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Full text of "Watt's Dictionary of chemistry"

Mtbi |9orfe 

S>tatc Collese of ^arfculture 

at Cornell ®ntber«itp 

Stbaca, B. S- 



Cornell University Library 
QD 5.W52 
V.2 

Watt's Dictionary of chemistry, 




3 1924 002 980 575 




Cornell University 
Library 



The original of tiiis book is in 
tine Cornell University Library. 

There are no known copyright restrictions in 
the United States on the use of the text. 



http://www.archive.org/details/cu31924002980575 



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 /lO O- 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 





0-99557 


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 ; 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 ; in 
some cases, e.g. ALfl,, B^Oj, 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 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 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 ; 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 
(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 
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 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. 
and 1 vol. CI. Then from the weights of 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 ob- 
tained was almost exactly double the total 
expansion of the gas ; but it the gas were 
CI2O3 the volume of 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 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 ; 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 to HClAq ; nor should 
we expect to form KOlOjAq by adding to KClAq, 
for [KClAq,0»l= -15,370 (Thomsen) ; the pro- 
duction of HClOAq by the direct combination of 
01 and in presence of H^O is also improbable, 
considering that [CP,0,Aq] = -8,490 (Thomsen). 
CI and 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 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, is evolved and ZCIO, and 
ECl are produced ; on raising the temperature 
EGl remains and all the 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 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 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 + ; 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 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 





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 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 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, 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 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, 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 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. 


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. 


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. 


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 - -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° ; = 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 


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. 

Triehlorh ydr in 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 (' ')-di-nitro- 
naphthalene, nitro-(7)-di-ohloro-naphthalene, 
('o') chloro-di-nitro-naphthalene [106°], ('3')- 
ohloro-di-nitro-uaphthalene, and nitro-(' ')-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 (' ')-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 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 - 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-OLTOXA LIKE . 

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). 

(■ ')-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 . 

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 

TJAfl nl flH 

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- - 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, 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 turning green. 
F6Ugot determined the quantity of 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 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 ; 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 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 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 ; 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, 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 ; 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 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 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 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 (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.