 746 mm. At 1000° the limiting pressure
is greater than the partial pressure of oxygen in
the air at atmospheric pressure ; it follows from
this that at temperatures below 1000° the iridium
oxide can decompose in air, and at temperatures
above this iridium is non-oxidisable.
Compomids of metallic chlorides With am-
m/)nia; studied by Isambert (0. B. 1878). — The
curves (taken from Lemoine) will Bu£Bce to ex-
plain the matter sufficiently (fig. 7).
Chloride of sulphur, and the compound
formed by the combination of cuprous chloride
Curves representing the pressures of ammonia-gas which limit the dissociations of
ammomacal chlorides at different temperatures.
20 40 80 100 120
Temperatures.
Scales : 0'( mm. for 1 degree of temperatnre, and 6-0 mm, for 100 mm. ol preasore.
Fia. 7.
11 peut se presenter des cas oft la combinaison,
tout en se faisant en mSme temps que la decom-
position, soit si lente que toutes sortes de oir-
oonstanoes acoidentelles influent sur eUe: il
peut, se faire que les 614ments mis en liberty
dprouvent des modifications aUotropiques, an
moins commenijantes, qui gtoent leur combi-
naison nouvelle. Dans tons ce? oas, I'fitablisse-
ment d'une tension limite, tout en 6tant I'ex-
pression g6n6rale du ph6nomtae, se manifestera
moins nettement, paroe que la loi est oompliqufie
par dif£6rentes ciroonstanoes aooessoires.'
Mercuric oxide (Myers, Bl. 1871). — The
experiments are so, complicated by the vapour
of mercury set free that no uSeful information
has yet been drawn from them.
and carbonic oxide, appear to dissociate, and
have given rise to some discussion (Berthelot,
A. Ch. [3] 46, 48; Michaelis, A. 170; Isambert,
C. B. 1878).
MetalUc hydrides (Troost a. Hautefeuille,
C. E. 1874 a. 1875).— These researches have
shown that hydrogen may be associated with
metals in three different ways : — 1. By simple
condensation as in the well-known case of
platinum black. 2. By solution. 3. By chemi-
cal combination. Heating the substance in a
closed space in connexion with a manometer and
air-pump will at onoe show which of the three
forms of combination is exhibited in any special
instance. If the gas is simply condensed
there will be no definite relation between ths
308
DISSOCIATION.
pressure and the temperature. It generally
happens that the second and third order of
phenomena are exhibited together. In this case
the gas that is dissolved will be simply evolved
on heating, aiid will leave a more or less definite
compound having a definite limiting dissociation
pressure.
For instance, potassium, hydride E^H ' dis-
solves ' forty times its volume of hydrogen, so
that on heating and exhausting tiiis gas is
evolved. It would probably, however, be more
accurate to say that two or more hydrides may
be formed of different degrees of stability. On
raising the temperature we get a definite dis-
sociation of the potassium hydride which re-
mains. The numbers are : —
Palladium hydride gives :
Pressures of
Temperatures
dissociation
Temperatures
dissociation
o
mm.
o
mm.
330
45
390 .
863
340
58
' 400
548
350
72
410
736
360
98
420
916
370
122
480
1,100
880
200
of
Pressures of
Pressures ol
Temperatures
dissociation
Temperaturei
dissooiatioii
o
mm.
o
nun,
20
10
120
467
40
25
140
812
60
50
160
1,475
80
106
170
1,840
100
232
The eonipoimd formed by ehlorme and water
dissociates very readily, giving the curve shown
in fig. 8.
Hydrogen selemde. — The dissociation of this
gas has been studied by Ditte (C B. 1872.
980). It apparently presents the extraordinary
anomaly of the dissociation-pressure not in-
creasing continuously with the temperature. It
must be noted, however, that below the tempera-
ture of 270° the velocity of the reaction is so
small that the composition of the gaseous mix-
ture has to be determined by a sudden cooling
of the sealed tubes containing the gas, and a
subsequent analysis of their contents. It may
be very fairly asked how, in the first place, this
DiswciaHon of ehlorme hydrate.
s
a
uoo"
1300
1000
400-
sao
TempeiatRies.
giales : 6 nun. for one degree of temperature, 5 mm. for 100 mm, of pressure.
Fio. 8.
And for sodium hydride, in which hydrogen is
much less soluble, the numbers are :—
Pressures of
Temperatures
dissociation
o
mm.
330
28
340
40
350
57
360
75
370
100
380
350
Pressures of
Temperatures dissociation
390
400
410
420
430
mm.
284
447
698
752
910
procedure gets over the velocity difficulty, and,
in the second place, whether it is likely to give
any information at all seeing that no cooling
can take place in an infinitely short time. The
following numbers will give an idea of the
velocity of the reaction when selenion is heated
with hydrogen : —
Number of
lioors
10
24
25
44
Temperature of 350°
Proportion per
lOOofHjSo
formed hours
31-4 63
33-1 74
34-3 96
36-6
Proportion pel
Number of 100 of HjSe
formed
37-8
37
37-8
DISSOCIATION.
399
^Amjierature of 440°
Nnmber of
15
21
Proportion per
100 of HaSe
formed
46-3
48-8
Proportion per
Nnmber of 100 of H,Se
hours formed
69 50-6
165 61-5
The effect in the velooity of changing the
pressure of the hydrogen is small, and acts so
as to diminish the velooity when the pressure
increases; but the limit of the reaction was
Probably never attained in these experiments,
'he effect of porous bodies has also been studied
by Ditte, and the result is that a small but
defibuite increase of velocity is due to their
action, which is less marked, however, at high
than at low temperatures.
Ammonia and carbon dioxide (Naumann,
A. 84; Horstmann, A. 1887). — The limiting
pressures of dissociation of ammonium carba-
mate are given by Naumann as follows : —
Tempera-
tures
o
-15
-10
- 5
0
6
10
16
20
Pressures of
dissociation
mm.
2-6
4-8
7-5
12-4
22
29-8
46-5
62-4
Tempera-
tures
o
26
30
36
40
46
sp
55
60
sol
dissociation
mm.
97-5
124
191
248
354
470
600
700
The velocity is small and increases with the
temperature; it also largely depends on the
extent of surface exposed by the carbamate.
Naumann and Horstmann have studied the
effect of the presence of an excess of ammonia
or carbon dioxide. They find that the effect of
an excess of either gas is to hinder ti^e dissocia-
tion. In other words, the limiting pressure is
diminished by the presence of an excess of
either gas. This does not appear to be the
same for the same excess of either gas. With a
given excess the limiting pressure is greater
in carbon dioxide than in ammonia.
Case in whieh cwrbon dioxide is im excesi
:—
Total
Partial
pres-
S
Vapour-
pressure of
,
e
sure ob.
served
after
sure of
the carba-
1
the gas
added
1
mate in a
vacuum at
Ratio
Ratio
p.
in
Q
temperature
i
iiiiTTuurc
considered
tJ
W
P
P-ir
P
P
P
P,
P
o
mm.
mm.
mm.
mm.
20-4
78-9
33-5
45-4
66-2
0-52
0-71
2i'a
105-8
69-9
35-9
71-0
0-98
0-81
18-3
112-4
87-4
25-0
55-0
1-59
0-45
18-3
145-4
122-3
23-1
65-0
2-22
0-42
17-9
167-9
148-9
19-0
53-3
2-79
0-36
18-6
203-4
185-6
17-9
56-3
3-28
0-32
17-9
193-3
175-7
17-C
53-3
3-30
0-33
17-8
225-3
208-4
16-9
53-0
3-93
0-32
17-6
243-6
228-5
15-1
52-3
4-37
0-29
18-6
302-9
288-3
14-6
66-5
5-10
0-26
17-7
297-5
285-6
12-9
52-6
5-43
0-24
17-7
328-8
315-8
13-0
62-6
5-99
0-25
18-4
353-7
340-7
13-0
65-5
6-14
0-23
18-4
426-4
416-8
9-6
S5-4
7-62
018
Casein
which
ammonia is in excess :-
-
Total
Partial
Vapour-
prea-
Bnre ob-
served
after
prea-
§
pressure of
1
snreot
the gaa
added
1
the carba-
mate in a
vacuum at
Ratio
Ratio
&!
in
n
temperature
exoeaa
considered
n
P
P-TT
=Pl
P
P
P
ft
P
0
mm.
mm.
mm.
mm.
21-8
69-5
24-4
45-1
70-9
0-36
0-67
20-6
75-2
35-4
39-8
65-3
0-54
0'61
20-8
86-9
57-1
29-8
66-2
0-86
0-45
17-7
68-9
48-6
30-3
52-6
0-92
0-39
20-8
88-5
66-1
22-4
66-2
1-00
0-34
22-0
103-5
89-1
14-4
72-1
1-24
0-20
20-8
108-1
93'4
14-7
66-2
1-41
0-22
20-4
111-8
92-6
19-2
64-3
1-44
0-30
17-3
99-7
860
13-7
51-2
1-68
0-27
21-7
132-1
125-2
6-9
70-4
1-78
0-10
20-7
154-5
141-6
12-9
65-8
2-15
0-20
17-3
128-0
1190
90
51-2.
2-33
0-17
21-7
168-1
165-8
2-3
70-4
2-36
003
17-4
i55-5
146-4
9-1
51-5
2-84
0-18
21-6
203-3
201-2
2-1
69-9
2-88
003
21-7
2350
232-9
2-1
70-4
3-31
0-03
17-1
180-3
173-3
7-0
50-5
3-43
0-14
20-6
231-1
226-4
4-7
65-3
8-47
007
21-8
293-6
292-2
1-6
70-9
4-15
002
20-8
295-6
289-2
6-4
66-2
4-43
0-10
21-6
325-9
324-8
1-1
69-9
4-61
0-oa
21-9
374-5
372-2
2-3
71-5
6-24
0-03
20-5
417-4
416-2
1-2
64-8
6-42
002
17-8
359-8
355-3
4-5
63-0
6-71
008
II. Dissociation in homogeneous sys-
tems.— Theoretically by far the simplest cases;
numerical results are, however, obtained with
greater difficulty than in the cases last con-
sidered.
Amylene bromide (Wurtz, C. B. 60, 729).
CjH^Br dissociates when heated into amylene
and hydrobrotaic acid ; the dissociation is com-
plete at 360°. Wurtz measured the thermal
changes produced by mixing amylene vapour
and hydrobromio acid, and found that at 360°
the change was zero, and became increasingly
positive as the temperature fell (C. B. 72). Here
then we have for the second time a proof of
dissociation ; the heat of combination of amyl-
ene and hydrobromio acid bears a simple relation
to the amount of dissociation as deduced from
the vapour density observations. Want of agree-
ment, however, was noticed in some experiments,
and attributed by Wurtz to the limit not
being obtained in all cases since the velocity is
small.
Pho^horus pentachloride PCI5. Owing to
the researches of Wurtz' on the vapour density
of this body we may consider that, subject to
the application of Avogadro's law, dissociation
has in this case been demonstrated. The pri-
mary object of Wurtz's experiments was to find
whether the vapour of phosphorus pentachloride
conformed to the law of Avogadro; assuming
this to be the case, it follows that dissociation
must take place in the observed cases of ano-
malous vapour density. Applying the principle
400
DISSOCIATION.
of the action of mass, Wurtz hit on the notion
of measuring the vapour density of the penta-
ohloride when it was vaponrised into an atmo-
sphere of phosphorus trichloride yapour. From
the analogy of other experiments the effect of
the trichloride should be to prevent dissociation,
supposing it to take place under ordinary cir-
cumstances. This was found to be the case,
and thus it was proved that phosphorus penta-
^hloride does obey Avogadro's law ; or if we as-
sume that Avogadro's law expresses the very
nature of the gaseous state under all circum-
stances whatever, then the dissociation of the
pentachloride under ordinary circumstances may
be considered to be demonstrated.
The experiments of Cahours were made at
ordinary pressures ; of Wurtz and of Troost and
HautefeuUle at low pressures; the low pressures
were produced by Wurtz by the method of mix-
ing air with the vapour, and by Troost and
Hautefeuille directly by means of an air-pump.
The numbers are : —
Experiments of Cahoii/rs at atmospheric
pressure.
.
1
1
Vaponr
Density
Batlo
of POI, combined
to FOl, possible
Ratio
1-x
of POI, dissooiat'ed
to POI, possible
182
6-078
0-58
0-43
190
4-987
0-55
0-45
200
4-851
0-51
0-49
230
4-302
, 0-32
0-68
250
3-991
0-20
0-80
274
3-840
0-12
0-98
288
2-67
003
0-97
289
3-69
004
0-96
300
3-654
0-02
0-98
327
3-656
0-02
0-98
336
8-656
002
0-98
Experianents of Wv/rtz.
Low pressures obtained by the diffusion of
the vapov/r imU) omr.
s
Partial pres-
snre sns-
tained by
the diffused
vapour
Density of
tbe vapour
of the
per-
ohloride
Eatio
of POI,
combined
to POI.
possible
Ratio
\-x
of pa,
dissociated
to PCI,
possible
'O
mm.
129
170
6-63
0-91
0-09
129
165
6-31
0-86
0-14
129
191
6-18
0-83
0-17
137
148
6-47
0-88
012
137
243
6-46
0-88
0-12
137
234
6-42
0-87
0-13
137
281
6-48
0-89
Oil
137
269
6-54
0-90
0-10
145
311
6-70
0-92
0-08
145
307
6-33
0-86
0-14
145
391
6-55
0-90
0-10
Experiments of Troost amd Hautefeuille.
Low pressures obtamed directly by a partial
1
Density of
Ratio
RiUo
Pressure of
tbe
the vapour
of the
of POI.
combined
of PCI,
dissociated
^
chloride
to POI,
possible
to PCI,
possible
o^
mm.
144-7
247
6-14
0-82
0-18
148-6
244
5-964
0-79
0-21
1501
225
6-886
0-77
0-23
154-7
221
5-619
0-72
0-29
167-6
221-8
5-415
0-67
0-33
175-8
253-7
6-235
0-62
0-30 ,
178-5
227-2
5-150
0-60
0-40
The results of Troost and Hautefeuille are
probably the best, because there is reason to
suppose that the Umit was not always reached
by Wurtz, and he had no right to treat the
vapour as accurately fulfilling the law of Boyle.
Lemoine has calculated the influence of an
excess of trichloride vapour from the experi-
ments of Wurtz and Cahours.
Hydriodic acid (Lemoine, C. R. 1875 and
1877 ; A. Oh. 1877). — Hydriodic acid was chosen
by Lemoine as the subject of an exhaus-
tive series of experiments for the following
reasons. The chemical constitution of hydriodic
acid is the simplest possible for a compound;
the products of its dissociation are gaseous at
manageable temperatures, and the thermal
changes undergone during dissociation are very
small; the velocity of the changes is large
enough to be manageable.
Veloeity of formation or decomposition of
hydriodic acid varies enormously with the tem-
perature. At 440° equilibrium is restored
almost in an hour ; at 350° days are required ;
while at 260° the period is one of months. The
decomposition of hydriodic acid at 260° appears
to be much slower than the combination of
hydrogen and iodine vapours.
Relation of free to total hydrogen at the end
of 8 hours, beginmng with (a) hydriodic acid,
(b) mixture of hydrogen and todine.
Mixture of hydrogen
and iodine
0-69
0-25
Again, the velocity depends on the pressure,
being greater the greater the pressure. Thus, at
the end of 8 hours —
At a pressure of 4 atmospheres 0-44 free,
leaving 0-56 combined.
At a pressure of 2 atmospheres 0-69 free,
leaving 0-31 combined.
At a pressure of 1 atmosphere 0-97 free,
leaving 0-03 combined.
At the end of 34 hours we shall have —
At a pressure of 4 atmospheres 0-29 free,
leaving 0-71 combined.
At a pressure of 2 atmospheres 0*48 free,
leaving 0-52 combined.
At a pressure of 1 atmosphere, 0-61 frea,
leaving 0-39 combined.
Temperatures
Hydriodic acid
350°
0-03
440°
0-22
DISSOCIATION.
401
The relation of velocity to pressure is rendered
clearer by the curves shown in figs. 9, 10, and 11.
The horizontal lines represent the time in
days. The vertical lines represent the relation
of the free hydrogen to the hydrogen introduced
(free hydrogen persisting if we begin with iodine
and hydrogen; set at liberty if we start with
hydriodic acid).
The value of the limit varies with the tem-
perature and pressure, but varies much less than
the velocity. The variation appears to be regular.
The effect of pressure is very small but real, and
more marked at high temperatures than at low
ones. Compression appears to make combina-
tion more complete. Special care was taken to
insure the attainment of the limit. A small
correction has to be made for the action on the
glass, this has been determined experimentally
and found to make the corrected value of the
limit greater than the uncorrected value : a very
curious result. The ratio of free to total hydro-
gen at 4-5 atmospheres is increased about 4 p.c,
and at 9 atmospheres about li p.c, but these
actual values can hardly be considered quite
satisfactory. The curve shown in fig. 12 indicates
the relation between the limit and the pressure.
i Sydrogen and iodme vapour heated to 440°
in variable proportions, the pressure rema/Mng
constant (Lemoine).
)uration of
Preasnre at
Batio of the
le experi-
440° of the
equivalents
Batio of free to
ment in
hydrogen
of iodine and
total hydrogen.
hours
alone
atm.
hydrogen
»
2-20
1-000
0-240
6
2-33
0-784
0-350
4
2-38
0-527
0-547
22A
2-81
0-258
0-774
26
0-37
1-360
0-124?
(Hantefeuille)
w
0-45
1-000
0-260
8
0-41
0-623
0-676t
14
0-45
0-580
0-614
94
0-46
0-561
0-600
22
0-48
0-526
0-563
22^
0-48
0-206
0-794?
t These three experiments, which lasted respeotlTely
8, 14, and 9} hours, were not ButBoiently prolonged, and
the limit was not reached.
In considering the gaseous volumes for a
point, TO, in the curve (fig. 13), jn» ia the volume
of hydrogen remaining free, mr is the volume of
Curves representing the proportion of gas remairdng free in a mixture of hydrogen oncZ iodine
vapour in equal volumes, or in hydriodie acid heated to the temperature of 360° (Lemoine).
Pressure = 4 atmospheres.
Hydrogen and iodine.
I-O-
0-8-
0-6
0-4.
0-2 .
— r-
10
ICdafi.
Fig. 9.
Pressure = 2 atmospheres.
Hydrogen and iodine (descending curve)*
Hydriodic acid (ascending curve).
10
ISdayl.
Fia. 10.
The ordinates marked by points represent
the relation of the free hydrogen to the total
hydrogen calculated when the action of the
glass is neglected; the ordinates marked by
crosses represent the same relation, taking this
action into account, for eight hours' heating.
Excess of one of the elements has the same
effect as diminishing the pressure as far as
velocity goes, that is, velocity diminishes with
an excess of either element.
The influence on the value of the limit is
much more marked. 'An excess of either element
gives stability to the compound.' This is shown
by the curve (fig. 13) and the following table :—
Tor,. II.
hydrogen combined, and consequently also the
volume of iodine vapour combined ; tiie volume
of iodine vapour introduced = Ar=r3 (since AB
is inclined at 45 degrees)^ ; toq is therefore the
volume of iodine uncombined. The ratio of the
hydriodic acid dissociated to the hydriodic acid
possible is therefore that of the lines nK[ and rq.
If all the iodine combined, the curve would be
reduced to the straight line AB. If with an in-
finitely small quantity of iodine there was no
dissociation, the curve would be tangential to AB;
this, however, does not occur.
We may take from the curve the ratio of the
hydriodic acid dissociated to the ' possible ' hy<
DD
402
DISSOCIA.TION.
driodio acid, that is to say, tHe amount of hy-
driodio acid which would be formed* were all the
iodine taken up by the hydrogen. In the case
where the temperature is 440°, and the partial
pressure of the hydrogen is 2-3 atmospheres, we
get the following :— '
Batlo of the nmnber
Batio of HI dis-
Ratio of HI per-
of equivalents of
sociated to HI
sistent to HI
Iodine and hydrogen
possible
possible
1-OOOH + I
0-24
0-76
1-000H + 0-7841
0-17
0-83
1-000H + 0-5271
0-14
0-86
1-000H + 0-2581
• 0-12
0-88
Again, if we cause 1 equivalent of iodine to
aot respectively on 1, 2, 3, &o., equivalents of
alter the velocity enormously, but have only a
small influence on the limit. The action of
sunliglit appears in some cases to destroy the
limit entirely, and to cause perfect combina.
tion.
Methyl ether wnd hydrochloric acid (Priedel,
C. B. 81). — When a mixture of methyl ether
and hydrochloric acid i^ passed through well-
cooled tubes a liquid is formed whose composi-
tion is variable, and may be considered to be
represented by the formula a!(OH3)jO + j/HCl.
If the gases are merely mixed a dissociable
system is obtained, behaving in many ways like
the one last considered, but differing from it in
that a contraction of volume takes place during
the combination of the ether with the hydro-
Pressure = 1 atmosphere.
Hydrogen and iodine.
1-0-
0-8-
r
0-8-
^^^...^____^
0-4-
0-3-
6
10
I
15 days.
Ecales : 0-2
mm. per hour or 4-8 mm. per day : 3 mm. for one-tenth of gas remaining tree.
Fio. 11.
Curve r^esenting the relation of the free hydrogen to the total hydrogen, that is to say the Ivmt
of decom^siUon of hydriodic acid, at 440° for different ^essures.
0-4
3 o-s
.2
S
a
S, 0-2
0-1-
0 I 2 3 4 R 0 atmospbeio.
Pressures.
Scales : 10 mm. for one atmosphere, and 10 mm, for 01 of hydrlodifc icid decomposed.
Fia. 12.
Composition of the
system introduced.
hydrogen, we get the following relations, which
may be put in a curve (fig. 14) : —
Batio of EI dls- Batlo of HI per-
Bociated to HI slstent to HI
possible , possible
H + I 0-26 0-74
2H + I 0-16 0-84
3H + I 0-13? 0-87
4H-HI 0-12 0-88
Lemoine considers it probable that an indefi-,
nite increase of one of the reacting bodies would
never tend to produce total combination of the
other. Berthelot doubts this.
Porous bodies, an/) especially platinum black,
chloric acid. This facilitates observaition, but
makes the application of theory more difficult.
The velocity of the reaction is so great as to be
unobservable.
The condensation amounts to one-half the
volume of the mixed gases.
Vapour density of oxide of methyl is
„ „ hydrochloric acid is .
„ „ compound if com-
pletely formed is .
„ (, mixture of equal vo-
lumes of methyl
oxide and ECl is
1-592
1-263
2-854
1-4^
DISSOCIATION.
403
I. Rise of temperatureincxe&Bes dissocia-
tion. Numbers are : —
Vapour density
If the combination be total . . 2'884 '
At the temperature of . 5° . 1-645
. 15° . 1-370
. 25° . 1-537
. 35° . 1-516
. 45° . 1-506
. 55° . 1-498
. 65° . 1-488
. 75° . 1-483
. 85° '. 1-474
. 95° . 1-467
If the decomposition be total . 1-430, orl-442
with the gaseous mixture employed by Frie-
del.
II. Influence of pressure.— Dissociaiion
diminishes with increasing pressure, thus : —
Vapour density
If the decomposition were total
At the pressure of 670mm. of mercury
750
850
950
1050
1100
If the combination were total
III. Influence of an inert gas, such as
air, is the same as that of a reduced pressure.
Curve representmg the ratio of free hydrogen to total hydrogen in a mixture of hydrogen and
iodine vapour heated to 440° in variable proportions.
. The TOlume of hydrogen OX = OB is constant, and in excess with respect to the iodine.
ll . .
1-430
mercury
1-537
1-548
1-565
. 1-583
1-602
1-611
2-854
1-0-
V
7*
0-8-
\
^
^
*;
0«-
5^^
^
X
0-4-
0-2 •
^^■-..^^
.t
^
B
0 0-2 p 0-4 0-e 0-8 1-0 !•«
Numbers of equivalents of Iodine for one equivalent of hydrogen.
Scales : 7-6 mm. represent 0-1 equivalent of Iodine for one equivalent of hydrogen ; 7-5 mm, represent O'l of hydrogen
remaining free for I'O of hydrogen introduced.
Xhe curve uniting the points represents the experiments at high pressures.
The crosses represent the experiments at low pressures.
Fio. 13.
Curve representmg
gaseous
able
the ratio of the hydriodio acid dissociated to the hydriodia acid jwssible in a
',, in which one egwnialent of iodine vapour is heated to d40° in presince of vari-
' of hydrogen.
0-4 ■
0-S
0-3-
__y
^
r-— ~-^___
9-1
; 1 2 3 1
Number of equivalents of hydrogen for one equivalent of iodine.
Scales : ?0 mm. for each equivalent of hydrogen : 7-5 mm. for 0-1 of hydiiodio acid dissociated.
Fja. I4f P P 8
404
DISSOCIATION.
IT. Effect of excess is the same as for hy-
driodic acid. When the temperature is about
20° and the pressure 1 atmosphere, the numbers
are the following •.' —
Excess of oxide of metbyl Contraction (with respect
(with respect to the to double the Tolume of
total TOlume of the mixture) the less abundant gas)
= 0 =5-8
0-10 7-7
0-20 8-9
0-40 10-8
0-60 11-8
Excess of hydrochloric acid
(with respect to the total
TOlume of the mixture)
=0 6-8
0-10 7-7
0-20 8-6
0-40 10-4
0-60 11-2
These may be put in a curve thus : — '
By a simple calculation the fraction of dis-
sooiation may be obtained from the vapour-
density observed. If y is the weight of compound
dissociated, and f is' the total weight per litre,
we find that the fraction V- may be calculated
P
It 2'88
from the equation i. =f-?- — li where d is the
P a
observed vapour-density. Thus the influence
of temperature is given by the numbers : —
ratio !■ dissociated at
Temperature
5°
15
25
35
45
55
65
75
85
95
dilfercut temperatiues
0-75
0-84
0-88
0-90
0-92
0-93
0-94
0-95
0-96
0-97 ^
Cv/rve representing the contraction of a mixture of hydrocJilorie acid and oxide of methyl, in
which one of the two gases is in excess.
012.
--. ^
1 8.
""^^^ ^^^
r^"
■^N. ^.'■<i \
t 6.
a
■ 1
8 S
•a
R ^
^ ^ ' i
©■e . M 0-2 0-1 0 0-1 0-2 0-4 0-8
Excess of oxide of methyl ^ Jilxcess of hydrochloric acid.
Excess in ratio of the total volume of the mixture.
Bodes : 17 mm. for a oontraotion of 10 per cent, with respect to double the volume of the less abundant gas ;
7*6 mm. for 0*1 of one of the gases in excess in a volume of the mixture equal to 1.
Fia. 15.
Cwtve re^esenting the fraction of Association ^im a mixture of hydrochlorie acid and oxide of
P
methyl, when one of the bodies is m excess.
\
l!0
h
0-8
■
r — ■— — r
4
*
1-
<0>B
1
I"
■a;ai
V-
1
■0-3
(>■« 0-« 0'4 03 0-2 O-l 0 0-1 0-2 0'3 0'4 0-5 frC
Ezoess of oxide of methyl + Excess of hydrochloric acl J.
Excess with respect to the total volume of the mixture.
SoalM : 6 mm. fot O'l of the possible combination dissooiated ; 7-6 mm. for 01 of one of the gases in excess
in a total volume of the mixture equal to 1,
Fia. 16.
DISSOCIATION.
405
The influence
of
pressure
is given by the
numbers : —
Eatio yL
p
Bame te
dissociated ali the
rressure
mperature and at
mm.
different pressures
670
0-88
750
0-86
8S0
0-84
950
0-82
1,050
0-80
1,100
0-79
When the combination takes place between
two gases, of which one is in excess, the reduc-
tion is more complicated. However, it is not
difficult, and is given by Lemoine, page 89 of
his book. The eSect of an excess expressed in
this way is given by the following numbers, and
in the curve, fig. 16 : —
Oxide of methyl in excess.
Contraotion
Excess with with respect
respect to to double the Fraction of
the total volums of Excess n dissociation
volume of the the less expressed in y
mixture abundant gas equivalents p
0 0-058 0 0-884
0-10 0-077 0-222 0-846
0-20 0-089 0-500 0-822
0-40 0-108 1-333 0-784
0-60 0-118 3-000 0-764
Hydrochhrio acid in excess.
0 0-058 0 0-884
0-10 0-077 0-222 0-846
0-20 0-086 0-500 0-828
0-40 0-104 1-333 0'792
0-60 0-112 3-000 0-776
The calculations involve an assumption ' of
the applicability of Boyle's law, which is, how-
ever, only justifiable in a limited degree, espe-
cially with respect to the ether vapour.
Amongst other dissociable systems which
have been more or less studied we may notice
Calomel, by Debray (C. R. 88, 30).
Ammomum chloride, by DeviUe (Lemons);
Pebal (A. Oh. [3] 77, 93) ; Marignao {Bl. 1867.
voL2).
Pebal's researches have been already com-
mented on.
Ammomiim sulphide. — Among others, by
Bineau (A. Oh. 70, 26); Beville and Troost
(O.B. 56, 891; 88, 1239); Horstmann {A. Svml.
1863); Salet (O. B. 86, 1080); Morteasier a.
Engel (0. B. 1879).
Chloral hydrate. — The subject of much
discussion by Troost, Wurtz, DeviLLe, Berthelot,
Naumann, &o. Bemarkable for an ingenious
test introduced by Troost to determine the
presence or absence of water-vapour, as well as
its pressure, in the vapour of chloral hydrate.
The method consists in exposing hydrated salts
of known vapour-pressure to the action of the
vapour and observing whether they become
more or less hydrated. This method, how-
ever, appears troublesome in practice, and has
hitherto led to contradictory results (v. Lemoine,
Abodes, 93).
Dissociation of salts in Bolutiou v. Solution.
Dissooiation produced by electrical agency
4 rough and provisional theory has already been
given of the action of the electrical discharge in
producing dissociation
Methods employed.
I. A series of sparks may be caused to pass
between the terminals of a eudiometer-tube
containing the gas to be experimented on. In
this case care must be taken to prevent thd
heating of the terminals, otherwise the rise of
temperature produced in their neighbourhood
will influence the effects to be observed in an
unknown manner.
U. The most powerful arrangement yet de-
vised is the apparatus of Siemens. This consists
essentially of two concentric glass tubes ; the
outer surface of the larger tube and the inner,
surface of the smaller tube are both coated with
some conducting material. The gas to be ex-
perimented on passes through the annular space
between the two glass tubes. Let the two con-
ducting surfaces be kept at difiereut potentials ;
then it can be shown that there will be an elec-
trical dist];ibution over the surfaces of discon-
tinuity of the dielectric. That is, there will be
a distribution over the inner surface of the outer
tube, and over the outer surface of the inner
tube. The difference of potential between these
two surfaces will increase as the difference of
potential between the conducting surfaces in-
creases. A point will finally be reached when
the diflerence of potential of the distribution
between the glass surfaces becomes sufficient to
produce a breaking down of the insulation of the
dielectric, and an ordinary discharge will be the
result. The electric field in the instruments
generally sold is fairly uniform,' and the apparent
electric strength of the insulating layer of gas
is proportionately large. The discharge, when
it does take place, consists of an enormous
number of smaU sparks. It is to this fact that
the efficiency of the apparatus is doubtless to
be traced.
Ozone. — The subject of many experiments.
EautefeuiUe and Chappuis (C. B. 1880) give
the following nmnbers, for the proportion of
ozone formed, as representing the limits at dif-
ferent temperatures and pressures : —
Proportion of ozone by weight.
100°
Pressure -23° 0° 20°
760 mm. 0-214 0-149 0-106
380 „ 0-204 0-152 0-125 0-0117
300 „ 0-201 0-153 0-112
225 „ 0-191 0-153 0-104 0-0118
180 „ 0-181 0-137 0-089
The slow resolution of the mixture of ozone
and oxygen produced in any of these experiments
into pure oxygen would form a convenient field
for experiments on velocity. A certain number
of such experiments has been made by Berthelot
(C. B. 1880) :—
Froportioa
of ozone
At the commencement 5*3
After 1 day ^ 2-9
2 days 2-1,
6 „ 1-2
14 „ 0-4
51 „ traces
60 ,, zero
406
DISSOCIATION.
Nitrogen and Oxygen. — May be caused to
combine under the influence of the electric
spark. This experiment is chiefly interesting
historically.
Nitrogen. — It has already been pointed out
that the efficiency of the spark in producing
dissociation of an observable character will de-
pend greatly on the form of the discharge. This
is a very obscure subject and cannot be treated
here. The reader is recommended to consult
a paper by J. 3. Thomson on the electric dis-
charge in gases (P. M. 1883). It is there shown
that the pressure must exercise a very important
influence on the phenomena to be observed.
At pressures of about 0-8 mm. a discharge of
a peculiar kind obtained from an induction coil
by inserting a large resistance in the circuit was
observed by Thomson and Threlfall (Pr. 1886)
to produce a contraction in an atmosphere of
pure nitrogen. On heating the resulting gas
the original volume was recovered. This effect
probably points to the production of an aUotropic
form of nitrogen.
Ammonia forms a dissociable system : the
limit is here very high : that is the ammonia
may be almost completely decomposed. On the
other hand, of course only a very slight combi-
nation is produced if we start from nitrogen and
hydrogen, though this may be made indefinitely
great by removing the ammonia formed. Some
peculiar views have been put forward in this
connexion by Johnson (P. B. 1886, No. 2 ; v. also
Pamphlet, ' Elementary Nitrogen, and on the
Synthesis of Ammonia, by Johnson [Churchill,
1885]).
Carbon dioxide is decomposable with a very
low limit. If a bit of phosphorus be placed
in the tube to absorb the oxygen as fast as it is
formed the reaction becomes unlimited. The
inverse case of carbonic oxide and oxygen is
curious. Theoretically, from the experiments
on carbon dioxide, combination should take place
easily, or rather the limit should be high. How-
ever, in an experiment continued- for six hours
very little carbon dioxide was produced, if any.
This may be accounted for if we assume the
velocity of the reaction to be extremely slow,
though there is no other reason for such an as-
sumption.
Water-vapoii/r, decomposed with difficulty.
Acetylene. — ^As the products of decompo-
sition are liquid the reaction is unlimited. If
the sparks are large, carbon is deposited and the
reaction goes on till the gas consists of about
seven volumes of hydrogen to one of acetylene.
In this case there is an approximate limit.
Berthelot has examined its relation to the pres-
sure, and gives the following numbers :—
Pressure in ^
metres
of mercury
3-46
0-76
0-42
0-41
0-31
0-23
0-18
010
Limiting proportion
of acetylene
per 100 volumes
11-9
120 to 12-5
11-9
120
~6^
3-5
31
31
It will be noticed that the relation is not con-
tinuous, this is probably to be traced to the fact
that the products of decomposition depend on the
kind of spark employed, and this is itself con-
ditioned by the pressure of the gas.
Syirocyamc acid. — This is formed from
acetylene and hydrogen by the action of the
spark. The reaction is complicated by the
production of other and more complex sub-
stances.
Theories of SisBOoiation,
A. Theories which endeavour to account for
the phenomena of dissociation and give results,
numerically comparable with experiment, based
on the principle of the action of mass ; Lemoine,
Guldberg a. Waage, Van 't Hoff.
B. Theories based on the kinetic theory of
gases ; Clausius and Lemoine.
C. Theories based on the generalisation of
the principles of thermodynamics ; Willard
Gibbs, Horstmann, PesUn, Van der Waals.
D. Theory based on the vortex-atoms hypo-
thesis ; J. J. Thomson.
E. Theory deduced from general equations
of dynamics ; J. J. Thomson.
Theoby ov the action of mass simpli
(Pfauudler and Lemoine). — Let two gases A and
B in a system be in circumstances permitting
combination. Let there be K molecules of
A, and N' molecules of B, in a certain closed
space. Other things being equal, the chance
of a molecule of A combining with a molecule
of B will be greater the greater the number
of molecules of B in its immediate neighbour-
hood. Similarly the chance of combination
of a molecule of B will depend on the number
of molecules of A in its immediate neighbour-
hood. If dy is the amount of combination in
time dt we shall have
||=6/(N)0(N').
If we assume that the functions are identical,
which amounts to Supposing that an excess of
either gas would have the same influence on the
result, this becomes
If the gases do not combine in equal volumes
the violent supposition is made that a combina-
tion takes place first of all by equal volumes,
and that then a further combination goes on
with the other volumes step by step. Taking the
case of a combination of one volume of A with
two of B first of all in time dt we have an amount
of compound formed given by tiie last equation,
viz.: —
%=6/(N)/(N')d«.
This then combines with another volume of
Bor
dt
= 6'/{N')/[6/(N)/(N0].
A further assumption, that the amount of
chemical change is simply proportional to the
masses in presence, reduces oar first case to
f =6NN'
DISSOCIATION.
4a7
and our second to
dt
where 5 is a constant.
This, however, except in a few oases, is found
to be insufficient to account for experimental re-
sults, and Lemoine, therefore, introduces a new
constant, thereby abandoning the theory of the
action being strictly proportional to the masses
in presence, and writes
at
snd
dy _
It'
6.N^N'=*
for the two cases respectively.
The same result may be arrived at from a
study of the kinetic theory of gases. Although
owing to the assumptions necessary no real
knowledge can be gained from the theory in
question, still it may be useful to give a sum-
mary of it here. The reader will notice the con-
fusion between atoms and molecules.
Let A and A' be two gases tending to com-
bine in equal volumes, N and N' the number of
' free molecules ' or atoms (?) per unit volume.
Let \ and \' be the mean distances of the two
kinds of molecules : then we have
Nx'= N'V»= 1.
We have to find the chance of combination
between the molecules of A and A'. To do this
Glausius assumes that two ' molecules ' will com-
bine when their centres approach to a distance
smaller than 22 where I is called the ' radius of
chemical activity ' of each molecule. The mole-
cules of both gases are supposed to be in motion
in accordance with the weU-knowu laws of the
kinetic theory, the whole of which as far as
principles go is here assumed. Instead of ex-
plicitly considering the velocities of both sys-
tems, Glausius shows that matters are simplified
if we consider the molecules of A at rest, and
the molecules of A' endowed with a velocity of
«= v + i%- if «'<'«, andM = o' + i %■ if i)'^ v;
V and v' being the velocities of mean square of
the two systems. The probability of a molecule
of A' 'penetrating the sphere of action ' of a
molecule of A during its passage between two
planes perpendicular to one another, and at a
small distance S apart, is found by Glausius to
be — S. During a time dt, however, a molecule
of A' will go over a space tidtviith respect to the
molecules of A supposed to be at rest. The
chance of combination during this time ^s there-
fore— «ii; or substituting for \*, nPudtN'S'.
\'
liherefore, the number of molecules —d!N = — dN'
combined in time dt is —NWirPtidt.
Let dy be the number of molecules of the
compound formed in time dt, then we have
^= ttZ^mNN'
dt
or oollecting constants, remembering that ' u ' is
a {auction of the temperature only,
4^= ANN'
dt
which we got before. But we know that this
formula is only ttpproximate, and therefore we
may as well admit at once that the theory ie
insufficient. At best, however, the idea of a
' radius of chemical affinity ' is only a dia-
grammatic way of regarding the process of com-
bination. If we consider the action of tempe-
rature and pressure the case is still worse,
for in default of any information at all we are
obliged to regard the radius of chemical activity
as remaining constant when the temperature
changes. This, of course, again leads to incor-
rect results, and, therefore, I is supposed to vary
in a maimer to satisfy the experiments, leaving
us exactly where we were before. Again, taking
Lemoine's form of expression involving the con-
stant P, we find that to account for the behaviour
of hydriodic acid the ' constant ' has to be made
to vary ; 'thus, at a temperature of 350° it has a
value assigned to it of "8, and at 440° it is re-
duced to '553 or '6 as seems most convenient.
Other people (Guldberg a. Waage for instance)
avoid the difficulty by putting several constants
in to begin with. We may also note the follow-
ing hints which are given us by the kinetic theory
of gases, and which do not involve any special
theory of the mechanism of chemical combina-
tion. Ghange of combination-phenomena with
change of pressure ought to be slow,since themean
distances of the molecules vary inversely as the
cube root of the pressure. Since the kinetic
theory gives a tolerably reasonable account of
the mechanical meaning of rise of temperature,
any information as to what chemical combina-
tion really is will most likely be, drawn from a
study of the dependence of chemical action on
the temperature.
The action of pressure and temperature has
been investigated by Glausius, but here again
special assumptions are made.
GuliDBERa AND WaAOE'S THZOBI OS- DISSOCIA-
TION is sufficiently indicated in the articles Affi-
nity and Chemioai. ohanoe (vol. i. ; v. especially
pp. 70, 73, 737, 746 ; v. also EQtriLiBEinM, ohe.
mcAii).
ThEOBIES BASED ON TEEBUODYNAMIO OON-
siDEBATioNS. — Certain very important ideas ay-
pear to have been put forward by Glausius in hi>I
discussion of the term 'Disgregation.' We shall
have to consider them when we come to the
formal theory of Horstmann. At present it ^rill
be more convenient to take a very simple case,
which seems first to have been deduced at some
length from Glausius' results by Feslin {A. Oh.
1871).
Feslin considers the case of carbonate of lime
and its decomposition by heat. According to
Debray the changes which take place are per-
fectly reversible, and Feslin applies the general
equation of Glausius for reversible systems to
this particular case. For information of this
general kind v. Glausius' Mechiamcal Theory
of Heat (translated by W. R. Brown), and Max-
well's Theory of Heat.
Assuming the reversibility of the reaction in
question (on which point v. stipra), 'we may
consider a reversible engine driven by the pas-
sage of heat from a mixture of carbonic acid,
carbonate of lime, and lime, in a hot vessel, to
the same mixture contained in a vessel at a
lower temperature.
408
DISSOCIATION.
Let T be the absolute temperature of the
hot vessel.
Let T — 6 be the absolute temperature of the
cold vessel.
Let u be the volume occupied by unit weight
of calcium carbonate before dissociation ; u' the
volume occupied by the same weight after dis-
sociation.
Let L be the 'latent heat ' of dissociation,
which in this case is positive ; p is the maximum
pressure of dissoci9,tion at the high temperature ;
J is the mechanical equivalent of heat.
Then «'— m is the volume developed by the
motion of the piston of the machine during
the dissociation of unit weight of substance, and
dm
j,-6 is the difference of pressure on opposite
sides of the piston.
The work done, therefore, during this pas-
sage is
(«'-«) Se.
By Carnot's principle the heat transformed
into work is
TrT-{T-0l _±T .
I'|-^'|=tI':
therefore the equation of heat transformation is
^ 'dt "S
whence
L = f(«'-.)|.
Now
«.-«=(x-^)«.= (l-^,)l±L^ ..appro.
where a is the coefficient of expansion, and this
wiU be nearly that of a perfect gas, and S^ is
the density of the carbonic acid of dissociation
reduced to 0° and pressure p^. Substituting
this value for it' — m and rearranging, we have
^^lVt^C] r <^i 1
Now — is constant ;
LS„
1-ii
is nearly so.
sufficiently nearl^r ^ot our present purpose
where we do not intend to deal with any very
great range of temperature. In fact between
1040° and 860° the expression does not change
in value more than '2 per cent.
I;E the engine works from a pressure F, to a
pressure F, we have
P.
P Pa [\ «*'''Jt, (1 + o.tf
where T, and T, correspond to Fj and F, re-
spectively.
Solving this equation
'°^'hL [r|] dw" 1^)-
Now we may get all these values from ex-
periment, and therefore choose one to calculate,
say L ; and then compare with experiment.
Feslin, however, uses a rougher method by con-
sidering the engine worked with steam, and
taking the expression 1 ^ — as the same for both
water and steam on the one hand, and carbonate
of lime and the products of its decomposition on
the other. Begnault's value for L for water at
69*1° is 558'2 cal., and the comparison will be
made at such temperatures that 69'1 is the mean
of T, =48-4; andT2 = 89-8, corresponding to the
vapour pressures P', = 85 mm. andP'2='520 mm.
This gives for the latent heat of dissociation
of carbonic acid, if A^ is the density of steam
corresponding to Z„
r 1 11
L = 558-2,
l + gj.
l + oi.
, 1 + oT,
1
1 + aT,
Putting m values, L = 666-7 ; finally comparing
this with the value deduced from Favre and
Silbermann's results, we find that it is 5 p.c.
smaller than it ought to be. Considering the
assumptions made as to the applicability of
Boyle's law, &a., this is at least as good as one
can expect, and may be taken as some evi-
dence that the dissociation process in question is
really a reversible operation. This example has
been dwelt on at more length than it intrinsically
deserves, because it affords a very iiistructive ex-
ample of the methods pursued in theories based
on thermodynamic considerations. We pass
onto
Hobstmann's theoby (^.170). — Clausius has
thrown Thomson's views on the degradation
of energy into the following form : ' The entropy
of a system will always tend towards a maxi-
mum defined by the other conditions to which
the system is exposed.'
There is no reason why this should not
apply to systems undergoing dissociation.
During dissociation some of the changes tend
to iiicrease, and some to diminish, the entropy of
the system ; according to the theory, equilibrium
will be attained when the entropy has arrived
at its maximum value, i.e. when its variation
vanishes. Clausius has introduced the term
* disgregation of a system,' and defines it as a
quantity depending on the arrangement of the
parts of a system, in so far as it is the value of
the entropy for the state of the system which it
thus defines.
' Let X be the proportion of a body expressed
in molecular weights which decomposes or com-
bines with another.' This quantity x may then
be regarded as a measure of the degree of disso-
ciation. All the other quantities which vary
during dissociation may then be regarded as
functions of x. Horstmann's condition of equi-
ps
librium is thus -=- = 0 where s is the entropy.
ax
Let Q be the quantity of heat which is concerned
in the dissociation of an amount of the body
equal to the formula weight expressed in grams ;
then Q, for instance in the cas3 of hydrochloric
acid, would be the heat required tp dissociate
36-5 grams. To produce the reaction in ques-
DISSOCIATION.
409
tion we should require Qx units of heat. If T
is the absolute temperature, and Z the disgrega-
tion of the system, we have
« = ^.Z
and the condition of equilibrium is found by
differentiation of
ixax/ dx
As an example, we may apply this equation
to the special case of a body decomposing into
two_ others. Let there be one equivalent at the
beginning of the process, and suppose there re-
mains undecomposed at the instant considered a
quantity a;, then the result is to give r molecules
of one and s of the other, and let m be the weight
of one of the substances in excess; then the
three bodies in presence are : —
r{l—x)+m
s(l-x).
If Z„ Z2, Z3 are the disgregations correspond-
ing to one equivalent of each of the three states,
we have^
Z = xZ, + [r(l-x) + m:]Z^+s(l-x)Z,. -
Suppose further that the system is one lite
carbonate of lime where one of the products is
solid and one gaseous ; then Z, and Zi S.re inde-
pendent of X, and Z, depends only on.the volume
available. It u is the volume of one equivalent
of the gas generated, Olausius gives
Z3 = Z', + AElog^
where Z', is the disgregation corresponding to
the same mass of gas reduced to standard con-
ditions, i.e. to a volume u^. E is the well-known
constant used by Clausius to express the gaseous
laws, i.e. -^a!!? where 0 = 273; and A is Joule's equi-
a
valent. If p is the pressure of the gas we have
Mp = ET.
Q in this case consists of two parts, of the heat
taken up in producing the chemical change, and
Q — 2 required to do external work, in this case
to the extent Apu or ABT.
The equation of equilibrium therefore reduces
to 2._Aiilog'i+C = 0,
if here C = Z,— rZ.^— sZj, the change of disgrega-
tion which would take place if the gas had the
volume Uf, ; this therefore is independent of x ;
u only varies as the action proceeds, and the
equation therefore expresses the fact that the
pressure must be determinate for the condition
of equilibrium.
The method has been applied by Horstmann
to calculate the pressures produced by the disso-
ciation of amylene bromide and phosphorus
pentachloride.
Phosphorus pentachloride. — The agreement
is fairly satisfactory, as may be seen by the fol-
lowing curves (fig. 17) which are given by the
theory; the points correspond to observations,
two of which are used to calculate each curve.
Lemoine has calculated the values of x by an
appropriate modification of the above equation
for hydriodic acid, and finds that the agreement
is within 5 p.c.
It may be noticed about this theory that if
the quantity of heat absorbed or given out during
the reaction was zero, the limit would be inde-
pendent of the temperature ; this actually occurs
very nearly in oases of etherification, and the
coriolusion coincides with experimental results.
A difficulty is that dissociation, according
to the theory, would go on to absolute zero,
while as a matter of fact it is generally supposed
only to begin at a certain point. As to this it
may be said that below a certain point the dis-
sociation has hitherto avoided detection.
The influence of an excess of one constituent
is extremely well and conoordantly brought out
by the theory. The influence of the pressure
will be zero as far as the limit is concerned if
no condensation or expansion occurs; as for
instance in the dissociation of hydriodic acid.
Phosphorus pentachloride (Wurtz).
~l r
ISO ISO 180 SIO 240 2r0 300
Temperatures.
Amylene bromide (Cahouis}.
No information is given by the theory as to the
progress of the reaction, i.e. we get no informa-
tion from it ss to velocity.
Thboby of Gibes (Am. 8. 18). — This theory
has many points of resemblance with that of
Horstmann, as will be seen by the following
statement of the principles : —
1. For the equilibrium of an isolated system
it is necessary and sufficient that in all the pos-
sible variations of the state of the system, the
energy being maintained constant, the variation
of the entropy shall be zero or negative. -
2. Similarly, if the entropy be constant the
variation of energy must be zero or positive il
equilibrium, is to be preserved.
Applying these principles to a mixture of
gases obeying Boyle^s law, &a., we have for the
energy of the mixture
M,(C,< + E,) + M2(Cj<-l-Ej)-H
M, and M, are the masses of the different gases.
G, and 0^ are the sp. heats at constant volume.
B, and E, are other constants, and t is the ab-
solute temperature.
410
DISSOOIATION.
Similarly the entropy is given by
M,(H, + G,log„*-o,log^)
M \
+ M2(H2 + OjlogeJ - aJt.0SY) + •"■ No-
where V is the volume, H„A„ Hj, A, are con-
stants depending on the nature of the gas such
that a, and a^ are inversely proportional to the
densities.
Gribbs assumes that these'equations wiU also
apply to a system of gases in which chemipal
change takes place. If we consider a system in
which ' the energy does not vary, and in which
the entropy has its maximum value, then we
have one case where equilibrium is established
according to the principles laid down. The con-
f'iition for maximum entropy comes to be the
condition that no variation of entropy shall occur
when the energy and volume are constants ;
these two conditions together will give the fol-
lowing : —
(H,-fl},-C,-^ + OMt - fflilog ^)<2mi
+ (H,
-flj-Oj-^^ +02log«-
t
■ aM y')^^^
+ &o.=0.
This equation leads to the result that when
the gaseous compound is capable of being formed
without condensation, the limit of dissociation will
be independent of the pressure. In other cases
the dissociation will be a functipn both of tem-
perature and pressure. Comparisons with ex-
periment in the two cases (hydriodio acid and
methyl ether and hydrochloric acid) show that
the experimental and calculated results agree
very well. A comparison with nitrogen te-
troxide, formic acid, acetic acid, and phospho-
rus chloride vapour, has been made by Gibbs ;
as an example of the agreement of theory and
experiment, we give the following table referring
to phosphorus pentachloride : —
Density
Tempe-
Pres-
Calcu-
01,- ~
Authors of the
rature
sure
lated
served
experiments
o
mm.
336
760
3610
3-656
Gahours
32r
764
3-614
3-666
300
766
3-637
3-664
jj
289
760? ,
3-666
3-69
283
763
3-659
3-67
ff
274
756
3-701
3-84
250
751
3-862
3-991
^
230
746
4-169
4-302
222
763'
4-344
4-85
Mitsclierlicli
208
760?
4-762
4-73
Cahours
200
768
6-018
4-851
jj
190
768
6-368
4-987
„
ira-B
227-2
6-063
6-160
TrooBt a. Hautef euille
176-8
253-7
6-223
6-236
,^
167-6
221-8
6-466
6-415
n
164-7
221
6-926
6-619
It
160-1
225
6-086
6-886 .
fi
U8-6
244
6-199
6-964
n
148
391
6-45
6-65
Wurtz
145
311
6-37
6-70
ji
145
307
6-36
6-33
„
144-T
247
6-287
6-14
Troost a. Hauteteuille
137
281
6-63
6-48
Wurtz
137
209
6-51
6-54
1»
137
243
6-48
6-46
n
137
234
6-47
.6-42
n
137
148
6-31
6-47
n
1S9
191
6-59
6-18
ft
129
170
6-66
6-63
tt
129
165
6-65
6-31
V
B. andL. Natanson have discussed the theory
in their paper on nitrogen tetroxide {W.A. April
1886).
If the thermal changes accompanying disso-
ciation are small, then the theory indicates that
the change of dissociation with temperature wiU
be slow. No account is taken either in this
theory or in the theory of Horstmann of the
supposed thermal change requisite before disso-
ciation begins : both theories would point to the
occurrence of dissociation down to absolute zero.
Again these theories are not in any sense
molecular. Entropy is a quantity referring to
the changes of heat into work and vice versd,
and a molecular" theory to be satisfactory must
obliterate the distinction between heat and
kinetic or potential energy.
Thboev OF J. J. Thomson (P. M. [5] 15, 427 ;
17, 233).— In this theory the views of Glausius
a. Wilhamson as to chemical combination are
expressed in terms of the vortex-ring theory of
matter. The principles and methods adopted,
however, are applicable to a»iy theory of matter,
provided only that it involves the principle of
discontinuity. The advantages of this theory
are that, while it is as general in its application
as the theories of Horstmann and Gibbs, it
affords a definitely^ mechanical view of the me-
chanism by which an equilibrium maybe brought
about. As has been pointed out several times,
any 'theory based on the kinetic theory of gases
is open to the same objection as that theory
itself, viz. that even supposing it were brought
into harmony with every conceivable experiment,
we should really be no further advanced in real
knowledge than we are at present, sinee the
assumptions on which it is based themselves
require explanation. .The vortex-ring theory,
however,'does not involve such assumption; its
premises are merely those of dynamics, and any-
thing we get from it is a real gain since it
cannot be twisted about to save appearances.
The account of the theory as given by Thom-
son is so exceedingly terse that it cannot well
be abstracted, and we therefore refer the student
to the original papers.
In the article BQurLiBEiuM, ohemioal, will
be found a treatment of dissociation-processes as
special cases of cheihical equilibrium.
E. T.
BibUography.
1. AmpAke, a. Ch. 1814 (Vapour densities).
2. AvooADBO, A. Ch. 1814 (Vapour densities).
3. Bbcquerel (a. Fbemy), A. Ch. [3] 35 (Limit
of ozone); C. B. 1877 (Vapour densities).
4. BeeiheiiOt, Essai de miccmiqm cMmAgue.
A. Ch. [5] 12, and [5] 20 (Heat of forma-
tion of chloral hydrate vapour) ; A. Ch.
1869 (Electric discharge in gases); A. Ch.
1862 a. 1863 (Etherification) ; A. Ch. [5]
17 (Amylene bromide); A. Ch. 1869 (In-
fluence of porous bodies) ; A. Ch. [5] 18.
Bl. 11, O. R. 1868 (Carbon and sulphur
compounds) ; C. B. 1880 (Iodine) ;
with PjSan de St. Gillbs, A. Ch. 1862 (on
Etherification) ;
„ Vieille, C. B. 1882 et seg. (on Dissociation
in explosions) ;
„ OoiEB, A. Ch. [5] 80 (Specific heat of
nitrogen tetro^de and acetio acid vapours).'
DISSOCIATION.
411
u. BlNBAU, Jowm. de Vlnstitut, 1848, A. Oh.
[3] 49 (Vapour densities of sulphur and
selenion) ; C. B. 1844, A. Oh. 1846 (Acetic
acid) • A. Oh. 1838 (Ammonia and car-
bonic acid); A. Oh. 1838 (Ammonium
sulphide (NH,)jS).
6. BiRNBAUM (a. Mahn), Bl. 1880 (Carbonate of
I lime).
7. BoGusKi, B. 1876, 1877 (Velocity of action of
acids on marble, &o.),
8. BoLTZMANN, W. 22, 1884 (Thermodynamioal
theory).
9. Bbodie, Calculus of Chermcal Operations,
10. BuNSBN, P. 131, A. [2] 9 (Explosions, &c.).
11. Cahoubs, 0. B. 1844 a. 1855 (Acetic acid) ;
A. Oh. [3] 20, O. B. 21, 28 (Phosphorus
pentachloride).
12. CAHiETET, 0. B. 1866, Bl. 1866 (Furnace
13. Clabsius, p. 105, Abhandlimgen Sammhing.
vol. ii. (Kinetic theory of gases) ; Mecham-
cal Theory of Heat.
14. Ceaems, O. B. 1880, Bl. 1880 (Iodine
vapour),
with Meieb, Bl. 1880, C.B. 1880 a. 1881 (Iodine
vapour) ;
15. Debeay, O. B. 1867 (Carbonate of lime) ;
O. B. 1868 (Hydrated salts) ; O. B. 1873
(Oxide of mercury and phosphorus penta-
chloride); 0. B. 1876 (Calomel).
16. DeviliiE, Lemons faits d, la sodeti chindgue
de Pwris, 1864, 0. B. 1877 (Vapour densi-
ties) -,0. B. 1862, 1868, and 1884 (Phos-
phorus pentachloride);
with Bebbay, G. B. 1878 (Oxide of iridium) ;
„ Tboost, a. Oh. 1860 (Sulphur) ; 0. B. 1863
(Ammonium sulphide) ; O. B. 1867 a. 1878
'Nitrogen tetroxide) ; C. B. 1879 a. 1880
(Chloral hydrate).
17. BiBBiTS, J. 1874 (Alkaline bicarbonates).
18. DiiTB, O. B. 1872 (Hydrogen selenida).
19. Dixon, T. 1884 (Chemical change in gases).
SO. DuHEM, J. de Ph. 1886 (Application of
Gibbs' theory).
21. Ddmas, a. Oh. 1834 (Chloral hydrate).
22. Engel (with Moitessieb), G. B. 1879 (Am-
monium sulphide) ; 0. B. 1878-1879,1880
(Chloral hydrate).
23. Favbe, 0. B. 1868, 1876, 1878 (Influence of
porous bodies) ;
with Valson, C. B. 1872 (Chrome alum).
24. Fbankiand, r.isei; O.B. 1868 (Luminosity
of flames).
25. Ebemy, v. Becquebel.
26. Fmedbi, Bl. 1875 (Oxide of methyl" and
, hydrochloric acid).
27. Gay-Ldbsac, a. Oh. 63 (Carbonate of lime).
28. Gatitieb, C. B. 1876 (Alkaline bioarbonates),
29. Gebnez, O. B. 1867 (Alkaline bicarbonates).
30. Gibbs, Am. S. 1879 (Theory).
31. Gladstone (with Teibe), Pr. 19, 0. J. 5
(Velocity of reactions, &o.).
33. Geovb, 27. 1847.
33. GuiiDBEBo a. Waaoe, Etudes sv/r les affinitis
chmdgues (published by Brogger and
Christie, Christiania, 1867) ; J. pr. 1879
(Theory).
84. Haeootibt a. Bsson, T. 1866 (Theory, &o.).
85. HAUTErEniLLB a. Chappuis, ,0. B. 1880
(Ozone). For other papers v. Tboost,
86. Hiiiowp, P. 126 (Phosphorus).
37. HoBSTMANN, A. 155, Bl. 1870, 1878 (Aoetio
acid) ; A. 1877 (Ammonia and carbonic
acid. Theory) ; A. 1863 (supplement), Bl.
1869 (Ammonium sulphide) ; A. 1873,
1877 (Theory).
38. IsAMBBET, O.B. 1878 (Dissociation of chlorine
compounds, (fee).
89. JocuN, A. Oh. 1873 (Carbonates of silver
and manganese) j A. Oh. 1881, 0. B. 1880
(Porous bodies).
40. Lecoq de BoisbatjdiSan, 0. B. 1874, 1875
(Chrome alum).
41. Lbmoine, Mudes sur les iqmlibres chimigues,
1881 (published by Dunod, 49 Quai des
Augustins) ; A. Oh. 1871 (Phosphorus.
Theory) ; 0. B. 1875 a. 1877, A. Oh. 1877
(Hydriodio acid) ; A. Oh. 1872 (Theory).
42. LiEBEN, Bl. 1865 (Vapour densities) ; 0. B,
1879 (Iodine' vapour).
43. LooKYEB, 0. B. 1873, N. 1870 et seg_. (Disso-
ciation).
44. Mabn, v. Bibnbaum.
45. Maeignao, Bl. 1867 (Ammoniuin chloride).
46. Mascabt, Bevue scientifique, 1873 (Vapow
densities).
47. Meiee, v. Cbaei'is.
48. Mbybe (Vioioe), B. 1879 a. 1880 (Vapour
densities).
49. Myebs, O.B. 1873 (Oxide of mercury); A.
1871 (Hydrogen sulphide).
50. MiCHAELis, A. 170 (Sulphur chlorides).
51. MiTSCHEELicH, P. 1833 (Nitrogen tetroxide).
52. Moitessieb (a. Engel), C. B. 1878, 1879,
1880 (Ammonium sulphide and chloral
hydrate).
53. MoNTiEE, A. Oh. 1874, O. B. 1871, 1873, 1874
(Theory).
54. MtJLLEB, A. 1862 (Nitrogen tetroxide).
55. MniB a. Wilson, Elements of Thermal
Onemistry.
56. Natanson (E. a. L.), W. 1886 (Nitrogen
tetroxide, and discussion of theory).
57. Naumanh, Qrundriss der Thermocherme, 1869,
B. 1874 (Hydrated euprio sulphate) ; B.
1878 (Nitrogen tetroxide) ; A. 1871 (Am-
monia and carbonic acid) ; B. 1876, 1879
(Chloral hydrate).
58. Ostwald, J.pr. 16 (Theory), i Also Lehrbiich
der Allgememen Chemie.
59. Pbbaii, a. Oh. [3] 67 (Ammonium chloride).
60. Peslin, a. Oh. 1871 (Theory).
61. PbaCndlbe, p. 182 (Jubelband), 131, B.
1876 (Theory).
62. Playfaib a. Wanklyn, Pr. E. 4 (Nitrogen
tetroxide an^ acetic acid).
62a. Eamsay a. Todng, T. 1886, 1887 ; P. M.
1887 ; 0. J. 1886.
63. Eaoult, 0. B. 1881 (Carbonate of lime).
64. Eobinson, v. Wanklyn.
65. BosE, P. 1839 (Ammonia and carbonic acid).
66. Salet, O. B. 1868 (Nitrogen tetroxide).
67. ScHLOEsaiNO, 0. B. 1872 (Bicarbonates of
calcium and barium). ,
68. Th&abd, O. B. 1872 (Discharge in gases).
69. Thomsbn, p. 1869, B. 1877 (Acids and bases).
70. Thomson, J. J., P. M. [5] 15, 17 (Chemical
combination in gases) ;
a. Thbeleall, Pr. 1886 (Nitrogen).
71. Teibe, v. Gladstone.
72. Tboost a. HAtriBi'EniLLE, Arm. scienHAqws
d« ViooU normale, 1873, A. Oh, "iS?*,
412
DISSOCIATION.
C. B. 1873 (Phosphorus) ; Ann. de I'dcole
sup&riewre, 1873, C. R, 1868 (Cyanogen
end cyanic acid); 0. B. 1874, A. Ch.
1874 (Metallic hydrides); C. B. 1871 a.
|.877 (Formation of compounds at high
temperatures) ; C. B. 1876 (Phosphorus
pentachloride).
Teoost, C. B. 1878 (Acetic acid) ; C. B. 1880
(Iodine); O.B.1877-1879 (Ohloralhydrate);
A. Ch. 1878 a. 1881 (Chloral hydrate).
73. Ubbain, O. B. 1876 (Alkaline bicarbonates).
74. Van deb Waals, On the Contmuity of the
Ligmd and Qaseovs States.
75. Van 't Hopf, B. 1877 (Theory).
76. ViBiLLE, C. B. 1882, 1883- e« seq. (Explosive
pressures and dissociation).
77. Vioaibb, C. B. 1868, A. Ch. 1870 (Theory).
78. Waaoe, v. Gcldbebo.
79. Wankltn (with Playtaib, v. PijAyfaib) ;
with BoBiNsoN, C. B. 66 (Sulphuric acid vapour
and phosphorus pentachloride).
80. Weinbou), p. 149, J. 1879 (Carbonate of
lime).
61. WiEDEMANii, C. B. 1878 (Dissociation of
salts) ; P. 1874 (Jubelband), J.pf. [2J 9,
(Hydrated salts) ;
with SoHULZE, W. 6 (Chloral hydrate).
82. WniiAMSoN, C. J. 4, P. M. [3] 37 (Chemical
theory).
83. WcETZ, O. B. 1865 a. 1877 (Amylene brom-
ide) ; O. B. 76, Bl. 1873 (Phosphorus
pentachloride) ; Leqons SocUti chimAgue,
1863, French Association, 1873 (Am-
monium chloride); O. B. 1877-1879
(Chloral hydrate).
DISTILLATION. The conversion of a sub-
Rtance into vapour, and the condensation of the
vapour into a liquid by cooling in another part
of the apparatus, is called distillation. It the
vapour is condensed to a solid the process is
called sublimation. The object of conducting
B distillation is usually to separate one body
from another which vapourises at a higher
temperature than the first. The name frac-
tional distillation is often Ifiven to the process
of separating two or more liquids by taking ad-
vantage of differences in their boiling points.
When a solid body is decomposed by heat, and
the products, or some of them, are condensed to
the liquid form and collected, the process is
called dry, or destmcHve, distillation ; for in-
stance, when coal is strongly heated in a closed
vessel, ammonia, various gaseous hydrocarbons,
many liquid and solid hydrocarbons, phenol, and
many other compounds, are produced.
The essential parts of all apparatus for dis-
tillation are (1) a vessel in which the substance
is heated, (2) a means for cooling the products
formed by heat, and (3) a receiver to retain the
condensed product or product^. The ordinary
form of distillation-apparatus is a flask con-
nected with a tube,, which passes inside a wider
tube through which a stream of cold water cir-
culates; a small flask or other suitable vessel is
used as a receiver. Various devices are em-
ployed in fractional distillation to insure as com-
plete a separation as possible of the more vola-
tile from the less volatile portion of the liquid
distilled.
Beferences.— The history of distillation is
fully treated in Kopp's BeitrOge der Oeschichte
der Chemie, Stiick i. 217 et seg[.i v. also E.
Wiedemann, Zeitsehr. dir deutsahm Morgen-
lUndischen Oesellschaft, 32, 575. Variqus forms
of apparatus for fractional distillation are de-
scribed by Konowalow, B. 17, 1531 ; Wurtz, A.
93, 108 ; Gliusky, A. 175, 881 ; Linnemann,
A. Ch. [3] 42, 131 ; Le Bel a. Henninger, B. 7,
1084 ; Hempel, Fr. 20, 502 ; Kreis, A. 224, 259.
Papers on the theory of fractional distillation,
with experimental results, will be found in C. J.
35, 544 (Thorpe), and 547 (Brown).
M. M. P. M.
DITA BABE. Bita, the bark of Echitei
schola/ris, a tree growing in the Philippine
Islands, contains ditaine, accompanied by two
other alkaloids, ditamine and echitenine, and by
several indifferent substances echicaoutchin,
echicerin, eohitin, echitein, ahd echiretin
(Gorup-Besanez, A. 176, 88 ; Jobst a. Hesse, A.
176, 326; 178,49; 203, 144; 11, 1546; B. 13,
1841 ; Harnaok a. Merck, B. 11, 2004 ; 13, 1648).
It is used as a febrifuge.
Ditaine GjjHjsNjO^. Echitwrmne. [206°].
[a]], = — 28-8° in a 2p.c. solution in 97 p.o. alcohol.
PrepwraUon. — Dita bark is boiled with hot
alcohol, the extract evaporated, and the residue
treated with dilute NH, and shaken out with
ether. The ether dissolves ditamine ; the residue
is treated with solid KOH and extracted with
CHCl,. The extract is evaporated and treated
with cone. HCLAq ; ditaine hydrochloride sepa-
rates while echitenine remains m solution.
Properties. — Vitreous prisms (containing
4aq). M. sol. water, CHCl,, and ether, v. sol.
alcohol, V. si. sol. benzene, insol. ligroiu.
Strongly alkaline, except after removal of all
water of crystallisation. Cone. H^SO^ dissolves
it with purple-red colour ; HNOg gives a purple-
red becoming green. Decomposes NaCl, setting
NaOH free. Kot ppd. from its salts by NH,.
After boiling with dilute HCl its solution re-
duces Fehling's solution. On evaporating an
aqueous solution of ditaine atmospheric oxi-
dation takes place with formation of 'oxydi-
taine.'
Salts. — B'HCl: crystalline, sol. water, si.
sol. HClAq and solutions of metallic chlorides,
[a]), = - 57°.— B'jHjPtCl, 3aq : yellow flocculent
pp.— B'HBr : prisms.— B'HI.—B'HjCOa l^aq :
prisms or crystalline powder. — Sulphate:
needles. — Picrate: golden flocculent pp. —
T annate: white flocculent pp. — B'^H^OgOf:
powder, si. sol. alcohol, v. e. sol. water.
Ditamine C,bH,3N0j. [75°]. Occurs in dita
bark to the extent of '04 p.c. Obtained as
above. Ammonia ppts. it from its solution in
dilute acids as amorphous flocculn. V. sol.
alcohol, ether, benzene, and CHCl,. — ^B'jHjPtClo:
pale golden flocculent pp.
Echitenine CjoHj^NO,. [above 120°]. Ex-
tracted from dita bark as above ; the solution
of its hydrochloride is ppd. by HgCl^, the pp.
decomposed by Hj,S, EOH added, and the base
extracted with chloroform. Brownish, very
bitter powder. V. sol. alcohol, si. sol. water,
chloroform, and ether, v. si. sol. ligroin. Alka-
line to litmus. Its solutions in cone. H^SO,
and HNO, are violet. Its salts are amor-
phous.— B'jHjPtClj : golden flocculent pp.—
DODECYLENE BROMIDE,
418
B'ELjHgCl, 2aq : yellow amorphous powder.
Yields trimethylamine when heated with alkalis.
Echicaontchin CjsH^Oj. A yellow resinous
body, present, according to Hesse, among the
products that may be extracted by ligroin from
dita bark, and freed from eohicerin by boiling
alcohol.
Eohicerin 0,ja,,0^. [157"]. [o]„=64<' (in
ether). Occurs in dita bark. Needles (from
alcohol) ; v. si. sol. cold alcohol, t. sol. ether,
ligroin, acetic ether, and OHCl,, insol. water,
alkalis, and ^cids. Bromine oonyerts it into
bromo-eohioerin OajH^BrOj, a white powder
[116°]. By treating a solution of eohicerin in
ligroin for two months with sodium amorphous
eohiceric acid C^oH^^O^ is said to be formed.
EohitinCj^H^^Oj. [170°]. S. -07 in 80 p.o.
alcohol at 15°; [o]d = 7S'' (in CHClj). Accdm-
panics eohicerin, from which it differs in being
less soluble in ligroin. Br gives crystalline
C,^„BrO, [100°].
Echitein O^jH^Oj. [195°]. S. •! in 80 p.c.
alcohol. [o;]d = 85° (in CHCl,), Occurs in
the mother-liquor from which the mixture of
eohicerin and eohitin has separated. Light
prismatic needles (from alcohol). Bromine gives
0,^„Br,0, [150°].
Echiretin CasHjjOj. [52°]. [o]d = 65° in a
2 p.o. ethereal solution. Occurs in the mother-
liquor from which echitein has crystallised.
Translncent mass, v. sol. ether, ligroin, and
boiling alcohol.
SITHIOITATES, salts of dithionio acid
H2S2O, ; V. under Sttlfhub, oxtacids of.
w-DODECANE 0,jHj„, [-12°]. (90°) at
10mm.; (126°) at 50 mm.; (146°) at 100 mm.;
(215°) at 760 mm. S.G. f -765; t» -755; i22
'693. Formed by reduction of launc acid or of
dodecyl alcohol with HI and F (Erafit, B. 15,
1698 ; 16, 1719) ; v. also Bbomo-dodboahb.
Sodecane C.^H;,. Dihexyl. (201°). S.O.
^ '774. Formed, together with hexane, by
treating sec-hexyl iodide with Zn and HGl or
with sodium, and by the electrolysis of potassium
heptoate (Schorlemmer, A. 161, 277 ; Wahl, B.
13, 210).
SODECENOIC ACID Oi^Jii. Amewyl-
amyl-aceUc acid. One of the substances obtained
by passing CO over a mixture of sodium acetate
and sodium isoamylate at 180° (Foetsch, A, 218,
75). Liquid.
Methyl ether UeAf. (240°-250°).
DODECINENE 0,^?- (190°-200°). From
diallyl by combination with HI and treatment of
the resulting C^H,,!! with an alloy of tin and
sodium (Wurtz, Bl. [2] 2, 164).
Dodecinene CijHjj. [o,9°]. (105°) at 15 mm.
S.G. £ -8030 ; f •7788. From di-bromo-dodecane
Ci^H^^Brj and alcoholic KOH at 150° (Krafft, B.
17, 1872).
Dodecinene G„B.^. Fossibly tri-methyl-pro-
pyl-benzene tel/rah/yd/ride. (211°). From anethol
CeH,(0Me).0,H5 and HI at 260° (Landolph, B.
9, 725).
SOSEGOIC ACII) V. Latibio acid.
DODECONENE 0,jHa,. (197° i. V.), S.G. %«
•8385. Boo 92-4(Albitzky,J.i?.16,624). From
di-methyl-allyl-oarbinol (hexenyl alcohol) and
diluted H,S0, at 100° (Nikolsky a. Saytzeff, J-ipr.
[2] 27, 380 ; 34, 475). Chromic mixture oxidises
it with formation of acetone, acetic acid, pro-
pionic acid, an acid C„H,bO„ which may be
(CH,)2C(0H).d(0H)(C0jH).C(CH,)s.CHj.C0jH,
and other bodies. Combines with bromine
HCl at 100° forms oily 0,^,01.
Dodeconene C,2H,„. (170°-180°). Fromma-
sitio ether C,jH,|,0 and ZnCl, (Baeyer, A. 140,
301).
bbdeconene OuH,,. Dvphtwyl decahydride.
(225°). From carbazole 0,^^ by treatment
with HI and F at 330° (Graebe a. Glascr, ^1.
163, 357).
w^m-DODECYL ALCOHOL C,jHjs.0H.
[24°]. (143°) at 15 mm. S.G. (Uqnid) »j* -8309 ;
*,» -8201 ; «? ^7781. Large silvery plates.
Formation. — ^Lanric aldehyde (obtained by
distilling barium laurate with barium formiate)
is reduced with zinc-dust and acetic acid.
Acetyl derivative CijHjj.OAo. ■ (151°) at 15
mm. Liquid which can be easily solidified
(Krafft, B. 16, 1718, 3018).'
Palmityl derwative O^ifit- [42°]. Large
plates.
Dodecyl alcohol OijHjsOH. (265°-275°). From
isoamyl isovalerate and sodium (Louren<;o a.
Aguiar, Z. 1870, 404).
DODECYL CHLORIDE C.^H^sCl. (0. 244°).
S.G. 2« -933. Got by chlorinating dodecane from
petroleum (Felouze a. Cahours, A. Ch. [4] 1, 5).
ra-DODECYLENE Oi^H,^ i.e.
CH3(CHj)„CH:CHj. [-31°]. (96°) at 15 mm.
S.G. 2 ^7729; V -7620; f •7511. Colourless
Uqnid. Formed oy the decomposition of dodecyl
palmitate on distillation (Erafft, B. 16, 3020;
17, 1371).
Dodecylene 0,^,. Tri4sobuiylme. (176°).
V.D. (air=l)&64. S.G. 2 -774. Tertiary butyl
iodide reacts with ZnO at 15° with separation of
water, and on fractional distillation the oily pro-
duct tri-iso-butylene is got : 6(Me,CI)+3ZnO
= 3ZnIj + 8HjO + 2C,jHji (L. Dobbin, O. J. 37,
241). It is also formed, along with di-isobutyl-.
ene, by heating a saturated solution of isobutylene
in tertiary butyl iodide with CaO at 100° (Ler-
montoff, A. 196, 116). Formed also by treating
isobutylene with ELjSOf (Goriainoff a. Batlerow,
B. 6, 661 ; A. 169, 146 ; J. B. 11, 198).
Properties. — ^Liquid. Slowly absorbs atmo-
spheric oxygen. Combines with bromine.
Chromio mixture forma tri-methyl-acetic,
methyl-di-isobutyl-acetic, and acetic acids.
Dodecylene CjjHj,. (213° cor.). S.G. 2 -836.
Got by distilling the potash-soap derived from
herring oil (Warren a. Storer, Z. 1868, 230).
Dodecylene CizHj,. (208°-215° cor.). In
petroleum from Burmah (W. a. S.).
Dodecylene C,JS^. Dihexylme. (c. 198°).
S.G. 2 ^809 ; i2 -798. Formed by the action of
H2SO4 (2pts.) and water (Ipt.) on methyl-di-
ethyl-carbinol (hexyl-alcohol) at —18° (Jawein,
A. 195, 261).
Dodecylene C,2H„. DoAeccmaphthene. (197°).
S.G. i* '806 ; 22 -801. Occurs in petroleum of
Baku (Markownikofi a. Ogloblin, J. B. 16, 338).
Dodecylene O^H,,. Dihexylene, (0. 19^°).
S.G. 2 -795 ; i2 .786. From di-methyl-ethyl-
ethylene (hexylene) and H^SO^ (Jawein, A, 196,
261).
DODECYLENE BBOMIDE V. Di-bboho-
PODBOAIHt.
414
DODEOYLENE GLYCOL.
DODECYLENE GLYCOL v. Di-oxy-dodeoakb.
DODECYLIDENE v. Dodeoinene.
POEGLIC ACID C,„H,eOp. The oWef acid
produced by the saponification of the train oil
obtained from the bottle-nosed whale found near
the Faroe Isles (Scharling, J.pr. 43, 257). Soli-
clifies a little above 0°.— BaAV— BtA'.
re-DO-ICOSANEOBiH„. [45°]. (225°) at 15mm.
S.G. w -765 ; isa -742. Formed by reduction of
the diohlorfde of the ketone obtained by distilling
a mixture of barium palmitate and heptoate
(Krafft, S. 15, 1718 ; 21, 2256). Present also in
paraffin derived from bituminous shale by dis-
tillation.
DOTEIACONTANE v. Dioetyi,.
DOUBLE SALTS. By a salt was meant in
the early days of chemistry a solid substance
e. sol. water and re-obtainable by evaporating
its aqueous solution. When the composition
and modes of formation of bodies with these
properties came to be examined, it was found
that many of them were formed by the inter-
action of an acid with an alkali, and were com-
posed of the elements of the acid and the alkali.
Hence the study of salts carried with it the
study of acids and alkalis. Acids and alkalis
were at first described as compounds with certain
characteristic properties, rather physical than
chemical (v. Acids and AleaijIs); the more
accurate study of these bodies showed that aU
acids are composed of hydrogen combined with
a strongly negative element or elements, and
that all alkalis are compounds of markedly
positive metals with hydrogen and oxygen. By
Composition of salt when
regarded as
„ J. (1) deri/vaiive of an (2) compound 0}
aiM. tworadiclm.
ENO3 K.N03(aoid = HNO,) K^O.NA
( = 2KN0,)
KjSOj K2.SO4 (aoid = H2S04) KjO.SO,
EHSO4 K.HS0,(acid = H2S0J K,0.2S03.HjO
{ = 2EB.80,)
AlPO, A1.P0, (acid = H3P04) AIA-PjO,
( = 2A1P0,).
There are many salts which cannot well be
formulated as derived from acids by replacing
hydrogen by a metal, but rather as compounds
of such salts with the oxide, or hydroxide, of
the replacing metal. As instances of these basie
salts may be mentioned Bi(N0,)|.Bi20, and
PbCjH30j.Pb{0H)j. Such salts may, however,
be formicated as compounds of two radicles,
one negative and the other positive; thus
3BiA-3NA= 2[Bi(NO,)s.Bij03],
2PbO.a2H3O.BLjO = Pb02H,O2.Pb(OH)j.
Some salts are composed of two ipetals com-
bined with an acidic radicle or radicles ; so far
as composition is concerned these double salts
may be regarded either as derived from an acid
or from two acids, by exchanging hydrogen for
two metals, or as composed of two positives
radicles combined with a negative, or with two
negative, radicles. They may also be formulated
as compounds of two salts. The following ex-
amples will illustrate these conceptions of
double salts : —
Double salt.
I. Derwative of acid or acids,
Composition of salt when regarded as
II. Composed of III. Composed of
radicUs. two salts.
AljKjS^O,, Al3Kj.4S04(acid = H2SO,) , Al2O3.KjO.4SO, Al^lSOJj.KjSO,.
MgNajCjOj MgNa3.2C03 (acid=H3C0,) MgO.Na3O.2CO, MgC03.NajC0,.
Cd(NH,),01, Cd(NHj4.601(aoid=HCl) Cd.4NH4.6Cl Cd0l3.4NH401.
HgjCaCyjClj HgjCa.CyjOlj (acids = HCy and HOI) Hgj.0a.0l2Cy, - HgCy3.CaClj.
HgAgCyjNO, ,HgAg.0yjN03 (acids = HCy and HNO3) Hg.Ag.CyjNO, Hg0y3.AgNO,.
To this class of double salts also belong compounds composed of a single metal combined with
two acidic or negative radicles, thus : —
HgjIjSO^ Hg2.l3S04(acids = H3S04andHI) Hg^.I^SO, Hglj.HgSO^.
the interaction of an acid and an alkali a salt
is formed ; the salt is not characterised by the
properties either of the acid or the alkali ; the
salt is composed of the metal of the alkali com-
bined with the more negative part of the acid.
Then it was found that salts could be formed in
, other ways than by the interaction of acid and
alkali ; but, however formed, the salt is a com-
pound of a positive element (a metal) with a
negative element or group of elements.
A salt may, then, be described either as a
derivative of an acid obtained by exchanging
the whole or a portion of the hydrogen of the acid
for metal, or as a compound of two radicles, one
positive and the other negative. If the latter form
of description is adopted, the positive radicle of
the salt may generally be regarded either as a
metal or as a group composed of a metal and
nnn-metal, the non-metal being usually oxygen,
and the negative radicle may be regarded as
either a non-metal or a group composed of
negative elements. The following formulae
represent the composition of some sftlti ; —
The most generally applicable way of looking
at double salts, when attention is paid solely to
composition, is evidently to regard them as com-
posed of two salts. AU double salts will thus
be brought within the general formula xM.ySi
where M is one salt and N another. But if the
constitution of the double salts is to be under-
stood, and the salts are to be classified, attention
must be paid not only to their composition but
also to their properties. Some double salts in-
teract with various reagents as chemical wholes ;
thus the body FeOyj.4KCy reacts with acids to
give the acid HjFeOya and a salt of K ; so also
it reacts with many metallic salts in solution to
give pps. of the composition M^jFeCyj or
M"jFeCy„ where M' is a monovalent, and M" a
divalent, metal. The double salt in question is
therefore regarded as the K salt of the acid
HjFeCyj, and its formula is written KjFeCyj, a
formula which is strictly conformable with
FeClj, Fe(N03)3, Fe2(SOJs, and other formnlffi of
simple salts. Other double salts interact with
various reagents as if the^ were composed pf two
DUALISM.
4ie
simple salts ; thus, AgCy.KCy reacts with acids
to produce HOy, a salt ol Ag, and a salt of K.
Other double salts react with some reagents in
one way, and with others in another way ; for
instance, HgCy2.2KCy is decomposed by acids
with evolution of HCy, but an aqueous solution
of this double salt reacts with lead or zinc salts
to, form a pp. of HgOyj-PbCyj or HgOyj.ZnCyj,
respectively. In the latter changes the double
salt HgCy2.2KCy reacts as if it were KjHgCy,.
A slight extension of the application of the
conception of compound radicles is probably
sufficient to bring the double salts within the
generally accepted notions of chemical constitu-
tion. If we examine a few reactions of a speci-
fied pompound, we may arrive at a conception of
its constitution which finds expression in a
structural formula representing the compound
as built up of certain radicles. But a more ex-
haustive study of the same compound may lead
to another structural formula. Thus, the f ormulsa
H.C2H,0„ O2H3O.OH, and CH3.COOH mark suc-
cessive advances in the chemical study of acetic
acid. The third formula is the best, because it
suggests more reactions than either of the others.
In the case of such a compound as acetic acid
we cannot actually build up the compound from
the radicles which we represent in the formula.
But we are generally able to build up a double
salt by bringing together two simple salts; hence
we are apt to think that the atomic complex
which forms the reacting unit of the salt must
be composed of these two radicles which have
actually been caused to combine. This may not,
however, be the proper view to take of the con-
stitution of the salt ; whether it is or is not the
proper view can be detej:mined only when an ex-
haustive study has been made of the reactions
of formation and decomposition of the com-
pound. But as most double salts have only been
superficially examined, our present conceptions
of the constitution of these bodies cannot be
regarded as final. In connexion with the subject
of double salts v. article Suts. M. M. P. M.
SBAGON'S BLOOD. A red resin. American
dragon's blood flows from incisions in Ptero-
car^iis draco growing in the West Indies. A
similar resin is obtained from Oroton draco.
Indian dragon's blood is found on the ripe fruits
and leaves of various species of Calamus. Ca-
nary dragon's blood comes from Dracmna draco.
It ^ssolves in alcohol, ether, and oils, forming
a red solution. It is partially soluble in alkalis
(Johnstone, Tr. 1839, 134; Herberger, Bmh/n.
Bepert. 37, 17 ; 40, 138). According to Dobbie
a. Henderson {Ph. [3] 14, 361) these resins may
be arranged in four groups : —
(a) Sol. CHOI3, OS2, and benzene.
(6J Sol. CHCI3, insol. CSj, and benzene.
(c) Sol. CHCI5, partly sol. CSj, sol. benzene.
{d) Insol. CHClj, CS2, and benzene.
The other properties of these resins are some-
what dissimilar : —
(a) OigHijO,. [80°]. From Calamus draco.
(6) C„H„0,. [0. 100°].
(c) OiuHisOi. [0. 80°]. From draotena.
The following properties probably relate chiefly
to the resin from Pterocarpus draco : —
On dry distillation it ^ves toluene and styren a
(Glfinard a. Boudault, O. B- 17, 503 ; 19, 505;
Blyth a. Hofmanu, A. 53, 326). Potash-fusion
forms benzoic acid, jp-oxy-benzoic acid, and
^hloroglucin (Hlasiwetz a. Barth, A. 134, 283).
Distillation with zinc-dust gives a large quantity
of styrene, together with toluene, ethyl-benzene,
and three oils, 0„H„0 (215°) V.D. 5-5, OjaHjoO
(258°) V.D. 6-96, and O.sHapOa (238°) (Botsoh, M.
1, 609).
DEUPOSE V. ScoAB.
pUALISm. As the study of chemical com-
position was developed by Lavoisier, Dalton,
Davy, Berzelius, and others, chemists gradually
drew a marked line of distinction between two
classes of compounds, those namely which when
dissolved in water had a- sour taste, dissolved
metals, corroded animal matter, and changed
the colour of some vegetable substances from
blue to red, and those whose aqueous Solution
had a soap-like action on the skin, did not dis-
solve metals, and restored the colour of the
vegetable substances which were altered by the
first class of compounds. But these two groups
of compounds comprised a minority of the bodies
which it was the business of chemistry to in-
vestigate. There were very many substances
which did not possess the characteristics of
either class ; as investigation proceeded it was
discovered that the greater number of the mem-
bers of the intermediate class could be produced
by the interaction of bodies belonging to one of
the extreme classes with bodies belonging to the
other. Compounds belonging to the first class
were called acids, the second class was named
bases or alkalis, and a compound formed by the
mutual action of an acid and a base was called a
salt.
The mode of production of salts suggested
the view that these compounds are built up of
two parts, one of which has the characters of an
acid, and the other the characters of a base.
This view was confirmed by the results of the
electro-chemical researches of Davy and Ber-
zelius. The passage of an electric current
through a salt very frequently produced one
body having the characters of an acid, and
another haying the properties of a base. Ber-
zelius supposed that every salt is essentially com-
posed of two parts, one of which is electrically
positive to the other ; in some cases each part
or radicle of a salt is itself an element, in other
cases each part is itself a group of elements.
Having expounded his view of chemical
action as an electrical phenomenon essentially
consisting in the attraction of one body, either
elementary or compound, by another with an
electrical polarity stronger than that of the
first, Berzelius proceeds thus : —
'It these electro-chemical conceptions ore just, it fol-
lows that every chemical compound is dependent on two
opposing forces, positive and negative electricity, and on
these alone ; and that every compound must be composed
ol two parts held together by their mutual electro-
chemical reactions. Therefore it follows that every com-
pound body, whatever be the number of its constituents,
can be separated into two parts, whereof one is positively
and the other negatively electrified. Thus, for eicample,
sodium sulphate is put together, not from sulphur, oxygen,
and sodium, but from sulphuric acid and soda, which again
can themselves be separated into positive and negative
constituents. So also alum cannot be regarded as im-
mediately built up from its elements, but must rather be
loolced on as the product of a reaction between sulphate of
alumina and sulphate of potash, the former acting as a
negutive, the latter as a positive element.'— JSeArlud* (1st
ed.), 3, pt, L 77.
416
DUALISM,
This ia tlie doctrine of Atialism, a, dootrine
which prevailed in chemistry for something
like half a century. As soon as a new salt was
prepared, the dualistio chemist set himself to
construct a formula which should represent the
salt as composed of t^yo parts, or radicles, one
positive and the other negative. The formula
given to the same salt was not always the same ; '
but in whatever way the formula was modified,
ill accordance with the known reactions of the
lalt, the fundamental conception of binary
structure remained. The following formnjaa,
among others, were given at difierent times to
sodium acetate — (0 = 6, 0 =8) : —
OiHsNaOs-HjO
OANaO^-Hj
(0,H.Na)0A-H20
04H,Na.04
The conception on which dualism was based,
the conception, namely, of binary structure, was
extended to acids and bases; every acid and
every base was regarded as composed of two
radicles, one of which was frequently, but not
always, an element. A complete system of
chemical classification was thus developed : one
element combines with another ; the compound
is evidently a binary one ; the compound inter-
acts with another binary compound; the pro-
duct is still binary although each part is itself
a compound; the new compound enters into'
chemical union with a compound as complex as
itself ; the product is stiU essentially built up
of twd parts. Each elementary atom was re-
garded by Berzelius as endowed with both posi-
tive and negative electricity, but one of these
predominated over the other, so that the atom,
considered as a whole, was either negatively
or positively electrified. When a positively
electrified atom combined with one which was
negatively electrified, Berzelius said that op-
posite electricities neutralised each other, but,
he added, the electricities formerly masked in
the separate atoms now come into play, so that
the new group of atoms, considered as a whole,
is either positively or negatively electrified, and
in virtue of this the new group of atoms is
ready to combine with other atoms or groups of
litems, provided, the predominating electricity
on these is of opposite sign to that on the first
group. As compounds become more complex
the less readiness do they exhibit to enter into
fresh combinations ; this was accounted for by
Berzelius as a consequence of the neutralisation
of the predominating or stronger electricities by
the first combination of the elementary atoms.
Suppose an atom to have a large charge of posi-
tive and a small charge of negative electricity,
and suppose this atom to come within the sphere
of action of another having a large charge of nega-
tive and a small charge of positiveelectricity ; these
atoms will have a great afljnity for each other —
according to the Berzelian dootrine of dualism —
they will combine, and the compound will be
either positively or negatively electrified, but the
total charge wUl be considerably smaller than
that on the original atoms.
Chemical affinity was regarded by the Ber-
zelian school as conditioned by, if not as synonym-
ous with, greater or smaller electrical charges.
Suppose that a series of binary compounds has
been produced, one of those being very stable,
another less stable, another unstable, and so on,
the ■electrical charges on ,the atoms of the most
stable compound must have been greater than
the charges on the atoms of the less stable com-
pounds ; therefore a greater qliantity of electri-
city will be required to tear asunder the atoms
which form the most stable compound than is
required to decompose an equivalent quantity of
one of the less stable compounds. But Fara-
day's researches on electrolysis showed that the
passage of the same quantity of electricity
through a series of electrol;;tic compounds of
varying chemical stability resulted in the de-
composition of chemically equivalent masses of
these compounds. This result was opposed to
the dualistic conception of affinity, and hence to
the whole system of dualism.
The researches of Liebig and Graham on the
constitution of acids gradually led chemists to
regard these bodies as essentially compounds of
hydrogen with negative elements or groups of
elements ; they came to look on the reaction be-
tween an acid and a metal as consisting in the
replacement of part, or the whole, of the hydro-
gen of the acid by the metal, and they recognised
that the hydrogen of some acids could be re-
placed by metal in two, three, or more, succes-
sive stages. An acid thus came to be regarded
as a whole, the functions of the parts of which
depend on the nature of these parts, and pro-
bably on their arrangement relatively to each
other. But the duaUstic chemist asserted that
hydrogen belongs to the class of metals, because
both are distinctly positive elements, and he
maintained that the replacement of one posi-
tively electrified atom by another positively elec-
trified atom might be expected to result in the
production of a compound resembling the ori-
ginal; the acid type is preserved, he asserted,
when a salt is formed by putting a metal in the
place of the hydrogen of an acid ; both acid and
salt are dualistic structures of the same kind.
It is impossible, asserted the follower of Berze-
lius, to replace the strongly positive hydrogen in
a compound by a distinctly negative element
without producing a compound of an entirely
different type from the acid ; a negative element,
such as chlorine, cannot, he said, be put in the
place of the positive element hydrogen ; if hy-
drogen is removed and a compound containing
chlorine is formed, this process must consist in
the breaking down of one dualistid structure and
the formation of another totally unlike the first.
But in 1839 Bumas prepared trichloracetic acid
and proved this compound to be very similar to
acetic acid, although it was produced by replacing
three atoms of hydrogen, in acetic acid by three
atoms of the markedly negative element chlorine
(0. iS. 8, 609). Dumas retained the notion of types
or families ; but he said that compounds were to
be placed in this or that family, because of their
actual reactions of formation and decomposition,
and not because a certain hypothesis required
them to be classified in a certain way.
Dualism had paid too exclusive attention to
composition; Dumas, and the founders of the
umta/ry hypothesis, maintained that no chemical
classification can be approximately final, which
does not endeavour to study the properties an
well as the compositions of the bodies to be
DULCITB.
417
olassified {v. Classifioation ; also Sai<ts, and
Types). M. M. P. M.
DTTBOISIITE. Identical with HyosoYAMnrai
(2- «•)■
DULCAMAEIN Cj,H„0,„. Occurs in the
stalks oJE the oommon nightshade, Solanum dul-
camara (Wittstein, Vierte^ahrb. f. pr. Pharm.
1, 364, 495 ; E. Geissler, Ar. Ph. [3] 7, 289).
Amorphous, with bitter taste followed by a per-
sistent sweet taste. Sol. alcohol and acetic
ether. Basio lead acetate ppts. C22H32PbO,g 3aq
and CjsHj^PbOio 5aq. Dilute acids resolve it into
glucose and resinous dulcamaretin 0,eELfi„
DULCITE OeHijO, i.e.
CHj(OH).(CH.OH),.OHjOH. Melampynte. Mol.
w. 182. [189°]. S.G.i^ 1-466. S. 3 at 15°. S.
(alcohol) -07 at 15°. H.F. 294,000 (v. Keohen-
berg) ; 317,600 (Berthelot a. VieiUe, A. Ch. [6]
10, 456; Bl. [2] 47, 868). H.C.v. 729,100;
H.O.p. 729,400 (B. a. V.).
Occurrence. — In Madagascar manna (Lau-
rent, Compt. Ohm. 1850, 364 ; 1851, 29 ; A. 76,
358 ; 80, 345 ; Jacquelain, Oorrvpt. CMm. 1851,
21 ; A. 80, 345). In Meldvipymm nemorosum
(Hunefeld, J. pr. 7, 233 ; 9, 47 ; A. 24, 241 ;
Gilmer, A. 128, 372) ; in Scrophularia nodosa
and BMnanthus Crista-galU (Eichler, Bep.
Chim. pure, 2, 103) ; and in the cambial cells of
Euomymtbs europcsus (Kubel, J. pr. 85, 372).
FormaHon. — By reducing galactose or milk
sugar with sodium amalgam (Bouchardat, A. Oh.
[4] 27, 68 ; O. B. 83, 199 ; 84, 665, 866, 1406 ;
Bl. [2] 18, 115).
Pr^araHon. — 1. From Madagascar manna
by reorystallisation.— 2. The decoction from
Mela/mpyrwm nemorosum is boiled with addition
of milk of Ume, and the solution concentrated ;
the hot solution is acidified with HGl, and on
cooling duloite crystallises out (Eichler).
ProperUes. — Glittering monochnio prisms,
nsuaUy aggregated in crusts. Slightly sweet in
taste. Inactive. SI. sol. acetone, chloroform,
and acetic ether, insol. ether. It does not reduce
Fehling's solution. Does not undergo alcoholic
fermentation. At 200° it loses water, becoming
duloitan CjHuOs, a thick syrup. Duloite is
neutral to litmus, but accorditig to Klein (C. B.
99, 144) a solution of duloite (1 mol.) mixed with
borax (^ mol.) is acid. Sodium paratuugstate
acts like borax.
BeacUons. — 1. Boiling dilute nitric acid
forms mucic, raoemio, and oxalic acids (Laurent;
Carlet, 0. B. 51, 137 ; 53, 343). Fuming HNO,
forms the hexanitrate. — 2. H2S04 forms a penta-
Bulphurio acid. — 3. HI forms secondary hexyl
iodide (Erlenmeyer a. Wanklyn, O. J. 15, 455) —
4. Cone. HClAq at 0° forms unstable crystals of
CeH,.0^C13aq (Bouchardat, A. Ch. [4] 27,
168).— 0. HClAq at 100° slowly forms the
dichlorhydrin C8H,2Cl204. This forms tables,
insol. water and alcohol ; it is split up at 180°,
or by boiling water, into HCl and dulcitan
chlcrhydrin CsHjiClO,, which crystallises
from ether in needles [90°], and is partially
converted by boiling water into dulcitan. The
dichlorhydrin is converted by alcoholic NH, into
durloitamine CsHisNO^, a strongly alkaline
syrup which absorbs 00^ from the air and forms
a crystalline hydrochloride B'HCl and platino-
ohloride B'jHJPtCl,. Sodium amalgam converts
dnlcitediohlorhydnnintogummyduloideC„H,jOj.
Vol. U.
Fuming HNO, gives OACyNCOj [108°].
6. HBr gives 0„H,jOeHBr3aq, C„H,jBr.^04, and
CjH„Br04 [143°] under conditions similar to
those under which the corresponding chlorine
derivatives are formed. The prolonged action
of a large excess of HBrAq at 100° forms syrupy
CjHjBrjO. Dulcitan chlorhydrin is converted
by HBrAq at 100=? into crystalline OsHijClBrO^.
Dulcite dibromhydrin is converted by fuming
HNO, into CeH»Brj(NOj), [100°]; while
OeH,,ClBr04 gives C,H8ClBr(N0,), [115°].—
7. HiAq (S.G. 2-0) at 15° forms 0„H,40sHI3aq,
which is completely resolved into its components
by water.— 8. Boiling AoCl forms CaH,01(0Ac)5,
which forms minute crystals. — 9. Ao^O forms
several acetyl derivatives («. infra). Butyric
acid at 200° gives oily di-butyryl duloitan
C„H,o(04H,0)j05-— 10- If bromme (5 g.) be added
to a solution of dulcite (5g.) in water (40 g.)
containing NajCO, (12 g.), and the product sub-
sequently tested with phenyl hydrazine, the
phenyl hydrazide OjsHj^NA [206°] of an alde-
hyde or ketone (' phenyl diUcitosazone ') sepa-
rates as yellow flakes (Fischer a. Tafel, B. 20,
8384). — 11. By heating dulcite with phenyl
cyanate there is formed OaHj(OH)(O.OO.NHPh),
[c. 252°], very sparingly soluble in all solvents
(Tessmer, B. 18, 971).
Metallic compounds. — CgHj^BaOgSaq:
prisms, v. sol. warm water. — CeHgFb,0, 3aq (at
100").— C5H80u,08 3aq (at 100°).
Hexanitrate C^^I^^O^^ Nitroduhite.
[c. 70°]. From duloite (1 pt.), fuming HNO,
(Spts.), and H2SO4 (lOpts.), the mixture being
immediately thrown into water (B^champ, 0. B.
51, 257 ; Champion, Bl. [2] 22, 179). Colourless
flexible needles (from alcohol). 'When kept for
a month at 30° to 45° it evolves red fumes,
and apparently changes to the tetranitrite
CA(0H)j(N0,)4 [130°-140°J, which crystallises
from alcohol in prisms.
Tri-sulphurio acid C8Hg(S04H)s(0H)5.
From dulcite and H^SO, (Eichler).— BajA'", :
gummy.
Penta-sulphuric acid 0eHB(S04H)5(0H).
When dulcite is added in small portions to
chlorosulphurio acid (CISO4H), and the product
is dissolved in water, a solution is obtained
whence a barium salt may be got in the form of a
hygroscopicpowder. Writing bafor^Ba,iti3either
(baS04)AH8(0H), 2aq or (baS04)5C6H„ 3aq.
The latter formula represents it as derived from
dulcitan, and, in fact, if the free acid is heated
on the water-bath dulcitan is produced (Claesson,
/.jpr. 128, 15).
Di-acetyl derivative C,Hg(OH)4(OAc)2.
[176°]. From boiling Ao^O ^12 pts.), HOAo
(120 pts.), and dulcite (10 pts.) (Bou(diardat).
Scales. SI. sol. cold water, insol. ether. A by-
product is diacetyl dulcitan CgHigAcjO,, a
bitter substance, sol. water and ether.
Penta-acetyl derivative
CsHe(OH)(OAc)s. [163° cor.]. From CsH8Cl(OAo),
by boiling with alcohol. Needles.
Hexa-acetyl derivative OjHj(OAo),.
[171° cor.]. From dulcite (Ipt.), AojO (5 pts.),
and HOAo at 185°. Hard crystalline plates;
sublimes at 210°- A by-product in its prepara-
tion is tetra-acetyl-duloitan 0,Hi,0(OAo)4.
an insupportably bitter resm.
EB
♦18
DULCHE.
Bexa-benzoyl derivative CjHj(0Bz)5.
[147°]. From dulcite (Imol.) and BzCl (8 mols.)
at 150°-200°- Crystals (from alcohol), insol.
water and ether. HNOj mixed with HjSOi con-
vert it into CeH,(O.CO.CsH4N02)a. Tetra-benzoyl-
dulcitan C,HgO(OBz)4 is a resin formed as a by-
product in preparing hexa-acetyl-dulcite.
Isoduleite CjHijO, or OuHijOs ag. Rhanmose.
[92°]. S.G. "f 1-471. S. 56-7 at 18°; 109 at
40°. '[«]], = 8'07° in a 21 p.c. aqueous solution
at 17°; [a]D = 13° in fresh solutions (Rayman
B. Kruis, O. C. 1888, 6). Prepared by the action
of dilute HjSO, upon queroitrin (the yield being
10 p.c., Hlasiwetz a. Pfaundler, A. 127, 362),
npon the glucoside of buckthorn berries {Bham-
rms infectoria) Liebermann a. Hormann, B. 11,
952 ; Berend, B. 11, 1353), and upon sophorin
(Foister, B. 15, 215). Monoclinic crystals, sol.
water and alcohol. In very dilute alcoholic
solutions it is Isvorotatory, in concentrated
alcoholic and in aqueous solution it is dextro-
rotatory. 10 c.c. of FehUng's solution, equivalent
to '05 g. glucose, are reduced by -055 g. isoduleite
(Will, B. 18, 1316). Isoduleite also reduces
ammoniacal silver nitrate, Enapp's reagent, an
alkaline solution of indigo, an alkaline solution
of KgFeCyg, and picric acid (to picramic acid).
It does not affect SchifE's reagent. H2SO4 dis-
solves it unchanged. Does not undergo alcoholic
fermentation with yeast. At 100° it gives off
H2O becoming CgHj^Oj, sometimes called iso-
dulcitan, which takes up E^O again on dis-
solving in water.
Beactions. — 1. Potash and iodine give a
very little iodoform. — 2. (a)-NaphtJwl and H^SOj
give a bluish-violet colour. — 8. Thymol and
E^SOj give a crimson zone rapidly turning
brown.— 4. Phenyl hydrazine mixture gives a
ueavy pp. CsH,„03(N,HPh)2 or 0,,n^^fi,
[171°] si. sol. water, v. sol. alcohol (Eayman,
Bl. [2] 47, 668; Herzog, M. 8, 227).— 4. Heated
with phenyl-hydrazine in alcoholic solution
it gives a phenyl-hydrazide CjjHigNjOj or
0^,A(N2HPh) [169°] V. si. sol. alcohol (Eay-
man, Bl. [2] 47, 760 ; Fischer a. Tafel, B. 20,
2566).— 5. Amixture of BLiSO, and HNO, forms a
very unstable explosive nitrate C5H3(N03)g02. —
6. Moist siVeer oxide oxidises isoduleite to acetic
acid. CrOa does the same. Bromine followed
by AgjCOj oxidises it to Cfi^fi^ [148°] ("Will a.
Peters, B. 21, 1813), or [142°] (Eayman, B. 21,
2046). This ' isoduleite saccharin ' forms needles,
v. Bol. water and alcohol, si. sol. ether ;
[o]d= -39° ; S.G. »/ 1-0325; S. 11.— 7. Aqueous
NaOH and BzCl form a crystalline mixture of
tri- and tetra-benzoyl derivatives. — 8. Ac^O at
120°-140° forms resinous acetyl derivatives.
Sodium salt C,H,2Na20e. From isodul-
eite and alcoholic NaOEt (Liebermann a. Ham-
burger, B. 12, 1186). Crystalline powder.
Isoduleite carboxylic acid C,H,40,. Lac-
tone CjHijO,. [168°]. Formed by heating iso-
duleite (25 g.) dissolved in water (25' c.c.) with
anhydrous HCy (7-5 c.c.) at 30° ; and subsequent
saponification (Fischer a. Tafel, B. 21, 1657 ;
2173). Concentrically grouped needles, v. sol.
water and alcohol, v. si. sol. ether. Eeduced by
HI and P to w-heptoic acid.
ISODTTLCITIC ACID CeB.,fi„. [100°]. Formed
by oxidising isoduleite with HNO3 (S.G. 1-33)
(MaHn, A. 145, 197). . Crystalline grains, t. sol.
water, v. si. sol. alcohol. Does not reduce Feh-
ling's solution. — CsHjPbjO,- — C^HfiiOg (at
120°). — CjHsBaOj (at 120°): white pp. —
C,HgOaO, (at 120?).
ISO-DULCITOHIC ACID OjH.A-.
Formation. — By oxidising isoduleite with bro-
mine the lactone of isodulcitonic acid is formed.
This is converted into salts of the acid by boil-
ing with the respective carbonates (Will a.
Peters, B. 21, 1814).
Properties. — The free acid is not known.
When liberated from the salts it is always the
lactone [148°] which is ppd.
DUMASIN CgH„0 (Kane) ; CjH.oO (Heintz,
P. 68, 279 ; Fittig, A. 110, 21). V.D. 5-2 (Kane).
One of the products obtained by passing ace-
tone or acetic acid through red-hot tubes (Kane,
P. 44, 494) or by the rapid distillation of ace-
tates. Oil. Lighter than water. Eesembles
mesityl oxide. Combines with NaHSOj the
crystalline compound CsH,|,ONaHSOs 2aq being
decomposed by boiling water. On distillation
with MnOj and HCl it gives C^Hfilfi (150°-
155°).
DirODECANBv. Dodecake.
DUKEKE C,„H,4 i.e. CgH2(CH3), [1:2:4:5].
g-Tetra-methyl-bemene. Mol. w. 134. [81°].
(196° i. v.).
Occvarence.—In the fraction 170°-180° of
coal-tar oils (Sohulze, B. 18, 3032 ; of. Berthe-
lot, Bl. [2] 8, 226).
Formation. — 1. From bromo-i(i-oumene [71°],
Mel, and Na (Januasch a. Fittig, Z. 1870, 161 ;
Nef, A. 237, 3 ; Gattermann, A. 244, 56).— 2.
From di-bromo-m-xylene Mel, and Na (Jan-
nasch, B. 7, 692 ; Gissmann, A. 216, 201).
Similarly from di-bromo-^j-xylene (Jannaseh, B.
10, 1357). — 3. By the action of MeOl in presence
of AljClij upon toluene, 0- or p- xylene, or
ifi-cumene (Friedel a. Crafts, A. Oh. [6] 1, 461 ;
11, 270 ; Ador a. Eilliet, B. 12, 331 ; Jacobseu,
B. 14, 2629).— 4. By the action of Mel on a
mixture of i^-oumene, CS2 and AljCl^ at 100°
(Glaus a. Foecking, B. 20, 3097).— 5. In small
quantity by passing oil of turpentine through a
red-hot tube (Montgolfier, A. Ch. [5] 19, 164).
Prcyperties. — Monoclinic crystals with faint
odour. Y. sol. alcohol, ether, and benzene, si.
sol. cold HOAo. May be sublimed.
Reactions. —1. Gives by oxidation pyromel-
litic acid C(Hj(C02H)„ tri-methyl-benzoic acid
0|jH2(CH3)3(C02H), di-methyl-benzoic acid
CsH2(OHs)2(C02H)2,andacetio acid (Eeuter.B. 11,
31).— 2. By leaving in contact with 10 times
its weight of ordinary cone. H^SO, about J of
it is converted into- a mojzo-sulphonic acid.
This sulphonic acid is very unstable, being par-
tially reconverted into dureue by cold cone.
H2SO4. By the prolonged (3 or 4 days') action
of cone. H2SO4 in the cold or for a shorter time
at 80°-100° upon dureue or its sulphonic acid a
complicated reaction takes place with produc-
tion of two pseudo-oumene-sulphonic acids
C3H2Mes(S03H)[l:3:4:5] and [1:3:4:2], a sul-
phonic acid of the (1:2:3:4) tetra-methyl-ben-
zene (prehnitene), and hexa-mpthyl-benzeno.
In this remarkable reaction the H2SO4 behaves in
a similar manner to AICI3. By the action of cold
fuming H2SO1 upon durene a disulphonio acid
is obtained which is much more stable than the
mono-sulphonic acid (Jacobsen, B. 19, 120y). —
DURENOL.
419
8. Heated with POI5 at 195" it gives a chloride
C,gE,gCl, which when treated with water at 175°
loses all its chloxine. As there is no acid
formed it is probable that this chloride contains
neither the group COlj nor the group OHClj. A
chloride C,„H„Gla may be obtained from the
ligroin which serves to purify the C,i,H,„Cli ; it
is changed by boiling water into a viscous mass,
b1. sol. ether (Colson a. Gautier, A. Ch. [6] 11,
30). — 1. Benzoyl chloride in presence of AljOlj
at 120° forms phenyl tetra-methyl-phenyl ke-
tone 0jH5.C0.0BHMe, [119°] (343°), and di-
phenyl tetra - methyl - phenylene diketone
(CbHsCOJAMsi [270°] (Friedel, Crafts, a. Ador,
O.B. 88, 880).— 5. Acetyl chloride and AiJOl,
give C,HMe4.CO.CH3 (253° uncor.) which may
be oxidised to OsHMej.CO.COjH whence sodium-
amalgam produces CjHMe4.CH(0H).C0jH [156°]
(Glaus a. Fcecking, B. 20, 3097).
M-Durene 0.hL(OH.), [1:3:4:5]. Isodurme.
(196° i. v.).
Formal^on. — 1. From bromo-mesitylene, Mel,
and sodium (Jannasch, B, 8, 356). — 2. By the
action of ZnCl, or I on camphor (Armstrong a.
MiUer, B. 16, 2259 ; Montgoiaer, A. Ch. [5] 19,
164). — 3. By treating penta-methyl-benzene with
HaSO, (Jacobsen, B. 19, 1216).— 4. From mesi-
tylene (or toluene), MeCl, and AljCl, (Jacobsen,
B. 14, 2629 ; Glaus a. Foecliing, B. 20, 8097 ;
Friedel a. Grafts, A. Ch. [6] 1, 461).
Properties. — OU. Gives on oxidation mello-
phanic acid 0,^(00^) t and three acids of the
formula C6B[j(CH3)3GO^.
c-Durene OoH^fGHs), [1:2:3:4]. Prehmtene.
[-4°]. (204° i. v.). Obtained by hydrolysis of
its sulphonio acid, which is found amongst the
products of the action of cone. H2SO4 upon s-du-
rene (Jacobsen, B. 19,1211). It appears also to
be formed by the action of Mel and sodium upon
bromo-i|'-cumene (Kelbe a. Fathe, B. 19, 1551).
Formed aJso by the action of H^SOj on penta-
methyl-benzene (Tohl, B. 21, 904). Dilute
HNO3 oxidises it to OoH2(GH3) jGO^H ;■ more ener-
getic oxidation gives prehnitio acid C5Hj(G02H)i.
The picric acid compound crystallises from
alcohol in yeUow needles [95°]. c-Durene forms
a di-bromo- derivative [210°], a nitro- derivative
[61°], and a di-nitro- derivative [178°].
T. also Bkomo-, Chloko-, and Niieo- dueenes.
Sarene dihydride 0,|,H,5. (166°). In animal
oil (Weidel a. Oiamioiau, B. 13, 73). Gives
isophthalio acid on oxidation. Successive treat-
ment with bromine and aniline converts it into
cymene. The oil appears also to contain an
iBomeride (172°).
DUEEKE CABBOXTLIC ACID v. Tetba-
UEIHYL-BENZOia ACID.
DTTBEWE SULPHONIC ACID G^BMeiiSOiB).
Obtained from Gauoasian petroleum by sulpho-
nation (MarkownikofE a. Ogloblin, A. 234, 99).
Formed, together with its chloride and di-duryl
Bulphone by treatment of powdered durene with
2J pts. of OISO3H at 0°. Grystalline boM. V.
sol. water, bui ppd. by JL^SO,. When left to
stand with HjSO, for 12 hours at 50° it is con-
verted into hexa-methyl-benzene, c-durene sulr
phonic acid, and two >)/-cumene sulphonio acids.
When distilled with dilute HjSO, hydrolysis
begins as soon as, through evaporation of water,
the temperature rises to 120° (Armstrong a. Mil-
ler, C. J. 45, 148). By fusion with KOH it gives
durenol [117°].
Salt s. — A'Na : pearly rhombic plates ; v. sol.
hot water, si. sol. cold water, nearly insol. dilute
NaOH. — A'E : thin rhombic plates, si. sol. cold
water. — A'^Ba: pp. of small scales or rhombic
plates, v. sol. hot water. — A'jCu : light blue six-
sided tables ; v. si. sol. water.
Chloride CsB.Mei{aOfil) : [99°] ; glistening
prisms ; v. e. sol. ether, si. sol. alcohol at 0°.
Amide 0,HMe4(S02NH2) : [155°]; long
prisms (from alcohol) or long slender needles
(from water) ; t. sol. hot, si. sol. cold, alcohol,
si. Bol. hot water, nearly insol. cold water (Jacob-
sen a. Schnapauff, B. 18, 2841 ; 19, 1210i.
u-Dnrene-sulphonic acid C,„H,g(S03H).
Plates. or tables containing 2aq. Prepared by
dissolving isodurene in ordinary HjS04 at 100°-
120°.
Salts. — A'Na: moderately sol. flat prisms.
— A'Kaq.— A'jBa: flat prisms, S. 57 at 15°.—
A'jGa 3aq.— A'jSr 9aq.— A'jPb 3aq.— A'jGo 7iaq.
^A' Gu. A'As.
Amide [118°] (J.); [143°3 (Kelbe a. Pathe,
B. 19, 1553). Long fine needles, v. sol. alcohol,
si. sol. hot, nearly insol. cold, water (Bielefeldt,
A. 198, 381 ; Jacobsen, B. 15, 1853).
c-Durene sulphonic acid GgHMe.,(S03H)
[1:2:3:4:?]. Prehrdtene sulphonic acid. Formed,
together with other products, by the prolonged
action of cone. HjSOj upon durene (g. v.) or its
sulphonic acid. Small needles. Sparingly soluble
in moderately dilute E2SO4.
Salts.^A'Naaq: small glistening soluble
tables. — A'jBa : small flat sparingly soluble
Amide C^BM.e^(m^SJB^) : [187°]; small
glistening prisms ; sol. hot alcohol, si. sol. cold
(Jacobsen, B. 19, 1211). The same acid ap-
pears to be formed by the Bulphonation of the
product of the action of Mel and sodium upon
bromo-i{'-cumene ; the amide of the acid so
formed melts, however, at 177° (Kelbe a. Pathe,
B. 19, 1552).
Durene - di - sulphonic acid CeMe4(S03H)2.
Prepared by dissolving powdered durene in cold
fuming sulphuric acid ; on pouring the melt
into ice and water the sulphonic acid crystallises
out. It is much more stable than the mono-sul-
phonio acid, only being hydrolised when steam
is passed through the H2SO4 solution, or when
the salts are heated to 170° with HGl.
Amide OeMe4(S02NH2)2 : [above 310°];
small glistening crystals ; si. sol. alcohol (Jacob-
sen, B. 19, 1217).
DTJEENOL G„HMe4(0H). [117°]. (250°i.V.).
Formed by fusing sodium durene sulphonate
with KOH. Large flat prisms. SubUmable and
volatile with steam. Its bromo- derivative
GgBrMe4(0H) forms long glistening prisms, ,
[118°] ; its mtro- dervuative CB(N02)Me4(OH)
yellow crystals, [130°]. By long melting with
KOH it is converted into oxy-durylio acid
CkHMe3(OH)003H [1:3:4:5:6] (Jacobsen a.
Schnapauff, B. 18, 2843).
Iso-Durenol C,2H,3.0H [108°]. Colourless
crystals. Prepared by fusing iso-durene-sul-
phonic acid with KOH (Jacobsen, B. 15, 1854).
c-Durenol C„H(CH,)4(0H) [1:2:3:4:5]. Prehn-
itol. [87°]. (266° i. v.). From c-durene sul-
phonio acid by potash-fusion (Tohl, B- 21, 904),
ssli
420
DTJKENOL.
Long silky needles (from ligroin) ; t. e. sol.
alcohol and ether. Not coloured by Fe^Clg.
Gives a bromo- derivative [151°].
Acetyl derivative 08H(CHs)4(OAc) :
[57T ; prisms.
DURIDINB C„H(CH3),(NHj). [14°]. (253°).
S.G. 24 -978. One ot the products obtained by
heating xyUdine hydrochloride with MeOH
(Hofmann, B. 17, 1913).— B'HCl (at 100°).—
B'jHjPtCls (at 100°).
Zso-Suridine OuHMe^.NHj. Amido-teira-
methyl-bensene. (250° i. V.) at 740 mm. Formed
by heating pseudooumidine or mesidine hydro-
chloride with methyl alcohol at 200°-300° (N61-
ting a. Baumann, B. 18, 1149). Colourless liquid,
which solidifies in a freezing mixture.
Salts. — B'HCl: small white prisms. —
B'2H.,CL.PtCl, : yellow tables.
AcetylderivativeGfiUo,.N'BiA.e:[2n°]i
white needles, v. sol. alcohol, si. sol. water.
DTJKOftTJINONE CaMe^Oa. [111°]. Prepared
by reducing di-nitrd-durene to durylene diamine
with zinc-dust and acetic acid, removing the zinc
by HjS, and oxidising the solution with FejClj.
Formed also by the action of warm NaOHAq
upon Me.CO.CO.Et (Pechmann, B. 21, 1420).
Long yellow needles. Sublimable. V. e. sol.
ether, chloroform, benzene, alcohol, and acetone,
V. sol. hot, but si. sol. cold, ligroin. Beduced by
zinc and HOAc to a substance [o. 210°], which
is easily reoxidised to the quinone (Nef, B. 18,
2806 ; C. /. 53, 428 ; A. 237, 5).
DTjaOYL-BENZOIC ACID v. Tetea-methyl-
BBNZOYL-BENZOIC ACID.
DITBYLIC ACID v. i('-Cuminio acid.
Quinone of durylic acid v. i|/-Ciimoquinone
CAHBOXYLIO ACID.
DUEYL METHYL KETONE
CHj.CO.CeHMe,[l:2:3:4:6]. (254°). From M-
durene, AcCl, and AlCl, (Claus a. Forsling, B.
20, 3098). Liquid. V. sol. alcohol and ether.
Oxim. [148°]. Small plates.
Phenyl hydrazide [215°]. Needles.
s-Duryl methyl ketone
■CH3.CO.C,HMe^[l:2:4:5:6]. [63°]. (251°). From
s-durene, AcCl, and AlClj (C. a. F.). Pearly
plates.
Phenyl hydrazide. Small silky crystals;
decomposing at 225°.
DI-DUSYL SUIPHONE CBHMe,.S02.CsHMe,.
Sulpho-dwride. [37°]. Formed, together with
durene sulphonic acid and its chloride, by the
action of sulphuric ohlorhydrin (2j pts.) upon
powdered durene at 0°. Long prisms. Can be
distilled in vacuo. V. sol. alcohol, ether, benzene,
and ligroin, insol. water (Jacobseu a. Schnapaufi,
B. 18, 2841).
DYNAMITE v. Glycerin.
DYS-ALBUMEH v. Peoteids.
DYSLYSIN CjjHsA. [above 140°]. A pro-
duct of the decomposition ofcholic acid obtained
either by heating it to 300° or by treating it
with dilute HCl or H^SO, (Berzelius, A. 33, 139;
43, 1; Theyer a. Sohlosser, A. 50, 235; Streoker,
A. 67, 22 ; Hoppe-Seyler, J. pr. 89, 83). Amor-
phous resin, insol. water, si. sol. boiling alcohol,
sol. ether. Insol. alkalis. Named from its in-
solubility. BoiUng alcoholic EOH reconverts it
into cholic acid.
DYSLYTE 0,HeN,Oa. [189°], S. -07 in
97 p.o. alcohol at 10°. Formed, together with
eulyte, by treating citraconio acid with cone.
HNOj (Baup, A. 81, 102 ; Bassett, Z. 1871,, 701).
Long slender needles (from alcohol). Insol.
water.
E
EASTHS. The term ea/rths is applied to the
oxides of a number of the elements which are
difficultly reducible to the metallic state. The
majority of elements of this class are of very
rare occurrence in the concentrated state, being
found accumulated in but few minerals, such,
for instance, as in gadoUnite, cerite, keilhamte,
orthite, samarskite, euxenite, and a few other
minerals. In minute quantities, however, the
earths are disseminated throughout the whole
mineral kingdom. Cossa has detected cerium
and didymium in all classes of volcanic rooks ;
certain kinds of clays contain as much as one
per cent, of cerium ; and didymium may even
be detected in sea- water by means of its absorp-
tion-spectrum. Yttria, an earth very rarely
found in quantity, may be detected in almost
every mineral species, in corals, and even in
animal bones. Samarium, an element of the
earth class, and even more rarely found in quan-
tity than yttrium, seems to have the same ubi-
quitous character, and is not unfrequently found
in appreciable traces in the minerals celestine,
stronUanite, and native carbonate of lead.
The oxides of the foUowing elements are usu-
ally classed together as earths : barium, stron.
tium, calcvwm, magnesium, berylUum, alumi-
nium, eirctmi/u/m, Uta/m/wm, tJwriwm, lanthanum,
didymium, cerium, yttrium, erbium,, terbium;
and the more recently discovered elements, about
the existence of some of which there is yet con-
siderable doubt, scandmm, ytterbiwm, dedfpium,
holmium, thuV/wm, samcurium, gadolinium, and
dysprosium.
From a chemical point of view some of these
elements exhibit characteristics so widely dif-
ferent as to render it necessary to divide them
into at least two groups ; viz., those whose salts
are not ppd. by ammonia, the hydrates being
soluble in water and possessing a strongly alka-
line reaction ; and those ppd. by ammonia. To
the first group belong barium, strontium, and
calcium, whose oxides are termed the alkaline
earths ; all the others are ppd. by ammonia.
The analogies shown by the oxides of some of
these elements vdth the oxides of the heavy and
easily reducible metals would seem to throw
them out of the list of earths ; such are mag-
nesium and beryllium; the existence of the
stable oxides MgO and BeO seems to indicate
EARTHS.
431
that these metals belong to the same group as
cadmium and zinc. The same maybe said of tho-
rium, zirconium, and titanium, which constitute
B natural group with tin, forming the oxides MOj.
As beryllium, thorium, zirconium, and titanium,
are almost invariably found associated with the
earths proper they are here retained in giving an
outline of the chemical methods of effecting the
separation of this numerous class of bodies from
@aoh other.
It is only within recent years that the list of
earths has been so much extended, and there is
every reason to believe that the number wil^ be
further increased, not so much, it may be, by
finding that rare and ill-examined minerals con-
tain new elements, as by discovering that some
of the bodies already well known are in reality
mixtures of two or more oxides ; it is, however,
to be remembered that the existence of all the
oxides of elements enumerated above is not yet
finally proved. The discoveries that have already
been made in this field have proved the hetero-
geneous character of some well-known oxides or
earths ; thib is exemplified below. This splitting
up of an earth into two or more constituents is
not to be looked upon as an act of dissociation
{q. v.), but is merely the result of more refined
methods of attacking the difficult problem of
isolating the several already known earths in a
state of purity, combined with a very close study
of variations in their spectroscopic characteristics
when the various elements are isolated from dif-
ferent mineral species. It is sufficient merely
to glance over the discoveries that have been
made relating to the earths, to understand the
difficulties under which this branch of mineral
chemistry labours, and upon what facts it is
possible to assume, with any degree of certainty,
the homogeneous or heterogeneous character of
a material. Owing to the great similarity in the
chemical reactions of many of the earths, to
isolate any particular earth is a most tedious
operation, as there are no known sharp methods,
such, for instance, as for the separation of silver
from copper, or copper from iron. When a pure
material has been prepared the further chemical
treatment of which fails to produce any variation
in the atomic weight of the element, or in the
depth of colour of the oxide, or in the intensity
of any of the bands in the absorption-spectrum
of the salts, it is assumed that the material is of
a homogeneous character. But in preparing
one particular earth it has been customary to
select gome mineral in which it predominates,
and to purify the earth from aU the others that
contaminate it in small quantity. Even then
only in one or two instances can it be asserted
that the oxide is pure ; in fact theoretical con-
siderations show that to obtain a pure material
by the methods employed is an impossibility.
For example, samaria, which is undoubtedly a
white oxide, is invariably tinted pale yellow be-
cauBe of a trace of adhering decipia, and the tint
may be diminished in depth by numberless repe-
titions of fractional precipitation ; so also yttria
is tinted pale yellow by a trace of terbia, al-
though Cldve in one instance obtained a small
quantity of a pure white colour ; gadolina, doubt-
less a white oxide, has a pale yellow colour due
to a trace of decipia ; lanthana, a white oxide,
can only with great difficulty be obtained free
from the last traces of praseodymia which colours
it grey, although the absorption-spectrum shows
no evidence of its presence. Inversely it may be
assumed that those oxides which are coloured are
more or less contaminated by the colourless ones,
as terbia with yttria, decipia with gadolina and sa-
maria, praseodymia with lanthana, and erbia with
ytterbia and scandia. The chemical history of
the earths indicates the above method of proceed-
ing to be fallacious, and would seem to show '
that the only alternative is to isolate the same
oxide from a number of different sources, and to
examine if there are any differences in the phy-
sical characters of the different specimens ; such
as in the molecular weights, the depth of colour of
the oxides, or in the iiltensity of the bands of
the absorption-spectra. The advisability of this
method is evident ; for it is highly probable that
two closely allied elements may exist in one
mineral in such quantity as to make it> appear
to be a homogeneous substance, while the same
material isolated from a different source by the
same chemical methods may consist of the two
oxides in such a totally different ratio as to show
its complex character by discrepancies in the
molecular weights, colour of the oxides, or the
intensity of the bands in' the absorption-spectra.
This has indeed been found to be the case in
several instances ; yttria was usually considered
to have a pale yellow colour, and this oxide and
erbia were the only two oxides which Bunsen and
Bahr, as well as Cldve, could isolate from gado-
limte, although Mosander had recorded the exist-
ence of a yellow or orange-coloured oxide, asso-
ciated with these two, which he named terbia.
In examining the yttria mineral samankite
found in North Carolina, L. Smith and Delafon-
taine observed that the yttria had a much deeper
yellow tint than was usually ascribed to it when
extracted from gadoUnite, and these chemists
ultimately succeeded in separating the orange-
coloured oxide terbia from the white yttria . More
recently Be Boisbaudran, examining terbia from
different sources, considers himself justified in
asserting the existence of a number of oxides
having an orange colour, showing no absorption-
spectrum, but differing in molecular weights. As
another instance : the salts of didymia obtained
from cerite show a very characteristic absorp.
tion-spectrum ; Delafontaine, when examining
the spectrum of the didymia from samarsftiie, ob-
served that the bands in the blue region of the
spectrum differed from those shown by the didy-
mia from cerite ; and De Boisbaudran, working
upon this material from sama/rskite, eliminated
the oxideof the element giving the blue bands and
gave the element the name samarium. The great
preponderance of didymia over samaria in cerite
had previously masked the existence of the latter,
whereas in sowarsftife samaria is relativelyabun
dant compared with didymia, and shows its pre-
sence at once by the absorption-spectrum. Ma-
rignac again, in examining erbia, discovered that
by many repetitions of the process of fractional
decomposition of the nitrate by fusion, the pink
material yielded a more easily decomposable salt
of a white colour, and named the oxide ytterbia ;
and Nilson, preparing this white oxide ytterbia
from erbia, found that the molecular weight dif-
fered from Marignac's material, and this he ulti-
mately found to be due to the presence of another
123
EARTHS.
white aside -wlioge nitrate ia more readily decom-
posed by heat than ytterbia ; this white oxide Nil-
son has called scandia. GUve, studying the ab-
Borption-speotra of different fractions of erbia,
concluded that this oxide ia really a mixture of
three, the true erbia, and two others which he has
called holmia and thulia. Holmia has been ex-
amined by De Boisbaudran (C. B. 102, 1003) by
fractional ppn. of the sulphate by alcohol; it ap-
pears to consist of two oxides, holmia, and one
which he names dysprosia, both showing absorp-
tion-spectra. Finally, the most striking discovery
relating to the earths is that made by Von Wels-
baoh (AT. 5, 508). This chemist has found that by
crystallising a mixture of the nitrates of didy-
mium, lanthanum, and ammonium in an acid
medium, certain double salts are formed, the frac-
tional crystallisation o( which, repeated several
hundred times, results in the separation of didy-
mium into two elements, one forming green-
coloured salts, hence named praseodymmm, and
the other forming salts of an amethyst colour ;
this second element Yon Welsbach calls neody-
mium ; these elements show absorption-spectra
of a totally different character. This is a most re-
markable discovery when it is considered how
much labour Clfeve and others have given to the
preparation of pure didymia and its salts by frac-
tional ppn. without apparently observing any
facts to indicate its complex character ; and more
particularly as one constituent gives green-
coloured salts, whereas didymium salts have
always been recorded as possessing a red or pink
colour [v. Didymium, p. 383).
The foregoing facts show how necessary it
is to isolate a particular earth from several
minerals which contain it in large as well as
small quantity, before it can be asserted to be a
homogeneous body ; and when several specimens
have been obtained, the absorption-spectra, the
atomic weights of the elements in each, and the
depth of tint of the oxides, must agree in all the
specimens. Kruss and Nilson {B. 20, 2184) have
worked upon several minerals, and in particular
upon large quantities of Fergvsomte, and from a
study of the absorption-spectra of various solu-
tions they conclude that samarium, erbium,
neodymium, praseodymium, and other bodies
showing absorption-spectra and considered to be
elementary, are in reality of a complex character
. and consist each of a large number of elements.
This result is arrived at judging only by the
variations in intensity of the absorption-bands,
but it would be premature to attach much weight
to the assertions of these chemists until fairly
pure specimens of the various bodies have been
isolated from the several sources, for it is not
improbable that in a mixture of a large number
of elements, the absorption-bands of one may
influence the intensity of those of another.
The following list of elements comprises the
metals of those earths which have as yet been
prepared in a fairly pure state, although a few
are, as aforesaid, looked upon by some chemists
as mixtures of several earths.
Aluminium Yttrium Lanthanum
Beryllium Erbium Neodymium
Zirconium Terbium Praseodymium
Thorium Holmium Samarium
Scandium Dysprosium Cerium
Ytterbium Thulium Gadolinium.
Decipium
Those elements whose salts show absorption-
spectra are erbium, holmium, dysprosium, thu-
lium, neodymium, praseodymium, and samarium.
The oxides are all white, with the exception of
erbia which is pink ; holmia and thulia, pink (?) ;
deoipia, orange,; neodymia, blue (Von Welsbach) ;
praseodymia, dark brown; ceria, pale yellow;
gadolina, white (pale yellow, Marignac) ; terbia,
orange.
The chemical methods for effecting the indi-
vidual separation of the earths are either by frac-
tional fusion of the nitrates, or fractional ppn.
with dilute ammonia; those oxides which are
ppd. by K2SO4 (v. post) are all much more basio
than those not so ppd., and the order of basicity
of the two groups is as follows, beginning with
the most basic (assuming the existence of the
bodies enumerated as distinct earths) : —
La>Prd>Nd>Sm>Gd>Dp;
and for the yttria group,
Y > Tb > ErHpTm > Yb > So.
An oxide is regarded as more or less basic than
another according as it is displaced from its salts
with more or less difficulty than the other oxide.
The relative basicities of two oxides are deter-
mined by fractionally ppg. a solution containing
salts of both oxides. Thus if an insufficiency of
a pptant. is added to a mixture of two earths in
A
solution in the ratio ^, and the pp. contains the
B
earths in the ratio ^, then A is said to be more or
b
less basic than B according as the ratio j-ia
A
<or> _ ; the less basic earth yields more easily
B I
to the pptant., the more basic resists its action
more.
In the cerite earths, decipia, being the least
basic, accumulates in the first pps. and lanthana
remains in solution ; while in the yttria group,
scandia and yttria stand at the two extremes.
The oxides ceria, thoria, zirconia, and beryUia,
as well as alumina, are easily separated by
methods other than fractional ppn. or fusion.
The sources from which the earths are ob-
tained are few. The best known mineral con-
taining these oxides, and apparently the most
abundant, is cerite, which consists largely of
ceria, with about 15 p.c. of lanthana, praseo-
dymia, and neodymia ; the amount of samaria
and decipia is small, being about three-tenths
p.c. ; gadolina only a trace ; and thereis generally
a small quantity of the yttria group of earths.
GadoUmte and euxemite are each rich in yttria,
erbia, holmia, with a small quantity of ytterbia
and scandia ; while scunarskite appears to be the
most abundant source of terbia, samaria, and
gadolina, together with much yttria.
Sepabation op the Eaeths. — Before attempt-
ing to isolate the earths individually, they are
first separated as completely as possible from the
heavy metals and the alkaline earths, and from
niobic, tautalic, and titanic acids ; fusing the
finely ground mineral, should it be a niobate or
tantalate, with KHSO4, and digesting with water,
will leave Nb^O, and TajOj insoluble ; if the
mineral is a siUcate, like cerite or gadoUmte,
HClAq or HjSO^Aq may be employed to decom-
pose it. The Cu, Bi, &o., in the solution arc
EARTHS.
423
ppd. by SHj, and ammonio oxalate ia added ; il
the oxalate is in large excess the filtrate will
contain the zireonia as well as beryllia and
alumina. The mixed oxalates are well washed,
dried, and strongly heated, and the oxides thus
formed are dissolved in HGlAq ; the evolution of
01 indicates the presence of CeO,; if the heating
has been too intense, ZrOj and ThOj remain in-
soluble The solution is ppd. by ammonia, and
boiled to separate CaO, BaO, and SrO ; the pp.
is redissolved, ppd. by oxalic acid, and the
oxaJates are heated. The colour of the strongly
heated nlaterial will now give some indication of
its character. It is invariably of a deep brown
or pale yellow colour ; the former indicates the
presence of much didymia (neodymia. and
praseodymia), and the latter tint indicates terbia,
decipia, or ceria ; the colouring materials didy-
mia, terbia, and decipia appear to be peroxides
which are reduced and become white, or green-
ish white, when gently heated in a reducing
atmosphere.
The oxides are dissolved in nitric acid ; the
solution is mixed with three or four times the
weight of the oxides of sodic nitrate, evaporated
to dryness, and the residue is subjected to gentle
fusion to decompose the eerie, thoric, and
zirconio nitrates, should these bodies be present ;
water is added and the liquid is filtered. The
spectroscope will nowreadily reveal the presence
of didymia, erbia, and such other earths as show
absorption bands ; the bands of samaria are very
faint and a somewhat cone, solution is required.
The next step in the separation of the
earths is to divide them into two groups by ppg.
the solution, either as chlorides, nitrates, or
sulphates, by KjSOj. To the nearly neutral
solution more than sufficient K^SO, is added in
fine powder to saturate the liquid, which is then
allowed to stand some hours with occasional
agitation ; the pp. that forms is filtered off and
washed several times with a saturated solution
of KjSOi, the operations being done cold. The
pp. and solution now contain the following
elements : — '
Di, La, Ce, Sm, Dp, Th, Zr, Gd;
MWate.
T, Tb, Er, Ho, Tm, Tb, So.
The pp. of Gd-salt is slightly soluble in a satu-
rated solution of KjSOj, but for the other elements
the separation is practically perfect (v. post).
Both pp. and filtrate are deopmposed with caustic
soda, the pps. are weU washed till free from
sulphates, and both are redissolved separately
in HNOjAq ; if much Ce, Zr, or Th is suspected,
the pp. from the solution is again fused with
sodic nitrate as before.
The earths Dip,, lia^O,, &o., are separated
from each other by fractional ppn. of their
nitrates by cold dilute ammonia : to the dilute
neutral solution su£Bcient ammonia is added to
ppt. a considerable portion of the whole, say
about nine-tenths ; the pp. is filtered off, re-
dissolved in nitric acid, and again ppd; in about
the same proportion as before, the operation
being repeated upon each pp. till about only
one-tenth of the original material remains. All
the filtrates are put together, and the operations
are repeated as before, bnd the final small pp. »
added to the previous one. The success of this
method of operating depends upon the slight
diSerences between the basicities of the various
earths, the least basic tending to be ppd. first,
and the most basic to remain in solution. The
basic powers are, in order of increasing magnitude
Dp<Gd<Sm<NdPrd<La; therefore the hafi,
tends to accumulate in the filtrates, and the
DpjOj, GdjOj and SmjO, in the pps. The ab-
sorption-spectrum will show that the intensity of
the Nd^O, and Prd^Oj bands becomes less, and
the colour of the oxide obtained by heating the
oxalate becomes more nearly white, in the first
filtrates as the process is repeated ; the least
basic material vnll do the same, inasmuch as
Gd,0, and SmjO, are white and Dp^O, is orange
yellow, whereas the intermediate fractions ricb
in NdjOj and PrdjO, give very strong absorption -
bands, and the strongly heated oxalates are of a
deep coffee-brown colour. The difference between
the basicity of La^O, and the other earths is
much greater than that between any of the other
two consecutive earths of the series, as Dp-Gd,
Gd-Sm, Sm-NdPrd, so that the purification
of La^Oj is easy compared with the labour re-
quiredf or the separation of the others. Assuming
that the less basic material is obtained free
from NdjOj and PrdjOj, as shown by the spectro-
scope, fractional pptn. is repeated on the material
tin the filtrates give an oxide of a white colour
consisting of Sm^O, and Gd^O,, which are
separated from each other by taking advantage
of the greater solubility of the double sulphate
of gadolinium and potassium in a cone, solu-
tion olK^SO,.
Another method of conducting the separation
of the earths consists in using a number of fiasks
in series, the central one being marked ' 0,' those
to the right marked -I- 1, -t- 2, + 3, &a., and those
to the left -1,-2,-3, <fec. The solution to be
fractionated is placed in the central flask marked
' 0,' and about one-halfof the material is ppd. ;
the pp. is dissolved and placed in —1, and the
filtrate is placed in -1-1. One half of —1 is
ppd., the pp. is dissolved and put into —2, and
the filtrate into 0; one half of +1 is thrown
down, the pp. is dissolved and placed in 0, and
the filtrate is put into -f 2. In this way the
operations are repeated till the -I- ro fiask contains
the most basic earths, and the —n flask the least
basic.
The earths not ppd. by E^^'^ii consisting of
T203,Er20s,Tb20s,&c.,are converted into nitrates
and are treated by either of two methods —
(1) by fusing the nitrates, or (2) by fractional
ppn. with dilute ammonia. The first method
would seem to be the more successful, as by its
use soandia, ytterbia, holmia, thuUa, and erbia
have been isolated. The basicities of the earths
being in the order So<Tb<Br Ho Sm<Tb<Y,
the nitrate of scandia tends to decompose at a
lower heat and more readily than the ytterbia
salt, the latter decomposes before erbia, holmia,
&e., and these decompose more readily than
yttric nitrate. Hence, if the fusion has been
carried nearly to complete decomposition, the
fused mass when treated with water will give a
solution rich in yttria and terbia, and containing
little or no scandia and ytterbia. The insoluble
material is redissolved in nitric acid, and again
434
EARTHS.
subjected to fusion as before ; the fused mass is
treated with water and filtered, the operations
being repeated very many times, as in fractional
ppn.
The methods given above for separating the
earths may be somewhat modified according as
one or other of the elements preponderates. In
working with the cerite earths the material, as
nitrates, is first mixed with sodic nitrate, and
subjected to the process of fusion to decompose
the very large amount of oeric nitrate present ;
as the amount of the yttria earths in cerite is
small, the solution from the insoluble eerie oxide
may at once be treated by fractional ppn.; the
yttria earths, being very much less basic than
La^Oj or Di^O,, collect completely with the Sm^Oa
in the first fractions, when this portion is then
separated by K^SO,. Again, in such minerals as
gadoUrvite or samarsJcite, the amount of the cerite
earths being small, fractional ppn. or fusion may
be at once resorted to with the nitrates, and the
most basic portions, containing all the La, Di,
Sm, &o., may be finally treated with KjSOj.
Several methods of limited application are
suitable for the separation of a few of the earths;
didymia, containing a trace of lanthana, may be
purified by ppn. in a strongly acid solution
(HNO,) with oxalic acid, lanthanic oxalate being
much more soluble than the didymic salt ; the
same process may be ^employed for separating
yttria from terbia, the oxalate of the former
being the more soluble ; or this separation may
be efiected by dissolving the oxides in formic acid,
and crystallising, the terbic formate being the
less soluble. Small quantities of cerium are
easily separated by ppg. with large excess of
soda, and passing chlorine through the liquid,
which leaves the CeOj insoluble.
The distinguishing characteristics of the ele-
ments scandium, ytterbium, and yttrium are their
widely different atomic weights, different spark-
spectra, and the slight differences in basicities,
these being in the order Sc<Yb<T. Erbia,
holmia, and thulia are recognised by the bands
in their absorption-spectra ; decipia and terbia
both give orange-coloured oxides, but differ
in the fact that the former is ppd. by K^SOj as
a double sulphate, while the latter is not so ppd.;
gadolina and samaria, two closely-aUied earths,
differ also in the solubility of their double sul-
phates with £2^04 ^^ ^ cone, solution of this
salt, and the former gives no absorption-
spectrum.
The earths, known as rare, resemble alumina
in being ppd. by ammonia, insoluble in excess,
but differ from alumina in being insoluble in
excess of soda or potash; they likewise resemble
CaO, SrO, and BaO in forming, with the excep-
tion of MrOj, oxalates which are insoluble in
water and oxalic acid or ammonium oxalate, but
are slightly soluble in acids ; ThO^ and ZrOj are
ppd., like AljOj, by sodium thiosulphate. The
oxides of the cerite and yttria groups are all as-
sumed to have the formula MjOg; most of them
form higher oxides by ppg. with ammonia in pre-
sence of HjOj. Our knowledge of the rare earths
is yet very incomplete. J. J. H.
EARTHS, UETALS OF THE. The term
tarths is one of those words which perpetuate
the connexion of chemistry with alchemy. The
meaning given to the term at different periods
marks the change from the vague conceptions ol
the earlier times to the more precise knowledge
regarding composition and properties which be-
longs to modern chemistry. Earth was one of
the four alchemical essences or elements. In
later times the term was applied to all bodies
which were insoluble in water and not changed
by heat. ' Terra est corpus fossile,' says Boer-
have, in his Elementa Chemia (1732), ' simplex,
durum, friabile, in igne fixum, in igne non
fluens, in aqua, alcohole, oleo, aere dissolvi non
potens.' As investigation advanced, a separation
was made between bodies which had many pro-
perties of earths and yet were soluble in water —
these were called the alkaline earths — and bodies
which were not dissolved by water. Silica,
alumina, gypsum, and ferric oxide, were taken to
be the typical earths. Lavoisier's demonstration
of the change which occurs when a metal is
burnt suggested that many earths might be
oxides of metals; Davy's discovery of sodium
and potassium marked a further step in the
acquisition of accurate knowledge of the compo-
sition of earths ; and the labours of Berzelius
and his followers completed the work which the
alchemists began.
The earths are the oxides of certain metals ;
these oxides are all insoluble, or only shghtly
soluble, in water; the oxides are reduced to
metals with difficulty. There is still difference
of opinion as to the list of metals whose oxides
are to be included in the class of earths, but the
matter is not one of great importance. The
term is used in the present article only for con-
venience' of classing together a number of ele-
ments which show distinct analogies. The
metals Al, Oa, In, Sc, Y, La, and Yb resemble
each other in so many respects that it is advi-
sable to place them in the same class ; thallium
also shows distinct analogies with Ai, Ga, and
In ; and the eight elements mentioned more or
less resemble the non-metallic element boron.
These nine elements form Group III. in the
periodic classification of the elements. This
group is divided as follows :^
Group III.
Even series
2 4 6 8 10 12
B(ll) Sc(44) Y (89) La (139) Yb (173) —
Odd series
3 5 7 9 11
Al(27) Ga (69-9) In (114) — Tl(204)
These elements are all metallic except boron;
scandium and ytterbium have not been isolated;
some of the properties of those metals of this
group which have been isolated are presented in
the table on the next page.
Chemical properties. — ;The earth-metals de-
compose water, some of them at ordinary tem-
peratures, e.g. Y and La, others at 100°, e.g. Al,
and others only at red heat, e.g. Tl. They are
all oxidised when heated in oxygen, Al and Ga
not at all readily; Tl is oxidised even by ex-
posure to air. The metals combine directly with
the halogens to form compounds MX,, and Tl
forms also the gasifiable chloride TlCl.
The well-marked oxides of the metals we are
considering belong to the form MjO,, but Tl also
forms the very characteristic oxide TljO; the
oxides MjOg are basic, Tl^O is distinctly alka>
ECGONINE.
425
ALmUNrou
Gallium
Tttbium
INDHTM
Lastuakum
T^ALLIOK
AUmui
^ wmghta
1 27-02
69-9
89-6
113^4
188-5
203-64
One or more compounds of each element, except T and La, have been gasified ;
specific heats have been directly determined, except for Y. Molecular weights
Melting
unknown.
points
700°
30°
(?)
176°
(?)
285°
Speeifie
gravities
2-8
frl
(?)
7-3
6-2
119
(approx.)
Specific
heats
•225
•08
(?)
•057
■047
•034
Occurrence
Very widely
In very small
With Sc, Tb,
In very small
With.Y.Yb,
In small
and prepa-
distributed,
quantities.
La, &c., as
quantities.
Ce, &c., as
quantities,
ration
chiefly as
as sulphide,
silicate in a
as sulphide.
siUcate in.
chiefly as se-
silicate. Ob-
insomezino
few rare
insomezino
a few rare
lenide, fair-
tained by
blendes.
Swedish
ores. Ob-
Swedish
ly widely
reducing
Obtained by
minerals.
tained by
minerals.
distributed.
Al,Cls.2NaCl
electrolysing
Obtained
reducing
Obtained
Obtained by
byNa
alkaline so-
by reducing
oxide by C
by reducing
electrolysis
lution of the
TjC1..2NaCI
orH.orppg.
La,ClebyK,
of salts in
sulphate.
by Na, or by
solutions of
or by elec-
solution; by
electrolysis.
salts by Zn.
trolysing
molten
T,aj01..2Naa
ppn. by Al
or Zn ; or
by reducing
oxide by
KCN or C.
Physieat
Tin - white,
SUver-white,
Greyish-pow-
White, very
White -grey,
Very lus-
properties
fairly hard,
fairly hard,
der (little in-
soft, lus-
fairly hard,
trous, mal-
very mal-
rather brit-
vestigated).
trous.
and ductile.
leability and
leable and
tle, very low
ductility
ductile, very
melting-
small, very
sonorous.
point.
soft.
line, forming the hydroxide TIOH, which is un-
doubtedly to be classed with the alkalis. The
most characteristic salts of the metals of the
earths belong to the form MjBX, where X= SO,,
SO,, CO,, 2N0„ 2C10s, |P0„ &o. ; Tl also forms
very characteristic salts, Tl^X, closely resembling
those of the alkali metals. The sulphates
M28SO, of the odd-seHes members of the group,
except Tl, i.e. the sulphates of Al, Ga, and In,
combine with alkali sulphates to form alums
Mj3SO,.X2SO,.24H20, where M = A1, Ga, or In,
and X= alkali metal usually K or NH,; thal-
lous sulphate Tl^SO, forms an alum in which
it takes the place of the alkali sulphate
(A]j3S04.TliSO,.24HjO). In the three elements,
Al, Ga, In, the tendency to form more than one
chloride increases as the atomic weight in-
creases, and also the tendency of the chloride
MjCl, to dissociate into MCI, increases as the
atomic weight increases. Al, Ga, and Y dissolve
in KOHAq with evolution of H ; in this respect
they show analogies with some of the non-metals.
Tl appears to form an oxide TIO^, and this oxide
seems to be acidic. The chlorides AlCl,, GaCl,,
and InOl, exist as gases at veryhigh tempera-
tures ; there is evidence of the existence as gases
of GaClj and InCL,, and possibly of InCl; TlCl
has heen gasified, but TlCl, is known only as a
solid. These data seem to indicate that the
atoms of the earth-metals are trivalent, and per-
haps also divalent, in gaseous molecules.
The investigation of the earth-metals is yet
very incomplete; so far as facts are available
one may say that Al, Ga, and In are very closely
related, that Sc, Y, La, and Yb form another
family, and that Tl shows relations with the Al
family, but is also most distinctly analogous to
the alkali metals on one hand and lead on the
other hand. Boron, which is the non-metallio
member of Group III., has already been con-
sidered (v. vol. i. p. 524). M. M. P. M.
ECEOLINE V. Ebooiikini:.
ECGONIBrE CjHuNO, i.e.
C,NH,Me.CH(OH).CHj.COjH. iKyovos, offshoot.
Tetrahydride of Tetrahydro-P-oxy-methyl-
P-pyridyl-propionie add. [198°]. Obtained,
together with benzoic acid and MeOH, by heat-
ing cocaine (CjNH,Me.CH(OBz).CHj.COsMe)
with HCl at 100° (Wohler, A. 121, 372 ; Lessen,
A. 133, 351}. Boiling baryta, acting on cocaine,
forms not only ecgonine but also ' isotropine '
CbHijNO (Calmels a. Gossin, C. B. 100, 1143).
Houoclinic prisms (containing aq) (from alco-
hol) ; a:b:e = •8136:1: •6277 ; )3 = 87° 8'. V. si. sol.
water, m. sol. alcohol, insol. ether.
Reactions. — 1. The product obtained by heat-
ing with Mel gives, after warming with silver
chloride andAg, amethylo-chloride, whence
(CjHisNOaMeC^jPtCl, may be obtained (Gintl a.
Storch, M. 8, 78).— 2. Oxidation with KMnO,
gives succinic acid (Einhorn,B.21,50). — 3. Heat-
ing with HjSO, forms an anhydride (7), whose
barium saltCigHjuBaNjOjis crystal,line (CalmeU
ECGONINE.
B. Gossin, C. B. 100, 1143).— 4. Distillation with
BaO gives methylamine.
Salts.— B'jH^tCle : [226°] ; yeUow powder,
extremely sol. water, si. sol. alcohol. When its
solution is heated there is formed B'jPtOlj as
yellowish needles, v. sol. water, nearly insol.
alcohol (C. a. G.).— B'HOl. [246°]. SI. sol.
alcohol (Liebermann, B. 21, 2351).
Benzoyl derivative CjHhOsNBz. [189°].
(M.) ; [192"] (S.) ; [195°] (L. a. G.). Formed
as a by-product in the preparation of cocaine
(Merck, B. 18, 1594). Formed also by boiling
cocaine with water for several hours (Einhorn,
B. 21, 47). Also from ecgonine and Bz^O (Iiie-
bermann a. Giesel, B. 21, 3196). Plat colour-
less prisms ; sol. water and alcohol, nearly insol.
ether. Crystallises also in prisms containing
4aq [92°] and [140°]. Decomposed by HCl into
benzoic acid and ecgonine. Partially converted
by Mel, dissolved in MeOH in presence of alkali
into cocaine, although the greater part is simply
resolved into benzoic acid and ecgonine (Skraup,
M. 6, 556 ; cf. Merck, B. 18, 2264). In the same
way, by heating benzoyl-eogonine with alkyl
iodides, the following homologues of cocaine
may be prepared, ethyl-benzoyl-ecgonine
CijHigEtNOj: [108°]; monoolinic prisms;
propyl -benzoyl -ecgonine C,8H,gPrN0,
[79°]; and isobutyl-benzoyl-eegonine
G„H„(CH„?r)N04 [62°] (Novy, Ph. [3] 18, 233).
According to Einhorn (B. 21, 3443) the first of
these homologues of cocaine is a liquid and the
second a solid [58°].
Salt of Benzoyl-ecgonine B'HAuCIj:
sparingly soluble golden leaflets.
Anhydro-ecgonine 0,H,sNO, i.e.
C5NH,Me.CH:CH.C0jH [235°]. Formed by the
action of POl^ (Merck, B. 19, 8002) or POClj
^(Einhorn, B. 20, 122l) on ecgonine. Crystals,
V. sol. water and alcohol, almost insol. other
solvents. With Br it forms OgHuBrjNOj, whose
hydrochloride CsH^BraNOaHCl melts at 184°. It
forms a perbromide [156°].
Salts.— B'HCl. [241°].— B'^jPtCl,. [223°].
— B'HAuCl,.— B'HI, [186°].— B'HBr [155°].
Ethyl derivativeCg'B.j^'EWOp Oil. Forms
. a hydrochloride [244°].— E'E^PtCls [211°].
ECHICEBIN V. DiTA Babe.
ECHITm V. DiTA Bark.
ECHITENINE v. Dita Baek.
EPFLOBESCENCE. The formation of a loose
powdery deposit on the surface of a solid body is
termed efflorescence. Some hydrated salts lose
water of crystallisation by exposure to the air,
and the surface becomes covered with a deposit
of the dehydrated salt ; crystals of Na^GOg.lOH^O,
for instance, efBoresce in this way, the surface
becoming Na2COj.5HjO. If a porous body is
filled with a salt solution, the solution -mil be
drawn by oapUlary action to the surface of the
solid, and if the body in solution crystallises on
the surface of the solid the phenomenon is called
efflorescence ; thus, the formation of nitre on
the surface of the soil, or of sodium carbonate
on walls, is an example of efdorescence. The
term is also applied to the creeping of a solution
up the sides of a vessel and dejiosition of the
dissolved body; thus, if a solution of salam-
moniac is exposed to the air, crystals are formed
where the surface of the liquid touches the sides
of the vessel ; the liquid then rises, by capillary
action, between these crystals, and more crystals
are formed above the first layer, and so on.
M. M. P. M
EGG ALBUffiEN v. Pboteids.
EIGOSANE V. IcosANE.
ELaiOMABGAEIC ACID C.jHaoOj. [48°].
Occurs as glyceride in the oil from the seeds of
Elceococca Vemicia (Cloez, C. B. 81, 469 ; 82,
501 ; 83, 943). Trimetric tables v. e. sol. ether.
Absorbs oxygen from the air, becoming resinous.
Sunlight converts the oil of Elseococca into a
solid fat, which on saponification gives elsBo-
stearic acid [72°].
ELaiOPTENE. The portion of a natural
essential oil that does not readily solidify.
ELAIDIC ACID. The solid polymeride ob-
tained by the action of nitrous acid on Oleic
AOlD {q. v.).
ELAIDIN. The solid polymeride of Olein,
V. OliEIO ACID.
ELASTIN V. Pboteids, Appendix 0.
ELATEEIN CaHjsOj. Occurs in the spurting
cucumber (Momordica Elaterium) (Zwenger, A.
43, 359 ; Morrus, A. 2, 866 ; Power, Ph. [3] 5, 645).
Hexagonal tables, insol. water, si. sol. ether, v.
sol. alcohol. Purgative. Gives a carmine colour
with phenol and H^SOj (Lindo, Fr. 17, 500 ; cf.
Johannson, Fr. 24, 156).
ELECIBOIYSIS. The separation of a com-
pound into parts effected by the passage of an
electric current. A compound which is decom-
posed by the passage through it of an electric
current is called an electrolyte ; the parts into
which it is separated are called the ions. When
different electrolytes are decomposed by a cur-
rent, the masses of the ions which carry with
them equal quantities of electricity are in the
proportion of the chemical equivalents of these
ions. Conversely the masses of several ions
which are chemically equivalent produce equal
quantities of electricity by their combination
with other ions ; thus, suppose 82-7 grams of
zinc were dissolved in sulphuric acid, 28 grams
of iron in hydrochloric acid, and 9 grams of
aluminium in potash, the quantity of electricity
set in motion by each action would be the same.
The electricity behaves as if it were divided into
atoms, one of which is attached to each mono-
valent ion, two to each divalent ion, and so on.
In some cases electrolysis proceeds as if the
mass of the electrolyte expressed by its chemical
formula were being separated into ions; in
other cases the action proceeds as if the mass of
electrolyte decomposed by the current were a
multiple of that expressed by the formula.
There are some binary compounds which are
not electrolytes, but which undergo electrolysis
when mixed with other compounds that also are
not themselves electrolytes. The application of
the facts of electrolysis to chemical processes
will be dealt vnth in the art. Fhssicad methods.
M. M. P. M.
ELEOTBONEGATIVE and ELECTBOFOSI-
TIVE. When a binary salt is electrolysed into
its elements, one of the elements separates at
the negative electrode and the other at the posi-
tive electrode ; the former element is said to be
electropositive towards the latter. An element
may be electropositive towards another element
and at the same time electronegative towards a
third element; thus in the Sectrolysis of a
ELEMENTS.
427
metallic sulphide the sulphur will separate at
the positive electrode, but in the electrolysis of
sulphur chloride the sulphur separates at the
negative electrode ; sulphur is negative towards
metals but positive towards chlorine. The terms
electropositive and negative are used in che-
mistry as practically synonymous with the terms
basylous and chlorous. The classification of
elements into positive and negative is of use,
inasmuch as with this property a number of
others are associated; thus, if we know that
an element is positive to many others we con-
clude that its chemical properties are those
characteristic of metals ; if, on the other hand,
the element is negative to a number of metals,
we conclude that its oxides will be acidic, that
it will not form salts by replacing the hydrogen
of acids, that it will possibly form a hydride,
and that generally it will be characterised by
non-metallic properties. M. M. P. M.
ELEMENTS. Although the notion of an
element or elementary body is one of the re-
motest antiquity, it has reached its present form
by a process of slow grpwth. The Aristotelian
elements — earth, water, air, and fire — represented
properties or conditions rather than actual sub-
stances ; and the same may be said of the al-
chemical elements — salt, sulphur, and mercury.
A very casual review of the older chemical
writings will show that these conceptions were
scholastic rather than scientific, and yet they
served their purpose in a primitive way and
aided to some extent in the classification of
material things. In a strictly chemical sense,
the modern idea of an element, together with its
implied distinction between elementary and com-
pound bodies, seems to have originated with
Boyle, who, in his Sceptical Chymist and other
essays, vigorously combated the earlier notions.
He taught that such substances were to be re-
garded as elementary as were not capable of
further separation, and which, being obtainable
from compounds, could yield like compounds
again. Such elements, however, he did not
specifically define, nor did he assign any positive
limit to their number.
From this point the conception of chemical
elements slowly developed, changing as the re-
sources of analysis changed, becoming more
definite with the introduction of quantitative
methods into chemistry, untU with the decom-
position of the alkalis and alkaline earths by
Davy, and the discovery of the true nature of
chlorine, it crystallised into its present form.
To-day the myriads of known substances are all
capable of ultimate analysis, and they are re-
duced at last to about sixty-nine or seventy simple
bodies, which resist all efEorts of the analyst to
decompose them further. These simple bodies,
or elements, are as follows : —
■ ■ Gold
Hydrogen
Indium
Iodine
Iridium
Iron
Lanthanum
Lead
Lithium
Magnesium
Manganese
Aluminium
Carbon
Antimony
Cerium
Arsenic
Chlorine
Barium
Chromium
Beryllium
Cobalt
Bismuth
Copper
Boron
Didymium
Bromine
Erbium
Cadmium
Fluorine
Ceesium
Gallium
Calcium
Germanium
Bubidium
Terbium
Buthenium
Thallium
Samarium
Thorium
Scandium
Tin
Selenion
Titanium
Silicon
Tungsten
Silver
Uranium
Sodium
Vanadium
Strontium
Ytterbium
Sulphur
yttrium
Tantalum
Zinc
Tellurium
Zirconium
Mercury
Molybdenum
Nickel
Niobium
Nitrogen
Osmium
Oxygen
Palladium
Phosphorus
Platinum
Potassium
Bhodium
To these may perhaps be added a few which
are still doubtful, such as norwegium, holmium,
thulium, (fee, and some which are but dimly
recognised as present in the cerite and gadolinite
earths. It is also probable that some of those
in the list are really not elementary substances,
e.g. didymium.
Upon comparison, these elements are found to
fall into well-marked natural groups, the mem-
bers of each group showing close kinship, both
as regards themselves and their compounds. At
first the classification of the elements was super-
ficial and tentative, being based upon partial
resemblances; and even the broad division of
them into metals and non-metals was far from
being satisfactory. To the earher chemists
nitrogen and bismuth had nothing in common,
carbon and tin were totally unlike, while vana-
dium and chromium were classed together, and
so too were tellurium and antimony. But by
means of the hypothesis of valency a clearer
insight was gained into the true relationships of
the elements, and in the announcement of the
periodic law (q.v.) by Newland, Mendelejeff, and
Lothar Meyer, their orderly sequence was at last
definitely perceived. To-day all classification of
the elements is based primarily upon that law,
and illustrates chemical function rather than
external properties. The former is fundamental,
the latter are but secondary. Furthermore, in
consequence of the periodic law all the physical
characteristics of the elements are now thought
to depend ultimately upon atomic mass, and
thus their classification is directly correlated
with the atomic theory.
Omitting a very few of the rarer and more
imperfectly known elements, the following ele-
mentary groups may be distinctly recognised.
For the connexion of the several groups with
each other the article on the periodic law should
be consulted (c/. also Classification, p. 203). By
suitable divisions the existence of sub-groups is
indicated : —
1
H
Li
Na
K
Bb
Cs
2
Be
Ca
Sr
Ba
Zn
Cd
Hg
3
B
Al
Ga
In
So
Y
La
Xb
•Tl
4
C
Si
Ti
Ge
Zr
Sn
Pb
Ce
Th
6
N
P
V
As
Sb
Bi
6
O
S
Se
Te
8
Fe
Ni
Co
Cr
— Mo
Nb W
Ta U
Di
Er
7
P
CI
Br
I —
— Cu
Mn Ag
Au
Bh
Bu
Pd
It
Os
•Pt
426
ELEMENTS.
In each of these groups, or, more precisely,
in each of the sub-groups, if the elements are
arranged in the order of their atomic weights,
there is a regular gradation of properties from
the lowest to the highest. Among their com-
pounds precisely similar regularities appear, and
exceptions are quite uncommon. If one element
in a group forms certain well-defined compounds,
we may fairly expect them to be paralleled by
every other element in the same series, and their
points of dissimilarity will follow a regular serial
order. Throughout each group, with a few excep-
tions, there seems to be one dominant valency
representing the maximum stability among the
derivatives of the members of the group, and
these derivatives are frequently isomorphous.
Indeed isomorphism between analogously con-
stituted compounds is good evidence of chemi-
cal kinship, although it is not proof positive.
As regards abundance, association in nature,
and modes of occurrence, the elements differ
widely. Including the atmosphere and the ocean,
the mass of the earth's crust is mainly made up
of thirteen of them, namely, oxygen, hydrogen,
nitrogen, carbon, chlorine, sulphur, aluminium,
calcium, magnesium, iron, potassium, sodium,
and silicon. Certain others, such as fluorine,
manganese, lead, and phosphorus, are relatively
common, and others, likp gallium, indium, and
germanium, are exceedingly rare. Compara-
tively few of the elements are found free in
nature, and these are oxygen, hydrogen, nitro-
gen, carbon, sulphur, tellurium, arsenic, anti-
mony, bismuth, copper, silver, gold, mercury,
zinc, tin, lead, iron, and the six platinum metals.
Of these only nitrogen, gold, and the platinum
group appear to be more abundant free than in
a state of union. Compounds are the rule, native
elements the exception. In general terms, like
elements occur under like conditions, and often
in association with each other. Thus cobalt and
nickel are seldom found entirely apart, the rarer
earths are almost always commingled, and the
platinum metals always occur more or less to-
gether. Apart from the commoner rock-forming
elements, the so-called ' heavy metals ' are chiefly
found segregated in veins which are produced by
infiltration ; while the cerium and yttrium groups,
beryllium, zirconium, thorium, &c., exist almost
solely in granitic intrusions. In sedimentary or
detrital rocks the rarer elements which perhaps
were present in the parent formations are so
widely scattered as to be no longer discernible.
The older rook masses yield by far the larger
proportion of the known elements. Even in vol-
canic outflows the number of elements present
seems to be relatively small, peirhaps because no
segregating influence has rendered the presence
of the scarcer substances distinctly manifest. In
organic matter the elements carbon, hydrogen,
oxygen, nitrogen, sulphur, and phosphorus are
the dominating constituents.
In the beginnings of chemistry the fact that
one substance could be transformed into other
substances gave rise to all manner of alchemical
speculations. Transmutations of matter gave
the young science its only raison d'etre, and no
good reason existed for assigning any limit to
such transmutability. The labours of the alche-
mists, therefore, were not at all uuphilosophical,
but on the contrary they represented efiorts at
generaHsatioD which were perfectly legitimate in
their day. But as the modern conception of an
element developed, limitations not previously
recognised became evident, and the pendulum of
chemical opinion swung over towards a belief in
the absolute independence and individual inte-
grity of the elementary bodies. From this point
of view all theorising as to the nature of the ele-
ments became unprofitable, and, indeed, was put
outside the proper range of scientiflc investiga-
tion.
Of late years, however, the question has been
reopened, the ultimate character of the elements
is no longer positively assumed, and the belief is
gaining ground that they have been derived from
still simpler forms, possibly one form, of matter
by some process of evolution. It will be observed
that the only evidence in favour of their elemen-
tary nature lies in our present inability to de-
compose them, and that evidence is purely ne-
gative. It signifies merely a limitation in our
immediate resources ; not a limitation essential
to the things themselves. On the other hand,
the elements are connected by so many intimate
relations that their complete independence of
each other is hardly supposable. These rela-
tions, being definite and surely not accidental,
need some hypothesis to explain them, and such
an hypothesis, if not fully framed as yet, is at
least progressing in its formative stages. The
chief lines of discussion now open are as follows :
First, on the basis of the periodic law (v,
CiiASsrFicATioN and Periodic i>aw). In his me-
morable paper upon that subject Mendelejeff ar-
ranged theelements in a tabular scheme,in which
certain gaps existed. These gaps, he claimed,
should be filled by undiscovered elements, for
three of which he predicted the properties in con-
siderable detail. Several years later, in 1876,
Lecoq de Boisbaudran discovered gallium, and
that metal was found to fill one of the gaps per-
fectly, conforming with curious accuracy to Men-
delejeS's predictions. Since then scandium has
been discovered by Nilson, and germanium by
Winkler, and they with striking definiteness con-
firm the remainder of the prophecy. In brief,
the prediction of these three metals and its sub-
sequent confirmation would not have been pos-
sible were the elements entirely distinct and un-
related. Again, if we plot graphically any set of
physical properties of the elements, using them
for abscissas and the atomic weights for ordi-
uates, the periodic relations become strikingly
manifest. This is seen in the case of Lothar
Meyer's curve of atomic volumes, in which simi-
lar elements occupy similar places, and by means
of which volumes not actually measured can be
approximately estimated. Although as yet no
such curve has been interpreted mathematically,
there is little doubt but that in time the relations
which are so expressed will receive accurate for-
mulation.
Secondly, there is spectroscopic evidence in
favour of elementary evolution. If we accept
the nebular hypothesis as to the origin of the
solar system, we must give weight to the varying
chemical complexity of the heavenly bodies.
Firsi, the nebulas themselves are gaseous, and
consist very largely of hydrogen. In the whiter,
and presumably hotter, stars a few other sub-
stances appear, more are found in the sun, and
ELEMENTS.
42fl
filially we have the cooled planet, seemingly the
most complex of all. This evidence was first
smnmed up by Clarke in 1873 {Popular Science
Monthly, January 1873), who drew from it
the conclusion that the evolution of planets
from nebulra had been accompanied by an evo-
lution of the chemical elements. In November
of the same year, in a letter to Dumas, Lockyer
put forth a similar conception, resting on the
same evidence, and argued that in the hotter
stars the elements are dissociated. This hypo-
thesis has since been somewhat amplified by
Lockyer in numerous pubUcations, and has at-
tained considerable notoriety. It may be further
emphasised by the fact that the thirteen com-
monest elements are aU of relatively low atomic
weight, while the higher, denser, and probably
more complex metals are, as a rule, scarce. Of
course the weight of the latter argument is weak-
ened by our ignorance of the earth's interior, and
the fact that the mean density of our planet is
much greater than that of its crust. The heavier
elements may be relatively more abundant near
the centre of the earth, as the lighter ones are at
the surface.
Still a third line of argument has been fruit-
ful in speculative literature, namely, the study
of relations between the atomic weights. In 1829
Doebereiner showed that certain elements con-
stituted triads, in which the middle term had an
atomic weight nearly the mean of the atomic
weights of the extremes. Such a triad is formed
by calcium, strontium, and barium, by chlorine,
bromine, and iodine, and by hthium, sodium,
and potassium. In 1851 this matter was dis-
cussed independently by Pettenkofer and by
Dumas, and since then many other writers have
studied it. It is now, of course, supplanted by
the more general periodic law ; but it led to one
conception of curious interest. It was early no-
ticed that each triad had certain resemblances
to the series formed by organic radicles, as in the
paraffin and define groups, and the question was
raised whether a real analogy might not exist.
Now in any organic series isomerism among the
derivatives increases as we ascend, and a similar
rule seems to hold in some- groups of elements.
One example will suffice. The metallic chlorides
and bromides rarely, if ever, assume allotropio
or isomeric conditions. But among the iodides,
allotropy seems to be common ; illustrations
are furnished by the iodides of antimony, mer-
cury, and cadmium. Each of these salts exists
in at least two distinct modifications, while the
corresponding chlorides and bromides show no
similar variability. In itself this argument car-
ries little weight, but with other evidence it adds
to the strength of the modem position.
Passing over all other discussions concerning
relations between the atomic weights, we now
come to one controversy which still has living
interest; the controversy over 'Prout's law.'
In 1815 Prout suggested that hydrogen, the
lightest of the elements, might be the one primal
form of matter, and claimed that the atomic
weights of all the other elements were whole
multiples of that of hydrogen. This hypothesis
as to the atomic weights broke down in its ori-
ginal form, but in 1859 Dumas endeavoured to
show that it held as regards half and even
juarter multiples. Then came Stas, with his
marvellous determinations of many equivalent'
ratios, which seemingly proved the absolute un-
tenability of Prout's law, even with Dumas' mo-
difications. In consequence of Stas' researches,
Prout's law has been of late years out of favour
among chemists, and it has generally been as-
sumed that the question was settled adversely.
But in 1880 Mallet published his paper upon
the atomic weight of aluminium (T. 1880. 1003).
In this paper he cites the atomic weights of
eighteen elements which he regards as fairly
well determined, and shows that ten of them
have values varying less than 0"1 from even
multiples of unity. This concordance may be
accidental ; but under the theory of probabilities
the chances are 1097*8 to 1 against mere coin-
cidence. Two years later, Clarke, in his 'Be-
calculation of the Atomic Weights,' extended
Mallet's argument to sixty-six elements, of which
forty had atomic weights, as then determined,
falling within the limit of 0*1 variation from
theory.' The forty agreements include nearly
aU the trustworthy determinations, while . the
twenty-six exceptions are mostly among elements
of which the atomic weights had been defectively
ascertained. This evidence strengthens mate-
rially the argument used by Mallet. It must
be remembered that the methods ordinarily em-
ployed for computing atomic weights tend to
develop apparent variations, through the multi-
plication of seemingly insignificant errors. The
conclusion to be drawn from the whole discus-
sion is, that some law like Prout's, if not iden-
tical with Prout's, actually exists ; for so large a
proportion of close coincidences could hardly be
due to mere chance. In this connexion the ob-
servation of Meyer and Seubert (C J. 47, 430),
that about one-fourth of the elements have
atomic weights approximating nearly to even
multiples of one-half the atomic weight of oxy-
gen, is surely worth noting. Eeoeutly there
have been several attempts to bring the atomic
weights under one general mathematical law,
but the work so far done is hardly complete
enough to warrant farther notice. The most
promising efiort is probably that of G. Johnstone
Stoney {Pr. 44, 115). The whole question,
however, is conditioned by discussions upon the
possible variability of the atomic weights and
the constancy of chemical composition, such as
have been raised by Schiitzenberger (Bl. 39, 268),
Butlerow {ibid. p. 268), and Cooke {Am. [3] 26,
310). Little weight is at present attached to
that class of speculations, although the argu-
ments which they involve cannot wholly be
ignored.
To a certain extent the nature of the elements
is considered by Sir Benjamin Brodie in his
' Ideal Chemistry ' and his ' Calculus of Chemical
Operations ; ' but along Unes of reasoning which
cannot well be entered upon here. Very recently
also the subject has been extensively treated by
Orookes, and from a novel point of view. He
has studied the phosphorescent spectra of the
rare earths; and has found that by working
with products which represent hundreds of frac-
tional precipitations, he can get strikingly differ,
ent spectra for what is to all chemical tests one
and the same oxide. Thus yttria, after many
* When 0 = 16 as tliG base ot the system.
4S0
ELEMENTS.
fractionations, divides into products which are
unlike spectrosoopically; justasif the nioleoules
of the original earth had either been sorted out
from a mixture, or else split up into new groups.
These products, differing from ordinary yttria,
are the oxides of what Crookes provisionally
calls ' meta-elements.' In the same category,
perhaps, we must place the neodymium and
praseodymium of Auer von Welsbaoh, derived
from didymium; and also the many doubtful
earths obtained from samarskite, gadolinite,
&o., by Marignao,De Boisbaudran, and Kriiss and
Nilson. Unfortunately we do not yet know how
to interpret all the phenomena, and the evi-
dence admits of various explanations. We may
have merely allotropes to deal with, or there
may have been a veritable splitting up of rela-
tively unstable elements. That the actual num-
ber of distinct earthy oxides should be very
largely increased is unlikely, for they fit no
vacant places in the periodic system. Crookes
himself interprets the evidence thus : — Following
along the line of elementary evolution, he con-
ceives that matter, as it developed from the
original 'protyle,' passed from stable point to
stable point through intervals of instability.
Around each accretion of the primitive stuff
into a definite element there may be gathered a
few particles of intermediate material; and these
' by-products ' of elementary manufacture, sepa-
rable only by long fractionations, may give rise
to the phenomena observed in the spectra of
yttria. The main line of evolution be repre-
sents by a lemuiscate curve.
This work of Crookes, as represented in his
address of 1886 before the British Association,
and in two later lectures before the Chemical
Society (O. J. 53, 487), biings us face to face
with the final question of all. Admitting that
the elements have been somehow evolved from
simpler primal forms, can the process ever be
repeated or reversed artificially ? To this ques-
tion no answer is now possible; but it seems
likely that if a transmutation of so-called ele-
mentary matter should ever be effected in the
laboratory, it will be by the very slow develop-
ment, under conditions of prolonged chemical
stress, of change in traces only.
P. W. C.
ELEMI, A name given to various resins.
Elemi occidentale is said to be the produce of
Idea loicariba ; Elemi orientale to come from
Amyris ceylonioa. Elerm cBgyptiacmn is perhaps
produced by Elmagnus hortensis. Translucent
resins, used in making varnishes. Some speci-
mens contain amyrin {q. v.) and elemin. Ele-
min forms thin six-sided prisms [200°] (John-
ston, A. 44, 338 ; Bose, A. 32, 297 ; 40, 307 ;
Hess, A. 29, 139 ; Baup, /. Ph. [3] 20, 321 ; Buri,
N. Sep. Pha/rm, 25, 193). " Arbol-a-brea resin
contains bryoidin Cj„HasOs [136°] (Pluckiger, J.
1875, 860). According to Stenhouse and Groves
(A. 180, 253) incense-resin (from Icica hepta-
phylla) contains conimene CuH^, and icacin
C^HijO. When elemi resin derived from Amyris
elermfera and A. ceylonioa is distilled with zinc-
dust it yields toluene, m- and ^-ethyl-toluene,
and ethyl-naphthalene (Ciamician, O. 9, 310;
B. 11, 1344).
Oil of elemi C,(,H,8. (166°) (Stenhouse, A.
85, 304); (174°) (DeviUe, A. 71, 352). S.G.
24 -852. V.D. 4-0. [on]=-yO°. Oil, obtained
by distilling elemi with steam. HGl forms solid
inactive C,„H„C1 and a liquid isomeride.
ELEmiC ACIDCsHssOj. [216°]. o„=-3-5°.
Occurs in elemi, and purified by means of the
K salt (Buri, Ph. [3] 8, 601).
Pr(^erties. — Large crystals (from alcohol).
Insol. water, sol. alcohol and ether, si. sol. CS^.
Its alcoholic solution reddens litmus.
Salt. — KA'lSaq : needles.
ELLAGIC ACID OnHjOj i.e.
,0.H(0H)3 ^C.H(OH),.CO.O^
\A/,^TT^/0>v ^C,H(0H)2.C0.0/
^C,(OH),<(fo>
(Schiff, B. 12, 1533). S.G. la 1-667. A consti-
tuent of Oriental bezoars (Chevreul, A. Oh. [2] 9,
629 ; Braconnot, A. Ch. [2] 9, 187 ; Pelouze, A.
Ch. [2] 64, 367 ; Taylor, P. M. [3] 24, 354 ; Wohler
a. Merklein, A. 55, 129). Occurs also in sprouts
of the divi-divi (Lowe, Fr. 14, 40 ; Barth a.
Goldsohmiedt, B. 11, 846 ; 12, 1239 ; Cobenzl,
M. 1, 671) and in oak bark (Btti, M. 1, 266) and
fir bark (Strohmer, M. 2, 539).
Formation. — 1. From gallic acid or tannin,
by treatment with iodine, POClj, POlj, or As^O,
(Griessmayer, 4. 160, 56; Lowe, Z. 1868, 603).
It is also deposited as a grey powder when a de-
coction of galhiuts is leit exposed to the air.—
2. By heating gallic ether with aqueous HaOH
at 60° (Schiff, B. 12, 1533).
Preparation. — ^Bezoars are dissolved in strong
aqueous KOH in the cold ; CO^ is then passed
in, when potassium ellagate is ppd. This is re-
crystallised from water, and the acid is liberated
by hydrochloric acid.
Properties. — Minute yellowish prisms (con-
taining 2aq). Insol. water and ether, si. sol.
alcohol. A solution in cone. EOHAq when ex-
posed to the air deposits black crystals of ' potas-
sium glaucomelanate ' 0,2HiK20, (?), which is
reconverted into ellagate by boiling water. Cone.
H2SO4 dissolves ellagic acid vrithout change.
FejClj gives a greenish colour becoming black.
Reactions. — 1. DistUlatiou with zimc-d/mt
gives fluorene C,4H,„. — 2^ Sodium amalgam in
alkaline solution gives ' glauoo-hydro-eUagic acid '
CnH|„0„ ' rufo-hydroellagic acid' C,4H,|,0,'
(Eembold, 5. 8, 1494; Cobenzl, M. 1, 671), an
acid 0,4H,„0j, and finally (7)-hexa-oxy-diphenyl.
3. Potash-fusion gives (/3)-hexa-oxy-diphenyl
(B. a. G.). — 4. BoUinj^ cone. KOHAq gives hexa-
oxy-diphenyleue ketone..
Salts. — KjA" (at 150°) : minute prisms. —
K2A"K0H (?) : grey 'powder.— Na2A"aq : pale
yellow crystalline powder, si. sol. water. —
MaHA"aq (at 100°).— Ba,H3A"j (at 140°) : lemon-
yellow insoluble pp. — PbA"aq : amorphous yellow
pp. ; -becomes olive-green on drying.
Tetra-aoetyl derivative C^fi^^ofig,
yellow crystalline powder, si. sol. water.
ELLAGITASiriO ACID C„H,„0,tf. Occurs
in divi-divi and myrobalanes (Lowe, Fr. 14, 44).
Amorphous brownish mass. Water at 110° con-
verts it into ellagic acid.— (0„H,„O,„)25PbO.
ELTTTBIATIOW. The separation of lighter
from heavier particles by washing.
EMETINE O^jH^oN^O, (7). [65°-74°]. S. I
in the cold. Occurs in ipecacuanha root (Pel-
letier a. Magendie, A. Ch. [2] 4, 172; Buchner,
Bepert. Pharm. 7, 289 ; Dumas a. Pelletier, A.
ENNOIO ACID.
431
Ch. [2] 24, 180 ; Lefort, J. Ph. [4] 9, 241 ; Pander,
C. C. 1872, 440 ; Glenard, G. B. 81, 100 ; Lefort
a. P. Wurtz, 0. B. 84, 1299 ; Power, Pli. [3] 8,
344 ; Kunz, Ar. Ph. [3] 25, 461 ; Podwyssotzky,
Ph. [3] 10, 642) ; Kremel, Ar. Ph. [3] 26, 419).
PreparaHon. — ^Ipeoaouanha is exhausted with
ether and ligroin and the residue extracted with
(85 p.o.) alcohol ; the extract is evaporated to a
syrup, and Pe^Cl, added to ppt. tannin ; excess
(ft NaXO, is added, and the emetine extracted
with hot hgroin.
Properties. — Needles (from ligroin). SI. sol.
water, t. sol. oUoroform, EtOAc, alcohol, CS2,
and essential oils, si. sol. ligroin, ether, and
benzene. Alkaline reaction. Coloured yellow
by sunlight. Produces vomiting. Except the
tannate, all its salts are amorphous. Solpho-
molybdio acid gives a brown colour, changed by
HCl to indigo blue. Potassium-bismuth iodide
gives a pp., as do other re-^agents for alkaloids.
Salts.— B'HjPtCl, : yeUowish- white powder.
— B'HjCrA-— B'Mel.— B'MeOH.
EUODIN V. Xbi-oxy-methyii-ahthraqdiiioke.
EUTJIiSIN. A neutral substance contained
in sweet and in bitter almonds, and possessing
the power of acting as a ferment on the amygdalin
of die latter in presence of water, converting it
into benzoic aldehyde, HCy, and glucose (Bobi-
quet, J. Ph. 24, 326 ; Thomson a. Biohardson,
A. 29, 180 ; Ortloft, Ar. Ph. 48, 16 ; Bull, A. 69,
145 ; Johannsen, Bied. Cent. 1888, 326). It may
be obtained by leaving an aqueous extract of
almond cake at 23° for a few days, filtering, and
ppg. with alcohol. White amorphous mass, sol.
water. The hydrolytic power of emulsin is
destroyed by boiling.
ENCEFHALIN v. Cebebbin.
»-ENNANE CjHa,. Nonane. Mol. w. 128.
[-51°]. (150°). S.G. £ -733 ; i^ -6541. From
pelargonio acid CjHisOj by distillation with P
and HI (Krafft, B. 15, 1692).
Ennane CjH,„. (148°). S.G. 5i -7124. V.D.
65*4 (for 64). Occurs in Galician petroleum
(Laohowioz, A. 220, 194).
Ennane 0^.- (136°). S.G. V "T^a. V.D.
4-59 at 180°. Ocoors io petroleum (Iiemoine,
Bl. [21 41, 163).
Ennane C,B^„. (130°). S.G. 2 -743. V.D.
4-47 at 190°. Occurs in petroleum (L.).
Ennane C^j„ i.e. ?r.CH,.CH,.CH,.?r. (132°).
S.G. 2 -725. Prom isoamyl iodide, isobutyl
iodide and Na (Wurtz, A. Ch 3] 44, 275).
Ennane 0,H2„. (130°). From isopropyl
iodide and Na (SUva, B. 6, 984).
ENNDECANE C,^„ i.e. CH3(CH.J„0H,.
Nonadecame. [32°]. (330°). S.G. f -7774 ; »,»
•7323. Prom C|bHj,CL, by heating with HI and
phosphorus. Occurs also in paraffin from bitu-
minous shale (Krafft, B. 15, 1704 ; 21, 2256).
ENNDECANE DI-CAEBOXYLIC ACID
0,^3s(COjH)2. [90°]. From oxy-henioosoio acid
0,ja„(GHjOH)(COjH) by heating with soda-lime
(Starcke, A. 223, 312). White powder (from
alcohol and light petrolemn).
Salt.— PbA".
ENKENOIC ACID 0,H, A»-«-CPr2:0H.C0i,H.
Di-P-prqpyl-acryUc acid. [81°]. Prom
Pr,C(0H).CHj.C0jHand dilute HjSO^ (Albitzky,
J.pr. [2] 80, 209). Needles (from benzene). SI.
Eol. water, t. sol. alcohol, ether, and benzene.—
LiA' 2aei.— BaA'2 aq.— CaA'j aq. S. (of CaA j) 3-3
at 21°.— PbA'j2iaq.
EnnenoicacidC„H,„Oji.«.08H,3.CH:CH.C02U.
Nonylen/io acid. Formed by heating heptoio
aldehyde (oenanthol) with NaOAo and AC2O at
170° for 30 hours (Schneegans, A. 227, 80). ,
Liquid, v. si. sol. water, very volatile with steam.
BeadUy combines with HBr forming bromo-
ennoic acid (q. v.). Not attacked by nascent
hydrogen. — BaA'j. — CaA'j 3aq : needles. — AgA'.
Ennenoic acid CgHigO^. Phoromc add.
[169°]. [bd] = 23° (in alcohol). Formed, together
with camphio acid, by exposing sodium-camphor
to the air (Montgolfier, A.Ch. [5] 14, 82). Tables
(from alcohol). Insol. water and CSj.
ENNENYL ALCOHOL G,H„0 i.e.
Pr.CH:0H.0Hj.CMe2.0H. Di-methyl-isopropyl-
allyl-carbmol. (176°). Eg, =72-27. Promdi-
methyl-allyl-carbinol (hexenyl alcohol), isopro-
pyl iodide, and zmo (Dieff, J. pr. [2] 27, 364).
Gives isobutyric acid on oxidation. Combines
with bromine forming CgHj^r^O.
Methyl ether C„H„OMe. (171°). S.G.
^ '8027. Boo 81'55. KMnO, gives methylated
oxy-valeric acid, CH3O.C4Hg.COjH, and isobuty-'
rio acid (Kononowitz, J.pr. [2] 30, 400 ; Bl. [2]
43, 381).
ENNENYLCHLOEIDECpH„Cl. (175°-185°).
From the alcohol and PClj (Dieff).
ENNINENE CgH.e. (136°). Campholme.
Obtained from campholio acid by the action of
P2O, or by distilling with soda-lime (Delalande,
A. 38, 340; Kachler, A. 162, 266).
Enninene C^B.,,. (135°-140°). From cam-
phor and HI at 200° (Weyl, B. 1, 96).
ENNINYL ALCOHOL OsH,„0 i.e.
{Cm^.CE..CS^^CKi.O'Z.Ethyl-di-allyl-cci/rhmol.
(176°). S.G. g -8776 ; ^ •8637. O.E. (0°-17°)
^00095. Prom propionic ether, aUyl iodide, and
zino (Smirensky, J. pr. [2] 25, 59).
n-£NNOIC ACID CgHigO,. Pelargonio acid.
Nonylioacid. Mol. w. 168. [13°]. (254° i.V.).
S.G. -If -9109 ; If -9103 ; ^ -8433. H.Q. 1287352.
M.M. 9-590 at 20° (Perkin, C. J. 45, 486 ; Longui-
nine,A0;j. [6]11, 222).
Occurrence. — In the volatile oil of Pela/rgo-
niirni roseum (Pless, A. 59, 54). In fusel oil
from beet root (Perrot, A. 105, 64).
Formation. — 1. From heptyl-aoeto-acetio
ether and KOH (Jourdan, A. 200, 105).— 2. By
action of HNOj on oleic acid (Bedtenbacher, A.
59, 52), on stearolio acid (Limpach, J. 190, 297),
and on oil of rue (Gerhardt, A. 67, 245).— 3. By
fusing hendecenoio acid CuH^gO, with KOH
(Krafft, B. 15, 1691).
Properties. — Oil at ordinary temperatures.
Salts. — CaA'j.— BaA'j : laminae, si. soL hot
water.— OuA'j [c. 258°].— ZnA'^ [132°].- AgA'.
Methyl ether UeA'. (214° i.V.). S.G.g
•8918. S.V. 245-7. C.B. (0°-10°) ^00091 (Gar-
tenmeister).
Ethyl ether EtA'. (228° i.V.). S.G. >rs
•8655 (Zincke a. Prauchimont, A. 164, 339;
15 •8703 ; II -8641. M.M. 11^571 at 18-2° (Per-
Bn, 0.^.45, 503).
Chloride C,H„OCL (220°) (Cahours, O.J.
3, 240).
Amide CjH.jONHj. [93°] (Sohalfejeff, B.
6, 1252) ; [99°] (Hofmann, B. 16, 984). Formed
433
ENNOIO ACID.
by heating ammonium ennoate at 230° under
pressure.
Anhydride (C,H„0)jO. [-6°] (Chiozza, A,
86, 231).
Nitrile OHaCOHJjON. (215°). S.G. M
•786. Prom w-ootyl iodide and KCN at 180°
(Eichler, B. 12, 1888).
Jso-ennoic acid CjHuOj i.e.
CH,(0H,)5CHMe.C02H. (245*' cor.). S.G. la
■9033. Prom its nitrile, which is obtained by
acting on methyl-hexyl-carbinyl iodide (octyl
iodide) with KOy (Kullhem, A. 173, 319). Oil.—
NaA'aq: slender needles. — KA.'. — CaA'^aq:
needles (from alcohol). — CuA'jKaq. — AgA'.
Ethyl ether EtA'. (214° cor.). S.G. ^
■8641.
Nitrile CB^(GR^)SyBMe.CT<i. (206°). S.G.
14 -8187.
Amide CH3(CH,)5CHMe.C0NHj. [91°] and
[105°] (7).
Ennoic acid CE^.(CE^i.CB.Uf>.C!R^.CO^.
(232°), Got by heating heptyl-malonio acid
(Venable, B. 13, 1652). Oil.
V. also BnoMO-ENNOia acid.
ESNYL ALCOHOL 0^a,0. Nom/l alcohol.
Mol. w. 144. (o. 188°). S.G. "2:5 ■SSS. From
petroleum ennane (Lemoine, Bl. [2] 41, 163 ; cf.
Pelouze a. Cahours, A. Ch. [4] 1, 5).
Acetyl derivative CbHuOAo. (o. 210°).
Ennyl alcohol GbH^jO. (205°-212°). S.G. ii
■847. Prom isoamyl isovalerate and sodium
(Louren^o a. Aguiai, Z. 1870, 404).
Acetyl derivative C,H,jOAo. (207°-
213°).
Ennyl alcohol FrjCEt.OH. Ethyl-di-propyl-
carbinol (Tschebotareff a. Saytzeff, J. pr. [2] 33,
195). (179-5° cor.) (T. a. S.) ; (176°) (Mensohi-
koff, J. pr. [2] 36, 351). V.D. 143-5 (for 144).
V. si. sol. water. S.G. "J" -8331 ; %° -8358. From
di-propyl ketone, EtI, and Zn. Gives, on oxida-
tion, CO,, acetic acid, propionic acid, and butyric
acid, also di-propyl ketone and ennylene.
Acetyl derivative, (c. 190°). S.G. %°
•8676.
Ennyl alcohol CeH.j.CHEt.OH. (195°). S.G.
?'839; "z" -825. From heptoic aldehyde (cenan-
fiiol) and ZnEtj followed by water (Wagner, Bl.
[2] 42, 330). Gives ethyl hexyl ketone on oxi-
dation.
Acetyl derivative Oi|H,jOAo. (211°).
S.G. S -878 ; f -861.
EHNYLAMINE CaH,jNHj. (191°). Formed
^y the action of NH, on the ennyl chloride de-
rived from petroleum (Pelouze a. Cahours, J.
1868,529; 4. Cfc. [4] 1, 5).
Ennylamine OgHisNHj. (195°). Formed by
the action of Br and EOH on the amide of decoic
(capric) acid (Hofmann, B. 15, 773).— B'^H^tCls.
ENNYL CHLOEIDE C„H,„C1. (c. 182°) (Le-
moine, Bl. [2] 41, 164) ; (196°) (Pelouze a. Ca-
hours, /. 1863, 529). S.G. is -899 (P. a. C);
S -908 (L.). From petroleum ennane by ohlori-
uation.
Ennyl chloride 0,H,gCl. (150°-160°). From
the ennyl alcohol obtained from isoamyl isova-
lerate and Na (Louren90 a. Aguiar, ^. 1870,404).
ENNYLENE C,H,s. Nonylene. Mol. w. 126.
(o. 135°). S.G. la -853. From the ennyl chlor-
ide which is derived from petroleum (JQemoine,
£1. [2] 41, 163).
Ennylene C,H,8. (138°). S.G. ^ -743. From
ethyl-dipropyl-oarbinyl iodide and alcoholic EOH
(Soooloff, J. B. 1887, 599).
Ennylene C,H,j. (140°). Among the pro-
ducts of the action of ZnCl^ on fusel oil (Wurtz,
A. 128, 232).
Ennylene 0,H,,. (145°). S.G. H? -757.
Formed by the action of lime on heptoic alde-
hyde (oenanthol) (Fittig, A. 117, 78).
Ennylene OjH,,. (c. 147°). From paraffin,
by strongly heating it (Thorpe a. Young, A. 165,
18).
Ennylene C„H,b. (o. 149°). S.G. ^787. Occurs
in oil of resin (Benard, Bl. [2] 39, 541).
Ennylene OsH„ (153° cor.). S.G. s ■762.
Obtained by distilling the lime soap made from ,
train oil (Warren a. Storer, Z. 1868, 230).
Ennylene 0,H„. (121°). S.G. -13 -753.
Found among the products of the distillation of
bituminous shale (Laurent, A. 25, 285).
V. also the Hexahydrides of Cumeni: and
DI-ENNYL-KETONE C„H,,Oi.e. (0,H„)jCO.
Caprinone [58°]. (above 350°). Obtained by
distilling calcium decoate (caprate). Pearly
laminss (from alcohol). Gives decoic acid on
oxidation (Grimm, A. 157, 270).
ENNYL - UEEA Decoyl derivative
C„H„NH.CO.NH.CO.CsH„. [101°]. White plates.
Formed by the action of KOH on a mixture of
the amide of decoic acid and bromine (Hofmann,
B. 15, 761).
EOSIN V. tTe^a-BBOMO-PIiUOBESCEIN.
EPIBEOMHYDBIN CHjBrO. (139°). S.G.
i* 1^615. From OaHsBr2(6H), and cone. KOHAq
(Beboul, A. Svppl. 1, 227 ; Berthelot a. De Luca,
A. Ch. [3] 48, 311). Formed also by distilling
the compound of acetone with Br (Limiemann,
A. 125, 310). NH3 forms CjHj^rNOj, an amor-
phous insoluble base.
Epidibromhydrin v. Di-BBOMo-pitof xlene.
EFICHLOSHYDEIN C,HjC10 t.e.
O
CH^Cl.CH.CH,. Chloro-propylene oxide. Mol.
w. 92i. (115-9°) (Schiff, A. 220, 99); (116-6
cor.) (Thorpe, G. J. 37, 207). S.G. % 1-2031.
C.E. (0°_10°) -001033; (0°-100°) -0011551.
V.D. 3-21 (for 3-19). S.V. 87-1 (S.) ; 87-3 (T.).
Formation. — 1. By treating di-chloro-pro-
pyl alcohol (glycerin dichlorhydrin) with fuming
or gaseous HCl (Berthelot, A. Oh. [3] 41, 299).
2. By the action of alkalis on either of the two
di-chloro-propyl alcohols CH201.CHCl.CHj0H or
CH,C1.CH(0H).CH2C1 (Eeboul, A. Suppl. 1, 221 ;
Tollens a. Miinder, Z. 1871, 252; Prevost, J.pr.
[2] 12, 160 ; Glaus, B. 10, 557 : Cloez, A. Ch. [6]
9, 145).
' Prqperiies.— Liquid with sweet taste, smelling
like chloroform. Nearly insol. water, mixes with
alcohol and ether.
Beactions. — 1. Water (J vol.) at 100° con-
verts it into ohlorhydrinCH2Cl.CH(OH).CHj(OH)
and glycerin. — 2. Fuming HCl readily acts upon
it,forming OHjCl.CH(OH).CH.,Cl (180°).-3. HBr
forms CH2Cl.CH(OH).CHJ3r (197°). S.G. 1*1-740.
4. HI acts with great violence, forming
CHjCl.CH(0H).CH2l as well as propyl iodide
and M-propyl chloride (Silva, C. B. 93, 418).—
6. PCI, forms CHjChCHCLCHjOl. PCI3 forma
CaHsCl,(OPCy (0.136°) at 100 mm. (Hanriot,£Z.
EQUATIONS, CHEMICAL.
433
I?] 32, 551;. — 6. Phosphorus pentabromide gives
CH,01.GHBr.0H,Br (Darmstadter, 4. 152,319;
c/ Wiohelhaus, A. Suppl. 6, 277).— 7. Bromine
at 100° forms ohloro-tri-bromo-acetone (Gri-
maux a. Adam, Bl. [2] 83, 257).— 8. A solution
of HCIO (7 p.o.) in water in darkness produces
C,H,0L,O, or CjH,01j(0H)j (Carius, A. 1^4, 71).
ft. Acetyl chloride in the cold, or more quickly
at 100°, forms CjH5Clj(OAo). By long heating
(30 hours) at 100° there is also formed
C„H,<,Cl,0(OAo) and C„H,5ClA{OAo). Butyryl
chloride forms CjHsCl^fO.OO.Pr). Benzoyl
chloride at 180° gives CjH5Clj(0Bz) (Truchot,
Bl. [2] 5, 447 ; 6, 481).— 10. Acetic anhydride at
180° gives C3H5C](OAo), and 0,H5Clj(0Ac) (T. ;
cf. Franohimout, R. T. 0. 1, 43). Heating -with
a.cetic acid at 100° forms CjHsClfOHjfOAo).
Benzoic anhydride at 190° gives CjHslOBz),
[74°] (Van Bomburgh, B. T. G. 1, 46).— 11. Cono.
KjSOsAq forms 03H5(OH)(SOsK)2 2aq and free
KOH (Pazsohke, Z. [2] 5, 512). — 12. NaHSOa
at 100° forms CH,C1.0H(S0,Na)CH20H (Darm-
stadter,^. [2] 4,342).— 13. Alcohol at 180° gives
rise to 0,H5CL,(0H), C,H5(0H)(0Et)j and
C,HjCa(OH)(OEt). Isoamyl alcohol at 220°
forms 0,H501(0H)(0C5H,J, CsHsOLjIOH), and
C3H,(OH)(OC5H„),.— 14. Ethyl bromide gives
03H5ClBr(OEt).-^16. Sodvum forms a yellow oil
C„H,„Oj (o. 218°), and an insoluble compound
C„H,„OjNajClj (Hiibner a. Miiller, A. 159, 186;
Hanriot, Bl. [2] 32, 552 ; Glaus, B. 10, 556).
16. Sodium ethylate free from alcohol forms
C3H5(OH)(OEt)jand white hygroscopic CibHjjOs
(Laofer, Jena. Zeit. [2] iii. 2 Suppl. 141 ; cf.
Louren90, A. Ch. [3] 67, 309).— 17. Alcoholic
KOPh forms crystalline CaHjOrOPh) (Lippmann,
Sitz. W. 62 [2] 605).— 18. Sodiurft amalgam has
little action, but forms a small quantity of allyl
alcohol (Tomoe, B. 21, 1282 ; cf. Buff. A. Suppl.
5, 247).— 19. H^SO, forms oily CaHjOKOH) (SO^H)
(Oppenheim, B. 3, 735). —20. Oxidised by HNO3 to
ohloro-oxy-propionicacid. — 21.Alcoholic or strong
aqueous a/mmorda forms gummy CeH,2ClN02(?)
Gaseous ammonia reacts in the cold forming
N(C,HsCa.OH), [93°] which forms a crystalline
hydro-chloride [173°], and is converted by alkalis
into a substance resembling gelatin (Eauconnier,
0. B. 107, 115).— 22. Triethylandne at 100° gives
rise to crystalline C,H,O.NEt,Gl (Beboul, O. B.
93, 423). — 23. Amline at 140° forms oily
Gg^HigN^O, the constitution of which is probably
CHjNHPh.GH(OH).GHj.NHPh. [54°] (290° at
10 mm.). It forms a hydrochloride B"HjCl2
[202°] crystallising in needles, insol. ether, sol.
alcohol and water, which gives the reactions
usually characteristic of alkaloids (Fauconnier,
C. B. 106, 605 ; 107, 250).— 24. Zinc and allyl
iodide followed by water give chloro-hexenoic acid
{3. 1;.), the first reaction being represented thus :
CjHsGlO + Zn + IG3H3 = G3H5Gl(OZnI)G,H, (Lo-
patkine, Bl. [2] 41, 318).— 25. HON forms chloro-
oxy-bntyronitiile G3H5Cl(OH)(ON), sol. water,
aloohbl, and ether (Hermann, B. 12, 23).— 26. KGy
forms epioyanhydrin. — 27. Boiling aqueous
KCNO forms 0,H„GlNOj [106°], crystallising in
prisms (Thomsen, B. 11, 2136). It forms an
acetyl derivative C.HjAcClNOj [79°].
Chlorinated epichlorhydrins «. Celobo-
ACEIONE.
Epidichlorhydrin v. Pi-CHioBo-PROPYiENB,
Vol. II.
EPICYANHYDEIN C.HjNO *.«,
O
HpCH-GHjON. [163°]. From epichlorhydrin
and aqueous EGy (free from alkali) in the cold
(Pazsohke, Z. [2] 5, 512 ; J. pr. [2] 1, 82),
Broad prisms (from water). Hot fuming HGl
O
converts it into CH2X!H.GH2.C02H [225°] which,
by further heating with fuming HCl for 6 hourg
at 160° is reduced to ra-butyrio acid (Hartenstein,
J. pr. [2} 7, 295).
EPIIOBHYDEIN C,HsIO i.e.
O
/\
0H2.CH.CH^. (160°-180°). S.G. i5 2-03. From
epichlorhydrin and EI at 100° (Eeboul, A. Suppl.
1,227). Oil.
EQUATIONS, CHEMICAL. The formula of
an element expresses a certain quantity of that
element, and the formula of a compound repre-
sents the composition of a certain quantity of
that compound. When elements and compounds
interact chemically, other elements and com-
pounds are produced ; a chemical equation re-
presents, primarily, the quantities of the interact-
ing bodies and the products of the interaction,
and the compositions of these bodies. The sum
of the quantities of the interacting bodies is
equal to the sum of the quantities of the pro-
ducts of the interaction. A chemical equation
then represents the distribution of the bodies
which take part in a chemical change before the
change begins and when the change is com-
pleted. But the equation does not give a full
account of the transaction ; thus the equation
Zn + HjSOj-ZnSOi+Hj teUs that, if zino and
sulphuric acid react to produce zino sulphate
and hydrogen, then 98 parts by weight of sul-
phuric acid react with 65*2 parts of zinc, and
the quantities of zinc sulphate and hydrogen pro-
duced are represented by the numbers 161'2 and
2, respectively. The equation does not indicate
the conditions which must be fulfilled in order
that zinc and sulphuric acid shall react to pro-
duce zinc sulphate and hydrogen ; as a matter
of fact a considerable quantity of water must be
present. Again, the equation CaCl2 + Na2C03
= 2NaGl + CaC03 merely asserts that when cal-
cium chloride and sodium carbonate react to
produce sodium chloride and calcium carbonate,
for every 111 parts of calcium chloride changed
106 parts of sodium carbonate are also changed,
but it does not tell that in order to effect the
change of 111 parts of calcitmi chloride into cal-
cium carbonate much more than 106 parts of
sodium carbonate must be present although only
106 parts are actually chemically changed. An
equation often represents a chemical occurrence
as more simple than it really is. For instance, ,
the equation FeOl3 + 3ECNS=Fe(CNS)j4-3EGl
seems to imply that if 162-5 parts of ferric
.chloride were mixed with 291 parts of potassium
sulphocyanide, 230 parts of ferric sulphocyanide
and 223-5 parts of potassium chloride would be
produced ; but in order to change 162-5 parts of
ferric chloride to ferric sulphocyanide something
hke 300 x 291 parts of potassium sulphocyanide
must be present, although only 291 parts of the
snlphocyanicle t»re actually chemically change^.
FF
434
EQUATIONS, CHEMICAL.
When the bodies which take part in a chemi-
cal change are gaseous the equation represents
the volumes of the gases which react and are
produced; thus the equation 31,+ 0=H|jO tells
that if hydrogen is combined with oxygen to
form water-gas, then the volume of hydrbgen is
double that of the oxygen and is equal to that of
the water-gas formed. The formula of a com-
pound gas always represents the composition of
that mass of the gas which occupies twice the
volume occupied by one part by weight of hydro-
gen at the same temperature and pressure as the
gas in question. The symbols of some elements
represent those masses of the gaseous elements
which occupy the same volume as one part by
weight of hydrogen, e.g. 01, 0, N, Br ; but there
are several exceptions to this statement, e.g. the
symbols P and As represent masses of phosphorus
and arsenic which, as gases, occupy half 'the
volume occupied, at the same temperature and
pressure, by unit mass of hydrogen, and the
symbols Eg and Cd represent masses of mer-
cury and cadmium which, as gases, occupy twice
the volume occupied by unit mass of hydrogen.
Chemical equations which represent changes
of composition occurring among gases may also
be read in the language of the molecular and
atomic theory; as thus regarded they tell the
ratio between the numbers of molecules of the
reacting bodies and the ratio between the
numbers of molecules of the products of the re-
action ; the equations also represent the distribu-
tion of the atoms of the elementary constituents
of the reacting bodies and the bodies produced.
Thus the equation 2Hj + 02=23^0 teUs that
when hydrogen and oxygen combine to form
water, two molecules of hydrogen react with one
molecule of oxygen to produce two molecules of
water-gas, and also that the hydrogen and oxygen
molecules are diatomic, and that the molecule of
water-gas is composed of two atoms of hydrogen
and one atom of oxygen. It is often the custom
to regard the formulas of liquid and solid bodies
as molecular, and so to regard every equation as
an expression of the molecular and atomic dis-
tribution of the bodies taking part in the chemi-
cal change ; but to do this at present is to go
further than is justified by the molecular and
atomic theory (c/. Atomic and moueculab
WEIGHTS, vol. i. 347-350). In connexion with
chemical equations v. FoBMniuE.
M. M. P. M.
EQUILIBBHTU, chemical. The nature
of the problems which we shall discuss in this
article may best be illustrated by consideriijg a
few simple cases. The simplest we can take is
when a given quantity of such a substance as
HjO which can exist at ordinary temperatures
in both the liquid and gaseous states is placed
in a closed vessel of given volume ; then if in
this volume we have a given quantity of HjO,
the system will arrive at, and remain in, a state
in which the quantities of steam and water have
definite values, say a and j8 respectively ; if on the
introduction of the H^O the quantity in the
gaseous state was greater than iS, condensation
wiU take place until it is reduced to j8 ; if on the
contrary the quantity was less than P, evapora-
tion will take place until it reaches this value.
Another case analogous to this, but in which the
(wQ states are the solid and the gaseous, is wh«o
instead of water and steam we have solid para<
cyanogen and gaseous cyanogen ; in this case, as
Troost and Hautefeuille (O. B. 66, 735, 795)
have shown, the system attains a state in which
the pressure of the cyanogen gas has a definite
value depending upon the temperature. Another
example is when a substance can exist in two
allotropic forms, such as phosphorus in its red
and, yellow modifications ; if a given quantity of
phosphorus be heated in a closed vessel it will
attain a state in which the quantities of the red
and yellow modifications have definite values
(v. Troost and Hautefeuille, A. Ch. [5] 2, 153).
The phenomena of dissociation afford excel-
lent examples of chemical equilibrium ; N^O^ for
example dissociates into NO^, but if the gas is
contained in a closed vessel the dissociation does
not go on indefinitely, but only untU a certain
proportion of the gas has been dissociated, after
which no further change takes place in the gas if
the temperature and pressure remain constant.
A more general case of chemical equilibrium is
when solutions of sulphuric and nitric acids,
and nitrate and sulphate of sodium are mixed
together ; chemical changes will go on until a
state is reached in which there is a certain rela-
tion between the masses of the four substances
present ; after this no further change will take
place in the constitution of the mixture.
In this article we shall discuss the relations
which in cases like these exist between the quan-
tities of the various substances, or the quantities
of the same substance in different states, when
there is equilibrium, and the way in which this
relation is affected by alterations in the physical
conditions, such as changes in pressure, tem-
perature, intensity of magnetisation, and so on.
Having seen the nature of the problems with
which we have to deal, it will be weU to consider
how chemical equilibrium resembles or differs
from ordinary dynamical equilibrium. In the
first place all chemical systems seem to reach
a steady state, while it is only under excepi
tional circumstances that frictionless dynamical
systems do so. Again, as far as our knowledge
extends, a chemical system gradually approaches
the state of equilibrium, and when it has once
reached it, remains in it ; nothing corresponding
to the oscillations of a dynamical system about •
its position of equilibrium seems to have been
observed. The dynamical systems whose be-
haviour most closely resembles that of the chemi-
cal systems are those in which the friction is
very large or the inertia very small ; such systems
always get into a steady state and sink gradu-
ally into it without ever passing through it.
Complete and Paeiial Equimbricm.
In the examples of chemical equilibrium pre-
viously considered, the state of the mixture is
definite when given quantities of various chemi-
cal elements are present under identical physi-
cal conditions. Such a system may be said
to be in ' complete ' equilibrium. There are many
cases, however, in which quite a different state
of things obtains ; thus at low temperatures we
may have given quantities of hydrogen and
oxygen in equilibrium when arranged in an in-
finite number of ways, for, since steam, hydrogen,;
and oxygen do not combine at such temperatures,
we may divide the hydrogen and oxygen in any
EQUILIBRIUM, CHEMICAL.
436
proportion between HjO, Oj, and Hj, and yet still
have equilibrium. The reason for the difierence
between this case and the previous one is obvious :
here the system has no (chemical) freedom and
must stay in whatever (chemical) state it was
placed initially ; in the previous cases, on the
other hand, the quantities of any of the sub-
stances could both increase and decrease : thus
in the case of the water and steam, the water
could evaporate and the steam condense; in the
dissociation of Nfi„ the NjOj could split up and
the KO, combine ; such oases are said to be ' re-
versible' and are characterised by the physical
and chemical conditions being such that pro-
cesses can occur by which the quantities of any
of the substances can -both increase and de-
crease ; in these cases the quantities of the acting
substances may be regarded as variable quanti-
ties, and when there is equilibrium there will be
a definite relation between them. If, however,
the circumstances are such that processes pro-
ducing both increase and decrease of the quan-
tities of the substances cannot occur, then we
can no longer regard these quantities as vari-
ables, and there wUl not be the same relation
between them as if such changes could take
place ; we may call the equilibrium in this case
' partial ' equilibrium ; it is definite with respect
to the physical conditions but not with respect
to the chemical. Thus in the case of the oxygen
and hydrogen at low temperatures, the quanti-
ties of steam, hydrogen, and oxygen, must be re-
garded as constants, and equilibrium may sub-
sist with any values for these quantities ; if, how-
ever, we raise the temperature to such a point
that the oxygen and hydrogen can combine and
the steam be decomposed, the quantities of hy-
drogen, oxygen, and steam may now be regarded
as variables, and there will be a definite rela-
tion between them when there is equilibrium.
The case of oxygen and hydrogen at low
temperatures is a somewhat extreme one, as no
chemical action at all goes on ; there are, how-
ever, cases in which some of the quantities may
change, but only in one way, they can increase
but not diminish, or vice versd. Thus at low
temperatures HI can be decomposed by Ught,
while H and I cannot combine, so that the ac-
tion is irreversible, and Lemoine has shown
that when a mixture of EI, H, and I is exposed
to the action of Ught the decomposition of the
EI goes on indefinitely.
ia Older to enable those processes to go on
which cause the state of the system to be re-
versible, something more than the mere collisions
between the molecules of the substances seems
to be required ; in fact, collisions alone seem un-
able to effect the decomposition of molecules of
simple composition. We shall see evidence of
this when we consider the phenomena attending
dissociation, but considerable evidence may be
derived from the fact that it is extremely dif-
ficolt in many cases to get two pure gases to
enter into chemical combination, though they
readily do so when a small quantity of a properly,
chosen third substance is introduced, which by
secondary chemical actions may.be supposed to
effect the decomposition of the molecule. Ex-
amples of this are afforded by Dixon's experi-
ments on 'the difBculty of making CO and 0
combine when perfectly dry, though they do so
readily when moist {T. 1884, 617). Pringsheim
(W. A. 32, 384) has lately shown that perfectly
dry chlorine and hydrogen do not explode when
exposed to light. The change in the conditions
required to enable the molecules to be decom-
posed is often exceedingly small. The most
striking illustrations of this are furnished by
catalytic agents, such as spongy platinum, which,
while remaining to all appearance unchanged
themselves, are yet able to alter completely the
conditions of the system in which they are
placed. We may suppose that the system before
the introduction of these agents was in partial
equilibrium only, in consequence of certain de-
compositions and recombinations not being able
to take place, perhaps because the collisions
alone were unable to split up the molecules ; but
that when these agents are introduced secondary
chemical actions produce decomposition of the
inolecules, and so render aU the processes rever-
sible, the equilibrium which was before only
partial becoming complete. Since a system in
'partial' equilibrium may be widely disturbed
by the introduction of an excessively small
change of some kind (such as the presence of a
minute quantity of spongy platinum), it corre-
sponds to tfhat in dynamics is called unstable
equilibrium, and might have been called so here
if it were not rather straining the customary use
of the word to apply it to a state which may last
for an indefinite time. On the other hand, if a
very small quantity of a catalytic agent were in-
troduced into a system in ' complete ' equili-
brium, it would not produce a finite change ; such
a state corresponds to what in ordinary dynamics
is called stable equilibrium. We may regaird
catalytic agents as reducing a system from partial
to complete equilibrium.
The difference between ' partial ' and ' com-
plete ' equilibrium may be summed up as fol-
lows : when a system is in 'partial' equilibrium
the quantities of some of the constituents may
be altered without any change in the others,
while in ' complete ' equilibrium a change in the
quantity of one of the constituents involves a
change in the quantities of some or all of the
others. The introduction of an indefinitely
small amount of a third substance, or the com-
munication of an indefinitely small quantity of
energy, to a system in 'complete' equilibrium,
will only produce an indefinitely small change
in the state of equilibrium, while the state of a
system in 'partial' equilibrium may be pro-
foundly modified by the same means.
EiNEUATICAL METHODS OF CONSISGBINa ChEMICAIi
Equilibbium.
We must now go on to discuss the theory of
chemical equilibrium, considering at first the cases
where the equilibrium is ' complete.' The question
maybe discussed from two points of view — the one
kinematical, the other dynamical. We shall begin
with theories founded upon kinematical princi-
ples, as, though their application is more limited
than those based upon dynamical ones, yet as far
as they go they afford us a clearer view of the
subject, and are therefore better fitted for an in^
trodnction to it. They have also the advantage
over the dynamical theories of giving us some
information about the behaviour of the system
before it reaches the state of equilibrium.
v^2
4^
EQUILIBRIUM, CHEMICAL.
The kinematical theoriee depend upon the
conception which we owe to Clausius and
Williamson, that in reversible chemical pro-
cesses, such as the dissociation of a gas, the
moleculps of the gas are continually splitting
up, and the atoms which are thus produced are
contiunally recombining. When the state of
equilibrium is reached the number of molecules
decomposed in unit time must equal the number
formed in the same time by the recombination
of the atoms. Let us now consider the applica-
tion of these principles to the simplest case of
chemical combination we can choose, that of the
dissociation of a diatomic gas into atoms. Since
the molecules are continually splitting up, the
time each molecule exists without decomposi-
tion is finite, and though this may vary from
molecule to molecule the mean of such time
will, however, be finite, and we shall call it the
' paired ' time of the molecule and denote it by
tf. The mean time an atom remains alone
and free from other atoms, we shall call the
' free' time, and denote it by t' ; since an atom in
order to recombine must come close to another
atom, the time an atom remains free will be
inversely proportional to the number of collisions
it has with other atoms, and therefore inversely
proporuonal to the number of such atoms in
unit volume. We may thereforoi put t' = -L^
where n is the number of free atoms in unit
volume. To simplify the calculations, let us
suppose that the time each molecule remains
paired is the same for all molecules and equal
to the paired time, and that the time an atom
is free is the same for aU atoms and equal to
the free time. Then if N be the number of
molecules in unit volume, the number of mole-
cules which split up in a short time, St, will be
-— -, for we may suppose that the rate at which
h
the molecules split up remains constant for the
time t„ but if so, N will split up during this
time, so that the number which splits up in
unit volume in the time St will be — — ; similarly
the number of atoms which pair in the time St
will be —,St, that is -St. Thus, if SN is the in-
the number c
V2 T - tj
crease in time St in the number of molecules in
nnit volume,
dN_l M»
dt 2 r
N
dn 2N
T
similarly,
When the gas has reached a steady state ~
dt
and ^ both vanish, so that ~ = ^'^ . . (1)
dt . N t,
From this expression we can find the vapour
density of the gas when it is in the steady
state. Iiet A be the density of the normal gas,
and A' that of the dissociated gas at the same
pressure ; then, if S is the number of molecules in
r^iit vgluuie pf ih§ normal gas before dissociation,
A'
A
S
'N + TO
Hence,
„_2S(A-A-)
A'
y^_S(2A--A)
A'
s.|
So that equation (1) becomes
2(A-A>)» T
(2A'-A)A''*-<, ■
But if the temperature remains constant S is
proportional to the initial pressure p, so that
we may write this equation as
p(A-A')* , T
(2A'-A)A'°'(^°°°^^^*)i; • • (2)
The result that ^j^~^| , is constant, was
(2A' — A}A'
obtained by Willard Gibbs from thermodynamioal
considerations, and was shown by him {Am. S.
17, 277) to agree with the results of experiments
on the vapour densities at different pressures
of nitrogen peroxide, and acetic and formic
acids. More recently a most elaborate deter-
mination of the vapour density of nitrogen
I peroxide at different pressures has been made
'by E. and L. Natauson {W. A. 24, 454),
with the result that at a constant temperature
r!rn — A-rr is constant. The preceding investi-
(2A* — A)A'
gation shows that when a dissociable gas obeys
this law -^ must be independent of the density,
and therefore, since r does not depend upon the
pressure, i, cannot do so ; but it t, is indepen-
dent of the pressure, the decomposition of the
more complex molecules cannot be produced by
collisions with molecules or atoms of the same
kind, for if it were t, would diminish as the
pressure increased. There does not appear to
be any reason for supposing that on the kinetic
theory of gfises the collisions between the mole-
cules must of necessity produce decomposition.
There must be a limit to the velocity with which
a particle is moving, for it is evident that the
kinetic energy possessed by a single particle
must be less than the kinetic energy in the
smallest quantity of the gas which eidiibits the
property of the gas when in bulk. Thus, if a
million molecules are sufficient to make the gas
possess this property, the greatest value of the
square of the velocity of a molecule would be a
million times the velocity of mean square at this
temperature, and therefore the square of the
relative velocity of the atoms in a molecule
after being struck by another molecule must be
less than this value. The atoms in the mole-
cule will not, however, part company unless the
square of the relative velocity exceeds a certain
value, depending upon the distance between the
molecules, the law of force between them, and
the intensity of this force at imit distance, so
that the force may be so intense and the atoms
so near that to spUt up the molecule the rela-
tive velocity of the atoms would have to be
greater than that which could be produced by a
cpllisipn with any molecule in the gas.
EQUILIBRroM, CHEMICAL.
437
To return to formula (1), we see that if x
denotes the ratio of the number of dissooiated
atoms, ro, to S, the number of molecules originally
present in unit volume, then
(3)
or if only a small fraction of the molecules is
dissociated
80 that in this case the amount of dissociation is
inversely proportional to the square root of the
pressure.
By observing the amount of dissociation
when the gas is in equilibrium, we can determine
XT
X, and hence by equation (3) -L or ^
''^ IT
this latter quantity is x times the ratio of the
free to the paired time, so that by determining
the vapour pressure of a gas when in a steady
state, we can determine the ratio of its free to
its paired time. Thus by comparing equation (3)
with the resalt of Lemoiue's experiments on the
dissociation of EI, we find that, under atmo-
spheric pressure, at 1250° the paired time is 1-32
times the free time, and at 900° only |. We
cannot, however, by observations on the gas in
the steady state determine the value of either
of these times absolutely ; if, however, we have
determined their ratio in this way, we can, by
observing the velocity of dissociation, determine
the 'free ' time of the atoms, for from equation
(1) we have :
dre^2N_w^
dt ti T
2S-n n?
h
which can be found
If we denote g- by c,
DC]
by observations on the steady state of the gas,
the solution of this differential equation, if
o = S/'2c +
(-*9
is H- log la ' = — + constant,
2a n + ^So+a r '
BO that if <, is the time required for the number
of atoms to increase from m, to n,
L loB {«; + iSc-a) (n^ + iSc + a) ^ tj -^,
2a ^ (», + |Sc+o) (»j + 4Sc-a) t
Hence, if we observe the time taken for the
dissociation of a known fraction of the gas we
shall be able to find from this equation the
' free time,' and then, as from observations on the
steady state we know the ratio of the paired to
the free time, we can find the paired time.
The same principles can be applied to more
complicated cases of equilibrium, such as the
combination of hydrogen and iodine to form
hydriodic acid. We shall suppose that the
molecules of hydrogen and iodine and hydriodic
acid are continually splitting up into atoms,
and that these atoms are constantly recombining
and forming molecules. In this case we have
five things to consider, the hydrogen molecules
and atoms, the iodine molecules and atoms, and
the hydriodic acid molecules.
Let m and n be the number of hydrogen atoms
and molecules respectively ;
p and 2 the number of iodine atoms and
molecules; i
r the number of hydriodic acid molecules ;
t„ fj, t„ the times two atoms remain paired
together in the hydrogen, iodine, and
hydriodic acid molecules, respectively ;
— ', —the times a hydrogen atom is free from
HI p .» o
a hydrogen and iodine atom respectively;
- the time an iodine atom is free from
P
another iodine atom;
M and N the total number of hydrogen and
iodiue atoms respectively, whether free
or in combination with other atoms.
Then by the same reasoning as in the case
of dissociation :
dm_2n r_2m?_mp
dt ti t, T, r,
dn_m!'_n
dt r, t,
dp_2g T_2^_mp
dt <2 t, T, T,
dq_p^ q
dt Tj tj
4r_mp_t
dt Tj t,
m + 2n + r = M
2> + 22+r = N.
When the system has got into a steady state,
m, n, p, 2, r are aU constant, so that the above
equations may be written :
r.
n p'
"il' ^
mp r
(5)
In solving these equations we may assume that
the number of free atoms of hydrogen or iodint
is very small compared with the number of
molecules; so thatM = |(M— r)andg = J (N— r);
hence from equation (S) we get :
— '^= -^(M-r)(N-r)
(6)
If equivalent quantities of hydrogen and iodine
are present M == H and we have :
-OS?}*^^-^^-
In this case the ratio =-, is independent of the
M
pressure.
Lemoine has made a very extensive series of
experiments on the combination of hydrogen
and iodine (A. Ch. [5] 11). In the following
table the results of his experiments are compared
with those given by equation (6) ; the value of
zlH^ being determined by making the observed
tit^T^'
and calculated results agree when N = M.
438
EQinXIBRroM, CHEMICAL.
Comhimation of hySrogen and iodine at 440°.
Proportion of Eatio of free hydrogen to the
H H- 1. total quantity of hydrogen.
Observed. Calculated.
H + I -240 -240
H + •784.1 -350 -342
H + -527I -547 '519
H+-258I -774 -750
We see too from equation (6) that if M is very
large compared with H, then r=N; that is, if the
iodine is enormously in excess, the whole of the
hydrogen is combined with iodine; in other
other words there is no dissociation of the
hydriodio aoid ; the effect of an excess of either
hydrogen or iodine on the dissociation of EI is
given by equation (6).
We could make other assumptions about the
way in which the hydriodio acid was formed
from the hydrogen and iodine which would lead
to the same results for the equilibrium-condition,
but which could be distinguished from the pre-
ceding assumptions by observations on the rate at
which dissociation takes place. Thus we might
suppose that the combination of hydrogen and
iodine takes place by a molecule of hydrogen
coming close to one of iodine, and that these
molecules emerge from the collision as two mole-
cules of hydriodic acid. The decomposition of
the hydriodio aoid might be supposed to be
caused by two of its molecules coming into
collision and emerging as two molecules of
hydrogen and iodin^. In this case, if n, j, r,
represent the number of molecules of hydro-
gen, iodine, and hydriodic acid respectively,
— the time a molecule of iodine exists without
combining with one of hydrogen, _ the time a
molecule of hydriodic acid exists without com-
bining with another to form two molecules of
hydrogen and iodine ; then
dt ti tj
and when there is equilibrium
This is an equation of exactly the same form
as that previously obtained on the other hypo-
thesis, so that by observations on the equilibrium-
condition we could not distinguish between them.
The two hypotheses lead, however, to quite dif-
ferent expressions for the velocity with which
various changes take place. Thus let us con-
sider the rate at which a quantity of HI would
dissociate according to the first hypothesis ; in
this case the initial rate of dissociation is given by
dr_ _r
dt ts
according to the second
dt" i^
Thus according to the first hypothesis the
quantity of hydriodic acid dissociated in a short
time is proportional to the pressure, while accord-
ing to the second it is proportional to the square
Of the pressure, so that the two hypotheses could
readily be distinguished by observations on th6
rate of dissociation.
We can apply the above principles to any case
of the combination of gases, but after what we
have given, the reader will have no difficulty in
making the investigation for himself, and we
shall merely give the results.
Three monovalent gases. A, B, C, are mixed
together ; A. can combine with both B and 0 to
form the compounds ABand AC respectively, hut
B and C cannot combine ; we wish to find how
much of each compound is formed.
Let n, q, s, u, v, be the number of molecules
in the steady state of A, B, C, AB, AC respec-
tively, then we can prove
(7)
where a and /3 are constants, of which a does not
depend upon C nor /3 upon B. Thus the number
of molecules of the compound AB formed is pro-
portional to the geometric mean of the number
of free molecules of A and B, and similarly the
number of molecules of the compound AC is pro-
portional to the geometric mean of the number
of free molecules of A and C.
We see from the equation that the same pro-
portion of gases will enter into combination at
all pressures. If M, N, P are the total number
of atoms of A, B, C, respectively, in the vessel,
then equation (7) may be written
M« = io(M-M— k){N-m)
»)^ = i/3(M-M-«)(H— «) '
(8)
hence
Suppose that C is largely in excess of A and B,
then F -V will be large compared with N— «, so
that V must be large compared with u, that is, C
absorbs practically the whole of A, and only a
very small quantity of the compound AB is
formed ; if, however, both A and C are largely in
excess of B then there is very little free B, the
whole of it being converted into AB. Equation
(8) enables us to find how much of each com-
pound is formed when the substances are mixed
in any proportions.
Another case we can solve by the same prin-
ciples is when we have four substances, A,B,C,D,
such that if their molecules are represented by
{A}, {Bj, {C|, {D( ; the way they act on each
other 13 expressed by the equation
olA}+i3{B}=7{C}-HS{D},
the action being reversible ; that is, A and B act
on each other to produce C and D, and C and D act
on each other so as to produce A and B. Then if
jp, 2, r, s are the numbers of molecules of A, B,
C, D respectively, we may prove by the method
j.ust described that
p'gf = Kt^s' (9)
when K is independent of jp, g, r, and s. If
a + $ = y + S, that is, if the chemical action does
not produce a changein the number of molecules,
the relative amounts of the substances produced
by the action will be independent of the pressure.
If P, Q, P', Q'are the masses of A, B, C, D present
initially, a|, ;8J the number of molecules of A
and B which have disappeared, and 7f, 5{ the
number of molecules of A and B which have ap-
EQUILIBRIUM, CHEMICAL.
peared when equilibrium is reached, then equa-
tion (9) may be written
{P-o|)-(Q-«)«=«(P'+7fl''(Q'+5f)' • (10).
Thus if P»Q* is greater than icP'rQ", | is positive,
that is, the A and B molecules combine to form
C and D ; but if P'Q* is less than kPVQ'* { is ne-
gatiye, that is, the 0 and D molecules combine
to form A and B ; thus the nature of the chemical
action depends on the relative amounts of the
combining substances initially present. This is
an example of what is called mass action, which
we shall consider more in detail in the following
paragraph. Por other examples of the applica-
tion of this method we may refer to a paper by
J. J. Thomson on chemical combination IP. M.
18, 232).
Ouldberg and Waage's Theory.
A theory of chemical action based to some
extent on Mnematical principles was given by
Goldberg and Waage in 1867 {Etudes sur Us
AffimUs Chimvigues), and an extended applica-
tion in 1879 (J. pr. 19, 69) ; the results of this
theory have been compared by the authors and
others with the results of a large number of ex-
periments. The theory may perhaps best be
illustrated by considering a special case. Let us
suppose that we have four soluble substances,
A, B, p, D, in solution, and that these substances
are such that A by its action on B produces C
and D, while C by its action on D produces A
andB ; we may suppose that the four substances
are hydrochloric acid, sodium nitrate, nitric acid,
and sodium chloride. Let^, g,r,sbe the masses
of these substances, respectively, expressed in
gram-equivalents, v being the volume in which
they are contained, then^, £,?!,£, are called
V V V V
by Guldberg and Waage the active masses of the
four substances, and they assume that the amount
of A and B which in unit time changes into G and
D is proportional to the product of the active
masses, and may be expressed by
where k is what they call the coefficient of affi-
nity of A andB ; similarly the amount of C and
D which in unit time passes into A andB is
* — t
V V
where k' is the coefficient of affinity of C and D.
When the system is in eqniUbrimn the amount
of A and B which passes into C and D in unit
time must equal the amount of C and D which
passes into A and B, so that
lepg = it'ri,
or if P, Q, B, S, are the amounts of A, B, C, D,
initially present, and | is the number of equiva-
lents of A and B which change into G and D,
this equation may be written,
'c(P-|)(Q-0 = «'(B + l)(S + f) . . (11)
This is a quadratic equation to determine | ; but
we may easily show that it has only one admis-
sible root, for if J is positive it must not be
s;reater than the smaller of the quantities P and
Q, and if negative it must not be greater than
439
This
the smaller of the two quantities B and S.
root is given by
,-*(P+Q) + «'(R + S)
2(k-k')
± / /«(P + Q + ic^(R?S) \ \ kPQ - Kits
V I 2(K-(t') / "-Kf
the -t- or — sign being taken according as
K—Kf is jiegative or positive.
From equation (11) we see that if F is
very much greater than Q, B, and S, Q — $ must
be very small, that is, nearly the whole of B
must combine ; thus if we mix a large quantity
of hydrochloric acid with smaller quantities of
NaCl, HNO„ NaNOs, nearly the whole of the
NaNOj wiU be changed into NaCl. Again, if
kPQ is greater than /c'ES, J is positive, but if less,
then f is negative; thus the way the reaction
goes will depend upon the relative amounts of
the combining substances initially present.
Thus, if, in tiie case before oonsidered, the
amounts of HOI and NaNO, are large compared
with those of NaCl and HNO,, the reaction which
goes on will be the conversion of NaNOj into
NaOl and ENO, ; but if the quantities of HCl and
NaNO, are small compared with those of NaCl
and HNOj the reverse action will go on, and
NaGl and HNO3 will be converted into NaNOj
and HCl. This effect of the quantities of the
various substances in determining the nature of
the chemical reaction is called mass action'.
If we put P = Q, E = 0, S = 0, equation (11)
becomes
Now if P and B are acids, Q and S salts, :^^
is the ratio in which the base divides itself be-
tween the acids A and B respectively, so that
for this case -, is the
square of the ratio in
which the base divides itself between the acids.
Cornpa/rison of Guldberg and Waage's Theory
with Experiment.
Etherification. — Guldberg and Waage
have compared their theory with the results of
the experiments of Berthelot and St. Gilles upon
etherification (A. Gh. [3] 65, 385 ; 66, 1 ; 68,
225). If A, B, C, D are respectively acetic acid,
water, ether, and alcohol, they find ^ = 4. The
observed and calculated effects of mixing these
substances in different proportions is given in
the following table : —
Quantity of acetioaold
InitiEa quantities of
which enters into
combination
acetic
acid
water
ether
alcoliol
observed
calculated
P
Q
B
S
f
f
1
0
0
, 1
■665
•667
1
0
0
2
■828
•845
1
0
0
4
•902
•980
2
0
0
1
■858
•845
1
0
1-6
1
•521
•492
1
3
0
1
JL
■407
■409
1
23
0
1
■116
•131
1
98
0
2
■073
•073
440
EQUILIBRIUM, CHEMICAL.
Division of a pase between two acids.
Thomsen's experiments. Thomsen, by measuring
the thermal changes accompanying the reaction,
VBS able to calculate the distribution of the
masses (Thomsen's Thermochendsche Unter-
sucJmngen, 1, 98). When A, B, C, D were respec-
tively nitric acid, sodimn snlphate, sulphuric
acid, and sodinm nitrate, Thomaeu found that
-, = 4, and when they were mixed in difierent
proportions the results were given in the follow-
ing table, where Q = l, K=0, S = 0 :—
p«
iquivalents of nitric acid -i- ]
equivalent of
sodium sulphate :—
Heat absorbed
t
(
• • observed
caloalated
1
•121
452
462
^
•232 .
808
828
^
■423
1292
1331
1
•667
1752
1773
2
•845
2024
1974
3
■903
2050
2019
The following tables, derived from Thomsen's
experiments, are given by Guldberg and Waage
(J.i>r. 19,87) :—
Eelative values of it.
Table I.
Substance A. >
Substance B
K
HCl
NaCl
1
HNO,
KaNO,
1
JHAOJ
iraa^SOO
KNaAOJ
•25
' ^0676
H,PO,
NaHjPO,
•0625
4(0.H,0,)
AC,H,NaA
•0025
iO,H,Na,0,i
•0025
CjHjNaOj
•0009
H±iUj
NaBO,
•0001
Table II.
Substance A
Substance B
(
HCl
i(H.SO,)
Chloride of a
metal
sulphate
1
•25
where the metal may be potassium, sodium, or
ammonium.
Table III.
Substance A
Substance B
K
HCl
J(H,S0J
Chloride of a
metal
sulphate
1
•5
where the metal may be Mg, Mn, Fe, Zn, Co, Ni,
Cu. We see, therefore, that the value of —, is
K
almost independent of the nature of the base.
Ostwald repeated the experiments, using the
^change in volume of the solution to determine
the distribution of the substances. . The experi-
ments are described and the results given in the
art. ArriMiTT (vol. i. p. 75).
Seterogeneous systems. — So far we have
only considered those cases in which the four
substances are in the same condition, being
either aU soluble or all gaseous; we can, how-
ever, apply the same considerations to the case
when one of them, D suppose, is an insoluble
solid. In this case if the extent of surface of D
exposed to the solution does not alter, its active
mass is constant ; thus, using the same notation
as before, we must regard s as constant, and
then the equation becomes
Kp2 = ic'rs,
or sincQ s is constant,
(P-|)(Q-J)=c{B-Ht),
This expression has been ven-
where c is — ,
fied by W. Engel (J.pr. 19, 94) for the case where
A, B, 0, D were respectively oxalic acid, chloride
of calcium, hydrochloric acid, and calcium oxal-
ate. The results are given in. the following
table : —
1 equivalent of calcium chloride -I- F eqni-
valents of oxalic acid.
If two of the four substances, B and D, are
insoluble, then if the surfaces remain constant
their active masses are constant, and the equation
Kp2 = ic'r*
will become
(P-|)=c(E + {),
where c is a constant and equal to — . This
expression has been tested by Guldberg and
Waage for two oases (J. pr. 91, 92). The first
case is when A, B, C, D are respectively potas-
sium sulphate, barium carbonate, potassium
carbonate, and barium sulphate ; they found that
when the system had reached its state of equili-
brium, the quantity of potassium sulphate was
^ that of the potassium carbonate. The effect
of mixing the substances in different proportions
is given in the following table : —
Initial quantities of
Quantity combined
potassium
sulphate
potassium
carbonate
'ob-
served
oalcu^
lated
P
0
B
3^5
•7W
*
•70C
0
2^5
•500
•500
0
2
•395
•400
0
1
•176
•200
•25
2
•200
■200
•25
2^5
•300
■300
■25
3
•408
•400
•25
3-8
•593
•560
•50
2
trace
•000
EQUILIBRIUM, OHEMICAL.
441
The second case ot this kind investigated by
Gkildbeig and Waage was when A, B, G, D were
respectively sodium sulphate, barium carbonate,
Bo£um carbonate, and barium sulphate; they
found that in this case when the system had
reached its state of equilibrium the quantity of
sodium sulphate was | of the quantity of sodium
carbonate. The effect of mixing the substances
in various proportions is given in the following
table : — r
Initial quantity ot
Quantity combined
sodium
-sodium
ob-
calcu-
sulphate
carbonate
served
lated
P
B
f
' f
0
5
•837
•833
0
3-5
•605
•583
0
2
•837
•333
0
1
•157
•167
•2956
3
•234
•254,
•2956
3-86
•438 '
1 ^396
•2956
4-10
•440
•437
•2956
4-73
•558
•543
The method we previously described will lead to
the same results for the equilibrium of hetero-
geneous substances as Guldberg and Waage's
method.
The preceding instances show that in a large
number of cases Guldberg and Waage's formula
iepq = i^p'^ represents accurately the state of
equilibrium ; nevertheless as given by Guldberg
and Waage the formula must be regarded as
almost empirical. The reasoning they give is
only applicable to the special case of combina-
tion when the two molecules A and B after
coming into contact separate as two molecules of
A' and B' ; the reasoning as they give it is not
applicable to the case where the molecules of A
and B have to split up into atoms before com-
bination can take place, though if we use the
kinematical method previously described we shall
arrive at the same formula, in this case, if the
chemical equivalents and the' molecules are iden-
tical. .The agreement of the formula with the
experiments in some cases throws some light on
the constitution of the molecules which take part
in the reaction. Thus take the case represented
by the equation
HjSO, + 2NaN0, = 2HNO3 + Na^SO^
p i r s
Now if the molecule of sodium nitrate is repre-
sented by NaNOs, the molecule of BCjSO^ has to
come into collision with two molecules of NaNO,
simultaneously for combination to take place,
and the number of such collisions is proportional
to pgf. Again the number of collisions which
can give rise to the reverse chemical action will
be proportional to rs'', so that for equilibrium
If we compare this formula with Thomsen's ex-
periments on this reaction we shall find that it
does not agree at aU well with the results, whUe
the formula Kpq = ic'rs does so. Again, if we
consider the question from the dynamical point
of view (v. V. 442) we shall also arrive at the
equation icpq'=ic'rs', if we assume that the
molecule of sodium nitrate is represented by
NaNO, ; if on the other hand we assume that the
molecule is represented by NajNjOj, both methods
lead to the equation Kpg = K'rs, which is verified
by experiment. Eencn we conclude, either that
the relative composition of the molecules is re-
presented by the scheme HjSO„ NajNjOj, NajSO,,
'S^THJii,, or else that a salt solution is in no way
analogous to a number of particles of the salt
moving about in a volume equal to that of the
solvent. It may be well to remark that we can-
not get over the di£fioulty by assuming the above
reaction to take place in two stages, thus
HjSO^ + NaNOa = HNaSO, + HNO,
HNaSO^ + NaNO, = Na^SO, + HNO,.
Ostwald's researches {v. Ajmjxnii) show that the
ratio in which a base divides itself between two
acids is generally independent of the nature of
the base, though if one of the acids is HjSO^
there are exceptions to this rule. We may
therefore regard k as the product of two
factors a and P, of which a depends only upon
the acid and j3 only upon the base, while k' will
be the product of P and another factor a' which
depends only on the other acid ; the ratio of k
to k' will then be the same as the ratio of a to
a', and wiU depend only upon the acids. If we
apply the method given on p. 436 to this case we
can see how this may be brought about. Iiet us
consider the reaction
HCl + NaNO, = HNO, -I- NaCl.
Let p, q, r, s be the number of molecules ot
HCl, NaNO,, HNO3, and NaCl respectively, t„ <„
t„ if, the paired time of these molecules, and let
X, y, a, w be the number of free atoms of H, CI,
NO3, and Na respectively, -^ the time an atom
''1
3
of H is free from one of CI, — the time an atom
of E is free from one of NO,, — the time an
atom of CI is free from one of Na, and — the
time an atom of NO, is free from one of Na ;
then, by the method on p. 437, we have the fol-
lowing equations : —
dp
di
_ ^1
■^1
P
dq
dt
ISW
2.
dr
dt
xz
^ ■^s ~
r
i.
ds
dt
wy
T4
s
So that when there is equilibrium
"f^n = ¥^^* ' • (12)
T„ T„ ti, t, are the only quantities which depend
upon the base. We may regard the salt as made
up of two systems, the radicle and the base, held
together by forces between them ; these forces
will depend upon the relative configuration of
the two systems, and we may suppose that this
force vanishes when the two systems have simul-
taneously the configurations a and jS. Now if
T„ T, are the times of vibrations of the systems
about the configurations a and fi respectively, the
time which elapses between the two systems leav-
ing this configuration and entering it again will, if
442
EQUILIBRIUM, OHEMIOAU
T, and T^ are incommensurable, be T, x T,, so
that if the system can get into the state in which
the force between them yanishes, the longest
time they can exist without doing so will be
T, X Tj, and thus the paired time will be propor-
tional to T, X Tj. The two systems will probably
vibrate approximately as if they were free, so
that, approximately, T, wUl only depend upon the
radicle and Tj on the base ; thus, since the base
in NaCl is the same as in NaNO,, the ratio of
(2 to tf will be independent of the base. Again,
when the base andradicle come together again after
having been dissociated, the force between them
will depend upon their configuration, and we
may suppose that unless the atoms are in cer-
tain configurations the force between them will
not be sufficient to cause them to enter into com-
bination. If T,', Tj' arp the times of vibration
of the radicle and the base about these configu-
rations, the time which will elapse between the
systems leaving this configuration and entering
it again will be T, ' x Tj' , the longer these intervals
are separated the less chance will there be of the
system entering into combination, and the free
time will be proportional to T,' x Tj' ; since one
of these factors depends only on the base, and the
other only upon the radicle, -? will be indepen-
dent of the base, and therefore by equation
(12) the proportion in which the base divides
itself between the two acids will be independent
of the base. (For another method, partly kine-
loatical, v. Ffaundler, P. Jubelbd. 182, 131, 55.)
Dykauicaii Methods.
In any dynamical system in a steady state
there is a certain quantity called the Lagrangian
Function (T — V, where T and Vare respectively
the mean kinetic and potential energies of the sys-
tem) which reaches a maximum value when the
system is in a steady state, and the knowledge
of the expression for this' quantity enables us to
determine the configuration of the system when
in this state. Exactly the same thing holds for
the physical and chemical systems whose equili-
brium we are now considering. It may be proved
(see Applications of Dyna/mics to Physios and
Chemistry, 3. J. Thomson, chap, iz.) that when
such systems are in a steady state their mean
Lagrangian Function has a maximum value, and
that all the circumstances of the equilibrium can
be obtained by making use of this property. We
shall for brevity call the mean Lagrangian Func-
tion, the quantity which has this property, the
' directrix' of the system, as the behaviour of
the system is entirely regulated by this func-
tion.
The directrix is closely analogous to what in
thermodynamics is called the entropy of the sys-
tem, and the theorem that in the steady state
the ' directrix ' is a maximum is analogous to
Clausius' theorem that the entropy of the sys-
tem tends to a maximum. Willard Gibbs (EquiU-
brivm of Heterogeneous Substances ; Am. 8. 16,
442), Horstmann (B. 12, 64), Liveing (Ghemical
Equilibrium, the result of the degradation of
Energy) (Planck, W. A. 30, 562 ; 31, 189 ; 32,
462), have treated the subject of chemical equili-
brium from this point of view. As the problems
can, however, be solved by purely mechanical
principles it seems preferable to do so. ThougU
we can obtain the conditions of equilibrium both
from mechanical principles and from the Second
Law of Thermodynamics, it does not follow that
we can therefore deduce the Second Law of
Thermodynamics entirely from mechanical prin-
ciples. The Second Law of Thermodynamics
consists of two parts : one, that every distribution
of heat tends to uniformity, by heat passing from
places of higher to places of lower temperature ;
the other, that the entropy is a perfect dif-
ferential ; the second of these statements, but not
the first, can be proved by purely dynamical prin-
ciples. It must be remembered that what we show
is that if the system does reach a steady state,
the directrix must be a maximum ; we cannot,
however, prove that it must reach this state;
this has to be deduced from observation.
In order to apply this method to find the
conditions of equilibrium for chemical systems,
we shall requirethe expressions for the directrix
both for a mass of gas and a mass of liquid. If L,
be the directrix for a mass J of a gas, which obeys
Boyle's Law, and whose density is p, and abso-
lute temperature 9, then (J. J. Thomson, Appli-
cations of Dynamics, chaps, x. and xi.)
L, = {R,e log i° + |Afl + (Be log fl - {V, . (13)
P
where B, is the value ot S., n being the pres-
pe
sure ; p„ A, and B are constants, and V, is the
mean potential energy of the molecules of unit
mass of the gas.
The directrix L, of a mass v of liquid, free
from strain, electrification, &e., is given by the
equation
L2=1*(9)->?V, . . . (14)
when ip (6) is a function of the temperature, and
Vj is me mean potential energy of the molecules .
of unit mass of the liquid. If the liquid is
strained or electrified, or if it possesses energy
in virtue of its surface tension, we can easUy
calculate the correction to the directrix ; for, since
the directrix is T-V, all that we have to do is to
calculate the potential energy arising from the
strain, &o., and subtract it from the expression
(14). Thus if the liquid is strained we must
subtract from (14) JfcVjir*, where k is the bulk
modulus of the liquid, V„ its volume when un-
strained, and <r is the compression ; again if the
liquid has a free surface it will possess potential
energy in virtue of its surface tension, equal to
ST when S is the area of the surface and T the
surface tension ; to get the directrix in this case
we must, therefore, subtract ST from the value
given by (14).
To illustrate the method of solving problems
by this principle, let us take the case of the
evaporation of a liquid in a closed vessel. We
have here two systems to consider : the vapour
and the liquid ; if | is the mass of the vapour,
which we shall assume to obey Boyle's Law, its
directrix L, is given according to (13) by
L, = iE,9 log t» + {Afl + {B9 log fl - JV, ;
P
while if 7) is the mass of the liquid, its directrix
L, is given by
L,=7,0(e)-„V,j
EQUILIBRIUM, CHEMICAL.
443
and if A is the directrix of the whole system,
When the system is in equilibrium A must be a
maximum, so that if we suppose a mass SJ of
the liquid to evaporate we must have in the
state of eqmlibrium
t = 0 . .(15)
Sitioe the sum of the masses of the vapour and
liquid is constant ^= _i, so that equation (15)
leads to the relation
Beiog?2 + Ee^ + Afl + Beiogs - <(){e) - (u, - ■Wj) = 0
(16)
where a is the density of the liquid. This gives
the expression for the vapour density p of the
liquid at the temperature 6.
It may be well to consider this case more in de-
tail. Let ns suppose that we start with some of the
liquid and no vapour : then the system will move
80 as to increase the directrix ; now at first when
/) = 0 the rate of increase of L, with | is infinitely
great, so that A will increase if a small quantity
of the liquid evaporates, and therefore, by the
principle just stated, evaporation will take place ;
as more liquid evaporates the rate of increase of
L, gets smaller and smaller, until a point is
reached where the increase in the directrix of
the vapour, when a small quantity of the liquid
evaporates, equals the dinunution of the direc-
trix of the liquid under the same circumstances ;
when this point is reached the directrix will be
a maximum and the system will remain in this
state. If the external circumstances alter so as
to affect the rate of change of the directrix of
either the vapour or liquid as evaporation goes
on, it will alter the point at which equilibrium
is reached. Thus, for example, suppose that
the liquid is in the form of a spherical drop :
then, in virtue of its surface tension, it wiU
possess potential energy proportional to its sur-
face; when it evaporates, the surface, and there-
fore the potential energy, will diminish; but
since the directrix of the liquid is T— Y, the
diminution in the potential energy of the liquid
when it evaporates .will cause the directrix to
diminish more slowly with evaporation than it
would if the liquid were of such a form that the
area of its surface did not change on evaporation.
The evaporation will, therefore, have to go on
further than before, in order that the rate of in-
crease of the directrix of the vapour shall sink
to that of the rate of diminution in the directrix
of the liquid. The vapour pressure, therefore,
when there is equilibrium wiU be greater when
the liquid is in the form of drops than when
its surface is plane. If the drop, however, had
been electrified, then, since the electricity is not
carried away by the vapour, the potential energy
of the liquid will increase as evaporation goes
on, and the drop gets smaller, so that the same
reasoning as before will show that the vapour
pressure over an electrified drop is less than over
one which is not electrified. These cases are
examples of a corollary from the principle we
are considering, which may be stated generally ,
by saying that when the physical environment
of a system is change4> and the consequent
change in the directrix of the system increases
as any physical process goes on, then this pro-
cess will have to go on further in the changed
state before equilibrium is reached than in the
unchanged one, while if the change in the direc-
trix diminishes as the process goes on it will not
have to proceed so far. The principle that the
directrix is a maximum in equilibrium readily
enables us to calculate the change made in
the extent to which the process goes on. Thus,
in the case of evaporation, if x is the change in
the directrix caused by any change in the con-
ditions, 5p the consequent change in the vapour
pressure when there is equilibrium, then we can
easily show that
E9 a-f di
In the case of the spherical drop, % is minus the
potential energy due to surface tension, or if a
be the radius -4)ra'T, and since ~= - — i—
we get
o--poEe
I>issociation. — We can apply the same
principles to oases of dissociation : let us suppose
that we have a gas A which dissociates into two
others, B and C ; let f , ?;, f be the masses of these
gases; p,, p^, p^ their densities ; u,, v^ v, the
mean potential energy of unit mass of their
molecules; E„ E,, Ej, the values of £■ for the
pfl
three gases respectively; then if L,, L^, L, are
the directrices of the three gases
Ii, = |E,e log fs + JA,e + JBS log 9 - JV, ;
ft
with corresponding expressions for L^ and L,.
A, the directrix of the whole system, is given
by the equation
A=Ii,+L2+L3;
if « is the volume in which the gases are con-
Wlien the system has
reached equilibrium, A is a maximum and
therefore — - is zero, if c„ c^, C3 are the com-
bining weights of the gases A, B, C,
finedp, = i,pj=I, p,=^.
V V V
dv_
■di
-l^andf=-
0, di
— m
So that the condition
leads to the equation
E.elog
ft Cl
E,9 log P""--!'
Pi "i
Eafllog
Pa
~{u,e-
1»E,9-
-3E,fl)-KA,-
or
JAJ.
+ (B,
- ?SBj
-■^B,)e log e
C]
-(«.-
I-'
or since
c
-i5«,)»(J,
*i
,Ei.= CjEj = CjE,
44^
thiB may be written
EQUILIBRIUM, CHEMICAL.
E,9
. (17)
Where C and a are constantB, in the case of
the dissooiation of an elementary gas into atoms,
we must suppose B and G to be the same, so that
V=Cot'='C, = ic,; thus equation (17) reduces to
:?! = cfl" 6 %rJL^ . . (18)
This equation is the same as that which we pre-
viously obtained from kinematical principles,
but expresses in addition the way the dissocia-
tion varies with the temperature. Formulas de-
rived from thermodynamical principles have
been given by Willard Gibbs {EqwiUbrium of
Eeterogeneoiis Substcmces, p. 169) and Boltz-
mann (W. A. 22, 39). In Willard Gibbs's foi;-
mula a is equal to —1, and in Boltzmann's it is
equal to zero. Natansou's experiments on the
dissociation of N^O^ show that neither of these
values of a agrees well with the observations.
We see from (17) that if we have given masses
of the substances, ^ is proportional to v, so that
the greater the volume in which the gas is con-
tained the greater is the dissociation. The effect
of an excess of one of the products of the disso-
ciation (v. art. Dissociation) follows at once
from (17).
— u,+ JOj— o, is the increase in the po-
c, c,
tential energy when unit mass of the gas disso-
ciates ; it may be approximately measured by H,
the amount of heat which must be supplied to
the system to keep the temperature constant
when unit mass dissociates ; when dissociation
is accompanied by an absorption of heat, H is
positive, when by an evolution, H is negative.
Introducing H into equation (17) we get
iv
ere '^'' (18)
BO that if H be positive ^^= 0 when B is 0, and,
Jo
therefore, either q or C must vanish, so that at
the absolute zero of temperature there is no dis-
sociation ; when 6 is infinite -— is infinite if a be
positive, t.e. £ must vanish, and therefore all
the gas be dissociated ; if a be zero — is finite,
and there is a finite amount of dissociation ; and
if a be negative ^- is zero, and there is again no
ii>
dissociation. We see from (18) that the greater
the thermal changes accompanying dissocia-
tion, other circumstances being the same, the
smaller will be the amount of dissociation at
a given temperature.
Dilute solutions. — So far we have only
considered gases, but Van 't Hoff (L'Equilibre
efmnigue dams les sysUirms gazeux ou dissous d
Vitat dilui, ArchAv. N^rlcmdais,20, 239 [1887])
has pointed out that Ffeffer's exper^iments on the
osmotic pressures produced by salts dissolved in
water (Pfefier, Oamotische XJntersuchvngen, Leip-
zig, 1887), and Baoult's experiments on the effect
of dissolved salts on the freezing points of solu-
tions (A. ph. [6] 4, 401), show that the molecules
of a salt in a diliite solution exert the same pres-
sure as they would exert if they were in the
gaseous state at the same temperature, and occu-
pying a volume equal to that of the liquid in
which the salt is dissolved, and that the pres-
sure exerted by these molecules obeys Boyle's
and Gay-Lussac's laws. This being so, the direc-
trix for the salt dissolved in the liquid must bf
the same as that for an equal mass of gas filling
the volume occupied by the liquid. The pre-
ceding remarks are strictly true for such solvents
as benzene or alcohol, but when the solvent is
water there are many exceptions to them ; most
inorganic acids and salts behave as if they exerted
a greater pressure than this rule would indicate,
and it has been suggested by Arrhenius that this
is due to the dissociation of the salt in the solu^
tion, though in some cases it would be necessary
to suppose that dissociation amounted to more
than 95 p.c. in order to explain the effect. We'
must remember that this representation of the
behaviour of a solution is founded on the hypo-
thesis that the solvent merely sustains the par-
ticles of the salt or acid, and it would require to
be modified if anything analogous to chemical
combination took place between the salt and the
solvent ; as such combinations do undoubtedly
in many cases take place, it does not seem
necessary to call in the aid of extreme dissocia-
tion untU it has been shown that the effects
could not be explained as due to the chemical
action between the salt and the water. The fact
that in order to produce comparable osmotic
pressures it is necessary to have in the solution
the same number of chemical equivalents rather
than the same number of molecules points also
to this explanation. If we assume that the direc-
trix of the dissolved salt is the same as that of an
equal mass of the substance when gaseous and
occupying the same volume, it is easy to calcu-
late the conditions of chemical equilibrium be-
tween them. For, let us take the case where we
have dilute solutions of four substances A, B,C,D,
such that when A acts upon B it produces C and
B, and when C acts upon D it produces A and B.
Let {A}, {B|, {C[, {D} represent the moleculea
of A, B, C, D respectively, and let the chemical
action which takes place be represented by the
equation
a{A}f6{B}=c{0}-l-d{D}.
Let {, 71, C, e represent the masses of these
substances respectively, and let the directrices be
{E,eiog^ + {(A,9-HB,fl log «)-{«;,
nEjfl log ^ + 7)(Aje + fij9 log 9) - „w,
tin "f
fR^elog^-h f(A,9-hB391og9)-f«;,
f B^9 log ^E^ + €(A,9 + B,9 log 9) - (w„
where « is the volume of the solvent, let Q
represent the directrix of the solvent, «>„ w„ w„
w„ being the potential energies of unit masses of
the substances. If c„ c„ c„ Cj are the com-
bining weights of the four substances, and di.
EQUILIBRIUM, CHEMICAL.
445
dii, d(, dt are cotreisponding increments in their
masses ; then the iuorements in the number
of molecules o{ each of the substances are pro-
portional to ^, ^, ^, ^; but by the nature
c, Cj c c,
of the reaction which goes on between these
substances, the increments in the number of
molecules must be proportional to a, b, —c, —d,
so that we have
ac, bc^ ce, ^ dc^
or ^ = ^, ^=_£^ l!=_^£l (19)
. di ac,' d| aCf dj ac,
Then, since in equilibrium the directrix is a
maximum, -=— must vanish; from this condition,
and remembering equation (19), and that B,c,
='E2Cj=EjC,=B4C„ we get
^= d)(9)u «+*-«-*« ^^ e~^ •'( (20)
when <t>{B) is a function of the temperature, and
w = {«;, + iWj + fwj + '«'«■
The value of -—■ will be zero if the proper-
di
ties of the solvent do not change as chemical
action goes on ; in any case since the solutions
are very dilute the properties of the solvent may
be assumed to be changed by an amount propor-
tional to the quantity of the salt dissolved, so
that Q will be a linear function of |, tj, f, e, and
therefore --^ will be independent of J ; thas the
di
existence of the term involving Q will not modify
the form of the equation, but is at most equiva-
lent to a slight alteration in the value of
_, the increase in the potential energy of the
di
system when the mass of J is increased by unity.
It may be shown {v. J. J. Thomson, A;ppUcaiions
of Dyncmdcs to Physics and Chemistry, p. 278)
that
<p(8) =C 9"'°'
where s„ Sj, s„ s^ are the specific heats of the
substances A, B, C, D respectively.
Equation (20) will enable us to find the effects
of pressure and temperature upon chemical com-
bination. V
Effect of pressure.— Fiom equation (20) we
see that, it a+b = c + d, then |— ^ is independent
of the volume; but if a+6 = c-l-d, the number
of .the molecules is not altered by the chemical
reaction, so that in this case the amount of com-
bination is independent of the pressure; if
a -h & is greater than c + d, then the greater the
volume V the smaller is the ratio J — j. Now,
the action of C upon D tends to diminisli this
ratio, while that of A on B tends to increase
it, and if a + 6 is greater than c + d the number
of molecules is inereased when C acts upon D
and diminished when A acts upon B. Thus,
when chemical combination alters the number of
nol^Qilles, th? State of ecjuilibrium depends upoii
the volume of the solvent, and the effect of in-
creasing the volume is to favour that reaction
which is attended by an increase in the number
of molecules. In other words, the chemical ac-
tion which produces an increase in volume is hin-
dered by pressure, while that which produces a
diminution^ is helped by it. This is an example
of the corollary stated on p. 443.
Effect of temperature. — In equation (20)
-yr represents the increment in the potential
energy of the system when f is increased by
unity, and may be approximately measured by
the amount of heat givcQ out when | diminishes
by unity ; if the combination of C and I) is ac-
companied by the production of heat, -^ is
negative, ai^d therefore, when 9 is zero, -^^ is
zero too, and therefore either C or e ihust
vanish ; that is, the combination of C and D
goes on until one of the components is, exhausted ;
in other words, the reaction which is attended
with the production of heat will go on as far as
possible.
Accordi;ag to Berthelot's law of maximum
work the reaction accompanied by the forma-
tion of heat goes on as far as possible at all
temperatures ; we see, however, from equation
(20) that in reality it only does so at the absolute
zero of temperature, though, if the reaction is
accompanied by large thencal effects, the law
will be an approximation to tiie truth for a con-
siderable range of temperature.
This equation shows, too, that if there is any
thermal elfect at all, the relative affinities of two
acids at the absolute zero of temperature ia
either zero or infinity.
If the substances obey Dulong and Fetit'B
law
and then
s,Ci = s.fi2 = SjCj = ijC, = io, say ;
If a 4- & is greater than c + d, then =— ^ is infinite
when 0 is infinite, that is, the reaction accom-
panied by a diminution in volume goes on as far
as possible at an infinitely high temperature. If
a + b = c + d, that is, if the combination does not
change the volume, the combination will only be
partial at an infinitely high temperature.
' We saw that Ostwald's experiments showed
that in the case of an acid and two bases the
value of
ar &
&&
was independent of the nature of the base;
equation (20) shows that for this to be the case
the amount of heat given out, when the number
of molecules of one of the salts incred^es by
ur^ity and that of the other diminishes by the
saine amount,mustbe independent of the nature
of the base. Now Thomson's thermochemical
researches havs shown that the heat of forma-
tion of a salt seetus to be the sunt of two paru
446
EQUILIBRIUM, CHEMICAL.
(v. Lothar Meyer, P. M. 23, 504), one of which
depends only on the base and the other only on
the acid. Thus, in the reactions of the kind we
are considering, where we have two salts of the
same base, one of which is formed whilp the other
disappears, the thermal efiects will be indepen-
dent of the nature of the base. We see, there-
fore, that thermochemical investigations confirm
Ostwald's results.
The greater the thermal effects which accom-
pany the reaction the more rapidly will the
conditions of equilibrium vary with the tem-
perature.
By the principle enunciated on p. 442 we can
readily find the effect of any alteration in the
physical conditions on the amount of chemical
combination which must take place before equi-
librium is reached. Thus, take for example the
effect of surface tension ;' if the energy due to the
surface tension increases as a chemical action
proceeds, then the larger the surface of the solu-
tion the smaller is the amount of this action which
takes place before the condition of equilibrium
is reached ; in other words, the surface tension
checks that reaction which is accompanied by
an increase in that part of the energy of the
system which depends upon surface tension. For
illustration of the eSect of surface tension on
chemical action v. Proc. Oamb. Phil. Soc. 1888.
The same principle will show that if the co-
efficient of compressibility of the solution alters
as chemical action proceeds, the amount of this
action which takes place before equilibrium is
reached will depend upon the pressure applied to
the solution ; since, if pressure is applied to the
liquid, the energy of the system, and therefore
its directrix, will alter as the chemical change
proceeds. Again, if the coefficient of magneti-
sation alters as chemical combination goes on,
the point at which equilibrium wiU be reached
will depend upon the intensity of the magnetic
field in which the solution is placed.
In fine, if the quantity of any kind of energy
changes as chemical combination proceeds, the
conditions for chemical equilibrium wiU depend
on the amount of the energy possessed by the
system.
The amount of the alteration in the value of k,
the value of •*-— produced by an alteration x
in the directrix, is given by the equation
Sk_ _ a dx
'k~ E^fl 'di'
If we apply dynamical methods to hetero-
geneous systems we shall get exactly the same
equations as those we previously deduced from
kmematical principles. J. J. T.
EQITINIC ACID. A crystalline acid said to
exist in fresh mare's-milk (Duval, 0. B. 82,
419).
IIQUISEIIC ACID V. AcoNiiic acid.
EftUIVALEHCY. The conception of chemi-
cal equivalence is founded upon the relations be-
tween acids and bases. In the latter part of the
last century some interesting and important in-
vestigations were carried on by Bergmann, Kir-
wan, Wenzel, and Eichter on neutralisation.
Their object was to determine the relative quan-
tities of acids and bases which are necessary to
eSecu aeutralisatiou. Taking a certain quantity
of an acid, they attempted to determine the
quantities of various bases which were necessary
to neutralise this quantity of the acid ; and on
the other hand, taking a certain quantity of a
base, they attempted to determine the quantities
of various acids necessary to neutralise this
quantity of the base. The important result was
reached that there is a simple relation between
the quantities of bases necessary to neutralise a
definite quantity of an acid, and the quantities
of acids necessarv to neutralise a definite quantity
of a base. No^ong after this discpvery was
made, the fact that the elements combine accord-
ing to a similar law, called the law of definite
proportions, was discovered. This discovery,
and that of the law of multiple proportions, sug-
gested at once an enlargement of the old atomic
hypothesis, and the connexion between the rela-
tive weights of the elements which enter into
combination and the relative weights of the
atoms was pointed out. Owing to serious diffi-
culties in the way of determining the atomic
weights, some chemists felt the necessity of
getting back upon a more solid foundation than
was afforded by the atomic theory in the form
which it then had. It was proposed to give up
the hypothesis in dealing with the proportions
by weight in which the elements combine ; and
it was at this time that WoUastou introduced
into chemistry the word equivalent. Wollaston
proposed to do for the elements what some of
his predecessors had done for the acids and
bases. He proposed to determine the relations
between the weights of the elements which
combine with one another, and then to state
these relations without reference to any hypo-
thesis. The figures expressing these relations he
proposed to call equivalents. The meaning of
the word is simple enough. When the statement
is made that 35-5 parts of chlorine are equiva-
lent to 80 parts of bromine and 127 parts of
iodine, the meaning is only that 35-5 parts of
chlorine, 80 parts of bromine, and 127 parts of
iodine combine with exactly the same number
of parts of some other element, as, for example,
with 1 part of hydrogen, 23 parts of sodium,
39-1 parts of potassium, &a. &a. The quantities
nauied of chlorine, bromine, and iodine, are equi-
valent in their combining power. Clearly, figures
determined in this way are independent of hypo-
thesis.
Turning back to the acids and bases, it will
be seen that the problem with which Bergmann,
Bichter, and others were engaged was of the
same general character. In their neutralisation
experiments they determined the equivalents of
the acids and bases. They determined how
much of a given acid is necessary to neutralise
a certain quantity of a base, and how much of a
second acid is necessary to neutralise the same
quantity of the same base; and the quantity
of the first acid was equivalent to the quantity
of the second acid. So also the equivalents of
the bases could be determined. Thus it is clear
that the equivalent quantities of all acids on the
one hand, and the equivalent quantities of all
bases on the other, might be determined. By
enlarging the meaning of the word equivalent,
a given quantity of a base and the quantity of
an acid which it can neutralise might be c^led
equivalent.
EQUIVALENCY.
447
On first thought, it would appear to be a
simple matter to determine the equivalentB of
aoida and bases ; bat difficulties are soon met with.
We can easily determine the equivalent quanti-
ties of hydroohlorio, hydrobromic, and hydriodio
acids, and as each of these acids forms but one
salt with a simple base, Mke caustic potash, the
results obtained leave us in no doubt. When,
however, we attempt to determine the quantity
of sulphuric acid which is equivalent to 86-5
parts of hydrochloric acid, we find that the acid
{orms two salts with such a base as caustic
potash. If we take one of these as the guide
the equivalent of the acid will be one number ; if
we take the other salt as the guide the equiva-
lent will be entirely different. It may be said
that one of these salts has an acid reaction, and
therefore, as it is obviously not neutral, it should
not be taken as the guide. But if we take the
case of phosphoric acid, we shall easily be misled
if we depend upon the reactions of the salts to
inform us which one should be used in deter-
mining the equivalent of the acid. This acid
forms three salts with caustic soda. The quan-
tities of the base necessary to form these salts
are to one another as 1 to 2 to 3. As is well
known, only the second salt has a neutral reac-
tion, the third one being distinctly alkaline, and
the first one acid. Why not then agree to mea-
sure the equivalentB of the acids by means of
those salts of the acids which contain the largest
proportion of the basic constituent? That
would lead us into another difficulty due to the
fact that some bases have the power to form
what are called basic salts, and others have not.
Should we determine the equivalent of an acid
by means of a base which forms basic salts, we
should get one result, while if we should deter-
mine the equivalent by means of a base which
does not form basic salts we should get quite a
different result. Similar difficulties are encoun-
tered in attempting to determine the equivalents
of the bases.
The determination of the equivalents of
ehlorine, bromine, and iodine is easily made.
Each of these elements combines with hydrogen
in only one proportion. As hydrogen has the
smallest equivalent, the idea suggests itself at
once of using this element as the measure of
the equivalents of all the other elements. The
problem would then be simply to determine the
quantities of other elements which enter into
combination with a fixed quantity of hydrogen,
and the figures representing these quantities
would bear to one another the relations of the
equivalents. Using this method, it is found that
the equivalent of sulphur is 16, that of nitrogen
4|, that of oxygen 8, &e.
The case of carbon presents peculiar difficul-
ties, for the reason that this element combines
with hydrogen in a great many different propor-
tions. In one of the compounds 1 part of hydro-
gen is combined with 3 parts of carbon, in
another with 4 parts, in another with 4| parts,
in another with 6 parts, &c.
But most of the elements do not combine
with hydrogen. In these cases how shall we de-
termine the equivalents ? It seems to be fair to
use some other element, as, for example, chlor-
ine, the equivalent of which has been determined
by means of the hydrogen standard. As 35-5
parts of chlorine are equivalent lo 1 part of hy-
drogen, it is only necessary to determine what
weight of some other element combines with
3S-6 parts pf chlorine in order to know the equi-
valent of this other element. Thus 39*1 parts
of potassium, 38 parts of sodium, 20 parts of cal-
cium, and 9 parts of aluminium, combine with
35-5 parts of chlorine, and, therefore, the figures
just given represent the equivalents of these ele-,
ments. If chlorine is used as a measure of equi-
valence, then in some cases results are obtained
which are different from those obtained when
hydrogen is used as the measure. Thus the
equivalent of phosphorus measured by hydrogen
is 10^, whereas measured by chlorine it is either
lOJ or 6|. We may, however, agree to measure
by means of chlorine the equivalents of only
those elements which do not combine with hy-
drogen, though it would be hard to give any rea-
son for this, except that we are led into difficulties
unless the use of chlorine is thus limited. Does
this end the difficulties ? By no means. Iron
combines with chlorine in two proportions; In
one of the compounds 14 parts of iron, in the
other only 9f parts of iron, are combined with
35-5 parts of chlorine. What is the equivalent
of iron 7 If we agree to regard 14 parts of iron
as equivalent to 35-5 parts of chlorine, in what
light shall we regard the 9§ parts which, in the
other chloride, also hold in combination 35-5
parts of chlorine ? Are these also equivalent to
35-5 parts of chlorine ? If so, then plainly
we are led to the startling conclusion that
14 parts of iron are equivalent to 9f parts of
iron.
It appears that any attempt to determine the
equivalents of the elements without reference to
some hypothesis must end in failure, or at least
it must lead to unsatisfactory results. There is
so much room for doubt in regard to which
figure to select as the equivalent that, in many
cases, two, and even more than two, equivalents
might with equal right be selected by difierent in-
vestigators. Plainly, the sohd foundation which
Wollaston desired, and which we all desire, is not
furnished by a system of equivalents. In dealing
with similar elements and similar compounds we
can speak of equivalent quantities without danger
of confusion. Thus, for example, we cannot be
misunderstood in speaking of equivalent quan-
tities of chlorine, bromine, and iodine ; of nitric
acid and hydrochloric acid ; of sulphuric acid
and sulphurous acid. At present, however, the
word equivalent is used very much less than if
was in the early part of this century, for the
reason that other and clearer conceptions have
been introduced into the science. What relation
the equivalent bears to the later conceptions will
be shown further on.
For the cases named above, and for similai
cases in which an element combines with another
in more than one proportion, it may be assumed
that in one compound a certain number of equi-
valents of the one element are in combination
with one equivalent of the other element, while
in the second compound another number of
equivalents of the second element are in com-
bination. Thus, in water, 8 parts of oxygen
are in combination with 1 part of hydrogen,
while in hydrogen dioxide 16 parts of oxygen are
in combination with 1 part of hydrogen. It may
448
EQUIVALENCY.
be assumed that in water one equivalent of oxy-
gen is combined with 1 equivalent of hydrogen,
while in hydrogen dioxide 2 equivalents of oxy-
gen are in combination with 1 equivalent qi
hydrogen. In this case, what is an equivalent ?
How can we properly speak of 2 equivalents of
one element combining with 1 equivalent of
another ? In doing so we nnconsciously make
use of an hypothesis, and, if we attempt to ex-
press this hypothesis in words clearly, we shall
certainly find that it is essentially the atomic
hypothesis of Daltou, according to which the
combination of elements takes place between
small particles which have definite weights. Call
these Wghts equivalents, combining weights, or
atomic weights, the hypothesis is essentially the
same. The moment we accept such an hypo-
thesis the problem of determining equivalents in
the new sense becomes the determination of the
relative weights of the smallest particles of the
elements which enter into chemical combination.
To these new weights the term equivalent is not
applicable. It may, however, be retained in its
old sense, while the name atomic or combining
weight is applied to the smallest weight of an
element which enters into chemical combination.
This atomic weight may or may not be identical
with the equivalent.
To make this clear we may consider the case
of nitrogen. As we have seen, the equivalent of
nitrogen, deduced from a consideration of the
composition of ammonia, is 4f . On studying
the compounds of nitrogen carefully we soon find
that the quantity of nitrogen' found in these is
generally considerably larger than is represented
by the figure 4f . Thus in nitric acid to 1 part
of hydrogen there are 14 ( = 3 x 4f ) parts of
nitrogen ; and when ammonia enters into com-
bination with other substances, as with hydro-
chloric and nitric acids, the quantity which thus
combines is three times as great as that which is
represented by one equivalent (4§- parts) of ni-
trogen and one equivalent (1 part) of hydrogen.
Or, instead of 6f parts of ammonia being the
smallest weight of the substance which enters
into combination, this smallest weight is 3 times
5f parts or 17 parts. When ammonia acts upon
hydrochloric acid, for example, 36'5 parts of the
acid combine with 17 parts of ammonia, and not
with 5f parts. Similar observations are made in
the cases of all compounds of ammonia. Farther,
a study of certain changes which can be effected
in ammonia shows clearly that the hydrogen con-
tained in. the substance can be taken out one-
third at a time in three stages, and other things
put in its place, thus proving that in the small-
est particle of ammonia there must be contained
at least three smallest particles of hydrogen. The
nitrogen cannot, however, be thus displaced in
parts. If it leaves the compound at all, all of it
leaves at once. Taking, then, all our knowledge
together, it appears that the smallest particle of
nitrogen which enters into chemical combination
is 14 times heavier than the smallest particle of
liydrogen, and that in ammonia one of these par-
ticles of nitrogen is in combination with three
of the smallest particles of hydrogen. We there-
fore call 14 the combining weight, or, now, ac-
cepting the hypothesis, the atomic weight, of
nitrogen. But the equivalent of nitrogen is not
changed by this; the equivalent remains 4|.
The atomic weight is three times as great as th«
equivalent.
The case of carbon is also instructive. Taking
marsh gas it appears that the equivalent of car-
bon is 3, as in this compound 3 parts of carbon
are combined with 1 part of hydrogen. But the
hydrogen of marsh gas can be easily displaced
by other elements, and four distinct steps in the
reaction can be recognised. In each step one-
fourth of the hydrogen is displaced. In all the
reactions of marsh gas a quantity takes part
which contains 12 parts of carbon and 4 parts of
hydrogen. Further, an extensive study of carbon
compounds has shown that the smallest par-
ticle of this element which enters into che-
mical action is twelve times as great as the
smallest particle of hydrogen found in combina-
tion. Therefore, we say the atomic weight of
carbon is 12. But the equivalent of carbon as
deduced from the analysis of marsh gas is 3. The
atomic weight is four times as great as the equi-
valent. Similar studies of oxygen compounds
have shown that the atomic weight of oxygen is
16, whUe its equivalent is 8, or the ratio of equi-
valent to the atomic weight is 1:2. On the otiier
hand, the atomic weights of chlorine, bromine,
and iodine are 35-5, 80, and 127 respectively, and
these are also the equivalents ; so that while, in
the case of carbon, the ratio of the equivalent to
the atomic weight is 1:4, in the case of nitrogen
1:3, and in the case of oxygen 1:2 ; in that of
chlorine, bromine, and iodine it is 1:1. This
suggests that there is some fundamental differ-
ence between chlorine, oxygen, nitrogen, and
carbon, which is not taken into consideration in
the atomic hypothesis of Dalton. Study of other
elements besides those mentioned shows that they
may be divided into classes according to the ratio
between the equivalent and the atomic weight.
This ratio varies from 1:1 to 1:6.
It has already been pointed out that the de-
termination of the equivalents of the elements is
a difficult problem. The determination of atomic
weights by chemical means alone is also a diffi-
cult matter. Although by analysing chemical
compounds and studying the chemical changes
which these compounds undergo, we can draw
conclusions as to the atomic weights of some of
the elements, yet as to others we should be left
in doubt if assistance were not furnished by a
study of some of the physical properties of the
compounds. In the article on Aiomo and mo-
UBOOLiB WEIGHTS (vol. i. p. 336) the application
of Avogadro'shypothesis,andof thelawofDulong
and Petit regarding the specific heat of the ele-
ments, to the problem of determining atomic
weights, has been discussed. It is an important
fact that the atomic weights determined by the
physical methods are in most cases those which
experience has shown to be best adapted to the
interpretation of known chemical reactions. Not
only does Avogadro's hypothesis give us a method
for determining atomic weights, but primarily .it
leads us to definite values for molecular weights.
By determining the molecular weights and ana-
lysing the compounds, and thus determining the
atomic weights, we are led to definite concep-
tions regarding the composition of the molecules
of compounds and of elements. At present wo
endeavour to express the composition of molo'
oules by our formulae.
EQUIVALENOT.
449
There are now three oonoeptions to be dis-
tinguished carefully from one another. These
are the molecule, the atom, and the equwaUnt.
By the molecule is meant the smallest gaseous
particle of a substance, whether elejnentary or
compound, which exhibits the characteristic pro-
perties of the substance ; by the atom is meant
the smallest particle of an element which enters
into the composition of molecules. The basis
upon which the conceptions of molecule and
atom rest is considered more fully in the article
on Atomic and moleoulak weights.
With these conceptions clearly in mind we
may now ask, what is the equivalent of an ele-
ment? It is that mass of the element which
combines with one atom of hydrogen. In the
case of oxygen it corresponds to half the atom,
in that of nitrogen to one-third the atom, and in
that of carbon to one-fourth the atom. With
those elements which do not combine with hy-
drogen some other element like hydrogen in re-
spect to the ratio between the equivalent and
atomic weight is, taken as the measure of the
equivalent. The results reached in this way
have already been referred to.
While those investigations were in progress
which finally led to the clear recognition of the
diflerence between atoms and molecules, chemists
came to recognise resemblances between different
classes of compounds, and it was finally sug-
gested that all compounds are related to a few
simple ones, which may be regarded as types.
For example, hydrochloric acid, HCl, hydro-
bromic acid, HBr, and hydriodio acid, HI, are
similar compounds and they have a similar com-
position. Of such compounds, hydrochloric acid,
HCl, may be taken as the type. Water H^O,
hydrogen sulphide HjS, and other compounds
belong to the water type. Ammonia NH,, phos-
phine PHj, arsine AsH,, belong to the ammonia
type. Marsh gas OH,, silicon hydride SiH,,
belong to the marsh-gas type. This classifica-
tion of compounds according to the type was
extended so as to include most compounds, even
those which are complex. Serious difSculties
were met with in many cases. In some, the
difficulty was due mainly to the. fact that one
and the same compound could belong at the
same time to two or more typos. This led to
the introduction of mixed types. In other cases
the difficulty was due to the fact that the re-
actions of the substance gave little or no clue
to its type. In such cases the imagination was
freely brought into play with highly unsatis-
factory results. Notwithstanding the difficulties
which were encountered in the attempt to classify
compounds according to types, the attempt led
to valuable results. It led to a clearer recog-
nition of differences between molecules, differ-
ences which are as real as the molecules them^
solves. The recognition of these differences does
not, however, carry with it any explanation. For
to say that each of these compounds belongs
to a certain type is not even to attempt an ex-
planation. It is simply the statement of what
appears to be a fact. We might determine with
certainty to which type or types every known
chemical compound belongs, and yet be no
nearer an understanding of the differences
between the compounds than before the deter-
mination. This was first clearly seen by Kekul6,
Vol. IL
who showed that, in order to understand the
relations which exist between the various
chemical compounds, it is necessary to go back
to the atoms themselves, and inquire what re-
lations they bear to one anotherin the molecules.
The cause of the difference between hydrochloric
acid, water, ammonia, and marsh gas, is to be
looked for in the atoms of, chlorine, oxygen,
nitrogen, and carbon. Obviously the first con-
clusion that forces itself upon us is that the
atoms of different elements differ with respect
to the number of hydrogen atoms with which
they can combine to form compound molecules.
While one atom of chlorine combines with only
one atom of hydrogen, one atom of oxygen com-
bines with two atoms of hydrogen, one atom ol
nitrogen combines with three atoms of hydrogen,
and one atom of carbon combines with four
atoms of hydrogen. Having recognised this dif-
ference, the question suggests itself whether an
atom of chlorine can hold more than one atom of
hydrogen in combination; further, whether an
atom of oxygen can combine with a larger or
smaller number of hydrogen atoms than two;
and similar questions arise with reference to
nitrogen and carbon. How far, in other words,
are the differences which we have observed fixed
and invariable? These questions can be an-
swered only by carefully studying the compounds
of the elements named. There is only one com-
pound of hydrogen and chlorine. It therefore
appears that one atom of chlorine can hold but
one atpm of hydrogen in combination, and simi-
larly one atom of hydrogen can hold but one
atom of chlorine in combination. Oxygen and
hydrogen, however, combine in two different pro-
portions forming the compounds H2O and HjO,;
while in water it appears that one atom of oxygen
holds two atoms of hydrogen in combination, in
hydrogen dioxide it appears that two atoms of
oxygen hold two atoms of hydrogen.' Nitrogen
and hydrogen form but one compound with each
other. Carbon and hydrogen on the other hand
form a large number of compounds with each
other. Of these only one contains a single atom
of carbon in the molecule. That is marsh gas,
and in the molecule of this compound there are
four hydrogen atoms to the atom of carbon.
There are three compounds of these elements
in vhose molecules there are two atoms of
carbon. They are O^He, OjH,, and G^. Before
attempting to explain this let us see what
general conclusion is justified by the facts above
recorded. What is true of the relations of
chlorine and hydrogen is equally true of bromine
and hydrogen, and of iodine and hydrogen.
What is true of oxygen and hydrogen is true of
sulphur, selenion, and tellurium, and hydrogen.
What is true of nitrogen and hydrogen is true
of phosphorus, arsenic, and antimony, and
hydrogen. And, finally, what is true of carbon
and hydrogen, so far as their relations in marsh
gas are concerned, is also true of silicon and
hydrogen. We are therefore justified in making
the statement that the atoms of different
elements differ from one another with reference
to the number of atoms of hydrogen they can
' But it is to be observed that as hydrogen peroxids
has not been gasified, the f otmula "Zfi^ does not necessarily
represent the atomic composition o£ the molecule of tbia
compound. — ^M. M. F. M.
G G
460
EQUIVALENCY.
combiiiu with to form componnd molecules. As
regards formation of molecules, the atoms of
the elements can be divided into at least four
classes : —
1. Those which combine with hydrogen in
the simplest proportion of one atom to one atom
of hydrogen.
2. Those which combine with hydrogen in
the proportion of one atom to two atoms of hy-
drogen.
3. Those which combine with hydrogen in
the proportion of one atom to three atoms of
hydrogen ; and
4. Those which combine with hydrogen in
the proportion of one atom to four atoms of
hydrogen.
Our conception of the chemical atom is thus
enlarged. It is not only a minute particle of
matter, which in chemical changes is not broken
up, and which has a definite mass, and the power
of combining with other atoms, but it also has
some power which determines how many atoms
of another kind it can combine' with. At present
we cannot form a clear conception as to the
cause of this power, and no hypothesis has as
yet been proposed to account for it. We can
represent the fact by means of symbols, but
these symbols do not help us to understand the
cause, though they are convenient. We may
also adopt figurative forms of expression sug-
gested by our symbols, but this has not as yet
advanced our knowledge of the cause of the
property of the atoms with which we are dealing.
On examining the composition of the mole-
cules of the compounds which any element forms
with other elements than hydrogen, we find that
just as the number of hydrogen atoms with which
one atom of the element can combine is limited
so the number of atoms of other elements with
which it can combine is limited. Thus phos-
phorus combines with chlorine to form the com-
pounds POl, and POI5, with hydrogen to form the
compounds PH, and PjHj, and with oxygen to
form the compounds PjOj and PjOj. Sulphur
combines with hydrogen to form the compounds
SH2 and probably SjS.^, with chlorine to form
the compounds SjClj, SClj and SCI,, and with
oxygen to form SOj and SOj, &o., &o. From
facts like these we conclude that atoms are so
constnicted, or act in such ways, that the num-
ber 0/ other atoms with which each can combine is
Umited, and that as regards the rvwmber of other
atoms with which they can combine, they differ
from one another.
The property of an atom which determines
the number of other atoms with which it can
combine to form a compound molecule is called
its valency. The relation between the atomic
weight of an element, its equivalent, and its
valency, will readily be understood by the aid of
a few examples. The atomic weight of nitro-
gen, as determined by chemical and physical
methods, is 14 ; its hydrogen-equivalent is
4ft. as this is the relative weight of nitrogen
which combines with one part by weight of
hydrogen. The number of atoms of hydro-
gen with which the atom of nitrogen com-
bines is 3 or i- V*-'^-.'. So also in the case of
4| (equiv.)
oarbon. The atomic weight of carbon ie 12, its
hydrogen-equivalent is 3 ; the number of hydr»
gen atoms with which an atom of carbon can coo*
bine is — ^*- 7*j = 4, &c. In general, the
3 (equiv.)
number of hydrogen atoms with which the
atom of any element can combine is expressed
by a figure which also expresses the relation
between the atomic weight and the hydrogen
equivalent of the element.
The recognition of the property called valency
proved of the highest importance for chemistry.
Discussions in regard to this property have now
been carried on for -liearly thirty years, and our
views in regard to the structure of chemical
compoirnds are based upon it. It is, therefore,
desirable to study it with some care, with the
object of determining exactly what is known in
regard to it, so that we may be in a position, on
the one hand, to recognise its value, and, on the
other hand, to avoid the dangers to which we
are exposed in fdUowing the conception blindly.
Before the introduction of the conception of
valency, each chemical compound was looked
upon as a whole. To be sure, the difference be-
tween atoms and molecules, first pointed out by
Avogadro, gradually came to be recognised, and
in a general way it was acknowledged that the
molecule is made up of atoms. But, beyond
this, inquiry was not pushed to any extent.
This is shown in an instructive way by a study
of the investigations of Hofmann, Wurtz, and
others, on the so-called substituted ammonias.
When Hofmann began his investigations on ani-
line, the prevailing view in regard to this com-
pound was that it was a conjugated compound
{gepdarte Verbmdung) ; that it contained ammonia
combined with a hydrocarbon. Using the modern
atomic weights, the view referred to is expressed
by the formula CjHj.NHj. The common reac-
tions of aniline were interpreted by supposing
that the group OoH, simply accompanied the
ammonia. Some time before this Liebig had
suggested that certain bases like aniline might be
regarded as containing the group NHj. Accord-
ing to this * amide theory ' of Liebig, aniline is to
be represented by the formula C5H5.NHJ. In this
compound,then, ammonia as such is not supposed
to be present, but, nevertheless, there is in it a
remnant of ammonia which gives to the com-
pound certain of the characteristic properties of
ammonia. Wurtz discovered the bases methyl-
amine and ethyl-amine at the time that Hofmann
was engaged in his studies on aniline, and at about
the same time each suggested that the substances
he -was working with might be regarded as am-
monia in which one of the hydrogen atoms is
replaced by a radicle. Before Hofmann closed his
work on aniline he furnished strong experimental
evidence against the theory of conjugated com-
pounds as far at least as it applies to aniline. He
showed that the reactions between ammonium .
oxalate and phosphoric anhydride are not the
same as those between aniline oxalate and phos-
phoric anhydride, and that the difference cannot
be understood if aniline be regarded as a conju-
gated compound, but that it is easily explained if
aniline be regarded as ammonia in which one
hydrogen has been replaced by the hydrocarbon
residue CjHj. The subsequent preparation of
substituted ammonias in which two and three
EQUIVALENCY.
461
hydrogen atoms of ammonia were replaced by
radicles, and of compounds derived from am-
monium by the replacement of all the hydrogen
atoms, furnished a solid foundation for the view
put forward in the so-called theory of types. As
has already been stated, according to the. theory
of types every compound is built according to
some plan, and the number of plans according to
■which compounds are built is small, the funda-
mental plans or types being hydrogen HH, hy-
drochloric acid HOI, water H^O, and ammonia
HjN. Much attention was now given to deter-
mining the type to which any given compound
belonged, and when, after investigation of the
properties and composition of a compound, a
definite statement regarding the type to which
it belonged could be made, the problem was
considered to be solved. No further questions
were asked. It was as if one should look alone
at the exterior of ' buildings, and compare them
solely with reference to the exterior, without
making any inquiry with regard to the interior
arrangements, the connexions between the
rooms, (fee.
Shortly after Hofmann'g papers appeared, an
important paper by B. Frankland was published
(1852). The author had been investigating a new
class of compounds containing metals. At the
close of the paper, the chemical structure of the
compounds is discussed. Attention is called to
the fact that when a metal has combined with a
hydrocarbon, as in the case of tin ethyl, SnO^Hj
(using old formulas), the power of the metal to
combine with other elements, as oxygen, is not so
great as that of the uncombined metal. While
tin alone combines with oxygen in two propor-
tions, forming the compounds SnO and SnOj,
tin-ethyl SnC4H5 combines with oxygen in only
one proportion, forming the compound SnO^HsO,
and this compound cannot take up any more
oxygen even when boiled with dilute nitric acid.
Similar observations were made with reference to
the corresponding derivatives of antimony and
arsenic. £a commenting further upon these re-
markable facts, the author shows Qiat they are
directly opposed to the theory of conjugated com-
pounds, according to which the compounds
under consideration are regarded as containing
the unchanged metals conjugated with hydro-
carbons. He then'says : ' When the formulss of
inorganic chemical compounds are considered,
even a superficial observer is struck with the
general symmetry of their construction; the
compounds of nitrogen, phosphorus, antimony,
and arsenic especially exhibit the tendency of
these elements to form compounds containing
3 or 5 equivalents of other elements, and it is
in these proportions that their affinities are
best satisfied ; thus in the temal group we have
NO,, NH„ NI„ NS3, POs, PH3, PCI3, SbO„ SbHj,
SbCaj, AsOa, AsH„ AsOlj, &c., and in the five-
atom group NOj, NH,0, NH,I, PO5, PHJ, &o.
Without offering any hypothesis regarding the
cause of this symmetrical grouping of atoms, it is
sufficiently evident, from the examples just given,
, that such a tendency or law prevails, and that, no
matter what the character of the uniting atoms
may be, the combining power of the attracting
element, if I may be allowed the term, is always
satisfied by the same number of these atoms '
{Phihsophdcal Transactions, 1852, p. 440).
Thus the conception of the saturation of
atoms was introduced into chemistry..' It was
soon taken up by others, as Williamson and
Odling, and filially, at about the same time in
1858, EekulS and Cooper showed how this con-
ception might be applied, to the explanation of
the constitution of chemical compounds in gene-
ral. Eekuld took up the problem in a broad
way, and it is largely due to his efforts that the
conception of valency became the controlling
conception in the discussions in regard to the
structure of chemical compounds. Kekul6 says :
'I consider it necessary, and, in the present con-
dition of chemical knowledge, in many cases
possible, in the explanation of the properties of
chemical compounds, to go back to the elements
themselves which make up the compounds. I
do not consider the chief task of investigation to
be the detection of groups of atoms which on
account of certain properties are to be regarded
as radicles, and thus to refer the compounds
to a. few types which are scarcely more than
sample formulss. I believe rather that investi-
gation may include the radicles themselves, and
point out the relations between the radicles, and
that, from the nature of the elements, the nature
of the radicles and of the compounds can be de-
duced.'
In the valencies of the atoms we now find the
explanation of types. The reason why most com-
pounds are to be compared with hydrochloric
acid, water, ammonia, and marsh gas, is that
the atoms of most elements are like chlorine,
oxygen, nitrogen, or carbon in respect to the
number of atoms of other elements with which
they can combine. The simplest kind of atom
is one like that of chlorine or hydrogen ; next
come those which are like those of oxygen.
The chlorine atom can hold in combination but
one atom of hydrogen : the oxygen atom has
twice this power, it can hold two atoms of hydro-
gen in combination ; the nitrogen atom can hold
three atoms of hydrogen in combination; and
finally the carbon atom can hold in combination
four atoms of hydrogen. Chlorine, oxygen,
nitrogen, and carbon represent these four dif
f erent kinds of elements.
Chlorine is called a monovalent element, be-
cause its atom combines with but one atom of
hydrogen to form a compound molecule ; oxygen
is called a dmalent element, nitrogen a trivalent,
and carbon a tetra/oalent, element. Further, thn
elements are called respectively monads, dyads,
triads, tetrads, pentads, hexads, Ssa.
From what has been said it will be clear that
valency is something quite different from affinity.
By affinity is commonly meant the unknown
cause of the combination of atoms. Hydrogen
and chlorine combine very readily ; they have,
as we say, a strong affinity for each other; yet
they are monovalent with reference to each other.
Carbon and chlorine do not combine readily:
they have not a strong affinity for each other;
yet carbon is tetravalent towards chlorine, its
atom is capable of holding four atoms of carbon
in combination. The two properties valency
and affinity are possessed by every atom, and ex-
hibit themselves whenever atoms act upon one
another, the latter determining the intensity of
the reaction, the former the complexity of the
resulting molecule.
ce3
i52
EQUIVALENCY.
In this discussion thus far the valency of an
element has been measured by considering the
number of atoms of hydrogen with which its
atom can combine to form a compound molecule.
It is, however, a fair question whether the valency
of an element towards other elements is neces-
sarily the same as towards hydrogen. Is it fair
to conclude that, because an clement is trivalent
towards hydrogen, it is also trivalent towards
chlorine and other elements 1 As we have yet no
conception in regard to the cause of the property
which we call valency, we have not a right to make
assumptions of this kind. The only way to answer
the question is to study the facts. For this pur-
pose let us take the case of carbon. This element
is tetravalent towards hydrogen. Towards chlor-
ine it is also tetravalent, as is shown by the mole-
cule CCl,. Towards oxygen it appears to be
tetravalent in carbon dioxide, COj, in which we
have the atom of carbon in combination with
two divalent atoms of oxygen. But in carbon
monoxide, CO, either carbon acts as a divalent
element or oxygen acts as a tetravalent element.
Towards sulphur carbon is tetravalent, as shown
in carbon disulphide, CSj, in which one atom of
carbon holds in combination two divalent atoms
of sulphur. Phosphorus is trivalent towards hy-
drogen, it cannot form a compound with hydro-
gen containing a larger number of atoms of hy-
drogen than three. It is, however, pentavalent
towards chlorine, as shown in the compound
phosphorus pentachloride, PCl^, and it is also
trivalent towards this element, as shown in the
trichloride PCI3. Phosphorus also combines with
oxygen in two proportions, forming the trioxide,
PjOj, and the pentoxide, PjO„ and the composi-
tions of these can be best explained by assuming
that, in the former, the phosphorus is trivalent,
and, in the latter, pentavalent. Sulphur is di-
valent towards hydrogen, forming the compound
SHj. With chlorine it forms the compounds S^Cl^,
SClj, and SCI,. With oxygen it forms the com-
pounds SOj and SO3, in which the' sulphur appears
to be tetravalent and hexavalent. lodincis mono-
valent towards hydrogen, but towards chlorine
it acts both as a monovalent and as a trivalent
element, as shown in the compounds ICl and
ICI3. Nitrogen, which is only trivalent towards
hydrdgen, appears to be pentavalent in the com-
pound NHjCl and other similar ammonium com-
pounds. With oxygen it combines in a number
of proportions, as is well known.'
The simplest interpretation of the facts just
stated is that the valency of an element towards
hydrogen is not necessarily its valency towards
otiier elements, and that the valency of one ele-
ment towards another may be one thing in one
compound and different in another compound.
Although this is the simplest interpretation, it
does not follow that it is the correct one. It is
possible that the valency of an element is always
the same, but that, owing to the surrounding
conditions and the character of the element with
' It is important to note tbat many of the compounds
cited above have not been gasified, and that therefore the
formulsB given are not all molecular ; It is known that
some of the compounds, e,ff. POl, and NH^Oi, are dissociated
by heat. It is doubtful whether arguments regarding the
valencies of atoms should be based on the compositions of
any compounds except those which have been gasified ;
as it is only to gases that the conception of the theory of
atoms and molecules can, at present, be strictly applied. —
M.M.F.M.
which it combines, the full valency is not always
exhibited. Until we have a clear conception in
regard to the cause of valency, or until we have
a satisfactory hypothesis of valency, discussions
on the question whether valency is constant or
variable must be more or less idle. If valency
be something inher&ut in the atom, like the
mass of the atom, then it is impossible to con-
ceive of it as being variable. If, however, it be
a condition of the atom; if, for example, it is
dependent on the motion of the atom, then, as
the motion may differ under different circum-
stances, the valency also may differ.
It is not uncommon to think of atoms as
joined together in some such way as small ob-
jects adhere to one another under the influence
of electric or magnetic attraction. It is supposed
that the monovalent atom has but one place
where another atom can be attached, or that it
has but one pole, or that there is but one direc-
tion in which another atom can enter into com-
bination with it. These phrases do not help us
much, and they do not differ materially from
one another. If such a view is held, it carries
with it, of course, a similar view in regard to
divalent, trivalent, and, in general, polyvalent^'
atoms. Each atom has a number of places where
other atoms can be attached, the number corre-
sponding to the valency of the atom. The
graphic symbols so commonly used to represent
the structure of chemical compounds in terms of
the conception of valency are well calculated to
give the idea that the view just stated is gene-
rally accepted. Of course, if it is accepted,
valency is considered as a constant property. In
this case it will be necessary to furnish explana-
tions of those compounds which seem to prove
that valency is variable. Some of the explana-
tions which have been offered will now be con-
sidered.
Among the compounds which appear to show
that valency is variable is the well-known series
of oxygen compounds of chlorine and of nitrogen.
While chlorine forms only one compound with
hydrogen, and is unquestionably monovalent to-
wards hydrogen, it appears to have a greater
valency towards oxygen. This is explained by
some by assuming that in those compounds of
chlorine and oxygen in which there is more than
one atom of oxygen in the molecule the oxygen
atoms are combined with each other as repre-
sented 'in the formulsB 01 — O — 0 — CI and
CI — 0 — O — 0— CI, in which the chlorine is re-
presented as monovalent and the oxygen as diva-
lent. To explain the existence of the series of
oxides of nitrogen, on the assumption that the
valency of oxygen is always two and that of
nitrogen three, a similar method is used; if
necessary, combination is assumed between ni-
trogen atoms, between oxygen atoms, and between
nitrogen and oxygen atoms. But even with
these possibilities all these compounds cannot
be explained withont the aid of a new concep-
tion. It is assumed that a polyvalent element
may be in combination with itself in more than
one way. Just as hydrogen in the hydrogen mole-
cule must be assumed to be in combination with
itself in the same way that it is in combination
with chlorine in the molecule of hydrochloric
acid, so oxygen must be in combination with
itself in the molecule of oxygen. But oxygen
EQUIVALENCY.
4S3
IS divalent ; i.6., on the present hjrpothesis, ita
atom has two places where combination with
other atoms can be effected. To express the con-
ception that both these places are occupied in the
molecule of oxygen, this molecule is represented
graphically thus 0=0, while the molecule of
hydrogen is represented thus H — H. The latter
condition is spoken of as single union, the former
as double union. So, too, triple union is sup-
posed to exist in the molecule of nitrogen as
represented thus N^N. Now, in explaining the
oxides of nitrogen it is assumed that in some
cases the nitrogen atoms are in combination by
single union, and in others by double union.
Thus nitrous oxide N^O is represented in this
N. N— 0.
way II >0 ; the trioxide thus || >0. The
n/ N— 0/
compounds KO and NO, plainly cannot be ex-
plained in this way. For these a new assump-
tion, which will be considered later, must be
made. The tetroxide NjO, may be represented
N— 0— O
in this way || | .
N— 0— 0
The question will now suggest itself, have we
any evidence that the structural formulsB above
given are correct? Is there any experimental
evidence in favour of them 1 The answer is that
we have no evidence whatever in favour of them,
and the only reason for accepting them is that
they are in accordance with the indefinite and
crude view in regard to the nature of valency
above referred to. The argument is this :
valency must be a constant property of ele-
mentary atoms; but nitrogen is trivalent and
oxygen is divalent ; therefore the compounds of
these elements must be constituted in the way re-
presented. It must, however, be distinctly borne
in mind that for some of the compounds there
are other formulffl, besides those given above,
which answer the requirements, and which are
just as probable. For example, nitrogen trioxide
/N-0
may be represented thus OC | I ; and the te-
\n— O
/N— Ov 0— N-0
troside thus Oc I ^O, or thus | | | .
\N— o/ 0— N— O
In explaining the existence Of the two series of
compounds of mercury, copper, iron, aluminium,
&c., the same method is commonly_ adopted.
Mercury and copper are regarded as divalent in
both series of compounds, and the structure of
the compounds is represented thus : mercuric
compounds Hg<^5;, Hg=0 ; cuprio compounds
Cu^pJ and Cu=0 ; mereurous compounds
Cu— CI
>0; cuprous compounds |
Cu— i
Cu— CI
^Cl
Hg-Cl Hg.
. I
Hg— CI Hg
Cuv
and I >0. '
Cu/
There are many oases which cannot be ex-
plained by any of the assumptions thus far
referred to. As good an example as any is that
of the two chlorides of phosphorus, PCI3 and
PCI5. Here, plainly, phosphorus is in combina-
tion with chlorine in more than one proportion,
and this cannot be explained by assuming that
in one of these compounds two atoms of phos-
phorus are in combination with each other, for
the molecular weights of the chlorides are pro-
perly represented by the above formulae. It has
been suggested by Kekul6 that the pentaohloride
is not a true chemical compound, but that it is
made up of a molecule of phosphorus trichloride
and a molecule of chlorine held in combination
by some force different in character from that
which holds the atoms together in a molecnle.
This conception may be represented thus
PCI3.CI2. The fact that when the compound
is heated it readily breaks down, forming the
trichloride and free chlorine, was regarded by
Eekul6 as evidence in favour of the view which
he put forward. He called compounds of this
kind 'molecular compounds,' to distinguish
them from true chemical compounds or atomio
compounds. He considered them to be similar
to salts with water of crystallisation, from which
the water is given off by heat.
One serious objection to this view is that
many of the cases which it was invented to
explain cannot be explained by it. While it is
true that phosphorus pentachloride does break
down under the influence of heat, the analogous
pentafluoride is stable, and there is no reason
for assuming that it differs from other chemical
compounds. Then, too, it has been shown that
the pentachloride itself can be converted into
vapour ip the presence of the vapour of the tri-
chloride. At present this hypothesis of molecu-
lar compounds does not play an important part
in dealing with the subject of valency.'
A more satisfactory suggestion which has
been made with reference to the variations in
valency is that while an atom may have a con-
stant maximum valency, its entire valency may
not be exhibited in certaiii compounds. Those
compounds of an element in which its full
valency is brought into play are called satv/rated
compounds, and those in which the full effect of
the valency is not shown are called tmsatwated
compounds. Thus, according to this view, phos-
phorus is pentavalent, and in the pentachloride,
which is a saturated compound, its full valency
is brought into play, while in the trichloride
only a part of its valency is brought into play,
the compound being unsaturated. The dif-
ference between carbon monoxide CO and the
dioxide CO^ is accounted for in the same
way. The expressions ' its full valency is brought
into play ' and ' only a part of its valency is
brought into play ' cannot at present be further
explained, but this is not a sufficient reason for
refusing to use them. The facts show clearly
that the manifestation of that power which we
call valency is subject to variations. We must
use some expressions to state these facts. The
chief objection to the expressions is that they
suggest the idea of parts of an atom acting
differently, or of some parts of an atom being
brought into action while other parts are not
acting, an idea which is not only improbable,
but absurd. But this idea is not necessarily in-
volved in the conception of saturated and un-
saturated atoms. Thus carbon has the power
* This is especially true If we agree to restrict our con-
ceptions of valency to the conslderatiou of gaseous mole-
cules.—M. M. P. M.
4M
EQUIVALENCY.
to combine with oxygen in the proportions indi-
cated by the formula CO and CO^. It is certain
that the carbon atom in the monoxide has the
power to take up more oxygen, and that when
more oxygen is presented to it under the right
conditions the additional oxygen is taken up.
Because the monoxide can take up as much
oxygen as it already contains, it does not follow
that the carbon atom in the monoxide is only
half employed, any more than it follows that,
because a magnet which can support two pounds
is supporting only one pound, it is therefore
only half employed. The whole magnet acts in
both cases : in the one case it is saturated, in
the other it is unsaturated. Xhere is, however,
this marked difference between the case of the
magnet and that of the atom. In the former
any weight, from the lightest to that necessary
for saturation, can be held in combination,
whereas in the latter the variations are deter-
mined by the weights of the atoms which are
held in combination. Although then it is most
probable that in every chemical compound,
whether saturated or unsaturated, every atom is
brought into action in every part, it appears
probable that the atoms can adjust themselves
in different ways with reference to one another.
Some investigations have been undertaken
with the object of throwing light upon the
question whether different parts of an atom can
act differently. To illustrate the methods the
case of carbon may be taken. The carbon atom
is tetravalent. It combines with four atoms of
hydrogen, chlorine, &c., to form compound mole-
cules. Are all the four atoms which it holds
in combination held with the same force ? The
facts appear to give an affirmative answer. If
the atoms were held in different ways, then
it should be possible to make more than one
compound of the formula CH3CI, or any other
mono-substitution product of marsh gas. But,
as a matter of fact, only one variety of these
mono-substitution products has ever been pre-
pared. Then, further, the theory in regard
to the structure of the hydrocarbons of the
paraffin series is based upon the assumption
that each of the four hydrogen atoms in marsh
gas is held in exactly the same way by the
carbon atom ; and this assumption is so perfectly
in accordance with a large number of facts that
it is worthy of the most serious consideration as
an argument. There is one experiment which
appears to show that in the case of sulphur the
four affinities, as the hypothetical individual
points of attraction, or the parts into which the
total valency may be divided, are called, are not
exactly the same. Kriiger asserts that the pro-
duct of the combination of (02113)28 and CH^I
is different from the product formed by com-
bining S(CH3)(C2Hs) with C2H5I; yet both com-
pounds are represented by the formula SBt2MeI.
If it is assumed that in these compounds
the sulphur is tetravalent, then it appears to
follow that the four affinities of the sulphur
atom are not identical in value ; because if
it were immaterial in what way the groups
Et and Me, and the atom I, were arranged
relatively to the S atom with which all are in
direct union, then only one, compound SEtjMel
could exist.' A similar conclusion seems
* £eceut research has iaraliijated Ki'Uger's results.
to be justified in the case of nitrogen, as shown
by Lossen's investigations on derivatives of
hydroxylamine. Lessen showed that when two
different radicles are introduced into hydioxyl-
amine in place of hydrogen, a large number of
isomeric substances are obtained instead of one,
as we should expect. The case of nitrogen has
been investigated by V. Meyer and by Laden-
burg, but the results obtained by these two in-
vestigators differ. Taking all the evidence into
consideration it appears that by far the larger
number of facts of chemistry clearly indicate
that the affinities of an atom are of the same
Idnd, while in the case of sulphur and of nitro-
gen the facts referred to require further investi-
gation.
It is sometimes held that, because a certain
number of atoms are readily given off from a
molecule of a compound, there are weaker and
stronger affinities. Thus, when phosphorus
pentachloride is heated it gives up two atoms of
chlorine. From this the conclusion is some-
times drawn that in phosphorus pentachloride
three of the atoms of chlorine are held in com-
bination more firmly than the other two. Such
a conclusion is, however, evidently unjustified.
All that we can say is, that at the higher tem-
perature the more complex compound can-
not exist, while the trichloride can. It is pro-
bable that in the trichloride the whole of the
phosphorus atom is employed in holding the
three chlorine atoms in combination, and that
this is also true of the phosphorus atom and the
five chlorine atoms in the pentachloride. If
this is true, then it follows that the pentachloride
must be a less stable compound than the tri-
chloride.
Whatever method of explaining the varia-
tions in the composition of the compounds of
any elements we may adopt, it is plain that
these variations are observed. Whether we
agree to say that carbon is divalent in carbon-
monoxide and tetravalent in carbon dioxide,
or to call carbon dioxide a saturated compound
and the monoxide an unsaturated compoimd,
the facts remain the same ; and the most im-
portant thing to be done is to discover the laws
which express the variationsin composition. This
subject has received considerable attention, but a
law which shall express all cases has not been de -
duced. Nevertheless a fact of great importance
has been learned. It is this, that the apparent
valency of an element in nearly all cases changes
from even to even or from odd to odd, and but
rarely from odd to even or vice versd. Thus the
valency of phosphorus changes from three to
five, and all compounds of phosphorus can be
explained by assuming that the element is either
trivalent or pentavalent, and there are no facts
known which indicate that it is ever divalent
or tetravalent. Sulphur, on the other hand,
is apparently divalent in hydrogen sulphide,
SHj, tetravalent in sulphur dioxide, SO2, and
in the tetrachloride, S01„ and hexavalent in
sulphur trioxide, SO, ; and there is no compound
of sulphur requiring the assumption that the
element is ever monovalent, trivalent, or penta-
valent. Elements whose valencies are expressed
by an even number have been called artiads, and
those whose valencies are expressed by an uneven
number have been osXledi 2>erissads. Although the
EQtirVALENOT.
466
division of the elements into arUads a,ndperissads
is justifiecl by many facts, there are a few which
show clearly that the law is subject to exceptions.
The most prominent of these are the oxides of
nitrogen, nitric oxide, NO, and the peroxide, NOj.
Plainly in neither of these is nitrogen trivalent
or peutavalent. In the former it appears to
be divalent, and in the latter tetravalent, the
compounds corresponding in composition to
the two oxides of carbon. It is true there is
nothing to prevent our regarding the nitrogen as
monovalent in nitric oxide, and perhaps repre-
senting its structure thus =N — O — ; but we
shall hardly make much progress if we are will-
ing to make use of such methods to deceive our-
selves by supposing that we are thus helped out
of difficulties; and it should be said, for the
credit of chemists, that this suggestion has not
been made, so far as is known to the writer.'
The law of variation in the composition of
compounds, or in the valency of the elements, is
higMy suggestive of the law which expresses the
variations in what may be called the valency of
certain hydrocarbons. The hydrocarbon, CgH,„
is a saturated compound, and is not capable
of combining direcUy with atoms or molecules.
In this sense it has no valency, and is to be
compared to the elements in the state of mole-
cules. As is well known, the simplest change
which can take place in hexane, to convert it
into a compound with active valencies, is the
abstraction of two atoms of hydrogen. In this
way the hydrocarbon, C„H,2, or hexylene, is
formed. This compound is divalent. An inter-
mediate monovalent compound cannot be ob-
tained. The next change of the same kind gives
a compound, CsH,,, which is tetravalent; and
thus successively are formed the hexavalent
compound, CsHj, and the octovalent compound,
CsHj. The valencies of these compounds are
then 2, 4, 6, and 8, the variations foUovring the
same law as is observed in the case of the ele-
ments. The variations in the case of the hydro-
carbons are commonly explained by assuming
difierent kinds of union between tho carbon
atoms. The hexavalent group --;C— C^ be-
comes tetravalent by the establishment of
double union between the carbon atoms, giving
a group C=C , and it becomes divalent by the
establishment of triple union between the carbon
atoms as indicated thus, —CSC—. Other pos-
sibilities present themselves when we have a
compound -containing more than two atoms of
carbon in the molecule. As has already been
shown this same method of explanation has been
used in the cases of the compounds of mercury,
copper, and iron, but it is plainly not directly
applicable to the phosphorus compounds, or the
sulphur compounds above referred to. It has been
suggested by Professor Sylvester (v. Am. 1, 54)
that the variation in the valency of elements may
' ' There are several exceptions to the so-called law of
artiadi and feriuadt ; InOl, and InCa„ and probably also
InOl, exist as gases ; WCl. and WOl. ; CrOl. probably
exists as a vapour, besides OrCl, ; HgOl is probably the
molecular formula of calomel, while the composition
of the molecule of corrosive sublimate is represented by
the formula HgOl..— M. M. F. M.
be' accounted for by supposing each M-valent
atom to be made up of n-trivalent atomicules
united in such a way as to leave one valency
of each atomicule free. The explanation is
fanciful, but may perhaps prove of some service.
In studying the valencies of the elements in
connexion with their position in the periodic
system, certain regularities appear which are of
great interest. As regards the hydrogen valency
it is a noteworthy fact that the elements of the
first three groups in HendelejeS's table do not
unite with hydrogen. Beginning with carbon
in the fourth group the hydrogen valency de-
creases regularly, as is shown in the following
table : —
Group 1,234 S 6 7
Element Li Be B 0 N OP
Hydrogen compound — _ _ OH. NH, OH, FH
Taking next the chlorine valency we find,
beginning with Group 1, a regular increase to
Oroup 4, and then a regular decrease, as is
shown in this table : —
Group 1 2 3 4 5 8 7
Element Na Kg Al Si F S Gl
Chlorine com-
pound NaCl MgOl. Aica. SiCl. POl, SOI, 01,
Towards oxygen the valency increases regu-
larly from Group 1 to Group 7, as shown thus : —
Group' 12 3 4 s 6 7
Element Na Mg Al SI F SI
, Oxygen com-
pound Na,0 Mg.O, A1,0, SiaO. PjO, S,0. 1,0,
This series of oxygen compounds is of special
interest. One cannot study it impartially with-
out reaching the conclusion that we have here
to deal with a regular increase in the valency
from 1 to 7. Any other conclusion involves an
explanation for the compounds P^Oj, SO3, and
I2O, entirely different from that which we make
use of for tiie other oxygen compounds in the
series. Further, when we consider the hy-
droxyl derivatives of these elements, we shall see
that it is impossible to deal with them satisfac-'
torily on any other assumption than that phos-
phorus is tetravalent, sulphur hexavalent, and
iodine heptavalent towards oxygen. This is
perhaps most strikingly shown in the case of
perio^c acid. This compottnd is compipnly
represented by the formula HIO4, and the struc-
ture H-O-O-O-O-I is given to it. It can easily
be shown, however, that on this assumption
most 'of the salts of periodic acid cannot be
explained. Whereas, if the periodates be con-
sidered as derived from several acids, all of
which are in turn derived from the normal
periodic acid I(OH),- by processes of dehydra-
tion, they can all be explained without serious
difficulty. The acid HIO4, according to this,
is derived from normal periodic acid thus :
I(OH), = 03l(OH) + 3HjO; and in it the iodine
is regarded as heptavalent, holding three atoms
of oxygen and one hydroxyl. In a similar way
sulphuric acid is regarded as derived from the
normal acid or maximum hydroxyl compound
S(OH). by loss of water :
S(0H),= 0sS(0H),-l-2H,0.
According to this, in sulphuric acid the sulphur is
hexavalent, holding two atoms of oxygen and two
hydroxyls. Severfi facts which have come to
light in the study of derivatives of sulphuric acid
speak in favour of this view, 01 at least against
456
EQUIVALENCY.
the view sometimes held that the acid is consti-
tuted thus, HO-0-S-O-OH. In short, whether
we study the elements with reference to their
positions in the periodic system or with refer-
ence to the chemical transformations of their
compounds, we are led to the conclusion that
the more probable view in regard to their valency
towards oxygen is that it increases regularly
from 1 to 7 from Group I. to Group VII. ; arid that
the valency of the elements towards hydrogen is
quite different from their valency towards oxygen,
except in Gropp N. Taking the last four groups
it is seen that as the valency towards hydrogen
decreases the valency towards oxygen increases :
Group
4
5
6
7
Hydrogen oompouna
SiH.
PH.
SH.
IH
Oxygen compound
Si.O.
P.O.
S.O.
I.O,
It appears from further study that the
valency of an element towards hydrogen is
constant, whUe towards chlorine and oxygen it
is evident from what has already been said that
the valency varies. Except in the fourth group
the maximum valency is never exhibited towards
hydrogin. Chlorine occupies an intermediate
place. In the fourth and fifth groups the
valency towards chlorine is the same as towards
oxygen. In the sixth group the valency towards
hydrogen is two, towards oxygen six, and towards
chlorine, as shown by the highest chlorine com-
pound of sulphur, it is four. In the seventh
group the valency towards hydrogen is one, and
towards oxygen seven, while the highest valency
shown towards chlorine by a member of this
groap is three, as in the compound 101,. To-
wards fluorine, however, the valency of iodine is
five, as shown by the compound IF5.'
The facts just referred to show beyond ques-
tion that the valency of an element is not a con-
stant property, residing as it were in the element,
but that it is determined to some extent by ex-
ternal circumstances, and particularly by the
character of the element with which an element
is brought in contact. We find analogy for this
in the conduct of some acids towards bases.
Thus, ordinary phosphoric acid is commonly
spoken of as a tribasic acid, but its basicity is to
some extent dependent upon the character of
the base with which it reacts. Strictly speaking
it is only dibasic towards sodium hydroxide,
while towards most other bases it is tribasic.
The intensity of the action of the acid towards
sodium hydroxide is greater than towards most
other bases, and after the acid has taken up two
atoms of sodium its power is nearly exhausted.
It can, to be sure, take up a third atom of
sodium, but the compound thus formed is very
unstable. But it can take up and hold firmly
in combination three atoms of silver. Consider-
ing the differences in the valency of any element
towards other elements, it appears in general
that the valency is small towards an element
with which it combines with much energy, while
it is larger towards an element with which it
combines with little energy. This is well illus-
* If by the valency of an element is meant the maximum
Dumher of atoms with which one atom of the given ele-
ment can be directly associated in a gaseous molecule, then
conclusions about the valency of this or that element must
be drawn, at present, only from a study of gaseous mole-
cules. In this case, some of the remarks about the valencies
Df 1, S, &c.,in these paragraphs would be rather irrelevant,
M. M. P. M.
trated by the compounds of chlorine with hydro-
gen and with oxygen.
The phenomena studied under the head of
valency show clearly that, when atoms combine
to form a molecule, they are not merged into
one homogeneous mass, but are arranged with a
certain definiteness ; and the study of the facts
of isomerism confirms this view in a striking way.
We speak of the atoms as being linked together,
and this linking is found to take places according
to the laws of valency. By the constitution or
structure of a compound is meant the way in
which the atoms are linked together. The con-
stitution is expressed by means of a formula
which is intended to show — on the basis of certain
assumptions, and by the help of several conven-
tions— how the atoms are linked together. Thus
the formulae H-O-H, 02S<^fj"Tj, &c., are consti-
tutional formula. These are determined by
methods which will be considered in the article
FoBMUL^E. It need only be remarked here that
they are determined chiefly by studying the re-
actions of compounds, and the methods by which
they are built up from simpler substances. The
reactions being, known, they are interpreted in
terms of the atomic theory and the hypothesis
of the linkage of atoms.
To sum up in a few words the chief conclu-
sions which we are justified in drawing in regard
to valendy : —
The so-called theory of types was the fore-
runner of the valency hypothesis.
Frankland first recognised the fact that the
power of atoms to unite with other atoms is
limited to a definite number of other atoms.
Kekulfi and Couper elaborated the valency
hypothesis, and showed how it may be used to
explain chemical compounds.
The facts show plainly that valency is not
a constant propelrty of the elements, but that
it varies : (1) according to the nature of the
uniting elements ; (2) according to surrounding
circumstances, such as the temperature.
Valency is not to be thought of as determined
by a certain number of points of attraction in
the atom, but rather as a condition^perhapS a
form of motion. Valency is a function of the
atomic weights of the elements.- I. E.
EBBITJM Er. At. w. 166. Mol. w. un-
known as element has not been gasified. Chief
lines in emission-spectra: 5826,5256,49?! (Cleve,
O. R. 91, 381).
In_1788 Gadolin, professor at Abo, found a
new earth in a mineral f rom Ytterby in Sweden;
the discovery was confirmed by Eckeberg in 1797,
and the new earth was called Tttria. The exami-
nation of yttria from OadolmUe (the mineral was
thus named after Gadolin) by Berzelius (1819),
Mosander (1839 and 1843), and Scheerer (1842),
led to the recognition of seven earths in what
had been regarded by Gadolin as a homogeneous
substance, viz. beryllia, lanthana.ceria, didymia,
yttria, erbia, and terbia. Many researches were
conducted in the years 1860-1878 on the earths
from GadoUnite ; some of the results pointed to
the non-existence of terbia as a distinct earth,
while others made the existence of this body very
probable; the investigations of Cleve seem to
show that terbia is a definite earth. The sub-
stance to which the name of erbia had been
ERGOSTEMN.
467
given was very carefully examined by Marignao
in 1878, and subsequently by Nilson, and then
by Cleve, with the result that it was shown to be
a mixture of the three earths ytterbia, soahdia,
and erbia, and to these Cleve afterwards added
two others, viz. holmia and thulia. The inves-
tigation of these earths is yet far from complete.
To obtain the crude earths from GadoUnite,
Bahr a. Bunsen (A. 187, 1) decompose the
mineral by HClAq, separate SiO^ by evaporation
to dryness and addition of HClAq, heat to boil-
ing, and ppt. by oxalic acid ; they wash the pp.,
convert the oxalates into nitrates, and ppt. the
cerium compounds by addition of K^SO^; the
earths of the erbium group are then ppd. from
the filtrate by oxalic aoid, the oxalates are heated
in a Pt dish, the carbonates thus obtained are
boiled in water (to dissolve out K3OO3), and di§^
solved in HNOjAq ; oxalic aoid is again added,
and the ppd. oxalates are onoe more converted
into carbonates by heating ; the carbonates are
tested for didymium by observing the absorp-
tion-spectrum of a very cone, solution in
HNOjAq; if Di is present the treatment with
KjSO, is repeated until a pp. is obtained free
from Di; the earths are then ppd. by NH.,Aq
free from (NHJ0CO3 : the pp. is dissolved in
HNOaAq, and the oxalates are ppd. by addition
of oxalic acid. There are different methods for
obtaining erbia from the mixed oxalates. Auer
v. Welsbach recommends the following (M. 4,
630). The oxalates are converted into oxides by
heating strongly, the oxides are made into a paste
with water and thrown into a quantity of hot
nitric aoid insufficient for their com^plete solu-
tion; a basic erbium nitrate containing yttria
forms on cooling ; the process is repeated several
times ; at last, when there is a considerable
quantity of undissolved oxide in the boiling nitric
acid, the whole becomes somewhat pasty and
greyish-fed in colour; the mass is now allowed
to cool, and cone, nitric acid is added in small
successive quantities untU the colour becomes
reddish. The acid dissolves compounds of Oe
and traces of Pe salts ; a compact rose-coloured
pp. settles down, from which the mother-Hquor
can be poured off. The pp. is washed with alco-
hol with the aid of a filter-pump ; the alcohol dis-
solves nitrates but leaves the basic nitrates. The
pp., which consists of basic erbium nitrate con-
■ taining yttrium nitrate, is purified by a long and
tedious process, based on the fact that basic
erbium nitrate is produced more readily than
the basic yttrium salt by heating the mixed
nitrates with the oxides of the metals, and that
the basic yttrium salt is more soluble than the
erbium salt in liquid containing the normal ni-
trates. Another method of obtaining basic er-
bium nitrate consists in heating the mixed
nitrates (formed by dissolving the oxides or car-
bonates inHNOaAq) in a Pt dish until red fumes
are evolved, and a portion of the residue is in-
soluble in water ; the insoluble portion is again
heated, and then treated with water, and so on
(Marignac, A. Ch. [6] 14, 247 ; Cleve, O. R. 91,
381).
Beferences. — For earlier work v. Cleve in
Fremy's Encyclopidie cMndgue, tom. 3. Ber-
ielius, Lehrhuoh, 2 (5th ed.). Mosander, J. ;pr.
30, 27. Bahr a. Bunsen, A. 137, 1. Cleve a.
Hoglund, Bl. [2] 18, 193, 289. Lawrence Smith,
C. E. 87, 146, 831. Marignac, Ar. Sc. [3] 3,
413. Delafontaine, C. B. 87, 600. Soret, 0. B.
89, 478, 521 ; 91, 378. Cleve, 0. B. 89, 478,
708 ; 91, 881. Eoscoe, B. 15, 1274. Marignac,
C. B. 87, 578. Nilson, C. B. 88, 645 ; 91, 118.
De Boisbaudran, C. B. 88, 322 ; 89, 212. Von
Welsbach, M. 4, 630.
The metal erbium has not yet been isolated.
The atomic weight was determined by Dela-
fontaine {Ar. Sc. 1866. 112), Cleve a. Hoglund
(BZ. [2] 18, 193, 289), Humpidge a.. Bumey (O. /.
35, 11), but the results were too high. Cleve re-
determined the at. w. by synthesising the sul-
phate from pure Er^Oa : he obtained the value
166-15 (0. B. 89, 706; 91, 381).
So far as the investigation of Er compounds
has gone, it shows that this metal is best placed
in Group V, in the odd series 9, between Sb and
Bi ; Br is, also analogous to the earth-metals Sc,
Y, La, and Yb, and it shows resemblances to Ce
(C/. NiTKOQEN OROUP OP ELEMENTS, and EARTHS,
METALS OF THe).
Erbium, haloid compounds of. Erbium
bromide, chloride, fluoride, and iodide, ErX,
(X=Br, CI, F, I), have been described; but as
the material worked with was not known to be
perfectly free from other metals of the yttria
g?:oup, but little stress can be laid on the descrip-
tions given. These compounds are said to be
rose-coloured and deliquescent.
Erbium, oxide of. Er^Oa. S.G. 8-64. S.H.
•065. S.V.S. 43-98 (Nilson a. Pettersson, B. 13,
1459). Emission-spectrum characterised by
bright lines 6546 (red), 5631 and 5387 (yellow),
5228 and 5204 (green) (Bahr a. Bunsen, A. 137,
1 ; De Boisbaudran, 0. B. 76, 1080 ; 88, 1167,
1342 ; 89, 212, 51G) ; the dark lines of the ab-
sorption-spectrum of the solution of an Er salt
correspond with these. Obtained by heating the
nitrate or oxalate in air. Pale rose-coloured
powder. Not changed when heated in H. In-
fusible; glows with intense green light when
heated, without volatilising. Slowly dissolved
by hot HNOjAq, H,SO,Aq, or HCUq. Does not
directly combine with water.
Erbium, salts of. Compounds obtained by
replacing H of acids by Er. These salts are
formed by dissolving Er^Oa in acids ; many are
also formed by double decomposition from the
sulphate or nitrate. Solutions of Er salts are
more or less rose-ooloured ; they generally have
an acid'reaction with litmus, and taste sweetish
but astringent. The salts all belong to the form
Erj3X where X= SO4, 2NOs, fPO,, &o. ; a few
basic salts, e.g. Er^Os.JSCOj, have been obtained.
The principal salts are the bromate, carbonate,
chlorate and perchlorate, formate, iodate and
periodate, nitrate, oxalate, selenate and selemte,
sulphate and sulphite, and phosphate {v. Car-
bonates, Nitrates, &o.). M. M. P. 'M.
ERGOSTEBIN C^^U^fi. [154°]. S.G. 1-04.
[o]n = - 114°. Extracted from ergot of rye
(Tanret, O. B. 108, 98). Pointed needles (con-
taining aq) ; sol. alcohol and ether ; insol.
water. Slowly oxidises in air, very rapidly at
100^. Is not attacked even by hot concentrated
alkalis. Besembles cholesterin in many re-
actions, but gives different results with sulphuric
acid and chloroform. The acid dissolves the
ergosterin, and agitation with chlorofpnn gives
468
ERGOSTERIN.
no colouration till evaporation takes place, when
a trace of violet appears.
Pormyl derivativeCjai^,{CnO)0. [154°].
[a]= -93-4°. Spangles, sol; ether. ' '
Acetyl derivative C.i^B.3^eO. [169°].
[»]»= —80°. Pearly spangles, sol. ether and
alcohol, insol. water.
. Butyryl derivative C^„(C;B.fi)0.
[95°J. [a]D = -57°.
EEGOTININE C^^^^fi^T EchoUm. S. (95
p.c. alcohol). -5 at 20° ; 2 at 78°. [o]j = 137-5°.
Occurs in ergot of rye, together (according to
Dragendorff) with ' scleromucin,' ' sclerotic acid,'
' Bclererythrin,' ' solerocrystallin ' CiuHuO^,
' scleroxanthin ' C,„H,oO< l^aq, a hydrate of
sclerocrystaUin, mycose, mannite, cholesterin,
leucine, lactic acid, methylamine, and trimethyl-
amine (Wiggers, A. 1, 171 ; Manassewitz, Z. [2]
4, 154 ; Denzel, Ar. Ph. [3] 22, 49 ; DragendorfE,
Ar. Ph. 7, 32 -, C. O. 1878, 125 ; Bombelon, C. C.
1888, 472). Ergot also contains a fatty oil (Her-
mann, Bep. Pha/rm. 20,283; Ganser, Bep. Pharm.
20, 301). Tanret (J. Ph. 26, 320 ; C. /. 34, 81)
also obtained from ergot a crystalline substance,
smelling like camphor [165°], (209°), insol. water,
sol. alcohol, and chloroform. Kobert {J. 1884,
1512) describes ergot as containing cornutine
and sphacelic (ergotic) acid.
Preparation. — The ergot is exhausted with
alcohol, caustic soda is added to alkaline reac-
tion, the alcohol is distilled off, and the residue
agitated with ether. The ethereal extract is then
shaken with a concentrated solution of citric
acid, the citrate is decomposed by KjCO^, and
the ergotinine extracted by ether, from which it
crystallises. In this way 1-2 g. is got from 1 kilo
of ergot (Tanret, A. Ch. [5] 17, 499 ; C. B. 81,
896 ; 86, 888 ; cf. Blumberg, Ph. [3] 9, 23, 598).
Prcfperties. — Delicate prismatic needles, turn-
ing brown in air. Insol. water, sol. alcohol,
ether, and CHCI3. When the ergot is old an
amorphous substance (? modification of ergoti-
nine) present, which increases its solubility in
alcohol. Its solutions fluoresce violet. The rota-
tory power of the amorphous ergotinine [^o]j = 122°
is less than that of the crystalline variety. Er-
gotinine gives aU the general tests characteristic
of alkaloids. When a drop of E2S04is added to
its solution in acetic acid a red colouration pass-
ing rapidly to violet and blue is formed. Ergo-
tinine when injected hypodermically produces
intoxication.
Salt s.— B'HCl.— B'HBr.
£BICIIT. A dye-stuff in Erica vulgaris. It
gives a bronze-green pp. with iron salts, a golden-
green pp. with tin salts, and a green colour with
copper salts (Savigny a. Oollineau, O. C. 1881,
708 ; C. J. 42, 309).
EEICINONE CjjHjA (?)• [0. 167°]. An in-
different crystalline substance, said by TTloth
{A. Ill, 215) to be obtained by the dry distilla-
tion of ericaceous plants. May be sublimed.
ESICOLIN C^eHjoO,. A. resinous glucoside
found in several plants of the heath family, e.g.
common ling (Calluna vulgaris), wild marsh
rosemary {Ledmn palusire),mthe redbearberry
{Arctostaphykis v/va uirsi), in GauUheria pro-
cimibens, in Bpigcea repens, and in Bhododendron
ferrugineum (Kochleder a. Sohwarz, A. 84, 354,
bC8 ; Kawalier, Site. W. 9, 29 ; Oxley, Ph. [3]
2, 1050; Thai, J. 1883, 1401). It has a bitter
taste. Dilute acids split it up into glucose and
erioinol.
Ericiuol CjoSjsOj. Formed, together with glu-
cose, by distilling ericolin or pinipicrin with di-
lute HCl or HjSO,. Volatile oil, turning brown
in the air (Bochleder; Kawalier; Thai; Frohde,
J. pr. 82, 181). Ericinol takes up water, be-
coming ' ericinol hydrate ' C,oH3„0„ which has a
very characteristic odour (Thai).
EBIGEBOK OIL. The volatile oil from
Erigeron canadense contains a terpene ((176°).
S.G. i2 -848. [a]j = 6° 15'), identical with oitrene
andhesperi'dene (Wallach,^. 227, 292 ; cf. Yigier
a. Cloez, J. Ph. [5] 4, 333).
EKUCIC ACID CjjH^Oj. Brassidic acid.
Mol. w. 838. [34°]. An acid occurring as gly-
ceryl ether in colza oil (Welsky, J. pr. 58, 449 ;
Staedeler, A. 87, 133; Otto, 4.127,182; 135,
226 ; Haussknecht, A. 143, 40), in the fixed oil
of white mustard (Sinapis alba), and of black
mustard (Darby, A. 69, 1 ; Goldschmiedt, Sitz.
W. [2] 70, 451 ; 74, 394), and in the fatty oU
from grape seeds (Fitz, B. 4, 442).
Prepa/ration. — Bape-seed oil is saponified by
alcoholic KOH ; after distilling off most of the
alcohol the fatty acids are precipitated with di-
lute £[,804, separated, and dissolved in three
times the weight of 95 p.c. alcohol ; on cooling
the solution to 0° the erucic acid crystallises
out, and is recrystaUised in the same way (Bei-
mer a. Will, B. 19, 3320). Long needles (from
alcohol). Decomposed by potash-fusion into
acetic and arachio acids. Br forms the di-
bromide CjaH^jBrjOj [43°] {v. Di-beomo-behenio
acid). Nitrous acid converts erucic acid into the
isomeric brassic acid (g. v.). EI and F at 200°
give behenic acid.
Salt s.— NaA'.— BaA'j.— PbAV— AgA'.
Ethyl ether EtA': (above 360°); colour-
less odourless oil ; converted by nitrous acid into
ethyl brassate.
Glycerin-di-erucic ether C^BiMUjA'p
Dierucin. [47°]. Silky colourless crystals (from
ether-alcohol). Occurs as a deposit from rape-
seed oil after long standing. Y. sol. ether and
ligroin, m. sol. hot alcohol, insol. cold alcohol.
By nitrous acid it is converted into glyoerin-di-
brassic ether.
Olycerin-tri-erucic ether C^'H.^A.',. Tri-
erucin. [31°]. From erucic acid and glycerin
at 300°.
Amide C^iH^.CDNH,: [84°]; colourless
needles ; t. sol. ether and benzene, si. sol. alco-
hol, insol. water. Formed by the action of NH,
gas upon the anhydride.
Anilide Oj.H^.CO.NHPh : [55°] ; crystals;
v. sol. ether and benzene, si. sol. alcohol.
Anhydride (C2,H_„.00)20 : oU which so-
lidifies in a freezing mixture ; v. sol. ether and
benzene, v. si. sol. alcohol. Formed by the ac-
tion of PClj upon erucic acid and subsequent
addition of alcohol (Beimer a. WiU, B. 19, 8320).
EBYIHBENE v. Bctinene. .
Erythiene bromide v. Tetba-bbomo-butane
and Di-BBouo-BniyLENE.
EEYTHRIN CjoHj^Ojo i.e. C4H,(C,H,0,)A-
Erythric acid. Mol. w. 422. [137°]. S. -42 at
100°; S. (ether) -3 at 20°. Occurs in Boccella
timctoria, B. Montagnei, B. fticiformis and other
lichens (Heeren, Schw. J. 59, 313 ; Eane, A. 39,
25 ; Schunck, A. 61, 69 ; Stenhouse, A. 68, 72 i
ERYTHRITE.
459
Pr. 12, 263 ; C. J. 20, 222 ; Hesse, A. 117, 304 ;
De Luynes, A. Ch. [4] 2, 385 ; Mensohutkin, Bl.
[2] 2, 424). Extracted by milk of lime, and ppd.
by HCl. Crystalline mass (containing 1| aq).
SI. sol. water, v. sol. alcohol and ether. Its al-
coholic solution gives a violet colour with FejOlj.
JReaclions. — 1. Boiling water or alkalis split
it up into orsellic acid CaHjO, and pioroerythrin
OiAbO?; tlie orsellic acid being resolved by
longer boiling into COj and orcin. Boiling aZ-
cohol produces, in the same way, orsellic ether
and pioroerythrin. Methyl and amyl alcohols
act in like manner. — 2. Boiling with excess of
lime-water gives erythrite, orcin, and COj
(Lamparter, A. 134, 255). — 3. Bromme forms
Os.H,»Br,0,r
Metallic derivatives.— CaoHjaPbO,, aiaq.
Pb3(C„H„0J, 3aq.-OaH,aPb,0,o-—
Pb,(C,„H„0,.),.
(;8)-Erythrin CjiHj^O,,. Occurs in Boccella
fuciformis (Mensohutkin, Bl. [2] 2, 424). White
crystalline powder (containing aq). Nearly insol.
water, sol. alcohol, and ether. Decomposed by
boiling alcohol or water into orsellic ether or
acid and (j8) -pioroerythrin. Boiling baryta splits
it up into erythrite, COj, and betorcin. —
PbA,Ha,0,..
Erythrin v. Bbomo-fluoeesoeis.
ERTTHEITE CJS.fi^ i.e.
CHj(0H).GH(0H).CH(0H).CH2(0H). Erythrol.
Mryihramanmte. ErythrogVucin. Eryglucm.
PhyoiU. Mol. w. 122. [112°]. (330°). S.G. 1-45
(Schroder, B. 12, 562). Boo 43'65 (in a 14 p.o.
aqueous solation) (Eanonnikoff, -J. B. 15, 449).
Heat of solution - 5200 at 9° (Colson, 0. B. 104,
113). Occurs ready-formed in Protococcus
vulgaris and is produced by the action of boiling
lime or baryta upon erythrin or pioroerythrin
(Stenhouse, Tr. 1848, 76 ; 1849, 399 ; Strecker,
A. 68, 111 ; Sohunok, P. M. 7, 33, 254 ;,Lamy, A.
Oh. [3] 35, 138 ; 51, 232 ; Wagner, J. pr. 61,
125; Hesse, A. 117, 327 ; Hofmann, B. 7, 512 ;
De Luynes, A. Ch. [4] 2, 339 ; O. B. 56, 803).
Properiies. — ^Large dimetrio crystals with
sweet taste. Inactive. Neutral to litmus. V.
sol. water, si. sol. jcold alcohol, insol. ether. Does
not reduce Fehling's solution. Is not ppd. by
lead subacetate. Its aqueous solution dissolves
lime, a pp. being formed on boiling or on adding
alcohol. Does not undergo alcoholic fermenta-
tion. Like other polyhydrio alcohols, it renders
a solution of borax acid (Dunstan, PTi. [3] 13,
257). In presence of vegetable mould it under-
goes butyric fermentation (Pitz, B. 11, 1890 ; 12,
475). Erythrite does not react when heated with
aldehyde or isobutyric aldehyde at 125° (Lochert,
A. Ch. [6] 16, 64).
BeacOons. — 1. Potash-fusion gives acetic
and oxalic acids. — 2. Fuming nitric acid forms
the nitrate. Dilute nitric acid oxidises it to
oxalic and tartaric acids (Przybytek, Bl. [2] 35,
108) ; at the same time there is formed an alde-
hyde or ketone whose phenyl - hydrazide
OijHisN^Oj melts at [167°] (Fischer a. Tafel, B.
20, 1088).— 3. CrO, and KMnO^ give formic and
oxalic acids. 4H2S04 forms a sulphuric acid
C8H„Oj(S04H)s (Hesse, A. 117, 329). The salts
Ca3A"'a6aq,Ba,A"'26aq,andPbjA"'2l2aqhavebeen
described.— 4. Heating with aqueous HI forms
secondary butyl iodide.— 5. PBrj gives CiHjBr,
[112°] (Colson, C. B. 104, 113) .-6. Yields
thiophene by heating with P^Sj (Paal a. Tafel,
B. 18, 688).— 7. DistiUation Vith SjClj under
100mm. pressure yields a substance (? CiHjSO,)
which crystallises from ether in needles [116°]
(Heiminger, A. Ch. [6] 7, 23l).— 8. Formic aoid
produces several formins, including the crystal-
line tetraformin OjHjJO.CHO),. When the
mixture of formins is distilled at 250° there is
given o£E CO^, bntinene, and CO, and a liquid
distils over consisting of water, formic acid,
orotonio aldehyde, di-oxy-butylene (crotonylene
glycol), C^H,(OH)j ' dihydrofurfurane ' {0,B.fi),,
(67°)j and the anhydride of erythrite C^HgOj
(Henninger, C. B. 98, 149 ; A. Ch., [6] 7, 210 ;
Bl. [2] 19, 2, 145 ; 21, 242).— 9. Phenyl cyanate
(4 mols.) heated with erythrite (1 mol.) forms
CiHs(O.CO.NHPh), [215°] a mioroorystalline
solid, si. sol. alcohol and ether (Tessmer, B. 18,
970).
First Anhydride CjHjO,. Erythrane.
(155°) at 18 mm.
Formation. — 1. A product of the action of
formic aoid on erythrite. — 2. By heating ery-
thrite with equal weights of water and cone.
H2SO4. — 3. In small quantity by the action of
HCl on erythrite.
Properties. — Liquid. Cone. HCl converts it
into erythrite diohlorohydrin (Henninger, A. Ch.
[6] 7, 225).
Second Anhydride C^fi^ i.e.
0 O
A /\
CHj.CH.CH.CH2 (?). Erythrite dioxide. Ery-
thrane. (138°). S.G. 2 1-132 ; ia 1-113. C.B.
(0°-18°) -00095. V.D. 3-16 (obs.). Formed by
treating erythrite dichlorhydrin in ethereal
solution with KOH, the yield being 70 p.c.
(Pryzbytek, B. 17, 1092 ; Bl. [2] 41, 393 ; 42, 322).
Mobile liquid, misoible with water. Slowly
unites with water to form erythrite. Combines
with HCl reproducing the dichlorhydrin. Unites
with HCN to form the nitrile of di-oxy-adipio
acid. Beadily combines with NH3 and amines.
Aniline forms a compound CjsHjjNjOj. Eeduces
AgNOj forming a mirror. Ppts. MgO from
magnesium salts.
Isomeride of the Second Anhydride
CiHjO^. [173°]. Formed, together with
C4Hs(OH)(OEt)2, by the action of NaOEt upon
erythrite dichlorhydrin, or by treating the
dichlorhydrin with powdered NaOH (Henninger,
A. Ch. [6] 7, 225). Plates (from alcohol).
Di-ethyl ether C4H8(OH)j(OEt)„. [13-5°].
(144°) at 22 mm. From the dichlorhydrin and
NaOEt at 100° (Henninger, A. Ch. [6] 7, 230).
Erythrite tetraultrate C4He(NO,)4. Nitro-
erythrite. [61°]. Formed by dissolving erythrite
in cold fuming HNO3 and ppg. by the addition ,
of HjSO, (Stenhouse, Tr. 1849, 399). Large
plates (from alcohol). Insol. cold water. Ex-
plodes when struck. Alcoholic ammonium
sulphide reconverts it into erythrite.
Erythrite tetra-sulphuric acid
C^JBO^)^. Deliquescent crystals got by
dissolving erythrite in ClSOjH. Boiling water
slowly resolves it into erythrite and hydric sul-
phate (Claesson, J.jgr. [2] 20, 7).
Salts. — KjA"",4aq. Nearly insol. cold
water. BaA"',4aq. Insol. water. Ppd. by
adding BaCl^ to a solution of the free acid but
not to one of the potassium salt (Claesson).
400
ERYTHRITE.
Mono -formyl derivative
C4HJOH)8(O.CHO). Erythrite monoforrmn.
(192°). Formed, together with the following,
by boiling erythrite (1 pt.) with formic aoid (2^
pts.) for 6hom-s (Heiminger, A, Oh. [6] 7, 215).
Tetra-fortnyl derivative OiHj(O.CHO),.
[150°]. Prepared by heating erythrite with
formic acid at 200° and extracting with dry
ether; the product being treated in the same
way with 20 pts. of formic acid (S.G. 1-18).
Long needles (from alcohol).
Benzoyl derivative C<Ha(OH)j(OBz).
Prom erythrite and HOBz at 250° (Berthelot,
CMmie organ/igue, 2, 224). Crystalline mass,
insol. water, v. sol. alcohol and ether.
Tetra-benzoyl derivative C4H|i(0Bz),.
From the preceding (1 pt.) and HOBz (15 pts.)
at 200° (B.). Nearly insol. water.
Orsellyl derivative G,^^fiji.e.
C.H,(OH)j(O.CO.O,H,(OH)jMe).
Picroerythrin. [158°]. Obtaiued by boiling
erythriu with water, alcohols, or alkalis (Schunck,
A. 61, 64 ; Stenhouse, A. 68, 76 ; Hesse, A. 117,
321). Silky prisms (containing 3aq). Tastes
bitter. V. e. sol. hot water. Decomposed by
boiling lime-water into erythrite, orcin, and
COj. Gives a purple colour with Fe^Clj.
(S)-Orsellyl derivative. Anhydride.
CisHjjOj. (B)-Ficroerythrin. Obtained by
boiling (i3)-erythriu with alcohol (Menschutkin,
Bl. [2] 2, 424). Needles, v. e. sol. water and
alcohol, insol. ether, Beduces hot silver solu-
tion. Split up by boiling with baryta into COj
erythrite, and betoroin CsHi^Oo.
Erythrite chlorhydrlu C4Hs(OH)3Cl. [66°].
Flat interlacing needles, sol. alcohol, insol.
ether.
Erythrite dichlorhydrin 04H8(OH)jCl2.
[126°]. (152°) at 30 mm. Prepared by heating
erythrite (200 g.) with cone. HOlAq (2400 g.) for
6 hours, and distilling the product under re-
duced pressure. Arborescent mass of crystals,
V. sol. alcohol (Henninger, A. Ch. [6] 7, 228 ;
Przybytek, B. 17, 1091). A mixture of HNO,
and H^SO, converts it into the nitrate
C4Hs(NO,)jCl2 [60°] (Champion, C. B. 73, 114).
Erythrite tetrachlorhydrin v. Teiba-chiiObo-
BUTANE.
Erythrite dibromhydrin C4Hj(OH)4Br2.
[130°]. From erythrite and cone. HBrAq at
110° (Champion, Z. 1871, 348; G. B. 73, 114).
Crystals (from ether), insol. water. A cold
mixture of fuming HNO, (1 pt.) and cone. H.SO,
(2 pts.) forms the nitrate C,Hs(N03)2Br2 [75°].
EBYTHBOCENTATJBIN C„Hj,0„. [136°].
S. -06 at 15° ; 7 at 100° ; S. (86 p.c. alcohol) 2 ;
S. (ether) '4 ; S. (chloroform) 7. A substance
allied to santonin which may be extracted by
alcohol from the common centaury {Erythraa
Centaurium). Tasteless crystals (from ether) ;
neutral to Litmus. Inactive. Sol. most menstrua ;
water ppts. it unaltered from its solution in H^SO^.
It turns bright red in sunlight, being affected by
the blue or violet rays; the red colour disappears
on solution or on heating to 130° (Mehu, J, Ph.
[4] 3, 265).
EEYTHR06LTICIC ACID C^HbO^ i.e.
CH2(0H).CH(0H).CH(0H).C0jH. Obtained by
(he oxidation of erythrite by air in presence of
platinum-black or by nitric acid (Sell, Bl. [2] 5,
384 ;Lamparter,^. 184, 243). Deliquescent mass ;
v. sol. water and alcohol. — BaOjHsOs aq (L.). —
(04H;Pb05)4Pb02H2(S.).— C,H,PbO,(atl60°;L.).
EBTTHEO-OXY-ANTHHAftUINONE v. Oxy-
ANTHKAQUINONE.
EBTIHBOFHLEllTE. Aa alkaloid in the
bark of Erythrophlcsv/m guimeense (Gallois a.
Hardy, Bl. [2] 26, 39). Sol. alcohol, si. sol.
ether. Gives a violet colour with MnOj and
H^SO,.
ESENEECKINE. An alkaloid in the bark of
Esenbeckia febrifuga (Buohner, Bep. Pharm. 31,
481 ; 37, 1 ; Am Ende, Ar. Ph. [2] 143, 112).
ESERINE CisHjiNsOj. Phytostigmme. [45°],
An alkaloid which may be extracted by moist
alcohol from Calabar beans (Petit, J. Ph. [4] 14,
255; a.B. 72, 569; Hesse, A. 129, 115; 141,
82). Besinous; v. sol. alcohol, ether, benzene,
and CHClj ; m. sol. water. Alkaline to litmus.
Poisonous, producing contraction of the pupil.
The sulphate evaporated with ammonia leaves a
blue residue. Bleaching powder colours its solu-
tion red.— B'HIHglj. [70°] (H.).
ESSENIIAI. OILS. Oils, usually obtained
from plants, which are volatile either alone or
with steam. They usually contain one or mora
hydrocarbons such as terpenes (g. v.) and one or
more substances containing oxygen, which some-
times separate in a solid form on cooling strongly
and are then called stearoptenes, the remaining
liquid being termed elseoptene {v. also Ons).
ESTEB. A name applied by Gmelin to com-
pound ethers derived from oxygenated acids to
distinguish them from simple and mixed ethers.
ETHALDEHYDE v. Aldehyde.
ETHANE CjHa i.e. CH3.CH3. Di-methyl-
ethyl hydride. Mol. w. 30. S. -0871 at 0° (Bun-
sen) ; S. (alcohol) 1-5 (Berthelot, J. 1867, 344).
H.P.p. 25,670 (Thomsen, J.pr. [2] 23, 158) ; 28,560
(Th.); 28,000 (Dulong; Favre a. Silbermann).
H.F.V. 24,510 (Thomsen) ; 27,400 (Th.).
Occurrence. — In the gases given off by natural
petroleum (Smith, A. Oh. [5] 8, 566).
Formation. — 1. By the action of methyl
iodide upon zinc or sodium (Frankland, O. J. 2,
173; A. 71, 213; Wanklyn a. Buckeisen, A.
116, 329). — 2. By heating propionitrile with
potassium (Frankland a. Eolbe, 0. J. 1, 60 ; A.
65, 269). — 3. By the electrolysis of potassium
acetate (Kolbe, A. 69, 279). — i. By the action of
water on zinc ethyl (Frankland, 0. J. 3, 338 ; A.
71, 203 ; 85, 360 ; 95, 53).— 5. By heating ethyl
iodide (9 pts.) with AljClj (2-6 pts.) at 150°
(Kohnlein, B. 16, 562). — 6. In small quantity
together with methane and COj by heating AajO
withBa02(Sohiitzenberger,BZ. [2] 5,278; Darling,
C. J. 21, 496).— 7. From HgEtj and H^SO^ (Sohor-
lemmer, A. 132, 234).— 8. From EtI, alcohol, and
zinc-dust (SabanejefE, B. 9, 1810).
Preparation. — ^By dropping a mixture ol
equal volumes of ethyl iodide and absolute alco-
hol upon the copper-zinc couple, the gas being
passed through a scrubber containing copper-
zinc, through alcoholic NaOH, through bromine-
water, through caustic soda, and finally through
slaked lime (Percy Frankland, O. J. 47, 236).
Properties. — Colourless gas. Burns with pale
flame. With water under pressure it forms a
crystalline hydrate (Villard, C. B. 106, 1602).
The identity of ethane from ZnBt2 with that
from KOAo may be shown by chlorination, both
yielding ethyl chloride (Sohorlemmer, A. 131,
ETHANE SULPHONIO ACID.
461
16 ; 132, 234) or by their heata of combustion
(Thomsen, J. pr. [2] 23, 158).
Derivatives v. Bbomo-, Bbomo-ioso-,
Bbomo-nitbo-, Chlobo-, Chlobo-iodo-, Chlobo-
NUBO-, NlIBO-ETHAKES, &a.
ETHAITE-AKSOinC ACID v. Absbnio oom-
FOCNDS, OBOANIC.
ETHANE-TRICARBOXYLIC ACID
C0jH.CHj.0H(a02H)j. [159°]. From the ether
by cone. EOHAq. Formed also by saponifying
ethane tetra-carboxylio aoid and from bromo-
Bucoinic ether by suooessive treatment with alco-
holic KCy and KOH (Orlowsky, J. B. 9, 278 ; B.
9, 1604). Small hard prisms (from ether). V.
sol. alcohol, ether, or water, si. sol. benzene.
When melted it splits up into CO, and succinic
acid.
Salts. — The ammonium salt gives pps. with
BaClj or Pb(OAo)2 in the cold, and with CaClj or
PeClj on warming. — 0ajA"'2. — Zn3A"'22aq.—
Ethyl ether C02Bt.CHj.CH(C0jEt)j. (278"
unoor.). S.G-. yf 1*089. From malonic ether,
NaOEt, alcohol, and chloro-acetio ether (Bi-
Bohoff, A. 214, 38). Oil. V. e. sol. alcohol or
ether. By the action of 01 on the ether chloro-
ethane-trioarboxylic ether is formed, which on
boiling with HOI gives fumaric aoid, and with
KOH gives malic acid. By the successive
action of sodium and chloro-acetic-ether on the
ether, the ether of propaue-tetra-oarboxylio acid
(C02H)CHj.0{C0yH)j.0H2(002H) is formed, and
this acid on heating gives 00, and tricarballylio
acid (002H)CH2.0H(C0jH).CHj(C02H) (Bischoft,
B. 13, 2161).
First nitrile v. CyANO-snooiNio etheb.
Ethane tetra-carboxylic acid CgH^Og i.e.
(C02H)jOH,OH(OOjH)j.
Acetylene tetra-cwrboxylio aoid.
Di-ethyl ether
C0jEt.CH{002E[).0H(002H).00jEt. [133°]. The
potassium salt is formed as a sticky pp. by the
action of KOH (36 g.) on the tetra-ethyl ether
(28 g.) dissolved in alcohol (720 g.) at 0°. Plates
with obtuse angles. Deliquescent, v. sol. alcohol
or ether, si. sol. chloroform or CSj. When heated,
it spUts off COj, becoming succinic ether
(Guthzeit, A. 214, 72). The salt Na^Bt^A"" is
converted by di-bromo-o-xylene C8H4(CH2Br)2
into naphthalene tetra-hydride tetraoarboxylio
aoid (Baeyer a. PerMn, B. 17, 449).
Tetra-ethyl ether Et,A"". [76°]. (305°).
From malonic ether, chloro-malonic ether, NaOEt
and alcohol (Conrad a. Bisohoff, A. 214, 68 ; B.
13, 601 ; 21, 2087). Formed also by the action
of iodine (1 mol.) on sodio-malonio ether (2 mols.),
dissolved in absolute alcohol (BischofE a. Bach,
B. 17, 2781). Needles. V. sol. alcohol, ether or
benzene.
Reactions. — 1. Very stable. NaOEt and
benzyl chloride do not form a benzyl derivative.
2. Heated with aqueous HOI, or with aqueous
KOH, it forms COj, ethane tri-oarboxylic acid
' and alcohol.
Amide C2H2(C0NHj)4. Crystals, v. si. sol.
water. Decomposes above 230°.
ETHANE-PHOSPHONIC ACID C A-P0(0H)2.
[44°]. From ethyl-phosphine and fuming HNOj
(Hofmann, B. 5, 106). Crystals, v. e. sol. water.—
Ag^A" : amorphous yellow pcwder.
Chloride C^Hs.POClj. (o. 1750). Liquid
(Michaelis, B. 13, 2174).
EIHANE-SELimc ACID v. Selenium cou-
ponuns, OEOANio.
ETHANE-SUEPHINIC ACID O^B.^.'&O^.
Ethyl-sulphimic add.
Fonnfition. — 1. By the action of ZnEtj
followed by water upon SO, (Wischin, A. 139,
364). — 2. From ethane-sulphonio chloride and
zinc-dust (Panly, B. 10, 941).~3. By the oxida-
tion of sodium mercaptide NaSEt. — 4. From
FbEtt and SO, (Frankland a. Lawrance, C. J,
35, 246).
Properties. — Syrnp. Gives ethane-sulphonio
acid when oxidised by HNO, (Glaesson, /. pr.
[2] 15, 222) and a compound CjHisNSaO, [81°]
(Zuoksohwerdt, A. 174, 308).
Salts. — NaA': crystals (from alcohol). —
BaA'j aq.— ZnA'j aq.— PbA',. Prom PbEt, and
SO2 (Frankland a. Lauranoe, B. 12, 846).— AgA' :
laminee, m. sol. water.
Ethane di-sulphinic acid 02H,S204 i.e,
OjH,(S02H)2.
EthyUne-disulpMnie acid. From ethane
disulphonio chloride C2H4(SO201)2, zinc-dust and
water (Otto, /. pr. [2] 36, 439). The free acid
is unstable. '
Salts. — ^Na2A"4aq: small laminsB from
alcohol), V. e. sol. water, si. sol. alcohol. — ZnA', :
small plates, si. sol. cold, v. sol. hot water.
Di-methyl ether Me^A". [190°]. Di-
methyl ethylene disutphone. From the sodium
salt and MeBr. Plates, insol. cold, sol. hot
water and alcohol.
Di-ethyl ether Et^A". [137°]. Ethylene
diethyl suVphbne. From Na^A" and EtBr (Otto,
J. pr. [2] 36, 436). Needles. SI. sol. ether,
benzene, chloroform andCS,, v. sol. hot alcohol. ,
Converted by PCI5 into CjH4(S0jCl)j [91°]. Be-
duced in alkaline solution to ethane sulphinia
acid. Aqueous KOH forms CjH4(0H)(S0jEt)
and ethane-sulphonic acid. Ammonia forms a
substance [83°].
Di-propyl ether PrjA". [155°]. From
Na2A"andBrPr (Otto). Iridescent plates.
CHj.SOs.CHj
Ethylene ether C.B..&." i.e. \ | .
CH2.SOj.CH,
From NajA" and ethylene bromide (Otto, J. pr.
[2] 36, 446). Prisms, insol. ordinary solvents,
m. sol. hot cone. HNO3.
ETHANE STTLFHONIG ACID CjHjSOjH.
Ethyl sulphordc acid.
Formation. — 1. By the oxidation of mer-
captan, of ethyl sulphocyanide, or of di-ethyl
disulphide (Lowig a. Weidmann, P. 47, 153 ; 49,
329 ; Kopp, A. 35, 346 ; Muspratt, C. J. 3, 18).
2. From KjSOj and Btl (Streoker, A. 148, 90;
Graebe, A. 146, 37).
Properties. — Deliquescent mass. Not acted
on by 01, but converted by XCI3 into CjHjCljSOjH
and OjClj (Spring a. Winssinger, B. 15, 445).
Salts.— NaA' a;aq.—NaA'JNaI (Bender, A.
148, 90). — KA' aq. — CaA', xaq. — BaA', aq. —
ZnA'27aq.— CuA',5aq.— HgA'jHgO (Glaesson, A.
148, 90).— PbA', aq.— AgA'.
Methyl etherUek'. (c.l99°). From ethane-
sulphonic chloride and NaOMe (Carius, J. pr.
[2] 2, 262).
Ethyl ether EtA'. Mol. w. 138. (213°
cor.). S.G. 2 1-1712 ;=j<' 1-1452. Eco 29-79. From
462
ETHANE SULPHONIC ACID.
CjHs.SOjCl and NaOEt (0.) ; or from EtI and
Ag^SOj (Kurbatoff, A. 173, 7 ; Nasini, B. 15,
2884; (3.13,304).
Chloride CjHsSOjCl. (178° cor.). S.G.
»:» 1-357. Prom the sodium salt and PCI,
(Gerhardt a. Chancel, C. R. 35, 691). Also from
di-ethyl sulphozide and chlorine in presence of
■water (S. a. W.). PCI5 decomposes it into EtCl
and SOOI2.
Amide CsHsSO^NHj. [58°]. Silky needles or
long prisms (from ether). Sol. water, alcohol
and ether (James, C J. 43, 43).
Methylamide CJEL^.SO^BMe. (276°).
S.Gr. IS 1-216. From the chloride and methyl-
aiaine, both being dissolved in cold ether (Fran-
chimont a. Klobbie, B. T. G. 5, 274). Liquid,
misoible with water. When poured into 5 pts.
of fuming HNOa (S.G. 1-5) it forms a nitramide
CjHj.S02.N(N02)Me [11°], a Kquid which defla-
grates at 100° and is si. sol. cold water. The
nitramide is volatile with steam.
Di-methyl-amide C^HsSOjNMej. (240°).
S.G. i- 1-146. Liquid, miscible with water.
When poured into 5 vols, of HNO3 (S.G. 1-5) it
gives di-methyl-nitramine NMe2N02. -
Ethyl-amideC^S.,.SO^j!iBMt: (272°). S.G.
is 1-154. Liquid, miscible with water, sol.
ether. HNO, (S.G. 1-5) gives the nitramide
OjH5.SO2.NEt.NO2 [20°], a crystalline substance
si. sol. cold water, volatile with steam.
Di-ethyl-amide CjHj.SOj.NEtj. (254°).
S.G. — 1-080. Liquid, with characteristic odour,
Bol. ether, sol. water, but not misoible therewith.
Fuming HNO, (S.G. 1-5) gives CjH^.SOj.NEt.NOj
(F. a. K.).
s-Ethane-disnlphonic acid
SO3H.CH2.CH2.SO3H. Ethylene disulphon/ic
add. [94°] (when anhydrous). .
FormaUm. — 1. Together with sulpho-pro-
pionio acid and CO^, by heating propionamide or
propionitrile with fuming H2S0j (Buckton a.
Hofmann, C. J. 9, 250; A. 100, 129).— 2. By
the action of fuming hitric acid upon ethylene
thiocarbonate C.,H,CS3 (Husemann, A. 126, 269)
or upon C„H4(SH)2. — 3. From nitro-ethane and
fuming H2SO4 (Meyer a. Wurster, B. 11, 1168).
Properties. — Deliquescent mass of radiating
crystals (containing aq). Potash-fusion gives
acetylene (Berthelot, Z. 1869, 682).
Salts. — (NHJjA': long monoclinio prisms.
— KjA" : thick, four-sided, monoclinio prisms. S.
38 at 17°.— KHA" liaq : hard crystalline crusts.
— Na^A." 2aq. S. -023 at 21° (Guareschi, G. 9,
88).: — Ag2A": thin monoclinio tablfes. —
Ag3HA"2 12aq. — BaA"aq : stellate groups of six-
sided tablets (B. a. H.). — BaA": monoclinio
prisms ; ppd. by alcohol, or from water. S. 2-85
at 17° (G.). — BaA' 2aq : trimetric octahedra
(Husemann). — CaA". — CuA"4aq : monoclinio
light-blue prisms. — PbA"l|aq: easily soluble
crystals. — PbA" 2aq. — MgA" 6aq. — HgA' 6aq :
long thin monoclinic prisms. — Hg2A"aq : white
crusts, which separate on warming into an acid
and a basic salt. — ZnA" 6aq : nacreous mono-
clinic tables.
Chloride CjH/SOjCl)^. [91°]. Neeidles
(from ether). Boiling alcohol decomposes it,
giving off SO2 and EtCl (Konigs, B. 7, 1163).
u-Ethane disulphonic acid CH,.CH(S0,H)2.
Ethylidene disulphonic acid. Obtained by oxi-
dising thio-jJdehyde (CjHjS), or thialdine by
KMnO, (Guaresohi, G. 9, 75; A. 222, 302).
Syrup, V. sol. water and alcohol.
Salts. — Na2A."aq: tables, nearly insol. al-
cohol.— K3A"2aq: prisms (from water). — KjA":
needles, ppd. by adding alcohol to its aqueous
solution. S. 64 at 17°.— MgA" 6aq.— CaA".—
BaA" 3aq : tables (from water). S. (of BaA")
11 at 17°. — BaA"3iaq: ppd. by alcohol.—
CaA" 2aq. — CuA" aq. — AgjA" aq : slender
needles.
Ethyl ether Et^A". From AgjA" and EtI
(Mauzelius, B. 21, 1551). Beddish oil, insol.
alkalis, v. sol. alcohol and ether. With NaOEt
it gives CHs.CNa(SOsEt)j, whence EtI gives
butane disulphonic ether.
Ethane-tri-sulphonic acid
CH2(SO,H).CH(S03H)2. ' Ethenyl-tri-sulphonic
add.' Formed by boiling tri-chloro-ethane
(chloro-ethylene dichloride) with a saturated
aqueous solution of neutral ammonium solphite
(Monari, B. 18, 1346). Large hexagonal tables.
Y. sol. water and alcohol. Strongly acid.
Salt s. — ^A"'Na3 4aq : large six-sided tables. —
A"'(NH4)3: large prisms. — A'-'^Ba, 5|aq : octa-
hedral crystals, somewhat sol. water,
EIHANE-IHIO-SULFHONIC ACID
C2H5.SO2.SH. Prepared by the action of KjS on
ethane-sulphonic chloride (Spring, B. 7, 1162).
Ethyl ether CJHs.SOrSO^s. Ethyl-di-
sulphoxide. (130°-14"0°). S.G. 1-24. Prepared
by the action of CjHjBr on the potassium salt
(Otto, B. 15, 122 ; 11, 2073). Formed also by
heating mercaptan or Et,S2 with nitric acid
(S.G. 1-23) (Lowig a. Weidmann, A. 35, 343 ;
Iiukaschewitoh, Z. 1868, 641). Oil, smelling of
onions ; volatile with steam ; v. sol. alcohol and
ether, insol. ligroin. Further oxidation by
HNOg converts it into ethane-sulphonic acid.
Zinc and dilute H2SO4 reduce it to mercaptan.
Aqueous potash forms EtjS:, ethane sulphonic
acid, and ethane sulphinic acid (Pauly a. Otto,
B. 11, 2073).
ETHENYI. The trivalent radicle , CHj.C:
Vinyl is the name given to the isomeric mono-
valent radicle CH,:CH.
ETHENYL-AMIDINE v. Aobtamidine.
ETHENTL-AHIDO-BENZAMIDE v. OxY-
METHTL-QUINAZOLINE.
ETHENYI TEI-AMIDO-BEWZEWE
C3H3(NH2)(N2HC2H,). The hydrochloride of
this base JB'H2Cl2 l^aq, formed by the action of
HCl on its acetyl derivative, crystallises in easily
soluble lustrous crystals.
Acetyl derivative
CeH3(NHAc)(NjHC2H3) 2aq. [85°-90°] (above
360°). From tri-amido-benzene and ACjO (Sal-
kowski a. Budolph, B. 10, 1692). Geodes of
prisms (from water) ; v. si. sol. cold water.
Ethenyl-tetra-amido-benzene CgH^Nj i.e.
C,H2(NH2)2<™^CMe [1:2:3:4]. Formed by
reduction of nitro-ethenyl-tri-amido-benzene.
The free base is at once oxidised by the air to
brown bodies. With quinones it forms quinox-
alines. — ^B"HjCl2: colourless plates. The
picrate forms sparingly soluble yellow needles
(Nietzki a. Hagenbach, B. 20, 833).
Si-ethenyl-tetra-amido-benzene C„H„Nj i.e.
C,nJl<^^yme)^ [1:2:3:4]. [210°]. Long
colourless needles (containing aq). Y. sol. alco-
ETHENYIj-AMIDOXIM.
463
hoi and hot water, si. sol. cold water, nearly insol.
ether. Formed by reduction of di-nitro-di-aoetyl-
p-phenylene-diamine with tin and HCl. It is a
very stable body and cannot be saponified.
Salts. — B"H2Cljaq: colourless soluble crys-
tals.—B"Hj01jPt01, 2aq : long yellow needles.—
B"HjS04 aq : colourless needles. — Picrate
B"0eHj(N02)30H : yellow needles (Nietzki a.
Hagenbach, B. 20, 329).
Di-ethenyl-tetra-amldo-benzene C,„H,„N4 i.e.
C»H,(<^>OMe), [1:2:4:5]. (above 360°).
Colourless needles. Formed by reduction of di-
acetyl-di-nitro-m-phenylene-dlamine.
Salts. — ^B"HjS04 : colourless needles. —
B"H2CajPtCl,Aq : yellow needles (Nietzki a.
Hagenbach, .5. 20, 386).
ETHENYI-DI-AMIDO-BENZOIC ACID
CjH,(C02H)<|^jj^C.CH3 [1:3:4]. Mhenyl-o.
pheavylene-diamine carboxylic acid. [o. 302°].
Formed by reduction of m-nitro-^-aoetamido-
benzoio acid [221°], or of p-nitro-m-acetamido-
benzoio acid [206°], with tin and acetic acid
(Eaiser, B. 18, 2944). White needles (contain-
ing aq). V. sol. hot acetic acid, less sol. hot
alcohol, nearly insol. ether, acetone, benzene,
and chloroform.
Salts. — A^K : very soluble microscopic
needles A'H,HC1 Jaq: easily soluble fine white
needles.— (A'H,HCa)^tCl,2aq: thick yellow
needles, sol. hot, si. sol. cold, water.
ETHENYL-AffllSO-jp-CBESOL
[l|].C.H,(CH,)<;°>O.CH.. (219° unoor.).
Formed by boiling the hydrochloride of amido-
2>-cresol with acetic anhydride and sodium
acetate (NSlting ' a. Kohn, B. 17, 361). Liquid.
Sol. alcohol, ether, and aqueous acids, t. si. sol.
water. ■
Salts. — B'HCl* : very soluble white crystal-
line powder. — ^B'^HjCl^PtCli : yellow powder, sol.
water and alcohol.
ETHENYIi - TBI - AMIDO - ij' - CTTMEHE v.
Amido-iJ'-obmtlbne-aoetamidine .
ETHENYL-TEI-AMIDO-IIAPHTHALEITE
C,jH„N, i.e. NH,.C,„H,<^2>0.CH,. From
the acetyl derivative of di-mtro-(a)-naphthyl-
amine by reduction with tin and HOI (Meldola a.
Streatfeild, O. J. 51, 692). The free base is ex-
tremely soluble in water, and is rapidly oxidised
by exposure of its solution to the air. Aqueous
solutions of its salts are oxidised by air.
Salts.— B"HjSO, Jaqf.— B'TBLjClj IJaq : stel-
late aggregates of thick stumpy needles. —
B"HiCL,|aq : long white needles.— B"HjPtClr—
B"H,Zn01i aq.
ETHENYl-(o)-AMID0.(;8)-IIAPHTH0L
CioHs<[q^C.CH,. Formed by heatmg acetyl-
(o)-amido-($1-naphtholC,„H5(NHAc)OH.—
B'jHjOliPtCli 2aq : yellow crystalline powder
(Bottoher, B. 16, 1939 ; C. C. 1884, 898).
ETHENYL - (o) - AMIDO - NAPHTHYL - M33R.
CAPTAN CoH^^^CCH,. [95°] (J.). Formed,
together with dioarbyl-amido-naphthyl mercap-
tan, by heating acetyl-(o)-naphthylamine with
sulphur (Hofmann, B. 20, 1800). Obtained by
oxidation of the thioacetyl derivative of {a)-
naphthylamine C,„H,.N:0(SH).CHs with potas*
slum ferricyanide ; the yield is 50 p.c. of theo-
retical (Jacobsen, B. 20, 1898). Colourless pris-
matic crystals (from alcohol) (J.). Insol. water;
volatile with steam (H.), Gives phthalio acid
when oxidised by EMnO. (Jacobsen, B. 21,
2624).
ETHENYL-AMIDO-PHENOL v. Amido-
PHENOii, vol. i. p. 170.
ETHENYL-AMIDO-PHENYL UEBCAPTAIT
C,H,NS t.e. CjHi^^^CCH,. (239°).
Formation. — 1. By heating o-amido-phenyl
mercaptan with aldehyde, acetic anhydride, ace-
tonitrile, or acetyl chloride (Hofmann, B. 13, 21,
1286).— 2. By oxidation of a cold dilute solution
of thio-acetaniUde in an excess of aqueous NaOH
by means of E,,FeCy, ; the yield is 33 p.c. (Jacob-
sen, B. 19, 1072).
Properties. — Colourless oil.
When an alkylo-iodide of this base is mixed
with an alkylo-iodide of methenyl-o-amido-phenyl
mercaptan, and the aqueous solution boiled with
NH,, colouring-matters are obtained analogous to
the cyamines {v. MBTHBNTii-o-AMrDo-PHENYL-MEB-
caftan). In this and other respects the base
shows considerable analogy with methyl-quinol-
ine (Hofmann, JB. 20, 2262). Phthalio anhydride
and ZnCl, at 190° give rise to the compound
G.H,<g^C.CH:(CjOs):C6H, [above 320°] (Jacob-
sen, B. 21, 2624),
Salt. — B'2H2PtClj : needles or prisms.
ETHENYL-TBI-AMIDO-TOLUENE
CA(CH3)(NHJ<^^>0.CH,
[1:5:3:4]. [o.
100°].
Preparation. — Di-nitro-acetyl-^-toluidine (1
pt.) is reduced with tin (5 pts.) and cone. HCl
(10 pts.) and boiled for five or six hours ; on con-
centration of the solution the hydrochloride
crystallises out.
Prc^erties. — Transparent mouoolinic crystals
(contaming aq), a:6:c=l-5813:l:0-8216. V. sol.
hot water and alcohol, si. sol. ether and benzene,
nearly insol. cold water.
Acetyl derivative
CeH2Me(NHAc).N2HC2Hs : [166°]; white con-
centric needles. Formed by the action of acetic
anhydride upon ethenyl-tri-amido-toluene, or
upon ^-aoetyl-tri-amido-toluene. By boiling
with cone. HCl it is converted into ethenyl-tri-
amido-toluene (Niementowski, B. 19, 719).
ETHENYL-AMIDO-TOIYI. ME&CAPTAK
CsH3(CH3)<^g^0.CH3. Prepared by heating
2J-amido-m-tolyJ merdaptan with acetic anhy-
dride.—(B'HCy^PtCU (Hess, B. 14, 493).
ETHENYL-AMIDOXIM C^H^NjO i.e.
CH3.C(NH2):NOH. Acetamidoayim. [135°]. Long,
pointed crystals. V. sol. water and alcohol. FejClg
gives a deep-red colour. On warming with water
it decomposes into hydroxylamine and acetamide.
The hydrochloride (B'HCl) is prepared by the ac-
tion of hydroxylamine on acetonitrile in aqueous
alcoholic solution at 30°-40°. It crystallises in
white glistening scales [140°] ; v. sol. water and
alcohol, insol. ether, benzene, and ligroiu.
With NaNOj it yields acetamide and NjO.
With CuSO, and NH, it gives a bluish-green
pp. of the formula CjH5NjOCu(OH).
161
ETHENYL-AMIDOXIM.
Bemyl ether CH3.C(NH;2):N(OCHjPh):
yellow oily liquid; v. sol. alcohol, ether and
benzene, nearly insol. water. Its hydrochloride
(B'HCl) forms silky white scales [168°], v. sol.
water and alcohol (Nordmann, B. 17, 2746).
ETHENYL - AMIDO -XYIiYL - MERCAPTAN
CBHjjMej-C^g^CMe. Oil. Fromthio-aoetyl-xyli-
dine and alkaline KjFeCy, (Gudeman, B. 21,
2549).
ETHENYL-AZOXIM v. Azoxims.
ETHENYL- BBOKO - (o(8) - ITAPHTHYLENE-
SIAUINE v. Bromo-eihenyl-haihthyiiEne-
DIAMINE.
TEI-ETHENYL-BTJTYBIC ACID v. Deoonoio
ACID.
ETHENYL TSICAEBOrLYLIC ACID v.
ElHANE TBIOAEEOXyiilC ACID.
ETHENYL - TKI - METHYLENE - DIAMINE
CsH,„Nj i.e. CHj<^^;^^^CMe. Obtained as
hydrochloride on treating tri-methylene-diamine
hydrate with ACjO, distilling off HOAo and
warming in an atmosphere of HCl (Hofmann, B.
21, 2336). The base is a brown oil.
Salts. — B'jHjPtOls: large rhombic crystals,
V. Bol. water. — ^B'HCl.AuCl3 : needles.
ETHENYL - (1:2) - NAPHTHYLENE - DI -
AMINE C,„H,<^^^^C.CH3. NaphthyUm-
acetamiMne. Formed by reduction of the
acetyl derivative of (l:2)-nitro-(B)-naphthyl.
amine with tin and HCl (Lellmann a. Bemy, B.
19, 799). Formed also by reducing bromo-
ethenyl-naphthylene-diamine [229°] in alcoholic
solution by sodium amalgam (Prager, B. 18,
2161), and by reducing acetyl-nitro-(i8)-naph-
thylamine with SnCl^ (Jacobsen, B. 14, 1794).
Salts. — ^B'HCl : small soluble colourless
needles. — B'2H2Cl2PtCl4: yellow crystalline pp. —
B'H2S04:[269°];whitepowder.— B'CsHj{N02)30H:
[242°] ; small yellow needles or plates.
ETHENYL-TRI-PHENOL v. Tei-oxt-ibi-
PHENYL-ETHANE.
ETHENYL-DI-PHENYL-AMIDINE v. Di-
fBENXL-ACETAMIDINE.
ETHENYL-PHENYL-AMIDOXIM
CHs.C(NHPh):NOH. Etheivyl-amlidoxim. [121°].
Formed by heating ethenyl-amidoxim with aniline
(Nordmann, B. 17, 2752). Large yellow glisten-
ing plates, Sol. alcohol, ether, benzene, and
hot water, nearly insol. cold water. Fe^Clj
colours it deep-violet to olive-green.
ETHENYL-DI-PHENYL-DIAMINE v. Di-
PHENTL-ACEIAMIDINE.
ETHENYL-PHENYLENE DIAMINE
0,H,N,i.e.C^,<^^>C.OH,. [170°] (H.);
[175°] (L.). Formed by reducing aeetyl-o-nitro-
aniline or its bromo- derivative with zinc and
glacial acetic acid (Hiibner, A. 209, 352 ; B. 8,
471). Formed also by boiling o-phenylene-diamine
with glacial acetic acid (Ladenburg, B. 8, 677),
Needles or leaflets. -^ The hydrochloride,
sulphate and nitrate form colourless needles.
— B"H01, B"HjSO„ B-'ASO, and B"HNOs.—
B"8HiJPt01sa!aq.
Ethenyl-phenylene-diamine carbozylic acid
V. ElHENTL-DI-AUIDO-BENZOIO AOXD.
ETHENYL-PEOPYLENE DIAMINE
CjH8<^j^jT^CMe. From di-acetyl-propylene«
diamine by heating a current of dry HCl (Hof-
mann, B. 21, 2332). — B'jHaPtCle: trimetrio
crystals, extremely sol. water. — ^E'EAuCl^: small
needles.
ETHENYL-TEI-STTLPHONIC ACID v.
Ethane-tki-sdlphonio acid.
ETHENYL-TOLYLENE-0-DIAMINE
C„HaMe<^^C.CH3. [199°]. Formed with
elimination of AcOEt and HjO, by heating
tolylene-o-diamine with aceto-aoetio ether
(Ladenburg a. Eugheimer, B. 12, 951 ; Witt, B.
19, 2977). It gives a nitro- derivative [202°].
ETHBE C,Hi„0 i.e. Et^O. Di-ethyl oxide.
Ethyl ether. Sulphuric ether. [-117°] (Ols-
zewsky, Jlf.5, 128). Mol. w. 74. (34-6°) (Sehiff,
A. 220, 332). S.G. f -7157 (Bruhl) ; ^'7201;
1 -7099 (Perkin, C. J. 45, 474). S. 8-3 at 17-5°.
S.V. 106-4 (Kamsay); 106-24 (S.) ; 106-1 (P.),
O.E. (0°J0°) -00152 (Dobriner, A. 243, 20). M.M.
4-777 at 20° (P.). n^ 1-3572 (B.; cf. Oude-
mans jun. iJ. T. C: 4,
Boo 35-53 (B.).
H.F.p. 70,040 (Th.) ; 53,000 (Berthelot). H.F.v,
67,430 (Th.).
Critical temperature 194° (Eamsay a. Young,
Pr. 40, 381 ; P. M. [5] 24, 196).
Effect of dissolved substances on the vapour
pressure of ether : Eaoult, C. B. 104, 976.
Coefficient of Compressibility -000183 at 21-5°
(Isambert, C. B. 105, 375).
Formation. — 1. From alcohol by treatment
with HjSOj (Valerius Cordius, a.d. 1S40;
Frobenius ; Valentin Eose, Scher. J. 4, 253 ;
Saussure, A. Ch. 89, 273 ; Dumas a. BouUay,
A. Ch. [2] 36, 294). Formed also from alcohol
by treatment vrith phosphoric acid (Boullay,
A. Ch. 62, 192), with arsenic acid (Boullay, 4. Ch.
78, 284), vrith BF, (Desfosses, A. Ch. [2] 16,
72), with ZnClj (Masson, A. 31, 63) or with
SnOli (Kuhlmann, A. 33, 97, 192).— 2. By the
action of ethyl iodide (bromide, or chloride) on
sodium (or potassium) ethylate (Williamson, .
C. J. 4, 106).— 3.FromEtIanddryAg30.— 4. By
heating alcohol with EtBr or EtI at 200°
(Eeynoso, A. Ch. [3] 48, 385).— 5. By heating
EtBr or EtI with water at 150°-200° (E.).—
6. By heating alcohol with HCl, HBr, HI, or
chlorides of Mn, Co, Ni, Cd, Zn, Sn, Fe", Hg",
Ca, 8r, &o. In the case of CaCl, a temperature
of 300° is required (Berth-elot, A. 83, 104).
Hglj and SiF, also etherify (E.).— 7. Alcohol ia
also etherified by heating with the sulphates of
Mg, Zn, Cd, Fe", Co, Al, and with alums
(Eeynoso). — 8. By heating EtI with Na^O at
180° (Greene, 0. B. 86, 1141).— 9. By heating
alcohol vrith Et^SO, (Erlenmeyer, A. 142, 373).
Preparation. — ^A mixture of alcohol of 90 p.o.
(5 pts.) and cone. H^SO^ (9 pts.) is toiled, and
alcohol (30 pts.) is allowed to run in continu-
ously through a tube, dipping under the sur-
face of the liquid at such a rate that the liquid
boils constantly at 140° (BouUay, J. Ph. 1, 97).
The distillate separates into two layers, the
upper consisting of ether containing alcohol and
water in solution, the lower of water containing
alcohol and ether in solution ; but towards the
latter part of the distillation, when the sulphuric
acid has become weaker, more alcohol passes
ETHERIFICATION,
46£
over tmchanged, and the separation of the ether
no Jonger takes place. The other is freed from
Bulphnrons and acetic acids by agitation with
milk of lime, and is finally rectified. The yield
is about 90 p.o. of the theoretical. The amount
of oleflant gas formed during the process may
be very greatly diminished by keeping the mix-
ture at 130° instead of 140° (Soubeiran, J. Ph.
[3] 16, 321). Ether may be freed from traces of
alcohol and water by fused calcium chloride ; or
it may be shaken several times with water, and
finally dried over quicklime.
Properties.— Colourless, .very mobile liquid,
with characteristic odour and burning taste.
Very inflammable, burning with a luminous
fiame; its vapour forms an explosive mixture
with air. When inhaled it produces insensi-
bility. 35 pts. of ether dissolve 1 pt. of water.
It mixes with alcohol, CS^, chloroform, acetone,
and many essential oils; in the latter case
presence of water or alcohol is indicated by
turbidity (Blanchet, A. 7, 157). Wet ether gives
turbidity with CSj. It dissolves iodine and
bromine and small quantities of sulphur and
phosphorus. It also dissolves AuCl,, FejCl^,
HgO^, Hg(N0,)2, fats, resins, and many other
organic bodies. Strong aqueous HCl dissolves
ether with evolution of heat, apparently forming
an unstable compound. By rapidly evaporating
wet ether Tanret (O. B. 86, 765) obtained a cryo-
hydrate C,H„02aq [-3-5°].
BecuiUons. — 1. The vapour of ether passed
through a red-hot tube produces C^H,, water,
GO, and aldehyde. — 2. When a mixture of ether-
vapour and air comes in contact with platinum
black, heated pZatinum-sponge, or other bodies
heated not quite to redness, it undergoes slow
and imperfect combustion, emitting a pale light,
and forming aldehyde, acetic, and formic acids,
CO2, water, &o. Oxidised by a red-hot platinum
spiral it gives formic acid, acetic acid, aldehyde,
acetal, formic aldehyde and trimetric prisms of
CuHsjOj, [51°]. These prisms are soluble in
water, alcohol, ether, or chloroform, and are de-
composed by alkalis into formic aldehyde and
formic acid. The compound liberates I from KI
solution, and reduces PbOj, and appears, therefore,
to be a derivative of HjOj (Legler, A. 217, 381).—
3. Dry ozonised oxygen acts violently, forming
acetic acid, oxalic acid, HjO,, and a little formic
acid (A. W. Wright, Am. S. [3] 7, 184). Accord-
ing to Berthelot {Bl. [2] 36, 72) syrupy EtjO, is
formed in this reaction.— 4. Sulphiaic acid at
120° forms ethyl-sulphuric acid BtHSOi. When
ether is boiled with sulphuric acid the tempera-
ture rises from 130° to 180°; SOj and.EtjSO,
pass over while isethionic acid, ethionic acid,
&o., remain in the retort.— S. The product of
the action of SO, separates into an aqueous and
a brown ethereal layer. The former contains
ethionic acid, whioh^ on boiling, changes to
isethionic acid. The latter consists of di-ethyl
sulphate (84 p.c), ethyl ethionate (12 p.c), and
ethyl mettiionateCHj(S03Et)2(4p.c.)(B.Hubner,
A. 223, 207). The reaction may perhaps be
represented as follows : —
EtjO + SO, = S02(0Et)j ;
S02(OEt)j + 3SO,=
HO.SOj.O.CjH,.SO,.OH + SO,H.CH:CH.SOjH ;
60j(OBt)j + 2SO,
=iHO.SO,.OEt + SO,H.OH:CH.SO,H: ;
Vox,, n.
S0aH.0H:0H.S03H + H^O
= SO,H.0H,.CHjO.SO3H ;
SO3H.CHj.CH2O.SOjH + 2S0,
= CKj(S03H)2 + 2S0j + COj + H2O.
6. Hot nitric acid forms CO,, acetic acid, and
oxalic acid. CrO, also oxidises it to acetic
acid. — 7. HCl gas forms ethyl chloride. — 8. Dry
chlorine forms di-, tetra-, and deca-, chloro-di-
ethyl oxides, aldehyde, chloral, EtCl, &c. In
presence of water acetic acid and other products
of oxidation are formed. — 9. A solution of
bromine in ether becomes colourless after a few
days, EtBr, bromal, and other products being
formed. According to Schiitzenberger (C. B.
75, 1511) n mixture of bromine and ether
deposits in a freezing mixture crystals of
(Et20)2Br8 [0. 22°]. Iodine acts but slightly on
ether.— 10. Sodium does not act on pure ether. —
11. Heated soda-lmte forms NajGO,, hydrogen,
and CH4. — 12. Bed-hot zinc-dust forms Gfi„
water, and hydrogen (Jahn, M. 1, 675).
Combinations. — Et„0SnCl4 : volatile plates,
sol. ether, decomposed by water (Euhlmann, A.
33, 106, 192 ; Lewy, J.pr. 36, 146).— SnBr,EtjO.— ,
EtjOSbClj: [69°] ; crystalline hygroscopic powder,
sol. alcohol and ether, decomposed by water and
by fusion (Williams, B. 9, 1135).— SbBraEtaO.-
SbBr32Et20 ' (Nioklfis, C. B. 52, 396). —
BiBr3Et20 2aq: deliquescentprisms.- — Et^OAsBr,.
— EtjjOTiOl,. [42°-46°]. (119°). Decomposed by
water (Bedson, C. J. 29, 309).— (Et20)3(TiCl4)2
(B.).— (EtjO)j(PCl,)3. White plates, formed by
dissolving FCl, in dry ether. Violently decom-
posed by water, giving ethyl-phosphoric acid, but
no ether (Liebermann a. Landshoff, B. 13, 690). —
BeOl22Et20 (Atterberg, B. 9, 856).— HgBrj3Et20
(NickWs, C. B. 52, 869). — Alfii„2Etfi. -r
TlCl3Etj0H01 aq.— TlBrjliEtjO (NicklAs, G. B.
58, 537).— Vd00l3Et20. [below 20°]. Lustrous
green crystals (Bedson, C. J. 29, 309).
Hydroiodide (EtjO)iBI. An oUformedby
direct combination of ether and HI (Messinger
a. Engels, B. 21, 327). Insol. ether. Decom-
posed by KOH into ether and EI, and by water
into ether, HI, and EtI.
Hydrobromide (EtjO)2HBr. Oil. Simi-
lar to the hydroiodide.
Beferences. — Auino-, Bbomo-, and Chlobo-,
DI-ETHTL oxide.
ETHEBIFICATION. The formation of ethers.
In the most general sense etherification means
the displacement by an alkyl of hydrogen at-
tached to oxygen (or. to a halogen in the case of
HCl, HBr, and HI). In the narrowest sense it
is applied to the making of common ether. The
reactions underlying the continuous manufac-
ture of ether maybe taken as typical of aU cases
of etherification. Alcohol was at one time re-
garded as the hydrate of ether, so that in the
manufacture of ether the sulphuric acid merely
abstracted a molecule of water from each mole-
cule of ether. It was pointed out by Mitsoher-
lich that ether and water distil over in equivalent
proportions (4 pts. of ether to 1 pt. of water), so
that the sulphuric acid must be supposed first
to take the water from the alcohol and then to
give it up again. Mitscherlich and Berzelins
therefore said that the sulphuric acid acted
• catalytically.' Liebig (A. 23, 39 ; 30, 129) then
pointed out that on mixing alcohol and sulphurio
acid hydrogen ethyl Bolpbate is formed, but
469
ETIIERIFICATION.
on distilling the mixture the quantity of
hydrogen ethyl sulphate constantly diminishes
as the ether .passes over, and he concluded
that the hydrogen ethyl sulphate must take part
in the formation of ether. He assumed the first
reaction to consist in the formation of hydrogen
ethyl sulphate from alcohol and sulphuric acid,
and that at 120°-140° that body was split up
into ether, hydrogen sulphate, and SO,, the SO3
then uniting with the water formed in the first
reaction. When, however, hydrogen ethyl sul-
phate is heated alone it gives alcohol and not
ether, although, when heated with alcohol, it
does give ether. Williamson (C J. 4, 106,
229; A. 77, 37; 81, 73; A. Gh. [3] 40, 98),
while adopting the first of Liebig's equations,
showed that the second reaction consisted in
the decomposition of hydrogen ethyl sulphate
by alcohol. At the same time, Williamson
doubled the formula then ascribed to ether for
several reasons :
(1) To bring it in accordance with Avogadro's
Ijaw.
(2) The difference between the boiling-points
of alcohol and of ether (44°) is exactly that
usually found between an acid and its ethyl
salt.
(3) By the same methods used in preparing
ordinary ether it is possible to prepare mixed
ethers, such as methyl ethyl oxide MeOEt, and
the boiling-points of these ethers are intermediate
between those of the two corresponding simple
ethers.
(4) There are other reasons for doubling the
atomic weight of oxygen.
The two equations proposed by Williamson,
and now universally adopted, are
(1) EtOH + HjSO<=EtHSO, + HsO
(2) BtHS04 + EtOH = EtjO + HjSO,.
That ether is alcohol in which an atom of hy-
drogen has been displaced by ethyl would appear
probable from its formation according to the
equations
EtOH + K = BtOK + H
EtOK+BtI = BtOBt + KI (Williamson).
The etherification of an acid by means of alcohol
and H2SO, probably takes place for the most
part according to such equations as
EtOH + H2SO4 = EtHSO< + H2O
EtHSOi -h HOAc = EtOAc + H^SO,.
Etherification by alcohol and HCl being repre-
sented thus :
EtOH + HOI = BtCl + H,0
2Et01 + 0,H.04 = Et AH A + 2HC1.
ETHEBS. Ethers may be simple, mixed, or
compound. Simple ethers are oxides of mono-
valent alkyls; the oxides of divalent radicles,
such as ethylene, are not usually classed as
ethers. A mixed oxide of two monovalent
alkyls, such as MeOBt, is called a mixed ether.
A compound ether (or ester) is a hydrogen salt
in which the typical hydrogen has been dis-
placed by an alkyl, and may therefore be regarded
as an alkyl salt of an acid.
Properties of simple and mixed ethers.
The simple and mixed ethers in general re-
semble ordinary ether in their properties. They
are insol. water, and are not decomposed by
ammonia, alkalis, sodium, dilute acids, P^^^ti °^
cold PClg. Gone. HjSO, and SO, decompose
^em (v. EiHSiB). Ni^rio aqid oxidises tbem to
the acids corresponding to the alkyls. If one
of the alkyls is benzyl, this becomes benzoio
aldehyde (Brrera, O. 17, 193). H^ forms an
alcohol and an alkyl iodide ; if one of the alkyls
is methyl, the iodide is methyl iodide (Silva,
O. B. 81, 328). Aluminium and iodine produce
alkyl iodide, and alnmininm iodoalkylate (Glad-
stone a. Tribe, O. J. 30, 357). Chlorine pro-
duces products of substitution.
Formation of compound ethers. When an
alcohol is heated with an equivalent quantity of
an acid, a reaction such as:
BtOH + HOAo = EtOAc + HjO
occurs ; but as soon as the products of the re-
action are formed they begiii to react in an
inverse sense :
BtOAo + HjO = EtOH -H HOAo.
Thus, these two reactions occurring simultane-
ously an equilibrium is ultimately set up (Ber-
thelot a. P^an de Saint-Oilles, G. B. 53, 474 ; 55,
39, 210, 324 ; 85, 883 ; A. Gh. [3] 68, 225).
When molecular mixtures of glacial acetic acid
and alcohols are heated to 154° the percentage
of acid etherified at the end of the first hour is
called by Menschutkin the initial velocity of
etherification, while the percentage etherified at
the end of 120 hours is called the final limit of
etherification.
The initial velocity is 55*6 for methyl alcohol,
46*7 for ethyl, propyl, and ra-butyl alcohols, 44-9
for isobutyl alcohol, 36-1 for aUyl alcohol, 38-0
for benzyl alcohol, 26'5 for isopropyl alcohol,
22-6 for sec-butyl alcohol, 10-6 for cU-allyl car-
binol, 1-4 for <ert-butyl alcohol, and 1-5 for
phenol. It will be seen that the initial velocity
is greatest for primary and least for tertiary
alcohols, while unsaturated alcohols etherify
more slowly than saturated alcohols.
The final limit is 69-6 for methyl alcohol,
about 66-8 for ethyl, propyl, butyl, and isobutyl
alcohols, about 60 for allyl, benzyl, and sec-
butyl alcohols, 10 for di-allyl carbinol, and 8-6
for phenol. The limit, therefore follows in the
main the same variation as the initial velocity,
although in the case of primary and secondary
alcohols the changes are less marked.
When the rate of etherification of various
acids by the same alcohol (isobutyl alcohol was
used) is examined it is found that the limit is
fairly constant at 67 to 74, while the initial
velocity varies from 44-4 for acetic acid to 3-5
for di-methyl-ethyl-aoetio acid. Here also the
normal compounds show greatest rapidity of
etherification. Formic acid shows a greater
initial velocity (61-7) and a lower limit (64) than
any other organic acid (Menschutkin, Bl. [2] 34,
87). In the etherification of alcohols by Acp
the greatest velocity is shown by methyl alcohol,
but in most cases the reaction is ultimately com-
plete (Menschutkin, C. B. 105,1016; v. vol. i.
p. 737).
Preparation of compound ethers. — 1. Vola-
tile ethers are prepared by distilling a mixture
of the alcohol, the acid (or a salt of the acid),
and H2SO4. — 2. Kon-volatile ethers are prepared
by passing HOI into a solution of the acid in
alcohol. — 3. The ethers may be prepared by
treating the silver salt of the acid with ethyl
iodide, and this reaction may be resorted to when
neither of the preceding is available. — 4. By dis-
tilling the potassium salt of an aoid with potas-
ETHYL-ALLYL-AMINE.
467
gium alkyl sulphate.— 5. By treating the alcohol
with the chloride or anhydride of the aeid.^6. By
the action of HOI or HjS04 on a solution of the
nitrile in an alcohol (Beckurts a. Otto, O. G.
1877, 5).— 7. According to Yeiel (A. 148, 160)
compound ethers are formed by the oxidation
of fatty acids byMnOj and dilute sulphuric acid.'
Thus, butyric acid is said to give propyl baty-
rate.
froperties of compound ethers.— The com-
pound ethers are almost all insol. water, but are
partially saponified by heating therewith ; they
are saponified by heating with alkalis or alkaline
earths, and by HCl or dilute HjSO,. Ammonia
splits up compound ethers derived from organic
acids into the amide and an alcohol. When a
compound ether is heated with an alcohol an in-
terchange of alkyls may take place ; thus, ethyl
acetate and amyl alcohol yield amyl acetate,
ethyl amyl oxide, and water (Friedel a. Crafts,
A. 130, 198 ; 131, 55). Compound ethers are
split up by heating with dry HBr at 100°, form-
ing alkyl .bromide and free acid (Gal, C. B. 59,
1049). Aluminium and iodine react upon com-
pound ethers of the fatty series, forming an alkyl
iodide and aluminium salt (Gladstone a. Ti;ibe,
C. J. 30, 357). Compound ethers unite with
titanium chloride, forming such compounds as
EtOAc(TiCy„ EtOAcTiCl,, and (EtOAc)jTiOl4
(Demar<;ay, Bl. [2] 20, 127 ; C. B. 76, 1414).
Acid ethers. When in polyhydrio acids a
part only of the typical hydrogen has been dis-
placed by alkyls the resulting acid ether is
usually very soluble in water, and readily saponi-
fied by boiling therewith.
References. — The particular characters of
each group of compound ethers may be gathered
by reference to the articles on the ethyl salts of
the acids, e.g. Ethtii bbomlds, Eihsii ohlobide,
EthyIi pekchloeatb, Bthtii iodide, Bthyii ni-
trate, Bthhii nitbitb, Di-ethyii selenide, Et&t:ii
silicate, EthIIi SUI.PHATE, Dl-ETHYIi BUIiPHIDE,
BtHTL SDMHITE, BtHYL THIOSUIiPHATE, &0.
£IHIIT£ or ETHIITENE i>. Acettlene.
ETHINE-DI-PHTHALYL v. Di-phthaltl-
ETEANE.
ETHIONIC ACID CjHjSA ».e.
so3H.cHj.ch;,.o. so,h.
FormaUon. — 1. By saturating anhydrous al-
cohol or ether with SO, and diluting with water
(Magnus, P. 27, 378 ; 47, 514 ; Marchand, P.
32, 466). — 2. Its mono-chloride is formed along
with ClBO^OEt by action of CISO^OH upon
ethylene: (a) Cl.S020H + CjH4=Cl.S0200X;
and then follows (b) Cl.SO^.OH+ClSOjOEt
= HCl + CjH4(SOj.OH)(O.S02Cl) (Olaesson, J.pr.
[2] 19, 255).— 3. From Et^SO^ and SOj (Hiibner,
A. 223, 208)^-4. By the action of HjSO^ on
isethionio acid S0sH.CHj.CHj0H in the cold
(Erlenmeyer a. Carl, N. Sep. Pha/rm. 23, 428).
Proparties.— Only known in solution, for on
evaporation it splits up into HjSO, and isethio-
nic acid.
Salts.— KjA"^ aq : orystaUine.— NajA"aq.
— BaA"aq. S. 10 at 20°.
CHj.0.S0,
Anhydride I \ . [80°]. Carlyl
ca,.sOj.o
sulphate. Obtained by durect union of ethylene
with SOj ; formed also by exposing alcohol to
the Tapoar of SQ, (Eegnault, 4. (!h. 65, 98;
Magnus, P. 47, 509). Deliquescent crystals;
dissolves in water forming ethionio acid.
Isethiouic acid v. Isethionio acid.
DIETHOXAIiIC ACID v. Oxt-hbxoio acid.
ETHOXY- COMPOUNDS v. the ethyl ethers
of OXT- COMPOUNDS.
ETHOXY-OXAIYL CHIOEIDE v. Chloeo-
OIiTOXILlO BTHEB.
ETHYL. The radicle OjH, or CH,.CHj. The
ethyl derivatives of hydroxylic compounds are
described under the compounds from which
they are derived,
Di-ethyl v. Butane.
DI-ETHYL-ACETAL v. Aoetal.
DI-ETHYL-ACETAMIDINE C.H„N, i.e.
CH3.C(KHBt):NBt. (o. 167°). Prom ethyl-
aoetamide and PCI, the resulting oily base
CgHisClNj being subsequently warmed with BoUd
KOH (Wallach a. Hoffmann, B. 8, 313 ; A. 184,
108). Syrup, miscible with water, alcohol and
ether. Strongly alkaline. Precipitates most
metallic salts and dissolves recently ppd. alu-
mina. Boiling alkalis split it up into acetic
acid and ethylamine.
ETHYI-ACETAMIDE v. Acetyl-EinYL-
AMINE.
ETHYI-ACETANILIDE v. Acetyl-EiBYi^'
ANILINE^
ETHYL ACETATE v. vol. i. p. 14.
DI-ETHYI-ACETIC ACID v. Hexoio acid.
Ethyl-diacetic acid v. ethyl aceio-aoetatb,
vol. i. p. 17.
ETHYl-ACETO-ACETIC ACID v. vol. i.
p. 23.
ETHYL-LIACETONAMINE v. vol. i. p. 28.
ETHYL-ACETO-NITRAWILIDE v. Acetyl-
NiIBO-BTHTL-ANHjINE.
DI-ETHYI-ACETOPHENONE v. Phenyl
AHYL KETONE.
ETHYL-ACETO-PEOPIONIC ACID v. j8-
AOETYIi-M-isO-VALEKIC ACID.
ETHYL - ACETO - SUCCINIC ETHEE v.
ACETYIi-ETHYL-BUCCINIO EIHEB.
ETHYL-DI-ACETYL-ACETIC ETHEB v.
vol. i. p. 23.
ETHYL-ACETYL-ACETONE v. Di-mbthyl
PEOPYLBNB DIKETONE.
DI-ETHYL-ACETYL-ACETONE v. Di.mbihyi,
AMYLENB DIEETONB.
ETHYL-ACETYLENE v. Botinekb.
ETHYL-ACETYLENE-TETEA-CAEBOXYLIC
ACID V. Butane ietba-cabboxylio etheb.
ETHYL-^SSCULETIC ACID v. Eif^l deri-
vative of ^SCULETIO ACID.
ETHYL ALCOHOL v. AloohoIu Derivatives
are described as Bbouo-ethyl alcohol, Chlobo-
ETHYL alcohol, &C.
Tfil-ETHYL-ALCAAIINE v. Oxy-tbi-ethyl-
AMINB.
ETHYL ALDEHYDE v. Aldehyde.
ETHYL-ALLYL v. Amtlbnb.
TETEA-ETHYL-ALLYL-ALCINE v. Tbtba-
ETHYL-OXY-PBOPYLBNE-DIAIVIINE.
ETHYL-ALLYL-AMINE (OjH,)(C,H5)NH.
(85°). Colourless ommoniacaJ liquid. Miscible
with water. Prepared by the action of ethyl
iodide on allylamine.
Salts. — B'HCl: small deliquescent plates.
— B'jHjCljPtOl, : orange needles [o. 165°]i—
B'HClPtCl,: yellow needles [220°], fonned by
boiling f^e preceding salt - with water.
168
ETHYL-ALLYL-AMINE.
— ^B'jHjSO, : tables v. e. sol. water, insol. alcohol
and ether. The acid oxalate forms sparmgly
soluble colourless plates (Binne, A. 168, 261 ;
Liebermann a. Paal, B. 16, 525).
Di-ethyl-allyl-amine (CjH5)2{CjHJN. (111°).
S. 5 at 18°. Colourless liquid. Its aqueous
Eolntion becomes turbid on warming. Prepared
by the action of ethyl iodide on allyl-amine
(Einne, 4. 168, 265).
Salts. — B'jHjCljPtCl, : large orange crystals
[129°].— B'HClPtClj: yellow needles [189°],
formed by boiling the preceding salt with water
(Liebermann a. Paal, B. 16, 526).— B'HOl : very
soluble crystals.
Ethylo-bromide (Cjgj)j(C3H5)NBr. Tri-
ethyl-alVyl-cmimonium bromide. From tri-
ethylamine and allyl bromide (Eeboul, C. B. 92,
1464). Deliquescent crystals. Split up on dis-
tillation into allyl bromide, ethyl bromide, tri-
ethylamine, diethylamine, ethylene, s-tri-bromo-
ethane, and, probably, aUylamine. From it may
be prepared (C2H5)3(C3H5)NC1 and the platino-
ohloride {(0jHj3(0jH5)NClj}PtCl„ both crystal-
line.
ETHYL -AILYL- ANILINE 0„H,5N i.e.
NPhEt(C3H5). (o. 223°). From aUyl-aniline
and EtI (Schiff, A. Suppl. 3, 364). Thick oil.—
WC^'BjOf : spherical groups of small needles (from
water).
ETHTL-DI-ALLTL-CABBINOL v. ENNnm.
UiCOHOIi.
Di-ethyl-allyl-carbinol v. Ocienyl aiiCohol.
ETHTL-ALLYL-CYANAMIDE C,H,„Nj i.e.
CN.NEt(C3H3). [100°]. From ethyl-allyl-thio-
nrea, Pb(OH)j, and KOH (Hinterberger, A. 83,
348). Needles (from ether). Insol. water, sol.
alcohol and ether. Tastes bitter. — ^B'2(HgCl2)3. —
B'^HjPtCle.
ETHYL ALLYL OXIDE CsH.oO i.e.
C2H5.O.O3H5. Ethyl-allyl ether. Mol. w. 86.
(67°). 8.0.^-7651.^^ 1-3939. Ea, =42-2. Criti-
cal temperature 245° (Pawlewsky, B. 16, 2634).
From allyl bromide and NaOEt, allylene being
also formed (Bruhl, A. 200, 178 ; cf. Berthelot a.
De Luca, A. Ch. [3] 48, 292; Cahours a. Hof-
mann, A. 102, 290). Formed also by treating
ethyl di-bromo-allyl oxide CjHs.O.CHBr.CHjBr
with sodium amalgam (Markownikoff, Z. 1865,
654). Combines with chlorine and bromine, but
is not reduced by sodium amalgam. ClOH forms
a compound C3H5Cl(OH)(OEt) (184°).
EXaYL-ALLYL-THIO-TTEEA CjH.jN^S i.e.
NHEtCS-NHCsHj. From allyl thiocarbimide
and ethylamine (Hinterberger, A. 83, 346 ;
, Weltzien, A. 94, 103). Syrup.— B'HJ'tCl,
B'HI.
Di - ethyl- allyl -thio- urea OgHuNjS i.e.
NEtj-CS-NHCaHj. [65°]. Ijong prisms or nee-
dles. V. sol. alcohol and benzene, si. sol. ligroin,
insol. water. ■ Formed by combination of aUyl
thiocarbimide and di-ethyl-amine (Gebhardt, B.
17, 3038).
ETHYL - ALLYL - UEEA C^H.^N^O i.e..
NHEt-CO-NHCaHj. From ethylamine and allyl
cyanate. Prisms (Cahours a. Hofmann, A. 102,
300).
ETETL-AIIABINE v. Bekzoio aldeetde,
AMMONrA DEBIVATIVES OP.
ETHYL-AMIDO-ACETIC ACID 04HsN02 i.e.
NHEt.CH4.COjH. Ethyl - glycocoU. Ethyl
flyeocine. (above 160°]. Prepared by prolonged
boiling of chloro-acetic acid mth ethylamine
(Heintz, A. 129, 27 ; 132, 1). Indistinct deU-
quescent lamince (from alcohol). Sweetish, al-
most metallic taste. On mixing with an aqueous
solution of cyanamide there are deposited long
needles of ' ethyl - amido - aceto - cyamidine '
HN:0^jj-c,I gn ^ a homologue of creatinin ;
S. 9 at 26° ; S. (alcohol) 1 at 25° (Duvillier, C. B.
103, 211).
S alt s.— HA'HCl : [c. 180°] ; trimetric prisms,
V. sol. water and hot alcohol. — H^A'jHjPtCl,, 6aq ;
large orange -red monoclinic prisms. —
HA'(HgCLj)j: small prisms (from water). —
HoA'^HgClj : syrup. — CuA'2 4aq : prisms, v. sol.
water and alcohol, insol. ether. — Derivative: Di-
OHIiOHO-ETHYli-AMIDO-AOETIC ETHEE (q.V.j.
Di-ethyl-amido-acetic acid C^HuNOj i.e.
NEtj.CH2.OOjH. Obtained by boiling diethyl-
amine with chloro-acetic acid (Heintz, A. 140,
217 ; Z. [2] 5, 162). Deliquescent rhombohedral
crystals ; v. sol. alcohol ; sublimes below 100°. —
CuA'j 4aq : small blue prisms.— HjA'jHjPtClj aq :
orange-red crystals.
Ethyl ether NEt3.CH3.C0jEt. (174° un-
cor.). S.G. i^ -919. From silver-glyoocoU and
EtI (Kraut, A. 182, 172 ; 210, 317). AlkaUne
liquid. — B'jHjPtCls: short monoclinic crystals.
— B'jHaBijI, : slender red needles.
EthyloOiydroxide. Anhydride.
CsH^NOj i.e. NEt,<^*^^>CO. ' Trietlvyl gl/y.
cocolV (210°). Prepared by heating NEtj with
chloro-acetic ether, boiling the product with
baryta water, and heating the resulting ethylo-
chloride with silver oxide (Eraut, A. 182, 172).
Formed also from NEt, and chloro-acetic acid
(Hofmann, Pr. 11, 525 ; Briihl, B. 8, 479 ; A.
177, 201). Deliquescent crystalline mass; partly
decomposed by distillation giving off NEtj.
Ethylo-chloride NEt3Cl.CH3.COjH. From
NEtg and chloro-acetic acid. Not decomposed
by boiling potash or baryta water.
Salts.— (NEt3Cl.CHj.C0jH)jPtCl, 2aq:mono-
olinic prisms.— (NEt3Cl.CHj.C0jH)AuCl,.
Ethylo-iodide NEtjI.CHj.COjH : orange
hair-like crystals. — (NEt3l.CHj.C0jH),BijI,:
orange tables.
Ethylo-nitrate NEt3(N03).CHj.C0jH :
needles, v. e. sol. water.
Ethyl ether of the ethylo-chloride
NEt,Cl.CHj.COjEt. From triethylamine and
chloro-acetic ether. Needles, v. e. sol. water and
alcohol. (NEtsCl.CHj.C0jEt)jPtCl4 : orange
crystals. — (NEt3Cl.CH,.C0jEt)AuCl, : [100°] ;
needles.
Ethyl ether of the ethylo-iodide
NEt,I.CHj.COjEt. From silver glyoocoll (3 mols.)
and EtI (4 mols.) in the cold.
ETHYL-o-AKIDD-ACETOFHENONE
C„H,(NHBt).C0.CH3. Oil. Obtained by heating
o-amido-acetophenone with ethyl bromide
B'jHjCljPtCl,: golden-yellow plates (Baeyer, B.
17, 970).
ETHYL-AUIDO-AZO- COUFOUNDS v. Azo-
COMPOUNDS.
ETHYL -AIIIDO- BENZENE «. Etb^
ANILINE.
ETHYL - AKIDO - BENZENE SDLFHONIC
AGIO NHEt.O^.SO,H, Froiu ethyl anilin»
ETHYL-AMIDO-ETHANE SULPHONlC ACID.
4fl9
and HjSO, at 200° (Smyth, B. 7, 1241).—
BaA'2 2aq.
Di-ethyl-amido-'benzeiie sulphonio acid
NEtj.CjH4.SO3H. Prom di-ethyl-amline and
HsSO4(S0.-BaA'2 2aq.
ETHYL-o-AMIDO-BENZOIC ACID. Amide
[2:l]0,H,(NHBt).CONH2. [129°]. From 0-
amido-benzamide and £tl in alcohol at 100°
(Finger, J. pr. [2] 37, 441). Crystalline mass,
Bol. hot water. Gives rise to a nitrosamin6
C^,(N(N0)Et).C0NH2 [110°].
Ethyl-m-amido-benzoic acid CjHuNOj i.e.
[3:l]C,H,(NHEt).C02H. [112°]. When potas-
sium m-amido-benzoate is boiled with alcoholic
EtI a mixture of ethyl- and di-ethyl-amido-
benzoio acids is produced ; these may be sepa-
rated by crystallisation of their hydrochloride
from hot dilute HCl (Griess, B. 6, 1038). Small
prisms, si. sol. hot water, v. e. sol. alcohol and
ether. Its solution is tasteless, but acid in re-
action. It forms salts with mineral acids but
not with EOAc. It gives a nitrosamine
CjHiN(N0)Et).C02H which crystallises (from
water) in yellowish-white long narrow plates,
and forms a crystalline silver salt CgHgAgN^O,.
Salts. — HA'HCl: small four- or six-sided
plates; also (from dilute HCl) in needles; m.
sol. cold, y. sol. hot, water; T. si. sol. cold
HClAq. — BaA'2 2aq : indistinct plates (from
alcohol).
Si-ethyl-m-amido-benzoic acid C„H,,K02 i.e.
[3:l]CsH,(NEt2).COjH. [90°]. Formed as above
(G.). White prisms (containing 2aq) ; may be
distilled. — HA'HCl aq : shining four-sided plates,
T. sol. cold water and HClAq.
I>i-ethyl.2)-amido-1ienzoic acid
[4:l]CjHi(NEtj).C0jH. [188°]. From ^j-amido-
benzoic acid, EOH, and alcoholic EtI. Also by
saponifying its chloride which is obtained by
treating di-ethyl-aniline with COCl^ (Miohler a.
Gradmann, B. 9, 1912). Small plates (from
alcohol).— H5A',H2PtCl».—AgA'.
Ethyl ether EtA'. (315°). Formed, to-
gether with the acid, by treating potassium p-
amido-benzoate with EtI in the cold (Michael a.
Wing, jlm. 7, 198). Oil.
Si-ethyl-di-amido-benzoic acid CnHi^KjO,
».e. 0,H.(NEtj)(NHj,).C02H. From di-ethyl-m-
amido-benzoic {icid by nitration and reduction.
Also from benzene-azo-di-ethyl-amido-benzoio
acid by reduction (Griess, B. 10, 527). Grey
needles or prisms (from alcohol).
2>-DI-ETHYI-AMID0-BEirZ0IC ALDEHYDE
C,H,(NEtj)CH0[l:4]. [41°]. Needles. Sol.
water, alcohol, ether, &o. Formed by the action
of alkalis upon di-ethyl-amido-phenyl-tri-chloro-
ethyl-alcohol CCl,.CH(OH).CjHi.NBtj, the con-
densation product of chloral and diethylaniline
(Boessneck, B. 19, 369).
DI - ETHYL - AMIDO - BENZOPHENOKE
CeHsCO.CjH^NEtj. [78°]. Benzoyl-phmyl-di-
ethyl-ainme. From tetra-ethyl-di-amido-tri-
phenyl-carbinol and cone. HCl at 180° (Doebner,
A. 217, 265). Trimetrio crystals (from alcohol).
Insol. water, si. sol. cold alcohol, v. sol. hot alco-
hol. Very feebly basic, dissolving in cone. HCl,
but leppd. by water.
Tetra-ethyl-di-amido-benzophenone
CO(C,H,NEtj)j. [96°]. Formed, together with
C,H,(NEg(C0.C,H,NEtj)2 [170°], by saturating
di-ethyl-aniline with COCl^, adding half the
original volume of di-ethyl-aniline and heating
at 120° (Michlera. Gradmann, B.9, 1912), Small
laminffi (from alcohol). — B''HJ'tCle.
EIHYL-a-AMIDO-it-BTJIYBIC ACID
CjHijNO^ i.e. CH3.CH2.CH(NHEt).COaH. Prom
o-bromo-butyrio acid and ethylamine (Duvillier,
A. Gh. [6] 20, 196 ; G. B. 88, 425 ; 97, 1486).
Crystalline leaflets, subliming above 110° without
fusion ; v. sol. water, si. sol. cold alcohol. Mixed
with cyanamide in aqueous solution, with addi-
tion of a f eW' drops of ammonia, there is formed
in a month crystals of di-oyan-di-amide, while
from the mother-liquor ethyl-a-amido-butyro-
,NEt.C:NH
oyamide CH3.CH2.Cffi
/
I may be ob-
\C0 .NH
tained in tabular crystals, v. sol. water and
alcohol. — HA'HCl: opaque, ill-defined, deliques-
cent crystals. — HjA'^H^PtClj : orange-red crys-
tals, V. sol. water and alcohol, si. sol. ether. —
CuA'22aq : blue leaflets.
Di-ethyl-a-amido-butyric acid C,H„NO. i.e.
CH3.CHj.CH(NEt2).CO^. [135°]. Froii o-
bromo-butyric acid (1 mol.) and NEt2H (1 mol.)
(Duvillier, C. B. 100, 860). Deliquescent crys-
talline solid, V. sol. water and alcohol, si. sol.
ether. May be distilled with partial decomposi-
tion. Thecupric salt forms violet-red crystals
and dissolves in water and alcohol, forming a
violet solution.
ETHYL- AMIDO-CHLOEO- v. CmoEO-ETHTrii-
AUID0-.
ETHYL-o-AMIDO-CINNAMIG ACID
C„H,3N05,i.e. C„H,(NEtH).CH:CH.CO»H. [125°].
From o-amldo-cinnamic acid, KOH, EtI, and
alcohol by boiling (Fischer a. Kuzel, A. 221,
267 ; B. 16, 653 ; cf. Friedlander a. Weinberg,
B. 15, 1423). Groups of smaU crystals (from
light petroleum). SI. sol. water, sol. alcohol,
ether, and CSj, forming a yellow solution with
green fluorescence.
Nitrosamine CeH4(NEtNO).CH:CH.C02H,
[150°]. Formed by the action of H^SOj and
KNOj on the above. Yellowish plates from dilute
(25 p.o.) alcohol. Insol. light petroleum, v. sol.
ether and chloroform. Insol. acids in the
cold. Beduced by zinc and acetic acid to
NH2.NEt.CeH4.CH:CH.COjH, which is oxidised
by the air to ethyl-quinazole carboxylic acid
(Fischer a. Tafel, A. 227, 332).
Dl-ethyl-o-amido-cinnamic acid CijHjjNO,
«.e. CsH4(NEt2).CH:CH.C02H. [124°]. From
amido-cinnamio acid, EOH, alcohol, and Eti
(Fischer a. Xuzel, A. 221, 269). Pale lemon-
coloured plates (from alcohol). Its solutions in
alcohol, ether, or CSj exhibit bluish-green fluor-
escence.
ETHYL-AMIDO-CUMINIC ACID C.^Hi-NOj
i.e. C,„H„(NHEt)0j. From amido-cuminic acid
and EtI at 105° (Lippmann a. Lange, B. 13,
1662).— AgA'.
ETHYL - AMIDO - ETHANE SULPHONlC
ACID NHEt.CH2CH2.SO3H. Ethyl -tav/rine.
[147°]. From ethylamine and j^-chloro-ethane
Bulphonic acid at 160° (James, J.pr. [2] 31,414).
Prisms (from water).
Di-ethyl-amido-ethane sulphonio acid
NEt2.CH2CH2.SO3H. [151°]. From diethylamina
and CICH2OH2SO3H (J.). Trimetrio tables (from
alcohoi). V. e. sol. water.
470
ETHYL-AMIDO-ETHYL ALCOHOL.
£IHTL-AHISO-£IEYL AICOHOL v. Oxi-
tKi-EiHYii-Aumi:.
EIHYE-a-AMIDO-HEXOIC ACID C,H„NO,
U. CH3(CHj)30H(NHEt).C02H. S. 10-7 at IS".
Prom o-bromo-hesoio acid and ethylamine (Du-
nllier, C. R. 90, 822 ; A. Ch. [5] 29, 172). Pearly
platds (from alcohol). SI. sol. cold, m. sol. hot,
alcohol, insol. ether. Its aqueous solution has a
neutral reaction and bitter taste ; it gives with
Fe^Clg an intense red colouration, and on boiling
a reddish-brown pp. Cyanamide forms the
/NEt.C:NH
creatinin CH3.(0Hj)j.0H< | , which
\00 .NH
crystallises in long needles, m. sol. hot water, T.
Bol. alcohol (Duvillier, C. R. 96, 1583).
Salts. — The hydrochloride forms deli-
quescent laminEB, y. sol. alcohol, insol. ether ;
the aurochloride is a golden crystalline mass.
(HA'H01)2PtCl, : orange prisms.— CuA'^. S. 1
in the cold.
EIHYL.AMISO-HYSBOCASBOSXYBIL v.
OxY-ETHYL-AIUDO-QUINOIjINB DIHyDBIDE.
ETHYL-o-AMISO-HYSBOCINNAHIC ACID
V. Ethxl-o-amido-phenyii-peopionio Aoro.
lEIBA-ETHYL-DI-AMIBO-METEANE v.
Tetba-eihtl-methylene-diamine.
DI ■ ETHYL - (a) ■ AMIDO ■ NAFHIHALENE
STJIPHONIC ACID NBt^.O.A.SOaH. Prom di-
ethyl-naphthylamine and H^SO, (Smith, O. J.
41, 184). Needles.-BaA'j.
Dl-ETHYL-AMIDO-HAFHTHOIC ACID
NBt2.C,„H|i.C0jH. Di-ethyl-(o)-naphthylamine
dissolved in benzene is converted By COClj into
a mixture of two isomeric chlorides of the formula
NEt2.C,„H„.C0Cl [70°] and-[225°] with the com-
pound NEtrO,„H5(CO.C,„Hj.NEt2)j [130°] (Smith,
C. J. 41, 185).
EIHYL-AaUDO-NAFHTHOQUIKOlSirE
C,„Hji02(NHEt). [140°]. From naphthoquinone
and ethylamine (Plimpton, C. J. 37, 639). Bed
needles ; may be sublimed ; v. sol. hot alcohol
and benzene, v. si. sol. ligroin.
TETBA-ETHYL-DI-AMIDO-DI-NAPHTHYE
C,,Ha,N, i.e. NEt,.C,.H„.0,„H,.NEt,. [190°].
(Much above 360°). Formed by heating di-ethyl-
naphthylamine (20 g.) with HjSOj (20 g.) for eight
hours at ig0°-210°. Crystallises in colourless
tufts (from alcohol). Sol. HCl (giving a red solu-
tion), strong HNOa (intense red colour). V. sol.
hot alcohol, m. sol. cold alcohol, si. sol. ether,
T. sol. benzene and CHCl,.
S alt .— B"2(HC1) (B. B. Smith, C. J. 41, 182).
o-ETHYL-AMIDO-PHENDL
C^,(NHEt)0H[l:2]. [168°]. Obtained by heat-
ing its ether with fuming HOI for five hours at
160° (Borster, /. pr. [2] 21, 350). The product
is mixed with NaOH, extracted with ether, the
extract dried over OaOl^, and the ether is then
boiled off. Trimetrio plates. V. sol. alcohol,
less sol. benzene, OS,, chloroform and ether.
Cannot be distilled undecomposed.
Salts. — Unstable, decomposing partially
when their solutions are evaporated, a resin
being formed.— B'HCl.-(B'HCl),PtCl,.—B'HBr.
Nitrosamine 0,Hj(OH)NEt(NO). [121°].
Formed by passing nitrous acid gas into a solu-
tion of the hydrochloride at 0°. Grey plates.
Neither acid nor basic.
Ethyl ether C„H,(NHBt)0Et[l:2]. (235°).
B.G. 1^ 1021. Prepared by heating 100 grms.
of o-amido-phenetol with 84 grmg. ol EtSr for
five hours at 60°. The product is mixed with
soda and extracted with ether. The base is
dried over CaClj and distilled (Forster, J. pr. [2J
21, 346). Oil. Gradually turns brown. Mis-
cible with ether, CS^, chloroform, benzene, and
methyl alcohol. Sol. ethyl alcohol. With
bleaching powder its solution gives a brown
colour. HoSO^and KjCr^O^give a brown colour.
HjSO^ dissolves it, forming a reddish-violet solu-
tion, the colour being destroyed by water. Ni-
trous acid gas forms a nitro-nitrosamina
CeH3(N02) (OBt)NEt(NO).
Salts.— B'HBr: trimetrio plates.— B'EI :
trimetric plates. — ^B'HOl: trimetrio plates. —
(B'HCl)2PtCl,. V. sol. water. Thrown down by
fuming HCl.— B'HAOi. Prisms.
Di-ethyl-o-amido-phenol
C„H4(NEt2)(OH)[l:2]. (220°). Obtained from
its ethyl ether by cone. HCl (Forster, J.pr. [2]
21, 367).
Properties. — Oil. Turns green, in air, but
when heated to its boiling-point suddenly loses
this colour. When moist it decomposes on dis-
tillation. It has a peppery taste, is volatile with
steam, and is sol. ether, benzene, chloroform,
and alcohol.
Reactions. — 1. With FcjClj a deep brownish-
red colour. — 2. HjSO, a,iii_'Kfiifi, a similar
colour. — 3. Solution of bleacMmg powder gives a
wine-red colour. — 4. Bromine water gives a
yellow pp., changing quickly to a brown resin. —
8. Cone. HjSO, dissolves it, forming a violet
solution.
Salts. — Crystallise very well. The base
cannot expel NH, from its salts. Solutions of
its salts decompose somewhat on evaporating.
B'HBr.— B'HCl.—(B'HCl)jPtOl4.
Ethyl ether C,H^(NEtj)OEt [1:2]. (228°)
The ethyl ether of o-amido-phenol (2 pts.) and
EtI (3 pts.) are heated together in alcoholic solu-
tion for twelve hours at 130° ; after evaporation
the residue is mixed with solution of soda,
shaken with ether, and the extract dried over
CaCl, and distilled (Forster). Oil. Miscible with
alcohol, ether, benzene, CHGI3 and OS,. Bleach-
ing-powder solutions give a red colour. HoSO, '
and K^Crfi, a reddish-brown colour. Cone.
H2SO4 forms a violet solution.
Salts . — Glue-like masses. B'HBr.
DI-ETHYL-AMIDO-DIPHENYL C„H„N i.e.
C^Hj-CsH^NEtj. [below 100°]. From ^-amido-
diphenyl and EtI, followed by AgjO (Hofmann,
Pr. 12, 389). Long white needles ; insol. water,
m. sol. alcohol, v. sol. ether ; may be distilled. —
B'jHjPtCl..— B'HBr.— B'HI.
Methylo-iodide CsHj.CjHjNBtjMel.
Forms crystalline (0eH3.0,H,NEt2MeCl)j,PtCl,.
Tetra-ethyl-di-amido-£phenyl
NEt2.CsHi.C3H,.NEt2. Tetra-ethyl-bemidine.
[85°]. . Formed by heating di-ethyl-aniliue with
HjSOj to about 200°, and by ethylation of benz-
idine (Michler a. Pattinson, B. 14, 2166). White
needles. Sol. alcohol and ether, insol. water.
Gives a green colouration with Fe^Olj or CrOj.
TETKA - ETHYL- DI- AMIDO - TSI - PHENYL
CAEBINOL C2,H„NjO t.e.
CjH3C(OH)(C,HiNEt2)2. Base of 'Brilliant
green.' From di-ethyl-anUiue, beuzotrichloride
and ZnClj (Doebner, A. 217, 261). Also from
di-ethyl-aniline and benzoic aUehyde and oxido-
ETHYL-AMlDO-PROPlONIO AOID.
471
tlun of the product (Fischer, B. 14, 2521). Bed-
dish amorphous solid ; si. sol. water, y. sol. alco-
hol. Its solution in ^cohol and in dilute acids
is green ; in concentrated acids it forms a yel-
lowish-brown solution. Heated with cone. EGl
at 180° it forms di-ethyl-amline and di-ethyl-
amido-benzo-phenone : OoHsCfOHXaH-NEt-).
= C.H5.CO.OeH,NEt2 + O^H^NEtj.
Salts. — Dye a yellower shade than mala-
chite green. — Oj^Hs^gH^SO^. Golden crystals.
Its solution in alcohol or water is emerald green.
— (0„H,jNjHCl)j,ZnCl2 2aq. — ^B'Kfifi^ aq :
golden prisms.
Leuco-base C|^:sCH(C„H,NEtj)2. [62°].
XIHTL- AMISO- FH£N YL- CHLOBO- JSTH7L
ALCOHOIi V. CBIiOBO-ETHTIi-AUIDO-FHENYL-ETHTIi
iLOOHOL.
ETHYL-o-AMIDO-PHEMTL-ETHANE
CioHisN i.e. C2Hs.CsH4.NHBt. From amido-
fuenyl-ethane and EtBr (Bernthsen, A. 181,
304). Laminae.— B'HBr : tables.— B'jHjPtClj.
' Seca-ethyl-pent- amide- penta- phenyl-ethane
(Bt»N.0jH4),C.CH(C5H4.NEt,)j. [158°]. Obtained
by heating 20 pts. of chloral hydrate, 50 pts. of
diethylaniline and 10 pts. of ZnCl, at 100° for
five hours. On oxidation it gave a bluish-green
dye-stufi (Boessneck, B. 19, 367).
TETSA- ETHYL - DI - AMIDO - TBI - PHENYL
METHANE CsH50H(0eH,NEt2)2. [62°]. From
the carbinol, zinc-dust, and HCl (Doebner, A.
217, 263). From di-ethyl-aniline, benzoic alde-
hyde and ZnCLj. Colourless glassy needles.
Y. si. sol. water, t. sol. ether, alcohol, or benzene.
B"HjCyPt01, 3aq.
letra - ethyl - tri -ppp - amide - tri - phenyl-
methane (CsH4.NBy.HC:{C„H^.NEtj)2. Tetra-
ethyl-para-TmcamUne. [118°]. Fine concentric
needles. Formed by reduction of tetra-ethyl-p-
di-amido-y-nitro-tri-phenyl-methane with zinc-
dust and dilute HGl. On oxidation it gives a
violet colouring-matter. The acetyl derivative
on oxidation yields a green dye-stufE, which dis-
solves in benzene with a strong fluorescence
(Eaeswurm, B. 19, 747).
Tetra-ethyl-tri -ppo - amido - tri-phenyl-mteth-
aue 0aHi(NHj).CH(08H4NEt2)2. o-Amido-lemo-
brilUant-green. [136°]. White needles (contain-
ing CaHu). Formed by reduction of the conden-
sation product of diethylaniline and o-nitro-
benzoic aldehyde, by means of zinc-dust and
HCl (Fischer a. Schmidt, B. 17, 1894).
Hexa- ethyl- tri - amido - tri - phenyl - methane
CH(C.H,NEt,)3. Triolinio crystals ;
a:6:c = 1-343:1:?; a = 86° 9'; i8 = 10a° 38';
7=91° 32' (Haushofer, Z. K. 9, 533).
TETEA-ETHYL-DI-AMIDO-DI-PHENYL-
NITEO-PHENYL-METHANE v. Niteo-tetba-
ETHXL-DI-AUlDO-TBI-PHENYIi-METHANB.
TETEA - ETHYL - DI - AMIDO - DI - PHENYL
OXIDE 0(CaH4NEt2)j. [89°]. From
S(C,H4NBtj)j and silver nitrate (Holzmann, B.
21, 2061). Needles, insol. water, si. sol. cold
alcohol and ether.-B"H^tCl,. [0. 100°].
Yellow flooculent pp., si. sol. warm alcohol. —
Pi crate B"20,Hj,(N02)aOH. [174°]. Yellow
crystalline pp., sL sol. hot alcohol.
Tetra-ethyl-di-amido-di-phenyl peroxide
Oj(C,H4.NEt2)2. [67°]. From the corresponding
sulphide by treatment with ammoniacal AgNO,
(Holzmann, B. 20, 1636). Needles or prisms.
Decomposed by moist air.
HEXA-ETHYL-TEI - AMIDO -DI-FHENYL-
PHENYLENE DIKETONE Cj^H^NsOj i.e.
CsH,(NEt2)(CO.C„H4NEtj)j. [o.l70°]. Fromtetra-
ethyl-di-amido-benzophenone, di-ethyl-aniline,
and COClj at 120° (Michler a. Gradmann, B, 9,
1912). Triclinic crystals (from alcohol).
TETEA - ETHYL - DI - AMIDO - DI-PHENYI-
PROPANE CMej(C5H4NBtj)j. [76°]. Prepared
by heating acetone (10 pts.) with diethylaniline
(50 pts.) and zino chloride (30 pts.) in sealed
tubes for 12 hours to 170° (Doebner a. Petschow,
A. 242, 834). Long needles. Insol. water, sl<
sol. cold, v. sol. hot, alcohoL Sol. ether, OS,,
petroleum-ether, and benzene. -
Salts. — ^B"H2l2: reddish yellow pp. ; t. BoL
hot water and alcohol. '
o-ETHYL-AMIDO - & . PHENYL - PEOPIONIC
ACID • C«H4(NHEt).0Hj,.0H,.C0jH. Ethyl-
amido-hydrocmnamicac'id. Fromo-ethyl-amido-
cinnamic acid and sodium amalgam in alkaline
solution (Friedlander a. Weinberg, B. 15, 2104 ;
Fischer a. Kuzel, B. 16, 1449; A. 221, 271).
DUute H2SO4 throws down the acid as a white
flocoulent pp., excess of H^SO^ dissolves it, and
on warming its anhydride oxy-ethyl-quinoline
dihydride (ethyl-hydrocarbostyril) separates as
an oil.
Nitrosamine
C.H,(NptN0).CH2.CHj.C0jH. [78°]. Formed
by adding NaNOj to a solution of the acid in
H2SO4. Groups of colourless oblong plates (from
dilute acetic acid). Decomposes at 150°. Sol.
alcohol, ether, benzene, and alkalis. Gives
Liebermann'B reaction. On reduction with zinc-
dust and acetic acid it gives
CBH4(NBt.NHi).CHj.CH2.COjH, which on eva-
poiating leaves its lactam, ethyl-quinazole di-
hydride.
TETEA-ETHYL-DI-AMIDO-DI-PHENYL-DI-
SULPHIDE S2(CjH,NEt2)j. [80°]. From di-
ethyl-aniline and S2CI2 in ligroin (Holzmann, B.
20, 1636 ; 21, 2056). Golden prisms ; si. sol.
ether, m. sol. alcohol and benzene. Decomposed
by water. Forms a crystalline pier ate [175°J
and platino-chloride.
TEI - ETHYL - TRI - AMIDO - DI - PHENYL-
TOLYL CAEBIHOL Cj^HssNgO i.e.
OjH3Me(NHEt).C(OH)(CsH4.NHEt)j. TH- (?)-
ethyl-rosanilme. From rosaniline (Ipt.), Btl
(Ipt.), KOH (Ipt.), and. alcohol (Hofmann, A
132, 163).— CjoHaaNjIHI : lustrous green crystals
which form a violet solution in water.
ETHYL-a-AMIDO-PBOPIONIC ACID
CsHi.NOj i.e. CH3.CH(NHBt).C02H. S. 50 at
25°- S. (alcohol) 2 at 25°. Formed by boiling
a-bromo-propibnic acid with ethylamine (Du-
viUier, A. Oh. [6] 7, 427; C. B. 99, 1120 ; 100,
916). MonocUnio crystals (containing f aq) or
nacreous plates (from alcohol) ; sol. water and
alcohol. Its hydrochloride forms deliques-
cent needles. It forms a crystalline platino-
chloride and aurochloride. — CuA'j2aq:
blue prisms, sol. water and alcohol. When its
saturated . solution is mixed with a solution of
cyanamide there is deposited in three months a
crystalline homologue of creatinin
.NBt.C:NH
CH.CHC I ; S. 27 at 17° ; S. (alcohol)
\OO.NH
5-6 at 16°.
472
ETHYL-AMlDO-rSOPROPYL ALCOHOL.
£Tfi7L-AMID0.IS0FR0PYL ALCOHOL e.
EtH^Ii-OXY-ISOPKOPYL- AMINE.
DI-ETHYL-AMIDO-PEOPYLENE-GLYCOLo.
Dl-ETHYL-M-OXY-PKOPYL-AMINE.
ETHYL-AMIDO-TOLUENE v. Amido-tolyIi-
ETHANE and ElHYL-TOIiTJIDINE.
Ethyl - tri ■ amido - toluene CgH^N, i,e.
C.HjMe(NHEt)(NHj.)j [1:4:3:5]. Obtained by
reducing di-nitro-^-tolyl-ethyl-nitramine with
tin and HCl (Van Eomburgh, B. 2". 0. 3, 412).
a-ETHYL-AMISO-ISOVALEEIC ACID
C,H,5N0j i.e. (CH3)j,CH.CH(NHEt).C02H. From
bromo-isovalerie acid and ethylamine (Duvillier,
A. Oh. [5] 21, 439 ; G. B. 88, 425). Groups of
slender white needles ; sol. water and alcohol,
insol. ether. Neutral to litmus. Suhlimes above
110°. — HA'HOl : confusedly crystalline ; v. sol.
water and alcohol, insol. ether. — OuA'^ajaq:
crystalline violet mass forming an intense blue
solution. — The platinoohloride and auro-
chloride are exceedingly deliquescent.
ETHYLAMINE CjH,N i.e. NH,Et. Mol. w.
45. (19'=). S.G. a -6964. V.D. l-5"767. H.E.p.
17,510. H.F.V. 15,770 (rfe.). x
Compressibility : Isambert, C. B. 105, 1173.
Formation. — 1. By boiling cyanic or cyan-
urio ether with potash (Wurtz, G. B. 28, 223,
323; A. Gh. [3] 30, 443).— 2. Together with
NHj by boiling ethyl-urea with potash (W.). —
3. By the action of ammonia on the ethers of
inorganic acids, e.g. : EtBr and EtI (Hofmann,
C. J. 13, 331), EtCl (Groves, 0. J. 13, 331),
EtaPO, (De Clermont, A. Gh. [3] 44, 335), Et.,S04
(Strecker, A. 75, 46), EtNO, (Juneadella, G. B.
48, 332), KEtSO, (Erlenmeyer a. Carl, J. 1875,
617), and Et^SOa (Carius, A. 110, 209).— 4. By
heating chloride, bromide, or iodide of ammo-
nium with alcohol or ether in sealed tubes (Ber-
thelot, A. Gh. [3] 38, 63).— 5. Formed, together
with di- and tri-ethyl-amine, by heating abso-
lute alcohol with ammoniacal ZnCLj at 260° ;
the yield of mixed bases amounts to about
46 p.c. of the alcohol used (Merz a. Gasiorowski,
B. 17, 63,7). — 6. From propionitrile, zinc, and
dilute H^SO, (Mendius, A. 121, 142).--7. By
the dry distillation of alanine (Limpricht a.
Schwanert, A. 101, 297). Occurs also among
the products of the dry distillation of beet-root
molasses (Duvillier a. Buisine, A. Gh. [5] 23,
317). — 8. Occurs among the products of the
putrefaction of yeast and flour (Hesse, J. pr. 71,
471 ; SulUvan, J. 1858, 231).— 9. With di- and
tri-ethyl-amine by heating white precipitate
NHjHgCl with EtI (Sonnenschein, A. 101, 20).
10. By heating acetamide with alcoholic so-
dium-ethylate at 170°-200° (Seifert, B. 18,
1357). — 11. By the action of alkalis on pro-
pionic bromo-amide, or of bromine and KOH on
propionamide ; yield 80 p.c. of theoretical (Hof-
mann, B. 15, 753). — 12. By reduction of a cold
solution of aldehyde-phenyl-hydrazide in 5 pts.
of alcohol by means of sodium-amalgam (2 p.c.)
and acetic acid^ yield 45p.o. of the theoretical.
B'jHjClsPtCl, : hexagonal prisms (Tafel, B.
19, 1926).
Preparation. — 1. Cyanic ether is boiled with
aqueous KOH, the escaping gas is absorbed by
HClAq, and the ethylamine hydrochloride dried,
mixed with quick-lime, and distilled (Wurtz).
The potassium cyanate from which the cyanic
ether is prepared (by distillation with KEtSOj) is
usually sufficiently impure to give off Uflj, whifih
then produces all three ethylamines, so that the
product is seldom quite pure. — 2. Ethyl nitrate
is heated with alcoholic ammonia. NH^Cl is
hardly soluble in alcohol, and the ethyl-amines
are separated by crystallisation of their picratea
(Carey Lea, G. N. 5, 118). — 3. A mixture of pro-
pionamide (1 mol.) and bromine (1 mol.) is
treated in the cold with a 5 p.c. solution of KOH,
and the solution run slowly into a 30 p.c. solu-
tion of (3 mols. of) KOH at 60°-70° as described
under methylamine ; the yield is 80-90 p.c. (Hof-
mann, B. 15, 767).— 4. EtBr is heated with
cone. NHjAq in sealed tubes at 100° (Hof-
mann, G. J. 3, 300).— 5. EtI is heated with
aqueous NHj at 100°. The product is distilled
with KOH. The mixture of the three ethyl-
amines is dried over KOH and mixed with oxalic
ether. Ethylamine forms diethyl-ozamide
NHEt.CO.CO.NHEt, di-ethyl-amine forms di-
ethyl-oxamio ether NEt^.CO.CO.COjEt, whilst
the tri-ethyl-amine has no action, and is removed
bj- distillation. The liquid di-ethyl-oxamio ether
is then separated by filtration from the crystal-
line di-ethyl-oxamide. On distilling the di-ethyl-
oxamide with potash ethylamine passes over.
EtCl obtained as a by-prodactin the manufacture
of chloral may be used instead of EtI in the above
preparation (Hofmann, B. B, 109, 776). When
EtCl is heated in equimolecular proportions with
cone. NHjAq at 90° a floating layer of tri-ethyl-
amine containing free NH, is formed, while
ethylamine and diethylamine remain dissolved
as salts, and constitute the chief product. The
same mixture of EtCl and NH,Aq when heated
at 150° forms NH^Cl, ethylamine hydrochloride,
and NEtjCl as chief products, only traces of
NHEtj and of NEtj (free) being formed (Malbot,
A. Gh. [6] 13, 477; 0. B. 105, 755).— 6. A good
modification of the preceding njethod, proposed
by Groves {G. J. 13, 331)', consists in heating
ethyl chloride (1 mol.) with a solution of am-
monia (1 mol.) in alcohol. After removing the
insoluble ammonium chloride the alcohol is dis-
tilled off, and the hydrochlorides are decomposed
by soda. The bases are received in water, sul-
phuric acid added, and the solution of the sul-
phates evaporated to a syrup. This is poured
into absolute alcohol, in which ammonium sul-
phate is insoluble (c/.,Wanklyn a. Chapman, Pr.
15, 218). The sulphates are again decomposed,
and the_ bases received in water, and to the solu-
tion ethyl oxalate is added, in a quantity calcu-
lated on the supposition that the alkalinity is
due to mono-ethyl-amiue. The separated diethyl-
oxamide is filtered oS and the syrupy mother
liquor is boiled for 12 hours with 10 times its
volume of water, so as to form acid diethylamine
oxalate and di-ethyl-oxamio acid. On concentra-
tion the f oriaer salt separates out in long needles,
and on decomposition yields pure diethylamine.
The molten liquor is decomposed with soda, the
separated bases received in alcohol and again
treated with ethyl oxalate, and the mixture dis-
tilled to remove the triethyl-amine and alcohol,
and to the residue milk of lime is added to pre-
cipitate calcium mono- and di- ethyl-oxamate,
which on decomposition yield diethylamine
(Davillier a. Buisine, A. Gh. [5] 23, 340 ; G. B.
88, 31).
Properties. — Colourless inflammable liquids
ETHYLAraNE,
473
does not solidify at — 140°. Possesses a pungent
anunoniacal odour, a strong alkaline reaction,
and burning taste, inflaming the tongue. It forms
dense white fumes with HCl. It mixes with
water, considerable rise of temperature taking
place, but it is oonipletely expelled again by
boiling. Solid KOH separates it from its aqueous
solution. It expels NHj from' ammonium salts.
An aqueous solution of ethylamine resembles one
of NH, in behaviour towards many metaUie
salts ; it differs in dissolving the ppd. oxides of
aluminium, gold, and ruthenium, and in not dis-
solving the pps. which it gives with salts of Cd,
Ni, and Co. It dissolves ppd. cupric hydroxide
less readily than NH^ does. With SnCl, it gives
a pp. very soluble in excess. Phosphomolybdio
acid gives a yellow pp. more soluble than the
corresponding pp. obtained with ammonia. An
alcoholic solution of ohloro-tri-nitro-benzene
(pioryl chloride) gives the characteristic ethyl-
pioramide C,H2(NOj)3{NHEt) with even small
quantities of ethylamine (Van Eomburgh, R.T.G.
2, 107). A concentrated aqueous solution of
ethylamine that has been dehydrated as far as
possible by KOH yields on distillation dry ethyl-
amine gas, followed very soon by a liquid boiling
below 75°, which is probably a hydrate of
ethylamine (WaUach, J3. 7, 326). From an ex-
amination of the compressibility of a solution of
ethylamine in water, Isambert also concludes
that chemical combin3.tion does take place be-
tween the water and the base (Isambert, G. JR.
105, 1173).
Beaations. — 1. On passing through a red-hot
tube there is formed NHj, hydrogen, HCy, CH„
CjHj, CsHj, CjHj, and carbon (MuUer, Bl. [2]
45, 438). — 2. Nitrous acid produces nitrogen and
alcohol (or nitrous ether). — 3. Chromic acid mix-
tv/re oxidises it to aldehyde, acetic acid, water,
and nitrogen (Wanklyn a. Chapman, 0. J. 20,
328). — 4. Cyanic acid forms ethyl-urea. — 5. Cy-
anic ether gives di-ethyl-urea. — 6. o-Oxy-benzoic
aldehyde forms syrupy CjHuNO (237°), sol. water
(Dennstedt a. Zimmermann, B. 21, 1553). —
7. Dry ethylamine hydrochloride is converted by
COClj into NHEtCOCl at 260° (Gattermann a.
Schmidt, B. 20, 118). — 8. AUyl thiocarbvmide
(oil of mustard) gives ethyl-aUyl-thio-urea (Hin-
terberger, A. 83, 346). — 9. Gaseous cyanogen
chlm-ide forms ethyl-cyanamide, which is con-
verted by boiling water into the isomeric iso-tri-
ethyl-melamine (Hofmann, B. 2, 602 ; Cloez a.
Cannizzaro, A. 78, 228). — 10. Bleaching-powder
gives ethyl-di-chloro-amine (Tcherniak, B. 9,
143). — 11. Di-chloro-naphthoqwmone forms
^W&i.C^^fi\Oi\llQ°'].—li. Benzoic aldehydein
aqueous or alcoholic solution forms benzylidene-
ethyl-amiue PhCH:NEt (195°), an oil which is
reduced by sodium-amalgam to benzyl-ethyl-
amine PhCH^NHEt (Zaunschirm, A. 245, 279).
13. SO3 forms ethyl sulphamie acid NHEt.SOsH.
Salts. — The sulphate, chloride, tar-
trate, and other salts differ from the corre-
sponding ammonium salts in being very much
more soluble in alcohol.— B'HCl [76°-80°]. Mol.
w. 81i. Boo 35'11 in an 11 p.o. aqueous solu-
tion (KanonnikofE). Large deliquescent lamina
(from alcohol) or striated prisms (from water).
On distillation it gives ethyl-amine, di-ethyl-
amine, EtCl, OjH„ and NH, (Pileti a. Piccini,
B. 12, 1508).— B'^ajPtOl,: orange hexagonal
rhombohedra. S.G. !|i 2-253 (Clarke, Am. 2,
175). Not decomposed by boiling water (Da
Coninok, Bl. [2] 45, 131).— B'HAuCl^: very
slender golden monoclinio prisms, sol. water,
alcohol, and ether (Wurtz).— B'jajHgCl, : small
white scales (from alcohol).— B'HHgCl,: deli-
quescent trimetrio crystals (Kohler, B. 12, 2211,
2324; TopsoS, Z. K. 8, 246).— B'HHg.Cl,, :
hexagonal rhombohedra.— E'EClHgCy^: large
laminee, permanent in the air, decomposed at
100° ; sol. water, si. sol. cold alcohol (Kohl a.
Swoboda, A. 83, 342).— B'jH^PdOlj : feathery
tufts of large black crystals ; red by transmitted
light (Eeckenschuss, A. 83, 343; c/. MuUer,
A. 86, 366).— B'jH^GuClj: trimetrio crystals. —
B'HBr : crystalline.— B'^H^SOi" : deliquescent
gummy mass, v. sol. alcohol. — B'HNO," : very-
deliquescent thin laminss. — MgB'HP04 5aq::
bulky pp. obtained by adding sodium phosphate
to a solution of magnesium sulphate mixed with
ethylamine or any of its salts ; becomes crystal-
line on standing. — B'2H2Mo20, : white scales, be-
coming brown on drying (Meyer, J. pr. 67, 151).
— B'jH2SO,Al2(SO,)3 24aq: S. 15 at 25°; regular
octahedra (Stenuer a. Kanmer, A. 91, 172). —
B'H2C03(?) : very unstable crystalline mass ob-
tained from B'HCl and Na^COj.— B'HOAc :
deliquescent crystalline mass. — B'H^S : crystals ;
vapour-tension 48 at 13° (Isambert, C. B. 96,
708).— B'HVO, (Bailey, C. J. 45, 692).—
B'4(HjO)2(V205)3 ^e^.—W^.fl(Jfi^i•. red prisma
(Ditto, O. B. 104, 1844).— B'HCyS: deliquescent;
not converted into ethyl-thio-urea at 150° (De
Clermont, Bl. [2] 27, 198).— E'lLCjO, : trimetrio
laminffi (Loschmidt, Sitz. TT. 51 [2] 7, 384 ; J. 1865,
376). — B'jH^CjO,: monoclinic crystals. — 0 am-
phorate B'jO,„H,bO,: small needles (Wal-
lach a. Kamensky, A. 214, 242). — Mucate
B'jCjHijOj 8aq : oblique rhombic prisms (Bell, B.
10, 1861).— Pimelate B'jCjHiA (Wallaoh a.
Kamensky, B. 14, 170). — Benzene sulphon-
ate OsHjSOaHB' [92°] (Norton a. Westenhoff,
Am. 10, 129). — p -Toluene sulphonate
B'HS03.C„HjMe [111°] (Norton a. Otten, Am. 10,
140).— Combinations with salts. — B'HgClj:
crystalhne pp. got by mixing alcoholic solutions
of ethylamine and HgCl^ (Kohler, B. 12, 2208,
2323).— B'jHgCLHgjOa : pp. got by mixing the
aqueous solutions. By boiling with excess of
HgClj there is formed an insoluble yellow salt
NHEt.HgClHgO, while crystalline NHEt.HgCl
remains in solution. — B'^PtClj: fawn-coloured
powder. — B'^PtCl^ 2aq : colourless crystals, v.
sol. water.— B'4PtSO,.—B'j(NH3)2PtClj (Gordon,
B. 3, 174).— B'CjHiPtClj (Martins a. Griess, A.
120, 326).
Formyl derivative NHEt.CHO. (197°)..
S.G. — -952. Mixes with water, alcohol, and
ether.
Acetyl derivative OjHsNO i.e. NHAoEt..
(202°) S.G. — -942. Formed by the action of
ethylamine on acetic ether; or of HOAc oni
cyanic ether (Wurtz, A. Ch. [3] 30, 491 ; C. B,
37; 180). Colourless liquid. Formed also by-
dehydrating ethylamine acetate. PGl^ converti-
it into OsHijClNj whence solid KOH forms, on-
warming, di-ethyl-acetamidine C|jHnN2 (Wal-
laoh a. Hoffmann, B. 8, 1567 ; A. 184, 108).
Di-acetyl derivative CgHnNO.. i.e,.
NEtAOr (185°-192°). S.G. 22 1-009. From
474
ETHYLAMINE.
cyanic ether and Ao^Oat 190° (Wurtz, A. Oh.
[3] 42, 43). Liquid.
Yaleryl derivative CM63.CO.NHBt.
[49°]. (204°). Crystals; V. sol. water, alcohol,
and ether ; has no smell. Pure HNO, attacks
it slowly, giving ofl N^O (Franohimont a. Klob-
bie, B. T. C. 6, 241).
Heptoyl derivative 0,H„.CO.NHBt. [6°].
(266(°). Formed by heating ethylamine hepto-
ate to 230° {F. a. K.). Pure HNO. gives off
N2O.
, Benzoyl derivative CjHs.CO.NHEt :
[67°] ; (260°) ; glistening needles (from water)
or plates (from dilute alcohol). From ethyl-
amine and BzCl (Eomburgh, B. T. G. 4, 390).
Formed also by the action of ethyl-carbamio
chloride OC(NHiEt)Cl upon benzene in presence
of .AljClg (Gattermann a. Schmidt, B. 20, 120;
4.244, 50J.
o-Amido-bemoyl derivative
C„H^(NH,)CO.NHBt. [105°]. From isatoio
acid,and ethylamine (Finger, J. pr. [2] 37, 487).
White colloid mass ; sol. alcohol and hot ligroin.
HNO2 converts it into CsH,<^°>NEt. [70°].
Ethyl - chloro - amine NHEtOl. Acetyl-
derivative NAcEtCl. Formed by passing
chlorine into NAcEtH at ~18° (Norton a.
Tcherniak, G.B. 86, 1409). Liquid, v. sol. water,
alcohol, and ether ; decomposed by heat. Boil-
ing soda-solution decomposes it into chloroform,
ethyl-di-chloro-amine, ethyl carbamine and
NHjEt.
Ethyl -bromo- amine. Acetyl deriva-
tive. NAcEtBr. From aoetyl-ethylamine by
warming with a solution of bromine in aqueous
KBr(N.a.T.).
Ethyl-di-chloro-amine NCl^Et. (89°). S.G.
f 1-240; if 1-230. Obtained by chlorinating
ethylamine at 0° (Wurtz, A. Ch. [3] 80, 474).
Prepared also by distilling ethylamine hydro-
chloride (100 g.) with bleaohing-powder (250 g.)
made into a thick cream with water (Tcherniak,
B. 9, 146). Pungent yellow oil; not solid at
— 80°. Insol. acids. Decomposes spontaneously
in damp air into NH4CI, ethylamine hydro-
chloride, chloroform, acetyl chloride, and aceto-
nitrUe. Eeduced to NH^Bt by HjS. Alkalis
give HOAo and NH,. Converts aniline into di-
and tri-chloro-aniline, being itself reduced to
NHjEt (Pierson a. Heumann, B. 16, 1047).
Beacts with ZnEt, diluted with ether with
formation of ethylamine and tri-ethylamine
(Kohler, B. 12, 770, 1869).
Ethyl-di-iodo-amiue NIjEt. From ethyl-
amine and iodine (Wurtz ; Baschig, A.2iiO, 221).
Dark red pp.
Diethylamine C^HhN i.e. NHEt^. Mol. w.
73. (56°). S.G. 2 -726 ; is -716; ?» -706 ; ^ -674
(Oudemans, B. T. C. 1, 56). S. V. 109 (SchiS).
H.F.p. 29,320 (Th.), 31,100 (M.). H.F.v. 26,420
ITh.). H.C. 724,400 (gaseous) ; 716,900 (liquid)
(MiiUer, Bl. [2] 44, 609).
Formation. — 1. By heating ethylamine with
EtBr (Hofmann, T. 1850, 120; C. J. B, 300).—
2. By heating ammonia with EtCl, EtBr, or
EtI as described under ethylamine. — 3. Together
with ethylamine by heating ethyl nitrate with
aramonia (Carey Lea, J.pr. 86, 176). — 4. Together
with mono- and tci-ethyl-amine by heating
absolute alcohol with ammoniaoal 2nClj at 260''
(Merz a. Gasiorowski, B. 17, 637).
Prepa/ration. — ^1. By treating its nitrosamine
with cone. HClAq (Geuther, Jeiiaische Zeitsehr.
7, 118). — 2. By acting on di-nitro-di-ethyl-
anUine C6Hs(N0j)jlSrEtj with dUute KOH, the
other product being OaHs(NOj)jjOK. The yield
is good (Van Eomburgh, B. T. 0. 2, 35).— 3. v.
Ethilamine.
IS. — Volatile inflammable liquid with
strong alkaline reaction ; v. sol. water. It differs
from ethylamine in not redissolving the pp,
which it forms with zinc salts, in not ppg. a
solution of PdCLj, and in the fact that the pp.
which it forms with HgClj is not soluble in
acetic acid, whereas the pps. formed by ethyl-
amine and by NH, are soluble in HOAc.
Beactions. — 1. When passed through a red-
hot tube it forms HCy, NHj, carbon, CH^, hy.
drogen, C^Hj, benzene, and nitrogen, but no
ethylene (Muller, Bl. [2] 45, 438).— 2. Iodine
forms an oily substitution product. — d. Potassium,
nitrite converts its hydrochloride into di-ethyl-
nitrosamine NEtjNO. This is a neutral yellowish
oil, (177°), S.G. ^' -951, V.D. 3-36 (calo. 3-53)
(Geuther a. Kreutzhage, A. 127, 43). It is split
up by alcoholic KOH at 140° into NH, and
ethylamine. — 4. Oj/amoei/ierformstri-ethyl-urea
(Hofmann, C. B. 54, 252).^5. Cyanogen chloride
forms liquid di-ethyl-oyanamide (190°) (Cloez
a. Cannizzaro, A. 78, 228).— 5. SO, forms di-
ethyl-sulphamic acid NEtjSOsH.
Salts.— B'HCl [217°], (320°-330°), non-
deliquescent plates (WaUach, B. 14, 748). V. e.
sol. water, m. sol. alcohol, v. .sol. chloroform
(Behrend, A. 222, 119).— B'jHjPtClj : orange
monocUilio crystals (Topsoe, ^. K. 8, 246). —
B'HAuCl^ : trunetrio crystals.— B'HHgClj : tri-
metrio crystals. — B'HCl (HgCl2)5: hexagonal
rhombohedra. — B'j,H2Clj(HgOl2)5 : dimorphous.
— B'jHjPtBrj : monoolinic. — B'H^S : crystalline ;
its vapour-pressure ia 150 mm. at 10° (Isambert,
O. i?. 96, 708).— B'HNO,. [100°]. Long needles
or prisms (Franohimont, B. T. O. 2, 33^).-
B'H;C204 : long needles, m. sol. water (DuviUier
a. Buisine, A. Gh. [5] 23, 342). Benzene sul-
phonate B'HS03.CaH5 : [139°] (Norton,
Am. 10, 129). — ^-Toluene sulphonate
B'HS03.CsH4Me: [88°] (N.).
, Formyl derivative NEt^OHO (178°).
S.G. — -908. From di-ethyl-oxamic acid by
heating (WaUach, B. 14, 745). Liquid, miscible
with water.— B'2H2PtCls.—B'jH„PtCl82aq. With
POls it forms a base ObH,-,Nj (WaUach, A. 237,
236).
Acetyl derivative CoHiaNO i.e. NEt^Ao.
(186°). S. G. !!' -925 (WaUaoh a. Kamensky, A.
214, 235).
Tri-chloro-acetyl derivative
CCl3.CO.NEtj. [27°] (F. a. K).; [90°] (0.). From
NHBtj and CC1,.C0C1 (Franohimont a. Klobbie,
B. T. C. 6, 236). From hexa-chloro-acetone and
NHEtj (Cloez, .4. Ch. [6], 9, 145).
Valeryl derivative CMea.CONEt,. (208°).
S.G. ia -891 (F. a. K.).
Heptoyl derivative CsHisCO.NEt,. [below
-15°], (258°). S.G.i^-881(F. a. K.).
Benzoyl derivative NEt^Bz. (282°).
S.G.lfi 1-019; oU,; sol. dilute HCl but reppd.
ETHTLAMINE.
47B
by water (Hallmann, B. 9, 846; Eomburgh,
B.r. C.4, 387).
Triethylamine C^HjsN i.e. NEt,. Mol. w.
101 (c/. Dewar a. Soott, Pr. 35, 347). (90°). S.Gr.
•J-7277 (BruU, A. 200, 186). S.V. 163-86 (Sohiff).
fi^ 1-406. Eoo 53-86. H.F.p.42,080 (Thomsen) ;
34,400 (MuUer, Bl. [2] 44, 609). H.P.v. 38,020
(r^s.). H.0.1,047,100 (gaseous); 1,038,300 (liquid)
(M.). Critical temperature, 267° (Pawlewsky, B.
16, 2633).
JFormoitioro. — ^1. By heating diethylamine with
EtBr. — 2. From cyanic ether and EOEt. — 3. By
heating ammonia with Btl, EtBr, BtCl, or EtNOs ;
V. EiHYLAMiNE (Hofmann, C. J. 3, 300 ; Carey
Lea, C. N. 6, 142).— 4. Together with ethylene
and water by the destructive distillation of tetra-
ethyl-ammonivun hydroxide (Hofmann). — 6. To-
gether with mono- and di-ethyl-amine, by heat-
ing absolute alcohol with ammoniacal ZnCl, at
260° (Merz a. Gasiorowski, B. 17, 637).
Properties. — Strongly alkaline liquid, in-
flammable, having an ammoniacal odour; si.
Eol. water. Its aqueous solution forms with
salts of Zn, Cd, Be, Zr, Ni, Co, Sn", Ag, Hg",
Cu, Pb, Fe, and Mg, pps. insol. excess ; with
salts of Al and Sn'' a pp. v. sol. excess ;
with AuClj it gives a yellow pp. insol. excess,
which soon blackens from reduction to AuCl, an
odour of aldehyde being formed.
BeacUons. — 1. At a temperature of 1200° it
gives HCy, ammonia, carbon, hydrogen, CE„
acetylene, and C^H,, but no benzene or N
(Muller, Bl. [2] 45, 438).^2. KMnO, oxidises it,
giving CO, and EOAo (Wallach a. Claisen, B.
8, 1237). — 3. Its hydrochloride is not decom-
posed by aqueous ENO, in the cold, but on boil-
ing some KEtj.NO is formed (Geuther, JS. [2] 2,
513). — 4. When heated with s-bromo-butyric
acid and water there is formed o-oxy-butyrio
acid and NEt,HBr. The same products appear
to be formed when no water is present (DuvilUer,
Bl. [2] 48, 3; cf. Briihl, B. 9, 34).— 5. SO,
forms EtjN<^Q^«^ [92°] which crystallises in
tables ; sol. alcohol, acetone, and hot water; si.
sol. cold water and ether. It is decomposed by
boiling water into acid triethylamine sulphate
(Beilstein a. Wiegand, B. 16, 1267).— 6. Tri-
ethylamine combines directly with the chlorides,
bromides, and iodides of primary alkyls, form-
ing ammonium derivatives that are not decom-
posed by EOH, but are converted by moist Ag^O
into non-volatile, caustic bases. When the alkyl
is secondary or tertiary an define and a salt of
ifiethylamine are the chief products. Thus,
isopropyl iodide at 100° forms NBtjHI and
CjHj, while MejCBr forms NEtjHBrand butylene
fBebonl, C. B. 93, 69).
Salts. — B'HCl: white, non-deliquescent
laminae. — B'^^tClg : orange monoclinic crys-
tals, v.'sol. water. — B'HAuCl,: monocUnio crys-
tals.—B'^HaHgCl^: hexagonal crystals (Topsoe).
— BBEgjClj : monoclinic. —B'HHgsCl,, : hexa-
gonal rhombohedra. — B'^HjCuCl,: monoclinic. —
B'HNOs. [99°] • Hygroscopic crystals (Franchi-
mont, B. T. 0. 2, 388). — ^B^HjPtBre : monoclinic,
— B'HBil, : scarlet prisms (Kraut, A. 210, 317).—
B'H.CjG,: trimetric plates (Loschmidt, J. 1865,
375 i Sitz. W. 51 [2] 7, 384).
Benzene sulphonate CgHvSO,E£'.
[121°] (Norton, Am. 10, 129).— ^-Toluene
sulphonate C^H^McSOsHB'. [65°] (N.).
Tetra-ethyl-ammonium hydroxide NEt^OH.
Obtained by decomposing its iodide by moist
AgjO or its sulphate by baryta. Very deUqnes-
cent, hair-like needles. Absorbs COj from the
air. Strongly alkaline, saponifying fats. Its
solution rubbed between the fingers feels like
caustic potash ; it strongly attacks the tongue,
and when dilute has a^ bitter taste. With
metallic solutions it behaves like potash, except
that alumina is less soluble in it, and hydrated
chromic oxide is quite insoluble. A very con-
centrated solution, as well as the dry base, is split
up at 103° into NEtj, water, and C^H,. Its
solution boiled |for 24 houra with EtI gives
NEt,I and alcohol. ~
Salts of Tetraethyl ammonium (Hof.
mann, 0. J. 4, 304 ; A. 78, 253).— NEt^Cl. The
union of NEt, with EtCl takes place with diffi-
culty in dilute alcohohc solutions (Malbot,.i.C^.
[6] 13, 545).— (NEt,)jPtCl„ : orange pp. ; si. sol.
water, v. si. sol. alcohol and ether. — NEt^AuOl, :
lemon-yellow pp. ; si. sol. cold water and
HClAq.— (NEtJjHgsClij : white orystaUine pp. ;
sol. water and boiling HClAq, from which it
separates as unctuous plates (Hofmann). -r-
(NEtJjHgCl, : dimetric crystals (TopsoS, J.
1883, 620).— NEt^HgClj : tricUnic— NBt^Hg^Cl, :
triclinic. -i- NBtjHgaCl, : monoclinic. —
NBtjHgsCl,, : hexagonal rhombohedra. —
NBtjCljI : regular crystals deposited, from a
hot solution of NBtjCI and IClin water (Tilden,
C. J. 19, 145).— (NBtJsBijCl, : six-sided tables
(Jorgensen, J. pr. ■ [2] 3, 344).— (NEt4)2CuCl, :
dimetric crystals. — NEt^Br. — NBt^Br, [78°]:
light-red pp. or orange-red needles (from al-
cohol) ; V. sol. alcohol and CSj. A solution of
iodine in aqueous KI added to its alcoholic
solution throws down NEt^I, (Clamor-Marquart,
J.pr. [2] 1, 429).— NEt4Br5: crimson pp. ; gives
oS I of its Br in air. — (NEtJjBijBr, (Jorgensen).
— NEt^I. The union of NEt, with EtI takes
place slowly in the cold, but when it is started
at 100° it goes on with great vigour. Large
crystals (from water) ; v. sol. cold water, sol.
alcohol, insol. ether. Decomposed on distilla-
tion into NEt, and Btl. Not acted on by
EOHAq, but less soluble therein than in water.
Decomposed by AgNO,, by Ag^SO,, or by moist
AgjO, yielding NEt^NO,, (NBtJ^SOj, or NEt^OH
respectively. — ^NBtil, : red needles (Weltzien, A.
86, 292 ; 91, 33).-NEtJ, : [108°] ; dark-violet
plates (Geuther, A. 240, 66).— (NEtiI)j5Hgl2 ;
from NEt^I and Hgl^.— (NBtj^aSHgl^ : yellow
crystals formed by the action of Btl on N^Hg,
or NHgjHjCl ; m. sol. alcohol, not decomposed'
by water (E. Miiller, A. 108, 6 ; Sonnensohein, A.
101, 20).— NBtJHgl^ : from NEtJ, and Hg
(Eisse, A. 107, 224).-C,JH„N4Hg,I„ : [150°] ;
fromNHj.HgOl and lEt: golden-yellow crystals,
insol. alcohol, ether, and water. — (NBt4l),Bi2l,
(Jorgensen, /. pr. [2] 3, 339).— (NBtJjWjO, :
deliquescent (Classen, J. pr. 93, 446). —
(NEtJaMo20, 3aq : deliquescent (C). — ^
(NEt,)206Sn02 aq : insoluble dimetric octahedra.
— (NiEt4)„07Sn02 aq.— (NEtJjCrO^ : not crystal-
lised.-(NBtJ^Cr.A : prisms (C.).— NEtjAsO, :
erystfiUine. — (NEt4)4Sb20j : deliquescent (C). —
Picrate [251°] (Lessen, A. 181, 375).—
(NEtJsFeCys 4aq : from AgjFeCy, and NEt J
476
ETHYLAMINE.
(Bernheimer, B. 12, 409).— NBt.VO, (Bailey,
C.J.45,693).
Tri-etliylaimne meth^lo-hydroxide
NEt,Me(OH). Methyl4ri-et}iyl-ammomum, hjf-
droxide. Deriootiwes : NEtjMel. FromNEts
and Mel (Hofmann, A. 78, 277). V.e. sol. water,
but ppd. from its solution by KOH.— NBtsMels :
[16°] ; dark green plates.— NEtjMel, : [42°] ;
brownish-violet plates.— (NEtjMeO^JPtCl, : di-
metrio crystals. — NEtaMeAuCl,: dimetric. —
(NEt,MeCl),HgCl,: dimetrio (Topsoe, Z. K. 8,
846). — (NEtjMeCl),5HgCl2 : monoclinie. —
NEtsMeOl^HgClj), : monoclinio crystals. —
(NEt.MeCl)sCuCl,.— HEtjMel, (Miiller, A. 108,
fi).— Picrate [268°] (Lessen, A. 181, 374).
Tii-etbylamine iodo-metliyl-liydrazide. De-
rivatives: NEt3(CHjI)I. From NEtj and
CHjI: (LermontoS, B. 7, 1253). Dimetric tables,
T. sol. water. Boiling with AgoO suspended in
water gives NEt,(CHjI)OH.— (NEt3CHjI)jPtCl. :
octahedra.
Tri-ethylamine amylo-hydroxide
NEta(C5H„)0H. Not obtained crystalline. The
iodide NBt3(CjH„)I forms slender unctuous crys-
tals, V. sol. water and alcohol, insol. ether (Hof-
mann, C. J. 4, 313).
SI-ETHTLAUISnE SISTTLFHOiriC ACID
C,H„NSA »■«• NH(CH2.CHj.S03H)2. Imido-di-
ethane disulphonic acui. Formed by heating
taurine with baryta-watei at 220° (Salkowsky,
£■ 7, 117).
HTHYL-AMMSLINES v. CyanvHc acid in
the article Cyanic acid.
ETHYL-AIUYL is Heptane.
DI - ETHYL - AMYX - AMINE NEt2(C5H„).
(154°). Obtained, together with water and
ethylene,by the dry distillation of NEt,(C5H„)0H
(Hofmann, C. J. 4, 315). Liquid, soL water.
EtHYL-ISO-AMYL-ANILINE 0,3Hj,N i.e.
NPhEt(05H,,). Mol. w. 191. (262°). From
isoamyi-aniline andEtBr; or from ethyl-aniline
and isoamyl bromide at 100° (Hofmann, A. 74,
156 J 79, 13). Liquid. Its hydrobromide is re-
solved by distillation into ethyl-aniline and iso-
amyl bromide. HNO3 and HjSOj give a product
[c. 72°] (Van Eomburgh, B. T. C. 2, 103).—
B'jHjPtCl„: [100°].
Methylo-^iodide NPhEt(C5H„)MeI. Moist
AgjO forms NPhEt(05H| ,)MeOH, which is re-
solved by distillation into ethylene, water, and
methyl -isoamyl -aniline. Gives the platino-
chloride (NPhEt(C5H, OMeCy^PtCl,.
DI-ETHYL-ISOAUYL BOBATE
Et2(0sH„)B0s. (174°). S.G. ss -858 (Schiff,4.
Suppl. 5, 154).
Ethyl-di-isoamyl borate Et(C5H„)jB03. (0.
213°). S.G.2-876.
ETHYL ISOAUYL CABBONATE
Et(CsH„)CO,. (182° cor.). S.G. ^ -92 (E5se,
A. 205, 230). PCI5 gives CsHnO.COCl and BtOl.
ETHYL AMYL KETONE Cjas.CO.CEtMe.,.
Ethyl-amyl-pinacolin. (151°). S.G. 2 '845;
2i -829. From 0BtMe2.C0Cl and ZnEt, (Wysch-
negradsky, A. 178, 107). Formed also by
boiling the pinaoone CMeBt(OH).CMeBt(OH)
virith diluted HjSO, (Lavrinovitch, A. 185, 126).
■Gives on oxidation acetic acid and CEtMej.CO^.
Ethyl amyl ketone CsH.bO. (154°). S.G.
"841. Occurs among the by-productsin the pre-
3)aration of ether (Hartwig, J. pr. [2] 23, 449).
'Oil, smelling like camphor. Beduces to a secon-
dary alcohol CsHjjO. Oxidation gives propionic
and valeric acids.
ETHYL ISOAMYL OXIDE C,H,.0 i.e.
Et.0.CsH„. Ethyl amyl ether. (112°). V.D.
4-04. S.G. is -764. H.F. 49,000 (Berthelot).
Prepared by the action of potassium isoamylate
KOC3H,, on Btl ; or of potassium ethylate on
isoamyl iodide (Williamson, C. J. 4, 233). Not
formed by distilling a mixture of ethyl and iso-
amyl alcohols, since amylene is given off (Guthrie, ,
A. 105, 37). Oil, lighter than water, smelling
Ethyl* tert-amyl oxide Et.O.CMCjBt. (102°).
S.G. a -779 ; iS .751. A by-product in the for-
mation of amylene by the action of alcoholic
potash on tert-amyl iodide : the yield being
2 p.c. (Kondakoff, J. B. 1887, 300 : Beboul, G.B.
64, 1243).
DI-ETHYL-ISO-AMYL-FHOSFHINE
Et2(C5H„)P. (186°). Formed by treating di-ethyl-
isoamyl-phosphine hydrochloride with NaHO.
A colourless slightly viscid liquid (Collie, C. J.
53, 722).
Tri- ethyl - iso - amyl - phosphouium chloride.
Formed by heating iso-amyl chloride with tri-
ethyl phosphine at 130° in a sealed tube (CoUie).
Very deliquescent. Decomposed above 300° into
ethylene and di-ethyl-isoamyl-phosphine hydro-
chlorideEtj(C5H„)PH01.Theplatinochloride
forms thick needles. M. sol. water.
IBI-ETHYL-ISOAMYL SILICATE
Et3(C5H„)SiO,. (216°-225°). From isoamyl alco-
hol and ClSi(0Et)3 (Friedel a. Crafts, A. Ch. [4]
9,5).
Di-ethyl-di-isoamyl silicate Et2(C5H„)jSi04.
(245°-250°). S.G. 2-915. From Cl^SiJOEtJj and
isoamyl alcohol.
Ethyl -tri -Isoamyl silicate Et(05H„)3SiO,
(280°-285°). S.G. 2 '913. From CljSiOEt and
isoamyl alcohol.
ETHYL-ISOAMYL SULPHIDE C,H,3S i.e.
Bt'S-CsH,,. (160° i.V.) (B.). S.G. 2 -832. From
NaSCsH,, and EtI; or from CsH,,! and NaSEt
in dry alcohol (B. 0. Beckmann, J. pr. 125, 449 ;
A. SaytzeflE, A. 139, 361). Colourless oil with
alliaceous odour. Mel at 100° gives SMe,!,
ethyl iodide, and CjH,,!. Hgl, forms a com-
pound Hgl22SEt(C5H,i).
Ethyl - amyl - di - sulphide (C.^Hj) (C5H„)S2.
Formed by oxidation of an ethereal solution of
ethyl- and amyl-mercaptans with bromine. Thin
colourless liquid. ' Volatile with steam. Lighter
than water. Miscible with alcohol and ether,
insol. water (Otto a. Bossing, B. 19, 3134).
ETHYL-ISO-AMYL SULPHONE
Et(C5H„)S0j. [14°J. (270° i.V.). S.G. is 1-032.
From ethyl-isoamyl sulphoxide (g. v.) and aque-
ous KMnO, (E. O. Beckmann, J.pr. 125, 450).
ETHYL-ISOAMYL STTLFHOXIDE
Bt(C5H,i)S0. From ethyl-isoamyl sulphide
(1 pt.) and (2 p'ts. of) HNO3 (S.G. 1-4). Crystal-
line (Beckmann, J.pr. 125, 449). Oil, solidified
by a freezing mixture at — 16°. May be reduced
to ethyl isoamyl sulphide.
ETHYL-ISOAMYL THIOCARBONATE v.
Ethyl thiocarbonate.
ETHYL-ANHYDKACETONE BENZIL jj. vol,
i. p. 462.
ETHYL-ANILINE C8H„Ni.e.NPhBtH. Mol,
w. 121. (204°). S.G. iS -954. Formed by heating
a mixture of aniline with excess of BtBrto boil-
ETHYL-ANTHRANOL.
477
tag ; on cooling, a mass o£^ crystals of its hydro-
bromide is formed (Hofmann, O. J. 3, 285). Pre-
pared by saponifying its acetyl derivative with
boiling alooholio KOH; the acetyl derivative
may be obtained by warming alcohol (300 g.),
acetaniUde (75 g.), KOH (31 g.), and EtBr (65 g.);
the reactioa is at first violent, and the yield of
ethyl-aniline is 41 p.o. of the theoretical (Pictet,
B. 20, 3422 ; c/. Hepp. B. 10, 327 ; Blsbach, B.
15, 690). Prepared also by heating aniline hy-
drochloride with ethyl alcohol (1^ mol.) for
8 hours at 150° ; the yield being 52 p.o. of the
theoretical (Beinhardt a. Staedel, B. 16, 29).
Commercial ethyl-aniline may be purified by
fractional treatment with phthalio anhydride
(Piutti, .4. 227, 181).
Properties. — Oil, sol. alcohol, smelling like
aniline. Gives no blue colour with bleaching
powder solution ; colours fir- wood and elder pith
less strongly yellow than aniline. Turns brown
in air and light.
Beacldons. — 1. HNO, gives off 00^ and red
fumes, but forms also tetra-nitro-ethyl-aniline
(Van Bomburgh, R. T. G. 2, 31).— 2. Nitrom
acidtouas the nitrosimine 0|jH5NEt(N0), a
heavy yellowish oil, v. sol. alcohol and ether,
neutral in reaction, and re-oonverted into ethyl-
aniline by treatment with zinc and dilute H^SO,
(Griess, B. 7, 218). — B. A solution of acetone
saturated with SO, forms large crystals of
C^HeOSOjNPhEtH (Boessneck, B. 21, 1906).—
4. Its phenyl-ethyl-phthalamate loses H^O at
200°, becoming CO<;Q«^«>C(NPhEt)j (Piutti,
A. 227, 181). — 5. Cyanogen chloride forms
PhNEtCy (271°) (Cloez a. Cahours, A. 90, 94).
Salts. — B'HBr: large trimetric tables (from
alcohol) ; v. e. sol. water (Hjortdahl, Z. K. 6,
473).— B'jBytClg : long needles ; v. sol. water
and alcohol. — B'HCl" : crystalline mass ; con-
verted at 320° into the hydrochloride of amido-
phenyl-ethane OjHjEt.NHj (Hofmann, B. 7,
526).— B'HBrCdBrj : trimetric— B'^H^SuBr, :
monoolinic. — ^B'HI : trimetric tables.— Ethyl
sulphate B'HEtS04Et2S04 : prisms: from
NPhEtH and Et^SO, in benzene (Claesson a.
LundwaU, B. 13, 1704).
Formyl derivative CeHsNEtCHO. (260°).
S.G. 12 1-063 (Pictet a. Or6pieux, B. 21, 1106 ;
cf. Tobias, B. 15, 2866).
Acetyl derivative CsHsNAcEt. [55°].
(249°) ; (258°) at 731 mm. (P. a. C). From
sodium aoetanilide and EtI. Also from di-ethyl-
aniline and AcBr. Prisms ; sol. ether (Elsbaoh,
B. 15, 690 ; Staedel, B. 16, 29 ; 19, 1948).
Benzoyl derivative CA-NEtBz. [60°];
large crystals ; v. sol. alcohol, ether, Ac, insol.
water. Formed by heating di-ethyl-aniline with
benzoyl chloride at 200° (Hess, B. 18, 687).
Di-ethyl-aniline C,„H,5N i.e. C^H^NEtj. Mol.
w. 149. (214°). S.G. iS -936. S.H. -476 between
8° and 80° (E. Schift, G. 17, 286). Formed by
heating ethyl-aniline with excess of EtBr (Hof-
mann, .4. 74, 135). Prepared by heating aniline-
hydrobromide (or hydroiodide) with (2JL mols.
of) ethyl alcohol to 150° fo." 8 hours ; the yield
is 98 p.o. of the theoretical (Beinhardt a. Staedel,
£.16,29).
Properties.— OH. Gives no colour _ with
bleaching powder. Does not turn brown in air.
Sewjoyl QWoride at 180° forms BtOl and benzoyj-
ethyl-aniline (Hess, B. 18, 687). AcBr forms
EtBr and NPhEtAc (Staedel, B. 19, 1948).
HNO, forms tetra-nitro-ethyl-aniline (Van Bom-
burgh, JR. T. 0. 2, 31). Nitrous acid gives ni-
troso-di-ethyl-aniline 05H4(NO)NiBtj, which crys-
tallises from ether in green prisms [84°], and
dissolves in dilute acids.
Salts. — B'HBr: four-sided tables ; sublimes
in needles. — B'jHjPtCl,: yellow prisms (from
alcohol) ; less soluble than the platinochloride
of ethyl-aniline. — B'gHjCljSnBr, : monoclinic
prisms (Hjortdahl, J. 1882, 524).— B'jH^BrjSnBrj.
Methylo-iodide B'Mel: [102°]; identical
with methyl -ethyl -aniline ethylo- iodide. By
treatment with KOH it gives methyl-ethyl-
aniline (Glaus a. Howitz, B. 17, 1326). The
corresponding hydroxide splits up on distillation
into ethylene, water, and di-ethyl-aniline. Its
salts are: (NPhEtjO^^PtCl,.- NPhEtjI, [81°].
NPhBtjIj [68°] (Dafert, M. 4, 502).
Ethylo-iodide NPhEt,!.— NPhEtaOH.-—
NPhEtjCl. — (NPhEt3Cl)jPtCl< (Hofmann, A.
79, 2).
Beferences. — Beomo-, Chlobo-, Chlobo-nitbo-,
and NiTEo- ethyl-aniline.
ETHYL-ANILINE AZYLUTE v. Di-e
armdo-bemene-Azo-di-ethyl-aniKne.
ETHYL-ANILINE STJLPHONIC ACID v.
EtHYL-AMIDO-BENZENE SOIiPHONIO ACID.
ETHYL-ANTHBACENE CigH,^ or
C„H«<^j°^^')>0^,. [61°]. Large plates.
Prepared by reduction of ethyl-oxanthranol with
zinc-dust and NHg (Liebermann a. Tobias, B.
14, 802; A. 212, 109). Picric acid com-
pound [120°].
ETHYL-ANTHBACENE-SIHYSBIDE C„H„
or C.H,<g™*>C,H,. (322° cor.). S.G. H
1-049. Prepared by reduction of ethyl-oxan-
thranol with P and HI (S.G. 1-7) (Liebermann,
B. 13, 1600; A. 212, 76). Clear fluorescent
liquid. Miscible with alcohol, ether, benzene,
and acetic acid in all proportions. Cautious
treatment with GrO, in glacial acetic acid recon-
verts it intoethyl-oxanthranol ; further oxidation
gives anthraquinone.
Si-ethyl-anthracene dihydride
0aH4<^2*>CeH4. [60°]. From di-ethyl-an-
throne, HIAq (S.G. 1-7), and amorphous phos-
phorus at 190° (Goldmann, B. 21, 1176). Colour-
less crystals, t. sol. hgroin, ether, and CSj. Oxi-
dised by CrOs in HOAc to di-ethyl-anthrone.
Ethyl-anthracene-hydride-nitrite
C„Hs(Oi,HJ(NOj),. [130°]. Large crystals. Sol.
benzene. Prepared by the action of HNO, on
an acetic acid solution of ethyl-anthracene-
hydride. On oxidation with CrO,it gives anthra-
quinone (Liebermann a. Landshoff, B. 14, 473).
ETHYL - ANTHBANOL Ethyl ether
.C(OEt)v
CeH,< I yCfi^. [77°]. Formed by the
\CEt /
action of ethyl iodide and KOH on anthranol
(Goldmann, B. 21, 2506). Needles (from dilate
alcohol) ; v. e. sol. benzene, ether, and petroleum
ether. Oxidised by chromic acid to ethyl-oxan-
thranol C,H4<c(0*S)Et>°«^» ^^^^'^'
478
DI-ETHYL-ANTHRONE.
DI-ETHYL-ANTHSONE CuH.sO i.e.
CjB[4<^„j,, ^^OjHj. Formed together with the
ethyl derivative of anthranol
/C(OEt)v
^i^iK I yCjH, by boiling anthranol with
\CH — /
pono. KOHAq and EtI (Goldmann, B. 21, 1176).
[136°]. Colourless crystals,^ v. sol. benzene,
ohloroform, alcohol, and ether, sol. ligroin,
insol. aqneous alkalis. Oxidised by CrO, in
HOAc to anthraquinone. Does not combine
with Br. Not affected by HCl in HOAo at 180°.
ETHYL ABSEBTATE (G.,^E,)^sO^. (237°).
S.G. - 1*326. Decomposed by water into al-
cohol and arsenic acid (Crafts, Bl. [2] 14, 99).
ETHYL AESENITE (CiHJaAsO,. (166°).
S.G. I 1-224. Formed from Ag,AsOj and EtI.
Prepared by the action of NaOEt on AsClj or
AsBr, in alcoholic solution. Only f of the cal-
culated quantity of NaOEt is used, to avoid
saponification of the ether. Excess of AsBr, is
removed by passing in dry NH, and filtering from
the pp. Arsenious ether is also formed by heat-
ing EtjSiO, with ASjOj at 200°. It is not affected
by dry NH3 but is decomposed by water into al-
cohol and AsjOj. HBr gives alcohol and AsBr^
(Crafts, Bl. [2] 14, 99).
ETHYL-ARSIXES v. Absenic, obqanic com-
pounds OF.
ETHYLATIOH OF BASES. The displace-
ment of hydrogen by ethyl in primary and
secondary bases is usually effected by heating
with ethyl iodide (bromide or chloride), the re-
sulting compound being decomposed by potash.
Another method consists in heating the hydro-
chloride (hydrobromide or hydroiodide) of the
base with 10 p.c. more than the calculated quan-
tity of ethyl alcohol at 150° for 8 hrs. ; the yield
varies from 28 p.c. to 99 p.o. of the theoretical,
according to the base. The reaction takes place
most readily with the iodide, and least readUy
with the chloride (c/. Beinhart a. Staedel, B. 16,
29).
ETHYL-ATEOLACTIC ACID v. Ethyl deri-
Vatwe of o-OxY-a-PHENTL-PBOPIONIO AOID.
ETHYL-ATKOPINE v. Atbopinb.
ETHYL-AZAUBOLIC ACID v. Azaubolic
ACID.
ETHYL-BAEBITUBIC ACID v. Ethyl deri-
val/ime of Babbitubio acid.
ETHYL-BENZENE C,H,„ii«. C^^.C^H,. Mol.
w. 106. (186° i. v.). S.G. "j" -8673 (Brflhl, A.
235, 12) ; ^ -8760 (Schiff, A. 220, 92). C. E.
(9-9° to 135-8°) -00129. V.D. 3-65 (calc. 3-66).
S.V. 138-9. Ai„ 1-496. S.H. -393 at 0° (Schiff,
A. 234, 300).
Occwrrenee. — In Dippel's oil (Weidel a. Cia-
mician, B. 13, 70).
Formation. — 1. Prom EtBr, CjHjBr and Na
(Fittig, A. 131, 310; 133, 222; 144, 278).— 2.
From benzene, AljCl,, and EtCl or ethylene
(Friedel a. Crafts, A. Ch. [6] 1, 457 ; 14, 456 ;
Bennie, C. J. 41, 38 ; Balsohn, Bl. [2] 31, 540 ;
SoUscher, B. 15, 1680). — 3. By heating benzene
(4 pts.) with ether (1 pt.) and ZnCI, (2 pts.) for
12 hours at 180° (Balsohn, Bl. [2] 32, 617).— 4.
Aooording to Berthelot (Bl. [2] 9, 289) it is
among the products obtained by heating naph-
thalene with Qono. EIAq (20 pts.). — 6. Accord-
ing to Friedel a. Crafts (Bl. [2] 39, 195) it ia
among the carbonaceous products of the action
of AljCl, on benzene at 200°. — 6. By heating
Btyrena with HIAq (20 pts.) (Berthelot, Bl. [2] 9,
455).
ProperiAes. — ^Liquid, resembling toluene.
Beactions. — 1. On passing through a red-hot
tube it is decomposed forming styrene (2 p.c.)
benzene (15 p.o.), toluene (1 p.c), naphthalene (2-2
p.c), naphthalene dihydride, diphenyl (-6 p.c),
phenanthrene (2-6 p.c), and anthracene (-4 p.c.)
(Berthelot, Z. [2] 4, 689 ; Ferko, B. 20, 663).
2. By prolonged oxidation with dilute HNO,
or CrOg it is converted into benzoic acid. When
the oxidation is incomplete there is formed a
small quantity (10 p.o.) of acetophenone (Friedel
a. Balsohn, Bl. [2] 32, 615).— 3. In carbon di-
Bulphide it yields with ohromyl chloride CrOjOl^
a chocolate crystalline pp. of ooniposition
PhEt2Cr02Cl2 converted by moisture into phenyl-
acetio aldehyde (liJtard, A. Oh. [5] 22, 246).— 4.
Converted by boiling with hXfil, into^-di-ethyl-
benzene and a little TO-di-ethyl-benzene (An-
schiitz, A. 285, 189). — 5. Chlorine under the in-
fluence of light forms a-chloro-ethyl-benzene
(Schramm, M. 8, 101). — 6. By the action of
iromine in the dark, or of bromine in presence
of 3 p.c. of iodine in diffused daylight it yields
a mixture of 0- and ^-bromo-ethyl-benzene
(Schramm, B. 18, 1272 ; M. 8, 304).
m-Di-ethyl-benzene. [-20°]. (182°). S.G.
*f -8602. Formed, together with the p-isomeride,
when benzene is acted upon by EtBr in presence
of AlCl, (Voswinkel, B. 21, 2829). Forms no
compound with picric acid. Dilute HNO, gives
isophthahc acid. Gives C,H,BrEt2 (238°) and
C,Br,Et, [74°].
jp-Di-ethyl-benzene C,„Hn t.e. C5H4(02H5),
Mol. w. 134. (181°) (A.). S.G. '^ -871.
Formation. — 1. From ^-di-bromo-benzene
[89°] by treatment with sodium and EtI (Asch-
enbrandt, A. 216, 212 ; B. 12, 1303).— 2. From
^-bromo-ethyl-benzene, Na and EtI (Fittig, A.
144, 285).— 3. A di-ethyl-benzene (179°-185°)
is formed by passing ethylene into benzene con-
taining AI2OI, (Balsohn, Bl. [2] 31, 540 ; Friedel
a. Crafts, A Ch. [6] 14, 456) 4. By passing EtCl
into benzene containing AljCl, a di-ethyl-ben-
zene is formed which on oxidation by chromic
mixture gives an acid C5H4(C02H).CHjC0jH
subliming at 210° (Allen a. Underwood, Bl. [2]
40, 100).
Becustitms. — 1. Gives ethyl-benzoic acid on
oxidation by dilute ENO,. Chromic acid mixture
forms terephthalio acid. — 2. CrOjClj forms a
compound CeHiBtj2CrOsCl, converted by water
into phenyl-acetic aldehyde (^tard, A. Oh. [5]
22, 252).
,s-Tri-ethyl-benzone 0,jH,5 i.e. OJB[,Et,
[1:8:5]. (218°). Formed by treatmg a mixture
of acetone and methyl ethyl ketone with H^SO,
(Jacobsen, B. 7, 1430). It yields triAiesic acid
CsHs(C02H), on oxidation. Tri-ethyl-benzenes
are also formed by the action of ethylene on
benzene in presence of Al^Cl, (Friedel a. Crafts,
A. Oh. [6] 14, 466), the chief product being
s-tri-ethyl-benzene. On oxidation by CrO, this
mixture gives an acid C,gH,Os ra^stalUsing in
large needles, and ultimately trimesio acid
(Fiiedel a. Balsohn, Bl. [2] 34, 635).
ETHYL-BENZOIO ACID.
479
s - Tetra - ethyl - Tjenzene CaH.;Et4[l:2:4:5].
[13°]. (250'). Formed, together with the oon-
Beoutive isomeride, by the action of EtBr and
AlCl, on benzene; the product (250°-255°) is
treated with C180,H, and the sodium salts of
the resulting sulphonio acids crystallised from
water. The Na salt of s-tetra-ethyl-benzene
Bulphonic acid .crystallises first, and the residual
acid is converted into Ba salt. After barium
c-tetra-ethylbenzene sulphonate has crystallised,
there may still be obtained from the mother-
liquor a sulphamide [100°], possibly belonging
to i-tetra-ethyl-benzene. The sulphonio acids
are hydrolysed (Jacobsen, B. 21, 2820). Crys-
talline mass ; oxidised by dilute HNO3 and by
KMnO, to pyromellitic acid, Br gives O^Br^Et,
[112-5°].
c-Tetra-ethyl-benzeno C„Hj(C2H5)4[l:2:3:4].
(254° cor.). V.D. (H = 1)189-5 (obs.). Colour-
less liquid. Lighter than water. Prepared by
heating benzene with ethyl bromide and Al^Cl,
at 100°. On oxidation with EMnOj it gives
prehnitic acid 0^(OOM)i (Galle, B. 16, 1745).
Forms CsBrjEt, [77°] (J.).
Penta-ethyl-benzene CjHEts. (277°). S.G.
^ -8985. Obtained from benzene by the action
of EtBr and AICI3. Purified by conversion into
the sulphonio acid by CISO3H, crystallisation of
the Na salt, and subsequent hydrolysis (Jacob-
sen, B. 19, 1209 ; 20, 896, 2857 ; 21, 2814). Oil.
Does not solidify at —20°. HNO3 does not give
a nitro- compound. When treated with cone.
HjSO,, followed by fuming £[280^ there is formed
C^jBti and CjEtj.
Hexa-ethyl-benzene 0j(0jH5)|,. [129°]. (298°
cor.). V.D. (H = l) 242-1 (obs.). Formed by
beating benzene with ethyl bromide and Al^Cl,
at 100° (GaUe, B. 16, 1745 ; Jacobsen, B. 21,
2820). Formed also by passing EtCl into
benzene containing AljClj (Albright, Morgan, a.
Woolworth, C. B. 86, 887). Long colourless
monoclinio prisms. Sol. alcohol and ether, si.
sol. acetic acid. Easily sublimes.
Beferences. — Bromo-, Beomo'Nitbo-, Chloko-,
Chloko-nubo-, Nitbo-, &o., ethul-benzenb.
ETHTL-BENZENE CABBOXYIIC ACID v.
FHENyL-FBOFIONIO ACID.
Ethyl-benzene di-carboxylic acid CuHijO,
i.e. 002H.C»H4.CHMe.C0jH. [147°]. From its
nitrile and fuming HCl at 200° (Gabriel, B. 20,
2S04). Crystalline powder.
Nitrile CN.CsH,.CHMe.CN. [37°]. (285°).
Prom CN.CsHj.CHjGN by treatment with alco-
holic KOH and Mel. Triolinio prisms (Foot, B.
20, 2501). v. sol. alcohol and ether. Cone.
H^SO, at 125° converts it quickly into the i mid e
C.H4<co.^NH t"^"^' '"^^'"'^ ^°°^' ** ^°°°
gives chloro-oxy-methyl-isoquinoline.
Isomeride v. Caeboxy-phentl-pbopionio acid.
ETHYL-BENZENE SULPHONIO ACID
CjH4Et(S0jH). Two acids of this composition
are obtained by digesting ethyl-benzene with
fuming HjSO, at 100°. The more abundant acid
forms the less soluble K salt, which crystallises
well and yields an amide [108°]; fused with
KOH it yields solid ethyl-phenol (ChrustsohofE,
B. 7, 1166).
m-Ethyl-benzene snlphcnic acid
C,H,EtjSO,H [1:3:4 ?]. From the hydrocarbon
»nd C1S0,H (Voswinkel, B. 21, 2830).— KA' aq :
dimetrio tables. — BaA', 3aq : prisms, m. BoL
water. — OuA'j4aq: blue plates.
Amide OaHjEtsSOgNHj : [102°]; needles
(from alcohol).
j>-Di-ethyl-benzene snlphonic acid
C|iHaEt2(S0sH). From di-ethyl-benzene and
fuming HjSO, (Fittig a. Konig, A. 144, 277;
Aschenbrandt, A. 216, 214 ; Bemsen a. Noyes,
Am. 4, 200). Deliquescent laminse.
Salts.— EA' 3|aq.— NaA'.— BaA',4aq: leaf-
lets. S. (of BaAy 5-1 at 28°.— SrA'j 4aq.—
OaA'„ 5aq. — CuA'^ 6aq : blue plates. — PbA'j 3aq.
— Hg'A'j. — NiA'j 6aq. — CoA'j 6aq. — MgA'j. —
AgA',
Amide CsH4Etj(S0jNHJ. [97-5° cor.]
Leaflets, si. sol. water.
s-Tetra-ethyl-benzene snlphonic acid
C„HEt,SO,H. From s-tetra-ethyl-benzene and
OISO3H (Jacobsen, B. 21, 2820).— NaA', 4aq :
plates (from water), or tables (from alcohol); si.
sol. cold water, insol. diluite KaOHAq. — BaA', 9aq :
scaly crystalline pp. SI. sol. boiling water.
Amide CjHEtjSOjNBLj: [122°]; trimetrio
plates (from dilute alcohol).
c-Tetra-ethyl-benzene snlphonic acid
C„H(C2H5),S0aH. Silky plates or long needles.
Formed by sulphonation of c-tetra-ethyl-benzene.
Salts. — A'Na5aq: microscopic plates. —
A'jBa 6aq : flat prisms. — A'^Cu 8aq : Ught-blue
plates. — A'^Cd 7aq : large flat prisms.
Amide C^(Cfi^)iSO.,'SBi^ : [107°] ; glisten-
ing scales or large monoclinio prisms, v. sol.
alcohol and acetic acid, si. sol. petroleum-ether
(Galle, B. 16, 1745).
Penta-ethyl-benzene snlphonic acid
OjBtsSOjH. From penta-ethyl-benzene and
OlSOsH (Jacobsen, B. 21, 2814).— NaA' 4aq :
thin pearly plates (from water) ; m. sol. cold
water, insol. dilute NaOHAq, v. sol. alcohol. —
ElA'2aq : six-sided, trimetric plates (from water),
prisms (from alcohol) ; si. sol. cold, m. sol. hot,
water, v. e. sol. alcohol.— -NH4A' aq : trimetrio,
six-sided plates, si. sol. cold water. — ^BaA'2 9aq :
from the Na salt and Ba(OAo)2. Small scales ;
T. si. sol. boiling water.
Beference, — Chiiobo-ethyl-benzene bulcho-
mo ACID.
ETHTL-BENZHTDBOXAUIC ETHEB «.
BeNZENYL-ETHOXIM BTHYXi ethbe.
TETEA-ETHYL-BENZIDINE v. Tetea-
BTHYIi-DI-AMIDO-DIPHENYL.
ETHYL BENZOATE v. Ethyl ether of Benzoio
ACID.
o-ETHYL-BENZOIC ACID C,H,A »-«•
C,H4EtCOjH[l:2]. Mol. w. 150. [68°]. Formed
by reduction of tri-chloro-, or di-chloro-bromo-,
vinyl-benzoic acid with sodium amalgam (Zincke,
B. 20, 2056). Formed also by reduction of ace-
tophenone carboxylio acid or of phthalyl-aoetio
acid C8H4(CA)CH.C02H with HI and P at 180°
(Gabriel a. Michael, B. 10, 2206),— Slender flat
needles. — AgA' : long needles.
. w-Ethyl-benzoio acid C,H,Et.C02H [1:3].
[47°]. Fprmed by oxidising w-di-ethyl-benzene
with dilute HNO3 (Jacobsen, B. 21, 2820).
Needles, insol. cold water. — CaiA',4aq: needles,
V. sol. water.
jp-Ethyl-benzoic acid CBH45!t.C02H[l:4].
[113°].
FormaUon. — 1. By the action of sodium and
00, upon y-broino-ethyl-benaene (Kekulfi, 4.
480
ETHYL-BENZOIO AOID.
137, 178; KekuU a. Thorpe, 0. J. 22, 366).—
2. By oxidising di-ethyl-benzene with boiling
dilute HNO, (Fittig a. K6nig, A. 144, 277;
Asohenbrandt, A. 216, 218).
Properties. — Small plates (from water) or
prisms (from alcohol), v. si. sol. cold -water, v.
Bol. alcohol, ether, ohlorofoim, and benzene.
May be sublimed. Melts under water. Gives
terephthalio acid on oxidation.
Salts.— BaA'j 2aq (A.).— BaA'j aq (P. a. K.).
5. 2.— CaA'j 3aq (A.)— OaA'^ 2aq (P. a. E.) :
feathery tufts of needles. — CuA'j aaq.-^AgA' :
needles (from hot water).
Di-ethyl-benzoic acid 0„Hu02 i.e.
C„HjEtj.COjH. Formed, together with benzoic
acid, by fusing di-ethyl-carbobenzoio acid
C,,H„02 with potash (Zagoumenny, A. 184, 171).
Oil. — AgA' : laminffi (from water).
References. — Chloro- and Nimo- ethyl-
BENZOIC Acms.
ETHYL-BENZOPHENONE v. PHEireii-BTHyi.-
PHENYIi-KETONE.
ETHYL- BENZOTL-ACETIC ACID v. Benz-
OYL-ACETIO AOID.
ETHYI-BEBTZYI- v. Benzyl-ethyl-.
ETHYl-DIBENZYL v. Phenyl-ethyl-
phenyl-ethane.
ETHYL-DI-BENZYI-PHOSPHINE
EtP(C^,)j. (320°-330°). Formed by treating
with NaOH the distillate from Et2P(C,H,)jCl
(«. infra) (Collie, C. J. 53, 725).
Benzylo-chloride iitP(C!,H,)gOI aq. De-
composed on distillation , giving ethylene, stilbene,
HOI, &c.
Di-ethyl-benzyl-phosphine EtjPC,H,. (250°
-256°). Formed by distilling EtsPC^HjOl and
treating the resulting EtjPC,H,Clia with NaOH
(ColUe, a. J. 53, 724).
Oxide Et2(C,H,)P0. (329°). Formed as
above, and also by heating Et2(C,H,)2P0H.
Long needles. Converted by Na into Et^FC^H,.
Sulphide Etj(C,H,)PS. [95°]. (300°-310°).
Formed by adding 8 to an ethereal solution of
EtjPC,H,. Crystalline; insol. water. When
heated with Ka the phosphine Et^PC^H, is
liberated.
Benzylo-chloride BtjP(0,H,)5;01. De-
composed on heating into CgH^ and
EtP(C,H,)j01H.
ETHYL BENZYL SULPHIDE «. Mhyl
deri/vatvue of Benzyl mebcaftan.
TBI-EIHYL-BISUVTHINE v. Bismuth
IBI-EIHIDE.
TBI - ETHYL . BIUBET CsH.jNaOj i.e.
NEt(C0.NHEt)2. Formed by warming oyanurio
ether with baryta (Limpricht a. Habich, A. 109,
104 ; Nenoki, B. 9, 1011). Thick oil, si. sol.
water, v. sol. alcohol and ether. Split up on dis-
tillation into cyanic ether and di-ethyl-urea.
ETHYL BOBATES.
Ethyl ortho-borate (C2H5)3B03. (120° i.V.).
S.G.a-887;'-^-861. T.D. 5-14 (calc. 6-07). Pre-
pared by the action of alcohol on BOl, (Ebel-
men a. Bouquet, A, Ch. [3] 17, 55; Bowman,
P. M. [3] 29, 546). Formed aJso by distilling a
mixture of dry KEtSO, with anhydrous borax
(Bose, P. 98, 245), and by the action of absolute
alcohol as powdered BA (SchifE, Bl. [2] 5, 372 ;
6, 36). Colourless liquid with alcoholic odour,
iiurns with green flame. Mixes with ether and
alcohol. Decomposed by water in a few minutes
into alcohol and boric acid. HNO3 gives nitric
ether and boric acid. Acetic acid forms acetic
ether and BJO^. POL forms EtCl, POOl, and
EtBOj.
Ethyl metaborate EtBOj. Among the pro-
ducts of the action of alcohol on B^O,. Dense
liquid, absorbs moisture from the air, being
split up into alcohol and boric acid. Gives with
alcohol EtjBOj. Acetic acid at 190° gives acetic
ether and HBO2. Cannot be distilled, for it
splits up at high temperatures into Et^BO, and
gummy EtBgOgi which behaves like EtBO, to-
wards water and alcohol.
ETHYL-BOEIC ETHEB EtB(0Et)2. The
compound EtB(0Et)2,B(0Et)3 (112°) is formed
by action of ZuBtj (2 mols.) on boric ether (1 mol.).
Water decomposes it into ethyl-boric acid
BEt(OH)j and alcohol (Frankland, Pr. 25, 165).
Di-ethyl-boric ether EtjfB.OBt (103°). Prom
ZnEtj and EtB(0Et)2,B(0Et)a. Dry oxygen con-
verts it into BEt(0Et)2. Water converts it into
diethyl-borio acid EtjB.OH, which absorbs oxy-
gen from air, forming crystals of EtB(OEt).OH,
whence H^O forms alcohol and EtB(0H)2.
ETHYL BEOMIDE CjHsBr. Bromo-ethane.
Mol. w. 109. (38-4°). S.G. V 1-4189 (Mende- .
lejeff) ; 1-4555 (Weegman, Z. P. C. 2, 218) ; i|
1-4499; If 1-4325. M.M.5-851atl9-7°. S.V. 77-07
(Schiff). Critical temperature : 236° (Pawlewsky,
B. 16, 2633).
Formation. — 1. The rate of formation from
alcohol and HBr has been studied by Villiers
(C. B. 90, 1488).— 2. When a mixture of ethyl-
ene and HBr is passed over Al^Br „ there is formed
Al.BrjCjHs, ethyl bromide, and saturated hydro-
carbons (Gustavspn, J. pr, [2] 34, 161). — 3. Toge-
ther with other products by heating alcohol (1 pt.)
with bromine (3pts.) (Lowig, A. 3, 291).
Preparation. — 1. By adding bromine (8pt3.)
gradually to alcohol (40 pts.), mixed with clear
phosphorus (Ipt.), and distilling (Serullas, A.
Ch. 34, 99). Personne (O. B. 52, 468) employed
red phosphorus (40 g.) with dry alcohol (160 g.)
and bromine (100 g.). — 2. By mixing H^SO,
(10 pts.) and alcohol (5 pts.), allowing to stand
for some time, and then diluting with water
(3 pts.), adding KBr (5 pts.) and distilling. The
yield is 80 to 100 p.o. (De Vrij, J. Ph. [3] 31
169 ; cf. C. J. 36, 127 ; D. P. J. 229, 284).
Prqperiies.— Colourless liquid with ethereal
odour and ansesthetic influence (Bobin, C. B. 32,
649). y. si. sol, water, miscible with alcohol
and ether. Burns with _di£Sculty, .forming a
smokeless green flame. Not acted upon by
HNO3, by H2SO4, or by potassium.
Beactions. — 1. When passed through a red-
hot tube ethylene and HBr are among the pro-
ducts.— 2. Ammonia gives ethylamines. Other
bases act similarly. — 3. Alcoholic potash forms
KBr and ether (Berthelot, A. 92, 351).— 4. Brom-
ine forms CHa-OHBrj, CHjBr.CHjBr, and
CHjBr.CHBrj (114°) (Tavildaroff, A. 176, 12).—
5. The dry copper-zinc couple forms BrZnEt, the
combination being facilitated by the presence of
a little EtI. In presence of water or alcohol
ethane is given off on warming (Gladstone a.
Tribe, C. J. 27, 410).— 6. A mixture of EtBr
passed over Al^Br,;, or the compound AlBrsGjH,
at 60° gives saturated hydrocarbons (Gustav-
son).
DI-ETHYL SEMI-CARBAZIDE.
481
Oomponnd EtBrE2S23aa (Forcrand, A.
Ch. [5] 28, 29).
ETHYL-BBOIIO-ACETO-ACEIIC ETHEB «.
Bbomo-aceto-acetio etbeb.
ETHYL-DI-BROMO-DI-ALLYI-AMINE
CiHiaBraN i.e. EtN(0,H<Br)j. From dibromo-
allyl-amine and Btl at 100° (Maxwell Simpson,
P. M. [4] 16, 257). Pungent bitter oil, alkaline
to test papers. Precipitates Gu(0H)2 from
capric salts.
ETHYL BROHO-ALLTL OXIDE CgHaBrO i.e.
Et.0.CH2.CBr:Ctt,. (133°). S.G. i^ 1-26. From
BtO.CH2.CHBr.CH2Br and NaOH (Henry, B. 5,
188). ,,
Ethyl di-bromo-allyl oxide
Et.0.CH2.CBr:CHBr. From ethyl propargyl
oxide and Br (Liebermann a. Eretschmer, A.
158, 234).
ETHYI-BSOMO-AIIINE v. Ethyiamine.
EIHYL-BBOMO-ANILIKrE v. BB0M0-ETEyi>-
ETHTL BEOMO-PENTENYl OXIDE
CsHsBr.O.Et. (179°). S.G. 12 1-23. From
bromo-amylene bromide(tri-bromo-pentane) and
alcoholic KOH (Eeboul, A. 183, 84).
ETHTL-BBOHO-PODOCABFIC ACID v.
FoilOCA£Fia ACID.
ETHYL ISOBUTYL CARBONATE C^H^Oa
i.e.Bt(C,H,)COa. (160-1° cor.). S.G. ^i -92 (Bose,
A 205, 230).
ETHYX-ISOBUTYL-GLYOXALINE C.H^Nj
i.e.0^^t{G^s)TS^. OxalethyUnoamyUne. (225°),
S.G. — -9291. The hydrobromide is formed
from isobntyl-glyosaUne (glyoxal-isoamyline) and
EtBr (Badziszewsky a. Szul, B. 17, 1294). Oil,r—
B'^HgPtCl, : orange prisms.
ETHYL ISOBUTYL KETONE
CjHs.CO.CH^r. (185°) at 735 mm. S.G. g
•829 ; « -815. Formed when CO is passed over
a mixture of sodium isovalerate and NaOEt at
160° (Loos, A. 202, 327). Also from isovaleryl
chloride and ZnEt, (Wagner, Bl. [2] 38, 264 ;
J. B. 16, 678). Gives on oxidation acetio and
iBov&il6i^c Acids
Ethyl «eri-butyl ketone Et.CO.OMe3. (126°).
S.G. a -SSI; i2 -810. From CMea.COOl and
ZnEtj (Wyschnegradsky, A. 178, 10'4). Liquid
smelling of mint and camphor. Oxidised by
CrOj to CMeaCOaH.
ETHYL-BUTYL-OXIDE CeH„0 i.e.
EiO.C^H,. (91-4°). S.G. g -768. S.V. 150-1.
C.E. (0°-10°) -00116 (Dobriner, ii. 243, 5; c/.
Lieben a. Bossi, A. 158, 167).
Ethyl isobutyl oxide EtOCH^Pr. (79°). S.G.
•75. From EtI and KOC4H5 (Wurtz, A. Ch. [3]
42, 129 ; A. 98, 117) or from CjEtBr and KOEt
(Meissler, O. C. 1887, 479).
Ethyl tert-butyl oxide EtOCMe,. (69°).
Formed by heating tert-butyl bromide (2 vols.)
with NBt, (5 vols.) and alcohol (5 vols.) at 100°
(lleboul, /. 1881, 409).
ETHYL ISOBUTYL SULPHATE ?
Et(C4H„)S0,. From C.HjO.SOjCl and alcohol
(Behrend, J. pr. [2] 15, 34). Decomposed by
water into alcohol and H(0,H9)SO,.
ETHYL ISOBUTYL (o)-THIOCAEBONATE
EtO.CO.SC^Hj. (192°). S.G. i« -994. From
ClCOjEt an^ NaSOA (MyUus, B. 6, 313).
Ethyl-isobutyl (a)-di-thio-carbonate
EtS.CO.OC^H,. (193°). S.G. is .994. From
Vol. II,
0100^045; and NaSEt (M.) ; v. Ethyi. thio-
OABBONAIES.
Ethyl-isobntyl dithiocarbouate
C4H,0.CS.SEt. (228°). From OjHbO.OS.SR
and EtI at 100° (MyKus, B. 5, 972). Yellow
liquid with unpleasant odour, with a taste like
aniseed.
ETHYL CAMPHENE 0,„H,5(0jH5). (198°-
200° cor.) at 742 mm. S.G. 22 -9709. V.D.
= 5-55 (found). Prepared by the action of sodium
on a mixture of solid camphor-diohloride [155°]
and ethyl iodide (Spitzer, B. 11, 1817). Mobile
fluid of turpentine-Uke smell.
ETHYL-CAMPHOB v. Camphob.
ETHYL CABBAMATE v. vol. i. p. 679.
ETHYL - CABBAMIC ACID NHEt.OOjH.
Ethyl-ammonium salt NEgBtA.'. From
ethylamine and OOj at —18°- Snow-white
powder. Decomposed by water although, like
ammonium <;arbamate, it does not immediately
ppt. BaCl, in the cold (Wurtz, A. Ch. [3] 30, 443).
Ethyl ether NEtH.C0jEt. (176°). V.D.
4-07. S.G. 2i -986. From OlCOjEt and NEtH,
(Sohreiner, J. pr. [2] 21, 125 ; 22, 353). Formed
also by heating cyanic ether with alcohol in
sealed tubes at 100° (Wurtz, C. B. 37, 182). Oili
Decomposed by potash into ethylamine, alcoholi
and KjCOa.
Di - ethyl ■ carbamic chloride Cl.CO.NBtj.
Chloro-formio acid diethylamide. (190°-195°).
Prepared by the action of P01,ondiethyl-oxamio
acid, CO being evolved (Wallach, B. 14, 746).
Liquid. By treatment with diethylamine it
gives tetra-ethyl-urea. By water it is decom-
posed into CO, and diethylamine hydrochloride.
ETHYL CARBAMINE ONCA. (78°). Mol.
w. 55. From ethyl iodide and silver cyanide
(v. vol. i. p. 680). Also from EtI and mercuric
fulminate (Calmels, J.pr. [2] 30, 319). Stinking
liquid. Does not solidify at —68°. Split up by
acids into formic acid and ethylamine. EgO
added to a solution of ethyl carbamine (1 vol.)
in ether (4 vols.) forms C^B^fii [112°]. Br
forms oily NCaHjBrj (Tsoherniak, Bl. [2] 30,
105).
Ethyl - carbamine cyamide v. Cabbimido-
BTHYli-UEEA.
DI-ETHYL SEMI-CAEBAZIDE OaHgNgO i.e.
NHj.C0.N2H2Et. [106°]. From ethyl-hydrazina
hydrochloride and cone, aqueous potassium
cyanate (Fischer, A. 199, 284). Laminae ; v. e.
sol. water and alcohol, si. sol. ether and cone,
alkalis. Beduces Fehling's solution and HgO
only when warm.
£-Dl- ethyl -semicarbazide 0,E,,N,0 i.e.
NHEt.CO.NEt.NH2. From the nitrosamine of
s-di-ethyl-urea NHBt.0O.NBt.NO by reduction
with zinc-dust and HOAo in alcoholic solution
(Fischer, A. 199, 284). Crystallises with diffi-
culty ; V. sol. water and alcohol. Beduces Feh- ■
ling's solution only when warm. Boiling cone.
EClAq splits it up into C02,ethyl-hydrazine, and
NHjEt.— B'HCl : slender needles.— B'jHjPtCl,.
u-Di-ethyl-semi-carbazide
NHj.00.NH.NHEt. [149°]. Formed by the
action of potassium cyanate on the neutral salts
of u-di-ethyl-hydrazine (F.). Long slender
prisms (from alcohol) ; v. e. sol. alcohol afld hot
water, v. si. sol. ether. Beduces boiling Fehling's
solution with much difficulty. — B'^H^PtOlg :
slender yellow needles (from alcohol).
4S?
DT-ETHYI. SEMI-CAEBAZIDE.
Nitrosamine NH2.00.N(NO).NEt2. YeUow
plates ; si. sol. water, v. sol. alcohol and ether.
Dilute KOH splits it up at once into diethyl-
amine, COj, ammonia, and NjO. \
ETHYl-CABBAZOLE O.^HjaN i.e. \
<]]^6^*^NEt. [67°]. From potassium carb-
azole and EtI (Graebe, A. 202, 23). Leaflets,
sol. ether and hot alcohol, insol. water. Its
piorate C„H,sNO|jHj,{N02)30H crystallises in
needles [97°].
ETHYL-CASBAZOLINE C„H„N i.e.
C,^„NEt. Hydroiodide B'HI. Promoarb-
azoline, EtI, and alcohol at 100° (Graebe a.
Behaghel, A. 202, 25). Thick tables, v. sol. hot
ETHYL - CABBIMIDO - METHYL - THIO -
UEEA SC<^g®>C:NEtorMeNH.CS.N:C:NEt.
Methyl-tJdo-carbamine-ethyl-cyaimde. [106°].
Formed by the action of ethyl iodid'e upon
sodium carbimido-methyl-thiourea (Wuuderlioh,
B. 19, 448).
. ETHYL-CARBIMIDO-PHENYL-THIO-irEEA
SC <;^]^>C:NEt or PhNH.CS.N:C:NEt. Phe-
nyl - thio - carbandne - etfi/yl - cywrmde. [119°].
Eoimed by the action of ethyl-iodide upon so-
dium carbimido-phenyl-thio-urea. Crystalline
solid. V. sol. water and alcohol. Indifferent
body (Wnnderlich, B. 19, 448).
ETHYL-CABfilKIDO-ITSEA
OC<^^^C:NEt or H^N.CO.NiCiNEt. Car-
bamme-ethyl-cyamide. [121°]. Formed by the
action of ethyl iodide upon sodium carbimido-
urea (' amido-dioyanio acid '). Neutral body
(WunderHch, B. 19, 448).
SI-ETHYL-CABBINOL v. Ann. alcohol.
Tri-ethyl-carbinol v. Hepiti. aloohol.
SI-EIHYL-CABBINYL v. Aim..
SI-ETHYL-CABBOBENZOIC ACID C„H,A
or C,sH,A? [102°]. (239°) at 11 mm. An
acid formed when deoxybenzom is heated with
alcoholic KOH (Limpricht a. Schwanert,^. 155,
66; Zagoumenuy, A. 184, 163; Anschutz a.
Berns, B. 20, 1392). Slender needles (from
ether). Converted by potash-fusion into benzoic
and di-ethyl-benzoio acids. Dilute HjSOj forms
crystalline C,gH,j02 [132°] and other bodies.
HJJO, gives a di-nitro- derivative [156°].
Salts. — AgA': amorphous. — EtA': oil.
ETHYL CARBONATE C.,H,oO, i.e. Et^CO,.
Mol. w. 118i. (126° cor.) (Kopp, A. 95, 325).
S.G.'y'-9762. /*;,= 1-3897. »«,= 45-41 (Briihl,
A. 203, 23). H.F.p. 152,500. H.F.V. 149,310
{Th. 4, 213). H.C. 641,448 (Louguinine, Bl. [2]
41, 389). V.D. 4-09 (obs. and calo. Cahours).
Formation. — 1. By the action of potassium
or sodium on oxalic ether at 130°, the metal
being added as long as CO escapes; water is
then added, and the Et^CO, dried over OaCL
and rectified (Ettling, A. 19, 17).— 2. By distil-
ling a mixture of KEtCOa with KEtSO, (Chancel,
C. B. 31, 521).— 3. By the action of NaOEt on
oxalic ether (Cranston a. Dittmar, O. J. 22,
441).— 4. Prom ClCO^Et and NaOBt (Schreiner,
J.JW-. [2] 22,353).
Properties. — Colourless liquid, burning with
blue flame. Insol. water, v. sol. alcohol and
ether. Chlorine gives products of substitution
(Cahours, A. Ch. [3] 9, 201). Saturated with
HBr and heated to 100° there are formed EtBr,
COj, and water (Gal, C. B. 59, 1049). By heat-
ing with sodium or NaOEt in sealed tubes it
yields NaEtCO,, carbonic oxide, and Et^O
(Geuther, Z. [2] 4, 656). Ammonia at 100°
forms carbamic ether ; at 180° ammonia gives
urea (Natanson, A. 98, 287). PCI5 gives EtCl
and ClCOjEt (Geuther, A. 205, 247).
Potassium ethyl carbonate EEtCO,. When
CO2 is passed into a solution of EOH in absolute
alcohol there is formed a crystalline deposit
consisting of KEtCOs, KHCO3, and K^COa ; the
mass is washed with ether, the KEtCO, is then
dissolved in alcohol and ppd. by ether (Dumaa
a. Peligot, A., Ch. [2] 74, 6). White nacreous
salt ; split up by water into alcohol and KHCOj.
NaEtCO, and amorphous Ba(EtC0s)2 are ob-
tained by passing CO, into alcoholic solutions
of NaOEt and Ba(0Et)2 respectively (Beilstein,
A. 112, 124 ; Destrem, A. Ch. [5] 27, 10).
Ethyl ortho-carbonate C(OEt),. Mol. w. 192.
(159°). V.D. 6-80 (calc. 6-65). Sodium (24 g.)
is added in small portions to a boiling solution
of ohloropicrin (40 g.) in absolute alcohol (300 g.);
as soon as the reaction is finished the excess of
alcohol is distilled oS and water is added to the
residue ; the oil is then dried by CaCl^ and
rectified (Bassett, G. J. 17, 198). Oil, with
peculiar aromatic odour. Decomposed by boil-
ing alcoholic KOH. Bfi, at 100° forms boric
ether and Et^COs. Bromine forms EtBr, Et2C03,
bromal, &c. (Ladenburg a. Wichelhaus, A. 132,
166). Ammonia forms guanidine.
Reference : Teiba-chloro-di-ethylcabbonatb.
ETHYL-OABBOPYEEOL-AMIDE v. Ethyl-
EYBEOLE CAEBOXYLIC ACID.
ETHYL -CARBOSTYBIL v. Ethyl ether of
OXY-QUINOLINE and OXY-ETHYL-QUINOLINE.
ETHYL CABBYLAMINE v. Ethyl-cabb-
AMINE.
ETHYL CETYL OXIDE (CjH5)(Ci5H3,)0.
[20°]. Fine white needles. From oetyl iodide
and EtONa (Becker, A. 102, 220 ; Walder, B.
20, 1754).
ETHYL PEBCHLOEATE CjHsClO,. Obtained
by distilling a mixture of Ba(EtSO,)j with
Ba(01O4)2 in quantities of 4 g. at a time (to
avoid explosion) (Clark, Hare, a. Boyle, P. M.
[3] 19, 370 ; Eoscoe, C. J. 15, 213). The distil-
late separates into two layers, the upper one
consisting of water which may be removed by
blotting-paper. Colourless heavy oil, with
pleasant odour and sweet taste. Explodes on
the least provocation with excessive violence.
It may be kept under water or in alcoholic
solution. It may be ^stilled under a. layer of
water, passing over at 74°. It is immediately
saponified by alcoholic potash.
ETHYL CHLOEIDE 0^01. Chloro-ethane.
Mol. w. 64J. (12-5°) (Eegnault, J. 1863, 67).
S.G. f -9230 ; | -9171 (Perkin, 0. J. 45, 449).
V.D. 2-22 (calo. 2-24). H.F.p. (gaseous) 28,000;
(liquid) 84,400 (Berthelot) ; 30,710 (Thomsen,
Th.). H.F.V. 29,550 {Th.). M.M. 4-039 at 5°
(P.). S.V. 75-8 (Eamsay).
FormaUon,. — 1. By chlorinating ethane
(Schorlemmer, O. B. 58, 703 ; A. 132, 234).—
2. By the action of HCl on alcohol alone or in
presence of ZuCl, (Bobiquet a. CoUn, A, Ch, [2]
ethyl-couMazonio acid.
483
1, 343 ; Eegnault, A. Oh. [3J 71, 355 ; Kuhlmann,
A. 33, 108 ; Lowig, P. 45, 346).— 3. By the action
of SCI, PCI5, k\G\, SbClj, FejCl,, Sn01„&o., on
alcohol. — 4. From EtI and chlorine. — 5. By
treating acetic and other ethers with HCl.
Prepa/ration. — 1. HCl is passed into a boiling
solution of ZnClg (2 pts.) in 95 p.c. alcohol
(3 pts.) in a flask with inverted condenser. The
escaping gas is washed with water. The yield
is nearly the theoretical (Groves, <7.e7'.27,637). —
2. By distilling a mixture of alcohol (5 pts.),
HjS04 (2 pts.), and NaCl (12 pts.).
Properties. — Gas, burning with green-edged
flame. Y. si. sol. water, y.i e. sol. alcohol and
ether. Gives no pp. with silver nitrate solution
in the cold.
Reactions.— 1. Aqueous HI (S.G. 1-9) at 130°
converts it into EtI.— 2. SO, forms ClSOrOEt
(E. Williamson, G. J. 10, 100). By-j)roducts
are also formed (Von Purgold, B. 6, 502). —
3. Aqueous AgNOj at 100° gives a pp. of AgCl
(G. C. Foster). — 4. BoiUng aqueous EOH slowly
forms alcohol ; alcohoho potash acts more
readily, forming KCl, ilcohol, and ether (Balard,
A. Oh. [3] 12, 302).— 5. Ammoma forms ethyl-
amines (Groves, O. J. 13, 331). Equal volumes
of C^HjCl and NH, gas submitted to a pressure
of 70 atmospheres for 48 hours at 175° do not
react. The introduction of a small quantity of
alcohol does not affect the result. la the cold
an alcoholic solution of NHj and CjHjCl requires
to be kept several days before any action com-
mences, and the reaction is not complete after
several months (Vincent a. Chappuis, Bl. [2] 45,
503).— 6. Alcoholic K^S and KHS give Et^S and
mercaptan respectively (Eegnault).— 7. Passed
over red-hot lime it forms acetic acid, CH„ and
hydrogen (Ii. Meyer, A. 139, 282 ; c/. Dumas a.
Stas, A. Ch. [2] 73, 154).
Derwati/ves. — Chlobo-ethanes and Ohlobo-
BBOMO-ETHANES, ETHYLENE OBLOBISE and EtHYIi-
IDENE OHLOBIDE.
ETHTL-CHLOBO-ACETO-ACEIIC EIHES
V. Chlobo-aoeio-aoetic bthek.
ETHYL CHIOEO-ACETYLENE CAEBOXY.
Lie ACID V. ChiiObo-buiane cabeoxyiiIC acid.
ETHYL - M - CHLOEO - DI - ALLYL - AMINE
NEt(C3H4Cl),. (0. 200). From NH(C,H,Cl)j and
Btl at 100° (Engler, Bl. [2] 9, 134 ; A. 142, 81).
Oil.— B'sHjPtCIj : crystalline.
Si - ethyl - chloro - allyl - amine. Ethylo-
chloride CjHiCl.NBta01. Two compounds of
this constitution are formed by heating s-tri-
chloro-ethane CHjC1.CHC1.0H:sC1 with NEt,
(Eeboul, C. B. 95, 993). They differ in the so-
lubility of their Pt salts. Two di-ohloro-propyl-
enes appear to be intermediate in the formation
of these ethylo-chlorides.
ETHYL o-OHLOEO-ALLYL OXIDE 0^010
i.e. Et.O.CHj.CCl:CH,. (110°). S.G. s 1-011 ;
!l?-995. From CHj:CCl.CHX!l and alcoholic
KOH (Friedel a. Silva, J. 18*3, 323). Formed
also from ethyl allyl oxide by successive treat-
ment with CI and KOH (Henry, B. 6, 189).
Ethyl j3-chloro-allyl ojtide
Et.O.CH,.CH:CHCl. (120°-12S''). S.G. 21.021;
8£-994 From CHj01.CH:CHCl and alcoholic
KOH (P.a.S.). Br form8EtO.CH2,CHBr.CHCIBr
(220°).
EXHYL-CELOSO-AUINE V. EimLAUiNi.
DI-ETHYL CHLORO-AMYL PHOSPHATE
Etj(0<H,.CHCl)PO<. From CA.CHj.PO(OH),
by successive treatment with FGl, and alcohol
(Fossek, M. 7, 20).
ETHYL-GHL0E0-AinLIN£v.GBLOBO-ETHn.-
AKI1.INE.
TSI . ETHYL . CHLOEO • AUEOFHOSPHITE
EtsPAuClO,. [0. -10°]. S.G. 2-025. Obtained
by adding absolute alcohol to a mixture of AuCl
and dry phosphorus and ppg. by water (Lindet,
C. B. 103, 1014). Crystalline mass ; decomposes
about 100°. Insol. water, sol. alcohol, ether,
and benzene. NH, forms EtaPAu010,NjH,.
ETHYL-CHLOEO-BENZENE v. Chlobo-
ETHTIi-BENZGNE.
ETHYL-CHLOEO-BEOMO-PBOFYL OXIDE
Et.CO.0,H501Br. (187°). From epiohlorhydrin
and EtBr at 200° (Eeboul a. Louren<;o, A. 119
238).
ETHYL CHLOEO-BDTENYL OXIDE
04H,C1.0Bt. (134°). From CH,.CH:CH.0H0l2
and alcoholic KOH (Kekulfi, A. 162, 98).
ETHYL CHLOEO-BXTTYL OXIDE
CHjCLCHBtOBt. (141°). S.G. 2 -974. V.I).
69-3 (calo. 68-8). From ZnEt^ and an ethereal
solution of di-ohloro-di-ethyl oxide (Lieben, A.
123, 130 ; 133, 287 ; 146, 220). Oil, miscible
with alcohol and ether.
Reactions. — 1. HI gives EtI and secondary
butyl iodide. — 2. With NaOEt it gives butylene
glycol diethylic ether: CHj,(0Bt)0HEt.OEt,
(147°).— 3. PBr, gives CHjCl.CHEtBr, ethyl
bromide, and CHjBr.CHEtBr.
ETHYL-CHLOAO-ETHAHE TETBA-CAE-
BOXYLIC ACID v. Chlobo-buiaiie tetba-cab-
BOXYIiIOAClD.
ETHYL- CHLOEO -MALOmC ETHEB v.
ChIiOBO-BTHYL-MALONIO ethee.
ETHYL-DI-CHLOEO-FHOSFHmE v. Etbyl-
FHOBFHINE.
ETHYL CHLOEO - I80FE0FYL OXIDE
CH„Cl.CH.Me.OBt. (118°). S.G. 2 -984. From
ZnMe, and dichloro-diethyl ether (Lieben, A.
146, 225). PBr, gives MeBr, CHjCl.CHMeBr,
and CHjBr.CHMeBr.
ETHYL-OHLOBO-aUIIfOLIXE «. Chlobo-
EIBYL-QUINOLniE.
ETHYL-CHLOEO-SULFHATE v. Eihyi. BDli-
fHATE.
ETHYL CHEYSOifDIK v. Bemene-A.zo-ethyl-
phenyUne-diamme.
ETHYL-CINCHEHICACID v. Cinchene.
ETHYL-CIHGHOH AMINE V. Cinchona bases.
ETHYL-CIHCHONIC ACID v. Bihyi. qdin-
OLINE CABBOXYIiIO ACID.
ETHYL-CINCHONIDINE v. Cinohonidinb.
ETHYL-CINCHONINE «. Cinchoninb.
ETHYL-CITEIC ACID v. Citbic acid.
ETHYL-CODEXNE v. Codeine.
ETHYL-CONHYDEINE v. Coniinz.
ETHYL-COHllNE v. Coniine.
ETHYL - COUMAZONIC ACID Ci.H.jNO,
.CMe,.0
(?). [202°]. Small
lEt
glistening pyramids. V.aol. alcohol, insol. water.
Formed by boiling (3:4:l)-amido-oxypropyl>
benzoic acid with propionic anhydride.
Salts. — A'E,HC1: very soluble white
needles. — A'H,HjS04: very soluble white needles
<Widmann, B. 16, 2576).
1x3
,0.H.(CO^<^^J,^
484
ETHYL CRESYL ETHER.
ETHTL CBESYL ETHEB v. Ethyl derivative
of CnEsoL.
ETHYL-CEOTONIC ACID v. Hbxenoio acid.
ETHYL ISOCBOIYL ETHEB v. Mtlvyl ether
of BuTENTIi ALOOHOIi, vol. i. p. 639.
ETHYIi-CITMENE v. Eihyl-fbofyIi-bekzehe.
ETHYI-CTTMIDINE 0„H„N i.e.
C.HjMe3NHEt. (220°-230°). Formed by heat-
ing comidine hydrochloride (1 mol.) with alco-
hol {X mol.) for 4 hours at 125° (Buttan, B. 19,
2383);
ETHYL CYANAUISE «. Cyanamide under
CXANIO ACID.
ETHYL-CYAHIC ACID v. Ctanio acid. -
ETHYL CYANIDE v, Peomoniikilb and
SiHYIi cabbamhie.
ETHYL-CYANUSIC ACID v. Cyanuric acid
under Cyanic acid.
ETHYLENE C^, i.e. CB.^.CB^. Mol. w. 28.
[- 169°] (Olszewski, jlf. 8, 71) ; ( - 103°) (Cailletet,
CM. 94, 1224 ; Wroblowsky, AT. 4, 338). Y.D.
•9784 (Saussure; cale. •9702). H.F.p. -8,000
fFavre a. Silbermann) ; -9,400 (Berthelot,.4. Ch.
[S] 23, 180); -4,160 (Thomsen, J. pr. [2] 23,
158); -2,710 (Thomsen, Th.). HJ-.v. -3,290
(Th.): Critical temperature, 13°. S. -25 at 0° ; S.
(alcohol) 3-6 at 0° (Carina, A. 94, 133). Dis-
covered by treating alcohol with HjSO, in 1795
by the four Dutch chemists : Deiman, Psets van
Troostwyk, Bondt, and Lauwerenburgh {Crell.
Ann. 1795, ii. 195, 310 ; Oilb. Ann. 2, 201). It
is a product of the dry distillation of most
organic bodies, e.g. formates, acetates, butyrates, .
fats, resins, caoutchouc, wood, and coal. It is
the most abundant illuminating constituent in
coal gas.
Fwmation. — 1. Formed, as well as other
hydrocarbons, when a mixture of CSj and H^S
or HjP is passed over red-hot copper ; or, more
abundantly, when a mixture of GS,, H^S, and
CO is passed over red-hot iron (Berthelot, C. B.
43, 236).— 2, Formed together with OH, and
batylene by the dry distillation of barium for-
mate.— 3. By heating a mixture of alcohol (1 vol.)
with cone. HjSO, (4 vols.) (Mitsoherlioh, A. Ch,
[3] 7, 12).— 4. By heating alcohol (1 pt.) with
fused BjO, (4 pts.) (Ebehnen,4. Ch. [3] IG, 136).
6. By Oie electrolysis of a concentrated solu-
tion of sodium succinate (Eekul6, A. 131, 79). —
6. Together with benzene, by heating styrene
with hydrogen in sealed tubes (Berthelot, J.
1866,544). — 7. By treating ethylidene chloride
with sodium (ToUens, A. 137, 311).— 8. From
ethyl iodide and zino (E. Frankland a. L.
Dobbie, C. J. 33, 545).
Preparation. — Alcohol (25 g.) and HjSO,
(150 g.) are heated in a flask to 165°, and a mix-
ture of alcohol (1 pt.) and HjSO^ (2 pts.) is run
in slowly. The gas is washed with KaOHAq
and HjSO, (Erlenmeyer a. Bunte, A. 168, 64;
192, 244).
Properties. — Colourless gas with faint ethereal
' odour (?). V. b1. sol. water, si. sol. alcohol, m.
sol. ether. Pure ethylene burnt at the rate of
5 cubic feet per hour emits a hght equal to 68*5
standard candles ; the illuminating power of a
given quantity of CjH, is increased by moderate
admixture with H, CO, or CH^, although the
actual amount of light given per cubic foot of
the mixture is less than that given by pure
ethylene. The iutringio illumina^g power ii
reduced by admixture with N, COj, or water-
vapour, but increased by 0 (P. F. Frankland,
C. J. 46, 80, 227). It unites directly with
chlorine, bromine, iodine, NjO^, SjCkf ^^^ SO,.
It is quickly absorbed by Nordhausen sulphurio
acid, forming ethionic acid and its anhydride.
Cone. HzSO, absorbs it, forming HEtSO, ; the
absorption takes place rapidly at 100°-170°, but
at ordinary temperature much shaking is re-
quired. Ethylene forms with vrater under pres-
sure a crystalline hydrate (Villard, C. B. 106,
1602).
Beactions. — 1. When passed througharec2-/to<
tube carbon is deposited and marsh-gas formed.
The decomposition commences at as low a
temperature as 355° ; at this temperature a
condensation change only takes place, and is
very slow, requiring 20 hours or more for its
completion. Heated to 400° for a sufQcient
length of time it is entirely decomposed with
formation of marsh-gas, ethane, and liquid pro-
ducts (Day, Am. 8, 153). According to Berthe-
lot (Bl. [2] 9, 456) these liquid products contain
benzene and styrene. Norton a. Noyes {Am. 8,
362) found benzene, naphthalene, andanthracene,
as well as methylene, propylene, batylene, and
crotonylene, CHij:CH.CH:CHj, with OH^, and
CjHg. When heated in a glass tube to dull red-
ness with an equal volume of acetylene it appears
to form butylene (Berthelot, J. 1866, 519). When
a mixture of ethylene and hydrogen is passed
over platinum, even in the cold, ethane is formed
(Von WUde, B. 7, 352). A mixture of ethylene
and diphenyl passed through a red-hot porcelain
tube forms phenanthrene, anthracene, benzene,
styrene, and naphthalene (Barbier, C. B. 79, 121).
2. With oxygen (3 vols.) it forms a highly ex-
plosive mixture. When a mixture of ethylene
and air is passed over red-hot platinum wire
some acetic acid is formed (Coqnillion, C. B. 77,
444). When ethylene is oxidised by weakly-
ozonised oxygen, formic acid and GO, result
(Houzeau a. Benard, C. B. 76, 572).— 3. It burns
in chlorine with a smoky flame :
CjH,-i-2CLj = 2C-l-4HCl.
In the dark and in the cold it unites with
chlorine, forming pily ' Dutch liquid ' CiJa^Clj.—
4. HI at 100° forms EtI (Berthelot, A. 104, 184;
115, 114; J. 1867, 344), HBr also unites with
ethylene, but HOI does not. — 6. Dry ICl form*
OjHiCljand iodine (Genther, J. 1862, 421 ; Thorpe,
C.e7'.37,179). — 6. Chromic acid solution oxidises
it to CO, (Ludwig, A. 162, 47). Chromic acid
mixture forms chiefly oxalic and acetic acids
(Zeidl'er, A. 197, 243) ; Berthelot (0. B. 68, 334)
found even aldehyde. — 7. Potassium .perman-
ganate solution containing HjSOj is decolourised
by ethylene, CO, and formic and acetic acids
being formed. Neutral and alkaline EMnO,
forms chiefly oxalic acid and COj, together with
a little formic acid (Zeidler ; Truohot, C. B. 63,
274 ; Berthelot, C. B. 64, 85). Neutral KMnO,
solution forms also glycol (Wagner, B. 21, 1230).
8. — ^Fuming HNO, absorbs it, forming oxalic
acid.— 9. ClSOjH absorbs dry ethylene with
rise of temperature ; at 90° isethionic anhydride
CjHjSO, is formed, but if the sulphuric chlor-
hydrin be kept cool and the product poured into
water an oil, C^HsSOjCl (154°), smelling like
mustard oil, is obtained; this oil is converted
by water at 100° into isethionio acid, and bj
ETHYLENE-DIAMINE,
486
ary NH, into deliquescent tables ol C„H,NSOa
(Baumstark, Z. 1867, 566).— 10. B(yr<m' fluoride
at 30° in sunlight forms CjHjBPj, an ethereal
liquid (125°) S.G. ^a 1-0478, V.D. 2-65, which
fumes in the air. It is decomposed by water
into ethylene, H,BO„ and HP (Landolph, C. B.
86, 671, 1267; 89,173). This 'fluoboro-ethylene'
acting upon camphor at 200° forms a hy^ocar-
bon C,sH,B. — 11. Ethylene and HBr passed over
Al,£r, form AlBr,C,Hg, and ethyl bromide.
CjH,, HOI, and AljCl, give AlCljC^Ha (Gustavson,
J. pr. [2] 34, 161). At the same time saturated
hydrocarbons are formed — very little at 0°, much
at 70° ; they are formed by the simultaneous ac-
tion of CjHj and HBr on AlBrjCiH,. Ethyl
bromide at 60° acts like CjHj mixed with HBr.
AlBr^O^H, gives saturated hydrocarbons, not
only with OjH, and HBr, but also with EtBr,
FrBr, isobutyl bromide, and MeBr. In aU these
cases the AlBrjO^Hg becomes richer in carbon. —
12. Chloride of sulphur forms S»(CHj.CH.01)j
(Guthrie, A. 119, 91 ; 121, 108" ; Spring a.
Lecrenier, Bl. [2] 48, 629).— 13. CljO forms
chiefly CH2CI.CO.O.CHJ.CH2OI (ohloro- ethyl
chloro-acetate (Mulder a. Bremer, B. 11, 1958). —
14. HCIO forms CHjCl.CH^OH (Carius, A. 126,
197).— 15. A solution of PtOlj in cone. HClAq
forms CjHiPtOla (Birnbaum, A. 145, 69). The
same compound is formed by boiling PtCl, with
alcohol (Zeise, P. 21, 497, 542 ; 40, 234 ; Griess
a. Martins, Pr. 11, 509). It is a yellow mass, si.
sol. water; decomposed by light. In aqueous
solution it is unstable imless HCl is present.
KOH ppts. on warming an explosive powder. It
forms the following combinations : NHgCjHjFtCl^ :
yellow pp. — NH^ClC^HjPtClj aq : lemon-yeUow
prisms.— KClC^H^PtClj aq. — KBrCjH^PtBrjaq :
pale-yellow needles (Chojnacki, Z. 1870, 421). —
CjH,PtjCl,(Et3P03)j (Schiitzenberger, Bl. [2] 18,
103). The corresponding NH^ClCjHJrClj and
(KClCjHJjIrCl, may also be prepared (Sadtler,
Bl. [2] 17, 54).— 16. When ethylene is passed
into cone, aqueous PeBr, in sunlight there
are formed greenish deliquescent crystals of
CjHjFeBrj 2aq (Chojnacki). The corresponding
CJHiFeClj 2aq is got by heating ether (50 g.) with
PejCl,(5g.),P (Ig.) and CSj(|g.) at 100° (Kachler,
B. 2, 510).
Derivatives of 'ethylene : v. Beomo-, Beomo-
KITBO-, BboMO-IODO-, ChLOBO-, CHI.OBO-NIIBO-,
ChLOEO-IODO- &C. ETHTIiENE.
EIHTLBHE-ACETOACETIC ACID v. Aceto.
AOETIO ACID.
ETHYLENE ALCOHOL v. Gltcol.
ETHYLENE • ORTHALDEHYBE v.
AliDE-
BYDE.
ETHYLENE -DI-ALLYL-DI-THIO-DI - T7BEA
C2H,(NH.CS.NHC3H5)2. Prom ethylene-diamine
and allyl thiooarbimide (mustard oil) in alcohol.
Brownish oil, misoible "with chloroform and with
alcohol. Has an unpleasant odour (Lellmann a.
Wiirthner, A. 228, 234)
ETHYLENE - DI - m- AffilDO - DIBENZOIC
ACID C2H^(NH.C^,.G0jH)j. [222°-226°]. Prom
ethylene hromide and TO-amido-benzoie acid by
boiling 24 hours in alcoholic solution (Sohiff a.
, Parenti, A. 226, 244). Hardly sol. water, sol.
boiling alcohol. Insol. dilute HCl, sol. aqueous
NaOH. With KOH (4mols.) and EtI (6molB.)
it forms needles of OjjHsjNA [100°].
Salt.— CuA"aq.
ETHYLENE-DI.i8-AMID0-DI.(o)-CB0T0NIC
ACID CoH^NjO^ i.e. C2H,(NH.CMe:CH.COsH)2.
[168°]. Obtained by saponification of the ether
or by heating ethylene diamine with three times
its weight of acetoacetic ether for an hour at
140°, White silky scales. V. sol. water and
hot alcohol, si. sol. ether, benzene, and cold
alcohol. Gives a violet colouration with FejCl,,.
Di-ethyl ether A."M^: [127°] ; obtained by
mixing ethylene-diamine and acetacetic ether in
aqueous or alcoholic solution; large white
prisms; sol. hot aleohol, ether, and benzene, si.
sol. these solvents when cold, insol. water ; cone.
HCl decomposes it into acetacetic ether and
ethylene-diamine (Mason, B. 20, 273).
ETHYLENE-DIAMINE C^,'S.i.e.
NHj.CH,.CHj.NHj. Mol. w. 80. [8°]. (117°).
Y.D. 2-00 (calc. 2-08). S.G. is -902.
FormaUon. — 1. From ethylene bromide and
alcoholic ammonia in the cold (Hofmann, Pr. 9,
154; 10, 224 ; cf Cloez, J. 1853, 468).-2. From
ethylene chloride and alcoholic NH, (20 mols.)
(Lellmann a. Wiirthner, A. 228, 226). The
fraction (70°-100°) from the preparation of
chloral contains ethylene and ethylidene
chlorides, and if it be heated' with alcoholic
NHj at 110° for 9 hours, the ethylene chloride is
converted into the diamine, while the ethylidene
chloride is not affected (Hofmann, B. 4, 666). —
3. From chloro-ethylene and NH,Bt 160° (Engel,
Bl. [2] 48, 96). — 4. By reducing cyanogen with
tin and HCl (Fairley,ii. Suippl. 3, 872).
Preparation. — A nearly theoretical yield of
the hydrochloride is obtained when ethylene
chloride (42 g.) is heated in a sealed tube to 115°-
120° with33p.c.aqueous ammonia (510 c.c). The
crystals are washed with absolute alcohol until
the washings cease to colour Nessler's solution.
The alcohol yields a fresh crop of crystals con-
taining asamonium chloride and di-ethylene-
diamine hydro-chloride. The hydrate of the free
base is obtained by the addition of freshly fused
and powdered caustic soda to the chloride, then
adding soda-lime and distilling. The anhydrous
base is obtained from this hydrate by again
heating with fused soda in a sealed tube for
several hours (Eraut, A. 212, 254).
Properties. — Volatile alkaUne liquid; it is
very difiScult to dry, requiring treatment with
sodium, v. sol. water. It forms a hydrate
B"aq [10°] (118°). S.G. i* -970, not miscible
with benzene or ether.
Beaeiions. — 1. Nitrous aeid forms nitrogen
and ethylene oxide. — 2. EtI forms CjH^NjHjEtjIj
whence C^H^N^HjEt^ aq, which is in turn con-
verted by EtI into O^^NjHjEtjIj, whence moist
AgjO yields a volatile base whence C^H^N^HEtjIj
and CjHjNjEtjIj may be obtained. The two
last iodides when treated with moist AgjO leave
fixed bases. C^HtN^MegL has also been prepared.
The compound C^H^N^EtiH^Brj may also be
obtained from ethylene-diamine and di-ethyl-
amine (Hofmann, Pr. 11, 423) ; it gives
CjH^NjEtjfHAuCljj. CjH^NjjH^EtjBrj is one
of the products of the action of ethyl-
amine on C^H^Brj; the corresponding base
CoH^N^HjEtjaq crystalline ; it may be dehydrated
by repeated distillation over bajyta, when its
V.D. (H=l) is 57-61 (calc. 58). The hydrated
base C^jK^H^Et^aq has a y.D. 33-2, showing
dissociation (Hofmann, JPr. 10, 597). By 00-
4Sd
ETHYLENE-DIAMINE.
hobating equal mols. of bemil and ethylene-
diamine hydrate for ^ hour, a base C,.H|,N2
CsH,.C = N.CHj,
possibly I I is formed [161°].
C,H5.C = N.CH,
Yellowish prisms. V. sol. ether, benzene, and
hot alcohol, sparingly in cold alcohol, insol.
water. By hot cone, mineral acids it is split up
into ethylene diamine and benzil (Mason, B. 20,
268). — i. CSj in presence of alcohol forms
CjHjNoHjCSj which may be crystallised from
water. Boiling aqueous HgClj converts it into
ethylene thio-urea (Hofmann, B. 5, 241). — 5.
Pyrocatechin heated with ethylene-diamine
hydrate at 205° forms C„H,<^g>CjH, [97°]
(Merz a. Eis, B. 20, 1190). — 6. Benzoic aldehyde
at 120° forms di-benzylidene-ethylene-diamine
(PhCH:N)2C2H, ^[54°] (Mason, B. 20, 270).
Substituted benzoic aldehydes act in the same
way. — 7. When ethylene diamine hydrochloride is
heated it is partly converted into ethylene-imine
OjHiNHfLadenburg a. Abel.B. 21,758).— 8. Hexa-
chloro-acetom forms GJB.i'S^,Cfil,0 [200°].
Penta-chloro-acetcme forms C^HjNjHjCjHCLjO
which orystaJlises from ether in fan-shaped
plates (OloBz, .4. Ch. [6] 9, 145).— 9. Ca/rhomc
ether at 180" forms white needles of ethylene-
urea C^H^^^g^CO. [131°] (Mscher a. Koch,
A. 232, 227). — 10. Di-methyl-methylene diketone
CHjACa forms a solid OiaHjoNA [111°], which
forms a violet copper salt [137°], and a hydro-
chloride B'-HjClj (Combes, Bl. [2] 60, 547).
Salts. — B"JE2Clj : long silvery needles, insol.
alcohol. — B''H2Pt01s : yellow plates (Griess a.
Martins, A. 120, 827).— B"(HSCy)2 : [c. 145°] ;
prisms, v. e. sol. water, v. sol. alcohol, insol.
ether. Split up by heat into ammonium sulpho-
eyanide and ethylene thio-urea (Hofmann, A. 70,
143). — Sulphate: dimetrio crystals (Von Lang,
C. C. 1872, 178).
Di-formyl derivative C^^^^i'^TS.O)^.
From ethylene-diamine and chloral. Syrup
(Hofmann, B. 5, 240).
Di-acetyl derivative C2H4(NHAc)2.
[172°]. Colourless needles. SI. sol. ether.
Forms a crystalline aurochloride B'HAuCl, and
platino-chloride B'.HjPtClj. When heated
in a current of dry HCl it forms ethylene
acetamidine C^H^-^^j^^^CMe [88°] (223°), of
which the aurochloride B'HAuCl, and platino-
chloride B'jHjPtClj are crystalline (Hofmann,
B. 21, 2332).
Benzoyl derivative CjH^NjHjBzj. [649°]
(Kraut a. Schwartz, A. 223, 43). S. (alcohol)
•076 at 22°. Needles (from alcohol). Insol.
water. When heated in a current of dry HCl it
forms ethylene-benzamidine C2H4<Qjj-rT^CPh
[101°], of which the salts B'HAuCl, and
B'jHjPtOlj are crystalline (Hofmann).
Di-ethylene-diamine C^HigNj i.e.
NH<;^'^*>NH. (0.170°). V.D. 2-7 (oalo. 2-9).
Formed, together with ethylene-diamine and tri-
ethylene-diamine by the action of ethylene chlo-
ride on alcoholic ammonia (Hofmann; Natanson,
A. 98, 291). Alternate treatment with EtI and
moist silvei oxide yields three bases, one vola-
tile and two fixed. The corresponding iodides
are (GJS.,)^^^t^, {G^^\^^'E,i,l^, and
(CjHJjNjEt,!^. Mel forms (CjHJjNjMeJj. By
the action of ethylene bromide on ethylamiue
there is formed (CjHJjNjHjEtjBr.^, as well as
CaHjNjHjEtjBrj. On distilling the former with
baryta the free base (C„H4),NjjEt2 (185°) is ob-
tained.
Tri-ethylenp-diamine CaH^Nj i.e. (C^HJ^Nj.
Mol. w. 112. (o. 210°). Formed by the action
of NHj on ethylene chloride (Hofmann, Pr. 10,
104).
Di-ethyleue-trlamine C^H^N,
t.e. NH(C2H4NH,)2. (208°). The bromide
(C2H4)jN,HgBr3 is among the products of the ac-
tion of ammonia on ethylene bromide (Hofmann).
The portion of the bases boiling from 200° to
220° consists almost whoUy of di- and tri- ethyU
ene-triamine, which may be separated by crys-
tallisation of their platinochlorides. Strongly
alkaline liquid, misoible with water and alcohol,
almost insol. ether. Neutralises acids completely,
giving beautifully orystaUised salts, generally
V. sol. water, si. sol. alcohol, insol. ether. The
aqueous solution is not ppd. by KOHAq, but
solid KOH causes the base to separate as a liquid
layer, which rapidly absorbs COj from the air.—
B"'H3Cl3. — B'-'H^Clj. — B"'23H2PtCl, : golden
needles ; cannot be reorystallised without de-
composition. — B"'H,PtCl5. — B"'^,PtCL. —
B"'HClHJPtCl,,.-B"',H,Cl4H2PtCl,.
Among the products of the action of ethyl-
amiue on ethylene bromide are salts of the
ethylated di-ethylene triamines (C^HjjjNjHjEt.
and (CjHJjNsHjEtj, which boil at about 220° to
250°, and of which Hofmann {Pr. 11, 420) has
prepared the following salts : (CjHJjNsHjEtjCl, :
nacreous leaves ; differs from the hydrochlor-
ides of related bases in being insol. alcohol.^ —
(0,H,)^3H,Etj2.-(C2H,)2N,H„Et2l3 : deposited
only when excess of hydric iodide is present. —
(C^HJjNjHjEtjSHNOj. — Platinochloride
{(CjHJjN2H2Et3}j3H2PtCl5. The formation of
(C2H4)2N3H3Et2 must be ascribed to the presence
of NH, in the ethylamine used.
Tri-ethylene-triamine (C^HJsNjHj. (216°).
Formed as above. Its triacid salts are only
formed in presence of a large excess of acid,
feebly acid solutions depositing salts with 1 or 2
equivalents of acid. — B'''j3HjPtCl, : long golden
needles, more soluble in water than the platino-
chlorides of di-ethylene-triamine and of the
ethylene-diamines. Decomposed by recrystalli-
sation. — B"'3HAuCl4 : yellow plates, sol. water,
alcohol, and ether ; may be reorystallised from
water, but decomposed by long boiling therewith,
gold being ppd.— B"'H2Brj.
The ethylated derivative (02Hj),N3Et, is an
alkaUne oil, boiUng between 220° and 250°,
formed by the action of ethylamine on ethylene
bromide ; it forms a platinochloride B"'j3H2PtCl8.
Tetra-ethylene-triamine (CjHJ^NjH. A mix-
ture of the hydrobromides ol this base appears
to be deposited when ethylene bromide is mixed
with alcoholic NH, and left to itself for several
months (Hofmann, B. 3, 762). Combines with 1,
2, or 3 equivalents of HBr forming amorphous
salts, insol. water, alcohol, and ether. By pro-
longed boiling with ammonia the corresponding
hydroxides are got in an amorphous uncrystal-
lisable form, insol. water, alcohol, and ether.
ETHYLEKE BROMIDE.
487
Tri-ethylene-tetramine {C^HOsN^Hj. Occurs
among the products of the action of ethylene
bromide on ammonia, but is best obtained pure
by treating ethylene-diamine with O^HjErj, and
separated from its hydrobromide by moist Ag^O.
Strongly alkaline liquid. — B''2H2PtCl5 : pale yel-
low, amorphous, powder, almost insol. water.
By the action of diethylamine on ethylene brom-
ide at 100° there is formed (C^HJsN^EtaH^r,,
together with the compound (CaH^jN^t^HjErj
already mentioned. If the mixture be treated
with AgaO arid the liberated bases distUled with
steam the volatile diethylamine and tetra-ethyl-
ethyleno-diamine pass off, while the fixed ooto-
ethyl-tri-ethylene tetrammonium hydroxide
(Oj5H,)aN,Et8H2(OH)4 remains behind. It forms
the following salts: (C2H4)3N4EtsH2Cl,2PtCl4 :
small crystalline plates, almost insol. water. —
(C,Hj3N.EtA0MAu01,. - (C^JeN^BtsHA:
white crystals (from alcohol) ; v. sol. water.
Further treatmentwithEtIgives(OsH,)sNiEtsHI„
which forms very fine crystals ; m. sol. alcohol.
Penta-ethylene tetramiue (02H4)5N4H2. When
ethylene bromide is heated with ethylamine to
100° the following products result, besides
NBtHjBr : OaHiNjEtjHjBrj— (C^H^j^NjEt^H^Brj
— (CJajjNaEtsH^rs — (CjHJsNJEtaHaBrj —
(OjHJsN^Et^ByBr.— (OjajjNiEtiBrj. The bases
corresponding to the first four salts have
already been mentioned as being volatile. The
product is therefore treated with moist Ag^O and
then distilled with steam ; the residual liquid is
powerfully alkaline and consists chiefly or alto-
gether of (CjH4)5N4Et,Hj(OH)4. The salts of this
base crystallise with difficidty. Hofmann de-
scribes (C2H,)5N4Et4H2Cl42PtCl4 and the auro-
ohlqride (6jBit)^flSittB.2Clt4AxL0ls as amorphous
or indistinctly crystalline and si. sol. water. EtI
forms (C^HJ^N^EtsHIj and (C^HJ^N^EtJ,.
Heza-ethyleue tetramine (OjHJbN,. The
ethylo-bromide {OJB.f)e'SiT^tfiit is formed as
above, but is better prepared by the action of
ethylene brom ide on CjHjNjEtaHj or (CjjH,) jN^Et^.
ETHYLENE SIISOAUYL DISXTLFHISE
C2Hi(S05H„)j. (245°-255°). Erom ethylene
bromide and sodium isoamyl meroaptan (Ewer-
lof , B. 4, 716). Gives C2H4(SOC5H„)2 [145°-150°]
on oxidation.
ETHYIENE-ANIIINE v. Di-phenyjc-ethyl-
ENE-DIAMINE.
ETHYLENE-BEIfZOATE v. Benzoyl derwa-
twe of Glycol.
ETHYLENE-SI-SENZOYL CABBOXYIIC
ACID V. Dl-PHBNTIi-ETHyLElIB DIKETONB CAE-
BOXYLIC ACID.
ETHYLEirE-BE»ZYL-CAEBOXYI.IC ACID
V. Dl-PHENYL-BUTANE Dl-OABBOXYLIO ACID.
ETHYLENE BROMIDE C^H^Brj i.e.
CHjBr.OHjBr. Di-bromo-ethane. [9^2°]. (131i°
cor.). S.G. If 2-1890; |f 2-1720 (Perkin) ; f?
2-1767 ;'-P 2-1901 (Thorpe, C. J. 37, 177); f
2-1768 (Weegmann, 2. P. C. 2, 218). C.E.
(0°-10°) -00096 ; (0°-100°) -001061. V.D. 6-49
(ealo. 6-56). M.M. 9-700 at 15-2° (Perkin, C. J.
45, 522). S.V, 91-65 (Schifl) ; 97-06 (Thorpe).
FormaUon. — 1. By combination of bromine
with ethylene (Balard, A. Ch. [2] 32, 875;
iowig. Das Brom, Heidelberg, 1829 ; Serullas,
A. Oh. [2] 39, 228; D'Aroet, J. pr. 5, 28;
Eegnault, A. Ch. [2] 69. 358 ; Hofmann, 0. J.
13, 67). — 2. By bromination of ethyl bromide in
presence of AlJ3r6 (Tavildarofl, B. 6, 1459 ;
13,2403; BZ. [2] 34,846).
Pr^araUon. — ^Ethylene is passed through a
series of bottles containing bromine covered by
water; the product is washed with alkali, dried
with CaOlj, and distilled (Erlenmeyer a. Bunte,
A. 168, 64).
Properties. — Colourless liquid with pleasant
smell; below 9° it is a crystalline mass. Insol.
water, sol. alcohol and ether.
Reactions, — 1. AlcohoKo potash on boiling
gives vinyl bromide and acetylene.— 2. KHS
forms Oj^i(SH)2.— 3. K^S gives OjH,S and
C^^Sj.— 4. AgOAe produces CjH4(OAc)2.— 5.
Alcoholic KOAc forms C2H4(OH)(OAo).— 6. KCy
forms OjtH4(CN)2. — 7. Ammonia forms ethylene-
diamine, di-ethylene-diamine, tri-ethylene-di-
amine, &c. — 8. Water at 160° forms aldehyde
(Carius, 4. 131, 172) ; Kriwaxin (Z. [2] 7, 263) ob-
tained no aldehyde. But when excess (26 pts.) of
water is used at 100° glycol isformed (Niederist, A.
196, 354). Water and PbO at 220° form aldehyde
(Eltekoff, B. 6, 558; Nevole, B. 9,447).— 9. Alco-
hoi at 160° gives water, aldehyde, ethyl bromide,
and ether (Carius). — 10. Euming HjSO„ SO, or
C1S0,H at 100° form CHjBr.CHj.SO^H (Wro-
blewsky, Z. [2] 4, 563 ; 5, 281).— 11. Eeduced in
presence of water or alcohol by eino slowly, but
more quickly by the copper-zinc couple, the pro-
duct being ethylene (Gladstone a. Tribe, G. J.
27, 406). Ethylene is also formed by heating
CaHjBr^ with aqueous KI. — 12. Water and AgjCO,
form glycol. Water and Ag^O give aldehyde
jBeilstein a. Wiegand, B. 15, 1368).— 13. AgjSO,
in benzene forms (CH2Br.0Hj)jS04. 'AgjSO, in
water gives (CH^Br.CHJSO.H (B. a. W.).—
14. Ethylene bromide (188 g.) boiled with water
(1,000 g.) and KOH (112 g.) is completely con-
verted (in 6 hours) into KBr and vinyl bromide
(Stempnewsky, A. 192, 240).— 15. Boiling with
dilute NajCOs forms glycol. — 16. Boiled with
aqueous sodium sulphite it probably forms sodio
isethionate, thus: CjHjBrj + NajSOj + HjO
= HO.CsH4.80sNa + NaBr + HBr (James, 6. J.
43, 44), as well as ethane di-sulphonic acid
(Strecker, A. 148, 90).— 17. SbOlj forms
CHi,Cl.CHjBr (Henry, C.B. 97, 1491).— 18. Et^S
forms EtBr, (C^^^^ EtjSBr, and perhaps
(CjHJjSjEtBr (Dehn, A. Suppl. 4, 83 ; B. 2, 479 ;
Masson, G. J. 49, 253).— 19. Euming HNO3
forms bromo^abetic acid and CBr2(N02)2 (Kach-
ler, M. 2, 559).— 20. Boiling cone. HIAq forma '
ethylene iodide (Sorokin, Z. 1870, 519).—
21. With socUum-aceto-acetic ether it gives
CH3.COV /CH,
>C^ I , acetyl-trimethylene oar-
CO^Et/ \0K,
boxylio ether and very small quantities of
CH,.C— O.CHj
II I (Perkin, jnn., O. J. 61, 822).
D CH,
Di-sodAMm acetone di-carboxyUc ether
C0,Bt.0Hi,.00v /CHj
forms ^CC^ I • The resulting
COjEt/ \CH,
acid when boiled with water gives acetyl-prbpyl
alcohol and 2CO2 (Perkin). — 28. Potassivm
phthaUmide at 200° forms bromo-ethyl-phthal-
imide G^fijU^.G^i^T which when heated
vitli concentrated faydrio bromide at 190"
COjEtC-
488
ETHYLENE BROIIIDE.
torms the hydrobromide of bromo-ethylamine
CHjBr.CHj.NHsBr [1S5°-160°]. Diluted aSO,
decomposes bromo-ethyl-phthalimide forming
oxyethylamine CHjOH.CH-NH, (Gabriel, B.
21, S66).
ETHYLESTE BBOIIO-IOBIDE v. Bboiio-
lODO-ETHANE.
ETHYLENE CABBAMATE 02H<(0C0NHj)4.
[149°]. Formed by the action of chloro-formio
amide on glycol, the later being in excess (Gatter-
mann, A. iii, 42). Crystalline flocculent mass.
SI. sol. ether, GS,, v. sol. hot water, alcohol,
HOAc.
ETHYLENE DI-CABBAMIC ETHEB
CjH,(NH.CO.OCjH5)2. Ethylene div/rethane.'
[112°]. Prepared by adding ethylene-diamine
to an ethereal solution of ethyl chloro-carbohate
^nd purified by distillation under 30 mm. Colour-
less needles. V. sol. alcohol and ether, y. b1. sol.
water (Fischer a. Koch, A. 232, 228).
ETHYLENE CARBONATE C^H^COj. [39°].
(236°). Prom glycol and COClj (Nemirowsky,
J. pr. [2] 28, 439). Needles (from ether). V.
sol. water, alcohol, and warm ether.
ETHYLENE BI-CABBOXYLIC ACID v. Fu-
UASIC ACID. .
Ethylene tetra-carbozylic acid CgHjO, i.e.
(C02H)2C:C(C02H)j. The free acid decomposes
very readily.
Salts. — KjHjA"": from the ether by cone.
KOHAq.— Ca,A""7aq.— Ag^A"". ,
Ethyl ether Et^A"". [58°]. (325°-328°).
Formed by the action of NaOEt on ohloro-ma-
lonic ether (Conrad a. Guthzeit, A. 214, 76).
Formed also by the action of iodine (2 mols.) on
di-sodio-malonic ether (2 mols.) in absolute al-
cohol (BisehofE a. Each, B. 17, 2781). Monoclinic
tables. V. e. sol. ether or boiling alcohol, insol.
water. Does not combine with bromine. Pre-
pared by digesting chloro-malonic ether, diluted
with anhydrous ether, for 20 hours with sodium ;
yield 60 p.c. of the theoretical. By heating with
alcohol and aqueous HGl to 190° it yields fu-
maric acid. By zinc-dust and HCl it is reduced
to ethane tetra-carboxylic acid (Courad a. Guth-
zeit, B. 16, 26'31).
ETHYLENE CHLOSHYSBIN v. Chlobo-
ETBTL AIiCOHOIi.
ETHYLENE CHLOBIDE CjH^Clj
i.e. CHjCLCHaCl. Di-chloro-ethane. Mol.w. 99.
(83-6°) 1 (Thorpe, C. J. 37, 182) ; (83-7° cor.) (Per-
kin, 0. /. 45, 528). V.D. 3-42 (oalo. 3-42). S.G.
s 1-2808 (Th.) ; ?jf 1-2656 (Schiff, A. 220, 96) ; =5°
1-2521 (Bruhl, 4. 203, 10); 1-2501 (Weegmann,
Z. P. C. 2,218) ; i| 1-2699 ; fj 1-2480 (P.). C.B.
(0°-10°) -001162; (0°-50°) -001218 (T.) ; (9-8° to
«3-3°) -001269 (S.). S.V. 85-34 (Thorpe) ; 87-2
(Eamsay); 85-24 (Schiff), M.M. 5-485 at 14-4°
(Perkin). /tp 1-144 (W.). fi^ 1-4502. B.^ 34-12
(B.). H.F.p. 34,280 (Th.). H.F.v. 33,120 (Th.).
Discovered inl796 by the fourDutch chemists
{0. Eteyleki:) and hence called 'Dutch liquid.'
Produced by admitting ethylene and moist
chlorine simultaneously into a large globe. It
may also be prepared bypassing ethylene through
a sUghtly heated mixture of MnOj (2 pts.), NaCl
(3 pts.), water (4 pts.), and H2SO4 (5 pts,).
Formed also by passing ethylene into SbCl^.
The product obtained from any one of these re-
actions is washed with alkali, dried over CaClj,
and rectified (Liebig, A. 1, 213 ; 9, 20 ; Dumas,
A. Ch. [2] 48, 185 ; Wohlcr, P. 13, 297 ; Laurent,
A. Ch. [2] 63, 377 ; Eegnault, A.Ch. [2] 58,301;
69, 251 ; 71, 871 ; Limpricht, A. 94, 245 ; Ma-
laguti, A. Ch. [3] 16, 6, 14 ; Pierre, C. B. 25,
430). It is formed also by heating glycol with
excess of HCl in sealed tubes at 100° (Siohorlem-
mer, O. J. 39, 144). It is obtained in large
quantity, together with some of its chlorinated
derivatives, from the by-products in the manu-
facture of chloral (Kramer, B. 3, 257).
Properties. — Oil, with sweetish odour; sol.
alcohol and ether. Dissolves phosphorus. Not
affected by H^SO, at 100°, but at 130° carbon is
separated (Oppenheim, B. 2, 212). Burns with
green flame. Ethylene chloride may be used
with great advantage as an ansesthetio in opera-
tions on the eye (Dubois a. Boux, Compt. rend.
Soc. Biol. 4, 684 ; C. B. 108, 191).
Beactions. — 1. Its vapour passed through a
red-hot tube forms carbon, naphthalene, chloride
of carbon, &o. — 2. When covered with water and
exposed to sunshine it is decomposed, yielding
HCl and acetic ether. — 3. It is chlorinated by CI
in heat or light. — 4. Dry ammonia does not act
upon it, but when dissolved in water or alcohol
it forms the various ethylene-amines (Eobiquet
a. CoUn, A. Ch. [2] 1, 213; 2, 206).— 5. Botas-
siwm attacks it violently, forming hydrogen,
vinyl chloride, and other products. — 6. Aqueous
potash has little action, but alcoholic potash
gives ethylene and vinyl chloride (Maumen6, C. B.
68, 931) — 7. KHS, K^S, KjSj, and KCyS give
the corresponding ethers of ethylene. — 8. PCI,
at 190° yields CHClj,.CH,Cl (121°-133°) and
CHClj-CHCLj (133°-146°) (Colson a. Gautier,
A. Ch. [6] 11, 31).
ETHYLENE CHIOBO-BBOMIBE v. Chlobo-
BBOMO-ETpANE.
ETHYLENE CHLOBO-IOBIDE v. Chlobo-
lODO-ETHANE.
ETHYLENE CHLOEO-THIOCYANATE v.
Chlobo-bthyl sulphooyanide.
ETHYLENE CYANIDE v. Nitrite of SnooiNio
Acro.
ETHYL-DI-ETHYL-DI-AMIDO-DI-BENZOIC
ACID. Ethylether. OeH4(NEt.CBH4.COjBt)j. [98°-
100°]. From CjH,(NH.C^4.C0ja)jbyK0H and
lEt (Sohift a. Parenti, A. 226, 246). Doubly re-
fracting prisms (from alcohol). Insol. water.
ETHYLENE-ETHYL-AMINES v. Ethyl den-
VativeS of ETHTLENE-AHraES.
ETHYLENE DIETHYL CAEBONATE
C2H4(O.COjEt)2. (226°). From sodium glycol.
CjH4(0Na)a and ClCOjBt in ether (WaUaoh, A.
226, 82). Split up by long boiling into carbonic
ether and ethylene carbonate.
ETHYLENE-ETHYL-PHOSPHINE v. Ethyi,-
PHOSPHINE.
ETHYLENE-DI-ETHYL DI-STJIPHIDE
''02H,(SEt)2. (212°). Formed by adding ethylene
bromide to a boiling solution of sodium meroap-
tide (1 pt.) in ether (3 pts.) (Ewerlof, B. 4, 716
Beckmann, J. pr. [2] 17, 468). Decomposed by
heat. Converted by EtI at 100"! into SEtjI and
C„H,S2 (Braun, B. 20, 2967).
ETHYLENE-DI-ETHYL DI-SULPHONE
C2H,(S02.Et)2. Ethylene disulphimc ether.
[137°]. Formed by oxidising ethylene-di-ethyl
di-sulphoxide with KMnO^ (Ewerlof; Beck-
mann, J. pr. [2] 17, 468). Also from sodium
ETHYLENE MEROAPTAN.
489
ethane solpliinate and ethylene bromide, and
from sodium ethylene disulphinats and EtBr
(Otto a. Casanova, J. pr. [2] 30, 172; 36, 433).
Short needles, sol. hot water and alcohol, si.
sol. ether, benzene, CHCI3, and cone. HNO,. Not
affected by reducing agents, PCI5, or KMnO^.
Nascent hydrogen in alkaline solution converts
it into sodium ethane-sulphinate and alcohol.
Successive treatment with aqueous KOH and
BzCl gives SOjEt.CHj.CH2.OBz [118°], It is
uncertain whether ethylene di-ethyl di-sulphone
has the constitution CitHJS(02).Et}j, or whether
it is not rather the ethyl ether of ethane disul-
phinio acid, under which it has also been de-
scribed.
ETHTLENE-DI-EXHYI DI-STIIPHOXIDE
CjH4(S0Et)j. [170°]. Got by oxidising ethyl-
ene-di-ethyl di-sniphide with HNO, (S.G-. 1-2),
neutralising, evaporating, and extracting with
alcohol (Beckmann, J. pr. [2] 17, 468). 'Wliite
scales, sol. water and alcohol, insol. ether. Ee-
duced by Zn and H^SOj, or by HI to the corre-
sponding sulphide. Attacked by PCI.. Eeduces
KMnO^.
Com?)inaiiore.^^With nitric acid it forms, on
evaporation, an acid syrup C„Hi(S0Et)2, HNO3.
ETHYLENE EIHYL DI-THIO-DI- CAR-
BONATE V. Ethtl thio-oaeeonates.
(o)-ETHYLENE-DI-ETHYI-DI-XrEEA
C^„NA»-«-C2H,(NEt.C0.NHj)j. [124°]. From
di-ethyl-ethylene-diamine, hydrobromide, and
silver oyanate (Volhard, Pr. 11, 268; A. 119,
349). Plat needles (from alcohol). V. sol. cold
water, v. e. sol. alcohol, insol. ether. Boiling
KOHAq gives NH3, CO,, and CjH,(NBtH)2.—
B'jHjPtOl, : orange grains, decomposed by hot
water.
(j3) -Ethylene-di-ethyl-di-urea
C2H4piH.CO.NHEt)j. [201^]. Erom ethylene-
diamine and cyanic ether (Volhard). Small
needles, v. sol. hot, si. sol. cold, water, v. si.
sol. alcohol. Decomposed by boiling KOHAq,
giving ethylamine and ethylene diamine. Is not
basic.
ETHYLENE GLYCOL v. Glycol.
ETHYLENE HEPTYLIDENE DIOXIDE
C^„.CH<Q>C2Hj. (c. 180°). Formed by
heating heptoic aldehyde (1 vol.) with glycol
(3 vols.) at 130° for 8 days (Lochert, Bl. [2] 48,
337, 716). Formed also by heating a mixture
of heptoic aldehyde (oenanthol) (1 vol.), glycol
(2 vols.), and HOAo (1 voL). Liquid.
ETHYLENE-IMINE O2H5N i.e. <ci^-'^-^'
or C,H.A i-e. <^in^' [159°-163°].
V.D. 2-93. Formed by subliming ethylene-
diamine hydrochloride (4 g.) ; the sublimate is
dissolved in water and ppd. by potassio-bismuthic
iodide, the pp. being then decomposed by KOH
(Ladenburg a. J. Abel, B. 21, 768, 2706). DeK-
quescent porcelain-like mass. Its V.I). oorre-
aponds to the formula CjHuNj, but when first
prepared it is possibly CjHsN. Insol. ether, v.
sol. alcohol ; absorbs CO^ from the_ air. The
base is perhaps identical with spermine.
Salts.— OjHsNHCl: tables, v, sol. water,
insol. alcohol. — B'jHjPtClj: yellow prisms. —
B'sHglsBijIs : garnet-red plates, insol. cold
water.— B'HAuCl^ : nacreous leaflets, decom-
posed by heating with water.— B'jHjCljSHgCl, :
clusters of quill-like groups of needles.
ETHYLENE IODIDE C-H.!,, t.e. CHJ.CHjI.
[82°].
Formation. — 1. By direct combination of
iodine and ethylene in sunshine (Faraday, Ann.
Phil. 18, 118), or by heating to 60° (Eegnault,
A. Ch. [2] 69, 367).— 2. One of the products
formed when EtI is passed through a red-hot
tube (E.Kopp, J. Ph. [3] 6, 110).— 3. From glycol
and cold BU. — 4. By heating ethylene chloride
with Calj S^aq at 75° (Spindler, A. 231, 265 ;
Van Eomburgh, R. T. C. 1, 161).
Preparation:— A pasty mixture of iodine and
absolute alcohol is saturated with ethylene and
agitated, fresh quantities of iodine being added
from time to time (Semenoff, Zeit. Ch. Phann.
1864, 673).
Properties. — Colourless needles or prisms;
may be readily sublimed in hydrogen or ethylene.
Insol. water, v. sol. ether and boiling alcohol.
Slowly split up, especially under the influence of
light, into ethylene and iodine ; this change takes
place rapidly at 85°.
Reactions. — 1. Chlorine gives iodine and
ethylene chloride. Bromine acts in the same
way. — 2. Aqueous KOHAq has but little action ;
but boiling alcoholic potash gives ethylene and
vinyl iodide. — 3. Water at 275° gives ethane,
COj, and iodine (Berthelot, A. Ch. [4] 3, 211).
4. Mercuric chloride in the cold forms C„H,C1I.
At 100° it forms G^JSi.^ (MaumeuS, C.'R. 68,
727). — 5. Silver picrate forms the compound
CHJ.CH„.O.CjH2(N02)3 [70°], crystallising in
light yellow prisms, insol. water, si. sol. cold
alcohol and ether, v. sol. chloroform (Andrews,
B. 13, 244).
ETHYLENE lODO-QHLOBIDE CH^LCHjCl.
Chloro-iodo-ethane. (140° cor.) (Thorpe, G. J.
37, 189). S.G. 2 2-1644 ; ^p 2-1386 (T.). Ob-
tained by agitating an aqueous solution of ICl
containing a trace of free iodine with ethylene
iodide or ethylene (Maxwell Simpson, Pr. 11,
590 ; 12, 278). Colourless oil with sweet taste,
si. sol. water. Moist AgjO at 180° forms glycol.
Silver at 160° gives Agl, ethylene, and ethylene
chloride (Friedel a. SUva, Bl. [2] 17, 242).
ETHYLENE LACTIC ACID v. Htdiiacetlio
ACID.
ETHYLENE MALONIC ACID ». Tbi-methyi..
ENE DICABBOXYLIC ACn).
ETHYLENE MERCAPTAN CjH.(SH).,.
(146°). S.G. '^ 1-123. Formed by the action
of alcoholic KHS on ethylene chloride or brom-
ide (Lowig a. Weidmann, P. 49, 132 ; A. 36, 322 ;
Kekul6, X 1, 655). Liquid, v. sol. alcohol. Sol.,
aqueous alkaUs. Oxidised by HNO, to the acid
C^4(S03H)2. When HCl is passed through a
mixture of ethylene mercaptan with chloral there
is formed the compound C2H4(S.0H(0H).CCl3)2
[116°], which crystallises from ether in shining
plates (Fasbender, B. 21, 1476). In general
ethylene mercaptan combines with aldehydes,
with evolution of heat, forming additive pro-
ducts, which are decomposed by water into their
constituents. When HCl is passed into equi-
molecnlar mixtures of ethylene mercaptan and
an aldehyde, condensation takes place, an alkyl-
ated ethylene mercaptan being formed.
490
ETHYLENE MEROAPTAN.
Salts.— CjH^SjPb: light-yellow.— CJIjS^Cu :
green.
Di-methyl derivative C2H,(SMe)2.
(183°). Prom ethylene bromide, and NaSMe
(Ewerlof, B. 4, 716).
Di-ethyl derivative C2H4(SEt)2. (e.
211°).
Di-isoamyl derivative CM,{SGJ3.,j)2.
(245°-255°). Gives on oxidation CjHiSO.aH,,);;
[145°-150'>].
Benzylidene derivative CjHjSjCH.CgHs.
[29°]. Prom benzoic aldehyde, ethylene mercap-
tan, and HCl. Insol. water, sol. alcohol and
ether (Fasbender, B. 20, 460 ; 21, 1476).
p-Methoxy-benzylidene derivative
CjH,S2CH.C„H^.0Me. [65°]. From anisic alde-
hyde and ethylene mercaptan (P.).
Acetylene derivative
CjHA-CH.CH.SjCjH,. [133°]. From glyoxal
and ethylene mercaptan.
Ethylidene derivative C^H^SoCHMe.
(173°). Oxidises to a disulphone [198°]."
Propylidene derivative CjHjSjCHEt.
(192=). Gives a disulphone [124°].
Iso-propylidene derivativeCfifSjCilLe^.
(171°). From acetone, ethylene mercaptan, and
HCl (F.). Potassium permanganate gives by
oxidation C2Hi(S02)2CMe2 [232°].
■ Di-phenyl-methylene derivative
C^H^SjCPhj [106°].
ti>-Ghloro~ethyl-ethyl derivative
EtS.C2H4.S.CHj.CHjCl. From ethylated ethyl-
ene mercaptan, Bt.S.C^Hj.SH by treatment with
KOH and glycolio ohlorhydrin, the product,
Et.S.CjH4.S.C2H,.0H being then ' mixed with
PCI3 in the cold (Demult a. V. Meyer, A. 240,
312). Needles. Decomposed by distillation into
EtOl and di-ethylene-di-sulphide.
ETHYIENE - METHYL- v. METHYi-ETHYii-
ENE-.
ETHYIENE-NAFHTHALESTE v. Acenafh-
IRENE.
ETHTLENE-NAFHTHOIC ACID
C2Hi;C,„Hj.C0jH. [217°]. Colourless needles.
Obtained by boiling its amide with alcoholic
KOH (Gattermann, A. 844, 58).
Amide CaH^-.OioHs.CONH,. [198°]. Formed
by the action of OICONH^ on acenaphthene in
presence of AljClj. Colourless plates.
ETHYIENE-NAPHTHYL BENZYL KE-
TOITE OjH,:C,„H5.CO.CH2.C„H5. [114°]. Prom
acenaphthene, phenyl-acetio chloride and AljCl^
(Papcke, B. 21, 1842). Long plates (from alco-
hol). V. sol. hot alcohol.
ETHYLENE -NAPHTHYL DI -PHENYL -
ETHYL KETONE C2H^:C,„H5.C0.CHPh.CH,Ph.
[104°]. From the preceding by treatment with
benzyl chloride and NaOEt (Papcke, B. 21, 1343).
ETHYLENE NITBITE C2H4(O.NO)2. (96°).
S.G. 2 1-2156. Prepared by distilling glyceryl
trinitrite with glycol (Bertoni, (?. 15, 351).
Yellow oil, sol. alcohol, ether, and chloroform.
Gives a violet colouration with cone. H^SO,.
When distilled with methyl alcohol it yields
methyl nitrite and glycol. Gradually converted
into oxalic acid on exposure to air. When in-
spired it produces vertigo and paralysis of the
respiratory system.
Isomeride of ethylene nitrite C2H,(N02)j?
[38°]. Formed by passing dry ethylene through
Lquid nitric peroxide, ojr by passing ethylene
into dry ether, to which NjO, is at the same time
added by drops (Semenoff, Zeit. Oh. Pharm.
1864, 129). White four-sided prisms or tables,
insol. watet, v. sol. alcohol and ether. _ When a
gaseous mixture of ethylene and NoO, is heated
to 65° there is formed, besides the compound
[38°], a pungent, volatile, and poisonous, heavy
oil, which is perhaps identical with the oil de-
scribed by Bertoni as the true ethylene nitrite.
ETHYLENE NITBITE-NITEATE
C,H4(N0J(N0,) ? S.G. 1-472. A pungent oil
formed when ethylene is passed through a Cooled
mixture of HNO3 and HjSO, or into fuming
HNO3 (Kekulfi, Z. [2] 5, 601). Decomposed by
distillation with steam, yielding NO, nitrous
fumes, oxalic, glycoUic, and glyoxylio acids.
Bases produce the same bodies. Sodium-amal-
gam reduces it in alkaline solution to glycol,
giving off NHj.
ETHYLSNE-SI-OXAMIG ETHEB
C2H4(NH.CO.C02Et)2. Prom oxalic ether and
ethylene-diamine, remaining in solution when
the following body is ppd. (Hofmann, B. 5, 247).
Scales, sol. water and alcohol.
ETHYLENE-OXAMIDE C^OjNjH^C^H,. From
oxalic ether and ethylene-diamine (Hofmann, B
5, 247). Amorphous, insol. water and alcohol.
ETHYLENE OXIDE C^H^O i.e. <C^^0.
Mol. w. 44. (13-5°). S.G. a -897. V.D.'l-42
(calc. 1-53). H.P.p. 18,090 (Th.). H.F.v.
17,220 (Th.). Formed by warming glycolio chlor-
bydrin (chloro-ethyl-alcohol) CKjCLCH^OH with
potash and collecting in a receiver at —18°
(Wurtz, O. B. 48, 101 ; 49, 898 ; 50, 1195 ; 53, 378 ;
54,277; 4.110,125; 114, 51; 116,249; A.Ch.
[3] 65, 418, 427; 69, 317; G. J. 15, 387).
Formed also by treating C^HjEr^ or C^HjIj with
AgjO at high temperatures (Greene, O. B. 85,
624). Prom CH2(0Ae).CHs,Cl and KOH (Demole,
A. 173, 125). Mobile colourless liquid. Misoible
with water and alcohol. Does not unite with
NaHSOj, or with NHj. Cannot be dried by
CaClj. Behaves as a strong base, uniting di-
rectly with HCl, HOAc, &c. Ppts. from magne-
sium, aluminium, ferric, and oupric salts, the
hydrates of the metals, e.g.
iG^fi + MgClj -1- 2HjO
= Mg(OH)j -I- 2CXC1-0H.
BeacUons. — 1. Sodium amalgam reduces it
to alcohol, glycol and polyethylenic glycols being
also formed. — 2. Unites with HCl forming
CHjCLCHjOfl. The union C^HjO-hHCl, both
being gaseous, evolves 3,600 units of heat (Ber-
thelot, C. B. 93, 185).-— 3. Unites with HOAc,
giving CHj(OH).CH2(OAc).^4. Ac^O gives
CH,(OAe).CH2(OAo) and the polyethylenic di-
acetates (C2H40)„AcjO. — 5. When heated with
water in sealed tubes it forms glycol and the
polyethylenic glycols. — 6. Bromine (1 mol.)
mixed with ethylene Oxide (2 mols.), and cooled
by a freezing mixture, forms (C2HjO)2Br2, crystal-
lising in prisms [65°], insol. water, sol. alcohol. —
7. Ammonia forms oxy-ethyl-amine and com-
pounds of the formula Ci,H.,(OH)(OC2HJ„NH2.—
8. Heated with NaHSOj in a sealed tube at 100°
it gives CH2(OH).CH2.SOsNa (Erlenmeyer, Z.
[2] 4, 342). — 9. Besinifies aldehyde when heated
with it in a sealed tube. — 10. PCI, gives ethylene
chloride. — 11. PhospJumium iodide gives PH,
and ethylene iodide (De Girard. C. B. 101, 478).
ETHYLENE SULPHIDE.
491
DUthylene dioxide C^Hj^^^CjH,. [9°].
(102°). S.G. 2 1-048. V.D. 3-10 (oalo. 3-05).
Formed by treating the compound (C2H40)jBrj
(«. sitpra) with HjS or, better, with mercury in
the cold (Wurtz). Liquid with faint odour. Sol.
alcohol and ether, not attacked by ammonia.
Polymeride of ethylene oxide (CaHjO)^;.
[56°]. Formed by leaving ethylene oxide for
some months after addition .of a very small
fragment of fused potash or ZnCLj (Wurtz, Bl.
[2] 29, 530 ; C. B. 86, 1176). A trace of HOI
will iiot effect the change. It is a nodular crys-
talline mass ; v. sol. water, insol. ether. It does
not reduce Fehling's solution.
Chloro-ethylene oxide CjEjClO. (70°-80°).
From CHChCHI (1 vol.) and water (45 vols.) at
210° (Sabanejeff, A. 216, 268).
Bromo-ethylene oxide CjHjBrO. (o. 91°).
PromCHBr2.CH20H and KOH in MeOH (Demole,
B. 9, 51).
ETHVLENE-FHENANIEBACITTIXOXALIXE
C„H..C-N-CHj
C,Mi^i i.e. I II I I 1 Ethylme-di-
CjH^.C-N-CH,
phenylene-quinoxaline. [181°]. Formed by
mixingphenanthraquinone and ethylene-diamine
in warm acetic acid solution (Mason, B. 19, 112).
DistUs undecomposed at a high temperature.
Yellowish needles. V. sol. ether, benzene, and
acetic acid, si. sol. cold alcohol, insol. water.
ETHYLENE - DI - PHENYL - DIAMINE v.
Dl-PHENYL-ETHYLENE DIAMINE.
ETHYLE M E- DI-PHENYL- DI- CAEBAMATE
t>. Ethylene ether of Phensl-caebamio acid.
ETHYLENE - PHENYLENE - DIAMINE v.
Phenylene-ethylene-diaminb.
' ' Ethylene-di-pheuylene-m-tetramine
[3:l]CeH,pjHj).NH.C2H,.NH.CeH,(NHJ [1:3].
■ JX-m-am,ido-di-phenyl-ethylene-diamine. [107°].
Formed by reduction of di-jre-nitro-di-phenyl-
ethylene-diamine. Silvery needles or tables
(from hot water). Nearly insol. cold water.
Salts. — With nitrous acid they give a brown
colouration. — B'l'HjCl, : soluble colourless plates.
The pier ate forms long brown sparingly soluble
needles. The tin-double-chloride is si. sol.
cold water (Gattermann a. Hager, B. 17, 779).
Di-ethyleue-di-phenylene-tetramine )
C^ CjH, . [221°]. Prepared by reduo-
\n^c^,.nh,
tion of dinitroso-diphenyl-diethylene-diamine
(Morley, B. 12, 1796). Silvery leaflets. SI. sol.
alcohol, ether, and CoHj. Violet colouration
with FcClj.
ETHYLENEDI-PHENYLENE-NITEAMINE
V. Dl-NITRO-DI-PHENYIi-EIHYLENE-DIAMlNE.
ETHYLENE-DI-PHENYL-DI-SrLPHONE v.
Dl-PHBNYL-ETHYLENE-DI-SniiPHONE.
ETHYLENE-DIPHTHALIMIDE
{C,'H.fifiJX).fi^B.,. [232°]. From potassium
phthahmide (10 g.) and ethylene bromide (12 g.)
at 200°, the chief product of the reaction being
CeH4.Cj02.N.CjH,Br [83°] (Gabriel, B. 20, 2224).
Long lustrous needles (from HOAo). Fuming
HCl at. 200° spUts it up into ethylene-diamine
and phthaUc acid.
ETHYLENE PSOPYLIDENE DISULPHONE
V. Ethylene mekcaptan,
ETHYLENE DIPBOPYL DISTILPHONE
02H,(SOjPr)2. [155°]. From sodium ethane
disulphinate and propyl bromide (Otto, J.pr. [2]
36, 446). Iridescent prisma.
ETHYLENE-DI-ftUINOLINE O^oH.eN, i.e.
.OH:CH OH:OH.C. N : CH
CaH,<( I 1 II 1 •
\ N: 0 . CH2.0Hi,.CH:CH.C.0H:CH
[106'5°]. Prepared by the action of HI and
amorphous phosphorus onacetylene-di-quinoline ,
[147°], itself prepared from ^-ainido-{Py. 3)-
styryl-quinoline by treatment with o-nitro-
phenol, glycerin, and HjSOj (Balach, B. 22,
289). Glistening prisms (from hot water).
ETHYLENE SELENOCYANIDE 02H4(SeCy)2.
[128°]. From potassium solenooyanide and
ethylene bromide (Proskauer, B. 7, 1281). White
needles (from alcohol), insol. cold water and
ether, si. sol. hot water and cold alcohol. Boil-
ing nitric acid oxidises it to 02H4(SeOsH)i, which
is deliquescent.
ETHYLENE SULPHIDE C.HjS. This per-
haps constitutes the amorphous pp. obtained
when ethylene bromide is mixed with alcoholic
KHS. It is nearly insol. alcohol, ether, and
CSj. At 160° it changes to di-ethylene-disul-
phide (LBwig a. Weidmann, P. 49, 123). When
ethylene sulphide is heated with Mel in a sealed
tube at 65° it forms a sulphine iodide which
resembles SMcjI rather than (C2HJ.^S2MeI in
crystalline form and solubility (Masson, O. J.
49, 249).
Di-ethylene di-suIpMde C2H4<^|]>C2Hj.
Mol. w. 120. [112°]. (200°). V.D. 4-28 (calp.
4-16). Formed by heating the preceding at 160°
(Crafts, A. 124, 110). Obtained also by heating
ethylene tri-thiocarbonate C^HiCSa or ethylene
mercaptide of mercury CHjSzHg with CjH^Brj
at 150° (Husemann, A. 126, 280).
Properties. — Monochnio prisms (from CSj),
sol. alcohol and ether. Eeadily sublimed.
Reactions. — 1. Bromine forms (CjHJ^SijBr,,
a yellow amorphous pp. [96°]. — 2. loMne gives
CjHgSJj [133°] : black monoclinic needles. —
3. Fuming HNO, forms (C^,)^i^^O)^ below
100°, but above 150° it gives (G,H,)2(S0,),
(Crafts, A. 125, 123).
GomlmaHons. — CjHjSuHgClj: crystalline pp.
got by mixing alcoholic solutions of C^HjS.^ and
HgClj. — CjHjSjHglj : minute trimetric tables. — ■
CjHgSjPtCl,: amorphous orange powder. —
04HsS22AnCls: Vermillion pp.— (C4HsS2)a4AgN0s:
small monoclinic crystals ; decomposing at 140°.
Methylo-iodide (CjHJjS^Mel. From di-
ethylene di-sulphide and Mel at 70° (Masson,
C. J. 49, 238). Opaque white needles, v. sol.
hot, si. sol. cold, water, v. sol. alcohol, insol.
ether. Sublimes above 100°, some (CjHJ^Sj
being regenerated.
Methylo-tri-iodide (C2H,)2S2Mel3. [89°]
(Masson) ; [93°] (Mansfeld, B. 19, 2658). From
the methyl-iodide and iodine. Thin lustrous
garnet-red plates, y. sol. hot, si. sol. cold, alco-
hol, insol. ether.
Di-methylo-iodide {CMt)SM^i^i- [208^.
Methylo-nitrate (CjHJjSjMeNO.,. [172°],
From the iodide and AgNOj (Masson). Pearly
plates or rhombic crystals, v. e. sol. water.
402
ETHYLENE SULPHIDE.
m. soluble in hot alcohol, insoluble in ether. —
(C2H4)2SjMeN03AgN03 : colourless barb-like
•urystals, v.- e. sol. water, m. sol. alcohol, insol.
ether; blackens in sunlight ; detonates slightly
when heated.
Methylo-sulphate{{C^,)„S,]^Me2SOJst(i.
[127°]. From the iodide and AgjSO^. Large deli-
quescent prisms (from water) or small needles
(from alcohol). Decomposed by fusion.
Methylo-ehloride (CijH4)2S.MeCl. [22^°]
(Mansfeld, B. 19, 2658). From' the sulphate
and BaCl^. Needles or tables ; v. sol. water, si.
Bol. alcohol, insol. ether (Masson, G. J. 49, 242).
(CjHaSjMeC^jPtCl^ : orange orystaUine powder,
got by adding PtCl, to a cold solution of the
chloride. — C„^,S,Pt2Cl, : formed by digesting'
the preceding compound with boiling water. —
(CiHgSjMeO^^SPtCl, : formed, together with the
foUowing, by adding FtCl^ to a hot solution of
the methylo-ehloride. Orange amorphous pp.,
insol. water, alcohol, ether, and dilute acids, si.
sol. hot cone. EClAq, sol. cone. NH,Aq. Gold
H^S does not affect it, but it is decomposed by
H^S at 100°.— CiHgSjMeClPtCl, : obtained by
fractionally ppg. a solution of the methylo-
ehloride with PtClj. Orange amorphous pp. —
CtHgSjMeOlAuCl, : light-yellow amorphous
powder; decomposed by heating with water. —
C^HsS^ClHgClj : needles and thin plates, ob-
tained by mixing aqueous solutions of its com-
ponents.
Methylo - hydroxide (CjHJjSzMeOH.
Formed in solution by treating a very dilute
solution of the iodide with moist Ag^O in the
cold. It ppts. solutions of metallic salts and ab-
sorbs GO, from the air. On boiling there is
formed a white flocculent pp. and an oil
0,^85; S.G. j^j 1-044. This oil has a dis-
agreeable odour, is insol. water, sol. alcohol and
ether: volatUe with steam. It combines with
Mel. This oil is also formed when an aqueous
solution of the chloride, iodide, sulphate, or
nitrate is heated with potash or baryta-water.
Mansfeld considers the oil to be CjHigS,, and
finds it can take up (2 mols. of) bromine.
Methylo-picrate{0^^)iSJAeO.0^n2(nO^,.
[193°]. Golden needles (Mansfeld).
Benzylo-bromide (C^B.,)^^,^,^!. [146°].
From (G^HJoSj and benzyl bromide at 150°
(Mansfeld, B. 19, 2666). Trimetrio crystals
(from water). SI. sol. water and alcohol. Potash
(1 mol.) converts it on warming into oily C„H,,S2,
which is slightly volatile with steam.
Bemylo-chloride (C^^SiG,'B.,C\. [143°].
From the bromide and AgCl. Colourless silky
needles.
Bemylo-iodide (C^JjSjCjH,!. Fromdi-
ethylene di-snlphide and benzyl iodide at 100°.
Pale-yellow needles, si. sol. water, m. sol. alco-
hol, insol. ether.
Benzylo-picrate
(C;^4)jSjC;a,0C.Hj(N0j),. [112°]. Golden
needles.
CH2.S.S.CHj
Oi-ethylene-tetra-salphida | | .
CHJ.S.S.CH2
[152°] ?
Formation.r~l. By the action of bromine
upon a chloroform solution of ethylene mercap-
tau C;jH,(SH), or of benzylidene-ethyleue-di-
.S.CH,
sulphide C^,.CHf^ | .—2. By treating
ethylene mercaptan with oono. HjSOi or with
SOjClj. — 3. By the action of hydroxylamine
hydrochloride on an alkaline solution of ethylene
mercaptan.
Properties. — Amorphous powder. Softens at
141°, melts at 152°. Almost insol. all sol-
vents. Sol. phenol. Not volatile (Fasbender,
B. 20, 462 ; 21, 1471). It forms a perbromidei.
C4HsS4Br8 : unstable brownish-red crystals.
HNOj gives ethylene disulphonic acid.
DI-ETHYLENE STILPHOBEOMIDE
(C2Hj)jSBrj. Formed by heating ethyl sulphide
with ethylene bromide' and water (1 vol.) at 130°
(Dehn, A. Suppl. 4, 83 ; cf. Masson, C. J. 49,
253). It is said to give (CjHj)jSCl2PtCl4.
EIHYIEHE SUIFHOCHLOBISE. A name
given by Guthrie to various oils got by the
action of the chlorides of sulphur on ethylene
(q.v.).
ETHTLENE SI-STTLFEOCYABIDE
CjH,(SCN)2. [90°]. S.G.J* 1-28.
Formation.— X. By heating an alcoholic solu-
tion of ethylene chloride or bromide with an
equivalent quantity of potassium sulphocyanide
at 106° (Sounenschein, J.pr. 65, 257; Buff, A.
96,302; 100,219; Glutz, .4. 153, 313).— 2. From
KSGN, C^iGLSCN, and alcohol (James, C. /.
43, 40).
Properties. — Stellate groups of small needles
(from water) or large trimetric plates (from
alcohol). Burning taste ; blisters ttte skin. Its
vapour excites sneezing. HNO, oxidises it to
ethane disulphonic acid C2H,(S03H)p Boiling
aqueous EOH or baryta saponify it, forming
sulphocyanides.
Beactaons. — 1. Tin and hydric chloride give
CyS.GjHi.SH^Ol, which crystallises from al-
cohol in scales, and forms a tin double salt
(CsHjNSjC^jSnCl, (Glutz). The corresponding
compounds, OsHjNSjJ which melts above [100°],
CjHbN.SjNOs Jaq, and GaHBNSjSCy are crystal-
line.—2. PBta forms PEtaS and 02Hj(PBt30N)j
(Hofmann, A. Suppl. 1, 55). — 3. A warm cone,
solution of NajSO, forms crystals of
CHjSjNOioNa, (7), while the mother-liquor con-
tains G^HioSjOi^Na, (Glutz).
SI-EIHYLENE DI-SULFHONE
c»^«<so:>cA-
Formed by heating di-
ethylene di-sulphide with fuming HNO, for
30 minutes at 150° (Crafts, A. 123, 124). Formed
also by the action of di-bromo-ethane on sodium
ethane disulphinate (Otto, J. pr. [2] 36, 446).
Prisms, insol. ordinary solvents, m. sol. hot
cone. HNO3.
ETHYIENE DISTIIPHONIC ACIDo. Ethanb
DISULFHOKIO ACID.
DI-ETHTLENE DISULPHOXIDE
C^j-C^Iq^OjH,. From di-ethylene di-sulphide
and fuming HNO3 (Crafts, A. 124, 113 ; 125,
123). Formed also by treating (CjHJjSjBrjWith
water (Husem^nn, A. 126, 290). Ehombohedra
or long white prisms ; decomposed by heat with-
out melting. Y. sol. water, si. sol. alcohol and
ether. Chlorine passed into its solution gives
a crystalline pp. of CJSfil^Sfii-
ETHYL FLUOEUDE.
483
ETHTLESE THIO-AIUIELINS C^HjNjS
i.e. n/
.C=(NH)— N,
C(NHJ-
Formed by
0,H„
[0. 267°], whicli
heating ethylene biomide, alcohol, and thio-
ammeline to 120° (Eathke, B. 21, 874).
Beactions. — 1. By passing chlorine through
a solution of the hydrochloride in water an
anhydride of 'tauroammeline* is formed.
This anhydride forms plates, insol. water, sol.
alkalis ; it may be written N<^Sf^^^H^O.OH.
N-SO^.e^H,
2. Oxidation with HKO, yields the compound
CioHisNjSjOg. This compound has been called
' tauro-di-ammeline,' and crystallises from
water in transparent prisms. It does not melt
below 290°. It reddens blue litmus, liberates
GO2 from carbonates, and forms very soluble
salts of K, Na, Ca, and Ba. Its ammoniacal
solution gives with AgNO, a pulverulent pp.
not affected by light. On boiling with baryta
it changes to ' tauro-ammelide '
„C{NBy.N.
Nf ^C.OH
\C0 N/.OjH,.SO,H
forms moderately soluble crystals, and gives
with ammoniacal copper solution a pp. of flat
amethyst^coloured needles.
ETHYLENE BI-THIO-CABBONATE
CjH^COSj. [31°]. Prom ethylene-tri-thio-oar-
bonate by treatment with moderately dilute
nitric acid (Husemann, A. 126, 269). Long thin
rectangular tables (from alcohol). May be dis-
tilled in a current of hydrogen ; insol. water, v.
Bol. alcohol, ether, chloroform, and benzene.
Ethylene tri-thio-oarbonate OjE^CSs. [37^.
S.G. 1-477. From NajCSj and an alcoholic
solution of ethylene bromide (Husemann,^. 123,
83). Large yellow crystals (from ether-alcohol),
with alliaceous odour, si. sol. alcohol, v. sol.
benzene, CSj, and chloroform. Converted by
ammonia into ethylene mercaptan and am-
monium sulphocyanide. KHS gives KjCSj
and ethylene mercaptan. Fuming EHOg gives
C^.(SO.H)r
ETHYLENE THIO-UEEA C,H.NjS i.e.
CS<^S5>CjH,. [194°]. An alcoholic solution
of ethylene-diamine mixed with CS2 deposits
in a short time amorphous OsHgNjSj (or
CS<[|"^^>C2H4 ?), insol. alcohol and ether,
which, when boiled with water, gives ofE HjS,
leaving ethylene thio-urea (Hofmann, B. 5, 240).
Prisms (from water). SI. sol. ether, v. sol. alco-
hol. Tastes bitter. Not altered by digestion at
high temperatures with CSj and PbO.
ComWwaiioras.— •(C3H„N2S)23HgCl^—
(C,H.N,S)2PtCl,.— (C,H.NjS)2H2PtCl, : obtained
by heating ethylene thio-urea with cone. EjSO^,
diluting with water, and adding platinio chloride.
Ethylene -di-thio-di- urea 04H,„N4S2 i.e.
C„H4(NH.CS.NH2)i,. The hydrobromide
B"H^r2 is formed by boiling thio-urea with
CjH^Br^ in alcohol (Andreasch, M. 4, 142). This
salt forms long broad prisms, sol. cold water.
HCl and KCIO, oxidise it to urea and
C2H4(SO.,H)5. The hydrochloride B"HjCl2
(orms geodes of slender needles.
ETHYLENE-TOLYL- v. ToLVL-BlHTLBNii- ;
and mjra.
ETHYLENE ■ 01 - p • TOLYLENE . TETBA-
AIIINE
0,H3(CH3)(NH,).NH.02H,.NH.0.H3(CH,)(NH2).
Bi-m-amido-di-p-tolyl-ethylene-dicmme. [159°
unoor.]. Formed by redaction of di-m-nitro-di-
p-tolyl-ethylene-diamine (Gattermann a. Hager,
B. 17, 779). Long colourless needles. Sol.
alcohol, si. sol. water.
ETHYLENE-SI-TOLYLENE-NITBAUINE v.
Dl-NlTKO-DI-TOIiTli-ETH^LENE-DIAMINB.
ETHYLENE-UBEA CaH^NjO i.e.
CjH«<™>CO. [131°]. Formed by heating
ethylene-diamine with ethyl carbonate ai 180"
(Fischer a. Koch, A. 232, 227). Needles v. sol.
water and hot alcohol, si. sol. ether. Gives with
HNO3 a di-nitro-derivative without any evolution
of gas (Franchimont, B. T. C. 6, 219).
Ethylene-di-urea C^HigN^O, i.e.--
CjH4(NH.C0.NHj)j. [192°]. From silver oyanate
and the hydrochloride of ethylene-diamine (Vol-
hard, Pr. 11, 268). Prisms, sol. water and alco-
hol. Dissolves in HClAq, but separates unaltered
on evaporation. Boiling cone. EOHAq gives
ethylene-diamine, CO,, and ammonia. With a
solution of mercuric nitrate it gives a flocculent
pp. It is immediately attacked by pure HNO„
giving off CO2 and N2O in equal volumes
(Franchimont, B. T. G. 6, 219).— B'2H2PtCls :
orange-red prisms. — B'HAuCl, : golden scales.
EXHYLENE-BI-VBEIHANE v. Eihtlene
SICABBAMia ETHEB.
ETHYL-ETHANE CABBOXYLIC ACID v.
BUIANE-OABBOXTUC ACID.
ETHYL-ETHENYL CABBOXYLIC ACID v.
BUTAI^E TBI-CABBOXnjIO ACID.
ETHYL ETHEB v. Etheb.
ETHYL-ETHYLENE v. Buitiene.
TETEA-ETHYL FEBBO-CYANIDE Et4FeCy,.
[214°]. Formed by the action of silver ferro-
cyanide on ethyl iodide (Freund, B. 21, 935).
Bhombic crystals (from chloroform). V. sol.
water, alcohol, chloroform, insol. ether, petro-
leum ether, and CSj. Is decomposed by cone.
H2SO4 with evolution of COj. EgCl, gives a
white pp.
ETHYL - FLAVANILINE C,eH„N2(C2Hi).
Orange colouring matter. — B'HI : long red
needles. Formed by heating flavauiline with
ethyl-iodide (Fischer a. Rudolph, B. 15, 1502).
ETHYL ELUOEIDE CjH^F. (-48°). V.D.
1-70. S. (gas) 1-98. Produced by distilling a
ihixture of fluor-spar, alcohol, and HjSO, or by
warming KEtSO^ with KHFj (Reinsch, J.pr. 19,
514; Fremy, A. 92, 247). Prepared by passing
EtI over AgF heated to 40° in leaden tubes, and
collected over mercury in dry glass vessels
(Moissan, O. B. 107, 260). Gas, v. sol. EtI and
EtBr. Under 8 atmospheres' pressure it lique-
fies at 19°. Burns with a blue flame. Heated
to dull redness in a glass bulb it gives a
mixture of hydrocarbons together with traces of
fluoride of sUicon. Subjected to a weak induc-
tion spark its volume increases, and it gives hy-
drofluoric acid, and small quantities of acetylene
and ethylene, but no free carbon. Subjected to
a strong induction spark it gives free carbon, also
acetylene, ethylene, propylene, &c. Passed
through a platinum tube heated to dull redness it
494
ETHYL FLUORTDK
yields hydrofluoric acid mixed with hydrocarbons,
partly capable of being absorbed by snlphurio
acid, and a little tree carbon is deposited. An-
esthetic. In large quantities the excitement is
followed by death (Moissan, C. B. 107, 992).
ETHTLtFOSMAHIDE v. Formyl derivative
of EiHYTiAMmE, and also under FoBma acid.
u-DI-ETHYL-FOBHAUIDINE
H0(NBt2):NH. Form-imid-di-ethyl-amide. Pre-
pared by allowing an absolute alcoholic solution
of the hydrochloride of formimido-ether (1 mol.)
and di-ethyl-amine (2 mols.) to stand at the
ordinary temperature for several weeks, and
then distilling oS the alcohol and excess of di-
«thyl-amine on the water-bath. When boiled
(rith alcohol it loses KH,, giving a condensation
product CigHjiN,. The hydrochloride
(B'HGl) forms glistening transparent prisms,
very hygroscopic and easily soluble in alcohol
[125°].— B'jHjCl^PtCl^: yellowish-red sparingly
soluble prisms [209°] (Pinner, B. 17, 179).
s-Di-ethyl-formamidine
HC(NHEt):NEt. Form-ethyl-imid-ethyl-amide.
Fonped by the action of an alcoholic solution of
ethylamine on the hydrochloride of formimido-
ether.
Salts . — B'HCl : large deliquescent plates. —
B'iHjCl JtCl, : thick red prisms [198°] (Pinner,
B. 16, 1649).
ETHYL FOSHAKILISE v. Fobmio acid.
DI-EIHYL-rTTMABAinDE v. Ethylamide of
Fduasic acid.
ETHYL-FTjaFUKIlIE «. Fubfurinii.
TEI-ETHYL-GAILIC ACID «. Galmc aoid.
/3-ETHYL-GLUTAEIC ACID
CH^.CB^.G3.(CB^.G0^)v [67°]. From malonio
acid, propionic ,aldehyde, and glacial acetic acid
at 100° (Komnenos, A. 218, 167). The yield is
very small (4 p.c. of the malonic acid). Small
prisms. V. sol. water, alcohol, ether, or
chloroform.
DI-EIHYL-OLTCIDAMINE C,H,,HO i.e.
O
A
CH2.CH.GH^Et2. This constitution is assigned
by Beboul (Bl. [2] 42, 261) to the substance
[160°] formed by the action of di-ethylamine on
epichlorhydrin. It is v. sol. water. »
Ethylo-chloride CgH^gNOCl i^.
O
'0Hj.CH.CHjj.NBt,01. Formed from epichlor-
hydrin and NBts at 100° (Eeboul, Bl. [2] 42,
261). Syrup. Moist AgjO gives a strongly
alkaline syrupy base. — (CgHajNOO^jPtCl,:
orange needles, v. sol. water, insol. alcohol.
EIHYI-GLYCOCOLL v. Eih».-aiiido-aoeiio
ACID.
ETHYI-DI-GIYCOLABIIC ACID v. Binn-
IMIDO-DI-AOETIO AOID.
ETHYL-GLYCOLLIC ACID «. Efhyl dama-
Hve of GiiTCOLLio acid.
ETHYL-GLYOXALINE C^B^iCJEL^ySy (210°).
S.G. -999. Formed by treating tri-bromo-
ethyl-glyoxaline with sodium amalgam (Wyss,
B. 10, 1373). .Prepared by heating glyoxaline
with ethyl bromide (Wallach, B. 16, 534).
Mobile colourless fluid. Miscible with water.
Methylo -iodide B'Mel : [75°]; large
prisms.— (B'MeI),CdIj: [152°]; plates.
Methylo-chloride B'MeCl: formed by the
action of AgCl on the methylo-iodide. —^
(B'MeCl)jPtOl4: [195°].— (B'MeCl),Zn01j : trans-
parent soluble crystals [158°].
StA^Zo-firomiie CjHsEtNjBtBr. Formed
by heating glyoxaline with EtBr (Wyss, B. 10,
1367). Syrup. -(B-BtC^jPtCajJaq: pearly
plates.
Tri - bromo - ethyl - glyoxaline C3Br3(02H5)Nj.
[62°]. Formed by bromination of ethyl-glyqx-
aline dissolved in dilute H^SOj (Wallach, B. 16,
537). Formed also from, silver tri-bromo-
glyoxaline and EtI (Wyss, B. 10, 1372). Colour-
less crystals. Insol. cold water.
Para-ethyl-glyoxaline GJELJlfi^^^p [77°]
(W.) ; [80°] (R.); (268°) (E.). Formed by isbmerio
change from the tertiary ethyl-glyoxaline by
passing it through a heated tube (Wallach, B.
16, 543). Prepared by the action of propionic
aldehyde-ammonia on glyoxal (Badziszewski, B.
16, 490). Long prisms. Sol. water, alcohol,
ether and benzene, si. sol. ligroin. Secondary
base. — B'jH2CytCl4: easily sollible prisms or
plates. Heated with propyl bromide it gives an
ethyl-propyl-glyoxaline which is probably iden-
tical with oxal-propyline (W.).
Fara- di - ethyl - glyoxaline C3Hj(C2H5)2N,.
Oxal-ethyl-propylme. (220°). S.G. -9813.
Formed by the action of ethyl bromide on ethyl-
glyoxaline (glyoxal-propyhne) (Badziszewski,
B. 16, 491). Colourless liquid with narcotic
smell. Sol. water, alcohol, and ether. Thq
double-zinc-chloride forms crystals melting at
[173°].
ETHYL-GIYOXYLIC ACID C^Ufi, i.e.
Et.CO.COjH. (74°-78°) at 25 mm. S.G. 1-25.
Prepa/raUon.—FioTpionyl cyanide (5 g.) is
mixed with HCl (2-6g. of S.G. 1-23) and kept for
2 hours at 0°. More HOI (2-5 g. of S.G. 1-23) is
added, and, after standing, the mixture is diluted
with water and heated for 3 hours on the water-
bath. The acid is then extracted with ether
(L. Claisen a. E. Moritz, C. J. 37, 693).
Properties. — Liquid with empyreumatio
smell. Miscible with water, alcohol, and ether.
Sodium amalgam reduces it to a-oxy-butyria
acid [43°].
Salts. — ^AgA': prisms. — ^BaA'2aq: m. soL
water.
Amide Et.CO.CO.NH,. [117°]. Prepared
from propionyl cyanide (2 g.) by mixing with
HCl (1 g. of S.G. 1-23) and keeping at 0° for. 2
hours. The semi-solid product is left for a week
over lime. The amide is then separated from
NH^Cl by sublimation (0. a. M.). It may be
crystallised from ether.
Phenyl-hydrazide Et.C(N2HPh).C0jH
[152°]. Obtained by hydrolysis of the product
of the action of diazobenzene chloride on ethyl-
aceto-acetic ether (Japp a. Elingemann, O.J. 5$,
519). Yellow silky needles, decomposed on melt-
ing. Beduced by sodium amalgam to benzene-
o-hydrazo-bntyrio acid Ph.NH.NH.CHEt.COjH.
ETHYL-DIGUANIDE C^Hi.Nj i.e. C^HjEtN,.
Formation. — By heating di-cyan-di-amida
(5 pts.) with CuSOtdaq (7 pts.), ethylamine (8
pts.), and water (32 pts.) for some hours at 100°
there is formed the salt (04Hi,N5)2CuSO,aq,
whence H^S removes the copper, and the re-
sulting (CtH„N,)2H2S04 is then decomposed by
baryta ^mich, M. 4, 895).
Preparation, — An alcoholic solution of di-
ETHYL-HYDRAZINE.
49f.
oyandiamide is heated with ethylamine hydro-
ohloride in a sealed tube for several hours
(Smolka a. Friedreich, M. 9, 229).
Properties. — ^Deliquescent crystalline mass,
V. sol. -water and alcohol, insol. ether.
Salts.— B"H01: six-sided , tables, v. e. sol.
water, insol. alcohol and ether. — B"H2Cl2.—
B"2H2S04 l|aq : small trimetrio crystals, a:b:o
= 1'04:1:1'36 ; v. sol. water, insol. alcohol.
[180°], when anhydrous.— B"H,S04 llaq. S. 4
in the cold. — B"2CuS04 aq : minute rose-coloured
needles (from cold aqueous solutions). —
B"2CuS0, : crimson orystaUine grains (from hot
solutions). S. -0214 in the cold.— B"jNiS04a!aq.—
Cu(04H,„N5)j : fromB"2CuSO, by cautious treat-
ment with aqueous NaOH. Eed needles, si. sol.
cold water. — ^(CjHijN,)^: obtained by boiling
,Ni(0H)2 with ethyl-diguanide. — Picrates
B"08Hj(NOj)30H and B"2C8H,(NOj)30H may be
eiystallised from hot water.
M-DI-ETHTL-GUANIDIIfE
NH:C(NBt2)(NH2). From oyanamide and di-
ethyl-amine hydrochloride (Erlenmeyer, B. 14,
1869). Monoclinic crystals, a:h:c = ■925:1:1-462.
;3 = 74°35' — B'HCl: monoclinic prisms; a:h:o
= ■960:1: -749; $ = &5°5^'.-'B'^^iC\s: orange
triolinio tables ; o:6:e = ■789:1: ■664 ; a=90° 21' ;
j8=92'' 50' ; 7=82° 9' (Haushofer, J. 1881, 330 ;
1882, 364; Z. K. 6, 130; 7, 267).
s-Tri-ethyl-guanidine NEt:0(NHBt)2. Formed
by boiling an aJooholio solution of di-ethyl-thio-
urea with ethylamine and EgO (Hofmann, B.
2, 601). Strongly alkaline liquid ; absorbs CO,
from the air. — B'^ELjPtClj : crystalline plates, v.
sol. water.
ETHTI-w-HEPTYL- OXIDE Et.0.C,H,5.
(166-6°). S.G.g^7949. S.V. 220^8. C.E. (0°-10°)
•001 (Dobriner, A. 243, 5 ; Cross, A. 189, 5).
Ethyl heptyl oxide Et.0.C,H,5. (177°). S.G.
M ^791. V.D. 5-10 (calc. 4-99). From EtI and
the sodium heptylate from castor oil (Wills,
C. J. 6, 312 ; Petersen, A. 118, 75).
ETHTL-HEXTL-GLYOXAIIIIE 0„Hj„Nj.
OxaUthyl-cenanthyKne. (271°). S.G. —
•921. From hexyl-glyoxaline and EtI (Earoz,
M. 8, 222). Oil.— B'jjHjPtCls : yellow soluble
ETHYL HEXYL OXIDE CBLjEt.OHEt.OEt.
(132°). S.G. 2 -787. Prom di-ohlorihated ether
and ZnBtj (Lieben, A. 178, 14). With HI it
gives EtI and secondary hexyl iodide.
ETHYL-HYDANTOIN CsHsNA i.e.
C0<;^^*^^>. Formed by heating ethyl-gly-
ooooll with urea at 125° (Heintz, A. 133, 65).
Tables, melting below 100°. V. e. sol. water and
alcohol. May be sublimed.
ETHYl-HYDEAZINE C^HgN^ i.e.
CjH5.NH.NHj. (99^5° at 709 mm.). Prepared
from s-di-ethyl-urea NHEt.CO.NHEt, which is
treated with nitrous acid and the resulting ni-
trosamine NHEt.OO.NEt.NO then reduced by
zinc-dust and acetic acid to NHEt.CO.NEt.NHj,
whence hot cone. HCl forms NHjEt, OOj, and
NHEt.NHj. Bthyl-hydrazine hydrochloride
being less soluble than ethylamine hydrochloride
may be separated from it by crystaUisatiou
(Fischer, A. 199, 281 ; B. 9, 111).
ProperUes. — Colourless mobile liquid of faint
ammoniacal odoui ; very hygroscopic ; v. eoI.
water, Alcohol, ether, and benzene, si. sol. cone.
EOHAq. It attacks cork and caoutchouc. It
fumes in moist air. It gives the carbamine re-
action with chloroform and alcoholic potash.
Bromine decomposes it, giving o£E nitrogen. It
ppts. metallic oxides from their salts.
Beaotiojis. — 1. Eeduces Fehling's solution in
the cold. — 2. Eeduces Ag^O. — 3. Eeduces HgO
forming HgEtj. — 4. Eeacts with aldehydes with
considerable evolution of heat, forming ethyl-
hydrazides E.OH:NjHEt. — 5. Decomposed by
jiiiroMs aciid gas. — 6. Its hydrochloride reacts
when heated with potassium cyanate in aqueous
solution with production of ethyl semi-carbazide
NH2.CO.NH.NHEt, which forms very soluble
leaflets [105°]. — 7. Its hydrochloride reacts on
phenyl cyanate in dilute ethereal solution, giving
rise to leaflets of phenyl-ethyl-semi-oarbazide
NHPh.CO.NH.NHEt [111°]; v. sol. alcohol, si.
sol. hot water, decomposed by dilute acids into
di-phenyl-urea COj, and ethyl-hydrazine. —
8. Phenyl thio-carbimide gives phenyl ethyl thio-
semi-carbazide NHPh.CS.NH.NHEt [109°],
which crystallises in white leaflets; si. sol.
ether, v. sol. alcohol. — 9. Oxalic ether gives
grouped needles of OA(NH.NHEt)j [204'=], of
which the nitrosamine CA(N(NO).N(NO),Et),
[114°] crystallises in prisms and give^ Lieber-
mann's reaction. — 10. Picryl chloride gives
NHEt.NH.C„Hj(N0j)3 [200°], which forms yel-
lowish-red needles ; si. sol. alcohol, sol. hot
benzene, and explode on heating.
Salts.— B"HjClj: needles, v. e. sol. water
and alcohol, but the solutions on evaporation
leave B"HC1 as a colourless deliquescent mass.
The sulphate forms readily soluble leaflets, the
oxalate is a crystalline pp. sol. hot alcohol.
M-Di-ethyl-hydrazine CjHjjNj i.e. NEt^.NHj.
(c. 98°). Formed, together with NH, and NEt^H,
by reduction of di-ethyl-nitrosamine NEt^.NO
vsdth zinc and glacial HOAo. The bases are con-
verted into hydrochlorides and, on evaporation,
NH,C1 crystallises first. The filtrate is treated
with potassium cyanate and evaporated, when
di-ethyl semicarbazide NHj.CO.NH.NEtj sepa-
rates ; and this is decomposed by heating with
cone. HCl for 12 hours at 100° (Fischer, A. 199,
308).
Properties.— Colourless, mobile liquid, of
faint ammoniacal odour, sol. water, alcohol, and
ether ; nearly insol. cone. KOHAq.
BeacUons. — 1. Eeduces hot, but not cold,
Fehling's solution, being for the most part con-
verted into diethylamine and nitrogen. — 2. Mer-
cti/ric oxide converts it in the cold into tetra-
ethyl-tetrazone Et|,N.N:N.NEt2, a non-vola-
tile oil, sol. alcohol, which is decomposed by
heat, is volatile with steam, and reduces ammo-
niacal AgNO,, forming a mirror. Dilute HCl at
80° splits up tetra-ethyl-tetrazoneinto aldehyde,
NEtHj, NEtjH, and nitrogen. The tetrazone
forms a platinochloride BtjNiHjPtCls, and gives
with mercuric chloride a crystalline pp.
BtiN^HgClj. — 3. Nitrous acid forms NjO and
diethylamine (or diethyl nitrosamine). — 4. Its
hydrochloride is converted by potassium cyanide
into M-di-ethyl semicarbazide BtjNiNH.CO.NHj,
which forms long prisms [149°], sol. hot water
and alcohol, insol. cone. KOHAq. It forms a
crystalline nitrosamine Et2N.N(N0).C0.NH,.
Salts. — The hydrochloride, sulphate,
496
ETHYL-IIYDRAZINE.
and nitrate are exceedingly sol. water and al-
cohol. The picrate and platinochloride
B'jHjPtCls form golden needles.
Ethylo-iodide NHj.NEtal. Needles, v.
sol. water and hot alcohol, insol. cone. KOHAq
and ether. Moist AgjO forms a strongly alkaline
hydroxide which is decomposed at a higher tem-
perature into water, ethylene, and di-ethyl-hy-
drazine. It may be reduced by zinc and H2S04
to tri-ethylamlne.
ETHYI-HYDEAZINE STJIPHONIC ACID
EtNjH,.SOsH.
Salt. — KA'. Prepared by heating K^SjO,
with ethyl-hydrazine at 90° ; the mass obtained
being warmed with aqueous KHCO, and eva-
porated below 70° (Fischer, A. 199, 300). Leaflets,
BOl. water, si. sol. alcohol. On boiling with
strong acids it is decomposed into ethyl-hydra-
zine and EHSO,. When its aqueous solution is
treated with HgO, even in the cold, it yields
potassium diazo-ethane sulphonate EtN^SOjK
in the form of glittering needles or leaflets, sol.
alcohol. Diazo-ethane sulphonate explodes vio-
lently when heated ; it may be reduced by zinc-
dust and acetic acid to the parent ethyl-hydra-
zine sulphonate.
ETHYL-HYDEOCABBOSTYEIL®. Oxy-btht!l-
QUINOLIHE MHTDKIDE.
ETHYL-HYDROXYIAMINE v. Hybroxyl-
AMINE.
ETHYL HYPOCHLOBITE C^HsOCl. (36°).
Pt'eparation. — Chlorine is passed through a
cold solution of NaOH (1 pt.) in alcohol (1 pt.)
mixed with water (9 pts.) as long as the bubbles
are absorbed. The ether rises as an oil to the
surface and is washed and dried over CaCl,
(Sandmeyer, B. 18, 1767 ; 19, 857).
Properties. — Yellow mobile liquid with very
irritating smell. It may be distilled. It is very
unstable. On superheating its vapour in a tube
it explodes violently. The explosion is also
brought about in the cold by contact with pre-
cipitated copper. Exposed to difiused daylight
it begins to decompose after a few hours' boiling
violently ; in direct sunshine this decomposition
begins in a few minutes and ends with an explo-
sion. It mixes without reaction with ether,
chloroform, and benzene. Upon aniline, phenol,
&c.,it acts likeClOH, oxidising and chlorinating.
With HCl, HBr, and HI it at once yields the
halogens with liberation of alcohol.
ETHYL HYPOPHOSPHATE Et,PA- S.G.
»5 1-117. Prom AgiPA and EtI in the cold
(Sanger, A. 232, 8). Thick colourless liquid.
Heated alone it is decomposed into ethyl phos-
phate and ethyl phosphite. It is saponified by
water.— EtCaHPjOjSaq. Needles.
ETHYLISENE. The .divalent radicle
CHj.CH. Unlike its isomeride ethylene, it is
not known in the free state. By heating ethyl-
idene chloride with sodium at 190° ToUens (A.
137, 311) obtained ethylene, acetylene, ethane,
and C2H3CI.
ETHYLIDENE DIACETATE v. Di-acetyl
derwatwe of O^iAo-AUJEHYDE, vol. i. p. 106.
ETHYLIBENE DI-ACETIC ACID «. Methyl-
GLUTABIO ACID.
ETHYLIDENE-ACETO-ACETIC ETHEE is
described under Aobto-acbtic acid.
ETHYLIDENE-DI-ACETOHAMINE «, AoE-
TOHAMINI!.
ETHYLIDENE-DI-ACETONE-ALCAMINE «.
AOETONE-ALCAUINEB.
ETHYLIDEHE-DI-ACETOITIKE v. Aobtc
NINES.
ETHYLIDENE ALDEHYDATE v. AcEiAi.
ETHYLIDENE-m-AMIDO-BENZOIC ACID
CjHgNOj i.e. CHs.CH:N.C„H^.CO^H. Formed
by mixing dilute aqueous solutions of m-amido-
benzoic acid and aldehyde (SchiS, A- 210, 117).
Amorphous mass, v. e. sol. alcohol and benzene ;
melts under boiling water. Long boiling with
water decomposes it, COj and ethylidene-aniline
being among the products. Gone. HNO, con-
taining E^^rjO, gives a transient violet colour.
ETHYLIDENE-DIAMINE. Benzoyl deri-
vative CisHieNA i.e. OH,.CIH(NHBz)j. [204°]
(H. a. S.) ; [188°] (N.). S. (alcohol) 1-24 at 22°.
Formaiion. — 1. From aldehyde-ammonia and
BzOl (Limpricht, A. 99, 119).— 2. By dissolving
benzamide in aldehyde to which a few drops of
HCl have been added; the reaction being at-
tended with rise of temperature (Nencki, B. 7,
158). — 3. By gradually adding benzonitrile
(2 mols.) to well-cooled cone. H^SOj containing
paraldehyde (1 mol.), leaving the liquid to itseU
for a few hours, and then ppg. the product by
water (Hepp. a. Spiess, B. 9, 1424).
Properties. — Long needles (from alcohol), v.
sol. CHCI3, CSj, ether, and hot alcohol, nearly
insol. water. May be sublimed.
Beactions. — 1. With water at 130° it' gives
aldehyde and benzamide.-r-2. Boiled with dilute
(10 p.c.) H2SO4 it gives aldehyde, NH„ and
benzoic acid.
Tri-ethylidene-diamine v. Axdehyde, Com-
bination 4, vol. i. p. 104.
ETHYLIDENE-ANILINE OjHsNiCH.CHa (?).
A Idehyde-aniUde. From ethylidene chloride and
aniline at 160° (Sohiff, B. 3, 415).
Preparation. — A mixture of aniline and al-
dehyde is made at — 18°, then left to itself for
some weeks at 15°, and finally heated to 100°.
Aniline is removed from the product by dilute
HOAc, and the ethylidene-aniline is separated
from ethylideue-di-aniline by alcohol, in which
it readily dissolves (Schift, A. 140, 127; 210,
114). Bedresin.- B'jHgOlp— B'lHjPtCl,: orange
crystalline pp.
Ethylidene - di - aniline (C,H5.NH)2CH.CH,.
Prepared as above. Yellow nodules. —
B'jHjCljHgOlj.— B'jHjPtOlj: orange crystalline
pp.
ETHYLIDENE-BITJSET 0,H,N,0, t.e.
NH<^^-^^>CH.CH,. Trigerm acid. Mol. w.
129. Formed by passing cyanic acid into cold
aldehyde (Liebig a. Wijhlor, A. 59, 296). Small
prisms (from water). SI. sol. water, almost
insol. alcohol. Acid to test papers. Decom-
posed on dry distillation with formation of am-
monia, ammonium carbamate, and an oil, which
is in all probability a tri-methyl-pyridine, iden-
tical with that obtained by Baeyer and Ador (A,
155, 294). When heated with Mel and alcohol
it yields ammonia and methylamine. With
NaOBr it evolves only traces of nitrogen. On
oxidation with HNO3 it is converted into cyan-
uric acid and carbonic anhydride, a reaction
which points to the above formula (Herzig, M,
8, 398). — AgA' : pulverulent pp. sol. hot water.
ETHYLroENE-METHYL-KETOLE.
407
ETHTUDENE BBOMIBE OjH,Brj i.e.
CHs.CHBrj. u-Di-bromo-ethane. (113°). S.G.
^^ 2089 (A.) ; if 2-1029 ; || 2-0854 (Perkin,
C. J. 45, 523); '£ 2055 (Weegmann, Z. P. 0. 2,
218). Md 1-5128 (W.). M.M. 9-1.
FormaUon. — 1. By brominating ethylbromide
in sunlight (Staedel, B. 11, 1741).— 2. From
vinyl bromide and HBr (Eeboul, O. B. 70, 399).
Pr&garation. — ^Prom PClaBrj and aldehyde
in the cold (Fatern6 a. Pisati, G. 1, 596 ; An-
schiitz, A. 235, 301).
Beactums. — 1. Benzene and AliCl„ form
ethyl-benzene, M-di-phenyl-ethane, and s-(A)-
di-methyl-anthraoene di-hydride. — 2. Alooholio
KOAo at 130° gives aldehyde, EtOAo, and acetal
(TavildarofE, A. 176, 12).— 3. Alooholio KHS has
no action (difference from ethylene bromide). —
4. Ammoma at 130° forms tri-methyl-pyridine
(coUidine).— 5. Water and PbO at 130° give al-
dehyde.— 5. SbClj forms exclusively CH3.CHCI2
(Henry, O. fl. 97, 1491).
ETHYIIDENE SSOMO-IOSIDE v. Bbomo-
lODO-ETHANE.
EIHYLISENE-SI-CABBAMICACID. Ethyl
ether C^.aNjOi i.e. CH3.CH(NH.C0^t)j.
EthyUdene-v/rethcme. [126°]. Formed by the
action of aldehyde or acetal on carbamic ether
in presence of HCl (Nencki, B. 7, 160 ; Bischoff,
B. 7, 629). Formed also from aldehyde-ammonia
and chloro-formio ether in the cold (Schmid,
J.pr. [2] 24, 124). Satiny needles; v. sol. ether,
alcohol, and hot water. Split up by hot dUute
acids into aldehyde and carbamic ether.
Propyl ether OB^.GB.{^B..C0J2^,\.
[116°]. From propyl carbamate, aldehyde, and
a little HCl (Bischoff, B. 7, 1082).
EIHYLIDENE GHLOBHYBBIX v.oi-Chloiio-
ETHYL ALCOHOIi.
EXHTLIDENE CHIOEIDE C^fH, i.e.
CH3.CHOI2. Mol. w. 99. (60-1°) (Thorpe, C. J.
37,183): (66-8°)at 749 mm. (Schiff); (57-3°)
(Perkin, C. J. 45, 529) ; (57-5°) (Bruhl). V.D.
3-42 (for 3-42) (S.)- S.G. 1 1-2039 (T.) ; ^-^ 11895
(Schiff, A. 220, 96) ; if 1-1845 ; || 1-1712 (P.) ;
I" 1-1743 (Briihl, A. 203, 11) ; 1-1750 (Weegmann,
Z. P. C. 2, 218). C.B. (0°-10°) -001304 ; (0°-50°)
-0013982 (Thorpe) ; (9-8 to 56-7) -001488 (Schiff).
S.V. 88-96 Thorpe) ; 88-56 (Schiff) ; 89-5 (Ram-
say). M.M. 5-335 at 14-4°. p.^ 1-4168 (W.).
;i^= 1-4223. Eoo = 34-10 (B.). H.P.p. 34,230
(2'fc.). H.F.V. 33,070 (Th.). 1 Critical tem-
perature 255° (Paulewsky, B. 16, 2633). By-
product in manufacture of chloral (Kramer, B.
3, 257).
Formaticm. — 1. By chlorinating ethylchloride
in dayUght (Eegnault, A. Ch. [2] 71, 355), or in
presence of heated animal charcoal (Damoiseau,
Bl. [2] 27, 113).— 2. By heating aldehyde with
POI5 (Wurtz a. FrapoUi, C. B. 47, 418; A. 108,
223; Beilstein, 4. 113, 110; Geuther, A. 105,
321). The POI5 is at first kept cool, and the al-
dehyde added slowly.
Properties. — Colourless oil, resembling chloro-
form in taste and odour.
BeacUcms. — 1. Alcoholic potashhaa no action
in the cold, though vinyl chloride is formed on
heating.— 2. Aqueous Na^SO, at 140° gives
CHs-CHOLSOsNa (Kind, Z. [2] 5, 165). Boiling
aqueous K^SO, gives CH3.CH(S0,K)j and
CH,.0H(OH)SO,K (Staedel, Z. [2] 4, 372),— 3.
Vol. II.
Sodium at 190° gives hydrogen, acetylene, ethyl-
ene, ethane, and vinyl ohlorideJToUens, A. 137,
311).— 4. Chlorine gives CHjCl.CHClj and
CH,.C01, (Staedel, B. 6, 1403).— 6. Bromine in
sunlight forms CHa.OBrClj (99°), OH^r.CBrOl,
(177°), and CHBrj.CBrOL, (217°) (Staedel, B. 11,
1739).— 6. Toluene and AljCl, give ^-ethyl-
toluene, «-j>-di-tolyI-ethane, and s-tetra-methyl-
anthracene dihydride (Anschutz, A. 235, 314).
»»-Xylene, and AljClj give (1, 3, 4)-ethyl-?«-xylene
and't<-di-zylyl-ethane.
ETHYLISEITE CHLOBO • BBOUIDE v.
Chlobo-bbomo-ethane.
ETHYLISENE CHLOBO-IODIDE v. Ghlobo-
lODO-EIHANE.
EIHYLIDENECYAirXrBAIIIDE is described
nnder Cya/n/wramide v. Ctakio aoio.
ETHTLIDEITE-ETHENYL CABBOXYUC
ACID V. BrTYLENE oabboxylio acid.
ETHYLIDENE BI-ETHYL BIOXIBE is
Acetal (q. v.).
ETHYLIDENE - DI - ETHYI -DI -STJIPHOITE
CH3CH(S0jEt)j. [75°-78°]. Prepared by treat-
ing CH,.C(SEt)3.C02H (obtained from pyruvic
acid and mercaptan) with KMnO, (Bscales a.
Bamuann, B. 19, 2814). Plates ; sL sol. water,
m. sol. alcohol and ether. Evolves hydrogen
when sodium is added to its solution in ^y ether
or benzene, the resulting salt is too unstable to
purify (E. Fromm, B. 21, 187). Its bromo- deri-
vative CH3.CBr(S0jEt)j [115°] crystallises in
small sparingly soluble prisms which are recon-
verted by boiling KOHAq into the original
CH3.CH(S0jEt)j.
ETHYIIDENE lOBIBE CHj.CHIj. (o.l78°).
S.G. 2 2-84.
Formation. — 1. From ethylidene chloride and
Aljlo in CS2 (Gustavson, B. 7, 731).— 2. From
CHsCHCL, and Cal^ 3Jaq at 100° (Spindler, A.
231, 267).— 3. From acetylene and HI (Berthelot,
A. 132, 122).
Properties. — Liquid. Converted by alcoholio
KOH into vinyl iodide.
ETHYUBENE-LACIAmiG ACID v. a-lmoo.
DI-FBOFIONIC ACID.
ETHYLIDENE-LACIIC ACID v. Laciio acid.
ETHYLIDEITE-MAIONIC ACID
CH3.CH:C(C02H)i,. Ethyl ethermj^". (115°-
118°) at 17 mm. 8.6.1^1-0435. Frommalonio
ether (1 mol.), aldehyde (2'mols.), and Ac^O (1^
mols.) at 100° (Komnenos, A. 218, 157). (The
yield is 54 p.c. of the malonic ether.) Liquid,
smelling something like camphor. Aqueous
baryta forms various salts,' including an easily
soluble one, which is possibly a salt of oxethyl-
malonic acid, CH3.CH(0H).CH(C02H)j. KOH
and dilute alcohol gives j3-methyl-glutario acid.
Ethylidene-di-malonic ether
CH3.CH(CH(C02Et)j)j. (209°-212°) at 20 mm.
A by-product in the preparation of etbylidehe-
malonic ether. (The yield is 8 p.c. of the ma-
lonic ether ; Komnenos, A. 218, 158.) It is formed
by the action of ethylidene-malonio ether upon
malonioether: CH3.CH:C(C02Bt)2 + CH2(C0aEt)j
= CH3.CH(CH(C0jEt) 2)2. Dilute alcoholio KOH
converts it into j3-methyl-glutaric acid.
ETHYIIDENE-MELAMmE described under
EthyUdene-cyanmramide v. Ctanic acids.
ETHYLIDEITE-IIETHTL-KETOLE v. Di-
WETHn-EIB^jIDENE-DI-INDOIiE. '
498
ETHyLIDENE-DI-(j3>NAPHTHYL-0XIDE.
ETHTLIDENE-DI - {fi) - NAPHTHYL-OXIDE
CH3.0H<'p'»S«>0. Anhydride of di-oxy-di-
napMhyl-ethane. [173°]. Crystalline solid.
Insol. alkalis. Formed by heating a solution
of (3}-naphthol and aldehyde in acetic acid with
EGl or H2SO4, or by the same treatment of the
previously formed cU-(3)-naphthyl orthaldehyde
OH3.CH(O.C,„H,)2 (Claisen, B. 19, 3318 ; A. 237,
270 : cf. vol. i. p. 105).
ETHYLIDENE-DIOXAMIDE CeHioN^O, i.e.
(NHj.CO.CO.NH)2CH.CH3. A pulverulent pp.
formed when cyanogen is passed into crude alde-
hyde (Berthelot a. Pfian de St. Gilles, A. 128,
338 ; cf. Schiff, A. 151, 211).
EXHTLIDENE OXT - GHLOBIDE v. Bi-
OHIiOIlO-M-ETHTIi OXIDE.
ETHYIIDENE-DI-PHENOL . v. Di-oxy-w-
PHBNTIi-KTHANE.
ETHYLIDENE-METAFYRAZOLONE v. Di-
OXT-ETHTUDENE-FYBAZOLE.
ETHTLIDENE STTIPHIDE v. Thio-aoeiio
AljDEHmE.
Di-ethylidene-tetra-sulphlde
CH,.CH<;^-^>CH.CH,. Formed by oxidation
of thialdiue by adding to the solution strongly
acidified with HGl a weak solution of iodine in
EI. Amorphous pp. (Fasbender, B. 20, 463).
EXHYMDENE-THIO-TJEEA OjHaNjS i.e.
OS<^^]>CHMe. From aldehyde and thio-
urea at 100° (Emerson Eeynolds, C. N. 24,-87).
Granules, insol. cold water, m. sol. hot alcohol,
si. sol. ether. BoHing water splits it up into
aldehyde and thio-urea.
Si-ethylidene-thio-nrea. Ammonia com-
pound (CH3.CH)2N2CSNH3. [180°]. Formed
by heating a moderately concentrated solution
of thio-urea with aldehyde-ammonia (Nencki,
B. 7, 158). Needles ; si. sol. boiling water, insol.
cold alcohol and ether. Its aqueous solution,
which is intensely bitter, is resolved by prolonged
boiling, or more quickly in presence of acids,
into aldehyde, thio-urea, and HH,.
ETHYLIDENE-TOLUIDINE
CH3.CH:N.CsHjMe ? Aldehyde-toluide. Yellow
nodules, formed by treating toluidine with alde-
hyde. Its salts are resinous (SchiS, Z. 1865,
400).
EXHYLIDES-E-UBEA CjH.NjO i.e.
C0<<^g>CH.CH3. [154°]. Formed by the ac-
tion of at) alcohoUo solution of aldehyde on urea
in the cold (SchifF, A. 151, 204). Small needles ;
V. si. sol. water and ether, si. sol. alcohol. De-
composed by heat into NH,, melanurenio acid,
and oxy-trialdine CjH, ,N0. Eapidly decomposed
by pure HNO3 with evolution of COj and NjO in
equal volumes, together with a little nitrogen
(Franchimont, B. T. O. 6, 221).
ETHYIIDENE T7BETHANE v, Eihylidene-
DI-CASBAMIO AOID.
ETHYL-IMIDO-DI-ACETIC ACID OjH„NO,
i.e. NEt(CH2.C02H)2. Ethyl-di-glycoUamic acid.
From ethylamine and chloro-aoetio acid (Heiutz,
A. 132, 1 ; 145, 229). Short trimetric prisms,
V. sol. water, si. sol. alcohol. — CuA": minute
blue dimetric tables, si. sol. water.
MIthyl ether EtjA". (0. 210°). OU.
ETHYLIStlDO-BI-FHENYLENE SULFHIOS
S(08H4)2NEt. Ethyl-tMo-diphmylamine. [102°].
From imido-diphenylene sulphide and EtBr
(Bernthsen, 4. 230, 93). Prisms. Fed, colours
its alcoholic solution pale brown.
TBI-ETHYLIN v. Tri-eihyl derivaUve of
GliYCERIN.
ETHYL-INDAZINE 0„H,„N *.«.
/OH.
CgHx I ^NCjHj. Formed by heating iudas-
\ N /
ine with EtI for four hours at 100°, saturating
with NaOH, and extracting with ether (Fischer
a. Tafel, A. 227, 303). Brown liquid, smelling
like indazine ; more sol. water than indazine.
Is a tertiary base. — B'HjSOj.
Bromo-ethyl-if'-indazine OjHaN^r. [48°].
Obtained as a sublimate by heating bromo-
ethyl-i((-indazine carboxylic acid, OOj being
evolved (F. a. T.). V. si. sol. water, v. sol. alco-
hol, ether, and chloroform. It shows no basic
properties.
ETHYL-il'-INDAZYL-ACETIC ACID
0„H„NA i-e. CsH,<^(^^f^5^. [131°].
Formed by atmospheric oxidation of ethyl-hy-
drazido-oinnamic acid which is obtained from
the nitrosamine of ethyl-o-amido-oinnamio acid
N0.NBt.05H,.CH:CH.002H by reduction with
zinc-dust and acetic acid (Fischer a. Euzel, B. 16,
654 ; Fischer a. Tafel, A. 227; 303). Colourless
plates, sol. alcohol, ether, and aqueous alkalis,
si. sol. water. At 100° it splits off OOj, forming
methyl-ethyl-i|'-indazine. It forms salts both
with acids and with bases. It does not reduce
Fehling's solution or HgO.
Bromo-ethyl-i/'-indazyl-acetic acid
OiiHiiNjOjBr. [173°]. Formed from the pre-
ceding by treatment with Br (65 pts.) in
HOAc (Fischer a. Kuzel, A. 221, 288). Needles,
grouped in fans, v. sol. alcohol and ether, almost
insol. water. Oxidation with KJCifi, and HjSO,
forms bromo-ethyl-<j/-indazine carboxylic alde-
hyde C,i;H,N20Br [88'] and, by further oxida-
tion, bromo-ethyl-iff-indazine carboxylic acid
CijHaNjOjBr [210°], which crystallises in needles
(from MeOH).
Di-bromo-ethyl-ij/-indazyI-acetic acid
C„H,„BrjN202. [196°]. From the acid (1 pt.)
and Br (1-7 pts.) in HOAc (5 pts.) in the cold.
Stellate groups of needles ; almost insol. water,
si. sol. alcohol, ether, and chloroform. Be-con-
verted into the parent acid by sodium amalgam.
DI-ETHYI-IHDIGO C^^.fi^^ i.e.
CjHiiCjOjNjEtjrCjH,. Prepared byreducing the
di-ethyl-derivative of pseudo-isatin-oi-oxim
CsH4<;^^j>0(NOEt) with alcoholic ammo-
nium sulphide, and then passing a stream of CO,
through the solution (Baeyer, B. 16, 2201). Blue
felted needles. V. sol. alcohol, forming a deep-
blue solution, the spectrum of which closely re-
sembles that of indigo. In ether, acetone,
chloroform, OS,, and aniline it is less soluble.
It sublimes as a purple vapour, condensing to
blue prisms. It dissolves in strong H^SO, with
a greenish-blue colour, and on heating is sulpho-
nated. With zinc-dust and alkalis it is re-
duced, and the solution then dyes like indigo. On
oxidation it gives ethyl-pseudo-isatin. By weak
ETHYL-ISATm.
499
(about 247°). Obtained by
leduotion the di-ethyl-derivative of paeudo-isatin-
H-oxim is formed.
ETHYL-INDOLE C,„H„N i.e.
heating at ISS'-ISO" the oarboxylio acid [183°]
which is formed by the action of HCl on phenyl-
ethyl-hydrazine-pyruvio acid (Fischer a. Hess,
B. 17, 566). Liquid. The HCl solution gives a
violet colour to a pine-wood shaving. By a cold
alkaline solution of chlorine, followed by hot alco-
holic NaOH, it is converted into ethyl-pseudo-
isatin. The picrate forms red needles.
Ethyl-iudole 7
0^<NH>02?
(283°
cor.). Formed by heating aniline (30 g.) with
ZnClj (50 g.), lactic acid (35 g.), and sand to pre-
vent frothing (Piotet a. Duparc, B. 20, 3415). Yel-
low oil without basic character, v. si. sol. water,
V. sol. alcohol, ether, benzene, and OHCI3. May
be distilled with steam. Colours pinewood
moistened with HCl red. Bromine added to its
solution in chloroform gives an intense violet
colour. The picrate melts at [143°].
EIHYL-INDOLE-CABBDX'irLXC ACID
C,,H„NOj i.e. C,H,< ^CH [183°]. Formed
by the action of hot aqueous HCl on phenyl-
ethyl-hydrazine-pyruvio acid (for theory of re-
action V. under IndoiiE derivatives) (Fischer a.
Hess, B. 17, 565). Colourless needles. V. sol.
alcohol, ether, benzene, and chloroform, less
sol. water. Heated to its melting-point for some
time it loses CO^, giving ethyl-indole. A cold
alkaline solution of chlorine, followed by alco-
holic NaOH, converts it into ethyl-pseudo-isatin.
ETHYL-INDOXYL v. Indoxil.
ETHYL-IWDGXYIIC ACID v. Indoxxmo Aoro.
EIHYL-DI-IODAMINE v. Ethyiamine.
ETHYL IODIDE G^U,l. Mol. w. 156. (72°)
(SehifE) ; (72-4°) (Perkin, 0. J. 45, 460). S.G. *|
1-9433; if 1-9243 (P.); § 1-9795 (Dobriner, 1.
243,24). C.E. (0°-10°) -00116 (D.). S.V.86-12
(S.); 85-6 (D.). V.D. 5-48 (calc. 5-41). M.M.
10-075 at 18-1° (P.). H.F.p. 5,660 (Iodine solid) ;
11,090 (I gaseous) (Th.) ; 7,000 (I gaseous, EtI
gaseous) (Berthelot) ; 12,700 (I sohd, EtI liquid)
(B.). H.F.V. 4,790 (I solid) ; 9,930 (I gaseous)
(2"^). Formed by distilling alcohol with HI
containing free I, or by the action of P and I on
alcohol (Gay-Lussac, A. Ch. 91, 89 ; Serullas,
A. Ch. [2] 25, 323 ; 42, 119 ; Marchand, J. pr.
33, 186 ; Frankland, C. J. 2, 263 ; 3, 322 ; Lante-
mann, A. 113, 241 ; Hofmann, O. J. 13, 69 ; De
Vrij, J. Ph. [3] 31, 169 ; Paterno, (?. 4, 149 ; H.
Sehiff, B. 7, 692 ; Personne, C. B. 52, 468). The
rate at which HI etherifies alcohol has been
studied by Villiers (0. B. 90, 1563 ; 91, 62).
Preparatimi. — 1. Amorphous phosphorus
(10 pts.), alcohol (50 pts. of 90 p.c.), and iodine
(100 pts.), are mixed and left to themselves for
24 hours ; the mixture is then distilled (Eieth a.
Beilstein, il.l26, 250).— 2. An alcoholic solution
of iodine is slowly run into a retort containing'
alcohol and clear phosphorus (Hofmann).
Properties. — Colourless liquid. Not very in-
flammable. When not quite pure it turns brown
IP light. ConQ. HNO, liberates iodine. Aqueous
KOH has little action. When a soluble salt of
silver is added to an alcoholic solution of EtI
silver iodide is ppd.
Beactions. — 1. Passage through a red-h^t
tube gives hydrogen, ethylene, and ethylene
iodide (E. Kopp, J. Phami. [3] 6, 109).— 2. Mer-
cury forms EtHgl. — 3. Heating with ZnEt^ in
ethereal solution at 170° gives butane, together
with a little ethylene and ethane (Brodie, C. J. 3,
405). — 4. SocUmn ethide gives ethylene and ethane
in the cold .— 5. Tin at 180° gives SnEtJ^
(Frankland, ' 0. J. 6, 57). — 6. Silver powder at
120° gives butane (Wislicenus, Z. [2] 4, 681).—
7. By heating in sealed tubes with excess of eirpo
there is formed zinc ethide ; when excess of EtI
is used the product is butane.— 8. The copper
zinc couple at 100° forms IZnEt. In presence
of water or alcohol ethane is evolved (Gladstone
a. Tribe, G. 3. 26, 445). — 9. Alcoholic ammonia
forms iodides of ammonium and of mono-, di-,
tri-, and tetra- ethyl-ammonium. — 10. When
saturated with PH, and heated, either alone or
with ZnO, there is formed tri- and tetra- ethyl-
phosphonium iodide (Hofmann, B. 4, 372). —
11. Chromic acid mixture gives iodine and ace-
tic acid. — 12. Chlorine gives EtCl and I (Dumas
a. Stas, A. 35, 162). — .13. Bromine gives EtBr
and I (Friedel,C. B. 60, 346).— 14. ICl gives EtCl
and I (Geuther, A. 123, 123).— 15. HI at 150°
forms some ethane (Butlerow, A. 144, 36). —
16. Heating with HgC^^ gives EtCl (Oppenheini,
0. B. 62, 1085).— 17. Heating with K^SO, gives
potassium ethane sulphonate EtSO,K (Strecker,
Z. [2] 4, 218). — 18. Sodium amalgam acting on
a moist mixture of EtI with CS^ forms EtjCS,
(Nasini a. Soala, G. 17, 236 ; cf. Lowig a. Schplz,
J.pr. 79, 441).— 19. Water at 150° gives ether
(Eeynoso, A. Ch. [3] 48, 385).
ETHYL-ISATIN C,„H,N02. [137°]. Long
red needles (Paucksch, B. 17, 2805). Formed by
heating with HCIAq the product of the action of
di-chloro-acetic acid on ^ -amido-phenyl-ethane
C.H,Et(NH,)[l:4].
Ethyl-pseudo-isatin Ca'B.^<^■Ji,^CO. Lac
tam of ethyl isatic acid. [95°].
Formation. — 1. By the action of a cold alka-
line solution of chlorine followed by hot alcoholic
NaOH on ethyl-indole-carboxylio acid [183°],
which is obtained by the action of HCl on phe-
nyl-ethyl-hydrazine-pyruvioaoid(Fisohera.Hess,
B. 17, 666).— 2. By reduction of the di-ethyl-
derivative of pseudo-isatin-w-oxim
C|,H4<^^^^C(N0Bt) with zinc-dust and oxida-
tion of the product with FejCl, (Baeyer, B. 16,
2193).
Properties. — Large red plates. Soluble in hot
water, alcohol and ether. With thiophene and
HjSOi it gives a blue colouring-matter soluble
in ether. It dissolves in alkalis with a yellow
colour at once forming a salt of ethyl-isatio acid
„ TT /CO.COjH
^s^iSNHEt •
Ethyl-pseudo-isatin-a-ozim
CaH,<;|<^°-^)>CO. [162°]. YeUow four-sided
prisms. Formed by the action of hydroxylamine
on ethyl-pseudo-isatin. On reduction with zinc-
dust followed by oxidation with FejOlj it yields
ethyl-pseudo-isatin. It does not yield indigo on
t»8
EOO
ETHYL-ISATIN.
treatment with ammonium Bulphide (Baeyer, B.
16, 2196).
Ethyl-psendo-isatin-a-ethylozim v. Di-ethyl-
derivaUve of pseudo-Jaxim-a-osjm.
ETHTL-KAIEIIIE v. Ethyl ether of {B. 4)-
Oxl-{Py. 4)-ETmtL-QriN0I(INE ietbahtdbidb.
DI-ETHYI-KETINE v. Di-mbihyl-di-bthzi.
FYKAZINE.
DI-ETHYL-KETONE 05H,„0 i.e. Et.CO.Bt.
Propione. Metacetone. Mol.w.86. (101°). S.G.2
•829;^*-815. S.4-2. H.0. 735,971 (Louguinine,
Bl. [2] 41, 389). A product of the distillation of
Bugar, Etarch, or mannite with lime (Fremy).
Formation. — 1. By the dry distillation of
barium propionate (B. Morley, A. 78, 187). —
2. By the action of ZnEtj on propionyl chloride
(Freund a. Pebal, A. 118, 9).— 8. From sodium
ethide and CO (Wanklyn, A. 140, 2U).— 4. By
oxidising oxy-hexoio acid (di-eth-oxalic acid)
with KjCrjO, and E2SO4 (Chapman a. Smith,
C. J. 20, 173) ; or by heating the ether of the
same acid for several hours with fuming HCl at
150° (Geuther, Z. 1867, 709).— 5. By oxidation
of di-ethyl-carbinolEt2CH(OH) (Wagner a. Sayt-
zeff , A. 179, 822).— 6. By the action of dry PeOl, on
propionyl chloride (Hamonet, Bl. [2] 50, 547).
Properties. — Mobile oil, lighter than water,
V. sol. alcohol and ether. Smells like acetone.
Slowly combines with KHSO3 on long agitation
(Schramm, B. 16, 1583). Chromic acid mixture
oxidises it to propionic, acetic, and carbonic
acids. Beduced by sodium in presence of water
to di-ethyl-oarbinoland the pinacoue C,|,Hgi,(0H)2.
Treated with di-methyl-aniline and ZnCl^ there
is formed tetra -methyl -di-amido- di- phenyl -
methane (Dobner a. Petsohoff, A. 242, 333).
Treatment with Zn, EtI, and then with water
gives tri-ethyl-carbinol (A. Saytzeff, J. pr. [2]
31, 320).
Cyanhydrin Bt2C(0H);CN. a-Oxy-hexo-
nibriU. 'Eiam the ketone and dilute HON
(Tiemann a. Kohler, B. 14, 1978). Litiuid,
lighter than water.
Oxim BtjOtNOH. (163°) at 726 mm. From
di-ethyl-ketone and an alcoholic solution of hy-
droxylamine (SchoU, B. 21, 509). Oil, insol.
water, sol. alcohol and ether. When dissolved
in ether and treated with N2O4 it gives amyl-
paeudo-nitrole Et2C(N0).N0jinthe form of large
tables [63°], which forms blue solutions in ether
and chloroform.
DI-ETHYL-KETONE DI-CARBOXYIIC ACID
C,H,„0, i.e. C0(CH2.CHj.C0jH)j. [138°] and
[c. 110°]. Formed by saponifying its ether.
Thin plates, decomposed on distillation. Not
reduced by sodium-amalgam. Does not combine
with Br. HNO3 oxidises it to succinic acid. —
Ag.A" : minute needles.
'Mono-ethyl etherBtnA". [68°]. From
EtjA" (1 mol.) and alcoholic KOH (1 mol.).
Needles, insol. ligroin, sol. water, alcohol, ether,
and chloroform. — AgEtA".
Di-ethyl ether EtjA". (286°). Formed
by heating furfuryl-acrylic acid with alcohol
saturated with HOI (Marckwald, B. 20, 2811 ;
21, 1398). Heavy oil. Alcoholic NHj forms
C,H„OA [292°]-
Oxim of the di-ethyl ether
H0.N:C(CHj.CH2.C0^t)s. [38°]. Slender
seedles, si. aol. water.
Phenyl-hydrazide
Nja.Fh.CiC^n^.GO,B.)^. [114-5°]. Minute pale
yellow crystals, insol. water, benzene, and light
petroleum, sol., alcohol and ether. Heating at
210° with HTAq (S.G-. 1-7) and amorphous phoa-
phorus reduces it to n-pimelic acid.
Phenyl-hydrazide of the mono-ethyl
e t her^S^^^h.C{C^U^.CO^) (CjHj.CO^Et). [112°].
Minute pale yellow crystals, insol. water and
light petroleum, T. sol. hot alcohol and ether.
TETEA-ETHYL lETTCAKILINE v. Tetra-
ETHYL-TEI-^-AMIDO-TBI-PHBNYIi-MEIHANB.
ETHYL-LEVCAZONE v. AzAimouc acid.
DI-ETHYL-MAIEIC ACID C,H„0, i.e.
COzH.CBtiCEt.CO^H. Xeronic acid. The an-
hydride occurs among the products of the dis-
tillation of citric acid, being formed by boiling
citraconic anhydride for a long time. This an-
hydride is converted into the Ca salt by digestion
with water and CaCOa (Fittig, A. 188, 59).
Formed also by treating aa-di-bromo-butyric acid
with reduced silver (Otto a. Beckurts, A. 239,
277). The free acid, liberated by adding HCl to
its salts, changes at once into the anhydride. It
does not combine with Br. HI reduces it to di-
ethyl-succinic acid. Chromic acid mixture oxi-
dises it to propionic acid (Boser, B. 15, 1321).
Salts. — AgjA". — CuA"aq. — CaA'aq. —
BaA" iaq.
Anhydride CsH,„03. (242° i.V.). Liquid;
volatile with steam, SI. sol. cold water.
ETHYL-MAIONIC ACID C5HSO4 i.e.
CHEt(COjH)j. Mol. w. 132. [112°].
FormaUon. — 1. By treating a-bromo-»-buty-
ric acid with KCy and boiling the product with
potash (WisUcenus, A. 149, 220 ; 165, 93 ; Tu-
polefE, A. 171, 243 ; Markownikoff, A. 182, 324).
2. By heating malonic ether (16 pts.), and
sodium (2 pts.) dissolved in alcohol (25 pts.) with
gradual addition of Btl (20 pts.). The resulting
ether is saponified by potash, neutralised by HCl,
and converted into the Ca salt. The Ca salt is
then decomposed by HCl and the acid extracted
with ether (Conrad, A. 204, 184).
Properties. — Short four-sided prisms or
feathery groups. V. sol. water, alcohol, and
ether. At 160° it splits -up into CO, and butyric
acid. The same decomposition occurs when its
aqueous solution is evaporated at too high a
temperature, especially in presence of mineral
acids. FejCl, gives no pp. in neutral solutions.
Salts. — KjA" xaq: small crystals, v. sol.
water, insol. alcohol. — Na2A"a!aq: efflorescent
granularmass. — ^BaA": small needles. — CaA"aq:
prisms ; si. sol. hot, v. sol. cold, water. —
ZnA"2Jaq: crystalline powder composed of
minute six-sided plates ; S. -22. — ZnA" 3aq. —
CuA" 3aq : bluish-green tablets. — PbA" : white
pp. becoming granular on boiling. — AgjA'' : spar-
ingly soluble needles. — The aniline salt when
treated in benzene with phosphorus pentaohloridd
gives PhN:CH.O.CClEt.C0NHPh [104°], (P3/.I).
chloro-(P2/. 3)-oxy-(P^. 2)-ethyl-quinoline [248°],
and the anilide of di-chloro-butyrio acid [200°]
(Kiigheimer a. Schramm, B. 21, 304). — The 0-
toluidinesalt gives with POI5 (Py. l)-chloro-
{Py. 3).oxy-(Py. 2).eihyl-(B. 4)-methyl.qmnoline
(E. a. S.) [225°].
Di-ethyl ether Et^A". (200° nncor.);
(210° cor.). S.G. if 1-0124 ; |f 1-0044. M.M.
9-278 at 1&-S° (Ferkin, C. J. 45. 612). From
ETHYL NITRATE.
601
the silver salt and EtI. Prepared also by the
Action of EtI (1 mol.) on a mixture of malonio
ether (1 mol.) and NaOEt (1 mol.) (Conrad, B.
12, 751 ; A. 204, 134). Formed also by heating
malonio ether with EtI and zinc (Schukoffsky,
/. B. 1887, 601). Above 250° it is partially
decomposed with formation of butyric pther.
Iodine appears to convert sodium ethyl-malonio
ether into CjH5.Cri(C0.,Et').j, whence alcoholic
KOH forms Et.C(OEt)"(COsK)j, while baryta-
water forms barium ethyl-tartronate (Bischofi a.
Hausderfer, A. 239, 120).
4mide CHEt(C0NH2)j. [208°]. From the
ether and NH, (Ereund a. Goldsmith, B. 21,
1243).
Amide-anilide CHEt(C0NH2){C0NHPh).
[182°]. Formed by heating the amide (1 mol.)
with aniline (1 mol.).
Anilide CHEt(CONHPh)j. [215°] (P. a.
G.) ; [223°] (Rugheimer, B. 17, 235). Needles
(from alcohol). Formed by heating the amide
(1 mol.), the acid, or the ether, with aniline (2
mols.).
Mono-anilide CHEt(CONHPh)(COjH).
[150°]. Formed by boiling the preceding with
excess of lime (F. a. G.).
Phenyl-hydraeideCSEt(CO.'SH.'S'SPh)^.
[233°]. Obtained by heating the amide with
phenyl-hydrazine (F. a. G.). Needles (from
HOAc) ; insol. water, si. sol. alcohol. COCl^
converts it into CisHuN^O, [above 300°].
Si-ethyl-malonic acid C,13.^fi^i.e.
CEtj(C0jH)2. [121°]. S. 65 at 16°. Formed
by treating malonic ether with NaOEt (2 mols.)
and EtI (2 mols.), and saponifying the product
(Conrad, A. 204, 138). Prisms ; v. sol. alcohol
and ether. At 170° it splits up into CO, and
CHEtj-CO^.
Salts. — CaA": moderately soluble crystal-
line pp. — ^AgjA'' : crystalline pp.
Ethyl ether M.M'. (230° cor.). S.G. i|
•9917; if -9844. M.M. 11-20 at 19° (Perkin,
C. J. 45, 513). Formed as above. Formed also
by treating malonic ether with ZnEt^ (MartinofE
a. Schukoffsky, J. B. 1887, 297).
Beferences. — Chmro- and Bbomo- ethyl-
malonio Acn> and eieeb.
^TKZL-TILALONYZ-VKEAv.Eth/yl-derivatwe
of Babbitubic acid. '
ETHYL-UEL&MINE. Described as Ethyl-
eycmuramide v. Ctanio acid.
ETHYL MEBCAFTAN v. Mebcaftan.
ETHYL-METHYl- v. Methyl-ethyl-.
ETHYL-METHYIENE- v. Methylene-
XTBYL-^
ETHTL VLVSTAXD OIL v. Ethyl thio-cabb-
IMIDE.
(o)- ETHYL -NAPHTHALENE 0,»H,j U.
0,„-E,.C^H,. (259° i.V.); (100° at 4 mm.). V.D.
6-35 (obs.). S.G. g 1-0204; "g" 1-0123. Prepared
by the action of sodium on a mixture of (a)-
bromo-naphthalene and ethyl bromide (Fittig a.
Bemsen, Z. [2] 5, 37 ; A. 155, 118). Colourless
liquid. Partially decomposed on distillation. Br
gives a tri-bromo- derivative [127°]. — ^Picric
acid compound: fine yellow needles [98°]
(Camelutti, B. 13, 1671 ; G. 10, 388).
(;8)-Ethyl-naphthalene C,oH,Et. (251°). S.G.
§1-0078. Colourless liquid. Solidifies at - 19°.
Prepared by the action of sodium on a mixture
of (is) -bromo- naphthalene and ethyl bromide
(Brunel,B. 17, 1179). It is also formed (probably
together with the (a) -ethyl-naphthalene) by the
action of Al^Clg on a. mixture of naphthalene
(100 pts.) and ethyl bromide or chloride (5bpts.)
(Marehetti, 0. 11, 265, 439J. EtBr gives the best
yield (Eoux, A. Oh. [2] 12, 289).— Picric acid
compound: [69°] (B.); [71°] (M.) ; yellow
needles or long plates.
(a) -ETHYL -NAPHTHALENE SULPHONIC
ACID Cj^jiSOaH. Forms an amorphous Ba
salt and a crystalline copper salt CuA'2 2aq, m.
sol. water.
(iS) -Ethyl-naphthalene snlphonic acid
CjjH^SOjH. From (/8) -ethyl-naphthalene and
HjSOj. Forms a lead salt FbA',, crystallising
in scales (Marehetti, (?. 11, 439).
ETHYL-NAPHTHOIC ACID. Amide
C,„H^t.CONHj [1:4]. [166°]. Formed by act-
ing on (a)-ethyl naphthaline with chloro-formio
amide in presence of AljClg (Gattermann, A. 244,
57). Colourless needles (from alcohol). On
hydrolysis (1-4) ethyl-naphthoic acid [132°] is
obtained.
(6)-ETHYL-NAPHTH0L C,„H„Et.OH. [98°].
Obtained by fusing (;8)-ethyl-naphthalene snl-
phonic acid with potash (Marehetti, Ct. 11, 442).
Silvery leaflets, insol. cold water, v. sol. alcohol
ETHYL-NAPHTHYL-AMINE v. Naphthyl-
ethyl-amine.
ETHYL - NAPHTHYLENE . DIAIIINE v.
Naphthylene-ethyl-diamine.
ETHYL NITKATE C^fH^NO,. Nitric ethir.
Mol. w. 91. (86°) at 728 mm. 8.Q. 2 1-132 ;
"51* 1-112 (Kopp, A. 98, 367). H.F.p. 40,780 (Th.) ;
30700 (Berthelot). H.P.V. 38,750 (Th.). S.V.
91-1 (Bamsay). Formed by distilling alcohol
with an equal weight of HNO, (S.G. 1-4) con-
taining 3 p.c. of urea ; the distillation must be
stopped when two-thirds of the liquid has dis-
tilled over, otherwise an explosive reaction will
set in (MUlon, A. Oh. [3] 8, 239; Carey Lia,
Am. S. [2] 32, 178). It may also be obtained
by dropping absolute alcohol (10 g.) from a very
fijie pipette into cone. HNO, (20 g.) cooled with
ice and salt (Persoz, Bip. Chim. pure, 5, 30).
Alcoholic AgNOj boiled with EtI or EtBr does
not yield ethyl nitrate, but aldehyde and ethyl
nitrite. The EtNO, may be supposed to b^ re-
duced by the alcohol at the moment of formation
thus : EtNOa -f CjH,.OH = EtNOj -I- 0^,0 + a,0
(Bertrand, Bl. [2] 33, 666).
Preparation. — A mixture o^ alcohol (300 g.),
urea nitrate (100 g.), and HNO3 (400 g. of S.G. 1-4)
is distilled to half its volume, after which a mix-
ture of alcohol (3 pts.) and nitric acid (4 pts.) is
run in slowly so as to keep the level of the liquid
constant. The nitric acid used must have been
previously heated to boiling with 1 p.c. of urea
and afterwards cooled (hoss&a, A. Sv^l. 6, 220 ;
Bertoni, Q. 6, 406).
Properties. — Colourless oil with pleasant
odour and sweet taste; miscible with alcohol
and ether. It bums with a white flame.
Beactions. — 1. Alcoholic NH, at 100° gives
ethylamine nitrate NEtjHNOj (JuncadeUa, O. B,
48, 342). A mixture of nitric ether (1 vol.), al-
cohol (1 vol.), and cone. NHjAq (1 vol.) at 100°
forms mono-, di-, and tri-, ethylamine (Lea). —
2. Ammonium suTphAde in alcoholic solution
yields mercaptan (B. Kopp, J. Ph. [3] 11, 321).
503
ETHYL NITRATE.
3. Tin and HCI reduce it to hydroxylamine and
di-ethyl-hydiozylamine (Loseen). — 4. When
heated mth feirons acetate nitrogen is given ofC
(Lea).
ETHYL NITEITE CjHsNOj i.e. Et.O.NO.
Nitrous ether. Mol.w.75. (18°). S.2. S.G. g
•919; 155-900 (Brown,Pfc.'15, 400). H.F.p. 30,610.
H.F.V. 28,870. Produced by the action of nitric
acid upon alcohol. The reaction is very violent,
the alcohol being oxidised to aldehyde, &c.,
while the nitric acid is reduced to nitrous acid
which etherifies the remaining alcohol (Eunkel,
A.D. 1681 ; Dumas a. Boullay, A. Ch. [2] 37, 15).
' S^eet spirit of nitre ' is obtained by distilling
an excess of alcohol with HNO,. Alcohol may
be saved by adding copper, starch, or sugar to
the mixture ; or the ether may be obtained by
passing nitrous fumes into alcohol (Liebig, A,
SO, 142 ; B. Kopp, /. Ph. [3] 9, 320 ; Giant, Ph.
10, 244 ; Feldhaus, A. 126, ,71).
PrejaaraUon. — 34'5 g. NaKO, dissolved in
120 c.c. of water are cooled below 0°; 13-S c.c.
HjSO, are added to 32 c.c. rectified spirit mixed
with an equal volume of water, and the mixture
diluted to 120 c.c. and cooled. The acid mixture
is added gradually to the nitrite solution and the
ether separated by a tap funnel, washed with
water, and dried over ignited E^CO,. Glycerin
(5 p.c.) added to the 2 p.c. alcoholic solution
prevents its decomposition (Dunstan a. Dymond,
Ph. 18, 861).
Properties. — ^Liquid,with characteristic odour ;
miscible with alcohol, si. sol. water. Decom-
poses when kept in a wet state, giving off NO.
Saponified by solid KOH giving EKOj and alco-
hol (Liebig a. Strecker, A. 77, 331). Beduced
by EjS or ammonium sulphide to alcohol and
KHj. Diazotises aromatic amido- compounds.
ETHYL-NITEO- v. Nitbo-eihyi,-.
ETHYL-NITROLIC ACID CjHjNA i.e.
CH,.C(NOj):NOH or CH3.CH(N0j).N0. [82°].
Formation. — 1. By the action of potassium
nitrite and H^SO^ on an alkaline solution of
nitro-ethane (V. Meyer, B. 6, 1494 ; 7, 425 ; A.
180, 170). — 2. From di-bromo-nitro-ethane and
hydroxylamine in the cold. '
Preparation. — From nitro-ethane (6 c.c),
ice, potash (15 c.c, containing 6'7 g. EOH), and
KaNOj (15 c.c. containing 8 g.). Dilute HjSO, is
added, and the product extracted by ether (v.
Meyer a. E. J. Constam, A. 214, 329).
Properties. — ^Light-yellow transparent tri-
metric prisms resembling ENO,. Tastes sweet,
and has an acid reaction. V. e. sol. warm, si.
sol. cold, water. Dissolves in aqueous alkalis
and in baryta, giving a deep red solution. An
ethereal solution is not coloured by dry NH3
until water is added. Lead acetate gives a bril-
liant orange pp., AgNO, gives an egg-yellow pp.
Beacticms. — 1. When heated to 82° it melts,
and is completely decomposed, thus :
2CH3.C(N02):NOH = 2OH3.CO2H + N, + NOj.
The same decomposition occurs slowly in the
cold, and quickly on boiling with an alkali. —
3. Sodium amalgam reduces it to acetic acid,
nitrous acid, and KH3. Tin and HCI act in the
same way. In the case of sodium amalgam,
ethyl-azaurojic acid is an intermediate product. —
3. Cone, sulphuric acid splits it up into acetic
acid and X.O,
Isomeride of ethyl-nitroUc add CfitTSfl^
[75°]. Formed by the action of sodium amalgam
upon nitro-ethane (Eissel, Bl. [2] 40, 72 ; /. B.
15, 91). Prisms or needles (from chloroform).
Acid in reaction,' and forms salts with alkalis,
but their solutions are not red.
ETHYL-NITEO-PHEHYL- v. Niteo-phenyi,.
ETHYL-.
DI-EIHYL-NIISOSAMIKE
V. Dl-BIHXL-
AMINE.
tl - ETHYL - ISO - NITBOSO - AUYL - AUINE
NEt2(03H,N0H). [72°]. Large flat crystals ob-
tained by acting on Guthrie's amylene nitrite
with diethylamine (Wallach, A. 241, 304).
ETHYL n-OOTYL OXIDE Et.O.CsH,,.
(189-2°). S.G. g -8008. S.V. 244-9. C.B. (0°-10°)
•00101 (Dobriner, A. 243, 6). (183°). S.G. n
-805 (Moslinger, A. 185, 57).
ETHYL-OXALIC ACID v. OxAuo Acm.
Di-ethyl-ozalio acid v. Oxy-nExoio Acm.
ETHYL-OXALYL-ANTHBAITILIC ACID v.
Cabboxy-fhenyl-oxamio acid. I
ETHYL-OXAMIC ACID C^HjNO, i.e.
NHBt.CO.COjH. [120°]. Formed by heating
the acid oxalate of ethylaraine (Wurtz, A. Ch.
[3] 30, 443). Its ether is obtained by treating
oxalic ether with ethylamine, and may be sapo-
nified by boiling water or by milk of lime (WaBach
a. West, B. 8, 760 ; A. 184, 58 ; of. Heintz, A.
127, 43). Six-sided tables, v. sol. water, alcohol,
and ether. May be extracted from its aqueous
solution by ether. Sublimes in woolly needles.
Cold cone. EOHAq decomposes it, giving off
ethylamine. Boiling NHjAq does not act on it. —
CaA'j 2aq : prisms. — CaA'j 4aq (Duvillier a.
Euisine, A. Ch. [5] 23, 349). S. 3-17 at 17-5°.—
BaA'2 aq.
Ethyl ether EtA'. Ethyl-oxamethane.
(245°). Formed as above. Liquid, miscible with
water, alcohol, and ether. Saponified by hot
water. HH, converts it into ethyl-oxamide
NHEt.CO.CO.NH3. PCI5 gives crystalline
Cd2Et.CCl3.NHEt [above 50°], which is slowly
decomposed at 100°, giving off EtCl and CO,.
Dl-ethyl-oxamic acid NEt3.CO.CO2H.
[101°]. Prepared by saponification of the ether
(Wallach, B. 14, 743; A. 214, 270). Large
monoclinic prisms. Y. sol. water and alcohol.
Split up by heat into OO2 and di-ethyl-formamide.
POlj forms NEt2.CO.COCl.— CaA'2 2aq : v. e. sol.
water and boiling alcohol.
Ethyl ether EtA'. (252°). Formed by
treating oxalic ether with diethylamine (Hof-
mann, Pr. 11, 66 ; B. 3, 779 ; Heintz, A. 127,
62).
Nitrite NEtj.CO.CN. (220°). From un-
symmetrical di-ethyl-oxamide, NEt2CO.CONH2,
and PjOs (Wallach, A. 214, 264). Liquid. SI.
sol. water. Volatile with steam. Lighter than
water. Gives with PCI3 a httle chloro-oxal-
ethyline.
ETHYL-OXAMIDE CtB.^j:>t i.e.
NH2.CO.CO.NHEt. [203°]. From ethyloxamio
ether and NHj, or from oxamio ether and ethyl-
amine (Wallach, A. 184, 65). Flexible needles ;
may be sublimed. V. sol. hot water.
M-Di-ethyl-oxamide CONHa.CONBtj. [127°].
(267° cor.). From diethyl-oxamio ether and
cold aqueous NHj (Wallach, A. 214, 260). Long
prisms ; sublimes at 100°. Sol. hot water and.
ETHYL-PHENOL.
603
alcohol. Converted by PCI. into ohloro-oxal-
ethyUne CACIN,. (Yield, bad.)
s-Di-ethyl-oxamide CO(NHEt).CO.NHEt.
[175°] (WaUaoh, A. 2U, 268) ; [179°] (Sohiff, B.
17, 1034). S.G. i 1-169 (Schroder, B. 12, 1611).
From oxalic ether and aqueous ethylamine
(Wurtz, .4. Ch. [3] 30, 490). Needles. More
soluble in water and alcohol than oxamide. May
be sublimed in crystals. Potash converts it into
ethylamine and oxalic acid.
Triethyl-oxamide NHEt.CO.CO.NEtj. (258°).
Obtained from strong aqueous ethylamine solu-
tion and diethyl-oxamic ether NEtj-CCCOOBt.
Liquid; miscible with water; decomposed by
PCI5 (WaUaoh, A. 214, 267).
ETHYI-OXANTHRANOL v. Oxamtheanoi..
DI-ETHYl-OXETHYL-AMINE v. Oxy-tei-
EIHYn-AMINB.
DI-ETHYl OXIDE v. Eiheb.
Ethyl peroxide {C^^)fi^{1) Obtained by
passing a slow current of dry ozonised oxygen
over dry ether (Berthelot, G. B. 92, 895; A. Ch.
[5] 27, 229). Syrupy liquid ; does not solidify
at —40°. Explodes when distilled. Decom-
posed by water into alcohol and HjO,.
ETHYL-OXINDOIiE v. Oxindolb.
ETHYI-OXY- V. Ethyl derwatives of Oxy-.
DI-ETHTL-OXYALLYL-AMINE
NEtyOjHjOH. (0. 160°). The most volatile of
the bases obtained by the action of epichlorhy-
drin on di-ethyl-amine (Eeboul, G. B. 97, 1488,
1556). Thick liquid with powerful odour resem-
bling that of diethylamine. V. sol. water. HOI fol-
lowed by PtOl, gives {NEtAHsCl(0H)jjHjPtCl8
crystallising in garnet-red prisms ; the. corre-
sponding base NBtj.CsHsC^OH) is the first pro-
duct of the action of NEt^H on epichlorhydrin.
ETHYI-OXY-PEOPTL-AMINE
(C,HpOH)(CjH5)NH. (c. 160°). Formed by
heating ethyl-aUyl-amine with H^SO, and pour-
ing the product into water. — B'2H2CljPt0l4 2aq :
V. sol. ^ater (Liebermann, B. 16, 581).
Ozy-propyl-di-ethyl-amine C,H,ON i.e.
CHj(0H).CHj,.CHj.N(CjH5).. THmethylene-M-
ethylalkine. (190°). S.G. | = -9199. Colourless
liquid. Miscible with water. Formed by heating
trimethylene-ohlorhydrih with di-ethyl-amine.
The platino-chloride forms very soluble
orange-red prisms; the aurochloride forms
thick plates; the picrate long soluble needles
(Berend, B. 17, 512).
Di-ethyl-oiypropyl-amine C,H„N0. (159°).
Di-ethyl-propyl-alkine. Prepared by the ac-
tion of diethylamine on propylene-ohlorhydrin.
(B'HOyjPtCl,. V. sol. water (Ladenburg, B. 14,
2407).
Di-ethyl-di-oxypropyl-amine CjH^NOj i.e.
NEtj.CHj.CH(0H).CB:20H. - Di-ethyl-propyl-
glycolUne. (234°). Colourless oil. Soluble in
water, alcohol, and ether. Formed by heating
di-ethyl-amine with glycerine-ohlorhydrin. —
BjHjOljPtCl, : reddish-yellow tables (Both, B.
15, 1151).
Benzoyl derivative
NEt2.CH2.CH(OH).CH,(OBz). Thick liquid. Its
picrate 0,4H2,NO,C„H2(OH)(N02)3 crystallises
in yellow plates ; v. si. sol. water.
ETHYl-OXYPROPYL-ANILINE
C„H5.N(0.ja:,)(C3H„.OH). Ethyl-phenyl-propyl-
alkine. (262°). Colourless liquid. Insoluble in
water. Very weak base. Formed by heating
ethyl-aniline with propylene-ohlorhydrin (Laun,
JB.17, 678). -^ "
DI - ETHYL - OXY - PEOP YLENE - DIAMINE
0H2(0H).CH(NHEt).CH2(NHEt). (0. 185°).
From epichlorhydrin and ethylamine (Beboul,
C. B. 97, 1488). Syrup, miscible with water,
Tetra-ethyl-ozy-propylene-di-amine
N2HEt4.03H40H i.e.
CHj(0H).CH(NEt,).CH2.NEtj.
According to Behrend {B. 17, 511) this base,
obtained from diethylamine and the dichloride
of allyl alcohol, is a liquid which cannot be
distilled, but which forms an aurochloride
B'(HAuCl4)2 that crystallises in plates, si. sol. .
water, and also a benzoyl derivative
CH2(0Bz).CH(NEt,).CH2NEt2, of which the pla-
tino-chlorideB"H2PtOl4formsorange-redneedleB.
Tetra-ethyl-oiy-propylene-diamine
(C,H3.0H)(C2H,)4N2 i.e.
CHj(NEtj).CH(0H).CK,(NBtJ.2'eira-e%Z-aZZ2/Z-
alUne. (235°). S.G. | -9002. Colourless liquid,
lighter than, and shghtly soluble in, water.
Formed by heating s-diohlorhydrin with diethyl-
amine, or by mixing epichlorhydrin with diethyl-
amine. The platino-chloride B'^jPtCl,
forms long thick soluble prisms; the auro-
chloride forms fine needles (Berend, B, 17,
510 ; Eeboul, O. B. 97, 1488).
Benzoyl derivative CH(0Bz)(CH2NEtj)2.
Gives an orange platino-chloride B"H2PtClj.
ETHYL OXYSULPHIDE v. Ethyl sotph-
OXIDE.
o-ETHTL-PHEN0L[4:l]CsH4Et(OH).PWoroJ.
Mol. w. 122. (211°) (0.) ; (220°) (C).
FormaUon. — 1. From o-amido-phenyl-ethane
by the diazo- reaction (Suida a. Plohn, Sitz. W.
[2] 81, 245 ; M. 1, 175). When the amido-
phenyi-ethane used is obtained by reducing the
crude product of the nitration of ethyl-benzene
the o-ethyl-phenol constitutes three-fourths of
the resulting product. — 2. By distilling barium
phloretate with lime ; phenol being also formed
(V. Oliveri, G. 13, 263).— 3. By fusing ethyl-
benzene (;8)-Eulphonic acid with potash. — 4.
From its methyl ether. — 5. By distilling gum
ammoniac (1 pt.) with zinc-dust (lOpts.) (Ciami-
cian, B. 12, 1658).
Properties. — Colourless liquid smelling like
phenol. Liquid at — 18°. SI. sol. water, v. sol.
alcohol and ether. Gives a greenish colouration
with ferric salts. Dissolves in alkalis. Yields
salicylic acid and a small quantity of m-oxj-
benzoic acid when fused with potash. Beacts
with cone. HNO3 with explosive violence.
Salt. — ^Ba(O.CeH4Et)2 2aq: leaflets, decom-
posing at 100°.
Methyl ether CBH^Et.OMe. (185°) (0.);
(191°) (S. a. P.). Heavy oil of pleasant ethereal
odour. Not attacked by chromic acid mixture
or by KMnOj.
(a)-Ethyl-phenol C„H4Et(0H). [47°]. (215°).
Formed by fusing ethyl-benzene (a)-sulphonio
acid with potash (Beilstein a. Euhlberg, A. 156,
211 ; Fittig a. Kiesoff, A. 156, 251). Needles.
SI. sol. water, v. e. sol. alcohol and ether. Its
aqueous solution is coloured greeuish-blue by
FejCl,,. When heated with P2O5 it gives phenyl
phosphate and ethylene (Chrustschoff, B. 7,
1165). Cone. HNO, gives CO, and oxalic acid.
Ethyl-phenol C„H,Et.OH.' (204°-215°) (E.).
S.G. ii 1-049 (A.). Prei^ared by heating a mix.
504
ETHYL-PHENOL,
tnre of phenol and ethyl alcohol with zinc-
chloride (Auer, B. 17, 669). A mixture of ethyl-
phenols is formed by this process (Errera, Cf. 14,
4S4). Its aqueous solution is coloured greenish
by ferric chloride.
Ethyl ether C,H,Et(OEt). (200°) (E.).
Oxidised by KMnO^ to ^-oxy-benzoio ether.
Acetyl derivativeCgB.fit(OAo). (c.225°).
Di-ethyl-phenol OjHjEt2(OH) [1:3:47]. (225°).
From m-di-ethyl-benzene. Gives a bluish-violet
colour with FeCl,.
Reference. — Di-bromo-ethyIi-phenoii.
SIHYI-FHENOL CAHBOXYLIC ACID v.Oxy-
ETHYL-BENZOIO ACID.
ETHYL -PHENOI-PHTEAIElN CjjH„0,.
Formed by heating ethyl-phenol with phthalio
anhydride and ZnCilj (Auer, B. 17, 671). Grey
crystalline powder (containing aq). V. sol.
alcohol and ether, insol. water. Dissolves in
alkalis forming a violet solution.
o- ETHYL -PHENOL SXTLPHONIC ACID
CsH3Bt(0H)S0aH. From o-ethyl-phenol and
cone. HjSO^ (Suida a. Plohn, Siiz. W. [2] 81,
245; M. 1, 179). Very deliquescent minute
needles. — BaA', xaq : pearly plates. Its solution
gives a white pp. with lead salts and a dirty-
green pp. with copper salts.
(a)-Etbyl-phenol sulphonlc acid
CjH,Et(0H).S03H. From (o) -ethyl-phenol and
cone. H^SO, (Fittig a. Kiesoff, A. 156, 254).—
BaA'2 : prisms. S. 4-7 at 17° (Baumann, H. i,
313).— BaCeHsOj : insol. water.
ETHYL-DIPHENYL CB^.Gfi.iC^B.^). [1:3].
(284°). S.G.fil-043. Formed by treating melted
diphenyl and AlCl, with G2H5CI, CjHsBr, or
with OjH,. The OjHjBr gives the best yield
(Adam, A. Ch. [6] 15, 251 ; Bl. [2] 47, 689).
Colourless, mobile liquid. Oxidised with chro-
mic acid it gives CsHs.CjHj.OOjH [1:3] [161°].
Traces of CgHg.O,H,.COCH, can be obtained as
an intermediate product. Bromine at 180° easily
produces a dibromide OnH,jBrj. [103°]. Insol.
alcohol and ether.
Di-ethyl-diphenyl Ofis.OeB.s{0^s)p S.G. 2
•999. (c. 307°). Formed by treating melted di-
phenyl and AlClj with OjH„ OJifil, or C^HsBr,
the latter giving the best yield (Adam). A colour-
less liquid. When oxidised with chromic acid
(1,3,5) dipheuyl-di-carboxylic acid is obtained.
Reference. — Di-amido-di-ethtii-diphentl.
ETHYL-PHENYL- v. Phenvi-ethyi-.
ETHYL-FHENYL-ACETIC ALDEHYDE
C,H,Bt.CH2.CH0. From di-ethyl-benzene by
successive treatment with CrOjCl^ and water
(Etard, A. Ch. [5] 22, 255). Liquid. Volatile
with steam. Decomposed by heating to 220°.
Combines with NaHSO,. '
' ETHYL - PHENYL - AMIDO - NAPHTHOQUI-
NONE V. NaPHIHOQUINONE-BIHYIi-ANIIiIDE.
ETHYL-PHENYL-AMINE v. Amido-phenyi.-
EIEAME.
TBI-ETHYL-PHENYL-AMMONnjM HY-
DBOXIDE V. Ethyh-hydroxide of Di-ethyi.-
AHILINE.
TBI - ETHYL - PHENYL - ABSONIUM com-
pounds V. Absknio, Organic compounds of.
ETHYL-PHENYL BENZYL KETONE v.
BeNZTIi ETHYIi-FHENTIi KETONE.
p-ETHYL-PHENYL-p-ISOBUTYL-PHENYI-
THIO-TJEEA C^H„.C.H<.NH.SCNH.C,H<(C2Hs).
Phenethyl-phenisobutyl-thMmrea.llM°].ioTnnied
from ^-ethyl-phenyl thiocarbimide and ^-butyl.
phenyl-amine (Mainzer, B. 16, 2025). Small
white prisms. Sol. hot alcohol. By phosphoric
acid it is split up into p-isobutyl-phenyl thio-
carbimide jj-ethyl-phenyl thiocarbimide, ^-iso-
butyl-phenyl-amine, and ^-ethyl-phenyl-amine.
ETHYL-PHENYLENE-DIAUINE v. Fhenti,-
ENE-KTHTL-DIAMINE.
ETHYL-DI-FHENYL-ETHANE v. Fhentl-
ETHyLPHENTL-BTHANE.
ETHYL-DI-PHENYL-ETHYLENE
C5H5.CH:CH.CsH4Et. [90°]. Formed from
Ph.CHj.CH(0H).C5H,Et and boiling dilute
HjSOi (Sollscher, B. 15, 1681). Plates, v. e. sol.
ether.
Di-ethyl-di-phenyl-ethylene
CeH,Et.CH:CH.C5H,Et. Di-ethyUsHlbene. [135°].
Obtained by distilling the product of the action
of H2SO4 on a mixture of ethyl-benzene and
Et.0.CHCl.CH201 (Hepp, B. 7, 1414). Pearly
plates (from alcohol) ; si.' sol. cold alcohol, v.
sol. ether. Boiling dilute HNO, oxidises it to
terephthalic acid. It combines with Br.
DI-p-ETHYL-PHENYL-GTJANIDINE
HN:C(NH.C||H4Et)j. Di-p-pheiiethyl-guarddine.
[188°]. Formed by the action of alcoholic NH,
and lead oxide upon di-p-ethyl-phenyl-thio-nrea
(Paucksch, B. 17, 2804). Large transparent^
tables. V. sol. alcohol, ether, and CSj.
— B"H2Cl2PtCl4 : glistening plates.
ETHYL-DI-PHENYL-KETONE o. Phentl-
ETHYL-PHEHYIi-KETONE.
DI-ETHYL-PHENYL-METHANE v. Amyl-
BENZENE.
p - ETHYL -PHENYL-(a)-NAPHTHYL-THIO-
TJBEA C,„H,NH.CS.NH.C„H,Et. Phenethyl-{a).
naphtlvyl-Mourea. [148°]. Prepared by mixiii','
(o).naphthyl thiocarbimide and ethyl-phenyl-
amine in alcoholic solution (Mainzer, B. 16,
2022). Small white needles. Sol. hot alcohol
and ether. By phosphoric acid it is split up
into p-ethyl-phenyl-thiocarbimide, (a)-naphthyl-
thiocarbimide, ^-ethyl-phenyl-amine, and (o)-
naphthylamine,
^-Etbyl-phenyl- (/3) -naphthyl-thio-urea
C„H,NH.CS.NHO„H,Et. [159°]. Prepared as
above, using (j3)-naphthyl-thiocarbimide ( (S)-
naphthyl mustard-oil) (M.). Small plates (from
alcohol). M. sol. hot alcohol and ether. Split
up like the (a)-isomeride by phosphoric acid.
DI-a-ETHYL-DI-PHENYL-PBOPIONIC ACID
C,.H«0, i.e. (C.H,.C,HJ3:C(CH,).C0,H. [116°].
Prepared by dissolving ethyl-benzene and pyr-
uvic acid in KjSO, (Bottinger, B. 14, 1597).
Transparent tables. Sol. ether, chloroform, and
Ugroin.
ETHYL- PHENYL -PEOPYL-ALKINE v.
ETHYL-OXYPKOPYL-ANrLlNB.
ETHYL PHENYL SULPHONE v. Phenyl
ETHYL SULPHONE.
ETHYL-PHENYL DI-SULPHOXIDE v. Ben-
zene THIOSULPHONIO ACID.
ETHYL-PHENYL-THIOBItTBET v. Ethyl-
derivative of PHENYL-THIOBItTBET.
0-ETHYL-PHENYL THIOCABBimDE
CjHj(C2H5).NCS. (240°-245°). o-Phenethyl^us'
tard oil. Colourless mobile liquid. Formed by
heating the thio-urea with phosphoric acid
(Paucksch, B. 17, 2802).
p-Ethyl-phenyl thiocarbimide
SCN.CjH,(CjHJ. Phenethyl mustard oil. (256°).
ETHYL-PHOSPHraE.
SOS
tilquid. Formed by distilling di-2)-ethyl-pheii7l-
thiouiea with phosphoric acid (Maiazer, B. 16,
2020).
DI-o-ETHYLPHEHYI-THIO-TrEEA
C„H„NjS i.e. SC(NH.CJH,Et)y [142°]. White
needles. Obtained by heating o-amido-ethyl-
benzene -with CSj and a little NaOH (Pauoksoh,
B. 17,767).,
Si-^-ethylphenyl-thio-nrea
C„Ha,NjS i.e. SC(NH.C5H4Bt)j. [145"|]. Obtained
by heating j>-amido-ethyl-benzene with CSj and
a little NaOH (Pauoksoh, B. 17, 768; cf. Main-
zer, B. 16, 2019). Pearly plates. Soluble in
hot, sparingly in cold, alcohol.
EIHTL-PHENTL-I0L17ENE «. Benzyl-
ETHYL-BENZENE.
LI-p-ETHYL-PHEKTL-TfEEA
OG(NH.C5H4Et)2. Di-p-phen-ethyl-'wrea. [217°].
Long transparent neefles. Formed by the action
of oarbonyl chloride (OOCy upon^-ethyl-phenyl-
amine (Paucksch, B. 17^ 2804).
PENTA-ETHYl-PHLOBOeLirCIN
CjEt^OaH i.e. CeEt02(Et2)j(0H). [92°] ?
' Prepa/ration. — Phlorogluoin (1 mol.) is
warmed with KHO (3 mols.) and EtI (3 mols.)
in alcohoUc solution. The alcohol is finally
distilled off and the residue dissolved with water
and extracted with ether.
Properties. — Yellow indiEEerent body; when
repeatedly crystallised from weak alcohol, it
forms white plates. It is not acted on by boil-
ing HIAq. It reacts with more EtI and KHO,
showing that it still contains a HO group, form-
ing an oil CijHj'dOj or hexa-ethyl-phloroglucin
CjOaEtn (Herzig a. Zeisel, M. 9, 217).
ETHYL PHOSPHATES
]!Iono-ethylortho-phosphateC2H50.PO(OH)2.
Ethylphosphoric acid. Formed by the action
^ of phosphoric acid on alcohol or ether (Lassaigne,
A. Oh. [2] 18, 294; Pelouze, A. Ch. [2] 52, 37;
Liebig, A. 6, 149; 13, 32; Church, Pr. 13, 520;
Vogeli, P. 74, 282). A mixture of alcohol (1
pt. of 95 p.o.) with syrupy ortho- or pyro-phos-
phorio acid (1 pt.) is heated for some minutes to
70°, left to stand for 24 hours, and then diluted
with water and neutralised with BaCOj. The
Ba salt is crystallised and decomposed by
H,SO,.
ProperUes. — Colourless viscid liquid miscible
with water, alcohol, and ether. It reddens litmus
and tastes sour. It gives off ether, alcohol, and
ethylene when heated. Distilled with KOAc it
yields acetic ether.
Salts. — Soluble in water and crystalline.
Most of them have a maximum degree of solu-
bility at 40° to 60°. The lead salt is the least
soluble: As^A",: feathery crystals (Church).—
BaA" 6aq : prisms or tables. S. 3-4 at 0° ; 6-72
at 20° ; 9-36 at 40° ; 2-80 at 100°.— BaA"aq (C).
— BaA"7aq (0.).—CaA" 2aq : micaceous scales.
— FejA"3 8aq: straw-yellow fihns (C). —
Fe,AlA",6aq (Church).— PeAlA", 3aq (C.).—
FeAlsA"„6aq (Church).- Fe5A"8 6aq (Church).
— PbA"aq.— Hg2A"2aq (?) (Church).— UrOjA':
lemon - yellow mass. — ^AgA'aq : crystalline. —
Tetra-ethyl-ammonium salt (NEtJjA":
deliquescent mass of crystals ; split up by heat
into triethylamine and tri-ethyl phosphate.
Chloride 'EtO.OFCL,. (167°). Formed by
the action of alcohol (1 mol.) on POClj (1 mol.)
or by passing chlorine into a mixture of alcohol
(2 mols.) and PCI, (1 mol.) (Wichelhans, 4-
Siippl. 6, 265). Formed also by heating EtaPOi
with POCl, at 110° (Chambon, J. 1876, 205).
Oil ; split up at 160° into EtCl, POCl, and PAi
but may be distilled in a current of hydrogen.
Decomposed by water into HCl and EtO.OP(OH)j.
PBr, gives EtBr, POBr,, and POBrCL,.
, Di-ethyl phosphate (EtO)jPO.OH. Di-ethyl-
phosphoric acid. Prepared by placing PjO, in a
dish over dry ether, or, better, alcohol under a bell-
jar. In a fortnight the acid will have deliquesced,
and the syrup may then be treated with PbCOj.
The resulting lead salt is decomposed by H^S
(V6geli, A. 69, 180). Syrup; decomposed by
heat. — CaA'2 : silky groups of crystals (from
water) ; v. sol. water, si. sol. alcohol ; gives oS
EtaPO, when heated.— PbA'j : [180°] ; groups of
crystals resembling caffeine (from water) ; v. sol.
cold water and hot alcohol. At 190° it gives off
BtaPOj leaving PbEtPO, The barium salt
forms needles or laminss, v. sol. water.
Chloride (EtO),OPCl. From POCl, (1 mol.)
and alcohol (2 mols.) also from EtjPO, and CI
fW.).
Bromide (EtO)jOPBr. From EtaPO< and
Br (W.). Cannot be distilled.
Tri-ethyl phosphate EtaPO, i.e. OP(OEt),.
Phosphoric ether. (215°). S.G.ia 1-072.
Formation. — 1. By heating Pb(Et2P04)j to
190° (v. supra). — 2. In small quantity in the
preparation of di-ethyl phosphate (V.). — 3. By
heating AgaPO, with Agl at 100°, exhausting the
mass with ether, and distilling i/n vaciio (De
Clermont, A. 91, 376). — 4. From POCl, and
NaOEt (Limprioht,.4. 134,847).— 5. By treating
dry alcohol with POCL, or P^O, (Schifl ; Carius,
A. 137, 121).
Properties. — Limpid liquid with peculiar
odour. In a current of hydrogen it bqUs at
203°- Sol. water, alcohol and ether. Slowly
decomposed by contact with water forming
HEt^O^. POCl, at 110° forms EtO.POCl^.
When PCI3 (1 pt.) mixed with pure ether is
dropped upon dry NaOEt (6 pts.j suspended in
ether and the product distilled in a current of
hydrogen there is obtained a compound (158°
cor.). S.G. i* -960 which may be C^HsoPjO, or
(Et3P04)(Et3POs)(EtOH) ; it is slowly split up by
distillation into its components (Geuther, A.
224, 275).
Ethyl metaphosphate EtPO, ? (below 100°).
From lead metaphosphate and EtI (Carius, J.
1861, 586). Water converts it into EtHjjPO,.
Tetra-ethyl pyrophosphate Et^P^O,. S.G.
— 1-172. From silver pyrophosphate by heating
at 100° with EtI (De Clermont, A. 91, 375).
Viscid liquid with peculiar odour and burn-
ing taste. Decomposed by heat. Bums with
whitish flame. Sol. water, alcohol, and ether.
It turns acid when exposed to the air. Potash
iorms KEtjP04.
ETHYl-PHOSPHINE CjH,P i.e. PH^Bt.
Mol. w. 62. (25°). When EtI and PHJ are heated
together with ZnO at 150° there is formed
PEtHjI and PEtjH^I. On treating the product
with water PEtHal is decomposed into HI and
gaseous PEtH, while PEtjHjI is not affected. If ,
after expelling PEtH^ aqueous NaOH be now
added it will liberate PEtjH (Hofmann,B. 4, 432).
PHjEt is also formed when ethylene bromide,
PH,I, end ZnO are heated together (Hofmann,
506
ETHYL-PHOSPHINE.
B. 6, 302). Vfery volatUa Kquid. It has no
action on litmus. Has an overpowering odour.;
its vapour produces an intensely hitter taste in
the throat. It bleaches cork. Takes iire vrith
CI, Br, or fuming HNOj. Combines with S and
CSj forming liquid bodies.
Salt. — ^PEtHjI: four-sided tables, decom-
posed by water, partially decomposed by alcohol ;
insol. ether. It is ppd. in crystalline form by
adding ether to its solution in cone. BIAq.
£thyl-di-chloro-phosphine EtPCl,. Mthyl-
^hosphorous chloride. (110°). Formed by heat-
ing FCl, (4 pts.) with mercuric ethide HgEt,
(1 pt.) (Michaelis,B. 13, 2174). Liquid smelling
like apples. Fumes in the air. Is readily de-
composed by water. With CI it gives EtPCl, a
solid which decomposes at 100°-150° and is con-
verted by water into EtPOClj, a liquid boiling
about 175°, which is decomposed by further
treatment with water.
Di-ethyl-phosphlne Et.^H. Mol. w. 90.
(85°). Is prepared as above (Hofmann, S. 4,
433). Oil with powerful odour; lighter than
water. Absorbs oxygen from the air, sometimes
taking fire. Combines directly with sulphur and
with CSj forming liquid compounds. Its salts
crystallise with difficulty.
Tri-ethyl-phosphine PEt,. Mol. w. 118.
(128°). S.&. iS .812.
Formation.— 1. By the action of PCI, on
ZnEt, (Hofmann a. Cahours, C. J. 11, 56 ; A.
104, 1 ; Swppl. 1, 2). The tri-ethyl-phosphine
remains combined with ZnCl^ but may be
liberated by distillation with aqueous potash. —
2. By the action of phosphide of sodium on Btl
(BerW, J. pr. 66, 78).— 3. When a mixture of
zinc, phosphorus, and -dry EtI is heated at 155°
there is produced, together with ZnEt,, a mix-
ture of (PEtjH^jZnlj with (PEtJ)2ZnI, and
(PEtsO)2ZnI^ These compounds may be
separated by water, the first being the least and
the second the most soluble. The first yields PEt,
when treated with cold potash, the third yields
it when heated with solid KOH (Hofmann, C. J.
13, 291). — 4. When zinc phosphide obtained by
passing dry PH, into a well-cooled ethereal solu-
tion of ZnEtj is heated with (5 pts. of) EtI at
150° it forms (Et3PHI)2Znl2 (Drechsel a. Pinkel-
stein, B. 4, 352).
Prepa/ratton. — 1. PCI, is allowed to drop
slowly into an ethereal solution of ZnEt^ placed
in a retort filled with COj connected with a
tubulated receiver. The reaction is violent, and,
to avoid loss, the other tubulure of the receiver
is connected with a V tube containing PClj com-
municating with a vessel full of CO^. The liquid
separates into two layers, the lower being the
zinc double salt of PEt,; this salt is distilled
with aqueous KOH in a current of hydrogen. It
is dried with solid KOH and rectified in hydro-
gen (Hofmann, O. J. 13, 290).— 2. PH,I (1 mol.)
is heated with alcohol (3 mols.) for 8 hours at
180°. The product containing PEt,HI and
PEtJ is distilled with potash (Hofmann, B. 4,
207).
Fraperttes. — Colourless, mobile, liquid. Its
odour is very penetrating but not disagreeable ;
when diluted it smells like hyacinths. When
freshly prepared it has no action on litmus, but
if exposed for a few seconds to the air it becomes
^oid. It is insol. water, miscible with alcohol
and ether. It unites with acids forming very
deliquescent salts.
BeacUons. — 1. Bapidly absorbs oxygen from
the air, becoming PEt,0. It often takes ire in
pure oxygen, forming P2O5. Its vapour mixed
with oxygen explodes when heated. — 2. Sulphvir
combines with it forming PEtjS. — 3. SeUmum
gives PEtjSe. — 4. Sulphide of carbon unites
with it forming red monocHnic crystals of
PEtjCSj [95°]. Hence CSj and PEt, may be
used to detect one another; thus, when the
vapour of CSj is poured over a watch glass in
which there is a liquid containing free FEtj, a
beautiful net- work of the red crystals wUl appear.
The crystals are insol. water, si. sol. ether, m. sol.
warm alcohol and CSj. They dissolve in cone.
HOlAq, forming a colourless solution from which
they are re-ppd. by KOH unaltered. Water at
100° gives PEtjS, PEtjO, and PMeEtjOH. Boil-
ing with alcohol and AgjO forms PEtjSand COj.
HjS also gives PEtjS and yellow crystals of
CgH^PSa, which are converted by hot water
into CSj and 0,H,sPSO, whence C,H„PSI may be
prepared. Platinic chloride forms the compound
(PBtsCS2)2H2PtCl|5 an amorphous light yellow
salt. — 5. When PEtj is poured into a flask con-
taining chlorine every drop takes fire, PCI,, HCl,
and carbon being formed. If the reaction be
inoderated a crystalline compound PEtjCL, is
formed. This melts near 100°, but has a very
high boiling-point. Bromine and iodme act in
the same way. — 6. Ethylene bromide forms
CHjBr.CH2.PEtJBr and CjH,(PEt3Br)2. Ethyl-
idene browdde, ethylidene chloride, and EtCl act
in like manner. Ethylene iodide, however, acts
with explosive violence, forming PEtjI, and
ethylene. — 7. Chloro - acetic ether forms
PEtjCLCHrCOjEt (Hofmann, Pr. 11, 525).— 8.
AUyl thiocarbimide (oU of mustard) forms
OaHsNCSPEtj possibly C3H5NEt.CS.PBt2. _ It
forms large crystals (from ether) [68°] and gives
with HJPtClj the salt B'oHjPtClj (Hofmann, Tr.
1860, 440). — 9. Phenyl-thAo-ca/rbanide forms in
like manner ' phenyl -tri- ethyl -phospho-thio-
urea- OS(NPhEt) (PEtj) [58°] (Hofmann, Tr.
1860, 432). It forms monoclinlc crystals (from
ether),isomorphous with CS(NC3H5Et)(PEt2) and
with allyl thio-urea. It decomposes at 100°. It
is insol. water, sol. alcohol and boiling ether. It
is very soluble in dilute acids, forms easily crys-
taUisable salts. HNO3 forms phenyl thiocarb-
imide and PEtjO. Boiling aqueous NH, forms
phenyl-thio-urea and- PEt,. KOH gives PEt„
di-phenyl-thio-urea, K2S, and KjCOj. CSjforma
the red PEtjOSj. Pheuyl-tri-ethyl-phospho-thio-
urea forms the following combinations : B'HGl .
cadmium yellow crystals, decomposed by boiling
water. — B'jHjPtClj. — B'Mel: golden needles
(from boiUng water). — (B'MeC^jPtCl^. —
B'MeOH: decomposed on boiling into PhNCS
and PEtjMeOH. — 10. Ethyl suVphocyanide forms
PEt3S and PEt^Cy. — 11. Tri-ethyl-phosphine
merely polymerises cyanic acid and its ethers. —
12. Mercaptan even at 100° has no action unless
air be present. — 13. Iodoform reacts with rise of
temperature, producing CH(PEt3)3ls which crys-
tallises from alcohol. It is v. sol. wat6r, si. sol.
alcohol, insol. ether. Aqueous Znl, gives in its
solution a pp. of {CH(PEts)3l3}23Znl2. Platinic
chloride gives {CH(PEt3)3Cl3}jPtCl„ which crys-
tallises from alcohol in rectangular laminiB.
ETHYL-PHOSPHINE.
607
Moist AgjO forma PEt3Me(0H) and PEt,0 (Hof-
mann, :Br. 10, 189 ; 11, 290).— 14. Chloroform
or COl, give CH{PEt3)301a.— 15. By dropping
PEt, upon cooled chloro-acetic aeid in a vessel
full of hydrogen there is formedEtsPCl.CH^.OOjH
'the hydrochloride of phosphorus betaine ''(Letts,
Tr. E. 30, 285 ; Pr.E. 11, 40). This compound
crystaUises from ether in colourless needles, it
has an acid reaction, and its platinochloride-
forms thick light orange needles. Vhe com-
pound Et3PCl.CHj.C0jjH splits up at 145° into
COj and PEtaMeCl. Solid KOH gives PEtjO
and potassium acetate. Moist Ag20 forms
EtjP(0H).CH,.C02H which, when dried over
PjO, in «acMO, becomes EtjP^^-g^CO, a very
deliquescent neutral substance. HBr converts
it into Et3PBr.OH2.CO2H, which forms dimetrio
plates (from alcohol and ether). It is split up
by heat into CO2 and PEtgMeBr. HI converts
Et3P(0H).CH2.C02H into very deliquescent
granular crystals of the acid Et,FI.CH2.C02H.
PEt,Cl.CH2.C02H is converted by Ag2S04 into a
very deliquescent sulphate which is split up by
heat into COj and (PEt3Me)2S04.— 16. PBt,
mixed with an equimolecular quantity of cooled
chloro - acetic ether forms very deliquescent
PEt3Cl.CHj.C02Et which melts below 100°, and
at a higher temperature is split up into FEtjMeCl,
COj, and ethylene. It forms a crystalline platino-
chloride, and is converted by moist Ag20 into
EtjP<^^^^0, alcohol, PEtjO, and acetic ether.
Solid EOH forms PEtjO, acetic ether, and ECl
(Letts, Tr. E. 30, 285).— 17. Bromo-aceUc ether
forms in like manner an extremely deliquescent
compound which melts below 100°, and is split
up by heat into PEtjMeBr, COj, and ethylene
(Letts). — 18. Bromo-acetic acid forms a colour-
less liquid which if heated to 100° and allowed
to cool solidifies. The product consists of at
least two substances : one of these substances,
(PBtaBr.O.CO.CHa?), when treated with potash
yields PEtjO andKOAo; the other, which is per-
haps PEtsH.0.C0.CH2Br, yields PEtj with KOH.
The first compound is also formed when PBt30 is
treated with acetyl bromide (Letts, 2V. E. 30,
285).
Salts. — The hydrochloride, hydro-
bromide, hydroiodide, sulphate, and ni-
trate are crystaUihe but extremely deliquescent.
— (PEtjH^jZnlj: tablets.— (PEt3)2H2PtCl, : crys-
talline, si. sol. cold water, insol. alcohol and ether.
By boiling PEt, with aqueous platinio chloride
there are formed two isomeric compounds of the
formula (PBt3)2PtOl2, a white substance insol.
ether, and a yellow substance crystallising from
ether in prisms [150°]. The yellow substance is
insol. water, and is converted into its isomeride
by heating with alcohol at 100°. When boiled
with water and PBt, it forms (PEt3)4PtCl2 (Oa-
hours a. Gal, Z. 1870, 350, 487).- (PEt,)jPdClj.
— (PEt3)4Pt201s.— (PEt3)4PtOl2AU2Cl,.—
/PBt3)2Au01.
Tri-ethyl-phosphine oxide PEtjO. Mol. w.
134. [44°] (H.); [53°] (P.). (243° uncor.).
V.D. 4-60 (calo. 4-66).
Formation.— 1. From PEtj by atmospheric
oxidation or by gently heating it with HgO or
kgfi (Cahours a. Hofmann, A. 104, 18).— 2. By
distilling PEtjOH, the other prodiict being
ethane. — 3. By decomposing (PEt4Cl)2ZnOl2with
solid KOH and a little water (Pebal, A. 120,
194).— 4. Prom BtOPClj and ZnEtj (Wichelhaus,
B. 1,80). — 5. By heating clear phosphorus (Ipt.)
with EtI (13 pts.) for 24 hours at 180°, and boil-
ing the product with alcohol. The residue is
evaporated and distilled with KOH (4 pts.) (Grafts.
a. Silva, Z. 1871, 359 ; cf. Carius, A. 136, 137),
When PI3 (1 mol.) is heated with EtI (3 mols.)
iodine is given o&, and a body is left whjch when
treated with solid KOH yields PBt,0 on distilla-
tion (Emmerton, Am. 4, 9).
Pr(^erUes. — Slender white deliquescent
needles. Dissolves in all proportions in water
and alcohol, less sol. ether. Very slightly vola-
tile with steam. Separates as a liquid when
Bohd KOH is added to its aqueous solution, or
when ether is added to its alcoholic solution.
Converted by HBr into FEtjBrj, and by HI into
PEtjIj. It is not affected by HjS or by halogens.
It forms crystalline compounds with some me-
tallic salts : (PEt30)3CuS04 : deliquescent, four-
sided, green prisms (Pebal). — (PBt30)2Znl2 :
[99°] ; crystalline pp. which, when crystallised
from alcohol, forms monoclinio crystals; a:b:o
= •905:1: -331; j3 = 83°13'.
Tri-ethyl-phosphine ozy-chloride (PEt3)20Cl2.
By passing dry HCl over fused PEtgO shining
crystals are formed, which are dissolvedinHClAq
and the solution is then evaporated (Hofmann).
Very deliquescent crystalline mass, sol. water
and alcohol, insol. ether. The solution treated
with pla&iic chloride in saturated alcoholic solu-
tion yields (P2Et302Cl4)3PtCl4, which crystallises
from dcohol in large orange monocliui'c prisms;
a:6:c = •631:1:1-678; j8 = 73°42' (Hofmann, Tr.
1860, 419).— (PBt,)20CLjZnClj: transparent oota-
hedra, sol. water and alcohol. By the action of
HCl on PEtjO Crafts a. Silva obtained a com-
pound PBt,(OH)Cl [128°].
Tri-ethyl-phosphine sulphide PEtjS. [94°].
Formation. — 1. By adding flowers of sulphur
to an ethereal solution of PBt,; after evapora-
ting the ether the residue is heated with boiling
water which dissolves PEtjS only, depositing it
in crystals on cooling. — 2. By distilling PBt,
with cini&bar. — 4. By decomposing PEtgCS,
with water or AgjO. — 5. By the action of mer-
captan on PEt, in presence of air.
Properties. — Long hexagonal needles (from
water) ; a:c = 1: '821. Sol. water, v. sol. alcohol
and ether, v. e. sol. CSj. Volatile with steam.
Decomposed by sodium giving Na^S and PEtj.
It may be separated from its aqueous solution by
KOH. Its aqueous solution is neutral to litmus,
but it dissolves more readily in HClAq than in
water, and the solution gives an unstable yellow
pp. with platinio chloride. The aqueous solution
is not affected by boiling aqueous lead acetate or
AgNO, or by HgO, but these substances become
sulphides when added to its alcoholic solution.
Tri-ethyl-phosphine seleuide PEtjSe. [112°].
From PEtj and selenium. Crystallises from
water, but turns red in air.
Tetra-ethyl-phosphoninm compounds.
PEt4{0H). When PEt,! is digested with water
and Ag20 there is formed a strongly alkaline
bitter solution, which dries up over HjSO, to an
extremely deliquescent crystalline mass. This
soUd hydroxide absorbs COj with avidity. Its so-
lution behaves like KOH towards solutions of me-
608
ETHYL-PHOSPHINE.
tallic salts ; alumina and zino hydrate, however,
dissolve less readily in excess of PBt^OHthanin
KOHAq. PBt,OH is split up by heat into PEtjO
and ethane.— {PBt4)2SO, : split up by heat into
PBtsS, PEtjO, and charred products. Chlorine
at 130° forms (PEtJjS0<01„ a yellow body
(Masson a. Eirkland, C. J. 55, 133). Bromine
vapour at 110° gives (PBtJjSO^Bru and
(PBt,)jSO,Brj.— (PEtJ^CO,: resolved by heat
into PEts, PEtjO, di-ethyl-ketone, C<H,„, and
CO,. — PBtjCl: deliquescent. Besolved by heat
into CJBi, and PBtsHCl (Letts a. Collie, 0. J.
Proc. 2, 164),— PEtjOlj : deliquescent ; decom-
posed by water, forming PBt^Ol (Masson a. Kirk-
land, 0. J. 55, 132).— PBtiAuCl, : yeUow needles
(from water). — (PEtjOl) JPtCl, : regular ootahedra
(from water); si. sol. boiling water, insol. alcohol
and ether.— (PEt4Cl)32BiOL,: six-sided tables
(JBrgensen, J.pr. [2] 3, 345).— (PEtiC^aZnClj :
from ZnEtj by gradual addition of POCIj fol-
lowed by water (Pebal, A. 120, 198) ; colourless
dimetric crystals, permanent in the air and v.
sol. water. — (PBtjBr),2B3r3 (J.). — PBt^Br, :
formed by evaporating an alcoholic solution of
the following salt. Bed crystals. — ^PEtjEr,: from
PEt^Br and bromine vapour at 110°. Violet
crystals (M. a. K.).— PBt,ICl„.— PEt^IBr,. —
PEtjIBr^. — PEtJ : formed with great violence
when PEtj and EtI are mixed. Ehombo-
hedra, isomorphous with Agl. V. sol. water,
m. sol. alcohol, insol. ether. The aqueous solu-
tion crystallises on addition of KOHAq in which
it is but slightly soluble. It is not decomposed
by KOHAq.— (PEt,I)2Znl2 : crystals ; formed by
heatingicrystallised phosphide of zino with EtI
at 175° (Cahours, A. 112, 228; 122, 192).—
PEtJj: [67°] ; brown plates (Jorgensen, ^.1871,
770).— PEtjITlIs (Jorgensen, J. pr. [2] 6, 82).—
(PEt4l),2BiCl3.--(PEtjI) j2Bil3 : brick-red crystals
(J.). The acetate is resolved by heat into
PEtjO, methyl ethyl ketone, C^H,, CH4, and CO,.
The benzoate is resolved by heat into PBtjO,
phenyl ethyl ketone, and benzene (Letts a.
CoUie).
Tri-ethyl-phosphine methylo-iodide
PEtsMeL From PEt, and MeL Gives rise to
PEtaMeOH, to (PBtaMeC^jPtCli, and also to
PEtaMeCl which decomposes above 800° into
ethylene and PEtjMeHCl (Collie, C. J. 53, 714).
Tri-ethyl-phosphine chloro-methylo-chloride
Et3P(CH2Cl)Cl. Formed by treatipg PEt, (1
mol.) with methylene chloride (1 mol.). Further
treatment with PEt, gives CH2(PBt3Cl)2, which
is decomposed by water into PBtjMeCl and
PEtjO (Hofmann, Pr. 11, 290).
Tri-ethyl-phosphine iodo-methylo-iodide
EtaP(CHjjI)I. Formed in like manner from
PBtj and methylene iodide (Hofmann, Pr. 10,
613). Moist AgjO gives EtjP(CH2l)0H whence
(Et3P(CHjI)Cl)jPtCl<.
Iri-ethyi-phosphine allylo-lodide PBtaCgHJ.
From . PEt, and aUyl iodide (Hofmann, Tr.
1860, 442). Splendid needles. Successive treat-
ment with moist Ag20 and hydrogen sulpho-
cyanide gives PEtjOaHiSCy 'which crystallises
with difficulty.
Tri-ethyl-phosphine propylo-chloride
PEtaPrCl. Split up by heat into BtjPrPHCl
and ethylene (Collie, 0. J. 63, 714).
Tri-ethyl-phosphine isoamylo-iodide
PEtjCjH„I. From PEt, and isoamyl iodide
in ethereal solution. Purified by solution in
alcohol and ppn. by ether. Gives with moist
Ag20 a hydroxide which on distillation appears
to give ethane " and di-ethyl-amyl-phdsphino
oxide. With HCl and PtCl^ the hydroxide gives
prisms of (PBt3C5H„01)jPtCl„ si. sol. water,
insol. alcohol, and ether.
Benzylo-chloride PEtjC^H^Cl. [178°].
Needles. Formed by heating PEt, with benzyl
chloride at 130° in presence of alcohol. Above
300° it spUts up into C^H^PBt^HCl and C^H,
(Collie, C. J. 53, 714). The benzyl-di-ethyl-
phosphine C,H,PEt2 so obtained boils about
253° and forms a crystalline oxide C^HjPBtjO
[330°] and sulphide C^HjPEt^S [95°] (300°-310°).
By treatmentof PBtjCjHjCl with Ag20,a strongly
alkaline solution of PBt3C,H,(0H) is obtained.
This base gives a very deliquescent crystaUine
iodide and a sparingly soluble pla tin 0 chloride
(PEtaOjHjC^jPtCl,. The.basePEtsC,H,(0H)i3
split up by heat into toluene and PEtjO (Collie,
P. M. 24, 27). The hydroxide does not form a
normal carbonate, but it forms an acid car-
bonate which is split up by heat into toluene
CO2 and PBtjO. The sulphate on distillation
gives PEt30, SO2, and PhCHj-CH^Ph. The
bromide gives on distillation HBr, PEtjHBr,
PEtjCjHyHBr, acetylene, &o. The aceta^te
gives PEt,0, methyl benzyl ketone, PBt,, and
benzyl acetate. The oxalate gives PBi,0,
toluene, CO, and CO.
Tri-ethyl-phosphine bromo-ethylo-bromide
Bt3P(CH2.0H2Br)Br. [235°]. Produced, together
with C2H4(PBt3Br)2, by adding ethylene bromide
to PEtj mixed with twice its volume of ether
until the liquid no longer gives with CSj the red
crystals of PEt3CS2. The two products are
separated by crystallisation from alcohol in
which C2H4(PEtjBr)2 is much the more soluble.
White unctuous elongated rhombic dodecahedra ;
V. sol. water, m. sol. alcohol. It gives off HBr
when heated.
Beactions. — 1. Silver salts added to its cold
solution throw down only half the bromine as
AgBr; on continued boiling the whole of the
bromine is ppd. with formation of salts of vinyl-
tri-ethyl-phosphonium. — 2. Moist Ag20 forms a
solution of Bt3P(02H40H)(OH).-3. Potash has
no action in the cold.— 4. Ziiic and dilute
H2S0, form PBt4Br.— 5. It unites with PMe^
forming C2H4(PBt3Br)(PMe3Br).— 6. PEt, gives
C2H4(PEt3Br)2. — 7. Ammonia gives rise to
C2H4(PBt3Br)(NH3Br) ; ethylamine,diethylamme,
and trimethylamine act in like manner. —
8. Triethylamine when pure has no action at
100° ; but in presence of moist alcohol it forms
PBt3(C2H40H)Br and NBtjHBr.
Tri-ethyl-phosphine bromo-ethylo-chloride
Bt3P(CH2.CHJBr)Cl. From the preceding and
AgCl. Crystallises with difficulty, v. sol. water
and alcohol. Bt3P(C2H4Br)CLAuCl3 : light yellow
needles (from boiling water ; si. sol. cold water). —
{Et8P(C2H4Br)Cl}2PtCl4: longmonochnic orange-
yellow prisms; a:6:c = '969:l"658. May be re-
crystallised from boiling water.
Tri-ethyl-phoephine bromo-ethylo-iodid»
Et3P(CH2.CH2Br)I. Scales, si. sol. cold water.
Obtained by deoomposmg the sulphate by Bal2.
The sulphate obtained from the bromide
by Ag2S04 forms long white needles. The
ETHYL PHOSPHITES.
600
hydroxide EtaP(CH2.CH2Br)0H obtained by
treating the sulphate -with baryta is unstable.
Tri-ethyl-phosphine ohloj-o-ethylo-chloride
PEta(0H20H201)Cl. Prom PEt, and ethylene
chloride in the cold.— (PEtj(C;tH4Cl)01)2PtCli :
orange-yellow crystals.
Tri-ethyl-phosphine oxy-ethylo-hydroxide
PEts(0Hj.CH[jOH)OH. From PEt3(CjH,Br)Br
aad moist AgjO. Very deUquesoent syrup. When
strongly heated it is resolved into ethylene,
PEtj, and water. It forms the following salts : —
PBtj(02H^OH)Gl : indistinctly crystalline; con-
verted by PCI5 into PEt3(02H,Cl)Cl, and by PBr^
into PEt3(03H4Br) 01.— PEts(C2H,0H)AuCl, :
golden needles, si. sol. boiling water. —
)PEt3(OjHiOH)Cl}jPtCl,: orange-yeUow oota-
hedra, v. sol. hot water. — PEt3(OjHiOH)I: long
needles which decompose at 100°.
Tri-ethyl-phosphine vinylo-coinpoiinds.
These are formed by prolonged boiling of tri.
ethyl-phosphine bromo-ethylo compounds with
silver salts. Thus silver acetate gives rise to
PEt,(CH:CHj)OAc whence platinio chloride gives
octahedra of {PEt,(CH:CHj)01}2Pt0l4. .The
hydroxide PEt3(02H.,)OH is formed when
H0.PEt3.0^4.NH3.0H is heated.
Heza-ethyl-di-phospMne ethyleno-dibromide
(EtaPJjCjHjBr^. Prepared by treating ethylene
bromide (1 vol.) with PEtj (3 vols.). Also from
Et3P(CjHjBr)Br and ethylene bromide in alco-
hoUo solution at 100°. White needles, v. sol.
water and alcohol, insol. ether; permanent in
the air. A boiling alcoholic solution dissolves
AgjO and on cooling deposits crystals of
(Et,P)20,HjBrjAgBr which is resolved by water
into AgBr and (m3P)fi,Mfir2.
Heza-ethyl-di-phosphine ethyleno-dihy-
drozide (Et3P0H)2C2H,. Prepared by adding
excess of AgjO and a little water to a solution
o! the precedang dibromide or of the correspond-
ing diriodide. Highly caustic deliquescent syrup
which absorbs CO2 from the air forming a crys-
talline carbonate. Its solution begins to de-
compose at 160° ; at 190° some of it forms an
isomeric base, and at 250° it is completely de-
composed into PEtj, ethylene, PEtjO, and water.
Its solution reacts with metallic salts in the
same way as KOH, excepting that the pp. of
zinc hydrate is not soluble in excess and that
stannous and antimonious salts give double-
salts crystallising in interlacing needles. It ex-
pels NH3, amines, and PEtj from their salts.
It dissolves sulphur forming a yeUow liquid
which gives off HjS when acidified. Its solution
also dissolves iodine forming a colourless solution
apparently containing its iodide and iodate.
Salts.— (Bt3P)2(C2HJ0l2: from the hydrox-
ide and HCl, from the dibromide and AgCl, or
from PEtj and ethylene chloride. Deliquescent
pearly flat lamina; v. sol. water and alcohol,
insol. ether. KOH ppts. it unaltered from its
solutions.— (EtaP)2(C2HJiAu2Cl8: golden needles,
si. sol. cold water, v. sol. boiling alcohol. —
{(Et3P)jOjH401j}j3HgCls: crystals, si. sol. water
and alcohol.— (Et3P)2{0jH4)2PtClj: monoolinio
prisms (from boiling HClAq) ; nearly insol.
boiling water.— (Et3P)j(0»Hj2Cl2(SnOyj ? large
prisms.— (Et3P)j(0jHJI(: [231°]; trimetric
needles. S. 458 at 100° ; 3-08 at 12°. SI. sol,
alcohol, insol. ether. Potash ppts. it in the crys-
talline state even from very dilute solutions^—
(Et3P),(C2H,)LZuI., : long needles (from hot
water).— (Et3P)j(02HJ(0104)j: very long needles,
detonates above 100°.
Ethylene-tri- ethyl-phosphammoninm com-
ponnda.— Et3PBr.CH2.0H;j.NHaBr. Formed from
EtsP(0H2.0H2Br)Br and alcoholic NH3 at 100°.
DeUquesoent. ^ EtjPCl.CHj.CHj.NHjC^AuCl,), :
slender golden needles, si, sol. water. —
Et3P01.CH^.CH,.NH3ClPtCl4: pale-yellow tri-
metric pnsms, si. soluble in boiling water. —
Et3P(0H).CjH4.NH30H. From the bromide and
moist Ag^O. Separated by KOH as oily drops.
Split up by heat into NH„ water, and
Et3P(0,H3).0H.
£thylene-tetra-ethyl phosphammonlum com-
pounds Et3PBr.02H,,.NEtH2Br. Formed from
Et3PBr(CjH4Br) and ethylamine. The corre-
sponding hydroxide is oily. The iodide
Bt3PI.GjH,.NEtH2l forms needles, v. sol. water,
slightly soluble in alcohol, insol. ether. —
Et,PC1.0jH4.NEtH301(AuCy3: golden sparingly
soluble needles. — Et5PC1.0jH4.NEtHjClPtCl4 :
orange monoclinic tables.
Ethyleue-penta-ethyl phosphammoniam bro-
mide Et3PBr.C2H4.NEtjHBr. From diethylamine
and EtsPBr(C2H4Br).— May be converted into
Et3PCl.CjH4.NEt2HClPtCl4 : rectangular plates.
Ethylene-methyl-tri-ethyl-phosphammonium
bromide Et,PBr.C2H4.NMeH2Br. Prepared from
Et3PBr(C2H,Br) and methylamine. Gives
Et3PC1.02H4.NMeHi,CIPt01. : long needles; v.bL
sol. water.
Ethylene-tri-methyl-tri-ethyl - phosphammo ■
nium bromide Et3PBr.Os5Hi.NMe3Br. Foniied
ill like manner, using trimethylamine. —
Et3PCl.C2H4.NMe3ClPtCl4 : needles.
Ethylene-heza-ethyl-phospharsoninm brom.
ide Et3PBr.OjH4.AsEt3Br. Prepared from
Et3PBr(C2H4Br) and AsEt,. Cold moist Ag^O
gives Et3P(OH).02H4.AsEt3(OH) which on boil-
iug splits up into Et3P(OH).C2H4.0HahdAsEts.—
Bt3PC1.02H4.AsEtsClPtCl4 : orange-red triclinio
prisms (from boiling HClAq); nearly insol.
water.
ETHTL - FHOSFHIXIG ACID v. Eihahb
PHOSPHOUIC ACID.
ETHYL PHOSPHITES
Mono-ethyl phosphite P(OEt)(0H)2. Ethyl-
phosphorous acid. Formed by adding PCI,
drop by drop to dilute alcohol in the cold. The
product is evaporated m vacuo and saturated
vrith BaCOj (Wurtz, A. Ch. [3] 16, 218). The
free acid is very unstable, splitting up in solution
into alcohol and phosphorous acid. — BaH2A"2 :
amorphous deliquescent mass. In solution it is
resolved gradually by atmospheric oxidation into
alcohol and barium metaphosphate. It is' v. sol.
water and alcohol, but ppd. from its alcoholic
solution by ether.— BaA". Obtained by treating
EtaPOj (1 mol.) with hot aqueous BaOjH2(lmol.).
Amorphous. Eesolved by boiling water into
BaHPOj and alcohol (Eailton, C. J. 7, 219).—
PbHjA''^ : unctuous scales, permanent in the
air ; sol. water and alcohol, insol. ether.
m-ehloride MO.VOl^. (118° cor.). S.G. 2
1-3053 (Thorpe, O. J. 37, 346). Formed by treat-
ing EtjPOj with PCI3, avoiding excess of Et,POj
(Chambon, Jena. Zeit. [2] 3 ; 2nd Suppl. 97).
Formed also when dry alcohol is treated with
PClj (Mensohutkin, A. 139, 343).
BeacHons.—!. l^a^ forms HCl, alcohol, and
610
ETHYL PHOSPHITES.
H3PO,.— 2. Bromine gives EtBr and POOljBr.—
3. El^POj reacts forming EtjPO,, phosphorus,
and EtOl.— 4. Heated to 165° in a sealed tube
it is resolved into EtCl, free phosphorus, PClj
and P2O5.— 5. Heated with H3PO3 there is evolved
EtCl and HCl, while free phosphorus and HgPO,
remain. — 6. PCI, does not act on it. — 7. PCI5 at
100° forms POCI3, PCI,, and EtCl (Geuther, /.
1876, 206).— 8. PBrs gives POBrOlj, PBr,, and
EtBr.
Di-ethyl phosphite (BtOJi^POH. The barium
salt BaA'2 is formed by adding a hot solution of
baryta (1 mol.) to EtgPOj. It formls a very de-
liquescent crystalline mass ; extremely sol. water,
si. sol. alcohol. It does not decompose at 108°.
Aqueous E2SO1 converts it into the deliquescent
salt EA.'. The free acid has not been isolated.
Chloride (EtO)2PCl. From alcohol (2mols.)
and POI5 (1 mol.) (Wichelhaus, A. Suppl. 6, 264).
May be distilled. Chlorine converts it into EtCl
and {EtO)PO:Cl3.
Tri-ethyl phosphite (EtO)3P. Phosphtirous
ether. (191°). S.G.iaa 1-075. V.D. (in hydrogen)
5-84 (oalc. 5-76). PCI, (1 mol.) diluted with five
times its bulk of ether is added by small portions
to NaOEt (3 mols.). The ether is distilled off,
and the residue distilled from an oil-bath at
200°. It is rectified in a current of hydrogen
(Bailton, C. J. 7, 216). At the same time another
body PjOjCuHa, is formed (157-5° cor.). S.G.
i4 -960. This is best formed from dry NaOEt
(4 mol.) and PCI, (1 mol.), both in ether (Geuther,
A.. 224, 277). It has a pleasant smell, and when
distilled it slowly splits up thus :
PjOsOuH,, = PO,Et, + PO^Et, + HOEt.
It is not decomposed by water at 100°.
Properties. — Phosphorous ether has a
pleasant odour (G.). It is sol. water, alcohol,
and ether, and burns with a bluish flame. '
. Reaetiorns. — 1. Heated with baryta-water it
gives Ba(Et2P0,)2 and BaEtPO,.— 2. ComsHo
potash gives phosphorous acid and alcohol. —
3. Gradual oxidation by nAtiHc acid gives phos-
phoric and oxalic acids 4. It absorbs oxygen,
especially on warming, forming EtjPOj. — 5. On
disUUaUon it gives PH,, phosphoric acid, and
probably ethylene.— 6. PCI, gives EtOPOl,; a
smaller quantity of PCI, gives Et3P04, phos-
phorus, and EtCl.— 7. PClj gives (EtOJPOCl,,
EtCl, and PCI, (Chambon). — 8. Bramme forms
EtBr and (BtO)^OBr.
OorofiMMsiiora.— Et,PO,PtClj. [83°]. Formed
from FCI3, alcohol, and PtCl, (Schiitzenberger,
Bl. [2] 18, 101). Yellow prisms. Its ethereal
solution absorbs' ethylene forming oUy
(EtjPOaPtCyjCjH,. CO forms in like manner
(EtjPOaPtCyjCO. Ammonia passed into the
ethereal solution of EtjPOjPtCLj ppts. coloutless
crystals of EtsPOjPtCljNjBij. The following com-
pounds of ethyl phosphite have also been described
(Bt,PO,)jPtCl, : prisms.— Et3P0,.PtCl,PCl,.—
(Bt3PO,)jPtOl3N,H.. — Et3P0,PtCljBr,. —
(EtjPOgisiPtClJBrij. — EtaPOsPtjCli (Cochin, Bl.
[2] 31, 499).— Et3P03PtCl4 (Pomey, Bl. [2] 35,
421).
TKI-ETHTL-PHOSPHOBETAlNE v. Tm-
EIH-XL-FHOSFHINI!, BMLCtUmS 12 tO 15.
EIHTL-FHOSFHOB-DIGHIiOBIDE isEiHn-
di-cMoro-vnosssisx.
ETSTTL . FHOSFHOSIC ACID «. Kian
>Bosra4i68f
ETHTL-FHOSFHOBOUS ACID v. Etbyi;
.-CEt,-
fbospehes.
DI - ETHTI - PHTHALIDE C,H,<^g'^»>
[52°]. Formed by adding ZnEtj to phthalyl
chloride mixed with benzene (Wischin, A. 143,
260 ; iFriedlander, Z. K. 6, 590 ; V. Meyer, B. 17,
818). Large dimetrio crystals (from ether).
Insol. water, t. e. sol. alcohol and ether. Does
not react with KHSO, or hydroxylamine.
ETHTL-FHIHALimiOE v. Ethylirmde of
PhIHAIiIO tXiJD.
ETHYL.FHTHAI,I]IIIDTI<-BEITZYL is de-
scribed as BENZTLIDENE-FHTHAIyETHTLIIinilNE.
a-EIHYL-HOaCO-0-FHIHALOmTSILE v.
O-GTANO-FHENYL-BUTVBOiniBIIiE.
EIHTL-FICBAmiSE v. TBi-mTBO-EiHxi.-
ANHimE.
EtHTI-FIFEBIDIITE «. Eibyl-fsbiddib
BEXABTDBIDE.
EIHTL FBOFABGTL OXIDE v. PBOFABaYi,
ALCOHOL.
ETHYL-ISO-FBOFENYI-OXIDE CsH.oO i.e.
Et.O.C,H,. (63°). S.G. 2 -79 ; S2 -769. Formed
by heating propylene bromide and alcoholic
potash in sealed tubes to 170° or by treating
propinene Me.C=CH in the same way (Faworsky,
J. pr. [2] 37, 533). Colourless mobile liquid.
Yields on decomposition with dil. H2SO4 ethyl
alcohol and acetone.
ETHyL-FEOFIONTl-PBOFIONIC ACID.
Methyl ether G,H„0, i.e.
CH,.CHj.C0.CMeEt.C03Me.
(208°). From methyl - propionyl - propionate,
EtI, and NaOEt at 100° (Pingel, A. 245, 84).
ETHYIi-FBOFIONYL-UEEA v.Propiora/l de-
rwatvoe of Eihtl-ubea.
ETHTL-PEOFTL ACETAI. Described under
ETHYL-FBOFTL-ACETIC ACID v. Hefioio
AOID.
ETHYL- FBOFYl- ACETYLENE v. Hep-
IINENE.
DIETHYL-FBOFYL-ALKINE «. Di-eihtl-
OZTFBOFYL-ASIIIIE.
TBI-EXHIL-FBOFYL-AKUONIirK IODIDE
C,H2,NI t.e. NEtjPrl. From NEt, and PrI
(Mendius, A. 121, 136). Needles.— B'sH^PtCl,:
octahedra.
ETHYL -FEOFYL- ANILINE CsHj-NBtPr.
[216° uncor.] Liquid. Formed by the action of
ethyl bromide upon propyl-aniline, or of propyl
bromide upon ethyl-anUine. — B'HCl: crystals,
[131° uncor.] (Glaus a. Hirzel, B. 19, 2787).
Methylo - iodide v. Propylo-iodule 0/
Methyl-ethyl- ANiLisE.
ETHYL-FBOFYL-BENZENE
[3:l]C3H,(C,H,)Et. (194°). S.G. ia -8588. V.D.
6-37. Occurs in resin oil (Benard, C. B. 97,
328). Gives isophthalio acid on oxidation.
H2SO4 gives a sulphonio acid of which the Ba
Bait (G„H,sSO,)^a aq crystallises in plates.
ETHYL . FBOFTL ■ CABBINOL v. Hexyl
ALCOBOL.
Ethyl-di-propyl-oarbinol v. Ennyl alooeol.
ETHYL-FBOFYL-CABBONATE
(Oja,0).CO.(00,H,). (146° oor.). S.G. =j° -9516.
Colourless liquid. Formed by adding AlCl, to
a mixture of propyl alcohol and ethyl chloro-
formate (Pawlewski, B. 17, 1606).
$THi;it'FBOFYLENE y. 4)(y;«khi!,
ETHYL-PYEIDINE.
511
ETHTl PROPYL ETHEE v. Ethzd pkopyl
OXIDE.
DI-ETHTL-PBOPYl-GLYOOILIirE v. Di-
EIHni-SI-OZXPBOBIli-AIIINE.
ETHYL-PEOPYI-GIYOXAIINE
C^,{G^i){G^,)^^. Oxal-prapylme. (231°).
S.G.12-952. V.D. 4-8 (obs.).
Wormal/um. — 1. Prom di-propyl-oxainide by
the action of PCI5, the resulting ohloro-ethyl-
propyl-glyoxaline (v. p. 66) being reduced by HI
and phosphorus (Wallach, A. 214, 314 ; B. 14,
423). — 2. By the action of propyl bromide on
secondary (para)-ethyl-glyoxaline B'jHLjOljPtCl,
(WaUaoh, B. 16, S43 ; Eadziszewski, B. 16, 491).
PrcfperlAes. — ^Liquid, with nareotio smell;
misoible with water. Its zinc double salt dis-
tilled with lime yields NH,, an olefine, pyrrol,
and a basic liquid (c. 253°).
Salts. — B'j^PtCl, : orange laminm. —
B'jHjZnCl<: [92°]; prisma.
Methylo-oompounds B'Mel: needles, sol.
water. — B'jMejPtOls: plates.
Ethyl-isopropyl-glyozalino 0^(0^,)^^.
Oxal-ethyl-butylme. (220°). B.Q. ^ -959
(Eieger, M. 9, 607).
DI-ETHYL PEOFYXIDENE DISULPHOHE
CMej(S02Et)2. Sulfonal. Bi- ethyl -sulphone-
da-methyl-methcme. Propane dAsulpMnlo ether.
[126°]. (c. 300°). S. 1 in the cold; 5 at 100°.
Frepa/raUon. — 1. By action of sodium on a
benzene solution of ethylidene-di-ethyl-sulphone
previously mixed with methyl iodide. — 2. By
hoiUng an alcoholic solution of ethylidene-di-
ethyl-sulphbne with methyl iodide and alcoholic
potash. — 3. By treating EtS.SO^.OH with ace-
tone and ECU, tiie product CMe2(S£t)2 being oxi-
dised by KMnO, (Baumann, B. 19, 2808).
Properties. — Thick prisms ; si. sol. cold water
and alcohol ; m. sol. hot water. Used as a sopo-
rific, being said to have no concomitant effects.
Does not evolve hydrogen when sodium is added
to its benzene solution (B. Promm, B. 21, 187).
ETHYL w-PEOPYL KETONE 0„H,20 i.e.
Et.CO.Pr. Mol. w. 100. (c. 123°). S.G. 112
•818.
Formation. — 1. Occurs among the products
of the distillation of calcium butyrate (Friedel,
A. 108, 125). — 2. From butyryl chloride and
ZnEtj followed by water (Butlerow,.BZ. [2] 5, 17).
3. By distilling a mixture of calcium propionate
and calcium butyrate (Volker, B. 8, 1019).
Properties. — ^Liquid. Does not unite with
NaHSOj in the cold, but on heating the mixture
and allowing it to cool a crystalline compound
is formed, which is resolved by water into its
constituents. Chromic acid mixture gives on^
propionic acid according to Popofl (A. 161, 285),
but Wagner (J. B. 16, 660) obtained acetic and
butyric acids also. Sodium amalgam reduces it
to a secondary hexyl alcohol and a pinacone
Ci^HjsOj. Zinc and Mel forms OMeBtPrOH
(140°) (Sokoloft, /. B. 1887, 587).
Ethyl isopropyl ketone Et.CO.Pr. (118°)
(P.); (114°) at 745 mm. (W.). S.G. g-830;
^» '814 (W.). Prom isobutyryl chloride and
ZnEtj (Butlerow, A. 189, 44 ; Pawloff, J. B. 8,
242 ; Wagner, J. B. 16, 697). Liquid. Does
not combine with NaHSOj. Gives, on oxidation
by chromic acid, propionic, acetic, and isobutyric
acids (W.).
ETHYL PEOPYL OXIDE CsH,jO i.e. Et.O.Pr.
(63-6°). S.G. g -7545 (Dobriner, A. 243, 4) ;
7 -7386 (Briihl, 4. 200, 177). S.V. 127-1. O.B.
(0°-10°) -00134 (D.). HIS 1-3740 (B.). Ea, 42-86
(B.). Critical temperature 233° (Pawlewsky, B.
16, 2634). Formed by distilling a mixture of
ethyl alcohol and propyl alcohol withHjSO^;
EtjO being also formed (Norton a. Presoott, Am.
6, 245). Also from w-propyl bromide and NaOEt
in alcohol, much propylene being given off.
Ethyl isopropyl oxide Et.CPr. (54°) (Mar-
kownikofl, A. 138, 374) ; (48°) (E.). S.G. 2 -745
(M.). Formed by heating isopropyl iodide
(1 vol.), triethylamine (2 vols.), and alcohol
(4 vols.) at 150° (Eeboul, J. 1881, 409). Dilute
'BJBOt at 150° BpUts it up into EtOH and iso-
propyl alcohol (Bltekoff, Bn. 1, 298).
DI-ETHYL-PBOPYL-PHOSPHIIIE PEt,Pr.
(146°-149°). From PEt,Pr01, by distiUing and
treating the product with NaOBAq (Collie, O. J.
63, 721).
ETHYL -PEOPYL. PINACONE e. Di-oxx-
DODBCANB. ^
{Py. 2:3) - ETHYL . PEOPYL - dUINOIINE
/CH:C(OJH.)
CjHX I . (291° at 720 mm.). Pre-
Nn : C(C3H,)
pared by slowly adding w-bntyrio aldehyde
(100 g.) to a cooled mixture of aniline (60 g.) and
fuming HCl (120 g.). Colourless liquid. Vola-
tile with steam. V. sol. alcohol, ether, <fco.,
nearly insol. water. On oxidation with OrO, it
gives {Py. 2)-ethyl-quinoline-(Py. 3)-carboxylio
acid.
Salts.— B'HG12aq: flat triclinic tables.—
BBNOaaq: long white needles. — B'HjSO,:
easily soluble concentric needles. — B'^HjOlJPtOl,:
yellow needles, sol. hot, insol. cold, water. —
B'^HjOrjO,: long orahge-yeUow needles. —
B'CeHj(N02)30H: [163°]; glistening yeljow
plates or needles, sol. hot water and hot alcohol,
very sparingly sol. cold alcohol, insol. cold
water.
Methylo-iodide BMelaq: [172°]; yellow
needles ; v. sol. water and alcohol, insol. ether.
— P'MeCl)^tCl4 : orange-yellow needles (Eahn,
B. 18, 3361).
ETHYL-FBOPYL-BI-THIO-CAEBOirATE «.
EtHYIi oabbonates.
(7)- or {Py. 1)-ETHYL-PYEIDIIIE
.CH=CH
Et.Ci
Vh-.
>N. (166°). S.G. 2 -9522; 22-9358.
Formation. — ^By heating pyridine ethylo-
iodide in sealed tubes to 320° and separating the
{Py. 3)- and {Py. l)-isomerides by means of the
platino-ohlorides or ferrocyanides. The salts of
the Py. 1 base are least soluble (Iiadenburg, A.
247, 18 ; af. B. 16, 2059).
ProperUes. — Unpleasant smelling liquid, si.
sol. water. Yields on oxidation with perman-
ganate isonicotinio acid [303°].
Salts.— (OjHjNHC^jPtCl, : [208°]; plates,
si. sol. water.— B'HAuCli : [138°]; golden-yel-
low prisms.— I'iorate : [163°] ; thin yellov
needles. — Mercuric chloride double salt
[150°]. According to 0. de Coninck this base
(or the mixture of isomerides) occurq in coal-tar
Itttidine (0. B. 98, 235).
612
ETHYL-PYRIDINE.
(o)- or (Py. 3)-Ethyl-pyridiiie
>OH=OH
CHC >N. (148-5° cor.) at 752 mm. S.G.
^CH— 0— Et
s -9498.
Preparaticm.—3 g. of pyridine are heated for
an hour with 6 g. Ktl to 320°. Some ethyl-
benzene is formed. The acid contents of the
tnbe are distilled from a copper retort with
steam. The residue is then supersaturated with
NaOHAq and distilled until the distillate is no
longer alkaline. The base is then separated by
means of solid EOH and fractionated. Purified
by means of gold salt, which is decomposed by
SHj ^adenburg, A.U7, 14). (Py. 1)- and {PyS)-
ethyl pyridines cannot be separated by fraction-
ation.
Properties. — Colourless liquid, si. sol. water,
miscible with alcohol. It gives picolinic acid
on oxidation.
Salts.— (C,H,NHCl),PtCl4: [164°]; orange-
yellow plates.— CjHsN.HClAuOl.: [121°]; yellow
plates, V. sol. water. — Piorate:
B'.CeH2(NO,)30H. [110°].
(Py. l:3)-Di-ethyl-pyridine
<CH=0— Et
. >N. (188°). S.G. 2 -9338. Is
CH-CH
formed, together with (Py. 1)- and (Py. 3)- ethyl
pyridine by the action of EtI on pyridine (Laden-
■ burg, A. 247, 48). Colourless liquid with a
very unpleasant odour, si. sol. water. Hr yields
lutidinio acid [235°] on oxidation.
Salts.— (C,H„NHCl)aPtGl,: [171°] ; orange-
yellow prisms, si. sol. water. — Picrate:
C„H„N.O,Hj(N02)sOH : [100°]; prisms (from
water), plates (from alcohol).
(o). or (Py. 3)-ETHYL-PYEIDINE HEXA-
CHj— CH.Et
HTDBIDE CHj/^ NnH. Ethyl-jmperi-
dine. (145°). S.G. -8674. Formed by reducing
{Py. 3) -ethyl pyridine with sodium and alcohol
(Ladenburg, A. 247, 70; B. 18, 29e8). Liquid
smelling of pyridine hexahydride.
Beaetions. — 1. Forms with Mel a v-methyl
derivative. — 2. Br and NaOTTAq convert it into
a base containing 2H less (cf.B. 20, 1645).
Salts.— (C,H,5N.HCl)2PtCl«: [178°]; plates
m. sol. water.
(y)- or [Py. l)-Ethyl-pyridine hezahydride.
OHj— CH,
Et.CH<^ \nH. {y)-Ethyl-jpiperidine.
CHj-CHj
(158°). S.G. 2 •8759. Formed by reducing
(Py. l)-ethyl pyridine with sodium and absolute
alcohol (Ladenburg, A. 247, 72 ; cf. C. B. 98,
516). Liquid with an unpleasant odour. More
soluble in cold than in hot water. Its hydro-
chloride acts physiologically like coniine
(Filehne, B. 16, 739).
Salts.-(0,H,5NH01)jPtOl4: [174°] ; orange-
oolonred plates, m. sol. water. — ^B'.HCl.AuCl^ :
[105°]; golden-yellow plates si. sol. cold, v.
sol. hot water.
Methyleno-di-iodide C,H„Kl2. Formed
by heating ethyl-piperidine with methyleue-
iodide. It forms sparingly soluble yellow plates.
Only one I atom can be removed by AgjO, ol
replaced by CI by means of AgCl. ,
The cMoro-iodide C^B.^'SICI is formed
from the di-iodide by AgCl.- (C,H„NICl),PtCl, :
orange oilystals.— (CgH^NIClJAuOl, : small
yellow crystals (Ladenburg, B. 14, 1843).
[Py. l,3)-Di-ethyl-pyridine hezahydrida
CHBt^g^'cH^'^^^- (o-l^B"). S.G. £-8722.
Formed by reducing' (Py. l,3)-di-ethyl-pyridine
with sodium and alcohol ^jadenburg, A. 247|
97).— B'.HjPtOl,. [174°].
CH=CHv
ETHn-PYEEOEECANi.e. |
"\i
NEt.
ch=ch/
(131°). S.G. i^ -888. Prepared by the action
of ethyl iodide on pyrrole potassium. Formed
also by distilling neutral ethyl-ammonium
mucate or saccharate (C. A. Bell, B. 9, 935 ;
Bell a. Lapper, B. 10, 1962 ; cf. Lubavin, Z. [2]
5, 399). Formed also by distiUing ethyl-sue-
cinimide with zinc-dust (BeU, B. 13, 878).
Colourless liquid; insol. water, miscible with
alcohol and ether. Its vapour turns acidified
pine-wood red. By long boUing with HCl it
gives a red powder of the constitution Oj^S^fij
[165°-170°]. Potassium does not attack it. Its
alcoholic solution gives a pp. with EgClj.
Tetra-bromo- derivative
CBr=CBrv.
I >KEt. [90°]. Colourless needles.
CBr=CBr/
Insol. water, sol. alcohol. Prepared by the
action of Br on ethyl-pyrrole (Bell, B. 11, 1810).
Ethyl-pyrrole CjH,EtN? (164°). Formed
by adding iJuClj (12 g.) to a mixture of pyrrole
(50 g.) and paraldehyde (50 g.), the reaction
beginning at once with evolution of heat
(Dennstedt a. Zimmermonn, B. 19, 2189).
Colourless, but turns brown in air. Gone. HCl
at 130° appears to give CHMefC^pgiQ^NH.
Acetyl derivative C^H^t.NAc. (225°).
Formed by boiling ethyl-pyrrole with AC2O and
KaOAc. An isomeric acetyl derivative [47°]
(250°) is formed at the same time. Benzoic
aldehyde and potash converts the acetyl deriva-
tive into C,HjEt.N.CO.CH:CHPh [150°].—
C^HjAgEtNAc.
ETHYI-PYEEOIiE-AZO- v. Azo- oompociids.
ETHYL-PYESOLE CABBOXYIIC ACID
CiHsEtN.CO^H. [78°]. Formed by heating its
ethylamide with alcoholic potash at 120° ^ell,
B. 10, 1864). Slender silky needles (from hot
water). Volatile with steam. Above 100° it
splits up into COj and ethyl-pyrrole. Boiling
dilute HCl decomposes it in like manner. Fe^Cl,
gives a red colour. — ^AgA': needles (from hot
water).
Ethylamide CjH^NjO i.e.
OjHsEtN.CONHEt. JDi-ethyl-carbopyrrolcmide.
[44°]. (270°). Formed, together with ethyl-
pyrrole and the diethylamide of ethyl-pyrrole di-
carboxylio acid by heating ethylamine mucate
in a paraffin-bath (BeU). Prisms (from water).
Soluble in cone. HCIAq without change ; even
boiling aqueous alkalis have little action, but it
is saponified by alcoholic KOH at 125°- Bromine
water gives a pp. of the tri-bromo- derivative
ETHYL SELENATE.
613
/CO.NHEt
C,H„Br3N,0i.«.<°|j:^->NEt [121°] while
C,H,^rjNjO, [197°] remains dissolved (Bell, B.
li, 1813).
Ethyl-pyrrole dicarbozylic acid
C4HjBtN{C02H)2. Obtained by heating its
ethylamide with alcoholic potash at 130° (Bell).
Needles (from dilute alcohol). Sublimes without
melting at 250°, being partly split up into ethyls
pyrrole and COj. Slowly split up in like manner
by strong acids in the cold. — Ag^A": insol.
water.
I>t-B«Ay Z-di-ami^e CiHjEtN(C0NHEt)2.
Tri-ethyl-dica/rbopyrrolamide. [230°]. Formed
in small quantity by distilUngethylamine muoate
(Bell). Needles. Insol. water, sol. cone. HOlAq.
May be subUmed. Saponified by alcoholic, but
not by aqueous, potash.
EXHYL-QTriNALDIIfIC ACID v. Ethyl-
QTW!iousm-{Py. 3)-CABB0XYi.ia Acn>.
(7)- or (Pj/.2)-ElHYl-ftTJIN0LINB
.OH:CBt
0„H„N ».a. O.H«< I . (273°oor.) (Eeher,
\ N:GH
B. 20, 2734). Colourless refraotive liquid.
Formed by distUlatiou of its {Py. 3)-oarboxylio
acid, 00, being evolved (Kahn, B. 18, 3870).
Obtained also by reducing (Py. 3, 2)-ohloro-
ethyl-quinoline'with HI in acetic acid (Baeyer a.
Jackson, B. 13, 121); and, together with the
following isomeride, by heating quinoline ethylo-
iodide at 280° (Eeher, B. 19, 2995). Gives
cinchonic acid on oxidation. On reduction it
yields a base boiling at (271°-275°).
Salts. — The hydrochloride is v. sol.
water and deliquescent.— B'HNOs: [116°] ; white
needles.— B'HHgClj : [154°] ; white needles, v.
sol. dilute HOlAq. — B'HAuOli : slender yellow
needles. — Ohromate: red needles. —
B'-BLCLPtCl.! [203°]; orange-yellow needles. —
Piorate: [163°] (K.); [178°-186°] (E.);fine
yellow needles. — Zinc double chloride:
[195°] ; concentric needles (E.).
Methylo-iodide B'Mel. [149°].
(o)- or {Py. 3)JEtliyl-quinoUiie CjHjNEt i.e.
.CH:CH
0M,< I • (258° cor.). Formed by distil-
\ N.CBt
ling (Py. 3)-ethyl quinoline (Py. l)-carboxylio
acid with 5 times its weight of soda-lime
(Dobner, A. 242, 272 ; Eeher, B. 19, 2995 ; 20,
2734). Formed also by heating quinoline ethyl-
iodide (v. siepra). , ,
Properties.— Colourless hygroscopic oil. SI.
sol. water, v. sol. alcohol and ether. Gives
quinoline (Py. 3)-carboxylio (quinaldinic) acid
on oxidation. May be reduced by tin and HCl
to a tetrahydride (c. 261°), which forms a
crystalline hydrochloride.
Salts.-r-The chloride, nitrate, and
snlph ate are v. sol. water. The chloride and
nitrate are efflorescent. The ohromate crys-
tallises in red needles.— (B-HC^^PtCli 2aq :
[189°] • orange-red needles or tables, si. sol.
water.— B'HHgC^: [118°]; slender needles.—
B'HAua4: [142°]; canary-yellow needles.—
B'oHjSnCU 2aq : crystalline: — Piorate
B'jC^^sOj: [148°]; lemon-yeUow needles
(from alcohol) si. sol. water.
Vol. II.
Methylo-iodide B'Mel: [180°] ; greemsh-
yellow needles (from alcohol). '
EthyI('?)-isoqTiinoIine C„H„N probably
.C(0^s):OH
CeHZ I . [65°]. (275° at 264 mm.).
Crystalline solid. Formed by complete de-
chlorination of di-ohloro-ethyl(?)-isoqainbline by
heating with HI and P at 200°.
Salts.-^B',HjjCljPtCl, 2aq: orange-yellow
flat needles. — B'sH^Cr^O,: orange-red glistening
needles (Gabriel, B. 20, 1207).
Di-ethyl-quinoline OjHjBtjN. (284° cor.).
Obtained as a by-product in the ethylation of
quinoline by heating its ethylo-iodide at 285°
(Eeher, B. 19, 2995). Liquid, smelling like
quinoline. On oxidation with chromic mixture
it gives an acid [190°].— B'jHjPtOl, : [217°];
orange-red needles, blackens before melting. — '
B'HHgClj: [116°]; needles.
B^erences. — ^Bbomo-, Ghlobo, and Oxy-
EIHYL-gUIHOLINE.
(Py. 2)-ETHYI-QTIIIirOLINE-(P2/, 3)-CAEB-
.OH:OBt
OXYLIC ACID CeH.< | . (Py. 2).
N N:0(C02H)
Ethyl-guindtdwAa acid. [148°]. Glistening
needles (containing ^aq). Sol. alcohol and hot
water, si. sol. ether. Formed by oxidation of
(Py. 2:3)-ethyl-propyl-quinoline with CrO, and
H2SO4. On distillation it evolves CO, and gives
(Py. 2)-ethyl-quinoline.
Salts.— (A'H,HCl)jPtCl4: fine needles.—
Picrate: [153°]; fine yellow needles, si. sol.
water and cold alcohol. — A'Ag : amorphous
white pp., or very fine microscopic needles. —
A'2Cu : bluish-green microcrystalline pp. (Eahn,
B. 18, 3368).
(Py. 3:l)-Ethyl-quinoline carbozylic acid
CaHsNBtCOjH. (Py. S)-Ei}iyl-cinchonio acid.
[173°].
PreparaUon. — Pyruvic acid (70 g.J and pro-
pionic aldehyde (50 g.) are dissolved m alcohol,
and aniliu (80 g.) is gradually added, and the
mixture heated on the water-bath with an in-
verted condenser (Dobner, A. 242, 270).
Properties. — Needles or plates. V. sol. alco-
hol, ether and hot water. Yields on heating
with soda-lime (Py. SJ-ethyl-quinoUne.
Salts. — Chloride, nitrate, andsnlphate
are v. sol. water. — (B'HCl);jPtCl4aq: orange-yel-
low needles, v. sol. water, si. sol. alcohol, insoL
ether.— AgA' : pp. v. si. sol. water.
ETHYI-airilirOIINE lETBAHTDBIDE
/CH2:GH2
y^e^i\. I V. QuiNoiiiNB. An isomeride ia
\NEt:CH2
obtained by reducing (Py. 3)-ethyl-quinoline
(e- «'•)■
(Py. l).ETHTI-aTTINOLIKE STTLFHOmC
ACID Cs,H5BtN.S03H. [above 315°]. Obtained
by .heating (7)- or (Py. l)^ethyl-qninoline with
fuming H2SO4 (10 pts.) a" 260° (Eeher, B. 19,
2905). Slender needles, insol. alcohol, T. sol.
hot water.
TEI-ETHYL-EOSANILINE i;.Tbi-bthyi.-tbi.
AMIDO-DI-PHENYL-TOLYIi-CABBUlOIi.
HONO-ETHYL SELENATE BtHSeO, i.e,
S02(0H)(0Et). An unstable acid obtained by
treating selenio acid with alcohol (Fabian, A.
LIi
614
ETHYL SELENATE.
Suppl, I, 244).— SrA'j: tables.— OuA'j 4aq :
plates.
ETHYL SELEITHYSBATE EtSeH. (above
100°). A liquid formed accotding to Wohler and
Siemens {A. 61, 360) when KSeH is distilled with
alcohol. It has a very disgusting odour, and its
alcoholic solution gives a yellow pp. with HgClj.
ETHYI SELENIDE O^HjoSe i.e. Et^Se. (108°).
Prepared by digesting equivalent quantities of
PjSej and KEtSOj with a small quantity of water
at 50°, the product being fractionally dfstilled
(Von PieverUng, A. 185, 331). Colourless mobile
liquid, smelling like a hydrocarbon. Insol.
water, miscible with alcohol and ether. Its solu-
tion in dilute HNO3 gives withHCl oily EtjSeCl^
whence aqueous ammonia forms crystalline
(Bt2Se)20CL; (Joy, A. 86, 35).
Ethylo-iodide SeEtjI. Tn-etti^l-seTxinium
iodide. Slowly formed by combination of SeEtz
with EtI in the cold (P.). White crystals, stable
in the air, v. e. sol. water and alcohol, si. sol.
ether. Sublimes between 80° and 120°, being
split up into SeEtj and EtI, which slowly recom-
bine in the cold.
Ethylo-hydroxide SeEtjOH. Formed by
treating the ethylo-iodide with moist Ag^O.
Powerful base, forming a syrupy solution which
absorbs COj with avidity. Its salts smeU like
leeks and, with exception of the tartrate, are very
deliquescent.
Acid tSirtrate SeEtaO^HsQs 2aq : pale rose-
red needles, v. e. sol. water, forming an acid so-
lution.—Platinoohloridc' (SeEtsQ^jPtCl, :
red rhombohedra. Monoclinic according to
Sohimper(^.£. 1,219).— Zinc double chlor-
ide (SeEtaC^jZnCljj : from SeClj and ZnBtj
(Bathke, A. 152, 210).
Di-ethyl di-selenide Et^Scj. (186°). Prom
KEtSOi and KjSej (Rathke). Beddish-yellow
liquid with highly disgusting smell. Its solution
in dilute HNOj gives with HCl crystals of
BtSeOaHjCl (7) ; these are v. sol. water, and are
reduced by SO2 to Et^Sej.
ETHTL DI-SELEXO-FHOSFHATE
CjHjsPOjSe i.e. EtsPO^Sd^. An oil obtained by
treating P^Se^ with alcohol (Garins, A. 124, 57).
Slowly decomposed by water.
ETHYI SILICATE Et^SiO,. (350°). S.G.
24 1-079. jPormed, according to Ebelmen {A. 57,
331), together with EtjSijOs, by treating SiOl,
with wet alcohol. Slowly saponified by water.
Friedel and Crafts (A. Ch. [4] 9, 5) could not ob-
tain this ether, but found instead EtsSi^O, (125°-
130° in vacuo). V.D. 12-03 (oalc. 11-86). S.G. 2
1-0196 ; ifi 1-0119. The ether Et.SijO, is also
formed by treating SiOCl, with alcohol (Friedel
a. Ladenburg, A. 147, 362) ; it is converted by
gaseous NHj into Et5Si20j(NH2) (280° in vacuo)
andEt4Si20j(NH2)j(Troosta.Hautefenille,4.0;i.
[5] 7, 472).
Ethyl ortho-silicate OsH^oSiOj i.e. EtjSiO,.
Silicic ether. (166^. S.G. 22 .933 (E.); -968
(Friedel a. Crafts, A. Ch. [4] 9, 5). V.D. 7-32
(calo. 7-2I). Formed by pouring absolute al-
cohol upon SiCl, and distilling the product
(Ebelmen, A. 67, 331). Also from alcohol and
SiF, (Khop a. Wolf, C. C. 1861, 899). Colourless
liquid, with ethereal odour; Bums with dazzling
flame. Insol. water, but slowly decomposed by
it with separation of silica. Ammonia and aque-
ous alkalis dissolve it. Ao^O at 180° gives
(EtO),SiOAo (c. 190°).
Chloride ClSi(OEt),. (157°). 2 1-0483.
V.D. 7-05 (calc. 6-81). Formed by heating SiOl,
(1 mol.) with Et,SiO< (3 mols.) at 150° ; by heat-
ing EtiSiOi (1 mol.) with AcCl (1 mol.) at 175° ;
or by distiUing Et.SiOi with POI5. Iiimpid
liquid ; does not fume in the air, but is quickly
decomposed by moist air or water yielding HCl
and silic^.
DichlorideOlSHOEt),. (137°). S.G.21-144.
V.D. 6-76 (calo. 6-55). From Et^SiO^ (1 mol.)
and SiCl, (1 mol.). Formed also by heating
ClSi(OEt)s (1 mol.),with SiCl, (2 mols.) and dis-
tilling. Liquid resembling the preceding.
Trichloride ClsSi(OEt). (104°). S.G. 9
1-291. V.D. 6-38 (oalc. 6-22). Formed by heat-
ing EtjSiO, or either of the preceding chlorides
with excess of SiCl, for a long time. Liquid.
Octo-ethyl tetra-silicate EtjSiiOiz. (270°-
290°). S.G.2 1-071. V.D. 19-54. From Si ACl,
and absolute alcohol (T. a. H.). Liquid. NH,
converts it into EtgSi40,o(NB!j,)2.
ETHYL-STIBINE v. Orgarno compounds of
Aniimont.
ETHYL-STILBEKE v. 'ETBYh-si-ssEnrzh-
EIHniENE.
Di- ethyl -stilbene v. Di-eih^i-di-pebnil-
ETHTIjENE.
ETHYX-SnCCimC ACID
C02H.GBL:.CEEt.C02H. Butane di-carboxylic
acid. [98°]. (243°).
FormaUon. — 1. By boiling a-acetyl-a-ethyl-
snocinic ether with cone, alcoholic KOH (Hug-
genberg, A. 192, 148). — 2. By oxidation of i8-ace-
tyl-propionio acid (Thome).— ^3. By distilling
butane tri-caiboxyhc acid (derived from malonio
and a-bromo-butyric ethers) (Polko, A. 242, 121),
Pr^aration.— o-Aoetyl-fl-ethyl-snocinie ether
is heated with very strong potash (2:1) at 100°.
Excess of the ether removed by shaking with
ether, the acids are then liberated by H^SO^ and
extracted with ether (L. T. Thome, O. J. 39,
338).
Prop^Hes. — ^Prismg (from chloroform and
petroleum ether) ; v. e. sol. water, alcohol, ether,
and chloroform, insol. petroleum-ether.
Salts.— KHA"; v. e. sol. water, insol. alco-
hol.—K^A" iaq : very hygroscopic- CaA"2aq:
prisms, v. si. sol. water. — CaH2A"2 3aq: si. sol.
water, insol. alcohol. — BaA" IJiaq : v. sol. water,
insol. alcohol. — SrA". — CuA" : blue insoluble pp.
— ZnA"2aq: v. e. sol. water, insol. alcohol. —
AgjA" : powder ; decomposes at 110°.
Methyl ether Me^A". (204°). S.G. || 1-051.
Does not solidify at — 19°.
E thy I ether T^tji.". (225°). S.G. |J 1-030.
Anhydride CsH^O,- S.G. f* 1-165:
Amide: [214°]; insol. cold water.
Si-ethyl-Buccinio acid
COjH.CEtH.CEtH.COjH. [190°]. S. -61 at 23°;
6-7 at 95°. Formed, together with an isomeride
[140°], from xeronio acid C02H.CEt:CEt.C02H
and HI (Otto, A. 239, 280). Monoclinic plates,
b1. sol. water, v. sol. alcohol and ether. Converted
by heating with HClAq into the isomeride [129°].
— Na^A". -CaA" 2aq.— CuA" aq,— ZnA" 2aq.
Ethyl etherMfk". (234°). S.G. is -991.
Formed, together with the isomeric ether, by
heating a-bromo- (or iodo- ) butyric ether with
finely-divided sUver at 120° to 130° (Hell, B. 6,
ETHYL SULPHATES.
616
28 ; 13, 475, 479 ; 22, 67 ; Hjelt, B. 20, 3078).
It is well to add some Mel;
Anhydride (o. 240°).
Di-ethyl-suooinio acid
COjH.OEtH.CEtH.COjH. [129^. S. 2-4 at 28°.
This acid is obtained, together with the preceding,
by heating hezane tri-oarbozylio aoid obtained
Erom a-bromo-butyiio and dthyl-malonio ethers
by treatment with NaOEt (Hjelt ; Hjelt a. Bis-
chofE, B. 21, 2098 ; Zdinsky a. Bitsohichni, B.
21, 8898). It is also formed by dissolving the
anhydride of the preceding in water. Trimetrio
plates, V. sol. alcohol and ether. By heating
quickly it is converted into the anhydride (246°).
By heating for 8 hours at 220° it is converted
into the isomeric acid [190°]. On heating with
resorcin and HjSO, it gives a fluorescein. —
NajA.".— CaA".aq.— CuA"aq.— ZnA"6aq.
ETHYL STTGCINIIIIDE v. Ethylimide of Suc-
omic Actn.
ETHYI-SUCCINTJRIC ACID 0,H,jNj,04 i.e.
NHBtCO.NH.CO.CjH«.COjH. [167°]. Formed
by the action in the cold of dilute H2SO4 on suc-
cinyl-ethyl-urea (the compound of succinimide
with cyanic ether) (Menschutkin, B. 7, 128).
Long needles (from alco&ol). Decomposed at
190° into succinimide, water, and cyanic ether.
SI. soL water and ooldi^cohol. — AgA' : plates or
needles (from hot water).
Amide NHEt.CO.NH.CO.CHj.CHj.CONHj.
[196°]. From succinyl-ethyl-urea and alcoholic
NH3 at 100°- Needles (from alcohol). Decom-
posed by heating with aqueous ammonia.
SI-EIHYL-SnCCINYL-STTCCnnC ACID v.
Di-ethyl dervoaii/ve of the dihydride of Di-oxt-
lEBEPHIHAIilO ACID.
ETHYl-STJIPHAMIC ACID HO.SOj.NHEt.
Prepared by the action of SOj on ethyl-amine
(Beilstein a. Wiegand, B. 16, 1265). Needles.
Sol. water, alcohol, and ether. Not decomposed
by boiling with water.
Salts. — ^A'2Ca2aq: large prisms, sol. water,
alcohol, and ether. — A'jBa l|aq : silvery scales.
S. (90 p.c. alcohol at 18°) = 1-33, v. sol. water.—
A'jPb : needles, sol. water and alcohol.
Di - ethyl - snlphamic acid HO.SO^-NEtj.
Formed by the action of SO3 on di-ethyl-amine.
A'2Ba2aq: sol. water and alcohol, insol. ether
(BeHstein a. Wiegand, B. 16, 1266).
CfcZoride NEtj-SOjCl. (208°). Formed by
the action of snlphuryl chloride on di-ethyl-
amine hydrochloride (Behrend, B. 15, 1612 ; A.
222, 134). Yellow oil, v. sol. alcohol, ether,
benzene, and CHOI,. Heavier than water.
TETEA-ETHYL-SUIPHAMIDE SOjfNEtj),.
(250°). Formed by the action of di-ethyl-amine
on di-ethyl-Bolphamic chloride at 60° (Behrend,
B. 15, 1612 ; A. 222, 135). Heavy yellow oil,
T, sol. alcohol, ether, benzene, and CHCI,.
ETHYL SULPHATES.
Uono-ethyl sulphate GjHgSOf i.e.
SO,(OH)(OEt). S.G. is 1-316.
* FormaMon. — 1. From alcohol and H^SO^
(Dabit, Ann. Chem. 34, 300; 43, 101 ; Sertumer,
GiU). Arm. 60, 53 ; 64, 6, 7 ; A. Vogel, Oilb. Arm.
63, 81 ; Gay-Lussao, A. Oh. [2] 13, 76 ; Dumas
a. Boullay, A. Ch. [2] 36, 300 ; Serullas, A. Oh,
[2] 39, 153 ; Liebig a. W5hler, A. 1, 37 ; Liebig,
A. 13, 27; Magnus, A. 6, 152; Marchand, P.
28, 454 ; 32, 345 ; 41, 595 ; Miiller, A. Oh. [3]
19, 83).—^. From ethylene and HjSO^ (Hennell,
Tr. 1826, 240 J 1828, 365; Berthelot, A. Ch. [3]
43, 385 ; 0. B. 36, 1098).— 3. By heating ethe*
with HjS04 (Hennell a. Magnus, P. 27, 386).—
4. From SjOlj and alcohol (Heusser, A. 151,
249).
Prepwratian. — A mixture of equal parts of
strong sulphuric acid and strong alcohol is
heated to about 100°, and, after standing in a
warm place for 24 hours, diluted with water,
and saturated with carbonate of barium or car-
bonate of lead ; the solution is then filtered from
the precipitated sulphate of barium or lead, and
' the filtrate carefully evaporated to the crystal-
lising point. The crystals of baric or plumbic
ethylsulphate are then redissolved in water, the
solution is decomposed with an e&actly equiva-
lent quantity of sulphuric acid — or better, in the
case of the fead-salt, with HjS — and! the filtrate
is concentrated in a vacuum over oil of vitriol
or chloride of calcium. Claesson (J. pr. [2] 19,
246) recommends taking 3 pts. of alcohol to
2 pts. of HjSO,; the yield is then 77 p.c.. If the
mixture be kept at 100° for more than an hour
a notable amount of ether is formed, and the
yield of acid is diminished (Yilliers, O. B. 91,
124).
Properties. — Colourless syrup, miscible with
waiter and alcohol, insol. ether. When heated
it gives ofi ether, leaving H^SO^. At a higher
temperature it gives off ethylene and SOj.
Beactions. — 1. The aqueous solution decom-
poses slowly in the cold, quickly on boiling, the
products being alcohol and H^SO^. — 2. Alcohol
at 130°-140° yields ether and H^SO,.- 3. MnO^
or KjuxO, give aldehyde (Jacquemin a. Li^s
Bodard,J'. 1857, 345). — 4. On electrolysis it yields
formic and acetic acids besides H and O (Benard,
A. Oh. [5] 17, 801).— 5. The K and Ba salts are
decomposed by dry HCl at about 80° completely
into EtCl and the corresponding sulphate (Kohler,
B. 11, 1929). — 6. BeactB with salts of organic
acids forming the corresponding ethyl ethers.
Salt s. — All the salts are v.. sol. water. Their
aqueous solution is decomposed by boiling, but
this is prevented by the addition of a few drops
of aqueous KOH. When heated with cone.
H3SO4 they give ofi ether, boiling dilute HjSO,
liberates alcohol. When heated with EOH they
give off alcohol. When distilled with other salts
tiiey form ethyl ethers of those salts. — NH,A' :
[62°] ; very deliquescent crystals, v. sol. water,
alcohol, and ether. — EA'. S. 125 at 17°. Large
monoclinic tables or laminee; a:d:c = '573:-616:l;
/3 = 80°27' (Schabus, J. 1854, 560). Deliquescent,
insol. alcohol and ether.— NaA'aq. [86°]. S. 164
at 17°. Very deliquescent hexagonal plates ;
e£9orescent in warm air. — LIA' aq : deliquescent
crystals. — BaA', 2aq : S. 109 at 17° ; S.G. SI'
2-080; monoclinic prisms; a:&:c = -823: -979:1;
j8 = 84° 39' (Schabus). The aqueous solution
becomes turbid on boiling„BaS04 being ppd. —
CaA'22aq: S. 100 at 8°; 125 at 17°; 157 at 30°. -
Monoclinic scales ; permanent in the air. SI.
sol. alcohol, insol. ether.— SrA'^ : v. sol. water. —
CdA'j 2aq : long prisms, v. sol. water and alco-
hol, insol. ether. — CoA'j2aq: dark-red crystals,
permanent in the air, v. sol. water and alcohol,
insol. ether. — CuA'j 4aq : rectangular prisms, v.
sol. water and alcohol, insol. ether. — PbA'^ 2aq :
tables, V. sol. water and alcohol, having an acid
ll2 '
516
ETHYI. SULPHATES.
reaction. — PbA'^PbO. S. 185 at 17°. Amorphous,
Bol. water and alcohol. — HLgA/^iaq: crystals, t.
Bol. water, insoL alcohol and ether. — MnA'^^aq :
roseate . tables, y. sol. water and alcohol, insol.
ether. — NiA'2 2aq: very soluble green crystals. —
ZnA'22aq : large tables, v. sol. water and alcohol,
insol. ether.— SmA', 9aq. S.G. 1-880. Large
crystals, sol. water (OUve, Bl. [2] 43, 171). —
DiA',9aq. S.G. 1-863 (G,).— AgA'aq : scales, sol.
water and alcohol.
Chloride EtSOsCl. Sulphiiria efhoxy'
chloride. (158° cor.).
FormaHon. — 1. From alcohol and ClSOjH,
along with ethyl-sulphuric acid. — 2. By dropping
SO^Ol, into alcohol.— 3. From EtCl and .SO, (R.
Williamson, G. J. 2, 629 ; 5, 576 ; Kuhlmann, A.
38, 108).— 4. From KBtSO, and POl, 5. From
ClOOjEt and fuming 'EL.aO, (Wihn, B. 6, 505).
Preparation. — Ethylene is passed into
ClSOaH, and the product distilled m vacuo.
The yield is 50 p.c. (M. Miiller, B. 6, 227).
Properties. — Slightly decomposed by distil-
ling. Insol. water. When heated with water
in sealed tubes it gives Et^O, EtCI, HCl, and
HjSO, (Purgoia, Z. [2] 4, 669).
BeactUms. — 1. With alcohol it reacts chiefly
thus : EtaSOjCl + EtOH = BtO.SOjOH + EtCl,
but also according to the two equations
(a) BtCSOjCl + HOEt = (BtO)jSO, + HCl,
(6) {BtO)2SOj-l-HOEt = (BtO){HO)SOs + EtjO,
the last equation taking place when there is an
excess of alcohol. — 2. With methyl alcohol the
reaction is
EtO.SOjCl + HOMe = MeCl + EtO.SOj.OH.
a. With wmyl alcohol BtO.SOaOl+CsHnGH
= CsHuSOaGH+EtOl. It thus appears that the
chloride of the smaller alcohol radicle is formed
(Claesson, J.pr. [2] 19, 248).
Di-ethyl sulphate C^HuSO, i.e, S02(0Et)2.
Mol. w. 154, [0. -24°]. (118°) at 40 mm.
S.G. 12 1.1887. Occurs in 'heavy oil of wine,'
an oily mixture sometimes obtained in the pre-
paration of ether (Marchand, J. pr. 16, 1 ; Serul-
las, A. Oh. [2] 39, 152).
Wormation. — 1. By passing vapour of SO,
into a flask containing ether surrounded by a
freezing mixture. The product is washed with
lime-water add rectified (Wetherill, A. 66, 117). —
2. From dry alcohol and SO,.- 3. From AgjSO^
and EtI {Stempnewsky, J.B. 1882, 95).— 4. From
ClSO,Et and alcohol (Claesson, J. pr. [2] 19,
257).
Prepa/raUon. — ^Absolute alcohol (200 g.) mixed
with cone. HjSO, (450 g.) is distUled very slowly
until the mixture begins to froth. The distillate
separates into two layers, the lower being pure
BtjSOi (28 g.) (ViUiers, O. B. 90, 1291).
Properties. — Oil, smelling of peppermint.
Solidifies at about —25°. It forms double com-
pounds with Bulpho-aoetates, sulpho-benzoates,
and isethionateB,but not with acetates,benzoates,
or methane sulphonates (Geuther, A. 218, 288).
Beactions. — 1. Warm ba/ryta-water converts
it into Ba(S04Et)2.— 2. When heated with water
it gives alcohol, HjSO„ and EtHSOj.— 3. When
heated with alcohol it forms ether and EtHS04. —
4. SO, gives ethionic ether and methionio ether
(B. Hubner, A. 223, 208).— 6, KHS gives mer-
captan and' K2SO4.— 6. NH, gives NBtjSO.Et
and NEtHjSO^Bt.
Beference. — Di-ebomo-di-eihil SDi<f bate.
ETHYL SHLPHIDE O^H ,8 t.e. Et^S. Mol
w. 90. (93° cor.). S.G. f -8868. V.D. 3-00
(oalc. 3-12). H.F.p. 28,550 {Th.). H.F.V. 26,230
{Th.). Boo 27-64 (Nasini, G. 13, 301).
Formation. — 1. By the action of KjS on
EBtSO,, on EtCl, or on other ethyl ethers
(Dobereiner, Schw. J. 61, 377 ; Begnault, A. Oh.
[2] 71, 387 ; Loir, 0. B. 26, 195 ; Biche, A. Oh.
I'S] 43, 297).— 2. By passing the vapour of
SOjClj in a current of 00^ over zinc ethide, and
distiUmg the product witii water (F. Gauhe, A.
148, 266). — 3. By distilling mercury mercaptide :
Hg(SBt)j=HgS-fBt2S.
Preparation.- An alcoholic solution of potash
is divided into two equal parts: one part is
saturated with H^S, and then mixed with the
other ; the liquid is introduced into a tubulated
retort ; vapour of hydrochloric ether is passed
through it to saturation; andheat'is then gradu-
ally applied, the stream of hydrochloric ether
vapour being still kept up. From the distillate,
which contains alcohol and ether as well as
sulphide of ethyl, the sulphide of ethyl is pre-
cipitated by water ; it is then purified by washing
with water, dehydrated by chloride of caloiam,
and rectified (Begnault).
Properties. — Oil, with alliaceous odour. Sol.
alcohol. Bums readily with blue fiame. Takes
fire when poured into chlorine. EgO has no
action on it, but lead acetate gives a yellow pp.
Beactixms. — 1. Nitric acid (S.G. 1*2) forms
di-ethyl sulphoxide Bt^SO. Fuming HNO, forms
di-ethyl sulphone (Oefele, A. 127, 370).— 2. Boil-
ing aqueous EOH has no action, but on distilling
over solid EOH there is formed EH3 and alco-
hol.^3. Heated with sulphur at 180° it is partly
converted into EtjS,, Bt^S,, BtgSf, and EtjS,
(Bottger, A. 223, 351).— 4. S^Cl, acts energeti-
cally, forming HCl, carbon, and sulphur (B.).—
5. SOCl, forms similarly HCl, carbon, S, and
SOj.— 6. CI.SO3H forms HCl, carbon, S, HjSO,,
and HjO.— 7. SOaOlj forms HCl, carbon, S, and
SO2. — 8. On passing through a red-hot tube it
yields thiophene. — 9. CAZorine forms chlorinated
products by substitution (Biche, A. 92, 358). —
10. Bromime forms crystalline Et^SBr,, whence
KI gives oily EtjSIa, which is reconverted by
ZnEt, into Bt2S (Bathke, A. 152, 214).
Beferenee. — Di-ohiiOiio-di-eihsl sulphide.
Oo»»6wtas*iojM.— EtjSHgClj. [90°]. Formed
as a crystaUine pp. by shaking aqueous HgCl,
with EtjS or its alcoholic solution. Monoclinio
prisms (from ether or MeOH) (Loir, ^.87, 369).—
(Et2S)JPt01,. [108°]. Tellowneedles(Loir,4.0*.
[8] 89, 441).— pEtjS)J'tCl2, [81°]. Formed by
shaking Et^S (1 mol.) with potassium platinous
chloride (2 mols.). Short, bright-yellow prisms.
Almost insol. water, m. sol. alcohol, si. sol. ether,
V. e. sol. CHGlg. Changed by shaking with water
and Et^S into an isomeride [100°] crystallising
in thin tables (Blomstrand, J.pr. [2] 27, 190).—
Et2SPbS047aq : large crystals ; v. e. sol. water. —
BtjSHglj. [110°] (Loir, A. 107, 234).— Et^STiCI,.
— (BtjS),TiCl4 (Demarifay, Bl. [2] 20,132).
Methylo- compounds Bt^SMel. ileth/yl'-
di-ethyl-suVphme iodide. Formed as a syrup
when BtjS and Mel are heated together wil^
a little water (Eriiger, J. pr. [2] 14, 195).
Moist AgCl gives syrupy Et,SMeCL The
hydroxide is a powerful base. The nitrate
and sulphate crystallise in long deliquescent
ETHYL SULPHITES.
517
— (EtjSMeCl) J'tCl, : [214°]; pale-red
monoolimo oiystals ; si. sol. cold water, insol.
alcohol and eUier. Crystallises from water in
cubes, ootahedia, and tetrahedra. — EtaSMeAuOL;
[192°]; long pale-yellow needles ; v. sol. aloohol,
ether, and hot water. — Et^SMeO^HgCyj :
[198°]; transparent prisms (from hot water).—
EtjSMeCyHgl,: [115°]; formed by mixing cold
solutions of EtjMeSI, HI, and HgOyj. HoS in
presence of water gives black HgS ; on continu-
ing the action of the gas it changes to red HgS
(difference from SEtjCl(HgCla) J.
Isomerides of theMethylo- compounds
EtMeSBtl. From EtSMe and EtI (Kruger, J.pr.
[2] 14, 207). Very deliquescent needles. The
chloride is a syrup, the nitrate and sul-
phate are deliquescent. — (EtMeSEt01)2PtCl. :
[186°] (K.); [205°] (N. a. S.); prisms of cubic
system (from water); insol. ether and alcohol
(Kasini a. Scala, O. 18, 62). By repeated re-
crystallisation it is changed into its isomeride. —
EtMeSEtAuOl, : [178°]; pale-yellow crystalline
powder; T. sol. hot water, alcohol, and ether. —
EtMeSEtCa(HgClj)2: [112°] ; white orystaUine pp.
Crystallises from water in trimetric plates.—
EtMeSEtCyHglj! [98°]; amber-yeUowpp.; insol.
water, alcohol, and ether. When strongly heated
it yields Hgl,, a carbamine and a sulphide.
Botii EtaSMel and its isomeride EtMeSEtl give
with AgOBz syrupy benzoates, which, when
heated to 11S°, yield methyl benzoate (Crum
Brown a. Blaikie, Pr. E. 10, 254).
EthylO'iodide EtjSI. TH-ethyl-suVphme
ioMde. From Et^S and EtI (Oefele, A. 132, 82 ;
C. J. 17, 106; Iiukaschewicz, Z. [2] 4, 648).
Formed also by the action of HI on EtjS or
EtSH; and by treating mercaptah with EtI
(Cahours, A. 135, 352; 136, 151). Trimetric
plates; t. e. soL water. Decomposed on dis-
tillation into EtaS and EtI. Moist Ag^O con-
verts it into a deliquescent hydroxide Et,SOH.
This hydroxide is strongly alkaline ; it absorbs
CO, from the air, ppts. metallic salts, expels
KH, from its salts, and turns red litmus blue.
It forms the following salts: — EtaSCl: deli-
quescent needles (from water) volatile with
steam. — (EtaSC^aPtCli : monocUnic prisms,
a:6:o = -676:l:l-107 ; j8 = 55° 6' (Dehn, A. Suppl.
'4, 92). S. 3-3 at 20-7°.— Et,SCl(HgCy,. S. 1-5
at 20°.— SEtjAuCl, : long golden needles ; si. sol.
cold water.— Et,SN03AgN03.—(Et3S)jS04 : in-
distinctcrystallineaggregates.— SEtjBr: needles ;
V. e. sol. water, si. sol. alcohol, insol. ether (cf.
Otto a. B8ssing, B. 19, 1839). The ethylo-iodide
also forms the following combinations with
metallic salt : SEtjIHglj.— SBtalTUa (Jorgensen,
/. pr. [2] 6, 82).— (SEt3l)s(BiIs), (Kraut, A. 210,
321).-SEt,IBil3.— (SEt,I)„(BiIa)j9aq.
Ethylo- cyanide SEtjCy. Formed by
digesting SEtjI with KCy at 100° (Gauhe, Z.
[2] 4, 622). Deliquescent needles. Besolved by
heating with acids pr alkalis into EtjS, pro-
pionic acid, and NH,. A crystalline compound
SEtaOyAgCy is obtained by digesting Et,SI with
alcohol and AgCy at 90°. It is decomposed by
heat into SEtjOy and AgCy (Patein, 0. B. 106,
861).
Di-ethyl di-sulphide EtjSj. Mol. w. 122.
(153° cor.). S.G. "f -9927. V.D. 4-27 (calc. 4-28).
Fonnatum. — 1. By distilling KEtSO, with a
toncentrated aqueous solution of EjS, (Zeise,
P. 31, 371 ; Pyr. Morin, P. 48, 483 ; A. 32, 267 ;
Lowig, P. 27, 550 ; 49, 326 ; Cahours, A. Ch.
[3] 18, 268 ; A. 61, 98 ; Muspratt, C. J. 3, 19).—
2. By distilling oxalic ether with EjSj. — 3. By
treating an aqueous solution of sodium mercap-
tide with iodine (KekulS a. Iiinnemann, A. 123,
279). — 4. By treating meroaptan with cone.
H2SO4, sulphurous acid being given off (Erlen-
meyer a. Lisenko, Z. 1861, 660).^— 5, By heating
mercaptan with sulphur for six hours at 150°
(M. MiJller, J. pr. [2] 4, 39).— 6. By heating
NaSEt (8 g.) with alcohol (10 g.) and sulphur
(1-5 g.) at 100° (Bottger, A. 223, 848):
2NaSEt4-S2 = Et2S2 4-Na2Sij.— 7. From mercap-
tan and SOjClj (Courant a. Bichter, B. 18,
3178).
Properlies. — Colourless oil ; sol. alcohol and
ether. It' first floats upon water, but after a
while it sinks, probably from absorption of water,.
Neutral to test papers. It has an alliaceous
odour, and is poisonous. It is very inflamiaable^
and burns with a blue flame. It is attacked l)y
CI and Br. With HgO it slowly forms a yellow
mass. Its alcoholic solutions are ppd. by HgCl,
and by Pb(0Ac)2.
Beactions. — 1. Dilute niirio acid oxidises it
to ethane thiosulphonic ether CjH^.SOjSEt. —
2. Cold HjSO, does not dissolve it ; on warming
it gives off SOj-^S. Heated in a sealed tube with
EtI it gives SEtjI and iodine (Saytzeff, Z. [2] 6,
109).— 4. Carbonised by SjClj, SOClj, CISO3H,
and SO^Clj.
Si-ethyl trisnlphide Et^S,. Obtained, to-
gether with EtjSj, by distiUing KEtSOj with F„S^
(Cahours). Formed also by heating Et^S, with"
sulphur. Heavy yellow oil, volatile with steam.
It cannot be distilled undecomposed. Mercury
removes one-third of its sulphur. Copper turn-
ings at 150° do so also. When suspended in water,
and oxidised by fuming HNO, there is formed
HjSO, and EtS03H. Moist AgjO gives EtSOjH
and AgjS (Miiller).
Si-ethyl tetrasuIpMde Et^S^. Formed by
treating mercaptan with S^Cl, in OS: solution
(Claesson, J. pr. [2] 15, 214). Oil with disgust-
ing smell. Split up by distillation in steam into
Et2S3 and sulphur.
, Si-ethyl pentasulphide Et^Sj. A semi-solid
mass got by heating the preceding with sulphur
at 150°.
TBI-ETHYL-STTXPHINE COMFOUNSS v.
supra.
ETHYL-SULFEINIG ACIS v. Etbaijb sul-
PHINia ACID.
ETHYL SULPHITES.
Uouo-ethyl sulphite. The potassium salt
KO.SO.OEt is formed when di-ethyl sulphite is
treated with cold aqueous KOH (Warlitz,^. 143,
75). Scales (from alcohol) ; very unstable. '
Chloride EtO.SO.Ol. (122°). From
(EtO)jjSO and PClj (Miohaelis a. '^agner, B. 7,
1073). Formed in small quantity by passing
HCl into alcohol saturated with SO^ and heating
the product in a sealed tube at 100°. Slightly
fuming liquid. Eeadily decomposed by water
into HCl, alcohol, and SOj. Not attacked by
POI5 at 120°, but at 180° it yields SOClj, POCl,
and EtCl.
Si-ethyl sulphite C,H,„S03 i.e. (EtO)jSO.
(161°). S.a. 15 1-085. V.D.4-78.
Formation. — 1. By the action of absolute
518
ETHYL tSULPHITES,
alcohol on SjOlj. The reaction perhaps takes
place thus: SjCl^ + HOEt = SOClj + HSEt ; and
80,01;, + 2HOEt = SO(OBt)j + 2HCl, but EtCl,
HCl, and sulphur are also "formed' (Oarius, A.
106, 291; 110, 221; 111, 93; J. pr. [2] 2, 279;
Ebelmen a. Bouquet, A. Oh. [3] 17, 66 ; War-
litz, A. 143, 74).— 2. By adding alcohol drop by
drop-to SOCI2 (Oarius).
Properties. — Oolourlessliquid, smelling some-
what like mint. Hisoible with alcohol and ether,
but insol. water. Slowly decomposed by water.
Aqueous alkalis aild Ha^CO, quickly decompose it
into alkaline sulphite and alcohol. Alcoholic
KHO gives a pp. of EtO.SO.OE. Alcoholic NH,
at 130° gives ethylamine and (NHJ^SO^. Bthyl-
amine gives NHEtj and (NH3Et)2S03. POI5
forms EtO.SOCl, which, however, on keeping,
or on distilling, rapidly splits up into EtOl and
SO2 (Geuther, A. 224, 223). Chlorine attacks it
strongly, and in bright sunshine forms GjOl,,
CC1,.C001, and SO^Ol^. SOOl^ at 120° gives SO,
and EtOl. Diethyl sulphite is split up at 200°
into SO2 and ether (Prinz, A. 223, 374).
Isomeride v. Ethyl ether of Ethane sulphonio
ACID.
ETHYL SULPHOCYAHIDE C3H5NS i.e.
EtS.Cy. (146° cor.). S.G. 2 1-033 ; 2a 1-002
■ (Buff, Z. [2] 4, 730) ; 1 1-071 (Nasini a. Scala, &.
17, 06) ; ifi 1-020. V.D. 3-02. Ba> 41-4
(N. a. S.).
FarmaOon (Cahours, A. Ch. [3] 18, 264 ;
Lowig, P. 67, 101 ; Muspratt, A. 65, 253).— 1.
By saturating a concentrated solution of potas-
' slum Bulphocyanide with EtCl ; the product is
diluted with an equal bulk of water and distilled,
the distillate mixed with ether, diluted with
water, and the ethereal solution dried over CaClj
■and rectified. — 2. From EtI and silver sulpho-
cyanide (Meyer a. Wurster, B. 6, 965). — 3. By
distilling equal p^rts of calcium ethyl sulphate
with potassium sulphocyanide, both in concen-
trated solution.
'Properties. — Mobile colourless oil, having a
taste of anise and a pungent odour resembUng
mercaptan. Insbl. water, miscible with alcohol
and ether. Its alcoholic solution does not ppt.
solutions of metallic salts.
Beaciions. — 1. Nitric add oxidises it to
ethane sulphonic acid. — 2. KCIO3 and HOI at-
tack it with great violence forming ethane sul-
phonic acid. — 3. Chlorine forms chloride of
■cyanogen OyjClj, and a liquid C^HaSOlj (135°)
(James, J.pr. [2] 30, 316).— 4. Aqueous KOH at
100° gives EtjSj, potassium oyanate, and KCy
(Bruning, A. 104, 193).— 5, Boiling alcoholic
KOH gives off NH3 and EtjS^.- 6. Alcoholic
KjS forms Et^S and potassium sulphocyanide. —
7. Dry armnonia appears to form a little ethyl-
thio-urea. Aqueous ammonia (S-G. -880) forms
black uncrystallisable products. Dilute aqueous
NH3 forms NH40y,urea, and Et^Sj (Jeanjean, C.
B. 55, 330 ; Kremer, J. pr. 73, 365).— 8. PEt, at
100° forms EtgPS and Et,PCy (Hofmann, B. 4,
611; A. Swppl. 1, 53).— 9. Dry H^S gives di-
thio-carbamic ether NH^-CSjEt. — 10. Thio-aceUo
acid gives NHAcOS^Bt.- 11. Mel at 105° gives
MejSI and other products (Dehn, A. Suppl. 4,
107).— 12. HBr forms a compound EtSOyH^Br,
(Henry, J. 1868, 652).
Be/erejiee.— Chlobo-exhyl sdlphocxanidb.
DI-ETHYL-SULPHONE C.HjoSO^ i.e. Et^BO™
Ethane suVphirde ether. Mol. w. 122. [70°j.
(248°). S. 16 at 16°. Boo 46-60 (in a 4-24 p.o.
aqueous solution) (Eanonnikoff).
Forr/Mtion. — 1. By oxidising di-ethyl sulphide
with HNO3 in sealed tubes at 100°.— 2. By oxi-
dising di-ethyl sulphide with a solution (1:30) of
EMnOj. — 3. From sodium ethane sulphinate and
EtBr (Otto, B. 13, 1278).— 4. By heating its o-
carboxylio acid to 200° (Otto, B. 21, 994).— 5.
From lead ethide and SO^ (Frankland a. Law-
ranoe, C. J. 85, 245). — 6. By the dry distillation
of itsdioarboxylioacid SO„(OHMe.CO„H)- (Lovfin,
5. 17,2823).
Properties.— Iximeiiic tables (from hot water
or alcohol). Does not reduce KMnO, ; is not
reduced by Zn and HjSOj (differences from di-
ethyl sulphoxide, , Beckmann, J. pr. [2] 17,
452). Not attacked by PGlj, chlorine, or ZnEtj.
IGl, at 150° gives CAClSOjand other products
(Spring a. Winssinger, B. IS, 446).
EIHYli-SUIFHOKO-ACETIG ACID v. Mz-
iHYii-Einyii sniiPHONE cabboxiiiIC Acm.
DI - ETHYL - SULPHOWE o - CAKBOXYIIC
ACID EtSOjCHMe-COjjH. a-Eth/yl-sulphmo.
propionic acid. The ethyl ether is obtained by
boiling the ethyl ether of a-chloropropionic acid
with sodium ethane sulphinate (Otto, B. 21, 994).
The free acid is a yellowish oil, miscible with
alcohol and water. Decomposed on heating into
di-ethyl-Bulphone and COj. The Na salt is a
gum.
Si-ethyl-snlphone jS-carbozylic acid
Et.SO2.CH2.CHj.COjH. P-Ethyl-sulphono^Q.
pionic acid. [112°]. The ethyl ether is obtained
by the action of j3-iodopropionio acid on sodium
ethane sulphinate in an alcoholic solution (Otto,
21, 995). The free acid forms plates, y. e. sol.
alcohol and ether. At 200° it gives SOj and pro-
pionic acid. The Ka salt crystaUises from alco-
hol in plates, and is t: e. sol. water.
Si-ethyl-sulphone di-carbozyllc acid
O2S(02H4.CO2H)j. Sulpho-di-propionic acid.
[156°]. ,
Formation. — 1. By oxidation of thio-di-a-
lactic acid S(02H4.002H)2 with KMnO,.— 2. By
the action of methyl iodide and sodium ethylate
upon di-methyl-Bulphone di-carboxylic ether
(Lovfin, B. 17, 28-22).
Properties. — Four-sided tables. V. sol. water,
alcohol, and ether. On heating it loses CO,,
forming di-ethyl-sulphone.
^THYL-SULPHONE-ETHYLAMIDEu. Ethyh
amide of Ethane suiiPHomo acid. i .
DI - ETHYL - SULPHONE - DI - METHYL .
METHANE v. Di - ethti. peopylidene di-
SrLPHONE.
ETHYL-SULPHONO-PEOPIONIC ACID v.
Di-bthil-sulphohe cabboxylio aoid.
ETHYL BULPHO-USEA v. Ethyl-thio-
TTBEA.
DI-ETHYL STTLPHOXIDE Et2S0. Ethyl
oxysulphide. Formed by heating BtjS with dilute
nitric acid (S.G. 1-2). Thick syrup, v. sol. water.
Cannot be distilled. Beduced by zinc and HjSO^
to Et2S (SaytzeS, A. 144, 153). Chlorine gives
EtCl find chlorinated derivatives of ethane sul-
phonic acid. Chlorine passed into its aqueous
solution forms HOI, EtOl, and EtSOjCl (Spring
a. Winssinger, B. 15, 447).
ETHYL-THIOj-OAEBAMlNE-METHYL CYAMIDE. \
619
Di-ethyl-di-Bulphozlde v. Ethyl ether of
STHANE THIOSULPBONIC ACID.
ETHYL SULPHYDRATE v. Meboastan.
ETHYL TARTSONIC ACID v. OxY-Biffn.-
MALONia kOTD.
ETHYL-TA1TBINE v. Ethyl-amido-bthanb
SUIiFHONIO ACID.
ETHYL-TELLUMDE Et^Te. (98°) (W.;
H.) ; (138°) (M. a. M.). From KjTe and KEtSO,
(W5Uer, A. 35, 111 ; 84, 69 ; Heeren, 0. C. 1861,
916). Keddish-yellow liquid ' with disgusting
odour, T. si. sol. water. Oxidised by air.
Chloride EtjTeClj. Prepared by treating
EtjTe with ENO„ dissolving the resulting crys-
talline nitrate in water, and ppg. by HOI. OH.
BeaaUons. — 1. Aqueous NH, gives (Et2Te)20l20,
crystallising in six-sided prisms, whence Ag2@04
gives crystalline (Et2Te)2H2S04.— 2. AgjO forms
an unstable alkaline oxide, whieh is reduced by
SOj to EtjTe.
Ethylo-ohloridel&tsHeGl. [174°]. From
iZnEtjand TeCl,in ether (Marquardt a.Michaelis,
B. 21, 2042). Deliquescent. Excess of ZnEtj
at 105° forms TeEt, and butane.
Ethylo-iodidem^Tel. [92°]. FromEt^Te
and EtI at 50° (Becker, A, 180, 263 ; Cahours,
A. Gh. [5] 10, 50). Monoclinio orystsils. Gives
with AgjO an unstable alkaline base.
DI-ETHYL-THETINE „OeH„SOs i.e.
EtjS(OH).CH2.002H. Obtained by adding Ag.,0
to an aqueous solution of its hydrobromide (IJetts,
Tr, E. 28, 684). Thick syrup.
Salts. — E1^SBr.CELj.C02B:. Formed by
shaking Et2S with bromo-acetic acid, and allow-
ing to stand for a few days. Colourless prisms,
sol. water and alcohol, insol. ether. It forms a
lead salt EtjSBr.CHj.COjPbBrPbBrj which crys-
tallises either in narrow plates or in needles, si.
sol. cold, V. sol. hot, water. Strong nitric acid
oxidises di-ethyl-thetine to ethane sulphonio
acid. — "EtjSOl.CHj.COjH : syrupy liquid.—
^t2SC1.0Hj.002H)2PtOl4 : large dark -orange
crystals.— '•(SBt2.0Hj.C0jH)2SO, : syrup.
ETHYL - THifiKYL HEXYL KETONE
CH— CH
C„H„SO i.e. II II . (330° cor,).
CEt.S.C.CO.C3H,3
From ethyl-thiophene, heptoyl chloride, and
AICI3 (Schleicher, B. 19, 660). Yellow oil of
aromatic odour. Yields on oxidation hexoic
acid and thiophene oa-dicarboxylio acid.^ By
heating with HjSOj it gives heptoio and ethyl-
thiophene sulphonic and disulphonic acids.
Oxim. — C4SH2Et.C(N0H).C.H,3. [39°].
Crystalline.
(m-ETHYL-THlfiNYL METHYL KETONE
O4SHjEt.CO.CH3. Aceto-ethyl-tUSnone. (249°
cor.). S.G-. S2 -096. Formed by the action of
acetyl chloride upon (o)-ethyl-thiophene in pre-
sence of nAIjCI, (Schleicher, B. 18, 3020 ; 19, 660).
Liquid. By alkaline KMnOi it is oxidised to
thiophene di-carboxyUc acid.
Oxim 04SH2Et.C(N0H).0H3 : [110°]; white
crystals.
Phenyl-hydrazide. [68°]. Needles.
Nitro.derivativeGtBSMl^O^ifiO.CB.^):
[71°]; white needles.
Si-ethyl-tUenyl methyl ketone
C4SHEtj.00.C:^. AcetodietTi/yltMSnone. (250°).
A mixture of di-ethyl.thiophene (1 g.), AcOl
(•6g.), petroleum-ether (5 g,) is slowly dropped
into petroleum-ether (30 g.), in which AlCI, (2 g.)
is suspended. The product is treated with cold
water and distilled (Muhlert, B. 19, 635). Oil.
Oxim 04SHEt2.C{N0H).0Hs. Oil.
ETHYL-(a)-THIOCABBAHIC ACID. Ethyl
e<fcerNHEt.CO.SEt. (204°-208°). Frommer-
captan and cyanic ether (Hofmann, B. 2, 118).
Heavy oil. Decomposed by acids or alkalis into
mercaptan, CO,, and ethylamine.
Benzoyl derivative ? NBzEt.CO.SH.
[74°]. From BzCl and potassium sulphocyaiiide
in alcoholic solution (Lossper, J.pr. [2] 10, 235).
On pouring the product into water the acid sepa-
rates as hard sulphur-yellow prisms, t. b1. sol.
water, v. sol. alcohol and ether. Eesolved by.
heat into mercaptan, benzonitrile, and CO,. Hot
aqueous EdH gives EOBz, potassium sulphide,
potassium carbonate, and potassium sulphocyan-
ide NBzEt.CO.SX: small needles (from alco-
hol), V. sol. water, si. sol. alcohol and ether. — '
AgA': flooculent pp. turns black on heating. — ^Et A'.
From the K salt and BtBr. Heavy non-volatile
on. At 105° it forms crystals [129°].— 0,H„A'?
small prisms, sol. water and alcohol; formed
from isoamyl alcohol and benzoyl sulphocyanide
(Miquel, A. Gh. [5] 11, 330).— CAA' : [93°] ;
minute needles (from dilute alcohol) ; insol. water,
V. sol. alcohol and ether.
Ethyl-(;3)-tIiiocarbamic acid. Ethyl ether
NHEt.CS.OEt. Ethyl-methcme. (204°-208°).
From ethyl thiooarbimide and alcohol by heating
for several hours at 110° (Hofmann, B. 2, 117).
Formed also by treating ethyl thio-carbimlde
with alcoholic NaOH. Oil, smelling of garlic.
Split up by alkalis or dilute acids into ethyl-
amine, HjS, alcohol, and GO,. Cone. H2SO4 gives
ofe COS.
Ethyl-di-tUo-carbamic acid NHEt.CS.SH.
The ethylamine salt is formed by adding CS,'
slowly to an ethereal solution of ethylamine at
-18° (Hofmann, B. 1, 25 ; EudnefE, J. ' B. 10,
188 ; B. 11, 987 ; Bn. 1, 998) ; the free acid is
ppd. on adding the calculated quantity of HCl to
a solution of this salt. It is crystalline. It is
decomposed by excess of ECl into CS, and ethyl-
amine.
Salts. — The silver salt is a white pp. de-
composed by boiling water into silver siUphide
and ethyl thiooarbimide. — ^Ethylamine salt
NHEt.CS.SNH»Et. [103°]. Six-sided tables
(from alcohol), v. sol. water and alcohol, m. sol.
ether. On boiling the alcoholic solution di-ethyl-
thio-urea is formed. Iodine attacks its alcoholio
solution forming di-ethyl-thio-urea, CSj, ethyl
thiooarbimide, NHjEt, and sulphur. ^ .
Ethyl ether EtA'. Di-ethyl-oscmthaniide,
Prepared by digesting mercaptan with ethyl-thio-
carbimide at 120° for several hours (Hofmann,
Z. [2] 5, 268). Heavy oil. Decomposed by dis-
tillation.
Di-ethyl-di-thio-carbamic acid. Diethyl-
amine salt NEtj.CS.S.NH2Et2. From CS, and
diethylamine (Grodzki, B. 14, 2754). Not de-
composed at 110°. Split up by iodine into di-
ethylamine and OioHjoNjSj or (NEt2.CS)2S, [70°]
which may be crystallised from alcohol.
ETHYL -THIO-CABB AMINE -CYAIIIDE v.
OABBIMmO-BTHTL-THIO-UBBA.
ETHYL-THIO-CAEBAMINE-METHYL CY-
AMIDE II. Methxl-cabbimido-sihxl-ihio-dbha.
eso
ETHYL-THIOOARBIMIDE.
ETHYL- THIOCAEBIMIDE C3H5NS i.e.
EtN.CS. Ethyl mustard oil. Mol. w. 87. (133°).
V.D. 303 (oalo. 3-02). S.G. £ 1-019 ; ^ -997
(BufE, Z. [2] 4, 730J ; | -995 (Nasini a. Scala, G.
17,66). Eco 43-35.
Formation.^-l. By heating oyanio ether with
PjSs (Miohael-a. Palmer, Am. 6, 260).— 2. By
adding an aqueous solution of ethylamine to
CSOlj (Eathke, A. 167, 218).— 3. By distilling
di-ethyl-thio-nrea with P^Oj or dry HCl (Hof-
mann, B. 1, 26). — 4. By distilling ethylamine
ethyl-di-thio-carbamate (from OS^ and NHjEt)
with aqueous silver nitrate, or, better, HgClj. An
excess of AgNO, must be avoided, or some of the
EtKCS vrill be changed into EtNOO. It is un-
neo6sBaiy to use pure ethylamine, the crude
product of the action of alcoholic NH, on £tl
answers just as well. — 6. Formed in small quan-
tity, together with ethyl sulphocyanide and
other products, by heating mercuric sulpho-
cyanide with EtI at 180° (Michael, Am. 1, 417).
Properties. — Pungent liquid, inflames the
tongue.
BeacUons. — 1. It unites directly with amino-
ma and primary amimes forming ethyl- and
ethyl-alkyl- thio-ureas. — 2. Digested for some
hours at 110° with alcohol it forms ethyl-(;8)-
thio-carbamic ether. — 8. JlTeT-capfawat 120° gives
ethyl-di-thio-oarbamic ether.— 4. WhencfeZorirae
is passed through a cooled mixture of equal
volumes of ethyl thiocarbimide and dry ether
there is formed a powder which by treatment
with aqueous NaOH is converted into (EtHGS)20
[42°]. This oxide of ethyl thiocarbimide crys-
tallises from alcohol in splendid colourless
tablets and prisms, insol. water. On treatment
with ammonium sulphide sulphur separates and
the filtrate deposits crystals [0. 60°] (Sell, B. 6,
322). — 5. Ethyl thiocarbimide (1 mol.) warmed
with aldehyde-ammonia (2 mols.) and alcohol
at 100° forms silvery needles of C^HjiKjSjO^
[119"], V. sol. alcohol, ether, and hot water.
Alkalis and dilute acids give ofl aldehyde, NH3,
ethylamine, &o.
ETHYL THIOCABBONATES. SuVphocarbo-
mc ethers. '
]|[ono-6th7l-(a)-thiocarbonate. Salts. —
EtO.CO.SK. Formed by the action of alcoholic
KOH or KSH on CS(0Et)2, or of KOH on
EtO.CS.SEt (Debus, A. 73, 130, 136, 142 ; 82,
. 253). Formed also bypassing CO2 into an alco-
holic solution of KSEt (Chancel, C. B. 32, 642).
Also from COS and alcoholic EOH (Bender, A.
148, 137). Long needles or prisms; t. sol. water
and alcohol, insol. ether, not deliquescent. The
aqueous solution decomposes on boiling into
Et2C0„ mercaptan, Et^S, and alcohol. The dry
salt decomposes at 170° into COS, Et^S, and
E^CO,. On adding acids to its aqueous solution
COS and alcohol are formed. By adding iodine
to its alcoholic solution there is formed
EtO.CO.S.S.CO.OEt, a heavy oil, which is de-
composed by alcoholic EOH giving EtO.GO.SE,
lulphur, and K2S. When "SR, is passed into its
alcoholic solution sulphur is deposited, whUe
EtjS and allophanio ether remain in solution
(Chancel, C. B. 32, 644; Debus, A. 75, 142).—
(EtO.CO.StgZn : m. sol. water and alcohol. —
(EtO.CO.S)jPb : crystalline powder, insol. water,
si. sol. alcohol.— EtO.CO.SAg:' unstable sticky
mass, insol. water,— (EtO.CO.S)8Cu^CujS Ob-
tained by adding cuprio sulphate to a solution
of the K salt until the milky pp. first fbrmed
becomes yellow. This is washed with ether. It
is a yellow amorphous powder.
Di- ethyl (a) - thiocarbonate EtO.CO.SEt.
(156°). S.G. iS 1-0285. B.^ 34-09 (Nasini, G.
13, 302). From the K salt and EtBr in alcohol
(Salomon, J. pr. [2] 6, 438). Also from NaSEIi
and OlCOsEt. Iiiquid with characteristic smell..
Split up by water at 160° into mercaptan, COj,
and alcohol. Alcohoho NH, gives mercaptan and
EtO.GO.NHj. Alcoholic KOH gives mercaptan,
alcohol, and potassium carbonate.
Amide EtS.GO.NHj. IsotMocarharrda ether.
IsotUourethame. [102°] (P.); [108°] (P.).
Formation. — 1. By passmg gaseous HCl into
an alcoholic solution of ethyl sulphocyanide
(Pinner, B. 14, 1082).— 2. From HCl and alco-
holic potassium sulphocyanide (Blankenhorn,
J. pr. [2] 16, 375).-3. From ClCO.SEt and NH,
(Salomon, J. pr. [2] 7, 256). — 4. From
NH3.CO.SNH4 and EtBr (Fleischer, B. 9, 991).—
5. In small quantity from C0(SEt)2 and NH,
(Salomon a. Conrad, J.pr. [2] 10, 32).
Properties. — Plates, may be sublimed ; si. sol.
water, v. sol. alcohol. In a sealed tube at 150°
it splits up into mercaptan and cyanuric acid.
Alcoholic NH, gives urea and mercaptan. Alco-
holic KOH gives CO,, ammonia, and mercaptan.
1*205 gi^BS ethyl sulphocyanide. HgCl,, CuSO^,
and AgNO, give pps.
Di-ethyl ethylene (ii)-dl-tliio-di-carbonate
(EtO.CO.S)AH4. From EtO.CO.SK and alco-
holic ethylene bromide (Welde, J. pr. [2] 15, 32).
Thick oil with unpleasant odour. Cannot be dis-
tUled. Alcoholic NH, gives in the coldC2Hj(SH)j
and oarbamio ether. Alcoholic KOH gives in the
cold EtO.CO.OK and C2H,(SH),.
Ethyl isobutyl («) -thiocarbonate
EtO.0O.S0.H„. (192°). S.G. ia -994, From
ClCOjEt and NaSC,H, (Mylius, B. 6, 318).
Alcoholic NH, converts it into HSC^H, and
BtO.CO.NHj. Alcoholic KOH or KSH forms
C,H,SH, alcohol, and COj.
Isobutyl ethyl (a)-thiocarbonate
CjH9O.CO.SEt. (193°). S.G. i2 -994, From
CLCOaC^Hj and NaSEt (M.). Liquid, smelling
like mercaptan. Alcoholic NH, gives mercaptan
and CjH,0.C0.NH2. Warm alcoholic KOH gives
EtSH, isobutyl alcohol, and CO,.
Ethyl- isoamyl thiocarbonate
C0(0Et)(SC5H„). From C1.C0.S.C,H„ and
NaOEt. A liquid (Schone, J. pr. [2] 32, 245).
BeacUons. — 1. Alcoholic NH, reacts accord-
ing to the equation C0(S.0,H„)(0Et)-hNH,
= HSC,H„-H00(NH,)(0Bt).— 2. Alcohoho KOH
reacts thus: CO(SC5H„)(OEt)+2KOH
= HSC,H„ -1- HOEt + KjCO,. .
Ethyl (i3)-thio-carbonic acid.
Chloride EtO.CSCl, (136°). Colourless
pungent oil ; formed in sfnall quantity by the
action of alcohol oh CSCl,. Converted by NH,
into the amide (Klason, B. 20, 2386).
Amide EtO.CS.NH,. XoMthogenamide.
[38°] (Salomon, J.pr. [2] 8, 115), Formed by
the action of alcoholic NH, on EtO.CS.SEt
(Debus, A. 75, 128), on EtO.CS.Cl (Klason), on
EtO.GS.SMe (Chancel, J. 1851, 618), or on
(EtO.CS)2S2. Monocliuio pyramids. M. sol.
water, v. e. sol. alcohol and ether. Split up by
y dry distillation into mercaptan, cyanic acid, and
ETHYL THIOOARBONATES.
621
cyanuric acid. Alcoholic KOH or baryta form
alcohol and a sulphooyanide. PjOj gives ethyl
sulphooyanide (Salomon a. Conrad, J. jpr. [2] 10,
84).
OojB&matoras.— (CsH,NSO)jOu2Clj. Formed
by adding CuSO, to the aqueous solution and
decomposing the pp. with HCl. Small rhom-
bohedra (from alcohol) ; v. si. sol. water. —
(C^,NSO),OnjClj. — (03H,NS0),CujCij. —
iO,H^SO)sOujOl5. — (OsH,NSO)jCnI. —
OftNSO ,OuI. — (O.H,NSO)2Cuj(SCy)2. —
G,H,NS0),3Caj(SCy)j.— CH,NS05Cuj(S0yi.^
OjfiyiSOhPtjOl, (Debus).
, Di - ethyl (;8)-tMocMbonate EtO.CS.OEt.
(162°). S.G. i 1-032. Boo Si-U (Nasini, (?. 13,
803).
Formation. — 1. By the dry distillation of
EtO.CS.S.S.CS.OEt, the other products being
CS, and EtO.OS.SEt (Debus, A. 75, 136).— 2.
From CSCa^ and KOEt (Salomon, J.pr. [2] 6,
441).
Properties. — Liquid with pleasant odour. In-
sol. water, v. sol. alcohol and ether.
Beacticms. — 1. Alcoholic KHS gives mercap-
tan and EtO.CO.SK.— 2. Alcoholic KOH gives
alcohol, EtO.CO.SK, and EtO.CO.OK.— 3. Cold
alcoholic NE, gives NH^SCy and alcohol.
Mono-ethyl (a3)-di-thio-carbonate
KtO.CS.SH. XanthogerUc acid. XantMc acid.
FormaUcm. — KOH (2 pts.) is dissolved in
alcohol (1 pt.), and CS, is slowly added until
the liquid is no longer alkaline. On cooling to
0° the potassium xanthate separates in colour-
less needles from which the acid may be obtained
by treatment with dilute H^SOj (Zei^e, Sch. J. 36,
1 ; 43, 160 ; P. 35, 457 ; Couerbe, A. Ch. [2] 61,
225 ; Saco, A. 51, 345 ; Debus, A. 72, 1 ; 75, 121 ;
82, 253 ; Desains, A. Oh. [3] 20, 496 ; Hlasiwetz,
A. 122, 87). Potassium xanthate is also formed
by treating xanthio ether with KHS.
Properties. — Colourless heavy oil, with strong
odour. It first reddens litmus, then bleaches it.
It is very inflammable. At 24° it seems to boil,
being split up into CSj and alcohol. It expels
COj from its salts.
Salts. — The soluble xanthates form a white
pp. with lead salts, a yellow pp. with cupric salts
(hence the name), and a light-yellow pp. with
silver and mercurous salts ; the last-mentioned
pp. turning black.— KA'. S.G. ?lis 1-5576 (Clarke,
B. 11, 1505). S. (alcohol) 20. Prepared as above.
Colourless prisms which turn slightly yellow on
exposure to air. V. sol. water and alcohol, insol.
ether. Its aqueous solution decomposes above
50° into KjCSj, alcohol, HjS, and COj. In the
dry state it may be heated to 200° without altera-
tion ; at a higher temperature it decomposes,
leaving a residue of K^S mixed with charcoal.
Hot KOHAq forms EtO.CO.SK. Iodine added
to its alcoholic solution gives EtO.CS.S.S.CS.OEt,
which is also formed by the action of iodine on
lead xanthate (Desains, A. Ch. [3] 20, 469;
Debus, A. 72, 1). This substance [28°] S.G.
1-260 (N. ar S.) forms prisms, v. e. sol. alcohol
and ether, insol. water. (EtO.CS)jS2 is split up
on distillation into EtO.OS.SEt, (EtO)jCS, CO,
sulphur, and CS^. Potassium unites with
(EtO.CS)2S2,formingpdtaasium xanthate (Dreoh-
sel, Z. 1865, 583). Alcoholic NHj converts
(EtO.CS)2Sj into xanthamide and ammonium
xanthate. Alcoholic KOH gives potassium
xanthate, COj, and sulphur. Alpoholic KSH also
converts (BtO-CSj^Sj into potassium xanthate,
HjS and S being set free. Aniline converts
rEtO.CS)2S8 intjo NHPh.CS.OEt and CS(NHPh)2
(Hofmann,.B. S, 773). Potassium xanthate is
converted by ClGOjBt into S(CS.0Et)2 [55°].
This body crystallises from alcohol in golden
needles, split up by alcoholic NH, into
EtO.CS.NHj and H^S, and by alcoholic KOH
into EtO.CO.SK and EtO.CS.SK (Welde, J. pr.
[2] 15, 45).— NaA' : yellow needles.— NH4A' ; '
colourless Ueedles, resembling urea. V. e. sol.
water and alcohol.— BaA'^ 2aq : from alcohol,
BaO, and CSj. Very unstable laminse ; sol.
water. — "CaA'^ : gummy mass. — AsA',. Pre-
pared by dropping a solution of AsCl, in CS^
into alcoholic NaOEt, with cooling. The liquid
is filtered from NaCI, and allowed to evaporate
spontaneously (Hlasiwetz). Colourless mono-
clinic tables (from CSj). V. e. sol. CS.„ De-
composed by heat, leaving ASjS,. Decomposed
by warm aqueous HCl. — SbA'^. Prepared in
the same way as the preceding xanthate, using
SbClj. Large lemon-yellow triolinic crystals. —
BiA'j : golden-yellow lamina and tables. — CrA'., :
shining dark-blue crystals; m. sol. CSj, form-
ing a violet-blue solution.— CoA'j : large black
crystals, m. sol. CSj forming a dark grass-
green solution (H.). 'insol. NH, (Phipson, C.
B. 84, 1459).— NiA'2 : large black monocUnic
tables, m. sol. CS, forming a yellowish-green
solution (H.). Sol. NH,Aq.— HgA'^. From
NaOEt and HgOlj in CS.^ (H.). Satiny scales,
m. sol. CS2.— SuA'j. From NaOEt, SuClj, and
CS2 in the same manner as AsA'j (H.). Golden.
laminfB and tables. — FeA',, : blq,ck monoolinio
crystals ; its solution in CSj is brownish-black
(H.). — CujA'j. Potassium xanthate added to a
solution of a cupric salt forms at first a brownish-
black pp. of cupric xanthate, but this quickly
changes to beautiful yellow flocculi of cuprous
xanthate. This salt is not sensibly attacked by
HjS, but ammonium sulphide decomposes it im-
mediately. It is decomposed by hot acids. It
is insol. water and NH,, sol. CSj. — PbA'j. Pre-
pared by adding CSj and lead hydroxide to
alcoholic KOH. Colourless sUky needles; insol.
water and ether, m. sol. boiling alcohol. Slowly
deconiposed by H^S, immediately by ammonium
sulphide. When boiled with aqueous KOH a
pp. of PbS is formed. Cupric sulphate solution
poured on the crystals immediately changes
them to cuprous xanthate (Debus). — ZnA'^:
granular pp. ; si. sol. water, m. sol. alcohol,
V. sol. NHjAq (P.).
Chloride and Amide v. supra.
Methyl ethyl (a;S)-dithiocarbonate
EtO.CS.SMe. Methyl xanthate. (179") (S.) ;
(184°) (C). S.G. j 1-119 (Nasini a. Scala, 0. 17,
66) ; U 1-123 (C.) ; iS 1-129 (S.). E „, 65-67.
•V.D. 4-65. Obtained by distilling KMeSO, with
potassium xanthate (Chancel, A. Oh. [3] 35,468).
Also from potassium xanthate and Mel (Salomon,
J.pr. [2] 8, 116). Pale-yellow oil; sol. alcohol
and ether. Alcoholic KOH gives MeSH and
xanthamide EtO.CS.NH2.
Di-ethyl (a;8)-di-thio-carbonate EtO.OS.SEt,
Xanthic ether. Mol.w.l50. (200°). S.G. 1 1-074
(N. a. S.). Boo 70-95.
FormaUon.—l. From EtO.CS.SK and EtCl
(Debus), or EtBr (Salomon, J. pr. [2] 6, 445)
622
ETHYL THIOCARBONATES.
2. By the dry distillation ol (EtO.CS)^
(Zeise).
Properties.— Pale-yellow oil, smelling like
garlic ; miscible with alcohol and ether. It
dissolves iodine. It is but slightly attacked by
potassium. It is not attacked by HCl. Its
alcoholic solution gives a white pp. with HgCLj.
HgO, PbO, and PbOj do not act on it. '
Beaciions.—Mooholio KSH gives meroaptan
and EtO.CS.SK. Alcoholic KOH acts in like
manner. KH, passed into its alcoholic solution
fotms EtjS, H^S, and EtO.CS.NHj. Aqueous
NHj at 135° forms alcohol, mercaptan, and
KHjSOy. Water at 160° gives mercaptan, alco-
hol, COj and HjS (Schmitt' a. Glutz, JB. 1, 168).
Chloride EtS.CSCl. (100° m otcmo). S.G.
i^ 1-1408. From meroaptan and CSClj,(Klason,
B. 20, 2385).
Amide EtS.CS.NHj. [42°], Formed by
passing HjS into ethyl siilphooyanide at 100°
under extra pressure (Jeanjean, J. 1866, 501 ;
Salomon a. Conrad, J. pr. [2] 10, 29). Trimetric
crystals (from ether) with unpleasant odour.
Insol. water, v. e. sol. alcohol and ether. Alco-
hoUo NH, or KOH gives mercaptan and sulpho-
cyanide. EtI forms crystalline EtS.CS.KH^tl.
HgClj, AgNOj, and CUSO4 give pps.
Acetyl derivative of the Amide
EtS.CS.l!ffiAc. [123°]. YeUow needles ; sol. al-
cohol, ether, and hot water. Boiled with baryta-
water it gives mercaptan, barium sulphocyanide,
and barium acetate. Formed by the combina-
tion of thio-acetic acid with ethyl-sulphocyanide.
On dry distillation it is decomposed into these
constituents (Chanlaroff, £. 15, 1987).
Ethylene ethyl (ai3)-di-thiocarbonate
(EtO.CS.S)2C2H4. [42°]. From potassium xan-
thate and alcohoUo ethylene bromide (Welde,
J.pr. [2] 15, 55). Long needles or tables (froin
ether). Alcoholio NH, gives EtO.CS.NH^ and
C^,(SH),.
Ethyl propyl (a3)-di-thiocB{bonate
EtO.CS.SPr. S;G-. 1 1-050. E 00 78-55 (Nasini a.
Soala, a. 17, 66).
Ethyl iso butyl (a;S)-di-thio-carbanate
C^HsO.CS.SEt. (228°). S.G. il 1-003. From
C,H80.CS.SK and EtI (Mylius, B. 6, 975).
Si - ethyl - (aa) - di - thiocarbonate C0(SEt)2.
(197°). S.G. 23 1-084.
Formation. — 1. By warming ethyl sulpho-
cyanide vrith cone. HjSOj (Schmitt a. Glutz, B.
1, 166).— 2. From NaSEt and COOL (Salomon,
J. pr. [2] 7, 255). — 3. From di-phenyl carbonate
and NaSEt (Seifert, J.pr. [2] 31, 464).
Properties. — Oil, smelling like garlic. Alco-
holic NH3 splits it up into urea and mercaptan.
Alcoholic KOH gives KEtCOj and mercaptan.
Water at 160° forms 00,, and meroaptan.
mono-ethyl tri-thio-carbonate EtS.CS.SH.
Salt.— KA'. Formed by direct union of CSj
with KSEt (Chancel, C. B. 32, 642). Sol. water
and alcohol. Its solution gives yellow pps. with
salts of Ag, Fb, and Hg; and with GuSO^a scarlet
pp. of the cuprous salt. These pps. decompose
when heated, leaving metallic sulphides. The
K salt decomposes at 100° into P2S5 and an oil
C.H,„S?
Di-ethyl tri-thio-carbonate EtS.CS.SEt.
(240°).
Formation. — 1. From KjCSj or NauCS, and
EtI or EtCl (Schweitzer, J.pr. 32, 254; Debus,
A. 75, 147; Husem^ann, A. 123, 67).— 2. By
acting on EtI and CSj with sodium amalgam
(Nasini a. Scala, 0. 17, 236; cf. Lowig a. Sch61z,
J", pr. 79, 441).— 3. From CSClj and NaSEt
(Klason, B. 20, 2385).
Properties. — ^Heavy yellow oil, v. sol. alcohol
and ether. Has a slightly alliaceous odour.
Bums with blue flame. When heated slowly it
partially decomposes into Et^S and CSj. Alco-
holic KOH gives K^CS,, mercaptan, &e. Alco-
holic NH3 at 100° gives mercaptan and ammonium
sulphocyanide. Unites with bromine, forming
EtsCSjBrg, which crystallises from ether in large
six-sided prisms, decomposed by water with
liberation of HBr, and by potash with liberation
of the original ether (Behrend, A. 128, 333).
Oxidised by HNO3 to ethane sulphonio acid.
Ethyl-ortho-thio-carbonate C(SEt)4. S.G.
1-01. Formed by treating OCl, vrith NaSEt
(Claesson, J.pr. [2] 15, 212). Oil, with un-
pleasant odour. Gives oS Et^S, when heated.
Volatile with steam. Oxidised by HNO, to
ethane sulphonio acid.
ETHYI. THIOCYAKATE v. Ethil sulfho-
SI-ETHTI-THIONINE
yCM, — NHEt
N< >S
-NEt
J
Obtained by the action of FojCl, upon a ^lute
solution of ethyl.^-phenylene diamine in pre-
sence of HjS and HCl. In its properties and
reactions it closely resembles the di-methyl-
thionlne (q. v.) (Bernthsen a. Goske, B. 20, 933).
(o)-ETHYL-THIOPHElIE C^HsS i.e. .
CH— CH
II II . (133° cor.). S.G.24-990. Formed
CEt.S.CH
by the action of sodium upon a mixture of (iS)-
bromo-thiophene and EtBr (Schleicher, B. 18,
3015 ; 19, 671) ; or upon EtI or EtBr and (3)-iodo-
thiophene (Meyer a. Kreis, B. 17, 1560 ; Egli,
B. 18, 544). Colourless oil. Gives Lauben-
hehner's reaction. By alkaline KMnO^ it is
oxidised to thienyl methyl ketone, thiophene-
(a)-carboxylio acid [127°], and 'thienyl-(a)-gly-
oxylio acid. ' Gives a tri-bromo- derivative
CiSBtBr^ : [108°] ; colourless plates.
CEt.CH
(;8)-Ethyl.thiophene || || . Obtained by
CH.S.OH
heating ethyl-succinie acid with P^Sj (Damsky,
B. 19, 3284). Oil. KMuOj gives thiophene (;8)-
oarboxylic acid [136°].
Di-ethyl-thiophene C^SHjEt,. (181° cor.).
S.G. ij -962. From iodo-ethyl-thiophene, Btl,
and sodium (Muhlert, B. 19, 633).
Beferences. — Bbomo-, Chlobo-, lono-, and
NlTEO-BTHIL-THIOPHBNB.
(a)-ETHYL-XHIOPH£NEGABBOXYIIG ACID
C4SH2Et.C02H., Ethyl-thiophemo add. [71°].
Obtained b^ the action of sodium amalgam upon
a mixture of iodo- (a) -thiophene and ohloro-
formid ether, and saponiflcatioh of the produqt.
Glistening colourless crystals. V. sol. alcohol,
ether, and hot water, si./ sol. cold watei:. By
alkaline KMniO, it is oxidised to thiophene di-
carboxylic acid.
Salts. — AgA': curdy pp., sol. hot water. —
CaA'2 2^q : colourless silky needles (Schleicher,
B. 18, 3018).
ETHYL-TOLUENE.
523
ETHTL TEIOFHOSPEATES.
Mono -ethyl thiophospliBte (EtO)PS(OH)j.
Ethyl-thiophosphoria acid. Oil toimed by the
action of alcohol on PSCI,. The K and Na salts
are formed by treating PSOl, with alcoholic KOH
or NaOH. They are v. sol. water and alcohol.
The salts of Ba, Sr, and Ca are orystalliaable.—
BaA" (Cloez, 0. B. 24, 388 ; Chevrier, Z. 1869,
413).
Dipethyl-thiophosphate (£tO)2FS(OH:). Di-
ethyl-thiophoyihorie add. Formed, together
with BtjPSjOj, by the action of PjS, on alcohol
(Carius, A. 112, 190). Viscid oil, having an
acid and bitter taste. It may be boiled in
aqueous or alcoholic solution without decompo-
sition, but when heated per se it gives off mer-
captan and leaves phosphoric acid. It forms
very stable salts, those of the alkalis, alkaline
earths, and of lead being v. sol. water, sol.
absolute alcohol and ether. The silver salt is
V. si. sol. water, but v. sol. alcohol and ether.
Tri-ethylthiophosphate(EtO),FS. Formedby
the action of alcohol on PSCl, or PSBr, ; and of
PSClj on NaOEt (Carius, A. 119, 291 ; Chevrier,
Z. 1869, 413 ; mchaelis,B. 6, 4). Oil, smelling
like turpentine, volatile with steam. Cone.
HjSO^ appears to form BtPSO, and Et4PjSj05-
Di-ethyldi-thiophosphateBtjHPOjSj.Pormed,'
together with BtjS, by heating BtjPOjSj with
mercaptan in a sealed tube (Carius). The E salt
is formed by the action of alcoholic KSEt on
Et3P02S2. Colourless amorphous mass.
Tri' ethyl di - thio - phosphate EtaPO^S^.
Formed, as above, by treating alcohol witii F-^S^.
Colourless oil, with aromatic and somewhat
alliaceous odour. Volatile with steam.
Di-ethyl tetra-thio-phosphate Bt^HPS^. The
E salt is formed by the action of alcoholic ESH
on Bt,PS4. Bt^HPSf crystallises in prisms
(Carius, J. 1861, 583).
Tri-ethyl tetra-thio-phosphate Et3PS4. Pro-
duced by the action of F^S, on mercaptan, or,
better, on mercury mercaptide (Carius, A. 112,
199). Light yellow oil. EOH forms, apparently,
EEtJPOS,.
letra-ethyl di-thio-pyrophosphate Et^P^S^O,.
Appears to be produced by treating EtjPSOj
with cone. H^SO, (Carius, Z. 1861, SOS). Liquid,
m. sol. water. Alcoholic EOH gives Bt,EPjSjOj.
Tetra-ethyl tri-thio-pyrophosphate
EtiP^SjO,, From FjSjBr^ and alcohol (Miohaelis,
B. 5, 8).
Tetra-ethyl penta-thio-pyrophosphate
EtjPjSA- [71°] (Carius, J. 1861, 686).
ETHYL THIOSnTAUIITE v. Bihyl-ai.ltl-
IHIO-UBEA.
MONO-ETHYL THIOSULFHATE
EtS-SOj-OH. Ethyl-tMosulphtmo acid.
Formation. — 1. By treating Et^S with an
equal volume of cone. B^O, (B. E. Smith, O. J.
22, 302).— 2. By heating BtBr (1 mol.) with
"SZi^fii (1 'BUil.) with an inverted condenser
(Bunte, B. 7, 646). — 3. By the action of iodine
on a mixture of mercaptan and Na^SO, (Spring,
B. 7, 1162).
Salts. — NaA' : silky six-sided needles (from
alcohol). Its aqueous solution is scarcely de-
eomposed at 100°, but on adding a small quantity
of HOI it rapidly splits up into mercaptan and
NaHSO^. The dry salt is slowly converted at
100° into dithiouate and Et^S,. Its aqueous
solution gives sparingly soluble pps. with AgNOj,
Pb(N03)2, and HgClj; the last pp. is quickly
converted on heating into EtSHgCl, while sul-
phuric acid remains in solution. HHO, oxidises
the sodium salt to sulphuric and ethane slilphonic
acids. Sodium forms mercaptan and NajSO^.—
BaA',2aq : colourless rectangular tables, v. sol.
water, si. sol. alcohol. The copper salt forms
small dimetric tables, v. sol. water. The silver
salt crystallises in small shining laminee.
Chloride EtS.SOjCl. From the Na salt
and PCI5. Split up by heat, giving Et^Sj (cf.
Bamsay, B. 8, 764).
ETHYL- THIO -UBAMISO- BENZOIC ACID
NHEt.OS.NH.OsH4.CO2H. Phen/yUthyl-ttm-
urea m-carboxyUc acid. [195° unoor.l. Formed
by boiling m-amido-benzoio acid with ethyl-
mustard-oil in alcoholic solution (Asohan, £;
17, 430). Small transparent prisms.
ETHYL-THIO-UBEA OjH,NjS i.e.
NHj.CS.NHEt. Mol. w. 104. [113°] (Hofmann,
JB. 18, 2788). From ethyl thio-carbimide by
direct addition of NH, in alcoholic solution
(Hofmann, Z. 1868, 686 ; 1870, 157; B. 1, 26),
Needles (from hot water). Sol. water and alco-
hol. Its solution in aqueous HOI gives a yellow
pp. with PtClj. In aqueous or alcoholic solution
it is easily desulphurised by FbO or HgO, the
ultimate product being tri- ethyl -melamine
0,N.(NHEt)3.
Benzoyl derivative NHBz.OS.NHEt.
[134°]. Obtained by treating benzoyl sulpho-
cyanide with ethylamine (Miquel, A. Oh. [5] 11,
313). Slender prisms, insol. water, m. sol. boil-
ing alcohol. Split up by boihng with aqueous
HOI, giving ethylamine and benzamide. HgO
gives NHBz.CO.NHEt.
Di-ethyl-thio-urea CS(NHEt)2. Mol. w. 132.
Formed by the addition of ethylamine to ethyl
thiocarbimide ; also, with evolution of HjS, by
heating ethylamine ethyl-thio-carbamate with
alcohol at 115° (Hofmann). Crystals, sol. alco-
hol, m. sol. water. Its solution in aqueous HCl
gives a yellow crystalline pp. with PtOl,. By
P2O5 or dry HCl it is resolved into ethylamine
and ethyl thiocarbimide. It is not decomposed
in aqueous or alcoholic solution by PbO, but
recently ppd. HgO converts it into CO(NHEt)j
[107°]. HgO in presence of ethylamine forms
tri-ethyl-guanidine.
Tri-ethyl-thiourea NHEt.CS.NEtj. [26°].
(205° uncor.). Prepared by the action of ethyl-
thiocarbimide on diethylamine (Orodzki, B. 14,
2755). Colourless crystals. Sol. alcohol and
ether, nearly insol. water. AlkaUne reaction.
Potash-fusion gives NHjEt and NHEt^. PjOj
gives ethyl thio-carbimide.
Tetra-ethyl-thiourea CS(NBtj)j,. (216° un-
cor.). S.G. i5 -9345 (Grodzki, B. 14, 2757).
Colourless liquid. Sol. alcohol and ether, insol.
water. Strong base of alkaline reaction. Very
stable. Prepared by ethylation of tri-ethyl-
thiourea.
ETHYL TITANATE BtjTiO,. By the action
of TiCl. (1 mol.) on alcohol (4 mols.) there is
formed Ti01,(OEt)jEtOH [105^-110°] whence
NaOEt gives Ti(0Et)4 (Demairijay, G. B. 80, 61).
Trichloride BtOTiCl,. [78°]. (187° cor.).
From TiOl, and ether (Bedson, A. 180, 235).
o-ETHYL-TOLrENE CsH,, i.e.
CsH,(CHs)(0jH5) [1:2]. Methyl-ethyl-bmzena
S24
ETHYIi-TOLUENE.
Mol. w. 120. (158° uncor,). S.G. w -8731.
Liquid at - 17°. Obtained by the action of
Bodium upon a mixture of o-bromo-toluene and
ethyl bromide. By dilute ENO, it is oxidised
to o-toluic acid, and by EMnO^ to terephthalio
acid (?) (Clans a. Mann, B. 18, 1121).
w-Ethyl-toluene 0,H<MeBt [1:3]. (169°).
S.G. sa -869. Formed by boiling an ethereal
Bolntion of EtBr and nt-bromo-tolueue with
sodium for two days (Wroblewsky, A. 192, 198).
Formed also by distilling abietio acid with zino-
dust (Ciamician, B. 11, 270). By oxidation with
CrO,,it yields isophthalic acid. H^SO^ forms
two sulphonio acids ; the Ba salt of one of these
BaA'j6aq forms large crystals, si. sol. water;
that of the other forms small prisms, t. sol.
water
Dihydridel 0,H„. (164°). Occurs in
animal oil (Weidel a. Ciamician, B. 13, 72).
Giyes isophthalic acid on oxidation.
Sulphonic acids CjHjMeEtSOjH. —
BaA'j 6aq.— BaA'j 3aq.
p-Ethyl-loluene 0,H,MeBt [1:4]. (161-9°-
162-1°) at 756-3 mm. S.G. '-^ -8694 (Sohiff) ;
f -864 (A.). V.D. 411 (oalc. 4-14). S.V. 161-9
(Schiff, A. 220, 93). Formed by treating
p-bromo-toluene with ethyl bromide and sodium
(Glinzer a. Fittig, A. 136, 303; Jannasch a.
Dieckmann, B. 7, 1513). Formed also from
ethylidene chloride, toluene, and AljCI,
(Anschiitz, A. 235, 314). Converted by KjCrjO,
and H2SO4 into p-toluic and terephthalic acids.
Beferences. — Bbomo-, Chlobo-, and Niibo-
STHTIi-TOIinENE.
Di-ethyl-toluene OjHsMeEtj [1:3:5]. (199°).
S.G. S2 -879. From acetone, methyl ethyl
ketone, and H^SO^ (Jacobsen, B. 7, 1434). ENO,
oxidises it to uvitic acid.
Isomeride v. Amyii-benzene.
ETHYI-o-TOLTnDINE C^„N i.e.
C„E,(OE,).NEEt. (214°) (B. a. S.) ; (206°) (N.).
S.G. !|;° -9534. Prepared by heating o-toluidine
hydrobromide (or hydroiodide) with 1 mol.
( -I- 5 p.c. excess) of ethyl alcohol at 160° for
8 hours ; the yield is 64 p.c. of the theoretical.
Acetyl derivative C,E,(CB|,).NAcEt.
(265°) (Eeinhardt a. Staedel, B. 16, 29 ; Norton,
Am. 7, 118).
Nitrosamine CjE^Me.NEt.NO. Oil;
volatile with steam.
Ethyl-p-tolnidine CBE,Me.NBEt[l:4]. (217°).
S.G. 1^1 -9391. From p-toluidine and EtI by
heating for 2 days at 100° (Morley a. Abel, C. J.
7, 68). Oil. Its sulphate and oxalate are
crystalline.— B'jE^PtOl, : pale-yellow crystals,
sol. water and alcohol, si. sol. ether; decomposed
at 100°.
Di-ethyl-o-toluidine CBE,(CE3).NEt2. (208°)
at 755 mm. ; (210° i. V.) (E.). Formed by heat-
ing ethyl-o-toluidine with excess of EtI at 100° ;
the yield being 70 p.c. (Norton, Am. 7, 119).
Prepared by heating o-toluidine' hydrobromide
(or hydroiodide) with 2 mols. ( -i- 5 p.c. excess)
of ethyl alcohol at 160° for 8 hours ; the yield is
90 p.c. of the theoretical (Belnhardt a. Staedel,
B. 16, 29). Oil. Fuming nitric acid yields
CeE,Me(NOj)jN(NO,)Bt [72°] (Van Eomburgh,
B. T. C. 3, 402).
Salt.— B'EIaq: [73°]; prisms.
Di-etliyl'i)-toluidine CBB,(CHs).NEtj, [1:4],
"°). S.G. »5 -9242. Formed by heating
ethyl-^-toluidine with EtI (Motley a. Abel).
Prepared by heating ^ -toluidine hydrobromide.
(or hydroiodide) with 2 mols. ( + 6 p.o. excess)
of ethyl alcohol at 150° for 8 hours ; the yield
is 95 p.c. of the theoretical (Belnhardt a. Staedel,
B. 16, 29). Oil. Nitric acid (S.G. 1-6) yields
Cja:,Me(NOj).NEt(NO,) (Van Eomburgh, B. T. G.
3, 408). Diazo-benzene chloride gives
CeB5.N».NEt.CsEjMe [38°] ; diazo-m-nitro-benz-
ene chloride reacts with formation of
[3:1] C8B,(NOJ.N2.NEtC,B,Me [55°]; while
diazo-p-nitro-benzene chloride gives rise to
[4:1] C.E,(NOj).Nj.NEt.C„B,Me [114°] (Noelting
a. Binder, Bl. [2] 49, 81).— B'jBjPtClj : rhombo-
hedra (SSffing, P. B. 8, ,190).— B'BClBgCIj iaq :
triclinio crystals.— B'BBr : monoolinic crystals.
— B'BI : crystalline. — ^B'BNOj : monoclinio
crystals.^
Ethylo-iodide OsEjMe.NEtjI. Beavy
oil. Decomposed by moist AgjO it gives the
strongly alkaline C^B^Me.NEtjOE, whence
(C„B^MeNEt3Cl)2PtCl4 which crystallises from
hot water in slender needles (Morley a. Abel).
ETHYI-DI-TOITI-AMINE v. Di-tolyl-
ETHTL-AMINE.
JETHYI-TOLYIENE-DIAMISE v. Tolylenb-
ETHTIi-SIAMIKE.
ETHYL-TOIYI- v. Tolyl-ethyIi-.
ETHYL-TBOFIC ACID v. tbofio acid under
B-OxY-a-PHENTL-PEOPIONIO ACID.
ETHTL-TTLTBAMABIHE. Prepared by heat-
ing in sealed tubes silver ultramarine and ethyl
iodide, to the solid residue a further quantity of
theiodide isadded and the process repeated until
all the silver is removed. A grey substance,
evolving ethyl sulphide when heated to 100°.
With sodium chloride it forms ordinary sodium
ultramarine and ethyl chloride (De Forcrand,
A. Ch. [6] 17, 564 ; O. B. 88, 30).
DI-ETHTL-UMBELLIC ACID v. Umbeimo
ACID.
ETHiL-UBAUIDO-BENZOIC ACID
C.oEj^NA i.e. NEEt.CO.NB.C„B,.COjBt. From
cyanic ether and m-amido-benzoic acid in alco-
holic solution (Griess, J. pr. [2] 6, 454). Slender
needles. V. si. sol. boiling water, v. e. sol. boil-
ing alcohol. Acid in reaction. — BaA'gSaq:
minute needles. — ^AgA' : laminae.
Be/erence. — Amido-ethii.-dramido-benzoio
ACID.
ETHYL-UBEA CsB.NjO i.e. COrSHMSEEt).
Mol. w. 88. [92°]. S.G. ia 1-213.
Formation. — 1. By the union of cyanic ether
with ammonia (Wurtz, C. B. 32, 414).— 2. By
the union of ethylamine with cyanic acid
(Leuckart, J.pr. [2] 21, 10).
Properties. —Large deliquescent prisms (from
alcohol) ; excessively sol. water, alcohol, chloro-
form, CSj, and boiling benzene. Insol. ether.
At 200° it decomposes with evolution of NBj and
a little NEjEt, leaving a residue containing di-
ethyl oyauurate (Wurtz, Bip. Chim. Pwe, 1862,
199).
Beactions. — 1. Nitrous acid forms alcohol, ni-
trogen, and GO2. NaOB acts in like manner.—
2. A boiling aqueous solution dissolves m^reurio
oxide, and on cooling deposits crystals containing
63-5 p.o. of mercury (L.).— 3. Evaporation with
AgNOj forms silver cyanute. — i. Aniliiie at ISO'
ETTIDINE.
525
forms di-phenyl-urea, NHjEt, and NHj (L.).—
6. Alcoholic KOH at 100° gives potassium
emanate and ethylamine (Haller, SI. [2] 45,
705).
Salts.— B'HNOa: rosettes of thick prisms.
Melts below 60° and then decomposes. Y. sol.
cold water, and alcohol. — B'HCl. Got by passing
HCl over the base at 100°. At 160° it gives off
ethylamine.— B'jHjOjOj: [o. 60°]; rectangular
plates, V. sol. water and alcohol.
Acetyl derivative CONjHjBtAo. [o. 120°].
From ethyl-urea and OLAo. Stout prisms (from
ether). Beadily sol. water, alcohol, and ether.
Sublunes in long needles. Boiled with EOH
it forms potassio carbonate and acetate, NH,, and
NEtH,.
Propionyl derivative
CO(NHEt)(NH.COEt). [100°J. Pine needles.
Sol. water, alcohol, and ether. Formed from
propionamide, Br, and NaOHAq (Hofmann, B.
16, 754).
s-Bensoyl derivative CO(NHEt){NHBz).
[168°] (L.) ; [192°] (M.). From ethyl-urei and
BzCl at 130° (Leuokart, J. pr. [2] 21, 33). Also
from the benzoyl derivative of ethyl-thio-urea by
treatment with ppd. HgO (Miquel, A. Ch. [5]
11, 318). Needles (from water). V. sol. iilcohol,
ether, and hot water.
u-Eenzoyl derivative NHj.CO.NEtBz.
From EtS.CO.NEtBz and cold alcoholic NH,
(LSssner, J. pr. [2] 10, 251). Bhombohedra
(from dilute alcohol). V. o. sol. absolute alco-
hol, m. sol. ether, v. si. sol. water.
s-Di-ethyl-urea CO(KHEt)j. Mol. w. 116.
[10C°] (L. a. H.) ; [109°-l,12-5°] (W.). (263°
cor.).
Formation. — 1. From ethylamine and cyanic
ether. Henoe formed also by the action of water on
cyanic ether (Wurtz, O. E. 32, 414).— 2.^ Formed,
together with cyanic ether, by the distillation
of tri-ethyl-biuret (Limpricht a. Habioh, A. 109,
105).
Properties. — Silky flexible needles (from alco-
hol). V. sol. water, alcohol, and ether.
Reactions. — 1. Gives oS ethylamine when
boiled with potash. — 2. Heated in sealed tubes
at 100° with aloohoUo KOH it gives potassium
oyanate and diethylamine (Haller, Bl. [2] 45,
706).
Salts.— B'HNOj: very acid deliquescent
prisms.
mtrosamine NHEt.OO.NEt.NO. [5°].
Formed by heating di-ethyl-urea with nitroUs
acid (Von Zotta, A. 179, 102 ; B. Fischer, A.
199, 284; B. 9, 111). Tables; si. sol. water.
Decomposed by heat, even below 100% into nitro-
gen, ethylene, and cyanic ether. Gives Lieber-
manu's reaction with phenol and HjSO,. Se-
duced by zino and acetic acid to di-ethyl-semi-
carbazide.
M-Di-ethyl-urea CO(NHj)(NEtJ. [70°]. From
diethylamine and cyanic acid (Volhard, A. 119,
360; A. P. N. Franchimont, B. T. 0. 2, 122).
Crystals, very sweet taste. V. sol. ether and
alcohol. Sol. HNO, with absorption of heat,
but afterwards a strong reaction sets in, and
heat is given out ; COj and a little NjO being
evolved, the liquid then yielding crystals of
nitro - di - methyl - amine (di-methyl-nitro-amide)
(CH3)i:N.N0, [57°].
Tri-ethyl-urea CO(NHEt)(NEtj). [63].
(o. 235°). From cyanic ether and diethylamine ;
formed also by treating triethylamine with vapour
of cyanic acid (Wurtz ; Hofmann, Pr. 11, 273).
Soft crystals, sol. water, alcohol, and ether. It
does not appear to combine with acids. _ Alkalis
convert it into ethylamine, diethylamine, and
COj.
Tetna-ethyl-urea CO(NEtj)j. (205°) (M.);
(210°-215°) (W.).
Formation. — 1. By passing OOClj into a sola
tion of diethylamine in ligroin (Michler, B. 8,
1664).— 2. From Ol.CO.NBt, and diethylamine
(Wallach, A. 214, 275).
PropertMs. — Oil. Dissolves in acids, but ia
reppd. by alkalis.
ETHYL-UEETIIANE v. Ethtti. thiooabbamio
ACID.
ETHYI-VIHYL v. Butinenb.
ETHTL-VINYL OXIDE v. Vinyi. ethyl
OXIDE.
SI-ETHTL-XANTHAmDE o. Eihyl-di-
TEIO-CABBAMIO ACID.
ETHYI-o-XYIENE OeHjMe^Et [1:2:4]. Di-
methyl-ethyl-hemene. (189°). From camphor
and ZnOl, or iodine (Armstrong a. Miller, G. J.
45, 148 ; B, 16, 2258). Also from bromo-o-
xylene, BtBr, and sodium (Jacobsen, B. 19, 2516).
Gives on oxidation CgHgHejCO^H.
Sulphonio aci<Z CsHiMe^EtSOjH. Tables.
— BaA',4aq.
4TOi<JeCsHjMejEtS0jNHj. [126°]. Needles
or prisms (from alcohol).
Ethyl-»rt-xylene OsHsMejEt [1:3:5]. (187°).
S.G. If -869. From ethylidene chloride, AljClj,
and xylene (Anschiitz, A. 235, 323). Formed
also by treating a mixture of acetone and
methyl ethyl ketone with H^SO^ (Jacobsen, .5.
7, 1432); and by treating (l,3,5)-bromo-iylene
with EtBr and sodium (Wroblewsky, A. 192,
217). Bromine forms a tribromo- derivative
[91°]. On osidation it gives uvitic acid
C^HaMefCO^H), [290°].
Ethyl-»t.xylene OaHsMcjEt [1:3:4]. (184°).
S.G. ^ -878. From bromo-»t-xylene, EtBr, and
sodium (Fittig a. Ernst, -4. 139, 184 ; Z.ii] 1,
572). Liquid. Gives a tri-nitro- derivative
[119°].
Sulphonio acid 0,H2Me.^Et.S0jH. Crys-
talline mass (J.). — BaA'j 2aq : trimetric laminse,
m. sol. cold water. — NaA'2aq: minute flat
prisms, v. e. sol. cold water.
^mideCjHsMa^Et.SOjNHj. [148°]. Ne'edles
or prisms (from alcohol).
Ethyl-i)-xylene CaH,MejEt [1:4:3]. (185°). '
From (3,l,4)-bromo-j)-xylene, EtBr, and sodium
(Jacobsen, B. 19, 2516). • It gives a tri-nitro-
derivative [120°].
Sulphonicacid OjHjMejEt.SOaH. Large
trimetric plates (from dilute H«SOJ.— NaA'aq :
tables; m. sol. cold water.— BaA'j: six-sided
plates, m. sol. boiling water.
Amide CsHjMe^tSOjNH,. [117°]. Pearly
plates (from very dilute alcohol); m. sol. cold
alcohol.
Be/ere?ice.— TKI-BEOMO-EIHYIi-XYLENE.
ETHYL-XYLYl v. XYiiTL-BiHYL.
ETTIDINE. A name given by GrevUle
Williams (Laboratory, 109) to a base C,jH„N
obtained by distilling quiuoline with EOH.
526
EUCALYN.
EUCALYN CjH,jO,aq. [o] = about 50°. A
Bweet, Bytupy substance produced, together with
glucose, by boiling melitose CijHjjO,, (the sugar
of the eucalyptus) with dilute sulphuric acid, and
obtained, together with alcohol, by feimenting
melitose with yeast i(Berthelot, A. CK [3] 46, 72).
Dextro-^otatory,andnon-fennentable. It becomes
coloured at 100°, and at 200° it forms a black
insoluble substance. Dilute H2SO4 does not
afiect it. Boiling baryta-water colours it strongly.
It reduces FehUng's solution.
EUCALTFIENE. This name was applied
by Cloez {A. 154, 372) to a hydrocarbon C,^,s 7
(165°) ; S.G. 13 -836; V.D. 6-3, obtained by dis-
tilling eucalyptol with PgOj. The same name
was applied by Faust a. Homeyer (B. 7, 63,
1429), and by Opponheim a. PfafE, {B. 7, 625) to
a terpene (172°-175°), V.D. 68-4, said to occur
in oil of eucalyptus.
EUCAIYPTOL C,oH„0. [1°]. (172°) (V.) ;
(176° i.V.) (J.). S.G. is -923 (J.) ; £ -940. Oc-
curs in the^ oil of Eucalyptus Ohbulus and is
isolated from the fraction 170°-180° by conver-
sion into the hydrochloride (Jahns, B. 17, 2941).
Optically inactive. Probably identical with
cineol. Oamphor-like smell. Oolonrless liquid.
Dry HCl forms the compound (0„H,bO)2H01
(Voiry, 0. B. 106, 1419). KMnOj oxidises it to
cineolic acid 0,„H,b05 [196°] (Wallach, A. 246,
265).
EUCALYPTUS MANNA v. Melitose.
EUCALYPTUS OIL. The essential oil of
Eucalyptus Globulus is a pale-yellow, slightly
dextrorotatory liquid. S.G. -932. At -50° it
solidifies, and the crystals thus formed melt at
-10°. On distillation the first fractions contain
water, formic and acetic acids, and butyric and
valeric anhydrides. At 159° there passes over a
terpene S.G. "88; [o]d=H-40°, which forms a
hydrochlorideO,„H„H01[127°] ; [o]d = 27J°. The
fraction 170°-^175° contains eucalyptol which
constitutes two-thirds of the oil of eucalyptus
(Voiry, O. B. 106, 1419 ; cf. Oloez, A. 154, 372).
According to Faust a. Homeyer {B. 7, 63, 1429)
oil of eucalyptus contains two terpencb (151°) and
(c. 174°), together with cymene and a camphor-
like body C,gH,sO. Oppenheim a. PfaS found in
Australian eucalyptus oil a terpene (173°) whence
iodine produces cymene. Wallach found in the
Australian oil (from E. oMygdalma) cineol and
a Iffivorotatory phellandrene (165°-180°). S.G.
la -855 (Wallach, A. 246, 265).
EUCHBOIG ACID v. Di-imide of Mellitio
icn>'.
EUCHLOBINE. This name was given by
Davy to a gas obtained by the reaction between
HCLAq and KGIO., ; it has been proved to be a
mixture of Cao^ and 01 {cf. p. 12). M. M. P. M.
EUBIOHETEIt. A graduated glass vessel used
in analysis of gases, and in titrimetric analysis
{v. vol.i.pp. 237and248). M. M. P. M.
EUGENOL OuB.,jO,i.e.
[1:3:4] C„H,(OH) (OMe).OHj.CH:OH,. Mol. w. 164.
V.D. 6-4 (oalc. 5-7). (242°) (S.) ; (251°) (Williams)';
(252°) (Gladstone) ; (252° cor.) (Church). S.G.
4 1-068 (W.) ; ^2 1-066 (G.) ; i^ 1-066 (Church,
C. J. 28, 118) ; 2 1-079 (Wassermann) ; m^ i-oes
(Wa.) -, ii 1-070 (Tiemann a. Kraaz, JB. 15, 2066).
Ho 1-540. fiB 1-554.
Odcwrrence. — In oil of cloves ; in oil of bay
{Laurua nobiUs) ; in the oil of cinnamon leaves ;
in oil of pimento ; in oil of, Canella alba ;
and in oil otIUcmmreUgiosum(Bonaatte,A. Ch.
[1827] 35, 274 ; Dumas, A. Oht. 53, 164 ; A. 9,
65 ; 27, 151 ; Ettling, A. 9, 68 ; Bockmann, A.
27, 155 ; Greville Williams, Chem.^ Gaa. 1858,
170; CahoQis, A. Oh. [3] 62, 201 ; Stenhouse, .i.
95, 103 ; Wohler, 4. 47, 236 ; Baeyer, A. 114, 163 ;
Gladstone, C. J. 17, 6 ; Oeser, A. 131, 277 ;
Eykman, B. T. O. 4, 33 ; Eilenmeyer, Z. 1866,
430 ; Wassermann, A. 179, 366).
Formation. — ^By reducing coniferin in weak
alkaline solution with sodium-amalgam ;' coni-
feryl alcohol being an intermediate product
(Tiemann, B. 9, 418 ; Chiozza, C. C. 1888, 443).
Preparation.— Oil of cloves, obtained by dis-
tilling cloves with water, contains eugenol and
a terpene. Aqueous EOH dissolves the eugenol,
and, on again distilling, only the terpene passes
over. On acidifying the residue the eugenol is
liberated.
Properties. — Colourless oil, with spicy odour.
Beddens litmus. Quickly resinifies when ex-
posed to air. V. si. sol. water, v. sol. alcohol,
ether, and HOAc. Has a burning taste. Does
not reduce Fehling's solution. Beduoes am-
moniacal silver nitrate. FeCl, colours its alco-
holic solution blue.
BeacUom. — 1. Distillation over BaO gives an
oU (142°) (Calvi, A. 99, 242; Church, P. M. [4]
9, 256).— 2. Distilled with HI it forms Mel and
a resinous mass having nearly the composition
C„H,„Oj (Erlenmeyer, Z. [2] 2, 430).— 3. Potash-
fusion gives acetic and protocatechuic acids
(Hlasiwetz a. Grabowski, A. 139, 95).— 4. F^Oj
forms a resin, intermediate in composition be-
tween C,^,202 and C,gH,20„ which on distilla-
tion yields a phenol which is coloured green by
FeCl, (Hlasiwetz a. Barth, Z. [2] 2, 83).— 5.
PCI, forms HCl, MeCl, an oily anhydride (?)
(C,gH„0)20,and an amorphous yellow compound
CiJHisPO, ; insol. ether (Oeser, A. 131, 277).—
6. Bromine forms di-bromo-eugenol di-bromide.
(s;.v.) . Acetyl-di-bromo-eugenol crystallises from
ether in hexagonal prisms [66°] (Boyen, B. 21,
1393). The acetyl and benzoyl derivatives of
di-bromo-eugenol dibromide melt at [91°] and
[113°] respectively. — 7. KMnO^ oxidises it to
vanillin, the methyl derivative of protocatechuic
aldehyde. — 8. Vapour of cyanic acid passed
into eugenol forms the crystalline aUophanate
O.H,(OMe)(C,Hs).O.CO.NH.CO.NHj (Baeyer, A.
114, 163).— 9. Phervyl cyanate at 100° forms
Cja,(0,H5)(OMe).O.CO.NHPh [96°] (Snape, B.
18, 2432 ; O. J. 47, 777).— 10. Chloro-acetic acid
acting on sodium-eugenol forms the acid
C,Hs(OMe)(C,H5).O.CH2.C02H [81°], which
crystallises from hot water in long needles, sol.
aqueous Na^CO,. Its sodium salt NaA'l^ aq ia
V. sol. cold water (Saarbach, J.pr. [2] 21, 161). —
11. ilcetocAZor^^ses converts potassium eugenol
into the gluooside C,H,(0.C8H„05)(0Me)C,H,
[132°]. This crystallises in needles, sol. hot al-
cohol, hot benzene, and hot water (Michael, Am.
6, 340).
Metallic derivatives NaC,^„Or —
HK(C,.H„08),aq.— Ba(0,JE„O,), : lamina, si.
sol. cold water.
Acetyl derivative G,H3(0Ac)(0Me).G,Hj.
[31°]. (270°). Prepared by boiling eugenol with
AcoO for three honrs. Crystals ; v. sol. alcohol
and ether, insol. water and oold dilate alkalis.
EUPHORBIUM.
637
Cone. HjSOj dissolves it with deep-red colour.
KMnOj oxidises it to acetyl vanillic acid C,„H,„05
and its bomologue C„H,j05 (Tiemann a. Nagai,
B. 10, 202).
Oarbonyl derivative
(C^,(OMe)(C3H5).0),00. [93»]. Pron> sodium
eugenol and COClj (Lowent)erg, C. C. 1886,390;
C. /. 60, 789).
Benzoyl ■ derivative
OA(OBz)(OMe)(C,HJ : [70°]; monosymmetri-
cal oiystals; si. sol. cold alcohol, insol. -water
(Tiemann a. Eraaz, B. 15, 2067).
p-Methoxy-bensoyl derivative
C^3(0.C0.CA0Me)(0Me}CaHr From eugenol
and anisyl chloride (Cahoors, A. Oh. [3] 52,189).
Crystalline.
Methyl ether C„H,40, i.e.
C,H3(0Me)j.C,H5. (245°). Obtained from
C,Hs(0Na)(0Me).CjH5 and Mel (Graebe a.Borg-
mann, A. 158, 282; Matsmoto, B. 11, 123).
Oxidised by KjCrjO,inHOActoCjH3(OMe)jC02H.
KMnO« gives an acid GijHijOj [163°]. Bromine
gives CsHiBr(0Me)2.CHj.CHBr.CH2Br [78°],
which, in alcoholic solution, is converted by zinc-
dust into liquid C|^2Br(0Me)j.C,H,. A mercury
salt Hg(C„H,302)2 [140°] is formed as a by-pro-
duct in the formation of CeHj(OMe)2(C3H5)C02H
by treatingCsHjBr(0Me)2C0jH with ClCOjEtand
Bodium-amalgam (Wassermann, 0. B. 88, 1206).
Ethyl ether GjjHieOj i.e.
C3H3(OEt)(OMe).C3H5 (254°). S.G. 2 1-026;
m 1-012. From eugenol (50 pts.), KOH (17 pts.),
water (40 pts.), and EtBr (33 pts.) by heating at
100° with inverted condenser (Wassermann,
A. 179, 366). Oil. Gives on oxidation
0,H,(OEt)(OMe).GOjH. When distilled it partly
polymerises, forming crystalline laminiB (from
alcohol) [125'']. Bromine forms G,jH,5BraOj
[80°], whence zinc and alcohol remove bromine,
leaving CuHisBrOj [48°], a product which is not
acted on by AgOAc.
Propyl-ether GsH3(0Pr)(0Me)C8H5.
(264°). S.G. is 1-002. Prom eugenol (100 pts.),
propyl iodide (100 pts.), and £0E (35 pts.) dis-
solved in alcohol. IJiquid, smelling like cloves.
Hot dilute KMnO, gives C5H3(0Pr)(0Me).C0^.
Isopropyl-'ether CjH3(0?r)(0Me).CjHj.
(258°). S.G. iZ-999.
Isobutyl ether G3H3(00H:2Pr)(0Me).G3H5.
(273°).. 8.G. 15 -985. Oxidised by KMnO^ to
C.H,(O0H25r)(OMe).COjH.
Isoamyl ether OsH3(005H„)(OMe).C3H5.
(284°). S.G. iS -976. KMnO^ at 80° forms
C3H/0C3H„)(a^e).C0jH.
Hexyl ether C5H3(0C,H,3)(0M6).0aH3.
(c. 298°).
Allyl ether 0eH3(0C,H5)(0Me).03H5.
(c. 269°). S.G. iS 1-018. From aUyl iodide and
potassium eugenol. A polymeride (284°-290°)
is formed at the same time.
Beneyl ether C^(OC,n,)(OUe).C,B.^.
Partially decomposed on distillation.
Ethylene ether 0,B.,(O.G^{pyL6).0,B.^)t.
[89°]. Formed by heating eugenol, ethylene
bromide, and alcoholic 'EOH in a sealed tube
(Cahours, C. B. 84, 157, 1195). Micaceous plates ;
insol. water and cold alcohol, sol. hot alcohol and
ether. KMnOj oxidises it to
C,H,(0.0.H3(0Me).C0jH)r
Trimethylene ether
C.H.(0.03H3(OMe).03HJ,. [83°]. Prom
OHjBr.CHj.CHjBr, potaseium-eugei^ol, and a
little alcohol at 100°. Satiny crystals (from
ether) or prisms (from alcohol). KMnO, gives
C3H,(0.03H3(OMe).CO,H),.
Propylene ether ■
C3^3(0.0,H3(OMe).03H3),. [o. 58°].
Prepared as above, using propylene bromide
CH3.CBffir.CHjBr (Cahours). Needles (from
ether).
Beferences. — Beomo-ebqenol and Niibo-
BCGENOL.
Iso-eugenol CjH,(0H) (0Me)(CH:0H.CH3)
[4:3:1]. (c. 260°). V.D. (H = l) 82-66 (obs.).
S.G. iS 1-08. Formed by splitting off CO^ from
homoferulic acid by heating to c. 250° or 300°
(Tiemann a. Eraaz, B. 16, 2064). Oil. Dis-
solves in H2SO4 to a red solution. FejClj pro-
duces a light-green colouration, turned violet by
NH3.
Benzoyl derivative
C3H3(OBz)(OMe)(C3H3). (160°).
EXTGETIC ACID ChH^O^ i.e.
C3H,(OMe)(OH)(G3H3)(C025[) [3:4:1:5]. [124°].,
Formed by dissolving sodium in eugenol and
passing COj over the resulting sodium eugenol
7Scheuch, A. 125, 14). Long colourless prisms
(from hot water); si. sol. cold water, v. sol. alco-
hol and ether. Its aqueous solution is coloured
blue by FeClj. The acid is resolved by heat into
CO2 and eugenol.
Methyl derivative
C3H2(0Me)j(0,H5).C0jH. [180°]. Formed by
saponifying its ether, which is produced by treat-
ing the methyl derivative of bromo-eugenol with
ClOOjEt and sodium-amalgam (Wassermann,
O. B. 88, 1206). Flat yellow needles ; si. sol.
water, v. sol. alcohol and ether. Gives on oxi-
dation by KMuO^ an acid [163°].
ETILYSIH C^iHjjOj. A substance which may
be extracted along with oerisin and decacryUc
acid from cork by boiling with alcohol. It is v.
sol. alcohol, but insol. water (Siewert, ' Z. 1868,
388).
ETJLYTE C,H,N,0,. [99-5° cor.]. S. -01 at
10°. Formed, together with dyslyte, by treating
citraconic acid with strong nitric acid (Baup, A.
81, 96 ; Bassett, O. J. 25, 98). Bulyte is the
more soluble, it crystallises from chloroform in
large dimetric crystals. Heated with alcoholic
KOH it forms ENOj and a brown resin soluble
in alkalis. Tin and HOI give NH3 and a volatile
base smelling like picoline.
ETTOmTMnf. A bitter resin obtained from
the oil of the spindle-tree, Euonyrrms europmVjS
(Biederer, Bv/ih. Bep. 14,. 1 ; Grnndner, Buch.
Bep. 97, 315). Insol. water, sol. alcohol and
ether, separating from the latter in warty crys-
tals.
The same name is given by Bonun (0. C.
1885, 442 ; C. J. 50, 72) to a gluooside which
may be extracted by dilute alorhol (70p.c.)from
the rinds of Euonynms atrcpwrpureiis. It may
be crystallised from ether.
EUFHOBBITTM. A resin consisting of the
concrete juice of several species of Euphorbia
growing in hot climates. ^ Cold alcohol extracts,
according to Johnston (J.pr. 26, 145), a brown- .
ish-red resin CaiH3„03, icsol. alkalis, but dis-
solving with red colour in concHjSO^. BoiUng
alcohol extracts from the residue another resin
C^gHjjO,, which separates in indistinct crystals
638
EUPHOKBIUM.
(H. Rose, P. 33, 33; 53, 865; Fluckiger, J.
1868, 809). Acoording to Henke {Ar. Ph. [B] 24,
729) euphorbium contains, besides eupjhorbone,
two resins, one soluble in ether, the other not.
EUPHOEBONE OjoHajO. [68°]. [o]d = 15-9°.
S- 'Ol (hot). Extracted from euphorbium by-
light petroleum at 70° and crystallised from al-
cohol-ether (Henke, Ar. Ph. [3] 24, 729; c/.
Fliickiger, Z. [2], 4, 221). Brilliant crystals,
persistent in the air, tasteless, and neutral in
solution. V. sol. light petroleum, chloroform,
ether, alcokol, benzene, and acetone. Kot af-
fected by dilute acids, alkalis, or ACjO. Heating
with PjOj gives heptane, octane, and xylene.
According to Hesse (A. 192, 193) euphorbone is
C.sHjjO [114°], [a]D = 18-8° at 15° (in chloro-
form) ; or 11-7° (in ether).
EUPITTONIC ACID O^K^fi,. [about 200°].
Occurs amongst the products of oxidation of
wood-tar oil (Liebermann, B. 9, 334; Gxatzel,
B. 11, 208S). Prepared by heating the dimethyl
ether of pyrogallol with CjGl, and alcoholic KOB.
(Hofmann, B. 11, 1455). Formed also by heating
a mixture of the di-metbyl ethers of pyrogallol
(OjH3(OMe)20H) and of methyl-pyrogallol
(Me.CBHj(0Me)20H) with NaOH at 210°, hy-
drogen being liberated (Hofmann, B. 12, 1877).
Long fine orange needles. Difficultly soluble in
boiling alcohol, easily in acetic acid. Alkaline
solutions are deep blue. By an excess of alkali
blue salts are precipitated. HCl at 100° gives
pyrogallol and HeCl. Alcoholic SB., at 170°
gives crystaUihe G29H„K,0,. Water (2 pts.) at
265° gives OjH3(OMe)20H and a crystalline body.
Salts. — NafiiiH^fiiXaq : prisms. —
BaCisHg^Og xaq : needles.
Di- acetyl derivative C2iiHj40,(OAo)2 :
[265°]; yellow needles.
Di-benzoyl derivative 025H240,(OBz)2 :
[232°] ; small yellow needles. Insol. alcohol,
sol. chloroform.
Methyl ether G2^B.ifl,{0M.e)2 \ [242°];
yellow needles.
•Ethyl ether 0,^^.^0,(0^)2: [242°] ; yellow
needles.
Periodide OjsHjjObI,: brown glistening
prisms (Hofmann, B. 12, 2216).
EVBHOXIINES is the name given by Witt to a
class of red colouring matters which have the
constitution of amido-quinoxalines. These bodies
are produced : (1) By the action of a tri-amine
(amido-o-diamine) upon a qtiinone or di-ketone.
(2) By heating an o-amido-azo- compound with
(ii)-naphthylamine hydrochloride. Quite recently
(B. 21, 2418) Witt has proposed to extend the
meaning of the term eurhodine so as to include
all poly-amido-derivatives of azines.
The eurhodine from o-amido-azo-toluene and
(a)-naphthylaim]ie has the constitution :
.0(NH2):CH
A-
-N
\/
C,H,(CH,)
(amddo-naphthylene-tbhiguinoxalin or amido-
tolu-rMphthazime). This compound crystallises
from aniline or phenol in dark orange needles,
almost insol. alcohol and ether. It may be sub-
limed. Its hydrochloride C„H„K3HClaq
forms garnet-coloured needles. Cone. HjSO,
dissolves it with intense red colour turned greeB
and then scarlet on gradual dilution. It dyea
silk scarlet in an acid bath. The tartrate dyes
cotton mordanted vrith Turkey-red oil a colour
similar to Turkey-red (Witt, O. J. 49, 391 ; B.
IS, 1119; 19, 914) ; ethyl nitrite decomposes the
eurhodine in alcoholic solution, one product
being lemon-yellow needles 0,,H,gN20 i.e.
0„H„BtN20 [175°].
The eurhodine &om (j3)-naphthylainine is
formed on adding quinone diohlorimide to (;S).
naphthylamine dissolved in alcohol the solution
becoming red and, on adding water, a eurhodine
CijHj.Nj.OsHjNHj (or, more probably;
C,gHj(NH2).N2.CsH4) separates. This crystallises
from benzene in dark yellow needles, m. sol.
alcohol and benzene, v. sol. aniline. Its alcoholia
solution is converted by nitrous acid into naphtho-
phenazine (Nietzki a. Otto, B. 21, 1598).
A di-methylated eurhodine
0,oH,.N2.08H3NMe2 [| 4] [205°] is formed by
heating nitroso-di-methyl-aniline hydrochloride
(3 mols.) with a solution of (i3)-naphthylamine
(2 mols.) in HOAc (Witt, B. 21, 719).
EUXAKTHIC ACID 0,sH,sO,„. Pwrreia acid'.
The .magnesium salt constitutes the essential
part of Purree or Indian yellow, said to be ob-
tained by evaporating the urine of cows fed on
mangoes (Stenhouse, A. 51, 423; Erdmann,
J. pr. 33, 190 ; 37, 385 ; Baeyer, A. 155, 257).
Purree is boiled with water and the residue ex-
tracted with dilute HGl ; on cooling the euxanthia
acid separates in stellate groups of needles.
Euxauthio acid is also excreted in small quan-
tity by a rabbit after taking euxanthone (£os-
tanecki, B. 19, 2919).
Properties. — Pale-yellow needles, containing
aq when crystallised from alcohol, but 3aq when
ppd. by HGl from its ammoniacal solution. It
has a sweet taste and a bitter aftertaste. It is
si. sol. cold water, v. sol. boiling alcohol, m. sol.
ether. Alkalis colour its solution deep-yellow.
When cautiously heated at 170° it gives o& water
and GO2, leaving a yellow sublimate of euxan-
thone. Alcohol and HOI also give euxanthone.
HNO3 gives tri-nitro-euxanthone. and tri-nitro-
resorcin. By heating with dilute H2SO4 (2 p.c.)
at 140° it is split up into euxanthone and glycu-
ronic acid (Spiegel, B. 15, 1965).
Salts. — The enxanthates of the alkalis~are
y. e. sol. water, but are ppd. by excess of alka-
line carbonate. The euxanthates of Ba, Ca, and
Mg are si. sol. cold, v. sol. hot,' water. The basic
Mg salt which occurs in purree is insol. water. —
NH,HA"aq: light-yellow needles.— KHA" aq.—
MgA" 9aq? : occursin purree.— PbH2A"2.—PbA".
Pl-bromo-enzanthic acid GigH^BrjOig. Minute ,
golden-yellow needles (oontainiug aq).
Di-chloro-enzantMc acid C„H,«Cl20,v
Formed by passing 01 into water in which
euxanthic acid is suspended. Golden scales ;
insol. water, V. sol. boiling alcohol. Its salts are
mostly gelatinous.
Nitro-euzanthic acid C,gH„(N02)0„. From
the acid and ooldHNO, (S.G. 1-31). Straw
coloured lamines (from alcohol).
EUXANTHONE O^JSfi, i.e.
0<q^»|qS>CO or more probably
EVEENINIO AOID.
529
CA(OH)-0
I I . [232°]. V.D.8-0{ealo. 7-9). A
CeH,(OH)-CO
product of the decomposition of euxanthic acid
(Stenhouse, A. 51, 425 ; Erdmann, A. 52, 365 ;
60, 239; Schmidt, A. 93, 88; Graebe, B. 16,
864). It is produced by heating the acid or its
Ba or Pb salt ; by treating the dry acSd with cone.
HjSO, ; or by treating its alcoholic solution with
HOI. Pale-yellow needles or lamina (from
alcohol) ; v. si. sol. water, v. sol. ether, si. sol.
alcohol (Kiilz, Z, B. 23, 475). It may be sub-
limed. It is neutral in reaction, dissolves in
alkalis, but not in dilute acids. The alcoholic
solution is ppd. by lead subacetate, but not by lead
acetate, baryta, or lime. FeClj gives a green
colour. Does not react with hydroxylamine or
with phenyl-hydrazine (Spiegler, B. 17, 808).
BeacHons. — 1. Nitric acid forms tri-nitro-
euzanthone and tri-nitro-iesorcrin. — 2. Passing
over heated zimo-chist forms CH2<[|^'=S:»^0 and
other products. — 3. Potash-fusion gives hydro-
quinone aijd euzanthonic acid (Baeyer, Z. [2] 5,
569).-74. Sodium-amalgam gives a colourless
compound which turns violet-black in the air
(Wichelhaus a. Salzmann, B. 10, 1398).
Salts. — ^A"Mg: insol. water, nearly insol.
alcohoL
Methyl ether A"Ue^: [130°]; yellow needles
or prisms, sol. alcohol and etiier (Graebe a.
Ebrard,'B. 15, 1675).
Ethyl ether A."E%: [126°]; long colourless
or yellow prisms, sol. alcohol and ether.
Acetyl derivative CjsHjACjO,: [185°];
yellowish prisms (from benzene); sol. alcohol,
si. sol. ether.
Benzoyl derivative : [214°] ; yellow crys-
stals, sol. aniline, insol. alcohol, ether, benzene,
&e.
Constitution. — Euxanthone is clearly a
' di-oxy- derivative of the so-caUed di-phenylene
ketone oxide, but as this substance does not
react with hydroxylamine, Spiegler suggests that
0.H,.0
it should be represented by the formula I I
O.Hi.CO
rather than C0<^«^*>0.
, Di-chloro-euxanthone C^^SgClJO,. From di-
chloro-enxanthio acid by dissolving in cone.
IIjSO, and ppg. by water (Erdmann, J. pr. 37,
397). Yellow powder.
Tri-nitro-enzanthone 0,3H5(N02)s04. From
euxanthone and HNO3. Minute yellow needles.
Further treatment with HNO3 gives tri-ijitrO-
resorcin. NH, forms reddish-black grains of
c„h,(nh,)(n6,)30,.
C3H,(0H).C0
Iso-euxanthone | { . Lactone of
C3H3(OH).0
tri-oxy-di^henio acid. [243°]. Obtained by
heating di-oxy-benzoic acid (iS-resoroylio acid)
with acetic aiUiydride ; the yield is about 4 p.c.
(Bistrzyoki a. Kostanecki, B. 18, 1986). Small
needles. V. sol. alcohol, ether, and aqueous al-
kalis forming yellow solutions, insol. water._ Sub-
limes in long yellow needles. FejCl, gives a
greyish-green colour. The alcoholic solution
gives a yellow pp. with MgSO^ Treated with
voL.n.
sodium-amalgam and water it dissolves with a
blood-red colour.
ETTXANTHONIC ACID 0„H,„Os i.e.
[i i]C3H3(0H)j.C0.03H3(0H)j[i|]. Tetra-oxy-
bensophenone (?). Formed from euxanthone by
potash-fusion (Baeyer, A. 165, 259). Yellow
needles (from water). Forms a reddish-yellow
pp. OijHjPbjOs with basic lead acetate. Its so-
lution in potash rapidly oxidises in the air,, be-
coming dark. FeCl, colours it red. Eesolvedby
heat into water and euxanthone, which sublimes.
Boiling aqueous NH, also forms euxanthone.
Potash-fusion converts it into hydroquinone
(Graebe a. Feer, B. 19, 2607).
EVEKNIC ACID 0„H,30,. [164°]. Obtained,
together with usnio acid, by macerating the
lichen Evemia prunastri with milk of lime and
ppg. the filtrate with HOI ; it is extracted from
the dried pp. with boiling alcohol and ppd. by
water (Stenhouse, A. 68, 83; Pr. 18, 222).
Groups of small needles (from alcohol). Insol.
cold water, v. sol. cold alcohol and ether. It
does not decompose solutions of NaHCOg in the
cold; its Ca salt is decomposed by OO,. De-
composed by boiling with water or baryta-water
into CO3, oroin, and everninic acid.
Salts. — ^BaA'^aq; small prisms, si. sol. cold
water, v. sol. dilute alcohol. — KA' : silky crystals,
si. sol. cold water, v. sol. dilute alcohol and
aqueous KOH.
Tetra-bromo-evernip acid 0„H,jBriO,. [161°].
From dry evernic acid and dry Br. Colourless
prisms (from alcohol) ; insol. water and OSj, si.
sol. hot benzene, v. sol. ether.
EVEENIIS 0„H, A (Stiide, A. 131, 241). A
substance extracted from. Evemia prunastri and
related to the sugars. The plant is macerated
with cold dilute soda-ley till the liquid acquires
a dark-green colour ; the filtrate is mixed with
alcohol ; and the brovm flocks thereby precipi-
tated are redissolved in water and purified by
repeated precipitation and boiling with animal
charcoal.
Everniin is an amorphous, yellowish, taste-
less powder, which swells up in cold water and
dissolves easily in hot water. Its aqueous solu-
tion gives with lead acetate and ammonia a pp.
soluble in acetic acid. It is ppd. by a large ex-
cess of glacial acetic acid. It prevents the ppn.
of lead by EjS or sulphuric acid, a property
likewise possessed by glycogen, inulin, lichenin,
and gum. Everniin is not coloured by iodine.
DUute acids easily convert it into glucose.
A substance closely related to, or perhaps
identical with, everniin is obtained from Borrera
EVEENINIC ACID C,H,A; 1157°]. Formed
by decomposing evernic acid with caustic alkalis
(Stenhouse,.i. 68, 86 ; Hesse,.^. 117, 299). Best pre-
pared by boning evernic acid with baryta water ;
BaCOj is ppd., and the filtrate, treated with HCl,
gives a pp. of everninic acid. LaminsB, si. sol.
cold, m. sol. boiling, water, t. e. sol. alcohol and
ether. FeCl, colours its solution violet. Cone.
HNO3 forms evernitio acid 0,Hg(N0j)j04 <"
CgH5(N02)30a? which forms pale yellow prisms,
si. sol. cold, m. sol. boiling water, and forms a
crystalline potassium salt C9H,Kj(N0i)j03 ^aq ?
(Hesse). Evernitic acid is perhaps di^nitro-
everninic acid. Everninic acid differs from ever-
MM
630
EVERNINIO ACID.
nio acid in not yielding oroin when boiled with
potash.
Salts.— Ba(OsHg04)22aq: long four-sided
prisms, nearly insol. alcohol. — AgA' : white pp.
Ethyl ether EtA'. [56°]. 'Prom evernio
Beid by boUing for 9 hours with strong alcohol,
or with alcohol containing KOH. Long colour-
less crystals (from alcohol), insol. cold, nearly
insol. boiling, water, v. sol. aloghol and ether.
Dissolves in aqueons KOH but not in aqueous
NH, or KjCO,.
JBXCBEMENT. Berzelius {Lehrbuch, [4] 9,
340) found in human feeces: water, 75-3 p.c;
bile, '9 p.c. ; alhumen, '9 p.c. ; soluble organic
matter, 2'7 p.c; salts, 1-2 p.c. ; insoluble residue
of digested food, 7'9 p.o. ; insoluble organic mat-
ter (mucus, bile-resins, and fat), 12 p.c. Human
excrement, acidified by H2S04, yields on distil-
lation acetic, n- and iso-butyrio, valeric and
caproic acids, phenol, indole, and skatole (from
<rKaT(is = ffflces) (Brieger, J. i)r. [2] 17, 124). V.
also Wehsarg, Vntersuchung. der Fcsces, Giessen,
1853; Porter, A. 71, 109 ; Fleitmann, P. 75,
,356; Maroet, T. 1854, 265; 1857, 403; O. J.
10, 162 ; Harley, Pr. 7, 122.
Thenard (0. B. 44, 980) found in fermented
manure an acid C3jH3jN20,j, which ma^ be ppd.
from an aqueous extract by HCl. It is a black
mass, insol. water, v. si. sol. alcohol and ether.
EXCEETIN CjoHssO (Hinterberger, A. 166,
213 ; cf. Marcet, Pr. 9, 308). Obtained by ex-
hausting fresh excrements with boiling alcohol
and leaving the solution to stand for a week. A
black pp. then separates out, containing excretin
and the salt CsjHusMgNO,!. The filtrate is ppd.
with milk of lime, and the dried pp. treated with
a hot mixture of ether and alcohol. On expos-
ing the solution during a week to a temperature
below 0°, crude excretin crystallises out in semi-
globular masses consisting of yellow needles. It
is purified by crystallising it repeatedly from al-
cohol, with addition of blood-charcoal, the tem-
perature being kept below J3°. Broinine converts
it into di-bromo-excretin, Cj^Hj^BrjO, which sepa-
rates from a mixture of ether and alcohol in hard
brittle crystals grouped in globular masses. A
crystalline chlorine-compound could not be de-
tained. 100 pounds of fresh excrements yielded
8 grams of pure excretin.
EXPLOSION'. If a system is in such a condi-
tion of physical or chemical equilibrium that a
variation of that condition involving a transfo;:-
mation of energy,' and initiated at any one point,
will spread rapi(Uy through the system of its
own unaided action and without the supply of
energy from without, then the system itself is
said to undergo explosive change, and the
change itself is called explosion. If the velocity
of change is small the explosion becomes a com-
bustion ; if large, a detonation.
BlBLIOQBAfBZ.
Abel, T. 1866, 1867, 1869, 1874; O. B. 1869,
1872, 1877; Pr. 1864, 1867, 1869, 1874; P.B.I.
1864, 1866, 1872 ; 0. J. 1867, 1870 ; P. M. 1866,
1867.
Abbot, ' Submarine Mines and Explosions.'
Berthelot, Sur la force des matures explo-
tims d^apris la Thermochemie, 2 vols., 1888 ; a
complete account of French work up to the date
of publication ; since then v. 0. B. 98 and 99;
A. Oh. 1885.
Bucknill, Engineering, 1887, 1888.
B'unsen, ' Untersuoh. liber die ehemische Ver-
wandsohaft,' A. 1883 ; v. also list in Dixon, T,
1884.
Clerk, Oas Engine, Longmans, 1887.
Davy, T. 1816, 1817.
Dixon, r. 1875, 1884. ,
Drinker, ' Explosive Compounds ; Machine
Eock Drills and Blasting,' Wiley & Sons, New
York,
Eissler, ' Modern High Explosives,' Wiley &
Sons, New York, 1886.
Horstmann, v. Dixon's list in T. 1884.
Janet, A. M. 1885 (a translation of the report
of the Prussian Commission on Explosions in
Coal Mines).
Klobb, A. Ch. 1877.
Maoh a. Wentzel, W. 1885.
Mallard a. Le Ghatelier, v. Berthelot'H book
up to 1883 ; since then A. M. [8] 4, 1888.
Meyer, v. Dixon's list.
Noble,P. iJ. I. [6] 1871.
Robins, C. B. 1887, 115.
Eumford, T. 1797.
Sarrau a. Vieille, v. Berthelot's book up to
1883 ; and since then with Berthelot, v. above.
Sprengel, Patent Eeports.
Threlf all, P. ikf. 1886.
Von Oettingen a. Von Gemet, W. 4, 1888.
From considerations of economy of space the
following account of the vast mass of work which
has been done in connexion with the theory of
explosions has been compressed as much as
possible.
BxpLosioK OF Gases. — First really studied
by Davy, and leading to the invention of the
safety lamp ; afterwards by Bunsen, Horstmann,
Berthelot, VieUle, Sarrau, Mallard and Le Gha-
telier, Dixon, Clerk {Oas Engine, Longmans,
1887), and Von Oettingen and Von Gemet. The
latter found {W. 4, 1888) that when a eudiometer
tube is filled with water-gas (H^ + 0) and explosion
is induced by an electric spark, the luminosity is
sufficient to enable a photograph to be obtained
when the dust of some copper salt is distributed
in the tube. By an ingenious combination of
apparatus the flash can be reflected from a rota-
ting plane mirror, and a real image of the ana-
lysed phenomena thrown on a sensitised plate
(Eastman's negative) contained in a camera. It
appears from, a study of the picture obtained that
the explosion is really very complex. The photo-
graphically active illumination does not occur
till -001 sec. after the passage of the spark, this
represents the time required for the copper salt
dust to become luminous. The explosion, how-
ever, is shown to be practically over by this
time. The photographs show waves of compres-
sion (indicated by excessive luminosity) to be
travelling up and down the tube. There is also
some indication (not convincing) of successive
partial explosions taking place at periods of
about -OOOl" to -0002". Bunsen has suggested
(P. 1867) that the temperature at first attained
is so high as to prevent complete combination,
or in other words to cause dissociation of steam,
and that as cooling takes place a number Of
secondary explosions occur until the combina-
tion becomes complete. These supposed sac-
EXPLOSION.
531
cessire explosiona ate indicated by secondary
waye-markings in the photograph. The explo-
sivo velocity appears to be about 2,800 metres
per second, and the velocity of the pressure
waves about 600 metres per second. If the tem-
perature reaches 3000°O., as indicated by Berthe-
lot, sound would travel through the gas with a
Yolooity of 1,160 metres per second ; the result
therefore shows (assuming the reasons given for
identifying the observedwave with waves of com-
pression to be valid) either that 3000°C.is far too
high a temperature, or that the displacements in
the wave inotion are such that the velocity is
less than the velocity of sound, which is unlikely.
Probably the conditions are such as to preclude
any comparison with the velocity of sound under
ordinary conditions ; even supposing the adiaba-
tio condition to be reaUy fulfilled (but from the
mere fact of the possibility of photographing we
know this cannot be the case) there is room for
great' speculation as to the value oiy. Again,
Eundt finds that powder in the tube has con-
siderable effect even with small disturhanoes, and
that in narrow tubes the velocity diminishes
both with the diameter of the tube and with the
wave length of sound (v. Eayleigh'a Soumd,
vol. 2, pp. 26-54). Besides all this, the displace-
ments are probably so large as to render the or-
dinary equations unavailable. The whole of the
photographically luminous phenomena are over
in '004 seconds. These researches, however,
require confirmation.
The further stages have been investigated by
other philosophers. In 1867 Bunsen published
an account of some experiments he had made
to determine the maximum pressure due to
an explosion as well as the velocity with which
explosion proceeds in gases. By estimating the
heat produced during any explosion — which may
be done from thermo-chemical data — and as-
suming that the specific heat of the products of
combustion is either constant, or varies in some
assumed way, it is clear that the maximum
pressure produced may be calculated by assum-
ing Boyle's Law or any modification of it — of
course on the further assumption that no heat
is lost from the exploding mixture before the
maximum pressure is attained. Bunsen found
that in certain explosive mixtures tested by
him the theoretical pressure was never even
approximately attained. The pressure gauge in
Bnnsen's experiments consisted of a sort of
safety valve loaded to a known extent. Now it
is clear, from the study of the equation of motion
of such a valve, that much will depend on the
period during which it is subjected to the high
pressure ; in fact to get a satisfactory result we
ought to take into account the period of time
during which the gases are rising to their real
maximum of pressure. This period was an un-
known quantity till Sarrau a. Vieille and Ber-
thelot determined it about twelve years later.
However, Bunsen concludes from his experiments
that the reason for the calculated maximum
pressure not beihg attained in his apparatus is
,to be sought in the dissociation or rather post-
poned combination of the explosive gases. ,_Bun-
sen also attempted to measure the velocity of
combination by allowing the mixed gases to
stream out by a narrow hole, and finding the
least possible velocity whiob vrould prevent ex-
plosion ru;an{ng back into the reservoir. The
assumption made is that when the velocity of
efflux equals or exceeds the velocity of explosive
propagation the flame will not run back. This
we know cannot be true because of the conduc-
tivity of the material through which the jet
passes ; and besides this there is the cooling of
the jet by expansion to be considered, tending
to cause the rate of combination thus obtained
to refer to gases at an undiscovered temperature.
For water-gas Bunsen got a velocity of 34 metres
per second, and for a mixture of equal volumes
of carbon monoxide and oxygen he obtained the
rate of one metre per second at atmospheric
pressure. Mallard and Le Ghatelier {A. M. 8,
[1871]) show that for different mixtures the ve-
locity becomes much smaller if an excess of one
component is employed, or if an inert gas be
present ; they also show that much depends on
the mode of inflammation. With the chemical
ideas we shall have to deal later on. The real
measure of the velocity, as well as of the later
phenomena of combination, we owe to Dixon (T.
1884, ' On Conditions of Chemical Change iu
Gases '), to Sarrau and Vieille, and to Berthelot
(Berthelot, TraiU sur la force des matUres ex-
plosives). The works in question are happily
easily accessible, and therefore a mere summary
will suiHce here: —
1. The iaitial velocity of explosion depends
on the diameter of the tube, on the pressure of
the gases, on the initial mode of inflammation,
and on the temperature of the iuixture.
2. If the pressure is not too low and the
diameter of the tube not too small, the reaction
velocity will be accelerated, and will finally rise
to a certain value which is henceforth pretty
constant.
3. This velocity is independent of the nature
of the material of the tube, and of its length,
provided this is above the ' critical value ' re-
quired to enable the so-called explosive wave to
get estabhshed. The same remark applies to
the diameter of the tube.
4. The velocity of the explosive wave does
not depend on the pressure between the limits
investigated, nearly to an atmosphere.
5. Theinfluence of the chemical nature of the
mixture is diffloult to estimate, because in vary-
ing the composition, the disengagement of heat,
and consequently the maximum temperature,
varies. In fact the velocity approaches the
velocity of molecular motion (of translation)
calculated by Clausius and given by his formula
V= 29-354
\/}
where T is absolute temperature on the thermo-
dynamic scale, and p is the density of the gas
referred to air (it is the density of the products
of combustion that should be taken, but as un-
known dissociation intervenes this is often
difficult to estimate). The approximate agree-
ment of this formula with the observed velocity
suggests that very possibly it may afford a better
means of measuring the real absolute tempera-
ture in the explosive wave than the thermo-
chemical data actually employed. For although
the same uncertainty exists as to the value of
e we need make no assumption as to the specific
MM 2
632
EXPLOSION.
heat of the gases at "the high temperature
attained.
6. The explosive wave may be initiated at
onoe by using a suitable detonator of mercury
fulminate. Berthelot used fulminating electric
interrupters to obtain registration on his chrono-
graph. Dixon used similar interrupters without
the fulminate, and found that Olausius' formula
gave good results when the gases were wet. In
fact the dryness or wetness of the gases is im-
portant for most mixtures, but not for water-gas.
Berthelot and Vieille used a falling rod chrono-
graph, Dixon a myograph. Dixon finds that in
mixtures of carbon monoxide and oxygen the
reaction products depend on the velocity of
explosion, i.e. on the temperature obtained;
carbon may even be deposited at high velocity.
Similarly Berthelot and Vieille succeeded in
completely decomposing acetylene into carbon
and hydrogen by starting the wave with mercury
fulminate. Finally Sarrau and Vieille (C. B.
105, 1222-4) find that the final equilibrium in
many exploded gaseous mixtures depends on the
pressure obtained; which in turn depends on
the density of charge. Density of charge is
defined as
charge in grams
vol. available for explosion in cubic centimetres.
The following table will give an idea of the
results obtained by Messrs. Berthelot and Vieille ;
the remarks are from Dixon's paper : —
N-^
IS.
>»o
>.
Mixture
Ill
IP
?3
II
11
g5
Kemarks
H»+0
■622
6780°
2831
2810
Wet or dry.
00-hO
1-629
ej'oo''
1941
1089
Dry ; when wet
agrees better.
C,H,+50
1-227
1007°
2660
2482
CA-i-30,
1-075
7880°
2517
2209
0.N.-H20.
1-343
9660°
2490
2196
Does not explode
dry at ordinary
pressures.
Mach and Wentzel {W. [1885] 26, 628) have
investigated the velocity of decomposition of
silver fulminate piled in a heap in free air.
This they did by an ingenious method of firing
two linear parallel heaps of fulminate on, or at
the edges of, a plate of smoked glass. The heaps
of fulminate were of equal length and were
ignited simultaneously at opposite ends by the
discharge of a Leyden jar. On examination, the
smoked glass showed markings due to the
motion of the air caused by the explosion. The
authors note particularly a line which appears
to be straight and inclined at an angle to the
parallel heaps. This is supposed to be the
line representing the locus of points of equal
time with respect to the detonating heaps. If
the velocity of the considerable aerial disturb-
ance be taken at 400 metres per second, then by
Huyghens' principle
400
metres per second,
where V is the velocity of ignition sought for.
An experiment gave V>1,700 metres per second
and <2,000 metres per second. ,
Notes as to chemical changes. — Bunsen, ex-
perimenting with a mixture of oarbQn inonoxide,
hydrogen, and oxygen (too little for complete
combustionyTconcluded that the ratio of water
to carbon dioxide formed did not vary continu-
ously, but by sudden jumps. Bunsen also found
that the more rapid the combustion the more
water and the less carbon dioxide was pro-
duced. Horstmann, by using pretty long tubes,
got numbers from which he deduced a theory of
the coefficient of affinity. Dixon discovered that
for uniform results it is necessary that the pres-
sure should be above the 'critical pressure.'
This ' critical pressure ' is the pressure beyond
which length of tube has no effect on the result ■
it is higher the less explosive is the mixture. For
instance, wet carbon monoxide with 12 p.c. of
free oxygen has a ' critical pressure ' of 400 mm.;
if there is 19 p.c. of oxygen the ' critical pres-
sure ' falls to 200 mm. The ' critical pressure '
is then the pressure above which the true ex-
plosion takes place. When the pressure ia
above the ' critical pressure,' and when the pro-
ducts of combustion are prevented from leaving
the sphere of action by condensation or other-
wise, and no inert gas is present to lower the
temperature, and there is less hydrogen than
twice the volume, of the oxygen, then the co-
efficient of affinity (to be defined below) remains
constant and is equal to 4 ; or in other words
the ratio of burnt to unburnt gas is constant.
A typical case is a mixture of carbonic oxide,
hydrogen, and oxygen.
2H, + 0, = 2H.,01
Direct actions are
2CO + 0, = 2CO.
}■■
reverse actions are H' + 00,=H,6 + cd /•
If H is the number of molecules of steam, H'
the number of molecules of hydrogen, K' the
number of molecules of carbon monoxide at the
beginning of the reaction, and E the number of
molecules of carbon dioxide at the end of the
K'H
reaction, then ■ — -. = a the coefficient of affinity.
KS
For real information on these points the
paper must be consulted. We can also do no
more than refer to the very important experi-
ments made by Mallard andLe ChateUeron the
pressure produced by gaseous explosions {A. M.
[8] 4, 272 [1883]), These philosophers used a
Bourdon gauge indicator, and obtained a dia-
gram showing the rate of cooling of the gases
of explosion. The experiments of Clerk (l.c.)
were directed to the practical application of
gaseous explosions in gas engines; his appa-
ratus consisted of a Bichards' indicator with a
drum travelling at constant speed; and his
results are of a definite practical importance.
Liquids akd Solids. Oeneral phenomena, —
For purposes of convenience the solid explosives
are generally divided into two classes: one
typified by gunpowder, the other by detonated
gun-cotton. The first class is for the most part
occupied by explosive mixtures ; the second by
explosive compounds. An accurate piacticu
distinction may be made between those sub-
stances in which detonation may be produced
as easily as in gun-cotton, say, and those in
which it cannot be so easily produced. The
general phenomena common to both clashes of
explosives are : —
1. A rapid chemical change attended by in-
EXPLOSION.
533
crease of volume and production of heat (this
excludes such cases as the action of tartaric
acid on sodium carbonate where heat disappears) .
2. A dependence of the rate, and hence
generally of the nature, of the decomposition
on the greater or less facility which the pro-
ducts have for escaping from the seat of the
reaction. This information we owe to Abel.
3. If the substance is inclosed in a confined
space the final pressure of the products wUl de-
pend on the ratio of the volume of the space to
the volume of the explosive substance ; on the
heat produced during the reaction ; on the
nature of the reaction as influenced by the
escape of the products ; on the greater or less
dissociation of the products; on the physical
state (solid, liquid, or gaseous) of the products at
the temperature of the explosion ; on the rela-
tion of tiie velocity of cooling to the velocity of
the reaction ; and finally on the mode of inflam-
mation in relation to the initial temperature.
We may at once premise that explosives of
the second class differ essentially when ■ deto-
nated ' from explosives of the first class, in that
their reaction is analogous in point of velocity
and means of propagation to the explosive mode
of ' decomposition ' observed in gases by Berthe-
lot and Dixon.
It is immaterial whether the reaction by de-
tonation or explosion of the ' first order,' as it
is sometimes called, is brought about by a
detonator of some other sudden explosive, or
whether it is produced by the gradual rise of
temperature and pressure produced by the pro-
ducts of the decomposition of some other part of
the same mass. A detonation of gun-cotton may
be produced equally well by using a detonator of
confined fulminate of mercury, and preventing
the escape of the products of combustion, or by
igniting a portion of the gun-cotton by the
application of a hot body or flame.
Many substances detonate or not according
to the circumstances in which they are placed.
Fulminate of mercury, for instance, piled in
small quantities on a sheet of iron may be in-
flamed by a wire laid on the top without pro-
ducing a much greater explosion than would be
produced by gunpowder under similar circum-
stances. If the wire is placed beneath the heap
- and heated by a current to a sufficient tempera-
ture the slight resistance to the escape of the
products of combustion first formed wiU be suffi-
cient to convert the pufi into & loud detonation,
which bruises the plate.
It is very easy to get the explosive wave es-
tablished in fulminate of mercury, and in fulmi-
nate of silver and iodide of nitrogen it is difficult
to prevent it becoming established. (In some of
Abel's experiments on the transference of ex-
ploding influence through tubes it was noted that
the fulminate of silver did not explode with its
usual violence.) In the nitroglycerin compounds
the relative ease or difficulty of estabUshing an
explosion of the first order, i.e. detonation, de-
pends largely on the physical state of the sub-
stance. In all' oases what is required is that the
pressure on, and the temperature of, a portion,
no matter how small, of the substance to be ex-
ploded, shall rise above a certain critical valuo
which depends on the nature, initial temperature,
knd physical state, of the substance. It is not
necessary to make any hypothesis such as that
long since suggested by Abel as to ' synchronism
of vibration,' the anomalies which it was framed
to account for having either arisen from mis-
apprehension, or having been accounted for in
other ways.
We proceed to the general theory.
Provided the reaction is complete the heat
given out may be obtained from the thermo-
chemical data which we owe to Berthelot. A
little care is requisite here, because it generally
happens that some of the products of combustion
are liquid at ordinary temperatures. Now if we
wish to determine the maximum pressure, this
will involve a knowledge of the heat of combus-
tion when all the products are kept gaseous.
Sometimes it may happen that a reaction taking
place at high velocity is not identical with that
at the velocity actually attained in the necessary
calorimetric experiments. In such cases we must
make sure (by analysis of the products) either
that the reaction has not changed, or if it has^
due allowance must be made in the thermochemi-
cal data. A much greater difficulty arises in esti-
mating the percentage of combination which has
occurred when the maximum pressure is reached.
We may either introduce a correction (if one is
to be found) in the data for the heat of reaction,
or in the data for the specific heat of the pro-
ducts. It will 'be convenient to assume, with the
higher explosives at all events, that the maximum
pressure is reached before any heat is lost to the
containing vessel. It will also be important to
note that a decomposition-reaction taking place
at constant volume may not be identical with the
reaction at constant pressure. With the higher
explosives the-reaction even in the open air is
more nearly at constant volume than at constant
pressure.
If Qv is the heat of the reaction available for
raising the temperature of the products at con-
stant volume, and Qp is the corresponding
number at constant pressure, and if the volume
of gas liberated is known, then Qv = Qp + thermal
equivalent of work done in overcoming external
pressure. For instance, for 227 grms. of nitro-
glycerin Qp will be 356-5 kilogram-degrees, and
Qv 360-6 kilogram-degrees. The volumes of
the gases of combustion being supposed to be
reduced to 0° and to expand against a pres-
sure intensity of one atmosphere, Qv comes
to 1,590 gram-degrees per gram of nitro-gly-
cerin at an initial temperature of 15°C. Sar-
rau and Vieille found by a calorimetric expeA-
ment 1,600 gram-degrees. To take a simple case :
Suppose the thermal value of the reaction (Q«)
can be obtained for a gram of substance, let this
quantity of substance be inclosed in a space of
V c.c, and suppose its own volume negligibly
small in comparison ; let the products of reaction,
supposed still gaseous and obeying Boyle's Law,
occupy a volume «' at 0° and 760 mm. ; let the
specific heat of the product supposed constant
be ir, and let m represent the ratio of the por-
tion burnt to the whole initial amount at the
epoch of inaximum pressure P, then the formula
will become
v <r
Now it is clear that as this calculation i3
534
EXPLOSION.
based on Boyle's Law, the temperature being
considerable, we must expect a merely approxi-
mate result, according to Amagat's experiments
at high temperatures and pressures. Again our
knowledge of o-, a quantity which is possibly de-
pendent on the pressure and temperature, is
mere guess work, and the same may be said for
m. The only at all satisfactory case is that of
fulminate of mercury (HgC2N202), the products
being 2C0 and. N,, a mixture not very suscep-
tible of dissociation, though Dixon noted that
even CO is decomposed at high velocities. Ber-
thelot shows that the effect of dissociation is in
all cases to lower the pressure, the heat used
being without exception insufficiently compen-
' sated by the increasedvolumeof the gas liberated.
For speculation as to the probable value of P
from theoretical considerations the reader is re-
ferred to Berthelot. We shall describe the prac-
tical way in which the pressure is measured, and
content ourselves with pointing out that Berthe-
lot's theory leads to results which sometimes
(according to his success in guessing m and a)
do not differ widely from the experimental re-
sults. Of Berthelot's experiments it is impos-
sible to speak too highly.
The instrument used in measuring pressures
is based on the crusher gauge invented by Bod-
man, and improved by Noble and by Abbot ; the
former by the introduction of a cylindrical
crusher and copper cylinder, the latter by the
addition of a clutch making its use possible
under water. For our purpose the best experi-
ments are those of Sarrauand Vieille, for to them
belongs the honour of having rightly interpreted
the indications afforded by the gauge. The dif-
ficulty of interpretation will be best understood
after a short description of the normal type of
crusher. This instrument consists essentially of
a hollow cylinder of mild steel, strengthened,
if necessary, externally by winding with wire.
The cylinder is open at one end and closed at the
other by a strong screw plug ; the explosive to
be investigated is placed in the hole and usually
rests near the plug ; the electrical firing arrange-
ments pass through the plug itself. The capacity
of the instrument used by Sarrau and Vieille was
about 24-33 cc, and the diameter of the bore
was 2-2 centim. A ram piston is inserted into
the open end of the bore, and is supported at its
outer end by a cylinder of pure copper, which in
turn rests on a massive anvil braced to the rest
of the apparatus. The instrument is strength-
ened by two plates, one at each end, braced to-
gether by strong bolts. The dimensions of the
soft copper cylinder are accurately determined
by a previous experiment, and the charge is
weighed and introduced below the plug, the
volume of the bore down to the piston head being
accurately measured. On firing, the increase of
pressure due to the explosive gases causes the
piston ram to ' crush ' the copper cylinder. The
plroblem is to find the maximum pressure ex-
erted on the cylinder. In Eodman's instrument
the piston was furnished with an indenting tool,
and the apparatus itself was of slightly modified
construction, being screwed into a gun and
the piston being acted on directly by the ex-
plosion of the gunpowder when the gun was
fired. Bodman's interpretation was based on
experiments made with a testing machine. His
assumption was that the dimensions of the ' cut '
of the copper depended on the maximum pres.
sure ; thq calibration was effected by producing
an equivalent cnt in a testing machine and
measuring the pressure at which it occurred.
This is rightly criticised by Abbot, who adopts
a rather different method. He uses a solid
cylinder of lead and crushes it by means of a
flat-headed piston. If the length changes during
the operation from Ii to L', and if F is the mean
resistance of the lead cylinder to deformation,
then the work done is
W = F(L-Ii').
W is next measured by the fall of a hammer head
pendulum. The distance through which the
pendulum falls is so arranged that it produces
the same crush as that observed in an experiment.
In Abbot's case the pressures measured were
pressures of explosion under water, and his ap-
paratus therefore more resembled Bodman's.
The kinetic energy of the blow being known, and
the assumption being made that all the energy is
effective in producing the crush, or^ what comes
to the same thing, that the efieotivity is the same
during the hammer-blow (he does not say this)
as it is during the experiment — ^we have a means
of obtaining in the first case an absolute measure
of W ; in tibie second ' a measure proportionate
toW.
It is clear, therefore, that if the resistance is
a known function of the length we shall be able
to obtain a value for F leading to a true result.
As a matter of fact the process of 'crush' is
complex, the resistance being very different be-
fore and after flow takes place.
It is probable that in the immense deforma-
tions employed by Abbot the chief resistance is
resistance to flow, and this will to a certain ex-
tent depend on the velocity of flow. In other
words, his calibration is inexact unless the piston
of the crusher moves with the velocity of the
hammer.
The explosion endues the piston with kinetic
energy, and this energy is spent in deforming the
cyUnder. It is clear at once that much will de-
pend on the time required fov the pressure to
reach its maximum considered in connexion with
the mass of the piston. Sarrau and YieUle (C. B.
95, 26, 180) use copper cylinders in connexion
with the instrument described above. The
equation of slow crush in the testing machine is
T = K„ + K6,
6 being the crush, or change of length produced.
Kg and K constants, and T the pressure pro-
ducing the observed crush. If the crush is not
very great, and the rate of crush slow, E seems
fairly constant up to pretty high values. It by
no means follows, however, that the case is the
same if the velocity of flow be great. When the
cylinder is crushed by one explosion two extreme
cases have to be considered.
1. The piston may be so light that the pres-
sure of the explosion is transferred to the copper
cylinder practically at the time of its develop-
ment in the explosion cylinder.
2. The explosive pressure is so rapidly pro-
duced, or the piston is so heavy, that the maxi-
■ Of course in the end all the energy, or nearly all, is
converted into heat in the cylinder and neighbouring
snrfacea.
EXPLOSION.
636
mum presanreisTeaohed hefcyre thepistcm begins
to move.
In practice' of course there are intermediate
oases. Let p=f{t) be the variable pressure at
the base of the piston, m the mass of the piston,
B the resistance of the cylinder, « the displace-
ment of the piston after time t. Neglecting the
compression of the piston, Ac, the equation
of motion is
within the limits E = K„ to Km. Neglecting the
work done within the elastic limits of the cylin-
der, and taking care that the charge is of such
a size as not to cause the crush to pass the
limit for which the equation holds, this becomes
mg+K„ + K«=/(<).
This may be integrated, and when the pressure
passes tluough its maximum P, we get a relation
between this maximum and the filial crush of
the cylinder. This solution is of the form
P = K.+ ^^
l + *l
(I)
t being the time from the origin to the epoch pf
maximum displacement, and t„ the period of
crush of the cylinder under a constant force
acting without initial velocity through the
mediation of a piston of equal mass m; 4> is
such a function that it is unity when the variable
vanishes, and decreases rapidly as the variable
increases. So the value of P depends on oui
knowledge of —, and this must be determined in
each case.
Now, tn is given by
it is the period (or, as we shonld say, half
period) of the piston, t is got by actual measure-
ment : . this is accompUshed fay allowing the
piston to carry a style pressing on a chronograph
drum.
In a general way the ratio is found to vary
according to the mass of the piston employed.
Sarrau and VieiUe, however, prefer so to vary
the mass of the piston that one or other of the
extreme conditions is fulfilled. If the pressure
rises slowly (within the sense of the equation)
then
P = K.-HKe.
If, on the other hand, the piston moves under
constant force,
Some interesting cases present themselves.
When — varies between 4*8 and 251, the crush
remains the same (or nearly so) with powder,
showing that with the piston used the first
equation must be employed. With potassium
picrate, on the other hand, no sensible value can
be assigned to t, and the second condition is ful-
filled. The same remark applies to gun-cotton
and fulminate of mercury ; with dynamite, on
the other hand, we have an intermediate case.
The first condition is wholly unattainable in
practice, and the second only when the mass of
the piston is very great (in the experiments of
Sarrau and Yieille it was 4 kilos.). If the piston
had a mass of from 3-8 to 6'9 grs.. onlyj then the
crush for a given quantity of dynamite was only
half what it was when the crush was given by the
heavy piston ; for intermediate values of the
piston weight the crush was also intermediate.
With the exception, therefore, of the diffi-
culty above mentioned as to rate of crush, we
may consider that Sarrau and Yieille's experi-
ments establish the right of the crusher to con-
sideration as an instrument of precision. It
must not be forgotten, however, that the indica-
tions afforded refer to mean maximum pressures
only. There may be much local variation at
points near the centre of explosion. By con-
sidering the nature of the possible means of
escape of the gaseous products, it appears that
vortex motion and jet motion may be set up.
This was noticed by Threlfall (P. M. 1886) in
the case of small explosions of fulminate of
mercury under water, by Abbot in the case of
large submarine dynamite explosions, and by
Berthelot as a result of his general experience.
The latter notes that metals subjected to the
influence of detonating compounds are ' creus^s
et sillonnSs,' and referring to the seat of such
explosions he remarks : ' En reaht£, les gaz
brusquementdevelopp4s par la reaction chimique
reprSsentent de v^ritables tourbillous, dans les-
quels il existe des filets de matiSre Sous des
£tats de compression trds difE^rents, et une
fluctuation int6rieure.'
It will be evident that there is much difS-
cnlty in answering such a question as ' What is
the strongest explosive ? ' — in fact, no answer
can be given unless the conditions of explosion
are specified. We may arrange explosives in
the order of maximum pressures developed per
unit mass in unit volume in a crusher gauge, or
we may construct a table showing the pressures
produced by unit masses in their own volumes,
or by equal volumes in their own volumes. For
instance, in the case of fulminate of mercury
with an actual density of charge at the rate of
3g. per o.c, the crusher indicates a pressure
intensity of about 6,000 kg. per sq. centim. for
unit density (the standard condition). For cotton-
powder the figure mounts to 10,000 kg. per sq.
centim. If, however, we consider equal masses
of these substances exploding in a space just
capable of containing them, the mercury ful-
minate (thanks to its specific gravity of 4*42)
wUl produce the enormous pressure of 27,000 kg.
per sq. centim., while the number for the cotton
powder will be only slightly increased. Now
detonators in practice consist of confined charges
in copper or tin tubes, and therefore it is clear
at once why fulminate of mercury is the detona-
tor par excellence, even though the energy ex-
pended per unit mass is surpassed by other ex-
plosives. The period of the attainment of the
maximum pressure of detonating substances, ex-
cepting nitro-glycerin compounds, may be taken
as less than loloo*^ °^ ^ second.
Fulminate of silver, though so remarkable as
a violent explosive, fails as a detonator through
lack of density. The peculiarity of it, and of
es6
EXPLOSION.
iodide o{ nitrogen, lies in the ease with which
the explosive wave can be established in them,
rather than in the energy run down by a given
Tolume, which is the practically important
point. With respect to the uncertainty in the,
method of calculation referred to at the begin-
ning of this article, it seems as if the very high
temperature in the crasher gauge tends to counter-
act the uncertainty produced by the enormous
pressures. We give the following example of the
ILCtual calculation in the case of fulminate of
mercury : —
The heat of formation of
OjN'sOjHg (= 284) is 114,S00 gram-units.
Deducting the heat of vaporisation of mercury,
this comes to 114,500-16,400 = 99,100 units
available. Taking 4'8 as the molecular specific
heat at constant volume of the mercury vapour,
the carbo^ monoxide, and the nitrogen, and
neglecting the difference between this value and
the value for liquid mercury, then
T=9?^=o,161».
4x4*8
The volume of gas formed (CO + N) reduced by
the ordinary assumption to 0°C. and 760 mm.
will be 22-32 litres. At a temperature 5161°
(taking into account the volume of gaseous mer-
cury) ve shall have under normal pressure
V=89-28(l + «^)
= 1,776 litres
as the quantity of gas given oS by 284 g. of ful-
minate in a certain crusher experiment.
Now, 10 g. of fulminate were actually fired in
a space of 50 o.c. ; the corresponding space for
284 g. would have been 1'42 litres, so by Boyle's
Law the pressure would be
i;^^ = 1,251 atmos.
or 1,293 kg. per sq. oentim.
The experiment in the crusher gave
f = 2-4 mm., and the time of reaching the maxi-
mum was negligible. Therefore (the constants
being previously known)
P = 641 -I- 535
= 1176 kg. per sq. centim.
Comparing these two numbers we get an idea
of the closeness of the results; they agree to
within about 10 p.c. The deviation may be due
either to the error introduced by the flow of the
copper or by any of the assumptions in the
theory. The gauge-estimate is probably the
more correct.
The following notes may be of service. It
is well known that many of the more rapid ex-
plosives do not require any tamping — i.e. a
charge of gun-cotton simply laid on a rock will
do nearly as much work in breaking and shatter-
ing as if it were covered with sand or clay-
tamping. The reason is that the increment
of volume tends to take place with greater
velocity than that with which sound is propa-
gated through air. Consequently it may happen
that 'the pressure rises above the crushing
strength of the rock, in which case fracture will
result. In order to produce any appreciable
effect at all the velocity of explosion must be
above some critical value; when this is surpassed
the amount of destructionperformed will depend
ou the energy available.
It is a well-known fact that a small charge
of fulminate of silver fired on a card or thin
sheet of glass wiU in general blow a hole through
the card or glass without doing other damage.
The cause of this phenomenon has been sought
by several observers, the most reasonable of
whom appear to be Mach and Wentzel (2.c.), who
begin by showing that the same effect can be
observed in a vacuum. This leads them to
measure the velocity of escape of the gases
formed during explosion, by observing their
effect on hollow cups forming convenient por-
tions of a ballistic pendulum. The resulting
velocity turns out to be between 3,500 and 17,500
metres per second, with a probability that the
lower limit is the one most nearly approached.
The authors argue that the density of the gases
evolved with this velocity must be very consider-
able, and hence that the eSect on an obstacle
must be comparable with the effect produced by
the impact of a projectile. This leads to the
interesting question of what occurs when a
soft body is caused to penetrate a hard one in
virtue of its high velocity, as when a tallow
candle or bit of soft wood is shot through a
door.
The so-called ' sympathetic explosion ' of
charges probably does not exist. Cartridges
both of gun-cotton and dynamite may be
shattered to dust by an explosion without being
ignited. Detonation may be produced equally
well in chemical compounds and in mixtures,
such as that of dinitrobenzene and potassium
chlorate ; in either case all that is required is
that the pressure and therefore the temperature
should rise to a sufScient value at any one point
of the mass.
The ease with which detonation may be
brought about will depend ceteris paribtts on
the physical state of the explosive as to hard-
ness, fluidity, &c. The most powerful— i.&
energy-liberating — explosive per unit volume is
fulminate of mercury; the most powerful per
unit mass is blasting gelatine (92 p.c. nitro-
glycerin and 8 p.c. nitroceUulose [the exact
composition of the particular nitrocellulose is
not stated]). The latter, owing perhaps to its
physical state, is most difficult to detonate ex-
cept in ha^d rock. For detailed information on
matters connected with explosions the reader is
referred to Berthelot. B. T.
FELLIO ACID.
537
F
rACHNE. An alkaloid said to ooour in beech-
nuts (Buohner a. Herberger ; Haberraann, G. O.
1884, 789 ; J. 1884, 1445).
PAT. The term fat was originally applied
to all compounds of carbon, hydrogen, and oxy-
gen, which leave a permanent ^grease-stain on
paper. They were divided into solid fats and
fatty oils, the latter being subdivided into drying
and non-drying oils. Chevreul showed that
most natoial fats are mixtures of olem, stearin,
and margarin, the last body being subsequently
proved by Heintz {A. 80, 293 ; 84, 297) to be a
mixture of stearin and pajmitih. Chevreul also
showed that on boiling with potash the potassium
salts of olmo, stearic, palmitic, or other.acids,
are formed as soaps, while glycerin is in most
cases also produced. Chevreul classes parafSn
and oholesterin as vmsaponifiable fats, the other
fats being saponifiable. The term fat is, how-
ever, usually confined to saponMable bodies.
Preparation. — ^Fat is obtained from animal
tissue by melting at 100°. The membranous
portions may be removed by adding 1 pt. of very
dilute HCl (containing -03 pts. HOI of S.G. 1-12)
to every 10 pts. of the raw fat, and heating in a
water-bath (Pohl, Z». P. J. 201, 254). The rancid
odour often acquired by keeping is due to volatile
fatty acids, which may be distilled off in steam
by boiling with water (Oubrunfaut, 0. B. 72, 87).
^e odour may also be removed by treatment
with aqueous Na^CO,. Vegetable fatty oils are
expressed from seeds ; a second quantity may be
got by grinding up the seeds and pressing them
a second time while hot. Nitrogenous substances
are removed from the oil by shaking with 1 p.c.
oono. HgSO^. Fats are also extracted from
animal and vegetable products by benzene.
Properties. — Solids or liquids, lighter than
water, cannot be distiUed. Lisol. water, v. sol.
ether, CS^, benzene, and light petroleum; sol.
alcohol. When strongly heated they give off a
pungent odour of acrolein. Alcoholic NH, slowly
converts the fats in the cold into glycerin and
amides of the acids (Eowney, J.pr. 67, 157).
Nitric acid oxidises fats, forming oxsdic, succinic,
and adipic acids. Nitrous aoid causes oils which
contain olein to solidify through the isomeric
change of that liquid to solid elajidin.
SapomficaUon. — Fats are broken up into
glycerin and fatty acids by treatment with super-
heated steam, or by boiling with aqueous alkalis
with water and PbO, or with dilute HjSO, (of.
Benedikt, M. 9, 518). Saponification may even
be effected at 45° by agitation of the melted fat
with aqueous NaOH containing NaCl (MSge-
MouriSs, 0. B. 58, 864 ; Legrand, D. P. J. 186,
161; Knapp, D. P. J. 180, 309; 192, 498; cf.
De Milly, D. P. J. 186, 146). Saponification
may be conveniently effected by heating with
lime (3 p.o.) and water at 172°, or with HjSOi
(8 p.c.) at 115°, glycerin being distilled off with
superheated steam.
Dr^iM^OiZs.—Theseoils become solid through
atmospheric oxidation. This tendency it in-
ereased by previous boiling with PbO. Linseed
oil IB the chief drying oil ; it contains glyceryl
linoleate.
Estimation. — The amount of fat in a mixture
is determined by extracting with ether, and eva-
porating the extract. The amount of free fatty
acid may be determined by titration (Stohmann,
J. pr. [2] 24, 610 ; Hausamann, Fr. 21, 447 ;
Groger, JSV. 22, 289 ; Kreohel, Fr. 23, 261). The
molecular weights of the higher alcohols and of
the oxy- acids present in fats have been deter-
mined by forming their acetyl derivatives and
then saponifying these bodies by alcoholic potash
and titrating the excess of potash, using alcoholic
phenol -phthalein as indicator (Benedikt a. Ulzer,
M. 8, 41).
OomposiHon. — The following fats and fatty
oils, amongst others, contain olein, stearin, and
palmitin : fat of men, sheep, oxen, geese, and
pigs, of cantharides, cocoa beans, oil from seeds
of species of Bassia, from Para nuts, from ooo-
culus indicus, and from maize. Olein and pal-
mitin occur in cotton-seed oil, in bicuhyba fat,
in palm oil, in the fat of beans, peas, and lupine
seeds, and in elephants' fat. Oil of rape and
of mustard seeds contain glycerides of erucic and
behenic acids. Earth-nut oil contains glycerides
of palmitic, arachio, and hypogseic acids. Cocoa-
nut oil contains glycerides of formic, acetic,
butyric, hexoic, ootoic, decoio, laurio, myristio,
and palmitic acids. The fat from the seeds of
AnacardiacecB contains olein and stearin. Cro-
ton oil contains glycerides of formic, acetic,
isobutyrio, isovaleric, tiglic, palmitic, stearic,
laurio, myristic, and oleic acids. Almond oil
consists almost entirely of olein. Nutmegs con-
tain myristin. Oastor oil contains glycerides of
stearic and ricinoleic acids. Linseed oil consists
chiefly of the glyceride of Unoleic acid, but con-
tains also those of palmitic and myristic acids.
Ood liver oil consists chiefly of olein and palmi-
tin, but it contains also small quantities of acetic
and butyric acid and some compound of iodine.
The oils from poppy seeds and from walnuts
contain glyceryl linoleate and other glycerides.
Butter contains glycerides of palmitic, stearic,
myristio, arachio, butyric, hexoic, octoio, and
decoic acids.
FATTY ACIDS v. Acms.
FATTT ALCOHOLS v. Alcoeolb.
FATTY COMPOUNDS. This term is applied .
to all organic compounds whose molecules are
supposed not to contain a closed chain of carbon
atoms.
FEHLING'S SOLUTION. An alkaline solu-
ton of potassio-tartrate of copper used in the es-
timation of glucose, which reduces the solution
with ppn. of red Cufi. Fehling {A. 72, 106 ;
106, 75) dissolves 192 grams NaK.CjH^Oj crys-
tals in a little water, adds 600-700 c.c. NaOHAq
S.G-. 1-12, and then 40 grams CuSO^.eHjO in
about 160 c.c. water, and dilutes to 1154-4 c.c. at
15°. Five milligrams of dry glucose ppt. all the
Cu as CUjO from 1 o.c. of this solution.
M. M. P. M.
FELLIC ACID Os,H„0,. [120°]. An acid
said to accompany chollo acid in human bilq
538
FELLIO ACID.
(Sohotten, B. 11, 268). Strongly electrical
powder, tastes bilter. it gives a red, but not a
crimson, colour with Pettenkofer's test. —
BaA'jiaq. S. 1-3.— MgA'j 2iaq.
FENNEt OIL. The oil of common fennel
(Anethum Fceniculum) co^tain3 anethol and a
terpene (phellandrene) (c. 187°) (Cahours, A. 41,
75).
FEEMENTATION AND PUTREFACTIOH.
Most organic compounds exposed to the air
undergo decomposition at a more or less rapid
rate. The decomposition takes place most
rapidly in the presence of moisture and at a
slightly elevated temperature. In most cases
the decomposition consists in the breaking down
'Of complex molecules either by the assimilation
of the elements of water [hydrolysis) or by a slow
'process of oxidation (eremacausis or decay). In
other oases the change seems to be one of mole-
>cular rearrangement resulting in the alteration
>of the physical properties of the body, such as
rthe conversion of a solidinto aliquidmetameride.
"When these changes are accompanied by the
■avolution of gases of unpleasant odour, the term
/putrefaction is used, and it may therefore be re-
igarded as a special case of fermentation. The
earliest experiments on these phenomena have
lestablished the facts that decomposition does not
itake place if air be excluded, if the materials be
dry, if the temperature be below 0°0. or above
100°C., or in .the presence of certain organic and
inorganic bodies, which, fromhaving the property
of arresting or preventing these changes, are
called anti-septics, anti-ferments or anti-putres-
cent substances. Formerly it was held that
these changes were due entirely to the action of
chemical and physical forces, but it is now known
that in most cases, and possibly in all, the de-
composition cannot take place without the inter-
vention of living organisms or of chemical
substances, which, although of an unorganised
constitution, are derived directly from living
protoplasm. The bacteria and certain fungi are
the best-known organisms which determine
these changes. Each bacterium characterised
by its particular foim and growth feeds on a
particular pabulum or chemical food causing it
to break up and form definite chemical products,
so that there is found in each kind of fermenta-
tion the same conditions and the same kind of
organism. The reasons which have led to the
above view are based not Only upon the conditions
which are found necessary for the fermentation
to take place but also upon the fact that a nitro-
genous body is always found in the liquid even
when the chemical change consists in the breaking
down of a non-nitrogenous compound. In some
cases fermentation is brought about in a manner
which appears to be different from the foregoing,
no organisms being present, and the addition of
certain anti-ferments fail to stop the decom-
position. In these cases bodies of complicated
constitution, and directly derived from vegetable
or animal organs, must be present. They are
without organic structure, and are known as
chemical or unorganised ferments or enzymes,
and may in most cases be extracted from the
organs in which they occur by means of glycerin,
and can subsequently be precipitated from the
solution in an amorphous condition by the
addition of alcohol. The enzymes seem to be an
intermediate product of organic life. None have
been prepared artificially, and plant and animal
organs by the secretion of these substances are
enabled .to perform their special functions. Theil
characteristic properties are destroyed when their
aqueous solutions are warmed to a temperature
near' to 100°C., and no action takes place when
the solution is qooled below another fixed tem-
perature. These critical temperatures vary vrith
the different enzymes, but the range of tempera-
ture approximates to 50°-75°O. Great concen-
tration of the solution and the addition of glycerin
or alcohol alter the temperatures at which the
enzymes cease to act. Dry enzymes can be heated
to the boiling-point of water and even higher
without destroying their property of fermenting.
Dried pepsin can be heated to 170° without losing
its fermenting action (Hiippe, C 0. 1881, 745).
Light also modifies the rate at which the enzymes
ferment.
Theories of fermentation. From the fact
that contact vtrith air and the presence of a
nitrogenous body are necessary for fermentation
or putrefaction to take place, Berzelius and
Liebig concluded that the nitrogenous matter
was decomposed by the atmospheric oxygen, and
that this reaction caused a rearrangement of its
elements which determined the decomposition of
the molecules of the fermentable substance
present. Schwann's discovery of the presence
of organic germs in the air led Pasteur to formu-
late the theory that fermentation is never excited
except under the influence of microscopic or-
ganisms, and further that each particular organ-
ism sets up a peculiar species of fermentation.
Schwann and Helmholtz showed that air which
had passed through a red-hot tube could not in-
duce fermentation, and thereby proved that
oxygen alone was not sufficient to bring nitro-
genous matter into the condition of a ferment.
Blondeau was the first to show that the con-
version of sugar into alcohol was due to the
growth of one particular organism (Torvula
cerevisicB), and that the conversion of sugar
into lactic acid was due to the growth of the
mould Penicillium gkmcum, and that beer yeast
contained the germs of both these organisms.
Blondeau also pointed out that in butyrous fer-
mentation or the formation of butyric acid from
sugar, and in the conversion of urea into car-
bonate of ammonia, a growth of PemcilUum
glaucum accompanied the change. These views
of Blondeau, Pasteur, and Schwann, were con-
tested by Liebig, who adduced experiments in
support of his own view. Schmidt {A. 61, 168)
pointed out that by adding the clear filtrate from
the paste produced by beating almonds with
water to a liquid containing urea or grape sugar,
fermentation took place, and when the latter
substance was employed, no tface of yeast cells
was manifest until the fermentation had taken
place for a considerable time. Pasteur (Bl.
1861, 67-79) produced additional evidence to
show that ready-formed yeast would germinate
and grow to a limited extent in a liquid con-
taining sugar and albuminous matter, even
when oxygen was completely excluded. He ex-
plained this result by assuming that the yeast
acted as a ferment in the absence of air by ab-
stracting oxygen from the sugar, and that upon
this deoxidising power its action as a ferment
FERMENTATION AND PUTREFACTION.
639
dependB. Organisms which are aerobic, and live
by means of the oxygen of the air, might become
anaerobic and derive their oxygen from some
ready-formed compound and thus act as fer-
ments. Pasteur also extended his researches
on the action of ferments to the phenomena of
putrefaction and decay, and (C. B. 5ti, 734, 1189)
defined putrefaction as a kiiid of fermentation
induced and maintained by organisms of the
genus Vibrio, whioh can only live in contact with
the air. He showed that when calcium lactate
ferments in the absence of air, calcium butyrate
and other products are the final result, whilst, if
air has access to the liquid, the butyrate likewise
ultimately disappears. The putrefaction of solid
bodies (animal carcases) is also due to the activity
of these organisms, whose development can be
checked by inclosing the substance in a closed
vessel containing a cloth soaked in spirit or by
other antiseptic treatment. The gangrene which
is subsequently produced under these conditions
is regarded by Pasteur as distinct from putre-
faction, and as analogous to the ripening of
fruits after their separation from the plant on
which they grow. These experiments of Pasteur
were criticised by Lemaire {G. B. 57, 958), who
regarded the various processes of fermentation
as due to the action of one and the same ferment,
and denied the existence of special ferments. He
also concluded that the unrestricted access of
air was essential to the progress and completion
of putrefaction. Pasteur (O. B. 73, 1419) drew
attention to the fact that properly selected
mineral salts were necessary for the growth of
fermentative germs. He found that the addi-
tion of small quantities of NH,, Mg, Ca phos-
phates and (NH4)2S04 to a solution of calcium
lactate increased the rate at which the lactate
disappeared on the addition of vibrios, and that
at the same time numerous fresh vibrios were
produced. As soon as the whole of the lactate
was decomposed the vibrios fell dead to the
bottom of the vessel. Again [C.B. 75, 784) he
showed that the same cells acquire or lose the
power of acting as a ferment according as they
are deprived of air or exposed to its action.
Yeast and other ferments can therefore live and
multiply without contact with the atmosphere by
obtainingthe oxygen necessary for their existence
from the decomposition of the oxygenated com-
pounds in which they live. The moulds, such as
PemcilUumglaiicum, become ferments when they
feed in this manner upon bodies rich in oxygen
instead of absorbing atmospheric oxygen. Evolu-
tion of heat usually accompanies fermentation;
the compounds, which are decomposed, being of
a high order of complexity, evolve heat in their
resolution into simpler molecules of a more stable
nature. The spontaneous combustion of some
organic bodies is probably due to the action of
ferments. Bodies rich in nitrogen are very
prone to putrefaction, but some, such as uric
acid, the alkaloids and indigo, do not undergo
any change. The gases evolved in fermentation
may be carbonic acid, ammonia, sulphuretted
hydrogen, hydrocarbons, nitrogen, and hydrogen.
BSrard drew attention to the fact that fruits ex-
posed to an inert gas evolve carbonic acid, and
Pasteur showed that alcohol was at the same
time produced which pointed to a sort of fer-
mentation taking place. The earlier experiments
on the action of reagents upon ferments showed
that neutral gases and dilute acids do not allect
the power of yeast, but that sulphur is reduced
to sulphuretted hydrogen when added to a fer-
menting liquid. Dilute alkalis retard fermen-
tation and large doses of dilute acids completely
stop it. The behaviour of other reagents upon
fermenting liquids is discussed under <mtisepHca
at the end of the present article. The influence
of pressure on fermentation has been studied by
H. T. Brovm (0. J. [2] 10, 570 ; 11, 973). Ac-
cording to his experiments, N, H, paraffin hydro-
carbons, and KO are evolved, besides CO^ in the
alcoholic fermentation of grape sugar or malt
wort. Diminution of pressure causes a large
increase of the gases unabsorbed by KHO. The
increase of hydrogen is accompanied by the
formation of acetic acid and aldehyde, and no
nitrogen is evolved from solutions free from
albuminoids. The nitric oxide is due to the re-
duction of nitrates under diminished pressure,
less sugar is decomposed, and the proportion of
carbonic acid to alcohol is greater. The in-
fluence of temperature on fermentation has been
studied by many observers chiefly from an in-
dustrial point of view. Pierre (0. B. 78, 317)
showed that high temperatures in alcoholic fer-
mentation were attended with a more abundant
formation of the higher alcohols. When the
temperature is kept down to the lowest point,
traces only of butyl and amyl alcohols are ob
taiaed. Propyl alcohol is always produced.
Contributions to the study of fermentation by
Brefeld (B. 7, 281), Mayer {B. 7, 579) and Traube
(B. 7, 872) conclusively proved that yeast re-
quires for its growth and propagation free oxygen.
Fermentation takes place in the absence of free
oxygen, but in this case the yeast does not in-
crease. Moritz (0. J. 1874, 599), Mohr (B. 7,
1421) and Pasteur (O. B. 80, 452) disagree with
their results, and stiU more recently Berthelot
has published the laboratory notes of C. Bernard
which tend to support the observations of the
former experimentalists. According to Bernard
(G. B. 87, 125), alcoholic fermentation is not
life without air, for alcohol is formed by contact
of sugar with air vrithout yeast. The ferment is
not derived from external germs, for in sterile
juices the ferment is not developed ; alcohol is
formed by a soluble ferment apart from the life
of the ripening fruit for which air is absolutely
necessary. The soluble ferment is found in the
juice expressed .from the fruit, and it pro-
duces alcohol in the expressed juice. It will be
seen from the above summary that the present
condition of the subject is very unsatisfactory,
and that further experiments in nearly every
direction are needed with pure materials aad
known organisms. Much of the past work has
been done by chemists who have neglected the
biological portion of the work, or biologists who
have not noted the exact chemical changes
which occur. Steps towards a better grasp of
the subject are being made by several investiga-
tors. .Experiments by Fitz, Marpmann, and
more recently by Warington and Percy Prankland,
have given definite data for future work. These
experiments were made with pure cultivations
of known organisms, and the amount and quality
of chemical change carefully determined. Beoent.
work seems to indicate that bacteria and moulds,.
540
FERMENTATION AND PUTREFACTION.
living anaerobic, bring about most fermentations,
and that, for these organisms to live, certain
conditions are necessary, the most important of
which is that their special nitrogenous pabulum
is present. The way in which the enzymes or
unorganised ferments act is still imperfectly
understood. The decomposition effected by
their agency is not so complete as in the other
eases. Generally the change appears to be one
of molecular rearrangement only, and no altera-
tion in the distribution of energy takes place.
Bacteria may, however, play an important part
in the changes which are now attributed to these
unorganised ferments, and they may, therefore,
only be the means of educating some of the
common bacteria into doing special work. All
the unorganised ferments contain nitrogen, and
it is certain that the bacteria cannot live without
some nitrogenous substance being present. It
is known that the same species of bacterium, by
varying the conditions of life, is capable of giving
very different chemical products. It may be
that the unorganised ferments do not by them-
selves determine the change, but that bacteria
are induced by them to work in special manners.
When we consider the various food-stuffs which
are resolved by the higher organisms into the
same products, we see that the same organism is
capable of a wide range of pabulum or can bring
about a great number of chemical decompositions.
Wbrtmann, on the other hand, is of opinion that
bacteria effect fermentation by producing first
an unorganised ferment which then brings about
the changes which are ascribed to the bacteria.
Yeast, for example, secretes an unorganised fer-
ment, invertin, which has the property of re-
solving cane sugar into glucose. Starch is also
converted into a sugar capable of reducing cuprio
oxide by bacteria in the absence of other sources
of carbon nutriment, and this action is due to
the secretion of a ferment by the bacteria. The
ferment is soluble in water and precipitable by
alcohol. It acts on starch in the absence of
oxygen and is secreted by bacteria in a neutral
starch solution. It does not possess any pepton-
ising properties, but under different conditions
the same bacteria can form (1) an amylolytic
(diastatic) ferment, and (2) a peptonising fer-
ment (Wortmann, S. 6, 287-329). Warington
has shown that Micrococcus gelatmosus, M.
wecB, B. fMorescens lAquescens, soil and Eooh's
cholera spirillum curdle nulk readily witiiout
producing any appreciable acidity. The curdling
cannot be due to the formation of lactic acid,
but points to the secretion of a rennet-like fer-
ment by these organisms (Warington, C. J. 1888,
737). Stutzer has likewise found that moulds
grown in a solution of salts and tartaric acid
formed albumen and nuclein (R. 6, 672-674).
Yeast, according to Hoppe-Seyler, also forms
nuclein.
Fermentation processes may for our present
purpose be conveniently classified according to
the principal products formed.
Ethyl alcohol is formed from sugars, starch,
and glycerin. Propyl, Butyl, Amyl, Mexyl,
and Heptyl alcohols are all produced under
suitable conditions. The formation of mannite
and gum from sugar, and the ferment oils may
also be included under the heading of alcoholio
fermentation.
Fermentation resulting in the production of
acid bodies includes the formation of acetic add
from alcohol, butyric acid from lactic acid, lactic
acid from sugar, and tUtrio and nitrous acids
from ammonia. Ammonia from urea andihe
ptomames from albumen are examples of basic
fermentation.
The enzymes as we have seen do not form
such simple products as are produced when the
fermentation is the result of the action of
bacteria and moulds. ' They may be classified
into: 1. Sugwr-formvng, including diastase,
ptyalin, myrosin, emulsin, invertin, and the
ferment of the pancreas. 2. Peptone-forming,
including pepsin, papain, and trypsin. 3. Albu-
men-formimg, the more important of which are
the ferments of the liver and blood and chy-
mosin. 4. Olycerme-forming or fat-decomposing,
of which the ferment of the pancreas and
Fremy's pectase are examples. S. According to
Musculus an unorganised ferment exists in
urine and forms ammonia from urea (Pf.
12, 214). Mayer (Le}i/re von den Chem.
Fermenten, 1882, 82^91) has examined the
quantity of enzyme required to produce a given
amount of decomposition, and has shown that
the amount of fermentation varies direetly with
the amount of ferment employed. He has also
established the fact that the enzyme is not
destroyed by its own ferment action. The
precise manner in which the chemical ferments
act has been the subject of much speculation.
Most of the facts can be explained on a theory
of action similar to that of sulphuric acid in
etherification, but a ' contact ' theory seems more
probable. If the enzymes by . their presence
raise the molecular temperatures of the decom-
posing molecules to the point at which their
molecular equilibrium is destroyed, then decom-
position is produced by rearrangement of energy
and not by any increase or decrease of the
amount present in the system.
1. Alcoholio or Vinous fermentation. Solu-
tions containing glucose CgHijOgin contact with
the air at temperatures between 20°-24°C.
become turbid, give off CO:, and after sometime
have the whole of the sugar converted into
alcohol. Glycerin, succinic acid, and the higher
alcohols are at the same time produced. Wh.ea
the evolution of carbonic acid ceases the ferment
or yeast (Torvula or Saccharomyces cerevisice)
separates leaving the liquid clear. The separated
yeast is capable of inducing fresh fermentation
in further quantities of sugar solution. Cane-
sugar and milk-sugar also undergo various fer-
mentations, but they are first hydrolysed by
the ferment or commercially in other ways.
Other ferments induce the vinous fermentation
of sugar, e.^. erythrozym the madder ferment
|Sohunck, J.pr. 63, 222) besides fungi. Beess
(Bot. Unterstich. U. d. AlcoholgSihrungspiie)
gives the following list of fungi which incite
alcoholio fermentation : — Saccharomyees eere-
visicB, S. elUpsoideus, 8, pastorianus, 8. apieu-
latus,8.exigwis, S.albicans, Mycoderma (rarely),
Mucor racemosus, U, oircimelloides, M. apinoaui,
M. stoUmifer, Exoascua almtorquus (Sadebeck),
Torula and Ewrotium aspergUUts glaueus.
The following fungi do not form alcohol when
sown in sugar solutions : — Saccharomycet
ghitims, Mycoderma {geJieia,llj),E!eoaaeuspnini,
FERMENTATION AND PUTREFACTION.
541
Oematvwm ptillulans and Fumago. The no-
menclature of the fangi is continually being
inodified, and Hansen of Copenhagen has re-
Btricted the genus Sacoharomyces to the three
species, cerevisicB, eUi^soideus, and pastorianus,
as they are the only sprouting fungi which form
ascospores. Chemically yeast consists of cellu-
lose (35), protein (45), peptone (2), fat (5), ash
(7), and extractive matter (4) (Nageli and Low),
and the various yeasts have approximately the
same composition. Schiitzenberger (C. B. 78,
493) has found that yeast when boiled with
water yields an extract containing phosphates,
gum arabin, leucine, tyrosine, carnine, xanthine,
guanine, hypoxanthine, sarcine, and a sweetish
uncrystallisable syrup still containing nitrogen.
According to BSohamp fresh yeast contains
neither tyrosine nor leucine (0. B. 78, 645).
Eey-Pailhade (O. B. 107, 43) has shown that an
organic compound named philothion, having the
property of hydrolysing sulphur in cold solutions,
is formed in the life processes of yeast. Con-
centrated methyl alcohol readily extracts it from
the yeast. Dumas had previously noticed the
property which yeast has, of forming SHj from
S. Pure yeast is best prepared by allowing fer-
mentation to take place in a sugar solution in
which a quantity of alcohol varying from 5-8
p.c. has been added, and the temperature not
allowed to exceed 15°G. Such yeast can be
grown in a solution rich in albumen at about
30°C. without any bacteria appearing (Traube,
B. 9, 183, 1239). Hansen has devised a com-
mercial method for obtaining pure yeast (Salo-
mon, J. Soc. Arts, 1888). (For the composition
of yeast V. Belohonbeck, J. 1875, 898 ; Schiitzen-
berger a. Destrem, C: B. 88, 287,383; Bommier,
O. B. 98, 1594.) Vinous fermentation only takes
place in dilute solutions of sugar, and as an
increase of yeast takes place in fermentation,
the liquid in addition to sugar must contain the
elements necessary to form cellulose and proto-
plasm (P, K, Mg, Ca, and S) and a nitrogenous
food. Proteids or peptones are the best form
for the nitrogen, but aeetamide, methylamine,
ethylamine, propylamine, asparagiae, and leu-
cine, are aU assimilated by the yeast cells
(Nageli). Oxamide and urea supply nitrogen
but not carbon, while cyanogen compounds yield
up their carbon but not the nitrogen to these
organisms. Formic and oxalic acids are also
unsuitable for the carbon supply of these fungi.
Yeast loses a considerable portion of its ferment-
ing power by pressure, and still more by washing
with water.
Glycerin also deprives yeast of its ferment-
ing power (Gunning, B. 5, 821). The influence
of the age of the yeast on fermentation has been
studied by Begnard (C. B. Soc. Bial. [8] 4, 442).
Maltose and glucose are the two sugars which
are most readily fermentable by yeast. AU the
true Sacoharomyces ferment maltose, but 8.
exiguus and S. wpiculalMs are unable to decom-
pose this sugar. The more complex carbohy-
drates are sometimes hydrolysed or inverted
before alcoholic fermentation takes place. The
higher dextrins are hydrolysed into malto-
dextrin and subsequently split up into_ maltose
and dextrin hyS.pastorianus and 8. elKpsoideus.
S. ceremsia is tmable to resolve malto-dextrin
into maltQse and dextrin. The conversioo ol
cane-sugar into glucose is apparently brought
about by a soluble ferment termed invertin,
which is secreted within the cells of all trui
sacoharomyces (Donath, B. 8, 795). This
soluble ferment has been isolated in the form of
a powder. It is not formed by S. apiculatiis nor
by four out of the five varieties of Pasteur's
Torula (Hansen). MoniUa Candida ferments
cane-sugar, but titere is no invertin formed, the
inversion being probably due to the secretion of
some other soluble ferment. Mucor racemosus
and M. mucedo both set up alcoholic fermenta-
tion in solutions of glucose. M. racemosus does
not ferment innlin, but readily ferments the
levulose prepared from it. The alcoholic fer-
mentation due to M. mucedo takes place in the
absence of oxygen at temperatures between
25°-28° 0. Succinic acid but no glycerin is pro-
duced by this fungus (Fitz, B. 6, 48). Dextrin,
inulin, and milk-sugar do not ferment under the
influence of mucor.
The alcoholic fermentation of milk-sugar
according to Blondlot is brought about by a
special alcoholic ferment which does not mani-
fest any action below 20°, and then only when
the Liquid is agitated. A small quantity of
butyl alcohol is at the same time produced.
Vieth has also shown that yeast does not readily
set up alcoholic fermentation in solutions of
milk-sugar. Eefir grains, which contain a
bacillus termed Diaspora caucasice by Kern and
a modified form of S. cerevisite, produce a rapid
alcoholic and lactic fermentation in milk-sugar
solutions (Analyst, 12, 2).
Ethyl alcohol is obtained from other sub-
stances by fermentation.
According to Fitz (B. 9, 1848 ; 10, 276 ; 11,
42) alcohol is produced when schizomycetes
are added to a solution of glycerin, mamiite,
starch, dextrin, milk-sugar, or dulcite, but, as
the fermentation only takes place in the presence
of some nitrogenous material, pepsin or am-
monium sulphate is added to the solution.
Acids are at the same time produced, n-butyrio
acid being the one most frequently formed.
Quercite yields no alcohol and only M-butyric
acid.
The quantities of the products formed in
alcoholic fermentation vary with many condi-
tions which have not yet been fully determined.
Glycerin, succinic acid, and traces of high alco-
hols are almost always produced. An analysis
of the products obtained by the fermentation
of 100 kilos, of sugar by S. Mpsoideus gives
the-following numbers in grams :
Ethyl alcohol 50615-0, n-propyl alcohol 2-0,
isobutyl alcohol 1*5, amyl alcohol 51*0, ethyl
beptoate 158-0, glycerin 2120-0, acetic acid 205-3,
succinic acid 452-0, and traces of aldehyde.
Small quantities of bases appear likewise to
be produced, and m-butyl alcohol and butyric
acid are frequently formed. An examination of
the products of the fermentation of sugar solu-
tions by different yeasts has been made by
Claudon a. Morin (Bl. 49, 178-189). Lindet
(O. B. 107, 182) has shown by experimenting
with the same yeast on the same wort that the
amount of higher alcohols produced varies with
the temperature. The maximum amount of
ethyl alcohol is produced at the same tempera-
ture (8°-lO°C.) AS that when the amount oi
542
FERMENTATION AND PUTREFAOTION.
higher alcohols is a miniTTHiTn (-52 p.o.). At the
temperature 2S°-27°C. -59 p.c. of the higher
alcohols was prodnced.
Formation of the higher alcohols by fermen-
tation.—Fitz (B. 13, 36, 1311) has shown that
the Echizomycetes form n-prqpyl alcohol from
glycerin. It is also a constituent of most fusel
oils.
n-Butyl alcohol has been obtained by the
same observer by the action of a bacillus allied
to, but somewhat larger than B. subtilis, on
glycerin in the presence of OaCO, {B. 11, 42,
1892 ; 9, 1348). Yigna {B. 16, 1438) has sug-
gested this formation of n-butyl alcohol as a
method of its preparation, since the yield is
9 p.o. of the glycerin used.
lao-butyl alcohol has been found in the fusel
oil from mangolds (Wurtz, A. Oh. [3] 42, 129).
Isoa/m/yl alcohol is the principal constituent
of the fusel oil formed in the ordinary fermenta-
tion of potatoes. Pierre (J. 1871, 832) has shown
that the higher the temperature of fermentation
the greater the quantity of this alcohol. An
active and an inactive amyl alcohol have been
separated from fusel oU. Iso-butyl and traces
of other alcohols are also formed (Perrot, A. 105,
64). In Swedish fusel oil Babuteau has found
propyl, iso-jpropyl, iso-batyl, iso-amyl alcohols,
methyl propyl carbmol and liquids boiling above
132° {Bl. 33, 178) («. Wyschnegradsky, A. 190,
365).
n-Bexyl and n-heptyl alcohols also occur in
fusel oils (Paget, A. 88,325 ; J. 1862, 412).
Lebel has shown that PemdlUiim, gloMCum
acts upon the methyl-propyl-oarbinol obtained by
the reduction of methyl. propyl ketone, yielding
an alcohol which has a lesvorotation of —12°
(Lebel, J. 1879, 492).
Manmte amd gvm, under certain conditions,
are formed from cane-sugar. Pasteur {Bl. 1861,
30) jiointed oat that when this wMxms fermen-
taUcm takes place in solutions of cane-sugar,
CO2, mannite, and a mucilaginous substance are
produced. Access of air and nitrogenous matter
are necessary for this fermentation. Neither
acid nor alcohol is produced, and the fermenta-
tion only takes place in neutral or slightly
alkaline solutions (Bauer, B. C. 1882, 630).
This kind of fermentation has been noticed in
solutions of oane-sugar, beet juice, carrot juice,
the juice of mangold wurzel, and in lemonade.
Baudrimont (O. B. 80j 1253) observed the oc-
currence of a spontaneous viscous fermentation
in a solution of crystallised cane-sugar (o. Hoch-
stetter, J.pr. 29, 30; Kircher, A. Gh. 31, 337;
Plagne, J. Ph. 26, 248 ; Commaille, M. Sci. 3,
435, 673, 772).
A white substance resembling cellulose is
formed Under certain conditions in beet juice
and beet molasses. It is precipitated from the
solution by the addition of alcohol. Certain
fatty seeds (rape, colza, &o.) form cellulose from
saccharose (Durin, C. B. 82, 1078 ; Pasteur,
C. B. 83, 176). For the fermentation of cellulose
itself V. Tappeiner,^. B. 24, 105 ; Hoppe-Seyler,
B. 16, 122 ; PopoS, Pf. 10, 113.
Lecuartier and Bellamy have shown that
certain fruits and roots under the influence of
oxygen become the seat of an alcoholic fermen-
tation characterised by the evolution of carbonic
acid and the disappearance of sugar in the
tissues of the plant cells. From these and
other experiments Pasteur considered that if
plants could continue to live in an atmosphere
of carbonic acid they would become ferments for
sugar. Muntz (C i^. 86, 49), on examining this
intracellular alcoholic fermentation of plants, has
arrived at the following results : — 1. That plants
preserved in air give no trace of alcohol. 2. That
plants placed in an atmosphere of nitrogen foia>
appreciable quantities of alcohol, sometimeK
amounting to 1,000 times the total weight of
the plants. 3. That the plants when returned
to the air remained perfectly healthy. The
living cell, then, in the higher plants is capable,
in the absence of oxygen, of acting like the
cells of fungi in producing a true alcoholid fer-
mentation. The volatile oUs, which are pro-
duced by the fermentation of various plants,
may owe their origin to some such similar action
of the living cells of the plant in the absence
of oxygen. They are known as rsnimNi oils,
and are formed when portions of the plant are
left to ferment in water, and can then be dis-
tilled from the liquid. The distillate is then
saturated with common salt and extracted with
ether. Little is known as to the constitution of
these bodies. Berzelius regarded them as pecu-
liar alcohols related to fusel oil {B. J. 27, 641).
They have been examined by Bley, Landerer,
Biichner, and others. The following is a list of
the more important plants from which ferment
oils have been obtained: — Chcerophyllum syl-
vestre, OheUdorwwm majus, Oomum maculatum,
Erythraa cenimmmn, Echium vulgare. Erica
vulgaris, Ma/rrubiwin vulgare, Achillea Mille-
foWwm, various species of PUmtago, Quercua
robwr, SaUx pentandra, Salma pratensis, Tri-
foUimifiMmwm, Tuasilagojairfara, Urtica wrens,
and ViUs iiinifera. A similar ferment oil is
produced in cellulostasis, a disease of the apple
XOm. 14, 413).
On alcoholic fermentation the reader may
consult for further information — Amthor, B. 12,
64 ; Bfichamp, O. B. 88, 719 ; Berthelot, 0. B.
89, 806 ; Cochin, O.B. 89, 786 ; 89, 992 ; Giacosa,
B. 12, 703; Hoppe-Seyler, B. 12, 702; Petit,
O. B. 73, 267 ; Schiitzenberger, C. 0. 1877, 73 ;
Sohutzenberger a. Destrem, C B. 88, 693.
The formation of acids by fermentation.
The conversion of alcohol into acetic acid seems
to be a catalytic action, as platinum black and
other finely-divided substances facilitate the
transfer of the atmospheric oxygen besides the
organisms which bring about the same change.
Acetous fermentation takes place in presence
of a fungus Mycoderma aceU, vinegar plant ot
mother of vinegar, and a bacterium (B. aceti}.
Both these organisms are usually present, anC
apparently the bacterium completes the work of
the mycoderma. It is believed that the function
of mycoderma is to convert starch into alcohol,
and that the alcohol produced in this or other
ways forms the pabulum of the B. acett, which
causes the oxidation of the alcohol to acetic
acid. K, Mg, NE,, and HjPOj are necessary for
the growth of mycoderma (Pasteur, /. 1861, 726;
1862, 475). The same organisms appear to be
capable of completely oxidising the acetic acid
which they form to carbonic acid and water, if
it be not removed. This is especially the case
if the growth be allowed to sink to the bottom
FERMENTATION AND PUTREFAQTION.
643
of thA liqnict. A temperature ranging from
20°-35° ia the best for the change, and above
60° all fermentation ceases.
The formation of acetic acid at times aooom-
panies alcoholic fermentation {B6ohamp, J. 1863,
773 ; Blondeau, O. B. 57, 958 ; Pasteur, Mudss
gar la mnaigre, Paris, 1868). Acetic acid is
also produced, together ■^th butyric acid, in the
fermentation of a mixture of malt, milk, chalk,
and rancid meat (Grillone). According to BS-
ohamp (O. B. 76, 836) it is normally present in
milk, together with alcohol, as a product of the
action of miorozymes.
Acetic acid and butyric acid are formed by
the action of yeast, at a temperature of 20°-
30°, on citric acid, to which excess of chalk has
been added. Putrefying curd and a base effect
the same change (How).
Lactoiis fermentation or the formation of
lactic acid from the sugars — glucose, cane- and.
mUk-sugar — takes place when these bodies are
mixed with fresh sour cheese, or with milk and
chalk. After some time the lactic acid is itself
attacked, and H, CO,, aind butyric acid are pro-
duced. The lactic fermentation only takes place
in a neutral or slightly alkaline solution. This
condition is obtained by adding chalk or zinc
white to the sugar solution. Traces of
manoite are also formed (Fremy, A. 31, 188;
Boutron, 4. 39,181; Bensoh, A 61, 174; Lau-
termann, A. 113, 242). The decomposition of
the calcium lactate into butyric acid appears to
be due to the action of a bacillus (Pasteur, J.
1862, 477). The schizomycetes resolve it into
propiordo add (Fitz, B. 11, 1898; 12, 479;
Strecker, A. 92, 80), acetic acid, and sometimes
n-vaUricmie acid (Pitz, B. 13, 1309). The fer-
mentation of calcium lactate by the butyric
ferment of Pasteur yields butyric acid, propionic
acid, ra-valerianio acid, and some ethyl alcohol
(Pitz, B. 13, 1310). The ordinary lactous fer-
ment, according to Pasteur {A. Ch. [3] 52, 404), is
PemcilUu/m glatuyu/m. It resembles beer yeast,
and is grey in colour, and has been described by
Pasteur and Blondeau. Free acid retards its
action, nitrogenous matter favours it, desiccation
or boiling with water weakens it. All the sugar
can be converted into lactic acid if ammonium
salts and phosphates be present. Lactous fer-
mentation often accompanies vinous fermenta-
tion (Blondeau, J. Ph. [3] 12, 257). The change
may be brought about by the presence of a
special bacterium {B. acidi lacUci) which accom-
panies the growth of P. glaMcvmi. The conditions
of lactic fermentation have been examined by
Bichet (0. B. 88, 750; 0. J. 36, 663) and
Berthelot {A. Oh. [3] 55, 351).
Butyric fermenUiiion. — We have seen that
butyric acid is flie final product in the lactous
fermentation of sugar solutions. The conversion
of lactic into butyric acid is accompanied by the
evolution of hydrogen and carbonic acid, and
butyl alcohol is also produced. The ferment,
according to Pasteur, is a bacillus (O. iJ. 52, 344),
which requires no oxygen for its life, and is not
killed when carbonic acid is passed into the
liquid. Ammonia and phosphates are necessary
for the development of this fermentation (Pas-
teur, Bl. 1862, 52). Bfichamp attributes the
ehange to a ferment existing in the chalk which
is added (Bl. [2] 6, 484), and Baudrimont to an
unorganised ferment (0. B. 80, 1253). Boehin
(B. 8, 634) has observed that butyric fermenta-
tion accompanies the evolution of marsh^gas and
aminonia, when plants are immersed in Water free,
from air. Twigs of Elodea canadensis immersed
in sugar syrup set up a fermentation which
gives butyric acid, butyric ether, carbonic acid,
and hydrogen (Sohutzenberger, 0. B. 80, 328,
497). According to Fitz (B. 9, 1348), glycerin
saturated with calcium carbonate undergoes fer-
mentation, yielding butyric acid, w-butyl alcohol,
and traces of 6thyl alcohol. Fibrin also forms
ammonium butyrate by fermentation (Wurtz, A.
52, 291), and Fitz has found that pepsin and
glycerin, in presence of chalk, is fermented by
schizomycetes at 40° into w-butyl alcohol, n-
butyric acid, besides traces of ethyl alcohol and
a higher acid, probably hexmc {B. 9, 1348 ; 10,
276; 11,42), Pribram (J. 1879, 614) has formed
butyric acid by the action of the ferment of
calves' liver on starch paste, and Fitz has found
that B. subtilis ferments potato-starch contain-
ing salts into butyric acid and small quantities
of alcohol, acetic and succinic acids (B. 11, 52).
Other contributions to our knowledge of this
kind of fermentation are by Iljenko a. Laskowsky,
A. 55, 85 ; Iljenko, A. 63, 268 ; Grillone, A. 165,
127.
Gltuxmic acid is produced by the fermenta-
tion of glucose solutions by Mycoderma aceti
(Boutroux, C. B. 91, 280). Maumenfi contends
that this change is merely oxidation, as copper
acetate and mercuric oxide give similar results
(C. B. 91, 331).
Britrifioation. The term given to the oxida-
tion of ammonia to nitrio and nitrous acids by
an organism or organisms present in the soil.
The formation of nitre in nature, and artificially
in nitre beds, is due to the same cause. Many
experiments have conclusively proved that the
direct combination of oxygen and nitrogen does
not take place to any large extent in nature, and
even ozone appears to be incapable of oxidising
nitrogen. Kuhhuann was the first to explain
the presence of nitric acid and nitrates in the
soU as due to the oxidation of ammonia. This
theory is now held, but the oxidation is indirectly
brought about by the action of organisms. The
first suggestion that the oxidation of ammonia
and organic nitrogen in the soil is the work of a
living organism was made by Pasteur in 1862.
Miiller, in 1873, showed that the ammonia of
sewage and of impure well waters changed spon-
taneously into nitric acid, whereas solutions of
pure ammonium salts and urea remained un-
changed. Schloesing and Miintz (C. B. 77, 208,
353; 84, 301; 85, 1018; 86, 982; 89, 1074)
have established this hypothesis by experiment;-
and Warington (O. J. 83, 44; 35, 429 ; 45, 653 ;
51, 118), at Bothamsted, has shown that the
nitrification in soil and in waters is due to an
organised ferment. The organism is destroyed
at 100°O., and by CHCI3, OS,, and phenol.
PemcilKwm glaucum, Aspergillus vAger, Mucor
mucedo, M. racemosus, Mycoderma vim and M.
aceti, as well as the ordinary forms of bacteria
present in the atmosphere, are all incapable of
effecting nitrification. Schlossing and Muntz
state that they have isolated the organism in
minute round or slightly elongated corpuscles,
which multiply by budding, and appears to be a
644
FERMENTATION AND PUTREFACTION.
micrococcas. The fermentation takes place in
presence of alkaline carbonates or calcium car-
bonate. Besides the humio matter of soil, tar-
taric acid, sugar, alcohol, glycerin, and albumen
are effective as food for the growth of this or-
ganism. Light is not favourable to nitrification.
The change commences slowly, gradually attains .
a maximum of energy, and then becomes slow
again. The formation of nitrous acid by this
organism is rare in the soU, but frequent in
liquids. The influence of temperature, concen-
tration of the solution, depth of liquid, propor-
tion of organic carbon, and degree of aeration
has been studied by Waringtoh and the French
observers. Warington (O. /. 1888, 727-755) has
tested for nitrates in cultivations of upwards of
twenty organisms with negative results. Herseus
{Zeit. f. Hygiene, 1886, 193) has, however, suc-
ceeded in isolating two or three organisms which
he states induce tiie formation of nitrite in urine
and in mineral solutions containing ammonium
sall;s. Percy Frankland has not succeeded in
isolating the organism ; Leone, on the other
hand (Atti d. B. Accademia d. Linoei, 1887,
37), concludes from his experiments that all
micro-organisms are more or less capable of pro-
ducing nitric acid, and that the same organisms
in the presence of organic matter are capable of
reducing nitrates. CeUi a. Zuco (Oazz. 17, 99),
^lajik (Forseh. a.d. Gebieted. AgricuHmrphysik,
10, 56) and Adametz (I. c. 1886, 381) may also be
consulted for further information on this subject.
Bases produced by Fermentation.
1. Ammonia from Urea.— The ammoniaoal
fermentation of urea which takes place in urinals
is due to the action of a bacterium (3. urece).
The urea is converted into ammonium carbonate,
but the change only takes place when mucus or
other organic substances are present, as urea
dissolved in pure water remains unaltered. In
presence of yeast the change takes place very
quickly (Schmidt, A. 61, 168). According to
Musculus (Bi 9, 357) an enzyme is present in
the urine of persons affected with catarrh of the
bladder, which also brings about this change.
It is precipitated by alcohol as a coagulum re-
sembling fibrin, and decomposes urea completely
into carbonic acid and ammonia at 35°-40°. It
has also the power of decomposing hippuric and
uric acids, creatine and guanidine. Its action
ceases in the presence of dilute HCl and most
other acids, but small quantities of phenol have
no retarding action. Dilute alkalis and sodium
chloride have no influence. More recently the
presence of ferments in normal urine has been
confirmed by Stadelmann (^. B. 24, 226, 260).
He finds that pepsin is always present in normal
uriiie, but in no instance has trypsin been
discovered. This conclusion agrees with that
arrived at by Leo and Hoffmann (Fr. 27,
128), and is contrary to the experiments of
Griitzner and his pupils Sahli, Gehrig, and
Holovtschiner. Baw fibrin does disintegrate in
alkaline urine, even in the presence of thymol,
owing, no doubt, to bacteria in tlie fibrin ; but in
no instance did digestion or disintegration take
place when boiled fibrin was used.
Waringtonhastested the ability of overtwenty
organisms to hydrolyse urea. A sterilised 25 p.c.
solution of urine was employed. Micrococaus
ffB.) urece gave a considerable increase of alka-
linity, and B. flvorescens non-liquescens a some-
what smaller increase. Arable soil gave a much
larger increase than either. The other organisms
used had no effect (' The Ohenjical Actions of
Some Micro-organisms,' Warington, C. J. 1888,
727-755).
2. Ammonia from Nitrates cmd Nitrites.
Partial redtuytion of Nitrates. — Meusel (A: [5]
7, 287) obsferved that water containing nitric
acid^nd. carbohydrates, and originally free from
nitrites and ammonia, contained the latter
after being subjected to the action of bacteria ;
and that water, freshly distilled ^nd mixed
with sugar, was not found to reduce nitrates
when the air was excluded from it. Percy F.
Frankland has recently shown (0. J". 53, 373) that
out of thirty-two different micro-organisms ex-
amined sixteen or seventeen have the power of
reducing nitrates to nitrites more or less com-
pletely. The absence of air has no influence on
the result. In many cases the change is a
quantitative one. Ammonia was also sometimes
formed ; but it was due to the decomposition of
the peptone, which was the only other nitrogenous
ingredient present. B. ramosus and B.pestifer
have very marked nitrate to nitrite reducing ac-
tion. The yield of nitrite was augmented by
increasing the amount of sugar and peptone
present. B. aquatiUs does not reduce nitrate to
nitrite, but causes the disappearance of nitric
nitrogen, the deficiency not being accounted for
by the small quantity of ammonia which was
generated in the solution. According to Waring-
ton, the organisms which appear to possess the
greatest power of reducing nitrates to nitrites
are B. fhccus, B.fluorescens non-Kguescens, B.
of swine fever, M. wrece, M. gelatinosus, Staph,
candidus, and Staph. Vutevs. The following also
reduce nitrates freely: B. termo, B. of typhoid
fever, B. of infantile diarrhoea, B. of cholera,
B. of septictemia, B. anth/racis, B. Demcke's
comma, and Staph, albus Uguescens, B. subtiUs
yields no nitrite in a urine solution, but forms a
trace of nitrite in broth after some time. Sirep-
tocoecits sca/rlatincB yields a mere trace of nitrite
in broth cultures. B. fl/uorescens Uguescens, B.
toruUformds, B. sulphu/reus, B. Finkler's comma,
B. comma noma and M. a/u/reus, failed entirely to
effect reduction J:o nitrites (Warington, 0. J.
1888, 727-755).
3. Bases formed im fermentation. — Foisonons
bases having properties resembling, the alkaloids
are produced in putrid fermentation, and also in
small quantities in alcoholic fermentation.
The bases formed in the putrefaction of meat
and fish are known as ptomaines, and a con-
siderable amoumt of literature on their formation
and properties now exists, which it is impossible
to deal with in the present article. Gautier a.
Etard (C.B.94, 1598) have shown that the com.
plex phenomena of putrid fermentation may be
regarded as brought about by the hydration of
the complex albimiinoid molecules into simpler
molecules. Two compounds are apparently first
formed, one of which is stable and gives rise to the
glauco-proteins and leucines, to which Schutzen-
berger attributes the formula O^'H.2„.,'if^0i, whilst
the other is unstable, and decomposes rapidly
into NH,, COj, formic, acetic, and oxalic acids. ,
In Schiitzenbergef's method of hydration
with barium hydrate, the amides are not by-
FERMENTATION AND PUTREFACTION.
645
drated, but bacteria in putrefaction slowly change
them into ammoniaoal salts. The crystalline
body C„H2gN,0g produced abundantly in the
putrefaction of fish also undergoes hydration
when similarly treated. Putrefaction being essen-
tially a process of hydration it follows that the
aromatic derivatives and the bases produced
during fermentation pre-exist as nuclei in the
flesh. The bases formed in the putrefaction of
the skate can be obtained by acidulating the
liquid products with sulphuric acid. On evapora-
tion, m vacuo, indole, phenol, and other volatile
products are removed and the residue, after
treatment with baryta, is extracted with chloro-
form. The bases are colourless oily liquids and
resemble those described by Sehni. They have
an odour like that of the carbylamines and hydro-
collidine. By fractionation two bases, CgH„N
and OsHijN, have been isolated. > The latter
(110°) closely resembles Cahours's and Etard's
hydrocollidine, with which it is probably iso-
meric. Two bases having the formula OjHnNOj
and C,H,jK02 have similarly been obtained from
the products of the putrefaction of flesh and fibrin
(Salkowski, B. 12, 648 ; 16, 1191). Brieger (B.
16, 1186) has extracted from putrefied horseflesh
the bases CgHi^N, and C^HjiN. A base having
the formula G,H,gN2 (171°) and soluble in most
solvents has been isolated by Morin from the
products of alcoholic fermentation. It forms a
doable Ft salt and gives precipitates with the
usual alkaloid reagents (O. B. 106, 360). Its
toxic effects have been studied byE.Wurtz (C.B.
106, 363). Tanret considers this base identical
with (3)-glacoBine obtained from glucose and
ammonia (C. B. 106, 418). An examination of
the amount of nitrogen bases present in fer-
mented liquids (brandy, rum, &o.), has also been
made by Lindet (C. B. 106, 280). ^
Sngar-forming ferments. — The more impor-
tant chemical ferments which belong to this
group are diastase, ptyalin, myrosin, emulsin,
invertin, animal invertin, and one of the fer-
ments which exist in the pancreas. They are
found in the animal and vegetable kingdoms, in
the former they are secreted by some of the prin-
cipal organs, in the latter they occur in various
parts of the plant. The sugar produced may be
either dextrose or maltose, and the substance
decomposed differs with the different ferments,
starch, cane-sugar, and the various glucosides
being the more important ; we have already seen
that the enzymes may be isolated by precipi-
tating the aqueous extracts of the organs con-
taining them with alcohol. They are also mostly
soluble in glycerin, which may be used to ex-
tract them from the finely divided material.
The glycerin extract is then dropped slowly into
strong alcohol, and the precipitated ferment
collected. The chemical composition of these
bodies has been investigated by Krauoh, Dubrun-
f aut, Huf ner, Donath, Barth, and others, and from
their analyses it is known that they all contain a
considerable percentage of nitrogen. Invertin,
emulsin, and the diastatic pancreas ferment also
contain sulphur. The infiuenoe of temperature
and light upon their action has already been
alluded to. Dried diastase can be heated to 158°,
and the pancreatic ferment to 162°, without
destroying their fermentative property. The
amount of work which they are able to perform
Voii. n.
in a given time is, however, diminished by heat-
ing above 100° (P. Huppe, O. O. 1881, 745).
Chloroform, carbon bisulphide, ether, prnssic
acid, do not retard the action of these ferments,
but most acids and alkalis hinder their action.
All salts and bodies which coagulate albumen
have the property of stopping this kind of fer-
mentation. The chemical change brought
about by the sugar-forming enzymes is one of
hydrolysis. Diastase, ptyaUn, and the diastatic
pancreas ferment convert starch or glycogen
into a sugar (maltose) and dextrin. The pan-
creatic ferment and ptyalin yield a dextrin
(achroodextrin) which differs from the dextrin
obtained by means of diastase in not re-
acting with iodine (Naffe, Pf. 14, 473). In-
vertin converts cane-sugar by hydrolysis into
dextrose and levulose. The ferment action of
emulsin consists in the hydrolysis of the glucos-
ides. Glucose is the constant product of the
action. The following ore those decompositions
which are best established. SaUcin to saligenin,
helioin to salicylic aldehyde, arbutin to hydro-
quinone and metbylhydroquinone, amygdalin to
benzoic aldehyde and prussic acid, coniferin to
coniferylalcoholanddaphninandconvolvulinare
similarly hydrolysed by emulsin. Nencki is of
opinion that in hydrolysis the water is split into
hydrogen and hydroxyl by emulsin {J. pr. 17,
108). Myrosin appears to determine the breaking
up of the molecule of potassium myronate or of
the free myronic acid into mustard oil, sugar,
and sulphate without the assimilation of the ele-
ments of water. It seems probable that with
further investigation the formula of myronic
acid may be modified and that this ferment
change will also be found to be one of hydrolysis
(Will a. Kdmer, A. 125, 263 ; Franchunont's
Kort Leerboek).
Feptoue-forming ferments. Digestion. — The
peptone-producing ferments, pepsin, trypsin,
pepsin (of plants), and papain, convert albumen
into peptone. This change apparently is brought
about in a similar manner to those of the last-
mentioned group, the elements of water being
taken up by the albuminoid substances. Other
bodies besides peptone are produced, trypsin and
papain yielding crystalline amido- compounds
(leucine). Wurtz is of opinion that papain acts
by combining first with the fibrin, and that an
insoluble product is thereby produced, which by
the action of water is reconverted into the fer-
ment and soluble substances resulting from the
hydration of the fibrin (Wurtz, 0. B. 91, 787 ;
93, 1104). Pepsin also seems to first form an in-
soluble compound with fibrin, which is subse-
quently broken up by water. Certain bacteria
resemble tliese enzymes in their action, and pro-
bably have this property from secreting a similar
ferment. The principal albumen-forming fer-
ments are the liver ferment, the blood ferment,
and chymosin. Ferments analogous to the liver
ferment exist in the vegetable kingdom. The
conversion of casein into cheese by rermet is an
example of this class of fermentation, and from
the analyses of these two bodies it seems pro-
bable tha^ in this case also the change is one of
hydrolysis. A ferment similar to that existing
in the Uveris found in certain plants, notably in
OxaUs Acetosella, 0. stricta, Cirsium arvense,
Bumex Patientia, in the leaves of artichokes, and
NN
646
FERMENTATION AND PUTREFACTION.
in the seeds of black pepper and Wilhamia co-
agulans. Ceitain bacteria separate a ferment
which behaves like chymosin.
A ferment also exists in the pancreas, which
is capable of decomposing the fats into gly-
cerin. Not only are the triglycerides attacked,
bnt complex molecules like lecithin are also hy-
drolysed.
Antiferments or Antiseptics. — Many inor-
ganic and organic substances have the property
of arresting or hindering fermentation. They
act by killing the organisms which bring about
. the fermentation, and most of the substances
which have poisonous properties have also anti-
eeptic properties. In the earlier experiments it
' was noticed that while creosote and phenol ar-
rested the development of fungi and germs tef-
mentationstillproceeded,andBaohholz(<7'. 1867,
742) found that milk tamed soar when phenol
was present. Naonyn {J. 1865, 606) noted that
benzene interfered with the action of yeast on
sugar solutions. Pienkowsky {J. 1865, 606) ex-
amined the antiseptic action of a considerable
number of salts on meat with the following re-
sults :—
No antiseptic action :
Alum, A1,3S0„ Na^HPO,, Sr2N03, Ba2N0.„
(NH,)A04, Na^OA. BaClj, NajSO,, Na^S^Oj,
NH,NO„ KCIO,, NajSO,, K^SO,, MgSO,,
(NH4)2S0<, Mn(AcO)j, and AsA-
Delayed putrefaction for one month :
KAoO.NaAcO, Ca(AcO)2, NaCl,NH401,SnCl„
MnClj, ZnClj, ZnS04,FeS0„ KjSO„and Pb2N0,.
Delayed putrefaction for more than six
months :
NH4AcO,Ba(AcO)2,CaClj,CuCl5,HgCl2,CuS04,
Pb(AcO)2, EjCrjO,, aniline nitrate, phenol, and
acetic acid.
Formic acid, according to the same inves-
tigator, is a powerful antiseptic for sugar solu-
tions. Severi (Z. [2] 4, 285) has examined the
antiseptic action of the animal secretions. Alco-
holic fermentation and putrefaction are arrested
by gastric juice, but not by pepsin. Lactous fer-
mentation is not retarded by either reagent.
Boric acid and most of its compounds have
antiseptic properties. Dumas found that borax
prevents the action of yeast water on sugar, of
synaptose on amygdalin, and of myrosin or my-
ronic acid. Calcium borate and boric acid either
alone or mixed with glycerin prevent the for-
mation of mildew and the putrefaction of meat.
Mercuric oxide appears to be the most powerful
. of all antiseptics, and next to it mercuric chloride.
Among organic bodies phenol, chloral hy-
drate, chloroform, salicylic acid, benzoic acid,
hydrocyanic acid, and thymol, all have marked
antiseptic properties.
Of the alkaloids, quinine prevents, while nico-
tine accelerates fermentation. Calvert (Pr. 20,
191) found that on the addition of one thousandth
part of the following antiseptics to a solution of
albumen he obtained the following results : —
1. Phenol and cresol prevented the growth of
fungi and bacteria.
2. ZnClj, EgCLj, and zinc phenol Bulphonate
prevented the development of vibrios, but did
not stop the production of fungi.
3. GaO, quinine sulphate, pepper, and EON,
permitted the growth of vibrios, but allowed the
fungi to develop.
4. Those which had no preventive action
(under these conditions). SO,, H^SO,, HNO,,
AsA. AcOH, KHO, NaHO, NH,, Cl,-NaCl, CaCl„
AlCl,, Ca(OCl)Cl, KCIO.,, OaSO„ PeSO^, CaSO„
NajSjOj. Na.,HPO„ Caj2P0„ KMnO^, K and Na.
Phenol snlphonates, picric acid, turpentine, and
wood charcoal. Sodium silicate (Babuteau a,
Papillon, 0. B. 75, 755) prevents the alcoholic
fermentation of grape-sugar, and the fluosilicateg
have also considerable antiseptic properties.
Salts of bismuth even in small quantities
completely prevent secondary fermentations in
worts (Gayon a. Dupetit, C. B. 103, 883-885).
The influence of calomel on fermentation and
the life of micro-organisms has been carefully
studied by WassiliefE (H. 6, 112-134). The com-
parative antiseptic properties of EgCy,, inercury
oxyoyanide, and HgCl,, have been determined
by Ohibret (C. B. 107, 119). Eatimoff {J. Ph.
[5] 11, 83-90) has determined the limits between
which lie the minimum quantities of various
antiseptics required to kill and to prevent the
development of microbes and bacteria in certain
media.
The relation of antiseptic power to chemical
constitution has been investigated by 3. B. Dug-
gan (Am. 7, 62-64) by noting the amount of sub-
stance required to prevent fermentation by bacil-
lus subtiUs in a solution of beef peptones.- The
following numbers show the relative antiseptic
values of the materials used : Salicylic acid, 4 ;
m-oxy-benzoio acid, 6 ; ^-oxy -benzoic acid, 8 ;
phenol, 20 ; pyro-catech, 20 ; resorcin (25) ; hy-
droquinone, 30 ; pyrogallol, 15 ; methyl alcohol,
300 ; ethyl alcohol, 600 ; normal propyl alcohol,
200. Of the three phenol sulphohic acids the
ortho-acid only has antiseptic and disinfecting
properties in a marked degree (Vigier, J. Ph. [5]
11, 145-152, 214-217). Phlorogluoin is pos-
sessed of no antiseptic properties, whereas py-
rogaUol is poisonous, and resorcin coagulates
both vegetable and animal albumen (Andeer,
C. C. 1884, 340-341). A paper by G. Marp-
mann (Ar. Ph. [3] 20, 905-924) deals with the
methods for determining the vitality of those
bacteria which cease to move when dead, and
points out the difference between antisepsis and
disinfection, and gives a list of the literature on
the subject to 1881.
Literature consulted. —
Euber a. Becker, Pathol, histol. u. bacterial.
Untersuchungsmethoden, licipzig, 1886.
Nageli, Theorieder G&hrung, Munohen, 1879.
Frazmowski, Untersuichungen il. d. Entwicke-
Umgsgeschichte u. Fermentwirkung einiger
Bacterien-Arten, Leipzig, 1880.
Mayer, Lehre v. d. chem. Fermenten o. Erusy-
mologie, Heidelberg, 1882.
Fremy, Swr la giniraUon des Ferments, Paris,
1875.
De Bary, VergleHohe/ndLi Morphol. u. Biolog. der
PUze, Mycetozoen m. Bacterien, Leipzig,
1884.
S.E.
FEBBATES. Salts of the hypothetical /erne
acid 'SL^e^O^. Neither the acid nor its anhydride
(FeOj) has been isolated.
Stahl noticed in 1702 that a violet solution is
obtained by fusing iron with saltpetre and wash-
ing with water, or by adding a solution of iron
in HNO, to oonc. KOHAq.
FERRITES.
647
*rrom measurements of the O evolved and the
FejOj formed in the decomposition of K ferrate,
Fremy gave the f6rmula FeO, to the hypothetical
acidic radicle of the ferrates ; this was confirmed
by H. Bose, who determined the quantity of I set
free from KI by reaction with Ba ferrate (A. 48.
230). '
The ferrates have been examined by Fremy
(C. B. 12, 23 ; 14, 442 ; 15, 1106 ; 16, 187) ; H.
Bose {A. 48, 230; P. 59, 315) ; Denham Smith,
(P. M. [3] 23, 217); Merz (J. pr. 101, 269);
PoggendorfE (P. 54, 373).
Barium ferrate, BaFe04.HjO, has been ob-
tained as a solid. The compositions of the soluble
EandNa ferrates were deduced from estimations
' of the ratio of Fe ppd. as FcjO, to O evolved by
decomposing the solution by heat (Fremy, Den-
ham Smith), and also by reducing by SOj and
then estimating the ratio of FejO, ppd. to SO, in
solution (H. Bose).
Barium ferrate BaFeOj.HjO. Obtained as a
purple-red powder by adding BaCIiAq or
Ba(XO,)^q to E^FeOtAq, washing, and drying
(Denham Smith). It is more stable than E^FeO, ;
dscomposed by HNOaAq, slowly by HjSOjAq ;
sol. in acetic acid, forming a red liquid, which
evolves O on heating ; scarcely decomposed by
organic salts.
Potassium ferrate, E^i^eO^Aq. Prepared by
beating 2 pts. ENO, in a large Hessian crucible,
arranged so that only the bottom is heated to
dull redness, and throwing in 1 pt. iron filings ;
the fused mass is extracted with cold water in a
dosed vessel (Fremy). More conveniently pre-
pared by passing a rapid stream of 01 into cone.
KOHAq warmed to about 40°, holding FeOjH, in
suspension ; Merz (Z.c.) recommends to dissolve
5 pts. EOHin8pts.H20,8nd toadd8pts.FeGl,Aq
of S.G. 1-109 ; excess of 01 must be avoided.
According to Fremy, crystals of EjFeO,, may be
obtained by making the EOHAq very cone, and
adding EOH from time to time as the 01 is
passed in ; the crystals may be freed from EOl
by solution in water and ppn. by potash, they
may then be dried on a porous ule and kept in
sealed' tubes. Foggendo^ (2.c.) says that crys-
tals of potassium ferrate may be obtained by an
electrolytic method ; a cylindrical vessel of porous
porcelain is placed in a beaker cooled by ice;
potash solution is poured into both vessels, a Ft
plate, which serves as negative electrode, is im-
mersed in the porous cylinder, and the positive
electrode is a plate of wrought iron (not steel)
which is placed in the beaker ; when a strong
current is passed, the liquid round the positive
pole becomes dark red, and crystals of E ferrate
form on the iron plate. Bloxam (C. N. 54, 43)
says that a solution of E^FeO, may be obtained
by adding a fragment of EOH to a little FojOl,
and then a few drops of Br, heating gently and
dissolving in water.
A cone, solution of EjFeO, is deep red ; it is
stable especially if a little EOH be present ; on
dilution and warming, FeOaH, is ppd., and O is
evolved ; the solution is decomposed by acids ;
it reacts towards SOjAq, Ac, as an oxidiser;
the solution is decolourised by metals and many
salts of earth-metals, e.g. alum ; it is also
decolourised by NH,Aq with evolution of N;
the solution acts as an oxidiser towards most
organic compdnnda which are oxidised by
EMn04Aq, e.g. alcohol, sugar, albumen, potas-
sium tartrate and oxalate.
Sodium ferrate NajFeO^Aq. Solution ob.
tained similarly to EjFeOjAq.
M. U. P. M.
FEBBIC COUFOUITDS v. Ibon.
FEBBICTANISES and FEBBOCYAHTISES.
Salts of ferrioyanhydrio acid HaFeCyu, and
ferrooyanhydric acid HiFeOyj, v. pp. 333, 337.
FEEBITES. Ferric oxide Fefi, forms com-
pounds with several metaUio oxides more basic
than itself ; these compounds belong to the
form FcjOs-MjO and Fefi,.UO, where Mj=E,
and Na,, and M=Ba, Ca, Ou, Mg, or Zn ;
they _ are analogous in composition to the
aluminates (q.v. vol. i. p. 141), and may be re-
garded as metallic derivatives of the hydroxide
FeAH2( = FeA-H20).
Barium ferrite BaO.Fe20,=BaFe204. Ob-
tained by List (B. 11, 1512), by ppg. Fe01,Aq by
BaOAq, as a brown, magnetic solid.
Caloinm ferrite CaO-FejOj = CaFojO,. Percy
(P. M. [4] 45, 455) obtained this salt in metal-
like lustrous crystals, S.G. 4-693, by heating
equal parts of GaOO, and FeJO, to white heat for
several hours. List (B. 11, 1512) obtained the
compound as a brown solid by adding CaOAq to
FeGljAq, washing with GaOAq, and heating (v.
also Pelouze, A. Oh. [3] 33, 5 ; also Bousseau a.
Bernheim, G. B. 106, 1726).
Copper ferrite Cup.FejOs = CuFej04. A
brownish-black, magnetic solid; by adding
EOHAq to a mixture of CuSO, and FeCl, in
quantity sufficient to ppt. all Ou, drying over
H2SO4 in vacuo, and heating (List, I.C.).
Magnesium ferrite MgO-FcgOj^MgEejO,.
Occurs native as Magnoferrite. Obtained by
mixing equivalent quantities of MgSp, and
NaOH and adding FeCl^q until the liquid is
still slightly alkaline, and heating the pp.
strongly (List, Z.c.). Kraut (C. C. 1864. 1088)
obtained Fe2O3.6MgO.9H2O by adding 6 equivs.
MgSO, and 1 equiv. of a ferrous salt to excess of
EOHAq, S.G. I'l, boiling for some hours until
the pp. was white, and drying at 120°.
Fotassium and Sodium ferrites
E20(Na20).FesO, = E2(Na2)Fe20,. Formed by
adding .FCjOj to molten E^CO, or Na^OO, (v. v.
Schafigotsch, A. Oh. 43rl7; Schneider, J.pr.
108, 19; List, B. 11, 1512). Bousseau a. Bern-
heim (0. B. 107, 240) describe E20.Fe20, as
transparent, red-brown crystals; obtained by
mixing crude E ferrite (best that made by fusing
FeOgH, with 4 parts EjGO,) with twice its weight
of ECl, and heating strongly until most of the
ECl is volatilised. Other crystalline compounds
of Fe20, with EjO and xE^O were obtained by
heating FeSO, with an equal weight of EGl.
Zinc ferrite ZnOJ'e^Og^ZnFejO,. Occurs
native as Franklimte. Obtained as minute,
black, octahedral crystals, which are slightly
magnetic, by heating to whitehess for 4 days a
mixture of 1 pt. Fe,0„ 2 pts. ZnO, and 2 pts.
fased H,BO„ and treating with dilute HGlAq.
S.G. 6-132 (Ebehnen, A. Oh. [3] 33, 47 ; v. also
DaubrSe, 0. B. 39, 153 ; Beich, J. pr. 83, ^66 ;
and List, B. 11, 1512).
Ferrites of lead, manganese, and silver seem
also to exist («. List, Lc; H. Bose, P. 101, 323 ;
Fischer, 8, 66, 861).
M. M. P. M.
JIII2
648
FJblRULIO ACID.
FERULIC ACID C,„H„0, i.e.
[3:4:l]C,H,{OMe)(OH).CH:CH.COjH. Mol. w.
194. [169°]. Occurs in asafoetida, from which it is
obtained by ppg. the alcoholic tincture with lead
acetate and decomposing the resulting lead salt
by HjSO. (Hlasiwetz a. Barth, A, 138, 64). Ob-
tained also by boiling its acetyl derivative with
aqueous EOH. Long trimetric four-sided needles
(from boiling water). Y. si. sol. cold water, v.
sol. cold alcohol, m. sol. ether. Its aqueous
solution is ppd. by Pb(OAo)2 and by FcjOlj.
Ammoniacal AgNO, gives an egg-yeUow pp.;
reduction takes place on boiling. Potash-fusion
gives protocatechuic and acetic acids. It re-
duces boiling FehUng's solution. Sodium-
amalgam reduces it to hydroferulic acid
C„H3(0Me)(0H).CHj.CHj.C0jH [90"].
Salts.— NHjA'aq : laminp.— KA' (at 110°) ;
straw-yellow deliquescent crystals. — AgA'.
Acetyl derivative
C„H3(OMe)(OAc).CH:CH.C02H. [197°]. Pre-
pared by boiling a mixture of aoetyl-vanUlin
(5 pts.), NaOAc (5 pts.) and Ac^O (15 pts.) for
i) hours (Tiemann a. Nagai, B. 11, 650). Vanil-
lin may be used instead of its acetyl derivative.
Slender needles, v. sol. alcohol and ether, si. sol.
water.
iBO-fernlic acid OuH,„0, i.e.
[4:3:1] C5H,(0Me)(0H).CH:CH.C02H. Eespere-
tic acid. [228°].
Wormaiion.—l. By the action of Mel and
KOH on caSeic acid (Tiemann a. Nagai, B.
11, 654).— '2. Together with phloroglucin by
boiling hesperetin with dilute NaOH.
Properties. — White needles or plates. Sol.
alcohol, ether, and hot water, si. sol. cold water,
benzene, and chloroform, insol. ligroin.
Beficiions. — 1. Fused with KOH it gives pro-
tocatechuic acid. — 2. By reduction it gives
hydro-isoferulic acid [146°]. On heating it gives
COj andhesperetol {C8H3(OMe)(OH).CH:CHj}.
, Salts. — A'jCa2aq: sparingly soluble needJes.
— A'Ag : slightly sol. pp. The salts of barium,
zinc, ' copper, and lead are also sparingly
soluble pps.
Methyl ether A'Me. [79°]. Colourless
needles. Soluble in alcohol.
Acetyl derivative
C.H3(OMe)(OAc).CH:CH.C02H. [199°]. Colour-
less plates. Soluble in alcohol and ether, in-
soluble in water. On oxidation with KMnO^ it
gives isovanillic acid.
Methyl-isoferulic acid
CeH,(0Me),.CH:0H.C02H. F. Vol. i. p. 659 (Tie-
mann a. Will, B. 14, 955).
FEatrilC ALDEHYDE C,oH,„0, i.e.
[3:4:l]0,H3(OMe)(OH).CH:GH.CHO. [84°]. From
its glucoside by treatment with emulsin at 35°
(Tiemann, £.18, 8484). Yellow needles. SI. sol.
cold water, v. sol. alcohol, ether, and benzene ;
insol. ligroin. Combines with KaHSO,. Its
aqueous solution is coloured green by FeCl,, and
on boiling with FeCl, ^ves off an odour of
vanilla.
Glucoside C^H^gO, i.e.
C,a:3(OMe)(O.Oja„05).CH:OH.CHO. [202°].
From the glucoside of vanillin by treatment with
aqueous KaOH and aldehyde (T.). Yellow
needles (containing 2aq) (from water). SI. sol.
cold water, v. sol. alcohol, insol. ether, chloro-
form, and benzene. Ltevorotatoiy.
Oxim of the glucoside \ ,
C5H3(OMe)(OC^„03)CH:CH.CH:NOH. [103°].
Needles, si. soL cold water, m. sol. alcohol, in-
sol. ether.
Phenyl hydra^ide of the glucosidt
0,H,(OMe) (OCsH, ,05).CH:CH.CH:NjHPh. [212°].
Amorphous, v. sol. alcohol, v. si. sol. water and
ether.
FIBRIIT V. Pboieibs and Bjlood.
FIBBIHOGEIT v. Fboieids.
FIBBINOFLASIIN v. Pboteids.
FIBBOIN V. FsoTEins, Appendix O,
FICHTELITECsHj^orCisH^j. [46°]. (above
320°). A fossil resin found in the Fichtelgebirge.
It is a hydro-carbon containing from 87 to 88 p.c.
carbon (Trommsdorff, A. 21, l26 ; Bromeis, A.
37, 304 ; Clark, A. 103,236; 119, 226; Schrotter,
P. 59, 37 ; Hell, B.22, 498). Monoclinio prisms.
Insoluble in, and lighter than, water ; v. si. sol.
alcohol, V. e. sol. other. With halogens it gives
products by substitution.
' FmCIC ACID C^HijOj. Isobutyryl-oxy-
naphtho-guinone? [180° uncor.] ; [185°] (L.).
Occurs in the root of the common male fern
{Aspidium FiUx-mas) from which ij) may be
extracted by dry ether. After a few days the
ether deposits the acid as a greenish -yellow
powder, which may be purified by washing with
alcohol-ether and recrystallising from ether
(Luck, A. 54, 119 ; B. 21, 3465 ; Grabowski, A.
143, 279 ; Daccomo, C. 0. 1887, 1357 ; B. 21,
2962; Patern6, B. 22, 463). Minute lamina,
insol. water, v. si. sol. alcohol, si. sol. ether, v.
e. sol. CS2, ligroin, and terpenes. After fusion
it melts at 150° to 160°. Its solution reddens
litmus. Potash-fusion gives butyric acid and
phloroglucin. Water at 180° gives isobutyrio
acid and a body C„gH„0„ KMnOf and HNO,
(S.G. 1*4) give isobutyric and oxalic acids. Zino
dust gives a body CnHj^O,,. — PbA', : curdy pp.
Benzoyl derivative C^i^^tfle- [123°].
Ethyl eifcer [142°]. Brick-red crystals.
Ethylene ether. [165°].
Propyl ether. [158°].
Phenyl-hydrhzide C„H„0(NjHPh)^
[198°]. Bed needles (from ether).
Anilide C„H„0,NHPh. [140°].
Bromo-fllicic acid 0„H,jBrOs. [122°].
Chlorofilicic acid C,jH,sC105. From chlorine
gas and solid filicio acid. Amorphous. Its
alcoholic solution gives with lead acetate a pp.
of PbA'j.
Tri-chloro-fiUcic acid OhHijCIjOj. Formed
by the action of chlorine on filicic acid sus-
pended in water. Amorphous. — PbA'j.
FILTBAIION. The separation of a solid
from a liquid by means of a membrane imper-
vious to the solid.
FISCIC ACID. 0. 67-33 to 6766 ; H. 4-73
to 5-08. [204°]. A substance extracted from
the Fiscia parietina, a lichen growing abun-
dantly in Sicily on the branches of shrubs. Pre-
pared by heating the lichen in a reflux apparatus
with boiling alcohol ; the black residue on treat-
ment wit^ ether leaves a black crystalline re-
sidue, which is frequently recryst^lised from
benzene in presence of animal charcoal. Yield
small. Forms red-brown crystals, soluble in
potash forming a rose-red salt. It exhibits con-
siderable resemblance to ohrysophanio acid, buti
FLAMfi.
649
differs fiom it in oomposition and higher melt-
ing-point (Patem6, G. 1882, 254).
FISETIN Oj,H„Og (J. Sohmid, B. 19, 1734 ;
c/. Kooh, B. e, 285 ; BoUey,BJ. [2] 2, 479). This
name was given by Chevreul to ' young fustic,"
the yellow colouring matter of Piset wood (the
heart-wood otBhus CoUntis, a species of sumach).
It occurs as a glucoside combined with a tannin.
Alkalis or acids split this compound up into the
tannin and the glucoside ('fustin '). The glu-
coside is split up by dilute H^SO, into fisetin and
a sugar. Fisetin crystaUises from alcohol in
small lemon-yellow prisms ; and from HOAc in
yellow prisma (containing 6aq). SI. sol. ether,
benzene, ligroin, chloroform, and boiling water,
V. sol. alcohol. It begins to blacken at 270° but
does not melt below 360". It may be sublimed in
small needles. Nitric acid oxidises it to oxalic
and picric acids. HjSOj forms a sulphonio
acid. It reduces Fehling's solution. Alkalis turn
its alcoholic solution brownish-red. Potash-
fusion gives protocatechuic acid and phloro-
gluciu.
Salt. — CjjHijNajO, : yellow needles.
Acetyl derivative C^E.,„Xafl,. [201°].
Needles, si. sol. boiling alcohol, v. sol. chloro-
form.
Benzoyl derivative CjjH,jBZ|,Oj. [185°].
Needles. With excess of BzCl it gives a com-
pound [195°].
Glucoside {(CsHiiOJ.CajHuOjjjO. Fustin.
[219°]. Obtained as above. Needles; v.sol.boiling
water, alcohol, and alkalis, si. sol. ether. Lead
acetate gives a yellow pp. Cuprio acetate gives
a brown pp. FeCl, produces a green colour
which, on addition of dilute soda, changes through
violet-blue to red.
Ethyl derivative CjaHioEtjO,. [107°].
Long pale-yellow needles.
Methyl derivative C^iBj^Mefl,. [153°].
riXED A1&. The name given by Black to
carbonic anhydride 00^ [v. vol. i. p. 691).
FLAME is gas or vapour raised to a tempera-
ture at which it becomes self-luminous. The
luminosity depends essentially on the specific
emissive power for light of the incandescent
gas, and according to the law of exchanges is
proportioned to the power of the gas to absorb
the same kind of light at the same temperature.
In nearly aU cases, the high temperature, and
hence the flame, is the result of chemical energy,
displayed (in the great majority of instances) in
the combination of two or more gaseous sub-
stances ; hence the production of flame is in
general essentially a synthetical process. There
are, however, oases in which flame is produced
by the breaking up of a complex molecule either
into simpler forms of combination, or into its
elements, as, for example, in the flame which ac-
companies the destruction of nitrogen trichloride
where no combination or rearrangement of the
constituent elements other than into molecules
takes place. Flames of this character are in-
variably ' solid,' i.e. they are wholly composed of
glowing particles, and are wanting in the internal
structure which is characteristic of all ordinary
flames. Flames of the synthetical class may,
however, be ' solid ' — such, for example, are the
flames of intimate mixtures of oxygen and hydro-
gen, of chlorine and hydrogen, or of vapour of
earbon disulphide and nitricoxide. In these cases
the chemical combination is exceedingly rapid ;
the heat developed is great, and the consequent
molecular vibration is so intense that it becomes
explosive in character.
According to Bunsen {P. A, 131, 161) in a
mixture of carbon monoxide, or hydrogen, with
oxygen in the exact quantity needed for complete
combination, only one-third of the carbon mon-
oxide or hydrogen is burnt at the maximum
temperature, the remaining two-thirds at the
high temperature (2558°-3033°) having lost the
power of combination. If an indifferent gas is
present the temperature of the flame is reduced,
and larger quantities of the gases combine to:
gether, as much as half the amount of carbon
monoxide or hydrogen combining within a range
of temperature between 2471° and 1146°.
It would appear, therefore, that gases in
combining together with the production of such
an amount of heat as to produce flame unite
per saltum, and that the combustion is not a
continuous uninterrupted process. Thus in the
case of carbon monoxide, when two vols, of this
gas are mixed with one vol. of oxygen, both
ga^es at 0°, and the mixture is ignited, the
temperature is raised to 3033°, and two-thirds
of the carbon monoxide is left unburnt ; by
radiation and conduction the temperature is
lowered to 2558° without any combustion of the ,
carbonic oxide ; at a little below this point com-
bustion recommences, and the temperature is
again raised to 2558°, but not above this point.
This temperature continues until half the carbon
monoxide is burnt, when the combustion ceases,
until by cooling and radiation the gaseous
mixture has cooled to 1146°, and these alternate
phases of constant temperature and of decreas-
ing temperature are repeated until the whole of
the combustible gas is burnt.
Bunsen has ■ also determined the rate of
propagation of the combustion of a mixture of
oxygen and hydrogen, and of carbon monoxide
and oxygen, mixed in the exact quantities for
complete combustion. In the oxyhydrogeii
mixture the velocity of inflammation was
34 metres per second ; in that of carbon mon
oxide and oxygen it was less than 1 metre per
second. By adding to the mixture increasing
amounts of an indifferent gas the rate is rapidly
diminished until the progress of the flame
throughout the mass may be followed with the
eye.
The flames with which we are ordinarily
familiar, as that of a candle or of coal-gas, are,
however, of a very different character from the so-
called ' solid ' flames. In ordinary flames a stream
of combustible gas comes in contact with atmo-
spheric air at a temperature sufficiently high to
effect the chemical union of the constituents of
the gas with the oxygen of the air with the con-
sequent production of heat and light. It is
obvious that this union can only take place at
the points of contact between the air and the
gas : hence such a flame is necessarily hollow,
its internal space consisting of 'combustible'
gas which has not yet come into contact with
oxygen in quantity sufficient to burn it. The
form of the flame for any particular gas will
therefore be dependent upon the mode in which
the gas is caused to issue into the air, and this,
in its turn, is controlled by the character of the
SGO
\
VLAHSS.
jet or burner, and by the ptegsure under which
the gas ia delivered.
It is obviously immaterial so far as the pro-
duction of a flame is concerned -whether the gas
issues into the oxygen, or the oxygen into the
' combustible ' gas. In either case we shall have
chemical combination occurring at the point of
contact of the two gaseous substances, provided
the temperature be raised to that of ignition,
and a flame will result from the heat of combi-
nation. In this way chlorine may be caused to
burn in hydrogen, and air may seem to burn in
coal-gas. Hence the terms ' combustible ' and
' supporter of combustion ' as applied to gases
which may be made to burn in each other have
no real significance ; the same gas may appear
to be ' combustible,' or ' to support combustion,'
in accordance with the manner in which it is pre-
sented to the gas with which it combines with
the production of sufficient heat to give flame.
The two main factors which determine the
interaction of two gases, which are susceptible
of chemical change when mixed, are tempera-
ture and degree of condensation. A stream of
hydrogen issuing into the air under ordinary
circumstances does not ignite. If, however, the
air or the hydrogen, or both, be raised to a
sufficiently high temperature just prior to ad-
mixture, chemical union will be initiated and
flame will result. Hence a red-hot wire, or the
flame of a taper, or electric sparks, cause
the hydrogen to bum ; these means have sufficed
to raise the temperature of the gases to the
point at which chemical combination can occur.
The union of oxygen and hydrogen may, how-
ever, be effected at a low temperature under
certain conditions, as, for example, by the ' cata-
lytic ' action of platinum or palladium. If a
perfectly clean piece of palladium or platinum
foil be suspended in a mixture of oxygen and
hydrogen at the ordinary temperature, water will
be seen to form on the surface of the metal in
' rapidly increasing quantity, the metal will be-
come hot and wiU eventually raise the tempera-
ture of the gases to the point at which an almost
instantaneous combination will occur, and flame
and explodon will result. This power to effect
union is dependent on the capacity of the metal
to ' occlude ' gas, and, as Berliner {W. 35, 791)
has shown, it is more efficacious in the case of
palladium than in that of platinum,in conformity
with Graham's observations of the relative
* occlusive ' capacities of the two metals for
hydrogen. The ' catalytic ' action is greatly
augmented by increase of temperature, which
explains the rapidly increasing rate of formation
of water and the eventual explosion. The
occluded hydrogen at the ordinary temperature
combines with oxygen, heat is developed, and this
accelerates the union of fresh quantities of the
gases, the metal is thereby rapidly raised in
temperature, and eventually brings the mixture
.to the point of inflammation. Precisely the
same principle is seen at work in the well-known
Dobereiuer lamp, in which a current of hydrogen
is caused to impinge upon a small quantity of
platinum-black which has been exposed to the
air. Under the influence of the finely divided
metal the gases combine with the generation
of sufficient heat to effect the ignition of the
hydrogen as it issues into the air. Dulong and
Thenard, and Turner and Senry.have shown
that copper and iron turnings, zinc foil, and even
charcoal, will bring about the same result, al-
though much less actively, at varying tempera-
tures np to the boiling-point of mercury.
Certain gases and vapours spontaneously in-
flame as they issue into the air, such, for
example, are boron and silicon hydrides, the di-
hydride of phosi^orus, thio-phosphoryl fluoride,
cacodyl, zinc-ethyl, &o. Thus too acetylene
spontaneously inflames in chlorine, and sul-
phuretted hydrogen in chloric oxide. The spon-
taneous inflammation may in some cases be due
to the fact that the ignition-temperature of the
mixture is as low as that of the ordinary tem-
perature of the air, or that the temperature has
been raised to the ignition-point by a preliminary
reaction between the substances. The spon-
taneous inflammation of ' engine-waste,' or wool
saturated with oil, is due, in the first instance,
to the development of heat attending the ab-
sorption of oxygen from the air by the oil;
Oxygen so absorbed by oil will indeed act as
energetically as if occluded by platinum. A
woollen rag or a bit of blanket sprinkled with
oil and suspended in a mixture Of sulphur di-
oxide and air will rapidly 'tinder' from the
formation' of oil of vitriol.
We have as yet no very exact information
concerning the ignition-temperatures of gases.
The experimental difficulties in the way of
carrying out such determinations are very con-
siderable. A. Mitseherlich has described a
method (Fr. 16, 67) of ascertaining the ignition-
point, but no determinations by means of it have
yet been published. It is, however, certain that
the ignition-temperatures of gaseous mixtures
are as a rule by no means so high as is commonly
supposed, and they lie within extremes of tem-
perature admitting of comparatively easy deter-
mination. When once initiated, the continuance
of the combination of unlimited amounts of the
constituents of a combustible mixture, or in other
words the continued existence of a flame, depends
primarily upon the condition that the combining
gases are maintained at the temperature required
to bring about their union. Any agency or con-
dition which lowers the temperature below this
point will extinguish the flame. A coal-gas
flame is extinguished by a cold mass of copper,
and a candle flame by a helix of cold copper wire.
The metal abstracts sufficient heat from the
gases to lower their temperature below the point
of combination. If the metal is heated prior to
its introduction into the flames they are not
extinguished.
The cooling action of metal is made use of
in the Hemming safety-jet used for burning
mixtures of oxygen and hydrogen, but a far
more important application of it is seen in the
Davy safety-lamp. This is simply a small oil-
lamp surrounded by a cylinder of wire gauze.
If the lamp is introduced into an explosive
mixture of fire-damp and air, combination occurs
within the cylinder, but the flame is prevented
from traversing the gauze by the cooling action
of the metal. Any circumstance which causes
the gauze to become hot, or which prevents it
from exerting its specific cooling action, renders
the lamp unsafe. Thus if the fiame impinges
on the wire gauze so as to heat it to redness, or
FLAM]^.
661
U the burning lamp be held in a current of air
and fire-damp exceeding in Telocity six feet per
gecond, or if it be struck hj a sound wave of
sufficient intensity, the flame will pass through
the meshes, and may ignite an explosive mixture
on the outside of the cylinder.
A- flame may be extinguished, however, in
other ways than by the cooling action of metals,
as, for example, by mixing the combustible gases
with a sufficiently large quantity of an indif-
ferent gas which will act by absorption of heat,
in the same way as metal. The effect even
of small quantities of indifferent or chemically
inactive gases in lowering the temperature of a
flame is very marked, and is well illustrated in
the different characters of the flame of hydrogen
burning in air and in oxygen. In extinguishing
a flame, say of a candle or coal-gas, by ' blowing
it out,' the puff of air acts partly by suddenly
scattering the glowing gases from the area of
supply and partly by its cooling action. Al-
though oxygen is essential to the existence of
the oxyhydrogen flame, it is readily possible to
extinguish the flame by an excessive supply of
that gas within the jet. The power which an
indifferent gas possesses in destroying flame has
received important practical applications in seve-
ral fire-extinguishing apparatuses.
If the flame of a candle or of coal-gas be
closely examined it Vfill be seen that the one does
not touch the rim of the burner nor the other
the wick (Blochmann, A. 168, 345). The inter-
mediate space in the case of coal-gas may be
increased by mixing it with an indifferent gas,
as nitrogen or carbon dioxide. These phenomena
are due to the cooling effect of the wick or the
burner. Whenever a cold object touches a flame,
a dividing space, similar to that noticed between
flame and burner, is observed, the size of which
iETdependent on the coldness of the object or its
specific heat, and the dilution of the burning,
gas. A thick metaUio wire, brought into a flame
diluted with carbon dioxide, causes a clear space
around itself, which increases with the proportion
of the iadifferent gas. The diluting gas lowers the
temperature of the flame, by diffusing the heat
needed to maintain a given quantity of the coal-
gas in a state of combustion throughout a greatly
increased volume of gas. If the temperature of
the flame is already low, the further decrease
resulting from the introduction of the cold ob-
ject suffices to cool a comparatively large extent
of gas below the ignition-point, and hence to ex-
tinguish the flame in the cooled space.
Barefaction of the gases prevents the con-
tinuance of combustion by retarding combi-
nation, whereby the temperature of the gases
sinks below that necessary to effect union.
A jet of hydrogen issuing into rarefied air
gives at first an increased size of flame, but it
ceases to bum when the air is rarefied to ^th
its ordinary pressure, and a mixture of 2 vols, of
hydrogen and 1 vol. of oxygen is not explosive
when rarefied to ^th its ordinary density. By
mixing oxygen with an indifferent gas many
phenomena of combustion are immediately ar-
rested, imless some extrinsic agency is at work
to maintain or even raise the temperature. The
combustion of iron wire in oxygen stops almost
immediately when the glowing metal is with-
drawn into the air.
On the other hand, instances are known in
which indden rarefaction will produce spon-
taneous ignition even at the ordinary tempera-
ture. Thus pure phosphine mixed with oxygen
is not spontaneously inflammable at ordinary
temperatures and pressures, but on suddenly
expanding the mixture it inflames with explosive
violence. In the same way thiophosphoryl
fluoride, if mixed with an indifferent gas and
thereafter with oxygen, will detonate on a sudden
diminution of the pressure. These phenomena
are in all probability connected with the extreme
instability of these gases, and are akin to the
cases of decomposition by shock which have
been studied by Berthelot and others (v. Ex-
plosiok).
It has already been stated that the form of
a steady continuous flame depends upon the
mode in which the combustible gas issues into
the air, and this is dependent upon the form
and size of the jet, or, in the case of a candle,
of the wick. The size of the flame from gas
issuing at a constant rate is dependent on the
temperature, pressure, and relative diffusibilfties,
of the combining substances. By increasing
the amount of oxygen in the air the size of a
flame may be considerably diminished. This
fact is well illustrated by plunging a jet of
hydrogen burning under constant pressure in
air into oxygen gas. The increased size of the
flame under ordinary conditions is due to the
fact that the air contains only one-fifth of its
volume of oxygen ; the ' combustible ' gas has
to seek, therefore, over a larger area for the
oxygen required for combination. The size of a
flame is also necessarily determined by the
volume of oxygen needed for the complete com-
bustion of the inflammable gas. Thus equal
volumes of hydrogen and of ethylene passing
through the same jet and at the same rate into
oxygen will give flames of very different size :
the hydrogen, which needs only haU its volume
of oxygen to burn it, forms a much smaller
flame than the ethylene, which requires three
times its volume. On the other hand, oxygen
burning in hydrogen gives a larger flame than
when burning in marsh gas ; in the former case
the oxygen needs 2 vols, of hydrogen for its
combustion ; in the latter only half a volume of
marsh gas.
The temperattire of flames is extremely vari-
able. Some, like that of sulphur burning in air,
are comparatively low; others furnish us with
some of the highest temperatures of which we
have any practical knowledge. The temperature
of a flame depends mainly upon the heats of
combination of the constituents and the specific
heats of the products of combustion. Flames
which depend upon the presence of oxygen are
much hotter when the combustion takes place
in an atmosphere of the pure gas than in air.
In the latter case the oxygen is mixed with four
times its volume of nitrogen, which plays no
part in the chemical reaction, and therefore
contributes nothing to the heating effect, but on
the contrary abstracts a considerable amount of
heat from the products of combustion, and
thereby lowers the temperature of the glowing
mass of gas. Hence sulphur burning in oxygen
gives a much hotter flame than when burning
in air, and the oxyhydrogen flame is much hotter
66d
FLAME.
than that of hydrogen in air. The eSeot of the I
indifferent gas in lowering the temperature is
well illustrated by the following numbers given
by Bunsen (P. U. [4] 34, 489).
Flame of hydrogen burning in air . 2,024°
» » .. oxygen 2,844°
„ carbonic oxide burning in air 1,997°
„ „ „ oxygen 3,003°.
The conditions under which a flame is produced
not only modify it's temperature, but also, as an
effect of temperature, its colour. Thus the pre-
vailing tint of sulphur burning in air is blue,
and the mantle is comparatively small and of a
violet colour. In oxygen the flame becomes
hotter, and the violet colour is more pronounced.
Precisely the same change is produced by heating
the air or by burning a jet of heated sulphur
vapour. Cold carbonic oxide gives a blue flame
in air, but it becomes yellowish-red if the gas
be previously heated.
The flame of a candle, whether of wax, tallow,
or paraffin, is seen to consist of four distinct
cones, which are comparatively sharply defined,
and which are rendered evident by their different
appearance. Immediately surrounding the wick
is a dark inner cone consisting of unburnt gases
or vapours distilled from the fatty matter raised
by the capillary action of the wick from the reser-
voir of melted material at its base. Below the
inner cone is a light-blue zone of small area
consisting of combustible matter from the wick,
which has become mixed with an amount of
oxygen sufficient to burn it completely to non-
luminiferous gases. Surrounding the inner cone
is a bright luminous area, from whic^ the greater
part of the light emitted by the flame is derived.
This area constitutes the main meeting-place of
the combustible gases with the oxygen, and
hence chemical combination is here most
vigorous. Surrounding the luminous area, which
seems to constitute the greater portion of the
visible flame, is an envelope or mantle of a faint
yellowish colour and of feeble luminosity ; this
consists of the final products of combustion of
the constituents of the luminous cone mixed
with atmospheric air heated to incandescence.
Owing to the intense glare of the luminous cone
the feebly luminous mantle is not readily per-
ceived, but it may be rendered evident by holding
a piece of card of the shape of the flame in such
a manner as to hide the luminous cone, when
the mantle is seen lining the outer edge of
the cone. The fact that the candle flame
is hollow, and that the internal cone immedi-
ately surrounding the wick consists of compara-
tively cold unignited gas free from oxygen, may
be demonstrated by thrusting a fragment of
burning phosphorus into the cone, when its com-
bustion ceases. A piece of stiff thick paper
thrust down on the flame to the level of the dark
internal area is seen to be charred on the upper
surface in the form of a ring ; if the paper be
placed simply across the luminous area and
above the dark cone the charring is simply a
circular patch.
In other steady, continuous flames these
areas or zones are very different in character
and in number. In some the luminous cone is
absent, and others have no mantle ; all have, of
course, the dark internal cone, and the majority
have an area corresponding to the blue zone in
the candle flame. In an alcohol flame the In-
ternal cone is large, owing probably to the ready
volatilisation of the combustible vapouB^ the
luminous cone is small, and the mantle seems
to be largely developed. The flame of carbon
monoxide consists of a dark internal cone of
unburnt gas surrounded by a yellowish-red
mantle somewhat ill-defined at its external edge,
and at the base is a comparatively large blue
zone.
Attempts have been made by Hilgard (A. 92,
129), Landolt (P. A. 99, 389), Blochmann {A.
158, 295), and others, to study the nature of the
chemical process in flames of candles and of
coal-gas, by aspirating the gases from different
parts of the flame and analysing them. Such in-
vestigations can only give a very partial concep-
tion of the changes which occur or have occurred
in the different areas of the flame owing to the
intense molecular movements, due to the high
temperature and speciflc differences of diffusive
power, of the gaseous constituents. Nevertheless
it is possible to obtain some idea of the manner
in which the several combustible gasbs in such a
complex mixture as that of coal-gas, or of the
gas obtained by the distUlation of wax or tallow,
behave towards oxygen, and to trace the rates at
which they are severally burnt. Thus, broadly
speaking, it is found that of these gases, the
hydrogen up toa certain point is most rapidly con-
sumed, then the carbonic oxide, next the marsh
gas, whiletheheavyhydrocarbons burn compara-
tively slowly. The amounts of these gases burnt,
and especially of the hydrogen and carbonic oxide,
are, however, modified by processes of dissocia-
tion, and by the mutual action of the products
of combustion at high temperatures; at very
high temperatures water vapour and carbon di-
oxide are dissociated, while carbon monoxide
is formed by the action of separated carbon upon
carbon dioxide. The process of breaking up
the hydrocarbons is one of gradual degradation,
the higher members of the paraffin series being
probably resolved into defines and paraffins of
lower molecular weight :
as in the case of butane, which is known to
be resolved into ethane and ethylene,
C,H,„ = 02H,H-C2H4. At a sufficiently high
temperature ethylene is further broken up aa
follows :
2C2I14 = G2Mg -f \J^^
2C2H, = 2CH, + 2C.
On the other hand, at high temperatures marsh
gas is known to form naphthalene 0,gH, and
acetylene ; while at still higher temperatures it
is resolved into carbon and hydrogen.
The main cause of the luminosity of a candle-
flame, and indeed of all our ordinary illumina-
ting flames, was first traced by Davy as the out-
come of the experiments which led' him to the
invention of the safety lamp. It is, to use his
own words, 'owing to the decomposition of a
part of the gas towards the interior of the flame,
where the air was in smallest quantity, and the
deposition of solid charcosS, which first by its
ignition, and afterwards by its combustion, in-
creases in a high degree the intensity of the
light ' (Tr. 1817, 45, 77). The proofs that soUd
carbon is present in luminous hydrocarbon flamei
FLAME.
658
are the following (v. especially Eeumann, P. M.
1877).
1. Chlorine causes an increase in the lumi-
nosity of feebly-luminous or non-lwmmous hy-
drocarbon flames. Since chlorine decomposes
hydrocarbons at a red heat with separation of
carbon, it follows that the increase in luminosity
is due to the production of solid carbon particles.
2. A rod held in the luminous fla/me soon be-
comes covered on its lower swface,i.e. the surface
opposed to the issuing gas, with a deposit of soot.
The solid soot is driven against the rod. If the
Boot existed as vapour within the luminous flame,
its deposition would be due to a diminution of
the tempeftiture of the flame, and would, there-
fore, occur on all sides of the rod.
3. A strongly heated surface also becomes
covered with a deposit of soot. This result could
not occur if the deposit were due to the ooohng
action of the surface.
4. The carbcm particles in the luminous flame
are rendered visible when the flame comes in con-
tact with another flame, or with a heated sur-
face. The separated particles are agglomerated
into larger masses, and the luminous mantle be-
comes filled with a number of glowing points,
giving a very coarse-grained soot.
5. The transparency of a Iwmmous flame is
no greater than that of the approximately equally
thick stratum, of soot which rises from the flams
of burning twrpentine, and which is generally
allowed to contain solid particles. A flame of
hydrogen made luminous with solid chromic
oxide, which is non-volatUe, is as transparent as
the hydrocarbon flame.
6. Flames which undoubtedly owe their lii-
minosity to finely divided solid matter produce
shadows in sunlight. The only luminous flames
incapable of producing shadows are those con-
sisting of glowing gases and vapours.
7. Luminous hydrocarbon flames produce
strongly marked shadows in sunlight; these
fla/mes, therefore, contain jmely divided soUd
matter. This solid matter must be carbon, since
no other substance capable of remaining solid
at the temperature of these flames is present
(Heuniann). Moreover, if the soot in luminous
flames is present as vapour, a high temperature
after condensation should again cause it to as-
sume the gaseous condition, but soot is absolutely
non-volatUe even at the highest temperatures.
The presence of solid matter is, however, not
the -sole cause of the luminosity of a candle or
hydrocarbon flame, sinqe a small portion of the
light is derived from the incandescence of the
gaseous matters. Methane, which when burning
under ordinary conditions gives no deposit of
soot, still afiorda a flame of considerable illumi-
nating power (equal to 5*2 candles according to
Lewis T. Wright, C. 3. 47, 200). Bright flames
may indeed be produced without the interven-
tion of solid matter. Arsenic burns in oxygen
with a bright flame, although the product of the
combustion (arsenious oxide) is volatile at the
temperature of its formation. A mixture of
nitric oxide and carbon disulphide burns with a
brilliant light although no separation of solid
matter occurs. It has already been pointed out
that substances burning in oxygen give much
hotter flames than when burning in air, and it is
also found that the flames in oxygen are much
more luminous than those in air. Hence the
temperature of a flaine very considerably affects
its light-giving power. B.Franklandhas pointed
out the connexion between the luminiferoua
character of flames and the density of their con-
stituents, as is exemplified by the greater illumi-
nating power of a hydrogen flame in chlorine
than in oxygen. The luminosity of a flame is
increased by condensing the surroundihg atmo-
sphere and diminished by rarefying it. Boyle, in
1658, minutely described the appearance of a
candle-flame as seen under diminished pressure
in the receiver of his ' new pneumatical engine.'
E. Frankland found that candles give much less
h'ght when burning at the top of Mont Blanc
than in the valley below, although' the rate of
combustion is not much affected by th,e differ-
ence in the density of the air. The flame of ar-
senic burning in oxygen is greatly diminished in
brightness by rarefying the oxygen, and the flame
of an alcohol lamp increases greatly in lumi-
nosity when burning in condensed air. Under a
pressure of 10 atmospheres the flames of hydro-
gen and of carbon monoxide become very bright
and give continuous spectra, and an electric
spark increases in luminosity with the density
of the gaseous medium through which it passes
(Frankland, Pr. 16, 419).
Similar observations have been made by
L. Cailletet {A. Ch. [5] 6, 429), who found that
the flames of candles, sulphur, potassium, and
carbon disulphide, but not of phosphorus, burned
in gradually compressed air with continually in-
creasing intensity of illumination up to pressures
of 35atmos. On the other hand, Wartha (J.pr.
[2] 14, 84) found that the flame of a stearin candle
burning in air under a pressure of 1*95 at. ia
from 13 to 17*4 p.c. less luminous than when
burning in air of ordinary density. At the higher
pressure candles burn with a dull yellowish-red
smoky flame fully twice as long as that of the
same candles burning in the open air. Candles
burning at a constant pressure of 90 nun. give
a large, clear, non-luminous flame, consisting of
an inner bluish-green cone, surrounded by a
violet zone, and inclosed by a very faint violet
mantle. The non-luminosity of flame under low
pressures was supposed by B. Frankland to ba
due to the increased mobility of the oxygen
molecules in the rarefied air in consequence of
which they were able .to penetrate more freely
into the interior of the flame. According to
Wartha, the difference is to be attributed to the
effect of the pressure on the dissociation-point
of the burning substance. When candles are
burned in air, under very high pressure, the
dissociation of the hydrocarbons takes place niore
rapidly than the products can be burned, and the
flame becomes smoky ; under reduced pressure
the reverse is the case.
A comparatively small admixture of air greatly
impairs the Uluminating power of coal-gas. Sil-
limann a. H. Wurtz (Am. 8. [2] 48, 40) found
that on adding varying quantities of air to a coal-
gas having an illuminating value of 14-8 candles
the loss of light was as follows :
Added air Percentage loss of Ugbt
3-00 p.c. 15-69
4-96 „ 23-83
11-71 „ 41-46
16-18 „ 67-SS.
664
FLAME.
On adding about 25 p.e. of air the iUuminating
powei diminished 84 p.o. With suoh an admix-
ture coal-gas bums mth a smokeless and practi-
oallj non-luminons flame.
It has been shown that a coal-gas flame
burning in air becomes non-luminous by pre-
vious admixture with nitrogen, hydrochloric
acid, carbon dioxide (Enapp), carbon monoxide,
hydrogen (Blochmann), or even steam (Sandow).
P-. f . FranUand foimd that while the illumina-
ting power of ethylene was diminished after a
certain point by admixture with ordinarily non-
luminous combustible gases, the loss of Light
depended on the nature of the diluent, and w^s
greatest with carbonic oxide and least with marsh
gas. An admixture of the combustible gas np to
40 p.c. hardly affects the illuminating power of
the ethylene (0. J. 45, 39). Mixtures of oxygen
with ethylene in quantity insufficient to form an
explosive mixture possess a greater illuminating
power than pure ethylene. By the addition of
carbon dioxide, nitrogen, or aqueous vapour, the
illuminating power of ethylene is duninished.
These gases act partly by dilution, and partly by
cooling; the cooUng action is proportional to
the specific heats of the gases, but in the case of
carbon dioxide and aqueous vapour it is aug-
mented by the absorption of heat which takes
place in the dissociation of the aqueous vapour,
and in the reduction of the carbon dioxide to
carbon monoxide (P. F. Frankland, C. J. 45,
236). "
Wibel has shown that a mixture of coal-gas
and air, which when burnt under ordinary con-
ditions is non-luminous, may be made to give a
luminous flame if it is heated previous to inflam-
mation (B. 8,. 226); andHeumann {A. 181, 129;
182, 1 ; 183, 102 ; 184, 206) has proved that the
luminosity is actually due to the added heat, and
not to any alteration in the composition of the
gaseous mixture, in consequence of the heating.
These observations have an important bearing
on the theory of the flame of the Bunsen lamp.
The nature of the chemical changes in this flame
has been studied by Blochmann (A. 168, 295).
The feebly luminosity of the Bunsen flame is
due (1) to a rapid oxidation of luminiferous ma-
terial to gases of feebly iUumiinating power by
the oxygen in the admixed air ; (2) to the pre-
sence of diluting gases which of themselves re-
duce the illuminating power ; and (3) to the heat
withdrawn by the indifferent gases, as nitrogen,
and the products of combustion, carbon .dioxide
and water. The loss of luminosity is not due to
any one of these causes acting singly. A flame
of mixed coal-gas and air has a higher tempera-
ture than that of the undiluted coal-gas, but it
requires a still higher temperature in order that
a separation of carbon shall occur.
When the flame of a Bunsen lamp retreats
down the tube and burns at the jet at the bottom
a much smaller quantity of air passes into the
tube. Under normal conditions 1 vol. of the
gas becomes mixed with about 2^ vols, of air:
when burning at the bottom the gas becomes
mixed with only about 1^ vols, of air. The effect
of this diminished amount of air is a large in-
crease in the amount of carbon monoxide, to-
gether with the production of notable quantities
of acetylene, to which substances the extremely
disagreeable nature of the gases evolved from
the burner under these circumstances is due.
(Compare Thorpe 'On the Theory of the Bunsen
Lamp,' C. J. 1877. 1, 627.) T. E. T
TLAVANILIKE C,eH„N2 i.«.
.CMe:CH
CaHZ I
\N = C.C^4(NH2) [1:4]. p-Amido-{Py.3)-
phenyl-{Py.l)-met}^l-gmnolme. [97°].
FormaUon. — 1. By heating equal mols. of
ortho-andpara-amidoacetophenone with an equal
weight of zinc-dust at 50°-100°; the yield is 60
p.c. — 2. By nitration and reduction of flavoUne.
3. By heating o - amido - acetophenone to 230°
with ZnClj. — 4. By the action of acet]|l chloride
on aniline sulphate.
PreparaUon. — By heating acetanilide with
ZnClj for several hours at 2§0°-270°, the melt
is dissolved in boiling dilute HCl, sodium ace-
tate added, and the product salted out (O. Fischer
a.Eudolph, £. 15,1500).
Theory of formaUon from acetanilide. At
the temperature employed the acetanilide under-
goes isomeric change, being converted into a
mixture of o- and^-amido-acetophenone, and the
latter (as shown in formation 1) gives the dye-
stuff by the elimination of 2H2O from two mols.
by means of the ZnCl, :
C.H/ • ■ I
^Ng"""" OjO— 05Hi(NBy (Besthom a.
O. Fischer,' B."l6C 68).
ConsUiuiion. — Contrary to the earlier sup-
position, flavaniline has the KH, group in the
pca-a- position not in the ortho-. The fact that a
small quantity of the dyestuff is formed by heat-
ing ort^o-amido-acetophenone with ZnCl, at 250°
must be due to an isomeric change of a por-
tion of the o-amido-acetophenone into2>-amido-
acetophenone.
Properties. — ^Long colourless needles. Dis-
tils undecomposed at a high temperature. Sol.
alcohol, insol. water. Strong di-acid base. The
salts form a splendid yellow dyestuff of green
fluorescence. By the action of nitrous acid it
yields fiavenol.
Salts. — ^B"H2Cl2: colourless soluble needles.
— B"HC1 : yellowish-red soluble prisms. —
B"H2Cl2PtCl,: sparingly soluble crystalline pp.
Beactions. — It cannot be reduced to a hydride
by tin and HCl; but on treatment with alcohol
and sodium it yields a fluid base, the salts of
which are colourless, and forms a crystalline
nitrosamine. Heated with glycerin, nitrobenzene
and H2SO4 it yields a methyl-diquinoliue [138°]
(0. Fischer, B. 19, 1036).
Beference. — Ethyl-jUwanilme.
Fseado-flavanilin Cu^uN, tA
,OH:CH
\ N=O.C^sMe(NHj) [1:3:4]. Amido-tolyU
gvmoKne. [112°].
PreparatUm. — By leading oxygen over a
mixture of quinoline and o-toluidine hydro-
chloride heated to 180° on platinised asbestos
(Weidel a. Bamberger, M. 9, 99).
Properties. — ^Flexible, hair-uke needles (from
water) . Converted by HNO2 into pseudo-flavenol
CjgHijNOH, which on further oxidation givei
qninaldinio acid C,gH,N02.
FLUORANTHENE.
655
Salts.— B"H2C1, ; long needles.— B"HC1 :
small yellow monoolinio needles.— B"njPt01j.
Acetyl derivative C.jk.^oN,. 1177°].
FIAVANTHBACENE-DI-SriPHOlIIC ACIB
V. AUTHBAOENE-DI-STJUHOIIIO AOID (floB-).
TLAVENOL 0„H„NO i.e. '
^CMe:CH
0A< I
^N = 0.0sH,0H[l:4]. [238"]. Formed
by the action of nitrous acid on flavaniline.
Sublimable. Colourless iridescent plates. Sol.
aloohol and aqueous NaOH. Has both pheuolio
and basic properties.
BeaeUms. — On distillation with zinc-dust it
gives flavoline. With acetic anhydride it forms
d substance crystallising in needles [128°] .which
distils undecomposed (O. Jischfer a. Budolph, B.
16, 1602). On oxidation with alkaline EMnO,
it is converted successively into lepidine-car-
boxylio acid, piooline-tri-carboxylic acid, and
finally pyridine-tetra-oarboxylio acid (0. Fischer
a. Tauber, B. 17, 2925).
Salts. — ^BBCl" : long colourless soluble
needles. — BfjHjSOi" : colourless needles. —
B'sHjOytOli" : yeUow sparingly soluble needles.
Acetyl derivative C„H,2K(0Ac) : long
needles or small plates [128°] (Besthorn a.
0. Fischer, B. 16, 69).
Fseudo-flavenol C,sH„NO t.e.
.CH:CH
\N=0.C8H8Me.0H [196°].
Prepa/ration. — ^From pseudo-flavaniline by the
action of nitrous acid ; oxy-pseudo-flavenol [89°]
and nitro-pseudo-flavenol are also formed. It is
separated from these by shaking with ether,
which extracts the oxy- compound, and then
ppg. the impure pseudo-flavenol by COj. Crys-
tallised from absolute alcohol.
Properties. — ^Plates. Sol. hot alcohol, ether,
benzene, and chloroform. Oxidised by CrO, to
quinoUne (Py. 3)-oarboxylio acid [167°]. It is
reduced by zinc-dust to the base pseudo-
flavoline C,gH„N, ortho-cresol, and quinohne.
Tin and HGl convert it into a tetrahydro-com-
pound, which, when fused with potash, is oxi-
dised to o-oxy-iso-phthalic, jj-oxy-benzoic, and
salicylic acids (Weidel a. Bamberger, M. 9, 99).
Salts. — B'HC12aq: pale yellow needles. —
(B'H01)2PtCl4: yellow crystalline powder.
Acetyl derivative CmH,j^OAc : [106°] ;
plates.
Nitro-pseudo-flavenol C„H,j(N02)N0. [160°].
FLATIIfE V. Dl-AMIDO-BEIIZOPH£IIONE.
FLAVOIDIITE. a name proposed by Meldola
(C, N. 60, 267) to denote azo- bases of the form
NHjE".Nj.B"NHj, isomeric with the chryso-
idines.
FLAVOL V. Dl-OXY-AMTHBAOENS.
FLA VOLUTE v. (P^. 3:l)-FHEim:i-iiETHYi;i-
qcnfoLiNE.
FLAVOFTTBFTrBIIT v. Ibi-oxy-anihea-
QDINONE.
FLAVOftTTINOLINE v. {Py. l)-MiiTHTi..
(Py. 3: B.3)-DiQtJiN0LiNE.
, FLUAVIL V. Gbtia pbboha.
FLXrO-. Use of tMs prefix a/ppUed to imor-
game ccmpov/nds : for fiuo-salts v. the salts to
the name of which fiuo- is prefixed. Ihns,
fhio-mobates, fluo-siUcates, and fiuo-stannates
will be described under Niobates, Silicates,
and SiAintATEB, and these salts will be found
under the general headings Niobiuu, Shjook,
and Tin. M. M. P. M.
FLUO-BEN'ZEN'E v. FLnono-BENZENE.
FLTTOBENZOIC ACIB v. Fluobobenzoio Aom.
FLXrOBOBIC ACIB and FLTTOBOBATES
HjBjO^.eSF and MjB,04.6HF (v. vol. i. p. 530).
FLrOBAmLIITE v. FiiUOBO-ANiLiint.
[EN]
H
HO CH
HO.
'^o/°\
CH
HO
I
HC,
\
/
\
CH
-CH
(Fittiga.Liepmann,B.12,164). Idryl. [110°].
(261° at 60 mm.). V.D. 6-64 (calc. 6-57).
Ocowrrence. — In coal-tar (Fittig a. Gebhard, '
A. 193, 142). Found also to the extent of 3 p.c.
amongst the soUd hydrocarbons obtained in
Idria in distilling mercury from its ore (Gold-
Bchmiedt a. Schmidt, M. 2, 1), and in American
petroleum (Prunier, Bl. [2] 31, 293).
Preparation. — Crude pyrene from coal-tar is
converted into the picric acid compound by treat-
ment with an alcoholic solution of picric acid.
The pic):ic acid compound of fluoranthene is
more soluble in alcohol than that of pyrene.
The hydrocarbon is hberated' from this com-
pound by KH,, and is recrystallised from alco-
hol. Fluoranthene may also be separated from
pyrene by fractional distillation under 60 mm.
pressure when pyrene boils 10° higher (Fittig a.
Liepmann, A. 200, 1).
Properties. — Large colourless monoclinic
plates (from dilute alcohol) a:b:c = l'495:l:l-025 ;
;3 = 82°50'; or thin needles (from alcohol). SI.
sol. cold, V. sol. hot, alcohol ; v. sol. ether, CS^,
and HOAc. Warm cone. E2SO4 dissolves it,
forming a blue solution. Its picric acid
compound C,sH,„OjH2(N02)30H [183°] forms
long reddish-yellow needles, which may be re-
crystallised from alcohol without decomposition,
Tri-chloro-flnoranthene C,sH,Cl,. [above
800°]. Needles (Goldschmiedt, M. 1, 222).
Bi-bromo-fluoranthene C,^B.gBi^. [205°].
From fluoranthene in CS, and Br (F. a. G.).
Light-yellow needles (from CSj).
Tri-bromo-flnoranthene Ci^HiBrs. From
fluoranthene in HOAc and Br. Needles. Does
not melt below 345° (G.).
Tri-nitro-flnoranthene C,jH,(N02),. [above
300°]. From fluoranthene and fuming HNOs.
Minute yellow needles. Insol. ordinary solvents,
sol. hot HNO,.
Fluoranthene dihydride C,5H,j. [76°]. From
fluoranthene by treatment of its alcoholic solution
with sodium amalgam, or by heating with HIAq
and red phosphorus at 180° (Goldschmiedt).
Needles (from alcohol). Its picric acid com'
pound C,5H,AH2(NOJ,OH [186°] crystallises
from alcohol in red needles.
656
FLUOEANTHENB.
FluoTantheiie octohydrida CuH„. (311°).
From fluoianthene, HTAq, and red phosphorus
Bt 250° (G.)-
Fluoranthene disnlplionic acid C,,Hs(S03H)2.
From fluoranthene (1 pt.) and H^SO, (2 pts.) at
100° (G.). Unstable syrup. Potash-fusion gives
crystalline 0,|,Hj„0,[246°].—KijA"aq,—OaA"4aq.
--BaA"2^aq: m. sol. water.— CdA" 2iaq. On
distilling the E salt with KCy and fusing the
product mth EOH there is formed the carbozylic
Boid C,5H,C0jH [165°].
Fluoranthene - quinone C.sHgOa. [189°].
Formed, together with a large proportion of di-
phenylene ketone carbozylie acid | >C0
CsHj/COjH
by oxidising fluoranthene with chromic acid
mixture (F. a. L.). After removing the acid by
aqueous NajCO, alcohol extracts the crystalline
compound C,jH,02(0,sH,g)2 [102°] whence aqueous
NaHSOj extracts the quinone. On addition of
HCl to the solution in NaHSO, there are ppd.
nearly colourless needles, apparently consisting
of the hydroquinone ; these are converted in
great part into the quinone during recrystallisa-
tion from alcohol, or more quickly by oxidation
with FeOlj. Small red neecUes (from alcohol) ;
m. sol. alcohol and HOAc.
FLTJOEENE 0,sH„ ».«. 1° *\cB^. {a).Di-
phetvylene-methame. Mol. w. 166. [113°]. (c.
302°) (A.) i (295° i. V.) (F. a, S.). V.D. 3-77
(calc. 5-78).
Ocewrrence. — In the portion of coal-tar boil-
ing between 300° and 400° (Berthelot, A. Ch. [4]
12, 222; Barbier,X. Ch. [5] 7, 472). '
Formation. — 1. From diphenylene ketone by
distUling with zinc-dust (Fittig,£.6, 187 ; Fittig
a. Schmitz, A. 193, 134) or by heating with
HIAqandamorphousphosphoruBatl60°(Graebe,
B. 7, 1625). — 2. By passing diphenyl-methane
through red-hot tubes (Graebe, A. 174, 194). —
3. From diphenyl and CH^Clj under the influence
of AICI3 (Adam, Bl. [2] 47, 686).— 4. By distilling
the di-carboxylic acid with lime (Bamberger a.
Hooker, B. 18, 1036). — 5. By distilling phenan-
thraquinone with lime (Anschiitz a. Schultz, A.
196, 44). — 6. By heating ellagic acid with zinc-
dust in a current of hydrogen (Barth a. Gold-
schmiedt, B. 11, 846).
Preparation.-i— By fractionally distilling the
hydrocarbons contained in coal-tar about 20
litres of a portion boiling from 300° to 320° is
collected ; this is solidified by cold, pressed, and
redistilled ; a fraction 290° to 310° (10 litres)
is then obtained by distillation. After one more
distillation the fraction 295° to 305° is recrys-
tallised successively from alcohol-benzene, alco-
hol, and HOAc (Barbier). Still further purifica-
tion may be effected by means of the picric acid
compound.
Proper^s. — Very small white plates (by
sublimation) exhibiting, when not perfectly
pure, violet fluorescence. If recrystaUised
several times from alcohol and then from glacial
acetic acid it is no longer fluorescent (Hodgkin-
son a. Matthews, C. J. 43, 163). Y. sol. ether,
benzene, CS2, and hot alcohol, si. sol. cold
Bloohol.
BeacHom. — 1. Boiling with CiO, in EOAo
forms diphenylene ketone, but no quinone. —
2. Potash-fvMm gives di-oxy-diphenyl[98°] and
other products. — 3. When its vapour is passed
over heated lead oxide there are formed two hy-
drocarbons, CjsH,* ^^^ Cse^ii!- ^1^3 latter forms
red trimetric crystals (from HOAc) [183°] (above
360°) ; gives an unstable picric acid compound
[178°] ; and is reduced in alcoholic solution by
sodium-amalgam to colourless OjuHu [242°] (De
la Harpe a. Van Dorp, B. 8, 1049). The hydro-
carbon CaiH,4 forms long yellow needles (from
benzene-alcohol) [270°]. — 4. When fluorene is
passed over red-hot MnOj a red mass is obtained,
and if this be freed from fluorene by heating some-
what above 300° and from the red body by washing
with ether, there is left the hydrocarbon Cj^H,,
[246°] termed ' para-difluoryl.' It forms long
thin prisms, v. si. sol. cold ether, m. sol. hot
HOAc. It decomposes above 250°. It forms a
tetra-bromo- derivative [302°], arid is oxidised by
CrOs in HOAo to Cj8H„0j [255°]. Two other
hydrocarbons, C^^ig, appear to accompany the
one described [246°] in the red mass (Hodgkin-
son, O. J. Proc. 1, 36j.— 5. Cone. HIAq (40 pts.)
at 275° forms CijH^g (240°), hexane and heptane
being also formed according to Berthelot (A. Ch.
[5] 7, 510). — 6. On adding the calculated quan-
tity of lyromine dissolved in CSj to a solution of
fluorene in CS^ dibromo-fluorene C,,,H^r2 [167°]
is formed. It crystallises from CS^ in mono-
clinic forms. By treatment with more Br in the
cold there is produced the tri-bromo-fluorene
CijHjBr, [162°] (v. Di-bbomo-fijUobene), Brom-
ine vapour passed into a cold solution of fluorene^
in CSj forms light-yellow needles of OuHnBr,
which is quickly converted by alcoholic KOH
into di-bromo-fluorene. By the simultaneous
action of bromine and EOH on fluorene there is
formed a bromo-fluorene [104°] (Hodgkinson,
C. J. Proc. 1, 36). — 7. Chlorine passed into a
solution of fluoreneinCSj forms G,sHgClj [118°]
and CisHjClj [147"^] (v. Dl-CHLOBO-FLtlOEENE). —
8, A mixture of fuming nAiric acid and HO Ac forma
nitro-fluorene C,5Hg(N02) [154°] and di-nitro-
fluorene C|jH5(N02)j [201°] {v. Niteo-fluobene).
The former may be reduced by tin and HCl to
2>-amido-fluorene [125°], which crystallises in
needles and forms an acetyl derivative [188°]
(Strasburger, B. 17, 108). Di-amido-fluorene
C,3Hs(NH2)„ [157°] is obtained by distilUng di-
amido-dlpheuic acid with lime ; its acetyl deriva-
tive [250°] crystallises in leaflets (Schultz, A.
203, 99). — 9. Treated with phenyl-acetic chloride
and Aids it gives the ketone CisHa.CO.CHj.CsHs
[156°] which crystallises in small tables, si. sol.
cold alcohol and ether (Papcke, B. 21, 1341).
This ketone is converted by benzyl chloride and
NaOEt into C,3H,.CO.CHPh.CHjO,H5 [150°]
which crystaUises from alcohol in slender
needles.
Picric acid compound
C,sH,„CaH2(N03)30H; [82°]. Obtained by adding
picric acid to an ethereal solution of the hydro-
carbon. Beddish-brown prisms. Decomposed
by boiling with water or alcohol.
Picryl chloride compound
C,3Hi„0eHj(N0j)3Cl. [70°]. Orange needles
(Xiiebermann a. Palm, B. 8, 377).
Flaorene sulphonio acid "GisHgSOsH. From
fluorene in CECl, and CISO3H (Hodgkinson a.
Matthews, C. /. 43, 166). Gummy. V. aoL
FLUORESCEIN.
557
water. Fused with KOH at a little above 400°
it forms two tri-oxy-diphenyls (2. v.), for not
only is SO,H displaoed by OH but CH, is dis-
placed by 2(0H).
Salts. — KA': minute jubes. — ^BaA'n2aq.
— CdA'^Baq.
Isomeride of flnorene. — Di - phenylbne-
UETHANE.
i'LTTOBENE ALCOHOL v. Di-phenylenb
OABBINOL.
fLTTOBEIfE CABBOXTLIO ACID
<CgHj
I Flvorenio acid.
C„H3.C0jH [3:2:1].
r246°]. Formed by reducing diphenylene ketone
carboxylio acid with sodium-amalgam (Fittig a.
Liepmann, A. 200, 13). Small crystals (from
alcohol). May be sublimed. SI. sol. boiling
water, v. sol. hot alcohol. Gives flnorene when
distilled with lime. Alkaline permanganiate
oxidises it to diphenylene ketone carboxylio
acid.
Salts. — BaA'2 3aq: glittering scales, si. sol.
water. — CaA'j 2jtac[ : bard white needles.
Ethyl ether EtA'. [54°]. Colourless
prisms, v. sol. hot alcohol.
Wluorene carboxyUa cusid
<CsH,
I
CjHj.COjH [2:3:1]. [175°]. From diphenyl
o-carboxylic acid by successive treatment with
FClg, alcohol, and zinc and HOAo (Graebe a.
Aubiu, A, 247, 257). Y. sol. alcohol, ether, and
HOAc.
Methyl ether UeX'. [64°].
Tluorene-di-carboxylic acid C,aHs(C02H)2.
Formed by reduction of diphenylene-ketone-dii.
oarboxylic acid with sodium-amalgam in the
cold, si. sol. alcohol, ether, and EOAc. On dis-
tillation with lime it gives flnorene (Bamberger
a. Hooker, B. 18, 1036; A. 229, 161).— Ag^A".
FLTTOBESCElC ACID G^^K^fi, i-e.
C0jH.0^4.0(0H) <o^^'[oh|>0- fluorescein
may be looked upon as the anhydride of this acid ;
but the acid itself is not known in the free state.
Its tetra-bromo- derivative O^^fixfl, is a red-
dish-yeUow pp., obtained by acidifying the pro-
duct of the action of cone, aqueous KOH upon
eosin. Its di-nitro- derivative is obtained in like
manner from di-nitro-fluorescein, and forms red
crystals (from alcohol).
rLUOBESCEitN Ca,H,jOj i.e.
CO<O.H,>c<gg}0|j>0 [1:4:6]. Anhy-
dri^e of tek'a-oxy-di-phenyl-phthaUde. Anhy-
dride of tetra-oiey-tri-phenyl-carbinol cwrhoxyUc
acid. Mol. w. 332. Formed by heating phthalic
anhydride (5 pts.) with resoroin (7 pts.) at 200°,
until the mass gets viscid ; the product is boiled
with water, washed with alcohol, dissolved in
aqueous alkali, and ppd. as a yellow powder by
an acid (Baeyer, B. 4, 658 ; A. 183, 1). Accord-
ing to Mulhauser (U. P. J. 263, 49) phthalic an-
hydride (17^ kilos.) is added with stirring to
melted resorcin (25 kilos.), and after heating for
1^ hours at 180° the reaction begins, and lasts
for 40 minutes. Eesorcin and di-oxy-toluene
C,Hj(OH)2Me[l:3:4] give with phthalic anhy-
dride fluorescent derivatives, while orcin,
C,Ha(OH)jMe[l:3:5] does not. Hence, to form a
fluorescent body the phthalio acid residue must
probably go/ into the position 6.
PrmerUes. — Dark-red prisma (from alcohol).
SI. sol. not water, more sol. dilute acids. When
freshly ppd. it is v. sol. alcohol and ether, but
in the crystallised state it dissolves only on boil-
ing. V. sol. hot HOAo, nearly insol. benzene
and chloroform. The ethereal solution is pale-
yellow, and not fluorescent ; the alcddolio solu-
tion exhibits green fluorescence. Fluorescein
dissolves readily in aqueous alkalis, the solution
exhibiting when dilute a splendid yellowish-
green fluorescence. It also dissolves in alkaline
carbonates, baryta, and lime-water. Fluorescein
begins to decompose at 290°. It dyes silk and
wool yeUow ; but it has little tinctorial value,
although it is the starting-point for the eosin
colouring matters, which are derived from it b'y
displacement of hydrogen by Br, I, NOj, Ac.
On adding alcoholic NH, to an ethereal solution
of fluorescein a reddish-ydlow pp. is formed,
which, however, loses NH, on drying.
Beactions. — 1. Boiling with aqueous NaOH
and zinc-dust decolourises it. On adding an acid
and shaking with ether fluorescin Cj|,H„Oj, or
C02H.O^^.CH<^'^»|°g|>0, is dissolved; on
evaporation it is left as a varnish. Its alkaline
solution is readily reoxidised to fluorescein. —
2. Fusion with caustic NaOH forms resorcin and
the acid C„H„Os or CO2H.0jH<.CO.0,H3(OH)j
[200°], which on further fusion splits up into
CO2, resoroin, and benzoic acid. — 3. Cone. H^SO,
forms a compound CjoH.jOsSOa [140°-150°],
which is resolved by warm water into its compo-
nents.— 4. Boiling with H^SO, for some time
forms resorcin-coerulin, which is ppd. by water
in dark-red flakes, and dissolves in alkalis, form-
ing a greenish-blue solution. — 5. Bromme, in
HOAo, forms di-bromo-fluorescein C2„H,|,BrjOj
[260°-270°] and eosin CjoHsBr^Oj.— 6. Aqueous
NHj when heated with it for 8 hours forms thick
orange monoclinio prisms and tables of
Cj^HijNjOj which is a direct yellow dye for wool.
It is probably C(NH)<Cg>o<gg(Ngs,o
(E. Meyer a. Oppelt, B. 21, 3376).
Metallio derivatives OaC2„H,„054aq.
Obtained by boiling fluorescein with water
and CaCO, (Schreder, B. 11, 1342). Slender
reddish-brown needles with green lustre.—
BaOjgHigOs 9aq : crimson plates.
Acetyl derivative O^oHijAcjOs. [200°].
Needles (from alcohol-acetic acid). SI. sol. alco-
hol, V. sol. HOAc, insol. ether, benzene, and
chloroform.
Benzoyl derivative C^o'B.ifizjOy [215°].
Crystals (from acetone) ; si. sol. alcohol and ether.
Ethyl derivative Ca,H„Bt05. [156°].
From fluorescein, KOH, and alcoholic EtBr at
120°. Pale-yellow needles (from ether) ; v. sol.
alcohol, chloroform, and benzene ; insol. dilute
alkalis.
Di-ethyl derivative G^^i^i^O^. Not
formed by the action of EtBr on potassium
fluorescein, but sparingly formed by thd action of
EtI on the silver derivative. Pale-yeUow plates
(from alcohol) ; si. sol. ether and alcohol ; the
alcoholic solution^ shows a vivid yellow fluores-
cence. Not dissolved by dilute alkalis, but split
558
FLUORESCEIN.
np into alcohol and fluorescein by cone. KOHAq
or HjSO,.
CfcZortde OjoHijOijClj. [252°]. From fluor-
escein.. (1 mol.) and PCI, (2 mols.) at 100°.
Prisms (from toluene-alcohol). V. sol. hot benz-
ene and toluene, si. sol. alcohol and ether. Not
affected by aqueous or alcoholic EOH, but de-
stroyed by potash-fusion. Water and slaked
lime at 230° reconvert it into fluorescein. Be-
duced in alcoholic solution by NaOH and zinc-
dust to CzoHijGl^O, [226°]. Sol. alcohol, benzene,
ether, and acetone (Orewsen, A. 212, 351). Fum-
ing HIAq at 150° gives CggHuO,!:, which crystal-
lises from alcohol in plates [230°]. Sol. dilute,
but insol. cone, EOHAq. ^
Be/erewces.— 7D1-BROMO-, Di-beomo-di-niibo-,
ChIiObo-, D1-OHLOBO-TETBA-10SO-, and NiTBO-FLr-
OBESOEIN.
Homoflnoresceui (so-called) C2,H„0,. Pre-
pared by the action of chloroform and NaOH
on orcin (Schwarz, B. 13, 543). Bed, metallic-
green needles or plates. SI. sol. water, alcohol,
and cold acetic acid, insol. ether, benzene, and
ligroin. Its dilute alkaline solutions have a
strong green fluorescence. It is a weak dibasic
acid. The sodium salt forms fine yellowish-red
needles, sol. water; the barium salt red needles
or scales, and the silver salt a dark-red powder.
Its substitution-products dye wool and sUk vari-
ous shades of yellow and red.
Tetra-acetyl derivative
Cj3H„0(OAc)4 + 2H20 1 Amorphous powder or
biownisn-yellow plates. Insol. water, sol. alcohol.
Tetra-bromo-homo-fl'Uoresce'Cn
C23H„Br405. Brown leaflets. Sol. alcohol. —
NaC-^i^r^O, 4aq : microscopic red needles, sol.
NaOHAq.
Tri-iodo-homofluoresce'in 02,H,,I,0,.
Microscopic red crystals. — 'SaO^fiiflJ.,. Bed
microscopio needles, sol. hot water and dilute
alcohol, instl. NaOHAq.
Sexa-nitro-oxy -homo fluorescein
02sH,j(N02)a08 aq. Eeddish-yellow leaflets.
Formed by nitration of homofluorescein. By
boiling with aqueous NH, , it forms the acid
CasHnNgO,,, and by the action of KCN the acid
CjsHijNgO,,. The nitrate is a yellowish-red crys-
talline powder, explodes at 180°, sol. alcohol. —
A'Na and A'Ag. Small red leaflets.
Hexd-amido-oxy-homofluoresce'in
G2,H,2(NH2)gOs. Colourless microscopic crystals.
Produced by reduction of the hexa-nitro- com-
pound.
Hexa-nitro-homofluorescein-eyamie
acid CjBH„N80„aq. Crystalline powder.
Sparingly sol. water and alcohol. Formed by
the action of ECN on the hexa-nitro- compound.
— X"Kj, Fine yellow soluble needles.
Compound C2,H„NjO„. Eeddish-yellow
powder. Formed by boiling the nitrate of the
hexa-nitro- compound with aqueous NH,.
— ^A"(NH,)p Beddish-yeUow scales or small
yellow needles (Schwarz, B. 13, 643),
PLTJOBESGElN CABBOXTLIC ACID
Prepared by heating resorcin with^ trimellitie
anhydride (Schreder, B. 11, 1340). Tellow
amorphous powder ; v. si. sol. water and HOAo,
T. >ol. alcohol, ether, and benzene. The metal-
lic derivatives EajA'", and CaaA'''^ are red amot-
phous powders.
Acetyl derivative C^HigAcjO, ; yello*
flocculi.
Di-bromo- derivative O^fiio'Btfl, : red
needles.
Tetra-bromo- derivati/oe G,^B^ifl,i
red amorphous powder. — KjCjiHsBrjO,.
. FIUOEESCEill-STrLPHOinc ACID
02|,H„05(S0,H). Eeddish-yellow needles or
prisms. Easily soluble in alcohol and hot water,
less readily in cold water, insoluble in ether. Its
aqueous solution is yellow, with a slight fluores-
cence ; the alkaline solution possesses a powerful
green fluorescence. Obtained by heating (j3)-sul-
phophthalic acid with resorcin. — A"'2Ca3. Bed
solid, very soluble in alcohol (Graebe, B. 18,
1129).
FIirOSHTDBIC ACID. HF. (Hydrofluoric
alAd. Hy^ogen fluoride.) Mol. w. 20. [-92-3°]
(Olszewski, M. 7, 371). (19-44°) (Gore, Pr. 17,
256). S.G. jf;^ -9879 (Gore, Z.c.). V.D. 0. 10 at
100° (Gore, Fr: 1869. 173) ; 19-6 at 30-5° (Mallet,
Am. 3, 189) ; 25-6 at 26-4°, 10-3 at 88-3° (Thorpe
a. Hambly, O. J. Trans. 1888. 765 ; 1889. 163).
Vapour pressure at 15° = 394 mm. (Gore).
Schwankhardt observed in 1670 that glass
could be etched by fluorspar and sulphuric aci^ ;
Scheele, in 1771, recognised that this etching
was due to the formation of an acid from the
fluorspar ; > Wenzel prepared the acid fairly pure ;
Gay-Lussao and Th^nard, in 1810, examined its
properties ; and Ampere suggested that the acid
was not an oxygen compound. Gore, in 1868,
obtained the pure acid.
Formation. — 1. By decomposing calcium
fluoride {flttorspar) by sulphuric acid. — 2. By
heating acid potassium fluoride, KHFy — 3. By
the reaction of dry H^S withPbFj. — 4. By heat-
ing AgF in a stream of H.
Pre^araUon.—!. 200 grams dry KHFj are
heated in a Pt retort so long as moisture comes
off ; the neck of the retort is then connected with
a small condenser made of Ft, the joint being
made tight by molten sulphur ; this condenser
is filled with a freezing mixture, more of which
can be supplied by a specially arranged charging
apparatus ; the condenser ends in a small Ft
fiask, from the neck of which a long Pt tube
passes upwards. On continued heating the KHF,
is decomposed to KF + HF ; the HF is condensed
and received in the Pt flask ; the air in the ap-
paratus escapes through the Pt tube, the length
of which prevents the entrance of moisture. The
figure shows the arrangement. — 2. Approximately
pure liquid HF may be prepared by gently heat-
ing a mixture of pure cone. H^SO, with so much
powdered CaF, (free from silica) that the whole
FLUORHTDRIO ACID.
559
Temaing quite liquid, in a Ft retort oonneoted
'with a small Pt flask or (J tube surrounded by a
freezing mixture. — 3. An aqueous solution of
HP is prepared by heating together powdered
CaF, and oonc. H,SOj in a leaden retort, and
leading the gas into water in a vessel of Pt or Pb
ikept cold by ice (for description of the apparatus
V. Brieglieb, A. Ill, 380). Commercial HFAq
may be purified by passing H^S into it, adding
enough KjCOj to saturate the £[2804 and H^SiF,
present, decanting from the pp., removing ECjS
by AgCO,, filtering and distilling from a retort
of Pb or Pt (Gtore, Z.c.). The aqueous acid is
kept in bottles made of gutta percha.
Properties. — A colourless, very mobUe liquid,
which fumes in the air and absorbs water very
rapidly. Barns and inflames if let fall on the
skin. The vapour is very irritating and very
poisonous. The anhydrous acid should be kept
in Pt flasks with tight-fitting Pt caps covered
with paraffin. Solidifies at — 102-5° and lique-
fies again at -92-3° (Olszewski, \M'. 7, 371). A
cone, aqueous solution of EF is a colourless,
strongly acid liquid, which fumes in the air;
when distilled at 760 mm. HP is evolved and a
liquid remains, containing 36-38 p.c. HF ; when
this acid is kept in contact with chalk for a little
the hquid then contains 32-5-32-7 p.c. HF ; when
dilute HFAq is distilled at 760 mm. water is
evolved until the liquid contains 32-2-32-4 p.c.
HF, when the composition remains constant
(Eosooe, O. J. 13, 162). S.G. of HFAq 35-9 p.c.
HF = 1-15; S.G. of most cone. HFAq =1-06.
Bineau regarded the acid of 35-9 p.c. as a hydrate
HP.2H20,but Eosooe's observations, which show
that composition varies with pressure, render
the existence of a definite hydrate improbable.
When HFAq is neutralised by soda much heat
is produced; [HFAq.NaOHAq] = 16,272 (Th.
1, 167). Addition of HFAq to the NaF thus formed
causes disappearance of heat [NaFAq,HFAq]
= — 288 (Thomson). The heat of neutralisation
*f HFAq is 18 to 19 p.c. greater than that of the
analogous haloid acids ; HF is the only haloid
acid the reaction of which with its own alkali
salts is attended by the disappearance of a con-
siderable quantity of heat. The relative affimty
of HFAq is extremely small, being less than 1
if that of HOlAq is taken as 100 (c/. APEiNiTy,
vol. i. p. 75). ,
Molecular weight. — H HF is the molecular
formula of flnorhydrio acid the vapour density
of the compound must be 10 (H = 1) ; Gore de-
termined the V.D. indirectly by heating a known
volume of H with a slight excess of AgF and
measuring the HF produced ; at 100° the volume
of HF was approximately double that of the H,
but at lower temperatures it was considerably
less (2V. 1869. 173). Mallet weighed the HF gas
in a flask coated internally with paraffin; at
30-5° the V.D. was found to be 19-6, which cor-
responds fairly well with the formula HjF^ {Am.
8, 189). Thorpe and Hambly (O. J. Trans. 1888.
765; 1889. 163) have determined the V.D. of
HP in a specitJly constructed apparatus of Pt ;
they made 14 experiments at temperatures be-
tween 26-4° and 88-3° ; the V.D. varied from 25-6
at 26-4° to 10-3 at 88-3°; these results rather
point to the gradual breaking down of a complex
molecular group as temperature rises, with final
production of molecules of HF, than to the exist-
ence of definite molecules of H2F2 at one tem-
perature and HF at another. They have also
examined the effect of altering pressure, at con-
stant temperature, on the Y.D. of HF. The tem-
perature chosen was 32°, because the V.D. at
this temperature and 760 mm. pressure corre-
sponds with the formula H^Fj. A. small lower-
ing of pressnre was accompanied by considerable
decrease of V.D. ; hence there is no evidence of
the existence of a stable gaseous molecule H^F^.
Nevertheless the results do not negative the view
that the composition of the chemically-reacting
unit of fiuorhydric acid is represented by the
formula H2F2. This view is in keeping with
the readiness with which fluorides such as
KPHF( = KHF2) are produced (w.FLUOEroEs). But
it might be argued that the existence of the salts
KF.2HF and KF.3HF (Moissan, O. B. 106, 647)
points to the existence of the acids H,F, and
H4F4.
JBeactions. — 1. When dilate HFAq is electro-
lysed in a Pt vessel, H and 0 (with ozone) only
are evolved ; if the solution contains 80 p.c. HF
the acid is decomposed, H is evolved at the
kathode, and the anode is attacked by the F
there produced (Gore, Pr. 17, 266). Electrolysis
of liquid HF kept at - 23° results in production
of fluoriiie at the anode (Moissan, C. B. 108, 202,
266) ; for details of apparatus, &e. v. Fluobine,
p. 461. — 2. Liquid hydrofluoric acid at —29°
to — 18° does not react with non-metals, nor with
metals except the alkali metals ; it reacts vio-
lently with many anhydrides, e.g. PsO,, SO^;
chlorides of alkali amd alkaline earth metals are
decomposed, also chlorides of phosphorus, anti-
morvy, and titarwwm ; many organic hodAes are
rapidly charred; jiaroj^ is unchanged ; glass is
unattacked by perfectly dry liquid HF, but if a
tra^e of moisture is present SiF, is formed (for
other similar observations v. Gore, Pf. 17, 256 ;
Tr. 1869. 173). — 3. An aguembs solution of hy-
drofluoric acid reacts with mstals and metallic
oxides very similarly to HClAq, forming fluo-
rides, and evolving H with metals, and forming
water with metallic oxides; silicon, boron, tan-
talum, and zirconium, are dissolved by HFAq. — :
4. SiUca and siUcates are rapidly decomposed by
HFAq with evolution of gaseous SiF, ; if water
is present in considerable quantity the SiF4 re-
acts with it to produce silicofluorhydric acid
H^SiPj {v. Sniioo-i-LUOBiDES under SrLicou). This
reaction is made use of in etching glass. — 5. Ti-
tandc, tin, tantalic, mol/yhdic, and tungstic oxides,
which are insoluble in most acids, are dissolved
by HFAq forming fluorides, which then combine
with HF (a. Titano-plooeides, Sianno-pluoeides,
Ac, under TiTAintiM, Tin, &o.). — 6. With metalUc
oxides HFAq reacts to form fluorides, and in
many oases these combme with xSS (v. Fluob-
n>EB)>
OonibmalAcms, — ^With Taa.n.yfhKirides to form
salts, of which KP.HF, NH4F.HF, BiF8.3HF, and
SiPj.SHF, are typical. Certain of these com-
pounds of HF with fluorides are best regarded as
distinct acids, e.g. SiF4.2HF reacts as an acid,
forming salts, M'^SiF,, known as siUco-fluorides ;
stanaio-fluorides, tantalo-fluorides, &a., are also
known ; these salts are described under their re-
spective headings as sections of the articles
SiuaoN, Tor, Tantuuh, &a. (v. also Fluobideb).
M. M. P. M.
560
FLUORIDES.
FLUOBIDSS. Binary com^ouiids of F with
other elements. Fluorides of all the metals with
the exception of 10 or 12 (and these mostly rare
metals which have not been at all thoroughly ex-
amined) have been prepared. Muorides of the
following non-metals are also known, viz. B, H, I,
P, Se, S, and Te; no fluoride of Br, C, CI, N, or
O has yet been isolated. Fluorides are prepared
(1) by the reaction between HFAq and metals or
metallic oxides ; ^2) by heating fluorspar and
H2SO4 with metallic oxides, this method is ap-
plicable to volatile metallic fluorides ; (3) by
ppn., applicable to insoluble metallic fluorides ;
(4) by heating non-metals with HgFj or PbPj.
Metallic fluorides are generally easily fusible
solids, similar to, and, as a rule, isomorphous
with, the chlorides. Some non-metaJlio fluorides
are gaseous at ordinary temperatures, e.g. SiFf
andPF^; others are liquids, e.g'.IFj-, and a few are
solids, e.g. SbF,. Metallic fluorides are generally
insoluble in water ; AgF and SnF, are soluble,
and FeF„ NaF, and KF, are sparingly soluble.
The fluorides of Bi and Sb are not decomposed
by water, whereas the chlorides of these metals
are at once decomposed. Most metaUio fluorides
are very stable, not being decomposed either by
beat, or by heating with carbon or in oxygen ;
solutions of these fluorides generally react slowly
with alkaline silicates forming lit' and basic
fluorides. Kon-metallic fluorides are generally
more stable than the corresponding bromides,
chlorides, or iodides; thus PCI, is dissociated
by heat, but PF, is an extremely stable gas.
Fluorides are decomposed by heating with CI or
with conc.'HjSOf. Almost all metallic fluorides
readily combine with HF forming acid salts,
aqueous solutions of which turn blue litmus red
and etch glass ; these acid salts are decomposed
by heat with evolution of HF. Some of these
acid salts are better regarded as distinct acids,
the negative radicle of which is formed of metal
and fluorine ; the following probably belong to
this class: SnF,.2HF, TiF4.2HF, ZnF4.2HF;
( = HjMFg). Fluorides, as a class, combine to-
gether to form double fluorides ; the fluorides of
the alkali metals show a remarkable readiness
to combine with other metallic fluorides ; in many
cases, but not in aU, as many molecules of alkali
fluoride combine, as there are atoms of fluorine
in the other fluoride, e.g. BeF2.2NaF, BiFj.SKF.
These double fluorides are generally more stable
compounds than corresponding double chlorides,
bromides, or iodides. The readiness with which
acid fluorides and double fluorides are produced
has suggested that the formula expressing the
composition of what may be called the chemieal
molecule of fluorhydric acid should be written
HjF, This is perhaps confirmed by the especial
ease with which alkali fluorides form acid fluor-
ides MHF^; thus KF and NaF react with an
acid so weak as acetic to formKHFj and NaHFj
respectively (2KFAq + Oj,HjO»Aq
= KF.HFAq + C2H,K0jAq). The fact that
the quantity of heat which disappears when
HFAq reacts with NaF amounts to about 2 p.c.
of the heat of neutralisation of HF by NaOH,
whereas when the other haloid acids react with
their alkali salts hardly any heat disappears,
tends to confirm the view that the reacting unit
of fluorhydric acid is H^Fj rather than HF. The
fery small affinity of HFAq (less than 1 when
that of HClAq = 100), especially taken in eom-
junction with the marked stability of the fluor-
ides, also marks off this acid from the other
haloid acids.
Fluorides are detected by gently heating with
cone. H2SO4 in a leaden or platinum vessel,
which is covered with a piece of glass coated
with wax, through which lines are traced with a
needle ; after a little the glass is removed and
the wax wiped off when warm ; the glass appears
etched where it was exposed to the vapour of
HF coming from the fluoride. Fluorides may
also be detected by mixing with miorocosmic
salt and heating strongly by a small blowpipe
flame in a glass tube open at both ends ; HF is
evolved and partially condenses with water on
the upper parts of the tube ; on evaporating the
water a duU spot is seen on the glass.
Fkiorides a/re estmnated by evaporation with
cone. H2SO4, the residual metallic sulphate ia
weighed, and the fluorine is determined by dif-
ference. Or the issuing vapour is led into water,
a weighed quantity of PbO is added, the whole
is evaporated to dryness and heated, and the re-
sidue is weighed ; in this process F is substituted
for 0 ; iid= increase in the weight of the oxide
of lead used, then
19
amount of F in residue = - — — d,
19-8
For details, and also for other methods of esti-
mating F and HF in presence of fluorides, and
for separation of F from other elements, a manual
of analysis must be consulted. M. M. P. M.
FLXrOBINE. P. At. w. 19. Mol. w. 38
(Moissan, G. B. 109, 861). For chief lines in
emission-spectrum, v. Salet {A. Ch. [4] 28, 34)
and Moissan (O. B. 109, 937).
History. — Schwankhardt, in Niimberg, ob-
served in 1670 that glass is etched by contact
with sulphuric acid and fluorspar. About 110
years after this, Scheele showed that the etching
observed by Schwankhardt was due to a distinc-
tive acid produced by the reaction between the
fluorspar and sulphuric acid. Gay-Lussac and
ThSnard obtained this acid in 1808 (J.. Ch. 69,
204) , and endeavoured, unsuccessfully, to demon-
strate the presence of oxygen in it. In 1810
Ampere declared the acid to be analogous to hy-
drochloric acid, and to be a compound of H with
an element resembling chlorine. To this element
he gave the name of Phtor (tl>e6pios = destroying) ;
but the name fluorine was generally employed in-
asmuch as it suggested that the etching com-
pound of the element was obtained from fluorspar
{spathum fluon-icwm). The investigations of
Fremy {A. Oh. [3] 47, 5) and Gore (Pr. 17, 256 ;
Tr. 1869. 173) rendered certain the composition
of the acid first obtained by Gay-Lussac and Th6-
nard. Davy, in 1809 and 1813 {Tr. 1809 ; 1813.
263) endeavoured to isolate fluorine by leading
01 over heated AgF ; as he obtained a gas which
seemed to be 0 he concluded that F had probably
been liberated, but had reacted with the glass.
He then used Pt vessels, but obtained fluoride
of Pt ; a trial with vessels of fluorspar was un-
successful. Baudrimont {J. pr. 7, 447) heated
a mixture of fluorspar, MnOj, and HjSOj in a
glass vessel, and obtained what he declared to
be a mixture of HF, SiF„ and F ; he described
F as a yellowish gas which bleached, did not aot
FLUORO-BENZENE,
661
on glass, and combined with gold ; tlie gas was
probably CI derived from chlorides in the fluor-
spar used. Euox attempted to decompose HgF
by CI in a vessel of fluorspar {,T. pr. 9, 118) ; he
obtained EgCl and a yellowish gas which rapidly
acted on glass. S. J. Knoz electrolysed HP and
FbF.^, and obtained a colourless gas, which did
not act on Au or Pt {J. pr. 20, 172). Louyet
{Ph. G. 1847. 321) again attempted to decompose
HgP by CI, using a vessel of fluorspar. He ob-
tained a colourless gas which did not attack
glass, decomposed water at the ordinary tempe-
rature, and combined directly with all metals
except Au and Pt. Kiimmerer {J. pr. 85, 457)
allowed I to react with AgP in a vacuous glass
tube at 70°-80° ; he obtained a colourless gas,
which was whoUy absorbed by KOHAq, but did
not combine with Hg. Phipson (J", pr. 88, 63)
thought fie had isolated F by the reaction be-
tween CaF,, KMnOj, and E^SO, ; he described it
as a colourless gas, which bleached, decomposed
water rapidly, and was without action on glass.
Prat (C. R. 64, 345, 511) decomposed KF by
heating with MnO, and KNO, ; he treated the
gas obtained with baryta, and described the re-
sidual gas as F; it was colourless, combined
with most metals, also with B and Si, but not
with SiO,. Gillis repeated Prat's experiments,
but obtained only O {Z. [2] 4, 660). Eenisch
{N. J. P. 12, 1) obtained what he regarded as a
mixture of O and F by heating cryolite with
PbOj and K^S^O,. Gore attempted to prepare
F by decomposing AgF by 01 (O. J. [2] 7, 368).
Varenne noticed the production of a gas which
attacked Pt by heating (NHJjCrjO, with HF
(C. B. 91, 989). 0. Low (B. 14, 1144, 2440)
thought that the greenish gas obtained by break-
ing up fluorspar from Wosendorf was F; he
traced the F to the presence of a fluoride of
Ce, which was decomposed with evolution of F.
Brauner in 1881 (B. 14, 1944) obtained a gas
more or less resembling CI by heating CeF„ and
also by heating PbP,. In 1886 Moissan electro-
lysed dry hquid HF in a Pt tube by means of a
powerful battery (C B. 102, 1543) ; H was ob-
tained at the negative pole, and at the positive
pole a gas was formed which decomposed water
withproduotion of ozone, and was wholly absorbed
by Hg with formation of HgFj ; the gas combined
energetically with P and Si. A little later (C. B.
103, 202, 256) Moissan repeated the electrolysis
of HF and obtained F.
Pfepan-ation. — The apparatus used by Mois-
san consists of a U-tibe of Pt, with stopper of
fluorspar and Pt delivery tubes ; the positive
electrode is formed of an alloy of Ptwith lO'p.o.
of Ir; KHFj is dried at 100°, and then in vacuo
over HjS04 and KOH ; the salt is then heated
in a Pt retort, and the HF is condensed in a Pt
receiver surrounded by a freezing mixture. The
HF is placed in the U-tnbe which is surrounded
bjr CHaCl boiling at -23° ; the current from 20
Bunsen cells, coupled in series, is passed through
the liquid; any traces of water in the HF are
decomposed with formation of gases at the posi-
tive pole ; when the HF is perfectly dry electro-
lysis stops, a little perfectly dry KHFj is dis-
solved in the HF, and the conductivity is thus
itacreased. H is now evolved at the negative
pole, while at the positive pole there is produced
A colourless gas in which 3ii S> As, Sbr 3i and I
Vol,. 11.
take fire, and which decomposes H^O, forming
HF and ozone, and possesses other distinctive
properties quite different from those belonging
to a mixture of HF and ozone {v. Properties and'
To determine whether this gas was really F
or a perfluoride' of H, Moissan connected the>
electrolytic apparatus with a Pt tube containing
KF, to remove traces of HF, and then connected
this tube with another made of Pt containing a
weighed quantity of iron wire, and attached to
an apparatus for collecting any gas which might
come from the tube. The whole apparatus was
filled with dry CO,, and an arrangement was
adopted for collecting and measuring the H
evolved at the negative pole. The tube contain-
ing the iron wire was heated to dull redness, the
U -tube was cooled to -50°, and electrolysis wais
begun. The weight of iron fluoride formed was
exactly equivalent to that of H evolved ; no gas,
except a trace of air, was obtained from the tube
in which the iron wire was heated. Hence the
gas evolved at the positive pole was fluorine.
Moissan says that as much as 1*5-2 litres F can
be obtained in an hour by this method. He
also states that the gas is formed by electrolysis
of fused KHF,.
Properties and BeacUons. — Fluorine is a
pale yellow-green gas. It decomposes water,
forming ozone and HF. Crystallised silicon,
boron, arsenic, antirnomy, sulphur, and iod/irie,
take fire at once in the gas. It attacks metals
less readily, probably because a film of fluoride
is soon formed on the surface. Powdered iron
and mangcmese burn briUiantly in F, when'
gently heated. Orgcmid compounds are rapidly
decomposed, alcohol, ether, benzene, &c., take
fire at once in the gas. F combines violently
with hydrogen even in the dark.
Fluorine is allied to 01, Br, and I ; the ana-
logy is shown in the composition and properties^
of its compounds, but there are points' of differ-
ence (v. FiiUOKHYDBic ACID and Fluobideb).
The atomic weight of fiuorine has been de-
termined (1) from determination of V.D., and
analyses, of HF (Gore, Pr. 17, 256 ; Tr. 1869.
173; Mallet, Am. 3, 189; Thorpe a. Hambly,
G. J. trams. 1888.765; 1889. 163); (2) by con-
verting CaFj into CaSO, (Louyet, A.. Gh. [3] 26^
295 ; Dumas, A. Gh. [3] 55, 170 ; DeLuca, C. B.
51, 299) ; (3) by converting NaF to NajjSOi, KF
to KjSO,, and PbF^ to PbSO, (Louyet, l.c.-,
Dumas, l.e.) ; (4) by treating Mn2F8.4NH4F with
HOI and KI, and estimating the I set free by
titration with NajS20s(Christensen, J.pr. [2] 34^
41). M. M. P. M.
OT-FITIOEO-ANIIINE C,H,FNH,[1:3]. From
CeH,(NHAc).N,.NOsH,„ and cone. HF (Wallaoh,
A.2-iS, 266). Gil.— (B'HCl)2PtCl4.
^-Fluoro-aniline CoH^F.NH, [1:4]. (o. 189°);
S.G. 2^ 1-153. From j>-fluoro-nitro-benzene,
SnOL,, and HCl (Wallaoh, A. 23S, 267). Liquid
which solidifies in a bath of ether solid and
CDj.
Salts .— B'Ha.— (B'HCl)sPtCl4.
Acetyl derivative CgHtF.NHAo. [161°]i
SI. sol. water (Wallach a. Heusler, A. 243, 222).
FLUOEO-BENZEKE C.H5F. Mol. w. 96i
(85°). S.G. y 1-0236. /«» 1-46773 (WaUaoh (b
Heusler, A. 243, 219). V.D. 3-13 (oalo-. 3,06).
formation' — !• By beating potassi^ani
99 '
562
FLUOBO-BENZENE.
flnoro-benzene Bulphonate -mih oouc. HdAq
(Patem6 a. Oliveri, 0. 13, 533) 2. By deoom-
posiug diazobeuzene piperidide with cone,
aqueous hydrofluorio acid, the escaping gases
being very well cooled (Wallaoh, A. 235, 255).
Properties.— Liqxiid. which solidifies in ether
and solid carbonic acid. The so-called fluoro-
benzene described by Schnutt a. Gehren (J. pr.
[2] 1, 394) was phenol.
jp-Di-fluoro-benzene CeHjFj[l:4]. (88°). S.G.
I'll. Formed by decomposing p-fluoro-benzene
diazo-piperidide with hydrofluoric acid (Wallach
a. Heusler, A. 243, 224). Liquid solidifies at a
very low temperature. i
p-FLTTOBO-EENZEirE STTLFHONIC ACID
CeH4F.SO,H[l:4]. From p-amido-benzeue sul-
phonic acid by displacing NHj by F (Lenz, B.
10, 1137 ; 12,. 580). The salts are v. e. sol.
water and alcohol.
Chloride OsH^F.SOjOl. [36°]. Trimetrio
tables or long needles ; sol. benzene, chloroform,
and ether.
Amide CoHiF.SOjNHj. [123°]. Trimetrio
plates or long needles. SI. sol. water and benz-
ene, V. sol. acetone and alcohol.
o-FLTJOEO-BENZOIC ACID CaH,F.C0jH[l:2].
Mol. w. 140. [118°]. Prepared by treating
0-diazo-amido-benzoic acid with cone. HFAq
NH2.C„H3(C02H).N,.0jH,C0jH + 2HF
= C,H4NH3F)COjH + OeH^F.COjH
(Patern6 a. Oliveri, G. 12, 85). Colourless silky
needles (from hot water). Y. sol. alcohol and
ether. More soluble in water than its isomerides.
BaA'2 2aq : laminss, v. e. sol. water. — CaA'^ :
laminae, v. e. sol. water.
OT-FIuoro-benzoic acid OjH4P.C02H[l:3].
[124°]. From m-diazo-amido-benzoio acid and
oonc. aqueous HF (P. a. O.). Iiauunes, resem-
bling benzoic acid. — NaA'aq: opaque scales. —
AgA' : colourless needles (from hot water) ;
quickly altered by exposure. — BaA', 3aq : v. sol.
hot water. — OaA'^ 3aq : pearly plates.
Methyl ether MeA'. (194°). Aromatic oil.
p-riuoro-benzoic acid CsH^F.COzH [1:4].
[182°]. Prepared by heating p-diazoamido-
benzoic acid with concentrated aqueous hydro-
fluoric acid ; on cooling, the greater part of the
flnoro-benzoic acid separates out, while the
hydrofluoride of p-amido-benzoic acid [211°] re-
mains in solution (Schmitt a. Gehren, J. pr.
[2] 1, 394 ; Patem6, 0. 11, 90 ; 12, 85). Obtained
also by oxidation of p-fluoro-toluene (Wallach,
A. 235, 263). Laminse or needles, smelling like
benzoic acid, si. sol. cold, v. sol. hot, water ; v.
Bol. alcohol, ether, and benzene. Volatile with
steam. Does not etch glass. Cono. HNO, gives
a fluoro-nitro-benzoio acid. Gone. EjSOi dis-
solves it without alteration.
Salts . — ^BaA'2 4aq : colourless ill-defined
laminsB, m. sol. hot water. — CaA', 3aq : large
prisms. — AgA' : yellow plates (from water).
Ethyl ether EtA': crystalline; may be
distilled.
Dl-flnoTO-benzoic acid CgH,F2.002H. [232°].
Formed by the action of chromium perfluoride
(from CaFj, Kfitfi, and E^SO,) upon benzoic
acid (Jackson a. Hartshorn, B. 18, 1993 ; Am. 7,
S43). Flat white needles, sol. hot benzene, si.
aoL hot water, nearly insol. cold water.
Salts. — ^A',Ca3aq: long silky needles. S. -6
9t IS'^A'sBft : sc»lM. S. 1-a 8tl6°,— KA'.
p.FLTr0B0-BB0H0-B£KZ£N£G,H,Br7[l:41,
[-15° to -20°]. (153°). S.G. 15 1-593. From
j)-fluoro-aniline by diazotisation and treatment
with cuprous bromide (Wallach a. Heusler, A.
243, 226). OU.
p-FLUOBO-CHLOBO-BENZEirE G^,C1F.
(131°). S.G. >^ 1-226. From i)-fluoro-aniline
by diazotisation and treatment with cuprous
chloride (Wallach a. Hensler, A. 243, 225). Oil;
volatile with steam. Solidifies at a very low
temperature.
o-FLUOBO-CINNAMIC ACID 0^,F0, i.e.
CeH4F.CH:CH.C02H. From the sulphate of 0-
di&zo-cinnamic acid and HF (Griess, B. 18,961).
Long needles. V. si. sol. boiling water, v. sol.
alcohol.
FLTrOBO->('-CTJMEWE OeH,Me^ [1:3:4:6].
[27°]. (175°). From diazo-ilf-cumene piperidide
and cone. HFAq (Wallach a. Heusler,'^. 243,
231). Volatile with steam.
FLTTOBO-HIFFTTBIC ACIDS
C8H4F.CO.NH.CHj.COjH. The fluoro-benzoio
acids are transformed by the animal organisms
into the corresponding fluoro-hippuric acids, and
may be extracted from the urine by evaporating
it to a syrup, treating with alcohol and filtering.
The residue, on distillation of the alcohol, is de-
composed with hydrochloric acid and taken up
with ether, which on distillation leaves an oily
mass from which the pure acid is obtained by
conversion into the calcium salt and decomposing
this salt with hydrochloric acid (Coppola, 0. 13,
522).
o-Flnoro-Mppnrio acid [121°]. Crystallises
in prismatic, iridescent needles, t. sol. ether and
alcohol, si. sol. chloroform, insol. carbon disul-
phide and benzene. It is decomposed by fuming
hydrochloric acid into glycocoll and o-fluoro-
benzoic acid.
m-Flaoro-hippnric acid [153°]. Prismatic
needles, V. sol. hot water, alcohol and ether, insol.
carbon disulphide and chloroform. — CaA'2 2aq:
rectangular laminae. — PbA'2 5aq: small laminee.
— AgA': flocculentpp.
jj-Fluoro-hippuric acid [161°]. Pearly
needles (from ether). Insol. benzene, CS,, and
chloroform, sol. alcohol, ether, and boiling
water. — CaA'2 2aq: four-sided tables, t. e. sol.
water and alcohol.
jp-FLTTOBO-IODO-BENZENE Oja^IF [1:4].
(183°). Formed by decomposing ^fluoro-diazo-
benzene piperidide with cono. hydriodic acid
(Wallach a. Heusler, A. 243, 227). Oil, volatile
with steam, solidifies at low temperatures. Gone.
HNO, liberates iodine with the formation of
fluoro-nitro-benzene.
p-FLTJOBO-NIIBO-BENZEKE CeH,F(NO,).
[24°]. (205°). S.G. 1^326. Formed from
OsB.,(T<lO^).'S,.TSCsBu and cone. HF (Wallach,
A. 235, 264). Formed also by nitration of
fluorobenzene. Oil, heavier than water ; smells
like almonds.
FLT;0B0-7)-0XY-BEKZ0IC ACID. Methyl
derivative 0^^(OMe).CO^. Fluoro-armie
acid. [204°]. From amido-anisio acid [181°]
by the diazo- reaction (Fatemd a. Oliveri, (?. 13,
92). Colourless needles, sol. water and alcohoL
p-FlUOBO-FHENOL C,H,F.OH [1:4]. (187°).
Formed by diazotisingp-fluoro-aniline and boil-
ing with water (Wallach a. Hensler, A. 943,
Solid »t prdinary temperatures.
FORMIC AOro.
Dl-riUOEO-DIPHENTL C^M.^., i.e.
P.O,H,.p«H,P. [89°]. (255°). Formed by da-
composing bi-diazo-diplienyldipiperidida with
cone. HPAq (Wallaoh a. Heusler, A. 243, 234).
Crystalliae, v. sol. alcohol, ether.
p-FITTOEO-TOLTIENE OH,.C,H,P. (llVi. V.).
S.G. as .992. Prepared by heating its sulphonio
acid (obtained from (1, 4, 2) amido-toluene sul-
phonio acid) with oonoi EClA.q in sealed tubes
(Patem6 a. OUveri, &. 13, 535). Obtained also
from j)-diazo-toluene piperidide and oono. HP
(WaUaoh, A. 235, 261). Smells like benzo-
nitrile. CrO, and aqueous H^SO^ at 160° give
p-fluoro-benzoio acid [182°J.
fLUOSO-TOLUIC ACID
CsH3MeP.0OjH[4:3:l]. [16^. From amido-
toluic acid [165°] by the diazo- reaction (Paternd
a. Ohveri, O. 12, 83). Needles, sol. water and
alcohol.
FITrOBSFAB. Calcium fluoride (v. vol. L
p. 665).
FOOI-KITCIII)' V. Pboteidb, Aj^mdiss O.
POBMAMIBINE CH^Nj i.e. NH,.CH:NH.
Atmdo4inida-methaMe. Forminddaimde, Me-
thenylamidine. Formed from the compound
(HGN)23HC1 by decomposing it with alcohol at
100° ; the products being formic ether and form-
amidine (Gautier, A. 145, 118 ; Claisen a. Mat-
thews, C J. 41, 266). Formed also by the action
of alcoholic ammonia on formimido- ether
NH:CH.OEt (Pinner, B. 16, 357). Hydro-
chloride B'HCL [81°]. Crystallises from
alcohol in warty masses or in flat transparent
plates. Very hygroscopic. Split np at 100°
into HON and NH4OI. Potash gives formic
acid and N&,. Heated with acetic anhydride
and sodium acetate it yields di-acet^l-form-
imidamide and tri - acetyl - formamidil
CjHjAOjNj. [224°] (Pinner, B. 17, 171),
Platinochloride B'sH^PtCl,: orange oota-
hedra, t. sol. water.
Di-aoetyl-derivative NHAc.CH:NAc.
Formed as above and together with a di-
basic isomeride by heating orthoformic ether
with acetamide at 180° (Wichelhaus, B. 3, 2).
Short thick prisms, sublimes without melting
(Pinner, B. 16, 1660). SI. sol. cold water, v. si.
soL alcohol.
F0BM:AMID0XIM:CH,NjOi.e.NHj.CH:NOH.
Isuretvne. Methenyl-amidoaiim, [105°]. Mol.w.
60. Formed by the action of an alcohoUo solution
of hydrozylamine on a concentrated aqueous solu-
tion of HCN in the cold ; the product is evapo-
rated at 40° (IJossen a. SchifCerdeoker, A. 166,
295). Trimetrio prisms (from alcohol). V. sol.
water, si. sol. cold alcohol. Its aqueous solution
is alkaline in reaction and ppts. s^lts of Ca, Pb,
and Hg. At 140° it splits up into OOj, NH,, and
Eonmelide. Boiling water resolves it into formic
acid, nitrogen, and NH, ; a small quantity (1 pt.)
of water when heated with it (1 pt.) gives biuret,
urea, guanidine, COj, nitrogen, and NH,. Dilute
acids split it np into formic acid, NH,, and hy-
droxylamine.
Salts.— B'HOl. [60°]. Very deliquescent
trimetrio tables, si. soL alcohol. — ^B'jHjSO,:
needles, v. e. sol. water. — S'SfiiO^: flat prisms,
m. soL water. -B CjHj(NOj),OH: yellow prisma;
m. Bol. water and alcohol.— OHjNjOHgHgOl, :
yeUow floccqlent pp. got by adding HgCl| to a
E63
Explodes when
solution of formaiiiidoxim.
heated. V. sol. HClAq.
FOBU-ANHYBBO- COUPOUITBS v. Ma.
THENTI.-C0MP0UNDS.
FOB1K[ICACISH.COOH. Hydrogenca/rboxyUe
acid. Mol. w. 46. [2°] (Bannooo) ; [8-6°] (Berthe-
lot, Pettersson, Ekstrand). (100°) (Sohiff, Lan-
doldt,Person) ; (100-8°) (Zander) ; (101°) (Eoaooe).
&.a. g 1-2415; 5 1-245; i^ 1-231; ^ 1-226;
1^ 1-22 ; ^p 1-209 ; 5f 1-2029 (Pettersson, J.pr.
[2] 24, 297); "£ 1-219 (Briihl) ; J 1-1829; §6
1-1649 (Perkin) ; WSI 1-117 (Zander). S.V. 41-08
(Schiff) ; 41-1 (Zander). V.D. (at 111-5°) 2-38
corresponding to molecular formula 2H.CO2;
(at 160°) 1-81; (at 214°) 1-62 (Pettersson and
Ekstrand, B. 13, 1194), S.H. (0°-100°) -519
(Pettersson). C.E. (0°-10°) -0097; (0°-20°)
•0196 ; (0°-509) -0509 ; (0°-100°) -11 (Zander, A.
224, 56). H.C. (at 100°) 70,750. H.F.p. 96,930.
H.F.V. 95,350 (Thomson). M.M. 1-671 (Perkin).
Ejo 13-61. A' {Constant of capillarity) 5-284
(H. Schi£(). Seat of solutioii in water 2-35 (sol.),
•08 (liq.) (Berthelot). Latent heat of fusUm
57-38 (Pettersson).
Occurrence. — 1. In the red ant (Wormica
rufa), from whence the acid derives its name
(Marrgraf, Diss. Upsala, 1777).— 2. In cater-
pillars, especially Bombyx processionea (Will, /.
1847-8, 646), and Cerura dicrarmra, the secre-
tion of which contains 37-5 p.o. of the acid
(Poalton, B. A. 1887, 766).— 3. In various secre-
tions of the human body, viz. the blood, spleen
(Scheerer, A. 69, 199) and sweat (Schottin, J.
1852, .704), — 4, In plants, viz, stinging nettles
(Gorup Besanez, A. 72, 267), the fruit of the
soap tree, Sapindtis saporuma (ibid. A, 69,369),
in tamarinds, and in the needles of Pimis abiea
(Bedtenbaoher, A. 47, 148). It is also found as
one of the products of oxidation of crude turpen-
tine oil (Weppeh, A. 34, 235 ; 41, 294; Laurent, -
J.pr. 27, 316). — 5. In the mineral waters of Priuz
Lofen (Pettenkofer, Kastn. Arehw, 7, 104), of
Bruckenau (Scheerer, A. 99, 257), ati in the
deposit from the waters of Marienbad.
Synthesis. — 1. By passing carbonic oxide
into damp alkali heated to 100°: CO + EHO
:=KCOOE (Berthelot, C. B. 41, 965); the re-
action takes place best with soda-lime heated to
190°-200° ; above this temperature the formate
is decomposed vrith production of carbonate. If
the materials are dry no combination occurs
(Merz and Tibiri^a, B. 18, 23). The addition of
alcohol promotes the absorption (Piritiringa,
Inaug. Diss., Zurich, 1879). — 2. By the action of
the sUent electric discharge on a mixture of car-
bonic acid and hydrogen C02 + H,=HjC0,
(Brodie, Pr. 21, 245).— 3. By passing a current
of damp carbonic acid over metallic potassium
2C0j+K,+0Hj = HC00K + KHC0, (Eolbe and
Schmitt, A 119, 251).
formation. — 1, By the oxidation of wood
spirit (Dumas a. Feligot, A. 15, 7 ; Dumas a.
Stas, iUd. 36, 137), — 2. By heating wood spirit
with a mixture of lime and potash (Dumas a.
Stas).— 3. By heating hydrocyanic acid with
concentrated alkalis or mineral acids (Felouze,
A. Ch. [2] 48, 395; Geiger, A. 1, 44).— 4. By
the decomposition of oSuuUo acid by heat (Gay-
Lussao, A. Ch. [2] 46, 218), The yield is much
increased bj (Mdition Qf glycerin or mannita
993
564
FORMIC ACID.
(Berthelot, v. infra). An aqneous solution of
oxalio acid in presence of uranic oxide is decom-
poBed by sunlight into CO, and f oimic acid (See-
kamp, A. 122, 113). — 5. By decomposition of
chloral and trihalogen derivatives of methane
(Liebig, A. 1, 198; Dumas, B. J. 15, 371), or
by heating chloroform with aqueous NH, in
sealed tubesat 200°-225°, 20H01,+ 7NHi + 3H;jO
= CO + 6NH,Cl + HCOONH4 (Andrfi, C.iJ. 102,
553). — 6. By adding sodium amalgam to a strong
aqueous solution of ammonium carbonate
(NHJjCO, + Naj = HCOjNa + 2NH, + NaOH
(Maly, A. 135, 119).— 7. By distilling starch,
sugar, and various albuminous substances with
manganese peroxide and sulphuric acid (Dobe-
reiner, A. 3, 144 ; Gmelin, P. 16, 56). Other
organic snbstances, such as tartaric acid, gum,
linseed oil, woody fibre, and cereal grains, yield
formic acid when distilled with concentrated sul-
phutio acid with or without manganese peroxide.
8. By the electrolysis of water through which a
current of COj is passed (Eoyer, Z. 1870, 318).
9. By the oxidation of coal-gas by ozone (Ma-
quenne, Bl. [2] 37, 298). — 10. By heating alcohol
with nitric acid (Gaultier de Clanbry, J. Ph. 25,
764). — 11. By oxidation of tri-methylamine with
alkaline permanganate (Wallach a. Claisen, B.
8, 1238). — 12. By the oxidation of carbon (from
carbon disulphide) with potassium permanganate
(Chapman, C. J. 5, 133). — 13. As an iron-salt
by heating carbon disulphide with water a^d
iron filings (Loew, B. 13, 324). — 14. By heating
lactic acid with snlphnric acid (Erlenmeyer).
Additional references. — Hulse and Fisher, T.
1670, voL V. 2063 ; Wohler, P. 15, 307 ; Hiine-
feld, J. pr. 7, 44; Guckelberger, A. 64, 89;
Stenhonse, P. M. [3] 18, 122 ; Sacc, A. 51, 214;
Hlasiwetz, J. pr. 51, 355 ; Liebig, A. 17, 69 ;
Gehlen, A. Oh. [1] 83, 208 ; Limprioht, A. 97,
361 ; Hurst, O. J. 15, 278.
Preparation. — 1. By heating to 60° in a
capacious retort a solution of sugar (1 pt.) in
water (2 pts.)withmanganese peroxide (2-5-3 pts.)
and 1:1 salphurio acid (3 pts.). One-third of
the acid is added at first ; when the violence of
the reaction has abated the remainder of the
acid is added. The acid formed is condensed in
a receiver, and at the end of the action the dis-
tillate is neutralised with chalk, and the filtrate
evaporated to the point of crystallisation. The
calcium salt is converted into the lead salt by
addition of lead carbonate, and the lead salt de-
composed by the requisite quantity of sulphuric
acid. — 2. By heating equal parts of anhydrous
glycerin (ormannite) and crystallised oxalic acid
in a retort to 75°-90°, until carbonic acid is no
longer evolved. A fresh portion of oxalic acid
is ^en added, and the distillation continued.
This process may be repeated several times.
The distillate finally contains 55 p.c. of the acid,
and is redistilled over anhydrous oxalic acid
when a 75 p.c. acid is obtained. This is neutral-
ised with sodium carbonate, the dry sodium salt
distilled with anhydrous oxalic acid, when a
99 p.c. acid is obtained (Lorin). The last trace
of water is removed by distillation over boric
anhydride, or the acid is subjected several times
to a freezing mixture, the crystals separated from
the liquor, and then allowed to melt, or the dry
lead (or copper) salt is heated at 130° in a
SV)iie)it of di^ hydrogen sulphide} i|i the letter
case the product is apt to be contaminated witb
sulphur products (Liebig ; Wohler).
In the above process the crystallised cxalie
acid decomposes into water, carbonic acid and
formic acid, the last of which combines with
the glycerin to produce monoformin, which
is subseqrently decomposed by water into
glycerin and formio acid, the equation being
C,H.(0H), + HA04
= C,H,(OH)j(OOHO) + HjO + CO,
= C,H5(0H)j + HjCOj + COj. The details of the
process have been worked out by Lorin, Bl. [2]
5, 7, 12 ; 20, 241 ; 24, 22, 436 ; 25, 517 ; 37, 104.
Properties. — The acid solidifies below 0° and
exhibits the phenomenon of superf usion. The
liquid acid is colourless, transparent, and mobile.
It has a pungent sour taste and odour, and
when concentrated blisters the skin (Liebig).
The vapour pressure of the acid at various
temperatures has been determined by Landoldt
{A. Suppl. 6, 154) and Bichardson (C. J. 49,
765), some of whose results are given below: —
Pressure
Fressnra
Temperature.
iamm.
Temperature.
in mm.
5-7
13-46 E.
45
102-7 L.
10
18-4 L.
60
191-2 L.
10-2
17-44 B.
70
280 L.
20
31-4 Ii.
80
399-8 L.
29-7
48-33 B.
82-7
391-2 R.
80
51-6 L.
90
558 L.
40
82-3 L.
91-2
529-3 E.
44-5
82-97 B.
Aqueous acid. — Formic acid mixes in all
proportions with water. By distillation of aqueous
formic acid at standard pressure a 77 p.c. acid
(107°) is finally obtained, whatever the original
strength : this corresponds to an acid of mole-
cular composition HCOOH + HjO, and has been
termed orthoformic acid CH(OH)„ the ethereal
salts of which are described below. But on
alteration of pressure the composition as well as
the boiling-point alter; thus at 1350 nun. an
80 p.c. acid (124-1°), and at 1830 mm. an 83 p.c.
acid (134-6°) finally distil (Bosooe, G. J. 16, 270).
Ferkm iC. J. 49, 778) also concludes that the
so-called hydrate S.G. * 1-1829 is only a mixture
of the acid and water.
' A 30 p.c. aqueous acid has the maximum
electric conductivity (Hartwig, W. 33, 58).
BeacHcms. — 1. The acid is completely re-
solved by strong suVphwrie acid into carbonio
oxide and water (Dobereiner) ; this reaction at a
temperature of 60°-80° starts at first slowly,
reaches a maximum and then decreases at a
rate proportional to the ngiass of acid undergoing
decomposition (Veley, T. 1888, 274, 286-297).—
2. The vapour of the concentrated acid bums with
a dull blue flame (Liebig). — 8. It is slowly burnt
when dropped on platinum black (Dobereiner). —
4. GraduaUy oxidised by chlorine (Oloez), more
rapidly by aqueous iodic or periodic acid
(Benckieser, A. 17, 258 ; Millon, O. B. 19, 271).
5. Decomposed by tiitrie acid (Arvidson). — 6.
Heated with zinc-dust it is decomposed into car-
bonic oxide and hydrogen (Jahn, M. 1, 679). — 7.
Forms with brcymine in presence of carbon disul-
phide an unstable addition product, which de-
composes into HBr and CO, (Hell a. Miihlhauser,
B. 11, 245).— 8. On electrolysis it yields 0„ H,
and as fk secondary po^aQt acetic ^eid (Bourgoiqi
FORMID ACID.
666
A.. Ch, [4] 14, 185).— 9. Decomposed by silent
electric discharge into COj, CO, and Hj, the pro-
portion of the two former depending on the pres-
sure (Maquenne, O. B. 96, 63). — 10. The acid
acts as a strong reducing agent, precipitating in
alkaline solution the heavy metals, gold, plati-
num, and palladium from their solutions. With
silver nitrate it precipitates silver formate, which
is subsequently reduced to the metal ; it converts
mercuric into mercnrous chloride, and only on
protracted heating to metallic mercury. In acid
solution it reduces potassium permanganate in
the cold, and chromic acid when heated, and is
thus distinguished and separated from acetio
acid. It also reduces Fehling's solution. These
reducing properties are attributed to the presence
of the aldehydic group CHO in the acid. — 11. The
acid and its salts act as powerful antiseptics and
anti-fermentatives (Jodin, C. B. 61, 1179 ; Hoff-
mann, Intmg. Diss., Greisswald, 1884). Injected
into the system they lower the temperature and
blood pressure, and retard the heart's action
(Jahresher. Fort. Phcrnn. 1879, 127).
Detection. — 1. The solution supposed to con-
tain the acid or its salts is heated with concen-
trated sulphuric ^cid, when carbonic oxide only
is evolved. — 2. With silver nitrate they give a
white pp. turning brownish-black on boiling
(«. supra). — 3. With mercurous nitrate they give
a white pp. turning grey from separation of the
metal.
Estimation. — 1. The acid or salt is heated
for 1^ hours with sodium acetate and a normal
solution of mercuric chloride, the excess of which
is titrated with potassium iodide. Besults 5 p.c.
too low (Portes a. Euyssen, 0. B. 82, 1S04).— 2.
By a standard solution of potassium permanga-
nate acidified with dilate sulphuric acid, — 3. By
measurement of the volume of carbonic oxide
given ofi by concentrated sulphuric acid.
Formates. — Formic acid is monobasic, the
general formula of its normal salts being
B„(HCOO)„ = B„A„ ; double salts are also known
of formula B.A„.E'„A..
Metaluo Fobuates. — The salts are all
soluble in water. Those of the fixed alkalis
when heated are converted into the oxalates
with evolution of hydrogen ; those of the heavy
metals yield the metal. The barium and
calcium salts heated with the barium or calcium
salts of the carboxylic acids yield the aldehydes,
vol. i. p. 107. The salts when heated with water
in sealed tubes at 176° are more or less com-
pletely decomposed, those of Ca, Mg, Mn, Fe, Co,
Ni, Zn, Sn", Pb, Cu, Hg", Ag, yielding an oxide
or carbonate with evolution of H2, GO^, and CO,
In the case of the Co and Ni salts some of the
metal separates, possessing highly magnetic pro-
perties; from the Cu salt Cu^O separates in
violet crystals mixed with the metal also in
crystals (Biban, C.B. 98, 1023, 1082; c/.Ber-
thelot, Md. 1051).
The formates have been examined by Odbel,
Schweig, DSbweiner and Liebig ; Crystallo-
graphic measurements by Heusser (P. 83, 37) ;
Handl, Sitz. W. 42, 747 ; Zepharovioh, i6id. 43,
ii. 545; v. Hauer, iUA. 648; cf. 3. 1861, 430;
Eammelsberg, Hc6ni. Kryst. Ohem. 274 ; Voss,
Jrumg. Diss., K5nigsberg, 1887 ; Specific Gravi-
ties, by Clarke, B. 12, 1399 ; SohrSder, B. 14,
81 ; Heats of Solution and Formation, Berthelot,
O. B. 77, 24 ; Befraction Equivalent, Gladstone,
Pr. 16, 441 ; Kanonnikow, J. B. 16, 124 ; Dis-
persion (crystals), v. Lang, Sitz. W, 31, 105}
Descloizeaux, Arm. M. 11, 261.
Aluminium forrbate, obtained by ppg.
barium formate with equivalent proportion of
aluminium sulphate; crystallises with difficulty,
decomposed by hot water with ppn. of aluminium
hydrate (Liebig).
Ammonium formate NH^A': monoclinio
crystals, o:6:c = •884:1:1-269 ; j8 = 1-269, S.G. 1-266
(Schroder). Heat of solution —2-94. Decom-
poses when quickly heated to 180° into form-
amide and water but no hydrocyanic acid
(Andreasch), whUe at a higher temperature
hydrocyanic acid only is produced (Dobereiner).
Barium formate BaA',: monoclinio crys-
tals, o:6:c= -765:1: -864 (Heusser). S.G. 8-212
(Schroder), 3-471 (Clarke). Heat of solution
-2-44. S. 20 to 26 in the cold; insol. alcohol
and ether.— BaA'22aq (Krasnicki, M. 8, 699).
Formomtrate BaN03A'2aq (Ingenhoes, B.
12, 1680).
Double salts. Barium-zinc BaA'2.ZnA'2 2aq:
triclinic crystals, a:b:c = -579:1: -452 ; $ = 108° 49'
(Heusser ; Voss). — Barium manganese salt
BaA'j.MnA', 2aq : monoclinio crystals, a:b:c
= 1: -759:917 (Heusser). — Barium cobalt salt
BaA'2GoA'2 2aq : triclinic, isomorphous with
the barium-zinc salt, as also Ba/ri/um-nickel
salt BaA'^NiA', 2aq, and Barvwm copper salt
BaA'jCuA'j 2aq (Heusser ; Voss). — Barvwm cop-
per 2BaA'2.CuA'j2aq: triclinic crystals, S.G. 22
2-747. Barium cadmium BaA'^CdA', 2aq : mono-
clinic crystals, a:b:c = -898:1:54. S.G. w 2-724.
Bismuth formate. White (Srystals,
readily sol. water.
Cadmium formate CdA'^aq: mono-
clinio prisms, a:6:c = 1-325:1:1-224; )8 = 97° 6'
(Kopp). S.G. f 2-429 (Clarke), 2-477 (BchrSder),
readily sol. water, dehydrated with difficulty.
CaloinmformateCaA',: rhombic crystals,
ffl:6:c = -759:1: -467. S.G. 2-021 (Schreder). Heat
of solution -66. S. 10 to 12-6 in the cold, insol.
alcohol. Forms methyl alcohol on dry distilla-
tion.
Cerium formate CeA'aq, prepared by
ppg. a solution of cerous chloride with sodium
formate, rose-coloured, crystalline powder, con-
verted into ceroso-ceric oxide, when heated.
Cobalt formate CoA'2 2aq: rose-red crys-
tals. S.G. *a 2-1286. S. 20 at 20° Voss.
Copper formate CuA',: blue transparent
monoclinio crystals, a:&:c = l:-996:-771. S.G.
1-831 (Schroder). Heat of solution -7-84
(hydrated), -62 (anhydrous). Prepared by neu-
tralising formic acid with copper carbonate or
freshly ppd. oxide, and spontaneously evapo-
rating. If the solution is heated the basic salt
separates out. S. 12-6 to 25 in the cold. S.
(80 p.c. alcohol) -25.
Basic salt CuA'22Cu(OH)2 : pale-green pow-
der, insoluble ; prepared by boiling an aqueous
solution of the normal salt.
Double salts. Gopher hy&rogen
CuA'2HA'l^aq: blue, rhombic, six-sided tables,
a:&:c- 1-324:1:1*765, separated, together with the
CuSr salt, from a strongly acid solution cf
2 mols. SrA'2 and 1 mol. CuA', (Zepharovich).
Copper stronUwm 2SrA'2.CuA'2. 8aq : triclinic
crystals, a:&:c = -744:1:1-0103 (Zepharovich), and
see
rORMIO AOID.
SrA'jCnA',4aq. S.G. M 2133 (hydr.), 2-612
(anhyd.), Sohioder.
Didyminm formate DiAV S.G. 3-43.
S.V.S. 80-8. Violet powder, Tt d. aol. water
(Cldve, Bl. [2] 43, 365).
Erbiam formate Kr2A',4aq: red crystfkls
(Cldve, C. B. 91, 382).
Iron formates. Ferrous formate
FeA',.2aq, v. si. boL water (Scheurer-Eestner,
A. Ch. [3] 68, 480).
Ferric formate FeA',aq: yellow glistening
crystals, obtained by dissolving recently pre-
cipitated ferric hydrate in formic aoid ; from its
solution ferric hydrate gradually separates, while
a basic salt remains in solution (Scheurer-Eest-
ner: c/. Ludwig, J. 1861, 433). Formo-nitrata
Fe2A',(N0s){0H)j 3aq : yeUow crystals, readily
decomposed. Formo-chloride Fe^A'^Cl^Saq:
reddish-yellow salt, t. bL sol. water (Scheurer-
Eestner).
Iiead formate PbA',: rhombic prisms or
needles, isomorphous with barium salt (Heusser).
S.a. i-5ll (Badeker, J. 1860, 17; Schrader).
Heat of solution -3-46. S. 1-6 at 16°, 18 at
100° (Barfoed, Z. 1870, 272). Insol. alcohol,
thus differing from lead acetate. The dry
salt decomposes at 190°, thus Pb(GH0)2
= 2C05+Hj-fPb. Basic salts. By boiling
aqueous solution with lead oxide the following
basic salts separate out. FbA^PbO, prisms, sol.
68-6 pts. cold water, FbA,2FbO. Sol. 26-5 pts.
cold, 7'6 pts. water (100°), of strong alkaline re-
action, PbA,3FbO crystallhie pp. sol. 90 pts. cold
water (Barfoed).
FormomU'ate 3FbA'jPb{N0,)j 2aq : rhombic
tables, T. si. sol. (Lucius, A. 103, 115).
Lithium formate LiA'^aq: rhombic crys-
tals, a:6:c=l: -651: -484 (Handl). S.G. 1-435-
1-479 (Schroder).
Magnesium formate MgA'2 2aq: rhombic
prisms and octahedra, S. 7-7, insol. alcohol
and ether (Sonchay a. Groll, J. pr. 76, 470).
Manganese formate MnA'2 2aq: mono-
clinic crystals, o:6:c=^ 1-317:1:1-213; /3 = 97°38'
(HeuBser; Voss). S.G. 1-953 (hydr.), 2-205
(anhyd.) (Schroder).
Merourons formate Hg^A',: glistening
scales. S. -4 at 17°, decomposed when boiled with
water, KgMS03)i^'Bg„ + RfiOi+CO^ (Gobel).
Nickel formate NiA'2 2aq: green crys-
tals. S.G. 22 2-1547 (Clarke).
Potassium formate EA'. Deliquescent,
rhombic cubes. S.G. 1-908. [150°]. Heat of
solution —'93.
Samarium formate SmA',: white powder,
▼. si. sol.
Silver formate AgA': crystalline pp.
formed by adding silver nitrate to an alka-
line formate, completely decomposed on boiUug
with water, 2AgGHO=Ag,-i-CO, + H2C02, thus
differing from the acetate.
Sodium formate NaA',; rhombic prisms,
o:6:c = -919:l:-97; P = 58'>9' (Fock, Z. K. 7,61).
M.F. 200°. M. sol. (water), si. sol. (alcohol),
insol. (ether). S.G. 1-919 (Schroder). Heat of
solution— -52. Decomposed when heated into hy-
drogen and the oxalate : 2NaOHOj = Hj -H NajCjO^.
— NaA^.aq, rhombic tables, sol. 2 pts. (water).
The acid salts of sodium and potassium described
by Bineau do not exist.
Strontium formate SrA'j2aq: rhom-
bic crystals, a:&:c = ■608:1: -595 (Heusser), exhl<
biting hemihedral forms (Pasteur, A. Ch. [3] 31,
98 ; Jacobsen, P. 113, 493). S.G. 2-25 (hyd.),
2-667 (anhyd.) (SchrBder). Heat of solution 2-73
(hyd.), -31 (aimyd.), m. soi. (water).
Terbium formate, white powder. M.
sol. water.
Thallium formate TIA',: v. sol. water;
melts below 100° without decomposition (Euhl-
mann, C. B. 65, 607).
Thorium formate ThA'4.4aq: tables,
deliquescent (Chydenius, P. 119, 54).
Ytterbium formate TC2A'34aq: crystal- '
line aggregates (Marignac, A. Oh. [5] 14, 247.
Yttrium formate, very soluble, deliques-
cent. The philippium formate described by De-
lafontaine, A. Ch. [5] 14, 238 is probably a mix-
ture of terbium and yttrium formates, which
separates in rhombic prisms, a:Z):c=: -89:1:1-484
(Boscoe, C. J. 41, 281).
Zinc formate ZnA22aq: monoclinic crys-
tals, isomorphous with Mn salt. S.G. 2-151
(hyd.) (Schrader); ?i? 2-157 (Clarke), 2-306
(anhyd.). Heat of solution -1-2 (hyd.), 1-97
(anhyd.).
AiiETL FOBMATEB. Formtc sthers.
Methyl ether CjHjO, or MeA'. MoL w.
60. S.G.?P -957 (S.); a -978 (E.); Jf -982,
If -969 (Ferkin) ; iS. .979 (GrodzH a. Eramer).
V.D. 2-084 (for 2-08) (Dumas a. Peligot). C.E.
(0°-10°) -00144 (B.). S.V. 62-67 (S.), 62-84 (E.),
63-2 (Bamsay). H.C.v. 241,620 (Thomson),
238,700 (Berthelot). H.P.p. 89,430. H.F.V. 88,270.
M.M. 2-495 at 16° (P.). A' 4-944 (S.).
, Occurrence. — In crude wood spirit (Mabery,
A. C. J. 5, 259).
Pr^a/ration. — 1. By adding calcium formate
(100 pts.) gradually to wood spirit (130 pts.),
saturated with hydrochloric aeid. The distillate
is poured back, redistilled, and finally rectified
over sodium carbonate and calcium chloride
(Volhard, A. 176, 133).— 2. By distilling a mix-
ture in equivalent proportions of sodium formate,
hydrochloric acid, and wood spirit (Bardy a.
Bordet, A. Ch. [6] 16, 561 ; cf. Dumas a. FeU-
got, A. Ch. [2] 68, 48).
ProperUes. — Colourless liquid of ethereal
odour.
Mono-ehloro-methyl formate
HCOjCHgCl. Prepared by passing chlorine in
the dark at 100° into methyl formate. '
Perchloromethyl formate ClCOjOOl, (180°-
185°). S.G.i21-724(Cahours,4.64,315). When
passed through a strongly heated tube it is con-
verted into carbon oxy-chloride. With alcohol
it forms ethyl chl6ro-f ormate, the equation being
Cfilfl, + 2EtOH = 2ClC0sEt + 2HC1.
Ethyl etherO^fit or EtA'. Mol. w. 74.
(63-5°) at 754-5 mm. (R. SohifE) ; (55") (Garten-
meister); (54-4°) (Elsasser). S.G. § -945 (G.)t
I -937 (Elsasser) ; «? -9064 (Briihl) ; if -9298, f|
■9188 (Ferkin) ; ^ -873 (S.) {cf. Naccari a. Pag-
liani, W.BeOil. 687).. V.D. 2-593 (for 2-565) (Lie-
big). O.E. (0°-10°) -001331 (B.). S.V. 84-5T
(S.); 84-6 (G.); 85-14 (B.). |U^ 1-3642. Bjo 28-61
(B.). M.M. 3-664 at 18-8. H.P.p. 95,900. HJ'.v,
94,160. A* 4'528. Critical Temperature 2386°'
(Fawlewski).
Pr^gouraUon.—l. By distilling a mixture of
FORMIC ACID.
667
90 p.o. alcohol (6 pta.), sodium formate (7 pts.),
and concentrated sulphurio acid (10 pta.) (Ijiebig,
/. 17, 72). — 2. By heating a mixture of glycerin,
oxalic acid, and alcohol in a reflux apparatus,
and then distUling (lorin, Bl. [2] 5, 12).— 3.
Starch (9 pts.) mixed with manganese peroxide
(29 pts.), is added to a mixture of sulphuric
acid (20 pts.), water (5 pts.), and 85 p.c. alcohol
(15 pts.), and the whole distilled (Stinde, D. P. J.
181, 402).^. As a secondary product in the
preparation of ethyl oxalate (/. pr. 83, 1), its
formation' being due to the decomposition, of
mono-ethyl oxalate (Anschfitz, B. 16, 2412).
Properties. — Liqtiid, of odour resembling
peach-kernels. S. 11 at 18°, sol. alcohol and
ether. Vapour-tension at various temperatures
(Kaccari a. Pagliani) : —
Temp. Pres. Temp. Pres.
20-2 193-7 50-3 6569
31-2 311-2 55-1 782-2
40-87 459-9 60'5 941-9
Beactions. — Beoomposed by sodium or
sodium-ethylate into carbonic oxide and alcohol
HCOjEt=CO-HEtOH (Geuther, Z. 1868, 665).
With chlorine it yields di-chloro-ethyl
formate HCOaCjHaClj, S.G. ^s 1-261, which is
decomposed when boiled, and by alkalis into
EGl, potassium formate, and acetate (Malaguti,
il. 32, 89); and ^er'c^Zoro ethyl formate
CICO2G2CI5 (c/. TBicHiiOBACBiic Acm) (Bucholz,
Crell. N. Mntdeck. 6, 55 ; Gehlen, S. 4, 18 ;
Dobereiner, A. 3, 145; Kopp, A. 55, 180).
Propyl ether PrA.'. Mol. w. 88. (81°)
at 760 mm. (Gartenmeister, Elsasser, Schumann) ;
(82-5°-83°) at 763-4 mm. (Sohiff). S.G. g -925
(G.) ; 2 -9184 (E.) ; a -9188 (Pierre a. Puchot) ;
M -9099, M -9002 (Perkin) ; ^^ -8075 (S.). C.B.
(0'»-10°) -001212 (B.) ; (0°-20'=) -0246 (Pierre a.
Puchot), S.V. 108-7 (S.) ; 106-2 (G.) ; 106-8 (B.).
HJ-.p. 102480. H.F.T. 100160. M.M. 4-584.
A' 4-486. S. 2-2 at 22° (Traube, B. 17, 2304).
Critical temperature, 267-4 (Pawlewski; Pierre
a. Puchot, A. 153, 262 ; 163, 271).
Isopropyl ether PrA'. (68°-71°). S.G. a
-8826 (Pribram a. Handl, M. 2, 685). Specific
viscosity 31-5 at 10-4°.
n-Butyl ether HOOjO^Hs. (104°-105°)
at 739-4 mm. S.G. s -9058. Specific viscosity
52 at 1-9° (Pribram a. Handl, iMd. 692).
Isohutyl ether. (97-9°) at 760 mm.
(Schumann, ElsSsser) ; (98-5°) at 759-8 mm.
(SchifE). S.G. ? -8854 (E.) ; 2 -8845 (Pierre a.
Puchot); 8|-4 -7784 (S.). S.V. 127-6 (G.); 130-7
(S.) ; 129-9 (E.). S. 1 at 22° (Traube, B. 17,
2304). CM. (0°-10°) -00112 (E.; of. Pierre a.
Puchot, A. 163, 281). H.F.p. 106,700. HJ'.v.
103,800. A" 4-064 (S.) (Wurtz, A. 93, 121).
Iso-amyl ether SCO fi,B.„. Mol. w. 116.
(123-3°) at 760 mm. (Schumann, Sohiff, El-
sasser) ; (130-4°) (Gartenmeister). S.G. 2 -9018
(6.); S -8944 (B.) ; «p -8802 (Bruhl) ; i2|-S -7554
S.). S.V.158-2(S.); 150-21 (B.); 150-5 (G.). C.E.
(0°-10°) -00107 (G.). /.^ 1-4027. B a, 51-06 (B.).
Critical temperatwe 304-6. A? 4-149 (S.). Pre-
pared by distillation of glycerin, oxalic acid, and
fusel oil.
Sexyl ether HCOjCeH,,. (153-6°) (Garten-
meister); (146°) (Erentzel). S-G. g 8977 (G.);
ii -8495 (F.). S.V. 173-3 (G.). O.E. (O'-IO")
■00106 (G.), ^
Heptyl ether SCO jD,U,„. (176-7°) (Garten-
meister). S.G. g -8937 (G.). S.Y. 196-7 (G.).
C.B.(0°-10°) -00097.
Octyl ether HCOjO^U,, lldS-l") (a.). S.G.
g -8929 (G.). S.V. 220-3 (G.). O.B. (0°-10°)
■00096.
A llyl ether HOOjOjHs. M0I.W. 86. (82-83°).
S.G. 'J» -9322 (ToUens, Z. 1866, 518,; 1868, 441).
H.F.p. 65,020. H.P.v. 63,280. Formed as a sub.
sidiary product in the preparation of formic acid
from glycerin and oxalic acid when the mixture
is not too strongly heated.
Phenyl ether HCO^Ph. (180° with de-
composition). Phenol and formic acid (equiv.
pts.) are heated at 80° and POCl, {i equiv.)
slowly added (Seifert, J.pr. [2] 31, 467). ■"
Obthofobuio acid. As stated above, though
orthoformic acid EC(OH), has not been isolated
as such, its ethereal salts are stable compounds,
prepared by heating chloroform with the al-
cohol in presence of an alkali metal or hydrate
CHOls + 3E0Na = 3Na01 + CH(OE), (Williamson
a. Kay, Pr. 7, 135). '
l^ethyl ether HC{0Me)3. (101°-102°)
(Deutsch, B. 12, 117); (102°) (Pinner, B. 16,
1644). S.G. ^ -974 (D.). V.D. 52-59 (obs.).
H.F.p. 130,460. H.F.V. 127,270. Prepared from
methyl alcohol, chloroform, and sodium.
Ethyl e«Ae»-HC(OEt)s.(145°-146°)(Kay);
(146°-148°) (Ladenburg a. Wiohelhaus, A. 152,
164) ; (147°-149°) (Deutsch) ; (145°) (Pinner).
S.G. -894.
Formation. — 1. From chloroform and sodium
ethylate (WiUiamson a. Kay). — 2. By decompos-
ing the hydrochloride of formimido-ether with
alcohol (Pinner).
Preparation.^-1. Sodium ethylate free from
alcohol is mixed with a little ether and chloro-
form added slowly. The mixttire is warmed on
a water-bath, then distilled and rectified over
CaOL, (Stapft, Z. 1871, 186).— 2. Sodium (7 pts.)
is added gradually to a mixture of CHOI, (12 pts.),
absolute alcohol (14 pts.), and a little ether
(Wiohelhaus a. Ladenburg, A. 152, 164 ; Deutsch,
B. 12, 116 ; cf. Bassett, 0. J. 2, 198).
Properties. — ^Liquid of aromatic odour^ liquid
at — 18° ; V. sol. water.
Beactions. — 1. Heated with acetic acid it is
decomposed into formic acid and ethyl acetate
(Sawitsch, J. 1860, 391).— 2. By sodium ethylate
it is converted into CO, alcohol, ether, and formic
acid (Bassett).— 3. With bromine it gives BtBr,
alcohol, ethyl, formate, and ethyl carbonate,
according to the equation: 2HG(OEt)3 -^ Br^
= 2EtBr + HCOjEt + CO(OEt)j + EtOH.
Dimethyl ethyl ether CH(0Me)20Et.
(115°-120°). Prepared by mixing the hydro-
chloride of formimido-ether with methyl alcohol
(Pinner, B. 16, 356).
Tripropyl ether CH(OPr)s. (196°-198°)
(Deutsch); (194°) (Pinner). S.G. ||-879. V.D.
95-64 (D.).
Dipropyl methyl ether HC(OPr)j[OMe.
(181°) (P.).
Dipropyl ethyl ether HC(0Pr)20Et.
(186°) (P.).
Dimethyl propyl ether HC(0Me)20Pr.
(152°) (P.).
Diethyl propyl ether HC(OEt)jOPt
(167°) (P.).
968
FOBMIO AOID.
Dipropyl iioamyl ethtr
HC(0Pr),0C5H„. (226°) (P.).
Propyl di-isohutyl ethtr
H0(aPr),(O0<H,)s. (208°) (P.).
Tri-isobutyl ether HC(OC,H,)j. (220°-
822°). S.G.-ii-861. V.D. 114-86 (Deutsch).
Dihutyl isoamyi ether
HO(OC,H,),(OC,H„). 232°) (P.).
Di-isoamyl ethyl ether
HC(OC,H„),OC.H,. (254°) (P.).
Triallyl ether CH(OC,HJ,. (196"'-205°).
Prepared from sodium (16 g.), allyl alcohol
(3S g.), and chloroform (24 g.), diluted Mrith
double its volume of petroleum (Beilstein a.
Wiegand).
Phenyl ether OH(OPh)j. [72°] (Tiemann,
B. 15, 2G86) ; [76°-77°] (Auwers, B. 18, 2657).
(270° at 56 mm.) (T^. Long needles; insol.
water, sol. ether, chloroform, and benzene.
Formed by the action of chloroform on alka-
line phenol solution. Beadily decomposed by
acids, not by alkalis.
o-Nitro phenyl ether CH(OCjH,NOjj),.
[183°]. From chloroform (2 mols.) and potassium
o-nitro phenol (3 mols.), heated to 150°. Yield
small. Needles (Weddige, J.pr. [2] 26, 445).
p-Nitro phenyl ether. [232°]. Needles.
Prepared as above (Weddige).
Formamide GH,NO i.e. HCOKH,. Amide of
formic add. Mol. w. 48. (192°-195°) with de-
composition into carbonic oxide and ammonia ;
(140° in vacuo) (Hofmann, 0. /. 16, 72); (208°)
(Claisena. Matthews, C. j: 41, 264) ; '(150° m
V9crto) (Schulze, J.pr. [2] 27, 516).
Formation. — 1. By heating ethyl formate
with ammonia (Hofmann). — 2. By heating am-
noninm formate together with urea at 140°
(Berend, A. 128, 385): 2H0OjNH, + CO(NHj)j
= 2HC!0jNHj+(NHJjC0a.— 3. By the action of
sodium-amalgam on a solution of potassium
oyanate (Basarow, B. 4, 409). — 4. By the action
of strong fuming HCSl on HCN (Claisen a. Mat-
thews).
Preparation. — 1. Ammoniumformateis heated
at 230° for five hours under pressure, yield
71p.c. of theoretical (Hofmann, B. 15, 980).— 2.
By heating dry formic acid (55 g.) with am-
monium sulphocyanide (31 g.) for two days,
and then distilling in vacuo. Yield 74 p.c.
ProperUea. — ^Liquid, sol. water, alcohol and
ether.
Reactions. — 1. Decomposed by alkalis in
the cold with evolution of NH,. — 2. SpUt up by
PClj into CO and a little HONJWaUaoh, B. 15,
210).— 3. With PA it yields HON (Hofmann).
4. It absorbs dry HOI in the cold with formation
of a crystalline addition product, which at a
higher temperature is completely resolved into
NHjOl and 00.-5. With bromine in equi-
molecolar proportions in presence of soda it
forms a crystalline bromo- derivative HCONHBr,
decomposed into EBr and HgOgNaO, (Hofmann,
B- 15, 753). — 6. With ethyl aceto-acetate in
presence of zinc chloride it yields di-methyl-
ethyl-pyridine carbozylic ether (Oanzoneri a.
Spica, G. 14, 448).
Methyl-formamide HOONHMe. (190°)
S.G. fl I'Oll. Formed by evaporating an aque-
ous solution of methylamine formate, and distil-
ling the residue. Liquid, sol. water and alcohol,
insol. ether. Decomposed by alkalis and acids
Into formic acid and KMeH, ; by PA into 00,
&0N, and NH^Me; and by ZnOl, into NH„
CO and hydrocarbons (Linnemann, 8iti. W.
[2] 60, 46).
Ethyl-formamide HCONHEt. (196°-
197°). S.O. ^ -952. Formed in the same way
as the above. Liquid, sol. water and alcohol,
insol. ether. Besembles the above in its re-
actions (Linnemann, ibid. 48).
Diethyl-formamide HCONEtj (176°-
178°) (Linnemann, Sitz. W. [2] 60, 61); (178°)
(WaUach a. Kamensky, A. 214, 240). S.G. is
■908 (L.), Prepared by distilling diethyl-amine
formate (L.) (W. a. E.), or diethyl-ozamic acid
(W. a. E.). Liquid, sol. water, but separated by
EHO and E^OO,.
Salt.— (B'HCl)jP101, : yeUow pp.
Beactiom. — 1. With acids, alkalis and ZnOI,
it behaves like the above compounds (Liune-
mann). — 2. PCI, gives HOCl^NEt, which splits
up thus 2HC01^Btj = 3HC1 + OioH^CUiTj. The
product is a base forming a salt (B'HCl)2Pt0l4
and decomposed when heated with formation of
pyrrole (Wallaoh a. Eamensky).
Isopropyl-formamide HCONHPr.
(220°). From isopropyl-carbamine and HCl in
the cold (Gautier, A. 149, 158).
Phenyl-formamide'H.GOTSS.C^y Form-
anilide [46°]. ,
Formation. — By distillation of eqnimole-
cnlar proportions of aniline and ozsJie acid
(Gerhardt, A. 60, 310 ; Hofmann, A. 142, 121),
CjH A + NHjPh = HCONHPh + 00^ + HA
Prepa/ration. — ^By heating aniline and formic
acid (equimols.). The product is heated on a
water-bath nnder reduced pressure to remove
the water, then distilled at ordinary pressure np
to 250°. The contents of the retort are then
poured out (Tobias, B. 15, 2443, 2866 ; WaUach
a. Wiisten, B. 16, 145).
Properiies.—iioiig needles or foor-sided
prisms, m. sol. water, sol. alcohol ; exhibits
phenomenon of superfusiota.
Beactions. — 1. Decomposed by dilute acids
into aniline and formic acid. — 2. Split np by
concentrated HCl into benzonitrile HCONHPh
= FhCN-i-HA — 3. If gaseous HOI is passed in
at 100° the amide is decomposed into formic
acid and diphenyl-formamidine CHNPhNHPh.
4. By cone. H^SO, it is decomposed into CO and
amido-benzene ^-sulphonic acid. — 6. With zinc-
dust it yields CO, GO,, H,, aniline and benzo-
nitrile (Gasiorowski a. Merz, B. 18, 1002). —
6. Heated with phenyl cyanate at 180° it yields
phenyl-carbamine, di-phenyl-urea and CO,
(Euhn, B. 18, 1477).— 7. Converted by alcoholio
solutions of alkyl bromides (1 mol.) followed by
alcoholic EOH (1 mol.) into aJkyl-formanilides
(Fictet a. Cr^pieux, B. 21, 1106).
Sodium formanilide HCONNaPhaq,
Formed by adding cono. soda to formanilide
(Hofmann). Glistening plates; v. si. sol. alcohol;
decomposed by water (Tobias, B. 15, 2443).
Nitroso-formanilide HCON(NO)Ph. [39°].
Formed by passing nitrous acid into a cooled
solution of formanilide in acetic acid. Yellowish -
white needles, v. sol. water; readily decomposed.
Mcthyl-formanilide HCONMePh (P);
(253°) at 716 mm. (P. a. C). S.G. V 1-097.
Formed from the hydrochloride of formimido-
ether and methyl aniline, the reaction being
FORMIC ALDEHYDE.
u IoUowb: NH:CB0Et.H01-(-NHMePbH-H,0
-HCONMePh + EtOH + NH.01 (Pinner, B. 16,
1652; P. 8. C).
Ethyl- formanilidt H.CO.NPhEt. (258°
i.V.) St 728 mm. S.G. ^ 1'063.
Propyl-formanilide H.CO.NPhPr. (267°
i.V.) at 737 mm. S.G. « 1-044.
Isopropyl-formanilide H.CO.NPhPr.
(263° i.V.) at 720 mm.
Isobutyl'formaniUde H.CO.NPh.0.Ha.
(274° i.V.) at 781 mm.
Isoamyl-formanilide H.CO.NPhC.H,,.
(286° i.V.) at 728 mm. S.G. V 1-004.
Phenyl -formanilide HOONPhj. Di-
ph&vyl-formamide. [73°-74°]. (210°-220° m
va6iio). Fonned from diphenylamine and formio
or oxalic acid. When heated with ZnCl, yields
aoridine (Willm a. Girard, B. 8, 1196),
fformo-o-toluide HCONHCsHiMe. [58°]
(Tobias, B. 15, 2446); [56-5°-57-5°] (Ladenburg,
B. 10, 1129). (288°) (L.). Formed from o-
tolnidine and formic acid. Glistening leaflets,
T. sol. alcohol. Decomposed into its constituents
by dilute anlphuric acid. Heated for some time
at its boiling-point it yields o-toluidine, methyl-
ditolylamine, CO, and CO,. Sodium deriva-
tive HCONNaC„H,Me aq.
Formo-p-toluide. [45°] (Hiibner, A. 209,
372) ; [52°] (Tobias, B. 15, 2446). Formed (1)
as the above (T.) ; (2) by heating ^-toluidine
oxalate (H.). Long needles, t. sol. water, and
^cohol. Converted into the nitrile of ^ -toluio
acid when heated with zinc-dust (B. 18, 1002).
Formo-m-xylide. [113°-114°]. Glisten-
ing needles or leaflets, v. sol. alcohol and ether
(Gasiorowski a. Merz, B. 18, 1011).
Wormo-cumidide HCONHCgH^Me,.
[121°]. Needles v. si. sol. water, sol. alcohol
and ether (Senier, C. J. 47, 768).
X'ormo-isobutyl-o-toluide
HCONHOJB[,MeCHj?r [1:2:4]. [105°]. Colour-
less tables, V. si. sol. water, sol. alcohol and
ether (Effront, B. 17, 2847).
Formonaphthalides ». Naphthyii-
AUINES.
Formopiperidide v. Pipemdinb.
V. H. V.
FOBMIC AIiSEHYBE CH^O. OxymetkyUne.
MoL w. 30 (observed by Baoult's method : 34,
ToUens a. Mayer, B. 21, 1566).
Formation,. — 1. By passing a current of air,
charged with vapour of methyl alcohol, over a'
glowing spiral of platinum wire or over platinised
asbestos; if the escaping gases are passed
through a Iiiebig's condenser a solution of formic
aldehyde in methyl alcohol will collect in the
riBceiver (Hofmann, Pr. 16, 156 ; cf. Volhard, A.
176, 128 ; Kablonkoflf, Bl. [2] 38, 379). When
platinum foil at 55° is used the yield is 12 p.o.
(Tollens, L. Y. 29, 355 ; O. J. 46, 293). Bed-
hot oxide of iron or copper may be used instead
of platinum (Loew, J.'pr. [2] 33, 322; Tollens,
B. 19, 2133).— 2. By decomposing chloro-methyl
acetate (2 pts.) with water (1 pt.) by heating for
30 minutes to 100° (Michael, Am. 1, 418).— 3.
Formed in small quantities by the action of ozone
on coal-gas (Macquenne, Bl. [2] 37, 298).--4. In
small quantity, together with formic acid and
0H„ by the action of the silent electric discharge
on a mixture of hydrogen and COj (Brodie, Pr.
S2, 172). — 6. When a mixture of methylal
CH,(OMe), and H^SO, is warmed, formic alde-
hyde is given off, but it quicljily polymerises giving
a sublimate of its solid modification. — 6. By
heating ethylene with oxygen at 400° (Sohiitzen-
berger, Bl. [2] 31, 482).— 7. In the incomplete
combustion of nitric ether (Pratesi, Q. 14, 221).
PropertHsi. — Formic aldehyde is only known
in solution ; by freezing the solution and remov-
ing the ice an aqueous solution may be concen-
trated until it contains 10 p.o. of the aldehyde
(Hofmann, B. 11, 1685 ; cf. Tollens, B. 15, 1629 ;
16, 917). The aqueous solution is pungent ; it
reduces ammoniacal AgNOj, forming, when
gently warmed, a silver mirror. When warmed
with aqueous KOH it gives a brownish oil
and an odour like that accompanying aldehyde-
resin. Dilute aqueous NaOH gives formio acid
and MeOE. After treating the solution with
H^S and heating the resulting liquid with oonc.
HOlAq, it solidifies on cooling to a dazzling
white mass of felted needles consisting of
(CHjS),. When evaporated with ammonia or
ammonium carbonate it leaves a residue of
hexamethyleneamine, by weighing which the
amount of formic aldehyde in the solution may
be determined (Loew, J.^. [2] 33, 322 ; cf. Leg-
ler, B. 16, 1333). A solution of formic aldehyde
deposits after some time iasolnble formic par-
aldehyde or tri-oxy-methylene.
Reactions. — 1. Beadily condensed by strong
bases, to a less extent by salts with alkaline re-
action. Calcined MgO has no action. BaHjO^Aq
gives formic acid and methyl alcohol; the
BaHjO, is, however, soon neutralised and ceases
to act. CaH^OjAq, MgHjOjAq, Pe, Pb, PbO,
many Fb salts, NEt^OH, and many organic
bases give rise to formose or methylenitan
CgHigOj. By boiling a 7 p.e. solution with tin a
body resembling formose, called (J3) -formose, is
formed. MgH^O^q at about 100° gives at least
two sugars, one of which yields an osazone in
yellow needles [152°]. Hone of these sugars fer-
ment with yeast. NaCl has no action alone, but
increases the activity of CaH^O^Aq, whilst Na AcO,
ENO„ and much Cu, Fe, or Sn diminish it (0.
Loew, B. 21, 270; J. pr. [2] 3?, 321; 34, 51;
Wehmer a. Tollens, A. 243, 840).— 2. Beadily
condenses with primary amines : CH^O + H^NB
= Hp + CH2NB. Thus methylamine, aniline,
o-tbluidine, and ^-toluidine give methylene-
methyl-amine (c. 207°), phenyl-methylene-amine
CsH5N:CH2 [138°], o-tolyl-methylene-amine
08H,MeN:CHj, and fi-tolyl-methylene-amine [c.
122°] respectively (KolotofE, Bl. [2] 45, 253;
Tollens, B. 17, 657 ; WeUington a. Tollens,, B.
18, 3309). These formulee ought, perhaps, to be
doubled. Primary and secondary bases also give
compounds of the form CHjINHE), and
CH^INEE'),, thus: aniline and di-ethyl-amine
give di-phe"nyl-methylene-diamine CHj(NHPh),
[49°], and methylene - tetra - ethyl - diamine
CHs(NEtj)j (167°) respectively (Pratesi, 0. 14,
353 ; KolotofE, Bl. [2] 43, 112 ; Ehrenberg, J.pr.
[2] 36, 118). In these condensations with bases
the paraldehyde may be used. — 3. By boiUng
with a solution of ammonium chloride it is con-
verted into NMe, and COj (Ploohl, B. 21, 2117).
4. By heating a 16 p.c. solution of formio alde-
hyde with a/mmomii/m sulphate on the water-bath
CO, IB given off and the sulphates of mono-, di-,
and iri-methylamine are formed. If methyl
570
FORMIC ALDEHTOE.
amine or dimethylamine hydrochloride be sub-
stituted foi the ammonium sulphate trimethyl-
amine is formed in both cases.— 5. Trimethyl-
amine hydrochloride does not act on formio
aldehyde (Ploohl, B. 21, 2117).
PhenylhydratideCS^-S^C^B.^{^)[18^°].
Colourless trimetrio tables. Formed by adding
phenyl-hydrazine to a solution of formic alde-
byde (Wellington a. ToUens, B. 18, 3300).
Formic paraldehyde (CHjO),? 2H-oxy-
methyUne. [152°].
Formation. — 1. By spontaneous polymerisa-
tion of formic aldehyde in aqueous solution. — 2.
From methylene iodide by the action of AgjO or
of silver oxalate. Also from methylene acetate
by heating with water at 100° (Butlerow, A. Ill,
242). — 3. By heating calcium glycoUate (1 pt.)
with HjSO, (7 pts.) at 175° (Heintz, A. 138, 43);
and in small quantity by heating glycoUic acid
at 220° (Heintz, J. 1861, 444).— 4. By the action
of water on chloro- or di-chloro-dimethyl oxide
(MeO.OHjCl or MeO.CHCl^) fPriedel, 0. B. 84,
247 ; Butlerow, Z. 1865, 619).— 5. By electro-
lysis of a solution of glycol, glycerin, mannite,
or glucose in dilute H^SO, (Benard, A. Ch. [5] 17,
303).
PnjperMes.— Crystalline mass. Even below
100° it sublimes, but its melting-point is thereby
raised from 152° to 172° (Tollens, B. 16, 919).
Formio paraldehyde is converted on vaporisation
into CajO(V.D. 1-06). It is insol. water, alcohol,
and ether, but dissolves in cold aqueous NaOH
or baryta. It is also dissolved by heating with
water at 100°, being thereby converted into or-
dinary formio aldehyde (Tollens a. Mayer, B. 21,
1571). Whenhot it has a pungent odour. Heating
with a trace of B^SO, in a sealed tube at 115°
converts it into '(o)-tri-oxy-methylene ' OaHjOj
[61°], V.D.44-9 (H=l) ; (o).tri-oxy-methylene is
sol. water, alcohol, and ether, and reduces am-
moniacal AgNO, in presence of KOH (Pratesi, Q.
14, 140). When a solution of formic aldehyde is
evaporated over HjSO, there is formed a soft
substance, v. sol. water, whose molecular weight,
determined by Baoult's method, corresponds to
the formula (OHjO)j (Tollens a. Mayer, B. 21,
3503).
Beactions. — 1. FI, gives methylene iodide. —
2. BoUing with alcohol and some H2SO4 gives
CH,(OEt)j. — 3. Boiling lime-water gives formose
(methylenitan) (Butlerow, 4. 120, 295). — 4. Heat-
ing with water and MgO at 130°, and afterwards
at 220°, gives formic acid and MteOH.— 5. AgjO
gives a silver mirror and formic acid (Heintz, A.
.138, 822).— 6. Cone. HClAq at 100° gives MeCl
and formic acid (Tischtschenko, J. R. 15, 321). —
7. Dry NH, forms hexamethylene-tetramine
O^HijN^, which crystallises from alcohol in
rhombohedra ; t. sol. water, si. sol. cold alcohol,
almost insol. ether (Butlerow, A. 115, 322). —
8. Ethylamine giYea (CHlj)j(NEt)2; di-ethylamine
forms CH2(NEt2)2 ; tri-ethylamine has no action.
Other bases act in like manner when heated with
formic paraldehyde (Ehrenberg, J. pr. [2] 36,
117). — 9. Chlorine in suidight forms COCl, and
HCl (Tischtschenko, J. B. 1887, 479). Bromine
gives (CH2Br)20, formio acid, HBr, methyl
bromide, CO, and CO,.— 10. ZnEtj, followed by
water, gives propyl alcohol. ZnPrj gives, in like
manner, butyl alcohol (Tischtschenko, Bl. [2]
43, 112).— 11. By heating with dilute BOl it it
resolved into formic acid and MeOH or MeOl (T.).
Dry HOI slowly forms {CRfil),0 (102P-108°).—
12. Dry HI is absorbed with formation of water
and (CH2l)20 (219°) (Tischtschenko, J. S. 1887,
464). — 13. Dry HBr acts in like manner, form-
ing (CHjBr)jO (150°). This body is a pungent
fuming oil, sol. ether, benzene, and acetone.
Water decomposes it into Mefl and HBr. — 14.
Aqueous HBr and formic paraldehyde at 140°
give methyl bromide and formic acid.
Formic orthaldehyde 0H2(0H)2.
Acetyl derivative CH2(OAc)2. Methylene
acetate. (170°). Formed by the action of methyl-
ene iodide on silver acetate (Butlerow, A. 107,
111; 111, 242; Baeyer, B. 5, 1094; 6, 220).
Formed also by treating CH2CI.OAC with KOAo
(Henry, B. 6, 739). Heavy liquid, sol. cold
water, but when heated in a sealed tube for twenty
hours at 100°, with a quantity of water insuffi-
cient to dissolve it in the cold, it is resolved into
acetic acid and formio paraldehyde.
Acetyl derivative of the Methyl ether
CH2(OMe)(OAo). (118°). From CH3.O.CH2CI
and KOAc (Friedel, B. 10, 492). Decomposed
by alkaUs into water, HOAo, and formic paralde-
hyde.
Methyl ether CH2(OMe)2. Methylene di-
methyl di-6xide. Methylal. Mol. w. 76. (42°),
S.a. '£ -8604 (BriJhl, A. 203, 12). Critical tern-
peratwe : 224°. S. 28. H.C.p. 433,900 (Berthelot
a. Ogier, A. Ch. [5] 23, 201). H.F.p. 88,240,
H.F.V. 85,920 (Th.). Formed by distilling a mix.
tnre of water (3 pts.),H2S04 (3 pts.), methyl alco-
hol (2 pts.),andMn02.(2 pts.) (Kane, A. 19, 175;
Malaguti, A. 32, 55). Formed also by electrolysis
of methyl alcohol (100 pts.) acidified with HjSO,
(1 pt.) diluted with water (4 pts.) (Benard, A. Ch.
[5] 17, 291). Methylal is a liquid." A dose ol
5g. to 8g. produces a hypnotic effect (Mairet a.
Combemale, O. B. 104, 1022).
Beactions. — 1. Methylalis employed by Baeyer
{B. 5, 1094 ; 6, 220) as more convenient than
formic aldehyde in obtaining derivatives of
methane by elimination of water between that
aldehyde and aromatic hydrocarbons. Thus, if
a mixture of benzene (120 pts.), methylal (40 pts.),
and acetic acid (400 pts.) be treated with a mix-
ture of equal parts of HOAc and HjSO, tiU the
greater part of the benzene has separated, and
the whole be then left for twenty-four hours, it
will be found, after mixing with cold HjSO,
(2000 pts.), diluting after some hours with water,
and shaking up with ether, that di-phenyl-
methane has been formed: CH2(OMe)„-i-20,H,
= CH2(C8Hs)2 + 2H0Me. Methylal may" serve as
a nourishment for algse ; under these conditions
they develop cellulose, but they only develop
starch in daylight (Loew a. Bokomy, J. or. [2]
36, 272).
Ethy^l ether CH2(0Et)2. (89° cor.) (G.);
(83°) (H.) ; (88°) (P.) S.G. |g -826 (H.) ; 2 -851
(G.) ; 2 -840 (P.). V.D. 3-44 (H.). Prepared by
the action of sodium on a solution of methylene
chloride in absolute alcohol (Greene, A. C. J. 1,
622 ; Bl. [2] 45, 164 ; C. B. 89, 1077). Formed
also by treating CHJt, with NaOEt (Henry, Bl.
[2] 45, 337; C. B. 101, 599) ; and by distilling
formic paraldehyde with alcohol and a little
HjSO, (Pratesi, GF. 13, 313). MobUe liquid, with
FORMIO ALDEHYDE.
671
ftgreeable odonr like mint. SI. sol. water, insol.
oonc. OaCl^q.
Di-propyl ether OB^(0iPT)t. (137°). S.G.
M -835 (Arnhold, A 240, 199).
Di-isopropyl ether CHafOPr),. (118°).
S.G. 3» -831.
Di-isobutyl etfcer OHJOOHja),. (164°).
8.0. 2fi -825.
Di-isoamyl ether CH,(00jH„)r (207°).
S.a. ^ -835.
Di-ootyl ether 0H,(00gH,,)™ (above
360°). S.Gi22.846.
Di-bensyl ether CH2(0CH2Ph)2. (aboye
360°). S.G. 22 1-053.
Di-phenyl ether OHij(OPh)j. (299°).
S.G. 22 1092.
Di-O'tolyl ether Cn2(0.0^B.^Ue)i. [32°].
S.G. ^ 1-019. From methylene chloride and the
sodium derivatiye of o-creaol (Amhold, A. 240,
Di-m-tolyl ether CH2(0CAMe),. [45°).
(aboye 360°). S.G. ^1-052.
Di-p-iolyl ether 0H;j(008H,Me)j. [40°].
(above 360°). S.G. S2 1.034.
Di-thymyl ether CH2(0C„H„)r [36°].
(above 360°). S.G. 52 -979.
Formose CgHi^O, dried at 90°. From formic
aldehyde by adding cold milk of lime to a 4 p.c.
solntion, Storing, and leaving the filtrate to
stand for some days (Loew, J. pr. [2] 33, 328).
Properties. — Syrup, si. sol. alcohol, insol.
ether. Sweet taste. -055 g. reduce 10 o.c. of Feh-
ling'a solution. By heating at 100°-120° for
five days it becomes ' methylenitan ' Cfiifi^,
which has a bitter, taste, and has only one-
fourth its reducing power. Prevents the precipi-
tation of cupric sulphate by potash. Hot cone.
HCl turns it brown, as it does cane-sugar and
levulose, but not glucose ; the filtrate can re-
duce Fehling's solution (Wehmer, B. 20, 2614).
Cold milk of lime slowly destroys it. Warm
alkaline solutions of piorio acid are turned
ted, and indigo is bleached, as by glucose and
levulose. Warmed with cone, alcoholic resorcin
and HOI a ruby-red colour is produced; cane-
sugar, levulose and glucose give paler colours
(Ihl a. Pechmann, C. G. 1885, 761). Aqueous
jyrogallol and HCl act similarly. Cone, alco-
holic diphenylamine and HOI give a brownish-
-violet colour on warming. Schiff's reaction
^ves no colour with formose. Formose can un-
'dergo lactic but not alcoholic fermentation. It
as, however, accompanied by_ a sugar that can
undergo alcoholic fermentation (tioew, B. 22,
470). Alkaline diazobenzene sulphonic acid
•gives a red colour, as with carbohydrates and
aldehydes. Phenyl hydrazine reacts thus:
<3.H,A + 2N,H,Ph = C„H,^A + 3H,0. The
product crystallises from dilute alcohol m slender
needles. Plants which readily produce starch
from glucose, cane-sugar, mannite, and glycerin
do not produce it from forinose (W.). When a
solution of formose (10 g.) in water (1 litre) is
boiled for a long time, the product extracted with
-«hloroform, and the residue after evaporation of
the chloroform treated with alcohol, aniline, and
-a little HCl, an intense red colour characteristic
■t)f furf urol is produced. This reaction is charac-
teristic of sugars. In fact, when formose is di-
Egested with 1 p.c. sulphuric acid at 100°, more
turfurol is formed than from other sugars (Loew,
£.20, 3039). Loew maintains that formose ia-
well characterised as a sugar. £. Fischer (B.
21,. 991) points out that the product of the action
of lime-water on formic aldehyde is a mixture of
three or more aldehydio or ketonic alcohols, one
of them being the artificial sugar from aorol^ui,
aorose, characterised by its phenyl-hydrazide
[217°] (Fischer a. Passmore, B. 22, 359).
Methylenitan 0„H,„05 (?). Obtained by the
action of lime water on formic aldehyde or paral-
dehyde (Butlerow, A. 120, 296; O. B. 53, 145 ;
Loew, J. pr. [2] 33, 321 ; 37, 203 ; Wehmer a.
Tollens, A. 243, 340). The product is saturated
with CO2, filtered, and evaporated. Formed also
by the action of heat upon formose. Amorphous
gummy_ mass. Has a bitter taste. Does not
react with phenyl-hydrazine. Sol. alcohol. When
boiled with Fehling's solution it reduces only
one-fourth as much CuO as glucose does. After
boiling with dilute acids the reducing power is the
same. It is optically inactive. It does not un-
dergo alcoholic fermentation. When boiled for
a long time with dilute H^SO^ it gives formic
and acetic, but no levulic acids. It has no action
on cold CaCO,, but dissolves it and gives off
CO2 on heating. According to Loew ( /. pr. [2]
33, 342), methylenitan CgH,gO, is the saccharin
of formose, and may be got by heating formose
with lime or baryta and water at70°-100°.
FBeudoformose. Got by boiling formic alde-
hyde in -7 p.c. solution with tin (Loew, J.pr. [2]
34, 51). Besembles formose in most respects.
Differs from formose (1) in giving orange, nOt
violet, colouration, with resorcin, HCl, and alco-
hol; (2) 10 C.C. Pehling reduce •052g.; (3) in
forming the phenyl-hydrazine composed more
quickly. Phenyl-hydrazine forms an osazone
[123°]; when this body is heated for 30 hours in
alcoholic solution at 100° its melting-point is
found to have risen to 148°.
(^)-Formose. Formed when a '1 p.o. soln-
tion of formic aldehyde is boiled for 6 hours
with much tin (Loew, B. 21, 270). Thick,
sweet, non-fermentable syrup ; does not become
brown at 100°. It yields humous substances
with HCl. Turned brown by potash. Its solu-
tion in alcoholic HOI yields a wine-red colour
with resorcin and a steel-blue colour with di-
phenylamine. 10 c.c. of Fehling's solution are
reduced by -0739 of (fl)-formose. Its phenyl-
hydrazide or • osazone ' CigH^^NjO, crystallises
in small yellow needles [148°].
Two other formoses or non-fermentable
sugars are said by Loew to be formed by heat-
ing formic aldehyde, 3 pts., at 100° with an
aqueous solution (1000 pts.) of magnesia ob-
tained by treating a 7 p.o. solution of MgSO,
with litharge. One of these gives with phenyl
hydrazine an osazone crystallising from benzene
in yellow needles [152°].
laomeride of Formose (?). In the electro-
lysis of glycerin (30 vols.) acidified with H^SO,
(2 vols.), diluted with water (20 vols.), there
is formed, together with formic paraldehyde, a
syrupy isomeride of formic aldehyde. It blackens
at 90°, giving an odour of burnt sugar. It is v.
e. sol. alcohol and water, is unfermentable, re-
duces Fehling's solution and ammoniacal AgNO,.
Its solution is ppd. by ammoniacal lead acetate
but not by lead snbacetate. HKO, oxidises it to
oxalic acid. Baryta added to its alcoholic sola*
678
FORMIO ALDEHYDE.
tion pptB. {C,'S,fi,),3BeX). This body is perhaps
identical with foimoae or methylenitan.
JOBM-IUIB-AUIDE v. Fobmamidinb.
Form-ethyl-imid-etliyl-amide v. <-i>i-Eibtii-
fOBMAUIBINX.
F0B1I-IMII).SI.ETHTI.-A1[II)E «. u-Di-
BIHTL FOBUAUIDINE.
FOBM-IMIDO-ETHEB 0,H,NO i.e.
NH:CH.OEt. (80°) ? Hydrochloride B'HCl.
Formed by the action of gaseous HCl (2 mols.)
on dry HOy (1 mol.) mixed \nth alcohol (1 mol.)
in a freezing mixture (Pinner, B. 16, 354, 1644).
Guttering prisms. Yery unstable, decomposing
on keeping with formation of NH^Cl. With
alcohol it gives NH,C1 and orthotormic ether.
Beacticms. — 1. Decomposed by heat into
EtCl, formic ether, and the hydrochloride of
formamidine. — 2. KOH separates a small quan-
tity of an oil (80°).— 3. Alcoholic NH, in the
cold gives formamidine. — 4. Bimethylamine
forms NHiCH.NMcj. — 5. Methyl-aniline forms
C,H5NMe(CH0).— 6. Phenyl-hydrazine forms
C,jH„N,. — 7. An alcoholic solution of NEt^H
slowly forms a base CioH^jN, which forms
a platinoohloride B'jHjPtCl, [153°] orystallia-
ing in flat prisms fPinner, B. 16, 1650; 17,
180).— 8. NaOAo and AojO give NH:0H.OAc
[70°] which crystallises from ether in short
prisms, v. sol. ordinary menstrua.
Formimido-methylene ether (NH:0H0)2CH2.
Hydrochloride B"2HC1. Formed by passing
HOI into glycol (1 mol.) and HCy (2 mols.) diluted
with ether at 0° (Pinner).
FOBMINS. Pormyl derivatives of poly-
faydric alcohols. They are described under the
alcohols from which they are derived.
FOBU-UETHYL-imD-UETHYL^IIIDE v.
di-Methyl-fobmamidine.
FOBUO-CTTMIDIDE v. CnMmiNE. Formyl
derivatives of bases are described for the most
part both under Fobmio acid and under the
FOEMOSUANAMINE C,HsN,. [above 350°].
Formed together with COj, ammonia, 00, and
water by heating guanidine formate at 200°
(Kencki, B. 7, 1584). Trimetrio needles, with
feeble alkaline reaction. V. sol. hot water, si.
sol. alcohol. May be sublimed with partial
carbonisation. — B'HCl: trimetrio plates. —
B'jH^PtClj.— BENOj : needles or prisms.—
B'H2C20t : granular-crystalline pp., insol. cold,
bI. sol. hot, water.
FOBUO-ITAFHTHALIDE v. Formyl derwa-
ti/Oe of NAFHTHYIiAMimS.
FOBMOSE V. FoBMIO AliDSHTCE.
FOBMO-TOLVIDE v. Formyl derwative of
ToiiumiNE.
FOBU-FHENYL-IUIS-FHENYL-AIIIDE v.
DI-PHENVIi-FOBMAMIDINE.
FOBUULA. Symbols have been in use in
chemistry from the earliest period of the science,
but as knowledge has grown their meaning has
become deeper and deeper ; and the difference
between the significance of the earliest symbols
and of the elaborate chemical formules of the
present is as great as the difCersnce between the
knowledge of chemical phenomena possessed by
the earUest chemists, and that possessed by the
chemists of to-day. The first attempt of any
importance to represent more than the name of
a substance was that of H^ssengiatz and Adel
in 1787. These ohenusts represented all metals
by circles, in which were written the first letters
of the Latin names thus : Copper ®, lead ?'.
All alkalis and alkaline earths were represented
by triangles placed in different positions ; oxy-
gen by a horizontal line, &o., &o. The compo-
sition of compound substances was represented
by placing side by side the symbols of the ele-
mentary substances contained in them. This sys-
tem was recommended by Lavoisier, BerthoUet,
and Fonrcroy in a report made by them to tho
French Academy in 1787, but it was not generally
accepted. The next suggestion of importance was
made by Dalton in 1808. He represented the
atoms of the elements by circles, and distin-
'guished them by various additions. Thus, hy-
drogen was represented by 0, oxygen by 0> ni-
trogen by d', sulphur by S, &c. The composi-
tion of compounds was represented by placing
side by side the symbols of the elements of which
the compounds were made up. Thus, water was
represented by the symbol ©O, ammonia by
QjQ, nitrous oxide by 0O(E/' *"• The present
system of symbols was introduced by BerzeUiis,
They are based upon the atomic theory, each
symbol of an element being intended to represent
an atom of an element. As is well known, the
symbol of an element is the first letter, or the
&cat letter and some other letter, of the name of
the element. In many cases the symbol is de-
rived from the Latin name of the element.
The composition of compounds was repre-
sented by writing side by side the symbols of the
elements which were in combination. The sym-
bol of a compound was thus an expression of the
view held regarding the structure of the com-
pound. As H represents an atom of hydrogen
and 0 an atom of oxygen, the symbol HO for
water meant that what was then called an atom
of water was made up of an atom of hydrogen
and an atom of oxygen. So far as it represented
that water is made up of hydrogen and oxygen
in the proportion by weight of 1 pt. of the for-
mer to 8 pts. of the latter, it represented a fact
in regard to which there could be no dispute.
But when it was interpreted as meaning that an
atom of hydrogen is in combination with an atom
of oxygen, a definite theory in regard to the stmo-
ture of matter was involved. The difficulties
in the way of determining atomic weights have
been referred to in previous articles (i;. Atomic
AND M011EOOI.AB WEIGHTS, vol. i.). Until the in-
troduction of the method of Avogadro, and that
of Dulong and Petit, for the determination of
atomic weights, there was much difference of
opinion in regard to the figures to be adopted,
and, therefore, the symbols did not always re-
present the same thing. At the present time
most chemists are agreed as to the system of
atomic weights, and the symbols of the elements
now in use are intended to represent atomic
weights as determined mainly by the methods
of Avogadro, and Dulong and Petit. These
atomic weights are strongly confirmed by the
discovery of the periodic law, which would be
meaningless with any other system than that
now generally adopted. There are some chemists
in France who refuse to accept the atomic
weights, and the symbols used by them do not
mean the same thing as those used by othei
ohemista.
FORMULA.
678
The ohemical (oinlula ot a compound is in-
tended primarily to represent the quantitative
cumpoaitioh of the compound. In terms ot the
aouepted theory of the struoture of matter, it is
intended to tell what atoms, and how many, are
comtjined to make the smallest particle of the
compound which exhibits the properties of that
compound. This smallest particle of the com-
pound is called a molecule. The formula then
is intended to represent a molecule. In the case
of gaseous compounds, or of compounds which
can be converted into gases without undergoing
decomposition, we have, of course, the means of
determining the relative weights of the molecules
on the basis of Avogadro's law. The methods,
then, which are involved in the determination of
molecular formulea are these : (1) the substance
must be analysed; (2) the molecular weight
must be determined. The formula must express
the results of both determinations. To show
how this is done one example wiU suffice. Let
it be desired to determine the molecular formula
of water. The analysis shows that it consists of
hydrogen and oxygen in the proportion of 1 pt.
by weight of the former to 8 pts. by weight of
the latter. This is a fact involving no specula-
tion whatever, and any formula adopted must be
in accordance with this fact. The next step is to
determine the specific gravity of water vapour.
As compared with air its specific gravity is
0-623. This gives the relative weight of the
molecule of water, and, adopting the usual stan-
dard, it shows the molecular weight of water to
be 18. The atomic weight of oxygen has been
shown to be 16, if that of hydrogen is 1, so that
we now have all the data for writing the mole-
cular formula. A molecule which consists of
hydrogen and oxygen in the proportions men-
tioned above, and the weight of which is 18 in
terms of an accepted unit weight, must con-
tain 2 atoms of hydrogen and 1 atom of oxygen.
This is expressed by the formula HjO. A mole-
cule thus made up weighs 18 times as much as
an atom of hydrogen, or the molecular weight of
the compound is 18, the 18 pts. being made up
of 16 pts. of oxygen and 2 pts. of hydrogen.
Thus tiie formula expresses the results of the
analysis and of the determination of the specific
gravity of water vapour, and these results are
interpreted in terms of the molecular and atomic
theory and the law of Avogadro. This is true of
every formula of a gaseous substance.
As regards the molecular formulffl of liquid
and solid substances we know but little. Many
facts indicate that the molecules of liquids and
solids are much more complex than those of gases,
bntno altogether satisfactory method hasyetbeen
discovered for determining the molecular weights
of BUOh substances. Among the facts which lead
to the conclusion that the molecules of liquids
and solids are complex may be mentioned, the
not uncommon observation that just above the
boiling-point vapours have a greater specific
gravity than at a higher temperature. It is not
probable that the molecules of liquid and solid
sulphur contain less than six atoms. The exist-
ence of allotropio modifications of the solid ele-
ments sulphur and phosphorus is probably best
explained by assuming that the molecules of the
ftllotropicmodificationscontaindiSerentnumberB
«f atoms.
An attempt has been made to establish •
method for the determination of the molecular
weights of solids by means of observations upon
the freezing-points of solutions. Many obser-
vations have shown that there is a definite con-
nexion bet\veen the mdectUar weights of solids
and the freezing-points of their solutions, and
the law expressing this connexion has been
stated provisionally by Baonlt, who finds that
quantities of chemically similar compounds pro-
portional to the molecular weights of these com-
pounds generally produce equal lowerings of the
freezing-points of water and other solvents.
There seem, however, to be exceptions to this law.
The formulsa ot liquids and solids are not
molecular formulce in the sense in which the
formula ot a gas of which the specific gravity is
known is. Even the formula of water H^O is
strictly applicable only to water in the state ot
vapour. Whether on condensing to the form of
the liquid several of the simple molecules unite
to form more complex molecules, we cannot posi-
tively say, but probably they do. So also, when
the Hquid water becomes solid ice, it is not im-
probable that a still further union of molecules
takes place.
If we consider the case of a solid compound
which cannot be converted into vapour, our
formula plainly cannot express the molecular
weight at all. In writitig the formula of sodium
chloride NaCl, we do so because that is the
simplest formula which vrill express the fact
that the compound consists ot 23 pts. of sodium
and 35*5 pts. ot chlorine. But the formulas
Na^Clj, NagCl,, KajClj, &o., express the results
of analyses just as well, and at the same time
are probably nearer the truth than the simpler
one. The time may come when it will be neces-
sary to express the molecular weights ot solids
and liquids, as well as ot gases, in chemical for-
mula. At present, so far as the tacts which we
generally have to express in our formolffi are
concerned, it is not a matter of any special im-
portance whether we know the true molecular
weights or not. Indeed, it is not improbable
that, even though the molecules of solids and
liquids are comparatively complex, they are re-
duced to the simple forms under the conditions
under which ohemical action takes place. Thus,
when a solid or a liquid is dissolved, probably
the complex molecules of which it is composed
are broken down and become simple in the
dilute solutions. This would be in accordance
with the fact that solutions act readily upon one
another; and it is in accordance with recent
work on the electrolytic conduction ot salts in
solntipn {v. Fhtsicai, methods).
£Vom what has been said it is clear that we
have to distinguish between molecular formulcB
and. eomposiUon-fommlcB, the former being ap-
plicable only in cases of gases, the latter being
used in cases in which molecular formulse.cannot
be written owing to a lack of knowledge of the
facts. In both these kinds ot tormulo the
atomic theory is involved.
But chemisljB have come to express much
more by their formulas than the composition
and the molecular weights of compounds. They
express views in regard to the arrangement or
relations of the parts which are in combination.
Neitiier the atomio theory nor the hypothesis el
674
FORMULAE.
A.vogadro has any direct connexion with the
arrangement of the parts constituting a molecule.
All that the former claims is that, when chemical
action takes place, it takes place between certain
minute particles called atoms ; that when an act
oi chemical combination occurs two or more
atoms combine. The hypothesis of Ayogadro goes
one step further. According to it the particles
formed by the combination of atoms,i.e.the mole-
cules, bear such relations to one another that they
always require the same space for the same num-
ber, no matter what their composition may be.
As a result of the study of the chemical
changes of compounds, however, chemists have
come to hold certain views in regard to the
relations of the parts, or atoms, which enter
into the composition of molecules. Formulas
which express these views are called in general
rational formulcB, or amstituiumal or stmotural
fommleB. Bational formulce have been in use
in chemistry for a long time. Lavoisier's studies
on oxygen and the phenomena of combustion led
him to ascribe to that element a degree of supreme
importance. According to him the oxygen was
the chief constituent of every eompoand. It was
oxygen which made acids what they are, and
oxygen which made bases what they are. When
a salt is formed the acid and base unite, and the
salt consists of the two parts in combination.
Thus potassium nitrate is KO.NO5, sodium sul-
phate NaO.SOj, &o. These f ormulss not only ex-
press the composition of the compounds which
they represent, they express the view that the
salts consist of two parts, each of which contains
oxygen. The same view was extended to other
compounds, and the attempt was made to ex-
press the constitution of every compound in a
similar way. The constitutional formula thus
introduced were based upon the hypothesis of
dtuiUsm. They were oaJled diiaUstio formulce.
The dualistio view found support in a study of
the action of the electric current on chemical
compounds. As compounds are decomposed by
the electric current into two parts, one going to
the positive, the other to the negative, pole, the
view that every compound consists of two parts
was thus plainly strengthened. The introduc-
tion of the electro-chemical theory by Berzelius
led to the general use of dualistio formulss.
These formulas were intended to represent the
electro-negative and the electro-positive con-
stituent of each compound. For a long time
these formulis were used exclusively, and in'
some books even at the present day they are
found, though many facts have been discovered
which show that the electro-chemical theory is
untenable— at least, in the form in which it was
put forward by Berzelius {v, Duawsm).
Owing to the complexity of the compounds
of carbon, and the fact that they readily undergo
changes, the chief studies which have led to the
views at present held have been made with regard
to 111 cse compounds. At one time what was caJled
the theory of radicles played an important part,
and at this time every formula expressed the
views of chemists regarding the particular radicle
or radicles contained in a compound. These radi-
cles were groups of atoms wMch could be trans-
lened from one compound to another without
undergoing change of composition. According
(o the Uteory of conjugate eomgowndt (Theorie
der gepaa/rten. Verbinchmgen), every complex
compound is made up of some simple compound
conjugated with a complex group. Thus aniline
was regarded as made up of ammonia conjugated
with a group OgH,, as represented in the formula
C,H,.NH,. The sulphonic acids were in the same
way regarded as made up of sulphuric acid con-
jugated with various groups of carbon and hydro-
gen. Next came the theory of types, which
regards all compounds as built according to a
few plans. The general plans of all compounds
were found in simple compounds like hydro-
chloric acid, water, ammonia, and marsh gas.
In saying that alcohol, for example, belongs to
the water type it was meant that it may be
regarded as derived from water by the substitu-
tion of the group C^^ for a part of the hydrogen
in water. The relation between the two was
represented by the formulte ■g\0 and ^} 0.
So, too, aniline was regarded as belonging to the
ammonia type, and the relation between them
was represented by the formnlu HtN and
h)
H f N. It will be seen that this method of olas-
h)
sification or of expressing constitution involves
the conception of substitution and, to some extent,
the conception of radicles i.e. at complex groups
playing the part of single atoms. The object of
a typical formula was to show to which of the
types a compound was related, and in what way
it was regarded as derived from the type. It was
found necessary to refer many compounds to
more than one type, and this led to what was
called the theory of mixed types. The compound
methylamine may serve to illustrate this. It
may be regarded as derived from ammonia, in
which case it must be represented by the formula
OH,,
H [ N, or it may with equal right be regarded
h)
as derived from marsh gas, and it must then be
represented by the formula -arO. Both these
hJ
views may, however, be harmonised, and the
compound represented as belonging to both
n(h
types thas ^
H °-
m
It is thus seen that ohemists for more than
a century have attempted by means of formula
to express their views in regard to the constitu-
tion of chemical compounds in terms of prevail*
ing hypotheses. But the formnles thus framed
were in most cases more than mere expressions
of theory. They attempted to express certain
facts that were known. In the dualistio formula
the fact was expressed that compounds are
formed by the union of two parts. lii the
electro-ohemical formula the fact was expressed
that compounds break down into two parts
under the influence of an electric current. In
the formola representing conjugate compounda>
FORMULiB.
675
the fact that some of the oompoands thus repre-
sented have properties highly suggestive of the
fundamental substance supposed to be contained
in them was recognised; and in the typical
formula the fact that the general conduct of the
compound represented is like that of the type to
which it is regarded as belonging is intended to
be expressed. When alcohol is represented as
belonging to the water type, for example, the
chemical conduct of the two substances is the
justification for the view expressed. All the
constitutional formula, then, are intended to
express facts established by study of the com-
pounds. Everything learned in regard to a
compound must be in accordance with the
formula, and must, if possible, find an interpre-
tation in the formula. It would be absurd, for
example, to represent a marked acid as belong-
ing to the ammonia type, unless it could be
shown that, together with its acid properties,
the compound also has certain properties which
suggest those of ammonia.
Let ns now consider the constitutional for-
mvitB used by most chemists of the present day.
These, like ^preceding constitutional formula,
are intended to express the facts in terms of the
prevailing hypotheses. The type theory gave
way to the valency hypothesis which was first
suggested by Franldandanda^terwards elaborated
by KeknlS, Gouper, Kolbe and others. According
to this the cause of the types is to be looked for
in the atoms of which the typical compounds
are made up. Atoms differ from one another in
the number of other atoms which they can hold
in combination at the same time. The so-called
types are simply representative compounds, il-
lustrating the forms of compounds possible in
the case of monovalent, divalent, trivalent, and
tetravalent, elements. Just as the atom of hy-
drogen is iii combination with chlorine in hydro-
chloric acid, so each atom of hydrogen is in com-
bination with oxygen in water, with nitrogen in
ammonia, and with carbon in marsh gas. This
view involves the conception of the linkage of
atoms. Instead of conceiving each molecule of
water, of ammonia, and of marsh gas, as made
up of a certain number of atoms all in direct
combination, we now conceive that in these mole-
cules there are direct connexions between some
of the atoms and not between others. While in
the molecules named the hydrogen is in direct
combination with oxygen, with nitrogen, and
with carbon, it is not believed to be in direct
combination with hydrogen. These views are ex-
piMsed by the following formula: —
H— O— H or
H
}»
or H.O.H
yH. fH .H
K^HorN<HorN-H
\h iH -H
C<gorO
Jh„ H.p.H
Each of the formula for water expresses exactly
the same view, and so do the different formula
for ammonia and for marsh gas. The facts
which lead to the acceptance of the valency
hypothesis have been considered pretty fully in
the article EguivAj>Bsoy (g. v.) and they need not
may wnie meinyi aiconoi : —
{OH jC
H \e
be repeated here. Suflice it to say that tha
evidence in favour of the view that there are
definite lines of connexion between the different
parts of molecules is extremely strong, and that
without this view it appears to be impossible to
explain the many cases of isomerism which
present themselves in the field of organic
chemistry. In our constitutional formu^ at
present we endeavour to state what lines of con-
nexion exist in the molecules. These formula
are based upon the molecular and atomic theory,
the hypothesis of the linkage of atoms, and to
some extent upon the valency hypothesis.
The difference between a typical formula
and a ImJeage-formula is very slight in simple
compounds, and when the linkage-formula ia
written without the use of lines or points to indi-
cate the connexions between the atoms, it is iden-
tical in appearanqe with the typical formula.
It is nevertheless intended to express something
which the typical formula did not express. We
may write methyl alcohol :
OH ^0— H
H
■H
H
Each formula is intended to express exactly the
same thing, and that is, that of the four hydrogen
atoms contained in the molecule of methyl
alcohol, three are in direct combination with
carbon alone, and one with oxygen ; while the
oxygen is in direct combination with carbon as
well as with hydrogen. The formula also ex-
press the relation between water and methyl alco-
hol, but that fact is not regarded as the principal
one, as it was when the theory of types was the
controlling idea. While it is not difficult to see
how by means of such formula it is possible to
express the constitution of compounds, it ia not
so easy to see how, when more than one formula
is possible for the same compound, the selection
is made. It is thought by some that, in order to
express the constitution of a compound, it is
only necessary to know the valencies of the atoms
which form the molecule of the compound, and to
arrange these atoms in such a way as to satisfy all
the hypothetical affinities or bonds. Thus the con-
stitution of sulphuric acid is written S^iI^J;~S
by some, because anlphnr and oxygen are divalent
and hydrogen is monovalent. In this case to be
sure there are two other ways in which the con-
stitutional formula may be written on the above
assumptions. They are H— 0— S— O— O— 0— H
and H— S— O— O— O— O— H. Such formula,
however, are conventional methods of expressing
certain matters which call for evidence. They are
aimply the results of the application of the hypo-
thesis of valency and express something in regard
to which we know nothing until the subject has
been investigated. Who, for example, can tell
without investigation whether in sulphuric acid
both hydrogen atoms are in combination with
oxygen, or whether one ia in combination with
oxygen and the other with sulphur ? One view ia
just as probable a priori aa the other, and there
is nothing in the hypothesis which will enable
ns to decide between them. And so in most
other cases. The hypothesis of the linkage of
atoms affords ns a ready method of expressing
facts which ar^ known to us, but it does not fiu*
576
FORMCLiE.
nisli us with the faots. What kinds of facts then
can be expressed by means of the hypothesis,
and how can we become tioqnainted with these
facts ?
Answers to these questions will best be given
by means of examples. There are two com-
pounds known which by the usual methods can
easily be shown to have the molecular formula
C2H,N. Without further information, any attempt
to express views in regard to the structure of
these substances would be mere speculation.
By studying the chemical conduct <fi both we
soon recognise marked differences between them.
One of them shows a tendency to decompose in
such a way that the nitrogen is given off in the
form of ammonia, while the two carbon atoms
remain. Thus, under proper conditions this de-
composition takes place :
OjHaN + 2H2O = CjH^Oj + NH,.
The other compound breaks down in an entirely
diSerent way, the nitrogen remaining in combina-
tion with one of the carbon atoms, and the other
carbon atom being given ofi thus :
O^N + 2H:jO = CH5N -t- HjCOj.
These facts suggest that the carbon and nitrogen
in these two compounds are held together in
different ways. In the first it appears probable
that the connexion is as represented in the for-
mula C — 0 — N ; while in the second it appears
that the connexion is this, C — N — C. As regards
the way in which the hydrogen atoms are held
in combination, it can be shown that the com-
pounds formed by decomposition of the two bodies
under consideration contain the methyl group
CH„ which, from its formation from marsh gas,
is easily shown to have the constitution repre-
H
Bented by the formula H — G — ^H ; or, to be
more strictly accurate, the formation from marsh
gas shows that if marsh gas has the formula
H H
H— C— H, methyl is H— C— H. As the va-
lency of the carbon atom is never greater than
foar, BO far as is known, it appears that the
first of the two compounds has the constitution
H,C — 0 — N, and the other the constitution
BCjC — N — C. These formulss are in accordance
with the decompositions above mentioned, and
they suggest the conduct of the substances.
Again, the methods of formation of the sub-
stances confirm the conclusions already drawn
in regard to their constitution. Both are formed
when a salt of hydrocyanic acid is treated with
a mono-halogen derivative of marsh gas such as
methyl iodide CH,I. According to the prevailing
notions, for which there is abundant evidence,
methyl iodide is marsh gas in which one atom of
hydrogen has been replaced by one atom of iodine.
Its constitution is therefore represented thus :
-O-L
When this is treated with silver
cyanide the silver and iodine unite and the
residue of marsh gas, i.e. methyl, OH,, unites
with the cyanogen. Thus a compound is formed
which is represented by the formula H,C(CN),
And, just as the silver salt is called stiver
cyanide, so this compound would naturally be
called methyl cyanide. But, as already stated,
there are two compounds formed. One is called
methyl cyanide, and the other: methyl isocyamde.
While the method of formation plainly indicates
the presence of methjd in both compounds, it
does not give any clue to the way in which the
carbon and nitrogen of the cyanogen are united
with the methyl. According to all we know con-
cerning carbon and nitrogen, either may act as
a linking element, so that the two possibilities
suggest themselves which are represented by
these formulas, H,C— 0— N and H3C— N— 0.
We do not know whether silver cyanide has the
structure Ag — 0 — N or Ag — ^N — C ; as both the
methyl compounds mentioned are formed by
treating silver cyanide with methyl iodide, it
seems not improbable that the salt contains
both varieties. However this may be, it is clear
that the method of formation of the methyl com-
pounds does not afford us any clue to the
structure of the cyanogen group. Our informa-
tion in regard to this is obtained solely by a
study of the decompositions of the compounds.
For the two f ormulie under discussion we have
experimental evidence, and the formulte express
the results of experiments. These results are
interpreted in terms of the linkage-hypothesis.
So far these formulss are practically independent
of the hypothesis of valency. The conception
that the molecule of marsh gas consists of one
carbon atom in oombination with four hydrogen
atoms is a necessary consequence of the view
that the molecule is symmetrical, and this view
is entirely in accordance with all facts known
regarding the compound. This conception is not
perhaps so much a result of the application of
the hypothesis of valency, as of our knowledge
of the conduct of marsh gas. On now examining
the formulss for methyl cyanide and methyl iso-
cyanide in the light of the hypothesis of vsJency,
we see that in that of methyl cyanide, HgO — 0 — N,
one carbon atom is represented as tetravalent,
the other as divalent, and the nitrogen as mono-
valent. In the formula of the isocyanide,
H3C — N — G, one carbon atom appears to be tetra-
valent, onemonovalent,and the nitrogen divalent.
But, as in most compounds carbon is tetravalent
and nitrogen either trivalentorpentavalent,it is
generally held that in these compounds they also
act in this way, and the formula are written so as
to indicate this. Methyl cyanide is represented
thus H,0 — CSN, and the isocyanide thui
HjO — NsG, the nitrogen being trivalent in the
former and pentavalent in the latter. It will
be seen that the chief reason for writing the
formulte in this way is to account for the dis-
tribution of the hypothetical bonds or af&nities.
No experimental evidence has been furnished
in favour of these formuls, and, so far as our
knowledge of facts is concerned, the simpler
formulis represent just as much as the more
complex ones.
The two examples discussed will give a fail
idea of the methods in use for determining the
structure or constitution of compounds and of
expressing the results by means of formula.
The results reached by a study of the reactions
of a compound are expressed by means of •
FORMTJhM.
677
reaeUon-formula. Those reached by a study of
the method of synthesis of a compound aie ex-
pressed by means of a synthesis-formula. As it
is found that in most cases the reaction-formula
is identical with the synthesis-formula, the ex-
pression is called a si/ructural or ccmsUtutional,
formula. The structure or constitution may be
expressed by means of a simple Unkage-foirmula
in which the connexions between the atoms as
' determined by experiments are pointed out ; or
a valency-formula in which an attempt is made
to express different kinds of connexions between
atoms. The linkage-formnla is based upon ex-
periments; the valency-formula, so far as it
expresses more than the linkage-formula, is
almost wholly an expression of an hypothesis.
The constitutional formuln of all the great
groups of chemical compounds have been deter-
mined by experiments, and they are of great
value in enabling chemists to express very con-
cisely in intelligible language the results of ex-
periments. As it is found that a certain kind of
constitution carries with it a certain set of pro-
perties, the formula conveys to the mind at once
a clear impression in regard to the general pro-
perties of the compound represented. It has
been shown by experiment that in every alcohol
hydrogen is linked to oxygen, and the group
thus formed, which is called hydroxyl, is in turn
linked to a hydrocarbon residue: Methyl alco-
hol, for example, is represented thus H,0 — O — ^H.
Now, whenever we see an expression of this kind
R — 0 — H, in whichB is any hydrocarbon residue,
we may expect that the substance thus repre-
sented has certain general properties which are
characteristic of all alcohols. The analogy be-
tween these sabstances and water and the me-
tallic bases is also clearly indicated by their
formnlsB. Thus we have tiiis series : —
H— O— S water,
K— O— H potassium hydroxide,
Na — O — H sodium hydroxide,
M — O — ^H any hydroxide of a monovalent
metal,
H,C— O — H methyl alcohol,
HjCj— O— H ethyl alcohol,
B — 0 — H any alcohol containing a mono-
valent residue of a hydrocarbon.
A very interesting piece of evidence in favour of
the linking represented in these formulsB is fur-
nished by the action of a reagent which has the
power of removing oxygen and putting chlorine
in its place. Such a reagent is pentachloridp
of phosphorus, PCI5. When it is brought in
contact with a substance containing oxygen this
element is abstracted and two chlorine atoms
from the pentaohloride take the place of each
atom of oxygen. If the oxygen serves the pur-
pose of a linking element, as it does in the com-
pounds above represented, the compound breaks
down in such a way that the parts linked to-
gether by the oxygen appear in separate mole-
cules. Thus, replacing the oxygen in the above
compounds by chlorine, we should have this
senes: —
Vol. n.
H-01
K— 01
Na— 01
M— 01
H,C— CI
HA-01
B— 01
01— H
01— H
01— H
01- H
01— H
01- H
01- H
In each case decomposition takes place, and two
molecules are formed from one. The general re-
action in the case of metallic hydroxides is:
M— O— H -1- POI5 = POOI3 -H MOl + HOI ; and in
the case of alcohols it is :
B— 0—H + POI5 = pool, + ECl -H HOI.
It is evident that oxygen has some power which
chlorine does not possess. It can link together
hydrogen and another element, while in the
cases mentioned chlorine cannot. In a similar
way an elaborate study of acids has shown
that in most of them the hydrogen which is
replaceable by metallic elements is in combina-
tion in the form of hydroxyl, but the hydroxyl
instead of being in direct combination with
a metal, as in the hydroxides above referred
to, is generally in combination with soma
element which is in turn in combination with
oxygen. The constitution of nitric acid, for
example, has been found to be probably re-
presented thus O2N — 0 — ^H; sulphuric acid
r\ TT
thus 02S<^Q S ; permanganic acid thus
OaMn— O— H; chromic acid thus 02Cr<^Q-g-»
&c., &o. So too the carbonates are found to
be derived from an acid which probably has
the structure represented by the formula
OO^qS. On studying the acids of carbon, or
the so-called organic acids, most of them are
found to contain hydroxyl in combination with
carbonyl, forming together the group known as 1
carboxyl which has the structure 00 — O — H.
The greater number of the monobasic carbon
acids may be represented thus 00<^qq or
B.CO.OH. These formulea show the relations'
which exist between the acids in question and
carbonic acid. If in the latter we suppose a
hydroxyl group replaced by a residue like
methyl, ethyl, &o., the result is a carbon acid or
an organic acid. Acetic acid is, OO^qW* ; pro-
pionic acid is 00<'fv^ ' ; or these formulas
may also be written 0H,.00.0H and OjHj.OO.OH
respectively. These are linkage-formulse based
upon experiments. If we write them thus
O O
II II
HjC- 0— 0— H and HjOj— 0— O— H, we then
have to deal with valency-formulte, and they, as
already remarked, convey no more information
than the linkage-formulae, unless by further ex-
periments we become acquainted with facts
which justify us in expressing the relation be-
tween the hydroxylio oxygen and carbon in a dif-
ferent way from thai: in which we express the
relation between the carbonyhc oxygen and car-
bon. In this case we are certainly justified in
making the distinction. It is found that when
the oxygen of the hydroxyl is replaced by
chlorine, one chlorine atom takes the place of
the hydrogen and oxygen of the hydroxyl, and
the other passes oS in combination with hydro-
gen as hydrochloric acid. It appears therefore
that but one chlorine atom can enter in the
place formerly occupied by the hydroxylio oxy-
gen. This is represented by the single line
0 — O — H. On the other hand, under a change
PP
678
FORMULA.
of conditions, it is found possible to replace the
carbonylic oxygen by chloxine, and in this case
two chlorine atoms enter into the molecule in
place of the oxygen. This we may represent by
two lines thus, C^O. In this case then the for-
O
mula — 0 — 0 — H is more than a mere applica-
tion of the valency-hypothesis, it is the expres-
sion in a particular language of a number of
facts, among which are some which justify the
use of the double line, if that is used simply as
an expression, of the facts.
It is not the purpose of this article to show
how the structural formulsa of all the different
classes of compounds are deduced from experi-
mentally determined facts, but rather to illustrate
the general principles which are made use of, and
to show in what way the formulse express the
facts. The question of single and double union
has just been touched upon in connexion with the
relations existing between carbon and oxygen.
The same question has frequently been discussed
with special reference to the relations between
carbon atoms. A concrete case is that of ethylene.
As is well known, this hydrocarbon has the mole-
cular formula C^H,. It is obtained from ethane
OjHj by the indirect abstraction of two atoms of
hydrogen, or from alcohol CjHj — 0 — H by the
abstraction of the elements of water. In ethane it
is assumed that the linkages occur as represented
H H
by the formula H — C — C— H : and in alcohol as
H H
lepresented by the formula, H — C — C — 0 — H.
Now when hydrogen is abstracted from ethane,
or water from alcohol, the action may plainly
take place in two ways so as to form a com-
H
pound of tho Btmcture, H— C — C — ^H, or one of
H H
A
the Btmcture
Lt.
Bat when ethylene is
H H
treated with chlorine a compound of the formula
CjH^GL; is formed, and it has been shown that
in this compound each chlorine is in combina-
tion with a different atom, as represented in the
H H
formula d — fr— C — 01. It appears from this
that ethylene is, in aU probability, made np as
H H
represented in the formula G — C. So far this
formula expresses all that we have learned, and
it appears that, in ethylene, carbon is trivalent.
But ethylene has a power which ethane has not.
It can take up two atoms of hydrogen, of chlor-
ine, bromine, &o. It is unsaturated. We may
H H
represent this fact by the formula
XL.
H H
which, if interpreted in terms of the hypothesis
of valency, means that two of the affinities of
each carbon atom are employed in holding hy-
drogen in combination, one of each in holding
the two carbon atoms together, and one of each
is unemployed. There are several objections to
this view. In the first place it implies that a
part of an atom can be acting while another part
is doing nothing, a state of things which it is
impossible to conceive. In the next place if a
compound with free affinities can exist, why
should we not be able to isolate the hydrocarbon
CE, ? This compound cannot be isolated. It ia
necessary to have a molecule containing at least
two carbon atoms before it is possible to get a
compound of theVthylene series. This makes
it appear probable that the kind of unsatnration
found in ethylene is dependent upon some change
in the relations of the carbon atoms. The differ-
ence between the relation in ethane and in ethyl-
ene may be represented by the signs 0 — C and
C— C. The second, or ethylene sign, suggests at
once the sign used to express the oarbonyl rela-
tion between carbon and oxygen. On com-
paring the reactions of ethylene compounds with
those of oarbonyl compounds, we find indeed
that they have certain features in common.
This is seen in their conduct under the influence
of nascent hydrogen. Ethylene is converted by
this reagent into the saturated compound ethane,
the action being represented in this way :
H H H H
II II
0=0 + 2H = H— 0— 0— H. So too acetone,
u u
which may be taken as a convenient example of
carbonyl compounds, takes up two iitoms of
hydrogen and is converted into <|he saturated
compound, isopropyl alcohol, as represented in
H 0 H
the equation H— 6— 0— 0— H+
2H -
H E H
-LU-
kU
H. While then it ia impoa.
sible at present to say what relation the con-
dition which we call single union bears to that
which we call double union, still we carmot avoid
recognising that there are at least two kinds of
relations between atoms, and these two kinds
may be conveniently expressed by the signs
under discussion.
A similar study of acetylene, O^H,, and cer-
tain cyanogen derivatives, shows that, if we
FORMULAE.
579
recognise the cUstinction between single and
double union, we must also recognise a third
kind of relation, which by analogy we should
call triple union. This condition is most dis-
tinctly represented in acetylene. It carries with
it, the power to take up four monovalent atoms,
just as the double union condition carries with
it the power to take up two monovalent atoms.
Acetylene becomes ethane under the influence of
nascent hydrogen as expressed thus : CjHj + 4H
= O^Bi,. The same power is seen in the cyanides.
Thus, methyl cyanide, which, assuming the con-
dition of triple union between the carbon and
nitrogen in the cyanogen group, is expressed
thus, CH, — C^N, takes up four atoms of hydro-
gen, and is opnverted into ethylamine; thus
CH,— CSN+4H = CH,— CHj— NHjj; a trans-
formation which is plainly of the same kind as
that which takes place when acetylene is trans-
formed into ethane. It should be distinctly
stated that the signs used to express double
union and triple union are not intended to con-
vey the idea that the condition of single union,
whatever that may be, is repeated twice or three
times. They simply express relations different
from that of single union, relations which we
recognise by means of definite reactions. The
double line certainly does not mean that the
union expressed by it is twice as strong as that
expressed by the single line. Indeed it is clear,
from a study of compounds in which the ethyl-
ene condition exists, that the double union is
less firm than the single, and the study of com-
pounds of the acetylene order shows equally
plainly that triple union is the least firm of the
three.
If we should examine all the linkage f ormulss
of complex compounds which have been deter-
mined experimentally, we should find that, in
general, &e linking takes place in accordance
with the laws of valency, fa. many oases, how-
ever, the linkages are less in number than we
should be led to expect from our knowledge of
the valencies of the elementary atoms. In th^se
oases, it is generally found that the compounds
have the power of forming additive compounds
in which each element acts with its maximum
valency.
The methods for determining constitutional
formulae thus far considered are purely chemical.
They are based upon a careful study of the de-
compositions, syntheses, and transformations,
of the compounds. The question will suggest
itself, whether it is possible by a study of
physical properties to throw any light upon
structure. Several attempts have been made in
the direction indicated. The methods will not
be considered here at all in detail, as they will
form the subject of other articles. The proper-
ties which have been most elaborately studied
are; specific volume, molecular refraction,
polarisation-phenomena, magnetic rotation, and
thermal phenomena.
The specific volume, or molecular volume, of
a substance is represented by a figurfe obtained
by dividing the molecular weight of the substance
by its specific gravity in the liquid form. It has
been shown that the specific volume of an element
in combination can sometimes be determined by
studying annmber of its compounds, the general
principle made use of being this : the specific
volume of a certain compound is determined and
then that of another compound differing from
the first by 1 or 2 atoms of the element ; the
difference between the two specific volumes is
regarded as the specific volume of 1 or 2 atoms
of the element by which the two compounds differ.
It appears from investigations thus far carried
out that the specific volume of oxygen has two
values according as it is in the hydroxylic or the
carbonylio condition. Assuming this to be estab-
lished, it is clear that, by determining the spe-
cific gravity of a compound in liquid form, and
without studying its chemical reactions, we might
be able to decide whether an oxygen atom con-
tained in it is in one or the other of the two
conditions mentioned.'
As regards molecular refraction, it has been
shown that, in general, compounds of the same
composition have the same refraction-equivalent.
The refraction equivalent is represented by the
expression pr^liV in ^hich P is the mole-
cular weight of the substance, n the index of refrac-
tion, and <2 the relative density of the substance. A
more elaborate study of this subject has shown
that the molecular refraction of a substance is in-
fluenced by the presence of the condition of double
or triple union. The occurrence in a compound of
one double linkage causes a definite increase in
the molecular refraction. So, also, the presence
of carbonyl, CO, causes an increase in the mole-
cular refraction above that found when the oxy-
gen is present in the singly linked condition, as
in hydioxyl C — 0 — H. B these rules can be
proved to be well founded we have a method
which will enable us to determine whether double
linkage between carbon atoms, or between car-
bon and oxygen, exists in compounds under ex-
amination. The method does not, however, help
US at present to understand what double link-
age is. It merely puts us in a position to say
that, if this condition is assumed in certain
compounds, it must be assumed in certain other
compounds which conduct themselves in the
same way.'
Becently some facts have been observed in
studying the magnetic rotary power of substances
which may be utilised in determining constitu-
tion. It has been shown that the addition of
CH, to a compound increases the molecular
magnetic rotation by a definite quantity. So
also a definite effect was shown to be produced
by the introduction of methyl. Other results of
the same general character were obtained. It is
not improbable that a further study of the mag-
netic rotary power of chemical compounds may
put us in possession of a method of consider-
able value. Up to the present the method as
thus far developed has not come into general
use. The method based upon a study of the
magnetic rotary power, like those based upon a
study of specific volumes and molecular refrac-
tion, does not give any information in regard to
the various conditions which it is its object to
detect. It merely attempts to tell us in which
compounds certain conditions exist, without
saying anything in regard to the naturerof these
> The connexionB between BpeciflcTolameandoonstitn-
tion, andbetweenrefraotlouandponstitatloii, are, hove rer,
not yet anythuig like clearly elaborated (e. Physical
MSTBODS).— IL II. F. M.
vr 2
680
FORMULA.
conditions. It is, however, quite within the
range of probability that continued study of all
the physical properties of compounds may lead
to a satisfactory hypothesis in regard to the
nature of those conditions of which we now
simply recognise the existence. Thus, if it is
found that, whenever double Jinkage occurs in
a compound, certain physical properties always
appear, it may be possible to frame a satisfac-
tory hypothesis in regard to the nature of the
condition which we call double linkage. If then
we could express this hypothesis in our formula,
these would be, more strictly than those now in
use, constitutional formMlcB.
The chemical methods and the physical
methods thus far discussed have nothing di-
rectly to do with the relations which atoms bear
to one another in space. The formulas deter-
mined by means of them do not attempt to
express space-relations, unless the fact that
two atoms are represented as being in direct com-
bination with each other implies that they are
nearer each other than two atoms in the same,
molecule which are not in direct combination with
each other. The formulss simply represent con-
nexions believed to exist between the different
parts of molecules. We know nothing in regard
to the forms of molecules, and the arrangement
of atoms in space. Nevertheless, some ingenious
speculations have been indulged in with refer-
ence to these space-relations. One which has
received much attention, and which is certainly
worthy of serious study, was suggested by obser-
vations of the effects produced by certain sub-
stances on polarised light. There are three
varieties of tartaric acid ; one of these turns the
plane of polarisation of a ray of light to the
right, a second turns it to the left, while the
third is optically inactive. The third is formed
by the union of the first and second, and is,
therefore, probably to be regarded as differing
from the active varieties in having a greater
molecular weight.
The difference between the first and second
tartaric acids cannot be expressed by means
of our ordinary Unkage-formulse. Both are
represented probably by the same formula,
CH(OH).0O.OH
I , which is in accordance with
CH(OH).CO.OH
the chemical reactions, decompositions, and
syntheses, of both. Nevertheless the two com-
pounds differ. Several other cases of the same
kind are known. This kind of isomerism,
which shows. itself in differences in the physi-
cal properties, and not in the chemical conduct,
is called physical isomerism. To account for
the particular kind of physical isomerism
here referred to, Le Bel and Yan't Eoff have
made the suggestion that it may be due to
a different arrangement in space of certain
parts of the molecules. If the four afSnities
of a carbon atom be supposed to be exerted
in the direction of the angles of a tetrahedron,
the carbon atom being at the centre of the
tetrahedron, there are two ways in which four
different atoms or groups can be conceived
to be combined with the carbon. Arranging
these atoms or atomic groups in any way, the
other possible arrangement is found by regarding
the refleotion of the first arrangement in aminor.
These two kipds of arrangement in space are
possible only in those compounds in Which a
carbon atom is in combination with four differ-
ent atoms or atomic groups. Such a carbon
atom is called an asymmetnc carbon atom. Now,
it is a remarkable fact that optically active com-
pounds always contain one or more asymmetrical
carbon atoms, Some attempts have been made
to express by means of formulsa the space-
relations suggested in the above hypothesis
(v. especially Wislicenus, K. Sitchsischen Oes.
der Wissenschaften, 14, 1).
It has been pointed out by Briihl that the
boiling-points, densities, and indices of refraction,
of isomeric compounds vary in the same way;
that for isomeric compounds the constants of that
one are largest which consists of an uninterrupted
chain of hydrocarbon residues, and that the con-
stants become smaller the more the structure of
the molecule is branched, and deviates from
one direction. The data thus far in our posses-
sion seem also to show that the shorter the mole-
cule of isomeric compounds, i.e. the more they
approach the spherical form, the larger is the mo-
lecular volume. The words ' shorter,' 'branched,'
&o., used in these statements, have primarily,
of course, reference to the appearance of the for-
mulae in common use, and which, as already
explained, are not intended to represent the
arrangement of atoms in' space. But, assuming
that they do in a rough way represent the shapes
of the molecules, it appears that there probably
exists a direct connexion between the variations
in the physical constants of isomeric compounds
and the shapes of their molecules. Thus, the
specific gravity of compounds with long mole-
cules would necessarily be greater than that of
compounds with branched or spherical molecules,
for the same reason that we can get more rods
in a given space than spheres of the same weight.
So also with "reference to the boihng-points. The
rod-shaped molecules offer the most points of
contact, the spherical the fewest. The cohesion
between molecules of the first kind will hence be
the greatest, and the conversion of a substance
made up of such molecules into vapour will re-
quire more heat, or the boihng-point will be
higher, than in the case of a substance made up
of molecules of the branched or spherical kind.
It will thus be seen that we have faint sugges-
tions that our linkage-fbrmula have some re-
lation to the arrangement of atoms in space,
though primarily they are not intended to ex-
press facts of this order. I. B.
rOEMTL. >The radicle CHO, the lower
homologue of acetyl. The term was at one
time applied to the radicle CH now called
methenyl. . The formyl derivatives of amines
are described under the amines from which they
are derived.
rOEMYL-CAMPHOR C„H,sO t.e.
/CH.OOH
Ci^u\ I Camphor aldehyde. [76»-78^.
\co
Formed on treating camphor with formic ethor:
/CH,
C,H„<^| +COH.OEt
-0,H,..
/
.CH.COH
Nio
+EtOH.
FRAXIN.
681
Separated by solution in alkalis, shaking with
ether, acidifying with aoetio aoid, shaking again
with ether and evaporating (Bidiop a. Glaisen,
B. 22,533). Crystalline. Its properties are like
those of the ketonio aldehydes R.OO.OHE'.COH.
It is a moderately strong aoid, y. sol. oaustio
alkalis. Fed, giVes a dark violet solution.
Salt. — ^A'jOu: bright green orystaiUine pp. ;
si. sol. water ; v. sol. organic solvents.
Anilide C,.H,50X!H:N.Ph : [153°] ; colour-
less, crystallising well.
FOBMYL-TBICARBOXYLIC ACID v. Me-
THANE-TRICAKBOXTLIO ACID.
FOBUYL CTANTTBAUIDE. Described
under CrAmo acid as a derivative of oyanur-
amide.
FOBSCYL-IIELAUIHE. Described, as a deri-
vative of oyanuramide, under CyANio acid.
FOBUTL-FHENTL-ACEIIG ACID
HCO.CHPh.COjH. Ethyl ether^A.'. (145°)
at 16 mm. Formed by suspending dry NaOSt
in ether (3 pts.), adding a mixture of formic
ether and phenyl-acetic ether, and keeping the
whole for several days in a closed vessel. The
product is shaken with water at 0°, acidified,
and extracted with ether (Wislicenus, B. 20,
2930). OU. Decomposed by boiling with
aqueous NaOE into formic and phenyl-acetic
acids. The alcohoUo solution gives a bluish-
violet colouration with PeClj. Phenyl-hydra-
zine forms CO<p^-^>CH [196°]. Formyl-
phenyl-acetic ether changes spontaneously, es-
pecially at 70°, into a crystalline isomeride [70°];
this isomeride is also split up by alkalis into
formic and phenyl-acetic acids.
BI-FOBUYL-FHENTLENE-DIAMINE v.
FBENTIiEIIE-DIAMIin!.
EOBMYL-FBOPIOITIO ACID
HCO.CHMe.COaH. (161°). Formed by the
action of NaOEt on a mixture of formic and
propionic ethers (Wislicenus, B. 20, 2930). Oil.
Gives an intense reddish-violet colour with
FeCl,.
FOBKYL-TTBEA v. Ubea.
FOBMYL-XYLIDIHE v. Xymdinb.
EBAGABIANIIT. Said to occur in the root of
the strawberry {Fragarid vesca) (Phipson, O. N.
38, 135). v. si. sol. water, alcohol, and ether ;
potash-fusion forms from itprotocatechuic acid.
BoUing aqueous HCl splits it up into glucose
and an amorphous red substance, fragarin.
FBANCEINS. A group of colouring matters
obtained by the action of cone. H^SO, upon the
haloid derivatives of benzene. From the penta-
chloro-benzene CjHCls, the franoeine has the
empirical formula OisHClsO, (Istrati, C. B. 106,
277 ; Bl. [2] 48, 35). All the franceins are sol. cone.
HjSOj, some are sol. water. Many of them dis-
solve in alkalis forming very soluble neutral
salts. They all dissolve in alcohol forming
highly-coloured diohroio solutions. They dye
cotton, linen, and especially silk with shades
varying from rose-colour to maroon. The depth
of colour and the tinctorial power increases with
the proportion of chlorine. Two franceins
C,gHO] A are obtained by boiling pentachloro-
benzene (300 g.) with Nordhausenaoid (2000 c.o.)
for 8 hours a day during 15 days ; HCl and SO,
are given off. At the end of 15 days the acid is
decanted, a fresh quantity added, and the heat-
ing continued for another fortnight. During
this process the franceins gradually separate as
a maroon-coloured substance. After washing
with water, the francein formed in greater quan-
tity is dissolved out in aqueous KOH, reppd. by
HCl, and, when dried at 60'', exhibits a metallic
green lustre. It dissolves in alcohol and in gly-
cerine but not in water. Its alcoholic solution
is red by transmitted, but yellowish-green by
reflected, light, and dyes silk a rose-colour. The
E salt is deep-brown with metallic lustre, and
is V. sol. water forming a deep-red non-dichroio
solution which gives pps. with salts of Ba, Fe,
Sn, Hg, Al, Mg, Cd, Ni, &c. The second fran-
cein, formed at the same time in much smaller
quantity from penta-chloro-benzene, is sol. warm
water but almost insol. EOHAq and is less
sol. alcohol than its isomeride. It dyes silk a
peach colour. "When tetra-chloro-benzene (200
c.c.) is boiled with cone. H^S04 (1,200 o.c.)
for 105 hours it is completely dissolved with
evolution of water, HOI, and SOj. No sulphonio
acid is formed, but on treatment with water a
reddish-brown solid is got. This solid dissolves
easily in EOHAq and in alcohol ; its alcoholic
solution is pale brown by transmitted, and dull
green, by reflected, light. According to Oeorgesco
a. Mincou {Bl. [2] 50, 623), this francein ifi
CigE^CljOg, and forms an insoluble silver salt
CieAg^ClaO,.
EBANGTrLIN Cj,,Ha,0,? (Sohwabe, Ar. Ph.
[3] 26, 560). [230°]. A yellow crystallisable
colouring matter contained in the bark of the
berry-bearing alder (Bhamnus Frangula). It is
accompanied by an amorphous yellow resin, and
occurs most abundantly in the older branches,
the younger branches containing more of the
resin (Casselmann, A. 104, 77).
Preparation. — The bark is digested for three
days with alcohol (90 p.c.) at 25° to 30° ; the
resulting tincture is concentrated by evaporation
and freed from tannin &o. by ppn. with lead
acetate ; lead subacetate is added to the filtrate,
and the pp. is suspended in alcohol and decom-
posed by B.JS. The boiling liquid is filtered,
and on cooling deposits crystals of frangulin
(Faust, A. 165, 229 ; Z. [2] 5, 17 ; Liebermann
a. Waldstein, B. 9, 1775).
Properties. — ^Lemon-yellow crystalline mass
with dull silky lustre. Insol.* water ; soluble in
160 pts. of warm dilute (80 p.c.) alcohol, nearly
insol. cold alcohol, si. scu. ether, sol. hot fixed
oils, benzene, and oil of turpentine. May be
partially sublimed as minute golden needles (C).
In aqueous alkalis it forms a deep cherry-red
solution from which it is reppd. by acids but
not by metallic salts. Cono. H2SO4 forms a
dark-re^ solution which becomes brown on heat-
ing ; it is reppd. by water. Boiling cone. HNO,
dissolves it without decomposition (C). Fuming
HNO, forms oxalic acid and so-called ' nitro-
franguUc acid' CjaHnNjOi, ? (Hesse, A. 117,
349) which crystallises in orange-red needles
(from alcohol). Frangulin is split up by boiling
dilute HCl into glucose and emodin, a tri-oxy-
methyl-anthraquinone (Sohwabe).
FBAXIX C,eH,sO,o^aq. Pamm. A sub-
stance occurring in the bark of the common ash
[Fraxinus excelsior), and also, together with
tesculin, in the bark of the horse-chestnut
(^seniles Hippocastanmm) , and in various species
582
FRAXBS.
of Pavia fSalm-Horstmar, P. 97, 327, 637 ; 100,
607; Eoclileder, P. 107, 331; J. pr. 90, 488;
Stokes, (7. J". 9, 17; Keller, Bep. Pharm. 44,
438 ; Eoohleder a. Schwarz, A. 87, 186 ; Sten-
house, P. ar.-[4] 7, 501).
Prepa/ration. — 1. A decoction of ash-bark
(taken at the flowering-time) is ppd. by lead
acetate ; the filtrate is ppd. by lead, subacetate,
and the pp. suspended in water and decomposed
by HjS (Salm-Horstmar). — 2. The aqueous de-
coction of horse-chestnut bark is mixed when
eold with such a quantity of FeClj that on add-
ing ammonia the pp. immediately separates ;
one-fourth of the ammoniacal filtrate is ppd. by
lead acetate, the pp. is redissolved in EOAc, the
rest of the filtrate is then acidified by acetic
acid', the two portions mixed together, and, after
again adding ammonia, the resulting pp. dis-
solved in acetic acid, freed from lead by E^S, and
left to crystallise.
Properties. — Tufts of colourless needles; it
has a slightly bitter taste. SI. sol. cold, t.
sol. hot, water; si. sol. cold, m. sol. hot alco-
hol ; insol. ether (Salm-Horstmar). Stokes
(O. J. 12, 17) found it more soluble in ether than
EBsculin. It gives off its water of crystallisation
at 110° to 150°, and melts at a higher tempera-
ture (320° according to Salm-Horstmar). The
concentrated aqueous solution is yellow, and has
an acid reaction ; when largely diluted it ex-
hibits strong bluish-green fluorescence ; this
fluorescence is increased by the presence of a
trace of alkali, but is destroyed by acids. The
alcoholic solution is likewise fluorescent. FeCl,
colours the aqueous solution green, and then
yields a lemon-yellow pp. Lead acetate also
gives a yellow pp. in its ammoniacal solution.
Boiling dilate HjSO^ splits fraxin up into glucose
and fraxetin.
Frazetin C,Jl.fis- S. (cold) -1 ; (hot) -33.
Formed as above, and also by the action of HCl
on a lemon-yellow crystalline compound G^^S^O^^,
also occurring in horse-chestnut bark (Eochleder,
C. C. 1864, 41$). Needles (from the dilute HjSO,
in which it is formed), or tables (from alcohol).
Has a slightly astringent taste, v. si. sol. water,
si. sol. alcohol and ether. Melts at the melting-
point of tin, without turning brown. Cone.
HjSO, forms a bright-yellow solution, whence
after dilution and 'addition of NH, it separates
in crystals. HClAq dissolves it. Cone. HNOa
is coloured by it dark- violet, changing to red and
yellow. The aqueous solution is coloured yellow
by NHj. FeCl, colours its aqueous solution
greenish-blue. Acid ammoniiJm sulphite dis-
solves fraxetin, and on adding NH, the liquid
becomes yellow, but does not turn red or blue
on shaking with air (difference from sesculetin).
ruCTTS AIDEHYDE C^HA. Fiicusol. {$)•
Pyrormcic aldehyde. (172°). S.G. iS-5 1-150.
S. 7 at 18°- A volatile oil, isomeric or possibly
identical with furfurol, obtained by distilling
sea-weeds (.FMOtts nodosus, W. vesiculosus, F.
serratv^, &d.) with dilute sulphuric acid (Sten-
house, P. M. [3] 18, 122; 87, 226; A. 35, 301;
74, 278). It is washed free from accompanying
acetone, distilled with steam, and dried oyer
CaClj. Colourless oil; turns brown on keep-
ing exposed to air. HjSO, colours it yellowish-
brown; HClAq turns it green ; when impure the
eolour in both cases is purple-red. KOHAq
colours it-yellow, the colour afterwards changing
to dark-red. Fucusol turns the skin deep-yellow,
the spots being turned rose-red by aniline (as
with furfurol). When boiled with water and
moist AggO the silver salt of (;3)-pyromucic acid is
formed CgHgAgO, ; (/3)-pyromucio acid prepared
from this salt crystallises \a small rhomboidal
plates [130°], whereas ordinary pyromucio acid
forms flat needles [133°] (Stenhouse, Pr. 20, 80).
Ammonium sulphide converts fucusol into thio-
fucusol CjHfSO, which resembles its isomeride
thiofurfurol. Moss (Sphagnum) and various
species of lichen (Cetraria islandica, XJsnea, and
Bamdlma) when distilled with dilute H2SO4
yield an oil apparently identical with fucusol.
rucusamide C,sH,jNjO,. S. -04 at 8°. This
isomeride of f urfuramide is obtained by the ac-
tion of ammonia on fucusol. It crystallises from
hot alcohol in groups of long needles! Its re-
actions are similar to those of furf uramide.
Fttcusine CisHuNjOj. When fucusamide is
boiled for twenty minutes with moderately con-
centrated aqueous EOH it melts, and is con- '
verted into an oil which solidifies on cooling to
a yellowish resin. From this resin HNO3 ex-
tracts the base, and, on coolings the nitrate
crystallises out. If a slight excess of NH, be
added to an aqueous solution of the nitrate
fucusine slowly separates in stellate groups of
small laminse.
Salts. — B'HNO, : stellate groups of long
prisms (from water), or large trimetric prisma
(from alcohol). Decomposes at 100°. —
B'jHjPtClj : four-sided prisms (the correspond-
ing salt of furf urine forms needles). — B'HjCjO,;
small silky needles ; m. sol. cold water.
rTTLMINATES. Described under Ctanio
AOID.
FULMINVSIC ACID. Described under
Cyanic aois.
YWULKRIlTSIC ACID v. Amide of Fduabio
ACID.
FTTMABAITCLIC ACID v. AniKde of FnuABia
ACID.
FUMARIC ACID C,H,0, i.e.
C02H.CH:CH.C0jH. Alh-maleic acid. Mol. w.
116. S. -67 at 16-5° (Carius, A. 142, 153) ; (cold
70 p.c. alcohol) -48. H.C. 318,176 (Louguinine,
C. B. 106, 1290). Heat of solution -5901 (Gal
a. Werner, Bl. [2] 47, 159). Seat of neutraUsa-
tion (by NaOH) 26599 (G. a. W.).
Occurrence.— In various plants and fungi:
fumitory {Fumaria officinalis), CorydaUs bul-
bosa, Glauciwm fla/imm, Iceland moss (Lichen
islandieus), Boletus pseudo-igna/rvus, and Aga-
ricus piperatMs (Winkler, Bep. Piumn. 39, 48,
868 ; 48, 39, 363 ; A. 4, 230 ; Wicke, 4. 87, 225 ;
Probst, A. 31, 248; PfafE, Schw. J. 47, 476;
Dessaignes, J. Ph. [3] 32, 48 ; A. 89, 120 ; BoUey,
X. 86, 44; Schodler, i. 17, 148; Trommsdorff,
N. Tr. 25, 2, 153).
Formation. — 1. Together with male'io acid by
the dehydration of malic acid by heat (Lassaigne
[1819], A. Ch. [2] 11, 93 ; Pelouze, A: Ch. [2]
56, 429 ; A. 11, 265).— 2. From malsio acid by
heating with aqueous HI, HBr, or HCl (Des-
saignes, /. 1856, 468; Kekul6, A. 130, 21;
Suppl. 2, 85).— 3. By treating calcium malats
with POij, and decomposing the resulting chloride
with water (Perkin a. Dnppa A, 112, 24).—
4. By fusing sulpho-suooinic acid with potash
FUMARIO ACID.
58a
(Messel, A. 157, 20).— 5. By heating bromo-suo-
oinio acid.— 6. By the action of aqueous KI and
copper upon di-bromo-sucoinic acid and its iso-
meride (Swarts, Z. 1868, 259). Also from di-
bromo-BUccinio acid and thio-urea (Nencki a.
Sieber, J. pr, [2] 25, 72).— 7. Prom di-bromo-
Euocinio ether by treatment with finely divided
eilver and saponification of the product (Goro-
detzky a. Hell, B. 21, 1802).— 8. By heating
succinimide with bromine at 130° in sealed
tubes (Kisielinski, Site. W. 74, 561).— 9. By
boiling silver malonate with di-chloro-acetio acid
and a little water (Komnenos, A. 218, 169). —
10. By treating asparagin or aspartic acid with
Mel and KOH (K6mer a. Menozzi, 0. 13, 352).—
11. from (S)-bromo-pyromucio acid, bromine, and
water (Hill a. Sanger, A. 232, 53 ; c/. Limpricht,
A. 165, 289).— 12. By treating ;8-di-ohloro-pro-
pionio ether with ECy, and decomposing the
product by KOH (Werigo a. Tanatar, A. 174,
368). — 13. By boiling chloro-ethane-tricarbozylio
ether (prepared by the action of CI on ethane
tricarboxylic ether (C0jH)CH2.CH:(C0^)j with
HCl (Bisohoff, B. 13, 2162J 14. According
to Muhlhauser {A. IQJ., 171) fumaric acid is
among the products of the action of aqua regia
on proteid compounds. — 15. By heating ethylene
tetra-carbozylio acid (Conrad a. Gothzeit, B. IS,
PreparaHon. — Malic acid is heated at 150°,
and finally to 180°, In a current of air as long as
water and maleic acid distil out. The residue is
washed with a Uttle cold water and dried at
100°. 250 g. malic acid treated in this way give
160 g. fumaric acid (Furdie, C. J. 39, 346 ; cf.
Baeyer, B. 18, 676).
Properties. — Small prisms, peedles, or plates.
Sublimes at 200°, and when strongly heated it
gives some maleio anhydride. It burns with a
pale flame. The initial rate of etherification of
fumaric acid (32'7) is less than that of maleic
acid (51-5), but ultimately the same proportion
of each (72-6 p.c.) is etherified by isobntyl alcohol
(Menschutkin, B. 14, 2630).
BeacUcma. — 1. Seduced to succinic acid by
adding sodium-amalgam to its aqueous solution,
or by heating with HIAq. — 2. Heated with
HBrAq at 120° it is slowly transformed into
bromo-succinic acid. — 3. It combines veryslowly
with brcmiine in the cold, but when heated with
bromine and water at 100° di-bromo-succinio
acid is formed in a few minutes (EekulS, A. Svppl.
1, 129 ; Petrie, A. 195, 56). — 4. Zinc dissolves in
aqueous fumaric acid, forming zinc-fumarate, and
giving off hydrogen (Keknl6, A. Swppl. 2, 108).
When zinc and fumaric acid are placed together
in cold water hydrogen is not evolved, , but zinc
fumarate is formed, while suooinio acid remains
in solution (Von Victor, Z. [2] 4, 454). When
fumaric acid is gently heated with zinc and
excess of potash-solution it is reduced to suc-
cinic acid (K.). — 6. Fumaric acid is not oxidised
by boiling HNO„ by water and PbOa, or by
KjCrjO,. Aqueous KMnO^ oxidises it to race-
mic acid. — 6. EleciroVysis of an aqueous solution
of sodium fumarate gives acetylene, OOj, and
hydrogen (Kekul6, 4. 131, 85).— 7. Chlorme forms
di-ohloro-sucoinio and tri-phloro-acetio acids
(Pfitriefl, BZ.[2] 41, 309).— 8. Hypochlorous add
forms a compound (COjH.CHCl.CH(OH).COjH),
-which yields inactive malic acid when reduced by
sodium-amalgam (F.).^. Aqueous NaOH at
100° slovfly forms inactive malic acid. — 10. Water
in large quantity at 150° also forms inactive
malic acid (Jungfleisch, B. 12, 370 ; Fictet, B. 14,
2648).— 11. Boiling aqueous KjSO, forms potas-
sium sulpho-sucoinate. — 12. Acetyl chloride, in
presence of HOAo at 100°, dissolves fumaric acid
in twenty-four hours, the product being maleio
anhydride (Perkin, C. J. 39, 560 ; 41, 268), while,
according to Anschiitz (B. 10, 1881; 14, 2792),
pure AcCl has no action on fumaric acid. By
heating fumaric acid with pure AcCl at 140°
Ferkin {B. 15, 1073) obtained maleic anhydride
and a little chloro-succinic anhydride ; the latter
being probably an intermediate body in the
formation of maleic anhydride (Anschiitz a.
Beimert, B. 15, 640).— 13. Pumamc chloride
alone, or dissolved in benzene, reacts with
silver fumarate, forming maleic anhydride.^
Fumaric chloride, dissolved in light petroleum,
is converted by Na^CO, into maleic anhy-
dride. It is evident, therefore, that there is
but one anhydride for the two isomeric acids,
fumaric and maleic. — 14. A dilute aqueous solu-
tion containing fumaric acid and aniUne in pro-
portion to form the acid aniline salt gives, on
heating, no anilide (difference from maleic acid)
(Michael, Am. 9, 180). — 15. Excess of alcohoUo
ammonia at 150° for twenty hours forms inactive
aspartic acid (Engel, C. B. 104, 1805).
Salts. — None of the fnmarates dissolve in
alcohol. Solutions of the alkaline fumarates
are not ppd. by salts of Zn, Al, or Cr. — (NH,)jA" :
V. sol. water, converted into the acid salt by
evaporation. — (WlT^)TTA''; monoclinic prisms
(Delffs, P. 80, 435 ; Pasteur, A. Ch. [3] 31, 91).—
E2A"2aq : large transparent trimetric tables and
four-sided prisms or radiating groups of laminas.
V. sol. water; from a concentrated solution
acetic acid throws down the acid salt. — KHA" :
tufts of needles, si. sol. cold, v. sol. hot, water
(Oarius, B. 4, 929; ul. 142, 153).— KjH,A",:
acicular prisms. S. 2-66 at 19-6°. — Na^A" aq :
crystalline powder; ppd. by adding alcohol to
its aqueous solution. — Na2A"3aq: needles and
prisms. V. sol. cold water.-^AgjA" : fine white
powder, thrown down by adding AgNO, to a
solution of (even 1 pt. in 200,000 of) fumaric acid.
Deflagrates when heated. Insol. water, sol.
HNOjAq and NHjAq. — AgjA" aq • (Carius) : sol.
hot water. — ^BaA"- Obtained by dissolving
fumaric acid in a hot solution of barium acetate
(fumaric acid does not ppt. baryta water). Crys-
talline grains. — BaA" l^aq. From KjA" and
BaCl,. Small ef3orescent prisms. S. (of BaA")
•966 at 17°.— BaA"3aq: small white prisms.
Converted by boiling with water into insoluble
grains of BaA" (Anschiitz, B. 12, 2282).—
SrA" 3aq : from fumaric acid and SrO^ACj. Crys-
talline powder, si. sol. water. — CaA" 3aq. Occurs
in fumitory. From K^A" and CaOjAoj. Shining
scales, si. sol. water, permanent in the air. Gives
calcium succinate when exposed in contact with
fermenting cheese to the air. — CaA" l|aq (dried
overH^SOJ. — MgA"4aq : white powder. — Hg^A":
white crystalline pp. (Eieokher, A. 49, 31)1 —
PbA"2aq. Formed by heating lead malate to
200° (R.). Also from K^A" and aqueous PbOjAo,
acidulated with HOAc. Tufts of shining needles.
Nearly insol. cold, sol. hot, water ; insol. HOAc ;
sol. HNO»Aq.— FbA" 3aq (Pelouze).- A"(PbOH),
684
FUMARIC AOID.
(at 100°). Fpd. by adding ommonio famarate
to boiling aqueous lead Bubacetate (Otto, A. 127,
178).— (PbA")jPbO xaq fB.).— PbA"(PbO)j a;aq
(B.). — CuA"3aq. From Cu02Ac2 and fumaric acid.
Bluish-green crystalline powder ; si. sol. water,
V. sol. HNOjAq.— A"PeOH. Pale brownish-red
pp. formed by adding FeCl, to ammonium fuma-
rate: insol. excess of ammonium fumarate
(difference from succinate) ; insol. NH,Aq, sol.
mineral acids. — NiA"4aq: pale-green powder,
sol. water and ammonia solution. — CoA" 3aq.
Obtained by adding alcohol to a concentrated
solution of fumario acid in aqueous CoOjAcj.
Bose-coloured powder, v. sol. water and NHjAq.
— MnA" 3aq. From f umaric acid and HnOjAc^
White powder, si. sol. water.— ZnA" 3aq : large
prisms (from hot solutions), v. sol. water. —
ZnA"4aq: efflorescent crystals (by spontaneous
evaporation).
Methyl ether Me^k". [103°]. (192° i. V.).
Formation. — 1. By the action of HCl or
E2SO4 on fumaric acid in MeOH (Anschiitz,
B. 12, 2282 ; OssipofE, J. B. 11, 288).— 2. By the
action of iodine on methyl maleate. — 3. From
methyl bromo-succinate by treatment with KCy
in ether, or by subliming the same ether with
NaOAo and CaCO, (Volhard, A. 242, 160).— 4.
By the action of NaOMe on a solution of fumaric
ether in MeOH (Purdie, G. 3. 51, 627).— 5. By
boiling methyl diazo-sucoinate with water or
MeOH (Curtius a. Koch, B. 18, 1296).
Pro'perties. — Triclinic prisms (Bodewig, Z. K.
6, 563). SI. sol. water, alcohol, ether, and GS2
in the cold. Combines with bromine forming
methyl di-bromo-sucohiate [62°]. With an
equivalent quantity of diazo-acetic methyl ether
CO2Me.CH.Nv
it forms | NOKCOaMe, an oil,
C02Me.CH.N^
whence the corresponding acid [220°] may be
obtained i(Buchner, B. 21, 2637).
Mono-ethyl ether EtHA". Formed by
hea,ting fumaric acid (2 pts.) with alcohol (3 pts.)
at 120° (Laubenheimer, A. 164, 297). Plates,
si. sol. water, v. e. sol. alcohol and ether. —
AgEtA". S. -3 at 12°. Crystalline pp.
Di-ethyl ether Bt^A". (215° uncor.) (P.) ■
(218° i. V.) (A.). S.G. ll:* 1-052 (A.) ; n 1-106
(H.). V.D. 85-5 (calc. 86). M.M. 10-119 (Perkin,
O.J.i'roc. 3, 98).
Formation. — 1. By treating an alcoholic
solution of fumaric or malic acid with HCl
(Hagen, A. 38, 274), Some chloro-succinic ether
is formed at the game time. — 2. By boiling
fumaric acid (149 g.) with alcohol (450 g.) and
UJSO, (15 g.), ppg. by water, drying over CaClj,
and distilling. The yield is good (123 g.)
(Purdie, C. J. 39, 346).— 3. From malic ether
and PCI5 (Henry, A. 156, 177).— 4. From EtI
and silver fumarate (Anschiitz, B. 11, 1644 ; 12,
2282). — 5. By the action of finely divided silver
on di-bromo-succinic ether (Gorodetzky a. Hell,
B. 21, 1802).
BeacUons. — 1. Combines with bromine form-
ing di-bromo-succinic ether [58°] (Ossipoff). — 2.
Combines with NaOEt (in alcoholic solution)
formmg 00jBt.CHNa.CH(0Et).CQ2Et. If the
product is boiled with aqueous KaOH, neutral-
ised with acetic acid and treated with Pb(OAc)j,
lead fumarate is ppd. The filtrate is acidulated
with HKO„ neutralised with NH9, and treated
with Pb(N03)2, when a lead salt is ppd., whenoe
HjS liberates a crystalline aoid OgHigOs or
C02H.CH2.CH(OEt)C02H, [86°] (v. MaliO aoid)
(Purdie, C. J. 39, 347). Sodium fumarate differs
from ethyl fumarate in not combining with
NaOEt. — 3. NaOMe (in methyl alcoholic solution)
reacts in a similar way forming first methyl
fumarate and then G02Me.CH2.CH(OMe).C02Me
or its sodium derivative (Purdie, O. J. 47, 855).
4. By heating with alcoholic NH, in sealed
tubes there is formed aspartic ether (152° at
25 mm.) together with a compound CfHgN^O.
[o. 250°], possibly an imide of aspartic acid
(Korner a. Menozzi, Q. 17, 226).
Iso-butyl ether (PrCH^)jA". (170°) at
160 mm. From silver fumarate and isobutyl
iodide (Purdie, O. J. 39, 353). Not obtained
quite pure. Combines with sodic isobutylate in
presence of isobutyl alcohol forming a product
whence^ on saponification, the isobutyl deriva-
tive of malic aoid (3. v.) is got.
Phenyl ether {CJB.^)^k". [162°]. From
fumaryl chloride and phenol. White needles,
si. sol. alcohol. On heating it evolves CO,,
yielding phenyl cinnamate and finally stilbene
CjH5.C2H2.CsH5 (Ansohutz a. Wirtz, B. 18, 1948 ;
O if 47 898)
" p-Tolyl ether (C,H,)2A" : [162°] ; v. si. sol.
alcohol. On heating it gives s-di-tolyl-ethylene
C,Hj.C2H2.C,H, [179°], and a substance crystal-
lising in scales [79°] (A. a. W.). ' ^
Chloride CjHj(C001)2 or C^<;i^^''^0.
Mdleyl chloride. ,(160°). From malie aoid and
PCI5 (Perkin a. Duppa, A. 112, 26). Formed
also by the action of PCI5 on fumaric acid or
maleic anhydride (KekulS, A. Suppl. 2, 86 ;
Perkin, B. 14, 2548). Bromine at 150° combines
with it, forming di-bromo-succinyl chloride.
Mono-amide C02H.CH:CH.C0NH2. Fu-
maramic aoid. Anhyd/ro-aspartic aeid. [217°].
Prepared by the action of methyl iodide and
caustic potash on asparagine C4H,N20, + 4MeI
= C<H50sN-l-NMe,I+ 3HI (Griess, B. 12, 2117 ;
Michael a. Wing, Am. 6, 420). Leaflets, sol.
hot water and hot alcohol, almost insol. ether.
Decomposed by alkalis or acids into NH, and
fumaric acid. Combines with bromine (1 mol.).
Salts. — BaA'jOaq: plates, si. sol. water. —
AgA' : small needles or leaflets, sol. hot water.
Methyl ether A'Me: [162°]; small colour-
less tables ; sublimable i si. sol. cold water, v.
sol. alcohol.' Formed by the action of cold|
slightly acidulated, water on methyl diazo-su^-
oinamate CO^Me.CJBLj.CNj.COjMe (Curtius a.
Koch, B. 19, 2461).
Amide GtB.,^fiJ.e. CONH2.CH:CH.CONH2.
[232°]. From fumaric ether and cold aqueous
ammonia (Hagen, A. 38, 275). Small white
needles (Curtius a. Koch, B. 18, 1296). Insol.
cold, sol. hot water, insol. alcohol. When heated
for some time with water it is converted into
ammonium fumarate. HgO is converted by
boiling with its aqueous solution into a white
powder C^HjNjOjB^O (Dessaignes, Ai 82, 233).
CH.COv
Imide 7 C^NHaOj i.e. || >NH? Formed
CH.CO^
by heating acid ammonium malate at 160° to
200° (Dessaignes, O. B. 80, 324 ; Wolff, A. 75,
293). White powder; sol. hot cone. HClAq and
FTJMARINE.
6S£
reppd. by water. By heating for 6 hours with
HClAq it is converted into' aspartio acid. Acid
ammonium maleate and f umarate yield on heat-
ing to 180° substances resembling this so-called
• Inmarimide ' (Pasteur, A. Oh. [3] 34, 30).
Di-ethyl-amide OjHjcO.NHEt)^. [ISS"].
White scales; may be sublimed (Wallach a.
Eamenski, B. 14, 170).
Mono-anilide 0O2H.CH:CH.C0.NHPh.
ShimaraniUc acid. [187°]. Prom the phenyl-
imide of maleic acid by treatment with baryta-
water at 35° (Ansohutz a. Wirtz, Am. 9, 240 ; A.
289, 137). _ Formed also when maleic anhydride,
dissolved in ether, is mixed -with aniline (An-
sehutz.S. 20, 8214). Prisms, si. sol. water. Con-
verted by alcoholic EOH into potassium fuma-
rate.
Di-anilide CjH2(CO.NHPh)2. Formed by
the action of aniline upon fumaryl chloride, both
being in ethereal solution (Anschiitz a. Wirtz,
Am. 9, 236). Minute white needles, browning
at 275°, v. si. sol. ether, si. sol. alcohol and glacial
acetic acid. Heated at 100° with alcoholic KOH
it gives aniline and fumaric acid. Takes up Br
(1 mol.), forming a white powder ; not melted at
100°.
Di-phenyl-amic acid
C0NPh2.0H:CH.00jH. Di-phmyl-fvmaramic,
<add. [120°]. Formed by heating fumaric or
malic acid with di-phenyl-amine at 210°; ex-
tracting the product with ether, shaking the
ethereal solution -with dilute NH„ and ppg. by
HCl (Piutti, a. 16, 22, 133). SmaU needles ;
Bol. alcohol and cone. HjSO,, the solution giving
with nitric acid the blue reaction of diphenyl-
amine. Decomposed by EOH into fumaric acid
and diphenylamine. Unites with Br forming a
crystalline product. Its alkaline solution gives
a light green pp. with cupric salts.
CH.CO V
Di-phenyl-imide7 U >0. [275°].
OH.C(NPhj)/
Formed by heating fumaric or maleic acid with
di-phenyl-amine at 225° as long as water is given
ofl (Piutti). Grlistening needles, sol. HOAo.
With cone. HNO, it yields a nitro- compound
giving a violet colouration with alcoholic KOH.
Phenyl-methyl-amic acid
CONMePh.CH:CH.COjH. [128°]. Formed by
heating maUo acid (1 mol.) with methyl-aniline
(not more than 2 mols.) at 150° (Piutti, G. 16,
24). It ia also one of the products of the action
of NH, on phthalyl-aspartic acid. Long tabular
prisms (containing aq) ; melting at 100° when
hydrated, apd at 128° when anhydrous. Insol.
water, sol. ^cohol and ether. Its alkaline salts
are very soluble ; its silver salt forms small glis-
tening prisms. Its di-bromo- derivative
[178°] forms glistening prisms, partly decom-
posed on recrystallisation.
Phenyl-methyl-imidel OigHjgNjOj i.e.
caco-^ . ,, , .
I ^O. [187°]. Formed by heatmg
CH.C(NMePh)/ .
malic acid with methyl-aniline at 200°. It is
also one of the products of the action of phenyl-
methyl-amine on phthalyl-aspartic acid at 240°.
Glistening prisms, sol. hot alcohol and chloro-
form. When heated with cone. HClAq at 180°
it yields fumaric acid and methyl-aniline. Br
in chloroform forms a di-bromo- derivative
C,8H,.Br,NA [0. 207°].
ConsUtution. — Inasmuch as both fumario
and maloLc acids are dibasic acids formed from
malic acid by elimination of water, and oa^pable
of reduction to succinic acid, they ought both to
be represented by the formula CjH2(C0jH)j. One
or both of them would then be002H.CH:CH.C0jH.
The usual interpretation given to structural for-
mula will not in this case account for the iso-
merism, ^nd it will be necessary, if we assign the
formula OOjH.CHtOH.COaH to both maleic and
fumaric acid, to consider that the difference in
structural formula is one that cannot be repre-
sented on a plane surface but only in space.
Various attempts have been made to express a
difference in structure upon paper. Thus while
the formula COjH.CHrCH.COjH has commonly
been assigned to fumaric acid, maleic acid has
been represented by CO2H.CH2.O.CO2H (Fittig,
A. 188, 42; c/. Hubner, B. 14, 210), by
CH.C(0H)2v CH.C(OH)- \
II >0. and by || >0 >) '
CH.CO / CH.C(OH) ^
(Anschutz, A. 239, 161; Am. 9, 258 ; W. Eoser,
A. 240, 138). Erlenmeyer, on the contrary, sug-
gests that maMc acid is C02H.CH:GH.C02H,
while fumaric acid may have the double formula
O0sH.CH:CH.C(OH)<;^>C(OH).CH:CH.COjH
(B. 19, 1936), although Eaoult's method of
determining molecular weights indicates that
this is not the case (Paternd, B. 21, 2168)^
Maleic acid is much more ^prone to react
with other bodies than fumaric acid, and
this would be represented by the formula
CO2H.CHJ.C.CO2H, containing a divalent carbon
atom, and perhaps also by the anhydride formula
CH.C(OH)„
II I >0 of Ansch&tz. Thus maleic acid
CH.OP /
combines at once with HBr and with bromine,
whereas fumaric acid requires to be heated (in
the case of Br the products are different). Again
acid aniline maleate readily splits off water when
its aqueous solution is left to stand for a few
days, or when it is boiled, a crystalline pp. of the
acid anilide COjH.CjHj.CONHPh being formed;
under these conditions the acid aniline f umarate
is quite stable (Michael, JB. 19, 1372). The che-
mical differences here noted between fumaric
and maleic acids hold good also between citra-
eonic and mesaoonic acids, and between (a)-cou-
maric and (i3)-coumaric acids. There is also bpt
one anhydride to each of these pairs of acids.
The fact that fumaric acid, on oxidation by
KMnOj, gives racemic acid, while maleic acid
gives inactive tartaric acid, has been explained
by Le Bel by the aid of forlnules represented in
three dimensions {>v. also Lossen, B. 20, 8810 ;
Anschiitz, B. 21, 518). According to Enops {A.
248, 175) thb molecular refraction of fumaric and
maleic acids and their ethers indicates that both
these acids contain the group C:G. The term
' allo-isomerism' -has been applied to such cases of
isomerism as that here described : fumario acid
may be called allo-maleic acid.
Beferences.—MAixio aoid, Bbouo-fumabic
ACID, and OHiiOBO-muAitic Aon>.
FUMABIITE, An alkaloid contained in ta-
imtorj{FtmariaofficmaUs)(Veseiiieii Hannon,
586
FUMABINE.
J. Chim. Mid. [3] 8, 705 ; Preusfl, 2. [2] 2, 414 ;
Bl. [2] 7, 453). The plant gathered in-fnll flower
may contain 6 p.o. of famarine.' The plant is
extracted by dilute acetic acid at 100°, the ex-
tract evaporated, the syrupy residue dissolved in
alcohol, and deoolonrised by animal charcoal.
Fumarine acetate crystallises from the alcoholic
solution in slender needles. Aqueous EOH and
Xa2C0, separate fumarine from its salts as u
curdy pp. It crystallises in six-sided irregular
monocUnic prisms, si. sol. water, insol. ether,
sol. alcohol, chloroform, benzene, and CS^. Its
solution has a bitter taste and alkaline reaction.
Cone. HNO, does not coloiur it. Cone. H^SO,
forms a dark-violet liquid. Its hydrochloride
and sulphate crystallise in prisms, sL sol.
water; its platinoohloride and aurochlor-
ide crystallise in octahedra.
fUMASYL CHLOBIDE v. Chloride of Ftiua-
BIO ACID.
FirBFTTBACBOLEiCN v. FmtFCBYL-ACB^iita
ALDEHTDE.
FTTSFITBACSTLIC ACID v. Fubfubyl-aobt-
Lia ACID.
FUSFTTBAL v. FobfubaiiDEHtde.
YVKEVRAL-compounds v. Fubfubtl-me-
ihyuene convpovmds.
FTTBFUSAL-ACZTOACETIC EIHEB. De-
scribed under Aoeto-acetio acid.
FUBFUBAL-ACFIONE v. FcbfubyIi-tikyi.
UEIHYIi KETONE.
FTTBFVSAI-BENZTLISENE^CEIONE «.
puefubyii-vinyl stybyi, ketone.
FUBFTTRAL-CABBAMIC EIHEB v. Fdbfu-
byl-uethylene-dicabbamic etheb.
FVBFITBALOOHOL v. FnBFiTBYi.-0ABBiNOL.
FUBFUBAIDEHYDECsH^Oji-e. O.HjO.CHO.
Pyrom/ude aldehyde. Fzt/rftirol. Furfural. Fv/r-
fwrane-carboxylic aldehyde {Furfur = hTa,n).
Mol. w. 96. (162°) (Briihl, A. 235, 7). V.D. 3-34
(calc. 3-32). S.G. V 1-1594 (B.). S. 9 at 13°
(Stenhouse) ; 8-8 at 15-6° (Fownes). /is 1-5261
(B.). S.V. 95-53 (B. Sohiff, A. 220, 108) ; 103
(Bamsay). E.F.p. 5985 (Bamsay, C. J. 35, 703).
Dispersion value : Briihl, A. 236, 259.
Occurrence. — Has been observed in brandy
(Morin, C. R. 105, 1019), and is a constant im-
purity in isoamyl alcohol prepared from fusel
oU (Udr&nsky, H. 13, 248).
Formaticm. — 1. A general product of the de-
structive distillation of the carbohydrates or of
substances containing them, such as wood.
Formed also in the torrefactiou of coffee and
cocoa and occurs in tobacco smoke (Volckel, A.
85, 65; Hm,il?».8, 36;. H. SchifE, &. 17, 355;
Gaus, Stone, a. Tollens, B. 21, 2148 ; V. Meyer,
B. 11, 1870 ; Forster, B. 15, 322 ; Jorisson, B. 15,
674). — 2. By distilling the following substances
with dilute sulphuric acid : bran, starch, oatmeal,
sugar, madder, sawdust, linseed cake, cocoa-nut
shells, mahogany, and even, according to Udran-
pky (H. 12, 377), of proteids (Doebereiner [1881]
Sahu). J. 63, 368 ; A. 3, 141 ; Stenhouse, P. M.
[8] 18, 122 ; 37, 226 ; A. 35, 301 ; 74, 278 ; 156,
197 ; Fownes, Tr. 1845, 253 ; A. 64, 52 ; Ph. 8,
118 ; Cahours, A. Ch. [3] 24, 277 ; Emmet,
Am. S. 32, 140 ; GndkoS, Z. 1870, 362 ; Guyard,
Bl. [2] 41, 289).— .1. By distiUing sugar with
MnO, and dUute sulphuric acid.-^4. By heating
bran with a very strong solution of ZnCL, (Von
Babo, A. 86, 100). — 6. By heating wood shavings
with water for four hours at 200° (Greville.
Williams, O. N. 26, 281, 298; H. Miiller, C. N.
26, 247). — 6. Formed in small quantity by boil-
ing sugar with water; this accounts for its
occurrence in brandy (F6rster, B. 15, 230, 322).
7. One of the products obtained by heating
(a)-acrosone to 140° (E. Fischer a. Tafel, B. 22,
99). Obtained also by heating a dilute aqueous
solution of glnoosone in a sealed tube at 140° (E.
Fischer, B. 22, 93).— 8. By heating a 5 p.o.
aqueous solution of mannite in a closed tube for
4 hours at 140° (E. Fischer a. Eirschberger, B,
22, 869).
PreparaUon. — 1. By distilling sugar (1 pt.)
with MnO, (3 pts.), H2SO4 (8 pts.), and water
(6 pts.) ; the distillate is neutraUsed by NajCO,,
re^stilled, and saturated with CaCl, (Doebe-
reiner).—2. HjSO, (100 pts.), water (300 pts.),
and bran (100 pts.) are ^stiUed together. The
product is neutralised by Na^CO,, redistilled,
saturated with NaCl and re-distilled (Schwanert,
A. 116, 257). The yieldis small (less thjan 3 pts.).
The crude furfuraldehyde is treated with ^ute
E2SO4 and a little E2Cr20, to remove <meta-
furfural,' dried over CaCl^, and re'ctifled. — 8. An
abundant source of furfuraldehyde is in the pre-
paration of ' garancin ' by boilmg madder with
dilute sulphuric acid.
Impa/rity. — Crude furfuraldehyde is liable to
contain a readily oxidisable oil of higher boiling-
p'oint, which is for the most part resinified
during the distillations. When this 'metafur-
furol' is present the furfuraldehyde gives a
purple colour when mixed with a few c&ops of
cone. H2SO4, of EClAq, or of HNO,; in this
case also the aldehyde, after boiling with
aqueous EOH, turns red on acidification.
Properties. — Colourless oil which, except
when quite pure, slowly turns brown when ex-
posed to hght. Its odour resembles that of a
mixture of the oils of cinnamon and of bitter
almonds. It bums vrith a smoky flame. Fur-
furaldehyde when present in a liquid imparts a
rose-red colour to paper saturated with aniUne
acetate (Guyard, Bl. [2] 41, 289) ; but its pre-
sence is best detected by a mixture of equal
volumes of xylidine and glacial acetic acid to
which a little alcohol is added when the intense
red colour of C4H30.CH(0jH2Me2NHj)j is pro-
duced : this reaction is exhibited by the product
of the distillation of -00005 g. sugar (H. Sohiff,
Q. 17, 355; B. 20, 540), Furfuraldehyde may
be substituted for sugar in Fettenkofer's reaction;
thus a drop of a solution of furfuraldehyde (1 pt.)
in water (20,000 pts.) gives a crimson colour on
the addition bf choUo acid and HgSO,. The
following substances also give the red colour
with H2SO4 and furfurald^yde : isobutyl alco-
hol, allyl alcohol, tert-\>\Ay\ alcohol, terf-amyl
alco]}ol, isoamyl alcohol, oleic acid, petroleum,
acetal, aldehyde, aceto-acetic ether, acetone,
glycol, malic acid, alizarin, aniline, anthracene,
anthraquinone, atropine, benzoic aldehyde,
bomeol, pyrocateohin, brucine, quinic acid,
oholesterin, cinchonine, codeine, ooniferin, '
coniine, coumarin, cytnene, digitalin, di-methyl-
aniline, di-phenyl-amine, gaJlio acid, cresoV
mesitylene, methyl alcohol, methyl-anilineil,
morphine, naphthalene, (a)-naphthol, orcin;
parafBn, phenanthrene, phenol, phenyl-hydra-
zine, phloroglucin, propionic aldehyde, pioto-
FUEFURALDEHYDE.
687
tateohuio acid, pyrogallol, resorcin, salioylio
noid, scatole, stearic acid, stTyohnine, toluene,
thymol, tyrosine, veratrine, and xylene, and (to
a slight extent) isopropyl alcohol. The follow-
ing do not give the red colour: alcohol, propyl
alcohol, acetic acid, isobutyrio acid, acrolein,
benzene, acetamide, aoetophenone, alloxan,
aspartic acid, benzonitrile, benzoic acid, succinic
acid, pyruyic.acid, butyric acid, caSeiine, quinine,
quinoline, quihone, qiiinoxaline, chloral hydrate,
chloroform, citric acid, crotonic acid, oyanamide,
dextrin, duloite, fumario acid, lactic acid, gly-
cerin, glycocoll, glycollic acid, uric acid, urea,
hippuric acid, isatin, malic acid, maltose, man-
delio acid, mannite, methylamine, oxalic acid,
phenylene-m-diamine, phenyl-acetic acid, picric
acid, piperidine, pyridine, hydroquinone, mucic
acid, starch, glucose, tannin, tartaric acid, and
cinnamic acid (Mylius, J?. 11, 492 ; Udr&nsky,
H. 12, 355).
Reactions. — 1. When its aqueous solution
is boiled with Ag^O silver is deposited, and silver
pyromucate crystallises out of the cooled fil-
trate.— 2. Hot mbric acid, forms oxalic acid. — 3.
Cold cone. H2SO4 dissolves it unaltered and
without becoming coloured ; carbonisation sets
in on heating. — 4. Aqueous KOH, even in the
cold, forms resinous products. Alcoholic EOH
forms pyromucio acid and furfuryl-carbinol
(Ubich, O. N. 3, 116 ; Limpricht, Z. [2] 5, 599).
5. Converted into furoin C,„HsO, by heating
with aqueous KCy. — 6. When mixed with ben-
zoic aldehyde (1 equivalent) and treated with
KCy it gives benzfuroiin C,5ja,„0j. [139^]
(Fischer, Ai 211, 228).— 7. With mtro-eihane
and aqueous KOH it gives furfuryl-nitro-ethyl-
ene CjHsO.CaCH.NOj [75°] which crystallises
in long ydlow prisms (Priebs, B. 18, 1862).— 8.
ZnEtj followed by water forms furfuryl-propyl
alcohol C4H30.CH(0H).C2H, (180°) (Pawlinoff
a. Wagner, B. 17, 1968). — 9. Condenses with
acetone in presence of alkalis forming f urf liryl-
vinyl methyl ketone CiHaO.CHiCH.OO.CHs and
di-furfuryl-di-vinyl ketone (OtBi,O.CK:CB.)fiO
(Claisen a. Ponder, A. 223, 145).— 10. By add-
ing aqueous NaOH to mixed aqueous solutions of
furfuraldehyde and bhloro-acetie-aldehyde there
is formed C4HsO.CH:CCl.CHO which crystal-
lises in broad yellow needles [79°] sol. hot water,
jether, and alcohol. This aldehyde forms a
phenyl-hydrazide [157°] and an oxim [165°];
moist AgjO oxidises it to a-chloro-furfuryl-
aorylic acid CjHaO.CHiCCl.COjH which crystal-
lises in tufts of white needles [142°]. The o-
ohloro-furfuryl-aorolein is converted by boiling
with sodium acetate and silver oxide into
C,H30.CH:CCLCH:0H.C02H which forms yel-
low interlacing needles [168°] (Mehne, B. 21,
423). — 11. When furfuraldehyde is adminis-
tered to dogs or rabbits in doses of 5g. daily
little toxic effect is produced ; the urine is found
to contain pyromucio acid, pyromucurio acid
(glycocoU pyromucate) 0,H,NO, [165°], and
glycocoll furfuryl-acrylate C,H^04 [215°].
Boiling baryta-water splits up the two last-
named compounds into^lyoocoU and pyromucio
or f urfuryl-aerylio acids respectively. Fowls are
soon killed by taking 1 g. of furfuraldehyde per
day; their excreta then contain pyromnoorni-
thuric acid C,»H„NA [186°] (JafEfi a. Cohn, B.
80, 2311 ; 21, 3461).— '12. A mixture 01 pyrmic
acid and amiUne dissolved in cold ether or alco-
hol forms the compound Qa,H,jNj02 [185°]
which crystallises in needles, insol. water, ether,
acids, and alkalis, si. sol. cold, m. sol, hot,
alcohol; t. sol. HO Ac. This compound gives
off aniline when warmed with acids or alkalis
(Doebner, A. 242, 284).— 13. A mixture of pyru-
vic acid and aniline in warm alcoholic solu-
tion forms furfnryl-quinoline carboxylio acid
0,H30.C,NH5.C05H [210°-215O] (Doebner).—
14. Furfuraldehyde may be substituted for ben-
zoic aldehyde in Ferkin's reaction. Thus with
NaOAc and AcjO it gives furfuryl-acrylic acid. —
id. ThioglycolUc acid reacts with formation of
C,HsO.0H(S.0Hj.COjH)j [105°] (Bongartz, B.
21, 478). — 16. Aqueous ammcmia in the cold
converts fuijuraldehyde in a few hours into
' furfuramide ' (C,H30.CH)3Nj [117^ a crystal-
line body analogous to hydrobenzamide. Boiling
aqueous KOH converts furfuramide into a base,
furfurine Oj^Ki^TSfi,. — 17. Combines with se-
condary and primary amines or with 1 mol. of
each to form coloured compounds. Thus with
mono-methyl-anihne it gives tlie compound
C5H,Oj2CBHj.NHMe, whose hydrochloride
(B'HCl) forms splendid violet crystals [94°]
which dissolves to deep-red solutions. With
aniline and mono-methyl-aniline it gives
CsH^O, |c«2=;^j^g. With aniline and tolylene
diamine itgives (C^H^OJ^ { |?^|nS' ' "^'^^^
aniline and benzidine it gives
(C3H,0j)j-[j?»g'-^^)« . The hydrochlorides
of these bases crystallise in bronzy metallic
crystals which dissolve in alcohol with violet
colour. With aniline and amido-benzoic acid or
with aniline and naphthylamine-sulphonic acid
furfurol yields the compounds:
^»^*"HC,H,(NH2)C0jH *"''
C^HA{g:5;fNHJS03H • W»«^ tl'^ '»'"'««'■
nium salt of di-nitro-amido-phenol (picramio
acid) it gives {C5H^O,}{C3Hj(NOj)2(NH,)(OH)f
whose ammonium salt crystallises in glistening
golden needles. Weak acids decompose it into its
constituents (Schiff, B. 19, 847 ; cf. Stenhouse,
A. 156, 199). Furfuraldehyde combines directly
with one equivalent of m-amido-benzoio acid, of
amido-salicylic acid, and of amido-cuminic acid
forming dichroic needles with neutral proper-
ties (Schiff, A. 201, 355 ; G. 10, 67). The com-
pound of furfuraldehyde with m-amido-benzoia
acid may be represented on the rosaniline type
thus: C4H30.CH(OH).C.H3(CO,H)NH2 (Schiff, (?.
17, 329). — 18. An alcoholic solution of cmiUne (46
pts.) and aniline hydrochloride (65 pts.) reacts
upon furfurol (48 pts.) forming the hydrochloride
of 'furfuranUine' C^fii{^^J^^)i^(^^ {«•
supra), which crystallises from alcohol in purple
needles, insol. water. The free ' furfiuaniline '
is an unstable brown amorphous mass. — 19.
m-Nibro-amMne forms CjH4(N.Oj)NH2(C5H40j)
[100°-120°] which crystallises from alcohol in
lemon -yellow crusts. Its hydrochloride
CuHjoNjO^HCl forms copper-coloured plates and
gives a crimson solution in alcohol.— 20. Di-
phenylamine (2 mols ) at 150° formg a com-
688
FDEFURALDEHYDE.
pound whose hydrochloride is copper-coloured
and forms a crimson solution in alcohol. Di-
phenylamine hydrochloride gives the same body.
21. ip-AmAdo-phenol in dilute aqueous solution
reacts with elimination of water, depositing
after some time small yellow prisms of ' oxyfur-
furaniline ' OjHaO.CHiN.CjHjOH [182°] which is
sol. alcohol, and forms a hydrochloride that
crystallises from alcohol containing NH4CI in a
form resemblingrosanUine hydrochloride (Schiff,
G. 10, 60; A. 201, 358). — 22. Phenylme-
o- diamine hydrochloride solution forms
(CjH30.CH)jN20oHi [96°] (Ladenburg a. Engel-
breoht, B. 11, 16S3). — 23. Tolylene-m-diamine
forms (C5Hi02)jCjH3Me(NH2)j a crystalline sub-
stance, decomposed at 125° without melting.
Its hydrochloride forms an intense crimson
solution in alcohol, but is much less stable
than the corresponding compound with tolylene-
o-diamine (Schifi ; cf. Ladenburg, B. 11, 595). —
24. Benzidine in alcoholic solution forms yel-
low needles of (04HjO.0H:NH)jC,2Hs; which
gives a hydrochloride crystallising in copper-
coloured scales, and a platinochloride, separa-
ting as a yellow crystalline powder. — 25. When
triturated with m-amido-bensoic acid it com-
bines to form (C5HjOj)CeH4(NH2).C02H which
crystallises in small dichroic scales resembling
a salt of rosaniline. Its hydrochloride forms
red velvety crystals and gives crimson solutions
in alcohol and HOAc. It dissolves in Na20O3AcL
without evolution of CO^. — 26. A mixture of
aml/i/ne hydrochloride and methyl-amit/me give a
ruby-red colouration turning green and £nally
violet; the body formed in this reaction
'cXOa{NHjPh)(NHMePh)HCl is a crystalline
mass, V. sol. alcohol, insol. water. — 27. ((l)'Naph-
thylamAne forms, with elimination of water,
iD,H30.CH:N.C,oH, [85°]. It crystallises from
alcohol in colourless scales. Its hydrochloride
B'HCl forms yellow needles dissolving in alco-
hol with a deep red colour (Sohiff, Q. 17, 340).—
28. Di-Tneth/yl-aniUne and ZnCl^ heated with fur-
furaldehyde form CjiHj^NjO [83°] which crys-
tallises from ligroin in needles. It forms a crys-
talline platinochloride B"H2PtClB and picrate
B"(C„Hj(N02)30H)2 (Fischer, A. 206, 141).— 29.
(Py.Z)-Methyl-giimoline heated with an equi-
valent of furfuraldehyde at 100° together with
a small quantity of ZnClj forms a base C,5H„N0
which crystaUises from ligroin in needles or
tables that turn black in daylight. Its salts
B'HCl, B'HNOj, B'HjSO^aq, B'j^t01e2aq, and
B'Cj,H2(NOj)aOH are crystalline (Srpek, B. 20,
2044). — 30. Carhamic ether in presence of HCl
forms C4H50.CH(NH.COjEt)j [169°] which may
be sublimed as long thin needles, insol. water,
V. e. sol. alcohol and ether (Bisohoff, B. 7, 1081).
31. A solution of urea niVrate is coloured
violet by furfuraldehyde and the solution gradu-
ally deposits a black substance (SchifC, B. 10,
773). — 32. Arrnnmdum sulphide forms thidfur-
furaldehyde C1H3O.CHS (Cahours, A. Ch. [3]
24, 281), which'is a yellow crystalline powder".
When heated thiofurfuraldehyde gives oS an un-
pleasant odour and yields a sublimate of a poly-
meride of furfuraldehyde [98°] (Schwanert, A.
134, 61)^—33. With benzil and' alcoholic NH, it
forma two componnds of the formula C^tH^gN^O,
[246°] and [above 300°] (Japp a. Hooker, C. J.
45, 684). — 34. With phenanthraquinone and
NH3 it gives 0„H5<^^C.O,H30 [231°] (Japp
a. Wiloock, 0. /. 39, 217).
Combination. C4H30.0H(OH).S03N8.
Formed by adding alcohol to a solution of fur-
furaldehyde in tionc. NaHSOjAq. White lamince,
with fatty lustre.
, Oxim CjHjO.OHiNOH. [89°]. (201°-208°),
Formed by the action of hydroxylamine (base)
on furfuraldehyde (Odernheimer, B. 16, 2988).
Long thin white needles. By heating with HCl
it is resolved into its constituents. Salts. —
C5H40.N0H,HC1 : white crystalline powder, sol.
water and alcohol. — C5H40.K(0Na) 3aq : white
scales. It gives characteristic pps. with the
salts of the heavy metals.
Ethyl ether G^fi.TS{0^t} : colourless
liquid, volatile with steam, lighter than water, in
which it is slightly soluble.
Phenyl hydrazide C4H30.CH:N.NHCeH5.
[98°]. Formed by adding a solution of phenyl-
hydrazine hydrochloride {i-v.) and sodium acetate
to an aqueous solution of furfuraldehyde ; 1 pt.
of furfuraldehyde in 10,000 i>ts. of water gives a
distinct crystalline pp. (Fischer, B. 17, 574).
Fine colourless plates. Insol. water, sol. ether,
from which solution it is ppd. in crystals by
adding ligroin.
Di-phenyl-hydrazide C4HsO.CH(NI'h)3.
[69°] (Cornelias a. Homolka, B. 19, 2240).
FTJEFTTEAMIDE 0,5H„NA i.e. (0,H40)3Nj.
[117°]. Formed as a crystalUne mass by allow-
ing furfuraldehyde to stand for some hours with
(5 times its volume of) cone. NHjAq (Fownes,
Tr. 1845, 253 ; A. 54, 55 ; E. SehiS.B. 10,1188).
Tufts of needles (from alcohol). Insol. coM
water, v. sol. alcohol and ether. When heated
with water it is slowly resolved into ammonia
and furfuraldehyde; this change is instantly
produced by acids. H^S yields thiofurfuralde-
hyde (v, supra). BoUing dilute KOH converts
furfuramide into the isomeric furfurine. When
heated with an alcoholic solution of phehyl
thiocarbimide it forms a crystalline compound
C22H,9N,S04, insol. water, si. sol. cold alcohol.
FUEFUBANE Ot^fi. Fmane. Tetra-
phenol. Tetrol. Tetrane. (31°). V.D. 2-4.
S.G. 2 -964; is -944. Formed by distilling
barium pyromucate with soda-Ume (Eohde,
B. 3, 90 ; Limprioht, A. 165, 281). Formed also
by the action of PCI5 on its dihydride. The
product is washed with EOHAq, dried by K2CO,,
and rectified (Henninger, A. Ch. [6] 7, 222)^ It
is a liquid. Unacted upon by EHO, aniline, or
hydroxylamine. Colours pilie-wood moistened
with Hdl emerald green (Canzoneri a. Oliveri,
Q. 16, 490). HCl converts it into a yellow-
black compound. PCI5 forms with it a black
compound. With Br, C.H^OBr, and C.HjOBrj
[5°] (65°) at 80 mm. are formed.
Furfurane dihydride CjH^O. (67°). S.G.
fi -967 ; 15 -95. V.D. 2-35.
Preparation. — A product of the action of
formic acid on erythrite. Separated from the
crotonic aldehyde, which is also formed, by frac-
tional distillation (Henninger, A. Ch. [6] 7, 218).
Properties. — Very stable liquid; does not
blacken nor polymerise. Forms a dibromide
CjHjBrjO. [12°]. (95° at 30 mm.). Yields fur-
furane (81°) when heated with FCl,. Gono. HI
FUKFURINE,
689
ind yellow phosphorus give sec-butyl iodide
(120°).
Debivativbs of inRTtjEANE. — FurfuTaue
/C4H,)0 is the oxygen analogue of thiophene
(0,HJS and pyrrole {C,n,)lSB., and all three
compounds are doubtless constituted in an ana-
logous manner. Since in their reactions they
resemble benzene ^and its derivatives rather than
the fatty group, it is generally held that their
molecules should be represented by ring formulas.
When pyromuoio acid is distilled with lime and
ammonia-zino chloride, it yields pyrrole as well
as furfurane. In this reaction we may suppose
the O of the furfurane directly displaced by NH
(Ganzoneri a. Oliveri, Gf. 16, 486). When a mix-
ture of pyromucic acid, aniline, and ZnCl^ is
heated (a)-naphthylamine is produced. In this
reaction the (nascent) furfurane acts (like an
alcohol, phenol, or glycide) as if it were the an-
hydride of the alcohol CH(OH):CH.CH:0H(OH),
the reaction being :
CH:CHv OH.CH=CH
I >0+ll I
CH:CH/ CH.C(NHj):OH
CH:OH.C.CH=CH
= 1 II I +H,0
CH:CH.C.C(NH2):CH
(C. a. O.). As another instance of the analogy
of furfurane with thiophene and pyrrole, we
may take the condensation of acetophenone-
acetonePh.OO.CHj.OHj.OO.Me or the alternative
Ph.C(OH):CH.CH.C(OH).Me, which by treatment
with PjOj loses H^O, giving phenyl-methyl-
CH— HO
furfurane | | . In an analogous man-
MeC— 0— CPh
ner, when heated with P^Ss, it gives phenyl-
CH— HC
methyl-thiophene | j ; and with alco-
MeO— S— CPh
holic NHj it gives phenyl-methyl-pyrrole
CH ^HC
I I (Paal, B. 18, 367). Just as
MeO— NH— CPh
Ph.CO.CHj.CHj.CO.Me yields a furfurane deriva-
tive by condensation, so acetonyl-aoetone
MeCO.CHj.CHj.CO.Me, di-acetyl-suooinio ether
Me.C0.CH(C0JEt).CH(C02Et).C0.Me, acetonyl-
aceto-acetio ether Me.CO.CHj.CH(COjEt).CO.Me,
and di-tolyl-ethylene CjH,.CO.CHj.CHj.CO,C,H,
yield corresponding derivatives of furfurane.
Diketones of the fctnn ECO.CR'(OH).CH,.CO.B"
and B.CO.CB':CH.CO.E" yield on reduction fur-
CR'.CH
furane derivatives / \ (Jappa.Klinge-
BO— O— CK"
mann, B. 21, 2932).
Furfurane being analogous to benzene, the
radicle C4H3O will resemble phenyl in its general
character. Baeyer proposed to call this radicle
' furfur ' ; but it is called furfuryl in this Dic-
tionary.
References.— BBNZo-Bi-METHTL-Di-njBrnBANB
Di-OABBOiHiio ACID, vol. i. P- 478; Bbomo-pub-
rUBANB, vol. i. p. 672; Dl-MBTHYIi-FUBrUBAUE,
MZIHYL-FUBFUBANE CABBOXYLIC ACIDS, Dl-PHENYL-
roBFUKAME and its oaeboxtlio aoid, Phentl-
METHHi-FnBFTIEANE and itS CAKBOXTLIO ACID,
PHENVIi-DI-METBTL-FiraFUBANB DI-OARBOXTMO
BTHEE, vol. i. p. 495 ; Di-toltxi-fubfueane, and
Pybohccio acid.
FUEFURANE-CAEBOXYLIC ACID v. Pyro-
MUCIC ACID.
Furfurane di-carbozylic acid v. Deliydro-
MUGIO ACID.
F1TBFTTBAN&ELIC AOID v. FuBFUBVii-AKaE-
IiIO ACID.
FTTKFUEBTITYLEIIE v. FuBFUBVL-BUTViiENB.
FUSFUE-CROXONIC ACID v. Fubfubyl-oeo-
loma ACID.
FTJEFTJE-CYANIDE v. Nitrile of Pteo-
UnCIC ACID.
FTJBFUEINE CsHiANj. [116°]. S. -75 at
100° ; -021 at 8°.
Preparation. — Furfuraldehyde, obtained by
distiUing bran with dilute H^SOf, is converted by
strong NH3 into furfuramide. Furfuramide is
boiled with very dilute EOH for 10 minutes, on
cooling furfurine separates as slender needles.
These are boiled with excess of oxalic aoid, the
solution is decolourised by animal charcoal and
allowed to crystallise. The acid oxalate then
separates. It is decomposed by NH, (Bahrmann,
J-pr. [2] 27,311; cf. Fownes, 2V. 1845, 253;
Stenhouse, A. 74, 289 ; Svanberg a. Bergstrand,
J.pr. 66, 239 ; Bertagnini, A. 88, 128).
ProperUes. — Soft white silky needles. Per-
manent in the air when dry, but turns brown
when exposed to moist air. SI. sol. water, v. e.
sol. alcohol and ether. Its solutions exhibit
alkaline reaction.
Beactions. — 1. Acetyl chloride added to an
ethereal solution of furfurine appears to form a
molecular compound, which, however, is decom-
posed by alcohol into furfurine hydrochloride and
acetyl furfurine, thus : 2C,5H,jO,N2-fAcCl
= CisHijOaNjiHOl + C.sHiiAoOjNj. — 2. Benzoyl
chloride appears also to form an unstable mole-
cular compound, it is decomposed by warm alco-
hol, and the product mky be C,5H,g(OEt)Bz0gN2.
3. Chloroformic ether, ClCO^Et, added to an
ethereal solution of furfurine, forms furfurine
carboxylic ether : C,5H„(C02Et)03N, [124°]
(Bahrmann, J. pr. [2] 27, 311).— 4. Fwfwrine
separates iodine from aqueous periodic acid
(Bodeker, A. 71, 64). — 5. A very dilute solution
of KNO2, added to one of furfurine sulphate,
gives app.of thenitrosamineC,5H„(NO)N203
which separates from ether in golden triclinio
crystals [112°] insol. water, m. sol. alcohol and
ether (E. Schiff, B. 11, 1250). But if the solution
of furfurine sulphate be not very dilute, a com-
pound 0^27^ fi,s [95°] separates after some
time. This is yellow and crystalline, and is also
formed by saturating an alcoholic solution of
furfurine sulphate with nitrous gas. It is insol.
water and ether, v. sol. alcohol, and forms a
platinoohloride(CaoHj,N50,5)iHjPt01,.
Salts. — ^Furfurine expels NH, from boiling
aqueous NH,C1, but is itself ppd. by NH, from
its salts in the cold. The salts of furfurine have
an extremely bitter taste. They are ppd. by
HgCl^ and by H^PtOlo.- B'HCl aq : tufts of silky
needles, v. sol. water, m. sol. HOlAq. Neutral
in reaction. Does not effloresce over H^SO^. —
B'jHjPtClB: longlight-yellow needles.— B'HIaq ;
slender, obUque, four-sided prisms. S. 18 in th? •
cold. — ^B'HBraq: short prismatic needles. S. 3-9
(Davidson, Ed. N. Phil. J. [2] 2, 284).—
B'jHjCr^O, : orange-yellow powder, si. sol. cold
water (p.). — B'HNO, : trimetric ; prisma (from
alcohol). — ^B'HClO^aq: long thin trimetric
690
FURFUKINE.
prisms [150°-160°]. EfBoresoes at 60°. V. sol.
water and alcohol (Bodeker, A. 71, 63 ; Dauber,
A. 71, 67).— B'HzSO, 3Jaq : prisms, v. sol. water,
m. sol. alcohol and ether, si. soL dilute H2S04.
Kfflorescent. — ^B'HjPOj : four-sided trimetrio la-
minsB. [200°-215°]. V. sol. hot water and alco-
hol, insol. ether. — ^B'^HgFO, : glittering, oblique,
four-sided prisms : v. sol. boiling water and al-
cohol, nearly insol. ether. Neutral in reaction. —
B'gHjFO,: long, oblique, four-sided prisms with-
out lustre ; permanent in the air ; t. sol. water
and alcohol, si. sol. ether. Has an alkaline re-
action.— B'jHjPjOiaq: glassy crystalline crust;
V. sol. water and alcohol ; neutral in reaction. —
B'H2C204: thin tables, v. si. sol. cold water.
Acetyl derivative CisHnAoN^O,. [c. 250°].
From furfnrine and AC2O by gently warming
(E. Sohifl, S. 10, 1188). White flocculent micro-
crystalline mass (from boiling alcohol). Insol.
water, m. sol. alcohol and ether. Not saponified
by boiling aqueous EOH. Does not combine
with acids. With bromine in HOAc it forms a
hexabromide CuHjjBrgAcN^O, which is ppd.
on adding water.
Ethyl-furfarine 0,5H„EtNjO,. The hydriod-
ide is formed by heating an alcoholic solution of
furf urine with EtI at 100° (Davidson) . It separates
by evaporation of the cold alcoholic solution in
prisms. S. 2-8. M. sol. alcohol and ether. Moist
AgjO converts it into a syrupy alkaline hy-
droxide which forms a platinochloride
(0,5H„EtNA)2ByPtCl,.
_ Isoamyl furfurine C,5H„(C5H„)N20j. The
hydro-iodide prepared by heating furfurine with
isoamyl iodide is a radio-crystalUne mass. The
platinochloride B'^H^PtCl, is a yellow pow-
der, si. sol. water.
' FVSFTTBO-SIiNZISINEv.FuBFUiuijjEHiDE,
Beaction 23.
FUBPUBOL V. VuRsnBMjmwzTm.
FTJEFUE0-(i8).NAPHTHYLAMINE v. Foe-
FOiiAu>EaTDE, BeociiUm 26.
FVBFUBONITBIIEv. Nitrile of FyBounoio
Aon>.
FirBFUBYL-ACBOLEitH v. Fubfubtl-aoby-
Lia ALSEHynE.
FUEFUBYI-ACETUC ACID C,H,0, i.e.
C4H30.CH:CH.00jH. FurfmacryUc acid.
[136°]. S. -2 (in the cold). Formed, by Perkiii's
zeaction, by heating furfuraldehyde (1 pt.) with
NaOAo (2 pis.) and Ac^O (2 pts.) at 250° for 11
hours; the solution solidifies on cooling, and
after dissolving in NazCO^Aq, the acid is ppd.
by HCl. The yield is 80 p.c. of the theoretical
(Baeyer, £. 10, 355; Marckwald, £.20,2811).
Formed also by oxidation of the corresponding
aldehyde, f urf uryl-acrylio aldehyde, by Ag^O (J. G.
Schmidt, B. 13, 2344). Formed, together with
glycocoll, by the action of boiling baryta-water on
f urfuryl-acrylurio acid, which is in the urine of
dogs that have taken furfuraldehyde (3.V.). Long
white needles (from water) ; volatile with steam.
The Ag salt is m. sol. hot water.
Beactions. — 1. Eednced by sodimn-amalga/m
to furfaryl-propionio acid. — 2. Bromine acting
on furfuryl-acrylio acid forms crystalline
C,HsBr,0„ which is decomposed by water into
di-bromo-furfuryl-ethylene and CO, (Hill, B. 20,
3359). — 3. When furfuracrylio acid is heated
with 95 p.c. alcohol (3'5pts.) and saturated with
HCl there is formed an ether CtHgO{C02Eit),
(286°), possibly (CO^t.CH,.CH2)2CO {since it
forms a phenyl hydrazide [115°] and an oxim
[38°]) ; it is a heavy oil, and the corresponding
acid forms thin prisms [138°], and has a crys-
talline silver salt. The acid CjH,0(C02H)2doeB
not combine with Br, is not reduced by sodium-
amalgam, and yields succinic acid when oxidised
by HNO, (Marckwald, B. 20, 2811 ; 21, 1398).
The acid ether 05Hj0(C0jH)(C0jEt) [68^ forms
a crystalline oxim [112°].
Ethyl ether -EW. (229°). Oil.
a-Chloro-forfaryl-acrylic acid
OACCHiCCLCOaH. [142°]. Prepared by di-
gesting a-chloro-fiufuryl-acrolom with Ag^O.
Properties. — Bosettes of white crystals, sol.
hot water, alcohol, ether, benzene, and chloro-
form, insol. light petroleum. It agglomerates
before melting. Cone. H2SO4 gives a red colour
changing to yellow on dilution.
Salts. — Gu salt is a greenish pp. dissolving
in ammonia with blue colour. — Pb and Hg salts
are white pps., sol. hot water. — Fe salt is a red-
brown pp.^Zn salt a white gelatinous pp. — Al-
kaline and alkaline earth salts are v. Bol. water
(P. Mehne, B. 21, 426).
FUEFTTEYLACBYLIC ALDEHYDE C,H,0,
i.e. C4H,0.CH:CH.CH0. [51°]. (above 200°).
Prepared by the action of aldehyde or paralde-
hyde and aqueous EOH on furfurol (Schmidt,
B. 13, 2342). Very volatile with steam. Long
colourless needles. V. sol. hot, si. sol. cold, water.
Beactions. — With aniline dissolved in acetic
acid it gives an intense green colouration. Se-
duces AgjO forming furfurylacrylic acid,
a-Chloro-farfaryl-acrylic aldehyde
C^HjCCHCCl-CHO. [79°]. From furfuralde-
hyde, chloro-acetic aldehyde, and aqueous NaOH
(Mehiae). Broad yellow needles, sol. hot water,
ether, and alcohol. Forms a phenyl-hydrazide
[157°] and an oxim [165°].
FUEFUBYLAMINE v. FuBFUBYL-cABBum^
AMnni.
FTTEFUEYL-ANGELIC ACID C,H,„0, i.e.
04H,O.CH:CEt.0O2H. [88°]. Formed by gradu-
ally heating furfuraldehyde with n-butyric an-
hydride and sodium ra-butyrate in an open vessel
to 180° (Baeyer, B. 10, 1364 ; Tonnies, B. 12,
1200). Silky needles (from hot water). Be-
duced by sodium-amalgam to furfuryl-valerio
acid.
FXrBFUEYL.BDTYIENE C4H,0.0H:0(0H,),.
(153°). V.D.=4-27. S.G.i|=-9509. Prepared
by cohobating a mixtdre of furfuraldehyde
(3 pts.), isobutyrio anhydride (7 pts.) and fused
sodium acetate (4 pts.) for twelve hours. Sodium
isobutyrate used instead of acetate gives the
same product.
Addition prodtiot toith Nfi,. — OgH,g04N2
[94°] ; large glistening tables ; easily soluble in
ordinary solvents. It decomposes at 145°-150°
into its constituents. On reduction with tin and
HCl it gives a mixture of furfurylbutylene oxide
C4HaO.CH:C(CH,), (a liquid (186°), sol. water
O
and volatile with steam) and amido-furfurylbntyl-
ene oxide (q.v.) C4H,O.C(NH,):C(CH,)2 (lonnies
O
a. Staub, B. 17, 851; cf. B. 11, 1511).
FUKFURYL-QUmOLINE.
691
rUBFUEYl-CAEBINOL C^B.fi,i.e.
CjHjO.OHjOH. Formed by reducing f urf uralde-
hyde with sodium-amalgam (Beilstein a. Sohmelz,
A.. Suspl. 3, 275). Formed also, together with
pyromuoio aoid, by the action of alcoholic KOH
on furfuraldehyde (Limpricht, Z. [2] 5, 699).
Syrup drying up to an amorphous resin; cannot
be distilled. HClA.q colours it green. Gives
Buocinic acid, HOAo, formic acid, and COj on
fusion with KOH. Aniline added to its aqueous
solution gives a yellow flocculent pp. of C„H„NO.
Aniline hydrochloride added to its alcoholic
solution ppts. reddish-green scales of
0„H„NO,NByhHCl (H. Sohifi, B. 19, 2154).
rUBFUEYL-CABBINYL-AMIlIE
0,H,O.CHj.NH,. (146°) (C. a.D.); (135°) (T.).
V.D. = 49-1 (obs.). Prepared by reduction of
pyromuco-nitrile with zinc and dilute H.^S04.
The product is distilled with steam, the distil-
late acidified and evaporated to a small bulk ;
on adding solid KOH the base separates (Cia-
mioian a. Dennstedt, B. 14, 1475 ; 0. 11, 332).
Obtained also by reducing the phenyl-hydrazide
of furfuraldehyde (45 g.) dissolved in alcohol
(600 g.) with 2^ p.c. sodium-amalgam (1350 g.)
in the cold {below 3°) (Tafel, B. 20, 398). Liquid.
Miscible with water. Strong smell. Powerful
base. Absorbs CO, from the air forming a crys-
talline mass [75°].
Salts. — ^B'HCl: colourless soluble prisms or
needles. (B'HCl)JPtCl4 : orange-yeUow trimetrio
plates, soluble in hot water, sparingly in cold. —
B'HjCjOiJaq: narrow scales. — The sulphate
forms minute needles. — The pi crate forms
golden prisms decomposing at 150° witiioat
fasion.
FirEFUIlYL-CEOTONIC ^CID 0^0, i.e.
C4H30.CH:CMe.00jH. [107°]. Formed by oxi-
dising the corresponding aldehyde with Ag^O
(J. G. Schmidt, B. 14, 675). Glittering plates
(from hot water) or slender needles (by sublima-
tion). Cone. H2SO4 forms with it a red solution.
FTrEFXTEYL-CSOTONIC ALDEHYDE
C,H,Oj i.e. C4H30.0H:CMe.CH0 (?) (120° at
110 mm.). Prepared by adding NaOH to an
aqueous solution of propionic aldehyde and fur-
furaldehyde (J. G. Schmidt, B. 14, 574). Colour,
less liquid. Volatile with steam. Gives a green
colouration with aniline and acetic acid, and a
yellow passing into violet with magenta de-
colourised with SO,. By Ag20 it is oxidised to
fnrfuryl-crotonic acid.
nJEnJEYI-ETHYL-CAEBINOI v. FoB-
nTETL-PBOPYL AIiOOHOL.
rUEFUEYL-EXHYl-PYEIDINE
Hexahydride G^^,O.CB.^.GB^O^^,^.
(246°). Prom furfuryl-vinyl-pyridine and sodium
in presence of alcohol (Merck, B. 21, 2709).—
B'HOl : [145°-148°].— B'HBr. [0. 136°].— -B'HI.
[c. 121°].
FUEFTTEYIiIDENE-ACETOIIE v. Fubbvbyl-
VlNtii METHYI. KETOItE.
PUEFUEYL - MEIHYLEITE ■SI^CABBAUIC
ETHEE 04H,0.CH(NH.C0ijEt)j. [169°]. Sepa-
rates immediately on adding a drop of HClAq to
a mixture of furfuraldehyde and carbamic ether
(Bisehofi, B, 7, 1081). Silky needles (from alco-
hol) ; insol. water, v. sol. alcohol and ether.
PUEFUEYl-METHYLENE-MAIONIC ACID
C4H,0.0H:0(C0^)^ [187°]. From its ether.
Prisms (from ether, alcohol, or HOAc) ; t. boL
water, insol. benzene, light petroleum, and
chloroform. Split up by heat into COa and fur-
furyl-acrylic acid. Beduced by sodium-amalgam
to furfuryl-isosuccihic acid.
Mono-ethyl ether EtHA". [103°].
Formed by gently Seating the diethyl ether with
potash. Trimetric prisms (from benzene). V.
si. sol. cold, m. sol. hot, water, m. sol. benzene
and chloroform, insol. light petroleum. Split
up by distillation into COj and fnrfuryl-aorylio
acid.
Bi-ethyl etherMik". Formed by heating
a mixture of furfuraldehyde and malonio ether
with AojO (Marokwald, B. 21, 1080). Oil; mis-
cible with alcohol. ,
Amide C4H,O.OH:C(CONH2)j. [180°].
Needles (from alcohol) ; m. sol. hot water, v. e.
sol. HOAc, insol. ether.
FUEFUEYL - DI - METHYL - P YBIDINE-DI .
HYSEIDE DI>CABBOXYLIC EIHEE 0„H2,N0.
OH,
C
^ EtO,0-/ \H-OO^t pg4^_ p^^j
CH,-0 CH— O.HiO
V
by beating a mixture of furfuraldehyde and
aceto-acetio ether with alcoholic KH,. Gdonr-
less crystals. On oxidation it gives furfnryl-di-
methyl-pyridine di-carboxylio aoid (B. Schiff a.
Puliti, B. 16, 1608).
PUEPUEYL-NIIEO-EIHYLENE
C4H,0.CH:CH(N0J. [75°]. Formed by the action
of furfuraldehyde upon an alkaline solution of
nitromethane (Priebs, B. 18, 1362). Long yellow
prisms. Easily volatile with steam. Gives on
nitration C4H2(N0J0.0H:CH(N0j) [144°] which
forms a crystalline dibromide [111°] and is oxi-
dised by CrO, to nitro-pyromujcio aoid.
PirEEirEYL-FEOFIONIC ACID
04H,O.OHMe.C02H. [51°]. From fnrfnryl-
acrylio aoid by sodium amalgam (Baeyer, B. 10,
357). Sol. water and ether. Coloured yellow
by HCl. Converted into furonic acid by suc-
cessive treatment with Br and Ag^O.
Amide OjHaO.CHMe.CONHj. [98°]. (270°).
Formed by heating the ammonium salt in a
closed tube for some hours at 220° (Marckwald,
B. 20, 2811). Needles, sol. water, alcohol, e^er,
and benzene, si. sol. light petroleum.
FVEFUEYL-FEOFYL ALCOHOL
C4E;,0.CH(0H).C^s. Fv/rfmyl-ethyl-earVimol.
(180° at 750 mm.). S.G. % 1-066 ; w 1-053.
Formed by the action of zinc ethyl on furfur-
aldehyde and treatment of the product with
water. Thick liquid (FawlinoS a. Wagner, B.
17, 1968).
(Py. 3)-FUEFUEYL.aTJIN0Lnra:
C^jNOjEjO. [92°]. (above 300°). Formed by
beating its carboxylic acid above its mdting-
point (Bobner, A. 242, 287). Long needles.
Insol, cold, V. si. sol. hot, water, v. e. sol. other
ordinary solvents.
Salts.— (B'H01)2PtCl42aq: small yellow
needles ; si. sol. cold, t. sol. hot, water. —
B'HOlAuCl, : lemon-yellow needles ; sol. hot
water. — ^B'HjCr^O, : orange-red needles ; sol. hot
water.— Pier ate: [186°]; large yellow plates.
60?
FURFURYL-QIJINOLINE CAEBOXYLIC ACID.
{Py. 3)-FTTEFUETL.ftTIIN0LINE (Py. 1).
CAEBOXYLIC ACID C5H5N(CAO)COjH. {Py.
S)-Fwrfuryl-cinchomc acid. [e. 215°]. Formed
by heating together furfuraldehyde, pyruvio
acid, and aniline in alcoholic solution (Dobner,
^.242,285). Greenish-yellow needles. SI. sol.
cold, T. sol. hot water, v. e. sol. alcohol, ether,
and benzene. Heated above its melting-point it
yields (Py. 3)-furfuryl-quinoiine.
. Salts.^-The Ag, Pb, and Cu salts are si. sol.
water. The chloride, nitrate, and sul-
phate, are v.sol. water. — (B'HCl)jPtClj: orange-
yellow needles ; si. sol. cold, v. sol. hot, water. —
(B'HCl)jAuOl, : lemon-yellow needles.
rUBFUHtL-ISOSTrCCINIC ACID
0,H,0.CH2.0H(C0,H)j. [125°]. Formed by re-
ducing furfuryl-methylene-malonio acid with
sodium-amalgam (Marckwald, B. 21, 1080). Long
slender needles, v. sol. water, ether, HOAc, and
alcohol ; almost insol. light petroleum. Split up
by distillation into 00, and furfuryl-propionic
acid.
FtrRFTTEYI-VALEEIC ACID CjH.jOj i.e.
C,H,0.0Hj.0HEt.C02H. Formed by redaoing
furfuryl-angelic acid by sodinm-amalgam (Baeyer
B. Tannies, B. 10, 1364; 12, 1200). OU. By
successive treatment with Br and Ag20 it is con-
verted into ' butyro-furonic acid ' OjHijOj.
DI-FUEFTJEYl-DI-VINYI, KETOITE
(C,H30.CH:CH)2CO. Di-fwfwral-acetone. [61°].
From furfuraldehyde (20 g.), acetone (6 g.), water
(400 g.), alcohol (300 cc), and NaOH (3 g.) dis-
solved m water (27 g.). Flat lemon-yellow prisms,
turning brown in air. Y. sol. alcohol, ether,
and chloroform, less sol. light petroleum. With
cone. H2SO4, AcGl, or fuming HCl it ^ives dark-
red solutions (Glaisen a. Fonder, A. 223, 146).
FTIEFTJBYE-VINYL METHYL KETONE
O4H3O.0H:CH.CO.Me. Fmfwal-acetone. [40°].
(135°-137°) at 34 mm. ; (229°) at 760 mm. From
furfuraldehyde (20 g.), acetone (30 g.), water
(1000 g.), and dUute (10 p.o.) NaOH (30 g.) left
24 hours in the cold, then extracted with ether
and distilled. TeUow oil, smelling of cinnamon
and of furfuraldehyde, but soon solidifies to thick
Erisms. V. sol. alcohol, ether, and chloroform,
iss sol. petroleum. In H^SO, it forms a brown-
ish-yellow colour turning wine-red on heating.
AcCl forms an orange liquid turning emerald-
green (Claisen a. Fonder, B. 14, 2468 ; A. 223,
145 ; J. G. Schmidt, B. 14, 1459).
FTJEFUEYL-(P^. 3)-VINYL-PYEIDmE
C4H,O.CH:CH.05H4N. [51°-53°]. From furfur-
aldehyde and (a)-methyl-pyridine at 165° in
presence of a little ZnOlj (Merck, B. 21, 2709).
Needles (from water) ; blackens in air ; v. sol.
alcohol and' ether. — B HHgClj aq [133°].—
B',HjPtCl„2aq. [155°].— B'08H2(NOj,).OH. [185°-
190°]; yellow needles.
mEFUEYL-VINYL STYEYL KETONE
C4HsO.CH:CH.CO.CH:CH.Ph. Fmfwral-henzyl-
idene-acetone. [56°]. From benzyhdene-acetone
(10 g.) and furfuraldehyde (7g.), or from fur-
f urtS-acetone (10 g.) and benzoic aldehyde (8 g.)
in presence of water (200g.), alcohol (130 g.), and
dilute (10 p.c.) NaOH (10 g.).
Propej-ties.— Straw-yellow plates (from boil-
ing light petroleum). Y. sol. alcohol, ether,
benzene, and chloroform,, less sol. petroleum.
Cone. H2SO4 forms a dark red, AcCl an orange
solution (Claisen a. Fonder, A. 223, 147).
FUEIL C,„HeO, i.e. C,H30.C0.C0.CjH,a
[162°]. Prepared by passing a stream of air
through a solution of furoin in alcohoHc NaOU
(E. Fischer, B. 13, 1337 ; A. 211, 221). Yellow
needles. Insol. water, si. sol. alcohol and ether,
V. sol. chloroform. By sodium-amalgam it ia re-
duced to furoin. By aqueous K0H(1:2) it is con-
verted into furilic acid. According to Jourdain
(B. 16, 659) alcohol containing a little ECy gives
furfuraldehyde and pyromucio ether.
Furil-octo-bromide CioHjO^Br,. [185°]. Crys-
talline. SI. sol. alcohol, m. sol. chloroform. Pre-
pared by the action of an excess of bromine on
f uril. On fusion it evolves Br and HBr, forming
dibromo-furil and a small quantity of bromo-
furil.
Bromo-furil C„HjBrO«. [110°]? Yellow
plates.
Di-bromo-faril CH^BrjO,. [184°]. Bnbli-
mable. Golden yellow plates.
Benz-furil v. vol. i. p. 462.
FTTEILIC ACID (C,H,0)jC(OH).CO,H.
Formed by rubbing furil with warm EOEAq,
adding dilute H2SO4, filtering from a separated
resin, and extracting the filtrate with ether
(B.Fiseher, 4. 211, 220). Unstable needles ; de-
composed at 100° ; m. sol. cold water, t. sol. al-
cohol and ether. A resin slowly separates from
the aqueous solution.
Di-bromo-furilic acid CijHjBrjOs. Formed
by the action of baryta-water on di-bromo-furil.
Its alcoholic solution is turned red by warming '
a^ter addition of some dilute H2S04.-r-BaA', :
slender needles.
FUEOlN C,„H,04. [135°]. Prepared by
boiling furfuraldehyde (40 g.), alcohol (30 g.),
water (80 g.), and potassium cyanide (4 g.) for
half an hour in a flask with inverted condenser.
Crystallised from toluene or alcohol (E. Fischer,
A. 211, 218 ; B. 13, 1334). Prisms. Distils un-
changed. SI. sol. hot water, alcohol, and ether.
Cone. H2SO4 forms a bluish-green colour. Weak
acid. Gives an absorption spectrum. The solu-
tion in alcoholic^ NaOH is bluish-green, and is
oxidised by the air to furil.
Acetyl derivative CigH^cO,. [76°].
Needles.
FXTRONIC ACID C,HsO,. [180°]. Formed
by adding bromine (1 mol.) to an aqueous solu-
tion of furfuryl-propionic acid (1 mol.), and
treating the product with AgjO (6 mols.) (Baeyer,
B. 10, 696, 1358). Colourless needles (from hot
water). SI. sol. cold water and ether. Cone.
H2SO4 forms a reddish-yellow solution. HClAq
is not coloured by it. Hydriodio acid and red
phosphorus at 200° reduce it to ra-pimelic acid
COjH.CHj,.CH2.CHj.CH,.CHj.C02H ? Sodium-
amalgam gives hydrofuronio acid C,H,,0,.—
AgjA".
Hydrofuronio acid 0,H,„05. [112°]. Formed
as above. Needles. — Ag^A" : m. sol. hot water.
PUSCO-SCLEEOTIC ACID C,4Hj40,. An acid
extracted by Dragendorff (C. G. 1878, 125, 141)
from ergot by ether, the ergot having previously
been treated with a solution of tartaric acid. It
may be separated from ' picrosclerotic acid' by
HjSO,, in which it is soluble (Blumberg, Ph. [3] "
9, 23). Its alkaline salts are soluble.
FUSEL OIL. A volatile liquid present in the
product of the alcoholic fermentation of the
saccharine liquids derived from potatoes, wheat,
QALANGIN.
593
&e., and of the juice of grapes, beet, &o. It
passes oyer in the latter portion of the distillate
when these hquids are rectified. Fusel oil always
contains amy! and ethyl alcohols, usually iso-
butyl and w-propyl alcohols, some fatty acids,
and ^ome ethers.
Fusel oil from potatoes consists chiefly of
isoamyl alcohol {q. v.) ; it often contains iso-
butyl alcohol and decoic acid (Dumas, A. 13,
80 ; Wurtz,'0. B. 35, 310; A. 85, 197; Johnson,
J.pr. 67, 262). Eeibstein (C. M. 87, 601) found
the following compounds in a litre of potato fusel
oil : 275 c.o. isoamyl alcohol ; 170 c.c. of pro-
ducts boiling above 132° and still containing
amyl alcohol; 150 c.c. isopropyl alcohol; 125
c.c. water ; 75 c.o. of a mixture of aldehyde, ethyl
alcohol, and ethyl acetate ; 65 c.c. m-butyl alco-
hol; 60 o.c. fec-amyl alcohol; 50 c.c. isobutyl
alcohol ; and 30 c.c. m-propyl alcohol.
Fusel oil tiommolasses contains isoamyl and
isobutyl alcohols (Wurtz, A. 93, 107), together
with palmitic (?) and heptoic acids and heptoic
ether (Mulder, /. 1858, 302). Bowney (0. J. 4,
372) found isoamyl decoate as well as isoamyl
alcohol, water, and EtOH in the fusel oil from
the Scotch whisky distilleries.
In fusel oil obtained in preparing alcohol,
ptirtly from wheat, partly from mwize, Wetberill
(Chem. Gaz. 1853, 281) found acetic and octoic
acids, isoamyl alcohol, but no butyl'alcohol.
In the fusel oil from heet-root molasses Feb-
ling (J". Ph. [3] 25, 74) found octoic and decoic
acids and an ether of decoic acid. In a fusel
oil from the same source Ferrot (C i2. 45, 309 ;
A. 105, 64) found ethyl, butyl, and isoamyl al-
cohols, compound ethers of the above alcohols
with caproic, heptoic, octoic, and ennoic acids
(c/. Muller, J. pr. 56, 103). Schrotter (B. 12,
1431) found in this fusel oil a liquid base CgHi^O,
(180°-230°) which forms a crystalline sulphate
B'HjSOf. He also observed another base
C,oH,eN,.
FUSIBLE METAL. An aUoy of Bi, Pb, and
Sn, which melts at 93-7° («. vol. i. p. 511).
FUSTIC. Two yellow dyes are known by
this name, viz. old fustic obtained from Moms
tinetoria and yowng fustic from Bh/us cala/mus..
The latter cohtains a glucoside ' fustin '
OsgHj^Oai? crystallising from water in needles
[219°], and split up by dilute H^SO, into
a sugar and Fiseiin la. v.) (Schmid, B, 19,
1735).
G
GALACTIN. This name was given by Morin
to a nitrogenous body resembling gelatin, said
to occur in milk, blood, &o. {J. Ph. [3] 25, 423 ;
[4] 14, 11). Wynter Blyth (O. J. 35, 531), after
freeing milk from casein and albumen, and
adding mercuric nitrate, obtained a pp. whence,
after removal of mercury as sulphide, and ppg.
a second time by lead acetate, a compound
(PbO)23C54H,sN4045 ? was formed. After remov-
ing the lead an amorphous alkaloid was left, called
by Blyth galaotin. More recently the same name
has been given by Muntz (C B. 94, 453 ; A. Gh.
[5] 26, 121; Bl. [2] 37, 409) to a non-nitrogenous
carbohydrate CsH,„05 occurring in the seeds of
leguminous plants. Muntz obtained it by ex-
hausting powdered lucerne seeds, Medicagb sati/va,
with water containing a little Pb(0Ac)2; ppg.
excess of lead by oxalic acid ; diluting with al-
cohol (IJ vols.) and purifying the pp. by redis-
Bolving in water and reppg. with alcohol. When
dried in the air it forms transparent nodules,
which swell up in water and dissolve slowly like
gum arable, forming a sticky solution which is
ppd. by basic, but not by normal, lead acetate,
and behaves generally towards metallic salts like
a solution of gum arabio. It is dextrorotatory,
[o]n = 84-6°. HNOj oxidises it to mucic acid.
Very dilute mineral acids at 100° give galac-
tose and a non-crystaUine sugar. Galaotin is
not inverted by saliva or pancreatic juice. A
substance resembling this galactin occurs in
agar-agar (Bauer, J.jor. [2] 30, 381).
Paragala«tin. This name is given by Sohulze
a. Steiger (B. 20, 290) to the (impure) substance
left after exhausting' finely-powdered lupin seeds
(Lu/pinus luteus) by ether, followed by very di-
lute cold potash. It constitutes 25 p.c. of the
Vol. II,
seed, is somewhat gelatinous, and is converted
into galactose by boiling dilute acids. After
treatment with hot 10 p.c. aqueous EOH alcohol
gives a gelatinous pp. whence an acetyl deriva-
tive CsH,Ac,Oj can be obtained.
GALACTONIC ACID C„H,jO,. Lactonio acid.
Small colourless deliquescent needles.
Formation. , — By oxidation of milk-sugar
(Barth a. Hlasiwetz, A. 122, 96 ; 158, 259), ara-
binose, or galactose (Eiliani, B. 13, 2307 ; 14,
651, 2529 ; 18, 1552) with bromine.
Preparation. — A solution of 100 grms. of
milk-sugar in 400 c.c. of 5 p.c. sulphuric acid is
boiled for 4 hours and freed from H^SO, by
Ba(0H)2. The filtrate concentrated to 300 o.e.
and cooled to about 35° is oxidised by treatment
with 200 grms. of bromine ; the yield is 70 p.c.
of the theoretical.
Beactions. — By heating to 100° it is converted
into its lactoile CjH,„0(, by loss of HjO. It is
reduced by HI to the lactone of y-oxy-ji-heioio
acid. HXOj oxidises it to mucic acid. Potash-
fusion gives oxalic and acetic acid. Galactonie
acid is slightly lasvorotatory. It does not reduce
Fehling's solution.
Salts.— ATSTa 2aq.— A'(NH4).— A',Oa 5aq.—
A'jOd aq : monoolinic needles (B. a. H.). —
A'jCd 4aq.
GALACTOSE v. Sugahs.
GALAHGIN C.sH.oOj. [215°]. Occurs, to-
gether with camphoride and alpinin, in the
galanga-root (Jahns, B. 14, 2807). Sublimes in
part. Light-yellow tables or flat prisms (con-
taining -lOaHjOH) ; needles (containing H^O).
Sol. ether ; S. (90 p.c. alcohol) 1-5 ; nearly insol.
water. Dissolves in alkalis forming a yellow so- '
Intion. Bedaoes alkaUne silver and copper solu-
QQ
£94
GALANOm.
tions. On oxidation with HNO, it gives benzoic
and oxalio acids. — CjjHgOjFb : amoipbous
orange pp.
Tri-acetyl derivative C,5H,0,(OAo)s :
[142°] ; colourless needles. ' Sol. alcohol, iqsol.
water.
Di-bromo- derivativeOiJSfiTjOi^ Yellow
needles.
GALBAinrm. a gum lesin supposed to be
the produce of Baton Galbanum or Ferula erii-
hescens, and imported from Africa and Persia.
Yellowish mass with bitter taste and strong
smell. It gives a yellowish-red or violet colour
with hydrochloric acid, and an orange colour
with a solution of bleaching powder (Hirschsohn,
0. 0. 1877, 182). Yields on distillation with
water a small quantity (7 p.o.) of terpene, S.O. -
■814, (160°), [o] = --18 (Mossmer, A. 119, 257).
According toWaUach (^.238, 81) oil of galbanum
contains a sesquiterpene C^^^ whose hydro-
chloride CisHjiHjClj melts at 118°. Potash-
fusion forms resorcin. Contains about 66 p.o.
resin, sol. alcohol, ether, and ligroin, and 25 p.o.
gum, sol. water. The resin contains 72 to 74 p.c.
carbon, and 8 to 8-5 p.c. hydrogen, and is sol.
lime-water. Alcoholic HCl acting on the resin
at 100° forms nmbellif erpn ; this body is also
formed by the dry distillation of galbanum and
other resins formed by umbelliferous plants
(Sommer, Ar. Ph. [2] 98, 1). The oily distillate
from galbaniim, when freed from umbeUiferon
by dilute XOHAg, has a splendid blue colour
(289°); it is soIa. alcohol, insol. aqueous alkalis,
coloured green by alcoholic FeOlj, resinified by
Br, and coloured yeHowish-red by HNO,. This
blue oU appears to be identical with oil of cha-
momile (q. V.) (Eachler, B. 4, 36).
GALIPEINE OjoHaNOa. [116°]. "An alka-
loid present in the Angustura bark. On evapora-
tion of the mother liquor from the oxalate or
sulphate of cusparine the salts of galipeine sepa-
rate out. White prisms, soluble in petroleum,
ether, and alcohol: Its salts are more soluble
than those of cusparine ; their solutions are of
a greenish-yellow colour resembling uranium
salts. — B'jHaSO, 7aq : [50°]; greenish -yellow
prisms. — Hydrochloride: prisms with tri-
angular base.— B'jHjPtOlj : bright yellow pp.
(£6mer a. Bohringer, Q. 13, 365).
GALITANNIO ACID C,HAia<l- A variety
of tannin said to occur in OaUvm verum and
O. Aparine (Schwarz, A. 83, 57).
OALLACEIomNE v. P^sbooauol.
OAI.LACEI0PHEN0NE v. iBi-ozy-iasio-
rHENONB.
SALLACTIC ACID C„H,,0,7 Formed by
bojling milk-sugar (200 g.) with oupric sulphate
(1,200 g.) and NaOHAq (Boedeker a. Struokmann,
A. 100, 267). YeUow syrup, miscible with water
and alcohol, insol. ether. Ppd. by lime-water
and by Pb(OAc)j.— CajA'' 3aq : flocculent pp —
HggA'^Saq: amorphous pp. — Pb^''6aq : powder.
GALIEIH OjdH.oO, ».&
CO<^«^.>0<^gjOg^>0.(7). Pyro.
gaJlol-phthaWCn.
Preparation. — By heating phthaUo anhydride
(Ipt.) with pyrogaUol (2ptB.) at 190°-200°; the
fused mass is dissolved in idcohol, filtered, and
water added to ppt. the gallein ; it is beat puri-
fied by means of the aoetyl-detivative (Baeyer,
B. 4, 457, 555, 663 ; Buohka, A. 209, 249).
Properties. — Brownish-red powder or glisten-
ing, minute crystals with green reflex ; si. sol.
hot, insol. cold, water, sol. alcohol, si. sol. ether,
insol. benzene. It dissolves in cone, sulphuric
acid with dark-red colouration. Its solution in
NHjAq and in lime- and baryta- water is violet.
Dyes fabrics mordanted with iron or alumina a
bluer shad? than logwood.
Beactions. — 1. With alkalis it forms salts,
which separate in metallic glistening green crys-
tals ; with excess of alkali a blue or blue- violet
colouration is produced; but acids reppt. un-
altered galleiu from this solution. — 2. On reduc-
tion with potash and zine-d/ust it yields at first
hydrogallem, and then gallin. — 3. On reduction
in amd solution gaUol CjoEuO, is formed. —
4. Fused with potash anhydro-pyrogallolketone
*^°<0 HioH)'>° ^^ produced.— 6. With con-
centrated sulphuric acid at 190° it yields coeru-
lein (q.v.). — 6. HNO, oxidises it to phthalio acid.
Tetra-chloro-gallem C20HSCI4O, 2aq (at 100°).
Formed by heating tetra-chloro-phthalio anhy-
dride with pyrogaUol at 195° (Graebe, A. 238,
337). Violet powder.
Si-bromo-gallein C,„'B.fiifi,. Formed by
adding Br to a solution of gallein in HOAc.
Golden crystals with metallic lustre, v. sol.
alcohol, si. sol. benzene. Its solution in NaOHAq
is brilliant blue.
Constitution of Gallein, The formula
CO<*^^<>C[CjHj(OH) JjO was at first assigned
to gallein from its analogy in its method of pre-
paration to phenol-phthalein, and the formation
of a tetracetyl derivative. But its behaviour
with reducing agents is not thus explained ; in
contact with potash and zinc-dust it takes up
two atoms of hydrogen, and the product should,
were the above formula correct, be analogous
to phenol-phthalin and possess acid properties.
But the hydrogallem shows no acid properties,
though on further reduction it yields an acid
substance, converted by sulphuric acid into cceru-
lin, the analogue of pheuol-phthalidin. Gallein
is thus possibly a peroxide, a view confirmed by
the fact that the tetracetyl derivatives of gallein
and hydrogaUein are identical (Buohka, A. 209,
249).
Hydiogalle'in C^gH^O, i.e.
C0< Y*>C <^^|^^jp>0 (?). Formed by
reduction of gallein {v. svpra). Crystalline pow-
der, sol. alcohol and HOAc, si. sol. water, insol.
benzene. It dissolves in alkalis with blue
colouration ; the solution becomes red through
oxidation if boiled for a long time.
Tetra-acetyl derivative OjoH^ACjO,.
[248°]. Formed by boiling hydrogaUein with
ACgO, or by heating gaUein with NaOAo and
AC2O. SmaU rhombohedra (from benzene) ; sol.
alcohol and HOAc, insol. ether. Gives with Br
in HOAc a di-brotno- derivative C^gH^rjAc^O^
[234°].
Tetra-bemoyl derivativ* 02oH,Bz,0_
[231°]. Formed by boiling gaUein with BzCL
Slender needles (from acetone) ; sol. alcohol and
benzene.
GALLIC ACID.
595
OalUn CjoEi^O, i.e.
CO,H.e^,.CH<g^^^|gj^jp>0(?). Formed by
redaction of galloin (q.v.). Small colourless
needles, turning red on exposure, sol. alcoh'ol
and acetone, si. sol. water. Decomposes car-
bonates ; converted by cone, sulphuric acid into
coeruleiDa.
Tetra-aeetyl derivative O^^t^kjofl,:
[220°] ; colourless leaflets (Buohka, A. 209, 268).
Gallein and gaUin dye mordanted fabrics like
barwood and logwood.
GALLIC ACID C,Kfl^ i.e. OaHj(OH),(OOjH)
[6:4:3:1]. Mol. w. 170. [220°-240^. S. 1 (in
the cold); 33 at 100°; S. (ether) 2-5 at 15°;
S. (alcohol) 28 at 15°. S.G. 4 1-694 (Schroder).
Occiarrence. — ^In gall-nuts, in sumach, in
hellebore root, in dividivi, in the acorns of
Quercus ^gilops, in green and black tea, in
leaves of Arctostaphylos wia-v/rsi, in sandal-
wood, in oolchicum, in strychnos bark, walnuts,
and in most astringent parts of plants (Soheele ;
Stenhouse, A. 45, 9 ; Kawalier, Sitz. W. 9, 290 ;
Hlasiwetz a. Malin, Z. 1867, 271; Fhipsbn,
C. N. 20, 116 ; BoUey a. BShi, Z. [2] 4, 501).
VormaVum. — 1. By exposing powdered gall-
nuts to the air for a month at 20° to 25° ; the
powder, which must be kept moist, becomes
covered with mould, which must be constantly
removed, and the product, as soon as the aqueous
extract ceases to ppt. a solution of gelatin, is ex-
hausted with water (Scheele ; Steer, Sitz. W. 22,
249 ; Wittstein, Ph. 12, 444 ; c/.Tieghem, C.B..
65, 1091 ; Weber, Ph.. [3] 10, 754).— 2. A solu-
tion of tannin is ppd. by cone. EjSO, and the
pp. added to boUing dilute H^SO, ; after a few
minutes gallic acid is deposited in crystals
(Iiiebig).— 3. By the action of hot cone. EOHAq
on di-iodo-salicylic acid ; a considerable portion
of the gallic acid being, however, converted into
pyrogallol (Lautemann, A. 120, 317). Demole
(^. 7, 1441) could not obtain gallic acid in
this way. — 4. By the action of aqueous KOH on
bromo-veratric acid (Matsmoto, B. 11, 139).
The acid so prepared melted at 197°- 200°.—
5. By potash-fusion from di-iodo-^-oxy-benzoio,
bromo-protooatechuio, and bromo-s-di-oxy-
benzoic acids (Barth a. Senhof er, B. 8, 754, 1477 ;
A. 142, 247 ; 164, 118).— 6. By heating gum kino
with cone. HClAq at 120 (Etti, B. 11, 1882).
Separation from tannin. — ^An infusion of a
plant which contains taimin and gaUio acid is
ppd. by gelatin ; the filtrate is evaporated to
dryness and exhausted with alcohol ; the alco-
holic extract is evaporated and the residue
crystallised from water, being, if necessary,
treated with animal charcoal.
Properties. — ^Long silky needles or triclinio
prisms (containing aq). Astringent taste but
no smell. Its solution is strongly acid. At
100°-120° it gives off its water of crystallisation;
at 215° it begins to decompose into GO, and
pyrogallol ; but if rapidly heated to 250° there
is formed, instead of pyrogallol, a black lustrous
insoluble mass, soluble in ajkalis (so-called
• Metagallic acid '). An aqueous solution of gallic
acid does not change if excluded from the air,
but in the presence of oxygen COj is evolved and
a black substance is deposited. This decom-
position is hastened by the presence of alkalis,
gpiling wi* exQess el KQB gives » bl»ck sub-
stance, the so-called ' tauromelanio acid.' Di-
lute alcoholic KOH gives ' gaUoflavin.' A solu-
tion of ammonium picrate gives a red colour
changing to a beautiful green (Dudley, Am. 2,
48): Gallic acid reduces Fehling's solution and
ammoniacal AgNO,. Ferric chloride gives a
bluish-black pp. (Chevreul, P. 17, 176) ; the pp.
dissolves in excess of FeCl, giving a green solu-
tion (Wackenroder, A. 31, 78 ; Etti, B. 11, 1882) ;
on heating CO, is evolved, the liquid becomes
colourless and contains ferrous salt. Pure fer-
rous sulphate gives ho colour at first, but the
liquid presently becomes blue. With a mixture
of EeClj and K,FeCy, gallic acid, like other re-
ducing agents; ppts. Prussian blue. Pure gallic
acid does not ppt. gelatin nor alkalis ; but when
mixed with gum it gives a pp. with gelatin. It
gives no pps. vrith albumen, gelatinised starch or
alkaloids, but tartar emetic and NH,C1 give a
heavy white pp. (Meissner, Ph. 1889, 626). A
solution of gallic acid containing CaCO, dis-
solved in 00, becomes blue when exposed to the
air. A solution of barium gallate gives with
excess of AgNO, a black pp. of silver, and the
filtrate contains an acid resembling quercitannio
acid (L5we, J.pr. 102, 111 ; Barfoed, J. pr. 102,
314). If a solution of barium gallate BaA', be
treated with excess of baryta-water a white pp.
is formed which quickly turns blue in Contact
with the air ; but if the ppn. and washing be
done with de-aerated water in an atmosphere
of hydrogen, the pp. quickly dried in vacuo ex-
hibits the composition BaC^HjO, 5aq (EClasiwetz,
J.pr. 101, 113). An aqueous or alcoholic solu-
tion of gallic acid, containing Na^SO,, is odloured
by iodine a transient purple-red (Nasse, B. 17,
1166), KCy colours an aqueous solution of
gallic acid red (difference from tannin) ; the
colour disappears on standing but reappears
again on shaking with air (Toung, Fr. 23, 227).
Beactums. — 1. The crystallised acid is un-
acted on by cold acetic anhydride and even
at 100° 2 g. require 2 hours for complete solu-
tion. The anhydrous acid behaves similarly
towards cold anhydride, but the same quantity
only requires |-hour for solution at 100°.
The products are in the first case almost
entirely the triacetyl deriviitive of gallic acid,
whereas in the second case there is formed in
addition to this a body [151°] having the pro-
perties of the pentacetyl derivative of tannin
(Bottinger, A. 246, 125),— 2. Aqueous EMnO^ is
quickly decolourised by gallic acid, so that it may
be estimated volumetrically in the same way as
oxalic acid (Morin, C. B,46,577), When rubbed
with dry EMnO, it even takes fire (BSttger,
P. Juhelhomd, 156). Dilute H^SO^ and KMnO,
in the cold give CnHnjOs ' hydrorufigallio acid '
a golden crystalline compound which gives a
crimson colour with the alkalis and their car-
bonates (Oser a. Kalmann, M. 2, 50), — 3. Com-
pletely oxidised to CO and CO, by electrolytic
oxygen (Bonrgoin, J. Ph. [4] 13, 376). Chromio
acid mixtwre acts in like manner (Bemsen, Am.
S. [3] 5, 354).— 4. An aqueous solution of KCIO,
and ECl gives iso-triohloro-glyceric acid
CsH,01,0« (Schroder, -4. 177, 282). If the
mother-liquor from which the iso-trichloro-
glycerio acid has orystaUised be boiled with tin
and HCl, the tin ppd. by E^S, and the liquid
ej^tracted by ether, prisms pf CiE^CLjO, are got.
993
596
GALLIC ACID.
It forms the ealts: OaHjA":: minate needles;
BaA"aq; and BaH2A"jlJaq. — 5. By heating
with bromine at 100° it is converted into tri-
, bromo-pyrogallol (Stenhonse, A. 177, 189). — 6.
Soda-fttsion gives pyrogallol, hexa-oxy-diphenyl,
and some phloroglucin (Barth a. Schreder, B.
12, 1259 ; M. 3, 649).— 7. Hot H^SO, converts it
into rufigalKo acid C,4HgOg {v. Hbxa-oxy-an-
thbaqdinone).— 8. KjSzO, acting upon a solution
of gallic acid in concentrated aqueous KOH forms
OA(OH),(O.SOi,.OK)(COjK) which crystallises
in slender needles {Baumann, B. 11, 1916). A
mixture of gallic and benzoic acids is converted
by H2SO4 into anthragallol ChHjOs (Seuberlioh,
B. 10, 38), V. Tri-oxy-ahihbaquinone. — 9. Gallic
acid is converted by warming with phosphorus
oxyohloride for some hours into digallio acid
C„HL,(OH)3.C0.0.08Hj(OH)jC02H which is pro-
bably identical with tannin (Schift, A. 170,49). —
10. Gallic acid (12 pts.) is converted by heating
with cirmamiic acid (10 pts.) and HjSO, (150 pts.)
at 50° into styrogallol 0,sH,„05 (E.'Jacobsen a.
Julius, B. 20, 2588).— 11. By heating with am-
moniwm carbonate in ■ a sealed tube an acid
CjHjO, is formed. — 12. Formic aldehyde forms
C,sH,jO,„ and C,sH,40„ (Baeyer, B. 5, 1096).—
13. By heating with arsenic acid to 120° ellagic
acid CnHeOj is formed (Lowe, Z. [2] 4, 603). If
the product insoluble in water and consisting
chiefly of ellagic acid be treated with sodium-
amalgam, acidified, and shaken with ether, several
substances are extracted, viz.: two crystalline
substances C,iH,„0, and 0,jH,„08, both si. sol.
water, and a rdore soluble crystalline body (Bern-
bold, A. 156, 116).
Salts. — NHjA'aq : slender needles (from
water). Obtained by passing NH, into an alco-
holic solution of galUo acid. — KjHA'jaq: pre-
pared by adding an alcoholic solution of EOH
gradually to an alcoholic solution of gallic acid
until the pp. begins to be permanent ; the liquid
is then shaken, when a flaky pp. separates. The
pp. is washed with alcohol, dissolved in water,
concentrated, and ppd. by alcohol in colourless
needles (Biichner, A. 53, 187). — NaA' 3aq :
slender needles ; prepared, as the K salt. —
BaA'2 3aq : prepared by neutralising a boiling
solution of gaUic acid with BaCO,, filtering, and
rapidly concentrating. Small plates; si. sol.
water, insol. alcohol. — Ba^CjEjOsSaq : v. sijupra. —
SrA'jiaq: small needles; prepared like'the Ba
salts ; si. sol. water, insol. alcohol; — GaA'2 2aq :
crusts of adherent needles ; prepared like the
Ba salt. — MgC,H405 2aq: obtained by boiling
magnesium acetate with excess of gallic acid,
evaporating to dryness, and treating with alco-
hol to remove free gallic acid. Light white
powder ; si. sol. water. — Mg3(C,H305)2 6aq. —
Al,(0,H20s)3 4aq ? Plocoulent pp. S. 2-02 at
20°; -84 at 100° (Lidoft, 3. B. 1882, 195 ; C. /.
42; 849).— ZnC^HjOsZnO ; deposited as a bulky
white pp. when gallic acid is added to a solution of
zinc acetate. — CoC^HjOsSaq: crimson powder. —
MnOjH^Osaq: crystalline powder, turns brown
in air. — PbO,HjOj|aq; obtained as a white pp.
which becomes crystalline by adding lead acetate
to an excess of a boiling solution of gallic acid
(Liebig, A. 26, 128).— Pba(0,H305)2PbO : yellow
crystalline salt ; formed by boiling the preced-
ing pp. in its mother liquor. — SnC.HjOjSnO :
f ^^e crystalline powder, obtained by adding
gallic acid to a solution of SnCl, previously
neutralised by NHj.
Acetyl derivative C5H2(OA6)3.C02H.
[166°]. Formed by boiling gallic acid with AcCl
or AcjO (Nachbaur, J. jjr. 72, 431 ; Sohiff, A.
163, 209 ; Bottinger, A. 246, 125). Prisms (from
water) ; si. sol. hot water, v. sol. alcohol and ether.
Gives no colour with FeOlj.
Bromo-acetyl derivative
CsHj(OH)j(O.C2H^rO).C02H. From gallic acid
and bromo-acetyl bromide (Priwoznik, B. 3, 644).
Amorphous.
Benzoyl derivative 0,Hj(OBz)sOOjH.
Amorphous; softens at 85° (Schiff).
Methyl ether CeH2(OH)3.002Me. [192°].
V. sol. water and alcohol (Will, B. 21, 2020).
Tri-methyl derivative
C3H2(OMe)8.0O2H. [167°]. Needles (from ether
or water) (W.).
Methyl ether of the trimethyl de-
rivative C3H2{0Me),.00jMe. [81°]. (275°). (W.).
Ethyl ether OjHj{OH)3.COJEt. [141°]
(Etti, B. 11, 1882) ; [150°] (E. a. Z.) ; [158°]
(G.). Formed by passing ECl into a solution
of gallic acid (1 pt.) in alcohol (4 pts. of 80 p.c),
evaporating at 70° until the liquid gets thick,
adding BaCOa, and extracting the solid masa
with ether (Grimaux, Bl. [2] 2, 94 ; Schiff, A. 163,
217). Prisms (containing 2^ aq) or anhydrous
crystals (from chloroform) (Ernst a. Zwenger,
A. 159, 28). [90°] when hydrated ; [140°-158°]
when anhydrous. SI. sol. cold, v. sol. hot, water ;
V. sol. alcohol and ether ; v. si. sol. CHCl,. Gives
a blue pp. with FeClj. Beduces ammoniacal
AgNOs and AUOI3. Split up by dry distillation
into alcohol, CO,, and pyrogallol. An aqueous
solution saturated by NaHGO, gives small
crystals of O^HiNaEtO^CiHsEtO,. SI. sol. cold
water; on heating with water sodium ellagate
C,,HjNaOs separates. Gallic ether gives a pp.
with aqueous Pb(OAc)j, which when <dried at
100° has the composition Pbs(C,H2Et05)2.
Tri-acetyl derivative of the ethyl
ether OeH2(OAc),CO,}Et. Oil, slowly becoming.
crystalline. Forms no pp. with lead salts.
Isoamyl ether OsH^{OB.),.GOJO^n. [139^.
Slender glittering needles ; si. sol. cold water,
V. sol. alcohol and ether.
Tri-ethyl-galUc acid C5H2(OEt)3.COjH.
[112°]. Colourless crystals. Sol. hot, si. sol.
cold, alcohol. Formed by boiling its ethyl-ether
with alcoholic KOH. Salts.— A'Ag : [c. 200°] ;
crystalline solid; si. sol. cold water. — A'2Ba:
very soluble crystals. Ethyl ether
C„H2(OEt)3COjEt: [51°]; glistening needles ; v.
sol. alcohol, ether, and benzene. Formed by
heating the ethyl-ether of gallic acid with ethyl
iodide and alcoholic KOH (Will a. Albrecht, B.
17, 2099).
Amide C,H2(0H)3C0NHj. [243°]. Formed
by the action of ammonia and ammonium sul-
phite on a moderately concentrated alcohoUo solu-
tion of tannin, the crude product being fraction-
ally crystallised from hydrochloric acid (A. a. W.
Knop, J. pr. 56, 329 ; H. Sohifi a. Pons, <?. 15,
177 ; B, 18, 487). Large plates (containing 1^ aq);
si. sol. cold water. Completely decomposed at
245°. Does not combine with HOl. Decomposed
by boiling with acids or (^alis into gaUio aqid
GALLIUM.
697
and NHj. The lead compound is a heavy white
powder, the copper compound
OaHj(OH)(02Cu).CONHj
is an azure-blue powder. The acetyl derivative
C5H2(OAo),.CONHj forms aggregates of colour-
less crystals, [o. 150°] sol. water, alcohol, HOAc,
and benzene.
Bromo-gallic acid CjHBr(0H),C02H. [above
200°]. Formed, together with the di-bromo- acid,
by rubbing gallic acid with bromine (Grimaux,
Bl. [2] 7, 479 ; Hlasiwetz, A. 142, 250). Mono-
chnic plates or needles (from water) ; si. sol. cold
water. Coloured by lime or baryta-water suc-
cessively red, greenish, and orange. PeCljColours
it blue-black ; alkalis give an orange-yeUow
colour.
Di-bromo-galUc add CjBr2(OH)3C02H. [140°]
(G.) ; [150°] (Etti). Formed as above, using
excess of Br. Long brittle needles or plates
(containing aq at 100°). Si. sol. cold water;
coloured successively rose, light green, and dark
red by lime or baryta-water. Its ethereal solu-
tion is turned indigo-blue by baryta- water. Al-
kalis form an orange solution, turned rose-red on
dilution. FeCl, gives a blue-black solution. With
AgjO it gives CO^ and pyrogaUol (Priwoznik, B.
3, 644). AcCl gives a tetra (? tri- ) acetyl deri-
vative crystallising in needles [91°] (P.).
GALLIN V. Gii/LEis.
GAILISIN OijH^A. [«]i = 77-3-82-7. The
cupric reducing power of 10-98 grams = that of
6 grams of glucose. Occurs in commercial
glucose (starch sugar), from the unfermentable
residue of which it is obtained by evaporating
to a syrup and repeatedly treating with absolute
alcohol, and finally with a mixture of alcohol
and ether, till all the water has been removed,
leaving the substance as a fine powder. White
amorphous powder. Very deliquescent. Not fer-
mentable by yeast. Slightly sweet insipid taste.
It is insoluble in ether, very slightly in absolute
alcohol, more easily in methyl alcohol and acetic
acid. It gives no pps. with Pb(OAc)j, HgClj,
FcjClj, or BaClj. It reduces AgNO, and Peh-
ling's solution. By heating with acids it is con-
verted into glucose.
Salts. — CjiHjjBaO,,, 3aq : white pp. formed
by adding baryta to gallisin in aqueous alcoholic
solution.— CijHmKOio : hygroscopic powder. —
GigHs^PbOigPbO : easily soluble white powder.
Hexa-acetyl derivative C,jH,804(OAc)j:
colourless glassy mass, insol. water, e. sol. alco-
hol, ether, benzene, CS,, &c. (Schmitt a. Cobenzl,
B. 17, 1000, 2456).
GALLIUUOa. At. w. 69-9. Mol. w. unknown
as y.D. of element has not been determined.
[30-15°]. S.G.If 5-96 solid; 6-07 liquid. S.H.
■079 solid ; -0802 liquid. Latent heat of fusion
= 1911 gram-units. Melted Ga remains liquid
at temperatures considerably under the H.P., but
solidifies by contact with a trace of solid Ga ;
other metals do not cause solidification. The
metal crystallises in quadratic octahedra. Cha-
racteristic lines in the emission-spectrum are
4170 and 4031 ; both lines have been reversed
by Liveing and Dewar {Pr. 28, 471).
GaUinm was discovered by Lecocq de Bois-
baudran in August 1875 in zinc-blende from
Pierrefitte (Hautes-Pyr6ndes) ; the observation
of two violet lines ia the spark-spectrum of this
blende led to the discovery of the new element,
The properties of Ga were found to be those of
the element e^a-aZummmm as predicted by Men-
delejefl {v. Chemical relations of Oallvmn).
Beferences. — The memoirs of Lecocq de Bois-
baudran are contained in 0. B. 81, 493, 1100 ;
82, 168, 1036, 1098 ; 83, 611, 636, 663, 824, 104* ;
86, 756, 941, 1240 ; 93, 294, 329, 816 ; 94, 695,
^54, 1227, 1439, 1625 ; 95, 18, 157, 410, 503,
703, 1192, 1332 ; and with Jungfleisch in G. B.
86, 475, 577. There are also meinoirs by Ber-
thelot in O. B. 86, 786; Dupr6, O. B. 86, V20,
Mendelejeff, C. B. 81,909; Nilson a. Pettersson,
C. B. 91, 232. A general account of gallium is
given by de Boisbaudran in Fremy's Encyclo-
ji4die Ohimigue, tome iii. cahier 5, pp. 202 et
sec[. [1884].
Occurrence. — In very small quantities in va-
rious zinc-blendes, and in many specimens of
commercial zinc. The best source of the metal
is the blende from Bensberg on the Bhine; de
Boisbaudran and Jungfleisch obtained 52 grams
of pure gallium from 4300 kilos, of this blende.
Teslmng blendes for galKwtn. — The blende is
treated with aqua regia, the solution is heated
to remove nitric acid ; when cold, zinc (free from
Ga) is added ; various metals are thus ppd. ;
while H is stiU being evolved the liquid is poured
through a filter ; large excess of Zn is added, and
the liquid is boiled until a white pp. forms ; this
pp. is collected, washed, and dissolved in HOlAq ;
the solution is concentrated to a small volume,
and examined by causing a small induction-
spark to play over the surface of the liquid, and
passing the light through a, spectroscope. 10
grams of a gallium-containing blende is sufficient
to give the chief spectral Unes of Ga.
Preparation. — 1. The powdered blende ia
treated with aqua regia, excess of blende being
always present in order to saturate the nitric
acid ; to the filtered liquid, when cold, Zn (free
from Ga) is added ; Sb, As, Bi, Cd, Cu, Au, In,
Pb, Hg, Ag, Tl, Sn, and Se if present, are thus
ppd.; while. H is still coming off, the liquid ia
filtered ; the filtrate is boiled with a large excess
of Za until a white pp. appears ; this pp. con-
tains all the Ga as hydrated oxide (or as a basic
salt) mixed with AljO,, ba^ic salts of Fe, Zn, Cr,
Co, and some SiO,. The pp. is dissolved in
EClAq, and H^S is passed into the liquid ; the
pp. is removed by filtration ; NHjC^HaOjAq or
NaC2H,02Aq, and acetic acid are added to the
filtrate, which is then ppd. by HjS ; it is advi-
sable to ppt. fractionally and to continue until
the filtered liquid ceases to show Ga lines in the
spectroscope ; if the filtrate from the last batch
of pp. shows the lines of Ga, a zinc salt must be
added and the process of ppn. repeated. The
pp. by HjS, which contains all the Ga, is well
washed and then dissolved in HClAq ; the Ga is
then ppd. by one of the following methods : (1)
the solution is boiled with as small an excess of
Zn as suffices to ppt. the Ga ; (2) the solution ia
boiled tiU HJS is all off, and then fractionally
ppd.byNHjAqorNaOHAq; (3) HjS is removed,
and Ga oxide is ppd. by addition of BaCO, or
CaCO,. The crude Ga oxide obtained by one of
these methods is washed and dissolved in HClAq ;
some Na^SOj is added (to reduce FeClj to FeCy,
and the liquid is boiled for some time ; excess of
CaCOj is then added, and the liquid is filtered at
698
aALLIUM.
nnce, as far as possible out of contact with air ;
this treatment is repeated twice; the greater
part of the imparities is thus removed. The
ppd. Oa oxide mixed with CaCO, is dissolved in
HClAq ; XH,Aq is added in excess, and the liquid
is boiled until it shows an acid reaction, water
being added from time to time ; the pp. is dis-
solved in HjSO^Aq, and the liquid is evaporated
until white fumes come ofi ; the last traces of
chlorides are thus removed. To the sulphate is
added considerable excess of pure EOH (free
from chloride). After gentle warming the liquid
is filtered (oxides of Fe and In are thus removed),
and the strongly alkaline liquid is electrolysed,
Ft electrodes are used, and the positive plate
should be 6 to 10 times larger than the negative.
The Ga is removed by the finger from the Ft
plate under warm water, and allowed to stand for
an hour or two in water acidulated with pure
HCl, and then in dilute pure potash solution for
a little at 60°-60°; it is then washed with water.
2. Iron may be used in place of zinc to efiect the
reduction of the solution of the blende ; only a
little Cd, Fb, &e,, are thus ppd., so that the first
filtration is omitted. The liquid containing Fe
is boiled till a white pp. forms, CaCO, in sUght
excess is added, and the liquid is filtered at once.
The pp. is dissolved in EClAq, and, the liquid is
reppd. by CaCO,, Ka2S0, being added to prevent
oxidation of ferrous iron. Finally the pp. is dis-
solved in HClAq, and oxides of Cr and Al are
removed by one of the following methods:
(1) tartaric acid and a Mn salt are added, and
then excess of NH,Aq ; addition of NH, sulphide
then ppts. MnS, and with it all the Ga; this
treatment is repeated two or three times; the
pp. is then dissolved in HClAq, digested when
cold with CaCO,, and the ppd. Ga oxide mixed
with CaCO, is heated as directed in 1 ; (2) K,FeCy,
is added to the solution in ECl; the pp. is
washed with water containing J to ^ its weight
cone. HClAq; the ferrocyanide pp. is then dried
and fused with EHSO,, and the fused mass is
treated with water ; to the solution excess of
NH,Aq is added, and it is then boiled for some
time ; the pp. is washed and dissolved in HClAq,
and this liquid is treated with NasSO, and CaCO,
as directed in 1.
Properties. — A grey metal, with greenish-blue
reflection ; fairly hard ; orystalUses in quadratic
octahedra ; brittle, but may be hammered into
thin plates, which can be bent without breaking.
When melted, Ga is a silver-white liquid with
faint reddish reflection. It melts at 30'16° and
remains liquid nearly to 2° ; if a small piece of
solid Ga is placed in the liquid metal below
30'1S° the whole solidifies; metals other than
Oa fail to produce solidification. According to
J. Begnauld, liquid Ga is electronegative to solid
Ga (C. B. 86, 1457). Ga is unchanged in air or
boiling water. Heated in air to full redness it
does not volatilise, and is oxidised only super-
ficially. It is superficially oxidised when heated
to redness in dry 0. The atomic weight of Ga
has been determined (1) by converting a known
mass of the metal into oxide (De Boisbaudran,
C. B. 86, 941) ; (2) by strongly heating gallium-
ammonium alum (De B., Ix.) ; (3) from determi-
nations of the y.D. of GaCl,, GaCl, (Nilson a.
Pettersson, C. J. Trans. 1888. 822) ; (4) by deter-
mining S.H. of Ga; (6) by establishing that
Ga-NHj sulphate is isomorphous with alum,
and hence assigning a formula to the Ga com-
pound {v. also Chemical relations of Gallium).
As the chlorides GaCl, and' GaCl, have both
been gasified (Niison a. Fettersson, O. J. Trams.
1888. 822) the atom of Ga appears to be both
divalent and trivalent in gaseous molecules.
Beactions. — 1. Heated to full redness in a/ir,
or oxygen, Ga is superficially oxidised. — 2. Does
not decompose water at 100°. — 3. Dissolved
slowly by hydrochloric acid with evolution of H.
4. Wa/rm rdtrie add dissolves Ga, forming
nitrate. — 6. Slowly dissolved by potash solution,
also by ammotUa. — 6. Combines rapidly with
chlorine at ordinary temperature, more slowly
with bromine, and with iodine only when heated.
7. AUoys very easily with as^MmimMwi; the alloys
decompose cold water rapidly.
Separation and Estimation of Gallium ; v.
De Boisbaudran, C. B. 93, 816 ; 94, 1154, 1227,
1439, 1625 ; 95, 157, 410, 503, 703, 1192, 1332.
Chemical relations of Gallium. — Gallium is
the fourth member of Group HI., in the group-
ing of the elements according to the periodic
law. When MendelejefE pubUshed his first ex-
tensive memoir on the periodic law, he was
obliged to leave the positions HI.-4 and in.-5 un-
filled; none of the known elements could be
placed in either of these places. Mendelejefi,
however, predicted the properties of the elements
which would be discovered to fill the vacancies.
One of the two unknown elements was assigned
a place in series 5. Now the differences between
the values of the atomic weights of the elements
in series 3 and 5, beginning with Group I. (and
omitting Group III. as the unknown element we
are considering is placed in that group) are, 40
in Group I., 41 in Group II., 44 in Group IV.,
44 in Group V., 47 in Group VI., and 44-5 in
Group Vn. Hence, it was' argued, the differ-
ence will be about 42 in Group in. ; but the
element in HI.-3 is Al with at. w. 27 ; hence the
unknown element in IH.-5 will have an at. w. of
about 27-1-42 = 69. By tabulating the differences
between the atomic weights of elements in series
4 and 5, of course omitting Group UI., the
following numbers are obtained ; 24, 25, — , 24,
24, 27, 26. Hence in Group in. the difference
will be about 25 ; but there was a gap in series
4 Group in., hence it was necessary first of aU
to calculate a value for the at. w. of the unknown
element which ought to find a place in III.-4,
and then to add 25 to this value. The result
was that the element in III.-4 should have the
at. w. 44 ; hence, 44 + 25 = 69. Ha^ng thus de-
termined the at. w. of the element which would
be placed in III.-6 when it was discovered, Men-
delejeff proceeded to determine the properties of
this element by studying (1) the properties of
the members of Group IH., (2) the properties of
the members of series 5, (3) the relations between
Group III. as a whole and other groups, especi-
aUy considering the position of the group in the
complete scheme of classification, and (4) the
relations of series 5 to other series. Group III. is
on the whole composed of metals; the only
decided non-metal is B ; but B is succeeded by
the metal Al. As the unknown element would
come next but one to Al, and would be followed
by T, La, In, Tb, Tl, it would certainly be a
metal, and would resemble Al generally. Then
GALLIUM.
oonBideiing that the unknown element woi^ld
follow the metals On and Zn, in series 6, and
would be followed by the element As which is
both metallic and non-metallic, As being suc-
ceeded by the non-metals Se and Br, it might
safely be asserted that the unknown element
would be metallic, but probably less metallic
than Gu and Zn. The composition and proper-
ties of the compounds of the Al group of ele-
ments determined the general composition and
properties of the compounds of the unknown
metal ; it would form an oxide Mfi,, a chloride
M2CI, or MClg, it would form salts MjSSO^
M3N0,, &o. Then, considering the position of
the element as regards Al, it was argued that the
relations of this body, when discovered, to Al
would be somewhat'similar to those of Zn to Hg,
or As to P, or Se to S. But as Zn is less like
Hg than As is like P, and as As is less like P
than Se is like S, it was concluded that the re-
semblance between the new element and Al
would be fairly close, although not quite so
marked as that between As and P, or Se and S ;
hence, it would probably form an alum. Guided
by such reasoning as this, MendelejefE was able
to tabulate precisely the properties of the ele-
ment which he placed in UI.-5, and to which he
gave the name of eka-alummiwm. The proper-
ties of galUimi were found to agree extremely
closely with those of eka-alwmamum (11. table in
vol. i. p. 352).
Lecocq de Boisbaudran calculated the at. w.
of Ga by comparing its spectrum with those of
analogous elements, and comparing this result
with the spectral relations of similar elements,
the at. ws. of all of which were known. The at.
ws. of the three similar elements E, Bb, Cs, show
the following relations : — 1
At. w. Differences
Eb . . 85-36 **'^^ 1-38
Cs . . 133 47-64
The increase in at. w. from Bb to Ca => increase
from K to Rb X 1 -I- -02983. Then comparing the
wave-lengths of the chief pairs of lines in the
spectra of these three elements, we get this
result : —
Wave-lengths Means Differences
„ 58311
*• • • 5812/
. Bb- -eaol} 625° "»
cs . . ^11} 6849
The increase in wave-length from Bb to Cs
'increase from £ to Bb xl + -3963.
Turning now to the three elements of which
Ga forms the middle member, we have : —
At. w. Differences
Al . . . 27-5T
Ga . . . ? ^ 8>0
In . . . 113-5J
And tabulating the wave-lengths of the principal
pairs of lines, we have ; —
Wave-lengtbs Means Differences
Ga. .%ll} 4100 59
^- -4101/
6821
429
599
206
4306
The increase in the wave-length from Ga to
In = increase from Al to Ga x 1 -h -4014. Theb
if it is assumed that theincrease in wave-length
(X) is related to theincrease in atomic weight (o)
similarly in both sets of elements, we have the
statement: —
XK to Cs : oE to Cs » aAI to In : oAI to In
■3963 : -02983 - -4014 : x
and X = -030214.
Kow, putting the difierence of at. w. between
Al and Ga as A, the difference between Ga and
In as B, we find that B = A(l + -080214) ; and as
Ax (2 + -030214) = 86, it follows that A=42-36,
and B== 43-64; hence the at. w. of Ga is found
to be (1) 27-5 + 42-36 = 69-86, and (2) 113-5 - 43-64
= 69-86. The observed at. w. is 69-9.
For the properties of the elements of Group
in., to which Ga belongs, v. Eabths, metals ov
TKB, p. 424.
Gallium bromideB. Ga and Br combine di-
rectly to form a colourless crystalline mass,
which is less volatile than GaCl,. Probably two
bromides, GaBr, and GaBr,, are produced ; but
they require farther investigation.
Gallium chlorides. Two are known, GaCl,
and GaCl,. Both have been gasified.
GauiXUII dichlobhii: GaCl,. Mol. w. 140-64.
V.D. at 1000°-1400° 60-6 (Nilson a. Pettersson,
C. J. 53, 825). Prepared by heating Ga in 01,
keeping the metal in excess ; or better, by heat-
ing GaCl, with Ga for a long time, and then dis-
tiUing in dry CO, (N. a. P., Z.C.). White'.transpa-
rent crystals, melting at 164°, and boiHng at c.
535°. When melted it may be kept for a long
time without solidifying. Vapour fumes in the
air. Deliquesces in moist air to a clear liquid ;
addition of water causes ppn. of a grey solid
{? oxychloride or suboxide, or GaCl v. N. a. P.,
i.e.), and evolution of H. Solution of GaCl, in
HClAq reduces KMnO,Aq. At a white heat
GaCl, appears to decompose into CI and a lower
chloride (K. a. P., Z.c.).
Galliuu tbichloiudi: GaCl,. Mol. w. 176-01.
V.D. 440° to c. 1000° 89; at 350° V.D. = 128
(Nilson a. Pettersson, C. J. 53, 824). V.D. 237°-
307° 161-6; at 377-6° V.D. = 113-2 (Priedel a.
Crafts, 0. B. 107, 306). These results point to
the existence of GajClg at c. 250°, and to the
gradual dissociation of this molecule into GaCl,.
S.G. ^ 2-36.
GaCl, may be prepared by heating Ga in
excess of Cl,,and distilling the product in N, or
by heating Ga in dry HCl gas free from air. II
forms long white needles, which melt at 75-5"
and boil at c. 215°-220°. When melted it re-
mains liquid at temperatures below its m.p.
Molten GaCl, absorbs gases readily, e.g. N
and CI, and gives them off again on crystallising.
It is deliquescent in moist air; dissolves in
water with production of much heat. When
this solution is evaporated an amorphous mass
is obtained, which absorbs moisture and becomes
gelatinous. When this gelatinous substance was
kept in closed tubes for several years small
crystals were obtained having the composition
Ga2Cl8.Ga,0,.13H,0 (L. de B.). At about 1100°
GaCl, begins to decompose into GaCl, and CI
(N. a. P., l.e.).
600
GALLroM.
Gallinm ferrocyanide is ppd. as a white salt
by adding K^FeCysAq to solution of GaCl,. Com-
position not determined.
Oalliam iodides. Two probably exist, cor-
responding with the two chlorides ; but they have
not been thoroughly investigated. Ga and I
combine when heated together.
Gallium oxides. Two probably exist.
GAI.LIUM MONOXIDE (? GaO) is probably formed
by heating Ga^O, to redness in a stream of H.
Tlie substance thus formed is a greyish-blue
mass, which dissolves in HNOjAq and in dilute
EOlAq; the solution in HClAq decolourises
KMnO,Aq.
GAUiiuM BGBQUioxiDE GfljOj. White solid,
formed by heating GaSNO,. Dissolves in acids
to form Ga salts. Does not melt at white heat.
Beduced to Ga by H at a high temperature.
S.H. -1062. Hydrated gallium oxide (? GaOsHj)
is ppd. from solutions of Ga salts by carbonates
and bicarbonates of the alkalis. It is sol. in
excess of the pptant., more sol. NH,Aq and
(NHJjCOsAq, and v. sol. KOHAq.
Gallinm; salts of. Only a few salts have
been prepared. The chief are GaSNO, and
' GajSSO, (v. NlTBATBs and Sulphates). They are
obtained by dissolving GajO, in acids and evapo-
rating. The sulphate forms an ammonia-alum
Ga23S04.(NHj2SO,.24H20.
Sulphyd/rio acid does not ppt. Ga salts. If,
however, the solution is alkaline, or is acidified
by a weak acid, and a metal is present whose
salts are ppd. by H^S, e.g. Zn, then the Ga is also
ppd. Potash ppts. Ga salts ; the pp. is e. sol.
in excess of the pptant. Potassiwmferrocyamde
gives a pp. with so little as ^^—^ part of a
Ga salt in an HCl solution. Bari/wm carbonate
ppts. Ga20g in the cold. Zino does not ppt. Ga
from acid solutions ; but as soon as the acid has
been neutralised by the Zn white flocks of GajO,
ppt.
Gallinm snlphide. The white pp. obtained
. by passing ElgS into a cone, solution of GaCl^ in
NHjAq, to which NH4 tartrate has been added, is
probably a sulphide of Ga. M. M. P. M.
GALLOCASBOXTLIC ACID v. FxiioaAi/i.01.-
M-OAEBOXYLIC ACID.
GAILOCYANINE Ot^,^fi,. Formed by
heating gallic acid and the hydrochloride of
nitroso-dimethyl-aniline in an alcoholic or HO Ac
solution (Nietzki a. Otto, B. 21, 1740 ; cf. Pabst,
Bl. [2] 38, 162 ; Kochlin, 0. N. 47, 170). Shiny
green needles, almost insol. water, alcohol, and
EOAo. Sol. alkalis with reddish colour. Cone,
acids dissolve it vrith reddish- violet colour. The
salts so formed are decomposed by water. Dyes
wool, mordanted with chromium, bluish-violet.
Anilide OjjHjjN.O,. Lustrous green
needles.
Methyl ether CisHnNjOsMe. 'Prune.'
Formed by the action of nitroso-dimethyl-
aniline hydrochloride on the methyl ether of
gallic acid. Is more basic than gaUocyanine
and forms a crystalline hydrochloride. Dyes
cotton, mordanted vrith tannin, or wool or cotton
mordanted with chromium, bluish-violet.
Di-aeetyl derivative of the methyl ether
OjiHgNgOfMeACp Small greenish needles (from
aloehol).
GAIXOPLAVnr C„H,0,? Obtained by dis-
solving gallic acid (50 g.) in alcohol (875 c.o.)
and water (1000 c.c), cooling to 0°, adding 135 0.0.
of 28 p.c. aqueous EOH, and passing air through
the solution (Bohn a. Graebe, B. 20, 2327).
Greenish-yellow plates, si. sol. water, alcohol,
and ether. Dissolves in alkalis and their car-
bonates forming yellow solutions. Dyes wool,
mordanted with chromium, yellow. — CjaHjEjOg:
greenish-yeUow crystals, t. si. sol. cold water ;
boiling water liberates free galloflavin.
Acetyl derivative CuHjAciO,. [230°].
White needles, v. sol. HOAo.
Chloro-acetyl derivative
C,3H,(C,C1H30),0,. [212°].
GALIOL CjjHijO, i.e.
0<^«^=|^|[|«>CH.CeH,.CH,.OH. Formed by
reducing gaUein (g. v.) with zinc-dust and dilute
H^SOi (Baeyer, B. 4, 556 ; Buohka, A. 209, 264).
Crystals, changing in the air to a reddish powder.
SI. sol. cold water and ether, v, e. sol. alcohol.
Penta-acetyl derivative C2,H,,Ac,0,.
[230°].
GAMBOGE. A gum-resin which appears to
be produced from Stala:gm,ites canibogioides, a
tree growing in Siam. It cohtains about 72 p.c
resin and 20 p.c. gum. Its powder is yellow.
It is a drastic purgative. It dissolves in alcohol
and ammonia ; the ammoniacal solution gives a
red pp. with BaOlj, and yellow pps. with ZnSO^,
with lead salts, and with AgNO,. Ether extracts
a red resin which forms a yellow powder; it de-
composes boUing alkaline carbonates forming
red salts (Buohner, A. 45, 94 ; Christison, A. 76,
344; Costelo, Ph. [3] 9, 1022). Potash-fusion
gives I phloroglucin, acetic acid, isouvitio acid
OjHj04, and pyrotartario acid (Hlasiwetz a.
Barth, A. 138, 61).
GABDENIN C„H,jO,. [164°]. Extracted
from ' dekamali,' a resin from Grordema Vucida.
After removing the volatile oil by distilling with
steam, the residue is extracted with weak spirit,
from which gardenin crystallises on cooling. It
may be purified by successive crystallisation
from benzene and petroleum spirit (Stenhouse
a. Groves, O. J. 31, 551 ; 85, 689 ; cf. Fluckiger,
Ph. [3] 7, 589). Deep yellow crystals. Almost
insol. water, m. sol. alcohol. Insol. alkalis, sol.
hot' HClAq. Its solution in - HOAc (30pts.)
treated with HNO3 (S.G. 1-45) gives gardenio
acid.
Gardenic acid 0,4H,„0,7 [0. 223°]. Deep
crimson needles, insol. water, light petroleum,
CSj, and almost insol. ether and benzene. Sol,
alkalis.
Acetyl derivative CuHjAcjO,. [244°].
Formed by the action of glacial acetic acid.
Insol. water, light petroleum, and CSj. Almost
insol. ether and benzene. Sol. alkalis.
Hydrogardenic acid OnH^Oj. [190°].
Formed by the action of HjSOa on gardenio acid.
Flat nee^es. May be re-oxidised to gardenio
acid.
GASLIC OIL. Contains allyl sulphocyanide
!Wertheim,.A.51,289) and a sesquiterpene C^H^^
254°) (Beckett a. Wright, C. J. 29, 1).
GABBTIHE. A substance crystallising in
iubea and occurring in the leaves and roots of
Qarrya Fremonti. It is sol. water and alcohol
GEOLOGICAL CHEMigTEY.
eoi
and gives a purple colour with H,SO, (Eosa, Ph.
[3:8,489).
GASES, ABSOEPTION OF. The more im-
portant chemical aapeots of the absorption of
gases are treated in the article Dissociation;
V. especially pp. 395-399.
GASES, ANALYSIS OF, v. ANAiysis, vol. i.
pp. 282-247.
GASES, COMBINATION OF, BY VOLUME,
V. Combination, chbmioaij, laws oi', pp. 286, 288.
GASES, DIFFUSION OF, vi. Dipfusion,
p. 384 ; and also Physioaii mi:thods.
GASES, TBANSPIBATION OF. The rate of
flow of gases through capiUaTy tubes is generally
called the transpiration of gases. Measurements
of transpirdtion-constants are more important in
physical than in chemical inquiries.
GASIFElNE, a misprint for Gampeine.
GAULTHEEIA OIL, or Oil of Wimtergreen, is
obtained from the leaves of GauUheria procv/m-
hens, growing in New Jersey, by steam distilla-
tion. It consists of methyl saUcylate (222°)
mixed with a small quantity of a terpene C,oH,j
(160°). V.D. 4-92 (Cahours, A. Gh. [3] 10, 327 ;
Procter, J. Ph. [3] 3, 276 ; A. 48, 66 ; Bieder-
mann, B. 8, 1677).
GEISSOSPEEMINE O.gHjjNA- [160°].
[o]d= —93-4° in a 1'5 p.o. solution at 15°. An
alksiloid occurring in the Pereira bark (Hesse,
A. 202, 148 ; B. 10, 2162). Small white prisms
(containing aq), sol. dilute acids but reppd. on
neutralisation. SI. sol. ether. Forms a purple
solution in cone. HNOjAq. It does not reduce
HjPtCle (Wulfaberg, Ph. [3] 11, 269). It gives
pps. with HgClu, with KjOr^O,, with potassio-
mercuric iodide, and with potassium picrate.
Salts. — B'^HjPtClj : yellow flocoulent pp. —
Aurochloride : brown amorphous pp. —
Oxalate: minute needles. — Sulphate: white
needles.
GELATIN V. Pboteids, Agpendiai G.
GELOSE CgHigOg. Forms the essential con-
stituent of China moss or Haii-Thao (Payen,
0. B. 49, 521 ; Morin, O. B. 90, 924). Used
for finishing cotton goods (Heilmann, D. P. J.
213, 622). When dissolved even in 500
times its weight of water it forms a jelly on
cooling. After drying it is insol. cold water,
alcohol, ether, weak alkalis or acids, and
Schweizer's solution. Dilute HNOj oxidises it
to muoio acid. Its aqueous solution is ppd. by
alcohol. Dilute HCl, acetic acid, and oxalic
acid deprive it of its. property of gelatinising;
heating with water under 6 atmospheres' pres-
sure has a like effect. A 10 p.c. aqueous solu-
tion is IsBvorotatory, [o]=-4°15'; but boiling
acidulated water sloWly changes this to a nearly
equal dextrorotation, the resulting solution re-
ducing Fehling's solution, and being no longer
ppd. by alcohol. By treating gelose with water
at 100° Porumbaru (C. B. 90, 1(381) got a Isbvo-
rotatory sugar C^jjOjaq.
GELSEMINE OajHagNjO,. S. (ether) 4. May
be extracted by alcohol from the root of
Gtdsemmm senvpervwens (Wonnley, Ph. [3] 13,
106 ; Gerrard, Ph. [3] 13, 502, 641 ; Bobbins, B.
9, 1182 ; Thompson, Ph. [3] 17, 803). Amor-
phous solid, melting below 100°- SI. sol. water,
m. sol. alcohol, v. sol. ether and chloroform.
Its solution has a bitter t^ste and is strongly
alkaline. It i8 very poisonous, producing con-
vulsions. Its hydrochloride is ppd. by the usual
reagents for alkaloids. Cone. B:2S04 gives a
greenish-yellow solution soon turning reddish-
brown; on adding KjCr^O, a cherry-red colour
turning to bluish-green appears. HNO, turns it
green.
Salts — B'HCl: amorphous. — B'jHjPtOlo!
amorphous. Using the formula 05jH|„,N,0,,.
Thompson describes the salts B'HjClj,
B'(HAuCl,)s, and B',(H,PtCy,.
Gelseminine. A resinous alkaloid which,
according to Thompson, accjompanies gelsemine.
Gelsemio acid. An acid which, according to
Wormley, occurs in Gelsemium sempervirens and
may be extracted by ether from the acidulated
root. It dissolves in 2,912 pts. of water and in
380 pts. of ether. HNO9 turns it yellow, the
solution becoming deep red on addition of am-
monia. Gelsemic acid forms fluorescent solu-
tions and is perhaps identical with sesculin.
TRIGENIC ACID v. Bthymdenb-biukbt.
GENTIANIN CnHioOj i.e.
CsH3(OH)j.CO.C|,HjMe02. QemUsin. OenUcmlc
add. The colouring matter of the root of
GenUana lutea growing in Switzerland and the
Tyrol and used as a tonic (Henry a. Caventou,
J. Ph. 7, 173 ; Baumert, A. 62, 106 ; Tromms-
dorff, A. 21, 134 ; Leconte, A. 25, 202 ; Hlasi-
wetz a. Habermann, B. 7, 662 ; A. 175, 63 ; 180,
348). Pale-yellow needles, v. si. sol. water, mi,
sol. ether, v. sol. boiling alcohol. Neutral to
litmus. Alkalis dissolve it, yielding a deep
golden solution. Between 300° and 340° it maly
be partially sublimed, but the greater part is
carbonised. It is not attacked by dUute acids.
Cone. HjSOj forms a yellow solution. HNO3
(S.G. 1-43) forms a green solution from which
water throws down green CnHj(N02)205aq.
Fuming HNO3' appears to form C,jH,(NOs)305.
Potash-fusion splits up gentianin into phloro-
gluoin, gentisic acid, and acetic acid. Gentianin
reduces AgNOj. Sodium-amalgam forms C„H,gO,
an amorphous red body.
Salts.— EHA"aq.—KH3A"2 2aq.—
K2H3A"5 17aq.— NaHA" 2aq : golden needles.—
Na2H4A"3aq. — NajH,„A", 2aq. — BaA"aq. —
PbA"Pb(bH)j.
Acetyl derivative Cj^HgACjOj. [196°].
Slender crystals (from alcohol).
GENTIANOSE Oj^HssO,,. [210°]. Prepared
from the juice of GenUana lutea .(taken in
September) by exhausting with alcohol (95 p.c.)
and fractionally ppg. with ether (A. Meyer,
B. 6, 135). Cplourless tables with sweet taste.
Sol. water. Its aqueous solution is fermented
by yeast. It is charred by HjSO,. It does not
reduce Fehling's solution. It is dextrorotatory.
GENTIOPICEIN C2„H3,0,2. [121°-125°].
Occurs in the root of Gentiana lutea (Kromayer,
Ar. Ph. [2] 110, 27). Needles ; v. sol. water, si.
sol. alcohol, insol. ether ; tastes bitter. Beduces
hot ammoniacal AgN03. Does not reduce Feh-
ling's solution. Split up by, dilute acids into
amorphous gentiogenin C^^ifi^ and a fer-
mentable sugar.
GENTISIC ACID v. Di-oxy-benzoio acid.
GENTISIC ALDEHYDE v. Di-oxt-benzom
ALDEHYDE.
GENTISIN V. Gentianin.
GEOLOGICAL CHEMISTEY. Since geology'
ic a science which deals primarily with the oon-
GEOLOGICAL CHEMISTRY.
stitution and histoiy of the earth, it is evident
that there must be many points at -which
it comes into relation, dh:ectly or indirectly,
with chemistry. Much of geological science is
devoted to the study of rooks, or those large
masses of mineral matter which build up the
crust of the earth. The chemist is of service to
the geologist not only in analysing these rocks,
or the mineral species of which they are composed,
but in explaining some of the processes by
which the rocks themselves may have been
originally formed, and in tracing the nature of
the alterations to which they have been subjected
since their formation. Hence the geological
chemist gives special attention to those natural
processes of rock formation in which chemical
reactions are involved, and he endeavours to
imitate the operations of nature by experiment
in the laboratory. The experimental method
was first introduced into geology by Sir James
Hall, of DunglasB, who, in order to explain the
origin of certain crystalline limestones, subjected
pounded chalk to a high temperature in closed
gun-barrels, and obtained, under certain con-
ditions, a crystalline mass of carbonate of cal-
cium some\<;hat resembling a saccharoidal marble
(T. E. 6, 101, 121). It must be remembered,
however, that much of the experimental work
recorded in the literature of chemical geology
refers to the synthesis of minerals rather than
of rooks. A rock may, it is true, be composed
of only a single mineral, but in most cases a
rock is an aggregate of several distinct mineral
species, and although the synthesis of each con-
stituent may be successfully effected, it by no
means follows that this work wiU throw light
upon the origin of the composite rock. (?or an
excellent account of the present condition of
mineral synthesis, see M. I4. Bourgeois, Bepro-
dtiction artiflcielle des min&raux, in Fremy's
Eney. Ch. 1884 ; and Fouqu6 and LSvy's Syn-
thise des Mmiraux et des Roches, Paris, 1882.)
Analysis of Bocks. — The simplest
method is of course to analyse the rock as a
whole, and in the case of a very fine-grained rock
in which it is impossible to separate the mineral
constituents individually, this is the only avail-
able method. The interpretation of the results
of such an analysis requires, however, consider-
able sagacity, more especially if the constitution
of the rock be complex. Two rocks, distinct in
composition, such as a granite and a trachyte,
may give the same biUk-analysis, while two
rocks of similar mineral composition may yield
different analyses. When the oxygen ratio, or
quantivalent ratio, of a rock is known, as also
that of each of its mineral components, it may
be possible to calculate the percentage of each
mineral in the rock (v. S. Haughton, Quart.
Jowm. Oeoiog. Soc. 18, 418).
Methods olfracUanal cmalysis have been in-
troduced for the purpose of effecting a chemical
separation of the constituents of certain rocks.
Gmelin, in his analyses of phonolites, was perhaps
the first to separate the part soluble in hydro-
ohlorio acid from that which was insoluble, and
to analyse each separately. Grave objections
may, however, be urged against this method, and
it is now rarely used. More trustworthy results
have been obtained by treating the rock, if com-
posed of various silicates, with hydrofluoric acid,
which attacks the several minerals in tmequal
degree. Such a niethod is sometimes useful in
controlling a balk-analysis.
Of late years considerable use has been made
of certain dense liquids for the purpose of effect-
ing the mechanical separation of the minerals
which compose a rock, in order that each con-
stituent may be isolated in a state of purity for
separate analysts. The S.G-. of the liquid is so
adjusted that when the rock is coarsely powdered
and thrown into the liquid certain of the minerals
float while others sink. Several such liquids
are now in common use in the geological labora-
tory (o. J. W. Judd, Proc. Oeoiog. Assoc. 8, 278 j
and F. Butley, Bock-formmg Minerals, London,
1888).
Sonstadt's solution, recommended by Church,
consists of a solution of Hgl, and KI ; it may
be obtained with S.G. 3-196 (O. N. 29, 127 ;
Neties Jahrb. '/. Min., Beilage 1, 179). It is also
known as Thoulet's solution. If a rock con-
sisted of plagioclase with S.G. 2-7 and augite
with S.G. 3'1, and these minerals were set free
by mechanical disintegration of the rock, a com-
plete separation might readily be effected in
Sonstadt's solution with S.G. of about 3. The
poisonous and corrosive character of the solu-
tion, however, tends to limit its use. Klein's
solution is a boro-tungstate of cadmium, less
dangerous than SQnstadt's, and capable of at-
taining to a higher S.G., the maximum being
about 3'6. The solution has, however, the dis-
advantage of being decomposed by carbonates,
and therefore if these be present in the rock
they should be removed before the solution is
used (Bull. Soa. Mm. France, 4, 149). Bohr-
bach's solution resembles Sonstadt's, but con-
tains Bal, in place of EI ; its maximum S.G. is
3-58. It is unfortunately decomposed in the
presence of water, so that all minerals used
must be perfectly dried {Neues Jahrb. 11, 186).
Brauns has recommended the use of methyl
iodide, which has S.G. 3-337 at 10". Br£on ad-
vocates the employment of fused FbCL,, either
alone or mixed with ZnClj; but though by
properly adjusting the proportions of the con-
stituents it may be prepared of high S.G., its
use in a state of fusion is attended with much
inconvenience (BuZ2. Soc. Mm. France, 3, 46).
, The S.G. of a heavy solution may be con-
veniently determined by means of Westphal's
hydro-balance (Neues Jahrb. f. Min. 2, 87).
The S.G. of very small fragments of minerals
and rocks may thus be accurately taken: the
fragments are placed in the dense solution, which
is then diluted nntil they remain suspended in-
differently in any part of the liquid (v. also
W. J. Sollas, ProcB. Dublin Soc., Jan. 19, 1885).
The separation of one mineral from another,
when in small particles, is bbst effected in a
special type of separating funnel, devised by
Harada and improved by Brdgger. (For the
subject generally v. Bosenbusch, Mikroskop.
Phydog. 2 Aufl. Bd. i. [Stuttgart], 1885, pp. 194,
215 ; English translation by Iddings, 1888. p.
91.)
The mechanical separation of the constituent
minerals of a rock, previous to chemical analysis,
is aided by the use of a powerful magnet. With
an electro-magnet of great power, silicates rich
in iron, such as hornblende, augite, and biotite,
QEOLOGIOAL CHEMISTEY.
603
may be picked out of the pulverised rook (Fouqufi
a. IiiYj, Min. Micrograph. [Paris, 1879J, 115).
(For a large oolleotion of analyses of rocks con-
sult J. Both, Die QesUims-Anaiyaen [Berlin,1861],
and his BeOarOge, 1873-84.)
Micro - chemical examination ot
rocks. — ^The miorosoopio examination of thin
sections of rocks, which forms an Important
branch of modem petrography, has led to the
introduction in recent years of certain micro-
chemical tests for distinguishing one mineral
species from another. The micro-chemical me-
thods do not aim at effecting a complete analysis
of the microscopic constituents of a rock, but
are used father for the purpose of controlling
optical determinations.
The rock maybe coarsely powdered in a steel
mortar, and the particles to be examined after
separation of the fine powder by a sieve may be
picked out by aid of the forceps, or if too small
maybe removed on the point of a needle moistened
with glycerine, from which the accumulated grains
may be detached by dipping the needle into water.
Any steel particles derived from the mortar may
be separated by a magnet. In other cases the
Gonstituentmineralsare so minute that it becomes
necessary to prepare a thin section of the rock
and subject it to examination under the micro-
scope. By means of a needle, the grains to be
examined may be picked out from the section.
It is convenient for the operator to commence
by detaching the fragments near the edge, and to
work patiently thence towards the centre of the
section. The section is, of course, not protected
by a cover-glass; and the Canada balsam by
which the slioe is cemented to the glass is dis-
solved off by treatment with alcohol.
In some cases the particles to be examined
cannot conveniently be separated, and it then
becomes necessary to attack the mineral in the
section itself. The particular mineral to be tested
is brought into the field of the microscope, and
a perforated cover-glass is then drawn over the
seciion in such a way that the mineral is just
under the perforation. Through this aperture
the balsam is dissolved, and the mineral exposed
ready for attack by the reagent. If hydrofluoric
acid is to be used the section is covered with a
perforated slip of platinum foil instead of a cover-
glass. Sy means of a pipette a drop of the solvent
is lodged on the slide, and the liquid may then be
conducted to the mineral exposed at the aperture
by the point of a platinum vrire.
The general method in these micro-chemical
reactions is to produce certain compounds which
present di^inctive crystalline forms capable of
recognition under the microscope. In Boricky's
method the microsoopicmineralsareattaoked with
H^SiFgAq, which forms a series of crystallised
sihcofluorides, many of which are sufficiently
characteristic in form to be readily recognised.
Uncertainty is, however, introduced by the fact
that several of the silicofiuorides are isoi^orphous.
Behrens attacks the rock with HFAq, and treats
the product with HjSOjAq. In Streng's pro-
cesses most of the salts crystallise out as chlorides.
For the special reactions, and for figures of the
microscopic crystals produced by these reactions,
reference may be made to Klement a. Benard,
Reactions ilficrocHmi2ites,Brussels,1886; Hans-
hofer, Mikroskopische Beactionen, Munich, 1885;
'Boreas, Mikrochemische Methoden gur Mineral-
analyse, Vers, en Med. d. k. Ak. Wetensoh.,
Amsterdam, 1882 ; and Ot. Borioky, El&nente
einer neuen chem.-rmk. Min.- u. OesteinsanaCyse
Arch. d. naturw. Landesfor. v. Bdhmen, Prague,
1877.
The geological chemist is often called upon
to decide the nature of a given felspar in a rook,
and for this purpose the method introduced by
Szab6 of Budapest is convenient. An extreniely
small particle of felspar is introduced into the
flame of a Bunsen burner provided with a special
chimney of sheet-iron. The proportion of soda
or potash may be approximately determined by
comparing the extent of the yeUowor red coloura-
tion with the standard plates issued by Szab6. In
experienced hands this process yields remarkably
precise results (v. Szab6, Ueber eine new Methode,
die Feldspathe in Gest&imen zu bestmimen, Buda-
pest, 1876 ; andF. Butley, Bock-formmg Minerals,
London, 1888, p. 9).
Olassification of Boekt, — Some rocks
have evidently been formed as deposits in a
watery medium, while others have existed at some
period at a high temperature and been more or
less completely fused; hence arise two great
groups of rocks; one of aqueous, the other of
igneoiis, origin. Certain rocks, whether aqueous
or igneous, have suffered such alteration since
their formation that their original characters are
no longer to be recognised by direct observation,
and hence these are known as meta/morphic
rooks. Of the so-called aqueous rocks a few
have been deposited directly from solution as
chemical precipitates ; but by far the larger num-
ber have been thrown down as sediments from a
state of mechanical suspension. The aqueous
deposits are known as sedimentary or stratified
rocks, while the igneous rocks are often de-
scribed as vmstratifl^d or m^issive. ' In addition
to these types there are a few rocks, like coal
and certain limestones, which owe their origin^
directly or indirectly, to organic agencies, and.
are hence termed orgame rocks. But though
the ultimate origin of such deposits is organic,
the changes through which they have passed in
reaching their present condition are essentially
chemical.
It usually happens that several modes ot
formation have contributed to the production of
a single rock. Thus, rocks formed as chemical
precipitates, though practically homogeneous,
may contain an admixture of foreign matter re-
presentingmaterial that was mechanically thrown
down during precipitation. On the other
hand, a sedimentary rock frequently has its con-
stituent grains bound together by mineral mat-
ter which has been precipitated in association
with, or subsequent to, the mechanical deposit,
and has acted as a cementing medium ; a sand-
stone, for example, may have its component
grains nnited by mineral matter precipitatedf rom
solutions percolating through the original mass
of sand. (On the origin and classification of
rocks, consult A. Oeikie, Text-hook of Geology,
2nd.ed., 1885 ; A. H. Green, Physical Geology,
vol. i., 3rd ed., 1882 ; J. J. H. Teall, British
Petrography, 1888 ; A. de Lapparent, Traiti de
Giologie, 2nd ed., Paris, 1885 ; and E. Credner,
Slemente de Geologie, Leipzig, 3rd ed., 1876.)
In dealing with igneous rocks it is always
604
GEOLOGICAL CHEMISTRY.
desirable io ascertain the proportion of silica in
the rock as a whole, since a comm n classifica-
tion of such rocks is based upon this datum.
Bunsen, in studying the rocks of Iceland, sug-
gested that aU igneous rocks have been formed
by admixture of two magmas which he termed
the normal trachytic and normal pyroxenic (P.
83, 197). Durocher afterwards developed a
theory which derived the rocks from two mag-
mas situated at difierent subterranean depths,
termed by him acid and basic, and practically
corresponding respectively with the trachytic
and pyroxenic magmas of Bunsen (Durocher,
Essaide Pitrohgie convpa/rie, Ann, de Mines, 40,
1857, pp. 217,676). At the present time most
petrographers define the acid or Ught locks as
those containing from 65 to 80 p.c. of silica, and
having S.G. 2'3 to 2-7 ; they usuaUy contain a high
proportion of alkalis, especially potash, and but
a small percentage of lime, magnesia, and oxides
of iron. On the other hand, the basic or dense
rocks contain only from 45 to 55 p.c. of silica,
but have S.G. rising from 2-5 to as high as
3-1 ; they are characterised by a low percentage
of alkalis, with more soda than potash, and by
a high percentage of lime, magnesia, and oxides
of iron (v. TeaU, Brit. Pet., cap. ii. ; and
on the classification of igneous rocks, Bonney's
anniversary address, Qeol. Soc, 41, 1885).
Chemically -formed Rocks. — The
chemical precipitates which are of interest to
geologists, as having been formed on a, large
scale in nature, belong chiefly to the groups of
carbonates, sulphates, and chlorides, represented
respectively by such rocks as limestone, gypsum,
and rock-salt. Perhaps the simplest example
is offered by rock-salt, since this has been
formed by the mere evaporation of a natural
brine. On the composition of sea-water — a sub-
ject of much interest to the geological chemist —
V. Dittmar, Bep. of Challenger, 1884; Forch-
hammer, T. 155, 203; J. Both, Allgemeine u.
Chemische Geolog., Bd. 1 [Berlin, 1879]; and
Bischof, Chem. u. Ph/ys. Geolog., 2nd ed., Bd. 1
[Bonn, 1863], p. 426.
Bock-salt has usually been formed in inland
sheets of salt-water. These are either isolated
portions of the sea or the relics of lakes which
were originally fresh but have acquired salinity
by the accumulation of salts introduced by
river-waters. The great Salt Lake of Utah,
situated in an area of inland drainage, receives
streams which bring in salt ; but, having no
outlet, the waters tend to become concentrated.
In this arid region evaporation is rapid, and
along the shallow margin of the lake vast quan-
tities of common salt spontaneously crystallise
during the dry season ; while in winter, whenever
the temperature falls below —6-5° NajSOj is
ppd., the quantity of this salt formed in a single
season amounting to thousands of tons. Many
ancient lakes have in the course of time com-
pletely disappeared by desiccation, and their
positipn is now marked by extensive saline de-
posits. For the chemical history of a fossil lake,
see J. C. BusseU's ' Lake Lahontan ' in Mono-
graphs of U. S. Oedlog. Swro. 1885.
On the evaporation of a salt-lake, or saline
lagoon, the least soluble salts will tend to crys-
tallise first, the order in which the salts are suc-
cessively deposited being inversely as the order
of their solubility. Such a process of fractional
crystallisation in nature is illustrated by the re-
markable salt-deposits at Stassfurt in Prussia.
In the lowest beds the rock-salt is associated
with gypsum, anhydrite, and carbonate of cal-
cium ; but above the rock-salt there are deposits
of deliquescent compounds, rich in potassium
and magnesium, which remained in the mother-
liquor after the NaCl had separated. The asso-
ciation of the rock-salt and anhydrite in alter-
nate layers has led to the suggestion that they
represent seasonal deposits, the former having
been deposited in the warmer, and the latter
in the colder, parts of the year. The soluble
salts above the main mass of rock-salt, known
locally as Abravmsalee, consist chiefly of poly-
halite (KjSO,.MgS04.2CaS04.2H20), kieserite
(MgS04.H20), and carnaUite (KCl.MgClj.6H2O) ;
V. Bischof, Die Steimsalz bei Stassfwrt, 2 Aufl.
1875 ; Ochsenius, Die Bildung der Steinsalz-
lagen, 1877 ; Preeht, Die Salsindustrie von Stass-
fwrt ; Bauerman, Proc. Civil Eng. 88, 415 ; and
0. Napier Hake, S. C. I.
Origin of Limestone. — One of the commonest
examples of a chemically -formed rock is afforded
by certain deposits of Umestonevihiah. have been
ppd. from calcareous waters. Such are the de-
posits known as calcareoiis sinter or tufa, so
commonly formed by springs flowing through
limestone districts, and forming in some cases
important rock-masses, like the tra/eertine, or
' Tibur stone,' of Tuscany. But while certain
limestones are the result of direct ppn., it ap-
pears that by far the greater number of such
rocks owe their origin to organic agencies. Such,
for instance, is the chalk which is largely made
up of the calcareous tests of foraminifera ; such,
too, are the coral-limestones, which are formed
in large measure of the hard corallia of certain
actinozoa. On the nature and origin of lime-
stones, V. H. C. Sorby's Presidential Address to
the Geolog. Soc.,. 1879 (Quairt. Joum. Qeol. Soc.
85, 66, 'Proc.') ; also F. Senft, ' Die Wanderun-
gen n.Wandelungen d. Eohlens. Kalkes ' (Zeitsch.
d. deutsch. Geolog. Ges., 13, 1861, 263).
When CaCO, is deposited from thermal
springs, the pp. usually takes the form of a/ra-
gonite, the orthorhombic species of CaCO,,
harder and denser than calcite. The ppn. of
aragonite is well illustrated by the Sprvdelstein
of Carlsbad. The water in which this is formed
has a temperature of about 73°G., and though
containing only 0*29 p.c. of CaCO,, it readily de-
posits this salt on cooling. The sprudelstein is
commonly oolitic or pisolitic, each little sphere
being formed of a series of concentric layers de-
posited'successively around a nucleus, and thus
imitating the oolitic structure famUiar to geolo-
gists in various limestones. The experiments of
G. Bose tended to show that when a solution of
carbonate of calcium is warm or concentrated it
deposits aragonite, while if cold or very dilute it
throws down calcite. It has been shown by
Credner that the deposition of aragonite is
favoured by the presence of gypsum, strontianite,
and certain other foreign bodies in the solution
from which ppn. proceeds.
Calcareous matter deposited on a large scale
is usually more or less impure, and hence lime-
stones become argillaceous, bituminous, &a. On
the solution of a limestone by natural solvents,
GEOLOGICAL CHEMISTRY.
605
a variable amount of insoluble matter is left,
and where the action has extended over long
periods the residual impurities, by their accu-
mulation, may acquire considerable importance :
such, for instance, is the origin of the deposits
on the chalk in this country known as ' olay-with-
flints;' and the reddish earth so common in
limestone caverns and known as ' cave-earth.'
On the solution of limestones in nature, v. T.
Mellard Beade, Chemical Denudation inrelation
to Geological Time [London, 1879].
Origin of Dolomite. — The origin of magnesian
limestone, or dolomite, has long been a chemical
enigma. Since dolomiteJfrequently occurs in as-
sociation with rock-salt, it has been suggested
that it must be of lacustrine origin. Bischof ,
however, showed long ago the difficulty of simul-
taneously ppg. OaCO, and MgCO, from a solu-
tion containing these salts. At the beginning of
the evaporation CaOOj alone falls ; towards the
close of the process MgGO, alone ; and it is only
at intermediate stages that the mixed carbonates
are thrown down. It might, therefore, be ex-
pected that the geologist would find pure lime-
stone below, succeeded by a deposit of dolomite,
and followed above by pure magnesite — a se-
quence, however, which is not observed in na-
ture. Indeed, dolomite seems to have been
formed not bo much by direct ppn. on the eva-
poration of waters in which the two carbonates
co-existed as by certain chemical reactions.
Sterry Hunt has pointed out that the inter-
action between carbonate of soditmi and the
chlorides of magnesium and calcium in sea-water
would give rise to dolomite, with simultaneous
production of chloride of sodium, thus explain-
ing the common association of dolomite with
rock-salt. There seems no difficulty in providing
the necessary quantity of Na^COj, inasmuch as
various soda-bearing silicates, notably the soda-
felspars, are commonly suffering decomposition
in nature by the action of carbonated waters,
with consequent formation of Na^CO, and sepa-
ration of silica. Another reaction suggested by
Sterry Hunt is that which may occur between
CaCOg and MgS04; the resulting MgCOj may,
under certain conditions, become associated with
fresh GaCOg, so as to form dolomite, which will
then be accompanied by a precipitate of GaSO,.
As a matter of fact, nothdrig is more common
th&n to find dolomite naturally associated with
gypsum {Chem. and Oeol. Essays,^ 1875, 90).
Hoppe-Seyler obtained dolomite by heating
carbonate of calcium in a solution of bicarbonate
of magnesium in a sealed tube at 100°C. (Zeits.
deutsch. geol. Ges. 27, 509). Possibly in some
cases dolomite has been formed under abnormal
conditions of temperature. The crystalline dolo-
mites, enormously developed in the triassio
series of the Eastern Alps, are believed to be
metamorphic rocks, or ordinary limestones which
have become dolomitised (v. infra).
Weathering of Bocks. — Most rocks on or
near the surface of the earth have suffered more or
less chemical change by the natural action of air
and water. This weathering usually takes the
form of oxidation and hydration; thus, rocks
such as basalt, which contain minerals rich in
iron, exhibit along their joint-planes a rusty ap-
pearance, due to &e formation of ferric hydrate.
Peposit8 pf blown iroQ-oie of great magnitade
may result from the alteration of masses of
iron-pyrites. Such, too, is the origin of the
gossan, or impure brown iron-ore commonly
found in the upper part of mineral veins where
anogenio action has been rife, and known to
Continental miners as the Chapeau de fer or
Eiseme Hut. Many clays and other rocks J)re-
sent in their unaltered condition a bluish Or grey
colour, due to the presence of finely-disseminated
iron-pyrites, which in like manner decomposes
on exposure, yielding ferrous sulphate, and finally
ferric hydrate, and the rock thus assuming brown
and yellow tints. (On the colour of certain
oolitic, rocks v, A. H. Church, C. J. [2] 2,
379.)
On the other hand, a process of deoxidation
may frequently be traced in the natural altera-
tion of rocks and minerals, the principal re-
ducing agent being organic matter. Sulphates
may thus be reduced to sulphides ; whence in
many cases the origin of iron -pyrites — a mineral
commonly found in association with coal, fossil
wood, shells and other organic remains (ti.Fepys,
Trans. Oeol. Soc. 1, 399). In like mannS
gypsum may be reduced to the condition of sul-
phide of calcium ; and this, if dissolved in water
containing carbonic acid, will yield isarbonate of
calcium and sulphuretted hydrogen, the latter
readily depositing free sulphur on exposure to
the air. Hence probably the origin of the asso-
ciated deposits of gypsum, sulphur, and lime-
stone, so familiar to the geologist in Sicily and
other sulphur-bearing localities. The removal
of crystals of selenite from clays ahd other rocks
may be due to similar reactions and not to mere
solution (Dnnban, Q. J. Geol. Soc. 22, 12)
It has long been known that the organic
acids resulting from the decomposition of vege-
table matter may exert a bleaching action upon
red and brown rocks, by reducing the ferric oxide
to a lower state of oxidation. It has been sug-
gested that some of the finest white glass-making
sands may have been derived from sands origin-
ally yeUow or brown, but decolourised in this
way. At the same time such reducing action
appears incompetent to explain the local de-
colouration observed in many variegated rocks
(v. an important paper by G. Maw in Q. J. Geol,
Soc. 24, 351).
Hydration, though usually accompanying
oxidation, may occur in nature without any
other chemical change. A common illustration
of such action is seen in the conversion of anhy-
drite into gypsum, by absorption of two mole-
cules of water. This change is accompanied by
a marked increase in bulk, 1 vol. of CaSOj be-
coming 1-6 vol. of CaS04.2H20. The galleries
of deserted mines in which anhydrite has been
worked have become closed by the swelling of
the waUs, consequent on hydration of the
mineral. G-eologists believe that a similar in-
crement of bulk, occurring on a large scale in
deep-seated deposits, may account for certain
minor movements of the Earth's crust.
Origin of Kaolin. — It is commonly said that
one of the most striking examples of weathering
is afiorded by the decomposition of the felspar
in granitic and other rocks. Meteoric waters,
containing carbonic and organic acids, readily
attack felspathio minerals, removing the alkalis
ina soluble form, wbU$th@ silicate gf aluwinioni,
606
GEOLOGICAL CHEMISTRY.
in a hydrated condition, lemains behind as clay.
KaoUn, or china-clay, the purest form of argil-
laceous matter, may thus he derived from fel-
spar-bearing rocks, especially granites. It was
seriously held that the great heat experienced
in working the Comstock lode was due to the
kaolinisation of the felspars in the surrounding
rocks — a suggestion, however, entirely disproved
by experiment. In Cornwall it is not uncommon
to find granite in which the orthoclase, or pot-
ash-felspar, is more or less decomposed, whUe
the associated silicates remain almost unaltered:
such a rock is known as china-stone ot petumite ;
while a rock in which the felspar is entirely
kaolinised is termed cMna-clay rock or earclazite.
It is frequently held that the simple action of
meteoric waters, charged with carbonic and
organic acids, is sufficient to explain the origin
of kaolin; but though kaolinisation may un-
doubtedly result from mere weathering, it seems
that superficial action is incompetent to explain
all the observed phenomena. The change ap-
l^ars rather to have been effected by means of
solutions derived from deep-seated sources, cir-
culating in the, joints of the granite. It has
often been pointed out that the decomposed
granite is associated with minerals containing
fluorine (like lepidolite) or fluorine and boron
(like schorl). Von Buch in 1824, and Daubr^e
in 1841, suggested that the change has been due
to hydrofluoric acid or other fluorides, which,
acting upon the granite at an elevated tempera-
ture, would decompose the felspar, removing its
alkali as a fluoride. Cassiterite (SnO,) is a
common associate of the kaolinised granite, and
there is reason to believe that this mineral has
been produced by the agency of fluorine.
Saubrle succeeded in producing crystals of SnO,
by passing the vapour of stannic chloride with
steam througb a heated porcelain-tube, the
chloride having been used in place of the fluoride
merely for convenience (v. Baubrie's l^tiides
synihitiques de Qedlogie expirimentale, Paris,
1879, where his researches are presented in a
collected form. For Cornish kaolin v. J. H.
Collins, The Hensba/nrow Oranite, Truro, 1878 ;
and Mimeralog. Mag^ 7, 205).
Metamorphism. — A rock, whether of
aqueous or of igneous origin, is said to be
metamcyrpMc when it has been altered not by
atmospheric agencies but by some profonnder
influence which has so affected its structure
and composition that its original character is no
longer to be recognised by direct observation.
Thus the intrusion of an igneous rock among
sedimentary strata may give rise to changes
known as contact metamorpJdsm. By such ac-
tion an ordinary limestone may be converted
into a crystalline marble — a phase of meta-
morphism conveniently distinguished by A. Gei-
kie as marmorosis. The production of a sao-
charoidal marble from an amorphous limestone
nnder the influence of heat and pressure was
iUnstrated by James Hall's experiments in the
early part of this century.
The effects of contact metamorphism are
partly physical and partly chemical. To the
former class may be referred not only the crys-
tallisation of limestone but the induration and
even fusion of various other rocks, and the de-
relopment of prismatic strootwe jn ^e neigl;.
bourhood of the heated mass. Among ordinary
chemical effects may be noted the expulsion of
water, the reddening of a calcined rock and the
conversion of coal into a natural coke. But the
most interesting phenomena are those attending
the development of new minerals. Thus, a slate
in the neighbourhood of an intrusive granite
frequently contains garnets, chiastolite, and
other crystallised silicates ; while metamorphic
limestones may inclose rock-crystal, garnets,
idocrase, micas, and other minerals which ap-
pear to have been produced by the rearrange-
ment and crystallisation of the materials of the
sand, clay, and other impurities originally pre-
sent in the Umestoije. The ejected limestone
blocks of Monte Somma, consisting originally
of the Subapennine limestone, are rich in mine-
rals of this character, and have lately been spe-
cially studied by J. H. Johnston-Lavis, of
Naples, and by B. Mierisch (Mm. u. Pet. Mitt.
[N. P.] 8, 113 [1887].)
When metamorphic rooks extend over a
wide area and are not visibly associated with
igneous rocks to which their alteration may be
referred, they are said to be due to regional
metamiorpMsm. The agencies by which such
phenomena have been produced are exceedingly
obscure, but while many of the changes are of a
chemical and molecular character, it is evident
that molar forces have been operating on a
large scale. Of late years it has been recog-
nised that the mechanical movements of the
rocks have largely contributed to the production
of the characteristic structures in those meta-
morphic rooks known as the crystalline schists,
not only producing deformation of the constitu-
ent minerals, but indirectly causing the passage
of one mineral into another. (On dynamic me-
tamorphism V. 3. Lehmann, Enstehung d, alt-
TcrystaWmschen Schiefer-Gesteim, Bonn, 1884 ;
Teall'p Brit. Petrog., 1888, cap. xiv. ; Mudes
sur les scMstes crystallins. Int. Geol. Congress,
1888 ; A. Harker, B. A. 1885. 845. For contaet-
metamorphism, v. Delesse'a Etudes siur le mita-
morpMsme des Boches. For the subject gener-
ally consult Bonney's address to Geol. Soc,
Quart. Jowm. Oeol. Soc, 42, 55 ; and A. Irving,
Bock-metamcyrpMsm, 1888.)
Sydrothermal action. — The effects of
thermal metamorphic agencies, even in the
neighbourhood of an igneous rock, are usually
due, not so much to dry heat as to hydrothermal
action. Although pure water at ordinary tem-
perature and pressure is capable of slowly dis-
solving the common mineral-constitqents of
rooks (Sogers, Am. S. [2] 5, 401)i its solvent
action is vastly increased by the great heat and
pressure to which it must be subjected in the
deeper-seated portions of the earth's crust, where
metamorphism probably has its normal seat.
Such action is well iUnstrated by the remark-
able experiments of DaubrSe. This observer
found that when water was heated in strong
glass tubes inoloaed in thick wrought-iron cylin-
ders, and exposed uninterruptedly to a tempera-
ture of at least 400°O. for several weeks, the
glass was transformed into a hydrated silicate,
analogous to a natural zeolite, while the interior
of the tube became lined with a crust of small
transparent crystals of quartz (Giolog. expirvm.
103). |n some cqses the ^r^igcial crystals Qf
GEOLOGICAL CHEMISTRY.
607
qnartz lined the walls of the tube like the quartz
in a natural geode {ib. 166).
The solvent action of water at great depths
accounts for the peculiar composition of the
water of geysers. Under enormous pressure and
at a high temperature these waters are capable
of decomposing the volcanic rocks which they
traverse and of dissolving out siUoa. Thus,
water from the Opal Spring in the Yellowstone
National Park contained as much as 53-76 g. of
silica to the imperial gallon (Lefimann). On
the evaporation of such water the silica is de-
posited in a hydrated form as a kind of opal or
siliceous sinter, known as florite or geyserite
(v. A. 0. Peale, • Thermo-hydrology,' in Twelfth
Bep. U.S. Qeol. and Qeog. Swrvey of the Terri-
tories, 2).
OolormUsat/um. — Among cases of metamor-
phism, that of the alteration of a normal lime-
stone into dolomite has long been recognised
and variously explained. Yon Bnch and certain
other German geologists, looking at the associa-
tion of orystalUne dolomite with basic igneous
rocks in the Tyrol, held that these erupted masses
had emitted vapours containing compounds of
magnesiimi which had acted upon the neigh-
bouring limestone, causing dolomitisation. ,In
support of such a view it was pointed out by
Durocher (C. 12. 23, 64) that when fragments of
limestone are heated with MgCl, in a closed
vessel, the limestone is partially converted into
dolomite. Such an action, however, if it occurs
at all in nature, must be limited to the imme-
diate neighbourhood of the heated body evolving
the magnesian vapours. In order to explain
the alteration of large masses of limestone it is
simpler to invoke the agency of percolating
water holding compounds of magnesium in solu-
tion. Even where limestone has' been dolomi-
tised in contact with basalt, Bischof contended
that the change was due to the action of water
containing MgCO, resulting from the decomposi-
tion of the magnesian silicates in the igneous
rock.
When water containing carbonate of magne-
simn percolates through a limestone, the magne-
sian salt tends to unite with part of the calcium
carbonate so as to form a double salt, while
CaOOg is af the same time dissolved out. For
every molecule of CaCO, removed, a molecule
of MgCO, is introduced, the change being accom-
panied by a diminution of volume to the extent
of 12 or 13 p.c. Now it is a remarkable fact
that natural dolomites are frequently marked
by a cellular or cavernous texture, and Elie de
Beaumont long ago suggested that the cavities
were due to shrinkage consequent on dolomitisa-
tion. It is estimated that in many magnesian
limestones the hollows represent about 12 p.c.
of the balk of the rock. The sulphate and
chloride of magnesium in sea-water may also
transform limestone into dolomite, but according
to Favre the action requires a temperature
of 200°O. favoured by great pressure. (For a
good review of the whole subject of dolomitisa-
tion V. A. H. Green's Geology, 3rd ed. 1882. 408 ;
alsoDoelter a. Hoemes, * Chem.-Genet. Betracht
u. Dolomit,' in Jdhr. d. k.-k. Qeol. Beichs, 187S.
26, p. 293 ; with a full bibliography to date.)
MgCO, is not the only carbonate which has
been introduced into certain limestones by lecon-
dary processes. In some cases beds of limestone
have been more or less completely transformed
into FeOOj — a change well illustrated on a large
scale in the important deposits of Cleveland
ironstone in the Middle Lias of N.E. Yorkshire.
Sorby believes that this ore has been formed
from an oolitic limestone by percolation of water
containing bicarbonate of iron in solution. Most
of the fossil shells associated with the ore have
suffered a like conversion, and in some cases the
ferrous carbonate has been further changed into
ferric hydrate (Proc. Qeol. and Polyt. Soe, W.
Bidmg, 1856-7). •
Serpentvrdsdtion. — The origin of serpentine
has been a subject of much discussion, in which
the geologist has had to appeal to the chemist.
By most modem petrographers it is regarded as
an altered eruptive rock, having been derived
mainly from olivine. Fseudomorphs of ser-
pentine after olivine are familiar to the mine-
ralogist, and an action similar to that which
produced this alteration appears to have been
concerned in the metamorphism of large rock-
masses. This view has. gained much credence
of late years by the study of the microscopic
structure of serpentine by Sandberger, Tsoher-
mak, Bonney, and other petrographers. Hydra-
tion is effected by water gaining access to the
olivine through the irregular fissures by which
the mineral is usu^y traversed; and in the
case of ferriferous olivines the iron is deposited
in the form of magnetite and limonite («. Teall,
Brit. Petrog., 1888, p. 104).
While many serpentines suggest by their oc-
currence as dykes and bosses that they have
been derived &om ei^ptive rocks, others' occur
in beds intercalated among crystalline schists,
especially in association with limestone. It has
been supposed that such serpentine may have
resulted £com the alteration of dolomite or some
other magnesian rock of aqueous origin. Sterry
Hunt, who is specially familiar with the serpent-
ines of the Laurentian series of Canada, has
always argued against the derivation of serpent-
ine tcoTD. igneous rocks, and regards it simply as
a product of direct precipitation from natural
waters. He holds that by the decomposition of
the various crystaUine silicates in nature, soluble
silicates of the alkalis and of lime are set free,
and passing into streams are ultimately mixed
with waters rich in magnesium salts — such as
the sulphate or chloride in sea-water — when
double decomposition ensues, and silicate of
magnesium is precipitated in a gelatinous con-
dition (Trans. S. Soc. Canada, 1, 165 ; Mineral
Physiology, Boston, 1886, p. 427).
Beoent formation of minerals. — Ob-
servations on the production of minerals under
known conditions in historic times are of much
interest to the geological chemist, inasmuch as
they suggest the processes which may have ope-
rated in nature during geological time. Daubr6e
long ago called attention to the production of a
series of minerals since the Boman period at the
hot springs of FlombiSres in the Vosges. Around
these springs the Bomans had built walls of
concrete, consisting of brick and stone cemented
by mortar. By the action of the waters at 50°
C. upon the concrete, there has been formed a
series of minerals including chabazite, harms-
tome, mesotype, and other zeolites, associated
GEOLOQIOAL OHEMISTKY.
with opal, calcite, &b. Similar effects have been
observed at other Boman baths, as at Luxeuil
(Haute 8a6ue) and at Bourbonne-les-Bains
(Haute Marne) (v. Oiologie Exp&rimentale,
p. 179 ; and Percy's Lectii/res on Chemical Geo-
logy in O. N. 9, 100).
Oeodes. — The production of certain minerals
at the Boman stations just cited recalls the
natural formation of similar substances in the
cavities of basaltic and other rocks. These
cavities, though perhaps in some cases due to
the removal of pre-existing crystals by solution,
usually represent bubbles produced by the dis-
engagement of gas or steam at^^ime when the
igneous rook was in a plastic condition. The
minerals occurring in such cavities are of
secondary origin, having been introduced
through the medium of solutions permeating
the rock long after solidification. When the
vesicles are filled with mineral matter the rock
is said to be amygdaloidal ; if the cavities are
not completely filled, and the walls are lined
with crystals, they are termed geodes. The
n^ost common of these secondary minerals are
oalcite and silica, the latter frequently forming
agates. In an agate, regular layers of colloidal,
crypto-orystalline, and crystalline, silica, succeed
each other with regularity. The exact manner
in which the silica has been introduced, and
precipitated on the walls, has given rise to much
discussion, but a clue is suggested by the ex-
periments of Fankhurst and I'Anson on the
artificial production of agates {Mineral Mag.
V. 34).
Origin of Mineral Veins. — The deposi-
tion of Bdcondary minerals in the cavities of
rocks tends to throw light upon the formation
of mineral veins, or lodes — a subject on which
the geologist has frequently appealed to the
chemist. It is now generally held that these
veins represent fissures, filled in by deposition
of mineral matter from a state of solution. The
chief difficulty is to trace the metalliferous
minerals to their origin. The most promising
modem researches are those of Prof. FridoUn
Sandberger, of Wiirzburg {Unterstichungen iiber
ErzgSmge, i. 1882 ; ii. 1885). By comparative
analyses of the ore, the veinstone, and the
country rook, he has shown that the contents
of the lode have been derived in certain cases
from the neighbouring rocks, and that the ores
have probably obtained their metallic elements
from the common constituents of the crystal-
line rocks, which had not previously been sus-
pected to contain such metals. Analyses of
ordinary rock-forming minerals, like mica,
augite, hornblende, and olivine, revealed the
presence in them of a large number of the
heavy metals. Nor is it only in the crystalline
rocks that such metals occur, Dieulafait having
shown that many of them are -iridely distributed
in minute proportion through the stratified
rocks. Such an occurrence is readily explicable
by the fact that most sedimentary strata have
been derived, directly or indirectly, from the
disintegration of the older crystalline rocks.
Thus it has been shown by A. Dick that
minerals containing zirconium and titanium
are widely distributed through sands of tertiary
age (Natwre, 36, 91), and Teall has foimd similar
mineralB in various clays {Min.Mag. 7, 201).
Some interesting phenomena tending to
illustrate the origin of certain mineral veins
have been studied in districts in California and
Nevada, where hydrothermal action is rife.
Hot water, steam, carbonic acid, sulphuretted
hydrogen, and other gases escape from fissures
in volcanic rocks, and on the walls of these
fissures they deposit siliceous sinter associated
with free sulphur, cinnabar, iron-pyrites, and
other metalliferous minerals, including metallic
gold — the whole assemblage being suggestive of
the contents of certain veins {v. A. J. Phillips,
P. M. 1868. 321 ; Laur, Ann. d. Mines, 3, 423).
Durocher and some other observers have
argued in favour of many metallic minerals in
lodes having been produced by sublimation. In
Durocher's experiments he succeeded in pro-
ducing galena, iron-pyrites, zino-blende, and
other metallic sulphides by passing certain
vapours through glass tubes at a high tempera-
ture (0. B. 38, 823 ; 42, 850).
As an illustration of the production of thin
strings of metallic minerals by decomposition of
vapours, attention may be called to the fre-
quent occurrence of specular iron ore sublimed
in the crevices of lava, this mineral having ob- ^
viously been formed by the reaction of steam and
ferric chloride: FejClj + 3HjO = FeA + 6HC1.
(On the general subject of mineral veins, v.
J. A. Phillips, Ore Deposits, London, 1884 ; Von
Cotta, Erzlagerst&Hen, Freiberg, 1859 [Trans-
lation by F. Prime, New York, 1870] ; and Von
Groddeck, LagerstHtten der Erse, Leipzig, 1879.)
Chemistry of the Volcano. — Thechemi-
oal operations involved in volcanic phenomena
are extremely obscure. It is generally admitted
that water is the prime factor in the produc-
tion of these phenomena, and as the tempera-
ture prevailing at volcanic foci probably exceeds
the critical point of water it must exist in the
form of vapour, notwithstanding the enormous
pressure to which it is subjected : possibly
the temperature is so high that the water is
dissociated. FouquS found in the lava of
Santorin of 1876 a notable quantity of free
hydrogen co-existing with free oxygen. The
volcanic vapours associated with steam are
chiefly HCl, SOj, COj,, HjS, free 0, H, and N,
and sometimes NH, and CH^. The HGl may
be due to access of sea-water, most volcanoes
being situated on islands, or, if on the mainland,
near to the sea-coast. Bicciardi has found that
finely powdered granite and lava mixed with
pure NaCl evolve HCl when heated, the quan-
tity being increased by blowing in a current of
steam (Oaesetta, 16, 38). The sublimed pro-
ducts of volcanic rocks include a large number
of metallic chlorides, notably those of NH^, Na,
Fe, Cu, Ca, and Mg.
The SO, of volcanic exhalations has been
'referred by Bicciardi to the reaction of silica
with CaSO, and MgSO,, whereby silicates are
produced, with separation of sulphur trioxide
which is resolved into sulphur dioxide and
oxygen. He found that granite mixed with the
sulphates cited above would evolve SO, when
heated. By the interaction of SO, and H2S
free sulphur is produced and deposited as an
incrustation on the lava. By oxidation, sol-
phurio acid is developed, and this by its action
on the volcanic rooks tends to decompose thenii
GERAlSflOL.
609
with production of various sulphates. Thus it
comes about that alum iS' manufactured in the
crater of Vulcano, one of the Lipari Islands, and
at the Solfatara, near Naples. .The term 'solfa-
tara ' ia_ now used by geologists as a general
designation for a volcano which is approaching
extinction and emits only vapours. Long after
other emanations cease, GO, may be exhaled, as
in many localities in the Eifel and in Auvergne.
Boric acid, in a finely-divided condition, is
produced from the nearly exhausted crater of
Vulcano, and from the mofette of Tuscany
where it has long been utilised indnstrially.
(On the general subject of volcanoes, v. Judd's
volume in the International Science Series.)
Synthesis of Igneous Books. — The
artificial reproduction of many igneous rocks
has been successfully accomplished in recent
years by FouqUd and LSvy in the geological
laboratory of the College de France, in Paris,
(for a full description of these researches, v.
their Synthase des Mmiraiuc et des Baches,
Paris, 1882.) These observers have shown that
a number of basic eruptive rocks can be formed
by the fusion of their constituents, and that the
products, examined in thin sections under the
microscope, are identical' in structure and com-
position with the corresponding natural rocks.
It had previously been supposed that water, in
some form, played a conspicuous part in the
liquefaction of igneous rocks, and that this was in
fact due not to dry fusion but rather to hydro-
thermal action. The syntheses performed by
Fouqufi and L6vy controverted this view, inas-
much as they were effected solely by dry igneous
fusion, without the presence of water or any
other volatile medium, and without flux or other
chemical agent.
The raw materials employed by these ex-
perimentalists were either the component
minerals of the rocks to be produced (such as
felspar, augite, &e.), or the chemical con-
stituents of these minerals (silica, alumina,
lime, &B.). These materials, corresponding in
their relative proportions with the composition
of the rock to be imitated, were introduced, in a
pulverised condition, into a platinum crucible of
about 20 c.c. capacity, furnished with a cover.
The crucible was heated in a furnace of For-
quignon and Leclero's type, heated by a Sohlo-
sing blowpipe, whereby it could be rapidly
raised to a white heat, or reduced at wiU to a
lower temperature, and the heat maintained
constant for a long period. The first fusion at
a white heat always yielded an isotropic glass,
and this if cooled suddenly maintained its
vitreous character. But if the fused product
was kept for some time at a temperature below
a white heat, yet above that of the melting-
point of the glass, various crystalline products
were developed; and by subjecting the material
to successively diminishing temperatures, other
products crystallised out, the least fusible being
the first to separate.
By a process of fractional crystallisation
conducted in this way, Fouqu6 and L^vy imi-
tated the conditions which appear to have
obtained during the formation of- volcanic rocks,
where the crystallised constituents represent
successive periods of consolidation. Artificial
basalt was obtained by fusing a mixture of the
Vol,, n.
elements of olivine, augite, and labradorite, and
subjecting the resulting black glass to a bright
red heat for 48 hours, when the olivine, which is
the least fusible component, was found to be
crystallised. Then on submitting the mass to
a cherry-red heat for another 48 hours, the
microlitic crystals of the more fusible minerals
separated: these were the lath-shaped crys-
tals of plagioclase and augite, which may be
regarded as minerals of the second period of
consolidation. Some of the most remarkable
experiments were those on the so-called ophites.
These are doleritic rocks, in which the augite
forms comparatively large plates moulded
around the crystals of plagioclase ; the former
having evidently been of subsequent consolida-
tion to the latter. By a succession of suitable
coolings and re-heatings this ophitio structure
was perfectly imitated.
Notwithstanding the remarkable success
with which the basic igneous rocks have lately
been imitated, all experiments on the synthe-
tical formation of the acid rocks have hitherto
been fruitless. The reproduction of these
natural products forms one of the most interest-
ing fields of investigation left open to the geo-
logical chemist. F. W. B.
GEOEETIC ACID 0, AzO,. A waxy acid
obtained from lignite found near Weissenfels.
Extracted by 80 p.c. alcohol, and ppd. by
Pb(OAo)j ; the acid is liberated from the pp. by
HOAo (Briickner, J. pr. 57, 1). Small needles
(from alcohol). Its solution gives a dirty-green
pp. with cnpric acetate. From similar lignite
Bruckner isolated resinous leucopetrin
CjoHsjO, crystallising from alcohol in tufts of
needles [above 100°]; geomyricin Oj^HjgOj
[c. 82°] crystallising from alcohol in minute
hair-like needles; geoceric acid CogH^gO,
[82°]; and geocerin OwK^fii [80°]. Geocerin
is a neutral wax.
6EBAHIENE 0„H,.. (163°). S.G. ^ -843. A
terpene obtained by treating oil of geranium with
PjOj (0. Jaoobsen, A. 157, 239). By treatment
with half the calculated quantity of iodine it is
converted into cymene (Oppenheim a. PfafE, B.
7, 625). Gives a liquid hydrochloride.
GEKANIOL C,„H,80. (233°). S.G. iS -885. A
compound occurring in oil of geranium (0. Jacob-
sen, A. 157, 282 ; Gintl, Ph. [3] 10, 24). Oil.
Inactive to light. Fragrant smell like roses.
Miscible with alcohol and ether. With calcium
chloride at 50° it forms a crystalline compound
(C,„H,80)jOaOL,decomposedby water. Slowlyoxi-
dised by air. Potash-fusion forms isovalerio
acid. Neutral aqueous EMnO, forms acetic and
isovalerio acids. Even boiling baryta-water slowly
forms isovaleric acid. Chromic acid mixture
forms also succinic acid. HNO, forms nitro-
benzene, HCy, oxalic acid, and a resin, but no
camphoric acid.
Geranyl chloride 0,„H„C1. S.G. ^ 1-020.
From geraniol and gaseous HCl. Inactive oil
smelling like camphor. Alcoholic AgNO, ppts.
even in the cold aU the CI as AgCl. KCy, KCyS,
KNOg, and other K salts displace the CI by their
acid residues.
Geranyl bromide C,i,H,^r. Oil.
Geranyl iodide C,oE„I. Oil. From the
chloride and cold alcoholic KI.
610
GERANIOIi,
Bi-geranyl oxide (0,„H„)20. (187''-190°).
From geranyl chloride and potassium geraniol
0,oH„OK. Oil, smelling of peppermint.
Si-geranyl sulphide (C,„H„)jS. Prom
C„H„Cland alcoholic KjS. Heavy yellowish
oil. With HgClj it gives a compound insoL
alcohol. When heated it gives geraniene.
GEEMANIUM. Ge. At. w. 72-3. Mol. w.
unknown, as Y.D. has not been determined,
[c. 900°] (WinMer, /. jgr. [2] 34, 177). S.G.
?|;j° 5-469 (W., I.C.). S.H. 100''-440° -0737 to
■0757 (W., Z.C.). Sharpest lines in emission-
speotram 6020, 6892, 4684-5 (Kobb, W. A. 29,
670). L. de Boisbaudran says that the charac-
teristic lines are 4680 and 4226 (0. B. 102, 1291).
In 1885 a silver ore from the Himmelsfiirst
mine, near Freiberg, was recognised by Eichter
as a new mineral species ; to ' it he gave the
name of argyrodite. The mineral was care-
fully analysed by Winkler with the result that
the percentages of Ag, S, Hg, Fe, and Zn found
added up to 93-94. Aiter much labour,
Winkler was able to announce that the rest of
the mineral was composed of a new element, to
which he gave the name germamum {B. 19,
210). Winkler was inclined to regard ger-
manium as belonging to the Sb-Bi family, but
fuller investigation showed it to be identical
with ekasiUcon, the properties of which had
been foretold by Mendelejefi, and the position of
which had been indicated by him as group IV.,
series 6. The reasoning which led Mendelejeff
to his statement of the properties of ekasiUcon
was similar to that on which he based his pre-
diction of the properties of eka-aVwiwimum,
with which element gallium was found to be
identical {v. Gaujum, Chemical relations of,
p. 598).
Occurrence. — Ge forms about 6-9 p.o. of
argyrodite. The composition of this mineral
is approximately expressed by the formula
2Ag2S.GeS2 ; it contains about -66 p.c, Fe, -22
p.c. Zn, and -31 p.c. Hg. Ge has also been
found in cv.xemite to the extent of about 7 p.c.
(Kriiss, B. 21, 131).
Pre;pa/rat/ion. — ^Powdered a/rgyrodate is
heated to moderate redness with calcined
NajOO, and flowers of S ; the product is ex-
tracted with water, and exactly enough
HjSO^Aq is added to decompose the Na^S,
After standing for a day the liquid is filtered,
and HClAq is added so long as a pp. forms.
The liquid is saturated with HjS, and filtered ;
the pp. is washed with 90 p.c. alcohol saturated
with HjS. The sulphide of Ge thus obtained is
roasted at a low temperature and warmed with
HNOjAq. The oxide thus produced is strongly
heated, and then reduced, either by heating in
H, or by making into small balls with starch
and water, and heating to bright redness be-
tween layers of charcoal, and then melting
under borax (Winkler, J. pr. [2] 34, 177). For
another method v. Winkler, J.;^. [2] 36, 177.
ProperUes. — Greyish-white, lustrous, very
brittle; melts at c. 900°, and crystallises in
regular octahedra on cooling. Only slightly
volatilised by heating in H or N at 1350° (V.
Meyer, B. 20, 497). Unchanged in air at
ordinary temperature, but oxidised when heated
In state of powder. Dissolved by H^SO^Aq but
not by HClAq. The atom of' Ge is tetraralent
in the gaseous molecules GeCl, and Gel,.
The at. w. has been determined by analysing
GeClj, and determining the Y.D., and hence
mol. w. of the same compound, and also Gel,
and GeS (Winkler, J. pr. [2] 34, 177). The
value 72-3 is confirmed by measurements of the
S.H. of Ge at 100°-400°. Lecocq de Boisbau-
dran has also calculated the at. w. from obser-
vations of the spectral lines of Ge (C B. 102,
1291). The difference between the mean wave-
lengths of the characteristic lines of Ge ana
Si is 443, and between Ge and Sn the difference
is 624 ; this may be stated as 443 (1 + -4051) =
624. In the cases of Ga and Al the difference
is 149, and the difference between Ga and In
is 205 -, this may be stated as 149 (1 + -38584)
= 205. The difference between the at. ws. of
Ga and Al is 42-4, and the difference for
Ga-In is 43-6 ; this may be stated as 42-4
(1 + -028302) = 43-6. The difference between the
at. ws. of Si and Sn is 90. From these data
the number 72-31 is found for the at. w. of Ge,
assuming that the relation between variation of
at. ws. and wave-lengths in the three elements
Si, Ge, Sn is the same as in the three elements
Al, Ga, In (o. GAiarou, Chemical BelaHons of,
p. 598).
Germanium belongs to the same family as
Si, Sn, and Pb ; these four elements form the
odd-series members of Group IV. Ge is both
metallic and non-metallic in its chemical re-
lations. The oxide GeOj dissolves in acids, but
no salts have yet been isolated ; this oxide also
dissolves in KOH and K^COs when fused with
these salts, and probably forms germanates
analogous to the stannates; GeSj also dissolves
in alkaline hydrosulphides probably forming
thiogermanates. The existence of the two
oxides and sulphides GeO and GeO,, GeS and
GeSj; the composition ahd properties of GeClj,
Gel,, and GeF, ; the formation of liquid GeHCl,
analogous to SiHOl, and CHGlg, And of liquid
Ge(O^s), similar to Si(C2H,), ; and the iso-
lation of H^GeFg and salts of this acid ; these
mark the similarity between Ge and Si. Ge
also appears to be capable of replacing Si in
ultramarine.
Beactions. — 1. Powdered Ge heated in air
burns to GeOj. — 2. Oxidised to GeO^ by nitric
acid. — 3. Dissolves in suJ^htmc acid, but not
in hydrochloric acid. — 4. Combines directly with
chlorine, bromine, and iodine, to form GeX,. —
5. Heated in a current of hydrogen chloride
GeHCl, is formed. — 6. Heated with mercuric
chloride or bromide GeCl, or GeBr, is produced.
Detection and Estimation. — The most cha-
racteristic reaction of Ge compounds is the pro-
duction of white GeSj by saturating an alkaline
solution with NH^HS, and then adding excess of
a mineral acid. In estimating Ge, excess of
NH,HS is added to an alkaline solution, a large
excess of dilute H^SOfAq is then added, and the
liquid is saturated with H^S ; after standing 12
hours the ppd. GeS, is collected, and washed
with dilute HjSOjAq saturated with HjS ; the
pp. is then washed ofl the filter, the residue on
the filter is dissolved in ammonia, and this solu-
tion, together with the water used in washing
oft the pp., is evaporated to dryness in a weighed
pornelain crucible, the main portion of the pp.
GEKMANIUM.
611
is now placed in the crucible, and iihe whole is
evapoiated to remove adhering HjSO, ; the resi-
due is heated, nitric acid is added, and the
whole is again evaporated and heated strongly ;
the residue is now digested with ammonia (to
remove H2SO4), then dried, heated strongly, and
weighed as GeOj. If the 6e is obtained as a
thio salt, along with thio salts of Sb, As, and
Sn, the solution is diluted to a definite volnme,
a measured portion is boiled with excess of
normal HjSOjAq, and the residual H^SO, is
determined volnmetricaUy ; the quantity of
E2SO4 required to neutralise the solution is thus
determined; the proper quantity of H2SO4 is
then added to another measured portion of the
liquid, and, after standing 12 hours, the liquid
is filtered and evaporated to a small volume ;
NHjAq and NH^HS are added, then excess of
HjSO^Aq, and the Ge is ppd. as GeS, by satu-
rating with HjS {v. supra).
Germanium bromide GeBr,; A strongly
fuming colourless liquid, which solidifies a little
below 0° to white crystals ; decomposed by water
with ppn. of GeOj and production of much heat.
Formed by heating Ge in Br, or with HgBr,
(Winkler, J. pr. [2] 36, 177).
Germanium chloride Gedf Mol. w. 213-78.
(86°). V.D. 107-5 at 200° to 0. 650° (Nilson a.
Pettersson,^. P.O. 1,27). S.G. |-g 1-887. Oriti-
oal temp. = 276-9° (N. a. P.) (vapour-pressures,
V. N. a. P., I.C.). A thin colourless Uqaid, fuming
in air ; decomposed by water to GeO^ ; partially
reduced to Ge by beating in H. Formed by heat-
ing Ge in CI, shaking the product with Eg and
distilling; or by heating powdered Ge with 8
times its weight of HgOlj (W., J. pr. [2] 84,
177).
When HCl is passed over heated GeS, a
ehloride lower than GeClj is probably obtained.
Germanium chloroform GeHCl,. Mol. w.
179-41. V.D. at 178° 80-3. A thin colourless
liquid, boiling at 72° : formed by gently heating
Ge in dry HCl, and separating the heavier liquid
from the lighter- (separation of the distillate
into two layers takes place slowly) (W., J.pr. [2]
86, 177).
Germanium ethide Ge(C2Hs)4. Mol. w.
188-06. V.D. 123. A colourless liquid of slightly
aUiaceous odour ; boiling at 160°. Prepared by
mixing ZnEt^ with GeClj, and keeping the mix-
ture cold, as the reaction occurs violently. SUghtly
lighter than, and immiscible with, water. Un-
changed by mixture with oxygen at ordinary
temperatures. Bums in air to GeOj (W., l.o.).
Germaainm flnorhydric acid ISjBteFjLq.
When vapour of GePi (obtained by strongly
heating GeF4.8H20) is led into water, the solu-
tion contains the acid 'E^QeF, (W., l.eX
Potassium GEBMASio-rtuoBiDE E,0eF, (W.,
I.C.; also Kruss a. Nilson, B. 20, 1696). Ob-
tained by adding KSE^ to a solution of GeO, in
HPAq (N. a. P.), or by using KCl instead of
KHPj (W.), allowing the pp. to settle, filtering,
and drying at dull red heat. According to
N. a. P. the salt is melted without loss of weight
at bright redness; and according to W. the salt
loses weight above a red heat. Not hygroscopic.
S. at 100° = 2-6 (N. a. P.). CrystalUses in hexa-
gonal forms; a:c = l: -80389; isomorphoua with
(NH4),SiP. (N. a. P.).
Germanium fluoride GeF^.SHjO. Very deli-
quescent crystals, obtained by dissolving GeO, in
cone. HFAq, and evaporating over H2SO4. When
heated, HP and HjO are evolved, and some GeO,
is formed; heated to redness GeF, is evolved,
and about half the Ge remains as GeO,. Furs
GeF4 has not yet been obtained ; Winkler
(J.pr. [2] 36, 17^) tried to prepare it, (1) by the
action of H on heated K^GeF, ; (2) by heating
GeF4.3H20 in dry 00, ; (3) by heating together
GeO,, CaF,, and HiS04 ; (4) heating a mixture
of KjGeF, with HjSO,. GeF, is doubtless a
solid capable of being volatilised (W.).
Germanium iodide 60X4. Mol. w. 578-42.
[144°]. (350°-400°) (W., /. pr. [2] 34, 177).
V.D. at 440° 272-5 (Nilson a. Pettersson, Z. P. C.
1, 36). Dissociation, probably into Gel, and I,
begins c. 650°. A yellow, very hygroscopic solid,
vapour is inflammable; mixed with air and
ignited, detonates feebly. Produced by heating
Ge in a current of CO, containing I vapour.
Germanium oxides. GeO has probably been
isolated. GeO, is a well-marked body.
Gebmakio oxide GeO,. Produced by burning
Ge in O ; or by oxidising Ge by HNO, ; or pre-
ferably by decomposing GeCl, by water. Dense
white gritty soUd ; S.G. |P 4-703. S. at 20° = -4 ;
at 100° = 1-05 (W., J. pr. [2] 34, 177). Separates
from solution in water as microscopic rhombic
crystals. Aqueous solution has a sour taste.
GeO, dissolves readily in fused KOH and K,CO,.
Probably forms salts with acids, but none has
yet been isolated.
Gebuaihous oxide CteO. Described by-
Winkler as obtained by boiling GepL with
KOHAq, and heating the hydroxide (probably
GeO,H2) thus formed in CO,; but there are
doubts as to the isolation of GeCI,, inasmuch as
the substance formerly supposed to be this chlor-
ide has been shown to be GeHCl, (W., J. pr. [2]
36, 177). GeO is also formed in small quantity
when powdered Ge is melted under borax. GeO
is described as a greyish-black solid; e. sol.
HClAq, forming a solution which reduces
EMnO,Aq to E^n04Aq and ppts. Au and Hg
from their salts.
Germanium oxychloride (7) GeOCl,. When
Ge is heated in dry HCl, two liquids of almost
the same S.G. are obtained. The distillate
slowly separates into two layers ; the lighter is
an oxychloride, probably GeOCl^. Winkler
{J. pr. [2] 86, 177) describes it as a colourless,
oily, non-fuming Uquid, which adheres to glass,
and boils much above 100°, seemingly without
decomposition.
Germanium, salts of. GeO, probably forms
salts by dissolving in acids, but none has yet
been isolated. ,
Germanium sulphides. Both GeS and GeS,
have been Isolated.
Gbbmanio sulfhide GeS,. Obtained by
adding NH4HS to an alkaline solution of GeO,,
then adding considerable excess of H2S04Aq,
saturating with H,S, washing first with :^S04Aq
saturated with H2S and then with alcohol, and
drying in vacuo. A white powder. Heated in
dry CO, it is partly ToiatUlsed, and apparently
also partially decomposed. If GeS, is washcid
with water untU free from acid, and then sus-
pended in water, an emulsion is formed which
bb2
612
GERMANIUM.
requires several weeks to clear. About 1 part ol
the sulphide treated thne dissolves in 229*1 parts
water ; the solution is feebly acid to litmus ; it
soon decomposes with evolution of H^S. GeS,
dissolves easily in »lkaluie hydrosulphides, pro-
bably with formation of thiogermanates.
Gbemanious sdIiPhide GeS. Mol. w. 104-28.
V.D. 1100°-1500° = 48 (Nilson a. Pettersson,
Z. P. O. 1, 37). Greyish-black plates; very
lustrous; red by transmitted light. Obtained
by heating GeS^ in a slow current of H. Heated
in air gives GeO^. Dissolves easily in warm
KOHAq, giving residue of Ge ; addition of HjS
to this solution ppts. GeS as a reddish-brown
amorphous solid. M. M. P. M.
6IIT6EB0L. An alkaline substance said to
occur in ginger, the root of Zingiber offidnaUs
(Thresh, Ph. [3] 12, 721). According to Thresh,
the ethereal extract contains, besides gingerol,
three resins CijHjjOj, O^HstOij, and CjjHjjOs,
and a terpene. By extracting ginger with
alcohol, and distilling the extract with eteam,
Stenhouse and Groves (C J. 31, 553; cf.
Papousek, A. 84, 352) obtained a light essential
oil which yielded protocatechuio acid on fusion
with soda.
GIIfGKOIC ACID CaH^Oj. [35°]. Occurs in
the fruit of Oingko biloba (Schw&rzenbach, /.
1857, 529 ; Viert.pr. Pharm. 6, 424).
GLASS. A mixture of E or Na silicate, or of
Doth, with one or more silicates insol. water,
such as silicate of Al, Ba, Ga, Fe, Pb, Mn, Mg,
or Sr. Pure silicate of K or Na is acted on by
water; silicate of Oa is decomposed by acids;
but a mixture of the two is only very slowly
acted on by water or the commoner acids. The
greater the proportion of silica and alumina in
the glass, the less fusible is it, and the more
slowly is it acted on by acids.
Glass is slowly acted on by hot water; the
more readily the greater the proportion of soda
or potash in the glass. Glass is corroded or
etched by HPAq vrith formation of gaseous SiP^.
Glasses poor in silica are acted on by most acids,
which dissolve out bases and separate silica.
Potash or soda dissolves out silica from glass,
especially when the solutions are hot and con-
centrated. Lead glass is blackened by heating
owing to reduction of some of the Pb silicate to
Pb. For details regarding different kinds of
glass, V. DrCTIONABY OF TEOHNIOAIi OHEMISTKT.
M. M. p. M.
GLATICINE. An alkaloid obtained by Probst
{A. 31, 241) from the leaves of the yellow homed
poppy {OUmoiMmfla/imm) growing on sandy sea-
shores. Colourless crusts of nacreous scales
(from water). It is ppd. from solutions of its
salts by KH, as a curdy mass which after some
time becomes pitchy. It is m. sol. hot water, v.
sol. alcohol and ether. Tastes bitter. Its solu-
tion is alkaline in reaction. Hot H^SO^ gives a
violet colour ; on adding water a red solution is
formed, whence NH, throws down an indigo-
blue pp. The hydrochloride, sulphate,
and phosphate of glaucineare crystalline, and
T. sol. water and alcohol, insol. ether.
GLATTCOUELANIC ACIB v. Ellaqio acid.
GLAirCOFICBINE. An alkaloid contained
in the roots of Olaticmm flamum {sime hiteum)
(Probst, A. 31, 254). Granular crystals, sol.
water and alcohol, si. sol. ether. Its salts have
I an extremely bitter and nauseous taste. Animal
charcoal removes glaucopicrine from solutions
of its Salts. Hot cone. H^SOf gives a dark green
pitchy product, insol. water, acids, and ammonia,
Thehydroohloride crystallises in rhomboidal
plates or in bundles of prisms, sol. water, insol.
ether. The sulphate and phosphate ara
also crystaUisable.
GLIADIIT V. Pboieids.
6L0BIN V. H^MOQLOBiN and PBOTsibB.
GLOBtrLABIET C^^B.^fig. Occurs in the leaves
of Qlohulcuria Alypum (Walz, N. J. P. 13, 281 ;
Heckel, A. Ch. [5] 28, 72; O. B. 95, 90).
Amorphous ; sol. water, alcohol, and ether.
Tastes bitter. Acid in reaction. Ppd. from its
aqueous solution by iodine and by tannin. Be-
solved by boiling dilute acids into glucose and
globularetin CsHjO. Globularetin is converted
into cinnamic acid by boiling EOHAq.
6L0B1TLIN V. Pboteids.
GIOBTTLOSE v. Pboteids.
GLTICIC ACID C,2H«0,jaq. (B.); C,.H,,d„
(M.). Olydc add.
Formation. — -1. A solution of glucose ia
saturated with lime or baryta and left for several
weeks. On adding lead subacetate a bulky pp.
of lead glucate is formed (Peligot, A, Ch. 67,
154). — 2. Glucose melted at 100° in its water of
crystallisation is mixed with warm cone. EOHAq ;
as soon as the first reaction has ceased the
liquid is diluted and the glucic acid ppd. by lead
subacetate (Persoz). — 3. Cane-sugar is boiled
with dilute H2SO4 in contact with the air. The
product is filtered, neutralised by CaCO,, evapo-
rated to dryness, dissolved in a Uttle watier, and
mixed with alcohol which ppts. calcium apo-
glucate while acid calcium glucate remains in
solution (Mulder, A. 36, 243).
Properties. — Amorphous mass, v. sol. water
and alcohol. Turns brown at 100°. The aque-
ous solution turns brown when boiled in contact
with the air or with dilute HjSO, or HClAq,
apoglucic acid being among the products. Ac-
cording to Grote and Tollens (A. 17S, 181) the
calcium glucate of Mulder is calcium levulate
C,H.0aO,.
Salts. — (Beichardt, Viertetjahr. pr. Phairm,
19, 384, 503.)— NasHjA'",: [100°]; hygroscopic.
— CaH,A"'2 aq.— BasHjA'", 3aq. — BaH,A"'j aq :
very hygroscopic. — MgHA'", aq. — AlA'" : yel-
lowish-white mass. — Fe,H,A"'2 3aq. —
Pb3C,^„0„ (at 150°).
Apoglucic acid C,jHjj0„ (dried at 100°)?
Formed by boiling glucic acid with water or dilute
acids or cane-sugar with dilute H^SO, (Mulder).
Amorphous brown mass, v. sol. water, si. sol.
alcohol, insol. ether. Its alkaline salts form
deep red solutions.^PbO,8H,,0,. — Ag2G,^„0„:
brown. — CaC,BHi,0,|, (at 130°) : brown amorph-
ous mass.
iBoapoglncic acid. Formed by heating ace-
tone with chlorine, potash, and HOI suocessive'y
(Mulder, Z. 1868, 51).— PbCHjO,.
GLUCINUM V. Bebylliom.
GLTJCO-COITfflABIC ALDEHYDE V. Qlucoside
of COUMABIO AIiDEETDE.
GLTTCODBUFOSE CmHjsOis. The chief con-
stituent of concretions in pears (Erdmann, A.
138, 1). Pale-yellowish grains. Insol. ordinary
solvents, »lkalis, cold d^ute acids, and
GLUTAOONIC ACID.
613
Sohweizer'a solution. Split up by boiling dilute
hcids into glucose and drupose Gyfi^fi,.
GLTTCOFEEULIC AIDEHYBE v. Fbrulio
BLTTCOLIGNOSE OjoHj^Oj, ? Occurs in pine
wood (Brdmann, A. Swppl. 5, 223). Yellowish
solid, insol. ordinary solvents, v. si. sol.
Sohweizer's solution. Split up by boiling dilute
HCl into glucose and lignose C,sH2„0„ ? (v.
CeLLTJIiOSe).
GircOHIC ACID CeH,jO, i.e.
CHj(OH).(qH.OH),.CO,H. [a]D = 5-8°.
I'ormation. — 1. From glucose, cane-sugar,
maltose, starcb, soluble starch, and dextrin by
successive treatment with bromine (or chlorine)
and Ag^O (Hlasiwetz a. Habermann, ^.155,120;
Habermann, B. 5, 167 ; JL. 162, 297 ; 172, 11 ;
Eeiohardt, B. 8, 1020; Kiliani, A. 205, 182;
Herzfeld, A. 220, 342).— 2. By oxidising glucose
with red mercuric oxide and baryta-water (Herz-
feld, A. 245, 32).— 3. By the fermentation of
glucose by mycoderma aceti in presence of
CaCO, and an infusion of yeast (Boutroux, J. Th.
1880, 52).
Preparation. — 1. Dextrin (30 g.) is heated
in a closed vessel with bromine (60 g.) and water
(500 CO.) for 6 hours at 100°. The product is
neutralised with Agj,0, filtered, freed &om silver
by HjS, and evaporated over the water-bath
(Herzfeld, A. 220, 342).^2. An aqueous solution
of cane-sugar is treated with bromine until' the
Br ceases to disappear. The HBr formed is re-
moved by PbO, the solution is then ppd. by HjS,
and the filtrate after concentration saturated
with ZnCO,. The zinc-salt is subsequently de-
composed by HjS (Grieshammer, Ar. Ph. [3] 15,
193).
Properties. — Uncrystallisable syrup (contain-
ing 2aq) ; loses aq at 100°, and the second aq at
125°. Sol. water, insol. alcohol. Does not re-
duce Fehling's solution. Decomposed by alka-
line hydroxides, alkaline carbonates, baryta, and
lime.
Reactions. — 1. Eeduced by HI and phos-
phorus to the lactone of oxy-n-hexoic acid
(Kiliani a. Kleemann, B. 17, 1296).— 2. Pro-
tracted treatment with bromime forms bromo-
form, bromo-aoetio acid, and oxalic acid. — 3.
AgjO forms glyoolHc acid.- 4. HNOj (S.G. 1-4)
oxidises it to saccharic and oxaUc acids.
Salts. — Ammonium salt: crystalline
(Boutroux, C. B. 91, 236 ; 104, 369). CaA'j aq
(from dilute alcohol). [a]„ = 5-9. S. (of OaA'J
3-8 at 16'5°. — CaA'2 2aq: groups of slender
needles.^ — CaC„H,„0, aaq. — BaA'^ 3aq : prisms.
S. (of BaA',) 3-3 at 15-5°.— BaA'5,2aq.— BaA'^ aq.
— BaC„H,„0,a!aq.— ZnA'25aq.— CdA'j.- PbA'j.-
PbjC„H,0, (at 120°).
Ethyl ether^tAf. Obtained in combina-
tion with CaCl^ as (EtA^CaOlj by passing HCl
into an alcoholic solution of the calcium salt.
The free ether crystallises in needles.
Penta-acetyl derivative of the ethyl
ether C5H„(OAo)5.COjEt. [102°] (Herzfeld, A.
245, 32).
Faia-glucouic acid CgE,20,.
Preparation. — ^If gluconic acid is left in con-
tact with nitric acid (S.G. 1-3) for some time,
and the solution neutralised with alkaline car-
bonates, salts of an isomeric paragluconic acid
are obtained, and .;an be separated from the me>
tallio nitrate by alcohol. The free acid is a colour-
less syrup, of strong acid reaction, sol. water,
insol. alcohol (Honig, M. 1, 48). The alkaline
earth salts of this acid cannot be obtained in a
crystalline form, thus differing from those of
gluconic acid. According to Volpert [B. 19, 2621)
it is identical with gluconic acid.
S alt s.— KA' (at 100°) : crystalline leaflets.T-
NHjA' (at 100°) : colourless monoolinio needles.
— Pb^CjHsO, : voluminous white pp.
GLTTCO-PEOTEINS v. Peoteids.
GLUCOSAMINE v. Peoteids ; Appendix C.
GLUCOSAN V. SuoAES.
GLTTCOSE V. Sugars.
6L1JC0SIDES. Substai^ces which, when de-
composed by dilute acids, yield glucose (or some
other sugar) and another substance not belong-
ing to the class of carbohydrates (Laurent,
A. Ch. [3] 36, 330). They are for the most part
natural products occurring in plants. They may
be viewed as compound ethers containing the
group (CjH||Oj), which is turned out on hydro-
lysis ECjH„0, + HjO = EH -f- CsHijOo. Some glu-
cosides may be obtained artificially by the use of
acetochlorhydrose 0,H,ClAc,Os : thus helicin is
formed by the action of this body upon potassium
salicylic aldehyde (Michael,.ilm. 1, 308). Inasmuch
as many sugars may be converted into glucose
by boiling with dilute acids, the appearance of
glucose after this operation does not necessarily
involve the pre-existence of the residue of that
particular sugar in the glucoside. The hjrdro-
lysis may be effected by boiling with dilute HCl,
dilute HjSOj, baryta-water, or dilute alkalis.
Some nitrogenous ferments, frequently existing
in the plants themselves, can efiect the hydro-
lysis even in the cold ; e.g. emulsin in almonds,
myrosin in mustard, and erythrozym in madder.
The glucosides are solid, soluble in water, and
usually crystalline. They give Pettenkofer's reac-
tion with bile salts and H^SO,. The following are
among the more important glucosides that yield
glucose when boiled with dilute acids : arbutin,
ruberythrin, salicin, daphnin, ^sculin, jalapln,
helleborin, turpethin, popuUn, bryonin, ononin,
and the nitrogenous glucosides amygdalin, sol-
anin,> indican, and chitin. The following phloro-
glucides resemble glucosides but yield phloro-
glucin instead of glucose on hydrolysis :
phlorctiu, queroetin, and madurin. The fol-
lowing ' phloroglucosides ' yield both phloro-
glucin and a sugar: phlorizin, quercitrin,robinin,
and rutin.
(a)-GH;C0SmE OeHgNj. (136°). S.G.2 1-038.
V.D. 3'81. A body formed by heating aqueous
ammonia with glucose at 100° (Tanret, Bl. [2]
44, 102). Limpid volatile liquid. Inactive to
light. — B'HOl: very deliquescent crystals. —
B'Etl : pearly crystals. ■
(/3)-61ucoBine C„HsNj. (160°). S.G. 2 1-012.
V.D. 3-87. Formed by the action of ammonia
on glucose at the same time as its isomeride
(Tanret, Bl. [2] 44, 104). Liquid. The platmo-
chlorides of the two glucOsines are partially de-
composed by boiling water (0. de Coninck, Bl.
[2] 45, 131).
GLTJTACONICACII) COjH.OHj.CH:CH.COjH.
[132°]. (Isomeric with citraconio acid.) From
di-oarboxy-glutaoonic ether (q.v.) and boiling
HCl (Conrad a. Guthzeit, A. 222, 253). -White
prisms. T. sol. water, alcohol, and ether. Not
614
GLUTAOONIC ACID.
decomposed below 180°. Gives no colour with
FeCIj. Sodium amalgam reduces it to glntario
acid.
Salts.— ZnA".—AgjA'.
Beference. — CHLOKo-aiinTAOomo acid.
GLUTAMIC ACID OsHsNO^ i.e.
C5H,(NHj)(C0jH)j. [202°]. S. 1 at 15°; S. (80
p.o. alcohol) -O? at 15°. Occurs, probably as
its amide, in pumpkin seeds (Schulze a. Bar-
bieri, B. 11, 710, 1233), vetch seeds (Gorup-
Besanez, B. 10, 780) and beet-root juice
(Scheibler, B. 2, 296 ; Schulze, B. 10, 85 ; 16,
312). It may be isolated from molasses after
the sugar has been removed by the strontium
process (Scheibler, B. 17, 1725). Formed, to-
gether with aspartic acid, by boiling vegetable
proteids with dilute H2SO4 (Bitthausen, J. pr.
99, 454; 107, 218). Formed also by boiling
casein with ECl and SnCI, (Hlasiwetz a. Haber-
mann, A. 169, 167). Among the products of the
decomposition of proteids by baryta Schiitzen-
berger {A. Ch. [5J 16, 375) found an acid
OsHsNO, [150°] which formed two silver salts
AgKA." and Ag^A", apparently not to be identified
with glutamic acid.
Preparation. — The portion of wheat gluten
that is soluble in alcohol (mucelin) is boiled for
20 hours with HoSO, (2 J pts.) diluted with water
(63 pts.) ; the product is neutralised by lime ;
excess of lime is removed by oxalic acid ; excess
of ozalic acid by lead carbonate ; and excess of
lead by H^S. The strongly acid liquid yields by
evaporation a crystalline mixture of tyrosine,
leucine, and glutamic acid, from which, by treat-
ment with hot water (which leaves the tyrosine
undissolved), and then with alcohol of 30 p.c.
(which chiefly dissolves the leucine), and re-
crystallisation from water with addition of
animal charcoal, and from alcohol of 30 p.c.,
the glutamic acid is obtained pure.
ProperUes. — Trimetrio tetrahedra ; a:b:c
= •801: 1:1-179 (Yon Bath); = -687: -855:1
(Oebbeke). SI. sol. cold water, insol. alcohol. Its
solutions are acid, and have an astringent taste.
In aqueous solution it is dextrorotatory,
[o]d=10-2 in a 2 p.c. solution at 21°. A solution
of its hydrochloride B'HCl is also dextrorotatory,
[o]n = 20° in a 4 p.c. solution at 21°; but its
neutral salts are lasvorotatory, thus for CaA"
[a]n=-3-7° in a 5 p.c. solution at 22°. Its
solution is not ppd. by lead acetate even on
addition of ammonia. Glutamic acid does not
reduce Fehling's solution. On distillation it
gives pyroglutamic acid CjHjNO,, and afterwards
pyrrole.
BeacUons. — 1. Nitrotis acid converts it into
an inactive oxy-glutario acid. — 2. Ba/ryta-water
at 155° renders it inactive ; but when some
PeniciUmm glaucum is placed in a solution of
the inactive glutamic acid it again becomes
active (Schulze a. Bosshard, B. 18, 388), The
inactive acid is m. sol. water (S. 1-7 at 17°).
Salts. — The glutamates of the alkalis and
alkaline earths are v. sol. water and alcohol, and
dry up to gummy masses; the copper salt is
characteristic and very sparingly soluble. —
HNaA". — (NH J^A". — NH.HA". — BaH^A"!
BaA"6aq: groups of needles. — CnA"2.^aq: S.
•03 in the cold ; -25 at 100° (Hoftneister,'Site. W.
75, 469). — OuA"2aq: blue crystalline powder
(Schulze a. Bosshard, B. 16, 313).— CuA"3aci.—
AgjA" (at 100°).— HjA"HCl (at 100=) : triclinic
tables ; si. sol. cone. HClAq.— HjA"HBr.
Mono-ethyl ether EtHA". [165°]. Cryg-
talline, v. sol. water, si. sol. cold alcohol, insol.
ether. Alcoholic ammonia at 150° converts it
into glutimide.
Amide C^'B.iJSJO, i.e.
0,H5(NBy(C02H)(C0.NHj). S. 4 at 16°. Occurs
in the juice of red beet-root, from which it ia
isolated by precipitation with Hg(N03)2 (Schulze
a. Bosshard, .5. 16, 312). Occurs also in pump-
kin-seeds (Schulze a. Barbieri, J.pr. [2] 20, 388 ;
32, 457). Slender white needles ; v. sol. hot
water; insol. absolute alcohol. Its aqueous
solution is inactive, but its solution in dilute
E2SO, or oxalic acid is dextrorotatory. Heated
with acids or alkalis it gives glutamic acid.
Imide 0^^(^S^<C^Q^y>NIL Formed by
heating ammonium glutamate for five hours at
190°. Needles. S. 8-7 at 15-6°.— CiHsNAHOl.
— OsH^gNjOj.
GLTTIAITIC ACID v. Oxt-glutasio acid.
GLUTAKIC ACID GJifi, i.e.
COjH.CH2.CH2.CHj.CO2H. Normal pyrotartaric
acid. Deoxyglutamic add. Mol. w. 132. [98°].
(0. 300°). S. 83 at 14°. S.H. (0°-94°) -3461
(Hess, W. [2] 35, 410). Occurs as the K salt
in the grease of sheep's wool (Buisine, C. B.
107, 789).
Formation. — 1. By heating oxy-glutario acid
(1 pt.) with cone. HIAq (4 pts.) at 120° for 8
hours (Dittmar, J. pr. [2] 5, 338).— 2. By the
saponification of trimethylene cyanide prepared
from trimethylene bromide and alcoholic KCy
(Lermontoff, B. 9, 1441 ; Beboul, Bl. [2] 25,
386 ; MarkownikofE, A. 182, 341).— 8. From
a-acetyl-glutaric ether (q.v.) and cone, alcoholio
KOH (Wislicenus a. Limpach, A. 192, 128).—
4. By heating menthol with HNO, (20 vols.)
(Moriya, C.J'.39, 78).— 5. By treating glutaconio
acid with sodium amalgam (Conrad a. Guthzeit,
A. 222, 254). — 6. By heating propane tetra-
carboxylio acid to 180° (Kleber, A. 246, 110).—
7. By boiling di-oxy-propane tri-carboxylic acid
with HIAq and phosphorus (Kiliani, B. 18, 640).
8. Among the products of the oxidation of
myristic acid by HNO, (Noerdlinger,B. 19, 1898).
Properties. — Large transparent monoclinio
prisms. V. e. sol. water, alcohol and ether.
When heated with bromine and water at 120°
some di-bromo-sucoinic acid is formed (E. Bour-
goin a. Beboul, C. B. 84, 556).
Salts. — NHjHA" : concentric crystals.—
(NHJjA".— NaHA"2aq. -NajA" icaq.- KHA".—
K2A"aq. — GaA"4aq: stellate groups of slender
needles, more sol. cold than hot water. S. 60 at
16°. — BaA"5aq: small transparent needles, v.
sol. water. — HgA"3aq: small needles (from dilate
alcohol); v. e. sol. water. — ZnA'': needles.
5. -1 at 18°. The solution deposits on heating
characteristic minute rectangular plates with
re-entering angles. — PbA"aq : heavy crystalline
pp.— CuA"4aq. — ^AgjA": needles (from hot
water).
Mono-ethyl ether EtBA". An oil formed
by the action of alcohol on the anhydride in the
cold (M.).
Di-ethyl ether Bt^A". (237°). S.G. "
1-025.
GLYCERIC ACID.
616
Chloride C,He(C0Cl)8. (217°) (Eeboul,
4. Cfc. [6] 14, 510). ^ " ^ ' ^
Anhydride CaHB(020s)- [57°]. (o. 287°).
From the sflver salt and Ac01(M.). Slender
Imide CsH^Oj. [162°]. Prepared by
heating at 175°-180° the mixture of neutral
and acid ammonium glutarates, obtained by
neutralising glutario acid with ammonia. Am-
monia and water are given ofE, and the imide
collects partly in the neck, partly at the bottom
of the flask. The product is obtained in the
pure state by orystallising from alcohol. Bril-
liant scales, subliming above its melting-point,
Bol. water and benzene, insol. ether. Its silver
salt is a crystalline powder. Heated with zinc-
dust it forms a hydrocarbon and a basic sub-
stance, probably a hydride of pyridine. After
heating with PCI5 at 60° on distilling the
residue in a current of steam, a substance
GsHsClgN is obtained, crystallising in needles
[60°] which appears to possess the constitution
CH2<^Q^^„„?^N, inasmuch as, when healed
with hydriodic acid and amorphous phosphorus,
it yields a substance approximately of the com-
position of chloropyriduie (Bemheimer, O. 12,
281).
GLTTTAZINE v. Di-oxy-amido-pybidine.
GLUTEN V. Pbotbids.
GLTTTEN-FIBEIN v. Pboteids.
GLUTIC ACID V. GiiTjtinic acid.
GLUTIMIC ACID CaH^NOa. [180°]. One of
the products of the decomposition of proteids
with barium hydroxide ; glistening, voluminous
prisms, sparingly sol. cold water, insol. cold
alcohol. A monobasic acid, forming a sparingly
soluble mercuric salt (Schiitzenberger, A. Ch.
[6] 16, 373).
GLUTIN V. Proteids.
GLUTINIC ACID O^flt »•«•
H02C.C:C.0Hj.C0jH. [146°]. Formed by the
action of alcoholic KOH upon /S-chloro-gluta-
conio acid H02C.0H:CC1.0H2.C02H ; the yield
is 30-40 p.o. of the theoretical. Slender needles,
V. sol. alcohol and ether, insol. benzene and
chloroform. On heating the acid or its mono-
potassium salt with water, it is converted with
evolution of CO2 into a very unstable mono-
basic acid, probably KdG.CSpOOJS., which
gives the acetylene reactions. — A"Pb : white pp.
— ''A"K2a!aq: long flat needles. — ''A"Baa;aq:
slender needles (Burton a. Pechmann, B. 20,
148).
GLYCEBAHINE v. Gi.yoiDAMinE.
GLYCEEIC ACID CsHoO, i.e.
CHj(OH).CH(OH).OOjH. Mol. w. 106. aP-Di-
oxy-vropiorda acid. Seat of neubraUsation by
iNa20 = 11,334; by Na20 = 12,127 (Gal a. Wer-
ner, Bl. [2] 47, 163).
WormaiAon. — 1. By the gradual oxidation of
glycerin by nitrio acid (Debus, P. M. [4] 15,
195 ; A, 109, 227; Socoloff, A. 106, 95).— 2. By
the spontaneous decomposition of nitroglycerin
(De la Bue a. MiiUer, A. 109, 122).— 3. By heat-
ing glycerin (1 mol.) with bromine (2 mols.) and
a large quantity of water at 100° (Barth, A. 124,
341). — 4. By heating n-ohloro-iS-oxy-propionio
acid or ^-chloro-a-oxy-propionio acid with moist
AgjO (Melikoff, C. C. 1881, 364 ; B. 13, 272 ;
Frank, A, 206, 348). — 6. By heating a;9-di-bromo-
propionic acid with moist Ag^O (Beckurts a.
Otto, JB. 18, 238).— 6. By heating oxy-aorylia
acid Gs'Efla with water (Melikoff).
Preparation. — 1. By mixing 60 g. of glycerin
with 60 g. of water in a large glass tube, and
adding, by means of a funnel reaching to the
bottom, 50 g. of fuming nitrio acid. After three
or four days the contents of three such tubes
are slowly evaporated on the water-bath down to
about 270 g., and the syrupy mass thus obtained
is preserved in a flask allowing the escape of
gas, which is slowly given off. 1,620 g. of the
syrupy mass are next mixed with 11 litres of
water, 2,400 g. of white lead are gradually added,
and the mixture is left to stand for a day. The
vessel is then wanned, with constant stirring,
to 61°-65°, and kept at this temperature for
two hours. The liquid is decanted and allowed
to deposit crystals, the mother-liquor added to
the solid mass, the water lost by evaporation
replaced, and the operation repeated two or
three times. The lead salt thus obtained is de-
composed by HjS (Mulder, B. 9, 1902 ; cf. Beil-
stein, A. 120, 226). — 2. Mercuric oxide and
baryta are added to a concentrated boiling aque-
ous solution of glycerin. When the liquid is
saturated with baryta the addition of HgO is con-
tinued until reduction po longer takes place. The
liquid is filtered, treated with CO.,, again filtered,
and evaporated to a syrup, which is freed from
glycerin by washing with alcohol. The residue
is dissolved in water, the Ba is ppd. by the cal-
culated quantity of HjSO^, and the glyceric acid
which remains purified, if necessary, by means
of its calcium salt. The yield is 45 p.c. of the
glycerin used (Bornstein, B. 18, 33S7).
Properties. — Unorystallisable . syrup ; mis-
cible with water and alcohol, insol. ether. When
heated for some time at 105° it is converted into
a soft, very tenacious, anhydride O3H4OJ ; fur-
ther application of heat gives formic, acetic,
pyruvic, and pyrotartaric acids and an acid
OsH.oOa [83°] (Moldenhauer, A. 131, 328 ; Bot-
tinger, A. 196, 92). Distillation with KHSO,
forms pyruvic acid (Erlenmeyer, B. 14, 321).
Glyceric acid prevents the ppn. of cupric and
ferric hydrates by potash. It is optically inac-
tive, but a solution of ammonium glycerate is
rendered lavorotatory by PemcilUum glaucum
(Lewkowitsoh, B. 16, 2720).
Beactions. — 1. Iodide of phosphorus forms
)3-iodo-propionic aoid,^ — 2. Boiling cone. KOHAq
forms oxalic and lactic acids. — 3. Potash-fusioii
gives formic and acetic acids. — 4. PClj gives
0HjCl.CH01.C0Cl (WichelhauB, A. 135, 248).
Sal ts .— NHiA' : radiating deliquescent crys-
tals.— EEA'2 : small crystals ; the neutral K salt
decomposes on evaporation. — CaA', 2aq : nodules
composed of minute tables or prisms; sol. water,
insol. alcohol; on adding alcohol to its aqueous
solution monoolinic crystals are got.— -SrA',:
crystals; nearly insol. cold, v. sol. hot, water
(GarzaroUi-Thurnlack, A. 182, 190).— BaA'^.
large spherical aggregates of concentric lamina,
V. e. sol. hot water, insol. alcohol. — MgA'^ 3aq :
stellate groups of small efflorescent crystals. —
ZnA'jaq : small crystals. — CdA'j2aq. — PbA'j. —
CnA'2 : minute sky-blue crystals, m. sol. cold
water. — MnA', 3aq. — AgA' : minute prisms (from
water).
Ethyl ether EtA'. (230°-240°). S.G. s
616
GLYCEillO ACID.
1'193. Formed by heating glyceric acid (1 pt.)
with alcohol (4 pts.) at 176° (Henry, B. 4, 701).
Sticky liquid. A mixture of HNO', and H.^SO)
converts it into its oUy di-nitrate C3Hj(N03)aOEt.
Anhydride or lactone O3H4O3. Separates
from an aqueous solutioii of glyceric acid evapo-
rated at 100° and left to rest. Slender six-sided
needles (from water). Insol. alcohol and ether.
It dissolves in 647 pts. of boiling water, by which
it is slowly re-converted into glyceric acid.
GLYCEEIC ALDEHYDE (?) OsHsOa or
«O.H,A.
Prepwratian. — By the action of platinum
black (best prepared by the method of Idrawko-
witsch) on glycerin mixed with double its weight
of water. The mass is extracted with water, and
concentrated on a water bath m vacuo.
Beaciions. — Eeduces Fehling's solution and
ammoniacal nitrate of silver. Is coloured yellow
on boiling with lime or baryta water. Becomes
strongly heated when shaken with a solution of
NaHSO,, after which alcohol ppts. a gummy
matter, but NajCO, or H^SO, do not set free an
aldehyde from this mass. Phenyl-hydrazine
hydrochloride and NaOAc gives a coloured pp. ;
on fractional ppn. several derivatives are ob-
tained, none of which have been obtained pure.
Of the part soluble in alkalis after a crystallisa-
tion from benzene, and one from weak alcohol,
the melting-point is constant [193°]. The al-
dehyde ferments with yeast, but the quantity of
CO2 obtained is smaU compared to its reducing
power (Grimaux, Bl. [2] 47, 885; cf. Eenard,
C. B. 82, 562). The same body occurs among
the products of the action of nitric acid upon
yeast, and it appears to be closely allied to the
sugars (Grimaux, C. B. 105, 1175).
GLYCEBIN OsHjO, i.e.
CHjOH.CH(OH).OaiOH. OVycerme. OTyeerol.
Mol. w. 92. [20°] (Nitsche, D. P. J. 209, 145).
(290° cor.). S.G. |g 1-2635 (Nicol, Ph. [3] 18,
802) ; i| 1-2624 ; || 1-2588 (Perkin, C. J. 45, 507) ;
=j° 1-2590 (Briihl). M.M. 4-111 at 16° (P.). H.F.p.
-1364 (Eamsay). /i^ 1-478. Ea, 33-70 (B.). S.H.
-612 (Winklemann, P. 153, 481). Isotomc co-
efficient : 1-78 (Be Vries, Ann. Agr. 14, 376).
Glycerin, as was first shown by Chevreul,
bears the same relation to the fats and fatty oils
that alcohol does to acetic ether, and is, there-
fore, formed from them by boiling with aqueous
alkalis, baryta-water, lime-water, litharge and
water, or even by heating (under pressure) with
water alone. It was discovered in 1779 by
Scheele, who obtained it in the preparation of
lead plaster by saponifying lard with lead oxide.
Formation. — 1. Always produced in the al-
coholic fermentation of sugar, the amount being
about 3 p.c. of the sugar used (Pasteur, C. 22. 46,
857 ; 47, 224). Hence it occurs in all fermented
liquors. Wine may contain about 1 p.o. of gly-
cerin. Brandy also may contain a little glycerin
(Morin, 0. B. 105, 1019).— 2. When s-tri-bromo-
propane CH^Br.CHBr.CH^Br is heated with
AgOAc there is formed glyceryl tri-acetate or tri-
acetin CHj(OAo).OH(OAo).OH2(OAo). Baryta-
water converts this tri-acetm into glycerin (Wurtz,
A. Ch. [3] 51, 97).— 3. Synthetically prepared
from acetone by successive conversion into iso-
propyl alcohol, propylene, propylene ohloro-io-
dide, propylene chloride, and tri-chloro-propane.
The tii-oUbro-propane was obtained by heating
propylene chloride with iodine chloride at 140",
and was converted into glycerin by heating with
water at 180° (Friedel a. Silva, O. B. 76, 1594).
Prepa/raUon. — 1. By saponification with ox-
ide of lead.—'FWe pts. of finely pounded litharge
are heated with nine pts. of olive oil or any other
glyceride and a small quantity of water, the mix-
ture being stirred, and the water renewed till the
oxide of lead is converted into a plaster ; the
watery liquid is then separated from this plaster,
and freed from lead by a stream of HgS, and the
filtrate is evaporated to a syrup over the water-
bath. For many years all the glycerin of com-
merce was obtained by this method ; but it was
very apt to retain small quantities of lead, the
presence of which is very objectionable in any
therapeutic application of glycerin. — 2. From the
alkaline mother-liquor of the soap-works glycerin
may be obtained by distillation with superheated
steam. — 3. By saponifying taUow with lime and
water, ppg. excess of lime by HjSO,, and evapo-
rating.— 4. By distilling fats in a current of su-
perheated steam at 300° ; the fats are then de-
composed, and the glycerin which distils over is
finally rectified in vacuo.
Properties. — Thick syrup with sweet taste.
Neutral to litmus. Miscible with water, alcohol,
and chloroform, but insol. ether. It is slightly
volatile with steam (Gouttolenc, Bl. [2] 36, 133).
Volatilisation of glycerin does not, however,
take place as long as 50 p.c. of water is present,
and even when there is only 26 p.c. water, mere
traces of glycerin pass over (Hehner, An. 12,
65 ; cf. Nessler a. Barth, Fr. 21, 44 ; 23, 329).
When distilled under atmospheric pressure it is
partially decomposed, but it may be distilled
under diminished pressure without decompo-
sition. It boils at 180° under 12-5 mm. pressure
(Bolas, C. J. 24, 84). Glycerin is hygroscopic
and may absorb as much as 58 p.c. of water from
the air (E. Williams, O. C. 1881, 76). The fol-
lowing table gives the specific gravity at 20° of
solutions of glycerin, compared with water at
20° (Nicol, Ph. [3] 18, 302) :—
Olyoerin per cent
Spcoifio gravity
100 .
1-26348
90 .
1'23720
80 .
1-21010
70 .
1-18293
60 ,
1-15561
50 ,
1-12831
40 .
1-10118
30 .
1-07469
20 .
1-04884
10 .
102391
A 10 p.o. solution of glycerin freezes at —1°; a
20 p.c. solution at —2-5°; a 30 p.c. solution at
- 6° ; a 40 p.c. solution at - 17-5° ; and a 50
p.c. solution at — 31°. Pure glycerin may be ob-
tained in deliquescent trimetric crystals melting
at 20° : a\b:c = -70 : 1 : -66 (Nitsche, D. P. 3. 209,
145 ; Von Lang, P. 152, 637). Glycerin burns with
a colourless flame. Glycerin dissolves iodine. An
aqueous solution of glycerin dissolves more AsjOj
than pure water (Sohiff, A. 118, 86). Aqueous
solutions of glycerin dissolve baryta, strontia,'
and lime. Pure glycerin dissolves KOH and
NaOH. Glycerin dissolves all deliquescent salts,
and also the sulphates of K, Na, and Cu, and the
chlorides of K and Na (Pelouze, A. 19, 210; 20,
QLYCERIN.
617
46). Aqueous and even dry glycerin dissolves
PbO. FeOlj mixed with much glycerin is not
ppd. by alkalis (c/. Puis, J. pr. 15, 83). Cupric
sulphate mixed with glycerin forms, with a small
quantity of potash, a pp. which dissolves in ex-
cess of potash ; but on boiling the resulting deep-
blue solution bluishflakesaredeposited. Glycerin
renders borax solution acid (D. Elein, 0. R. 86,
826; Senier a. Lowe, Ph. [3] 8, 819; G. J. 33,
438 ; Donath a. Mayrhofer, Fr. 20. 379 ; Dun-
Btan, Ph. [3] 13, 257).
ilssfs.— Glycerin is optically inactive, so that
adulteration with sugar may readily be detected
by the polariscope. The presence of glycerin in
a saccharine liquid may be detected by mixing
with slaked lime and sand, evaporating over a
water-bath, and extracting the nearly dry residue
with alcohol-ether ; the alcohol-ether on evapo-
ration leaves the glycerin behind ; a borax bead
after dipping in the glycerin colours a flame
green (Senier a. Lowe, C. J. 33, 438 ; Donath a.
Mayrhofer, Fr. 20, 383). If a mixture of equal
volumes of glycerin, phenol, and H^SOj be heated
to 120°, diluted with water, and treated with
NHj, a crimson colour is developed (Beiohl, B.
9, 1429).
Estimation. — 1. When an aqueous solution
is shaken with benzoyl chloride and sufficient
NaOHtomakeit alkaline, an insoluble crystalline
pp. is produced, which chiefly consists of the di-
benzoyl-derivative C3H5(OBz)2(OH). When crys-
tallised from petroleum-ether it forms long
colourless needles [70°], v. sol. alcohol and ether,
insol. water. Other hydroxylated compounds
must be absent. The reaction can be used for
the quantitative determination of glycerin in
beverages (E. Baumann, B. 19, 3221 ; Diez, H. 11,
472). — 2. Commercial glycerin (1 g.) is boiled for
1 hour with (7 g. of) ACjO and (3 g. of) dry NaOAc
in a flask with inverted condenser ; the product
is diluted with water (50 c.c.) and heated to boil-
ing. In this operation the glycerin is converted
into the tri-acetin, and the amount of tri-acetin
can be determined after filtration by neutral-
isation of free acid by NaOH, saponiflcation
with standard NaOH and titration with standard
HCl (Benedikt a. Cantor, M. 9, 621).— 3. Cham-
pion and Pellet f^Bl. [2J 19, 493) estimate the
amount of glycerin in commercial samples by
treatment with a mixture of nitric acid and
HjSO,, the resulting nitroglycerin being dried
at 100° and weighed. — 4. A safer method con-
sists in mixing the liquid (1 pt.) with lead oxide
(25 pts.) and evaporating to a constant weight at
130° ; the increase in weight of the lead oxide is
noted (Morawski, Fr. 21, 130).— 5. For the esti-
mation of glycerin in vnne, Macagno (D. P. J.
216, 95) digests a litre of the wine with recently
precipitated lead hydroxide; evaporates the
liquid on the water-bath, then adds a further
quantity of lead hydroxide ; exhausts the mass
with absolute alcohol, and precipitates the dis-
solved lead by a stream of carbon dioxide. The
iUteredliquid when evaporated leaves nearly pure
glycerin. — 6. The estimation of glycerin in wine
or beer may be effected by mixing with milk of
lime and chalk, evaporating to dryness, and ex-
tracting with alcohol. The alcoholic extract is
evaporated to a small bulk, mixed with alcohol-
ether, filtered if necessary, dried at 105°, and
weighed (Weigert, C. C. 1888, 1511 ; cf. Claua-
nizer, Fr. 20, 80) . Instead of weighing the glycerin
it may be oxidised either by boiling with KjCr^O,
and HjSO,, or by heating with KMnOjandH,,-!!),
at 40° ; in either case the amount of carbonic
acid evolved or the amount of reduction effected
may be noted (Legler, An. 12, 14; Hehner, An.
12, 44, 65 ; Planohon, O. B. 107, 246 ; Cross a.
Bevan, O. N. 55, 2).— 7. An aqueous solution of
glycerin (about -25 g.) may be oxidised by KMnO,
after addition of KOH (5 g.), and the oxalic acid
formed ppd. as calcium salt (Fox a. Wanklyn,
C. N. 53, 15 ; Benedikt a. Zsigmondy, Fr. 25,
587 ; Allen, An. 11, 52 ; JoUes, Fr. 27, 521).
Reactions. — 1. Partially decomposed by dis-
tillation yielding acrolein, acetic acid, CO^, and
polyglyceric compounds. When distilled with
P2O5 or KHSOj it yields acrolein. When dis-
tilled with CaClj it yields acrolein, acetone, pro-
pionic aldehyde, phenol, &a. (Linnemann a.
Zotta, A. Stippl. 8, 254 ; 174, 87).— 2. Glycerin
is oxidised by the air in presence oi platinum-
black to CO2 and water ; at the same time the
so-called glyceric aldehyde (a kind of sugar) is
formed. This body is fermentable by yeast
(Grimaux, Bl. [2] 49, 251 ; G. B. 105, 1175). A
substance resembling glucose is also formed by
placing glycerin in contact with iron that is'
undergoing oxidation in moist air (Kosmann, Bl.
[2] 27, 246). — 3. Propionic and formic acids are
among the products of the oxidation of glycerin
in alkaline solution \by ozone (Gorup-Besanez,
A. 125, 211).— 4. MnOj and HCl or H^SO, yield
COj and formic acid. — 5. If fuming nitric acid
and dilute glycerin are left in contact in two
layers in the cold, gradual oxidation takes place
with formation of glyceric, racemie, glycollic,
glyoxyUc, oxalic, formic, and hydrocyanic acids
'(Debus, A. 106, 79; Beilsteiu, A. 120, 228;
Heintz, A. 162, 325 ; Przybytek, Bl. [2] 35, 108).
By the action of HNOj on glycerin in the cold
Przybytek (Bl. [2] 36, 145 ; 37, 342) also ob-
tained an acid C„H,gOg, apparently identical
with saccharic acid, and inactive tartaric acid,
as well as racemio acid. Werigo (C. G. 1881,
612) by oxidising glycerin with HNO3 obtained
an acid OgHjO,. On warming glycerin with
dilute nitric acid (S.G. 1*18) a violent reaction
ensues, and after removal of the nitrous acid
with urea a liquid is obtained which reduces
FehUng's solution and gives with phenyl-hydra-
zine hydrochloride the crystalline di-phenyl-
hydrazide, ' phenyl glyoerosazone ' OisHjjNO, or
OHj(OH).C(NjHPh).CH(NjHPh) [131°] (Fischer
a. Taf el, B. 20, 1088).— 6. If lead hydroxide (500 g.)
be added to boiling aqueous (85 p.c.) glycerin
(1,000 g.) and, after cooling to 0°, the resulting
lead compound be washed with alcohol and
ether, dried at 100°, and exposed to bromine
vapour, ' glycerose ' is formed. It may be ex-
tracted by alcohol, and after evaporating the
alcohol and treating the residue with BaCO, to
remove acids, it can be dissolved in ether.
Glycerose is a syrup which reduces Fehling's
solution, ferments with yeast, and when treated
with phenyl-hydrazine yields phenyl-glycer-
osazone. However, it appears to be a mixture,
since it yields two oxy- acids when warmed with
cone. HCyAq (Fischer a. Tafel, B. 21, 2634). If
glycerin (10 pts.), Na^COjlOaq (35 pts.), water
(60 pts.), and bromine (15 pts.) be mixed at 10"
and the solution be mixed with phenyl-hydra-
618
GLYCERIN.
Eine solution two osazones are got, CigH^sN^O,
[217°] anda59°] (Fischer a. Tafel, B. 20, 3384).—
7. A mixture of HNO,and cone. H^SO, gives the
trinitrate, commonly called nitroglycerin. — 8.
Alkaline EMnOj forms GO,, formic acid, pro-
pionic, and traces of tartronic acid. The latter
is often present as the acid manganese salt
Mn(00p0H(0H).C02H)j (Campani a. Bizzarri,
G. 12, 1). By nsmg strongly alkaUne KMnO^, ox-
alic acid (1 mol.) and CO, (1 mol.) were obtained by
Fox a. Wanklyn (O. N. 63, 15 ; cf. Planohon, 0. B.
107, 246). — 9. A solution of glycerin acidulated
with 5 p.o. of HjSO, yields on electrolysis formic
paraldehyde (tri-oxy-methylene), formic, acetic,
oxalic, and glyceric acids, and a glucose (polymer-
ide of tri-oxy-methylene) which forms a barium
compound CeH,20e3BaO, is not fermented by
yeast, and is oxidised by HNO, to oxalic acid (Be-
nard, A. Oh. [5] 17, 303). Bartoli a. Papasogli
(0.13, 287) obtained acroleiuiformic paraldehyde,
glyceric acid, and formic acid by electrolysing
glycerin.^10. Lime and AgjO form glycollic and
formic acids (Eiliani, B. 16, 2415). — 11. Accord-
ing to Dumas a. Stas {A. '35, 158) by gently
heating glycerin with KOH it is converted into
potarssium formate and acetate with evolution of
hydrogen, Herter (B, 11, 1167) also obtained
lactic acid. — 12. On distillation with caustio
soda it is on the one hand reduced to propylene
glycol, and on the other hand oxidised to formio
acid ; other products are methyl, ethyl, and
»-propyl alcohol, hexylene and other hydrocar-
bons, acrolein, and various ketones (Belohoubek,
B. 12, 1872 ; Letts, B. 5, 159 ; Fernbach, Bl.
[2] 34, 146).— 13. Distillation of the calcium
derivative CaO,HgOg gives methyl, ethyl, and
hexenyl alcohols, aldehyde, acetone, di-ethyl-
ketone, a ketone C,H,20 (124°), mesityl oxide,
and phorone (Destrem, A, Oh. [5] 27, 20). —
14. By heating with bromine and water at 100°
glyceric acid and bromoform are produced (Barth,
A. 124, 341). Bromine dropped into heated dry
glycerin forms acrolein. For the action of
bromine and Na^COj v. Reaction 6. — 15. HIAq
converts glycerin into allyl iodide and propylene;
an excess of HI forms isopropyl iodide (Erlen-
meyer, A. 139, 211). When glycerin is heated
with HCl mono- and di-chlorhydrins are formed,
togetherwithacrystalline compound [110°],whioh
appears to be a polymeride of epiuhlorhydrin
(Fauoonnier a. Sanson, Bl. [2] 48, 236). HBr
forms mono- and di-bromhydrins. — 16. Iodide
of phosphorus PI, forms propylene, aUyl iodide,
and a little allyl alcohol (Berthelot a. De Luca,
A. Oh. [3] 43, 257 ; 44, 350 ; Henry, B. 14, 403).
Glycerin may be conveniently converted into
allyl iodide by running a solution of iodine
(440 g.) in aUyl iodide (160 g.) into a heated
mixture of glycerin (2,000 g.), iodine (60 g.) and
red phosphorus (200 g.) (BShal, Bl. [2] 47, 875).
Glycerin (200 g.) may also be converted into
allyl iodide by mixing with iodine (135 g.), add-
ing clear phosphorus (40 g.) cautiously and dis-
tilling in a current of CO,. When glycerin (2 pts.)
is mixed with iodine (30 pts.) and red phosphorus
(5^ pts.) is cautiously added to the cooled mix-
ture, isopropyl iodide is formed, and may be dis-
tilled over. Aluminium foil and iodine also
form allyl iodide (Hodgkinson, C. N. 35, 237).—
17. PBr, and PBr^ form mono- and di-bromhy-
driu and s-tri-bromo-propane (Berthelot a. De
Luca, A. Oh. [3] 48, 304). PCI, and PCI5 act in
like manner. — 18. SjClj forms di-chlorhydrin
and s-tri-chloro-propane (Carius, A. 124, 222;
cf. Wolff, A. 150, 59).— 19. When glycerin is
distilled with ammonium chloride a chlorinated
compound (176°) is formed, together with some
acids, and a base 'glycoUne' CfHigNj (156°).
S.G. 13 1'008. This base forms a platinocmoride
B"HjPtClj, a deliquescent crystalline hydro-
chloride B"HC1, and a crystalline ethylo-iodide
B"EtI (6tard, C. B. 92, 795).— 20. When gly-
cerin is heated with acids one or more acid
radicles usually displace its hydroxylic hy-
drogen. Thus acetic acid forms the acetins,
citric acid forms the citrine, phosphoric acid
forms glycero-phosphoric acid, sulphuric acid
gives glycero-sulphuric acid. — 21. Excess of
oxalic acid is split up by glycerin at 100° into
formic acid and CO, (Berthelot, A. 98, 139).
When excess of glycerin is heated with oxalic
acid at 200°-250° it is reduced to allyl alcohol
(ToUens, A. 166, 130). Distillation with formic
acid also converts glycerin into allyl alcohol
{Henninger, Bl. [2] 21, 242).— 22. When glycerin
is distilled with dtrio add there is formed gly-
cide pyruvate CHj.CH.CHj,.O.CO.CO.CHs [82°]
O
(241°) (De Clermont a.Chautard, O.B. 105,620).
23. Distillation with Na^S gives an oil (58°)
whence HgO gives a crystalline compound [35°]
(SchlagdenhauSen, C. B. 76, 1021).— 24. Heated
with anhydrous borax it forms NaBO, and the
borin GgH^O, which is decomposed by water
into boracio acid and glycerin (Dunstan, P%.[3]
14, 41J. — 25. Glycerin acts upon benzoic aldehyde
at 200°, forming benzylidene-glycerin
C,HrOH<(^ ^C3H5(OH)
a liquid that is not volatile under atmospherio
pressure, but boils under 20 mm. pressure at
190°-200° (Harnitz-Harnitzky a. Menschutkin,
A. 136, 127 ; Bl. [2] 8, 253). In a similar
manner it reacts with aceUo aldehyde, forming
ethylidene-glycerin CHj.Ch/^ \CjH5(0H)
(184°-188°), S.G. 2 1-081, V.D. 4-162 ; and with
valeric aldehyde forming amyUdene-glyoerin
(224°-228°), S.G. £ 1-027, V.D. 5-526 (calc.
6-644). — 26. Glycerin in dilute solution under-
goes fermentation (due to BacilVus butyKcus 1)
in presence of chalk forming w-butyl alcohol,
ethyl alcohol, n-propyl alcohol, n-amyl alcohol
(138°), trimethylene glycol,hexoic, butyric,lactic,
and acetic acids, and evolving GO, and hydrogen
(Fitz, B. 9, 1348 ; 10, 276 ; 11, 42 ; 13, 36, 1311;
15, 876; Morin, C. B. 105, 816; c/. Berthelot,
A. Oh. [3] 60, 346 ; Bechamp, Z. [2] 5, 663 ;
Hoppe-Seyler, S. 8, 353; O. J. 40, 82; Freund,
M. 2, 638).— 27. Distillation of glycerin (1 kHo.)
withzinc-i2us< (2 kilos.) yields propylene, acrolei'n,
allyl alcohol, hexenyl alcohol C„H,oO (c. 140°),
and a compound 0,^2oO, (c. 200°) (Kerstein, B,
9, 695 ; Glaus, B. 18, 2'931).— 28. Distillation
with calciMm chloride gives a liquid CeH,oO,
(172°) formerly called glyceryl oxide, but which
appears rather to be the anhydride of acetyl-car-
binol (GHs.G0.CHj)20. The same liquid is found
in the black residue in the preparation of allyl
GLYCERIN.
619
aloohol fiom glycerin and oxalic acid. It may
be reduced by HI to glycerin. It is misoible
with water, alcohol, and ether. Water at 100"
converts it into glycerin. Br forms dibrom-
bydrin. Sodium-amalgam does not attack it.
Chromic acid mixture gives formic acicl and
acetic aldehyde. Hot dilute HCl converts it
into a substance that reduces Fehling's solution
and anunoniacal AgNO, (Linnemann a. Von
Zotta, A. Suppl. 8, 254 ; Von Gegerfelt, B. 4,
919; Zotta, A 174, 87; ToUens, ^. 1871, 528;
Tollens a. Loe, B. 14, 1947 ; Silva, O.B. 93,418).
29. Aniime, mitro-benzene, and H^SO, form
quinoUne (Skraup, 'M. 2, 139 ; 3, 381).— 30.
AceUanide and PjO, give {Py. 2)-methyl-pyridine
(Zanoni, B. 16, 628).— 31. Heated with am-
momMtn sulphate at 255° for seven hours there
is formed a mixture of bases of the pyridine
series, including pyridine, {Py. 2)-methyI-pyri-
dine, and a di-methyl-pyridine (Storch, B. 19,
2456, ef. BeacUon 19).— 32. By heating with
. aniline and ZnOl, it forms skatole (O. f ischer
a. German, B. 16, 710). — 33. Growing algss
(Spirogyra) are capable of converting glycerin
into starch (Bokorny, C. C. 1888, 858).
Metallic derivatimei. — The heat developed by
the action of alkalis upon glycerin has been
studied by De Fororand (0. B. 103, 696 ; 104,
116, 291, 361; 106, 665, 746; 107, 269).
NaG,H,0,. Obtained by heating glycerin with
sodium-amalgam or with NaOEt. Prepared by
• adding glycerin to an alcoholic solution of
NaOEt, when radiating stars composed of
minute crystals of NaC,H,OsHOEt separate (the
ppn. is exothermic, but the ppn. of GgH-NaO,
woold have been endothermic) ; when these crys-
tals are heated in a current of dry hydrogen
they give off their alcohol of crystallisation
(Letts, G. J. 25, 450 ; Blaas, M. 2, 785). White
deliquescent powder, decomposed by water into
NaOH and glycerin. CS, heated with it at 55°
forms NaS.CS.O.C3Hj(OH)2 ; an orange mass,
insol. ether, decomposing at 65°, and crystallising
from alcohol with HOEt (Lobisch a. Looss,
M. 2, 372). Glycerin (1 mol.) mixed with a
concentrated solution of NaOMe in MeOH de-
posits NaCsH^OsHOMe in deliquescent needles,
which give oft MeOH in a stream of hydrogen
at 120°. The corresponding NaCaH,0,HCrr,
NaO,H,0»HOO^!Pr, and ^a.0^0^00^,,
may be obtained in like manner (De Forcrand,
G. S. 104, 291). Sodium-glycerin and methyl-
ene chloride form syrupy
(CH,(OEQ.CH(OH).CH.O)jCHj (Holand, A. 240,
242). NajCAOa- [220°]. When NaCjHjOa is
mixed with alcoholic NaOEt and evaporated at
100° to 120° in hydrogen the residue is
NaO^jOsNaOEt, but at 180° the di-sodium
derivative Na^CgHsOj is left (Lobisch a. Looss,
M. 2, 843 ; De Fororand, O. B. 106, 665). Deli-
quescent crystalline mass ; readily decomposed
by moist air. The compound NajCgH^O, has
not been obtained, — KCjHiOsHOEt : lamince. —
ECsHjO, : obtained in the same way as the cor-
responding Na derivative (De Forcrand, G. B.
104, 116). Does not react with EOMe even at
180°. — KCsH^OsHOMe. — KCsHjO,HOPr, —
KCsHAHOCjH,,. — BaOsHA- Prepared by
heating glycerin with BaO at 50° (Destrem,
C. B. 90, 1213 ; A. Gh. [5] 27, 17, 44). White
deliquescent powder, turning yellow in dry air;
decomposed by water into baryta and glyeeria.
On distillation it gives hydrogen, BaCOa, me-
thane, propylene, and various alcohols of the
series 0„H2„0. — GaCAOg. Prepared in the
same way as the prececUng which it resembles
in physical properties. Decomposed on distil-
lation into aldehyde, acetone, di-ethyl-ketone,
mesityl oxide, phorone, methyl alcohol, ethyl
alcohol, and hexenyl alcohol (D.).— Pb.OjHjOa :
formed by mixing a hot solutionof Pb(0Ac)2(22g.)
in water (250 c.c.) with glycerin (20 g.) and KOH
(15g.). Slender needles.— Pbs(C3H50s)s- A sticky
pp. formed by boiling 60 grms. of lead acetate
with 250 c.c. water and 26 grms. of PbO, filtering
and mixing with 75 grms. of glycerin (S.G. 1-24)
and a solution of 20 g. EOH (in 100 c.c. water)
which has been boiled with excess of PbO. —
2(03H503Pb.PbN03),Pb(OH)N03. Formed by
adding NH, (2-57 grms.) to a solution of lead
nitrate (26 grms.) and glycerin (80 grms.) in
water (250 c.c.) (T.Morawski, J.pr. [2] 22, 408).
Na2Mn(G3H50j)j. Formed by boiling hydrated
HnO, (from Mn(0Ac)2 and chlorine) withglycerin
and aqueous NaOH (Schottlander, A. 155, 280).
Yellowish-red mass, insol. alcohol and ether,
V. sol. aqueous glycerin. Boiling water decom-
poses it with ppn. of hydrated MnOz- Its solu-
tion gives pps. with AgNOj, with Pb(N0s)2 and
with Hg2(N0,)j.— SrMn(CaH50a)2. Obtained by
dissolving strontium hydroxide (12 pts.) in gly-
cerin (160 pts.) and adding ppd. hydrated man-
ganese dioxide (3 pts.) to the boUing solution.
Light oohre-yeUow powder.
Glycerin mono-nitrate CjHjNOs i.e.
C,H5(OH)2(ON02). From glycerin and HNO,
diluted with (3 pts. of) water (Hanriot, A. Oh.
[6] 17, 1 18). Liquid, v. e. sol. water, si. sol. ether.
Explodes when struck.
Glyceryl tri-nitrate 03Hj(0N0j),.
Nitro-glycerm. [-20°]. S.G. 1-60 at 15° S.
■0125 ; S. (alcohol) 42 ; S. (MeOH) 125. Mol.
w. 227. Prepared by dropping glycerin (dried
at 100°) into a mixture of fuming ENO,
and cone. HjSO, kept below 10°. After
some hours the product is poured into water,
and the ppd. nitroglyberin dried at 70°
(Sobrero, A. 64, 398 ; Williamson, A. 92, 305 ;
Boutmy a. Fauoher, Bl. [2] 27, 383 ; Matthew
Hay, Tr. E. 32, 67). Viscid liquid, without
odour (when cold) but with sweet taste. Almost
insol. water, v. sol. alcohol, ether, chloroform,
HOAc, benzene, and phenol ; nearly insol. gly-
cerin. Solidifies in a freezing mixture in long
needles. Poisonous. When quite pure it may
be kept for any length of time, otherwise it
gradually decomposes forming glyceric, oxalic,
and nitrous acids (De la Bue a. MiiUer, A. 109,
122). When struck it explodes violently. A
mixture of nitroglycerin with silica in the form
of infusorial earth is called dynamite (Nobel,
D. P. J. 90, 124). Beactions.—l. Alcoholic
notoTt forms nitrite, nitrate, acetate, oxalate, and
formate of potassium, a reddish-brown resinous
m^ss, and a substance which when dissolved in
even 30 volumes of hot alcohol forms a jelly
when cold (Hay). — 2. Alkaline carbonates pro-
duce the same quantity of nitrous acid (contain-
ing 33 p.c. of the nitrogen) as alcoholic KOH.
Ammonia acts in like manner but less energeti-
cally. Na2HP04 behaves like NH,.— 3. HClAq
decomposes it, as does hot (but not cold) H^SO^
620
GLYCERIN,
4. HIAq decomposes nitro-glycerin into glycerin
and. NO (MiUs, J. 1864, 494).— 5. Cone. H^SO,
and Hg also give oS NO by the measurement of
which the nitro-glycerin might be estimated
(Hempel, Fr. 20, 85; Hess, Wr. 22, 128).—
6. When evaporated ■with yellow ammonium sul-
phide it is reduced to glycerin (Bloxam, C. N.
47, 169).
Glyceryl tri-nitrite CjHjINOj),. (o.
150°). S.G. i^ 1-291. Formation. — 1. Dry
nitrous acid gas from As^O, and HNO, (S.G.
1-35) passed into cold glycerin forms two layers,
the smaller is an aqueous solution of nitrous
acid, the larger is impure glyceryl trinitrite
C,Hj(0N0)3. It is purified by distillation in a
current of hydrogen (0. Masson, C. J. 43, 348).
Properties. — Boils at about 150° with partial
decomposition. TeUowish oil. Burns with
whitish flame, does not explode when struck.
Bleaches the skin. Sol. ether, chloroform and
benzene, but insol. CS^. With cold glacial acetic
acid, it forms a green solution which gives ofF
nitrous fumes when heated. It decomposes spon-
taneously giving ofE NO. Beactions.—l. ILjSO,
violently decomposes it. — 2. KjCOj forms KNO2.
3. Alcohol forms EtONO.— 4. It does not mix
with water, but is slowly decomposed by it,
glycerin and HNO^ being apparency formed in
the first instance.
Glyeero-sulphuric acids: —
Mono-sulphwrim C3Hj(OH)2SO,H. Olycerin-
sulphuric acid, l^rom glycerin (1 pt.) and sul-
phuric acid (2 pts.) (Pelouze, A. Oh. 63, 21). Un-
stable liquid, being decomposed by evaporating
its solution even below 0°. It decomposes car-
bonates forming salts which are v. sol. water
and very unstable. — GaA',: needles, begins to
decompose at 140°, giving off acrolein, acrylic
acid, and SO, (Bedtenbacher, A.il, 118).
Di-sulpfmrin C,B.^{80tB.)2{0S.). Formed by
slow action of water on the tri-sulphurin which
it much resembles (Claesson, J, pr. [2] 20, 6).
Tri-svlphurm 0,Hs(S04H),. QVyeeryl tri-
suTphiurio acid. Formed by adding glycerin
slowly to chloro-sulphuric acid (CISO3H) as long
as HCl is briskly given off. The crystals obtained
are dried over H^SO, (Claesson, J. pr. [2] 20, 4).
Slowly decomposed by water : 03H5(S04H)3 -f HjO
= C3H5(S04H)2(0H) + HjSO,. Boiling water de-
composes it into glycerin and sulphuric acid. —
BajA'j.
Glycero-phosphoric acid CjHjPOj i.c.
C3H5(OH)20.PO(OH)ij. Exists in smaU quan-
tity in human urine (Sotnitschewsky, If. 4, 214).
Obtained from lecithin or the yolk of eggs by
boiling with aqueous alkalis or baryta (Gobley,
/. Ph. [3] 9, 161 ; Streoker, C. B. 52, 1270).
Formed by heating glycerin with H3P04 or PjO^
(Pelouze, C. 22. 12, 718). The free acid is decom-
posed by evaporation of its aqueous solution.
Salts. — BaA" (Thudiohum a. Kingzett, G.
J. 30, 20).— BaA" aq.— CaA".— CaH^"j.-PbA":
insol. water.
Di-stearyl-glycero -phosphoric acid
C3Hs(0.C„H,5O)jO.PO3H2. [55»-63°]. Obtained
by heating di-stearin with PjOj at 110°. The
product is treated with alcohol 85 (p.c). The
residue is extracted with boiling alcohol and fil-
tered ; powdered Na^CO, is added to the filtrate
when a mixture of sodic phosphate and sodic di-
stearyl-glycerophosphate in ppd. This is ex-
tracted with hot benzen« which dissolves tbe
latter. A mixture of glacial acetic acid and
E0SO4 liberates the free acid from its sodium-salt
(Hundeshagen, J. pir. [2] 28, 235). Fat-like
mass. Beddens moist litmus. The fused acid
swells up when moistened. . SI. sol. hot water
and dilute acetic acid, insol. dilute mineral acids,
V. sol. aqueous alkalis, glacial acetic acid, alco-
hol, ether, benzene, and benzoline. Separates
from hot solutions in a paste-like mass of small
needles. Heated with dilute acids or alkalis it
gives glycerin, stearic acid, and phosphoric
acid. The ammonium salt is decomposed by
heat into NH, and the free acid. The sodium
salt melts about 180°; on cooling it soliUi lies
to a glassy mass which swells up in warm water
forming a mass of globules resembling the mye-
line condition of lecithin.
Chloride C3H5(O.C,8H3jO)i,O.PO.Clj. [24°].
From di-stearin (4 pts.) and POCI3 (1 pt.) ; the
product being extracted with ether. The ether
is then mixed with alcohol, filtered, and placed
over HjSO, and KOH. Wedge-shaped plates.
V. sol. alcohol, ether, and benzene. Decomposes
at 100°, forming stearic acid. Water soon de-
composes it into stearic acid, glycero-phosphoric
acid, and HCl,
Neurine salt
C3H,(O.C„H3,,0),O.PO(OH).ONMe,C,H,OH.
Prepared by digesting di-stearyl-glycerophos-
phorio acid with an alcoholic solution of the
proper quantity of neurine carbonate. Waxy
mass. Sol. alcohol. Swells up in warm water,
forming round globules like the myeline form of
lecithin. An alcoholic solution of PtCl4,2HCl
gives a pp. of neurine platino-chloride only.
Lecithin (j. v.), on the other hand, gives a pla-
tino-chloride of its own under similar conditions.
Formyl derivative C3H5(0H)3(0CH0).
Monoformm. Formed by heating glycerin with
oxalic acid at 190° (ToUens a. Henninger, Bl.
[2] 11, 395)4 Formed also by the action of
monochlorhydrin upon sodium formate at 160°
(Van Bomburgh, B. T. 0. 1, 186). Decomposed
on distillation into CO,, water, and allyl alcohol,
Di-formylderivativeCfi^{aE){O.CE.O)y
Diformin. (c. 165° at 20 mm.). S.G. 15 1-304.
may be extracted by ether from the residue
obtained in preparing formic acid by distilling
anhydrous oxalic acid with glycerin (Van Bom-
burgh, O. B. 93, 847). Liquid, sol. alcohol,
ether, and chloroform, insol. CSj. Inactive to
light. Decomposed by water into formic acid
and glycerin. Decomposed by distillation into
water, CO,, and allyl formate. When heated
with anhydrous oxaUc acid it gives off CO, and
formic acid, and may therefore be an interme-
diate product in the preparation of formic acid.
When heated with glycerin • (5 pts.) at 220° it
gives CO, CO,, and allyl alcohol.
Mono-acetyl derivative C,H,„04 i.e,
C3H3(OH)j(OAo). Mol. w. 134. S.G. 1-20. Ob-
tained by heating a mixture of equal volumes of
glycerin and glacial acetic acid at 100° for a long
time (Berthelot, A.Ch. [3] 41, 277; Berthelot a.
De Luca, A. Ch. [3] 52, 433). Neutral liquid,
having a faint ethereal odour. Miscible with
ether. When mixed with half its bulk of water
it forms a clear liquid, which becomes turbid oa
GLYCERIN.
621
addition of a larger quantity of water, by which
it is partially decomposed. With alcohol and
HCl it yields glycerin and acetic ether.
Bi-acetyl derivative C.B.^jO^i.e.
CjHs(OH)(OAc),. Diacetm. Mol.w. 176. (280°).
S.G. 1^' 1'184. Formed by heating glycerin
(1 pt.) with glacial acetic acid (4 or 5 pts.) at
300°. Liquid; becomes viscid at —40°. Scarcely
attacked by AcOl (Hubner a. MiiUer, Z. 1870,
S44).
Di-acetyl derivative 03H5(0H)(0Ac)2.
(252°). S.G. 22 1-148. Prom epichlorhydrin and
AgOAo (Laufer, J. 1876, 343).
' Triacetyl derivative OM,fl. i.e.
C,H,(OAo),.
J'riacetin. Glyceryl triacetate. Mol. w. 218.
(268° i. v.). S.G. 2 1-174. S. 18, at 27°., Occurs
in some fats, as in the oil from the seed of the
spindle-tree (Euonyimis eurqpceus) (Schweizer,
J. pr. 53, 437). Formed by heating diacetin
with glacial acetic acid (18 pts.) for 3 hours at
250°. Formed also by heating s-tri-bromo-pro-
pane with AgOAc (Wurtz, A. 102, 339), Pre-
pared by boiling glycerin (150 pts.) with HOAo
(300 pts.) for 40 hours, fractionally distilling the
product, dissolving in water, and extracting with
ether (H. Schmidt, A. 200, 99). The rate of
etherifioation of glycerin by acetic acid has been
studied by Menschutkin (B. 13, 1814). Liquid,
sol. dilute alcohol and ether.
Mono-butyryl derivative C,H,40i i.e.
03H5(OH),(O.CO.Pr). S.G.il 1-088. S. 267.
From butyric acid and glycerin by heating for 3
hours at 200° (Berthelot, A. Ch. [3] 41, 261).
Neutral liquid ; mixes with | vol. of water, but
on adding more water the solution becomes tur-
bid. Decomposed by alkalis and alkaline earths
into glycerin and butyric acid. Alcohol andEGl
yifeld butyric ether and glycerin.
Di-butyryl derivative
C,H5(0H)(0.C0.Pr)j. (320°). S.G. " 1-083.
Formed by heating glycerin with butyric acid
for several hours at 275°. Liquid. Not solid
at —40°. Aqueous NB[, decomposes it, forming
butyramide.
Tri-hutyryl derivative C3H5(O.OO.Pr)j.
(285°). S.G. S2 1-052. Occurs in butter, along
with other glycerides. Obtained by heating
mono-butyrin (1 pt.) with butyric acid (15 pts.)
at 240° for 4 hours (Berthelot). 'Formed also
by boiling glycerin (1 mol.) with butyric acid
(3 mols.) for 60 hours (Lebedeff, H. 6, 150).
Oil, v. sol. alcohol and ether.
Mono-valeryl derivative
C3H5(0H),,(0.C0.C<H,), S.G.ie 1-100. Formed
by heating valeric acid with excess of glycerin
for 3 hours at 200°. Mixes with half its bulk
of water, but the solution becomes turbid on
further addition of water. Alcohol and HCl
form valeric ether and glycerin. NHjAq gives
valeramide.
Bi-valeryl derivative
C,H5(0H)(0.C0.C4H,)j. S.G. is 1-059. From
glycerin and valeric acid at 275°. ' Oil, with
fishy odour. Becomes semi-solid at —40°.
Tri-valeryl^ derivative
03Hs(0.C0.C4H:s)3; From glycerin (1 pt.) and
valeric acid (9 pts.) at 220°. , Oil ; sol. alcohol
and ether. Occurs in the oil of Delphinus
globiceps (Chevreul).
Mono-bemoyl derivative
C,H.(0H)3(0Bz). Bmztiicm., S.G. '-^^ 1-228.
Formed by heating benzoic acid with excess of
glycerin at 200° (Berthelot, A. Ch. [3] 41, 290).
Thick viscid oil, iusol. water, si. sol. CS.^, v. sol.
alcohol and ether. Decomposes at 320°, giving
off acrolein and benzoic acid.
Di-henzoyl derivative 0^s(0'E.)(0'Bz)2.
[70°]. From glycerin, BzOl, and dilute NaOH
(E. Baumann, B. 19, 3221). Long needles (from
ligroin) ; insol. water, v. e. sol. alcohol and
ether.
Tri-henzoyl derivative 08H5(OBz)3.
Trihenzolcim. [74°]. S.G. iS 1-228. Obtained
by heating benzoicin with benzoic acid (12 pts.)
for 4 hours at 250° (B.). Formed also by heating
epichlorhydrin with HOBz; or from epibrom-
hydrin and KOBz at 200° (Van Bomburgh,
B. T. 0. 1, 46, 143). Large needles (from ether).
Y. e. sol. ether, v. sol. boiling alcohol, si. sol.
ligroiiu.
o-Oxy-bensoyl derivative
03H3(OH)j(O.0O.C3H,.0H). S.G. 1-1366. From
salicylic acid, glycerin, and HCl at 100° (Gottig,
JB. 10, 1817). Colourless liquid ; v. sol. alcohol,
ether, and CS,.
Benzoyl-suocinyl derivative C„HuOj
t.e. CS.i(G.Si^OpO^^.O'Bz. Benzosucainin.
Formed by heating glycerin with benzoic and
succinic acids at 200° (Tan Bemmelen, J. jir.
69, 84). Soft mass, decomposed by boiling
water or alcohol, more readily by alkalis, into
glycerin, benzoic acid, and succinic acid.
Tri-myriatyl derivative C^HjjO, i.e.
08H5(0.0,«Hj,0),. [55°] (Masino, A. 202, 173) ;.
[46°] (in Otoba). Occurs in nutmegs (from
Myristica mosehata), from which it may be ex-
tracted by ether (Playfair, A. 37, 165 ; Comar,
J. 1859, 366 ; Cimento, 9, 185). Occurs also in
otoba, a fatty substance derived from Myristica
Otoba (Uricoechea, A. 91, 369). Crystallises from
ether in lamina. Split up by boilmg alkalis into
glycerin and myristic acid.
Mono-palmityl derivative G,gH,g04
t.e. 03Hs(OH)j(O.C,3Hj,0). Monopalmitm. [58°]
(B.); [63°] (p. a. S.). S. (alcohol) 5-306 at 22-5°.
Obtained by heating a mixture of glycerin and
palmitic acid for 24 hours at 200°; the product
is shaken with lime-water and extracted with
ether, from which tripalmitin separates first,
then dipalmitin, and finally monopalmitin
(Berthelot; Chittenden a. Smith, Am. 6, 225).
Badiating prisms ; may be distilled in vacuo, but
is decomposed when heated under atmospheric
pressure, yielding acrolein and other products.
Di-palmityl derivative C35H5SO5 i.e.
0,H5(OH)(O.0„H3,O)a. Dipalmitm. [50°] (B.) ;
[61°] (C.a. S.). S. (alcohol) -2i0 at 20°. Formed
by heating palmitic acid with glycerin for
14 hours at 100° (B.). Tables or needles. Like
the, other palmitins, it is rapidly saponified by
water and PbO at 100°.
Tri-palmityl derivative CjiHjgOj i.e.
03Hs(O0,3H3,O)j. Tripalmitin,. Mol. w. 806.
[62°]. S. (alcohol) -0043 at 21°. Occurs in
those natural fats that yield palmitic acid on
saponifica|ion {v. Fats and Acms). Obtained
from palm oil by expressing the liquid portion,
washing the residue with boiling alcohol, and
orystallising it from ether (Stenhouse, 2. 36,
«23
GLYCERIN.
54). , It may be formed by heating monopalmitin
(1 pt.) trith palmitio acid (10 pts.) for 28 hours
at 250° (Berthelot). Crystalline mass, t. si. sol.
alcohol, y. e. sol. ether. According to Duffy
(C J- 5, 197) some varieties of natural pahnitin
melt at 46°.
Mono-stearyl derivative C^iH^O, i.e.
C5H5(OH)j(O.C,gHa50). MmosteaHn. [62°].
Prepared by heating steario acid with excess of
glycerin at 220° as long as the former increases
in volume. The upper layer is recrystallised
from alcohol and ether (Berthelot, A. Ch. [3]
41, 221 ; ¥. Hundeshagen, J. pr. [2] 28, 226).
Dendritic groups of needles. Beadily soluble in
warm alcohol and ether. May be distUled m
vacuo. Easily saponified by alcoholic potash.
Gives off acrolein when strongly heated.
Di-stearyl derivative OjjHjjOj i.e.
C3H5(OH)(00„H350)2. ■Di-stea/rim. [77°]. S.
(alcohol) '7 at 78°. Prepared by heating mono-
stearin with the calculated quantity of stearic
acid at 180° as long as water is evolved. Crys-
tallised from alcohol and then from benzoline
(Berthelot; Hundeshagen). Clumps of glitter-
ing plates (from alcohol) ; or small spheroids,
formed of radiating clusters of minute needles
(from ether, ligroin, benzene, and CHCI3).
Saponified by alcoholic KOH. Metallic de-
rivatives. — C3H508(C„H350)jONH4. From
NH3 and an ethereal solution of di-stearin. —
C3H5O3(0,sH,5O)2ONa. Acetyl derivative.—
C3HA(C,sH3.0)^c. [30°].
Tri-stearyl derivative CsjEujOb i.e.
03H5(O.C,8H35O)3. Tristearin. Stearin. [55°]
and [72°]. S.G. (liquid) -925 at 66°. Occurs in
many fats, especially in the solid tallows and
lards from animals (Chevreul, Becherches sv/r Us
corps gras ; Braconnot, A. Ch. 93, 225 ; Vogel,
A. Ch. 68, 154 ; Lecanu, A. 12, 25 ; Liebig a.
Felouze, A. 19, 264 ; Bedtenbacher, A. 35, 195 ;
Francis, A. 42, 254; Arzbacher, A. 70, 239;
Heintz, P. 84, 221 ; Duffy, C. J. 6, 197, 303 ;
Berthelot, OfiAmie OrgwnAqv^, 2, 52 ; A. Oh.
[3] 41, 216, 482; 47, 297; Kopp, A. 93, 194;
Bouis, C. B. 45, 35 ; Bouis a. Pimentel, G. B.
44, 1355). It is very difficult to free stearin
from palmitin by fractional crystallisation, but
it may be obtained from the fat of the seeds of
Brindama indica. Best prepared in a pure state
by heating monostearin (1 pt.) with stearic acid
(18 pts.) at 270° for 3 hours (Berthelot) ; or by
heating glycerin with stearic acid for 24 hours
at 200° (Heintz, A. 92, 300). Pearly nodules or
laminas and slender needles. V. si. sol. cold
alcohol, V. sol. boiling alcohol, v. e. sol. ether.
Has no taste or odour. May be distilled m vacuo.
When heated it melts -at 55°, but when further
heated it becomes solid again, and finally melts
at 72°. These two melting-points are lowered
by impurities, thus when the stearin has been
prepared from fats they may be 52° and 62°
respectively. According to Duffy this pheno-
menon may be explained by assuming the exist-
ence of three modifications of stearin.
Arachyl derivative CjjH^O, i.e.
C3H5(OH)j(OC2„Ha,0). From arachic acid and
glycerin (Berthelot, A. Ch. [3] 47, 355).
Granules, v. si. sol. cold ether.
Di-arachyl derivative C^gHg^O, i.e.
C3H,(0H)(0C3^3„O),. [75°]. Slender grains.
V. si. aol. cold ether.
Tri-arachyl derivative Cg^^^O^ i.e,
C,H5(O.Ca,H3„0)3. Triarachm. Occurs in the
kernels of Nephelium la/ppaceum, and probably
also in butter and in the oil from the ground nut
{Arachis hypogcea) (Goldschmiedt, J. 1877, 728 ;
Sitz. W. [2] 74, 394; Oudemans, Z. 1867, 256 ;
Gossmann, A. 89, 1). SI. sol. ether.
Mono-oleyl derivative G2,H,gOt i.e.
C8H5(OH)j(OC,8HoO). Mono-ole'in. S.G. 3*
*947. Formed by heating oleic acid with excess
of glycerin for 18 hours at 200° (Berthelot).
Oil ; may be solidified.
Di-oleyl derivative G3gH.,.J0^i.e.
C3H3(OH)(OC„H330),. S.G. 21 -921. Oil.
Tri-oleyl derivative C,,H,g,Og i.e.
C3H5(OC,sH330)s. Tri-ole'Cn. OMn. The chief
constituent of fatty oUs ; occurs also in solid
fats. May be formed by heating glycerin with
excess of oleic acid at 240° (Berthelot). Oil.
May be distilled in vacuo. Decomposed by dis-
tillation under atmospheric pressure, n-hexane
andn-heptane being among the products (Engler,
B. 22, 594). Slowly saponified by water and
PbO at 100°. V. si. sol. alcohol, v. e.
sol. ether. Cone. HjSOf converts it into oily
/O.0O.CH:CH.C,5H„
0,H/-0.00.CH(S04H).CHj.C,5H3, (Turkey red
\0.00.0H(0H).CHj.C,5H„
oil) (Geitel, J. pr. [2] 37, 85). Nitrous acid con-
verts it into the isomeric solid elaidin, a crystal-
line substance, almost insol. alcohol, v. e. sol.
ether, melting at [38°] (Duffy, C. J. 5, 197).
Olycero-tartaric acid 0,H|jOg i.e.
C3H3(0H)j.0.00.CH(0H).CH(0H).C03H.
Formed by heating equivalent quantities of
glycerin and tartaric acid to about 150° (Berze-
lius, Handbuch; Des Plats, C. B. 49, 216).
Semi-solid mass ; insol. ether, v. sol. alcohol,
slowly resolved by water into glycerin and tar-
taric acid.— CaA'2 3aq : deliquescent amorphous
mass. — BaA'j.
Olycero-di-tartarie acid C„H,gO,3i.e.
C3H3(OH).(O.CO.OH(OH)CH(OH).OOjH)3. From
glycerin (1 pt.) and tartaric acid (1 pt.) by heat-
ing at 100° for 50 hours. An acid 0„H„0|2 is
formed at the same time.
Glycero-tri-tartaric acid CuH^O,,.
Formed by heating glycerin (1 pt.) with tartaric
acid (26 pts.) at 140°. Tetrabasic acid.
Mono-ethyl ether O^B.,J[), i.e.
0,H,(0H)2(0Et) or CH2(0H).CH(0H).0H,0Et,
(225°-230°). Formed by heating ohlorhydrin
with NaOEt at 200°, treating the residue with
water, then with KjCO,, agitating with ether,
and fractionally distilling the extract (Beboul,
A. Ch. [3] 9, 5). Liquid, sol. water, but separated
therefrom by KJCO3.
Di-ethyl ether 0.,'B.„0,i.e.
CHj(OBt).CH(OH).CHj(OEt). (191°). S.G. -92.
Formed by the action of NaOEt on didhlorhydrin
(Beboul) ; or by heating glycerin with EOH and
EtBr (Berthelot).
Tri-ethyl derivative Ofi^O,i.e.
C,H5(0Et)3. TriethyUn. (180°-190°). From
the preceding by successive treatment with PGl,
and NaOEt (Beboul a. LonrenQO, C. B, 62,466).
Oil.
Isoamyl derivative C^,,0, i.e.
0,Hs(OH),(00,H„). Isoamylm. (261°). 8.0.
GLYCERIN.
629
52 -98. Formed by heating CHj.0H.CHj.O.0sH„
O
with water for some hours at 200° (Beboul).
OU.
Di-isoamyl derivative C,3Ha,0j i.e.
C,H5(0H)(00jH,X. (273°). S.G. 2 -907. Prom
dichlorhydrin and NaOOsH,,.
Ethyl-isoamyl derivative C,„H«,Oa i.e.
0^5(0H)(OEt)(OC5H„). (239°). S.G. -92.
From the mono-isoamylin by suooessive treat-
ment with fuming ECl and NaOEt. Oil.
Mon,o-allyl derivative CsH,„0, i.e.
C.H,(OH)j(00,H,). (240°). S.G. 2 1-116. Occurs
in the syrupy liquid left in the preparation of
allyl alcohol by heating ozalio acid with excess
of glycerin (Tollens, B. 5, 68; A. 156, 149).
Liquid, m. sol. water. Br forms oily G^i^x.fl„
Tri-allyl derivative Oi^HjoOa i.e. ,
C3H5(0C,H5)3. Tri-alVyKn. (282°). From
glycerin, aUyl iodide, and KOH (Berthelot a.
De Luoa, A. 100, 361).
Di-phenyl derivative 0,sH,jO, i.e.
CHj(0Ph).CH(0H).CH2(0Ph). [81°]. Formed
by adding s-dichlorhydrin (70 g.) to phenol
(100 g.) and KOH (60 g.) (Bossing, B. 19, 64).
Pearly plates (from alcohol). Insol. water, m.
sol. alcohol, V. e. sol. ether. When heated with
AoOl (1 mol.) it gives C.sHjjAoOa [71°], but with
4 pts. AcOl it forms liquid CjiH^^Og. In like
manner BzCl (1 mol.) forms OisHjsBzO, [67°]
but boiling BzCl (7 pts.) forms oily OjjHajOa.
Forms a stable sodium derivative CiaHjaNaOa.
On sulphonation it gives the disulphonio acid
CH(OH)(CHjO.OaH4.S03H)a of which the salt
EjA" 2aq is v. sol. water.
Di-nitro-phetiyl derivative OjHiaNjO,
i.e. 0,H5(0H)j.00.H3(N0j)2. [o.83°]. From
chloTo-m-di-nitro-benzene, glycerin, and KOHAq
(Willgerodt, B. 12, 764).
Benzylidine derivative
CaHi.CH<[Q>0aH5.OH. From glycerin and
benzoic aldehyde at 200° (Earnitzky a. Men-
schutkin, A. 136, 127). Oil. Decomposed by
water.
w-Chlorhydrin CgH^ClO, i.e.
CH301.CH(0H).CH20H.
Ohloro-pnrpylene glycol. Mol. w. 110^.
(213°) (Hanriot). S.G. 2 1-338. Formed, to-
gether with smaller quantities of the isomeric
CH2(0H).CHC1.CH20H, by saturating glycerin
with HGl and keeping the liquid for some hours
at 100° (Berthelot, A. Ch. [3] 41, 296). Formed
also by heating epichlorhydrin with water
(Beboul; Hanriot, A. Ch. [5] 17, 62).
Prepwmticm. — The product of the action of
dry HGl on damp glycerin in sealed tubes at
100° is distilled under 18 mm. pressure, the
u-chlorhydrin passing over at 139°, the s-iso-
meride at 146° (Hanriot). There is obtaiaed
about 16 times as much of the u- as of the
s-ohlorhydrin.
ProperHes. — Liquid, misoible with water,
alcohol, and ether. Unless quite free from HGl
it suffers condensation when distilled.
BeaoUons. — 1. Sodium amalga/m reduces it
to propylene-glycol (Louren^o, C. B. 52, 1043 ;
Buff, Bl. [2] 10, 123). — 2. Potassium cyardde
forms a nitrile which is decomposed on distilla-
tion, but is converted by boiling with dilute
HNOa into di-oxy- butyric acid (Haniiot, 0. R.
86, 1139 ; Bl. [2] 27, 256).— 3. .Barj/to acting on
its ^thereal solution forms small quantities ot
glycide and epichlorhydrin. — 4, When heatou
with an aqueous solution of trimethyla/mine in
sealed tubes it yields C3H3(0H)2NMe301 and
0aH5(0H)2NMeH3Gl. The former gives a crys-
talline platinoohloride (03H5(0H)jNMe3Gl)2PtCl,
and aurochloride GsH5(OH)jNMe3Au0l4 (Hanriot ;
V. Meyer, Z. [2] 5, 439).
Di.nitrate OHjGl.GH(O.NOj).CHa(O.NOi,).
S.G. 2 1-511. From ohlorhydrin, HjSO,, and
HNO3 (Henry, A. 155, 164).
Di-formyl derivative
0H3C1.0H(00H0).GHj(Q0H0). (185°-195°) at
22 mm. Formed from the ohlorhydrin by heat-
ing with nitro-methane at 180° (Ffungst, J. pr.
[2] 34, 36).
Acetyl derivative CjHs(0H)(0Ac).0H2Cl.
(250°). Aceto-chlorhydrin. Formed, together
with dichlorhydrin, by passing HOI into a mix-
ture of acetic acid and glycerin at 100°; also,
together with the following, by the action of
AcOl on glycerin (Berthelot a. De Luca, A. Ch.
[3] 52, 433). From epichlorhydrin and HOAo
at 100° (Beboul, A. Svppl. 1, 232).
Di-acetyl derivative
GH,(OAo).CH(OAc).CH,a. (245°). S.G. *
1*243. From acetyl chloride and a mixture of
eqaal volumes of glycerin and HOAo (Berthelot
a. De Luca, A. Ch. [3] 52, 401 ; cf. Franchi-
mont, 22. T. O. 1, 43). Also from epichlor-
hydrin and AcjO at 180°, a compound C„H„G10,
(240° at 20 mm.) being formed at the same time
(Truchot, A. 138, 2S9).
Di-palmityl derivative
G3H,01(00,aH3,0)j. [44°]. From glycerin and
palmityl chloride (YiUier, B. 9, 1933).
Stearyl derivative
C,HaGl(OH)(OG,aH330). [28°]. Produced by
passing HGl into a mixture of stearic acid and
glycerin (Berthelot).
Benzoyl derivative G3H5Cl(OH)(OBz).
[-40°]. From glycerin, HOBz, and HGl (Ber-
thelot, A. Ch. [3] 41, 302).
Ethyl derivative
GHjGl.GjH3(0H)(0Et)? (188°). From epi-
ohlorhydrin and HOEt at 180°. Formed also from
CHj.GH.GHjOBt and HCl (Beboul, A. Suppl. 1,
0
Isoamyl derivative
0H,Gl.G.;H3(0H)(00aH„). (235°). _ S.G. ^2 1-0.
Formed from epichlorhydrin and isoamyl alco-
hol at 220° (Beboul).
s - Ohlorhydrin GHj(0m.0HCl.GH,(0m.
Chloro-frimefhylene glycol. (145° at 10 mm.).
S.G. 2 1-328. Occurs in small quantity among
the products of the action of HGl on glycerin
at 100°, and may be isolated by fractional dis-
tUlation in vacva (Hanriot, 0. B. 86, 1139 ;
A. Ch. [5] 17, 73). Formed also by the action
of HOGl on ally! alcohol (Henry, A. 155, 322).
Liquid, resembling the et-isomeride. It has a
great tendency to form polyglycerio derivatives.
Acetyl derivative
CH3(OH).GHGl.CH2(OAc). (230°). S.G. 2 1-27.
From allyl acetate and HOGl.
Ethyl derivative
CH,(OH).GHGl.CHj(OEt). (183°). B.G. «
624
GLYCEkijn.
1'117. From ethyl allyl oxide andHOCI (Lauch,
B. 18, 2287). Thick liquid.
Di-ethyl derivative
CH2(0Et).CHCl.CHj(0Et). (184°). S.G. i^
1-005. From di-ethyl-glycerin and PCI5 (Eeboul
a. Lourenfo, A. 119, 237).
SicMorliydTins v, Di-chlobo-fboftl aiiCo-
HOLS.
Chloro - bromhydrins OHjBr.CjHjOl(OH).
(198°). S.G. i2 1-740. From allyl bromide and
HOC! (obtained from chloride of Ume and borio
acid) (Lauch, B. 18, 2288). Also from epiohlor-
hydrin and HBr and from epibromhydrin and
HOI (Beboul, A. Suppl. 1, 225). Liquid. Cone.
EOHAq gives epichlorhydrin.
Acetyl derivative OjH5Br01(OAc).
(228°). From glycerin, AcCl, and AoBr (Ber-
thelot a. De Luoa, A. Oh. [3] 52, 462). SI. sol.
water.
Ethyl derivative CaHsBrO^OEt). (187°).
From epichlorhydrin and EtBr (Beboul a.
Louren(jo, A. 119, 238).
Bromhydrin CsH-Br02 t.e.
CHj(0H).CHBr.CH2(0H) ? (180° at 10 mm.).
Formed by adding glycerin (500 g.) in small por-
tions to liquid bromide of phosphorus (550 g.),
the liquid being kept cool and the product after
24 hours fractionally distilled in vacuo (Berthe-
lot a. De Luoa, A. Ch. [3] 48, 304 ; 52, 483).
Oil, sol. ether. In its preparation there is also
formed CjH^rO (below 200°) and crystalline
CjHjBrjP wMch is not affected by aqueous KOH
at 100°-
Acetyl derivative 03H5Br(OH)(OAc).
(170°-180°) at 10 mm. Prepared by the action
of AcBr (1-5 pts.) on dry glycerin (1-2 pts.) the
crude product being distilled under 10 mm. pres-
sure ; the yield is good (2-2 pts.) (Hanriot, A, Ch.
[5] 17, 84). Eeduoed by the copper-zinc couple
to tri-methylene glycol.
Di-ethyl derivative C8H5Br(0Et)2.
(195°-205°). S.a a 1-258. From di-ethyl-
glycerin and PBrj (Henry, B. 4, 704).
Bromhydrin OsH,Br02 i.e.
CH,(OH).CH(OH).CHjBr. (138° at 17 mm.). A
product of the action of Br on aUyl alcohol in
presence of water (Fink, M. 8, 561). By the
action of HBr on dry glycerin, Veley (C. N. 47,
89) obtained a bromhydrin (160°) at 60 mm.;
S.G. J 1-717.
Di-bromhydrinB v. Di-bkomo-pbopyii aloo-
BOIiS.
Tri-bromhydrin v. Tki-bkomo-peopanb.
lodhydrin OA(OH)jL S.G. 12 203. From
chlorhydrin and KI (Eeboul, A. Ch. [3] 60, 5).
Di-iodhydrin v. Di-iodo-pbopyii alcohol.
Chloro-iodhydrin v. Chloeo-iodo-peopyl alco-
hol.
Methyl derivative 03H5ClI(OMe). (0.
200°). Formed by heating epichlorhydrin (1
mol.) with Mel (1 mol.) at 190° ; the yield being
20 p.o. of the theoretical (Paal, B. 21, 2971).
Oil, volatile with steam.
Ethyl derivative 03H501I(0Et). (200°-
210°).
Isopropyl derivative OjH5ClI(OPr).
(208° -212°).
n-Propyl derivative 03H501I(0Pr).
(200°-210°).
Diplyoerin OjHuOj i.e.
0,H5(OH)j.O.C3H5(OH)r PyrogVycerin. (220°-
230°) at 10 mm. When glycerin, diluted with
one-third of its bulk of water, is saturated at
100° with HCl, then mixed with an equal bulk of
glycerin, and heated with inverted condenser for
13 hours at 120°, there is obtained a mixture of
dichlorhydrin, diglycerin chlorhydrin, diglycerin
dichlorhydrin, diglycerin, and triglycerin ; these
may be separated by fractional distillation in
vacua (Lourenfo, C. B. 52, 359). Thick liquid,
insol. ether, si. sol. cold, v. sol. hot water, mia-
oible with alcohol.
Mono-stearyl derivative
03H3(O.0„H,,O)(OH).O.03H.(OH),. [about 30°].
Formed by heating glycerin alone for some time
and then with stearic acid for several days at
240°. Crystallised from alcohol (Hnndeshagen,
J. pr. [Z] 28, 252). Wax-like solid, sol. ether.
Beadily saponified by alcoholic potash.
Tri-ethyl derivative Of^^Oni-e.
C,H3(0H)(0Bt).0.0,Hs(0Et)j. (0. 290°). S.O.
^ 1-90. Formed, together with di-ethyl-
glyoerin and tetra-ethyl-triglycerin, by the
action of NaOEt on epichlorhydrin (Eeboul a.
Louren^o, G. B, 52, 401). Liquid, sol. water,
alcohol, and ether. Ppd. from its aqueous solu-
tion by KjC03.
Diglycerin chlorhydrin CeH,3C104.
(270°). Formed together with diglycerin dichlor-
hydrin C3H,2Cl204 by heating glycerin saturated
with HCl. By heating either chlorhydrin with
alcoholic KOH at 100° there is formed pyro-
glyoide OsH.A (245°-255°). This body is
also got by heating polymerised glycide acetate
with NaOH (Breslauer, J. pr. [2] 20, 193). It
is miscible with water and alcohol.
Di-ethyl derivative of diglycerin
chlorhydrin Oi„S^010ti.e.
003H,„(0H)(0Et)jCl. (285°). S.G. ^ 1-11.
Formed by heating' di-ethyl-glycerin with epi-
chlorhydrin at 200°. Formed also, together with
ethyl- and di-ethyl-ohlorhydrin, by heating
epichlorhydrin with alcohol at 200°. Liquid,
si. sol. water, miscible with alcohol and ether.
Acetyl derivative of diglycerin tri-
chlorhydrin C8H,3Cl30, i.e. OCaH,„(0Ao)0l3.
(190°) at 20 mm. A product of the action of
AcCl on epichlorhydrin (Tnichot, A. 140, 245).
Triglycerin CbHjoO, i.e,
03H5(0H)2.0.C,H3(0H).0.C,H.(0H)2. (275°-
285°) at 10 mm. Formed as described nnder
diglycerin. Thick liquid.
Tetra-ethyl derivative of triglycerin
0„H330, i.e. 0„H,502(0H)(0Et)4. (200°) at 10
mm. S.G. 14 1-023. A product of the action of
NaOEt on epichlorhydrin. Liquid, sol. water,
alcohol and ether.
Acetyl derivative of triglycerin
tetra - chlorhydrin 0„H,30l40i t.e.
C|,H,502(0Ac)Cl4. (260°) at 20 mm. From
epichlorhydrin and AoCl at 100° (Truchot, A.
140, 245).
Hexaglycerin bromhydrin
CjgHj^rO,. One of the products of the action
of PBr, on glycerin. Crystalline. SI. sol. boiling
ether.
Thioglycerin CaHgOaS i.e. C3H5(0H)j(SH).
Mol. w. 108. S.G. '-^ 1-295. From chlorhydrin
and boiling alcoholic KSH: the product is
acidified and evaporated below 50° (Carius, A.
122, 72; 124, 222). Thick liquid; v. si. sol.
GLYOIDIC ACID.
625
water, insol. ether, miscible with alcohol.
Beacta like meroaptan with metallic oxides and
Baits. Decomposed by heat into water HjS and
thiopyroglycido CeHijOjS an amorphous
body, insol._ water and ether, si. sol. boiling
alcohol. Nitric acid oxidises thioglyoerin to
0,H.(0H)jS03H. — Hg(0,H,0,S), : [SC-eO"] ;
white powder.— Pb(C3H,0jS)j ! [o. 80°] ; yellow
pp.
Di-thio-glyoerln OsHjOSj i.e.
C,H,(0H)(SH)2. Mol. w. 124. S.O ^^ 1-342.
From 5-dichlorhydrin and alcoholic KHS
(Carius). Thick liquid, insol. ether, t. b1. sol.
water, v. e. sol. alcohol. Split up on distilla-
tion into water,~H2S, and trithiopyroglycide
C^ijOS,. HNO, forms an acid 0sH,jS30,„.—
HgC,H,OSj [o. gO'G. — PbCjHjOSs: yellow
powder.
TritMoglycerin CaHsS, i.e. CsHjISH),. Mol.
w. 140. S.G. y^ 1-391. From s-triohloro-pro-
pane and alcoholic ESH (Carius). Xiquid, m.
sol. alcohol, insol. ether and water. Split up by
heat into H,S and dithioglycide C3H5S(SH).^
Cn,(0,H3S,),.-Pb,(C3H,S,)2--Ag303HA.
GIiYCEBOL V. Gltcebin.
GLYCEaoSE V. Olycebik, Beactum 6.
GLYCEBYIu The trivalent radicle OjHj.
GLYCEKYL BOEATE CaH^Oj. Formed by
heating glycerin with B^O, (Schiff a. Bechi, Z.
1866, 147). Glassy mass resolved by hot water
into glycerin and boric acid. Not affected by
boiling alcohol.
GI.YCEEYL CAEBAMATE 03Hs(O.CO.NH,)3.
[215°]. From ohloroformamide and glycerin
(Gattermann, A. .244, 42). Needles (from
HOAc). Insol. most solvents.
GLYCEBYL CHIOBISE v. Tbi-chlobo-fbo-
FANE.
GLYCEBYL TBI-FHENYL-TBI-CABBAUATE
CjH5(0.C0.NHPh)a. Phenyl-carbamio-glyoeride.
Formed by heVting glycerin (1 mol.) with
phenyl oyanate (3 mols.) (Tessmer, B. 18, 968).
White powder or fine needles. Sol. alcohol,
acetone, ether, and chloroform, si. sol. water and
benzene. By heating with Ba(0H)2 and water
to 150° it yields glycerin, aniline, and BaCO,.
GLYCEBYL STJLPHOCYANIDB 0»H3N3S3 i.e.
C,H3(SCy),. [126°]. S. (alcohol) .-25 at 18°.
From j)-tri-bromo-propane and alconolic ESCy
at 100° (Henry, B. 2, 637). Small brittle needles
(from alcohol). Insol. water, v. sol. boiling alco-
hol. Gives off HCy when heated.
GLYdDAUINE OJE[,NO U.
CH2.G^CH2NH2. Olyeeramine. Formed, toge-
Y
ther with ' diamidohydrin ' CjHjoNjO by the
action of alcoholic NH, on s-didblorhydrin
(Clans, A. 168, 29).— BHCl: crystals, ppd. by
adding ether to the aloohoUo solution ; very hy
groscopic. — ^B'^HjEtClg: transparent needles.
GLYCIC ACID V. Glucic acid.
GLYCIDE Ofifi,i.e. 0<^]^oH,.OH. (1^°°)
(B.) ; (157°) (H.). . S.G. 2 1-165. Prepared by
adding powdered caustic soda (but not potash)
to an ethereal solution of its acetate (Breslauer,
J. pr. [2] 20, 192 ; cf. Gegerfelt, SI. [2] 23, 160).
Obtained by the aotion of BaO (28 g.) upon chlor-
hydrin (48 g.), dissolved in ether (50 g.) (Hanriot,
. Vol. II.
C. B. 88, 387). Mobile liquid, misoible with
water, alcohol, and ether. Heated with, water
it forms glycerin. Eeduoes ammoniaoal silver
nitrate in the cold. In presence of glycerin it
rapidly forms products of condensation. Dilute
HNO3 forms glycerin mononitrate. Distillation
with KHSOj gives acrolein.
Acetyl derivative
0<O^CH,.OAo- (166») (B.);(169°) (G.). S.G.
^ 1-129. Obtained by heating dry powdered
potassic acetate with an equivalent quantity of
epichlorhydrin over an oil bath, the temperature
of which is slowly raised from 110° to 150°.
After 20 hours the mass is extracted with ether
and fractionated. An isomeric liquid (260°).
S.G. 32 1-204 is got as a by-product (Breslauer).
Beduces ammoniacal AgNO,.
Ethyl derivative O^qh CH .OEt
(129°). S.G. 12 -94. Formed by the" aotion of
EOH on the ethyl-ohlorhydrin derived from
ethyl allyl oxide and KOH (Beboul, A. Oh. [3]
60, 5 ; Henry, B. 5, 449). Liquid, sol. water.
Beadily combines with HGl. PCI. gives
CaHjCyOEt).
Isoamyl derivative G3H,03.C3H„.
(188°). S.G. 22-90. From isoamyl-ohlorhydrin
and KOH.
Pyruvyl derivative CjHgO^ ».e.
0<6aCH,0.C0.C0.CH.. (?)[82°](B.); [78°]
(J.). (260°). Formed by heating eqni-molecular
proportions of glycerin and glyceric acid at 120°,
and crystallising the product from alcohol
(Erhart, M. 6, 511). Formed also by distilling
glycerin with tartaric acid (Jowanowitsch, M. 6,
467). Needles, sol. hot water, but slowly saponi-
fied thereby, sol. alcohol, benzene, and ether,
Monoclinic: a:6:c = l-48:l:-77 ; j8 = 105° 38'.
Beadily saponified by alkalis, alkaline earths,
and their carbonates. Bromine forms di-bromo-
pyravic acid. Sodium-amalgam gives lactic
acid. It forms the following salts which are de-
rived from its hydrate CjHioOs.—KCjHjOs: silky
needles. — Ca(CsH,05)j 2aq. — Cu(03H,0 J, 3aq !
blue crusts. — ^AgCgHgOg : needles.
GLYCIBIC ACID C^Ufl, i.e.
G<^Qjg-=QQ^ Oxy-acrylio acid.
Formation. — 1. By the action of alcoholio
EOH on the a-chloro-3-oxy-propionic acid that
is formed by the union of acrylic acid with HOCl
(Melikoff, & 13, 271 ; 14,939).— 2. InUkeman-
uer from the isomeric j3-chloro-a-oxy-propionio
acid (Erlenmeyer, B. 13, 458).
Properties. — Liquid, miscible with water,
alcohol, and ether. Slowly combines with water,
becoming glyceric acid. Its caloiimi salt
readily takes up water, changing to calcium
glycerate. Cone. HGlAq forms iS-chloro-a-oxy-
propionic acid.
Salts.^NH4A'.— KA'^aq: small prisms. —
NaA'^aq. — ZnA'^aq: amorphous. — AgA': tri<
metric tables; when its aqueous solution is
boiled it deposits a silver mirror.
Ethyl ether EtA'. (162° anoor.). S.G.
'^ 1-0933. From silver /S-chloro-a-oxy-pro-
pionate and EtI (Melikoff, B. 21, 2052). Oil ;
smelling somewhat like malonio ether.
SS
636
GLYCIDIO ACID.
HomologiieB of glycidic acid v. M.¥.tbxl-
QLYOIDIO ACID.
GIYGIN'E V. Gltcoooll.
GLYCO-DI-AMIDO-BEITZOIC ACID
0,3H,sN,0, i.e.. COjH.C,H3(NH)20bH,oOs.
Formed by heating a couo. aqueous solution of
glucose (2 mols.) and diamido-benzoic acid (1
mol.) for some hours at 90° (Griess a. Harrow,
B. 20, 2210). Small sUvery plates (from water) ;
V. si. sol. cold water, nearly insol. alcohol and
ether. Decomposed by melting. Not affected
by boiling with aqueous HCl or baryta. Strongly
dextrorotatory.^BaA'j (at 100°) : amorphous. —
EA'HOl: small plates; t. e. sol. water and
alcohol.
GLYCOCHOLIC ACID CjeH„NOs. S. -33 in
the cold ; -83 at 100° (Strecker) ; •038 at 20° ;
■85 at 100° (Emioh). S. (ether) -093 at 20° ; S.
(benzene) -009; S. (CHCII3) -Oil. [a]„ = 29-9°
(Eoppe, O. C. 1859, 65). Occurs as sodium salt
in the bUe of animals, and in ox-bile it is accom-
panied by sodium taurocholate, cbolesterin, pig-
ments, &c. (Gmelin ; Strecker, A. 65, 9 ; 67, 1 ;
70, 161, 166; Emich, M. 3, 326; M. 4, 108;
Gonip-Besanez, A. 157, 286).
Preparation. — 1. The pp. formed in fresh ox-
bile by Pb(OAo)2 is treated with boiling (85 p.c.)
alcohol, and the hot filtrate decomposed by H^S,
mixed with water and set aside to crystallise. —
2. Fresh ox-bile is evaporated to dryness oyer
the water-bath; the residue is extracted with
cold alcohol, and the filtrate mixed with a little
ether. After some time the liquid is decanted
from the sticky deposit, and more ether is added
when the mixed sodium salts (Plattner's ' crys-
tallised bUe ') slowly deposit. They are dissolved
in water and dilute H2SO4 added, whereupon
glycocholic acid slowly crystallises. — 3. The
readiest way of obtaining glycocholic acid con-
sists in covering fresh bile in a tail cylinder with
a layer of ether, and adding 2 c.c. of cone. EClAq
for every 50 o.c. of the bile. The whole then
usually solidifies after a while to a crystalline
pulp of glycocholic acid, whjoh may be re-orys-
taUised from water (Hufner, J.pr. [2] 10, 267).
In this experiment the bUe of castrated oxen
and of calves does not crystallise ; of other oxen
it always crystallises ; the bUe of cows usually
crystallises (Hiifner, J. jpr. [2] 19, 302). Bile
which when mixed with ether and HCl produces
a crystalline pp. of glycocholic acid, contains in
100 pts. of mixed taurochohc and glycocholic
acids from 71 to 88 pts. of the latter acid, while
bUe which does not produce such crystaUisation
contains only from 47 to 57 pts. of glycocholic
acid to 63 and 43 pts. of taurocholic acid respec-
tively (G. Hiifner, J.pr. [2] 25, 97). Neverthe-
less it cannot be held that taurocholic acid
hinders the crystaUisation of glyeocholio acid,
because a solution containing even 7 pts. of pure
sodic taurocholate to 1 pt. of pure sodio glyco-
oholate gives crystallisation when treated with
HOI and ether. The cause of non-crystallisation
is therefore not yet explained (H.). — 4. According
to Marshall {B. 11, 233), the quickest method of
obtaining glycocholic acid in colourless crystals
is as follows : — A drop of hydrochloric acid is
added to fresh bUe ; the mixture shaken and
filtered; ethyl ether and hydrochloric acid are
then added to the filtrate ; the mixture shaken
and allowed to remain. The crystals formed are
I collected on a filter, washed with water holding
hydrochloric acid and ether in solution, and dried
in the air. By re-crystallisation ihey are ob-
tained perfectly colourless.
Properties. — Bulky groups of slender needles.
V. si. sol. water, v. e. sol. alcohol, v. si. sol. other
solvents. Its aqueous solution has a sweet and
slightly bitter taste. It reddens litmus. It is
readily soluble in ammonia, aqueous alkalis, and
baryta-water ; the addition of acids to these solu-
tions reppts. the acids in a resinous form which
slowly becomes crystalline ; this change is rapidly
brought about by ether. The free acid and its
salts are dextrorotatory. It is antiseptic. By
heating above 140° it is converted into glyco-
cholonic acid CasH^NOj. With sugar and cone.
HjSO, it gives on warming the crimson colour
characteristic of Pettenkofer's test (v. Bile).
Solutions of glycocholic acid are not ppd. by
gelatin (Maly a. Emich, M. 6, 95).
BeacHoris. — 1. Boiling aqueous KOH splits it
up into glycocoll and eholic acid CjjH^Os. Boil-
ing baryta-water effects the like hydrolysis. — 2.
Cone. HClAq and cone. H2SO4 dissolve it in the
cold, and water reppts. it from these solutions, but
the boiling acids deposit oily drops of glyco-
cholonio acid which solidify after a while. — 3.
Boiling dilute HCl forms choloidic acid, dyslysin,
and glycocoll. — 4. Nitrous acid vapour passed
into its solution forms ' chologlycollic acid '
CjoH^O, (iiang, Bl. [2] 25, 180). This acid is
amorphous, but forms a crystalline barium salt
Ba(CaiH„0,)2 3aq.— 5. When mixed with HOAc
and HjSO, and heated it forms an orange colour-
ing matter possibly related to the bUe-pigments
(Michailofi, B. 17, 444, Bef. ; J. R. 1884 [1]
684).— 6. By heating with alcoholic NH, at 170°
for 24 hours there is formed a substance
CjjH^iNO,, which on evaporation crystallises in
long silky deliquescent needles [125°] (PeUizzari,
O. C. 1888, 1350).
Salts . — Solutions of the alkaline salts lather
like soap. All the glycocholates are soluble in
alcohol, those of the alkalis and alkaline earths
dissolve easily in water, the rest are sparingly
soluble and may be obtained by precipitation. —
NaA' (at 100°). S. (alcohol) 1-5. The alcohoUo
solution deposits crystals when very slowly
evaporated in a flask. Dry ether added to its
alcoholic solution throws it down in an amor-
phous state, but if the ether is wet it becomes
crystalline (Stadeler, J. pr. 72, 257).— BaA',
100°) amorphous, S. 16-2 at 15°.— PbA'^
100°).
Ethyl ether CssH^jEtNOj. S.G. •90» Pre-
pared by saturating an alcoholic solution of the
acid with HCl and heating in sealed tubes
(Springer, Am. 1, 181). Slowly saponified by
water.
ParaglycochoUo acid OjsHjsNOe. [184°].
When glycocholic acid, is ppd. by HjSO, from a
solution of its Na salt, and the pp. is boiled vrith
water paraglycocholio acid remains undissolved.
Alcohol and boiling alkalis reconvert it into tha
ordinary modification.
GLYCOCOLL CjHjNOj i.e. CH,(NH2).C0jH
.(at
(at
„„ /CO.O.NH,V f,rr
*^^«<sNH,.O.cd>™?
«3^<NH>0-
Amido-acetic acid. Mol. w. 75. (232''-236° eor.).
S. 23. S.G. 1-161. H. C. 228,000 (Stohmann,
GLYOOC!OLL.
627
/. pr. [2] 31, 285). Occutb in the mussel Pectm
irmdians (Ohittenden, A. 178, 273).
Formation. — 1. Disooveied by Braoonnot
{A. Ch. [2] 13, 114), who obtained it by boiUng
gelatin with dilute HjSO,. — 2. Formed also by
boiling gelatin with potash or baryta (Mulder,
J. pr. 16, 290).— 3. By boiling hippuric acid with
dilute HOI (Dessaignes, A. [3] 17, 50 ; Kraut a.
Hartmann, A. 133, 99). — i. By decomposing
glycocholic or hyoglycocholio acid with dilute
acids or alkalis (Strecker, A. 67,25 ; 70, 188).—
5. From bromo-aoetio acid and NH, (Perkin a.
DUppa, A. 108, 112).— 6. Together with COjand
KH, by heating uric acid with cone. HIAq at
165° (Strecker, Z. [2] 4, 215).— 7. By the aotipn
of aqueous EI on hydantoio acid (Mensohutkin,
A. 153, 105). — 8. From nitroso-thio-hydantoin
or nitroso-thio-glycollio acid and HI (Andreasoh,
M. 6, 827).— 9. From glyoxal by successive
treatment with ammonium cyanide and dilute
HjSO, (Lnbavine, Bl. [2] 38, 379).— 10. By
passing cyanogen into boiling HIAq (S.G. 1'96)
(Enmierling, B. 6, 1351). — 11. From oyanoformio
ether, zinc, and HOI (Wallaoh, A. 184, 13).— 12.
To the extent of about 7*5 p.o. by boiling silk
with dOuteH^SO, (Weyl, B. 21, 1531).
.Preparation.— 1. Hippuric acid 500 g. is
boiled with cone. HOI for 12 hours. The benzoic
acid formed is removed by filtration and extrac-
tion with ether, after which the liquor containing
the hydrochloride of glycocollis evaporated until
crystallisation sets in. The salt is washed with
absolute alcohol. The yield is 90 p.c. (Ourtius a.
Goebel, J. pr. [2] 37, 157).— 2. Hippuric acid
(1,200 g.) is boiled for 12 hours with H^SO,
(1,600 g.) diluted with water (3,200 g.). The pro-
duct is allowed 24 hours to cool, it is then filtered.
The filtrate is evaporated and shaken three
times with ether to remove the last traces of
benzoic acid. The liquid is diluted and neutral-
ised with baryta (free from iron). The liquid is
decanted from BaSO, and evaporated. Some of
the dissolved barium can be removed by 00.^.
Theglycocoll crystallises out from the evaporated
filtrate (T. CurtiuB, J. pr. [2] 26, 153).— 3. By
heating ohloro-acetic acid (1 pt.) with solid
ammonium carbonate (3 pts.) to 70° and finally
to 130° (Nencki).— 4. Chloro-aoetio acid (50 g.)
and sodium carbonate (£3g.) are warmed with
excess of aqueous ammonia. After boiling for
7 hours hydrochloric acid is added and the liquid
evaporated, ppd. with alcohol and filtered. The
filtrate is digested with Cu(H0)2, warmed, fil-
tered, and treated withi alcohol, and then with
hydrogen sulphide (Manthner a. Suida, M. 9,
728). — 5. By heating phthaloxyl-amido-acetie
acid C0^.C8H,.00.NH.CHj.C0JB: with double
its weight of 20 p.o. pure HCl, diluting with
water, filtering, evaporating, and treating with
ice-cold water, which leaves behind phthalic acid.
On evaporating and washing with absolute al-
cohol, hydrochloride of glyoocoll remains as a
snow-white crystalline powder (S. Gabriel a. K.
Kroseberg, B. 22, 428).
Properties. — Monoclinio tablets ; a:b:c
= l:l-857:2-204 ; i3 = 68° 20' (Schabus). Slight
impurities change the crystalline form remark-
ably : traces of NaOH or TIOH cause it to form
rhombohedra, while traces of baryta induce the
formation of very long thin prisms (Ourtius).
Olycocoll is inactive. It has a sweet taste. SI.
sol. water, insol. ether and alcohol. Neutral to
litmus. It prevents the ppn. of cupric hydroxide
from its sulphate by potash (Horsford, A. 60, 1).
FeCL gives a deep-red colour (Engel, Fr. 16,
344).
BeacUons. — 1. Distillation with BaO gives
methylamine and BaOO,. Solid KOH acts. in
like manner but KH„ hydrogen, and potassium
oxalate are also formed (Oahours, A. Ch. [3] 53,
322 ; A. 109, 29).— 2. Dilute H^SO, and MnOj
give off COj and HCy. — 3. Nitrous acid gas con-
verts it into glycollic acid (Soooloft a. Streckei,
A. 80, 18 ; Dessaignes, C. B. 38, 44).— 4. When
heated with benzoia acid in sealed tubes, hippuric
acid is formed (Dessaignes, J. Ph. [3] 32„ 44).
Hippuric acid is also formed by treating zinc or
silver glycocoU with BzOl (Dessaignes, G. B. 37,
251).— 5. Cyanamide forms glycocyamine
OaHjNaOj (Streokqr, C. B. 62, 1212),— 6. Phenyl-
cyanamide in ammoniacal solution mixed with
an alcoholic solution of glycocoll forms on stand-
ing crystalline grains of CjHijNaOj (Berger, B.
13, 992). — 7. With sodiwm hypobromite nitrogen
is evolved (Denigfes, G. S. 107, 662).— 8. When
a concentrated solution of glycocoll is mixed
with NaOH ani phenyl-acetic chloride a reaction
takes place and on acidifying phenyl-aoeturic
acid separates. Its ether On^uNOjEt crystal-
lises in broad prisms [79°]. — 9. When benzoic
aldehyde is added to an aqueous solution of gly-
cocoll saturated with SO^^ there is formed syrupy
CjH|,NSO, which slowly solidifies over HjSOi
(Schiff, A. 210, 125). CEnanthol forms a similar
compound C,H„OOjHsNOjHjSOs.— 10. Heated
with choUc acid at 200° for 20 hours there is
formed a product whence NaOH ppts. amorphous
glyoodyslysin O^HjuNOj (Lang, Bl. [2] 25,
180). — 11. Chloroform and KOH form isocyano-
acetio acid 0:N.0Hj,C02H (Calmels, Bl. [2] 42,
266). — 12. Gtiamdme carbonate forms the com-
pound GjH5N02(CH5Nj)200.,aq (Nencki a. Sieber,
J. pr. [2] 17, 480).— 13. Urea (10 pts.) at 230"
forms urio acid (Horbaczewski, B. 16, 2678).
Salts. — The fact that glyoocoll only forms
salts with such metals as can displace the hy-
drogen of amidogeu tends to show that the salts
have the formula 0H2(NHB)002H, and not
CHj(NH2)C02B. Thus it forms no salts with
alkalis, and probably none with alkaline earths.
Barium salt. — If excess of baryta be added
to glycocoll sulphate and the solution be filtered
the liquid may perhaps contain glycocoll-barium,
but on adding alcohol a pp. is got, which con-
tains variable ainonnts of glycocoll and baryta.
If this pp. be recrystallised from alcoholit be-
comes pure glycocoll. Hence glycocoll-barium
i& very unstable, if indeed it exists (Ourtius,
J. pr. [2] 26, 151).
Zinc salt OjHtNOjZn aq. Partially decom-
posed by hot water. Boiling Na^CPa removes
one-third of the zinc.
Silver salt AgA'. Prepared by heating
silver, oxide (38 g.) nearly to boiling with a solu-
tion of glycocoll (100 g.). The hot liquid is fil-
tered and aUowed to cool in the dark. After an
hour the liquid is poured off from the silver gly.
cocoll and heated with the remaining silver
oxide. This process is repeated until the quan-
tity of silver glycocoll that separates on cooling
begins to decrease when a fresh quantity of silver
oxide (38 g.) is added to that which still remains,
8S2
628
OLYOOOOLL.
and the process is continued till all the silver
oxide is either used up or reduced to silver.
Yield 73 p.c. (Ourtius, J.jjr. [2] 26, 165). Crys-
tallises in tablets. Turns grey in daylight. It is
not hygroscopic. It is strongly alkaline. It de-
composes at 100°. Warmed with a mixture of
benzene and benzoyl chloride it forms silver
chloride and the three following acids : (1) Hip-
puric acid (Dessaignes, C B. 37, 251) ; (2) an acid
C„H,j^jOs!.[207°], which when boiled with di-
lute acids gives benzoic acid and two molecules
of glycocoU, and hence it may perhaps be written
Ph.CO.NH.OH;,.CO.NH.CHj.COjH; (3) an acid
CigHisNgO,, which blackens at 240° without
melting, but with acids gives also benzoic acid
and glycoooU on boiling (T. Curtius, J. pr. 132,
239). Silver glycoooll is converted by EtI into
NEt3l.CH2.C02Bt.— AgA'HOEt. Obtained by
ppg. a solution of silver glycocoll by alcohol.
Other salts. — PdA'^: 'yellow needles
(Dreohsel, J. pr. [2] 20, 475).— CdA'j aq : silky
foliated crystals. — OuA'j aq : blue needles. S. '6
at 15°. — PbA'j aq : needles. — HgA'^ aq : small
crystals.
Salts with aoids. — ^ELA'HCl: deliquescent
crystals, v. e. sol. water, si. sol. alcohol ; has an
acid, slightly astringent taste. — EjA'gHCl: tri-
metric crystals; a:6:c = 1 : 1'llOS : '3091. —
HjA'jHjPtCle.— HA'HNOj : [145°]. Decomposed
by fusion (Pranchimont, E. T. C. 2, 839). Tri-
metrio crystals; a:6:c = 1:3-412 : 2-969 (Nickl^s,
Compt. CMm. 1849, 256); = -0687 : -750 : 1
(Loschmidt, Sitz. W. 61 [2] 386). According to
Horsford they are monochnic. — ^HjA'jHNO,. —
HjA'^HjSOj, Large prisms, permanent in the
air; sol. water, insol. alcohol and ether. Ac-
cording to NickUs the crystals are trimetrio;
a:b:c = 1 : -424 : -321.— HA'HOAo 4aq : crystal-
Uses from water. — H2A'jH„C204 : trimetric crys-
tals ; a:b:c = 1 : 3-072 : 2'792 (N.).
Combinations with both acids and
base s. — KA'HCl. — BaA'^HjClj : trimetrioprisms.
— KA'HNOs : needles (Boussingault, A.39, 310).—
CuA'2Cu(N03)2 2aq : blue needles.— AgA'HNOj :
needles. — EHA'2H2S04: prisms.
Acetyl derivative v. Aceiubic acid.
Benzoyl derivative v. Hipfubio acid.
Salicyl derivative v. Oxt-benzoio agio.
Methyl ether NHj.CHj.C0jM6. (54°) at
50 mm. Obtained by suspending its hydro-
chloride in ether, shaking with the theoretical
amount of Ag^O, evaporating the filtrate, drying
over BaO and fractionally distilling (Curtius a.
Goebel, /. pr. [2] 37, 165). Liquid, misoible with
aU ordinary menstrua; boils with decomposition
at 130°. It forms a copper salt crystallising in
blueueedles, v.sol. water. Cu(NH.0H2.00jMe)2aq.
Hydrochloride NH3C1.0Hj.C0jMe. [175°].
Formed by passing dry gaseous HCl through
methyl alcohol containing glycocoll hydrochlor-
ide in suspension until solution takes place
(Curtius a. Goebel, J. pr. [2] 37, l69). Prisms,
V. sol. cold alcohol. Tieldsethylaminewhen dis-
tilled with NajCO,. Its platinochloride is v. sol.
alcohol and water.
Acetyl derivative of the methyl ether
V. AcETTBia AOID.
Ethyl ether NHj.CHj.COjEt. (149°) at
748 mm. ; (65°) at 40 mm. V.D. 3-47 (calc. 3-57).
Formed by treating its hydrochloride in ethereal
solution with A^^O as in the preceding case
(6. a. C). Formed also from bromo-acetio ether
by treatment with silvernitrite and reduction of
the resulting nitro-acetic ether (De Forcrand,
C. B. 88, 974). Colourless liquid, miscible with
water, alcohol, ether, benzene, CHOI3, and petro-
leum-ether. Somewhat volatile with steam. Ab-
sorbs COj. Does not solidify at —20°. Gives
n-propylamine when distilled with NajCO,. Its
copper salt Cu(KH.CH2.C02Et)2 2aq crystallises
in blue plates, v. sol. water. Hydrochloride
NHsCLCHpCOiJlt. [144°]. Formed by passing
dry HCl into alcohol containing glycocoll hydro-
chloride in suspension until solution occurs
(G. a. C). Long needles ; may be sublimed. Its
platinochloride forms needles [212°]. Hydro -
iodide NHJ-CHyGO^Et. Formed by heating
glycocoll with alcohol and EtI or even Mel at
120° (Schilling, A, 127, 97 ; Kraut, il. 177, 267).
Trimetric crystals. With AgjO it gives glycocoll,
alcohol.andAgl.— NitrateNHs(NO,)OKjCOjBt.
Crystals (Curtius, B. 17, 953),
Acetyl derivative of the ethyl ether
V. ACETDEIO ACID.
Allyl ether. Hydrochloride
NH3Cl.CHj.C0,AH5. [170°-180°]. Prepared by
suspending glycocoU hydrochloride in aUyl al-
cohol and passing HCl until a solution is ob-
tained (C. a. G.). Thin plates, m. soL cold
alcohol.
Isoamyl ether. Hydrochloride
NH3CI.CH2.CO2C3H,,. From glycocoU, isoamyl
alcohol, and HCl. Syrup.
Phenyl, ether NH2.CH2.COjCjH5. From
phenyl chloro-acetate and alcohoUcNH,at 140°.
Needles, sol. water, r. si. sol. alcohol and ether
(Prevost, J.^. [2] 4, 379).
Anhydride CjH,NO i.e. CH^^^q"^ or
CH,<^^j°^>CHj. [276°]. Prepared by de-
composing an aqueous solution of the hydro-
chloride of glycocoU ethyl or methyl ether with
silver oxide and extracting the mixture of silver
chloride and anhydride with hot water, by which
the latter is dissolved out and crystaUises on cool-
ing (Curtius a. Goebel, J.pr. [2] 37, 173). Plates.
Y. sul. hot water and dilute alcohol. Neutral to
litmus. It does not combine with ammonia and
the alkali metals, but forms salts with sUver
(C^H^AgNOl) and copper. It forms a hydrochlor-
ide crystallising in long needles [130°], con-
verted by boiling water into glycocoU hydro-
chloride.— Platinochloride
B'4(H01)2PtCl4 3aq. Large orange-yellow crys-
tals, m. sol. water, si. sol. alcohol.
Amide NH2.CH2.CO.NH2. Amido-acetamide.
Formed in smaU quantity by heating glycocoll
with alcohoUc NH, at 160°. It is also one of the
products of the action of alcoholic NH, on
chloro-acetic ether (Heintz, A. 148,190 ; 160,67).
Obtained from its hydrochloride by treatment
with Ag^O. SoUd; v. e. sol. water; alkaline
in reaction. Decomposed by boUing water into
NH3 and glycocoU.— B'HCl: monocUnio needleg;
T. e. sol. water, si. sol. alcohol. — B'jHjPtCl,.
Ethyl-glycocoU v. Eihtl-amido-aceiic acid.
Phenyl-glyeoooUu.PHBira-AMiDO-AOBTioAciD.
Nitio-phenyl-glycoooU v. Nitbo - phenyl-
AUIUO-ACEIIC ACID.
Sulphs-phenyl-glycocoU v. SuiiFHo-fhentl-
AMIDO-ACETIC ACIP.
GLYCOGEN.
629
Nitro-tolyl-glycocoU v. Nitho-tolyl-amido-
^CEIIC ACID.
GLYCOCOLONIC ACID a„H„N05. A pro-
duct of the action of cone. EClAq on glycooholic
acid (Streoker, A. 67, 26 ; 70, 166). Formed also
by heating glycooholio acid above 140°- Needles
(from aJcohol). Insol. water and ether, t. sol.
alcohol. Decomposed by boiling EClAq into
glycocoll and cholio acid. NaA' : crystals (from
alcohol) (Mulder, J. 1847-48, 907).
GLTCOCYAMIira C,H,N,Os i.e.
NH:C(NHj),NH.OHj.CO^. Guanido-aceUoacid.
Mol. w. 117. S. -8 (Strecter), -44 (Nencki).
Formation. — 1. By adding a few drops of
ammonia to an aqueous solution of glycocoll
mixed with cyanamide (Strecker, G. B. 52, 1212).
2. By heating an aqueous solution containing
glycocoll and guanidine carbonate, glycocyamine
and ammonic carbonate are formed (Nencki a.
Sieber, J. pr, [2] 17, 477) ; the reaction taking
place as followa: 2C^5NO,+ (CH5N,)jH2C03
= 20aH,N,0j+ mHs)jHjOOa. Probably the guan-
idine first breaks np into cyanamide and am-
monia.
Properties. — Transparent needles. SI. sol.
odd, T. sol. hot, water; insol. alcohol. Boiled
with oupric acetate it gives microscopic crystals
ofCu(03H,NA)ii-
Salts. — HA'HCl: prisms ; t. sol. water. —
HjA'jHsPtCl,3aq.
Olycooyamidine CjHjNjO i.e.
The hydrochloride is obtained by heating gly-
cocyamine hydrochloride/ to 160° (Streoker).
The base may be liberated by boiling this salt
with lead hydroxide and water. Laminae ; v. e.
sol. water. Has an alkaline reaction. It forms
a compound with ZnCl, crystallising in needles
resembling theoorrespondUig salt of creatinin.—
BBCl: V. sol. water.— B'j^Pt01j2aq: needles.
Beference. — ^BENz-aiiTaocTAMrontE.
QLYCOSRITFOSE v. CelluijOSE.
GLYCOSTSLTSINCjsHggNO^. An amorphous
powder formed by heating glycocoll with cholio
acid at 195° (Lang, Bl. [2] 25, 182). SI. sol.
water, v. sol. ether, ▼. e. sol. alcohol. Not
attacked by alcoholic EOH. Boiling HClAq
forms glycocoll.
GLYCOGEN C,H„Os.
OcctiArence. — ^ the liver and in the placenta,
entering largely into the constitution of most of
the tissues of the embryo (Gl. Bernard, C. B. 41,
461 ; 44, 578, 1325 ; 48, 77, 763, 884 ; Sanson,
O.B. 44, 1159, 1323 ; 45, 140, 348 ; Schifl, C. B.
48, 880 ; E. Pelouze, C. B. 44, 1321 ; Bonnet,
C. B. 45, 139, 573 ; KeknU, 0. O. 1858, 300 ;
Poggiale, J. Ph. [3] 34, 99 ; Harley, Pr. 10, 289 ;
Pavy, P. M. [4] 17, 142; Pr. 10, 628; 11, 90;
Gornp-Besanez, A. 118,227; McDonnell, Pr, 12,
476; Wittich,J5'r. 14, 227; Aldehoff, ^.B. 25,
137; Manchfi, J?. B. 25, 163 ; Chandelon,P/.13,
626; Schmelz,^.B.24,180). As much as 11 p.c.
has been found in the liver of new-bom puppies
(Demant, H. 11, 142). Occurs also in blood,
muscle, spleen, kidneys, pancreas, and brain
(Pavy, Pr. 32, 418), and in the white and yolk of
egg. Glycogen is uniformly distributed through-
out the liver, but in the mnscles of the heart,
where it also occurs, it is unevenly distributed
(Cramer, Zeit. Biol. 24, 67). Occurs in the urine
in diabetes melUtus (Leube, G. C. 1888, 1278).
In vesicular cells of the connective tissue of
mollusoa, such as oysters (Bizio, G. B. 62, 675 ;
65, 175 ; . Blundstone, Pr. 38, 442). In the cook-
roach {Blatta orUntaUs), and in Bombyx^ mori
(a butterfly) and its chrysalis (Anderlini, 0. 0.
1888, 451). It is present in a large number of
fungi, where it seems to take the place of the
starch of higher plants (Errera, G. G. 1888, 252).
It is present in beer-yeast (Errera, C. B. 101,
253 ; Laurent, 0. G. 1888, 252). Found in
ciliated infusoria (Maupas, G. B. 101, 1504).
When the following substances are introduced
into the systems of starved dogs or rabbits no
appreciable quantities of glycogen are found in
the liver : inosite, maunite, quercite, erythrite,
and fats. But glucose, milk-sugar, cane-sugar,
IcBvulose, inulin, glycerin, gelatin, and proteiids
promote the formation of glycogen. It is not
clear whether the glycogen is directly formed
from these substances or whether their presence
promotes its formation from some other source,
or hinders its destruction when formed (Von
Mering, Pf. 14, 274 ; c/.Porster, J/'.iJep. Phartn.
25, 738 ; Wolf berg, Zeit.f. Biol. 12, 266 ; Seegen,
Pf. 40, 48 ; Chittenden a. Lambert, Dissertation,
1885). Asparagine, glycocoll, and, above all,
ammonium carbonate, when given to rabbits
with a carbohydrate diet greatly increase the
amount of glycogen in the liver (BShmann, Pf,
39, 21).
Prepa/ratUm. — 1. Glycogen is best obtained
pure by Brucke's method (Sitz. W. 63 [2] 214),
which readily separates all proteiids from it. A
solution of potassio-mereuric iodide is prepared
by precipitating mercuric chloride with potassium
iocQde, washing the precipitate and then satura-
ting a boiUng solution of potassium iodide with
it. A watery solution of glycogen, mixed with
albuminous matters, is prepared by cutting a
perfectly fresh liver into pieces about the size of
a hazel-nut, and throwing them into boiling
water for a couple of minutes, so as to destroy
the liver ferment, which would otherwise convert
the glycogen into sugar ; the pieces are then
bruised in a mortar and extracted with boiling
water, and the solution is filtered. As soon
as the filtrate is cold it is treated alternately
with hydrochloric acid andthepotassio-mercuiic
iodide solution as long as these agents produce
any precipitate, and after standing for five
minutes the solution is again filtered. Alcohol
is then added until about 60 p.c. of absolute
alcohol is present in the liquid : this throws down
the glycogen alone, but more alcohol precipitates
other bodies with it. The precipitate is collected
on a filter, washed first with weak, then with 90
p.c. alcohol, and finally with ether, and is then
transferred to a tile to dry. Glycogen is thus
obtained as a snow-white amorphous powder;
if impure or not quite dry, it forms a semi-
transparent brittle mass. — 2. The boiling aqueous
decoction of liver is treated with ZnCl, ; the
filtrate is evaporated and mixed with dilute (60
p.o.) alcohol, acidified with HCl. The ppd. gly-
cogen is washed with alcohol (Abeles, J. Th.
1881, 68 j Pf. 24, 485).
Properties. — White mealy amoi'phous pow-
der. According to Kiilz a. Borntrager {Pf. 24,
10) at 100° it is (CjH^OJjaq. With water it
forms an opalescent solution. On evaporating
880
GLYCOGEN.
this solution the glycogen separates in films.
Its aqueous solution is dextrorotatory [b]d vary-
ing from 203° to 234° according to concentration
(KvUz, Pf. 24, 85 ; Landwehr, Z. 8, 171) ; but
the polariscope may be used in its estimation
(Cramer, Z. B. 24, 180). It is insol. alcohol.
Its.ppn. from aqueous solutions by alcohol is
greatiy promoted by the presence of NaCl and
other salts (Kiilz,B. 15, 1300). Charcoal removes
it from its aqueous solution. Iodine colours
its aqueous solution red. Glycogen does not
reduce Fehling's solution. Glycogen dissolves
in cold cone. H^SO, forming an amorphous acid.
With baryta-water it gives a pp. of BaO(C^,gOg)s,
while lead subacetate forms PbO(C,H,g05)2.
EsUmatton.—^Iha substance is extracted with
hot dilute KOH, the proteids are ppd. from the
solution by HCl and potassio-mercurio iodide,
and the glycogen is then ppd. by alcohol, dried,
»nd weighed (Kiilz, Z. B. 22, 161),
Beactions. — 1. Diastasb and salima trans-
form it into maltose, a little glucose, and an
achroo-dextrin (Musculus a. Mering, H. 2, 413 ;
Siegen, G. C. 1877« 8). It is not changed to
sugar, to any significant extent, by contact with
blo'od (Pavy, Pr. 32, 418). Boiling dilute mineral
acids convert it into glucose (Eiilz a. Borntrager,
Pf. 24, 28). — 2. Does not ferment with yeast. —
8. Boiling dilute HNO, forms oxalic scid. — 4.
Bromine followed by Ag^O forms glycogenic acid.
5. Cold cone. HNO3 forms amorphous 'nitro-
glycogen' 0,2H,9(N02)0,|„ insol. water, alcohol,
and ether, sol. alkalis > and dilute HCl (Lustgar-
ten, M. 2, 634). — 6. A mixture of fuming HNO3
and HjSO, forms ' di-nitro-glycogen '
C|,Hj{N02)205, a white powder, insol. water, alco-
hol, ether, alkalis, and dilute acids, which ex-
plodes at 80° to 90°. It is converted by ammo-
nium sulphide into a dextrin which has but
slight power of reducing Fehling's solution, and
is dextrorotatory [a]D = 194 at 27° (Lustgarten).
7. AojO at 155° forms an amorphous tri-aoetyl-
• derivative C^B^Ajifi^, insol. water, alcohol, and
ether (Schtitzenberger, A. 160, 80).
Achroo-glycogeu CbH,„05. Obtained from
snaU's mucin, by treating with 5 to 10 p.o.
aqueous KOH, separating proteids by potassio-
mercuric iodide, filtering, and ppg. the achroo-
glycogen by alcohol (Landwehr, Z. 6, 74).
Amorphous white tasteless solid, v. sol. water,
forming a strongly opalescent solution. It does
not reduce Fehling's solution. By treatment
with saliva, diastase, or boiliiig dilute acids it
is 'converted into dextrin and glucose. It differs
from glycogen iti giving no colour with iodine.
GLYCOGENIC ACID 0„H,A- Formed by
treating an aqueous solution of glycogen at 100°
with bromine, and then adding AgjO (Chitten-
den, A. 182', 206). Very acid syrup. Is perhaps
identical with gluconic acid. — CaA', : minute
needles ; si. sol. cold water. — BaA', 3aq : prisms.
— PbjCjHjO,.— CoA'j5 2aq.
GLYCOL CAOj i.e. CHj(OH).CHj(OH).
Ethylene alcohol. Mol. w. 62. [-11'5°] (Bou-
chardat, C. B. 100, 452). (198° cor.). S.G. i|
1-1168 ; li 1-1121 (Perkin, C. J. 45, 504) ; ^
1-1072 (Brai). M.M. 2-943 at 15-1° (P.). m^
= 1-4325. Eoo =23-32. H.F.p. 100,890 (iTA.).
H.F.V. 99,150. S.V. 65-6 (Eamsay).
Formation. — 1. Prom ethylene iodide by dis-
tilling with silver acetate and saponifying the
resulting diacetate CjH,(0Ac)2 with solid KOH
(Wurtz, G.B. 43, 199 ; A.Ch. [3] 55,400 ; A. 100,
110 ; Siippl. 1, 85).— 2. By heating for 2 days
in a sealed tube at 100° a mixture of ethylene
bromide (60 g.) with potassium acetate (60 g.)
and (85 p.c.) alcohol (120 g.), and saponifying
the resulting mono-acetate CBLj(OH).CH20Ao
with potash or baryta (Atkinson, P.M. [4] 16,
433). Debus {A. 110, 316) recommends saponi-
fying the mono-acetate with water in sealed
tubes at 100°. By heating a mixture of ethylene
bi^omide (195 g.), KOAc (102 g.), and dilate alco-
hol (200 g. of S.G. -82), Demole (A. 173, 117) ob-
tained glycol and acetic ether. From 600 g.
ethylene bromide Erleimieyer (A. 192, 246) ob-
tained 125 g. glycol. — 3. Together with poly-
ethylenic glycols by heating ethylene oxide with
water (Wurtz). — 4. From ethylene chloro-iodide
and moist Ag^O at 160° to 200° (Maxwell Simp-
son, A. Suppl. 6, 253).— 5. Together with NMe,
by boiling a cone, aqueous solution of neurine
(Wurtz, A. S«^l. 6, 200).— 6. By heating ethyl-
ene bromide (1 pt.) with water (12 pts.) and PbO
at 150° (EltekofE, B. 6, 558).— 7. From ethylene
bromide (55| pts.), water (180 pts.), and Ag^CO,
(41 pts.). Ag^O and Ag^SO, used instead of
AgjCOs do not give glycol (Beilstein a. Wiegand,
B. 15, 1368).
Preparation. — 1. Ethylene bromide (188 g.)
is boiled with water (1000 g.) containing KjCQ,
(138 g.) in solution in a flask with inverted con-
denser. A large quantity of vinyl bromide
escapes. As soon as all the ethylene bromide
has disappeared the liquid is evaporated to dry-
ness, and the glycol separated from the EBr by
solution in alcohol. The alcohol is then dis-
tilled, when the glycol (13 g.) passes over at 198°
(Zeller a. Hufner, J. pr. [2] 10, 270). In this
process Na^CQ, (106 g.) may be used instead of
KjCO,, whereby the yield may be increased (to
35 g.), although the product is not so pure
(Stempnewsky, A. 192, 242). BaCO, used in-
stead of EjC^s yields no glycol. — 2. By heating
ethylene bromide (1 pt.) with water (26 pts.) for
130 hours in sealed tubes at 100° ; the yield
being 60 p.c. (Niederist, A. 196, 354).
Properties. — Colourless liquid, with sweet
taste, but no smell. Miscible with water and
alcohol; si. sol. ether. It dissolves EOH,
Ca(OH)j, OaOL,. NaCl, ZnOl,, SbCl„ and HgClj.
In a freezing mixture it sometimes solidifies to a
mass of crystals.
Beactions. — 1. When dropped upon pZaitwMm
black, CO2 is given off and the metal may even
become incandescent. If in this experiment
the glycol be diluted with water and the air with
CO2, glycollic acid is produced by the oxidation.
2. Cold dilute niirio acid forms glycoUio acid,
at higher temperatures it forms oxalic acid.
When glycol diluted with four times its volume
of water is placed in a tall vessel and strong
nitric acid is introduced so as to form a layer at
the bottom, and the whole is kept for some time
at 30°, there is formed glycollic acid, glyoxylic
acid, and perhaps also glyoxal (Debus, A. 110,
316). — 8. VaTisius potash at 250° forms oxalig
acid with evolution of hydrogen.^4. By heating
with zinc chloride, at 250° there is formed alde-
hyde and crcytonio aldehyde (Bauer, Bip. chim.
pwe, 1860, 244).— 5. By heating with a largo
quantity of water at 210° there is also teamed
GLYCOL.
631
.aldehyde {Nevole, BJ.r[2] 25, 289).— 6. By heat-
ing with acids it yields ethers by displacement
of one or both of its hydroxyls by acid residues
(Lourenijo, A. 114, 122).— 7. PCI5 gives ethylene
chloride (Wurtz, A. 104, 174) 8. Acetyl chloride
forma CHjjGl.CHjOAo. — 9. By heating with
ammonium chloride at 180°-190'' for 8 hours
there is formed tri-methyl-pyridine (coUidine)
CgH„N ; the yield being 15 to 20 p.o. of the
theoretical (Hofmann, B. 17, 1905).— 10. Heated
with fuming HCl in a sealed tube at 100° it
forms ethylene chloride (Sohorlemmer, O.J. 39,
143) ; but when saturated with HCl in an open
vessel and then distilled the product is glycol
ohlorhydrin.— H. Chlorine forms oily OjHuO,
(240°) and a crystalline chlorinated body [89°]
(0. 200°) (A.Mitscherlioh,0.iJ.56,188).^12. An
aqueous solution of glycol acidulated with H^SO^
is converted by electrolysis into CO, oxygen, and
CO3, together with formic paraldehyde (tri-oxy-
methylene), formic, acetic, and glyoollio acids,
and a polymeride of formic aldehyde resembling
glucose (Eenard, A. Gh. [5] 17, 315).— 13. By
heating glycol (2 pts.) with soda-Ume (5 pts.) at
250° there is formed an acid CjjjHjjO, [103°]
which may be crystallised fromligroin and ether
(Stfiicke, A. 228, 300).— 14. When heated with
aldehydes BCHO, glycol forms ethylene deriva-
/O.CH2
lives of the ortho-aldehydes ECH^ I (Wurtz,
, \0.CH,
Rip. chim. pwre, 1862, 16; Lochert, A. Ch,
[6] 16, 35). Thus isobutyrio aldehyde gives
PJCH<;°>C2H4. (125°). S. 10.-15. Chloral
unites energetically with glycol, and the result-
ing compound treated with pentachloride of phos-
phorus gives a compound (S. Or.^1-73) which may
be CCl,.CH01.0.CH2.CHj.0.CH01.CCl, (Henry,
B. 7, 762). If a mixture of fequivalent quantities
of glycol and chloral be left to stand for some days,
hard transparent crystals of C^HClgOC^eOj
[42°], H.P. 15,400, separate fDe Porcrand,
C. B. 108, 618).— 16. Phosgene' COClj forms
OjH4<^?>CO [39°] (286°) crystallising in prisms
sol. water and alcohol, insol. ether (Nembrowsky,
J.pr. [2] 28, 439).— 17. Distillation with oxalic
acid gives formic acid, and the dif ormyl derivative
of glycol (c. 174°) (Lorin, C. B. 79, 387 ; Bl. [2]
21, 409; 22, 104);- 18. Algce (Spirogyra) are
able io convert glycol into starch (Bokomy, C. C.
1888, 858).
Sodium derivatives.— C2H4(OH)(ONa).
Formed by dissolving sodium in glycol. White
crystalline deliquescent substance. Heated with
vinyl bromide in a sealed tube it yields ethylene,
glycol, sodium bromide, and apparently formic
acid. With methyl alcohol it crystallises as
C2H4(OH){ONa)MeOH in brilliant spangles.—
With ethyl alcohol: C2H,(OH)(ONa)BtOH.—
OjH4(OH)(ONa)C,H,OH. With glycol it forms
crystalline CjH4(0H)(0Na)CjH,(0H)j (Porcrand,
C. B. 107, 348, 1160 ; 108, 240).— C^H4(0Na)j.
Formed by fusing the preceding with excess of
sodium. Deliquescent mass. When distilled
with ethylene bromide it yields vinyl bromide,
glycol, and NaBr. With ClCO^Et in ether it
forms OjH,(O.C02Et)2 (0. 226°) (Wallach, A. 226,
Mono-rdtrate C^HsNO, i.e.
CHj(0H).CH20N0.,. S.G. iil'31. From glycol'
bromhydrin and AgNO, (Henry, A. Ch. [4] 27,
243). Liquid, sol. water.
Di-nitrate CaHiNjOji-e.
CHj(0N0j).CHj{aN02). S.G. a 1-484. From
glycol (42 g.), fuming HNOa (100 g.), and HjSO,
(200 g.) at 0° (H. Champion, Z. 1871,469). Ex-
plosive oil.
Nitrite-nitrate (7) OfiiN20^i.e.
OHj(ONO).CHj(ONOj). S.G. 1-47. Forrtted by
passmg ethylene into a cooled mixture of HNO,
and HjSO, (Kekul6, B. 2, 329). Oil. Sodium-
amalgam forms glycol and gives off aU the N as
NH3.
Aceto-nitrate CHj(OAo).CH2(N03). S.G.
1^ 1-29. From the mono-acetin, HNO,, and
HjSO, (Henry, A. Ch. [4] 27, 259). OU, v. e.
sol. dilute HCl.
Mono-su'lphuric acid
CH2(0H).CHj(0.S0sH). From glycol, and sul-
phuric acid (Simpson, A. 112, 146). Formed also
by the action of sulphuric acid on glycol ohlor-
hydrin (Oppenheim, B. 3, 735). Its chloride
CHj(0H).CH2(0.B02Cl), is formed by treating
glycol with SOjOla (Eeinhard, J.pr. [2] 17; 342).
The free acid is unstable, being decomposed by
hot water into glycol and H,S04. The potas-
sium salt is hygroscopic. The barium salt
BaA', is V. sol. water, almost insol. alcohol.
Disulphuric acid 1
CHjj(OSOsH).CH2(OS05H). From glycol and
CISO3H at 0° (Claessoil, J. pr. [2] 20, 5). Thick
syrup, decomposed by water, especially on warm-
ing, into glycol and HjSO,. Its salts are insoli
alcohol. — BaA"2aq: hair-like needles.— KjA" :
silvery mass.
Borate (CH2(OH).CHjO)i^. [162°]. .From
glycol by treatment first with gaseous, flien with
liquid BCI3 (Councler, B, 11, 1106). Minute
laminie, nearly insol. ether. Decomposed by
moist air.
Mono-acetyl derivative C^JO, {.e.
CH2(OH).CH2(OAo). Glycol monacetim. ', Mol.
w. 104. (182°).. Prepared by heating ethylene
bromide (1 pt.) with KOAc (1 pt.) and 85 p.c.
alcohol (2 pts.) at 100° in a closed bottle for two
days (Atkinson, P. M. [4] 16, 433; A. 109, 232 ;
Erlenmeyer, A. 192, 246) or by boiling the same
mixture with inverted condenser (Maxwell Simp-
son, Pr. 9, 725). The product is fractionally
distilled. Glycolic mono-acetin may also be
prepared by heating glycol (1 mol.) with Ac^O (1
mol.) for several hours at 170° (Maxwell Simp-
son). Colourless liquid, heavier than water.
Miscible with water and alcohol. Its aqueous
solution is neutral but it is easily decomposed
by potash and baryta yielding glycol. BoUing
with ethylene bromide and alcohol (S.G. '82)
converts it into glycol (Demole, A. VTl, 45).
AoOl forms 0^H4(0Ac)j and OHjCl.CHj.OAo
(LourenQO, A. 114, 127).
Di-acetyl derivative CgHigO, i.e.
CH2(0Ac).CHj(OAc). Glycol diaceUn. Mol. w.
146. (187°) (Wurtz) ; (190°) (Perkin). S.G. 2
1128 (W.) ; «f 1-1561 (Briihl) ; *| 1-1108 ; §5
1-1018 (P.). M;9 1-4268. Boo 51-79 (B.). M.m".
6-454 at 18° (Perkin, 0. J. 45, 505). V.D. 4-74.
S. 14 at 22°., Bate of formation ; Menschutkin,
B. 18, 1812. ,
Formed by heating ethylene bromide or iodide
632
GLYCOL.
with silver acetate (Wurtz, C. B. 43, 199 ; A.
100, 110 ; A. Oh. [3] 55, 400). From the mono-
acetin by heating with AcCl in a sealed tube at
100° and fractionally distilling the upper layer
of the resulting liquid. Obtained also by heat-
ing ethylene bromide with KOAo at 150° to 200°
(Demole, ^. 177, 49). Neutral liquid ; dissolves
in 7 pts. of water at 22°, and is separated by
CaClj from this solution, Miscible with alcohol
and ether. Boiling dilute alcohol (S.G. '82) de-
composes it into monoacetin, HO Ac, and EtOAo.
Besolved by bases into acetic acid and glycol.
Di-propionyl derivative CjH4(OC3H50)j.
(211° cor.). S.G. If 1-0544; || 1'0457. M.M.
8-318 at 21-2° (Perkin, C. J. 46, 505).
Mono-butyryl derivative
CH2(OH).CH2(O04H,O). (220°). From glycol
(1 mol.) and butyric acid (1 mol.) at 200°
(Louren<jo, A. Oh. [3] 67, 267). Oil.
Di-butyryl derivative C2H4(00,H,0)2.
(240°). S.G. a 1-024. Obtained by heating
ethylene bromide with silver butyrate and a
little free butyric acid for several days at 100°,
and fractionally distilling the product (Wurtz,
A. Oh. [3] 55, 400). Oil; sol. alcohol and ether.
Acetyl butyryl derivative
CH,(0Ac).CHj(0C4H,0). (212°). Formed by
heating glycol ohloro-acetin CH2(0Ac).CH2Gl
with- silver butyrate at 110°; or from glycol
chloro-bntyrin and AgOAc at 150°; in either
case the product is digested with ether, and the
ethereal filtrate is distilled (Maxwell Simpson,
Pr. 10, 115). Formed also by heating glycolio
mono-acetin with butyryl chloride, or glycolic
mono-butyrin vrith AcOl (LourenQo). Heavy
oil ; sol. alcohol. It is but slowly decomposed
by aqueous EOH even at 100°.
Acetyl-valeryl derivativt
CHj(OAo).CH2(OC5H,0). (230°). From glycol
mono-acetin and valeric acid (Loareni;o, A. 114,
122). Neutral oil, sol. alcohol and ether.
Mono-valeryl derivative
CHj(0H).CH,(O0,H,O). (240°) (LourenQO, A.
Ch. [3] 67, 268).
Di-valeryl derivative OjHi(OCsH|,0)2.
f265°).
Stearyl derivative C,^^fi^ i.e.
CjH,(0C,„H,50),. , [76°]. From silver stearate
and ethylene bromide, the product being ex-
tracted with ether (Wurtz, A. Ch. [3] 55, 436).
Small shining scales, resembling stearin.
Di-henzoyl derivative GgsHi^O, i,6.
C2H,(OBz)2. [67°]. (above 360°). Formed by
heating silver benzoate (68 g.) with ethylene
bromide (29 g.) for several days at 100°, extract-
ing the product with ether, treating extract with
Blamed lime andrectifying (W.). Trimetricprisms.
Succinoxyl derivative C^^JO^ i.e.
CH2(0H).CH,.0.C0.CHj.0H2.C0sH (?) [below
100°]. Formed by heating glycol (1 mol.) with
succinic acid (1 mol.) at 195° for 10 hours
(Lonren^o, Bip. Chmi.pwre, 1860, 179; A. 115,
358). Small crystals ; sol. water and alcohol,
si. sol. ether.
Suecinyl derivative 0,Kflt t.«.
^'^<0^0>^^*- tbelow 90°]. (212°)
'(Bichter, J. pr. [2] 20, 207). Obtained by heat-
ing the preceding to nearly 300°. Small crys-
tals (from alcohol); insol. water and ether, m.
aol. boiling aloohol.
Mono-ethyl ether C^,„0.ii.e.
CHj(0H).0H2(0Bt). (134°) at 722 mm. S.G.
IS -926 (Demole, B. 9, 745). From mono-sodium
glycol CH2(0H).CH2(0Na) and EtI (Wurtz, A.
108, 84).
Di-ethyl ether CsH„Oj i.e. 02H4(0Et)j.
(123-5°). S.G, 2 1-799. V.D. 4-10 (calo. 4-09).
From the preceding compound by successive
treatment with potassium and EtI (W.).
Colourless oil with ethereal odour. Isomeric
with aoetal.
Ethyl-phenyl ether C2H4(OPh)(OEt).
(230°). S.G. a 1-037 (S.) ; " 1-018 (H.). Formed
by the action of alcoholic KOEt on phenyl bromo-
ethyl oxide Ph.O.C^H^Br (Sabanfieff, Bl. [2] 41,
253), or on phenyl chloro-ethyl oxide (Henry,
C. B. 96, 1238),
Ethylidene ether O^fi^Le,
<;^^-^>OHMe. (82-5°). S.G. 2 1000. V.D.
3-19 (calc. 3'05). Obtained by heating aldehyde
with glycol for a week at 100° (Wurtz), Liquid;
dissolves in 1^ vols, water, but separated from
the solution by CaClj and by KOH. Not attacked
by KOH. HNO3 forms oxalic and glyooUio
acids. PCI5 gives aldehyde and CjH^Ola. Brom-
ine gives liquid CjHjBrO, (c. 150°), whence dilate
H2SO, liberates glycol bromhydrin.
Propi/lidene ether C^ifi^^-^-
<p&;Q>CHEt. (106°). V.D. 3-46. S.G. S
-98. Obtained by heating propionic aldehyde
(1 mol.) with glycol (2 mols.) at 100° in a sealed
tube ; the yield being 75 p.c. (Lochert, A. Ch.'
[6] 16, 30). Colourless limpid liquid; smelling
like propionic aldehyde. Dissolves in 5 vols,
water ; miscible with alcohol and ether. EOH
and CaClj separate it from its aqueous solution.
Completely saponified by heating with water at
130°, or by treatment with cone. HClAq. Does
not reduce ammoniacal AgNO^, Bromine gives
a liquid bromo- derivative.
Isohutylidene ether 0^jjOii.e.
<^]^^-^>CH5r, (125°), V,D, 4-13 (calc
4-02). 'S.G. 2 -964. Obtained by heating iso-
butyrie aldehyde (1 mol.) with glycol (2 mols.) at
100°; the yield being 70 p.c. (L.). Liquid; dis-
solves in 6 times its volume of water, miscible
with alcohol and ether. Saponified by water at
130°, by cone. HClAq, and by dilute HjSO,.
Does not reduce ammoniacal AgNO,. , Bromine
gives a bromo- derivative CgHiiBrO, (o, 190°), in-
sol. water, sol. alcohol and ether.
Isoamylidene et%er G,H,,02t.e,
<oh:o>°^-°^-
(145°). S.G, 2 -944.
Prepared like the preceding, using isovaleric
aldehyde (L.). Liquid, v. si, sol. water, v. sol.
alcohol and ether. Saponified by water at 130°,
Does not reduce ammoniacal AgNOg. Bromine
gives a bromo- derivative CjHisBrOj (94°
at 10 mm.) which is insol, water, sol, alcohol
and ether, and when saponified by dilate HjSO,
gives bromo- valeric aldehyde. Alcoholic EOH
attacks the bromb-derivative, removing HBr and
forming <:^pg2-Os^cH.OH:OMe2 and a small
quantity of <^|[»;Q>OH.CH(OH).CHMej.
GLYCOt.
633
Beptylidene ether <^^^-0>qjj q^U^^
(180°). Formed by heating glycol (3 vols.) with
oenanthol (1 vol.) at 130° ; or from glycol (2 vols.),
oenanthol (1 vol.), and a trace of HOAo at 180° ;
the yield being 66 p.c. (Lochert, Bl. [2] 48, 337 ;
A. Ch. [6] 16, 36). Limpid liquid, Emelling like
Oenanthol ; v. si. sol. water, v. sol. alcohol and
ether. Completely saponified by water at 130°,
or by oono. HOlAq. Gaseous HOI does not act
on it in the cold, but at 100° it forms glycol
ohlorhydrin and oenanthol, and its polymeridcs.
PCI5 gives ethylene chloride and cenanthol.
Bromine gives a liquid mono-bromo- derivativei-
Glycol ohlorhydrin C^aClOj i.e.
CH2(0H).CH2C1. (180°). Is described as Chioko-
ethyl'aiiCoboii on p. 61.
Glycol ohloro-acetin v. Acetyl derivative
of ChLORO-ETHYIi ALCOHOIi, p. 61.
Glycol bromhydrin OjHsBrOji.e.
CHj(0H).0H2Br. Bromo-ethyl alcohol. (147°)
(H.) ; (155°) (L.). S.G. a 1-66 (H.). Formed,
together with di-ethylenio glycol, by heating
glycol (1 pt.) with ethylene bromide (1 pt.) at
120° in a sealed flask (Lourenpo, Bl. 1, 77).
Formed also by treating glycol with HBr at 100°
(Henry, A. Oh. [4] 27, 250), and from glycol
(3 mols.) and PBr, (1 mol.) (Demole, B. 9, 48).
Liquid.
Nitrate CHj(0N02).CHjBr, (165°). S.G.
s 1'735. From the bromhydrin, HNOj, and
HjSO, (Henry, A. Ch. [4] 27, 258).
Acetyl derivative (!!H2(0Ac).CH2Br.
Glycol bromo-ace^m. (162°). From glycol
mono-acetin and HBr at/lQO° (Demole, A. 173,
121). Liquid, si. sol. water. Gone. NaOHAq
decomposes it, liberating ethylene oxide.
Brom.o-acetyl derivative
CHjBr.CO.O.CHj.CHfBr. (230°-240°). From
glycol chlorhydnn and bromine, the other pro-
ducts being ethylene chloro^bromide, bromo-,
and di-bromo-acetio acids, and ethylene brom-
ide (Demole, B. 9, 557). Slightly decomposed
on distillation..
, Glycol iodhydrin CjHjIOi.e.CHj(OH).0HjI.
lodo-ethyl alcohol. Obtained in impure con-
dition from glycol and HI in the cold ; but if the
temperature is allowed to rise only ethylene
iodide results (Maxwell Simpson, Pr. 10, 119).
More easily prepared by heating the ohlorhydrin
with excess of powdered EI at 100° for 24 hours
(Butlerow a. Ossokih, A. 144, 42; 145, 257).
Non-volatile liquid, m. sol. water, separated from
its aqueous solution by KgCO,. ZnMe^ followed
by water gives isoprppyl alcohol. ZnEtj fol-
lowed by water gives sec -butyl alcohol.
Acetyl derivative CB^(OAo).0H2l. Qly-
coUc iodo-acetin. From glycol mono-acetin and
HI ; or from glycol, HOAc, and HI (Maxwell
Simpson, A. 113, 123 ; Pr. 10, 115). Oil, which
crystallises in tables at a low temperature. KOH
gives ethylene oxide.
GlyoolcyanhydrinOjH4(OH)CN. Eyd/raorylo-
nitrile. (0. 220°). S.O. 2 1-0588. S. (ether)
2-3 at 15°. From ethylene oxide and HCy (Br-
lenmeyer, A. 191, 273). MisoiWe with water and
with alcohol, insol. CSj. HOI (S.G. 1-10) or
aqueous NaOH give, on boiling, hydraorylio and
acrylic acids.
Di-echylenic glycol C^HuO, i.e.
QO.C,H..O.CX-OH. (245°-250°). S.G. 2 1-132.
V.D. 3-78 (oalc. 3-67). When an excess of ethyl-
ene oxide is heated with water in sealed tubes
there is formed glycol, di-ethyleziio glycol, and
a small quantity of tri-ethylenio glycol i^xatz,
A. Ch. [3] 69,330). By heating oxide of ethylene
(1 pt.) with glycol (1 pt.) there are formed di-
and tri- ethylenic glycols. By heating glycol
with ethylene bromide at 115° in sealed tubes
glycol bromhydrin, diethylenio , glycol, other
polyethylenio glycols, and water are produced ;
if the temperature of the mixture is allowed to
rise above 130° the liquid turns brown and yields
the bromhydrins of the various polyethylenio
glycols (Louren(fo, C. B. 51, 365). By using
glyoolic ohlorhydrin instead of the bromhydrin
the polyethylenio ohlorhydrins may be obtained.
Diethylenio glycol may also be obtained from its
diacetate by treatment with an alkali. Obtained
also by treating glycol mono-acetin with sodium-
glyool (Mohs, Z. 1866, 495). Sweetish syrup ;
sol. water^ alcohol, and ether. Kitrio acid (S.G.
1-42) oxidises it to ' diglyoollio acid '
C02H.OH2.0.CH2.002H,glyoollio aoid, and oxalio
aoid. Oono. HIAq gives ethylene iodide.
Mono-formyl derivative
CH2(0H).CHj.0.0Hj.0Hj(0CH0). (0. 220°).
From the ohlorhydrin and nitro-methane by
heating for 10 hours at 200° (Ffungst, J. pr. [8]
34, 37).
Di-aoetyl derivative
OHj(OAc).OH2.0.CH2.CH2(OAo). (245°-251o).
Formed, together with C2H4(OAc)2 and the di-
acetyl derivatives of other polyethylenio glycols,
by heating ethylene oxide with glacial HOAo or
with A02O at 100°, and fractionally distilling the
product. Formed also from glycol diacetin and
ethylene oxide fWurtz, C. B. 50, 1195 ; A. 116,
249).
Ohlorhydrin CjHgOlOj i.e.
CHj(OH).CHj.O.CHj.CH201. (180°-185°). From
ethylene oxide and glyoolic ohlorhydrin at 140°
(Wurtz, A. Ch. [3] 69, 338). AI50 from ethylene
oxide and gaseous HCl; and from glycol and
glycol ohlorhydrin at 140° (Lourenfo, .i. CA. [3]
67, 290).
Bromhydrin OjHjBrOj i.e.
HO.OjHj.O.OjHjBr. (205°). From glycol and
OjH^Br^ at 160° (L.),
Tri-ethylenio glycol 0^„0, i.e.
CH,(OH).OHj.O.'OH2.0Hj.O.OHj.CH2(OH). ' (0.
290°). S.G. 1-138. Formed by heating glycol
with ethylene oxide (v. supra). Thick liquid,
miscible with water and alcohol, si. sol. ether.
Oxidised by nitric acid to ' diglycolethylonio '
acid (C02H.OHj.O)20jH4 ; a syrupy aoid which
crystallises with difSculty and forms cry9talline
salts : KHA".— CaA" 3aq.— AgjA".
Di-acetyl derivative O2(0jH,)j(OAc)2.
(290°-300°). From ethylene oxide (2 mols.) and
glycol diacetin. Liquid, miscible with water,
alcohol, and ether.
Ohlorhydrin 0,H,sC10,. (222°-232°).
From ethylene oxide ^2 mols.) and glycolio
ohlorhydrin (1 mol.). Liquid, sol. water.
Bromhydrin G^B.,^tOt. (250°), Slightly
decomposed on distillation.
letra-ethylenic glycol C,H,aO, i.e.
(OHj(OH).OHj.O.C2HJjO. (300°); (230° at 25
mm.). Formed as above from glycol and ethyl-
ene bromide.
634
GLYCOL.
Diaeetyl derivative C,H,„Ao205. (above
390°). From ethylene oxide (3 mols.) and glycol
diaoetin (1 mol.). '
Chlorh^drin CsH„010,. (262°-272°).
Liquid, sol. water.
Penta-ethylenic glycol C,„HjjOj i.e.
(CHj(0H).CH3.0.CjH,.0)AH4. (281° at 25 mm.).
Liquid, sol. water, alcohol, and ether.
Hexa-ethylenic glycol OiaHjjO, i.e.
(CH2(OH).CHj.O.CjH4.0.CjHj20. (325° at 25
mm.). Viscid liquid (L.).
GLTCOLAMIC ACID v. GlyooIlamio acid.
DI-GLTCOL-ETHYLENIC ACID v. Tri-ethyl-
erdc OLYcoL.
GLYCOLIGNOSE v. Cellulose.
GLYCOLINE OeH„Nj. (155°). S.G. iS 1-008.
A base formed by distilling glycerin (6 pts.) with
ammonium chloride in a current of NH, (Eturd,
C. B. 92, 460, 795). Liquid, smelling like pyri-
dine. Miscible with water, alcohol, and ether.
With'Etl it forms a compound CgHioNjEtl crys-
tallising in lemon-yellow needles. — CgHigN^HCl :
needles, v. e. sol. water and alcohol.
GLTCOIIAMIC ACID NHj.CHj.COfl v.
Gltcocoll.
DiglycoUamic acid C,H,NO, t,e.
NH(CH2.C02H)2. Imido-di-aceUc acid. 8. 2-43
at S°. When ohloro-aoetic acid is boiled with
cono. NHjAq for 12 hours there is formed a mix-
ture of glycocoU, diglycoUamio acid, triglyeol-
lamic acid, and a little glycoUic acid. The solu-
tion, after being freed from most of the NH4OI
by ppn. with alcohol is boiled with Pb(0H)2. The
pp. thus obtained contains lead triglycoUamate
(whence the acid may be liberated by HjS), and
the solution, freed from lead by H^S, is boUed
with ppd. ZnCOg, when insoluble ainc diglycol-
lamajie is formed, zinc glycocoU remaining in
solution .(Heintz, A. 122, 257 ; 124, 297 ; 136,
^13 ; 145, 49 ; 156, 54). Trimetric prisms, insol.
alcohol and ether; m. sol. water, forming an
acid solution. Forms a nitrosamine with nitrous
acid.
Salts. — NHjHA": prisms, v. e. sol. water,
ihsol. alcohol. — ^BaHjA",: amorphous, v. sol.
water. — CuA" 2aq : small blue prisms, si. sol.
boiling water. — PbA": slender needles. — ZuA":
minute tables, nearly insol. water. — AgjA":
crystalline pp., insol. water. — AgjA"HNO, 4aq :
prisms, insol. alcohol. — H2A"HC1 : tables, t. e.
sol. water, m. sol. alcohol. — H2A"HN03. —
(HjA")jH2S04 : small prisms. Decomposed by
water into HjSO, and HjA".-H2A"HjS0,:
formed by boiling the preceding with alcohol.
' Amide CflsNA »■«■ NHIOHj.OO.NHj)^.
Prepared, together with the amide of triglycol-
lamic acid, by heating ohloro-^cetic ether with
ammonia at 60° to 70°, evaporating, washing
with ether, dissolving . in water, and ppg. the
mixed hydrochlorides with alcohol. The amides
are liberated by Ag^O, and may be separated by
alcohol, which dissolves only the amide of di-
glycoUamic acid (Heintz, Z. [2] 6, 161). Tri-
metric tables (from water) ; m. sol. water, si. sol.
hot, nearly insol. cold, alcohol. Its aqueous so-
lution is alkaline. — B'HCl : prisms (from water),
si. sol. alcohol. — B'jHjPtClj: six-sided tables
(from water), insol. alcohol. — B'HAuCl,: thin
six-sided tables (from water) or long needles
(liOin alcohol).
Anilide NH(CHj.CO.NHPh)r [141°].
Formed by digesting the ohloro-aoetyl derivative
of aniline with alcoholip ammonia at 100°, eva-
porating, and crystallising from water (Pi J.
Meyer, B. 8, 1154). Needles; m. sol. hot water,
V. sol. ether and alcohol, si. sol. cold water.
When boiled with aqueous NaQH it gives oS
aniline. Its nitrate crystallises in needles
[172°]. Tommasi {Bl. [2] 22, 3) by the action
of alcoholic NHj on the chloro-aoetyl derivative
of aniline at 50° obtained an amorphous com-
pound OgHjiNOs
p-Toluide NH(CHj.CO.NHC,H,)j: [150°].
From the ohloro-acetyl derivative of toluidine
and alcoholic NH3 at 100° (Meyer, B. 8, 1155).
Bosettes of long silky needles (from dilute alco-
hol) ; si. sol. boiling water, m. sol. cold alcohol,
V. sol. ether.
VreUe NH(CH2.C0.NH.C0.NHj)j. [195°-
200°]. From bromo-acetyl-urea and dry or al-
coholic NH, at 80°-100° (Mulder, B. 5, 1011).
Slender needles ; si. sol. cold, m. sol. warm,
water. V. sol. dilute HClAq and reppd. by NHj.
— B'HCl: crystals. — B'jHjPtCls : needles or
pjrisms.
Nitrosamine N0.N(CH2.C02H)2. [above
100°]. Small pale yellow tables, m. sol. water,
alcohol, and ether.— CaA"aq: more sol. cold
than hot water, nearly insol. alcohol. — BaA" f aq :
crystalline crusts. — Ag^A" : sparingly soluble
prisms (Heintz, A. 188, 301).
Triglycoliamic acid CgHgNOg i.e.
N(CH2.C02H)3. S. -134 at 5°. Formed by boiling
ohloro-aoetic acid with NH, {v. supra), or digly-
collamic acid with chloro-acetio acid (Heintz,
4. 122, 239 ; 136, 221 ; Luddecke, .4. 147, 272 ;
Ziegler, Zt [2] 5, 659). Small prisms. Does
not combine with acids. Fuming HCl at 200°
splits it up into diglycoUamic and glycollio
acids. Nitrous gas does not act on it. Zinc
and dilute HjSO, reduce it to ethyl-diglyooUa-
mio acid.
Salts.— (NH4)2HA"'aq:needles.—K2HA"'aq:
needles, v. sol. water. — BaHA"'aq: prisms, si.
sol. water. — BaaA"'8 4aq : laminse, insol. water. —
PbHA" 2aq : prisms. S. 3-3,- Pb,A"'s : laminss.
— ^AgjA'" : crystalline pp.
Ethyl ether EtjA'". (280°-290°). From
the silver salt and EtI (Heintz, A. 140, 264).
Liquid, more sol. cold than hot water.
Amide N(0H2.00.NHj)j. From the pre-
ceding ether and NH,. Also from chloro-acetio
ether and NH,. Bectangular tables (from alco-
hol) ; V. sol. hot water, si. sol. alcohol. Neutral
to litmus. — ^B'HCl : trimetrio prisms (from water).
— B'2H2PtClg : tables or lamiuse, insol. alcohol
and ether.— B'HAuClj.
GLYCOLLIC ACID CjH^O, i.e. HO.CHj.COjH.
Oxyacetie acid. Mol. w. 76. [79°].
Occurrence.— In the grease of sheep's wool
as the potassium salt ; separated therefrom by
forming the lead salt, decomposing this with
H2S04, and extracting with ether (Buisine, C. B.
107, 789). Occurs also in the juice of jjnripe
grapes and in the leaves of the wild vine (Ampe-
lopsis hederacea) (Erlenmeyer, Z. 1866, 639 ;
Qorup-Besanez, A. 161, 229).
Formation.— 1. From hippuric acid either by
treatment with nitrons acid and decomposition
of the resulting benzoyl-glycollio acid by boiling
dilute H,SO„ or by treatment with dilute HjSO,
and decomposition of the resulting glycocoU by
GLYCOLLIG AOID.
6S5
nitrous acid (Soooloff a. Streoker, A. 80, 18).—
2. Tartronio acid C0jH.CH(0H).C02His heated
to 180° ; the residue, consisting of nearly pare
glycollide, is dissolved ia aqueous EOH, silver ni-
trate is then added, and the ppd. silver^ glycol-
late decomposed by HCl (Dessaignes^ 0. B. 38, 44),
8. From glyozal by the action of alkalis (Debus)
and even of water. Thus, when glyoxal is heated
with water at 150°, one-third of it is converted
into glyoollio acid (De Fororand, 0. B. 98, 295).—
4. By boiling silver bromo-acetate with water.
By boiling iodo-aoetio acid with moist AggO, or
lead iodo-acetate with water (Perkin a. Duppa,
P. M. [4] 18, 5^). In like manner by boiling
chloro-acetic acid with caustic alkalis or by heat-
ing crystallised ohloro-acetate of potassium or
sodium (Eekul£, A. 105, 286). By boiling ohloro-
acetonitrile with lime-water (Beckurts a. Otto, B.
9, 1591). — 5. By allowing a solution of glycol
(1 vol.) in nitrio acid (4 vols, of B.G. 1-33) to
stand for some days (Wurtz, C. B. 44, 1306).—
6. Together with other products from propylene
glycol by oxidation with EKO,, or with air and
platinum black (Wurtz, C. B. 45, 306).- 7. By
placing in a tall cylinder layers of alcohol, water,
and couc. nitrio acid one above another, and
leaving the liquids to mix by diffusion, which
they do in about a week (Debus, A. 100, 1).
Glyoxal, glyoxylic acid, oxalic acid, aldehyde,
and acetic acid are formed at the same time. —
8. Found in the mother-liquor in the prepara-
tion of mercuric fulminate (Cloez, C B. 34, 364 ;
Fahlberg, J.^n [2] 7, 331).— 9. By the action of
zinc and dilute H2SO, on oxalic acid (Schulze,
Z. 1862, 616, 682 ; Church, C.J. 16, 301).— 10. By
boiling an aqueous solution of oxalic acid for eight
days with zinc (Orommydis, Bl. [2] 27, 3 ; De
Forcrand, Bl. [2] 39, 310).— 11. By the action of
nitrio acid on acrolein (Claus, A. Swppl. 2, 119).
12. When tartaric acid is warmed with cone.
HjSO^ at 45° it gives off CQ, CO,, and SOj, and
the residue contains glyoollio and pyruvic acids
as well as tartaric and racemic acids. The acids
are separated by crystallisation, first of their
barium, and then of their calcium, salts (Bou-
chardat, 0. B. 89, 99).— 13. From acetylene
tetrachloride and alcoholic EOH at 100° (Ber-
thelot, Z. 1869, 683).— 14. From di-chloro-vinyl
ethyl oxide and water at 130° (Geuther a. Brocks
hoff, J. pr. [2] 7, 114).— 16.' Occurs among the
products of ttie action of HNO3 on glycerin. —
16. Together with gluconic and formic acids, by
the action of red HgO and baryta-water on gly-
cerin (Herzfeld, A. 245, 27). Also from glycerin
and AgjO (Kiliani, B. 16,2415).— 17. By heating
cupric acetate (2 pts.) with water (5 pts.) at 200°,
cuprous oxide being ppd. (Cazeneuve, C B. 89,
,525) . — 18. By oxidising inulin with HNO, (Eiliani,
A. 205, 168). — 18. From glucose or Iffivulose by
oxidation with Ag^O.
Preparation.— X. A solution of 10 grms. of
commercial glycerin (85 p.c.) and 6 grms. of
Ca(OH), in 200 o.c. of water is heated on a water-
bath with precipitated Ag^O (prepared from 60
grms. of AgNOs) for four hours. The liquid is
then filteredi saturated with COj, boiled, again fil-
tered, and evaporated till the calcium glycollate
Cl-ystallises out ; the yield is 4-6 grms. (Eiliani,
B. 16, 2414).— 2. Crude sugar (1 pt.) isheated with
'i p.c. sulphuric acid (20 pts.), the sulphuric acid
removed by barium carbonate, and to the filtrate
are added calcium carbonate (2 pts.) and silver
oxide (10 pts.). The mixture is heated to 80°
until gas ceases to be evolved ; it is then filtered
and evaporated, when calcium glycollate separates
out (Eiliani, 4. 205, 191).— 3. A few grammes of
strong alcohol are gentty heated in a capacio;a3
vessel, with a small quantity of nitric acid, till
the vessel becomes flUed with red fniues of
nitrous acid ; and when the action has been thus
set up, about 500 grms. dilute alcohol of 20 per
cent., and 440 grms. nitric acid of specific gravity
1-34 are poured in. The reaction, which must
be moderated by immersing the vessel in water
at 20°C., is complete in about 12 hours. The
liquid is evaporated in small portions over a
water-bath, neutralised vrith lime and the mix-
ture of glycollate of calcium, glyoxal, and gly-
oxylate of calcium boiled for several hours with
milk of lime, whereby both the glyoxal and the
glyoxylic acid are converted into glycoUic acid.
The hot filtrate freed from excess of lime by car-
bonic acid yields tolerably pure glycollate of
calcium ; and by decomposing this salt with
oxalic acid, neutralising the filtrate with car-
bonate of lead, and evaporating, the neutral
glycollate of lead is obtained in weU-developed
crystals. The hot aqueous solution of this salt,
decomposed by an equivalent quantity of dilute
sulphuric acid, yields a solution of glycollic acid^
which may be crystallised by evaporation to a
syrup at 60° or 70°C., afterwards m vacuo over
oil of vitriol, and purified by recrystallisation
from anhydrous ether (Lautemann, Kolbe's Org.
Chem. ; Drechsel, A. 127, 150).— 4. By boiling
chloro-acetic acid with water or with water and
calciuin carbonate (Fittig, B.9, 1198 ; Thomson,
A. 200, 76 ; Holzer, B. 16, 2955).
Properties. — Needles (from water)(, or plates
(from ether). When not quite pure it is de-
liquescent. V. sol. alcohol and ether. .Scarcely
extracted by ether from its aqueous solution.
Very slightly volatile with steam. When strongly
heated it gives off pungent fumes and forms gly-
collide and formic paraldehyde (Erupsky, Z. [2]
6, 177). Cone, HNO3 oxidises it to oxalic
acid. According to Claus (A. 145, 256) - it
may be reduced to acetic acid 'by zinc and
HjSOi. Cone. HBrAq at 100° slowly con-
verts it into bromo-acetic acid (Eekul^, A. 130,
11). Glycollic acid yields methane (2 vols.)
and hydrogen (1 vol.) when distilled with excess
of quicklime (Hanriot, Bl. [2] 45, 80 ; O. B. 101,
1156). With chloralide at 125° it slowly forms
ca,.o
I "SCaCClj [41°], which forms small
CO.O
crystals, sol. alcohol, ether, and chloroform
(Wallaoh, A. J.93, 35).
Salts. ^NHjHA'j: slender needles; v. sol.
water and hot alcohol. — NaA'aq : small crystals
(from water). — NaA'iaq (from dilute alcohol), —
NaHA',: silky needles. — Na202H20s2aq: small
deliquescent needles (De Forcrand, Bl. [2] 40,
104).— TLA': long pointed needles.— EA'^aq:
silky needles. — GaA'28aq (Lubavin, J. B. 14,
287).— CaA'25aq.— CaA'j4aq (Fittig, J.pr. [2] 10,
271).'— CaA'j 3aq (Debus ; B6ttinger, 4.198, 228) .
— CaA'jlfaq: stellate groups "of asbestos-Iilce
needles; si. sol. cold water. — CaA',. Obtained
by evaporating a solution at 100° (Fahlberg;
CaiiuB, /. pr. [2] 9, 303). Crusts of small
636
GLYCOLLIO AOID,
crystals. S. 1-2 at 10° (Debus, A. 166, 117) ; 5-3
at 100° fPahlberg).— CaA'jCaCl^eaq: separates
from a highly concentrated solution coataining
the two salts in large octahedra, permanent over
sulphuric acid in the exsiccator (Jazukovitch,
Z. 1864, 62). — CaA'2CaCl,2aq (Bottinger). A
double calcium salt of glycollic and glyoxylic acids
CaC4H„Oa(Ca04HjOj)2 2aq crystallises from the
product of the oxidation of alcohol. — SrA'^Saq :
minute slender needles, nearly insol. alcohol
(Scheiber, /. pr. [2] 13, 436). S. 3-3 at 19°.—
BaA', : monoclinic prisms. S. 13 at 17°. —
MgA'2 2aq: extremely thin minute needles. S. 8
at 18° (Scheiber). V. sol. boiling water. —
ZnA'2 2aq: tufts of needles or prisms. S. 3 at
17°. Beadily forms supersaturated solutions
(Schulze). — PbA'^: monoclinic crystals resem-
• Ming gypsum. S. 3 at 15°.— PbA'jPbO : from
the calcium salt and lead subacetate. Crystalline.
S. -01.- PbA'jPbClj. Formed by adding lead
chloride to the ammonium salt (Engel, Bl. [2]
44, 424).^CuA'j : blue crystals. S. -7 in the
cold. — HgA'jHgOLj ! prisms, si. sol."^ cold water.
Formed by boiling ohloro-acetic acid with HgO.
— AgA' : spangles, si. sol. cold water ; decom-
posed by boiling water. Insol. alcohol (KekulS).
— AgA'aq : large crystals (Dessaignes) . — AgA'^aq :
monocUnio lamineB (Naumann, A. 129, 278). '
Acetyl derivative AcO.CH^.COjH. From
glycollic acid and Ac^O at 160° (Senff, A. 208,
277). Small prisms, t. e. sol. water, t. b1. sol,
alcohol. Decomposed by alkalis into acetic
and glycollic acids. — OaA'3 2aq : from acetyl-
glycoUic ether by boiling with lime (Heintz, A.
123,325).
Benzoyl derivative BzO.CH2.CO2H.
Formed by the action of nitrous acid on hippuric
acid (Strecker, A. 68, 54 ; Strecker a. Socoloff, A.
80, 18). It may also be prepared by slowly
passing chlorine into a solution of hippuric acid
in moderately dilute KOH, neutralising with HCl,
evaporating and extracting with ether (G-ossman,
A. 90, 181; Strecker, A. 91, 359). Prisms (from
alcohol) or laminee. SI. sol. cold, m. sol. hot, water ;
T. sol. alcohol and ether. Melts under water.
Gives off benzoic acid when heated strongly.
Decomposed by boiling water into benzoic and
glycollic acids ; this hydrolysis is accelerated by
the presence of mineral acids. Sodium-amalgam
forms ' ben^oleiq ' acid C,H„02 and an acid '
C„H2,0„ which has an odour of excrement, is
insol. water and ether, but v. sol. alcohol, and
forms gummy 'Ba.C^^^O,. (Otto, A. 145, 350).
Salts.— NaC8H,043aq. — CaA'22aq. — CaA'^aq:
slender needles. S. 2-36 at 11°; 13-3 at 100°.
Jleadily forms supersaturated solutions. Forms
a double salt with CaCl^. — BaA', 2aq : deli-
cate silky needles.— PbA'j.—(PbAyjPbO 3aq.—
(FeA',)2(Fe203)331aq: voluminous flesh-coloured
pp. — ZnA'j 4aq. — ^AgA'.
m-Ohloro -benzoyl derivative
C|^,Cl.C0.0.CHj.C02H. From m-ohloro-hip-
puiio acid and nitrous acid (Otto, A. 122, 164).
Waxy crystalline mass, si. sol. water.
Methyl eifcer HO.CHj.COjMe. (151° i.V.).
S.G. g 1-1868 (Sohreiner, B. 12, 179; A. 197, 1).
Ethyl ether HO-CHj-CO^Et. (160° i.V.).
S.G. g 1-1078 (Schieiner). Formed by treating
chloro-acetio ether with rather more than an
equivalent quantity of sodium glycoUate (or of
podium acetate in presence of alcohol) at 140°
(Heintz, P. 114, 440 ; A. 123, 326 ; Sohreiner.
A. 197, 5). Prepared by heating glycoUide with
alcohol in sealed tubes at 200° (Norton a. Tscher-
niak, C. iJ. 87, 30). Liquid, which dissolves in
water forming a neutral solution from which it
may be separated by K-fiO^. Boiling alkalis
decompose it into alcohol and glycollic acid.
With aqueous NH, it forms the amide {v.infra).
It combines with CaCl,. With FCl, it reacts in
the cold forming chloro-acetic ether (Henry, B.
3, 705); excess of PCI5 at 150° gives chloro-
acetyl chloride. A mixture of HNO, and H^SO,
forms N02.0.CHj.C0jEt (181°). S.G. is 1.211
(Henry, A. Ch. [4] 28, 424). Cyanic acid forms
the allophanyl derivative [144°] of which the
corresponding acid melts at 192° (Traube, C C.
1888, 1435).
Acetyl derivative of the ethyl ether
AoO.CH2.C02Et. (179°;. S.G. i^ 1009. Pre-
pared by heating chloro-acetic ether with dry
NaOAc at 170°. Formed also by the action of
alcoholic KOAc on brpmo-acetic ether (Gal, A.
142, 370). Formed also by passing chlorine into
a cooled alkaline solution of aceturic ether (Cur-
tius, B. 17, 1673). Liquid, si. sol. water. NH,
converts it into acetamide and the amide of gly-
collic acid. Solid KOH saponifies it. HBr forms
ethyl bromide, HOAc, and bromo-acetio acid.
HI, even in the cold, forms EtI, acetic ether, and
HOAo.
Propiony I derivative of the ethylether
C3H50.0.CH.,.C02Bt. (200°). S.G. ^ 1-005.
From chloro-acetic ether and sodium propionate
at 175° (Senff, A. 208, 274). Colourless, strongly
refracting, liquid, v. si. sol. cold water.
Butyryl derivative of the ethylether
C4H,0.0.0Hj.C0jEt. (206°). S.G. '^ 1029.
From bromo-acetic ether by heating with potas-
sium butyrate (Gal, Bl. [2] 7, 329).
Isobutyryl derivative of the ethyl
ether Pr.C0.0.CH,.C0.JEt. (197°). S.G. 23
1-024 (Senff, A. 208, 271).
Garbony I derivative of the ethylether
CoH^O, i.e. C0(0CH2.C0jEt)2. Carbo-diglycolUe
ether. ("280°). Formed, together with ethyl-
chloro-formate and glycoUide, when gaseous car-
bonyl chloride COCI2 is passed through glycoUio
ether (Heintz, 4. 154, 257). Viscid heavy oil, v.
sol. alcohol and eiher. Beadily decomposed by
bases into carbonate and glycollate.
Carboxy-glycollie ether C,H,j0, i.e.
C02Et.0.CH2.C02Et. (0. 240°). Formed by
heating chloro-formic ether with glycollic ether
(Heintz). Heavy oil, v. e. sol. alcohol and ether.
Benzoyl derivative of the ethyl ether
C„H,j0, i.e. BzO.CH,.COjEt. (287° cor.). S.G.
— 1-1509. From chloro-acetic ether and NaOBz
at 180° (Andrejeff, A. 133, 284). Also from
diazo-acetic ether by heating with benzoic acid
(Curtius). Oil.
Propyl ether B.O.CK^.GO^i. (171° i.V.).
S.G. § 1-0640 (Sohreiner, A. 197, 1).
Chloride HO.CHj.COCl. From glycollia
acid and PCI5 (Fahlberg, J. pr. [2] 7, 343). Ex-
cess of PCI, at 120° gives chloro-acetyl chloride.
4mideH0.CHj.C0NHj. [120°]. Formed by
dissolving glycoUide in aqueous ammonia
(Heintz, A. 123, 322). Formed also by the
action of aqueous NH, on glycoUio ether. Left
as a residue when ammonium tartronate il
GLYOOLLIO ACID.
637
heated above 160° (DesBaignea, G. B. 38, 47).
Crystals (&oin water). V. sol. water, m. sol.
alcohol (its isomeride glyooooll is nearly insol.
alcohol). Does form salts with bases. Does not
hinder the ppn. of Cu(OH)j. Boiling KOHAq
converts it into glycollic acid. Dilute HClAq
does the same.
Ethylamide HO.OHj.CO.NHEt. (250°).
From chloro-aoetio ether and alcoholic ethyl-
amine (Heintz, A. 129, 27). Syrup; miscible
with water and alcohol, sol. ether. Decomposed
by alkalis, even in the cold, into ethylamine and
glycoUio acid.
4j1iZideHO.CH2.CO.NHPh. [108°]. S. 6
at 20° ; 100 at 100°. Prom glycoUide and ani-
line at 130° (Norton a. Tsoherniak, C. B. 86,
1332). Monoclinic needles ; v. e. sol. alcohol and
ether.
Di-bronio-o-toluide
HO.CH2.CO.NH.C5HjBrjMe. [182°]. From its
acetyl derivative AcO.CH^.CO.NH.OjHjBrjMe
[172°], which is got by heating the compound
Br.CELrCO.NH.CeH2Br2Me with acetamide at
160° (Abenius a. Widmann, J", pr. [2] 88, 285).
Needles (from alcohol).
Acetyl derivative of the nitrite
C^H,NOji.e.AoO.CH,CN. (175°). S.G. iS? 1-100.
From chloro-acetonitrile and alcoholic EOAo
(Henry, G. B. 102, 768). Liquid, smelling like
acetic acid. Has a sweetish bitter taste. M. sol.
water. With HCl it yields chloro-acetio acid (?).
Anhydride v. Gtv^ooujIdis.
Methyl derivative MeQ.CH^.COiH.
(178°). S.G. 1-180. Prepared by dissolving so-
dium (2 atoms) in methyl alcohol and mixing
the solution with chloro-acetic acid (1 mol.).
Purified by means of its zinc-salt. Thick syrup,
miscible with water. Not decomposed by boiling
alcoholic NaOH. Salts. — KA'4aq : largeprisms
(from water); permanent in the air. Beadily forms
super-saturated solutions. Sol. alcohol. — NaA' :
deliquescent. — CaA'2 2aq: gnmhiy, but becomes
crystalline over H2SO4. — BaA',,: prisms, v. sol.
water, nearly insol. alcohol. — PbA',: crystalline
mass, sol. water and alcohol. — CnA'22aq : greenish
monoclinic prisms, sol. water and alcohol.— ^
ZnA'2 2aq : acute trimetrio octahedra. S. 27*4
at 18-4°. Sol. alcohol.-^AgA' : delicate £at
needles (from hot water).
Methyl derivative. of the methyl ether
MeO.0H,.COjMe. (133°) (Schreiner, B. 12, 179) ;
(127° i.y.) (Falsing, B. 17, 486). S.G. g 1-0890
(S.). Volatile with steam.
-Methyl derivative of the ethyl ether
MeO.CHj.CO^t. (139°) (S.); (131°) (F.). S.G.
g 1-0740.
Methyl derivative of the propyl ether
MeO.OH,.COjPr. (147° i.V.). S.G. g 1-0552.
Ethyl derivative BtOi.CH2.CO2H.
Ethyl-glycoUicadd. (199°) (Sohreiner). Formed
by the action of alcoholic NaOEt on chloro-
acetio acid (Heintz, P. 109, 489 ; 111, 552). The
resulting mixture is filtered from NaCl, evapo-
rated, dissolved in water, and mixed with cnprio
sulphate in quantity rather more than equivalent
to the sodium used. The mixture is evaporated
over the water-bath, and the residue is exhausted
with alcohol which extracts ouprio ethyl-glyool-
late. After purification by crystallisation this
tftU is decomposed by H^. Ethyl-glycoUio acid
is also formed from CH^Cl.CClg and excess of
iNaOEt (Geuther a. Brockhoff, J.pr. [2] 7, 101).
Liquid. Partially decomposed on distillation with
production of formic paraldehyde. When boiled
for a long time with inverted condenser it forms
glycollic acid and ethyl-glycollio ether, HIAq
gives EtI and glycollic acid. Salts. — BaA'2 :
crystallises with difficulty ; v. sol. water and
alcohol. — CaA'2 2aq : minute needles (from aleo-
hol-ether). — CuA'2 2aq: blue prisms. S. 14-2 at 14°.
Ethyl-derivative of the methyl ether
EtO.CH2.C02Me. (142^ i.V.) ; (148°) (F.). S.G.
g 1-0145 (Schreiner, A. 197, 1).
Ethyl derivative of the ethyl ether
Et0.CHj.C0..Bt. Ethyl-giycolUe ether. (158°)
(S.) ; (152°)' (F.). S.G. g -9996. Obtained as
above ; also from chloro-acetic ether and NaOIJt
(Hemry, J5. 4, 706). Formed also by treating
EtO.CH2.002Na with alcohol and EtI.
Ethyl derivative of the propyl ether
EtO-CHj-CO^Pr. (166° i.V.). S.G. g -9944.
Ethyl derivative of, the isoamyl,ether
Btb-CHj-COjOsH,,. (180°-190°). From sodium
ethyl-glycollate and isoamyl iodide in alcohol
(0. Siemens, J. 1861, 452).
Ethyl derivative of the chloride
EtO.CH2.COOL (128°). S.G. 1 1-145. From the
acid and PCI5 (Henry, B. 2, 276).
Ethyl derivative of the amide
EtO.CHyCONHj. (225°). From EtO.OHj.COjEt
and cold NH,Aq. Trimetric prisms. Melts
below 100°. V. e. sol. water, v. sol. alcohol and
ether. Gives with Br and EOHAq ^he urea
EtO.CH2.NH.CO.NH.CO.CH2.OEt [80°] (Hof-
mann, B. 18, 2734).
Ethyl derivative of the nitrite,
EtO.CH2.CN. (133°). S.G. 22-909. Formed by
distilling the amide EtO.CH2.CONH2 (40 g.) with
PA.(60g.) (Norton a. Tscherniak, 0. B. 87, 27).
Liquid, si. sol. water, v. sol. alcohol and ether.
Tri-chloro-ethyl derivative
C01,.CH2.0.CH2.C02H. [70°]. Formed, toge-
ther with chloro-acetio acid, by warming tri-
chloro-ethyl alcohol with aqueous KOH (Gar-
zaroUi-Thumlackh, A. 210, 71). Small plates
(from water). V. sol. alcohol, ether, and boiling
water. — CaA', 3aq : needles, m. sol. water. —
AgA': needles.
Propyl derivative of the methyl
ether PrO.CH2.C02Me. (179° i.V.). S.G. g -9850
(Schreiner).
Propyl derivative of the ethyl ether
PrO.0H2.0O^t. (185° i.V.)., S.G. g -9760. '
Propy I derivative of the propyl
ether PrO.CH2.G02Pr. (192° i.V.). S.G. g
•9778.
Isoamyl derivative C5H,,O.CH2.C02H.
(235°). S.G. 1-003. From sodium isoamylate,'
isoamyl alcohol, and chloro-acetic acid (Heintz,
P. 109, 301). Liquid, si. sol. water, naisciblo
with alcohol and ether.— NaA' 2aq : [190°-200°] ;
thin rectangular plates (from alcohol); v. sol.,
water and alcohol, insol. ether. — KA' aq : [200°-
210?]; long prisms or thin plates. Pp. by adding
ether to its alcoholic solution.— Hg2A'j : [170°] ;
white powder, v..sl. sol. water, si. isol. alcohol. —
CuA', : minute bluish-gieen prisms; v. si. sol.
water, m. sol. alcohol. — AgA': slender needles
(from water).
Isoamyl derivative of the ethvl
««fcerCjH„0.CH8.C0jEt. (212°). From sodium
638
GLYOOLLIC ACID.
isoamyl-glyooUate CjHuO.CH^.CO^Na and EtI in
alooholie solution at 100° (Siemens).
Phenyl derivativeC^^O^ifi.
CeH5O.CHj.OOjH. Phmoaiy-aceUc acid. 197°].
(285°). S.l. J'ormaiioTO. -1. By heating NaOPh
with chloro-acetic acid (Heintz, J. 1859, 361). —
2. By heating tri-bromo-ethylene with alcohol,
EOH, and phenol at 170° (SabanejefCa. Dworko-
witsch, A. 216, 284). Preparation. — 1. Equiva-
lents of phenol (1 part) and chloro-acetio acid
are melted together and (300 pts. of) solution of
NaOH (S.0. 1-3) is added. The lesultipg crystal-
line mass is pressed out, dissolved in water and
acidified with HCl. The acid separates as an
oil which soon becomes crystalline (Giaoosa,
J.pr. [2] 19, 396). — 2. By stirring in an iron-pan
a concentrated solution of sodio chloro-acetate
(12 pts.) with sodic phenylate (10 pts.). As soon
as the first reaction is over', the mass is heated,
with constant stirring until it becomes pasty.
This is dissolved in water before it is quite cold.
The acid is thrown down by HCl and crystallised
from water (Pritzsche, J.pr. [2] 20, 269). The
yield is 90 per cent. Properties. — White needles
(from water). Taste both aoid and bitter. Anti-
septic. Scarcely volatile with steam. Soluble
in ether, glacial acetic acid, benzene and CS,.
Etherified on keeping in alcoholic solution for
24 hours. BeaoUons. — 1. EeCl, gives a yellow
pp. — 2. Dilute mtric add (S.G. 1*19) converts
it intodi-nitro-phenol.— 3. Bromme-water lottos
CaH,Br.0.0Hj.C0jH (Giacosa).— 4. Violently at-
tacked by PCI5 forming PhO.CClj.COlj' and
CsH,C1.0.CH,.C001 (Michael, J. pr. [2] 35, 96).
Salts. — NaA'^aq. Needles (from alcohol). — KA.'.
Scales (P.). Needles (G.).—NH,A'. Scales (P.).—
CaA' 3^aiq. — BaA'j 3aq. — CuA'j 2aq : sparingly
soluble minute prisms. — AgA': slender needles
grouped concentrically. Methyl ether. —
MeA'. (245° uncor.). S.G. !!!:* 1-150. Ethyl
ether.— EtA'. (251° nncor.). S.G. '« 1-104.
Amide.— CHj(OPh)CO.NHj. [102°]. Prom NH,
and EtA'. Nitrile.— OHj(OPh)CN. (237°).
S.G. ^IP 109. Prom FjO, and the amide.
Thio-amide. — OH,(OPh)CS.NHj. [111°].
Prom the amide and alcoholic sulphide of
ammonium. Anilide. — OHj(OPh)CO.NHPh.
[99°]. Pormed by heating phenyl-glyooUate of
aniUne to 150°.
Bromo-phenyl derivative
CjH^Br.O.CHj.COjH. Bromo-phemyl-gVycolUc
add. [154°]. Solidifies at 143°. Pormed by
saponifying its ether. Also from the phenyl
derivative and Br. It forms dimetrio prisms, v,
Bol. alcohol, hardly soluble in water. Salts. —
NaA'2aq.— BaA'jliaq. Ethyl ether.— BVA.
[59°]. Solidifies at 28°. Prom phenyl-glyoollic
ether (70g.) dissolved in CSj (140g.), cooled to
0°, and treated gradually with bromine (65g.)
(Pritzsche, J. pr. [2] 20, 296). ProperWes.- In-
soluble in water, crystallises from t^cohol.
Chloro-phenyl derivative
CjH,C1.0.CHj.C0^. [152°]. Pormed from
CgHj.O.CHj.COjH by successive treatment with
PCI5 and water (Michael, J. pr. [2] 3S, 96).
Prisms.
o-NitrO'phenyl derivative
(NOj)C„H,O.CHj.COjH. [157°]. PreparaUon.—
o-Nitrophenol (30g.), chloraoetic aoid (20g.)
neutralised with strong NaOH are heated at 100°
tor 11 hours. The yield is fair (15g.) (A. Thate,
J.pr. [2] 29, 148). PrqpertMS.— Yellowish-white
pyramids (not regular octahedra). Doubly lo-
fracting. BeactUms. — 1. Reduced in alkaline
solution by sodiaim amalgam to azozy-, azo-,
hydrazo-, and amido- phenyl-glycoUic acid suc-
cessively. The azo- aoid N,(CeH,.0.CH2.C0.^H),
is crystalline [152°]. — 2. Beduced hjiron-fiUngs
teaAaceUo add to amido-phenylglyoollio aoid, or
rather its anhydride 0»H4<^2J^2q> [le?"]
(Thate, J. pr. [2] 25, 266). This anhydride
IS not affected by AojO at 180°. When heated
with zinc-dust it yields a very small quantity of
a base C,H,NO (0. 200°) (Duparc, B. 20, 1942).—
3. Beduced hy stannoits chloride and HCl to the
anhydride of chloro- amido- phenyl -glyoxylic
acid together with variable quantities of the
anhydrideof amido-phenyl-glycoUic acid (Thate).
Salts. — NaA'aq. — BaA'2aq. — CuA',2iaq
(Pritzsche, J.pr. [2] 20, 284).
o-Nitro -phenyl derivative of the
ethyl ether [2:1] C„H,(NO^.O.OHj.COjEt.
[49°]. Colourless needles, sol. alcohol, . ether,
and benzene, insol. water (Duparc, B. 80, 1942).
Beduced by tin and HCl to a base GgH^GlNOj,
which crystallises in long needles [195°], sol.
alcohol and alkalis, insol. ether.
p-Nitro -phenyl derivative
[4:l]0^,(N0J0.CHj.C0jH. [183°]. Prom
sodium ^-nitro-phenol, sodium chloro-acetate,
and caustic soda, each in concentrated solution.
The mixture is evaporated, extracted v^ith water,
and treated with HCl. The acid is recrystallised
from water (P.). Pale yellow plates. May be
reduced to very unstable j}-amido-phenyl-gly>
collie aoid. Salts. — NaA' 3aq.— BaA'j lOaq. —
CuA'j lOaq.
o- Amido -phenyl derivative
"NHj.CsH^.O.CHj.COjH. . o-Amido-phemyl-gVy.
colUc add. This acid splits up at the moment
of its formation into HjO and an anhydride:
*^«^*<^NH?TO>- '^^^''°3- Solidifies at 144°.
Prepa/raHon. — o-Nitro-phenyl-glycollic acid is
reduced by iron filings and dilute (25 p.o.) acetic
aoid. The product is diluted, filtered, evapo-
rated, and extracted with alcohol. The alco-
holic extract is evaporated and the residue
crystallised from water (A. Thate, J. pr. [2] 29,
178). Projperties. — ^White cubes (from dilute al-
cohol), which nevertheless are doubly refracting.
Sickle-shaped needles (from water), composed of
small prisms joined in staircase fashion. Sol.
ether, benzene, and alkalis. Can not be con-,
verted into a chloro- derivative by boiling with
HCl. Boiled with alkalis the anhydride forms
salts of amido-phenyl-glycollio acid. Salts.—
EA'._ Solutions of this salt give ynOi BaClj no
pp. in the cold, a white pp. on boiling; with
Pb(OAo),j a heavy white pp. ; with AgNO,, a co-
pious white pp. ; with PeOl,, a dark brown pp.;
with CUSO4, a crystalline green pp. Aoids ppt. tha
anhydride described above. — FbA',. — AgA'.
Ghloro-o-amido -phenyl derivativ$
»0ja,(NHj)01.O.CHyCOjH. Chloro-o-amido-
phemyl-glycolHc add.
y. O.OHj
Anhydride OMfiK I [197°].
\nh.co
Preporatiow.— o-Nitro-phenyl-glycoUie acid ia
digested at 100° with a solution of SnCl, and HCl
GLYCOLLIC AOID.
R36
As soon BB the liquid is filled -mth orystalB it is
allowed to cool, filtered, and recrystallised from
alcohol (A. Thate, J. pr. [2] 29, 183). Pr(^er-
ttea. — White silky branching needles, insol. cold
water, si. sol. hot water, ether, and benzene, sol.
alcohol. Salts. — KA'. Obtained by digesting
the anhydride with KOH. Its solntion gives with
BaOl,, no pp. ; Pb(OAo)s, white crystalline pp. ;
with AgNO,, white flooculent pp. ; FeCl,, dark
wine-red colour and, after a time, finely-divided
oherry-red pp.; CuSO„ yellowish-green pp.—
NaA'.— AgA'.-PbAV
Aldehydo-phenyl derivative v. vol. i.
p. 110.
p-Tolyl derivative CgHjjOsi.e.
CH,.CsH4.0.CH2.COjH. [135°]. Prom chloro.
acetic acid, j)-cresol, and NaOHAq (Gabriel, J3.
14, 923 ; Napolitano, Q. 13, 73). Transparent
prisms. — NaiA'Jaq : thin prisms. ^ HaA' aq :
laminffi. — ^BaA'^Qaq: tables or prisms; si. sol.
cold water. — ^PbA'j aq : lamincB. — ^AgA'.
o-^Oumyl derivative G„H,,0, i.e.
[a:l]Pr.C,H,.O.CH2.C02H. [130°]. From o-iso-
propyl-phenol, chloro-acetio acid, and aqueous
NaOH (Pileti, ff. 16, 129). Needles (from water).
Forms a crystalline Ba salt and amorphous Pb
and Cu salts.— -AgA' : white needles.
p-Gumyl derivative
[4:l]Pr.C^4.0.Ca,.C02H. [81°]. From ^j-iso-
propyl-phenol, chloro-acetic acid, and NaOHAq
(Spica, G.. 10, 248). Silky needles, sol. water, v.
sol. alcohol and ether. TJnlike its o-isomeride,
its solution is ppd. by HgClj, . by AuCl,, and by
PtOlj. — BaA'2 2aq : micaceous scales, m. sol. hot.
water. — PbA'^ 2aq : scales with hexagonal bases,
si. sol. water, sol. alcohol.
Thymyl derivative
0,H,.0,H,Me.O.O]aj.CO^H. [148°]. Solidifies
at 132°. Formed by adding 30 g. of a solution of
NaOH (S.G. 1-34) to a fused mixture of thymol
(15 g.) and chloro-acetic acid (10 g.). Long nee-
dles (from alcohol). SI. sol. water, v. sol. alco-
hol and ether. May be distilled with slight
decomposition {Saaxbaoh, J. pr. [2] 21, 159). —
BaA'2 2aq : prisms. — PbAV — ^AgA' : flooculent
pp.
Ethyl ether of the thymyl derivative
0JH,-C,ftMe.O.CHj.0O4Et. (290°).
Amide of the thymyl derivative
C3H,.CAMe.0.CH2.C0.NH;,. [97°]. V. sol. hot
water, alcohol, and ether (Spica, G. 10, 245).
■ Garvacryl derivative
0,H,.CeH3Me.O.CHj.C02H. [149°]. Formed
from carvacrol and chloro-acetic acid (Spica, G.
10, 245). White needles ; si. sol. water, v. sol.
alcohol and ether. — BaA'2 4aq : prisms, sol.
water.— PbA'j : gummy mass (by ppn.), or
minute prisms (from alcohol). — AgA' : minute
needles.
Ethyl ether of the carvacryl deriva-
tive 0,H,.0^,Me.0.CHj.C0jEt. (289°). Oil.
Amide of the carvacryl derivative
C3H,.0AMe.0.CHj.C0.NHj, [68°]. SI. sol.
cold water, sol. alcohol and ether.
Eugenyl derivative
C,H5.CaH,(0Me).0.CHj.C0sH. [81°]. Formed by
adding30g.of solution ol NaOT (S.G, 1-34J to a
fused mixture of chloro-acetio acid (10 g.) and
eugenol (10 g.). Forms long satiny needles
(from water). Not v. sol. water (L. Saarbach,
/, pr. [2] 21, 158).— NaA'liaq.
(a)-Naphthyl derivative
C„H,.O.CHj,.COjH. [190°]. Formed by heating
(n)-naphthol with chloro-acetic acid and gradu-
aOly adding KOHAq (Spica, G. 16, 437). The
product is diluted with water, acidified with
EGl, and the pp. dissolved in aqueous ammo-
nium carbonate to separate the unaltered (a)-
naphthol. Small pale-red prisms, si. sol. water,
V. sol. ether and alcohol. — EA'aq : long acicu-
lar crystals, v. sol. water. — PbA'2 4^aq: white
crystalline pp.— BaA'j 4|aq : white needles.—
MgA'2 6|aq: pink scales. S. 2-46 at 28°.
Ethyl ether of the (a)-Naphthyl
derivative Oi^,.O.CB^.GO^i. [173°].
Colourless crystals, sol. alcohol and ether.
Alcoholic NH, gives a crystalline pp. of the
amide 0,„H,.O.CHj.CONHj. [155°].
(P)-Naphthyl derivative
C,„H,.O.C]^.00,H. [151°]. Prepared in like
manner, nsing (;3)-naphthol (Spica). Trimetrio
prisms ; v. si. sol. water, sol. alcohol and ether.
— NHjA': white unctuous scales [180°].— KA'.
— BaA'^Sfaq: laminae. — (PhA'j)jPbO: white crys-
talline pp.— MgA'jSaq. S. -62 at 26°.
Ethyl ether of the (0^-naphthyl
derivative C,„H,.0.CH2.00jBt. [49°]. Large
transparent scales ; converted by alcoholic NH,
into the amide C,„H,.O.0Hj.CO.NHj. [147°].
Tolylene derivative
Me.C5Hs(0.0Hj.C0jH)2. [217°]. From orcin
(62 grms.), chloracetic acid (100 grms.) and
caustic soda solution (540 grms. of 31 per cent.).
The reaction is violent (Saarbach, J. pr. [2] 21,
162). Thin crystals (from water). SI. sol. water,
V. sol. alcohol and ether. Its solutions give an
orange pp. with Fed,. — Na^A" 3aq. V. sol. water.
Needles (from alcohol). — KjA"3aq.— OaA"2aq.
Ethyl ether.— EtjA". [107°]. Amide.—
Me.C„H,(O.0Hj.0ONH2)ij. Amorphous.
Nitro-tolylene derivative '
Me.C.Hi(N0J(0CHj.C0jjH)j. [140°]. Formed
by the action of HNO3 (S.G. 1-12) at 100° on
the tolylene derivative. Crystallised from alcohol
(Saarbach, J.pr. [2] 21, 168).
Pyrogailyl derivative
C3H3(OCH2.CO,H)3. [198°]. S. 1-3 at 15°,
Formed , by melting pyrogallol (12 pts.) with
chloro-acetic acid (30 pts.) and then boiling with
(200 pts^ of) solution of soda (S.G. 1-3), and
acidifying when cold (Giacosa, J.pr. [2] 19, 398),
— K3A'".— KH2A"aq.
DiglycolUo acid C;B.fi^ ».e. 0(CH2.C0jP),.
ParamaUc add. Mol. w. 134. [148°]. Ba,
41-90 in al4p.c. aqueous solution (Eanonnikofi).
Formation. — 1. Occurs in the preparation of
glycollic acid from chloro-acetic acid by boiling
with aqueous NaOH (Heintz, P. 109, 470), with
alkaline earths, and yrith water and PbO or
magnesia (Schreiber, J.pr. [2] 13, 486).— 2, By
oxidising di-ethylenic glycol with nitrio acid or
platiuum-blapk (Wurtz, 0. B. 51, 162).— 3. A
by-product in the preparation of glycollide by
heating glycollic acid to 220° (Heintz, ,P. 115,
280, 452).
ProperUea. — Thick prisms (containing aq).
Has no action on light. V. sol. water and al-
cohol. On distUlation it gives formic paralde-
hyde and other products (Heintz, A. 128, 129).
By heating with HIAq it is suecessivsly con-
verted into glycollic and acetic acids. Fuming
HGlAq at 136° yields glycollic acid (Qeiu'vz, A,
640
GLYCOLLIC AOID.
130, 257). Potash-fusion gives oxalio and acetic
acids. FGlg forms obloro-acetjl ohloiide.
Salts. — The neutral alkaUne salts are easily
soluble in water, other diglycollates are but
sparingly soluble. — NH4HA.": long monoclinio
prisms, insol. alcohol. S. 3-26 at 16°.— KHA" :
trimetrio crystals, si. sol. water. — KjA" : long deli-
quescent needles. — NaHA" : small tables, si. sol.
water, insol. alcohol. — NaKA"3aci: small tabu-
lar prisms with nacreous lustre, insol. alcohol.
[100°].-Li2A"5aq. S. 45 at 18-5°.— Li^A." 2iaq
(Schreiber, J. pr. [2] 13, 436).— BaHjA", : hard
granular crystals. — BaA" aq : white crystalline
pp. S. -17 at 100°. — CaA"6aq: long shining
needles. Much less soluble than calcium gly-
coUate. — OaA" aq. — OaA" 3aq. — CaA" 4aq. —
CaA" 5aq. — SrA" aq. — SrA" 4aq : limpid, non-
efSorescent crystals. — MgA"3aq : small prisms.
— PbA" : minute crystals, si. sol. water. —
CuA" ^aq : blue crystalline pp. — ZnA". —
ZnA" 3aq. — AgjA" : white granular pp.
Bthyl ether EtjA". (240°). From the sil-
ver salt and StI (Heintz, A, 144, 95). Also from
chloro-acetic ether, sodium glycoUate, and NajGOg
at 190° (Heintz, A. 147, 200). Heavy oil. De-
composed by boiling water into alcohol and di-
glycoUic acid. Alcoholic NH, forms the amide
0{CH,.CONH.,),.
First Amide NHj.CO.CHj.O.OHj.COjH.
Diglycollamia acid. [135°]. Formed by heating
the imide with baryta-water. Formed also by
heating the second amide with water at 100°
(Heintz, A. 128, 140). Trimetric prisms ; m. sol.
hot water, si. sol. alcohol, nearly insol. ether. —
BaA'2 aq : crystals ; sol. water.
S«co»(i4mic?«0(GHj.OONHj)j. From the
ather and cold alcoholic NH,. Trimetric prisms;
V. e. sol. hot water, v. si. sol. alcohol. HCl de-
composes it into NH, and diglyoollio acid..
Imide 0<^^;^^>NH. [142°]. S. 1-8
at 14°. Formed by distilling the preceding.
Formed also by distilling acid ammonium
diglycoUate. Long needles. — AgC^H^IfOs :
laminee. ,
Triglycolllc acid C^K^fi,. A syrupy acid,
said to be formed by the action of Ctfl on a
mixture of Ac^O and iodine (Schiitzenberger,
C.B. 66,1340).— Ca3A"V—Ba3A"'.2aq: prisms.
GLYCOLLIC ALDEHYDE G^fl, i.e.
HO.CHj.CHO. It is doubtful whether this sub-
stance has been obtained. It is described by
Abeljanz (A. 164, 213, 223) as a syrup, sol. ether,
readily oxidised by Ag^O to glycoUic acid, and
obtained by treating CH^Cl.CHCl.OBt with water
at 115''. Abeljanz obtained the same body by
treating CHj(0H).CHC1.0Et with cdnc. H^SO,.
Glycollic orthaldehyde CH2(0H).CH(0H)j.
Di-ethyl derivative CH,(OH).CH(OEt),.
(167°). V.D. 66-6 (calc, 67). From
CH^Br.CH(OEt)j by heating with alcoholic KOH
for twelve hours at 170° (Pinner, B. 5, 150).
Fragrant liquid. Decomposed by cold cone.
HjSO, and by gaseous HOI. AcjO at 120° yields
a liquid resembling aldehyde, which may be
glycollic aldehyde.
Tri-ethyl derivative
0H,(0Bt).CH(0Et)2. (164°) (P.); (168°) (L.).
S.G. 2i -892. From bromo-acetal and NaOEt at
160°. Also from OH^Gl.OHCl.OEt and NaOEt
at 150° (Lieben, A. 146, 196). Fragrant Uquid.
GLYCOLLIDE C^HjO, ix.-C^yO cr
CH2.O.CO
[ I . [220°] (N. a. T.) ; [180°] (D.).
CO .O.GH,
Formatum. — 1. By heating glycoUic acid to
240°, small quantities of diglycoUic acid and of
formic paraldehyde being formed at the same
time (Heintz, P. 115, 452). — 2. By heating an-
hydrous potassium chloro-acetate at 115° (Ee-
kulS, .i. 105, 288). If the crystallised salt be
used most of the glycoUide unites with water
forming glycollic acid. — 3. GlycoUide was first
obtained by heating tartronio acid to 180° as
long as CO2 escapes ; after a few days the pro-
duct solidifies, and is then washed with hot water
(Dessaignes, O. ii.'38, 46).
Prepwration. — An alcoholic solution of chloro-
acetic acid is added to a solution of sodium in
IS times its weight of dry alcohol; anhydrous
chloro-acetate of sodium is ppd. and, after dry-
ing at 100°, this salt is gradually heated to 150°
and kept for two days at that temperature. The
product is freed from NaCl by washing with
water, and may be dried at 200° (Norton a.
Tseherniak, O. B. 86, 1832).
Properties. — Light white powder ; neutral to'
litmus. SI. sol. hot nitrobenzene. Dissolves in
caustic potash, forming potassium glycollate.
Ammonia forms the amide of glycollic acid.
Ethylamine forms HO.GHj.GO.NHEt. Aniline
at 130° gives HO.GHrOO.NHPh. [108°].
Another anhydride of glycollic add O^B.fls^.
[130°]. Obtained by heating glycollic acid at
100? for a long time (Drechsel, ^1. 127, 154).
Also from glycollic acid and the vapour of SO,
(Pahlberg, J. pr. [2] 7, 336). Powder, insol.
ether, alcohol, and cold water. Boiling water
forms glycolUc acid. Further heating converts
this anhydride into glycoUide.
GLYCOLLTTBIC ACID v. Htdanioic aoid.
GLYCOLLYL-AMIDO-BENZOIC ACID
GHjOH.GO.NH.O,H,.COsH. [212°]. From m-
amido-benzoic acid and glycollic acid at 150°
(Pelizzari, A, 232, 153). Needles, (from water).
Sol. alcohol, si. sol. ether.
Acetyl derivative
CHj(OAc).CO.NH.0eH,.GO2H. [198°].
CO
Anhydride.— GB./^J!!.C^K,.CO.,B..(n8°l
From CHoOH.GO NH.G„H,.G0.;H by heat.
GLYCOLLYL-UEEA v. Hydantoin.
GLYCOLUBIL v. Aoeiylene-ubea, vol. i,
p. 44.
GLYCOSE V. SvoAS.
GLYCOSIHE C,H,N,t.«.
^OH-N^>°-°'^^N-CH^- ^^'>''«'^i^-
Formation. — 1. By acting on glyoxal with
ammonia (Debus, A. 107, 199 ; Japp a. Clemin-
shaw, C J. 51, 553). — 2. From tri-chloro-lactic
acid and cone. NHjAq (Pinner, B. 17, 2000)..
Properties. — 'White needles (from alcohol),
V. si. sol. alcohol.
Salts.— B"2H2Pt01j: buff-coloured needles.
— B"HjPt0l8.— B"(HjPtCgj: deep-yellow crys.
tals, stable at 120°.— B-'AgNO, (Wyss, B. 10,
1375).— B"(HjC,04),: small nodules, m. sol. cold
water.
GLYOYRRHIZIC ACID.
641
Dl-benzyl-glycosine CjHiNj(N0,H,)2. [145°].
Fonued by heating glycosine with benzyl chloride
and extracting the product -with dilute hydrio
chloride (Japp a. Oleminshaw, G. J. SI, 555).
Colon^rless plates, v. sol. benzene, si. sol. petro-
leom ether.
Tetra-pheuyl-glycosine
-NH
l/
NH— C— Ph
<| .>O.Cr |> . [above 300°].
Ph-^0_N ^N _C_Ph
Formed by acting on a mixture of benzil and
glyoxal with ammonia (Japp a. Gleminshaw, C. J.
51, 553). White felted needles, m. sol. hot, si.
Bol. cold, alcohol, v. sol. HOAc.
GLYCOSTJRIC ACID. [140°]. Occurs in urine
in disease (Marshall, Ar. Ph. [3] 25, 593).
Prisms ; T. sol. water, alcohol, and ether, insol.
benzene and light petroleum. Beduces Fehhng's
solution more strongly than glucose. An ethereal
Eolation becomes red on evaporation. FeGl, gives
B transient blue colour.
GLYCITEONIC ACID OsH;„0,.
Formation. — 1. Euxanthio acid (which oc-
curs in puree or Indian yellow) is spUt up by
heating with HOI or with dilute (3 p.o.) HjSOj
into glycuronic acid and euxanthone (Spiegel,
B. 15, 1965 ; KiUz, Z. B. 23, 475 ; Baeyer, A.
155, 257 ; Thierfelder, 3. 11, 388). The decom-
position is best effected by water at 125°.— 2. By
boiling (a)- or (|S)- camphoglyouronio acid with
dilute (5 p.c.) HOI (Schmiedeberg a. Meyer, H.
3, 422). -3. By boiling urochloralic acid with
dilute HjSO, (Mering, H. 6, 489).— 4. When a
rabbit is treated with tert-a,m.yl alcohol its urine
contains ' di-methyl-ethyl-oarbinol-glyouronio '
acid 0„H2„0„ which is spUt up by boiling dilute
H2SO4 into iert-amyl alcohol and glycuronic
acid. Tert-hutyl alcohol acts in hke manner
(Thierfelder a. Mering, JS. 9, 515).
Properties. — Syrupy acid, v. sol. alcohol. On
evaporation of its solution, or even on standing,
it changes to the crystalline anhydride. Gives
on oxidation camphoric and formic acids. Bro-
mine converts it into saccharic acid (Thierfelder,
B. 19, 3148). Sodium-amalgam reduces it to
gluconic acid. Its K salt dissolved in 90 p.c. al-
cohol reacts with aniline forming NPhtOgHjOsK,
the potassium salt of the ' anilide of glucose '
[177°]. TO-Tolylene-diamine forms, in like man-
ner, G,H,(N:CeH,OsK)j. Cone. KOHAq decom-
poses glycuronic acid, forming oxalic acid,
pyrocatechin, and a little protocatechuio acid.
Glycuronic acid gives lactic and acetic acid
when fermented in presence of cheese and
chalk.— KA': needles.— BaA'^ : amorphous, v.
80I. water.
Anhydride 0^0,. [167°]. [o]„ = 19-25<'
at 18°. Monoolinic tables, with sweet taste.
v. e. sol. water, insol. alcohol. Dextrorotatory.
Eeduces hot FehUng's solution. -989 pts. reduce
as much as 1 pt. of glucose. Hinders the ppn.
of cnprio hydroxide by alkalis.
Benzoyl derivative OjHjBzjO,. [107°].
Obtained by treating the acid (1 mol.) with BzOl
(9 mols.) and NaOH (12 mols.) in a 10 p.c. solu-
tion (Thierfelder, H. 13, 275). V. sol. alcohol.
Beduces Fehling's solution.
Phenyl-hydrazide G„H45N,„0,„. [115°].
From the K salt and phenyl-hydrazine mixture.
Yellow needles.
Vol.. II.
GIYCYPHTILIN GjiHj^O,. The sweet prin-
ciple of Smilax glycyphylla. Extracted from
the leaves and stem by alcohol, the extract being
evaporated and the residue dissolved in water
and extracted with ether (Wright a. Bennie,
C. J. 39, 237 ; 49, 857). Grystallises from wet
ether with 3aq, and from water in prisms con-
taining 4|aq. Has no definite melting-point.
SI. sol. cold water, v. sol. hot water and alcohol,
m. sol. ether. Insol. chloroform, benzene, and
light petroleum. Dissolves in aqueous EOH, the
solution turning red in air. Does not reduce
Fehling's solution. Is ppd. by lead subacetate.
Boiling dilute H2S04 converts it into phloretin
GjsHuOs and isodulcite GjH,j0j.
GLYCYEBHIZIC ACID G.iH^NO.g. Occurs,
probably in combination with ammonia, in the
liquorice root (Qlyeyrrhiza glabra and G. eehin-
ata) (Vogel, jun., J.pr. 28, 1 ; Lade, A. 59, 224;
Gorup-Besanez, A. 118, 236 ; Hirsh, Ph. [3] 1,
749 ; Eoussm, Ar. Ph. [3] 8, 156 ; Eobiquet,
A. Ch. [4] 72, 143 ; Sestini, (3. 8, 454 ; Haber-
mann, A. 197, 105). Occurs also in large quan-
tities in the rhizomes of Polypodium vulgwrt
and of P. semipennatifldum, both of which ferns
are used as substitutes for liquorice (Guignet,
O. B. 100, 151). Habermann finds in liquorice,
besides glycyrrhizic acid, a brown resin, which
yields jp-oxy-benzoio acid when fused with potash,
and an amorphous bitter substance 0,sHj„NO,„
si. sol. water and ether, v. sol. HOAc and aqueous
NajCOj.
Prepa/raUon. — 1. The dried and powdered
root is extracted with dilute acetic acid ; alcohol
is added ; and the filtrate evaporated to a syrup
and washed with water (Guignet).— 2. The root
is extracted with boiling water containing a little
milk of lime ; the concentrated extract is ppd.
with HOAc. The gelatinous pp. is dissolved in
50 p.c. alcohol, deodorised by charcoal, and eva-
porated at 100° (Sestini). — 3. Commercial ' Gly-
cyrrhizin ammoniacale ' is boiled with glacial
acetic acid and filtered while hot. The acid am,-
monium salt then crystaUises from the filtrate
(Habermann). The acid may be obtained by
conversion into the lead salt and decomposing
by H,S.
Properties. — Gelatinous mass (from hot
aqueous' solution). When dry it forms an amor-
phous solid, which swells up in cold water. V.
si. sol. ether and alcohol, sol. boiling HOAo.
Turns brown at 100°. It has a sweet taste and
an acid reaction. Expels CO, from GaCO, sus-
pended in hot water. Beduces Fehling's solu-
tion on heating. Boiling dilute acids spUt it
up into glycyrrhetin and parasaccharic acid
OoHijOj.
Salts. — ^NHjHjA'": laminae (from alcohol
or HOAo) ; -prepared as above. Insol. ether, si.
sol. alcohol, V. e. sol. boiling water. Separates
from dilute alcohol or hot water in a gelatinous
form. — (NHJjA'" : amorphous gummy mass, v.
sol. water, insol. alcohol. Has an intensely
sweet taste. — KHjA'": crystalline grains. Swells
up in cold water, forming a jelly; v. sol. hot
water, v. si. sol. alcohol. Extremely sweet. —
K3A'": yellowish amorphous mass ; v. sol. water,
V. si. sol. alcohol. From its solution in HOAo
the salt KHjA'" crystallises out.— Ba3A"'j: floc-
oulent pp. — Pb3A"'j : yellowish-brown mass, si.
K>1. water, insol. alcohol, sol. HOA«.
TT
642
GLYCYRRmZIC ACID.
Glyoyrrhetin OjjHjjNOj. [200°]. Formed
by boiling glyoyrrhizio acid with dilute acids
(Habermaim, B. 10, 870 ; Griessmeyer, D. P. 3.
209, 228). Crystalline powder; has no taste.
Insol. water, ether, and alkalis; sol. alcohol,
HOAc, and HzSO^. Does not give jp-oxy-benzoio
acid on potash-fusion (Habermann ; ef. Weselsky
a. Benedikt, B. 9, 1158).
Di-acetyl derivative C^^^jAc^NO^.
[217°]. Prom glyoyrrhetin and AcGl. Crystal-
line powder; insol. water. Gives on oxidation
amorphous 0,jH„NOs.
Bromo-glycyrrhetin CjjHjjBrNO,. From
glyoyrrhetin and Br in HOAc. Crystalline
powder, insol. water and alcohol, si. sol. HOAc,
V. sol. CHClj.
Sitro-glycyrrhetin Os2H,s(NOj)N04._ Formed
by treating a solution of glyoyrrhetin in HOAc
withHNOj. Powder.
GLYOXAL CaHjO^ i.e. CHO.CHO. Oxalic
aldehyde. Mol. w. 58. Formed by the action
of nitric acid on alcohol (Debus, A. 102, 20 ; 107,
199 ; 110, 316 ; 118, 253), aldehyde or paralde-
hyde (Lubavin, B. 8, 768).
Preparation.— 1. Obtained from the mother-
liquor in the preparation of glyoxylio acid by the
slow oxidation of alcohol by HNO, ; the liquid
is mixed with several times its volume of cone.
NaHSOjAq. The crystalline compound is sub-
sequently decomposed by dilute H2SO4.— 2.
Paraldehyde (25 g.) is mixed with water (25 g.) ;
HNO3 (20 o.c. of S.G. 1-37) is poured in so as to
lorm a lower layer of liquid, and below this again
fuming HNO3 (1 c.c.) is introduced. After a
week the liquid is evaporated at 100°, taken up
in water, neutralised by OaCOj, glyooUio and gly-
oxylic acids ppd. by lead subacetate, filtered, freed
from excess of lime by oxalic acid, again filtered,
and evaporated (De Fororand, Bl. [2] 41, 240).
ProperUes. — ^Amorphous, slightly deliques-
cent mass. After drying at 100° it contain^ xaq
and is v. e. sol. water, but after drying at 120°
it is V. si. sol. cold water. At 170° it is partially
converted into glycollide. It is v. e. sol. alcohol
and ether. It reduces ammoniacal AgNO,,
forming a mirror. Water at 150° converts two-
thirds of it into glycoUic acid.
Beactions. — 1. A small quantity of very
dilute nitric acid oxidises it to glyoxylio acid ; a
larger quantity of nitric acid forms oxalic acid.
2. Aqueous alkalis convert it into glycollic acid,
even in the cold. — 3. Cold aqueous KCy forms a
black substance. — 4. Anmumi/u/m cyanate forma
glycoooll (Lubavin, J. iJ. 1882, 281; O. J. 44,
178). — 5. Cone, aqueous NHj forms, in the cold,
glycosine C^HsN, and glyoxaline CjHjNj. — 6.
An alcoholic solution of amiline forms C^^S^^
(SohifE, B. 11, 831), a crystalline base, insol.
water, sol. alcohol, forming the platinochloride
B'jHjPtCl, and the nitro- derivatives
CmHj„(N02),N, and G^^JNO^^Sfit.-l. Aniline
heated with the compound of glyoxal with
KaHSO, forms the anilide of phenyl-almido-
acetic acid NHPh.CH,.CO.NHPh [113°] (Hins-
berg, B. 21, 110).— 8. (o)- and {0)-Napht}iyl.
amine heated with the compound of glyoxal
with NaHSO, form the sodium salt of the sul-
phonate of (a)- and (j8)-naphthoziadole
CioH,<^^g^]>CO (Hinsberg).— 9. Aeeto-acetio
ether and cone, aqueous ZnCl, form methyl-Qftri^-
oxy-furfuryl-acetio acid and an ether 0,4H„0,
[139°] which crystallises in plates, v. sol. most
menstrua, insol. alkalis, and on saponification
gives an acid [75°] (Polonowsky, A. 246, 17).— 10.
Gaseous HGl passed through a mixture of gly-
oxal and ethylene mercaptam forms
CH2.SV vS.CHj
I >OH.CH< I [133°] (Fasbender, B.
CHj.S/ \S.CH^
21, 1476). — 11. Makmic ether (2 mols.ya,oted on
by glyoxal (1 mol.) and zinc chloride giveg
rise to di-oxy-butane tetra-carboxylio ether
(COjEt)j.CH.CH(OH).CH(OH).CH(OOjBt),
(Polonowski, A. 246, 1). — 12. Aeeto-acetic ether
and cone. ZnCLgAq forms di-methyl-furfurane
di-carbozylio acid 0<C(C^^O^)jg>, a
compound C,4H,sO, [139°], and oily
„ ^C(CHAc.CO.Bt):CH-v ,a a „ a-
0<CMe = C(CO,Et) >-^3- ■^«™°"' ^'-
methyl-urea evaporated with glyoxal and a little
HCl forms tetra-methyl-glyoolurile
ilMe.CH.NMe^
C0< I >CO[217°](Franchimonta.
\NMe.CH.NMe/
Klobbie, B. T. C. 7, 236).
GombinationsC^^OJ^^^BO^^: prisms,
y. sol. water, insol. alcohol (De Forcrand, C. R.
100, 642).— 0^A(NaHS0,)j aq : small crystals,
V. sol. water, insol. alcohol.— C2H202(EHS0 J,:
prisms (De Fororand, C. B. 98, 1537).—
C2Hj02Ba(HS03)2 2^aq : concentrically-grouped
masses. S, -85 at 18°.
I)ip;icreyZ%(?raa«?eHC(NjHPh).CH(NjHPh).
[170°]. Got by warming glyoxal or its com-
pound with NaHSO, with excess of aqueous
phenylhydrazine hydrochloride and sodic acetate
(Piokel, A. 232, 231; Fischer, B. 17, 575).
Formed also by the action of phenyl-hydrazine
on tri-ohloro-lactic acid (Pinner, B. 17, 2001).
Bosettes of slender needles or plates (from
alcohol). Nearly insol. water and light petro-
leum, sol. benzene and chloroform. By warming
with alcoholic FeCl, it is oxidised to the ' oso-
tetrazone'<^^2;^:^|^ [152°] which crystal-
lises from alcohol in dark red plates (Von Peoh-
mann, B. 21, 2761).
Salt.— B'HCl. [156°]. Saponified by water.
Phenyl-ethyl-hydrazide
HC(NjEtPh).CH(NjEtPh). [149°]. Formed by
adding the compound of glyoxal with NaHSO,
to a dilute solution of phenyl-ethyl-hydrazine in
HClAq (Blbers, A. 227, 340). Crystals (from
alcohol) ; v. sol. benzene and chloroform, m. sol.
ether and cold alcohol.
Oxim CjHAOj i.e. HC(NOH).CH(NOH).
Qlyoxim. [178°]. Formed by the action of
hydroxylamine on glyoxal (Wittenberg a. Meyer,
B. 16, 605). Formed also by the action of
hydroxylamine upon tri-chloro-lactio acid (Pin-
ner, B. 17, 2001). Sublimable. Colourless
trimetrio tables. Sol. hot water, alcohol, and
ether. Boiled with aqueous acids it is resolved
into its constituents. By heating with acetic
anhydride it yields cyanogen ^ach, B. 17,
1573). Phenyl-hydrazine added to its alco-
holic solution forms an addition-compound
CjHjNjOjNjHjPh [110°], which crystallises from
alcohol in white scales, insol. water (Polonowskyi
5. 21, isa).- AgO^aNjO, : white powder.
GLYOXALINES.
643
Di-acetyl derivative 02H,(NOAo),:
[120°] ; oolourlesa orystals. By fuither heating
with acetio anhydride it yields cyanogen OLach,
B. 17, 1573).
Reference. — ChiiOBO-oltozhi.
Paraglyoxal hydrate OijHuO,, i.e.
(C2H202),E20. Foimed by passing HGl into a
solution of glyoxal (1 vol.) in EOAo (5 vols.)
(Sohiff, Q. 4, 16; A. 172, 1). Powder, insol.
water, ether, benzene, and chloroform, si. sol.
boiling alcohol. Prolonged boiling with water
oonverts it into glycolUo acid. Caustic alkalis
also form glycollates. Boiling AOjO forms
amorphous insoluble C,2H„AcO„. BzCl gives
amorphous Ci^H^BzO;,.
Orthoglyozal CH(0H)2.GH(0H)2. Oxalic
orthaldehyde.
Ethyl derivative CH(0Et)2.CH:(0Et)2.
(o. 180°). Formed by the action of NaOEt upon
di-ehloro-aoetal CHCl2.CH(0Et)j (Pinner, B. 6,
147). Oil. Entirely destroyed by strong acids.
GIiYCZAL-AUYLIITE v. Buin.-aLTOXALiiiE.
OLYOXAL-ISOBUTTLINE v. Fbofyl-qlt-
OXAlirNE.
GLTOZAL - EIHTLIHE «. Meibtl-olt-
OZALINB.
CH.NHv
OLYOXALINE C.H.N, t.e. || >CH
CH.K'^
CH.Nv ,
(Japp, C. J. 43, 17) or |1 | >OHj. Methylene.
aixtylme-aeine. [89°]. (255°). V.D. 2-35 (oalo.
2-26). Formed, together with glycosine, by
the action of strong aqueous ammonia on glyoxal
(Debus, A. 107, 204 ; Lubavin, J. B. 7, 254 ;
Wyss, B. 9, 1543 ; 10, 1365 ; Wallach, B. 15,
645). Formed also by the simultaneous action
of formic aldehyde and NH, on glyoxal (Badzis-
zewsky, B. 15, 1495).
BregwraiAon. — Glyoxal is treated very gradu-
ally with ammonia in sUght excess, the tempera-
ture being kept down. Glycosine then separates
as a brown powder, and the filtered solution
contains the glyozaline together with ammonia,
chiefly as acetate. This liquid is boiled with
Tnillr of lime to expel the ammonia, then evapo-
rated to a syrup, treated with absolute alcohol
to separate mineral salts, and filtered ; the
residue is strongly pressed to separate as mnch
as possible of the liquid; and the whole of this
liquid is distilled from a wide-necked retort.
After one rectification the glyoxaline is perfectly
pure, and soUdifies to a radiate, dazzling-white
crystalline mass (Wyss).
ProperVies. — Thick nacreous prisms, v. sol.
water, alcohol, and ether ; is not deliquescent.
Has an alkaline reaction. Kot attacked by
chromic acid. Not affected by reducing agents,
by AOjO, by AeOl, or by BzCl.
Beaaiicms.—\. KMnO, oxidises it to formic
acid and CO,.— 2. EtBr forms 0,H,EtNjHBr
and CjHoEtN^tBr.— 3. Benzyl chloride forms
in like manner C,H,(0,H,)N,0,H,C1 (Wyss).-4.
The hydrochloride treated with AgNOj forms a
nitroBO-derivative. — 5. Hydrogen peroxide
forms oxamide (Eadziszewsky, B. 17, 1289).—
6. Bromine added to an aqueous solntioii of
glyoxalhie forms tri-bromo-glyoxaline
CjHBrjNs, which crystallises, from water in
needles. It is t. si. sol. cold water, t. sol. ftlw*
;.CH, + 3H,0
hoi, si. Bol. ether. It dissolves in alkalis and is
reppd. by acids, behaving as an acid. Its silver
salt 0,AgBr,N, is converted by Mel into
G,MeBr,N2, which may be reduced by Bodiam>
amalgam to methyl-glyoxaline.
~~ Salts. — B"2H2FtCla: orange-red prisms
(from hot water) (Debus). — B"jHjPtCl8 sraq
(Wallach).— B",HjZnCl<: very soluble crystals.—
B"H20204 : prisms. S. 206 at 19°.— 0,AgH,N,;
white amorphous pp. ; insol. cold water.
Beferences. — Methtl-, Meibyii-eihtl-,
EiHTii-, Fbofyii-, Buixl-, and IsoAim-aLY-
OXALINES.
fiLYOXAIIITES. These compounds are de-
CH— NHv
rivatives of glyoxaline i| J^CH.
OH N'^
Oeneral modes of formation. — They are
formed by the condensation of compounds con-
taining the dioarbonyl-gioup — CO.CO — (a-di-
ketones and s-dialdehydes) with aldehydes and
ammonia jointly, the reaction taking place ac-
cording to Equation II. of the general reactions
of this class («. vol. i. p. 466). Thus glyoxal,
aldehyde, and ammonia yield methyl-gly-
oxaline : —
OHO
I -fCH^OHO-l-aNH,
OHO
OH-NHv
-II >c.(
OH — ^^
(Badziszewski, B. 15, 2706 ; Japp, C. J. 1883,
197 ; V. also imder Equation II., vol. i. p. 465).
The aldehyde necessary for the reaction is
sometimes furnished by the preUminaiy hydro-
lysis of a portion of the dicarbonyl-compound.
Thus the reaction discovered by Debus (T. 148,
209), in which glyoxaline itself is obtained by
treating glyoxal with ammonia, is supposed to
occur in two stages:
(a) CHO,CH0 + H,O=H.C00H + H.0HO
Formlo aldehyde.
OHO
(6) I ■^H.CH0+2NH,
CHO
CH— NHv
- II >CH + 3H,0
CH — W^
(Badziszewski, J5. 15, 1496; Japp, B. 15, 2419).
In a similar manner lophine (triphenyl-gly-
oxaline) is obtained from benzil and ammonia,
benzoic aldehyde being first formed (v. vol.i. pp.
467-8) ; and trimethyl-glyoxaUne from diacetyl
and ammonia (Von Pechmann, B. 21, 1417).
Glyoxal also reacts with ammonia without
first undergoing hydrolysis, yielding glycosine
(D.), which is a diglyoxal^Une. In tins case
3 mols. of glyoxal take part in the reaction, one
of these exercising the function of the aldehyde
(here a dialdehyde) and the other two that of
the dicarbonyl-compound in the iddehyde-di'
ketone-ammooia condensations :
OHO
a I ■(■CH0.CH0-I-4NH,
CHO
CH— NHv JSSa—CB.
OH — W ^N — OH
(HyooBiM,
SZi)
644
GLYOXALINES.
(Japp a. Cleminshaw, C.J. 1887, 553; cf. also
formation of tetraphenylglycosine, vol. i. p. 465).
Wallach , has ahown that chlorinated gly-
oxalines are formed by the action of phosphorus
pentaohlo^de on s-dialkjlozamides {A. 184, 33 ;
214, 278; B. 16, 546; v. also Japp, B. 15,
2418; G.J. 1883, 197). In the first stage an
imido-ohloride is formed: thus s-dimethyloz-
OCliN.CH,
amide would yield | . (The imido-
CC1:N.CH3
chloride was not isolated in this particular
case, but the corresponding diethyl-compound
was obtained.) The imido-chloride parts, either
spontaneously or on gently heating, with the
elements of hydrochloric acid, yielding a chlori-
nated glyoxaline. Thus with dimethylozimido-
chloride :
OChN.CHa
001:N.CH.
-HC1 =
CCl— N(CH,).
CH-
\CH
Chloroxalmethyliiie
(Hethylchlorglyozaline).
The mechanism of this reaction is not under-
stood (Wallach, B. 16, 546). By heating with
hydriodic acid and amorphous phosphorus, the
compound is reduced to the corresponding
' oxalmethyUne ' (tertiary methylglyoxaline).
The name ' oxalines ' was given to this class of
compounds to denote their connection with
oxalic acid, before it was recognised that they
were derivatives of glyoxaline. The general
formula of the ' oxalines ' derived from s-di-
alkylozamides of the formula
CONH(C„H^„)
thus
CONH(0„H^„)
CH-N(0„H,„„).
CH N^
IS
.i)Har„-i
i)+i ■
' oxalethyline ' from s-diethyloxamide is
CH-N(OA)\
II >0.0H3.
CH S^
Another class of glyoxalines aretheanhydro-
bases derived from orthodiamines : thus anhy-
dracetdiamidobenzene (ethenylphenylenedia-
mine)
CH
CH^"
CH
C— NH.
3— N-^
VCH,
is obtained by reducing o-nitracetanilide with
tin and hydrochloric acid :
^NH.CO.CH,
C.H.
■NO,
.NH.
+ 3H,
<
C»H,/ ^C.CH, + 3HjO
•N
(Hubner, A. 209, 353). The same compounds
Tuay be prepared from the orthodiamines by
heating them with oarboxyUo acids : thus o-di-
amidobenzene and acetic acid yield the fore-
going anhydracetdiamidobenzene (Ladenburg,
B. 8. 677). '
Ladenburg (B. 11, 690) obtained by the con-
densation of aldehydes with orthodiamines a
elasB of stable bases to which he gave the
name of ' aldehydines.' Einsberg (B. 19, 2025)
has shown that these compounds are tertiary
anhydrobases. Thus (1, 3, 4)-tolylenediainine
and benzaldehyde form benzyl-anhydrobenzdi-
amidotoluene :
\nh,
\^%«^» + 2H,0.
-C,H.<^N^O.O,
The aldehydines, therefore, also belong to the
class of the glyoxalines.
General properties and reactions. — Glyoxaline
and most of its true homologues are solid com-
pounds ; but the derivatives in which the alkyl-
group is attached to nitrogen are generally liquid.
The glyoxalines are monacid bases, and behave
towards alkyl iodides like secondary bases ; thus
glyoxaline yields with methyl iodide the com-
pound C3H3(CH3)N2,CH3l, which by treatment
with moist silver oxide is converted into an am-
monium hydroxide; this by distillation yields
CH-N(CH3)v
the tertiary methylglyoxaline || jiOH.
CH N'^
The conversion of the secondary glyoxalines into
tertiary compounds by the introduction of an
alkyl-group lowers the boUing-point : thus gly-
oxaline boils at 265°, tertiary methyl-glyoxaline
at 197°-199°. When the tertiary alkyl-glyoxal-
ines are distilled through a red-hot tube, the
alkyl leaves the nitrogen and attaches itself to
the ' meso ' carbon atom : i.e. the carbon atom
which is situated between the two nitrogen atoms.
In this way the foregoing tertiary methylgly-
oxaline may be converted into ?n«so-methyl-
CH— NH.
glyoxaline || ^O.CH,, identical with the
CH m
compound (v. supra) obtained from glyoxal, al-
dehyde, and ammonia (Wallach, B. 16, 542;
Ead^iszewski, B. 15, 2706). By oxidation with
hydrogen peroxide, glyoxaline and its meso-
homologues yield oxamide; whilst the tertiary
alkyl-glyoxalines and their wieso-homologues
yield monalkyl oxamides: thus oxalethyline
CH-N(OA)\ ^
II ^C.CH, gives ethylozamide (Bad-
ziszewski, B. 17, 1290).
It has not been found possible to replace the
imidic hydrogen in glyox^ and its homologues
by acid radicles, and from this Eadziszewski {B.
IS, 1494 and 2706 ; 16, 492) has argued that
glyoxaline contains two tertiary nitrogen atoms,
OH:N.
formulating it thus : | >OHj ; but the re-
CH:N/
suits of alkylation and of the oxidation of the
alkyl- derivatives prove conclusively that imidic
hydrogen is present, and far outweigh this
merely negative evidence (Japp, B. 15, 2419 ; 16,
284 ; Wallach, B. 16, 538). Besides, glyoxaline
gives oS ammonia when heated with aaUins
hydrochloride, and sulphuretted hydrogen when
its aqueous solution is heated with carbpn di-
sulphide— reactions which a tertiary base would
hardly exhibit (Wallach, B. 16, 539).
The glyoxalines ore amidineg
GLYOXYLIO acid;
645
in which two hydrogen atoms — one in the amido-
and one in the imido-group — have been replaced
by the dyad group — OIl'=CB'— bo as to con-
vert the complex B'.C^™" into
<H-O.E'
II .
— C.R'
forming a closed-chain com-
NH
pound. Thus glyozaline itseU is formamidine
^^"^NH ^*^ ""^^"^ ^^ eroup — CH=:OH—
has been introduced. The amidines, like the
glyozalines, are monacid bases.
Glyozaline is one of the two possible com-
pounds which may be derived from pyrrhole as
pyridine is derived from benzene— by replacing
a CH- group by triadio nitrogen :
CH— CH CH— CH CH-N
II II n II 11 I!
CH CH CH N CH OH
\/ \/
JH NH NH
Pyrrhole. Pyrazole. GlyoxaUne.
P. E. J.
6LT0XAI (ENAITTHYLINE v. Hexsl olt-
oxAiiDn:.
GIYOXAIIG AGIB v. Gi.yozTi.ia Aom.
GLYOXAL-FBOFYIINE v. Ethyl-gltoxal-
ISE.
GLYOXIM V. Di-oxim of Gltoxai..
GLYOXYIIC ACID Ofifi^ i.e. H.CO.COjH.
Qlyoxalic acid.
Oec/u/rrence. — In the leaves and unripe fruits
pf many plants (Brunner, B. 19, 595).
Formation. — 1. By the action of nitric acid
upon alcohol, glycol, glyoxal, or glycerin (Debus,
P. M. [4] 12, 361 ; A. 100, 1 ; 102, 28 ; 110, 316 ;
Heintz, A. 152, 325).— 2. By boiling silver di-
bromo-acetate with water (Perkin, 0. J. 21, 197 ;
32, 90). — 3. By heating di-chloro-acetia ether
with water (Fischer a. Geuther, J. Z. 1, 47). —
4. By boiling silver di-chloro-acetate with water
(Beckurts a. Otto, B. 14, 581).— 5. By heating
silver bromo-glycollate with ether in sealed tubes
there is formed an amorphous substance (? gly-
oxylio anhydride) which is converted by boiling
water into glyoxylic acid (Perkin a. Duppa, C. 3.
21, 197). — 6. By heating dry silver di-ohloro-
aoetate at 80° there is formed an oil OjHjCljO^
which is BpUt up by water into glyoxylic and di-
chloro-acetio acids (Beckurts a. Otto, B.14, 586).
Prepaa-aiion. — 1. Di-bromo-aoetic acid (Ipt.)
is heated with water (lOpts.) for 24 hours at
135° (Grimaux, Bl. [2] 26, 483).— 2. 220 g. of
alcohol of 80 p.o. are poured into a tall narrow
flask capable of holding about l^lb. of water ;
100 g. of water are introduced below the alcohol
by means of a funnel having its neck finely
drawn out; and below this are poured 200 g.
of red fuming nitric acid, so that the three liquids
may remain one above the other and mix as
little as possible at first. The whole is left for
six or eight days, at a temperature of 20°-22°C.,
tiU the liquids have become completely mixed,
and the resulting nitrite of ethyl has volatilised.
The residual liquid— containing nitric, acetic
and formic acids, compound ethers, glyoxal and
other aldehydes, glyooUio acid and glyoxylic acid
— is evaporated to a syrup over the water-bath
in portions of 20 to 30 g. each; the residues, con-
taining oxalic, glycollic, and glyoxylic acids,
together with the less volatile aldehydes, are
dissolved in small quantities of water ; the
united solutions are neutralised with chalk ; the
neutral liquid is mixed with an equal volume of
alcohol ; and the resulting pp. of calcium-salts
pressed and repeatedly boiled with water. The
aqueous extract yields crystals of glyoxylate of
calcium, and a further quantity of this salt may
be obtained by concentrating the mother-liquor.
The subsequent mother-liquors yield a double
salt of glycoUate and glyoxylate of calcium, and
the last contain glycoUate of calcium (Debus).
7,500 0.0. alcohol yield 808 g. glyoxylic acid (Bot-
tiuger, A. 198, 207).
ProperUes. — Thick syrup (S.G. 1'3), which
crystallises over HjSOj in trimetrio prisms con-
taining aq, and which may therefore be looked
upon as orthoglyoxylic aci,d CH(0H)2.C0jH. V,
sol. water. When strongly heated it gives off
a,cid vapours, leaving a carbonaceous residue.
Volatile with steam. Its calcium salt reduces
boiling ammoniacal silver nitrate forming a
mirror. Glyoxylic acid forms compounds with ,
NaHSOj, with B.JS, and with NHj. An aqueous
solution of calcium glyoxylate is ppd. by excess
of lime-water, and the pp. Ca3(C4Hj0,)2 is con-
verted by boiling water into a mixture of glycol-
late and oxalate. When a solution of calcium
glyoxylate is mixed with aniline oxalate, and the
Uqnid is filtered from calcium oxalate, a colour-
less solution is obtained, which, when boiled or
even when left to itself for a few hours, deposits
a bright orange-coloured precipitate (Perkin a.
Duppa). Aniline (75 g.) acts upon syrupy gly-
oxylic acid (42 g.) forming PhN:CH.CdjH, and
its aniline salt PhN:CH.C02NPhH, ; the aniline
salt is converted by long boiling with water into
a red powder CjjH.jNA (Bottinger, A. 198, 222).
The barium salt (PhNiCH.COaJaBa is v. e. sol.
water, insol. alcohol. Phenyl-hydrazine solution
gives a pp. in an aqueous solution of glyoxylic
acid.
Beactions.-^l. Zinc is dissolved by glyoxylic
acid, the acid being reduced to glycollic acid. —
2. Nitric acid oxidises it to oxalic acid.— 3. PBr,
forms di-bromo-aoetyl bromide (Perkin a. Duppa,
C. J. 21, 197). — 4. PCI5 acting on the potassium
salt KA'aq forms di-chloro-acetyl chloride, KCl,
di-ohloro-acetic acid, and free glyoxylic acid
CHO.CG^H (Beckurts a. Otto, B. 14, 1619).—
5. Boiling aqueous KOH forms glycollic and
oxalic acids (Bottinger, B. 13, 1932).- 6. By
treatment with potassium cyanide and boiling
the product with baryta there is formed tartronio
acid' C02H.0H(0H).C02H. — 7. TolyUne-o-di-
amine on boiling with calcium glyoxylate forma a
crystalline acid 0,'E.i,^,-^S0.C0JB.aq,1 si. sol,
water, v. sol. alcohol, and decomposing at 160°
(Hinsberg, A. 237, 358).
Salts. — With the exception of the ammo-
nium and potassium salts, these might equally
well be described as salts of ortho-glyoxylic acid.
— ^NH,A' : small prisms, v. sol. water (Perkin; cf.
Engel, O. B. 98, 628). Its concentrated solution
turns yellow when boiled. Gives pps. with AgNOg,
with Pb(OAc)j, and with CuSO,. — EA': ppd. as an
oil by adding alcohol to its aqueous solution ; so-
lidifies after a time. Insol. alcohol. — BaA'.; 4aq :
small white crystals ; partly resolved by boiling
water into glycoUate and oxalate. — CaM^iu^;
646
OLYOXTLIO AGID.
thin needles or hard prisms. S. -67 at 8°. It
does not give off water at 170°, bnt at 180° it
gives oS water and COj, leaying glycollate and
carbonate.— Ca,(04Hj08)2.—CaA'j 4aq : gelati-
noQS pp. got by adding alcohol to the aqueous
solution.— (OaA',),(NH,),2aq.—(CaAy,(NH,),:
formed by adding ammonia to an aqueous solu-
tion of calcium glyoxylate at 50°.— Pb(OH)A'.—
Zn(OH)A'aq: white crystalline pp. got by adding
a cone, solution of c^cium glyoxylate to zinc
acetate. — AgA'aq: white crystalline powder; ri.
sol. cold water. — (AgA')4(NHj)j (Debus).
Combinations with bisulphites. —
NaA'NaHSO,: formed by adding a cone, solu-
tion of XaHSO, to one of glyoxylic acid. Crys-
tals, V. sol. water.— (CaAyjCa(SOsH)jlOaq:
formed by passing SOj into water, in which cal-
cium glyoxylate is suspended.^Caloium gly-
oxylate and glycollate
(Ca{C2H03)2)2Ca(CjH5Os)j4aq.— Calcium gly-
oxylate and lactate
Ca(C,H0,),Ca(C,HA)2 aq.
Phenyl-hydrazide CjHsNH.NiCH.COjH.
Formed as a pp. of fine yellow needles by adding
a solution of phenyl-hydrazine hydrochloride to
an aqueous solution of glyoxylic acid (Fischer, B.
17,677). Tellow needles. Decomposes at 137°.
Sol. alcohol and hot water.
Phenyl ethyl hydraxide
C,HsNEt.N:CH.C02H. Ppd. by adding phenyl-
ethyl-hydrazinehydroohloridetoa dilute solution
of calcium glyoxylate acidified by HCl (Elbers,
A. 227, 340). White needles, m. sol. hot water,
y. sol. alcohol and acetic acid.
Orthoglyoxylic acid CH(0H)j.C02H. This
is perhaps the true formula of glyoxylic acid.
Di-ethyl-derivati'oeCS.(0^t)i.OO^.
Formatwn. — 1. From tetra-ohloro-ethylene
and NaOEt at 100°-120° (Geuther a. Fischer,
J. 1864, 316).— 2. By boiling di-chloro-acetic
acid (18 pts.) with alcohol (90 pts.), in which
sodium (10 pts.) has been dissolved (Schreiber,
Z. 1870, 167).
Properties. — ^Unstable oil; split up by boUing
with HCl into alcohol and glyoxyUo acid. —
Ba(C,H„0,)2: deliquescent amorphous mass. —
AgC,H„04 : m. sol. water.
Ethyl ether of the di-ethyl deriva-
tive CH(0Et)j.C02Et. (199° cor.). S.d. ^
•994. Formed from CH(0Bt)j.C02Na and EtI at
120° (Schreiber, Z. 1870, 167). Formed also by
heating glyoxylic acid with alcohol at 120° (Per-
kin, B. 8, 188). Obtained by passing HCl into
a solution of HCy in dry alcohol (Pinner a. Klein,
B. 11, 1476).
Isobutyl ether of the di-isobutyl
derivative CH(0C4H,)jC0j.C,a,. (251°).
Formed by passing HCl into a solution of dry
HCy in isobutyl alcohol (P. a. K.). Oil. After
saponification it givesthe salt CH(OC4H,)2.G02Ag,
which crystallises in small needles, si. sol. cold
water.
Amide of the di-ethyl derivative
CH(OEt),.CONHj. [77°]. (Schreiber, Z. 1870,
168) ; [82°] (Pinner a. Klein, B. 11, 1477). From
GH(0Et)2.C02Et and cold alcoholic NH,. Tables
or needles (by sublimation), V. sol. water and
alcohol).
Amide of the di-isobutyl derivative
CH(0C,H,)2.C0NHp [c. 44°]. Crystalline (P.
a. K.).
Beference. — CHT^oiio-aLyozTUa bther.
GIYOXYLYI CYANIDE xCHO.CO.CN.
Phenyl-hydrazide 0HO.C(NjHPh).CN.
[161°]. Formed by the action of a concentrated
solution of hydrochloric acid upon the di-oxim
of the phenyl-hydrazide of mesoxalic aldehyde
CH(N0H).C(N2HPh).CH(N0H) (Von Pechmann
a. Wehsarg, B. 21, 30U0). Sulphur-yellow nee-
dles, insol. water, sol. other solvents. Decom-
posed on melting. Cone. H^SO, forms a yellow
solution not affected by FeCl,. Boiling HIAq
liberates aniline. When its dilute alkaline solu-
tion is poured into a neutral solution of diazo-
benzeue chloride there is formed C9H,N,0(N2Ph)
[163°] which crystallises from alcohol in brown
plates, insol. alkalis.
Oxim of the phenyl-hydrazide
CH(NOH).C(NjHPh).CN. [240°]. Formed by
treating the preceding with hydroxylamine hy-
drochloride in alcoholic solution. Lemon-yellow
difficultly soluble needles, decomposed by fusion.
Its solution in H^SO, is not effected by FeCl,.
Di-phenyl hydraside
CH(NjHPh).C(NjHPh).CN. [161°]. Formed by
the action of phenyl-hydrazine on a hot alco-
holic solution of the monophenylhydrazide
CH0.C(N2HPh).CN (Von Pechmann a. Wehsarg,
B. 21, 3000). Orange-red needles, decomposed
on fusion; sol. alcohol and HOAc, si. sol. most
other solvents. The solution in H2SO4 is not
affected by FeCl,. FeCl, or K2Cr20, acting on its
solution in dilute HOAc forms the'osotetrazone'
^CCv-NNPh^' ^^'■'^^ crystallises in bronzed
hair-like needles, melting, with decomposition,
at 137°.
The corresponding acid
CH(N2HPh).C(N2HPh).C02H [203°] is formed by
treating di-bromo-pyruvio acid with phenyl
hydrazine (Nastvogel, A. 248, 85). f-Tolyl
hydrazine and (a)-naphthyl hydrazine form
similar acids, melting at 188° and 196° respeo-
tively.
Phenyl-methyl-hydraside
CH0.C(N2MePh).CN. [114°]. Prepared from
CH(N0H).C(N2MePh).CH(N0H) by treating its
solution in acetone with cone. HClAq. Con-
verted by phenyl-hydrazine in acetic acid solu-
tion into CH(NjHPh).C(N2MePh).CN [181°],
which forms yeUow plates. Aniliue produces
the compound CH(NPh).C(N2MePh).CN, which
crystallises from alcohol in slender yellow
needles [151°].
Oxim of the phenyl-methyl-hydra-
Bide CH(N0H).C(N2MePh).CN. [178°]. Formed
from the preceding and hydroxylamine. Tellow
needles. Boiling acetic anhydride forms
CH(NOAc).C(NjMePh).CN, which orystaUises
from alcohol in yellow needles [122°].
QLYOXYLYl TJREA C^H^NA »•«•
NHj.C0.NH.C0.CH0. . The potassium salt is
formed with evolution of CO2, on adding acetic acid
to a solution of the potassium salt of oxonicacid
C^H^NjO, (Medicus, A. 175, 280; B. 9, 1162;
10, 644). Thick shining needles, si: sol. cold, t.
sol. hot, water. — £A' : crystalline powder. —
AgA' : amorphous powder.
Isomeride v. AuiAiitubic aoid.
ONOSCOPINE CwHajN^O,,. [238°]. S. (cold
alcohol) -07. An alkiiloid obtained from the
mother-liquors in the purification of narceiina
GOLD.
647
(T. B. H. Smith, Ph. [3] 9, 82). Sol. chloroform
and CS2, si. Bol. benzene. Insol. ac[ueous or
alooholic NaOH. Dissolves in acids. The solu-
tion in cono. 21,804 is yellow, turned crimson by
a trace of KNO,. A solution of the hydrochloride
gives a buff-oolonred pp. with platinic chloride.
GOA FOWBEK v. Chbysabobin, p. 173.
GOLD. Au lAimm). At. w. 196-85 (Thorpe
a. Laurie, C. J. 51, 565, 866). At. w. 196-64
(Kruss, B. 20, 205, 2365). Mol. w. unknown.
[1045°] (VioUe, O. B. 92, 866) ; [1240°] (Eiems-
dyck, G. N. 20, 23 ; for other determinations v.
CameUey's Melting and BoiUng-point Tables).
S.G. ^ 19-3 to 19-33 (G. Bose, P. 73, 1). S.H.
00-100° -0316 (VioUe, O. B. 89, 702) ; 12°-98°
■03244 (Eegnault, A. Ch. [2] 73, 1). C.E. at 40°
•00001443 (Fizeau, C. B. 68, 1125) ; 0° to 100°
■0000147 (Matthiessen, Pr. 15, 220). T.G. 58^2
(Ag = 100) (Wiedmanna.Franz,P.ilf. [4] 7, 33).
E.G. at 0»=4B^84 to 44-62 (Hg at 0° = 1)
(Matthiessen a. Von Bose, T. 152, 1). For
description of emission-spectrum v. de Bois-
bandran's Spectres Lrimimeitx.
Gold has been known and used from pre-
historic times. The names by which the metal
is known in different languages generally express
the property of brightness. The method of sepa-
rating gold by amalgamating it with mercury is
fully described by Pliny.
Occmrence. — Gold is found native, gene-
rally more or less alloyed with Ag. It occurs in
the crystalline, the compact metamorphic, the
trachytic, and trap, rocks, and in alluvial soils.
The greatest quantity is obtained from alluvial
deposits formed by the disintegration of ancient
auriferous strata. Gold is most abundant in
Europe in Hungary and Transylvania; but it
occurs in small quantities in very many primi-
tive mountains or in the sands of rivers issuing
from such mountains, e.g. in the southern slopes
of the Alps, in North WaJes, in the Scottish
Highlands, and in the Ural mountains. It is
also found in fair quantities in Brazil and Chili,
and other parts of S. America ; abundantly in
CaUfomia, and parts of Australia, and in British
Columbia. The purest specimens of native gold
contain about 99 p.c. Au. The Cahfornian gold
averages from 87*5 to 88^5 p.c, and the Austra-
lian from 96 to 96-6 p.c. Au.
ExtracUon of Qold. — (1) By washing
away the earthy particles with water.
This is effected on a large scale in California by
means of a head of water rushing through a
pipe with a narrow nozzle. Sometimes the sands
of an auriferous stream are washed in a wooden
cradle, which is rooked by hand. (2) By
amalgamation. The richer gold-containing
rocks are crushed and mixed with mercury,
whereby an amalgam of Au and Hg is formed ;
this amalgam is separated from the earthy
matter and heated in specially constructed iron
retorts ; the gold remains and the Hg is re-
covered. Poorer ores are washed before amal-
gamation. (3) By smelting. Ores which con-
tain small quantities of Au mixed with Cu and
Fb, and sulphides, are sometimes roasted, and
then mixed with quartz and smelted ; the mass
is powdered and treated with dilute EjSO^Aq ;
the residue is mixed with fresh quantities of ore
and the treatment ia repeated; when a fair
quantity o{ Au has accumulated in the residue
it is boiled with cone. H^SO^ to dissolve Ag, Cu,
&a., and the insoluble matter is subjected to a
process of parting. (4) By wet processes.
The principal process is that based on convert-
ing Au into soluble AuCl, by treatment with CI.
The ore is thoroughly roasted to remove S, As,
and Sb ; the moistened residue is then treated
with CI which must be free from HCl ; on ad-
dition of warm water, the AuClj dissolves ; the
Au is ppd. generally by ferrous sulphate. In
whatever way the Au has been separated it is
usually still alloyed with Ag ; this is separated
by parting. Sufficient Ag is added to ensure
the presence of S parts Ag to 2 parts Au ; the
alloy is granulated and treated with pure nitric
acid in which the Ag dissolves, while the Au
remains insoluble. Or the alloy, which should
contain from 19 to 25 p.c. Au, is treated with
hot cone. H2SO4; Ag dissolves and Au is in-
soluble. The treatment with HNOj or H2SO4 ia
repeated; the Au is washed and melted with
borax and nitre. For details of these and other
processes of gold extraction v. Dioiionaby or
TECHNIOAIi OHEMISTBY.
Prepa/ration. — Au may be obtained from any
alloy with Ag in which it is present by treating
with a mixture of 2 measures of cone. HClAq
and 1 of cone. HNO3, filtering, evaporating at
100° until acid vapours are no longer evolved,
dissolving the residue in warm water acidulated
with HCl, filtering, and ppg. Au by addition of
FeS04Aq: Or an alloy of Ag and Au, or of Ag,
Cu, and Au, containing not more than 20 p.c.
Au, may be granulated, heated with 2| times its
weight of H2S04Aq S.G. 1^815 in a Ft vessel as
long as SO2 is evolved, boiled with a little more
HjSOiAq S.G. 1-65, and allowed to settle ; the
liquid is then poured off and the treatment with
H2SO4 S.G. 1-815 is repeated once or twice;
finally the residual Au is washed and dried.
Eriiss {A. 238, 30) prepared pure Au, for his
determination of the atomic weight, by dissolving
the purest commercial Au in aqua regia, evapo-
rating to dryness at 100° with HCl, dissolving in
water, diluting largely, and filtering; he then
ppd. the Au (1) by SOj, followed by washing with
HClAq and water, drying at 180°, digesting with
cone. H2SO4 in a Ft dish, washing with hot
water, drying, fusing (in Ft) with EHSOf (to
remove Fd), then fusing with KNO3 (to remove
Ir), redissolving in agua regia, and reppg. by
SO2. By method (2) the Au was ppd. from the
dilute AuCI, solution by oxahc acid ; in method
(3) the pptant. used was FeCl^. In each case the
Au was washed, dissolved in agua regia, and
reppd. by SOj, again washed, and redissolved in
agva regia, and finally ppd. by oxalic acid.
Thorpe a. Laurie (0. J. 51, 570) prepared pure
Au, from old assay cornets, by dissolving in aqua
regia, evaporating to remove excess of nitric
acid, diluting with much water, allowing to settle
for several weeks, pouring off from traces of
AgCl, ppg. by SO2, and boiUng the pp. with water
tiU every trace of CI was removed.
ProperUes. — ^Au is the only metal of a yellow
colour; in thin sheets it appears greenish by
transmitted Ught. Au ppd. from solution by
SOjAqor FeS04Aq appears as a lustreless, brown-
yellow to reddish, powder. Au crystallises in
regular forms chiefly octahedra and dodecahedro.
648
GOLD.
Au is softer than Ag but harder than Sn. When
pure, An is the most malleable of all metals,
sheets '0001 mm. thick have been obtained. The
ductility of Au is nearly limitless; a grain of
Au has been dra\m into a wire 500 ft. long. Au
is not oxidised by heating in air ; it is volatilised
and perhaps partially oxidised whta a strong
electric current is passed through thin leaves or
wires. Insoluble in HNOj, cone. HClAq, or
HjSO,; dissolved by aq^la regia. CI and Br
combine direct with Au forming AuCl, and
AuBr, respectively; the metal also cojnbines
directly with P ; and it forms alloys with several
metals {v. infra, AmiOys). Compounds of Au
are generally easily decomposed by heat, yielding
Au. Purple of Cassius is probably a mixture of
SnOj with Au (v. Tin, oxides of).
Gold is distinctly and decidedly metallic in its
physical properties ; but in many of its chemical
relations it belongs to the non-metals. The com-
position of the aureus compounds Au^O, AUjS,
AuOl, &c., marks the resemblance between Au
and the alkali metals ; the solubility in water of
AujS and Au^O emphasises this resemblance.
The marked instability of the salts of Au, the
acidic character of the hydroxide AuOjH,, of the
sulphides AUjS andAuS, and the existence of the
acids HAuCl, and HAuBr„ mark the analogy
between Au and the non-metals. In the classifi-
cation based on the periodic law, Au is placed
both in Group I. which contains the alkali metals,
and in Group VIII. which contains the metals
Fe Ni Co and also the Ft metals. Au is the first
member of series 11, in which it is followed by
Eg, Tl, Pb, and Bi; these four elements are
decidedly metallic, but both Pb and Tl form
salts in which they play the part of negative
elements. (For a further discussion of the
chemical relations of Au v. Copfeb qboup or
Ei^siBiiis, p. 250.)
The atomic weight of Au has been determined
very carefully by Thorpe a. Laurie, from (1) the
ratio An:EBr, and (2) the ratio Au:AgBr ; the
salt used was KAuBr, (O. J. 51, 565, 866). Kriiss
{B. 20, 205, 2365) has also determined the at. w.
from analyses of EAaBr4, and also of AuGl,.
(For an account of older determinations v. paper
of Thorpe a. Laurie.)
I Alloiropic form of Gold. — According to Thom-
sen {Th. 3, 398) the Au ppd. by SO^Aq from
solutions of AuBr, differs from that ppd. from
AuClgAq ; the thermal measurements of the two
reduction-processes show, according to Thomsen,
that Au ppd. from AuBr, possesses energy equal
to 3,210 gram-units of heat, per 197 grams of
gold, more than the Au ppd. from AuCl,.
Gold, alloys of. Gold alloys with most
metals. The alloys which are of most technical
importance are those with copper and silver.
Pure Au is too soft for making jewellery, watches,
coins, &o. ; alloying it with Cu increases the
hardness, and produces a' redder colour than that
of pure Au. Alloying with Ag gives a lighter
colour. Alloys of Au with Cu and Ag are more
fusible than pure Au. The standard coinage of
the United Kingdom is 11 Au to 1 Cu. Au
forms amfxlgams with Eg. By dissolving 1 pt.
Au in aoout 1,000 pts. Eg, pressing through
chamois leather, and treating the residue with
ENOjAq, a solid amalgam approximating to the
composition AugHg is B&id to be obtained
(Henry, P. M. (4) 9, 468). An amalgam,
approximately AujHgj, is found native in
CaJifomia. Another amalgam, approximately
Ag^AUsEg,,,, is found in New Granada. The pasty
amalgam of 2 pts. Au with 1 pt. Hg is sometimes
used for gilding articles of copper and bronze.
The surface of the article is cleaned thoroughly
by heating and immersing in dilute H^SO^Aq,
it is then amalgamated by rubbing with
Hg(N03)2Aq, and then pressed on the pasty
amalgam of Au ; the Hg is then driven off by
heat, and the surface is polished. Copper may
also be gilded by immersion in boiling AuCl,Aq
to which an alkaline carbonate has been added.
The process of gilding generally consists in de-
positing Au from solution of the cyanide in
KCNAq by an electric current, the object to be
gilded being made the negative pole, while the
positive consists of a bar of gold (v. Dictionaby
OF lECHNICAIi CHEMISTBY).
Gold bromides. Aureus bromide AuBr, and
aurio bromide AuBr,, have been isolated, and,
according to Thomsen, a third bromide AuBr,
also exists ; as none of the bromides has been
gasified, the above formulsB may or may not be
molecular. Thomsen gives the following ther-
mal data {Th. 3, 412) [Au, Br]= -80; [Au, Br»]
= 8,850; [Au, Br», Aq] = 5,090; [AuBr», Aq]
= - 8,760 ; [AuBr'Aq, 3HClAq] = 4,280. AuBr,
combines with EBr to form HAuBr, (v. infra).
AuBons BEOMiDB AuBr (or Au^Br^).
EAuBrj.SHjO {v. infra) is placed in a porcelain
basin, the bottom, but not the sides, of which is
gently heated; the salt melts and then evolvesH^O
and EBr ; the dish is then kept in a drying oven
at 115° until the colour is yellowish-grey (Thom-
sen, Th. 3, 390). AuBr is described by Thomsen
as a greyish -yellow body with atalo-like appear-
ance, unchanged in air and insoluble in water ;
decomposed somewhat above 115° into Br and
Au ; reacts with EBrAq to form EAuBr, and
Au.
AtiBo-AUBic BBOMiDB AuBr, (or AuBr.AuBr,).
According to Thomsen {Th..S, 386), this com-
pound is produced by treating Aii which has been
reduced by SO^Aq and dried at 170° with excess
of Br, removing the excess of Br by tilting
the vessel, powdering the residue, and again
treating with a little Br. Thomsen describes
AuBr, as a compact, almost black, non-deU-
quescent, mass ; at c. 115° it is decomposed to
AuBr and Br; it dissolves slowly in water to
form AuBr and AuBr, ; it is decomposed rapidly
by acids and also by anhydrous ether into AuBr,,
which dissolves, and a residue, probably AuBr,
which slowly decomposes to AuBr, and Au.
According to Kruss a. Schmidt (B. 20, 2684)
AuBr, does not exist.
AuBic BBOMiDE AuBr,. Ppd. Au is dissolved
in Br Aq, or better in EBrAq containing ENO„ and
the solution is evaporated at a low temperature.
Thomsen (Th. 3, 387) recommends to treat
AuBr, with anhydrous ether, which is kept cold
by the passage tiirough it of a current of air, and
then to evaporate the cone, solution thus ob-
tained by sucking a rapid current of air through
it (if temperature is not kept low, reduction of
AuBr, takes place), to allow the residue to stand
over lime until dry, then to powder and dry at
70°. AuBr, is a dark-brown, non-deliquescent,
powder ; soluble in water and ether ; the sola-
GOLD.
640
tiong when eouo. are nearly black. AuBrjAq is
partially reduced by boiling; SOjAq forms AuBr
and then Au. AuBr, combiuea with HBr to
form HAuBr, {v. infra) .
AnBO-BROMBTEDRio AOH) HAuBrj.SBCjO (Auro-
bromicacid. Bromo-auricacid. Hydrogenbromo-
cmrate). Finely divided Au is treated with excess
of Br ; when the reaction is completed, HBrAq
S.G. 1"38 is added in the proportion of 100 g. to
every 100 g. Au used, and then enough Br is
added to dissolve completely all the Au; the
liquid is poured into a porcelain dish which is
allowed to stand in a cool place. Large, dart,
vermillion-red crystals soon separate ; after an
hour or so the mother liquor is poured off, and
the crystals are dried at a temperature not ex-
ceeding 20°. The crystals melt at 27° ; they are
unchanged in ordinary air. HAuBr^Aq is reduced
to An by SOjAq {Th. 3, 389). Thomseri (Th. 3,
411) gives the thermal data : [AuBr'Aq,HBrAq]
= 7,700 ; [AuBr', HBrAq] = 3,880 ;
[AuBr», HBr, SffO] =85,280; [Au,Br», HBrAq]
= 12,790 ; [HAuBr'Aq, 4H01Aq] = -510 ;
[3AuBr, HBrAq] = 3,650; [AuBr'Aq, 2S0'=Aq]
= 61,790 ; [HAuBr*. SlLfl, Aq] = -11,400.
Aurobromate of potassium KAuBrj.
Potassium bromo-aurate. Monoolinio crystals ;
a,:6:c = -79688:l:-361 ; ;3 = 85° 34' 2" (Schott-
lander, A. 240, 846). Prepared by dissolving a
mixture of finely- divided Au and KBr, in the
ratio Aa:KBr, in excess of Br with addition of
a considerable quantity of water, evaporating,
and crystallising from water (Thorpe a. Laurie,
G. J. 51, 671). The salt is decomposed by heat
to Au and KBr. According to Eruss {B. 20, 2365)
KAuBr, cannot be obtained perfectly free from
traces of Au ; but this is denied by Thorpe a.
Laurie (C J. 51, 866). The salt in solution is
very easily partially reduced.
Gold chlorideg. Two chlorides AuCl and
AuClj certainly exist ; Thomson says that a third
chloride, AuOlj, is also produced by the reaction
between Au and CI; this is denied by Eriiss,
but re-asserted by Thomson. The formulsa
AuCl, AuCl:, and AuCl, are the simplest that
can be given ; but as the compounds have not
been gasified these formulas are not necessarily
molecular.
AuBons OHLOBiDE AuCl. Best prepared ac-
cording to Thomsen {Th. 3, 386) by heating
AuCl, to 185". Yellowish-white powder ; iusol.
water, but decomposed by water, quickly on
heating, to AnOljAq and Au. [Au, CI] = 5,810;
[SAuCl, HClAq] = 4,980 (Th. 3, 411).
Arso-AUBio OHLOBIDE AuClj (or AuCLAuCl,).
Thomsen {Th. 8, 383) describes this compound
as a hard, dark red, very hygroscopic, solid ; de-
composed by water to AuCl and AuCl,Aq ; de-
composes at c. 250° giving some AuCl,; pre-
pared by leading dry CI over Au ppd. by SOjAq
from AuCl,Aq, the reaction being started by
gentle heating and then allowed to proceed until
all the Au is changed to AuCl, (Th. 3, 383 ; v. also
Thomsen, J. pr. [2] 37, 105). Kruss a. Schmidt
(J3. 20, 2634 ; and also J. pr. [2] 38, 77) assert
that the products of the action of Cl on Au are
a mixture of An and AuCl,, and that no AuCl,
is produced.
Kruss (B. 20, 211) says that when finely-
divided Au is heated in dry Cl to 140° auro-
Butio chloride is produced; at 180°-190° this
is decomposed with formation of AuCl and a
little AuCls ; at 220°-230° a little more AuCl,
is obtained and the AuCl decomposes to Au and
Cl, and that the Au thus produced remains un-
changed in the Cl ; on cooling these reactions
are reversed. But in a subsequent memoir Kriiss
a. Schmidt say that the only products of the
reaction of Au with Cl are AuCl and AuGl,, and
finally AuCl, and Au.
AuBio OHLOBIDE AuCl,. Formcd by dissolv-
ing Au in agua regia, evaporating, and crystal-
lising, and drying on a porous tile over cone.
HjSO, for several days. A purer product is
obtained by evaporating the solution in aqua'
regia to dryness, heating the residue to 185° so
long as Cl is evolved, decomposing the AuGl
thus formed by a very little hot water, allowing
to settle, decanting from Au, and evaporating to
dryness the cone. AuCl,Aq thus obtained over a
flame arranged so that the bottom and not the
sides of the vessel is kept hot ; when the residue
is heated to 150° pure AuCl, is obtained. Thom-
sen (Th. 3, 384) recommends to treat AuCl,
instead of AuCl with water in the manner di-
rected. If cone. AuClgAq is evaporated to the
crystallising point, and then allowed to stand in
dry air, large orange crystals of the hydrate
AuCla.2HjO separate; these are dehydrated by
standing on a porous tile over cone. H^SO, for
some days (Th. 3, 386). AuCl, is also formed
by heating finely-divided Au in Cl (v. supra).
Lindet (C. B. 101, 1492) recommends to heat
Au in Cl in presence of AsCl,, SiClj, SbClj, SnCl„
or TiCl, ; AuCl, is formed and dissolves in the
other chloride, but separates in crystals on cool-
ing.
Auric chloride crystallises in large red-brown
leafiets; it is very deliquescent, and dissolves
in water with production of heat. AuOljAq is
easily reduced ; Au is ppd. by P, many metals,
PeSOj, Kfifit, AsjO,, SbjO,, and by organic
matter ; reduction also occurs by the ^action of
light (v. Foussereau, C. B. 103, 248) ; AuCl^Aq
is not reduced by pv/re NaOH, but if organic
matter is present reduction occurs (Kriiss, A.
287, 274). AaCl, dissolves in hot AsClj, SiCl„
SbCl,, SnCl,, and TiCl,, but separates again on
cooling. When Au is heated with SjCl, the com-
pound AuGlj-SGlj is formed; and when Au is
heated with SeGlj dissolved in molten AsGl,, and
Cl is passed in, the compound AuGlj.SeGlj is
produced (Lindet, C. B. 101, 1492). AuGl, com-
bines with HCl to form HAuGl^ (v. infra). HBr
reacts with AuCl, to form HAUCI4, HAuBr^, and
HGl (Th. 3, 410). Thomsen (Th. 3, 411) gives
the thermal data :— [Au, Cl^] = 22,820 ; [AnGl», Aq]
=4,450; [Au, Cl',Aq] = 27,270 ; [AuGl».2ffO,Aq]
= - 1,690 ; [AuGl'Aq, 4HBrAq] = 15,210.
AuBo-CHLOBEYDBio ACID HAuGl4.4H,0. (Auro-
chloricacid. Ohloro-aurioaeid. Hydrogen chloro-
aurate). Long yellow needles, formed by dis-
solving Au in agua regia, adding a large excess
of HCl, evaporating to a syrup, and allowing
to crystallise. Also by dissolving AuCl,Aq
in HClAq and evaporating; in dry air
HAnClj.3HjO is formed {Th. 3, 407). HAuCl,
is also formed, along with HAuBr, and HCl,
when excess of HBrAq is added to AuCli^Aq
(rfc. 3, 410). [AuCl'Aq, HClAq] = 4,530 ; [Au^
Cl», HClAq] = 31,800 ; [AuCl», HCl, 4ffO]
-82,130; [AuCl'Aq, 4HBrAq] = 16,210i;
660
GOLU.
[HAuCl^Aq, 4HBrAq] = 13,800;
[HAuClUHH>^q] = - 6,830 ; [HAu01*.3H'0,A(j]
= -8,550.
Ammonium auro-chlorate, (NHJAuCli
(Ammomum chloro - aurate). Sy dissolving
NH,CI in AnClgAq strongly acidified with HOI,
and eyapoiating,monoolinio yellowtablets are ob-
tained, having tiie composition 4NH,AnCl4.5H20 ;
if these are dissolved in water and re-cryatallised
rhombic plates are formed 2NH,AuClt.5H20.
Both salts are dehydrated at 100°.
Potassium auro-chlorate or ehloro-
aurate, KAuCl,. Formed similarly to the NH-4
salt ; crystallises in yellow needles, QSAuOl^.E^O ;
the crystals effloresce in the air; when heated
they melt with evolution of CI, and the liquid
BoHdifies to EAuCl,.
Sodium auro-chlorate or ehloro-
auirate, NaAuCl,.2H20. Pormed similarly to the
N'H« salt.
Aurochlorates of Ba, Cd, Ca, Co, Mg, Mn, Ni,
Sr, and Zn have been obtained by Yon Bonsdorff
(P. 17, 261 ; 83, 64).
Gold cyanides; and doable cyanides, also
anricyanides, v. pp. 331-2.
Gold, fulminating, v. aubic oxide, infra.
Gold hydroxides v. qold, oxides and
BYDBoxiDEs OF, imfra.
Gold iodides. Two are known, Aul and
Aul,.
AuBODs IODIDE Aul. A citron-ycllow powder,
insol. cold, si. sol. hot, water. Formed by
adding HIAq to AojOj, I being set free in the
reaction; or by adding an equivalent quantity
of EI in solution, little by little, to AuCljAq
(AuCljAq + 3KIAq = Aul + 3KClAq + 21) . Decom-
posed at 120° to Au and I; decomposed by
KOHAq with ppn. of Au. [Au,ri= -5,520 (Th.
3, 412).
AuBio IODIDE Aul,. A dark-green pp. formed
by adding AuCl,Aq, little by little, to KIAq.
When less than AnCl, is added to 4KI
a dark-green liquid is formed, and then a,
pp. which dissolves on shaking; on then
adding a little more AuGIjAq ti^ie liquid is
decolourised and Aul, is ppd. (probably
(1) 4KIAq + AuCl3Aq = 3K01Aq + KAuI,Aq and
(2) SKAuIiAq -I- AuCl,Aq = SKClAq -H 4AUI3). Aul,
is very unstable ; exposed to the air it changes
to Aul. It combines with HI, but little is known
of the properties of the compound ; with EI it
forms KAuI,.
Potassium auro-iodate or iodo-aurate
EAuI,. Black, lustrous, four-sided prisms ;
formed by dissolving Aul, in EIAq, or by mixing
Aul, and EIAq in the ratio AuI,:4EI, and al-
lowing the liquid to crystallise. Soluble, with
partial decomposition, in water. Decomposed
by heat to Au and EI (c/. Johnston, P. M. [3J 9,
266). [Au01»Aq,3EIAq] = 45,660 {Th. 3, 411).
Gold, oxides and hydroxides of. Three oxides
of An have been isolated : aurous oxide Au^O,
avro-aurio oxide AuO, and auric oxide Au^O,.
Aurylio hydroxide AuO.OH (or Auj02(0H)g) has
been obtained, and perhaps one or two other
hydroxides intermediate between AuO.OH and
AuO,H,. There is still doubt as to the isolation
of auric hydroxide AuOaH,. Oxides of Au con-
taining more 0 than AujO, have been described,
but according to Eriiss none of these exists {v.
ErUss, B. 19, 2541 ; references to older papers
are given by Kriiss). The hydrate AUjO.aHjO
described by Baschig (A. 235, 341} does not exist
according to Eriiss.
Anitous OXIDE AujO. This oxide is best pre-
pared by adding SOjAq, drop by drop, to
EAuBrjAq kept at 0° until the red colour just
disappears, pouring ofl the liquid, warming the
residual AuBr wi& EOHAq, washing the ppd.
hydratedAujO with boiling water, and drying
over P2O, (EruBS, B. 19, 2543). AugO is a
greyish- violet solid; when freshly ppd.it is some-
what soluble in cold water, but is ppd. on boil-
ing ; also slightly soluble in EOHAq ; soluble in
HClAq or HBrAq with separation of Au ; un-
acted on by other acids ; decomposed at c. 250°
to An and O. Solutions of AujO in water
give a marked absorption-spectrum (Eriiss, Z.c.).
Baschig (A. 235, 341) deschbes bodies produced
by reactions between aurous oxide and ammonia,
and the same oxide and methylamine; when
cone. NH,Aq is added to Au^O suspended in
water, a black explosive compound, NAu,.NH„
is obtained, and when this is boiled with water
or dilute acids triawramine, NAn,, is produced ;
NH^Me forms NMeAu^.
AuBO-AUBio OXIDE AuO (oi An20.Au20,). Ac-
cording to Eriiss (P. 19, 2544) this oxide is best
obtained by heating AuO,H, (u. infra) to 160°.
AuO is described as a dark olive-brown powder;
very hygroscopic, and must be kept over P5O,
(ErQss; v. also Schottlander, A. 217, 312).
Cone. NHj^q acting on AuO is said to form
the very explosive body sesqmhydr(mfr\jlamme
NH3.N(AuOH), (Baschig, A. 235, 341).
AuBio OXIDE AujO,. AaCl,Aq is obtained by
decomposing 1 pt. AuCl with 50 pts. water and
filtering; the Uquid is heated to boiling and
maqtiesia alba (not tista) is added until the red
colour of the liquid disappears; the pp. of
AuO,H, is filtered off, suspended in 20 pts. water,
and kept in contact with 10 pts. HXO,Aq, S.G.
1-4, for 12 hours ; the residue is then digested at
100° for 6 hours, with reversed condenser at-
tached, with HKO,Aq and water as before ; the
residue from this digestion is washed with hot
water until every trace of HNOjis removed ; the
AuOjH, is then dried and very carefully heated
(? to under 100° ; the directions given by Eriiss
are not clear). AUjO, gives ofi 0 at c. 110° ; at
160° AuO remains ; at 250° Au remains. It is
easily reduced to Au.
When moist AUjO, is treated with excess of
NH,Aq, or when excess of NHgAq is added to
AuGl,Aq and the pp. is suspended in boiling
NH,Aq, or in water containing a little EOH,
and then allowed to dry, a yellowish-brown
solid, with a tinge of purple, is obtained, which
explodes 'loudly when struck by a hammer ot
when heated to a little above 100° ; the products
of the decomposition are Au, NH,, N, and H2O.
This substance is generally known asfuVminating
gold. Dumas (A. Ch. [2] 44, 167) gave to it the
formula (AuN.NH,)2.3H20 ; this is confirmed by
Baschig {A. 235, 341) for the body obtained by
the action of NH,Aq on Au^O,, but B. says that
the product of the action of NH,Aq on Au01,Aq
is a mixture of the preceding auric diamine
with auric inddo-chloride, NH.An01, Dilute
HjSOtAq with fulminating gold forms a very
explosive body, (AnNjH5)i.HjS0j (E.).
AuBic BTDBOxiDES. According to ErusB (J3.
GRASDIFLORINE.
651
19, 2S46) the aotmal hydroxide
Au20,.3H20(=AqO,H,) is obtained by ppg.
AuCl,Aq by magnesia alba, and lei^ovittg the
excess of magnesia by HNOjAq (for details v.
supra, AUBio oxide) ; Kriiss does not say at
what temperature the pp. must be dried, nor
does he give analyses. When this pp. is kept
for some \reeks over PjOj the hydroxide
AujOs.H20( = Auj02.02H2) is obtained (Kruss).
Schottlander {A. 217, 312) failed to isolate
AuOjEg; the highest percentage of water he
obtained agreed with the formula 2An203.8H20,
and the lowest with the formula AU2O3.H2O.
Schottlander (Ix.) by decomposing AuSO^ {v.
Sulphates) by water obtained the compound
3AuO.HjO( = Au302.02Hj). These hydroxides,
or hydrated oxides, yield Au when heated to 0.
250° (e/. also Pelletier, A. Ch. [3] 15, 5, 113 ;
Fremy, A. Ch. [3] 31, 478; Thomsen, Th.
3, 391).
Moist auric oxide (? AuO^H,) is a weak base ;
it dissolves in cone. H^SO, and HNOjAq but the
solutions are decomposed by water with ppn. of
hydrated AujO,. Schottlander [A. 217, 312)
obtained Au(NOa)s.HNOs.3H20 by dissolving the
hydrated oxide in HNOjAq, S.G. 1-492, at 20°,
heating to 100°, separating from ppd. Au, and
crystallising by surrounding by a freezing mix-
ture ; by heating this acid nitrate to above 73°
he obtained the normal nitrate Au(N0s)s.xH20.
The same chemist obtained the sulphates
AuCHSO, and AuSO, from the nitrate. Hy-
drated auric oxide dissolves in alkalis, and
from such solutions salts have been obtained
known as aurates, e.g. KAuOj.BH^O. These
salts are very easily reduced to Au (v. Aubates,
vol. i. p. 863). Thomsen (Th. 3, 411) gives the
following thermal data : [AuOsH»,4HClAq]
= 22,970; [AuO'H»,4HBrAq] = 36,780 ;
[AuO'H»,3HClAq] = 18,440 ; [AuO=ff ,3HBrAq]
= 29,080 ; [Au^O»,H^O] = - 13,190.
Gold phosphide Au^Pj. A grey solid, S.G.
6-67, formed by gently heating Au in P vapour ;
decomposed by heat (Schrotter, W. A. B. 1849.
301).
Gold purple. A name given to pwrple of
Cassius, which is probably a mixture of, SnOj
with finely divided Au {v. Tm, oxides of).
Gold, salts of. Pew compounds have been
isolated produced by replacing H of acids by
Au ; those which are known are very easily re-
duced, like all the compounds of Au. The
normal nitrate and sulphate Au(N0s)3, and
AUSO4 have been isolated {v. supra) ; also some
hasic mbrates and sulphates, and a few double
salts, e.g. gold-a/mmonium sulpMte and gold-
ammormimthiosulphate {v. NiTBATES,SniiPHATES,
iSici):
Gold selenide. The pp. obtained by adding
HjSe to solutions of An is probably a selenide
(Berzelius, P. 8, 178).
Gold selenocyanides v. p. 348.
Gold sulphides. Two sulphides, AUjS and
AnS, have been isolated; these sulphides form
tliio- salts by reacting with alkaline sulphides,
but the salts have scarcely been examined.
When HjS is passed into AuOljAq, kept at 100°,
Au is ppd. ; if local cooling takes place the pp.
contains varying proportions of combined S,
but no definite compound is produced (Ij. Hoff-
mann a. Kriiss, B. 20, 2369).
AuEous suLFHinB Aii^S. Obtained by passing
H^B into a solution of EAuCy^ and then adding
HClAq. The KAuOy^ was prepared by decolour-
ising AuClgAq by KGy, concentrating at 100°,
adding dilute HOlAq, evaporating, and washing
the pp. with hot water. The KAuOy, was dis-
solved in KCyAq ; the liquid was saturated with
HgS, excess of HOlAq was added, and the whole
was heated to boiling. The grey, pp. which
formed was washed vrith HClAq, then with
CjHgO, ether, and CS,, in succession, and finally
with ether (L. Hoffmann a. Kriiss, B. 20, 2373).
AujS is a brownish-black powder ; when freshly
ppd. it dissolves in water, but after drying it is
insoluble in water, and not decomposed by boU-
ing dilute HGlAq or H^SO^Aq. Dissolved by
BrAq, forming • AuBrj and HjSO, ; oxidised
readily by ojMfls regia, &o. It is not acted on by
KOHAq even at 100°; slowly dissolved by
alkaline monosulphides, easily by alkaline poly-
sulphides, with formation of thio- salts of Au.
AUjS is soluble in KCyAq, and is reppd. by
HOlAq. It is completely decomposed by heating
to 240° (H. a. K.).
AnBO-AUEIO SUIiPHIDE AuS( = AUJS.AU2S3) (L.
Hoffmann a. Kriiss, B. 20, 2704). Obtained by
passing H^S into cold AuCl,Aq until the
liquid is colourless, washing the pp. repeatedly,
by decantation, with water, then with abso-
lute alcohol, dry ether, and CS2, successively,
and finally with ether, and drying at 120°-130°
(8AuCl3Aq + 9H2S + 4HjO
= 8AuS + 24H01Aq + H,SO,Aq). AuS is a black
powder ; when finely divided it transmits reddish
light. Heated to 140° SO^ is evolved, and at
250°-270° all S is removed, without the inter-
mediate production of Au^S. AuS is insoluble
in all acids except aq^M regia ; it is gradually
oxidised by BrAq to AuBrj and HjSO^ ; it is dis-
solved by alkaline siflphides; acids ppt. AuS
from these solutions. Gone. KOHAq has no
action when cold, but on heating Au is ppd.
and K aurate and thio-aurate go into solution.
H. a. K. (I.e.) have repeated the experiments
of Berzelius, Oberkampf, Yorke, and others, but
have failed to obtain any other sulphides of gold
except AujS and AuS. (For references to the
older memoirs, v. H. a. K., l.c.)
Sodium aurosulphide NaAuS.4H20.
Monoclinic prisms; very easily decomposed in
air; obtained by fusing together Au, NajS, or
Na^GOj, and S, lixiviating with water in an at-
mosphere of N, and evaporating in the same
atmosphere m vacuo.
Gold sulpfaocyanides v. p. 350.
Gold telluride. Probably obtained by ppg.
AuCljAq by H^Te (BerzeUus, P. 8, 178).
M. M. P. M.
GOSSYPOSE is identical with Eafeinosb.
GEAMININ 6G„H,„05aq. [209°]. S.G. 1-522.
[o]„= -38-89°. S. 22-8 at 10°. A carbohydrate
found in the roots of Trisetum alpestre and other
plants (Ekstrand a. Johanson, B. 21, 597).
GBAirAIINE. An alkaloid in the bark of
the root of the pomegranate (Durand, J. Ph.
[4] 28, 168).
GBANDIFLOBINE. Mol. w. 236-4. Obtained
from the fruit of Solanum grandiflorum by ex-
tracting with water and alcohol. White powder
giving the usual alkaloid reactions. Cono.
HjSOj and alittle MnOj give a yellow colouratioi^
652
GEANDIPLORINE.
taming green and then violet (Domingos Fieiie,
C. B. 105, 1074).
GBAN1TL0SE v. Stabch.
GRAPHITE, a form of carbon; v. vol.' i.
pp. 685-687.
GKAPHITIC ACID ChHjOj. Formed in small
quantity in the electrolysis of mineral acids and
Ealts when the positive pole is pure graphite
(Bartoli a. Papasogli, G. 12, 114 ; 13, 37).
' Pr^aration. — Graphite, purified by boiling
with acids and fusion with caustic potash, is
intimately mixed with KClOj (3 pts.) ; the
strongest nitric acid is added in sufficient quan-
tity to render the mixture fluid; and the whole
is either exposed to sunshine or heated to 60°
for 3 or 4 days. When no more yellow vapours
are evolved, the mixture is shaken into a large
quantity of water, and the undissolved portion
washed by decantation, dried at 100°, and treated
with EClO, and HNO, as before. This process
is repeated three or four times, the residue being
graphitic acid (Erodie, A. 114, 6).
Prc^erties. — Thin transparent yellow crys-
tals ; si. sol. pure water, insol. water containing
acids or salts. When heated it explodes with
incandescence, giving off gas and leaving a black
residue. When suspended in petroleum (boiling
at 270°) and heated, water comes over between
100° and 200°, COj being also evolved ; the
petroleum acquires a deep-red colour, and a
black carbonaceous residue (O^fi,?) is left.
When a solution of ammonium or potassium
sulphide is poured upon graphitic acid it de-
composes with decrepitation, forming a graphi-
toidal substance with metallic lustre. Acid
solutions of cuprous and of stannous chloride
behave in like manner. Gottschalk [Z. 1865,
652) represents graphitic acid by the formula
C„H,Oe.
Salts. — Wlien graphitic acid is shaken with
aqueous ammonia it is transformed into a trans-
parent jelly, without dissolving; after adding
acids and drying in vacuo the residue has the
same weight as the original graphitic acid.
Moist graphitic acid shaken up with baryta-
water, washed, and dried at 100° yields a com-
pound containing 21-1 p.c. Ba ; after being sus-
pended in water and decomposed by a stream of
CO,, the salt, dried at 100°, contains 13-3 p.c.
Ba. This may be Ba(0i,H305)2. It is hygro-
scopic and detonates ^hen heated.
Nitro-graphitoic acid Oj2H„NO,s. An
amorphous brown substance got by treating
graphite from iron (Spiegeleisen) with HNOj
(Schiitzenberger a. Bourgeois, B. 8, 547). Sol.
water, nitric acid, alkalis, and alcohol, insol.
solutions of salts.
GBAFHON, a name given by Brodie to a
supposed form of carbon of which graphitic acid
was a compound (v. vol. i. p. 687).
GEATIOIIN Ca,H3,0,. A glucoside occurring
in Qratiola officinalis (Marchand, J. ChAm. Mid.
1845, 357; Walz, Jahrb. pr. Pharm. 21, 1).
Amorphous substance, insol. ether, si. sol. water,
V. sol. alcohol. Cone. H^SO, forms a purple
solution, the colour being destroyed by water.
Its aqueous solution is ppd. by tannin. Boiling
dilute H2SO, splits it up into a sugar, gratio-
letin C„H2sOg a crystallisable substance insol.
water and ether, and gratioleretiu C„H2gO, a
resin, insol. water, sol. ether.
■*-nother glucoside
occurring in Gratiola officinalis. Easily resolved
by acids, alkalis, and even PbO into glucose and
gratiosoletin CjgHfgO,,, a substance soluble
in water and ppd. by tannin. Gratiosoletin is
further resolved by boiling with dilute acids into
glucose and a resinous mixture of gratiosoleretin
CsjHj^Og, sol. ether, and gratiosoleretin
hydrate C,4EsgO,„ insol. ether. It need hardly
be observed that all these formula are extremely
doubtful.
GRAVITY, SPECIFIC, synonymous with
relative density, v. p. 371.
GREVILLEA GV^. Occurs on the bark of
Grevillea robusta. Yellowish-red, slightly trans-
lucent mass ; swells up in water, forming a white
emulsion, whence alcohol ppts. the gum, leaving
6 p.c. of a red resin in solution. If soaked in
water containing a little EOH, lime, or KfiO^,
the resultiug solution gelatinises on addition of
FeCI,. The aqueous solution is Isevorotatory,
gives no pp. with lead acetate, but a blue gela-
tinous pp. with CUSO4. It does not reduce Feh-
ling's solution. It is oxidised by HNO, to mucio
and a little oxalic acid. Boiling dilute HjSO^
forms a sugar (G. Meury, J.Ph. [5] 9, 479).
GUAIACENE C^HjO. (118°). Obtained by
distilling gum guaiacum. Identical with Tiolic
iLDEHyDB (j. «.).
GUAIACOL V. Methyl derivaUue of FtBo-
CATBCHIN.
GTTAIACUII. Besina guajacisaUva. A resin
which exudes from the stem of Ottajacum offi-
cinale, a tree growing in the West Indies. It is
composed of yeUowish-brown lumps usually
covered by a greenish-grey powder which renders
it opaque. It is brittle. S.O. 1-205 to 1-226.
When heated it emits an odour somewhat like that
of gum benzoin. Alcohol dissolves about 90 p.o.
of the resin, the solution being ppd. by water.
Ether and oil of turpentine dissolve much of it.
It is nearly insol. water. It dissolves in alkalis.
HgSO, dissolves it, forming a splendid red solu-
tion, which yields a violet pp. with water ; alco-
hol first colours the liquid violet-blue, and in
larger quantity imparts to it a dirty bluish-green
tint (Sohiff, A. Ill, 372). Both the powdered
resin and its alcoholic solution turn green when
exposed to the air and light (especially violet
rays). The alcoholic solution is coloured blue
by nitrous fumes, by CrO,, by ozone, by chlorine,
by EsFeCys, by AuCl,, by KMnO„ by M0O3, and
by FeCl,; the blue colour is removed by SO,.
Guaiacum tincture is coloured blue by concen-
trated, but not by dilute, cuprio sulphate solu-
tion. Even dilute OuSO,, in presence of HCy
or of organic nitriles, also colour tincture of
guaiacum blue (Schonbein, Fr. 8, 67; Schaer,
Fr. 9, 430). According to Sohonn (Fr. 9, 210)
guaiacum tincture is coloured blue by a dilate
solution of CuSO, in presence of NHjCl, BaClj,
NH^Br, KI, KCy, and NH^F. Schonn also ob-
serves that guaiacum resin is coloured blue by
solid lead acetate, by solid CaCl,, by solid BaOO,
on addition of a little HClAq, by MnCl,, by mer-
curous nitrate, by a cone, solution of sodium
sulphocyanide, and by cupric chloride even in
very dilute solutions. Arterial blood colours
tincture of guaiacum blue. According to Schon-
bein {J. pr. 102, 164) exposure to light deprives
tincture of guaiacum of the power of being
GUANIDINE.
65S
turned blue by ozone. Heat also deprives the
resin of this property (Eager, Fr. 26, 261).
FotaBh-fusion forms protocatechuic acid from
guaiacnm. Dry distillation forms tiglio alde-
hyde C5H3O (118°), guaiaool CsHiOH)(OMe)
(200°), oreosol C.H,Me(OH)(OMe), and pyro-
guaiaoin C.sH^O, [181°] (fflasiwetz, A. 106, 361).
Distillation with zino-dust forms oreosol, toluene,
m- and2;-xylene, ifi-cumene, and guaiene OijHu
(Botsch, M. 1, 615). Alkalis extract guaiaretio
acid from guaiacum (Unverdorben, P. 16, 369).
According to Hadelicn (J.pr. 87, 321) guaiacum
also contains guaiaconio acid (sol. ether), and a
resin 0„H„0, or C^'B^O, (insol. ether) [200°],
sol. alkalis and reppd. by acids.
Guaiaretio aoid OajHaOi. [75°-80°].
Powdered guaiacum is boiled with milk of lime
for half an hour, and the dried insoluble residue
exhausted with hot alcohol ; the alcoholic solu-
tion is evaporated and the residue dissolved in
warm aqueous NaOH (S.G. 1"3). On cooling,
sodium guaiaretate separates, and may be puri-
fied by reorystallisation. The free aoid is then
got by adding HClAq (Hlasiwetz a. GUm, A.
119, 266 ; cf. Thierry, J. Ph. 27, 381 ; Hlasi-
wetz, A. 112, 182).
Properties. — Brittle, concentrically grouped
needles (from EOAc). Colourless ; permaneat
in the air. Sol. alcohol, ether, hot HOAc,
and CS,. Sol. KOHAq ; insol. NE^q. Ppd.
by addmg NHjOl to its solution in KOHAq.
Fpd. as a resin by adding water to its alcoholic
solution. Its alcoholic solution is Isevorotatory,
and is coloured grass-green by FeClj. Chlorine-
water does not colour the alcoholic solution
either green or blue. The aqueous solution is
not coloured blue by fuming HNOa. Whein
slowly distilled it yields guaiacol and pyro-
guaiacin CggH^jOs. [183°]. Potash fusion gives
protocatechuic acid. When bromine is dropped
into a solution of guaiaretio acid in CS^ there
is formed CafH^jBrjOj which crystallises from
alcohol in needles.
Salts. — The guaiaretates of the alkalis are
crystallisable ; those of the alkaline earths are
amorphous pps. The neutral salts are stable
only in presence of alkali; when boiled with
water they are converted into acid salts. —
KjA"2aq: scales (from alcohol). — KjA"3aq. —
HkA"aq: obtained by boiling the prece£ng
salt with dilute alcohol ; crystalline pp. —
NajA"2aq : shining laminse. — NaHA"aq :
lamins. — ^BaA"a!aq. — Pb2Ca,H2204 : amorphous
pp.
Guaiaconic acid C^^fi^i?). [95°-100°].
Bemains in the mother liquor from which
sodium guaiaretate (v. sv/pra) has crystallised
(HadeUcb, J.pr. 87, 321). The solution is eva-
porated, the residue extracted with alcohol, and
the alcoholic solution treated with CO^. Amor-
phouB. Y. sol. alcohol, ether, chloroform, and
HOAc. LsBvorotatory. When heated with
EClAq at 180° it forms MeCl and pyrocateohin
(Uerzig, M. 3, 125, 823). Nitrous acid gas passed
into its ethereal solution forms di-nitro-guaiacol.
The K and Na salts are sol. water and alcohol ;
the Ba and Pb salts are insoluble.
GTJAIEKE C,jH,2. [98°]. Obtained by ^s-
tilling resin of guaiacum or pyroguaiacin with
Bino-dust (Botsch, M. 1, 618 ; Wieser, M. 1, 602).
Laminffi (by sublimation) with bine fluorescence.
Volatile with steam, Sol. alcohol and ether.
Gone. H^SO, forms a green solution ; on adding
water the hydrocarbon is not reppd. CrO, in
HOAc forms gnaiene-quinone C,2H,g02 which
by sublimation forms lemon-yellow needles,
[122°], m. sol. water, insol. NaHSOjAq. Guaiene
forms with picric acid a compound crystallising
in slender needles, [123°], v. si. sol. alcohol.
GXTAIOL V. Tiauo aiiDEHtde.
GUAITAHINE. The substance to which this
name was given by Nencki, was subsequently
called by him Fobmoquanamine (^. v.).
DIGUANIDE C,H,N. i.e. nH:C(NhJ>^^-
Bigiuumde. Ouwnadyl-gtumidine.
Formation. — 1. By heating a salt of guan-
idine with cyanamide; the yield being small
(Rathke, B. 12, 776).— 2. By the action of PCI,
or bromine on a mixture of tbio-urea and
guanidine sulphocyanide ; the yield is very
small. — 3. By heating di-cyan-di-amide with an
ammoniacal solution of Cu(0H)2 at 110° ; the
resulting copper derivative being decomposed by
HjS (Herth, if. 1, 88).
Preparation. — ^An alcoholic solution of di-
cyandiamide is heated with ammonium chloride
in a sealed tube for 8 hours at 105° (Smolka a.
Friedreich, M. 9, 228).
Properties. — The free base, liberated from its
sulphate by baryta, is amorphous and alkaline
in reaction. It expels ammonia from its salts.
Boiling diluted H^SO. splits it up into NH, and
COj.
Salts. — B"H2S04aq : crystals, v. sol. water.
— B"2H2S04aq : from the sulphate of the copper
derivative and H^S (Bmich, M. 4, 409) ; large
colourless crystals, with neutral reaction, v. sol.
water. — The hydrochloride and nitrate
crystallise in soluble needles. — ^B"H2FtClg 2aq :
soluble crystals. — Copper derivative
(C2HgNs)2Cu 2aq. Obtained by heating an am-
moniacal solution of cupric oxide with di-oyan-
di-amide (Herth, ilf. 1, 88). Large flat prisms
of brick -red colour; v. si. sol. cold, sol. hot,
water, forming a deep-violet solution, turned
blue by acids. Alkaline in reaction. —
(C2H,Nj2CuH2S04 3aq: slender red needles, si.
sol. water. Formed by adding ammoniacal
CUSO4 to a solution of a salt of diguanide.
References. — Iso-buiyi., bthtl-j methyIj-, and
Phentij diouanidb.
GUANIDINE CH5N3 i.e. HN:C(NH2),. Mol.
w. 59.
Formation. — 1. Together with parabanic
acid, and small quantities of xanthine, oxalurio
acid, and urea, by the action of HCl (S.G. 1*10)
and KCIO, (12 g.) on guanine (20 g.) in the cold
(Streoker, A. 118, 151). — 2. By heating biuret
to 165° in dry gaseous HCl (Finckh, A. 124,
335). — 8. By heating chloro-picrin for several
hours at 100° with a strong alcoholic solution of
ammonia (Hofmann, Z. [2] 2, 1073 ; 4, 721 ; B.
1, 145 ; A. 139, 107).— 4. In small quantity by
the action - of aqueous ammonia at 150° on
ortho-carbonio ether (Hofmann, A. 139, 111). —
5. Together with urea by the action of dry am-
monia on carbonyl chloride COCl, (Bouchardat,
G. B. 69, 961 ; Fenton, O. J. 35, 79a).^6. By
heating cyanamide in alcoholic solution with
ammonium chloride at 100° (Erlenmeye^, Z.
[2] 7,28; A. 146, 259).— 7. Byheatingoyanogen
651
GUANIDINE.
iodide with alcoholic NH, for 3 hours at 100°
(Bannow, B. 4, 161). According to Ossikovsl^
{Bl. [2] 18, 161) other products, including a
volatile fatty acid, are formed at the same time.
8. Together with urea, ammelide, and biuret,
by the electrolysis of a solution of ammonia
with carbon electrodes (MiUot, Bl. [2] 46, 244).
9. Among the products of the oxidation of egg-
albumen by KMnOf in presence of magnesia
(Iiossen, A. 201, 369).
Preparation. — Dry ammonium sulphocyan-
ide is heated for 20 hours at 180^-190°. The
residue consists mainly of guanidiue sulpho-
cyanide.no gaseous product being given off. The
guanidine sulphooyanide is purified by recrys-
tallisatiou from water or alcohol, and is con-
verted into the carbonate by mixing a solution
of it (100 g.) with a solution of K^COs (58 g.),
evaporating, and dissolving out the potassium
sulphocyanide with alcohol. The guanidine
carbonate is then recrystallised from water, and
the base liberated by dissolving in the cal-
culated quantity of dilute HjSO, and adding
the calculated quantity of baryta (Delitsch,
J. pr. 2] 8, 240 ; 9, 1 ; Volhard, J. pr. [2] 9,
10).
Properties. — Crystalline, strongly alkaline
mass, having a caustic taste. When exposed
to the air it deliquesces and absorbs carbonic
acid.
Reactions. — 1. When boiled with baryta
water it gives ammonia and urea ; the urea sub-
sequently breaking up into GO^ and ammonia
(Baumann, B. 6, 1376). Hence boiling concen-
trated acids and alkalis give only 00^ and NH,
(Ossikowsky, B. 5, 668). — 2. With hypobrondte
or hypochlorite of sodAwm, two-thirds of the
nitrogen is evolved, one-third remaining behind,
probably as cyanate (Fenton, O. J. 36, 14). —
3. Benzoic anhyd/ride acting at 100° on guan-
idine carbonate forms s-di-benzoyl-urea [210°]
(McCreath, B. 7, 1739).— 4. With chloro-fomdc
(chloro-carbonic) ether it forms guanidine dicar-
boxylie ether HN.C(NH.COjEt)j. This ether is
converted by alcoholic ammonia at 100° into
guanidine mono-carboxyUc ether (so-called
guanoUne) : HN:C(NHj)NH.COjEt (M. Nencki,
J. pr. [2] 17, 237).— 5. When the salts of guan-
idine ■mXia. fatty acids are heated there are formed
' guanamines.' Thus guanidiae formate forms
formo-guanamine CgH^Nj while guanidine acetate
gives acetoguanamine GjHjNj (v. infra). — 6.
Salts of guanidine heated with cyanamide form
diguanide (v. supra). — 7. When fused with urea,
guanidine carbonate forms guanyl-urea C^HgN^O.
8. An aqueous solution of guanidine carbonate
(2 mols.) boiled with an alcoholic solution of
phena/rM/raguirwne forms small colourless
prisms of the base C,bH,4N, probably
CsH,.C:N.0(NH2):NH
II . It is alkaUne in reao-
C.H,.C:N.C(NH,):NH
tion, absorbs CO, from the air, and forms a
crystalUne hydrochloride B"HjClj (Wense, B.
19, 761). — 9. In like manner benzil (1 mol.)
boiled with guanidine carbonate (2 mols.) in
dilute alcoholic solution forms benzil-di-gnan-
idide C,jH,5N, which may probably be written
HN:C(NHJ.N:CPh.CPh:N.C(NH J :NH. It forms
granular crystals, reacts alkaline, absorbs CO,
tcom (be air, and gives a hydiocbloride crystal-
lising in' long needles, and a platinochlorida
B"HjPt01, crystallising in plates (Wense, B. 19,
763).— 10. When benzil (1 mol.) is boiled with
a smaller quantity of guanidine carbonate (1
mol.) in aqueous-alcoholic solution, there is
formed benzil mono-guanidide C,5H,,N,0 pro-
bably 0:0Ph.CPh:N.C(NH2):NH. This body
iorms white oblong plates, sol. alcohol, insol.
water. It is alkaline in reaction (Wense, B. 19,
762). — 11. Aceto-aceUoacidiLigast&i. in alcoholic
solution with guanidine carbonate for a few
hours forms ' methyl-guanacU ' CjHjNsO t.e.
HN:C<^2.C0^>^°- ^^^ ^°^^ crystaUises
from water in prismatic needles; sol. hot, si.
sol. cold, water, v. si. sol. alcohol (Behrend, B.
19, 219). — 12. Phenyl-tMo-carbimide (3 pts.)
heated with alcohol and guanidine carbonate
(2 pts.) at 100° forms the crystalline compound
NHPh.CS.NH.C(NH2):NH [176°] (Bamberger,
B. 13, 1581 ; 14, 2638).
Salts. — B'HOl: regular needles; v. sol.
alcohol.— B'jHjPtClj: yellow needles or prisms,
V. sol. water, v. si. sol. alcohol. — ^B'HClHg^Cl,. —
B'HAuCl, : long needles. — B'HBr, : from guan-
idine carbonate (1 mol.) and bromine (3 mols.).
Large red prisms which easily lose bromine
(Kamenski, B. 11, 619).— B'HI,: prisms.—
B'HNOj : ppd. as a crystalline powder by adding
ENO, to a solution of the hydrochloride. Formed
also by rubbing guanidine sulphocyanide with
pure HNO, and filtering before deflagration
ensues (Jousselin, C. B. 88, 1086). Laminie
(from hot water) ; si. sol. cold water. Mixed
with silver nitrate it gives the crystalline com-
pound B'AgNO,. — Sulphate crystallises in
the regular system and is v. e. sol. water. —
B'^HjCOj. May be obtained by boiling the
sulphocyanide vrith diluted HjSO,, filtering,
treating with BaCOg, and allowing the liquid to
evaporate spontaneously (Jousselm). Dimetric
octahedra or prisms; v. sol. water, insol. alcohol.
Permanent in the air. When heated above 120°
it gives off water, CO, and NH„ and leaves a
yellow residue resembling meUon. — Oxalate
B'HjCjOjaq : colourless crystals, si. sol. water. —
Lactate forms regular crystals. — Cyanurate
B'CsNjOsHs : silky needles (Bamberger, B. 20,
68).— Sulphooyanide B'HSCy. [120°]. S.
73at0°; 135 at 16° (Bngel, £i. [2] 44, 424).
Formed as above. Large flexible laminm with
fatty lustre (from water or alcohol). Not deli-
quescent. At 150° it gives off NH3 and leaves
melam. Upon this salt mercuric oxide has no
action in alcoholic solution, but in aqueous
solution it gives a pp. composed thus:
B'.HSON,Hg(SCN)jHgO. The reaction taking
place as foUows: 3B'HSCN + 2HgO + 3HjO
= B'HSCN, Hg(SCN)„HgO -1- 6NH3 + 200^. The
pp. is converted by acetic acid into a mixed
acetate and sulphooyanide of mercury. The
same pp. is converted by concentrated HCl into
crystalline plates of ONsH„HC12HgCl2 (Byk, J.pr.
[2] 20, 330). Fused guanidine sulpho-cyanide
treated with finely divided lead (got by reducing
the oxide by hydrogen) is partiiUly converted into
'cyano-melamidine,' 0,H,3N,50, a body
which is soluble in water but is separated from
the original salt by its insolubiUty in alcohol.
Cyanomelamidine forms salts of melamine when
treated with HCl, FeCl, or E,SO,. With HNO,
GUANIDO-BUTYRIO ACID.
665
it forms the nitrate of ammeline. With KMnO^
it gives melamine (Byk, J. pr. [2] 20, 338).
Nitroso-gaanidine CH^N^O i.e.
N0.N.0(NBQ J. Formed by passing nitrons acid
gas through dry guanidine nitrate suspended in
oono. HNOj. The salt slowly dissolves, and on
adding water to the solution, nitroso-guanidine
is ppd. in slender needles, which are reorystal-
lised from boiling water (Jousselin, C. R. 88,
814). Needles ; si. sol. cold water and alcohol,
insol. ether. Boiling oono. KOHAq decomposes
it, giving ofE NH,. Warm oouc. HNOj dis-
solves it, and on cooling the salt B'HNOa sepa-
rates in large plates; this salt is efflorescent
and decomposed by water. HCl&q dissolves
nitroso-guanidine yielding slender iridescent
plates which are decomposed by water. On
dissolving nitroso-guanidine in water, adding a
drop of very dilute aqueous KOH and a drop of
aqueous FeSO, a purple colour is produced. If
alcohol and ether are added to the coloured
solution minute dark-red crystals are deposited.
Finely divided iron acting on nitroso-guanidine
suspended in water at 40° also forms a purple
colour, bat after some time this disappears,
NSC, being evolved. The solution evaporated at
60° leaves an unstable sulphur-yellow residue
which appears to be CH,N,0.
Acetoguanamine CjHjNj i.e.
CMe<^^£^(^^)j>NH (Weith, B. 9, 458), or
OMe<^^:^|^^KN (Glaus, B.9, 722). Ethemyl-
dagua/mde. Di-amido-meihyl-iriamUne. [265°].
Formed by heating dry guanidine acetate for
15 minutes at 230° ; the resulting acetoguan-
amine acetate being extracted by water and de-
composed by NaOHAq (Nencki, B. 7, 776, 1585).
Trimetric laminae ; si. sol. cold, v. sol. hot, water.
V. sol. alcohol. Slightly alkaline in reaction.
Chlorine passed into acetoguanamine suspended
in water forms a granular pp. C4H5CI2N5
(Nencki, B. 9, 237). This is insol. water, sol.
alkalis ; by heating with dilute HOI it is con-
verted into an isomeric body which crystallises
from dilate acetic acid in needles, is insol.
alkalis and forms the salts (C,Hs01jN5)jH2PtCla
and C^HsOLjNsAgNOa.
Salts. — B'H012aq: tables or prisms. —
B'jHjPtOls: yellow crystalline pp.; v. sol.
water. — B'HNOj : prisms, v. sol. water. —
B'jH2S04 2aq- plates, v. e. sol. water. —
B'jA^NOa : small plates (from hot water).
Acetognanide O^HgN^O i.e.
CM««&^^>H or CMe<^;H)>^-
Oxy-amido-methyl-MazoUne. Formed by boil-
ing acetoguanamine (1 pt.) with KOH (2 pts.)
and water (4 pts.) for 1^ hours, and ppg. with
HOAc (Nencki, B. 9, 233). CrystaUine pp.
Almost insol. water, alcohol, dilute HOAc, and
aqueous NH,, v. sol. alkalis and HCLAq. —
CANaN,02aq.-:C4H5KN,02aq.-C,H,N.OH01:
needles.— C^HjNjOAgNOs.
Acetognanamide CfH^NjO^ i-6-
C^<n£oS>NS or CMe<^;gH>N.
Di-oxy-methyl-iriazolme. From acetoguan-
amine (1 pt.), by warming with cone. HjSO, (2
pts.) at 150°. Small needles (from alcohol) ; v.
s. iwl. water, acids, ftnd ^P^^UB; b1. sol. alcohol.
On warming with nitric acid (S.Gr. 1-3) it yields
oyanuric acid. Chlorine passed into its aqueous
solution forms crystalline GjEsCljNsO,. SI. sol.
hot water, being decomposed thereby with forma-
tion of oyanuric acid. — B'HCl: needles.—
B'jHjPtCl, 4aq.
References. — ^Bbomo-, Chlobo-, Ozy-, Bekztii-,
EiHyii-, Methyl-, Naphthyl-, Niteo-phbnyii-,
Phenyii-, TolyIi-, and Xylyii- ouANmmEB,
GUANIDINE GABBOXTLIC XIHEB
C^H^NsOs i.e. HN:C(NHJ.NH.C02Et. Ouaniline.
[116^. Formed as below. Trimetric lamina
(from water or alcohol) ; the crystals contain aq
and melt at 100° ; when anhydrous it melts at
115°.— B'HNOa : trimetric prisms.- B'^HjSOi.—
B',HjPtCl,.
Guanidine dicarbozylic ether G,H„N,0, i.e.
NH:0(NH.002Et)s. [162^. Formed by slowly
adding ClGO^Etto a concentrated alcoholic solu-
tion of guanidine (Nencki, J. pr. [2] 17, 237).
Needles ; insol. water, v. sol. alcohol and ether.
Alcoholic NHg converts it at 100° into guanidine
oarboxylie ether.
GUANIDO-ACETIC ACID C^HjNjOj i.e.
NH:C(NH2).NH.GHj.G0jH. eiycocyamine.
Formed by allowing an aqueous solution of gly-
cocoll, cyanamide, and a little NH, to stand for
some days (Strecker, C. B. 52, 1212). Formed also
by heating glycocoll with guanidine carbonate
(Nencki a. Sieber, /. pr. [2] 17, 477). Crystals,
si. sol. water, insol. alcohol. — B'^HjPtClj 3aq. —
(0jHsN,O2)Cu : blue pp.— B'HCl : prisms.
By heating to 160° it is split up into water and
the hydrochloride of ' glyoocyamidine ' CjHjNjO
or NH:C<^jj-g-'QTTj>, a base which crystallises
in laminffi, v. sol. water, and forms the salts
CaH^NjOHCl and (C3H5N30)2H2PtCl, 2aq.
GTTANIDO-BENZENE p-STTLFHONIC ACID
C,HaN,S03 i.e. S0sH.C„H,.NH.C(NH2):NH.
Formed by heating amido-benzene ^ -sulphonic
acid (10 g.) with cyanamide (3 g.), water (200
CO.), and ammonia (23 drops) at 100° for three
days (Ville, C. B. 104, 1281). Brilliant needles,
V. si. sol. cold water, insol. alcohol and ether.
Neutral to litmus. Decomposes at 180°. Dis-
solves without alteration in H^SO, and HClAq.
NaOBr gives a purple colouration, with evolution
of nitrogen.
GTJANIDO-BENZOIC ACID G,H,NA *•«•
NH:C(NH2).NH.CeH,.C0jH. Benzglycocy.
amine. Formed by allowing an alcoholic solu-
tion of m-amido-benzoic acid and cyanamide to
stand, after addition of a little ammonia (Griess,
B. 7, 575). Formed also by boiling the dicyanide
of m-amido-benzoic acid with caustic potash
(Griess, B. 3, 703), and by treating the compound
NH:C(0Et).NH.CeH<.C02H with cone. NHjAq
(Griess, B. 8, 323). Thin four-sided plates (con-
taining aq) ; m. sol. hot water. Boiling baryta-
water gives uramido-benzoic acid, m-amido-
benzoic acid, urea, and NH,. — ^B'jHjPtOl,. —
B'HCl.
Beferenee. — Vol. i. p. 462.
Ouanido-di-benzoic acid v. vol. i. p. 157.
GrANIDO-BUTYRIC ACID CsHnNjOj t.e.
NH:G(NHjj).NH.CHEt.COjH. Oxybutyroey-
amme. Amidobutyro-oyamme. Formed by
adding cyanamide and a few drops of NH,Aq to
9i Qql4 saturated solntion of a-tunido-butyrie aoid.
856
GUANIDO-BOTYEIC ACID.
CryBtals are deposited in about a month, and are
pnrified by recrystallisation from water contain-
ing a little NH, (DuviUier, C. B. 91, 171). Long
slender needles, si. sol. cold water, t. sol. dilute
acids, almost insol. alcohol and ether. By boU-
ing with dUute ILgSO, it is converted into the
anhydride CSEt<j^^^^^, which crystal-
lises from water in long transparent needles
(containing aq) ; sol. alcohol.
guanioo-ethanb: suLPHomc acid
NH:C(NH:j).NH.CHj.CH;,.SO,H. Tawo-cyamme.
[226°]. Prepared by heating taurine (1-578 grm.)
with cyanamide (-85 grm.), and enough water to
dissolve them, for five hours at 120°. Evaporated
to crystallisation. The yield is 1-6 grms. (Bit-
trich, J. pr. [2] 18, 76). Hexagonal prisms.
Beadily sol. water. Insol. alcohol and ether. No
salts have been obtained.
GUAWIDO-HEXOIC ACID CH.sNsO^ i.e.
NH:C(NH2).NH.CH(CH;jI'r).C02H. 4mi&>-c<^pro.
eyamme. Formed by mixing an aqueous solu-
tion of leucine with cyanamide and a few drops
of NHjAq, and allowing the liquid to stand for
some time (DuvilUer, C. B. 104, 1290). Badia-
ting plates ; si. sol. cold, m. sol. hot, water, si.
sol. alcohol. When boiled with dilute H2SO4 for
several hours it changes to the anhydride
/NH.CO
NH:G^ I , which crystallises in
\nh.ch.c,h,
groups of needles; S. (alcohol) 17 at 22°; si.
sol. cold, m. sol. hot, water. This anhydride
(' amido-oaprooyamidine ') readily takes up water,
reproducing guanido-hexoio acid.
a-GTTAHIDO-FBOFIOSriC ACID v. Ala-
CBEATIHE.
j3-Guauido- propionic acid 0,'E,'S,0. i.e.
NH:0(NH2).NH.CHj.CHs.C02H. Formed by
adding a little NHjAq to a solution of iS-amido-
propionic acid (20 pts.) and cyanamide (7 pts.)
(Mulder, B. 8, 1261; 9, 1902). Crystals; not
decomposed below 200°. — B'HCl : very deUques-
eent needles.
o-6TrANID0-VALEBIC ACID C^M^^fi^ i.e.
NH:C(NH,).NH.CHPr.CO,H. ' Oxy - valero -
t^amine.' From a-amido-valerio acid, an
aqueous solution of cyanamide, and a little
NH, (Duvillier, C. B. 91; 171). Small cubic
crystals, si. sol. water, v. si. sol. alcohol ; insol.
ether. Boiling dilute H2SO4 converts it into the
/NH.00
anhydride CsH„N,0 or NH:C<; | , which
\NH.OHPr
forma delicate needles (containing ^aq) ; m. sol.
water and alcohol.
OTTANIliINE V. Guasidine oasboxyuc eiheb.
GUANINE OsH^NsO i.e.
<NH.OH:O.NHv
I >C0 (Fischer, B. 15, 455).
NH- — C : n/
Mol. w. 151. Occurs in all kinds of guano,
especially in Peruvian guano (Unger, A. 61, 395 ;
59, 58). Constitutes the greater part of the
excrement of the garden spider, and found in
the green gland of the fresh-water crayfish, and
in the Bojanian organ of the pond-mussel
(Qorup-Besanez a. F. Will, A. 69, 117 ; Griffiths,
Pr. 38, 187). Found in the pancreas of horses
(Soberer, A. 112, 257) and oxen (Baginsky, S.
i), 396), in the scales of the hleak (Barreswil,
C. B. 53, 246), and in the excrement of the
heron (Hoppe-Seyler, Med.-Ghem. Unters. 1871,
682). Guanine occurs as a concretion in tha
knee-joints of pigs suffering from guano-gout
(Virchow, Z. 1866,377), and perhaps also in the
urine of such pigs (Fecile, A. 183, 141). It has
also been found to the amount of 5 or 6 p.o.
in the sperm of the salmon (Piccard, B. 7, 1714),
and, together with other bases, in the extract
obtained by boiling yeast with water (Schiitzen-
berger, B. 7, 192). Kossel {H. 8, 404) finds
guanin in the liver, spleen, and embryonic
muscle of oxen.
Preparation. — Guano suspended in water is
gradually mixed with milk of lime ; the liquid
is heated to boiling, and the brown solution is
strained through a cloth filter, this treatment
being repeated till the liquid becomes colour-
less. Guanine and uric acid remain almost
wholly undissolved, and this residue is now re-
peatedly boiled with carbonate of sodium, and
the united solutions are mixed with acetate of
sodium, and then with hydrochloric acid in
sufficient quantity to produce a strong acid re-
action. The pp., consisting of guanine and uric
acid, is washed with moderately dilute hydro-
chloric acid, then boiled with the acid, and the
solution of hydrochloride of guanine, filtered
from the uric acid, is evaporated. The hydro-
chloride of guanine thus obtained stUl contains
uric acid, to remove which the guanine is ppd.
from the solution by boiling with dilate am-
monia, then dissolved in hot nitric acid to de-
compose the uric acid ; and from the nitrate of
guanine, which crystallises from this solution,
the pure base is ppd. by ammonia (Strecker, A.
118, 151). AccoriUng to Neubauer and Kerner
{A. 101, 318), pure guanine is most easily ob-
tained by dissolving the compound of guanine
with mercuric chloride in very dilute hydro-
chloric acid, decomposing the compound with
H2S, and ppg. the colourless filtrate with am-
monia.
Properties. — ^White amorphous powder, insol.
water, alcohol, and ether. It is si. sol. cone.
NHjAq, and is deposited as crystals by spon-
taneous evaporation of the ammoniacal solution
(Dreohsel, J.pr. [2] 24, 44). When guanine is
evaporated with fuming HNO3 a yellow residue
is left, which is turned red by ammonia, and
then becomes purple on warming (c/. Von Briicke,
M. 7, 617). A solution of a salt of guanine
gives an orange pp. with KjCrO, and a brown
pp. with KaFeCyj. A saturated solution of picric
acid gives an orange-yellow pp. (Capranica, S,
4, 233).
Beactions.—l. Nitrous acid converts it into
xanthine, imidogen being displaced by oxygen
(Strecker, A. 108, 141) 2. KCIO, and HOI form
guanidine and parabanic acid, together with
smaller quantities of ozalurio acid, xanthine,
and litea.— 3. KMnO, and NaOH at 80° form
oxyguanine C,^tJS,0„ which may be ppd.
by acids as a jelly, insol. water, alcohol, and
dilute HClAq, sol. alkalis (Kerner, A. 103, 251).
With ammoniacal AgNO, oxyguanine gives a
silver derivative.
Salts. — The compounds of guanine with
acids are decomposed by water. Guanine does
not appear to form an acetate or formate. —
B'HOlsq: delicate needles, deposited fram a
GUM AMMONIAC.
657
Bolution ot gnanine in hot oono. HCIAq. —
B'HCa2aq (Soberer, A. 112, 277).— B'HjClj:
from guanine and gaseona HCl; gives off half
its acid at 100° (Unger).— B'EBr aq : prismatic
needles.— B'HI aq : prismatic needles, b1. sol.
water, v. aoL HIAq.— B'HOlPtOl, 2aq (?) : orange-
yellow crystals (U.).— B'jHjCLtHgOlj aq : ppd.
when alcoholic HgOl, is a^ded to a strong solution
of gnanine hydrochloride.— B'jHjOLjZnOljSaq:
large crystals, obtained by adding guanine hydro-
chloride to a strong solution of ZnClj. —
B'^HiCUOdjOl,, 9aq;. — B'HNOj l|aq : hair-Uke
interlacing needles, deposited from a solution
of guanine in boiling HNO, as it cools. —
B'(HN0,),2aq: short prisms.— B',(HN0s),4aq.—
B;.(HN0,)5 5W— B'^SO, 2aq : obtamed by
diluting with water a solution of guanine in
oono. HjSOi. Long needles. — B',(Hj0204), :
separates as crystals on mixing a solution of
guanine hydrochloride with one of ammonium
oxalate.— Tartrate B'sfHjOjOJj 2aq : yellowish
radiating nodules.
Metallic .derivatiTes C,H,Na2N,0 4aq :
deposited on adding alcohol to a strong solution
of NaOH saturated with guanine. Confused e£Qo-
rescent lamins, which rapidly absorb GO, from
the air. Decomposed by water. — OjHjBaNsO (at
110°) : pointed prisms. Separates on cooling
from a solution of gnanine in baryta-water. —
B'HgCl, 2^aq : obtained as a crystalline powder
on adding cold saturated aqueons HgCl, to a so-
lution of guanine hydrochloride. V. sol. acids
and KCy aq.— B'AgNOa : flocculent pp. ; formed
by mixing solutions of silver nitrate and guanine
nitrate. Crystallises from hot HNO, in slender
needles (Streoker).
Seference. — BBOMo-OTiAiiiinE.
GtVASOJiTS'&v. GuAinnmE CABBOzyuoEiHEB.
GUANYI-PHENYL-THIO-TTKEA C.SN.H,.
».e. NHPh.CS.NH.C(NHj):NH. [176^. Prepared
by heating a mixture of phenyl-thiecarbimide
(3pts.), guanidine carbonate (2 pts.), and alcohol'
at 100° (Bamberger, B. 13, 1680 ; 14, 2638).
Colourless monoclinic crystals. Y. sol. alcohol.
Alkaline in reaction. Slowly decomposed by
boiling water into guanidine, phenyl thiooar-
bimide, aniline, HjS, and CO,. BoUmg HCIAq,
forms guanidine, aniline, H^S, and CO,.
S alts. — 'B'HCl : long glistening needles, more
Bolnble in alcohol than in water ; on boiling with
water it evolves H2S ; CnSO^ produces a violet
pp. turning black on heating. — B'^H^SOf" : pearly
plates. — B'^H^C^Of" : white glistening sc^es. —
B'C„H;j(NOJaOH: yellow felted needles.
GUANYL-THIO-rEEA CjHjN^S i.e.
SC(NH2).NH.C(NH2):NH. ThAodAeyamMcmmlme.
White glistening prisms ; m. sol. cold water.
S'ormaUon. — 1. By digesting di-cyan-diamide
with aqueous H^S (Bamberger, B. 16, 1469). —
2. By heating guanyl-nrea with aqneous H^S
(B.).— 3. I^om CSOl, and thio-urea at 110°.—
4. 1^ small quantity by the action of PCl^ (1 mol.)
on thio-nrea (3 mola.) (Bathke, B. 11, 962).
BeacUom. — Silver salts readily displace the
S by 0. On heating with ammoniac^ AgNO,
it is resolved into HjS and di-cyan-diamide.
When heated alone at 100° it changes to lihe
isomeric guanidine sulphooyanide.
Salts.— B",H,C204 2aq : sparingly soluble
crystalline ■pp.—'B"'B^Ot* : white si^ needles.
— B"HC1.
Vol. IL
OUANn-TOEA 0 ANiO lA
00(NHj).NH.C(NH,):NH. Di^m-cK-amidme.
Formation,. — 1. By evaporating a solution of
di-oyan-di-amide (CN)2(NH,)2 in dilute HjSO^
(Haag, A. 122, 26), and is therefore also formed
by the action of dilute HgSO, or E,PO« on cyan-
amide (Banmann, B. 6, 1374). — 2. By fasing
guanidine carbonate (1 pt.) with area (2 pts.)
(Banmann, B. 7, 446, 1768).— 3. By heating a
mixture of oarbamio ether (2 pts.) and guanidine
carbonate (1 pt.) at 160° as long as alcohol dis-
tils over (Bamberger, B. 20, 68). — i. A mixture
of guanidine hydrochloride and potassinm cyan-
ate is heated at 180° (Bamberger).
Prejaaration. — The base, prepared by any of
the above processes, is ppd. from the aqneona
solution of the product by OuSO, and NaOH.
The resulting copper derivative is then decom-
posed by HgS.
JProp&^s. — Strongly alktJine crystals ; ab-
sorbing CO, from the air. V. sol. water and al-
cohol. EGIO, and HCl oxidise it to guanidine.
Boiling baryta-water converts it into urea, CO,,
and NHa. On evaporating a solution of guauyl.
urea carbonate there is left guanidine carbonate,
NHg and CO, having been given oS.
Salts. — ^B'HGl|aq: laminie, v. sol. water
and alcohol. — B',H^tCl, : small orange crystals.
— B'HNOj: needles. — Aurochloride: long
golden needles. — B',H2S04 2aq : long needles.—
BOBCjCOs: crystalline powder. S. -67 at 18°.—
B',H2C204.
GTTII. This term is applied to carbohydrates,
whether produced by plants or animals, which
are amorphous, insoluble in alcohol, but form
a sticky Uqnid with water, in which they either
dissolve or swell up greatly. By nitric acid the
vegetable gums are oxidised to mncio and oxaUo
acids. They give no colouration with iodine
either before or after treatment with cono. H,S04.
Boiling dilute H,S04 converts them into glucose
or a sugar C,H,20,. Thus dextrose (glucose) is
formed from lichenin ; lavulose is formed from
leBvnlin; galactose is formed from galactin,
agar-agar, some kinds of gnm arable, and a gnm
in lucerne and other leguminous plants ; whil^
arabinose is formed from gum-arabic, cherry
gnm, gum tragaeanth, and the gum in. the ceU
walls of beet-root and poppies (Bauer, J.pr. [2]
30, 388). Gums are described under Aoas-aoab,
Abasik, Bassobin, Cebasin, DBSnUNB, DieXIBIN,
Gamboqe, Gelose, GbevhiLea ouu, Eaubi gum,
IlAOIOSIN, LffiVUIiAKE, L^IVCLIN, LlOHENIN, MUOI-
uflE, Pboibids, Appendix C, Quebbacho ocii,
Shellao, SdisiBni, Tbhioin.
GTm AMUONIAC. The dried sap of Dorema
aimmomaawn. It is partly soluble in water, but
contains also an insoluble resin (Johnston, A,
44, 328 ; Hirschsohn, J. 1876, 869 ; Moss, J.
1873, 867). When fused with potash it givea
resorcin and protocatechuic acid. The portion
of gum ammoniac (from Morooco]| soluble iq
alcohorgives by potash-fusion an acid C,^„O0
which forms minute crystals, sL sol. water, n).
80I. alcohol, melting with decomposition at 265°,
and giving with FeCl, a violet colouration (Gold-
Bohmiedt, B. 11, 860). HNO, acting on gum
ammoniac forms tri-nitro-resoroin. Distillation
with zinc-dust forms m- and j)-zylene, m-ethyl-
toluene, [2:l]C,H4Et(OMe), and a hydrocarbon
C„H„ (235°) whidi 00 oxidation with chromig
6S8
GUM AMMONIAC.
mixtate fonas benzole and acetic aoidB and le-
sinous productB (Ciamician, B. 12, 1663 ; O. 9,
313).
GITU, ANIMAL, v. Pboteids, AppencUx O.
GXrU ASABIO V. Ababih.
eVM BENZOiiir v. vol. i. p. 477.
GTJM, BBITISH, v. Dextbin.
GUMMIC ACID C^,oO,o (Beichardt). This
name was applied by Fremy to aiabin, but trans-
ferred by Beichardt {A. 127, 300) to an acid
formed in the oxidation of glucose by Fehling's
solution. Felsko (A. 149, 356; Z. [2] 5, 228),
working under Beiohardt's direction, gave the
formula CeH,jO,„ but according to Clans (J. pr.
[2] 4, 63) gommio acid is more or less impure
tarironic acid.
Uetagnmmic aoid v. Ababd? and Gebisin.
GITII BESIirS. "Iho hardened milky juice
which exudes from incisions in the stem or roots
of some plants. They are partly soluble in water
(gum) and part of the residue is soluble in alco-
hol ^esin). Examples: asafoetida, aloes, gal-
bannm, gamboge, gum ammoniac, myrrh, oUba-
num, opoponax, and seammony.
GUTS. SENEGAL v. ABism.
GUN COTTON v, Ceudulose.
GUNFOWSEB. A mixture of charcoal, nitre,
and sulphur, which when burnt produces large
volumes of gases chiefly CO, COj, N, H, HjS, and
0 {v. DiOTIONAET OF XEOHNIOiL OHEMISIBT).
GUBJUN BALSAU v. Wood on..
GUBJUNIC ACID v. Wood oil.
GTTTTA FEBCHA. A substance resembling
caoutchouc obtained by boiling to dryness the
milky sap which exndes from incisions in the
bark of the Isoncmdra Percha, Sapota MiielUri
(Bleekrode, 2242'. cM». a'j^. 1, 403), and Bassia
FairMi.
Gutta percha is a brownish-red mass, S.G,
•98. It is a very bad conductor of electricity.
It softens at about 48°, but never possesses the
elastic character of caoutchouc. It is deposited
from its solution in CS2 in a very porous mass.
Gutta percha is insol. water. It dissolves easily
in benzene, CSj, chloroform, and oil of turpen-
tine. It is not attacked by solutions of HCl,
KOH, or HP. Hot cone. HjSO, carbonises it.
HNO, converts it into a yellow resin.
According to Payen (C B. 35, 109) gutta
percha, purified by solution in CS,, consists of
three hydrocarbons : 'gutta' a portion insoluble
in boUing alcohol, amounting to 75 to 82 p.c. ;
* alban ' a portion soluble in boUing, but inso-
luble in cold, alcohol, amounting to 19 to 14 p.c. ;
and a yellow resin ' fluavil,' soluble in cold al-
cohol, and amounting to 6 to 4 p.o. of the whole.
Gutta CigH,,. Obtained by exhausting gutta
percha with boiling alcohol and ether, dissolv-
ing the residue in chloroform, and ppg. by al-
cohol (Oudemans, Bep. chmi. app. 1, 455 ; Yon
Baumhauer, J. pr. 78, 277 ; Adriani, Z. 1860,
496; Hofmann, 4, 116, 297). White powder,
cakes together and becomes transparent at 100°,
begins to melt at 150° ; at 180° an oil distils
over, and at 280° it froths strongly. It is insol.
alcohol and ether, sol. cold chloroform and CSj,
sol. hot benzene and oil of turpentine. After
exposure to the. air it becomes soluble in ether.
Gutta is strongly attacked by ozonised oxygen.
Gone. HGlAq attacks it, apparently forming com-
pounds containing chlorine. On dry distillation
it behaves like caoutchouc, giving isoprene CsH„
caoutohene C,gH,„ heveene (Greville Williams,
C. J. 16, 124), and a volatile aoid. When
exposed to air and light, especially at 25° to 30°,
it is completely deprived of ^flexibility through
oxidation (Hofmann, C J. 13, 87 ; Adriani, O.N.
2, 227, 289, 313). Gutta percha may be keptfor
a long time nnohanged under water or in the
dark (W. A. Miller, 0. J. [2] 3, 273).
Alban. White crystalline resin; best ob-
tained by extracting gutta peroha with ether,
and boiling the resulting extract with alcohol
to remove fluavil. Begins to melt at 100°, and
is perfectly fluid and transparent at 180°. InsoL
water, alkalis, and acids ; v. sol. oil of turpentine,
benzene, CS2, ether, chloroform, and hot alcohol
(Payen, C B. 35, 109). According to Oudemans
(B6p. cMm. app. 1, 455) alban from Indian gutta
percha may be represented by the formula
0,oH,eO, and at 130° by C^oH^O, and melts at
140° ; S. (alcohol) -61 in the cold ; 6-4 at 78°.
V Fluavil CjoHajO. [42°] (Oudemans); Yellow
resin ; sol. alcohol, ether, benzene, oil of tur-
pentine, CS2, and chloroform, remaining as an
amorphous mass when these solutions are
evaporated. Cono. HGL&.q dissolves it without
decomposition.
Gutta percha from Bassia Parkii resembles
ordinary gutta percha in its physical properties,
and has S.G. '976. It is much less soluble in
light petroleum, ether, HO Ac, and oil of turpen-
tine, but is.ec[ually soluble in CS^, chloroform
and benzene. It consists of gutta (91*5 p.c),
alban (6 p.c), and fluavil (2-5 p.c.) (Heckel a.
SohlagdenhauSen, O. B. 101, 1069).
GYBOFHOBIC AOID CjAjOis. An aoid
obtained from two lichens, Qyr(^hora pustuUUa
and Lecanora tartarea, collected in Norway for
the manufacture of archil. The lichen is mace-
rated with milk of lime, and the flltrate ppd. by
HCl; the pp. is dissolved in boiling alcohol,
containing animal charcoal, from which the
acid crystallises ' on cooling (Stenhonse, P. T.
1849, 398). Small soft crystals; nearly insol.
water, v. si. sol. ether and cold alcohol, m. sol.
boiling alcohol. Its solutions do not redden
litmus. Boiling aqueous EOH or baryta resolve
it into CO, and orcin. Bleaching-powder reddens
its solution. When mixed with NH, and ex-
posed to the air it forms a purple substance.
Boiling alcohol forms orsellic ether. Gerhardt
{TraAti, 3, 818) regarded gyrophorio acid as
identical irith leoanorio 01 evermo aoid.
HiBMATOXYLTO.
659
H
HXUATEIK V. HxiUTomiM.
KMTHMIS V. HdiMoaLOBiH.
ILSMATO-CAYSTALLIN v. H^emoslobin.
H^UATO-GLOBULIIT v. H^moslobih.
ELSUAXOISHT v. Qsmoslobin.
HXUATOIN V. HiBMOoiiOBiN.
HJBUATOIIN p. HajMOGLOBPt.
E2:mAX0-F0BFHTRIN v. Hjbuoolobin.
RSlIATO-FOJElFHyBOIOIII v. HiEMo-
OLOBIN.
BLSKATOXTLIN C.jHuO,. HiBwaWw. A
oolonrless crystalline sabstance from which the
colouring matter of logwood {Htematoxylon,
canvpecMawum) la derived (Chevreul, A. Ch. [2]
80, 128; 82, 53, 126 ; Gtolfier-Besseyre, A. Ch.
[2] 70, 272 ; Erdmann, A. 44, 292 ; Hesse, J. pr.
75, 216 ; A. 109, 332). Prepared by leaving the
commercial extract of logwood, previously mixed
with sand, in contact with five times its volume
of wet ether for several days, with frequent
shaking; the extract is evaporated, and the
residue recrystallised from water containing a
little ammonium sulphite. Dimetric crystals
(containing 3aq). When a supersaturated solu-
tion is allowed to stand in the cold it deposits
hemihedral trimetric crystals (containing aq).
The monohydrate is also obtained in granular
crystals by pouring a solution that has been
saturated at 100° into a cold vessel containing
a small quantity of a solution of acid ammonium
sulphite. Hsematoxylin is si. sol. cold water, v.
sol. alcohol and ether. It dissolves in a satu-
rated solution of borax more easily than in pure
water, the solution being neutral or slightly acid,
and exhibiting a bluish fluorescence. Alcohol
does not ppt. borax' from this solution. From
the solution in borax the heematoxylin is ppd.
by acids in the monohydratedform, and by salts
(e.j. NaCa, KCl, NH^Cl, K,FeCy„and HNH^SO,)
as an amorphous mass. Heematoxylin dis-
solves in warm NajS^O, forming a purple liquid
from which it is deposited on cooling in the
amorphous form. It also dissolves freely in
NajHPO,, the solution remaining alkaline.
Hsematoxylin has a sweet taste, resembling
liquorice. Its solutions are dextrorotatory,
[o] = 92-5° in a 1 p.c. solution. It reduces Feh-
iing's solution and ammoniacal AgNO, in the
cold. An aqueous solution of hsematoxylin is
not altered by contact with pure air or oxygen,
but, if the slightest trace of ammonia be present,
the liquid acquires a red colour due to hsema-
tein {v. infrc^. Thus if the solution is boiled
in a glass vessel it becomes purple by dissolving
alkali from the glass (Maschke, B. 7, 163S;
Ar. Ph. [3] 6, 34 ; Mitchell, Am. Ch. 6, 91).
PNOs oxidises it at first to hsBmatein, but ulti-
mately to oxalic acid. HjSO, and HCI have but
little action on it. Hematoxylin dissolves in
■ alkalis and alkaline carbonates forming a purple
solution, the colour being destroyed by acids
(Wildenstein, JV. 2, 9). Baryta-water added to
a eolation of hfematoxylin freed from air b^
boiling forms a white pp. which tnma blue u
exposed to air. Basic and normal lead acetates
Jive a white pp. turned blue to ait ; capric aoa>
tate gives a greenish-grey pp. which soon be-
comes dark-blue with a coppery lustre. SnCl,
gives a rose-coloured pp. Alum colours the solu-
tion red but gives no pp. BaCl, colours the
liquid red, and then forms a red pp. AuCl, is
reduced by hasmatoxylin. Ammonium vanadate
gives a bine-black colour (Wagner, D. P. J. 223,
681). According to Schiitzenberger a. Faraf (Z.
1862, 42) the violet solution of hematoxylin in
ammonia may be decolourised by heating for 48
hours at 100° in an exhausted tube ; the colour- '
less product, called ' haematinamide ' is re-
oxidised on exposure to air, becoming violet.
Besorcin and pyrogallol are among the products
of the dry distillation of hsematoxylin (B. Meyer,
B. 12, 1392). Potash-fusion gives pyrogallol and
formic acid (Erdmann a. Schultz, A. 216, 240).
Sodium-amalgam or zinc and dilute H^SO^ do
not reduce hasmatoxylin (Beim, B. 4, 329).
Chlorine, bromine, PClj, and HI yield resinous
products. According to Frfibault (J. Ph. [4] 23,
338) the red colour of alkaline solutions of
hsematoxylin is^estroyed by iodine.
Penta-acetyl derivative CieHgAcjO,.
[166°]. From hsematoxylin and AoOl (Brd-'
mann a. Schultz, A. 216, 232 ; cf. Beim, B. 4,
831). SUky crystalline tufts; becomes coloured
in moist air.
Bromo-hcematoxylin C,sE„BrO,. Dissolves
in aqueous EOH or NaOH with a blue colour, in
aqueous NH, with a red colour.
Pent-acetyl derivative C,eH,BrOeAo, :
[210°] ; fine colourless needles ; sol. alcohol,
acetic acid, benzene and chloroform. Formed
by adding bromine to a cold acetic acid solution
of penta-Boetyl-hsematoxylin (Buchka, B. 17,
683).
Si-bromo-heematozylin C„H,^r20,. From
hsematoxylin and Br in HOAc (Dralle, B. 17,
373). Deep-red needles. Decomposes above
120°. Its aqueous solution is brownish-red.
Penta-acetyl derivative CjsH^rjjApsOo.
From penta-acetyl-haematoxylin and Br in
HOAc at llO!' (D.). Crystals ; decomposes above
180°- without melting.
Esematoxylin-phthalein C^HagO,,. Pre-
pared by heating hsematoxylin with phthalic
anhydride (Letts, B. 12, 1651). Brown amor-
phous mass, insol. water, sol. alkalis, forming a
purple-red solution.
Esemateiu 0, AiOf S. -06 at 20° ; S. (ether)
■013 at 20°.
Preparat/ion. — ^Extract of logwood is dissolved
in hot water and, after cooling, NH, in slight ex-
cess is added. The solution is exposed to air
which changes hematoxylin to hsemat^n, the
ammonia compound of which is ppd. This pp.
(40 g.) is dissolved in hot water (1000 g.) contain-
ing acetic acid (100 c.o.), and the solution is
filtered. On cooling crystals of hematein
appear (Hummel a. A. O. Perkin, O. J. 41, 367 ;
cf. Halberstadt a. Beis, C. J. 41, 368 ; B. 14,
611).
Prc^erHes. — Mioroscopio reddish-brown
plates with yellowish-green lustre. Sparingly
soluble in water, alcohol, ether, and, acetic acid.
vu3
HiEMATOXYLIN.
Forms with NH3 a brown-violet Bolution, with
ccno. NaOH a purple-blue solution ; in air these
liquids turn red and finally brown. Freely
. soluble in cone. HClAq. It dissolves in alkaline
bisulphites, and is reppd. by hot dilute E2SO4.
Beactitms. — 1. Gold cone. EjSO, dissolves it.
On pouring the solution into water a reddish-
brown pp. of altered hsmatein is formed. On
adding glacial acetic acid to the solution in cold
cono. HjSO, an orange crystalline powder iso-
hsematein sulphate, G,sE„0j.S04H, is ppd.
This body is converted by dilute (80 p.o.)
alcohol into lustrous orange-red crystals of
{C,eH„Oe) AeHi.OsSO^H.— 2. With HOI at 100°
it forms orange-red needles ofiso-hsematein-
chlorhydrin C,gE„Og.Gl, soluble in water with
decomposition and separation of HCl. Its solu-
tion is orange. With alcoholic KOH it gives a
reddish-violet solution. Gone. H^SOj converts
it into iso-hsBmatein sulphate. — 3. With HBr
it gives a corresponding bromhydrin, C,GH„O^Br.
4. Decolourised by Zn and dilute H^SO,, but
not reduced to hsematoxylin thereby. Boiling
aqueous SO^ behaves in Uke manner (Beim). — 5.
AcCl gives no acetyl derivative.
Ammonium derivative G^HiolNHjjjO, :
violet-black grains ; forming a purple solution
in water, and a brownish-red solution in alcohol,
gives off NHj over HjSO,.
Iso-hsematein C,sH,jO,. A solution of the
chlprhydrin 0,aH„0501 gives with AgjO a solu-
tion which, on evaporating, leaves amorphous
iso-hsemat^n with green lustre.
Properties.— Solution in NaOH is red- violet,
' in NH, is dull red-purple ; with ammonio sul-
phide a red-purple pp. is got (hsematein is
nearly decolourised by this reagent). Lead
acetate gives a red-purple pp.
Iso-hcBmatein compounds dye with alumina
chocolate-red, with iron, slate to black. The
colours are faster than those of hEemateiu. The
generation of iso-hasmat^in in place of ordinary
hiematein from 0,eH„0j01 is peculiar. Perhaps
it is (0,sE,20s), as indicated by the sulphate.
(/3)-HaBmatein GeHijOsSaq. Deposited as
Bmall brownish-red tofts tcova an ethereal solu-
tion of hematoxylin to which a few drops of
HNO, have been added (Beim, B. 4, 331). It is
more soluble in boiling water than hGematein
(Erdmann a. Schultz, A. 216, 236). It is recon-
verted into hsBmatoxylin by boiling with aqueous
SO, 01 with zinc and dilute HjSO^. AoCl gives
an acetyl derivative [216°-219°].
H^mill' V. H^uoaLosiN.
HaiMOCHROMOGEN v. HiEMOOLOBis.
HaSMOCTASIN ». Pbotbids.
KffiMOGEOBIN (syn. Hcemato - ghbuUn,
hamato-crystalUn). This pigment composes
from 86-90 per cent, of the solid constituents of
the red blood corpuscles of vertebrates; it is
also found in the blood plasma of many inverte-
brate animals, and in the red odrpuscles of the
hsemo-lymph of a few invertebrates (Laukester).
For a complete list of the animals in the blood
of which it has been described «. Halliburton
{J. Physiol. 6, 332). It is found in the muscle-
plasma of most animals, even when none occurs
in the bloOd, as in some invertebrates (Iiankester,
PflOger's Archim, 4, 316) ; it is most abundant
ID the red musoles of rodents. It is also found
in the nerve-cells of Aphrodite aeuleata (Gamgee,
Physki. Chem. 420).
PrepwraUon. — ^Leidig (Zeits. f. wiss. Zool. 1,
116), Eeichert {Mailer's Archm, 1849, 197),
KoUiker (Zeits. f. mss. Zool. 1, 216) first ob-
served that blood from difierent sources de-
posited crystals of a red colour. Funke (Zeit. f.
rat. Med. N. F. 1, 184 ; 2, 204, 288) recognised
that they consisted of the red pigment of the
blood. Lehmann (Sitz. W. 46, 65), Lang (ibid.),
and Freyer (Die Blutkrystalle, Jena, 1871) have
also worked at the subject. The principal
methods for prisparing these crystals will be
found in detail in Gamgee's Physiol. Chem.
85-88. The crystals may be obtained with ease
from the blood of some animals (rat, guinea
pig) by simply adding water to the blood ; this
first dissolves the hemoglobin from the cor-
puscles, and vrithout further treatment the crys-
tals form in a few minutes. A very excellent
method consists in adding to the defibrinated
blood one-sixteenth of its volume of ether, or a
mixture of alcohol and ether; on shaking the
mixture the corpuscles dissolve, forming a lake-
coloured fluid, and in a period varying in differ-
ent animals from a few minutes to three days,
a thick magma of crystals is formed, which may
be purified by washing with 25 p.c. alcohol, and
by re-crystalhsation. In other methods the cor-
puscles are broken up by repeatedly freezing and
thawing the blood with or without the previous
addition of a quarter of its volume of alcohol,
and crystals are thus obtained. The blood of
the mouse is said to crystallise when drawn,
without any further treatment ; in septic diseases
in man, or by adding putrid serum to the blood,
there is the same crystalline tendency (C. J. Bond,
Lancet, Sept. 10 and 17, 1887). The crystals
obtained by all these methods are microscopic ;
larger crystals are formed by sealing blood which
has stood in the air for twenty-four hours in
narrow glass tubes, and keeping them for soule
days at 37°0. On then emptying their contents
into watch glasses the crystals form (Gschleid-
len, Physiol. Methodik, 361). For microscopical
investigation a very convenient method is to
mount a drop of blood in Canada balsam, and
the crystals separate in a few minutes (Stein,
Virchow's ArcMv, 97, 483). The crystals in all
these oases are generally spoken of as hemo-
globin crystals ; it would be more correct to
speak of them as crystals of oxy-heemoglobin,
the loose combination of oxygen and hemo-
globin that exists in arterial blood. Crystals of
pure or venous hemoglobin have, however, been
obtained by Hiifner and by Nencki and Sieber
{Chem. Soc. Abst. 1886, p. 482).
Crystalline form. — Not only does the hemo-
globin of different animals differ in the readi-
ness with which it crystallises, and in its solu-
bility in water, but also in crystalline form. As
obtained from the majority of animals, the
crystals are prisms or plates belonging to the
rhombic system ; the exceptions to this rule are
the guinea-pig, in which the crystals were at
first supposed to be regular tetrahedra (Kunde,
Zeits. far rat. Med. N. F. 2, 276), but have
since beeii shown by Von Lang to be rhombic
tetrahedra. In birds the crystals are often
tetrahedral. These crystals are doubly refract-
ing and pleoohiomfttiq, In three animals, tb|
HiSlMOGLOBIN.
661
fequirrel (E^Ulide), haUiBtdl (t'rejr^r), and mouse
(Bojanowski), six-sided plates have been de-
scribed. The statement regaiding mouse's
crystals is, however, erroneous. Bhombohedia
have been obtained from hamster's blood. Oc-
casionally six-sided plates are obtained from
rat's blood (Halliburton, Qtiart. Jow. Mic. Sci.
1887, 190). These crystals, if they are lying
flat, appear dark between crossed nicols, and
therefore belong to the hexagonal system. The
amount of water of crystallisation varies greatly
in the crystals from different sources, and it is
probably owing to this that the difference in
crystalline form is due (Hoppe-Seyler, Physiol.
Chem. 377 ; 0. Bohr, Untersuch. ilber d.
Sauerstoffaufnahme des Bhitfwrbstoffes, Kopen-
hagen, 188S; Halliburton, I.e.).
ComposiHon. — Hcemoglobin differs from most
' of the other proximate constituents of the body
in containing iron. Freyer's formula for it is
•C,„|fH„„N,5,FeSjO,„. Determinations of the
rsulphur by other observers were, however, con-
tradictory; on this ground Lehmann and others
-advanced the theory that hsmoglobin is not a
'Chemical unit, but consists of a colouring matter,
hffimatin, which contains the iron, mechanically
mixed with a crystallised proteid. A seeming
confirmation of this theory was advanced by
•Strnve {Zeit. Prakt. Chem. 1884), who extracted
hiematin from the crystals by alcoholic am-
inonia, leaving them colourless. Zinofisky
•\Zeit. Physiol. jOhem. 10, 16) points out, how-
>ever, that alcoholic ammonia is a powerful re?
agent, and shows that the conflicting results as
io the quantity of sulphur present are due to bad
suethods of preparation of the hemoglobin.
Adopting the ether method of preparing the
crystals (for the modifications of the method as
already described the original paper must be
consulted), he found that the empirical formula
for hsBmoglobin is CnjHujjNjHSjFeOj^s. By
heat, or by the action of strong acids or alkalis,
heemoglobin is decomposed into hsmatin
(CsBH,„N,Fe20,„) and a proteid or mixture of
proteids known under the name Globin (for the
properties of globin v. Proikcdb).
Properties. — Though crystallisable, haemo-
globin is not diffusible ; its colour differs with
the amount of oxygen with which it is combined;
the pure pigment has a purplish tinge ; the
oxygenated condition in which it usually exists
is a yellowish-red. In both conditions solutions
of the pigment show with the spectroscope typi-
cal absorption bands. The spectrum of oxy-
hcemoglobin varies with the concentration of the
solution ; in addition to a certain amount of ab-
sorption of both ends of the spectrum there are
two typical bands between the d and n lines,
the o band has for its centre the wave-length
579 ; the j8 band, which is wider and less well-
defined,has its centre at wave-length553(Hoppe-
Beyler) (see spectrum, 2). Stokesfirst showed that
on the addition of reducing agents to such a solu-
tion the colour of the liquid changes to that of
heemoglobin, and this has only one absorption
band, which occupies approximately the light
space between the two bands of oxyhsemoglobin
(see spectrum, 3). The most convenient redu-
cing agent to use is ' Stokes's reagent,' which
must always be freshly prepared by adding a
•mall quantity of citric or tartaric acid to a
solution of ferrous sulphate, and then ammonia
till the reaction is alkaline. Or a solution of
anmionium sulphide, or a stream of a neutral
gas like hydrogen may be used. If the solu-
tion which shows the spectrum of reduced hemo-
globin be agitated with the air or oxygen it once
more becomes brighter in colour, and shows the
two bands of oxyhemoglobin. This spectro-
scopic test is the one most usu4Ily applied for
the identification of hemoglobin. The bands
are still perceptible when the solution contains
only 1 part of hemoglobin in 10,000 of water.
Another test frequently used is to obtain crystals
of hemin (^. v.). The crystals of oxy-hemo-
globin dried in vacuo still retain 3-4 per cent,
of water of crystallisation, which is driven
off by heating to 110°-120°C. The dried sub-
stance may be heated to 100°C. without under-
going decomposition.
Hemoglobin gives all the tests of proteids.
Oxyhemoglobin has the power of decomposing
hydrogen peroxide. Freyer finds that 1 grm. of
hemoglobin can link to itself 1-67 c.o. of re-
spiratory oxygen ; Htif ner (Zeit. physiol. Chem.
i. 317) gives approxinmtely the same figure ; the
theory of A. Schmidt that hemoglobin has the
power of ozonising the oxygen it thus links to
itself has been disproved by Fflilger (PflMger's
ArchAv, 10, 252).
EsttmatUm of hcemoglobim. — (a) From the
amount of iron ; dry hemoglobin contains 0-42
p.c. of iron. A weighed quantity of blood is
calcined ; the ash is exhausted with hydrochloric
acid to obtain ferric chloride, which is trans-
formed into ferrous chloride, and titrated with
potassium pepnuanganate. (6) CdUrrimetrically
(Hoppe-Seyler ; Bajewsky ; Malassez) : the most
convenient instrument is Grower's hemoglobino-
meter (Lancet, vol. ii. 1878, p. 822). (c) Spectro-
Ecopically, by comparing the amount of absorp-
tion of light with that of a standard solution (v.
Hiifner, 2.c., Freyer, l.e. On the Spectrophoto-
meter, V. S. Lea, J. Physiol. 6, 239). The ab-
sorption coefficient of oxyhemoglobin increases
each time it is recrystalllBed (F. Eriiger, Zeit.
Biol. 24, 471). V. also Fleischl, MaVy's Jahrb.
zv. 149 ; Otto, ibid. 146 ; Quinquaud and Brany,
ibid. 151 ; E. Lambling, Arch, de Physiol. [4]
12,1.
Compounds. — Ozyheemoglobin. This loose
combination of oxygen and hemoglobin is formed
in the pulmonary or branchial capillaries, and
forms the oxygen carrier to the tissues to which
it goes, and where it parts with its oxygen, re-
turning in the venous blood for a fresh supply.
As already stated, this compound can also be
made artificially from hemoglobin when in solu-
tion outside the body. For the most recent work
regarding the dissociation of oxyhemoglobin v.
Hiitner, Zeit. physiol. Chem. 12, 568 ; 13, 285.
Carbonic oxide hemoglobiu is formed when car-
bonic oxide is breathed instead of, or mixed in
undue proportions with, oxygen. The formation
of this substance is the cause of death in poison-
ing from this gas, which is contained, for in-
stance, in the fumes of burning charcoal. The
compound has a bright cherry-red colour, is
much more stable than oxyhemoglobin. Its
absorption bands are very like those of oxyhemo-
globin, but they are situated rather nearer to
the b^ue end of the spectrum (see spectrum, 4) ;
663
H/EMOGLOBIN.
the addition ot reducing agents does not cause
any reduction to the condition of hasmoglobin.
It can be obtained in a crystalline condition,
and the crystals are of the same form as those
of ozyhffimoglobin, but are more stable. For
other tests for CO hemoglobin v. Eoppe-Seyler
{Zeit. physiol. Chem. 2, 131), Salkowski (ibid.
12, 227), Katayama (Virch. Arch. 1888, p. 63).
Nitric oxide hGemoglobin forms similar crystals,
Bnd in solution has an absorption spectrum re-
sembling those of the two preceding substances.
These three compounds are isomorphous, one
molecule of each gas being replaceable by one of
dither of the other two, and is presumably linked
with one molecule of hemoglobin. Compounds
of hemoglobin with acetylene and with hydro-
cyanic acid have been also described (Eoppe-
Seyler, Med. Chem. Unters. 2, 207).
llethsBiuoglobin. This is occasionally found
in the body ; e.g.ia sanguineous effusions and in
the urine. Our chief knowledge of it is, how-
ever, obtained from preparations of it from
hemoglobin made artificially. By simply allow-
ing blood to stand for some days it turns aoid,
and of a brownish tint, and its hemoglobin is
found to be whoUy or partially transformed into
methemoglobin. It may also be obtained by
adding oxidising agents to blood, or to solutions
ot oxyhemoglobin or hemoglobin, e.g. potassium
permanganate, potassium ferricyani^e, nitrites,
&o. (for a list of such substances v. G. Hayem,
Compt. Bend. 102, 698). On' the subsequent
addition of reducing agents, first oxyhemoglobin
' and then hemoglobin is again formed. This is
seen best by spectroscopic examination. The
reduction, however, cannot be efiected by simple
mechanical means like a vacuum or a stream of
hydrogen. The typical band of methemoglobin
is situated in the red between the c and c lines,
rather, nearer to the former (see spectrum, 5) ; in
a dilute solution three other bands are seen (see
spectrum, 6). Methemoglobin may also be ob-
tained in a crystalline form (guinea-pig, tetra-
hedra; rat, squirrel, horse occasionally, hexa-
gonal; in most other animals, rhombic). A
ready method of obtaining these crystals for
microscopic examination is by shaking a few
drops of amyl nitrite with a few c.c. of defibrin-
ated blood, and then on mounting on a slide a
drop of the mahogany-coloured mixture that
results, crystals appear in a few minutes (Halli-
burton, Quart. J. of Mic. Sci. 1887, 201). Other
methods consist in adding a nitrite and alcohol,
find freezing (Gamgee, PMl. Trans. 1868, 689,
where they are described, however, as a com-
pound of hemoglobin with nitrous acid), or ferri-
cyanide of potassium maybe used instead (Hiif-
ner, Zdt. Physiol. Chem. 8, 366). Sorby con-
sidered methemoglobin as a peroxyhemoglobin
(Quart. J. Mic. Sci. 1870, 400). Hoppe-Seyler
on the contrary believed that it was a suboxyhe-
moglobin, intermediate between oxyhemoglobin
and hemoglobin,' but that the oxygen was more
firmly combined than it is in oxyhemoglobin ;
he found by removing some of the oxygen from
oxyhemoglobin by means of an air-pump, or by
nascent hydrogen, that methemoglobin was
formed (Zeit. Phyiiol. Chem. 2, 150). Hufner
and Eiilz (ibid. vol. vii.), having been able to
obtain pure crystallised methemoglobin, have
found that the oxygen in both that compound
and in oxyhemoglobin are equal in amount bat
combined more feebly in the latter.
ParahamoghbiM. — This was described by
Nencki and Sieber (Arch. Exper. Path. u.
Pharmakol. 10, 331 ; Ber. 18, 2126) as a special
compound; but is regarded by Eoppe-Seyler
(Zeit. Physiol. Chem. 10, 331) as a coagulation
product brought about by the action of f^cohol
DsBIVATIVEg OF EaiMOQIiOBIN.
Hsmatin (CjaE^NgFejOio) is the brown pig.
ment obtained by thi action of acids or alkaUs on
hemoglobin in the presence of oxygen. This
decomposition occurs more readily in the hemo-
globin of some animals (dog, man, &o.) than in
others (herbivora) (Eriiger, Zeit. Biol. 24,
318). It may be obtained by adding acetic acid
to blood, and then extracting the hematin with
ether. Mac-Munn recommends the following
method: blood clot is extracted with rectified '
spirit containing sulphuric acid (1 in 17) ; the
extract is filtered and agitated with chloroform,
which assumes a reddish-brown colour and ia
separated, filtered, and washed with water to
remove the acid. On evaporating the chloroform
the hematin is obtained as a bluish-black powder
(J. Physiol. 6, 22). Eoppe-Seyler obtains hema-
tin from hemin, which is first dissolved in solu-
tion of potassium hydrate, and the hematin ppd.
by hydrochloric acid (Med. Chem. Unters. i,52S).
Hematin dissolved in an acid solution shows
four absorption bands (4 banded hematin or
hematoin) ; first, one between the c and n lines,
this is the most distinct and is nearer to the c
line than the corresponding band of methemo-
globin ; secondly, a faint narrow band close to
D ; thirdly, two much broader bands, one between
D and E and another between e and f (see spec-
trum, 7). When hematin is dissolved in an alka>
line solution (alkaline hematin) one band only
is seen, viz. a faint shading on the red side of
the D line (see spectrum, 8). There is, however,
a large absorption of the violet end of the spec-
trum. On adding reducing agents to alkaline
hematin, the bands of reduced hematin (hemo-
chromogen) are seen.
Eematm is insol. water, ether, alcohol, and
dilute acids ; v. sol. solutions of caustic alkalis,
and hot alcohol holding sulphuric acid in so-
lution. It can be heated to 180° without under-
going decomposition; at a temperature above
this it burns and evolves hydrocyanic acid, and
leaves an ash of oxide of iron amounting to 12-6
p.o.
Hemochromogen (CjjHjiN^FeOs). When
hemoglobin is decomposed in the absence of
oxygen, instead of hematiif, a substance of a
purple colour called hemoohromogen is pro-
duced, which is converted into hematin in con-
tact with oxygen. A solution of oxyhemoglobin
is freed from oxygen by a stream of hydrogen,
and then mixed with an alcoholic solution of
sulphuric acid or caustic potash (Hoppe-Seyler,
Med. Chem. Unters. 4, 623, 377 ; Zeit. physiol.
Chem. 1, 138). This substance is identical with
the reduced hematin of Stokes, obtained by
adding a reducing agent like ammonium sulphide
to alkaline hematin in the presence of proteidH
(Jaderholm, Maly's Jdhrb. 6, 85 ; Linossierr
0. B,. 104, 1296). Eemochromogen shoys two>
absorption bands, one midway between the n-
HiEMOGLOBIN.
663
aiid a lines, and the other oooupylng the space
between e and b (see speotraitt, 9). In testing
(or blood where the hsmoglobin has undergone
decomposition, as in old stains, the most readily
obtained spectrum is that of hsBmochromogen.
The stained fabric is extracted with a little
eaustio alkali, and ammonium sulphide or hypo-
sulphite of soda added; the two bands of hsmo-
immediately below d, and another nearly inter-
mediate between d andn (see spectrum, 10). The
alkaline solution has four bands: one between a
and D, two between d and e, and a fourth, whichi
extends through | of the space between b and
F (see spectrum, 11). A second iron-free deriva-
tive has been obtained from heematin by Hoppe-
Seyler ; he calls it hamatolm (C,sH„N,0,), it
1. Solar apectrum.
5. Spectrum of oxybsBmoglobin (0-37 p.c. solution). First band, A (89-664 ; seoond band, S55-S17.
3. Spectrum of hsemoglobin. Band, A S97-53S,
4. Spectrum of CO biemoglobin. First band, A S83-li84 ; second band, BiJ-BSl.
6. Spectrum of metbsemoglobin (concentrated solution).
6. Spectrum of metluemoglobin (dilute solution), First band, A 647-622 ; second band, A 687-671 ; tblrd band, A 662-
632 ; touxtb band, A 614-490.
7. Spectrum of acid basmatin (ethereal solution). First band, A 666-615 ; second band, A 697-677 ; tbicd band, A 667-
629 ; fourth band, A 617-488.
8. Spectrum of alkaline hssmatin. Band from A 630-662,
9. Speotrum of heemoohromogen (reduced hsematin). First band, A 669-542 ; second band, A 635-604.
10. Spectrum of acid hssmatoporphyxln. First band, A 607-593 ; second bai^d, A 585-536.
11. Spectrum of eU^aline heematoporphTrin, Fiist band, A 633-612 ; second band, A 689-664 ; third band, X 649-629 ;
fourth band, A 618-488,
The above measurements (after MaoMunn) are in millionths of a millimetre. The liquid was examined in a layer
one centimetre tbick. The edges of Ill-defined bands vary a good deal with the oonceutration of the solution, '
ohromogen or in weak solutions the better marked
band (that between n and e) then appear.
HsBmatoporphyrin (CesHjjNgOij). This pig-
ment is obtained by adding blood or purehsema-
tin to cone, sulphuric or hydrochloric acid ; the
action of the acid is to remove the whole of the
iron in the condition of a ferrous salt. It can
be ppd. by adding water to this compound. The
pp. is soluble in water and in alkaline leys. The
acid solution exhibits spectroscopically one band
is nearly insoluble in sulphuric acid and caus-
tic alkalis. Various derivatives of hematopor-
phyrin (hcBmatoporphyroidin, isohsBmatoporphy-
rin, &a.) are described by Nobel, (O. O. 1887,
538). HfiBmatoporphyrin occurs as a natural
pigment in many invertebrates ; e.g. in the dorsal
streak of the earth-worm. It is probably deriveo
here not from haemoglobin, but from histo-
hcematins which occur in these animals, and
which yield many of the decomposition products
664
ELfiMOQLOBlN.
of hsmoglcbin (MacMuun, 3. Physiol. 8, 384).
A deriTative called uro-basmatoporphyrin may
Occur in morbid homan urine (MaoMunn, J.
Physiol. 10, 71).
Hsemin. Hyd/rochloride of HtemaUn. This
is obtained for microscopical examination by
boiling blood vrith glacial acetic acid and a crys-
tal of sodinm chloride (fresh blood contains,
however, sufficient sodium chloride) on a slide ;
on cooling, rhombic crystals of a dark-brown
colour separate (Teichmann) ; this is one of the
best tests for blood. It has been prepared on a
large scale by Hoppe-Seyler, who ascribes to it
the formula 08jHj„NjFe20,„2HCl. Similar crys-
talline compounds are obtainable in which hy-
drobromic and hydriodio acids respectively take
the place of HCl in the above formula (V. D.
Harris, Brit. Med. J. 1886, 2, 103). Nencki a.
Sieber {Ser. 17, 2267; 18, 392; Monatschr. 9,
115; Arch. f. exp. Path, und Phcmmah. 24)
ascribe to hcematin the formula C,2H32N4£'e04 ;
and say hsemin crystals are composed of the
hydrochloride of its anhydride CsjHsoNiFeOs.HCl.
Their formula for hsematoporphyrin is C32H35N jOj.
Of this they describe an anhydride and a crystal-
line hydrochloride. It is isomeric with bilirubin.
Cyan-hsematiu. A compound with this name
is said to be formed when potassium cyanide is
added to an ammoniacal solution of pure hsema-
tin. It exhibits spectroscopically one band ex-
tending from s and e, and split into two by re-
ducing agents.
Nitric oxide ScBmatin. — This is produced
by passing nitric oxide into an alcoholic solution
of htematin. Its absorption bands resemble
those of oxyhemoglobin (Ijinossier, 0. B. 104,
1296).
Hsematoidin. Bverard Home (A Short Tract
on the Formation of Tumowrs, London, 1830)
first described certain microscopic crystals in
old extravasations of blood; e.g. in apoplectic
clots; to these Virohow (Virch. Archm, 1, 383)
gave the name hamatoidin, and recognised that
they were derived from the colouring matter of
the blood. The same substance occurs some-
times in an amorphous condition. The crystals
have also been found in the urine (v. BeckUng-
hauseik, Landois). The crystals are identical in
form with those of bilirubin, the chief colouring
matter of human bile, and give GmeUn's colour
reaction with fuming nitrio acid. It has the
same formula C^^^fl,. ' Neither hsematoidin
nor bilirubin show spectroscopic bands, but
absorb the violet end of the spectrum powerfully.
Although Holm (J. jpr. 100, 142) and Preyer (Die
Blutkrystalle, 187) deny the identity of the two
substances, Salkowski (Med. Chem. Unters. 3,
436) and the majority of physiological chemists
are, however, now of the opinion that the two
are identical. Holm and Preyer probably mis-
took the lipochrome (lutein) of the cow's ovary
for hiematoidin (Thndichom, Proc. B. S. 17,
255).
Other animal pigments. Bilirubin and the
other colouring matters of the bile, stercobilin,
the pigment of the feeces, certain urinary pig-
ments, melanin, the black pigment of the skin,
tetina, and of melanotic sarcomata, are aU pro-
bably derived from hssmoglobin. The allied pig-
ments myo-hsBmatin and the histo-hsematins
^?ill be desciibed nnder Musou. W. D. H.
HALOGHN ELEKEITTS. The toqr elements,
P, CI, Br, and I are classed together under the
name halogens, or salt-formers. The name was
given by Berzelius (Leh^buch, 1, 266 [5th ed.])
to those non-oxygenated radicles, simple or com-
pound, which combine with metals to form salts.
Berzelins regarded all salts as formed by the
union of a positive and a negative radicle. He
applied the name salt-former to the negative
radicles, more especially to those which do not
contain oxygen, and yet more partionlarly to the
simple radicles F, CI, Br, I, and the compound
radicle cyanogen. The nomenclature has been
maintained as regards the elements F, CI, Sr,
and I. The binary compounds of these elements
are usually called haloid salts. This name was
also introduced by Berzelius ; he used it to dis-
tinguish salts formed by the union of metals
with F, 01, Br, I, or CN from salts formed by the
union of two radicles, each of which contained
a common element, e.g. oxygen-salts, snlphar-
salts, selenion-salts, &o.
The halogens are found in combination very
widefy distributed. Metallic chlorides are very
numerous ; bromides, iodides, and fluorides occur
in smaller quantities. The elements themselves
are scarcely found in the free state in nature ;
iodine is said to exist in minute quantities in sea
water. Fluorides of all elements are known
except Br, C, CI, N, O, and some ten or twelve
metals (mostly rare metals which have not been
thoroughly examined) ; chlorides of all elements
except F have been isolated ; bromides of almost
all elements except F and 0 are known; and
iodides of all, or almost all, elements except F
have been obtained.
The compounds of the halogen elements
show resemblances both in composition and pro-
perties. If X = F, CI, Br, or I, the chief metallic
halogen compounds may be grouped under the
forms : —
(1) MX; Ms: alkali metal, Ag, Cu, or Au;
also Hg and Tl.
(2) MXj,; M = Be, Mg, Ca, Zn, Sr, Cd, Ba,
Hg; also Cu; In; Sn, Pb; Fe, Ni, Co; the Ft
metals.
(3) MX,; M:=A1, Ga, In, Tl; As, Sb, Bi;
Fe, Cr.
(4) MX«; M = Ti, Ge, Zr,Sn,Ce,Pb,Th,Mo,
U ; the Pt metals.
(5) MX,; M = Nb, Sb, Di, Ta; Mo, W.
(6i MX^; M = W.
The non-metallic halogen-oomponndB for the
most part belong to the following forma ^—
'i.) MX; M = H.
ii.) MX,; M = S, O, Se, Te.
iii.) MX,; M = B,N,P,Aa.
iv.) MX,; M = 0, Si, Te.
[v.) MX5; M=P.
The resemblances in the composition of the
halogen-compounds are further brought out by
the formulas of oxyacids. These oxyaoids for
the most part belong to the four classes HXO,
HXO2, HXO„ HXO, ; but no oxyacid of F has
yet been isolated.
The halogens are all strongly electronegative;
none of them replaces the hy&ogen of acids to
form salts. They combine directly with very
many elements, and much heat is usually pro-
duced in the process. F is especially energetic
in its reactions ; it reacts with cold water to form
HALOGEN ELEMENTS.
666
oaoniaed O and EF, whereas 01 only reaots
rapidly with water at a red heat, and the reao-
tionsot Br and I with water at high tempera-
tures are very slow.
A comparison of the binary compounds of
the halogens with H, and of the ternary com-
pounds withH and O, brings ont the resemblances
and differences between tiie four elements. The
compounds HX are all gases at ordinary tem-
peratures ; the formula HX expresses the com-
position of the molecules of each, but at low
temperatures the YJ>. of hydrogen fluoride is
greater than that calculated ftom the formula
HF. According to Thorpe and Hambly (C. 8.
Trans. 1888. 765 ; 1889. 163) there is no proof
of the separate existence throughout any con-
siderable temperature-interrtd of molecules
heavier than those whose composition is ex-
pressed by the formula HF. Aqueous solutions
of HX all contain acids ; whether the acidic re-
actions of these solutions are the reactions of
HX, or of a compound or compounds, HX.nH^O,
(?E2X.0H), cannot be regarded as yet finally
determined (v. vol. L p. 534 ; ii. p. 8). The
readiness with which stable acid fluorides, e.g.
EF.HF, BiFs.SHF, are formed, whereas corre-
sponding chlorides, bromides, and iodides are
few in number and unstable, points to the prob-
able existence of SL^, as the chemically reacting
unit of hydrofluoric acid. The formation of
these stable acid fluorides, and also of such
definite acids as SiP4.2HF ( = HjSiFa),BF3.HP
( = HBF,), SnF4.2HP ( = HjSnF5), differentiates
F from CI, Br, and I. But it is to be noted that
ECl, HBr, and HI combine with chlorides, bro-
mides, and iodides of Hg, Au, and Ft, to form
compounds which react as definite acids, e.g.
HjHgCl,, HjHgl,, HjPtBrj, HAuBr,. The heat
of neutralisation of HFAq is 18 to 19 p.c. greater
than that of the other acids, HXAq; on the
other hand, the relative affinity of HFAq is very
smaU, while HClAq, HBrAq, and HIAq are very
strong acids (c/. Ari'iNrrY, vol. i. p. 75).
According to the electrolytic dissociation-
hypothesis of chemical change in solution (v.
Fhtbical methods), the small affinity of HFAq
indicates that in solution only a few molecules
HF (or ? HjFj) are dissociated into their ions ;
whereas most of the molecules HCl, HBr, and
HI are dissociated in aqueous solutions of these
compounds. If this is so, it is probable that
the affinity of F for H is much greater than
that of either 01, Br, or I for H. The stability
of the fluorides generally, and especially the
stability of some non-metallic fluorides contain-
ing relatively much F, compared with the rela-
tively unstable character of corresponding chlor-
ides, bromides, and iodides, points to the affinity
of F for metals and non-metals generally, as
being greater than that of any of the other three
halogen elements ; e.g. compare PFj with PClj,
or BiF, with BiCla.
Br decomposes most iodides with liberation
of I ; CI decomposes both bromides and iodides
with liberation of Br or I respectively; the re-
actions of F with chlorides, bromides, and
iodides have not been yet examined.
The atoms of the halogens are monovalent
in gaseous molecules. T^he gaseous molecules
of CI, Br, and I are diatomic ; but the vapour-
densities of bromine and iodine indicate the
gradual dissociation of the diatomic molecaleg
Br, and I, into the monatomic molecules Br
and I as temperature increases. In the case of
iodine dissociation is almost complete at about
1500°, but the lowest S.G-. obtained for bromine
(at c. 1570°) agrees approximately with that cal-
culated for fBr,. The results ' obtained with
chlorine at c. 1500° indicate only a very slight
dissociation of the diatomic molecule G^. Ex-
periments in this direction have not yet been
made with fluorine. (For details v. Bbomine,
vol. i. p. 636 ; Celorinb, vol. ii. p. 11 ; 'and
Iodine.) I dissolves in ether and some other
solvents to form red solutions, and in CS2, &o.,
to form violet solutions ; Loeb's ^results (C. 8.
Trans. 1888. 805) indicate that the molecule of
I in the red solutions is probably l„ and that in
the. violet solutions the molecule is less complex
than this ; the values obtained were between I,
and Ij.
The halogens show a gradation of prominent
physical properties : F is a colourless gas, CI is
a yellowish-green gas easily condensed to a
liquid, Br is a dark-red liquid with low B.P.,
and I is a lustrous greyish-violet solid.
None of the halogens combines directly with
O. In their compounds with O and with 0 and
H the halogens show considerable differences.
No oxide of F or Br has yet been isolated ; the
oxides of CI which certainly exist are CLjO and
CIO2 ; only one oxide of I, viz. 1,0s, has been
certainly isolated. The oxides of CI are very
unstable explosive gases ; 1,0, is a stable well-
defined solid. CljO is the anhydride of hypo-
chlorous acid HCIO ; CIO, reacts with water to
form both .chlorous and chloric acids HCIO, and
HCIO3 ; I2O5 is the anhydride of iodic acid HIO,.
The oxyacids of CI are HCIO, HCIO,, HClOj,
and HCIO, ; only the last has been obtained apart
from water, the others are known in aqueous
solutions only. The oxyacids of Br are HBrO
and HBrO,; neither is known otherwise than
in aqueous solution. The oxyacids of I are
HIO, and HjIO^; both have been isolated as
solids. No oxyacid of F has yet been obtained.
Solutions of the two acids HCIO and HBrO are
obtained by similar processes, viz. by reactions
between HgO and ClAq or BrAqj when
Ba(C103)2, Ba(Br03), or Ba(IO,), is decomposed
by the proper quantity of dilute HjSOjAq, a
solution of the corresponding acid, HCIO,,
HBrO,, or HIO„ is obtained. Salts of these
acids are also obtained by oxidising chlorides,
bromides, or iodides; the conditions differ some-
what in each case (v. vol. i. p. 537 ; ii. p. 15 ; and
Iodine, oxyacids op, in vol. iii.). The following
thermal data regarding the formation of
hydracids and oxyacids of the halogens are
taken from Thomsen : —
m;=01 M=Br 11=1
[H,M] . . 22,000 8,440 -6,040
[H,M,Aq]. . 89,815 28,380 18,170
[H,M,0,Aq] . 29,930 26,080 —
[H,M,0»,Aq] . 23,940 12,420 55,800
Thomsen also gives these data : —
[M^O,Aq] . -8,490 -16,200 —
[HMAq,0»] .-15,880 -15,960 42,630
These numbers connect the differences between
the relative stabilities of the acids of CI,' Br, and I,
with differences between the quantities of energy
degraded in their formations from their elements.
660
HALOGEN ELEMENTS.
From Tbomsen'B thennal values we might
fairly expect HIO, to be a more stable acid than
HClOj or HBrO, ; we might also expect HIO,Aq
to be more readily produced by oxidising HIAq,
than HClOjAq or HBrO,Aq from a solution of
the corresponding hydracid ; and we might also
expect HI or HIAq to be more unstable than
the corresponding compounds oC CI or Br.
Chlorine water is an oxidising agent; but
the oxidising action of bromine water is very
small. Thomsen's thermal measurements con-
nect these facts with energy-changes ; he gives
the following constants of oxidation : —
(i) 2[H,Cl,Aq]-[HS0] = 10,270
(ii) 2[H,Br,Aq] - [H',0] = - 11,600.
(i) represents the heat produced when chlorine
decomposes water with formation of HClAq and
O ; (ii) represents the heat which disappears in
the corresponding reaction of Br with water.
The heats of formation of Cl^O and I^O, are
ve^ different : [Cl^O] = - 17,930 ; [ISO=] = 45,030
(Thomsen). If we compare the heats of forma-
tion of the oxyacids of Gl and Br with the heats
of formation of the oxyacids of I, we see that
the quantity of heat produced in the cases of 01
and Br decreases as the quantity of O increases,
but increases in the case of I as the quantity of
0 increases {v. sv^ra). The heat of formation of
periodic acid H^IOg is very much greater than
that of any other oxyacid of I ; Thomsen gives
[HM,0",Aq] = 18i,400, and [HIAq,0*] = 84,510.
Chlorine ani iodine are the only halogens
which form oxyacids higher than HMO,; per-
chloric acid is HOIO4, but the only periodic acid
which has been isolated is H^IO,. The compo-
sition of these two acids marks a point of differ-
ence between 01 and I. A great many periodates
are known which have few it any analogues
among the salts of 01 oxyacids. The periodates
may be arranged in four classes :
meta-periodates, e.g. EIO^, derived from the
hypothetical acid HID, ( = HsI0j-2Hj0) ;
meso-periodates, e.g. Fb3(I0j)2, derived from the
hypothetical acid H3IO5 ( = H5l0,-Hj0);
para-periodates, e.g. 'Ba^{IOg)„ derived from the
acidH^IO.;
^-periodates, e.g. Kffi,, derived from the hypo-
thetical acid B.J.JO, ( = 2H5lOs-3HjO).
(For details «. Periodates, under Iodine, oxx-
Acms or.)
.The oxyacids of CI and Br are all mono-
basic ; but periodic acid H5IO, is peutabasic,
and iodic acid EIO, or H^IjOg is probably di-
basic {v. Iodine, oxyacids of).
The affinities of the hydracids of CI, Br, anid
1 are approximately equal; the affinity of HFAq
is very small, less than i^th of that of HClAq.
The affinities of the oxyacids of the halogens,
except that of HClOjAq, have not yet been de-
termined ; HClOjAq is nearly as strong an acid
as HOlAq. The data for comparing the increase
in the affinity of an acid when H is substituted
by F, 01, Br, and I respectively are as yet very
meagre; from the measurements which have
been made the substitution of 01 seems to raise
the affinity a little more than substitution of Br
orF.
In the classification of the elements on the
basis of the periodic law (v. vol. i. p. 351 ; also
Classification, vol. ii. p. 203) the halogens are
placed in Group YIL, 01, Br, and I in odd series,
j (3, S, and 7), and F in an even series (3).
Group Vn. also contains Mn. The analogiei
between Mn and the halogens are but feebly
marked. Physically, Mn is a metal ; chemically
it is both metallic and non-metallic. The per-
manganates M'MnO, are generally isomorphoua
with the perchlorates, and with some of the
meta-periodates. There are many gaps in
Group yu. ; at least four elements belonging
to even series, and two belonging to odd series,
have yet to be discovered. The position of Mn,
following a series of metallic elements, and fol-
lowed by the metals Fe, Ni, and Co, would lead
US to expect pronounced metallic properties in
this element. Looking generally at the varia-
tions of properties in groups and series, we
should expect the analogy between CI, which is
the first member of the odd series of Group VII.,
and Mn, which belongs to the even series, to be
but feebly marked; we should also expect to find
the resemblances between the other even-series
members, of the group (when they are discovered)
^o be less distinctly marked than is the case in
the lower groups, and we should expect to find
all the odd-series members (01, Br, I, and two
elements yet to be discovered) to resemble one
another fairly closely.
For details about the individual halogens v.
Bbomine, ObiiObine, Fluobine, and Iodine.
M. M. P. M.
HAXOOENS, BINABY COUFOirNDS OF
THE. ' The four halogen elements form nume-
rous binary compounds both with metals and
non-metals. The compositions of the chief com-
pounds in question are represented by general
formulsB in the preceding article. Metallic
fluorides, chlorides, bromides, and iodides may
generally Jbe prepared by dissolving metals or
their oxides or carbonates in solutions of HF,
HOI, ECBr, or HI, and evaporating; many are
also formed by the direct union of the elements ;
some are prpduced by reactions between metaUio
oxides or hydroxides, and 01, Br, or I (probably
a similar reaction will be found to occur with
F). Metallic fluorides are not decomposed by
heat alone ; many of them are unchanged even
when heated with carbon or oxygen ; a few me-
taUio chlorides are decomposed by heat alone to
metal and d, e.g. PdCl4 ; some are reduced by
heat to lower chlorides, e.g. CuCl, to CuCl ; but
the majority are volatilisable without decompo-
sition ; metallic bromides and iodides as a class
resemble chlorides in their behaviour towards
heat ; many chlorides, bromides, and iodides are
decomposed with formation of oxy-haloid'com-
pounds or of oxides by strongly heating in moist
air or oxygen. As a class, metallic chlorides,
bromides, and iodides are soluble in water ; some
are decomposed to oxy-haloid salts ; on the
whole the iodides are less readily decomposed by
water than the chlorides or bromides ; metallic
fluorides are generally insoluble in water ; they
are distinctly more stable towards water than the
other haloid salts. Metallic fluorides very readily
combine with HF to form acid salts, which are
generally decomposed by heat with formation of
the normal salt and HF. A few chlorides, bro-
mides, and iodides combine with HCl, HBr, and
EI respectively ; but such acid chlorides are com-
paratively few in number, and are much lest
stable than the acid fluorides.
HARMALINE.
The non-metallio halogen binary compounds
as a olass are gasifiable ; some, however, are de-
composed'by heat, e.g. ohloiides and bromides
of S ; generally speaking the fiaorides are more
stable than the correBpouding compounds of the
other halogens. Most non-metallic chlorides and
bromides are decomposed by water with forma-
tion of haloid acid and an oxyacid of the non-
metal ; in this respect iodides are more stable
than chlorides and bromides, and fluorides are
more stable than iodides.
Chlorine forms binary compounds with all
non-metals except F; bromine with all except
F, Q, and perhaps N ; iodine with all except B ;
and fluorine with all except Br, CI, C, 0, and K.
The binary compounds of the halogens with H
are acids, HCl, EBr, and HI are strong acids,
but EF has a very small affinity. The binary
compounds which the halogens form by com-
bining one with another are not numerous ; the
chief are IF5, ICl, IClj, IBr, BrCl ; the only one
of these which has been gasified without decom-
position is ICl. M. M. P. M.
HALOID SALTS. Binary compounds of the
halogens F, CI, Br, I, with metals.
HAMATHIOmC ACID C,^„SO„. An acid
produced by the action of E^SO, on euxanthio
acid (Erdmann, A. 60, 240). Syrup ; decomposed
by boiling water. — PbaCiaHuSO,,.
HASMALINE OijH^NjO. Sarmime di-
hydride. [e. 238°]. Occurs, together with harm-
ine, in, the seeds of Perganum ha/rmala, a plant
growing in Southern Bussia. These alkaloids
make np i p.o. of the seeds, and are found in
the seed coating, not in the kernel (Gobel, A.
38, 363 ; Fritzsche, A. 64, 360 ; 68, 351, 355 ;
72, 306 ; 88, 327). Occur probably in the form
of phosphates.
Preparation. — The seeds are extracted with
dilute HOAc or HjjSO,, and the brown extract
mixed with NaCl. The hydrochlorides of the
bases are ppd. together with colouring matter ;
the pp. is washed with brine, and then treated
with pure water, which dissolves the hydrochlor-
ides of the bases. The solution is treated with
animal charcoal and the filtrate heated to 60°
and mixed with ammonia. Earmine comes down
first in minute needles, on further addition of
ammonia harmaUne is ppd. in minute scales.
Properties. — Trimetric octahedra (from al-
cohol) ; a:&:c = 1:1'804:1-416. SI. sol. water and
ether, m. sol. cold alcohol, v. sol. boiling alcohol.
On oxidation with ENO, it forms harmine.
Earmine is also formed when the acid chrom-
ate of harmaline is heated to 120°. By heating
with ECl it is converted into harmalol.
Salts.—^The salts of harmaline are yellow
and exhibit strong fluorescence. — B'ECl 2aq :
long yellow prismatic needles ; m. sol. water and
alcohol.— B'jEjPtCl,: yeUow pp.— B'^E^Cr A =
crystalline.— Acetate is crystalline.— B'HCy:
from harmaline hydrochloride and KCy. Formed
also by dissolving harmaline in boUing dilute
HOy. Thin tables (from alcohol). By heating
to 180° or by boiling with water or alcohol it is
resolved into harmaline and HCy. It combines
with acids ; thus ECl forms B'ECyBCl, a crys-
talline powder composed of small octahedra.
Methyio-iodide B'Mel. [260°] (0. Fischer
R. Tiiuber, B. 18, 400).
Mitro-harmaline C„H,3(N0j)N20. [120°].
Chrysoharmme. Formed by suspending harm-
aline (1 pt.) in alcohol (7 pts. of 80 p.c^) adding
cone. E2SO4 (2 pts.) and, when the solution is
complete, moderately concentrated nitric acid
(2 pts.) ; the mixture is heated to 100°, and when
the reaction is over it is cooled quickly. The
liquid then deposits the sulphate of nitro-har-
maline, which is washed with alcohol contain-
ing E2SO4, dissolved in water, and treated with
£0H. It may be further purified by sulphurous-
acid with which, unlike harmaline and harm-
ine, it forms a sparingly soluble salt. Orange
powder, composed of minute prisms (by ppn.) ;
larger crystals are deposited from the alcoholic
solution. SI. sol. cold water, to which, however,
it imparts a yellow colour ; m. sol. boiling water ;
si. sol. cold ether. More soluble in alcohol than
harmine or harmaline. It expels NH, when
heated with ammonium salts.
Salts.— B'BCl: small yellow prisms. —
B'^jPtClai yellow pp., which ultimately
assumes the for^n of minute prisms. — Nitrate :
yellow needles; si. sol. dilute ENO,. —
C,jE,2Ag(N02)N20 aq : yellowish-red flocculent
pp., obtamed by adding ammoniacal silver ni-
trate to a solution of nitro-harmaline nitrate. —
Normal sulphate: crystalline pp. — ^B'HjSO,:
pale-yellow crystalline powder, nearly insol.
cold water. — ^B'ECy : obtained by dissolving
nitro-harmaline in hot alcoholic HCy. Slender
yeUow needles. Besolved by boiling water into
ECy and nitro-harmaline.
Harmine CisE.jNaO. [257°]. Occurs in the
seeds of Perganum harmala (v. supra). Formed
also by the oxidation of harmaline by a mixture
of equal parts of alcohol and HClA.q to which
a little nitric acid has been added ; the liquid
is boiled, and on cooling harmine hydrochloride
crystallises out in slender needles. The solution
of this salt decomposed by NH, yields the base.
Properties. — Long colourless monoclinic
prisms (from alcohol) ; nearly insol. water, less
soluble in alcohol than harmaline, v. si. sol.
ether. Expels ammonia from boiling solutions
of its salts. By heiating with fuming HClA.q at
140°, harmol and MeCl are fcrmed (Fischer a.
Tauber, B. 18, 400). CrO, oxidises it to harm-
inic acid.
Salts. — Colourless; but in solution they
exhibit indigo-blue fluorescence.— B'HCl 2aq :
needles, sol. water and alcohol, v. si. sol. EClAq.
—B'ECl (from alcohol).— B'jEjPtCl, : flocculent
pp., becoming crystalline when the liquid is
heated. — ^B'^EjSO^ 2aq : concentrically grouped
needles.— B'HjSO, (from alcohol).— B'jHjOrjO,'
— B'EjOjOi aq : radiating needles.
Methyio-iodide B'Mel. [c. 298°]. Long
white needles (F. a. T.).
Di-chloro-harmine C^EioCljN^O. Formed
by heating a solution of harmine hydrochloride
(2 pts.) in water (100 pts.) to boiling and adding
cone. EClAq (15 pts.), followed by KClOj in
small quantities until the brownish-red colour
which at first appears i^ changed to pure yellow ;
on cooling, di-chloro-harmine hydrochloride
separates and is washed with dilute ECLAq,
The salt is recrystallised from alcohol, and de-
composed by boiling NaOHAq. Needles (from
alcohol); insol. oold,,T. si. sol. boiling, water,
aol. alcohol, ether, benzene, and CSg. Witii
HABMAXINE.
iodine it fomiB a compound containing 46*5 p.a.
iodine (OnHigGljNjOI, reqaires 47*5 p.o.).
Salts. — The salts of di-ohloio-harmine are
T. si. sol. dilute acids; the noimal salts aie
partially decomposed by much water, di-chloro-
hanuine separating. Ammonia ppts., the base
from its salts as a jelly ; NaOHAq also forms a
gelatinous pp. which, howeTer, becomes crystal-
line on long boiling with a large excess of
NaO^Aq.— B'HCl 2aq ; needles (from water);
separated from its aqueous solution by NaCl as
a jelly which subsequently becomes crystalline.
B'HNO, : ppd. as a jelly, changing to needles, by
adding HKO, to a solution of di-ohloro-harmine
in dilute HNO,.
Nitro-harmine C^,B.^^Qii02)Sfi (Fritzsche,^.
88, 328 ; 92, 330). Produced by the action of nitric
acid on harmaline or nitro-harmaline. Prepared
by dissolving harmaline (1 pt.) in water (2pts.) and
the requisite quantity of HOAc, and then adding
HNOj (12 pts. of S.G. 1-40) in a thin stream.
The Uquid is boiled as long as nitrous fumes
escape, and the nitro-harmine then ppd. by EOH.
Yellow octahedra which soon change to needles
(from alcohol) ; si. sol. cold, m. sol. boiling, water,
si. sol. ether. — Hydrochloride: B'HC12aq:
slender yeUow needles. — Di-iodide B'lj.
Separates as minnte yeUowish-brown needles on
mixing the boiling solutions of iodine and nitro-
harmine in alcohol. In water, alcohol, and ether
it is nearly insol. in the cold, but si. sol. on
warming. Boiling alcohol resolves it into iodine
and nitro-harmine ; boiling dilute HjSO, acts in
like manner.
Bromo-nitro-harmine C,sH,JBr(N02)N20.
Ppd. by addition of bromine, followed by am-
monia, to a dilute solution of a salt of nitro-
harmine. When bromine-water is added to its
solution in hot dilute alcohol there is deposited
on cooling minute yellow needles of tiie di-
bromide C,3H,„Br3(N02)NjO.
Chloro-nitro-harmine C„H,pCl(N02)N20.
Produced by the action of chlorine on nitro-
harmine or of aqua regia on harmaline.
Preparation.— HarmaMne (1 pt.) is dissolved
in water (2 pts.), and the requisite quantity of
EtOAc, and the solution is poured into boiling
nitric acid (12 pts. of S.G. 1-40) mixed with
fuming HClAq (2 pts.). When the reaction is
over a solution of KH4CI mixed with lumps of
ice is poured into the liquid, which is afterwards
further diluted, and ppd. by NaOHAq. Bright
yellow brittle mass composed of minute needles.
Ppd. from its salts by NH, as a jeUy. SI. sol.
cold, m. sol. boiUng water and boiling alcohol.
SI. sol. ether. Iodine solution forms slender
needles of 0„H,„Cl(N02)N20ij, sol. alcohol.
Salts. — ^B'HCl : slender, hair-like needles,
m. sol. water. Ppd. from its aqueous solution
by HClAq as a, jelly, and by NaCl as white
flocculi. — S'jHjPtClg : slender yellow prisms
(from alcohol).
Hardline tetiabromide CuHi^N^OBr,. Ob-
tained as a reddish-yellow flocculent pp. on
adding excess of bromine to a cold solution of
harminein dilute HjSO, (0. Fischer, JS. 22, 638).
Beconverted into harmine by SO, or by warm
aqueous Na^GOs.
Harmine tetrahydride CjsH,eN,0.
Harmaline dihydride. [199°]. Obtained by
[educing a hot concentrated solution of harmaline
in alcohol by means of sodium (0. Fischer, B,
22, 638). Formed in the same way from harmine.
Irregular pointed needles (from alcohol). Its
solutions fluoresce pale bluish-gieen, becoming
deep-green on addition of FeCl, or AgNO,. Gives
a nitrosamine G„H„N,02.
Apoharmine CsH,N,. [183°]. Got by distilling
harminio acid (v. infra) in a partial vacuum in
portions of -5 g. at a time (0. Fischer, B. 22,
640).— B'HAuCl, : yellow needles.— B'HIaq:
fan-shaped groups of white needles (from HeOH),
decomposing at 220° without melting.
Apoharmine tetrabromlde CgHgNjBr^. A
lemon-yellow pp. got by adding excess of bromine
water to a solution of apoharmine in dilute
HjSO,.
Apoharmine dihydride CgHjoN,. [49°].
(262°). Obtained by reducing apoharmine with
cone. EIAq and red phosphorus at 160°. Tables
(from ether-ligroin). Smells of excrement of
mice. From ether it separates with ether of
crystallisation. Its solution in dilute H^SO,.
exhibits violet fluorescence. Its hydrochloride
colours pine-wood deep-orange. — B"H01 : felted
needles. — B"H2Pt01j 2aq : orange crystals. —
B"HAuGl4 [149°] : reddish-brown needles.
Nitrosamine Cs'H^CSiO)^^. [135°]. Small
needles (from hot water). May be sublimed.
Harmol CiaHuN^O. [821°]. Formed by
elimination of a methyl group from harmine
CijHijNjO, by heating it with faming HOI at
140° (O. Fischer a. Tauber, B. 18, 402). SmaU
needles. V. e. sol. aqueous alcohol, si. sol.
absolute alcohol, nearly insol. water. Dissolves
in acids and in caustic alkalis. The acid solu-
tions have a violet fluorescence.
Harminic acid CipHjN^Oj. [345°]. Formed
by oxidation of harmine in HOAc with CrO, (0.
Fischer a. Tauber, B. 18, 403). Formed in like
manner from harmaline. Silky needles, si. sol.
hot water, nearly insol. alcohol, ether, chloroform,
and benzene. On heating to its melting-pomt
it evolves CO,, and yields apoharmine CgHgN,
which melts at [183°].
Harmalol Ci^H^NjO. Obtained as hydro-
chloride by heating harmaline (3 g.) with cone.
HCLAq (lOcc.) at 150°. The base may be
liberated by NaOH. Bed needles, sol. hot water,
si. sol. benzene, sol. chloroform and acetone.
Beadily oxidised by air. It crystaUises from
dilute alcohol with 3aq. — ^B'HC12aq: crystals. —
B',H,PtCl..
Acetyl derivativeCi^iiJi.e^JL)- Nodules.
Harmolic acid G,^B.,„'Sjli^. [247°]. Formed
by fusing harmol with KOH, and ppg. the aqueous
solution of the melt with H^SO,. Small needles
(from hot water) . The solution of its ammonium
salt gives amorphous pps.,with salts of Pb, Cu, Ca,
and Ag. On £stilling in a partial vacuum har-
molic acid yields a sublimate C„H,gN20 in small
needles, b1. sol. ether, m. sol. alcohol, forming a
solution that fluoresces violet. This body appears
to be a phenol and a base. It forms a platino-
chloride B'jHjPtClj crystallising from hot water in
small prisms united in stars, al. sol. cold water,
decomposing at about 180° (0. Fischer, B. 22,
642).
HAETIN 0,(^,sO. Psatyrin. [210°].
(260°). A fossil resin resembling hartite. Crys-
tallises from petroleum in triolinio needles. Si-
HELIOIN.
8oI. ether and boiling alcohol (Sohr5Uer, P. 54,
45).
HABTITE (C,H„)a,. [74»]. S.G. 1-05. A
fossil lesin found in Styria (Haidinger, P. 64,
261 ; Emnpf , J. pr. 107, 189). White triclinio
crystals. V. sol. ether, m. sol. alcohol.
HATCHETIN. 0. 86 p.o. H. 14 p.o. [46°].
8.G. — '916. A transparent fossil resin found
in the coal measures of Glamorganshire (John-
ston, P. M. 12, 338). Bl. sol. boiling alcohol,
m. sol. hot ether.
HEAT V. Fhtbical meieoss, section Ther-
mal.
HECSECANE v. Hexadboakb.
EEDEBIG ACID CigH^gO^. A substance
occurring in the berries and leaves of the ivy
^Hedera heUx) (Fosselt, A. 69, 62; Hartsen,
Ar. Ph. Apra 1875 ; Davies, Ph. [3] 7, 275 ; 8,
^05). Needles or delicate scales (Posselt). Davies
found it to be uncrystallisable. V. sol. hot alco-
hol, T. si. sol. ether, CSj, chloroform, benzene,
and water. Its solution does not redden litmus.
Cone. HjSO, colours it a splendid violet, the
colour lasting some days ; on pouring into water
a fiooculent greenish pp. is formed. According
to Davies ' hederic acid ' is not ah acid. ENO,
forms a nitro- derivative 0,5H25(N02)04, v. sol.
chloroform. Block (Ar. Ph. [3] 26, 9S3)' finds in
ivy-leaves a glucoside Cs2Hs20,g2ac[.
HELENIN CsHbO. [110°]. Occurs in the
root of elecampane (inula Selmvum), from which
it may be extracted with hot alcohol (Gerhardt,
A. 34, 192 ; 52, 389 ; Gerh. 4, 296 ; KaUer, B. 6,
1506). Keedles, nearly insol. water, v. sol. alco-
hol. The crystals first obtained from the alco-
hol melt at 72°, being a mixture of helenin and
inula-camphor [64°] ; the latter is got rid of by
repeated crystallisation from alcohol.
HELIANTHIC ACID 0„H,80s- . A^ acid
occurring in sunflower seeds (Ludwig a. Krom-
ayer, Ar. Ph. [2] 99, 1, 285). BoiUng dilute HCl
splits it up into a fermentable sugar and an acid
violet colouring matter.
HELIAKTHIIT v. Di-methyl-amido-ienzene-
Azo-bemene-sulphonde acid.
HELICHBYSIX. A yeUow pigment con-
tained in the involucral bracts of HeUchryswrn
bracteatum (Eosoll, M. 6, 94). Amorphous
yellow mass, si. sol. cold, v. sol. boiling, water,
alcohol, and ether.
HELICHJ C„H,A *•«• (C,H„OrO)C,H,OHO.
QVucoside o/ o-oxy-benzoio aldehyde. Mol. w.
284. [170°] (S.); [174°] (P.); [175°] (M.),
[o]„= —60-43 in a 1-4 p.c. aqueous solution at
20° fWegscheider, B. 18, 1600). S. 1-6 at 8°.
formation. — 1. By the action of very dilute
HNOjuponsalicin (C„H„0,.0)C8H,CH20H (Piria,
A. Oh. [3] 14, 287; B. 14, 304; Sorokin, J. pr.
[2] 37, 382).— 2. By boiling its benzoyl derivative
with, magnesia (Piria, A. 96, 380).— 3. By the
action of acetoohlorhydrose Ofi^Clkofi^ on
potassium salicylic aldehyde, the substances
being mixed in alcoholio solution and left for
several days (Mjohael, Am. 1, 808; 0. B, 89,
365).
Pr«para*M)».— Pulverised salioin (1 pt.) is
mixed with nitrio acid (lOpts. of S.G. 1-167) and
the mixture left to itself; after 24 hours the
BjJicin is dissolved wid crystals of helioin have
(epar^ted. They aie washed with ether.
Proper^*.— Very slender, white silky nee-
dles (containing |aq). Keutral, slightly bitter,
ll. sol. cold, v. sol. boiling, water, sol. alcohol,
.insol. ether. At 100° it gives ofi its water of
erystallisation. Its solutions are lasvorotatory.
FeCI, gives no colouration. Gone. H^SO, dis-
solves it with yellow colour. With NaHSO,
heUcin forms a hygroscopic crystalline mass of
0,sH,BO,NaHSO, (Schifl, A. 210, 126).
BeacUons. — 1. Under the influence of etnul-
sin or of boiling dilute adds or alkalis, helicin
is resolved into glucose and o-oxy-benzoio (sali-
cylic) aldehyde. — 2. Sodmm-amalgam reduces
helicin to salicin (Iiesensko, Z. 1864, 577 ; cf.
Swarts, InsU^t. 1865, 825).— 3. When hot alco-
holio solutions of helicin and urea are mixed
together, and the liquid is allowed to evaporate,
there is formed a thick syrup which, when kept
over H2SO4, slowly solidifies. The product is
the di-ureide C^„05.0.CsH4.CH(NH.OO.NHy,
and forms a hygroscopic crystalline powder, v.
sol. water, forming a solution that is ppd. by
Hg2(NO,)8but notbyHNO, (H. Sohiff, 0.12,460).
4. An alcoholic solution of tMo-urea forms
CeH„0,.0.0,H4.CH(NH.CS.NH,)„ a very hygro-
scopic crystalline powder (Schiff). — 6. Aniline
forms the anilide CeH„05.0.CjH,.CH:NPh, a
yellow powder (containing aq), sol. alcohol and
ether, insol. water. It is prepared by gently
heating helicin with aniline, treating the product
several times with acetic acid to remove excess
of aniline, dissolving the residue in alcohol,
adding ether, filtering, and ppg. with water
(H. Schifl, .Z.[2] 4, 638 ; 4. 154, 31). By heating
with aniline at 120° it is converted into the ,di-
anilide CmHjsNjOs. Both anilides are resolved
by boiling dilute E^SO^intoglucose, helicin, and
aniline. — 6. Tolylene-m-diamine forms in like
manner (CjH„Os.O.C,H4.CH:N)20jH3Me, which
crystallises in orange-red tufts ; its solution
e^ibits marked green fluorescence. — 7. By dis-
solving m-amido-bemoio add in a cold aqueous
solution of helicin a transparent vitreous mass
is produced, which crystallises from alcohol
in colourless plates [142°]. This compound
is 0„H„0,.0.CeH,.CH(0H).NH.C,H4.C0jH. On
hbating with acids it is split up into glucose,
m-amido-benzoic acid, and salicylic aldehyde
(H. Schiff, G. 10, 470). — 8. Aimdo-ev/ininic acid
forms in like manner the crystalline compound
CijHijOiOioHijNOj.— 9. By the action of glucose
and excess of EOAo on helicin there is formed
amorphous OeH„0,.0.0^4.CH<°> CbH.jOs
(H. SohiS, A. 244, 26).— 9. By adding leucine to
an aqueous solution of helicin saturated with
gaseous sulphurous acid there is formed
C.H„Oj.O.C„H..CH(OH)S03NH3.0sH„.CO^,
which crystallises with difficulty. Other amido-
acids behave in like manner. — 10. A solution of
helicin (16 pts.) in water (600 pts.) heated to
55° and alternately treated with an aqueous
solution of caustic soda (6 p.c. solution) and
acetone (6 pts.) dissolved in water (40 pts.) de-
posits on cooling crystals of the glucoside of di-
oxy-di-styryl ketone (C„H„0,.O.C„H,.CH:CH)jCp
[257°], while the filtrate on evaporation deposits
the glucoside of oxy-di-styryl methyl ketone
C,H„05.0.C.H,.CH-.0H.00.CH3 [192°], of Which
the osim melts at 17S° (Tiemann a. Eees, B. IQ,
1964).
670
HELIOm.
Tetra-acetyl derivative
CjH^o,05.0.0,H4.CHO. Formed by mixing
heliciu vrith AoCl; after 24 hours the solution
is heated to 60°, and the product extracted with
ether and crystallised from alcohol (H. SchiS, Z.
[2] 5, 1 ; ^. 164, 22). Shining prisms ; insol.
water, si. sol. ether and cold alcohol, v. e. sol.
hot alcohol. Besolved by boiling dilute H^SO,
into glucose, EOAc, and salicylic aldehyde.
With aniline at 80° it forms the aniUde
CsH^c<05.0.C^4.CH:NPh, a yellowish powder,
sol. alcohol.
Benzoyl derivative
CeH,gBzO,.O.CeH4.CHO. Obtained by disBolving
populin (1 pt.) in nitric acid (11 pts, of S.G.
1'3). Formed also by treating helicin withBzGI.
Tufts of silky needles; si. sol. boiling water,
m. sol. alcohol, insol. ether. Not attacked by
emulsin, but boiling dilute acids and alkalis
split it up into benzoic acid, glucose, and sali-
cylic aldehyde. Boiling with water and mag-
nesia resolves it into magnesium benzoate and
helicin. Sodium-amalgam reduces it to populin
0sH,„Bz05.0.CsH4CH20H. Aniline at 150° forms
a brown resinous di-anilide Oj^HjgNjO,.
Tetra-bemoyl derivative
C^^zfl^.O.C^yCaO. From helicin andBzCl
at 160°. Amorphous. Sol. alcohol and ether,
nearly insol. water. Aniline at 150° formiS a
brown resinous di-anilide G^^t^fi^.
Phenyl hydrazide
C,H,(00^„05).CH:NjH0A : [o. 187°]; white
slightly crystalline solid. Sol. alcohol, ether,
and hot water, nearly insol. cold water. By
emulsin it is split up into glucose and salicylic
aldehyde phenyl-hydrazide (Tiemann a. Eees,
B. 18, 1657).
Oxim CjH^IOOeHi.OJ.OttNOH: [190°];
fine white needles containing aq. Sol. water,
more sparingly sol. alcohol, insol. ether. By
emulsin it is split up into glucose and salicyl-
aldoxim. It is Uevorotatory (Tiemann a. Eees,
B. 18, 1662).
Bromo-helicin G,3H,sBrO, aq: gelatinous,
drying up to an amorphous mass.
(o)-Chloro.heIioin 0,»H,5010,. Obtained by
agitating helicin with water in a vessel filled
with chlorine. Small needles containing ^aq
(from water). Sometimes it separates as an
amorphous jelly. Nearly insol. cold, m. sol. hot,
water ; m. sol. alcohol. Emulsin or boiling
dilute acids hydrolyse it, forming ohloro-salicylio
aldehyde and glucose.
(i8)-Chloro.helicin 0„H„C10,. A white
granular substance obtained by passing chlorine
into an alcoholic solution of helicin. Insol.
water, nearly insol. boiling alcohol, not decom-
posed by emulsin, acids, or alkalis. '
Isohelicin C,sH,eO,. Formed by heating
helicin to 185°. Formed also by moistening
helicin with dilute (1 p.c.) nitric acid, leaving it
for some days exposed to the air, and then heat-
ing to 110° (H. Sohifl, B. 14. 818; <?. 11, 112).
Jelly ; drying up to an amorphous powder. De-
composes at 250° without previous fusion. SI.
sol. water, alcohol, cold EOHAq, and HOAo.
Boiling dilute HjSO^ slowly splits it up into
glucose and salioylio aldehyde. By wanning
with very dilute HOIA^ it i$ changed into
ardinaiy bflioin.
__ __ _ This substance, whioh
may be regarded as a compound of helicin with
salioin, is obtained by treating salioin with very
dilute nitric acid (S.G. 1-088) (Piria, A. Ch. [3]
14, 292). Xeedles containing l|aq (from boiling
water). Split up by emulsin and by dilute
alkalis into glucose, salicylic aldehyde, and
saligenin. Aniline at 70° forms the amorphous
di-anilide 0,JB.,fJ!iJd,^.
Octo-acetyl derivative OjjHLjffACjO,,.
[80°]. From helicoidine and Ac^O at 100°
(H. Schiff, A. 154, 28). Drusio aggregates ; insol,
water, v. sol. alcohol and ether.
HELLEBOBIN CseHiA- A glucoside that
oocnrs sparingly in black hellebore {Selleborus^
mger) and more abundantly in green hellebore
(M. viridis) (Husemann a. Marm^, A. 135, 55 ;
cf. Weppen, Ar. Ph. [3] 2, 101, 198). Prepared
by extracting old roots of green hellebore with
alcohol, evaporating the extract, boiling the
residue with water, and evaporating the aqueous
extract tiU crystals are deposited on cooling.
White, concentrically grouped needles (from
alcohol), insol. cold water, si. sol. ether, v. sol.
boiling alcohol and chloroform. Decomposes
when heated above 250°. Cone. H2SO4 colours
it deep red, and then dissolves it with the same
colour. Helleborin is a stronger narcotic than
helleborein. It is resplved by boiling with dilate
acids, or more completely with cone. ZnCljAq,
into glucose and helleboresin OjgHjgO,.
Helleboresin is a resinous body, insol. water, si.
sol. ether, v. sol. boiling alcohol ; water separates
it from its alcoholic solution as a flocculent pp.
Helleborein G3^^^0^^. Occurs more abun-
dantly in black than in green hellebore, but is
present in greater quantity than helleborin even
in the Ijatter. The aqueous decoction> of the
root is ppd. with lead subacetate, the concen-
trated, filtrate freed from excess of lead by sodium
sulphate and phosphate, and the nitrate concen-
trated and ppd. with tannin. The pp. is stirred
up with alcohol and PbO, dried, and exhansted
with boiling alcohol; the helleborein is ppd.
from the strongly concentrated alcoholic solution
by ether. Transparent nodular groups of minute
needles (from alcohol) ; on exposure to air these
crumble to a yellowish- white hygroscopic powder.
Helleborein has a sweetish taste, is v. e. sol.
water, m. sol. alcohol, and insol. ether. It is
poisonons. The aqueous solution, which scarcely
reddens litmus, dries up to an amorphous mass
which loses water at 120°, becomes straw-yellow
at 160°, brown at 220°, and carbonises above
280°. Cone. HjSO, dissolves it with brownish-
red colour changing to violet. Alkalis and
alkaline earths have no action upon it. Boiling
dilute acids split it up into glucose and helle-
bore tin. Helleboretin is deposited as a dark
violet-blue pp. which, when dry, forms a grey-
green amorphous powder, melting above 200°,
insol. water and ether, sol. cone. HjSO, forming
a brownish-red solution whence it is ppd. by
water in its original state. The alcoholic solu-
tion of helleboretin is red, and gives a brown
colouration with HjSO, (Greenish, O. J. 88, 719 ;
Ph. [3] 10, 909, 1018). EeUeboretin iB not
poisonons.
EEUEIiIITHEirB v. Eeuimbi^iiheni.
HEUELLIIHENE-CABBOXTUO A.CID «.
Tbi-hbxhsl-bensoio aoip.
HEMIPIO ACID.
671
HEUELLITHENE STTLFHONIC ACID «.
TSI-METHYL-BBNZENB-SCliPHONIO AOID.
HEUI-AIBUUEN V. Pboteids.
HXUI-COLLIN V. Fboieids, Appendix C.
HEMIMELLITHENE OaH,Me, [1:2:3]. c-Tri-
methyl-benzene. (17S°). Formed by distilling
(a)-ouminio aoid 'witii Ume (0. Jacobaen, B. 15,
1857 ; 19, 2517). Formed also by the aotion of
Bodium upon a mixture of (2,l,3)-bromo-zyIene
and Mel (O. Jaoobsen a. Deike, B. 20, 903).
Hemimellithene may also be isolated from
coal-tar oil. It forms atri-bromo-deriTative
C^r,Me, [209°]. Coal-tar oil also contains an-
other hydrocarbon boiling at 175° which yields
a very soluble sulphamide [123°] and gives on
oxidation two aoids [121°] and [99°] (Jaoobsen,
B. 19, 2511).
HEMIUEI.i:.ITHEIIOL O^.^O i.e.
CAMe3(OH)[5:4:3:l]. [81°]. Formed by fusing
the solphonio aoid of hemimellithene with
potash (O. Jacobsen, B. 19, 2518). Long fiat
needles, sol. alcohol and ether. Not coloured by
FeCL,.
HEMIMELLITHIDIITE v. CummNEi
HEUIUELIITHYLIC ACID v. Di-ueihyi.-
BENZOIC ACID.
HEMIMELLITIO ACID C^fi, i.e.
C|iH,(COjH).,[l:2:3]. HemimellUMc euAi. Benz-
ene c-iri-carboxylio acid. Mol. w. 210. [185°].
Formed, together with phthalio anhydride, by
heating the hydride of mellophanio aoid
0^{C0j;H)4 with H^SO, (Baeyer, A. Svppl. 7,
31). Needles ; begins to melt at 185°, being de-
composed into phthalic anhydride, benzoic aoid,
CO2, and HgO. M. sol. cold water. Ppd. from
its concentrated aqueous solution by ECl (dif-
ference from phthalio acid). — ^Ba,A"'2 5aq : short
thick needles, v. sol. water. — ^Ag,A"': fiocculent
PP-
HEMI-FEFIONE v. Pboteids.
HEMIFIC ACID C,„H,„0, i.e.
0^(OMe),(CO^H)2[l:2:3or5:4]. . Di-methyl
derivative of di-pocy-phthalic acid. MoL w. 226.
[180^.
S'ormaUon. — 1. By the oxidation of opianio
acid C;aL,(OMe)j(OHO)(COjP) byPbO, and HsSO«
(Wohler, A. 50, 17), by aqueous PtOl^ (Blyth. A.
50, 36, 43), or by chromic acid mixture (Matthi-
essen, Pr. 17, 341).— 2. By the oxidation of nar-
cotine by dilute HNO, (Anderson, A. 86, 194),
by PbOj and HjSO<, by MnO^ and H,SO, (W5hlor ;
Liechti, A. Suppl. 7, 150), or by aqueous PtCl,
(Blyth). In these reactions the narcotine is first
eonverted into opianic acid. — 3. Together with
meconine 08H2(OMe)j<^g^>0, by fusing opi-
■nic acid with potash (Matthiessen a. Foster,
Pr. 11, 58; O. J. 15, 346; Beckett a. Wright,
C. J. 29, 281). — 4. By the oxidation of narceine. —
6. By the oxidation of berberine (B. Schmidt, B,
16, 2589 ; Perkin, jun., O. J. 55, 71).— 6. By the
oxidation of papaverine by KMn04(Uoldschmiedt,
M. 6, 380J. — 7. By boiling di-azo-hemipio acid
(from amido-hemipio acid) with alcohol (Lieber-
mann, B. 19, 2278; Griine, B. 19, 2303). -8.
Formed, together with cinchomeronio acid, by
the action of 4 p.c. alkaline EMnO, on the di-
methyl derivative of di-oxy-isoquinoline (Gtold-
Bohmiedt, M. 9, 327).
Preparatiow.— Opiamo aoid is converted by
b^droxylamine hydioghignde into opianio ozim
anhydride which is .then boiled with aqneoni
EOH. The product is acidified and the hemipio
acid is extracted with ether (Ooldschmiedt, M.
9, 766).
Properties. — Monoclinic efSoresqent crystals
(containing |aq, aq, 2aq, or 2|aq). After drying
at 100°, its melting-point varies from 157° to
175° according to the rapidity with which it is
heated (Or.). SI. sol. cold water, m. sol. alcphol
and ether. Its aqueous solution is acid in re-
action. Sublimes in shining laminEB. Gives an
orange colouration with FeCl,. Gives the fluor-
escein reaction.
Bea,ctions. — 1. By boiling with EClAq or
EIAq it is resolved into MeCl (or Mel) and the
methyl derivative of di-oxy-phthalic acid (nor-
bemipio acid) CeH:2(OH)(OMe)(C02H)2, which
then splits up into CO2, and the methyl deriva-
tive of protocatechuio acid (isovanUlic acid)
C„H,(0Me)(0H)(002H) [251°].— 2. By heating
with HGlAq at 170° it is resolved into MeCl,
protocatechuio acid and CO^ (Wegscheider, 'M.
4, 270). — 3. Heated with seven times its weight
of KOH and a little water at 210° for fifteen
minutes; it is converted into protocatechuio
aoid. — 4. Distillation with soda-lime gives the
di-methyl derivative of pyrocatechin (Beckett a.
Wright). — 5. Cone. H2SO4 converts it on heating
into rufiopin (Liebermann a. Chojnacki, A. 162,
327).
Salts.— NH,HA"aq. Needles.— KHA"iaq :
large hexagonal tables, v. sol. water and alcohol,
insol. ether. — ^Ag^A" : white pp. insol. water. —
Barium salt: when a solution of the barium
salt is boiled, shining crystalline plates are de-
posited ; the liquid on cooling redissolves this
pp., but after standing for some hours, feathery
tufts of very small silky needles separate ; these
dissolve on heating, and the crystalline plates
are again deposited (Matthiessen a. Foster). —
Ferric salt: orange-yellow pp. — ^Lead salt:
white pp. insol. water, sol. Fb(OAo)2Aq whence
it separates as transparent nodules.
{a)-Methyl ether
cX(OMe)j(00,Me)(CO^) [4:3or5:2:l], [122°].
Formed by oxidising methyl opianate with
aqueons KMnO, at 90° fWegscheider, M. 3, 359).
Long trimetrio needlles (containing aq or 1^ aq).
Melts at 98° in its water of crystallisation. SI.
sol. cold, m. sol. hot, water, v. sol. alcohol, ether,
and benzene, almost insol. ligroin. Its aqueous,
solution is feebly aoid in reaction, and gives a
golden pp. with FeCl,. On heating to 200° it
gives hemipio anhydride. Distillation with
lime gives the di-methyl- derivative of methyl
piotocatechnate, methyl-di-oxy-phthalio aoid,
hemipic acid, the methyl derivative of pro-
tocatechuio aoid (isovanillic acid) and protoca-
techuio acid. By heating with cono; EGLAq
at 120° it is resolved ' into MeCl, hemipio
acid C,H2(OMe)(OH)(C02H)2, isovanillic acid
CsH,(0Me)(0H)(C02H) [4:3:1], and protocateoh-
nio aoid.
(P)-Methyl ether
0^(OMe)j(0OjMe)(CO2H) [4:3or6:l:2]. [138'1.
Formed by passing HCl into a solution of hemipio
acid in MaOH (Wegscheider, M. 3, 359; ef,
Anderson, A, 86, 195). Trimetrio crystals (from
chloroform); a:i:c= '624:1: -758. V. sol. water,
•Icohol, etbei, and benzene. Its (tqaeouB sola*
872
HEMIPIO ACID.
tion gives no pp. with FeCI,. At 200° it yields
hemipic anhydride.
Mthyl ether C„H2(OMe)2(COjEt)(C02H).
[132°] (A.); [142°] (W.). Formed by passing
HCl into a solution of hemipio acid in alcohol.
Needles (from MeOH) or monocUnic prisms
(from benzene] ; t. b1. eoI. cold, m. sol. hot,
water; v. e. sol. MeOH, v. sol. alcohol and ether.
Its aqueous solution is ppd. by FeCl,.
Anhydride 0,„HsO5. [167° oor.]. Formed
by heating hemipic acid at 180° for an hour,
and crystallisingfromalcohol (Beckett a. Wright,
C. J. 29, 281). Formed also by treating hemipio
acid with POl, (Prinz, J. pr. [2] 24, 370). Shining
needles. V. e. sol. hot benzene, t. eoI. hot
alcohol, m. sol. ether, insol. ligrom. Beduced
by boiling with zinc-dust and HOAo to pseudo-
meconine. Boiling dilute alcoholic potash con-
verts it into mono-ethyl hemipate (Matthiessen
a. Wright, Pr. 17, 341).
Imide CjoHjNOi t.e.
C,Hj(OMe),<^Q>NH (?). [230°]. Formed by
distilling ammonium hemipate (Liebermann, B.
19, 2278). Formed also by molecular change
from the isomeric compound opianic-oxim-
auhydride by heating the latter to its melting-
point [115°], heating it with cone. H^SOj, or with
alcohol containing a trace of HCl. Hence it is
produced in place of the oxim-anhydride by
boiling opianic acid with an alcoholic solution
of hydrozylamine hydrochloride (Liebermann,
B. 19, 2923). Ziong slender colourless needles
(from alcohol). The dilute alcoholic and aqueous
solutions fluoresce blue. Sublimable. Dissolves
in caustic alkalis but not in Na^COjAq. Hot
KOHAq converts it into hemipic acid and NH,.
Boiling with tin and cone. HOlAq converts it
into 'hemipimidine' G,oH„NO, or
CA(OMe),<g^'=>NH (?). [181°], which
crystallises from benzene-Iigroin in laminse and
gives a nitrosamine 0,„H,„(NO)NOj [156°],
whence hot aqueous NaOHAq forms nitrogen
and pseudo - meconine C,gH,g04 (Salomon,
B. 20, 884).— OjbHbKNOj: crystalline solid.—
C,„HjAgN04 : white pp.
Ethyl-imide C^B.^{OUe)i<^^ySEt (?).
[98°]. Formed by heating the potassium de-
rivative of the imide with EtI, or by distilling
ethylamine hemipate. Needles (from water) ; v.
e. sol. alcohol and ether (L.).
Jso- imide C,„H,N04. [above 320°]. Formed,
together with other bodies, by ozi&ising papa-
verine with KMnO, (Qoldschmiedt, M. 8, 512).
Small needles (from water). May be sublimed.
V. si. sol. hot water, alcohol, and ether, m. sol.
hot HOAc. The alcoholic solution exhibits
blue fluorescence. Boiling KOHAq splits it up
into NH, and hemipio acid.
Ethyl-iso-imide 0,„HsEtNO,. [227°].
Formed by oxidising papaverine ethylo-bromide
with EMnO, (Q.). Needles (from alcohol) ; si. sol.
boiling alcohol ; sublimes in colourless needles.
Potash converts it into ethyl-hemipamic acid
O.H2(OMe)j(COjH)(OONHEt) which resembles
the corresponding benzyl derivative.
Benzyl-iso-imidei C,oH,(CH2Fh)NOt.
[226°]. Formed, together with other products,
by oxidising pajjaverine benzylo-ohloride (30 g.)
with 2 p.o. aqueous KMnO, (lOOg.) (Goldsohmie
M. 9, 327). Needles (from alcohol). May be
sublimed. Neutral; insol. dilute acids and
alkalis. Split up by boiling KOHAq into hemi-
pic acid and benzylan^ine, an intermediate
product being the mono-benzylamide of
hemipio acid C„Hj(0Me)2(C0jH)(C0NHC,H,),
which orystaUises from alcohol in very slender
needles, reconverted by heat into the imide.
The mono-benzylainide is v. sol. aqueous alka-
lis; its K salt crystallises in needles, t. sol.
water ; its Ag salt is amorphous.; the Ca salt,
CaA'2, crystallises in small needles, m. soL
Nitro-liemipio acid C,H(N0j)(0Me)j(C02H),
[166°].
Formation. — I. By boiling nitro-opianio
acid with HNO, (4 pts.) (Liebermann, B. 19,
2285 ; Griine, B. 19, 2303).--2. Together with
nitro-pseudo-meconine, by heating meconine or
pseudo-meconine (Ig.) with HNO, (10 o.c. of
S.G. 1-14) for 1 hour at 160° (Salomon, B. 20,
888).
Preparation. — ^When opianic acid is nitrated
by HNO, and the solid cake produced crystal-
lised from water, nitro-opianic acid separates
and nitro-hemipio acid remains in the mother
liquor. Nitro-hemipio acid is obtained in larger
quantity by heating opianic acid (50 g.) with HNO,
(50 g.) as long as red fumes come oS. The mass
is crystallised from water and the mother liquor
mixed with NH, and BaCl,. Baric nitro-hemi-
pate separates. The free acid is got by decom-
posing this with H2SO4 (Prinz, J. pr. [2] 24,
359).
Properties. — Yellow prisms (containing aq).
Salts. — A"Kj: yellow prisms, v. sol. water
and aloohol.-^A"Ag2: yeUow pp.
Anhydride CeH(NO,)(OMe),<;^^>0:
[145°] ; thick yellow prisms ; formed by heating
the acid to 160°-165° (Liebermann, B. 19,
2286 ; Grune, B. 19, 2303).
o-Amido-hemlpic acid 0„H„0,N i.e.
CsH(0Me)2(NHJ(C0,H),. Amddo-M^methoxy-
phthalie acid. The free acid was not isolated
as its solution easily decomposes on evapora-
tion.
Formation. — 1. By reduction of nitro-hemi-
pic acid with FeSO, andNaOH.— 2. By boiling
the anhydro-acid (so-called ' azo-opianio acid ')
yOOH
C,H(OMe),(CO,H)^ || with excess of baryta-
water.
Beacl>ion.—Bj diazotisation and boiling with
alcohol it may be converted into hemipic acid
O.H,(OMe),(CO,H),.
Salts. — A"Na23aq: easily soluble long
white needles. — A"Ba : glistening golden-yellow
spangles, si. sol. water.— A"Cu7aq: slender
green needles. — A"Ag,'' : yellowish-white pp.
(Grune, B. 19, 2301).
Acetyl derivative
CsH(0Me)2(NHAc)(C0jH),: [160»-170°]; colour.
less needles containing aq. Heated to 12S° it
is converted by elimination of water into the
acetyl derivative of the anhydro-acid (Iiieber<
mann, B. 19, 2921).
HENDECOIC ACID.
67S
lAnliydro-o-amido-liemipio acid (so-oalled
' cuo-opiamc acid ') CuHaOsN i.e.
0^(OMe),(CO^)<gO
-COH
or O.H(OMe),(CO,H)< |i
\n
[200°]. Formed by boiling mtro-opianio acid
with SnCLj and HCl (Prinz, J. pr. [2] 24, 364).
Long white slendei needles (from hot water).
Decomposed on fusion. It dissolves in oonc.
HjSO, and is thrown down unaltered by water.
It is not affected by sodium-amalgam, or by
KMnOf in presence of H^SO,. By boiling with
baryta water it is converted into amido-hemi-
pio acid C8H(OMe)2(NH2)(C02H)2 (Liebermann,
JB. 19, 2275 ; Griine, B. 19, 2299).
Salts. — A'K: white crystalline powder. —
A'Ag : white pp. — BaA'^ 6aq : slender needles.
Methyl ether A/Me: [127°].
Ethyl ether A.'Et: [93°]; needles, sol.
alcohol, ether, &a.
Phenyl hydraside
/CO.NPh
Oja(OMe)j^C=N : [222°] ; small glistening
\NH
yellow tetragonal pyramids, a:e = 1:0'5947.
Acetyl derivative
C.H(0Me),(C0^)<§5^ : [165°]; yellow
needles. Formed by aeetylation of the an-
hydro-acid; by heating amido-hemipic acid with
AojO and NaOAc ; or by heating acetyl-amido-
hemipio acid to 125°. By warming with aqueous
alkalis it is converted into acetyl-amido-hemi-
pic acid (Liebermann, B. 19, 2920).
Propionyl derivative C,|,Hg(C3H50)0jN :
[139°].
Iso-hemipic acid CeB^(OUe),{CX>^),lS:i:S:l'].
[246°]. Formed by oxidising iso-opianic acid
with a dilute solution of EMnO^ (Tiemann a.
Mendelsohn, B. 10, 398). White needles (from
hot water) ; nearly insol. cold water, v. sol. al-
cohol and ether. May be sublimed. The salts
of the alkalis and alkaline earths are easily solu-
ble and crystallise well.
Mono-methyl ether MeBA". [167°].
Hor-methyl-hemiplc acid v. Methyl deriva-
tive of Dl-OXT-PHTHAUC ACID.
Nor-methyl-nitro-hemipic acid v. Methyl de-
rivative of NiTBO-DI-OXT-PHTHAIiIO ACID.
Xor-methyl-anhydro-amido-hemipic acid v.
Methyl dervoati/iie of ^m%(2ro-Di-oxy-Aiii]>o-
PHIHAUO ACID.
HUMP. Cannabis sativa. Hemp-seeds con-
tain about 25 p.o. of a drying oil, S.G. ^ -928,
which on saponification yields an acid C,,H,202.
When Has acid is dissolved in HOAc and treated
with bromine there is formed Cit'S^JBifl^ [115°]
and C^Hj^BrjOj [177°]. The acid C.gHs A yields
on oxidation sativic aoidO,BH32(OH),02(Hazura,
M. 8, 147). Hemp leaves yield on distillation an
essential oH C.^Hj, (257°), V.D. 7-1, S.G. g -93,
[o]j'='-10-8° at 25-5° (Valente, G. 10, 479; 11,
196).
Indian Hemp v. Cannabis indica.
KEITDECAXAPHTHENE ti. Hendecxleki;.
TO-HENDECAHE C„Hm. [-26-5°]. (195°).
S.G.J -7559; Sf -6816. Formed by the action
of HI and phosphorus at 230° upon hendecoio
Vol. XL
(undecylio) acid, or upon OnH^jCIj obtained by
treating oil of rue with POI5 (Krafft,B. 15, 1697).
HENDECENOIC ACID C„E[j<,Oj i.e.
CHj:CH(CHy j.COjH (?). JJndecylemlcacid. [24-5°].
(165° at 15 mm.) (B.) ; (275° at 760 mm.) ; (199°
at 90 mm.) (K.). Formed by distilling castor oil
under diminished pressure (KrafEt, B. 10, 2035 ;
Brunner, B.19, 2228). Large plates; distils with
decomposition at 275°. Split up by potash-
fusion into acetic acid and w-ennoic acid CjH,jO,.
Fuming HNOj oxidises itto sebaoio acid 0,„H,80,.
With bromine it forms Ct^B^^rfi^ [38°]. HBr
forms C„H„BrO, [35°]. HI gives C„H„IO,
[24°]. — BaA'j : flat needles or laminsB, S. "093 at
15-5° (Becker, B. 11, 1412).
Di-hendecenoio acid (C„Ha,0j)2 i.e.
0,„H,,.C0.0.0,„H2„.C0jH. DiMndecylerme acid.
[30°]. (276° at 15 mm.). Formed, together with
the following acid, by heating the preceding acid
in a sealed tube above 300° (Krafft a. Becker, B.
10, 2034 ; 11, 1412 ; Krafft a. Brunner, B. 17,
2986). Formed also by, the action of silver hen-
deoenoate on iodo-hendecenoio acid (Brunner, B.
19, 2224)._ Crystallises from dilute alcohol. On
heating with KOH hendeoenoic acid is among the
products. Br forms CjjH^BrjOj, an almost
colourless oil.
Poly-hendeoenoic acid (C„Ha,02)a,. Poly-
undeoylenic add. Formed as above, and also
found in the residue after distilling castor oil.
Amorphous. Gives ennoio acid on fusion with
potash, and sebaoio acid on treatment with
HNO,.
Hendecenoic acid CnHjoO,. Petroleumic acid.
(250°-260°). S.G. « -982 ; ss .969. Occurs in
petroleum (Hell a. Medinger, B. 7, 1217; 10,
451 ; Markownikoff a. Ogloblin, J. B. 15, 345).
Extracted from rectified petroleum by aqueous
alkaUs, and ppd. by HjSO«. Liquid. Not affected
by potash-fusion or by nitrous acid. Does not
combine with bromine. Boiling HNOj (S.G. 1'3)
forms acetic acid and an acid CgH,,0,. — AgA' :
flocculent pp.
Methyl ether MeA'. (236°-240°) at 739
mm. S.G. 2 -939 ; SI -919.
HENDECINENE CnHj,. RutyUdene. (o.200°)
(Giesecke,^. 1870,431); (210°-215°) (Bruylants,
B. 8, 413). Formed by the action of alcoholic
KOH at 130° on 0„HaCL„ obtained from
CsH,3.C0.CH, (in oil of rue) and PCI5. Liquid.
Gives a white pp. with ammoniacal AgNO, and
a brownish-yellow pp. with ammoniacal Cn^Clj.
HENDECINOIC ACID C,;H,sOj. UndecoUc
acid. [59"5°]. From the dibromide of hende-
cenoic (undecylenic acid) CuH^gBrjOj and alco-
holic KOH (Krafft, B. 11, 1414). Thin laminis ;
decomposed on distillation. V. si. sol. water, v.
sol. alcohol. Fuming HNO, oxidises it to
aracbic acid CgHigOj.
S alts.— CaA'j aq.— BaA',. S. -47 at 16'5°.—
AgA'.
Hendecinoic acid C„H,80ij. (270°-280°).
Among the products obtained by passing CO at
160° over a mixture of sodium isovalerate and
sodium ethylate (Looss, A. 202, 321). Liquid.
HENDECOIC ACID C.iHjA- UndecyUe
acid. [28-5°]. (228° at 160 mm.). Formed by
heating hendecenoic acid (undecylenic acid) with
HIAq and red phosphorus at 210°. Formed
also by oxidising methyl hendecyl ketone
Me.CO.C„Hu with chromic acid mixture (Kra&t,
XX '
674
HENDECOIC ACID.
B. 11, 2219; 12, 1667). Crystalline mass.
Insol. water, v. e. sol. alcohol, sol. ether. —
BaA',.— J
(MejCj^CMe.COjH. Meihyl-di-Urt-hutyl-aeelAe
acid. [66°-70°]. (266° cor.). Formed by oxidis-
ing tri-iso-butylene with chromic acid mixture
(Butlerow, J. B. 11, 203). Crystalline mass.
Insol. water, v. e. sol. alcohol and ether. —
NaA'faq: crystalline. Absorbs COj from the
air, the acid being liberated. — Magnesium
salt : T. si. sol. cold water.
Methyl ether MeA'. (217°-220'').
Ethyl ether BtA'. (225°-230°).
Heudecoic acid CjiH^jO,. UmbelhiMo acid.
[0. 23°]. (275=-280° cor.). The glyceryl de-
rivative of this acid constitntes the greater part
of the fatty substance in the kernels of the
Calif ornian laurel {TJmbellulcma eaUforrdca)
(StiUman a. O'Neill, Am. 4, 206). Crystalline.—
AgA'.
Methyl ether M6A'.. (245°).
Ethyl ether EtA'. (254°).
Isoamyl ether O^Bij,&.'. (295°).
HENDECOKEHE 0„H„. (182°). Occurs,
together with the following, in Dippel's animal
oil (Weidel a. Ciamician, B. 13, 80). Boes not
combine with HOI.
Hendeconene G„H„. (203°). V. swpra.
Hendeconene (C„E,s)a.. [196°]. Extracted
by ether from Cascara amarga and Phlox cwro-
Vma (Abbot, B. 21, 2598). Needles, sol. ether,
HOAc, chloroform, hot alcohol, petroleum ether,
and AcjO.
HENBECYL ALCOHOI. 0,^,0 i.e.
C»H„.0H(0H).CH3. (229°). S.G.i2-827. Prom
oil of rue by reduction with sodium amalgam
(Giesecke, Z. 1870, '428).
Hendecyl alcohol C„BL„0. (245°-255°). A
product of the action of sodium on isoamyl iso-
valerate (Lourenpo a. Aguiar, Z. 1870, 404).
HEHDECYL BROMIDE CiiH^sBr i.«.
CgHjg.OHMeBr. From the corresponding alco-
hol (v. sti^a), Br, and P (Giesecke). Splits up
on distillation into HBr and hendecylene CnHjj.
HENDECYL CHLORIDE C„HaCl. (220°-
224°). Formed by chlorinating the hendecane in
petroleum (Felouze a. Cahours, A. Ch. [4] 1, 5).
HENDECYLENE C,jHb, Undecylme.
(193°). Formed by distilling hendecyl bromide
(Giesecke).
Hendecylene 0„Hij. (195° cor.). S.G. 2
•791. Occurs among the products of the distil-
lation of the lime salts obtained by saponifying
train oil (Warren a. Storer, Z. 1868, 230).
Hendecylene C„Hj2. (196° cor.). S.G. 2
■840. Occurs in Burmese petroleum (W. a. S.).
Hendecylene C„Hj2. (194°). A product of
the action of heat on paraffin (Thorpe a. Young,
A. 165, 23).
Hendecylene CuH^,. Sendecana/phthene.
(180°). S.G. 2 -812. Occurs in petroleum from
Baku (Markownikoff a. Ogloblin, J. B. 15, 335).
On chlorination it gives a mixture (210°-225°)
of chlorides 0„H2,C1, whence alcoholic KOH
forms hydrocarbons 0„Hj|,, which combine
directly with Br and BL^SO, but do not ppt.
ammoniaoal AgNOj.
HENICOSANE C„H„. [40°]. (215° at
15 mm.). B.G. *j° -778; f -74. Formed by re-
flaetion of the diohloride (C,„H2,)jCClj of the ke-
tone (C,„H2,)2C0, obtained by the dry distillation
of barium hendecenoate {'SiaSt, B. 15, 1718).
Obtained also from brown coal paraffin by frac-
tional distillation (KrafEt, B. 21, 2263). Silvery
plates.
HENICOSENOIC ALDEfiYDE O^VLJi U.
CH3(CHj),.CH:C<[3g.^ jj2(Q»2Q)^Q3j^(,g^^
m-hepiyl-heptoic aldehyde, (a. 320°) at 300 mm,
S.G. ^ -874. Formed by the action of sodium
amalgam on heptoio aldehyde ; the yield being
5 to 10 p.o. (Parkin, jun., C. /. 43, 71). Slightly
yellow oil ; sol. OS,. Beduces ammoniacal sil-
ver solution. Does not appear to combine with
NaHSO,. Combines with bromine (1 mol.) in
CSj. Decomposed by boiling with dilute H^SOj.
Blackens when heated with potash.
TO-HENTRIACONTANE C„H„. [68°]. (302°
at 15 mm.). S.G. « -773; «f -762. Occurs in
bee's wax (Schwalb, A. '285, 106). Formed by
reduction of the diohloride (G,5H3,)2CCl2 of pal-
mitone (CuHsOjCO with HI and P (Krafft, B. 16,
1714). SI. sol. ether.
HEFTACOSANE v. Heftaicosane.
TO-HEPTADECANE CjjHj,. [23°]. (163° at
10 mm.) ; (223° at 100 mm.) ; (303° at 760 nmi.).
S.G. «f -775; \» -771; i|2 -724. Hexagonal
tables. Formed by reduction of the diohloride
of methyl hexadecyl ketone, or of margario acid
with P and HI (Krafft, B. 15, 1702). Occurs
in crystalline commercial scaly paraffin (Eraflt,
B. 21, 2256). ■
HEFTADECOIG ACID v. Maboabio Aon>.
HEPTADECYLAMINE C„H,5NHj. [49°].
(335°-340°). Formed by distilling stearyl-hep-
tadeoyl-urea 0,jH350.NH.CO.NH.O„H,5 with
lime (Hofmann, B. 15, 774; Turpin, B. 21,
2486). Fatty crystalline mass, sol. alcohol and
ether. Absorbs moisture and CO, from the air.
Not volatile with steam. Its ethereal solution eva-
porated with CSjforms O^HasNHj.S.CS.NHC.iHj,
[90°], which on boiling witii alcohol forms di-
heptadecyl-thio-urea [94°]. The hydrochl or-
ide is insol. water, and crystallises from alcohol
in plates with a fatty lustre. — B'^H^PtCl,: minute
yeUow crystals.
Benzoyl derivative C,rH,sNHBz. [91°].
Crystallises from benzene in plates.
HEFIADECYL-OARBAMIC ETHER
CuHasNaOOjEt. [62°]. Formed by the ao^
tion of boiling alcohol on heptadecyl cyanate
CijHjsNiCO, an oil which is obtained by heating
heptadecylamine hydrochloride with COGl, in
benzene at 100° (Turpin, B. 21, 2486). Lustrous
plates.
DI-HEPTADECYL KETONE (C^HaJjCO.
[88°]. One of the products obtained bydistiUing
stearyl-heptadecyl-urea with lime (Turpin, B.
21, 2487). SI. sol. alcohol.
HEPTADECYL THIOCARBIMIDE
C„Hs5N0S. [32°]. Formed, together with a
small amount of di-heptadecyl-thio-urea, when
heptadecylamine is heated with alcohol and CS^
at 100° (Turpin, B. 21, 2486). V. sol. alcohol
and ether. Cannot be distilled.
HEFTADECYL-THIO-TTREA
C„H35NH.CS.NHj. [111°]. From the preceding
and alcoholic N^ at 100° (T.). SI. sol. alcohol.
Di - heptadecyl - thio - urea (0, ,Hj5NH)2CS.
[94°]. Prom heptadecylamine by boiling with
alcoholic CS,.
HEPTENE.
676
HEPTADECTL-TrREA O.jH^sNH.CO.NHj.
[109°]. Prom heptadecylamine hydrochloride
and alcoholio potassium oyanate (Turpin, B. 21,
2186). SI. sol. alcohol.
Stearyl derivative
C,^NH.CO.NH.C,8H,sO. [112°]. Formed by
the action of bromine and KaOH on the amide
o{ stearic acid. Pearly lamins (Hofmann, B.
15, 761).
Di-heptadecyl-urea (0„Hs5NH)200. [73°].
From di-heptadeoyl-thio-urea and HgO.
ro-HEPTAICOSANE C^Hja. [60°]. (270° at
15 mm.). S.G. «> .779; laa .754. pormed by
reduction of the dichloride of myristone
(C,sHj,)jCO with HI and P (KrafEt, B. 15, 1713).
Appears also to be present in bee's wax (Schwalb,
A. 235,106). Occurs also in commercial paraffin
{KrafEt, B. 21,2264).
HEPTAKAPHTHEBTE 0,H„. (101°). A hy-
drocarbon in Caucasian petroleum (Milkowsky,
Bl. [2] 45, 182).
ji-HEPTANE C,H„ i.e.
CH,.CH2.CH2.CHj.CH2.CH2.CH3. Heptyl hydride.
Meihyl-hexane. Ethyl-amyl. IH-propyl-methane.
AMetme. Mol. w. 100. (98-43°) (Thorpe);
(98-4° cor.) (Perkin, O. J. 45, 447). S.G. «
•7005 (T.) ; if -6885 ; || -6814. M.M. 7-669 at
14-1°. C.E. (0°-10°) -001222 ; (0°-100°) -001489
(T.). H.C. 1137450 (Louguinine, O. B. 93, 274).
&.V. 162-56 (T.) ; 165-0 (Bamsay). V.D. 500
(Theory 49-9). /1d = 1-3879. Ed = 56-4 (oalo.
55-8). Coefficient of viscosity : -004236 at 15-3°.
Angle of cwpiUcmty 167° (Thorpe). Critical
temperature, 281° (Thorpe a. Biioker, C. J. 45,
165). Occurs almost absolutely pure in the
exudation of the nut pine (Pimiis sabimana)
(Thorpe, C. J. 35, 296 ; 37, 213 ; c/. WenzeU, Ph.
[3] 2, 789). Occurs also in American petroleum,
in coal-tar oil (Pelouze a. Cahours, O. B. 56, 505 ;
Warren, J. 1865, 516 ; Schorlemmer, C. J. 15,
423 ; 26, 319 ; Pr. 14, 164, 464), and in GaUoian
petroleum (Lachowioz, A. 220, 193). Formed
by distilling azelaao acid with baryta (Dale, C. J.
11, 258). Occurs, together with heptylene,
amongst the hydrocarbons obtained by fistiUing
the lime-soap of Menhaden oil (Warren a. Storer,
Z. [2] 4, 231). Obtained also by distilling tri-
olein under pressure (Engler, B. 22, 596).
Treated with chlorine heptane gives a mixture'
of ohloroheptanes (143°-158°). These may be
converted into a mixture of a primary heptyl
alcohol (165°-170°) and a secondary heptyl
alcohol (156°-158°). By oxidising with chromic-
mixture the former gives heptoio acid, the latter
methyl amyl ketone and, by further oxidation,
valeric and acetic acids; hence the alcohols are :
0H3.CH2.CHj.CBL,.CH2.CH2.CHjOH and
CHs.CHj.CHj.CHj.CH2.CH(0H).0H,
(Schorlemmer a. Thorpe, T. 174, 270 ; A. 217,
150). The mixture of chlorides {143°-157-5°) is
converted by alcoholic potash partly into hep-
tylene (98-5°), partly into a mixture of ethyl
heptyl oxides. The heptylene gives on oxida-
tion valeric and acetic acids, hence it is
C,H,.CH:OH.OHs. Liquid bromine acting upon
hot w-heptane forms chiefly secondary heptyl
bromide; gaseons bromine forms primary and
secondary heptyl bromides in about equal quan-
tities. Liquid Br dissolved in cold heptane forms
chiefly di-bromo-heptanes (Venable, Am. 10,
237).
Heptane MejCH.CH,.Et. Eihyl-isoamyl.
(90-35°) (Thorpe, 0. J. 37, 216). S.G. | -69692
(T.); m -6833 (G.). O.E. (0°-10°) -001253;
(0°-50°) -0013318; S.V. 161-98. V.D. 3-45
(calc. 3-47). A product of the distillation of
whale oil under pressure (Engler, B. 22, 595).
Formed by the action of sodium (14 pta.j on a
mixture of EtI (60 pts.) and iso-amyl iodida
(70 pts.) (Wurtz, A. Ch. [8] 44, 275). Formed
also by gradually adding sodium to a mixture of
ethyl and iaoamyl bromides at 25°, then heating
for a few hours at 100° and fractionally distilling
(Grimshaw, G. J. 26, 309). Obtained also from
CH,.0H(0H).CHj.CH2.CHMe by successive treat-
ment with EI and with Zn and HCl (Furdie,
0. J. 39, 467). According to Berthelot {Bl. [2]
9, 455) phthalic and terephthalio acid heated
with (80 pts.) saturated HIAq yield a heptane
(91°-93°) ; Berthelot also obtained by this treat-
ment heptanes from toluene and from o- and p-
toluidine (O. B. 68, 606).
Heptane CMeEtPrH. Methyl-ethyl-propyl-
methane. (91°). S.G. fg -6895. [0] + 2-70 for 100
mm. From active amyl iodide, propyl iodide
and sodium (Just, A. 220, 153).
Heptane CHEtj. Tri-ethyl^methane. (96°).
V.D. 101-6. S.G. ^-689. Formed by the action
of ZnEtj and sodium upon orthoformic ether
(Ladenburg, B. 5, 762). Colourless liquid.
Heptane CMe^Etj. (87°). S.G. 2 '7111;
^ -6958. Formed by the action of ZnBtj upon
CHj.CClj.CHj (from acetone), the distillate being
mixed with water and fractionally distilled
(Friedel a. Ladenburg, A. 142, 310). Besides
n-heptane, Pennsylvanian petroleum contains a
heptane (90°). S.G. is .709 which is either
CMCjEtj or CHMeEtPr for it gives on oxidation
a ketone CjH„0 (142°-146°) which on further
oxidation yields nothing but acetic acid (Schor-
lemmer, 0. J. 26, 319) . The heptane in question
gives rise to a mixture of heptyl chlorides (144°-
158°), to a heptylene (90°-92°), to a primary
heptyl alcohol (165°-170°),to a secondary heptyl
alcohol (148°-150°), and to a heptoio acid (209°-
213°).
Beferences, — Di-bbomo- and Bi-celobo-
EEFTAKB.
HEFXAITE FHOSFHONIG ACID
C,H„CHjPO(OH)j. [106°].
Formed by heating oxy-heptane phosphonio acid
CbH,3CH(0H).P0(0H)j with cone. HIAq at
200° (Fossek, M. 7, 29). Swells up in a little
water, forming a jelly. Sol. alcohol, ether, and
ligroin.
Oxy-heptane phosphonic acid
0,H,5.CH(OH)PO(OH)2. [186°]. From oenan-
thol by successive treatment with PClj and water
(Zepharovitch, M. 7, 28). Tables.
ra-HEPTAHE SULPHONIC ACID C,B.,^m,B.
(Winssinger, Bull. Acad. Belg. [3] 14, 12). Is
converted by chlorine into a chloro- derivative of
which the Ba salt is (C,H,3Cl2S03)2Ba. A tri-
chloro-Bulphonio acid is also formed. Id, yields
two compounds, the one insoluble in water is
djHsOlaO, and the other is C^HjOlsO^. The Ba
salts of these acids crystallise out together
forming crystals which on analysis correspond to
the formula
2(0^„0I,S0,)jBa -I- 8(C,H,Cl,Oj)2Ba + 24aq
(Spring a. Winssinger, Bl. [2] 49, 68).
HEPIENE v. Eefiylenk.
zs2
676
HBPTENOIO ACID.
HEPTENOICACID CjHijOj. TetmcryUoaeid.
(218° i. v.). Formed by the dry distillation of
turpenylio acid CgHijO* (Kttig a. Krafft, A. 208,
79). Liquid, smelling like valeric acid ; lighter
than water. SI. sol. water. Gives acetic acid
by potash-fusion. Combines with TTBr forming
CjH,sBrOj which, on standing, changes to the
anhydride of ozy-heptoic acid. Combines with
bromine. — CaA', Saq : needles or prisms, v. sol.
water. — ^AgA' : small needles (from water).
SthyletherEU.'. (190°). (Amthor,.4r.Pa.
[3] 18, 536).
HeptenoicaciaPr.CH2.CH:OH.C02H. Formed
by heating isovaleric aldehyde with HOAc and
NaOAo (Fittig, B. 16, 1438). Liquid, volatile
with steam.
Heptenoic acid Pr.OH:OH.CHj.OOjH. (225°).
Formed, together with the lactone of oxy-heptoic
acid, by heating propyl-paraconic acid (the lac-
tone of osy-butyl-succinic acid) (Fittig, B. 20,
3179).
Beference. — Chlobo-heptenoic aoid.
HEPXENYL BBOMIDE OjH.sBr. (165°).
Formed by the action of alcoholic KOH on di-
bromo-heptane derived from cenanthol and FBr^
(Eubien, A. 142, 294 ; B. 8, 409).
HEPTEHYIi CHLOBIDE 0,H,301. Chloro-
mnwnthylene. Chloro-hspiylene. (155° cor.).
From di-chloro-heptane (ceuanthylidene chloride)
CiHhCIj and alcoholic KOH (Limpricht, A. 103,
82). Heated with alcoholic KOH it yields C,H,2
which forms with alcoholic AgNO, a pp.
C,H„AgAgN03 (BShal, Bl. [2] 49,581).
Heptenyl chloride C,H,sCl. (141°). From
di-propyl ketone and PCI5 (TavUdarofE, B. 9,
1442).
Heptenyl chloride C,H„C1. (119°). S.G.*
•951. From di-isopropyl ketone and POI5 (Henry,
B. 8, 400). AlcohoUc EOH converts it into
tetra-methyl-allylene (70°).
Heptenyl chloride C,H,,C1. (55° in vacuo).
From the heptiuene derived from perseite and
HCl (Maquenne, O. B. 108, 101). Crystalline.
Does not combine with Br. Potash reproduces
the heptinene.
HEPTIC ACID (so called) CjHiA (Pawlofl,
C. B. 97, 99) ; C,H,„02 i.e. CH,.00.C(C02H):C,Hs
(Demar(jay). [151°]. One of the products of
the action of alcoholic KOH on bromo-isobutyl-
aceto-acetic ether (Demargay, C. B. 86, 1185).
Flat needles (from water) ; sol. chloroform, si.
sol. cold water. Colours FeCl, pale brown. De-
composes carbonates only on heating.
HEPTINENE C,H,j M. Pr.CH^.CHj.CiOH.
'CEnanthylidene. Beptme. Amyl-acetylene.
(107°) (E.) ; (102°) (B.). S.G-. 2 -7508. Formed by
boiling di-chloro-heptane Pr.OHj.OHs.CHj.CHClj
with alcoholic KOH and heating the resulting
heptenyl chloride with alcoholic KOH at 150°
(Limpricht, A. 103, 84; Bubien, A. 142, 294).
Oil, with alliaceous odour, lighter than water,
V. sol. alcohol and ether. Bromine acts vio-
lently upon it, forming 0,H,jBr2 and CiHi^Brj.
Ammomacal AgNOa gives a white pp. ; ammo-
niacal CojClz forms a yellow pp. (Bruylauts, B.
8, 409). An alcohoho solution of AgNO, gives
a pp. of C,H„AguN08, sol. excess of the precipi-
tant (B6hal, Bl. [2] 49, 335). When heated for
36 hours at 145° with alcohoUo KOH in a sealed
tube it changes to methyl - butyl - acetylene
C,H,.C:CMe (B6hal, A. Ch. [6] 16, 428). When
dissolved in excess of HjSO^ and distilled with
water it gives methyl amyl ketone CjHu.CO.CH,
(B6hal, A. Ch. [6] 15, 270).
Heptinene C,H,.„ (104°). S.G. ^ -803.
From the product of distillation of rosin (Tilden,
B. 13, 1605 ; Eenard, C. B. 91, 419 ; Morris,
C. J. 41, 173). Occurs also among the products
of the action of boiling HIAq upon perseite
(Maqnenne, C. B. 107, 583 ; 108, 101). Liquid,
not precipitated by ammomacal AgNO,.
BeacUons. — 1. Absorbs oxygen readUy. Thus
in 10 days it absorbs 100 volumes of oxygen, and
if the product be distilled crystalline C^H^O, is
got. — ^.HjSOiConvertsitintodi-heptineueCijHj.
(246°) ; V.D. 94-2.— 3. HNO, (S.G. 1-3) forms a
little di-miro-hejptylene 0,H,2(N02)j (j. v.), COj,
formic, acetic, butyric, and snccinic acids.—
4. KjCrjO, and H^SO^ give COj and acetic acid. —
5. Forms two bromides, O^Hi^Brj and CjHijBr,.—
6. When heated to a dull red heat it gives pen-
tinene, hexinene (72°), benzene, toluene, and
hydrogen, the two last named being the chief
products (Eenard,_ C. B. 104, 574).— 7. Cone.
HIAq forms, even in the cold, crystalline C,H„I.
8. Cone. HClAq at 150° forms crystalline
CjHjsOl which boilB in vacuo at 55°.
Constitution. — MeCH:C:CHPr would give
butyric and acetic acids on oxidation. Maquenne,
however, considers the hydrocarbon to contain a
tetra-methylene nucleus.
Heptinene 0,H,2 i.e. CHj.CrO.CtH,. Methyl-
butyl-acetylene. (113°). S.G- 2 -763. Formed
by heating G5H„.C:CH with alcoholic KOH at
150° (B6hal, A. Ch. [6] 15, 428). Liquid. Gives
no pp. with ammoniacal Cu^Clj, with ammoma-
cal AgNO,, or with alcoholic AgNO,. Gives a
ketone on hydration. Forms a compound with
HgCl,.
Heptinene C,H,2 i.e. Et.C:C.C3H,. Ethyl-
propyl-acetylene. (106°). S.G.-2 -760. Prepared
from di-propyl ketone by treating with PCI,, and
heating the resulting (C3H,)2CCl2 with alcoholic
KOH for 20 hours at 140° (Bfihal, Bl. [2] 48,
216 ; A. Ch. [6] 15, 413). Liquid, with strong
odour resembling acetylene. Does not react with
ammoniacal CujClj. Forms a white compound
with HgClg, which when treated with dilute
HCl reproduces di-propyl ketone. Combines
energetically with bromine. If the hydro-
carbon be dissolved in cone. HjSO,, and the
solution be diluted with ice, di-propyl ketone is
obtained.
Heptinene G,H,2 i.e. MejCiCiCMe^. Tetra-
methyl-isoallylene. (70°). From di-isopropyl
ketone by successive treatment with PCI5 and
alcoholic KOH (Henry, B. 8, 400). Does not
ppt. ammoniacal AgNO, or CujCl^.
Heptinene C^Hi^. Heptylidene. (115°-125°).
Formed in small quantity in distilling calcium
succinate (Funaro, O. 11, 276).
HEPTINENE GLYCOL v. Di-oxy-hepitlene.
HEPTINOIC ACID C^.oOj i.e.
Pr.CHj.CJO.COjH. Butyl-acetylene ca/rboaylic
acid. (135° at 20 mm.). ' From methyl-propyl-
aoetylene (hexinene) by heating with sodium at
155° and treating the product, suspended in
ether, with OOj (Favorsky, J. B. 1887, 553). Oil,
which does not solidify at -20°. The silver
salt soon decomposes into COj and silver-
hexinene.
SEPTOTC ACID.
677
Salts. — CaA'g : slender needles (from water).
— BaA'j: small spangles (after drying over
H,SO,).
HEPTINYl ALCOHOL 0,H,jO i.e.
(CH,:0H.0Hj)2CH.0H. Di - alM - carbinol.
(151° cor.). S.G. § -8758 ; V° -8644. Formed by
the action of zinc on a mixture of allyl iodide
(2 vols.) and formic ether (1 vol.) ; the mixture
is kept cold, and is finally mixed with water
and distilled (Saytzeff, A. 185, 129 ; B. 9, 1600).
A by-product in its preparation boils at c. 211°,
and appears to be C,„H,jO, or di-aUyl-carbinol,
in wMch one H is displaced by propyl (W.
SohestaiofE, J.pr. [2] 30, 215). Di-allyl-carbinol
is an oil. It unites with bromine, forming a
tetrabromide. Chromic acid mixture oxidises it
to formic acid and COg, no acetic acid being pro-
duced. EMn04 gives oxalic acid and an acid
CsHjOj (Sohirokoff, J. pr. [2] 23, 207). With
HCIO, followed by elimination of CI, it gives,
not 0,H„(0H)5, but its anhydride C,H„(OH)sO
(S. Beformatsky, J.pr. [2] 31,318).
Acetyl derivative OtELhOAo. (170° cor.).
S.a. 2 -9167 ; !^ -8997 (Saytzeff, A. 185, 136).
Methyl ether (OsHJ^CH-OMe. (136° i.V.).
S.G. 2 -826 ;f -810. O.E. (0°-20°) : -001. Formed
by the action of sodium and Mel on the alcohol
(K. Ejabinin, J.pr. [2] 23, 270). Beactions.—l.
When bromine is added to an ethereal solution
combination takes place, a tetra-bromide,
(C3H5Brj)jCH(OMe), being formed.— 2. Oxidised
by KMnO,, the double unions are broken, the
product being the methyl derivative of /S-oxy-
glutaric acid (COjH.CH2)20H.OMe (q. v.).
Ethyl ether (0JS,),GB..O^t. . (U4° i. V.).
S.G. 2-821; %°-802. C.E. (0°-20°) -0012. From
the alcohol by sodium and EtI (Ejabinin, J.pr.
[2] 23, 272).
HEPTINYI CHLOKIDE C,H„C1 i.e.
(CHj:CH.CH2)2CHCl. (144°). From heptinyl
alcohol and POI5. Converted by alcoholic KOH
into heptonene C,H,„ (115°).
HEPTINYL GLYCOL v. Di-oxy-heptzlems.
m-HEPTOIC ACID 0,S^fii i-e.
Pr.CH2.OH2.OH2.CO2H. (ErumtMa acid. Mol. w.
130. [-10-5°]. (223°); (222° cor.) (Perkin, G.
J. 45, 484). S.G. 2 -9313 (Zander, A. 224, 69) ;
If -9225; H -9160; f -9160 (Bruhl). O.E.
(0°-10°) -00087. M.M. 7-552 at 14-5°. ^« 1-4266
(B.). Boj 58-19. S.V. 174-6 (Z.).
WwrmaUon. — 1. By the oxidation of oenanthol
with nitric or chromic acid (Bussy, J. Ph. [3] 8,
329; A, 60, 248 ; Tilley, A. 67, 107; Schneider,
A. 70, 112 ; Sohorlemmer a. Grimshaw, 0. J.
26, 1073 ; A. 170, 141 ; Mehlis, A. 185, 358).—
2. By oxidation of castor oil (THley, A. 39, 160 ;
c/. Arzbacher, A. 73, 200 ; Brazier a. Grossleth,
A. 75, 249).— 3. By the action of HNO, on oleic
acid (Laurent a. Eedtenbacher, A, 59, 50). —
4. By saponification of hexyl cyanide, obtained
from TO-hexyl alcohol (Lieben a. Janecek, A. 187,
126).— 6. By oxidation of M-heptyl alcohol
(Schorlemmer, Pr. 14, 171; A. 161, 279; 170,
141). — 6. By reducing isodulcite carboxyUc acid
with HI and phosphorus (B. Fischer, B. 21,
2175). — 7. By the action of HNO3 on Chinese
wax (Buckton, C. J. 10, 166), on azelaic acid,
and on spermaceti (Arppe, A. 120, 288).— 8. By
fusing sebacic acid with potash (Koch, A, 119,
173).— 9. By boiling the barium salt of mannita
carboxylic acid with aqueous HI and red phos-
phorus, diluting, and extracting with ether.
The ethereal solution is shaken with mercury,
and the product treated with H2SO4 and zinc-
dust. The acid is finally distilled over with
steam (E. Fischer a. Hirschberger, B. 22, 372).
I Preparation. — CEnanthol (1 pt.) is treated in
the cold with dilute HNO3 (2 pta. composed of
1 vol. HNO3 S.G. 1-4 and 2 vols, water) ; the re-
sulting acid is distilled im vacuo (Krafit, B. 15,
1717). •
Properties. — Liquid. Gives propionic and
Buccinio acids when oxidised by chromic acid
mixture.
Salts. — ^Ammonium salt is v. sol. water,
alcohol, and ether, and non-crystalline. — KA'
(at 100°): silky mass.— NaA': needles; often
obtained as a jelly. — CaA'jt thin flat needles.
S. -914 at 8-5° (S. a. G.).— CaA', aq : thin needles.
S. (of CaA'j) -94 at 12° (L. a. J.).— BaA', : thin
lamina or broad needles. [239°] (M.). S. 1-76
at 12° (G. a. S.) ; 1-56 at 22° (M.) ; 1-68 at 9°
(L. a. J.). — ZnA'2 : prisms (from alcohol) ; si. sol.
water, v. sol. alcohol. [132°].— ZnA'jiaq.— OdA'2 :
laminsB. [96°]. — PbA'2: laminse (from hot water).
— OuA'j: green prisms (from alcohol). — AgA :
smaU wooUy needles (from hot water) ; insol.
cold water and alcohol, si. sol. boiling water.
Methyl ether MeA'. (180°) (Neuhof, J.
1866, 323) ; (173°) (Cahours a. Demar(;ay, Bl.
[2] 34, 481) ; (172°) (Gartenmeister, A. 233, 249).
S.G. 2 -887 (N.) ; " -889 (0. a. D.) ; g .8981 (G.).
S.V. 196-2. C.E. (0°-10°) -00102.
Ethyl ether EtA'. (188° i. V.). S.G. 2
-8879 (L. a. J.) ; § -8861 (G.) ; ^| -8718 ; |f -8648
(Perkin, 0. J. 45, 502). M.M. 9-54 at 14-9°-
C.E. (0°-10°) -00101 (G.). By boihng the ether
(20 CO.) with TO-amido-benzoio acid (10 g.) for
eighthoursthereisformedCiH.sO.NH.OBH^.COjH
[202°] (PeUizzari, A. 232, 149).
Propyl ether VtM. (206-4°). S.G. g-8824.
C.E. (0°-10°) -0097. S.V. 246-5 (G.).
Butyl ether PrOHjA'. (225-1°). S.G. 8
-8807. O.E. (0°-10°) -00092. S.V. 271-3 (G.).
n-Septyl ether CjH.jA'. (274-6°) (G.);
(277° cor.). S.G. is -870 (Cross, C. J. 32, 123 ;
B. 10, 1602); If -8652; if -8593 (Perkin);
2 -8761. O.E. (0°-10°) -00086. S.V. 350-2.
M.M. 14-655 at 13-6°.
Ootyl ether CsH^A'. (290-4°). S.G. g
-8757. S.V. 876-2. O.E. (0°-10°) -0086 (Garten-
meister).
Phenyl ether CjHjA'. (275°-280°). From
the chloride C,H,30C1 and phenol (Cahours, C.
B. 39, 257).
Amide C3H„.CONH2. [96°]. (250°-258°).
Formed by heating the ammonium salt to 230°
(Hofmann, B. 15, 983), and by the action of
NHa on the anhydride (MehUs, A. 185, 368).
Laminse (from water) or needles (from alcohol).
Converted by a mixture of XOH and bromine
into 03H,3NH.CO.NH.C0.03H,3 [97°] (Hofmann,
B. 15, 759).
Methyl-amide CeHiaOONHMe. (266°).
S.G. i£ -895. Thick liquid. Obtained by heat-
ing the acid with methylamine for 5 hours at
230°, dissolving the product in ether, and adding
KjCOs (Franchimont a. Klobbie, B. T. C. 6, 247).
Di-methyl-amide OsHjaCONMe^. (243°).
S.G. iS- -894.
Ethylamide C^„.CO.NHEt. [6°1. <268°),
678
HEPTOIO ACID.
Formed by heating the ethyl-ammonium salt at
230°. Decomposed by pure HNO, with evolu-
tion of N,0 (JFranchimont a. Klobbie, B. T. O.
6, 248).
Di-ethyl-amide 08H,3.CO.NEt2. (258°).
S.G. ^ -881. Liquid (P. a. K.).
Anhydride (CeH,s.00)20. Mol. w. 242.
(268°-271°). S.G. 21 -gsg. Obtained by dis-
tilling the acid with PCI5, and heating the re-
sulting heptoyl chloride with potassium heptoate
(Mehlis ; cf. Chiozza a. Malerba, A. 91; 102).
mtrile C8H„.CN. (175°-178° i. V.). S.O.
-- SSS. Formed by heating heptoio acid with
potassium snlphooyanide (Mehlis). Formed also
by the action of AojO on the ozim of heptoio
aldehyde (Lach, B. 17, 1572) ; and, together
with heptylamine, by allowing a mixture of the
amide of octoic acid (1 mol.) and bromine (3
mols.) to run into a 10 p.c. solution of NaOH
(Eofmann, B. 17, 1407). Oil; sol. alcohol and
ether.
Chloride OsH,sOOOI. With di-methyl-
aniliue in presence of ZnCl^ it gives as conden-
sation products, CgH,3.00.CeH,NMe2, and a base
CogHg^N,- Xhis latter body has all the proper-
ties of a leuoo-base. Heated with Mel at 100°
it gives the salt C23Hs2N22MeI. Oxidising agents
act on it very easily, and develop a fine blue
colour ; FCjClj gives OjjHjoNjHCl, having a fine
blue colour. This is reduced by Zn in acid
solution to the original leuco-base. The blue
colour disappears with excess of acid. KOH or
KaOH does not set free the base, but causes a
complete decomposition (Auger, Bl. [2] 47, 48).
Isoheptoic acid Pr.CHj.CHMe.OOijH. Me-
thyl-butyl-acetic aeid. Butyl-propiomc acid.
(212°). S.G. s -9305 ; =gi -9138. S. -36 at 4°.
]?brmed by sS,ponifioation of the corresponding
nitrile which is obtained from ECy and the
secondary hexyl iodide derived from mannite
(Hecht, A. 209, 809; Heoht a. Munier, B. 11,
1781). Colourless oil; si. sol. water, miscible
with alcohol, ether and chloroform. On oxida-
tion with chromic acid mixture it yields acetic
and butyric acids. A solution of its Na salt gives
white pps. with salts of Ca, Al, Zn, Cd, Mn,
Hg, Pb, and Ag; a brown pp. with FeClj, a
green pp. with NiClj, and a blue pp. with
CUSO4.
Salts. — KA': very deliquescent, and v. e.
sol. water. — NaA': very deliquescent. — LiA':
crystalline, v. sol. water, m. sol. alcohol. —
CaA'j4aq: S. 11-9 at 1°; 13-9 at 6-7°; 12-1 at
16-8°; U-3 at 28°; 6-1 at 100°.— SrA'j 2aq :
grouped needles. S. 19-2 at 3°.— BaA'j IJaq :
crystalline aggregates. S. (of BaA',) 30 at 1°.—
AgA'. S. -23 at 4°.
Methyl ether MeA'. (157° i.V.). S.G.
«-879.
Ethyl ether EtA'. (173° i.V.). S.G. if
■8685 ; fl -8570.
Propyl ether PrA'. (192° i. V.). S.G.
!f8635:
Isopropyl ether PrA'. (177°). S.G. if
•859. 1 / IS
Heptoio acid C,H„02 i.e.
Pr.CH2.OHMe.GO2H. (210°oor.)i Formed from
methyl-bntyl-aoeto-acetio ether and oono. alco-
holic KOH. Formed from Isevulose by shaking
with HCy, decomposing the resulting CjHisNOj
by fuming HCUq, aud reducing the product
with HI and phosphorus (Kiliani, B. 18, 3066 ;
19, 221). Oil.— OaA'j 6aq : long needles. S.
(of CaA's) 7-8 at 17-5°.— SrA'2 5aq. This acid
should be identical with the preceding, bat dees
not seem to be so.
Heptoic acid
{CB.^)fiK.GB..,.GB.^.GB.^.COJB. (?) Iso - amyl ■■
acetic or iso-csnanthylic acid. (216'5°-218°
cor.). S.G. " -926. Formed when CO is
passed at 180° over NaOAc mixed with
NaOCjH,, (Poetsoh, A. 218, 67).
Salts . — ^NaA'aq. — CaA'j 3 |aq.
Methyl ether MeA'. (166°-167-5° cor.).
S.G. IS -884.
Ethyl ether EtA' (182° cor.). S.G. 15
•872. Not attacked by alcoholic NH, at 120°.
Heptoic acid C,H„02. (210°-213°). Formed
from _ isoheptane (ethyl-isoamyl) Pr.CH2.Pr by
chlorinating, displacing CI by OH, and oxidising
the resulting heptyl alcohol (Grimshaw, A.
166, 168). Oil, with unpleasant odour. Proba-
bly identical with isoheptoic acid. — CaA'2 2aq:
small needles. — AgA': small needles. The
barium salt is amorphous.
Heptoio acid (CH3)2CH.CH2.CH2.CH2.C02H.
Isoamyl-acetic acid. An oil, formed by
treating acetic ether with sodium and isoamyl
iodide successively, the resulting isoamyl-aoeto-
aoetio ether being saponified (Frankland a.
Duppa, A. 138, 388). Probably identical with
the acid of Poetseh.
Heptoic acid C,Hn02. (209°-213°). Formed
by oxidising the isoheptane (90°) in Pennsyl-
vaniau petroleum (Schorlemmer, C. J. 26, 319).
Its bariuila salt is amorphous. The calcium
salt crystallises by spontaneous evaporation
in long transparent needles or prisms. The
silver salt is a floooulent pp.
Heptoic acid C,H„02 i.e. CHs.CEt2.CO2H.
Di-a-ethyl-propionic add. (208°). Formed by
acting on ZnEt2 with acetyl chloride ; converting
the resulting CMeEtjOl into the corresponding
iodide ; heating this compound with KCy for a
week; and digesting the resulting CMeEt,Cy
with fuming HOlAq (IdanofE, Bl. [2] 26, 460).
Oil. — BaA'jSaq: separates on rapid cooling in
EteUate groups of flat needles ; on slow cooling in
flat prisms. — KA': very soluble, and non-crys-
talline.— KHA'2 : stellate groups of needles. —
The silver salt is si. sol. boOing water, sepa-
rating as tufts of small needles. — The lead
salt is a white pp. si. sol. cold water, the
solution becoming turbid when heated.
Heptoic acid CHuOj i.e.
(CHs)2CH.CHMe.CH2.C02H(?). (220°). Formed
by passing CO over a mixture of NaOBt and
sodium isovalerate At 160° (Looss, A. 202, 321).
OU.
Heptoic aeid G^'K^fl^. Amethenic acid.
(185°-230°). Obtained, together with COj and
acetic acid, by oxidising diamylene with KgCrO^
and dilute H2SO, (Von Schneider, A. 157, 185).
Oil, lighter than water. Its salts are decom-
posed even by CO2. The K, NH,, Ca, and Mg
salts are crystallisable and v. sol. water. —
SrA'jSaq: small needles (Wyschnegradsky a.
Pawloff, J. B. 7, 170).— ZnA'j: nodules, si. sol.
cold water; the aqueous solution deposits a
gelatinous pp. when heated. — AgA' : pulverulent
pp., Bl. sol. water.
HEPTOIC ALDEHYDE.
679
Heptoie aeid CHa.CHj.OHj.CHBt.OOjH.
Ethyl-prcyayl-acetic add. (209° oor.). From
Bthyl-propyl-aoeto-acetio ether by saponifioation
with oono. alcoholic KOH (Kiliani, B. 19, 227).
Oil.— CaA'a2aq : soft needles. S. (of OaA',) 11-4
at 19-5° — SrA'j2aq: small prisma. S. (of SrA'J
27-9.-PbA'23aq.— CuAV The silver, barium,
and lead salts form colourless needles. The
acid is perhaps identical with that of Hedht.
Beferences. — Auido-, and Bbouo-, eifioio
iOIDS.
HEPTOIC ALSEHTSE 0,H,iO i.e.
OHs.OHj.CHj.OHj.CH,.OHj.CHO. CEnanthol.
Mol. w. 114. (155°). S.G. f -8495 (Briihl) ;
if -8226 ; -?s -8158 (Perkin, O. J. 45, 477). V.D.
4-14 (calo. .3-95). ij.g 1-4309. Ea, 55-59. M.M.
7-422 at 16-2°. The name oenanthol is due to
the belief of Liebig that heptoie acid was the chief
product of the saponifloation of fusel oil from
wine (Liebiga. Pelouze, A. 19, 241). Obtained by
distilling castor oil (Bussy, A. 60, 246 ; J. Ph.
13, 62 ; [3] 8, 321 ; H. Sohifl, Z. 1870, 77 ; KrafEt,
B. 10, 2035). Purified by preparing its com-
pound with NaHSOj, which is subsequently dis-
tilled with Na^COs (Bertagnini, A. 85, 281).
Dried over NajSO, and rectified (Erlenmeyer a.
Sigel, A. 176, 342). The yield is 12 p.o. of the
castor oil (Jourdan, A. 200, 102). OQ, miscible
with alcohol and ether. Has a strong odour.
When moist heptoie aldehyde is exposed for a
long time to a low temperature it deposits crys-
tals of a hydrate G,H,40|aq (? heptoie orthalde-
hyde) (Bouis, A. Ch. 44, 87). Heptoie aldehyde
reduces AgNO,, forming a mirror.
Reactions. — 1. Heptoie aldehyde is poly-
merised by prolonged contact with K^CO,. The
product is a crystalline solid [53°] which, when
heated, begins to decompose at 115° into'heptoic
aldehyde, the aldehyde CigH^jCHO, and an alde-
hyde Cj^mO, (c. 385° at 250 mm.). The solid
polymeride when treated in acetic acid solution
with sodium yields heptyl alcohol and a sub-
stance Cj,Hj,Oj (Bruylants, IS. 8, 414 ; Perkin, jun.,
C. J. 43, 67). — 2. Alcoholic (1-6 p.c.) potash yields
tetradecenoio (amyl-hexyl-acrylic) acid Ci^H^gO,,
its aldehyde C^HssO, the aldehyde CiAgO,
and heptoie acid (Perkin, jun., O. J. 48, 67 ; B.
15, 2806).— 8. Cone. KOHAq also forms con-
densation products, together with heptoie acid.
4. Solid EOH polymerises heptoie aldehyde even
at 0°, forming a solid and a liquid polymeride.
Each of these bodies when distilled gives heptoie
aldehyde, tetradecenoio aldehyde, and G^^fls
(Borodin, B. 5, 481 ; 6, 982). Solid KOH at
120° forms an oil ChHjuO which boils, with de-
composition, at 260° (Tilley, P. M. 33, 81 ; A.
67, 109). — 5. ZnCl, forms the aldehyde C,4H,jO.
6. Cold cone. HNO, forms a solid isomeride
' metoenanthol.' — 7. Dilute chromic acid mixture
forms heptoie acid. — 8. When left for some
weeks in contact with quicklime, there is formed
heptyl alcohol, heptoie acid, heptylene (95°-100°),
octylene (122°-125°), ennylene (145°), and the
ketone C„Ha,0 fPittig, A. 117,76).— 9. In acetic
acid solution sodAum reduces it, forming heptyl
alcohol, tetradeeenyl alcohol CiaHjsCHjOH, and
tetradecenoio aldehyde O^^B^GKO (Perkin). In
a wet ethereal solution Na forms heptyl alcohol,
heptoie acid, tetradecenoio aldehyde, and a body
CjiHjjO. — 10. PCI, forms di-ehloro-heptane
C,H„CHOV— 11. PCljBrj forms G^iJCfSBt^
Chlorme forms oily OiHhCIjO (A. W. Williamson,
A. 61, 44). — 12. Besorcin and dilute HCl form a
resin in t^e cold (Michael a. Byder, Am. 9, 134).
13. Heptoie aldehyde (20 g.) heated with tri-
methylene glycol (30 g.) at 160° gives rise to
C^„.CH<;°;°gp.CHj, an on, (c. 216°), S.G.
2 -938. With ghjcol, in like manner, it forms
CsHu-CH^qIq]^ (Lochert, A. Ch. [6] 16, 35,
52). — 14. NaOAo and AcjO at 170° give ennenoio
acid (Sohneegans, A. 227, 85). — ^16. Ao,0 and
barium succinate give hezyl-paraoonio acid
(Schneegans). — 16. Aqueous ammoma (150 g. of
S.G. -89) added to cooled heptoie aldehyde (80 g.)
forms an oUy layer of heptoie aldehyde
ammonia CgH,3.CH(OH)NH2 (Erlenmeyer a.
Sigel, A. 176, 343). — 17. Dry ammonia passed
into dry heptoie aldehyde forms heptoie hy-
dramide (CsH,3CH)3N2, which boUs above 400°
and does not combine with acids. The hydramide
is converted by boiling water into a yellow oil
CjiHjjNO, and by water at 125° into CjsHjsNO,
which is also ayellow neutral oil (SchifF, A. Su^ppl.
3, 367 ; Siippl. 6, 24). — 18. Colourless ammormum
sulphide in concentrated solution formsheptoio
thialdine Cj,H„NS2 a colourless oil, S.G. SJ
-896. It forms a hydrochloride B'HCl, which is
insol. water, and crystallises from alcohol in
needles (Schifi). — 19. A solution of heptoie alde-
hyde saturated with ammonia is converted by
hydrogen cyanide into oily C5H,5CH(NHj).0N,
and another oil CjgHjgN, (Erlenmeyer a. Sigel, A.
177, 111).— 20. If heptoie aldehyde (100 pts.) be
mixed with a little PCI5 (1 pt.) and dry hydrogen
sulphide be passed in, there is formed the com- '
pound CjH,s.CH<;°>CH.C,H,3, (200°-250°).
S.G. 22 -875 (SchiflE).— 21. An alcoholic solution
of heptoie aldehyde, on saturation with HCl,
yields C8H,sCHCl(0Bt), a light oil, which is de-
composed on distillation into a mixture of hydro-
carbons and other bodies (Williamson ; Schiff,
Z. [2] 6, 74).— 22. Phosphomum iodide at 0*=
forms (C|iH,j.0H.0H),PI, which crystaUises in
minute leaflets, [122°], insol. water, si. sol. ether,
V. sol. alcohol (Girard, A. Ch. [6] 2, 40).—
23. Isoamylamine forms CeH,3.CH:KC5H„, a
yeUow, non-volatile, basic oil (Sohiff, A. 140,
93).— 24. Heptoie aldehyde (70 g.) heated with
ardlme (57 g.) and HOAc (150 g.) at 100° forms
CBH,s.CH(OH).NHPh, a red oil with pleasant
odour (Leeds, A. G. J. 5, 2). — 25. By heating
with aniJ4me or di-phenyl-urea there is formed
OjHia.CHrNPh (or (CsH,3.CH)2(NPh),), a neutral
yellow oil, which combines with isoamyl iodide
at 100° forming C^jHsaNjC^HnI (Sohiff, A. 148,
336; Swppl. 3, 351). — 26. Bemoyl-aniline tonus
C8H„.CH(NP1lBz)2, which is spUt up on distil-
lation into BzjO and (C3H,3.CH)j(NPh)2 (SchifE).
27. Ethyl-amUm forms OsHia-CHlNPhEt),
(215°-220°), a neutral oil.^28. AUyl-ardUne
forms CjH,s.CH(NPh03H5)2, a neutral oil.—
29. Di-phev/yl-tMo-urea in the cold forms
OsH,3.CH<^j,prJ>OS, a neutral solid, sol. ether
(SchifE).^ — 80. Xj/Wmein glacial acetic acidforms,
accordmg to Leeds (A. G. J. 5, 2), a red liquid
C8H„.CH(OH).NHOsH3Me2 with pleasant odour.
31. (a)-Na/phth/ylarmm,B in HOAc forma, in like
manner C,H„.CH(OH).NHC,„H„ a red Uquid.
680
HEPTOIC ALDEHYDE.
BmelUng like piue-apples (Leeds). — 32. {a)-Na^h-
thylarmne added to a diy ethereal solntion of
heptoio aldehyde forms a yellow, amorphous,
nentral substance (CjH,5.CH)2(N0,i,H,)j ; insol.
water, sol. alcohol and ether (FapasogU, A. 171,
139).— 33. Treated with di-meihyl-amlme in
presence of ZnOlj there is formed (together with
products resulting from the polymerisation of
the aldehyde) a condensation product C23E34N2
or CBH,a.CH(CjHjNMej)j. This forms long
colourless needles [59-5°], (275° at 15 mm.) ; si.
sol. cold alcohol, insol. water. On oxidation
this base does not yield the corresponding car-
binol, but gives a passing colouration and an
odour of cenanthol (Auger, Bl. [2] 47, 42). —
34. ZnEtj followed by water forms the alcohol
C,H,s.CHEt.OH (195°) (Wagner, B. 17, Bef., 315,
Bef .). — 35. Heptoio aldehyde (75 g.) heated with
amline (20 g.) and cone. HClAq (60 g.) for 2 hours
at 100° forms amyl-hexyl-quinoline (Doebner a.
MiUer, B. 17, 1719).
Combinations with sulphites. — The
combinations with bisulphites of the alkalis may
be obtained directly, or by passing SO, into an
alcoholic solution of heptoic aldehyde containing
potash, soda, orNH,.— OjH,s.CH(OH).SO,Na aq :
brilliant unctuous scales ; v. sol. water, v. e. sol.
hot, nearly insol. cold, alcohol. Decomposed by
acids and alkalis, with liberation of heptoio al-
dehyde. With BaCl, its solution gives a pp. of
(0,H„SO,)^a, whence H^SO^ liberates oily
C,H,4S0„ a compound which is also formed by
passing SO^ into an aqueous solution of heptoic
aldehyde (Mendelejeff, A. 110, 241). —
OjHijSOjNH,: small shining prisms, al. sol.
water and alcohol. Decomposed by boiling water
into heptoic aldehyde and acid ammonium sul-
phite. When heated with potash-lime at 265°
it yields tri-hexyl-amine (Petersen a. Gossmann,
C. 0.1857, 198).— (0,H„0)2S0j,(NHjPh)j: nee-
dles. Obtained by mixing heptoic aldehyde with
an ethereal solution of aniline sulphite (Schifi, A.
140, 129).— C,H,jS0,NH3Ph : usuaUy obtained
in attempting to prepare the preceding (Sohiff,
A. 210, 127). Decomposed by water at 65° into
Oja,3.GH:NPh and crystalline
C3H,3.CH(OH).SO,NH3Ph aq.—
C,H„.CH(0H).S03.NH3.CH2.C02H : crystalline
mass, insol. ether, si. sol. alcohol. Obtained
by dissolving heptoic aldehyde in an aqueous
solution of glyoocoll saturated with SO, (SchifE,
4.210,125).
Phenyl-hydraeide 0,H„:N.NH(C,Hs).
(240° at 77 mm.). Oil. Formed by the action
of phenyl-hydrazine on oenanthol (Beisenegger,
B. 16, 663).
Oxim C,H,4.N0H. [50°]. (195° cor.).
Formed by the action of hydroxylamine (base)
on oenanthol (Westenberger, B. 16, 2992). Large
white tables. Sol. alcohol, ether, and hot water.
With FcjClj it gives a rose-red .colouration. HCl
resolves it into its constituents. By the action
of AcjO it is converted into thenitrile of heptoic
acid piiach, B. 17, 1572).
Ethyl ether 0,H„.NOEt. (186°). Oil.
HEPTOLACTONE v. Lactone of Oxt-hepioio
ACID.
HEPTONENE C,H„ i.e.
CH,:CH.CH2.CH:CH.CH:CH,. Heptane. (115°).
From di-allyl-carbinyl chloride and alcoholic
EOH (Saytzeff, A. 185, 144). Bromine forms
liquid C,H,(^re.
Heptonene CaH.i.CiCH. (0. 112°). S.G. »»
■7458. /in 1-4207. From heptoio aldehyde and
PCI5 followed by alcoholic KOH (Briihl, A. 235,
10).
Isomeride : Toi^uene DiHYnittDE.
HEPTONITEILE v. Nitrile of Hbpioio Aoro.
HEPTOYL. The radicle C3H,3.00.
HEPTOYL-ACETIC ALDEHYDE. Sodium
derivative CjH.s.CO.CHNa.CHO. Obtained by
treating methyl hexyl ketone (1 mol.) and formic
ether (1 mol.) with NaOEt suspended in ether
(Meyerwitz, B. 21, 1144). Phenyl-hydrazine
converts it into phenyl-hexyl-pyrazole CuE^gK,,
a thick oil (319°).
HEPTYI. The radicle CjH„.
Diheptyl v. Tetjsadeoanb.
HEPTYI. ACETATE v. HBPriL alcohol.
HEPTYL-ACETIC ACID v. Ennoio acid.
Di-heptyl-acetic acid v. Hexadbcoio acid.
HEYTYE-ACETO-AOETIC ETHEK v. Aoeto-
ACETIC ACID.
HEPTYI-ACETONE v. Meihtl ociylkeione
re-HEPTYL ALCOHOL C,H,eO i.e.
CH3.CH„.CH2.CH2.CH,.CH2.GH20H. Mol. w,
116. {175-8= i.V.) (Zander, A. 224, 84); (176-5'
i.V.) (G-rimshaw a. Sehorlemmer, G.J. 26, 1081)
(175-5°) (C. P. Cross, G. J. 32, 123) ; (176° cor.)
(Perkin). S.G. g -8342 (Z.) ; 2-838(0.); 4|-8308;
§1 -8252 (P.). M. M. 7-850 at 12-6°. OJB. (0°-
10°) -00083 (Z.). S.V. 168-3 (Z.). Occurs to a
small extent (1-5 g.) in brandy (100 litres) (Ordon-
neau, G. B. 102, 219 ; cf. Faget, Bl. 1862, 69).
Formation. — 1. By reducing heptoic alde-
hyde (oenanthol) in acetic acid solution with
sodium-amalgam ; the resulting heptyl acetate
being saponified with potash (Schorlemmer, A.
m, 304 ; c/.Bouisa. Carlet, 4. 124, 352; Jourdan,
A. 200, 102; Sorabji, C. J. 47,, 41).— 2. By re-
ducing heptoic aldehyde with zinc-dust and
HOAc (KrafEt, B. 16, 1723).— 3. From w-heptyl
chloride (Schorlemmer a. Thorpe, T. 174, 270).
4. Among the products of the distillation of
sodium ricinoleate with NaOH (Chapman, Z.
1865, 737 ; WUls, C. J. 6, 307 ; Petersen, A. 118,
69 ; Bailton, C. J. 6, 205).
Properties. — ^Liquid ; gives w-heptoio acid on
oxidation.
Acetyl derivative 0,H,50Ao. (191-5° cor.)
(Cross); (191-3° cor.) (Gartenmeister). S.G.
is -874 (C.) ; g -8891 (G.). S.V. 221-0. C.E.
(0°-10°) -00096. When obtained by heating
heptoic aldehyde (oenanthol) with zinc and
glacial HOAo it boils at 180° according to Bouis
a. Carlet (0. B. Bo, 140). The rate of formation
of this ether has been studied by Menschutkin
(Z.P.G.1,U1).
Methyl derivative C,'H.^fi'M.e. Methyl
heptyl oxide. (161°) (W.) ; (150°) (D.). S.G.
]^ -830 (W.) ; 2 ■7958 (D.). C.E. (0°-10°) -001
(Dobriner, A. 243, 3). From Na00^,5 and Mel
(Wills, C. J. 6, 307).
Ethyl derivative 0,B.ifl'Et. Ethylheptyl
oxide. (166°). S.G. is .790. From m-heptyl
iodide and NaOEt (Cross). Wills obtained from
NaOC,H„ and EtI a compound (177°); S.G.
is -791.
w-l80-heptylalcoliolCH3.(OBy3.0HMe.CHjOH
or (CH,).,CH.(CH,)3.CH20H. (165°) (G.) ; (104°)
(S.). S.G. iJiS -829 (S.). Obtained, together with
HEPTYL ALCOHOL.
631
mothyl - iso - amyl - carbinol, by passing dry
chlorine into the vapour of boiling isoheptane
{0Hj)2CH(0H2)3CH3, oonvorting the resulting
mixture olohlorides into acetates, and saponify-
ing these (Grimshaw, A. 166, 167 ; Sohorlemmer,
:Br. 14, 164, 464). It gives a heptoio aoid (210°-
213°) on oxidation.
Acetyl derivative C,H,.OAo. (179°).
S.G.1£5-871.
Heptyl alcohol C,H,50H. (165°-170°). Ob-
tained by ohlorination, &e., from the heptane
(90°) whioh occurs along with n-heptane in
Pennsylvanian petroleum (Sohorlemmer, O. J.
26, 319). Perhaps identical with the preceding
alcohol. Gives on oxidation a heptoio acid
(209°-213°).
Acetyl derivative C^ijOAo. (180°).
Sec-heptyl alcohol OH3(OHj),CH(OH).CH3.
Methyl-amyl-carbinol. (161°) (Sohorlemmer,
C. J. 26, 319 ; A. 161, 279) ; (167°) (Sohor-
lemmer a. Thorpe, 2". 174, 270). Formed from
the sec-heptyl chloride which is obtained by
chlorinating n-heptane. Formed also from
petroleum heptylene by treatmept with cold
cone. HClAq, and heating with HIAq at 120° the
portion which does not combine with HCl ; the
resulting iodide is then heated with Pb(0Ac)2
and the acetate saponified (Morgan). On oxida-
tion it gives a ketone (151°), and finally acetic
and n-valerio acid.
Acetyl derivative C,H,50Ac. (170°).
(Sohorlemmer, A. 188, 254).
Sec-heptyl alcohol Pr.CHj.CHj.CH(OH).CH,.
Methyl-isoamyl-carbmol. (147°) ; (148°-154°)
(P.). S.G. ?I5 -8185. One of the alcohols ob-
tained from isoheptane Jr-CHj-Pr by ohlorination
&o. (Grimshaw, 0. J. 26, 309). Obtained also
by reducing methyl isoamyl ketone with sodium
amalgam, tiie yield being 72 p.c. (Bohn, A. 190,
309 ; Purdie, C. J. 39, 467). Gives on oxidation
methyl isoamyl ketone (143°) and finally acetic
and isovaleric acids.
Acetyl derivative C^uOAc. (167°). S.G.
j^ -8595.
Sec-heptyl alcohol 0,H,50H i.e.
Et.CH(0H).CH2Pr. Ethyl-butyl-ca/rbmol. (141°).
Formed from petroleum heptane by successive
conversion into heptyl chloride, heptylene, heptyl
chloride, and heptyl acetate (Morgan, C. J. 28,
801). On oxidation it gives a ketone (141°),
and finally acetic and ra-butyric acids.
Sec-heptyl alcohol C,H,|,0H:. (149°). Formed
together with a primary alcohol (165°-170°)
from one of the heptanes (90°) in Pennsylvanian
petroleum, by ohlorination, &o. (Sohorlemmer,
C. J. 26, 319). Gives on oxidation a ketone
(142°-146°), and finally nothing but acetic acid.
S«o-heptyl alcohol PrjOH.OH. Di-propyl-
sarUnol. (160°) (K.); (154°) (S.) ; (155°) (U.a.
S.). S.G. §^ -8188 ; "■§ -8106 (U. a. K.) ; as -814
(K.) ; 2 'SS^Sl Formed by the action of sodium
on di-propyl-ketone mixed with a little water
(Friedel, A. Ch. [4] 16, 310 ; Kurz, A. 161, 205),
or by treating w-butyryl chloride with zinc propyl
foUowed by water (Stcherbakoff, Bl. [2] 34, 347 ;
37, 344). Formed also from di-propyl ketone
(1 mol.), -propyl iodide (3 mols.) and zinc
(Ustinoff a. Saytzeff, J. jor. [2] 34, 468). Oxida-
tion produces di-propyl-ketone, and finally pro-
pionic and butyric acid.
Acetyl derivative (170°-172°). S.G. f
•8587. Volatile liquid, with camphor-like odour,
si. sol. water, miscible with alcohol.
Sec-heptyl alcohol PrjOH.OH. Di-isopropyl-
ca/rUnol. (131°). S.G. ^^ -8823. Formed by
reducing di-isopropyl-ketone by sodium-amalgam
(Miinch, B. 7, 1370; A. 180, 333). Liquid,
smelling like peppermint, si. sol. water, v. sol.
alcohol and ether. Chromic acid mixture
oxidises it to di-isopropyl-ketone.
Sec-heptyl alcohol Pr.CH2.CBtH.OH. Ethyl-
isobutyl-cmhinol. (148°). S.G. a -827. Formed
by treating isovaleric aldehyde with ZnEtj and
water successively (Wagner, Bl. [2] 42, 330).
On oxidation it gives ethyl isobutyl ketone, and,
finally, acetic and isovaleric acids.
Acetyl derivative C,H,50Ac. (168°).
Ter^heptyl alcohol CEtaOH. Tri-ethyl-cwr-
binol. (141°-143° i.V.). V.D. 3-74 (for 4-01).
S.G-.V -8389 ; %» -8299 (B. a. S.) ; 2 -859 (N.).
Formation. — 1. Fromdi-ethyl ketone (Imol.),
EtI (3 mols.) and zinc (Barataeff a. Saytzeff,
J. pr. [2] 34, 463).— 2. From ZnEtj- and pro-
pionyl chloride (Nahapetian, 2. [2] 7, 274 ; A.
162, 44).
Gives on oxidation COj, di-ethyl ketone,
heptylene, propionic acid, and acetic acid.
Acetyl derivative C,H,.OAc. (160°-
163°).
Teri-heptyl alcohol Pr.OHj.CMe.OH. Di-
methyl4sobutyl-carbinol. (130°). From pseudo-
heptylene MCaCrCH.Pr by passing gaseous HI
into the hyirooarbon, and decomposing the
resulting iodide with moist Ag^O (Markownikoff,
Z. 1871, 268). Formed also by dropping iso-
valeryl chloride (1 mol.) into cooled zinc methyl
(2 mols.), leaving the mixture to itself for a
month, and then decomposing it with water
(Pawloff, A. 173, 192). Colourless liquid, lighter
than water and nearly insoluble therein. Smells
like camphor. Gives acetic and isobutyric acids
on oxidation.
Terf-heptyl alcohol 0Mes.CMe20H. Di-
methyl-tert-butyl alcohol. Penta-methyl-ethyl
alcohol. [17°]. (131°). Formed by the action
of ZnMe, on CMe3.CO.Cl, the product being de-
composed by water (Butlerow, A. 177, 176).
Formed also from o-bromo-isobutyryl bromide
by treatment with ZuMe, followed by water
(Easohirski, 0. C. 1881, 278) ; and from
CCl,.C001 (1 mol.) and ZnMcj (5 mols.) (Bogo-
moletz, A. 209, 78). The oily liquid obtained
by any of these processes is distilled with steam,
and a hydrate C,H,,0^aq is got which crystal-
lises in long prisms, si. sol. water, v. sol. alcohol
and ether ; it has a burning taste and an odour
like camphor. This hydrate melts at 83° and
begins to boil at 100°, giving off water, and at
130° the anhydrous alcohol passes over. The
dehydration may also be effected by leaving the
hydrate in a closed vessel over baryta at 100°.
The anhydrous alcohol is hygroscopic, readily
changing to glistening leaflets of the hydrate.
Tert-heytjl alcohol CHijOH i.e.
CHMeBt-CMejOH. (139°). S.G. 2 -8487; 22
•8329. Formed by treating a-bromo-w-butyrio
bromide with ZnMe, followed by water (Xa-
sohirski, C. C. 1881, 278). Oil, smelling like
camphor. Gives methyl ethyl ketone, acetone,
and HOAc on oxidation. Gives rise to a heptyl-
ene (92°-95°).
G83
HEPTYL ALCOHOL.
r«rMieptyl alcohol MeBtPrC.OH. Methyl-
ethyl-prqpyl carbinol. (135°-138°) (P.); (140°)
(S.). S.G. 22 .823; 25 -sn. From butyryl
chloride, ZnHe^, and Zn&t^, followed by water
(Pawloff, A. 188, 122). Formed also by treating
ethyl propyl ketone with Mel and zino (Sokolofi,
/. B. 1887, 587). Gives rise to a heptylene (75°-
80°). Chromic acid oxidises it to acetic and pro-
pionic acids, GO2, and some ethyl propyl ketone,
together with a small quantity of a heptylene
C^„ (97-4''), S.G. 29 -718 ; sa -709.
Acetyl derivative GM.s'EiiViO^. (159°).
Teri-heptyl alcohol MeEtPrO.OH. (124°-
127°). S'rom isobutyryl chloride, ZnMej, and
ZnEtj (P.). Gives rise to a heptylene (75°-80°).
Beferences. — Tetra-bbomo-hepiyii aioohoii
and Chlobo-eeftyl aiiCoeol.
w-HEPTYI-AMINE C,H,5.NHj. (154°) (H.);
(156°) (H. a. D.).
Prepwration. — 1. A mixture of equal mols.
of ootoio amide and bromine is run into an ex-
cess of a 5 p.e. solution of KOH at 60° ; the
yield is 30 p.o. (Eofmann, B. 15, 772 ; Hooge-
werfi a. Van Dorp, B. T. C. 6, 386).— 2. An alco-
holic solution of ra-heptoio aldehyde-phenyl-
hydrazide is reduced by means of sodium-
amalgam and acetic acid at 25°-30° ; the yield
is 23 p.o. of the theoretical (Tafel, B. 19, 1928).
FroperUes. — ^Liquid; forms a carbonate on
exposure to the air. — ^B'jHjPtClj: blackens be-
tween220°-230°.— Piorate B'OjHaNsO,: needles
[121°].
Heptylamine C,H„NE[2. . (146°). Formed
by heating heptyl chloride (from petroleum
heptane) with ammonia at 120° for several
days ; di- and tri-heptylamines being also pro-
duced (Schorlemmer, C. J. 16, 221 ; cf. Cahours
a. Felouze, A. Ch. [4] 1, 5). Light oU, smelling
like ammonia, m. sol. water, but separated from
its aqueous solution by KOH. — The hydro-
chloride crystallises in small scales, v. sol.
cold water'. — B'jHjPtClj: small yellow scales, si.
sol. cold, y. Bol. hot, water; sol. alcohol and
ether.
HEPTYL-BENZEITE C„Ha, i.e. 0,H,5.CsH,.
(110° at 15 mm.). Formed, together with
0,'n.if{Cfii)i, by the action of AlCl, on a mix-
ture of CeHij.OHClj and benzene (Auger, Bl. [2]
47, 50 ; KrafEt, B. 19, 2982). When nitrated at
20° it gives 0,H|5.C|jH,.N0j as a yellowish oil
(178° at 10 mm.), whence tin and HCl produce
0,H„.C„Hi.NHi, (175° at 15 mm.).
w-HEPTYI BEOMIDE C,H,,,Br. Bromo-
heptane. (179°). S.G. is 1-133. From ra-heptyl
alcohol and HBr (Cross, G. J. 32, 123).
Sec-heptyl bromide OsHn.CHBr.GHs. (167°).
S.G. IS 1-422. Prepared by the action of bromine
on boiling ra-heptane (Yenable, B. 13, 1649).
Colourless liquid.
Ifej-t-heptyl bromide MejC.CMejBr. [150°].
From penta-methyl-ethyl alcohol and PBr,
(Kaschirski, G. O. 1881, 278). Formed also
from Me2C:CH.CHMe2 and HBr. Solid, sol.
alcohol, v. e. sol. ether.
TC-HEPTYL CHLORIDE 0,H,5C1 i.e.
CH,(CH2)5CHjCl. Ghloro-heptam. (159°).
S.G. is .881. From n-heptyl alcohol and HOI
(C. F. Cross, G. J. 32, 123). Formed also, to-
gether with CH3(CHj)4CHCl.CH3, by chlorinating
heptane from Pinus Sabiiviana.
7i-Sec-heptyl chloride C.H,,,C1 i.e.
CH,(CHj),CHCl.CH3. Formed as above (Schor-
lemmer a. Thorpe, A. 217,' 150). Not obtained
free from the preceding, the mixture of the two
boiling between 143° and 158°. When chlorine
acts upon M-heptane (98°), from petroleum, a
mixture of heptyl chlorides (145°-160°) is ob-
tained (Schoi^lemmer, C. J. 26, 319 ; cf. Pelouze
a. Cahours, A. Oh. [4] 1, 6). When passed over
heated lime this mixture of chlorides gives a
mixture of heptylenes (96°-99°), with one of
which HOI combines in the cold, forming a sec-
heptyl chloride (138°-142°) (Morgan, A. 177,
307).
Heptyl chloride 0,H,5C1. By chlorinating
the isoheptane (90°) in petroleum, there is ob-
tained a mixture of heptyl chlorides (144°-
158°), whence KOAc forms a mixture of heptyl
acetates (160°-185°), whence a mixture of a pri-
mary and a secondary heptyl alcohol may be
got (Schorlemmer).
Heptyl chloride 0,H,5C1. By chlorinating
isoheptane Pr.OHj-Pr there is formed a mixture
of heptyl chlorides (140°-150°), whence KOAo
gives a mixture of acetates (160°-175°), from
which a primary and a secondary heptyl alcohol
may be obtained (Schorlemmer).
Sec-heptyl chloride Pr.OHj.CHj.CHMeCl.
(136°). From the corresponding alcohol and
HCl (Bohu, A. 190, 312).
Terf-heptyl chloride CMej.CMeaCl. [135°]
(K.); [123°] (B.). Prom the corresponding alco-
hol and PCI, (Butlerow, A. 177, 176 ; Kaschirski,
0. C. 1881, 278 ; Eltekoff, /. B. 14, 384). Small
crystals. With aqueous AgNOj it gives a pp. of
AgCl.
Tert-heptyl chloride CMeEtPrCl. (135°-
138°). S.G. 2 -899. From the alcohol and HCl
(Kaschirski, J. B. 13, 90).
w-HEPTTLENE C,H„ i.e. CH,(CHj),CH:CHj.
n-Amyl-ethylene. Mol. w. 98. (99°). S.G.
'?' -703. Formed from m-heptane (of petroleum)
by chlorinating, and heating the resulting mix-
ture of heptyl chlorides with KOAc and A.afi at
160° (Schorlemmer, O. J. 26, 322), or by passing
them over heated lime (Morgan, G. J. 26, 303).
The mixture of heptylenes so obtained is treated
with HCl, which combines only with ilf-heptylena
leaving ji-heptylene free. 71-Heptylene occurs
amongst the products formed in the preparation
of oil gas (Armstrong, O. J. 49, 74). n-Heptylene
combines with HCl when heated with fuming
HClAq at 120°. With hydriodic acid at 120° it
forms CjHii.CHI.CH,. With water it forms, ac-
cording to Le Bel (0. B. 81, 967), a hydrate,
which is resolved by heat into water, a resin,
and an unsaturated alcohol (140°).
ifr-Heptylene O^Hj.CHiOH.OH,. (98-5°). The
mixture of ohloro-heptanes from the heptane of
Piivus Sabimana, containing 0Hj(CH2)5CHjCl
and CH3(0H:2)4CH01.0H3 if heated with alco-
holic KOH at 100° forms a mixture of heptylenes
and ethyl heptyl oxides. The heptylene, purified
by distilling over sodium, boils at (98-5°). This
heptylene, placed vrith fuming HCl in the dark
for six weeks, is but slightly aSected, only 10 p.c.
combining. On the other hand, petroleum hep-
tylene combines under the same conditions to
the extent of 50 p.o. But after several months
the first heptylene (from Pinus) is almost com-
pletely combined with HCl, while more of the
HEPTYL IODIDE.
683
petroleum heptylene has combined. Thus cold
HCl will not separate isomeric olefines. Firms
heptylene is oxidised by H2SO4 and KjOrjO, to
valeric and acetic acids only (Sohorlemmer a.
Thorpe. A. 217, 151 ; of. Venable, A. 0. -J. 4, 22).
It rapidly absorbs ClOH in the cold (Grissom,
Am. 10, 225).
Heptylene 0,H„. From heptylidene chloride
and sodium (Limpricht, A. 103, 86).
Iso-heptylene Pr.CHj.CH:OH.OH,. (91°).
S.G. ifi -706. From EtO^H,,, by chlorinating and
heating the resulting mixture of heptyl chlorides
with KOAo and Ao^O at 160° (Grimshaw, 0. J.
26, 313). The product, however, is probably a
mixture ; for a part only combines in the cold
with HCl.
Heptylene C,H„ i.e. Pr.CH2.CH,.CH:0BL, ?
(76°-80°). From Pr.OHj.CHj.OHI.OH3 and alco-
holic KOH (Bohn, A. 190, 314).
Heptylene 0,H„. (91°). From the isohep-
tane in petroleum (Schorlemmer, C, J. 26, 820).
i|--Heptylene Pr.OHiOMcj orPr.0Hj.0Me:0Hj.
(84°J. S.G. 2 -7144. From di-methyl-isobutyl-
carbinyl iodide and alcoholic EOH at 100°
(PawlofE, A. 173, 194). Unites with HI, repro-
ducing the parent iodide.
Heptylene Pr.CH:CMej. (B2=). S.G. 14-6995.
From oxy-iso-ootoio acid (03H,)jC(0H).C0jH by
heating with water and a few drops of H^SO^ at
180° (Martownikoff, Z. 1871, 268). Unites with
HI, forming PrOMCjI, and is perhaps identical
with the preceding heptylene.
Heptylene CMej.OMeiOHj. (80°). From
CMea-OMejI and alcoholic KOH (Butlerow, J. B.
7, 44; Kaschirski, C. O. 1881, 278). Formed
also by heating GMejiCHMe with Mel and PbO
at 225° (EltekoS, J. B. 14, 382 ; B. 16, ^95).
Combines with HI, forming CMej.CMejI.
Heptylene CMejiCMeBt. (75°-80°) (PawlofE,
A. 188, 122) ; (92°_95°) (Kaschirski, O. C. 1881,
278). S.G. 2 -7355; 21 -7188 (K.). From
MeEtPrO.OH.
Heptylene HCEt:CMeEt (?). (90°-95°).
From MeEtPrC.OH (P.). Socoloff {J. B. 1887,
587) among the products of the oxidation of
CMeEtPrOH found a heptylene (97°), S.G. 22
'718 which on further oxidation yielded acetic
and propionic acids but no ketone.
Heptylene C,H„. (96°). S.G. -742. Occurs
in the product of the distillation of colophony,
and separated from toluene by sulphonating the
latter (Eenard, Bl. [2] 39, 540 ; cf. C. B. 91, 419 ;
Emmerling, B. 12, 1441).
Heptyleues have also been obtained with the
following boiling-points : (a) by strongly heating
paraffin (94°-97°) (Thorpe a. Young, A. 165, 11) ;
(6) by heating heptoic aldehyde with lime (95°-
100°) (Fittig, A. 117, 77) ; (c) by heatmg fusel
oil with ZnOlj (80°-85°) (Wurtz, Bl. 5, 307) ;
(i) by distilling a lime soap formed from train
oil (94° cor.) (Warren a. Storer, Z. 1868, 229).
Beference. — ^BBOMO-HBPraiBiiB.
HEPTYLENE BBOUIDE v. Di-Biiouo-asF-
lANE.
HEPTYLENIC ACID v. Hefienoic acid.
DI-HEPTYL-HEPTOIC ALDEHYDE v. Hks-
nOBENOIO ALDEBYDE.
HEFITL HYDBIDE v. Heptane.
HEFTYLIC ACID v. Hefioio aoid.
HEFTYLIDEIfE. The radicle Oja.„.CE.
HEPTYLIDENE DI-ACETONAMINE v. Aob-
ionamine.
HEFIYLIDENE-DI-AHINE Di-henzoyl
derivative G^JS^^fit i.e. C8H,8.CH(NHBz)2.
[128°]. Formed by heating heptoic aldehyde with
benzamide (Medicus, A. 157, 44). Insol. water,
HOlAq, and KOH ; si. sol. boilmg ether, t. sol.
boiling alcohol. Split up by hoping HClAq into
benzamide and heptoic aldehyde (oenanthol).
Di-nitro-di-bemvyl derivative
OeH„.OH(NH.OO.C.H,.NOj)j. [170°]. From
heptoic aldehyde and nitro-benzoic aldehyde.
HEFXYLIDENE BBOUIDE v. Di-bbouo-
EEFTANE.
HEFXYLIDENE CHLOEIDE v. Di-chlobo-
BEPIANE.
HEPTYLIDENE THIOCABBIUIDE
C,H,a.OH(NCS)jj. From OeH,3.0H(NH.CS.NHj),
by warming with alcohol and HCl (H. Sohiff, B.
11, 833). Oil, with disgusting odour. Combines
with NH3 reproducing the parent substance.
HEFIYLIDENE-DI-THICDI-XTBEA
CjHj„N,0, i.e. C3H,3.CH(NH.CS.NHj)j. Formed
by adding a drop of HCl to an alcoholic solution
of thio-urea and heptoic aldehyde (oenanthol)
(H. Schiff, B. 11, 838). Decomposed by HCl
forming the preceding body.
HEPrYLIDEKE-DI-UEEA G^S.^'Sfii i-e.
CeH,3.CH(NH.C0.NHj)j. [166°]. Formed by
adding heptoic aldehyde (oenanthol) to an alco-
holic solution of urea. Small needles ; v. si. sol.
alcohol and ether. Decomposed by heat. Boil-
ing dilute acids split it up into urea and heptoic
aldehyde. When warmed with an alcoholic
solution of benzoic aldehyde there is formed
C5H5.CH(NH.CO.NH.CH(CaH,5).NH.CO.NHJj ;
a powder insol. water, si. sol. alcohol and ether
(Schifi, A. 151, 195).
Di - heptylidene - tri - urea CiiHa^NjOa i.e.
(1^H2.C0.NH.CH(CbH,3).NH)j.C0. [162°].
Formed by triturating urea with heptoic alde-
hyde. Crystalline powder. Boiling dilute acids
convert into it urea and heptoic aldehyde.
Benzoic aldehyde forms CeH5.CHINH.OO.NH.
CH(C„H,3).NH.OO.NH.CH(CeH,3).NH.CO.NHj}j
a gelatinous substance that swells up in water
(Schiff).
Tri - heptylidene - tetra - urea CmHjjNjOi.
[155°]. Formed, together with penta-heptyl-
idene-hexa-urea C4,Hj4N,j08 [0. 150°], by heating
either of the preceding ureides with heptoic
aldehyde at 100°. Amorphous yeUow powder ;
insol. water, si. sol. alcohol and ether. Swells
up in cold water (Schiff ; cf. Leeds, B. 16, 293,
who questions the above formulsB).
w-HEFTYL IODIDE CjH.^I i.e.
CH3(CHj)30HjI. (208-8°). S.G. § 1-4008. S.V.
198-6. O.E. (0°-10°) -00091. From m-heptyl
alcohol and HI (Cross, A. 189, 4 ; Dobriner, A.
243, 28).
ra-Sec-heptyl iodide CHj.(CH3),CHI.CH3.
(98°at50mm,). From the corresponding bromide
by treatment with KI (Venable, B. 18, 1649).
Converted by NaOEt into heptylene. When
distilled imder atmospheric pressure it splits up
into HI and heptylene.
Heptyl iodide C,H,5l. (170°). Obtained from
heptylene (from petroleum heptane) and HI at
100° for 12 hours (Schorlemmer, C. J. 16, 220).
Heptyl iodide C,H,5l. (190°). Obtained by
the action of iodine and phosphorus on tho
684
HEPTYL IODIDE.
heptyl alcohol derived from heptane of pe-
troleum (Sohorlemmer, O. J. 16, 219 ; cf. Peter-
sen, A. 118, 74). Heavy oil ; alcoholic AgNOj
separates the whole of its iodine as Agl.
Heptyl iodide 0^,J i.e. Pr^OHI. (180°)
(K.) ; (185°) (R). S.G.221-2. From di-propyl-
carbinol, I, and P (Kurtz, A. 161, 205 ; Friedel,
A. Ch. [4] 16, 310).
Heptyl iodide 0,H,sI i.e. fl.CHj.GMeJ.
Prom di-methyl-isobutyl-oarbinol and HI (Paw-
loff, A. 173, 192). Also from Me2CE.CH:CHe2and
HI. Heavy oil.
Heptyl iodide CMes-CMe^I. [142°]. From
the alcohol and HI (Butlerow, A. 177, 184;
Easohirski, C. C. 1881, 278). Solid, smelling
like camphor.
Heptyl iodide Pr.OHj.CHj.OHI.Me. (165°-
175°). From the alcohol and iodide of phos-
phorus (Bohn, A. 190, 313).
Heptyl iodide MeEtPrCI. (146°). S.G.
2 1-93 ; so 1.373. From the alcohol and HI
(Kaschirski, J. B. 13, 90). Suffers much de-
composition when distilled..
DX-HEPTYl KETONE C^^B^file. {0,Bi,^)fiO.
[40°]. (178°). Obtained by distilling barium
octoate (caprilate) with excess of lime (Guckel-
berger, A. 69, 201). Waxy solid.
n-Seo-HEPTYI-MALOlTIC ACID CioHisO^ i.e.
C5H„CHMe.CH(C02H)j. [98° unoor.] White
crystals. Sol. alcohol, chloroform, and ether, si.
sol. water.
Salts (Leeds, A. C. J. 5, 10).— BaA": white
powder, insol. water and alcohol. — CuA" : light-
blue crystals, si. sol. water, sol. alcohol. — PbA" :
[235°]. White mass, insol. water, si. sol. alcohol.
— ZnA": [247°]; minute crystals. — Ag^A" :
[244°] ; minute crystals, insol. boiling water.
Ethyl ether Mm. (263°-265°). Colourless
liquid. Prepared by the action of n-sec-heptyl
iodide and sodium on a mixture of alcohol and
malonic ether. On heating the acid to 160° it
gives heptyl-acetio acid and 00^ (Yenable, B. 18,
1651).
HEPTYL OCTYL OXIDE C,H,50C,H„.
(278-8°). S.G. § -8182. S.V. 376-8. O.E. (0°-10°)
•00085 (Dobriner, A. 243, 10).
DI-HEPTYL-OXIDE (OjH.JjO. (261-9°).
S.G. g -8152. S.V. 352-7. C.E. (0°-10°) -00098
(Dobriner, A. 243, 9).
HEPTYL -UBEA Oetoyl derivative
, C,H,jNH.OO.NH.CO.C,H„. [102°]. Formed by
the action of an alkaline solution of bromine on
octoic amide (Hofmann, B. 15, 760 ; 17, 1408).
HEBACLEVM OIL. The essential oil of the
cow-parsnep (Heracleiwm Sphondyliwm) is light-
green, mobUe, S.G. — -864, and consists mainly
of ootyl acetate (200°-212°), whence by saponifl-
oationoctyl alcohol (191°) may be obtained. The
portions boiling at a higher temperature contain
octyl hexoate (270°) (Zincke, A. 152, 1). The
oil also contains ethyl butyrate, hexyl acetate,
octyl decoate, and octyl laurate in small quan-
tities (MSshnger, A. 185, 26). The water with
which the oil has been distilled contains methyl
alcohol, ethyl alcohol (in smaller quantity), acetic
acid, and caproio acid.
The volatile oil of Heracleum giganteum is
a mixture of octyl acetate, hexyl butyrate, and
ethyl butyrate (Franchimont a. Zincke, B. 4,
S22 : J. 103, 193 ; Gutzeit, A. 177. 344).
HERACLIN Oa'OJ),^. [185°]. S. (alcohol)
■14 in the cold ; 1-7 at 78°. S. (OS2) -083 in the
cold ; -25 at 46°. Occurs in the seeds of Sera-
cleum giganteum (Gutzeit, J. 1879, 905). Silky
needles (from alcohol). Insol. water, v. sol.
chloroform, m. sol. ether.
HESPEBETIC ACID v. Isofebulio acid.
HESPEBETIB' v. HESPBBTDn;.
HESPERETOL
C5H3(OMe)(OH).CH:OH2 [4:3:1]. [57°]. Prepared
by the dry distillation of calcium isoferulate
(Tiemann a. Will, B. 14, 967). Crystalline solid,
sol. alcohol and ether. Dissolves in caustic alkalis.
Gives a red colouration with H^SO,.
HESPERIC ACID O^^^fi,. An acid whioh
may be extracted by alcohol from orange-poel
(Tanret, Bl. [2] 46, 500). Slender white crystals;
not volatile ; insol. water and ether, si. sol. cold
alcohol, sol. boiling (90 p.c.) alcohol and chloro-
form. Its K, Na, and Oa salts are amorphous,
and decomposed by OOj. — CaA'j.
HESPEEIDENE C,„H„. (178° cor.). S.G. 22
-846. A terpene contained in the volatile oil of
orange-peel (Wright, G. J. 26, 549). It forms a
tetrabromide 0,„H,5Br, [105°], and with NOCl a
nitroso- derivative [71°]. Identical with citrene,
carvene, limonene, &o. (v. Tbepenes).
HESPERIDIN OjjH^O.j (T. a. W.), or
CsoHsjOj, (Tanret). [251°]. S. (hot water) -02
(Hilger, B. 9, 26) ; 1-3 at 100° (T.) ; S. (alcohol)
-5 in the cold; 1-8 at 78°; S. (EtOAc) -67
(Tanret, Bl. [2] 46, 502). [a]D= -89°. Dis-
covered by Lebreton (J. Ph. 14, 377) in many
fruits of the genus Citrus ; thus it may readily
be obtained from the white spongy inner coating
of the peel of unripe Seville oranges, or from
dry unripe bitter oranges (Citrus Bigaradia).
Pr^aration. — Dried unripe orange-peel is
thoroughly extracted with water to remove other
substances, and the residue then dissolved out
with dilute alcoholic NaOH; the impure hes-
peridin is ppd. from the solution by adding
HCl and purified by extraction with alcohol,
solution in NaOH, and reppn. with COj; the
yield is at most 10 p.o. (Tiemann a. WiU, B. 14,
946).
White minute hygroscopic needles. Nearly
insol. alcohol and water, insol. ether. Wef^
acid, dissolving in aqueous NaOH. It does not
react with AoGl, or form a compound with picric
acid (Patemd a. Briosi, O. 6, 169).
Beactions. — 1. On reduction with sodium
amalgam it gives a body which dissolves in alco-
hol with a magenta-like colour. — 2. By boiling
dilute H2SO4 it is split up into sugars and hes-
peritin (CnjHuOj). The sugar obtained is a mix-
ture of 2 pts. of glucose with 1 pt. of isodulcite
(Tanret, Bl. [2] 49, 20) ; these sugars may be sepa-
rated by means of their phenyl-hydrazides, that
of isodulcite [180°] being soluble in acetone
(Will, B. 20, 1186). — 3. Hesperidin dissolves in
dilute EOH, the solution becoming gradually
yellow ; if it be evaporated to dryness, and the
residue be treated with dilute HjSO,, it is turned
red, and afterwards violet. — 4. Potash-fusion
forms protocatechuio acid.
Hesperetin O.bHuO, i.e.
[4:3:1] O.H,(OM:e)(OH).CH:OH.OO,0.0,P,(OH).[l:3tf] ?
[226°]. Prepared by heating hesperidin with
dilute H2SO, to 120° (B. Hoffmann, B. 9, 687 ;
Tiemann a. Will, B. 14, 951). White plates.
HEXAMIDINE.
685
7. Bol. alcohol, m. sol. ether, si. sol. water,
benzene, and chloroform. Weak phenolic acid,
dissolving in NaOH, ppd. by COj. Has a sweet
taste. Like hesperidin, on reduction with
sodium-amalgam it gives a substance which
dissolves in alcohol forming a magenta-like solu-
tion. On boiling with aqueous EOH it decom-
poses into phloroglucin and isoferulio acid (hes-
peretio acid). FeCl, gives a brownish-red colour.
Lead acetate gives a pp. Potash-fusion yields
protocatechuio acid. ^
Iso-hesperidin 02jH250,22aq or CsoHuoOj, 5aq.
[a]i,= -89°. S. 200 at 100°. S. (90 p.c. alcohol)
11 in the cold. Obtained froin orange-peel by
extracting with (60 p.c.) alcohol, evaporating,
and shaking the residue with oUoroform
(Tanret, Bl. [2] 46, 502; 49, 20).- Minute
needles from water (containing 2aq), with
slightly bitter taste. SI. sol. cold water, v. e. sol.
hotwater. Lsavorotatory. Split up by boiling dilute
E2SO, into hesperitin, duloite, and glucose. The
substance called hesperidin by De Vrij is de-
scribed as Naiunqin.
HETERO-ALBUUOSE v. FBOiEiba.
HEVEENE OjsH,,? (315°). S.G. si -921.
The least volatile part of the product of the dry
distUlation of caoutchouc and gutta-percha
(Bouohardat, A. 27, 30). Amber-yellow oil.
Misoible with alcohol and ether. HOI forms
unstable OuHjiHOl. V. Tebpenes.
ji-HEXADECAlTE C^^,^. Secdecane. Di-
octyl. [14°] (E.) ; [18°] (K.) ; [20°] (L.); [21°]
(Z.). (150° at 10 mm. ; 209° at 100 mm. ; 288°
at 760 mm.) ; (278°) (Z. ; S.) ; (158° at 15 mm.)
(K.). S.O. *j° -774; 122 -719. Odourless solid.
Formed by reduction of pahuitic acid with P and
HI (Krafft, B. 15, 1701; 16, 1722; 19, 2218).
Also fromre-ootyl iodide and sodium (Lachovitoh,
A. 220, 180 ; cf. Zinoke, A. 152, 15 ; Krafft, B.
19, 2222); and by heating Hg(08H„)j at 200°
(Eichler, B. 12, 1882). Probably the same hydro-
carbon [20^, (278°), V.D. 7-9, is formed by digest-
ing an alcoholic solution of cetyl iodide with
zinc and fuming HCl for a week (Sorabji, C. J.
47, 37). Pearly plates, sol. hot alcohol and ether.
Hexadecane CsHia.CHMe.CHMe.OsH,,. Di-
Uo-octyl. (26B°-265°) (L.); (269° cor.) (A.).
S.G. W -800 (L.) ; | -802 (A.). V.D. 114-8 (for
113). From secondary octyl bromide (or iodide)
and sodium. Liquid smelling of freshly extin-
guished tallow candles (Laohovitch, A. 220, 187 ;
cf. Alechin, Bl. [2] 40, 186).
Hexadecane G^^t- Cetyl hydride. , Ceta/ne.
(280°). V.D. 8-08 (oalo. 7-96). Obtained from
American petroleum by fractional distillation
(Pelouze a. Cahours, C. B. 67, 62). Probably
identical with M-hexadecane.
Beference. — Di-bbomo-hexadeoane.
HEXADECOIC ACID B.C{0, 3,^)^00^ Di-
n-heptyl-aceUc acid. [26°]. (240°-250°) at
80-90 mm. Obtained by decomposing its ether
with concentrated alkalis. Crystalline. Insol.
water, sol. alcohol or ether.
Salts.— The salts of the alkalis are soapy
and V. sol. water or alcohol. The salts of the
alkaline earths and heavy metals have a great
tendency to form basic salts, — BaA'j: slender
needles (from alcohol); insol. water.— CuA', :
bluish-green crystalline pp. [227°].
Ethyl ether EiX'. (c. 310°). Fromheptyl-
aceto-acetio ether, KaOEt, and heptyl iodide
(Jourdan, A. 200, 114). OU.
Isomeride v. Palmitic acid.
HEXADECYl. The radicle CioHj,, also
called Cetyl {q. v.).
H£X*DECYL AICOHOL v. Cetyl alcohol.
HEXASECYL ALLOFHAKATE
C,„H3,.0.C0.NH.C0.NH,. [70°]. Formed by the
action of chloro-formamide on an ethereal solu-
tion of cetyl alcohol (Gattermann, A. 244, 41),
Colourless plates (from alcohol).
HEXADECYL-BENZEUE CicHaa.CjH,. [27°].
(230° at 15 mm.). S.G. Y •8567. From cetyl
iodide, iodobenzene, and Na. SI. sol. cold al-
cohol, V. sol. ether, benzene, CS.^, and chloro-
form (KrafEt a. Gottig, B. 19, 2683 ; 21, 3180).
Gives a nitro- derivative [36°] which reduces to
C,sHsj.0sH4.NH2 [53°] (255° at 14 mm.) whence
C,eH,3.C,H,.NHAo. [104°].
HEXADECVL-CSESOL CBH„.C„H3Me.0H.
[62°]. (268°). Formed from^-hexadecyl-toluene
sulphonic acid by potash-fusion at 150°. Crystals
(from alcohol).
Ethyl ether O^^.O^B.^'ULe.OM. [26-5^.
Fromhexadecyl-cresol, ethyl iodide, and alcoholic
KOH (Krafft a. Gottig, B. 21, 3180).
HEXADECYLENE v. Cetbnb.
HEXADECYLENE BBOSflDE v. Di-bbomo-
HEXADECANE.
HEXADECYL-MESITYIENE
CjH,aC„H2Me,[6:5:3:l]. [c.40°]. (258° at 15 mm.).
From bromo-mesitylene, oetyl iodide, and sodium
(Krafft a. Gottig, B. 21, 3180).
HEXAD ECYL-PHENOL C,eH3,.CsH,.0H.
[77-5°]. (261° at 15 mm.). From hexadeoyl-
benzene by sulphonating and fusing the result-
ing sulphonic acid with KOH (Krafft, B. 19,
2683 ; 21, 3180).
Ethyl derivative CjjHjs.CjH^OEt. [43°].
Plates; gives on oxidation [4:l]OjH4(OEt)(C02H).
o-HKXADECYL-TOLTTENE
C,aH3,.C,H,Me[l:2]. [9°]. (239° at 15 mm.).
S.G. '-J -8676 ; «f -8072. From o-bromo-toluene,
cetyl iodide, and sodium (Krafft a. Gottig, B. 21,
3181].
m-Hezadecyl-toluene C,iiHj3.C5H,Me[l:3].
[12°]. '(237° at 15 mm.). From m-bromo-tolu-
ene, cetyl iodide, and Na (K. a. G.).
ji-Hezadecyl-toluene p,5H53C5H,Me[l:4].
[27-5°]. (240° at 15 mm.). -Converted by HNO,
(S.G. 1-2) at 125° into J)-toluic acid. Fuming
H2SO4 sulphonates it.
HEXA-SECYL-m-XYLEITE
Cfi„.C,BJiel4::3:l-]. _ [33-5°]. (250°). From
bromo-m-zylene, cetyl iodide, and sodium. Crys-
tallises from ether-alcohol (Krafft a. Gottig, B.
21, 3180).
HEXA-ICOSANE CJS.,i. [44f>]. A soft waxy
substance found among the products of the dis-
tillation of oerotio acid (Nafzger, A. 224, 236).
HEXAlN SEGA-CABBOXYLIC ETHEB v.
HeXANE SEGA-CABBOXYLIC ACID.
HEXAMIDINE CsH„Nj t.«.
Pr.CH2.CH2.C(NH2):NH, Capronamidine.
Heated with acetic anhydride and sodium ace-
tate it yields the nitrile of hexoic (caproic) acid.
Salts.— BTECl: large plates [107°], v. sol.
alcohol. — B'jHjCl^PtCl^ : yellowish-red plates
[199°], flol. hot, si. sqI. «o]4i water (Pinner, B.
17,175).
HEXAMIDOXIM.
HEXAMIDOXIM C5H„.0(N0H)NH,. Ca-
prarrddoxvm. Isobutylacetamidoxim. [58°].
Formed by direct combination of hexonitrile
(oapronitnle) with hydrozylamine. Glistening
white silvery tables. V. sol. alcohol, ether, &o.,
b1. sol. water. Dissolves in aqueous acids and
alkalis.— B'HOl : [116°] ; white needles, v. sol.
water and alcohol, si. sol. ether.
Ethyl ether 0,H„C(NHj)NOBt : [85°];
very hygroscopic, long white needles; v. sol.
alcohol, ether, &o., si. sol. water.
Acetyl derivative CsH„.C(KH2)NOAo :
[87°] ; very fine silky white scales ; v. sol. alco-
hol and ether, nearly insol. water.
Benzoyl derivative OaH„0(NHj)NOBz :
[106°] ; felted white needles ; sol. alcohol, ether,
and benzene, insol. water.
Hexoyl derivative
CsHii.CCNHJNOCOCsH,,: [115°]; silvery scales;
V. sol. aJcohol, ether and benzene, b1. sol. water.
, Carbonyl derivative
(C5H„.C(NH2)NO)jiCO : [114°]; felted silky
needles ; T. sol. alcohol and chloroform, nearly
insol. water and benzene. Penned by the ac-
tion of carbonyl chloride upon hezamidozim
(Jaooby, B. 19, 1500).
TC-HEXANE qjH„ i.e.
CH3;CHj.CH2.0Hj,.CH2.0H3. Di-n-propyl. Sexyl
hydride. Methyl - pentane. Methyl - amyl.
Ethyl-butane. Ethyl-butyl. Mol. w. 86. (68-7°)
at 751 mm. (Schiff, 4. 220, 88); (69-0° i.V.)
(Zander, A. 214, 165); (68-6°) at 744 mm.
(Bruhl, A. 200, 184) ; (69°) (Perkin, O. J. 45, 446).
V.D. 3-06 (calc. 2-99) (Schiff). S.G. g -6753 (Z.);
V -6603 (B.) ; '-^ -668 (S.) ; if -6739 ; || -6662
(P.). M.M.6-670atll°(P.). S.V. 139-7 (Schiff) ;
140 (Z.) ; 138-7 (Eamsay). nt^ 1-3799. Ea, 47-59
(B.). Critical temjoerature 250-3° (Pawlewaky, B.
16, 2634). Occurs in Pennsylvanian petroleum, in
the light oils from coal tar (Schorlemmer, T. 162,
111), and in Galioian petroleum (Lachovitoh, A.
220, 192). Is the chief constituent of so-called
' petroleum ether ' or ' ligroin.'
Eommtion. — 1. By reducing with zino and
dilute HCl the sec-hexjl iodide derived from
mannite ; the product being freed from hexylene
by treatment with bromine (Schorlemmer; cf.
Erlemneyer, Z. 1863, 274).— 2. By heating
Tt-tpropyl iodide dissolved in ether with sodium
at 145° (Schorlemmer, A. 161, 277).— 3. By dis-
tilling suberic acid with lime or baryta (Dale,
C. J. 17, 258 ; cf. Kiohe, A. 113, 106).— 4. Among
ithe products obtained by distilling tri-olein under
pressure (Engler, B. 22, 596).
Properties. — Oil, with faint oharaoteristio
lOdour, unlike petroleum.
ReacUons. — 1. On passing through a red-hot
iube the following products were obtained:
ethylene, propylene, butinene 0^^, amylene,
liexylene, benzene, and gases not absorbed by
bromine. Decomposition begins at 600° to 700°,
but benzene is not formed except at a high tem-
perature (Norton a. Andrews, Am. 8, 1). — 2.
Chlormatim gives CH3.0H2.CH2.GH2.0H2.0H2G1
and CH3.CHj.CHj.CHj.OHOl.OHa (Schorlemmer,
A. 199, 139; cf. Morgan, 0. X 28, 301).— 3.
Bromine vapour passed through boiling hezane
forms only secondary hexyl bromide (Schor-
lemmer, T. 1878, 1 ; A. 188, 250). Bromine at
^2.5° fprma -crystalline C,H^Jtir^ arid iilpp P^HjBr,
and CsHjBr, ; at 185° it forms C„Brj, which, at
a higher temperature, is resolved into bromine
and heza-bromo-benzene (Wahl, B. 10, 402,
1234).
/See-hexane OjH,4 i.e. Pr.Pr. Isohexane.
Propyl-isopropyl. _ Ethyl-isobutyl.
Isopropyl-propane. (62°) (W.); (59°
62°) (PeiMn, C. J. 45, 447). S.G. 2 -701 ; J|
•6633 ; §1 -6534 (P.). M.M. 6-769 at 17° (P.)!
V.D. 3-05 (calc. 2-98). Prepared by decomposing
isobutyl iodide (40 g.) with EtI (34 g.) and sodium
(11 g.) (Wurtz, A. Ch. [3] 44, 275). Occurs in
Galician and in American petroleum (Warren ;
Lachovitoh, A. 220, 192). By passing through
a red-hot tube it is decomposed into ethylene,
propylene, butylene, amylene, hezylene, butinene,
and some paraffins (Norton a. Andrews, Am. 8,
Sec-hezane CjH„ i.e, Pr.Pr. Di-isoprc^l.
Isohexane. (58-0°) (Zander, A. 214, 167). S.G.
s -6829 (Z.) ; -668 (Perkin, C. J. 45, 447). M.M.
6-784 at 15° (P.). S.V. 136-5 (Z.). Formed by
the action of sodium on an ethereal solution of
isopropyl iodide (Schorlemmer, A. 144, 184).
Formed also by the action of HI on pinaeone
OMej(OH).CMej(OH) (Bonchardat, C. R. 74,
809). According to Berthelot (Bl. 9, 268) this
hexane is also obtained by heating diallyl with
HI. Biohe {A. Ch. [5] 9, 432) obtained it by
distilling barium n-heptoate at a red heat. It
also occurs among the products obtained by dis-
tilling whale oU under pressure (Bugler, B. 22,
595). It is an oil, with faint odour. Chromic
acid oxidises it to COj and acetic acid.
Sec-hexane OeH,, i.e. CHa-CHEtj. Methyl-
di-ethyl-methame. (64°). S.G. ^* -6765. One
of the products of the reduction of
CHj.CHI.CHMeEt with zinc and glacial acetic
acid CH,.C(OH)Etj and CH2:0H.CHMeEt being
also formed (Wislicenus, A. 219, 315). The same
hydrocarbon, (60°), was said by Le Bel (Bl. [2]
25, 546) to be formed, together with ethane and
decane, by the action of sodium on a mixture of
Mel and optically active amyl iodide ; Just (A.
220, 150) failed, however, to obtain it by this
method.
rert-hexane 0jH„ i.e. CMcjEt. Tri-methyl-
ethyl-methcme. (43°-48°). Prom tert-hxA-jl
iodide ajid ZnEtj (Goriainoff, A. 165, 107).
References. — Di-bbouo- and Di-ohlobd-
HEXAKE.
HEXANE CABBOXYLIC ACID v. HEfioio
Acm.
Hezane di-carbozylic acid v. Di-EiHXL-sno-
CnnO, TETBA-MEIHYL-SUCCINia, AuyL-MALONIO,
SuBEBio, and Di-aiiDanic acids.
Hezane tri>carboxylio aoid
CHEt(0OjH).0Et(0OjH)j. [150°]. Ethyl-bu-
temyl tri-carboxyUo akd. Formed by saponify-
ing the ether (1 mol.) with EOHAq (9 mols.) to
which a little alcohol has been added (Hjelt, B.
21,2089). Crystalline solid, V. sol. water. At
150°-160° it is split up into CO, and di-ethyl-
Buccinic acid.
Ethyl ether Et,A"' (186° at 36 mm.);
(281° at 760 mm.). S.G. ^ 1-024.
Formation. — 1. By the action of o-bromo-
butyric ether on sodium ethyl-malonio ether
(Hjelt, B. 21, 2089; cf. Hjelt, B. 20, 3078).—
2. Sodium (11-5 g.) is dissolved in alcohol
HEXENOTC ACID.
687
(200 o.e.) Rnd biUane tri-oarboxylio ether
CH(002Bt)j.0HEt(C0.,Et) (137 g.) is added to-
gether with EtI (80 g.). The reaction is com-
plete after heating at 100° for 4 hotirs (Bisohoff,
B. 21, 2092).
Properiies. — Oil, which distils with partial
decomposition. By boiling with H^SOj it is
Bapoiu£ed, COj being given off, and two isomeric
di-ethyl-snccinic acids formed, one being v. sol.
ether, the other si. sol. ether.
First nitrile CO^Et.OCyBt.OHEt.CO^Et.
(280°-286°). A product of the action of alco-
holic KCy on a-bromo-butyrio ether (Zelinsky a.
Britsohinin, B. 21, 3393). Oil.
Hezane tri-carbozylio acid OaH,,(002H)s.
Subero-carboxylie acid. S. 85-6 at 14°. Formed
by boiling ohloro-suberic acid with KCy and de-
composing the resulting cyano-snberio acid with
KOH (Groger, M. 1, 510; Bauer, M. 4, 341).—
PbaA'", (at 100°).— FeA'": brown pp.— Ag,A"'.
Hezane tetra-carbozylic acid. Ethyl
ether CEt(OOjEt)j.CEt(COjEt)j. Di-efhyl-
O/cetyUne-tetra-ca/rhoxyUo ether. (199°atllmm.).
S.G. ^ 1-043. Formed from ohloro-ethyl-malpnio
ether and sodinm ethyl-malonio ether (Bischoff,
B. 21, 2085). Oil. On saponification it yields
di-ethyl-sucoinio acid [188°].
Hezane deca-carbozylic acid Ethyl ether
C„H,(CO^t),„ i.e.
CHj(COitEt).0(OOjEt)j.O(COjEt),
I . So-called
CBL,(C0jEt).0(C0jEt)2.0(002Et)2
' hesoaHn ' decaea/rboxyUc ether. A thick oil, ob-
tained by treating
CHj(0OjBt).0(COjEt)j.C(COjEt),Clwith
CH2(COjEt).0(CO.^t)j.C(C02Et)jNa (Bisohoff, B.
21, 2115).
HEXANE SULFHONIG ACID CH^.SOaH.
Formed by oxidising hezyl mercaptan (from
petroleum hezane) (Pelouze a. Cahours, A, 127,
192). Syrup.— BaA'j (at 100°): scales.
HEXECONTANE Cj„H,jj. [102°]. Obtained
by heating (10 pts. of) myrioyl iodide [70-5°]
with potassium (1 pt.) at 135°, the product being
boiled successively with water, alcohol, petro-
leum-ether, and glacial acetic acid, and finally
crystallised from benzene (Hell a. Hagele, B.
22, 502). V. si. sol. hot alcohol and ether, si.
sol. petroleum-ether and HOAc, m. sol. chloro-
form and benzene. Partially decomposed by
distillation. On distilling under reduced pressure
there is formed a paraffin-like mass, v. sol. petro-
leum-ether, which extracts a hydrocarbon [70°].
HEXENOIC ACID C„H,„0j*.e.
CH,.CH:CEt.002H. a-Ethyl-erotomlc acid. Mol.
w. 114. [41°]. (209°).
EormaUcm. — 1. From oxalic ether by treat-
ment with ZnEtj and decomposition of the re-
sulting COjEt.CBt2.OH with PCls. By this
means the ether is obtained, and is subsequently
saponified (Frankland a. Duppa, O. J. 18, 138 ;
Fittig a. Howe, A. 200, 21).— 2. By heating
CO2Et.OBt2.OEt with HOI at 150° (Geuther, Bl.
[2] 10, 34).— 3. By treating 002H.0Et20H with
PClj, and decomposing the distillate with water
(Geuther). — 4. By distilling oxyhexoio acid
CH,.0H(0H).CHEt.C02H (Waldschmidt, A. 188,
245).
ProperUes. — ^Large four-sided prisms (after
fusion) ; si. sol. water, v. e. sol. alcohol and
ether. Its aqueous solution reddens litmus, but
its salts easily give up part of their acid when
evaporated. Sublimes in the cold. Beadily
polymerised by heating or ezposing to the air.
Not affected by reducing agents.
Reaotkms. — 1. Potash-fiision forms acetic
and w-bntyric acid (PetriefE, B. 6, 1098).— 2.
HBr forms CsHnBrOj [25°] which when boiled
with water or alkalis gives amylene and oxy-
hexoio acid [48°-52°] (Fittig a. Howe).— 3. Bro-
mme forms CjHioBrjOj [80'5°].— 4. Ghrormc
acid nmitwre forms CO, and acetic acid (Chap-
man a. Smith, P. M. [4] 36, 290).— 5. KMnO,
added to a very dilute solution of the K salt forms
CH,.CH(0H).CEt{0H).002H [96°] (Fittig, B. 21,
919).
Salts. — OuA',: greenish-blue pp. —
Cu(OH)A' : formed from the preceding by heat-
ing with alcohol. — ^PbA'2 aq : crystalline pp., si.
sol. water. — AgA' : scales (from hot water).
Ethyl ether EtA'. (165°). S.G. ia -920.
MobUe oil, smelling of peppermint and of fungi
(F. a. D.). Saponified by boiling alcoholic KOH.
Hezenoic acid OgHnO, i.e,
CH2Et.CH:CH.C02H (?). y-Ethyl-erotcmie acid.
(0. 126° at 26 mm.). From tri-methyl-leucine
Pr.0H2.0H(NMe30H).C02H by heating at 125°
(Komer a. Menozzi, 0. 13, 354). Liquid. Com-
bines with HBr. Its Cd salts form long prisms.
Hezenoic acid CgHioO^ i.e. Et.GH-.CMe.COjH.
fi-Ethyl-methaeryUe acid. [24°]. (213° cor.).
S.G. II -9812. One of the products of the oxida-
tion of the corresponding aldehyde (methyl-
ethyl-aoroloin) (Lieben a. Zeisel, M. 4, 70 ; Solo-
nina, J. B. 1887, 302). Monoclinio prisms;
a:6:c = 1-41:1: -385; /3 = 104° 38'. VolatUe with
steam ; si. sol. water, v. e. sol. ether and benzene.
Combines with bromine, forming di-bromo-hezoio
acid. Eeduced by zinc and HBr (or HI) to^
methyl-propyl-acetic (hexoic) acid. Its soluble
salts give white pps. with salts of Zn, Ag, and
Pb, a blue pp. with CuSO,, and an oily pp. with
FeCla.— CaA',4aq: prisms or silky needles. —
AgA' : sparingly soluble needles or leaflets.
Hezenoic acid C,H,g02 i.e.
(CH3)2C:0H.CH2.C02H or
CH2:CMe.CH2.CH2.00aH. PyrotereUc add.
Formed, together with teraconio acid and the
lactone of oxy-isohexoic acid, by the dry distilla-
tion of terebic acid (Chautard, /. Ph. [3] 28, 192 j
WiUiams, B. 6, 1095 ; Mielok, A. 180, 52). If
the process be conducted slowly the lactone is
the chief product, if rapidly, pyroterebic acid ia
mainly produced. The distillate is heated with
baryta- water, and CO, is passed in until the ppd.
BaCOj is redissolved ; the lactone is then ex-
tracted with ether, and on evaporating the resi-
due barium teraconate orystaUises out. The
mother-liquor is treated with H2SO4, and pyro-
terebic acid distilled over with steam, and puri-
fied by means of its Ca salt. The yield is about
14 p.o. (Geisler, A. 208, 37).
Properties. —Liquid, not solidifying at - 15° ;
si. sol. water. On adding 3 or 4 vols, of water
to the dry acid a homogeneous liquid is obtained,
but further addition of water causes separation
into two layers, the up{)er one being the acid.
The acid is not affected by boiling for some time
with water.
BeacUons. — 1. Converted by prolonged heat-
ing at its boiling-point into the isomeric lactone
of ozy-isohexoio acid. {The same change occurs
ess
HEXENOIO ACID.
when HBr is passed into the aoid, probably
through intermediate formation of the acid
(CHjIsCBr.CHj.CHj.CO.^.— 2. Bromine forms a
di-bromo-isohezoio acid.
Salts. — CaA'jSaq: glisteningprisms. — AgA':
leaf-li^e crystals, si. sol. water.
Hezenoic acid CgH^Oj. Formed by oxidising
hezenyl alcohol with chromic aoid mixture (Dest-
rem, A. Ch. [5J 27, 72). Liquid, volatile with
steam. Split up by potash-fusion into acetic and
bntyric acids. Its salts are amorphous. Pro-
bably identical with the preceding acid.
Hezenoic acid C,H„02 t.e.
CHj:CMe.CHi,.CHj.COjH or
lCB.,)fi:CB..GB.._.0O^. (203° nnoor.). Formed
from the lactone of y-ozy-isohexoic acid by boil-
ing with alcohol and NaOEt for 12 hours (H.
Erdmann, A. 228, 183). Colourless liquid with
pungent odour and aoid taste. When boiled for
a long time it partially changes to the isomeric
lactone of 7-oxy-isohexoio acid. — CaA'jaq. —
CaA'j Baq : trimetric crystals. — AgA'.
Hezenoic acid OjH,„02 i.e. ?r.CH:CH.C02H(?).
Isopyroterebic acid. Formed, together with iso-
sorbic acid, by the action of 00^ on crude OjH,Na,
possibly through presence of C^HgNa as an im-
purity (Lagermarok a. Eltekoff, Bl. [2] 83, 159 ;
J. B. 11, 125). Liquid, si. sol. water; heavier
than water. Slightly volatile with steam. Conl-
bines with HBr. Bromine forms CjHuBrjOj.
[99°]. The silver salt dissolves in water.
Hezenoic acid CjH,„Oj i.e. Pr.CH:CH.C02H(?),
Hydrosorbic acid. (205° cor.); (208° i.V.)
(Pittig, A. 200, 42). S.Gt. ia -969. Formed by
reducing sorbic acid with sodium-amalgam
(Pittig a. Barringer, B. 9, 1198 ; A. 161, 309).
Liquid ; on prolonged boiling it is decomposed,
the boiling-point being raised. Combines with
bromine. Combines with fuming HBrAq readily
in the cold, forming liquid bromo-hexoic acid
(Stahl, B. 9, 120). Potash-fusion gives acetic
and >i-butyrio acid. On warming with HjSO, it
changes to the lactone of oxy-hexoio acid. Its
rate of etherifioation has been studied by Men-
sohutkin (B. 13, 163).— CaA'^ aq [0. 125°]. S. (of
CaA'j) 6'2 at 16°. Needles, more sol. cold than
hot water.— BaAV [above 265°]. Needles.—
CuA',: green pp. [185°-190°].— AgA' : pp. SI.
sol. cold water.
Ethyl ether MA'. [167°].
Hezenoic aoid 0J3.,fi2- Isohydrosorbie acid.
[-rlO°]. (209° i.V.). Formed, together with the
lactone of ozy-hexoio acid, by boiling bromo-
hexoic acid (the hydrobroroide of hydrosorbic
aoid) with water (Hjelt, B. 15, 618 ; cf. Lands-
berg, A. 200, 51). Combines with HBr, forming
theparent bromo-hexoic aoid. — CaA'jaq ilaminaB;
more sol. hot than cold water.
Hezenoic acid CaH,„Oj. HexyUrdc acid.
[39°]. Prom tri-chloro-hezoio acid, zinc, and
HOlAq (Pinner, B. 10, 1054). Long flat needles
(from ether), or lozenge-shaped plates (from
ligroiin) ; nearly insol. water, v. sol. alcohol. Does
not sublime in the cold.
Hexeuoio acid O^K^fi,. (208°). Occurs in
small quantity in croton oil (Schmidt a. Berendes,
A. 191, 121).
iJe/ereraces.— Bbomo- and Chloho-hexenoio
AQIDS.
HEXENOIC ALDEHyDE 0„H,„0 i.e.
Et.CH:CMe.CHO. Methyl-eihyl-acroleU. (137°
cor.). S.Gr. 2 -SO. Formed by heating pro, ionia
aldehyde at 100° with an equal volume ol u, avj-
lution of NaOAc (containing 21 p.c. NaOAc) ; on
fractionally distilling the product the chief por-
tion passes over at 135°-140° (Lieben a. Zeisel,
M. 4, 16). Colourless liquid, with penetrating
odour, insol. water. Gradually turns yellow on
exposure to air. It forms a crystalline com.
pound with NaHSO,.
Beactions. — 1. HCl forms unstable CjH„C10.
2. Bromine forms CjHijBrjO, a heavy oil which
forms crystalline OsH,irBr2(OH)S03Na 3aq.—
3. IronflUngs and HO Ac reduce it to a miztnre
of a hexyl alcohol PrCHMe.CH^OH, the corre-
sponding aldehyde, and an alcohol OjH,jO,
which is readily converted into tri-oxy-hexane
Et.0H(OH).CM6(OH).CH2OH. — 4. Oxidation
with chromic add mixture, free oxygen, or moist
silmer oxide gives carbonic, formic, acetic, pro-
pionic, hexenoic (ethyl-methaorylio), and di-oxy-
hezoic acids, together with methyl propyl ke-
tone.— 5. Ammonia unites with it, forming a
solid product (? CisHj^N, or OijHjjNj), which is
converted at 140° into parvoUne OjH,jN, a
homologne of pyridine (Waage, M. 4, 725). By
heating the compound of hexenoic aldehyde with
NH3 to 200° there is formed piooline, parvoline
(196°), a base C„H„N (233°), and a base C,jH,jN,
which is a mobile liquid, with pale-blue fluor-
escence. The parvoline gives, on oxidation,
pyridine (a;3).di-carboxylio acid (Hoppe, M. 9,
634). — 6. Heated with aqueous SOj for 4 hours
at 80° there is formed, after neutralising with
BaCOj, a salt CaH,20(S0s)2Ba 2aq, which is split
up by heating with baryta-water into barium
sulphite and hezenoic aldehyde. If the contents
of tiie tube are boiled with water before neutral-
ising there is obtained amorphous C5H,j(S0J.;Ba.
7. IE the aldehyde be left in contact with
aqueous SOj for some days and the product be
saturated with BaCO, and oxidised with bromine
water, there is formed a salt of sulpho-hexoio
acid: OsHjnSOsBa crystallising in hexagonal
plates (Ludwig, M. 9, 658).
Hezenoic aldehyde CeH,„Or (1B5°-138°).
Formed, together with allyl chloride and di-allyl-
oxide by heating allyl alcohol with dilute (10
p.c.) HOlAq at 100° for 20 hours (Solonina, J. B.
1887, 302). Oil. Absorbs ozygen eagerly from
the air, producing hexenoic (ethyl-methaorylio
acid). Forms an ozim [49°] (194°). Probab^
identical with the preceding aldehyde.
HEXENYL ALCOHOL CeH,jO i.e.
CHjiCH.CHj.CMejOH. Di-methyl-allyl-cwrhmol,
(120° cor.). S.G. % -8438 ; w -8307. Ba, 49-84 '
(Kanonnikoff). H.C. 914,000 (Lougninine, A. Ch.
[5] 23, 385).
PreparaUon. — By slowly pouring a mizture
of acetone and allyl iodide on granulated zinc at
0° (M. a. A. Saytzeff, A. 185, 151, 175). The
product is mixed with- water and distilled. In
the preparation of this body from allyl iodide,
zino, and acetone, a by-product of the formula
OgHjaO (0. 176°) occurs if the allyl iodide con-
tains isopropyl iodide. Its specific refractive
power, B 05, = 72-27, indicating a double union of
carbon atoms. It combines with bromine form-
ing CjHijBraO. With PCI5 it forms CaH„Cl,
which boils about 180°, with partial decompo-
sition. The same body is also formed by the
action of isopropyl iodide and zinc on the pure
HEXIO ACID.
689
hexenyl alcohol (W. Dieff, j.pr. [2127, 364). A.
mixture of acetone (75 g.), aUyl iodide (205g.),
and isobutyl iodide (230 g.), is converted by zinc
into di-methyl-allyl-carbinol, but a small quan-
tity (2g.) of an alcohol 0,„Ha,0 (o. 195°) is
formed. These bodies appear to be di-methyl-
allyl oarbinol, in which an atom of hydrogen is
displaced by isopropyl and by isobutyl respec-
tively (E. Schatzky, J.pr. [2] 30, 216). The al-
cohol CgHijO is converted by Na and Mel into a
methyl ether CMe2(0Me).0sH„ (169°-172° un-
cor.), Bop 77-01, S.G. '-1^ -8027, which is oxidised
by KMnO, to acetic, isobutyrio, oxalic, and
methoxy-valeric acids (Kononovitch, J. pr. ^2]
30, 399).
• Properties. — Liquid, smelling like' camphor ;
si. sol. water, with which it forms a hydrate
C^ijO aq (117°).
Reactions. — 1. Gnomic acid mratore oxidises
it to formic acid, iS-oxy-isovaleric acid, and ace-
tone. KMnOf acts in like manner (Schirokoff,
J.pr. [2] 23, 205).— 2. JBrowirce forms OaHijBr^O.
3. HOCl, followed by displacement of CI by OH,
gives tri-oxy-hexane (hexyl-glycerin) (Keformat-
sky, J. ^. [2] 31, 818).— 4. By heatmg the al-
cohol (1 vol.) with HjSO, (2 vols.) and water
(1 vol.) for 3 days at 100°, and distiUing the oily
product, two hydrocarbons are got, viz. OjH,,
boiling below 100°, and OuHj, boiling at 180°-
200°. The latter is purified by shaking with PjOj
and redistilling, and exhibits the following pro-
perties: (194°-199°). V.D. 80-3 (H = l). S.G.
a -853; "j* -839. C.E; (0°-21°) -00082. Bgo
89-34. It combines readily with bromine. With
fuming HOI it appears to form a compound
OijjH^o.HOl. It is oxidised by chromic mixture
to acetone, acetic acid, propionic acid and a fixed
acid with the formula 0,„H,sO„ or 0,oH„Oj (W.
Nikolsky a. A. Saytzefl, J.pr. [2] 27, 380). Its
specific rotation is 5-22 more than that calculated
from Bruhl'a numbers. This would indicate
three 0:0 groups (Albitzky, J. pr. [2] 30, 214).
The hydrocarbon OjHio is formdd by removal of
H,0 from the alcohol, so that it is either
(CH3),0:CH.CH:0H, or CH,:0<^g» pHrOH,.
The hydrocarbon C^^^ is a polymeride of this.
Acetyl derivative CsHiiOAo. (138° cor.).
S.G. g -9007 ; ^' -8832.
Secondary hexenyl alcohol
CE^.^'B..CK^.CB^.CR{OB.).0'B^.Di-allylhydrate.
AUyl-isopropyl alcohol. (139°). S.G. if -842
(Orow) ; 2 -861 (Wurtz).
Preparation.— 1. Allyl-acetohe (1 vol.) is
mixed with ether (1 vol.), and put into a flask
containing water (2 vols.). Small pieces of so-
dium are thrown into the flask, which is cooled
meanwhile by standing in water. The ethereal
solution is poured off, dried over KjCOj, and dis-
tilled (J. K. Crow, G. J. 33, 53 ; cf. Kablukoff,
J. B. 1887, 513).— 2. Prom hydriodide of di-
aUyl and Ag^O (Wurtz, A. 07i.,[4] 3, 172).
ProperUes. — ^Sl. sol. water, v. sol. alcohol and
ether. Sweet taste, but rather pungent odour.
Combines violently with bromine. Gives acetic
acid on oxidation (Sorokin, J. pr. [2] 23, 20).
Acetate 0,fl5-CH2.0H(OAc)OH3. (148°)
(Grow) ; (158° cor.) (Markownikofe, J. B.IS, 355).
Formed from the alcohol by heatiug with Ac^O
in a flask with inverted condenser. Formed
, Vol. II.
also from di-allyl di-hydro-iodide and AgOAo.
Liquid with pleasant refreshing odour.
Dibromide
CH2Br.0HBr.0H2.0H,.CH(0H)0H3. Formed by
adding bromine to a solution of the alcohol in
OHOla. The chloroform is then distilled off in
vaciw. It cannot be distilled. KjOOj converts
it into an oil, CeH„Br(0H)2 ; volatile with steam.
Hexenyl alcohol OgHijO i.e.
0H3.0H:CH.0Me2.OH. (ll0°-115°). From the
chloride of crotonic acid and ZnMe, (Fawlow-
sky, B. 5, 331).
Kexenyl alcohol OgHj^O i.e.
OH3.CH2.CH:OMe.CH,OH. One of the products
of the action of iron filings and HOAo on hexe-
noic aldehyde (methyl ethyl-aorolein). Forms a
bromide CsHiJBrjO, which is converted by distil-
lation with water into a tri-oxy-hexane (Lieben
a. Zeisel, M. 4, 28).
Hexenyl alcohol O^ifi- (137°). S.G. M
-891. S. 10 at 10°. Formed by distilling calcium
glycerin CaCaHBO, (Destrem, A. Oh. [5] 27, 58).
Liquid, smelling like peppermint and aUyl alco-
hol. Not reduced by sodium-amalgam. Na
and E form gelatinous OeH„ONa and CgH,,OE.
Chromic acid oxidises it to pyroterebic acid.
Bromine forms OeHi^BrjO (252°-255°); S.G.
i2 1-99. PCI, gives C^.fil (71°). HBr forms
C„H„Br (100°) ; S.G. i2 1-35; Chlorine forms
CeH,jC],0 (205°-210°) ; S.G. is. 1.4. pi, forms
C„H„I (131°) ; S.G. i2 1-92, whence K^S forms
(C,H„)2S (169°).
Acetyl derivative CeH„OAc. (145°).
Benzoyl derivative C|,H„OBz. [105°].
(275°-280°). Yellow prisms.
Beference. — Chloeo-hexentl aiiCohol.
KEXENYL CHLOBIDE OeH„01. Chhro-
hexylene. (71°). From the corresponding
alcohol (Destrem, A. Ch. [2] 27, 5). Light oil.
' Hexenyl chloride
CH,:CH.0H2.0Hj.0HC1.0H3. (130°-140°).
Formed, together with di-ohloro-hexane, by
heating di-aUyl (hexinene) with fuming HGlAq
(Wurtz).
Hexenyl chloride 0„H„C1. (122°). S.G. a
•9036. V.D. 4-02. Formed by the action of cone,
alcoholic KOH on the di-chloro-hexane, which
is a by-prbduct in the action of HOCl on hexyl-
ene from mannite (Henry, C. B. 97, 260).
H2SO4 converts it into a ketone C|jH,j0 (125°) ;
S.G. ii -8343 ; V.D. 3-45.
HEXENYL BLYCESIN v. Tei-oxy-hexane.
DI-HEXENYL OXIDE (O^H.OaO. Dialh/l
oxide. (180°). A product of the action of AgjO
on the mono- or di-hydroiodide of diaUyl (Wurtz,
A. Ch. [4] 3, 175).
Di-hexenyl oxide (CjH,,)^©. (117°). From
hexenyl iodide and HgO. Also from OsH„I and
OsHijONa {v. Hexenyl alcohol). Oil, heavier
than water (Destrem, A. Oh. [5] 27, 58).
DI-HEXENYL SULPHIDE (CeH„)2S. (169°).
From iodo-hexylene and KjS (Destrem, A. Ch.
[5J 27, 58). Heavy oil, of nauseating odour.
Gives a maroon-red colouration with'HjSOj.
HEXIC ACID CjHijOs ? [126°]. An acid
formed from propyl-aoeto-acetio ether by suc-
cessive treatment with bromine and alcoholic
KOH (Demarijay, O. B. 88, 126 ; ef. Fittig, B.
16, 1939 ; PawlofE, B. 16, 486). Large pearly
plates (from hot water).
YY
690,
HEXIO ACID.
Isohexic acid C,H,„Os 7 [124°]. Formed in
like maimer from isopropyl-aoeto-aoetio ether.
Prisms (from ether).
HEXINESE CjH,„i.e.Pr.CH2.0:C.H. Butyl-
acetylene. (70°). Formed by the action of
metaUio sodium on methyl propyl acetylene at
160°, and decomposition of the sodium com-
pound with water (Paworsky, J. pr. [2] 37, 428).
Gives pps. with ammoniacal copper and silver
solutions. Yields on treating the sodium com-
pound with CO, a oarboxylic acid.
Hexinene MejCC-CH. (39°). Formed by
ihe action of alcoholic potash at 140° for
12 hours on di-chloro-tetra-methyl-ethane
(Faworsky, J. pr. [2] 37, 393). Forms pps. with
ammoniacal cuprous and silver solutions. Is
not altered by heating with alcoholic potash to
200°.
Hexinene C,H,g i.e.
CHj:0H.CHj.CH2.0H:0Hj. This compound has
been described as Di-m^yl (q. v.). When heated
with bromine it gives a crystalline mass [46°].
This is a mixture of two substances, [65°] and
[56°], both having the formula OjH,|fBr4. From
this it appears that the di-allyl obtained by the
action of Na on C,HjI is a mixture of two isomeric
bodies, probably CHj:CH.CHj.0H2.CH:CH2 and
CHa.CH:CH.CH:CH.CH3 (dipropenyl) (Sabaneeff ,
Bl. [2] 45, 182). When diallyl is diluted with
(1 vol.) paraffin oil and treated with H2SO4,
the lower layer separated and distilled with
water yields ' hexylene oxide,' a liquid Cg'H.,fi,
smelling like menthol (93°). Oxidation of this
OjHi^O gives HOAo and OO, ;■ sodium-amalgam
has no action ; HI at 100° gives 3-hexyl
• iodide (166°) (Jekyll, Bl. [2] 15, 233). Another
method of hydration is to add the diallyl drop
by drop to well cooled H^SO,. The acid is
diluted with ice, neutralised, and distilled, when
hexylene oxide passes over at 92°-95°. Some
of the salt of the undecomposed sulphuric acid
remains behind iu the flask. The Ba and Ca
salts can be obtained in this way (Bfihal, Bl. [2]
48, 43).
Hexinene C^„. (c. 80°). S.G. ia -71. V.D.
2-84 (calo. 2-79). Formed from petroleum
hexane by bromination, followed by treatment
of the resulting hexenyl bromide with alcoholic
EOH at 155° (Caventou, C. B. 59, 449 ; Beboul
a. Truchot, O. B. 65, 73). Forms a liquid di-
bromide and a crystalline tetrabromide.
Hexinene CHj.CH^.CH^.C^C.CHa ? (80°-83°).
S.G. a -7494 ; f -7377. Formed by the action
of alcoholic EOH on the hexenyl bromide de-
rived from mannite vid di-bromo-hecane (Hecht,
B. 11, 1050). Does not ppt. ammoniacal silver
or cuprous solutions. Oxidised by chromic acid
mixture to acetic w-butyric acids.
Hexinene (CH,)jC:CH.CH:CH2? (80°). From
(CH3)jCCl.CH2.CH:CHj and alcoholic KOH
(M. a. A. SaytzefE, A. 185, 157; «. Hexenyl
AI/COHOL).
Hexinene 0„H,„. (c. 80°). In coal tar
(Sohorlemmer, A. 139, 250). Forms OsH,„Br.
[112°].
Hexinene eaH,„. (70°-73°). V.D. 2-97. Ob-
tained, with other products, by passing the
vapour of heptiuene through an iron tube heated
to incipient redness (Benard, O. B. 104, 574).
Rapidly absorbs oxygen. Does not ppt. ammo-
niacal AgNO, or OugCI,. Bromine forms un-
stable, oily CjHijBrj. Cone. H2SO4 polymerises
it, forming CuHj, (210°-215°).
Beferenees. — Di-bboiio- and Tbtea-ohlobo-
HEXINENE.
HEXINENE GLYCOL v. Di-oxt-hexinene,
HEXINENE DIOXIDE C,H,„Os i.e.
CQ.2-GS. GSj' CHIj* Cm. C52
V V • (182°). Formed
O O
by acting with KOH on the dichlorhydrin pre-
pared by treating diallyl with hypoohlorous
acid (Przybytek, Bl. [2] 48, 110). Colourless
mobile liquid. Heated with water it forms
CeH„(0H)4 sol. alcohol, water, insol. ether.
Treated with HCl a dichlorhydrin is formed.
HEXINOIC ACID 0^0, i.e. Pr.CtO.CO.OH.
[27°]. (125°) at 20 mm. Formed by the action
of CO, on the sodium compound of propyl
acetylene suspended in ether (Faworsky, tT.^.
[2] 87, 419). Feathery crystals. SI. sol. water, v.
sol. alcohol, ether, and petroleum ether. Deli-
quesces in the air. Decomposes on heating or
keeping into CO, and propyl-acetylene. Its
silver salt at once decomposes in the same way.
Salts.-^(CsH,02)jtBa 3aq. V. sol. water.—
A',Ca. Thin needles, v. sol. water. — A',Ca 2aq.
Bine plates, v. sol. water.
Hexinoic acid CjHsO,. [93°-96°]. From
pyroterebic acid, by successive treatmept with
bromine and alcoholic KOH (Mielck, A. 180, 56).
Crystalline mass ; m. sol. water. Volatile with
steam. — ^BaA',: amorphous.
Hexinoic acid v. Sobbic acid.
Hexinoic acid CJSfi, i.e.
(CHs)j.CH.C:C.C02H. Iso-sorbic add. From
f r.C:CNa and CO, (Iiagermark a. Eltekofi, J. B.
11, 125). Liquid. Combines with HBr, forming
0„H,„Br,0,.
Hexinoic acid Pr.OiC.COjH. Isopropyl-
acetylene carboxylic acid. [38°]. (107° at
20 mm.). From di-methyl-aUylene sodium, and
CO, (Favorsky, J. B. 1887, 553). Should be
identical with the preceding.
HEXINYL ALCOHOL C,H,„0 i.e. C^OH
(140°). A by-product of the action of glycerin
on zinc-dust (Glaus, B. 18, 2931). Forms CjHjI
(133°).
Acetyl derivative OjHgOAo. (127°).
HEXINYL CHLORIDE C,H,01. CMoro-
diallyl. (150°). S.G. H? -9197. VJ). 4-15 (calo.
4*02). A product of the action of PCI, upon
allyl-aoetone (Henry, C. B. 87, 171). Oil; com-
bines with bromine, forming oily CgHgClBr,.
Alcoholic KOH at 100° forms hexonene (di-'
allylene). This hexinyl chloride is perhaps a
mixture of the chloride OjHj.CHyCCliCH, with
CsHs-CHtCCLCHs.
Hexinyl chloride 0^01. (130°). From
mesityl oxide, by treatment with PCI5 and dis-
tillation of the resulting 0^1,01, with lime
(Baeyer, A. 140, 298).
HEXIIAMALIC ACID v. Ozz-BEfiTii-suo-
cnno Aon>.
m-HEXOIC ACID 0^„0, i.e.
CH,.CH2.CH,.CH,.CH,.C0,H. n-Caproic acid.
M0I.W. 116. [-1-5°] (Fittig, 4.200,49). (205°).
S.G. 2 -9446 (Zander, A. 224, 67) ; -9453 (Garten-
meister, A. 283, 277); f -9237 (Briihl). C.E.
{0°-10°) -00095 (Z.). S.V. 152-5 (Z.). /i^ 1-4190.
Rob 50-56 (B.). H.C. 830,209 (Louguinine, A. Oh.
HBXOIO ACID.
691
[5] 2£1, 140). Seat of neutralisation: Gal a.
Werner, Bl. [2] 46, 802.
Occurrence. — Among the products of the
bntyrio fermentation of sugar (Grillone, A. 165,
127 ; ef. Stioht, Z. 1868, 220 ; Linnemann, A.
160, 225 ; Lieben, A. 170, 89).
Formation. — 1. By the oxidation of m-hexyl
aloohol (Zinoke a. Franphimont, A. 163, 199). —
2. By the action of boiling alcohoUo EOH on its
nitrile (w-amyl cyanide) (Lieben a. Eoasi, Q. 1,
314; 3,27; 4.159,75; 165,118).— 3. Together
with other fatty acids by the oxidation of pro-
teids. — 4. From re-bntyl-aoeto-acetic ether and
alcoholic KOH (Gartenmeister, A. 233, 277).
Prepaa^ation. — ^By fractionally distilling crude
fermentation butyric acid, and shaking the
portion boiling above 180° with 6 volumes of
water.
ProperHes. — Oil, with faint unpleasant
odour.
Reactions. — 1. Oxidised by nitric acid to
acetic and succinic acids (Erlenmeyer, Sigel a.
BeUi, B. 7, 696 ; A. 180, 215).— 2. Maguesic
caproate in solution subjected to an alternating
electric cv/rrent produces butyric, valeric, oxy-
caproic, oxalic, succinic, glutaric, and adipic
acids (Drechsel, J.pr. [2] 34, 135).
Salts.— CaA'jaq. S. 2-6 at 18° (Kottal, 4.
170, 95) ; 4-6 (Grillone) ; 2-73 at -7° (Keppich,
M. 9, 589).— BaA'j. S. 9-3 at 18-5° (Lieben a.
Eossi) ; 9-1 at 22° (Grillone) ; 9-47 at -5° (Kep-
pich).—BaA'j2aq. S. (of BaA'j) 12-5 at 10-5°
(Lieben a. Janeoek, A. 187, 128).— BaA'2 3aq. S.
(of BaA'j) 12-9 at 23° (K.).— SrA'^ 3aq : laminae.
S. 9-7 at 24° (K.).— ZnA'^aq. S. 1 at 24° (K.).—
CdA',2aq. S. 1 at 24° (K.).— CuA'^. Insol. ether,
sol. aloohol. — AgA' : pp. (Frauohimont a. Zincke,
A. 163, 200). S. -077 at 0° (Keppich).
Methyl ether MeA'. (150°). S.G. § -9039.
C.E. (0°-10°) -00105. S.V. 172-2 (Garten-
meister).
Ethyl ether 'E^tk'. Mol. w. 144. (166-6°)
(G.). S.G. g -8888. 0.B: (0°-10°) -00103.
S.V. 197-7.
Propyl ether PrA'. (186°). S.G. § -8844.
O.E. (0°-10'') -00101. S.V. 222-2.
Butyl e«^erPr.CHjA'.(204°). S.G.§-8824.
O.E. (0°-10°) -00099. S.V. 246-0.
n-Hexyl ether C^„A'. (246° cor.). S.G.
^li -865 (Franchimont a. Zincke, A. 163, 197).
JSeptyl ether Gfi,^'. (259°). S.G.g-8769.
C.E. (0°-10°) -00088. S.V. 328-9.
n-Octyl ether G,B.,Ji.'. (275°). S.G.2-8748.
C.E. (0°-10°) -00088. S.V. 349-6 (Gartenmeister).
Occurs in oil of Heracleum (Zincke, A. 152, 18).
Chloride CoHnOCl. (c. 138°) (B^champ,
A. 130, 364).
Anhydride (CeH,iO)jO. Liquid (Chiozza,
A. 86, 259).
Acetyl-hexoia anhydride OjHjjO.OAc.
(165°-175°). Liquid, lighter than water. Formed
by heating hexoic acid with AcjO (Autenrieth,
B. 20, 3187).
Amide [100°]. (255°) (Henry, B. 2, 490).
Plates. Sol. alcohol and hot water. Prepared
by heating ammonium hexoate at 230° under
pressure ; the yield is 70 p.o. (Hofmann, B. 15,
983 ; 17, 1411).
Anilidt CsHn.CONHPh. [95°]. Formed by
heating the amide with aniline (Kelbe, B. 16,
laOO). Needles, v. sol. alcohol and ether.
Phenyl hydrazide CsH.i.CO.NH.NHPh.
[117°].
Nitrile C5H„CN. n-Amyl cyamde. Mol.
w. 97. (154°). S.V. 141-1 (B. Sohifl, B. 19, 568).
Formed, together with hexylamine, by allowing
a mixture of the amide of heptoio acid (1 mol.)
and bromine (3 mols.) to run into a 10 p.o. solu-
tion of NaOH (Hofmann, B. 17, 1410).
Isohexoic acid CeH,j02i.e.Pr.OH2.CH2.COjH.
Isocaproic acid. Isobutyl-acetio acid. (200° i.V.).
S.G. ^2 .925. Heat of neutralisation: Gal a.
Werner, Bl. [2] 46, 802).
Occurrence. — As glyceryl ether in butter
(Chevieul, Becherches sur les corps gras), in
cheese, and in cocoa-nut oil (Fehling, A. 53, 406).
Occurs in the free state, together with butyric
and valeric acids in the f owers of Satyrmm
hircvnwm, which have an odour of bugs (Chau-
tard, Bl. [2] 2, 56) ; and, together with several of
its lower homologues, in the sarcocarp of Qimgko
biloba (B6champ, A. 130, 364). Found by C.
Kraut {A. 103, 29) in the water of a brook
running out of a peaty soil. Formed also by
the fermentation of wheat bran (Freund, J. pr.
[2] 3, 224).
Formation. — 1. By saponifying its nitrile
(isoamyl cyanide), which is obtained from iso-
amyl iodide by boiling with alcohol and calcined
KjFeCyo(Franklauda.Kolbe,4. 65, 303; Wurtz,
A. 105, 295). — 2. By the action of COj on sodium
isoamyl (produced by treating ZnEtj with so-
dium) (Wanklyn a. Schenk, G. J. 21, 31).— 3. By
the oxidation of proteids, fats, and oils, hexoic
acid is often formed, but in most oases it has
not been detemiined whether it is n- or iso-
hexoic acid (£edteubacher,.i.59,41; Schneider,
A. 70, 112; Arzbacher, A. 73, 203; Guckel-
berger, A. 64, 70). — 4. From 7-oxy-isohexoio acid
by heating with HI and red phosphorus (Mielck,
A. 180, 45). — 5. By decomposing isobutyl-aoeto-
acetic ether with baryta (Eohn, A. 190, 316). —
6. Either n- or iso-hexoic acid occurs to the ex-
tent of 3 p.c. among the acids produced by the
fermentation of the perspiration of sheep (yolk).
7. From leucine and nitrous acid. — 8. One of
the products of the action of zinc isoamyl on
oxalic ether (Frankland a. Duppa, A. 142, 17).
Properties. — Liquid, with rancid smell. Not
solidified by cooling to — 18°- When its potas-
sium salt in aqueous solution is decomposed by
an electric current decane is produced (Brazier
a. Grossleth, A. 75, 249).
BeacUon. — Oxidised by KMnO, to 7-oxy-iso-
hexoic acid (0H5),C(0H).CHj.CHj.002H which
splits off water, giving the lactone
{cs,)fi<:^^^^>.
Salts.— CaA'jSaq. S. (o! CaA',) 12-7 at
18-5° (Lieben a. Eossi, A. 165, 124) ; 5-8 at 21°
(Mielck) : 9-9 at 19° (Eohn).— BaA'^aq. S. (of
BaA'j) 21 at 22° (Mielck).— BaA'2 2aq. S. 53 at
18-5° (L. a. E.); 25 at 14° (Eohn).
Methyl ether MeA'. (150°). S.G. « -898
(FehUng, A. 53, 410).
Ethyl ether MA.'. {16V eoT.). S.G. §-887;
|g-8705(L.a.E.).
Isoamyl ether OjH„A'. (215°-220°)
(Frankland a. Duppa, A. 142, 18).
Amide Pr.CH^.CHj.CONHj. [120°]. Pre-
pared by heating ammonium isocaproate at 230°
X y3
392
HEXOIC ACIT).
under pressure; the yield is 63 p.o. of the theo-
retical (Hofmann, B. 15, 983 ; 17, 1411).
Nitrile ft.CH2.CHj.CN. Isoamyl cyanide.
(155°) (Wurtz, A. 105, 296). S.G. =-° -806. V.D.
3-34. Formed by heating isoamyl oxalate,
chloride, or iodide with KCy (calcined KjFeCyj)
(Balard, A. Ch. [3] 12, 294; Franklanda.Eolbe,
A. 65, 288 ; Brazier a. Gossleth, A. 75, 251 ;
Medlock, A. 69, 229 ; Wurtz, A. 105, 296). So
prepared it is dextrorotatory ; [o]d = 1"59, and is
therefore impure. It forms the following com-
pounds : (C5H„N)2TiCl,. — (C5H„N)2SnClj. —
C.H„NSbClj. .
Hexoic acid CeH^Oj i.e. CHPtMe.COjH.
MethyUpropyl-aciUc (md. (194° cor.). S.G. "
•9231 ; W -9279 (Liebermann a. Scheibler, B. 16,
1823) ; ^ -9286 (Liebermann a. Eleemann, B.
17, 918). CJ!. -00075.
Formation. — 1. From amylene by combina-
tion with HI, treatment of the product with
KCy at 115°, and saponification of the product
(A. Saytzeft, B. 11, 511 ; 4. 193, 349).— 2. By oxi-
dising PrCHMe.CHaOH with chromic acid mix-
ture (Lieben a. Zeisel, Jlf.4, 37). — 3. By reducing
BtCH:CMe.COjH with HI (L. a. Z.).— 4. By re-
duction of the lactone of 7-oxy-o-methyl-valerio
acid (caprolactone) by heating with HI and red
phosphorus at 200° (L. a. S.). — 5. By the action
of n-prppyl iodide on sodium methyl-aoeto-aoetio
ether and saponification of the product (L. a.
K.; B. J. Jones, A. 226, 294).— 6. Froni iso-
saccharin by reduction with HI and P (Kiliani,
B. 18, 632). — 7. In oil of resin, obtained by the
dry distillation of colophony (Kelbe a. Warth, B.
15, 308).
Properties. — Inactive liquid, si. sol. water.
Weak acid. FeCl, gives, in a solution of the
ammonium salt, a flesh-coloured pp. soluble in
excess of the reagent (S.).
Salts. — CaA'j. Prisms (from alcohol) (S. ;
Ii. a. Z. obtained CaA'^aq). — CaA'^aq: small
needles (from a solution saturated at 50°) (K.
a. W.).— CaA'j2Jaq: long needles. S. 11-8 at
17°; 7-6 at 100°. — CaA'^ 3aq (L. a. Z.). —
CaA'j4aq (L. a. Z.).— CaA'^Saq (L. a. Z.).
— OaA'2 8aq : silkyneedles (KiUani). S. (of CaAy
32 at 18-5° (A. Saytzeff, J.pr. [2] 23, 293).— BaA'^ :
gummy; v. sol. water (S.). — ZnA'^: more sol. cold,
than hot, water (S.). [72°] (K. a. W.).— CuA'^:
green pp. — CuA'jCUjOj : light green pp. — AgA' :
slender needles. S. -47 at 20° ; -9 at 100° (S.).
Ethyl ether EtA'. (153° i.V.). S.G. §
-8816 ; « -8670 (A. Saytzeff, A. 193, 352).
JBexyl ether C,Ta.,sA'. (224° cor.). Formed
in the oxidation of CMePrH.CHjOH by chromic
acid mixture (L. a. Z.).
Amide OsEifiOy^B^. [95°]. Needles (K. a.
W.).— (C5H„.CO.NH)2Hg. [0.158°]. Needles.
Hexoic a;cia O^.jOj i.e. CHftMe.COjH.
Methyl4sopropyl acetic acid. (190°). S.G. is
•928.
Formation. — 1. From CHftMel vid
CHJrMeON (Markownikoff, Z. 1866, 502).— 2.
From methyl-isopropyl-aoeto-acetio ether, ob-
tained by treating aceto-aoetio ether successively
with NaOEt and PrI followed by Mel ; or with
Mel followed by PrI. Neither method gives a good
yield (VanEomburgh, B. T. C. 5, 228).— 4. From
malonic ether by like processes (R.).
Properties.— la^nid, smelling like its isomer-
ides.
Salts.— flaA',. Less sol. hot, than cold,
water. S. 20 at 15°. Slender needles (from al-
cohol).— AgA': needles (from water).
Amide CsHn-CONHj. [129°]. Sol. water,
alcohol, ether, and benzene. Easily sublimed
(E.).
Hexoic acid CjHijOj i.e. CEtMe^.CO^H. Di-
methyl-ethyl-acetic acid. [—14°]. (186°). Ob-
tained from the correspondingiodideCEtMejCHjI
by heating ■with potassio-merouric cyanide, frac-
tionally distilling the resulting nitrile, and then
heating it with fuming HCl for 6 days at 100°,
and then for 2 days at 120° (Wischnegradsky, B.
7, 730 ; A. 174. 56 ; 178, 103). Formed also by
reducing methyl ethyl ketone with sodium amal-
gam and oxidising the resulting pinacolin CjHuO
with CrOj (Lavrinovitch, A. 185, 126).
Salts. — ^BaA'j5aq: large transparent plates
(from water) ; v. sol. water. — ZnA'j: white pp. —
AgA' : slender needles (from hot water).
Chloride CMe^Et.COCl. (132°).
Nitrile CMe^Et.CN. (130°).
Hexoic acid CeHjjOj i.e. CEtjH.OOjH. Di-
ethyl-acetic acid. (190° i.V.) (Saytzeff). (191°)
(Burton, Am. 3, 393) ; (196°) (Sohnapp, A. 201,
70). S.G. § -936 ; f -920 (Saytzeff) ; ^ -946
(Sohnapp).
FormaUon. — 1. From oxy-hexoio ether (di-
ethyl-oxalio ether) CEt2(0H).Cd2Et by treatment
with PCI5 which gives CEtjCl.COjEt, which is
then reduced by sodium amalgam (Markowni-
jkoff, B. 6, 1175). The same chloro-hexoic ether
is resolved by ^stillation into HGl and hexenoio
ether, which may be reduced in like manner by
sodium-amalgam. — 2. From di-ethyl-aceto-acetio
ether (Frankland a. Duppa, A. 138, 218).— 3. By
passing CO over a mixture of NaOEt and NaOAfc
heated to 205° (Frohlioh, A. 202, 308).— 4. To-
gether with aldehyde, by distilling j8-oxy-di-a-
ethyl-butyrio acid CH3.CH(OH).CEt2.COjH
(Schuapp, A. 201, 70), or by treating the same
acid with PCI5 followed by water (Burton). Also
from the same acid and HI (B.). — 5. From CHEtjI
m(i the cyanide (A. SaytzefE,4. 193,349).— 6.From
di-ethyl-malonio ether (Conrad, A. 204, 141). —
7. From ethyl-crotpnic acid CHjiCH.CEtH.CO^
by combining with HBr and reducing the result-
ing bromo-hexoic acid (Howe a. Fittig, A. 200,
24; A. Saytzeff, J.pr. [2] 23, 288). ,
Properties.— Liquid; not solidified at -15°.
Salts.— CaA'.,. S. 25 at 23°. Gummy (from
water) or twin-crystals (from alcohol). — CaA'^aq:
lamina. S. (of CaA'j) 33 at 18^5° (H. a.F.) ; 30
at ^7° (Keppich, U. 9, 589). On evaporating the
solution a thin crust forms which dissolves again
on cooling. Crystals may be obtained by stirring
duringevaporation. — BaA'22aq. — ZnA'j: less sol.
hot than cold water. — ^AgA'. S.-4at-7° (Keppich) ;
■5 at 20"?; -75 at 100°.
Ethyl ether Etk'. (151°). S.G. g -883;
w -869 (Saytzeft).
Hexoic acid C^jJO, i.e. CHEtMe.CHj.COjH.
$-Methyl-P-ethyi-propioTdc-acid. (c. 197°). S.G.
i^-930. [o]d = 8-92?. Formed by oxidising active
hexyl alcohol by K^CraO, and H^SO, (Van Eom-
burgh, B. T. C. 5, 222).
Salts. — CaA'jSaq: tufts of small needles
(from water). — AgA': needles (from hot solu-
tions).
Bexyl ether C^„A'. (233°). S.G. ^
HEXYL ALCOHOL.
693
■867. [o]d = 12-86<'. Formed in the oxidation of
the alcohol.
Amide CsHi.CONHj. [124°].
References. — Amido-, Bbouo-, and OhIiOEO-
EEZOia ACIDS.
ra-HEXOIC AIDEHYDE 0,H,jO i.e.
Pr.OH2.CHj.CHO. n-Ca^oie aldehyde. Mol.
w. 100. (128° cor.). S.G. s .850; ^ -834.
Formed by distilling calcium oaproate (10 pts.)
with calcium formate (7|pts.) (Lieben a. Janecek,
A. 187, 130 ; G. J. 32, 879). Limpid liquid,
BmeUing like aldehyde. Forms a crystalline
compound with NaHSO,. Is readily ojddised
and readily polymerised.
Hezoic aldehyde Pr.CHj.OHj.CHO. Iso-
caproic aldehyde. (121°). Formed by distilling
sodium formate with sodium isohexoate (Bossi,
A. 133, 178). Liquid with pungent odour, si. sol.
water, miscible with alcohol and ether. Beduces
ammoniacal AgKO,. Gives on oxidation iso-
hexoio (isobutyl-acetic) acid. Bednced by
Bodimn-amalgam to hexyl alcohol (150°). . Com-
bines with NaHSOj.
Hexoic aldehyde C^,fi i.e. Pr.OHMe.CHO.
(116° cor.). From Et.CH:CMe.CHO, iron, and
dilute HOAc by standing in the cold for a month
(Lieben a. Zeisel, M. 4, 23). Combines with
NaHSOj. Gives Pr.CHMe.COjH on oxidation.
Beferenee. — iKC-OHiiOfio- and Di-bbomo-bbxoio
AI^EHTDE.
HEXONENE CeH,. (80°-85°). S.G. -80.
Among the products deposited on compressing
the gas obtained by heating oils (Couerbe, J. pr.
18, 165). The same hydrocarbon (85'5°) occurs
in petroleum from Amiano (Dumas, A. 6, 257).'
Isomeride : Ciallylene (2. v.). V. also
Bbomo-hexonene.
HEXONITEIIE v. Nitrile of Hexoio aoid.
HEXOinrii BBOMISE CsH,Br. Bromo-di-
allylene. (150°). From di-bromo-diallyl and KOH
(Henry, B. 14, 400). Liquid, heavier than
water. Combines with bromine. Fpts. anmio-
niaoal AgNO, and CujCl,.
HEXUNENE C,H„. [64°]. (130°). V.D. 2-81.
Formed by distilling cuprous aUylide with an
alkaline solution of KjFeCy, (Griner, C. B. 105,
283). In presence of CSj it combines with
bromine forming crystalline OsHjBrj [44°]. It
does not ppt. ammoniacal cuprous chloride.
iBomerides. Bekzene and DiPBOFAitciTii.
SI-HEXTL V. DosECANis.
HEXTL ACETATE v. Acetyl dervoatvoe of
HeXVI< ALCOHOL.
HEXYL ACETTIENE v. Ootinene.
M-HEXYL AICOHOI CsHnO i.e.
Pr.CH,.OH-.OHjOH. Mol. w. 102. (157° cor.).
S.G. a -832. C.E. (0°-10°) -00087. S.V. 146-2
(Zander, A. 224, 82). Occurs in fusel oil from
brandy (Faget, .4.88, 325) to the amount of -6 p.o.
(Ordonneau, G. B. 102, 219). ra-Hexyl acetate
and butyrate occur in the essential oil of Sera-
cleum (Franchimont a. Zincke, B. 4, 822 ; A. 163,
193 ; Moslinger, A. 185, 41). Perhaps the hexyl
aloohbl in these cases is 5r.CHj.CH2.CH20H.
Forrmtton. — 1. Through the acetate, from
»-hexyl chloride which is formed, together with
«ec-hexyl chloride, by chlorinating hexane
(CaSours a. Pelouze, O. S. 64, 1245 ; Schorlemmer,
A. 161, 271).— 2. By reducing the corresponding
aldehyde with sodium-amalgam (Lieben a. Bossi,
A. 133, 178 ; Lieben a. Janecek, A. 187, 126).
1 Formyl derivative CeH,30CH0. (140°).
S.G. i2 -8495. Smells like apples.
Acetyl derivative (JjH,aOAo. (170° i.V.).
S.G. "-^ -889 (F. a. Z.) ; f -8902. C.E. (0°-10°).
■00100. S.V. 197-7 (Gartenmeister).
Benzoyl derivative CjHiaOBz. (272°).
S.G. il -998. Oil, smelling like apples (Frentzel,
B. 16, 745).
Hexoyl derivative CjHijO.CO.CjH,,.
(246°). S.G. '^'-865.
Ethyl ether C„H,sOEt. (134°-137°).
Isohexyl alcohol gr.CHj.CH^.CHjOH. (150°).
Formed by reducing the corresponding aldehyde
with sodium amalgam (Bossi, A. 133, 180).
Hexyl alcohol CHa.CHj.CHMe.CHj.CH^OH.
$-Ethyl-butyl alcohol. (154° cor.). S.G. i^
•829. [o]i, = 8-2°. Obtained among the products
of saponification of Boman oil of chamomile
(Van Bomburgh, B. T. G. 5, 220). Gives on
saponification a dextrorotatory hexoic acid and
ahexylhexoate (234°), S.G.i^ -867, [0],, = 12-86
at 19°.
Hexyl alcohol OHs.CHj.CHj.OHMe.CHjOH.
a-Propyl-jpropyl alcohol. (147°). S.G. g •8375.
One of the products of the reduction of
CHEt:CMe.CHO, and separated from the ac-
companying CHEtiCMe.OHjOH by treatment
with bromine and water, whereby the latter is
changed to CHEt(0H).CMe(0H).CH20H (Lieben
a. Zeisel, M. 4, 28). Optically inactive liquid.
On oxidation with chromic aoid mixture it yields
CH2Et.CHMe.CO2H and methyl propyl ketone.
Acetyl derivative C.H.jOAc. (162° cor.).
S.G. If -8717.
Hexyl alcohol ^Pr.CHMe.CHjOH (?). '(153°
i.V.). S.G. — -830. Occurs as augelate and tig-
late in Boman oil of chamomile (Kobig, A. 195,
102). Formed also from ¥t.¥i by chloriiiation,
&c. (Silva, B. 6, 147).
Acetyl derivative OaHuOAo. (155°-160°).
/Sec-hexyl alcohol
OH,.CH2.dH2.CH2.CHMe.OH. Methyl-butyl-ca/r-
Unci. (eS-Hexyl alcohol. (137°) (B. a. W.) ;
(141°) (S.). S.G. 2 -833 ; iS -821.
FrnnaUon. — 1. By digesting (3)-hexyl iodide
with water and AgzO (Wanklyn a. Erlenmeyer,
C.J. 16, 221; Heoht, A. 165, 146), or with a
large excess of boiling water (Niederist, A. 196,
351) . — 2. From the corresponding chloride which
is formed together with n-hexyl chloride by
chlorinating n-hexane (Schorlemmer, A. 161,
272). — 3. From the mixture of chlorides obtained
from w-hexane by conversion into hexylene and
treatment with HCl (Morgan, A. 177, 307).' — i.
By converting (j8) -hexyl iodide into hexylene,
treating the product with H2S04aud distilling tha
resulting CsHiaO.SOjH with water (W.a.B.).— 5.
Formed also by treating hexylene from inannite
with HOCl and reducing the product with iron
filings and acetic acid (Domao, Jlf. 2, 320; A.
213,124).
Properties. — Thick liquid with pleasant
odour, very unlike that of isoamyl alcohpl.
Chromic acid mixture oxidises it to an aldehyde,
and afterwards to butyric and acetic acids.
Acetyl derivative CsS,sOAc. (156° cor.).
S.G. fi -878.
Ethyl ether CsHjaOBt. (133°). S.G. i'
•776.
694
HEXYL ALCOHOL.
fiec-hezyl alcohol
CH3.CH2.CHMe.CHMe.OH. Methyl-sec-butyl-
earUnol. (134° i.V.). S.G. ^i -8307. Formed
by reducing methyl sec-butyl ketone dissolved in
wet ether by sodiam. A pinaoone CijHjjOj
(249°) is also formed, and this, when warmed
with dilute H2S04 gives two pinacohnes Ci^H^iO
(Wislioenus, A. 219, 319). Colourless oil.
£iec-liezyl alcohol
CH,.CHj.CH{OH).CH2.CH2.CH3. Ethyl-propyl-
carUnol. (135° cor.). S.G. 2 -834; M .gig.
Formed by reducing ethyl propyl ketone by
sodium-amalgam (Volker, B. 8, 1019 ; Oeohsner
de Coninok, Bl. [2] 25, 7 ; B. 9, 193). Gives on
oxidation ethyl propyl ketone and propionic
acid.
Acetyl derivative C^^fikxi. (150°).
Hexyl alcohol CjH„0. (138°). Prom di-
chloro-di-ethyl oxide CBLjCl.CHCl.OBt by treat-
ment with ZnEtj and treatment of the resulting
CH^Et.CHEt.OBt with HI, KOAo, and KOH
successively (Lieben, A. 178, 22). Gives acetic
and butyric acids on oxidation, and would there-
fore appear to be identical with methyl-butyl-
carbinol.
Ethyl ether CsH^OEt. (131°). S.G. 2
•787 ; ^ -770.
Sec-hexyl alcohol (CH3),.C.CHMe.0H.
Methyl-tert-hutyl-ca/rUnol. [4°]. (120-5°). S.G.
- '635. Formed by reducing tiie corresponding
ketone (pinacolin) with sodium-amalgam (Friedel
a. Silva, C. B. 76, 226). Liquid smelhng like
camphor, solidifying in a freezing-mixture to a
mass of long sUky needles. Oxidised by chtomic
mixture to pinacolin and tri-methyl-acetic
acid.
Acetyl derivative OeHuOAc. (0. 142°).
Jfert-hexyl alcohol CMeEtjOH. Methyl-di-
ethyl-carbinol. (123°). S.G. 'I" -8237 ; f -8194 ;
f -8104.
Formation. — 1. By treating acetyl chloride
with ZnEt^, leaving the product for two days
until it has become viscid ; then heating to 100°
and mixing with water (Butlerow, Bl. [2] S, 17).
2. Together with hexylene, hexane, and other
products by treating CHj.CHI.CHMeBt dissolved
in alcohol with HOAb and zinc (Wislioenus, A.
219, 315).— 3. From the corresponding iodide
CMeEtjI and cold very dilute KOHAq (W.).— 4.
By acting on di-ethyl ketone (1 mol.) with Mel
(3 mols.) and zinc, followed by water (Eefor-
matsky, J. pr. [2] 36, 340). Colourless mobile
liquid, smelling like ^r^butyl alcohol. Chromic
acid mixture oxidises it to acetic acid only.
Acetyl, derivative CMeEtj.COAo. (148°
cor.). S.G. f -8824 ; %= -8772 ; %= -8679.
Tert-hexyl alcohol CMcjPr.OH. Di-methyl-
propyl carbmol. (115°) (B.) ; (123°) (J.). Formed
by treating butyryl chloride with ZnMej followed
by water (Butlerow, Z. 1865, 617 ; Jawein, A.
195, 254). Bather viscid liquid, lighter than
water, and somewhat soluble therein. ' Does not
solidify at — 38°. Gives on oxidation acetic and
propionic acids.
Teri-hexyl alcohol CMe^PrOH. Di-methyl-
isopropyl-ca/rbinol. (113°) (P.) ; (117°) (Pavloff,
A. 196, 128) ; (119°) (Z.). S.G. 2 -836 ; 12 -823
(P.) ; 2 -837 (K.). C.E. (0°-50°) -00099. .
Formation. — 1. By treating isobutyryl chlor-
ide with ZnMcj followed by water (Prianisoh-
nikoff, Bl. [2] 10, 303).— 2. From a-bromo-pro-
pionyl bromide by successive treatment with
ZnMej and water (Kaschirski, C.C. 1881, 278).—
3. By acting on ZnMe.^ (5 pts.) ,with phloral (2
pta.) (Bizza, Bl. [2] 38, 164).— 4. iProm ZnMe,
and di-chloro-aeetyl chloride, the yield being
6 p.c. (Bogomoletz, Bl. [2] 34, 330).
Properties. — ^Liquid, smelling of camphor,
BoUdif y ing at — 14°. On oxidation with chromic
acid mixture it gives acetone and acetic acid.
References. — Bbomo- and Chlobo-hextii-
ALCOHOL.
(n)-HEXYI-AMIN£
CBL,.CHj.CHj.0Hj.0H2.0Hj.NHj. (129"). S.G.
— "77. Occurs in cod-liver oil (Gautier a.
Mourgues, C. B. 107, 254). Obtained from
OT-hexyl chloride (derived from m-hexane in
petroleum) and NH, (Felouze a. Cahours, A. Oh.
[4] 1, 5).
Preparation. — A mixture of equal mols. of
the amide of hexoic acid and bromine is run into
an excess of a 10 p.c. solution of KOH at 60° ;
the yield is 70 p.c. (Hofmann, B. 16, 771;
Frentzel, B. 16, 744).— B'HCl : lamina. —
B'jHjPtCls: scales.
Isohexyl-amine Pr.CHj.CHj.CH^NHj. From
isohexyl iodide and alcoholic NHj (Eossi, A.
133, 181).— B'^HjPtClj : scales.
(iS) - Kcxylamine Pr.CHj.CHMe.CHjNHj.
(116° i.V.). S.G. -76. Formed, together with '
hexylene, by heating (i8)-hexyl iodide with NH,
(Uppenkamp, B. 8, 56 ; Jahn, B. 15, 1292 ; M.
3, 170).— B'jHjPtCls : golden plates.
Tert-hexylamine CMeEtjNHj. (109°). From
the oarbamine CMeEtuNC audHClAq (Sohdanoff,
A. 185, 123).
Di-ra-hexyl-amine (CeH„)jNH. (190°-195°).
From alcoholic NH, and w-hexyl chloride
derived from M-hexane of petroleum (P. a. C).
Tri-TC-hexyl-amine (C„H,3)sN. (260°). From
TC-hexyl chloride and alcoholic NH, (P. a. C).
Formed also by distilling with lime the com-
pound of heptoic aldehyde (oenanthol) with NH,
and SO2 (Petersen, A. 101, 310 ; 102, 312).—
B'HCl.— B'jHjPtClB : glittering laminas.
Ethylo-iodide (C5H,5)3NEtI : liquid.
HEXYL-BENZEHE
Ph.CHj.CH2.CH2CH(CHs)2. Oapryl-bemene.
(212°-213°) at 733 mm. S.G. i2 -857. From '
benzyl bromide, iso-amyl bromide, benzene, and
sodium (Schramm, A. 218, 391 ; c/. Aronheim,
A. 171, 223).
iJeociioK. — Bromine vapour at 150° forms
PhCHBr.CHj.CH,.CH(CH3)2, which, on distiUa-
tion, gives HBr and phenyl-hexylene, whose di-
bromide Ph.CHBr.CHBnCHj.CHMej forms
needles or plates [79°-80°].
Reference. — Di-bbomo-hexyl-benzbne.
w-HEXYL BEOMIDE CsHiaBr. (156° cor.).
S.G. 2 1-194 ; 22 1-173. From «-hexyl alcohol
and HBr (Lieben a. Janecek, A. 187, 137).
Hexyl bromide Pr.CHMe.CHjBr. (0. 144°
cor,). From the corresponding alcohol and cone.
HBrAq at 130° (Lieben a. Zeisel, M. 4, 33).
Converted by water (30 pts.) at 150° into
hexylene.
Sec-hexyl bromide Pr.CH2.CHMeBr. [144°].
From boiling w-hexane and bromine (Schor-
lemmer, A. 188, 250).
HEXYL - CHLOBAIi v. Tbi-ceiiObo-hexoio
HEXYLENE.
696
n-HEXYL CHLOBISE OsHuCl i.e.
Pr CHj.CH4.CH.,Cl. Ghloro-hexane. (133°)
(Lieben a. Janecek, A. 187, 139 ; Frentzel, B. 16,
745). Formed, together with (/3)-hexyl chloride,
by chlorinating n-hexane (Cahours, O. B. 10,
1241).
/Sec-hexyl chloride
0B,.0B.01.CB.^.CK,.CH^.CB.^. {$).Rexylchloride.
(125°). From cold fuming HCl and hexylene,
derived from w-hexane (got from mannite) by
ohlorinatiou and subsequent treatment with
alcoholic potash (0. Schorleihmer, Pr. 29, 365 ;
T. 171, 452; Domao, M. 2, 313). Formed also,
together with w-hexyl chloride, by chlorinating
ra-hexane (Schorlemmer, A. 161, 272), and by
saturating (j8)-hexyl alcohol with HCl and heat-
ing in a sealed tube at 100° (Erlenmeyer a.
Wanklyn, C. J. 17, 190). With Pb(OAo)j and
glacial acetic acid at 125° it forms hexyl acetate
CjH,sOAc. If this is ppd. by water and saponi-
fied by strong potash an alcohol or mixture of
alcohols (130°-140°) is got. This alcohol gives
on oxidation acetic and butyric, but no propionic
acid.
Hexyl chloride gr.CHMe.CHjCl. (124=). A
product of the ohlorination of Fr.Pr (Silva, Bl.
[2] 6, 36 ; 7, 953).
Sec-hexyl chloride CjHisOl. (117°). Formed
by passing HCl through a mixture of cone.
HClAq and the mixed hexylenes obtained
by the actioh of alcoholic KOH upon the mix-
ture of hexyl chlorides got by chlorinated n-
hexane (Morgan, C. J. 28, 301). The same
hexyl chloride is probably also got from the
hexylene found among the products of the dis-
tillation of glycerin with NaOH (Fembach, Bl.
[2] 34, 146). The corresponding alcohol boils at
125°-129°, and gives on oxidation a ketone
(c. 123°).
Sec-hexyl chloride C^.aCl. (123°). Ob-
tained by heating with HClAq for 10 hours at
135° the hexylene left uncombined in preparing
the preceding hexyl chloride (M.). Probably
identical with (/3)-hexyl chloride. When heated
vrith Pb(OAc)j and HOAo at 120° it gives a
hexyl acetate which, on saponification, yields a
hexyl alcohol (132°-137°), which is oxidised by
chromic acid mixture, even in the cold, to a
ketone (125°).
Sec-hexyl chloride CMes.CHMe.Cl. (114°).
S.G-. - "899; 2£ •876. From the corresponding
alcohol and HCl (Friedel a. Silva, Bl. [2] 19,
'rert-hexyl chloride CMe^PrCl. (100°).
From the alcohol and PCI, (Butlerow, J. 1864,
497). Partially decomposed on distillation.
Tert-hexyl chloride CMe^PrCl. [-2°]. (111°).
S.G. 2 -897 ; ^^ -878. From CMe^iOMea and HCl
(Pawloff, A. 196, 124 ; Kasohirski, 0. C. 1881,
278). Also from frfr and CI (Silva).
Tert-hexyl chloride OMeBtjCl. (110°).
From the alcohol and PCI5 (Butlerow).
Hexyl chloride C,H,„C1. (122°). S.G. "
•8943. From di-ieopropyl (hexane) ?rPr and
chlorine (Schorlemmer, A. 144, 184). SUva (Bl.
[2] 6, 36 ; 7, 953) obtained, however, CMejjPrCl
(118°) and Pr.CHMe.CH,Cl (124°).
HEXTI-CTAITIC ACID v. CYAmc acid.
w-HEXYIENE C„H,2 i.e.
CH,.CHj,.CHj.CH2.0H:CHj. Buiyl-ethylme.
{aj.Heayylme. Mol. w. 84. (69°). Fromji-hexyl
chloride and alcoholic KOH (Morgan, A. 177,
305 ; Schorlemmer, A. 199, 141). The same
hexylene is perhaps formed by treating the di-
hydro-di-iodide with sodium. It boils at 69°,
and has S.G. s,-694 (Wurtz, A. Oh. [4] 3, 129).
GreviUe WiUiams {T. 1847; A. 108, 384) found
a hexylene boiling at 71° among the products of
the distillation of Boghead coal. Thorpe and
Toung (A. 165, 8) obtained a hexylene boihng
about 65° to 70° from strongly heated paraffin.
7i-Hexylene is among the products of the manu-
facture of oU gas (Armstrong, 0. J. 49, 74).
Properties. — ra-Hexylene does not combine
with fuming HCl in the cold ; hut at 100° it
forms hexyl chloride (123°). With bromide of
nitrogen it fqrms a heavy oil (A. K. Miller, C. J.
Proc. 3, 110).
(fl)-Hexylene CHa.0Hj.CH2.0H:CH.CH3.
(69°) (W. a. B.); (67°) at 738 mm. (Heoht a.
Strauss, A. 172, 62). S.G. 2 -700. V.D. 2-92
(calo. 2-90). Obtained, apparently in the pure
state, from the ra-hexane derived from mannite
by chlorinating and heating the resulting, mix-
ture of hexyl chlorides (121°-134°) with aloohoUo
KOH at 100° (Schorlemmer, Pr. 29, 365).
Formed also by treating (;S) -hexyl iodide with
alcoholic KOH at 100° (Erlenmeyer a. Wanklyn,
A. 135, 141 ; of. Heoht, B. 11, 1060), and, to-
gether with the preceding, from the ra-hexane of
petroleum by ohlorination, followed by treatment
with alcoholic KOH (Morgan, A. 177, 306 ; C. J.
28, 301). Also from (;8)-hexyl iodide and ZnMcj
at 125° (Purdie, O. J. 39, 465).
Reactions. — 1. Combines with cold fuming
HClAq ; the combination being complete in the
course of a few wseks, the product being
CH,.CH2.CH2.CHj.0Hqi.0Hj (125°) (Schorlem-
mer).—2. HI forms (/3)-hexyl iodide (168°).—
3. Chromic acid mixture oxidises it to ra-butyrio
and acetic acids. — 4. CIO2 gas (from KCIO,
(2 pts.), HjOjOj 2aq (1 pt.), HjSO, (1 pt.), and
HjO (2 pts.)) forms acetic and butyric acid, and
a body that can be reduced by nascent hydrogen
to secondary hexyl alcobAl (Domao, X 213, 124).
5. HOlO gives CsH,jCl(OH) (140°) (Domac, M.
2, 309).— 6. H2SO4 (3 pts.), diluted with water
(1 pt.), dissolves (j8)-hexylene, and on adding '
water (i8)-hexyl alcohol is ppd.
Hexylene CMe2:CMe2. Tetra-mAfhyl-ethylene.
(73°). S.G. 2 -712. Formed by the action of
alcoholic KOH on CMe^Prl (Jawein, A. 195, 253 ;
Pawloff, A. 196, 124 ; Eizza, J. R. 1882, 99 ;
C. J. 42, 491). Formed also, together with a
heptylene, by heating CMe^iCHMe with PbO
and Mel for eight hours at 225° (Eltekoff, J. R.
14, 380). Forms a dibromide CeHijJBrj [169°].
A 10 p.c. solution of CrO, completely oxidises
tetra-methyl-ethylene to acetone. Butlerow (/.
R. 11, 219) also obtained tri-methyl-acstio
acid by oxidation. H2SO4 (2 vols.), mixed with
water (1 vol.), polymerises it to C,jHj4 at 60°.
Hexylene CMca.CH-.CHj. (70°). From pina-
colin iodide by distiUatioU with water (Friedel
a. Silva, C. B. 76, 226). Forms a orystallino di-
bromide.
' Hexylene CHMe:CMeEt. (70°). S.G.
•712 ; i-» -698. O.E. -00116. From CMeEtjI and
alcoholic KOH (Tsohaikowsky, J. 1872, 360;
Jawein, A. 195, 255) It is also aproduct of the
action of zinc and glacial acetic acid on
CH3.CHj.CHMe.0HMeI (Wislioenus, A. 219,
696
HEXYLENE.
313). Combines with HI forming CMeEt,I.
Ohromio acid oxidises it with difiiioulty forming
aeetio acid and a small quantity of a ketone.
By agitating the hexylene (1 vol.) with (2 vols.
of) a mixture of HjSOj (2 pts.) and water (1 pt.)
at 0° until it is dissolved, and subsequently
exposing the solution to the air, there is formed
an oUy dodeoylene 0,jH„ ,(196°-199°) ; S.G. a
•809 ; *-» -798. O.E. -00080.
Hexylene OHBt:CMej. (66°). S.G. 2 -702 ;
J2 '687. O.E. •00117. From CMejPrI and al-
coholic KOH (Jawein, A. 195, 255). Chromic
acid oxidises it to acetic and propionic acids
and acetone. Polymerised in the same manner
as the preceding body, forming a dodecylene
CijHa (195°). S.G. 2 -795; i2 -786. C.B.
•00065.
Hexylene CsH.j. (60°-70°). Obtained by dis-
tilhng fusel oil with ZnOlj (Wurtz, A. 128, 228).
Forms a dibromide O^i^r^ (190°-200°).
Hexylene 0»H„. (65°). S.G. a •694. Ob-
tained by distilling the lime-soap obtained
from whale oil (Warren a. Storer, Z. 1868, 228).
Hexylene C,H,j. (67°-70°). In oil of resin
(Eenard, A. Ch. [6J 1, 227).
Hexylene OjH,j. (70°-80°). DipropyUne.
From propylene bromide, zinc, and HOAc (Pru-
nier, O. JR. 76, 98).
Beferences. — ^Bnoiio- and Di-ohlobo-hexyl-
ENE.
Di-hezylene v. Dodecylene.
HEXYLBNE ALCOHOL v. Di-oxy-hexanb.
H£XYLEI7E CHLOBHYDEIN v. GHiiOEO-
BEXYIi AIiCOHOL.
HEXYLENE GLYCOL u. Di-oxy-hexane and
PmACONE.
HEXYLENE IODIDE v. Di-iodo-hexanb.
HEXYLENE OXIDE CeH,„0 i.e.
°<CMe'>- (^^°)- Fortaed from CMe^iCMe,
by conversion into CMe2Cl.CMe20H [55°] and
treatment of this ohloro-hexyl alcohol with KOH
(Eltekofl, Bl. [2] 40, 23; J. B. 1882, 355).
Combines with watewvith .evolution of heat, the
product being pinacone.
Hexylene oxide CjH„0 i.e.
0<p™®>. (110°). S.G. m •8236. From
(i8)-hexylene Pr.CH:CHMe, by successive treat-
ment with ClOH and cone. KOHAq ^ (Blte-
koff, Bl. [2] 40, 23 ; Henry, A. Ch. [5] 29,
553), Liquid. Does not combine with cold
water, but at 100° it forms di-oxy-hexane
PrCH(OH).CH(OH)Me. A mixture of HjSOi
and HNO, forms the nitrate CsHij(N03)2.
Hexylene oxide CsH,„0 i.e.
0<cEl:>? (^'°>- S.as-837. S. 7
in the cold.
Formation.-yl. Together with hexenyl alco-
hol, by the action of AgjO on the di-iodo-hydride
of diallyl (di-iodo-hexane) (Wurtz, A. Ch. [4] 3,
175).— 2. By treating diallyl with H^SO, and
distilling with water (Jekyll, Z. 1871, 36).
Prcfperties. — Liquid, does not react with
NaHSOj, hydroxylamine, ammoniacal AgNO,,
cold HCLAq, or water at 170°. Does not ppt. a
solution of MgCl^. Sodium-amalgam does not
reduce it.
fleacfcjts. — l.HClAqat 150° forms a chloro-
hffliyl alcohol (170°-180°) (Bfihal, Bl. [2] 43, 43 ;
A. Ch. [6] 16, 200) and, finally, di-ohloro-hexane.
2. Fuming HIAq at 100° forms sec-hexyl iodide.
3. Chromic add mixture oxidises it to COj and
acetic acid. — 4. Excess of bromine forms di-
bromo-hexane and an aldehyde.
Hexylene-S-oxide 0<Qg^^Q&>CH,.
(104° at 720 mm.). S.G. a -8739. Very mobUe
colourless liquid of strong ethereal smell. V.
sol. alcohol and ether, si. sol. water. YolatUs
with steam. Prepared by heating the glycol with
3 pts. of HjSOi (65 P.O.) at 100°. It is not
affected by heating with water or with aqueous
or alcohohc NH, even at 200°. By boiling with
dUute HCl it is converted into the ohlorhydrin
(Lipp,B.18,3283).
Hexylene oxide 0<°]^(^5^> ? (115°).
Prom Pr.CH2.0H(0H).CH,(0H) by conversion
into the ohlorhydrin' (chloro-hexyl alcohol) and
treatment of the latter with KOH (Wurtz, A.Ch.
[4] 3, 184).
Hej^ylene oxide? CjH,„0. (185°). From
PrPr by conversion into C5H,2Br2 and treatment
of this di-bromo-hexane with AgOAc and KOH
successively (Silva, Bl. [2] 19, 147). .
HEXYLENIC ACID v. Hbxenoio Acn>.
HEXYL-GLYCEEIN v. Tei-oxy-hexane.
HEXYL-GLYCOL v. Di-oxy-hexanb.
HEXYL-GLYOXALINE C,H,eN,i.e.
C3H,(0gH,3)N2. Glyoxal-cena/nthyline. [84°]
(Badziszewski, B. 16, 748) ; [51°] (Karoz, M. 8,
218) . (295°) . Prepared by the action of glyoxal
on heptoic aldehyde-ammonia (osnauthol-ammo-
nia) in alcoholic solution (B.), or by passing NH,
into a mixture of glyoxal and heptoic aldehyde
(K.). Thin gUstening needles ; sol. alcohol, si.
sol. ether, insol. water. Karcz attributes the
difierenoe in the melting-point, as observed by
himself and by Badziszewski, to the existence of
two aUotropic forms of the hexyl-glyoxaline.
Mel gives C3HjMe(CeH,3)Nj (262°) ; EtI and PrI
act in hke manner. -
Salts. — B'HCl: colourless deliquescent
needles.— B'HBr.—B'jHjCjO,. [121°].
HEXYL HEPTADECYL KETONE CaH„0 i.a,
CyH,3.C0.0„H„. (248°) at 10 mm. Formed by
distUUng barium stearate with barium heptoate
(Krafft, B. 15, 1718).
HEXYL HYDBIDE v. Hexane.
ra-HEXYL IODIDE CsH.sI i.e.
Pr.CHj.OHj.CH2I. (177°) (Dobriner,^. 243, 27);
(179-5°) (Franchimont a. Zincke, A. 163, 196) ;
(182° cor.) (Liebena. Janecek,4.187,138). S.G.
§ 1-4661 (D.) ; iZ5 1^412 (F. a. Z.) ; 2 1^461 (L. a.
J.). C.B. (0°-10°) -00095 (D.). S.V. 173-8. Pre
pared from n-hexyl alcohol and HI.
Hexyl iodide O^^J.. (172°-175°). S.G. is
1-43. Obtained from petroleum hexane oi(i hexyl
alcohol (Pelouze a. Gahours, 0. B. 54, 1241).
Sec-hexyl iodide CaH„I i.e. Pr.CHj.CHI.CH,.
{pyhexyUodMe. (168° i.V.). S.G. 2 1-45 ; U
1^4269 ; 1 1^4163 (Perkin, 0. J. 45, 463). C.E.
(0°-50°) ^00092. M.M. 14-229 at 23-9°.
Formation. — 1. By boiling mannite or dul-
cite with a great excess of cone. HIAq (Wanklyn
a. Brlenmeyer, Z. 1861, 606 ; 1862, 641).--2. By
the action of HI on (i3)-hezylene obtained by
treating the di hydro-di-iodide of diallyl with
HEXYL TinO-UEiEA.
997
sodium (Wurtz, A. 132, 306).— 3. Prom hexylene
oxide (93°) and HI (Jekyll, G. N. 22, 221).
Pr&pa/ration.—l. Mannite (24 g.) iB distilled
with aqueous HI (300 o.o. boiling at 126°) ahd
clear phosphorus in a current of COj. The yield
is nearly the theoretical (E. a. W.). — 2. Iodine
(75 g.) and water (130 g.) are treated, in an at-
mosphere of COj, with clear phosphorus until
colourless ; mannite (25 g.) is then added, and
the mixture distilled in a current of CO^ (Domac,
M. 2, 310 ; cf. Hecht, A. 165, 148).— 3. A mix-
ture of mannite (200 g.) ahd red phosphorus
(lOOg.) is added slowly to HIAq (500 g. of 57
p.c), and the mixture distilled in a current of
CO2 (Hecht, A. 209^ 311).— 4. A good yield is
obtained by distilling mannite with fuming
HIAqand a little amorphous phosphorus (Sohor-
lemmer, T. 171, 453).
PropBrt4^s. — Liquid, smells like isoamyl
. iodide.
ReaeUons. — 1. Akoholio potash gives {$)-
hexylene.— 2. By heating with water at 190° it
gives hexylene. By boiling for a long time with
a large excess of water (45pt3.) sec-hexyl alco-
hol is the chief product, hexylene being also
formed (Niederist, A. 196, 351).— 3. With moist
AggO, with zina and water, with zinc and alco-
hol, with silver oxalate, with sodium, with mer-
cury, and with ZnMe^, it yields hexylene. — 4.
When (;8)-hexyl iodide (100 g.) is heated with
iodine (25 g.)for 5 hours to 256° it yields hexane,
HI, a little Mel, and a combustible gas (Eayman
a. Preis, A. 223, 322). — 5. Chloride of iodine at
240° gives hexa-chloro-benzene, COl,, CjClj, and
C^Cl, (KrafEt, B. 9, 1085).— 6. Chromic acid
mixture oxidises it to acetic and butyric acids
(Hecht, B. 11, 1421).
Sec-hexyl iodide CjH.sI i.e. Pr.CHEtl (?)
Di-ethylated ethyl iodide. , (100°) at 70 mm.
From di-ohloro-di-ethyl oxide' OS2Ol.OHCl.OEt
viA OH2Et.CHEt.OEt (Lieben, A. 178, 18). Pro-
bably identical with the following.
Sec-hexyl iodide Pr.CHEtl. (165°). From
the alcohol and HI (Oeohsner de Coninok, Bl.
[2] 25, 9).
Seo-hexyl iodide CHMeEtOHMel. From
the corresponding hexyl alcohol and HI (Wisli-
eenns, A. 219, 310). Liquid; decomposed on
distillation. Zinc and acetic acid reduce it to
OHMeEt.CHjiMe, a hexylene, and a dodeoylene,
some methyl-di-ethyl-carbinol being also formed.
Sec-hexyl iodide (CH3)3C.CHMeI. (142°).
S G 2 1'474 ; 2S 1-442. From the corresponding
aicohol and PI2 (Friedel a. Silva, G. B. 76, 226).
Partially split up on distillation with water into
HI and a hgxylene (70°).
Hexyl iodide OeH,sL (c. 150°). Formed by
eombination of HI with the hexylene derived
from fusel oil (Wurtz, 4. P8, 228).
Teri-hexyl iodide 0MeEt2L (142°). Formed
by leaving equal volumes of methyl-di-ethyl-
carbinol and fuming HIAq to stand in the cold.
Formed also from CH3.CH:0MeBt and HI (Wis-
licenus, A. 219, 318; Tschaikowsky, J. 1872,
350; Eeformatsky.J.pr. [2] 36,340). Liquid;
martially decomposed on distillation.
2Vi-hexyl iodide CMojPrl. (142°). Formed
by the action of HI on di-methyl-propyl-carbmol
or on CMe»:CHBt (Jawein, A. 195, 254). ,
reri-hexyl iodide CMe^Prl. (142°). S.G.
8 1-394 • is 1 ■373. From CMejiCMej and HI
(J^awloff, A. 196, 125). Solidifies at 0° (Ka-
schirski, O. 0. 1881, ^78). Slightly decomposed
by distillation.
DI-HEXYL KETONE 0,sH2.0 i.«. (0TB.,^)j:iO.
[30°]. (264° cor.). S.G. 5a -825. Formed by
the dry distillation of calcium heptoate (oeuah-
thoate) (Uslar a, Seek^mp, A. 108, 179). Large
colourless laminee (from alcohol).
Sac-HEXYL-MAIONIC ACID
C„H,s.CH(002H)2. \o. 86°]. From the ether by
saponification. Nodules, v. sol. water, alcohol,
and ether.
I Ethyl ether M^^k". (251°). From sodium
malpnic ether and (i3)-hexyl iodide (Lundahl, B.
16, 789).
w-(?)-HEXYI. MESCAPTAN C,H,sSH. (145°-
148°). From petroleum hexane by conversion
into hexyl chloride followed by treatment with
KSH (Pelouze a. Oahours, A. 124, 291).
Sec-hexyl mercaptan Pr.CH^.CHMe.SH.
(142°). S.G. 2 -886. From/(;3)-hexyl iodide and
cone, alcoholic KSH (Wanklyn a. Brlenmeyer,
A. 135, 150). Colourless oil, with unpleasant
smell.— Hg(SCsH,3)2. Liquid. S.G. 2 1-650.
HEXYL-NITBOUS ACID so-called.
OeHijNjO^. (212°). S.G. a 1-1381. Formed by
the action of HNOj on methyl-hexyl ketone
(Chancel, G. B, 94, 399 ; 100, 601). OU, sUghtly
decomposed by distillation. May be reduced to
ji-hexoic acid. — CeHuKN^O, : slender yellow
plates (from water) ; si. sol. water. Decomposes
without detonation when heated. The silver
salt is a similar body.
DI-sec-HEXYL OXIDE (C,H„)20. (204°-
209''). Formed, together with a hexylene and
hexyl alcohol, by the action of moist Agfi on
()3)-hexyl iodide (Erlenmeyer a. Wanklyn, Z. 1863,
274). Thick' yellowish oU.
HEXYL-PAEACONIC ACID v. DxY-HEPira-
SUOOIMIO ACID.
HEXYI PEHTADECYL KETONE CjaH^O i.e.
ObH,3.00.0i5H3;. (281°) at 10 mnl. Formed by
distilling a mixture of barium palmitate and
barium heptoate (Krafft, B. 15, 1718).
HEXYL SULPHIDE (C,H,j)2S. (230°).
From petroleum hexane vid hexyl chloride
(Pelouze a. Oahours, A. 124, 291). Oil.
HEXYL SULPHOCYANIDE CaH„SCy.
(215°-220°). S.G. 12 -922. Formed by heating
potassium sulphocyanide at 100° with an alco-
holic solution of hexyl chloride derived from pe-
troleum (Pelouze a. Oahours, A. Gh. [4] 1, 5).
Fetid Kquid.
Sec-hexyl sulphocyanide Pr.OH2.CHMe.SOy.
(207°). Prepared by boiling equal parts of (/3)-
hexyl iodide with potassium sulphocyanide dis-
solved in alcohol (XJppenkamp, B. 8, 55). Oil,
with alliaceous odour.
TO-HEXYL THIOCARBIMIDE OaH,sNOS.
(212°).. Formed by distilling cuprio w-hexyl-di-
thio-oarbamate with steam (Frentzel, B. 16,
746). Pungent oil.
Sac-hexyl thiocarbimide Pr.CH2.CHMeNCS.
(198°). S.G. -92. From (0)-hexylamine by boil-
ing with OS2 and alcohol, evaporating, and heat-
ing the residue with a solution of mercuric,
chloride (Uppenkamp. B. 8, 56). Oil. Converted
by hot cone. HjSO^ into (3)-hexylamine.
w-HEXYL THIO-TJEEA 0,H,„N2S i.e.
CS(NH2)(NH.0„H„), [83°]. From ;»i-heiyl
HEXYL THIO-UREA.
thiocarbimide and alcoholic NHj (Frentzel, B.
16, 746). White plates (from alcohol).
Di-n-hexyl thio-urea CS(NH0sH,3)2. [40°].
Obtained by heating M-hexylammonium n-hexyl-
di-thio-carbamato (F.). White plates (from
alcohol).
KEXYI-TRIDECYL-KETONE Oj,H„0 i.e.
C,H„.CO.C,jHj,. (210° at 11 mm.). Formed by
distiUing a mixture of barium heptoate and
barium myristate (Krafft, B. 15, 1717).
HEXYL-1TBEA. Eeptoyl derivative
C^„NH.CO.NH.CO.C„H„. [97°]. Formed by
the action of EOH on a mixture of the amide of
heptoic (oenanthoic) acid and bromine (Hofmanu,
B. 15, 759). Pearly plates ; insol. water.
Sec-hexyl-urea NH2.C0.NH.CHMe.CHjPr.
[127°]. (o. 220°). From (;8)-hexyl iodide and
silver cyanate, the resulting thiocarbimid,e being
decomposed by shaking with aqueous ammonia
(Chydenins, Bl. [2] 7, 481). Slender needles
(from water) ; v. sol. water, alcohol, and ether.
Not decomposed by cone. KOHAq below 200°.
HIPPAEAFriN V. Dibmzoyl derwaiwe of
Mbihxlbiie-siamine.
HIPPTTEIC ACID OjHjNOa i.e.
NHBz.CH2.CO2H. Benzoyl-glycodoU. Beneoyl-
amido-acetic acid. Benzamido-acetic acid. Mol.'
w. 179. [187°]. S.a 1-308 (Sohabus, Sitz. W.
1850,211). S. ■17at0°. ,S.(isoamylalaohol)2at
9° ; 33 on boiling (Campani, S. 11, 1247).
Occmrence. — 1. In the urine of lierbivorous
animals and in small quantity (c. 1 g. daily) in
that ot man (Liebig, A. 12, 20; Henneberg,
Stohmann a. BaUtenberg, A. 124, 181; Bence
Jones, C. J. 15, 81 ; Thudichum, O. J. 17, 55 ;
Weismann, J. pr. 74, 106 ; Wreden, J. pr. 77,
446; Hofmeister, L. V. 14, 458; Wildt, B. 6,
1410 ; Kraut, C. 0. 1858, 881; Loew, J.pr. [2] 19,
809 ; Stadehnann, J. 1879, 982 ; Schwarz, A.
54,82; Weiske, Wildt a. PfeifEer, B. 6, 1410;
Hallwaohs,4. 106, 164; E. Salkowski,B.ll,500;
Weyl a. Aurep, B. 13, 1092 ; Garrod, Pr. 35, 63 ;
37, 148 ; Minkowski, J. 1883, 1440).— 2. In the
blood of oxen (Verdeil a. DoUfus, A. 74, 214).—
3. In the human epidermis in ichthyosis
(Schlossberger, A. 93, 347).
Formation. — 1. Excreted by th? animal or-
ganism after introduction of benzoic acid (Bouis
a. Ure, B. J. 22, 567; Ure, J. Ph. 27, 646;
Keller, A. 43, 108; Garrod, P. M. [3] 20, 501).
Quinic acid (Lautemann, A. 125, 9), ciunamic
acid (Erdmann a. Marchand, B. J. 23, 646)
toluene (Naunyn a. Sohultzen, Z. 1868, 29),
and phenyl-propionic acid also yield hippurio
acid when passed through. the animal organism.
Since phenyl-propionic acid is produced by the
pancreatic fermentation of proteids, hippurio
acid is, at any rate in part, due to the decom-
position of proteids (E. a. H. Salkowski, B. 12,
654 ; Baumaim, H. 10, 131). — 2. From benzoyl
chloride and zinc glyooooll or from glyoocoU
and benzoic acid at 100° (Dessaignes, C. B. 37,
251). The yield is very bad.— 3. From ohloro-
acetic acid and benzamide (Jazukowitch, Bl.
[2] 8, 361). The yield is bad.— 4. By heating
glycoooll with benzoic anhydride (Curtius, B.
17, 1662).— 4. From sUver glyooeoU and BzOl
(Curtius, J. pr. [2] 26, 170).- 5. By adding
benzoyl chloride to an aqueous solution of gly-
cocoU and making alkaline with NaOH (Baum,
B. 19, 602).
Pr^aration. — 1. The urine of horses or oows
is boiled with addition of some milk of lime,
filtered, neutralised by HCl, evaporated, acidi-
fied by HCl and allowed to stand. Hippurio
acid is then deposited as a yellowish-brown pp.
(Gregory, A. 63, 125 ; cf. Riley, Q. J. 5, 97).
When horses' urine is quickly evaporated the
hippurio acid is partly converted into benzoic
acid. Crude hippurio acid, obtained as above,
is then mixed with rather less water than will
dissolve it at 100°. The liquid is then heated
to 100° and chlorine passed in until the nn-
pleasant odour of the crude product has dis-
appeared. The liquid is filtered hot, and the
acid that separates on cooling is subjected a
second tinle to the same treatment,' chlorine
being passed in this time until the liquid is ,
bright yellow. The yield is 65 p.o. of the crude
acid (T. Curtius, J.pr. [2] 26, 149 ; cf. Dauber,
A. 74, 202 ; Conrad, /. pr. [2] 15, 242 ; Gossmann,
A. 99, 374 ; Sohwarz, A. 54, 29 ; Hansen, J. Th.
1881, 117). — 2. Silver glycocoU is suspended in
a mixture of benzene (1 vol.) and ether (2 vols.)
and benzoyl chloride is added. On wanning
AgCl is formed together with several acids. The
liquid is evaporated and benzoic acid removed
by solution in ether. Three nitrogenous aoida
remain. They are dissolved in NaOH; reppd.
by HCl, dried and extracted thoroughly with
chloroform. This dissolves the hippuric acid,
which is present in greatest quantity. One of
the remaining acids is hippuryl-glycocoll (g. v.)
(Curtius, J. pr. [2] 26, 168). The other has the
formula G^a'B.^JS^Oi. Both these acids split up
with formation of hippurio acid when they are
heated with dilute HCl.
Properties. — Crystallises from water in very
large trimetric prisms ; a:6:c="974:l-161:l.
Has a slightly bitter taste, and strongly reddens
litmus. SI. sol. cold, v. sol. boiling, water. V.
sol. hot alcohol, v. si. sol. ether. Less soluble
in water containing HCl, and hence is ppd. on
adding a considerable excess of HCl to cow's
urine. Dissolves readily in water containing
sodium phosphate, the solution becoming acid ;
in this respect it resembles uric acid. Insol.
benzene, CSj, and cold chloroform. Sol. EtOAc.
FeClg forms, in a dilute solution of an alkaline
hippurate, a cream-coloured pp. of basic ferric
hippurate FeA'sFe^Oj l^^aq, which is moderately
soluble in excess of feme chloride (E. Salkowski,
Z. [2] 4, 313).
Estimation in wine. — 1. Eecently calcined'
MgO is added to 1 litre of urine, the liquid ia
concentrated, acidified with HCl and extracted
with ether (A. W. Blyth, Pr. 37, 50).— 2. 250
c.c. of urine are evaporated to 80 c.c, 4 g. of
sodium phosphate are added, and the evapora-
tion continued to syrupy consistence. Plaster
of Paris is then added till the mass can be
powdered, after which it is extracted first with
light petroleum and then with ether. The
ethereal extract is evaporated, and the hippurio
acid decolourised with oharooal, crystallised from
water, and weighed (Voelker, Fr. 26, 402).
Beactions. — 1. On heating to 240° hippuric
acid begins to boil, giving off benzoic acid and
benzonitrUe (Gossmann, A. 100, 69 ; Limpricht a.
von Uslar, A. 88, 133). — 2. Boiling aqueous hy-
drochloric acid splits it up into benzoic acid aad
glycocoU. Dilute HjSOt, HNO„ and oxalic acid
HIPPUKIO ACID.
behave in like manner. — 3. By boiling for half
an hour -with aqueous catistic potash it is re-
solved into glyooooU and potassium benzoate.
Boiling mUk of lime does not effect its hydro-
lysis.— 4. Some ferments hydrolyse hippurio
acid (Buohner, A. 78, 203). — 5. Nitrous acid
converts it into the benzoyl derivative of glycoUio
aoid, with evolution of nitrogen. — 6. When
boiled with NaOBr and an excess of alkali for a
long time, a bright-red powder is deposited on
cooling (Denigfis, C. B. 107, 662).— 7. HCl and
KCIO3 form ohloro- and di-chloro-hippurio acids
(Otto, A. 122, 129).— 8. A cold mixture of H^SO,
and HNO3 forms nitro-hippuric acid. — 9. SO3
gives sulpho-hippuric acid. — 10. Chlorine passed
into a solution of hippurio acid in dilute KOH
forms benzoyl-glycoliio aoid, nitrogen being
evolved (Gossmann). — 11. The prolonged action
of PCI5 forms ObHjNOI, probably hexa-chloro-
GC\ CHGl
isoquinoline tetrahydride OjH4<^„„j'''j,„, ^
[134°] (Biigheimer, B. 19, 1169). This body
crystallises in plates. By distilling hippurio
acid (1 mol.) with PClj (2 mols.) Schwanert (A.
112, 69) obtained CsH„ClNO [50°] (220°) and
(XHsCIjNO.— 12. Boiling with MnO^ and very
dilute HjSOj forms benzoic acid, NH3, and C0.„
13. When heated with PbO^ and excess of HNO3
or H2SO4 the product is the di-benzoyl derivative
of methylene-diamine (hipparaifin). — 14. Boil-
ing with water and PbOj, vrith addition of only
enough H^SO, to combine with the lead, pro-
duces benzamide (Fehling, A. 28, 48 ; Schwarz,
A. 75, 190). — 15. Ozone oxidises it to benzoic
and acetic acids (Gorup-Besanez, A. 125, 217). —
16. By boiling with KMnO, and KOH all the
nitrogen is expelled as NHj (Wanklyn a. Chap-
man, C. J. 21, 161). — 17. A coacentrated aqueous
solution of ZnCl^ at 120° forms benzoic acid and
glyeocoU. DistUlation with dry ZnClj gives
benzonitrile (Gossmann, A. 100, 69). — 18.
•SodAv/m amalgam added to an alkaline solution
of hippurio acid forms 'hydrobenzurio acid'
CisHjjNjO, and 'hydrobenzylurio acid'
CjjHjiNO,; the latter dissolves in ether, the
former does not (Otto, A. 134, 803). Both acids
give glycocollwhen boiled with alkalis; the latter
forms also benzyl alcohol and hydrobenzoio acid.
When hydrobenzylurio acid is heated witn
alkaUs and at the same time exposed to the air,
there is formed 'hydroxybenzyluric acid '
C.sHaNOs [60°-70^, which when left in a desic-
cator over HjSOi changes to an acid 0,sH„NO,.
19. Pyrvmic add (6 g.) digested with sodium
hippurate (11 g.) and ACjO (25 g.) at 100° forms
a compound CjjHjNO, which crystallises from
petroleum in flat needles [157°], v. sol. alcohol,
ether, and HOAe, insol. water. It seems to be
an anhydride, for baryta forms the salt
Ci^H^BaNOs 2aq (A. Hoffmann, B. 19, 2554).—
20. By mixing hippurio acid with salicylic
aldehyde and excess of Ao^O and allowing the
mixture to stand for some weeks there is formed
a compound Cj^H^NjO, [160°] (Ploohl a. Wolf-
ram, B. 18, 1184). Eebuffat (G. IS, 527) by
boiling sodium hippurate (62 g.) with salioylio
aldehyde (40 g.) and AOjO (120 g.) obtained a
compound C,jH,3N0, which erystallised from
alcohol in canary-yellow prisms [136°], and is
converted by hot aqueous (10 p.o.) EOH into
benzoyl-imido-coumarinC,aH„NO,[171°] and an
acid C„H,3N04 [185°].— 21. Phthalic anhyckida
yields a compound 0^^^j^g (E. Krlenmeyer,
jnn., B. 22, 792).
Salts.— NHjA'HA'aq: formed even in pre-
scAce of excess of KHj. Square-based prisms
with four-sided summits, v. sol. water and
alcohol, b1. sol. ether. Gyrates when throvm on
the surface of water.— KA' aq : prisms, sol. water
and alcohol.— KA'HA' aq.— NaA'^aq : v. sol. hot
water and alcohol, si. sol. ether. — ^BaA'^aq:
prisms, sol. water; forms with barium benzoate -
the double salt BaA'2Ba(OBz)2 5aq. — GaA', 3aq :
trimetrio prisms. S. 5-6 in the cold ; 17 at 100°.
S.G. 1-32. — SrA'jSaq: si. sol. cold water and
alcohol. — MgA'Saq: white nodules, sol. water. —
ZnA'jSaq : laminss. S. (of ZnA'J 1-8 at 17-5° ;
25 at 100°.— CuA'gSaq: azure prisms, si. sol.
cold water. — PbA'j 2aq : silky needles, deposited
on diluting a boiling solution. — PbA'jSaq : broad
laminsB. — CoA'j 5aq : rose-coloured needles. —
NiA'jSaq : si. 'sol. cold, m. sol. boiUng water and
boiling alcohol, insol. ether. — CeA', 4|aq (Gzud-
novitch, J.pr. 82, 277).— LaA',4 Jaq (Czudnovitch,
J.pr. 80, 31).— FeA'3 (Wreden, C. C. 1859, 552).—
Fe(OH)A'j (Salkowski, J.pr. 102, 327 ; cf. Putz,
J. 1877, 795).— AgA'^aq: may be crystallised
from water.
Methyl ether MeA'. [80-5°]. S. -85 in the
cold ; 1-3 at 30°. Formed by passing HOI into
a solution of hippurio acid in methyl alcohol at
60° (Jacquemin a. SchlagdenhauSen, C. B. 45,
1011 ; Conrad, /. pr. [2] 15, 247 ; Campani a.
Bizzari, G. 10, 260). White needles. Decom-
posed at 250°, giving off NH3 and benzonitrile.
Ethyl ether EtA'. [60°]. S.G. ^ 1-043.
Formed by passing HCl into a boiling alcoholic
solution of hippurio acid (Stenhouse,2.31,148),
or by heating amido-acetio ether with benzoic
anhydride (Curtius, B. 17, 1662). White needles,
si. sol. hot water, v. sol. ether. When hippurio
ether (5pts.) is heated with dry NaOEt (Ipt.) to
160°, alcohol distils over, and there is left a
mixture of two sodium salts, which may be
separated by water. The less soluble salt, when
decomposed by HCl, yields the di-benzoyl-dei
rivative of di - oxy - di - amido - tetramethylene :
NHBz.C^^IqS^CNHBz [138°]; the more
soluble salt yields the tri-benzoyl derivative of tri-
NHBz.C:0(OH) — C.NHBz
amido-phloroglucin | |
HO.C:C(NHBz).0.OH
[153-5°-158-5°] (Eiigheimer, B. 21, 3325). When
hippurio ether is heated with PCI5 for eight
hours ai 160°, and the product poured into
alcohol, ' hippuroflavin ' separates. It crystal-
lises from hot HOAc in small yellow crystals,
and partially decomposes, without melting, at
300°. Hippuroflavin is v. si. sol. glacial HOAc,
and almost insol. water, alcohol, and ether. It
. /NBz.C.CO ^
has perhaps the cdnstitution ^ {| )
\C0 . CNBz/
(Eiigheimer, B. 21, 3321).
n-Butyl ether PrCHj-A'. [41°]. From
silver hippurate and w-butyl iodide (0. a. B.).
Iridescent prisms, insol. water, sol. alcohol, ether,
and chloroform.
Isobuty.l ether PrOH^A'. [46°]. From
AgA' and isobutyl iodide in presence of isobutyl
700
HIPPURIC ACID.
alcohol (C. a. B.). Iridescent pj-isms. Decom-
posed by damp air.
Jsoamyl ether C;^„k'. [28°].
Benzyl ether PhCHjA'. [86°], From
AgA' and benzyl bromide (Del Zanna a. Guares-
chi, Atti Real. IsUt. Veneto [5] 6). Silky ^
needles. Converted by HNO3 into benzoic alde-
hyde.
Amide CsHjNOjNHj. [183°]. S. 1 in the
cold. Formed by the prolonged action of aqueous
ammonia on methyl hippurate (Jacquemin a.
Schlagdenhaufien, C. B. 45, 1011). Formed also
by heating hippuric acid in a current of NH, at
160° (Conrad, J, pr. [2] 15, 248). Small thick
crystals, v. si. sol. cold water, alcohol, and ether.
Forms an unstable compound with ECl.
Vreide NHBz.CHj.CO.NH.OO.NH2. [216°].
Formed, together with another compound [189°],
by heating ethyl hippurate with urea at 160°
(Curtius, B. 16, 757) ; and by heating hippuric
acid with alcoholic NH, at 220° (Pelllzzari,
C. G. 1888, 1350). Silvery plates; decomposed
by boiling dilute acids into hippuric acid and
urea. Split up by alcoholic NH, at 260°, giving
benzamide and EtOBz.
Beferences. — Amido-, Bbomo-, CbiiObo-, Iodo-,
N11E0-, OxT-, ^nd SuLPHo-HippnRic acid.
HIPPUETI-GIYCOCOLL Ci.HuNA i.e.
Bz.NH.CH,.C0.NH.CHj.C02H. [207°].
Preparation. — Silver glycocoll (40 g.), benzoyl
chloride (15-5 g.), and benzene (200 e.c.) are
heated together until HCl begins, to come off.
The product is evaporated, extracted with ether,
then with NaOH. The mixed aCids are ppd. by
HCl, dried and exhausted with alcohol. The
alcoholic extract leaves on evaporation a mixture
of hippuric acid and hippuryl, glycocoll. The
greater part of the former may be removed by
chloroform, and the hippuryl glycocoU is then
purified by recrystaUising 20 or 30 times from
30 p.c. alcohol (Curtius, /. pr. [2] 26, 170). In
this reaction benzoyl chloride acting on silver
glycocoU forms silver chloride and hippuric acid.
This hippuric acid acts upon benzoyl chloride
. forming benzoic acid and hippuryl chloride, which
then attacks silver glycocoU, forming silver chlor-
ide and hippuryl-glyoocoU.
Properties. — Satiny trimetric plates (from
water). The crystals are small, and feel fatty.
Insol. ether, CHCl,, benzene, and CS^ in the cold,
but si. sol. these solvents when boiUng. Readily
80I. boiling dilute (30 p.c.) alcohol.
Beactions. — 1. Boiled with HCl or KOH it
gives glycocoU (2 equivalents) and benzoic acid (1
equivalent). — 2. At 150° in a sealed tube with an
aqueous solution containing the calculated quan-
tity of HCl it splits up into glycocoU and hip-
puric acid.
Salts. — AgA': white crystalline pp., sol. hot
waterwithout reduction. — TIA': six-sided tablets.
— BaA'2 5aq(?). Little plates. — CuAj'S^aq: tri-
metric prisms. — ZnA'j Ifaq.
Ethyl ether MA'. [117°]1 Large needles
(from water).
Amide BzNH.CHjCO.NH.CH,CO.NHj.
[202^. Forms an unstable compound vrith HCl,
which is at once resolved by water into its con-
stituents.
HISTb-H^MATINS v. MusonE.
HOFMANN'S VIOIET v. Pehtjl-meihiii-iri-
IMICO-CI-fHENYIi-IOLyii-CAIlBINOJa
HOMO-ANISIC ACID v. Methyl derivative of
OXYTOJ.niO ACIJ).
HOMO-BENZ-AMIDOXIM v. ToiiU-AMinoxiM.
HOMO-CINCHONIDINE v. Cinchona bases.
HOMO-FEBTILIC ACID v. m-Methyl deriva-
tive of (4:3:l)-Di-oxY-PHENHi-CBOTONio Aom.
HOUOIOGOTJS SEBIES. A series of closely
related compounds of which the molecules differ
from one another by CH^ or a multiple thereof.
Homology is usually the result either (a) of the
introduction of one or more methyl radicles in
place of the equivalent quantity of hydrogen,
or (6) of the insertion of a methylene group
between two contiguous carbon atoms ; thus
benzoic acid C^HsCOaH is homologous with
toluic acid CbH4(CH3).C02H in the first way,
and with phenyl-acetio acid CjHs.CH^.COjH in
the second way. In each homologous series
there is a nearly constant difference in the
properties of any two successive members of the
series ; this rule, however, does not apply to the
difference between the first and second members,
particularly where the first member does not
contain CH^. Although the alkyl derivatives of
hydroxylic compounds differ from these com-
pounds by a multiple of CH,, and might there-
fore be considered homologbus with the parent
substance, yet as they belong to the group of
ethers while their parents are acids or alcohols,
this cannot be considered a case of true
homology.
HOMO-NICOTINIC ACID v. Methyl-
FYBinlUE CABBOXYLIC AOID.
HOMO-OXY-BENZOIC ACID v. Oxt-toldio
ACID.
HOMO-PHENACYL-ANILIDE v. oj-Phenyl
AMIDO-PHENYL-ETHYL KETONE.
HOMO-PHTHAIIC ACID v. Cakboxy-phenyl
ACETIC AOm.
HOMO-FBOTOCATECHiriG ACID v. Di-oxY-
PHENYL-ACETIO ACID.
HOMOFYBOCATECHIX, Methyl ether of, v.
Cbeosol.
HOUO-PYBBOLE v. Methyi,-pybbole.
HOMOQUININE V. Cinchona bases.
HOMOSAIICYLIC ACID v. Oxy-toluio Aom.
, HOMO-VEEATEIC ACID v. -Di-methyl de-
ri/oatvoe of Di-oxy-phenyl-acetio acid.
HOPEiNEOisHjoNO^aq. S. -125 at 15°, An
alkaloid said to occur to the extent of '15 p.c. in
American wUd hops, and of -05 p.c. in English
hops (WiUiamson, J. Ph. [6] 12, 460; Ghem.
Zeit. 10, 491). BriUiant white needles (from dilute
alcohol). Narcotic. SubUmes partiaUy below
160°. Slightly IsBvorotatory. Its dilute solu-
tions are ppd. by alkaUs, FtCl.,, AuCl,, HgClj,
picric acid, and tannin. According to Laden-
burg {B. 19, 783), hopeine is identical with
morphine, or is a mixture of morphine with an^
alkaloid that gives no colour with FeClj or with
HjSOj and molybdio acid, and is insol. NaOHAq,
v. sol. wet ether.
Lupnline. According to Griessmayer (D.P.J.
212, 67), when the aqueous extract of hops is
distilled with lime or magnesia the distillate
contains NHj, trimethylamine, and an alkaloid
Inpuline. If the bases be converted into
hydrochlorides, and these be treated with alco-
hol, NH,C1 is left undissolved, whUe NMesHCl
crystallises from the evaporated alcoholic solu-
tion, and the mother liquor contains lupnUne
HYDRAOIDS.
701
hydrochloride. The base may be obtained by
decomposing its hydrochloride with KOH and
shaking with ether. It smells like coniine, has
a cooling, but not bitter, taste, and gives the
usual reactions of alkaloids. Cone. HjSO, and
potassium chromate give a violet colour. HNO3
gives a yellow solution, becoming green or blue
at its edges, and afterwards colourless.
HOP OIL. At the base of the membranous
cones of the hop there is a bitter yellow
powder called lupulin. This powder contains
resin, wax, a tannin, and a bitter principle also
called Lupulin (q.v.). When distilled with steam
it yields hop oil, which consists of a terperie
C,„H,j (175°), and various compounds containing
oxygen (Wagner, D, P. J. 128, 217 ; Personne,
/. Fh. [3] 26, 241, 329 ; 27, 22 ; Kuhnemann, C. C.
1875, 573). One of the oxygenated constituents
of oil of hops is converted into valeric acid by
oxidation.
HUMIC ACID. The brown or black sub-
stance, or mixture of substances, produced by
the decay of vegetable matter. The decomposi-
tion is promoted by heat, air, moisture, and by
the presence of putrefying nitrogenous matter.
Humic acid may be extracted from peaty soil
by aqueous NajCOg and ppd. by HCl (Mulder,
A. 36, 243 ; Detmer, L. V. 14, 248). Detmer
assigned the formula GegHjtOj, to humic acid,
and described it as amorphous, beginning to de-
compose at 145°, and requiring 8,333 parts of
water at 6°, or 625 at 100", to dissolve it. After
drying it required 18,784 parts of boiling water
for solution. It reddened litmus, expelled 00,
from its salts, and formed the following amor-
phons salts. — (NHJaCeoH^sOj,. S. 45. —
Ca3(NH,)A.H4eO„. - Fe,(NH,)AoH„0„. —
Ag,Ce„H„0„. P. Thenard (C. B. 83, 375) de-
scribed humic acid as CjiHuO,,,. ' Ulmic ' acid
prepared from brown peat is identical with
humic acid. Crenic and apocrenic acids (g. v.)
are, perhaps,products of oxidation of humic acid.
Thenard obtained it by dissolving crude humic
acid in potash, ppg. with a slight excess of HCl,
washing the pp. well, and keeping the spongy
mass at — 14° for 24 hours. As the mass thaws
the humic acid separates as a dense pp. Humic
acid is not capable of converting atmospheric
nitrogen into NH, (Prevost, G. J. 39, 370 ; cf.
Simon, Instit. 1875, 133 ; D6h6rain, C. B. 73,
1352). Lettenmayer (B. 7, 408) observed that a
piece of rotten beech-wood which had fallen into
a cleft of the tree protected from the rain, was
covered with a brittle black layer readily soluble
in cold water, and was composed of the K, Na,
and NH, salts of an acid (? humic) containing
53-6 p.c. C and 4-9 p.c. H. When cane sugar is
boiled for a long time with dilute HCl, HNO3,
or H2SO4, there is produced a substance greatly
resembling humic acid, called Saooulmio acid
{q.v.). A brown substance is formed by heating
cellulose with water in a platinum tube at 200° ;
and brown substances are formed by the action
of alkalis on glucose, cane-sugar, and many
other substances. If all these brown bodies are
included in the term humous substances, they
may be subdivided into three groups : (a) those
insol. alcohol and alkalis ; (6) those insol. alcohol
but sol. alkalis ; (c) those soluble both in alcohol
«!id svlkalis (Hoppe-Seyler, H. 18, 66).
HYJENIC ACID OaH„Oj- MolT w. 382.
[78°]. The glyoeride of this acid is said to occur
together with palmitin and oleiin in the anal
glandular pouches of the striped hysena (Carius,
A. 129, 168). According to Sohulze a. Ulrioh
{B. 7, 670), it also occurs in the product of the
saponification of the grease of sheep's wool.
Granules composed of minute curved needles
(from alcohol) ; resembles cerotic acid ; si. sol. cold
alcohol, V. si. sol. ether. Ppd. by alcoholic lead
acetate sooner than palmitic acid. — CaA', : [90°];
white crystalline powder. — PbA'j : white pp.
HTAIiINS V. Peoteids, Agpendix G.
HTALOCrENS v. Pkoteids, Appendix C,
HYDAHTOIH 0,H,N,0, i.e.
CO<j
;nH.CO^>- <''2'«°^'
■urea. Di-oxy-meta-
Mol. w. 100. [215°].
Formation. — 1. Together with urea, by the ac-
tion of cone. HIAq at 100° on allantoin (Baeycr,
^..117, 179; 130, 158).— 2. Together with a
small quantity of allanturic acid, by the action
of HI on alloxanic acid (B.). —3. By the action
of an excess of alcoholic NH, on bromo-acetyl
bromide (Baeyer, B. 8, 612).
Properties. — Colourless needles, m. sol. cold,
V. sol. hot, water. Neutral to litmus. Has a
somewhat sweet taste. Not attacked by boiUng
dilute acids, but converted by boiling baryta-'
water into hydantoic acid. May be oxidised to
aUanturic acid. Ammoniacal AgNQ, gives a
pp. of AgCjHjNjOj aq.
Hydantoic acid CsHgNjO, i.e.
NHj.CO.NH.CH2.CO2H. Uramido-aceHc acid.
Olycollv/ric acid.
Formation. — 1. By boiling hydantoin with
baryta-water or potash (Baeyer, A. 130, 160). —
2. Together with urea, by boiling glycoluril
C4HJN4O2 with baryta-water (Bheineck, A. 134,
222). — 3. By heating glycocoU with a slight ex-
cess of urea at 120° (Heintz, A. 133, 70 ; Griess,
B. 2, 106). — 4. By the action of cyanic acid on
glycocoll; i.e. by heating glycocoU sulphate with
potassium oyanate, ppg. potassium sulphate by
alcohol, and allowing the liquid to evaporate
spontaneously (Wislicenus, A. 165, 103).— 5« By
heating glycocoll with urea ; or, better, by boil-
ing these substances with baryta-water (Bau-
mann a. Hoppe-Seyler, B. 7, 34).
Properties. — Monoclinio prisms ; a:b:c
= •662:1: -535; ^8 = 81° 0'. M. sol. cold water
and alcohol, v. sol. hot water and alcohol, nearly
insol. ether.
BeacUons. — 1. Decomposed by heating with
cone. HIAq at 165° to OOj, NH,, and glycocoll
(Menschutkin, A. 153, 105).— 2. Pure HNO,
forms a nitro- derivative, no gas being evolved
(Franchimont, B. T. C. 6, 217).
Salts. — These are all, except the Ag salt, v.
sol. water. — KA': minute, six-sided tables and
rhombohedra. — NaA' aq : extremely soluble silky
needles. — NH^A'aq: large crystals, becoming
opaque from loss of NH,. — BaA'j 2aq (at 100°) :
amorphous, insol. alcohol. — PbA'j 3aq : nodules.
— AgA' : pearly scales.
Beferences.SiHYij, Methyl-, Phenyl-, Phe-
nyl-ethtl-,Styryl-,Nitbo- and Thio-hydantoin
and Hydantoic acid.
HYDRAOIDS. As explained in the articlb
Acids (vol. i. p. 47) those compounds of hydrogen
which, in presence of water, resjct with l(iet^ll|9
ro2
HYDRAOIDS.
oxides, hydroxides, and carbonates, and exchange
the whole of their hydrogen, or a portion of it,
lor metal, are called adds. The element common
to all acids is hydrogen ; but it is only when hy-
drogen is intimately associated in a compound
with one or more strongly negative elements that
the compound has the properties of an acid. The
greater number of acids contain oxygen, but the
presence of this element is not necessarily ac-
companied by acidic function, nor is its absence
proof that we have to deal with a non-aoidio
compound. Solutions of the following com-
pounds contain acids: HP,HC1, HBr, HI, HON,
HSCN, HSeCN, H,Fe(CN)„ H3Fe(CN)„
H,Co(CN)„ H,Co(CN)„ H:Au(CN)„ H,Ir(CN).,
H,Mn(CN)„ H,Os(CN)„ H^t(CN)„ H,Bu(CN)„
H2Pt(SCN)„ HjPt(SCN)„ HAuCl,, H^Hgl^, HBP<,
HjS, H^SnSs, HjCSj. These acids, and a few
more, do not contain oxygen. Acids which are
not compounds of oxygen are sometimes classed
together as hydracids. The name is more par-
ticularly applied when it is desired to distinguish
between two classes of compounds of the same
elements, or group of elements, both of which
classes are acids, but only one class is formed of
oxygen compounds ; thus we speak of the oxy-
acids and the hydracids of the halogen elements.
The terms hydracid is then only a convenient
word when we wish to emphasise the fact that
an acid under consideration is not an oxygen
compound. AB acids are hydracids, as all are
compounds of hydrogen. M. M. P. M.
HYDEACRTLIC ACID 0;B.fi, i.e.
CHi(OH).CH2.C02H. P-Oxy-prapwrm acid.
EthyUne-lactic acid. {ff)-Lactic acid.
Formation. — 1. By digesting j8-iodo-propionio
acid with excess of moist Ag^O, decomposing the
resulting silver salt by H^S, filtering, neutralising
with NajCOj, and evaporating (Beilstein, A. 122,
366; Sokoloff, A. 150, 167). AoryUc, dihydra-
crylic G^B-ifi^, and the isomeric para-adipo-malic
acids (v. vol. i. p. 63) are formed, but are left
undissolved when sodium hydraorylate is dis-
solved in 95 p.o. alcohol (Wislioenus, B. 4, 522 ;
A. 166, 6). — 2. Together with acrylic acid by
boiling i8-iodo-propionic acid with milk of lime.
The impure acid may be converted into the zinc-
calcium salt, which can be purified by recrystal-
lisation, and then decomposed by H^S and the
calculated quantity of oxalic acid (Heintz, A.
157, 291). — 3. By boiling j3-iodo-propionic acid
with a large excess (25 pts.) of water (Thomson,
A. 200, 81). — 4. By boiUng sodium acrylatewith
aqueous NaOH (Linnemann, B. 8, 1095 ; Erlen-
meyer, A. 191, 281). — 5. From glycol ohlorhydrin
and KCN, followed by saponification of the pro-
duct (Wislioenus, A. 128, 4 ; Brlenmeyer, A. 191,
268).— 6. From ethylene oxide and HON and
saponification of product (Erlenmeyer, A. 191,
269).
Properties. — Strongly acid syrup, resolved by
heat into water and acrylic acid* Unlike lactic
acid it does not yield iodoform when heated with
iodine and potash (Lieben's reaction).
BeacUons.—l. Boiling withHjSO< (1 pt.) di-
luted with water (1 pt.) converts it into water
and acrylic acid. — 2. Chromic acid oxidises it
to COj and oxalic acid. Nitric acid acts in like
manner.— 3. Ag^O oxidises it to oxalic and gly-
ooUic acids. — 4. Potash-fusion gives formic and
^getic acids. — 6. HI gives iS-iodo-propionic acid.
9alts.— NaA': [143°]; flat deliquescent
prisms, si. sol. boiling alcohol. At 250° it gives
acrylic and para-adipo-malic acids (Wislicenus,
A.ni, 286).— 0aA'j2aq: [140°-145°] ; prisms,
very easily soluble in cold water, insol. alcohol.
Forms with calcium acrylate a compound
Ca(CjH,Os)(C3Hs02)aq.— ZnA'j4aq: [60°]; tri-
clinio crystals. S. 112 at 16"5° (Wislicenus). —
CaZnA'j : crystalline pp. formed on mixing the
concentrated solutions of the zinc and calcium
salts. S. 9 at 15°. Scarcely more soluble in
hot than in cold water. Insol. boiling alcohol
and ether. — AgA' : delicate prisms and needles,
v. sol. cold water, insol. alcohol.
Nitrile CH2(0H).CH„.CN. Glycol cyanhy-
drim. (221°) at 724 mm. S.G. s 1-059. S.
(ether) 2-3 at 15°. From ethylene oxide and dry
HCy at 55° (Erlenmeyer, A. 191, 273). Liquid,
miscible with alcohol and water.
Dihydracrylic acid CgH^Os i.e.
0(CH2.CH,.C02H)j. One of the products ob-
tained by boiling j8-iodo-propionic acid with AgjO
and water (Wislicenus, A. 166, 39).— NaiA":
silky crystalline mass; insol. 95 p.c. alcohol,
sol. hot 90 p.c. alcohol. Converted by HI into
/3-iodopropionic acid. Its aqueous solution gives
with lead nitrate a fiocculent pp., sol. excess.
HYSEAMIDES. Compounds of the form
N2B3, obtained by the action of ammonia on
certain aldehydes, chiefly aromatic, e.g. furfur-
aldehyde and benzoic aldehyde. They are crys-
talline solids, insol. water, sol. alcohol. They
are not volatUe, and are decomposed by acids
into NH, and the parent aldehyde.
HYDRASTIWE Cj,Hj,NO,. [132°] (F. a. W.).
[o]d= -67-8° (2-5 g. dissolved in 100 c.c. chloro-
form) ; = -I- 127° in HClAq. An alkaloid dis-
covered by Perrins {Ph. [2] 3, 546) in the root of
Syd/rastis canadensis, or G-olden Seal, in which
it exists to the amount of 1^ p.c, together with
berberine, and possibly a third alkaloid, cana-
dine (Van derBspt, Ph. [3] 3, 604 ; Hale, Ph. [3]
4, 105; Burt, Ph. [3] 6, 467 ; Lloyd, Ph. [3] 10,
125 ; Freund a. Will, B. 19, 2797 ; 20, 88, 2400 ;
Schmidt a. Wilhelm, Ar. Ph. [3] 26, 329 ; Eijk-
man, B. T. C. 5, 290 ; Power, Ph. [3] 15, 297 ;
16, 1092 ; Lyons, Ph. [3] 16, 880 ; Mahla, Am.
S. [2] 86, 57). Occurs also in Stylophorum di-
phyllum (Eijkman).
Hydrastine is best obtained by extracting the
root of flydrastis with ether., and recrystallising
the extract from alcohol (F. a. W.). Trimetric
crystals, a:b:c = -846:1: '376. Almost insol. water,
si. sol. cold alcohol, v. sol. boiling alcohol and
chloroform. It has a bitter taste, producing a
feeling of numbness in the mouth. It does not
appear to be poisonous.
Beactions. — 1. Boiling dilute nitric acid
forms opianic acid and hydrastinine. MnQ^ and
H2SO4 give the same products. — 2. KMnOj, in
presence of HCl, also forms opianic acid. —
3. KMnO, in alkaline solution forms hemipio
acid and pyridine carboxylic (nicotinic) acid.—
B'HCl.— B'jH^tCl,.— B'(HAuCl<)j.— B'H,SO,.—
Piorate. B'CjH2(N0j)30H 4aq : yellow needles
(from alcohol).
Methylo-iodide B'Mel. [208^. Needles
(from water or alcohol). ..With" moist AgjO it
gives crystals [237°].
Ethyl6-iodide B'EtL [20G°] (S. a. W.);
[124°^ (Eijkman) ; [183°] (Power). Gives rise to
HYDRATES,
70S
(BTEtO^jPtCI, [207^, B'EtClAuCl, [c. 110°], and
B'EtOH, whioli may be crystallised from hot
water.
HydraBtiiiine 0„H„N02aq or 0„H,3NOs i.e.
OHO.O,HA-OHj.OHj.NHMe (?) (W. Boser, A.
249, 166). [117°]. Obtained, together with
opianio aoid, when hydrastine is treated with
oxidising agents (P. a. W.). White needles (from
ligroin), v. e. sol. aloohol and ether, m. sol. hot
water. CryataUises from all solvents with aq.
Somewhat decomposed when recrystallised from
benzene or EtOAc. Its aqueous solution is
strongly alkaline and intensely bitter. Ppd.
from its solution in acids by KOH but not by
NHj or NajCOs- Eeduoed by Zn and HCl to
hydrastinine dUiydride. BoUing aqueous KOH
forms hydrastinine dihydride and oxyhydrastin-
ine. Mel forms a volatile base and an indif-
ferent oil which yields an oxim [129°].
Salts.— B'HOl: [o. 212°]; needles, v. sol.
alcohol and water. Its aqueous solution shows
a feeble fluorescehce, and is optically inactive. —
B'HjSOi: sol. alcohol.— B'HjCrjO, : slender
golden needles, sol. water. Decomposes at 175°.
— B'BLjPtClj.
Methylo-iodide B'Mel: slender 'yellow
needles, sol. water and alcohol.
Oxim C.oHisNOaCHrNOH. [146°]. Formed
by boiling the base (1 g.) with hydroxylamiue
hydrochloride (^ g.) and alcohol (20 c.o.) for a
few minutes, and then adding NHgAq (Freutid,
B. 22, 457). Needles (from alcohol).— B'jHjPtCl, :
crystalline pp. ,
Hydraatio acid OjH,N04. [232°]. Formed
by boiling hydrastine with dilute HNO, until
KOH no longer ppts. the product. Crystalline,
sol. alcohol and water. Besembles apophyllio
aoid. — ^AgA': needles.
Hydro-hydrastinine 0„H„N02 i.e.
C,nfl,<:;^^^^y(1) (S.oser). [66°]. Formed
by reducing hydrastine with zinc and HCl.
White crystals, v. e. sol. alcohol, ether, benzene,
and CS,. Be-oxidised by chromic acid mixture
to hydrastine.
Salts.— B'HOl : [274°]; crystals, si. sol.
water.— B'jHjPtCla: [216°]; yeUow scales.—
B'HBr : [272°] ; tufts of small white needles si.
sol. water.— B'HI: [232°].— B'^HjCrA = red
scales ; explodes at 150°.
Ethylo-iodide B'Btl: [207°]; needles.
Oxy-hydrastinine C„H„NO, i.e.
C,HA<cHfc^>(^) (^°''')-. t^^"l- (^'"'^^
350°). Formed, together with the preceding, by
the action of aqueous KOH upon hydrastinine.
Prepared by robbing up hydrastinine with water
and potash-ley, shaking, and adding a cold
saturated solution of KjlMnjO, till decolourisa-
tion proceeds slowly ; then filtering, extracting
the residue with ether, neutralising, and eva-
porating the filtrate (Martin Preund, B. 22, 457).
Needles, v. e. sol. alcohol, chloroform, and benz-
ene. Feeble base. By dissolving in dilute HNOa
it is converted into a crystalline nitro- derivative
C,,H,„(N0»)N03 [271°!, insol. HCl, ammonia, or
l,a.CO,Aq,sol.warm NaOHAq.-B'HOl : [138°] ;
cvvstalline. Decomposed by water and by alco-
hnl.— B'.,H,Pt01e: [160°]; yellow needles^-
iJVijAuCl/: [100°] ; reddish-brpwn mass.
Dibromo - hydrastinine C„HjBrjNO,. [o.
280°]. Formed by exposing a solution of the
hydrobromide of hydro-hydrastinine to bromine
vapour (Freund). Broad white needles (from
hot water). In solutions of its salts NH3, caustic
soda, and TSa,jOO, give a pp. which crystallises
from alcohol in slender thread-like needles
[125°].
Di • iodo - hydrastinine hydriodide (so-
called) CijHiiIjNOjHI. [134°]. A substance
formed by boiling hydrastinine for some minutes
with fuming HIAq. (Freund). OrystaUiBes from
alcohol in splendid brown needles.
ConsUiution. — Narootine C,(|H,4(OMe).,N04 is
perhaps methoxy-hydrastine, hydrastine being
0, jH,5(0Me) 2N04. Hydrastinine would then con-
tain no metnoxyl, while cotamine would be meth-
oxyl-hydra!stinine (Schmidt a. Wilhelm, Ar. Ph.
[3] 26, 829). '
HYDRATES. Compounds of water with
other compounds or with elements. If 01 is
passed into ice-cold water a yellowish white
solid is produced, which when dried between
paper at 0° forms a white mass of crystals having
the composition C1.5HjO ; heated to 35° in a
closed tube the crystals separate into 01 and
water, and on cooling to 15° the compound .
CI.5H2O is again produced. The compound
Cl.SHjO is a hydrate of 01, i.e. it is a compound
of 01 with water. When BaO is brought into
contact with water combination occurs, and
BaO.HjO is produced; this compound is 'not
changed by the action of heat alone. It is cus-
tomary to call BaO.H20 an hydroxide, and to
regard it as a compound of Ba, 0, and H, rather
than a compound of BaO with H^O. If water
is added to OaO (an oxide very similar to BaO),
combination occurs, and OaCHjO is produced ;
at a full red heat this compound is resolved into
its constituents, OaO and HjO. The compound
formed by the union of OaO and H^O is some-
times called a hydrate, and its formula is written
CaO.H^O ; but by some chemists it is called an
hydroxide, and the formula assigned to it is
CaOjH^ or Oa(OH)j. Compounds formed by the
union of molecules of H2O with other molecules
or atoms, without a rearrangement of the atoms
of the group HjO, are called hydrates; com-
pounds formed by a reaction of molecules of
H2O with other molecules or atoms, such that
the group H^O is separated into its constituent
atoms, which are rearranged in the new molecule,
are calledhydroxides. But it is often impossible to
tell whether a given compound is an hydrate or an
hydroxide. The definition given above is a theore-
tic^ definition ; we have no certain means of telling
to which class a specified substance belongs.
Another way of stating the theoretical difference
between hydrates and hydroxides is to say that
hydrates contain water as such, and that hy-
droxides contain the elements of water. Another
form of words sometimes used is to speak of
water of hydration, or water of crystalUsation,
and to contrast this with water of constitution.
Cane sugar, for instance, has the composition
OijHhOij. Did we know nothing about cane
sugar except its composition we might write the
formula Oj^HajO,, as Gi^-llH^O ; but the proper-
ties of cane sugar make it evident that it is not a
compound of carbon with water, but a compound
of C, H, and 0, in which the H and Q are iii tU«
704
HYDRATES.
same ratio as in HjO. We may say of cane
sugar that it is an hydroxide, or that it contains
the elements of water, or that it contains water
of constitution. Copper sulphate, CnSOj, com-
bines with watertoformblue crystals CuSO^.SH^O;
when these crystals are heated to 220° or so, the
water is all removed, and white CuSO, remains ;
these changes — ^hydration and dehydration — may
be repeated indefinitely. We may say then that
the blue crystals of copper sulphate contain
water of crystallisation.
The term hydroxide is sometimes used in a
narrower sense than explained above ; by some
chemists it is applied only to compounds whose
reactions are best explained by supposing them
to contain the group or radicle OH.
The problem suggested by the terms hydrate
and hydroxide is not one merely of nomencla-
ture ; it is a typical problem of chemistry. The
two terms attempt to summarise certain concep-
tions regarding connexions between the pro-
perttes and the composition of certain com-
pounds. Here, as in other chemical problems,
we must study composition and properties, and
we must beware of divorcing the one study from
the other.
When Zn reacts with dilute Hj80,Aq to form
ZnSO,, we know that the ZnSOj must contain
the zinc as such ; yet the properties of the Zn are
modified by its combination with the radicle SO4.
The ZnSOj produced is a substance by itself ; it
has its own properties very different from those of
any of its constituents. In a sense it is hardly
accurate to say that zinc sulphate contains zinc ;
zinc sulphate is a new thing in which the pro-
perties of Zn, S, and 0 are merged. Zinc sul-
phate is as distinctly a definite homogeneous
kind of matter as any of the elements which
combine to form it. From it we can obtain Zn,
S, and 0 ; none of these three kinds of matter
have we yet been able to separate into unlike
parts. But when water combines with other
substances, we are dealing with a body which we
are able to separate into unlike parts ; and,
therefore, we may suppose either that the water
combines as a whole with the other substance,
or that a rearrangement of the atoms of the re-
acting bodies occurs, and that in the new com-
pound the relation of the 0 and H atoms are
different from those which hold good in the mole-
cule HjO.
The problem is similar to that presented by
questions about the presence of this or that
radicle, or group of atoms, in the molecules of
carbon compounds; it also presents analogies
with questions regarding molecular and atomic
compounds. We cannot, as a rule, isolate the
radicles which, we suppose, form groups of
closely related atoms in the molecules of carbon
compounds ; we can, however, isolate the radi-
cles which form groups of closely related atoms
in the molecules, or at least in the chemically
reacting weights, of double salts {v. Double
SALTS, p. 414). We can isolate the radicle, or
group of atoms, H^O; the molecule, or the
chemically reacting weight, of a hydrate is sup-
posed to be so constituted that one of its radicles
is the group B.jO ; whereas this group is sup-
posed to be absent from the molecide of an
hydroxide. If a compound is a hydrate we
»b9uld expect it to reveal its constitution hj its
properties and reactions: the radicle HjO.wiU
carry with it certain characteristic properties
different from those which belong to the radicle
OH.
The methods by which attempts are made to
differentiate hydrates from hydroxides consist
partly in studying the chemical reactions of the
compounds, and partly in determining their
physical properties and comparing these with
those of well-defined compounds belonging some
to one class and some to the other.
Compounds formed by the reactions of water
with other compounds or elements, and which
are separated by heat into water and the other
constituent from which they have been produced,
are usually, but not in every instance, classed
as hydrates. Some compounds are decomposed
by heat with production of water and another
substance, but are not produced by the direct
union of water with the other substance ; some
of these compounds are classed as hydrates,
some are not. Thus the compound CuOjHj,
which is decomposed by heat to OuO and HjO,
is generally regarded as hydrated copper oxide,
CuO.HjO ; it is obtained by"ppg. a solution of a
Cu salt by an alkali, but it is not formed by the
direct union of CuOandHjO. But the compound
ASO4H3 is not called a hydrate, although it is
resolved by heat into As^O. and HjO (2H,AbO,
= AsA + 3H,,0).
The reasons for regarding OuOjH^ as a
hydrate, and for not placing AsOjHj in this
class, are based on the chemical analogies of
these compounds. CuO^Hj is very similar, in
its methods of formation and properties, to
compounds which are undoubtedly hydrated
compounds. AsO^H, is an acid ; the hydrogen
of this compound can be replaced by certain
metals ; now acids as a class exhibit properties
which undoubtedly show that they are ijot com-
pounds of water.
Some compounds formed by the reaction of
water with another compound are classed as
hydrates, and some are not placed in this class.
A compound may be formed by the union of
water with another substanbe, and the compound
may be resolved into water and the other sub-
stance, either by the action of heat or a dehy-
drating agent, and yet the compound in question
is not necessarily placed among the hydrates.
Water, for instance, reacts with NjOg to form
nitric acid, and nitric acid loses water, forming
N2O5, by reacting with PjOj; yet nitric acid is
not to be classed as a hydrate. Here again the
properties and reactions of the oompoundformed
by the reaction of water forbid us to regard it as
a hydrate. The arguments against calling nitric
acid a hydrate are not drawn solely from the
reactions, of this compound, but also from the
general reactions of acids.
In discussing whether a specified compound
is or is not a hydrate, regard must be paid to
the chemical analogies of the compound, and to
the reactions of compounds with which it is
allied. Thus it is the custom to regard the com-
pounds M02Hj,whereM = Ca, Sr, orBa, ashydrox-
ides rather than hydrates. One of the reasons
for this is based on the undoubted similarities
between these compounds and the compounds
MOH, where M = an alkali metal. The latter
compounds are certainly hydroxides ; among
HYDRATES.
706
the reasons for this statement jls the analogy in
chemical leactions — e.g. leaotions with acids
and with FCI5 — between these compounds and
the monohydric alcohols 0„Hj„+,OH. These
alcohols cannot be called hydrates ; they aie not
formed by the union of water with the hydro-
carbons C„H2„+2 i ^h^y S'l^e produced by reactions
between iodo- derivatives of the paraffins and
KOH; they react with PCI5 to form chloro-
paraffins 0„Hj„+,01. The compound formed by
the reaction of NasO with H^O may be formu-
lated, so far as composition goes, as Na^O-E^O
or as NaOH. If the molecular weight were found
to be 40, the fonnula NaOH would necessarily
be adopted. In the absence of this evidence, we
must have recourse to a study of the reactions of
the compound. The weight of caustic soda which
reacts with one molecular weight of hydrochloric
acid (HGl) is expressed by the number 40 ; the
same number expresses the weight of this com-
pound which reacts with one atom of sodium ;
hence we adopt 40 as the reacting ^weight of
caustic soda ; and hence we write the formula
NaOH and not Na^CHjO (or NaOjPj). One
reason for writing the formula of caustic baryta
BaOjH, ^^^ 1^°^ BaO.HjO is found in the close
analogies between this compound and caustic
soda. Caustic baryta combines with water to
form a compound Ba02Hj.8H20 ; this compound
is said to be a hydrated hydroxide ; a hydrate,
because SH^O can be removed by heat; an
hydroxide, for the reasons already given. A
great mass of data regarding the dehydration of
metallic hydroxides and hydrated oxides by
heat is given in a paper by Carnelley a. Walker,
C. J. 53, 59.
The specific volumes, or molecular volumes,
of compounds formed by interaction of water
with other compounds throw some light on the
distinction between hydrateg and hydroxides.
The specific, or molecular, volume of a solid
compound is defined as - 2 — ; this
^ spec. grav.
quotient may be represented by (F). Clarke
(Am. 8. [3] 8, 428) has determined (F) for a
number of compounds formed by interactions of
water with other compounds. He finds that for
many hydrated chlorides the mean value of
(F)MClya!H,0 - (F)MCla
X
is 13-76 ; the maximum value being 15 and the
minimum 12*5. In the chlorides examined M
was Ca, Sr, Ba, Mg, Ou, ¥e, and Co; and x
varied from 2 to 6. Values for (F) for the
following compounds were also obtained :
BA-SHjO, IiO,.HjO, KjO-HjO, CaO.H^O,
SrO.HjO, BaO.H20, AljOj-HjO, MnA-HzQ,
FejOs.HjO. Values were also obtained for (F)
for the oxides B^O,. Ij^s' ^0, Ac. The difierenoe
(F) oxide xSfi - (F) oxide
X
yaried from 7-4 to 19-4.
Hence it appears that the specific volume of
each HjO in hydrated chlorides has a mean
value of about 13-76, and that in no case does
the actual value differ much from this; but
that no simple relation can be traced between
(F) for an oxide and (F) for the product of the
combination of that oxide with water in those
cases in which we have reason to believe that a
vot. n.
74.
rearrangement of the atoms of the molecule
H^O has taken place.
Perkin (C. J. 1886, 777) has used measure-
ments of the magnetic rotatory powers of com-
pounds (Mol.B.) to attempt a distinction between
water of constitution and^ water of hydration.
(Mol. B.) of water is taken as unity; if then
(Mol. B.) of a compound is x, and if (Mol. B.) of
the compound formed by adding water to this
compound is increased by about 1 for each H^O
that has entered into combination, we may con-
clude that the new compound is a hydrate. The
following examples are taken from Ferkin'g
paper : —
(Mol. B.) of H.COjH = 1-671 ;
(Mol. B.) of HC02H.HjO = 1-676 + -996.
(Mol. B.) of CH,.COjH = 2-525 ;
(Mol. B.i of 0H,.C0jH.H20 = 2-525 + 1-029.
(Mol. B.) of many organic acids
(Mol.B.) of the corresponding anhydride = a
(Mol. B.) of HjSOj- 2-315;
Mol. E.) of HJSO4.H2O = 2-315 + -873.
Mol. B.) of H2S04.HjO = 3-188;
Mol. B.) of H2S04.2Hj0 = 3-188 + -926.
Mol. B.) of CC1,.CH0 = 6-591 ;
|Mo1. E.) of COCCHCH^O = 6-591 + -446.
The compounds formed by the union of
formic and acetic acids with %ater appear to be
hydrates. The compound formed by the union
of sulphuric acid with water in the ratio
H^SOjiHjO appears to be an hydroxide (Ferkin
thinks it may be S0(0H)4), but the combination
of more watdr with the compound thus produced
is probably a process of hydration. Chloral
hydrate is probably not a hydrate, but rathei
triohloro-ethylidene glycol CClj.CH(0H)2.
Differences can be traced between the various
HjO groups in some hydrated salts. Thus
CUSO4.5H2O loses 4H2O at about 100°, but the
fifth H,0 only at 0. 220°; Na2COs.l0H2O at
12-6° loses SHjO, at 0. 38° thehydrate NajCOa-H^O
remains, and complete dehydration occurs by
heating towards redness. (Begarding the forma-
tion of different hydrates of the same salt from
solutions V. Hammerl, M. 3, 419.) Thorpe and
Watts (O. J. Trans. 1880. 102) have determined
the specific volumes of various hydrated and de-
hydrated sulphates, MSOj.aHjO, where M = Mg,
Zn, Cu, Mn, Fe, Co, and x varied from 1 to 7.
Putting (F) S as specific volume of the dry sul-
phate, they get the following results : —
Mean difference between
(F)Sand(F)S. HjO = 10-7
F)S.2HjO = 13-3
y)S. 3B.fi = U-5
F)S.4HzO = 15-4
,F)S. 7HjO = 16-2.
Hence each HjO group raises (F) to a different
extent.
Sodium phosphate crystallised from solutions
at the ordinary temperature has the composition
Na2HP04.12HjO ; the crystals which separate
at 33° are Na2HP04.7H20 ; there are also hy-
drates intermediate between these, and hydrates
vrith less 'water than 7H2O. If one of these hy-
drates is heated in a closed space water is evolved,
and the pressure increases until at a certain pres-
sure the change stops and equilibrium is pro-
duced. A study of the equilibrium-pressures dis-
closes a marked difference between the hydrates
21 g
?06
HYDRATES.
with 7 an4 12 HjO. Debray (C. R. 66, 195)
gives the following numbers : —
Equilibrmm pressv/res.
Temp.
12-3°
le-s"
20-7''
24-9°
ai-s"
Salt with more than 7 Salt with 7 or less
and np to 12H'0
7-4 mm.
8-9 „
141 „
18-2 „
30-2 „
thanTE'O
4-8 mm.
6-9 „
9-4 „
12-9 „
21-3 „
It is evident that the distinction between hy-
drates and hydroxides is not one which can be
rigidly drawn. One class of compounds shades
off into the other. There is no means by using
which we can refer anyspecifiedoomponnd to this
class or to that. Many reactions must be studied
for each compound, and the classification finally
adopted is generally only provisional.
M. M. P. M.
HYBBAZIDES v. Hidbazones. The phenyl-
hydrazides of aldehydes and of ketones are de-
scribed under the aldehydes and ketones from
which they are prepared. Hydrazides are formed
by elimination of water between an oxygenated
body and a hydrazine. Elimination of water
between an oxygenated body and an amine forms
an amide or imide.
HTDBAZIDO-BENZENE SUI.FEONIC ACID
V. FHENYb-HYDRAZnTE} STJLFEONIC ACID.
HYDBAZIDO-BENZOIC ACID v. Fhunyl-
HYDBAZINE CABBOXTIiIC ACID.
o-HTSBAZIDO-CINNAUIC ACU)
NH2.NH.0eH4.CH:CH.C0jH. [171°]. From
diazo-cinnamic acid by converting it first by
Na^SO, into SOsNa.N2.08H4.0H:CH.C02H, then
reducing by hy^ochloric acid and zinc-dust to
S03Na.NH.NH.C,Hi.CH:CH.C0,H, and finally
decomposing this by HCl gas (Fischer a. Kuzel,
A. 221, 276 ; A. 227, 303). Yellowish crystals.
Nearly insol. water, alcohol, ether, benzene, or
light petroleum. Sol. alkalis and acids-. Its
acetic acid solution bleaches litmus and indigo
(unlike the simpler hydrazines), reduces alkaline
copper solution, and ammoniacalsUver solution.
When melted it forms indazole (q. v.).
S a It.— HABCl : [146°] ; yellowish crystalline
powder, soluble in alkalis, reduces Fehling's so-
lution in the cold. Heat changes it to indazole
(q. v.), not into its anhydride.
Anhydride v. AMiDO-CAEBOSlYElt.
o-HYDBAZIDO-PHENOL.
Methyl ether CsH,(OMe)NH.NHj. [43°].
Methoxy-phemyl-Ti/ydramme. From
C^,(OMe).NH.NH.SOjH and cone. HCU (Eeis-
enegger, A. 221, 319). Slender white needles,
which turn brown in air. Insol. water, v. sol.
alcohol, ether, and benzene. Bednces Fehling's
solution, HgO, and ammoniacal Ag^O,. With
cyanic ether it forms a urea (semicarbazide)
MeO.CeH,.NjHj.CO.NHEt [110°] needles.
Salt s.— B'HCl.— B'jHuCjO.-—
B'CA(NOJ,OH.
Acetyl derivative 05Hj(OMe)N2HjAo 2
[125°]; needles.
o - HTDBAZIDO - PHENOL - v - STTLFHOIf IC
ACID.
Salt. — HO.CeH,.NH.NH.SOsK. From
HO.C,H4.Nj.S08K, zino-dnst and glacial HOAe
'Beisenegger, A. 221, 315). White plates.
Quickly turns red when moist. V. »ol. water,
the solution being very unstable. Bedac«B
Fehling's solution.
Methyl derivative
MeO.OsH,NH.NH.S03H.
Salt.— NaA'aq. From OeH,(OMe)NHj by
diazotisation and treatment with Na^SO, (B.).
Plates. Beduoes cold Fehling's solution.
Warmed with cone. HCl it forms o-hydrazidO'
phenol methyl ether (j. v.).
j)-Hydrazido-pheiiol c-snlphonic acid.
Salt. — HO.O.H4.NH.NH.SO3K. Prepared
in a similar way from the p- compound (B.).
White scales, more stable than the 0- compound,
Beduces cold Fehling's solution.
o - HTDBAZIDO ■ /3 - FHEim. - FSOFIONIO
ACID.
Sodium salt. —
NHj.NH.CeHi.CH2.CH2.C0jNa (E. Fischer a.
Euzel, A. 221, 282). This salt may be got by
reducing C,H4(NH.NH.S0,Na).CH:CH.C0jH by
sodium amalgam in alkaUne solution. Precipi-
tated by adding NaCl and acetic acid. Small
crystals, v. sol. water. HCl liberates the acid
which at once changes into its anhydride, amido-
hydrocarbostyril (q.v.) [143°].
Ethyl-hydrazido-phenyl-propionic acid
CeH,(NEt.NH2).CH2.CHjC02H. Ethyl-hydrai-
ine-hydrocimia'mic acid. Formed by reduction
of the nitrosamine of ethyl-o-amido-phenyl-
propionic acid by zinc-dust and glacial acetic
acid (E. Fischer a. Kuzel, A. 221, 294; B. 16,
1451). Beduces Fehling's solution on warming.
Evaporated with glacial acetic acid it changes
to ettiyl-hydro-oarbazo-styril.
Salts.— BaA'j! crystals.— HABCl. [146°].
At 160° it gives oft HCl and H^O becoming
ethyl-hydro-carbazostyril.
Anhydride G^tK.^^'^^y^- -E^M-
h/jjdro-oarbazo-styril. [165"5°]. Long white
needles, si. sol. water, v. sol. alcohol and ether.
Insol. alkalis, may be distilled unchanged.
Warmed with HCl it changes back to the ethyl-,
hydrazido-phenyl-propionic acid, differing in
this respect from hydrocarbostyril- which is not
changed by hot HCl.
Isomeride of the anhydride
-•CH CH s^
C8H,<^jj,j|'gj,|._>C0. Oxy-ethyl-amido-guimU
vne-dihydride. [74°]. Formed by heating the
anhydride of o-hydrazido-ciunamio acid with
alcohol and EtI at 100° (F. a. E.). Crystals, v.
sol. alcohol, si. sol. water. Gives a nitrosamine.
HTDBAZIDO-TOLXIEITE SULFHONIC ACID
V. ToiiTIi-hzdhazinb suiiPHomo acid.
HTDBAZIMIDO- COMPOTTNDS v. o-Aiimo-
AZO- COMPOUNDS, VOl. I. p. 370.
HYDEAZIWE N^Hi i.e. NH^.NHj. Di-
amidogen. Formed by treating diazo-aoetic
ether with hot cone. KOHAq, decomposing the
resulting crystalline potassium salt by HCl, and
digesting the yeUow crystalline acid so liberated
with very dilute sulphuric acid. No gas is
evolved, but the solution becomes colourless, and
hydrazine sulphate separateson cooling (Curtius,
B. 20, 1632). Hydrazine sulphate is best ob>
tained by warming tri-azo-acetic acid (250 g. in
2'litres of water) with H2SO, (300 g.) until efferves-
cence ceages. Further quantities may be obtained
trom the mother-liquor after hydrazine sulphate
HYDRAZINES.
ror
has crystallised out, by shaking with benzoic
aldehyde, and decomposing the resulting crystal-
line compound with dilute sulphuric acid (Curtiua
a. Jay, J.pr. [2] 39, 27). Hydrazine is only known
in its salts and in the form of a hydrate N^H^H^O
which is got by heating the hydrochloride in a
silver tube with quick lime. This hydrate is a
fuming liquid (119°), with very slight odour. It
corrodes glass, attacks coi^ and india-rubber,
and has an alkaline and burning taste. Hydraz-
ine reduces Fehling's solution and ammoniacal
AgNOj in the cold. With CuSO, it gives a thick
red pp. cf CujO ; with HgOlj a white pp. of calo-
mel ; with alum a pp. of alumina. With aro-
matic aldehydes and ketones it gives sparingly
soluble crystalline compounds. Kitrites decom-
pose its salts with evolution of gas.
Salts . — NjHjHjSO, : tables ; si. sol. cold, v.
sol. hoi, water ; insol. alcohol. Not decomposed
by heating to 250° ; but at a higher temperature
it decomposes with explosive evolution of gas,
liberating sulphur.— NjHjHjOLj. [198°]. From
the preceding and BaCl^. Large regular crystals ;
V. sol. cold water, m. sol. alcohol. FtCl, de-
composes it with evolution of gas. — B'HCl : [89°] ;
long white needles (from hot alcohol). Decom-
posed at 240° into NH4CI, water, and nitrogen, v.
sol. water.— Formate B"(H20O2)2 : [128°] ; got
by heating triazo-acetic acid with water. Beet-
angular tables.
Si-benzylidene hydrazine N2(CHFh)2. [93°].
From hydrazine sulphate and benzoic aldehyde.
Long lustrous yeUow prisms ; insol. water, sol.
hot alcohol. Decomposed by heat into nitrogen
and PhOH:CHPh, a by-product being N2(CHPh)„.
[78°]. The molecular weight of di-benzylidene-
hydrazine has been, confirmed by Baoult's
method.
Si-benzyl hydrazine N2H2(CH2Ph)2. Formed
by reducing the preceding with sodium-amalgam.
Its hydrochloride B'HCl [140°] crystallises from
alcohol in smaU lustrous tables, v. sol. water.
Si-ozy-di-benzylidene hydrazine
Nj(OH.C,Hj.OH)j. [205°]. From saUeylio aide-
hyde and salts of hydrazine. Tables, insol.
water and cold alcohol.
Bi-nitro-di-benzylldene hydrazine
Nj(CH.0eH4.N02)j. [181°]. Prom o-nitro-ben-
zoic aldehyde and salts of hydrazine. Orov^s of
bright yellow needles.
Si-cinnamylidene-hydrazine
Nj(CH.CH:CHI>h)2. [162°]. From cinnamio
aldehyde and hydrazine salts. Yellow tables.
HYDBAZIITES. The name ' hydrazine ' was
applied by Emil Fischer to the then hypothetical
diamidogm H2N.NH2, which he regarded as the
parent substance of the hydrazines, a large and
important class of bases discovered by him, de-
rived from diamidogen by the replacement of
either one or two atoms of hydrogen by monad
hydrocarbon radicles. The name was intended
to indicate the connection of these bases with
the azo- and diazo- compounds, and in particular
with hydrazobenzene CjHs.NH.NH.OjHj (sym-
metrical diphenylhydrazine), the oldest known
member of the class of the hydrazines, whilst at
the same time the termination ' azine ' was
{ormed on the analogy of ' amine,' in order that
a parallel nomenclature might be employed in
the case of corresponding derivatives of the hy-
drazines vni amines; thus th9 }vyd,rn?omuin
compounds would correspond with the ammo-
mwm compounds (A. 190, 70).
Hydrazine itself has recently been prepared
by Ourtius, and the analogy between its reac-
tions and those of the compounds discovered by
Fischer fully justifies the foregoing classification.
The hydrazines are divided into primary and
secondary, according as one or two hydrogen
atoms in the original diamidogen molecule have
been replaced by hydrocarbon radicles. If the
two radicles are attached to different nitrogen
atoms the resulting secondary hydrazine is
termed symmetrical ; if to the same nitrogen
atom it is v/nsymmeirical. The unsyinmetrical
secondary hydrazines behave like tertiary amines ;
they unite with the alkyl halogenides to form
hydrazonium compotmds :
NBVNHj -1- El = N'B'jLNHj.
PrepuwdiioTO. — Hydrazine NHj.NH^ is formed,
together with oxalic acid, when tri-azo-acetio
acid is warmed with water or with mineral
C,HjN,(C00H)3 + 6H2O = 30 AHj + SN^H^,.
It is as yet known only in the form of its
BEllts and of its hydrate NJ3.^,'^.fi (Ourtius a.
Jay, J.i>r. [2] 39, 27).
The derivatives containing alkyl and other
radicles are obtained by reactions which have no
analogy with the foregoing.
Primary hydrazines. — ^1. The primary hydra-
zines, of which phenyl-hydrazine NHPh.NH,
may be taken as a type, are most simply obtained
by reducing diazo-salts with stannous chloride :
Ph.N:NCl + 2SnCL,-f 4HC1
= Ph.NH.NHj,,HCl + 2SnCl4
(V. Meyer a. Leooo, B. 16. 2976).— 2. The method
originally employed by E. Fischer (A. 190, 71),
in which sodium sulphite is used as a reducing
agent, is more complicated. It gives in some
cases a better yield, although occasionally the
reverse is the case (B. 17, 572). In the first
stage of the reaction the diazo-salt is converted
by the sodium sulphite into a diazo-sulphonate :
PKN^Ol + Na^SOs = Ph.N2.S0,Na + NaCl.
Hydrochloric acid is then added, which decom-
poses another molecule of sodium sulphite, and
the liberated sulphurous acid or acid sulphite
reduces the reddish-yellow sodium diazo-sulpho-
nate to the colourless sodium phenylhydraziue-
Bulphonate :
Ph.N:N.S03Na + NaHSO, + H^O
= Ph.NH.NH.S03Na + NaHS04. -
Zino-dust and acetic acid are added to complete
the reduction, and the sodium hydrazine-sul-
phonate is then hydrolysed by heating it with
concentrated hydrochloric acid, when it yields
phenylhydrazine hydrochloride :
Ph.NH.NH.S03Na + HCl + HjO
= Ph.NH.NHi,H01 + NaHSO,,
from which the base can be liberated by caustic
alkali (B. Fischer, A. 190, 78).— 3. When a diazo-
amido-compound is treated in alcohohc solution
with zinc-dust and acetic acid the diazo-group
is reduced and the corresponding hydrazine ia
formed together with an amine :
Ph.Nj.NHPh -h 2H, = Ph.NH.NH, + Ph.NH,.
Diazo-amido-benzsne.
Ph.N2.NEtj + 2Hj = Ph.NH.NHj + NHEt,.
Dlazobenzene-
dletbylamlne.
^s iqethod 19 OQt of practicsl importance (SV
703
HYDEAZINES.
Fischer, A. 190, 77). — 4. The primary hydrazines
containing aUsyl radicles cannot be obtained by
the foregoing reactions, as the diazo- derivatives
of the alkyls are unknown. They may, however,
be prepared from the nitroso-alkyl-ureas. Thus
when nitroso-di-ethyl-urea is reduced with zinc-
dust and acetic acid the nitroso- group is con-
verted into an amido- group :
This amido' compound is then hydrolysed by
heating with fuming hydrochloric acid, when it
yields ethylhydrazine and ethylamine :
™VN(NHj)Et + "^"
= Et.NH.NHj +,NHjEt + CO^ (E. Fischer, A. 199,
287).
Secondary hydrazines. — 1. The unsymme-
trical secondary hydrazines, both in the fatty
and in the benzene series, may be obtained by
the reduction of the nitrosamines with acetic
acid and zinc-dust :
NPhMe.NO + 2Hj = NPhMe.NH^ + H^O
(E. Fischer, A. 190, 146).— 2. The unsymme-
trical secondary hydrazines are formed, along
with the isomeric symmetrical compounds, by
the action of the alkyl haJogenides on the pri-
mary hydrazines ; thus phenylhydrazine yields
with ethyl bromide the compounds NPhEt.NHj
and NPhH.NEtH (E. Fischer a. Ehrhard, A.
199, 325). By employing in this reaction sbdium-
phenylhydrazine NPhNa.NHj, instead of free
phenylhydrazine, only the unsymmetrical com-
pound is formed :
NPhNa-NBL, + EtBr = NPhEt.NHj + NaBr
(MichaeUs, B. 19, 2450 ; Philips, B. 20, 2485).
The unsymmetrical secondary hydrazines formed
by alkylation are identical with those obtained
by the reduction of the corresponding nitros-
amines.
Properties. — The fatty hydrazines are liquids
boiling without decomposition ; those of the
benzene series are either solids of low melting-
point or oUy liquids, and boil with partial de-
composition. Hydrazine itself and some of the
fatty hydrazines are diacid bases; others are
monacid ; the hydrazines of the benzene series
are all monacid bases.
Beactums. — 1. The hydrazines are very stable
towards reducing agents, but are readily at-
tacked by oxidising agents. Thus the primary
' hydrazines reduce Pe'hling''ssoluiAon in the cold,
the secondary on warming. By shaking with mer-
curic oxide the salts of the primary hydrazines
are oxidised to diazo- salts ; this is most readily
shown with potassium phenylhydrazine-sulpho-
nate Ph.NH.NH.SOjK, which is thus converted
into the diazobenzene-sulphonate Ph.NiN.SOjK
(E. Fischer, A. 190, 97). The unsymmetrical
secondary hydrazines are converted by mercuric
oxide into tetraztmes :
2NPhMe.NHi, + Oj = NPhMe.N:N.NPhMe + 2HjO
Dimetliyl-di-plienyl-
tetiazone
(P., X. 190, 167) , whilst the symmetrical secondary
hydrazines are oxidised to azo- compounds :
Ph.NH.NHEt + 0 = PH.N:N.Bt + HjO
Azo-phenyl-etliyl
(E. Fischer a. Ehrhard, A. 199, 328).— 2. Nitrous
Ufivi 09i»v9rt$ the primary hydra^inea into oi-
troso-compounds ; thus with phenylhydrazine
Ph.NH.NH, + HNOj = Ph.N(NO).NHj + H,,0, and
when the nitroso- compound thus formed is
treated with dilute alkalis it yields diazo-
benzenimide :
Ph.N.NH, = Ph.N— N + H^O
I \//
NO N
(F., A. 190, 89). The unsymmetrical secondary
hydrazines, on the other hand, when treated
with nitrous acid, are converted with evolution
of nitrous oxide into the nitrosamines from which
they were obtained: NPhMe.NHj + 2HN0,
= NPhMe.NO+'NjO + 2HjO (F., 4.190,159).—
3. With the alkyl hahgenides the primary
hydrazines yield a mixture of symmetrical aiid
unsymmetrical secondary hydrazines, whereas
sodium-phenylhydrazine gives only the unsym-
metrical compound (v. supra). The unsymme-
trical secondary hydrazines unite directly with
an alkyl bromide or iodide to form a hydraio-
vmm compound :
NEtj.NH2 + EtI = N'EtsLNHj
Trietbylhydrazonlum
iodide.
That triethylhydrazonium iodide has the fore-
going constitution is shown by its behaviour on
reduction vrith zinc-dust and dilute sulphuric
acid, when it yields triethylamine, ammonia, and
hydiiodic acid :
N'EtaLNHj + Hj = NEt, -^ NH, + HI
(B. Fischer a. Ehrhard, A. 199, 316-18).— 4. By
the action of addoyl chlorides on the primary
hydrazines mono- and di- acidoyl derivatives
are obtained. Phenylhydrazine yields, by the
limited action of benzoyl chloride, symmetrical
benzoyl -phenylhydrazine Ph.NH.NH.CO.Ph,
which by oxidation in chloroform solution with
mercuric oxide is converted into benzoyl-diazo-
benzene Ph.N:N.CO.Ph (E. F., A. 190, 125). By
acting with benzoyl chloride on sodium-phenyl-
hydrazine the unsymmetrical benzoyl-phenyl-
hydrazine Ph.CO.NPh.NH, is obtained (Michaelis
a. Schmidt, B. 20, 1713). Both these mono-
benzoylphenylhydrazines, when treated with
benzoyl chloride, yield the same dibenzoyl-
phenylhydrazine, which has therefore the con-
stitution Ph.CO.NPh.NH.CO.Ph (E. F., A. 190,
128 ; M. a. S., 2.C.). These acidoyl- derivatives of
the hydrazines are the hydrazides of the acids
and correspond with the amides, anilides, &c.'
Thus:
Ph.CO;NjH^h
Benzphenylhydrazide
(Benzoyl-phGuylhydrazIne).
Ph.CO.NHPh
Benzunilide
(Benzoyl-aniline).
A large number of similar derivatives cor-
responding with the amides and alkyl-amides
have ibeen prepared ; thus phenylhydrazine hy-
drochloride reacts with potassium cyanate to
form phenylsemicarbazide Ph.NH.NH.CO.NHj
(the semi-urea of phenylhydrazine) ; phenyl-
hydrazine unites with cwrbon dioxide yielding
as product phenylhydrazine pkenylcarbazate
PH.NH.NH.CO.O.N,H,Ph, and with carbandisul-
•ohide to form phenylhydrazine phenylthJuxa/rb-
azate Ph.NH.NH.CS.S.N2HiPh (corresponding
respectively with ammonium carbamate and
ammonium thio-carbamate), and on heating the
* It is, therefore, inaccuiate to applj tU« name * hydros
HYDRAZONES.
709
Ifttter compoand it yields the thio«urea diphenyl-
tUocarhazide CS(NH.NHPh)j (E. F., A. 190,
113-118). In like manner azidines are known,
corresponding with the amidines ; thus bemenyl-
diphenylazidine ^^•C^^g'^HPjj (Pinner, B.
17, 182). — 5. Phenylhydrazine unites directly
with cyanogen to form dioyano-phenylhydraz-
ine (P.).— 6. One of the most important reac-
tions of the hydrazines is that in which they
undergo condensation with compouitds contain-
ing carbonyl- groups : thus
Ph.CHO + H^.NHPh = Ph.CH:N.NHPh + H^O
Benzylideue-pbeuyl-
hydraziae (Benz-
aldehydxazoue ).
Ph,CO + H,N.NHPh = Ph,C:N.NHPh + K,0
Benzoplienone-
plieiiyltiydrazane.
In this way phenylhydrazine may, Uke hydroxyl-
amine, be employed in testing for the presence
of carbonyl-groups in compounds (E. Fischer,
A. 190, 134 ; B. 17, 572). The compounds thus
formed are known as hydrazones {q. v.). The
reaction is occasionally complicated by the pre-
sence of other reactive groups, in addition to the
carbonyl group, iu the molecule of the com-
pound acted upon by phenylhydrazine; thus
although compounds containing the a-ketone-
alcoJwl group — CH(OH).CO — react in the
cold with only one mol. of phenyl hydrazine
to form colourless compounds containing the
group — CH(OH).C(N.NHPh)— , yet when the
compound thus formed is heated with excess of
phenylhydrazine, the alcohol group undergoes
dehydrogeuation, reacting at the same time with
a second mol. of phenylhydrazine and giving
rise to a yellow compound containing the complex
— C(N.NHPh).C(N.NHPh)— . Such compounds
in which two hydrazine- residues are attached to
contiguous carbon atoms are known as osazones
(v. Hydbazokes) and may also be obtained di-
rectly by the action of the hydrazines on the
a-diketones. They are of great importance in
connection with the carbohydrates, which may
frequently be recognised by means of their
characteristic osazones (E. Fischer, B. 17, 579 ;
20, 821). Again, an unsaturated hydrocarbon
group, ii contiguous to the carbouyl-group, may
also take part iu the reaction with phenylhydraz-
ine:
CHjiOH.CHO + HjN,NHPh
AGrole![n
N N.Ph
= II I +H,0
Fheuylpyrazolme
(E. Fischer a. Knoevenagel, A. 239, 194; v.
also Knorr a. Blank, A. 238, 139). An analogous
case is that of ethyhc aceto-acetate, which reacts
with phenylhydrazine in the cold with elimina-
tion of water to form the hydrazone
CH3.C(N.NHPH).0Hj.000Et ;
but on heating this compound, it parts with
alcohol yielding a phenylpyrazolone of the
formula
N.Ph
A
IN CO
CH,
« i
:,.c-Ci
the oarbethoxyl-group also taking part iu the
reaction (Kuorr, A. 238, 146). Similar complex
condensations have been described with 3-di-
ketones and with some 7-diketones (E. Fischer
a. Bulow, B. 18, 2135 ; Paal, B. 17, 914 ; Japp
a. Huntly,O.J. 1888, 184).
Various other reactions of hydrazines are
known, and some of these are doubtless of
general application, although they have as yet
been applied only in special cases. They will
be described under the appropriate hydrazines.
F. B. J.
HYBBAZO-BEITZENE v. s^Di-fhbnxi.-
HYDBAZINE.
HYDSAZO-EEITZOIC ACID v. Di-pbemtl.
HTDBAZINE W-CAKBOXYUO ACID.
HYDEAZO- COMPOUNDS. Symmetrical di-
derivatives of hydrazine, of the formula
ENH.NHB' where E and R' represent radicles
attached by means of carbon to the two atoms
of nitrogen (c/. Hydeazines and s-Di-PHENyi<-
hydbazine). They are described iu this dic-
tionary as derivatives of hydrazine.
HYDBAZO-HYDSOQTTIITOirE d-Teiea-oxt-
M-PHENYL-HYDEAZINE.
HYDEAZO-DI- METHYL- HYDEOaumOlfE
V. Tetra-methyl derwative of Tsiba-oxx-si-
PHENYL-HYDEAZINE.
HYDBAZO-NAFHTEALENE v.Di-naphihzi.-
HYDBAZINE.
HYDBAZONES. The compounds formed by
the condensation of substances containing the
carbonyl group with phenylhydrazine were named
by many chemists ' phenylhydrazides,' or more
shortly, ' hydrazides.' E. Fischer, however {B.
21, 984), has pointed out the impropriety of
the term. A 'hydrazide' corresponds with an
' amide ' ; the phenylhydrazido-gronp isPh.N^Hj;
thus the phenylhydrazide of benzoic acid is
Ph.CO.NjHjPh. In order to avoid the ambiguity
which the above erroneous use of this term in-
troduces, Fischer has proposed to name the com-
pounds in which the dyad group NPhH.N— re-
places the oxygen of a carbonyl group ' phenyl-
hydrazoues' — the termination one serving to
suggest their connection with ketones or with
carbonyl compounds generally. Further, as iu
the very great majority of cases it is phenyl^
hydrazine which is employed in the preparatioa
of these compounds, the abbreviated form ■ hy-
drazone ' may be applied in all such cases, and
is to be taken to signify ' phenylhydrazone ' un-
less the contrary is stated. The name 'osazone'
is, for reasons to be explained later, applied to
any compound containing- two dyad groups
NPhH.N:= attached to two contiguous carbou
atoms. Thus iu the case of the two compounds
obtained from glyoxal and phenylhydrazine wa
have:
CHO
Glyozalhydrazone |
CH:N.NHPh
CH:N.NHPh
CH:N.NHPh
Glyoxalosazone
(E. Fischer, I.e.).
: FormaUon. — The fact that phenylhydrazine'
reacts with aldehydes was first pointed out by
710
HTBRAZONEa.
E.Fischet(^. 190, 134); thnawilih benzoic alde-
hyde:
Ph.OHO+H^.NHPh = Ph.CaN.NHPh+HjO.
Beiizylidene-plienylliydiazina
(Benzaldebydrazone) ■
Later (B. 16, 661, footnote; 17, 572) he ex-
tended the reaction to ketones, diketones, ke-
tonic acids, and caibonyl compounds generally,
and proposed the use of phenylhydrazine as a
teagentj analogous in its action to hydroxyl-
ttmine, to be used in testing for the presence of
ttarbonyl groups in compounds. At first (B. 17,
£73) he recommended that the compound to be
Investigated should be heated with an aqueous
Solution of phenylhydrazine hydrochloride mixed
with excess of sodium acetate, to which alcohol
might be added to ^ssolve the compound ; but
later {B. 82, 90, footnote) a mixture of equal
volumes of free phenylhydrazine and 50 p.o.
acetic acid was substituted. The hydrazone
generally separates as a sparingly soluble and
frequently crystalline compound. The forma-
tion of a hydrazone under these circumstances
is a proof that the compound under examination
contains at least one carbonyl group in the
ketonic or aldehydio form, i.e. attached with
both its affinities to carbon atoms, or to a
carbon and a hydrogen atom, or to two hydrogen
atoms. Carbonyl groups attached with one or
both affinities to oxygen or to nitrogen — as in
CO.OH, CO.NH2, &o.— do not react with phenyl-
hydrazine. In some respects phenylhydrazine is
to be preferred as a reagent to hydroxylamine :
it is more readily obtained, and compounds con-
taining more than one carbonyl group frequently
react with two mols. of phenylhydrazine, thus
showing the presence of two carbonyl groups,
when they would only react with one mol. of
hydroxylamine. The hydrazones of mono-
carbonyl compounds are formed Uke the alde-
hydrazones iJiceady mentioned : thus, acetone-
hydrazone (CH3)2C:N2HPh, aniphemylhydraeone'
pyrwoic acid CH3.C(l!T2HPh).C00H. The action
of phenylhydrazine on dicarbonyl compounds,
however, varies with the relative positions of the
two carbonyl groups. a-Dicarbonyl compounds,
in which the two carbonyl groups are directly
united, react either with one or with two mols. of
phenylhydrazine, according to the proportions
employed, to form respectively hydrazones and
osazones ; thus, diacetyl CH,.CO.CO.CH, yields
diacetylmotiohydrazone CH3.C(N2HPh).CO.CH,
and duuietylosazone
CHs.C(NjHPh).C(N8HPh).CH,
(v. Pechmann, B. 21, 1413). Glyoxal and benzil
iorm similar osazones (Pickel, A. 232, 230).
J3- Dicarbonyl compounds, in which the two
'Carbonyl groups are separated by a carbon atom,
react with one mol. of phenylhydrazine to form
an unstable hydrazone, which spontaneously
parts with water yielding a pyrazole :
Ph.CO.CHj.CO.CH3 + Ph.NH.NH,
Benzovlacetone
N.Ph
A
-- N C.CH,-4-2H,0. This reaction does not,
II II
Ph.O— OH
Uetbyl-diplieiiyl-pyiazole
> Abbreviation for ' benzaldeliyde -liydrazone,* Uke
"lieDzaldaxim' for ' beuzaldetayde-oxim.'
however, occur with j3-diketones oi the forts
— CO.CE's.C0— , in Which both hydrogen atoms
of the methylene group are replaced by alkyls
(Fischer a. Biilow, B. 18, 2185 ; Knorr, A. 238,
139). 7-Dicarbonyl compounds, in which the
two carbonyl groups are separated by two carbon
atoms, react sometimes with 2 mols. of phenyl-
hydrazine to form dihydrazones, thus :
CH3.CO.CHj.CHj.CO.CH3 + 2Ph.NH.NHj =
Acetonyl-acctoue
CH,.C(NjHPh).CH,.CHj.C(NjHPh).CH,+2HjO
(Paal, B. 18, 60), and sometimes with only 1
mol. of phenylhydrazine, eliminating, however,
2 mols. of water :
CH3.CO.CH2.CHj.CO.C5H5 + CjH5.NH.NH,
Acetonyl-aoetopbenone
= C„H„N, + 2HjO.
The constitution of the compounds of the latter
class is unknown (Paal, B. 17, 914).
Allusion has already been made to the simi-
larity in the action of phenylhydrazine and of
hydroxylamine on carbonyl compounds. The
phenylhydrazo- group N.NHPh corresponds with
the hydroximido- group N.OH. V. Meyer has
shown that hydroximido- (isonitroso-) compounds
are also formed by the action of nitrous acid on
compounds containing the group CH, or CHB'
attached to two electro-negative radicles, B' being
a readily displaoeable radicle (acetyl or carb-
oxyl). Japp and Elingemann (C J. 1888, 523 ;
B. 20, 3284 and 3398 ; 21, 549) have found that
by the action of diazo- salts on compounds which
yield hydroximido- compounds with nitrous acid
(or aa- their sodium compounds) hydrazones are
formed.' The following equations, in which for
the sake of simplicity /ree diazobenzene is em-
ployed instead of a diazo- salt, will illustrate
the analogy between the action of nitrons acid
and diazo- salts on compounds of the above-men-
tioned type.
Thus with ethylic aceto-acetate the reactions
may be expressed as follows :
CH,.C0.CHj.C020jH5 + HNO,
- CH3.C0.C(N.0H).C0,0 A + HjO
Etbylic bydiozlmido-acetb-
glyoxylate
and CH,.C0.CHj.C0jCjHj+Ph.N,H0
Diazobenzene
- CH,.C0.C(NjHPh).C03CjH5 + HjO.
Btbylic pbenylhydrazone-
Boeto-glyoxylate
In the case of moualkyl derivatives of ethylio
aceto-acetate, the acetyl group is expelled :
CH3.C0.CH{CH3) .COjCjHj + HNO,
^ CH3.C(N.OH).COjGjH5 + G^fit
Ethylic bydroximido-
pyruvate
and 0H3.CO.CH(0H,).COjCjH5 + Ph.NjH0
= CH3.C(NjHPh).COjCjH5 + G^fir
Etbyllo pbenyUiydrazone-
pyruvato
With free aoeto-acetio acid, or monalkyl-
aceto-acetic acids, the carboxyl group is elimi-
nated instead of the acetyl group :
CH,.CO.CHj.COOH + HNOj
= CH,.OO.CH:N.OH + CO, + H,0
Pymvaldebydroxime
and CH3.C0.CH,.C00H-HPh.N,H0
= CHs.CO.CH:NjHPh + CO, + H,0,
Pyruvaldehydrazone
* Beyer and Olaisen have, bowever, sbown tbat in oe>
tain cases mixed azo- compounds are formed (A 31,
1897).
HYDRAZOKES.
rii
whilst metuaoeto-aoetio acid reacts with diazo-
benzene forming the monohydrazone of di-acetyl
CH,.OO.C(NjHPh).CH, {«. supra) and ethaoeto-
acetio acid yields the corresponding compound
of the formula CHj.CO.OpijHPhj.CjHs. Those
of the foregoing hydrazones wnioh contain a
oarbonyl group contiguous to the phenylhydraz-
one group may be made to react with phenyl-
hydrazine to form osazones (J. a. X., Z.c).
Phenylhydrazine is capable of expelling the
hydrozimido- group to form hydrazones :
Ph,C:N.OH + Ph.NH.NHj
Siphenyl-acetozime
= PhjC:N.NHPh + NHj.OH
Beuzophenoue-
phenyUiydrazone
(Just, B. 19, 1206).
PropertUs. — A few of the hydrazones are
liquid, but the majority are crystalline solids.
By warming the solution of a carbonyl compound
with phenylhydrazine and determining the melt-
ing-point of the hydrazone formed, the hydraz-
one, and thus the carbonyl compound from
which it is derived, may frequently be identified.
Many of. the hydrazones decompose on melting ;
in determining the melting-point, therefore, the
temperature must be raised as rapidly as is con-
sistent with accuracy, otherwise too low a melt-
ing-point will be found (E. f'ischer, B. 17, 573;
20, 827).
Beactions. — 1. The hydrazones are readily
reduced either with sodmm amalgam and acetic
acid or with zmc-dust and acetic acid. Accord-
ing to the length to which the reduction is
carried the hydrazone either talces up two or four
atoms of hydrogen — in the latter case with dis-
ruption of the molecule at the point ot union
of the nitrogen atoms. Thus phenylhydrazone-
pyruvio acid CH3.C(N.NHPh).C00H yields in the
first stage of reduction benzene-hydrazopropionic
acid CH,.CH(NH.NHPh).COOH (B. Fischer a.
Jourdan, B. 16, 2243), and this by further reduc-
tion breEiks up into alanine CHg.0H(NH2).C00H
and aniline (Japp a. Elingemann, G. J. 1888,
535). This latter mode of reduction into a mix-
ture of two bases was discovered by Tafel (B. 19,
1924), who proposed to employ the reaction as a
method of preparing primary amines from carb-
onyl compounds ; thus benzaldehyde could be
converted, by the reduction of its hydrazone,
into benzylamine. — 2. The action of heat on the
hydrazones has not been much studied. Many
of them decompose when heated, yielding
amongst other products aniline. When alde-
hydrazone is heated for some time to boiling it
is partially converted into diacetyl-osazone (v.
tiipra):
2CH,.CH(NjHPh)
= 0H,.C(NjHPh).C(N2HPh).CH3 + H,
(Japp a. Klingemann, C. J. 1888, 542).— 3. By
the action of sodmm and an alkyl halogenide on
ft hydrazone (Philips, B. 20, 2487), an alkyl
group may be introduced ; thus with benzalde-
faydrazone :
Ph.CH:N.N<^^ + Ph.0Hj01
Sodium benzalde-
hydrazone
-Ph.CH:N.N<^^j,j^+NaCl ;
and as the compound resulting in this case is
identical with that obtained by the action of
benzaldehyde on unsymmetrical benzyl-phenyl-
hydrazine, it is thus proved that the hydrazones
have the constitution E'.CH:N.NHPh and not,
as was otherwise conceivable, the constitution
/NPh
B'.CH< I (Philips, Z.C.). Sodmm alcoholatea
may be substituted for sodium in the above re-
actions (Landsberg, O. /. 1888, 519). — 4. By
heating a hydrazone with an amhydride of an
orgamc acid an aoidoyl group may be introduced ;
thus, benzaldehydrazone, when heated with
acetic anhydride, yields the compound
Ph.CH:N.N(CjHsO)Ph (Miohaelis and Schmidt,
B. 20, 1717 n.). — 5. By heating hydrazones with
mineral acids they may generally be hydrolysed
into the carbonyl- compound and hydrazine &om
which they are derived (B. Fischer, A. 190, 135).
The hydrazones of o-ketonie acids, however —
thus, of pyruvic acid — are not hydrolysed by
dilute mineral acids, whilst with strong acids
they undergo complex decomposition (B. Fischer
a. Jourdan, B. 16, 2243). Some secondary
hydrazones are converted by hydrochloric acid
into indole- derivatives, ammonia being elimi-
nated in the process :
Methyl-plienylliydrazone-pyruvioaoid
-C,H,<' ^CCOOH + NH,
Methyl-indole-carboxylic acid
(B. Fischer a. Jourdan, B. 16, 2249 ; E. Fischer,
A. 236, 116). — 6. If a phenylhydrazone contain
a methyl- or a methylene -group directly
attached to the carbon atom of the original
oarbonyl-group, it may generally be converted
into an indole- derivative by heating with zinc
chloride. The reaction occurs with elimination
of ammonia, and resembles the foregoing forma-
tion of an indole- derivative by the action of
hydrochloric acid, but is applicable to primary
as well as to secondary hydrazones :
CeH,.NH.N:0(0H3)2= C.H,<^^O.CH, + NH,
Acetone-phenylbjdrazone Methyl-ketole
(E. Fischer, A. 236, 116). Aldehydrazoue, how-
ever, when heated with zinc chloride, does not
yield indole, but its homologues are converted
into homologues of indole.
Some hydrazones undergo specific chemical
changes,'not general to the class, but depending
on the presence of certain reactive groups in
the molecule of the particular hydrazone. Such
changes are, for example, the formation of a
pyrazolone from the hydrazone of ethylio
aceto-acetate and of pyrazolines from the hy-
drazones of unsaturated carbonyl- compounds
(v. Htdkazines).
Osazones. As already mentioned, the name
osazone denotes a compound containing in its
molecule two dyad groups NPhH.N~ attached
to two contiguous carbon atoms. E. Fischer
{B. 17, 579) obtained from carbohydrates a series
of characteristic compounds formed by the
introduction of two phenylhydrazone groups
712
HYDRAZONES.
into the moleonle of a carbohydrate (v. infra).
The compound from dextrose was termed
yhemyl-ghicosazone; that from galactose, f/ien<^Z-
gaUustosaicme, and so on. Later, when it was
found that in these compounds the two phenyl-
hydrazine residues were in contiguous positions,
the name osazone was applied to all compounds
containing this paitionlar grouping (E. Fischer,
B. 21, 985).
Various methods for the preparation of
osazones have already been incidentally men-
tioned in the course of this article. Thus, they
are formed (1) by the action of 2 mols. of phenyl-
hydrazine on an o-dicarbonyl compound ; (2) by
the action of 1 mol. of phenylhydrazine on a
hydrazone containing a carbonyl-group con-
tiguous to the hydrazone-group, such hydrazones
being formed as intermediate products in the
first-mentioned reaction ; and (3) by heating an
aldehydrazone. In addition to their formation
by the foregoing reactions, which have been
already described, osazones may be obtained
(4) by heating iso-nitroso-ketones, in which the
iso-nitroso- group is contiguous to the carbonyl-
group, with phenyl-hydrazine :
CH3.C0.CH(N.0H) + 2Ph.NH.NHj
Isonitroso-aoetone
= CH,.C(NjHPh).CH{N2HPh) + NHj.OH
£;xuTaldeliyde-osazone
fv.Fechmann, B. 20, 2543). They are also formed
(5), by the action of phenylhydrazine on com-
pounds containing the group — CII(OH).CO — ,
thus, on a-ketone.-alcohols and a-aldehyde-alco-
hols ; and it is the members of the carbo-
hydrate fanuly belonging to these classes which
yield osazones. In the cold — unless on long
standing — only the carbonyl- gi'oup reacts with
phenylhydrazine, and a hydrazone containing
the group — 0H(0H).C(N2HPh)— is formed;
but this compound, on heating with excess of
phenylhydrazine, is converted into an osazone,
the tuoohol- group also taking part in the re-
action. The mol. of hydrogen which is removed
in this process reduces a mol. of phenyl-
hydrazine to aniline and ammonia :
— CH(OH).CO— I- 3NHPh.NHj
= — C(NjHPh).C(NjHPh)—
+ NH2Ph + NH, + 2HjO
(B. Fischer, B. 17, 579 ; 20, 821 ; 21, 988, 2631).
a-Dicarbonyl- compounds, on the other hand,
react with excess of phenylhydrazine to form
osazones even in the cold.
The osazones are of a yellow colour: the
yellow colouring matters known as ' tartrazines '
are the osazones of dihydroxytartaric acid.
Cone, sulphuric acid dissolves the various
osazones, giving characteristic colourations, and
the solution generally exhibits some definite
colour-change on standing (Japp a. Elingemann,
B. 21, 649). Fuming hydrochloric acid hydro-
lyses the osazones in the cold into phenyl-
hydrazine and the a-dicarbonyl- compound from
which they are derived (E. Fischer, B. 21,
2631).
Osotriazones. The osotriazones contain the
— 0=Ny
closed-chain complex I pN — . They are
formed : 1. From the osazones either by boiling
with dilute acids (v. Peohmann, S. 21, 2758), or
by heating (Auwers a. V. Meyer, B. 21, 2806),
the latter process giving the better yield :
OH,.C:N.NHPh CH,.0:Nv
I = I >N.Ph + NH^h.
0H3.0:N.NHPh OHa-CiN/
Diaoetyl-osazone Dimethyl-plienyl-
osotr^oae
2. From a hydrazone-hydroxim by the action of
the chlorides of phosphorus :
CH3.C:N.0H CH3.C:Nv
I = I >N.Ph + H3O
CH3.C:N.NHPh CHj.CiN/
Diacetyl-hydxazone-
hydrozizQ
!v. Pechmann, Z.C.). — 3. From the osotetrazones
V. infra).
The osotriazones are feebly basic, very stable
compounds.
Osotetrazones. The osotetrazones contain
_C=N— N—
the closed-chain complex I I . They
— C=N— N—
are obtained by oxidising the osazones with
potassium dichromate in dilute acetic acid solu-
tion:
CH3.C:N.NHPh CH3.C:N.NJ'h
I _ +0= II +H,0
CH3.C:N.NHPh CH3.C:N.N.Ph
Diacetyl-osazone Biacetyl-osotetzazone
(v. Pechmann, B. 21, 2755). They are dark-
red neutral compounds, the formation of which
has been recommended as a characteristic test
for the osazones (v. P.).
By boiling the osotetrazones with dilute
hydrochloric acid they are converted into oso-
triazones :
0H3.G:N.N.Ph
I I +H,0
CH3.C:N.N.Ph
CH3.C:Nv
I >N.Ph + NHjPh + 0.
CH3.C:N/
Dixnethyl-plieziyl-
OBotrlazone
The oxygen is not liberated, but oxidises a por-
tion of the substance (v. Pechmann, J5. 21, 2757).
Neither the osotriazones nor the osotetraz-
ones have been much studied. F. B. J.
HYDEAZOPHEHINE C3,H3,N5. [174^.
Formed by heating azophenine with alcoholic
ammonium sulphide at c. 140°. Colourless
needles (0. Fischer a. Hepp, B. 20, 2483).
HYDBAZO-FHEirOL v. Di-oxY-Di-PHENn-
HXDEAZINE.
HYDRAZO-DIPHENYL
CaH5.0eH4.NH.NH.CsH,.CeH5. Di-dApJimyl hy-
drazine. [247°]. Prepared by reducing azoxy-
diphenyl with alcoholic ammonium sulphide
(Zimmermann, JS. 13, 1961). White pearly
plates, insol. water, si. sol. alcohol and EOAc,
m. sol, ether.
HYDBAZO-PHENTI-METHYIi v. s-Phenh,-
MEIHTL-HyDRAZINE.
HYSBAZO-TEBEFHTHALIC ACID v. Di-
fHENYL-HTTDBAZINE TETBi-OAItBOXTLIO ACID.
HTIIBAZO-TOIiTTENEv.Di-TOL^-HTDSAzniE.
ETOBAZO-TOLUISINE 0. Di-mnda- ni-
ZOIi'CL-HTDBAZIin!,
HYDEOBENZOter.
71S
KY1>SAZ0-XT££N£ v. Di-zyLzii-HxsBAziNE.
HTSBAZTJLUIN v. Azuzmio acid.
HYDBIDSS, Binaiy oompounda of hydrogen.
Hydrogen forms binary compounds with all the
distinctly non-metaUio elements, also with As
and Sb. A hydride of Ga is known, and there
probably exists a definite but unstable hydride
of Fd, and perhaps of one or two of the other
platinum metals. There are also indications of
the existence of hydrides of E and Na.
The non-metaUio hydrides may be classified
in accordance with their composition as follows :—
(i.) HM: HP, HCl, HBr, HI.
(ii.) S^M: HjO, H,S, H^Se, H,Te.
(iii.) fljM: .H,N, H,P, ? H3B, HjAs, H,Sb.
(iy.) H^M: H,C, H,Si.
(v.) Various : HjOj, ? HjSa, H^Pj, H.Nj ; nu-
merous hydrocarbons.
A definite hydride of Cu, GujH,, has been
obtained. It decomposes at 60° into Cu and H.
K and Na absorb H rapidly at c. 300° ; com-
pounds, E^H and Ka2H, appear to be formed.
Fd, Ft, Fe, Ni, Au, and some other metals, when
nsed as the negative electrodes in the electrolysis
of water, absorb considerable quantities of H.
A compound Fd^H is probably formed. In the
other oases it is doubtful whether the absorption
is purely physical, or partly chemical and partly
physical. As a class, the metals do not form
definite hydrides, while the non-metals do form
hydrides. The greater number of the non-me-
tallic hydrides may be produced by direct union
of their elements ; a few are produced by evolv-
ing H in contact with solutions of compounds of
the elements, e.g. AsH,, and a few by more indi-
rect methods.
The non-metaUic hydrides vary much in pro-
perties: HCl, HBr, and HI are strong acids;
H^S is a very weak acid ; NH, is markedly alka-
line; FH, is feebly alkaline; H^O is neutral;
hydrocarbons difCer extremely in their proper-
ties, although none is either distinctly an acid
or an alkali. Some hydrides are easily decom-
posed by heat, e.g. H2O2, HI; others are ex-
tremely stable as regards the action of heat, e^.
HCl, HjO- M. M. F. M.
HTSSINSIC ACID is a-oxT-o-AMino-PEENTii-
AOETic ACID, of whioh di-oxindole is the an-
hydride.
HYDEINDINE v. Indinb.
HYDBINDONAFHTHEITE v. Indonapeihemb
DIHYDBIDE.
EYSSIODIC AGU) v. Iodhxi>bic acid, vol. iii.
HTSBO-. Organic compounds whose names
begin with this prefix will usually be found de-
scribed as hydrides of the substances to whose
names it is attached.
Use of this prefix applied to vnorgame acids
and salts. For hydro- acids and hydro- salts v.
the acids or salts sought for. Thus, hydrofluo-
boric acid will be found under BoBorLUOBHYDBio
ACID ; hyd/roferrocyama acid will be found under
Pebeootanhydbio acid; h/ydrofliiasiUcates will be
found under Silicates.
ETSBO-ACBIDIKE v. AcBiDunB octoez-
dbide.
ETSBO-ANISOlN
C^4(0Me).CH(0H).CH(0H).C^,0Me. Di-
methoxy-hydro-benzo-in. [170°-172°]. A small
quantity of this body is formed from anisic
aldehyde in ethereal solution by sodium amal-
gam (C. Saytzeff, Z. [2] 3, 678; Samosadsky,
Z. [2] 4, 6U ; Bossel, Z. [2] 5, 562 ; M. Wallach,
A. 226, 78). Pyramids, v. si. sol. warm water,
m. sol. ether, v. sol. hot alcohol. When dis-
tilled in a current of CO^ it partly sublimes,
and is partly converted into anisic aldehyde.
Cone. HNOs forms nitro-anisic aldehyde. Chro-
mic acid mixture gives anisic acid. FCl, forms
0»H,(OMe).CO.Cl.
Isohydroanisoin C,„H,g04. [125°]. Separates
only after the addition of water to the alcoholic
solution of anisic aldehyde which has been
treated with sodium. Slender interlacing needles,
T. e. sol. alcohol and ether.
Seoxyanisoin OuHuO,. [95°]. Fojmed by
boiling hydro-anisoin or iso-hydro-anisoin with
dilute H2SO4. Tufts of needles, v. sol. alcohol
and ether. Oxidised by chromic acid mixture to
anisic aldehyde and anisic acid.
Isomeride of Deoxyanisoin C„H,eO,. [215°].
Formed by the action of Zn and HCl on hydro-
anisoitn or on anisic aldehyde. CrystaUine;
insol. ether.
HYSBO-ANTHBACEITE v. Anibbacene hv-
DEiDE. A hydride 0„Hj, [88°] (0. 270°) has
been obtained byliucas (B. 21, 2510) by heating
anthracene (3 g.) with redphosphorus (3 g.) and
HI (16g. of S.G. 1-7) for twelve hours at 250°.
HTSBO-AITTHBACEITE CABBOXTXIC
ACIDS V. vol. i. p. 278.
HYSBO-ANXHBAHOL v. Authkanoi. mHT-
dbide, vol. i. p. 279.
HYSBO-AFO-ATBOFINE v. Atbofike.
HYDBO-ATBOFIC ACID v. a-FHENYi.-PB0Pi-
ONIC Aon>.
HYDBOBEITZAMIDE v. Benzoic AiiDEHYDE.
HYDBO-BEirZENE DI-CABBOXYLIC ACIDS
V. Hydrides of the Fhthatjo acids.
HYDBOBENZOIC ACID v. Benzoleio aoid.
HYDBOBENZOlN C„H„Oj i.e.
C,H5.CH(0H).CH(0H).C8H5. Stilbene alcohol.
Mol. w. 214. [138°] (Faal, B. 16, 637) ; [134°]
(Zincke) ; [133°] (A.), (above 300°). S. -25 at
15°; 1-25 at 100°.
Formation. — 1. By the action of granulated
zinc upon benzoic aldehyde dissolved in alcohol
which has previously been partially saturated
with HCl. The hydrobenzoin is ppd. on subse-
quent addition of water (Zinin, A. 123, 125).—
2. Together with isohydrobenzoin and benzyl
alcohol by the action of sodium-amalgam on
benzoic aldehyde dissolved in alcohol (Ammann,
Z. [2] 7, 83; A. 168, 69).— -3. From benzoin by
heating with alcohoUc potash at 155° in an ex-
hausted tube, benzilic acid being also formed
(Zinin, Bl. [2] 7, 260).— 4. By the action of so-
dium-amalgam on benzoin (Grimaux, B. 2, 281)
or on benzil (Porst a. Zincke, A. 182, 259).—
5. Prom OaH5.OHBr.CHBr.CjH5 by treatment
with silver acetate or oxalate and saponification
of the product (Limpricht a. Sohwanert, Z. [2]
a, 684 ; A. 160, 177).
Properties. — Silky needles (from water or di-
lute alcohol) or monochnic tables (from absolute
alcohol) ; v. sol. alcohol.
Reactions. — 1. Nitric add oxidises it to benz-
oin and finally to benzil ^Zinin). — 2. Chromus
acid mixture forms benzoic aldehyde (Zincke,
A. 198, 121).-3. PCI5 forms (o). and (i8).di-
chlord-di-phenyl-ethane CeH5CHCl.CHCl.CsH5.
4. FBr, forms in like manner a bromide-
714
HYDEQBENZOlN.
C„H,sBri,— 5. jDUute ajSO, at 200° forms di-
phenyl-acetic aldehyde and an anhydride Ci^HijO
(Breuer a. Zineie,£. 11, 72 ; Weise, A. 248, 34).
Acetyl derivative
C,H5.CH{OAc).CH(OH).0,H5. [84°]. Promhy-
drobenzoin and HOAo at 180° (Limprioht a.
Bohwanert, A. 160, 190; Forsta. Zincke, A. 182,
254). Iiong needles (from aqueous HOAc), v. e.
Bol. alcohol, ether, and HOAc.
Di. acetyl derivative (CbH5)2C2Hj(OAo)2 :
[135°] ; formed by aeetylation of hycGrobenzoiin,
or by the action of zinc-dust on a mixture of
benzoic aldehyde and acetyl chloride (Faal, B.
16,636). Formed also from di-bromo-di-phenyl-
ethane CjH5.OHBr.CHBr.CeH5 and AgOAc (Lim-
prioht a. Sohwanert, A. 160, 177). Monoclinic
prisms (from ether) ; m. sol. cold alcohol, sol.
ether and benzene. POI5 converts it into (a)-di-
chloro-di-phenyl-ethaneOjH5.CHOl.CHCl.OaH5.
Benzoyl derivative
C.H5.0H(OH).CH(OBz).CjH5. [181']. Formed,
together with the di-benzoyl derivative by heat-
ing hydrobeuzoin (1 pt.) with Bz^G (3 pts.) at
160° (Forst a. Zincfce, A. 182, 277). Needles or
plates (from alcohol) ; v. sol. alcohol, ether, and
chloroform.
Di-bemoyl derivative
Ph.CH(OBz).CH(OBz).Ph. [246°]. Small white
needles, si. sol. most solvents. Formed , together
with the di-benzoyl compound of isohydroben-
zoin, by the action of zinc-dust on a mixture of
benzoic aldehyde and benzoyl chloride (Faal, B.
17, 909). Formed also by treating the compound
PhCHBr.CHBrPh with AgOBz (Forst a. Zincke,
A. 182, 277).
Ph.0H.O,
Carbonyl derivative
'\
CO.
Ph.dH.o/
[126°]. Obtained by the action of ClOOijEt on
the sodium derivative of hydrobenzoin, which is
itself got by heating hydrobenzoin in benzene
solution with sodium-amalgam (Wallach, A. 226,
81). Needles (from alcohol). Saponified by al-
coholic EOH.
Anhydride C„H,20 i.e. <CcPhH/^'' °^
PTTPI1 PTTPh
^^CHPh'cHPhi^^' ^■P^i^y^-^if'^^^"^ oxide.
[132°]. Formed by boiling hydrobenzoin with
dilate (20 p.c.) sulphuric acid, distilling off di-
phenyl-acetic aldehyde and extracting the resi-
due with ether. Monoclinic crystals (from ether).
Not volatile with steam. Insol. water, v. sol.
benzene,HOAc, andhot alcohol. At 250° it splits
up into s-di-phenyl-ethylene and benzoic alde-
hyde. Beactions. — 1. When heated for 17 hours
with BzjO at 240° it gives di-benzoyl hydrobenz-
oin and some s-di-phenyl-ethylene.— 2. HOAo
at 170° forms di-acetyl-hydrobenzoin. — 3. AcjO
does not act below 240°, at which temperature
it gives di-acetyl-hydrobeuzoin, s-di-phenyl-
ethylene, and benzoic aldehyde. — 4. BzCl gives
(o)-di-chloro-di-phenyl-ethanePh.CH01.0HCl.Ph
[192°]. PCI5 forms the same body.— 5. By heat-
ing for 8 hours at 200° with cone. HIAq and
phosphorus it is reduced to s-di-phenyl-ethane
[52°].— 6. CrOj in HOAo forms 0j,^0„ which
crystallises from hot alcohol in small felted
nfiedles [155°] and C,5H,sOj [145°] (Breuer a.
Zincke, A. 198, 169).— 7. Dilvite (20 p.c.) HjSO.
at 200° forms di-phenyl-aoetio aldehyde. —
8. HClAq (S.O. 1-19) at 170" gives di.phenyl-
acetic aldehyde and (a).di-c^loTO-di-phenyl.
ethane.
Isohydrobenzoin G^H^Oj i.e.
CeH5.0H(OH).CH(OH).CjH5. [120°]. S. -19 at
15°; 1-25 at 100°. Formed, together with a
smaller quantity of hydrobenzoin, when sodium-
amalgam acts on benzoic aldehyde in presence
of water. The presence of alcohol diminishes
the proportion of isohydrobenzoin to hydro-
benzoin (Ammann a. Fittig, A. 168, 70). The
separation may be effected by repeated crystalli-
sation from alcohol, in which isohydrobenzoin is
somewhat the more soluble. Formed also by
saponifying its di-acetyl derivative. Glistening
hydrated needles (froni water), anhydrous hexa-
gonal crystals (from alcohol), or monoclinic,
prisms (from ether). The hydrated crystals
melt at 96°. V. sol. alcohol, ether, and chloro-
form.
Beactions. — 1. POI5 gives (a)-di-chloro-di-
phenyl-ethane Ph.CHC1.0Hgi.Ph [184°], and a
resinous compound O^sH^gClO [150°] (Breuer a.
Zincke, A. 198, 167) ^. Boiling dilute HjSO,
forms di-phenyl-acetic aldehyde and the an-
hydride C„H,j,0 [102°].— 3. By heatingwith Bz^O
there is formed mono- and di-benzoyl-isohydro-
benzoin and also di-benzoyl hydrobenzoin.
Sodium derivative
Ph.CH(0Na).0H(ONa)Ph (?). In an ethereal
solution of isohydrobenzoin sodium-amalgam
forms a powdery sodium derivative. Some of
the isohydrobenzoin appears to be changed at
the same time into a crystalline isomeride [125°],
which is slowly dissolved by boiling water, being
changed to isohydrobenzoin.
Acetyl derivative
OjH5.CH(OH).CH(OAo).C5H5. [88°]. Formed
by the action of EOAc or of AgOAc on
Ph.CHBr.OHBr.Ph (Forst a. Zincke, A. 182,
282). Short thick needles.
Di-acetyl derivative
C,H5.CH(OAc).CH(OAc).C„H5. [118°]. Formed
by digesting isohydrobenzoin with acetyl chlor-
ide for 24 hours. Formed also by boiling
Ph.CHBr.CHBr.Ph (1 pt.) dissolved in HOAo
(3 pts.) with an excess of KOAc for 12 hours
(Zincke, A. 182, 262 ; 198, 154). Plates (from
alcohol). Occurs sometimes in trimetric prisms
[106°]. V. sol. alcohol, ether, and chloroform.
Benzoyl derivative
C„H5.CH(0H).CH(0Bz).C,H5. [130°]. Formed,
together with the di-benzoyl derivative, by heat-
ing isohydrobenzoin with excess of Bz^O at 160°
^Forst a. Zincke, A. 182, 285). Small needles
(from dilute alcohol). Y. e. sol. alcohol, ether,
and chloroform.
Di-benzoyl derivative C„H,j(0Bz)2:
[151°]; fine silky needles; v. e. sol. ordinary
solvents. Formed, together with the di-benzoyl
derivative of hydro-benzoin, by the action of
zinc-dust on a mixture of benzoic aldehyde and
benzoyl chloride (Paal, B. 17, 909). Formed
also, together with its isomeride, by heating iso-
hydrobenzoin with BzjO ; also by the action of
Ph.OHBr.CHBr.Ph on AgOBz.
Carbonyl derivative phnH 0^*^'^'
[110°]. Prepared by dissolving benzoic alde-
hyde and Cl.COjEt in ether and treating with'
sodium amalgam. A violent reaction occurs;.
HYDROCARBONS.
715
when it abates the flask is heated for some time
with inverted condenser. The liquid is filtered
and evaporated, the residue is crystallised from
alcohol. The yield is bad. Formed also by
treating the sodium derivative of isohydrobenz>
oin in ether or benzene with OlCOjEt, an inter-
mediate body Ph.0H(0C0jEt).CH(0C02Et).Ph
being perhaps formed. Monoclinic plates (from
alcohol). Insol. cold water, si. sol. boiling water.
SI. sol. cold alcohol or ether. Insol. CS^, sol.
benzene. Decomposed by boiling potash into
potassium carbonate and iso-hydro-benzoin. It
is not aSected by Ac^O. FClg converts it into
(o).di-chloro-s-di-phenyl-ethane [186°] (Wallaoh,
l.pr. [2] 25, 262 ; A. 226, 80).
Anhydride OnH,jO. [102°]. Formed,
like the corresponding anhydride of hydrobenz-
oiin, by boiling isohydrobenzoiu with dilute E^SO,
(Zincke a. Breuer). Monoclinic crystals (from
ether). More soluble in alcohol than its iso-
meride.
BeacUons. — 1. When heated with BzjO it
gives £-di-phenyl-ethylene and di-benzoyl-isohy-
drobenzoin. — 2. HOAc has no action even at
250°.— 3. AcjO does not act at 170°.— 4. BzCl
yields Ph.CH01.CHCl.Ph [192°]. PCI5 forms a
compound O^gH^ClO, which is finally converted
into Ph.CH01.CHCl.Ph.— 5. HIAqand P at 200°
forms-di-phenyl-ethane [52°].— 6. CrOsinHOAc
acts upon it in the same way as upon its iso-
uieride.
HYI)BOB£NZOlN-SI^.CABBOXyi.IC ACID
C,.H„0, i.e.
CeH<(C0jH).CH(0H).CH(0H).C„H,(C02H). Ob-
tained by reduction of the sodium salt of benz-
oiin-di-carboxylic acid with sodium-amalgam.
Infusible. Unsublimable (Oppenheimer, B. 19,
1817).
HTBBOBEBBESINE v. BEBBEamE.
HTDBOBBOmC ACID v. Bbouhydbio Acm,
vol. i. p. 532.
HYDBO-BBOHO-CINCHENE v. Cihobene
bbouoh^dbide.
HYSBO-BBOMO-CINCHONINE v. CmcHON-
INE BBOMOHTOBIDE.
HTSBOBTTIYBAIIIDE v. Isobuiybic aiiSE-
HTDE.
HYDBOBTITYBOFTJBONIC ACID OsH„Oj i.e.
C0»H.CK,.CH,.C0.CHj.CH,.0H,.CH2.C0^. An
indistinctly crystalline acid formed by reducing
butyro-furonio acid CjHijOsWith sodium-amal-
gam (Tonnies, B. 12, 1201).— Ag^A".
ETDBO-CAEFTTBIC ACID v. Capfeine.
HYDBOCAUFHEIfE v. Decinen]s.
HTDBOGABBONS. Compounds containing
carbon and hydrogen only. Liquid hydrocar-
bons, especially terpenes C,oH,g and their iso-
merides, are commonly found in essential oils
from plants ; solid hydrocarbons have been ob-
tained from the fruit of Beracleum Sphondylmm,
H. giga/ntewm, Pastinaca satima, and from other
plants (Guthzeit, B. 21, 2881). The chief source
of hydrocarbons is, however, the dry distillation
of organic bodies, the nature of the product de-
pending upon the temperature at which the
distillation takes place, since a red heat tends
to deprive hydrocarbons of a part of their hy-
drogen. Thus when coal is distiUed at the
lowest possible temperature, the distillate con-
sists chiefly of paraffins and defines ; whUe dis-
tillation at a bright-red beat forms large quan-
titles of aromatic hydrocarbons. Ameiican
petroleum, formed by the slow decomposition of
vegetable matter under the surface of the earth,
probably at a moderate temperature, is very
largely composed of paraffins (c/. Engler, B. 21,
1816).
The hydrocarbons are insoluble in water;
they are neutral, and do not form salts with
acids or alkalis; they are not saponified by
boiling with dilute acids or alkalis, and are for
the most part not affected by that treatment.
They do not unite with alkaline bisulphites, nor
do they react with hydroxylamine or phenyl
hydrazine.
According to Berthelot (C. £. 84, 714) when
liquid hydrocarbons are decomposed by passing
powerful induction sparks through them the
gases given ofC consist of hydrogen, methane,
ethane, ethylene, and acetylene, but no hydro-
carbon of higher molecular weight; carbon is
deposited in the case of terpenes and aromatic
hydrocarbons, but not from paraffins.
The hydrocarbons with which bromine com-
bines even in the dark are known as unsaturated
fatty hydrocarbons ; the remaining hydrocarbons
may be divided into saturated fatty hydrocarbons
and aromatic hydrocarbons, which may be dis-
tinguished by treatment with fuming nitric acid,
which forms nitro- derivatives with aromatic hy-
drocarbons, but never does so with the saturated
fatty hydrocarbons.
The saturated fatty hydrocarbons are also
called paraffins, andcontaina larger percentage
of hydrogen than any other hydrocarbons ;''they
may be included in the general formula C^Hj,^,-
Unsaturated fatty hydrocarbons of the formula
C„H2„ are called defines, since olefiant gas is
the first member of the series. Of the hydro-
carbons C„Hg„.2 those which give pps. with am-
moniacal solutions of cuprous chloride and of
silver nitrate are held to contain the group C:CH
and belong to the acetylene series.
Vowel nomenclature, first proposed by Lau-
rent in naming the chlorinated derivatives of
naphthalene, was adopted by Hofmann to dis-
tinguish the different classes of hydrocarbons.
Thus, according to Hofmann, the names of the
compounds :
CjHai+j end in - ane
0„H^
— ene
— ine
C„Ha,-2
0„Ha.-4 •! -one
C„H2„., „ -una.
Inasmuch as ine is the usual termination of
bases, and one that of ketones, in this dictionary
the names of unsaturated hydrocarbons have
been made to end in ene, thus : <
Hydrocarbons C„Hj„ end in — ylene .
„ 0„Ha,.j „ -inene
» ^^^-A « -onene
„ 0„H2„.a „ -unene.
Paraffins. The saturated fatty hydrocarbons
or paraffins are named as follows :
Methane CH,
Ethane C^H,
Propane CgH,
Butane C,H„
Pentane C^H,,
Eexane CSgH^
Heptane C^,,
Octane C^u
716
HyDROOARBONS.
Bunane or Konane
C.H,.
Decane
C,„Ha
Eendeoane
or tJndecane
OijHjj
Dodecane
CijHj,
Tridecane
CisH,,
Tetradecane Gi^Hg,
Pentadecane C,jHj2
Hexadecane
C,»H,.
Eeptadecane C„Hj^
Oetodecane
C,sH3,
Bnndecane
C19H4J
looEane
^20^42
, Eenicosane
CjiHj,
Do-icosane
c,^„
Tri-ioosane
C^H„
THacontaue CjoHg,.
From a Btructural point of view any para£Bn
may be regarded as formed from the next lower
Uomologae by displacement of H by CH,. As
the hydrogen atoms in methane are similarly
situated there can be only one ethane, and as the
atoms of hydrogen in ethane CH3.OH3 are simi-
larly situated there can . be only one propane.
But in propane CH3.CH2.0H,it is possible to dis-
place a hydrogen atom either in the methylene
group CE2 or in one of the two methyl groups ;
thus we arrive at two butanes : CH,.CH(CH,).CH3
and CH3.CHj.CHj(CH3).
Proceeding in this way we find that there are
theoretically possible 3 pentanes, 5 hexanes, 9
heptanes, 18 octanes, 85 ennanes, 75 decanes,
159 hendecanes, 355 dodecanes, 802 tridecanes,
&e.
The paraffins are said to be normal when
they contain only two methyl groups, and may
consequently be represented by a chain that has
no branches, e-jr. CHs.CHj.CHj,.CH2.CHj.CHj.
The boiling-points of the normal paraffins are :
Pentaue (37°)
Hexane (70°)
Heptane (99°)
Octane (124°),
after which they rise 19° for each increment of
CH,. The other paraffins boil at lower tempe-
ratures than their normal isomerides.
Occwrrenee. — Among the products of the
destructive distillation of coal, bituminous shale,
peat, &o., and in American petroleum. Natural
or artificial petroleum yields on distillation : (a)
petroleum ether or ligroin boiling from 35° to
90°, containing chiefly pentane, hexane, and
heptane ; (6) benzoline or petroleum spirit, boil-
ing from 90° to 150° and containing heptane,
octane, and ennane; (c) kerosene, petroleum-
naphtha, or paraffin oil boiling from 150° to
20U°, containing decane, hendeoane, and dode-
cane; {d) solid paraffinwax, a mixture of saturated
liydrooarbons of stUl higher molecular weight
(GreviUe WUliams, Tr. 1857, 737 ; C. J. 15,180 ;
Schorlemmer, C. J. 15, 419 ; Felouze a. Cahours,
A. 124, 289 ; 127, 196 ; 129, 87).
Formation. — 1. By distilling the acids
0„H2„02 with excess of potash, Imae, or baryta.
2. By the action of water on the zinc alky Is;
thi^ reaction may be carried out by simply heat-
ing the alcoholic iodide with zinc and water, or
by treating them with the copper-zinc couple in
presence of water or alcohol. — 3. By the reduc-
tion of the chlorides or iodides of alcohol radicles
by zinc and hydrochloric acid, by HI, or by
sodium-amalgam. — 1. By the action Of dodiuai
or of reduced silver on an iodide or mixture of
iodides EI + E'I + Naj = 2NaI + EB'. This pro-
cess is known as Wurtz's reaction (Wurtz,
A. Oh. [3] 44, 275).— 5. By the action of
alcoholic iodides on zinc-alkyls. — 6. By the
electrolysis of the sodium salts of the fatty
acids.
Properties. — Methane, ethane, propane, and
butane are gaseous at ordinary temperatures;
the specific gravity of the higher paraffins in the
liquid state steadily rises with increasing mole-
cular weight. The paraffins are distinguished
by their chemical indifference (jgarwm affirm).
They are not attacked by KOH, by H^SO^, or by
cold fuming HNO,.
Beactions. — 1. Chlorine acting on a normal
paraffin forms only primary and secondary
chlorides, the latter containing the group
CHOI.GH3. Bromine forms, however, only
secondary bromides of similar constitution
(Schorlemmer). The isomeric mono-chlorin-
ated paraffins got from petroleum yield, by
abstracting HCl, a mixture of olefines one por-
tion of which combines readUy with cold HCl,
whilst the rest only combines on heating. The
chloro- derivatives formed in the cold distil
with partial decomposition and at a lower tem-
perature than those formed by heating. The
latter distil without decomposition and have the
general formula CHj.CHC1.C„K„^h (Schor-
lemmer, C. /. 26, 819 ; Pr. 29, 364 ; T. 171,
451 ; Morgan, C. J. 28, 301 ; Le Bel, Bl. [2] 28,
460). — 2. Bromine does not act upon them in
the dark, in sunlight its colour disappears, a
molecule of HBr being formed for each molecule
of bromine used up. — 3. Sypochlorous add does
not unite with paraffins.— 4. Ch/romic acid and
hot nitric acid (S.G. 1-4 to 1-5) oxidise them to
CO,, forming in some cases intermediate fatty
acids (Schorlemmer, Pr. 16, 373).
Olefiuea C^H,,,. The names of the olefines
are: —
Ethylene C^H,
Propylene CjH,
Butylene C,H,
Amylene C^H,,
Hexylene CjH,j
The higher members are named by writing
-ylene in place of the -aue in the names of the
paraffins {v. supra). Methylene CH, does not
appear capable of existing ; in reactions where it
might be expected ethylene is formed instead.
It will be observe that the olefines have all the
same percentage composition. The hydrocarbons
in Caucasian petroleum, although isomeric with
the olefines, appear to be hexahydrides of the
homologues of benzene (Markownikoff, B. 20,
1850).
Formation. — 1. By dehydration of the
saturated fatty monohydric alcohols CoH^^j^-
This may be done by means of H^SO^, ZnClj, or
PjOj. In the case of the higher alcohols a
mixture of hydrocarbons is, however, produced.
2. By the action of alcoholic KOH on the alkyl
iodides. — 3. By passing alkyl chlorides over red-
hot lime. In some cases mere distillation is
sufficient to split up the alkyl chlorides into
olefine and HCl.— 4. A large number of olefines
are produced in the manufacture of illuminating
gas from oil (Armstrong, C. J. 49, 74), — 5. By
HYDROCARBONS.
717
tbe electrolysis of the alkaliae salts of dibasic
tatty acids.
BeacUons. — 1. The defines combine readily
vnth chlorine, bromine, and iodine forming oily
compounds {e.g. Dutch liquid); hence their
name.— 2. They combine with SO,, and are
therefore absorbed by Nordhausen sulphuric acid.
Cone. H2SO4 forms alkyl sulphuric acids. —
3. They combine with HCl, HBr.and HI. Cone.
HIAq, however, at 100°, soon reduces them to
paraffins. Olefines of the formula CHjiCHE
combine with HCl only on heating (Le Bel, Bl.
[2J 28, 460). Those of the formula CH^rCEB'
or CHR:CHE' combine with cold HCl (Le Bel ;
cf. Sohorlemmer a. Thorpe, A. 217, 151).—
4. Alkaline KMnOj oxidises them to oxalic,
acetic, formic, carbonic, and other acids (Ber-
thelot, O. a. 64, 35). — 5. Many olefines may be
oxidised by CrO, to aldehydes or ketones (Ber-
thelot, C. B. 68, 334).— 6. HCIO unites forming
chlorhydrins of dihydric alcohols or glycols. A
very simple method of preparing hypochlorous
acid for employment in the preparation of or-
ganic chlorhydrins consists in acidifying a solu-
tion of bleaching powder with boric acid. The
theoretical quantity of the unsaturated organic
compound is then added, allowed to sta&d for
some time in the dark, and the ohlorhydrin ex-
tracted with ether (Lauch, B. 18, 2287).— 7. The
olefines are prone to polymerisation especially
iin presence of ZnCl^ or H^SO,.
Acetylene series C„Ha,.j. The hydrocar-
bons C^Hj,., may be divided into (a) acetylenes
proper : B.CiCH ; (6) dialkyl - acetylenes :
BCiCB' ; (0) di - ethylenic hydrocarbons :
BCH:CH.CH:CHB' ; and <d) isoaUylenes :
BB'C:C:CB"B"' (cf. Bdhal, A. Oh. [6] 15, 268).
WormdUon. — 1. By heating bromo-olefines, or
the dibromides of olefines with alcoholic potash.
Thus they may readily be obtained from alde-
hydes and ketones by successive treatment with
PCI5 and alcoholic potash. — 2. By electrolysis of
the sodium salt of unsaturated dibasic acids. —
3. In the destructive distillation of organic
bodies, and in the incomplete combustion of
coal-gas.
BeacUons. — 1. The hydrocarbons BC:CH
form pps. in ammoniacal solutions of cuprous
chloride and of silver nitrate. These pps. are
decomposed by HCl with liberation of the hy-
drocarbon.— 2. They combine with either one
or two molecules of bromine, HCl, HBr, HI, and
HOCl. — 3. By successive treatment with HjSO^
and water they can be hydrated; acetylene
changing to aldehyde, and allylene to acetone. —
4. The hydrocarbons BC:CH give pps. in an
aqueous solution of HgClj ; when the product is
treated with acids aldehydic or ketonic products
of hydration are liberated (Kutscheroff, B. 17,
13).— 5. A saturated alcoholic solution of AgNO,
gives crystalline pps. with acetylenio hydrocar-
bons ; thus heptinene gives C,H„AgAgN03 which
deflagrates when heated (BdhaX, A. Oh. [6] 15,
423).— 6. KMnO, and chromic acid attack the
hydrocarbons at the unsaturated point ; thus
diallyl gives CO, and succinic acid. BShal
(A, Oh. [6] 16, 368) thinks that no hydrocarbon
of the isoallylene type has as yet been isolated.
Thus by heating CHjCl.CH:CH01 in dry benzene
with sodium he failed to obtain isoallylene. He
was equally unable to obtain GB^.Q:GUt by beat-
ing CHiCLOChCH, with sodium; while ally!
iodide heated with FbO in excess only gave
propylene ; and by heating with HgO, CuO, or
AgjO at 125°-160°, CO is formed, but no iso-
allylene. When allyl alcohol is dehydrated by
P^O, no trace of isoallylene is obtained, the pro-
ducts being ethylene and propylene. Ethyl allyl
oxide behaves in like manner, the decomposition
proceeding with greater regularity (B^hal, A. Oh.
[6] 16, 360). According to Gustavson {/. pr. [2]
38, 203), however, isoallylene can be obtained by
the action of zinc-dust on di-bromo-propylene
CHjBr.CBr:CHj in presence of alcohol. He de-
scribes it as a gas which unites with bromine
forming C^H^Br^, and which, when treated with
H^SO, and water successively, yields acetone.
Benzene series CgH,,.^- ^^e hydrocarbons
of this series are named as follows : —
Benzene CgHj
Toluene C,H, or CjHj.CH,
Xylene C,H,„ or C„H.,(CH3)j
Mesitylene and ifi-oumene OjPu or C,H3(CH,),.
Durene C,„Hn or C|iHj(CHj)4.
Propyl-benzene is called cnmene, and propyl-
toluene is called cymene, the other members being
usually named as substitution derivatives of
benzene. Their constitution is discussed under
Benzene (q, v.).
Occurrence.— In coal-tar, in Galician petro-
leum, and as hydrides in Caucasian petroleum.
FormaMon. — ^1. By distilling their oarboxylic
acids with lime.— 2. By adding strips of sodium
to an ethereal solution of a mixture of an aroma-
tic bromide and an alkyl iodide (or bromide)
(Fittig's reaction). This reaction takes place the
more readily the higher the molecular weight of
the alkyl iodide, and where there is already a
side chain it succeeds best when this is in the
para- position (Krafft a. Gottig, B, 21, 3184). —
3. By adding AlCl, to a mixture of an aromatic
hydrocarbon with an alkyl chloride, HCl being
evolved (Friedel a. Crafts, A. Oh. [6] 1, 459 ; 14,
457 ;.c/. Aluminium omiOEiM!, vol. i. p. 147).
Friedel a. Crafts consider that this reaction
takes place in two stages :
CA+ A1,C1,- C,H,Al,Cl5 -I- HCl
CAA1,01, + ECl = CeH5B-l-Al,Cl,
the latter reaction being analogous to
ZnEtj + 2EC1 = 2BtE + ZnCl^
They have, however, hitherto failed to isolate
the hypothetical intermediate body CgHsAlgCl,,
but they have equally failed to obtain the com-
pounds AlCl,(CsH,), and AlBr,(C,H,), described
by Gustavson (J. B. 1882, 354), which they re-
gard as mixtures. When MeCl acts on benzene
(5 pts.) containing AlCl, (1 pt.) there is formed
s-durene. MeCl acting on toluene in presence
of AlCl, forms 0-, m-, and p- xylene, ilr-omnene,
mesitylene s- and u- durene, penta-methyl-benz-
ene, and hexa-methyl-benzene (Ador a. Eilliet,
B. 12, 329 ; O. Jacobsen,^. 14, 2627). MeCl and
AlCl, converts the three xylenes into t|r-cumene,
7»-xylene giving also mesitylene. The higher
homologuesof benzene are more readily methyl-
ated than the lower. Ethylene passed through
a heated mixture of benzene and AlCl, gives
ethyl-, di-ethyl-, and tri-ethyl-benzene (Balsohn,
Bl. [2] 31, 539). Isomeric changes often occur
in these syntheses. Thus isobutyl bromide
(300 g.) acting on benzene (900 g.) and Aid,
(300 g.) at 0° forms <er(-butyl-benzene (l&7°at
718
HYDROCARBONS.
736 mm.), -which is also got from tert-hntjl
chloride ; while w-butyl chloride gives sec-butyl-
benzene (174° at 735 mm.) (Schramm, M. 9, 613).
In like manner isoamyl chloride gives an amyl-
benzene (188° at 737 mm.) which appears to be
CjHs.OHMePr or OjHs.CMejBt. w-Propyl brom-
ide gives isopropyl derivatives, since PrBr is
changed to PrBr in presence of AlCl, (Kekuld a.
Sehrotter, B. 12, 2280). Schramm supposes the
alkyl chloride to be split up into HOI and olefine,
the latter then acting like ethylene (v. supra).
By the action of AlCl, on boiling toluene there is
formed benzene, ethyl-benzene, and the three
xylenes (Friedel a. Crafts, G. B. 101, 1218). In
a similar manner m-xylene is converted byAlCl,
into benzene, toluene, mesitylene, and i^-cumene;
while ethyl-benzene gives benzene and di-ethyl-
benzene (Anschutz a. Immendorff, B. 17, 2816 ;
18, 657). - The transference of side chains may
be readily effected by passing HCl through the
heated mixture of AlClj with the hydrocarbon,
e.g.
CsHaMe, -t- HOI = C,H,Me2 + MeCl
CjHjMej + MeCl = OjHjMe, + HOI
(Jacobsen, B. 18, 343).— 4. When aromatic hy-
drocarbons are heated with Mel or EtI and
iodine in sealed tubes at high temperature. Me
or Bt can be introduced, although very many
other products are formed at the same timei. In
this way benzene heated with Mel gives toluene,
toluene (with Mel) gives xylenes, and hydrocar-
bons 0,H,2, C,gH,4, and C„H„; while psendo-
cumene mixed with mesitylene (with EtI) gives
C^H^MejEt (here Et turns out Me) (Bayman a.
Preis, A. 223, 315). — 5. By heating ketones with
H^SO,; thus acetone gives mesitylene.— 6. By
heating benzene and its homologues with ZnClj
and (the higher) fatty alcohols, water being
eliminated (Goldschmidt, B. 15, 1066).— 7. By
heating diazo- compounds with alcohol. — 8. By
boiling hydrazines with OuSO, or EeOl,.
BecLctions. — 1. Fuming niiric acid dissolves
them, and on adding water nitro- derivatives are
ppd. — 2. Fuming sulphuric acid dissolves them,
forming sulphonic acids. By distilling the re-
sulting sulphonic acids with superheated steam
the hydrocarbons can be recovered, and thus
separated from fatty hydroo3,rbons, and even
from one another (Beilstein, A. 133, 84 ; Arm-
strong a. Miller, C. J. 45, 148 ; Kelbe, B. 19, 93).
3. Halogens form products by substitution.
Heat and direct sunshine both cause the halo-
gen to enter the side chain instead of the benz-
ene nucleus (Schramiu, B. 19, 212 ; M. 8, 299).
Yellow light has the maximum effects. Accord-
ing to Eadziszewski (.4. 218, 386) the halogens
acting upon alkyl-benzenes go in the cold into
the p- position ; as the heat is raised they go
into the o- position, then into the CH^ attached
to the CjHs, and at a still higher temperature
into the next CH^, and so on {v. Cbloko- com-
FouNDs, and Bbouo- compounds). — 4. Chromie
acid mixture oxidises all the side chains to
carboxyl, while nitric acid (S.G. 1-2) frequently
attacks only one side chain. In the oxidation by
means of dilute HNOjOf the di-alkylated benzenes
it has usually been assumed that the longest side
chain is oxidised first, becoming CO^H. This is
not always the case, for m- and ^-iso-bntyl-
toluenes give isobutyl-benzoio acids, and the
oxidation of all such hydrocarbons ia greatly
modified by the introduction of halogens into the
ring, thus tetra-chloro-m-isooymene can only be
oxidised with very great difficulty, and then is
entirely broken up (Kelbe a. Pfeifier, B. 19,
1723). Propyl-isopropyl-benzene is oxidised to
w-propyl-benzoio acid. — S. Chromiyl chloride
forms addition compounds C„Hj„.„(Cr02Clj)j.
These compounds give ofi HCl at 200°, becoming
CjHj^.BfCrOjCl)^. If they contain methyl they
are converted by water into aldehydes. In the
case of benzene, water produces quinone (6tard,
A. Ch. [5] 22, 218 ; C. B. 87,989).— 6. By heat-
ing with HIAq the hydrocarbons CoHa,., can be
made to take up 2, 4, or 6 atoms of hydrogen.
The hydrides C„H2,.|jH8 occur in Caucasian
petroleum (Beilstein a. EurbatoS, B. 13, 1818)
and may also be obtained by the distillation of '
colophony (Benard, A. Ch. [6] 1, 227).
Homolognes of Anthracene C^Hj,.,, may be
formed as foUows : 1. From anthranols by ab-
straction of water (Liebermann a. Tobias, B. 14,
795). — 2. From halogenated hydrocarbons, by
heating under pressure (Dorp, A. 169, 210).—
3. From halogenated methanes, aromatic hydro-
carbons, and AICI3 (Anschiitz a. Bomig, B. 18,
664; Elbs a. Wittich, B. 18, 348).— 4. From
homologues of diphenylmethane by abstraction
of hydrogen (Weiler, B. 7, 1185 ; Fischer, B. 7,
1195). — 5. From homologues of o-tolyl-phenyl
ketone by abstraction of water (Behr a. Dorp, B.
7, 17 ; mbs, J. pr. [2J 33, 186).— 6. Phthalio an-
hydride, aromatic hydrocarbons, and AlCl, give
homologues of o-benzoyl-benzoic acid, whence
by cone. HjSO, homologues of anthraquinone
may be obtained. Thus toluyl-benzoic acid
[2:l]CjH,(C02H)OO.OeH,(OH,)[l:4]fromphthaUo
anhydride and toluene gives (B. 2)-methylran-
thraquinone [175°], while m-xyloyl-o-beuzoio acid
gives a dimethytanthraquinone [162°] (Elbs,
J.Jir. [2]33, 318).
Hydrocarbons of the tri-phenyl-methane
series C„Ha,.jj (Elbs, J.pr. [2] 33, 181) may be
formed as follows: 1. From chloroform orohloro-
picrin, benzene or homologues of benzene, and
AlCl,. — 2. From benzylidene chloride, benzene
or homologues of benzene, and zinc-dust. — 3.
From secondary aromatic alcohols, aromatic
hydrocarbons, andPjOj (best method).— 4. From
aromatic (i3)-pinacolins and alkalis (Thorner a
Zincke, B. 10, 1475; 11, 65).— 5. From benzyl-
idene chloride (or its homologues) and Hg(0,H5),
(or its homologues). — 6. From benzoic aldehyde,
benzene or its homologues, and ZnCl, at 250°.
HTSBOCABBOSTYBIL v. o-Ainno-jS-FHEim-
PBOPIOmO AOID.
DI-HYDBO-CABBOXYLIC ACID (so-called)
V. Tbtra-oxt-qthnone.
Tri-hydTO-carbozylic acid (so-called) v.
Hbxa-oxt-benzene.
HTBBO-CABOTINE v. CaSboiin.
HYSBOCHELIBONIC AGIO v. CHELmoma
ACID.
HYBBO-CHIOBANILIC ACIB v. Di-ohlobo-
tetba-oxt-benzene.
HTBBOCHIiOBIC ACID v. Gblobh^deio
Aon>, p. S.
HYDBOOHLOBOCABVOL v. Cabtoi. chlobo-
HIDBIDB.
HYDBOCHLOBOGINCEOSriNE v, ClNCBomNB
OBIiOBOSXDBISB.
HYDEOGEN.
719
HYDEOCHLOROCONQTJINmE v. Cinohona
BABES.
HTDBOCIITCHOITISIITE v. Cinchona bases.
HTDSOCIKCHONUTE v. Cinohona bases and
CnjOHONINB.
HYDBOCINNAHENYL-ACRYLIC ACID v.
PhBNYIi-PENTENOIO AOID.
HYDBOCINNAMIC ACID v. Phentl-pro-
FIONIO ACID.
HTDEOCINNAMIDE Cj,Hj,N, t.e.
N2(0H.CH:CHPh)s. [106°]. White needles.
Formed bjr the action of NH, on an alcoholic or
ethereal solution of cinnamio aldehyde. It is
very stable towards HOI at a high temperature.
Salts. — ^B'HClSaq: flat colourless tables:
[220°] ; sol. alcohol and chloroform, insol. water,
ether, benzene, and ligroin. — B'^BaCl^PtCl,
(Laurent, Bev. Scient. 10, 119 ; Peine, JB. 17,
2110).
HYDBOCOLLIDIITE v. Tbi-uethyl-fyridinb
HYDBIDE.
HYDBOCONQiriNINE v. Cinchona bases.
HYDBOCOBiriCTTLAEIC ACID v. Cobnicu-
LABIC ACID.
HYDBOCOTABNINE v. Nabootine.
EYDBOCOTOIN v. Coto babe.
HYDBOCOTONE v. Coio babe.
HYDSO-jj-COUIIABIC ACID v. p-Oxt-P-
PHENTL-PKOPIONIO ACID.
EYDBOCOUIIABILIC ACID v. CouiiABii.ia
ACID.
HYDBOCOUMABIH v. Anhydride of Oxy-
PBENYL-PBOPIONIC ACID,
HYDBOCBOCONIC ACID v. Sydride of Cbo-
OONIC ACID.
HYDBOCUMINOiN v. CunnNoiN.
HYDEO-if'-CTIMOQTTINONE C5HMe3(0H)3
[1:2:5:3:6]. [169°]. Formed by reducing ifr-
oumoquinone (Nolting a. Baumann, B. 18,
1152). Needles (from water) ; si. sol. cold, t.
sol. hot, water.
HYDBOCYANAIDINE v. vol. i. p. 104.
HYDBOCYAlfIC ACID v. Cyanhydbic acid,
p. 300.
HYDBOFEBBICYANIDES v. Febbioyanides,
p. 337.
HYDBOEEBBOCYAmDES v. Febbocyanides,
p. 333.
HYDBO-FEBtJLIC ACID v. Methyl derimatme
of Dl-OXY-PHENYIi-PBOPIONIC ACID.
HYDBOFIiXrOBOEIC ACID v. BoBorLTroBHY-
DBIO ACID, vol. i. p. 526.
HYDEOFLUOBIC ACID v. Fluobhydbio acid,
p. 558.
HYDBOFIUOSILICATES v. Fluosilioates,
nnder Simoates.
HYDBOGAXiLEIIir v. Gallein.
HYDBOGAEDEKIC ACID c. Gabdenin.
HYDEOGEN H. At. w. 1. Mol. w. 2. S.G.
(air = 1) -06926 (Eegnault, at 0° and 760 mm. At
sea-level latitude of Paris). Eatio of S.G. of H
to that of 0 = 15-884 (Bayleigh, N. 3r, 418; 39,
462). S.G. at 3,000 atmos. (water = 1) = -0887
(Amagat, C. B. 107, 522). S.G. liquid at
0° = -025, at -23° = -082 (Cailletet a. Haute-
feuille, C. B. 92, 1086). S.H. 2-411 referred to
equal weight of water; -99 referred to equal
volume of air; ratio of S.H.'s at constant pres-
sure and constant volume 1-3852 (Clausius,
Mecham..Wamnetheorie,l,&i). C.B. (0°tolOO°)
H)036678 (constant volume) ; -0036613 (constant
pressure) (Eegnault, A. Ch. [S] 5, 52). S.
(0° to 20°) -0193 ; S. (alcohol atO°) -0BQ25 (Bun-
sen, Gasomet. Methoden, 154).
Compressibility-coefficient 1000-1600 atmos.
•000408, 1500-2000 atmos. -000272, 2000-2500
atmos. -000197, 2500-3000 atmos. -000158 (Ama-
gat, C. B. 107, 522). On the compressibility of
H for temperatuies from - 183° to -i- 100° and
pressures from 1 to 70 atmos. u.Wroblewski (Mj
9, 1067; or Natwre, 39, 583). H.C.p. [H=,0]
= 68,860 at o. 18°, product liquid HjO;
[H«,0] = 57,903 + 1-6 f, elements and product
gaseous (Thomson). Chief lines in emission-
spectrum Ho 6562-1, H3 4860-7, H7 4389-3,
HS 4101-2 (Angstrom, Svecire solai/re, Upsala,
1868).
The recognition of H as an individual gas
was made by Cavendish in 1766. The name
hydrogen was given by Lavoisier.
Oeov/rrence. — In small quantities in the gases
from volcanoes and fumaroles (Bunsen, P. 83,
167). In the gases issuing from the salt beds at
Stassfurt (Eeichardt, Ar. Ph. [2] 103, 347;
Precht, B. 13, 2326) ; and at Wieliczka (H. Rose,
P. 48, 353). Also condensed in certain meteorites
(Graham, Pr. 15, 502 ; Mallet, Fr. 20, 865). In
the intestines of several animals, produced by
decomposition of organic material (Tapp^iner,
B. 14, 2375). Occurs also in the sun and many
fixed stars. Compounds of H occur in large
quantities ; the chief compound is water ; H is'
a constituent of almost all organic matter; com-
pounds of H with 01, S, and N also occur in
fairly large quantities.
WormaUon. — 1. By electrolysis of acidulated
water. — 2. By the reaction of many metals with
HjO ; E, Na, and other alkali metals' decompose
cold HjO rapidly, forming hydroxides and H;
Zn, Fe, Mg, Al, and many other metals decom-
pose steam, forming oxides and H. — 3. By pass-
ing steam over hot C, COj is also formed. — 4. By
heating CaO^H,, BaOjHj, NaOH, or KOH, with'
C; C-l-CaO + 2H20 = qaCO, + 2Hj.— 5. By the
reactions of many metals with dilute solutions
of acids, especially of HOI and H^SO,; HNOj
cannot be used, as oxides of N are produced.
6. By heating KOHAq with Zn and Fe, or with
Al, or Mg, or certain other metals.— 7. By de-
composing NH, salts (not NHjNOjj) in solution
by Zn ; the action proceeds at c. 40° (Lorin,
C. B. 60, 745). — 8. By heating alkali formates
or oxalates with KOH.
PreparaUon. — 1. Pure granulated zinc is
placed in a capacious flask, and a cold mixture of
about 1 yoLpv/re H2SO4 witho. 8 vols. H^O isadded.
Addition of a little^itre CuSO^Aq prevents evo-
lution of fljS (by forming CuS) which may be
produced even witii pure acid and Zn (Lowe,
D. P. J. 211, 193). The contents of the flask
must remain quite cold during the process ; jf
temperature rises, traces of HjS and SO, begin
to be evolved. The gas is passed through (1)
cone. KMnOjAq to remove traces of AsH„ SbHj,
and PH, (Sohobig, J. pr. [2] 14, 289); (2) a U
tube containing pumice soaked in AgNOjAq or
HgCljAq to remove the last traces of H2S,AsH3,
&a., the pumice should be first moistened with
HjSOj and strongly heated in a crucible, to re-
move chlorides ; (3) a U tube containing pulmice
or glass beads moistened with cone. KOHAq to
reinove anj^ acid that may bavQ b$en Q^rneiJ
720
HYDROGEN.
ovei from the generating flask ; (4) a series of
tubes containing (a) dry CaCl, in small lumps,
(&) dehydrated, white CixSO,, (c) a considerable
length of FgO,. If the E is not required to be
dry the last series of tubes will he omitted. If
the H is to be used for reducing metallic oxides,
&e., Winkler recommends to pass it through a
red-hot tube packed with iron-wire gauze rolled
together (B. 22, 896 note).— 2. Pure KOHAq is
heated with pieces of Al; the gas is passed
through the same purifying tubes as 1, omitting
the EOH tube. — 3. By heating a mixture of
HCOjK and EOH, or CjO^Kj and KOH :
2HC0,E + 2K0H = 2KjC08 H- iK^iCfiJH^ -f- 2K0H
= 2K,003 + H,(c/,Pictet, A.Ch. [5] 13,216).—
4. By electrolysing 10 p.o. pure B^SOjAq, the
positive electrode being immersed in a mass of
liquid Zn-omalgam (v. Analysis, vol. i. p. 240).
Properties. — A colourless, tasteless, odourless,
gas ; liquefied under great pressure and at a very
low temperature. Olzewski (C. B. 98, 913 ; 99,
133) liquefied H by surrounding the gas with N
boiling m vacuo, the temperature of the N was
— 213°; the liquid E appeared as colourless
drops on the sides of the tube. According to
Olzewski the critical temperature of E is lower
than —198°; Sarrau gives — 174-2° as the cri-
tical temperature (O. B. 94, 639; 718, 845).
Wroblewaki (M. 9, 1067) gives critical tempera-
ture —240° ; critical pressure 13-3 atmospheres;
and critical volume -00335. If these results are
confirmed, they show that Fictet's statement
that H is liquefied at —149° is erroneous.
Fictet (0. B. 86, 106) subjected E at o. -140°
to a pressure of 360 atmospheres ; on opening
the stopcock an opaque steel-blue jet issued;
Fictet describes the fall of this jet on the floor
as producing a sound like the rattling of shot.
Oailletet obtained liquid E by suddenly reducing
the pressure on the gas at 300 atmospheres
(A. Ch. [5] 15, 132).
E is the lightest known substance ; 1 litre at
0° and 760 mm. at the latitude of 45° weighs
■08952289 gram (mean of results of Begnault
[Acad. 21, 158] and Jolly [W. 6, 520]). B is about
14^ times lighter than an equal volume of air,
11,160 times lighter than water, 151,700 times
lighter than Eg, and 236,000 times lighter than
Ft. H is only v. si. sol. water. It diffuses rapidly
through porous membranes, such as porcelain
or paper; also through several metals at red
heat (Graham, Pr. 15, 223 ; 16, 429 ; 17, 212,
600).
Large volumes of E are absorbed by Fd
and several other metals, especially when the
metal is made the negative electrode in the elec-
trolysis of EjO. Graham {Fr. 15, 502 ; 16, 422)
found that Pd foil which had been heated m
vacuo occluded 376 vols. E at the ordinary tem-
perature, 643 vols, at 90°-97°, and 526 vols, at
245°. A Pd wire used as the negative electrode
in electrolysing water occluded 935 vols. E, and
increased in length from 609-14 mm. to 618-91
mm. From such data Graham calculated the
S.G. of the occluded E to be -733 ; later deter-
minations by Dewar gave -62 (P. M. [4] 47, 324).
V. mfra Etdboqenium. According to Troost a.
Eautefeuille (O. B. 78, 968) Fd and E form a
definite compound Fd2E ; they think that this
componnd is formed when E is occluded by Pd,
and the compound then oontinnes to ooclude or
absorb more B. T. a. B. heated the Fd whioL
had occluded E in a closed space in connexion
with amanoineter, a portion of the E was evolved
without establishment of any definite relation
between the pressure and temperatuire, but when
the E remaining was in the ratio E:2Pd, a defi-
nite relation was established between pressure
and temperature, ao that for each temperature
there was a certain pressure whereat evolution
of E ceased, and this pressure was independent
of the relative masses of E and Pd. According
to Pavre (0. B. 77, 649 ; 78, 1257) for each gram
of E occluded by Pd, about 9,000 gram-units of
heat are produced. T. a. B. found that E and
Na also occlude B, 1 vol. of E occluded 126 vols.
Eat 0. 300°, the formula E^B requires 124-6
vols. E. Na also seems to form a compound
NajB. Li at 500° and 760 mm. occluded 17
times its volume of B; Tl only 3 times its
volume. (For the dissociation-pressures of the
compounds PdjB, E^E, and Na^E v. Dis'socuiioh,
p. 398 ; for more details as to the properties of
these bodies v. Palladiuu, FoiAssitm, Sodhtm.)
Thoma has carefully investigated the absorp-
tion of B by metals (Z. P. C. 3, 69). Be finds
that Pd, made the negative electrode during
electrolysis of water, takes up and retains a defi-
nite quantity of B ; but that after this satura-
tion-point is reached the Fd continues to absorb
E, which, however, it readily gives up again; the
total quantity of E absorbed depends on the
strength of the current ; when no more is taken
up, it is very probable that E continues to be
absorbed, but that as much is evolved as is ab-
sorbed in a given time ; the increase in the
volume of the Pd, for a given quantity of H
absorbed, is greater when the saturation-point is
passed than before it is reached, hence the rela-
tive density of what may be called the occluded
B in excess is less than that of the E absorbed
up to the saturation-point. Thoma has shown
that Fe, like Pd, may be supersaturated with H,
provided the B is produced in contact with the
Fe. Plates or wires of Ni, and also Al, ppd. Cn,
Cu wire. Ft black. Ft wire, and Ag wire, absorb
B showing phenomena similar to Fe (Thoma,
Z.C. ; Baoult, O.B. 1869. 826; Bellati a.Lussana,
Atti del B. mstituto veneto d. Scienze, lettere ed
arU, 6, 6 [1888]).
E is a reducer; it removes 0 and most other
negative elements from their compounds. Oc-
cluded B is a very active reducing agent:
KNOsAq is reduced to KNO^Aq (BSttger, B. 6,
1396) ; ferric salts are reduced to ferrous,
EsFeCy^Aq is reduced to EjFeCyjAq (Graham,
Pr. 17, 500); EOlOsAq is reduced to EClAq;
BjSOjAq gives E^S, AsjOgAq is reduced to As
(Gladstone a. Tribe, C. J. Trans. 1878. 308 ; cf.
Berliner, W. 35, 791 ; also Cooke, 0. N. 68, 103).
The atomic weight of E is taken as unity;
the relation between the atomic weights of E and
O is very important as so many atomic weights
are determined in terms of that of 0. Various
experiments have recently been made to deter-
mine the ratio of the densities of B and 0
directly; if this is known, and the ratioof the
combining weights of these elements is also
known, the ratio of the atomic weights of E and
O wiU be directly determined. The most accu-
rate determinations (which cannot, however, be
regarded as final) give the ratio S.G. of B:S.O.
HTDKOGEN.
721
of 0 = 1:15;884 (v. Eayleigh, N. 39, 462). The
atom of H is the standard monovalent atom in
terms of vrhioh the yalenoies of the other atoms
are stated. The S.G. of gases is also generally
stated in terms of H.
H is a combustible gas; it may be burnt in
O, CI, I, S vapour, cSio. ; if O is caused to flow
from a narrow orifice into a quantity of H which
has been ignited at the opening of the contain-
ing vessel, combination ooours at the edges of
the moving stream, and hence the 0 appears to
barn, and the H to act as the supporter of com-
bustion. The flame of H is almost non-lumi-
nous ; the temperature is very high.
Hydrogenium. This name was given by
Graham to hydrogen when it is occluded by Pd
(Pr. 17, 212, 500). The experiments of Graham,
Dewar, Troost a. HautefeuiUe, and Thoma, have
shown that when H is occluded by Pd it is very
much condensed (for references v. supra). Gra-
ham looked on H as a metal, and Pd charged
with H he regarded as an alloy, hence to H
alloyed with Pd he gave the name hydrogenium
(names of metals generally end in wm). There
seems little doubt that a certain definite quan-
tity of H is held by Pd in firmer union than the
rest of the H which it is able to occlude (v.
Thoma, svpra).
Reactions. — 1. H is burnt to H^O by mixing
with 3 its volume of oocygen, and applying a light
or passing an electric spark ; the process is ex-
plosive. The exact ratio of the volumes of H
and O which combine cannot yet be regarded as
settled ; according to the experiments of Scott
{T. 184, 543) the most probable value is 0:H
= 2-002:1 (cf. Wateb, vol. iv.).— 2. H reduces
many metallic oxides, sulpfndes, and chloride^ :
e.g. CaO and 'Sefi, heated in H are reduced to Cu
and Fe respectively; SbjS, is reduced to Sb;
FeClj is reduced to Fe. PdO is reduced at the
ordinary temperature (Wohler, A. 174, 60). Be-
garding the temperatures at which various ox-
ides, sulphides, and chlorides are reduced by H
V. Miiller (Z. [2] 5, 507; also Wright a. LufE,
C J. Trans. 1878. 1). H also reduces many me-
tallic salts in solution ; e.g. warm solutions of
chlorides of Ft, Pd, Ir, or Bh, are reduced with
ppn. of the metals ; some salts in solution are
reduced only under considerable pressure, e.g.
HgCljAq is reduced at 100 atmos. The reduc-
tion of AgNOjAq by H proceeds very slowly at
ordinary temperature (v. Bussell, O.J. [2] 12, 3).
As already stated (supra) Pd or Pt charged with
H is a very energetic reducing agent. (Begard-
ing the reaction of H and 0 in presence of CO
V. Cabeon, vol. i. p. 690.)
Combinations. — 1. H combines indirectly vrith
copper to form Cu^Hj {v. Copper hydbide) ; it
probably also combines with palladium, potas-
sium, and sodium (v. supra). — 2. H combines
with aU the non-metals ; directly with C, N, 0,
S, Se, Te, ?P, 01, Br, I; indirectly vrfth P, As,
Sb, Si, ?B {v. the various elements).
Nascent hydrogen. — Certain reductions not
brought about by H are effected when a chemical
change in which H is produced is carried out in
presence of the body to be reduced; e.g. KClOjAq
is not reduced by passing H through the solu-
tion, but if Zn and dilute H„SO,Aq are placed in
the solution KCl is formed ; so CjHsNOj is not
lednoed by H under ordinary conditions, bat if
Vol.. II.
Fe filings and dilute acid are brought into con-
tact with CjHsNOa aniline (CjHjNHJ is formed.
It is customary to speak 5f such reactions as these
as brought about by nascent hyd/rogen. That
the reduction of EC10,Aq, for instance, is
not to be wholly traced to the H produced iti
contact with it is proved by the fact that Na-
amalgam does not reduce this salt, although H
is plentifully produced when Na-amalgam is
placed in the solution (Tommasi, P. B. 2, 205).
Nascent H is generally regarded as synonymous
with atomic H, and it is contrasted with ordi-
nary or molecular H. It is probable that H con-
sists for the most part of atoms at the moment
of its production from a compound, and that
these then combine to form molecules. As
energy must be degraded in the falling together
of the atoms into molecules we should expect
atoms of E to be capable of bringing about
chemical changes that could not be accomplished
by molecules of H. But the facts cited with re-
gard to the reduction of KCIO3, and there are
many similar facts, show that — granting that H
is produced in atoms when Zn andH^SOjAq, or
Na-amalgam and water, react — the whole of the
chemical change must be looked to, and atten-
tion must not be concentrated only 'on the
H. If we start with the system Zn, H^SOjAq',
KCIOjAq, we may pass to the system ZnSO^Aq,
H,, KClOaAq, or to the system ZuSO^Aq, KClAq,
HjO, or to a system which consists of all these
products ; more energy is probably degraded in
passing to the third system than to any of the
otljiers ; this system is produced. But this view
does not hinder us from saying that when the Zn
and HjSOjAq form ZnSO,Aq and hydrogen, it is
atoms of H that are formed, and that some of
these combine to form molecules, and others re-
act with the KClOj to form KCl and HjO. la
the case of Na-amalgam and KClO^Aq it is pro-
bable that much more energy is degraded in
passing to the system NaOH, H2, Eg, EClOj,
than to the system NaOE, Eg, ECl, EjO. Pro-
bably also in the case of Zn and EjSO^Aq the
energy produced suffices to decompose some of
the KCIO,, and so ECl and E^O are formed;
whereas the energy produced in the reaction of
Na-amalgam with EjO is not (by hypothesis)
sufficient to decompose any KCIO,.
Chemical relations of hydrogen. — ^E stands
apart from the other elements. In its relations
to 0, CI, S, and cither negative elements, it plays
the part of a metal; in its relations to the
paraffins G^E^^+j ^^^ paraffin alcoholic radicles
C„E2„^, it exhibits properties not at all charac-
teristic of metals. E is a constituent of all acids,
and also of all alkalis. Some of the binary com-
pounds of E are powerful acids, some are alkalis,
some are neutral bodies. In the periodic ar-
rangement of the elements E is placed as the
only member of series 1. The difference be-
tween the atomic weights of two consecutive
members of the same group, in odd and even
series, is about 22 ; the difference between the
atomio weight of E and that of Li, which follows
E In Group I, is 6.
References to older works on hydrogen.-^
Scheele, Crell Arm. 1785. ii. 229, 291 ; Caven-
dish, Crell Ann. 1785. i. 324; Watt, Crell
Arm. 1788. i. 23, 36 ; Meusnier a. Lavoisier,
Crell Ami. 1788. i. 354, 441, 528 ; Berzelius a.
S A
722
HYDROGEN.
Dulong, A., Ch. 15, 386; Dumas, C. B. 14,
537.
Hydrogen antimonide. Described under An-
timony, vol. i. p. 288.
Hydrogen arsenides. DeBcribed under Ab-
' SBNic, vol. i. p. 310.
Hydrogen boride v. Bobon htdbide, vol. i.
p. 526.
Hydrogen bromide v. Bbgubydbio acid,
vol. i. p. 532.
Hydrogen carbides v. HycBOCABBONS, this
vol. p. 716.
Hydrogen chloride v. Chlobetdbio acid, this
vol. p. 5.
Hydrogen fluoride v. FiiUobhydbic acid, this
vol. p. 658.
Hydrogen iodide v. Iodbtdbic acid in vol. iii.
Hydrogen nitride v. AumoNliL, vol. i. p. 196.
Hydrogen oxides. Two oxides of hydrogen
are known, H^O and Hfip The former has
been gasified, and its molecular composition is
represented by the formula HjO ; the latter is
decomposed by heat, the gaseous molecule H^O,
cannot exist, therefore the formula H2O2 repre-
sents the composition of the chemically reacting
atomic aggregate of this compound. Water is a
stable compound; in its chemical relations 'it is
a neiutral oxide ; its typical reaction with a metal
is to produce an oxide and H, its typical reac-
tion with a non-metal is to produce a hydride
and O. Hydrogen peroxide readily parts with
^ of its 0, and therefore acts generally as an
oxidiser. Water combines with many compounds
and with some elements to form hydrates, with
other compounds and elements it reacts to form
hydroxides {v. Htdbateb and HtdboxIdes, pp.
703, 733) ; hydrogen peroxide directly combines /
with but few other bodies.
Hydbooen monoxide or Wateb, v. Watee, in
vol. iv.
Htdbooen dioxide BijO,. {Hydrogenperoxide.
Oxygenated water. Sometimes also called hy-
droxyl, but this term is now almost universally
retained for the radicle OH.) This compound
was first prepared by Thtoard in 1818. (Th^-
nard's chief memoirs are contained in A. Ch. 8,
306; 9, 51, 94, 314, 414 ; 10, 114, 335 ; 11, 85,
205 ; 50, 80.) KjO, has not been obtained quite
free from water.
Ocewrrence. — In rain-water and snow{Strnve,
Z. [2] 5, 274 ; Houzeau, C. B. 70, 519 ; cf. Ai-
MOSPHEBE, vol. i. p. 333). Acording to Clermont
(0. B. 80, 1591) HjOj occurs in the juices of
tobacco plants, vines, and lettuces ; Wurster (B.
19, 8195) asserts the occurren(ie of 'H.fi^ in many
animal and vegetable secretions; but Bokorny
(B. 21, 1100) points out that his test was incon-
clusive.
formation. — 1. By decomposing various per-
oxides by dilute acids, e.g. BaOj by HoSO,Aq,
HClAq, COjAq, or H^SiPeAq, or KjO, by tartaric
acid (v. Thdnard, I. c. ; Duprey, J. pr. 88, 440 ;
, Schonbein, J. pr. 77, 263 ; Osann, 0. O. 1862.
97 ; C. Hoffmann, A. 136, 188).— 2. By shaking
Zn or Fe powder with water in presence of air
(Schonbein, /. pr. 105, 219^; Hoppe-Seyler, H.
2, 25 ; 10, 36).— 3. By the action of hydrogenised
Pd on water in presence of O (Traube, B. 15,
659, 2434, 2451 ; 16, 1201).- 4. During the eleo-
trolysis of fairly cone. HjSO^Aq; dilute H^SO,
gives little or no HjO, Eicharz {W. 31, 912)
says that 70 p.c. acid is the best concentration to
use. Much work has been done on the source of
HjOj in the electrolysis of H.SOiAq. Bicharz
{I.e. and W. 24, 183) regards the HjO, as a pro-
duct of the reaction of H^S.^, (formed by electro-
lysis) and B..fl ; when 68 p.c. HjSO^Aq is used,
the amount of H^O.^ increases, and then becomes
constant, but the H^S^O, goes on increasing, on
stopping the current H^O^ increases for a time,
and HgSjOg notably decreases. In a solution
containing H^SO, and HjSjOg the latter slowly
disappears, and H^O, is produced. Traube holds
that the HjOjis directly produced by the reaction
of ordinary (molecular) 0 with water and nascent
H {l.e. and B. 19, 1111; 20, 3345). The H^O,
is always formed at the negative electrode.—
5. According to Berthelot (0. B. 86, 71) H^Oj is
formed by shaking ozone with ether, and then
adding water. — 6. By the oxidation of very
dilute NHjAq by ozonised O [?2NH3Aq + 20,
= NH,NO^q + HiOJ (Carius, B. 7, 1481).—
7. By placing a solution of pyrogallol under a
bell jar (Struve, W. A. B. 68 [2nd part], 432).—
8. By burning H in air (Struve, J. 1870. 199,
209). — 9. By shaking Various essential oils con-
taining terpenes with water in presence of aif
(Schijnbein, J. pr. 99, 11 ; Badenowitsch, B. 6,
1208 ; Kingzett, C. J. [2] 13, 210).— 10. During
many processes of oxidation in presence of water
{v. Soh5nbein, J.pr. 89, 14 ; 98, 257).
Preparation. — By deoomposingBaO, by dilute
acids. — 1. Th^nard prepared BaOj by heating
BaO in small pieces to low redness in a stream
of 0 free from COj ; the BaO was obtained by
strongly heating Ba(N0,)2 ; the stream of 0 was
maintained for fifteen minutes after 0 had ap-
parently ceased to be absorbed. (For method of
preparing pure BaO, v. vol. i. p. 443.) The BaO,
was allowed to cool in 0, and then placed in a
stoppered bottle. 200 grams H^O were then
mixed with sufficient HCl to neutralise about
15 grams BaO^H,; this dilute HOlAq was placed
in a Ft vessel surrounded by ice, and 12 grams
BaOj, slightly moistened and rubbed to powder
in an agate mortar, were added; the Ba was
then ppd. by iHjSO,Aq; 12 grams BaO, were
again added, and the Bti was again removed;
the liquid was filtered, and addition of BaO,
in two portions, with ppn. by HjSOjAq, was
repeated. These processes were repeated until
about 100 grams BaO, had been used. SiO,,
Al^Oj, FcjOj, &c., were removed by adding cone.
HjPOiAq and excess of BaOj. After rapid filtra-
tion traces of HCl were separated by cautious
addition of powdered AgjSO^ to the liquid sur-
rounded by ice. After another rapid filtration,
HjSO^Aq was removed by addition either of
BaOjHj suspended in water, or of ppd. BaCO.,.
2. Felouze {v. Berselius' Lehrbuch, 1, 411)
decomposed BaO, by HjSiF^q, the liquid.being
kept cold, and filtered from BaSiF,.
3. Thomson (B. 7, 73) dissolves finely-pow-
dered BaOj in dilute HOlAq until the acid is
nearly neutralised; after filtration the liquid is
cooled, and BaOAq is added sufficient to ppt.
SiOj, AljO,, and other oxides, and to produce a
slight pp. of BaOj.SHjO; the liquid is again
filtered and mixed with cone. BaOAq, whereby
crystalline BaOj.8HjO is ppd. ; this moist pp.
may be kept unchanged in a stoppered bottle.
Thomson decomposes the moist BaOs-SHjO by
HYDKOGEN.
728
adding it to cold dilute HjSO^Aq (not more oono.
than I part by weight HjSOi to 5 parts H2O)
with constant stirring, until the acid is nearly
neutralised; after settling and filtering, he ppts.
the remaining acid by cautious addition of dilute
BaOAq.
4. Mann {Ghenmker Zdbwng, 12, 857) recom-
mends to add a J p.c. HaPOjAq to commercial
H2O2, and then, while stilrring vigorously, to add
BaOjKi until exactly neutral to litmus ; then to
pour the clear liquid into cold cone. BaOAq,
to wash the ppd. BaOj.8H,0, and to decompose
it by dropping into cold dilute HjSOiAq contain-
ing 12 p.o. BtjSO,, removing any excess of acid
by dilute BaOAq (v. also Schone, A. 192, 257).
The solution of HjOj obtained by one or
other of these methods is concentrated i»i uoctto
over HjSOj, with agitation from time to time ;
if SiOj separates it must be removed, else it
will decompose some of the H^Oj. The liquid
begins to give off O when it is so oono. that one
volume of it will yield about 250 vols. O, a drop
or two of H2SO4 is then added, and evaporation
is continued. Nearly pure HjOj is thus obtained.
1 vol. will give 475 vols. O. It is kept in stop-
pered glass tubes surrounded by ice (ThSnard).
Hanriott (O. B. 100, 172) concentrates iLjOjAq
by distillation under reduced pressure ; a solu-
tion, 1 vol. of which will give 267 vols. 0, can
thus be obtained. A solution so cone, that 1 vol.
yields c. 70 vols. 0 is obtained by freezing dilute
BLjOjAq, crystals of pure HjO separate (Hanriott,
C. B. 100, 57).
Properties. — The most cone, solution of H^Oj
obtained as described under PreparaUcm is a
syrupy liquid S.G. = l-453 ; it does not freeze at
—30°; m vacuo it volatilises unchanged (Th6-
nard). Has a harsh bitter taste ; corrodes the
cuticle. Thomsen gives the thermal data:
[H^O^Aq] = 45,300; [H»0,0,Aq] = - 23,060;
[HWAq,H^ = 91,420 (Th. 2, 59) ; Berthelot gives
[H'0''=H20 + 0] = 21,480 {A.Ch.[S] 6, 209). Ac-
cording to Hanriott (Bl. [2] 43,468) cone. HAM
has an acid reaction towards turmeric, and an
odour resembling that of nitric acid. H^O^Aq
slowly decomposes ; if very dilute it may be kept
indefinitely (Berthelot, O. B. 90, 897) ; very di-
lute solutions may even be boiled without change
(Hanriott, C. B. 100, 57). Traces of impurities
greatly modify the stability of H^OAq; acids
increase, alkalis decrease, the stability. Very
cone. HjOjAq rapidly evolves 0 at 20° ; heated
quickly to 100° O is evolved with explosion ; 1
vol. of the most cone, solution obtained by
Th^nard gave 475 vols. O at 0° and 760 mm.
It is customary to state the cone, of commercial
HjOjAq as so many volumes, e.g. ' 20 volumes; '
this means that 20 volumes O are obtainable
from 1 vol. of the solution. H^O, is soluble in
aU proportions in water, also in alcohol ; but it
slowly reacts with the alcohol; si. sol. ether.
On shaking this solution with water theH,0, all
goes into solution in the water (Schonbein, J.pr.
78, 92). An acidified solution of H2O, is de-
composed to H and O by electrolysis. Ac-
cording to Schone (A. 197, 137), the H^O, does
not undergo electrolysis, but is decomposed by
reacting with the products of electrolysis of the
dilute acid present, probably (i.) Sfi, + 0
= H,0-l-0„ (ii.) SO«+BtO,=HjS04+0, (iii.)
H,+HiOj=2H,0.
Beactions. — HjOj contains a larger per-
centage of 0 (94-1 p.o.) than any other com
pound; it readily parts with ^ of its 0, and
therefore reacts as an oxidiser ; in some cases,
however, it acts as a reducer, e.g. Ag^O is re<
duced to Ag and PbO^to PbO (v. infra).
1. Alumim/um, iron, magnesium, and thal^
Uum are oxidised to the hydrates FeOsHj,
AIO3H3, MgOjHj and TlOjH,, according to
Weltzien {A. 138, 129).— 2. Most metaU except
Au and the Ft metals are changed to oxides.
3. Several non-metals are oxidised, generally to
their highest oxides, e.g. Se and As.^ — 4. Very
many oxides and oxyacids are converted into
more oxidised compounds, e.g. As^O, to AsjOj,
H3PO, to HjPO^, CaO, SrO, and BaO to the di-
oxides MOj, ferrous to ferric compounds, PbS to
PbSO„ TljO to TljO, (v. Schone, A. 196, 98),
KiFeCy, to KaFeOy, (Weltzien, A. 138, 129).
Several metallic salts yield peroxides when
treated with HjO, in presence of ammonia, e.g.
salts of Bi, Oe, Co, Ni.^5. Sulphwretted T^dvo-
gen very slowly forms HjO and S (Pairley, 0. J.
[2] 16, 23).— 6. Bydrogen iodide forms HjO and
I.— 7. A solution of chromic hydrate in potash
is oxidised by HjOj to KjCrO, (cf. Beaction 11
infra). — 8. Ammonia in solution is oxidised to
NH^NO, [4NH3Aq + 6HA = 2NH,N0,Aq +-8H20]
(Weith a. Weber, B. 7, 1745).— 9. According to
Pairley (O. J. [2] 16, 125) the unstable compound
Na^Oj.SHgO is formed by adding alcohol to a
mixture of equivalent weights of BijO^aJxicausUc
soda (v.also Schone, ^.192, 241). Ctmsttepotash
reacts somewhat differently, giving a mixture of
KA with KOH.a;HjO (Schone, Ix.).
10. H2O2 reduces ozone, fonmng H^O and
oxygen. Brodie (T. 1850. 759) showed that ^ of
the O comes from the ozone and ^ from the
E2O2 ; this result was confirmed by Schone (A.
196, 239) ; Schone used neutral solutions of
E2O,, Brodie used alkaline solutions. — 11. Seve-
ral metallic peroxides are rediiced by H^O, in
presence of acid. For instance CrO, in H^SO,
solution gives a blue colour, but this soon
goes, and green CrjSSO, is produced (cf. Be-
action 7 supra)} Berthelot thinks that per-
chromio acid HCrO^is formed and then reduced
by the excess of H^O, ; Moissan regards the blue
body as GrOj.HsO, {v. CrO, under Ghbouiuu, p.
166) ; MnO, in presence of an acid forms a salt
of MnO and evolves O ; for every MuO, used, O,
is evolved (cf. Beaction 19 infra). Brodie showed
that in such cases ^ of the 0 evolved comes
from the H^O, and ^ from the metallic peroxide
(0. 7.4, 194; 7,304; of. Aschoff, J.pr. 81, 401).
According to Lenssen (J. pr. 81, 278) H^O,
oxidises metallic oxides in presence of alkalis
when the alkali can combine with the higher
oxide produced by the HjO,, to form a salt — e.g.
CtjO, to CrO, in presence of KOH — but it re-
duces higher to lower oxides in presence of acids
when the acid forms a stable salt with the lower
oxide, e.g. CrO, to Cr20, in presence of H2SO4.
12. Potassium dichromate is reduced by H^O,
in neutral solutiong to CrOj, in acid solutions
to a salt of CrjO, (Schonbein, /. pr. 70, 257 ;
Aschoff, J. pr. 81, 401). — 13. Potastmm per-
numgamate in presence of H^SO, ia red/uced to
MnSO^, thus gKMnO^Aq + SHsSO, + SH^O,
= E2S04Aq-i-2MnS04Aq + 8H20 + 60r In this
case also ^ the O comes from the HgO, and 1
3a2
724
HYDROGEN.
from the KMnO^. Accc rding to P. Thdnard (O.
B. 75, 177) H2O2 and KMnOjAq react when kept
at a low temperature, ba.t no 0 is evolved ; Ber-
thelot (C. B. 90, 656) confirms this, he thinks
an oxide HjOj.a;0 is formed. — 14. Silver oxide,
AgjO, is reduced to Ag by H^Oj; Ag^O + HjOj
= HjO + 0„ + 2Ag: HgO reacts similarly. Ber-
thelot (O. it. 90, 572) thinks that an oxide AgjO,
is produced. — 15. According to Hanriott {Bl. [2]
43, 468) HjOj reduces Fehling's solution.
16. HjOj reacts with chlorine to form HCl
and 0; HA + Clj- 2HCl + 0j. Schone (A.
196, 254) thinks the reactions may be
HA + OHj + Clj = HjO + O2 + 2HC1.— 17. Iodine
forms HI and 0, by reacting with dilute HjOjAq ;
but HI decomposes more cone. HjO^Aq to form
HjO and I. In the reaction between I and
H^Oj, an oxyacid of I may be produced and then
decomposed ; when I is added to KOHAq con-
taining H,P2, only KI ia formed (no KIO3) and
O is evolved (c/. Fairley, G. J. [2] 16, 22).
H2O2 is decomposed toH20 and O by several
substances which at the close of the reaction
remain the same as they were at the beginning.
18. Platinum, gold, silver, and charcoal,
added to H^O,, cause evolution of 0 and forma-
tion of.H^O. Fibrin and some other organic
substances bring about the same change.
19. Manganese dioxide added to HjO, produces
O and HjO, and the same quantity of MnOj
remains as was originally added (for action
when an acid is present v. Reaction 11 supra).
20. Potassium iochde with pure H^OjAq causes
evolution of 0, but no I is liberated (Kingzett,
C. J. 37, 805; Schone, A. 195, 228). Schone
' supposes that a series of changes occurs, pos-
sibly the K salt of an oxyacid (? hypoiodite)
is formed and then reacts with more HjO, to
give KI, HjO, and O. Ordinary commercial
HjGjAq liberates I from KI. — 21. Potassium
bromide and chloride both cause evolution of 0 ;
KBr more slowly than KI, and KCl more slowly
than KBr ; no Br or CI is liberated (Schone, l.c.).
22. Certain salts, e.g. Na^SO^, also decompose
H2O2, but the salt is the same at the close as at
the beginning of the reaction {v. Schone, l.c.).
23. The caustic alkalis decompose H^Oj
with formation of 0 and H^O ; Schone has ex-
amined these reactions ; he thinks that the first
products are HjO and compounds MJUfi, (M
= alkali metal), these compounds have been
isolated (v. Combinations, infra) ; these com-
pounds then decompose to alkali, H^O, and
O. Schone shows that the rate at which HjO,
is decomposed by alkalis is modified by tempera-
ture, light, concentration, traces of impurities,
and the condition of the surfaces of the contain-
ing vessels,
H2O2 is a representative peroxide; its re-
actions are similar to those of BaOj, SrO,,
&o., and the organic peroxides such as acetyl
peroxide (C^fi)^^ ; it cannot be said to have
distinctly basic or acidic properties, but on the
whole it is more acidic than basic, e.g. in the re-
action Ba02H2.8H20 + HjOj^BaOj.SHjO -1- 2H2O
there is probably an exchange of the H of H^O,
lur the metal Ba.
Combinations. — Schone (A. 192, 257) has
obtained bodies which are probably compounds
of H2O2 with the peroxides of the alkali and
alkaline earth metalB. When 1 equiv. KOH in
solution was added to about 3 equiv. H3O,,
the liquid was evaporated in vacuo and the
residue dried at —10°, a white solid K2O2.2H2O,
( = K2H4O,) was obtained. Using about the same
proportions of NaOH and HoOj, the compound
NaX0,.4H20 (? = Na2Q2.2H202.4H20) was ob-
tained. Both these compounds are easily de-
composed by warming with evolution of 0. The
compound Ba02.H202 was obtained by direct
addition of its constituents, or by adding a
certain quantity of NH,Aq to a Ba salt solution
in presence of H2O2; this compound is very un-
stable, it easily goes to BaO,, HjO, and 0 ; if
the decomposition is effected by warming under
water, crystals of Ba02.8H20 are formed. In.
dications of the existenon of compounds of HjO,
with CaOj and Sr02 were obtained, but the
compounds could not be isolated on account of
their great instability.
Detection and Estimatinri. — H202Aq producea
a blue colour in a dilute solution of guaiacum
mixed with an infusion of malt. Addition of a
few drops of Fb acetate solution, followed by
KIAq and starch and a little acetic acid, pro-
duces a blue colour (Schonbein, /. pr, 86, 129 ;
Struve, Z. 1869. 274). Eioharz ( W. 31, 912)
says the best reagent for detecting HjO,, espe-
cially in presence of S2O,, is a solution of titanic
acid in H2SO4; a very yellow pp. is obtained;!
this pp. decolourises the same quantity ol
KMnOjAq as the H2O2 in the solution from
which the pp. was obtained (c/. Schonn, Fr. 9,
41, 330 ; D. P. J. 210, 317).
According to Hanriott (PI. [2] 43, 468) HjO,
is best estimated by measuring the amount of
O liberated by reacting with MnO,. It may also
be estimated by measuring the quantity of
KMnOj reduced, or the O liberated by reacting
with KMnOjAq;. Kingzett (G.J. 37, 806) says
no acid should be present : the reaction is
2KMnOiAq -I- 3H2SO4 -^ 5H,02
= KjSOjAq H- 2MnS0<Aq + SHjO + SOj.
KIAq may be brought into contact with
HjOjAq, and the I estimated by dilute standard
Na2S203Aq ; best in presence of much dilate -
H2S0«Aq (Kingzett, l.a. ; cf. Schone, B. 7, .
1696; Hamel, G. B. 76, 1028).
Hydrogen phosphides v. Fhosfbobub, by-
SBIDEB OF.
Hydrogen selenide HjSo. (Seleniettei or
seleniuretted hydrogen. Selenhydric add. &y- <
droselenicaeid. Selenion hydride.) Mol. w.80'8.
This compound is the Se analogue of SH,.
Formation.— 1. By leading H over Se heated
to 0. 400°-500'' (Corenwinder, A. Gh. [3] 34, 77 ;
Wohler a. Uelsmann, A. 116, 122) ; or by heating
H and Se in a closed tube to c. 440° (Haate-
feuille, C. E. 64, 608). According to Ditte
(C. B. 74, 980) combination of H and Se begins
at c. 250°, is at its maximum at c. 520°, and
then decreases to 750°, where it ceases.— 2. By
the action of Se . on HI gas at the ordinary
temperature (Hautefeuille, Bl. [2] 7, 198) ; in
presence of water, however, SeHj and I give Se
and HI. According to Hautefeuille (C B. 68,
1654) BeH2 and I are produced by heating Se
with fairly cone. HIAq in a sealed tube, but on
cooling Se crystallises and HIAq remains.—
3. By the action of water on Se phosphide
(P,Se. + BHjOAq = 2HP0,Aq + 5H2Se). Berzeliui
recommends this as the best method for pre-
HYDROGEN.
725
paring HjSe (Lehrbuch [5th ed.], 2, 211).— 4. By
treating FeSe (obtained by strongly heating Pe
with Se) with fairly diluted HClAq (v. Divers a.
Shhnidzu, C. J. 47, 441).
Properties. — A colourless gas with most
irritating odour, i;esembline that of SH^ and CI
combined. Extremely poisonous. A 'minute
quantity of the gas inhaled remove^ the sense of
smell for a time, and produces violent headache.
In workingwith this compound great precautions
must be taken. Berzelius thus describes the
effect of allowing a bubble of the gas to pass
into his nostrils : * Bei meinem ersten Versuche,
den Geruch dieses Gases kennen zu lernen,
hatte ich, als eine Gasblase, vielleicht nicht
grosser als eine Erbse, in eines der Nasenlocher
gelangt war, fiir mehrere Stunden so ganzlich
den Geruch verloren,dass ich ohne das geringste
Gefiihl das starkste Ammoniak unter die Nase
halten konnte. DeT Geruch kam nach fiinf bis
sechs Stunden wieder, aber ein sehr hef tiger und
beschwerlicher Sohnnpfen hielt vierzehn Tage
lang an ' (Leh/rbuch [5th ed.], 2, 213). SeH^ is
more soluble in water than SHj; the solution
reddens litmus; it quickly decomposes in air
with ppn. of Se.
Reactions. — ^1. Seat decomposes SeB!^ into
Se and H. Ditte (C. B. 74, 980) says that the
change begins at 150°, is considerable at 270°,
bat then decreases until it reaches a minimum
at 520°, after which it again increases ; if H is
passed over Se heated to c. 500° SeH, is formed,
but is again decomposed on coming into the
colder part of the tube, so that crystals of Se
are formed on those parts of the tube. Ditte's
results would show that the dissociation-pres-
sure of SeH, does not increase regularly with
increase of temperature {v. remarks x>n the
action of heat on SeH^ under Dissociation, p.
398). — 2. Moist air causes decomposition of
SeHj with separation of Se.— 3. Electric sparks
cause separation into Se and H (Berthelot, Bt.
[2] 26, 101). — 4. Many metals decompose SeH^
when heated in it ; by heating with Sn a volume
of SeH, gives its own volume of H. — 5. Towards
metallic oxides and salts SeHj acts very similarly
to SHjj it ppts. selenides from solutions of many
salts.— 6. DUute sulphurous acid reacts with ex-
cess of H^Se to form Se and a little SH^; the re-
actions probably are (1) 2SeH2+H.S03Aq
= 2Se -H S + 3H,0Aq, (2) SeH^Aq-l- S = SH^q + Se
(Divers a. Shimidzu, C. J. 47, 441). When
HuSe gas ia passed into SOjAq a pp. is formed
containing both S and Se, probably a seleno-
thionio acid (D. a. S., U.).—7. When H^Se ia
brought into contact with su^hur H^S and Se
are at once produced (D. a. S., l.c.).
Hydrogen silioido SiH^ v. Silicon hydbide
in vol. iv.
Hydrogen, sulphides of. Two sulphides of
H are known, H^S corresponding with HjO, and
a persulphide H„S.a;S probably corresponding
with HjOj. The sulphide HjS in solution acts
as a weak acid; the persulphide is generally
analogous in its reactions to Sfi^.
Hydbogen sulphidb HjS. (Hyd/rogen mono-
tulphide. Sulphuretted hyd/rogen. SuVphy&rio
acid. Hydrosulphwric add. Syd/rofhimicaeid.\
Mol. w. 33-98. [0. - 85-5°] (Faraday, T. 1845. 1,
155). (o. - 61-8° at 760 mm.) (Begnault, Acad.
86, 658). VJ). 34. S.O. K«uid o. -9. S.H.p.
■2423 (CroulleboiB, A. Ch. [4] 20, 186). S. at 6"»
3 96, at 15° 3-23, at 20° 2-9, at 25° 2-6, at SO"
2-33, at '40° 1-86 (Sohonfield, A. 93,26; 95,10).
5. in alcohol at 5° 14-78, at 15? 9-54, at 20° 7-41,
at 25° 5-62 (Carius, A. 94, 140). H.F. (from
white amorphous S) [H^S] = 4,740: [H^S.Aq]
= 9,200 ; [H''S,Aq] = 4,560 {Th. 2, 63). Vapour-
pressures of condensed HjS in atmos. (Faraday,
T. 1845. 1, 55) -70° = 1-09, -50° = 2-0, -40°
= 2-86, - 31° =3-95, - lS-9° = 5-96, - 3-33° = 6-36,
+ 8-9° = 13-7, 11-1° = 14-6.
The gas was known in the 16th and 17th
centuries; it was first accurately examined by
Scheele, who regarded it as a compound of sul-
phur, phlogiston, and heat.
Occurrence. — In gases from volcanoes and
fumaroles. In maiiy mineral waters, e.g. the
Harrogate water. Sometimes in small quanti-
ties in sea- water. It is said to be found in some
new wines, probably formed by the acids decom-
posing sulphides produced by the reduction of
sulphates during fermentation.
Formation. — 1. By the decay of organic
matter containing S compounds, or dt organic
matter free from S in presence of gypsum. —
2. By heating various organic bodies, e.g. suet or
paraffin (Eeinsh, J.pr. 1838. 42 ; Galletly, C. N.
24, 162) with S.— 3. By the dry distillation of
S-containing organic material, e.g. gas-coal. —
4. By reactions between various acids and me-
tallic sulphides. — 5. By the reaction of cone,
hot HjSOj with Zn and some other metals. —
6. By the electrolysis of cone. BLjSO^.- 7. By
heating S with very cone. HIAq. — 8. The direct
union of H and S occurs when H and S vapour
are passed over pumice at c. 400° (Corenwiuder,
A. Ch. [3] 34, 77), or when H is passed over
boiling S or is burnt in S vapour (Cossa, B.
1, 117 ; Merz a. Weith, B. 2, 341 ; cf. Myers, B.
5, 259), or by passing electric sparks through a
mixture of H and S vapour (Chevrier, C. B. 69,
136 ; cf. Boillot, O. B. 70, 97 ; and also Grove,
C. J. [2] 1, 263).— 9. Boiling water is said not to
be decomposed by S (J. de Girard, C. B. 66, 797;
Gelis, C. B. 56, 1014 ; Geitner, A. 129, 351 ;
Cossa, B. 1, 111), but the experiments of Cross a.
Higgins (O. J. 35, 249) make it very probable -
that when S is boiled with water smaU quantities
of HjS are produced. By heating H,0 with S to
200° (Geitner, A. 129, 351), or by passing steain
and S vapour through a glowing glass tube (Myers,
J.pr. 108, 123) H^S is produced.
Preparation. — 1. Iron sulphide, FeS, in small
pieces is placed in a flask connected with a
washing apparatus containing water, and dilutfr
H2S04Aq, or HClAq, about 3 to 4 parts water to
1 part cone, acid, is added little by little, with
shaking. (The FeS may be conveniently pre-
pared by heating three parts Fe filings with 2
parts powdered S.) If the H^S is to be collected
over water, hot water should be used ; if it is
necessary to store it in a gasholder a solution
of brine should be employed in the gasholder.
The gas may be dried by passing through a suc-
cession of CaCl, tubes (H^SO^ must not be used,
as it decomposes HjS). The HjS thus prepared
usually contains H (as the FeS usually contains
Fe) , and frequently hydrides of As and Sb. Yarioua
methods have been suggested to get rid of pos-
sible traces of AsH, ; 0. von der Pfordten reoom-
meuds to pass the dried gas through a tube con>
726
HYDROGEN.
taiiu'ng commercial 'liver o{ sulphur ' heated to
350°-360°, and then through NajOO^q (B. 17,
2897). Jacobsen {B. 20, 1999) says that every
trace of As may be removed by passing the
gas through 2 or 3 grams of coarsely-powdered,
air-dried I, interspersed with glass-wool, placed
in a tube at the ordinary temperature. — 2. Pure
SHbnite Sb^S, is decomposed by dilute HClAq ;
the H^S is nearly pure. — 3. Fresenius {Fr. 26,
339) recommends the use of calcium sulphide.
It is prepared by strongly heating a mixture of
plaster of Paris and charcoal ; the sulphide is
mixed with one-fourth its weight of plaster of
Paris and enough water to make a cream ; the
whole is poured into shallow paper trays ; after
setting the block is cut into pieces, which are
dried at a gentle heat. By placing the dried
pieces in a Kipp's apparatus and adding dilute
HClAq, a stream of H2S is obtained which can
be readily controlled. — i. According to Divers a.
Shimidzu (C. J. 45, 699) an aqueous solution of
Mg hydrosulphide is a most convenient source of
HjS, as the pure gas is evolved by heating this
solution to c. 60 ". The solution is prepared by
passing HjS (made from ordinary FeS) into a
large flask about half full of water containing
magnesia (preferably freshly calcined) in suspen-
sion; not more than about 1 part commercial
magnesia should be used to 10 parts water;
when the magnesia has all dissolved the solution
is placed in a flask with delivery tube and warmed
to c. 60° on a water-bath, when a steady evolu-
tion of pure KgS proceeds ; by raising the tem-
perature to 90°-100° more H^S is obtained. The
solution of Mg hydrosulphide may be kept un-
changed by closing the flask with a cork covered
with paralfln. When the solution has been ex-
hausted it is allowed to oool, and then again
charged with H^S, when it is ready for use again.
Many pieces of apparatus have been intro-
duced for the preparation and use of HjS in
laboratories ; they are described in Mamials of
Analytical Chemistry.
Properties. — H^S is a colourless gas with a
' most offensive odour; it is very poisonous; sol.
in c. ^ vol. of HjO, more sol. in alcohol {v. data
at beginning of art.). HjS is liquefied by pres-
sure and cold. The most convenient method, on
the small scale, is to place some H persulphide
(not thoroughly dried) (v. p. 727) in a A shaped
tube ; the persulphide is gradually decomposed
by the moisture into HjS and S ; after a few
weeks the other limb of the tube is placed in a
freezing mixture, and H2S distils into, and
liquefies in, this limb. Melsens (C. B. 77, 781)
allows charcoal to absorb H^S, places the char>
coal in one limb of a A tube, the other limb
being in a freezing mixture, and distils. If
H^S made in the ordinary way is to be liquefied by
pressure, care must be taken that the gas is free
from H. Liquid HjS is a very mobUe, trans-
parent, refractive liquid ; S.G. 0. '9 ; boils at
— 61-8° at 760 mm. pressure, and solidifies at
— 85-5°. EjS is easUy burnt in air to H^O and
SO2 ; it is decomposed by passing throngh a hot
tube at e. 400° (Myers, A. 159, 124), or by pass-
ing electric sparks through it. l^SAq decom-
poses by exposure to air vrith separation of S.
For an examination of the rate of decomposition
' of H^SAq under different conditions v. Baab
[N. B. P. 19, 10). The solution keeps best in »
corked bottle inverted under water. In its
chemical relations H^S is similar to H^O, but
it is more decidedly acidic ; EjSAq reacts as a
monobasic acid.
Beactions. — 1. H^S is easily decomposed;
when heated to o. 400° it is separated into its
elements (Myers, A. 159, 124) ; it is also decom-
posed by electric sparks. — 2. When burnt in air
SO, and H2O are produced. — 3. H^SAq soon de-
composes, with separation of S, by exposure
to the air.— 4. Moist H^S warmed in presence of
air or oxyyen produces H^SO,. — 5. Most oxi-
dising agents react with HjSAq to form HjO, S,
and SO^q or SOjAq ; thus HNOjAqand HNOjAq
produce H,0, S, and XO; HOOlAq produces
H2O, HCl, and S ; alkaline iodates are reduced
to iodides. — 6. Ferric salts are reduced to fer-
rous salts, with separation of S. — 7. When K,3
is passed into S02Aq until thelatter is completely
decomposed the solution is known as Waeken-
roder's solution ; this liquid probably contains S
in suspension, a colloidal form of S in solution,
H2SO4, H2S3O,, HjS^O., HjSjO., and a higher
thionic acid, probably H^SgO, ; if the passage of
HjS is continued until all chemical- change
ceases the final products are S and H.p, thus
2H2S + SOj= 3S + 2H2O (Debus, O. J, 53, 2S2 ; ».
Thionio acids, in vol. iv.). — 8. H^S or H,SAq
is decornposed by chlorine and bromine to HX
and S ; H^SAq is similarly decomposed by
iodine, but if water is not present E^S does
not react with I. — 9. Very many nietals decom-
pose HjS when heated with it, forming sulphides,
and H ; several metals, e.g. Ag, Qu, Hg, react at
ordinary temperatures. The decomposition of
H2S by hot Sn or Pt has been employed in the
analysis of the compound ; a specified volume
of the gas is thus found to give its own volume
of H. — 10. Many metallic oxides and salts react
with HjS to form sulphides, and water or acids.
The metallic sulphide, if insoluble in, and un-
acted on by, the acid produced in the reaction, is
ppd. when H,S is passed into a solution of the
metallic salt ; if the metallic sulphide is decom-
posed by the acid produced in the reaction, or if
it cannot exist in presence of water, no pp. is
formed. These reactions are applied in the sys-
tematic qualitative analysis of metallic salts (v.
Analtsis, vol. i. p. 220).
11. HjSAq reacts as a weak monobasic acid,
e.g. with KOHAq it forms KSHAq. Thomsen
{Th. 1, 262) gives the following heats of neu-
tralisation :
[2NaOHAq,2H»SAq] = 15,476 ;
[4NaOHAq,2ff SAq] = 15,604 ;
[BaO^'ff Aq,2Hi'SAq] = 15,748 ;
[2NH»Aq,2H^SAq] = 12,390.
Combinations. — ^By compressing HjS in pre-
sence of a little water De Fororand a. Villard
obtained a solid hydrate H^S JH^O (C. B. 106,
1402 ; cf. 106, 849 a. 939) ; this hydrate is easily
decomposed by heat. The formation of the hy-
drate occurs with a large absorption of H^S gas
by the water ; when formed at 0°, the pressure
being about 60 mm. above the ordinary, 1 c.o.
water absorbed about 100 0 0. HjS, whereas the
solubility of HjS in water at 0° and ordinary
pressure is only about 4 vols, in 1 vol. water.
Wohler {A. 33, 125) obtained ice-like crystals by
leading H^S into alcohol containing water at
- 1 8°, the quantity of water being such that no
HYDROGEN.
727
ice was formed at the temperature of experiment ;
these crystals may have been a solid hydrate of
Deteciion and estimation. — HjS is detected by
its smell, by its reaction with a salt of Pb or Ag
in solution to give brown-black PbS or black
AgjS, and by the production of a deep purple-red
colour when brought into contact with an alka-
line solution of Na nitroprusside (FeCy5(NO)Na2),
Finely divided Ag shaken with water containing
HjS forms Ag^S ; it does not, however, decompose
alkaline sulphides ; these reactions may be ap-
plied to detect alkaline sulphides in presence of
HjS ; air must not be present, else salts of S
oxyacids may be formed. BLjS in aqueous solu-
tion may be determined by adding a standardised
solution of I in EIAq until a permanent blue
colour ia produced in presence of starch. The
. solution of HjS must be so dilute that not more
than -04 p.c. HjS is present.
Htdboqen pbksulphide ?BL,S2 or H2S5.
When an acid is added to an aqueous solution of
an alkaline or alkaline earth persulphide, H^S is
evolved and the rest of the S is ppd. But if the
alkaline persulphide solution is poured into the
acid, oily drops sink to the bottom ; the oil is a
compound of H and S containing relatively
more S than H^S (Sohcek, Von der Luft und
dem Fezier, 153 ; Berzelius, Lehrbueh, 2, 218 ;
Th^nard, A. Ch. 48, 79 ; Liebig, A. 2, 27 ; 18,
170). Analyses of the oil thus obtained have
given discordant results; Eamsay's analyses
(0. J". [2] 12, 857) showed a composition vary-
ing from HjS, to H^S,,. According to Sabatier
(0. B. 100, 1346), if the oil is thoroughly dried,
it may be distilled at 60°-85° under a pressure
of 40 to 100 mm. ; and the liquid thus obtained
has the composition H^Sj. The analyses of Bebs
{A. 246, 356) also point to this formula : he de-
composed Naj^j, Na^Sj, NajS,, and NajSj, sepa-
rately with cold HClAq, also different polysul-
phides of Oa and Ba ; in each case he got an
oil the composition of which agreed with the
formula H2S5. Sabatier thinks that the liquid
obtained by him contained S produced by the
decomposition of part of the persulphide ; he is
in favour of the formula HjSj for the persul-
phide.
Hofmaim {B. 1, 81) by the reaction between
yellow NHj sulphide and strychnine obtained a
welUcrystallised compound C21H22N2O2.HJS3
which was decomposed by acids with separation
of H persulphide ; this formula was confirmed
by Eamsay (0. J. [2] 12, 857). Schmidt allowed
HjS to react with strychnine in presence of air,
and obtained crystals of SG^j'R.^il/i.fli^^iSi;
with brucine he got the compounds
CaH.^NA-HjSj.2H20 and CJdJSfit.2B.^Si;
these compounds were decomposed by acids
giving a yellow oil which had the properties of
H persulphide. ,
The composition of H persulphide cannot be
regarded as settled; possibly more than one
compound H^SxS exists.
Preparation of S persulphide. — An aqueous
solution of an alkaline polysulphide is slowly
poured into excess of a solution of about equal
parts of cone, hydrochloric acid and water;
the liquid is placed in a filter in the neck of
which oily drops collect, this oil is run off and*
dried over CaCI^ To prepare the alkaline poly-
sulphide, cone. EOEAq may be boiled with S ;
or 2 parts KoCO, may be fused with 1 part S,
the mass dissolved in water, boiled with excess
of S, and allowed to clear; or 1 part CaO may
be made into a thin cream with water and boiled
with 2 parts S. As solution of polysulphidea
prepared as described may contain thiosulphates,
Berthelot {A. Ch. [3] 49, 450) reconmiends to
saturate EOHAq with H^S out of contact with
air, to add an equal volume of the same EOHAq,
and to boil with S ; or Na^SOj, or CaSO^, may
be strongly heated with powdered charcoal, the
mass treated with water, and boiled with S.
Sabatier (C. B. 100, 1346) thdroughly dries the
oil, places it in a small flask with short neck
connected with a bulb-tube surrounded by ice
and having a pump attached ; when the pres-
sure is reduced to 40-100 mm. he heats the
flask to 60°-80° in a water-bath..
Properties. — ^A yellow, mobile, oily liquid ;
S.G. 1-734 (Bamsay), 1-71 at 15" (Eebs). Odour is
very irritating ; taste bitter-sweet ; the liquid
raises blisters on the skin ; it is soluble in GgR„
CHCl,, and OS^; decomposed by alkalis, alcohols,
and slowly by ether ; also by the action of light;
slowly decomposed by EMn04Aq,Br, I, HNOjAq
(Sabatier, C. B. 100, 1585). Hydrogen persul-
phide is more stable when the Uquid contains
some S or H^,S (Sabatier). When quite dry, the
liquid may be preserved unchanged in a sealed
tube (Bunsen, P. 46, 103) ; if the liquid is not
quite dry, it slowly decomposes into crystals of
S and liquid H^S, if this change proceeds the
tube may be broken by the pressure of the HjS.
Hydrogen persulphide is readily inflammable.
iJeaciiojts.— Hydrogen persulphide resembles
H2O2 in its reactions ; it is decomposed to HjS
and S by those substances which change H^O,
into HjO and 0, e.g. Pt, Au, Ag^O, charcoal
powder, &c. ; it acts as a reducing agent, e.g. it
decolourises indigo. Water decomposes it to
HjS and S, slowly at ordinary, quicMy at higher
temperatures. AmmorUa causes a ppn. of S ;
ether acts slowly producing nacreous S ; accord-
ing to Sabatier (l.c.), hydrochloric acid, dry air,
and dry hydrogen have no action.
Hydrogen tellniide H^Te (Telluretted hydro-
gen. Tellurhydric acid. Hydrotelluric acid.
Tellurium hydride). Mol. w. 127. This com-
pound, discovered by Davy (Q.A. 37, 48, [1810]),
resembles H^S and H^Se. It is formed by
direct union of its elements, by heating Te in a
stream of H (Lowe, W. A. B. 10, 727 ; Becker,
A. 180, 257) ; also by decomposing ZnTe by
dilute HClAq. Berthelot a. Pabre (A. Oh, [6]
14, 103) recommend the use of MgTe, prepared
by action of excess of Te vapour on heated Mg
in an atmosphere of pure H ; they decompose
the MgTe in an atmosphere of pure N by very
dilute HGlAq. TeH, is a colourless gas, with
disagreeable smell, which is different from that
of HjSe or H^S ; when inhaled, the effects are
not so irritating as in the case of HjSe {g. v.)
(B. a. F., Z.C.). TeHj is very unstable ; it soon
decomposes over dry Hg, even in the dark ; in
presence of moist air, decomposition is instan-
taneous (B. a. F., I.e.). TeHj is decomposed by
heat; according to Ditte (O. B. 74, 980) this
decomposition is less complete at higher than
at lower temperatures ; the behaviour is exactly 1
similar to that of SeH^ (j. v. p. 725). TeH^ is
728
HYDROGEN.
readily comtustible ; it is fairly soluble in water,
the solution is very quickly deooBiposed if ex-
posed to air. Pure TeH, is rapidly and com-
pletely absorbed by solutions of alkalis, with
production of alkali tellurides, if a trace of 0
is present the solution becomes violet or purple,
and if much 0 is present Te is ppd. (B. a. P.,
Ix.). leHj passed into solutions of metallic salts
ppts. metallic tellurides. M. M. P. M.
, HTDBO-HOUO-i'£BirLIC ACID v. m-Methyl
dervoatiAie of (4:3:l)-Di-oxT-FHE:NTL-iao-BnTYBia
AOID.
HYDBOIODOAHGELIC ACID v. Iodo-talebio
Aon>.
HYDROIODOCINNAUIC ACID v. lono-
PEEirZL-PBOFIONIC ACID.
(a)-HYDKOJUGLONEC,„HB03.0a!2/.(a)-%iro-
naphthogtiincme? [170^. S. (at 25°) = -S. Occurs,
together with about g as much (j8)-hydrojuglone,
in the leaves and unripe green shells of the
walnut. Formed by reduction of juglone (Mylius,
B. 17, 2411 ; 18, 475, 2567). Colourless plates
or needles. Y. e. sol. alcohol, ether, and acetic
acid, nearly insol. benzene and petroleum-ether,
insoi. chloroform. It dissolves in aqueous NaOH
with a yellow colour, which almost instantly be-
comes violet on exposure to air from formation
of juglone. It is odourless, but possesses a burn-
ing taste, and is poisonous ; i g. killed a rabbit
in 2 hours. By treatment with acid anhydrides
it is converted into the alkoyl derivatives of (j3)-
hydrojuglone. On heating (a)-hydrojuglone above
its melting-point it is converted into the (S)-
isomeride. On the other hand the inverse change
takes place if (;3)-hydrojnglone is boiled with
dUute HCl for a long time. Potash-fusion gives
m-oxy-benzoic acid, together with phenol, sali-
cylic acid, and pyrocatechin. Oxidising agents
very readily convert it into juglone. On distilla-
tion with zinc-dust it gives naphthalene.
Tri-acetyl derivative 0,|,H5(0Ac)j,
[124°].
(i8)-HydTOJuglone CioHjOj. Tri-oxy-naphthal-
ene? [97°]. S. (at 25°) = -11. Occurs, together
with about 5 times as much (a)-hydrojuglone, in
the unripe shells of the walnut Silvery six-
sided tables or flat needles. V. sol. chloroform
and benzene, si. sol. cold alcohol and ether.
Volatile with steam. Aromatic smell and burn-
ing taste. Formed by heating (t^)-hydrojuglone
above its melting-point. Converted into the (a)-
hydrojuglone by long boiling with dilute HOI.
Dissolves in alkalis with a yellow colour, which
becomes red on exposure to the air. FejClg gives
a blood-red colouration. It is not oxidised to
juglone, except under conditions which allow of
its previous conversion into (a)-hydrojuglone.
Its alkoyl derivatives are formed by the action
of anhydrides upon either (a)- or (|3)-hydro-
jnglone.
Tri-acetyl derivative 0,oHj(OAc),:
' [130°]; colourless prisms (from alcohol).
Tri-bemoyl derivative C,gH,(0Bz)3:
[129°]; colourless needles, si. sol. alcohol and
acetic acid, insol. water (Hylius, B. 18, 2567).
HTSBOLVTIDIIIE v. Di-hydride of ci-
UEIBYIi-PTBIDntE.
HTSBOMECONIC ACID v. Meconio aoid.
HTDBOUELUIIC ACID v. Hexahydride ol
Meuuiic Aom.
HTDBO-METHYL-EETOIE v. Methsl-M.
DOLE dihydride.
HYDKO-METHTL-FTBIDINES v. Hydrides
of Methyl-pybidines.
DI-HYDBO-TRl-METHYL-FYBIDINE DI.
CABBOXTLIC ETHEB v. JH-hydride of Tbi-
METHYL-PYEIDINE Dl-CAEBOXYLIO ETHEB.
HTDBO-HETHYL-PYBBOLE v. Sydride ot
MeTHYIi-PYEBOLE.
HTDBO-UETHTL-QUINALDIXES v. By-
drides of Di-methyl-quikolines.
HYDBO-UirCONIC ACID G^fit »■«■
(C02H).CH:CH.CHj.CHj(C0jH). [195°]. S. -9 at
16°. Formed by partial reduction of diaoetylene-
di-carboxylic acid with sodium-amalgam. On
further reduction it gives adipic acid (Baeyer,
B. 18, 680). Formed also by treating dichloro-
muconlc acid C^^Gifi^ with sodium-amalgam
(Bode, A. 132, 98). Colourless prisms ; v. sl.sol.
cold water, v. sol. hot water and alcohol, m. sol.
ether. Beduced by sodium-amalgam to; adipic
acid (Limpricht, A. 165, 263). By treatment
with bromine it may be converted into bromo-
hydromuconic acid [183°], di-, tri-, and tetra-,
bromo-adipic, and iso-di-bromo-adipic acids. —
ZnA".— AgjA".
Anhydride CjHjOj. Trimetrio crystals;
o:6;c = -206:1: -332 (Fock, Z. K. 7, 48).
HEXA-HYDBO-NAFHIHALENE v. Naph-
IHAIiENE HEXAHYDBIDE.
TETBA-HYDBO-NAFHTHAXENE DI-CAB-
BOXYLIC ACID v. Tetrahyd/rideot Naphthalene
DI-OABBOXYLIC ACID.
'DIHYBBOXAPHTHOIC ACID' so-called v.
Mbthyl-ikdonaphthene-cabeoxylio acid.
(a)-HYDRO-NAFHTHOftUINONE C,oH,Oi
i.e. C,„H,(0H),[1:4]. [173°] (P.) ; [176°] (G.).
Formed by the action of fuming HIAq on (o)-
naphthoquinone (Groves, A. 167, 359) ; or, better,
from (a)-naphthoquinone,tin,andHClAq (Plimp-
ton, C. J. 37, 635). A small quantity may be
obtained by heating (a) -naphthoquinone with
aqueous SOj at 150° (Plimpton). 'White needles;
m. sol. bomng water, v. sol. boiling alcohol, ether,
and HOAc, si. sol. hot benzene, almost insol.
CSj and ligroin. Oxidising agents convert it
into (a) -naphthoquinone ; with a solution of (a)-
naphthoquinone it forms dark-purple crystals
of the quinhydrone Cj„H,40,.
Di-acetyl derivative C„H|i(0Ac)2. [o.
130°]. Easily soluble tables (from alcohol)
(Korn, B. 17, 3025).
(j8)-Hydro-naphtlioquin6ne C,„H„(0H)j[l:2].
[o. 60°]. Formed by treating (;3)-naphthoquinone
with cold cone. SOjAq (Liebermaun a. P. Jacob-
son, A. 211, 58). Silvery plates. It dissolves in
aqueous alkalis forming yellow solutions which
turn deep green in the air. Violently inflames
the skin.
Di-acetyl derivative C,„Hj(OAo)s. [c.
106°]. Very soluble plates (from HOAo) (Kom,
B. 17, 3025).
Isohydronaplithoqninone 7 0,oH,02. Formed
by the action of water (30 pts.) on the compound
C,(,Ha(H0Cl)2 (so-called di-chloro-naphthydrene
glycol) at 160° (Grimaux, Bl. [2] 19, 397). SmaU
needles ; sol. water and ether, insol. CHCL, and
benzene. Its alkaline solutions turn red in
the air. It reduces ammoniacal AgNO,. FeCl,
gives, in its aqueoos solution, a brown pp. soL
alkalis.
HYDROQtlNONE.
729
HlTBEO-o-OZY-BENZ-AUIDX v. Tbi-oxt-
HXDBOBBMZAMIDB.
HYSB0-0XY.0AM7H0BONIC ACIB v.
Oampbob.
HYDEO-OXY-METHYL-aTTINOUNE v. Hy-
driae of Ozy-meieyii-quiiiolinb.
DI-HYBEO-OXT-QUIITOIIirE v. Hydro-car-
bostyril nnder AuiDO-PHENYL-FBOPioiiia aoid ; v.
also Hydride of OzY-QuiNoitiNE.
HYDBO-FHENOL-FHTHALIBIIf CHLOEIDE
V. Dl-CHLOBO-PHEMTL-ANTHBAMOIi DIHYDBIDE.
HYDEO-PHEKYI-ACEIDINE v. Phenyl-
AOsmraE hydride,
EYBBO - PHENYL - CEOTONIC ACID v.
FHENYIi-BUITBia ACrD.
TETBA-HYDBO- PHENYL ■aTTINOLINE v.
Tetra-hydride of PHENyL-QQiNoiiitiE.
HYBBOPHLOBONE v. Etdboxyloquikone.
HTOBOFHIHALIC ACIBS v. Hydrides of
FaXHAIiIO ACID.
HYDBO-PICOLINE v. Hydride of Mexhyi.-
PYBIDINB.
HEXA-HYBBO-PICOLINIC ACIB v. Hexa-
hydride of Pyeedine carboxylic aoid.
HYBEO-PIPEEIC ACIBS CjjHiA. Jo) [78°].
(J8) [131°]. By reduction of piperio aoid by so-
dinm-amalgam two hydio-piperic acids are got.
They may be separated by crystallisation from
alcohol, when the (/3)-acid separates first. The
(a)-acid is the chief product (Foster, A. 124, 117 ;
Fittig a. Mielck, A. 152, 56). The {j8)-acid forms
thin needles (from alcohol). Its ammonium salt
is more soluble than that of the (a)-acid. The
(i3)-acid is only formed when the liquid becomes
very alkaline, if the alkali be constantly neutral-
ised during the reduction only (ct)-acid is got.
The (a)-acid may be converted into the (/3)-acid
by heating with (lOpts. of) dilute (10 p.c.) NaOH
9 hours at 100° (Lorenz, B. 14, 785 ; Fittig a.
Buri, A. 216, 171; 2^7, 31; VVeinstein, A.
227, 32). Br in 08^ converts the (o)-acid into
its dibromide, di-bromo-piperhydronic acid
CijHijBrjO, [187°-140°], while the (;8)-acid gives
a product of substitution, bromo-hydro-piperic
acid [171°]. The (fl)-acid is reduced by sodium
amalgam in neutral solution to piper-hydronic
acid, while the (a)-acid is not reduced thereby.
(a)-Eydropiperic acid
CH,<Q>CA.CHj.CH:OH.OH2.C02H ? [78°].
Thin needles (from hot water) ; si. sol. hot water,
V. e. sol. alcohol and ether. Oxidised by CrOa to
acetic acid. KMnOj gives piperonal, oxalic aoid,
and di-oxy-piperhydronio acid CHjOjOnHijOi
(Biegel, B. 20, 415). Not attacked by AcCl at
100°. Potash-fusion gives protocatechuic acid
and HOAc.
Salts.— NH4A': small laminse. — KHA'^ :
amorphous, formed by adding KfiO, to an alco-
holic solution of the acid. Decomposed by water.
— AgA' : crystalline pp.
(j3)-Hydro-piperic acid
CH,<g>C.H,.OH,.CH,.CH:CH.CO^ ? [131°].
Got from its (o)-isomeride by heating this acid
(1 pt.) with NaOH (1 pt.) and water (9 pts.) at
100° for some days. The aoid is separated from
ondecomposed (o)-isomeride by crystallisation
from alcohol (90p.c.). Thin needles (from alco-
hol) ; less soluble than its isomeride in the
usual menstrua. Bromine forms a substitution,
not an addition, product. EMnO, oxidises it to
di-oxy-^perhydronio acid OH^OuOuHi^O, and
methyl-anhydro-oaffeic aoid OHjOjCgHgOj.
HYDEOPYRENEaUINONE v. Pybenb.
BIHYBBOFYEIBINE v. Fybisinb dihy-
DBIDE.
HyDEO-PYBO-CINCHONIC ACID v. Di
METHYL-SnOOINIO ACID.
HYDBOPYBOMELLITIC ACIB v. Pybo
IiIELLIIIC ACID.
BIHYDROFYBEOLE t). Pybbole diht-
DRIDE.
TETEA-HYDRO-ftUINALDINE v. {Py. 3)-
Methyl-quinoline tetbahydride.
HYBKOQUINANISOL v. Methylether of OxY-
qtiinoline-tbtba-eydbidb.
HYDKOftUINICINE ij. Cinchona bases.
HYDEOaUINIDINE v. Cinchona bases.
HYDEOQUININE v. Cinchona bases.
HYDEOaUINOLINE v. Quinoline hydride.
TETEA-HYDBO-aUINOLINE HYDRAZINE
V. Amido-tetea-hydbo-quinoline.
HYDROftUINONE Gjaj)^i.e. CsH,{0H)j[l:4].
p-Di-oxy-benzene. Quinol. PyrogenUsic acid.
Mol. w. 110. [169°] (Hlasiwetz a. Habermann,
B. 8, 684). S.G. 1-826 (Schroder, B. 12, 563).
H.F. (from diamond) 86,100 (Berthelot a. Lou-
guinine, A. Ch. [6] 13, 337 ; C. B. 104, 1576) ;
100,880 (Stohmann, J. jpr. [2] 33, 471). S. 6-21
at 15°; 10-44 at 28-5°.
Formation. — 1. By the reduction of quinone,
and by the dry distillation of quinic acid (Wiihler,
A. 51, 152).— 2. Prom arbutin by boUixig with
dilute HjSO,, or by the action of emulsin (Eawa-
lier, A. 84, 858 ; Strecker, A. 107, 229).— 3. By
boiling ji-diazo-phenol sulphate with dilute (12
p.c.) H2SO4, and extracting the cooled product
with ether. The yield amounts to 46 p.c. (Weael-
sky a. Schuler, B. 9, 1159). In like manner hy-
droquinone may be obtained by the action of
water at 140° on [4:l]C„H,(OMe).N:N.S03H, de-
rived from the methyl ether of j>-nitro-phenol
(H. Salkowski, B. 7, 1010).— 4. By gently heating
a dilute solution of nitroso^phenol in NaOHAq
with hydroxylamine hydroohlpride, nitrogen
being given off (Hepp, B. 10, 1654).— 5. From
bromo-saUoylic aoid [4:l:2]CsH3Br(OH)(COja) by
fusion with NaOH, and heating the resulting di-
oxy-benzoic acid [197°] in a bath of HjSO, at
215°, when pure hydroquinone sublimes (Bakow-
ski a. Leppert, B.8, 788; cf. Demole, B.l, 1441 ;
Hlasiwetz, A. 175, 67).— 6. By passing a current
of air for 3 hours through an alkaline solution of
succinylo-saccinic ether, and heating the result-
ing di-oxy-terephthalic acid ' with EOH (Herr-
mann, B. 10, 107).— 7. A product of the distilla-
tion of succinates (VonBiohter, J.pr. [2] 20, 207).
8. By passing a rapidly alternately electric dis-
charge through a solution of phenol (q. v.).^-
9. From^-iodo-phenol by potash-fusion (Eorner,
Z. 1866, 662, 731).— 10. Occurs in the urine of
dogs that have taken benzene (Baumann, H. 6,
190), phenol (Baumann a. Preusse, B. 12, 706),
or arbutin (Mering, Ar. Physiol. 62, 276).
Prejpa/ration. — Aniline (1 pt.) is dissolved in
H2SO4 (8 pts.) diluted with water (30 pts.), and
to this solution, after cooling, powdered KjCrjO,
(8^ pts.) is gradually added, too great a rise of
temperature being avoided. The thick pulpy
mass of aniline-black produced at first changes
after a time to a dirty-brown solution, which is
730
HYDROQUINONE.
then treated with exoeas of SOj, boiled with
Bnimal charcoal, filteied, and shaken -with ether.
The ethereal extract when distilled leaves hydro-
qninone (Nietzlii.B. 10, 1934 ; 19, U68 ; A. 215,
128; Ekstrand, B. 11, 713).
ProperUes. — Dimorphous, crystallising by
sublimation in monocUnic plates; aib:o
= 2-605:l:l-668 ; j3 = 73°; and from aqueous so-
lutions in hexagonal prisms; a:c = l: '659 (Leh-
mann, Z. K. 1, 44 ; Groth, B. 3, 450). Has a
slightly sweet taste. Y. sol. alcohol, ether, and
hot water, y. si. soL cold benzene,~may be dis-
tilled. When FeCl, is added to its aqueous so-
lution there is formed a mass of lustrous dark
green spangles of quinhydrone, and at the same
time tike odour of quinone is apparent. A farther
addition of FeCl, converts the quinhydrone into
quinone, the crystals redissolving. Silver nitrate
gives a brownish-white pp., and, on warming,
reduction to black metallic silver takes place.
Hydroqninbne reduces a boiling acidulated solu-
tion of EMnOf, 1 molecule of hydroquinone
requiring 10 atoms of oxygen. Its reducing
power is intermediate between that of pyro-
oatechin and that of resorcin (Dreyfus, C. B. 105,
523). Hydroquinone reduces Pehliug's solution,
even is the cold. An aqueous solution of hydro-
quinone slowly turns brown when exposed to the
air, losing its reducing power. An alkaline so-
lution turns brown much more rapidly. Lead
acetate gives no pp. in dilute solutions, but if
hydroquinone be dissolved in a moderately con-
centrated warm aqueous solution of lead acetate
prisms of CsHg02Pb(OAc)2 l^aq separate on cool-
ing (WShler, A. 69, 299). Hydroquinone pre-
vents the alkaline fermentation of urine (An-
draeff, Vrach, 1887, 230).
Beacticms. — 1. Oa?wsai to quinone by FeClj,
chlorine, dilute HNOg, and chromic acid. —
2. By passing through a red-hot tube it is split
up into quinone and hydrogen (Hesse, A. 114,
297).— 3. Bydroxylamine in acid solution gives
the di-oxim of quinone. — 4. Strong miria acid
decomposes hydroquinone in the cold, forming
oxalic acid and HCy (Nietzki, A. 215, 138). —
5. Nitrous acid gas passed into an ethereal so-
lution of hydroquinone at 0° forms small golden
needles of di-nitro-di-oxy-quinone (Nietzki, B.
10, 2147). — 6. Not affected by potash-fusion
!W61z, A, 168, 91). Soda-fusion converts it into
1,2,4) -tri-oxy-benzene, (B) -hexa-oxy-diphenyl,
and tetra-oxy-diphenyl 0,2H,„04 (Earth a. Schro-
der, M. 4, 176 ; 5, 589).— 7. When heated with
POlj it appears to form first C8H,(0H)(0PCy
and then CjH4(0PCL,)j (Scheid, A. 218, 207).
8. HjS passed into a cold saturated solution of
hydroquinone forms colourless rhombohedra
{t^fi^^B^ decomposed by boiling water into
its components (Wohler, 4-69, 297). HjS passed
into a solution of hydroquinone saturated at 40°
forms long prisms of (CbH502),H2S.— 9. SOj
passed into a cold saturated solution of hydro-
quinone forms yeUow rhombohedra (0^005)3802,
which quickly decompose (Clemm, A. 110, 357 ;
Hesse, A. 114, 300).— 10. Aldehyde in presence
of dilute HOI forms a resin on heating (Michael
a. Ryder, Am. 9, 133).— 11. With aceUme it forms
an unstable compound C8H,0j0,H,0, which
forms triclinic crystals, decomposed into its
components by solution in alcohol, acetone, or
hot water, and even by exposure to air (Haber-
mann, M. 5, 329). — 13. HCy forms needles
(CeHj02)3H0y decomposed by heat or by water
into its components (MyUus, B. 19, 1008). —
13. AniUme when boiled with hydroquinone
forms C,Hs02(NH2Fh)2, which crystallises in
large plates [90°], sol. alcohol and hot water. Its
solution on exposure to the air is oxidised to
quinone dianilide. By boiling with benzene it
is resolved into hydroquinone and aniline (Hebe-
brand, B. 15, 1973). Hydroquinone (1 moL)
heated with aniline (4 mols.) and OaCl, at 260°
gives C3H4(0H)(NHPh) [70°] (Cahn, B. 16, 2786).
In like manner o-toVwidme and CaCl: at 245°
give O.H,(OH)(NHC,H,) [90°].— 14. p-Tolmdim
forms C,H50j(C,H,NH2)2 [98°] (Hebebrand, B.
15, 1974). — 16. By heating mSiphenyl cyanate at
100° there is formed CjH4(0.C0.NHPh)2, which
crystallises from alcohol in prisms [c. 207°]. It
is insol. benzene. At its melting-point it begins
to decompose into phenyl cyanate and hydro-
quinone (Snape, G. J. 47, 772).— 16. Ohhro-
formic ether ClCOjE't acting on sodium hydro-
quinone forms ^-phenylene di-carbonio ether
CsH,(O.C02Et)2. This crystallises from alcohol
in long needles, [100°], (310°), and appears to be
split up by heat into 00, and mono-ethyl hydro-
quinone (245°-250°) (Bender, B. 13, 696 ; Wal-
lach, A. 226, 85). — 17. Chloro-formamide gives
0^4(0.C0NH2)2, which crystallises from alcohol
in small needles [236°^.— 18. Heated with ZnCl,
and glacial acetic a(M it gives di-oxy-phenyl
methyl ketone (Nencki a. W. Schmid, J. pr. [2]
23, 546). — 19. Di-chloro-di-ethyl oxide in warm
EtOAc forms 08Hs(OH)j.OH2.0H{C,H,(OH)2)2, an
amorphous substance, sol. alcohol, acetone,
HOAc, and alkalis, and forming a hexa-acetyl
derivative. FeOl, converts it into a green colour-
ing matter C2oH,,0„ whence bromine forms
CjoH^rjO,. When an excess of di-chloro-di-
ethyl oxide acts on a solution of hydroquinone
in EtOAc there is formed a resin and a soluble
compound 0,jH,3C10, (Wislicenus a. Siegfried,
A. 243, 171).— 20. Forrmo acid forms a com-
pound (C,H,02)4CH202, which crystallises in
needles, and melts at 60°, giving ofi formic acid.
It is also decomposed into its constituents by
solution in water (MyUus, B. 19, 1003). When
hydroquinone (1 pt.) is heated with orystalUsed
formic acid (2 pts.) for 4 hours at 250° there is
formed a crystalline mixture of (CsH,02)4CH20,
and an anhydride thereof. The arihydride
{C^O^fi^'^s crystallises in colourless glassy
needles, split np by water, alcohol, or ether;
into 00, formic acid, and hydroquinone (MyUus,
B. 19, 999). — 21. KHCOs (4 pts.) heated
in a digester with hydroquinone (1 pt.) and
water (4 pts.) forms di-oxy-benzoio acid, the
yield being about 20 p.o. (Senhofer a. Sarlay, M.
2, 449).— 22. MaUo acid and H^SOt form oxy-
CHCH.=00.— CO
coumarin'l || I [250°] (Von Pech-
C(OH):CH.C.CH:CH
mann a. Welsh, B. 17, 1646).— 23. With KOH and
E2S2O7 it forms potassium oxy-phenyl sulphate
C3H,(0H)S04K crystallising in trimetric tables
(Baumann, B. 11, 1913).
Acetyl derivative CbH4|OAc)2. [121°].
Formed, slowly, by the action 01 AcCl on hydro-
quinone in the cold (Nietzki, B. 11, 470). Formed
also by heating quinone with NaOAo and AC2O
or glacial HOAo at 100° (Hesse, A. 320, 865), or
HYDROQUINONE OARBOXYLIC ACID.
731
by heating quinone with AOjO at 260° (Sarauw,
A. 209, 128). Long needles (from alsohol),
plates, or tables. V. sol. benzene, chloroform,
and ether, m. sol. alcohol and hot water. May
be sublimed. SpUt np by long boiling with
water into HOAo and hydioquinone. It it be
treated with PCI5 and the product distilled with
steam, white needles of OgClsHgO, [66°] are got
(Michael, Am. 9, 211). This bo^y, which may
be OjH,(OH)(0001:CCy,is si. sol. hot water, sol.
cold ether, benzene, and alcohol. It dissolves in
BlkaUs and is reppd. by acids. With AcCl it
gives an acetyl derivative.
Propionyl derivative C^iipO^fi)^
[113°]. Large plates (from alcohol) ; v. sol.
chloroform and ether, si. sol. hot water (Hesse,
A. 200, 246). Gives a nitro- derivative [86°]. '
Benzoyl derivative 0^t{aB7.)^. [199°].
Silky needles (from benzene) ; y. A. sol. boiling
alcohol (Dcebner, A. 210, 263).
Methyl ether CsH.,(OH)(OMe). [53°].
(242°). Formed, together with hydroquinone,
by boUing arbutin with dilute HjSOj ; formed
also, together with the di-methyl ether, by heat-
ing hydroquinone with KOH and EMeSOj at
170° (Hlasiwetz a. Habermann, A. 177, 338).
J^epared by heating hydroquinone (2 pts.) with
EOH (1 pt.), Mel (3 pts.), and some MeOH at
110° (Hesse, A. 200, 254). Plat white needles
(Xiemann, B. 14, 1989) or trimetric plates. Not
TolatUe with steam (difference from the di-
methyl ether). V. sol. cold benzene (difference
from hydroquinone). Sol. boiling water. FeGlj
converts it into quinhydrone. It reduces hot
ammoniacal AgNOj. Fuming HNOa dissolved
in ether forms a mono- and a di-nitro- derivative,
melting at 88° and 102° respectively (Weselsky a.
Benedikt, Sitz. W. [2] 84, 258).— C5H4(OMe)(OK) :
crystalline powder; insol. ether (Michael, Am.
5,177).
Di-methyl ether CeH^(0Me)2. [56°].
H.F.p. 81,924 (C,Oj= 94,000 ; H2,0 = 69,000)
(Stohmann, J.pr. [2] 35, 28). Formed by boil-
ing hydroquinone (78 g.) under 960 mm. pressure,
with KOH (93 g.), and Mel (234 g.) dissolved in
MeOH (Miihlhauser, A. 207, 252). Large plates.
Eeduces hot ammoniacal AgNO,. FeClj forms
quinhydrone.
Mono-ethyl e^er C.H,(OEt)(OH). [66°].
(247°). From the ethyl derivative of the sulphate
of diazo-phenol by boihng with water and ex-
tracting with ether (Hantzsoh, J.pr. [2] 22, 464).
Also from hydroquinone, KOH, and MeI(Wichel-
haiM, B. 12, 1501). Thin plates (from water).
SI. sol. cold water ; v. sol. hot water, alcohol, and
^ther. Slightly volatile with steam. Boiled with
dilute hy£io iodide and a httle alcohol it forms
hydroquinone. Cone. HI at high temperatures
carbonises it. Although hydroquinone forms no
aldehyde by Tiemann a. Eeimer's method, yet
ethyl-hydroquinone (14 g.) with NaOH (20 g.)
and water (35 g.) at 60° is converted into a di-
oxy-benzoio aldehyde by running in chloroform
(15 g.).
Di-ethyl ether C.H,(0Bt)2. [124°]. Prom
hydroquinone, NaOH, and EtI (Nietzki, A. 215,
145). Plates ; volatile with steam. V. sol. al-
cohol, ether, chloroform, and benzene.
Methyl ethyl ether 0;a<(OMe)(OBt).
[39°]. Prepared by heating the mono-methyl
ether with KBtSO^ and KOH, and distilling the
product (Piala, M. 5, 2£!2). Colourless crystal-
line mass, smelling like oil of fennel. InsoL
water, sol. benzene and ether.
Methyl propyl ether OeH<(OMe)(OPr).
[24°]. From the mono-methyl ether, KOH, and
potassium propyl sulphate. Purified by fre-
quent distillation with steam (P.). Leaflets; in-
sol. water, sol. benzene, el^er, and alcohol.
Ethyl propyl ether CaH4(0Bt)(0Pr).
[36°]. Pearly plates (from HOAc).
Methyl isobutyl ether
CsHifOMeHOOHjPr). (227''-230°). From
CaHj(OH)(OMe), KOH, and potassium isobutyl
sulphate. Purified by fractional distillation.
Heavy oil, with aromatic odour; sol. benzene,
ether, and alcohol (P.).
Ethyl isobutyl ether
C^H4(0Et)(0CHj?r). [39°]. Laminss (Piala, Jf.
6, 910).
Propyl isobutyl ether
0;a4(0Pr)(0CHsPr). (245°). Oil.
Di - isobutyl ether C„H4(0CHjPr)j.
(262°). Formed by heating hydroquinone with
KSO^CHjf r and KOH in sealed tubes at 150°,
being isolated by distilling the product with
steam (Schubert, M. 3, 680). Leaflets; insol.
water, sol. alcohol and ether. Chlorine foims a
di- and a tetra-ohloro- derivative, together with
tetra-chloro-quinone. Bromine forms a di-bromp-
derivative as well 'as tetra-bromo-quinone. A
mixture of HNO3 and H2SO4 forms a tetra-nitro-
derivative. AH these derivatives are crystalline,
insol. water, and sol. alcohol and ether.
Methyl isoamyl ether
C5H4(OMe)(OCH2.0H^r). (234°-237°). Oil
(Piala, M. 6, 910).
Ethyl isoamyl ether
OaH,(OEt)(OCH,.CHjPr). (252°). Oil.
Benzyl derivative CsB.fiB^.O.C^flB..
[122-5°]. Formed from benzyl-arbutin {v. Aebu-
tih) by boiling dilute HjSO, (Schifi a. Fellizzari,
A. 221, 369). Formed also ^om hydroquinone,
KOH, alcohol, and benzyl bromide. Silvery
scales (from water). V. si. sol. cold water ; v.
sol. alcohol, ether, and benzene. Sol. KOHAq.
HNO3 forms a di-nitro- derivative [137°].
Di-benzyl derivative C^jH,,©, i.e.
C,H,(O.C^,)s. [130°] (S. a. P.); [128°] (Colson,
Bl. [3] 1, 347). Prom hydroquinone, KOH,
benzyl bromide, and alcohol. Tables (from alco-
hol). Insol. water and KOHAq ; sol. benzene,
ether, and chloroform. Cone. HN^O, dissolves
it, forming a nitro- derivative crystallising in
lemon-yellow needles CijoH„(NOj)Os. [85°] (S.
a. P.) ; [78°] (C).
Bromo-phenyl etherO^Jfm){pG^^t).
Formed by the action of boiling HBr on a solu-
tion of j)-diazo-phenol sulphate :
(i.) 0„H,(OH)NjSOjH + HBr
= CX(OH)Br + Nj + H^SO,
(ii.) C„H,(OH)Br + C,H4(0H)NjS0,H
= C|iH,(0H).0.0.H4Br + HjSO, + Nj.
A pungent oil. Sol. alkalis, alcohol and ether.
Its constitution is somewhat doubtful, as its
vapour density has not been taken (Bohmer,
J. jw. [2] 24, 473).
References. — Auido-, Bbomo-, Chlobo-, Iodo-
and N1TB0-, HTDEOQumoira.
Sihydroquinone v. Tetba-oxy-diphektii.
HTSSOQTriNONE CABBOXYLIC ACIO *.
Dl-OXT-EENZOIC AOID.
r39
HYDROQUmONE CARBOXYLIO ACID.
Eydrnqninone di-carbozylic acid v. Di-ozi-
IBBEFHIEALTC ACID.
Hydioqniuone tetra-carbozylio acid C,gHgO,,
t.e. C»H,(0H),(C08H), [1:4:2:3:5:6]. Di-oxy.
pyromellitic acid. Obtained b; saponifying the
etbei ^th KOHAq (Nef, A. 2S7, 32 ; C. J. 53,
428). Flat, pale yellow, needles (containing 1^
■q), V. sol. hot water, the yellow solution ex-
hibiting green fluorescence. FeCl, colours its
solution blue. Nitric acid does not act on it in
the cold, but on warming complete decomposition
occurs. Chromic acid behaves in like manner.
Ha,A'»: characteristic faint yellow prisms, v. si.
sol. NaOHAq. — Ag,A'' : lemon yellow flocculent
pp. The lead salt is a light yellow granular
pp. Thebarium saltisapale yellow granular
pp.
Ethyl ether Et,A'\ [128°]. Formed by
treating a solution of quinoue tetra-carboxylic
ether in HOAc with zinc-dust (Nef). Pale
yellow needles, V. sol. alcohol, ether, and HOAc,
(he solutions exhibiting blue fluorescence.
Crystallises in two forms, both monoclinic, viz.:
(i.) o:6:c = 2-388:l:3-060; 8 = 64° 36'; and (ii.)
a:b:e = 1-790:1 :3-321 ; /3 = 81° 53' (Groth). Its
alcoholic solution is coloured bluish-green by
FeCl,. It dissolves in dilute NaOHAq. NaOKt
gives a red colour. Nitric acid (S.G. 1-4)
oxidises it to quinone tetra-carboxylic ether.
Zinc and HCl reduce it to the following body.
Dihydride of hydroquinone tetracarboxylic
ether C,gHj,0,„ i.e. C„H2(OH)j{COjEt)4. p-Diketo-
methylene tetracarboxylic acid. [144°]. Formed
by adding zinc-dust (10 g.) and cone. HCl to an
alcoholic solution of the preceding ether (2 g.)
(Nef). Colourless needles or prisms (containing
xaq). In the hydrated condition it is v. sol.
alcohol and ether ; in the anhydrous condition it
is but slightly soluble in these liquids. Its
solutions show feeble blue fluorescence. Its
alcoholic solution js coloured cherry -red by FeClj.
Bromine added to its solution in CSj, forms
hydroquinone tetra-carboxylic ether. It reacts
with phenyl-hydrazine and with hydroxylamine;
and on this account its formula may also be
written CjHj02(C02Et), i.e. tetra-hydride of
quinone tetra-carboxylic acid. Hence Nef sug-
gests that one of the two crystalline forms in
which he obtained hydroquinone tetra-carboxylic
ether may be the di-hydride of quinone tetra-
carboxylic ether C,Hj02(C02Et)<.
HYSBOQVINOXE CABBOXYLIC ALDE-
HYDE V. Dl-OXX-BENZOIC AliDEHYDE.
HYDBOQXriNONE-GLirCOSIDE v. ABBnim.
HYDROftUINONE-PHTHAIElK CjoH.A i.e.
C0<C«f ^>C<CAjOH)^0 Mol. w. 332.
[227°]. Formed, together with quinizarin, by
heating hydroquinone (2 mols.) with phthalio
anhydride (1 mol.) and a quantity of SnCl, equal
to 13 times the weight of the mixture, the whole
being heated at 125° for 18 hours (Grimm, B.
6, 506; Ekstrand, B. 11, 718). Tables (contain-
ing aq from water) or needles (from ether) ; si.
sol. hot water, v. sol. alcohol and ether. Crys-
tallises from alcohol in needles (containing
HOEt). Alkalis turn its aqueous solution deep
violet. Bromine, added to its solution in HOAc,
forms penta-bromo-hydroqoinone phthalon
C^gHiBr^O, [abgve 3Q0°], a colourlesa crystalUne
powder, insol. all ordinary solvents, tt givef
colourless solutions with alkalis.
Di-acetylderivativeG^i^afi^. [2M^.
Colourless crystals (from MeOH).
Hydroquinone phthalin CaiHuO.,. [203° un-
cor.]. Formed by heating hydroquinoncrphthal-
ein for 4 hours with zinc-dust and aqueous
NaOH. Crystallises from benzene in large tables
(containing C,He). Its alkaline solutions are
colourless. H2SO4 forms a red liquid, whence
water gives an olive-green flocculent pp. of hy-
droquinone-phthalidin, which dissolves in ether
with green fluorescence. Hydroquinone-phthalin
readily yields the corresponding plithalein when
treated with oxidising agents.
Di-acetyl derivativeG^^'H.^^c.jO^. [191°].
Colourless prisms (from MeOH).
HYDEO-ftUINOlTE STTLPHONIC ACID
CsH,(0H)„S03H. Prepared by heating hydro-
quinone (i pt.) with 8 pts. of HjSO, at 50° for
3 hours (Seyda, B. 16, GS8). Crystalline solid.
Gives a blue colouration with FcjCla. By fusion
with NaOH or by heating to 180° with aqueous
or alcoholic NH, the HSO, group is eliminated
as sulphate and hydroquinone regenerated.
Salts. — A'K : long monocUnio crystals,
o:6:c = •96:1:2-2256; B = 107°23'; v. sol. water,
si. sol. alcohol ; reduces AgNOj. — A'jBa : amor-
phous powder, sol. water. — A'^Zn 4aq : concentric
needles, v. sol. water and alcohol.
Hydroqaiuone disulphonic acid
CjH2(OH)j(S03H)2. Formed by treating quinio
acid with" fuming H.^SO< (Hesse, A. 110, 195).
Syrup ; v. sol. water and alcohol, insol. ether.
Solutions of its alkaline salts give a deep blue
colour with FeClj and reduce AgNOj. Converted
into quinizarin by heating with phthalic acid and
aSOj. — K2A"liaq: prisms. — CaA"3aq. —
BaA" 4aq : monoclinic prisms, m. sol. cold water.
— A"(PbOH)2.
Hydroqninone-di-BuIphonic acid
C„Hj(OH)j(S03H)2. Prepared by heating hydro-
quinone (1 pt.) with 5 pts. of fuming H^SO, for
1 hour at 100°-110° (Seyda, B. 16, 690). Formed
also by heating potassium thioohromate with
water at 135° (Graebe, A. 146, 43). Long deli-
quescent needles. V. sol. alcohol, v. si. sol.
ether. Gives quinizarin when heated with
phthalio acid and HbSO^.
Salts. — A"K2 4aq: long prisms, sol. hot
water, si. sol. cold water, insol. alcohol. FeClj .
colours its aqueous solution blue. It reduces a
boiling solution of AgNOj. — A"Na2« : white
amorphous powder, sol. water, insol. alcohol. —
A'BaS^aq: glistening needles or long prisms,
sol. hot, si. sol. cold, water, insol. alcohol. —
A"Zn 6aq : concentric needles or long prisms,
sol. hot water.
Hydroquinone di-sulphonic acid
C|jHj(OH)2(SOjH)2. From p-diazo-phenol disul-
phonic acid (Wilsing, A. 215, 239). Does not
crystallise. Gives with FeCl, a violet colour.
Eeduoes AgNOj. BaClj and Pb(OAc)j give pps.
sol. HOAcAq.
Salt.— K2A"aq.
Hydroquinone-disulphonic acid. Di-methyl
derivative C8H2(OMe)2(HS03)j. Prepared by
sulphonating the di-methyl ether of hydro-
quinone (Kariof, B. 13, 1673). Colourless deli-
quescent needles. V. e. sol. water and alcoholi
insol. etbet.
HYDROXONIO ACID.
733
Salts.— A"K,: large colourless tables, sol.
water. FeCl, colours its solution deep violet-
blue. — ^A"(NH4)2: colourless soluble prisms. —
A"Ba : white amorphous powder, v. sol. water,
Inaol. alcohol. — A"Zn : felted needles.
HYSBOBETENEQTTINONE v. Betbnb.
HYSBOSORBIC ACID v. Hexbnoic acid.
HYDBOSULPHISBS. (SuVphohyd/rates.)
Compounds of an element or radicle witib hydro-
gen and sulphur. The name is sometimes re-
stricted to those compounds which on account
of their reactions probably contain the group
SH. The hydrosulphides are the sulphur ana-
logues of the hydroxides. The name sulpho-
hydrates, sometimes given to these compounds,
is badly chosen, as it suggests a compound of
water with a sulphur-containing substance. The
hydrosulphides are not numerous. Many non-
metallic sulphides combine with more positive
sulphides to form salts the negative radicle of
(rhich is the non-metallio sulphide ; such salts
tnay be regarded as derivatives of acidic hydro-
sulphides; but very few of these hypothetical
acidic hydrosulphides have been isolated. As^S,,
for instance, combines with many metallic sul-
phides to form salts of the three classes
As^Ss-M'^S, AsjS3.3M'jS, and ASjS3.2M"S ; the
hydrosulphides of As corresponding to these
salts would be As2S4H2 or AbS.SH, AsjSbHb or
As(SH)3, and As^SsH, or As2S(SH),; but none
of these hydrosulphides has been isolated. The
compounds H.SH and CS(SH), are acidic hydro-
sulphides. The metallic hydrosulphides which
have been isolated, e.g. CaS.^,, BaS.^Hj, are few
in number and on the whole unstable ; the pro-
duction of a hydrosulphide seems to be fairly
characteristic of a markedly positive metal.
M. M. P. M.
HYDEOSXTLPHOCYANIC ACID v. Cranio
(SULPHO) ACID, p. 303.
HYDBO-TEEEPHTHALIC ACID v. Hydrides
of TeBEPHTHAIiIO ACID.
HYDBOTHYMOQTriirONE 0,„H„0, i.e.
CsHjMe(C3H,)(0H)jt [140°]. (290°). Formed
by reducing thymoquinone with SOj (Carstan-
jen, J. pr. [2] 3, 64 ; Lallemand, A. 101, 121 ;
102, 121). v. si. sol. cold, m. sol. hot, water ;
v. sol. alcohol and ether. May be sublimed.
Gives thymoquinone on oxidatioii. Its methyl
ether constitutes 80 p.c. of the essential oil de-
rived from the roots of Arnica nunvtaiM (Sigel,
A. 170, 363).
Sulphonic acid CeHMe(C,H,){0H)j.S03H.
Potassium salt EA'. Formed by warming
thymoquinone with aqueous K^SO, (Carstanjen,
J. pr. [2] 15, 478). Crystalline. FeCl, colours
its aqueous solutions emerald green, the colour
changing to yellow. It reduces silver solution
forming a mirror. Decomposed by boiling
HClAq into H^SO, and hydrothymoquinone.
HYDSOTIGLIC ACID v. Valeric acid.
HYDEOTIC ACID CsHjNO,. A syrupy acid
occurring in perspiration (Favre, J. pr. 58, 365).
Sol. alcohol.— AgA' : v. si. sol. alcohol.
HEXA-HYDEO-TOLUENE v. Toluene hbxa-
HTDBIDE.
HYDSOTOLTTQTTINONE C.H3Me(OH),[l:2:5].
[124°]. (N.) ; [126°] (Eiedel, JB. 13, 126).
Formation.— 1. By reducing toluquinone
with SO, (Nietzki, A. 215, 159).--2. By oxidising
0-toluidine with chromic acid mixture (Nietzki,
B. 10, 1935).— .3. By treating amido-o-cresol with
nitrous acid (Nevile a. Wiuther, C. J. 41, 415 ;
B. 15, 2979). Pearly plates. May be sublimed.
V. e. Bol. water, alcohol and ether, m. sol. benz-
ene. Oxidised readily to toluquinone. In
aqueous NaOH it forms a bluish-green solution,
turning dark brown. Its ammoniacal solution
turns brown in air. FeCl, gives a brownish-red
colour. Bleaching powder gives a bluish-green
colouration, turning brown. It combines with
aniline, forming C,Hj(0H)2(NHjPh)j, which crys-
tallises in small white plates [85°], sol. water
(Hebebrand, B. 15, 1974). With p-toluidine it
forms in like manner C,H3(OH)2(C,H,NH2)2,
crystallising in pearly plates [90°].
Di-acetyl derivative C,H,(OAo)j. [52°],
Mono-methyl ether G,H,(OH)(OMe).
[72°]. (240°-246°). Formed, together with the
di-methyl ether, by heating hydrotoluquinone
(12pts.) with NaOH (8 pts.), Mel (30pts.) and
MeOH (100 pts.) at 100°- Plates. Sol.
NaOHAq.
Di-methyl ether C,HB(0Me)2. [15°].
(214°-218°). Differs from the preceding ether
in being volatUe with steam and insol. alkalis.
Oxidised by chromic acid to a compound
CisHggO,, crystallising from alcohol in thin,
almost black, needles [153°], wiiioh may be re-
duced by aqueous ammonium sulphide to
CijHiiiO,, which separates from benzene in slen-
der needles [173°]. The compound C„H,,04 is
converted by heating with cone. HClAq at 100°
into MeCl and C„H,20, [232°], which separates
from alcohol in plates (containing aq).
Isohydrotoluquinone CgHgO^. [204°].
Formed by allowing toluquinone (2 pts.) to stand
for 24 hours with a mixture of H^SO, (5 pts.) and
water (Spts.) and reducing the resulting isotolu-
quinone with SO, (Spica, Q. 12, 225). Pearly
needles, sol. benzene, v. e. sol. alcohol and ether.
Keoxidised by moist air to isotoluquinone. As
only one toluquinone is indicated by theory, this
body is perhaps a polyraeride thereof.
HYDBOXAMIC ACIDS v. Exdboxvlaminb
DBIIIVAIIVES.
HYDBOXIDES. Compounds of an element
or radicle with oxygen and hydrogen, not with
water. The term is restricted by some chemists
to compounds whose reactions indicate the pre-
sence of the group OH {v. Htdkates). If an
hydroxide is defined to be a compound of an
element or radicle with the group OH, a classifi-
cation of hydroxides may be made, on the basis
of composition, into mono-, di-,. . . .ra-hydroxyl
compounds. Hydroxides vary much in pro-
perties; some are alkaline, e.gi. EOH and NaOH;
bome are acids, e.g. NO^.OH and $02(0H)2; some
are neutral, e.g. H.OH (cf. Hydbaies).
M. M. P. M.
HYDBOXONIC ACID C,H„N,0,. ^ An acid
produced by the action of sodium-amalgam on
acid potassium allantoxanate C4H2N30,K (Pono-
maroff, J. B. 11,56). Heavy crystalline powder,
si. sol. boiling water. Not affected by boiling
HClAq or HNO,. HCL&.q at 150°_ forms OOjj
ammonia, and a little CO. Boiling bromine
water gives biuret, CO, and CO,. Alkaline
EMnO, oxidises it to allantoxanio acid. —
(NH,),!." : small needles, si. sol. cold water. —
EjA" : email prisms. S.l-6<— Na^".— BaA"2aq:
784
HYDROXONIC AdW.
crystalline pp. — MgA"4aq. — PbA"l|aq. —
AgA" 3aq : crystalline pp.
HYSBOXY- GOmFOlTNDS v. 0x7- com-
pounds.
HYDEOXYIi. The radicle OH. This group
occurs in alcohols and in most acids. Its pre-
sence in organic componnds is shown by the
tollomng reactions : 1. Sodium gives off hydro-
gen. — 2. Zinc ethyl gives off ethane (Japp,
0. J. 37, 665):— 3. PCI5 gives off HCl.— 4. AcCI
and BzGl react, giving off HCl, and forming
acetyl and benzoyl derivatives of the substance.
5. Ac^O and BzjO also form acetyl and benzoyl
derivatives. The nimiber of hydroxyls present
may be determined by saponifying the acetyl
derivative with standard alkali, and titrating the
product with standard acid (Schift, B. 12, 1532).
Jackson a. BoUe (Am. 9, 82) prefer to prepare
the j7-bromo-benzoyl derivative by means of ^-
bromo-benzoyl chloride or anhydride, and then
to determine by analysis the percentage of brom-
ine in the product. — 6. According to Landwehr
(B. 19, 2726) if a substance is added in excess to
15 CO. of a very dilute solution of ferric chloride
(prepared by adding 2 drops of a 10 p.c. solution
of FeCl, to 60 c.c. of water), the production of a
Bulphur-yellow colour denotes the presence of
hydroxyl. «
Hydrogen dioxide has sometimes been termed
hydroxyl.
HYSBOXTLAMINE NH.OH. {Oxyam-
moma). This base was prepared by Losseu in
1865 by reducing C,HjNO, by the action of Sn
and HGlAq. It is a product of the reduction of
nitroparaffins and nitrolio acids, of HNO,, HKD^,
some nitrates and nitrites, and is also produced
by the union of H with HO. NH^OE has not
been isolated; it is known only in aqueous solu-
tion.
Fmrniation. — 1. By the partial reduction of
ENO3, by Sn and certain other metals with
HClAq or H2S04Aq, or by an acidified solution
of SnClj. Divers (C, J. 43, 443) and Divers a.
Shimidzn (C. J. 47, 597) have examined the
reaction of Sn, Zn, and some other metals on
HNOjAq in presence of HCl or H^SO,. They
conclude that NH^OH is a product of the inter-
action of both acids and the metal, and that it
is not produced by the reducing action, on the
HNOg, of hydrogen formed by the reaction be-
tween the metal and the HCl or H2SO4 present.
NH3 is formed along with NH^OH ; according to
D, a. S. the KH, is a product of the reaction be-
tween the metal andHNOj. Von DumreicherlM*.
1,724) found that SnCl, in presence of HCl reduces
HNO, to NHjOH ; Divers a. Haga (C. J. 47, 623)
find that if sufBcient water is present to prevent
any reaction between the HCl and HKO, no
NHjOH is produced ; the SaGl^ thus appears to
react with a product of the interaction of the
two acids. — 2. By reducing NH4NO3 by Sn and
HClAq (Maumenfi, C. B. 70, 147) ; or NaNOj by
the same reagents (Donath, W. A. B. [2nd part]
75, 566). — 3. By reducing NO by passing it into
Sn and HClAq, or by reaction with SnCl^ and
HClAq (Ton Dumreioher, M. 1, 724 ; Divers a.
Haga, O. /. 47, 623). According to D. a. H.
there is no action between NO and acidified
SnCL, solution at 100°. — 4. By the action of Sn
and HOI, or SnCL, in HClAq, on CjHjNOa (Lossen,
Z. [2] 1, 651). — 5. By reducing various nitro-
paraffins bySn and HCl (Meyer a. Looher, B. 8,
215) ; also by reaction of nitroparaffins with
HjSO, (Preibisch, J. pr. [2] 7, 480 ; 8, 316 ;
M. a. L. l^.). — 6. By reducing nitrites of K or
Na, and some other nitrites by H^S (Divers,
C. J. 43, 454 ; 51, 48). — 7. By reaction of oonc.
HClAq with fulminates {v. p. 317, Reactions 10
and 11).
PreparaUon. — 1. A mixture of 120 grama
C2H5NO,, 400 grams granulated tin, and 800-
1,000 C.C. HClAq S.6. 1-19, to. which are added
about 2,500-3,000 0.0. water, is placed in several
large flasks; action proceeds without heating;
the flasks are shaken from time to time ; when
the action ceases the contents of the flasks are
mixed, at least an equal volume of water is
added, and the Sn is ppd. by passing in H^S ;
the filtrate from SnS is concentrated, at first
over a flame, then on the water-bath; NH,G1
separates out, then a compound, of NH,C1 with
SnCl,; these crystals are removed, and the
mother-liquor is evaporated to a small bulk,
when crystals of NHjOH.HCl mixed with NH,C1
separate (the mother-hquor contains various
compounds of C, and chlorides of Fe, &e., de-
rived from the HCl or the Sn used). The crystals
are shaken with a very little cold absolute alco-
hol, the liquid is poured off ; a few drops more
absolute alcohol are added, and again poured off;
the crystals are now kept in contact with boihng
absolute alcohol until they are dissolved, the
liquid is filtered hot, and (while still hot) enough
FtCl, in alcohol is added to ppt. the NH4CI as
2NH,Cl.PtCl, ; the filtered liquidyields crystals of
pure NH2OH.HCI on cooling ; by evaporating the
mother-liquid a further 2n^^d of crystals is ob-
tained ; these should be recrystallised from hot
absolute alcohol. About 47 grams NH2.OH are
obtainable by this process from 120 grams
CsHjNOj (Lessen, A. Svppl. 6, 220). To pre-
pare the C^HjNOj for making NHjOH, 400 grams
HNOjAq S.6. 1-4, which have been boiled for a
few minutes with about 7 grams urea nitrate
and allowed to cool, are mixed with 300 grams
commercial absolute alcohol; 300 grams urea
nitrate are added, and the whole is distilled from
a tubulated retort until from f to f have distilled
over, when a funnel with glass stopcock is placed
in the tubulus of the retort, and a freshly pre-
pared mixture of 400 g. HNO,Aq with 300 g.
alcohol is allowed to flow into the retort,
drop by drop, while distillation proceeds. The
CjHjNO, thus obtained is washed with water,
and then used as already described. — 2. You
Dumreicher (Sit2. W. 82, 660) recommends
the reduction of C2H,.N0, by a solution of
SnClj in HClAq ; about 90 p.c. of the theoretical
yield of N^OH is thus obtained. CjHjNO, is
mixed with a solution of SnCL, in cone. HClAq
in the ratio shown by the equation
02HjNO, + 3SnClj + 6HCl
= NH2.OH + OjHjO + SSnCl, + H2O ;
alcohol is added so as to make a homogeneous
liquid, and after a little the whole is gently
warmed until a little of the liquid gives a clear
yellow pp. with HjS. The Sn is removed by ppn.
with HjS, the filtrate is evaporated and treated
as directed in 1. Instead of the tedious process
of ppg. Sn by HjS, and the long-continued eva-
poration of the filtrate, Y. Meyer (B. 15, 2789) re-
commends to concentrate the liquid considerably,
HYDROXYLAMINE.
785
and when cold to add axcesa ol Na^CQ,, to filter
from the pp. which contains Sn, and also Fe, Ca,
&8., present as impurities, to carefully acidify
with HCl, and evaporate on the water-bath ; by
treating the residue with hot absolute alcohol,
filtering from NaOl and NHjCl, and cooling,
crystals of NHjOH.HOl containing only "about
10 p.o. NHjOl are obtained. These crystals are
gufiSoiently pure for most purposes for which
NHjOH is used.— 3. Ludwig a. Hein {B. 2, 671)
pass NO (made from HNO„ HjSO<, and FeSO„
and stored in a gasholder) through a series of
bottles containing Sn and cone. HClAq to which
a little FtCl, has been added ; the dissolved Sn
is removed by ppn. as SnS ; the rest of the pro-
cess is as described in 1. In this reaction some
N is always produced, but KjO is not formed
pivers a. Hager, C. J. 47, 623). If air is ex-
cluded no NH, is produced'acoording to D. a. E. ;
but Von Dumreioher (M. 1, 724) says that NH,
is formed by reduction of NHjOH by the SnClj.
4. NH2OH is not economically prepared by the
reduction of ENO,. In one case, however. Divers
obtained fully 80 p.o. of the ENO, as NE^OE
(C J. 43, 445) ; in this experiment 58 c.c. cone.
E01A.q were mixed with 5 c.o. ENOsAqS.G. 1-42,
and the mixture was at once poured on to 85 g.
granulated tin in an atmosphere of CO,, the
flask being placed in cold water. If this method
is employed the liquid must be kept very de-
cidedly acid throughout the reaction ; about 5-6 g.
S2SO4 (supposing that acid to be used) should
be present in every 100 c.o. liquid, the amount
of ENO, in 100 cc.not exceeding •7g. (Divers a.
Shimidzu, C. J. 47, 597). Divers (C. J. 48,
4S3) has examined the action of various metals
on a mixture of ENO, and ECl or EjSO,.
NEjOEAq is obtained from one of the salts
prepared as described, (i.) by forming the sul-
phate, by evaporating the other salt with an
equivalent quantity of EjSO,, and crystallising
from alcohol, and (ii.) by decomposing the sul-
phate in aqueous solution by an equivalent
quantity of BaO^E, in solution, and filtering
from BaSO,.
Properties. — NH^OH has not been isolated.
When NE^OEAq is distilled NH3 and water
pass over, the distillate also contains some
NBLjOE. NEjOEAq is colourless and odourless ;
it has an alkaline reaction, and acts as an ener-
getic reducer. An alcoholic solution of NE^OE,
obtained by decomposingoono.2NE20E.E2S04Aq
by EOE in alcohol, reddens and inflames the
skin. NEjOEAq produces pps., insol. excess,
in solutions of ZnSO„ NiSO,, FeCl,, alum, Cr-
almn, and Pb acetate; pps. are not produced
from salts of Mg, Ca, Sr, Ba. NEjOBAq
is nnstable, it is decomposed by KOEAq.
NE,OEAq is distinctly basic; in its reactions
with acids it resembles NE^Aq, both combine
with the acids to form salts M.EC1, Mj.E^SOt,
Ac, when M = NEjOE or NE,. The heat of
neutralisation of NEj,OEAq is considerably less
than that of NE^Aq ; Thomsen (Th. 1, 405) gives
these numbers: [2NH^OEAq,2E01Aq] =18,520;
[2NE'0EAq,B^S0*Aq] = 21,580 ; the values for
NB, are 24,540 and 28,150 respectively. The
introduction of the acidic group OE in place of
E considerably decrease^ tiie basic character of
the molecule. More heat is produced in the
formation, from the elements, of an aqueous
solution of NEjOE than of NE, ; Thomaen's
numbers are [N,E»,0,Aq] = 24,290 ; [N,E»,Aq]
= 20,820; similarly with the hydrochlorides
[N,ES0,C1] =76,510 ; [N,asCl] - 75,790 {Th. 2,
84).
As NE,.OE cannot be gasifled its molecular
weight is unknown. Lessen has shown that
there are three isomerides of the form NBB.OB,
and three of the form NBjBi.OB, where B is one
monovalent radicle and Bi is another monova-
lent radicle. It appears then as if each E in
NEjOE were differently related to the rest of
the molecule from the other E atom: the
forinula NE^.OE, however, shows two E atoms
similarly related to the rest of the molecule.
This formula is confirmed by the production of
hydroxylamine by reducing nitrites (NO2.OE),
and by the general reactions and combinations
of the body. If the molecule of hydroxylamine
is represented bytheformula HO-H^N — NE^.OE,
the existence of all the observed isomeric' deriva-
tives is accounted for {v. Ezdboxylamine deri-
vatives).
Detection and Estimation. — Traces of salts
of NEjOE ppt. CujO from fairly cone. KOEAq
or NaOEAq to which a little CuSOjAq
has been added (Lossen) [2NH3O H- 4CuO
= NjO + 2CujO-i-3E20]. NEjjOH may be esti-
mated by titration with standard I, in presence
of MgO added to neutrahse EI [2NE,6-l-2Ij
= NjO + EjO + 4EI] ; or by warming wilii solu-
tion of Pej(SO,), to 80°-90°, and determining the
ferrous iron by standard EMnO^Aq
[2I'e2(S04), + 2NE,0
= 4FeS04 + 2EjS0, + N,0 -I- EjO]
{v. Meyeringh, B. 10, 1940),
Reactions. — 1. NTT^nTTAg reduces many me-
tallic salts in solution ; CuSO^Aq gives a grass-
green pp., becoming reddish, on boiling CU2O
ppts. ; the pp. in the cold is sol. in excess of
NEjOEAq, access of air to the solution causes
a brown-green pp. sol. on gently warming ; am-
moniacal CuS0,Aq is decolourised by NE^OEAq,
CUSO4 with excess of EOE is reduced to Cu^O ;
EgCl^Aq is reduced to EgCl; AgNO, gives Ag
with evolution of gas (NjO and N);' salts of
Au and Ft are reduced to metal, the latter on
warming (Premy, C. B. 70, 61, 1207; Lossen,
B. 8, 357) ; EjCrOjAq is reduced, but only on
warming, addition of a little E^SOt causes rapid
evolution of gas and formation of a brown pp.
(Lossen, A. Swppl. 6, 235). In these reactions
the NE2OE is generally completely decomposed
to E^O, NjO, and N ; according to Meyeringh
(B. 10, 1940) and Donath (W.A. B. 75 [2nd part],
566), only NjO is evolved. — 2. According to Ton
Dumreicher (M. 1, 724) amcUfied stamious chlor-
ide reduces NE^OE to NE, at 100° ; but Divers
a. Eaga (C. 3. 47, 623) assert that no NE, is pro-
duced if access of air is prevented. — 3. Tin and
hydroohlorie acid slowly reduce NEjOE to NE,
(Lossen) ; according to Divers a. Eaga (l.c.) Sn
and hot cone. EClAq have hardly any action on
NE2OE.ECI ; Divers a. Shimidzu (0. J. 47, 597)
say that Zn and E.;SO,Aq likewise have practi-
cally no actionon2NE20E.BjS04.— 4. NE^OEAq
and salts of NE^OE are decomposed hy potash
with evolution of N, NE„ and a little N^O. —
6. lodme quickly decomposes NE^OE and its
salts to N,0 and E^O with formation of EI. —
6. Ferric sulphate is reduced by NH,0H and its
738
,nYDEOXYLAmNE.
Baits to FeSO,, with evolution of N^O. — 7. Con-
tact with zinc, in absence of acid, decomposes
NH20H and its salts (Divers a. Shimidzu, C. J.
47, 597). — 8. SocUvm, nitrate causes evolution of
NjO from 2NHjOH.H2S04Aq ; dilute solutions
of KNOj and 2NH20H.H2S04 only react when
boiled (V. Meyer, C. C. 1876. 620).
Ccmilmiations. — NHjOHAq combines with
many acids to form salts. In these reactions
NHjOH behaves similarly to NH, ; the acid and
base combine, and the salt is the only product
of the interaction. The salts of NH^OH have
the composition BAj B^Au B,,A„i, where B
E^NHjOH, 'Ai= monobasic acid, Aii = dibasic
Bcid,'Ani=:tribasic acid. The salts of NH^OH
crystallise without water; they are easily de-
composed by he»t, generally with evolution of
N and N2O. The chief salts are acetate
TS'Kfl'H.C^fli, crystallises from warm absolute
alcohol ; hydrochloride NHjOH.HCl, crystallises
from alcohol or water, melts at 100°, and then
decomposes violently to N, HCl, HjO, and NHjCl.
V. Meyer (B. 15, 2789) says that the presence of
10-15 p.c. NH,C1 in NHaOH.HOl is not objec-
tionable for most purposes for which the salt is
used, and that the salt is perfectly stable when
it is mixed with some NH,C1. If, however, it
should contain any HOI or PeClj the whole of
the NH2OH.HOI is slowly changed to NHjCl.
Nitrate NH2OH.HNO3, easily sol. in absolute
alcohol ; phosphate, NH2OH.H3PO,, separates in
small crystals on mixing dilute solutions of
Na^HPOi, and an easily sol. salt of NH2OH;
sulphate 2NH2OH.H2SO4, very sol. in water, ppd.
by alcohol. Meyeringh (B. 10, 1946) describes
some double salts: hydroxylarm/ne alum
(2NH20H.HjS04).Alj(SO,)3.24H20, and a chrome-
alum (2NHjOH.H2SO<).Crj(SOj3.24H20, and
ircm. aUm (2NH20H.HjS04).Fe2(S04)3.24H20.
These double salts are formed in octahedral
crystals by mixing cone, solutions of their consti-
tuent salts and allowing to crystallise ; the double
salt (2NH:20H.HjS04).MgS04.6H20 was obtained
by mixing solutions of the constituent salts.
M. M. P. M.
HTSSOXYLAMIXE DEBI7ATIVES. Hy-
. droxylamine is a very important reagent in or-
ganic chemistry, since it reacts with aldehydes
and ketones with elimination of water, forming
the oxims (V. Meyer a. Janny, B. 15, 2783 ; 16,
167)
E.CHO + H^NOH = ECNOH + HjO
E.CO.R' -I- HjNOH = EE'CNOH + H^O.
The oxims are also called isonitroso- compounds,
and are frequently interchangeable with nitroso-
Gomponnds. Thus, nitroso-phenolis identical with
the mono-oxim of quinone ; and the oxim of pyr-
uvic acid is identical with ;3-nitroso-propionio
acid. The reaction of hydroxylamine on ketones
sometimes does not take place when there are no
hydrogen atoms attached to the carbon united
with the carbonyl (Herzig a. Zeisel, B. 21,
3493).
Thioaldehydes react upon hydroxylamine in
the same manner as aldebydes, producing the
same compounds.
Alkoyl derivatives of hydroxylamine
Benzoyl derivative BzNH.OH. Benz-
hydroxamic add. [125°]. S. 2-2 at 6°. If
hydroxylamine hydrochloride (1 pt.) be dissolved
in water (9 pts.) and the solution) «ft9r neDtrttU-
sation with NaOH, be mixed with benzoyl
chloride (8 pts.) in the cold, di-benzoyl-hydroxyl-
amine separates while the benzoyl hydroxyl-
amine which remains in - solution may be ppd.
as Ba salt by baryta, and then liberated by
H2SO4 (Lessen, A. 161, 347). Trimetric plates
(from alcohol); a:&:c = -356:1: -322 (Elein, A.
166, 180). M. sol. water, v. e. sol. alcohol, si.
Bol. ether and CS„ insoL benzene. Decomposed
somewhat violently by heat. Acid in reaction.
Boiling dUute HCl or H^SO, split it up into
hydroxylamine and benzoic acid.
Salts. — BzNH.OK(BzNH.OH) : trimetrio
prisms or plates, m. sol. warm water, si. sol,
alcohol. Crystallises from an alcoholic solution
even in presence of excess of caustic potash
(BzXH.ONa)(BzNH.OH) 3aq: plates. Effloresces
in dry air. Its aqueous solution gives whits
pps. with solutions of CaSOf, alum, MnCl,, and
lead nitrate; a nearly white pp. with CuSO,; a
green pp. with chrome alum ; a whitish-green
pp. with NiSOj ; a peach-coloured pp. witii co-
balt nitrate ; and a yellow pp. with mercuric
chloride. All these pps. dissolve in excess.
Silver nitrate gives a white pp., insol. excess,
and rapidly blackening. FeClj gives a dark-red
pp. dissolving in excess with formation of an
intense red solution. This characteristic coloura-
tion is destroyed by cone. HClAq but reappears
on dilution. — ^Ba(0.NHBz)2 : minute needles,
formed by neutralising the acid potassium salt
vdth ammonia and ppg. with barium chloride.
— Ba(0NHBz)2(H0NHBz)s: crystallises insmall
prisms, together with free benzoyl-hydroxyl-
amine, when the neutral Ba salt is decomposed
by an insufficient quantity of H^SO, and the
filtrate is allowed to evaporate. V. si. sol.
water and alcohol. — Ca(0NHBz)2 : amorphous
pp. — Zn(ONHBz)j : crystalline pp.
Ethyl ether v. Ethyl-hydroxylamint
,(mfra).
Di-henzoyl derivative BzjNOH. Di-
henzhydroxa/ime acid. [153°] (Steiner, Jl. 178,
226 ; cf. Heintz, Z. [2] 5, 733). Formed by the
action of BzOl on hydroxylamine or on benzoyl-
hydroxylamine (Lossen). Formed also by treat-
ing nitro-ethane with BzCl and extracting the
product with boiling benzene (Kessel, Bl. [2] 38,
171). Needles or prisms. SI. sol. water, cold
alcohol, ether, and CSj, m. sol. hot alcohol,
almost insol. benzene. Acid to litmus. Decom-
poses violently ^hen heated above its melting-
point, forming bei^zanilide phenyl oyanate,
HOBz, and CO, (Fieschel, A. 175, 305). Boiling
dilute acids split it up into hydroxylamine and
benzoic acid. Boiling baryta- water forms benzoio
acid and benzoyl-hydroxylamine. Fed, does
not colour solutions of di-benzoyl-hydroxylamine,
but in neutral solutions it gives a reddish-yellow
pp. A solution of the K salt gives white pps.
with nitrate of Pb, Ag, and Oo,withMnClj, with
ZnSO, and with CdSO,; a bluish-green pp. with
chrome alum; and an apple-green pp. with
NiSO,. Unlike mono-benzoyl-hydroxylamine it
gives no pp. with salts of the alkaline earths. —
BzjNOK: thin pearly plates (from alcohol) or
minute six-sided tables; decomposed by hot
water into potassium benzoate, di-phenyl-urea,
and COj ; and by NaOH into benzoyl-hydroxyl-
amine and NaOBz.— Bz^ONa.— (Bz,NO)^b.—
Bzp^OAg.
HYDKOXYLAMINE DEEIVATIVES.
737
Tri • Mntoyl ' derivative BZ2NOBZ.
found among the prodnots of the aotion of
benzoyl chloride dissolved in toluene on dry
hydroxylamine hydroohloride. It is also formed
by heating BzjNOK with BzOl at 100°, after-
wards removing excess of BzGI with ether, and
EGl with water, and crystallising the residue
from alcohol (Lessen, A. 161, 360; 17S, 282,
299 ; 186,3, 34; Steiner, A. 178, 225). Itooonrs
in three modifications, and is best prepared by
drenching 10 pts. of silver di-benzoyl-hydrozyl-
smine with 30 pts. of dry benzene and adding
4 pts. of benzoyl chloride diluted with 8 pts. of
benzene. The mixture gradually separates into
a pp. and a liquid; the pp. is washed with ether
which takes up chiefly the (a)-modification, and
then with boUing alcohol wnioh dissolves the
(/S)-and (7) -modifications, together with di-
benzoyl-hydroxylamine. The alcoholic solution,
treated with a solution of NajCO,, yields a pp.
oonsisting of the (jS)- and (7)-modifications, which
may be purified by recrystalliaation from ether or
alcohol, when the many-faced prisms or needles
of the (/3)-oompound must be separated by hand-
picking from the short thick rhombohedra of
the (7)-isomeride. All three modifications are
split up by dry distillation into phenyl cyanate
and benzoic anhydride; and are converted by
alcoholic EOH into EOBz and the di-benzoyl
derivative.
(o)-Tri-benzoyI-hydroxylamine [100°].
Monoclinic crystals; o:6:c = l-856:l:l'142; ;8 =
81° 42' (Lehmann, Z. K. 1, 627 ; Klein a. Treoh-
maun, A. 186, 76 ; Z. K. 1, 637). V. e. sol.
ether and boiling alcohol, t. sol. boiling benzene.
Boiling HdAq (S.G. 1'05) in one hour completely
splits it up into benzoic acid and di-benzoyl-
hydroxylamine.
(3)-Tri-benzoyl-hydroxylamine [142°].
Monoclinic crystals; a:6:c= •897:1: -300; 3 = 83°
21'. Less sol. benzene than the preceding.
Insol. ether, m. sol. boiling alcohol. Not affected
by boiling dilute HClAq; but at 150° it is split
up by cone. HCSAq into HOBz, hydroxylamine,
and BzjNOH. Unlike the (o)-isomeride it dis-
solves in aqueous NajCO,.
(7)-Tri-benzoyl-hydroxylamine [112°].
Short monoclinic prisms; o:6:c = -926:1:? ; 3
= 65° 55'. Converted by hot dilute HOlAq into
the (|8) -isomeride. Alcoholic KOH forms EtOBz
and BzjNOEt.
Anisyl derivative OaH4{OMe).NH.OH.
p-MetTioxy-henzoyl derivative, [157^. When
anisyl chloride is added to a solution of hydroxyl-
amine hydrochloride in ten times its weight
of water, together with enough NajOOj to make
the liquid a&aUne, there separates anisic acid,
anisyl-hydroxylamine, and di-anisyl-hydroxyl-
amine. The pp. is boiled several times with
water, when anisic acid and anisyl-hydroxylamine
are dissolved, and may subsequently be separated
by their barium salts, that of the latter being
insoluble. The di-anisyl derivative which re-
mains undissolved in the boiling water is freed
from anisic acid by cold aqueous NajCO, (Los-
sen, A. 175, 284). Laminffl, v. sol. alcohol and
boiling water, si. sol. cold water, v. si. sol. ether,
insol. benzene. PeOl, colours its solutions deep
Tiolet. — C^/OM:e)NHOK,0;E,(OMe)NH.OH :
long flat needles, moderatol>' soluble in cold
Vob. II.
water. — OjH,(OMe)NH.O.PbOAo : pulverulent
pp. (Hodges, A. 182, 218).
Di-anisyl derivative
(C,a,(0Me)00)2N0H or
05H^(0Me).C0NH 0.0^,(OMe).CO. [143°].
Needles, v. si. sol. ether, insol. benzene. Split
up by boiling baryta-water into anisic acid and
anisyl-hydroxylamine.
Beneoyl-anisyl derivative
BzNH.0.C0.CeH4.0Me. [132°]. Formed by
treating benzoyl-hydroxylamine with anisyl
chloride. Needles or prisms (from alcohol).
Split up by heating with baryta-water into anisic
acid and benzoyl-hydroxylamine. The potas-
sium salt is split up by boiling water into anisic
acid, s-di-phenyl-urea, and CO,. Benzoyl-anisyl-
hydroxylamine is resolved by distillation into
anisic acid and anisyl-anilide.
Anisyl-benzoyl derivative
C,H4(0Me).C0.NH.0Bz. [148°]. Formed by
treating anisyl-hydroxylamine with benzoyl
chloride. Needles or prisms. Split up by heat-
ing with baryta-water into benzoic acid and
anisyl-hydroxylamine. The potassium salt is
split up by boiling with water into benzoic acid,
s-di-ji-methoxy-di-phenyl-urea, and CO,. Anisyl-
benzoyl-hydroxylamine is split up by distillation
into benzoic acid, benzoyl-anisidine, CO,, and
methoxyphenyl cyanate.
Benxoyl-anisy I -benzoyl derivative
BzN(00.0^,.OMe).OBz ? Formed, in three
modifications, by the action, of BzOl on the
silver salt of benzoyl-anisyl-hydroxylamine. In
one prepaiation 35 pts. of (a), 6 pts. of {$), and
6 pts. of the (7) variety were got.
(a)-Modifiaation [114°]. Short triclinio
prisms. This is the modification formed in
largest quantity. When heated with dilute HCl
it is spUt up into benzoic acid and benzoyl-
anisyl-hydroxylamine ; while cone. HClAq gives
hydroxylamine, benzoic acid, and anisic acid.
Alcoholic EOH forms benzoic ether and benzoyl-
anisyl-hydroxylamine ; aqueous EOH forms
chiefly benzoic acid and benzoyl-anisyl-hydroxyl-
amine, but produces also a small quantity of
anisic acid and di-benzoyl-hydroxylamine. On
dry distillation the (a) -modification is decomposed
with slight carbonisation into phenyl cyanate
and benzoyl-anisic anhydride, a small quantity
of j)-methozy-phenyl cyanate and Bz^O being
also produced.
(3)-Modification [125°]. Trimetric prisms;
chiefly found in the alcoholic mother-liquor of
the first crystallisation of the crude product of
the aotion of BzCl on benzoyl-apisyl-hydroxyl-
amine. Not affected by boiling for one hour
with 9 pts. of dilute HOlAq (S.G. 1-05) ; fuming
HOlAq converts it into benzoic acid, anisic acid,
and hydroxylamine, a little benzoyl-anisyl-
hydroxylamine being likewise formed. Alcoholio
EOH converts it into EtOBz and benzoyl-anisyl-
hydroxylamine.
(7) -Modification [110°] ? Monoclinic
tables ; separated from ttie crystals of the (a),
variety by hand-picking. After fusion it takes a
long time to solidify, and then melts at 120°,
having perhaps been converted into the (/3)-mo-
dification. Boiling dilute HCl (S.G. 1-0^ forms
benzoic acid, benzoyl-anisyl-hydroxylamine, and
a quantity (40 p.o.) of the (3) -modification of
beuzoyl-anisyl-benzoyl-hydroxylamine.
SB
738
HYDROXYLAMINE DERIVATIVES.
Di-hemoyl-anisyl derivative
BzjN.O.CO.CjSi.OMe. Formed, in two modifi-
cations, by tiie action of anisyl chloride on di-
benzoyl-hydrozylamine (Lossen, A. 186, 21).
(a)-Modifioation [110°]. Monoclinio
needles or prisms. Boiling dilute HCl (S.G.
1-05) easily splits it up into anisic acid and di-
benzoyl-hydrozylamine. Alcoholio EOH gives,
on the contrary, benzoic acid and beuzoyl-anisyl-
hydroxylamine. Split up_ by heat into phenyl
oyanate and benzoic anisic anhydride, together
with smaller quantities of ^-methoxy-phenyl
oyanate and Bz^O.
(i3).Mpdifioation [110°]. Bosettes of
small crystals, occurring in the last crop of crys-
tals of its (a)-isomeride. It is scarcely attacked
by boiling dilute HCa (S.G. 1-05) ; while pro-
longed heating with acid of S.0. 1*14 forms di-
beuzoyl-hydroxylamine, most of the substance
being, however, converted into hydroxylamine,
benzoic acid and anisic acid.
Anisyl-di-henzoyl derivative
MeO.O^-CO.NBz.OBz? Two modifications of
this body are formed by the action of benzoyl
chloride on silver anisyl-benzoyl-bydrozylamine
(Lossen, A. 186, 25).
(a)-Modification [137°]. Monoclinio
tables. Slowly decomposed by dilute HCl (S.G.
1-05), more readily by stronger HCl (S.G. 1-14),
into benzoic acid and anisyl-benzoyl-hydroxyl-
amine. Alcoholio KOH also gives benzoic acid
and anisyl-benzoyl-hydroxylamine. When heated
alone it yields j>-methoxy-phenyl cyanate and
BZjO, together with small quantities of phenyl
oyanate and benzo-anisic anhydride.
(j3)-Modification [110°]. Small rosettes.
Not decomposed by Hd of S.G. 1-05, and only
partially attacked by acid of S.G. 1-14. Alco-
holic EOH forms anisyl -benzoyl -hydroxyl-
amine.
Anisyl-benzoyl-artisyl derivative
C.H4(0Me).00JiIBz.0.C0.C8H,(0Me). Formed,
in two modifications, by the action of anisyl
chloride on the silver salt of anisyl-benzoyl-hy-
droxylamine.
(a)-Hodification [153°]. Very small
monochnic tables (from ether) •,a:h:c = ■866:l:-380 ;
3 = 75° 22'. DUute HCl (S.G. 1-05) easUy de-
composes it, forming anisic acid and anisyl-
benzoyl-hydroxylamine. Alcoholic EOH forms,
on the contrary, benzoic acid and di-anisyl-hy-
droxylamine.
(/3)-Modifioation [149°]. Only Ipt. of
this modification is formed to 34 pts. of the pre-
ceding. It crystallises in monoclinic tables;
o:6:c = 1002:1: -789; ;3 = 89°61'.
Di-anisyl-henxoyl derivative
(CA(OMe).CO)jNOBz? [148°]. Formed, in
only one modification, by the action of BzCl on
silver di-anisyl-hydroxylamine. Monoclinic crys-
tals. Slowly attacked by HOI of S.G. 1-05,
more rapidly by stronger acid, forming benzoic
acid and di-anisyl-hydroxylamine only. Alco-
holic EOH reacts in like manner, but forms also
a little anisic acid and anisyl-benzoyl-hydroxyl-
amine.
Benzoyl-di-anisyl derivative
BzN(C0.0ja<.OMe).OBz ? Formed, in two
modifications, from the silver derivative of benz-
oyl-anisyl-hydroxylamine and anisyl chloride.
(a)-Modifioatiou[138°]. Triclinic prisms;
a:6:c = -803:1: -955; a = 99°45'; 3 = 116° 5»\
7=74° 43'. Easily decomposed by HCl of S.G,
1-05 into anisic acid and benzoyl-anisyl-
hydroxylamine. Alcoholic EOH acts in like
manner.
(3)-Modification [138°]. Triclinic tables;
oA-x = •428:1:1-400 ; o = 103° 7' ; /3 = 96° 16' ;
<y=89° 25'. Behaves like the (a)-modification
when treated with HCl or EOH.
Oinnamoyl derivative
CA-CH:CH.CO.NH.OH. [110°]. Formed, toge^
{her with the di-cinnamoyl derivative and cin-
namic acid, by the action of cinnamoyl chloride
on hydroxylamine in aqueous solution ^ostoski,
A. 178, 213). Crystalline; si. sol. cold, m. sol.
hot, water ; v. sol. alcohol and ether, insoluble
in benzene. Ferric chloride colours its solu-
tion deep violet.— (C,H5.CH:0H.C0.NH.0)jHKi
very easily decomposable yellow crystals.—
(0,Hs.CH:CH.CO.NH.O)jHNa: yellow plates.—
(C,H,0.NH.0)2Ba : sparingly soluble yellow crys-
talline powder whidi, when heated, gives oS
COj and NH,.— (C,H,0.NH0)2Pb : yellowish-
white pp.
Di-oinnamoyl derivative
(OiHj.CH:OH.CO)jN.OH. [152°]. Formed as
above. Prisms or laminas; si. sol. ether, insol.
water and baryta-water, v. sol. hot alcohol. Its
salts when once separated from the aqueous solu-
tion are no longer soluble in water. The E salt
is decomposed by boiling with water and con-
verted for the most part into cinnamate. When
the compound is heated to incipient carbonisa-
tion a resin is formed, from which small quan-
tities of a crystalline powder C,^„N,0, may be
extracted. — (09H,0)jNOE: yellow powder. —
((C,H,0)jN0)2Pb : amorphous yellowish pp. —
(0^,0)2N0Ag : white pp.
o-Amido-hemoyl derivative
NHj.CeH,.00.NH.0H. [82°]. From anthranil
I'-oarboxylio acid and hydroxylamine. Glittering
plates (from water) (E. von Meyer a. BeUmami,
J.ijr. [2]33,20).
(a^-Naphthoyl derivative
C,„H,.CO.NH.OH. p.87°]. From hydroxylamine
and (a)-naphthoyl chloride (Ekstrand, B. 20,
1353). Glistening scales, soL boiling water,
almost insol. alcohol. Its potassium salt decom-
poses very readily with formation of (a)-naphthyl-
amine.
(ff^'Naphthoyl derivative
0,„H,.CO.NH.OH. [168°]. From hydroxylamine
(1 mol.) and (3)-naphthoyl chloride (Ekstrand,
B. 20, 1353). Small dimetrio scales, v. sol.
alcohol.
Di-lai-naphthoylderivative
(0,.H,.00)jN.OH. [150°]. Formed, together
with the mono-(a)-naphthoylderivative (v. suproi),
by the action of (a)-naphthoyl chloride on hy-
droxylamine. Needles, soL boiling alcohol. Its
E salt crystallises in needles, sol. alcohoL
Di-(fi)-naphthoyl derivative
(C,„H,00)jNOH. [171°]. Formed like the pre-
ceding. Small needles. Forms a crystalline
potassium salt.
{a(i)-Di-navhthoyl derivative
(0,„H,C0)2N0H. [160°]. From (3)-naphthoyl-
hydroxylamine and (a)-naphthoyl chloride at
100°. Needles (from alcohol).
Phthalyl-derivative C,H4:0ij02:N0a
[230°]. Formed by the action of phthalyl
HYDROXYLAMINE DERIVATIVES.
739
chloride 01 o( phthalio anhydride on hydrozyl-
amine (Cohn, A. 205, 295 ; Laoh, B. 16, 1781).
Needles or plates (from alcohol) ; v. si. sol.
water, t. sol. boiling alcohol, insol. ether and
benzene. EOHAq dissolves it, forming a red
solution. When boiled with KOH (1 mol.) dis-
solved in alcohol it is split up into CO, and o-
omido-benzoic acid. When boiled with a larger
quantity of KOH (2 mol s.) in alcohol it gives the
phthaloxyl derivative— CaH4:0202:NONa: red
amorphous powder. — 0„H4:CjO„:NOK : red pp.,
obtained by adding caustic potash (1 mol.) to an
alcoholic solution. ICeadily decomposed by treat-
ment with water.— Ba0lj4(CaH,:0jOj:NO)^a.—
(OsH,CANO)sPbj(OH)3aq: Ught-red pp.—
OA:OA:NOAg : dark-red pp.
Phthaloxyl derivative
OO2H.CaH4.CO.NH.OH. Formed from the
phthalyl derivative by warming vrith alcoholic
EOH. Its solution is acid in reaction, and gives
a violet colour with FeCl,, but it quickly decom-
poses with separation of its anhydride, the
phthalyl derivative. — ^KC8HsN04 : yellowish
crystals (from water); y. e. sol. cold water. —
PbCgHjNOi : white pp.
AUETL DEBTVAIIVES 07 HTDBOXXLAMim!.
Methyl-hydroxylamine H2N(0Me). The hy-
drochloride forms pearly scales (148° uncor.) ;
does not reduce alkaline solutions of copper. It
is formed by boiling the methyl ether of the oxim
of benzoic aldehyde with HCl (Fetraczek, B. 16,
827). — ^B'jHjPtCl,: orange-red tables or prisms
(Waldstein).
Benzoyl derivative BzMeN.OH. [65°].
Fromdi-benzoyl-methyl-hydroxylamineby warm-
ing with cone. KOHAq and passing COj into the
product (Lessen a Zanni, A. 182, 226). Beet-
angular tables (from ether-benzene). Decom-
posed by HCl into hydroxylamine and methyl
benzoate.
Di-hen2oyl derivative BzMeNOBz.
[c. —15°]. Formed by the action of Mel on an
ethereal solution of potassium di-benzoyl-hy-
droxylamine. Oil.
Ethylene-di-hydrozylamine.
Di-henssoyl derivative ^SiBzjO)20^^.
[148°]. Formed by boiling silver di-benzoyl-
bydroxylamine with an alcoholic solution of
ethylene bromide (Eiseler, A. 175, 342). Prisms,
bI. soL oold ether and alcohol ; moderately stabla
towards EOHAq.
Eth7l-hydroxylaiui]ieNH2.0Et orEtHN.OH.
(68°). S.G. tP -883. Formed by decomposing
ethyl-benzoyl-ethyl-hydroxylamine with HCl,
and liberated from its hydrochloride by cone.
EOHAq (Lessen a. Zanni, A. 182, 223 ; Giirke,
A. 205, 274). Combustible liquid, with powerful
odour; miscible with water, alcohol, and ether.
Alkaline in reaction. Gives a white pp. with
silver nitrate, and on boiling reduction takes
place with evolution of gas. When added in
excess to cuprio sulphate solution it forms a deep
blue liquid, whence an apple-green pp. is formed
on boUing, reduction not taking place. With
HgCl, it gives a golden flocoulent pp. — ^B'HCl.
[128°]. Scales; obtained by heating ethyl-
benzoyl-ethyl-hydroxylamine with HCl in ether.
Volatile. HClAq (S.G-. 1'14) at 150° decomposes
it into EtCl and hydroxylamine. -B'jHjPtClj :
prisms; v. sol. water and alcohol.— B'HjSOi: v.
e. sol. water and alcohol. — B'HjCjO, : colourless
powder.
Beneoyl-ethyl-hydroxylamine
NHBz.OEt. [65°]. Formed by the action of
EtI on potassium benzoyl-hydroxylamine (Wald-
stein, A. 181, 385) ; the proportions being :
benzoyl-hydroxylamine (1 mol.), cone, alcoholic
EOH (2 mols.), and EtI (1 mol.); after being
left for 24 hours, with frequent agitation, the
solution is filtered from EI, freed from alcohol
by evaporation, dissolved in water, and subjected
to a stream of CO,, and the NHBz(OEt) ex-
tracted with ether. The same compound is also
formed by treating ethyl-hydroxylamine with
benzoyl chloride (Giirke, A. 205, 278 ; Bertram,
A. 217, 16) ; and by treating benzoic ether with
hydroxylamine (Tiemann a. Eriiger, B. 18,
740).
ProperUes. — Triclinio crystals (from alco-
hol); o:6m! = -610:1:-852; o = 109°31'; e
= 85° 32'; 7=100° 31'. V. e. sol. ether and
alcohol; m. sol. water. Soluble in aqueous
EOH (1 mol.) forming a solution from which it
is reppd. by CO, and by acids, and which gives
pps. with salts of Ag, Hg, and Pb. Hot cone.
HClAq in sealed tubes splits it up into benzoic
acid and ethyl-hydroxylamine hydrochloride.
By heating alone to 190° it is converted into
phenyl cyanate, benzamide, aldehyde, and alco-
hol. PCl,gives benzoyl-ethoxim chloride
Ph.CCl:N.OEt. (230°).— BzAgN.OBt : white pp.
Ethyl-bensoyl-hydroxylamine
EtNBz.OH.
(a)-Modification [64°]. 8.0.1-208. S.
(ligroin of 8.G. -65) 1-8. Formed, together with
EOBz, by heating (a)-di-benzoyl-ethyl-hydroxyl-
amine with cone. EOHAq. Formed also, to-,
gether with the (i3)-isomeride, by treating benz-
imido-ethyl ether with cone, hydroxylamine
hydrochloride (Lessen, B. 17, 1587) . Monochnic
tables or prisms (from benzene-ether) ; a:b:c
= 1*49:1:1*53 ; inclination of optical axes = 117°.
V. sol. alcohol and ether, m. sol. water. Sol.
EOHAq, forming a solution which is ppd. by
metallic salts. On heating with HClAq it is
resolved into hydroxylamine and benzoic ether.
Decomposes at 180° into benzonitrile, BzOEt,
alcohol, water, and nitrogen, with smaller quan-
tities of benzamide, benzoic acid, and CO,.
(/3)-Modifioation [68°]. S.G. 1*185. S.
(ligroin of S.G. *652) 2*21. Formed as above,
and by the action of boiling EOH (1 pt.) dis-
solved in water (Ipt.) upon (^)-di-benzoyl-ethyl-
hydroxylamine (Giirke, A, 205, 286), and upon
ethyl-benzoyl-anisyl-hydroxylamine (Pieper, A.
217,5). Monoclinic crystals ; a:&:c = 1*24:1:1*40;
iacUnaUon of opUcal aa;es = 72*5° (Tenne, A.
217, 5). Less soluble in alkalis than the (a)-
modification. Decomposed by HCl, and by dis-
tillation, into the s^me products as the (a)-iBo-
meride.
Anisyl-ethyl-hydroxylamine
(C8HA)EtN0H. [84°]. From ethyl-hydroxyl-
amine and anisyl chloride (Pieper, A. 217, 16).
Mouoclinio tables (from ether). Forms with
EOH a salt. Cone. HCl gives anisic acid and
ethyl hydroxylamine.
Ethyl-anisyl-hydroxylamine
C8H,02NH.OEt. [32°]. Formed by treating
anisyl-benzoyl-ethyl-hydroxylamine with cone.
KOHAq, and ppg. by COj (Eiseler, A. 175, 338).
3b2
740
HYDROXYLAMINE DERIVATIVES.
Crystals ; v. e. sol. alcohol and ether. Split up
by HCl into anisic ether and hydroxylamine.
Di'benzoyl-ethyl-hydroxylamine
BzgN.OEt. Two, or possibly thrse, modifica-
tions of this compound are formed in the reac-
tion between silver di-benzoyl-hydroxylamine
and EtI ; the (a)-yariety is formed in the greater
quantity, and crystallises out first ; only 2 or
3 p.c. of the (3) -modification is formed ; there is
perhaps also an oily variety {Gurke, A. 205,
280).
(a).Modification [58°]. S.G. wi< 1-243.
Trimetric crystals; o:6:c='697:l:'591. V. sol.
ether and alcohol, insol. benzene. Decomposes
at 180° into benzoic acid, benzonitrile, and alde-
hyde. Cone. EOHAq converts it into benzoic
acid and(a)-ethyl-benzoyl-hydrozylamine. Cone.
HClAq gives benzoic acid, benzoic ether, and
hydroxylamine (Eiseler, A. 175, 830).
(;8)-Modification [63°]. S.G. is 1-239.
Formed as above. It is also the chief product
of the action of BzCl on (a) or (0) ethyl-benzoyl-
hydroxylamine. Triclinic crystals; a:b:c
= ■556:1: -714; o=118° 25'; i8 = 102° 37'; y
•=90° 52'. More soluble in alcohol and ether
than the (a)-modification ; insol. ligroin. When
heated it yields the same products as its iso-
meride, but requires a temperature of 225°.
Gone. HClAq also acts upon it in the same way
as upon the (a).variety. KOHAq acts upon it
with more difiiculty than upon its isomeride,
and produces (i3)-ethyl-benzoyl-hydrozylamine.
Semoyl • ethyl - benzoyl hydroxyl-
amine [49°]. From NBzEtAgO and BzCl
(Lessen, B. 10, 2223) ; or from NBzBtHO, BzCl,
and KOHAq (Pieper, A. 217, 8). Trimetric
crystals, a:&:c = -624:1:2-587. V. sol. alcohol or
ether, insol. water or petroleum. Split up by
ECl into benzoic acid and hydroxylamine.
Senzoyl-anisyl-ethyl-hydroxylamine
BzN(C,H,02).0Et. Formed, in two modifications,
by the action of EtI on silver benzoyl-anisyl-
hydroxylamine (Eiseler, A. 175, 326 ; Pieper, A.
217, 2).
(o)-Modifieation [74°] (P.); [69°] (B.).
Monoclinic tables (from ether-benzene) ; a:b:c
= 1-518:1: -666. Decomposed by alcoholic KOH
into potassium anisate and (a)-ethyl-benzoyl-
hydroxylamine [54°]. ECl forms benzoic ether,
aiiisic acid, and hydroxylamine.
(i8)-Modifioation. Oil.
Ethyl-bemoyl-anisyl-hydroxylamine
EtNBz.OCaHjOj. [89°]. Formed by treating
3thyl-benzoyl-hydroxylamine with anisyl chlor-
ide and aqueous EOH (Pieper, A. 217, 4). Mono-
clinic crystals (from ether); a:6:c = -748:1: -803.
With cone. KOHAq it gives (;3)-ethyl-benzoyl-
hydroxylamine [68°] and potassium anisate. On
distillation it gives benzonitrile, anisic acid, and
aldehyde.
Anisyl-bemoyl-ethyl-hydroxylamine
BzN(CjE,OJ.OEt. [79°]. Formed, together with
an oily isomeride, by treating silver anisyl-
benzoyl-hydroxylamine with Btl (Biseler). Tri-
clinic prisms. Decomposed by KOB into ethyl-
anisyl-hydroxylamine and KQBz. ECl gives
hydroxy lamine, anisic ether, and benzoic acid.
Bemoyl-ethyl-anisyl-hydroxylamine
BzNBt.0C,H,02. [64°]. Prom silver benzoyl-
ethyl-hydroxylamine and anisyl chloride (Pieper,
A. 217, 10). Triclinic crystals (from ether);
<x:6:c = -773:1: -855. M. sol. alcohol and ether,
insol. water and ligroin. Not attacked by a so-
lution of 2 pts. of KOE in 3 pts. of water; but s
solution of equal weights of potash and water
forms potassium anisate and benzoyl-ethyl-hy-
droxylamine [67°]._ Dilute ECl at 100° forms
benzoic acid, anisic acid, and ethyl-hydrozyl-
amine ; a still more dilute acid gives anisic acid
and benzoyl-ethyl-hydroxylamine [67°]. On dis-
tillation it is split up into anisic ether and phenyl
cyanate.
Anisyl-ethyl-benzoyl-hydroxy lamine
CsHjOaNEt-OBz. [94°]. From anisyl-ethyl-
hy droxylamine, BzCl, and the calculated quantity
of aqueous KOE (Pieper, A. 217, 18). MonocUnio
crystals (from ether). SI. sol. alcohol or ether,
insol. water or light petroleum. Hot cone. EOHAq
gives anisyl-ethyl-hydroxylamine [84°] and benz-
oic acid. ECl at 100° acts similarly, the anisyl-
ethyl-hydroxylamine being subsequently broken
up into anisic acid and ethyl-hydroxylamine. On
distillation it is decomposed, but not neatly.
Phthalyl-ethyl-hy droxylamine
C,Ej:CA:NOEt. [104°]. (o.270°). From sU-
ver phthalyl-hydroxylamine and EtI (Cohn, A.
205, 295). Trimetric needles, sol. ether and
petroleum, insol. NajCOjAq. When heated with
potash it yields ethyl-amido-benzoio acid. It
resembles the nitrolio acids in giving a led
colouration with alkalis.
Iletliyl-ethyl-hydrozylamine.
Methyl-athyl-benzoyl-hydroxylamint
MeNEt.OBz. Prepared by the action of EtI on
methyl-benzoyl-hydroxylamine dissolved in al-
coholic KOH. Oil, with pleasant odour. De-
composed by dilute HCl into methyl benzoate
and ethyl-hydroxylamine.
Benzoyl-methyl-ethyl-hydroxylamini
BzNMe.OBt. From silver benzoyl-ethyl-hydroxyl-
amine (1 mol.) and Mel (1 mol.) in ether (Wald-
stein, ^. 181, 393).. Oil; misoiblewith alcohol
and ether. Decomposed by hot dilute HCl.
E thy l-benzoyl-methyl-hy droxylamine
EtNBzOMe. . Formed by liie action of Mel on
(a)-etbyl-benzoyl-hydroxyIamine dissolved in
alcoholic KOE. Oil. Decomposed by HCl into
methyl-hydroxylamine and benzoic ether.
Di-ethyl-hydiozylamine NBt^.OE or
KEtH.OEt. Formed, together with hydroxyl-
amine, by reducing nitric ether with tin and HOI
(Lessen, A. Suppl. 6, 238). Its hydrochloride
remains in the mother-liquor, from which by-
droxylamine hydrochloride has crystallised. The
free base, separated from its salts by KOH
and extracted by ether, is a strongly alkaline
syrup, V. sol. water, not easily volatile with steam.
Its aqueous solution forms with FeCl, chrome-
alum, cobalt nitrate, and lead nitrate, pps. in-
soluble in excess and with CUSO4 a bluish-whita
pp., dissolving in excess to a violet-brovn solu-
tion. It reduces silver oxide onheating. It also
reduces boiling aqueous HgCl,.
Salts.— B'ECl : syrup.— B'jHjPtCl,: orange-
red crystals (from alcohol).— B'jEjSO, : minute
laminee ; ppd. by ether from its solution in alco-
hol.—B'^EsPOj : prisms (from water) or hair-
like needles (from alcohol).— B'E^C A : stellate
groups of prisms (from water) or minute needles
(from boiling alcohol).— B'^,C,0,: prisms (from
water); insol. alcohoL
HYDROXYLAMUfE DERIVATIVES.
741
Bineoyl derivative Et^NOBz or
EtNBz.OEt. (244° i.V.). S.G. 15[ 1026. Formed
by the action of EtI on ethyl-benzoyl-hydroxyl-
amine disBolved in alcoholic KOH. Yellowish
aromatic oil ; v. sol. alcohol and ether. Besolv^d
by heating with HClAq into benzoic ether and
ethyl-hydrozylamine.
Tri-ethyl-hydrozylamine KEt^OEt. S.G.
* -SSaS. Formed by mixing ZnEtj with nitro-
ethane and ether in an atmosphere of CO,, and
after a fortnight decomposing the product with
water (Bevad, J. R. 20, 125). Oil; v. si. sol.
water, misoible with alcohol, ether, and benzene.
Its salts are very hygroscopic, and reduce silver,
cupric, and mercuric salts. — B'^^OjO,.
Benzyl-hydroxylamine
(a) - modification XH^-OCH^h. Formed
by warming the benzyl derivative of the oxim
of acetone with aqueous ECl ; thus :
MejO:NOC,H, + OH, = UejDO + HjNOC,H,-
(Janny, B. 16, 175). Formed also in like manner
by treating the (a)-benzyl derivative of benz-
aldozim ((a)-benzy]idene-benzyl-hydroxylamine)
with cone. HClAq (Beckmann, B. 22, 515).
Hydrochloride B'HCl. Soft, silvery plates,
si. sol. water, v. si. sol. cold, v. sol. hot, alcohol.
Acid in reaction. Sublimes between 230° and
260° without previous fusion. Beadily con-
denses with benzoic aldehyde. Boiling HI con-
verts it into iodo-benzene and NH,. Ureide
NHj.CO.NH.OC,H,. [139°] (Behrend a. Leuchs,
B. 22, 385).
(/})-modification C,H,.NH.OH. [58°]. Ob-
tained from the (0) -benzyl ether of benzaldoxim
by the action of cone. HClAq at a high tempera-
ture (Beckmann, B. 22, 514). Formed also by
heating (j3)-di-benzyl-hydroxylamiQe with cone.
HClAq at 130° (Behrend a. Leuchs, jB. 22, 615).
Needles (from petroleum-ether).— B'HCl [110°].
Broad needles, v. sol: cold alcohol, v. e. sol.
water. Beduces Fehling's solution in the cold.
Si-beuzyl-hydrozylamine (CeH,.CH2)2N.OH
[123°] uncor. Prepared by heating for two
hours on the water-bath a solution of 30 g.
hydroxylamine hydrochloride, 60 g. NajCOj lOaq
and 30 g. benzyl chloride in water and sufficient
alcohol to just dissolve the benzyl chloride ; on
cooling the product crystallises out (yield : 14 g.)
(Schramm, B. 16, 2184 ; Walder, B. 19, 1626).
It is perhaps accompanied by a more strongly
basic isomeride (Behrend, B. 22, 385). Long
white needles. V. sol. alcohol, ether, benzene,
si. sol. Ugroin, CS^, HOAc, and hot water. Dis-
solves in HCl but not in NaOH or NH3. Not
decomposed by cone. HClAq at 130°. By long
boiling with acetic acid saturated with HCl it is
split op into benzaldehyde and benzylamine ;
acetyl chloride has the same effect. Boiled with
alcoholic benzyl chloride it yields tri-benzyl-
hydroxylamine (Ph.CHJjN.OCH^.Ph. By the
action of PCI, and treatment with water di-
benzyl-amine is formed, the reaction probably
being :
(C,H,),N.OH + PCI, = (0,H,),N.0.PC1, + HCl and
(C,H,),N.O.PCl2-h3H,0
^ "' =(C,HO.,NH + PO,H, + 2HC1.
Mel and NaOEt gives acompound (0,H,)jNjOHI
which appears to be the hydriodide of the an-
hydride (C,H,)jN.O.N(C,H,)j. Heated with ethyl
iodide and alcoholic sodium ethylate it gives
di-benzyl-ethyl-amine (0. 300°) and a base
C^HjiN which fomis felted crystals [84°]. Pro-
pyl iodide and a solution of sodium in propyl
alcohol give benzyl-amine, propyl ether, and
a small quantity of benzyl-benzoata. Witt a
very dilute colourless solution of FojOl, it gives
a yellow colour on standing. By the action of
nitrous acid without coohng,' di-benzyl-nitros-
amine is formed; when kept cold the product
is the nitrous ether (C,H5.CHj)2N.O.NO :
[84°] which crystallises from dilute alcohol in
flat white needles ; v. sol. alcohol and ether, si.
sol. ligroin, insol. water (Walder, B. 19, 3287).
Salts.— B'HCl: pearly plates.— B'^H^PtCl,:
sparingly soluble brownish - red crystals. —
B'HCl, HgClj : white plates, sol. warm alcohol,
nearly insol. water. — Ficrate B'CjHj(N02),0H :
[151° cor.]; glistening yellow plates, v. sol.
alcohol and ether, insol. water (Walder, B. 20,
1751).
Anhydride? {(CjHJjNljO. The hydro-
iodide (B"HI) [148°], erroneously called ' tetra-
benzyl-oxy-ammonium iodide,' is formed by'
heating di-henzyl-hydroxylamine with methyl
iodide ; from this salt the base is obtained by
the action of Ag„0. Strongly alkaline colourless,
very deliquescent crystals. V. e. sol. water, si.
sol. ether. Distils at a high temperature. —
B"H20l2 : pearly prisms, m. sol. water, insol.
ether. — B"HI: see above. — B"HjIj : [27°];
white crystals.— B"(HN03)j : [159°] ; white flat
needles, si. sol. water.— B"H2S04 : [152°] ; soluble
prisms.— B"HjCljPtCI,: [152°]; smaU yeUow
needles, si. sol. hot water, insol. cold water
(Walder, B. 19, 3289).
Acetyl derivative (C,H,)2N.OAo. [178°].
From di-benzyl-hydroxylamine (1 mol.) and
AcCl (1 mol.). Feathery crystals (from dilute
alcohol) ; m. sol. water, v. sol. alcohol.
Benzoyl derivative (C,H,)2N0Bz. [97°].
From di-benzyl-hydroxylamine and BzCl (Beh-
rend a. Leuchs, B. 22, 385). Needles (from
alcohol). Converted by boiling alcoholic EOH
into di-benzyl-hydroxylamine and benzoic acid.
(;8)-m odifi cation OsH^.CHjNH.O.CHjCaHs.
An oil, which accompanies the preceding. Cone.
HClAq at 130° splits it up into benzyl chloride
and the (iS) -modification of benzyl-hydroxyl.
amine (Behrend a. Leuchs, B. 22, 616).
Iri-benzyl-hydroxylamine
(CeH5.CH.)2N.0.CHj.CeH,. [119°]. Formed by
boiling di-benzyl-hydroxylamine for a long time
with an alcoholic solution of benzyl chloride
(Walder). Behrend and Leuchs (B. 22, 613)
could omy obtain by this method an oily tri-
benzyl-hydroxylamine of basic character, mixed
with an indifferent, probably isomeric, oil.
Short white prisms, v. sol. alcohol and ether,
insol. water.
Salts.— B'HCl: [172°]; white crystals,
si. sol. water, insol. ether. — B'jH^CljPtCli : [c.
150°]; small reddish-yellow crystals, si. sol.
alcohol (Walder, B. 19, 1631 ; cf. Behrend, B.
22, 385).
Tri-benzyl-hydroxylamine
{CaB.,.Cn.^)^^.O.CK.fisB.^. Formed, together with
di-benzyl-hydroxylamine, by the action of an
alcoholic solution of benzyl chloride (3 mols.) on
benzyl-hydroxylamine hydrochloride in presence
of NajCOj. Dilute HClAq dissolves the di-
benzyl-hydroxylamine, but not the tri-benzyl-
hydroxylamine, since the hydrochloride of this
743
HTDROXTL AMINE DKKIVATIVBS.
body is decomposed by water. The tri-benzyl
derivative is then extracted with ether (Behrend
a. Leuchs, B. 22, 614). Oil. With oono. HClAq
at 160° it gives di-benzyl-hydroxylamine [123°].
Salts.— B'HCl: [91°]; needles.— B'JBjPtCl.:
[157°] ; prisms, v. si. sol. cold alcohol. —
Piorate : [132°] ; v. si. sol. water.
Tri-nitro-phenyl-hydrozylainiiie
C^(N0j)3NH.0H. [100°]. Formed by the
action of picric ether C|jHj(N0j)30Et on hy-
droxylamine (Michael a. Browne, J. pr. [2] 35,
358). Silky needles. Its solution is turned
brown by the least trace of ammonia.
Heza-nitro-di-phenyl-hydroxylamine
{CgH2(N02)9}2N0H. Di-picryl-h/ydroxyXa/mine.
[170°]. Formed by adding picryl chloride
CjHjprOJsCl in alcoholic solution to an aqueous
solution of hydr'oxylamine (M. a. B.). Yellow
crystals, which may be sublimed.
Benzylidene-hydrozylamine CgHj.CHiKOH is
described as Beiizai<doxim, u. vol. i. p. 447. Ac-
cording to very recent researches of Beckmann
(B. 22, 432), when HOI is passed into an ethe-
real solution of benzaldoxim there is obtained an
isomeride. This (j3)-benzaldoxim yields the same
products on treatment with HCl as the ordinary
or (a)-benzaldoxim, and both their ethyl ethers
are oily and are split up by HCl into EtCl,
NH,C1, and benzoic acid. The benzyl ethers
of the two oxims, however, are different.
(a)-Benzylidene-benzyl-hydro3£yIamine
C„H5.CH:N0C,H,. Formed, at ordinary tem-
peratures, by the action of benzyl chloride on an
alcoholic solution of (a)-benzaldoxim, Oil. In-
sol. water, sol. alcohol, and ether. Split up by
HCl into benzyl chloride, benzoic acid, and
NH,C1; but under certain conditions it yields
benzoic aldehyde and {o)-benzyl-hydroxyl-
amine.
(3)-Benzylidene-benzyI-hydrozylaniiiie
C.H..CH:NOC^, or C,H5.0H<°^>. [82°].
Formed by the action of benzyl chloride upon
(/3) -benzaldoxim dissolved in alcohol containing
NaOEt. Formed also from (j3)-benzyl-hydroxyl-
amine and benzoic aldehyde. Slender needles
(from ether). It forms a crystalline hydro-
chloride [148°]. On treatment with HCl it
yields benzoic aldehyde and (j3)-benzyl-hydroxy]-
amine.
Other derivatives of hydrozylamine are de-
scribed as oxims of aldehydes, ketones, and ke-
tonic compounds generally, and as nitroso-,
isonitroso-, or oximido- compounds.
HSZA-HYSRO-XTLENi: v. Xtlbne bexa-
nixyena.
HTSBO-o-XYLOQTTIHONE
CftMe,(OH)j[l:2:3:6]. [221°]. Formed by re-
ducing o-xyloquinone with SOj (Nolting a. Forel,
B. 18, 2673). Separates from water in crusts.
Partially decomposed on melting.
Hydro-m-zylaqninone
C,H,Me,(OH)j[l:3:2:5]. [151°]. Obtained by
reducing w-xyloquinone (Nolting a. Th. Bau-
mann, B. 18, 1151).
Hydro-p-xyloquinone CaH2Mej(OH)j[l:4:2:5].
Hydrophlorone. [212°] (N.) ; [208°] (Carstan-
jen, J. pr. [2] 23, 421). Obtained by passing
SOj into a saturated aqueous solution of
p-xyloquinone (phlorone) (Von Bad, A. 161,
164 ; Nietzki, B. 13, 472). Colouvless pearly
plates (from water). May be sublimed SI.
sol. cold, m. sol. hot water ; v. sol. alcohol and
ether ; m. sol. boiling benzene. FeClf and other
oxidising agents readily re-convert it into
^-xyloquinone. Ammonia turns its solutions
brown. It reduces boiling cnpric acetate solu-
tion with ppn. of CUgO. It reduces silver
nitrate.
Di-ethyl ether GjH,MejfOEt)j : [106°];
glittering plates (from alcohol) (Staedel a. Hols,
B. 18, 2919).
HYSBirVIC ACID «. Ptbuvio aois.
HYDTJRILIC ACID CsH^N^O, i.e.
00<^i:OH:CH<CO.NH>eov
Formation. — 1. Discovered by Schlieper {A.
56, 11) among the products of the action of
dilute nitric acid on uric acid, being found on
one occasion in the mother-liquor from which
alloxan had crystallised. He was, however,
unable to repeat the experiment. — 2. By heating
dialuric acid with glycerin (which acts merely as
a solvent) at 160°, the products being acid am-
monium, hydurilate, formic acid, and GOj, thus :
SC^H^N A = 2C,H3(NH JN,0. + HjCOj + 3C0j
(Baeyer, A. 127, 11). — 3. By heating air-dried
alloxan at 170°, the products being hydnrilio
acid, formic acid, CO2, ammonia, and GO (Mur-
doch a. Doebner, B. 9, 1102). The same pro-
ducts araobtained by heating air-dried alloxantin
for three or four hours in a sealed tube at 170°.
4. Among the products obtained by passing H^S
for several hours through a boiling solution of
alloxantin. — 5. By heating uric acid with H^SO^
at 130°, glyoocoll being also formed, while COj
is given off (Schultzen a. Filehne, B. 1, 150). —
6. By treating di-bromo-barbituric acid with a
small quantity of HI (Baeyer, A. 130, 133^.
Preparation. — 9 pts. of perfectly dry dialnrio
acid are mixed in a capacious flask with 5 pta.
of glycerin, and heated in an oU-bath to 140°-
150°. A brisk and regular evolution of carbonic
anhydride then takes j^lace, and as soon as this
ceases, and the contents of the flask have be-
come solid, the temperature is raised for a shoi^
time to 160°, and the glycerin, after cooling, is
removed by washing. A yellowish- white granular
powder is then left, consisting of acid hydurilate
of ammonium. To obtain the free acid the crude
ammonium-salt is dissolved in boiling water,
ammonia is added in slight excess, and solution
of cupric sulphate is added to the filtrate. The
liquid then assumes a dark-green colour, and, if
hot, deposits on cooling red warty crystals of
neutral hydurilate of copper. This salt is then
decomposed by hot hydrochloric acid, and the
hydurilic acid which crystallises out is washed
with dilute hydrochloric acid and dried over the
water-bath.
Properties. — Crystallises from water in small
four-sided prisms (containing 2aq). From a hot
concentrated solution in HClAq, or from an am-
moniacal solution by ppn. by HCl, it separates as
a crystalline powder composed of small tablets
(containing aq). Y. si. sol. cold, m. soL hot,
water; v. si. sol. alcohol. Dissolves in cono.
H2SO4, and is reppd. unaltered on adding water.
Scarcely sol. aqueous HCl. Not attacked by re-
ducing agents. Not attacked by aqueous alkalis ;
melting potash slowly forms oxalic acid. Oives
a dark-green colour with FeClj. This colour ia
HTMENODIOTYONINE.
748
also given by ita soluble salts, but is destroyed
by stiong acids and alkalis ; heat also destroys
it, changing it to red.
Reactions.— 1. When heated with ferric
ehhride it yields oxy-hydnrilio acid, cha-
racterised by producing a blood-red colour with
ferric salts.— 2. HOI mixed with KOlOj forms
di-chloro-hydnrilic acid 3. Faming mtrie add
gives only alloxan ; nitric acid of S.G. 1'4 gives
alloxan, violnrio acid (nitroso-barbiturio acid),
violantin, and diliturio acid, the last named
being the ultimate product when heat is em-
ployed.
Salts. — ^Hydurilic acid is dibasio. It is a
strong acid, and can decompose metallic chlor-
ides, expelling EOl and forming acid salts. It
dissolves readily in aqueous aJkalis, and the
solutions give pps. with metallic salts ; the pps.
are, however, acid salts. The neutral salts must
be prepared from the free acid. HGl added to
solutions of salts of hydurilic acid ppts. the acid
as a chalk-white amorphous powder, which,
when placed in hot water or hot H01A.q, becomes
crystalline. — NH,HA" : small octahedra (by ppn.
of an ammoniacal solution by acetic acid). M.
sol. boiling water, separating as granules and
crusts on cooling. — (NH,)2A"aq: needles, sepa-
rating on rapidly cooling a hot saturated solu-
tion. Obtained in the same form by ppn. with
ammonium sulphide, in which it is insoluble. —
(NH,)2A.''2aq : large shining monoclinic efflores-
cent prisms, obtained by slow evaporation ; m.
sol. water, v. sol. aqueous NH„ but reppd. by
alcohol. — NajA" 4aq: small prisms; obtained
by dissolving the acid in NaOHAq, acidulating
with acetic acid, and ppg. with alcohol. —
BaA." aq : amorphous pp., soon becoming crys-
talline, got by adding a hot solution of hydurilic
acid to barium acetate. — CaHL^A", 8aq: small
shining prisms, which separate when hydurilic
acid is added to a solution of CaCl,. — CaA" 3aq :
amorphous pp., soon becoming crystalline, ob-
tained by decomposing calcium acetate by hydu-
rilio acid CuHjA" 8aq. Obtained by mixing
the acid with oupric acetate or with cupric sul-
phate. Separates from concentrated solutions
in green needles, from more dilute solutions in
yellow prisms. When heated the anhydrous
salt is left as a red powder, which may also be
obtained by ppn. from hot solutions. — OuA" 4aq.
Obtained by adding the acid to excess of cupric
acetate, or by mixing the neutral ammonium
salt with cupric sulphate. From cold solutions
it is ppd. in short red needles of the hydrated
salt ; from warm concentrated solutions as a
brownish-red pp. of the anhydrous salt. —
ZnH2A"j : feathery groups of lustrous needles,
which separate when a solution of ZnCI, is
mixed with hydurilic acid.— ZnA" 2aq: white
amorphous pp., soon becoming crystalline.
Si-chloro-hydnrilio acid G^B. file's, O,. Pre-
pared by adding EClO, in small portions to a
pasty mixture of hydurilic in cone. HGlAq.
Snow-white powder; v. d. sol. water. Purified
by dissolving in HjSO, and reppg. by water,
when it separates as small trimetrio crystals
(containing 2aq). Warm nitric acid slowly
converts it into diliturio acid. — KjA" 2aq : small
six-sided tables (from water) : si. sol. cold water.
HT6BIN E. A Volatile alkaloid said to accom-
pany eocene in coca leaves (Wohler a. Lessen, A.
131, 874). The leaves are exhausted with distilled
water at 70°, the extract ppd. with lead acetate,
freed from lead by ppn. with aqueous Na^SOi,
rendered shghtly alkaline by Ka^CO,, and ex-
tracted with ether. The ether extracts cocaine,
and if the residual solution be now rendered
strongly alkaline by XajCO,, ether will extract
hygrine together with a neutral oil. These
may be partially separated by distillation in a
current of hy^ogen, the greater part passing
over below 140° i (Lessen). Thick yellow oil,
with strong alkaline reaction, burning taste, and
characteristic smell resembling tri-methylamine.
Fumes with HOI. Slightly volatile with steam.
M. sol. water, sol. alcohol and ether. Its aqueous
solution gives a white pp. with SnCl,, and a
light blue pp. with CuSO^, not rediiced on boil-
ing. It also ppts. HgClj and AgNO,. It forma
a deliquescent hydrochloride, the aqueous solu-
tion of which gives a brown pp. with iodine in
KI; a white pp. with HgClj; yellowish flakes
with PtCli ; a yellow powder with picric acid ;
and a white pp. with tannin. The platino-
chloride is decomposed by boiling water (O. de
Coninck, Bl. [2] 45, 131). The above are the
properties of the hygrine described by Lessen,
who states that it is not poisonous. Stockman
(Ph. [3] 18, 701) found in dried coca leaves a
very minute amount of an oily alkaloid with
burning taste and strong odour, which, however,
was very poisonous. W. C. Howard {Ph. [3] 18,
71) obtained, by adding PtCl^ to a solution of
crude cocaane, a semi-crystalline pp. insoluble
in water at 80° ; this platinochloride contained
18*5 p.c. Pt and yielded a base that gave no
orystalhsable chloride, did not smell of trimethyl-
amine, and had a bitter taste. Hesse {Pharm.
Zeit. 1887, 669) came to the conclusion that
hygrine was tri-methyl-quinoline, but he worked
with only a few grammes of the substance.
According to Liebermann (B. 22, 67S) the so-
called hygrine is a mixture of oxygenated bases.
He found that crude hygrine, a very dark liquid
BmeUing like piperidine and nicotine, was
strongly alkaline, and almost entirely soluble in
water. After dissolving in ether, drying with
sticks of EOH, and fractionally distilling under
50 mm. pressure, two colourless liquids are ob-
tained, beUing under 50 mm. pressure at 128°-
131° and 215° respectively, and having the con-
stitution OjHisNO and ChHjjNjO.
Base C^isNO. (o. 130° at 50 mm.); (194°
cor. at 760 mm.). S.G. if -940. V.D. (H = l)
68. This base, which is isomeric with tropine,
may be distilled in a current of nitrogen. —
B'C,Hj(N02),0H: [148°]; yellow needles, m. soL
oold water.
Base OnHjjjNjO. (215° at 60 mm.). S.G.
^1 '982. Decomposed by distillation under atmo-
spherio pressure. — Salts. — B"HjCl2 (dried at
100°): white crystalline powder.— B'TttjAujOls :
egg-yeUow pp. — B"(C,Hj(NOj),OH)j: crystals
(frem boiling water) ; v. si. sol. cold water. —
Methylo-iodide B"Me2l2: white crystalline
powder.
HYMEKODICTTOinWE Oj,H„Nj. An alka-
loid contained in the bark of HymenodMtyon
exceUum from which it may be obtained by
mixing with lime and extracting with chloro-
form (Naylor, Ph. [3] 13, 817; 15, 195). By
extremely slow evaporation of its ethereal solu-
744
HYMENODICTYONINE.
tion it may be obtained in a orystalline form,
but otherwise it is an amorphous deliquescent
mass. Its solutions are alkaline in reaction,
have a persistent bitter taste, and are optically
inactive. Its hydrochloride gives pps. with the
usual alkaloidal reagents. Gone. H2SO4 gives
a lemon-yellow colour changing to wine-red with
bronzy lustre.— B"HjPtCl, : yellow amorphoas
powder.— B"HjOL,.
Ethyloiodide B"Et2l2: rosettes of needles
(from alcohol).
HTOCAFFEINE v. Oi^Tmia.
HTOCHOLIC ACID C2sE„04. An acid ob-
tained together with glycocoU, by boiling hyo-
glycooholic acid with aqueous KOH (Strecker,
A. 70, 191). Granules (from ether). Scarcely
sol. water, v. sol. alcohol and ether. The solu-
tion of its ammonium salts is ppd. by solutions
of metallic salts.— BaA'^ (dried at 180°). SI.
Bol. water, sol. alcohol.
/3-HyocIiolic acid CssH^g^v An acid obtained
in like manner from (i3)-hyoglycocholio acid
(Jolin,^. 13, 205). It difiers from the preceding
chiefly in requiring a larger amount of Na^SOt
or KaOl to ppt. its sodium salt from aqueous
solution.
HYODYSLTSIN CjjHssOs. An amorphous
substance, homologous with dyslysin, produced
by the continued aotion of boiling hydrochloric
acid onhyoglycocholio acid (Strecker, A. 70, 189).
Insol. water, KOHAq, and aqueous NH„ d. sol.
boiling alcohol, m. sol. ether.
HYOGiyCOCHOIIO ACID OjjH^NO,. Occurs
as sodium salt, together with a smaller quantity
of hyotaurooholio acid, in pigs' bile (Strecker a.
Gundelach, A. 62, 205).
PreparaUon. — Fresh pips' bile is completely
saturated with Ka^SOf; the mixture is heated
for some hours, and then left to cool. The re-
sulting pp. is washed with a cone, solution of
Na^SO,, dried at 110°, and treated with absolute
alcohol. The alcoholic solution of sodium hyo-
glycocholate is decolourised with animal charcoal,
and the salt ppd. by ether. The aqueous solu-
tion of the sodium salt is ppd. by HjSO,, and
the pp. dissolved in alcohol and thrown down
again with water. The acid separates in trans-
parent drops.
According to Jolin (S. 11, 417) hyoglycocho-
lic acid is accompanied by a smaller quantity
of a (3)-isomeTide, the sodium salt of which is
less readily ppd. by NajSOj. A solution of
NasSO, saturated at 0° ppts. Streoker's' acid
only.
Froperttes. — White reain, si. sol. water, im-
parting an acid reaction ; v. sol. alcohol, insol.
ether. It melts under hot water, and then has a
silky appearance. Dissolves readily in alkalis
and alkaline carbonates. Dextrorotatory,
[o] = 2°; the sodium salt is optically inactive
(Hoppe, G. G. 1859, 65). It differs from glyoo-
cholic acid by its sparing solubility in water, and
by forming pps. insol. water with baryta and
lime. A solution of its sodium salt is ppd. by
metaUic salts, even by NaCl, KCl, and NH.Cl.
It gives Pettenkofer's test for bile.
BeacUona. — 1. Dilute mVphuric acid has no
aotion ; cone. HjSO, blackens it with evolution
of SOj.— 2. Cone. HNO3 gives oft nitrous fumes,
and leaves a yellowish mass, chiefly consisting
of oxalic acid and cholesteric acid C„H„0^ —
3. Boiling cone. HClAq forms hyodyslystn and
glycocoU. Boiling aqueous ^potosh acts in likt
manner.
Salt s. — NH4A'. Ppd. by adding ammonium
chloride, carbonate, or sulphide, to fresh pig's
bile, or to a solution of the sodium salt. Crys-
talline powder; v. sol. water, v. si. sol. cone,
solutions of ammonium salts. Decomposed by
boiling with water. — NaA' Jaq : white non-deli-
quescent powder. Its alcoholic solution yields,
on evaporation, a transparent varnish. It has a
persistent bitter taste. — EA'-^aq: white amor-
phous mass ; ppd. by adding ECl to a solution
of the Na salt. Melts under water or alcohol,
but when quite dry it does not melt, even at
120°.— BaA'2 2aq: si. sol. water, v. sol. alcohol,
— CaA'j2aq. — ^AgA': gelatinous pp. which be-
comes flocculent on boiling.
(i3)-Hyoglycooholic acid C2,H„NO,7 Be-
mains in the mother-liquor when the ordinary
or (a)-hyoglycocholate of sodium is ppd. by ice-
cold saturated Na,SO, (Jolin, H. 11, 417; 12,
612 ; 13, 205). When this mother-liquor is eva-
porated sodium iS-byoglycocholate sepa-
rates in dark brown oily drops, which solidify to
a sticky mass. This is washed with ether, and
then presents a white curdy appearance. It is
V. sol. alcohol and water. The free acid and its
salts greatly resemble their (a)-isomerides, bat
the salts of the (i3)-acid melt, as a rule, more
easily, and have a less bitter taste. (;3)-hyoglyoo-
cholio acid gives Pettenkofer's reaction. The
(a)-acid is ppd. by dilute acids more readily than
the (i8)-acid. The alkaline salts of the (/3)-acid
are more soluble in water than those of the (a)-
acid. The Ba, Ca, and Mg salts of the (|3)-acid
differ from those of the (a)-acid in dissolving in
excess of the sodium salt. The sodium salt of
the (/3)-acid is dextrorotatory.
ETOSCIirE. This name was first used to
denote the base, subsequently proved to be tro-
pine, obtained by saponifying hyoscyamine. It
was then given to a base that accompanies
hyoscyamine {q.v.).
HYOSOINIC ACID is identical with Tbofio
Aom.
HYOSCTAMINE C^HjsNOj. Duboisine.
Datturine. [109°]. An isomeride of atropine
occurring in henbane (Syoseyamus niger) and
in other species of Hyoseyamus (Geiger a. Hesse,
A. 7, 270 ; Hohn a. Beichardt, A. 157, 98). It
occurs both in the seeds and in the juice of these
plants, and is accompanied by hyoscine (Laden-
burg, A. 206, 282). It accompanies atropine in
the seeds of the deadly nightshade {Atropa
Belladonna) ; indeed Ladenburg (B. 21, 3065) is
of opinion that atropine is an optically inactive
base standing to hyoscyamine in the relation of
racemic acid to leevotartario acid. From 20 g.
of commercially pore atropine auroohloride
Ladenburg isolated by recrystallisation 1 g. of
hyoscyamine auroohloride, and to this he attri-
butes the statement that atropine can be con-
verted into hyoscyamine. Hyoscyamine occurs,
mixed with atropine, in the seeds of Datura
Stramonium (Pesoi, 0. 12, 39; Ladenburg, G.B.
90, 874; B. Schmidt, A. 208, 196), and in the
leaves and twigs of Duboisia myoporoides (P. v.
Muller a.Eummel, 0.^.35,32; Gerrard, Ph. [3] 8,
787 ; Ladenburg a. Petersen, B. 20, 1661). Hyos-
cyamine mixed with hyoscine occurs in the root
HYPOXANTHINE.
746
of Seopolia ja/ponica ; hyosoyamine also occurs
in the loot of ScogoUa Slardnaekiana (E.
Schmidt a. Hensohke, Ar. Ph. [3] 26, 185, 214).
Pr^aration. — Henbane seeds are extracted
with boiling alcohol (90p.c.) acidulated with
tartaric acid, and when the alcohol is distilled
off the residue separates into two layers. The
upper layer is a green oil, which is shaken with
dilute HjSOf, and the acid liquid, after nearly
neutrahsing with K^CO,, is filtered and evapo-
rated to a syrup. When alcohol is added to this
syrup EjSO, separates, and the alcoholic solu-
tion must be freed from alcohol by distillation,
mixed with a little water, and shaken with
E^OO, and chloroform. The alkaloid is ex-
tracted from the chloroform by dilute HjSO^,
and the acid solution, decolourised by animal
charcoal, evaporated, and allowed to stand in
contact with CaCO,. The liquid is finally
mixed with sand, evaporated over H2SO4, and
the alkaloid extracted by chloroform, from which
it crystallises in long prisms (Duquesnel, J. Ph.
[5] 6. 131).
Properties. — Needles (from dilute alcohol), or
prisms (from CHCl,). More soluble in water
and dilate alcohol than atropine. Lsevorotatory :
Md = — 21°. It enlarges the pupil of the eye in
the same way as atropine. It will not sublime
(Blyth).
Beaeiions. — 1. Converted into atropine by
heating for 6 or 6 hours above its melting-point
(E. Schmidt, B. 21, 1829). The optical activity
of hyoscyamine may likewise be diminished by
allowing its alcoholic solution to stand in the
cold after a slight addition of one of the follow-
ing bases: NaOH, KOH, NH„ NMe^H, and
NMe^OH (Will, B. 21, 1717; Will a. Bredig, B.
21, 2777). The optical activity cannot be re-
duced below [o]d = — 1'89° by this method, so
that if Ladenburg is correct in holding atropine
to be optically inactive, the conversion of hyos-
cyamine into atropine is incomplete. — 2. Split
up by boiling dilute HOI into the same products
as atropine, viz.: tropine and tropic acid
(Ladenburg, £. 13, 607). Baryta- water gives the
same products.
Salts. — B'ECAnCl^: [159T (L.); [162°]
(Will); golden leaflets with brilliant lustre
(Ladenburg, B. 13, 109). The corresponding
•nrochloride of atropine melts at 137° and has
no lustre. The atropine aurochloride melts
under water, that of hyoscyamine does not.
Hyoscyamine aurochloride is less soluble in
water at 60° than atropine aurochloride. —
B'jHjSO, (dried at 100°). Slender needles.
[206°]. — Cadmioiodide: needles (from alco-
hol); almost insol. water. — Hydro bromide:
compact prisms (from water). — ^P i c r a t e : yellow
oily pp. quickly changing to rectangular plates.
— Flatinochloride: triclinio (Fock, B. 21,
1720).
Hyoieine C^H^NO,. Amorphous hyoscyam-
ine. Colourless syrupy fluid. Occurs in the
mother-liquor from which hyoscyamine has crys-
tallised. It closely resembles hyoscyamine, both
in its mydriatic action on the pupil of the eye
and in other respects. Boiled with water it splits
np into tropic acid and psendotropine. Solution
of hyoscine hydrochloride is precipitated by
HgCt HgKA. and K,PeOy,.
Salts.— B'HAuCl,: [198°]; yellow prisms.
— B'HI^aq: (dried at 100°) ; small monoclinic
prisms; a:&:c = ■938:1:1-857. M. sol. water.—
B'HBrS^aq: trimetricprisms ; a:b:e = '601:1: -411;
V. e. sol. water.— B'jHjPtOlj : octahedral crys-
tals, sol. water and ether-alcohol.— Pier ate
B'CsHj(N0j)30H : prisms (Ladenburg, B. 13,
1649 ; 14, 1870).
HYOIAUKOCHOLIC ACID C„H,,NSO, (?).
Occurs in very small quantity in pigs' bile
(Strecker, A. 70, 180). Apparently split up by
boiling with HCl into taurine and hyocholio
acid^
HYPO-. Use of this prefix applied to morganie
compoimds : for hypo- compounds v. the element
the hypo- compound of which is sought for, or
the salts to the name of which hypo- is prefixed.
Thus hypo-iismuthic oxide will be found under
Bismuth, oxtoes of; hypo-bromous acid and
hypo-brormtes will be found under Bbomine, oxt-
AciDB ot; hypo-phosphdtes will be found under
Peospeobus, oxt-acids or.
HTFOa^IC ACID. This name was given
by Gossmann a. Scheven (A. 94, 230) to an acid
of the oleic series CgeHggO,, melting at 33°, sup-
posed to exist in earth-nut oil (c/. Schroder, A.
143, 22; Caldwell a. Gossmann, A. 99, 310).
According to Schon (A. 244, 253), however, no
such acid can be obtained from the oil, which
contains oleiin and not its lower homologue.
HYPOQTTEBEACHINE C,^,Nj.Oj- [80°].
An alkaloid occurring in quebracho bark (Hesse,
A. 211, 264). It is a strong base with bitter
taste, V. sol. alcohol, ether, and chloroform.
Forms yellow amorphous salts. — B'2H2FtCl,4aq.
HYPOXAKTHINE OjH^N^O. Sarcine. Sar-
kine. S. -33 in the cold ; 1-28 at 100°. S. (al-
cohol) -11 at 78°. Occurs in the spleen of men
and oxen (Scherer, A. 73, 328), in the bone-
marrow of men and calves (Heymann, Pf. 6,
194). Occurs also in the muscular tissue of
horses, oxen, and hares (Strecker, A. 108, 137),
and in the blood of corpses (Salomon, JET. 2, 94).
It is a product of the reduction of uric acid
CsH^NjOa by sodium-amalgam (Strecker a.
Bheineck, A. 131, 121). It is formed from blood-
fibrin by the action of pancreas-ferment, and in
much smaller quantity by the simple decay of
blood-fibrin (Erause a. Salomon, B. 11, 574;
12, 95 ; 13, 1160) ; in both cases its formation
may be due to the presence of nuclein in the
blood-fibrin, since it is not formed from purified
fibrin (Kossel, H. 5, 156 ; Chittenden, J. Th.
1879, 61). Formed, together with xanthine,
leucine, tyrosine, guanine, and carnine, in the
decomposition of the proteid constituents of yeasi
(Sohiitzenberger, Bl. [2] 21, 204 ; Kossel, R. 3,
291). Hypoxanthine is also formed by the action
of chlorine-water on carnine C^HgNjOj (Weidel, A.
158, 362). Hypoxanthine accompanies caffeine
and xanthine in tea (Baginsky, H. 8, 395).
Preparation. — Extract of meat is dissolved
in water and ppd. with lead subacetate. The
filtrate is freed from lead by H^S, concentrated,
and ppd. with ammonia and AgNO,. The pp. is
dissolved in the smallest possible quantity of
dilute HCl (S.G^. 1*1). The compound of hypo
xanthine and AgNO, separates on cooling, and is
subsequently decomposed by H^S (Neubauer, Fr.
6,41).
Properties. — Minute crystals, si. sol. water,
T. si. sol. alcohol. Beadily soluble in aoids and
746
flYPOXANTHINE.
alkalis. Fpd. by CO, from its solution/ in aque-
ous EOH. Keutral to litmas. Fpd. by phos-
phomolybdic acid in acid solution. According
to EoBsel (S. 6, 428) it cannot be oxidised to
xanthine as formerly supposed.
Salts.— CsH^N^OHClaq: tables.—
(05H,N,0)jH^tCl,: yellow crystals, si. sol. cold,
very soluble in hot, water. — CJ3.^T>(flBBi. —
CJiJKfiiBSO,; (at 100°): large crystals.—
CsH,N,OBaOjHj : crystals.— OjH^gjN.O ^Aq :
gelatinous pp. — CjHjNjOAgNO, : floccnlent pp.
Crystallises from boiUng HNO, in small scales.
Dissolves in 4,960 pts. of cold dilute HNO, (S.Q.
1-1). The ppn. of hypoxanthine by AgNO, is
prevented by the presence of gelatin in t£e solu-
tion (SalkowsM, Pf. 6, 91).
HTSTAZASINE v. Di-oxx-isisaupusosa.
IBOTIK. A glaeoBide said to occur in the
aqueous extract of the seeds of Ligustrwn Ibotu
(Martin, Ar. Ph. [3] 13, 338). The solution is
ppd. with lead acetate, and the pp. decomposed
by HjS and exhausted with alcohol. It is a
yellowish-white powder. Cone. H^SO^ dissolves
it, forming a red solution, which loses its colour
on addition of water.
ICACIN 0„H„0 or (05H,),H,0 (Fliickiger) ;
C,iH„0 (Stenhouse a. Groves, A. 180, 255; C. J.
29, 175) ; C„H„(0H) (Hesse, A. 192, 181). The
last formula represents it as amyrin in which
one hydroxyl has been displaced by hydrogen.
Icacin is the crystalline resin of conima or In-
cense resin (Scribe, A. Ch. [3] 13, 166). Steam-
distillation expels an essential oil, conimene
(q. v.), the remaining resin being almost entirely
soluble in alcohol, fiom which it is deposited in
silky needles on cooling. It may be purified by
recrystaUisation from Bgroin. It crystallises in
needles [176°]. Insol. water, m. sol. boiling
alcohol and petroleum, v. sol. ether, CS,, and hot
benzene. Hot cone. E^SO^ blackens it.
n-ICOSAKE C„H„. [36°]. (205° at 15 mm.).
S.G. Y -778 ; f -749 ; ifa -736. Formed by reduc-
tion of the dichloride of heptyl tridecyl ketone
with HI and P. Produced by treating n-decyl
, iodide with slices of sodium ; the reaction which
begins in the cold is finished by heating to 150°,
and the product is mixed with alcohol, i^ater
being then added, and the hydrocarbon rectified
and finally crystallised from ether-alcohol. Ob-
tained also by fractionating paraffin from brown
coal (Kraft, B. 15, 1717; 19, 2220; 21, 2262).
ICOSIKENE Cj„Hjj. EicosyUne. (315°).
S.G. — •818. Prepared from ozokerit, or the
solid paraffin [37°] from brown coal by heating
with PCI5 at 170° and distilling the resulting
C^AgCl, (Lippmann a. Hawhczek, B. 12, 69).
Combines with Br and 01 forming oily C2„HagBr,
and C^^ggCl, (v. Di-chlobo- and Di-bbomo-
icosylene).
ICOSONENE Ca;H,,. mdecene. (330°-
335°). S.G. IS -936. [o]^ 2°. Obtained
from the fraction (330°-340°) of the product of
the distillation of colophony, by removing other
unsaturated hydrocarbons by treatment with
HjSOj or HNO, (Benard, C. B. 106, 1086). Co-
lourless, non-fluorescent, oil. Does not alter
when exposed to air, and is not affected by
H,SO„ by HNO,. by HCl, or by bromine in the
cold. Ocenrs to the extent of 10 p.o. in the
resin oil.
ISBIAIIN Cg AA. The essential consti-
tuent of idriaUte, a mineral foimd mixed with
cinnabar in the mercury mine of Idria (Dumas,
A. 5, 16 ; Schrotter, A. 24, 336 ; Laurent, A. Ch.
[2] 66, 143; Bodeker, A. 62, 100; Goldschmiedt,
J. 1879, 365 ; B. 11, 1579). Extracted by boil-
ing idrialite with xylene. Glittering plates. Maj
be distilled in a current of CO,. Almost insol,
alcohol and ether, v. sol. boiling oil of turpen-
tine, V. e. sol. CS,. Fuming H2SO4 forms a sul-
phonic acid. It gives no acetyl derivative.
Oxidised by chromic acid to palmitic and stearic
acids and oxyidrialin CggH^gO,,, a red substance
which forms a deep-violet solution in H,SO,.
Oxyidrialin may be reduced to idrialin by distil-
lation with zinc-dnst, but it gives stearic acid
when distilled in a current of hydrogen.
Bromine-water converts idrialin into
C,„H„Br„0,. Br in HOAo forms C,„H,jBr„0„
a reddish-yellow powder, v. sol. hot chloroform
and benzene. Boiling cone. HNO, forms
C8„H43(NO,)„Op Fuming HNO, produces
Cg.H„(NO,),eO,.
IDBYL is identical with Fluobakiheiie (q.v.).
IGASURINE is impure Bbuoine (Shenstone,
C. J. 39, 457).
ILIOYL ALCOHOL C,gH«0 (Personne, C. B.
98, 1585 ; Bl. [2] 42, 150) ; CjjHggO (Divers a.
Kawakita, C. J. 53, 274). [176°] (P.) ; [172°]
(D. a. E.). (above 350°). Birdlime, obtained
Dy fermentation of the inner bark of the holly
Ilex AqmfoUwn, is a greenish tenacious sub-
stance, which when dried at 100° and extracted
by chloroform or ligroiin leaves an ash mainly
composed of calcium phosphate. The evaporated
extract contains a compound ether, which may
be saponified by alcoholic EOH. An elastic sub-
stance resembling caoutchouc separates, and
when the liquid portisn is poured into water a
gelatinous pp. is obtained, which can be purified
by repeated crystallisation from alcohol. Needles
(from alcohol or by sublimation); insol. cold
water, m. sol. alcohol, miscible with boiling light
petroleum, ether, and chloroform. On heating
with palmitic acid a substance resembling bird-
lime is formed.
Acetyl derivative [206°J.
ILIXANTHIN C„HaO„. [198°]. Occurs in
the leaves of the hoUy {Ilex Agmfolmm). Ob»
tained from the leaves gathered in August by
BIIDO-DI-FORMIO ETHER
747
eztraoting them with dilute (80 p.o.) alcohol, le-
moving the greater part o{ the alcohol by distil-
lation, washing with ether the granules which
separate in a few days, and recrystaUising from
alcohol and hot water (Moldenhaner, A. 102,
846). Minute straw-yeUow needles. Decomposes
with ebullition at 215°. Nearly insol. cold
water, v. sol. hot water, forming a yellow solu-
tion ; sol. alcohol, insol. ether. It does not re-
duce boiling Fehling's solution. Dissolves in
HCL^q. Alkalis and alkaline carbonates torn
its aqueous solution orange-yellow. FeCl, colours
its solution green. Lead acetate and subaoetate
give a splendid yellow pp., soluble without colour
in acetic acid. Ilixanthin dyes cloth, mordanted
with iron or alumina, yellow. A yellow crystal-
line substance, CisHjoO,,, which may be extracted
from the leaves of buckwheat {PolygomuTn Wago-
pyrum), differs from ilizanthin only in giving an
oUve-brown odlouratibn with FeCl, (Schnnck,
Chem. Oaz. 1859, 201).
IMABENZIL V. vol. i. p. 467.
IMIBES. Compounds containing the diva-
lent group imidogen NH united to a divalent
acid radicle. They are for the most part described
under the acids which may be obtained from them
by displacing NH by (OH)^.
lUISO-SI-ACEIIC ACID v. Di-oltcoij^amio
Aom.
SMHISO-s-DI-AMISO-BEirZENE
C^(NEL,)j(NH), [1:4:2:5]. The nitrate
C^THniJNB^mXO,), is obtained as a pp. of
small green needles by adding an excess of
Fe^Cl, to a solution of s-tetra-amido-benzene
hydrochloride (1 pt.) and ordinary £070, (2 pts.)
in water (15 pts.). By solution in cone. H^SO^ it
is converted into s-di-nitro-di-amido-quinone
C.(NOj)j(NHj)jOs [1:4:2:5:3:6] (Nietzki, B. 20,
2115).
IMIDO - AUIOO-EIHENYL-o-AMISO -FHE-
HTL-UEBCAFTAH C,H,N,S probably
C.H,<|^C.O(NH:j):NH. [160°]. Obtained by
dissolving o-amido-phenyl mercaptan in an ex-
cess of alcoholic cyanogen. Colourless needles
(front alcohol) or plates (from benzene). Weak
base. By heating with aniline it is converted
into the mono- and di- phenyl derivatives
C^,<^^C.C(NHPh):NH and
C,H4<;[^^C.C(NHPh):NPh, with evolution of
NH,. Warmed with an alcoholic solution of o-
amido-phenyl mercaptan it is converted into the
anhydro-oxalyl derivative of the latter
CeH,<[g^O.C.^>C,H„ ammonia being
evolved. Cold alcoholic KOH splits off NH,,
giving the acid C,H4<^g^0.C0jH. Salts.—
B'HjOIjPtOl..— B'HClAuOl, (Hofmann, B. 20,
2252)
DI'IHIDO-AUISO-OSCIN v. Amido-dmmido-
OBCIN.
IMISO-AmDO-SI-FHENYI. SULPHIDE v.
AMIDO-IMIDO-DI-PHEirni SrLFHIDE.
OI-IMIDO-AKIDO-BESOBCIN v. Amido-oi-
mmo-BEsoBatH.
lUIDO-BENZTI. ISOAMYI. STTLFHIDE
0,jH,^S i.e. C,H,.C(NH).S.C5H„. Ponned by
passing fiCl into a mixture of isoamyl mercaptan
and benzonitrile, and decomposing the resulting
crystalline hydrochloride B'HCl with aqueous
NaOH (Pinner a. Klein, B. 11, 1825). Oil.
lUIDO-BENZTL ETHTI. STTLFHIDE
0,H„NS i.e. C,H,.C(NH).S.Et. From benzoni>
tdle, mercaptan, and HOI. Also from thiobenz-
amide and EtI (Bemthsen, A. 197, 348). Oil.
Readily splits up into benzonitrile and mercap-
tan. Its alcoholic solution gives pps. with
CuSO^and HgCl^— B'HCl: [188°]; short thick
prisma, V. e. sol. water and alcohol. — B'^jPtCl, :
needles. — B'HI : [142°] ; monoclinio prisms.
IMIDO-DI-BENZTL STTLFHIDE
0,H,C(NH).S.CH,.0,H,. The hydrochloride
B'HCl [181°] is formed by heating thiobenzamide
with benzyl chloride, or by passing HCl into a
mixture of benzonitrile and benzyl mercaptan
(Bemthsen, A. 197, 350).
IMIDO-BTTTYBIC EIHEB v. Ackio-aoetio
EIHEB IMIDE, vol. L p. 19.
IMIDO-CABBAMINE-THIO-BTTITBIC ACID
V. THIO-mUMISO-BUTTKIO ACID.
IMIDO-CABBONIC EIHEBS. These com-
pounds, having the formula NH:C(0B)2, are more
properly described as ethers of imido-formic
orthaldehyde {q.v.).
lUIDO-COTTUABIN v. Coumabht.
IMIDO-DIETHANE DISTTLFHONIC ACID
V. D1-EIHVI.-AIIINE ni-SUIiPHONIC ACID.
IHIDO-ETHEBS. Compounds containing
the group 0(OEt)(NH) (Pinner, B. 17, 182, 184,
2002, 2007). The hydrochlorides of the imido-
ethers are formed by the action of dry HCl on a
mixture of a nitrile and an alcohol, dissolved in
dry ether. The hydrochloride of a chloro-amido-
ether B001(NH2)(0Et) is first formed, but this
rapidly splits up into HCl and BC(NH)(OEt).
The hydrochlorides of the imido-ethers react
with alcohols, forming orthoformic ethers :
KC(NH)(OEt) + 2E'0H = RC(OB')j(OEt) +NH,.
Alcoholic NH, turns imido-ethers into amidines :
EC(NH)(OE') + NH3=EC(NH)(NHj) + HOE'.
Primary amines act like ammonia, but potash
and tertiary amines do not act upon free imido-
ethers.
lUIDO-FOBUIG OBTHALDEHYDE
HN:C(0H)2. Irmdo-Borbomc add.
Methyl ether HN:C(0Me)2. Obtained like
the ethyl ether by reduction of its chloro- deriva-
tive ClN:C(0Me)2 (chlorimido-carbonic-methyl-
ether) with potassium arsenite. Very volatile.
Ethyl ether HN:0(OEt)j. Prepared by
shaking 15 pts. of ' chlorimido-carbonio ether '
(ClN:C(OEt),) with a solution of 11 pts. of AsjO,
and 30 pts. of EOH in 120 pts. of water, not
allowing the temperature to exceed 50°. Alka-
line liquid with odour resembling trimethylamine,
Miscible with water but separated by addition of
Na or OHKOH. On distillation a large part de-
composes. By acids it is decpmposed into N^
and carbonic ether. By hypochlorites it is con-
verted into ' chlorimido-carbonic ether' (Sand-
meyer, B. 19, 864). The hydrochloride formed
by passing HCl, in the dry ethereal solution, is a
thick liquid, which decomposes on heating into
urethane and ethyl chloride.
lUIDO-DI-FOBKIC EIHEB C,H„NO. i.«.
NH(00jEt)j. [50°]. (226° at 760 mm.) ; (145°
at 20 mm.). One of the products of the action
of chloro-formic acid on potassium cyanate in
presence of ether (Wurtz a. Henninger, C. R
748
mroO-DI-FOEMIO ETHEE.
100, 1419; B2. [2] 44, 26). Longpiismg. Forms
biuret when heated with aqueous NH,. —
AgCsHggKOt : cubes, blackens at 100°.
jS-IMIBO-GLTTTAUIC ETHEB
COjEt.CHj.C(NH).OH,.OONHj. [86°]. Formed
by the action of aqueous ammonia on acetone-
di-carboxylio ether C0(CH,.C0^t)2 (Stokes a.
V. Fechmann, Am. 8, 377). Long, flat, colourless,
flexible needles; si. sol. cold water and ether;
Bol. hot water and alcohol ; m. sol. hot CHCl,.
Heated above 86° gives off water and ammonia.
Fe^Gl, gives deep red colouration. Soon de-
composes in aqueous solution. PtOl^ gives
(NHJjPtCl,. NaKO, in acid solution gives a
yellow pp. [178°]. Boiled with NajCO, it gives
di-oxy-amido-pyridine (CjHgN^O,).
lUISO-HEXOIC ACID. Nitrile
NH:CEt.CHMe.CN. [48°]. (258°). Formed by
the action of Na on propionitrile dissolved in
ether, the product being decomposed by water
(Meyer, J. pr. [2] 38, 336). Plates, si. sol. water,
V. sol. alcohol and ether. Cold cone. HClAq
converts it into Et.CO.GHMe.GN. Cone. HClAq
at 150° forms di-ethyl ketone, NH,, and COj.
Be'duced by sodium in alcoholic solution to
propylamine.
Imido-di-isohezo^c acid. Nitrile
EN(0^,g.CN)2. Imidmsocaijaro-mtrile. Formed
as a by-product of the action of urea upon
valerio-aldehyde-oyanhydrin. The hydrochloride
(B'HCl) forms white silky needles, [159°], v. sol.
alcohol, insol. ether (Pinner a. Lifschiitz, B. 20,
2356 ; cf. Erlenmeyer, B. 14, 1868).
lUIDO-IUISO-DIFEENYL STIIFHIBE
N /°«^«Ns. Formed by treat-
ing amido-imidd-diphenyl sulphide hydrochloride
with FeCl, (Bernthsen, A. 230, 103). Brown
needles (from dilute alcohol) ; v. si. sol. water,
m. sol. hot alcohol. Beduced by alcoholic am-
monium sulphide to amido-imido-diphenyl sul-
phide. Its salts dye silk violet.— B'HCl : insol.
ether, v. e. sol. water and alcohol. — B'^H^ZnCl, :
long, dark-violet, needles ; m. sol. water.
IHIDO-BI-MALONIC ACID. Amide
HNiCH(CO.NHj),}j. Formed by heating chloro-
malonic ether with alcoholic NH, at 140° (Conrad
a. Guthzeit, B. 15, 606). Prisms; sol. hot
water.
IMIDO-VEIHYL ALCOHOL v. Fobmimido-
ETHBB.
DI-IMIDO-NAFHIHOL t). AuiDo-NAf^THO-
qniNONE-IUIDE.
IMIDO-DIITAPHTHYL Ca,H„N i.e.
I ySH.IHna^hthylcarbazoh.[216°].'Foimei
C..H/
by boiling di-a-amido-dinaphthyl (dinaphthyl-
ine) with an excess of h61 or other acid, NH,
being eliminated (Nietzki a. Goll, B. 18, 3259).
Crystallises in long colourless needles or silvery
plates. Sublimes in colourless needles. It dis-
solves in HjSO, with a reddish-brown colour, a
trace Of nitric acid added to this solution pro-
duces a dark-green colouration.
Eicrate B'C.H4(N0j),0H : [226°]; red
needles (from benzene or alcohol) ; sublimable.
Acetyl derivative C^H^NAo: [above
800°]; colourless plates; sol. acetio acid and
alcohol, insol. benzene.
CjjHjNjS i.e. /,
Nitrosamine Oa,H,jN(NO) : [above 800"] 5
small yellow plates ; very sparingly sol. ordinary
solvents.
Imdo-(/3j3)-dinaphthyl NH<p'°2«>. [170°].
Obtained by heating (3)-imido-dinaphthyl sul.
phide with powdered copper in a current of CO,
(Bis, B. 19, 2240). Almost colourless needles ;
si. sol. alcohol, V. sol. ether, v. e. sol. benzene.
Its solution shows intense bluish-violet fluor-
escence.
PicrateB'C,Hj(N02),0H. [221°].
Acetyl dirivative CjgHijKAc. [143°].
Long yellowish needles (from benzene) ; si. sol.
ether, and alcohol.
IMIDO-DI-KAPHTHYL OXIDE Cj„H„NO t.«,
NH<^^'»2«>0. Oxy-ai-nwphthylamme. [301°].
Formed by heating imido-di-naphthyl sulphide
with cupric oxide at 270°, and extracting with
boiling benzene (Bis, B. 19, 2244). Lemon-yellow
crystalline powder (from benzene). Cannot be
distilled. SI. sol. alcohol, ether, HOAc, and
boiling benzene ; v. sol. HjSO^.
Acetyl derivative Ca,H,jAcNO. [235°].
Almost insol. alcohol and ligroin, m. sol. ether
and benzene.
IMIDO-DI-NAFHTHYL STTLPHIDE
CjoHigNS i.e. NH<^"^p>S. Thiodinaphthyl.
amine. [236°]. Formed by he&ting di-(4)-
naphthylamine (10 pts.) with sulphur (2'4 pts.)
for 10 hours, the temperature being slowly raified
to 250° (Bis, B. 19, 2241). The product is ex-
tracted with hot benzene, and boiled with copper
powder. Pale yellowish-green needles. Sol.
ether and HOAc, v. sol. boiling benzene. Cono.
H2SO4 forms a violet solution. Distillation over
reduced copper forms imido-di-napbthyl. Dis-
tillation over CuO at 270° gives imido-di-
naphthyl oxide.
Picrate B'{C^(NO^fiB.),. [c. 256°].
Dark plates or yellow needles; almost insol.
alcohol, ether, and benzene.
IMIDO-DI-OCTOIC ACID CiA.NO, t.e.
NH{CH(C8H,s).C0jH)j. Imido-caprylic acid.
[210°-215°], Formed, together with formic acid, '
HCy, and heptoic aldehyde, by boiling its nitrile
(1 pt.) with HClAq (15 pts.) for an hour (Erlen-
meyer a. Sigel, A. 177, 136). When the nitrile
is heated with fuming HClAq at 100° it yields
the acid and the imide, from which mixture the
acid may be extracted by Na^COjAq. White
tasteless powder, which becomes pasty at 180°.
Almost insol. cold water and alcohol. Dissolves
unaltered in boiling dilute (20 p.c.) HCl, brilliant
needles of its hydrochloride separating again on
cooling. Strong (40 p.c.) HClAq at 180° resolves
it into amido-octoic acid and heptoic aldehyde,
CaHjA"j : oryptocrystalline pp.
Imide 0,gH.gJSJ[), i.e.
NH<Cigi::J:00>NH. [79•6^. Forme-ia,
above. Needles, insol. cold, nearly insol. boil- '
ing, water ; v. sol. alcohol and ether. B'HCl :
minute needles, formed by passing HCl into_ its
ethereal solution. Boiling water splits it up into
HCl and the imide. Boiling cone. KOHAq con-
verts it into the acid.
Nitrile 0,.H»Ns. [0. €°]. From heptoifl
aldehyde (cenanthol) by combining it with NH|
IMIDO-DI-PHENYL SULPHIDE.
749
»nd treating the resulting oenanthol-ammonia
with HCy. Dilute HCl then dissolves out the
nitrile of amido-octoio aoid, leaving the nitrile of
imido-di-ootoio aoid undissolved. Thick oil ; v.
sol. alcohol and ether, v. si. sol. water and dilute
HGIAq. Split up by boiling with AgNO, giving
heptoio aldehyde and AgCy. B'HCl : crystals,
sol. alcohol ; decomposed by water into HCl and
the nitrile.
lUISO-OXY- V. Oxy-hqdo- .
SI-IUIDO-DI-FHEKYL-ACETTLENE (?)
0„H,oO,i.e. C-^o^^^>NH(?). Syckazido-
di-phenyl-acetylene. XH-imido-tolame. [o. 380°].
Formed by treating an alcoholic solution of iso-
di-nitro-benzil with tin and HCl (Golubefl, J.B.
16, 577). Thin tables. Sublimes at 250°. V. si.
Eol. boiling alcohol,iorming a solution exhibiting
violet fluorescence.' HNO, (S.G. 1-3) converts it
into an amorphous indigo-blue compound. It
does not combine with acids.
Benzoyl derivative CnHjBZjNjOj.
[240°]. PtJe yellowish needles (from toluene-
alcohol), m. sol. boiling benzene, from which it
crystallises as C,p^z^ fijij^ on addition of
a little alcohol.
lUIBO-PHENYI-BESrzOLYCOCYAIIIBINE
17. vol. i. p. 462.
lUISO-FHENTL-FBOFIOinc ACID
C,Hj.CH.GH.C02H. Imido-cinnamic acid.
NH
Benzoyl <2eriva<ii;e C,eH„NO, t.e.
Fh.CH.CH.CO2H. A body which probably has
\y
NBjs
this constitution is obtained by saponification of
its anhydride which is prepared by heating
hippuric acid with benzoic aldehyde and acetic
anhydride. The acid forms monoclinic needles.
[225°]. Sol. alcohol and ether, nearly insol.
water. Heated with aqueous HCl or NaOH it
yields an acid CgH,0, which is probably the
true phenyl-glyoidio acid CeHj.CH.CH.GOjH
O
(P16chl, B. 16, 281S).
Benzoyl derivative of the anhydride
CjjHmOsNj. [165°]. Yellow needles, sol. hot
alcohol, si. Bol. ether, insol. water. Formed as
above.
o-IMrDO-DI-PHENYl-DI-FEOFIONITEILE
C„H„N, t.B. (Ph.CH,.CH(CN))jNH. Formed to-
gether with a-amido-phenyl-propionitrile by the
action of NH, on the compound of HCN and
phenyl-acetic aldehyde (Erlenmeyer a. Lipp, A.
219, 191). White crystalline powder [87°] or
small needles (from water). SI. sol. alcohol or
ether, insol. petroleum, v. si. sol. water, m. sol.
benzene. From ether it forms six-sided prisma
[106°] or rhombic tables [109°], both belonging
to the monoclinic system. They are perhaps
polymerides.
Salt.— B'HCl : insol. ether.
lUIDO-DI-FHEKYL-SULFHISE C^H^KS
M.NH^^S'S'^S. TModvphewylamme. Di-
phervgUhiazine. [180°]. (0. 371° unoor.);
(290° at 40 mm.).
FormaUcm. — 1. By heating diphenylamine
with sulphur or bodies that give off sulphur, such
as SjCl, (Bernthsen, A. 230, 75).— 2. By the action
of SCI2 on diphenylamine dissolved in benzene
(Holzmann, £.21, 2064).— 3. In small quantity
by heating o-amido-phenyl mercaptan with pyro-
catechin for 30 hours at 230° (Bernthsen, £. 19^
^255).
Preparation. — By boiling diphenylamine
(1,500 g.) with sulphur (580 g.) for 8 hours. The
product is distilled in small portions (250 g.)
and the distillate (60 g.) fractionated (Bernthsen,
A. 830, 77 ; B. 16, 2897).
ProperUes. — Slightly yellowish plates (from
alcohol or benzene). Sol. hot alcohol, HOAc,
benzene and ether, si. sol. ligroin. May be sub-
limed in plates. Has no basic properties, being
insol. dilute HCl. It oxidises readily, the alco-
holic solution turning red in air. FeCl, colours
its alcoholic solution dark green. Bromine va-
pour does the same. The green colour is de-
stroyed by alkalis. HNO, colours the solution
in HOAc green. Cold cone. HjSOf gives off CO,
and forms a greenish-brown solution which in
thin layers appears rose-red. Hot cone. H^SO,
forms a bluish-violet liquid. HNO, forms nitro-
derivatives which are reduced by SnClj toaleuco-
base, which on addition of FeCl, forms a violet
dye. Cold alcoholic solutions of imido-diphenyl
sulphide give : (a) with aqueons AgKO, a green
colour and a black pp. ; (&) with FtCl, a green
pp. ; (c) with CuSO,, HgClj, and Pb(OAc)„ no
pps.
BeacUons. — 1. Distillation over red-hot zmo-
dust gives some diphenylamine. — 2. By boiling
with copper powder it gives CuS and carbazole.
3. By heating with benzoic acid and ZnCl, there
is formed phenyl-acridine. — 4. EtBr gives ethyl-
imido-di-phenyl sulphide NEt<;^«g'>S [102°]
which crystallises in long thin white plates. — 6.
Mel forms the corresponding SC^H^NMe [100°].
Acetyl derivative CuHjAoNS. [197°].
Prisms. V. si. sol. hot HOAc, alcohol, and benz-
ene. Its alcoholic solution is not turned green
by Feci,.
Benzoyl derivative C,jH,BzNS. [171°].
Plates (from alcohol) ; m. sol. hot alcohol (Fran-
kel,,B. 18, 1844).
Constitution. — The imide group is shown by
the ready formation of the acetyl and methyl
derivatives. The sulphide character of the sul-
phur is shown by the oxidation of the methyl
derivative to a sulphone. The imido-di-phenyl
sulphide itself cannot be oxidised to a sul-
phone because the imidogen is . first attacked.
The body does not combine with Mel, but neither
does PhjS, although Me^S does. The S is not in
p- position, because that is still unoccupied.
Probably the formula is
CH NH CH
oh/\c/\c-'
HCiv^C^/Cs
CH S CH
which would also be indicated by its formation
from o-amido-phenyl-mercaptan.
References. — Amido-, Niieo-, Mbtbyi>-auido-,
and OxT- iMino-DiPBEirzL sulphide.
Imido-di-phenyl disnlphide NH<p^*>Sr
[60°]. Formed by the action of 8,01, on di-
760
IMIDO-DI-PHENYL SULPHIDE.
phenylamine dissolved in petroleum ether (Holz-
mann, B. 21, 2063). Small yellow needles,
insol. water, t. si. sol. cold aloohol, ether, and
benzene.
a.Iun>0-SI.FBOFIOinC ACID 0,H„NO« t.«.
KHICHMe.GOsH),. 'DiethyUdmelactamieeuiid.'
DidenlactaMc actd. Dilactamie add. Fonaed,
together with alanine, by treating aldehyde-
ammonia with HCl and HCy snccessively
(Heintz, A. 160, 35; 165, 44; 202, 875). The
product is boiled with lead hydrate, filtered, fleed
from lead by H^S, concentrated, and mixed with
alcohol. Alanine then separates, and the mother-
liquor is mixed with ZnCO, and evaporated to
dryness. The residue of zinc imido-dipropion-
ate is washed with water, and decomposed by
H^S. Minute slender needles, t. boL water,
insoL alcohol.
Salts.— NH4HA": rectangular tables (from
alcohol) or needles (from alcohol-ether). V. soL
water, si. sol. alcohol, insol. ether. — ZnA":
minute dimetrio tables, v. si. sol. water, v. sol.
HGlAq. — CdA"aq : minute needles (from water),
V. sol. cold water, but can exist also in a less
soluble form. — FbA" : crystalline crusts (ppd. by
adding alcohol to the aqueous solution). —
CnA"3aq: blue grains, v. si. sol. water and
alcohol.— AgjA" : white pp.; explodes slightly
when heated. May be crystallised from boiling
water.— HA'HCl : extremely soluble crystals.
Nitrosamine NO.N(CHMe.C02H)2. The
calcium salt of this acid is formed by treating
the acid, dissolved in HNO„ with calcium nitrite,
neutralising with lime, evaporating, and mixing
with alcohol and ether. The free acid, obtained
from this salt by treatment with oxalic acid,
forms flat colourless needles, v. sol. water and
alcohol, sol. ether.
mtrile CeH,N, t.«. NH(CMe.ON),. [68?].
When aldehyde-ammonia (1 mol.) is dissolved in
dilute (30 p.o.) HCy (1 mol.), and HCl or HjSO,
is added to acid reaction, a-amido-propionitrile
separates as an oil. If, after removing this oil,
the mixture be allowed to stand for several days,
needles of imido-dipropionitrile separate ; after
some time these are followed by crystals of hy-
drocyanaldine and finally of para-hydrocyan-
aldine (Erlemneyer, A. 200, 120 ; cf. Urech, JS. 6,
1115). It is.perhaps one of the products formed
by passing a mixture of anunonia and alcohol-
vaponr over red-hot iron (Monari, Cii.98,106).
MonooUnio needles (from ether); a:b:e
= l-086:l:l-247 ; /3 = 70° 21' ; m. sol. alcohol and
ether, si. sol. water. BeadUy sublimes. When
heated with dilute HCl it yields a-imido-dipro-
pionio acid. With AgNO, it gives on warming a
pp. of AgCy. Aqueous EOH has no action in
the cold, on warming it gives NH, and aldehyde.
B'HCl : white crystalline powder, insol. ether,
decomposed by water into HCl and the free
mtrile. Nitrosamine N0.N(CHMe.CN)2 :
pale yellow oil, heavier than water, sol. alcohol
and ether.
p-lmido-dipropionic acid NH(CHj.OHj.COjH) j.
Obtained, together with /3-amido-propionic acid,
by boiling 3-ibdopropionic acid with NH,(Heintz,
A. 158, 40 ; ef. Mulder, B. 9, 1904, who could not
obtain it). Syrup, which slowly crystallises.
— PbH^'',: very slender tableB.~Ag^" : pp. —
AgHA"AgKO,: soluble crystals.
di • luioo ■ besobcin c.h2(oh)2< i .
\nh
Formed by oxidation of di-amido-resoroin with
Fe,Cl„ Kjbtfi, or exposure of the alkaline solu-
tion to the air (Typke, B. 16, 556). Small
spangles. Insol. water. Dissolves in aqueous
HCl to a magenta-red solution, in strong E^SO,
to a violet solution. By tin and HCl it is re-
duced again to di-amido-resoroin.
DI-miDO-TEBEFHTHALIC ACID. Tetra-
/C(NH).CH(COjH)v
hydride. CHC >0H. This
\OH(CO,H).C(NH)/
acid is obtained by saponifying its ether With
alcoholic EOH and ppg. with HOAc (Boninger,
B. 21, 1765 ; cf. Baeyer, B. 19, 429). It crystal-
lises in greenish-yellow prisms, almost insol.
ordinary solvents. It forms a colourless hydro-
chloride B'HjCl,, crystallising in plates. In its
colourless derivatives the acid has become the
desmotropio di-amido-terephthaUc acid
at-IUIOO-DI-m-TOLinC ACID
[1:8] C5H4(COsH).CH,.NH.CHj.C,H,(COjH) [1:3].
[above 800°]. Formed by reduction of the acid
C5H4(C0jH).C(NH).S.C(NH).C,H,(C0sH) (from
m-oyano-benzoio acid and HjS) with zinc and
HCl. Crystalline. V. sol. alcohol, ether, benz-
ene, and CS, ; si. sol. hot water. SnbUmable.
Its characteristic zinc-salt is v. sol. water, alco-
hol, ether, benzene, and CS, (Bromme, B. 20,
lUISO-SI-ISO-VALEBONITBILE 0„H„N,
i.e. NH(CHPr.CN)j. [52"^. Formed, together
with a-amido-isovaleronitrile and oxy-isovalero-
nitrile by treating isobutyrio aldehyde-ammonia
(25 g.) with (30 g. of) a 30 p.c. solution of HCy
in the cold. The product is shaken with dilute
(5 p.c.) HClAq (200 g.) and ether. The ethereal
solution is dried over calcium chloride, and
saturated with HCl, whereupon the hydro-
chloride of imido-di-isovaleronitrile separates
(Lipp, A. 205, 1; B. 13, 905). The hydro-
chloride is decomposed by NH^q, and the free
nitrile extracted by ether, which leaves it on
evaporation as an oil, slowly crystallising over
HjSO,. Monodinic prisms ; v. si. sol. water, v.
sol. alcohol and ether.— B'HCl. Insol. water,
wluch removes its HCl.
lUINES. Compounds of divalent hydrocar-
bon radicles with imidogen, e.g. ethyUne-imiue
<C^NH.
IMFEBATOBIH 0„H„0, i.«.
CH,.0.0^«.0.C,H,.0.CH,.0.CH3? Peueedawin.
[76°] (Heut). Occurs in the root of masterwort
(imperatoria Ostruthmm) , together with terpenes
(170°-220°) (Wackenroder a. Wagner, J. 1854,
638) ; and also in the root of Peucedamim
officmale (Schlatter, A. 6, 201 ; Bothe, J. pr. 46,
371 ; Heut, A. 176, 71). May be extracted from
the root of Peueedemum by 90 p.c. alcohol, and
reorystallised from ether-ligrmn. Small trimetnc
six-sided prisms. According to Hlasiwetz a.
Weidel (A. 174, 69) it melts for the first time at
82°, and afterwards at 75«'. InBol. water; v. si,
sol. cold, V. sol. hot, alcohol; soL ether. Has no
taste. HNO, gives nitro-imperatorin, oxalic
acid, and tri-nitro-resorcin. Decomposed by
[ND AMINES.
751
heating with HClAq into MeCl and oroselone
OijIXijO,. Boiling alcoholic KOH gives formic
ftoid and oroselone.
Nitro-imperatorin, so-oalled. C,2H„N0j?
[above 100°]. Plates (from alcohol). Converted
by heating in _ gaseous NHj into OuHijNAi
■which crystaUisea from alcohol in tiimetrio
prisms, reconverted by acids into ' nitro-impera-
torin.'
IMPEWALINE OajH^NO^? [254°]. [o]i,=
— 35'4° (in chloroform). Occurs in lie bulbs
of FrUillaria imperialis. Extracted from the
bulbs by rubbing up with hme, drying at 100°,
and exhausting with hot chloroform. The ex-
tract is shaken with water acidified with tartaric
acid, the alkaloid ppd. from the concentrated
aqueous solution by Na^CO,, washed, and re-
crystallised from alcohol (Fraguer, B. 21, 3284).
The yield is -1 p.c. Short colourless needles,
turning yellow at 240°. V. e. sol. chloroform ;
m. sol. hot alcohol ; si. sol. ether, benzene, light
petroleum, and isoamyl alcohol ; v. si. sol. water.
Its solutions have a bitter taste, and are Isvo-
rotatory. Solutions of its sKlts are ppd. by the
usual reagents for alkaloids. Cone. H2SO4 turns
it pale-yellow. A mixture of the base with sugar
is turned by EgSO^ yellowish-green, pale-green,
flesh-colour, cherry-red, and dark violet succes-
sively. H2SO4 and KNO, give an orange-yellow
colour. A solution of the base in HClAq is
fluorescent, and becomes brownish-green when
warmed. — ^B'HCl : large crystals (from alcoholic
HCl); V. sol. water and alcohol.— B'jHjPtCla :
yellowish-red crystals (from hot dilute HClAq). —
B'HAuCl, : yellow crystals. The aurochloride
and platinochloride are both ppd. in oily drops
when ether is added to their hot alcoholic solu-
tions, but after washing with ether they may be
crystallised from hot dilute HCl. Thesulphate
is very hygroscopic. The oxalate crystallises
only from very concentrated solutions.
IKACTOSE. According to MaumenS (Bl. [2]
32, 652; 48, 773) this inactive sugar may be
formed by dissolving silver nitrate (20 g.) in a
solution of cane-sugar (20 g.) in water (100 c.c.) ;
after 24 hours the solution becomes dark-brown,
and it is then heated to 100°, filtered, and evapo-
rated on a water-bath. The residue is heated to
140°, dissolved in water, and filtered. To free
the solution from silver it is treated with a little
CaCl,, and filtered; the sugar is then ppd. by
alcohol. Inactive syrup. Its solution readily
dissolves lime.
INCENSE V. CoNiMENi:, IcAcm, and Ou-
BAKUM.
INSAUINES. Colouring matters, the chromo-
gen of which has the general formula
B"<[S5,^, where E" is an aromatic nucleus,
the nitrogen atoms occupying the para- position
to one another, and E' a hydrocarbon radicle
(usually aromatic) . The colouring matters them-
selves are derived by the introduction of a
basylous or chlorous group into one of the hydro-
carbon radicles (usually IS/). The indamines may
therefore be represented as derived from the (un-
known) di-imide of quinone OsHj^^jj-g-^, which
is probably the true chromogen. In the ind-
amines proper the chromophor is amidogen or
alkylated amidogen, the corresponding com-
pounds in which the ohroinophor is hydroxyl
being termed inddphenols.
ladamines are formed by the oxidation of a
mixture of a ^-diamine with an amine in which
the position para- to an amidogen is occupied by
hydrogen. Thus a mixture of tolylene-f -diamine
and o-toluidine reacts thus :
OAMe(NByj+ C»H«Me(NHj) + O,
= C,H,Me(
/
.NH
+ 2H,0
\N.C^,Me(NHj)
(Nietzki, B. 10, 1157 ; Nietzki a. Otto, B. 21,
1736). In this reaction we may suppose that
the tolylene-f -diamine is first oxidised to tolu-
JNH
quinone di-imide CeH,Me^ I , and that this
\nh
unstable substance then reacts upon the o-
toluidine.
The indamine hydrochloride
.NHjOi
\N.Cja4NMej
obtained by the oxidation of a mixture of p-
phenylene-diamine with di-methyl-aniline ia
different from the indamine hydrochloride
aT^McjOl
obtained by oxidising a miz-
.C»H,NH,
ture of di-methyl-27-phenylene diamine with
aniline.
The red dye obtained by oxidising di-methyl-
f -phenylene-diamine with bromine in HOAo
(Wutster, B. 12, 2072) is also a derivative of
/NH
quinone di-imide : 0|jH4<^ I , and reacts
\NMeyBr
with amines forming indamines, and with
phenols forming indophenftl.
Nitroso-di-methyl-aniline and quinone chlor-
imide also react with amines and phenols forming
indamines and indophenols respectively; thus,
nitroso-dimethylaniline hydrochloride acts upon
m-tolyleqe diamine, forming tolylene-blue (Witt,
B. 12, 933): O^K^Me^HCl ^ ^^^^
/NMejCl
= C,P,< I +H,0, while with
\N.CeH2Me(NH,)j
gallic acid it forms gaUocyanine :
C,H4<^^«^H'^1 + 0^(0H)3C0,H
-f-Hj0 + 2Hr
yNMejCl
i \N.CsH(OH)j.COj,H
J 0 1
In the last reaction the hydrogen represented
as liberated is in reality employed in reducing
another portion of the nitroso-di-methyl-aniline
(Nietzki a. Otto, B. 21, 1740). The (j3)-naphthol
violet obtained by Heldola {C. J. 89, 37) by the
action of nitroso-di-methyl-aniline upon (;3)-naph-
thol may also be represented as an indophenol
.NMejCl
C,Hi< I, , or perhaps as containing
\S.0,^V0H
/NMcjCl
two atoms of hydrogen less: CgH,/^ |
I \n.c,^.
' 0- !
A similar violet dye may be obtained by the
7f-2
INDAMKEa.
aotion of quinone di-ohlorimide upon an alco-
holic Bolntion of (J3)-iiaphthol:
,N01 vNH
Gfi,<;'\ +C,„H,OH =
'\l
CI
C^/| +2HC1.
*\
N.C,^,
L_or3'
j^-Amido-phenyl-piperidine
NH,.C,H<.N<^|=;pg'>CHj reacts like p-
amido-di-methyl -aniline in the formation of ind-
amines (LeUmann a. OeUer, B. 21, 2287).
Thus, if to a cold neutral solution of iJ-aniido-
phenyl-piperidine hydrochloride and »n-phenyl-
ene-£amine hydrochloride there be added the
calculated quantity of a solution of E^Cr^O,,
there is formed a deep-blue solution, from which
the colouring matter may be ppd.hy zinc chloride
as a brown powder.
The deriyatives of imido-di-phenyl sulphide
may be represented as indamines ; thus, in
Lauth's violet, 0^,< | , the tincto-
I \n.c,H3.nh,
! S— -'
rial properties need not be connected with the
presence of sulphur. The sulphur in Lauth's
violet is represented by oxygen in gallocyanine
and in (;3)-naphthol violet.
IITOAZINE 0,HA i.e. CeH,/) NnH.
Indamle. [146-6°]. (270°) at 743 mm. Formed
by heating hydrazido-cinnamic acid, when it
splits up into acetic acid and indazine
CsH,(NH.Na,).CH:CH.COja
= C^.<§^>NH + CH,CO^
(Fischer a. Kuzel, A. 221, 280). Formed also by
beating sulpho-o-hydrazido-cinnamio acid with
cone. HOlAq at 100° (Fischer a. Tafel, A. 227,
809). Slender needles. May be sublimed or
distilled. SI. sol. cold water or alkalis, v. sol. hot
water, alcohol, and ether. Sol. dilute HOI. Gives
ofF, when hot, an odour resembling resorcin.
With HCl and NaNO, in the cold it forms
yellow crystals of a nitrosamine, which gives
Iiiebermann's reaction. It does not reduce boil-
ing Fehling's solution. It ppts. several metallic
salts. Its hydrochloride separates from alco-
hol-ether in brownish crystals. Its sulphate
forms colourless nodules. The picrate crys-
tallises in yellow needles. Indazine is a much
stronger base than indole CjH4<\,-g3,CH,
and resists oxidation more powerfully.
OH
Nitrosamine C^.< I >N.NO. [74°].
N
Small yellow needles (from benzene).
Bromo-indazine C«H^r<^^>NH. [124°].
Obtained by heating bromo-indazine carboxylio
acid with a large quantity of water at 200°.
Colourless needles, si. sol. cold, m. sol. hot,
water.
Di-bromo-indazine CjHjBrjN,. [240°]. Ob-
tained by saturating the warm aqueous solution
of bromo-indazine with bromine. Formed also
by brominating indazine or indazine hydrochlor-
ide in aqueous solution, and by treating bromo-
indazine carboxylio acid with bromine-water.
Colourless needles, v. sol. alcohol, ether, and hot
aqueous NaOH. In alkaline solution it may ba
reduced to indazine by sodium-amalgam.
Bromo-indazine-carboxylio acid 0,EjBrN,0,
.CO^
i^. 0^,Br^ I ^NE . Formed by dissolving
bromo-indazyl-acetic acid in glacial HOAc, di-
luting somewhat, and boiling with gradual addi-
tion of chromic acid (Fischer a. Tafel, A. 227,
303). Small yellowish needles, v. sol. alkalis
and alkaline carbonates, almost insol. water and
HClAq.
Bef&rences. — EiaYL-, MEiBYL-aiHyi.-, and
ETBTIi-INnAZINE.
Iso-indazine. This term is given by Fischer
and Tafel to C^4<^^^^X^ some of the alkyl
derivatives of which have been prepared {v
ETHTL-l|'-IIIDAZni-AOETI0 ACID, Dl-HBIBIh-^-OI.
DAZINX, and METHYL-ETKni-l|'-Iln>AZIIIIS).
INSAZTIrACETXC ACID C^l^A t.<.
riHyCOaH
[170°]. Formed by
C.H.<;^<>NH
warming sodinm-v-sulpho-diazo-cinnamio acid
(which may be called diazo-cinnamio acid
sodium sulphite) C5H,(N:N.S0,Na).CH:CH.C0»H
with HOI (Fischer a. Tafel, A. 227, 303). Pre-
pared by aissolving o-hydrazido-cinnamio acid
CeH,(NH.NHJ.CH:OH.COaH in alkalis, and
shaking with air nntil it no longer reduces
Fehling's solution. The acid is then ppd. by
HCl.
Frc^erUes. — Slender, yellowish needles, v. e.
sol. alcohol, acetic acid, acetone, and hot water,
m. sol. ether, v. si. sol. chloroform, benzene, and
ligroin. Dissolves in alkalis and in mineral
acids. On distillation it is split np into CO,
and methyl-indazine. It is completely decom-
posed by oxidising agents.
Salt. — CaA'2 2aq : pale green slimy pp., in-
sol. hot water. Crystallises from hot iJcohol in
Blender green needles.
.<^>.N0
Nitrosamine CJi,
Formed by adding a 4 p.c. solution of sodium
nitrite to a very dllnte solution of indazyl-acetio
acid in aqueous H.SO, in the cold. Golden-
yellow needles. Insol. water and ligroin, v. e.
sol. ether, chloroform, alcohol, HOAc, alkalis,
and warm EtOAo. Beduced by zinc-dust and
HOAc to indazyl-acetic acid. It appears to exist
in two modifications, one of which decomposes
at 90° with evolution of gas, but without melting,
while the other, which is obtained by crystallisa-
tion from HOAc, melts at 123°.
Bromo-indazyl-acetio acid 0,H^rN,0, i4.
,CHj.CO^
4>'
Cfifii<r I >NH
[200°]. Formed by
adding bromine-water to a solution of indazyl-
acetio acid in dilate HClAq. Nearly aolonrless
needles (from HOAc), v. sol. alcohol and HOAo^
si. sol. hot water.
INDENE V. iKDONAFBTHEtn.
INDIGO.
768
OrsiA BTTBBEB «. OAouxaBOTia
IKDICAH V. Ihdigo.
INUUrULYIir ff. IxBiao.
INDITUSOIK V. Indioo.
INSIOIXrCIH V. Insiso.
IKDiaO 0„H,oNA probably
digotim. M. w. 262. y.D. 9-45 (foi 9*06) (Som-
maruga), A blue oolouiing mattei ocomring as
• oolourless glucoaide {Indican) in varioas species
of Indigqfera, i.e. Indigofera Aral, Indigofera
tmetoria, and in other plants, i.e. PoVygonma
tinetorvum, IsaHs Unctoria, &o. Commercial
indigo, obtained from the juice of the indigofera
by fermentation, forms coppery blue lamps, and
contains about 50 p.o. of pure indigo, together
withindiinbin,indifulTin, indirectin, indiglucin.
History. — ^Indigo was probably one of the
earliest baown colouring matters, for its employ-
ment dates back to the most ancient times. The
Egyptian mummy cases were certainly dyed with
indigo, and it has been employed in £idia for
many thousands of years (Gterardin, Jovm. de
Chiim. Med. 1838, 224). It was well known to the
Greeks and Bomans, who imported it from India,
and hence called it tvSiK6v or indicii/in, FUny
mentions it, and gives as a test for its genuine-
ness that it sho^d bum with a purple flame
when thrown on to glowing charcoal. In the
Middle Ages indigo was used for dyeing and paint-
ing, but only to a small extent, and so little was
known about it that it was generally believed to
be a mineral. From the commencement of the
sixteenth century the employment of indigo (from
Irtdigofera) for dyeing began to rapidly increase.
Prior to this time woad {Isatts tmetoria) was
grown in great quantities in various parts . of
Europe, especially in Thiiringen, and largely
employed for bine dyeing (called Persian blue).
The importation of indigo from India, which
from the sixteenth century rapidly increased, in
spite of much protective legislation soon re-
placed the woad indigo, until at the present time
woad is only used as an adjunct to the indigo
vat in order to start the fermentation. The pre-
sent annual production of indigo is estimated as
abont 8,200 tons (value 4,000,0002.) of which
6,100 tone are produced in India, 1,100 tons in
AJnerica, ^nd 1,000 tons in China and other
oonntries.
Mamufaetureofcommereialindigo. — 1. From
Indigofera. As carried out in Ibidia the pro-
cess is performed as follows : the cut plants
are first steeped in water, where they ferment
with evolution of CO,, the yellow liquor is then
run ofl into another vat, where it is vigorously
mixed with air by means of long stirrers. By
tlds means the lenoindigo (indigo-white) con-
tained in the solution is oxidised, and the indigo
separates out as a blue scum which finally settles
to tibe bottom. The supernatant liquor is then
ran away, and the indigo is boiled with water for
■everal hours, pressed, and dried. The forma-
tion of lenoindigo from the glucoside indican,
which 18 present in the plant, is effected by a
special baoiUus, which is strongly pathogenic
and closely resembles the bacilli of pneumonia
and rhinosclsroma (E. Alvarez, O. E. 105, 286).
Vol. n.
2. From woad. The leaves are crushed, the
mash is fermented, formed into balls and dried.
PreparaUon of pure indigo. — 1. From com-
mercial indigo: (a) Finely powdered indigo
(126 g.) and glucose (125 g.) are covered with
hot 75 p.o. spirit in a flask of 6 litres capacity.
After adding 200 g. of saturated alcoholic NaOH
the flask is filled up with hot spirit and left
to stand. The dear liquor is then decanted off
and left exposed to the air, when the leucindigo
(indigo- white) it contains is reoxidised to indigo-
blue, which separates in small glistening needles.
This is washed with alcohol, water, and finally
with HCl, and is then sublimed under 30-40 mm.
pressure (Fritzsche, A. 44, 290 ; Sommaruga, A.
195, 305). — (b) Boiling water (160 pts.) is poured
on a mixture of finely-powdered crude indigo
(1 pt.) and slacked Ume (2 pts.). Ferrous sul-
phate (1^ pts.) is then added, and the mixture
is kept warm for several hours with exclusion of
air. The alkaline solution of lenoindigo is run
into diluted HCl, by which it is precipitated, and
by exposure to air is oxidised to indigo. — (c) In
place of glucose or ferrous sulphate the reduc-
tion can be conveniently effected with alcohol
and sodium stannite (SnCl, and excess of NaOE)
(Schunok, Z. 1865, 671).
2. Synthetically : (a) Together with indi-
rubin by reduction of isatin chloride (from isatin
and PCI5) with ammonium sulphide or with HI or
zinc-dust andacetic acid. Theindirubinis removed
by extraction with alcohol (Baeyer, B. 11, 1297 ;
12, 456).— (6) Cinnamio acid CJH5.CH:CH.C0ijH
is converted into its ether by means of alcohol
and sulphuric acid. This is nitrated at a low tem-
perature with the theoretical quantity of HNO,
mixed with H^SO^. The product is a mixture of
about equal quantities of a and f -nitro-cinnamio
ethers CeH,(NOj)CH:CH.CO^t from which the
ortho- ether is separated by means of its greater
solubility in alcohol. The ortho- ether is then
converted into the acid by warming with cone.
H2SO4, dried and converted into the dibromide
C^4(N0j).CHBr.CHBr.C0jH [1:2] by treatment
with an equivalent quantity of bromine. By
leaving the dibromide in contact with cone.
NaOH the sodium salt of o-nitro-phenyl-propiolic
acid C^,(N02).C:C.C02H is formed from which
the free acid is precipitated by the addition of
EgSO,, and is filtered off and washed. The
o-nitro-phenyl-propiolio acid (2 pts.) suspended
in cold water (1 pt.) is neutralised with potas-
sium carbonate (1 pt.), and then carefully mixed
with potassium xanthate (3 pts.). On allowing
the mixture to dry at the ordinary temperature
indigo is slowly formed (Baeyer, B. 13, 2260 ;
E.P. 1880, 1177; G. 0. 1882,366). The o-nitro-
phenyl-propiolic acid can also be converted into
indigo by boiling its solution with glucose and
sodium carbonate (Baeyer) or with glucose and
potassium cyanide (Michael, J.pr.li] 36,254).
(e) By adding NaOH (3 pts.) dissolved in cold
water (130 pts.) to a solution of o-nitro-benzalde-
hyde (10 pts.) in acetone (16 pts.). The separa-
tion of the indigo is complete in two or three days.
A better yield is obtained by previously pre-
paring the aldol-like intermediate compound
Cja,^0,).CH(OH)CHj.CO.CH, by slowly drop-
ping a 1 p.e. solution of NaOH (about 6 pts.)
into a cold solution of o-nitro-benzaldehyde (2
pts.) in pure acetone (14 pts.) diluted with an
8G
764
INDIGO.
equal Tolnme of water. The NaOH solation'is
added until the mixture is slightly alkfiline and
a trace of indcgo begins to be formed ; the ace-
tone is then distilled off and the condensation
product is left. The latter is converted into indigo
by dissolving it without purification in about
250 pts. of boiling water, cooling, and adding
NaOH. The yield upon the o-nitro-benzalde-
hyde is 76 p.c. of the theoretical (Baeyer a.
Drewsen, B. 15, 2856 ; Eng. Pat 1882, 1266).
Syntheses. — 1. By warming isatin
C<|H,<'ij*^C(OH) with PC1„ phosphorus, and
some acetyl chloride at 70°-80° (Baejrer a. Bm-
merling, B. 3, 615). Isatin (j.v.) is formed
synthetically by oxidation of omido-oxindole
C;a,<°^j^^^)>CO (Baeyer, B. 11, 1228), by
reduction of o-nitro-phenyl-glyoxylio acid from
o-nitro-benzoic acid (Olaisen a. Shadwell, B. 12,
350), or by boiling a solution of o-nitro-phenyl-
propiolic acid with alkalis (Baeyer, B. 13, 2259).
2. Together with indirubin, by adding zinc-
dust or HI to an acetic acid solution of isatin
chloride CgH,^ >^ ^CCl, formed from isatin
and POls (Baeyer, B. 11, 1297 ; 12, 457).
3. By the action of ammonium sulphide upon
isatin chloride, upon ^'-isatoxim
C,H4<^^Q^C(N0H), or upon isatin ethyl ether
CA<*]?>e(OEt) (Baeyer, B. 15, 2093; 16,
2203).
4. By the action of air or Fed, upon indoxyl
C^,<[^jj2 '^OH, or upon indozyl-sulphurio
aoidO.H,<:;;°(°^jg»^)^CH (Banmann a. Tie-
mann, B. 12, 1098).
5. In small quantity by oxidation of indole
0,H4<^^^0H with ozone (Nenoki, B. 8, 727).
6. By the action of reducing agents such as
glucose, lactose, sulphides or xanthates upon
o-nitro-phenyl-propiolio acid in alkaline solution,
the yield being about 40 p.a. of the ' propiolic
acid ' :
O.H,(NO,)C50.CO^ -I- 2H,
•=0„H,„N20,+2CO,+2HjO (i>. supra; Baeyer,
B. 13, 2260).
7. In small quantity by heating o-nitro-
phenyl-oxyacrylic acid
OeH,(NOj).C(OH):0H.0OjH by itself, or with
phenol or acetic acid (Baeyer, B. 13, 2263).
8. Indoxyl C.H,<^^^)^CH, indoxyUo
acid 0,H,<*'^J^^O.COA or ethyl-indoxylio
acid C.H.<*^(^;^*)>G.CO^ readily give indigo
on oxidation with FeCl,, CuCl,, &o. or by atmo-
spheric oxidation of the alkaline solution. Indox-
ylic acid is obtained from its ethyl ether, which
is formed by the action of alkaline reducing agents
Q-Q
^0-C.COJSt
nponisatogenioethet 0,E4^ V • ^^•
oxyl is obtained by heating indoxylio acid
(Baeyer, B. 14, 1743; Germm Patent 17,656).
9. By wanning a mixture of indoxyl or ind-
oxylio acid with o-nitro-phenyl-propiglio aoid
and NafiO, (Baeyer, B. 14, 1743).
10. Diisatogen Q—Q O— Q
yG .0.6 . a.
o.hZ\/ \/>a^..
formed from the isomeric di-o-nitro-di-phenyl-di-
acetylene 08H,(N02).C:0.0:0.0;H4(N0J by treat-
mentwith fuming H^SO., is readily converted into
indigo by reduction with ammoniimi sulphide,
zino-dust and alkalis, glucose and alkalis, &o.
With ammonium sulphide in the cold the reduc-
tion takes place quantitatively. The dj-o-nitro-di-
phenyl-diaoetylene is obtained by oxidation with
potassium ferricyanide of the cuprous compound
of o-nitro-phenyl-acetylene CsH,(NOJ.C:CH
which is formed byboiling an aqueous solution of o-
nitro-phenyl-propiolic acid C,H,(NO^.OiO.CO^
(Baeyer a. Landsberg, B. IS, 53 ; O. P. 19,266).
11. By the action of dilute alkalis npon a
mixture of o-nitro-benzaldehyde C,H,(NO^CHO
with acetone, pyruvic acid, aldehyde, or aceto-
phenone. Acetone and pyruvic acid giva tiie
best yields. In these reactions aldol-hke con-
densation products are first formed and are con-
verted into indigo by the further action of tiie
alkali. Thus under the influence of a small
quantity of alkali, o-nitrobenzaldehyde with acet-
one gives o-nitro-)3-phenyl-i8-oxy-ethyl-methyl
ketone qja4(NO,).CH(OH).CH,.0O.CH, ; whilst
with aldehyde o-nitro-ben2oic aldehyde appears to
form o-nitro-j3-phenyl-3-oxy-propionic aldehyde
C„H,(NOs).CH(OH).CHj.CH0, with pyruvic acid
o-nitro-/3-phenyl-i8-oxy-propionyI-formio aoid
CeH,(N0,).CH(6H).CHrC0.CPjH. By treat-
ment with a further quantity of an alkali all
these condensation products yield indigo,
whilst acetic, formic, or oxalic acid is split oS,
thus : 2C^,(N0s).0H(0H).CH,.C0.CH, -H 2HjO
= C,,H,„NjOs-f2CH,.COjH + 2H,0 (Baeyer a.
Drewsen, B. 15, 2856 ; S. P. 1882, 1266).
12. By the action of aqueous alkalis npon
o-nitro-cinnamoyl-formio acid (o-nitro-styryl-
glyoxylio acid) C^4(K0^.GH:CH.C0.G0^, ob-
tained by saturating a mixture of o-nitro-benz-
aldehyde and pyruvic acid with gaseous hydrio
chloride at 10°: 2G,H4(NO,).OH:CH.GO.GO^ =
G,eH„N,0,+2CH,.C0aH (Baeyer a. Drewsen,
B. 15, 2862).
13. o-Nitro-benzylidene-acetone
C,H4(|T0,).GH:GH.G0.CE:, which is obtained
by nitration of benzylidene-acetone, or by heat-
ing o-nitro-/3-phenyl-j3-ozy-ethyl methyl ketone
G^«(KOJ.0H(OH).CH2.CO.CH, with acetic an-
hydride, gives mdigo by treatment with alcoholic
EOH, precipitating with an aoid, and then boil-
ing with water or aqueous alkalis. The yield
is small (Meister, Iiucius, a. Brnning, E. P. 1882,
1453; Baeyer a. Drewsen, B. 16, 2858).
14. By heating the lactone of o-nitrq-/S-phenyl-
/3-oxy-propionic acid with water or acetic aoid
(Einhom, B. 16, 2212).
15. Bybrominationorohlorinationof »cetyl-
o-amido-acetophenone C,H4(NBAo).CO.GH„ or
of acetyl-o-amido-phenyl-acetylene
GgH4(NHAc).G=0H, esorbromo- and ehloro-
derivatives are obtained. These are converted
by cono. HgSO, (10 to 20 pts.) into intermediate
products, which give indigo on dissolving in
aqueous ^D^alip mi exposuf? ^ %v. Indoxyl
INDIGb.
76d
11 pix>babl7 an intermediate prodaot in this re-
action (Baeyer a. Bloem, B. 17, 963 ; German
Patent 21,592).
16. By the action of ammonium salphide
' npon the eso-mono- or di-ohloro- (or bromo-) nitro-
acetophenone (e.?. CHiPSfO J.CO.CHCy, formed
by oUorination or bromination of o-uitro-aceto-
phenone (Oevekoht, B. 15, 2084 ; A. 221, 331;
Q. P. 23,786).
17. By heating indoin OiAiN^O,.
Formation, — In addition to the above syn-
thetical methods indigo is produced: 1. From its
glucoside indioan by the action of acids and air,
by Fed,, or by fermentation under the influence
of a special microbe (Schunck, J. 1855, 660;
18S7, 564 ; 1858, 465 ; C. N. 37, 223 ; 39, 129 ;
Schunck a. Bomer, B. 12, 2311).— 2. The potas-
sium salt of indozyl sulphuric acid, incorrectly
called ' Indican,' is a normal constituent of the
urine of animals, being formed in the organism
by the oxidation of indole C^4<^|K>CH,
which is a decomposition product of proteids.
Indoxyl-snlphurio acid is readily oxidised to
indigo by FeCl,, &e., and under certain condi-
tions ia conyerted into indigo in the urine
(Schunck a. Eoppe-Seyler, Arch. Pathol. Anat.
27, 388 ; B&umann, Pf. 13, 291 ; Baumann a.
Brieger, H. 3, 254; JaffS, Pf. 3, 448 ; Baumann
a. Tiemann, B. 12, 1098, 1192; 13,408 ; Michai-
low, B. 20, 605 ; J. B. 1887, 326 ; Weber, B. 12,
271 ; Baeyer, B. 12, 1600).— 3. By oxidation of
leucindigo (indigo-white) by air, &e. This re-
action performed npon the fibre forms the usual
method of dyeing indigo.
Property. — Pure indigo begins to sublime
at 170° (Schunck, G. J. 37, 617), forming a
purple-red vapour and condensing to dichroio
plates belonging to the rhombic system, aib:e
= •7883:1: -7265, 0 = 76° 30', ^ = 108°. Under
60-80 mm. pressure it sublimes without any
decomposition, and the vapour density has been
taken under these conditions by Sommaruga
(A. 195, 312), and found to correspond to the
formula G^HioN^Oj. Insol. water, alcohol, ether ;
dilute acids or alkalis. V. si. sol. hot alcohol,
amyl alcohol, acetone, or turpentine. SI. soL
chloroform or acetic acid. Y. sol. hot aniline,
nitrobenzene, or phenol; from the latter sol-
vents it crystallises on cooling (Stokvis, J. 1868,
789 ; Wartha, B. 4, 334 ; Jacobsen a. Mehu, J.
1872, 682). Sol. cone. E^SO, without alteration
to a yellowish-green solution, which exhibits a
characteristic absorption spectrum between the
D and d lifles (Vogel, B. 11, 1364). The E^SO,
solution by long standing or on warming becomes
blue from formation of indigo-sulphonic acids.
Beactions. — 1. Distilled with EdE it yields
aniUne (Fritzsche, A. 39, 76).
2. It dissolves in boiUng aqueous EOE (S.0.
1*45) to a yellow solution of isatic acid and
leucindigo (indigo-white): 3C„E,|,NjO,-h4EjO
- 2C,E,N0, + 20„B,jN A-
3. By fusion with EOE anthranilic acid
C.E<(NBj)0OjE [1:2] is formed (BSttinger, B.
10, 269) ; by heating with EOE at 300° CahOurs
(A. Oh. [3] 13, 113) obtained salicylic acid.
4. By b6i£ing with EOH and MnOj it yields
anthraniWo and formic acids (Bottinger).
6. Oxidising agents, such as chlorine, oxides
of chlorine. HNO„ ferric saltSi Ac, convert it
into isatin CjE^^I^g^OO.
6. By damp chlorine it is converted into
chlorisatin, dichlorisatin, trichloraniline, and
trichlorophenol. Bromine acts in the same way
(Krdmann, Jf.pr. l9, 330).
7. With ENO, it yields in succession isatin,
nitrosalicylio acid, and finally picric acid.
8. Alkaline reducing agents, such as FeSOt
and XaOE, glucose andNaOE, SnCl, and NaOE,
convert it into leucindigo (indigo-white)
C.6E„NA-
9. By heating with aqueous sodium hydro-
sulphite Na^SO, and excess of NaOE at 180°,
indoline 0,E^<^^-°^;^g>O.E.is formed (Gi-
raud, B. 12, 2155). This body is also obtained
by heating leucindigo (indigo-white) with zinc-
dust and aqueous barium hydrate at 180°.
10. By heating with an excess of saturated
EI, hydrocarbons and NE, are produced (Ber-
thelot, Bl. [2] 9, 189).
11. Unaltered by long boiling with cono.
aqueous NE, (Liiibawin, J. B. 15, 17).
12. By digestion of indigo with cone. E^SO,
or with slightly fuming E^SO, a mono-sulphouio
acid OigEgXAiSOjE) (phoenicine-sulphuric
acid) and a di-sulphonic acid C,sE,N,02(^0,E),
(sulphindigotic acid) are formed.
13. By reduction to leucindigo (indigo-white)
and distillation with zinc-dust it gives a mixture
of indole CiE4<^^g^CE and scatole
C„E,<;^^^^CB (Baeyer, B. 13, 2339).
Detection of indigo on fabrics.
(W. Lenz, Fr. 26, 535; Prior, iJep. d. Anal.
Chem. 13, 193, 1884.)
1. A drop of nitric acid gives a bright-yellow
spot.
2. When indigo alone is present the following
reactions should be given : alcohol extracts no
colour even on gentle warming. Cold saturated
oxalic acid and borax solutions, 10 p.c. alum so-
lution, and 33 p.c. ammonium molybdate solution,
removes no colour even on boilidg. Stannous and
ferric chloride destroy the colour on warming.
Glacial acetic acid dissolves all the colour on re-
peated boiling, and after mixing the solution with
ether and water the aqueous layer is colourless and
not coloured by strong hydrochloric acid. When
the indigo may be accompanied by other colours
the following methods of testing may be adopted.
3. The stuff is warmed with an acidified 10
p.c. solution of SnCl,. Prussian blue remains
unchanged. Indigo (vat-blue)^ indigo-carmine,
and aniline-blue (tri-phenyl-rosanUine-tri-sul-
phonate) are completely removed from the'fibre,
and yield pale-yeUow solutions. Logwood is also
removed, but gives a rose-red solution. On add-
ing a large excess of hydrogen peroxide to these
solutions the rose-red of logwood is destroyed,
anUine-blue gives a blue solution, whilst indigo
is not regenerated.
4. Glacial acetic aCid dissolves indigo from a
fabric. In presence of logwood the cold acid ac-
quires a rose-red colour, which on heating passes
into yellowish-red, and is soon obscured by the
dissolving indigo. Prussian blue and indigo.
8c?
768
INDIQO.
(unnine are not dissolved. On mixing the acetic
acid Bolufion with' ether, and then adding water
nntil the ether separates, the indigo ia removed
from the aqueous layer, which then in the pre-
sence ot logwood shows a feeble reddish-yellow
tint. If now a few drops of cone. ECl are added,
the smallest trace of logwood it revealed by the
Production of a rich ted colon]' in the aqueous
lyer. Aniline-blue obBOures this reaction.
EsUTnatUm. — In fabrics: l^he dyed stuff
(10 g.) is treated in a flask with 200 o.o. of a so-
lution made by adding 2 litres of water and 100
O.C. of milk of lime to 100 o.c. of a solution of
NasSO, prepared from a solution of sodium bi-
sulphite of 35° B. The mixture is heated at
60°-70°, a stream of coal gas being passed
through the flask during the reduction. When
all the colour has disappeared, a portion of the
solution is decanted, cooled, its volume measured,
the indigo precipitated by HCl, and after 12
hours' standing collected on a filter, washed, and
dried. It is then dissolved with the filter-paper
in about 10 c.c. of fuming H2SO4, and the solu-
tion titrated by the hydrosulphite (Miiller's)
method {v. infra) (Benard, Bl. 47, 41).
In commercial indigo : 1. The indigo is
reduced to leucindigo (indigo-white) by glucose
and NaOH in an aqueous alcoholic solution ; the
clear solution is separated from the insoluble
impurities, and by oxidation with a stream of
air the indigo is precipitated and weighed (Bau,
Am. C. J. 7, 16; Manley, Chem. Centr. 1887,
605; Somen's Journal, 1887, 16). This gives
the value in indigo-blue only, as the indirubin
remains in the alcoholic solution (Bawson,
8. C. 1. 1886, 491).
2. By reduction with FeSOt and NaOH and
subsequent oxidation (Graoe-Calvert).
3. By reduction with sodium hydrosulphite
Na^SO, and subsequent oxidation by air. The
finely powdered indigo (1 g.) is made into a paste
with water and placed in a flask with 600-600
e.c. of lime water ; the flask is closed with an
indiarubber stopper bored with four holes, one
carrying a syphon, another a tap-funnel, the re-
maining two serve for the entrance and exit of a
current of coal gas. The whole is heated at 80°,
and 100-150 c.c. of sodium hydrosulphite (equi-
valent to an ammoniacal copper solution con-
taining 19'04 g. of CUSO4 6aq per Utre) is intro-
duced and kept near the boiling-point for half
an hour. After allowing to settle 500 c.c. of the
clear liquid are siphoned off, oxidised by aspi-
rating air through it for 2.0 mins., an excess of
EGl added, and the precipitate of indigo and
indirubin washed and weighed. The liquid re-
maining in the flask is measured, and from it is
oalcnlated the combined percentages of indigo
and indirubin. If the proportion of indirubin is
required the filter and precipitate are extracted
with alcohol, which dissolves the indirubin.
This method gives very good results (Bawson,
C. N. 67, 7, 19, 29, 34 ; 8. C. 1. 1885, 489).
4. The indigo is sulphonated and the solution
it reduced by a solution of sodium hydrosulphite
of known strength, the excess of which is then
estimated by titration with ammoniacal CuSO^
(Miiller, J. 1874, 1019; Am. Chemist, 6, 128;
Bemthsen a. Drews, B. 13, 2283 ; Bawson, S. C. I.
1885, 490).
5. By sulphouation and subsequent oxidation
of the sulphonic acid by means of potassium fer-
rioyanide (Allgren), chlorine-water (Bolley),
KjCr,0, and H^SO, (Penny), or EMnO, (Mohil.
The finely.powdered indigo (1 g.) is mixed with
an equal weight of ground glass, and gradually
added to 20 co. of HsSO^ (S.G. 1-846) ; it is then
placed for 1 hour in a steam-bath at 90°. The
sulphuric acid solution is diluted to 1 litre, and
50 CO. of the filtered solution is mixed with 60
c.c. of water and 32 g. of NaCl. Sodium snlph-
indigotate being almost insoluble in strong salt
solution separates, and after two hours is col-
lected, washed with salt solution (S.0. 1-2), dis-
solved in hot water, and when cool acidified with
1 c.c. of E2SO4, then diluted to 300 c.c, and ti-
trated with KMnO, ('6 g. per litre). A small cor-
rection ( + 1-6 p.c) has to be made for the sulph-
indigotate which remains in the salt solution ;
the result gives the combined percentages of in-
digo and indirubin (Bawson, 8. C. 1. 1885, 489).
6. By loss of weight on sublimation (Lee,
Am. C. J. 6, 186). According to Bawson (I.c.)
this method is not accurate, since the other com-
pounds present in the crude indigo affect the re-
sult ; with inferior qualities the result is often
too high, whilst in superior qualities it is too
low.
7. By spectrum analysis : ■6g. of the sample
is sulphonated and diluted to a litre. This so-
lution is then further diluted according to its
depth of colour, and is examined spectroscopically
in a layer of 1 c.c thickness. The coefficient of
extinction is direotiy proportional to the per-
centage of pure indigo present (Vierordt ; Wolff,
Fr. 17, 310 ; 23, 29 ; D. P. J. 253, 256).
8. By Bulphonation and quantitative dyeing
on wool or silk (Chevreul).
Dyeing methods. — ^Indigo-blue is used for
dyeing silk, wool, and cotton, to which it is ap-
plied by the following methods :
1. By vat-dyeing, ix. reduction of the indigo
to leucindigo (indigo-white) by means of some
reducing agent, steeping the material in the
colourless solution and &ially exposing it to the
air, by which the leucindigo is oxidised to indigo,
which being insoluble remains firmly fixed in the
fibre. This is the best method of indigo dyeing,
and gives the fastest colours. Various reducing
agents are employed to effect the reduction, and
of these different 'vats' the following are the
most important :
Cold vats (used chiefly for cotton): a. Blue
vat, composed of indigo (2 pts.), ferrous sulphate
'3 to 4 pts.), slaked Ume (3 to 5 pts.), and water
200 pts.). h. ^inc-dttsfvaf, composed of indigo
'2 pts.), zinc-dust (1 pt.), slaked Ume (1 pt.),
and water (200 pts.). e. HydrosulpMit vat,
composed of indigo (1 pt.), 20 p.c. of lime-milk
(1 to 1-3 pts.), and the sodium hydrosulphite
solution (NajSO,), obtained by reducing 8-10
kilos of sodium bisulphite solution (S.G. 1-275)
with zinc-dust or zinc foil, the whole being sub-
sequently diluted with water, d. Tin salt vat
(SnClj and an alkali) is only used for printing.
e. Arsenic vat (As^O, and an alkali) is only used
for printing (SnjZisfcPafent 1884, 421; 8.0.1.
1885, 63). /. 8tigwr vat (glucose and an alkali).
Warm or fermentation vats (only used
lor wool and silk) ; a. Wood vat, composed oi
INDIOO.
767
indigo (16 ptB.), woad (800 pti.), bran (10 pta.),
madder (2 to 15 pta.), slaked lime (12 ptg.), and
water (4,000 ptsl). The liquid is iJlowedto
ferment for aboat two days, keeping the tempera-
ture at 45°-60<*, and the vat ia uien ready for
nae. b. Potash vat, composed of indigo (10 pta.),
madder (2 to 6 pta.), bran (2 to 6 pta.), and
E^GO, (10 to 15 pts.), and water (4,000 pta.), the
whole being left to ferment for two daya. e. Soda
vat, oompoaed of indigo (10 pta.), bran (60 to
100 pta.), or treacle (10 to 15 pta.), aoda oiyatala
(NojCO, lOaq) (20 pta.), alaked lime (6 pta.), and
water (4,000 pta.), fermented for two or three
daya. For otiier methoda of preparing vats v.
Ooppelardder, D. P. J. 261, 465; 263, 245, 381;
C. S. I. 1884, 618; Oollin a. Benoist, Qermcm
Patent 30,449 ; S. C. 1. 1886, 493 ; Bohmuckert,
EngUth Patent 1887, 7,333.
Indigo ia also applied to fabrioa :
2. By printing with a paste of reduced indigo
and developing the indigo by exposure to air.
3. By printing with a paste of sodium o-
nitro-phenyl-propiolato, aodium or zinc xanthate,
borax, and a thickening agent, the colour being
slowly developed by leaving the material at the
ordinary temperature for two days (Bad. Anil.
n. Soda-Fabrik, E. P. 1881, 466 ; S. C. I. 1882,
148, 360 ; 1885, 454). The blue obtained in thia
way anrpaaaes in purity of shade that obtained
witii natural indigo, and also haa the advantage
that it can be readily employed in conjnnotion
with other steam colonra, alizarin, &c.; its
high price, however, haa hitherto prevented ita
extended application.
4. By dyeing from a bath of indigo-di-
snlphonic acid (' aulphindigotic acid,' 'indigo-
carmine,' or 'indigo-extract '). This method ia
only employed for wool and silk, as the aulph-
indigotic acid haa no afSnity for cotton. The
colour obtained by thia method, called ' Saxony
blue,' ^though much brighter than ' vat-blue '
is not nearly ao fast either to soap or light.
Constitution. — The determination of the oon-
•titution of indigo is mostly due to A. Baeyer
and his pupils. The molecular formula
Ct^tJSfii was established by the vapour density
determinations of Sommamga. Isatin CgH^NOj,
which is obtained from indigo by oxidation, gives
on treatment with reducing agents dioxindole
CgH^Oj, oxindole CgHjNO, and finally indole
C,H,K(Baeyera.Enop,i4.140, 1,295). From this
Baeyer concluded at that time that indole was
the parent substance of the dye-stuS, and repre-
sented the latter by the formula cH*C^}*^»-
Soon afterwards Strecker proposed for indigo the
formula
OJB..<{ ScO~00?' \ifit. In 1869 Ke-
knl6 (B. 2, 748) had aaaigned to isatin and isatio
acid the formulas Ofit^-^^^00 and
0^4<^S~ *^, thus explaining their ready
conversion into o-amido-benzoic acid and sali-
eylic acid, and this view was subaequently con-
&ined by the inveatigationa of Baeyer a. Suida
(B. 11, 582, 1228) and of Claisen a. Shadwell
{B. 12, 360). At the aame time it was proved
that dioxindole and oxindole were respectively
the inner anhydrides of o-amido-mandelio acid
and of o-amido-phenyl-aoetic . acid, and hence
were constituted thua: 0fi^<;^^^y0O
(dM»MKtoZe),C^4<^^^>C0 (oxindole). In 1870
Baeyer a. Emmerling (B. 8, 617) aaaigned to
indole the formula OjH«<^^OH[l:2]. In the
same year Emmerling a. Engler {B. 3, 885 ; cf.
B, 9, 1106, 1422) obtained small quantities of
indigo by diatUlingnitro-acetophenonewith zinc-
dust and aoda-lime, from which they concluded
that it was an azo- compound, and represented
it by the formula Cfi,<(^^^^^;^C,n„
leuoindigo being the corresponding hydrazo-
compound 0^.<^^^^^C.H,. In
1878 Sommamga (A. 194, 107) propoaed the
p O
formula 0^i<^^^^'>Ofit ; in 1879
Baumann a. Tiemann suggested that indigo
might be a derivative of diphenyl :
HC/ \h,0..6.H,/ ScH;whilatinl882
Iijubavin (B. 16, 248, 728), regarding indigo as a
Bubatitution product of indoUne CisHj^N,, pro-
>0:O.HNv
posed for it the formula : OfiX^'^ yCKy^t^f
\nH.C:0^
Baeyer'a aynthesea of indigo in 1882 from
indoxyl and diisatogen (B. 15, 54) led him to
conclude that it had the constitution
y°\° — 0/°\
C^i'v' l/>CH.HC^| ^C,H4, but hia subse-
quent researches (B. 16, 2200 ; 17, 976) caused
him to modify this formula to
O.H<<^^>0:0<;^!^>C,H„ representing it aa
the indogenide of i^-isatin or diindogen. The
latter formula which is now tolerably well esta-
blished is based upon the following considera-
tions: i. Indigo contains an NH group, ii.
The carbon atoms are arranged in a line
GsHj.C.C.C.C.CgHj, as follows from its formation
from di-phenyl-diacetylene. iii. It can only be
obtained from compounds in which the carbon
atom directly united to the benzene nucleus is
also united to O, or capable of becoming so
united, iv. Its formation and properties indi-
cate a close relationship to the jB-indogenide of
ethyl-if'-isatin Oja4<<^g>0:C<;(3°^ >NEt,and
to indirubine, which is proved to be the iS-indo-
genide of .^-isatin Ofit<^^yO:0<^^^ >NH.
The two latter bodies are formed by direct con-
densation of indoxyl OJSit<^^^^'^CE yiitix
ethyl-if'-isatin O^i^j^g^CO, or with isatin
CO
0^4'^ jT ^C(OH), in which reactions the ind-
oxyl is probably first transformed into ilf-indoxyl
0,H,<^^g[^OH„ and the iaatin into ili-isatin
768
INDIGO.
CA'^nQ^OO. Oombination then takes plaoe
between the a-carbon atom of the ^'-indo^I and
the iS-carhon atom of the i|i-iBatiii, thus :
-OA<OT>°'^O^P>^^- Indigo is con-
seqaently the isomeric a-indogenide of ^-isatin,
though it oannot be formed from isatin and
indozyl owing to the greater tendency to reaction
of the jS-CO group.
SubsUtuHon products. Indigo-mono-snl-
phonic acid Ci^NfiJ^SO^). Phcenicine-sul-
phwric cusid. Formed by allowing to stand for
some time a mixture of indigo (1 pt.) with or-
dinary sulphuric acid (20 pis.), and separates
as a bine powder on pouring the solution into
water. It is easily soluble in alcohol, and in
water free from acid, forming blue solutions.
Its s<s are sparingly soluble in water. In the
dry state they are red, in solution blue. — A'Kaq :
purple pp. (Crum, Betg. J. 4, 189 ; Berzehus,
Berg. J. 4. 190 ; 7, 262 ; Dumas, A. 48, 340 ;
Haeffely, dm. 6, 462).
>~ Indigo-di-sulphonie acid 0„H,N202(S0,H)2.
SulpMndigoHe acid. Ocerulmisulphuric acid.
Indigo-exbract. Prepared by heating indigo with
16-20 pts. of ordinary, or better with 7-8 pts. of
fuming, sulphuric acid. Amorphous blue solid.
V. sol. water and alcohol. Completely removed
from solution by wool or charcoal. The aqueous
solution gives a continuous absorption spectrum
(Vogel, B. ll, 136S). By oxidising agents it is
converted into isatin sulphonic acid, byreducing
agents into lencindigo-sulphonic acid. Its salts
are mostly sparingly sol. water. The sodiiut
salt (A'lTa:) appears in commerce under the
name of vndigo-canmtie or sohMe-indigo and is
used for dyeing the so-called ' Saxony-blue '
upon silk and wool. — U'^^i amorphous blue
coppery powder; S. (at 15°) = -7. — ^A''Ba: m. sol.
hot water (Crum, Berg. J. 4, 190 ; Berzelius,
Berg. J. 7, 262 ; Dumas, A. 22, 72 ; Joss, Berg.
J. 14, 316). According to Berzelius (Qm. 6,
485) there is formed, together with the di-sul-
phonic acid, another acid, the so-called 'indigo-
hyposulphaaic aeid,' which difiers from the di-
sulphonio acid in its ammonium salt being
soluble in alcohol.
Indigo-di-carbozylic acid CigHigNjOs t.e.
O.H,(00,H)<gO>C:C<00>O.H,(CO,H).
Prepared by warming nitro-benzaldehyde-car-
boxyUo acid C,H,(CHO)(NOs,)COjH[l:2:4] with
acetone and dilute NaOH. Also by reduction
of o-nitro-phenyl-propiolic-carboxylic acid
CjHs(NOj)(COjH).C:C.COjH with glucose and
NaOH. Coppery blue powder. £isol. water,
alcohol, ether, and chloroform. Dissolves in
H,SO« with a deep-blue colour, in alkalis with
a blnish-green colour.— A"Ba.—0,8H^20jAg, :
insoluble.— A"Et2 : sublimes in prismatic tables,
si. BoL chloroform and benzene, nearly insol.
alcohol and ether (Ii5w, B. 18, 950 ; A. 231,
865).
Si-ohloro-indigo CHjCljNjO. Obtained by
the action of acetone and NaOH upon chloro-o-
nitro-benzaldebyde (Miiller, Qerman Patents
30,329 and 33,064).
Xetra-ohloro-indigo 0„H,Cl,Nj,0, ia
by the action of acetone and NaOH upon di-
chloro-o-nitro-benzaldehyde [188°] (Bad. AniL
n. Soda-Fabrik, G'. P. 32,288). Besembles indigo.
Sublimes in violet-red vapours, condensing to
bine coppery needles. Does not snlphonate or
form a ' vat ' so readily as ordinary indigo (Gnebm,
B. 17, 753).
Si-bromo-indigo G,fifitJSJO, i.e.
C ABr<^g>C:0<;°° >C.H,Br. Formed by
adding bromo-isatin chloride (from bromo-isatin
and POl,) to an excess of an 8 p.c. solution of
HI in acetic acid (Baeyer, B. 12, 1315). Also
obtained by boiling the acetyl derivative of tri-
bromo - o - amido - acetophenone with Na^CO,
(Baeyer a. Bloem, B. 17, 968). Soluble in phenol,
from which it separates on adding alcohol in
small black needles. Nearly insol. alcohol, ether,
acetic acid, or chloroform. Dissolves in cone.
HjSO, with a green colour. Sublimes in putpla
vapours. Forms a ' vat ' like indigo. The ab-
sorption spectrum is the same as that of indigo.
Si-nitro-indigo C„H5(NOs)2NjOj i.«.
C.H,(NO,) <^° >C:0<^>OA(NOJ.
Formed by adding nitro-isatin chloride (from
nitro-isatin and PCI5) to a solution of HI in
acetic aeid. Dark-red powder. Nearly insol.
alcohol, ether, acetic acid, and chloroform; v.
sol. phenol and hot nitrobenzene. The absorption
spectrum is analogous to that ef indigo. Dis-
solves in cone. HjSO, with a violet-blue colour
(Baeyer, B. 12, 1315).
Si-ai&ido-indigo C,aH,NA(NH2), tA
d^(NH,)<^^>0:C<0°>CA(NH.).
Formed by reduction of the foregoing nitro- com-
pound with zinc-dust and acetic acid. Dark-blue
pp. Nearly insol. alcohol, ether, and chloro-
form; V. e. sol. acetic acid with a pure blue
colour. Its absorption spectrum is like that of
indigo. It dissolves in dilute acids with a blue
colour. It forms a ' vat ' like indigo.
Di-benzoyl-indigo Cj^uNjO, ».«.
°«MnBz>°'°<^NBz>°«S. [108°]. Formed
by heating indigo with BzCl. Brown amorphous
pOwder. Insol. water and acetic acid, si. sol.
alcohol, m. sol. ether (Schwartz, J. 1868, 637).
Si-methyl-indigo CigH^Me^NgO, i.e.
C.H,Me<^°>C:C<°°>C.H,Me. Formed by
the action of acetone and NaOH upon o-nitro-to-
luic aldehyde. Blue coppery powder. Sol. alcohol.
Besembles ordinary indigo (Meister, Lucius a.
Briining, 0. P. 21,683 ;£. P. 1882, 3,2l6).
v-Di-ethyl-indigo C^gH^NsO, i.e.
C.H«<NBt>°=0<mN>0«=*- P^^eP^^dbyre.
ducing the di-ethyl derivative of ^-isatine-u-
oxim C,H,<;^g^O(NOEt) with alcoholic am-
monium sulphide, and then passing a stream of
CO2 through the solution. Blue felted needles ;
v. sol. alcohol, forming a deep-blue solution, the
spectrum of which closely resembles that of in-
digo. Less soluble in ether, acetone, CHOI,, OS,!
and aniline. It sublimes as a purple vapour,
INDIGO.
760
Mndenging to blue prisms. It dissolves in cono.
H2SO4 with a greenish-blue colour, and on heat-
ing is Bulphonated. With zino-dust and alkalis
it gives a vat. On oxidation it gives ethyl'^'-
isatin (Baeyer, B. 16, 2201).
Di-isopropyl-indigo O^HjsN^O, i.«.
0A5r<^^>C:0<§°>C,H.5r. Formed by
the action of acetone and NaOH npon o-nitro-
cuminio aldehyde CBHaPr{NOs)OHO [4:2:1] (Ein-
hom a. Hess, B. 17, 2019). Also in small quan-
tity from the dibromide of o-nitro-cumyl-acrylic
acid 0,Hj?r(NOj).CHBr.CHBr.OOjH by heating
with dilute KaOH and then adding glucose
(Widman, B. 19, 261). Blue crystals with cop-
pery lustre. Sol. alcohol, chloroform, and ether,
insol. water. Shows the indigo spectrum. Sub-
limes in red vapours. Gives a ' vat.' dissolves
in cold cono. E2SO4 with a brown colour which
on heating becomes green and finally blue.
Tetra - methozy • indigo - di - carbozylic acid
0^(OMe),(00^)<g^>OK3<^>O.H(OMe).(CO^).
Obtained by the action of dilute aqueous NaOH
and acetone upon nitro-opianic acid. Bluish-
green soUd. Sol. phenol and aniline with a
green colour, insol. alcohol, benzene, chloroform,
and acetone. Dissolves in hot dilute KH, with
a blue colour, the solution showing the absorp-
tion spectrum of indigo-di-sulphonic acid. The
solution of the NH^ salt is precipitated by salts
of Ga or Ba. It dissolves unaltered in cono.
H2SO4 with a violet-blue colour. On heating it
evolves violet vapours and a smell of vanUlin
(Liebermann, B. 19, 352).
Allied compounds.
Iiencindigo 0„H,,N20, m.
cA<^g5i?-°-^^i>CA (7).
Indigo-wMte. Formed by reduction of in-
digo by means of alkaline reducing agents such
as FeSOf and lime, orpiment and NaOH, glu-
cose and NaOH, sodium hydrosnlphide, &o. In-
digo (^ kUo.) is allowed to stand for one or two
days with a mixture of lime and FeSO, in a
closed vessel of 100 litres' capacity, filled with
water. The clear liquor is then siphoned off into
another vessel, filled with CO,, and HCl is added.
The ppd. leucindigo is then dried in a stream of
CO, or H (Dumas, A. 48, 257 ; Ullgren, A. 136,
96). Oreyish-white silky solid. Sol. alcohol and
ewer, insoL water. Dissolves in alkalis and be-
haves like a weak acid. By exposure to air it
is quickly oxidised to indigo. By heating with
zinc-dust and aqueous Ba(0H)2 at 180° it yields
indoline. On distilling with zinc-dust it gives
indole and acatole (Baeyer, B. 15, 54).
Iiencindigo-snlphuric acid. Indigo-white-
sulphwric acid. The potassium salt is obtained
by shaking damp pressed leucindigo (25 g.) dis-
solved in 25g. of aqueous E0H(1:2) with 12-15 g.
of EgSgO,. The solution is diluted with an
eqaal bulk of water, exposed to the air, filtered
from indigo, shaken with ether, and freed from
potasBinI^ snlphate by mixing with six times its
volume of absolute alcohol (Baeyer, B. 12,
1600; Baumann a. Tiemann, B. 13, 411). By
the action of air or FeCl, it is oxidised to indigo.
The solution of tiie E salt is resolved by dilute
adds into leucindigo and H2SO4. This com-
pound was regarded by Baeyer as identical
with ' indoxyl-Bulphurio acid,' but according to
Baumann and Tiemann this is not the case.
Indican C2sH„N0„(?). Plant imdican.
Olucoaide of mdigo or teucmdigp. Occurs in
the Indigofera, in Isatis tmctoria (woad). Poly-
gotwwm imetorimn, Bletta tcmkervillicBtGallanthi
verairifoUa, and other plants (Schunck, J. 1885,
659 ; 1858, 465 ; C. N. 37, 223). Prepared by
extracting dried and powdered woad leaves with
cold alcohol. The extract treated with a little
water is evaporated at the ordinary temperature
of the air, the aqueous residue shaken with OuO,,
filtered, freed from copper by H,S, filtered, and
again evaporated in the cold. The syrup is
taken up with alcohol, precipitated with twice
its volume of ether, and the filtrate evaporated
at the ordinary temperature. Light-brown
syrup. Slightly bitter taste. SoL water and
alcohol. In alcoholic solution it gives a yellow
pp. with lead acetate. Boiled with EOH it
evolves KE,. By long boiling with water it is
decomposed. It is decomposed by baryta water
in the cold with formation of a syrupy body
called mdicanine Cg,H„K0|2 (?)• By heating
with dilute acids it is resolved into indigo and
indighioin (a sugar). Simultaneouslyare formed
imdmtbm C,^,gN,02, indiretin C,,H„NOs
(dark-brown resin, sol. alcohol), indifulvin
(reddish-yellow resin, insol. alkalis), indiJiMmin
C,,HgHO, (brown powder, insol. water and al-
cohol, sol. alkalis), indifuscin G^JBl^^O, (ana-
logous to inhnmin), acetic acid, formic acid,
and CO2 (Schunck a. Bomer, B. 12, 2311; C. N.
39, 119). When fresh indican solution is mixed
with strong acid and boiled, only indigo and
indiglucin are obtained, but if the indican solu-
tion is previously boiled for a short time indi-
rubin is also formed (Schunck, C. J. 35, 528).
The name 'indican' has also been erro-
neously given to indoxyl-sulphurio acid which
is a normal constituent of the urine of animals
(Baumann a. Tiemann, B. 12, 1098 ; 13, 411).
Indirnbin CnHigN^O, i.e.
C^<N^O=0<VnH or
Indigo-red. ^-Isatine-a-indogemde. formed
together with indigo when a solution of indican,
previously boiled for a short time, is treated
with an acid. Also together with indigo by the
action of zinc-dust and acetic acid upon isatin
chloride. Obtained synthetically by condensa-
tion of isatin and indoxyl: — ^An indoxyl solu-
tion prepared by boiling 1 pt. of indoxylio acid
in 100 pts. of water for a short time is filtered
into a solution of | pt. of isatin in 200 pts. of
boiling water. Na^CO, is added and the precipit-
ated indirubin is filtered o£E and washed. Needles.
Sol. alcohol, ether, benzene, and acetic acid form-
ing purple solutions; insol. water. Begins to
sublime at 140°, condensing in fine reddish
needles (Schunck, C. J. 37, 617). Oives an ab-
sorption spectrum which is different from that of
indigo. Forms a ' vat.' Is more stable towards
oxidising agents than indigo. By zinc-dust and
acetic acid it is reduced first to leucindirubin
CigHj^^O, and finally to indileucin 0,^„NjO
(Schunck, B. 12, 1220 ; C. N. 39, 119 ; Baeyer,
B. 12, 467 ; 14, 1746 i 15, 60 ; 16, 2200).
760
INDIGO.
The brotno- derwative C,JB.fiiNJO, from
indozyl and biomisatin resembles indirubin.
The di-bromo- derwative CigHgBr^NjO, is ob-
tained in very small quantity together with di-
bromoindigo by rednotion of bromisatin chlor-
ide yfith HI. Needles: soL alcohol and ether
(Baeyer, B. 12, 1315).
The di-mtro- dervoalwoe Ot^l^O^^fit is
formed in small qaantity together with niiro-
indigo by reduction of nitroisatin chloride with
HI. Sol. alcohol with a red colonr.
Ethyl-indimbin CigH^NA i.e.
C.H4<^2>0:C<J<2 >NEt. a-Indogmide of
ethyl-fli-isatm. [198°]. Prepared by adding a
hot aqueous solution of indozyl to a hot aqueous
solution of ethyl-ifi-isatin mixed with HCl;
brownish-red needles of the product separate at
once (Baeyer, B. 16, 2200). Coppery needles :
sol. chloroform to a red solution, si. sol. alcohol
and acetone. Dissolves in cone. H^SO, with a
brown colour which becomes violet on beating
with formation of a sulphonio acid. It gives a
' vat' with zinc-dust and alkalis.
Indilencin Ojfi,^fi i.e.
CA<°i?^>>0.0<«H>^Hor
C,H,<^2^0.C< q(^^>NH. Obtained by
redaction of indirubin with zinc-dust and acetic
acid ; the yield is 35 p.o. Colourless glistening
needles ; sol. acetic acid, si. sol. alcohol, ether,
benzene, and chloroform. Fe,Cl, gives an in-
tense yellowish-green colour. Nitrous acid
colours the acetic acid solution orange. P i c r a t e
C,^,2NjOC,Hj{N02)jOH: orange crystals.
Methyl ether C,^„N2(0Me): [192°]; large
glistening prisma ; sol. alcohol and ether.
Triacetyl derivative C,„H^CjNjO: [278°];
flat yellow needles (Forrer, B. 17, 977).
Iso-indileucin CgeHi^NjO i.e.
.C(C,H.).CH:NH(?)
C^,.CO.C/ I - [192°]. Formed
^N
by shaking a benzene solution of «-di-bromo-
acetophenone CsHj.CO.CHBrj with strong aque-
ous NH,. Tellow plates. Sol. hot alcohol,
insol. water, and cold benzene. Weak base. It
gives a splendid red colouration on the addition
of phenol to its H2SO4 solution. By reduction
in alcoholic solution with tin and ECl it yields
hydroisoindileucin. Piorate
C,;H,XOC,Hj(NOj),OH aq : [150°] ; yellow
needles (Engler a. Hassenkamp, B. 18, 2241).
Hydro-iso-indilencin C^'B.j^fi i.e.
.C(0^J.CH:NH(7)
C.H,.0H{0H).C4| . [160°]
with decomposition. Formed by (be action ot
tin and HCl on an alcoholic solution of isoindi-
leucin. Plates. V. sol. alcohol, ether, and
GHCl^ SoL H2SO, with a blue colour. Oxidised
back to isoindileucin by treatment with GrO,.
MethyMso-indilencin C,^,,MeN,0. CL16°].
Formed by beating isoindileucin with Mel, and
alcoholic EOH at 100°-110°. Plates. Sol. alcohol
and ether. No colouration with HjSO, and
phenol (Engler a. Hassenkamp, B. 18, 2242).
Indoin CH^N^O,. Formed by adding FeSO,
to a solution of o-nitro-phenyl-propiolio acid in
H2SO4, or by the action of the propiolic acid on
an H2SO4 solution of indoxyl. Also by action of
FeSOf and cone. H2SO4 upon o-di-nitro-di-
phenyl-diaoetyleneCsHj(NOj).C:C.C:C.C'sH,(NOJ
or upon the isomeric diisatogen CigH^jO, ; and
by treatment of isatogen-snlphurous acid with
cone. H2SO4. Blue dye-stufi, resembling indigo
in many points. Dissolves in cold H2SO4 with a
blue colour, but is not readily solphonated.
Also dissolves to a blue eolation in cold aniline
or aqueous SO,. Combines with SO,. Gives a
• vat ' (Baeyer, B. 14, 1742; 16, 62, 67, 212).
ludoline C„H„N, t.«.
^•H.<SaCH^H>OA. rUndole. [246°].
Formed by heating leucindigo (indigo-white)
!1 pt.) with barium hydrate (2 pts.), zinc-dust
1^ pts.) and water (180 pts.) for 24 hours at
180° (Schiitzenberger, J. 1877, 611) ; the product
is extracted with alcohol, the alcohol evaporated,
and the residue heated with zinc-dost when
indoUne sublimes. More readily obtained by
reduction of flaviudine dissolved in dilute NaOH,
with 3 p.c. sodium amalgam (Giraud, J. 1880,
586). Long yellow needles by sublimation. Sol.
alcohol and ether with a blue fluorescence, insol.
water. Forms salts with acids. The picrate
C,sH,jN,C,Hj(NOJjOH is si. sol. alcohol.
Di-ohloro-indolineC,sH,2Cl,N,. Got by
passing CI into a CHCI, solution of indoline.
Di-nitro-iudoline C,^„(NO,)^r Got
by dissolving indoline in warm nitric acid. Oxya-
tallises from alcohol in orange-yellow crystals.
Indoline-di-sulphonic acid
C,^,2(SO,H),N2 is formed by heating indoline
with faming E^jSO, at 180°. Its sodium salt
A"Na2 is crystalline.
Other references. — Sommaraga, B. 11, 1085;
Einhorn, B. 16, 2208 ; Alexejew, B. 17, Bet. 172;
Bl. 42, 320; MiiUer, A. 212, 122 ; Eolbe, J.pr. [2]
30, 84 ; Bosenstiehl, A. Ch. [B] 21, 286 ; 0. J.
40, 98. V. also Isatin, Isaiio acid, Oziin>oi>s,^
Insozzl, Indoztuc acid, DnsAiooEN, Indooem-
IDES, IkDINE, ImDOUI, NlXBO-PBEinX-PBOFIOUa
ACID, Dl-NITBO-SI-rHEimi-DI-AOErXLBNII, ISAIO-
OJSNIO ACID. ▲. G. G.
BMD OJf XHE 8E00ND TOIiUMB.
SfltimiuiU, BaUmHtyiu A* C«. Ltd., Prinien, Lomltn, Cekhuttr Sf Mten, a^imA
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