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I 



/ 



JOURNAL 



OF 



THE CHEMICAL SOCIETY. 



ABSTRACTS OF PAPERS. 



H. Brereton Baker, M.A 

F.R.S. 

Horace T. Brown, LL.D., F.R.S. 
J. N. Collie, Ph.D., F.R.S. 
A. W. Crossley, D.Sc, Ph.D., F.R.S. 
F. G. DoNNAN, M.A., Ph.D., F.R.S. 
Bernard Dyer, D.Sc. 
M. 0. FoRSTER, D.Sc, Ph.D., F.R.S. 



€ammiikt of IBtiblitatbn : 
D.Sc, 



P. F. Frankland, Ph.D., LL.D. 

F R S 
C. E. Groves, F.R.S. 
A. McKenzie, M.A., D.Sc, Ph.D. 
J. C. Philip, D.Sc, Ph.D. 
A. Scott M.A., D.Sc, F.R.S. 
S. Smiles, D.Sc 



€Mt0r : 
J. 0. Cain, D.Sc, Ph.D. 



^ttb-€Mt0r : 
A. J. Green AWAY. 



E. F. Armstrong, Ph.D., D.Sc 

F. Barrow, M.Sc, Ph.D. 
R. J. Caldwell, D.Sc 
W. A. Davis, B.Sc 

H. M. Dawson, Ph.D., D.Sc 
C. H. Desch, D.Sc, Ph.D. 
W. H. Glover, Ph.D. 

"W. GODDEN, B.Sc 

E. GOULDING, D.Sc 

W. D. Halliburton, M.D., F.R.S. 

T. A. Henry, D.Sc 

H. B. Hutchinson, Ph.D. 

L. De Koningh. 

G D. Lander, D.Sc 

F. M. G. Micklethwait. 
N. H. J. Miller, Ph.D. 
T. H. Pope. B.Sc 



g^bstrattorfi! 



T. Slater Price, D.Sc, Ph.D. 

E. J. Russell, D Sc * 
S. B. SCHRYVER, D.Sc, Ph.D. 

G. Senter, Ph.D., B.Sc. 
W. P. Skertchly. 

C. Smith, D.Sc 

F. Soddy, M.A., F.R.S. 

J. F. Spencer, D.Sc, Ph.D. 

L. J. Spencer, M.A. 

R. V. Stanford, M.Sc, Ph.D. 

D. F. Twiss, D.Sc 

A. Jamieson Walker, Ph.D., B.A. 
J. C. Withers, Ph.D. 

W. 0. WOOTTON, B.Sc. 

H. Wren, M.A., D.Sc, Ph.D. 
W. J. Young, M.Sc, D.Sc. 



1912. Vol. CII. Parts I. & II. 



LONDON: 
GURNEY & JACKSON, 33, PATERNOSTER ROW, E.G. 

1912. 



RicBARO Clay & Soks, Limiitd, 

BRVNSWICK STREET, BTAMFOBD STRBS-T, B.fc., 
AMD BUMQAV, SUFFOLIC 



^1> 

it 



/ 



JOURNAL 

OF 

THE CHEMICAL SOCIETY. 



ABSTRACTS OF PAPERS 



ON 



OEGANIC CHEMISTRY. 



€ommttttt of ^wblitatton: 



H. Brereton Baker, M.A., D.Sc, 

F.R.S. 
Horace T. Brown, LL.D., F.R.S. 
J. N. Collie, Ph.D., F.R.S. 
A. W. Crossley, D.Sc, Ph.D., F.R.S. 
F. G. DoNNAN, M.A., Ph.D., F.R.S. 
Bernard Dyer, D.Sc. 
M. 0. Forster, D.Sc, Ph.D., F.R.S. 



P. F. Frankland, Ph.D., LL.D. 

F.R.S. 
C. E. Groves, F.R.S. 
A. McKenzie, M.A., D.Sc, Ph.D. 
J. C. Philip, D.Sc, Ph.D. 
A. Scott, M.A., D.Sc, F.R.S. 
S. Smiles, D.Sc 



€bltor : 
J. C. Cain, D.Sc, Ph.D. 

A. J. Greenaway. 



gibstractors : 



E. F. Armstrong, Ph.D., D.Sc, 

F. Barrow, M.Sc, Ph.D. 
R. J. Caluwell, D.Sc 
W. A. Davis, B.Sc 

H. M. Dawson, Ph.D., D.Sc 
C. H. Desch, D.Sc, Ph.D. 
W. H. Glover, Ph.D. 

W. GODDEN, B.Sc 

E. Goulding, D.Sc 

W. D. Halliburton, M.D., F. 

T. A. Henry, D.Sc 

H. B. Hutchinson, Ph.D. 

L. De Koningh. 

G. D. Lander, D.Sc 

^. M. G. Micklethwait. 
N. H. J. Miller, Ph.D. 
T. H. Pope, B.Sc 



R.S. 



T. Slater Price, D.Sc, Ph.D. 

E. J. Russell, D.Sc 

S. B. Schryver, D.Sc, Ph.D. 
G. Senter, Ph.D., B.Sc 
W. P. Skertchly. 

C. Smith, D.Sc 

F. SoDDY, M.A., F.R.S. 

J. F. Spencer, D.Sc, Ph.D. 

L. J. Spencer, M.A. 

R. V. Stanford, M.Sc, Ph.D. 

D. F. Twiss, D.Sc. 

A. Jamieson Walker, Ph.D., B.A. 
J. C. Withers, Ph.D. 

W. 0. WOOTTON, B.Sc 

H. Wren, M.A., D.Sc, Ph.D. 
W. J. Young, M.Sc, D.Sc 



1912. Vol. CII. Part I. 









LONDON 



GURNEY & JACKSON, 33, PATERNOSTER ROW, E.C, 

1912. 



RirnARD Clay & 3ons, Limitkd. 

BRUNhWICK STREET, STAil*-ORD STREKT, 8,3., 
AlTD BUNOAT, SUFFOLK. 




',«' 



JOURNAL 



OF 



THE CHEMICAL SOCIETY. 



ABSTRA.CTS OF CHEMICAL PAPERS PUBLISHED IN 
BRITISH AND FOREIGN JOURNALS. 

PART I. 



Organic Chemistry. 



New Dodecane. Maurice Delacre {Bull. Soc. chim., 1911, [iv], 
9, 1023— 1024).— Crude yy-dimethyl-A"-butylene, CMeg-CHlCHa 
(Abstr., 1906, i, 476), furnishes with hydrogen bromide the com- 
pound CMeg-CHg'CHgBr {loc. cit.), and this on treatment with sodium 
yields, in addition to th^. products described already {loc. cit.), the 
dodecane [ftp-qrj-tetramethyloctane], CMe3-[CH2]4'CMe3, b. p. 185 — 190°, 
which crystallises in needles and melts at the temperature of the 
hand to a colourless liquid, possessing a faintly aromatic odour. 

T. A. H. 

Very Sensitive New Colour Reaction for Bthylenic Linkings 
and for Tautomeric Modifications. Iwan Ostromisslensky {J. pr. 
Chein., 1911, [ii], 84, 489— 495).— Tetranitromethane dissolved in 
petroleum (or other paraffin hydrocarbon) produces intense colorations 
with substances containing ethylenic linkings. The test is responded 
to by unsaturated hydrocarbons, alcohols, ketones, ethers, esters, and 
aromatic substances, but not by aromatic nitro-compounds or by many 
unsaturated carboxylic acids. 

The view is generally accepted that a tautomeric substance exists in 
one definite form in the solid phase, but acquires, in the liquid or 
gaseous phase, a state of equilibrium between two (or more) modifica- 
tions, determined by external conditions. This view is substantiated 
by experiments with tetranitromethane. In aqueous, alcoholic, or 
ethereal solution, phloroglucinol and ethyl acetoacetate develop 

VOL. cii. i. h 



1- ^ ABSTRACTS OP CHEMICAL PAPERS. 

lospectively a brownish-red and a golden-yellow coloration The 
eiiohc form of ethyl benzylidenebisacetoacetate, in the Holid state or in 
solution, instantly develops a citron-yellow coloration, whilst the 
ketonic form remains colourless under similar conditions, although its 
sodium derivative produces an intense yellow coloration. 

Tetranitromethane acts as a mild oxidising agent. It converts quinol 
into quinhydrone (nitric oxide, nitrous and nitric acids, but not uitro- 
form, have been detected among the products of the reaction), 
and dimethylaniline into crystal- violet. C. S. 

Chemistry of Amyl Compounds. Arthur Michael and Fritz 
Zkidler {AnnaUn, 1911, 386, 227— 292).— The structural theory 
based on a purely mechanical conception of valency does not suffice to 
explain many organic reactions, in particular, that of substitution 
Many facts are known which show that, for example, the conversion of 
an alcohol into an alkyl lialideby an acid is not merely the substitution 
of the halogen atom for a hydroxyl group, but must be due to an 
elimination of water from the alcohol followed by the addition of 
hydrogen halide to the olefine thus produced. It has been commonly 
accepted that the elimination of water from the alcohol is due to the 
dehydrating action of the hydrogen halide. The authors show, how- 
ever, that in the series of isoannyl alcohols the production of an 
*»w.^i\°^'^'' ^® effected at 100° by 4-5iV^-dichloroacetic acid or by 
iV/50-hydrochIoric acid, although not by water alone; they regard the 
action of an acid in causing an elimination of water from an alcohol 
as being due to catalysis, the rate of formation of amylene being 
faster the more concentrated the acid. This being so, with the neces- 
sary consequence that the formation of abnormal substitution pro- 
ducts must be conditioned by the molecular structure of the alcohol 
the two following problems require solution : (1) which of the several 
isomerides that could be formed from a given substance in a re- 
action IS actually produced ; (2) which of two isomerides that can be 
converted into the same unsaturated substance is the more easily 
decomposed. The law of entropy, the "law of addition and elimina- 
tion, and the thermochemical structure law (Abstr., 1906, i, 550; 
1 909, i 494) are applied in answering these questions. The 'applica- 
tion of these laws leads to the expectations that (1) yS-methyl- 
A^-butylene, not ^-methyl-A'-butylene, will be foru.ed by the dehydra- 
tion of ^-methylbutane-^-ol; ^2) y3-methylbutane-y-ol will yield 
^-methyl-A^-butylene almost exclusively : (3) the elimination of water 
from ^-methylbutane-8-ol will be more difficult than from B-melhyh 
butane-y-ol, and from^-methylbutane-a-ol moreeasy thanfrom /S-methyi- 
butane-8-ol; (4) by the action of hydrobromic acid, )8-methylbutane-^-ol 
will yield only the tertiary bromide, ^-methyl butane y-ol mainly the 
Ujriiary bromide, /3-methylbutane-8-ol only the primary bromide, and 
^-methylbutane-a ol the primary bromide, together with a little of the 
tertiary bromulu. The experimental results show that these expecta- 
tions are fulfilled completely in practice. The ease with which the 
preceding piimary, secondary, and tertiary woamyl alcohols yield 
amylcnet, varies so much that the authors have based on this property 



ORGANIC CHEMISTRY. 1. 6 

a method for the detection of each of these alcohols in mixtures of all 
of them. 

The remainder of the paper is mainly an extension of Michael and 
Tieupold's work on the intramolecular transformations of alkyl 
bromides (Abstr., 1911, i, 250) to the isoamyl bromides. C. S. 

Metallic Alkyloxides. E. Chablay (Oompt. rend., 1911, 163, 
953 — 955. Compare Abstr., 1911, i, 939). — Further experimental 
details are given for the preparation of metallic alkyloxides according 
to the methods outlined in an earlier communication. Calcium meth- 
oxide,ethoxide, isobutyloxide, and isoamyloxide have thus been obtained. 
Barium methoxide is particularly easy to prepare by the interaction of 
sodium methoxide and barium nitrate in liquid ammonia solution. It 
crystallises in slender needles. Barium ethoxide and strontium meth- 
oxide and ethoxide have also been prepared. Lead methoxide, ethoxide, 
isobutyloxide, and isoamyloxide were obtained by the action of the 
sodium alkyloxide on lead iodide or nitrate dissolved in liquid ammonia; 
they are exceeding sensitive to the action of heat or of moisture. 

W. 0. W. 

The Action of Certain Acid Chlorides on Potassium Nitrate 
and the Formation of Acid Anhydrides. Otto Diels and 
Harukichi Okada (Ber., 1911,44, 3333— 3336).— The authors have 
investigated the action of acetyl chloride, chloroacetyl chloride, and 
benzoyl chloride on potassium nitrate, whereby they have obtained 
good yields of acetic anhydride, chloroacetic anhydride, and benzoic 
anhydride respectively. They consider that a mixed anhydride is first 
formed, which subsequently reacts with the excess of acid chloride to 
form the acid anhydride. This is supported by the fact that acetic 
anhydride is obtained in 93% yield by the action of acetyl chloride on 
acetyl nitrate. H. W. 

The Photochemical Transformations of Solutions of Ferric 
Trichloroacetate. Frans M. Jaeger {Proc. K. Ahad. Wetenach. 
Amsterdam, 1911, 14, 342 — 356). — On exposure to light a concentrated 
(32 — 33% by weight) solution of ferric trichloroacetate is decomposed, 
carbon dioxide being evolved and hexachloroethane deposited as a 
heavy, white precipitate. A dilute solution, owing to hydrolysis, is 
orange-yellow in colour, and is not sensitive to light ; it becomes 
sensitive, however, if it is rendered colourless by the addition of an 
excess of trichloroacetic acid. No reaction takes place in the dark. 

In the presence of free oxygen, the separation of hexachloroethane 
may be prevented (in all cases it is diminished) by another reaction, 
which gives rise to chlorine, hydrogen chloride, and, in the absence of 
excess of free acid, ferric oxide ; a little chloroform is also produced. 
Trichloroacetic acid acts as an oxygen carrier, the free acid itself being 
oxidised with liberation of chlorine. 

The photochemical reaction takes place in blue light, less rapidly in 
green light, and not at all in red or yellow light. The light obtained 
from uviol lamps is convenient to use for the reaction. Rise in tem- 
perature first increases the hydrolysis of a solution, and then causes 

b 2 



i. 4 ABSTRACTS OF CHEMICAL PAPERS. 

the liberation of carbon dioxide ;* at the same time, deposition of ferric 
oxido takas place nnd some clilorofoim is formed. Similarly, thallous 
tribromoacetate and ferric tribromoacetate both give carbon dioxide 
and bromoform. 

When a ()68iV-solution of trichloroacetic acid is electrolysed between 
platinum electrodes, hydrogen is, at first, evolved continuously at the 
cathode, whereas a discontinuous evolution of gfis occurs at the auode. 
After a time an oily drop forms at the surface of the liquid above the 
auode, finally bocoming of such a size that it breaks away from the 
liquid surface and falls to the bottom of the solution. The evolution 
of hydrogen ceases after a time. The electrolyte finally contains 
carbonyl chloride, chlorine, and hydrochloric acid ; the oil formed was 
trichloromethyl trichloroacetate (compare Kaufler and Herzog, Abstr., 
1909, i, 870) ; it generally solidified at 22°, and the solid had m. p. 
32 — 34°. The presence of carbonyl chloride, etc., in the electrolyte 
was probably due to the decomposition of this ester by water, according 
to the equation : CCls-COg'CCl., + HgO = CCia-COgH + HCl + COCJg. 

The author confirms the results of Anschiitz and Emery (Abstr., 
1893, i, 188) that trichloromethyl trichloroacetate is a different 
substance from pentachloroethyl chloroformate, Cl'COg'CgCl^. 

Solutions of ferric pentachloropropionateare very sensitive to light, 
carbon dioxide being evolved and tetrachloroethylene formed, probably 
according to the equation : 

FeCCO^-C^Cy 3 -> CO2 + C2CI, + Fe(CO./C2Cl5)2Cl. 
The formation of hexachloroethane in the photochemical decomposition 
of ferric trichloroacetate is possibly due to the decomposition of the 
anion, thus : 2CC18-CO-0' — > 200^ + CgClg. T. S. P. 

Action of Acid Chlorides on Ethyl Diethoxyacetate. Bruno 
Mylo {Ber.j 1911, 44, 3211— 3215).— By the action of phosphorus 
pentachloride on ethyl diethoxyacetate, ethyl chloroethoxy acetate, 
OEt-CHCl-COgEt, is formed ; it has b. p. 79712 mm. On heating 
with copper powder, it is converted into ethyl a^-diethoxysuccinate, 
C2H2(OEt)j(C02Et)2, b. p. 140—143712-5 mm. In the above reaction 
phosphorus pentachloride may be replaced by thionyl chloride, acetyl 
bromide or chloride. Ethyl diethoxyacetate and acetyl bromide give 
rise to ethyl ethoxybronioacetate, b. p. 90 — 91-5711 mm. When acetyl 
chloride is used, a little copper bronze is required as a catalyst. 
Benzoyl chloride reacts with the acetal in presence of zinc chloride, 
but the reaction is obscured by secondary changes. E. F. A. 

The Optically Active Dibromosuccinic Acid. Bror Holm- 
BKRG {Svensk Kem. I'idskr., Ko. 5, 1911, Reprint, 5 pp. Compare 
Abstr., 1911, i, 767.) — The author has shown that r-a/3-dibromo- 
succinic acid is obtained by addition of bromine to maleic acid or 
maleic anhydride, whilst 7?i«so-a)8-dibromosuccinic acid is formed by 
direct bromination of succinic acid or by addition of bromine to 
fumaric acid. 

r-a^-Dibromoftuccinic acid was resolved by means of cinchonine. 
A crystalline salt, 2Ci9H220N2,C4H.^04Br2,6H20, separates whe^ 
aqueous solutions of cinchonine nitrate and sodium a^-dibromosuccin- 
at© are mixed. From this salt, /-a)3-dibromosuccinic acid m. p, 



ORGANIC CHEMISTRY. i. 5 

152 — 154**(decomp.), was isolated. In ethyl acetate it has [aj^ - 101-4°, 
which remained unchanged during two days. In ether it has 
[a]g -105-4°; in water, [[a]g -48-3°. After nine days this value 
had decreased to [a]g - 20-15°. Further purification was effected by 
dissolving this acid in a mixture of ethyl acetate and carbon tetra- 
chloride. After removal of a crop of less active acid, the filtrate, on 
evaporation, left a residue of Z-acid, m. p. 152 — 153°, which had 
[a]u - 137-6° in ethyl acetate. This was the most highly active acid 
obtained by the author. 

Impure r/-a/3-dibromosuccinic acid was obtained from the filtrate 
from the original cinchonine salt. The crude acid had [aj^ + 84'9° in 
ethyl acetate. When purified in the manner adopted for the ^acid, 
it had m. p. 151—153°, and [a]?/ +126-3° in ethyl acetate. 

Attempts to resolve r-ay8- dibromosuccinic acid by means of quinine 
were less successful. 

meso-DibromosLiccinic acid could not be resolved by means of 
morphine or brucine. H. W. 

Preparation of Esters of Orthotrithioformic Acid. Josef 
HouBEN and Karl M. L. Schultze {Ber., 1911, 44,3235—3241).— 
Esters of thiolformic acid should be formed by direct formylation of 
the mercaptans, according to the equation : 

R-SH + H-COgH = H-CO-SR + H2O. 
Owing probably to the fact that the ester produced contains the 
aldehyde group, the reaction proceeds further, with the formation of 
esters of orthotrithioformic acid : 

R-S-CHO + 2R-SH = R-S-CH(SR)2 + HgO. 
The reaction is readily carried out by heating the mercaptan with 
anhydrous formic acid under reflux for some time ; in the case of 
methyl meicaptan, the reaction mixture is kept in a sealed tube for 
forty-eisht hours at the ordinary temperature. 

Methyl orthotrithioformate^ CH(SMe)3, is a colourless oil, b. p. 
9.6°/9 mm., 220°/760 mm. (decomp.), which becomes yellow on warming ; 
it solidifies at 16°. The odour is characteristic, but by no means 
disagreeable. The solution in chloroform decolorises bromine at first, 
but further addition of bromine leads to the evolution of hydrogen 
bromide and the formation of a brownish-red coloration, which is not 
due to bromine. Ethyl orthotrithioformate has b. p. 124 — 125°/ 
1 1 mm., 235°/760 mm. (decomp.) ; the odour is only slight, the ester being 
purer than that prepared by Holmberg (Abstr., 1907, i, 474). Benzyl 
orthotrithioformate has m. p. 102*5°. It can be prepared by using 
oxalic acid in place of formic acid, carbon dioxide being first evolved. 
"^'Tolyl orthotrithioformate, IIC(8*CgH4Me)3, forms snow-white crystals, 
m. p. 109°. fX'Naphthyl orthotrithiojormate, HO(S'CioHjw)3, has m. p. 
134°. On exposure to light, it gradually becomes pale green in 
colour. Allyl orthotrithioformate could not be obtained pure. 

T. S. P. 

Carbithionic Acids. V. Preparation of New Eaters of 
Carbithionic Acid and of Ethyl Chlorocarbithionate. Josef 
HouBEN and Karl M. E. Schultze {Ber., 1911, 44, 3226—3234).— 
The ethyl esters of the carbithionic acids are readily obtained by the 



1. 6 ABSTRACTS OF CHEMICAL PAPERS 

action of ethyl sulphate on a(]ueona Folutions of the acids prepared 
by the action of carbon diaulphide on the organo-magnesium compounds 
(compare Abstr., 1906, i, 847; 1907, i, 382, 474). The method of 
preparation is similar to that described for the methyl esters, but the 
eaterificAtion with ethyl sulphate does not take place so readily as 
with methyl sulphate, it being necessary to warm for some time on 
the water-bath. Moreover, excess of ethyl sulphate does not produce 
decomposition to the same extent as methyl sulphate, so that in the 
treatment of the reaction mixture it is not usually necessary to 
decompose the excess of ethyl sulphate with steam. The yields 
obtained are generally small, except in the case of a-naphthylcarbithionic 
esters, where they amount to 40 — 43%. 

Ethyl methylcarbithionaie {ethyl dithioacetate), CHg'CSgEt, is an 
intense yellow liquid, possessing an odour somewhat similar to that 
of ethyl acetate. It has b. p. 42—43711 mm., DJ" 1*036, and 
is rapidly oxidised by the air or oxidising agents. With mineral 
acids or aqueous-alcoholic sodium hydroxide, it gives acetic acid and 
mercaptan. 

Ethyl ethylcarbithionate (ethyl dithiop'opionate), CgH^'CSgEt, has 
b. p. 60 — 61°/10 mm. It is a yellow liquid with a pronounced, 
characteristic odour. Methyl phenylcarbithionate (methyl dithio- 
benzoate), CgHg-CS^Me, was obtained in a slightly purer condition than 
the specimen prepared by Hohn and Bloch (Abstr., 1910, i, 256), and 
had b. p. 141 — 142°/ 12 mm. At the temperature of liquid air it 
forms a flesh-coloured, solid mass. Methyl a-naphthylcarhithionate 
(methyl dithioa-naphthoate), CjQH^'CSgMe, forms orange-yellow needles, 
which melt to a dark red oil at 54°, b. p. 2 10°/ 15 mm. It is quite 
stable in the air, as also is ethyl a-naphthylcarbithionate (ethyl dithio-a- 
imphihoate), C^oH^'CSgEt, which forms orange-yellow crystals, melting 
to a dark red oil at 39 — 40°. Both these esters are stable towards 
dilute and concentrated hydrochloric acid, but are decomposed in the 
usual way by aqueous-alcoholic sodium hydroxide. 

Ethyl chlorocarhithionate (ethyl chlorodithioformate), Cl'CSgEt, is 
obtained by the gradual addition (lasting twenty-four hours) of 
thiocarbonyl chloride (25 grams) to a solution of ethyl mercaptan 
(13'5 grams) in carbon disulphide (75 c.c), and fractiooation of the 
reaction mixture, after further keeping for two day?, under diminished 
pressure. It forms an intense reddish-yellow oil, which excites to 
tears and has a penetrating odour, b. p. 80 — 81°/ 19 mm. and 
74 — 75°/15 mm. It is stable when kept away from air and moisture. 
It reacts with amino-acids ; for example, on shaking with an aqueous 
solution of potassium anthranilate, a red oil is formed, which rapidly 
crystallises, and is probably COgH'CgH^'NH'CSgEt. With organo- 
magnesium compounds, it reacts according to the equation : 

RMgX + Cl-CSaEt = R-CSgEt + ClMgX. 
W^ith a solution of sodium iodide in acetone, it gives the corresponding 
iodo-compound. When reduced with potassium arsenite in alkaline 
solution, a brown oil is obtained, which, on fractional distillation, 
gives a light yellow oil with b. p. 131 — 132°/19 mm. and 115°/11 mm. 
The composition corresponds with that of ethyl thioformate 



ORGANIC CHEMISTRY. 1. 7 

(II'CS2Et), but the high boiliug point indicates that it is probably 
a polymeride of that substance. 

In the preparation of ethyl chlorocarbithionate, a by-product, 
b. p. 115 — 125719 mm., is obtained, especially if the reaction 
mixture is not too strongly diluted with carbon disulphide, which 
is probably ethyl trithiocarbonate. T. S. P. 

a-Bromoacraldehyde. Robert Lespieau {Gompt. rend., 1911, 
153, 951 — 953). — Pyrazole is produced when a-bromoacraldehyde is 
added to a solution of hydrazine hydrate. The aldehyde does not 
unite with hydrogen cyanide unless a trace of potassium cyanide is 
present, when the action becomes violent. Hydrolysis of the resulting 
nitri/e leads to formation of fS-bromo-a-hydroxy-A^-butenoic acid, 
CH2:CBr-CH(OH)-C02H, m. p. 119—120°; i\\Q potassium salt is very 
deliquescent; the ethyl ester has b. p. 216—2177750 mm. 

ISPy-Tribromo-a-hydroxybutyric acid, CH2Br-CBr2-CH(OH)'C02H, 
obtained by the action of bromine on the foregoing unsaturated acid, 
has m. p. 140 — 141°. The high boiling residue from the distillation 
of a-bromoacraldehyde yields a nitrile under the above-mentioned 
conditions. On hydrolysis a mixture of acids is obtained, from which 
crystals, m. p. 104 — 105", have been isolated; they probably consist 
of f^yy'tribro7no-a-hydroxybutyric acid, which arises from the presence 
of fiyy-tribromopropionaldehyde in the original aldehyde. 

W. 0. W. 

Attempt at the Direct Preparation of Tetrolaldehyde. 
Paul L. Viguier (Compt. rend., 1911, 153, 955— ^957).— In the 
expectation of obtaining tetrolaldehyde, diethylformamide (1 mol.) was 
treated with the magnesium derivative of bromopropinene (1 mol.). 
After the usual treatment, the product was found to consist of 
ucaltered amide with h-diethylamino-A^^heptadi-inene, 

CMe:C-CH(NEt2)-C:0Me, 
an oily liquid, b. p. 99— 99*5714— 15 mm., Bf 0-871, n]! 1-477. The 
picrate occurs in slender needles, m. p. 169°; the platinichloride crystal- 
lises with 2H2O, and decomposes at 120°; the ethiodide decomposes at 
148—150°. 

When the magnesium derivative of bromopropinene is treated with 
excess of ethyl formate, S-hydroxy-A^^-heptadi-inene, 

CMe:C-CH(OH)-C:CMe, 
results instead of the expected aldehyde. This substance resembles boric 
acid in appearance, and has m. p. 105 — 106°. The required aldehyde 
appears to be produced when the sodium derivative of propinene 
is treated with ethyl formate, but the reaction is so slow that decom- 
position occurs and no definite product can be isolated. W. O. W. 

Catalytic Reactions at High Pressures and Temperatures. 
XXIII. Hydrogenation of Acetone in the Presence of Copper 
Oxide and Zinc Dust. Wladimir Ipatieff and G. Balatschinsky 
{Bar., lyil, 44, 3459 — 3461). — The action of zinc dust and of copper 
oxide as catalysts on the hydrogenation of acetone under pressure has 



i, 8 ABSTRACTS OF CHEMICAL PAPERS. 

been inveBtigatod (compare Abstr., 1907, i, 828). An iron tube was uRed, 
the temperature being 280 — 300°, it having been proved that iron has 
no catalytic effect at 300". The initial preRSure of the hydrogen was 
100 — 130 atmospheres. 

With copper oxide as catalyst the resulting product contains 65% 
of tsopropyl alcohol, whilst the percentage when zinc is uHcd is 
about 50%. 

Tt was also shown that with initial hydrogen pressures of 40 atmo- 
spheres, wopropyl alcohol gives acetone and hydrogen at 300°, with 
zinc dust as catalyst. Also, with acetone and copper oxide, condensa- 
tion products of an unsaturated character are formed. Thus the 
reaction: CHMeg'OH z:!: Hg + COMeg is reversible in the presence 
of zinc dust or copper oxide. T. S. P. 

The Electrolytic Reduction of Ketones. Julius Tafel [with 
WiLHELM ScHEPSs] {Zeitsch. EUktrochem., 1911, 17, 972 — 976. Compare 
Abstr., 1911, i, 784). — Acetone and methyl ethyl ketone are readily 
reduced electrolytically to the corresponding saturated hydrocarbons 
at a cadmium cathode in sulphuric acid solution. With the higher 
aliphatic ketones, for example, methyl woamyl ketone, similar results 
can only be obtained with very high current densities (compare Abstr., 
1909, i, 766). 

Similar results are obtained with mercury and lead cathodes in the 
case of acetone, but the yield of propane is not so great, owing to side 
reactions, such as, in the case of lead cathodes, the formation of iso- 
propyl alcohol, pinacone, and lead alkyls. 

i>oPropyl alcohol does not undergo reduction under conditioLS which 
lead to the formation of propane from acetone. T. S. P. 

The Action of Chlorine on Hexonic Acids (Hexonsauren) 
[Maltol]. Paul Dreverhofp {Chem. Zeit, 1911, 35, 1323).— The 
substance (maltol ; compare Abstr., 1910, i,'225, 544) which is formed 
when moist malt, etc., is heated, is decomposed by chlorine, 2 molecules 
of the substance yielding first salicylic acid and then phenol. Traces 
of maltol are present in certain dark-coloured beers, and may be 
detected by adding a very small quantity of chlorine to the beer, an 
odour of phenol being produced immediately. W. P. S. 

Degradation of woRhodeose. Emil Votocek and Cyrill Krauz 
(Ber., 1911, 44, 3287— 3290).— The configuration, 
OH H OH 

CHO-C C C'CH(0H)-CH3, 

H OH H 
previously assigned to worhodeose (Abstr., 1911, i, 354) has now been 
confirmed by oxidation of the sugar with bromine to isorhodeonic acid, 
treatment of the calcium salt of this with hydrogen peroxide and iron, 
and oxidation of the methyltetrose formed with nitric acid to tartaric 
acid. The modification formed is shown to be /-tartaric acid, 

H OH 

COaH-C C-COgH. 

OH H E. F. A. 



ORGANIC CHEMISTRY. i. 9 

Behaviour of Sucrose and its Decoraposition Products 
on Heating. IV. Reducing Substances in the Refinery 
Products. J. E. DuscHSKY (Zeitsch. ver. deut. Zuckerind.y 1911, 
989—1005. Compare Abstr., 1911, i, 769).— In the refinery, sugar 
solutions are only exposed to a high temperature for a relatively short 
time, but undergo protracted treatment at lovver temperatures. The 
formation of reducing substances has been followed quantitatively in 
great detail throughout every stage of the process. 

In the melting department there is an increase of reducing substance 
which is greatest when the crude sugar is dissolved in waste water, 
and least when dissolution is effected in pure water. 

There is a considerable increase of reducing substance in a relatively 
short time when the syrup is left at a high temperature in the boilers 
of the melter. The filtration of the syrup through bone charcoal 
does not cause any increase in the reducing substances. During 
the boiling of the raffinade syrup there is no noticeable increase 
in the reducing substances ; the same applies to the interval during 
crystallisation and subsequent drying of the crystals. E. F. A. 

Sugar Solutions and Lime. P. J. H. von Ginneken {Proc. 
K. Akad. Wetensch. Amsterdam^ 1911, 14, 442 — 461. Compare 
Claasen, Abstr., 1911, i, 606), — From the point of view of the phase 
rule the author first gives a theoretical discussion of the phenomena 
which are likely to be observed in systems containing the three 
components : lime, sugar, and water. Details are then given of 
experiments on the decomposition of the trisucrate, and on the posi- 
tion of the eutectic line at 80°. The solubility of calcium hydroxide 
in sugar solutions of varying concentrations at 80° was also 
determined. 

The results obtained are applied to the explanation of various 
well-known facts. T. S. P. 

Methylethylammonium Chlorides. John E. Mackenzie {J. pr. 
Chem., 1911, [ii], 84, 549 — 554). — For the purpose of a comparative 
study of their toxic actions, the methylethylammonium chlorides 
intermediate between tetramethyl- and tetraethyl-ammonium chloride 
have been prepared by the direct interaction of an amine and an alkyl 
chloride in alcoholic solution at 40 — 60°. C. S. 

The Behaviour of Certain Hydroxides towards Solu- 
tions of Alkylenediamines. Wilhelm Traube (JBer,, 1911, 44, 
3319 — 3324). — Whilst copper hydroxide is only slightly soluble in 
aqueous solutions of primary aliphatic amines and insoluble in 
solutions of secondary aliphatic amines, it dissolves readily in aqueous 
solutions of aliphatic diamines. Whether in concentrated or dilute 
solution, two molecules of ethylenediamine were found to dissolve one 
molecule of copper hydroxide. The formula, [Cu(C2H8No)2](OH).^, 
is ascribed to the compound so formed, which could not, however, be 
obtained in the solid state. The solutions have a deep bluish-violet 
colour, absorb oxygen from the air, and readily dissolve cellulose. 



i. 10 ABSTRACTS OF CHEMICAL PAPERS. 

A similar reaction occurs with propylenediamine and copper 
hydroxide. 

The hydroxides of nickel, cobalt, zinc, and cadmium, and the oxides 
of silver and mercury are also soluble in solutions of alkylenedianiines. 
The respective formula, [Ni(C2H8N2)3](OH)2, [Zn(C2H8N2)6](OH)2, and 
[Ag(C2HgN2)3]OH, have been assigned to the nickel, zinc, and silver 
complexes. 

The solutions were prepared by shaking the metallic hydroxide, or 
oxide in the case of silver, with aqueous solutions of ethylenediamine. 
The solutions containing zinc and nickel were found to be more readily 
obtained by shaking the metal with aqueous ethylenediamine in the 
presence of oxygen. H. W. 

The Asymmetric Cobalt Atom. III. and IV. Alfred 
Werner {Ber., 1911, 44, 3272—3278, 3279— 3284).— III.— The 
present paper deals with the resolution of 1 : 2-chloronitrodi- 

ethylenediaminecobaltic salts, ^^ Co eng X, into their optical iso- 

merides. Theoretically, the optical isomerism of these salts is of the 
same type as that of 1 : 2-chloroamminediethylenediaminecobaltic 

salts, IT 1^ Co eng Clg, dealt with in the first paper of this series 

(Abstr., 1911, i, 613), except that two acid groups are now in direct 
combination with the cobalt atom, so that the complex is univalent. 

Although the 1 : 2-chloronitrodietbylenediaminecobaltic salts show a 
great tendency to form aquo-salts in aqueous solution, it was found 
possible to resolve them by means of the silver camphorsulphonates. 
The least soluble isomerides are Z-chloronitrodiethylenediamine- 
cobaltic c?- camphorsulphonate and c?-chloronitrodiethylenediamine- 
cobaltic Z-bromocamphorsulphonate and from these the iodides could 
be obtained by means of sodium iodide. Owing to the formation of 
aquo-salts, however, it was difficult to obtain the active isomerides in 
quantity by this method. Much better results were obtained by a 
method similar to that used in the resolution of chromium compounds 
(Abstr., 1911, i, 960). When rf-ammonium camphorsulphonate or 
J-ammonium bromocamphorsulphonate is added to a freshly prepared, 
saturated solution of 1 :2-chloronitrodiethylenediaminecobaltic chloride, 
crystals of Vchloronitrodiethylenediaminecohaltic d-camphorsufphonate 
or of d-chloi'onitrodiethylenediaminecobaltic d-bromocamphorsulphonate 
are deposited in a pure condition after a short time. From these 
the corresponding chlorides can be obtained by solution in concentrated 
hydrochloric acid and precipitation with alcohol. 

The active chloronitrodiethylenediaminecobaltic salts show the 
phenomenon of mutarotation. The initial rotation gradually increaj-es, 
the colour of the solution at the same time changing from red to 
yellow, owing to the formation of cw-nitroaquo-salts, in accordance 

with the equation: [^^ Co en^l CI + HgO = [^^ Co englcig. 

Also, by interaction with sodium nitrite they can be transformed 
without loss into the dinitro-salts, and the diuitro-perchlorates so 
obtained have [aj^ + 39° and - 40° in a 1% solution, which is the 



ORGANIC CHEMISTRY. 



11 



same as that obtained with the active dinitro- salts obtained by direct 
resolution (Abstr., 1911, i, 838). 

d- and 1-1 : 2-Chloronitrodiethylenedia'niinecobaUic chlorides^ 
^Cl 



[no2 ^^ ^" Jci, 



have [a]i) + 20° and - 21*5° respectively. In 50% (by volume) 
hydrochloric acid solution they have [a]c+16° and -16-5°, and 
[a]^ ± 25° ; the hydrochloric acid solution is more stable than 
the aqueous solution. In aqueous solution the rotation gradually 
increaf^es to [a], + 31° and -35°, [a]o + 52° and -48°, owing 
to the formation of the d- and \-nitroaquodiethylenediaminecohaltic 

[HO n 
^^ Co eug CI. From these solutions potassium iodide 

precipitates a periodide, from which the active iodide can be isolated. 
After keeping for weeks, the solutions become inactive. 
1-1 : 2-Nitrothiocyanatodiethylenedia7ninecohaliic chloride, 

is obtained from the chloronitro-salt by interaction with potassium 



CI, 



thiocyanate. It has [a 
enediaminecobaltic nitrate, 



50°, Wd 
Co enolNO, 



84°. 



\-Ghloronitrodiethyl- 

Cl 1 

^^ Co eug NO3, is prepared from the 

chloride by interaction with nitric acid. It has [a]c - 10°, [a]i, --36*5°. 
IV. — The 1 :2-dichlorodiethylenediaminecobaltic salts, [Clg CoengjX, 
are of the same type as the corresponding dinitro-salts (Abstr., 1911, 
i, 838), and can be resolved into the optical isomerides. Owing to the 
ready formation of the chloroaquo- and diaquo-salts in aqueous solution, 
the resolution is best accomplished by means of d- and Z-ammonium 
bromocamphorsulphonates, the method used being similar to that just 
described. The least soluble salts are \-dichlorodiethylenediamine- 
cohaltic d-bromocamphorsulphonate and d-dichlorodiethyle7iedia7nine- 
cohaltic l-bromocamphorsulphonate. From these salts the chloride, 
bromide, and nitrate are readily obtained by treatment with the 
appropriate acids. The sulphate and dithionate are prepared from the 
chloride by reaction with ammonium sulphate and sodium dithionate, 
respectively. The optical rotations (for white light) of these salts 
are as follows : 



Chloride {+18J" 



Bromide 



Nitrate i'^\^ 



168° 
176 



64° 
164 



[M]. 

+ 558° 
-607 

+ 554° 
-581 

+ 511° 
-511 



Sulphate 



Dithionate 



/ +180° 
t -182 

+ 160° 
-164 



[M]. 
+ 536° 
-540-5 

+ 542° 
-556 



The above values are not very accurate, owing to the fact that the 
rotations of the aqueous solutions diminish very rapidly, geLcrally 
becoming zero after about three hours. The solid salts preserve their 
activity unchanged, so that the racemisation in solution must be 
referred to the action of the solvent, which forms chloroaquo- and 



i. 12 ABSTRACTS OF CHEMICAL PAPERS. 

(liaquo-salts. The exact process of racemisation cannot be given as 
yet. In some cases the chlorine atoms in the complex can be replaced 
by other acid radicles without loss of activity ; for example, with 
potassium carbonate, an active carbonatodiethylcnediaminecobaltic 
salt is formed, which is readily isolated from some inactive salt 
produced at the same time ; the salt rotates in a direction opposite to 
that of the dichloro-salt from which it was made. In other cases the 
replacement of the chlorine atoms in the complex gives inactive s^lts, 
for example, inactive 1 : 2-hydroxyaquo- and 1 : 2-dinitro-diethylene- 
diaminecobaltic salts. 

Racemic 1 : 2-dichlorodiethylenediaminecobaltic chloride is best 
prepared as follows : Finely powdered carbonatodiethylenediamine- 
cobaltic chloride is heated on the water-bath with a saturated solution 
of hydrogen chloride in absolute alcohol until the red colour of the 
salt changes to violet. The violet salt is collected and digested at the 
ordinary temperature with successive portions of aqueous alcohol 
(1:1) until the filtrate is no longer coloured green, but violet. The 
salt is then washed with absolute alcohol and ether. 

1 - Dichlorodiethylenediaminecohaltic d - hromocamphorsulphonatey 
[ClgCo en2]03S-CioHj40Br, forms violet crystals, and has [M] -414°. 
The corresponding d-l-sa^4 has [M] + 381°. Active \-dichlorodiethyl- 
enediAminecohaJtic chlorides, YC1,H20, where Y = [Cl2Co eog], crystal- 
lise in violet-coloured leaflets. The active bromides, YBr, form crystals, 
which are coloured almost indigo-blue. The active nitrates, YNO3, 
give small, violet crystals ; those of the sulphates, YgSO^, are coloured 
dark violet, whilst those of the dithionates, YgSgOg^gO, are light 
violet in colour. T. S. P. 

Action of Sodium Hypochlorite on Hexamethylene- 
tetramine. Marcel Delepine {Bull. Soc. chim., 1911, [iv], 9, 
1025 — 1029). — Sodium hypochlorite reacts with aqueous solutions of 
hexamethylenetetramine to form iV-dichloropentamethylenetetramine, 
but in presence of acetic acid gives -^-trichlorotrimethylenetriamine 
(1 : 3 :5-trichlorohexahydrotriazine), which is isomeric with Cross, 
Bevan, and Bacon's methylenechloroamine (Trans., 1910, 97, 2404). 

'^-Dichloropentamethylenetetr amine, CgHjQN^CIg, crystallises in bril- 
liant lamellae from water, or in octahedra from ether, possesses the odour 
peculiar to compounds containing chlorine and nitrogen, is sparingly 
soluble in water, and moderately so in ether or benzene, and deflagrates 
at 78 — 82°, giving an odour of carbylamines. It can be kept for long 
periods in sealed tubes, but decomposes in the course of a few days on 
exposure to air, forming ammonium chloride and hexamethylene- 
tetramine hydrochloride. With sodium hydroxide in alcohol, ammonia 
is produced, and the chlorine is removed as alkali chloride. 

1 : 3 : 5-Trichlorohexahydrotriazine (Abstr., 1899, i, 326), 

OH <^^'-CH2>jjc] 



2^NC1— CH 



crystallises in brilliant needles, has a slight cdour of chlorine, is nearly 
insoluble in water, but solublein alcohol or chloroform, and deflagrates at 
78°, evolving fumes having the odour of hydrogen cyanide and carbyl- 
amines, and leaving a residue of ammonium chloride. It decomposes in 



ORGANIC CHEMISTRY. 1. 13 

air, or when kept in solution in organic solvents. With sodium hydroxide 
in alcohol, it yields ammonia and sodium chloride, and the residue on 
distillation with a dilute acid gives formic acid : this decomposition 
appears to take place in accordance with the equations : 

(1) (CH^iNCOs + 3NaOEt = 3NaCl + 3CH(NH)-0Et ; 

(2) CH(ISrH)-OEt. + 2H2O = H-COgH + EtOH + NH3. 

T. A. H. 

Condensation of Amino-acids in Presence of Glycerol : cyclo- 
Glycylglycines and Polypeptides. Louis C. Maillard (Compt. 
rend.y 1911, 153, 1078 — 1080). — Attempts to prepare glycerides of 
amino-acids have proved unsuccessful. Glycine is converted into 
diketopiperazine by heating with four or five times its weight of glycerol 
for some hours. The yield of the pure anhydride is 80%. Other 
condensation products are also formed under these conditions ; tri- 
glycylglycine occurs as an intermediate product, but this in turn loses 
water, forming the anhydride, together v/ith pentaglycylglycine and a 
brown oxidation product. The yield of polypeptides is greatly increased 
by employing a smaller proportion of glycerol. By the same method 
sarcosine and alanine have been transformed into their cyclic anhydrides, 
and leucine into leucinimide. The reaction appears to be general, and 
can be applied to the preparation of mixed anhydrides. It probably 
involves formation of an unstable glyceride, which decomposes, losing 
glycerol and water. The suggestion is made that the synthetic reactions 
eHected by enzymes are of this type. 

The author proposes to use the prefix cyclo for the anhydrides of 
amino-acids; thus diketopiperazine is termed cyc^oglycylgiycine, and 
the condensation product of tyrosine and leucine becomes cyclo- 
tyrosyl-leucine. W. O. W. 

Synthesis of Amino-acids. IX. Racemic Arginine 
(a-Amino-S-guanidino-Ti-valeric Acid) and the Isomeric 
8- Amino- a-guanidino-/*- valeric Acid. Soren P. L. Sorensen, 
Margrethe Hoyrup, and A. C. Andersen {Zeitsch. phyaiol. Ghem., 
1911, 76, 44—94. Compare Abstr., 1910, i, 227).— In part already 
published. 

When ornithuric acid is treated with warm concentrated hydro- 
chloric acid, pure 8-monobenzoyiornithine, 

COPh-NH-CH2-CH2-CH2-CH(NH2)-C02H, 
is obtained. On boiling ornithuric acid, however, with ^/5-barium 
hydroxide, the product is a-monobenzoylornithine, 

NH2-CH2-CH2-OH2-CH(NH-COPh)-C02H. 
Under suitable experimental conditions the yield of both these 
compounds is satisfactory. 

When the amino-group is eliminated, a-monobenzoylornithine is 
converted into 8- hydroxy-a-benzoylamino-7i- valeric acid, 

OH-CH2-CH2-CH2-CH(NH-COPh)-C02H, 
whilst 8-monobenzoyiornithine yields a-hydroxy-S-benzoylamino-w- 
valeric acid. When the benzoyl group is eliminated, the 8-amino- 
a-hydroxy-7i-valeric acid described by Fischer and Zemplen (Abstr., 
1910, i, 100) is obtained. 



i. 14 ABSTRACTS OF CHEMICAL PAPERS. 

From botli the ibomeric monobenzoylornithines the corresponding 
guanidinomonobenzoylamino-n-valeric acids are obtained on the 
addition of cyanamide, and these after removal of the benzoyl group 
are converted into the isomeric aminoguanidino-n-valeric acids. That 
from a-monobenzoylornithine, which must have the formula 
NH2-C(:NH)-NH[-CH2-CH2-CH2-CH(NH2);C02H, 
proved to be in every way identical with racemic arginine. The 
isomeric 8-amino-a-guanidino-n-valeric acid had entirely different 
properties, and readily lost water, forming an anhydride. 

The yield in each of these operations amounted to 60% or more of 
the possible, and a rearrangement at any stage is considered im- 
possible. It is also proved that the cyanamide addition takes place at 
the free primary amino-group and not at the secondary amino-group, 
since the monobenzoylguanidinovaleric acids cannot be titrated in 
presence of formaldehyde. 

a-Monobenzoylotnithine, m. p. 264 — 267° (Maquenne block), forms 
long crystals, some rectangular, others flat needles. On treatment 
with barium nitrite, a-benzoylamino-8-hydroxy-n-valeric acid is 
obtained. 

a-Monobenzoylamino-8-guanidino-n-valeric acid is obtained by the 
addition of cyanamide to a-monobenzoylornithine dissolved in barium 
hydroxide; it has m. p. 315°, shows no alteration in acidity on the 
addition of formaldehyde, and is in every way identical with natural 
racemic monobenzoyl arginine. Synthetic arginine nitrate, arginine 
copper nitrate, and arginine picrate are in every respect the same as 
the natural racemic products. 

8-Monobenzoylornithine (Fischer, Ber., 1901, 34, 463), m. p. 
285 — 288°, crystallises in rhomboidal or six-sided plates ; with barium 
nitrite, a-hydroxyh-benzoylamino-n-valeric acid is obtained, forming a 
colourless, crystalline mass of bundles of prismatic needles, m. p. 85°. 

8-Monobenzoylamino-aguanidino-n-valeric acid, 

CgH5-CO-NH-CH2-CH2-CH2-CH(NH-C[:NH]-NH2)-C02H, 
forms a cheese-like precipitate, consisting of lumps of slender needles, 
m. p. 175°. When boiled with concentrated hydrochloric acid, it does 
not form a-proline. On heating for three hours at 140 — 150° with 
33% hydrochloric acid, the hydrochloride of S-amino-a-guanidino-n- 

7 • 7. ^ v7 xrxx^^^ CH-[CH2]3-NH2,2HC1 . ^, . , 

valeric anhydride^ •^^'\ri/-vrTT\ -vrtr '■'*■'*'' , is obtained 

as colourless, prismatic crystals in stellar aggregates, m. p. 2U0°. 
The picrate forms long, yellow needles, m. p. 240 — 245°. 
Ethyl y-cyanoaminopropylphthaliminomaloiiatef 

C6H,:c202:N-c(C02Et)2-[CH2]3-N:c:NH, 

from ethyl y-bromopropylphthaliminomalonate and sodium cyanamide, 
separates in well-formed colourless, short, stout, prismatic crystals, 
m. p. 191°; it can be titrated as a monobasic acid, using 
phenolphthalein. 

Ethyl y-cyanoaminopropylphthaliminomalonamide^ 

C6H,:C202:N-C(C02Et)(CO-NH2)-[CH2]3-N:c:NH, 
prepared by the action of concentrated ammonia on the above. 
Crystallises in prismatic needles. 



Organic chemistry. i. 15 

y 0*/anodminoorop7/lphthaliminomalonamic acidj 

C6H4:c202:n-c(co2H)(co-nh2)-[ch2]3-n:c:nh, 

forms long, prismatic, obliquely-cut prisms. It behaves as a dibasic 
acid. 

y-Gyanoaminopropylphthaliminomalonic acidj 

0,h,:ca:n-c(C02H)2-[ch2]3-n:c:nh, 

crystallises in stellar aggregates of microscopic needles ; it is tribasic. 
On treatment of these compounds with aqueous ammonia, anhydrous 
ammonia, or ammonium salts, it was not possible under any conditions 
to obtain guanidino-compounds. E. F. A. 

Hypoiodous Amides. Etienne BoisMenu (Compt. rend., 1911, 
163, 948 — 951. Compare Abstr., 1911, i, 957).— lodoacetamide, 
CHg'CO'NHI, is obtained as a colourless substance, m. p. 143° 
(decomp.), by the alternate addition in small quantities of iodine 
(7 grams) and silver oxide to a solution of acetamide (1*475 grams) in 
ethyl acetate (100 cc), the liquid being finally evaporated to dryness, 
and the residue washed with chloroform. lodopropionamide occurs in 
crystals, m. p. 128° (decomp.). lodoformamide, m. p. 95° (decomp.), 
is less stable than the foregoing, and rapidly decomposes at the 
ordinary temperature, even in a vacuum. lodobenzamide could not 
be obtained in the pure state. The substances described closely 
resemble the corresponding bromo-derivatives. W. 0. W. 

The Formation of Symmetrical Dialkylcarbamides by 
Heating the Corresponding Carbamates. Feitz Fighter and 
Bernhard Becker {Ber.y 1911, 44, 3481 — 3485. Compare this vol., 
ii, 45). — The alkyl substituted ammonium carbamates when heated 
under pressure give, like ammonium carbamate, an equilibrium with 
the corresponding carbamide ; the optimum temperature is, however, 
generally higher and the yield better than in the formation of the 
unsubstituted carbamide. 

Methylammonium methylcarhamate was obtained from dry carbon 
dioxide and methylamine gas in crystalline crusts which smell 
strongly of methylamine and have m. p. 105° ; it is deliquescent, and 
its aqueous solution is strongly alkaline, owing to hydrolysis. After 
heating in a sealed glass tube and subsequent removal of unchanged 
methylcarhamate, practically pure s-dimethylcarbamide (m. p. 96°) 
remains. 

Mhylammonium ethylcarbamatej prepared similarly, is a white, 
crystalline salt, m. p. 118° (in sealed tube). On heating, it gives 
diethylcarbamide (m. p. 106°), the optimum temperature being about 
150°, the equilibrium mixture at this temperature containing 59 — 60% 
of the diethylcarbamide. 

Benzylammonium benzylcarbamate, obtained by the action of 
carbon dioxide on a dry ethereal solution of benzylamine, separated as 
a gelatinous precipitate, which slowly changed to a crystalline mass, 
m. p. 100° (compare Tiemann and Friedlander (Abstr., 1882, 56). On 
heating it yields dibenzylcarbamide. 

Benzhydrylammonium be7izhydrylcarbamate, formed by the action of 
carbon dioxide on benzhydrylamine in ethereal solution, is a white 



1. 16 ABSTRACTS OF OHEmCAL PAPERS. 

substauce which decomposes on warming with water, and has m. p. 
165° (with decomp.). On heating, instead of the expected carbamide, 
there is formed tribenzhydrylamine^ N(CHPh2)jj ; this amine crystal- 
lises in needles, m. p. 144°, and forms a picrate insoluble in benzene. 

Diethylammonium diethylcarhamate was produced by the combination 
of carbon dioxide with the vapour of diethylamine ; it is a white, 
crystalline mass, melting at room temperature, and turning brown 
when kept. If carbon dioxide is led into diethylamine in the liquid 
or dissolved state, the product is diethylammonium hydrogen carbonate^ 
which in a sealed tube melts and decomposes at 70°. if the above 
diethylcarbamate is heated, although the reaction product always 
possesses the characteristic odour of tetraethylcarbamide, no weighable 
quantity of this substance is isolable. 

Hydrazine hydrazinecarboxylate is exceptional in its behaviour, and 
on heating under reflux at 140° gives a practically theoretical yield of 
carbohydrazide (compare Stolle and Hofmann, Abstr., 1905, i, 28) ; 
however, ammonium hydrazinecarboxylate^ an unstable, deliquescent 
substance obtained by the action of ammonia on hydrazine hydrazine- 
carboxylate or on hydrazinecarboxylic acid, behaves analogously to 
the above-mentioned carbamates in being incompletely converted 
by heat into semicarbazide. D. F. T. 

Storage of Calcium Cyanamide in the Tropics. C. J. Milo 
{Chem. Zentr.j 1911, ii, 1655 — 1656; from Med. Proefstat. Java- 
Suikerind., 1911, 3, 311 — 363). — When a concentrated aqueous extract 
of calcium cyanamide is kept for some days, a crystalline, basic calcium 
salt, C(N'CaOH)2, is obtained. The same salt is produced, along 
with cyanamide, dicyanamide, and carbamide when calcium cyanamide 
is kept for a long time in warm, damp air. N. H. J. M. 

Interaction of Thiocyanates and Bromine in Aqueous 
Solution. W. KoNiG {J, pr. Chem., 1911, [ii], 84, 558—560).— 
2^-Bromine in 10% potassium bromide reacts quantitatively with 
aqueous potassium or ammonium thiocyanate in accordance with the 
equation : KSCN -f 4Br2 + 4K^0 = KBr -h CNBr + H.^SO^ + 6HBr ; so 
also does chlorine, but not iodine. The strengths ot aqueous bromine 
or thiocyanate solutions, therefore, can be determined by titration 
with standard potassium hydroxide. C. S. 

Constitution of Aliphatic Diazo-compounds and of Azo- 
imide. Johannes Thiele (Ber., 1911,44,3336. Compare Abstr., 
1911, i, 845). — The author acknowledges that Angeli has previously 
proposed a formula, which contains the group CIN:N, for a diazo- 
compound of indole ; also that he has put forward the formula 
N:NICHo and NrNII^H for diazomethane and azoimide respective^. 

H. W. 

1 : 2-DimethylcycZopropane. Nicolai D. Zelinsky and M. N. 
XJjEDiNOFF {J. pr. Chem., 1911, [ii], 84, 543 — 548).— a-Acetylwopropyl 
alcohol (hydracetylacetone), for the preparation of which an improved 
method is described, is reduced by sodium amalgam and water in an 
atmosphere of carbon dioxide to pentane-j^S-diol, 
OH-CHMe-CHg-CHMe-OH, 



ORGANIC CHEMISTRY i. 17 

b. p. 197-5— 198-57750 mm. or 97—98713 mm., D'f 0-9635, n^ 1-4349, 
which is converted by phosphorus tribromide ab 100°, and finally at 
140°, into ^8-dibromopentane, b. p. 6O712 mm., Df 1-6659, and 
w^ 1-4987. By reduction with zinc dust and 80% alcohol in a freezing 
mixture, the dibromide yields 1 : '2-dimethylcyc\op'opane, b. p. 
32—33°, D^ 0-7025, Df 0-6806, < 1-3763, 'n}^ 1-3823, which is 
oxidised by 1% potassium permanganate, and, in contrast to 1 : 1-di- 
methylcv/c^opropane, reacts slowly with bromine and is sparingly 
soluble in diluted sulphuric acid (2 vols, of acid to 1 vol. of water). 

C. S. 

A Hydrocarbon of the cycloButsbue Series. Edgar Wedekind 
and M. Miller (Ber., 1911, 44, 3285— 3287).— An account of the 
synthesis of 1 : 1 : 3 : 3-tetramethyl-2 : 4-diethylc2/c/obutane. 

1:1:3: 3-Tetramethyl-2 : 4:-diethylcyclobutane-2 : 4:-diol, 

0H-CEt<^^^2>cEt-0H, 

obtained by the interaction of magnesium ethyl bromide and tetra- 
methylc2/c^obutane-2 : 4-dione (Wedekind and^ Weiss wange, Abstr., 1906, 
i, 437 ; Staudinger and Klever, ibid.^ i, 234) is an oil, having an 
aromatic odour, b. p. 128 — 130730 mm., and reacts with hydriodic acid 
to form the corresponding di-iodo-comipound, which on account of its 
instability could not be obtained in a pure condition. When reduced 
with zinc and glacial acetic acid, this yields 1:1:3: 3-tetramethyl- 

2 : 4:-diethylcyc\obutane, CHEt<^pTy|- 2p>CHEt, which is a colourless, 

mobile liquid, b. p. 124 — 125°, and resembles in its chemical behaviour 
a saturated hydrocarbon of great stability. 

1 : 1 : 3 : 3-Tetramethylcyclobutane-2 : A:-diol, obtained in small yield 
by the reduction of tetramethylc2/c^obutane-2 : 4-dione with sodium 
amalgam, and purified by means of its diacetyl derivative, is also 
mentioned. F. B. 

The cycloOGtsjne Series. V. c?/cZoOctatetraene. Richard 
WiLLSTATTER and Ernst Waser [Ber., 1911, 44, 3423 — 3445. 
Compare Abstr., 1905, i, 515; 1907, i, 303; 1908, i, 407; 1910, i, 
366). — a-Dedimethylgranatenine, CgHjjNMeg, was prepared by distil- 
ling in a vacuum the quaternary base obtained from 7t-methylgrana- 
tenine. It unites with methyl iodide to form a quaternary ammonium 
iodide, the hyclroxide of which, on distillation, yields c//c/oo tatrione. 
Two series of attempts were made to prepare C2/c^ooctatetraene from this. 
In the first series bromiue was added, and the dibromocyc/ooctadiene so 
formed heated with quinoiine. In this manner a hydrocarbon of the 
formula CgHg was obtained, which, however, on reduction in the 
presence of platinum black yielded a mixture of dic?/c/ooctane (CgHj^) 
and tric2/cfooctane (CgH^g), thus showing that bridged rings had been 
formed during its preparation, probably owing to the rather high 
temperature employed. The second method was more successful. 
Dibromoc2/c/ooctadiene was converted iuto tetramethyldiaminocyc^o- 
octadiene. When the quaternary base obtained from this was heated 
in the vacuum of a Geryk oil pump, it was split up into trimethyl- 

VOL. CII. i. c 




i, 18 ABSTRACTS OF CHEMICAL PAPERS. 

amine and cyc/ooctatetraene. When the distillation was carried out in 
the vacuum of a water-pump, the hydrocarbon formed contained 
considerable quantities of a dicyclic impurity. 

cycZoOctatetraene, in the presence of platinum black, readily unites 
with 4 molecules of hydrogen. It readily reduces permanganate 
and absorbs bromine. On treatment with nitrosulphuric acid it 
becomes resinified, but yields no nitro-derivative. It passes into more 
stable isomerides by the formation of bridged rings. 

The contrast between the properties of ci/cZooctatetraene and benzene 
leads to a criticism of the formulae propo.'^ed for the litter substance. 
The benzene foimulse of Kekule and Thiele do not express these 
differences. The authors therefore prefer the centric benzene formula 
of Armstrong and von Baeyer, and consider that the centric equili- 
brium of the fourth carbon valencies does not occur in the 

'l\ /"^ case of an eight-carbon ring because the distance of the 
I carbon atoms from the centre is greater than in the case 
/^ of rings of six-carbon atoms. Having preferred the 
centric formula for benzene, the authors are led to propose 
the appended formula for naphthalene. 

The authors have also prepared /3 dedimethylgranatenine by 
complete methylation of methylgranatenine. When treated with 
hydrochloric acid, it yields granatal (A^-c^/c^ooctenone), together with a 
new base which has not been fully investigated. 

iV^-Methylgranatenine was prepared by heating iV-methylgranatoline 
with acetic acid and concentrated sulphuric acid at 180°. It crystal- 
lises readily, and has m. p. 17-2— 17*4°, b. p. 62— 62-2<'/9 mm., and 
186—186-57732 mm. Ciamician and Silber (Abstr., 1894, i, 154) 
give the b. p. 186°. It has Df 0*961. Its picrate^ which decomposes 
at 286°, platinichloi^de, m. p. 221° (decomp.), and methiodide were 
examined. 

a-Dedimethylgranatenine, CgH^^NMeg, obtained by distilling the 
quaternary amnionivm base from i\^-methylgranatenine under diminished 
pressure, is a colourless oil, which has b. p. 71 — 71*5°/8 mm., D" 0*925, 
Df 0*910. When heated at the ordinary pressure, it becomes trans- 
formed into the /S-babe. Its platinichloHde has m. p. 168 — 169°, and 
decomposes at a higher temperature. The methiodide melts at 
172— 173° (decomp.). 

^- Dedimethylgranateniiie was prepared by the complete methylation 
of methylgranatenine. It is a colourless oil, b. p. 218 — 220°/ 
721 mm. When exposed to air it become brown and gradually 
deposits a resin. On treatment with hydrochloric acid, it yields a 
base which has not been completely examined, together with granatal 
(A^ cj/c/ooctenone) (compare Ciamician and Silber, Abstr., 1894, i, 154). 
The constitution of the latter follows from its reduction to cyclo- 
oct^none. The latter has b. p. 78-6— 78*8°/13 mm. and 200—202° 
(corr.)/713 mm. It crystallises readily, and has m. p. 29*5°, which, by 
spreading on clay, is raised to 32*3 — 32*8°. Wallach (Abstr., 1907, 
i, 602) gives the m. p. 25—26°. 

cy cXoOctatriene, obtained by distillation of the quaternary base 
derived from a-dimethylgranatenine under diminished pressure, is 
a colourless, mobile oil, b. p. 147*2 — 148-2(corr.)/ordinary pressure, 



ORGANIC CHEMISTRY. i. 19 

31*2 — 3r8°/8 mm., and 33'5°/ll mm. Its density is much greater 
than that of cj/c^ooctadiene, and somewhat higher than that of 
tropilidene. It has 7i^ 1-52281, < 1-52810, < 1-54131, and 
n^Q 1*55322. On reduction with hydrogen in the presence of 
platinum black, it yielded c?/c/ooctane, b. p. 149 — 150*3° (corr.), m. p. 
11*6 — 11-8° A former pure preparation had m. p. 14° (Abstr., 1910, 
i, 366). On oxidation with concentrated nitric acid, it yielded only 
pure hexane-a^-dicarboxylic acid. 

Bibromocyclooctadiene was prepared by mixing chloroform solutions 
of ci/c^ooctatriene and bromine. On evaporation of the solvent in a 
vacuum, the di bromide remains as a faintly brown-coloured mass, 
which appears to undergo a certain amount of transformation when 
distilled under diminished pressure. It has b. p. 129*5 — 130°/9 mm., 
136 — 137-5°/14 mm. It is very susceptible to the action of air. 
When heated with dimethylamine it yields tetramethyldiaminocyclo- 
octadiene, together with dimethylaminocyclooctatriene. The latter can be 
readily isolated by fractional distillation, and has b. p. 81 — 91°/10 mm., 
D2 0-946, Df 0-936. Its platinichloride has m. p. 200° (decomp.), and 
its methiodide, m. p. 224 — 225° (decomp.). 

Tetramethyldiaminoc^/cZooctadiene is best prepared by the actioa 
of dimethylamine on the undistilled dibromocyciooctadiene dissolved in 
benzene. It is a pale yellow oil, which, on exposure to air, rapidly 
becomes dark brown. It has b. p. 126— 127°/14 mm., D^ 0-944, 
Df 0'935. The product was probably not quite pure. Its platinichloride 
darkens at 210° and decomposes at 220°. Its methohromide has m. p. 
195 — 196° (decomp.), and its methiodide, m. p. 170 — 171° (decomp.). 

The platinichloride of the diammonium base, CgHjQ(NMeg)2ClgPt, 
has no definite melting point, but darkens at 225°. 

On reduction, tetramethyldiaminoc^/c/ooctadiene passes into tetra- 
methyldiaminocyclooctane, a pale yellow oil, b. p. 259 — 261°/718 mm. 
D°0-926,Df 0-913. 

By cautiously heating dibromoc?/6'^ooctadiene with quinoline, a hydro 
carbon was obtained, which had the following constants : b. p 
31-6— 32-8°/10 mm., 142-8— 143-8°/737 mm., D^ 0-927, Df 0*912 
r4« 1*53460, n^ 1-54107, n^ 1*55764, ri^ 1*57243. Analyses agreed 
with the formula CgHg, but the substance is probably not uniform 
since, on reduction by hydrogen in the presence of platinum, it yields 
a mixture of approximately equal quantities of dicj/c^ooctane (C^Hj^) 
and tricyc^ooctane (CgHjg). The reduced hydrocarbon has b. p. 
136°/728 mm. 

For the preparation of cy clooctatetraeney the quaternary ammonium 

base of tetramethyldiaminoc^c/ooctadiene was distilled in the vacuum 

^^of a Geryk oil pump. In this case a temperature of 85 — 95° sufficed 

^^■for decomposition of the base, whilst, when a water pump was used, 

^"heating had to be continued to 110°. The hydrocarbon was obtained 

as a yellow oil of sweet, powerful odour. When exposed to air it 

deposits amorphous, white particles. Two specimens boiled at 

, 36*2— 36*4°/14 mm. and 42*2— 42*4°/l7 mm. respectively. It has 

BD\ 0-943, Df 0-925, < 1-5389. On reduction with hydrogen in the 
presence of potassium black, it yields c?/c/ooctane, b. p. 145 — 147°/ 
pO mm., D:; 0-855, Df 0841. Pure cyc^ooctane has b. p. 147—148°/ 



i. 20 ABSTRACTS OF CHEMICAL PAPERS. 

720 mm. and Df 0*839. Since the cyc/ooctane also could not be 
cryptallised, it was not perfectly pure. On oxidation it yielded 
hexane-a^-dicarboxylic acid. 

cvc^oOctatetraene was kept for three days and then reduced as 
above. The cycZooctane formed was found to contain dicycZooctane. 
The reduction of cyc/ooclatetraene, obtained by heating the quaternary 
base in the vacuum of a water pump, yielded still more unsatisfactory 
results. The product was a mixture of much dicycZooctane with but 
little cycZooctane. H. W. 

Two Methods of Treating the Problem of Substitution in 
the Benzene Nucleus. Arnold F. Holleman {Ber., 1911, 44, 
3556 — 3562). — Mainly polemical. Areply to Obermiller (Abstr., 1911, 
i, 960). Holleman has based his laws of substitution on a study of the 
complete literature, showing that the position taken by a second sub- 
stituting group in the benzene nucleus depends on the group already 
present, and, with but few exceptions, not on the nature of the entering 
group. This is also the case with a third substituting group. 

E. F. A. 

Propenylbenzene from Cinnamylammonium Salts. Hermann 
Emde {Ber., 1911,44, 3224— 3226).— Propenylbenzene, CHPhlCHMe, 
has been obtained by the reduction of quaternary cinnamyl- 
ammonium salts with sodium amalgam (Emde, Abstr., 1909, 
i, 708) with a b. p. as high as 176—177°. The possibility of the 
material so prepared containing allylbenzene or propylbenzene 
is considered ; it was divided into four fractions, and each of 
these decomposed by ozone. In no case was phenylacetaldehyde or 
phenylacetic acid obtained, all four fractions yielding benzaldehyde 
or benzoic acid. Allylbenzene was, therefore, not present, E. F. A. 

Simultaneous Formation of Isomeric Substitution Products 
of Benzene. XVI. The Introduction of a Second Halogen 
Atom into Monohalogenated Benzenes. Arnold F. Holleman 
and T. van der Linden {Rec. irav. chim., 1911, 30, 305 — 380). — The 
authors have studied the chlorination of monochloro- and monobromo- 
benzene, and their bromiuation also, directing the reaction so that only 
one halogen atom enters the benzene nucleus. The amount of each 
isomeride formed has been estimated, and the effect of certain catalytic 
agents (AlCl,, FeClg) on the proportions of the isomerides formed has 
also been studied. 

The method employed for the quantitative estimation of the isomeric 
dihalogenated benzenes in their mixture from the halogenation consisted 
in (1) fractional distillation in a jacketed distilling flask, whereby 
almost all the unaltered monohalogenbenzene is removed. The residue 
is treated with 95'2% sulphuric acid, whereby the last trace of mono- 
halogenbenzene is removed, whilst the dihalogenbenzene is unattacked 
by acid of this strength. It is essential that the acid be exactly this 
strength. This leaves behind a ternary mixture of the ortho-, meta-, 
and para-dihalogenbenzenes, the percentage of each isomeride being 
calculated after determining the initial point of solidification, when 
the para separates, and the second point of solidification, when the 



ORGANIC CHEMISTRY. i. 21 

whole mixture solidifies. Knowing these two values, the amounts of 
each i^omeride in the mixture can be determined from tables and 
curves constructed previously from known mixtures of the pure 
substances. 

Chlorobenzene was chlorinated at a temperature of 60 — 65°, slightly 
more than half the theoretical amount of chlorine being employed. 
In one set of experiments aluminium chloride was the catalyst, and in 
another ferric chloride. The amounts of the three isomerides present in 
the mixture differed considerably from the values given by Mouneyrat 
andPouret(Abstr., 1899,1,263). Only about 5 5% of the meta-compound 
was found, and its presence was confirmed by sulphonating the mixture, 
separating the barium salts of the sulphonic acids by fractional crys- 
tallisation, and from these preparing and identifying the corresponding 
sulphonamides. Two interesting microcrystalline reactions are quoted : 
one with rubidium chloride given by both the meta- and para-bariutn 
salts, and the other with sodium chloride given only by the para-salt. 

Similar experiments were conducted with chlorine on bromobenzene 
and bromine on chloro- and bromo-benzene. For the removal of the last 
traces of bromobenzene a slightly different strength of sulphuric acid 
(95%) must be employed to that for chlorobenzene (95*2%). 

It was found that the results obtained in different experiments, using 
aluminium chloride as catalyst, were not always in agreement. This 
is due to the fact that the aluminium chloride attacks the halogenated 
benzenes to a greater or less extent, and some benzene is produced. 
This is not the case with ferric chloride. 

In chlorinating chloro- or bromo-benzene, aluminium favours the 
formation of the para-isomeride, iron, on the other hand, favouring the 
formation of the ortho. In bromination the reverse is the case. 
Without a catalyst the amounts of products obtained are situated 
between those with aluminium and those with iron. The substituent 
present in the compound has very little influence on the reaction, but 
the substituent entering seems to exert a great influence on the 
amounts of the three isomerides obtained. The amounts of ortho- and 
meta-isomerides seem to increase or diminish together, as opposed to 
the para-isomeride. W. G. 

6-Iodo-l-methyl-3-ethylbenzene and its Derivatives contain- 
ing Multivalent Iodine. Conrad Willgerodt and Max Jahn 
(Annalen, 1911, 385, 328— 340).— By the usual method, 5-ethyl-o- 
toluidine is converted into Q-iodo-l-methyl-3-ethylbenzene, C^HgMeEtl, 
b. p. 242°, which reacts with chlorine in cold acetic acid to form 
^-methyl A-ethylphenyl iododichloride, C^jHgMeEt'lClg, yellow needles. 
Q-Iodoso-l-methyl-o-ethylbemene, CgHgMeEt'IO, decomp. 162°, obtained 
from the iododichloride and 10% sodium carbonate, forms a diacetate^ 
C^H3MeEt-I(OAc)2, m. p. 104°, and is converted by distillation with 
steam into Q-iodoxy-\-methyl-3-ethylbenzene, CgHgMeEt'IOg, which 
explodes at 161°. Equal molecular quantiti^^s of the iodoso- and the 
iodoxy-compounds react with silver oxide and water at 40 — 50*^ to 
form ultimately a solution of di-^-methylA-ethylpheiiyliodonium 
hydroxide, OH'I(C(.H3MeEt)2, from which the chloride, m. p. 148°, 
platinichloride, m. p. 163°, mercurichloride, m. p. 109 — 110°, bromide. 



i. 22 ABSTRACTS OF CHEMICAL PAPERS. 

m. p. 162°, iodide^ m. p. 134", nitrate^ m. p. 150" (decomp.), and 
(lichromate, deconrip. 132°, Jiave been prepared. Jododi-2 -methyl - 
\-ethylphenylxodonium hydroxide, .CgHgMeKt*I(0H)'CrtH2MeEtI, the 
sulphate of which is obtained by the careful addition of the preceding 
iodoso-componnd to concentrated sulphuric acid cooled by a freezing 
mixture, forms a chloride, ra. p. 88°, plaiinichloride, m. p. 110 — 111° 
(decomp.), merctirichloride, m. p. 87°, bromide, m. p. \0\°, iodide, m. p. 
82°, and dichromate, m. p. 52°, resolidifying at 87°. 0'7'olyl-2-methyl'i- 
ethylphemjliodonium hydroxide, C6H4Me*I(OH)*Cgll3MeEt, obtained 
in solution from o-iodoxy toluene and 6-iodoso-l-mfcthyl-3-ethylbenzene 
and moist silver oxide, forms a chloride, m. p. 174°, platinichloride, 
m. p. 174° (decomp.), mercurichloride, m. p. 133°, bromide, m. p. 167°, 
iodide, decomp. 135°, and dichromate, decomp. about 138°. 
2-Methyl-4:-ethylphenyldichlorovinyliodonium chloride, 
CeHgMeEt-ICl-CgHClj. 
m. p. 144°, obtained by triturating 5-ethyl-o-tolyl iododichloride and 
acetylene silver chloride with water (compare Thiele and Haakh, 
Abstr., 1909, i, 865), has been converted into the platinichloride, 
mercurichloride, m. p. 67°, bromide, m. p. 126°, iodide, decomp. 71°, 
nitrate, m. p. 93 — 94°, hydrogen sulphate, m. p. 56°, and unstable 
dichromate. C. S. 

6-Iodo-«/^-cumene and its Derivatives. Conrad WiLLGERODTand 
Robert Meyer {Annalen, 1911, 385, 341 — 351). — 5-Iodo-\l/-cumene, 
CgHgMegl, m. p. 37°, is most conveniently prepared by heating on the 
water-bath a mixture of «/^-cumeLe in petroleum, sulphur iodide, and 
nitric acid, D 1*34. It yields the following derivatives containing 
multivalent iodine. xp-Cumyl iododichloride, CjjH2Meg'IClo, decomp. 
66°; 5-iodoso-\l/cume7ie, C^HgMeg'IO, decomp. 171° {acetate, m. p. 
123°) ; b-iodoxy-xp'cumene, OgH^Meg^IOg, explodes at 210° ; di-if/cumyl- 
iodonium chloride, (CgH2Me3)2lCl, m. p. 107°, and the corresponding 
platiniclUoride, m. p. 159°, aurichloride, m. p. 90°, bromide, m. p. 118°, 
iodide, m. p. 120°, and dichromate, exploding at 120°; 5-iodo-di- 
il/-cumyliodonium chloride, C^HjMeg'ICl'CgHMegl, m. p. 106°, and the 
corresponding platinichloride, m. p. 150°, mercurichloride, m. p. 108°, 
auricJdoride, bromide, m. p. 105°, iodide, m. p. 112°, and dichromate, 
decomp. \\3° ; phenyl-{f/-cumyliodonium chloi'ide, m. p. 186°, and the 
coTTev>^OTidi'\ug platinichloride, aurichloride, m. p. \\1°, mercurichloi^vie, 
m. p. 161°, bromide, m. p. 173°, iodide, decomp. 147°, and dichromate, 
exploding at 184°; p-tolyl-il/cumyliodonium chloi'ide, m. p. 171°, and 
the corresponding platinichloride, aurichloride, w. p. 71°, mercuri- 
chloride, m. \\ 81°, bromide, m. p. 148° iodide, decomp. 108°, and di- 
chromate, decomp. 149°; \p cumyldichlorovinrjliodonium chloride, 

C«H,Me3-ICl-C2HCl2, 
m. p. 169°, and the corresponding ;;/aiinic/<^or/(^, aurichloride, m. p. 134° 
approx., bromide, m. p. 131°, and iodide, m. p. 96°. 

When chlorine is passed into an uncooled solution of 5-iodo- 
i/^>cumene in chloroform, the product is 4 : 6-dichloro-5iodo-il/cumene, 
OgMegCJjI, m. p. 188 — 189°; derivatives of this, containing multi- 
valent iodine, cannot be prepared. C. S. 

Nitroalkylates. Iwan Ostromisslensky (J. pr. Chem., 1911, [ii], 
B4, 495 — 506. Compare this vol., i, 1). — The colorations produced by 



ORGANIC CHEMISTRY. i. 23 

the addition of aliphatic nitro-compounds to organic substances con- 
taining ethylenic linkings are due probably to members of a new class 
of additive compounds, which are analogous to the picrates and which 
the author proposes to call nitroalkylates. 

The tetranitromethanates of pyreoe, acenaphthene, anthracene, and 
naphthalene are relatively the most stable, and are precipitated 
together with their components by the addition of water to their 
dilute alcoholic solutions. The cryo^copic behaviour of their dilute 
solutions in nitrobenzene indicates that the tetranitromethanates are 
almost completely dis^sociated into their components. 

Eeasons are advanced for ascribing the constitution : 

NO, . . • -CR' 

^NOg CR" 

to the nitroalkylates. The following are described : anthranilic 
acid 1 : 3 : 5 - trinitrohenzenate, N'H2'OgH4*C02H,CgET3(N02)3, m. p. 
186 — 187°, orange needles; aminoazobenzene 1:3: d-trinitrobenzenate, 
IS[H2-CgH4-N:NPh,C6H3(N02)3, m. p. 156—157°, orange leaflets; 
phenylhydrazine 1:3:5 - trinitrobenzenate, NHPh*NH2,CgH3(N02)3, 
orange needles ; fluorene ^-1:3:6: 8-tetranitronaphthalenatej 

m. p. 154 — 155°, brownish-yellow needles ; aniline ^-hydroxynitro- 
benzenate, PhNH2,N02'CgH4'OH, m. p. 41 — 42°, pale yellow prisms. 

A list is given of nineteen substances which unite with 2 molecules of 
picric acid or other nitrocompound. It is claimed that the molecules 
of the picric acid, picryl chloride, trinitrobenzene, tetranitronaphthal- 
ene, or other nitro-compound are combined, not with the whole com- 
plex of the ethylenic molecule, but at a definite portion thereof, 
namely, at the ethylenic linking. It is shown, by Zerewitinoff's 
methud with magnesium methyl iodide, than the NH, or NK groups 
in nitroalkylates containing such groups do not experience any 
change, and still retain two and one active hydrogen atoms respectively. 

C. S. 



aK-Diphenyldecane and the Preparation of axo'-Diarylated 
Patty Hydrocarbons. Walther Borsche and J. Wollemann (^er., 
1911, 44, 3185 — 3188). — Sebacyl chloride combines with benzene to 
form diphenyldecanedione, COPh*[CIl2]8*COPh (Auger, Ann. Chim. 
Phys., 1891, [vi], 22, 361), in presence of aluminium chloride, w-benzoyl- 
nonoic acid, m. p. 85 — 86° (Auger, loc. cit.), being also formed. The 
dioxime of the ketone is readily reduced by sodium to the diamine, 
which on distillation of its phosphate forms aK-diphenyl-A*'-decadiene ; 
this, when shaken in methyl-alcoholic solution with colloidal 
palladium and hydrogen, is reduced to aK-diphenyl-n-decane. 

a/c - Dioximino - uk - diphenyldecane, OH*N!CPh*[CH2]8*CPhIN*OE[, 
forms yellowish-white crystals, m. p. 120 — 121°; it slowly decomposes 
when kept. 

aK-Diamino-aK-diphenyldecane is a colourless oil, b. p. 260°/18 mm., 
with a characteristic basic odour ; the dibenzoate forms a colourless 
powder, m. p. 198 — 199°. Dicarbamidodiphenyl decane separates in 
microscopic needles, m. p. 183 — 184°. aK- Diphenyl-^'^'-decadieney 
CHPh:CH-[CH2]6-CH:CHPh, forms large needles, m. p. 53°. With 



i. 24 ABSTRACTS OF CHEMICAL PAPERS. 

two molecules of bromine, a^iK-tetrahroino-aK-dipJienyldecane is obtained 
as a colourless, crystalline mass, m. p. 164 — 165°. 

aK - Dihydroxy - uk - diphenyldecane, OH-CHPh-[CH2]8-CHPh'OH, 
obtained by reduction of diphenyldecanedione with sodium and ethyl 
alcohol, forms colourless, matted needles, m. p. 70 — 72°. 

aK-Diphenyl-n-decane is a transparent, strongly refractive oil, b. p. 
234°/12 mm., solidifying to colourless crystals, m. p. 16 — 17°. 

E. F. A. 

Some Secondary Aromatic Amines Related to Diwopropyl- 
amine. M. C. de Leeuw (Rec. trav. chim., 1911, 30, 239 — 269). — 
The behaviour of some secondary amines, in which one or more of the 
methyl groups of diisopropylamine are replaced by phenyl, as com- 
pared with that of diisopropylamine itself, has been studied. The 
amines experimented with were a-phenylethyli«opropylamine, di-a- 
phenylethylamine, diphenylmethyh'«opropylamiue, diphenylmethyl-a- 
phenylethylamine, and di-diphenylmethylamine. These were all 
prepared by Hofmann's method, namely, the condensation of an alkyl 
halide (1 mol.) with an amine (2 mols.). 

a-Phenylethylisopropylamine, CHMePh'NH'CHMcg, is obtained by 
heating together a-phenylethylamine (2 mols.) and isopropyl iodide 
(1 mol.) in sealed tubes at 100°. The hydrochloride forms colourless 
crystals, m. p. 235*5°. By treatment with potassium hydroxide, it yields 
the base, a colourless, mobile liquid, b. p. 90-5— 92°/20 mm., D^' 0905, 
nL* 1-4996. The picrate has m. p. 157 '5°. The nitrite, m. p. 122°, when 
warmed with water, yields the corresponding nitrosoamine, a pale yellow 
liquid, b. p. 162°/19 mm., Di'' 1034, v}^' 1-52657. 

Di-a-phenylethyl-amine, NH(CHMePh)2 (compare Busch and 
Leefhelm, Abstr., 1908, i, 151), was obtained from a-phenylethylamine 
and a-phenylethyl bromide. With sodium nitrite, it yields a nitroso- 
amine, which was not, however, isolated. 

Diphenylmeihylisopropylamine, CHPh2*NH*CHMe2,„is prepared by 
the condensation of diphenylmethylamine and wopropyl iodide as a 
highly refractive, colourless liquid, which crystallises on cooling, m. p. 
11-5°, b. p. 181-5— 182°/25 mm., Di=^ 1-001, < 1-56015. It yields a 
hydrochloride, m.p. 213 — 214°, which crystallises from water with IHgO. 
The nitrite, m. p. 107°, is very unstable, decomposing if heated in 
benzene solution above 55°, and yielding if heated to fusion the 
corresponding nitrosoamine, m. p. 75°. The picrate has m. p. 
189—190°, and acetyl derivative, m. p. 89-5°. 

DipJienylmethyl-a-pJienylethylamine, CH Phg'NH'CHMePh, results 
from the condensation of a phenylethylnmine and diphenylmethyl 
bromide. It is a colourless liquid, b. p. 234-5— 235°/19 mm., Df "^ 1*060, 
n}?^ 1-59824, and yields a hydrochloride, m. p. 232 5—234°. No 
nitrite could be isolated, but from a solution of the hydrochloride in 
absolute alcohol by treatment with sodium nitrite, the nitrosoamine, 
m. p. 80-5°, was obtained. T\\q picrate, m. p. 1845°, crystallises with 
1 mol. of benzene. 

Di-diphenylmethyl-amine, NH!(CHPh2)2 (compare Friedel and 
Balsohn, Abstr., 1881, 279), was obtained by the action of diphenyl- 
methylamine on diphenylmethyl bromide. The hydrochloride has 
m. p. 200—202°. 



ORGANIC CHEMISTRY. L 25 

It is noticeable that the melting points, boiling points, specific 
gravities, and refractive indices of the bases rise as the base contains 
more phenyl and fewer methyl groups. The basic character diminishes 
with increase in the number of phenyl groups in the substance, as is 
shown by the stability of the hydrochlorides and nitrites towards 
water. None of the bases yielded a picryl derivative with picryl chloride, 
thus resembling ditsopropylamine itself. W. G. 

Optically Active Amino-oxides. Jakob Meisenheimer {Annalen, 
1911, 385, 117 — 155). — The existence of substances of the type 
a : N6co? in enantiomorphous configurations, previously exemplified by 
the methylethylaniline oxides (A.bstr., 1909, i, 20), has been sub- 
stantiated by the isolation of the active forms of /3-naphthylmethyl- 
ethylamine oxide and of kairoliue oxide. According to Jones (Trans., 
1903, 83, 1400; 1907, 91, 1821), substances of the type >C : N 6c(Z 
exist in only one form. The author suggests that in these cases the 
double linking stands in the place of two of the non-ionisable groups, 
whilst in the amino-oxides it is in the place of the linking binding the 
acid group and one of the other four Unkings {loc. cit.). 

Further information is given regarding the methylethylaniline 
oxides. The (i-base is obtained most conveniently by resolving the 
racemic base by means of c^-tartaric acid. The active and the racemic 
modifications of the base have been obtained anhydrous and crystal- 
line ; their composition corresponds with the formula: OINMeEtPh. 
The active forms have [M]d±24° in 1 — 2% aqueous solution, and ±8° 
in I — 2% benzene solution. dL-Hydroxyphenylmethylethylammonium 
d-tartrate, CgliigONjC^HgOg, has m. p. 134—135° and [M]d 81-9° in 
alcohol. 

[With Martha Hofpheinz.] — r-P-Naphthylmethylethylamine oxide^ 
OINMeEt-CioHrjSHgO* »i- P- 7o°, colourless leaflets, is obtained by 
oxidising methylethyl-/?-naphthylamine by Caro's acid at the ordinary 
temperature. It is not resolved by c^-bromocamphorsulphonic acid ; 
the bromocam.phorsulphonate obtained has decomp. 135°, after repeated 
crystallisation, and [M]d + 282°, as against the initial value + 273°. The 
resolution is accomplished by means of the tartaric acids. The racemic 
base and ^/-tartaric acid in alcoholic solution yield d-hydroxy-^-7iaph- 
thyhnethylethy I ammonium d-tartrate,Q^^\\^^0^^(^^]AQOf^j m.p. 132 — 135°, 
decomp. 135° [MJ^ -f- 107-8° whilst \-hydroxy-pnaphthylmethylethyi- 
ammonium l-tartrate, obtained in a similar manner by means of 
Z-tartaric acid, has m. p. 132—135°, decomp. 135°, and [M]d - 107'8° 
in aqueous solution. Each of these tartrates is converted through the 
picrate, decomp. 118 — 119°, and the chloride into the free base, 

C\3Hi^ON,3H20, 
m. p. 67 — 70°, needles; the o(-base and the ^base have [MJj, 4-38° and 
— 39° respectively in aqueous solution. 

[With Jacob Dodonow.] — Kairoline is oxidised by 3% hydrogen 
peroxide at 60 — 65° to v-kairoUne oxide, CjoHjgON, m. p. 124° (decomp. ), 
which is isolated in the form of the hydrochloride, C^oHj30N,H.Cl, 
m. p. 144° (decomp.) (platinichloride, m. p. 153° decomp.), or better as 
the picrate, m. p. 122° (decomp.). The resolution of the r-base is 
effected with extraordinary ease. An alcoholic solution is treated 



i. 26 ABSTRACTS OP CHEMICAL PAPERS. 

with alcoholic rf-tartaric acid, the crystals of Vhydroxykairolinium 
A tartrate which are deposited in 90% yield, are removed, the filtrate is 
freed from the excess of (/-tartaric acid by the addition of aramoninm 
chloride, and is then concentrated and treated with aqueous ammonium 
rf-bromocamphorsulphonate, whereby d-hydroxi/kairolinium d-bromo- 
camphorsxdphonate is obtained in 80% yield. This salt has decomp. 
165° and [M]d + 362°, and is converted as usual through the d-picrate, 
m. p. 126° (decomp.), and d-chloinde, decomp. 138°, [M]d +88°, into 
d-kairoline oxide, CioHjgON,H20, hygroscopic plates, which has 
[M]d + 45° in water and (anhydrous) + 1 34° in benzene. \-Hydroxy- 
kairolinium d-tartratey m. p. 1 45° (decomp), [M]i^ - 48° is converted 
through the \-picrate,vc\. p. 126° (decomp.), and l-c/i/oWc/«, decomp. 138°, 
[M]d-88°, into \-kairoline oxide, C^^H^^Ol^ yE.fi, [M]d-45° in water 
and (anhydrous) - 137° in benzene. 

r-Kairoline oxide reacts with methyl iodide in the presence of 
methyl alcohol to iovm vt. periodide, CjQHjgONIg, decomp. 145°, dimethyl- 
tetrahydroquinolinium iodide, and kairoline ; the last substance is 
optically inactive even when the experiment is performed with 
/-kairoline oxide. Similar products are obtained when methyl sulphate 
is used. C. S. 

Salts and Esters of Alky lam inodithiocarbamic Acids. 
Ernest Fournkau and Vila {Bull Soc.chim., 1911, [iv], 9, 985—989. 
Compare A bstr., 1911, i, 528).— It has been shown (A bstr., 1911, i, 528) 
that alkylaminoacetic acids react with carbon disulphide to give the 
corresponding dithiocarbamates. It is now shown that, if an aryl- 
aminoacetic acid is employed, the product is a thiothiazolone. 

When ethyl or bromophenylacetate reacts with methylamine in 
benzene solution it yields tthyl methylaminophenylacetate, an oil readily 
Faponified by boiling water, b. p. 136°/ 10 mm. This ester reacts in 
ether with carbon disulphide to form 2-thio-4-phenyl-3-methylthiazolone, 

CHPh<^ ^^ , voluminous prisms, m. p. 137°. This, when 

treated with ammonia, does not yield the amide of the corre- 
sponding dithiocarbamic acid, but methylaminophenylacetamide. 
When warmed with sodium hydroxide in alcoholic solution, it yields 
the sodium derivative, C02Na*CHPh*NMe'CS2Na. The potassium 
derivative is prepared in a similar manner. If to a solution of the 
sodium salt in water freshly precipitated mercuric oxide is added, the 
unstable co7npoun(/, (C02Na'CHPh*NMe*CS2)2Hg, is precipitated in the 
form of pale yellow crystals. Orgatio-mercury compounds, such as 
mercuryaniline, behave in the same way as the mercuric oxide. 

If a solution of antimony trichloride is added to a solution of the 
potassium salt in water, there results an ill-defined compound, which 
should theoretically be (C02K-CHPh-NMe-CS2)3Sb, but, judged by the 
estimation of the antimony, seems to correspond more nearly with 
the formula (C02K-CHPh-NMe-CS2)2Sb-OH. This substance is of 
therapeutic interest. W. G. 

Diamidothiophosphorlc Acid. Fritz Ephraim (Ber., 1911, 44, 
3414 — 3416. Compare Abstr., 191 l,i, 284). — Diamidothiophosphoric 



ORGANIC CHEMISTRY. i. 27 

acid is obtained from the compound PCIg'OPh by the addition of 
sulphur, replacement of the chlorine atoms by the amino-group, and 
saponification of the resulting ester. 

Phenyl dichlorothiophosphate, PSClg'OPh, is formed when the 
compound PCl2*0Ph (1 mol.) is heated with sulphur (1 atom) for 
half an hour in a sealed tube at 220 — 230°. Fractional distillation of 
the product gives a colourless, highly refractive liquid, possessing a 
slight but unpleasant odour, b. p. 260° (decomp.) or 133°/22 mm. 
Owing to its insolubility in aqueous solutions, it is practically unacted 
on by dilute acids or concentrated sodium hydroxide. Nitric acid 
(D 1'4) gives rise to phenyl or else nitrophenyl phosphate. When 
dissolved in alcohol and treated with aqueous ammonia (I) 082), 
crystals of phenyl diamidothiophosphate, PS(NH2)2'OPh, are readily 
obtained, m. p. 118°. This compound cannot be hydrolysed by 
boiling with aqueous sodium hydroxide. To bring about hydrolysis, 
it is necessary to mix it with 2*3 mols. of solid sodium hydroxide and 
add a few drops of water ; the heat of solution of the sodium hydr- 
oxide starts the hydrolysis. Addition of acetic acid and alcohol then 
precipitates an oil, which is doubtless diamidothiophosphoric acidy 
PS(NH2)2*OH. It is very unstable, gradually decomposing with 
evolution of hydrogen sulphide, so that it could not be obtained pure. 
The silver salt is characteristic. T. S. P. 

Hydrazidophosphoric Acid. Fkitz Ephraim and M. Sackheim 
(Ber.y 1911, 44, 3416 — 3423) — In order to prepare monohydrazido- 
phosphoric acid, PO(OH)2'N2^8' ^^® authors wished to nitrate 
amidophosphoric acid, PO(OH)2*NH2, and from the nitroamide so 
produced, obtain the hydrazide by reduction (compare the analogous 
process for the derivatives of sulphuric acid, Abstr., 1911, ii, 286). 
Since free amidophosphoric acid is very unstable, the nitration 
experiments were carried out with the phenyl ester, but it was found 
that nitration always took place in the phenyl group, the amido- 
group being split off at the same time. The following method was 
therefore used : Diphenyl chlorophosphate was transformed into the 
hydrazide, from which salts of hydrazidophosphoric acid could be 
obtained by saponification, in accordance with the scheme : 

OP«^(^P^)2 N2H4 ^p^(0Ph)2 NaOH op.^(ONa)2 

Diphenyl hydrazidophosphate, PO(OPh)2*N2H3, is obtained by the 
interaction of diphenyl chlorophosphate (1 mol.) and hydrazine 
hydrate (1 mol.) in alcoholic solution. A precipitate of the hydro- 
chloride is first formed, and water is then added until the precipitate 
dissolves and the liquid becomes milky. On cooling, crystals of the 
desired compound are obtained, m. p. 112°. On hydrolysis with 
solid sodium hydroxide and a few drops of water (compare the 
previous abstract), sodium phenyl hydrazidophosphate, 

OPh-PO(ONa)-N2H3, 
is produced ; it crystallises in needles from alcohol. The disodium 
hydrazidophosphate, PO(OIS'a)2*N2H3, results when the reaction 
mixture is heated for ten minutes, after hydrolysis with the formation 
^f the monosodium salt is complete. It is best prepared by hydrolysis 



i. 28 ABSTRACTS OF CHEMICAL PAPERS. 

of the diphenyl ester with 25% sodium hydroxide under reflux. 
Sodium hydrogen hydrazidophonphate, UNa*PO(OH)'N2H3, on account 
of its sparing solubility, is precipitated from a solution of the normal 
salt by the careful addition of acetic acid. The normal potassium 
salt and the j}0tas8ium hydrogen salt are prepared similarly to the 
sodium salts. Ammonium and barium phenyl hydrazidophosphates, 
OPh-PO(0-NH4)-N2H3 and [PO(OPh)(N2Hg)-6]2Ba, are obtained from 
the diphenyl ester by hydrolysis with concentrated ammonium hydr- 
oxide and barium hydroxide respectively. Barium hydrazidophosphate 
couM not be obtained pure. The lead salts of hydrazidophosphoric 
acid and of phenylhydrazidophosphoric acid are obtained by double 
decomposition of the corresponding sodium salts with lead acetate. 

Free hydrazidophosphoric acid, as also its phenyl ester, were 
obtained in solution by interaction of the lead or barium salts with 
hydrogen sulphide or sulphuric acid. The solutions reduce silver 
nitrate and Fehling's solution with difficulty at the ordinary tempera- 
ture, somewhat more quickly on boiling. The solid acids could not 
be isolated. 

When diphenyl hydrazidophosphate is heated gradually to 150°, 
1 mol. of hydrazine is lost from 2 mols. of ester, with the 
formation of diphenyl hydrazidodiphosphatey 

OPh-PO-NH-NH-PO-OPh. 
This compound forms microscopic needles ; it does not react with 
aldehyde, nor does it reduce alcoholic ammoniacal silver nitrate, so 
that it probably does not possess the formula NH2*N[PO(OPh)2]2. 
It is changed by boiling water in some way, the solution then readily 
reducing silver nitrate. When the hot alcoholic solution is pie 
cipitated with water, hydrazine is split off, the precipitate consisting 
of monophenyl phosphate, P0(0H)2*0Ph (compare Kapp. Abstr., 
1884, 1337). 

Nitration of diphenyl amidophosphate gives rise to a mixture 
of Or and /j-dinitrophenyl phosphates, OII*PO(0'C(;H4*N02)2, which 
melts to a turbid liquid at 95 — 97°, the fusion clearing suddenly 
at 165 — 167° (compare Rapp, loc. cit.). The mixture contains only a 
very small proportion of the ortho-compound (about 0'2%). Sodium 
p-dinitrophenyl phosphate forms light yellow, slender needles ; the 
silver salt forms slender, white needles. T. S. P. 

The Reactions of 4-Nitro8ophenol, 2 : 6-Dibromo-4-nitroso- 
phenol, and 6-Nitro80-m-cresol with Bromine. Henki van Erp 
{Rec. trav. chim., 1911, 30, 270—304. Compare Bridge, Abstr., 1894, 
i, 25 ; Raiford and Heyl, Abstr., 1910, i, 273, 730). — A determina- 
tion of the products obtained by the action of bromine on solutions of 
phenol containing nitrosophenol. From his experiments the author 
draws the conclusion that, when nitrosophenol is treated with excess of 
bromine, the principal product is 2:4: 6-tribromophenol, probably 
formed according to the equation: NO'CgH^'OH-h 8 Br -f 2H20 = 
CgH2Br3-OH-HHN03-l-5HBr. Other products are 4 : 6-dibromo- 
2-nitrophenol, 2 : 6-clibromo-4-nitrophenol, and 2 : 6-dibromo-/?-benzo- 
quinone in small quantity. 

2 :6-Dibromo-4-nitrosophenol was prepared both from the nitroso- 



ORGANIC CHEMISTRY. i. 29 

phenol and bromine (Fischer and Hepp, Abstr., 1888, 456), and by the 
action of hydroxylamine on 2 : 6-dibromo-p-berjzoquinone, and, contrary 
to Kehrmann's results (compare Abstr., 1889, 243), the products in the 
two cases were identical. 

2:4: 6-Tribromo-m-cresol yields an acetate and a henzoate, m. p. 87°. 

The diacetate of 2 : 6-dibromoquinol is obtained in colourless prisms, 
m. p. 116*5°; the dibenzoate has m. p. 136°. 

Dibromodianilino-ip-benzoquinone is obtained by the addition of 
aniline, dissolved in alcohol, to a warm solution of 2 : 6-dibromo-;?- 
benzoquinone in alcohol. It forms an olive-coloured, microcrystalline 
powder, which does not melt at 300° (compare Niemeyer, Abstr., 
1885, 1065). 

By the action of bromine in excess on 4-nitrosophenol in alcoholic 
solution and subsequent distillation in steam, there resulted (1) a non- 
volatile product, which was shown to be 2 : 6-dibromo-4-nitrophenol ; 
(2) a volatile portion, which formed the major part of the products, 
and consisted chiefly of 2:4: 6-tribromophenol with a little 
4 : 6-dibromo-2-nitrophenol. 

Working with water as a solvent instead of alcohol, the products 
were the same, but in this case some 2 : 6-dibromo-p-benzoquinone was 
also isolated. In each case the hydrogen bromide obtained from the 
reaction was in excess of the amount demanded by the equation. This 
the author considers was due to the formation of brominated resinous 
by-products and consequent generation of hydrogen bromide. 

That the 2 : 6-dibromo-4-nitrophenol does not result by isomeric 
change from 4 : 6-dibromo-2-nitrophenol, or vice versa, in this reaction 
is shown by taking solutions of each of these separately in acetic acid, 
gradually adding sodium nitrite, and allowing the solutions to remain. 
After three days the starting materials can be recovered unchanged 
without any trace of the isomeride being present. 

2:4: 6-Tribromophenol is the product of the action of bromine in 
excess on an alcoholic solution of 2 : 6-dibromo-4-nitrosophenol. 
With 6-nitroso-m-cresol, bromine yields 2:4: 6-tribromo-m-cresol. 

W. G. 

Action of Magnesium Ethyl Bromide on Anthraquinone. 
Latham Clarke and Paul Whittier Carleton (J. Amer. Chem. Soc.y 
1911, 33, 1966— 1973).~lt has been shown by Clarke (Abstr., 1908, 
i, 330) that magnesium ethyl bromide reacts with anthraquinone with 
formation of 9 : lO-dihydroxy-9 : 10-diethyldihydroanthracene. A 
further study of this reaction has shown that when the magnesium 
ethyl bromide is in excess, dihydroxydiethyldihydroanthracene is 
formed, but that when the anthraquinone is in excess, ethyloxanthranol 
is produced. 

9 : lO-Dihydroxy-9 : 10-diethyldihydroanthracene hasm. p. 172°, and 
its di7nethyl ethei\ m. p. 178°; the diethyl ether has also been 
prepated. When the compound is treated with acetyl chloride, 
a cream-coloured substance, C^^gH^^^' ^- P- 135-5 — 136°, is produced 
which crystallises in needles and dissolves in methyl alcohol to form a 
solution with a blue fluorescence. By the action of zinc dust and 
glacial acetic acid, the dihydroxy-compound is converted into diethyl- 



i. 30 ABSTRACTS OF CHEMICAL PAPERS. 

anthracene. Wlien the compound is heated with dilute hydrochloric 
acid, a mixture of two isomeric substances, Cg^Hg^O, is obtained. One 

of these compounds, probably ^CHMe:C<^«g4>CEtVo, m. p. 161°, 

forms yellow, rhombic plates, and the other, possibly 

(cHMeEfC^^c)/,, 

m. p. 226°, crystallises in yellow prisms, and gives fluorescent solutions. 
These substances are also formed as by-products in the preparation of 
9 : lO-dihydroxy-9 : 10-diethyldihydroanthracene. E. G. 

Synthesis of Butein. A. Goschke and J. Tambor (Ber., 1911, 
44, 3502 — 3505). — The authors will describe shortly a method of 
synthesising polyhydroxychalkones. Amongst others, butein (Perkin 
and Hummel, Trans., 1904, 86, 1459) has been obtained by treating a 
boiling alcoholic solution of equal molecular quantities of proto- 
catechualdehyde and resacetophenon© with 50% potassium hydroxide. 
The product, which is obtained by acidification and purified through 
the tetra-acetyl derivative, is shown to be identical with natural 
butein by direct comparison. The 4' : 5' -methylene ether, 

CeH3(OH)2-CO-CH:CH-C,H3<^>CH„ 

m. p. 185°, yellow needles, prepared in a similar manner from 
piperonal and resacetophenone, yields 2 : i-dimethoxy-4:' : b'-'Hoxy- 
methylenechalkone, m. p. 168°, by treatment with warm methyl sulphate 
and 50% potassium hy<iroxide. C. S. 

a-MoDypnopinacolin. Maurice Delacre (i5tt/^. Soc. chim.f 1911, 
[iv], 9, 1024 — 1025). — In this preliminary communication it is shown 
that dehydrodypnopinacolin, C32H24O, can be obtained by the oxida- 
tion of a-tsodypnopinacolin, CggHge^* with bromine (compare Abstr., 
1896, i, 662). Oxidation with chromic acid in acetic acid gives 
rise to dehydrodypnopinacone, CggHggOg. The latter by dehydration 
furnishes dehydrodypnopinacolin, and this on treatment with sodium 
amalgam gives a substance, CggHggO, isomeric with dypnopinacolin, 
but which behaves as an alcohol, and with acetyl chloride gives a 
hydrocarbon, which may be isodypnopinacolene (da Costa, Th^se, 1911). 

T. A. H. 

Cholesterol. III. Leo Tschugaeff and P. Koch (Annalen, 1911, 
385, 352—358. Compare Abstr., 1910, i, 734).— Recently several 
investigations of the behaviour of cholesterol and its immediate 
derivatives towards ozone (Molinari and Fenaroli, Abstr., 1908, i, 
882; Doree, Trans., 1909, 95. 638; Diels and Abderhalden, Abstr., 
1904, i, 880 ; Diels, ibid., i, 728) have thrown doubt on the usually 
accepted view that the molecule of cholesterol contains only one 
ethylenic linking. The authors, therefore, have determined the 
molecular refractions of cholesterol, cholestane, cholestene, a-chol- 
esterylene, methyl cholesterylxanthate, and methyl dihydrochol- 



! 



ORGANIC CHEMISTRY. i. SI 

esterylxanthate in benzene, land have obtained values which agree 
closely with those calculated on tlie assumption that only one 
ordinary ethylenic linking is present in the molecule of cholesterol. 

C. S. 



Synthesis of aa-Diaryl Substituted Arabitol, Carl Paal and 
Max Kinscher {Ber., 1911. 43, 3543—3555. Compare Abstr., 1906, 
i, 802). — On treatment of triacetyl-^arabonolactone with magnesium 
phenyl bromide and decomposition of the product with dilute acids, 
aa-dipheD} 1-Z-arabitol is obtained. In a similar manner, aa-di-/>-tolyl- 
and aa-dibenzyl-arabitols have been prepared. 

On benzoylation of diphenylarabitol, which is strongly dextro- 
rotatory, an inactive tetrabenzoyl derivative is obtained, 
HO-CPh2-[CH(OBz)]3-CH2-0-COPh. 

Diphenylarabitol is converted on oxidation into benzophenone and 
aliphatic compounds, of which only mesotartaric acid could be isolated. 
Dilute nitric and other mineral acids eliminate water, forming 

anhydrodiphenyl - 1 - arabitol, C^^H^gO^. 

, : This does not react with aldehyde or 

I H OH j ketone reagents, and when oxidised 

CPhg'C C C'CHg'OH with potassium permanganate yields 

OH H H an acid, Cj^HjgOg, without the elimin- 

(I.) ation of the phenyl groups as benzo- 

phenone. 

j Accordingly, constitution (I), namely, 

I H OH 3 : i-dihydroxy-2 : 2 - diphenyl - 5 - methyl- 

CPhg'C C C — COgH oltetrahydrofuran, is assigned to the 

OH H OH anhydro-compound, whilst the acid is 

(II.) 3:4:5- trihydroxy -2:2- diphenyltetra- 

hydro/uran-5-carboxylic acid (constitution II). 

On rearrangement this acid will form an a-ketonic acid, 
OH-CPh2-CH(OH)-CH(OH)-CO-C02H, 
as witnessed by the formation of a dark red, oily hydrazone or osazone 
on treatment with phenyl hydrazine. 

Triacetyl-l-arabonolactone forms large, transparent, well-formed, 
prismatic crystals with many faces, m. p. 52 — 54°, [aj^'^ -60-45°. 

aa- Diphenyt-\-arabitol separates in small, colourless, ilat needles, 
grouped concentrically, m. p. 171°, [ajo -t-85'6°. 

PySe-Tetrabenzoyl-aa-diphenylai-abitol crystallises in colourless, silky, 
glistening needles, m. p. 181 — 182°, which are optically inactive. 

Anhydrodiphenylarabitol crystallises in transparent, large, thin plates, 
m. p. 172—174°, [a]^ -114-8°. 

3:4: b- Trihydroxy -'2, : 2 -diphenyltetrahydrofuran-6-carboxyliG acid 
forms short, stunted needles, which sinter at 111°, m. p. 117°, 
[a]ll +201-7°. 

aa- Bi-^-tolyl-l-arabitol crystallises in small, glass-like, colourless, flat 
prisms with oblique end faces, in renniform aggregates. It has a 
faint aromatic odour, m. p. 186—187°, [a]J>^ +71-62°. 

aa DibenzylA-arabitol forms transparent, colourless needles, m. p. 
156—157°, [aY^ +31-5°. E. F. A. 



i. 32 ABSTRACTS OF CHEMICAL PAPERS. 

The PolymorphiBm of a//oCinnamic Acid. Julius Meyer 
{ZeiUch. KlektrocJiem.., 1911, 17, 976— 984).— A more detailed account 
of results already published (compare Abstr., 1911, i, 975). 

T. S. P. 

Acylated Salicylic Acids. Alfred Einhorn, Leo Rothlauf, 
and Rudolf Skuffekt {Btr., 1911, 44, 3309— 3313}.— Contrary to 
the experience of Lfissar Cohn and Lowen^tein (Ab-tr., 1908, i, 984), 
Einhorn and Seuffert find that benzoylsalicylic acid [o-benzoyloxy- 
benzoic acid] may be readily prepared by the interaction of benzoyl 
chloride and salicylic acid in pyridine solution or by the action of 
benzoyl chloride on sodium salicylate. It crystallises in needles, 
m. p. 132°. The sodium salt was alno analysed. The pyridine method 
was also found available for the preparation of o-i«ovaleiyloxybenzoic 
acid, m. p. 95°, and of o-cinnamoyloxybenzoic acid, m. p. 150 — 152°. 

Einhorn and Rothlauf have prepared othymylcarhonaiohenzoic acidj 
CgHsMePr-O-CO-O-CgH^-COgH, m. p. 118°, by the action of thymol- 
carbonyl chloride on salicylic acid and dimethylaniline in benzene 
solution, and o-menthylccirbonatohenzoic acidy 

C6H9MePr-0-CO-0-06H4*C02H, 
m. p. 1215°, by mixing sodium salicylate and menthylcarbonyl chloride 
in acetone solution. 

None of these compounds gives a coloration with ferric chloride. 

H. W. 

a-Chloro-/3-phenyl-lactic Acid and Phenylacetaldehyde. 
Berthold Rassow and Fritz Burmeister (J. pr. CJiem., 1911, [ii], 84, 
473 — 489). — By passing carbon dioxide into an aqueous solution of 
potassium hypochlorite and potassium cinnamate and subsequently 
acidifying, the authors obtain crystallised a-chloro-/8-phenyl-lactic acid 
without a trace of oily by-product (compare Erlenmeyer and Lipp, 
Abstr., 1883, 992). The hydrated acid containing HgO has m. p. 
56 — 57°. By keeping over sulphuric acid, it changes to a labile, 
anhydrous acid, m. p. 86^, which in time is converted into a stable 
modification, m. p. 102 — 103° ; the last is also obtained by repeatedly 
crystallising the hydrated acid from dry chloroform. The ammonium 
salt, m. p. 185° (decomp.), and the aniline salt, m. p. 82°, are described. 
Phenylacetaldehyde is best obtained by neutralising an aqueous solu- 
tion of a-chloro-/^-phenyl-lactic acid with sodium hydroxide and subse- 
quently heating ; it resinifies by keeping, and yields a crystalline 
substance, C7H7O, m. p. 148°. C. S. 

The Anhydride of Mandelic Acid. Karl Stutz {B&i\, 1911, 
44, 3485—3487. Compare Biedermann, Abstr., 1892, 473 ; Bischofl: 
and Walden, Abstr., 1894, i, 525 ; Staudinger, Abstr., 1911, i, 308). 
— The vitreous amorphous anhydride of mandelic acid can also be 
obtained by heating the acid with a little sulphuric or hydrochloric 
acid in the steam-oven ; obtained thus, it is soluble in ether, but 
insoluble in cold water and sodium hydrogen carbonate solution. 

Although analysis and the equivalent weight indicate the formula 
CggHggOg, the fact that the action of ammonia yields a larger quantity 



ORGANIC CHEMISTRY. i. 33 

of the amide than this formula would indicate leads the author to the 
opinion that either mandelic acid gives, like salicylic acid, several 
anhydrides, of which the vitreous substance is a mixture, or that the 
vitreous product represents the lactide, CgHgOj, which, on account of 
its amorphous nature, has not yet been obtained free from water. 

D. F. T. 

Additive Products of Derivatives of Trinitrobenzene with 
Some Nitrogenous Aromatic Substances. Roberto Ciusa and 
L. Yecchiotti {Atti E. Accad. Lincei, 1911, [v], 20, ii, 377 — 383. 
Compare Abstr., 1911, i, 810; Sudborough and Beard, Trans., 1910, 
97, 773 J Ciusa and Agostinelli, Abstr., 1907, i, 553 ; Ciusa, Abstr., 
1906, i, 962). — In addition to the additive products with picryl 
chloride formerly described, other compounds have now been prepared. 
Benzaldehyde-/?-nitrophenylbydrazone and picryl chloride form a com- 
pound, CHPh:N-NH-C6H4-N02,2C6H2(N02)8Cl, which crystallises in 
carmine-red needles, m. p. 132°. The compound of benzaldehyde- 
phenylmethylhydrazone and picryl chloride, 

CHPh:N-NMePh,2C6H2(N02)3Cl, 
crystallises in dark red needles, m. p. 65°. The compound of cinnam- 
aldehydephenylhydrazone and picryl chloride has m. p. 122 — 123° 
(formerly given incorrectly by printer's error). The compound of 
m-nitrobenzaldehydephenylhydrazone and picryl chloride, 

N02-C6H4-CH:N-NHPh,C,H2(N02)8Cl, 
forms dark red needles, m. p. 98°. The compound of piperonaldehyde- 
phenylmethylhydrazone and picryl chloride, 

CH2:02:C6K3-CH-N:NMePh,C6H2(N02)3Cl, 
crystallises in black needles with a violet lustre, and has m. p. 1 15°. 

The compound of benzaldehydephenylhydrazone with trinitrotoluene, 
CHPh:N-NHPh,2C6H2Me{N02;': forms dark red needles, m. p. 84°. 

The compound of benzaldehydephenylhydrazone and trinitrophenol, 
CHPh:N-NHPh,2CgH2(N02)3-OH, cr^^stallises in violet-black needles, 
m. p. 117°. 

The compound of o-nitrobenzaldehydephenylhydrazone with trinitro- 
benzene, ISr02-C6H4-CH:N-NHPh,CgH3(N02)3, crystallises in dark red 
needles, m. p. 132°. 

The compound of benzaldehydephenyl-jo-tolylhydrazone with trinitro- 
benzene, CHPh'N:NH-C6H4-Me,2CeH3(N02)3, forms lustrous, black 
scales, m. p. 142°. 

The compound of cinnamaldehydephenylhydrazone and trinitro- 
benzene, Cj5Hi4N2,2CgH.3(N02)3, crystallises in reddish-brown needles, 
m. p. 167°. 

The compound of m-nitrobenzaldehydephenylhydrazone with trinitro- 
benzene, N02-CgH4-CH:iS[-NHPh,C6H3(N02)3, forms dark red needles, 
m. p. 136°. 

The compound of m-nitrobenzaldehydephenylhydrazone and trinitro- 
toluene, NO,-CgH4-CH:N-NHPh,C6H2{N02)3Me, crystallises in red 
needles, m. p!" 105—106°. 

The compound of p-nitrobenzaldehydephenylhydrazone and trinitro- 
benzene, N02-C6H4-CH:N-NHPh,C6H3(N02)3, forms dark red, lustrous 
scales, m. p. 144°. 

VOL. CII. 1. d 



i. 34 ABSTRACTS OF CHEMICAL PAPERS. 

The compound of anisaldehydephenylhydrazone with trinitrobenzene, 
OMe-C6H4'CH:N»NHPb,C«H8(N02)3, crystallises in reddish-brown 
scales, m. \\ 1KJ°. 

The compound of piperoualdehydephenylhydrazone and trinitro- 
benzene, CH2:02:C«H8-CH:N-NHPh,C^.H8(N02)8, crystallises in almost 
black needles with a violet lustre, and has m. p. 147°. 

The compound of benzaklehyde-jo-nitrophenylhydrazone and trinitro- 
benzene, CHPh:N-NH-C,5H4-N()2,CgH3(N02)3, forms red needles, m. p. 
164—165° 

Additive compounds of a very unstable kind were also obtained 
with trinitrophenol and benzaldehydephenylmethylhydrazone, piperon- 
aldehydephenylmethylhydrazone, and m-nitrobenzaldehydephenyl- 
methylhydrazone, as well as from ?n-nitrobeDzaldehydemethylhydrazone 
and picryl chloride. R. V. S. 

Derivatives of c?/cZoPentanone. Marcel Godchot and Felix 
Taboury (Compt. read., 1911, 153, 1010 — 1011. Compare Abstr., 
1911, i, 385). — The ketone prepared by the catalytic bydrogenation of 
cyc^opentanone is shown to be a-c^/cZopentylcycZopentanone by the fact 
that on reduction, it gives a-cyclopantylcyclopeiitanol, CjHg'CgHg'OH, 
needles, m. p. 20°, b. p. 125 — 120°/ 15 mm. ; the phenylurethane has 
m. p. 88 — 89°. This substance has also been prepared by acting on 
cyc/opentanone with sodium ethoxide and reducing the resulting com- 
pound with alcohol and sodium (Wallach, Abstr., 1896, i, 572). 

W. 0. W. 

Products of the Dry Distillation of Calcium Pinate. 
Waldemar Bonsdorff {Ber., 1911, 44, 3208 — 3210). — Calcium pinate 
was expected to yield on dry distillation a cyclic ketone, 

/CH\ CO 

CJiie2< >CH2 I . 

^CH^- CH2 

The actual product wis an oil, distilling between 50° and 100°/8 mm., 
which formed a semicarbazone, CgHj^ONg, crystallising in colouiless 
plates, and yielded an unsaturated ketone on decomposition, probably 

\'isopropyle^i6-2-cyc\opentanoneiCM.Q^,i^<^ Att^- This is a trans- 

parent oil, b. p. 69— 71°/8 mm., Df 0*9355, n^ 1-4666. E. F. A. 

Fluorescence in the />-Benzoquinone Group. M. M. Richter 
{Ber.j 1911, 44, 3469 — 3473). — When chloraniland potassium cyanide 
react in solution in methyl alcohol, there is formed the potassium salt 
of "cyananilic" acid, OgO^NgKg; the same substance is obtained when 
chloranilic acid is used instead of chloranil. These methods of pre- 
paration, together with the properties, show the free acid substance to be 
2 :5dicyano-3 : Q-dihydroxy-^benzoquinone. It is a brown solid, which 
does not crystallise well, and contains two firmly attached molecules of 
water of crystallisation; on heating, it carbonises without melting. 
It is a strong acid, and has a feeble quinone-like odour. Towards 
reducing and hydrolytic agents it is surprisingly stable. It is sparingly 
soluble in most solvents, but all the solutions show a strong fluores- 
cence, the colour of which varies with the solvent. This fluorescence 



ORGANIC CHEMISTRY. i. 35 

(the first case with a /;-beDzoquinone derivative) leads the author to 
prefer the peroxide to the diketone structure for this compound (com- 
pare Kauffmann, Abstr., 1907, ii, 215). The amw,onium salt, which 
exhibits a more beautiful fluorescence than the other ?alts, is precipi- 
tated from solution by concentrated ammonia solution as a dark brown, 
amorphous powder ; the silver salt is also brown. 

Monocbloro-, 2 : 5-dichloro-, and trichloro-/?-benzoquinone also react 
with potassium cyanide, yielding intensely fluorescent solutioos ; the 
product from the last-named is probably identical with cyananilic 
acid. D. F. T. 

Phenanthrene Series. XXXII. Transition from the 
Phenanthraquinone to the Phenanthrene Series. Julius 
Schmidt and Eberhard Sauer {Ber.y 1911, 44, 3241 — 3255. Com- 
pare Abstr., 1911, i, 626). — When reduced with phosphorus and fuming 
hydriodic acid at 140°, 3-nitrophenanthraquinone yields two isomeric 
^-aminophenanthrene hydriodides, of which the less soluble modification 
forms lustrous, rhombohedial crystals, m. p. 140°, whilst the more 
soluble isomeride, which forms the main product, crystallises in slender, 
white needles, m. p. 244 — 245°. Both isomerides on treatment with 
aqueous sodium hydroxide yield the same 3-aminopheDanthrene, m. p. 
87° (Werner, Abstr., 1902, i, 437). 

2:9: \0-Trichlorophenanthrene, prepared by heating phenanthra- 
quinone with phosphorus pentachloride at 200°, crystallises in white 
needles, m. p. 144 — 145°, and on oxidation with chromium trioxide in 
aqueous acetic acid solution yields '2-chlorophenanthraquinone. This 
forms yellowish-red needles, m. p. 252 — 253°, and reacts with 
o-phenylenediamine hydrochloride in alcoholic solution, yielding 

C H CI* CIN 
9-chlorophenanthraphenazinej ^^^ I i^CgH^, crystallising in 

white leaflets, m. p. 238°; the'' oxime, G^JIfi^'NCl, m. p. 170—175°, 

and semicarhazone, Q^^Ii.^fi^fi\ slender, pale yellow needles, m. p. 

220°, are described. 

CIN'OO 
^•Ghloro-?>-hydroicyphenanthrairiazine, ^ifi^^^<^)^,^ -L^ or 

prepared by the interaction of the preceding oxime and semicarbazide 
hydrochloride in alcoholic solution, has m. p. 288° (decomp.). 

2-Chlorophenanthraquinone is oxidised by potassium dichromate and 
dilute sulphuric acid to 4-chlorodiphenic acid (Schmidt and Schall, 
Abstr., 1907 i, 26), which forms a silver salt, m. p. 270° (decomp.). 
When boiled with fuming nitric acid, it yields %chlorodinitrophenan- 
,, . NO.-C.HnCl-CO 
thraqmnone, -vtq A Vr Aq» which forms lustrous, yellow crystals, 

m. p. 274°, and is oxidised by potassium dichromate and sulphuric 
acid to 2'Chlorodinitrodiphenic acid, Ci^H^OgNgCl, m. p. 269°. 

NO 'C H Cl'CIN 
2-Chlorodimtrophenanthraphenazinef ^J^X^jJ X* vr^^^6^4' P^^" 

pared from 2-chlorodiuitrophenanthraquinone and o-phenylenediamine 

d 2 



i. 36 ABSTRACTS OF CHEMICAL PAPERS. 

hydrochloride in alcoholic solution, forms a white, crystalline powder, 
ni. p. 357° 

The interaction of 9 : 9-dichloro-lO-phenanthrone (Schmidt and 
Lumpp, Abstr., 1909, i, 34) or O-chloro-lO-hydroxyphenanthrene and 
alcoholic potassium sulphide yields di-9-h^droxi/-lO-pItenanthryl 

sulphide, ^6^4^cloU\^^ 2^* '^^^^ forms a light brown, crystal- 
line powder, m. p. 223 — 224° (decomp.) ; the dibenzoyl derivative has 
m. p. 262—263° F. B. 

The Methyl-1 :2-benzanthraquinone Group. I. Roland 
ScHOLL and Walter Tritsch {Monatsh., 1911, 32, 9^7—1018. Com- 
pare Bally and Scholl, Abstr., 1911, i, 676, 1097).— The authors 
have attempted with partial success to extend the .anthraflavone and 
pyranthrone syntheses to the above group (compare Scholl, Abstr., 
1910,1,271). 

"I'-Methyl-a iiapkthoylhenzoic acid and the ^:'-m&thyl isomeride were 
obtained by the action of phthalic anhydride and aluminium chloride 
on 2- and 1-melhylnaphthalene respectively; the former product has 
m. p. 190—191°, and the latter 167—169°. 

The latter substance (formula I), on reduction with zinc and acetic 
acid, yields the lactone of u)-hjdroxy-o)-4:'-methyl-a-7iaphthyl-o-toluic 
acid, m. p. 163 — 164°. On the other hand, reduction by sodium 
hydroxide and zinc dust gives m-^'-methyl-a-naphthyl-o-toluic acidj a 
white, crystalline substance, m. p. 183 — 184°; the ammonium salt, 
unlike that of the parent ketonic acid, is easily soluble in water. 
The ammonium f^alt of the ketonic acid, when heated with strong 
sulphuric acid, condenses to 5 - methyl -1:2- henzanthraquinone 
(formula 11). consisting of yellow needles, m. p. 176 — 177°. By 
heating the last with alkali and a little anhydrous sodium acetate, 
simultaneous oxidation and condensation occur, with formation of 
\ :2:\' •.2'-dihemaiithrafiavone (forujula III); this gives orange-red 
crystals from nitrobenzene ; with alkali and sodium hyposulphite it 
gives a vat which dyes unmordanted cotton yellow. 

By careful nitration of 3-methyl-l : 2-benzanthraquiDOue, there is 
obtained \-nitro-b-methyl-\ '.2-henzanthraquinone in yellowish-brown 

crystals, m. p. 248—251° Bromina- 
y/\^ tion produces ^-bromomethyl-i : 2-benz- 

aiithraquinone, yellowish-green crystals, 
m. p. 219—221°, which by methyl- 
alcoholic potash is also condensed to 
dibenzanthraflavone (see above). Fur- 
ther bromination gives rise to a penta- 
bromo-b- methyl -I : 2-dibenzanthraquin- 
one. Careful nitration of the mono- 
bromo-compound yields \-niiro-6-bromo- 
methyl-1 : 2 - benzanthra^uinone, m. p. 
215— 225° (decomp.). 

If l-nitro-5-methyl-l : 2-benzanthra- 
quinone be reduced by phenylhydr- 
azine there is formed Q-hydroxy-i-m^thyl- 




ORGANIC CHEMISTRY. i. 37 

dihydroindoloanthrene (formula lY) ; this substance, which is 
greeo, yields brown solutions. Air oxidises these solutions, giving 
a violet-brown precipitate of A:-methylindoloanthrone, which remains 
unmelted even at 360°. The last substance resembles benzoquinone 
in its behaviour as an oxidising agent, for example, towards phenyl- 
hydrazine and sulphurous acid. In certain aqueous solvents two 
molecules combine with one molecule of water to form a black 
substance, CggHg^OgNg. 



00 A 


10 1 II 


CO 


\l 1 1 JcH 
OH 


(II.) 


(IV.) 




D. F. T. 



no I 

(I.) 

Determination of Unsaturation in Hydroaromatic Sub- 
stances. IsiDOR J. Klimont and Wilhelm Neumann {Chem. Zentr., 
1911, 82, ii, 953 ; from Pharm. Post, 44, 587— 588).— A decigram of 
the terpene is dissolved in chloroform, and a known volume of an 
aqueous solution of potassium bromate (1 mol.) and potassium 
bromide (5 mols.) is added, followed by sulphuric acid (50%). 
Potassium iodide is added in known excess, and the iodine liberated is 
titrated. T. A. H. 

Catalytic Reactions at High Pressures and Temperatures. 
XXIV. Hydrogenation of the Terpen es. Wladimir Ipatieff 
and G. Balatschinsky {Ber., 1911, 44, 3461— 3466).— The experi- 
ments were carried out with nickel oxide as catalyst, the iuiti;il 
pressure of the hydrogen being 100 — 130 atmospheres. 

In the hydrogenation of the terpene ketones the double linkings 
add on hydrogen at 220 — 240°, irrespective of whether they are 
situated in the nucleus or in the side-chain. The reduction of ihe 
carbonyl group takes place at 260 — 280° ; in the menthol series the 
temperature must not exceed 260°, otherwise menthane is formed. 
The optical rotation of the compounds produced is all the greater the 
lower the temperature of hydrogenation. 

The above conclusions are drawn from the following experiments : 
at 280°, carvone gives carvomenthol, from which a mixture of two 
menthenes was obtained by loss of water in the pressure apparatus at 
365°, with alumina as the catalyst. At 220° and 240°, carvomenthone 
was formed from carvone, the specific rotation of the product being 
greater at 220° than at 240°. At 280° pulegone gives menthane, 
but at 220 — 240° menthone is produced. At 250°, menthone gives 
menthol on prolonged hydrogenisation. Thymol gives i-menthol at 
260°, m. p. 9°, D20 0-8970, no 1-45659. T. S. P. 

Action of Nitrosyl Chloride on the Essential Oil of 
Bupleurum fructicosum. Nitroso-chlorides. Derivatives and 
Decomposition Products. Dihydrocuminaldehyde. III. Luiqi 
Francesconi and E. Sernagiotto {Atti R. Accad. Lincei, 1911, [v], 20, 
ii, 388— 392.2LCompare Abstr., 1911, i, 1000).— When the nitroso- 



I 38 ABSTRACTS OF CHEMICAL PAPERS. 

chloride previously described is warmed with 25% acetic acid a 
vigorous decomposition occurs, accomj^anied by the evolution of gas, 
chiefly hydrogen chloride. When the product is distilled with steam 
the non-volatile portion is a nitrogenous suhsf.ance, m. p. 68°. The 
part volatile with ateaui is an oil, a portion of which readily yields a 
bisulphite compound, and behaves in other respects as an aldehyde. 
On oxidation with silver oxide, it yields cuminic acid, and is regarded 
by the authors as a dihydrocuminaldehgde. It has the formula 
C,oH,40, b. p. 136—140715 mm., D^3 0-9825, n„ 1-5280— 1-5305, 
and is dextrorotatory. The semicarhazone crystallises in silvery 
laminae, m. p. 197 — 198°. The aldazine, {C-^qH.^^^)2, forms yellow 
plates, m. p. Ill — 112°. The pheni/lhydrazone, Cj^^HgoNg, has m. p. 
123 — 126°. The ^-bromopheni/lhi/drazonet CjgHjgNgBr, crystallises in 
pale yellow laminae, m. p. 127 — 129°. The semicarbazone and 
especially the two hydrazones are phototropic, and all the compounds 
mentioned are dextrorotatory. R. V. S. 

Essential Oil of Litsea odorifera Leaves. Pieter van 
RoMBCROH {Proc.K.Akad, Wetensch. Amsterdam^ 1911, 14, 325 — 327). — 
The oil, known as" trawas oil " in Java, has D'' 0-836— 0846, a^ - 10' 
to -7° in a 20 cm. tube, and boils mostly at 120 — 125°/10 mm. 
pressure or at 233°/760 mm. ; it is pale yellow and possesses a dis- 
agreeable odour. 

The oil contains Z-methyl-7i-nonylcarbinol, ao — 5°40' (compare Power 
and Lees, Trans , 1902, 81, 1593), \-undecenyl alcohol^ 

CH2:CH-[CH2]7-CHMe-OH, 
D^o 0-835, b. p. 233°, a„-5°10', and undecencme, CH2:CH-[CH2]7-COMe, 
m. p. - 7°, b. p. 235°, D"-'' 0-848, MR = 52-47 (calc. for CnHgoO = 52-51), 
which yields a semicarbazone ^ m. p. 116°, and a dibromide, b. p. 
204°/15 mm. From the latter the unsaturated ketone can be recovered 
by treatment with zinc dust and alcohol. T. A. H. 

Essential Oil of Santolina chamsecyparissus. III. Formula 
of Santolinenone, Cj^H^gO. Luigi Francesconi and P. Scarafia 
(Aiti R. Accad. Liiicei, 1911, [v], 20, ii, 383—387.. Compare Abstr., 
1911, i, 1001). — The authors discuss the constitution of the ketone, 
CiqHj^O, obtained from this essential oil, and assign to it the formula 
of A' "-menthene-2-oiie. R. V. S. 



Fresh Dammar Resin from Central Borneo. Em. Gottlieb 
(Arch. Pharm., 1911, 249, 701— 705).— This variety of dammar is 
known in Borneo as " Dammar Daging," and is possibly derived from 
Retinodendron Rassak. The figures in brackets give the percentage of 
the material dissolved by the solvents named : alcohol (82), methyl 
alcohol (70), acetone (60), chloroform (18). The resin had the 
following constants : acid number, direct, 1400 — 142*0, indirect, 
148-4—151-2; saponification value, cold, 159-6 — 162-4, hot, 
163-5- 165-2. 



ORGANIC CHEMISTRY. i. 39 

The portion soluble in ether yielded in turn to (a) sodium carbonate 
solution {\%), (laying olic acid, O^^^fi^, m. p. 170°, and {b) potassium 
hydroxide solution (1%), digingolic acid, CjgHggOg, m. p. 125 — 126°. 
The residue, freed from ether, yielded on steam distillation an essential 
oil and dagingoresen, CggHggO. The two acids and the resen give 
phytosterol-like colour reactions with the usual reagents. T. A. H. 

Recent Fossil Dammar Resin from Central Borneo. Em. 
Gottlieb {Arch. Fharm., 1911, 249, <05 — 710). — The following figures 
give the percentage solubilities of the resin in the solvents named : 
ether (65), acetone (40), turpentine oil (35), alcohol (28). 

The portion soluble in ether yielded to [a) ammonium carbonate 
solution (1%), a resin acid, CigH^gO^, m. p. 135°, (b) sodium carbonate 
solution (1%), a resin acid, Cj^Hg^^Og, m. p. 103 — 105°, (c) potassium 
hydroxide solution (1%), a resin acid, G^^^^^O^, m. p. 120 — 122°, and 
the residue on steam distillation furnished essential oil and an impure 
resen. 

The portion insoluble in ether was dissolved, in part, on further 
addition of alcohol, and from this, by means of potassium hydroxide 
solution, a substance, CJ2H22O, was obtained, leaving a resen, 052^22^2- 
The three acids and the resene all gave phytosterol-like colour reactions. 
The resin contained a bassorin-like substance. T. A. H. 

Decomposition of Gynooardin by the Enzyme of the Leaves 
of Pangium edule. Anne W. K. de Jong {Eec. trav. chim., 1911, 
30, 220 — 221). — Gynocardin is decomposed at the ordinary tempera- 
ture by the enzyme, giving dextrose and a. compound, C^HgO^, according 
to the equation: C13H19O9N + HgO^C^H^gO^ -f-HCN -fCetlgO^. This 
substance, CgHgO^, is a diketone, and yields a phenylhydrazone, which 
decomposes at 177°. 

If the fermentation takes place in a closed vessel, and the quantities 
of hydrogen cyanide and the diketone formed are estimated from time 
to time, the yields are a maximum after four hours, and then they 
diminish proportionately. The specific rotatory power also diminishes 
with the duration of the reaction. W. G. 

Saponins. Ernst Winterstein and H. Blau [Zeitsch. physiol. 
Chem., 1911, 75, 410 — 442). — Saponin prepared from Sapindus utilis 
forms, on hydrolysis with sulphuric acid, laevulose, arabinose, and 
rhamnose ; dextrose and galactose do not appear to be formed. 
Lsevulose is split off by dilute mineral acids at low temperatures, and 
also a small quantity of an amorphous product which, by the action of 
stroni>er acids at higher temperatures, produces arabinose and rham- 
nose. This amorphous substance, " pentoside," still belongs to the 
group of the glucosides, and differs from saponin by being insoluble 
in water, and its great solubility in alcohol. Its decomposition by 
strong acids into arabinose and rhamnose is accompanied by the 
formation of a crystalline compound, to which the formula CjgHggOg 
has been given. This is the true sapogenin ; it gives, on distillation 



i. 40 ABSTRACTS OF CHEMICAL PAPERS. 

with zinc dust, higher hydrocarbons, and also a gas which consists 
partly of butylene. 

Sapogenin forma a nionomethyl and monoacetyl compound. By 
acetylation saponin ia greatly affected in its chemical constitution and 
physiological action. 

Saponin from horse chestnut gives, on hydrolysis, sapogenin, 
arabinose, dextrose, and Isevulose. H. B. H. 

The Constitution of Xanthotoxin and its Relationship to 
Bergaptene. Hermann Thoms [with Hans Preis] (Ber., 1911,44, 
3325 — 3332). — Two crystalline substances have been isolated from the 
residue left after the steam distillation of the fruit of Fagara 
Xanthoxyloidea. One of thes-e, m. p. 190 — 191°, has been shown to be 
identical with bergapten obtained from oil^of bergamot. The second 
substance, xanthotoxin, CjgHgO^, has m. p. 145 — 146°. On nitration 
in acetic acid solution, xanthotoxin yields nitroxanthotoxin, CjgH^O^N, 

m. p. 233°, whilst, when treated with 

OMe methyl iodide in methyl-alcoholic alkaline 

/\ solution.it becomes transformed into 7^i«i/i2//- 

(^jj/ ^*| 1'^ i xanthotoxic acid, C-^^H^fi^'CO^H , m. p. 

\CH*\/'CH^CH 114— 117°, and 7we%/ methylxanthotoxate, 

m. p. 44°. When fused with potassium 

hydroxide, xanthotoxin yields pyrogallolcarboxylic acid. From these 

experiments the annexed formula is proposed. A pharmacological 

comparison of the effect of xanthotoxin and bergapten on fishes shows 

the former to be the more powerful poison. H. W. 

Chlorophyll. XVII. Absorption Spectra of the Com- 
ponents and of the Primary Derivatives of Chlorophyll. 
EiCHARD WiLLSTATTER, ARTHUR Stoll, and Max Utzinger (Aunalen, 
1911, 386, 156— 188).— The absorption spectra of the following 
substances in ether (0*03 — 0*04 gram per litre) have been measured : 
chlorophyll a andj6, methylchlorophyllide a and b, phseophytina and b, 
methylphseophorbide a and b, phytochlorin e andy", and phytorhodin g. 
The authors find that chemical methods are more sensitive than 
spectrum analysis for the examination of chlorophyll derivatives ; 
thus the presence of a little chlorophyll a in chlorophyll 6, or vice 
versa, cannot be detected by the spectrometer, neither are the changes 
through which chlorophyll passes in its conversion into the feebly 
basic products of hydrolysis betrayed by the absorption spectra ; 
phytochlorin e and / show almost identical spectra in spite of their 
great chemical dissimilarity. 

The absorption spectra of chlorophyll a and b respectively exhibit 
very slight differences from those of the methylchlorophyllides a and b. 
The same is true for the magnesium-free derivatives of the four 
substances, namely, the phaiophytins a and b and the methylphseo- 
phorbides a and b. Willstatter and Benz's crystallised chlorophyll 
(Abstr., 1908, i, 199) is a mixture of ethylchlorophyllides a and b, rich 
in the former. 

The absorption bands in the spectrum of phytochlorin e show, in 
intensity, brc^adth, and position, a remarkable similarity to those in 



ORGANIC CHEMISTRY. i. 41 

the spectrum of phseophytin a\ also the comparatively simple 
spectrum of phytorhodin g is nearly related to the far more com- 
plicated spectrum of phseophytin 6, or of methylpheeophorbide h. 
These similarities are very remarkable when the differences in the 
compositions of the substances are considered. The absorption spectra 
of phytochlorin e, phytorhodin g, and isochlorophyllins a and h (Abstr., 
191 l,i,659)in dilute methyl-alcoholic potassium hydroxide are described, 
and the constitutions of chlorophyll derivatives containing potassium, 
zinc, iron, or copper in place of the magnesium of the natural product 
are discussed. C. S. 

Chlorophyll. XVIII. Reduction of Chlorophyll. Kichard 
WiLLSTATTBR and Yasuhtko Asahina {Annalen, 1911, 385, 
188 — 225). — Malarski and Marchlewski have shown that chlorophyll- 
pyrrole and hsemopyrrole yield identical azo-compounds with diazonium 
salts (Abstr., 1910, i, 692). With the primary object of comparing 
these two pyrroles, the authors have reduced (i) hsemin by hydriodic 
acid, D 1*96, and phosphonium iodide by a modification of Nencki 
and Zaleski'ri method, (ii) hsematoporphyrin by Piloty's method 
(Abstr., 1909, i, 539), and (iii) various chlorophyll derivatives 
(phytochlorins, phytorhodins, ethylchlorophyllides a and 6, but best 
of all, phylloporphyrin) by both methods. In each case the reduction 
products are basified by sodium carbonate and distilled with steam, 
and the ethereal extract of the bases is freed quantitatively from 
pyrrolines and pyrrolidines by sodium dihydrogen phosphate, and is 
finally separated into three substances, hsemopyrrole, ^sohsemopyrrole, 
and phyllopyrrole, by fractional salt-formation with ethereal picric 
acid (compare this vol. i, 50, 56). 
OMe'CFt 

Haemopyrrole, NH< * i , b. p. 1987730 mm. or 86—87°/ 

12 mm., T>1 0*930, and Df 0*918, which resembles most closely the 
''hsemopyrrole" of the literature, is a colourless liquid, which resinifies 
rapidly in the air, and responds to the pine-shaving and to Ehrlich's 
dimethylaminobenzaldehyde tests for pyrroles ; it forms a picrate, 
in. p. 111° (corr.), chloropicrate, m. p. 123° (decomp.), and styphnate, 
CgHigNjCgHgOgNg, m. p. 120 — 121° (decomp.) (styphnic acid forms 
with pyrroles salts which are better suited than the picrolonates for 
the identification of the bases, on account of their stability, sparing 
solubility, and crystallisability), and reacts with nitrous acid to form 
an oxime^ m. p. 201°, of methylethylmaleinimide. 

I isoHaemopyrrole, ^^Knjr^^n^^^ ^' P- 16—17°, b. p. 198°/ 

725 mm. or 88°/ll— 12 mm., Df 0-915, is a colourless liquid with a 
characteristic odour. It exhibits the colour reactions of pyrroles, 
reddens and resinifies in the air, and forms a picrate, m. p. 119°, 
chloropicrate, m. p. 126°, and styphnate, m. p. 136°, decomp. 140°. 
With nitrous acid it forms an oxime, m. p. 221 — 222° (corr.), of 
methylethylmaleinimide. It is reduced by hydriodic acid and 
phosphorus at 240° to a mixture of the pyrroline and the pyrrolidine, 
which is completely reduced by hydrogen and platinum to i^ohaemo- 



i. 42 ABSTRACTS OF CHEMICAL PAPERS. 

pyrrolidtM, CgHj^N, b. p. 155— 156°/730 mm., DJ 0845, Df 0-830 
{pl<Uinichlorid€t m. p. 191 — 192°; a-naphthylcarhamide, m. p. 138°). 

PhyllopyrroU, NH<^^^:^^®, m. p. 63°, b. p. 2137725 mm. or 

1)2—93712 mm. (m. p. 66—67° b. p. 88— 90°/ 10 mm., when obtained 
from chlorophyll cUrivativea), white leaflets, resinifies rapidly in the 
air, and does not react with a pine-shaving or dimethylaminobenz- 
aldehyde or with mercuric chloride. It forms a pico'nte, m. p. 95°, 
and yields by reduction (as above) phyllopyrrolidine^ CgHj^N, b. p. 
160—161°, Df 0-824 (a-naphthylcarbamide, m. p. 145°). C. S. 

Anthocyanins. I. An Anthocyanin-like Oxidation Product 
of Quercitin. Maximilian Nierenstein and Muriel Wheldale 
{Ber., 1911, 44, 3487—3491. Compare this vol., ii, 80).— The red, 
violet and blue colouring matters of flowers are regarded as oxidation 
products of the tannins ; they are also related to the yellow plant 

dyes. On oxidation of quercetin with 
O O chromic acid in acetic acid solution, 

xx/^/\/\ p XT /OTT^ fiff^fcetonti (annexed formula), crystal- 

I I lloTT ^ lising in small, deep red needles, 

\/\/ m. p. above 360°, is obtained. Like 

Q CO anthocyanin, it dissolves in alkali 

hydroxides with a blue, and in concen- 
trated sulphuric acid with a red, coloration. 

It could not be methylated or acetylated ; the tetrahenzoylquercetone, 
prepared by the action of benzoyl chloride on quercetone dissolved in a 
mixture of quinoline and pyridine, crystallises in small, pointed needles, 
m. p. 281 — 283°. On fusion of quercetone with alkali, protocatechuic 
acid was obtained. 

When heated with acetic anhydride and zinc dust, acetylated hydroxy - 
TT^ ^ quercetin is obtained as a colourless, 



,/\/\ 



amorphous powder, yielding on hydro- 



HO,^ I |l ^6^s(^H)2 ^y^^^ 1:3:4:3': i' -ptntahydroxyjlavonol 



V XV yOH (annexed formula). This crystallises 

^^ \^ in small, yellow, microscopic needles, 

which lose a molecule of water at 
160°, m. p. 352 — 355°. Both alkali hydroxides and sulphuric acid 
dissolve it with a yellow coloration. 1 : 3 : 4 : 3' : 4'-/*«n^a/«e^Ao.T.?/- 
flavonol forms small, colourless needles, which sinter at 136 — 138°, 
m. p. 147 — 149°. It is probably converted into veratric acid when 
heated with alcoholic potassium hydroxide at 170°. E. F. A. 

Melanins. Maurice Piettre {Compt. rend., 1911, 153, 1037 — 1040. 
Compare Abstr., 1911, ii, 1006). — The melanin fiom Sepia officinalis 
on hydrolysis with sulphuric acid gives tyrosine, leucine, amorphous 
amino-acids, and an insoluble pigment. After alkali hydrolysis, 
alanine and amorphous amino-acids are obtained, together with a 
pigment which is readily soluble in alkalis*. Artificial melanin, 
prepared by the action of Russula extract on tyrosine, gave no 
tyrosine on hydrolysis ; leucine, however^ was recognised amongst 
the products. The two melanins, therefore, resemble those already 



ORGANIC CHEMISTRY. i. 43 

examined, in containing a protein group united to a pigment. The 
name melainin is suggested for the latter substance. W. O. W. 

The Composition of Tannin. Leo F. Iljin {Ber., 1911, 44, 
3318 — 3319). — The author points out that the hygroscopic nature of 
tannin may account for the differences in the analytical results 
obtained by him and by Steinkopf and Sargarian (Abstr., 1911, 
i, 1004). He quotes an experiment which shows the great readiness 
with which moisture is absorbed by tannin. H. W. 

Carboxonium Compounds. Friedrich Kehrmann and Joseph 
Knop {Ber., 1911, 44, 3505—3513). — The reaction between ethereal 
magnesium phenyl bromide and 3 : 6-dimethylxanthone in benzene 
leads ultimately to the formation of ^-phenyl-'^ : 6-dimethylxanth-hydrol, 

CeH3Me<^^^^ ^-^^> CgH3Me, m. p. 152° (corr.). The fact that this 

substance forms an anhydrous, blackish-green, crystalline iodide^ 
CgiHj^OI (and also the corresponding bromide and chloride), which is 
remarkably stable in the presence of water, is regarded as additional 
evidence that such coloured halides are oxonium salts, not quinonoid 
carbonium salts, as stated by Gomberg and Cone (Abstr., 1910, i, 55). 
Still more stable is the chloride of methyl d-phenyl-3 : Q-dimethyl- 

xanthonium-o-carhoxylate, COgMe-CgH^'C^^^'jj^^^^Q.Cl^ orange- 
yellow needles, which is prepared by saturating a cold methyl-alcoholic 
solution of 3 : 6 dimethylfluoran with hydrogen chloride ; the corre- 
sponding bromide, iodide, and platinichloride are described, as also are 
the chloride, bromide, and platinichloride of the corresponding ethyl 
ester. 

9-Phenyl-2 : 1 -dimethylxanth-hydrol, obtained by the oxidation of 
9-phenyl-2 : 7-dimethylxanthene, forms oxonium salts, which are 
redder than those of the preceding isomeride, and are completely 
hydrolysed by water; the ferrichloride, CgiH-^^OCljFeClg, crystallises 
in orange-red prisms. C. S. 

Studies in the Coumarone Group. Josef Tambor [with S. 
GuNSBURG, O. Keller, Chanschy-Herzenberg, B. Rosenknopf, and 
J. Lichentenbaum] {Ber., 1911, 44, 3215— 3223).— Alkyl ethers of 
1-hydroxybenzoylcoumarone are obtained (1) by the action of alcoholic 
potassium hydroxide on o-acetoxychalkone dibromides ; (2) by the 
interaction of coumarilyl chloride with phenol ethers and aluminium 
chloride (Zwayer and Kostanecki, Abstr., 1908, i, 443), and (3) by 
the condensation of salicylaldehyde with a-bromoacetophenone in 
alcoholic alkaline solution. A number of substituted 1-benzoyl- 
coumarone derivatives have been prepared by these methods. 

%Rydroxy-2' : b' -dimethoxychalkone, 

OH-0,H4-CH:CH-CO-CoH3(OMe)2, 
from quinacetophenone dimethyl ether and salicylaldehyde, crystal- 
lises in orange prisms, m. p. 119'5°. Neither the acetate nor 
the dibromide is crystalline. 



i. 44 ABSTRACTS OF CHEMICAL PAPERS. 

2' : b'-Diiiiethoxy-\ -benzoyl coumarone^ 

C,H4<^^>C-CO-CoH3(OMe)2, 

crystallises in yellow plates, m. p. 98° which when moistened with 
concentrated sulphuric acid become dark red, and give an orange 
solution. The 2)/ienylhydrazo7ie crystallises in slender needles, 
m. p. 161°. 

a-Bromo-S : 5-dimethoxyacetophenone, CgHj(OMe)2'CO*CH2Br, from 
quinol dimethyl ether, bromoacetyl bromide, and aluminium chloride, 
crystallises in colourless needles, m. p. 91°. It condenses with salicylic 
aldehyde to form dimethoxybenzoylcoumarone. 

2' : A'-Diethoxy-\-benzoylcouma7'one, from resorcinol diethyl ether 
and coumarilyl chloride, crystallises in almost colourless prisms, 
m. p. 87°. The crystals are coloured orange by concentrated 
sulphuric acid. 

2-I/ydroxy-2' 'A'-diethoxychalkone crystallises from dilute alcohol in 
greenish-yellow prisms, and from concentrated alcohol in sulphur-yellow 
needles, m. p. 164° (decomp. and green coloration) in each case. 
With concentrated sulphuric acid, the crystals become yellow. 

2-Acetoxy2' : A! -diethoxychalkone forms small, colourless needles, 
m. p, 69° 

2-IIydroxybenzylidene-bis-2' : A:' -diethoxyacetophenone^ 
HO-C6H4-CH[CH2-CO-C,H3(OEt)2]2, 
from salicylaldehyde and resacetophenone diethyl ether, separates in 
greenish-yellow needles, m. p. 75°. 

On bromination of 2-acetoxydiethoxychalkone, 2-acetoxy-2' : 4'-(/i- 
ethoxy-5'-bromochalkone dibroniide is obtained in colourless prisms, 
m. p. 139°. 

^'-Bromo-2' :4:'-diethoxy-l-benzoylcoumarone, obtained by the action 
of potassium hydroxide on the foregoing and also on brominating 
diethoxybenzoylcoumarone, crystallises in colourless prisms, m. p. 143°. 

Resacetophenone diethyl ether and 5-bromosalicylaldehyde condense 
to form 5'bromo-2-hydroxy-2' : 4c'-diet/ioxychalkone, 

OH-CoH3Br-CH:CH-CO-CgH3(OEt)2, 
which crystallises in lustrous, yellow needles, m. p. 175° (decomp.). 
The acetyl derivative forms lustrous, ligtt yellow needles, m. p. 1 12°. 

b-Br<ytno-2-aceloxy-2' :A'-diethoxychalkone dibromide gives colourless, 
rhombohedric crystals, m. p. 147". 

b-Bromo-2' li'-diethoxy-l-benzoylcoumarone forms colourless, riiombo- 
hedric crystals, m. p. 126°, which are coloured red by concentrated 
sulphuric acid ; the compound is totally different from the isomeric 
5'-bromo-derivative just described. 

b-Methoxy-2 : Sdiinethylcoumarilyl chloride forms faintly green- 
coloured needles, m. p. 137°. 

Condensed with auisole and aluminium chloride, 5 :i' -dimethoxy-l- 
benzoyl-2 : "d-dimethylcoumarone^ 

OMe-C6H2Me<^^^C-CO-C6H4-OMe, 

yields lustrous, colourless needles, m. p. 145°. 

5:3': A'-Trimethoxy-\-benzoyl-2 : 'S-dimethylcoumarone forms lustrous, 
colourless needles, m. p. 156°. 



ORGANIC CHEMISTRY. i. 45 

5:2': i'-Trimethoxy-\-benzoyl-2 : ^-dimethylcoumarone crystallises in 
yellow needles, m. p. 115°. 

5:2': 6'-Trimethoxy-l-benzot/l-2 : S-dimethylcoumarone separates in 
yellow cubes, m. p. 135°, 

5 : 2' : 4' : Q'-Tetramethozy-l-henzoyl-2 : 3-dimethylcoumarone crystal- 
lises in well-formed, yellow, prismatic columns, m. p. 196 — 197°. 

5 : 2' : 3' : ^'-Tetramethoxy-\ -benzoyl -2 : 3-dimethoxycoumarone forms 
slender, yellow needles, m. p. 158°. 

5-Methoxy-2-methylcoumariliG chloride forms green needles, m. p. 
104 — 105° It has been condensed with phenol methyl ethers 
to form the following compounds : 

5 : 4:'-Dimethoxy-l-benzoyl-2-methylcou7narone forms pale yellow 
platelets, m. p. 140°. 

6 :3' :4:'-Trimethoxy-l-benzoyl-2-methylGOU7naroHe crystallises in small, 
colourless platelets, m. p. 153 — 154°. 

5 : 2' : 4' : 6'-Tetramethoxy-l-benzoyl-2-methylGoumaron6 crystallises in 
dark yellow, microscopic plates, m. p. 178°. 

5 : 2' : 3' : 4:'-Tetramethoxy-l-benzoyl-2-7nethylcoumarone forms pale 
yellow, clearly-defined needles, m. p. 72 — 73°. 

These compounds are all coloured red by concentrated sulphuric 
acid. E. F. A. 

Interaction of Homologous Phenols with Methylcoumaric 
Acid Dibromide. II. Richard Stoermer and C. Friemel {£er., 
1911, 44, 3256 — 3266). — In continuation of previous work (Abstr., 
1911, i, 632), the authors have studied the interaction of methyl- 
coumaric (o-methoxycinuamic) acid dibromide and m-cresol. When 
equal parts of these substances are heated for ten minutes on the 
water-bath, the following products are obtained : (1) j^-o-methoxyphenyl- 
ap-di-])-hydroxy-o-tolylpropioniG acid, 

6iV[e-C,H4-CH(C^H3Me-OH)-CH(C6H3Me-OH)-C02H, 
which crystallises from dilute acetone in colourless needles, m. p. 
274°, and yields a methyl ester, crystallising in small columns, m. p. 
225° ; the di-y-nitrobenzoyl derivative, CggHggO^^Ng, forms light yellow, 
rhombic plates, m. p. 216°. (2) i-o-Methoxyphenyl-l-inethylcoumariny 

CMe:CH-C CO , . ^ ... . ... 

CHzCH.C.C(C,H,.OMe):CH' "^"^ crystallises from glacial acetic 
acid in rhombic columns, m. p. 220°, and is also obtained by the 
removal of hydrogen bromide from the compound (3) described below 
by means of quinoline. (3) 3- Bi'omo-i-o-methoxy phenyl -7 -methyl - 

. . . CMelCH-C CO ^. , ^ ... 

^y^^^<><^^--^-^^-^ CH=:CH-C.CH(C,H,.0Me).6HBr' "^"'^ crystallises 
in rectangular plates, m. p. 123°, and, when heated with strong 
aqueous sodium hydroxide, loses hydrogen bromide, yielding 2-o- 
7nethoxyph6nyl-5-methylGoumaran-l-carboxyhG acidy 
CMelCH-C-O-CH-COgH 

CH=CH-C — CH-CeH^-OMe* 
This crystallises in rhombic platelets, m. p. 199°, having a pale blue 
fluorescence, and yields a sparingly soluble, yellow sodium salt ; the 
piperididcj CggHgjOgN, forms slender, colourless columns, m. p. 



i. 46 ABSTRACTS OF CHEMICAL PAPERS. 

148 — 149°; the methyl ester crystallises in hexagonal plates, m. p. 
75°. The hydrazuUj prepared by heating the methyl ester with 
hydrazine hydrate in alcoholic solution, has m. p. 110°, and yields the 
correvsponding azoimide when treated with sodium nitrite in aqueous 
acetic acid solution. 

lCarbethoxi/ainino-2o-methoxi/phenyl-5^ethylcouviaran, 

^''^»*^'<-CH-C„H,-0M6' 
obtained by boiling an alcoholic solution of the azoimide, crystallises in 
very thin, colourless leaflets, m. p. 143 — 144°, and is converted on 
heating with concentrated hydrochloric acid and alcohol into 2-o- 

fneihoxyphenyl-5-m«thylcoumaronej CgHgMe^p/p tt .oiti \^CJH, which 

is an oil, b. p. 220 — 223°/25 mm., gives an intense orange-red colora- 
tion with sulphuric acid, and, on reduction with sodium in alcoholic 
solution, yields ^-o-methoxyplienyl-b-methylcouinaran, 

r\ 

CgH8Me<Q|^^^^ jj^. 0Me)'^^^2- 

This crystallises from alcohol in lustrous, silky needles, having a pale 
blue fluorescence, m. p. 96 — 97°. 

The constitution of the two last-mentioned compounds has been 
established by their synthesis from o-methoxymandelonitrile and 
m-cresol. When heated with sulphuric acid, these condense to form 
the lactone of o-methoocyphenylo-hydroxy-ip-tolylacetic acid, 

JMelCH-CH-O-CO 

JHZCH-CH — C-CeH^-OMe' 
which has m. p. 116 — 119°, and is converted into 2-o-methoxyphenyl- 
5-methylcoumarone by heating with phosphorus pentasulphide. 

F. B. 



s 



Corydalis Alkaloids. XI. Corytuberine. Johannes Gadamer 
(Arch. Pharm., 1911, 249, 641—669. Compare Dobbie and Lauder, 
Trans., 1893, 63, 485 ; Gadamer and Wagner, Abstr., 1902, i, 391 ; 
Schmidt, Abstr., 1909, ii, 85, and Gadamer, Abstr., 1911, i, 1011, 
1012). — A general discussion of the constitutions and relationships of 
the corytuberine group of alkaloids has been given already (Abstr., 
1911, i, 1011), and in the present paper the experimental data on 
which the formula then assigned to corytuberine was based are 
given. 

The alkaloid is best obtained by distilling the alcohol from an 
alcoholic extract of Corydalis roots, dissolving the residue in water, so 
that the aqueous mixture weighs twice as much as the weight of roots 
used, filtering, adding ammonia solution iu very slight excess to the 
filtrate, shaking rapidly with ether, and removing the separated 
aqueous layer as quickly as pos'^ible. The aqueous liquid so treated 
continues to depoi^it impure crystals of corytuberine for several days. 
This may be puritied by fractional precipitation by ammonia solution 
from the hydrochloride, washing with water, alcohol, and ether in 
turn, and finally recrystallising from boiling water. The alkaloid 
has the formula C^^^i^^^^H^^ (compare loc. cit.). 



OUGANIC CHEMISTRY. 1. 47 

With benzoyl chloride, by the Schotten-Baumann method, it 
furnishes a crystalline monohenzoyl derivative, m. p. 211 — 214° 
[a]^ + 151*5° in chloroform, and a dihenzoyl derivative, m. p. 
135— 140°, [a]|? +128-8— 133-5° in chloroform, which is amorphous, 
but yields a crystalline hydrochloride. On boiling with benzoyl 
chloride a tribenzoyl (possibly tetrabenzoyl) derivative, m. p. 140 — 142° 
(approx.), [a]j?=0°, crystallising in glandular masses of crystals, 
is formed. 

On methylation with methyl sulphate by Pschorr and Karo's 
method (Abstr., 1906, i, 878), a mixture of two methylcorytuberine 
methosulphates with some corytuberine methosulphate is produced. 
With diazomethane a mixture of two methylcorytuberines with two 
methylcorytuberine methylhydroxides is formed. One of the methyl- 
corytuberines is identical with corydine (see following abstract), and 
the other has been named isocorydine {Joe. cit.). When diazomethane 
is generated in presence of corytuberine suspended in zsoamyl ether, 
dimethylcory tuber ine is produced ; the acid \- tartrate, m. p. 219 — 224° 
(decomp.), [afo + 150° in water, crystallises in groups of needles. By 
applying methyl sulphate in excess to methylcorytuberine metho- 
sulphate and neutralising the solution from time to time as it becomes 
acid, complete methylation of the alkaloid was eventually secured, and 
from the dimethylcory tuberine methosulphate formed, a small amount of 
the corresponding methochloride was prepared j it crystallises as needles, 
m. p. 234 — 237° (decomp.), [af^ + 197*4° in water, and gives an auri- 
chloride, m. p. 160° (decomp.). The crude methosulphate on treat- 
ment with alkali gives dimethylcorytuberimethine, CggHg^^O^N, the 
hydrochloride of which is crystalline and optically inactive. The 
methine base forms a Tnethiodide, which meltslabove 260°, and a metho- 
sulphate (yellow needles) ; the latter, on treatment with alkali, furnishes 
trimethylamine and 3:4:5:6- tetramethoxy - 8 - vinylphenanthrene, 
m, p. 69°, which on bromination in chloroform yields a pentahromo- 
derivative, C2oH^704Br5, m. p. 175 — 178°, and a hexabromo-conn^oxxndi, 
CgoH-^gO^Brg, m. p. 185° (decomp.) ; the latter, on recrystallisation 
from acetic acid, gives a j»e/i^a6?'omo-derivative, CgoHji^O^Brg, m. p. 
185° (decomp.). On distillation with zinc dust, tetramethoxyvinyl- 
phenanthrene yields a-ethylphenanthrene (Pschorr and Karo, loc. cit.), 
and on oxidation with permanganate in acetone gives 3:4:5: ^-tetra- 
methoxyphenanthrene-S-carboxylic acid, m. p. 165 — 167°, crystallising 
in leaflets from alcohol, along with a small amount of a neutral 
substance, which is probably the corresponding glycol (compare 
Pschorr and Karo, loc. cit.). T. A. H. 

'HpCorydalis Alkaloids. XII. Corydine. isoCorydine. Johannes 
~ADAMER (Arch. Fharm., 1911, 249, 669— 680).— In part IX of 
this series of papers (Abstr., 1911, i, 1011), formulae for corydine 
and isocorydine were given, based on the fact that they are mono- 
methyl ethers of corytuberine, and are produced by the methylation 
of the latter alkaloid with diazomethane (see preceding abstract). 
In this paper the experimental details of this work are given. In a 
previous paper (Abstr., 1902, i, 391) the formula CgjHggO^N or 



i. 48 AHSTRACTS OF CHEMICAL PAPERS. 

was assigned to corydine, but this is untenable in view of its relation- 
ship to corytuberine. New analyses of natural and synthetic 
corydine give results in agreement with the formula CgoHggO^N. 
When crystallised from alcohol, corydine contains JEtOH, and then 
melts at 124 — 125°; on exposure in a vacuous desiccator and re- 
crystallisation from ether, it melts at 149°. These two kinds of 
crystals are identical in form both for synthetic and natural corydine 
[a:c=l : 0*39896]. On treatment with methyl iodide in the cold, 
corydine gives a methiodide, m. p. 190—191°, [a]2* +157-3° in 50% 
alcohol, crystallising in slender, voluminous needles with 1 JHgO. If 
the mixture is heated, the methiodide formed has m. p. over 200°, 
[aj^ + 154*6°, and forms compact crystals with l^Kfi. 

On treatment with iodine in alcohol, corydine furnishes dehydro- 
corydine hydriodide, CgoHj^O^N,!!!, which separates from water in 
yellow, compact crystals and gives a red coloration, and eventually 
a flocculeut, red precipitate, with solutions of sodium hydroxide. 
On reduction with zinc and dilute sulphuric acid, it gives ^\-corydine, 
m. p. 165 — 167°, which is somewhat less soluble in ether than the 
optically-active forms. The acid c?-tartrate, on crystallisation from 
water, deposits \-corydine hydrogen 6-tartratef from which \-corydinej 
[ajo — 206*2° in chloroform, was prepared. 

iaoCorydhve, CgoHggO^N, m. p. 185°, [a]^ +195*3° in chloroform, 
prepared as described already (see preceding abstract), crystallises 
in glistening, four-sided tablets, and is less soluble in ether than 
corydine. In its colour reactions it resembles bulbocapnine rather 
than corydine. The methiodidey m. p. 213 — 214° (decomp.), 
[ajn + 143*3°, is crystalline, and, unlike the corresponding corydine 
derivative, is sparingly soluble in water. On treatment with 
iodine in alcohol, wocorydine gives a greenish-black product. 

T. A. H. 

Corydalis Alkaloids. XIII. Glaucine Sub-group. Johannes 
Gadamer (Arch. P/uirm., 1911, 249, 680— 701).— Pschorr has 
described (Abstr., 1904, i, 612) the synthesis of phenanthreno-^V- 
methyltetrahydropapaverine from c?/-aminolaudanosine (amino-iV^- 
methyltetrahydropapaverine), but the substance he described under 
this name was probably ciZ-iaudanosine, since it gave a methiodide, 
m. p. 215°. The author has repeated Pschorr 's work, and 6nds that 
pheuanthreno-iV-methyltetrahydropapaverine is actually produced in 
this synthe.-^is, and is rfZ-glaucine ; in addition, the f^-forms of 
laudanosine, hydroxylaudanosine, and dilaudanosine are also f'^rmed. 
Formulae for aminolaudanosine, laudanosine, and glaucine have been 
printed already (Abstr., 1900, i, 685; 1904, i, 612), and constitutions 
are now assigned to hydroxylaudanosine (I), dilaudanosine (II), and 
dicentrine (III), to which allusion is made later. 

The solution resulting from the addition of copper powder to a 
diazotised solution of aminolaudanosine (Pschorr, loc. cit.) is reduced 
with zinc and dilute sulphuric acid ; excess of ammonia is then 
added, and the solution shaken with ether, which removes all the 
alkaloids. The residue left on distilling the ether is separated into 
phenolic base (hydroxylaudanosine) and non-phenolic bases (laudanosine, 



ORGANIC CHEMISTRY. 



i. 49 



glaucine, and dilaudanosine) by solution in dilute hydrochloric acid 
and treatment of this liquid with excess of alkali hydroxide. Full 



OMe, 
OMe' 



CHg NMe 

\ H /\ 



OMe 



(I.) 



I I 



OMe 



OMe 
OMe 



CHg NMe 



I I 



\|- 






OMe 



II.) 



OMe 



OMe 
OMe 




(III.) 



details of the isolation of these constituents from these two fractions 
are given. 

dl-Glaucine, Cg^IIggO^N, m. p. 137 — 139°, gives a crystalline hydro- 
chloride, which is less soluble than those of the d- and Z-forms ; the 
methiodide, m. p. 218 — 220°, is crystalline. dl-Glaucine hydrogen d- or 
l-tartrate crystallises in needles, and has [aj^ ± 33°. On recryatallisa- 
tion from water these tartrates yield the corresponding salts of d- and 
/-glaucine, from which the free bases are obtainable ; the c£-glaucine 
so obtained is identical with the natural alkaloid (Fischer, A.bstr., 
1901, i, 743). 

c?/-Laudanosine, obtained in this reaction, is identical with that 
described by Pictet and Athanasescu (Abstr., 1900, i, 685). 

dl- Hydroxy laudanosine, CgiHg^OgN, m. p. 189 — 190*5° (decomp.), 
gives colour reactions resembling those of glaucine. By recrystallisa- 
tion of the hydrogen tartrates it was separated into d- and Z-forms. 
These crystallise in masses of long, colourless needles, and have m. p. 
188 — 190-5° and [ajo +50°. The nitrates crystallise well, and are 
sparingly soluble. 

d\-Dilaudanosi7ie, C^^^^fi^N^f is amorphous ; it is produced in very 
small quantity in this synthesis, and was not obtained pure. Its chief 
colour reactions are described. 

Dicentrine, isolated by Asahina (Abstr., 1909, i, 601), closely 
resembles glaucine in its colour reactions, physiological action, and 
chemical properties, and for that reason is regarded as glaucine, in 
which the -OMe groups in positions 5 and 6 are replaced by a dioxy- 
methylene group. A synthesis of dicentrine is being attempted. 

T. A. H. 



Isomerism of Corynanthine with Yohimbine. Ernest Four- 
NEAU and FiORE (Bull. Soc. chim., 1911, [iv], 9, 1037— 1040).— In view 
of the possible isomerism of these two alkaloids already referred to 
(Abstr., 1910, i, 501), the authors have re-examined yohimbine, and 
find that, like corynanthine, it has the composition represented by the 
formula CgiHggOgNg. Yohimbine hydrochloride has [a]o+105°; 
corynanthine hydrochloride has [a]i? -64' 15°. T. A. H. 

Red Compounds from Brucine. Josef Buraczewski and 
Z. Zbijewski (Bull. Acad. Sci. Cracow, 1911, Aj 464—469). — Various 
reagents act on brucine to give red soluble compounds without oxidising 
or decomposing the brucine molecule. 

VOL. Cil. i. c 



i. 60 ABSTKACTS OF CHEMICAL PAPERS. 

By the action of dry chlorine on brucine, until the evolution of 
hydrogen chloride begins, a reddish-brown Rubstance, 

is obtained. When the action of the chlorine is prolonged until no 
more hydrogen chloride separates, a dark grey powder is obtained, 
soluble in water with a red coloration ; this has the composition 
CjiH^<,0,N2Cl8,HCl,2H20. 

When bromine is allowed to act on brucine in absolute alcohol, a 
brownish-red powder is obtained, which is considered to be a mixture 
of C2iH220,N2Br,2H20 and C^.,ll,fi,l^^Br,nHr,n^O. 

The production of a red coloration when the product of the action of 
dry chlorine on brucino is boiled with alcohol is characteristic of this 
alkaloid, and may be used for its detection. E. F. A. 

Hsemopyrrole. Hans Fischer and E. Bartholomaus (J5er., 1911, 
44, 3313 — 3317). — Knorr and Hess have recently published (Abstr., 
1911, i, 1019) a synthesis of 2 : 4:-dimethyl-3-ethylpyrrole which they 
consider not to be identical with haemopyrrole investigated by 
Piloty (Abstr., 1910, i, 133). The main difference is a discrepancy 
of 23° in the melting point of the picrates. 

The authors show that haemopyrrole picrate has m. p. 120 — 122°, 
instead of 108*5° as previously described. In attempting to obtain 
2 : 4-dimethyl-3-ethylpyrrole according to the method of Knorr and 
Hess, the authors obtained, in place of the expected hydrazone, a 
ketazine, the m. p. of which varied between 195° and 215°. This, on 
energetic reduction, yields an oil, the b. p. of which agreed with that 
given by Knorr and Hess, but the picrate melted indefinitely at 
82 — 83°. This oil, when treated with benzenediazonium sulphate, 
yielded an azodye, Cj^Hj^OgNgS, which crystallises in red needles 
(compare this vol., i, 41, 56). H. W. 

Picrylpyridinium Chloride. Max Busch and Walter Kogel 
(/. jyi'. Chem., 1911, [ii], 84, 507— 514).— When equal molecular 
quantities are heated in alcohol on the water-bath, picryl chloride and 
pyridine yield at first a little picrylpyridinium picrate, yellow needles, 
m. p. 223°, and finally, after cooling, almost colourless crystals of 

picrylpyridinium chloride, C^HgN^p tt (^r\ \ , m. p. 128° ; the latter 

changes to the former after long keeping, or after prolonged boiling in 
alcoholic solution. The chloride is converted by alcoholic potassium 
hydroxide into the potassium salt of a pyridine dye, probably 
N02K:C6H2(N02)2'NC^H^-CH0, which forms reddish-brown crystals 
with a green lustre. Picrylpyridinium picrate is decomposed almost 
quantitatively into pyridine and picric acid by boiling water, and 
yields with potassium iodide, pia-ylpyridiidum iodide, m. p. 155°, 
orange leaflets. In ether, pyridine and picryl chloride (2 mols.) yield 
an additive com/)oitnrf,CiiHyOgN4Cl,CgH2(N02)3CI, m. p. 151° yellowish- 
green needles. C. S. 

New Derivatives of Dioxindole. Moritz Kohn and Alfons 
Ostersetzer {Monatsh., 1911, 32, 905 — 916). — Various substituted 
dioxindoles with a tertiary hydroxyl group have already been obtained 



ORGANIC CHEMISTRY. i. 51 

by the application of the Grignard reagent to isatin (Kohn, Abstr., 
1910, i, 697). 

S-Phenyldioxindole by methylation with methyl sulphate gives 
^-phenyl - l-methyldioxindoh methyl ether ; this forms leafy crystals, 
m. p. 83°. The action of acetic anhydride yields a monoacetyl com- 
pound, probably l-acetyl-3-phenyldioxindole, which crystallises from 
benzene in short, columnar crystals, m. p. 141°. 

3-Benzyl-l-methyldioxindole methyl ether, obtained analogously to the 
corresponding phenyl compound, forms needles, ra. p. 97°. 

3-Methyldioxindole, obtained by the action of magnesium methyl 
iodide on isatin, forms white, granular crystals, m. p. 160°; methyla- 
tion gives 1 : S-dimethyldioxindole methyl ether, cubical crystals, 
m. p. 78'5° ; it yields a diacetyl derivative, m. p. 125°. 

5-Bromo-S-phenyldioxindole is produced when magnesium phenyl 
bromide reacts with 5-bromoisatin ; it 'forms thin rods, m. p. 243° 
with decomposition. 

b-Bromo-3-methyldioxindole is obtained similarly from bromoisatin 
with magnesium methyl iodide, and also by the action of bromine 
water on 3-methyldioxindole ; on heating it turns brown at 240°, and 
melts at 258°. When methylated, it produces 5-broono-l : 3-dimethyl- 
dioxindole methyl ether, needles, m. p. 142°. D. F. T. 

Spirans. IV. History and Theory. Dan Radulescu (Chem. 
Zentr., 1911,82, ii, 1535; from Bull. Soc. Sti. Bucuresti, 1911,20, 
281—284. Compare Abstr., 1911, i, 497).— The chemical properties 
of a spiran ACB, composed of rings CA and CB of known structure 
and properties, are qualitatively the sum of those due to AC and CB, 
except where there are large accumulations of groups on the same 
carbon atom. With the exception of those formed from three or four 
atom rings, the spirans are stable. They show optical activity in some 
cases, although no asymmetric atom is present. Compounds in which 
two rings share a common nitrogen atom are quite different from 
the spirans, although they present a superficial resemblance to them. 

T. A. H. 

Compounds of Ferric Salts with Antipyrine. Filippo 
Calzolari (Boll. chim. farm., 1911, 50, 763 — 767). — The molecular 
weight of antipyrine, determined cryoscopically in aqueous solutions, 
is normal, but when ferric chloride is present higher values are 
obtained, so that the red coloration which antipyrine gives with ferric 
chloride is probably due to the formation of a complex cation. Ferric 
fluoride gives only a pale yellow coloration with antipyrine, and 
corresponding with this the molecular weight of antipyrine is lower in 
this solution than in the presence of ferric chloride. The compound of 
ferric chloride and antipyrine is an orange-red, crystalline powder 
having the composition 2FeCl3,3C^iHi20N2, and ferric bromide also 
yields a compound, 2FeBrg,3CiiHi20lS2, which forms reddish- brown 
crystals. l\, Y. S. 

l-Phenyl-3-methyl-5-pyrazolone and 4-Amino-l-phenyl- 
3-methyl-5-pyrazolone. Alfred Heiduschka and O. Kothackek 
(./. pr. Chem., 1911, [ii], 84, 533— 542).— The heating of 1-phenyl- 

6 2 



i. 52 ABSTRACTS OF CHEMICAL PAPERS. 

3-methyl-5-pyrazolone and o-, m-, or ;t)-nitrobenzalclehyde at 140° for 
ten minutes yields a mixture of the nitrobenzylidene derivative and a 
bispyrazolone derivative, which is separated by means of benzene. 
i-o-Nilrobenzi/Udsne-l-phenyl-S'meihi/l-bpyrazolone, m. p. 157°, crystal- 
lises in red needle." ; the corresponding meta- and para-i.'>omerides have 
m. p. 162° and 171° respectively. ^:•.^'-o^Nitrohen^ylidenehi8^\-phenyl- 
Z-imthyl^ -pyrazolone, N02*CgH^'CH(CioHQON2)2, m. p. 146° (decomp.), 
and the meta-isomeride, m. p. 150° (decomp ), form yellow leaflets. 

When heated with zino chloride at 140°, l-phenyl-3-methyl-5-pyrazo- 
lone condenses with acetophenone to form l-phenyl-i-a-phenylethyl- 

QQ N'Ph 

ident-Smethy 1-5 -pyrazolone, CMePh!C<^ I , m. p. 89° orange 

crystals, and with benzophenone to form a corresponding auhstance, 
CjgHigONj, m. p. 133°, orange-red leaflets. 

4-A.mino-l-phenyl-3-methyl-5-pyrazolone reacts with cinnamaldehyde 
and with o-nitrobenzaldehyde to form the corresponding Schiff's bases, 
CigHj^ONg, m. p. 192°, and Ci^Hj^OgN^, m. p. 198°. Also with 
piperonal and with anisaldehyde it yields the substances, C^^HggOj^N^j, 
m. p. 235°, and C^^H^gO^Ng, m. p. 252°, respectively. C. S. 

Conversion of the Nitro- into the Keto-group. Wilhelm 
WiSLiCENUS and Hermann Goz {Ber., 1911, 44, 3491— 3496).— The 
potassium salt of 4-oximino-l-phenyl-3-methyl-5-pyrazolone separates 
in lustrous, silky, deep yellow needles, m. p. 250 — 255°. By the 
action of bromine, 4:-bromo-4:-nitro-l-p-b7'07noplie7iyl-3-methyl-5-pyrazolone 
is formed; this crystallises in well formed, small, dark yellow 
prisms, m. p. about 85°, to a red oil (decomp.). On heating, it is 
converted into ^-keto-l-p-bromoph^.nyl-3-methyl-6-pyrazolone, 

this separates in small, flat prisms, yellowish-red in transparent, 
bluish-red in reflected, light, m. p. after sintering 171 — 172°. On 
boiling with water, it forms colourless needles, probably indicating an 
additive product ; a colourless additive product is formed also with 
sodium hydrogen sulphite. 

When dissolved in sodium hydroxide or carbonate the keto- 
pyrazolone ring is opened ; from the reddish-yellow solution a yellow 
acid is precipitated by strong mineral acids. This a^-diketobutyric 
acid fip-bromophenylhydrazone, CgH^Br'NH'NICMe'CO'COgH, crystal- 
lise-t in microscopic, canary-yellow prisms, m. p. 153 — 154° (decomp.). 
On boiling with acetic anhydride the deep red keto-T^-bromophenyl- 
methylpyrazolone is re-formed. With phenylhydrazine a golden-yellow 
plitnylosazone, m. p. 211°, is obtained. The yellow insoluble silver salt 
reacts with methyl iodide to form the methyl ester, 
CeH^Br-NH-NICMe-CO-COgMe, 
which crystallises in brownish-yellow, microscopic prisms, m. p. 
165—170°. 

When warmed for several days with acetic acid, keto-/?-bromophenyl 
methylpyrazolone is converted into dibromorvhazonic acid, 



1 



^m ORGANIC CHEMISTRY. i. 53 

^Hhis has m. p. 305 — 308°, and dissolves in alcoholic potassium 

^Rydroxide and in concentrated ammonia with a violet-red coloration. 

N— CMe 
4:-Bromo-4:-nitro-3-methyl-6-pyrazolone, NH<^ I , obtained 

L'0*0rJr*JN(J2 

from the golden-yellow prisms of the potassium salt of 3-methyl- 

4-zsoDitro-5-pyrazolone, crystallises in small, yellowish-white prisms, 

m. p. 84 — 85° (decomp.). On heating, a red, amorphous substance is 

obtained, which could not be purified. E. F. A. 

Hydantoins. VII. Synthesis of 2-Thiohydantoin. Treat 
B. Johnson and Ben H. Nicolet (/. Amer. Chem. Soc, 1911, 33, 
1973 — 1978). — 2-Thiohydantoin has been synthesised by Komatsu 
(Abstr., 1911, i, 683) by the action of potassium thiocyanate on 
glycine in presence of acetic anhydride, and also by Wheeler, Nicolet, 
and Johnson (Abstr,, 1911, i, 1031) by heating acylthiohydantoic acids 
with hydrochloric acid. 

A large quantity of 2-thiohydantoin being required for certain 
investigations, Komatsu's method was employed, and it was found that 
the compound could be very easily prepared in this way. Koaiatsu's 
interpretation of the mechanism of the reaction is incorrect, and his 
statement tbat thiohydantoic acid is produced could not be confirmed. 
It is shown that acetylglycine is first produced, and combines with 
thiocyanic acid to form a thiocyanate, which undergoes re-arrangement 
to acetylthiohydantoic acid. This compound suffers an inner conden- 
sation, with formationof 2-thio-3-acetylhydantoin, which is subsequently 
converted into 2-thiohydantoin. 

When glycine is heated with potassium thiocyanate and acetic 

QQ — ;nH 
anhydride, 2-thio-3-acetylhydantoinf CH2<[^ i ,m. p. 175 — 176°, 

is produced, which crystallises in square blocks, and when heated with 
hydrochloric acid is converted quantitatively into 2-thiohydantoin. 
The compound can also be obtained by the action of potassium 
thiocyanate on acetylglycine (aceturic acid). 

By the action of potassium thiocyanate on hippuric acid in presence 
of acetic anhydride (9 parts) and glacial acetic acid (1 part), 2-thio- 

S-benzoylhydantoin, CH2<^„-p ' ^^ , m. p. 165°, is obtained in a yield 

of 86%; it crystallises in square plates. When the compound is 
hydrolysed with concentrated hydrochloric acid, it yields 2-thio- 
hydantoin, and when condensed with benzaldehyde in presence of 
glacial acetic acid and anhydrous sodium acetate, it is converted into 
2-thio-4-benzylidenehydantoin. E. G. 

Condensation of Methyluracil and Formaldehyde. Wilhelm 

IRCHBR {Annalen, 1911, 385, 293— 314).— 4-Methyluracil and 40% 

formaldehyde (3 mols.) condense in acid solution to form 4:-methyl- 

S-hydroxy methyluracil, CO<^^tt.P^ ^C'CHg'OH, plates or needles, 

lecomp. 305 — 310°; in alkaline solution, the same product is obtained 
the form of the sodium salt, CgH^OgNgNa. The substance is 



i. 54 ABSTRACTS OF CHEMICAL PAPERS. 

reconverted into its generators by boiling water, and is clianged to a 
substance, CjjHj^OgN^, decomp. 303—307°, by boiling dilute hydro- 
chloric acid. By reduction with tin and 36% hydrochloric acid at 
58 — 60°, it yields 4 : 5-dimethyluracil and a substance, C|iHj204N4 
decomp. 302 — 307°. 4 : 5-Dimethyluracil has also been prepared by 
passing the vapour of cyanic acid (3 mols.) in a current of dry carbon 
dioxide into an ethereal solution of methyl /3-amino-a-methylcrotonate 
in a freezing mixture, boiling the product with 10% potassium 
hydroxide, and acidifying after the removal of the cyamelide by 
filtration. 4 : 5-Dimethyluracil is oxidised to acetylcarbamide and 
oxalic acid by 4% potassium permanganate, and when heated with 
aqueous potassium hydroxide, 95% alcohol, and methyl iodide yields 
a mixture of 1:3:4 : 6-tetram.ethyluracil, m. p. 123 — 125 5°, 1:4:5- 
trtmethyluracil, m. p. 220*5 — 222°, and 3:4: 6-trimethyluracilf m. p. 
172—174°. 

A suspension of 4 : 5-dimethyluracil is converted by bromine into 
^-hromo-bhydroxy-^ : 5-dimethyldihydrouracilf 

CO<NH^eB>CMe-OH. 

m. p. 226 — 227° (decomp.), which changes to ^-hromo-i-methyl-b methyl- 
enedViydrouracil at 105°, and to 4:-bromo-5-ethoxy-4: : 5-dimethyldihydro- 
uracil, m. p. 225 — 226° (decomp.), when boiled with alcohol. The last 
substance at 105° also yields 4-bromo-4-methyl-5-methylenedihydro- 
uracil, which is converted by bromine water into i-hr omo-b -hydroxy - 
i'methyl-b-h'Oinomethyldihydrouracil, CgHgOgNgBrg, m. p. 165 — 167° 
(decomp.) ; the latter is also obtained by treating 4 : 5-dimethyluracil 
with bromine and subsequently boiling with water. 

When 4-bromo 5-hydroxy-4 : 5-dimethyldihydrouracil is treated with 
5% potassium hydroxide in the cold, a substance, C^HjQO^N^.HgO, 
m. p. 168'5 — 169'5° (decomp.), is obtained, which may be 4:5- 
dihydroxy -4:5- dimethyldihydrouracil or acetylmethylhydantoin 
(compare Bremer, Abstr., 1911, i, 160). C. S. 

Alkyl Derivatives of Methyluracil. Oskar BOckendorpf 
(Annalen, 1911, 385, 314— 327).— 4-Methyl-3-ethyluracil (Hoebel, 
Abstr., 1907, i, 557) reacts with aqueous bromine to form 5 : 5-dibromo- 

i'hydroxyA-methyl-Sethyldihydrouracily NEt<^p^ ^OH^OR ^^^* 

m. p. about 160°, which is converted by 95% alcohol into 5-bromo- 
A-methyl-Z-ethyluracil, m. p. 234 — 236° (decomp.); the latter reacts 
with aqueous ammonia at 150 — 160° to form b-aminoA-methyl-^-ethyl- 
uracily m. p. 234 — 236°. The following compounds are obtained from 
4-methyl-l-ethyluracil by similar methods : 5 : b-dibromoA-hydroxy- 
A-methyl-l ethyldihydrouracil, m. p. about 160°; b-bromo-i-methyl- 
l-ethylurncil, m. p. 203 — 206°; 5amino-4:-'niethyl-l-ethyluracil, m. p. 
203 — 205°. 4-Methyl-l-ethyluracil is converted by sulphuric and nitric 
acids on the water-bath into b-nitrol-ethyluracil-i-carboxylic acid, 
CyHyOgNgjHgO, m. p. 189° (decomp.), and a substance, C^HgOgN^, 
decomp. 180 — 220°; at 140—150° the former yields 5-nitro-l-ethyl- 
uracil, m. p. 159 — 161°, which is reduced by aqueous ammonia and 
aluminium amalgam to 6-amino-l-ethyluracilf m, p. 171 — 172°. 



I 



ORGANIC CHEMISTRY. L 55 



4:-Methyl-3-propyluracil, m. p. 170 — 172°, and i-methyl-l-propyluracil, 

. p. 184°, are prepared and separated in a similar manner to the 
methylethyluracils (Hoebel, loo. cit.). Their constitutions are proved 
as follows : 4-Methyl-l-propyluracil by ethylation, and 4-raethyl- 
3-ethyluracil by propylation, yield the same ^-methyl-3-ethyl-\-propyl- 
uracil, m. p. 63 — 65°. Also, 4-methyl-l-propyluracil by methylation, 
and 3 : 4-dimethyluracil by propylation, yield the same 3 : i-dimethyl- 
1-propyluracil, m. p. 85 — 87°. Finally, 4-methyl-3-propyluracil by 
methylation, and 1 : 4-dimethyluracil by propylation, yield the same 
1 : 4:-dimethyl-3-propyluraGil, m. p. 52 — 54°. 

Methylallyluracils have been prepared and their constitutions 
proved by similar methods. 4:-Methyl-\-allyluraGil and 4:-methyl- 
3-allyluracil have m. p. 180 — 182° and 168 — 169° respectively; 
1 : 4:-dimethyl-3-allyluracU and 3 : ^-dimethyl-\-allyluracil have m. p. 
45 --47° and 59— 61° respectively. 

Afethylisobutyluracils, m. p. 195 — 196° and 133 — 135°, have been 
obtained, but have not yet been fully investigated. C. S. 

Phenylraethyltriazole. A Correction. Eugen Bamberger 
{Ber., 1911, 44, 3564— 3565).— It was previously stated (Abstr., 
1894, i, 23) that l-phenyl-5-methyltriazole-3-carboxylic acid yielded 
phenylmethyltriazole, m. p. 191°, when heated in a stream of carbon 
dioxide. Pellizzari has shown that this compound is in reality cyano- 
phenylacetamidine, NPhlCMe-NH'CN. It was also stated that the 
compound was a base, but it is now shown to be an acid soluble in 
sodium hydroxide, and is precipitated in colourless needles, as stated 
by Pellizzari (loc. cit.). E. F. A. 

i\^-Quinhydrones. M. M. Richter (Ber., 1911, 44, 3466—3469). 
— The action of iodine on p-phenylenediamine in benzene solution gives 
rise to an almost black substance of the composition 

nh:c6H4:nh,nh2-C6H4-nh2,2hi,I2, 

a nitrogen analogue of the quinhy drones. This ^-benzoquinhy drone 
dihydriodide periodide is an almost black substance, which loses iodine 
on warming. On account of its instability, the corresponding base 
could not De isolated. 

Benzidine treated with iodine in a similar manner gives ^-henzidine- 
quinhydro7ie dihydriodide periodide, 02^1122^4,2111,14, a greyish-black 
powder, which loses iodine even at the ordinary temperature. 

o-Phenylenediamine treated with iodine behaves quite differently, 
jand yields 2 : 3-diaminophenazine. 

References are given to papers describing compounds which must be 

^regarded as derived from the above bases or from bases of the same 

type. The author ascribes to all these bases a structure analogous to 

.that which he has already attributed to the quinhydrones (Abstr., 

1911, i, 136), for example, NHICgH •NH2-NH-C6H4-NH2,2HI.I,. 

D. F: T. 

Preparation of Solid Diazonium Salts by means of Nitrosyl 
Chloride. M. Struszynski and Wojeiech Sventoslavsky {Bull. Acad. 
JSci. Cracow, 1911, A, 459 — 463). — Nitrosyl chloride, which is now an 



i. 56 ABSTRACTS OF CHEMICAL PAPERS. 

easily accessible product, is an energetic diazotising agent, and it is 
conveniently used for preparing solid diazonium salts in a state of 
purity. 

The amine is dissolved in alcohol, and an alcoholic solution of 
hydrogen chloride containing 2'5 — 3 mols. of the acid added ; the 
mixture is cooled in ice, and the solution of nitrosyl chloride in toluene 
added. Action is rapid and complete, and the insoluble diazonium 
salt separates. When sulphuric acid is substituted for hydrochloric 
acid, the corresponding sulphates are obtained. E. F. A. 

Cazeneuve'e Diphenylcarbodiazide and Diphenylcarbazone. 
EuGEN Bamberger (Ber., 1911, 44, 3743— 3754).— From a com- 
parison of the properties, the author shows that the diphenylcarbo- 
diazide of Cazeneuve (Abstr., 1901, i, 297) is identical with the 
betaine of diphenylhydroxytetrazolium hydroxide (Bamberger, Abstr., 
1899, i, 355) ; the latter name gives the correct description. 

Reasons are also given for believing that whilst the formula 
NgPh'CO'NH'NHPh correctly represeuts the structure of free 
diphenylcarbazone (compare Heller, Abstr., 1891, 1212), the salts, 
which have a much more intense colour, are derived from the structure 
NjPh-C(OH):N-NHPh. D. F. T. 

Heemopyrrole. Lad. Leyko and Leon Marchlewski (Bull. Acad. 
Sci. Cracow, 1911, A, 345 — 349). — The hydrochlorides of dyes obtained 
by coupling heemopyrrole with benzenediazonium chloride have been 
described previously (Leyko and Marchlewski, Abstr., 1910, i, 144). 
To obtain the free base, NjPh'CgHgN'NgPh, the hydrochloride is 
decomposed with sodium acetate in alcoholic solution. 

Bisbenzeneazohaemopyrrole forms fine, lustrous needles, m. p. 
171 — 172°. In ethereal solution it shows two absorption bands in 
the visible region of the spectrum, whereas biscymeneazopyrrole and 
bisbenzeneazopyrrole are characterised by only one band. Taking into 
account Kiister's proof that hsemopyrrole, CgHjgN, yields methylethyl- 
maleinimide on oxidation, the bisbenzeneazo-derivative is formulated 

as I'hN2-N<^^^^p^^.Y^^^ [compare this vol., i, 41, 50]. E. F. A. 

The Changes in Physical Conditions of Colloids. XII. The 
Properties of the Protein Ions. Carl Schorr {Biochem Zeitsch., 
1911, 37, 424 — 451). — According to the theory of Pauli, proteins act 
both as acids and bases, but under certain conditions of hydrogen 
ion concentration, the protein ions themselves exist in solution, and 
not protein salts of either acids or bases. The protein ions, according 
to the theory, differ from the protein salts in that the ions, as hydro- 
phil colloids, are capable of existing as highly hydrated aggregates, 
from which the water is extracted only with some difficulty. This 
theory is supported by the fact that under such conditions the solu- 
tion of protein contains protein not in form of salts ; the protein is 
only slightly, if at all, precipitated by dehydrating agents, such as 
alcohol. Such solutions, furthermore, owing to the large aggregates, 
have a high viscosity, and also, owing to the large size of the hydrated 



ORGANIC CHEMISTRY. i. 57 

protein ions and their slow motion, have only a relatively small 
capacity for conducting electricity. In the presence of neutral salts, 
furthermore, the protein ions lose their electric charge, and all those 
properties disappear which are due to the presence of protein ions. 
In the presence of salts there is therefore a restitution of such 
properties as the precipitability by alcohol and a diminution of 
viscosity. The above theory is substantiated by numerous experi- 
ments on the precipitability of proteins in the presence of varying 
quantities of acids and bases, and by numerous physical measurements 
of the properties of the solutions under the varying conditions. 

S. B. S. 

Action of Bromine and Iodine on Proteins. A. Krzemecki 
(Bull. Acad. Sci. Cracow, 1911, A, 470 — 488). — Previous observers of 
the action of iodine or bromine on proteins have worked under con- 
ditions in which more or less oxidation took place. The experiments 
now described were made so as to alter the protein molecule as little 
as possible, merely introducing halogen partly in a very loosely bound 
condition. 

Egg-albumin was found to retain 28*3 — 29'6% of iodine and 18% of 
bromine, serum-albumin 28*5% iodine and 20*5% bromine, casein 19*1 
to 24'9% iodine, and plant protein 34*6% iodine. The halogen is 
attached to the protein molecule in several different ways, part being 
removed by boiling with acetic acid ; thus, after treatment, egg- 
albnmin contains 24-45% iodine, serum-albumin 24*5% iodine, and 
casein 17*37% iodine. Acetone at the ordinary temperature eliminates 
a further proportion of halogen, egg-albumin now containing 15*6% 
iodine, and serum-albumin 14%. Finally, treatment with sodium 
thiosulphate reduced the iodine in egg-albumin to 6*26%. 

a-Hydroxyprotosulphonic acid, under similar conditions, was only 
able to take up 11-12% of iodine when made from egg-albumin, and 
9*8% of iodine when prepared from serum-albumin. When the halogen 
proteins are heated with water, a large amount of decomposition takes 
place. The halogen proteins are digested both by trypsin and pepsin. 

The halogens in ethereal solution were allowed to acton the protein, 
absorption being usuiUy complete within a few hours in the case of 
iodine. Even better results were obtained, using methyl alcohol as 
solvent. E. F. A. 

3 : 5 Di-iodotyrosine from lodoprotein. IV. Gorgonin and 
Spongin. Adolf Oswald {Zeitsch. physiol. Clmn., 1911, 75, 
353 — 362). — The iodoproteins differ in the relative proportions of 
fixed iodine and iodine eliminated as hydrogen iodide on decom- 
position with barium hydroxide (compare Oswald, Abstr., 1911, 697, 
812). Of the total iodine in gorgonin, 82% is fixed, and 18% can be 
eliminated ; the amount of di-iodotyrosine isolated was 0*9%. Tyrosine 
is not the only iodine-fixing group of gorgonin. Spongin yields 64% 
of fixed iodine, 36% being eliminated on continued boiling ; 15*7% of 
the total iodine was isolated in the form of di-iodotyrosine. Spongin 
is regarded as containing at least two forms of iodine compound. 

E. F. A. 



i. 68 ABSTRACTS OF CHEMICAL PAPERS. 

The Physical Chemistry of the Bence -Jones Protein. Wolf- 
gang Pauli (Chem. Zentr.f 1911, ii, 371 ; from Zentr. Physiol.^ 1911, 
25, 110 — 111). — The author, in view of the recent work of Hopkins 
and Savory on the Bence-Jones protein, calls attention to the fact that 
he has already explained the peculiar properties of this substance as 
regards its solubility in salt solutions as a special case of the general 
properties of proteins. S. B. S. 

Formation and Estimation of Methaemoglobin. Joseph 
Barcroft and Franz Mt)LLER {Proc. physiol. Soc, 1911, xx. ; J. 
Physiol., 43). — Methaemoglobin is formed quantitatively when potass- 
ium nitrite is added to blood, the amount of haemoglobin converted 
containing an amount of dissociable oxygen equivalent to that 
necessary to convert nitrite into nitrate. Hydroxylamine sulphate 
acts similarly. Magnesium chlorate does not do so. Methaemoglobin 
in blood may be estimated by combining two operations: (1) a com- 
parison of the oxygen capacity with that of a standard blood, and 
(2) colorimetric comparison of the blood for estimation with the same 
standard, the haemoglobin in both being first turned into methaemo- 
globin. Two mild cases of methaemoglobin poisoning in cats produced 
no change in the dissociation curve of the blood. W. D. H. 



Preparation of Nucleic Acid. Amos W. Peters (J. Biol. Chem., 
1911, 10, 373 — 379). — Barium hydroxide with sodium chloride is used 
for the extraction of the tissue. The alkalinity thus obtained is 
sufficient to decompose the nucleo-proteins. One advantage of this 
new method is the comparative insolubility of the barium compounds 
formed with constituents of the tissue, and so little protein goes into 
solution that a separate precipitation of protein is unnecessary. The 
solution of barium hydroxide and sodium chloride dissolves nucleic 
acid freely. Barium, proteins, and guanylic acid are absent from the 
final product. W. D. H. 

Tyrosine as an Agent for the Fixation of Iodine in the 
Preparation of lodopeptones. Paul Macquaire {Compt. rend., 
1911, 163, 1084 — 1085). — Di-iodotyrosine has been isolated from 
peptones which have been treated with iodine. W. O. W. 

Oxyprotosulphonic Acids. I. Josef Buraczewski and L. 
Krauze {Zeitsch. physiol. C/iem., 1911, 76, 37 — 43. Compare Abstr., 
1911, i, 408). — Crude oxyprotosulphonic acid from egg- albumin, blood- 
serum, and casein is divided into fractions : (a) insoluble in hot acetic 
acid ; (^) crystallising from acetic acid solution in the cold ; (y) soluble 
in acetic acid, insoluble in alcohol ; (y^) insoluble in cold alcohol ; (yg) 
soluble in alcohol, but precipitated by ether. Each of these fractions 
has been analysed completely ; they differ in the intensity with which 
they show the biuret coloration, and also as regards the blackening 
with a lead salt due to sulphur in a loosely combined state. The 
intensity with each test falls from the a- to the y^-acid, that is, with 
the increase in solubility, and possibly corresponds with the increased 



ORGANIC CHEMISTRY. i. 59 

oxidation of the protein. The a-oxyprotosulphonic acid comprises more 
than one-half of the total product. E. F. A. 

Hydrolytic Decomposition of Proteins by Pepsin, Trypsin, 
Acids, and Alkalis. Valdemar Henriques and J. K. Gjaldb^ek 
{Zeitsch. physiol. Chem., 1911, 75, 363— 409).— The hydrolysis of a 
number of proteins by pepsin and trypsin has been followed by 
Sorensen's method of titrating in presence of formaldehyde, the 
titration of the aminoacids being effected in four stages (Henriques 
and Sbrensen, Abstr., 1910, ii, 164, 466). The liquid is made neutral 
to litmus paper, phenolphthalein added, and then iT/S -sodium 
hydroxide until a faint red coloration is obtained (stage 1) ; the 
addition is continued until the deep red colour of the control is 
matched (stage 2), when the neutral formaldehyde solution is added, 
and the titration continued until a faint red (stage 3) and a deep red 
(stage 4) colour are obtained. The ratio of the figure in stage 4, less 
the alkali used in the control, to the figure in stage 1 is calculated 
for each test. The other determinations made were the total 
nitrogen, the nitrogen as ammonia, and the nitrogen which could 
be titrated as formaldehyde expressed as a percentage of the 
total. 

Pepsin contains about 25% of titratable nitrogen ; trypsin some 
28%. On auto-digestion these figures increase to 37% and 58% 
respectively. 

Egg-white, casein, lean beef, edestin, gliadin, gelatin, and Witte 
peptone were incubated with pepsin or trypsin, and the above measure- 
ments made every few days. With pepsin, after about one hundred and 
seven days' action, from 30 — 38% of the total nitrogen can be titrated 
with formaldehyde. The action of the pepsin itself very soon falls off and 
stops altogether, subsequent digestion being due to the action of the 
acid ; accordingly, fresh pepsin was occasionally added. It is evident 
that the products of very prolonged peptic action are in the main due 
to the action of the acid present. 

Much evidence as to the nature of the hydrolysis is given by the 
ratio of the alkali required in the 4th and 1st stages of titration. 
In the case of glycine this is 48*9 ; for glycyl-glycine it is only 2*1 . 
Alanine has a value of 647; arginine, lysine, cystine, and tryptophan 
have values below 10; the values for aspartic acid, 162, and glutamic 
acid, 194, are very high. The formation of amino-acids during hydro- 
lysis will therefore be indicated by a large increase in the value of the 
ratio. 

The experiments with pepsin show a low value, 2"1 — 2 7, for the 
ratio, which does not materially change during hydrolysis, indicating 
that the products of hydrolysis are polypeptides and not amino-acids. 
The amount of ammonia formed increases throughout hydrolysis ; it 
differs considerably in magnitude in the six proteins investigated, 
but is far larger in the case of pepsin and hydrochloric acid than with 
trypsin. 

The trypsin experiments show variations of from 25% in the case 
of gelatin to 60% in the case of egg-white in the amount of nitrogen 
which can be titrated in presence of formaldehyde. The titration 



i. 60 ABSTRACTS OF CHEMICAL PAPERS. 

ratio is, as a rule, larger with trypsin, being markedly so in the case of 
egg white, and it tends to increase during the progress of hydrolysis, 
indicating the formation of amino-acids. The results show clearly the 
differences between the action of the two ferments. 

The addition of pepsin to the products of a completed tryptic 
hydrolysis slightly increased the amount of nitrogen whicli could be 
titrated, and tended to lessen the titration ratio. The addition of 
trypi^in to a completed peptic digestion caused the greatest total 
hydrolysis measured, and an increase in the titration ratio, which, 
however, did not become so large as in the case of the f-imple tryptic 
digestion owing to the presence of the peptide constituents. 

For comparison, hydrolysis has also been effected by hydrochloric 
acid and by sodium hydroxide. The proportion of ammonia formed 
is greatest in the last case. The titration ratio indicates that acid 
hydrolysis is very similar to that caused by pepsin ; possibly pepsin 
acts as a catalyst for the weak acid. The titration ratio is higher 
in hydrolysis by alkali, but not as great as with trypsin ; probably 
the difference in the mode of action in the two agents depends 
mainly on the secondary changes produced by the alkali. 

E F. A. 

Inactivation of Trypsin by Dialysis against Distilled Water ; 
Reactivation of the Diastase by Addition of Salts. Albert 
Frouin and Arthur Compton {Compt. rend., 1911, 153, 1032 — 1034). 
— The proteolytic enzyme of pancreatic juice is rendered inactive when 
the liquid is submitted to dialysis for sixty-six to seventy-two 
hours, but can be activated by addition of certain salts, such as sodium 
chloride, bromide, iodide, fluoride, acetate, citrate, magnesium 
sulphate, and others, or by alkali hydroxides. If dialysis is prolonged 
beyond the period stated, the enzyme undergoes a permanent loss of 
activity. W. 0. W. 



Protection of Trypsin from Destruction by Heat. D. H. de 
SouzA (/. Physiol, 1911, 43, 374— 378).— A temperature of 80° 
destroys trypsin in five minutes; the protective actioa of peptone in 
the solution is very slight, but rather greater if the reaction is acid 
or neutral. Lower temperatures (65 — 70°) take longer to destroy the 
enzyme, and the protective action of peptone is somewhat greater. 
The protection is too small to be of any value in sterilising enzymes 
by heat. Experiments without antiseptics are not trustworthy. 

W. D. H. 

Tryptic Digestion of Silk. I. W. S. Hubbard (/. Amer. Chem. 
Soc.j 1911, 33, 2032 — 2035). — Experiments are described which show 
that silk is slowly hydrolysed by trypsin with formation of tyrosine, 
tryptophan, or a compound of this substance, and dextrorotatory 
tryptic peptones. E. G. 

The Conditions for Optimal Action of Invertase. Aristides 
Kanitz (Biochem. Zeitsch., 1911, 37, 50 — 51). — In view of various 
recent investigations on this subject, the author calls attention to his own 
work published in 1903, in which he showed that the optimal action 



i 



ORGANIC CHEMISTRY. i. 61 



of invertin from Aspergillus niger takes place in a medium with 
hydrogen ion concentration of 3*3 x 10"^ to 3'3 x 10"^ at a temperature 
of 56° (compare Abstr., 1904, i, 158). S. B. S. 

Mechanism of the Destruction of Diastases by Light. 
Henri Agulhon {Compt. rend., 1911, 153, 979 — 982. Compare this 
vol., ii, 243). — Enzymes are divisible into three classes according to 
their sensitiveness to light. Sucrase, tyrosinase, and laccase are 
destroyed by visible rays only in presence of oxygen ; in a vacuum 
they are destroyed only by ultra-violet light. Probably in the 
absence of molecular oxygen, hydrogen peroxide is the effective agent 
of decomposition. Emulsin and catalase are destroyed by light of all 
wave-lengths, even in a vacuum, but more rapidly when oxygen is 
present. Rennet is an example of a third type, the activity of which 
is not impaired by visible rays, but is rapidly destroyed by ultra- 
violet radiation in a vacuum. W. 0. W. 

The Mode of Action of Phosphatese. A. von Lebedeff {Zeitsch. 
physiol. Chem., 1911, 75, 499 — 500). — Polemical against Euler and 
KuUberg (Abstr., 1911, i, 1057). The results obtained by these 
authors were vitiated by the use of impure yeast-extract. 

H. B. H. 

The Influence of Temperature on the Action of 
Phosphatese. Hans von Euler and Hjalmar Ohlsen (Biochem. 
Zeitsch., 1911, 37, 312 — 320). — The aqueous extract of yeast dried at 
50° does not produce a synthesis of phosphoric esters of sugars from 
dextrose and phosphoric acid unless the former substance is previously 
partly fermented with living yeast. A synthetical enz}?me can 
therefore be separated from other enzymes in yeast. The extract of 
dried yeast becomes more active synthetically if it is warmed 
to 40° before acting on the mixture of phosphate and partly 
fermented dextrose. The explanation of this phenomenon has not 
yet been found, but preliminary experiments indicate that it is not 
due to the destruction of inhibitory substances. S. B. S. 

5-Nitro-2-aniinophenylarsinic Acid. Ludwig Benda (Ber., 
1911, 44, 3293— 3297).— It has been shown previously (Abstr., 1908, 
i, 591) that in the preparation of aminoarylarsinic acids from aromatic 
amines, the arsenic always enters the para-position to the amino- 
group, provided that this position is unoccupied. In the case of 
para- substituted amines, either the introduction of arsenic cannot be 
effected, or exceedingly small yields of o-aminoarylarsinic acids are 
obtained (Benda, Abstr., 1908, i, 747). An exception to this rule 
has been found in ;?-nitroaniline, which is readily converted into 
b-nifro-2-aminophe7tylar8inic acio?, N02*CgH3(OH)'AsO(OH)2, by heating 
it with arsenic acid at 210°. The acid crystallises in lustrous, orange- 
yellow prisms, m. p. 235 — 236° (decomp.), and yields an acetyl derivative 
and an almost colourless diazO'COjnpoxxnd. The constitution of the 
acid has been established by its conversion into 2-iodo-4-nitroaniline 
(Michael and Norton, Ab^tr., 1878, 406) by the action af potassium 
iodide and sulphuric acid on the aqueous solution of its sodium salt. 



L 62 ABSTRACTS OP CHEMICAL PAPERS. 

When heated with aqueous sodium hydroxide, it yields d-nitro- 
2-hydroxyphenylar8inic acid, N02'C6H8(OH)'A80(OH)2. This forms 
stout, lustrous, pale amber-yellow crystals, m. p. 247 — 248° (decomp.), 
and yields a monopotassium salt, CgH50gNKA8,H20, crystallising in 
almost colourless needles or leaflets ; the dipotassium salt forms 
intensely yellow, felted needles. 

3 : b'Dinitro-2-hydroxyphenylar8inic acid, 

OH-CeH2(NOo)2-AsO(OH)a, 
prepared by nitrating the mononitro-acid, crystallises in pale yellow 
needles, m. p. 237°. 

Reduction of 5-nitro-2-hydroxyphenylar8inic acid by means of 
sodium hyposulphite yields 5 : b' -dia7nino-2 : 2' -dihydroxyarseno- 
bemene, which forms a yellow powder, yields a microcrystallioe 
dihydrochloride, and, when oxidised with sodium hypochlorite in 
alkaline solution in the presence of p-xylenol, gives a cornflower-blu3 
solution of the corresponding indophenolarsinic acid. F. B. 

Constitution of the Isomeric Aminophenylarsinic Acids, 
and of Michaelis's Nitrophenylarsinic Acid. Alfred Bektheim 
and LuDWiG Benda (Ber., 1911,44, 3297— 3300).— m-Aminophenyl- 
arsinic acid has been prepared by eliminating the amino-group from 
3-nitro-4-aminophenylar8inic acid (Abstr., 1911, i, 1055) and 5-nitro- 
2-aminophenylarsinic acid (preceding abstract), and fonnd to be 
identical with the acid previously obtained (Bertheim, Abstr., 1908, 
i, 590) by the reduction of the nitrophenylarsinic acid prepared by 
Michaelis and Loesner (Abstr., 1894, i, 187) by directly nitrating 
phenylarsiric acid. Michaelis and Loesner's acid is accordingly 
m-nitrophenylarsinic acid. 

The elimination of the amino-group from 3-nitro-4-aminophenyl- 
arsinic acid was accomplished by diazotisation and subsequent 
treatment of the resulting diazo-compound with hypophosphorous acid. 
In the case of 5-nitro-2-aminophenylarsinic acid, the replacement of 
the diazo-group was effected by means of copper bronze and alcohol. 
The w-nitrophenylarsinic acid thus obtained was isolated by means of 
the ziiic salt, and reduced with sodium amalgam to 7/i-auiinopbenyl- 
arsinic acid. F. B. 

p-Phenylenediaminearsinic Acid. Ludwig Benda (Ber., 1911, 
44, 3300 — 3304). — i^Phenylejiediaminearsinic [2 : b-diaTninophenyl- 
arsinic] acid is prepared by reducing 5-nitro-2-aminophenylarsinic acid 
(preceding abstracts) in aqueous sodium hydroxide solution with 
ferrous chloride. It crystallises in slender needles, which become 
violet on exposure to air and light, and decompose at 210 — 215°. It 
reacts with only one molecule of nitrous acid to form a diazo -corapoundj 
which yields reddish-violet, yellowish-orange, and red azo-dye^i with 
^-salt, resorcinol, and yS-naphthol respectively. When the diazo- 
compound is treated with copper and alcohol, and the resulting mono- 
aminophenylarsinic acid again diazotised and coupled with /3-naphthol, 
a red azo-dye is obtained, which is reduced by sodium hypo- 
sulphite to m-aminoplienylarsinic acid. The diazotisation of 2 : 5-di- 
aminophenylarsinic acid therefore takes places at the amino-group in 
the 2-position. 



I 



I 



ORGANIC CHEMISTRY. i. 63 



Attempts to prepare o-aminophenylarsinic acid (see following 
abstract) by acetylating 2 : 5-diaminophenylarsinic acid, diazotising 
the resulting 2-amino-b-acetylaminophenylar8inic acid, and combining 
the diazo-compound thus obtained with /8-naphthol, followed by hydro- 
lysis and subsequent removal of the amino-group from the resulting 
azo-dye, were only partly successful. o-Aminophenylarsinic acid was 
identified in the product, but could not be isolated in a crystalline 
condition. F. B. 

o-Aminophenylarsinic (o - Arsanilic) Acid. Ludwig Benda 
{Ber., 1911, 44, 3304— 3308).— 5-Nitro-2-aminophenylarsinic acid 
(preceding abstracts) and oxalic acid react when heated with con- 
centrated aqueous sodium hydroxide at 160 — 165° to form 4 : ^'-di- 
nitro-oxanilide-2 : 2'-diarsinic acid, 

AsO(OH)2-C,H3(N02)-NH-CO-CO-NH-C6H3(N02)-AsO(OH)2, 
which is reduced by iron and acetic acid to 4 : 4:'-diamino-oxanilide- 
2 : ^'-diarsinic acid. The amino-group is eliminated from the latter 
compound by diazotisation and treatment of the resulting diazo- 
compound with copper and alcohol. 

The oxanilide-2 : 2' -diarsinic acid, 

AsO(OH)2-C6H4-NH-CO-CO-NH-C6H4-AsO(OH)2, 
thus obtained crystallises in lustrous, silvery leaflets, and is hydro- 
lysed by dilute sulphuric acid to o-aminophenylarsinic acid, 

NH2-C6H4-AsO(OH)2. 
This crystallises in needles, m. p. 153°, and is distinguished from its 
isomerides by its much greater solubility in water and the ease with 
which the arsenic acid residue is removed. When heated with 
potassium iodide and dilute sulphuric acid at 80°, it is instantly con- 
verted into o-iodoaniline. Its toxicity is much greater than that of 
the jo-isomeride. The crystalline barium and silver salts are described. 

F. B. 

Nitrohydroxyarylarsinic Acids. Ludwig Benda and Alfred 
Bertheim {£er., 1911, 44, 3445 — 3448). — The nitration of jo-hydroxy- 
phenylarsinic acid and of 4-hydroxy-5-methylarsinic acid has been 
studied. 

3 - Nitro - 4 - hydroxyphenylarsinic acid is formed when sodium 
^-bydroxyphenylarsinate dissolved in concentrated sulphuric acid is 
treated with the theoretical quantity of nitric acid (D 1-4), the 
temperature not being allowed to rise above 0°. It forms nearly white 
crystals, which decompose when heated. The mono-, di-, and tri-sodium 
salts were prepared, the last-named existing in two forms. Its 
"p-toluenesulphonic ester, colourless leaflets, m. p. 171° previously 
sintering, was also investigated. 

3 : 5-BiniCro-i-hydroxyphenylarsinic acid was prepared by nitrating 
sodium jp-hydroxyphenyiarsinate dissolved in concentrated sulphuric 
acid by means of nitric acid (D 1*52), the temperature being maintained 
at between 15° and 20°. It decomposes when heated. In alkaline 
solution it yields a deep red coloration on the addition of sodium thio- 
sulphate. The mononitro-acid shows no change in colour on similar 
treatment. 

b~Nitro-^-hydroxy-n\-tolylarsinic acid was prepared, from 4-hydroxy- 
m-tolylarsinic acid according to the method used in the preparation 



i. 64 ABSTRACTS OF CHEMICAL PAPERS. 

of 3-nitro-4-hydroxyphenylar8inic acid. It crystallises from 50% 
acetic acid in faintly yellow leaflets or needles. H. W. 

3-Nitro-4-bydroxyphenylar8inic Acid. Ludwig Benda (Ber., 
1911, 44, 3449 — 3451). — Diflficulties were encountered in applying the 
method given in the previous abstract to the technical preparation of 
3-nitro-4-hydroxyphenylarsinic acid, the latter being required for the pre- 
paration of the drug salvarsan. Attempts were therefore made to pre- 
pare an azo-compound from crude /?-hydroxyphenylarsinic acid, which, 
on reduction, would yield either 3-amino^4-hydroxyphenylarsinic acid or 
di-7n-aminodi-;^hydroxyarsenobenzene |(the base of salvarsan). The 
compounds obtained by coupling jt?-hydroxyphenylarsinic acid with 
/>-nitrodiazo benzene or with diazobenzene were, however, found 
to be completely free from arsenic. 

3-Nitro-4-hydroxyphenylarsinic acid was finallyobtained in quantitative 
yield by warming 3-nitro-4-aminophenylarsinic acid (compare Bertheim, 
Abstr., 1911, i, 1035) with potassium hydroxide and subsequent treat- 
ment with hydrochloric acid. When similarly treated, 5-nitro- 
6-amino-m-tolylarsinic acid yielded the corresponding 5-nitro- 
6-hydroxy-77i-tolylarsinic acid. H. W. 

Preparation of Mercury Derivatives of Indoles. C. F. 
BoEHEiNGEE k SoHKE (D.R.-P. 236893). — The action of mercuric 
acetate on indole derivatives in alcoholic solution yields products 
which are readily decomposed by hot dilute mineral acids into their 
generators. 

The following compounds were prepared : (I) CigHjgOgNHg (a red 
precipitate) from phthalylmethylindole ; (II) CuHijOgNHg (needles) 
from 1-methylindole; (Hi) CjoHgOgNHg from 1-methylindolecarboxylic 
acid; (IV) CjgHigOgNHg (a brown precipitate) irom anisi/lindole, m. p. 
226°, obtained by the action of zinc chloride on acetylanisolephenyl- 
hydrazone ; (V) C22H240gN2Hg3 (a yellow precipitate) from 2-methyl- 
indole. 



-TjC-Hg-O-COMe / V iiC-Hg-0-COMe 

•Ic-Me I I l!CH 

N-CO-CgH^-COgH NMe 

(I.) . (11.) 

||C-Hg-OH 
l!c-C02H 

NMe 
(III.) 

NH \ NH 

(IV.) (V.) 

F. M. G. M. 



I 66 



Organic Chemistry. 



Three Normal Saturated Hydrocarbons : Triacontane, 
Tetratriacontane, and Hexatriacontane. Albert Gascard 
(Compt.rend., 1912, 154, 1484:— 1487). — Pentadecyl alcohol (Simonini, 
Abstr., 1892, 1301) was converted into pentadecyl iodide, brilliant 
scales, m. p. 24*5°. This was boiled with xylene and sodium for 
twelve hours, when n-triacontane^ CgQHgg, was obtained as brilliant 
scales, m. p. 65*2 — 65*5°, isomeric, if not identical, with the hydro- 
carbons isolated from plants by Klobb (Abstr., 1910, ii, 1100), and 
from the products of electrolysis of potassium palmitate by Petersen 
(Abstr., 1906, i, 331). 

Heptadecyl stearate was prepared by heating silver stearate with 
iodine. The compound crystallises in silky lamellae, m. p. 64'7°, and 
on hydrolysis yields n-heptadecyl alcohol, pearly scales, m. p. 54". 
Heptadecyl iodide, brilliant lamellae, m. p, 33" 6°, when treated with 
sodium gives n-tetratriacontane, Cg^H^-Q, occurring as very brilliant 
scales, m. p. 73*2'^. 

Similarly, octadecyl iodide, m. p. 33*5°, has been converted into 
n-hexatriacontane, CggH^^, a substance crystallising in brilliant lamellae, 
m. p. 76°. W. 0. W. 

Catalytic Action. V. Friedel and Crafts' Reaction. Jacob 
BoESEKEN {Rec. trav. chim., 1911, 30, 381 — 39l. Compare Abstr., 
1910, i, 152). — In continuation of the previous work it is shown that 
dissociable chlorides, such as sulphuryl chloride, pentachloroethane, 
and chloral, act as a mixture of the non-decomposed molecule, in which 
the chlorine atoms are activated, and of its products of decomposition. 
The first-named chloride has been tried with benzene, toluene, and 
anisole. With the two former the products of reaction are those of 
the condensation of the non-dissociated molecule as well as those of 
the products of dissociation. The latter are in excess, since the 
equilibrium SOgClg Z^ SOg -I- Clg is displaced to the right by the 
catalyst. In the case of anisole the reaction only yields the sub- 
stances formed from the products of dissociation, probably owing to 
the fact that the anisole is attacked so energetically by these products. 

With pentachloroethane, it is only the activated chlorine in the 
undecomposed molecule which attacks benzene, although at the same 
time some of the pentachloroethane is decomposed into tetrachloro- 
ethylene and hydrogen chloride. 

Chloral and benzene give a very complex reaction, a large number 
of substances being formed, owing to the fact that the products of 
decomposition of the chloral can re-combine to form other substances. 

W. G. 



^uTien 



utoxidation of Trichloroethylene. Ernst Erdmann {J, pr. 
1912, [ii], 85, 78 — 89). — Trichloroethylene was prepared by 
VOL. on. 1. / 



1. 66 ABSTRACTS OF CHEMICAL PAPERS. 

the action of alcoholic potash on tetrachloroetbane ; it has b. p. 
85'8— 86-0774 1-6 mm., m. p. -83°, Df ]-4640, J)'/' 1-4695. 

In contact with air this liquid undergoes autoxidation ; at elevated 
temperatures and increased pressure, for example, in an autoclave, the 
reactions are complex, a mixture of halogen compounds boiling between 
100 and 240° being obtained, due to polymerisations and secondary 
actions ; at the ordinary pressure and below 60° the process is much 
simpler, the final products being hydrogen chloride, carbon monoxide, 
carbonyl chloride, and dichloroacetyl chloride, the latter being the 
only liquid product. In order to obtain measurable quantities of the 
products the experiment may have to extend over several weeks; the 
rate of reaction varies as the ratio of trichloroethylene to oxygen. 
With excess of oxygen, after twenty-eight days, the amount of oxygen 
removed is between I and 2 atoms for each molecule of trichloro- 
ethylene originally present, thus indicating the simultaneous reactions : 
CHCirCClg + O = CHClg-COCl and CHCKCClg + Og = CO + HCl + COCI2. 

On passing ozonised oxygen through trichloroethylene, hydrogen 
chloride, carbonyl chloride, and carbon monoxide are formed, but no 
dichloroacetyl chloride. By using a solution of trichloroethylene in 
hexahydrotoluene at - 79°, the increase in weight due to ozonide 
formation could be directly determined and indicated an addition of 
one molecule of ozone to each molecule of trichloroethylene ; the 
ozonide, which was too unstable and explosive to be examined in a pure 

state, is therefore formulated 1 A*n^* ^^® gases from an explosion 

of the ozonide contained carbon monoxide, carbonyl chloride, hydrogen 
chloride, and an oxide of chlorine ; the decomposition can be moderated 
by solution in chloroform or hexahydrotoluene, but the products are 
the same with the exclusion of the oxide of chlorine. In decomposition 
in the presence of water, hydrogen peroxide is formed. The spon- 
taneous decomposition of the ozonide in a dilute solution (for example, 
excess of trichloroethylene), in the absence of water, indicates that an 
atom of oxygen is first removed, being chemically absorbed by the 
solvent, and after removal of excess of trichloroethylene in a vacuum, 

CTTOl'PPI 
a pungent oil remains, to which is attributed the formula ' 1 ^ ; 

it rapidly decomposes, giving carbon monoxide, hydrogen chloride, and 
carbonyl chloride, the first two of which can be regarded as the decom- 
position products of the intermediate formyl chloride. No indication 
of dichloroacetyl chloride was detected in any decomposition of the 
ozonide. 

The author, theiefore, t-uggests an explanation of the autoxidation 
of trichloroethylene described by the formulae : 

CHClICClj -^ CHC1-CC12 --> CHCl-CClg --> CHCla'COCl. 
\o/ ^0^ 

O +0 

(I.) (II.) (III.) (IV.) 

The method of formation of the dichloroacetyl chloride is thus 
explained. The nascent oxygen formed at (III), together with ordinary 



I 



ORGANIC CHEMISTRY, 1. 67 



oxygen, then attacks another molecule of trichloroethylene, like a 
molecule of ozone, giving the ozonide, which then decomposes as 
described above. 

The possibility of autoxidation is not restricted to unsymmetrical 
substituted ethylenes (compare Demole, Abstr., 1878, 847 ; Demole and 
Diirr, Abstr., 1878, 846; Anschutz, Abstr., 1880, 98). 

The action of other oxidising agents on trichloroethylene was also 
investigated ; anhydrous ferric chloride attacks the substance in a sealed 
tube first at 85°, the former being reduced to the ferrous salt, whilst the 
latter gives pentaehloroethane ; at higher temperatures the last 
substance loses a molecule of hydrogen chloride, and the resultant 
tetrachloroethylene becomes further converted into hexachloroethane. 

D. F. T. 

The Distillation of Methyl Alcohol. Gustav Birstein, 
H. Denneler, and Alfred Heiduschka {Zeitsch. angew. Chem.^ 1911, 
24, 2429 — 2430). — Two series of experiments on the volatility of 
solutions of methyl alcohol have been carried out. In the first series, 
in which the solutions were distilled under constant pressure, it was 
shown that even dilute solutions of methyl alcohol yielded distillates 
comparatively rich in methyl alcohol. In the second series, in which 
the temperature was kept approximately constant, and air drawn 
through the solution, the concentration of alcohol in the distillate was 
found to be invariably slightly greater than in the original solution. 
The bearing of these results on the commercial preparation of 
formaldehyde is discussed. H. W. 

Action of Potassium Hydroxide on Primary Alcohols ; 
Preparation of the Corresponding Acids. Marcel Guerbet 
^{Compt. rend., 1912, 154, 1487— 1489 ; J^. Pharm. Chim., 1912, [vii], 
6, 58— 64).— Dumas and Stas (Ann. Chiin. Phys., 1840, [2], 73, 
113) found that potassium hydroxide acts on methyl, ethyl, and amyl 
alcohols at 200 — 230°, transforming them into the corresponding 
acids, with liberation of hydrogen. It is now shown that in the case 
of the lower alcohols, dehydration also occurs with formation of 
©thylenic hydrocarbons. The higher alcohols, however, form only 
hydrogen and the potassium salt of the acid. This method of 
oxidation is very advantageons for alcohols above the Cg terms, since 
it is unnecessary to employ sealed tubes, and the yield is practically 
theoretical. 

^-Methylpentanol gives a 95% yield of the corresponding acid, 
which was characterised by conversion into its amide, m. p. 85°. 
P-Heptylhexoamide, CH3-[CH2]3-CH(C7Hi5)-CH2-CO-NHo, has m. p. 
108°. "W. O. W. 

Calcium Ethoxides. Robert de Forcrand {Compt. rend., 1912, 
164, 1441—1444. Compare Abstr., 1895, i, 259; Doby, Abstr., 
1903, i, 546 ; Chablay, this vol., i, 3).— Calcium ethoxide, 

Ca(GEt)2,2EtOH, 
when allowed to remain over concentrated sulphuric acid, slowly loses 
alcohol. A specimen prepared in 1905 now approximates in com- 



i. 68 ABSTRACTS OF CHEMICAL PAPERS. 

positiou to the formula 3CaO,EtOH,2H20 or Ca(OKt)2,5CaO,5H20. 
The suggestion is put forward that a process of catalytic decom- 
position occurs, calcium oxide, the active agent, behaving as the 
thorium dioxide in Sabatier and Mailhe's experiments (Abstr., 1910, 
i, 294). Calcium ethoxide is analogous to the hypothetical compound 
ThO(OEt)2, losing ethylene or ether like this substance, but having 
greater stability at the ordinary temperature. W. O. W. 

Tbe Crystallographic Distinctions of Nitroglycerol. Sigurd 
Nauckhoff {Zeitsch. IScJieiss. Sprengstoffw.^ 1911, 6, 124 — 125). — The 
paper contains sketches and measurements of two forms of nitro- 
glycerol crystals ; they are of the bipyramidal class of the rhombic 
system, but when obtained from supercooled nitroglycerol have a 
flattened, tabular habit, whilst those deposited from saturated ethereal 
solution are of rhombic character ; their optical properties are also 
described. 

The author discusses the work of Kast {Atti VI Cong. Internaz. 
chim. appl. Illb), and considers that the m. p. of nitroglycerol is 
- 12-6°, instead of - 13-5° (Kast). F. M. G. M. 

Transformations of Thio- and Seleno-phosphoric Esters. 
P. PisTSCHiMUKA (J.p\ Chem., 1911, [ii]. 84, 746—760; from Mem. 
Inst. agr. forest., Nowo Aleotxcndria, 1911, 1 — 148). — The esters of 
thiophosphoric acid should exist in two isomeric forms, P0(0E,)2*SK. 
and PS(0K)3, but, hitherto, only the latter series have been prepared. 
It is found that the esters of this series combine with a large number 
of metallic salts, yielding additive compounds, which undergo decom- 
position, either at the ordinary temperature or when heated, with the 
formation of derivatives of isothio phosphoric acid, P0(0H)2'SH; 
thus, the additive compounds of the alkyl esters with silver nitrate, 
PS(OR)8,AgN03, readily lose one molecule of alkyl nitrate and form 
salts of the composition P0(0R)2'SAg. The isomeric esters are 
obtained from these salts by the action of alkyl iodides. 

A similar transformation into derivatives of the isomeric acid is 
caused by alkalis, alkyloxides, alkyl halides, and ammonia, although 
the formation of intermediate additive products with these compounds 
could not be observed. The transformation is, however, not confined 
to esters of monothiophosphoric acid, but is common to all esters of the 
type PS(XU)2-0R (where X = or S), derivatives of P0(XH)2-SH 
being produced. 

Esters of selenophosphoric acid, PSe(0R)3, have also been prepared 
and converted into the isomeric forms by methods similar to those 
employed in the case of the thiophosphates. 

The alkyl thiopho.sphates of the type PS(0R)3 were prepared by 
the method described previously (Abstr., 1909, i, 5); the ethyl ester 
has b. p. IO672O mm., DJ 1*0944; the propyl ester, b. p. 133—134°/ 
20 mm , D^ 1*0409 ; the isobutyl ester, b. p. 155720 mm., 
D" 0*9907. On treatment with nitric acid, they yield esters of 
phosphoric acid, and are converted by sodium into the corresponding 
alkyl phosphites. 

The compound, PSClg'SEt, obtained by heating the acid chloride, 



ORGANIC CHEMISTRY. i. 69 

PClg-SEt, with sulphur, has b. p. 92710 mm., D^ 1-4453; it reacts 
with sodium ethoxide, yielding ethyl dithiophosphate, PS(0Et)2*SEt, 
b. p. 130720 mm., DJ5 M340. 

Ethyl trithiophosphate, obtained from the chloride PSClg'OEt and 
sodium ethylmercaptide, is a liquid, b. p. 155720 mm., DJ 1*1716. 

The following additive compounds with mercuric chloride were 
prepared : PS(OMe)3,2HgCl2, transparent needles, melting at 102° 
and simultaneously losing methyl chloride, forming the compound, 
PO(OMe)2'SHgCl,HgCl2, which passes at 150° into tbe compound^ 
SHgCl-Po(OMe)-OHgCl ; SHgCl-PO(OEt)2,HgCl2, forms stout, trans- 
parent prisms, m. p. 66°, which at 85° yield the compound^ 

SHgCi-PO(OEfc)-OHgCl; 
PS(OPr«)3,2HgCl2 ; PS{OCH2Pr^)3,2HgCl2 ; PS(SEt)2-OEt,2HgCl2, 
white needles, m. p. 81°; PS(SEt)3,2HgCl2, m. p. 84°. All additive 
compounds of the type PS(XR)2*OR,2HgCl2 lose one molecule of 
alkyl chloride at a relatively low temperature. 

The esters of thiophosphoric acid form with ferric chloride additive 
compounds of the general formula 3PS(OP)3,2FeCl2, which lose three 
molecules of alkyl chloride when heated ; the methyl compound forms 
large, yellow prisms, m. p. 125°; the ethyl compound is crystalline; 
thQ propyl and i^ohutyl compounds are oils. 

The ethyl esters ot di- and tri-thiophosphoric acid yield with ferric 
chloride oily additive compounds having a similar composition. 
Compounds of the same type are formed with ferric bromide, but 
only the mtthyl compound, 3PS(OMe)3,2FeBr3, m. p. 99°, is 
crystalline 

Ethyl thiophosphate combines with platinic chloride, yielding the 
compound, 3PS(OEt)3,2PtCl4, orange-yellow needliBS, m. p. 103°. The 
crystalline com,pound of methyl thiophosphate and auric chloride has 
m. p. 110°. 

Silver nitrate dissolves in methyl thiophosphate, yielding methyl 
nitrate and the silver salt, P0(0Me)2*SAg, and in ethyl thiophosphate 
to form the additive compound, PS(OEt)3,AgN03, which decomposes 
slowly at the ordinary temperature into ethyl nitrate and the silver 
salt, P0(0Et)2-SAg, m. p. 82°. 

Similar compounds are formed by the propyl and isobutyl esters. 
The phenyl ester reacts with silver nitrate, yielding o-nitrophenol and 
the compound, P0(0Ph)2*SAg. The behaviour of silver nitrite 
resembles that of the nitrate. 

Mercuric iodide combines with the alkyl thiophosphates, PS(0R)3, 
to form additive compounds, which are derivatives of the isomeric 
ester, P0(0R)2*SE,. Thus, ethyl thiophosphate, when heated with 
mercuric iodide at 180°, yields the compound, PO(OEt)2*SEt,2Hgl2. 

Similar compounds are formed by the esters of di- and tri-thio- 
phosphoric acid. The interaction of alcoholic ammonia and ethyl 
thiophosphate yields ethylamine and the compound, NH2*PO(OEt)2. 

Sodium hydroxide, sodium ethylmercaptide, and sodium alkyl- 
oxides react with the alkyl thiophosphates to form sodium salts of 
the composition P0(0R)2*SNa. The action of sodium hydroxide and 
sodium alkyloxides on the esters of di- and tri-thiophosphoric acids 
leads to the formation of a mercaptan or alkyl sulphide, together 



i. 70 ABSTRACTS OF CHEMICAL PAPERS. 

with sodium salts coDtaining a smaller number of atoms in the 
molecule. Sodium ethylmercaptide, on the other hand, gives rise to 
the Bodium salts, SNa-PO(SEt)-OEt and P0(SEt)2-SNa. 

The isomeric thiophosphoric esters of the type P0(0R)2'SR are 
obtained by the action of alkyl iodide on the above-mentioned silver 
salts, P0(0R)2'SAg, in alcoholic solution. The methyl ester has 
b. p. 107720 mm., Vl 1-2685; the ethyl ester, b. p. 122720 mm., 
D2 11245; the propj/l ester, b. p. 156720 mm., D° 1-0532; the 
isobutyl ester, b. p. 170720 mm., Dg 10102. 

The esters of selenophosphoric acid of the formula PSe(0R)3 are 
formed by the combination of " molecular " selenium and esters of 
phosphorous acid ; the methyl ester is a liquid, b. p. 95720 mm., 
DS 1-5387 ; the ethyl ester has b. p. 117720 mm., D° 1*3189. 

The following additive compounds were prepared : PSe(OMe)3,HgCl2 ; 
PSe(0Et)g,HgCl2 ; PSe(OMe)3,Hgl2, m. p. 66°, and is simultaneously 
transformed into its isomeride, PO(OMe)2'SeMe,Hgl2; PSe(OEt)3,Hgl2, 
large, yellow prisms, m. p. 32°, which pass at 75° into the isomeride, 
PO(OEt)2'SeEt,Hgl2, m. p. 95° and when warmed under diminished 
pressure lose ethyl iodide, yielding the compound, P0(0Et)2'SeHgI. 

Ethyl selenophosphate and sodium ethyl mercaptide react to form 
the sodium salt, P0(0Et)2*SeNa, m. p. 196°; the corresponding lead 
salt is unstable, and yields with ethyl iodide the ester, P0(0Et)2*SeEt, 
a liquid, b. p. UO72O mm., D^ 1*3593. 

Esters of the type PS(XR)2'0R are transformed by prolonged 
heating with an excess of alkyl iodide into their isomerides. Thus, 
ethyl thiophosphate, PS(0Et)3, is converted by ethyl iodide into its 
isomeride, P0(0Et)2'SEt, and by tsobutyl iodide into the ester, 
PO(OEt)2-S'CH2Pr^. 

With respect to the mechanism of the above-mentioned transforma- 
tions the author considers that, in all cases, additive compounds 
containing either a quadrivalent or sexavalent sulphur or selenium 
atom are first produced, and that these subsequently undergo 
tautomeric change and decomposition ; the action of sodium ethoxide 
on ethyl dithiophosphate is represented as follows : 

PS(OEt)2-8Et ^^ NaS-S(0Et):P(0Et)2-SEt -> 

NaS-S-P(0Et)3-SEt -■> NaS-P0(0Et)2 + EtgS. 

F. B. 

Complex Compounds of Platinous Bromide with Organic 
Sulphides. Leo A. Tschugaeff and (Mile.) D. Fraenkel (Compt. 
rend., 1912, 154, 33—35. Compare Abstr., 1910, i, 354).— When an 
aqueous solution of potassium platinobromide is treated with ethylene- 
dithioglycol ether, the compound, [Pt2C2H4(SEt)2]PtBr^, separates as 
a grey, microcrystalline precipitate, m. p. 157°. At 100° this substance 
changes into a yellow isomeride having the same m. p., but a greater 
solubility in water and chloroform. The above constitution is assigned 
to the substance on the ground that it unites with Reiset's bromide, 
forming the salt, [PtiNHgJPtBr^, together with a yellow compound, 
m. p. 157—158°. The latter has the constitution [C2H4(SEt)2]2PtBr2, 
since it can also be prepared by mixing the grey salt with ethylenedi- 



ORGANIC CHEMISTRY. i. 71 

thioglycol ether and potassium platino bromide in equimolecular 
proportions. 

Potassium platinobromide reacts with methyl sulphide, giving an 
unstable grey compound, [Pt4Me2S]PtBr4, m. p. 160°. On crystal- 
lisation from chloroform this changes into Blomstrand's salt, 
(Me2S)2PDBr,. 

Platinoiodides do not form derivatives with organic sulphides. 

W. O. W. 



Intramolecular Rearrangements of Aliphatic Sulphoxides. 
Thomas P. Hilditch {Ber., 1911, 44, 3583— 3589).— By treatment with 
alcoholic hydrogen chloride or with boiling acetic anhydride, diisoamyl- 
sulphoxide is converted into isoamyl mercaptan and ^sovaleraldehyde ; 
by the former reagent, thionyldiacetic acid is decomposed into 
thioglycollic and glyoxylic acids. a-Thionyldiisobutyric acidy 

SO(C]y[e2;C02H)2, 
m. p. 186°, is unchanged by alcoholic hydrogen chloride. 

An explanation of these decompositions is given which assumes the 
intermediate formation of thionium compounds. C. S. 

Complex Compounds of Platinum with Organic Selenides. 
I. E. Fritzmann {Zeitsch. anorg. Chem., 1911, 73, 239—255).— 
The isomerism of the compounds of platinous chloride with organic 
sulphides has been discussed by Tschugaeff and Subbotin (Abstr., 
1910, i, 354). The corresponding selenium compounds have not been 
examined, with the exception of those derived from ethyl selenide 
(Petren, Zeitsch. anorg. Chem., 1899, 20, 62). 

The isomerism observed is similar to that of the sulphur compounds. 
The a-compounds are more soluble than the /8-compounds, and are 
darker in colour. The former are to be regarded, in accordance 
with Werner's views, as m-modifications, and the latter as trans- 
modifications. The y-compounds are less stable than those of 
sulphur. 

A 4% solution of potassium platinochloride (1 mol.) is shaken with 
the alkyl selenide (2 mols.) until decolorised. The a-compound is then 
chiefly obtained. In order to prepare the )8-compound, 4 mols. of 
selenide are used, and the mixture is digested at 70 — 75° in a closed 
vessel until all is dissolved. The cooled solution is evaporated in 
a vacuum over calcium chloride and solid paraffin or rubber, and 
potassium chloride is then removed by washing. For analysis, the. 
compound is decomposed with sulphuric acid, and heated in hydrogen, 
to remove selenium, the residual platinum being weighed. Selenium, 
is estimated by boiling with aqua regia in a quartz vessel, evaporating, 
and precipitating the slightly acid solution with a hot saturated solu- 
tion of hydrazine sulphate. The precipitated mixture of platinum and 
selenium is collected, dried at 100°, and weighed, and the selenium is 
then removed by heating in hydrogen. 

Methyl selenide platinous chloride^ PtCl2,2Me2Se, has m. p. 163 — 163-5°. 
The a-form is partly converted into the /3-form by repeated crystallisa- 
llion from chloroform, and the reverse qhange is also observed. A^t a, 



i. 72 ABSTRACTS OF CHEMICAL J'AI'KKS. 

low temperature it ih possible to obtained the y- modification, but it 
can only be isolated in the form of the green Magnus salt, 

(Pt,4Me2Se)Cl2, 
by the addition of a solution of Reiset's salt, (Pt,4NH3)Cl2. 

Methyl aelenide platinous bromide, PtBrg.SMegSe, is red, and has 
m. p. 171° (decomp.). Propyl selenide forms the compound,VtC\2i2Pr^H9, 
m. p. 42'5 — 43°; only the a-modification has been obtained. ?i- Butyl 
selenide only yields an oily product, iso Amyl selenide yields an 
a-compound, PtC]2,2(C5Hi^)2Se, m. p. 97— 97'5° and a jS-compound, 
m. p. 115 — 116°. The phenyl selenide a-compound has m. p. 180°, and 
the p-compound, m. p. 178 — 179° 

Diethyl trimethylene diselenide forms an a- and a (3-compound, 
2PtCl2,2CH2(CH2-SeEt)2, both of which have m. p. 176—176-5°. A 
y-modification has been recognised by conversion into the Magnus 
salt. . C. H. D. 

Chemico-crystallographic Notes. L, Wagner (Zeitsch. Kryst. 
Min.^ 1911, 60, 47 — 56). — Fhosphonium iodide, PH^I ; tetragonal, 
D 2*860. Tetramethylphosphonium iodide ; tetragonal, a:c=l : 7310, 
D 1-746. Calcium formate, Ca(CH02)2 ; orthorhombic (bipyramidal) 
[a:6:c = 0-7599:l :0-9363 (Plathan)], D 2-023. Strontium formate, 
Sr(CH02)2; orthorhombic (bisphenoidal), a :6 : c = 0-7846 : 1 :0-8292, 
D 2'693. Mixed crystals of calcium and strontium formate resemble 
those of either one or other of the simple salts, but they also sliow an 
intermediate tetragonal form ; the two salts are therefore isotri- 
morphous. Strontium formate forms the hydrate, Sr(CH02)2j2H20, 
D 2'259 ; but calcium formate forms no hydrate. Anhydrous oxalic 
acid;orthorhombic, a:6:c = 0'8301 :1 : 0-7678, D 1-900. Nitrobenzene; 
monoclinic (domatici), a :6 :c = l-280 : 1 : ?; )3=117°21', m. p. 3-8°. 

L. J. S. 

Direct Synthesis of the Glycerides. Giuseppe Gianoli (Atti R. 
Accad. Lincei, 1911, [v], 20, ii, 653 — 654. Compare Abstr., 1911, 
i, 349 ; Bellucci and Manzetti, ihid.f i, 259). — Polemical. 

K. V. S. 

Formation of Cork. Max von Schmidt (J. pr. Chem.y 1911, [ii], 
84, 830— 832).— A reply to Zeisel's criticism (Abstr., 1911, i, 768) of 
previous work of the author (Abstr., 1910, i, 540). F. B. 

Derivatives of Tetrolaldehyde and its Acetal [Diethoxy- 
butinene]. Paul L. Viguier {Compt. rend., 1911, 153, 1231—1233. 
Compare Abstr., 1909, i, 691). — On treating diethoxybutinene with 
aniline hydrochloride, the hydrocJUaride, 

NHPh-CMe:CH-CH:NPh,HCl, 
is obtained as yellow crystals decomposing at 160°. No definite com- 
pound was obtained from aniline, and phenylmethylpyrazole was the 
only definite product with phenylhydrazine. Urethane combines with 
the acetal, in presence of hydrogen chloride, giving the compound, 
CMe:C-CH(NH-C02Et)2, slender needles, m. p. 188—189°. 
Acetal unites with alcohol, in 'presence of sodium ethoxide, for; 



ORGANIC CHEMISTRY. i. 73 

aay-triethoxy-^^-hutyUne, 0Et-CMe:CH-CH(0Efc)2, b. p. 190— 195^ 
under ordinary pressure, 82—86715 mm., D^^ 0-908, < 1-430. 

Exposure to air converts triethoxybutylene into ^-ethoxycrotonic 
acid. On hydrolysis, it appears to form acetoacetaldehyde, but this 
rapidly polymerises to triacetylbenzene. When treated with semi- 
carbazide hydrochloride, it yields a compound, m. p. 127 — 128°, 

having the constitution i^' J^>N-CO-NHg. W 0. W. 

Action of Monochlorocarbamide on Ketones. Auguste 
Behal and A.. Detceuf {Compt. rend., 1911, 153, 1229—1231. Com- 
pare Abstr., 1911, i, 957). — On allowing chlorocarbamide to act on the 
calculated amount of an aliphatic ketone in aqueous solutions for 
three to five days, an excellent yield of a monochloro-ketone is 
obtained. Symmetrical ketones give the halogen derivative, in which 
the chlorine is next to the carbonyl group, whilst unsymmetrical 
ketones give two halogen derivatives, the secondary one pre- 
dominating. 

On boiling the semicarbazones of chloro-ketones with water, hydrogen 
chloride is eliminated and a ketol formed ; thus the semicarbazone of 
^-chloropropane-y-one gives ^-hydroxypropane-y-one. 

Chlorocarbamide and methyl hexyl ketone give a chloro-octanone, 
m. p. -25°, b. p. 104—108720 mm., D 1-0034; the semicarbazone 
has m. p. 133°. Acetophenone forms only w-chloroacetophenone ; 
cyclic ketones also undergo chlorination. W. O. W. 

Action of Dilute Nitric Acid on Starch and on Dextrin. 
William Oechsner de Coninck and Albert Raynaud {Eev. gen. Chim. 
pure appl., 1910, 14, 169 — 170). — An investigation on the action of 
dilute nitric acid on dextrin and starch. The dilution of the nitric 
acid varied from 1 to 5 c.c. of acid (36°Be) in 50 c.c. water, and 
the results indicated that the amounts of dextrose formed during the 
same interval of time increased with the concentration of the acid, but 
that this increase was less rapid with dextrin than with starch. 

With low concentrations, more dextrin than starch underwent 
hydrolysis, but at the highest concentration dextrin yielded 87*7% 
dextrose as compared with 90% from starch, indicating that in the 
former oxidation had to some extent interfered with saccharification. 

F. M. G. M. 

Modifications Undergone by Nitrated Celluloses and 
Powders Derived from them, under the Influence of Heat. 
R. Eric (Compt. rend., 1912, 154, 31 — 32). — The changes produced in 
nitrated celluloses by heat can be followed by measuring the viscosity 
of an acetone solution in the usual way. The effect of heating the 
solid at 110° is to diminish the viscosity of the solution. 

W. 0. W. 

The " Cause " of the Beckmann Rearrangement. Pietrr J. 
Montagne {Chem. Weekblad, 1911, 8, 968—976. Compare Abstr., 
1910, i, 623). — In the author's opinion, the Beckmann rearrangement 



i. 74 ABSTRACTS OF CHEMICAL PAPERS. 

18 a simple exchange of position between the alkyl group attached to 
carbon and that attached to nitrogen. The assumption of the inter- 
mediate formation of an oxime-ester is at variance with the experimental 
facts. A. J. W. 



New Compounds of the Choline Type. G. A. Menge (J. Biol. 
Chem., 1911, 10, 399— 406).— The chloride of a - methylcholine, 
NClMeg'CHMe'CHg'OH, has been prepared as follows : allyl chloride 
was converted into the chlorohydrin, and then into the corresponding 
acetate ; this by treatment with hydrochloric acid was converted into 
the acetate -chloride, and saponified to give the desired chlorohydrin, 
CHMeCl-CHg-OH. On heating at 100° in a sealed tube with 
trimethylamine dissolved in alcohol, the choline was obtained as a 
viscous, yellow oil, from which a hygroscopic, colourless solid separated 
on cooling. The yellow jylatinichloride decomposes at 254 — 255° ; the 
aurichlorid-e is definitely crystalline : it sinters above 180°, m. p. 
198—199-5°. 

By condensing monochloroacetone with magnesium alkyl halides, 
the chlorohydrins of /S-methylpropylene ayS-glycol and y8-methyl- 
butylene a/?-glycol are obtained. With trimethylamine these yield 
)8-disubstituted cholines. 

P- Dimethylcholine chloride, NClMeg'CHg'CMeg'OH, is obtained as 
a colourless, hygroscopic solid. The platinichloride crystallises in 
yellow, short, individual prisms or foliated clusters, which blacken at 
240°, decomp. 245°. ^- Methyl- P-ethylcholine chloride, 

NClMeg-CHa-CMeEt-OH, 
forms a platinichloride, which sinters at 240°, m. p. 242 — 243° 
(decomp.). E. F. A. 



Stereoisomeric Cobalt Compounds. Alfred Werner (Annalen, 
1911, 386, 1 — 272). — The author's investigations on the stereo- 
isomeric cobalt compounds have now reached such a stage, that stringent 
proofs have been obtained for the stereochemical conceptions, and 
methods which are free from objections have been devised for the 
determination of the configurations of the various isomerides. A 
summary of the methods used, and of the results obtained, is given in 
the present paper, the greater part of the work consisting of hitherto 
unpublished investigations. 

The general results arrived at may be briefly summarised as 
follows : The investigation of inorganic compounds containing the 
complex radicle CoAg has shown that in all these compounds the six 
groups A are in direct connexion with the central cobalt atom. Any 
space formula used to represent these compounds must be such that 
positions occupied by the groups A are all equivalent ; this follows 
from the fact that no stereoisomerides are known having the 

formula Co -r»^ • It has hitherto been impossible to prepare more 
than two stereoisomerides of the formula Co o* L so that the groups 



T^ai 



ORGANIC CHEMISTRY. i. 75 



and B must occupy the corners of an octahedron, the cobalt atom 
being in the centre ; the plane formula and prism formula would each 
give three possible isomerides. The groups B in the stereoisomerides 

Co ^4 must consequently occupy the cis- and ^ra^is-positions. 

Investigation has shown that in all cases when the two groups B are 
replaced by a bivalent group, giving three-, four-, five-, or six-membered 
ring«, the same compound results, no matter whether the cis- or trans- 
isomeride was used in the preparation. It appears, therefore, that 
there is only one position in the complex (the cis-position) favourable 
to the formation of such rings, this being in accordance with the 
octahedral arrangement of the groups, and in analogy with the forma- 
tion and non-formation of anhydrides from organic cis- and trans- 
isomerides. Use has been made of this result in the determination of 
the configuration of the various stereoisomerides, but great caution is 
necessary in drawing conclusions, owing to the ready transformation 
of one isomeride into the other 

Diaquo-^2i\tB, Y\^r\ Co eng Xg, — The ots-isomerides have been 

characterised by their preparation from the carbonato-salts, as also 
from the hexol- and diol-dicobaltic salts. The cts-compounds only are 
known in the tetrammine series, whereas both cis- and frans-compounds 
of the ethylenediamine series have been prepared. The configuration of 

the hydroxo-aquo-SB.\ts, \ jt r\ ^o en^ X, is deduced from that of the 

diaquo-salts because of their formation from the latter by loss of a 
molecule of acid. Both cis- and trans-isomerides are known. 

Bihalogeno-seilts, [Xg Co eUgJXg. — The two stejeoisomeric dichloro- 
salts are known, both in the tetrammine and diethylenediammine 
series. The m-isomeride (violeo-salt) is the first product of the 
action of concentrated hydrochloric acid on the carbonato-salt ; it 
readily changes into the ^raws-isomeride (praseo-salt) under the 
influence of concentrated hydrochloric acid. The cis-dibromotetra- 
ammine salts are not known. Stereoisomeric halogenoaquo-ssiltSj 

TT ^ Co eug Xg, are not known ; in all cases the ciVisomeride is 

alone formed. 

Halogeno-isothiocyanato-sBMs, qoxt ^° ^^2 r^- — Stereoisomeric 

chloro- and bromo-isothiocyanato- salts are known. Their configuration 
has to be decided chiefly by their colour (see later), since they so readily 
undergo transformation. The isothiocyanate group deepens the colour 
of the cobaltammines, and it follows that the violet chloro-salts and 
indigo-blue bromo-salts are the irans-isomerides, the czs-isomerides 
being red and bluish-red respectively. Similar results hold for the 

isothiocyanato-aqi^o-ssihs, lt o ^^ ®°2 P^2' ^^^ violet salts forming 

the trans-, and the orange the cis-isomerides. The configuration of 

the halogeno-amininediethylenediamine salts, L^ ^ Co eug Xg, has 

been determined by oxidation of the corresponding halogeno-isothio- 



i TH ABSTRACTS OF CHEMICAL PAPERS. 

cyanato-salts with hydrogen peroxide ; both the chloro- and bromo- 
saltB have been prepared. The conRtitution of the aquo-ammine- 

disihylenediamine salts, pT^ Co eng Xg, is determined by their 

transformation into the halogeno-amniine-salts by interaction with 
the halogen acids. The stereoi^omeric di\%othiocyanato-QB\t»f 

[SON 1 

apT»T Co eng X, have already been described (Abstr., 1900, i, 86), 

but the wrong configuration given to them. The ciVisomerides are 
those which were formerly characterised as dithiocyanato-saits, as 
may be deduced by their oxidation with hydrogen peroxide and 
subsequent evaporation with hydrochloric acid, whereby the m-chloro- 
ammine salts are formed. The irawa-isomerides on oxidation with 
chlorine yield <rans-diamminediethylenediaminecobaltic salts, and were 
formerly characterised as diwothiocyanato-salts. The configuration 

of the diamminediethylenediamine salts, I tt*>t Co en^ Xg, was 

determined by their solubilities, the cia- being more readily soluble 
than the ^ran«-isomerides (compare below). The configuration previously 
ascribed to them (Abstr., 1907, i, 290) is incorrect. Oxidation of 

TT >g- Co eug Xg, 

with hydrogen peroxide gives rise to the diammine salts, whereby the 
structure of the former salts is ascertained. The configuration of the 

niiroamminediethylenediamine salts, p^ Qq eng Xg, follows from 

£heir formation from the isomeric aquo-ammine salts, or from their 
transformation into the chloro-ammine salts. On oxidation of 

rscN n 

the isothiocyanatoniirodiethylenediamine salts, r) >t Co en^ X, with 

hydrogen peroxide, nitroammine-salts are formed, whereby the 
configuration of the former salts can be ascertained. Of the dinitro- 
dieihylenediamine salts, [(N0jj)2 Co engJX, the croceo-salts are the 
trans-f whilst the flavo-salts are the cis-isomerides. This is ascertained 
by their formation from the stereoisomeric diaquo-salts by the action 
of nitrous acid, the dinitrito-salts first formed transforming into 
the dinitro-salts. The configuration of the chloronitro-ssilts, 

[CI n • . 

^ ^ Co eUg X, is ascertained by their transformation into the 

dinitro-salts by interaction with sodium nitrite. 

Influence of the Constitution oftlie Complex Radicle, Co p.* , o:i the 

Existence o/ Stereoisomeric Cobalt Ammonias. — The m-compounds of the 
ammonia series are less readily produced than those of the diethylene- 
diamine series, and transform much more readily into the trans- 
isomerides. cis-Dichloro-compounds of the trimethylenediamine 
series cannot be prepared, all methods of preparation giving the green 
<ra7w-isomerides. The nature of the halogen has an effect, in that, 
although cis- and <r«n*-isomerides have been prepared in the dichloro- 
and dibromo-diethylenediamine series, no ci«-dibromo-compounds have 
been obtained in the ammonia series : in neither series could iodo- 



ORGANIC CHEMISTRY. i. 77 

compounds be obbained. The influence of the bivalent group Z in the 
salts [Z Co engJX, is shown by the fact that, although sulphito-, 
carbonato-, oxalato-, and malonato-salts have been prepared, no com- 
pounds derived from succinic, malic, and tartaric acids have been 
obtaiued. The formation of a seven-ring does not, therefore, take 
place, which is in accordance with the results obtained with the 
alkyldiamines (compare Abstr., 1907, ii, 161). 

lonisation Isomerides. — A full list of such compounds is given ; for 
example, the cis- and irans-isomerides of the chloronitrothiocyanate, 
nitroisothiocyanato-chloride, and chloroisothiocyanato-nitrite in the 
diethylenediamine series. 

Relation between the Solubility of the Cobalt Ammonias and titeir Con- 
stitution and Configuration. — The cis-isomerides are generally more 
soluble than the ^raTis-isomerides. There are exceptions, as, for 
example, with the dinitrodiethylenediaminecobaltic iodides. It is pro- 
bable, also, that the solubility of the salt increases with the number of 
ionogenic radicles. 

Relation between tlie Colour of the Cobalt Ammonias and their 
Constitution and Configuration. — The chief influence on the colour is 
exerted by the radicles directly connected with the cobalt atom, and is 
the only one considered here. No colourless cobalt compounds are 
known. The influence of the element directly attached to the cobalt 
atom is shown by the series, C, N, S, O, CI, Br, I, the elements being 
arranged in the order of their bathochromic action. This series can be 
extended as follows, when the various radicles are taken into account : 
CN, CO ; NO2, en, NH3, NCS ; SO3 ; OH^, 0-NO, 0-Acyl, OH ; CI, 
Br, I j thus the least-coloured compounds of cobalt are the pale 
yellow cyanocobaltammonias, [Co(CN)g]R3. Amines, for example, 
ethylenediamine, propylenediamine, hydroxylamine, and pyridine, have 
the same effect as ammonia. It is noteworthy that substitution in the 
iraws-position has a much greater bathochromic effect than substitution 
in the cis-position. 

Differences in the Reactions of Stereoisomeric Cobalt Ammonias. — 
Radicles which are in the cis-position with respect to each other are not 
so firmly combined as those in the trans-position, and enter into 
reaction much more readily ; for example, by the action of hydro- 
chloric acid on cw-dinitrotetramminecobaltic salts, both nitro-groups 
are replaced by chlorine, with the formation of the trans-dichloro-saAts, 
whereas when the iraws-dinitro-salts are heated with hydrochloric 
acid, only one nitro-group is replaced, the ^9-ans-chloroaitro-salts being 
formed. Differences of this kind have caused many difficulties in the 
determinations of the configuration of the stereoisomerides. These 
difficulties are especially marked in the case of the isothiocyanato-salts, 
a full discussion of which compounds is given. Differences also occur 
in additive reactions; for example, the ^7ar^s-chloroamuuinediethylene- 
diamine salts readily give the diammiue salts when dissolved in liquid 

CI 3, whereas the 

hours dissolved 



ammonia : 



jein^N C° «"Jci2 + NH3= [HsN Co en, 



i 



2 

CIS-compounds are unacted on, even after keeping for 
in liquid ammonia. 

Intramolecular Reactions with the Cobalt Ammonias. — The various 



i. 78 ABSTRACTS OF CHEMICAL PAPERS. 

cases are summarised in which there occurs : (a) Intramolecular 
reactions with expuLsion of ammonia or water ; for example, the 
chlorides, bromides, and sulphates of chloro-aquo- and bromo-aquo- 
diethylenediaminecobaltic salts are stable, whilst the nitrites, on keeping, 

r CI ~i 

change in accordance with the equation : jj q ^^ ^"2 (^^2)2 — ^ 
O N ^^ enj NOg + HgO. (b) Intramolecular reactions in which inter- 
change of the acid-residues takes place ; for example, when a drop of 
water is added to the pure, green <rans-dichlorodiethyleoediamino- 
cobaltic nitrite, fCL Co en„lNO„, it immediately changes into the 

. r CI I 

yellowish-red chloronitrodiethylenediamine chloride, rv -m- Co en^ CI. 

(c) Transformation of stereoisomerides into each other. Direct 
transformations have hitherto been observed in comparatively few 
cases, and even then it is probable that intermediate products are 
formed which have not so far been isolated. 

Additive Compounds of the Cobalt Ammonias. — A full discussion is 
given of cases such as the following : By the addition of silver 
nitrate to a solution of the intensely-red coloured salt, 

I SCN 1 

golden-yellow prisms of the composition tr j^ Co eu^ S20g,AgN03are 

obtained. The change in colour observed, and the various reactions of 
this compound, point to its having the constitution 
TAgSCN Q 1N03 

that is, it is a silver thiocyanatoamminediethylenediaminecobaltic salt. 
The study of such compounds is of great service in elucidating the 
mechanism of the various reactions of the cobalt ammonias. 

Spatial Change of Position during Reactions of the Stereoisomeric 
Cobalt Ammonias. — (Compare Abstr., 1911, i, 424.) 

[With Jos. Rapiport.] — Carbonatodiethylenediaminecobaltic salts, 
YX, where Y = [CO3 Co eUg], are prepared from any dichloro- or 
dibromo-salt by the action of sodium or potassium carbonate. The 
mixture with water is boiled until the solution becomes an intense 
blue colour, when the reaction is complete. The chloride, YCljHgO, is 
thus obtained from 1 : 6-dichlorodiethylenediaminecobaltic chloride by 
interaction with sodium carbonate. The hot filtrate from undissolved 
salt deposits, on cooling, dark red, flat, columnar crystals, which 
become anhydrous at 70 — 80°. It may also be obtained from a 
concentrated solution of the bromide by shaking with silver chloride. 
The bromide, YBr,H20, is obtained from the chloride by precipitation 
with potassium bromide. On recrystallisation, it deposits partly as 
hydrated and partly as anhydrous salt. The hydrated salt forms large, 
dark red, hexagonal, efflorescent columns, the anhydrous salt being 
brownish-red in colour. One gram of the salt dissolves in 30 c.c. of 
water at 50°. The iodide, YI, is obtained similarly to the bromide, 
and forms shining, dark red, flat prisms, which are soluble in water to 
the extent of 1 gram in 70 c.c. of water at 80°. The nitrate, YNOgjHgO, 



ORGANIC CHEMISTRY. i. 79 

results from the interaction of the bromide and silver nitrate ; it 
crystallises in dark bluish-red, shining, flat needles. Twenty c.c. 
of water dissolve 1 gram at 60°. The thiocyanate^ YSCN, the 
dithionate, Y^^fiQ,2'Rfi, and the sulphate, Y2S04,5H20, were also 
obtained by reactions involving double]decomposition. They crystallise 
respectively in red, hexagonal prisms or needles, long, dark red prisms, 
and reddish-black, flat prisms. The sulphate loses SHgO at 100°. 

[With R. Hartmuth.] — Oxalatodiethylenediaminecobaltic salts, 
[C2O4 CoeUgJX, have been known for some time (compare Abstr., 
1899, ii, 660), and an attempt has now been made to introduce 
ammonia into the radicle to find out if a spatial transformation takes 
place. As a matter of fact, ammonia does enter into the inner 
sphere, but cis-diamminediethylenediaminecobaltic salts, Y2(C20^)X4, 

are alone formed, where Y= Co ^ ^'^ . Four grams of the oxalato- 

L ®"2 J 
diethylenediamine salt are heated with 15 c.c. of saturated ammonia 

solution for two hours in a bomb-tube at 110°; the contents of the 
tube are taken up with water, the solution concentrated, and 
potassium iodide added. The sparingly soluble oxalatodiethylene- 
diaminecobaltic iodide is first precipitated, and from the mother 
liquor brown, monoclinic, columnar crystals of the iodide oxalate, 
^2(^2^4)^4' ^^^ obtained. By interaction with silver chloride, 
irregular, light yellow, crystalline aggregates of the chloride oxalate, 
^2(^2^4)^^4' ^^® obtained. In contradistinction to the aqueous 
ammonia, liquid ammonia has no action on the oxalato-chloride. 

Malonatodiethylenediaminecohaltic salts, YX, where 
Y-CC^HACoen^]. 
— The AycZro^cnmaZona^ejYCgHgO^, is obtained from car bonatodiethylene- 
diaminecobaltic bromide by first preparing the hydroxide by shaking 
the solution with freshly precipitated silver oxide. Malonic acid 
(2 mols.) is added to the filtrate from the silver bromide, and on con- 
centrating, carmine-red crystals of the desired salt are obtained. By 
double decomposition with potassium nitrate and ammonium thio- 
cyanate respectively, red, shining leaflets of the nitrate, YNO3, and 
thiocyanate, YSCN, are obtained. Attempts to prepare corresponding 
salts by using succinic, malic, or tartaric acids were unsuccessful. 

[With Marie Pokrowska.] — Sulphitodiethylenediaminecobaltic salts, 
YX, where Y = [SO3 Co en2].— The chloride, YCljJHgO, is obtained by 
boiling down a solution of sodium sulphite (10 grams) with trans- 
dichlorodiethylenediaminecobaltic chloride (10 grams, free from 
hydrochloric acid) in 50 c.c. of water to half its bulk. After filtering, 
dark brown crystals of indefinite shape are deposited. The same 
results are obtained if the cis-dichloro- chloride is used in the prepara- 
tion. The sulphito-group is co-ordinately connected with the cobalt in 
the m-position, since on heating with concentrated hydrochloric acid, 
cis-dichlorodiethylenediaminecobaltic chloride is produced. Moreover, 
the brown colour of the salt shows that the SOg-radicle is linked 
up with the cobalt by means of a sulphur valency, thus : 



i. 80 ABSTRACTS OP CHEMICAL PAPERS. 

since if it were linked through two oxygen atoms it would be red in 
colour. On triturating the eemihydrate with hydrochloric acid, a 
reddish-brown solution is formed, from which orange-brown, shinin*^' 
scales of the trihydratey YCl.SHgO, can be obtained. The solution gives 
characteristic precipitates with potassium iodide, acetic acid, and sodium 
nitrite, and with chloroplatinic acid. On trituration with fuming' 
hydrobromic acid and subsequent gentle warming, green crystals of 
^raTW-dibromodiethylenediaminecobaltic bromide are obtained. Both 
hydrates can be dehydrated at 105°. By double decomposition with 
potassium thiocyanate, brownish-yellow, shining needles or scales of 
the thiocyanate^ YSCN,2H20, are obtained. The platinichloride, 
Y2PtClg,4H20, forms brown, star-shaped crystals ; the aurichloride, 
YAuCl^,3H20, crystallises in thin, yellowish-brown, shining scales. 
[With K. R. Lange.] — Diaquodiethylenediaminecohaltic salts, YXg, 

where Y= jJ^^Oo qu^ . — The salts of the cis-series are all much 

more soluble than the irarw-isomerides. The latter are remarkable 
in that by precipitation of their aqueous solutions with potassium 
iodide, the ^rans-hydroxoaquo-iodide is formed and not the diaquo- 
iodide, which shows that in aqueous solutions the diaquo-salts are 
hydrolysed in accordance with the equation : 

[(H^O)^ Co enJXg ^ [^q ^o en^Jx^ + HX. 

A number of salts have been prepared in addition to those previously 
described (compare Abstr., 1907, i, 188). The cis-nitrate, Y(N03)3,H20, 
was obtained from ciVdiaquodiethylenediaminecobaltic bromide by 
the action of concentrated nitric acid at a low temperature. It forms 
red, glistening plates, and can be dehydrated over calcium chloride. 
The cis-8ulphate, Y2(S04)3, was prepared from the bromide by inter- 
action with silver sulphate, and crystallises in red, glistening needles. 
Other cis-salts could not be obtained. 

New methods of preparation of the cis-bromide are as follows : 
(1) 10 grams of carbonatodiethylenediaminecobaltic bromide are 
mixed with 18c.c. of cold water, and 5 c.c. of concentrated nitric acid 
added drop by drop. The solution is neutralised with potassium 
hydroxide, half as much again of the hydroxide added, and then 
precipitated with sodium bromide (23 grams). (2) The hydroxo- 
aquobromide is triturated with a little concentrated hydrobromic acid, 
and then washed with alcohol and ether. The dry product is dissolved 
in cold water containing a little hydrobromic acid, saturated (at 0°) 
hydrobromic acid added, and the solution allowed to crystallise in a 
freezing mixture. 

The iraius-7iiiraie, Y(N03)3, was prepared from the trans-hromide by 
a method similar to that used for the c?s-salt. It could also be 
obtained by interaction with silver nitrate. It forms brownish -red 
needles. The trans- sulphate, Y^iSO^)^, was obtained from the bromide 
by interaction with sulphuric acid as brownish-red leaflets. The trans- 
dithionate, Y2(S20g)3, and the tv9kiis-thiocyam,ate, Y(SCN)3,JH20, crys- 
tallise respectively as slender, brownish-red needles and as dark brown 
plates. The iodide could not be obtained, for the reason already given. 



ORQANIO CHEMISTRY. i. 81 

An account is given of the transformation of the diaquodiethylene- 
diaminecobaltic halogenides into dihalogenodiethylenediaminecobaltic 
salts on keeping for some time or on heating at 105 — 115°. 

A number of hydroxoaquodiethylenediaminecohaltic salts, YXg, 

where Y= tt o ^^ ®^2 » li^ve been previously described (Abstr., 

1907, i, 189). They have been further studied because the different 
stereoisomerides may be obtained from the same starting material 
under conditions of reaction which are only slightly different from 
each other ; thus, in the former paper the cis-bromide was prepared 
from m-dichloro-chloride (violeo-chloride), but it is now shown that 
when the latter compound is dissolved in concentrated aqueous 
ammonia and the solution triturated with solid sodium bromide, the 
^rayis-bromide, YBrg, is formed. The trsmsthiocyanate is reddish-brown 
in colour. 

When dichlorovioleo-chloride (5 grams) is dissolved in concentrated 
ammonia (25 c.c.) by heating on a water-bath, the solution then kept 
in a vacuum over phosphoric oxide until the odour of ammonia has 
disappeared, and then precipitated with sodium bromide, a bluish-red 
precipitate of cis-ckloroamminediethylenediaminecobaltic bromidej 

[h^ Co enjBr,, 
is formed. The production of this compound is not due to the inter- 
mediate formation of the diaquo-bromide, since this salt when dissolved 
in concentrated ammonia gives rise to the hydroxoaquo-bromide only. 

The trans -bromide may also be prepared by carefully heating the 
^raws-nitrate with dilute ammonia (1:1) until crystals begin to form 
on the side of the dish. 

[With R. BossHARD.] — The formation of carbonatodiethylenedi- 
aminecobaltic salts from the stereoisomeric hydroxoaquo-salts has been 
studied. In all cases one and the same series of carbonato-salts 
was formed, it being impossible to prepare stereoisomerides. The 
carbonato-salts were prepared by the action of carbon dioxide either 
on alkaline solutions or on aqueous solutions of the hydroxoaquo- 
salts. 

Dichlorotetramminecobaltic salts, YX, where Y = [CI2 Co(NH3)4]. — 
The constitution of the silver and bismuth salts described previousl y 

(Abstr., 1897, ii, 264) must be altered to f^^^j Co(NH3)4lci2and 

-'CI ~I 

^^Qj Co(NH3)4 Clg. A new method of preparation of the ci^-chloride 

is given. Carbonatotetramminecobalt chloride is shaken up with a 
saturated (at 0°) solution of hydrogen chloride in absolute alcohol 
until the evolution of carbon dioxide ceases. The greyish-blue reaction 
product, which is a mixture of the cis- and <rans-dichloro-salts, after 
being washed free from acid with alcohol and dried, is extracted with 
a small quantity of ice-cold water, the cis-isomeride going into solution. 
The filtrate is immediately precipitated with sodium dithionate in 
order to obtain the violeo-dithionate, from which the chloride and 
other salts can be obtained in the manner previously described 
(Abstr., 1908, ii, 42). There is always a considerable loss of violeo- 
VOL. cii. i. g 



i. 82 ABSTRACTS OF OHBMICAL PAPERS. 

salt, owing to it« ready transformation, in aqueous solution, into 

chloroaquo-Halt. The preparation by means of aqueous hydrochloric 

acid cooled with liquid air was by no means so satisfactory. 

Dictdorodiethylenediaminecobaltic salts, YX, where Y =-= \Q\^ Co engJX. 

— A new method of preparation of the normal traiis-chXoi'idie is to 

precipitate an aqueous solution of the acid chloride with solid lithium 

chloride. The trans-m'iriie, YNOg, is obtained as small, green 

crystals by precipitation of an aqueous solution of the chloride, 

acidified with acetic acid, with sodium nitrite. When sulphuric acid 

is used as the precipitant, green crystals of the tr&ns- hi/drogen 

sulphate, YHSO^, are obtained. The addition of silver nitrate to a 

solution of the chloride cooled with a freezing mixture gives a 

precipitate consisting of greenish-white, glistening leaflets, having the 

.,. TAgCl ri 1 SO, „ ,. 

composition *=p. Co en^ (Kn \ »^2^- 

New methods of preparation of cis-dichlorodiethylenediaminecobaltic 
salts from carbonatodiethylenediaminecobalt chloride are given ; they 
are similar to those already described for the corresponding tetiammine 
salts, except that the product of reaction is washed with cold water to 
free it from impurities, than which the cts-dichloro-salt is less soluble. 
A characteristic ci&sulphate, Y2SO^,2H20, is described ; it crystallises 
in small, reddish-violet needles. 

[With L. Gerb, S. Lorie, and Jos. Rapiport.] — Dibromodiethylene- 
diaminecobaltic salts, YBr, where Y = [Br2 Co eUg.] — Only the trans- 
isomerides have hitherto been prepared (by Jorgensen), for which new 
methods of preparation are now given, as follows : (a) a solution of cobalt 
bromide in 10% ethylenediamine is oxidised by leading air through it, 
and then evaporated to dryness. The residue is then repeatedly treated 
with hydrobromic acid and evaporated until a uniform green salt 
remains, which consists of ihe acid bromide. On treatment with a 
little water, the <ra?i«-bromide is obtained. (6) Carbonatodiethylene- 
diaminecobalt bromide is heated on the water-bath with a solution 
of hydrobromic acid (D = r49) until the solution is green. On 
cooling, the acid bromide separates, from which the normal bromide 
is best obtained by heating at 110° until it no longer gives an acid 
solution. The tioxi^-thiocyanate, YSCN, is precipitated as a canary- 
green, crystalline salt by the addition of potassium thiocyanate to a 
solution of the trans-hiomidie. 

The methods for the preparation of the cia-bromide, YBr, are as 
follows: (1) a solution of the trwiis-hromide is evaporated on the 
water-bath several times to a syrupy consistency. On keeping in a 
vacuum desiccator, black crystals are then obtained, which give a 
greyish-violet powder ; they consist chiefly of the m-isomeride mixed 
with a little of the <raws-isomeride. The latter can be extracted with 
a small quantity of water, leaving the m-form, which can be purified 
by solution in water and precipitation with sodium bromide. (2) By 
fission of tetraethylenediaminedioldicobaltic bromide with concentrated 
hydrobromic acid into diaquo-bromideand therequireddibromo-bromide. 
The diaquo-salt is removed from the mixture by solution in absolute 
alcohol. (3) From carbonatodiethylenediaminecobaltic bromide by 
treatment with an alcoholic or aqueous solution of hydrogen bromide 



ORGANIC CHEMISTRY. i. 8S 

by a uioUioJ siuiilar to that described for the coiTespoiidin<^ dichloro- 
salts. The cin-bromide, YBr, forms scaly crystals, possessing a colour 
and glance similar to that of graphite. By double decomposition with 
the appropriate salts of the alkali metals, the following compounds 
were prepared. The cis-iodide, YI, is similar in appearance to the 
bromide; the ci^-nitrate, YNO^, forms small, gteyish-violet crystals, 
as also does the cis-thiocyanate, YSCNjHgO ; the crystals of the cis- 
dithionate, Y2820g, are somewhat lighter in colour than those of the 
other salts. 

Chlorohroniodiethyleiiediaminecohaltic salts, YX, where 

~C1 



Y = 



g^CoengJx. 



— Both the cis- and iraws isomerides have been prepared ; the former 
are readily obtained pure, the latter only with difficulty, since they 
are generally mixed with ^raris-dibromo-salts. Two methods of pre- 
paration are given: (1) Two grams of chloroaquodiethylenediamine- 
cobaltic bromide are covered with 2 c.c. of concentrated hydrobromic 
acid, and the mixture heated until complete solution takes place. On 
cooling, a mixture of the green and violet salt is obtained, which is 
washed with alcohol and ether, dried, and then treated with a small 
quantity of water to dissolve out the green salt. The violet salt 
(m-isomeride) is collected, washed with water and alcohol, and dried. 
The green filtrate gives precipitates with metallic salts, which give 
analytical results corresponding with a mixture of dibromo- and 
chlorobromo-salts. (2) Chloroaquodiethylenediaminecobaltic bromide 
is heated for two houis at 110°, whereby a mixture of the cis- and 
<r«?is-chlorobromo-bromides is produced. This is separated as in 
(1), the ^r«ws-nitrate being precipitated from the green filtrate by 
ammonium nitrate. 

The trans-?u'^rrt^(3, YNOg, forms small, light green, glistening leaflets. 
The trans-dithionate, YgS^Oj., and irams-thiocyanate, YSCN, are 
prepared from the green filtrate mentioned above by double decom- 
position with the appropriate alkali salts ; they form respectively 
glistening, green, flat crystals, and a light green precipitate. The 
cis-bromide, YBr,H20, is a greyish-violet, microcrystalline salt ; the 
ch-nitrate, YNOg, forms dark violet needles, and the cia-dithioiiate, 
YgSgO^., small, violet leaflets. 

When the cis-bromide is gently warmed with concentrated hydro- 
bromic acid until a *^olution is formed, it is changed into trans- 
dibromodiethylenediaminecobaltic bromide, which is deposited on 
cooling in canary-green crystals. 

TT .\ OO 

the cis-isomerides have so far been obtained ; the cold aqueous solu- 
tions are fairly stable, but, on heating, complicated changes take 
place. By the action of concentrated aqueous ammonia on the chloro- 
aquo- and bromoaquo-bromides, hydroxochloro- and hydroxobromo- 
bromides are obtained. 

cis-Chloroaquodiethylenediami'iiecobaltic salts, YXg, where 

._ Y = [^2 ^" "' J- 

■ ',2 



en. 



Xg.— Only 



i. 84 ABSTRACTS OF CHEMICAL PAPERS. 

— The stUphaie, YSO^.lJHjO, is prepared by beating 20 grams of trans- 
dicblorodiethyleuediaminecobaltic chloride with 20 c.c. of water until 
a deep blue solution is obtained. After cooling, and keeping for one 
hour, ammonium sulphate (10 grams) is added; on keeping for a 
further twelve hours, bluish-red crystals of the sulphate are deposited, 
mixed with some green crystals which can be removed by shaking 
with a little cold water. The sulphate dissolves in concentrated 
ammonia, and the solution gives a bluish-red precipitate of chloro- 
amminediethylenediaminecobaltic bromide with concentrated hydro- 
bromic acid. The chloride^ YClgt and the bromide, YBr2,H20, are 
obtained from the sulphate by interaction with the respective halogen 
acids. The former is microcrystalline, and the latter forms small, 
crystalline leaflets ; both are reddish- violet in colour. The bromide- 
nitrate, YBrNOg, prepared from the bromide and lithium nitrate, is 
reddish- brown in colour. The nitrite, Y(N02)2, from the chloride and 
sodium nitrite gives dark violet micro-crystals. It is unstable, 
changing to cw-chloronitrodiethylenediaminecobaltic nitrite. 

[With R. Schmidt.] — cis-Bromoaqiwdiethylenediaminecobaliic salts, 

YXj, where Y= Ljr ^^ Coeng . — The following methods are given for 

the preparation of the bromide, YBrgjHgO. (1) A solution of neutral 
1 : 6-dichlorodiethylenediaminecobaltic chloride containing nitric acid is 
heated with a concentrated solution of silver nitrate until it assumes a 
Bordeaux-red colour. After collecting the silver bromide, the filtrate 
is saturated with sodium bromide, first filtering off any more silver 
bromide which may be formed. After a few hours the bromide has 
deposited as a violet, microcrystalline powder. (2) A concentrated 
solution of the iran«-dibromo-bromide is heated at 40° until it becomes 
violet in colour ; after cooling, it is saturated with sodium bromide. 
Any green crystals of praseo-bromide which are precipitated with the 
bromoaquo-bromide are removed by fractional solution in ice-cold 
water, the praseo-bromide being the lesser soluble salt. (3) A solution 
of fraTW- dibromonitrate is treated similarly to the dibromo- bromide, 
except that it is heated over the bare flame. (4) The carbonato- 
chloride or bromide is treated with concentrated hydrobromic acid 
(D«=l*4). The bromoaquo-bromide is separated from the less soluble 
cw-dibromo-bromide, which is formed at the game time, by fractional 
solution. (5) cw-Diaquo-bromide is heated at 40° with just enough 
water to give complete solution until a violet-coloured solution 
is obtained ; the bromoaquo-salt is then precipitated with sodium 
bromide. 

The bromide forms dark violet, leaf-like crystals. By double 
decomposition with sodium nitrate and sodium nitrite respectively, it i 
gives the nitrate, Y(N08)2,H20, and nitrite, Y(N02)2, as bluish-violet, 
crystalline powders. When triturated with Erdmann's salt, 

[(NOj),Co(NH3),]NH„ 
it gives a yellowish-green, tetranitrodiamminecobalt compound. 

Hydroxohalogeno-ssAts, -j,^ Co A^ X. — Hydroxockloi'otetrammine- 
cobaltic dithionate, ^,. Co (NHg)^ SgOj, is precipitated as a violet-blue 



■| ORGANIC CHEMISTRY. i. 85 

salt when solid chloroaquotetramminecobaltic chloride is dissolved in a 
saturated solution of sodium dithionate in concentrated ammonia, 
ammonium dithionate remaining in solution. The colour corresponds 
with that of the cis-dichlorotetrammine salts. The corresponding 

hydroxochlorodiethylenediaminecohaltic bromide, ^^ Co en2 Br, is 

obtained as a brownish-violet, crystalline paste when chloroaquo- 
diethylenediaminecobaltic bromide is treated with concentrated 
ammonia ; when heated with concentrated hydrogen chloride, this salt 
gives a mixture containing a little 1 : 6-dichloro- with much 1 : 2- 
dichloro-diethylenediaminecobaltic chloride. cis-Hydi-oxobromodiethyl- 

e7iediaminecobaltic bromide, g^ Co en^ Br, is similarly obtained as a 

brownish-violet salt from the bromoaquo-bromide and ammonia. 
When warmed with a little water, addition takes place with the 
formation of the czVhydroxoaquo-bromide ; similarly, when triturated 
with concentrated hydrobromic acid, the m-diaquo-bromide is 
obtained. 

Ghloroisothiocyanatodiethylenediaminecobaltic salts, YX where 

[CI ~i ' 

SCN ^^ ®°2 • — ^ f®^ of the trans-isomerides, which were, 

however, impure, have been described previously (Abntr., 1900, i, 86). 
The tra.Bs-thiocyanate, YSCN, is obtained by precipitating a solution 
of 1 : 6-dichIorodiethylenediaminecobaltic chloride with potassium thio- 
cyanate. The precipitate consists of a mixture of about two-thirds of 
the trans- and one-third of the cis-isomeride. By appropriate treatment 
the pure ^m?2s isomeride is obtained as sparingly soluble, violet leaflets. 
When triturated with hydrobromic acid, it gives glistening, bluish- 
violet crystals of the tr sms-bromide, YBr,2H20. This salt may also 
be prepared from praseo-chloride (Abstr., 1907, i, 291), With sodium 
dithionate, it gives bluish-violet, glistening crystals of the trans- 
dtthionate, YgSgO^,, and with perchloric acid, violet leaflets of the 
tmns-perchlorate, YCIO4. The perchlorate may al.o be obtained 
directly from the ^myis-dichlorothiocyanate and perchloric acid. 

The ^mns-isomerides dissolve readily in liquid ammonia, giving red- 
dish-yellow solutions which deposit mixtures of the stereoisomeric iso- 
thiocyanatoammine salts. If the trans-perchlorsite is boiled with 
sodium nitrite in concentrated aqueous solution until a reddish-brown 
colour IS obtained, the solution cooled, and ammonium thiocyanate 
added, an isomorphous mixture of the 1 : 6-chloro2Sothiocyanato- and 
1 : 6-nitroisothiocyanato-thiocyanates is precipitated. If the solution 
IS boiled until brown in colour, small quantities of the m-nitro^so- 
thlocyanato-salt crystallise on cooling. On heating a solution of trans- 
chioiwothiocyanato-bromide with potassium thiocyanate and cooling 
needles of the imns-diisothiocyanato-thiocyanate separate, and from the 
mother liquor small quantities of the ctVisomeride can be obtained ; 
oxidation of the imm-salt with hydrogen peroxide gives the tra^is- 
diammine salt. or e, 

On boiling a concentrated solution of the «mns-chloroisothiocyanato- 
bromide (1 mol.) with silver nitrate (3 mols), filtering fr,.m silver 
bromide, and cooling, light violet, slender needles of an additive com^ 



i. 8C) AHSTflACTS OF CHEMICAL PAF'EHS. 

pound, . „p^ Co en^ (N03)2, are obtained. On boiling the aqueous 

solution of this salt, silver chloride is slowly precipitated. 

cxs-ChloroiRolhioci/anatodiethylenediaminecobaltic chloride, YCl, is 
obtained in the purification of the <ran«-thiocyanate in the form 
of bluish-red needles. It is purified by transformation into the per- 
chlorate and precipitation of the solution of this salt with concentrated 
hydrochloric acid. By double decomposition of a solution of the per- 
chlcrate with the appropriate salts of the alkali metals, the following 
compounds were obtained: c\h- Dilhionate, YgSgO^jHg^* brownish-red 
needles; cis-m7ra^, YNOg, dark bluish-red needles; ciF-sulpkate, 
YgSO^, violet-red powder. The ch-bromide, YBrJJHgO, was obtained 
from the chloride by interaction with hydrobromic acid. A method 
of preparation of the cis-chloride from cis-i«othiocyanatonitro chloride 
by interaction with hydrochloric acid is also given. 

The action of hydrogen peroxide, liquid ammonia, potassium 
thiocyanate, sodium nitrite, and silver nitrate on the cw-salts is fully 
described. 

Brmnohothiocyanaiodiethylenediaminecohaltic salts, YX, where 

Y = cn>j ^o ettg . — Both series of isomerides are known, but the cia- 

salts are difficult to isolate, since in aqueous solution they are readily 
transformed into aquo-salts. The <ran«-isomerides on oxidation with 
hydrogen peroxide under certain conditions give 1 : 6-bromoamine 
salts, and under other conditions 1 : 6-dibromo-s.alts. Hydrogen 
peroxide completely oxidises the thiocyanate residue of the cis- 
jsomerides, but if the aqueous solution is kept some time before 
hydrogen peroxide is added, a salt of the aquo-series is formed, which 
then gives rise to the bromoammine salt. With ammonia both 
isomerides give a mixture of cis- and <ra?i«-isothiocyanatoammine- 
diethylenediaminecobaltic salts. 

The tTdin^-thiocyanate, YSCN, is prepared from 1 : 6-dibromo- 
diethylenediaminecobaltic bromide by precipitation with potassium 
thiocyanate. The green precipitate and mother liquor are heated until 
a deep red solution is obtained. On cooling, and further addition of 
potassium thiocyanate, green, glistening needles of the required salt 
are obtained. Trituration with concentrated hydrobromic acid gives 
dark blue, prismatic crystals of the irarw-bromide, YBr,2H20, and pre- 
cipitation with perchloric acid, the tra.nR-perchIorate, YCiO^, as dark 
blue, almost black, slender needles. The tr a.ns-dithio7iatfi, YgSgOg, 
forms violet-blue leaflets. 

Three methods of preparation of the cis-bromide, YBr, are fully 
de.scribed, namely, from 1 : 6 dibromodiethylenediaminecobaltic 
bromide, 1 : 2-aquowiothiocyanatodiethylenediaminecobaltic dithionate, 
and 1 : 2-nitrowothiocyanatodiethylenediaminecobaltic sulphate. It 
forms garnet-red, glistening, prismatic crystals, and is used as a 
source of preparation of the other salts by methods involving double 
decomposition. The vis^-nitrate, YNOj, is violet-brown in colour, the 
ci9-dithumate, YgSgOg, brownish-red, ^hilst the cis-siUphate, Y^SO^, 
gives reddish-lilac, silky, thin leaflets. 



¥ 



ORGANIC CHEMISTRY. i. 87 



Y=| Tx ^ Co en^ . 



is^oThiocyanatoaquoduthylenediaminecohaltic salts, YXg, where 

rscN 
Lh,o 

— Both series of isomerides have been obtained, whereas with all other 
acidoaquo-salts it has been possible to prepare one series only, either 
the cis- or trans-. The salts of the cis-series are yellowish-red to 
crimson in colour, whilst those of the irans-series are violet ; the 
former are obtained from the stereoisomeric chlorozsothiocyanato-salts 
by the action of concentrated ammonia, and the latter from the same 
salts by the action of potassium hydroxide. 

The c\s-dithionate, YS20g,H20, is prepared by warming 1 : 6-chloro- 
isothiocyanatodiethylenediaminecobaltic bromide with concentrated 
ammonia until a red solution is formed. The cooled solution is then 
poured into absolute alcohol, the precipitate dried on a porous plate, 
dissolved in cold water, and glacial acetic acid added to the solution 
until a precipitate begins to form. On further keeping, orange-coloured 
needles of the dithionate separate. With potassium thiocyanate the 
solution gives a crimson precipitate of the cis-thiocyanate, Y(SCN)2. 
With hydrogen peroxide, the dithionate gives a mixture of the cis- and 
trans-chlovosimmme salts; with concentrated hydrochloric acid, cis- 
chloroisothiocyanato-salts ; with nitrous acid, cis-nitroisothiocyanato- 

diethylenediaminecohaltic dithionate, opiu- Co eng 2^2^6' ^"^ ^^® form of 

slender, yellow needles ; with potassium thiocyanate, m-diwothio- 
cyanato-salts. With silver nitrate and perchloric acid, an orange- 
coloured additive product, » ^ Co eng L^ *''2,2H20, is obtained. 

The trans-6romic?e, YBr2,2H20, is prepared as follows : 1 ; 6-chloro- 
isothiocyanatothiocyanate dissolves in* potassium hydroxide to a red 
solution ; on cooling, brownish-red leaflets of 1 : 6-hydroxoisothio- 

cyanato-thiocyanatey ^p^Coeng SCN,H20, separate. These are dis- 
solved in a little water, excess of concentrated hydrobromic acid added, 
and the solution kept over sulphuric acid in a desiccator. After a 
few days, dark red crystals of the required bromide separate. From 
this salt, by the method of double decomposition, the trans-^/wo- 
cyanate, Y(SCN)2,H20, is obtained as a violet precipitate, the trans- 
nitrate, Y(N03)2,H20, as bluish-red needles, and the trans-nitrite^ 
Y(N02)2, ^^ dark violet-red crystals. On the addition of excess of 
silver nitrate to a well-cooled solution of the nitrate, bright red 

needles of an additive product^ ,^^J^Coen^\(NOQ)^yIl2^f 
deposited. 

On oxidation with nitric acid or hydrogen peroxide, and subsequent 
evaporation with concentrated hydrochloric acid, the trans -Siquoiso- 
thiocyaiiato-salts give only «r«ns-chloroammine salts. 

When solid sodium nitrite is added to a concentrated solution of 
1 : 6-isothiocyanatoaquo-nitrate acidified with a few drops of acetic 
acid, a bright red precipitate of 1 : Q-nitrito'isothiocyanatodiethylene- 

diaminecohaltic nitrite, YN02,H20, where Y = L^p^^^ Co eng L is 



are 



88 AHSTKACTS OF CHEMICAL PAPERS. 

produced ; with potassium thiocyanate the solution gives red needles 
of the 1 : ^'thiocyanate, YSCN. 

Chloroaniminediethylenediaminecobaltic salts, YXg, where Y = 

I CI ~l 

TT XT Co en, . — The isomerides of this series are best distinguished 
HgJN \\ 

by means of the dithionates ; the ct8-dithionate forms thick crystals, 

whilst the irarw-dithionate crystallises in long, glistening needle.s. 

Both series of salts are bluish-red in colour. The ^raws-salts react 

very quickly with liquid ammonia, forming diammine salts, whereas 

the cM-isomerides are scarcely acted on. Jorgensen has already 

prepared a number of the cts-isomerides. 

The best method of preparation for the ci«-chloride, YClg, is the 
trituration of 1 : 6-dichlorodiethylenediamiiiecobaltic chloride with 
concentrated ammonia. The green salt first dissolves, and then a red 
paste of the required chloride separates. The addition of solid sodium 
perchlorate to a solution of the chloride precipitates long, red prisms 
of the cis-chlw'ide-perchloratef YCI(CIO^) ; on recrystallisation from 
concentrated hydrochloric acid it is transformed into the chloride. 
The ch-nitrite, Y(N02)2, forms brick-red crystals. The actions of 
sodium and silver nitrites, of potassium thiocyanate, and of liquid 
ammonia on the cw-chloride are fully described, as also the changes 
which aqueous solutions of the m-nitrite undergo on warming. 

To prepare the traiis-cA/<wic£«, YCIgtHgO, 1 : 6-chlorot«othiocyaDato- 
diethylenediaminecobaltic thiocyanate is oxidised with hydrogen 
peroxide in aqueous solution acidified with sulphuric acid. Precipita- 
tion with hydrochloric acid then gives a chloride-sulphate, which is 
recrystallised from hydrochloric acid several times, and the aqueous 
solution then precipitated with barium chloride to remove the 
sulphuric acid. It forms bright ruby-red prisms. It may also be 
prepared from 1 : 6-nitroammine salts by heating with concentrated 
hydrochloric acid, and from 1 : 6-dichloro-salts by the action of a 
methyl-alcohol solution of ammonia. The trsms-chloride-perchloratej 
YCI(CIO^), is prepared from 1 : 6-chlorowothiocyanatodiethylene- 
diaminecobaltic perchlorate by a method similar to that used for the 
chloride ; it forms bright red, glistening leaflets or flat needles. The 
tTAUs-cMoride hydrogen sulphate, YC1(HS04), is obtained by repeated 
evaporation on the water-bath of 1 : 6-nitroammiDedithionate with 
hydrochloric acid ; it crystallises in thick, ruby-red plates. The 
tr Aus-dithionatey YSjOg,H20, crystallises as bright red, slender needles 
when sodium dithionate is added to a solution of the chloride- 
perchlorate. The dichromate, nitrate, and nitrite have also been 
obtained. The actions of sodium and silver nitrites, of potassium 
thiocyanate, and of liquid ammonia on the iran«-chloride-perchlorate 
are fully described, as also the changes which aqueous solutions of the 
<raw«-nitrite undergo on keeping or on warming. 

Bromoamminediethyletiediaininecobaltic salts, YXg, where Y == 

I TT j^ Co euj . — Both series of isomerides have been prepared, the 

cis-isomerides being the more easily obtained. The determination of 
their configuration depends on the formation of the ira7is-isomerides 

.„ ....^..,^..„ ., .... .,. ..... 



ORGANIC CBEMISTRY. i. 89 

peroxide. Both series are very similar in colour. The cis-dithionate 
forms short, compact crystals, whilst the trans-ifioiaeride gives long, 
slender needles ; also, the former salt readily dissolves in concentrated 
hydrobromic acid, with the formation of the bromide, whereas the 
latter is unaltered. 

[With W. E. Boiis.] — The cis-bromide, YBr2,2H20, is obtained when 
moist 1 : 6-dibromodiethylenediaminecobaltic bromide is treated at a 
low temperature with ammonia (1 : 1), drop by drop, until the green 
colour changes to a dark violet. At higher temperatures, the diammine- 
salt is produced, owing to the addition of a further molecule of 
ammonia. When recrystallised from water, it forms bundles of 
reddish-violet, glistening needles ; when precipitated from the aqueous 
solution by the addition of concentrated hydrobromic acid, the 
anhydrous salt, YBrg, is obtained as dark brownish-red prisms or 
needles. It may also be prepared (1 ) by the action of ammonium bromide 
on tetraethylenediaminediaquotetroldicobalticobaltous sulphate, and 
(2) by the action of hydrobromic acid on 1 : 2-nitroamminediethylene- 
diamifiecobaltic salts or on 1 : 2-aquoamminediethylenediaminecobaltic 
salts. By appropriate double decomposition the following salts were 
obtained : ci^-bromide-nitrate, YBr(N03), as reddish-violet crystals ', 
the cis-dithionate, YSgOg, as reddish- violet, thin leaflets; the cis- 
platinochloride, YPtCl^, as reddish-brown leaflets. The cis-nit7'ate, 
Y(N0g)2, was obtained from the bromide by trituration with 
concentrated nitric acid as dark reddish-violet, long, rectangular 
columns. 

The tra,ns-dithionate, YSgO^, is obtained from 1 : 6-bromoisothio- 
cyanatodiethylenediaminecobaltic bromide by oxidation at 50° with 
hydrogen peroxide in aqueous solution acidified with acetic acid, and 
subsequent precipitation with sodium dithionate. It forms bluish, 
rose-coloured, slender needles. With ammonium iodide the solution 
gives reddish-brown, glistening, flat needles of the trsms-iodidef 
Yl2,H20. The trsms-bromide, YBr^,Jifi, was prepared from 
1 : 6-aquoamminediethylenediaminecobaltic bromide by evaporation 
with concentrated hydrobromic acid on the water-bath. It forms 
large, dark reddish-violet prisms, and serves as the source of the 
trsins-nit7'ate, Y(N03)2,H20, and the trams-perchlorate, Y(C104)2, the 
latter crystallising in violet needles. 

Aquoamminediethylenediaminecobaltic salts, YXg, where 

— Both series of isomerides have been prepared. They are obtained by 
the action of potassium hydroxide or of freshly precipitated silver oxide 
on the stereoisomeric chloroammine- and bromoamminediethylene- 
diaminecobaltic salts. In every case, partial transformation takes place, 
so that a mixture of the isomerides is produced. The product of action 
of the alkali is an hydroxoammine salt, the aquoammine salt being 
produced when the solution is acidified. Potassium hydroxide produces 
a greater relative transformation than silver oxide ; more trans- 
isomeride seems to be produced at low than at ordinary temperatures. 
The mixture of the isomerides is separated by taking advantage of the 
fact that the irrtns-aquoammine-bromide is much less soluble in dilute 



i. 90 ABSTRACTS OF CHEMICAL PAPERS. 

hydrobromic acid than the m-isomeride. The ifiomerides can be dis- 
tinguished from each other (1) by tranfiformation into the chloro- 
amminedithionate (q.v.) by warming with hydrochloric acid, and 
subsequent precipitation with sodium dithionate ; (2) by warming the 
aqueous solution to which sodium nitrite and a little acetic acid has 
been added to 60 — 70°. A yellow solution is produced, which, on the 
addition of sodium dithionate, gives an insoluble precipitate if the 
CM-isomeride is present, or a precipitate which can be recrystallised 
from water if the trans-isomeride is present. 

The trRUs-brojnide, YBrgjHgO, forms pale brick-red needles, and is 
used as the source of other salts, methods of double decomposition 
being employed. The trsms-iodide, Yl3,H20, forms brownish-red, flat, 
prismatic crystals ; the trans-nitrate^ Y(N03)3, crystallises in fire-red, 
glistening prisms ; the tra.n8-platinichloride, Y2(PtCI^)3,2H20, gives 
small, dark, brownish-red crystals, and the trsms-platinochloridej 
Y2(PtCl^)3.2H20, forms slender, light brown crystals. 

The cis-bromide, YBr3,H20, forms clumps of small, red crystals. 

The diisothiocyanatodiethylenediaminecobaltic salts, YX, where Y = 
[(SCN)2 Co eng], have already been described (compare Braunlich, 
Abstr., 1900, i, 86). Their true configuration has now been deter- 
mined as follows. By violent oxidation with concentrated nitric acid 
and subsequent evaporation with hydrochloric acid, the ^raws-isomerides 
give mainly <r«xws-chloroammine salts, together with some trans- 
diamraine salts ; oxidation with hydrogen peroxide gives only the 
latter salts. Under the same treatment the ci«-isomerides give 
respectively i?'an«-dichloro-salts, together with a little cis-chloro- 
ammine-salt, and ci«-chloroammine salt. On oxidation with chlorine 
the <ran8-isomerides give ^rans-diammine salts, and the ci«-isomerides, 
<ra?i«-dichloro-salt8. 

[With C. Rix.] — A new method of preparing the cis-salts is as 
follows : 1 : 2-nitrosoisothiocyanatodiethylenediaminecobaltic thiocyan- 
ate is evaporated with hydrochloric acid, whereby pure cis-diiiso- 
thiocyanatodiethylenediaminecobaltic chloride, YC1,|H20, is obtained. 

The solubilities at 25° of the various salts in grams per 50 c.c. of 
water containing acetic acid aie as follows : chloride, 2766 ; bromide, 
0-1996 ; iodide (at 24°), 0-465 ; nitrate, 0-1968 ; thiocyanate, 0-1860. 

Stereoisomeric diamminediethylenediam.inecohaltic salts, YXg, where 
Y = [(NH3)2Coen2]. have already been described (Abstr., 1907, i, 290), 
but the wrong configuration has been assigned to them ; those which 
were formerly characterised as cw compounds are now found to be the 
iraTis-isomerides, and vice-versa. The evidence for this is based on 
their relation with the diisothiocyanato- and wothiocyanato-ammine- 
salts, which has already been indicated, and on the resolution of the 
c»s-compounds into the optically active isomerides. The ^rans-salts are 
sparingly soluble, whilst the ci«-salts are readily soluble. A new 
method of preparation is described, by the oxidation of the isoihio- 
cyanatoamminediethylenediaminecobaltic salts with hydrogen peroxide 
in the presence of halogen acid. 

[With R. Samanek.] — Mixtures of the two series of salts have also 
been obtained by the action of liquid ammonia on the following com- 
pounds : 1 : 6-dichloro-, 1 : 6-dibromo-, and l:2-dibromo-diethylene- 



ORGANIC CHEMISTRY. i. 91 

diaminecobaltic salts; 1 : 6-chlotOimmine-, 1 : 6- and 1 ; 2-bromo- 
ammine-diethylenediaminecobalfcic salts. The separation of the 
isomerides can be brought about by taking advantage of the fact 
that the bromide of the trans-series is only sparingly soluble in 
hydrobromic acid, whereas the cis-bromide is readily soluble ; or, 
better still, by precipitation of concentrated solutions of the salts with 
sodium dithionate, whereby the ^ra?2s-dithionate is obtained, it being 
practically insoluble in water; from the mother liquor the cis-periodide 
is precipitated by the addition of a solution of iodine in hydriodic acid, 
and by trituration of this salt with sodium thiosulphate the cis-iodide 
is obtained. 

In all reactions leading to the formation of diammine salts, the 
cis-isomerides are formed in preponderating amount. If the action of 
ammonia on the 1 : 6-dichloro-salts is not sufficiently energetic, some 
1 : 2-chIoroammine salt is formed. 

isoThiocyanatoamminediethylenediaminecohalliG salts, YXg, where 

rscN "I 

Y = ^ Co eng . — The two series of isomerides have been obtained, 

and are very important, because of their genetic relations with other 
series, in the determination of configurations, etc. A mixture of both 
isomerides is always obtained in their preparation, no matter whether 
1 : 2-chloro-, 1 : 2-bromo-, or 1 : 6-chloro-, 1 : 6-bromo-isothiocyanato- 
diethylenediaminecobaltic salts are used to obtain them by inter- 
action with liquid ammonia. The relative proportion of the isomerides 
produced is not independent of the nature of the ionogenic radicle in 
the salt used. 

The cis- and tmns-thiocyanates, Y(SCN)2, are obtained by dissolv- 
ing 1 : 6-chloroisothiocyanatodiethylenediaminecobaltic thiocyanate in 
liquid ammonia and allowing the solution to evaporate at the ordinary 
temperature. The residue is dissolved in water containing acetic acid, 
and, on keeping, the trans-thiocysmsite is deposited as slender, glisten- 
ing, reddish- orange needles ; the m- thiocyanate is precipitated from 
the mother liquors by the addition of much potassium thiocyanate in 
the form of reddish-brown, crystalline crusts. By appropriate double 
decomposition the following salts were obtained : cis-dithionate, YSgOg, 
brilliant, orange-red leaflets; cis-iodide, Ylg, short, columnar, reddish- 
brown crystals ; tra,us-iodide, Yl2,H20, small, brick-red prisms. The 
trsLua-bromide-dithionate, Y2Br2(S20g),2H20, was prepared by trituration 
of the thiocyanate with hydrobromic acid and subsequent precipitation 
with sodium dithionate ; it forms brownish-red, prismatic crystals. 
With silver nitrate the cis-dithionate gives glistening, yellow crystals 

of an additive product, . Qpisr ^^ ^^2 rJ^o^' whilst the trans-per- 

chlorate, prepared from the thiocyanate and perchloric acid, gives 

yellow needles of the additive product, . Qnisr ^^ ^"^2 (-'^^3)4- 

A detailed account is given of the action of oxidising agents and of 
potassium thiocyanate on the cis- and ira/is -isomerides. 
Nitratoanmiinedi ethyl enediaminexohaltic salts, YXg, where 



i. 92 ABSTRACTS OP CHEMICAL PAPERS. 

are obtained by the evaporation of the stereoisomeric aquoammine- 
diethylenediaminecobaltic nitrates with concentrated nitric acid. In 
the preparation of the ^rarw-isomeride from the 1 : 6-aquoammine salt, 
some cts-isomeride is formed at the same time, but the two are readily 
separated by taking advantage of the fact that the c/s-dithionate 
is almost insoluble in water. Their configuration is determined by 
evaporation with concentrated hydrochloric acid, which gives the corre- 
sponding chloroaramine Falts. Liquid ammonia gives a mixture of 
the stereoisomeric diammine salts. 

The c\B nitrate, Y(N03)2. forms small, glistening, 'orange-red crystals ; 
the cis^-dithionate, YSgO^^jHgO, is an orange-coloured powder. The 
tTAUf^-iIithionatey YSgO^, crystallises in orange-coloured needles. 

[With W. E. BoES]. — Nitroamminediethylenediaminecohaltic salts, 

YXg, where Y= tj2 Co eng . — Both series of isomerides have been 

prepared, and are distinguished from each other by the fact that the 
cis-salts are much more soluble than the i?*ans-salts, this difference 
being especially marked in the dithiouates. The configuration is best 
decided by evaporation of the salt to dryness with hydrochloric acid, 
solution of the residue in water, and precipitation with sodium 
dithionate of the chloroamminediethylenediaminecobaltic dithionale, 
the cw- and frans-isomerides of which are very characteristic. 

The cis-6romtc?e, YBrg, is obtained by adding an excess of a 
saturated solution of sodium nitrite to a saturated (at 25°) solution 
of 1 : 2-aquoamminediethylenediaminecobaltic bromide, acidifying 
with acetic acid, and warming at 40° until the solution becomes 
orange-yellow in colour. After keeping for twenty-four hours a 
precipitate consisting of a mixture of the bromide and nitrite is 
deposited ; it is dissolved in water, and the solution saturated at 35° 
with potassium bromide. On cooling, large, dark yellow plates of the 
bropiide are obtained. The following salts were obtained from the 
bromide, for the most part by the usual methods of double decomposi- 
tion. The cWcfdoride, YClg, forms orange-yellow prisms or else a 
microcrystalline precipitate; the cis-iodide, Ylg, crystallises in 
reddish-brown needles ; the cis-nitrate, Y(N03)2, in flat, tabular, or 
needle-shaped crystals. The c'ls-dithionate, YSgOg, forms small, golden- 
yellow leaflets, whilst the cis- sulpfiate, YSO^, crystallises in long, 
radiating, light yellow, prismatic needles. The ci6-bromide~nitrate, 
YBr(N03), is prepared by the gradual addition of concentrated nitric 
acid to a well-cooled solution of the nitrate; it forms large, glistening, 
reddish-brown prisms. 

The following methods of preparation of the m-isomerides are also 
described : (1) By the action of silver nitrite on 1 : 2-chloroammine- 
diethylenediaminecobaltic chk)ride. (2) By the action of ammonia 
on 1 : G-dinitrodiethylenediaminecobaltic salts. (3) By oxidation of 
1 : 2-nitroi«othiocyanatodiethylenediaminecobaltic salts. 

The tr&us-nitrate, Y(N 03)2,^3^20, is prepared by dissolving 
1 : 6-nitronitratodiethylenediaminecobaltic nitrate in liquid ammonia, 
and allowing the solution to evaporate spontaneously. The residue is 
recr} stallised from water, whereby a mixture of large, dark brown 
plates and small, light yellow crystals is obtained, which are 



ORGANIC CHEMISTRY. i. 93 

mechanically separated. The latter crystals consist of 1 : 6-dinitro- 
nitrate, whilst the former are the required ^rans-nitrate, and, after 
further recrystallisation, are obtained as flat, rhombic tablets. By 
appropriate double decomposition, the nitrate yielded the following 
salts : the tr sins-iodide, YlgjHgO, as brown, glistening, prismatic 
crystals ; the tr sms-bromide, YBr^, as thick, short, columnar or 
tabular, dark brown crystals; the tvsins-thiocyanate, Y(SCN)2, as 
thick, glistening, brownish-yellow plates; the tra.iis-dithionatef 

YS,0e,H20, 
as long, glistening, fluted prisms. This latter salt was also obtained 
from a solution of the i{r<*ns- chloride, prepared by the interaction 
of 1 : 6 - chloronitrodiethylenediaminecobaltic chloride and liquid 
ammonia. 

The solubilities of the various ^ra?is-salts, expressed in grams of salt 
per 10 c.c. of water at 27°, are: nitrate, 2*827 ; thiocyanate, 1*458; 
bromide (at 26°), 0*6867 ; iodide, 0*7707. 

Nitroi9,othioGyanatodiethyle7iediammecohaltic salts, YX, where Y = 

^^^2 Co eng . — The salts of the ^raws-series are more easily soluble 

than the cis-isomerides, the sulphates showing the greatest difference 
in solubility. There is also a marked difference in the colour of the 
salts, the cis-compounds being brownish-yellow, whilst the trans- 
compounds are dark brown. 

The following reactions are different in the two series. Hydrogen 
peroxide partly oxidises the C2S-salts to cis-nitroammine-salts, and 
partly oxidises the thiocyanate group completely away ; the ^raws-salts, 
under similar conditions, give only <raws-nitroaquo-salts, the thio- 
cyanate group being split off completely. On heating with concentrated 
hydrochloric acid, the cis-isomerides give the cis-chloroisothiocyanato- 
salts, whereas the ^raws-isomerides are not affected by the same treat- 
ment. On oxidation with nitric acid and subsequent evaporation with 
hydrochloric acid, the cis-salts give 1 : 6-dichloro-salts, whilst the 
iraws-salts give 1 : 6-chloronitro-salts. 

[With C. Rix.] — The cis-chloride, YCl.HgO, is obtained by intra- 
molecular transtormation from 1 : 2-chloronitrodiethylenediamine- 
cobaltic thiocyanate, a solution of which in water containing acetic acid 
is evaporated to half its volume. The red colour changes to brown, and 
on cooling brownish-yellow needles of the cis-chloride deposit contain- 
ing 2H2O, but IH2O is lost in* a desiccator over calcium chloride. 
The chloride serves for the preparation of the other salts, for the most 
part by the method of double decomposition. The ch-bi'omide, YBr, 
forms light brown, nodular crystals ; the els-iodide^ YI, crystallises in 
brown prisms ; the cis-sulphate, Y2SO4, forms yellow, glistening scales ; 
the cis-nitrate^ YNO3, forms brown, thick crystals ; and the cis-thio- 
cyanate, YSCN, crystallises in brown leallets. The cis-sulphate may 
also be obtained by heating a solution of cis-chloroisothiocyanato- 
diethylenediaminecobaltic chloride with sodium nitrite and subsequent 
precipitation with ammonium sulphate. The cis-thiocyanate is also 
prepared by heating a solution of the cis-chloronitro-chloride with 
potassium thiocyanate. 

[With N. Goslings.] — The trsms-thiocyanatej YSCN, is obtained as 



i. 94 ABSTRACTS OF CHEMICAL PAPERS. 

brown, prismatic crystalh when polaHHiutu tbiocyausile i>> added to a 
solution of 1 : 6 chloronitrodiethylenediaminecobaltic nitrate. Methods 
are also described for its preparation by the action of potassium thio- 
cyanate on nitratonitrodiethylenediaminecobaltic thiocyanate and on 
1 : 6-nitroamminediethylenediaminecobaltic nitrate. The trans- cA/oriV/«, 
YCl.HgO, is obtained us reddish-brown, tabular crystals by di.ssolving 
the thiocyanate in concentrated hydrochloric acid and precipitation 
with alcohol ; the other salts are prepared from it by appropriate 
double decomposition. The tva.uH-bromide, YBr/HgO, forms brown, 
tabular crystals ; the trans-iodidef YI, crystallises in glistening, 
brown, irregular leaflets ; the tra.xis-nitrate, YNOa.HgO, forms brown 
plates, as also does the trans-wi^riie, YN02,H2(^- With silver nitrate 
the Ira7i8-mtr&te gives long, yellow needles of an additive compound, 

Dinitrotelramminecohallic salts, YX, where Y = [(N02)2Co(NH3)4]. — 
[With L. CoHN.] — By the addition of rubidium nitrate to a solution of 
the cis-nitrate (flavonitrate), a rubidium double nitrate, YN0g,E,bN03, 
is obtained as brown, rhombic, tabular crystals. It is analogous with 
the potassium double nitrate already prepared by Jorgensen. 

Dinitrodiethylenediaminecobaltic salts, YX, wht^re 
Y = [(0,N),Coen,]. 
— A number of the stereoisomerides have been described previously as 
dinitrito-salts ( Abstr., 1901, i, 511) ; the true dinitrito-saltswereprepared 
later (Abstr., 1907, i, 291). It has been found that the cis-nitrate is 
transformed into the trans-nitraite when its aqueous solution is heated. 
The cis-thiocyanate, YSCN, is obtained from the m-nitrate by precipi- 
tation with potassium thiocyanate ; it forms glistening, yellowish- 
brown, tabular crystals. The trains-thiocyanate, YSCN, forms orange- 
yellow, glistening, thick crystals. The trujis-hydrogeji sulphate, YH SO^, 
has been prepared from the iodide by interaction with silver oxide and 
subsequent neutralisation with sulphuric acid ; it forms glistening, 
yellowish-red needles. 

Stereoisomeric chloronitrodiethylenediaminecobaltic salts, 

[o^^CoeD,]x, 

have already been described (Abstr., 1901, i, 512). It has since been 
found that the i7-aw«-salts can be exposed to the action of concentrated 
hydrochloric acid for a long time without effect, whilst the cM-i?alt8 
rapidly give 1 : 2- and 1 : 6-dichloro-salts. 

trAUB- Nitrooiitratodiethylenediaminecobaltic salts, YX, where 

Y = ^2^ Co eujj .—Only the nitrate, YNO^, has been obtained. It 

is prepared by the oxidation of 1 : 2-dinitrodiethylenediaminecobaltic 
nitrate with concentrated nitric acid, and forms glistening, chamois- 
coloured crystals. By precipitation of the aqueous solution with 
concentrated nitric acid, an acid nitrate, YN03,HN03, is obtained. 
tT&ns-Nitroaquodiethylenediaminecobaltic salts, YXg. where 

Y = jj ^ Co eug . — The sulphate, YSO^, is obtained as follows : 2*8 
grams of solid ammonium sulphate are added to a solution of 4 grams 



ORGANIC CHEMISTRY. 1. 5^5 

of 1 :6-nitroTiitrato-diethyleD<-diainiDecobaItic uitrate in 10 c.c. of 
water, and then alcohol added until no further precipitate forms. It 
crystallises in orange-coloured needles. No other salts could be 
obtained, owing to their great solubility. 

Bichloroethyle7i6diaminediam7ninecobaUic salts, YX, where 

— Both series of stereoisomerides have been obtained. The method 
of preparation is briefly as follows : By warming trinitrotri- 
amminecobalt with ethylenediamine, trinitroethylenediamineammine- 
cobalt is obtained 



(NO,)3Co(NH3)3 + en = (NO,)3Co JJ-jj^ + 2NH,. 

By heating with concentrated hydrochloric acid, the latter salt is 
transformed into dichloroaquoethylenediamineamminecobaltic chloride, 

TT o ^^ >?R r^^' ^^ which 1 gram is then dissolved in 25% ammonia 

(3 J c.c). After five minutes, 3*5 c.c. of concentrated hydrochloric 
acid are added to the solution, which is then heated until it becomes 
greenish-blue in colour. On cooling, green crystals of the trans- 
chloride, YC1,JH20, are deposited, from which, by the method of 
double decomposition, the following salts were obtained, generally as 
green precipitates : tv'a.n&-nitrate, YNOg ; trans-^oo?^<ie, YI ; trans- 
bromide, YBr ; trams-thiocyanate, YSCN ; tra.ns-hydrogen sulphate, 
YHSO^.HgO ; tr Sius-dithionate, YgSgOg. The iodide is sensitive to 
light. 

The cis-isomerides were prepared from the ^raris-compounds as 
follows : By heating a solution of the ^raws-chloride with potassium 
carbonate until the colour had changed to red, and then cooling, garnet- 
red crystals of carhonatoethylenediaminediamminecohaltic chloride^ 

were obtained. By treating this compound with concentrated hydro- 
chloric acid in the cold, a solution of the required czs-chloride was 
obtained, from which, on the addition of ammonium bromide, the cis- 
bromide, YBr, was deposited as a bluish-violet precipitate. The 
CIS- dithionate J YgSgOg, is a violet precipitate obtained from a solution of 
the bromide by the addition of sodium dithionate. 

[With G. LiNDENBERG.] — Diacidoditrimethylenediaminecobaltic salts, 
[XgCo (tn)2]X. — Only the 1 : 6-dinitro- and 1 : 6-dichloro-salts have so 
far been prepared. The 1 : 6-dichloro-salts are distinguished from the 
corresponding diethylenediamine salts by their ready hydration 
(formation of aquo-salts) in aqueous solution. The neutral, green 
solution of a dichloroditrimethylenediamine salt rapidly becomes violet 
in colour ; the addition of concentrated hydrochloric acid restores the 
green colour. 

Carbonato-salts have been prepared from the 1 ; 6-dichloro-salts, 
but could not be made to furnish the stereoisomeric 1 : 2-dichloro- 
salts. 

tr&ns-Dinitrodit'i'imethylenediammecobahic salts, YX, where 

kY = [(NO,),CotnJ. 



1. 96 ABSTRACTS OF CHEMICAL PAPERS. 

— The nitrite f YNO^jis obtiiitied byheatiog potassium cobalti nitrite with 
trimethylenediamine in aqueous (solution. it forms large, thick, 
yellowish-brown, pleochroic, rhombic crystals. The bromide^ 

YBr,H20, 
and the iodide^ YI,2H20, are obtained from the nitrite by interaction 
with potassium bromide and iodide respectively, the former a 
brownish-yellow, monoclinic crystals, and the latter as yellow to 
yellowish-green, pleochroic, rhombic prisms. The chlm-ide, YCljHgO, 
and nitrate, YNOg, are best obtained from the iodide by interaction 
with silver chloride and nitrate respectively ; the former gives light 
to dark brown, pleochroic, monoclinic crystals, and the latter rhombic 
plates. 

1 :6-Dichloroditrimethylenediaminecobaliic chloride, [Clg Co tn2]Cl, i> 
obtained by heating the dinitronitrite with hydrochloric acid ; a green 
solution is obtained, which, on cooling, deposits green, prismatic, 
columnar crystals. The solution is turned red by sodium hydroxide 
and ammonia, and gives characteristic precipitates with the bromide, 
iodide, thiocyanate, permanganate, ferro(tyanide, ferricyanide, or nitrate 
of potassium, and with sodium thiosulphate. Hydrogen sulphide 
precipitates cobalt sulphide. Potassium platinichloride gives green 
crystals of the platinichloride, [Clg Co tngJgPtClg. 

Garhonatoditrimethylenediaminecohaltic chloride, [CO3 Co tnglCKHgO, 
was obtained by heating a solution of the 1 : 6-dichloro-chloride with 
sodium carbonate until it became bluish-red in colour. The addition 
of alcohol precipitated a white salt, and the red solution remaining 
deposited the required chloride in red, needle-shaped crystals. By 
interaction with hydrogen chloride, no matter under what conditions, 
the green 1 : 6-dichloro-chloride was always obtained. T. S. P. 

Optically-active Compounds of Cobalt and Chromium. 
Alfred Werner {Arch. Sci. Phys. Nat., 1911, [iv], 32, 457 — 467). — 
A gteneral account is given of results which have, for the most part, 
been already published (Abstr., 1911, i, 613, 838, 960; this vol., 
i, 10). In addition, the author mentions that optically-active com- 
pounds of the tetraethylenediamiiM-fx-aminoperoxodicobalt and tetra- 
ethylt^iediamine-fi-amino-ol-dicobalt series have been obtained. The 
rotations of the compounds of the first series are very large, the nitrate 
of the first series having a specific rotation of 840°, which corresponds 
with a molecular rotation of about 6000°. 

From a consideration of the results hitherto obtained it follows that 
the sign of the rotation is not connected with the configuration of the 
diethylenediaminecobaltic radicle. This is well shown by the fact that 
Z-tetraethylenediamine-/x-aminoperoxodicobalt salts furnish d-tetra.- 
ethylenediamine-/A-amino-ol-dicobalt salts on reduction : 

engCo ,Q f Co en^ X^ — > en^ Co ^ /-vu . Co en^ X^. 

Also, /-chlorowothiocyanatodiethylenediaminecobaltic salts and 
d-chlorouitrodiethylenediaminecobaltic salts both give rise to rf-nitro- 
tsothiocyanatodiethylonediaminecobaltic salts by interaction with 
sodium nitrite* and potassium thiocyanate respectively. 



ORGANIC CHEMISTRY. i. 97 

An examination of the compounds hitherto prepared shows that it 
is not always the isomeride of the same sign of rotation which 
gives the least soluble salt with o?-bromocamphorsulphonic acid. 

Preparation of Acid Chlorides from Two or More Molecules 
of Carbamide Chloride by Elimination of Hydrogen Chloride. 
Vereinigte Chininfabriken Zimmer & Co. (D.R.-P. 238961). — When 
carbamide chloride is heated in the abseoce of moisture either with or 
without a solverit, two or more molecules condense with evolution of 
hydrogen chloride. 

Allophanic chloride^ NHg'CO'NH'COCl, a fuming, colourless, readily 
decomposable powder, which reacts energetically with water according 
to the equation: NH2-C0-NH-C0C1 + H20 = C0(NH2)2 + C02 + HC1, 
was thus obtained at 30°, whilst at about 100° three molecules 
combined, yielding hiuretcarhoxyl chloride, C2H4N302*C0C1, a colour- 
less, non-fuming powder, decomposed by water with elimination of 
hydrogen chloride and carbon dioxide: CgH^OaNg'COCl-fHgO^ 
HCl + CO2 + NH2-CO-NH-CO-NH2. F. M. G. M. 

Hypochlorous [ Acid and] Amides. Etienne Boismenu (Compt, 
rend., 1912, 154, 1482—1484. Compare Abstr., 1911, i, 957).— 
The action of an aqueous solution of hypochlorous acid on amides at 
0° gives rise to monochloro- or dichloro-amides, according to the 
proportion of amide and of water employed. The dichloro-derivatives 
are yellow liquids, the stability of which diminishes as the molecular 
weight increases. On treatment with amides, they yield monochloro- 
derivatives. » 

Acetyldichloroamide, CHg'CO'NClg, has an odour of chlorine, and is 
insoluble in water. It decomposes above 0°, depositing crystals of acetyl- 
chloroamide. Propionyldichloroamide and fwmyldichloroamide have 
also been prepared. The latter is very explosive, and must be kept in 
well cooled vessels (compare Mauguin, Abstr., 1909, i, 892). 

W. 0. w. 

Cobalt Thiocyanates, and the Cause of the Colour Changes 
in Cobalt Salts. Arthur Hantzsch and Yuji Shibata {Zeitsch. 
anorg. Chem., 1912, 73, 309 — 324). — Cobaltous thiocyanate is largely 
bimolecular in urethane solution at 49°, but almost completely uni- 
molecular in alcoholic solution at 78°. The existence of complex ions 
in the alcoholic solution is shown by the method used by Donnan and 
Bassett (Trans., 1902, 81, 944). The absorption spectra show the blue 
cobalt band, and a broad band in the ultra-violet with its maximum at 
1/A. 3400 and minimum at 1/X 3850. The absorption is slightly 
increased at 55° and 80°. Beer's law is departed from at considerable 
dilutions. 

The colour of the blue solution is attributed to the presence of the 
complex salt, Co(SCN)4Co, in confirmation of which it is noted that 
the compound, Co(SCN4)Me2, is blue. The salt, 00(80^)4X3, is blue, 
but its spectrum in absolute alcohol is practically identical with that 
of cobalt thiocyanate, indicating dissociation into its components. 
Amyl alcohol gives an almost identical solution, whilst moist ether 

VOL. CII. i. h 



i. 98 



ABSTRACTS OF CHEMICAL PAPERS. 



contains the salt in an almont undis^ociated condition. The action of 
alcohols in promoting dinRociation \h attributed to the formation of the 
known alcoholateu of cobalt thiocyanate. The decomposition is still 
more pronounced in aqueous solution, but is lessened by the addition 
of potassium thiocyanate. 

The blue colour of cobalt thiocyanate is changed to pink by the 
addition of mercuric chloride or zinc chloride. The colour of the salt, 
Co(SCN)2,HgCl2, is not altered by further addition of mercuric 
chloride. This salt has not been isolated, but when the alcoholic 
solution is evaporated with a further quantity of mercuric chloride, 
pink crystals of a compound, 2Co(SCN)2,3HgCl2, are obtained. The 
change of colour in cobalt chloride solution is also due to the formation 
of a compound, [CoCl4,(HgCl2)2]Co, and not, as assumed by Donnan 
and Bassett, to (HgOl^JCo. 

The molecular weight of cobalt thiocyanate in aqueous solution 
shows that it only dissociates into two ions, except in very dilute 
solutions, whilst the chloride and bromide yield three ions, even in 
concentrated solutions. It is therefore considered to exist in solution 



as the compound 



SON. The whole of the colour changes 



(H,0)J' 

may be explained as changes of the co-ordinative unsaturated complex, 
CoX^, into the saturated complex, CoXg. C H. D. 

Systems Formed by Antimony Chloride and Bromide with 
Monosubstituted Benzene Hydrocarbons. Boris N. Menschut- 
KiN (J, Muss. Phys. Chem. Soc, 1911, 43, 1275—1302. Compare 
Abstr., 1911, i, 273). — The author has subjected to thermal analysis 
the systems formed by antimony chloride and bromide with toluene, 
ethylbenzene, propylbenzeue (see Abstr., 1911, i, 532), and isoamyl- 
benzene. The results are given in the form both of curves and of 
tables. 

Rosenheim and Stellmann (Abstr., 1902, i, 68) state that antimony 
trichloride forms with toluene a compound having a composition 
analogous to that of the benzene compound, namely, SSbCig.CgHgMe ; 
but this compound is really 2SbCl3,CgH5Me, the solid phase 
corresponding with 3SbCl3, C^H^Me being antimony trichloride 
itself. 

The melting points of the thirteen compounds formed by the eight 
systems examined are as follows : 

2SbCl3,CeH5R. SbCl3,C6H5R. 2Sb*Rr3,C6H6R. SbBrg.CeHgR. 

SbXj-CgHjMe 42-5° 15—16" 38—39" 9° (decomp. ) 

(decomp.) (decomp.) 

SbXs-CeHoEt 370 39-0" — 33 „ • 

SbXg-CeHjPr 9—10 15 — 1 ,, 

(decomp. ) 

SbXj-CsH.-CsHii ... 7-5° -205 — -15 
(decomp.) 

It will be seen that increase of the magnitude of the benzene sub- 
stituent is accompanied by decrease in the stability of the compounds 
formed with antimony trichloride and tribromide. 

The transition (/>) and eutectic («) points, and the corresponding 



ORGANIC CHEMISTRY. 



99 



com^iositions (mols. of hydrocarbon per mol. of antimony chloride), are 
given in the following table : 

2SbCl3,C6H5R- 

SbCl3,C6H5l{. 2SbCl3,C6H5R-SbCl3. SbCla.CfiHjjR-SbCla. 

Temp. Composition. Temp. Composition. 

40-0° 0-46 {e) — — 

3t5-8 0-47 (e) 33° 0-52 {e) 

8-5 0-88 ip) 1 0-98 (e) 

-21-0 1-3 ip) -5 1-2 ip) 



SbCla-CeHsEt.. 
SbCl,-CfiH,Pr.. 



Temp. 
11° 
35 

-33 



Composition. 
1-8 ip) 
0-62 [e) 

3-1 ip) 



The transition points for SbBrgjCgHglil-SbBrg are as follows : 

Composition. 



Temp. 



SbBra-CgHgEt 29° 1-17 

SbBivCeHgPr -5 3-1 

SbBr-j-CeHj-CgHn - 17 5-07 

This continual fall in the transition temperature again indicates 
diminution of stability of these compounds as the magnitude of the 
hydrocarbon increases. T. H. P. 

Systems Formed by Antimony Trichloride and Tri- 
bromide with Disubstituted Benzene Hydrocarbons. Boris 
N. Menschutkin (/. Muss. Phys. Chem, Soc,, 1911, 43, 1303—1328). 
— The systems here described contain o-, m-, or jt?-xylene or jt?-cymene. 
The results of the thermal analyses are given as curves and tables. 

The replacement of a second hydrogen atom of benzene by an alkyl 
radicle (compare preceding abstract) produces no change in the 
character of the system, the temperature diagrams being similar to 
those given by the systems containing monosubstituted benzenes. 
Also, here too, antimony chloride gives compounds of the two types 
2SbCl3,CgH4R2 and SbCl^jCgH^Eg* whilst the bromide, as a rule, yields 
only one compound, SbBrgjC^H^Rg. The compounds are of approxi- 
mately the same stability as those formed with toluene orethylbenzene. 
The results obtained with the three xylenes show that isomerism 
exerts a marked influence on the physical properties of these 
compounds. 

The melting points of the hydrocarbons and of the various com* 
pounds they form are given below, the numbers for methylbenzene 
being inserted for purposes of comparison : 
Hydro- 



r 


carbon. 


2SbX„C6H4Ro. 


Diff. 


SbX3,C«H4l?2. 


DifF. 


SbC]3-^-C6H4Me2 


14° 


70° 


56° 


56° 


42° 


SbCJ3-7/i-C6H4Me2 


-57 


38 


95 


7-5 
(decomp.) 


64-5 


SbCl3-o-C6H4Me2 


-29 


33-5 


62 5 


19-5'' 


48-5 


SbClg-CeHeEt 


-93 


37 


130 


39 


132 


jSbCl3-i?-C6H4MePr)3... 


-75 


40 


115 


5—6 
(decomp. ) 


80 


SbBr3-^-C6H4Me2 


14 


67*5 


53-5 


— 


— 


SbRr3-m-CfiH4Me2 ... 


-57 


— 


— 


13-5 


70-5 


,SbBivo-C6H4Me2 


-29 


— 


— 


24 


53 


i SbBr,-C«HsEt ... 


-93 






33 


126 










(decomp. ) 




.SbBr,-l>C„U,U<i?t».. 


-75 






10 
(decomp. ) 

T. H 


85 
P. 



h 2 



i. 100 ABSTRACTS OF CHEMICAL PAPERS. 



Relations of Trieubstituted Benzene Hydrocarbons 
Antimony Trichloride and Tribromide. Boris N. Menschutkin 
(./. Ru88. rhi/8. Chem. 6'oc., 1911, 43, 1329— 1341).— The Byatems 
formed by antimony trichloride and tribromide with 1 : 3 : 5- 
and 1:2: 4-trimethylbenzenes (mesitylene and ip-ciimene) have been 
examined. 

Mesitylene forms compounds of the two types 2SbX3,CgH3Mejj and 
SbXg.CgHgMeg with both antimony chloride and bromide, and the 
hame is the case with i/^-cumene. The only other benzene hydrocarbon 
with which this has been found to occur is toluene. 

The melting points of these compounds are as follows : 

2SbX3,C6H3Me5. SbXg.CeHgMeg. 

SbClj-1 : 3 : S-CgHaMeg 755^ 43° (decomp.) 

SbOla-l : 2 : 4-CfiH3Me3 56-0 - 4 to - 5° „ 

SbBr,-l : 3 : S-CeHgMes 69-5 38—39 

SbBr^-l : 2 : 4-C6H3Me3 36 '0 (decomp.) 13 ,, 

The eutectic points and the corresponding compositions are as 
follows : 

System ... (1) CfiHgMeg-SbXa.CeH^Mea. (2) 2SbX3,C6H3Me3-SbX3. 

f * ^ , ^ s 

M. p. of 

Com- hydro- Com- M. p. of 

Temp. position, carbon. Temp, position. SbX3. 

SbCL-l : 3 : S-CgHsMea -55-6' 126-2 -54-4° 58-5° 0-15 73° 

SbClj-l :2:4-C«H8Me3 -60-0 8-25 -57-4 51-0 0-27 73 

SbBr3-l : 3 : S-CgHgMes -55-2 147*0 -54 '4 69-0 0-42 94 

SbBrg-l : 2 : 4-CeH8Me3 -58 '8 28-4 -57 '4 — — — 
(Tha composition is given in mols. of hydrocarbon per mol. of SbXg. ) 

The transition points, SbX3,CgH3Me3-2SbX3,Cj.H,Me3, are as 

follows : 

Temp. Composition. 

SbCl3-l:3:5-C6H3Me3 38° 1-8 

SbClg-l : 2 : 4-C6H,Me3 -5 183 

SbBr3-l:8:5-(^6H3Me3 29 3-45 

^ SbBfa-l : 2 : 4-CeH3Me3 7 172 

Increase of the number of hydrogen atoms of benzene replaced by 
alkyl radicles does not diminish, but rather increases, the capability of 
these hydrocarbons to form compounds with antimony trichloride and 
tribromide. T. H. P. 

Electrolytic Reduction of Nitrobenzene. Ralph Cuthbert 
Snovvdon {J. Physical Clism., 1911, 15, 797— 844).— The author 
endeavoured to develop an electrolytic method of reducing nitro- 
benzene which should not require the use of a porous cup or a 
platinum anode. 

Nitrobenzene was vigorously stirred with ferrous chloride solution 
at 100° in a long cell provided with iron electrodes. The amount of 
anode iron dissolved was largely in excess of the electrolytic equivalent, 
a,nd dissolution of iron also occurred at the cathode in increasing 
proportion as the current density was lowered. With high current 
•densities (10 amp./<6/i^), cathode corrosion was very small, and the 



1 

to ■ 






ORGANIC CHEMISTRY. 1. 101 



yield attained 95% of aniline on the total iron dissolved. Although 
sheet iron in ferrous chloride solution will not reduce nitrobenzene on 
boiling, it was found that under the emulsifying influence of rapid 
stirring the iron electrodes dissolved equally, without electrolytic aid, 
and gave a 78% yield of aniline calculated on the iron dissolved, so 
that the commercial reduction of nitrobenzene by massive iron might 
be rendered possible by suitable agitation to bring the substances 
into intimate contact. The presence of a dissolved ferrous salt is 
essential in the electrolytic as in the chemical reduction. Ferrous 
chloride is apparently without action on nitrobenzene, so that its 
catalytic activity must be attributed to a depolarising influence on 
the iron. In this respect ferrous chloride and acetate are more efficient 
than the sulphate and benzoate. 

Nitrobenzene is reduced at 100° by alkaline sodium sulphide, freshly 
precipitated ferrous hydroxide, and sodium arsenite, but not by alkaline 
potassium ferrocyanide. 

Sodium arsenite gives 60 — 90% of azoxybenzene, 5 — 14% of aniline, 
and a trace of azobenzene. This is contrary to electrolytic experience 
where azobenzene is produced above and azoxybenzene below 90°. 
Alkaline sodium sulphide and ferrous hydroxide give aniline and 
small amounts of azobenzene. The yield appears to vary with the 
order in which the three components, nitrobenzene, sodium hydroxide, 
and reducing agent, are mixed. E,. J. C 

Aromatic Nitro-derivatives. Roberto Ciusa (Atti E. Accad. 
Lincei, 1911, [v], 20, ii, 523—524. Compare Abstr., 1911, i, 931).— 
The observation of Werner (Abstr., 1910, i, 20) that trinitro- 
mesitylene gives yellow solutions in some organic solvents, although 
it is not dissociated in formic acid solution, indicates that there is no 
connexion between the dissociability of the aromatic nitro-deriv- 
atives and their power to form additive products. The author now 
finds that tetranitromethane also is not dissociated in formic acid 
solution, although it can form additive products. R. V. S. 

Isomorphous Mixtures: the Systems Chloronitrobenzenee- 
Bromonitrobenzenes. Robert Krbmann (Zeitsch. Kryst. Min., 1911, 
60, 86; from Jahrb. k.h. geoL Reichs., 1908, 68, 659— 672).— The 
time-cooling curves and the freezing curves of the three systems 
(ortho, meta^ para) show that the crystallisation interval for mixtures 
of the ortho-series is very small ; that of the meta-series is also small, 
but it is larger in ohe para-series. The fusion curves of the two last 
systems belong to Roozeboom's type Y. L. J. S. 

l-Bromo-2 : 4 : 6-tri-iodo-3 : 5-dinitrobenzene and Some of its 
Derivatives. 0. Loring Jackson and Harold E. Bigelow {Amer, 
Ohem. J., 1911, 46, 549—574). — It has been shown by Jackson and 
Robinson (Abstr., 1890, 377) that 1 :3:5-tribromo-4:6-dinitrobenzene 
is converted by ethyl sodiomalonate into ethyl 3-bromo-4 : 6-dinitro- 
phenylmalonate. It has now been found that when l-bromo-2:4:6-tri- 
iodo-3 : 5-dinitrobenzene is treated with ethyl sodiomalonate at the 
ordinary temperature, l-bromo-2 : 6-di-iodo-3 : 5-dinitrobenzene and 
ethyl ethanetetracarboxylate are produced, whilst if the mixture is 



i K'J ABSTRACTS OF CHEMICAL PAPEIIS. 

lieated, ethyl 2-brorao-3-iodo-4 : 6-dinitrophenylmalonate is obtained. 
This shows that the explanation given previously (Jackson and Moore, 
Abstr., 1890, 497; Jackson, Abstr., 1890, 983) is not correct, but 
that it must bo assumed that ethyl sodiomalonate reacts in the enolic 
form, and that the iodine atom and the •CflBrr2(N02)2 group are added 
at the double bond with production of the compound 

C02KfCHI-C(OEt)(ONa)-C^T2Br(N02)2. 
On acidification, the hydrogen of the 'OH group might combine with 
the substituted phenyl group with formation of the compounds 
CflHBrl2(N02)2 and CHI(C02Et)2 ; the latter would then react with 
the excess of ethyl sodiomalonate to produce ethyl ethanetetra- 
carV)oxylatP. 

\Bromo-2 -AiQ-tri-iodobenzene, C^^HgBrl,, m. p. 146°, obtained by 
treating a mixture of 2:4: 6-tri-iodoaniline, glacial acetic acid, and 
hydrobromic acid with sodium nitrite, crystallises in pale yellow 
needles, and when heated with fuming nitric acid is converted into 
l-bi'OTno2:4t:Q-tri-iodo'3:5-dinHrohenze7ie, C^Brl3(N02)2> m. p. 292^^, 
which forms white needles. When tri-iodoaniline containing dark- 
coloured impurities was employed, the crude l-bromo-2 : 4 : 6-tri-iodo- 
benzene yielded, on nitration, some 1 : 3-dibromo-2'A:6t7'i-iodo-5-nitro- 
benzene, C^jBrglg'NOg, m. p. about 256° (decomp.), which crystallises in 
hexagonal prisms. 

I-Bromo'2 :6-di-iodo-3 :6-dinitrobenzene, C^^HBrl2(N02)2, m. p. 187°, 
crystallises in straw-coloured needles. Ethyl 2-bromo-3-iodoA : 6-di- 
nitrophenylmalonate, CgHBrI(N02)2-CH(C02Et)2, m. p. 107°, forms 
stout, lemon -yellow crystals. A small quantity of another compound, 
m. p. about 250° (decomp.), was also isolated from the product of the 
reaction between ethyl sodiomalonate and l-bromo-2 : 4 : 6-tri-iodo- 
3 : 5 -di nitrobenzene. 

By the action of sodium ethoxide on l-bromo-2 : 4 : 6-tri-iodo-3 : 5-di- 
nitrobenzene, 3-bromo-2 : 4 : Q-tri-iodo-b-nifrophenetole, 

CgBrT3(N02)-OEt, 
m. p. 148°, is obtained, which crystallises in light pink needles, and is 
reduced by zinc and acetic acid to m-aminophenol. 3-Bromo-2'A:6-tri- 
iodo-5-nUroani8ole, CgBrl3(N02)*OMe, m. p. 163°, forms pale yellow 
needles. 

When 2-bromo-l :3:5-tri-iodo 4:6-dinitrobenzene is heated with zinc 
and acetic acid, 5-bromo-77i-phenylenediamine is produced, but on 
reduction with ferrous hydroxide it is converted into \-bromo- 
2 :A : Q-tri-iodo-m-phenylenediaminej C^Brl3(NH2)2, m. p. 187°, which 
forms stout, greyish-white needles, and yields a ^ hydrochloride, 
decomposing at 100°. 

Reduction experiments have been carried out with several other 
iodo-com pounds. Zinc and acetic acid remove iodine from 1:3: 5-tri- 
iodo-4 : 6-dinitrobenzene. 2:4: 6-Tri-iodoaniline is not affected by 
tin and hydrochloric acid, and only very slightly by zinc and acetic 
acid. l-Bromo-2 : 4 : 6-tri-iodobenzene is reduced by zinc and acetic 
acid with formation of ;?-iodobromobenzene. These experiments show 
t.hat iodine is more easily replaced by hydrogen than is bromine. 

Sodium ethoxide does not react with 2:4: 6-tri'iodobenzene, and 
only very slightly with l-bromo-2 : 4 : 6-tri-iodobenzene. E. G. 



ORGANIC CHExMISTRY. i. 103 

Preparation of Alkylamines by Catalysis. Paul Sabatier and 
Alphonse Mailhe (Gompt. rend., 1911, 153, 1204 — 1208. Compare 
Abstr.j 1909, i, 292; 1911, ii, 627).— An extension of the general 
reaction already described to the preparation of new amines. 

^soPropyl alcohol is transformed into isopropylamine when its 
vapour mixed with ammonia is passed over thorium dioxide at 250° ; 
the yield is 20%. At higher temperatures propylene is formed 
together with diisopropylamine. The reaction proceeds with difficulty 
in the case of diphenylcarbinol. At 280° the corresponding amine is 
obtained, but the chief product is tetraphenylethylene ; this substance 
is easily obtained at .300° in absence of ammonia. 

cyc^oHexanol and also its 2-, 3-, and 4-methyl derivatives yield the 
primary and secondary amines at 290 — 320°. 4:'-Methylcyc\ohexyl- 
aminoA-methylcjclohexane, (CgHjQMe)2NH, b. p. 275° (decomp.), forms 
2i phenylcarhamide, m. p. 181°. 

The following secondary amines were prepared by passing a mixture 
of c?/c/ohexylamine and an alcohol over thorium dioxide at 320°. Ethyl- 
aminocyc^ohexane, CgHu'NHEt. FropT/laminocjclohexane, h. p. 185°; 
the phenyl carbamide has m. p. 113°. \soButylaminocyc\ohexane, h. p. 
193°; the phenyl carbamide has m. p. 90°. iso A mylaminocjclohexanSf 
b. p. 205° ; the phenylcarbamide has m. p. 129°. Benzylaminocjclo- 
hexane, b. p. 195°/80 mm., the phenylcarbamide has m. p. 121°. 

Gyc\oHexylamino-2-methylGyclohexaney b. p. 260° with slight decom- 
position ; the hydrochloride has m. p. 182°, and the phenylcarbamide, 
m. p. 140°; the d-methyl derivative, b. p. 270° (decomp.), forms a 
hydrochloride, m. p. 197°, and 2i phenylcarbamide, m. p. 191°, whilst the 
i-methyl derivative, b. p. 270°, gives a phenylcarbamide, m. p. 108°. 
The yield of the latter was 20% ; the lowest yield was obtained in the 
case of methylaminocyclohexane. W. O. W. 

Behaviour of Nitrosomonoarylcarbamides towards Primary 
Amines and Phenols. J. Haager {Monatsh, 1911, 32, 1089 — 1102). 
— Nitrosomonoarylcarbamides condense in alcoholic solution with 
primary aromatic bases to diazoamino-compounds, which contain the 
aromatic nuclei of both components, and to arylcarbamides which 
contain the nuclei of the bases. Accordingly, the rest of the carbamio 
acid, and not the nitroso-group,is eliminated from the nitrosocarbamides. 
The change is the same when the mixture of the components is heated. 

Nitrosoarylcarbamides react aLso with alkaline, and with alcoholic, 
solutions of phenols and their derivatives, with the formation of, 
hydroxyazo-compounds and alkaline salts of cyanic acid, which 
have been formed by the elimination of -C0*NH2 from the nitroso- 
carbamides. 

Nitrosophenylcarbamide reacts with aniline to form diazoamino- 
benzene and phenylcarbamide ; with jo-toluidine, benzenediazoamino- 
toluene, m. p. 85°, and ;?-tolylcarbamide are obtained. Nitroso-/)-tolyl- 
carbamide and aniline yield the same compounds. 

Nitrosocarbamide with phenol yields benzeneazophenol ; with 
resorcinol it gives benzeneazoresorcinol, m. p. 161°. ;?-Nitrosotolyl- 
carbamide and resorcinol give rise to «-tolueneazoresorcinol, m. p. 
183—184°. E. F. A. 



K 



i. 104 ABSTRACTS OF CHEMICAL PAPERS. 

The Action of Phosphorus Thiochloride on Alkaline 1 
Solutions of Phenols. Wilhklm Autenrieth (B&r.^ 1911, 44, ( 
3754 — 3755). — The author draws attention to the fact that several of | 
the substances prepared previously by himself (Abstr., 1898, i, 419): 
have since heen described afresh with different nomenclature (Ephraim, 
Abstr., 1911, i, 284 ; this vol., i, 26). D. F. T. 

Dinitrophenols. Fritz Ullmann and Shrirang M. Sane (Ber., 
1911,44,3730—3737. Compare Abstr., 1908, i, 525; 1909, i, 21, 
23). — On warming 4-chloro-2 : 6-dinitrophenol with toluenesulphonyl 
chloride and diethylaniline, 1 : A^-dicMoro^ : 6-dinitrobenzene is obtained ; 
it forms colourless leaflets, m. p. 105° (corr.). If, however, the diethyl- 
aniline is replaced by sodium carbonate solution, the product is 
4-c/i/oro-2 : Q-dinitropfienyl ^^-toluenesvlphonate ; this crystallises in 
colourless needles, m. p. 127° (corr.) ; the action of ammonia on a boil- 
ing xylene solution of this ester yields 4-chloro-2 : 6-dinitroaniline 
(compare Korner, Abstr., 1876, i, 230) ; similarly, the action of aniline 
on an alcoholic solution of the ester produces orange-yellow needles of 
4:-chloro-2 : ^-diniirodiplienylamine, m. p. 130°, the same substance being 
obtained also from aniline and 1 : 4-dichloro-2 : 6-dinitrobenzene. The 
last-named substance also reacts with dimethyl- 
NOg amine, yielding 4-chloro-2 : 6-dinitrodimethyl- 

/\_^Tl /\ aniline as orange-yellow crystals, m. p. 111° (pro- 
^.| i n ~l I b*bly identical with that already described by 
^\/~^~\/ Pinnow, Abstr., 1899, i, 203). By the action of 
the above-mentioned dichlorodinitrobenzene or 
chlorodinitrophenyl ^? toluenesulphonate on o-aminophenol there is 
obtained 2-chloro5-nitrop/uinoxazine (annexed formula) in violet 
needles, m. p. about 192°. 

1 : %Dichlm'0-Z : 5-dinUrobenzene is obtained from 6-chloro-2 : 4- 
dinitrophenol in a similar manner to the 1 : 4-dichloro-ipomeride 
above ; it forms hexagonal, pale yellow tablets, m. p. 56° ; in boiling 
alcoholic solution with ammonia it yields yellow needles of 2-chloro- 
4 : 6 dinitroaniline (m. p. 157°), and with aniline, brick-red crystals of 
2-chlorO'A : 6-dinitrodiphenylamine. Heated in alcoholic solution with 
o-aminophenol, it yields 3 : 5-dinitrophenoxazine (compare Turpin, 
Trans., 1891, 69, 722). 

2-Chloro-3 : 5-dinitrotoluene, m. p. 63° (corr.), is obtained by the 
action of toluenesulphonyl chloride and diethylaniline on 3 : 5-dinitro- 
o-cresol ; the lower m. p. previously obtained for this substance 
(Nietzki and Rehe, Abstr., 1893, i, 15) was due to impurity. In the 
above procesR, 3 :5dinitro-o-tolyl p-toliienesulphonate (colourless needles, 
m. p. 167°), is obtained as a by-product. If the above chlorodinitro- 
toluene is allowed to react with o-aminophenol, 2 : 4-dinitro-Q-methyl- 
2' -hydroxy diphenylamine is obtained, which crystallises in reddish- 
brown tablets, m. p. 177° (corr.), and by treatment with dilute soda 
passes into 3-nitro-b-methylp1ienoxazine (brown needles, m. p. 205° with 
decomp.). 

The methyl esters of 3 : 5-dinitro-2-hydroxybenzoic acid and of 
3 : 5-dinitro-4-hydroxybenzoic acid on treatment with toluenesulphonyl 
chloride and diethylaniline give the methyl esters of 2-chloro-3 : 5- 



ORGANIC CHEMISTRY. i. 105 

dinitrobenzoic acid (compare Purgotti, Abstr., 1902, i, 777) and 
4-chloro-3 : 5-dinitrobenzoic acid (compare Ullmann, Abstr., 1909, 
i, 475) respectively. D. F. T. 

The Action of Metals on Fused Picric 4-cid. J. Saposhnikoff 
(Zeitsch. ges. Schiess. Sprengstoffwesen, 1911, 6, 183 — 185). — Kast's 
work is discussed (Abstr., 1911, i, 852). The author heated one gram 
of various metals (in shavings or powder) with two grams of picric 
acid at 125° ; the amount of dissolved metal was estimated and found, 
with the exception of tin, to be in proportion to the equivalent weights of 
the metal. The respective weights dissolved by the picric acid were : 
tin, O'OO ; aluminium, 00488; iron, 0*153; copper, 0-1754; nickel, 
0-1862 ; zinc, 0-2046, and lead, 0*2798 gram. R M. G. M. 

Electrolytic Reduction of Nitrated Phenyl Thiocyanates. 
Fritz Fighter and Theodor Beck {Ber., 1911, 44, 3636—3648).— 
Miiller has shown that the reduction of o-nitrophenyl, jo-nitrophenyl, 
and 2 : 4-dinitrophenyl thiocyanates by alcoholic ammonium sulphide 
causes elimination of the thiocyano group and the formation of nitrated 
diphenyl disulphides, whilst their reduction by stannous chloride 
yields thiazole derivatives {Zeit, Farh. Ind., 1906, 6, 357). The 
authors now show that different products are obtained by the electro- 
lytic reduction of these thiocyanates at lead or copper cathodes ; the 
thiocyano-group is only attacked when lead cathodes are used. The 
reduction of phenyl thiocyanate in 2iV-alcoholic sulphuric acid at 
a rotating lead cathode and with a current density of 0*02 ampere 
per sq. cm. (the anodic compartment contains a lead plate in 
2ir-sulphuric acid) yields hydrogen cyanide and 57*5% of phenyl 
mercaptan. Under similar conditions the reduction of o-nitrophenyl 
thiocyanate yields 1-aminobenzthiazole, which is probably produced by 
the secondary interaction of the o-aminophenyl mercaptan and hydrogen 
cyanide initially formed. With a copper cathode and a current 
density of 0-019 ampere per sq. cm., o-nitrophenylthiocyanate is 
reduced to the sulphate of 2-amino-5-hydroxyphenyl thiocyanate, 
C^HgON2S,H2S04,H20, probably through the intermediate formation of a 
hydroxylamine derivative. 2- Amino-b-hydroxy phenyl thiocyanate, 

NH2-C6H3(OH)-SCN, 
m. p. 121°, yields an N-acetyl derivative, m. p. 206° (decomp.) (the 
methyl ether of which has m. p. 81°), a diacetyl derivative, m. p. 183°, 
and, after diazotisation, couples with )8-naphthol to form an azo- 
compound, m. p. 130°. 

jo-Nitrophenyl thiocyanate is reduced to jo-aminophenyl thiocyanate 
at a lead or copper cathode, but in the latter case the intermediate pro- 
duct, ^-thiocyanoazoxybenzene, ON2(CgH4*SCN)2, m. p. 170—171°, 
reddish-yellow leaflets, can be isolated. 

The electrolytic reduction of 2 : 4-dinitrophenyl thiocyanate, on 
account of its slight solubility and the consequent large volume 
of solution, must be effected with large stationary cathodes of lead or 
copper foil ; also the solution (in alcoholic sulphuric acid) must be hot, 
and a large current density, 0-033—0-038 ampere per sq. cm., Diust be 



i. 106 AHSIRACTW OK CKEMICAL PAPERS. 

employed. With a lead cathode, the product is 1 : A-diarnino-^-hydroxy^ 
bmzthinzole sidphate, NH2-CoH2(OH)<^>C-NH2,H2SO^. the formi 

tion of which is readily explicable in view of the course of the redu< 
tion of the o- and /^nitrophenyl thiocyanates. In favour of thii 
constitution is the fact that the sulphate yields a (iiacetylamint 
derivative, m. p. 268°, which is soluble in sodium hydroxide, and forma 
l-amino-i-acefylamiiioS-methoxybenzthiazole, m. p. 257 — 258°, witi 
methyl sulphate and sodium hydroxide. When reduced at a coppei 
cathode and with a current density of 0*05 — 006 ampere per sq. cm., 
2 : 4-dinitrophenyl thiocyanate yields, at fir.-«t the sulpfiate of i-nitrc 
2-a'niino - b - hydroxyphenyl thiocyanate^ SC-H^OgNgSjHgSO^ {diacetyl 
derivative, Cj^HgO^NgS, yellow, microcrystallme powder), and finall; 
the sulphate of 2 : 4:-diamino-b-hydroxyp/ienyl thiocyanate^ 

(^'N-dia^etyl derivative, m. p. 217°; triacetyl derivative, m. p. 156°). 

C. S. 



New Halogen Compounds of the Normal Butane Series 
Julius von Braun and H. Deutsch (Ber., 1911, 44, 3699—3706^ 
Compare Braun, Abstr., 1911, i, 610). — Phenoxybubylene, C^H^'OPh, 
obtained on decomposition of phenoxybutyltrimethylammoniui 
hydroxide, OPh*[CH2]4'NMe3'OH, yields with bromine phenyl-yl 
dihromohutyl ether, OPh'C^HyBrg, which is converted by hydrogei 
bromide into aph-trihromobutane, CHgBr'CHg'CHBr'CHgBr. Mag- 
nesium removes two atoms of bromine, forming magnesium hutylei 
bromide, MgBr'ICHgJg'CHICHg, and this is readily converted into' 
Ay-pentenoic acid, CJHg^CH'CHg'CHg'COgH, confirming the structural 
formula assigned to the preceding compounds. 

Phenoxybutylene unites with hydrogen bromide to form phenyl 
y hromobutyl etJier, OPh-[CH2]2-CHMeBr. 

Phenoxybutylene is an oil, b. p. 208— 210°/760 mm., 94—95°/ 
16 mm. 

Plienyl yh-dihromohutyl etiier is a colourless, odourless oil, b. p. 
191— 194°/13 mm. 

a^h-Trihromohutane is a colourless liquid of pleasant odour, b. p. 
115— 117°/10mm. 

The magnesium compound interacts with a variety of substances, so 
introducing the homoallyl complex, CH2lCH»CH2*CH2 ; thus with 
benzaldehyde, phenylbutenylcarbinol , ()H*CHPh'[CH2]2*CHIOH2, is 
obtained as a viscid, colourless liquid of ethereal odour, b. p. 
125°/ 11 mm. 

Phenyl -y-bromobutyl ether is a colourless, odourless oil, b. p. 
130 — 131°/9 mm. After prolonged boiling with potassium cyanide, 
the nitrile is obtained as a colourless, odourless oil, b. p. 156 — 157°/ 
10 mm., and this, when boiled for ten hours with alcoholic potassium 
hydroxide, gives y-plienoxy-a-m^thylbutyric acid, 

OPh-CH2-CH2-CHMe-C02H, 
which separates in lustrous, colourless crystals, m. p. 79°. The silver 
salt is a colourless, caseous precipitate. E. F. A. 



ORGANIC CHEMISTRY. i. 107 

Simple Method of Formation of Hydroxyhydrindones. 
Karl Auwers {Ber., 1911, 44, 3692—3699. Compare Abstr., 1910, 
i, 629). — On heating p-tolyl a-bromopropionate with aluminium 

chloride, 7-hyclroxy-4-methyl-l-hydrindone, OH-CgHgHe^Q^Z^OHg, 

is obtained instead of o-bromopropionyl-;o-cresol as expected. The 
structure of the hydrindone is established by the facts that it yields a 
semicarbazone and phenylhydrazone both soluble in alkali, and 
containing therefore a phenolic hydroxyl. The nucleus can be 
benzoylated and methylated, and this methyl derivative still forms a 
semicarbazone. 

In a similar manner, the homologous isomeric methyl derivatives 
have been obtained from the ^-tolyl a-bromobutyrate and a-bromoiso- 
butyrate. It is characteristic of these oxyhydrindones that their aqueous 
or alcoholic solutions are coloured deep blue by ferric chloride. 

It is probable in the above reaction that ;?-cresol vinyl ketone^ 
OH'C^HgMe'CO'CHICHgt is formed as an intermediate product. 
The yield of hydroxyhydrindones is only about 50% of the possible ; 
coumaranone derivatives are also formed. 

^-Tolyl a-bromopropionate forms colourless, lustrous needles, m. p. 
33°, b. p. 145— I507I8 mm. 

^-HydroxyA-rtiethyl-l-hydrindone separates in flat, colourless, lustrous 
needles, m. p. 110 — 111°. The semicarbazone crystallises in colourless 
needles, m. p. above 280° ; the phenylhydrazone forms lustrous, almost 
colourless, fatty needles, m. p. 183°. The benzylidene compound crys- 
tallises in faintly yellow-coloured needles, m. p. 129°. The benzoate is 
characterised by short, colourless, lustrous, fatty needles, m. p. 
124 — 125°, and the methyl ether by stellate aggregates of slender, 
colourless, lustrous needles, m. p. 112 — 113°. This methyl ether 
forms a semicarbazone, colourless needles, m. p. 220 — 224°, and a 
benzylidene derivative, colourless, lustrous needles, m. p. 185 — 186°. 

^-Tolyl a-bromoisobutyrate forms slender, colourless needles, m. p. 
39—40°, b. p. 152°/18 mm. 

7-IIydroxy-2 : 4:- dimethyl-1 -hydrindone ^ 0H*CgH2Me<^p^_^^CHMe, 

crystallises in colourless needles, m. p. 53°; the benzoyl derivative 
yields lustrous, colourless needles, m. p. 113 — 114°; the semicarbazone 
gives colourless, glass-like crystals, which gradually become citron- 
yellow on exposure; they become brown at 220°, m. p. 230 — 232°. 
This hydrindone does not form a benzylidene compound. 

7-IIydroxy-Z : i-dimethyl-l-hydrindone, OH*CgHgMe<C pp, ^CHg, 

separates in stunted, colourless, lustrous crystals, m. p. 53 — 54°. 
The semicarbazone forms stunted crystals, m. p. 217°; the benzylidene 
compound gives glass-like, yellow, flat needles, m. p. 114°. 
T^-Tolyl a-bromobutyi^ate is an oil, b. p. 160 — 163°/20 mm. 

E. F. A. 

Retene. II. Alfred Heiduschka and H. Grimm {Arch. Pharm., 
1912, 250, 33—45. Compare Abstr., 1910, i, 397).— Retenequinone 
reacts with organomagnesium haloids to form dihydroxydialkyl- 



i. 108 ABSTRACTS OF CHEMICAL PAPERS. 

dihydroretenes, and these were isolated in a crystalline condition in 
the case of the phenyl, benzyl, ;?-tolyl, naphthyl, and methyl 
derivatives, but could not be obtained pure in the case of o-tolyl, 
t»-xylyl, bromocamphor, ethyl, or i-amyl derivatives. Experiments 
on the reduction and dehydration of dihydroxydiphenyldihydroretenc 
are also recorded. 

DihydroxydiphenyldihydrorBUne, Cj,f,H2g02, m. p. 172°, obtained by 
condensing magnesium phenyl bromide with retenequinone in ether, 
forms colourless crystals, and is coloured red by sulphuric acid, 
yellow by fuming nitric acid. Heated with acetyl chloride, it yields 

the corresponding anhydride^ ^i6^i6'*\Xpu^^» ^- P- ^^^ — 144°, crys- 
tallising in clusters of needles, and giving when heated with potassium 
hydroxide in alcohol, in closed vessels, an acid, which probably 
corresponds with the product described by Acree (Abstr., 1905, i, 216) 
as obtained from diphenylphenan throne; its ethereal solution is coloured 
blue by ammoniacal copper oxide, and then yields a copper derivative, 
{Q^^^^O^,p\\, m. p. 142°, which at 125 — 140° slowly loses ammonia 
and turns green. 

When heated with zinc dust, dihydroxydiphenyldihydroretene yields 
diphenijb'etene, m. p. 200°, crystallising in colourless needles from 
alcohol or acetone. Reduction with hydriodic acid and phosphorus 
gives rise to diphenylhexahydrwetene (which forms colourless crystals, 
sinters at 82°, and melts completely at 118°), and eventually to 
Liebermann and Spiegel's retenedodecahydride. 

On bromination in carbon disulphide, dihydroxydiphenyldihydro- 
retene gives a pale yellow, finely granular powder, which on distillation 
with zinc yielded diphenylretene. Chlorination produced a similar 
product, containing 39*5% chlorine. 

Dihydroxydi-^-tolyldihydroretene, m. p. 203°, obtained in a manner 
analogous to that described for the phenyl derivative, forms glancing, 
colourless leaflets. The anhydride, m. p. 152 — 154°, occurs in 
colourless, transparent, small tablets. The products of bromination 
and chlorination resemble those of the lower homologue. Dihydroxy- 
dihenzyldihydroretene, m. p. 200 — 201°, forms stellate clusters of small, 
glancing needles. Dihydroxydinaphthyldih'ydroretene, m. p. 217 — 218°, 
was isolated with some difficulty by treating the crude product with 
warm toluene; it yields an anhydride, m. p. 188°, which forms small 
glancing crystals from acetone or alcohol. Dihydroxydimethyldihydro- 
retene, m. p. 166 — 167°, was eventually obtained in poor yield as small, 
colourless crystals, giving a violet-brown coloration with sulphuric 
acid. 

On chlorination in carbon tetrachloride with iodine as carrier, 
retene furnishes a viscid product, which on precipitation from 
alcohol with water forms an amorphous, colourless substance, 
CigHi^Clg [?], m. p. 98—100°. T. A. H. 

Influence of Sulphur and Sulphur-containing Groups on 
the Order of Substitution of Hydrogen Atoms in Benzene by 
Bromine. Edouard Bouhgeois and A. Abraham (Eec. trav. chim., 
1911, 30, 407—425. Compare Abstr., 1904, i, 28).— Substances 



ORGANIC CHEMISTRY. i. 109 

containing either of the groups ~SH, >SIO, -SO^H, are completely 
transformed by bromine. The authors have studied the action of 
bromine on aromatic sulphides and disulphides, sulphones and 
sulphonic acids. With bromine, the sulphides give rise to dibromides 
of the type SRR'IBr2, which show no tendency to split up into the 
sulphide and free bromine, but readily become transformed into 
substitution products. 

Phenyhnethylsulphoniuvfh dibromide, SMePhBrg, is obtained as a red, 
crystalline substance, m. p. 87 — 88°, when bromine acts on phenyl 
methyl sulphide in carbon tetrachloride solution below 0° Above this 
temperature it gives off hydrogen bromide, and is transformed into 
i^-bromophenyl 7nethyl sulphide, m. p. 37 — 37*5°. This, when oxidised 
by potassium permanganate in acetic acid solution, yields the corre- 
sponding sulphone, m. p. 102'5 — 103°, which with phosphorus 
pentachloride gives jt?-chlorobromobenzene. The sulphide can also 
be obtained by the action of methyl iodide on the sodium salt of 
j9-bromothiophenol. 

Diphenylsulphonium, dihromide, ^^h^v^, is obtained by a similar 
reaction to the above as a red, crystalline precipitate, which still 
more readily passes into the corresponding p-bromophenyl sulphide. 

Phenyl disulphide when dissolved in bromine yields jp-dibromophenyl 
disulphide (compare Hiibner and Alsberg, Annalen, 1870, 156, 328). 

Phenyl methyl sulphone is not attacked by bromine unless a 
catalyst, such as ferric chloride, is employed, in which case there is 
produced y^-bromophenylmethylsulphone, identical with that obtained 
by the oxidation of the corresponding sulphide with potassium 
peroaanganate {loc. cit.). 

In all the above cases, the bromine atom enters the para-position to 
the sulphur-containing group, whilst, in the case of the sulphonic 
acids, the group -SO3H directs the bromine to the meta-position. 

W. G. 

Oxonium Compounds. George L. Stadnikoff {J. Russ. Phys. 
Chem. Soc, 1911,43, 1244— 1257).— According to Nef's theory, the 
first stage of the interaction of an alkyl halide with alcoholic alkali 
hydroxide consists of the dissociation of the alkyl halide into halogen 
hydracid, which is neutralised by the alkali, and the methylene residue 
li'CH!, which either combines with the alcohol, forming a simple 
ether, or undergoes isomeric change into an olefine. The fact that 
tert.-hutyl iodide, which is incapable of methylene dissociation, gives 
no ether when treated with alcoholic alkali hydroxide, is regarded as 
confirmation of Nef's theory. The author finds that this evidence 
is fallacious, since tertiary alkyl halides, such as tert.-smiyl bromide, 
do give ethers under the above conditions, although the yield is very 
small; also ieri.-butyl iodide yields an appreciable amount of ether 
if treated with the alcoholic alkali in a sealed tube. Another 
observation which is not in agreement with Nef's theory is that 
triphenylmethyl chloride reacts with alcohols, giving ethers in 
theoretical yields. 

The most obvious method of explaining these reactions is to 
assume that the alkyl halogen compound, RX, dissociates into alkyl 



i. 110 ABSTRACTH OF CHEMICAL PAPERS. 

and halogen, which then combine with the alcohol, forming an oxonium 
compound, K'lIIOlRX. The latter may then decompose in two ways, 
giving (1) K'-O-R + HX or (2) 11'H:0:HX4- an olefine. These 
reactions would hence be closely analogous to those between alkyl 
halides and amines (see this vol., i, 116). 

Owing to the doubt which exists concerning the intermediate 
formation of oxonium compounds in such reactions as the above 
and in the Grignard reaction, the author has studied the following 
reactions. 

(1) The action of propyl iodide on triphenylmeth\l ethyl ether in 
presence of magnesium. Here the first stage of the reaction con- 
sists in the formation of the oxonium compound, CPhg'OEtlPrI, 
which then decomposes, giving triphenylmethyi iodide and ethyl propyl 
ether. 

(2) With the same ether as in (1), zsobutyl iodide in presence of 
magnesium combines to form an oxonium derivative, which is 
subsequently resolved into triphenylmethyi iodide and ethyl isobutyl 
ether. 

(3) Diphenylmethyl propyl ether and isobutyl iodide react in 
presence of magnesium, giving the oxonium compound, 

CHPh2-0PrI-C^Hj), 
which decomposes in three ways, giving (a) CHPhgl + C^Hf^'OPr ; 
(6) C4Hc,T+CHPh2-OPr; and (c) C3H7l-hCHPh2-0-C4H9(?). 

Diplienyhiiethyl propyl ether, GHPhg'OPr, prepared by the inter- 
action of diphenylbromomethane and propyl alcohol in presence of 
potassium hydroxide, is a colourless, mobile liquid, b. p. 161°/ 11 mm. 

T. H. P. 

Some Chlorine Derivatives of Cholesterol. Stephan Minovici 
and Bella Hausknecht (Biochein. Zeitsch., 1912, 38, 46 — 52).—^ 
When cholesterol in alcoholic solution is treated with chlorine gas, 
two substances are formed ; one, 04011,72^3^^^2 ^^ CJ42^72^3^^^2» ^^ 
soluble in alcohol and contains water of crystallisation, m. p. 125°, 
and when anhydrous, m. p. 130°; the other, O^gHjQ^OgClg, m. p. 195° 
(precipitated from ethereal solution by alcohol), is insoluble in alcohol. 
The formation of the former substance can be explained on the assump- 
tion that two molecules of cholesterol combine to form an ether, from 
which by the chlorinating and oxidising action of the chlorine, two 
vinyl and two wobutyl groups are eliminated and replaced by hydroxyl 
and chlorine. By the action of hydrogen chloride and hydrogen 
peroxide, a third chlorine derivative, CggH^yOCl, was obtained ; it 
forms slender needles containing water of crystallisation, m. p. 123°. 

S. B. S. 

Preparation of Arylpolymethylenechloro - compounds. 
Emanuel Merck (D.R.-P. 238959). — When benzo-c-chloroamylamide, 
CgH5'CO'NH'[OH2]501 is heated with aluminium chloride in benzene 
solution and the mixture subsequently treated with steam, it yields 
benzo-i-pJienylamylamide, CgH.'CO'!NH*[CH2]5*Ph, a yellow oil, b. p. 
273 — 275°/15 mm., which on hydrolysis furnishes €-phenylamyl- 



ORGANIC CHEMISTRY. i. Ill 

amine, NH2-[CH2]5Ph, b. p. 131715 mm., picrate, m. p. 152—153°, 
and platinic/doride, m. p. 220°. 

i-Ghloroamylhenzene, obtained by heating the foregoing benzophenyl- 
amylamide with phosphorus pentachloride, has an unpleasant odour 
andb. p. 134718 mm. 

Benzo - Z - phenylhutylamide, glistening needles, m. p. 83-5°, is 
analogously prepared from benzochlorobutylamide with phosphorus 
pentachloride ; it furnishes 8-chlorobutylbenzene, CgH5'[CH2]4Cl, b. p. 
122—123717 mm. F. M. G. M. 

Preparation of Derivatives of o-Thiolbenzoic Acid. Badische : 
Anilin- & Soda-Fabrik (D.R.-P. 237773).— When dichloroethylene 
(1 mol.) reacts with an alcoholic solution of a thiolbenzoic acid (2 mols.), 
it yields acetylftisthiolbenzoic acids (ftwmethinethiolbenzoic acids) of 
the general formula COgH'-H'S-CHICHIS-R-COgR', where R is a 
benzene or naphthalene residue, and R' a metal, aryl, or alkyl group. 
The preparation of acetyleneftisthiolbenzoic acid is described. 

F. M. G. M. 

Products Formed by the Action of Heat on jo-Sulphamido- 
benzoic Acid. W. B. Stoddard {Amer. Cheni. J., 1912, 47, 1—20). 
— Remsen and Muckenfuss (Abstr., 1896, i, 481) found that when 
;?-sulphamidobenzoic acid is heated at 220° for eight hours, there are 
formed jo-sulphobenzoic acid, ammonium hydrogen jt?-sulphobenzoate, an 
" infusible diamide of jo-sulphobenzoic acid," and " iso-j9-sulphamido- 
benzoic acid." 

When the " infusible diamide " is heated with phosphorus penta- 
chloride at 194 — 197°, jo-chlorobenzonitrile is produced. An attempt 
was made to remove one of the nitrogen atoms, whilst leaving the 
other, by heating the compound with hydrochloric acid, but without 
success. It was also found that the desired result could not be attained 
by diazotisation or by heating with sodium carbonate solution. When 
a current of steam was passed through a mixture of the diamide and 
magnesium hydroxide, ammonia was liberated, and a rnagnesium salt 
was obtained of an acid, isomeric with ^-sulphamidobenzoic acid, but 
entirely different from '^ wo-/>-sulphamidobenzoic acid." The corre- 
sponding potassium salt reacts readily with phosphorus pentachloride, 
but the infusible diamide is not thereby regenerated. These facts 
indicate that the nitrogen atoms of the infusible diamide are both 
attached to carbon, and that the acid isomeric with jt?-sulphamido- 
benzoic acid is probably jo-carbamidobenzenesulphonic acid. 

When Remsen and Muckenfuss* " iso-jo-sulphamidobenzoic acid " is 
heated in a sealed tube with concentrated hydrochloric acid at 100°, 
the infusible diamide is produced. If the acid is heated in a sealed 
tube with water at 220°, a small quantity of a substance is produced 
which crystallises in thin plates. Analyses of the barium and sodium, 
salts of ** zso-jD-sulphamidobenzoic acid " have shown that this acid is 
not isomeric with jo-sulphamidobenzoic acid, but has the composition 

of an anhydride of the latter, CqH4<C^^ >NH. Determinations have 

1 



i. 112 ABSTRACTS OF CHEMICAL PAPERS. 

been made of the el©ctric;al conductivity of solutions of both these 
acidn. 

It is suggested that the action of heat on jt7-suIpbamidobenzoie acid 
may be represented by the equation : 

4COsH-CeH^-S02-NH2 = C6H^<^^'>(NH2)2 + COaH-C^H^-SOgH + 
C02H-C6H,-S02-ONH, + C,H,<s^NH. ^ ^ 

Bornylene from /3-Iodohydrobornylenecarboxylic [/8-Iodo- 
oaraphanecarboxylic] Acid : Dibromobornylenecarboxylic [a^- 
Dibromocamphanecarboxylic] Acid and Dihydrobornylene- 
carboxylic [or^/io-Camphanecarboxylic] Acid. Julius Bredt 
and W. HiLBiNG (J. pr. Chem.y 1911, [ii], 84, 778— 786. Compare 
Abstr., 1910, i, 498). — p-Iodocamphanecarboxylic acid, 

prepared by the action of hydrogen iodide on a glacial acetic acid 
solution of bornylenecarboxylic acid, crystallises in needles, m. p. 
129 — 130°. It dissolves in hot aqueous sodium carbonate, yielding a 
crystalline sodium salt, together with the hydroxy-acid, CjjHjgOg, pre- 
viously described (loc. cit.). When heated with strong aqueous sodium 
hydroxide, the sodium salt yields bornylene, which has [aj^ — 2368° 
in toluene, and [a]^ - 23*94° in benzene. A glacial acetic acid solu- 
tion of bornylene, when heated at 70° with sulphuric acid, yields a 
bornyl acetate, b. p. 103 — 104°/14 mm., which, on hydrolysis, furnishes 
a borneol of m. p. 175—178° 

OTJr'CO IT 
aB-I)ibromocamphanecarboxylic acid, CsH,.<^i ^ , obtained 

by the addition of bromine to bornylenecarboxylic acid in carbon 
tetrachloride solution, and purified by means of the sodium salt, 
crystallises in needles, m. p. 159 — 160°. 

or^Ao-Camphanecar boxy lie acid (loc. cit.), prepared by reducing ^-iodo- 

camphanecarboxylic acid, yields a chloride, b. p. 114 — 115°/14 mm., 

and an amide, m. p. 166 — 167°, which is con- 

CHg'CH — CH-NHg verted by the Hofmann reaction into an 

L^ I awwW of the annexed formula. Improvements in 



CMog 



the preparation of bornylenecarboxylic acid are 
CHg'CMe'CHg also described. 

Ethyl bornylenecarboxylate, obtained as a by- 
product in crystallising the anhydride from alcohol, has b. p. 
121— 122°/16 mm. F. B. 

Electrolytic Reduction of Camphononic Acid to cis trans- 
Camphonolic Acid : Camphonololactone. Julius Bredt [and, in 
part, with Wilhelm Lund and August Amann] (J.pr. Chem., 1911, [ii], 
84, 786 — 799). — When subjected to electrolytic reduction, camphon- 
onic acid yields a mixture of two stereoisomeric camphonolic acids, 
0H-CH-GMe2^^„ ^^ ^ 



ORGANIC CHEMISTRY. i. 118 

which may be separated by distillation, whereby the cis-cam phenolic 

acid is converted into the corresponding lactone, whilst 

^^2 Y ( the cis-trans-isomeride distils unchanged. 

CMog cis-Camphonololactone (annexed formula) has m. p. 

CHg-CMe-CO 160-161°, b. p. 239-2°, [a]}J-16-2° in alcohol. 

cis-Camphonolic acid is obtained by the addition of 
the calculated amount of cold dilute hydrochloric acid to it^ barium 
salt, which is prepared by the action of barium hydroxide on the 
preceding lactone. It has [ajo - 33*4° in alcohol, and a varying m. p. 
according to the rapidity of heating ; when rapidly heated, it has 
m. p. 197—198°. 

The isomeric cis-tv?ins-ca7nphonolic acid has m. p. 249 — 250°. 

y-BromocamphonaniG acid, i ^">CMe*C02H, obtained by 

Cllg C/xi2 
the action of saturated aqueous hydrobromic acid on the m-lactone, has 
m. p. 146 — 147°, and when treated with aqueous sodium carbonate 
is reconverted into the lactone. 

Both cis-ira^is-camphononic acid and cis-camphonololactone are 
oxidised by concentrated nitric acid to camphoronic acid. 

Improvements in the method of preparing camphononic acid 
(Lapworth and Lenton, Trans., 1901, 79, 1287) are also described. 

F. B. 

Resolution of Mandelic Acid into its Active Components 
by means of Phenylethylamine. Lennart Smith {J. pr. Chem,, 
1911, [ii], 84, 743 — 744). — The resolution of r-mandelic acid has been 
accomplished by crytetallising the Z-)8-phenylethylamine salt from 
water, the salt of the rf-acid being the less soluble. The pure cZ-acid 
is obtained from the mandelic acid, recovered from the mother liquor, 
by crystallisation with cZ-phenylethylamine. F. B. 

Atrolactio [a-Hydroxy-a-phenylpropionic] Acid. Lennart 

8MiTH(y.;}r.(7/iem., 1911, [ii], 84,731 — 743). — The tirst part of this paper 
contains an account of a large number of experiments on the formation 
of aeetophenonecyanohydrin, and the hydrolysis of the latter compound 
to atrolactic acid. This is followed by a description of the resolution 
of the acid into its optically active components, and of its behaviour 
towards hydrochloric acid. 

In the preparation of atrolactic acid by Spiegel's method (Abstr., 
1881, 277; compare Staudinger and Buzicka, Abstr., 1911, i, 462), 
better yields are obtained by replacing the hydrochloric acid by 
glacial acetic acid. 

Atrolactic [a-hydroxy-a-phenylpropionic] acid crystallises with ^HgO, 
and the potassium^ sodium, and magnesium salts with 2H2O ; the 
strontium salt, Sr(C9 £1903)2,41120, and calcium salt, CaH2(C9H()03)4, 
m. p. 216° (decomp.), are also described ; the affinity constant 
^=0-0341. 

The resolution of the acid into its optically active component is 
accomplished by crystallisation of its salt with ^;8-phenylethylamine, the 
salt of the tZ-acid being the less soluble (compare McKenzie and Clough, 
^VOL. cil. 1 i 



i. 114 ABSTRACTS OF CHEMICAL PAPERS. 

TranB., 1910, 07, 1016). The pure lucid is obtained by crystallising 
the acid recovered from the mother liquors with rZ-plienylethylamino. 
The \ p/ienyUthylamive salts of both ihed- and the /-acids were analysed. 
The barium, BsiX^t^lA^O, calcium, CaXg.SjH^O, and potassium, 
KX,2H20, salts of the active acids are also described (X = C^HgOg). 

Hydratropic acid is readily obtained from atrolactic acid by heating 
it with concentrated hydrochloric acid for three-quarters of an hour 
on the water-bath, and reducing the product with sodium amalgam. 
When heated with concentrated hydrochloric acid for four hours at 
130 — 135°, atrolactic acid yields )S-chloro-a-phenylpropionic acid 
together with a- and ^-isoatropic acids. By heating tropic acid at 
170 — 180°, it is converted into atropic acid, which is accompanied by 
small quantities of a- and ^-i«oatropic acids. 

From these experiments the conclusion is drawn that the action of 
hydrochloric acid on atrolactic acid yields successively atropic, )8-cbloro- 
a-phenylpropionic, and woatropic acids. F. B. 

a-Phenyl-a-ethylglycollic Acid. Lennart Smith (/. pr. Ghe^n. 
1911, [ii], 84, 744— 745). — a-Phenyl-a-ethylgly collie [a-hydroxy- 
a-phenylbutyric] acid is best prepared by the addition of glacial acetic 
acid to a mixture of potassium cyanide and propiophenone, and 
hydrolysis of the nitrile thus obtained by means of hydrogen chloride 
in ethereal solution, the resulting amide being finally hydrolysed by 
aqueous sodium hydroxide. It crystallises in needles, m. p. 132° 
(corr.) (compare Grignard, Abstr., 1903, i, 32), and is resolved into its 
optically active components by crystallisation of the rf-j8-phenylethyl- 
amine salt, l-a- Uydroxy-a-plienylbutyric amd has, in aqueous solution, 
[a]!,' -14° F. B. 

Ethyl Anisoylacetates. Andre Wahl and C. Silberzweig 
{Bull. Soc. chim., 1912, [iv], 11, 25—34. Compare Abstr., 1908, i, 
647; 1910, i, 263). — Ethyl m- and j9-methoxy ben zoylacetates have been 
prepared by condensing ethyl acetate with ethyl m- and p-methoxy- 
benzoates in presence of sodium. The corresponding oriAo-compound 
has already been prepared by Tahara (Abstr., 1892, 844). 

£tkyl p-anisoylacetate, OMe'CgH^'CO-CHg'COgEt, is a pale yellow 
liquid, b. p. 180 — 190°/10 — 12 mm., decomposing partly into 
jt?-anisoyldehydracetic acid. It yields a green copper salt, (C^^^u^d-i^^^ 
m. p. 210°, and a miroso- derivative, ra. p. 113 — 114°. 

Ethyl m-methoxyhemoylactlate also decomposes very readily on dis- 
tillation. It yields a green copper salt, m. p. 168 — 169°, and a nitroso- 
derivative, m. p. 94°. W. G. 

Preparation of Halogenated 2-Anthraquinonylaininobenzoic 
Acids. Fritz Ullmann (D.R.-P. 238106. Compare Abstr., 1906, i, 
426, 953 ; 1910, i, 270). — 4:-Bromo-2-a7ithraquino7iylaminobenzoic acid, 
Cj4H702*NH*CgH3Br*C(>2H, a violet powder, which does not fuse at 
300°, is obtained by heating 1-chloroanthraquinone (24*2 parts) with 
4-bromoanthranilic acid (22 parts), potassium acetate (20 parts), copper 
acetate (1 part), and copper powder (1 part) at 160° in amyl-alcoholi 
solution. F. M. G. M 



b 

i 



I 



ORGANIC CHEMISTRY. i. 115 



Fagaramide, a New Nitrogenous Substance from the Root- 
bark of Fagara xanthoxyloides. Hermann Thoms and F. Thumen 
{Ber., 1911,44, 3717 — 3730). — The root-bark of Fagara xanthoxyloides 
contains a nitrogenous substance, Ci^H^^OgN, crystallising from 
alcohol in well-formed crystals, m. p. 119 — 120°. Thirty grams were 
obtained from 40 kilos, of the drug. The compound tQvxnQdi fagaramide 
is identified as the isobuti/lamide of jyiperonylacrylic acid, 
CH2:02:CeH3-CH:CH-CO-NH-CH2-CHMe2. 
On prolot'ged boiling with 50% alcoholic potassium hydroxide, it is 
decomposed into isobutylamine and piperonylacrylic acid. 

Fagaramide is prepared synthetically by condensing piperonyl- 
acrylic chloride and isobutylamine in ethereal solution. In a similar 
manner, the isomerides are prepared, namely, the normal, secondary, 
and tertiary butylamides of piperonylacrylic acid. All four isomerides 
form characteristic, crystalline dibromo-derivatives. 

Fagaramide reacts neutral, and does not form salts ; it belongs to 
the same group as piperine. 

All four isomerides have the same physiological action, namely, 
narcotic on cold-blooded animals, but practically none on warm-blooded 
animals. 

Fagaramide is obtained by extraction with benzene. The dibromide, 
Cj^H^^OgNBr^, forms slender, colourless needles, m. p. 154 — 155°. 

On oxidation of fagaramide, piperonal and piperonylic acid, m. p. 
230° (not 227-5—228°), are obtained. Piperonylacrylic acid has m. p. 
242° (not 238° or 232—234° as stated in the literature). isoButyl- 
amine hydrochloride has m. p. 177—178° (not 160°). 

Piperonylacrylic chloride, CH202lCgH3'CHICH'COCl, is conveniently 
prepared by the action of thionyl chloride on the acid. 

Piperonylacryl-n-butylamidey 

ch202:c,,H3-ch:ch-co-nh-[ch2],-gh3, 

forms very minute crystals, m. p. 85 — 86°. The dibromide separates 
in small, colourless needles, m. p. 134 — 135° (decomp.). 

Fiperonylacryl-sec.-butylamide, 

CHaOglCeHg-CHICH-CO-NH-CHMeEt, 
yields colourless needles, m. p. 161 — 162°; the dibrornide has m. p. 
164— 165° (decomp.). 

Piperonylacryl-tevt.-butylamide,CH^O^:C(.R^'CK:OIi.'CO-l<lR'CMe^, 
forms strongly refractive, pale yellow prisms, which are colourless 
when powdered, m. p. 138 — 139° ; the dibromide crystallises in slender, 
colourless needles, m. p. 182—183° (decomp.). E. F. A. 

Aminosulphones and Allied Oompounde, Siegmund Gabriel 
and James Cgi.man {Ber., 1911, 44, 3628— 3636).— The analogous 
behaviour of ketones and sulphones in many reactions led the authors 
to hope that y- and 8-aminosulphones might yield heterocyclic bases, 
just as y- and 8-amino-ketones yield pyrrolines and tetrahydropyridines 
respectively. This expectation has not been fulfilled, but the work 
has led to the production of the following substances. 

When warmed with phosphorus pentachloride, phthalyltaurine 

yields pht/udyltauryl chloride, C^.H4<^^>N-C2H^-S02C1, m. p. 160°. 

i 2 



i. 116 ABSTRACTS OF OHBMIOAL PAPERS. 

This Kubstance is very Ktable to hoi water, does not react with benzene 
and aluminium chloride, but ia converted into the imthyl ester, 

C6H,<co>N-02H,.S03Me, 

m. p. 103 — 104°, by methyl-alcoholic sodium methoxide. 
Phenyl ^-phthalimidoeUiyl aulphone^ 

C8H,<^^N-CH2-CH2-S02Ph, 

m. p. 185 — 185'6°, obtained from benzenesulphinic acid, alcoholic 
8odium ethoxide, and /8-bromoethylphthalimide at 100°, yields, by 
hydrolysis by acetic acid and hydrochloric acids at 140°, pJi^nyl- 
p-aminoethylsulphoiie hydrochloride, NHg'CH^'CHg'SOgPhjHCl, m. p. 
165 — 155*5°, glistening needles. Phenyl-y-phtlialinddopropylsulpJione, 
m. p. 126°, and phenyl 'y-aminojwopylsulphonn hydrochloride, m. p. 
222° are obtained by similar methods from y-iodopropylphthalimide. 
Phenyl mercaptan and /8-broraoethylphthalimide react with boiling 
alcoholic potassium hydroxide to form phenyl ^-phtJialimidoethyl 

sulphide, C6H4<^^N-CH2-CH2-SPh, m. p. 59—60°, long needles, 

by the hydrolysis of which phenyl p-arninoethyl sulphide hydrocJdoride, 
NH2-CH2-CH2-SPh,HCl, m. p. 160—161°, is obtained. 

)8-Phthalimidoethyl mercaptan is converted by warm nitric acid, 
D 1'2, into ^'phthalimidoethyldisulphoxide, 

f CgH^\^Q/*N*CH2*CH2 J2S2O2, 

m. p. 155 — 156°, which reacts in benzene with aluminium chloride 
on the water-bath to form, after treating the product with hydro- 
chloric acid, ^phthalimidoethylsulphinic acid, 

C,H,<^^>N-CH2-CH2-S02H, 

m. p. 149 — 149-5° (decomp.), glistening, white leaflets. This acid, 
which is also obtained by reducing the disulphoxide or phthalyltauryl 
chloride by zinc dust and 96% alcohol, is decomposed by boiling 20% 
hydrochloric acid, yielding phthalic acid, taurine, and ^-phthalimido- 
ethyldisulphoxide. C. S. 

Action of a- Hydroxy i«obutyronitrile on the Nitrile Ester 
of Iminodi-phenylacetic Acid. George L. Stadnikoff {J. Russ. 
Phys. Cfiem. Soc, 1911, 43, 1235— 1244).— It has been previously 
suggested (Abstr., 1909, i, 771, 772; 1910, i, 825) by the author 
that in the action of a-hydroxypropionitrile on the nitrile esters of 
propionyliminocyc^oheptanecarboxylic and iminodi-phenylacetic acids, 
an intermediate, unstable compound of the ammonium hydroxide type 
is formed, this then undergoing decomposition into other hydroxy- 
nitriles and nitrile asters of imino-acids. Such intermediate forma- 
tion of ammonium hydroxide compounds is assumed also (1) in the 
formation of amines and amino-, imino-, and nitrilo-acids by the 
action of hydroxy-nitriles on either ammonia or its derivatives ; 
(2) in the interaction of alkyl halides or halogen derivatives of acids 
with ammonia or its organic derivatives, and in a number of other 
reactions. 



r 



ORGANIC CHEMISTRY. i. 117 



Most of the reactions represented in this way are explained equally 
well by Nef's " methylene- dissociation " j thus the interaction of 
the nitrile ester of iminodi-phenylacetic acid and a-hydroxypropio- 
nitrile may be regarded as occurring in the following stages : (1) the 
hydroxynitrile dissociates into methylene derivative and water : 
CH3-CH(0H)-CN = CH3-C(CN): + H^O ; (2) water and the nitrile 
ester give the ammonium hydroxide compound, 

CN-CHPh-NH2(OH)-CHPh-C02Et ; 
(3) the ethylidenecyanogen combines with the ammonium hydroxide 
compound, giving the nitrile ester of a nitrilo-acid, 

CN-CHPh-NH(0H)(CHMe-CN)-CHPh-C02Et, 
which then decomposes into derivatives of an imino-acid of lower 
molecular weight and mandelonitrile. 

In order to arrive at a decision between these two explanations, 
the author has investigated the action of a-hydroxy«sobutyronitrile, 
which is incapable of methylene dissociation on the nitrile ester of 
iminodi-phenylacetic acid. The result confirms the author's view 
of these reactions, the product of the reaction being anhydronitrilo- 
diisobutyricphenylacetic acid, 

C02H.CHPh.N<^5JvCO>(^, 

which is formed as follows: CN-CHPh'NH-CHPh-COgEt + 
OH-CMe^-CN = CN-CHPh-NH(OH)(CMe2-CN)-CHPh-C02Et = 
OH-CHPh-CN + CN-CMe.-NH-CHPh-COgEt ; the latter + 
OH-CMeg-CN = CN-CMe2-NH(bH)(CMe2-CN)-CHPh-C02Et = HgO + 
CN-CMe2-N(CMe2-CN)-CHPh-C02Et. This nitrile ester then under- 
goes hydrolysis to the substituted triacetic acid, which is subsequently 
transformed into the corresponding anhydride. 

Anhydronitrilodiisohutyricphenylacetic acid, CigHjgOgN (see above), 
crystallises from aqueous alcohol in silky needles, m. p. 180 — 181° 
(slowly heated in sealed capillary). As would be expected from the 
fact that iminodicarboxylic acids are rendered neutral to phenol- 
phthalein by one equivalent of alkali hydroxide, two equivalents 
of the latter are sufficient to neutralise this anhydride. T. H. P. 

Photochemical Behaviour of Nitroterephthalaldehyde. 
Hermann Suida (J. pr. Ghem., 1911, [ii], 84, 827— 830).— The author 
finds that nitroterephthalaldehyde is very sensitive to light. A cold 
xylene solution of the aldehyde on exposure to direct sunlight rapidly 
becomes turbid, and deposits a yellow solid consisting of 2-nitroso- 
i-aldehydohenzoic acid, CHO*CgH3(NO)'C02H. The acid slowly chars 
at 250 — 300°, but when placed in a bath at 300° instantly melts with 
decomposition. It dissolves in alkalis and alkaline carbonates, yield- 
ing yellowish-green solutions. Its solution in concentrated sulphuric 
acid develops with a trace of phenol an emerald-green coloration. 

Details of a lecture experiment illustrating the photochemical 
transformation of the aldehyde are given. F. B. 

Angeli- Rimini Reaction of the Aldehydes. Angelo Angeli 
{Atti R. Accad. Lincei, 1911, [v], 20, ii, 445—449. Compare 
Balbiano, Abstr., 1911, i, 987). — The author has prepared Wallach's 
ketone, OMe'CgH^-CHg-COMe, and Balbiano's product from anethole 



1. 118 ABSTRACTS OK CHKMICAL PAPERS. 

glycol, and finds that they are identical, and do not ^ive tlie Anpeli- 
Kiiuini reaction when it is carried out as originally described. The 
reaction, however, is given by these substances when an excess of 
alkali is employed. This explains Balbiano's results. It is advisable 
to add the calculated quantity of alkali in small portions (compare 
Angeli and Castellana, Abstr., 1909, i, 392), and in the qualitative 
test, it is better to use the sodium salt of Piloiy's acid. Deoxy benzoin, 
benzoin, benzil, and dibenzyl ketone behave similarly, giving the 
reaction only when an excess of alkali is employed. R. V. S. 

o Hydroxyacetophenone, 5 Chloro-o-hydroxyacetophenone, 
and Certain Chlorocbalkones and Chloroflavones. Franz 
KuNCKELL [with Albert FCrstenberg] {Ber., 1911, 44, 3654 — 3656. 
Compare Abstr., 1901, i, 213). — The authors describe the preparation 
of o-hydroxyacetophenone from 5-acetylamino-2-hydroxyacetophenone, 
and ol" bio-dichloro -^-hydroxyacetophenone (m. p. 64°) from o-chloro- 
5-amino-2-hydroxyacetophenone. The corresponding w-chloro-b-bromo- 
1 -hydroxyacetophenone has m. p. 68°. 

5-Chloro-2-hydroxyacetophenone condenses with benzaldehyde in the 
presence of sodium hydroxide to form b-chloro-2-hydroxychalkone, m. p. 
108°, which readily combines with bromine to form a dihi'omide of 
m. p. 185°. H. W. 

Cbalkone and Hydrochalkones. Guido Bargellini and Leda 
BiNi {Gazzetta, 1911, 41, ii, 435 — 445). — Hydrochalkones may be 
prepared convenient^ly by reducing chalkones with hydrogen in the 
presence of platinum -black. In this way, from an ethereal solution 
of 2-hydroxychalkone, 2-hydroxydihydrochalkone was obtained ; the 
product is best purified by conversion into the seonicarbazone, 
CigHj^OgNg, which forms white needles, m. p. 174 — 175° (softening at 
170°). 

The reduction of 4-methoxychalkone with zinc dust and acetic acid 
yielded a substance (probably a diketonic condensation product), 
CggHjjoO^, which crystallises in colourless needles, m. p. 224 — 225°. 
When 4-methoxychalkone in ethereal solutionis reduced with hydrogen 
iu presence of platinum-black, A:-inethoxydihydrochalkone, ^i6^i6^2' ^^ 
obtained ; it crystallises in colourless needles, m. p. 59 — 60° (softening 
at 55°), and it gives a yellow coloration with concentrated sulphuric 
acid. The semicarbazone, Cj^HjgOgNg, forms colourless needles, m. p. 
118—120°. 

3 : 4-Dimethyleneoxychalkone, when reduced with zinc and acetic 
acid, yields a substance, CggHg^O^j, which crystallises in colourless 
needles, and is solid at 260°. When the reduction is effected with 
hydrogen in the presence of platinum-black, 3 : A:-dimethyleneoxydi- 
hydrochalkone, CjgHj^Og, is produced ; it crystallises in colourless 
needles, m. p. 39 — 40° (softening at 35°), and gives a red coloration 
with concentrated sulphuric acid. The semicarbazone, Cj^Hj-^OgNg, 
forms colourless needles, m. p. 153 — 154°. K. V. H. 

Preparation of Benzoylaminohydroxyanthraquinones. 
Farbenfabriken vorm. Friedr. Bayer & Co. (D.R.-P. 238468). — 
When 1 :5-dibenzoyldiaminoanthraquinones are oxidised with either 



1 



I 



ORGANIC CHEMISTRY, i. 119 



raanganese dioxide, a persulphate or a perchlorate, a hydroxy-group is 
introduced into either position 4 or 8. 

] : 5-DibenzoyldiamiDoanthraquiuone (10 parts) dissolved in 
100 parts of sulphuric acid (10% SO3) was slowly treated at 5 — 10° with 
manganese dioxide (3*5 parts), maintained below 15° with continual 
stirring during two hours, and the ^-hydroxy-! : b-dibenzoyldiamino- 
anthraquinone subsequently isolated by known methods. 

A:-Chloro-^-hydroxy-\ : ^-dihenzoyldiaminoanthraquinone was prepared 
in a similar manner with potassium persulphate from 4 chloro-1 : 5- 
dibenzoyldiaminoanthraquinone, whilst 2-chloro-l : 5-dibenzoyldiamino- 
anthraquinone furnished 2-chloro-4:(8)-hydroxy-l : 6-dibenzoyldiamino- 
anthraquinone. F. M. G. M. 

Preparation of Dianthraquinonyl- or Polyanthraquinonyl 
carbamides. Farbwerke vorm. Meister, Lucius & Bruning (D.R.-P 
238550, 238551, 238552, and 238553. Compare Abstr., 1911, i, 469, 
655, 995). — Tiae preparation of dianthraquinonylcarbamides has 
previously been described, and the reaction has now been extended 
to the case of heteronuclear /S^'-diaminoanthraquinones. 

These compounds, orange-yellow powders, are obtained by the 
action of j^^'-anthraquinonylenedicarhoxyl chlorides (obtained from 
2 : 6- or 2 : 7-diaminoanthraquinones with excess ef carbonyl chloride) 
on amino- or diamino-antiiraquinones. 

The second and third patents state that /8^'-dianthraquinonyl- 
carbamide can be readily prepared by heating ^-aminoanthraquinone 
at 170° with carbamide or ethyl urethane, either with or without 
solvent, until evolution of ammonia (and in the latter case, alcohol) 
ceases. The fourth patent deals with the employment of substituted 
aryl- or diaryl-carbamides, and describes ip-tolyl-2-anthraquinonyl- 
carbamide, yellow crystals, obtained by the prolonged boiling of 
p-toluidine with 2 : 2'-dianthraquinonylcarbamide. F. M. G. M. 

[Preparation of Anthracene Derivatives.] Badische Anilin- 
& Soda-Fabrik (D.R.-P. 238980). — It is now found that the compounds 
previously described (Abstr., 1907, i, 226) can be prepared from 
1 : r-dianthraquinonyl-2 : 2'-dialdehyde by reduction with either an 
alkaline solution of sodium hyposulphite or with zinc in concentrated 
sulphuric acid solution. F. M. G. M. 

Decomposition of Alkylidenehydrazines : Conversion of 
lonone and i//-Ionone into the Corresponding Hydrocarbons, 
C,3H22. NicoLAi M. KijxVER {J. Rus8. Phya. Chem. Soc, 1911, 43, 
1398 — 1402). — The decomposition of iononehydrazone in presence of 
potassium hydroxide is an exothermic reaction, and gives rise to a-ionane, 

CHEt:CH-CH<^^^Lp^>CH2, which is a colourless liquid with a 

faint odour of turpentine, b. p. 220— 22r/747 mm., J)f 0-8530, 
Wd 1*4784. It readily oxidises in the air, combines with 4 atoms of 
bromine, and in acetic anhydride solution gives a raspberry-red 
coloration with a drop of sulphuric acid. It shows the normal 
molecular refraction, whereas the similar hydrocarbon corresponding 



i. 120 ABSTRACTS OF CHEMICAL PAPEK8. 

with /?-ionone should exhibit considerable exaltation, owing to the 
presence of conjugated double bonds. 

if^-lonane, GHKt:CH-CH2-CMe:CH-CH3-CH:CMe2(?), obtained in a 
similar manner from i/^-ionone, is a colourless, faintly-smelling liquid, 
b. p. 224—2257751 mm., D^ 0-8151, ?io 1'4725; it rapidly turns 
yellow in contact with the air, unites with 6 atoms of bromine, and 
is converted into o-ionane when its acetic acid solution is boiled with 
a small quantity of sulphuric acid. The formula given above is of 
doubtful accuracy, as the hydrocarbon does not exhibit optical 
exaltation. T. H. P. 

Crystalline Form and Optical Characters of Pinocampheol 
Methyl Xanthate. N. I. Surgunoff {Zeitsch. Kryst. Min.^ 1911, 
60, 62—63; from Bull. Soc. Nat. Moscow, 1907, 543— 551).— The 
crystals of pinocampheol methyl xanthate (Tschugaeff, Abstr., 1908, 
i. 93) are orthorhombic with a :6 :c = l-3747 : 1 : 09787. L. J. S. 

Constituents of Essential Oils. The Constitution of the 
Active Caryophyllenes ; Transformation of the Active 
Caryophyllenee into Monocyclic Derivatives. Friedrich W. 
Semmler and Erwin W. Mayer (^er., 1911,44, 3657— 3679).— The 
authors have subjected caryophyllene to the action of ozone, and 
studied the decomposition products of the ozonide so formed. They 
consider that crude caryophyllene is composed chiefly of three caryo- 
phyllenes, namely, Deussen's inactive a-earyophyllene and two active 
caryophyllenes, which they name <erp.-caryophyllene and Zim. -caryo- 
phyllene, and to which they assign the respective provisional 
formulae : 

CMe CH CMe CH, 






.? 



\ 

CMe 



H 

HC — CMcaC Me HC — CMezC CH 

\ /\ \ / 



^ 9^^ and H,C CH „ 

) CMezC 



CHg Me CH Me 

Commercial caryophyllene, when dissolved in ethyl chloride and 
subjected to the action of ozone, yields a soluble ozonide, Ci5H240g, 
together with a small quantity of an insoluble ozonide, which probably 
contains seven or eight atoms of oxygen. When the soluble ozonide 
is heated in glacial acetic acid solution, it yields carbon dioxide and 
formaldehyde, together with a mixture of acidic and neutral products. 
From the acidic products a keto-acid, Cj^HjgOg, a diketo-acid, 
^14^22^4' ^^^ *^ 2iQ\d, CgHj^Og, were isolated. 

The ^to-acid, Cj^HjgOg, is a pale yellow, mobile oil of b. p. 
183—187711-5 mm., D^o 1-040, a* 4-44°, n^ 1-4677. Its silver salt 
was analysed. The methyl ester has b. p. 139 — 142°/15*6 mm., 
D20 0-9913, w^ 1-4527, a^ -f 42°. The 8emicarhazone has m. p. 183°. 
When oxidised with nitric acid, the ketoacid yields dimethylsuccinic 
acid and dibasic caryophyllenic acid, CgHj^O^. The latter forms a non- 
crystalline syrup of b. p. 215— 218°/9 mm., 222— 225°/13 mm. It is 



ORQANIC CHEMISTRY. i. 121 

remarkably stable towards nitric acid. The silveo' and copper salts 
were prepared. The methyl ester has b. p. 127 — 13P/11 mm., 
D20 10456, n^ 1-4462, a^ +44°. When boiled with acetic anhydride, 
caryophyllenic acid yields an anhydride of b. p. 152 — 158°/10 mm., 
D20 11399, n'^ 1-4755, 4" - 28°. Similar products were obtained 
when the keto-acid was oxidised by bromine in alkaline solution. 
Oxidation with permanganate also gave caryophyllenic acid, to which 

the formula CH2\pTT/p/^ ^rxZ^CIMeg is assigned. 

The diketo-Sicid, C^^H^fi^, is a viscous, yellow oil of b. p. 229—232°/ 
11-5 mm., D20 1-0830, < 1-4804, a'l? +41°. Its silver salt begins to 
darken at 130°, and has m. p. about !;145°. Its methyl ester has b. p. 
184— 188°/12 mm., D^o 1-047, ag* + 38°, 7ij, 1-4680. With semi- 
carbazide hydrochloride it gives no product of definite m. p. When 
oxidised with nitric acid, it yields succinic acid and caryophyllenic acid. 
On treat merit with bromine in alkaline solution, it yields caryophyllenic 
acid, together with a mixture of acidvts of high boiling point. 

The acid, C8Hi402,has b. p. 120— 128°/9 mm., D2o 0-9827, n,, 1-4457, 
[aji) + 17°, and is monobasic. Its inethyl ester has b. p. 64 — 68°/ 
9 mm., D20 0-922, [a\^ + 20°, n^ 1-4316. Its amide melts at 96°. 

From the neutral portion (see above), a ketone, CjQlIjgO, a probable 
keto-aldehyde, Cj^HjgOg, a diketone, CjgHgoOg, and a deketo-aldehyde, 
C^^HggOg, were isolated. 

The ketone, CjQHjgO, is a mobile, pale green liquid of b. p. 73 — 76°/ 
11-5 mm. It has D20 0-8823, < 1-4387, a,y - 7°. Its semicarbazone 
has m. p. 176°. When reduced by sodium amalgam it yields an 
alcohol, C10H20O, b. p. 87— 89°/ll-5 mm., D20 0-8707, < 1-4507, 
[a]o - 6°. This, on treatment with phosphorus pentachloride, passes 
into the corresponding chloride (b. p. 70— 73°/10 mm., D2o 0-882), 
fc which, when heated with quinoline, yields the hydrocarbon, Cj^^Hig. 
The latter has b. p. 50— 54°/ll-5 mm., D2« 0-812, < 1-4410, aS -6°. 
When oxidised by bromine in alkaline solution, the ketone yields 
carbon tetrabromide, together with a monobasic acid, OgHjgOg, b. p. 
131— 133°/13-5 mm., D23 0*9773, < 1-4500, 4° -7°, the silver salt 
of which had m. p. 219°, after darkening at about 160°. The methyl 
ester has b. p. 86— 89°/15 mm., D23 0-9208, y4° 1-4360, a^ -5-5°. 
The amide has m. p. 114°. On oxidation with nitric acid, the ketone 
yields an acid, O^^^fi^, b. p. 119— 122°/12 mm., D20 0972, < 1-4457, 
a^ +7-5°. This yielded a methyl ester of b. p. 69— 73°/15 mm., 
D20 0-9359, n^ 1-4307, a?," +22°, and an amide, m. p. 115—116°. The 
formation of ihese compounds is represented by the scheme on p. 122. 

The diketone, CjgHgoOg, after treatment with permanganate to 
destroy any aldehyde present, is a colourless, mobile oil, b. p. 
137— 142°/9 mm., D20 0-9600, n'^ 1-4677, a'^ +34° The b. p. was 
unaltered by a second treatment with permanganate, whilst the follow- 
ing values were found for the remaining constants : D20 0-9598, 
n^ 1-4622, ttu +39°. Its semicarbazone had m. p. 219°. On oxidation 
with nitric acid, the diketone yields dimethylsuccinic acid and caryo- 
phyllenic acid. Oxidation with bromine in alkaline solution leads to 
the same products. 

The diketo- aldehyde, Cj^HggOg, is a viscous, yellowish-green oil of 



i. 122 



ABSTRACTS OF CHEMICAL PAF»EUS. 



b. p. 181— 184°/13 mm., D20 1-0280, < 14774, a?," -25°. Jt doc8 
not yield a uniform semicarbazone. When oxidiged with perman- 
ganate, it yields the acid Cj^HgjO^ (see abovd). Nitric acid converts it 
into succinic acid and caryophyllenic acid. 



CMe 



CH 



/|\ / 



"„■? 



\ 



! f] ^Me 

CMe^C Me 

\ /\ 

\/ \ 
OHg Me 

terp. -Caryophyllene. 

HNOs 



CHMe 



CHMe 



CHMe 



B,(f 



NaOH + Br 
V 



HC-CMej 



/ 
H,C 

HC-CMe. 



H2V 



HC-CMoo 



OHa-COMe 



\ 
C 

Acid, C8H]402. 



CO2H 



\ 
CH^-COgH 

Acid, CgHifiOa. 

Deussen's caryophyllene was converted into caryophyllene dihydro- 
chloride, which, on treatment with methyl-alcoholic potassium hydroxide, 
yielded the previously-described " recovered " dextrorotatory caryo- 
phyllene (Abstr., 1911, i, 73). An attempt to transform this, through 
the nitrosite, into Deussen's Isevorotatory caryophenyllene was 
unsuccessful. 

Reduction of the blue nitrosite (Deussen, Abstr., 1907, i, 945) led 
to the formation of a substance, C^^HgrN, which is probably an amine. 
It has b. p. 148 -15071a mm., D20 0'9297, a?? -Hl3°, < 1-5030. 

H. W. 

New Philippine Essential Oils. Benjamin T. Brooks (Philippine 
J. ^ci., 1911, 6, 333—351. Compare Abstr., 1911, i, 1000).— The 
essential oil from the flowers of AficheHa longifolia contains linalool, 
eu^enol methyl ether, and methylbutyric and acetic acids, and a very 
small percentage of thymol. 

The leave*; of Toddcdia asiatica (L.) {T. Aculeaia Pers., Kurz) yield 
0*08% of an essential oil, which gave the following constants: n^ 1'4620, 
D^ 09059. The oil is largely linalool, but also contains a white, 
crystalline, camphor-like compound, m. p. 96*5 — 97°, which is very 
unstable. 

The leaves of Clausena anisvmi olens yield 1*20% of an essential oil 
with the following constants: ri^\-b2^b D^ 0-963, ester number 3-6. 
It contains chavicol methyl ether to the extent of 93%. 

About 02% of an es.sential oil with D^* 850 is obtainable from the 
leaves of Limnophila sp. 

Orange-peel oils were also examined, the naranjita variety giving 
a much greater yield than the cajel. The two oils resemble one 



I 



ORGANIC CHEMISTRY. i. 128 



anoMer very closely, the former having constants: vt^ 14700, 
[af^ 90-85°, ester number 8-0; the latter, <« 1-4675, B'^ 0-8390, 
ester number 8-5. 

The leaves of Citrus decumana yield 1*7% of an essential oil, with 
constants: < 1-4644, D^^ 0-8700, [a^i? 22-90° ester number 10. It 
contains dipentene and linalool and a trace of an aldehyde. 

The oil from the leaves of Citrus hystrix has the following constants : 
< 1-4650, D^2 0-9150, [a]?,'' -10-50°, ester number 50-2. W. G. 

The Essential Oil of Seseli bocconi. Luigi Francesconi and 
E. Sernagiotto (Atti R. Accad. Lincei, 1911, [v], 20, ii, 481 — 486). — 
The essential oil of this plant has been obtained by distilling it in 
steam. By fractional distillation of the oil a number of fractions 
were isolated, of which the more volatile consist of terpenes, Z-pinene 
and y8-phellandrene having been identified. The oil also contains 
compounds with carbonyl g^roups (probably aldehydes), and ethers 
and alcohols are also present. R. V. S. 

Chemistry of Caoutchouc. III. Theory of Vulcanisation. II. 
David Spence [with J. H. Scott] {Zeitsch. Chem. Ind. Kolloide, 1911, 9, 
300—306. Compare Spence and Scott, Abstr., 1911, i, 657).— Further 
experiments have been made on the extraction of sulphur from 
vulcanised caoutchouc by treatment for measured time intervals with 
equal successive quantities of boiling acetone. These show that 
equilibrium between the adsorbed sulphur and that in the acetone solu- 
tion is rapidly attained, and this fact is regarded as favourable to the 
interpretation which has already been given to the exponential form 
of the extraction curves. From two series of observations made with 
the same mixture of para-caoutchouc and sulphur which had been 
subjected to the vulcanising process for different periods of time, it 
it is found that the proportion of chemically combined sulphur 
increases with the period of vulcanisation, and that the initial portions 
of the extraction curves, corresponding with the removal of the free 
sulphur, are also different in the two cases. When a non-vulcanised 
mixture of caoutchouc and sulphur is similarly extract(3d with boiling 
acetone, the form of the extraction curve obtained is quite different. 
The removal of the sulphur from the unvulcanij-ed mixture is, how- 
ever, also a slow process by reason of the inclusion of the free sulphur 
in the jelly-like mass which the non-vulcanised caoutchouc foims in 
contact with the boiling acetone. 

An extraction experiment with ebonite gave an extraction curve 
differing from those obtained with samples of vulcanised caoutchouc, 
but in this case, also^ there appears to be a considerable amount of 
sulphur which is present in the chemically combined form. 

H. M. D. 

Brazilian Copal. Stanislaus Machenbaum {Arch. Pharm., 1912, 
250, 6 — 12). — The copal was red to yellow in colour, and was in small 
pieces, showing a thin, weathered layer. It sintered at 127°, melted 
completely at 160°, and had the following percentage solubilities in 



i. 124 ABSTRACTS OF OHEMICAL PAPERS. 

the 8olveDtA named : alcohol 76, acetone 80, alcohol and ether 92, 
light petroleum 20. The copal jjave the following constants : acid 
numbers (a) direct 123*2, (6) indirect 128*5 ; saponification numbers 
(a) cold 136*2, (b) hot 144*2. 

An ethereal extract of the resin was shaken with ammonium 
carbonate solution, which (1) extracted two acids, of which one, brazil- 
copcUic acidy C24H^oOg, m. p. 170 — 175°, yielded a lead salt insoluble 
in alcohol, and (2) precipitated a mixture of two acids, of which one, 
m. p. 195 — 200°, gave a lead salt insoluble in alcohol. Sodium 
carbonate solution then extracted from the ethereal solution two acids, 
of which hrazilcopalolic acid, CjgHggOg, m. p. 95 — 100°, gave an 
insoluble lead salt. The residual ethereal solution yielded nothing to 
potassium hydroxide solution, but on steam distillation furnished a 
volatile oil, boiling chiefly at '245 — 255°, and a residue of a-brazil- 
copaloresen, as a brownish -yellow, viscid mass. 

The portion of the copal insoluble in ether was dissolved in a mixture 
of alcohol and ether, and extracted with potassium hydroxide solution, 
which removed a mixture of resin acids. These were dissolved in 
alcohol, precipitated as lead salts by lead acetate, regenerated, and 
separated into two portions by treatment with cold alcohol : the soluble 
portion is a-brazilcopalinic acid, CigHg^Og, m. p. 180 — 185°. The solution 
after extraction with potassium hydroxide contained (3-brazilcopaloresen 
and a little volatile oil. All the substances described are amorphous. 
The acids give phytosterol-like reactions, and their acid numbers are 
recorded. T. A. H. 

Columbia Copal. Stanislaus Machenbaum (Arch. Pharm., 1912, 
250, 13 — 19). — The copal was in large pieces, and had a slight 
turpentine-like odour. It sintered at 120°, melted completely at 155°, 
and had the following percentage solubilities : ether 56, alcohol 78, 
alcohol and ether 90, light petroleum 18. Its constants were as 
follows: acid numbers (a) direct 105, (i) indirect 106*1, saponifica- 
tion numbers (a) cold 106*8, (i) hot 110*6. An ethereal extract of 
the resin was extracted with (1) ammonium carbonate solution and (2) 
sodium carbonate solution. In each case a mixture of two resin acids 
was extracted, and was separated into its components by solution in 
alcohol and precipitation by lead acetate. The acid giving an insoluble 
lead salt alone was examined in each case, the other being viscid and 
intractable. As in the case of Brazilian copal (preceding abstract), 
ammonium carbonate precipitated two resin acids from the ethereal 
extract ; of these, the one giving an insoluble lead salt had m. p. 
170 — 175°. That extracted by ammonium carbonate is Columbia- 
copalic acid, C22H4QO3, m. p. 145 — 150°. The acid subsequently 
removed by sodium carbonate is columbiacopalolic acid, C22H40^2' 
m. p. 90°. 

The residual ethereal extract contained volatile oil, boiling chiefly 
at 210 — 220°, and brown, viscid a-columbiacopaloresen. The portion 
of the crude copal insoluble in ether was dissolved in a mixture of 
alcohol and ether, and extracted with potassium hydroxide solution, 
which removed a-columbiacopalinic acid, CJ4H24O2, m. p. 180 — 185°, 
soluble in cold alcohol, and ^-columbiacopalinic acid, CgHgoOg, m. p. 



ORGANIC CHEMISTRY. i. 125 

190°, soluble in hot alcohol. P-Golumbiacopaloresen remained in the 
solution. 

All the products mentioned are amorphous. The acid numbers 
and phytosterol-like reactions of the resin acids are recorded. 

T. A. H. 

So-called Chicle Gum. J. E. Quintus Bosz and N. H. Cohen 
(Arch. Pharin., 1912, 260, 52— 62).— Tschirch and Schereschewski's 
work on this material (Abstr., 1905, i, 685) has been repeated, and it 
is shown that their a-chiclalban is a-amyrin acetate, their ^-chiclalban 
is a mixture of esters of lupeol and j8-amyrin, their y-chiclalban con- 
tains as its principal constituent a substance, CggH^jgO, Cg^Hj^^O, or 
CggHjjgO, m. p. 68°, which on admixture with Hesse's /5-cerotinone 
melts at 66—68°, and is possibly identical with that substance (Abstr., 
1893, i, 57). Chiclafluavil is a mixture of all the substances mentioned 
above. On steam distillation, chicle " gum" yielded a minute quantity 
of an alkaline distillate with an odour of amines, and on hydrolysis by 
alkalis furnished acetic, hexoic, and cinnamic acids. The portion of 
the **gum" insoluble in acetone is brittle, and has none of the 
properties of caoutchouc, so that the properties of chicle " gum," 
which render it suitable for '* chewing gum " manufacture, do not 
depend on the presence of caoutchouc-like substances. T. A. H. 

Occurrence of Chitin. Edmund 0. von Lippmann {Ber., 1911, 
44, 3716 — 3717). — A colourless, thin, tough skin, forming a light 
grey, amorphous powder when dry, which collected on the surface of 
some waste liquors in a sugar factory which had been set aside for 
several months, is shown to be composed of chitin produced by 
bacterial action. E. F. A. 

Lutein from Yolk of Egg. Richard Willstatter and Hein- 
RiCH H. EscHER {Zeitsch. physiol. Chem., 1912, 76, 214— 225).— The 
chemically indifferent yellow pigments of plants and animals are 
divided into the hydrocarbons of the carrotene group, C^qUqq, soluble 
in light petroleum, and the oxygen compounds of the xanthophyll 
group, G^oK^QOq, soluble in alcohol (Willstatter and Mieg, Abstr., 
1907, i, 865). Lycopene, the colouring matter of tomatoes, has been 
shown (Willstatter and Escher, Abstr., 1910, i, 330) to belong to the 
carrotene group, and it is now proved that lutein from the yolk 
of eggs is a xanthophyll isomeric with, and closely related to, that 
derived from chlorophyll. 

The methods of separating lutein from the phosphatides, fats, 
and cholesterol of the yolk are described : the pure pigment crystal- 
ises slowly from carbon disulphide in well formed prisms, or quickly 
in fire-red conglomerates of pointed, microscopic needles, m. p. 
195 — 196° (corr.). It crystallises from methyl alcohol in prisms 
with V-shaped indentations, which are amber-yellow with metallic 
lustre. 

Lutein forms an additive compound with iodine in ethereal solution ; 
the iodide is a dark violet powder consisting of microscopic, pointed 

eedles. It absorbs oxygen to the extent of 23% of its weight. 



f 



i. 126 ABSTRACTS OF CHEMICAL PAPEKS. 

In alcoholic solution ii hhows absorption bands in the blue and 
indigo-blue, corresponding with those of xanthophyll from leaves, but 
differing from carrotene. K. t' A. 

[Preparation of Thionaphthen Derivatives.] Kalle «fe Co. 
(D.R.-P. 239089. Compare Abstr., 1911, i, 666, 667, 1009).— An 
account of the preparation of substances having the general formula 
RS-CgH3(S-CH2-C02H)-C02H, some of which have been previously 
described (Abstr., 1911, i, 666). 

The following new compounds are mentioned : 

2-Carboxy-6-methi/Uhiolphenylthiolaceiic acid, yellowish-white needles, 
m. p. 220° (decomp.). 

S-Keto-Q-methi/Uhiol-(\)-thionaphthen-2-carboxi/lic acid, a colourless 
powder, and 3-ktto-Q-methi/Uhiol-(\)-thio7iap/Uhen, glistening needles, 
m. p. 133—134°. F. M. G. M. 

[Preparation of Thionaphthen Derivatives.] Kalle & Co. 
(D.R.-P. 239092). — o-Nitro-7n-xylidine was diazotised, and converted by 
the action of potassium cyanide and copper sulphate into 2nitro-m- 
xylonitrile, needles, m. p. 126°; this when heated at 100° during twelve 
hours with 80% sulphuric acid yielded 6-m^ro-2 : ^climethylheMzoic acid, 
yellow needles, m. p. 180°, and on reduction furnished the correspond- 
ing 6-amino-2 : ^-dimethylbenzoic acid, a yellow, crystalline powder, 
m. p. 126° (decomp.). The foregoing amino-acid when diazotised, 
xanthogenated, and treated with chloroacetic acid yielded 4:-carboxy-m- 
xylyl-b-thiolacetic acid, COgH-CgHgMeg'S-CHg'COgH, a microcrystalline 
powder, m. p. 158 — 159°, which on fusion with sodium hydroxide 
furnished ketoA : Q-dimethyUhionaphthencarboxylic acid^ red flakes, and 
was subsequently converted into keto-i : ^-dimet/iylthionaphthen, needles, 
m. p. 93°, which rapidly darkens on exposure to ligbt. 

F. M. G. M. 

[Preparation of Anthraquinonethioxanthones.] Fbitz Ull- 
MANN (D.R.-P. 238983. Compare Abstr., 1911, i, \010).—Anihra- 
quinone-thioxantho>ie, orange-red leaflets, m. p. 335°, is prepared by 
heating anthraquinone-1-o-thiolbenzoic acid with phosphorus penta- 
chloride in nitrobenzene solution ; the autbraquinone-thioxanthone, 
m. p. 272°, described previously (Abstr., 1910, i, 270) has now been 
obtained by fusing anthraquinone-2-o-thiolbenzoic acid with p-toluene- 
sulphonyl chloride at 205°, whilst anthraquinonyl-1 : 5-di-o-thiol- 
benzoic acid and phosphorus pentachloride furnish an atithraquinone- 
dithioxanthone, glistening, orange needles, which do not melt at 
350°. F. M. G. M. 

[Preparation of " Thioindigo " Derivatives.] Kalle & Co. 
(D.R.-P. 239673).— When 3-oxy-(l)-thionaphthen-2-carboxylic acid and 
its derivatives containing a free or substituted amino-group in the 
benzene nucleus are oxidised in either alkaline solution or neutral 
suspension, they yield " thioindigo " derivatives. 

" 6 : Q'-Diaininothioindu/o " was obtained as a brown, flocculent pre- 
cipitate by the oxidation of an aqueous alkaline solution of 6-amino- 



ORGANIC CHEMISTRY. i. 127 

3-oxy-(l)-thionaphtbeu-2-carboxylic acid with air at 70 — 80°; other 
oxidising agents can also be employed. F. M. G. M. 

Lysine Platinichloride. Max Siegfried {Zeitsch. physiol. Ghem., 
1912, 76, 234 — 237). — The platinichloride of active lysine, when dried 
over sulphuric acid, has the composition CgHi402N2,PtH2Cl(j,EtOH, 
and crystallises in needles more slender and darker than those of the 
platinichloride of inactive lysine, which forms stouter, paler yellow 
prisms, having the composition Q^^fi^^,V{M<fj\Q. Racemic and 
active lysine may be sharply differentiated in this manner. 

E. F. A. 

Hsemopyrrole. EicnARD Willstatter and Yasuhiko Asahina 
{Ber., 1911, 44, 3707 — 3710). — Hsemopyrrole from hsemin or from 
chlorophyll has been shown to contain phyllopyrrole, CgH^^N, iso- 
hsemopyrrole, CgHjgN, and another base, CgH^gN. The constitutions 
2:3:4- and 2:4: 3-dimethylethylpyrrole respectively were ascribed 
to the two latter compounds (Willstatter and Asahina, this vol., i, 41), 
but further investigation is necessary, as neither of them proves to be 
identical with the 2 : 4-diruethyl-3-ethylpyrrole synthesised by Knorr 
and Hess (Abstr., 1911, i, 1019; compare also Fischer and Bartholomiius, 
this vol., i, 50). 

The synthesis of Knorr and Hess is confirmed ; 2 : 4-dimethyl- 
3-ethylpyrrole has b. p. 84710 mm., 1977710 mm., Df 0-913. The 
styphnate forms four-sided prisms, m. p. 1 36° ; the chloropicrate gives 
prisms, m. p. 140°. On oxidation with nitrous acid, methylethyl- 
maleinimideoxime is obtained, crystallising in prisms, m. p. 215 — 216° 
(Knorr and Hess give 201°). 

The pyrrole base was reduced with hydrogen iodide and phosphorus 
at 240°, and finally with platinum and hydrogen. The pyrrolidine 
obtained has b. p. 145°, and forms a platinichloride , crystallising in 
pointed prisms, m. p. 220°, and an a-naphthylcarhamide, crystallising in 
irregularly-defined, rhombic plates, m. p. 109 — 110°. It is essentially 
different from isohsemopyrrolidine. E. F. A. 

Asymmetric Selenites. Luigi Marino and V. Squintani {Atti 
li, Accad. Lincei, 1911, [v], 20, ii, 666 — 670. Compare Marino, 
Abstr., 1908, ii, 833). — When absolutely dry, recently sublimed 
selenious anhydride is mixed with an equimolecular quantity of a 
solution of pure piperidine in anhydrous benzene cooled with ice, a 
colourless, crystalline mass is deposited. The reaction is complete in 
eight or ten hours. The product, after being washed with anhydrous 
benzene, gives on analysis figures corresponding with the formula 
CgHjjN'SeOg, but allowance has to be made for absorbed water, owing 
to the extremely hygroscopic nature of the substance. The compound 
has m. p. 70 — 71°, but traces of water may lower it to 64—65°. It 
probably reacts with alcohol, but the reaction product has not been 
isolated. The piperidine group is not involved in the reaction. 

R. V. S. 



t 



Cyclic Ammonium Bases. Johannks Gadamer (J. pr. Ghem., 
911, [ii], 84, 817— 820).— A reply to Decker and Kaulman (A.bstr., 



i. 128 ABSTRACTS OP CHEMICAL PAPEKS. 

1911, i, 807), who erroiioously attributed to the author the view thsu 
the cjirbinol bases have iu all cases the structure of amino-aldebydc.^ 
or ketones. F. B. 

Action of Methylamine and Aniline on Benzoyldehydracetic 
Acid. [Mutual Replacement of Ammonia and Amines in 
Pyridone Derivatives.] Pavel I. Pktrenko-Kritschenko and Joh. 
ScHOTTLE {B«r., 1911, 44, 3648—3654. Compare Abstr., 1911, i, 
1020). — ^The interaction of benzoyldehydracetic acid with methylamine 
and aniline has been studied, whereby the methyl- and phenyl-lactams 
of benzoyldehydracetic acid have been obtained. These have m. p. 
188° and 203° respectively. Unlike the lactam described previously 
{loc. cit.), neither of these compounds yields a pyridonecarboxylic acid 
when warmed with alkali. The methyl-lactam, on treatment with 
hydrochloric acid, yielded 2 : 6-diphenyl-4-pyridone, the platinichloride 
of which, m. p. 218 — 221° (decomp.), was analysed. When similarly 
treated, the phenyl-lactam yielded 2 : 6-diphenyl-l : 4-pyridone. 

The methyl- and phenyl-lactams were also prepared by the action of 
alcoholic solutions of methylamine and aniline on the lactam. Con- 
versely, the methyl-lactam, when treated with alcoholic ammonia, 
yields the lactam which was identified by conversion into 2 : 6-diphenyl- 
4-pyridone-3-carboxylic acid and 2 : 6-diphenyl-4-pyridone ; on treat- 
ment with an alcoholic solution of aniline, it yields the phenyl-lactam. 

Similarly, the anilino-group of the phenyl-lactam is replaceable under 
the action of ammonia or methylamine. H. W. 

The Condensation of Acetonedicarboxylic Ester with 
Aldehydes, Ammonia, and Amines. Pavel I. Petrenko- 
Kritschenko {J. pr. Chem., 1912, [ii], 86, 1 — 37). — A resume of the 
results of already published investigations by the author and various 
co-workers (Abstr., 1906, i, 452; 1907, i, 708; 1908, i, 564; 1909, i, 
605, 959; 1910, i, 188). D. F. T. 

Preparation of Derivatives and Homologues of Indole. 
Gksellschaft fUr Teerverwertung (D.R.-P. 238138). — When aryl- 
hydrazones (or their keto- or aldehyde derivatives) are heated with 
zinc chloride they furnish indole derivatives. 2-Methylindole was 
obtained in 75% yield by heating acetonephenylhydrazone (1 part) iu 
3 parts of solvent naphtha with zinc chloride (1 part) at 150° during 
one hour, extracting with water, and subsequently fractionating in 
a vacuum. 

3-Methylindole, previously prepared by E. Fischer in dS% yield, 
was produced in 80% yield from propionaldehydephenylhydrazone at 
200°, whilst ethyl phenyl hydrazonepyruvate furnished a 60% yield of 
2-indolecarboxylic acid at 130°. F. M. G. M. 

New Synthesis of Benzylidine-2-methylquinoline. von 
IsMAiLSKY (/. pr. C/iem., 1912, [ii], 85, 90 — 92). — In the presence of 
sodium hydroxide solution, o-aminobenzaldehyde slowly condenses 
with excess of fstyryl methyl ketone, yielding benzylidene-2-methyl 
quinoline. The product agrees entirely with previous descriptions 



ORGANIC CHEMISTRY. L 129 

(Wallach and Wiisten, Abstr., 1883, 1096 ; Jacobsen and Reimer, 
Abstr., 1884, 335; Doebner and Peters, Abstr., 1890, 176; Eibner, 
Abstr., 1901, i, 64). D. F. T. 

Condensation of para-Quinones -with Indoles and Pyrroles 
Containing Hydrogen in the 3- Position. Richard Mohlau and 
Alfred Redlich Ber., 1911, 44, 3605— 3618).— 2-Methylindole and 
/?-benzoquinone (2 mols.) react in boiling alcohol to form l-methyl- 

indyl-d-benzoquinonef CH^^p^^pTT^C — C^p tt !x^NH, dark violet, 

bronze needles, m. p. about 185°, and quinol in quantititive yield. 
That the reaction occurs directly at the 3-hydrogen atom, not at the 
iminic hydrogen atom, is proved, not only by the fact that the 
colourless ^ewco-compound, obtained by the action of hydrazine 
hydrate, forms a diacetate, m. p. 132° (a triacetate should be formed 
had the reaction occurred in position 1), but also because 1 : 2-dimethyl- 
indole and jt?-benzoquinone yield in a similar manner an almost quanti- 
tative amount of 1 : 2-dimethylindyl-3-benzoquinonef CjfjHjgOgN, m. p. 
about 160°, violet-black needles. In a similar manner, 2-methylindole 
and toluquinone yield a corresponding substance, C-^qK^^O^N, m. p. 
about 195°(decomp.), reddish-violet needles; the colourless diacetate of 
its leuco-compound has m. p. 146°. 2-Phenylindole and ;?-benzo- 
quinone give about 40% of 2-phenylindyl-3-benzoquinone, CgoHjgOgN, 
m. p. about 205°, blue needles ; 2 : 5-dimethylindole reacts with 
7>-benzoquinoue and with toluquinone to form about 90% of 2:5- 
dimethylindyl-3-benzoquinone, OjgHjgOgN, m. p. about 201° (decomp.), 
violet-black, bronze needles, and 2 : ^-dimethylindyl-^-toluquinoney 
CjyHjgOgN, reddish-violet needles. 

As is to be expected from the preceding, pyrroles unsubstituted in 
positions 3 and 4 react with jp-quinones (4 mols., two of which are 
utilised in oxidising the initially-formed leuco-compound) to form 
diquinonyl pyrroles ; thus 2 : 5 -dimethyl pyrrole yields 3 : i-diquinonyl- 

GMe'C'O TT O 
2 : 3-dimethylpyrrole, NH<^ '\ ^^^^^y black, microcrystalline 

powder, whilst 5-phenyl-2-methylpyrrole yields 3 : i-diquinonyl-^- 
phenyl-2-7mthylpyrrole, ^23^15^4^' brownish- black powder. 

Whilst with the preceding indoles and pyrroles only one nucleus 

enters the benzoquinone mole- 

CH2-CHMe S^. / \ cule, it is found that the more 

X;t^ — / \ \ / strongly basic 2-methyldihydro- 



I I-n/ 



indole reacts like the following 
bases with jt?-quinones, in that 

\ / O CHMe'CHg two nuclei enter the quinone 

molecule ; thus 2-methyldi- 
hydroindole yields a substance (annexed formula), m. p. 187°, brown 
needles ; methylaniline yields bismethylanilinoquinone, 

(NPhMe)2C6H202, 

reddish-brown leaflets ; tetrahydroquinoline yields bistetrahydroquino- 

linoquinone, {(^Q^B.^o\Cf.Ii^O^, m. p. 189°, brown ntedles, and 

4-methyltetrahydroquinoline yields bis-^-methyltetrahydroquinolino- 

■gwinone, (CgHgMeN^gJeHgO^, m. p. 197°. C. S. 

H VOL. CII. i. ]c 



i. 130 ABMTRACT8 OK CHEMICAL PAPERS. 

Products of the Condensation of 9 Methylcarbazole and 
Phthalic Anhydride. Fkanz Eiirenkeich {Monaish., 1911, 32, 
1103—1114. Compare Scholl and Neovius, Abstr., 1911, i, 567). — 
By the interaction of molecular proportions of 9-methylcarbazole and 
phthalic anhydride, the main product is 9-methylcarbazole-3-phthaloylic 

acid, CgH4 \|^w y CflHa'CO'CgH^'COgH, together with small quantities 

of 9-methylcarbazole-3 : 6-diphthaloylic acid, 

C0,H-C,H,-C0-C,H.^jj-jj^C,H3-C0-C,H,-C0,H. 

When twice as much phthalic anhydride is used, the quantity of the 
latter is increased considerably. 

9 -Methylcarbazole is conveniently prepared by the action of methyl 
iodide or of methyl sulphate at the ordinary temperature on potassium 
carbazole. 

9-Afethylcarbazole-'S-phthaloylic acid, prepared by the interaction of 
the components in benzene solution with aluminium chloride, crystal- 
lises in large, well-formed rhombs, m. p. 232° ; it shows a character- 
istic, cherry-red coloration with concentrated sulphuric acid, changing 
to green or the addition of strong nitric acid. The methyl group is 
only very slowly and partly eliminated on boiling with hydrogen 
iodide, and the attraction of alkyl to nitrogen is apparently increased 
by the phthaloyl group ; indeed, no trace of halogen alkyl is obtained 
on heating the diphthaloyl derivative with hydrogen iodide. 

The same methyl ester is obtained from the silver salt and methyl 
iodide, or from the acid chloride and methyl alcohol ; it crystallises in 
monoclinic prisms, m. p. 146°. 

9-Methylcarbazole-S : Q-diphthaloylic acid crystallises in slender 
needles, m. p. 330°; the cherry-red coloration with sulphuric acid 
turns yellow on the addition of strong nitric acid. 

The dimethyl ester crystallises in large, colourless prisms, m. p. 196°. 

2:3:6: 7-Diphthaloyl-9-methylcarbazole, 

C6H4'^CO^^«^2\JNM^^6^2\C0^^6^4» 

prepared by heating 9-methylcarbazole-3 : 6-diphthaloylic acid with 
sulphuric acid at 90° (compare SchoU and Neovius, loc. cit.), crystal- 
lises in reddish-yellow plates, which have not melted at 400°. With 
concentrated sulphuric acid a bluish-violet solution is obtained, which 
becomes orange when strong nitric acid is added. E. F. A. 

Ester Acids of Thiocarboxylic Acids with Aliphatic Alcohol 
Acids. V. Bror Holmberq {J. pr. Chenu, 1911, [ii], 84, 634—686. 
Compare Abstr., 1910, i, 361, 834). — A detailed account of the 
action of amines towards the following acids : xanthoacetic acid, 
OEt-CS-S-CHj-COgH ; ethyl dithiocarboglycollic acid, 

SEfCS-0-CH2-C02H ; 
dithiocarbodiglycollic acid, COgH-CHg-S-CS-O-CHg-COgH ; carbo- 
dithiogly collie acid, CO(S*CH2'C02H)2, and trithiocarbodiglycoUicj 
acid, CS(S-CH,-C02H)2. 

The previously-observed formation of diphenylcarbamide by th< 
action of aniline on xanthoacetic acid is considered by the author toj 



I 



ORGANIC CHEMISTRY. i. 131 



be due to the intermediate formation and decomposition of an additive 
compound with aniline, according to the following scheme : 
C02H-CH2-S-CS-OEt-^CO,H-OH2-S-C(S-NH3Ph)(NHPh)-OEt 

— ^ CO^H-CHg-SH + EtOH + HgS + C0(NHPh)2. 

Evidence in support of the author's view is furnished (I) by t'le 
non-formation of diphenylcarbamide in acid solution and in the 
absence of excess of aniline, and (2) by the isolation of similar 
additive compounds of the thiocarbamylglycoUic acids with amines 
(see b-low). 

/3-Phenylethylamine reacts with xanthoacetic acid, yielding an oily 
thiourethane, CHMePh-NH-CS-OEt. 

Ethyl dithiocarboglycollic acid forms with aniline in aqueous solution 
the aniline salt, SEfCS-O-COg'NHgPh, m. p. 77-5— 78°; when 
heated with aniline in alcoholic solution, diphenylcarbamide is 
produced. 

Dithiocarbodiglycollic acid reacts with ethylamine to form ethyl- 
thiocarbamylthioglycollic acid and the anhydride of ethylthiocarbamyl- 
glycoUic acid mentioned below. With aniline in ethereal solution it 
yields the aniline salts, CgHg05S2,2NH2Ph, lustrous, pale yellow 
leaflets, m. p. 97— 97'5° and C5Hg05S2,NH2Ph, m. p. 110— 110-5° 
When heated with aniline in aqueous solution, dithiocarbodi- 
glycollic acid gives rise to a mixture ol substances, the nature of which 
depends on the ratio of aniline to acid, and the temperature and 
duration of the reaction ; the following compounis were isolated from 
the product : s-diph'3nylthiocarbamide, phenylrhodanine, trithiocarbo- 
diglycollic acid, glycollic acid, thioglycoUic acid, phenylthiocarbamyl- 
glycoUic acid and its anhydride, and phenylthiocarbamylglycoUanilide. 

Trithiocarbodiglycollic acid reacts with primary amines, yielding 
thioglycoUic acid and rhodanines (compare Abstr., 1910, i, 361); with 
^-phenylethylamine it forms 3-p-pheni/lethylrhodanine, 

pale yellow, tabular crystals, m. p. Ill — 112°. 

EthyltrithiocarboglycoUic acid and aniline in aqueous solution yield 
phenylrhodanine and ethyl trithiocarbonate. 

iV-Sabstituted derivatives of thiocarbamylglycoUic acid are readily 
obtained by the interaction of amines and ethyldithiocarboglycollic 
acid. 

Ethylthiocarhamylglycollic acid, NHEt'CS'O'CHg'COgH, prepared 
from ethylamine in aqueous solution, crystallises in stellar aggregates 
of smill, white needles, m. p. 97*5 — 98° ; t\\Q sodium salt is amorphous; 
the barium salt, (NHEfCS-0-CH^-0O2)2Ba,3H2O, forms colourless 
plates. It is oxidised by bromine to ethylcarbamylglycollic acidy 
colourless prisms, m. p. 85 — 86°, and when warmed in aqueous 
solutioQ forms an anhydride {2-thion-3-ethyl-i'Oxazolidone)j 



o— cs 

CH2-C0^ 



NEt, 



^hich crystallises in colourless plates, m. p. 40 — 40-5°. 
^kDiethylthiocarbamylgly collie acid, NEtg'CS'O'CHg'OOgH, prepared 
HE^ni diethylamine, crystallises in fla«-, colourless piisms, m. p. 90*5 —91°, 

H VOL. CII. i. I 



i. 132 ABSTRACTS OF OHBMIOAL PAPERS. 

and yields cryHtalline sodium and barium saltH ; the ethijl ester 
is an oil. 

Phviiylthiocarbamylglycollic acid^ NHPh'CS'O'CHg'COjH, m. p. 
Ill — 112°, obtained together with phenylrhodanine and diphenyl- 
carbamide by heating aniline with ethyldithiocarboglycollic acid in 
aqueous solution, crystallises with one molecule of acetic acid in long, 
oolourless prisms, which lose their acetic acid on exposure to air ; the 
sodium salt and barium salt, (NHPh-CS-0-CH2-C02)Ba,3H20, were 
analysed. It readily loses water, forming the anhydride {2-thion- 

3-phenylA-oxazolido7ie)y Y ^NPh, which crystallises in stout, 

irregular plates or short prisms, m. p. 172 — 173°, and dissolves in 
aqueous sodium carbonate to form the sodium salt of the original 
acid. When heated in neutral or alkaline solution, it yields glycollic 
acid and diphenylcarbamide ; in aqueous ammonia, phenylthio- 
carbamide is produced. Oxidation with potassium permanganate 
yields phenylcarbamylglycollic acid. 

Phenylthiocarbamylglycollanilide, NHPh-CS-O-CHg'CO'NHPh, pre- 
pared by heating the acid with aniline in aqueous solution, forms 
lustrous, white needles, m. p. 133 — 134°. 

2 - Thion - 3 - phenyl - 4 - oxazolidone is oxidised by bromine to 

2 : 4-diketo-3-phenyloxazolidine. When dissolved in alcoholic sodium 

CO'NPh 
ethoxide, it forms a gelatinous sqdium salt, I ">C(8Na)-QEt, 

which is decomposed by acetic acid, yielding 2-ethoxy-2-thiol-3- 

CO'NPh 
phenylA-oxazolidwuSy I _>C(SH)-OEt. This crystallises in colour- 
less needles, m. p. 73 — 73 5°, and dissolves in alkalis, forming salts of 
phenylthiocarbamylglycoUic acid. The above-mentioned sodium com- 
pound reacts with ethyl iodide, yielding a reddish-yellow oil, probably 

pr "^C(SEt)'OEt, which, on treatment with aqueous sodium 

hydroxide, is converted into ethyl mercaptan and phenylcarbamyl- 
glycollic acid ; with ethyl chloroacetate it forms the compound, 

CO'NPh 

T^_^C(OEt)-S-CH2.C02Et, 

which, by dilute hydrochloric acid, is hydrolysed and converted into 
2 : 4-diketo-3-phenylthiazolidine, and by acetic acid is hydrolysed to 
phenylcarbamylglycollic acid and a substance crystallising in small, 
flat prisms or white needles, m. p. 171—172°. The latter substance 

is probably diphenylhohydantoin, V "^CINPh. 

The interaction of chloroacetanilide and the sodium salt of 
2-thiol-2-ethoxy-3-phenyl-4-oxazolidone yields a thiazolidone compound, 

6o-NPh>^'^^^ '''* So-NPh'^^'^^^' '''^'''^ ^'''"'^^ P^^® ^^^^""^ 
crystals, m. p. 174 — 175°. 

The prolonged action of alcoholic sodium ethoxide on 2-thion- 
3-phenyl-4-oxazolidone at the ordinary temperature gives rise to 



I 



ORGANIC CHEMISTRY. i. 138 

sodium phenylthiocarbamylgly collate ; at 100°, xanthanilide is 
produced. 

Piperidine combines with 2 - thion - 3 - ethyl - 4 - oxazolidone in 
alcoholic solution to form '2-thiol-2-piperidyl-3-ethyl-4:-oxazolidone^ 

Y"' '>C(SH)-N:C5Hio, colourless prisms, m. p. 146—147°, and 

with the corresponding phenyl derivative, yielding 2-thiol-2-piper- 

CO'NPh 
idyl-3-phenyl-4:-oxazoUdone, i />C(SH)'05NHiq, which forms 

OXI2 ^ 
white needles, m. p. 130—132° 

2-Thion-3-ethyl-4-oxazolidone condenses with benzaldehyde in 
the presence of sodium ethoxide, yielding a-keto-)8y-diphenylbutyro- 
lactone (Erlenmeyer and Knight, Abstr., 1894, i, 592); the same 
compound, accompanied by s-diphenylthiocarbamide, is obtained by 
the condensation of 2-thion-3-phenyl-4-oxazolidone with benzaldehyde 
by sodium ethoxide. 

NEt'CO 
2 - Thion - b-benzylidene -'3 -ethyl- ^-oxazolidone^ » ^CICHPh, 

prepared by condensing 2-thion-3-ethyl-4-oxazolidone with benz- 
aldehyde in the presence of piperidine, crystallises in colourless 
plates or short prisms, m. p. 94*5 — 95° ; when the condensation is 
effected by means of acetic anhydride, a stereoisomeride^ crystallising 
in long, pale yellow prisms, m. p. 137'5 — -138°, is obtained. 
2 - Thion- 3 -phenyl-^ -benzylideneA-oxazolidoTie, 

OS — o>^-^"^*'' 

prepared by condensing 2-thion-3-phenyl-4-oxazolidone and benz- 
aldehyde by means of acetic anhydride, forms slender, golden-yellow 
needles, m. p. 181-5-182°. 

3-Phenylrhodanine reacts with piperidine in alcoholic solution, 
yielding phenylpiperidylthiocarbamide, NHPh'CS'C^NHjQ, thin, white 
prisms, m. p. 100 — 100*5°, and with alcoholic sodium ethoxide to 
forDi a sodium salt, which on acidification with acetic acid yields 

CO'NPh 
4:k66o-2-thiol-2-et/ioxy-3-phenylthiazolidiney I ^C(SH)*OEt; this 

crystallises in colourless, flat, prismatic needles, m. p. 61*5 — 62°. 

The formation of the latter compound furnishes additional evidence 
in support of the thiazolidine formula assigned to the rhodanines. 

F. B. 

Nitro derivatives and Nitro-hydrazonea. Roberto Ciusa {Aui 
E. Accad. Lincei, 1911, [v], 20, ii, 578 — 583. Compare Hantzsch, 
Abstr., 1910, i, 475). — The author refers to the different coloured 
modifications of hydrazones of nitro-aromatic aldehydes which he has 
described, and suggests that they are chromo-isomerides like the nitro- 
anilines of Hantzsch. According to him, a nitrohydrazone of the 
formula NOgAr-CHIN-NRPh can exist in the two forms : 

OgN-Ar-CHIN-NPhR , ,, ^ r. xr a ^.tt-vt xtt^ut^ / n n 

: ^ : (red) and 02N-Ar-CH.N-NPhR (yellow). 

Since the hydrazones contain a -CIN- linking, thoy can exist in 

I 2 



i. 134 ARHTRACTS OF CHEMICAL PAPERS. 

syn- and anit-forma, and it is suggested that the red isomeride.s ate the 
«y7i forms, because that configuration would favour the origin of the 
internal additive product containing a secondary valence. 

E. V. S. 

Constitution of Buchner's so-called Pyrazolinecarboxylic 
Acids. Carl BCixdw (Ber., 1911, 44, 3710— 3716).— By the inter- 
action of phenylhydrazine and acraldehyde, Fischer and Knoeve- 

y — QJJ 

nagel obtained phenylpyrazoline, NPh<^ I . Subsequently 

pyrazoline, NH<^ Y , was obtained by Curtius and Wirsing by 

the interaction of hydrazine and acraldehyde. This is very unstable 
towards oxidising agents, but it can be distilled unchanged, and is 
stable towards hydrochloric acid. 

On the other hand, the pyrazolinecarboxylic acids described by 
Buchner (Abstr., 1893, i, 430; 1894, i, 348), obtained from aliphatic 
diazo- compounds and unsaturated mono- or di-carboxylic acids of the 
ethylene series, are characterised by giving up all their nitrogen on 
heating or distillation and forming c^c/opropanecarboxylic acids. 
When boiled with dilute mineral acids, hydrazine is eliminated. 
Lastly, they are readily converted into pyrazole derivatives. 

These facts are not in agreement with the relatively stable nature 

of heterocyclic five-membered rings, and it is considered that Buchner's 

cids are more correctly formulated as mixed azines of glyoxylic and 

oxalacetic acid esters ; thus the product from ethyl diazoacetate and 

ethyl fumarate has the formula 

COgMe-CHIN-NiqCOaMej-CHa-COgMe. 

Azines such as benzylideneazine, CHPhIN*N!CHPh, give up the 
whole of their nitrogen on heating, and the other properties of 
Buchner's acids are shown to be in accord with formulating them as 
mixed azines instead of as pyrazolinecarboxylic acids. E. F. A. 

Pyrimidines. LIV. Condensation of Carbamide and 
Guanidine with Esters of Allylmalonic and Some Alkyl- 
substituted Allylmalonic Acids. Treat B. Johnson and Arthur 
J. Hill (Amer. Cheiii. J.^ 1911, 46, 537 — 549). — In an earlier paper 
(Abstr., 1911, i, 502) it has been shown that ethyl allylmalonate reacts 
with thiocarbamide to form ethyl 2-amino-4-keto-7-methyltetrahydro- 
hexathiazole-5-carboxylate instead of the expected allylthiobarbituric 
acid, whilst ethyl benzylallylmalonate and diallylmalonate condense 
with thiocarbamide with production of acylthiocarbamides or their 
y-lactones. In view of this abnormal behaviour, experiments have 
been carried out to ascertain whether barbituric acid derivatives are 
formed by the condensation of ethyl allylmalonates with carbamide and 
guanidine. 

5 Allylmalonylcarbamide (allylbarbituric acid), 

m. p. 167°, obtained by the action of carbamide on ethyl malonate in 



ORGANIC CHEMISTRY. 1. 135 

presence of sodium ethoxide, crystallises in nearly colourle.^s plates, 
ar)d is hydrolysed by potassium hydroxide with formation of ally]- 
malonic acid. 6-Allylmalonylguanidine^ 

nh:c<^^;^^>ch-ch2-ch:ch2,2H20, 

m. p. 265 — 266°, crystallises in pink prisms or hexagonal tablets. 
5 : 5-Diallylmalonylcarbamide {diallylharhituric acid), 

co<Cj^jj.qq>c(ch2*ch:ch2)2, 

m. p. 173°, obtained by the action of carbamide on ethyl diallyl- 
malonate, forms colourless, rhombohedral crystals, and on hydrolysis 
with potassium hydroxide yields diallylmalonic acid. 5 : 6-DiallyI- 

malonylguanidine, NHIC<^-p^TT,p^^C(CH2*CHICH2)2, crystallises in 

colourless, rhombohedral prisms, does not melt below 300°, and is 
hydrolysed by potassium hydroxide with formation of diallylmalonic 
acid. 

5-Benzyl-5-aUylmalonylcarbamide {6-benzyl-5 -allylbarbituric acid), 

^^'^NH-C0'^^(^^2I*^)'^^2*C'H:CH2, m. p. 198°, prepared by the 

condensation of carbamide with ethyl benzylallylmalonate, crystallises 
in prisms ; it can also be obtained by the action of allyl iodide on 
silver benzylbarbiturate. The compound is not hydrolysed smoothly 
by potassium hydroxide. When guanidine is heated with ethyl benzyl- 
allylmalonate in presence of sodium ethoxide, benzylallyliminomalonuric 
acid, NH2-C(NH)-NH-CO-C(CH2Ph)(CH2-CH:CH2)-C02H, or, more 

probably, NH:C<^^~^^>C(CH2Ph)-CH2-CH:CH2, is produced, 

which crystallises in needles, does not melt below 300°, and is imme- 
diately transformed by dilute hydrochloric acid into 5-benzyl-5-allyl- 
malonylguanidine hydrochloride. 5-Benzyl-6 -allylmalonylguanidine, 

NH:C<^^;^^>C{CH2Ph)-CH2-CH:CH2, can also be obtained by 

the action of benzyl iodide on 5-allylmalonylguanidine ; it forms a fine, 
colourless powder, and does not melt below 300°. Attempts to obtain 
pure benzylallylmalonic acid by the hydrolysis of this compound with 
potassium hydroxide were not successful. 

Benzylallylmalonic acid, CH2 1 CH-CH2-C(CH2Ph)(C02H)2, was 
obtained as a viscid, uncrystallisable liquid by the hydrolysis of its 
ethyl ester with potassium hydroxide ; the silver salt was prepared. 

E. G. 

Preparation of l-;;-Dimethylaminophenyl-2 : 3 : 4-trimethyl- 
5-pyrazolone. Farbwerke vorm. Meister, Lucius <fe Pruning 
(D.R.-P. 238256). — \-^-Aminophenyl-2 : 3 : 4z-trimethyl-b-pyrazolone, 
m. p. 225 — 227°, prepared by the reduction of 1-p-nitrophenyl- 
2:3: 4-trimethyl-5-pyrazolone, crystallises from water in colourless 
crystals containing 2H2O. When heated at 90—100° with methyl 
iodide, it yields lip-di'methylaminophenyl-2:3-A-trimethyl-5-py7'azolone, 
which crystallises with 2HJo, and has m. p. 140° (anhydrous). 

The following compounds are also described : l-^'Aminoj^henyl- 



i. 18(> ABSTRACTH OF CHEMICAL PAPERS. 

3 : \-diniethyl-b-pyi'azohney a colourless, cry ata! line f)owder, m. p. 232°, 
obtjiined by reducing the corresponding nitro-com pound. ft-Kthoxy- 
l-p-ami7iopheni/l-3:4:-dimethi/lpyrazole, m. p. 95 — 97°. l-p-Acetylamino- 
pJienyl-^ : i-dini^thylb-pyrazolone, a colourless, crystalline powder, m. p. 
272 — 273°. b-Ethoxy-\-y)-acelylaminop1ienyl-^'A'dimethylpyrazole, m. p. 
130° b-Atietoxy-\-\>-acetylaminoph6nyl-^ : A-dimethylpyrazole, m. p. 
167 — 168°. l-p~Methylatninophenyl-3 : A-dwiethyl-5-pyrazolonej needles 
or leaflets (IHgO), m. p. 108 — 110°. X-p-Dinmthylaminophenyl- 
3 : 4:dimetIiyl-5 -pyrazolone, id. p. 199 — 200°. l-jp-Aceiylmethylamino- 
phenyl-3 : 4:'dimethyl-5-pyrazolone crystallises with 2H2O, m. p. 80° or 
162° (anhydrous). 5-Ethoxy-l-pmfiMylaminophenyl-3 : 4:-dimethyl]^yrazole 
is an oil ; its miroso-derivative has m. p. 75°. 

l-p-Ac6tyl7nethylaminophenyl-2 : 3 : A^-trimathyl-b-pyrazolone has m. p. 
139 — 140°. l-i>- Methylaminophenyl-2 : 3 : ii-irimethy 1-5 -pyrazolone has 
m. p. 168°. F. M. G. M. 

[Preparation of Substituted Pyrazolones.] Farbwerke vorm. 
Mkister, Lucius & BriJnino (D.R.-P. 238373). — It is found that i-iso- 
valerylamino-l-phenyl-3-methyl-5-pyrazolone and its derivatives can 
be methylated (methyl sulphate) without eliminating the ?>ovaleryl 
group in position 4 ; the following compounds are described : 4-iso- 
Valerylainino-\-phenyl-2 : '6 -dimethylrb -pyrazolone forms colourless crys- 
tals, m. p. 203°. 4:-ii>,oValerylaniino-i -phenyl -3-7nethyl-5-pyrazolone forms 
colourless crystals, m. p. 230°. i-iaoValerylamino-b-ethoxyl-phenyl- 
3methylp9/razole has m. p. 115°. 5-Chloro-4c-hovalerylamino-\-phenyl- 
3-inethylpyrazole has m. p. 120°. A-iaoValerylamino-^-isovaleryloxy- 
l-jjhenyl-S-methylpyrazole has m. p. 122 — 123°. ^-a-Bromo\9,ovaleryl- 
aniino-l-phenyl-2 : 3-dimethylb-pyrazolone forms colourless crystals, m. p. 
206°. 4-a- Bromoi80valerylami7io-5-a-bromo\sovaleryloxy-l-phenyl-3^methyl- 
pyi'azole, colourless crystals, m. p. 114 — 116°, is obtained by treating 
an aqueous solution of 4-amino-l-phenyl-3-methyl-5-pyrazolone hydro- 
chloride with a-bromoi«ovaleryl bromide in the presence of sodium 
acetate. F. M. G. M. 

Hydantoins. VIII. Action of Bromine on Tyrosinehydan- 
toin. Treat B. Johnson and Charles Hoffman (Arner. Chem. J!, 
1912; 47, 20— 27).— It has been found by Wheeler, Hoffman, and 
Johnson (Abstr., 1911, i, 923) that tyrosinehydantoin is converted by 
chlorine into the 3 : 5-dichloro-derivative, and that the latter is hydro- 
lysed by barium hydroxide with formation of 3 : 5-dichlorotyrosine. 

It is now shown that iodine reacts in a similar manner with tyrosine- 
hydantoin with production of a nearly theoretical yield of 3:5-di- 
iodotyrosinehydantoin. With bromine, however, tyrosinehydantoin 
behaves abnormally, giving 3 : 5-dibromobenzylidenehydantoin as the 
chief product of the reaction, and only a small quantity of 3:5- 
dibromotyrosinehydantoin. 

3 : 5-Di-iodotyro8inehydantoiny OH'CqH2I2*CH2*CH<^ ' , m. p, 

235° (decomp.), crystallises in hexagonal plates. 

3 : b'Dihromo-\:-hydroxyhenzoylhydantoic acid (3 : 5-dth'i'omotyrosin 
hydaMoic acid), NH2-CO-NH-CH(C02H)-CIl2-CjH2Br2-OH, " m. 



ORGANIC CHEMISTRY. i. 137 

191°, obtained by the action of potassium cyanate on 3 : 6-dibromo- 
tyrosine, forma rhombohedral plates or square prisms, and is hydrolysed 
by concentrated hydrochloric acid with formation of 3 : b-dihromotyrosine- 

hydantoin, OH-CgHgBrg-CHa'CH^ i , m. p. 223— 225° (decomp.), 

which crystallises in prisms. 

3 : h-DihromoA-hydroxyhenzylidenehydantoin^ 

0H-C,H,Br,-0H:C<J^7j^, 

m. p. above 295° (decomp.), obtained by condensation of 3 : 5-dibromo- 
4-hydroxybenzaldehyde with hydantoin, forms small, brownish-yellow 
needles, yields a yellow mnmonium salt, and is reduced by hydriodic 
acid with production of 3 : 5-dibromotyrosinehydantoin. 3 : 5-Dibromo- 
4-hydroxybenzylidenehydantoin is also produced by the action of 
bromine on tyrosinehydantoin and on 3 : 5-dibromotyrosinehydantoin. 

E.G. 

The Reduction of Aromatic Aldazines. Theodor Curtius 
(/. pr. Ghem., 1912, [ii], 85, 37—77. Compare Abstr., 1900, i, 610). 
— The paper first gives a summarised account of the results of the 
investigations published hitherto by different workers on the products 
obtained by the reduction of benzaldazine (benzylidenehydrazine) and 
its substituted derivatives under various conditions. 

[With Franz Schneiders.] — Benzylhydrazine easily undergoes 
atmospheric oxidation, giving a deposit of benzaldehydebenzyl- 
hydrazone (private communication from August Darapsky). 

Towards the esters of p- and y-ketonic acids, benzylhydrazine 
behaves like phenylhydrazine. Warmed with benzoylacetic ester it 
yields 3-phenyl-l-benzyl-6-pyrcczolone, a white, crystalline powder, 
m. p. 204 — 205°. Ferric chloride solution is without action on the 
substance (contrast the 1-benzy 1-3 -methyl compound below). When 
treated in glacial acetic acid solution with sodium nitrite, i-oximino- 
S-phenyl'l-benzyl-6 -pyrazolone is obtained; it forms deep red needles, 
m. p. 161—162°. 

On warming benzylhydrazine with ethyl laevulate, 1-benzyl-S-methyl- 

Q-pyridazinone, CJI^^ri^ -Tsr^^N'CHgPh, is obtained ; this crystal- 
lises from light petroleum in colourless, prismatic crystals, 
m. p. 56—57°. 

When cautiously added to ethyl acetoacetate, benzylhydrazine yields 
l-benzylS-methyl-b-pyrazolone, a white, crystalline solid, m. p. 
175—176°, b. p. 192— 194°/14 mm.; the intermediate benzylhydr- 
azone of acetoacetic ester could not be isolated. The product is acid 
to litmus, and the copper, cobalt, nickel, and silver salts are described ; 
the hydrochloride forms prismatic crystals, m. p. 120°. 

1 -Benzyl- 3-methyl-5-pyrazolone is exceedingly reactive. Ferric 
chloride solution in the cold gives a brown coloration, and on 
boiling causes oxidation to the corresponding pyrazole-blue. 
Heated with phosphorus pentachloride, it yields 4:-dichloro-l-benzyl- 
3-methyl-5 -pyrazolone, which crystallises in leaves, lu. p. 59 — 61° ; the 
analogous i-dibromo-compound forms small, hard crystals with a tinge 



i. 138 



ABSTRACTS OF CHEMICAL PAPERS. 



of yellow (m. p. 81 — 83°); these two dihalogen compounds are, unlike 
the original Bubstance, indifferent to both acid and alkali. 

i-p-Tolueneazo-\-benzyl-3-77iethyl-5-pyrazolone, obtained by the actionj 
of toluenediazonium sulphate, forms slender, yellow needles, m. p. 
123—124°. 

\-Bepzyl-i-benzylidene-2-methyl-5-pyrazolone, obtained by the action 
of benzaldehyde on benzylmethylpyrazolone, forms red crystals, m. p. 
111—112°. 

On heating benzyl methylpyiazolone with phenylhydrazine, ammonia 
is tvolved, and ihi s-l -benzyl d-methyl'5-pyrazolone, 
N:CMe CMeIN 

CHgPh-N— CO^ ^CO— N-CHgPh' 

obtained, which forms white needle crystals, meltinjr above 330°; by 
oxidation with various oxidising agents it past-es smoothly into 

N:CMe XMeIN 



1 'henzyl-3-methylpyrazole • blue, 



CH^Ph-N- 



■co>^-^<co- 



•N-CHaPh' 



this crystallises in almost black needles, m. p. 142 — 144°, and is 
decomposed by strong acids and boiling alkali solutions. Careful 
oxidation of benzyl methylpyrazokne by potassium permanganate gives 
a white acid substance of indefinite m. p., which could not be further 
purified ; the silver salt was obtained as a white precipitate, m. p. 
185 — 189°; txcess of permanganate causes oxidation to benzaldebyde 
and benzoic acid. 

On treating l-benzyl-3-metLyl-5-pyrazolone in dilute hydrochloric 
acid solution with sodium nitrite, 4:-oximinol-benzyl-3-methyl-5- 
2)yrazulone is obtained, crystallising in yellow needles or prisms, 
m. p. 152 — 152-5°. By reduction with zinc dust in acetic acid 
solution, the oximino-compound gives a solution of i-amino-\-benzyl- 
3-met/tyl-5-pyrazolone, which was not isolable, and attempts to isolate 
it as the benzylidene derivative merely caused oxidation to the 
corresponding rubazonic acid of l-benzyl-3-meihyl-5-pyrazolone, 

CHgPh-N— CO-^ ^ ^CO— N-CHgPh' 

this, mere conveniently prepared by oxidation of the amino-com pound 
with ferric chloride, forms cinnabar-red crystals, m. p. 160 — 161° ; its' 
solutions in alkalis are violet-red. 

The ammonium salt of 4-oximino-l-benzyl-3-methyl-5-pyrazolone 
forms a yellow powder (m. p. 175 — 176°) ; with silver nitrate it yields 
the silver salt as a reddish-brown, insoluble, amorphous powder, which 
decomposes completely at 179°. 

On the other hand, silver nitrate decomposes an acetic acid solution 
of the free oximino-compound, nitrous fumes are evolved, and finally 
microscopic needles of the silver salt of 4-nitro-l-benzyl-3-methyl- 
5-pyrazoloDe are obtained, which decompose at 245 — 246°. 

A:-Nitro-\-benzyl-'6-methyl-b-pyrazolone can be obtained from tlie' 
silver salt, or by oxidation of the oximino-compounds with nitric 
acid ; it forms colourless needles, m. p. 144 — 145° (decomp.). 

The silver salt of the nitro-compound gives with anilire a, siihgtanceA 
NICMe i 

r.u T)u xr* fi/^^^'^(N^^^)2'^^-&' ^hich .«ieparat«s on cooling in 



I 



ORGANIC CHEMISTRY. i. 139 



yellow, capillary crystals ; treatment with solvents removes aniline 
from the substance, regenerating the original silver salt. 

\- Benzyl-^ :^-dimethyl-b-pyrazoJ one (1-benzylantipyrine) is obtained 
by methylating l-benzyl-3-m(.tbyl-5-pyrazolone. It forms anhydrous, 
hygroscopic crystals, m. p. 84 — 86° ; from moist solvents, it crystallises 
with IH2O, and then has m. p. 102 — 103°. The picrate forms long, 
yellow needles (from hot water), m. p. 143 — 145°. i-Oximino- 
l -benzyl-2 : 3-dimethylpyrazolone is an unstable, de(^p green, viscous 
oil. If benzylantipyrine is oxidised with concentrated nitric acid, 
4: -nitro -I- benzyl- 2 : 3-dimethylpyrazolone is obtained as colourless, 
, prismatic crystals, m. p. 161 — 162°. 

I The physiological action of benzylantipyrine was investigated ; it 
' appears to possess certain advantages over ordinary antipyrine. 

[With GusTAV Sprenger.] — ;?-Methylbenzylhydrazine (compare 
Abstr., 1900, i, 612) is best prepared by reduction of />-methyl- 
benzaldazine by sodium amalgam ; on dilution with water and 
cooling, crystals of the jt?-methylbenzylhydrazone of /?-tolualdehyde 
separate, and can be decomposed by hydrochloric acid. The dihydro- 
chloride, m. p. 150° (decomp.), the sulphate, m. p. 178 — 179°, and the 
oxalate, m. p. 180°, were obtained. 

Benzaldehyde-p-methylbenzylhydrazone forms large, transparent 
tablets, m. p. 88°; the diacetyl derivative, CgH^Me'CHg'NgHAcg, 
forms crystals, m. p. 75° (indefinite). The stable ntVroso-compound, 
CgH^Me'CH2*N(NO)'NH2, crystallises from water in needles, m. p. 78°, 
and when warmed with dilute sulphuric acid yields /j-methylbenzylazo- 
imide, Cj-H^Me'CHg'^SJ ^' P* 94°/12 mm. (compare Curtius and Darap- 
sky, Abstr., 1902, i, 844). With ethyl acetoacetate, j9-methylbenzyl- 
hydrazine gives 1 -/>-methylbenzyl-3-methyl-5 -pyrazolone (compare 
Abstr., 1900, i, 612); its hydrochloride has m. p. 130°. By treat- 
ment with nitrous acid the above pyrazolone is converted into yellow 
4:~oximino-l-i>'methylbenzyl-3-methyl-6~pyrazolone, m. p. 154°. By metbyl- 
ation the pyrazolone is converted into l-ip-methylbenzyl-2 : 3-dimethyl- 
b pyrazolone, which forms prismatic crystals, m. p. 78°. The sub- 
stance behaves analogously to antipyrine and benzylantipyrine towards 
nitrous acid and ferric chloride. Its physiological effect has not yet 
been investigated. D. F. T. 

Ethyl Cyanoanilide-o-carboxylate. Ralph H. McKee (/. pr. 
Chem., 1911, [ii], 84, 821— 826).— By the interaction of ethyl 
cyanoimidocarbonate and ethyl anthranilate, Finger and Zeh (Abstr., 
1910, i, 382) obtained a compound which they considered to be ethyl 
cyanoanilide-o-carboxylate. The author has investigated the action 
of cyanogen bromide on ethyl anthranilate, and finds that the resulting 
compound, which undoubtedly has the structure of ethyl cyanoanilide- 
o-carboxylate, is different from Finger and Zeh's compound. The 
latter substance is considered to be ethylbenzoyleneisocarbamide, 

[2-eth( xyquinazolone], < ^C-OEt or J ^C*OEt, and this 

view is supported by the formation of the corresponding methyl com- 
pound by the interaction of nietliy.l cyanoimidocarbonate and ethyl 
anthranilate. According to Finger and Zeh the products obtained 



i. 140 



ABSTRACTS OF CHEMICAL PAPERS. 



from both the methyl and ethyl cyanoimidocarbonates should be 
identical. Finger and Giinzler had already shown that it is a quinazo* 
line derivative (Abstr., 1911, i, 237). 

MeXhyl ci/anoimidocarbonate, NHIC(CN)'OEt, prepared by the action 
of hydrogen chloride on methyl alcohol and potassium cyanide, is 
a colourless oil, b. p. 115°/760 mm., having an odour of mice excre- 
ment. It reacts with ethyl anthranilatc at 80'^ in the presence of 

cuprous chloride, yielding 2-metfioxyquinazolone, Y ^C*OMe, 

m. p. 231 — 232° (corr.), which is hydrolyaed by hydrochloric acid to 
2 : 4-diketodihydroquinazoline, m. p. 357° (corr.) ; Griess {Be7\, 1869, 
2, 416) gives 344°. 

Methyl cyanoanilideo-carboxylate, CN'NH'CgH^'COgMe, obtained by 
the action of cyanogen bromide on methyl anthranilate in ethereal 
solution, crystallises in needles, m. p. 105° (corr.). When heated at 

^^•^^ n XT rk xr 

6» 



Cg^Hj 



.O.N, 



100°, it polymerises to tri-o-carbomethoxyplienr/lmelamine 
which has m. p. about 160°. 

Ethyl cyanoanilide-o-carboxylate, prepared from cyanogen bromide 
and ethyl anthranilate, has m. p. 93 — 94°, and polymerises to tri-o- 
carbethoxyphenylmdamine^ CgoHgoOgNg, m. p. 190° with previous 
sintering. 



Methyl anthranilate forms a picrate^ 



NH^-C.H.-CO^Me.O.HgO^Ng, 

106° (corr.); 
F. B. 



crystallising in deep yellow, microscopic needles, m. p. 
t\\Q picrate of ethyl anthranilate has m. p. 116"^ (corr.). 

Preparation of Derivatives of Indophenols. Leopold Cassella 

& Co. (D.R.-P. 238857). — Indophenols prepared from carbazolecarb- 

QQ T> oxylic acids and nitrosophenols 

y\2 /NHs^ ys^ have previously been described; 



u — K^--■ 



these substances on reduction 
>0H furnish leuco-derivatives having 

the annexed general constitution, 
which, when slowly dropped into a hot solution of sodium polysulphide, 
yield dark blue sulphur cotton dyes which are extremely fast to light, 
washing, or chlorine. F. M. G. M. 

Preparation of Anthraquinone Derivatives. Farbenfabrikebt 
voRM. Friedr. Bayer <k Co. (D.R.-P. 238981. Compare following 
abstract). — When acyl o-diaminoanthraquinones are treated with 
dehydrating reagents, the following action takes place : 



A< 



NR-COR' 
NH„ 



= A<^^>CR' 



HgO, 



where A is an anthraquinone residue (substituted or otherwise), Ri 
hydrogen, alkyl, or aryl, and R' alkyl, aryl, or an ethoxy-group. 

1 : 2-PJienylanthraquinoneiviinazoley prepared from benzoyl- 1 : 2- 
diaminoanthraquinone, and i-amino- I : 2 - phenylanthraquinoneimin- 
azoUf obtained from benzoyl- 1 : 2 : 4-triaminoanthraquinone by the^ 
action of sulphuric acid at 150°, form yellow crystals and glistening, 
metallic needles respectively. 

1 : 2-Hydroxyanthraquinoneiminazole (I), prepared by the action 
carbonyl chloride on 1 : 2-diaminoanthraquinone, crystallises from^ 
quinoline in needles. 



ORGANIC CHEMISTRY. i. 141 

4 - Hydroxy- 2 - ethoxy- 1 -^^-tolylanthraquinoneiminazole (II), yellow 
needles, was obtained by the fusion (at 100°) of p-toluidine with 
dinitro-yS-aminoanthraquinoneurethane ; it yields a sulphonic acid when 
heated with fuming sulphuric acid. 

1 : ^-Methylanthraqidnoneiminazole, yellow needles, obtained from 
1 : 2-diaminoanthraquinone and acetic anhydride, and the compound, 
from the same base and formic acid, are also mentioned in the 
original. 

NH— C-OH N(C^H^)-C-OEt 

II III loR 

v.o/^/ \/\co/\/ 

(I.) (II.) 

F. M. G. M. 

Preparation of Anthraquinone Derivatives. Fakbenfabriken 
VORM. Friedr. Bayer & Co. (D.E.-P. 238982). — Condensation products 
of benzaldehyde and /3-aminoanthraquinones have been described by 
Kaufler (Abstr., 1904, i, 207); this condensation is now found to 
take place readily with o-diaminoanthraquinones and either aliphatic 
or aromatic aldehydes. 

The compounds prepared from 1:2- diaminoanthraquinone and 
1:2: 4-triaminoanthraquinone respectively with benzaldehyde are 
identical with those obtained from the benzoyl derivatives of these 
compounds when heated with sulphuric acid (compare preceding 
abstract), whilst 1 : 2-diaminoanthraquinone with para-acetaldehyde in 
concentrated sulphuric acid at — 10° yields the 1 : 2-methylanthra- 
quinoneiminazole also previously described. F. M. G. M. 

[Preparation of Anthraquinoneacridone Derivatives.] 
Aktien-Gesellschaft fur Anilin-Fabrikation (D.R.-P. 238977 and 
238978). — Anthraquinoneacridone can be conveniently nitrated with 
nitro-sulphuric acid at — 5° ; the nitrated product is yellow, and does 
not fuse at 300° ; when reduced with sodium sulphide at 100°, it 
furnishes aminoanthraquinoneacridone (not melted at 300°). 

Benzoylaminoanthraquinoneacridone separates in crystalline form 
when a nitrobenzene solution of aminoanthraquinoneacridone is boiled 
with benzoyl chloride ; the acetyl compound has also been prepared. 
The second patent states that the foregoing benzoylaminoanthra- 
quinoneacridone can be obtained by boiling a nitrobenzene solution of 
bromoanthraquinoneacridone with benzamide in the presence of copper 
and sodium carbonate during twenty-four hours. F. M. G. M. 

Nature of the Indanthren Fusion of 2-Aminoanthra- 
quinone: 2-Hydroxylamino- and 2 :2'-Azoxyanthraquinone. 
Roland Scholl and Fritz Eberle (MonatsL, 1911, 32, 1035 — 1042). 
— 2-Hydroxylaminoanthraquinone, obtained in small quantity by 
reduction of 2-nitroanthraquinone, could not be converted into 
indanthren by fusion with an alkali hydroxide. In alkaline solution 
hydroxylaminoanthraquinone is very readily oxidised by atmospheric 



i. 142 



ABSTRACTS OF CHEMICAL PAPERS. 



oxygen to 2 : 2'-ozoxyanthraquinone. This compound could not be] 
reduced to the corresponding hydrazoanthraquinone, 2-aminoanthra-| 
quinone always resulting. 

The formation of indanthren from 2-aminoanthraquinone 
explained on the assumption that on fusion with an alkali hydroxide 
2-aminodihydro-l : 2'-dianthraquinonylamine, 

NH2-Cj4He(OH)./NH-Ci,Hy02, 
is formed, and that this loses hydrogen, forming dihydroindanthren, 

C„H„(OH),<^g>Ci,HA. 

Hydroxylaminoaiithraquinone, C^^H^Og'NH'OH, was obtained as an; 
orange-red solid, sintering at 140°, m. p. 158 — 160°. It dissolves in 
dilute sodium hydroxide with an intense green coloration. 

2:2'-Azoxyanthraquinone, ON2(CgHg<^p!x^CgH^)2, crystallises in I 

small, light brown prisms and prismatic plates, m. p. 342-5°. The 
solution in concentrated sulphuric acid is red. A solution in hot 
acetone gives a very characteristic cornflower-blue coloration on the 
addition of a few drops of sodium hydroxide. E. F. A. 

[Preparation of Dime thylin dan thren.] Badische Anilin 
Soda-Fabhik (D.R.-P. 238979). — 3 : d'-Dimethyhndant?iren, a bluish- 
grey, crystalline powder, can be prepared by* boiling an acetic acid 
solution of 2-amiDO-3-methylanthraquinone (1 part) with lead peroxide 
(3 parts) during three hours, or by boiling a naphthalene solution 
of l-bromo-2-amino-3-metl)y]anthraquinone with copper oxide and 
anhydrous sodium acetate during four to five hours. A similar 
compound can be obtained from 2-amino-6(7)-methylanthraquinone. 

F. M. G. M. 

Action of Semicarbazide on Hydroxamic Acids. Hans 
RuPE and F. Fiedler {J. jyr. Chem., 1911, [ii], 84, 809— 816).— It 
has been shown previously (Rupe and Kessler, Abstr., 1910, i, 93) 
that the action of semicarbazide hydrochloride on aliphatic oximino- 
ketones leads to the n placement of the oximino-group by the semi- 
carbazide residue, IN'NH-CO'NHg. A similar elimination of the 
oximino-group is found to take place with hydroxamic acids, resulting 
in the formation of semicaibazidts. The reaction is, however, not a 
general one. The replacement occurs readily with benzhydioxamic 
and acetbydroxamic acids, and with difficulty in the case of phenyl- 
acethydroxamic acid, whilst with salicyl hydroxamic and cinnam-] 
hydroxamic acids no reaction takes place. 

Benzoylsemicarbazide, obtained by heating benzhydroxamic acid 
with semicarbazide hydrochloride in aqueous solution, has m. p. 215°, 
and may also be prepared by the action of ethyl benzoute or benzoic; 
anhydride on semicarbazide. The high m. p. (225°) given by Widmanni 
and Cleve (Abstr., 1898, i, 335) is due to the presence of hydrazo- 
dicarboxylaniide. The acetyl derivative, CjoHjjOgNg, forms lustrous,, 
white leaflets, m. p. 174°, and is instantly hydroiy.^ed by cold aqueous 
sodium hydroxide. 

Cinnamoylsemicarbazide, ^nfiifi^^y prepared by heating cinnamic] 



ORGANIC CHEMISTRY. i. 143 

anhydride with semicarbazide, crystallises in needles ; the acetyl 
derivative forms slender, white needles, m. p. 177 — 178°. 

Phenylacetylsemicarhazide, OyH^jOgNg, obtained from the acid 
chloride or anhydride in a similar m inner, or by the interaction 
of phenylhydroxamic acid and semicarbazide hydrochloride in aqueous 
solution, crystallises in slender needles, m. p. 167 — 168°. F. B. 

Azines and Quinonediazides of the Anthraquinone Series. 
Roland Scholl, Fritz Eberle, and Walter Tritsch {Monatsh., 1911, 
32, 1043 — 1056). — (1) Azines from Triaminoanthraquinone. — On con- 
densing 1:2: 3-triaminoanthraquinone with o-dicarbonyl compounds, 
azines of entirely different nature are to be expected, according as the 
pycazine nucleus becomes attached in the angular 1 : 2-position or the 
linear 2 : 3-position. The linear derivatives should possess the same 
properties as the azines from 2 : 3-diaminoanthraquinone (Scholl and 
Kacer, Abstr., 1905, i, 88), characterLsed by their giving brown 
reduction products with alkaline sodium hyposulphite (Scholl and 
Edlbacher, Abstr., 1911, i, 756). 

Oxalic acid, benz'l, 1 : 2-naphthaquinone, phenanthraquinone, and 
isatin yield azines with triaminoanthraquinone, which all form 
insoluble brown products in alkaline sodium hyposulphite. The azines 
are accordingly regarded as linear (for nomenclature see Scholl, Abstr., 
1911, i, 677). 1:2: 3-Triaminoanthraquinone has m. p. 325° 
(decomp.). 

Dihydroxy-^ : Z-pyrazino-\-aminoanthraquinone (annexed formula), 

VO NFT N produced on condensation with oxalic acid, 

2/^ sublimes in lustrous, dark brown needles. 

It is not melted at 400°; in boiling with 

dilute sodium hydroxide, it dissolves, giving 

a red solution, from which a red sodium salt 

separates on cooling. 

Diphenyl-2 : 3-pyrazino-l-aminoanthraquinonp., 

c.h4«>c,h(nh,)4:?^;, 

prepared by condensation of triaminoanthraquinone and benzil, 
crystallises in tiny red or brownish-red needles, m. p. 241°; it sublimes 
without decomposition, and gives a red coloration with concentrated 
sulphuric acid. 

2 :'d{V : 2'-)-N'aphthazino-l{ov i-)-aminoanthraquinone is obtained 
as a dark brown, amorphous compound, m. p. 266 —267°. 

2 : 3(9' : 10' -)-Fhenanthrazino-l-aminoanthraquinon« crystallises in 
well formed, reddish-brown, lustrous needles, m. p. 361°. 

2 : 3-Indazino-l {or ^-)-aininoanthraquinone forms a dark brown, 
indefinitely crystalline powder, m. p. above 400°. When heated with 
sodium hyposulphite and sodium hydroxide it forms a reddish-brown 
vat, which dyes cotton yarn light brown. 

(2) Quinoneazides of the Anthraquinone Series. — The quinonediazides 
of the anthraquinone series in contrast to those of the benzene 
series cannot be coupled with naphthol or naphthylamine to azo- 
dyes. With resorcinol they couple only very slowly on prolonged 
heating. 




i. 144 ABSTRACTS OF CHEMICAL PAPERS. 



2 :6-I)ibroinoanlhraquinofie-l :b-bifidiazonium sulpJtate (I), produce 
on diazotisiiig dibromodiaminoauthraquinone, separates in yellowish 
red cryatals, m. p. 185 — 186^. When boiled with dilute sulphuric 
acid it is converted into anthrckquinone-l : 1 : 6 : b-hiaquinonediazide (II). 

CO N2-S04H 
Br 



I 






(11.) 

This crystallises in well-formed, metallic-green, lustrous crystals, 
which explode at 156°. 

4:6: S-Tribr07HO-b-hydroxyanthraquinone-2 : \-quinonediazide (III), 
prepared by diazotising 2:4:6: 8-tetrabromo-l : 5-diaminoantlira- 
quinone and boiling the crude diazo-product, was obtained in a brown, 
crystalline form from acetone, which blackens and sinters above 360°. 

E. F. A. 

[Preparation of j/r-Azimino-compounds.] Chemische Fabrik 
Gkiesheim-Elektron (D.R.-P. 238253). When the azo-compounds 

obtained by the combination 
of )3 - diazoanthraquinones with 
p - naphthylamine are oxidised 
they yield i/^-azimino-corapounds, 
such as ap-naphthylene-\l/-azimino- 
P - anthraquinonyl (annexed 
formula). The sulphonic derivatives are soluble in water, and form 
valuable cotton dyes. F. M. G. M. 

Action of Hydrazoic Acid on Cyanogen. Formation of 
Cyanotetrazole. E. Oliveri-Mandala and T. Passalacqua 
{Gazzetta^ TJl 1, 41, ii, 430 — 435. Compare Oliveri-Mandala, A bstr., 
1910, i, 343; 1911, i, 337; Oliveri-Mandala and Coppola, Abstr., 
1910, i, 593; Oliveri-MandaU and Alagna, Abstr., 1911, i, 243; 
Dimroth and Fester, Abstr., 1910, i, 645). — When cyanogen is passed 
into a 40% aqueous solution of azoimide, cyanotetrazole [tetrazole-5 
ccvrboxylonitrile], CjHNg, is produced. The substance becomes slightly 
red at 70° and melts at 99°, forming a reddish-brown liquid. It 
yields ammonia quantitatively when boiled with potassium hydroxide 
solution. The silver salt, CaN^Ag, and the barium salt, 

(C2N,)2Ba,3JH20, 
were prepared. 

When the silver salt of cyanotetrazole is treated with ethyl iodide, 

C^CNVNEt 
l-ethyltetrazole-5-carboxylonitrile, I xr^-^' ^^ obtained; it is a 

coloui'less liquid, b. p. 127°/46 mm. On distillation at ordinary 
pressure, it explodes at about 200°. l-EthyUetrazole-5-carboxylamide, 
C4H7ON5, is prepared by heating at 50 — 60° an alkaline solution of 
l-ethyltetrazole-5-carboxylonitrile with hydrogen peroxide solution ; 



ORGANIC CHEMISTRY. i. 145 

it crystallises in minute, lustrous scales, m. p. 125 — 126°. \-Elhyl- 
tetrazole-5-carboxylic acid, C^HgOgN^, is obtained by heating l-ethyl- 
tetrazole-5-carboxylonitrile with methyl-alcoholic potassium hydroxide, 
and neutralising the potassium salt with sulphuric acid. The acid 
crystallises in acicular prisms, m. p. 124 — 125°. In addition to the 
potaasium salt, C^HgOgN^K, the silver salt, C^HgOgN^Ag, was pre- 
pared. When l-ethyltetrazoie-5-carboxylic acid is kept at 130 — 140° 
it loses carbon dioxide, and 1-ethyltetrazole (identified as platini- 
chloride) is obtained, identical with the iV^-ethyltetrazole formerly 
described. K V. S. 

Identity of the Guanine Pentoside from Molasses with 
Vernine. Ernst Schulze and Georg Trier {Zeitsch. physiol. Ghem., 
1912, 76, 145 — 147). — Yernine (guanine-c?-ribose), for which the com- 
position C^oQ-^fi^ r^,213.^0 was recognised by Schulze and Castoro 
(Abstr., 1904, ii, 506), is identical with the guanosine obtained by 
Levene and Jacobs from nucleic acid, and with the guaninepentoside 
isolated by Andrlik (Abstr., 1911, i, 397) from molasses. In 1*5% 
sulphuric acid it has [a]g^ - 8-4°. E. E. A. 

The Fastness to Light of Hydroxyazo-compounds. Some 
Derivatives of a-Methoxy naphthalenes. N. Woroshzoff {Zeitsch. 
Farb.-Ind., 1911, 10, 169— 173).— It is found that the alkylation of 
the hydroxy-group in hydroxyazo-compounds increases the fastness to 
light of the colouring matters obtained therefrom, and that methyl- 
ation can be conveniently carried out by shaking an alkaline solution 
of the compound with methyl sulphate. 

Sodium i-methoxynaphthale7ie-4:-sulphonate, prepared by shaking 
a-naphthol-4-sulphonic acid with methyl sulphate in the presence of 
sodium hydroxide, separates in glistening leaflets. 

4:-Nitro-l-methoxynaphthalene, yellow needles, m. p. 81°, is obtained 
by slowly adding an intimate mixture of the foregoing acid (10 parts) 
and anhydrous sodium carbonate (0*6 part) in small portions to a 
cooled solution of 1*5 grams of carbamide in 20 c.c. of nitric acid 
(D 1 -4) ; on reduction with stannous chloride and hydrochloric acid it 
furnishes ^-methoxy-a-naphthylamine hydrochloride in colourless crystals; 
the free base is a dark oil ; its acetyl derivative has m. p. 180 — 181°. 

E. M. G. M. 

Salicylic Acid Azo-dyes. Eugen^ Grandmougin {Ber., 1911, 44, 
3756). — A claim for priority against Bulow (Abstr., 1911, i, 338). 

D. E. T. 

Decomposition of Azines by Heat. I. and II. Paul Pascal 
and L^ON Normand {Bull. Sac. chim., 1911, [iv], 9, 1029—1037, 
1059— 1068).— Curtius and Jay (Abstr., 1889, 393) showed that 
benzaldazine decomposes when heated, forming stilbene, and Bouveault 
obtained di-/>-methylstilbene in a similar way from tolualdazine 
(Abstr., 1897, i, 347, 530), but failed to generalise the reaction. lu 
the first of these papers the authors show that, in general, the aromatic 
aldazines melt with very slight decomposition, but when the tempera- 



i. 146 ABSTRACTS OF CHEMICAL PAPERS. 

ture ia raised above the melting point, evolution of gas commences and 
increases with rise of temperature, the principal reaction being the 
production of nitrogen and the stilbene corresponding with the aldazine 
used. At the higher temperatures some ammonia and hydrogen are 
formed, with, as a solid product, the corresponding phenanthrene, due 
to loss of H atoms at positions contiguous to the azine side-chain. 
The rate of decomposition was determined by measuring the gas 
evolved. By plotting temperatures as abscissae and volumes of (1) 
nitrogen and (2) ammonia disengaged as ordinates, two curves were 
obtained cutting one another on the temperature axis, and thus giving 
the temperature of decomposition, which is sometimes 50° below that 
actually observed subjectively. When the evolution of gas ceases, the 
contents of the tubes were distilled, and give as a rule (1) a mixture of 
aldazine and the stilbene ; (2) green oils containing the phenanthrene ; 
(3) red oils, and (4) a resinous or coke-like residue. In the case of the 
*' red oils " from benzaldazino the chief constituent is a substance, 
m. p. 261°, b. p. 460°, crystallising in long needles and giving a yellow 
picrate, m. p. 198°; it may be identical with the product CggH^gNg 
obtained by Curtius from benzoin-hydrazine. The amounts of this 
substance and its homologues produced increase with rise in the 
molecular weight of the aldazine employed. 

Benzildazine, CHPh.'NgiCHPh, begins to decompose at 275°, furnish- 
ing stilbene, phenanthrene, and the product C28H23N3 already referred 
to. Tolualdazine, C.^H^MelNglCgH^Me, begins to decompose at 314°, 
forming di-p-methylstilbene, ui. p. 181°. Cumincddazine, 

CfiH^Pr^-OHrNglCH-CeH^Pr^ 
m. p. 1136°, forms yellow leaflets, aud begins to decompose at 281°, 
yielding di-p-isopropylstilbetie, CgH^Pr^-CHICH-CgH^Pr^, m. p. 129°, 
which separates from alcohol in colourless scales, and yields a dibromide^ 
m. p. 186 — 187° (approx., decomp.), crystallising in small, brilliant, 
•colourless spangles. 

ip-Methylbenzaldazine, CHPhlNglCH'CgH^Me, m. p. 112°, forms pale 
yellow crystals from alcohol, and when heated gives jt?-methylstilbene 
m. p. 119'6°. Aldazines in which the benzene nucleus is replaced by 
naphthalene decompose only at high temperatures, and the unsaturated 
product is difficult to free from tarry by-products. Furfuraldazine, 
C^OH^'CHINgiCH'C^OH^, is decomposed by heat, yielding furfuryl- 
stilbene, m. p. 97*4°. 

The aliphatic azines of low molecular weight distil easily, and 
decompose only at a red heat. The higher terms decompose slowly 
on distillation, forming a fluoi'escent liquid with an odour of 
petroleum and of pyridine bases ; there is no evolution of nitiogen or 
ammonia. 

Di-^-c1dorobenzaldazinef m. p. 211°, forms yellow spangles from 
alcohol or boiling benzene ; it begins to decompose at 284°, furnishing 
di-p-chloro8tilbene, m. p. 153'8°, in silver-grey spangles, which yields a 
dibromide, m. p. 195 — 197°. Di-^-iminobenzaldazine, m. p. 245°, 
obtained by the interaction of /?-aminobenzaldehyde with hydrazine 
sulphate, is a yellow powder ; it begins to decompose at 307°, giving off 
a little nitrogen and much ammonia, so that it was impossible to 
isolate di-^aminostilbene from the accompanying tarry by-products. 



ORGANIC CHEMISTRY. i. 147 

Di-0-methoxybeDzaldazine begins to decompose at 270°, and yields 
80% of di-o-methoxystilbene, m. p. 136°, which separates from alcohol 
in colourless crystals and gives a dihromide, m. p. 190°; the corre- 
sponding 77ie)5a-compound furnishes di-m-methoxystilbene, m. p. 97*5°, 
the dibrornide of which, m. p. 183*5 — 184*5° is colourless and crystal- 
line. Di-jo-methoxybenzaldazine begins to decompose at 289°, and 
yields di-jt?-methoxystilbene, m. p. 213°. Di-o-ethoxyhenzaldazinej 
m. p. 131*6°, forms yellow crystals, and commences to decompose 
at 287°, giving di-o-ethoxystilhene, m. p. 87*5°, colourless crystals, the 
dibromide of which, m. p. 218 — 219°, forms pale yellow crystals. 
Bi-ip-ethoxybenzaldazine, m. p. 172*3°, crystallises in pale yellow lamellae, 
and begins to decompose at 308°, furnishing di-/?-ethoxystilbene, 
ra. p. 208° 

Di-o-benzyloxybenzaldazine^ m. p. 157*7°, yellow plates, gives di- 
o-benzyloxystilbene, m. p. 117*6°, in small, brilliant, colourless 
spangles, whilst the corresponding para-compound, m. p. 209*3°, pale 
yellow leaflets, decomposes less easily, forming a bulky " coke " from 
which no stilbene derivative has yet been isolated. T. A. H. 

Decomposition of Azines by Heat. III. Paul Pascal and 
Leon Nokmand {Bull. Soc. chim., 1912, [iv], 11, 21 — 25. Compare 
preceding abstract). — The methoxynaphthaldazine gives only a small 
yield of dimethoxynaphthylethylene at 362°. Veratraldazine gives but 
little 3:4:3': 4'-tetramethoxystilbene, whilst the azine from piperon- 
aldehyde, N2(ICH*CgH3l02lCH2)2, does not yield a corresponding 
stilbene. The main conclusions arrived at from results described in 
this and the preceding abstracts are as follows. 

Aromatic azines decompose at about 300°, evolving nitrogen and 
ammonia, and giving stilbene derivatives, the yields being increased if 
the position ortho to the group 'CHINg! is filled by any radicle. In 
the same homologous series the yield diminishes on ascending the 
series. If a substituent group, such as amino-, in the nucleus of the 
azine possesses a residual affinity, the yield of stilbene compound is 
considerably lowered. Esterification in the case of several hydroxy- 
groups attached to each aromatic nucleus does not prevent decom- 
position. 

A study of the physical constants of the azines and stilbenes shows 
that the introduction of one or more atoms of oxygen into the molecule 
produces a rise in the melting point. The reverse is the case if a 
hydroxyl group is replaced by a methoxy- or ethoxy-group. Finally, 
the more symmetrical the molecule the higher is the melting point. 

W. G. 

The Existence of Sulphur Fixed as Sulphite in Wool. 
H. Strunk and Hans Priess (Zeitsch. physiol. Chem., 1912, 76, 
136— 144).— Eaikow (Abstr., 1905, i, 725; 1907, i, 666; compare 
Grandmougin, Chem. Zeit., 1907, 31, 174) has stated that wool, when 
kept for some time in contact with large quantities of concentrated 
phosphoric acid, liberates small quantities of sulphurous acid. This is 
confirmed, but the amount, 0*0064 gram of sulphur dioxide from 300 
grams of wool, is too small for it to be assumed that part of the 



i. 148 ABSTRACTS OF CHEMICAL PAPERS. 



^ 



Hulphur in the keratin molecule is united with oxygen as sulphite 
Dry wool has a very pronounced affinity for hydrogen sulphide ; this 
is sufficient to explain the variations experienced in the amount of 
sulphur in wool. The hydrogen sulphide fixed by the wool is easily 
oxidised to sulphurous and sulphuric acids, and it is probable that a 
small quantity of sulphurous acid may arise in the wool of the living 
animal in such manner. E. F. A. 

The Separation of Rennet and Pepsin. W. E. Burge (Amer. 
J. Physiol. f 1912, 29, 330 — 334), — The passage of a direct current of 
10 milliamperes for twenty-four hours through a solution containing 
both enzymes causes a complete destruction of peptic activity, but 
leaves the rennet apparently unchanged. W. D. H. 

Activation of Sucrase [Invertase] by Different Acids. 
Gabriel Bertrand, M. Rosenblatt, and (Mme.) M. Rosenblatt 
{Gompt. rend.f 1912, 154, 1515 — 1518). — The effect of the more common 
organic and inorganic acids on the diastatic activity of sucrase has 
been determined under conditions more precisely defined than those of 
other observers. In each case the optimum concentration of acid was 
determined. The results, which are displayed in tabular form, show 
that, generally speaking, the order of efficiency in which the acids stand 
as activating agents is the same as Ostwald's order for their activity 
as catalysts in hydrolysis. Hydrochloric and nitric acids, however, 
are exceptions to the rule, being less effective as activators than as 
catalysts. W. O. W. 

Action of Phosphatese. Hans Euler and Sixten Kullberg 
{Zeitsch. physiol. C/tem., 1912, 76, 241. Compare Abstr., 1911, i, 1051 ; 
this vol., i, 61). — Reference is made to von Lebedeff's work, which 
does not agree with that of the authors ; perhaps different kinds of 
yeast will explain the discrepancy ; no further experimental work is 
adduced. W. D. H. 

4-Amino-3-hydroxyphenylarsinic Acid and its Products of 
Reduction. Ludwig Benda {Ber., 1911, 44, 3578 — 3582. Compare 
this vol., i, 61 — 64). — 3-Nitro-4-aminophenylarsinic acid can be 
diazotised in the usual way, yielding a solution of a diazonium salt, 
which loses the •AsO(OH)2 group when boiled with dilute sulphuric 
acid. However, by treatment with sodium acetate to destroy the 
mineral acid, the solution of the diazonium salt exchanges its nitro- for 
a hydroxyl group ; the solution of the resulting diazonium salt can be 
coupled with alkaline ^-naphthol to form a red azo-dye, which is 
reduced by sodium hyposulphite or by sodium hydroxide and aluminium, 
yielding l-amino-2-naphthol and Ai-amino-Z-hydroxyphenylarsinic acid, 
NH2-C0H3(OH)-AsO(OH)2, the sodium salt, C6H704NAsNa,5H20, and 
silver salt of which are described. 

Under suitable conditions, the red azo-dye is reduced by sodium 
hyposulphite, yielding 4:4'- diamino -3:3'- dihydroxyarsenobenzene, 
As2[CgH3(NH2)*OH]2, the hydrochloride and sulphate of which are 
(iescribed. C. S. 



i. 149 



Organic Chemistry. 



/^1 



Catalysis and the Formation of Petroleum. Carl Engler 
and E. Severin {Zeitsch. angew. Chem.^ 1912, 25, 153 — 158). — Re- 
petition of KUnkler's experiments on the distillation of crude oleic and 
stearic acids at atmospheric pressure {Chem. Zentr.^ 1910, i, 2031) 
shows that decomposition begins at 34U° and 358° respectively, and 
that the formation of hydrocarbons is small and commences at about 
400°. The suggestion of Kiinkler and Schwedhelm (Abstr., 1909, 
i, 281) that soaps may first be formed by the interaction of lime or 
alumina with fats, and that these under the influence of heat may give 
rise first to ketones, and eventually to the hydrocarbons of petroleum, 
is untenable, since ketones have not been found either in bitumens or 
petroleum, and no indication of the existence of soaps in bitumen could 
be found by the authors. Various investigators have suggested that 
rock-forming materials by their action on organic remains may play 
some part in the formation of petroleum, and some support to this 
view is afforded by the work of Sabatier, Senderens, and Mailhe on 
the catalytic decomposition of aliphatic acids and their esters by 
metallic oxides (compare Ipatieff, Abstr., 1904, ii, 644, 645; 1911, 
i, 937), and Grafe (Petroleum, 1910, 6, 71) has pointed out that 
Lycopodium spores distilled with fuller's earth afford a distillate 
similar in character to Scottish shale oil. The authors have therefore 
examined the distillates obtained from mixtures of oleic or stearic acid 
with diatomite, fuller's earth, quartz sand, and finely powdered quartz, 
and find that these materials lower the temperature of decomposition 
and give rise to distillates richer in hydrocarbons than are obtained 
when the acids are distilled alone. Powdered quartz is the most 
efficient of the four, followed by fuller's earth, which is better than 
either diatomite or sand (compare Hviid, Petroleum, 1910, 6, 429). 
The distillates, full details of which are given in the original, in 
general resemble those obtained by distillation of fatty acids under 
pressure (Abstr., 1888, 928), but contain more undecomposed acid 
and less low-boiling hydrocarbons. The conclusion is drawn that in 
the conversion of organic remains into petroleum, the influence of rock- 
forming materials as well as of time, temperatute, and pressure must 
be taken into account. T. A. H. 

Presence of Cholesterol in Java Naphthas. Carl Engler and 
WiLHELM Steinkopf {J. Russ. Phys. Chem. Soc, 1911, 43, 1820—1825). 
— The work of Koss (Abstr., 1911, i, 761), which was carried out 
partly under the supervision of the authors, and also its unauthorised 
publication are severely criticised. T. H. P. 

IK Valency of Carbon in So-called Unsaturated Compounds. 
IBiEXEi E. TscHiTSCHiBABiN (J. Russ. Phys. Chem. Soc, 1911, 43, 
|B90 — 1735). — A discussion of the various explanations which have 

IK ^^^' ^^^' •• '^ 



i. 150 ABSTRACTS OF CHEMICAL PAPERS. 

been advanced of the unsaturated character of the carbon atom in 
different classes of organic compounds. T. H. P. 

/9)8y-TrimethylpeDtane. Latham Clarke and Webster Newton 
Jones {J. Avier. C/iem. JSoc, 1912, 34, 170 — 174). — In continuation of 
a study of the octanes (Abstr., 1911, i, 354, and earlier abstracts), 
)8^y-trimethylpentane has now been synthesised. By the action of 
magnesium ethyl bromide on pinacolin, )8^y-trimethylpentan-y-ol was 
produced, nnd was converted into y-iodo-^^y-trimethylpentane by the 
action of iodine and amorphous phosphorus. On treating this carbinyl 
iodide with alcoholic potassium hydroxide, ^)8-dimethyl-y-methylene- 
pentane was obtained, and on passing this over finely divided 
nickel at 160° in a current of hydrogen, fl^y-trimethylpentane was 
produced. 

P(3y-Tri7nethylpentan-yol, CMe3-CMe(OH)-CH2Me, b. p. 149—152°/ 
760 mm., is a colourless liquid with a camphor-like odour. The 
octylene {(3(i-dimethyl-y-rnethyle7iepentane)f CMe3'C(ICH2)*CH2Me, b. p. 
110*4 — 110*8°/760 mm., is a colourless, mobile liquid with a faint, 
musty odour. IS/3y-Trimethylpentane, CMeg'CHMe'CHgMe, b. p. 
110-5— 110-8°/760 mm., l)]l 07219, nff 1-4164, is a colourless, mobile 
liquid with a very faint odour. E. G. 

/88-Dimethylheptane. Latham Clarke and Sydney A. Beggs 
(J. Amer. Chem. Soc, 1912, 34, 60 — 62). — In continuation of the 
work on the nonanes (following abstract), ySS-dimethylheptane has 
been synthesised. 

When )8-methyl-8-pentanone (methyl isobutyl ketone), obtained by 
the hydrolysis of ethyl isopropylacetoacetate, is treated with magnesium 
w-propyl iodide, the nonylene (^-methyl-S-rfiethyleneheptane), 

CH2Me-CH2-C(:GH2)-CH2-CHMe2, 
b. p. 132 — 133°, is obtained as a colourless liquid with an odour 
resembling that of petroleum. The position of the double bond was 
not established, but there is little doubt that the formula assigned to 
the compound is correct. On passing a mixture of the nonylene and 
hydrogen over freshly reduced nickel, (SS-dimethyUiejitane, 

CH2Me-CH2-CHMe-CH2-CHMe2, 
b. p. 132-9— 133°/752 mm., D}'^ 0-7206, <' 1-4014, is produced as a 
colourless liquid with a petroleum-like odour. E. G. 

/EJc-Dimethylhept^Cie. Latham Clarke and Sydney A. Beggs 
{J. Amer. Chtm. Soc.^ 1912, 34, 54 — 60). — In a study of the octanes 
(Abstr., 1911, i, 354, and earlier abstracts), certain relations have 
been discovered between the chemical constitution and physical 
properties. An investigation has been undertaken in order to ascer- 
tain whether similar relations occur in the nonane series, and an 
account is now given of the synthesis and properties of ySc-dimethyl- 
heptane which has been obtained previously in an impure state by 
Welt (Abstr., 1896, i, 332). 

The synthesis was effected in the following manner. )3-Methyl-c- 
heiuinone, obtained by the hydrolysis of ethyl rsobutylacetoacetate, 
was converted into /Se-dimethyl-c-heptanol by means of magnesium 



ORGANIC CHEMISTRY. i. 151 

ethyl bromide. The iodide of this alcohol was prepared, and when 
boiled with alcoholic potassium hydroxide yielded ^-methyl-e-methylene- 
heptane, which was then reduced to j8e-dimethylheptane. 

Pe-DimethyU-heptanoh CH2Me-CM:e(OH)-CH2-CH2-CHMe2, b. p. 
172 — 174°, is a colourless liquid with an odour of musty apples. The 
nonylene (p-methyl-e-rnethyleneheptane), 

CH2Me-C(:CH2)-CH2-CH2-CHMe2, 
b. p. 139 — 140°, is a colourless liquid with a sweet, petroleum-like 
odour. /?e-Dimethylheptane, CH2Me-CHMe-CH2-CH2-CHMe2, b. p. 
135-6— 135-97760 mm., Dl^ 0-7190, n^ 1-4020, obtained by passing a 
mixture of the nonylene and hydrogen over freshly reduced nickel at 
160 — 180°, is a colourless liquid with a petroleum-like odour. 

E. G. 

Conjugated aci-Nitro-compounds. Arthur Hantzsch and Kurt 
VoiGT (Beo'., 1912, 45, 85 — 117). — A number of nitro-compounds, 
chiefly aliphatic substances containing NOg attached to carbon, have 
been examined spectrometrically to determine how the absorption 
spectrum is affected when the real nitro-group is changed to an aci- 
nitro-group. The chief result of the investigation has been the 
discovery of a new type of nitro-compound, which is called a 
conjugated aci-nitro-compound. 

The nitro-group may be present in a substance in three forms, each 
of which has its characteristic absorption curve. Aliphatic real nitro- 
compounds show very feeble selective absorption, the curves exhibiting 
a very flat band or a kink beginning at oscillation frequency 3413. 
It is immaterial whether the nitro-group is the only negative 
substituent in the molecule or whether another- (JSr02, NOH, CO, 
CO2H, COgEt, C0-NH2, CN, Ph) is present, provided that the 
introduction oi the latter does not produce a constitutive change 
in the nitro-group. A simple aci-nitro-group, ^CINO'OH, causes 
weak general absorption ; such groups are present only in the salts 
of the nitroparatfins, CHRINO'OM. When, however, an aci-nitro- 
group is present together with another negative group, X (one 
of those mentioned above), then, without exception, the substance 
exhibits very strong, selective absorption, the curve exhibiting 
a very deep band for thicknesses corresponding with 10 to 100 mm. 
of i\^/ 10,000 solution. Since the introduction of a negative group 
into a real nitro-compound has little optical influence, whilst a 
simple aci-nitro-group alone causes general absorption, it follows that 
the strong selective absorption exhibited by a substance containing 
both an «ci-nitro- and another negative group must be conditioned 
by the influence of these two groups on one another. This influence 
is represented by a peculiarly constituted, six-membered ring, pro- 
duced by the union, by a supplementary valency, of a metallic or 
hydrogen atom, or of an alkyl group with a negative atom of the 

v. 

negative (unsaturated) group X : R'C%j^^^'^^(Na,H,Me). For 

examples, X is a nitro-group in aci-dinitro-compounds (salts of di- and 
tri-nitromethane), an K'CO group in a-aci-nitroketones (the nitio- 
barhituric acids ; ethyl rtc?-nitromalonate), and a cyano-group in a-cyano- 

7fl 2 



i. 152 ABSTRACTS OF CHEMICAL PAPERS. 

oct-nitro-oompoiinds (fulminuric eaters ; aci-nitrocyanophenylmethane). 
An act-nitro -group in this state is called a conjugated act-nitro-group. 
Its presence explains why the introduction of a third negative group 
into the molecule exerts so slight an optical influence ; the third group 
can only have a feeble auxochromic effect. aci-Nitrophenylmethane 
and its salts contain a conjugated aci-nitro-group ; consequently the 
benzene nucleus, by means of a supplementary valency (in the ortho- 
or para-position), can form part of the six-membered complex. 

Certain conjugated aci-nitro-compounds (fulminuric acid and the 
nitrobarbituric acids) are so stable that they cannot be converted, even 
by concentrated sulphuric acid, into real nitro-com pounds. Further- 
more, substances containing a simple aci-nitro-group together with 
another unsaturated group are incapable of existence ; therefore, when 
a real nitro-compound containing another unsaturated group is trans- 
formed into an act-nitro-compound, a conjugated aci-nitro-group is 
always produced. 

The chromoisomerism of certain conjugated aci-nitro-compounds, for 

example, the yellow and the colourless salts of the nitrobarbituric 

acids, cannot be explained by regarding the yellow salt as containing 

a conjugated aci-nitro-group and the colourless salt as containing a 

simple rtci-nitro-group, because the latter group cannot exist in such 

compounds. Both salts contain the conjugated aci-nitro-group. The 

colour of the yellow salt is due to a shifting of the absorption band 

towards the red end of the spectrum. Chromoisomerism in such cases, 

therefore, is merely valency isomerism and is represented thus : 

-CIO- M , -C-0— M 

1 • and II : . 

-CINO-O -C-NOIO 

When the ionisation of a substance containing a conjugated aci- 
nitro-group is unaccompanied by secondary changes, the ions are 
optically identical with the undissociated acid, and therefore contain 
the peculiar pix-membered ring. This result leads to Werner's theory 
that the formation of ions is, in the first step, a case of hydrate 
formation. For the particular examples under discussion, the ionisa- 
tion is represented by the scheme : 

R-C<^.-^H,0'+H-. 

In conclusion, attention is drawn to the extensive optical and 
chemical analogies between negatively substituted nitrocompounds on 
the one band, and negatively substituted ketones (ethyl acetoacetate) 
on the other. C. S. 



Aliphatic Nitro-compounds. XII. Constitution of aci- 
Nitro-compounds. Wilhelm Steinkopf and Boris Jukgens (J. pr, 
CJiem., 1911, [ii], 84, 686—713. Compare Abstr., 1911, i, 530).— The 
formation of hydroxamic chlorides by the action of hydrogen chloride 
on aliphatic nitro-com{)Ounds is referred by the authors to the decom- 
position of the aci-nitro-compound into the corresponding aldehyde 
and nitroxyl, which then combine to form a nitroso-alcohol (I) ; the 
latter compound reacts with hydrogen chloride, yielding a chloronitroso- 



ORGANIC CHEMISTRY. i. 153 

compound (II), whicli then undergoes transformation into the hydrox- 
amic chloride (III), as shown in the following scheme : 
R-CH:N0-0H -> R-CHO + INOH — > (I) R-CH(NO)-OH -> 
(II) R-CHCl-NO -^ (III) R-CCKN-OH. 

This view is supported (1) by the observations of Nef (Abstr., 1895, 
i, 3), and also of Hantzsch and Veit (Abstr., 1899, i, 401), who find 
that aci-nitro-derivatives of hydrocarbons readily decompose into 
aldehyde, nitrous oxide, and water; (2) by the formation of hydr- 
oxamic acids by the direct combination of aldehydes and nitroxyl 
(Angeli), and (3) by the production of blue or green colorations, due to the 
formation of chloronitroso-compounds, R'CHCl'NO, when salts of the 
nitro-derivatives of aliphatic hydrocarbons are acidified in aqueous or 
ethereal solution. Attempts have been made to isolate these coloured 
compounds in the case of nitromethane, nitropropane, and nitro- 
ethane, but only with the last-mentioned compound were the attempts 
successful. When a suspension of the sodium salt of aci-nitroethane 
in a large volume of ether is treated with an excess of hydrogen 
chloride, and the resulting solution, after removal of the sodium 
chloride, rapidly evaporated, chloronitrosoethane (Piloty and Steinbeck, 
Abstr., 1902, i, 735) was obtained. If a small volume of ether is used 
and excess of hydrogen chloride avoided, the product consists of ethyl- 
nitrolic acid. The formation of the latter compound is due to the 
action of nitrous acid, produced by the decomposition of the 
intermediately formed nitroso-alcohol, NO'CMeH'OH, on unchanged 
nitroethane. 

Salts of nitro-compounds, such as nitroacetic acid and nitroaceto- 
nitrile, which contain strongly negative groups do not give blue or 
green colorations when treated with acids, and the conclusion is there- 
fore drawn that in these cases decomposition of the aci-nitro-compound 
into aldehyde and nitroxyl does not take place. 

This view is supported by the behaviour of w-nitroacetophenone, 
which on treatment with hydrogen chloride in ethereal solution yields 
(o-chloro-oo-oximinoacetophenone (Thiele and Haeckel, Abstr., 1903, i, 
160), without the intermediate formation of a coloured nitroso- 
compound. acz-Phenylnitromethane, which contains the feebly negative 
phenyl group, occupies an intermediate position ; with ethereal 
hydrogen chloride, it develops the blue coloration very slowly, instead 
of instantly as in the case of the nitro-derivatives of aliphatic hydro- 
carbons, and this coloration gradually disappears owing to the formation 
of benzhydroxamic acid. 

These differences in the behaviour of nitro-compounds are best 
explained on the assumption that the «ci-nitro-derivative has the 
CKH — N'OH, proposed by Hantzsch, and not the 



O 

Michael-Nef formula, CHRINO'OH, now generally accepted. The 
stability of the carbazoxy-ring depends on the nature of the sub- 
stituents. When K = H or alkyl, the ring is unstable, and readily 
suffers complete rupture, as indicated in the following scheme : 
R-CH-i-N-OH 

\y _^ R-OHO-t-IN-OH. 

O 



i. 154 ABSTRACTS OF CHEMICAL PAPERS. 

On the other hand, when K is a stron^'ly negative group, the 
stability of the ring is greatly increased, so that rupture occurs only 
at one jK)int, either between and O, with the formation of a nitro- 
compound as shown in (I) below, or between N and 0, with the formation 
of a hydroxamic acid as indicated in (II) : 

^ .. R-CH— N-OH 

R-CH5,-N<Q or R-CH2-N<i ^- \>< — > 

(II.) R-C<^H^H. 
The evidence furnished by Nef in favour of the formula 

r-ch:no-oh 

for aci-nitro-compounds is subjected to a critical examination, and the 
conclusion is drawn that Hantzsch's formula affords a simpler and less 
forced explanation of the behaviour of these compounds. 

Numerous examples of the reactions* of nitro-com pounds and of 
a large number of other classes of compounds containing the 
carbazoxy-ring are cited in support of the authors' view. F. B. 

Specific Gravity Table of Alcohol- Water Mixtures at 
17*5°. WiLHELM Fresenius and Leo GRt)NnuT (Zeiisch. anal. Chem., 
1912, 51, 123— 124).— A useful table giving Df' for a number of 
mixtures of alcohol and water, together with the corresponding 
alcohol % by weight and by volume, and also alcohol in grams per 
100 c.c. L. DE K. 

Action of Potassium Hydroxide on Secondary Alcohols ; 
Diagnosis of Primary and Secondary Alcohols of High 
Molecular Weight. Marcel Guerbet {Gompt. rend.y 1912, 154, 
222 — 225. Compare this vol., i, 67). — When secondary alcohols are 
heated at 230° with potassium hydroxide, some oxidation occurs with 
production of potassium salts of acids, but the greater part of the 
alcohol forms condensation products ; thus isopropyl alcohol yields 
formic and acetic acid, together with ^-methylpentan-S-ol and 
)38-dimethylheptan-^-ol. The corresponding higher homologues are 
obtained from «ec.-butyl alcohol and octyl alcohol. The ease with 
which the reaction is carried out renders it suitable for distinguishing 
between secondary and primary alcohols. W. O. W. 

Specific Gravity and Hygroscopic Power of Glycerol. 
Anton Kailan {Zeitsch. anal. CJiem.y 1912, 51, 81 — 101). — 
Anhydrous glycerol has DY' 1 •26413. The density between 14° and 
20°^can be calculated by the expression Dl= 1-26413 + (15 - 1) 0-000632, 
and a table is given of densities from 14-3° to 20- 6°. Boiling points 
under various pressures between 9 and 32 mm. are also recorded. 

Glycerol rapidly absorbs moisture from the air, and a number of 
determinations of the hygroscopic power of anhydrous and hydrated 
samples are given. It appears that a mixture containing 80% of 
glycerol is in equilibrium with air containing an average amount of 
moisture. 

The author also noticed that alcohol containing but little water 
absorbs, in the same circumstances, water four times more rapidly 
than does a similar glycerol. L. de K. 



ORGANIC CHEMISTRY. i. 155 

Preparation of Bpichlorohydrin from Dichlorohydrin and 
Alkalis. Farbenfabriken vorm. Friedr. Bayer &, Co. (D.R.-P. 
239077).— When dichlorohydrin (129 parts) in 200 parts of water 
is slowly treated with 133 parts of 30% sodium hydroxide solution, it 
yields 85 parts of epichlorohydrin ; the sodium hydroxide may be 
replaced by its equivalent of potassium or ammonium hydroxide, but the 
above concentrations must be carefully maintained. F. M. G. M. 

Tautomerism of the Dialkyl Phosphites. Thaddeus 
MiLOBENDZKi (Ber., 1912, 45, 298 — 303). — Previous investigations 
(Abstr., 1897, i, 391 ; 1908, ii, 488; 1903, i, 733; 1907, i, 8, 1899, 
i, 659) have indicated that dialkyl hydrogen phosphite in the free 
condition has the constitution (I) 0!PH(0fl)2. From the behaviour 
of the esters in aqueous solution, the author shows that they also 
exist in the tautomeric form (II) 0H'P(0R)2. 

Silver salts of the composition Ag'P0(0R)2 are precipitated from 
aqueous solutions of ditsopropyl hydrogen phosphite (b. p. 74 — 75°/ 
9 mm.) and diethyl hydrogen phosphite (b. p. 66 — 67°/9 mm.) by the 
successive addition of silver nitrate and aqueous alkalis (ammonia, 
sodium hydroxide, and barium hydroxide) ; the addition of the 
reagents in the reverse order produces no precipitate. 

According to the author the silver salts, 0Ag*P(0R)2, are readily 
soluble in water, and the non-formation of a precipitate, when the 
alkali is added before the silver nitrate is due to the transformation 
of the keto-ester (I) into the enolic form (II). 

The silver salts, Ag'P0(0R)2, dissolve in excess of alkali owing to 
change into the tautomeric form, induced by the hydroxyl ions ; on 
acidifying the alkaline solutions, the original salt is precipitated. 

Dialkyl hydrogen phosphites show the phenomenon of gradual 
neutralisation. The percentage of the ester (T) present in aqueous 
solutions has been determined by adding the equivalent amount of 
aqueous ammonia, followed immediately by the addition of silver 
nitrate ; the amount of silver salt, Ag'P0(0R)2, precipitated cor- 
responds with that of the ester of the formula (I) originally present ; 
with diethyl hydrogen phosphate the amount is 35%. 

That the enolic modifications of the esters are capable of existing 
in aqueous solution has also been shown by neutralising with aqueous 
barium hydroxide, and then adding the equivalent amount of sulphuric 
acid ; the solutions thus obtained do not show the phenomenon of 
gradtial neutralisation, nor yield insoluble silver salts. 

Triethyl phosphite is hydrolysed by excess of aqueous sodium 
hydroxide to sodium diethyl hydrogen phosphite ; dialkyl hydrogen 
phosphites are not hydrolysed by alkalis. 

Experiments are also described showing that sodium diethyl phosphite, 
prepared from sodium and diethyl hydrogen phosphite in ethereal 
solution, exists in aqueous solution in the form NaO*P(OEt)2. 

F. B. 

Constitution of Glycerophosphoric Acid Prepared by 
Eaterification of Phosphoric Acid or Sodium Dihydrogen 
Phosphate. Paul Carre (Compt. rend., 1912, 154, 220—222.^ 
Compare Abstr., 1904, i, 133, 215). — Sodium glycerophosphate, 

* and BiUl. Soc. chim., 1912, 11, 169—172. 



i. 156 AB8TKACT8 OF CHEMICAL PAPERS. 

propart'd by Poulenc's method, was converted into glyceropho8f)horic 
acid by tlio process previously described. The product is idpiilical in 
every respect with the acid formed in the direct esterification of 
phosphoric acid by glycerol. The same acid is obtained when glycerol 
bromohydrin (3 mols.) is heated with silver phosphate and the 
resulting unstable esUr, OP[0-CH2-CH(OH)-CH/OH]3, submitted to 
hydrolysis. Poulenc's compound must, therefore, be a salt of 
a-glycerophosphoric acid, and not of the /?-acid as stated by Paolini 
(Abstr., 1911, ii, 774). The author has been unable to obtain Paolini's 
brucine salt crystallising with 7H2O. W. O. W. 

Preparation of Glycol and Qlycolhydrin Esters of Phosphoric 
Acid Glycerides. Adolf Ghun and Fritz Kade (D.R.-P. 240075). 
—Compounds of general formulaX-C2H4-0-PO(OH)-0-C3H5(0-CO- 11)2, 
whtre R. is an alkyl group and X halogen or hydroxyl, can be readily 
prepared by the action of phosphoric oxide on distearin and ethylene- 
glycol or halogenhydrins. 

The following products are described : the compound ^ 
C2H,Cl-0-PO(OH)-0-C8H5(0-CO-Ci7H35)2, 
m. p. 65 — 66° ; the compound, 

OH-C2H,-0-PO(OH)-0-C3H,(0-CO-Ci7H,5)2, 
from ayS-distearinphosphoric acid ester, ethylenechloiohydrin, and 
glycol. The tHmethylamine salt, 

C2H4Cl-0-PO(0-NHMe3VO'C8H5(0-CO-Ci7Hg5)2, 
m. p. 69° ; and by the interaction of another molecule of trimethyl- 
amine, the salt, 

NMe3Cl-C2H,-0-PO(0-NHMe3)-0-C3H5(0-CO-Ci7H35)2. 

F. JVi. G. M. 

The Agglutination of Lecithins and Lecithin-protein 
Mixtures by Acids. J. Feinschmidt {Biochem. Zeitsch., 1912, 38, 
244 — 251). — Aqueous susjensions of lecithins of various origins have 
agglutination optima at definite hydrogen ion concentrations, which 
are identical with the isoelectric point. This varies in the different 
preparations between 10"^ and 10"*, that is, in somewhat strongly acid 
solutions. Neutral salts increase the turbidity of the solutions, but 
make the actual agglutination point less sharp. When lecithin and 
protein are mixed, a new complex is formed, in which the agglutination 
point shifts towards the less acid side ; in this case the precipitation 
is more energetic and coarser. S. B. S. 

Catalytic Decomposition of Formic Esters. Paul Sabatiee 
and Alphonse Mailhe (Compt. rend., 1912, 154, 49 — 52. Compare 
Abstr., 1911, i, 258 — 416).— The catalytic decomposition of alkyl 
formates below 400° is somewhat complicated, and follows a different 
course from that of esters of higher acids. In general, two principal 
reactions occur, represented by the equations: (1) 2H'C0^R = 
H-CHO + CO2 + Rg^' followed by the dehydration of the aldehyde 
with production of an unsaturated hydrocarbon ; (2) H*C02R = C0-H 
R'OH, followed by dehydration or dehydrogenation of the alcohol. 
The water set free may effect hydrolysis, the resulting formic acid 
then decomposing in the manner already described. 



ORGANIC CHEMISTRY. 1. 157 

The nature of the catalyst considerably influences the course of 
reaction; thus in the case of methyl formate and titanium oxide, 
reaction (1) predominates, whilst with zinc oxide reaction (2) occurs 
almost exclusively. Both reactions take place with thorium dioxide. 
Finely divided platinum, nickel, and copper readily effect catalysis, 
principally in accordance with equation (2). W. O. W, 



Catalytic Pormation of Saturated Aliphatic Esters from 
Formic Esters. Paul Sabatier and Alphonse Mailhe (Gompt. 
rend., 1912, 154, 175 — 177. Compare preceding abstract). — When 
the vapour of methyl formate and isobutyric acid in equimolecular 
proportions is passed over titanium oxide at 250°, carbon monoxide is 
liberated, and the condensed liquid contains 20% of methyl isobutyrate, 
together with methyl alcohol and some zsobutaldehyde. The esterification 
is explained by the decomposition of the methyl formate in the manner 
previously described, whilst the aldehyde arises from reduction of the 
acid by formic acid. Thorium oxide acts in the same way, but requires 
a higher temperature ; thus at 300 — 330°, isovaleric acid and methyl 
formate give 40% of methyl zsovalerate by volume and 16% of iso- 
valeraldehyde. Under these conditions the amount of ketone formed 
is inconsiderable, but at 370° the condensed liquid contains 50% of 
ester, 10% of isovalerone, 15% of isovaleraldehyde, and also methyl 
alcohol. 

Similar results have been obtained with higher acids and other alkyl 
formates. The direct reduction of acids by means of formic acid 
will be described in a further communication. W. 0. W. 



Optically Active Dialkylacetic Acids. Emil Fischer, Julius 
HoLZAPFEL, and Hans von Gwinner (Ber., 1912, 45, 247 — 257. 
Compare Fischer and Flatau, Abstr., 1909, i, 628). — a-isoButylhexoic 
acid has been resolved into optically active components by crystal- 
lisation of the brucine salt. The difference between the butyl and 
isobutyl radicles is apparently enough to cause pronounced optical 
asymmetry. a-isoButylvaleric acid has also been resolved, but 
definite results were not obtained with a-isopropylvaleric acid. 

Ethyl hutyli&ohutylmalonate, prepared by the interaction of n-butyl 
bromide on ethyl zsobutylmalonate and sodium, has b. p. 137 — 140°/ 
10 mm. When hydrolysed by means of feodium hydroxide, hutyl 
hobutylmalonic acid is obtained in colourless crystals, m. p. 136 — 138°. 
The neutral solution of the ammonium salt gives a colourless 
precipitate with silver nitrate, and crystalline precipitates of the 
corresponding salts with barium and calcium chlorides. On heating 
at 160°, butylisobutylacetic [a-isobutylhexoicl^ acid is obtained as a colour- 
less oil, b. p. 145 — 145*5° (corr.)/10 mm. The hruciyie salt forms 
small, microscopic prisms. The first separations were hydrolysed 
by heating with sulphuric acid. The optically active d-a-isoh\ity\- 
hexoic acid had [a]t; -l-5'73°. 

Ethyl j)ro2)yl\iiobutylmalonate was obtained as an oil, b. p. 126°/ 
9 5 mm. 



i. 158 ABSTRACTS OF CHEMICAL PAPERS. 

Propi/l'xsobuti/lfnalonic acid cryntallises in stunted prisms or platps, 
m. p. 147 — 149^ (corr., decomp.). 

Vrojyyl\f>>ohutylacetic [a-iHohutylvaleric] acid is a colourless oil, 
D^o 0-8928, b. p. 122° (corr.)/8-5 mm. ; it forms a colourless silver 
salt, crystallising from ammonia in microscopic, slender needles. Tlie 
calcium salt also consists of microscopic, slender needles. The hrucine 
salt forms microscopic, small prisms, and yields d-a-mobutylvaleric acid 
as a colourless oil, m. p. 10070-5 mm., D22 0-8876, [a]f;^ +9-8°. 

The iiionoamide of jrropylisopropijlmalonic acid, 
COgH-CPr-Pr^-CO-NHg, 
obtained by heating cyanowopropylvaleric acid with concentrated 
sulphuric acid, crystallises in colourless bunches of intergrown 
prisms, m. p. 137° (corr., decomp.). When heated over the flame in a 
distillation flask, a-isopropylvaleramide is obtained at about 250°. It 
crystallises in slender, colourless needles, m. p. 131 — 133° (corr.). 

By the action of sulphuric acid and sodium nitrite at 80'^, jtropyl- 
i^ojrropylacetic [a-i^opropylvaleric^ acid is obtained, b. p. 116° (corr.)/ 
12 mm., 112— 113°/9mm., D^^ 0'9076. 

A partial resolution was obtained by means of the quinidine salt, 
the acid formed having [af^ +077°. E. F. A. 



Composition of Linseed Oil and the Distribution of Oxygen 
in Dried Layers of the Oil. II. E. I. Orloff {J. liuss. Phys. 
Cliem. aSoc, 1911, 43, 1509—1524. Compare Abstr., 1910, i, 810).— 
The author criticises Fokin's work (Abstr., 1907, i, 820), the results 
of his own experiments being in agreement with Genthe's theory 
(Zeitsch. angew. Chem., 1906, 19, 2087), except that he finds that 
when a layer of the oil, 100 — 108 sq. cm. in area, weighs O'l — 0'15 
gram, 16 — 16% of oxygen is taken up, although setting occurs when 
only 12% has been absorbed. 

Experiments in which a cobalt dryer was employed give for the 
rates at which oxygen is fixed results corresponding with the formula 



re- 



dx/dt = k{A-x)(B + x) or ^ = ^^2+^* ^°^\X^' ^^/' ^^®^® "^ 
presents the total amount of oxygen absorbed expressed as reduction 
of pressure, x the atmospheric pressure, and B a constant. After 
the oil has combined with 12% of its weight of oxygen, a solid phase 
is formed, and the further velocity of the absorbing process is expressed 
by dx/dt = k{A -fx){B +/a;), where /, the correction coefficient, is less 
than unity, and corresponds with the product of combination of the 
solid phase, A;/" being a constant magnitude. 

In parallel with this chemical process proceeds a physical one of 
diffusion of the oxygen into the oil, the amounts of oxygen in 
successive layers, starting from the surface, being in the proportions 
of n, n^, 71^, n* . . . nP, where n is less than 1 (0-5, 0-6, etc.). The 
quantity of oxygen combined is related to the factor n, according to 
the expression S/Q = n/(\ - ii), where Q is the quantity of combined] 
oxygen corresponding with the iodine number, and S is the amount of 
oxygen found in each separate case. Assuming complete distribution: 




ORGANIC CHEMISTRY. i. 159 

of the oxygen by diffusion, the value of n must be taken as two-thirds. 

T. H. P. 

Molecular Rearrangements in the Camphor Series. IX. 
LauronoHc Acid and Campholactone. William A. Noyes and 
Charles E. Burke {J. Amer. Ckem. Soc, 1912, 34, 174—183).— 
Tiemann (Abstr., 1901, i, 6) found that lauronolic acid prepared from 
bromocamphoric anhydride has a rotatory power which differs con- 
siderably from that of the acid obtained by the distillation of camphanic 
acid, and suggested that the acid produced by the latter method con- 
sisted of a mixture of optical isomerides. This has now been proved 
to be the case. 

Lauronolic acid, prepared from active bromocamphoric anhydride 
by Aschan's method (Abstr., 1895, i, 154), has been obtained in the 
form of rosettes of long needles ; it has m. p. 6-5 — 8°, b. p. 230 — 235° 
under the ordinary pressure, vapour pressure 99 — 100 mm. at 184", 
Dr 10109, Df 1-0133, Djo 1-0249, [aj +187'7°,71d 1-47586, and the 
dissociation constant K 1-36x10"^. The calcium salt crystallises 
with 3H2O, instead of only 2H2O as stated by Bredt (Abstr., 1911, i, 
417), and when heated with sroda-lime yields laurolene. 

When hydrogen iodide is passed into a solution of lauronolic acid 
in light petroleum, the hydriodide is obtained in the form of yellow 
plates, and is very unstable. On reducing this compound with zinc 
dust and alcohol, dihydrolauronolic acid, CgHj^'COgH, is produced, 
which has Df 0*9008, [a]?^+l-74°, vapour pressure 100 mm. at 
178° and 749 mm. at 215"^, and [n]jy 1-45786; the amide has m. p. 
50-51°. 

By decomposing inactive bromocamphoric anhydride prepared from 
synthetical camphor, inactive lauronolic aud camphanic acids were 
obtained. Inactive lauronolic acid has m. p. 5 — 8-5°, vapour pressure 
100 mm. at 192°, Df 1-0318, and [n]^, 1*47655; its calcium salt 
crystallises with IHgO. 

Campholactone, prepared in various ways from lauronolic acids of 
widely different rotatory powers, has m, p. 50° and [a]^ -21-7°, and 
when warmed with barium hydroxide solution is converted into the 
corresponding hydroxy-acid, m. p. 143° and [ajg' +16-0°. E. G. 



Molecular Rearrangements in the Camphor Series. VIII. 
Camphonolic Acid and Camphonololactone. William A. 
NoYES, E. E. GoRSLiNE, and R. S. Potter (J. Amer. Chem. Soc.^ 
1912, 34, 62 — 67). — Four hydroxy-acids and three lactones have been 
described which retain the tertiary carboxyl group- of camphoric acid. 
Tlie structural formulae assigned to these compounds have not been 
well established, and the present work was therefore undertaken with 
the object of obtaining further evidence as to their constitution. 

Camphononic acid, prepared by a modification of Lapworth and 
Lenton's method (Trans., 1901, 79, 1287), has m. p. 229—230°, [a]S« 
in benzene (2*4 grams in 100 c.c.) +17-8°, [a]rf in alcohol (2 grams 
in 100 c.c.) -3*9°. On reducing this acid with sodium and amyl 



I ItJO AIJSTKACTS OF CHEMICAL I'APEllS. 

alcohol, amyl camplionolate is obtained as a yellow, vipcons oil of 
b. p. 222 — 223°/4() mm. ; tiie calcium^ copper, and silver salts were 
prepared. 

It is shown that the lactone obtained by Noyes and Taveau (Abstr., 
PR •PM 'CO ^^^^j ^» ^^7) ^y decomposing the nitroso-derivative 

12 , . of aminolauronic anhydride with sodium hydroxide is 

CMe^ identical with cis-camphonololactone (annexed formula) 

prr .r'lTT k prepared by Bredt (Abstr., 1909, i, 498) by the 

2 electrolytic reduction of camphononic acid. cis- 

Camphonololactone has m. p. 165 — 167°, [a]^ in alcohol (5 grams in 

CH -CMe-COH ^^^ ^•''•) ~^^'^° """"^ W'> ^^^ ^""^"^^ '"^ ^^^ ''•'^•) 

12 , 2 _ 2 2 3°. The corresponding hydroxy-acid, cis- 

CMeg cam phenolic acid (annexed formula), has m. p. 

CR '(''R/^OR^ ^^^ — ^^^° when rapidly heated, [a]o in alcohol (10 
2 ^ ^ grams in 100 c.c.) +29'2°, and on oxidation with 
chromic acid is converted into camphononic acid. E. G. 

The Melting Point of Oxalic Acid. Eyvind Bodtker {Chem. 
Zeit., 1912, 36, 105). — Pure crystallised oxalic acid does not appear 
to have a definite melting poiut ; a small crystal placed in a capillary 
tube had m. p. 99*5 — 101*5°, whilst a layer in the capillary tube, 
1 mm. in height, had m. p. 100 — 102*5° when the temperature was 
raised very slowly and maintained at 100° for about one minute. 

W. P. S. 

Conversion of Maleic into Pumaric Acid. Sebastian M. 
Tanatar (J. Russ. Phys. Chem. Soc, 1911, 43, 1742— 1746).— It 
was discovered by Skraup (Abstr., 1891, 1338) that the interaction of 
hydrogen sulphide and sulphur dioxide in aqueous solution in presence 
of maleic acid is accompanied by transformation of the latter acid into 
fumaric acid ; this effect he termed "resonance." 

Since the reaction liquid, after filtration from the sulphur formed, 
contains nothing capable of bringing about this transformation, the 
author has investigated the action of sulphur on maleic acid. Milk 
of sulphur is without effect, and the same is apparently the case with 
the sulphur separated by the action of hydrogen sulphide on ferric 
chloride in presence of maleic acid. With sodium thiosulphate and a 
mineral acid, however, which normally give precipitation of sulphur, 
maleic acid prevents such precipitation and is simultaneously con- 
verted into fumaric acid ; a similar transformation is produced, also 
without separation of sulphur, by addition of the thiosulphate to a 
solution of maleic acid alone. That these solutions contain no dissolved 
sulphur is shown by extraction with carbon disulphide, and the con- 
clusion is drawn that it is the reaction of the thiosulphuric and maleic 
acids, with formation of an unknown product, that induces the isomeric 
change. 

This same change is brought about by treatment of maleic acid with 
ammonia or potassium polysulphide (liver of sulphur), although in 
the latter case it may be due to the presence of thiosulphate. 

T. H. P. 



ORGANIC CHEMISTRY. i. 161 

Relation between the Configuration and Rotation of the 
Lactones in the Sugar and Saccharinic Acid Groups. Krnest 
Anderson (J. Amer. Gkem. Soc, 1912, 34, 51 — 54). — Hudson (Abstr., 
1910, i, 220) has pointed out that dextrorotatory sugar lactones have 
the ring on one side of the structure, whilst Isevorotatory lactones 
have it on the other. 

It is now shown that this relation is true, not only for the lactones 
to which Hudson referred, but for nearly all monobasic and some 
dibasic acid lactones in the sugar and saccharinic acid groups. The 
configurations and specific rotations of eighteen such lactones are 
tabulated. The relation affords a new method for determining the 
configuration of the lactones formed by certain dibasic acids. 

E. G. 

Ethyl Orthotrithioformate. Bror Holmberg (Ber., 1912, 45, 
364 — 365). — In reply to Houben and Schultze (this vol., i, 5) it is 
claimed that the product obtained by the author (Abstr., 1907, i, 474) 
was pure. D. F. T. 

Action of Potassium Hydroxide on Tetrolacetal. Paul L. 
ViGUiER (Compt. rend., 1912, 164, 217—220. Compare Abstr., 1909, 
i, 691 ; this vol., i, 7). — When tetrolacetal (diethoxybutinene) is 
dropped on potassium hydroxide at 180 — 200°, a liquid distils, and on 
fractionation yields a compound, C^-HgO, b. p. 29 — 33°/16 mm., 
D^^^' 0-826, n'^-" 1*462. This probably has the constitution 

OH:C-CH:CH-OEt, 
since it forms an explosive silver derivative, CgH^OAg, and is 
hydrolysed by acids, forming an unstable substance having the 
properties of the aldehyde, CHrC'CHg'CHO. The latter changes 
spontaneously into triacetylbenzene, acetoacetaldehyde probably being 
produced first. Hydroxy lamine yields 1-methyh'sooxazole. On treat- 
ing the aldehyde with semicarbazide hydrochloride, a semicarbazone, 
C^HgONgCl, is obtained; this yields the corresponding aldehyde, 
C4H5OCI, on hydrolysis. W. O. W. 

Tartardialdehyde. Alfred Wohl and Bruno Mylo {Ber., 
1912, 45, 322— 349).— From the result of their endeavours, the 
authors conclude that the synthesis of tartardialdehyde by the 
symmetrical linking together of two molecules each containing two 
carbon atoms presents excessive difficulties, and they have finally 
attained success by other means. 

The action on acetyl chloride of copper hydride gives ethyl 
acetate and ethylidene diacetate, whilst the action of copper on the 
additive product of dibromoacetaldehyde and acetyl bromide yields 
hiomovinyl acetate. Dibromoacetaldehyde also reacts slowly with 
magnesium methoxide, the product being a /3y88(or hh^-)4rihromo-y' 
keto-n-hutyl alcohol, b. p. 77 — 79°/14 — 16 mm. 

Glyoxal sodium bisulphite in acetic anhydride solution reacts 
with hydrogen chloride producing unstable s-dichloroglycol diacetate, 
b. p. 110— 115714 mm. (compare Prud'homme, Zeit. Chem., 1870, 
380). 



k 



i. 162 ABSTRACTS OF CHEMICAL PAPERS. 

Ethyl diethoxyacetato in ethereal solution witli potassium gives as 
chief product an undistillable syrupy substance, p-hy(lrox!/-y-keto- 
succiiulicdcWtyde diethylacetal, CH(OEt)2-CO-CH(OH)-Cll(OKt)2 ; the 
substance was not obtainable in a pure state, and the action of 
^iodium gave still less satisfactory results. The action of sodium on 
the piperidide of diethoxyacetic acid (Wohl and Lange, Abstr., 1908, 
i, 943) yields monoethoxyacetopiperidide^ b. p. 72 — 74°/0*08 — 0*11 mm. 
Diethoxyacetohydrazidcj obtained from the ethyl ester with Ijydrazine 
in alcoholic solution, forms capillary crystals, m. p. 43 — 45°, and has 
b. p. 110°/0'05 mm. ; it reacts with mercuric oxide or metaboric acid, 
eliminating nitrogen and forming his-diethoxyacelohydrazide^ 

CH(OEt)2-CO-NH-NH-CO-CH(OEt)2, 
which crystallises in needles, m. p. 67 — 70° ; the mercury, copper, and 
lead compounds are described. Iodine removes mercury from the 
mercury compound with the formation of azo-a-ketodi-(3-ethoxyethane, 
CH(OEt)2*CO-]S:N-CO-CH(OEt)2, a viscous, colourless oil, b. p. 
131 — 134°/0'07 — O'OS mm., which on warming decomposes, giving 
ethyl orthoformate, instead of the desired tetraethoxydiacetyl, 
CH(OEt)2-CO-CO-CH(OEt)2. 

Success was attained by starting with di-magnesium acetylene 
dibromide (from acetylene and magnesium ethyl bromide), which on 
treatment with ethyl orthoformate gives acetylenedialdehyde diethyl- 
acetal, CH(OEt)2-C:C-CH{OEt)2, D'«^ 0-955 (compare Jotsitch, Chem. 
Zeit., 1907, 31, 979) ; by reduction with hydrogen in the presence of 
colloidal palladium, this passes into ni(deinaldehyde diethylacetal, b. p. 
112— 11 2-5°/ 11 mm., D^'^^ 0-926, which is oxidisable by potassiui 
permanganate (compare Wohl, Abstr., 1898, i, 556) into tartar- 
dialdehyde diethylacetal, a viscous oil, b. p. 157 — 160°/11 mm. Th< 
hydrolysis of this acetal is most satisfactorily accomplished by NjlO- 
sulphuric acid in the cold, when a sweet solution of tartardialdehydei 
is obtained ; this solution on slow evaporation deposits microscopicf 
needles, which, having a bitter taste and being sparingly soluble] 
in water, probably represent a polymeric form; they re-dissolve] 
slowly in warm water, giving a sweet solution, which from its 
cryoscopic behaviour contains the substance in a unimoleculari 
condition ; this solution on evaporation gives a sweet amorphous] 
residue. 

The diphenylhydrazone of tartardialdehyde forms yellow crystals,! 
m. p. 197*5° (corr., decomp.) ; no osazone was obtainable; the' 
di-seniicarbazone has m. p. 2275° (corr., decomp.); the dioxime, 
153*5° (corr., decomp.). 

Oxidation of the tartardialdehyde by bromine water gives meso- 
tartaric acid ; for this reason the above ethylenic aldehyde is supposed 
to be that corresponding with maleic acid. D. F. T. 

Dihydroxyacetone as an Intermediate Product of Alcoholic 
Fermentation. Arthur Slator (Ber., 1912, 45, 43 — 46). — It is 
sometimes assumed that dihydroxyacetone is an intermediate product 
of the alcoholic fermentation of dextrose (compare Buchner and 
Meisenheimer, Abstr., 1910, ii, 737). If this is the case, dihydroxy- 
acetone must be fermented by the yeast at least as quickly as 



ORGANIC CHEMISTRY. i. 163 

dextrose. Experiments are quoted to show that during tweuty 
minutes no dihydroxyacetone is fermented, although an equal weight 
of dextrose is entirely fermented by the same yeast during this time. 
The conclusion is drawn that dihydroxyacetone is not directly 
fermented, and that it is therefore not an intermediate product of 
alcoholic fermentation. E. F. A. 

The Physico-chemical Bases of the Seliwanoff LaBVulose 
Reaction. Harry Koenigsfeld (Biochem. Zeitsch., 1912, 38, 
310 — 320). — It is shown that the Seliwanoff reaction for Isevulose is 
also yielded by dextrose when the latter is present in a concentration 
higher than 2%, and also when the hydrochloric acid exceeds 
12 — 12*5% in strength. As the reaction appears to be due to hydroxy- 
methylfurfuraldehyde formed from the Isevulose, and as under certain 
conditions Isevulose can be formed from dextrose, the author draws the 
conclusion that the latter sugar only gives a positive result in the 
Seliwanoff reaction when the conditions are such that it can be con- 
verted in appreciable quantity into the former sugar. This hypothesis 
is supported by the investigation of the action of acids and bases 
on dextrose, 'jWhich, it is shown, probably changes under certain 
conditions into fructose. S. B. S. 

Chemistry of the Wood Dextrins. C. A. Yllner [Zeitsch. 
angew. Ghem., 1912, 25, 103 — 107). — The dextrins obtained by Honig 
and Schubert (Abstr., 1887, 125) are mixtures of homologues, from 
which the individual substances can be obtained only after repeated 
precipitation. The reducing power increases with the rotation of the 
dextrin ; 1 gram of a dextrin with the rotation + 25° corresponds 
with approximately 0*1 gram of cuprous oxide, a rotation of +50° 
corresponding with about 0*2 gram of cuprous oxide. 

The velocity and extent of hydrolytic decomposition with acids was 
determined. T. S. P. 

Photolytic Decomposition of Smokeless Powders by Ultra- 
violet Light. Influence of Stabilisers. Damaged Powders. 
Daniel Berthelot and Henry Gaudechon (Compt. rend., 1912, 154, 
201 — 203. Compare this vol., ii, 210). — Exposure of nitroglycerol to 
the light from a quartz-mercury lamp results in decomposition with 
production of the following gases: COg (24 vols.), CO (19*5 vols.), 
Ng (39 vols.), NgO (7 vols.), NO (9 vols.), with a considerable amount 
of nitrogen peroxide, which, however, is not evolved from the 
gelatinised material treated with stabilisers. At a distance of 20 mm. 
from the lamp, powders stabilised with amyl alcohol withstood 
decomposition better than those containing diphenylamine, whereas 
at 50 mm. diphenylamine was the more effective stabiliser. Damaged 
French naval powders showed themselves less resistant to the rays 
than sound powders of the same composition. W. O. W. 

General Method for the Preparation of Aliphatic Amines by 
Catalytic Reduction of Alkyl Nitrites. Georges Gaudion {Aim. 
Chim. Phys., 1912, [viii], 25, 125— 136).— The author has applied 
Sabatier and Senderens' method (Abstr., 1905, i, 333) of catalytic 



i. 164 ABSTRACTS OF CHKMICAL PAPERS. 

reduction by moans of finely divided nickel or copper in presence of 
hydrogen to a series of alkyl nitrites, and finds that these are 
reduced, giving the corresponding secondary amine, with small amounts 
of the primary amine and very small quantities of the tertiary amine. 
Nickel generally acted at a lower temperature than copper ; thus in the 
case of woamyl nitrite the former gave good results at 220 — 230°, and 
the latter at 350°. 

Several possible explanations of the reaction are discussed, and it is 
considered that it is best explained by assuming that the alkyl nitrites 
are first isomerised into the corresponding nitro-paraffins, which are then 
reduced in the ordinary way. This explanation is the more probable 
in view of the fact that the reaction seems to take place in the same 
way as the catalytic reduction of the nitro-paraffins investigated 
by Sabatier and Senderens (Abstr., 1902, i, 701). T. A. H. 

Ammonium and Sulphonium Perchlorates. Relations 
between Solubility and Constitution. Karl A. Hofmann, 
Kurt Hobold, and Fritz Quoos {Annalen, 1912, 386, 304 — 317. 
Compare Abstr., 1910, i, 818; 1911, i, 608). — Ammonium and 
sulphinium perchlorates are eminently suitable substances for the 
study of the relationship between solubility and constitution, because 
they do not form hydrates, are nearly allied crystallographically, and, 
whilst not being hydrolysed in aqueous solution, are electrolyticaily. 
dissociated to the same order of magnitude ; several factors, therefore, 
which might possibly mask the relationship are eliminated from the 
field. The following perchlorates are described (the numbers in 
brackets denote the grams of water in the saturated solution at 15° 
containing one gram-molecule of the salt) : NH^'CIO^ (635) ; 
NHMe3-C104 (800); NMe^-ClO^ (32,640); NMegEfClO^ (1710); 
NMogPr'ClO^, doubly refracting, rhombic plates or prisms, m. p. 118° 
(1310); NMe8(C3H5)-Cl04, thin, rectangular plates, m. p. 90° (100); 
Cl04*NMe3*C4H9, almost rectangular plates, m. p. 186° (5810) ; 
ClO^'NMeg'CgHjj, doubly refracting, rhombic plates or prisms (10,300) ; 
NMegPh-ClO^, rhombic crystals, m. p. 175° (decomp.) (1315); 
CHgl'NMeg'OlO^, rhombic or monoclinic plates, m. p. 184° (decomp.) 
(9535); Cl04-NMe3-CH2-CH(OH)-CH2-OH, thin, doubly refracting, 
rhombic plates, sinters at 86° (150) ; NEt4-ClO4(6130) ; NMeEtg-OlO^, 
rhombic plates (915); NEtgPr'ClO^, quadratic prisms, m. p. 275° 
(3090) ; NMe.Etg-ClO^ (150) ; C2H4(NH3-C104)2, rhombic plates (200) ; 
C2H4(NMe3-0104)2, stout, rhombic plates (28,700); C3Hg(NMe3- 0104)2, 
doubly refracting leaflets (23,500) ; SMe3*C104, stout, rhombic prisms or 
elongated plates, m. p. above 267° (1280); SMe2Et-C104, elongated, 
rhombic plates (840) ; SMe2Pr-Cl04 (1700); C104-SMe2-C4H9 (16.^0); 
C2H4(SMe2-C104)2, rhombic prisms, m. p. 250° (2360) ; 

C104-SMe2-CH:CH2, 
elongated plates (1368) ; C3H6(SMe2-C104)2 (2480). 

The most striking result is the sparing solubility of the quaternary 
ammonium perchlorates in comparison with the great solubility of 
uietliylammonium perchlorate (120), dimethylammonium perchlorate 
(70), diethylammonium perchlorate (115), and ethylammonium per- 
chlorate (70). Another striking fact is the enormous difference in the 



ORGANIC CHEMISTRY. i. 165 

solubilities of quaternary ammonium perchlorates containing like 
alkyl groups from those containing unlike alkyl groups ; for example, 
NMe^-ClO^ (32,640), NMegEfClO^ (1710). These two groups of per- 
chlorates also differ in their stability towards alkaline potassium 
permanganate, those of the type NK^'CIO^ being stable, whilst members 
of the other group are rapidly oxidised, at the ordinary temperature. 

The molecular dilutions of glyceryltriraethylammonium perchlorate 
(150) and of choline perchlorate (70) show how enormously the 
solubility is increased by the introduction of hydroxyl groups ; when 
the hydroxyl groups are esterified, however, the solubility is very 
largely diminished, as shown in the case of nitratocholine perchlorate 
(40,000). Deductions similar to the preceding can be drawn in the 
case of the sulphinium perchlorates. C. S. 

Decomposition of Quaternary Ammoniuni Hydroxides. 
II. Julius von Braun (Annalen^ 1912, 386, 273 — 303. Compare 
Abstr., 1911, i, 610). — The decomposition by heat of diammonium 
hydroxides of the type OH']SrMe3'[CH2]a;*NMe3*OH may result in the 
formation of di-olefines, unsaturated tertiary amines, or ditertiary 
diamines. Substances in which x is 3, 5, 7 and 10, have been 
examined. All four yield by decomposition unsaturated tertiary 
amines, CH2!CB[*[CH2]a;_2*NMe2, the amount of which increases as x 
increases j thus hexamethyldecylenediammonium iodidej 

I-NMe,-[CHJ,„-NMe3l, 
white leaflets, m. p. 231°, obtained from aK di-iododecane (Abstr., 1910, 
i, 25) and alcoholic trimethylamine at 100°, is converted by the usual 
treatment into a syrupy mass of hexamethyldecylenediammonium 
hydroxide, by the distillation of which very little di-olefine (unex- 
amined) is formed, the chief product being a mixture of 30% of 
dimethyldecenylamine, CH2lCH-[CH2]8*NMe2, b. p. 118 — 120717 mm. 
(platinichloride ', picrate, m. p. 137°; methiodide, m. p. 137 — 140°), and 

50% of aK-teiramethyldiaminodecane, C-^^Hq^^^'^' V- 1^7 — 158°/ 17 mm., 
(platinichloride, m. p. 189° [decomp.]; picrate, ra. p. 139 — 140°). The 
distillation of trimethyldecenylammonium hydroxide gives a 75% yield 
of dimethyldecenylamine ; hence the latter can be obtained from hexa- 
methyldecylenediammonium hydroxide with comparative ease and in 
good yield. 

Hexamethylheptylenediammonium bromide, 

Br-NMe3-[CHJ7-NMe3-Br, 
m. p. 245°, prepared from ayy-dibromoheptane and alcoholic trimethyl- 
amine at 100°, forms a diammonium hydroxide, the distillation of 
which yields about 15% of a heptadiene, 28 — 29% of dimethylheptenyl- 
amine, CH2:CH-[CH2]5-NMe2, b. p. 166—169° or 60— 65°/10 mm. 
{picrate, m. p. 88° ; methiodide, m. p. 120°), and 51% of arj-tetramethyl- 
diaminoheptane, NMe2*[CH2]7*NMe2, b. p. 225 — 230° (decomp.) or 
101— 102°/10 mm. {picrate, m. p. 136°; dimethiodide, m. p. 242°). 
Unlike the two preceding diammonium hydroxides, hexamethyl- 
amylenediammonium hydroxide, prepared from the iodide {loc. cit.), 
begins to decompose during the evaporation of its aqueous solution. 
Its complete decomposition yields mainly trimethylamine, water, and 
piperylene, very little tetramethyldiaminopentane, b. p. 193 — 194° 

VOL. CII. i. n 



i. Ifi6 ABSTRACTS OF CHEMICAL PAPERS. 

(platiiuchloi-iffe, m. p. 218° [decomp.] ; picrate, m. p. 149°), and 
dimethylpentenylamine (isolated as the methiodide, m. p. 200°) being 
produced. Similar results are obtained by the decomposition of hexa- 
methylbutylenediammoniuni hydroxide and hexamethylpropylene- 
diammonium hydroxide; in the latter case, the non-nitrogenous pro- 
duct is not allene, but a mixture of viscous oxidation products, from 
which an unsaturated substance, C^^HjqO {semicarhazone, m. p. 192°), 
probably an isomeride, CHa'CO-CHa'CMelCHg, of mesityl oxide, has 
been isolated. 

The experiments indicate that in the decomposition of diammonium 
hydroxides, whilst the lower members of the series decompose 
simultaneously at both ends of the chain, the higher members 
experience changes first at one end of the chain only. For example : 
OH-NMe3-[CH2i,o-NMe3-OH -^ Me-OH + OH-NMe3-[CH2VNMe2 
and H20 + ]SIMe3 + OH-NMe3-[CH2]8-CH:CH2 ; 

then OH-NMe3-[CH2]io*NMe2— >MeOH + NMe2-[CH2]io-NMe2 and 

H2O + NMe3 + CH2:CH-[CH2]8-NMe2, 
whilst OH-NMe3-[CH2]8-CH:CH2 -> MeOH + NMe2-[CH2]8-CH:CH2 
and H20 + NMe3 + CioHi8. 

It has been shown {loc. cit.) that the presence of an ethylenic linking 
in an aliphatic group in a quaternary ammonium hydroxide facilitates 
the elimination of the group when the point of unsaturation is 
adjacent to the nitrogen atom. The decomposition of the hydroxides 
OH'NMe3*[CH2]x*CHICH2 shows that the loosening influence of the 
ethylenic linking weakens as its distance from the nitrogen atom 
increases ; trimethyldecenylammonium hydroxide yields not more 
hydrocarbon than does the corresponding saturated quaternary 
ammonium hydroxide. C. S. 

The Asymmetric Cobalt Atom. V. Alfred Werner (Ber.i 
1912, 46, 121 — 130). — According to the author's theory, there are 
two possible salts of triethylenediaminecobalt which stand to each 
other in the relation of object and mirror-image, and are not super- 
posable. These may be represented thus : 



-n 


y^- 




A^en 


/ ' 


.V\ 


' \ 


enN^^^ 




ym 



Such compounds form the simplest possible case of molecular 
asymmetry, being specially characterised by having all the co-ordination 
positions of the central atom occupied by structurally identical groups, 
the asymmetry being caused by the special spatial arrangement of 
these groups. Such asymmetry the author denotes as 'molecular 
asymmetry II (compare Abstr., 1911, i, 838), and he has been 
successful in resolving some of the salts into the optically active 
isomerides. Resolution by means of the camphorsulphonates, a-bromo- 
camphorsulphonates, etc., was unsuccessful, since the salts would not 
crystallise. Triethylenediaminecobaltic tartrate was obtained in the 



ORGANIC CHEM18TRY. i. 167 

crystalline condition, however, and proved to be a partial racemate, 
which underwent slight resolution on fractional crystallisation, the 
extent of the resolution being ascertained by taking advantage of the 
very strong rotation dispersion of these compounds. The lesser 
soluble crystals contained an excess of the Isevo-isomeride, the final 
mother liquors containing the excess of the dextro-isomeride ; the pure 
isomerides could then be isolated by making use of the fact that their 
bromides were readily soluble in concentrated hydrobromic acid, the 
racemic bromide being almost insoluble. The yields of the active 
components were very poor by this method, which was then replaced 

by the following : The chloride tartrate, Co eng p tt /-v > does not 

form a partial racemate, and by one recrystallisation can be separated 
into the sparingly soluble c/-tiiethylenediaminecobaltic chloride-c?- 
tartrate and the readily soluble ^-triethylenediaminecobaltic chloride- 
c?-tartrate, from which other salts can be obtained without 
difficulty. The bromide tartrates behave similarly to the chloride 
tartrates. 

The specific rotations of the various salts are very large, and 
the rotation dispersion is very marked, as shown by the following 
table : 

[«].'^ K- [M]^. ^ [M]^,. 

Chloride 1"^???° +45° "f "^560*^° ±153-6° 



{till ±32 {t 

^'t^^ta {till {'M {t 



Bromide -! "^^ ±32 "^ ^592^ "^1^5 

561 +195-5 

552 -187 



The active salts are very stable ; their solutions can be evaporated 
down with concentrated hydrochloric or hydrobromic acid without 
suffering any loss of activity. The active isomerides are much more 
readily soluble than the racemates. 

The triethylenediaminecobaltic salts, (Co en3)X3, are best prepared as 
follows : 10 grams of cobalt chloride are dissolved in 150 grams of 
10% ethylenediamine and oxidised by leading air through the solution. 
The brown solution so obtained is acidified with hydrochloric acid, 
evaporated to crystallisation, the crystals dissolved in water, and 
ammonium nitrate added to the solution, whereby 1 : 6-dichloro- 
diethylenediaminecobaltic nitrate is precipitated. After collecting 
this salt the filtrate is precipitated with sodium bromide, giving pure 
triethylenediaminecobaltic bromide. 

Triethylenediaminecobaltic tartrate, (Co eD^)2(C^Ilfi(.^^, is obtained 
from the bromide by double decomposition with silver tartrate ; 
it crystallises in spherical aggregates of light yellow needles. Tri- 
ethylenediaminecobaltic chloride-tartrate, Co eng p xi f) > is prepated 

by interaction of 1 molecule of the chloride with 1 molecule of silver 
tartrate, the precipitate of silver chloride being extracted with boiling 
water until pure white in colour. The solutions thus obtained are 
3oncentrated and allowed to crystallise, columnar and tabular crystals 
separating ; these are collected and the filtrate further concentrated. 

n 2 



i. 168 ABSTRACTS OF CHEMICAL PAPERS. 

A second crop of crystals often separates, and then the concentrated 
sohition seta to a jelly-like mass. The crystals consist of d-triethylene- 

diamiiiecobaltic cfiloride-tartrate, M^*^ ®"8 n tt n >^-^2^' ^^^ ^^® 

pnriBed by one recrystallisation from water; they have [a]i, +101°, 
[M]d +517-6°, [a]c+35°, [M]c +179-4° The gel consists of the 
corresponding ^aevo-salt, mixed with small quantities of the (/-isDmeride. 

d-Triethjlenediaminecohaltic hromide-tartrate, M^o ^"3 n xr o j^HgO, 

is obtained similarly, and forms a felted mass of light yellow, silky 
needles, which, in contact with the solution, slowly charge to 
much darker, stout, plate-shaped crystals ; they have [aj^ + 98°, 
[M]d + 555°, [a]c + 38°, [MJe, + 211-7°. The corresponding laevo- 
isomeride forms, a gel. 

d-Triethylenediaminecoballic bromide, [Co en3]Br3,2H20, is prepared 
from either the bromide -tartrate or the chloride-tartrate by trituration 
with warm concentrated hydrobromic acid. The solution, after 
filtering, deposits large, hexagonal plates, which are probably an acid 
bromide; on recrystallisation from water, large, columnar crystals of 
the bromide are obtained. The \-bromide, [Co en3]Br3,2H20, is 
similarly prepared from the gel of Z-bromide-tartrate or Z-chloride- 
tartrate, the sparingly soluble racemic bromide remaining undissolved. 
The d- and Vchlorides, [Co engjClg.HgO, are obtained from the bromides 
by reaction with silver chloride; they crystallise in small, golden- 
yellow, needle-shaped crystals. The d- and \-nitrates, [Co en3](N03)g, 
are prepared from the bromide by treatment with the theoretical 
quantity of silver nitrate ; they form pyramidal crystals, which art 
readily soluble in water. T. S. P. 

Preparation of Hexamethylenetetramine Borocitrates. 
Athenstaedt and Redeker (D.R.-P. 238962). — Alkali and magnesium 
borocitrates have been previously described. The hexamethylene- 
tetramine derivatives have now been obtained by thoroughly mixing 
the required proportions of the ingredients in either concentrated 
aqueous or alcoholic solution. They form colourless, crystalline 
powders, and are readily soluble in water or alcohol. 

Hexamethylenetetramine borocitrates hnYing the following composition 
are mentioned : 

C6H807,3HB02,2C6Hi2N4, decomp. 182°; 

C6H807,3HB02,3C«Hi2N, „ 192°; 

2C,H307,2HB02,3C«H,2^\ „ 185°; 

2C,H307,4HB02,30«Hi2N4 „ 180°; 

2C6H807,6HB02,3CeHi2N, „ 178°. 

F. M. G. M. 

Compounds of Chromic Hydroxide with Amino-acids 
Derived from Proteins. Louis Hugounenq and Albert Morel 
(Compt. rend,, 1912, 154, 119— 120).— Chromic hydroxide (1 mol.) 
dissolved in a boiling aqueous solution of glycine (6 mols.) gives a 
purple-red solution which deposits red crystals containing four mole- 
cules of the amino-acid and two hydroxy 1 groups to two atoui 



ORGANIC CHEMISTRY. i. 169 

of chromium. The excess of chromic hydroxide is removed by 
lixiviation or treatment with acid. The filtrate from the red crystals 
ou slow evaporation deposits brilliant, vermilion, acicular prisms of 
a compound containing six molecules of the amino-acid to two atoms 
of chromium. Both compounds are soluble in acids, and are slowly 
decomposed by alkalis. They do not show the ordinary reactions of 
chromium salts, but resemble more closely the chromoxalates. 

W. 0. w. 

Action of Amino-acids on Sugars ; Formation of Substances 
Resembling Melanins. Louis C. Maillard {Gompt. rend., 1912, 
154, 66—68. Compare this vol., i, 13).— Continuiug his experiments 
on the action of natural polyhydric alcohols on amino-acids, the author 
finris that when glycine is heated on the water-bath with four times its 
weight of dextrose and the same amount of water, it rapidly loses 
carbon dioxide and forms dark brown, cyclic^ condensation products, 
the molecules of which contain at least two dextrose residues to one 
nitrogen atom. They are said to be identical with the melanin pig- 
ments obtained in the hydrolysis of proteins. If this is so, the 
comparatively low yield of amino-acids in such hydrolyses receives an 
explanation. The reaction is instantaneous between glycine and 
xylose or arabinose, rapid in the case of galactose and mannose, slow 
with lactose and maltose, whilst several hours elapse before it occurs in 
the case of sucrose. Of the common amino-acids, alanine is the most 
active. ^ Q ^y 

The Action of Moist Sulphur on Cholic Acid and Taurine. 
J. A. A. AuziES {Rev. gen. chim. pure appl., 1911, 14, 278— 280).— A 
study of the composition of the gall and bile of cattle and pigs, from which 
the author corroborates the results of Langheld (Ab-tr., 1908 ii 211) 

Cholic acid, OH-NMeg-CH^-CO^H, is prepared by mixiog cllcium 
chloroacetate (1-92 parts) with trimethylamine (1-18 parts) and heating 
the chloride of calcium trimethylammoniumacetate so obtained with milk 
of lime at 120—150°. 

Taurine is prepared on an industrial scale as follows : Acetaldebyde 
IS heated at 140° with chlorosulphonic acid 

CHg-CHO -f SO3HCI = HCl + SOgH-CH^-CHO, 
the product converted into its calcium salt, (CHO•CH2•S03^2Ca, which 
sl^^""^'^^^^ ^'^^^ ammonium hydroxide yields the aldehyde ammonia, 
lJNll2-CH(OH)-CH2-S03]2Ca, this loses water (2 mols.) on heating, and 
IS converted into the imine, (NH:CH-CH2-S03)2Ca, which alter 
reduction to the corresponding amine and elimination of calcium with 
sulphuric acid furnishes the required taurine. F. M. G. M. 

Preparation of BromoacyH^focarbamide Ethers. Farben- 
FABRiKEN voRM. Friedr. Bayer k Co. (D.E.-R 240353).— When iso- 
carbamide ethers of the general formula NH2-C(0R):N1I (Il = alkyl 
or alkylaryl) are treated with bromodiethylacetyl halides, they yield 
bromo-a-ethylbutyryhsocarbamide ethers, which are of therapeutic 



value, 
m 



Bromo-a-ethylbutynjlhocarhamide methyl ether, colourless crystals, 
p. 72 , was obtained by boiling bromo-a-ethylbutyryl bromide with 



i. 170 ABSTRACTS OF CHEMICAL PAPERS. 

methyl wocarhamido hyclrochIorid« (Absfcr., 1900, i, 340) in aqiieoiiB 
solution, cooling, and rendering alkaline when the product separated. 

F. M. G. M. 

Specific Rotatory Power of Glutamine. Ammonium 
Qlutamate. Ernst Sciiulze and Geoiig Trier {Ber.^ 1912, 45, 
257 — 262). — Supposed pure preparations of glutamine obtained from 
different plant preparations by precipitation with mercuric nitrate and 
continued crystallisation show [a]„ varying from +5*4° to 8*9°. By 
purification of the copper salt, these preparations all yield glutamine 
of constant rotatory power, [a] „ +6° to 7°. The higher values are due 
to the presence of traces of glutamic acid, which, acting as an acid, 
increases the rotatory power of glutamine. 

Glutamic acid forms a monobasic ammonium salt, [aju - 3-6°, which 
begins to lose ammonia when kept over concentrated sulphuric acid, 
and readily loses ammonia when evaporated in aqueous solution. 
Since glutamine when boiled in aqueous solution is to some extent 
hydrolysed to the ammonium salt, the presence of glutamic acid is 
explained. E. F. A. 

Action of Ammonia on Ammonium Thiocyanate. Walter 
P. Bradley and W. B. Alexander (/. Amer. Chem. Soc, 1912, 34, 
15 — 24). — Comparatively few substances become deliquescent ou 
exposure to dry ammonia, and of the.se animonium thiocyanate appears 
to possess the property in the highest degree, the deliquescence 
continuing up to a temperature of 88°. The absorptive power of the 
salt was determined at various temperatures between 0° and 100°. 
At 0°, the product contained 43 '10% of ammonia ; at 25°, 31*16% ; at 
50°, 19-40%; at 75°, 6 17%, whilst at 100° none was absorbed. F.-p. 
determinations were made of solutions of ammonium thiocyanate in 
ammonia, the concentrations ranging from 0% to 100% of the latter. 
On plotting the results, it is shown that there are certainly three, and 
probably five, compounds formed. The former are : NH^CNSjNHg, 
m. p. - 16° (metastable) ; NH4CNS,3NH3, m. p. - 38° ; and 

NH4CNS,8NH3, 
m. p. about -87°. The other two compounds are NH^CNSjGNHa, 
m. p. -76°, and NH4CNS,7NH3, m. p. -84°. Indications were 
also obtained of the possible existence of the compound 

2NH4CNS,13NH3, 
ni. p. about - 80°. The lowest eutectic point was in the vicinity of 
- 96°. E. G. 

The Composition of Prussian Blue. P. Woringer {Cheiu. Zeit., 
1912, 36, 78). — Evidence for regarding Prussian blue as a ferro- 
cyanide hns been given by Hofmann, Heine, and Hochtlen (Abstr., 
1905, i, 38). On the other hand, when a ferric salt is precipitated with 
an excess of potassium ferrocyanide, the filtrate contains considerable 
quantities of potassium ferricyanide, formed by the reactions: 
FeCl3 + KjFe(CN)« = FeCl, + K3Fe(CN)« + KCl = KFeFe(CN)g + 3KC1, 
and in the filtrate, 3KFeFe(ON)6 = Fe8[Fe(CN)g]2 + K3Fe(CN)6. 

If ammonium carbonate solution is added to a boiling suspension of 



ORGANIC CHEMISTRY. i. 171 

Prussian blue, ammonium ferricyanide as well as ferrocyanide is found 
in the tiltrate, and the iron remains as FegO^. This is considered to 
prove that Prussian blue is a ferricyanide. C. H. D. 



Organic Boro-Nitrogen Compounds. Arden Richard Johnson 
(/. Physical Chem., 1912, 16, I — 28). — A series of compounds of 
boron tribromide with amines and nitriles was prepared in which 
boron as well as nitrogen is supposed to function as quinquevalent. 
Various additive compounds of boron trichloride, tribromide, and 
tri-iodide with ammonia are known, in which the proportion of 
ammonia varies from 1*5 to 15 molecules per molecule of boron 
compound. 

Boron tribromide reacts with amines and nitriles with liberation of 
heat, and additive compounds of the type (XjNIBBrg are apparently 
formed in most cases. The nitriles and tertiary amines, except 
trimethylamine, give fairly stable crystalline products. Compounds 
of this type were also isolated from the primary isoamylamine and 
aniline. The compounds of the aliphatic secondary amines im- 
mediately lose hydrogen bromide, amorphous products of the type 
RgN'BBrg resulting. Similarly, the product from ethylamine has the 
constitution NHEt'BBr2 With methylamine, the reaction apparently 
goes a stage further, and the product isolated has the formula 
B(NHMe)2Br. Piperidine and diphenylamine give compounds of the 
type (YNH)3,BBr3. 

The compounds were prepared by passing the dry gaseous amines 
into a carbon tetrachloride solution of boron tribromide or by adding 
the bromide solution from a burette to the anhydrous amine or nitrile 
dissolved in carbon tetrachloride. In some cases an oily insoluble 
product containing excess of amine was first formed, and afterwards 
converted into a solid product by further addition of bromide. 

The substances, (NHMe)2:BBr, NHEt-BBrg, NH2(C5Hii):BBr3, 
NHgPhlBBrg, NMe2'BBr2, and NPrg'BBrg, are white, amorphous solids 
sparingly soluble in carbon tetrachloride. The monoisoamylamine 
compound, which may be handled in the air, turns yellow in sunlight, 
but does not dissociate very rapidly below 40°. When heated up 
quickly, it appears to melt and decompose simultaneously. It burns 
furiously, colouring the flame intensely green. 

The i&oamyl compound, N'(C5Hij)2lBBr2, may be crystallised from 
carbon tetrachloride. It dissolves in water, giving diisoamylamine 
hydrobromide and boric acid. The substance, SCgHj^NjEBr^^, "is formed 
from piperidine in a violent reaction, which must be moderated by 
careful cooling. It has been obtained as a pale yellow precipitate, 
which readily loses hydrogen bromide when exposed over sodium 
hydroxide in a desiccator, being converted into the substance, 

C5H,„N-BBr,(C,HiiN),. 
The latter is a stable solid giving greenish-yellow, fluorescing solutions 
in organic solvents. The substance, 3NHPh2,BBr3, is a white precipitate 
comparatively stable in air. 

Trimethylamine reacts with boron tribromide with development of 

at. White fumes were given off, and no solid compound could be 



if 



i. 172 ABSTRACTS OF CHEMICAL PAPERS. 

isolated. The substaiice, NEt3'BBr3, crystallises from carbon tetra- 
chloride in long, slender prisms. The substance, NMcgPhlBBrg, formsa 
camphor-like, crystalline, hygroscopic mass. When exposed in a 
desiccator over sodium hydroxide, the elements of methyl bromide are 
removed, and the substance, NMePh'BBr2, remains. The latter is 
very rapidly decomposed by hot alkali with precipitation of boron 
nitride, BN. The j^yridine compound, C5Hr,NIBBr3, is a snow-white, 
amorphous mass, fairly stable in the air, but tending to dissociate with 
rising temperature ; at 120° it turns brown and sinters. When 
placed in a desiccator over sodium hydroxide, the elements of hydrogen 
bromide are removed, and the substance, C^H^N'BBrg, remains as a 
stable powder. It is suggested that boron is probably combined with 
the carbon as well as the nitrogen of the pyridine nucleus in this 
compound. The white substance, CgH^NIBBrg, formed from quinoline 
is more stable than the pyridine compound, and scarcely fumes in the 
air. 

The substances, CNMelBBrg, CNEtlBBrg, and CNPhlBBrg, are 
obtained from their carbon tetrachloride solutions as white crystals. 
The methyl compound dissociates very rapidly at 30°, and the ethyl 
compound is slightly more stable. The substaTwe, CHgPh'CNIBBi-g, 
which is difficult to purify by crystallisation, was obtained as a slightly 
yellow, crystalline mass. It melts with some decomposition. 

Most of the above boron tribromide compounds decompose or 
sublime without melting. Some of the nitrile compounds may be 
heated to nearly 200° before decomposing. Of the amine products 
those of pyridine and quinoline are the most stable. The products of 
decomposition by heat probably contain boron nitride in most cases. 
The substances described are violently decomposed by water, absolute 
alcohol, acetaldehyde, and acetic acid, the products containing boric acid 
accompanied by hydrogen bromide, ethyl bromide, bromoacet aldehyde, 
and acetyl bromide respectively. Acetone, the esters, and ether have 
a less violent action, and crystalline products containing boron and 
carbon have been obtained. Hydrocarbons usually exert no solvent 
action on boron bromide compounds, but with prolonged contact in 
sunlight the hydrocarbon assumes a red to brown tint. A slow decom- 
position also occurs in contact with chloroform and bromoform. 
Carbon tetrachloride and tetrabromide, in which the substances are 
but slightly soluble, have no chemical action on them. R. J. C. 



Preparation of Methylcyc^opentane. S. S. Nametkin {J. Russ. 
Phys. Ckem. Soc, 1911, 43, 1611— 1613).— The preparation of methyl- 
cycZopentane by the action of fuming hydriodic acid at 100 — 105° on 
cycZopentanylcarbinol (compare Zelinsky, Abstr., 1908, i, 727) and 
deduction of the iodide thus obtained by means of zinc dust in aqueous 
alcoholic solution gives a product containing cycZohexane. Hence, 
when heated with hydriodic acid, the c?/c/opentanylcarbinol undergoes 
partial isomerisation into a six-carbon atom ring compound. Similar 
cases of the ready isomerisation of substituted cyclic carbinols have 
been observed by Demjanoff (Abstr., 1910, i, 838) and by Kijner 
(Abstr., 1905, i, 772 j 1908, i, 530, 864 ; 1911, i, 42). T. H. P. 



ORGANIC CHEMISTRY. i. 173 

Polymerisation of Diethylene Hydrocarbons. Polymerisation 
of rt.s-Dimethylallene. IV. Sergius V. Lebedeff {J. Russ. Fhys. 
Chern. Soc, 1911, 43, 1735 — 1739). — For an unsymmetrical di- 
substituted allene, six dimerides are possible, three of each of the 

C~CIC C— C-0 

types : A Jl,!^ and ^_ • ' . Two of the compounds of the former 

of these types have been obtained (Abstr., 1911, i, 774), failure to 
isolate the third being due probably to its high velocity of polymerisa- 
tion. The author's results indicate that the velocity of polymerisation 
of hydrocarbons with conjugated systems of double linkings, lOIC'CICI, 

increases with diminution of the loading of the extreme carbon atoms 
and with increase of that of the intermediate ones. Hence, of the 
three dimerides of cts-dimethylallene of the first type, 1 : 2-diiso- 
propenylc^/c^obutane should be the most stable, 1:1:2: 2-tetramethyl- 
3 : 4-dimethylenec?/c^obubane should occupy an intermediate position 
in this respect (loo. cit.), and the third, 3 : 3-dimethyl-2-methylene- 
l-isopropenylc2/c^obutane, should readily polymerise. By the choice of 
suitable conditions, the remaining dimeride (the second) has now been 
obtained. 

1:1:2: 2-Tetramethyl-3 : i-dimethylenecyclobutane, 

has b. p. 140—1417760 mm., 66—67755 mm., Df 0*7927, < 1 -46063, 
w'J 1-45701, < 1-46988, r4° 1*47807, and yields tetramethylsuccinic 
acid when treated with ozone. 

The physical properties of these three dimerides, some of which 
were given wrongly in thq previous paper, are as follows : 

• Optical 

exalta- 
B. p. D20. tion. 

l:2-Disopropenylc2/cZobutaiie 179—181° 0-8422 2*34 

1 :l-Dimethyl-2-mcthylene-3-i5opropenyk2/cZobutane 149 — 150 0'7982 209 
1:1:2: 2-Tetramethyl-3 : 4-dimethylenec2/cZobutane 140—141 7927 1 '81 

As regards the non-formation of dimerides of the second of the two 
types given above, it is pointed out that the relations of unsaturated 
compounds to reactions of combination indicate clearly that the 
tensions of the affinities in the molecule are distributed unequally. 
For the complex ICICICI they are directed the most strongly towards 
the middle carbon atom, so that combination of the two molecules 
takes place first at this place, there being possible the two annexed 

2 3 1 2 3 arrangements. 

CHglCICMeg CH2=C:CMe2 With the former of these arrange- 

and i ments, further saturation of the free 

CHglCICMeg CMeglCICHg affinities gives the two dimerides, 

^ ^ ^ ^ ^ ^ 1:2- diisopropenylci/cZobutane and 

1:1:2: 2-tetramethyl-3 : 4-dimethylenec2/c/obutane, whilst with the 
latter, owing to its symmetrical character, only one dimeride, namely, 
1 : l-dimethyl-2-methylene-3-isopropenyk?/c^obutane, is obtained. This 
scheme hence excludes the possibility of formation of dimerides of the 
second type. T. H. P. 



i. 174 AIJSTKACTS OK CHEMICAL PAPERS. 

Ohemical Action of Light. XXII. Autoxidations. I. Giacomo 
L. CiAMiciAN and Paul SiLnEK(/?er., 1912,45, 38 — 43; Aui It. Accad. 
Lincei, 1911, [v], 20, ii, 673 — 677). — Aromatic hydrocarbons on 
prolonged exposure to the action of light in presence of water in au 
atmosphere of oxygen in sealed vessels are partly oxidised to the 
corresponding carboxylic acids ; small quantities of the corresponding 
aldehydes and of formic acid are also formed. 

Thus toluene yields benzoic acid and benzaldehyde ; p-xylene gives 
/;-toluic acid, m. p. 181°, and a little terephthalic acid, as well as traces of 
the aldehyde ; m-xylene forms 7;i-toluic acid, m. p. 111°, and isophthalic 
acid; o-xylene forms o-toluic acid, m. p. 107 — 108° p-Gymene yields 
some aldehyde, ;?-cuminic acid, m. p. 119°, /?-propenylbenzoic acid, 
m. p. 165° and a-hydroxy-/hcuminic acid, m. p. 156° 

In the dark the hydrocarbons are unchanged, p- and o- Nitrotoluene, 
also phenanbhrene, are practically unaltered after prolonged exposure 
to light. E. F. A. 

[Orientation in the Benzene Nucleus.] Julius Obermillkr 
(Ber.y 1912, 46, 165—167. Compare Abstr., 1911, i, 960).— The 
author upholds his claim of priority over Holleman (this vol., i, 20), 
and maintains that there is no essential difference between their views 
concerning substitution in the benzene nucleus. F. B. 

Benzene Hexachlorides and their Decomposition into 
Trichlorobenzenes. T. van der Linden (Ber., 1912, 45, 231 — 247). 
— a- and /3-Benzene hexachlorides, prepared by the action of chlorine on 
benzene in sunlight, form a eutectic solidifying at 155*5°. This 
jx)int was mistaken for the melting point by Matthews (Trans., 1891, 
69, 166). In addition to the a- and /3-isomerides, two new benzene 
hexachlorides are formed in the reaction : all four compounds are 
stereoisomerides. The y-isomeride crystallises in needles and lozenge- 
shaped forms, m. p. 112 — 113° ; the h-isomeride forms slender, lustrous, 
twin platelets, m. p. 129—132°. 

On^decomposition of a- benzene hexachloride with alkali, a mixture 
of 1:2:4-, 1:2:3-, and 1 : 3 : 5-trichlorobenzenes is obtained. The 
temperature at which decomposition is effected has no influence on the 
relative proportions of these, or is this proportion altered on replacing 
potassium hydroxide by sodium hydroxide or substituting methyl 
alcohol for ethyl alcohol. The proportion is, however, altered by the 
use of pyridine or quinoline, more of the 1:2:4- and less of the 1:2:3- 
isoraeride being obtained, the amount of the 1:3: 5-trichlorobenzeue 
remaining constant. 

)3-Benzene hexachloride, when decomposed by potassium hydroxide in 
ethyl alcohol, yields the same three trichlorobenzenes as the 
a-isomeride, but in different proportions, which are very similar to 
those obtained on decomposing the a-isomeride with pyridine. 
Pyridine, however, has hardly any action on the y8-compound. 

y-Benzene hexachloride yields the three trichlorobenzenes in slightly 
different proportions than either of the a- or /8-isomerides. 

It was not found possible to eliminate the chlorine in stages, neither 



ORGANIC CHEMISTRY. i. 175 

\\i\d hydrogen chloride be split off by means of aluminium or ferric 
chlorides. 

The fact that a considerable proportion of 1:2: 3-trichlorobenzene 
is formed indicates that the elimination of hydrogen chloride is not 
entirely between two neighbouring carbon atoms. E. F. A. 

Preparation of y-Chloropropylbenzene and its Homologues. 
Emanuel Merck (D.R.-P. 239076). — y-Ghloropropylbenzenej 

CgHg'CIIg'CIIg'CHgCl, 
a colourless oil with penetrating odour, b. p. 219 — 220° or 
110°/21 mm., is obtained in 78% yield from y-chloropropylaniline by 
diazotisation and subsequent reduction with stannous chloride in 
alkaline solution. F. M. G. M. 

2-Chloro-3 : 5-dinitrotoluene. Walther Borsche and Anna 
Fiedler {Ber., 1911,45, 270— 273).— 2-Chloro-3 : 5-dinitrotoluene is 
formed in only small quantity by nitrating o-chlorotoluene, and does 
not constitute the main product of ^e reaction as stated by Nietzki 
and Rehe (Abstr., 1893, i, 15). It crystallises from alcohol in stout, 
yellow rhombs, m. p. 63 — 64° ; Nietzki and Rehe give 45°. It is 
best prepared by heating 2-chloro-3-nitrotoluene or 2-chloro-5- 
nitrotoluene with a mixture of equal parts of sulphuric and fuming 
nitric acids for two hours on the water-bath. 

The above-mentioned mononitro-compounds are conveniently pre- 
pared by nitrating aceto-o-toluidide and hydrolysing the product with 
hydrochloric acid ; the resulting mixture of 3-nitro- and 5-nitro-o- 
toluidine is separated by steam distillation, and the amino-group 
replaced by chlorine according to Ullmann's method. 

4-Chloro-3 : 5-dinitrotoluene has m. p. 116 — 117°, and not 48° as 
given by Honig (Abstr., 1887, 1034). F. B. 

Conversion of the Bromonitrobenzenes into the Corre- 
sponding Dichlorobenzenes by Phosphorus Pentachloride. 
Julius Schmidt and Hans Wagner (Annalen, 1912, 387, 164 — 165). — 
When heated with phosphorus pentachloride in a sealed tube at 180° for 
six hours, o-, 7n-, and jo-bromonitrobenzenes are converted more or less 
smoothly into o-, m-, and /?-dichlorcbenzenes. 0. S. 

Action of Nitric Acid on c?/c^oPentane and Methylc?/c^open- 
tane. S. S. Nametkin(/. Russ. Fhys. Ghem.Soc, 1911, 43, 1603—1611. 
Compare Abstr., 1910, i, B>oO).~ Mtrocyclopentane, CgHc^'NOg, 
obtained by the interaction of aluminium nitrate and c^/c^opentane in 
a sealed tube, is a colourless liquid, b. p. 90 — 91°/40mm., D:;^ 1*0776, 
ir^ 1'4518, with the characteristic odour of secondary nitro-compounds. 
On oxidation with nitric acid, it yields glutaric acid, which is also 
formed when cyc^opentane itself is oxidised. 

Nitration of methylcyc^opentane by means of nitric acid yields 
l-nitro-l-methylc2/c^opentane and 2-nitro-l-methylc2/c^opentane, b. p. 
98— 99°/40 mm., Df 1-0381, < 1-4488 (compare Markownikoff, 
Abstr., 1899, i, 799). 

Thus, m the secondary nitro-product of methylc2/c^opentane the 



i. 176 AHSTKAPTS OK CHEMICAL FAI'KKS. 

nitio-group occupies the a position, whilst in that of methyk/jclo- 
litxaiie it oc!cupio8 the/J-position. 

The abovo two nitro-compounds formed by the nitration of 
uu'thylcyc/opentano are accompanied by succinic and a-methylghitaric 
acids; probable schemes are given for the formation of thet-e two 
acids. T. H. P. 

The Preparation of <o-2-Dinitrotoluene, its Homologues and 
Derivatives. Soci^xfe Ciiimique des Usines du Rh6ne (D.K.-P. 
239953). — u)-2-Diniirotoluene, NO./C^H^'CHg'NOg or 

N02-CeH,-CH:N0(0H), 
m. p. 67°, is readily prepared in 70% yield by heating o-nitrotoluone 
(2 parts) at 110 — 120° during eight hours with the gradual addition 
of 70% nitric acid (1 part), o-nitrobenzaldehyde and o-nitrobenzoic 
acid being simultaneously produced as by-products. The following 
compounds are de!«cribed : uiA-dinitrotoluene^ m. p. 91°; 4-c/<Zoro-a>-2- 
dinitrotoluetie, m. p. 112°; i-hrorno-(i)-2-(linitrotolue7ie, m. p. 113"5°; 
{j-chloro-(i)-2-dinitrotoluene, m. p. 82°; whilst o-nitro-m-xylene yields a 
mixture of <i}-Q-dinitroiai-x)/leiw, m. p. 86 '5°, and (aA-dinitro-m-xyleite^ 
m. p. 64° F. M. G. M. 

Preparation of Chloroalkylarylsulphonic Acids and of 
Chloroalkylarylcarboxylic Acids. Badische Anilin- & Soda- 
Fabhik (D.R.-P. 239311). — io-Cklorotoluene-p-sulphonic acid is readily 
pre{>ared by slowly dropping water (18 parts) into w-chlorotoluene-/?- 
sulphonyl chloride (225 parts) dissolved in 80 parts of hot alcohol. 
The sodium salt, SOgNa-CgH^'CHgCl, is sparingly soluble in water. 

o}-DicMorotoluene-m-sulpkonyl chloride, a crystalline powder insoluble 
in water and prepared by the action of phosphorus pentachloride on 
benzaldehyde-7/i-sulphonic acid, is converted by the foregoing treatment 
into u}-dichlorotoluene-m.-8ulphonic acid ; the sodium salt is moderately 
soluble in water. 

to-Chloi'0-ip-toluo]/l chloride, a colourless oil, b. p. 150 — 155° (pre- 
pared by chlorinating a hot solution of p-toluoyl chloride), when 
dissolved and maintained at — 5° in 98% sulphuric acid until the 
evolution of hydrogen chloride ceases, furnishes oi-cldoro-ip'toluic 
acid, m. p. 190 — 192° (decomp.), and insoluble in water. 

F. M. G. M. 

Preparation of Aromatic Sulphonyl Ammonium Com- 
pounds. Badische Anilin- &, Soda-Fabrik (D.R.-P. 239763). — 
When sodium w-chlorotoluene-jo-sulphonate is heated with dimethyl- 
aniline at 70°, it yields the compound, OqU^<^^^^ 2^NMePh, a 

colourless powder. 

Ethyl w-2-dichlo7'otoluene-p-sulphovnte, a colourless oil prepared by 
hydrolysing the corresponding sulphonyl chloride with sodium ethoxide, 
when similarly treated furnishes the compound, 

SOaEt-CcHaCl-CHg-NClMegPh, 
in colourless, hygroscopic crystals readily soluble in water and alcohol. 

F. M. G. M. 



ORGANIC CHEMISTRY. 



i. 177 



System of Nomenclature for ''Bridged Rings." Victor 
Grignard {Bull. Soc. chim., 1912, [iv], 11, 124— 129).— The author 
proposes to avoid the inconveniences of von Baeyer's system of 
nomenclature for such structures by (1) selecting for the nucleus of 
the name that of the fundamental ring, which is immediately apparent, 
traversed by one or more bridges ; (2) numbering the atoms in the 
bridges, after those of the fundamental ring, so that the bridges 
appear to be merely particular substituents attached at two points, 
and identified in the name by their "characteristic." This character- 
istic consists of the numbers of all the atoms, which appear in the 
" bridge," and the highest number in it indicates the total number 
of carbon atoms in the structure. The number of constituent rings, 
apart from the fundamental ring, is always twice the number of 
bridges, and is indicated by prefixes, bicyclo, tetracyclo, etc. Where 
the bridge contains an ethylenic linking, these prefixes become 
bicycleno and tetracycleno respectively, and the number of the 
atom at which the double linking begins is accented in the "character- 
istic." The following examples of the application of the system may 
be given : 

1 1 1 



./!\ 



""''J^l:'' Tet.acyelo.p-^-^]-hexane. ^^'^^^^^P ' ^ ^' 



T. A. H. 



Compounds of Antimony Trichloride and Tribromide 
with Polynuclear Benzene Hydrocarbons. Boris N. 
Menschutkin (/. liuss. Phys. Chem. Soc, 1911, 43, 1805—1820).— 
Diphenyl and diphenylmethane form with antimony trihalides mole- 
cular compounds containing 2 mols. of antimony salt to 1 mol. of 
hydrocarbon: 2SbCl3,C,,H,Ph, m. p. 71°; 2SbBr3,C6H,Ph, 60-5°; 



2Sbi3,C6H5Ph, ler 



2SbOl3,CH2Ph. 



m. p. 90°. Each concentration-temperature 
eutectic points, as follows : 



m. p. 100°; 



2SbBr8,CH2Ph2, 



I 



System. 
SbClg— CeHsPh 
SbBt'a— CeHgPh 
Sbl3-C„H,Ph 

SbCig— UH.J^h2 



M.p. 
Hydro- 
carbon. 
70-5° 
70-5 
70-5 
26 
26 



1st eutectic point. 



diagram exhibits two 

2nd eutectic point. 



Tempera- 
ture. 
50° 
47 
68 
22-5 
22-5 



n. 

2-2 

1-75 

89-4 

15-6 

14-6 



Tempera- 
ture. 

57° 

60-5 
160 

67 

82 



n. 
0-18 
0-52 
0-2 
0-6 
0-18 



M. p. 
SbXg. 

73° 

94 
166 

73 

94 



With antimony 
compounds, which 



trichloride and tri-iodide, 
melt without decomposing, 
tribromide it yields a compound with a melting point in the region of 
unstable equilibrium. 



diphenyl gives stable 
whilst with antimony 



i. 178 ABSTRACTS OF OHEMICAL PAPERS. 

Triphenylmethaiie forms no molecular compound with anlimony tri- 
bromide, but with the trichloride it gives the compound HbCig.CHPhg, 
melting at 49-6° in the region of unstable equilibrium. The diagram 
consists of three branches, the first eutectic point, corresponding with 
SbCl3,0-93CHPh3, lying at 49°, and the second with SbCl3,0-37CHPh3, 
at 35°. 

The diminished capacity to form compounds with antimony tri- 
halidea observed in the case of triphenylmethane may be related 
to the fact that this hydrocarbon differs considerably in its chemical 
properties from diphenylmethane ; thus, it forms molecular com- 
pounds with benzene and other hydrocarbons, and yields metallic 
derivatives, etc. 

Colorations are often observed on fusing these polynuclear hydro- 
carbons with antimony trihalides (compare Watson Smith, Abstr., 
1879, 831). T. H. P. 

Halogen Derivatives of Flaorene and Bisdiphenylene- 
ethylene. Julius Schmidt and Hans Wagner (Annalen, 1912, 387, 
147 — 164). — The method of converting 9 : 9-dichlorofluorene into 
bisdiphenylene-ethylene by heating with copper powder in benzene 
(Abstr., 1910, i, 550) has been applied to other halogenated fluorene 

derivatives j thus 9 : 9-dicIdwo-2-bromoJluorene, \^^^^ ^CClg,, m. p. 

178°, colourless needles, obtained from 2-bromofluorenone and phos- 
phorus pentachloride at 160 — 180°, is converted into 2 : 2'-dibromo-' 

C W Br C TT Rr 

bisdipli^nylene-ethylene, \^^ ^0:C<^\^^ ,m. p. 312°, red crystals, 

or, by sublimation, yellowish-green needles. This substance is con- 
verted into 2 : 2'-dihromobi8diphenylene-ethane^ 

m. p. 272°, colourless needles, by heating its ethereal solution with 
platinum black for eight hours in a current of hydrogen, and reacts 
additively with chlorine in chloroform and with bromine in carbon 
disulphide in sunlight to form respectively 9 : ^S -dichloro-2 : 2'-dibromo- 

bisdiphenylene-etlmne, A^„^^^CC1-CC1<V^^8^'", m. p. 268°, colour- 

less crystals, and 2 : 2' : 9 : ^'-telrabromobisdiphenylene- ethane y m. p. 
258° ; the latter in benzene reacts with silver acetate to form the 
diacetaU, A'S'^>C(0Ac)-C(0Ac)<V«^3Br^ ^ p 285°. 

O FT Rr 
9 : 9-Dichloro-2 : 7-dibromq/luorene, X*ttV >CCl2, m. p. 260°, colour- 

UgH3Br 

less needles, obtained from 2 : 7-dibromofluorenone and phosphorus 

pentachloride at 210 — 220°, is converted by copper into 2:2' :7:T-tetra- 

bromobisdiphenylene-ethylenej JI,^tt^t)'^CIC<^ i^ /^, m. p. 364°, red 

CgHgBr^ CgH3Br 

crystals, from which the following substances have been prepared : 

9:0'-dic/doro-2:2':7:1'-tetrabromobi8diphen7/le7ie-etJMne, m. p. 298—299°, 



ORGANIC CHEMISTRY. i. 179 

colourless needles ; 2 : 2' : 7 : 7' : 9 : 9'-hexabromobisdiphenylene-ethane, 
m. p. 310°, colourless crystals ; 2 : 2' : 7 : 1' tetrabromohisdiphenylene- 
ethane, m. p. 284°, colourless leaflets. The disappearance of colour 
coincidently with that of the ethylenic linking is noteworthy. 

When heated in a sealed tube at 180° for six hours, fluorenone and 
phosphorus pentachloride yield 9 : ^'-dichlorohisdiphenylene-ethane^ m. p. 
235—236°, 2:7:9: d-tetrachlorq/luorene, m. p. 215°, and a little 
2:7-dichloroJluorenone (i), m. p. 187 — 189°. 2 : 7-Dichlorofluorenone, 
m. p. 185 — 186° (which appears to be identical with Goldschmiedt and 
Schranzhofer's /8-dichlorofluorenone), is obtained best by heating 
2 : 7-diDitrofluorenone with phosphorus pentachloride in a sealed tube 
at 170 — 180°, and boiling the resulting 2:7:9: 9-tetrachlorofluorene 
with water ; it forms an oxime, decomp. 2iS°, phenylhydrazone, decomp. 
186 — 187°, and semicarhazone, decomp. 345°, and is converted by 
copper into 2 : 2' : 7 : I'-tetrachlorohisdiphenylene-ethylene, a red 
substance, m. p. above 380°. C. S. 

The Preparation and Reactions of Bis-a-hydrindone-(2 : 2-)^ 
spiran. Hermann Leuchs and Dan Radulescu {Ber., 1912, 45, 
189 — 201). — DibenzylmaloDic acid, the preparation of which is fully 
described, is converted, by means of phosphorus pentachloride, into 
dihenzijlmalonyl chloride, b. p. 216— 218°/17 mm., 232— 235°/32 mm., 
m. p. 68 — 69°. When dissolved in ether and treated with ammonia 
and aniline respectively, this yields the corresponding amide (m. p. 
198 — 199'') and anilide (m. p. 196 — 197°). Boiling alcohol converts 
it into the ester. During distillation of the chloride under diminished 
pressure, as also when it is heated at 250 — 270° for some time, 
hydrogen chloride is evolved, and small quantities of his-a-hydrindone- 
(2 : 2-)spiran formed. The latter is best prepared by distilling the 
chloride under diminished pressure in the presence of 2% of aluminium 
chloride. It has b. p. 255— 257°/12 mm. (corr.), m. p. 174°. Phenyl- 
hydrazine converts it into bis-a'hydrindone-{2 : 2-)spiranbisp/ienyl- 
hydrazone, colourless prisms, m. p. 200 — 201° (decomp.). When 
treated with hydroxylamine, a substance^ Cj^H^gOgN, is formed 
(m. p. 214 — 215°), which possibly has the formula 

'^■Under the action of sodium hydroxide, bis-a-hydrindone-(2 : 2-)-spiran 
readily yields the sodium salt of a strong, monobasic acid, which is 
stable towards excess of alkali. The free acid has m. p. 140 — 142°, 
and, when heated at 220°, evolves water vapour with the reforma- 
tion of spiran. The composition of the acid is probably expressed by 

the formula C,H,<'^^q^|^HC<*^^^!>C,H,. 

It can be resolved into optically active forms by crystallisation of 
the brucine salt from acetone. Attempts were made to prepare the 
methyl ester of the acid by the action of methyl iodide on the silver 
salt. The ester could not be obtained in the crystalline state. When 
distilled under diminished pressure, it decomposed with the 
regeneration of spiran. 

Bis-a-hydrindone-(2 : 2-)-spiran, when treated with alcoholic ammonia, 



i. 180 ABSTRACTS OF CHEMICAL PAPERS. 

forms two compoundft, Cj^IT^gON, m. p. 246 — 248° (decomp.), and 
C^^Hj^OgN. The latter, when rapidly heated, ruelts at 124—128 
(deeomp.), and is readily transforiiie«l into the former by lioating it, 
above its m. p., or by treating it with concentrated hydrochloric acid. 
These substances are probably not the nitrile and amide of the abov* 
described acid, since neither evolves ammonia when treated with 
potassium hydroxide. The following formulae are provisionally 

proposed for them : CQK^<^'^^'^^G<i^^^£>CQU ^ and 



5H(0H)-NH' 

Anhydrohi8-a-hydrindonespira7i, obtained in small quantity by the 
distillation of dibenzylmalonyl chloride under ordinary pressure in the 
presence of 4% of aluminium chloride, crystallises from glacial acetic 
acid in light red needles, m. p. 256—257°. H. W. 

Reactivity of Side-chaiDS in Nuclear Nitrated Homologues 
of Benzene. Walther Borsche (Annalen, 1912, 386, 351 — 373). — 
One of the halogen atoms is readily substituted, the other only with 
difficulty, when 1 : 3-dichloro-4 : 6-dinitrobenzene is warmed in ether 
with an excess of ethyl sodioacetoacetate. On the other hand, 
both methyl groups react readily when 4 : 6-dinitro-m-xylene and 
benzaldehyde (2 mols.) are heated at 190° with a little piperidine ; the 
main product is 4 : 6-dinitro-l : 3-distyrylbenzenej 

m. p. 186°, yellow needles, very little 4 : ^-dinitro-Z-methylstilheiie, 
CgH2Me(N02)2*CH:CHPh,m. p. 145°, being formed. Trinitromesitylene, 
dinitromesitylene, trinitro-j/^-cumene, and 2 : 4-dinitroethylbenzene 
do not react with benzaldehyde. 2:4: 6-Trinitrotoluene yields 
trinitrostilbene (UUmann and Gschwind, Abstr., 1908, i, 622). 
2:4: 6-Trinitro-7?i-xylene, benzaldehyde, and a little piperidine, 
when heated in boiling amyl alcoholic solution, yield 2:4: Q-trinitro- 
l iddistyrylbenzenej OggHisOgNg, m. p. 147 — 148°, yellow needle?. 
Corresponding substances, C24Hj()OgN3, m. p. 155°, and C22Hj30jqN5, 
m. p. 268° (decomp.), are obtained with anisaldehyde and p-mtro- 
benzaldehyde respectively. Theso*condensations proceed most smoothly 
in the toluene series, less readily in the xylene series, and badly or not 
at all in the mesitylene series. The author is of opinion that in these 
nitrated methylbenzenes the distribution of the residual affinity of 
the benzene nucleus is such that, when only one methyl group is 
present, the influence of the residual affinity is concentrated on the 
carbon atom of this methyl group, its hydrogen atoms, therefore, 
becoming more mobile ; as, however, the symmetry of the whole 
molecule is increased by the introduction of two and three methyl 
groups, the influence of the residual affinity is distributed between the 
methyl groups, with the result that their hydrogen atoms become 
less and less mobile. In the case of the chloronitrobenzenes, the 
elimination of the halogen atom is due, according to the author, not to 
any weakening of the union between it and the carbon atom, but 
rather to a striving of the molecule to assume an ortho- or para- 
quiuonoid structure; the reagent s then held additively, the finai 
product being obtained by the elimination of a halide ; thus : - 



ORGANIC CHEMISTRY. i. 181 



CI 



--> (I i::: --> 



( I— X ~^ ll X 

\/\ci \^ 

Ullmann and Gschwind (loc. cit.) have shown that the reactivity of 
the methyl group in 2 : 4-dinitrotoluene still persists when one of the 
nitro-groups is replaced by a carboxylic, sulphonic, or cyanogen group. 
The author finds, however, that in 6-nitro-4-cyano-m-xylene only one 
methyl group reacts with benzaldehyde and a little piperidine at 
190 — 200°, giving a very poor yield of Q-nitro-i-cyano-S-methyl- 
stilbene (?), IsrO/CgH2Me(CN)-CH:CHPh, m. p. 183—184°, yellow 
needles. 2 : 4-Dicyanotoluene does not react with benzaldehyde. 

4 : 6-Dinitro-l : 3-distyrylbenzene forms a tetrabromide, 
C«H2(N02)2(CHBr-CHPhBr)2, 
m. p. 207 — 208° (decomp.), and by reduction with stannous 
chloride and acetic and hydrochloric acids yields 4 : Q-diamino- 

1 : 3-distyrylbenzene, m. p. 204°, yellow crystals with green fluor- 
escence. The base forms fluorescent solutions, yields a dibenzoyl 
derivative which is unchanged at 275°, and reacts with benz- 
aldehyde in boiling alcohol to form the dibenzylidene derivative, 
CgH2(N:CHPh)2(CH:CHPh)2, m. p. 238—239°, deep yellow, non- 
fluorescent needles. A methyl-alcoholic solution of the base is reduced 
by hydrogen in the presence of a little colloidal palladium, yielding 
4 : ^-diamino-\ : 3-di-^-phenylethylbenzene^ CgH2(NH2)2(CH2'CH2Ph)2 
(diacefyl derivative, m. p. 224°; dibenzoyl deriva.tive, m. p. 273°). 

4-Cyano-m-xylene and nitric acid, D 1*52, at 0° yield a mixture of 
sparingly soluble (in alcohol), yellowish prisms, m. p. 107 — 108° 
(probably Q-nitroA-cyano-m-xylene), and easily soluble, white needles, 
m. p. 120 — 121° ([.>rob:ibly i-cycono-2-nitrO'm.-xylene). By diazotisa- 
tion and treatment with cuprous cyanide, 4-cyano-o-toluidine yields 

2 : 4:-dicyanotoluenej m. p. 144 — 145°, white needles. C. S. 

Non-Bxistence of «/^-Diphenyleneketone [i/^-Pluorone]. A 
New Red Hydrocarbon. Rudolf Pummerer (Ber.j 1912, 45, 
294 — 298). — The red modification of fluorone, obtained by Kerp 
(Abstr., 1896, i, 238; compare also Stobbe, ibid., 1911, i, 651) by 
the distillation of calcium diphenoxide, is shown to be the ordinary 
yellow variety of fluorone, contaminated with traces of the red 
substance, first observed by Fittig and Ostermayer (this Journ., 1873, 
892), and shown by them to be produced simultaneously in the 
distillation. This red impurity is insoluble in alcohol 
and solvents of low b. p., but dissolves to a slight 
extent in solutions of fluorone, from which it may be 
removed by shaking in the cold with animal charcoal. 

It may be isolated by repeatedly triturating the 
" red fluorone" with cold alcohol and crystallis- 

\ y N- A ing the residue from benzene. It forms slender, 

jB^ ^"^^ lancet-shaped crystals, m. p. 306°, yields strongly 

■re 



/% /\ 

I 



-II I 



'^OL. CII. I. 



i. 182 ABSTRACTS OP CHEMICAL PAPERS. 

yellow, fluorescent solutions, and has the composition CgjjHj^. On 
account of its bright red colour, the hydrocarbon is termed by the 
author rubiceyie. 

Its constitution has not yet been definitely established, but argu- 
ments are advanced in favour of the formula given on the preceding page. 
With bromine in chloroform solution, it forms a 6romo-8ubstitution 
product ; the picrate crystallises in very slender, brownish-red prisms. 

Kerp's " red fluorone " contains in addition to rubicene a white 
substance, which remains behind on dissolving the ketone in concen- 
trated sulphuric acid. F. B. 

Isomeric Schififs Bases. Bronislaw Pawlewski (Chem. Zentr., 
1912, i, 29; from Chem. Pohki, 1911, 11, 121— 122).— Of the five 
substances obtained by the author by condensing benzoin with 
benzylamine, one, m. p. 88 — 90°, is the trans-modification of benzylidene- 
henzylamine^ CHPhlN'CHgPh, and is stereoisomeric therefore with, 
the liquid benzylidenebenzylamine, b. p. 200 — 202°/ 10 — 20 mm., 
described by Mason and Winder (Trans., 1894, 65, 191). C. S. 

The Homo-chromoisomerism of the Phenylmethylpici 
amides. Arthur Hantzsch (Ber., 1912, 45, 360—363).- 
Polemical ; a reply to Biilmann (Abstr., 1911, i, 963). D. F. T. 

Nitration of the Acyl Derivatives of jo-Anisidine. Frederk 
Reverdin and Armand de Luc {Ber., 1912, 45, 349 — 354). — . 
continuation of earlier work (Abstr., 1909, i, 377, 913 ; 1910, i, 470)^ 
in which a study has been made of the effect of the substitution of 
the nitrobenzoyl group into the amino-group of p-anisidine on th< 
behaviour of the base towards nitration. 

m-MtrobenzenesiUphonyl-p-anisidide, NOg'CgH^'SOg'NH'CgH^'OMi 
obtained by the action of the acid chloride on the base, forms whil 
needles, m. p. 135°; the acetyl derivative forms needles, m. p, 
181—182°. 

o-Nitrotoluene-'p-sulpIionyl-^-anisidide, obtained similarly, formi 
needle crystals, m. p. 81°; acetyl derivative, m. p. 161°. 

The nitration of the above nitrobenzenesulphonyl-/?-anisidide witl 
nitric acid, D 1*38, without cooling (max. temperature 36°), gives as 
chief product an orange-yellow rfmiiro-derivative, m. p. 170°, which cai 
be hydrolysed to the corresponding free base, 2 : 5-dinitro-jt?-anisidine 
If the temperature is allowed to rise to 62°, a mixture of the previoi 
dinitro-compound with the isomeric 3 : 5-c^im7ro-compound, m. p, 
165 — 166°, is obtained; this forms white needles, and hydrolyses 
3 : 6-dinitro-4-aminoanisole. If the mixture during nitration is heatec 
over a free flame, there is obtained the nitrohenzenesulphonyl derive 
ative of 2:3: 6-trinitro-4-aminoanisole, which forms small, prismati 
crystals, m. p. 189—190°. 

When nitrated as an emulsion in acetic acid at 70° with nitric aci< 
D 1*38, the main product is the above 3 : 5-dinitro-derivative. 

With nitric acid, D 1*52, between 0° and 5°, the product consists oj 
a mixture of the 2 : 5-dinitro- and the 2:3: 6-trinitro derivatives ; 
higher temperatures decomposition occurs ; if the nitration with aci< 
of this strength is performed at 5 — 10° in an emulsion in acetic acid, 



ORGANIC CHEMISTRY. i. 183 

& monoriitro-derivative is obtained (yellow needles, m. p. 127°), which 
on hydrolysis gives 3-nitro-4-aminoanisole. 

With nitric acid, Dl'38, the above-mentioned nitrotoluenesulphonyl- 
^-anisidide at 36° yields a ??i07iom>o -derivative (prismatic crystals, 
m. p. 132°), the constitution of which is shown by its hydrolysis to 3-nitro- 
^-anisidine. At higher temperatures, the nitrotoluenesulphonyl 
derivatives of 3 : 5-dinitro- and 2 : 3 : 6-trinitro-p-anisidine are obtained 
(m. p. 125—140° and 184—185° respectively); the former of these is 
also the product of nitrating a solution in acetic acid. 

With nitric acid, D 1-52, at 5—10°, the product contains the nitro- 
toluemsulphonyl derivatives of 2 : 3-dinitro-j(?-anisidine and 2 : 5- 
dinitro-;?-anisidine (m. p. of acyl derivatives, 180° and 154° 
respectively) ; on nitrating in acetic acid in the cold, the above- 
mentioned nitrotoluenesulphonyl derivatives of 3-nitro-^-anisidine 
and 2 : 5-dinitro-jo-anisidine are obtained, the latter preponderating. 

D. F. T. 

Decomposition of Mixed Phenyl Oxides in Presence of 
Nickel and Hydrogen. Alphonse Mailhe and M. Mueat (Bull 
SoG. chim., 1912, [iv], 11, 122— 123).— It is shown that all phenyl 
alkyl oxides when passed over heated nickel in a current of hydrogen 
are decomposed in accordance with the equations (1) C^H.-O-R + H = 
C,H,.OH + RH, and (2) C,H,.O.R + H, = C,H, Vr-OH: the alcohol 
and the paraffinic hydrocarbon formed being destroyed by the further 
action of the nickel. Anisole is most readily attacked, and yields 
52% of the possible weight of phenol, whilst phenyl tsoamyl oxide 
yields only 22%. Diphenyl oxide is attacked with great difficulty, and 
gives only 6% of the possible weight of phenol. Veratrole at 205° 
yields 16% of the possible weight of guaiacol, and the latter, on 
turther treatment at 205°, yields a mixture of phenol and catechol. 

T. A. H. 

[Preparation of ;?-Aminophenyl Methyl Mercaptole.l Aktien- 
(iESELLscHAFT FUR Anilin-Fabrikation (D.R.-P. 239310).--p-^mmo- 
phenyl methyl mercaptoU, a colourless oil, comparing favourably with 
phenacetin in therapeutical action, is obtained by reducing «-nitro- 
phenyl methyl mercaptole (Blanksma, Abstr., 1902, i, 281); the salts 
are colourless and crystalline, and the«ce«y derivative forms colourless 
needles, m. p. 127—128°. j^. ^ q ^ 

Preparation of 4-Chloro-a-naphthol. Aktien-Gesellschaft 
fUR Anilin-FabrikatioxX (D.R.-P. 240038).-It is found that 4-chloro- 
i-naphthol can be prepared by treating a-naphthol arylsulphonyl ethers- 
^ith chlorinating agents. a-Naphthyl ^-toluenesulphonate, colourless 
leedles, m. p. 83—84°, prepared by the action of jt^-toluenesulphonyl 
mioride on sodium a-naphthoxide in alcoholic solution, was dissolved 
n carbon tetrachloride and treated with chlorine, when a satisfactory 
^leld of 4-chloro-a-naphthol (m. p. 116°) was obtained. 

„ F. M. G. M. 

■ 2 



i. 184 ABSTRACTS OF CHEMICAL PAPERS. 

The Red Coloration Produced in the Ferric Chloride 
Reaction with Catechol in Alkaline Solution. I. Rudolf 
Friedrich Weinland and Karl Binder (Ber., 1912, 45, 148 — 154). 
— The green coloration of an aqueous catechol solution produced by 
ferric chloride is changed to deep red on the addition of sodium, 
potassium, ammonium, barium, calcium, and magnesium hydroxides. 
The red coloration is due to the formation of salts of an acid, 

H,[l'V"(CeH,0,)3]> 
analogous to the ferricyanides or ferrioxalates. 

The potassium salt, K3[Fe"'(CgH402)3],2H20, is obtained as a lustrous, 
crystalline, brownish-black to dark bronze-red powder, consisting of 
microscopic ti iangular prisms, by the addition of fei ric acetate to a 
solution of catechol in strong aqueous potassium hydroxide. It readily 
dissolves in water to deep red solutions, which are decolorised by 
excess of acid with the liberation of catechol. When heated with 
sodium sulphide or potassium cyanide in aqueous solution, the potassium 
salt is decomposed, yielding ferrous sulphide and potassium ferro- 
cyanide respectively, although in the presence of potassium hydroxide 
the aqueous solutions may be heated with the substances without 
undergoing change. 

The tendency to form salts of the above acid is so pronounced, that 
freshly precipitated ferric hydroxide in the presence of aqueous alkalis 
or ammonia dissolves on the addition of catechol, forming the 
correspondiDg alkali or ammonium salt. 

The ammonium salt, (NH4)3[Fe"'(CgH^02)3],H20, prepared in a 
similar manner to the sodium salt, is a brownish-black powder, 
consisting of microscopic, flat, violeb-red needles. 

The sodium salt, Na3[Fe"'(C6H4O2)3],10H2O, forms microscopic, red, 
hexagonal columns, capped with truncated pyramids. 

The lead salt is precipitated quantitatively on the addition of lead 
acetate to an aqueous solution of an alkali salt. The morphine and 
strychnine salts are crystalline; the quinine and hrucine salts are 
amorphous. 

Similar complex salts, stable towards alkalis, are obtained from 
catechol and aluminium, cupric, nickel, cobalt, and manganous salts, 
and also from pyrogallol, salicylic, gallic or protocatechuic acids, and 
ferric salts in alkaline solution. F. B. 

Derivatives of 4-AniiDO-orcinol (2-Amino-3 : 5-dihydroxy- 
toluene). Ferdinand Henrich, G. Taubert, and H. Birkner {Ber., 
1912, 45, 303—314. Compare Abstr., 1903, i, 413).— 2-Amino- 
orcinol has now been isolated in the free condition by the addition 
of sodium hydroxide to a cold aqueous solution of the hydro- 
chloride in quantity just insufficient for complete decomposition. 
It crystallises from ethyl acetate in lustrous, silvery-white leaflets, 
decomposing at 188 — 190°, with previous darkening at 160 — 180°. 
Its hydrochloride is oxidised by chromic acid in aqueous solution to 

^-chloro-Z-hydroxytoJuquinone^ CO\pTTl— piij'^^CO, which forms 

intensely yellow crystals, m. p. 181 — 182°, volatile in ether vapour, 
dissolves in alkalis, yielding intensely red solutions, and is reduced by 



ORGANIC CHEMISTRY. i. 185 

sulphur dioxide in aqueous solution to i-chloro-^ : 3 : b-trihydroxytoluene, 
C7H7O3CI, colourless needles, m. p. 137-5°. Acidification of the 
solutions of the quinone in aqueous ammonia or sodium carbonate 
results in formation of a substance having the same composition as the 
original quinone. This substance separates from benzene or chloro- 
form in yellow crystals, darkening at 220°, dissolves in water less 
readily than the original quinone, and is not volatile in ether vapour ; 
but whether these differences are to be referred to isomerism or 
polymerism has not yet been determined. 

That the quinone has the above constitution and not that of the 

isomeric 6-chloro-3-hydroxytoluquinone, CO<Cpp,LJp,^^^CO, has 

been established by the synthesis of the latter compound from 
2-amino-orcinol hydrochloride. This is converted by amyl nitrite 
in alcoholic solution into orcinol-2-diazomum chloride, a yellowish- 
white powder, which forms, with cuprous chloride, a red, crystal- 
line additive compound, CgH2Me(OH)2*N2Cl,Cu2Cl2. When heated 
under diminished pressure the additive compound melts at 80 — 90°, 
and decomposes at a higher temperature into 2-chloro-orcinol, 
C^HyOgCl, m. p. 138 — 139°, with previous sintering at 
115°. 

The last-named compound reacts with amyl nitrite and potassium 
hydroxide in alcoholic solution to form the potassium salt of 2-chloro- 
6-nitroso-orcinol, from which the free nitroso-compound is obtained by 
acidification with dilute sulphuric acid. 

2-Chloro-Q-nitroso-orcinol, C^HgOgNCI, exists in two modifications : 
a stable, yellow, crystalline form, melting at 159 — 160° with previous 
darkening, and a brown modification, which passes into the yellow 
variety when heated. 

2-Chloro-6-amino-orcinol hydrochloride is obtained in slender, white 
needles by reducing the preceding nitroso-compound with stannous 
chloride and hydrochloric acid. It is oxidised by chromic acid in 
aqueous solution to Q-chloro-3-hydroxy toluene, ruby-red crystals, m. p. 
165—166° (decomp.). F. B. 

Constitution of Dmoeugenol. Ernesto Puxeddu (Atti B. Accad. 
Lincei, 1912, [v], 21, i, 42-46. Compare Abstr., 1909, i, 225).— The 
paper deals with the action of light on isoeugenol and on its methyl, 
fithyl, and propyl ethers, as well as the action of light on eugenol and 
its ethers. The author has also examined the action of nitrous acid 
on isoeugenol ethyl ether and on diisoeugenol diethyl ether. 

When a solution of 100 grams of woeugenol in 200 c.c. of alcohol is 
treated with 25 c.c. of hydrochloric acid and exposed to light in a 
sealed tube, crystals of diisoeugenol are quickly deposited, and if the 
precipitate is collected after two days, the yield amounts to 60%. If 
the filtered solution is again exposed to light, a further quantity of the 
polymeride can be obtained. The mother liquors show a splendid blue 
fluorescence. Under the same conditions, sulphuric acid also acts 
feebly as a polymerising agent. isoEugenol methyl ether, isoeugenol 
ethyl ether, and isoeugenol propyl ether yield the analogous polymerides 
when treated in the same way. isoEugenol propyl ether, Cigll^gOg, 



i. 186 ABSTRACTS OP CHEMICAL PAPERS. 

prepared from woeugenol with sodium propoxide and propyl iodide, 
crystallises in long, prismatic needles, m. p. 54". Diisoeugenol dipropyl 
ether^ {0^%H.]fi<i)2^ forms prismatic needles, m. p. 94°. 

Eugenol and its methyl and ethyl ethers under the same conditions 
are not acted on by light. 

When woeugenol ethyl ether is treated with glacial acetic acid and 
potassium nitrite, a substance, CjgH^^O^Ng, is obtained, which 
crystallises in yellow, tabular prisms, m. p. 85". It is assigned the 
formula of the peroxide^ 

C«H3(OMe)(OEt).C==N.9, 

CMeiN-C) 
analogous to that from zsoeugenol methyl ether (compare Malagnini, 
Abstr., 1895, i, 35). Diisoeugenol diethyl ether does not react with 
nitrous acid, and therefore probably does not contain an unsaturated 
side-chain. R. V. S. 



Action of Phorone on Catechol and Pyrogallol. Mario 
GuiGhiE^o (Atti B. Accad. Sci. Torino, 1912, 47, 16 — 22).— Fabinyi 
and Szeki (compare Abstr., 1905, i, 591, 888) obtained products by 
heating acetone with catechol and with pyrogallol in a sealed tube at 
145°. In the present paper it is shown that the formulae ascribed to 
these substances are incorrect. Under the conditions of experiment 
the acetone is condensed to phorone, which reacts with the phenols, 
giving substances of the following constitutions, respectively : 

C(CH:CMe2)2[CeH3(OH),]2 
and C(CHICMe2)2[CgH2(OH)3]2. This explains the existence of the 
tetrabromo- and dibromo-derivatives. In confirmation of this view, 
the authors have prepared the same substances, using phorone instead 
of acetone. It is not necessary to heat the mixture at 145°; the 
same products are obtained when phorone and the phenol are heated 
together in a sealed tube at 100°, or even in an open flask with 
condenser. In the case of the product from pyrogallol the somewhat 
discordant analyses of Fabinyi and Szeki are explained by the fact 
that the substance contains 1 mol. HgO, which it loses completely 
only at 130 — 140°, and which it re-absorbs very readily on exposure 
to air. R. V. S. 

Action of Formic Acid on Triarylcarbinols. Alfred Guyot 
and A. Kovache (Com;)^ renrf., 1912, 154, 121— 122).— Triarylcarbinols 
are readily reduced when treated with twenty times their weight of 
crystallisable formic acid, giving the corresponding hydrocarbons with 
formation of water and evolution of carbon dioxide. The reaction 
may be made use of for accurately determining the number of hydroxyl 
groups in such carbinols, by weighing the carbon dioxide evolved from 
less than a gram of the substance. Quantitative results were obtained 
with triphenylcarbinol, phenyldi-jt>-tolylcarbinol, o-benzoyltriphenyl- 
carbinol, and 9 : 10-diphenylanthranol, whilst 9-phenylanthranol and 
9 : lO-dihydroxy-9 : 10 : 10-triphenyldihydroanthraceue gave less than 
the calculated amount of carbon dioxide, although the yield of 
hydrocarbon was theoretical. W. O. W. 



ORGANIC CHEMISTRY. i. 187 

The Walden Inversion and Substitution Processes. Emil 
Fischer {Annalen, 1912, 386, 374—386. Compare Abstr., 1911, i, 
418). — An amplification of the author's view that the phenomena met 
with in the addition of halogens or halogen hydracids to stereoisomeric 
unsaturated compounds are probably of a similar type to the Walden 
inversion. Reactions such as that whereby both inactive dibromo- 
succinic acids result by the addition of bromine to maleic or to fumaric 
acid have been regarded by Werner and by van't Hoff as exceptional 
and due to a specific action of the halogen. Examples are given, 
however, to show that similar results may be obtained by the addition 
of groups or atoms other than halogens. It is true that the oxidation 
of cinnamamide by potassium permanganate yields only one phenyl- 
glyceramide, 0H-CHPh-CH(0H)-C0-NH2, m. p. 161—162° (corr.) 
(which yields the phenylglyceric acid, having m. p. 141°, by hydrolysis), 
and the oxidation of cinnamoylglycine gives only one phenylglyceryl- 
^^2/cm.?,OH-CHPh-CH{OH)-CO-NH-CH2-C02H,m. p. 144—145° (corr.). 
However, Baeyer has shown that A^-tetrahydrophthalic acid yields two 
stereoisomeric hexahydrophthalic acids by reduction, whilst Fittig has 
obtained two dimethylsuccinic acids by the reduction of dimethyl- 
fumaric acid. C. S. 

Spectrochemical Differentiation between Hydroaromatic 
Compounds with Endocyclic and with Semicyolic Double 
Linkings. Karl Auwers and Philipp Ellinger {Annalen^ 1912, 
387, 200 — 239). — Unsaturated hydroaromatic hydrocarbons contain- 
ing semicyclic double linkings exhibit a moderate exaltation of the 
specific refraction and a marked exaltation of the specific dispersion. 
Unsaturated hydroaromatic hydrocarbons containing endocyclic double 
linkings are optically normal. These statements are based, not only 
on the spectrometric examination of the many alkylidenec^/c^o- 
paraffins wliich have been prepared by Wallach, but also on a direct 
comparison of the alkylidenec?/cZohexanes (methylene-, ethylidene-, 
and isopropylidene-c?/c?ohexanes) with the isomeric alkyl-A^-c^/c^o- 
hexenes (methyl-, ethyl-, and tsopropyl-c^/c^ohexenes) ; the latter are 
optically normal, whilst the former exhibit an exaltation of 0'28 — 0*47 
of ^j), and an exaltation of 6 — 10% of %y - %„,. 

The spectrochemical method of differentiating between the two 
classes of isomerides has been utilised to show that Sabatier and 
Mailhe's alkylideneci/c^ohexane derivatives are really unsaturated 
endocyclic compounds, and that Zelinsky and Gatt's 3-methyl-l- 
ethylidenecyc/ohexane must be, on account of its optical normality, 
3-methyl-l -ethyl- A^-c^/cZohexene. 

A^-c^/c^oHexenylacetic acid and its esters and their homologues 
containing a methyl group in position a, 2, 3, or 4 are optically 
normal. c^/c^oHexylideneacetic acid and its homologues containing a 
methyl group in position 2, 3, or 4 have too high m. p.'s to be 
suitable for spectrometric examination, but their methyl and ethyl 
esters show a marked exaltation, 0*79 — 1*05, of the specific refraction, 
^D» and still more pronounced exaltation, 31 — 40%, of the specific 
dispersion, '%y - 2^- These are due, not only to the semicyolic, bub 
also to the conjugated, double linking. Esters of the acids contain- 



i. 188 ABSTRACTS OF CHEMICAL PAPERS. 

ing a methyl group in the a-poHition contain a dieturbed conjugation, 
and therefore show smaller exaltations, but even in these cases the 
exaltations are so pronounced that there can be no uncertainty in 
distinguishing such esters from those of a-substituted c^/cZohexenyl- 
acetic acids. 

The authors regard the spectrometric method as far safer than any 
chemical process for the determination of the constitution of such 
easily changeable substances as cyc/ohexenyl- and the cyc^ohexylidene- 
acetic acids. 

The following new compounds are described ; they have been 
obtained by Wallach's methods as a rule, l-ifioPropy'cyclohexanol, 
CgHigO, b. p. 176-4— 176 7°, Df' 09142, n^ 146064, rijy 1-46419, and 
ny 1-47387 at \b-b° \ ethyl ^}-cyc\ohexenyJ acetate, C^Hg-CHg'COgEt, 
b. p. 100712 mm., Df2 0-9829, n^ 1-46422, n^ 1-46906, w^ 1-48017 
at 16-2°; methyl a-l-hydroxycyclohexylpropionate, 
OH-CgH,o-CHMe-C02Me, 
b. p. 132°/ 18 mm., Df 10537; methyl a- A' -cy clohexenylpropionate, 
CeHg-CHMe-COgMe, b. p. 108— 108-5°/18 mm., Df^ 0-9864, 
na 1-46373, r?^ 1'46648, riy 1*47885 at 18*3°; methyl 2-methylcyc\o- 
Jiexylicleneacetat'i, CgHgMelCH'COgMe (prepared from methyl iodide 
and the silver salt of the acid, m. p. 68°), b. p. 119-9°/15 mm., 
Di-'^ 0-9767, Tia 1-47681, 7ij, 1-48072, riy 1-49802 at 14-2°; the corre- 
sponding ethijl ester has b. p. 128-2°/13 mm., J)\^^ 0-9587, n^ 1-47524, 
Wp 1*47906, and rty 1-49639 at 14 8°; methyl 3-methylcyc\ohexylide,ne- 
oce^afe, C6H9Me:CH'CO.^Me, b. p. 117°/13mm., Df« 0-9752, n, 1-47534, 
Tijy 1-47926, 7iy 1-49668 at 15-5°; the ethyl ester has b. p. 131-4°/ 
18 mm., -D\' 0-9571, n^ 1-47347, n^ 1*47730, ny 1-49464 at 15°. 

C. S. 

Correlation of lonieation and Structure. II. Negatively- 
Substituted Benzoic Acids. C. G. Dkrick (J. Amer. Chem. /Soc, 
1912, 34, 74 — 82). — It was shown in an earlier paper (Abstr., 1911, 
ii, 713) that the free energy of ionisation for neg^atively substituted 
monobasic fatty acids in aqueous solution at 25° is the sum of the 
separate effects of each atom in the molecule. Hence it was demon- 
strated that the position of a negative atom or group in an acid can 
be determined if its a-" place factor " and the ionisation constant of 
the substituted acid are known. In the present paper it is shown that 
the additive relationship in the free energy of ionisation is also true 
in the case of aromatic acids, and that it is therefore possible to 
determine the structure of substituted benzoic acids containing 
negative groups or atoms, if the ortho-, meta-, and para-" place factors " 
are known for each negative radicle. 

The " place factors " have been determined for benzoic acid for the 
acetoxy-, carboxy-, chloro-, hydroxy-, and nitro-radicles for the ortho-, 
meta-, and para-positions ; for the aldehydo-, benzoyl-, bromo-, carb- 
methoxy-,carbethoxy-,iodo-,andmethoxy-radicles for the ortho-position; 
and for the cyano-, fluoro-, and iodo-radicles for the meta-position. 
From these numbers the ionisation constants for the substituted 
benzoic acids were calculated, and agreed closely with the experimental 
values in nearly all cases. 



ORGANIC CHEMISTRY. i. 189 

There is no simple relation between the " place factors " for the 
same radicle substituted in the ortho-, meta-, and para-positions in 
benzoic acid. lonisation will not differentiate between 2 : 3- and 
2 : 5-di-substituted benzoic acids, in which the substituting radicles in 
the 3- and 6-positions are the same and those in the 2-positions 
are also the same. The fact that the 3- and 5-positions are equivalent 
with respect to the 1 -position has been proved in terms of the free 
energy of ionisation. E. G. 

Barium Hippurate. Eyvind Bodtker {Chem, Zeit., 1912, 36, 
105). — Analyses of this salt, prepared by neutralising hippuric acid 
with barium hydroxide, crystallising it from water, and drying the 
crystals between blotting paper, show that it contains SHgO. The 
statement that it contains only IHgO may be due to the salt having 
been dried over sulphuric acid before analysis, although the strontium 
salt, when similarly dried, does not lose water. Attempts to prepare 
ferric hipp jrate were not successful. W. P. S. 

Preparation of Cinnamic Esters of Polyatomic Alcohols. 
Farbenfabriken vorm. Friedr. Bayer & Co. (D.R.-P. 239650. Compare 
Abstr., 1911, i, S5S).—^-Chloroethyl cinnamate, CHPhrCH-COg'CgH^Cl, 
a colourless solid, m. p. 31°, b. p. 188 — 191°/20 mm., is prepared by 
the interaction of chloroethyl alcohol and cinnamic acid in the presence 
of concentrated sulphuric acid ; when heated at 140° with sodium 
acetate and dilute acetic acid, it furnishes glycol cinnamate^ b. p. 
170_175°/15 mm. 

y-Chloro - ^-hydroxypropyl cinna mat€f 

CHPh:CH-C02-CH2-CH(OH)-CH2Cl, 
a yellowish, viscid liquid, b. p. 210 — 218°/20 mm., prepared from 
monochlorobydrin and cinnamic acid, by similar treatment yields 
glycerol cinnamate. Other weak acids and their salts can replace 
acetic acid in this reaction. F. M. G. M. 

Sodium Phenyl Carbonate as Intermediate Product of 
Kolbe's Synthesis for Salicylic Acid. Carl H. Sluiter (Ber., 
1912, 45, 59 — 62). — It has been asserted (de Bruyn and Tymstra, 
Abstr., 1905, i, 209; Tymstra, Abstr., 1905, i, 439) that under the 
conditions of Kolbe's process, sodium phenyl carbonate cannot be an 
intermediate step on account of its dissociation into carbon dioxide 
and sodium phenoxide ; in their opinion the carbon dioxide molecule 
inserts itself directly between the carbon and hydrogen atoms in 
the ortho-position of the sodium phenoxide, giving the phenolic sodium 
derivative of salicylic acid. 

The author takes diphenyl carbonate (m. p. 78-2— 78 4°, D^^ 1272, 
D^oo 1-1032), and examines carefully the reaction products obtained 
by heating to 160° with an equimolecular quantity of dry sodium 
hydroxide (compare Hentschel, Abstr., 1883, 588) in a current of 
nitrogen. The evolution of carbon dioxide ends after two to three 
minutes, and the residue contains sodium phenoxide, sodium carbonate, 
and sodium salicylate with some unchanged diphenyl carbonate. Two 
reactions are, therefore, believed to occur concurrently : 

(1) PhO-CO-OPh + 2NaOH = 2PhOH + Na.COg ; 



i. 190 ABSTRACTS OP CHEMICAL PAPERS. 

(2) PhO-CO-OPh + NaOH = Ph-OH + PhO-CO-ONa ; the sodium 
phenyl carbonate then partly dissociates into carVjon dioxide and sodium 
phenoxide, and partly is rearranged into sodium salicylate. The 
alternative explanation given above for the formation of the last 
substance cannot hold in this case, as the pressure of carbon dioxide 
would be quite insufficient for reaction with the sodium phenoxide. It 
appears, therefore, that under the conditions of Kolbe's synthesis, 
sodium phenyl carbonate can undergo rearrangement into sodium 
salicylate. D. F. T. 



Two Phthaloximes and Some of Their Derivatives. William 
R. Orndorff and David S. Pratt (Amer. Chem. J., 1912, 47, 89—125). 
—It has been shown by R Meyer (Abstr., 1905, i, 440; 1909, i, 652) 
that quinolphthalein yields three oximes, of which two are coloured, 
whilst the other is colourless. The coloured oximes, 

o<c:H:iCi!>c<^''o"^c:NOH, 

were regarded as cis- and irans-stereoisomerides, and the group 
CINOH was considered to be the chromophore. In order to ascertain 
whether this group behaves as a chromophore when present in a five- 
membered ring, a study has been made of phthalylhydroxylamine, 
first described by Lassar-Cohn (Abstr., 1881, 585), which the authors 
prefer to term phthaloxime. 

The compound was prej ared-by Lach's method (Abstr., 1883, 1104), 
which consists of heating a mixture of phthalic anhydride, hydroxyl- 
amine hydrochloride, sodium carbonate, and water for an hour at 60°. 
As the reaction product cooled, colourless crystals of phthaloxime 
separated, in quantity equivalent to a 70% yield. When the mother 
liquor was heated at 100° for one and a-half hours and then left to 
cool, lemon-yellow crystals of an isomeric phthaloxime appeared. 

These oximes, CflH^<^^'^Q^^>0. both melt at 220—226°, and are 

slowly decomposed when heated at 110°. Both forms dissolve in 
alkali hydroxides with the production of red solutions, which gradually 
become colourless, owing to the formation of salts of the hydroxamic 
acid. If the colourless oxime is heated with a solvent containing a 
hydroxyl group, it is partly converted into the yellow isomeride, and, 
if boiled for an hour with glacial acetic acid, it is quantitatively 
transformed into the yellow form. The yellow oxime can be quanti- 
tatively changed into the colourless variety by boiling it with acetic 
anhydride, the same colourless acetate^ m. p. 183 — 185°, being obtained 
in this case as when the colourless isomeride itself is acetylated. 
When the colourless acetate is treated with a solution of ammonia and 
afterwards acidified, the white oxime is precipitated. A yellow acetate, 
also of m. p. 183 — 185°, can be obtained from the yellow oxime by the 
action of acetic anhydride at the ordinary temperature. 

Both oximes yield red ammonium^ sodium, sodium hydrogen, 
potassium hydrogen, and silver salts, from which the original oxime is 
regenerated in each cavse on treatment with acids. When the silver 
salts are treated with ethyl iodide, that of the colourless oxime yields 



ORGANIC CHEMISTRY. i. 191 

a colourless ethyl ether^ and that of the yellow oxime, a lemon-yellow 
ethyl ether, both melting at 95 — 100°. 

Each oxime has been submitted to a crystallographic examination. 
The colourless oxime forms monoclinic needles, elongated in the 
direction of the 5-axis, and usually flattened parallel to a pair of faces 
in the ortho-zone ; the crystals have Wj, 1-522 in a direction parallel 
to the elongation. The optical properties of the yellow oxime closely 
resemble those of the colourless form except in respect of colour. 
The colour of the yellow variety is due mostly, if not entirely, to 
fluorescence. A crystallographic study has also been made of the 
salts, acetates, and ethyl ethers. 

The constitution of these oximes is discussed, and evidence is 
adduced to show that in all probability they are not structural 
isomerides, but stereoisomerides of the formulae 

i-co-, ,-co-, 

O-C-CeH. and O-C-C.H,. E. G. 

HO-N N-OH 

isoPhthalanil. Rudolf Pummerer and Gustav Dorfmuller {Ber.y 

1912, 45, 292 — 294). — The transformation of isophthalanil into 

C0*0 CO 

phthalanil, I _>C:NPh -^ C6H4<^^>NPh, takes place slowly 

at the ordinary temperature, as indicated by the rise in m. p. of a 
specimen of the former compound from 116° to 150° after being kept 
for six months, and also by the isolation of phthalanil from the 
product. When shaken with concentrated aqueous sodium carbonate 
at the ordinary temperature, isophthalanil undergoes complete trans- 
formation in the course of five hours. With dilute sodium carbonate 
it is converted, after several days, mainly into phthalanilic acid, only 
traces of phthalanil being produced ; phthalanil undergoes no change 
when subjected to the same treatment. The transformation has also 
been effected by boiling solutions of zsophthalanil in pyridine, quinoline, 
and nitrobenzene ; with water and light petroleum no change occurs. 

isoPhthalanil reacts with benzene in the presence of aluminium 
chloride, yielding o-benzoylbenzanilide. F. B. 

Simple Fatty Amines containing Sulphur. Wilhelm 
Schneider {Annalen, 1912, 386, 332— 350).— The possibility that 
derivatives of aminosulphones, other than cheirolin (methyl-y-thio- 
carbimidopropylsulphone) (Abstr., 1910, i, 658), may occur in nature 
has led the author to prepare aliphatic aminosulphones and the corre- 
jSponding thioc^rbimides, aliphatic aminosulphides, and amino- 
lulphoxides. 

[With Max MuLLERand Wilhelm Beck.] — ^'Phthalimidoethyl methyl 

ilphide, C6H4<^^>N-CH2-CH2-SMe, m. p. 89°, prepared from 

sodium methyl mercaptide and )8-bromoethylphthalimide, yields by 

'lydrolysis methyl ^-aminoethyl sulphide, NHg'CHg'CHo'SMe, b. p. 

[146 — 148°, a colourless liquid having the odour of piperidine and 

strongly basic properties {hydrochloride, m. p. about 120°; picrate, 

p. 119° 3 picrolonatej decomp. 187°; oxalate, m. p. 197°; benzoyl 



i. 192 ABSTRACTS OF CHEMICAL PAPERS. 

derivative, m. p. 57°). By treatment with alkali and an excess 
of methyl iodide, it yields, not an iV^^'-dimethiodide, as does methyl- 
y-aminopropyl sulphide {loc. cit.), but the methiodide of methyl 
)8-dimethylaminoethyl sulphide, SMe-CHg'CHg'NMe,!, decomp. 220-5°, 
colourless leaflets, which is decomposed by warm alkalis with evolution 
of trimethylamine. 

P-PhthaUmidodiethyl sulphide, C6H4<^^N-CH2-CH2-SEt, m. p. 

39°, yields by hydrolysis p-aminodiethyl sulphide^ C^Hj^NS, b. p. 
163° (hydrochloride, m. p. 147°; hydrogen oxalate , m. p. 145*5°; 
picrate, m. p. 148°; picrolonate, decomp. 184°; benzoyl derivative, 
b. p. 221— 222°/40 mm. [decomp.]). The methiodide of /8-dimethyl- 
aminodiethyl sulphide decomposes at 216-5° 

By oxidising its hydrochloride with hydrogen peroxide and treating 
the product with alcoholic sodium ethoxide, methyl yS-aminoethyl 
sulphide yields methyl p-aminoethyl sulphoxide, 

CHg-SO-dHg-CHg-NHa, 
which cannot be distilled, but is volatile with steam. It forms an 
oxalate, m. p. 165°, picrate, m. p. 158°, and picrolonate, decomp. 205°, 
and is decomposed when treated with methyl iodide. p-Aminodiethyl 
sulphoxide, prepared in a similar manner, forms an oxalate, m. p. 176°, 
picrate, m. p. 138°, joicro/ona^e, decomp. 190°, and, when heated with 
the calculated quantities of methyl-alcoholic methyl iodide and sodium 
carbonate, is converted into the methiodide of /5 dimethylaminodiethyl 
sulphoxide, m. p. 168°. Methyl y-aminopropyl sulphoxide, 

CH3-SO-[CH2]3-NH2, 
forms an oxalate, m. p. 197°, picrate, m. p. 143°, and picrolonate, 
decomp. 210°. 

M ethyl- P-aminoethylsulphone, obtained in the form of the hydro- 
chloride, CHg-SOa'CHg-CH^-NHgjHCl, m. p. 169°, by oxidising the 
hydrochloride of the sulphide by potassium permanganate, forms a 
picrate, m. -p. 167°, picrolonate, decomp. 22b°, platinichloridCj decomp. 
227°, and benzoyl derivative, m. p. 134°, yields the methiodide of 
methyl /3-dimethylaminoethylsulphone, m. p. 220°, with methyl- 
alcoholic methyl iodide at 120°, and is converted into di-^-methyl- 
sulphonethylthiocarbamide, SC(NH-CH2*CH2-SOoMe)2, m. p. 141°, by 
carbon disulphide, and into methyl p-thiocarbimidoethylsulphone, 

S02Me-CH2-CH2-NCS, 
m. p. 46 — 47°, by Hofmann's method with carbon disulphide. 
P-Aminodiethy!sulphone,prepsireda.s the hydrochloride, m. p. 101 — 102°, 
in a similar manner, forms a picrate, m. p. 163°, picrolonate, decomp. 
210°, platinichloride, decomp. 227°, aurichloride, m. p. 197°, benzoyl 
derivative, m. p. 86°, and thiocarbamide, m. p. 141°; the thiocarbimide 
could not be isolated. 

[With WiLHELM LoHMANN.] — Phthalimidodimethyl sulphide^ 

C6H,<^^NCH2-SMe, 

m. p. 114°, is obtained from bromomethylphthalimide and sodium 
methyl mercaptide in alcoholic solution. It is oxidised by hot aqueous 
potassium permanganate to the sulphone, CjoHgO^NS, m. p. 203°. 
Both the sulphide and the sulphone decompose completely when 
hydrolysed. C. S. 



ORQANIC CHEMISTRY. i. 193 

Chemical Action of Light on Vanillin and its Ethers. 
Ernesto Puxeddu {Aui R. Accad. Lincei, 1911, [v], 20, ii, 717—723). 
— When vanillin in solution in alcohol, benzetie, or other solvents is 
exposed to light, dehydrovanillin is obtained in small quantity, and 
no other product can be detected except a viscous oil. Vanillin 
methyl and ethyl ethers behave differently when exposed to light in 
benzene solution, the corresponding methyl and ethyl ethers of 
vanillic acid being formed respectively. R. V. S. 

Reactivity of the Carbonyl Group. Hermann Staudinger 
(Annalen, 1912, 387, 254 — 255). — A note explaining more fully the 
pictorial representation of the unsaturation of an atom by the length 
of the dotted line representing its residual affinity (compare 
Staudinger and Kon, Abstr., 1911, i, 876). C. S. 

Behaviour of Antimony Trichloride and Tribromide 
towards certain Oxygenated Organic Compounds. Boris N. 
Menschutkin (/. Buss. Phys. Chem. Soc, 1911, 43, 1785 — 1804). — 
The concentration-temperature diagrams given by acetophenone or 
benzophenone with antimony trichloride or tribromide are all nearly 
identical, each system being characterised by the formation of one 
molecular compound, which contains 1 mol. of the ketone to 1 mol. of 
antimony salt, and melts unchanged. Each diagram consists of four 
branches, corresponding with (1) the lowering of the m. p. of the 
ketone by addition of antimony salt, (2) the solubility in the ketone 
of the molecular compound, (3) the lowering of the m. p. of this 
compound by the addition of SbXg, and (4) the loweriDg of the m. p. 
of SbXg on addition to it of the molecular compound. Each diagram 
exhibits two eutectic points. The melting points of the various 
compounds are: SbC)3,C0MePh, 60-5°; SbBr3,00MePh, 37*5°; 
SbCl3,COPh2, 76°; SbBrg.COPh,, 48-5° The eutectic temperatures 
and the corresponding numbers of ketone mols. (n) per mol. of 

itimony salt are as follows : 

1st eutectic point. 2nd eutectic point. 

M. p. . ' N . ' ^ M. p. 

System. Ketone. Temperature, n. Temperature, n. SbXg, 

SbClg- -OOMePh 19-5° 1° 4-05 32° 0-36 73° 

SbBr3— COMePh 19-5 1-5 317 31 0-6 94 

SbClj— COPbg 48 35 4*63 39 0-26 73 

SbBrg— OOPha 48 29 2-82 40 0'5 94 

Benzoic acid (m. p. 1*20°) forms a molecular compound with neither 
mtimony trichloride nor tribromide, the concentration-temperature 
liagram consisting, in each case, of two branches meeting at the 
Followicg eutectic points : SbCl3,0-52Ph-CO2H, 46° ; 
SbBr3,0-42Ph-CO2H, 79°. 
The system SbCIg-CHg'COgH gives a molecular compound which 
Forms only with difficulty. The first branch of the curve terminates 
fat the eutectic point - 9°, corresponding with the composition 
lbC)3,3-43CH3»C02H. Then begins the curve of solubility of the 
[molecular compound in acetic acid, but this is observable only on 
seeding with the molecular compound ; unless this is done, branch 1 
is prolonged below the eutectic point, and probably meets branch 4 in 



i. 194 ABSTRACTS OF CHEMICAL PAPERS. 

another eutectic point. Branch 1 shows no arrest corresponding with 
the eutectic point CHg'COgH-SbOlg.CKg'COgH, as the compound is 
not formed on cooling the sohition. Branch 3 cuts branch 4 (lowering 
of m. p. of SbClg on addition of CHg'COgH) at the eutectic point, 
about 19°, corresponding approximately with SbClgjO'QlCHg'COgH ; 
branch 3 can be followed below this eutectic point, but then represents 
an unstable condition. 

The system SbBrg-CHg'COgH forms no molecular compound, the 
curve consisting of two branches meeting at the eutectic point 4°, 
which corresponds with SbBr3,4-34CHg*C02H. 

Benzoyl chloride forms no molecular compound with antimony 
chloride or bromide, each curve showing a single eutectic point : 
SbCl3,l-95Ph-C001, -33°, and SbBr8,6-45Ph-COCl, -6°. T. H. P. 

The Reduction of Polyunsaturated Ketones with Crossed 
Double Linkings by Paal's Method. Walther Borsche {Ber., 
1912, 45, 46 — 53). — The author has already successfully applied 
Paal's reduction method to the preparation of saturated ketones from 
such unsaturated ketones as cinnamylideneacetone (Abstr., 1911, i, 
880), and now extends the investigation to ketones in which each of 
the two carbon atoms adjacent to the carbonyl group has a double 
linking. The results indicate that where there is only one double 
bond on each side of the carbonyl group, the reduction proceeds 
smoothly, but that in other cases there is considerable formation of 
resinous substances as by-products. 

The reduction of distyryl ketone yields di-^-phenylethyl ketone, b. p. 
224°/18 mm. ; the oxime melts at 95 — 96° (compare Dunschmann and 
von Pechmann, Abstr., 1891, 674) ; a small quantity of a substance^ 
C34H34O2, m. p. 126°, was also obtained. Di-jo-methoxystyryl ketone is 
reduced to ai-di-^-methoxyphenylpentan-y-one^ which crystallises in 
needles, m. p. 52°. 

Di-o-hydroxystyryl ketone gives ae-di-o-hydroxyphenylpentan-y-one, a 
viscid mass, which, when heated, loses water with the formation of teti^a- 
hydrodibenzoB^iYopyran (compare Decker and Felser, Abstr., 1908, i, 
906), wliich crystallises in needles, m. p. 110°, b. p. 217°/16 mm. 

1 : 3-Dibenzylidenec2/c/opentan-2-one gives 1 : Z-dihenzylcjc\opentan-2- 
one as an oil, b. p. 232 — 233°, which slowly crystallises in needles, 
m. p. 47°. In a similar manner, 1 : 3-dibenzylidenec?/c/ohexan-2-one and 
1 ; 3-dibenzylidenecycfeheptan-2-one give the corresponding 1 : 3- 
dibenzylcycio/iexan-2-one, m. p. 114°, and 1 : 3-dibenzylcyc\oheptan-2-one, 
b. p. 261— 262°/28 mm. 

Phenyl cinnamylidenemethyl ketone produces plienyl h-phenylbutyl- 
ketone, b. p. 225 — 226° ; the oxime forms prismatic crystals, m. p. 
81 — 82°, and by the Beckmann rearrangement changes into the anilide 
of 8-phenylvaleric acidy m. p. 89 — 90°. 

Styryl cinnamylidenemethyl ketone gives arj-diphenylheptan-y-one, 
b. p. 2 3 9°/ 14 mm. ; the semicarbazone is an oil, whilst the hydrazone 
phenylcarbamate, CH2Ph-CH2-C(N-NH-CO-NHPh)-[CH2]o-CH2Ph, has 
m. p. 122—123°. 

Dicinnamylideneacetone gives ai-diphenylnonan-e-one (h-phenylbutyl 
ketone)^ an oil, b. p. 258 — 260°/ 13 mm., which solidifies in a freezing 



ORGANIC CHEMISTRY. i. 3 95 

mixture ; the oxime and semicarhazone are liquids, whilst the hydrazone 
phenylcarhamate forms silky needles, m. p. 129 — 130°. 

2 : 6-Di-cinnamylidenec?/c/ohexanone gives 2 : Q-di-o)-pkenylpropyl- 
cjclohexanone as a viscous oil, b. p. 276 — 278°. D. F. T. 

Synthesis of Butin. A. Goschke and Josef Tambor {Ber., 1912, 
45, 186—188. Compare Abstr., 1912, 1, 30).— The authors have 
succeeded in transforming synthetic butein into butin (compare 
Perkin and Hummel, Trans., 1904, 85, 1459), thus completing the 
synthesis of both these natural products. Butin triacetate has 
m. p. 123°. 

By the action of 3 : 4-dimethoxybenzaldehyde on resacetophenone 
and resacetophenone dimethyl ether respectively, they have prepared 
the 3' : 4:' -dimethyl ether of butein (m. p. 203°) and butein tetramethyl 
ether (m. p. 89°). 

2' : 4' : 2-Trihydroxychalkone, prepared by condensation of salicyl- 
aldehyde with resacetophenone, crystallises in orange needles +IH2O, 
and has m. p. 185°. Its transformation into 3 : 2'-dihydroxyflavanone 
appears to be difficult. H. W. 

Preparation of Benzanthrone and its Derivatives. Roland 
ScHOLL (D.K.-P. 239761). — When aromatic mono- or poly-ketones 
containing a free peri-position with regard to the carbonyl group are 
heated at about 140 — 150° with either aluminium chloride or bromide, 
or ferric chloride, condensation occurs, yielding benzanthrone or 
pyranthrone derivatives. 

The following compounds have been prepared : Benzanthrone from 
phenyl a-naphthyl ketone. Naphthabenzanthrone from 1 : 1'-dinaph- 
thyl ketone, which can be prepared by the interaction of naphthoic 
acid with naphthalene in the presence of aluminium chloride. 

Dibenzoylpyrene (I), m. p. 155°, and tribenzoylpyrene, m. p. 235 — 237°, 
are prepared by the action of benzoyl chloride on pyrene in the 





(11.) \/\/\, 

I I I I 

\/\A/ 

CO 

presence of aluminium chloride and separated by fractional crystallisa- 
tion from acetic acid; when the former is heated at 160° with 
aluminium chloride, it yields pyranthrone (Abstr., 1910, i, 271). 

Tri-a-naphthoylpyrene, m. p. 218 — 219°, prepared from pyrene and 
a-naphthoyl chloride, furnishes naphthapyranthrom. 

Dibenzoyl'l : V-dinaphthyl, obtained from 1 : i'-dinaphthyl and 
Jjwazoyl chloride, furnishes violanthren (II), a violet powder, whilst 



i. 196 ABSTRACTS OF CHEMICAL PAPERS. 

naphthylanthraquinonyl kHone (from anthraquinone-2-carbonyl chloride 
and naphthalene) gives phthaloylhenzanthron«y and w-tolyl-1-naphthyl 
ketone yields rnAthylbenzanthron^ brownish-yellow needles, m. p. 
164—165°. F. M. G. M. 

Ketones Derived from woMyristicin. Everardo Scandola 
(Atti R, Accad. Lincei, 1912, [v], 21, i, 47 — 54) — The author has 
prepared the a- and )S-keto- derivatives of womyristicin, and has 
attempted to obtain the dimeric form of ?«omyristicin. 

The a-ketone is prepared by heating together for some hours the 
dibromo-derivative of isomyristicin (Thorns, Abstr., 1904, i, 47) and 
sodium methoxide, removing the excess of methyl alcohol, and 
distilling the residue with steam. After fractionation in a vacuum of 
the oil which passes over, the pure a A;«^o- derivative of ?«omyristicin, 
Oj^HjgO^, is preferably obtained by way of the semicarbazide or oxime. 
It crystallises in small, silky needles, m. p. 93°. It yields a crystalline 
hisvlphite compound, which does not melt below 230°. The oxime, 
C^^HisO^N, crystallises in very small prisms, m. p. 124°. The 
semicarhazone, CjgHjgO^Ng, has m. p. 180°. The ketone does not give 
an hydroxamic acid with Pilot y's acid. 

The /^-ketone of isomyristicin was prepared by Hoering's method 
(Abstr., 1905, i, 902), When the dibromo-derivative of tsomyri^ticin 
is heated with water and acetone in the presence of calcium carbonate 
(marble) for two hours, the acetone solution separated, and heated for 
a further two hours and then distilled, p-hromo-a-hydroxydihydro\^o- 
rnyristiciriy Cj^HjgO^Br, is obtained. It is a very dense, yellowish- 
brown oil, with a pungent odour, and it cannot be crystallised or 
distilled in a vacuum. On treatment of this substance with alcoholic 
potassium hydroxide, a glycol, OH*CHR*CHMe*OH, should be 
produced, from which the oxide, Ar*CH*CHMe, and finally its 

\o/ 

isomeride, the yS-ketone, Ar'CHg'COMe, could be obtained. Actually, 
the raw product of the reaction does not combine with bisulphite, and 
it gives analytical figures intermediate between those required by the 
glycol, Cj^Hj^O^, and the oxide, CuHjgO^, but when it is distilled in a 
vacuum, most of it passes over at 230 — 240°/30 mm. ; the distillate 
readily crystallises, and has m. p. -44 — 45°. After recrystallisation, it 
forms long, silky needles, m. p. 54 — 55°, and gives on analysis numbers 
corresponding with the formula CuHj^O^. This substance gives a 
bisulphite compound, and is evidently the ^-ketone. The isomerisation 
of the oxide is best effected by heating the substance in glacial acetic 
acid with a few drops of concentrated sulphuric acid, and purifying the 
product by way of the bisulphite compound. The semicarbazone, 
CijHijO^Ng, has m. p. 143—144°. The oxime, C^^B.^fi^^, crystal- 
lises in tufts of prisms, m. p. Ill — 112°. The ^-ketone was also 
prepared by reduction of ^-nitrotsomyristicin and hydrolysis of the 
oxime produced. 

Numerous attempts were made by various methods to polymerise 
tsomyristicin. In only one case was any new product obtained. 
When ?somyristicin is heated for five to ten minutes in glacial acetic 
acid solution with a trace of concentrated sulphuric acid, a substance 



ORQANIC CHEMISTRY. i. 197 

is obtained, which crystallises in small prisms, m. p. 232 — 233° and 
may be the dimeric form of isomyristicin. The yield is less than 2%. 

R. Y. S. 

Constitution of Chrysophanic Acid. Eugene Leger {Compt. 
rend., 1912, 154,281 — 283. Compare RobinsoQ and Simonsen, Trans., 
1909,95, 1085; Oesterle, Abstr., 1911, i, 887).— In order to deter- 
mine the position of the methyl group in chrysophanic acid, the tetra- 
nitro-derivative was oxidised with nitric acid (D 1'5). 2:4: 6-Trinitro- 
3-hydroxybenzoic acid was isolated from the products, but chrysammic 
acid could not be detected. It follows that the nitro- and hydroxy- 
groups in tetranitrochrysophanic acid occupy the same positions as they 
do in tetranitroaloe-emodin, and therefore that the methyl group in 
chrysophanic acid can only occupy the position assigned to it by 
Fischer, Falco, and Gross (Abstr., 1911, i, 309). Chrysophanic acid is 
therefore 1 : 8-dihydroxy-3-methylanthraquinone. This conclusion is 
confirmed by fusing the acid with potassium hydroxide, when 5-hydroxy- 
isophthalic acid is formed, together with a much smaller amount of 
4-hydroxyisophthalic acid and other substances. W. O. W. 

. Preparation of Anthraquinone Derivatives Containing 
Sulphur. Farbwerke vorm. Meister, Lucius & Bruning (D.R.-P. 
239762). — When diazotised aminoanthraquinones are treated with thio- 
carbamides, intermediate compounds are formed, which evolve ammonia 
on treatment with potassium hydroxide, and furnish the corresponding 
mercaptan. Garhamylthiolanthraquinone^ Cj^H^Og^S'CO'NHg, orange, 
yellow crystals, was prepared from a-aminoanthraquinone and thio- 
carbamide, whilst with phenylthiocarbamide a similar compound was 
produced. F. M. G. M. 

[Preparation of Benzoylaminoanthraquinone Derivatives.] 
Farbwerke vorm. Meister, Lucius & Bruning (D.R.-P. 240079). — 
The preparation of benzoylaminoanthraquinones and their condensa- 
tion products has previously been described ; it is now found that more 
valuable colouring matters are produced by employing nitrobenzoyl 
chlorides, subsequently reducing the nitro-group and combining with 
another molecule of benzoyl chloride before condensing to form the 
dye. 

Benzoyl-^-aminohenzoyl-\-aminoanthraquinonef yellow crystals, m. p. 
315°, is prepared by benzoylating p-aminobenzoyl-1-aminoanthra- 
quinone in nitrobenzene solution ; benzoyl-^-aminobenzoyl-2amino- 
anthraquinone has similar properties. 

The tinctorial properties of the following final condensation joroc^wc^s 
are tabulated in the original ; jo-aminobenzoyl-l-aminoanthraquinone 
with succinic acid, m. p. above 300°, with anthraquinonecarbonyl 
chloride, m. p. 280°, and with 2-anthraquinonylcarbamyl chloride, 
m. p. above 300°. 

^Aminobenzoyl-2-aminoanthraquinone with 2-anthraquinonylcarb- 
amyl chloride. 

m-Aminobenzoyl-1-aminoanthraquinone with 2-anthraquinonylcarb- 
amyl chloride, m. p. 285°. 

VOL. CII. i. p 



i. 198 ABSTRACTS OF CHEMICAL PAPERS. 

3 : 5-Diaminobenzoyl-l-aminoanthraquinone with 2-anthraquinonyl- 
carbamyl chloride (2 mols.), m. p. 235°. 

Benzoylaminoanthraquinonecarhoxy-\-aminoanthraquinone has m. p. 
above 300°. F. M. G. M. 

Preparation of o-Aminodianthraquinonylamine Types of 
Compounds. Farbenfabriken vorm. Friedb. Bayer & Co. (D.R.-P. 
240276). — The p'oduct (annexed formula), dark blue needles, was 

(\ CO /\ prepared by boiling together l-amino- 

y Y N 4-hydroxyanthraquinone (10 parts), 

/\rO/\ / — "^^ naphthalene (100 parts), anhydrous 

'^^ NTT I sodium acetate (5 parts), copper 

2 'v p^ yv powder (0'2 part), and slowly adding 
/ y Y I ^ ■ bJ'omo - 1 - aminoanthraquinone (5 
I J\pr)/\ / parts) ; when the latter component is 
/yrr replaced by 2-bromo-l-methylamino- 

anthraquinone a similar compound is 
obtained, likewise from a-amino-4-hydroxyanthraquinone with 1 : 3-di- 
bromo-2-aminoanthraquinone, and from a-aminoanthraquinone with 
2-bromo-l-aminoanthraquinone. F. M. G. M. 

A Supposed Compound of Camphor and Naphthalene. 
JouNiAUX {Bull. Soc. chim., 1912, [iv], 11, 129— 132).— When 
naphthalene containing increasing quantities of camphor is melted 
and allowed to cool, the temperature at which solidification begins 
falls steadily from 80° to 32-6°, at which point the mixture contains 
58 mols. of camphor to 42 mols. of naphthalene ; a similar fall, reaching 
the same point at the same composition, occurs when increasing 
quantities of naphthalene are added to camphor. For every mixture, 
the finishing point of solidification is 32*5°. In view of these facts 
Girard's supposed compound of these two substances, 

(C'ioHi60)io>(CioH8)., 
m. p. 32-6° {J. Pharm. Chim.^ 1891, [v], 24, 105), appears to have been 
a eutectic mixture. T. A. H. 

Constitution of woPenchocamphoric Acid and of Some 
Compounds of the Fenchone Series. Ossian Aschan [with 
W. Sjostrom and A. Peterson] (Annalen, 1912, 387, 1 — 85). — The 
fractions obtained from a very large quantity of pinolene, b. p. below 
150° (Abstr., 1907, i, 630), have been separately oxidised by 8% 
potassium permanganate at 60 — 80°, whereby carbonic, oxalic, and 
c?/-camphoric acids are produced. From these facts and from the 
molecular refractions of the various fractions, the author deduces that 
pinolene contains at least three hydrocarbons : (i) r-bornylene, b. p. 
148 — 149°, m. p. 40 — 42°, which yields c?/-camphoric acid by oxida- 
tion ; (ii) a-pinolene, b. p. 144 — 146°, a dicyclic terpene, and (iii) 
^-pinolene (cyclo/enchene), CjoHjg, a tricyclic terpene, which probably 
contains a trimethylene ring on account of its stability towards 
potassium permanganate. 

)8-Pinolene (cycZofenchene), obtained from the pinolene fractions, 
b. p. 140 — 142° and 142 — 144°, by oxidation as above, has b. p 



ORGANIC CHEMISTRY. i. 199 

i4i.5_i43.50, Df 0-8588, [ajo +0-28°, andng 1*44769 j its molecular 
refraction, therefore, exceeds by about 0*6 the value calculated for a 
tricyclic terpene, a fact which furnishes additional evidence for the 
presence of a trimethylene ring. By further prolonged oxidation with 
potassium permanganate, /5-pinolene yields a very small quantity of 
isophthalic acid. This may be due to the presence of a little a-pinolene ; 
its formation, however, shows that the pinolene hydrocarbons can be 
converted into benzene derivatives of the meta-series, y8-Pinolene in 
dry ether at — 15° forms an unstable, crystalline hydrochloride j 
C^oHig,HCl, m. p. 27-5—29°. 

a-Pinolene hydrochloride, m. p. 38°, has been previously described 
as pinolene hydrochloride {loc. cit.). a-Pinolene probably has the 
annexed formula ; the halogen atom in its hydro- 
CHg'CH — CHg chloride is attached to the CMe group. 

A,;j^ /S-Pinolene is unchanged by eight hours' boiling 

I 2 with 20% sulphuric acid, but when heated for four 

CHg'C^— CMe hours with 96% alcohol and 96% sulphuric acid yields a 

dicyclic ether, Q^^M^^-O'Et, b. p. 197—200°, Df 0-8904, 

7i^M-45217. 

Fractions, b. p. 144*5 — 146° and 146 — 148° respectively, of un- 
oxidised pinolene, purified ^-pinolene, and also isopinene, have been 
separately treated at 60 — 70° with glacial acetic and 50% sulphuric 
acids by Bertram and Walbaum's method, and the resulting acetates 
have been hydrolysel. In each case the main product is (i^-i6'ofenchyl 
alcohol (m. p. 43 — 44°), identified as the phenylurethane, m. p. 95 — 96°. 
In the case of the fraction, b. p. 146 — 148°, a little isoborneol is 
obtained (produced probably from the r-bornylene), whilst from thb 
purified y8-pinoletie a mixture of c?^-2sofenchyl and c?Z-fenchyl alcohols is 
formed. By oxidation with potassium permanganate, therefore, the 
mixture yields c?^-2sofenchone and c^^fenchone, in addition to the chief 
product, c^Z-isofenchocamphoric acid (Wallach, Abstr., 1908, i, 809). 
These facts prove that dl-isoiQnchy\ alcohol is the chief product of the 
hydratisation of the mixture of fenchenes (consisting mainly of 
isopinene) obtained from a- and y8-pinolenes. A diagrammatic 
representation of the transformations is given. 

A description is given of the preparation in quantity and the 
purification of d!/-isofenchocamphoric acid. It is best obtained from 
the pinolene fraction, b. p. 140 — 150°, which is converted into iso- 
fenchyl alcohol as above ; the alcohol is then oxidised by alkaline 5% 
potassium permanganate without warming. 

The constitution, CHo<'^,,\ -,?^ J^^ \^ ^, is ascribed to wofencho- 
^^CMe(C02H)-CH2 
camphoric acid on the following grounds. The saturated dibasic acid 
readily forms an anhydride, m. p. 94 — 95°, by distillation or by 
treatment with acetyl chloride ; the acid, therefore, has the cis-con- 
figuration. From the anhydride the anilic acid, 
COaH-CgHj^-CO-NHPh, 
m^, p. 191—192°, ethyl ester, Q^U^^{QO^^t)^, b. p. 267—268°, Df 1-0054, 
n'% 1*44626, methyl hydrogen ester, m. p. 72 — 74°, and ethyl hydrogen 
ester, b. p. 289—292° (decomp.), are prepared. The distillation of the 

^ 2 



i. 200 ABSTRACTS OF CHEMICAL PAPERS. 

calcium pall, CjoHj^O^Ca, does not produce a cyclic ketone, indicating 

that the acid is a substituted succinic or glutaric acid. When heated 

with acetic and hydrochloric acids at 180° for ten hours, 

rf^cts-wofenchocamphoric acid is transformed into the less soluble 

trans-wommcifl, m. p. 169 — 170"5°; hence, one of the carboxyl groups 

is attached directly to a ring carbon atom. When c//-cis-isofencho- 

camphoric acid is treated with phosphorus pentachloride and the 

product is brominated as in the case of camphenic acid (Abstr., 1910, 

i, 709), two stereoisomeric a-bromo'isofenchocamphoric acids, 

CgH.gBrlCO^H),, 

m. p. 208—210° and 160—162° respectively, are obtained. (The 

author's explanation of the production of the two stereoisomerides is 

given below.) The former acid, which is the main product, yields an 

anhydride, m. p. 97°, and an ethyl ester, b. p. 155 — 156°/5 mm., 

Djs 1*2425, and by reduction with zinc and acetic acid regenerates 

c^/-cts-tsofenchocamphoric acid. The introduction of only one bromine 

atom, even when an excess of the halogen is employed, indicates that 

there is only one hydrogen atom in the a-position to a carboxyl group, 

whilst the formation of the two stereoisomerides is regarded as 

evidence that the carbon atom, to which this hydrogen atom is 

attached, forms part of the alicyclic ring. Other facts in harmony 

with the preceding constitution of isofenchocamphoric acid are the 

following. When heated with aqueous sodium carbonate or barium 

hydroxide, the a-bromo-acid, m. p. 208 — 210°, yields iso/e)2c/ioZaitrowo/ic 

OH— CH 
acid, C02H'CMe<^ i , m. p. 44 — 45°, a-hydroxyhofenchocam- 

phoric acid, C8Hi3(OH)(C02H)2, m. p. 185—186° (decomp.), and 
dehydroi&ofenchocamphoric acid, C8Hj2(COoH)2, m. p. 189 — 190°; 
methods for the separation of these three acids are described. The 
same three acids are produced by the action of aqueous barium 
hydroxide on the a-bromo-acid, m. p. 160 — 162°. When heated above 
its m. p. or warmed with 50% sulphuric acid, a-hydroxyi8r>fencho- 
camphoric acid is converted into the lactonic acid, iso/eoichocamphanic 

acid, CyHjg'^pxp^ ^0, m. p. 177°, which is also produced by 

heating the a-bromo-acid, m. p. 208 — 210°, with quinoline at 160° 
(best method), and is re-converted into a-hydroxywofenchocamphoric 
acid by boiling 10% potassium hydroxide. 

a-Hydroxyisofenchocamphoric acid is oxidised by lead dioxide and 
acetic acid to i&ofenchocamphononic acid, 

CO.H.CMe<^;jSe.- 
m. p. 68 — 70°, which forms a semicarbazone, Cif^Hj^OgNg, m. p. 221°. 
Finally, the fusion of a-hydroxywofenchocamphoric acid with potassium 
hydroxide at the lowest possible temperature yields formic acid and 
an acid, C^Hj^O^, m. p. 192 — 193°, which is regarded as identical with 
Michailenko and Jaworski's aayy-tetramethylglutaric acid, m. p. 
185 — 189°, on account of its stability towards bromine and the forma- 
tion of an anhydride, m. p. 88°, and p-toluidino-acid, 

COgH-CgHi^-CO-NH-C^Hy, 
m. p. 160— 161°. 



ORGANIC CHEMISTRY. i. 201 

From the preceding constitution of isofenchocamphoric acid, it follows 

that isofenchone and ^-pinolene 
CMeg-CH— CHg CMeg-CH— CHg probably have the constitutions (I) 
I CHo I I CHg I and (II) respectively ; the latter 

CH "CMe'CO CH CH ^^^ produce fenchyl and isofenchyl 

^ ^. / alcohols by fission of the trimethyl- 

^Xqi^q/ ene ring and the addition of water 

,-r . ,jT s in the two possible ways. 

The author assumes the trans- 
formation ^CH'CO' — >■ ^CIC(OH)' to account for the bromina- 
tion of aliphatic acids (or, better, their chlorides), the formation of two 
stereoisomeric a-bromo-acids by the bromination of alicyclic acids, and 
the transformation, without substitution, of geometric isomerides ; 
thus : 

(1) RR'CH-CO-Cl -^ RR'CICCl-OH ^'^ 



RR'CBr-OOlBr-OH -^ RR'CBr-CO-Cl ; 

(2) J,>oH-co-ci -* ?>o:cci-OH ^ S.><Kotb,.oh ""' 

|><™"«-.|,>o<-. „,„.!><-, 

(3, |>o<« _, it |>o:c<» ^ 5><>H 

Although this explanation is equally applicable to transformations 
of the maleic-fumaric acid type, the author prefers, in such cases, 
Wislicenus' explanation, because the additive capacity of an ethylenic 
linking so greatly exceeds that of the carbonyl group in a carboxyl 
group. C. S. 

Constitution of Camphene. Karl Auwers (Annalen, 1912, 
387, 240— 253).— See this vol., ii, 214. 

The Constituents of Ethereal Oils (Derivatives of Natural 
Cedrene). Friedrich W. Semmler and Felix Risse (Ber., 1912, 
45, 355 — 360. Compare Semmler and Hoffmann, Abstr., 1907, i, 
946). — Natural cedrene has been oxidised on a larger scale than 
previously by the action of ozone. The main neutral products are a 
ketone, C^Jl^fi ^r Cj^UggO, b. p. 120 — 130°/13 mm. (semicarbazone, 
m. p. 218°), and the ketonic aldehyde, C15H24O2 (loc. cit.) ; the chief 
constituent of the acidic portion of the oxidation product is cedrene- 
ketonic acid {loc. cit.), b. p. 205 — 215710 mm. (methyl ester, b. p. 
165— 170710 mm., D^o 1-0509, rij, 1-4882, ai> -32'4° at 20°). 

The ketonic acid is probably a methyl-ketonic acid, as it is oxidisable 
by sodium hypobromite to the dibasic acid, cedrenedicarhoxylic acid, 
m. p. 182-5°; the methyl ester (loc. cit.) has b. p. 179— 183°/13 mm., 
D20 1-0778, rij, 1-48084, a^ - 31-6°. D. F. T. 



Synthesis of an Aliphatic Terpene. C. J. Enklaar (Ckem. 
Weekhlad, 1912, 9, 68—72. Compare Abstr., 1909, i, 690).— A descrip- 
tion of a method for the preparation of labile hydrocarbons of the 



i. 202 ABSTRACTS OP CHEMICAL PAPERS. 

olefine series from tertiary alcohols, of the formation of an aliphatic 
tcrpene by the dehydration of linalool, and of the behaviour of this 
product on hydrogenation and ozonisation. 

"When linalool is brought into contact with active copper at 
130 — 140° in a rapid current of carbon dioxide, the formation of a 
cyclic hydrocarbon is in large measure obviated, the main product 
being an aliphatic hydrocarbon. The copper was obtained in a very 
active condition by reducing copper oxide with hydrogen, the oxide 
being prepared by gentle ignition of copper nitrate. The excess of 
hydrogen was expelled by carbon dioxide at 170°. The hydrocarbon 
was separated from the unchanged linalool by repeated vacuum distil- 
lation, finally over Fodium. It is a liquid, D^^ 0*804. Acraldehyde, 
geraniol, and citral were by-products. 

The same hydrocarbon was obtained by heating linalool with phenyl- 
carbimide : 2C0:NPh + Q^^'R^fi = C0(NHPh)2 + CjoH^g -f CO2. The yield 
is best with a slight excess of linalool and a temperature of 150 — 170°, 
a non-volatile brown oil being obtained as by-product. When the 
carbimide was in excess, the proportion of this oil was increased by 
60%. The hydrocarbon had D^'' 0811. The substance was not 
obtained quite pure, but the following physical constants are given : 
Di* 0-802, <' 1-470, b. p. 62°/14 mm., hence it is probably myrcene. 

Reduction with nickel and hydrogen at 130° and fractionation of 
the product yielded a decane, b. p. 159 — 160°/760 mm. (uncorr.), 
D^^ 0*739, identical with )8^-dimethyloctane obtained from ocimene 
(Abstr., 1908, i, 664). Reduction with sodium and alcohol yielded a 
hydrocarbon with the odour and b. p. (165 — 167°) of dihydromyrcene. 
This substance probably has the formula Cj(jHjg, because bromination 
by Baeyer and Villiger's method yielded a crystalline bromide, m, p. 88°, 
which produced no depression in the m. p. of dihydro-ocimene tetra- 
bromide (compare Rec. trav. chim., 1907, 26, 167, and 27, 448). 

Ozonisation of the terpene by the method previously described 
{ibid.^ 1908, 27, 422) precipitated an explosive ozonide, inflamed by 
concentrated sulphuric acid, and decomposed by water with formation 
of acetone, probably succinic acid, and other products not identified. 

The impure hydrogenation product yielded an ozonide with similar 
properties. The liquid obtained by the action of water gave the 
pyrrole reaction distinctly, and probably contained acetone peroxide. 

A. J. W. 

Reduction of Sabinene. Otto Wallach (Ckem. Zentr., 1911, ii, 
1802 ; from Nachr. K. Ges. Wise. Gottingen, 1910, 544). — In the presence 
of metallic catalysts, sabinene takes up 2 atoms of hydrogen with the 

formation of dihydrosahtneney CHg^V ^CHg, having b. p. 

156—157°, D20 0-8120, n^ - 2°2'. '^ W. P. S. 

Leaf-Oil of the Washington Cedar (Thuja plicata). Robert 
E. Rose and Carl Livingston (/. Amer. Chem. Soc, 1912, 34, 
201 — 202). — As only a superficial examination of the oil obtained from 
the leaves of Thuja plicata (Brandel, Pharm. Rev., 26, 248) has hicherto 



ORGANIC CHEMISTRY. i. 203 

been made [compare, however, Blasdale, Abstr., 1907, i, 630], a detailed 
study has now been carried out. 

On distillation with steam, the leaves and twigs yielded about 1% 
of light yellow oil, which had a cedar-like odour, D^^ 0913, n^ 14552, 
[ajo -4'77°; acid number, 0*518; ester number, 2 28 ; saponification 
number, 2'8, and acetylation number, 8'8. The product was free from 
phenols, soluble in all proportions in 70% alcohol, and about 85% of it 
boiled at 100—110740 mm. The oil contains tanacetone 80—85%, 
pinene 3 — 5%, tanacetyl acetate 1 — 2%, and tanacetyl alcohol 1 — 3%. 

E. a 

The Chemical Degradation of Ohitin. Hugo Brach {Biochem. 
Zeitsch., 1912, 38, 468 — 491). — A description is given of the preparation 
of the material from Nephrops norvegicus. The analyses showed that 
the substance had a composition corresponding with the formula 
^32^54^21^4' '-^^® estimation of the acetyl groups by a modification 
ot Wenzel's method, which is described by the author, showed that for 
each nitrogen in the atom there exists an acetyl group. The results 
indicate that the simplest formula for chitin is one made up of a 
complex of four acetylglucosamine groups. Lenk's chitosan appears 
to be formed from chitin by the scission of half the acetyl groups. 
By the action of nitrous acid, the whole of the nitrogen in the molecule 
can be eliminated, a fact which the author shows does not contradict 
the assumption of the presence of acetylamino-groups. S. B. S. 

Constitution of Rhein. Otto A. Oesterle {Ghem. Zentr., 1912, i, 
Wl—UZ '/horn Schweiz. Woch. Ghem. Pharm., 1911, 49, 661—665). 
— Contrary to the view of the author and Riat (Abstr., 1909, i, 946) 
that aloe-emodin and its most nearly related derivatives are derived 
from 1 : 8dihydroxyanthraquinone (chrysazin), Robinson and 
Simonsen (Trans., 1909, 95 1085) regard 1 : 6-dihydroxyanthra- 
quinone (tsoohrysazin) as the parent substance of rhein. The 
author, therefore, has converted rhein through rhein chloride, yellow 
needles, and the amide, dark red needles, into an aminodihydroxy- 
anthraquinonej Cj^HgO^N, m. p. 255*^ or 258°, red needles, from which, 
by elimination of the amino-group, impure 1 : ^-dihydroxyanthra- 
quinone, m. p. 182—183° instead of 191—192° (acetate, m. p. 232°), 
has been obtained. 0. S. 

Phylloxanthin. Leon Marchlewski (Ber., 1912, 45, 24 — 25). — 
The phylloxanthin described by Schunck (Abstr., 1885, 1241) is 
shown to be identical with aZ^chlorophyllan (Marchlewski and 
Marszatek, Abstr., 1911, i, 735). Phylloxanthin yields 30-02% of 
phytol instead of 31 "8%. On prolonged exposure to concentrated 
hydrochloric acid, phylloxanthin is converted into basic products, 
including a substance soluble in 20% hydrochloric acid. 

A more recent preparation of phylloxanthin gave a solid substance 
instead of phytol on hydrolysis. E. F. A. 



I 



Tannin. VIII. Maximilian Nierenstein (Annalen, 1912, 386, 
8 — 332. Compare Abstr., 1910, i, 265). — Purpurotannin, the 



i. 204 ABSTRACTS OF CHEMICAL PAPERS. 

amorphous, red oxidation product of penta-acetyl-leucotannin (Abstr., 
1909, i, 402), has the composition Cj^HgOj,, forms a quinoline salt, 
Ci^Hg09,2CpNH7, dark red needles, and dissolves unchanged in boiling 
2JV^-potas8ium hydroxide. It forms a tetra-acetate, m. p. 324 — 327° 
(decomp.), tetrahanzoate, m. p. 279 — 281° 
COgH COgH (decomp.), and tetramethyl ether, 

/\ /\ C„H,0,(OMe)„H,0, 

-ttqI I I U-rr m. p. 242 — 244" (decomp.), and yields diphenyl- 

\/\/\/ ene, not naphthalene, as stated {loc. cit.), by 

HO OH distillation with zinc dust. It is shown to be 

1:2:7:8- tetrahydroxydiphenyleneoxide -4:5- 

dicarhoxylic acid (annexed formula). When heated with piperidine 

(but not with quinoline) at 180°, it yields I : 2 : 7 : S-tetrahydroxy- 

diphenylene oxide, C^g^gOg, red needles, m. p. 334 — 338° (decomp.) 

{tetra-acetate, m. p. 247 — 251°), whilst by reduction with hydriodic acid 

and phosphorus at 180° it is converted into diphenylene oxide. 

A course of formation of purpurotannin from leucotannin is 
suggested. The cause of its colour will be discussed later ; apparently 
it is connected with the presence of hydroxyl groups in the peri- 
position to the oxygen of the furan ring. 0. S. 

" Luteo-acid " (A Correction). Maximilian Nierenstein {Ber., 
1912, 45, 365). — The analytical results for the composition of "luteo- 
acid" (pentahydroxydiphenylmethylolidecarboxylic acid) (Abstr., 1908, 
i, 897 ; 1909, i, 174 ; 1910, i, 265, 389) were low in the percentage of 
carbon ; as the more carefully dried substance gives results agreeing 
well with the formula Cj^HgOg, it is probable that the earlier 
discrepancies were due to occluded solvent. D. F. T. 

Decomposition of Alkylidenehydrazines. Conversion of 
Purfuraldehyde into 2-Methylfuran. Nicolai M. Kijker 
{J. Muss. Phys. Chem. Soc, 1911, 43, 1563— 1565).— When heated in 
presence of a small quantity of potassium hydroxide, furfurylidene- 
hydrazine decomposes, giving nitrogen and 2-methylfuran, a colourless 
liquid, b. p. 64°/757 mm., D^*' 0*9159, n^ 1*4344. The constants given 
for this compound by Atterberg (Abstr., 1880, 663) and by Harries 
(Abstr., 1898, i, 232) are inaccurate, doubtless on account of impure 
products being examined. T. H. P. 

Coumarandione, the Oxygen Analogue of Isatin. Karl 
Fries and W. Pfaffendorf {Ber., 1912, 46, 154 — 162. Compare 
Abstr., 1910, i, 186; also Stoermer, ibid., 1909, i, 174, and following 

abstract). — Coumaran-1 : 2-dione, CgH4<C!^^^C0, is readily prepared 

by heating a solution of o-hydroxyphenylglyoxylic acid in light 
petroleum with phosphoric oxide, or by distilling the acid under 
diminished pressure. It crystallises in large, yellow, prismatic 
plates, m. p. 134°, b. p. 142°/17 mm., and dissolves in concentrated 
sulphuric acid, yielding a yellowish-red solution, which gradually 
becomes colourless owing to the loss of carbon monoxide and 
conversion of the diketone into salicylic acid. 



ORGANIC CHEMISTRY. i. 205 

With o-phenylenediamine it yields 2-hydroxy-3-hydroxyphenyl- 
quinoxaline (Marchlewski and Sosnowaki, Abstr., 1901, i, 415). On 
exposure to air it takes up water with the formation of o-hydroxy- 
phenylglyoxylic acid or its hydrate, m. p. 43°. 

When heated at 220° under ordinary pressure, it loses carbon 
monoxide, yielding a ruby-red glassy mass, which sinters at 150°, forms 
a transparent, viscid liquid at 200°, and finally becomes mobile at 
240°. The latter substance is hydrolysed by alkalis in alcoholic 
solution to salicylic acid, and gives a colloidal solution in chloroform. 
It probably consists of a polymeric salicylide, which, however, is 
different from the polymerides described previously. 

Ethyl o-hydroxyphenylglyoxylate, CjqHjqO^, prepared by boilmg 
coumarandione in alcoholic solution, is a yellow oily liquid, which 
solidifies in a freezing mixture, m. p. 15°. It readily loses alcohol 
yielding the original ketone. 

Coumaran- 1:2- dione-2-phenylhydrazone, 0<C_pQ£^CIN*NHPh, 

obtained from its components in glacial acetic acid solution, crystallises 
in lustrous, yellow plates, m. p. 185°, and is hydrolysed by alkalis in 
alcoholic solution to the phenylhydrazone of o-hydroxyphenylglyoxylic 
acid, Cj^HjgOgNg. This crystallises in light yellow needles, m. p. 
148° (decomp.), and is also obtained by heating o-hydroxyphenyl- 
glyoxylic acid with phenylhydrazine in aqueous solution. It readily 
loses water, yielding coumarandione-2-phenylhydrazone. 

The anil of o-hydroxyphenylglyoxylic acid, Cj^H^^OgN, prepared by 
heating coumarandione with aniline in benzene or alcoholic solution, 
crystallises in pale yellow plates, m. p. 102°, and shows no tendency to 
form a lactone ; the acetyl derivative has m. p. 138°. 

The ip-dimethylaminoanil, OH*C^^H4*C(IN*CgH4'NMe2)*C02H, crys- 
tallises in dark red needles of a metallic lustre, m. p. 153°; the mono- 
sodium salt and monohydrochloride, crystallising in yellow prisms, are 
mentioned. On treatment with phenylhydrazine^ the jt?-dimethyl- 
aniline residue is eliminated with the formation of the phenylhydr- 
azone of o-hydroxyphenylglyoxylic acid. With o-phenylenediamine it 
yields 2-hydroxy-3-hydroxyphenylquinoxaline. 

When hydrolysed with aqueous alcoholic sodium hydroxide and the 
resulting solution neutralised with acetic acid, coumaran-1 : 2-dione-l- 
;)-dimethylaminoanil (Fries and Hasselbach, Abstr., 1911, i, 151) is 
converted into o - hydroxy phenylglyoxylo - p - dimethylaminoanilide, 
OH-CgH^-CO-CO-NH-O^H^-NMea, which, however, could not be 
obtained in a pure condition, and was, therefore, characterised by 
means of its benzoyl derivative, CggHgoO^Ng, stout, red prisms, 
m. p. 138°. 

With excess of bromine in glacial acetic acid solution, coumaran- 
dione yields 3 : 5-dibromo-2-hydroxyphenylglyoxyIic acid, which has 
m. p. 148° (decomp.) (compare Abstr., 1910, i, 332), and forms a 
hydrate, CgH^O^BrgjHgO, crystallising in slender, pale yellow needles, 
m. p. 110°. 

\-Bromo-2-coumaranone, CgHgO^Br, prismatic needles, m. p. 87°, and 
1 \\-dihromo-2-coumaranone, CgH^OgBrg, pale yellow needles, m. p. 
142°, are obtained by brominating 2-coumaranone in carbon tetra- 



i. 206 ABSTRACTS OF CHEMICAL PAPERS. 

chloride solution. When warmed with sulphuric acid, the dibromo- 
compound is converted into coumarandione, and finally into palicylic 
acid. On treatment with o-phenylenediamine it yields coumaro- 
phenazine. 1 : \-Dichloro-2-coumara7ioney prepared by chlorinating 
2-coumaranone in glacial acetic acid solution, forms white, pri.smatic 
needles, m. p. 70°. F. B. 

Coumarandione, the Analogue of Isatin in the Ooumarone 
Series. A Correction. Richard Stoermer (Ber., 1912, 45, 
162 — 163. Compare preceding abstract). — The compound described 
previously (Abstr., 1909, i, 174) as the hydrate of coumarandione is 
now found to be the acetyl derivative of l-oximino-2-coumaranone, 

c„h,<^(^>c:n-oac. 

It is shown that the substance is formed by the action of acetic 
acid on aci-nitrocoumaranone, and not by the oxidation of ** leuco- 
oxindigo," as previously supposed. 

With respect to the mechanism of the reaction, the author imagines 
that an intermediate compound of the composition 

C6H4<P^>CH-NO(OH)-OAc 

is first produced by the combination of acetic acid and aci-nitro- 
coumaranone, and that this is subsequently reduced by the nitrous 
acid formed by the spantaneous decomposition of the aci-nitro- 
compound, loss of 1 mol. of water taking place simultaneously. 

F. B. 

Constitution of the Desaurins. C. Kelber and A. Schwarz 
(Ber., 1912, 45, 137 — 147). — By the interaction of carbon disulphide, 
potassium hydroxide, and ketones of the type R'CO'CHg'R, Meyer 
(Abstr., 1888, 484; 1890, 1144 ; 1892, 340, 1127) obtained a number 
of desaurins, to which he ascribed the constitution : 

R-CO-CR:C<g>C:CR-CO-Il (R = aryl). 

This formula has now been confirmed by the synthesis of similarly 
constituted desaurins (II) by the removal of hydrogen sulphide from 
2 mols. of the aryl /SyS-dithiolvinyl ketones of the formula I : 

(I) R-C0-CH:C(SH)2 = (II) R-C0-CH:C<g>C:CH-C0R-l-H2S. 

A number of desaurins of the type R-CO-CMe:C<g>C:CMe-COR 

have also been prepared by heating aryl ethyl ketones, R'COEt, with 
carbon disulphide and finely-powdered potassium hydroxide. 

The compound, COPh-CHICISalCrCH-COPh, is obtained in small 
yield by heating phenyl )3^-dithiolvinyl ketone (Kelber, Abstr., 1910, 
i, 390) at 100°. It is also produced together with carbon oxysulphide, 
benzophenone, and benzoyl sulphide by rapidly heating the dibenzoyl 
derivative of the ketone (lac. cit.) either alone at 210°, or in solvents 
of high b. p., such as ethyl benzoate or acetophenone. It crystal- 
lises from ethylene dibromide in yellow, rectangular prisms, m. p. 
212 — 214° (decomp.), and dissolves in strong sulphuric acid, yielding 
orange-r^ad solutionis h&ying an intense green fluorescence. 



ORGANIC CHEMISTRY. i. 207 

The lead salt of phenyl /3^-dithiolvinyl ketone, CgH^jOSgPb, is a 
heavy, reddish-brown powder; the me7xuric salt, C^gHj^O^S^Hg, is 
soluble in organic solvents, and crystallises from toluene in orange 
needles, which have m. p. 185 — 190° (decomp.), with previous darken- 
ing at 130 — 140°. When heated in solvents of high b. p., both the 
lead and mercuric salts are decomposed with the formation of metallic 
sulphide and the above-mentioned desaurin. 

The monothiour ethane, COPh'CgHgSg'CO'NHPh, obtained from 
phenyl )8y8-dithiolvinyl ketone and phenylthiocarbimide in benzene 
solution, crystallises in slender needles, m. p. 94° (decomp.), and when 
carefully heated gives a small yield of the corresponding desaurin. 

The compound, (C4H3S*CO*CH!C)2S.2, may be prepared from 
a-thienyl j8;8-dithiolvinyl ketone (Abstr., 1911, i, 740) by methods 
similar to those employed in the case of the preceding desaurin. It 
crystallises in moss-like aggregates of slender, yellow needles, which 
decompose at 260° with previous darkening, and yields with sulphuric 
acid deep red solutions having a green fluorescence. 

The mercuric salt of a-thienyl )8^-di thiol vinyl ketone, C^H^OSgHg, 
is obtained from mercuric chloride and the ketone in alcoholic 
solution. 

The thiourethane, O^HgS'CO'CgHgSg'CO'NHPh, prepared from the 
ketone and phenylthiocarbimide, decomposes at 80°. 

The desaurin horn. p-to\y\ /?y8-dithiol vinyl ketone {loc. cit.) crystallises 
in yellow, rectangular prisms. 

The compound, COPh-CMelCISglCICMe-COPh, prepared by heating 
phenyl ethyl ketone with carbon disulphide and potassium hydroxide, 
crystallises in lustrous, golden-yellow leaflets, m. p. 225°; the compound, 
(C^H4Me-CO-CMe:C)2S2, from jt?-(?)tolyl ethyl ketone in strongly 
refractive, yellow needles, m. p. 263 — 265°. The compound, 

(C4H3S-CO-CMe:C)2S„ 
from a-thienyl ethyl ketone forms yellow needles, m. p. 258 — 260° ; 
the compound, (CjQH7*CO*CMe!C)2S2, from ^S-naphthyl ethyl ketone 
crystallises in yellow leaflets, which have m. p. 264°, and decompose 
at 268—269°. F. B. 

The Simplest Thiopyronine. Friedrich Kbhrmann and L. 
LowY {Ber., 1912, 45, 290— 292).— The chloride of the simplest 
thiopyronine, 3 : Q-diaminothioocantkinium, chloride (annexed formula) is 
pxT obtained in small yield by the addition of a 

glacial acetic acid solution of di-/>-acetyl- 
aminodiphenylmethane to a solution of 
flowers of sulphur in faming sulphuric acid 
^Cl^^ at a temperature not exceeding 10°, and 

subsequent hydrolysis of the resulting 3 : 6- 
diacetylaminothioxanthinium sulphate (not isolated). It crystallises 
from alcohol in metallic green needles or prisms, which yield scarlet-red 
solutions having a greenish-yellow fluorescence. The carbonate, 
acetate, iodide, dichromate, and also the nitrate, crystallising in scarlet- 
red needles, are described ; the platinichloride, (Ci3HiiN2SCl)2PtCl4, 
was analysed. 

Elimination of one of the amino-groups from the preceding chloride 




i. 208 ABSTRACTS OF CHEMICAL PAPERS. 

by succeRsive treatment with nitrous acid (I mol.) and alcohol results 
in the formation of iiTpothiopj/roninel(3aminothioxanthinium) chloridej 

NH2•CgHg'^^P|]>Cf,H^, which was converted into a red, crystalline 

nitrate and platinichloride, (Ci3HioNSCl)2PtCl4. F. B. 

[Preparation of Ketonaphthathiophen.] Kalle &, Co. 
(D.R.-P. 239093). — Derivatives of o-carboxynaphthylthiolacetic acids 
yield valuable dyes, and the following series of compounds have been 
prepared : a-Naphthylamine-2-sulphonic acid is converted by diazotisa- 
tion and subsequent treatment with copper sulphate and potassium 
cyanide into sodium \-cyanonaphthalene-2-8ulphonate, leaflets, which 
furnishes an acid chloride, long needles or prisms, m. p. 143°; this 
when reduced with zinc dust in sulphuric acid solution and treated with 
chloroacetic acid yields a mixture of \-cyanonaphthalene-2-thiolacetic 
acid and \-carhoxynaphthalene-2-thiolacetic acid^ which can be separated 

by fractional crystallisation from water, 

|~"\/-S-\^ when the acid is obtained in long, colourless 

|~\_| NCH'COgH needles, m. p. 93° and (when anhydrous) 
\_| \C0/ 127—128°. 

Ketonaphth thiophencarhoxylic acid (an- 
nexed formula), colourless aggregates, is obtained by the fusion of the 
foregoing mixture with sodium hydroxide, and is converted by 
treatment with mineral acids into naphthoxythiophen, glistening, grey 
crystals, m. p. 118—119°. F. M. G. M. 

[Preparation of Indigoid Compounds.] Kalle & Co. (D.R.-P. 
2 399 16). — When indoxyl, oxythionaphthens, or compounds of the same 
type (2 mols.) are condensed with a dialdehyde or diketone (1 mol.;, 
substances are obtained having the general formula : 

C6H,<|^C:CR'-Il-CR":C<^^>CeH„ 

where R is a hydrocarbon ; R', R" hydrogen or hydrocarbon 
residues ; X and Y alike or different atoms or groups, such as sulphur, 
oxygen or the imino-group. 

The yellow, crystalline compound, 

C,H,<?g^C:CH-C,H,-CH:c<Pg^C6H„ 

was prepared from ketothionaphthen (2 mols.) and terephthalaldehyde 
(1 mol.), whilst the analogous compound obtained from the bisulphite 
derivative of glyoxal (1 mol.) forms brownish-yellow needles. The 
ketothionaphthens can be replaced by indoxyls in these reactions. 

F. M. G. M. 

[Preparation of " Dihalogendimethylthioindigos."] Kalle 
& Co. (D.R.-P. 239094).— The symmetrical "dihalogendimethylthio- 
indigos " of the annexed general formula 
(where R is a halogen atom and R' a 
|R methyl group, or vice versa) are of 
technical value, and in this connexion 
the following compounds have been 
prepared. 






I I I c:c I I I I |_ ISo7i^-"^' 




ORGANIC CHEMISTRY. i. 209 

5-Chloro-3-amino-o-toluic acid, needles (prepared by the reduction of 
the corresponding chloronitrotoluic acid), when diazotised, xantho- 
genated, and treated with chloroacetic acid, yields 5-chlorophe7iyl-3- 
methyl-%carhoxyphenylthiolacetic acid, colourless needles, which on fusion 
with sodium hydroxide furnishes 6-chloro-3-hyd7'oxy-4:-methyl-{l)-thio- 
naphthen-o-carboxylic acid, and subsequently on treatment with mineral 
acid, Q-chloro-3-hydroxy-4:-methyl-{l)-thionaphthen, glistening, colourless 
needles. 

The reaction is stated to be applicable to other halogenated nitro- 
toluic acids. F. M. G. M. 

[Preparation of " Naphthioindigo."] Kalle <fc Co. (D.R.-P. 

240118). — ^' Naphthioindigo^' (formula 1) is prepared as follows: 

S S 



/ 



^S-CHo-COoH 
CO CO ^^ 

(I.) (II.) 

2-amino-3-naphthoic acid is diazotised and converted successively into 
2-ihionaphthol-3-carboxylic acid, a yellow powder, m. p. 275 — 276°, and 
S-carboxynaphthyl-2-tkiolacetiG acid (II), a colourless, crystalline powder, 
m. p. 203° ; this when treated with alkali or acetic anhydride yields 
3-keto-{l)-thioanthren, and by subsequent oxidation with potassium 
ferricyanide the foregoing " naphthioindigo." F. M. G. M. 

Bromo-derivatives of the Alkaloids of Peganum harmala 
and their Basic Derivatives. V. Hasenfratz (Compt. rend, 1912, 
154, 215—217. Compare Fischer, Abstr., 1889, 730; 1898, i, 160). 
— On treating harmaline, harmine, apoharmine, and methylapoharmine 
with bromine in acetic acid, the hydrohromides of the corresponding 
monobromo-derivatives are obtained. Bromoharmaline, CjgHjoONgBr, 
crystallises in colourless, slender needles, m. p. 195° ; the hydro- 
chloride and plaiinichloride are yellow. In the case of harmine, two 
isomeric compounds are formed, and may be separated by heating the 
hydrohromides at 50°, hromoharmine hydrohromide alone fusing at this 
temperature. Bromoharmine, CjgHjjONgBr, occurs in orthorhombic 
prisms, m. p. 275° ; the salts crystallise from alcohol, but form jellies 
with water. tsoBromoharmine crystallises in long needles, m. p. 203°, 
and its salts crystallise from water ; the plaiinichloride is orange-red. 
Bromoa,i^oharmine, CgH^NgBr, crystallises in long needles, m. p. 229°, 
and bromomethyl'dpoharmine, CgHgNgBr, in needles, m. p. 196°. 

On brominating harmine in presence of sulphuric acid, and sus- 
pending the product, Fischer's supposed tetrabromide, in hot dilute 
alcohol, slender needles of dibromoharmine monohydrobromide are 
obtained ; when treated with ammonia this gives dibromoharmine, 
CjgH^QONgBrg, m. p. 209°. Fischer's compound appears to be the 
dihydrobromide of this base. W. 0. W. 

Preparation of a Compound of Codeine with Diethyl- 
barbituric Acid. Knoll & Co. (D.K.-P. 23'^'dl3).— Codeine 



i. 210 ABSTRACTS OF CHEMICAL PAPERS. 

diethylbarhiturate^ prisms, m. p. 86°, is readily prepared by mixing 
molecular proportions of codeine and dietliylbarbituric acid (veronal) 
in aqueous or alcoholic solution, or by intimately mixing codeine 
hydrochloride with sodium diethyl barbiturate in the absence of 
solvents. F. M. G. M. 

Degradation of Sparteine. Formation of a Hydrocarbon : 
Sparteilene. Charles Moukeu and Am and Valeur {Compt. rend., 
1912, 154, 161—163. Compare Abstr., 1908, i, 43, 44, 563).— When 
methylhemisparteine is treated with methyl iodide, the product has the 
composition, CjgHgjNgMegl, but appears to consist of a mixture of at 
least two isomerides. On treatment with silver oxide, it gives a 
quaternary ammonium base, which, on heating in a vacuum, yields 
inactive dimethylhemisparteilene, Ci^Hg^NMeg, b. p. 201 — 202°/27'5 mm. 
This substance forms a methiodide and a quaternary hydroxide ; the 
latter decomposes at 75^^ in a vacuum, giving trimethylamine and 
sjyarteilene, Cj^Hgo. The new hydrocarbon is a colourless, odourless, 
optically inactive liquid, b. p. 157 — 159°/18 mm., showing a molecular 
refraction corresponding with the existence of six ethylenic linkings. 
Its production with trimethylamine, taken in conjunction with the 
formation of methylsparteilene and trimethylamine from dimethyl- 
sparteine, is sufficient to establish the symmetrical character of the 
sparteine molecule. Oxidation of sparteilene by means of potassium 
permanganate leads to the formation of an acid, Cj^HjoOg, m. p. 
300—305° on the Maquenne block. W. O. W. 

Strychnos Alkaloids. XIV. Derivatives and Decomposition 
Products of Brucinolone. Decomposition of Dihydrobrucinonic 
Acid into isoBrucinolone and GlycoUic Acid. Hermann Leuchs 
and J. F. Brewster {Ber., 1912, 46, 201—221. Compare Abstr., 
1908, 1, 563 ; 1909, 1, 253, 954).— For the preparation of brucinolone, 
brucine, dissolved in acetone, was oxidised by potassium permanganate, 
whereby brucinonic and dihydrobrucinonic acids were obtained. The 
two acids are difficult to separate completely. Brucinolic acid was 
obtained by reduction of brucinonic acid (containing some dihydro- 
brucinonic acid). This latter acid appears to be formed even when 
the most carefully purified keto-acid is reduced, and the authors have 
come to the conclusion that it is stereoisomer ic with brucinolic acid, 
since they were also able to show that the two acids are similarly 
affected by sodium hydroxide. Since dihydrobrucinonic acid is formed 
by the direct oxidation of brucine, it follows that the latter must 
contain a secondary alcoholic group. 

For the conversion of brucinolic acid into brucinolone^ the authors 
recommend the use of normal sodium hydroxide (IJ mols. instead of 
1 J mols. previously employed). The m. p. of brucinolone is now given 
as about 270°, and [a]^ -34-7°. The latter value is somewhat 
dependent on concentration and source of light used. 

By means of ice-cold nitric acid (D 1*4), brucinolone was converted 
into nitrobiaai^omethyldehydi'obrucinolonef which forms orange-coloured 
leaflets. 

Bisa/?omethylbrucinolone (bisdemethylbrucinolone of Abstr., 1909, 



ORGANIC CHEMISTRY. i. 211 

i, 954) was converted into the triacetate by treatment with acetic 
anhydride and sodium acetate. It crystallises in colourless leaflets, 
m. p. 260—261°. 

In brucinolone hydrate I. (in which the ~N-CO- of brucinolone is 
supposed to have been transformed into -NH HOgC"), the presence of 
the imino-group has been proved by the regeneration of brucinolone 
by the action of heat on the hydrate I., and by the formation of a 
derivative when treated with phenylcarbimide. The latter is a non- 
crystallisable, amorphous, white powder, m. p. 192° (decomp.) after 
previous softening. The presence of the carboxyl group is shown by 
the^isolation of the hydrochlorides of the methyl ester, m. p. 189 — 190° 
(decomp.), and of the ethyl ester, m. p. 181° (decomp.). 

The isolation of a by-product, C2iH240gN2, during the action of 
sodium hydroxide on brucinolic acid has been previously described 
(Abstr., 1909, i, 954). This substance when heated with 5iy-hydro- 
chloric acid yields a hydrochloride , which is completely melted at 255° 
after previous gas evolution. The free base obtained from this, which 
has been named brucinolone hydrate II., separates from water with vary- 
ing amounts of water of crystallisation. It has m. p. 240° (decomp.), 
after softening at 190°. It differs from the hydrate I. in possessing 
less tendency to lose water. When the by-product, CgiHg^OgNg, is 
heated with sodium hydroxide, brucinolone is formed. 

In order to gain further insighb into the oxidation products of 
brucine, hruciyiolone acetate (m. p. 253 — 254°) was prepared by heating 
brucinolone with acetic anhydride and sodium acetate. This was 
oxidised in acetone solution by potassium permanganate. In this 
manner an acid, CggHg^OgNg, was isolated, which gave a brownish-red 
coloration with alcoholic ferric chloride, and thus appears to be a keto- 
acid. When heated, it softens at 120°, melts at about 160° (decomp.), 
then solidifies, becoming yellow at 240°, and melting again at about 
275°. When heated during ten minutes at 160 — 180°, it evolves 
carbon dioxide and leaves a neutral substance, CgoHg^O^Ng, which has 
m. p. about 281°. During the oxidation, a nQ\xiv2i\ product^ CgaHggOgNg 
(m. p. about 312°), is also formed. 

By the action of normal sodium hydroxide (IJ mols.) on dihydro- 
brucinonic acid, glycollic acid was obtained together with hobrucinolone. 
The latter forms yellow crystals, m. p. 308° (decomp.), and has 

'i^ +26*9° in glacial acetic acid solution. H. W. 

ction of Acetic Anhydride on Some Benzylideneanthr- 
io Acids. John B. Ekeley and Paul M. Dean {J. Amer. Ghem. 
^., 1912, 34, 161— 164).— The products of the condensation of 
anthranilic acid with aromatic aldehydes (compare Wolf, Abstr., 1911, 
I, 735) react with acetic anhydride to form a series of oxazines which 
|g^ crystalline, very stable, and usually colourless, 
■enzylideneanthranilic acid, m. p. 126°, yields l-keto-i-acetyl-3-phenyl- 

mydro-2 -A-benzoxazine, CcH4<^^ ^ i ^^^, , m. p. 108°, which when 
■ ^ *^NAc*CHPh ^ 

iBated with hydrochloric acid is decomposed into benzaldehyde 

itid acetylanthranilic acid. 9/i-Nitrobenzylideneanthranilic acid, m. p. 

202°, and jt?-nitrobenzylideneanthranilic acid, m. p. 164°, yield l-keto- 



i. 212 ABSTRACTS OF CHEMICAL PAPERS. 

A-ctceiyl'S-m' and 'p-nitropheni/ldihydro-2 : i-henzoxazinea, m. p. 192° and 
199° respectively. When /;-hydroxybenzylideneanthranilic acid, m. p. 
207°, is heated with acetic anhydride, \-keto-4:-acet^l-3-i^-acetoxi/pheni/l- 
dihydro-2 : i-henzoxaziney m. p. 148°, is produced. Salicylidene- 
anthranilic acid, m. p. 195°, Bimilarly gives l-keto-4:-acef,yl-3-o-acetoxi/- 
phenyldihydro-2-A-benzoxazitie, in. p. 162°. Vanillylideneanthromilic 
acidf m. p. 170° crystallises in lemon-yellow needles, and when heated 
with acetic anhydride yields \-keto-iacetyl-Z-^-htjdroxy-m-7nethoxy- 
phenyldihydro-2 : i-henzoxazine, m. p. 184°, which forms pale straw- 
coloured needles. E. G. 

Thiazines. Richard Mohlau, Heinrich Beyschlag, and H. 
KoHRES {Ber., 1912, 45, 131—137. Compare Abstr., 1910, i, 337).— 
The authors have repeated the work of Kehrmann and Steinberg 
(Abstr., 1911, i, 1034), and agree with them that the dinitrophen- 
thiazine, obtained by the interaction of picryl chloride and o-amino- 
thiophenol, has the constitution originally ascribed to it by Kehrmann 
and Schild (Abstr., 1900, i, 61). The synthesis of the isomeric 
2 : 4-dinitrophenthiazine is also described. 

Di-o-aminodiphenyl disulphide is best prepared by reducing di-o-nitro- 
diphenyl disulphide (Blanksma, Abstr., 1901, i, 460) with hydrazine 
hydrate in alcoholic solution. 

The c?i6en«o?/Z derivative, (NHBz*CgH4)2S2, crystallises in pale yellow 
needles, m. p. 141°, and is reduced by aqueous sodium sulphide to 
o-benzoylaminophenyl mercaptaii, which reacts with picryl chloride in 
the presence of sodium acetate, yielding trinitrophenyl o-benzoylamino- 
phenyl sulphide, NHBz'CgH4*S*CgH2(N02)3. The latter compound 
crystallises in yellow prisms, m. p. 169°, and when boiled with sodium 
hydroxide in aqueous alcoholic solution is converted into 2 : 4c-dimtro- 
^-rr phenthiazine (annexed formula), which crystallises 

.\ y. ,. in almost black, lustrous prisms, m. p. 218° 

/ ^^ ^^ |N^2 (appearing reddish-brown by transmitted light), 

I dissolves in alcoholic sodium hydroxide, yielding 

^ Kin bluish-violet solutions, and on reduction with 

2 stannous chloride and hydrochloric acid is 

converted into 2 : ^-diaminophenthiazine stannichloi'ide, 

4CeH,<^g^>C,H2(NH2,HCl)2,SnCl4. 

This forms brownish-yellow needles, and is oxidised by ferric chloride 
in alcoholic solution in the presence of hydrochloric acid to 2 : 4-o?i- 

aminopkenazthionium chloride, CgH^<C^g^,^CgH2(NH2)2. The ferri- 

chloride, Ci2HjoN3SCl4Fe,H20, forms greenish-black, microscopic crys- 
tals, which lose their water of crystallisation at 110°; the platini- 
chloride, chr ornate, carbonate, and the thiazonium base itself are 
briefly mentioned. 

Kehrmann and Steinberg's 1 : 3-dinitrophenthiazine has m. p. 187°. 

F. B. 

Decomposition of Alkylidenehydrazines. Nicolai M. Kijnee 
(/. Russ. Phys. Chem. Soc, 1911, 43, 1554— 1562).— The author has 



ORGANIC CHEMISTRY. 1. 2l3 

been able bo pass from carone through carylidenehydrazine to carane 
(compare Abstr., 1911, i, 1028), the hydrocarbon thus obtained being 
structurally identical with that prepared from pulegone, but exhibiting 
a Isevo- instead of a dextro-rotation. 

n 1-^1^ ' n^/r ^9H-C(:N-NH2)-CHMe , , . , ^ 
(Jarylidenehydrazine, Kjm.Q^<^\ Au- » obtained by 

Old. ^1^2 ^^2 

the action of hydrazine hydrate on carone, is a viscous liquid, b. p. 
131720 mm., Dg" 0-9683, i^D 1-5082, [ajn + 375-7— 378-8° (absolute 
alcohol). Its thioureide, NHPh'CS'NH'NICjoHjg, forms hexagonal 
plates, m. p. 100 — 101°. Hydrolysis of carylidenehydrazine by either 
boiling dilute sulphuric acid or hydrochloric acid at the ordinary 
temperature yields a product showing all the physical properties of 
carvenone with the exception of a slight Isevo-rotation, apparently due 
to admixture of a small quantity of an intermediate compound in the 
hydrolysis. 

\-Carane, CjoHig, has b. p. 169— 169-5°/761 mm., Bf 0-8411, 
Uj) 1-4569, [ajo —47-06°, is very stable towards permanganate, and 
combines, with generation of heat, with halogen hydracids and 
bromine. The 6romo-derivative, CjoHjgBr, obtained by the action of 
hydrobromic acid, has D?« 1-1774, n^ 1-4910, [a]i, -6-40°, and yields 
A^^^'-m-metithene and A^'^*-m-menthene in the same way as c?-carane 
{loc. ciL). T. H. P. 

Refutation of Bulow's Views Concerning Pyrazoline- 
carboxylic Acids. Eduard Buchner {Ber., 1912, 45, 117 — 121). — 
Many arguments are advanced to disprove Bulow's view (this vol., 
i, 134) that a mixed azine, CHXIN'NICX'CHgX, not a pyrazoline 

CX— OHX 
derivative, N«^ Auv' ^^ produced by the action of ethyl diazo- 

acetate on an unsaturated ester of the type CHXICHX (X = CO^Et). 

0. S. 

Derivatives and Decomposition Products of Methyl Methoxy- 
benzoylacetates. Andr^ Wahl and 0. Silberzweig (Bull. Soc. 
Chim.^ 1912, [iv], 11, 61 — 69). — The methoxybenzoylacetates are 
convertible into a;8-diketonic esters, and, as these may react with various 
reagents giving compounds identical with those obtainable from the 
initial yS-ketonic esters, the following compounds have been prepared 

i^^d characterised so that they may be readily identified, 
^k Methyl a-oximino-o-7nethoxyhenzoylacetate, 
^ OMe-C6H4-CO-C(NOH)-C02Me, 

m. p. 146 — 147°, produced by the action of nitrous acid on the 
)8-ketonic ester in acetic acid, crystallises from ether. The original 
ester reacts with phenylhydrazine to form Tahara's l-phenyl-3-o- 

methoxyphenyl-5-pyrazolone, PhN<^~"^'^^^*'^^®,m. p. 133—134° 

00*032 

yellow needles, and with j9-nitrophenylhydrazine to form l-p-m<ro- 
Ai^^enyl-'^-o-methoxyphenyl-b-pyrazolonef m. p. 217 — 218°, brown needles. 
i^K Methyl a-phenylhydrazonoazo-o-methoxybenzoylacetate, 
W OMe-C6H4-CO-0(:N-NHPh)-C02Me, 

j^t VOL. cii. i. q 



i. 214 ABSTKACTS OF CHKMICAL PAPERS. 

m. p. 138 — 139°, obtained by the action of benzenediazoninm chloride 
on the ester in the cold, forms yellow crystals from alcohol, and reacts 
with phenylhydrazine to form i-phenylhydrazono-l-p/ieiiyl-^-o-Tnethoxy- 
phenyl-b -pyrazolone^ m. p. 139°, orange crystals, and with /?-nitrophenyl- 
hydrazine to form A-phenylhydrazono-[-'p-niirophenyl-3-o-methoxyphenyl- 
5'pyrazolone, m. p. 200°, red crystals, from pyridine. 

Methyl p-nitrophenylhydrazono-oniethoxybenzoylacetate, m. p. 170°, 
obtained by the action of the sodium derivative of ^-nitrophenylnitroso- 
amine on the )8 ketonic ester, forms yellow cryhtals, and reacts with 
phenylhydrazine to give 4-p-nitrophenylhydrazono-l-p/ienyl-Z-o-methoxy- 
pfienyl-b-pyrazolone, m. p. 267°, red crystals. 

Methyl oximinom-methoxyhenzoylacetate, m. p. 115 — 116°, forms 
colourless needles from ether and light petroleum, and on treatment 
with phenylhydrazine gives 4:-oximino-l-pfienyl-3-ui'methoxyphenyl-5- 
pyrazolone, m, p. 157°, which forms red crystals from acetic acid. 

Methyl plienylhydrazono-ui-methoxybenzoylacetate, m. p. 72 — 73°, 
forms yellow crystals; the free acid^ m. p. 118 — 120°, forms 
yellow needles. Methyl T^-nitroplienylhydrazono-m-methoxyhemoylacetate^ 
m. p. 155 — 156°, crystallises in yellow needles. l-Fhenyl-3-m-methoxy- 
phenyl-b -pyrazolone, m. p. 124°, forms pale yellow crystals. A:-Pfienyl- 
hydrazono-l -phenyl-Z-m-methoxyphenyl-b -pyrazolone, m. p. 137°, and the 
corresponding 4:-p-nitrophenylhydrazo'ne, m. p. 235°, both form red 
crystals. 

Methyl oxtminoanisoylacetaie, m. p. 154°, forms colourless crystals 
from boiling methyl alcohol. 

Methyl phenyl hydrazonoanisoylacetate, m. p. 121 — 122°, forms orange 
crystals ; the Jfree acid, m. p. 149 — 150°, is yellow. The acetyl deriv- 
ative of the ester has m. p. 116°, crystallises in colourless needles, and 
on reduction furnishes some acetanilide, whence it is believed to have 
the constitution 0Me'CgH^'C0*C(IN*NPhAc)'C02Me (compare Auwers, 
Abstr., 1909, i. 222). 

Methyl i>nii7'ophenylhydi'azonoani8oylacetate,Txi. p. 175°, forms yellow 
crystals ; the/ree acid, m. p. 236 — 238°, is also yellow, but dissolves 
in all%lis with an intense red colour. 

l-Plienyl-S-'p-niethoxyphenyl-b -pyrazolone has m. p. 137 — 138°; the 
4-oa7imino-derivative, m. p. 244°, forms red crystals. p-Nitrophenyl- 
3 '"p-meUioxy phenyl -b-pyrazolone, m. p. 204 — 205°, is brown. 4:-Fhenyl- 
hydrazono-l -phenyl-3-p-methoxyphenyl-5 -pyrazolone, m. p. 177°, is red; 
the corresponding i^-nitrophenylhydrazone, m. p. 213 — 214°, separates 
from acetic acid in violet crystals, and the isomeric A^-phenylhydrazono- 
l-p-nitrophenyl-o-p-methoxyp)ienyl-5-pyrazolone, m. p. 239°, is red. 

The methoxybenzoylacetic esters are hydrolysed by boiling with 20% 
sulphuric acid into the corresponding o-, m-, and ;?-methoxyaceto- 
phenones. The semicarbazone of m-methoxyacetophenone has m. p. 
195—197° (compare Klages, Abstr., 1904, i, 45) and that of the 
;>-com pound melts at 197°. T. A. H. 

Quinazolines. XXVIII. 4-Quinazolone-2-phthalones and 
Certain of their Derivatives. Marston T. Bogert and Michael 
Heidelberger (J. Amer. Chem. Soc, 1912, 34, 183—201). — An 
account is given of certain phthalones obtained by the action of 



ORGANIC CHEMISTRY. i. 215 

phthalic anhydride on 2-methyl-4-quinazolone (2-methyl-4-hydroxy- 
quinazoline) and its derivatives. These compounds, like the quino- 
phthalones, behave as yellow dyes, but are inferior to the latter 
in tinctorial power. 

4:-Quinazolone-2-phthalone [^-hydroxyquinazoline-^-phthalone^ 2-in- 
dandionylA-quinazoloTief or p-\^'-quinazolonyl-2')-diketohydrindene\ 

V«f^A*^>C-CH<^|^>C6H4, m. p. 318° (corr.), obtained by heating a 

mixture of 2-metbyl-4-q«inazolone and phthalic anhydride to about 
200°, forms pale yellow, prismatic needles or hexagonal plates, and 
when heated above 200° sublimes in woolly masses of minute needles. 
In one experiment in which a large excess of phthalic anhydride was 
used, on extracting the reaction product with hot water, 2-methyl- 
i-quinazolone phthalate was obtained, which crystallises in pale yellow, 
fluorescent needles with IHgO ; the anhydrous salt has m. p. 171° 
(corr.). The di-sodium salt of the phthalone is orange-red, whilst the 
mono-sodium and silver salts are pale yellow. On reducing the 
phthalone with zinc dust and sodium hydroxide, 4:-quinazolone-2- 

hydrindone, OqH.^<^ . I 1 1 -r| > is obtained, which forms olive- 
CO . rs Jtx L'0~L'gxl^ 

yellow, microscopic crystals, sublimes above 160°, and melts at about 

328° (decomp.). When the phthalone is heated with aniline in 

presence of zinc chloride, the anil, 

m. p. 284 — 285° (uncorr.), is produced, which crystallises in brilliant, 
scarlet needles ; its sodium salt and compound with zinc chloride are 
described. From the product of this reaction, a small quantity of 
another anil, m. p. 258°, was obtained, which forms red crystals and 
appears to be a condensation product of 1 mol. of aniline with 2 mols. 
of the phthalone. 4:-Quinazolone-2-phthalonemonophenylhyd7'azone, 
m. p. about 225° (uncorr.), was obtained as an orange-brown, micro- 
crystalline powder. 4:-Quinazolone-2-phthalone-Q-sulphonic acid, m. p. 
about 355 — 360° (uncorr.), crystallises in minute plates or needles ; its 
mono- and di-sodium and barium salts are described. Solutions of the 
di-sodium salt dye wool or silk light yellow shades. By the action of 
bromine on the sulphonic acid, there were formed a di- and a penta- 
bromo-2-methyl - 4 - quinazolone, a bromo - 2 - methyl - 4 - quinazolone- 
sulphonic acid, phthalic acid, and sulphuric acid. Dihromo-2-methyl- 
^-quinazolone, m. p. about 293° (decomp.), forms masses of delicate, 
colourless needles. Fentabromo-2-methyl-4:-quinazolone, m. p. about 
243*5° (decomp.), crystallises in colourless, prismatic needles. Bromo- 
2-methyl-4:-quinazolone8ulphonic acid, m. p. 285 — 286*5° (uncorr.), 
forms a grey, amorphous solid containing IHgO; its barium salt 
crystallises with 4JH2O. 

Attempts to prepare 4-quinazolone-2-phthalines by heating the 
ammonium salt of the phthalone with alcoholic ammonia in sealed 
tubes did not meet with success. Bis-(4:-quinazolone-2)-^-phthaline, 

C8H50N2-CH:C<~-^>C:CH-C8H50N2, obtained by heating a 

Q 2 



i. 216 ABSTRACTS OF CHEMICAL PAPERS. 

mixture of phthalimide and 2-methyl-4-quinazolone, is an orange-brown 
aiihstanie which darkens gradually when heated ; its solution in 
dilute acetic acid acts as a powerful yellow dye. 4:-Quinazolone- 

%P-phthali7i6, C8H50N2-CH:C<^^>CgH^, m.p. about 349° (decomp.), 

is also produced in this reaction, and forms orange-brown, microscopic 
pli^m8. 

2-Methyl-4-quinazolone reacts with succinic anhydride with 
production of a tarry mass, from which a small quantity of a suhstancey 
m. p. *J74 — 277° (decomp.), was isolated in the form of thin, colourless, 
lustrous plates. 

6-Nitro-i-quinazolone-2-phthalo7ie, obtained by heating 6-nitro- 
2-methyl-4-quiuazolone with phthalic anhydride at about 210°, forms 
minute, yellow crystals and does not melt below 355°. 

7-Acetylamino-4: quinazolone-2phthalone, resulting from the action 
of phthalic anhydride on 7-acetylamino-2-methyl-4-quinazolone, 
crystallines in bright yellow, lustrous plates, and does not melt 
below 356°. 

N=iCMe 

2 MetJiyiyethylA-quinazolone^ ^6^4<Cn/-K xri^i. » ™- P' ^'^° (corr.), 

CO • JN iiit 

obtained by heating acetylanthranil with excess of an aqueous solution 

of ethylamine in presence of a little potassium hydroxide, forms 

colourless, slender needles ; its platinichlm'ide decomposes at about 

229°. In one experiment in which potassium hydroxide was 

not added, anthranilethylamide, NHEt'CO'CgH^'NHAc, m. p. 

139 "5 — 140 5° (corr.), was isolated in the form of transparent, 

prismatic plates. 

Z-EfhylA-quiiiazolone-%phihal(me, m. p. 198-5° (corr.), obtained from 

2-methyl-3-ethyl-4-quinazolone and phthalic anhydride, forms bright 

yellow, lustrous, prismatic needles with a slight green fluorescence. 

E. G. 



Formation of Pyrimidines by Use of Nitromalonaldehyde. 
William J. Hale and Harvey C. Brill {J. Amer. Chem. Soc.^ 1912, 
34, 82— 94).— Hill and Torrey (Abstr., 1899, i, 788) have shown that 
nitromalonaldehyde reacts readily with primary amines. This work 
has now been extended to other amino-compounds. 

When carbamide is allowed to react with the sodium derivative of 
nitromalonaldehyde in presence of a few drops of piperidine, the mono- 
ureide and 5-nitro-2-hydroxypyrimidine are produced. 

Nitromalonaldehyde moiw-ureide, NH2-C0-N:CH'0H(N02;*CH0, 
m. p. 154° (corr.), forms pale yellow crystals; its sodium salt 
crystallises with 3H2O. The anil, 

NH2-CO-N:CH-CH(N02)-CH:NPh, 
m. p. 211° (corr.), crystallises in lustrous, red needles. The oxime, 
NH2-C0-N:CH-CH(N02)-CH:N0H, m. p. 174—175° (corr.), forms 
yellow leaflets. 

5-miro-2-hydroxypyrimidiney 0H-C<^;^^>C-N02, m. p. 203-5° 

(corr.), crystallises ?n small, yellow plates; the sodium, potassium, 



ORGANIC CHEMISTRY. i. 217 

barium, and silver salts are described. The methyl ether, m. p. 
168 — 169° (corr.), forms colourless plates. 

5-Mtro-2-phenylpyri7mdine, CPh'^^.pTT^C-NOg, m.p. 219° (corr.), 

obtained by the interaction of benzamidine hydrochloride and sodium 
nitromalonaldehyde, crystallises in white plates. 

^-Nitro-2-aminopyrimidine, NHg'C'^i^.pTT^C-NOg, m. p. 236° 

(corr.), prepared by the action of guanidine carbonate on sodium 
nitromalonaldehyde, forms colourless, slender needles, and when 
heated with solution of alkali hydroxide is converted into 5-nitro- 
2-hydroxypyrimidine ; the acetyl derivative, 

NHAc-C<^:^^>C-N02, 

m. p. 172'5° (corr.), crystallises in long, colourless needles. When 
a small quantity of potassium hydroxide is added to a mixture of 
5-nitro-2-aminopyrimidine and carbon disulphide at 60°, 5 ; b'-di- 

niiro-2 : 2' - dipyrimidylthiocarhamide, CS[NH'C"^-j^.p^^C'N02]2» 

m. p. 230 — 231° (corr.), is produced, which forms a mass of glistening 
leaflets. 

Nitromalonaldehyde phenylureide, CH0-CH(N02)-CH:N-C0-NHPh, 
m. p. 176 — 177° (corr.), was obtained by the condensation of nitro- 
malonaldehyde with phenylcarbamide. The corresponding henzyl- 
ureide, m. p. 150 — 151° (corr.), and methyl^ireide were also prepared. 

E.G. 

Chlorides of Amino-acids. Carl Mannich and R. Kuphal 
(Ber.j 1912, 46, 314 — 322). — By the internal condensation of benzyl- 
aminoacetyl chloride and of similar amino-acid chlorides in the presence 
of aluminium chloride, the authors hoped to prepare derivatives of 

O FT 'N^IT 
zsoquinoline, CH2Ph-NH-OH2-COCl — > CQB.^<C.nn—nTj • ^^ ^^^ 

found, however, that the chlorides readily lost hydrogen chloride 
even in the absence of aluminium chloride with the formation of 
diketopiperazines. 

Ethyl benzyl aminoacetate, prepared by the interaction of ethyl 
chloroacetate and benzylamine, is a colourless liquid of aromatic odour, 
b. p. 153 — 154°/13 mm., and is readily hydrolysed by hydrochloric 
acid to benzylaminoacetic acid (Mason and Winder, Trans., 1894, 67, 
187). It is accompanied by a substance, which crystallises from 
dilute alcohol in lustrous, white leaflets, m. p. 238 — 239°, consisting 
probably of benzylaminoacetobenzylamide hydrochloride, 

C^H7-NH-CH2-CO-NH-C^Hy,HCl. 
The amino-acid is converted by the action of phosphorus pentachloride 
and acetyl chloride (Fischer, Abstr., 1905, i, 263) into henzylamino- 
acetyl chloride hydrochloride, C7H^*NH'CH2*C0C1,HC1, which forms 
slender, white needles, and when heated in nitrobenzene solution 

yields 3 : &-diketo-\ : i-dibenzylpiperazine, C7H^'N<!no.CH ^^'^7^7' 
crystallising in white needles, m. p. 172 — 173°. 



i. 218 ABSTRACTS OF CHEMICAL PAPERS. 

3 : A-Metht/lenedioxi/h^nzylaminet GK^'02\G^yLj^'CH.2*J^K2, prepared by 
reducing piperonaldoxirae with sodium amalgain and alcohol, the 
solution being maintained continually acid by the addition of acetic 
acid, is a colourless liquid, b. p. 138 — 139"/13 mm.; on exposure to air 
it foims a solid carboiiale ;. the hydrochloride^ lustrous, white leaflets, 
has m. p. 227° ; the benzoyl and cldoroacetyl derivatives crystallise in 
slender, white needles, m. p. 117 — 118° and 107 — 108° respectively. 
It reacts with ethyl chloroacetate, yielding ethyl 3 : 4L'7nethylenedioxy- 
henzylaminoaceiale, CHglOjICgHg'CHg'NH'CHg'COgEt, which forms a 
hydrochlo)'idej white needles, m. p. 157 — 158°, and is hydrolysed by 
aqueous potassium hydroxide to the corresponding acid. This has 
m. p. 206 — 207°, and is converted by acetyl chloride and phos- 
phorus pentachloride into 3 : i-inethylenedioxyhenzylaminoacetylchloride 
hydrochloride, CjoHj^OgNCI^. 

3 : ^'Diketo-\ : 4:-di-{6' : ^'ymethylenedioxyhenzylpiperazine, 

CH,:o,:C,H3-CH2-N<^^.2^^^>N-CH,-C,H,:o:CH„ 

prepared by heating the preceding chloride hydrochloride in 
nitrobenzene solution, forms white needles, m. p. 234 — 235°. 

Etfiyl benzyhyiethylaminoacetate, C^HY'NMe'CHg'COgEt, obtained 
from ethyl chloroacetate and benzylmethylamine, has b. p. 138°/ 
13 mm. ; the syrupy hydrochloj-ide, the orange platinic/doride, and the 
picrate, crystallising in stout, yellow needles, m. p. 122 — 123°, are 
described. When hydrolysed with concentrated hydrochloric acid, it 
yields the corresponding acid, CjQHjgOgN, which forms a hydrochloride, 
sintering at 174°, m. p. 180 — 181°, and a chloride hydrochloride, 
CyHy-NMe-CHg-COC^HCl. 

The latter compound reacts with aluminium chloride at 100°, 
yielding carbon monoxide, formaldehyde, and benzylmethylamine, 
together with a-dibenzyldirnethylmethylenediamine, CH2(NMe*CKH^)2, 
a pale yellow oil, b. p. 172 — 175°/8 mm. The constitution of the 
last-named compound has been established by its synthesis from 
benzylmethylamine and formaldehyde. F. B. 

Preparation of Halogen ated Dehydroindigotin Salts, their 
Nuclear Homologues and Substitution Products. Badische 
Anilin- »t Soda-Fabrik (D.K-P. 239314). — Halogenated dehydro- 
indigotin salts have previously been described, and the preparation of 
higher halogenated derivatives is now recorded. 

Trichlorodehydroindigotin acetate, a canary-yellow powder, is 
prepared by passing chlorine into a cooled acetic acid solution of 
dehydroindigotin acetate until the product has completely separated ; 
when nitrobenzene is employed as solvent, a tetrachlorodehydroindigotin 
hydrochloride is obtained, whilst under these conditions indigotin 
yields trichlorodehydroindigotin hydrochloride (isolated in the form of 
its bisulphite compound), and 5 : 5'-dibromoindigotin in acetic acid 
solution furnishes dichlorodibromodehydroindigotin hydrocMoride. 
Other solvents, such as acetyl chloride or carbon tetrachloride, can be 
employed, and the formation of other halogenated iudigotins is 
discussed. F, M. G. M. 



ORGANIC CHEMISTRY. 1. 219 

Action of Alkyloxides and Amines on Benzoyl isoCy&no- 
chloride [Benzoylcarbylamine Chloride]. Treat B. Johnson and 
Lewis H. Chernoff (J. Amer. Chem. Soc, 1912, 34, 164 — 170). — 
Benzoylcarbylamine chloride/CgHg'OO'NICCIg, obtained by Johnson 
and Menge (Abstr., 1904, i, 949) by the action of chlorine on benzoyl 
thiocyanate, is decomposed by water with formation of hydrochloric 
acid, benzamide, and benzoic acid. It combines with sodium alkyl- 
oxides to form compounds of a new class, the acylimidocarbonates, and 
reacts with amines with production of substituted guanidines, which 
yield stable salts with mineral acids and are hydrolysed by alkali 
hydroxide with formation of the free guanidines and benzoic acid. 

Diethyl henzoylirnidocarhonate, NBzIC(0Et)2, b. p. 93 — 100°/20 mm. 
and 110 — 120°/32 mm., was prepared by the action of benzoylcarbyl- 
amine chloride on sodium ethoxide. Dimethyl benzoylimidocarhonate, 
b. p. 95 — 102720 mm., is a colourless oil. 

Benzoyl-ay-diphenylguanidine, NBzIC(NHPh)2, m. p. 212° (decomp.), 
obtained by the action of benzoylcarbylamine chloride on a solution of 
aniline in benzene, forms colourless needles. /S-Benzoyl-ay-di-o- and 
-m-tolylguanidinea, NBz:C(NH-C(5H4Me)2,have m.p. 126° and 177—178° 
respectively. Di-m.-tolylguanidine^ NHIC(NH'CgH4Me)2, m. p. 
108 — 109°, was obtained from the benzoyl compound by hydrolysis with 
potassium hydroxide. /3- Benzoyl- ay-di-ip-tolylguanidine, m.p. 190°, yields 
a hydrochloride, m. p. 190 — 191° (decomp.). The following guanidines 
were also prepared: benzoyltetraphenylguanidine, m. p. 142 — 144°; 
p-benzoyl-ay-diphenyl-ay-dimethylguanidine, m. p. 135°; p-henzoyl-ay-di- 
panisylguanidine, m.p. 128°, and di-p-anisylguanidinef m.p. 153°; 
^-henzoyl-ay-di-p-naphthylguanidinef m. p. 162°, and di-fi-naphthyl- 
guanidine^ m. p. 197° (decomp.). E. G. 

Reduction of Semicarbazones. Sidonius Kessler and Hans 
RuPE {Ber., 1912, 45, 26 — 30). — Semicarbazones are readily reduced 
by sodium amalgam in dilute alcoholic solution at a slightly elevated 
temperature. In some instances, for example, those of cinnamaldehyde 
and styryl methyl ketone, the influence of the constitution of the 
semicarbazone prevents reduction to semicarbazide. 

Benzylsemicarbazide, CHgPh'NH'NH'CO'NHg, from benzaldehyde- 
semicarbazone, crystallises in lustrous platelets, m. p. 155°. It is 
distinctly basic, dissolving in cold dilute acids, and reduces Fehling's 
solution on boiling. The hydrochloride forms silky, lustrous needles, 
m. p. 178 — 180°; the sulphate yields slender needles, m. p. 158°; the 
picrate gives slender, yellow needles, m. p. 161 — 162°, and the oxalate 
has m. p. 178 — 179° (decomp.). The acetyl derivative crystallises in 
beautiful, colourless plates, m. p. 207°; a diacetate could not be 
obtained ; the benzoyl derivative forms colourless needles, m. p. 230°. 

Nitrosobenzylsemicarbazide, CB[2Ph'N(NO)*NII*CO*NH2, prepared 
by the action of sodium nitrite and hydrochloric acid on benzyl- 
semicarbazide, crystallises in long needles, m. p. 133° (decomp.). 

^-Methylbenzylsemicarbazide crystallises in slender, colourless needles, 
m. p. 158°; the hydrochloride forms colourless needles, m. p. 138° 
(decomp.); the sWp/iaie decomposes at 187°; the picrate yields yellow 
needles, m. p. 178° (decomp.), and the acid oxalate decomposes at 



i. 220 ABSTRACTS OF CHEMICAL PAPERS. 

1 75°. The acetyl derivative crystallises in glistening, colourless platelets, 
m. p. 225° (not decomp.). 

Nitroso-p-methylbenzylsemicarbazide separates in colourless platelets, 
and decomposes at 126 — 127°. 

When cinnamaldehydesemicarbazone is reduced, )8-phenylprop- 
aldehydesemicarbazone, m. p. 128°, is the sole product. 

Similarly, from the semicarbazone of styryl methyl ketone, the 
product is the semicarbazone of phenylethyl methyl ketone. 

E. F. A. 

Reduction of Semicarbazonee and the Preparation of Some 
Hydro xytriazoles. Hans Rupe and "E. Oestreicher (Ber., 1912, 
45, 30 — 38. Compare preceding abstract). — The property of semicarb- 
azones of being reduced to semicarbazide is closely dependent on their 
constitution. A phenyl residue must be attached directly to the group 
CIN. Aliphatic hydrocyclic and compounds in which phenyl is replaced by 
benzyl cannot be reduced. The semicarbazones of benzoylpropionic acid 
and of jt?-benzoquinone could not be reduced. The semicarbazides vary 
considerably in their basic properties ; those from benzophenone, aceto- 
phenone, and deoxybenzoin dissolve in dilute acids in the cold, whereas 
those from salicylaldehyde or piperonal dissolve only when boiled with 
acids. 

3 : ^-Methylenedioxyhenzylsemicarhazidej 

CH202:C6H3-CH2-NH-NH-00-NH2, 
from piperonalsemicarbazone, forms transparent prisms, m. p. 18i°. 
The acetyl derivative crystallises in slender, transparent needles, 
m. p. 203 — 204° ; the formyl derivative forms long, transparent, rhombic 
plates, m. p. 204—205°. 

Z-Hydroxy-ira^-methylenedioxyhenzyiyb-methyl-X : 2 : i-triazolcy 

CHA:CeH,-CH,-N<^|!:^Q, 

prepared by boiling the acetyl derivative with 30% sodium hydroxide 
and decomposing the sodium salt formed with hydrochloric acid, forms 
opaque, square crystals with stunted ends, m. p. 190° ; it forms 
characteristic metallic salts. From the formyl derivative of the semi- 
carbazide, S-hydroxy-{mp-inethylenedioxybenzyl)-\ : 2 : 4:-triazole is ob- 
tained ; it crystallises in stout, transparent plates, m. p. 246 — 247°. 
a-Phenylethylsemicarbazide, CHMePh-NH'NH-CO-NHg, from aceto- 
phenonesemicarbazone, crystallises in four-edged, transparent prisms, 
m. p. 142 — 143°. The acetyl derivative forms platelets, m. p. 
228 — 230°, the formyl derivative crystallises in slender, matted 
needles, m. p. 187° 

3- Hydroxy- l-a-phenylethyl-5-methyltriazole, 

crystallises in short, well formed prisim«, m. p 146 — 147°. 

3-Hydroxy-\-a-phenylethyltriazo(e is obtained in transparent, slender, 
intergrown prisms, m. p. 140°. 

Diphenylmethylsemicarbazidey CHPhg'NH'NH'OO'NHg, crystallises 
in long, lustrous, transparent needles, m. p. 164 — 165°; it gives an 



ORGANIC CHEMISTRY. 1. 221 

intense yellow coloration with concentrated sulphuric acid. The 

acetyl derivative crystallises in small, transparent prisms, m. p. 237° ; 

theformyl derivative yields small, colourless needles, m. p. 182°. The 

nitrosoamine, CHPh2'N(NO)']SrH'00'NH2, forms slender, faintly 

yellow-coloured needles, m.p. 122°. 

CMeIN 
^•Hydroxy-\-diphenylmethyl-^-methyltriazol6i CHPh2'N<^ 1 » , 

crystallises in glistening needles, which appear under the microscope as 
prisms with two superposed pyramids. 

S-IIydroxy-1-diphenylmethyltriazole forms slender, matted needles, 
m. p. 253°. 

ap-Diphenylethylsemicarhazide, prepared from deoxybenzoinsemicarb- 
azone, crystallises in long, slender, transparent needles grouped in 
stellar aggregates, m. p. 139°. The acetyl derivative forms slender, 
woolly needles, m. p. 196°; the formyl derivative gives small, trans- 
parent prisms, m. p. 194°. 

o-Hydroxybenzylsemicarbazide, from salicylaldehydesemicarbazone, 
crystallises in four-edged prisms, m. p. 128°. The acetyl derivative 
separates in slender needles, m. p. 204° ; the formyl derivative 
forms flat, transparent plates, m. p. 183 — 184°. 

S-[Iyd7'oxy-l-o-hydroxybenzyl-5-methyltriazole forms crystals, m. p. 
192°, and gives a reddish-violet coloration with sulphuric 
acid. 

3-Hydroxy-l-o-hydroxybenzyltriazole forms platelets of silvery lustre, 
m. p. 211° (decomp.). 

S-IIydroxy-5-benzyl-l-methyltriazole crystallises in transparent prisms, 
m. p. 168°. 

3- Hydroxy -l-benzyltriazole forms lustrous, nacreous platelets, 
m. p. 147—148°. E. F. A. 



Determination of Configuration of Stereoisomeric Hydr- 
azones. Max Busch {Ber.^ 1912, 45, 73 — 85). — Stereoisomeric 
diphenylsemicarbazones of unsymmetrical esters of dithioearbonic 
acid, NHPh'CO*NPh*NIC(SR)*SR', analogous to the stereoisomeric 
phenylhydrazones (Abstr., 1911, i, 811) have been obtained. 

Ethyl dithiocarbonate-diphenylsemicarbazidey 

NHPh-C0-NPh-NH-CS2Et, 
stout needles, m. p. 149 — 150°, obtained from equal molecular quan- 
tities of phenylcarbimide and ethyl phenyldithiocarbazinate in warm 
benzene, dissolves readily in aqueous alkalis, and is decomposed by 
prolonged boiling with alcoholic potassium hydroxide, yielding ethyl 
mercaptan and, after acidifying, 3-thiol- 1 : 4-diphenyltriazolone 
(Abstr., 1911, i, 689). By treating its alcoholic solution with equi- 
valent quantities of potassium hydroxide and methyl iodide, it yields 
{a) methyl ethyl dithiocarbonate-diphenylsemicarbazone, 

NHPh-CO-NPh-N :C(SMe)-SEt, 
m. p. 93 — 94°, rhombic needles. The stereoisomeric (b) methyl ethyl 
dithiocarbonate-diphenylsemicarbazone, m. p. 87 — 88°, monoclinic needles 
or prisms, is prepared in a similar manner from methyl dithiocarbonate- 
diphenylsemicarbazide, ethyl iodide, and potassium hydroxide. These 



i. 222 ABSTRACTS OF OHBMIOAL PAPERS. 

two btereoisomeric semicarbazones behave very similarly. However, 
when warmed at 50 — 60° with alcoholic potassium hydroxide, the 
former yields ethyl mercaptan and the methyl thio-ether of 3-thiol- 
1 : 4-diphenyltriazolone, whilst the latter yields methyl mercaptan and 
the ethyl thio-ether, m. p. Ill — 112°, of the same triazolone ; in both 
eases the alkyl group, which was introduced first, is eliminated as a 
mercaptan. 

Another pair of stereoisomeric semicarbazones are described. 
j»-Nitrobenzyl phenyldithiocarbazinate and phenylcarbimide in benzene 
yield ^nitrohenzyl dithiocarbonate-diphenylsemicarbazide, 

NHPh-CO-NPh-NH-CSg-CyHfl-NOg, 
m. p. 119 — 120^, colourless needles, which is converted by alcoholic 
potassium hydroxide and methyl iodide into (a) p-nitrobenzyl methyl 
dithiocarhonate-diphenylsemicarhazone, 

NHPh-CO-NPh-N:C(SMe)-S-C7H6-N02, 
m. p. 126°, stout, yellow needles. The stereoisomeric (6) ip-nitrobenzyl 
methyl dithiocarbonate-diphenylsemicarbazone, m. p. 147°, colourless 
plates, is prepared in a similar manner from methyl dithiocarbonate- 
diphenylsemicarbazide and /?-nitrobenzyl chloride. Either of these 
semicarbazones is converted, when fused or heated in alcohol for one 
to two hours, into an equilibrium mixture of approximately equal 
quantities of both forms. When warmed with alcoholic potassium 
hydroxide, the yellow form yields the methyl thio-ether of 3-thiol- 
1 : 4-diphenyltriazolone, whilst the colourless form yields methyl 
mercaptan and the ^-nitrobenzyl thio-ether , m. p. 178 — 179°, of the 
same triazolone ; in both cases, again, the alkyl group which was first 
introduced is eliminated by the action of the alkali. C. S. 



Influence of the Acridine Ring on the Colour of Certain 
Colouring Matters. A. E. Pouai-Koschitz, Y. I. Auschkap, and 
N. K. Amsler (J. Hues. Phys. Chem. Soc, 1911, 43, 1587—1603).— 
In order to decide between the chromophore and dynamic theories 
(compare von Baeyer, Abstr., 1907, i, 757) of the colour of triphenyl- 
methane colouring matters, the authors have prepared and studied 
acridylmalachite-green and acridylpyronine. The results obtained 
are distinctly in favour of the latter of the two hypotheses, since the 
absorption spectra of the two colouring matters scarcely differ from 
those of malachite-green and rosamine, the absorption bands being 
displaced towards the red end of the spectrum to an extent approxi- 
mately such as is usually observed with any more or less considerable 
increase in the molecular weight. A further consequence of the 
replacement of the benzene ring by an acridine nucleus consists in a 
marked diminution in the " permanency " of the spectral bands, this 
being expressed in a decrease in the dyeing properties of the colouring 
matters. In the case of acridylmalachite-green, the quinonoid base 
was obtained in the pure state. 

The action of 5-aldehydoacridine (compare Abstr., 1911, i, 688) on 
dimethylaniline in presence of zinc chloride and subsequent treatment 
with dilute hydrochloric acid, followed by oxidation of any leuco- 
compound with lead dioxide, yield a small quantity of a violet colour- 



ORGANIC CHEMISTRY. i. 223 

ing matter, which was not investigated further, and dimethylaminophenyl- 
acridyhnethylenequinonodimethylimonium chloride, 

which is a green colouring matter with a bronze lustre, dissolving 
slightly in water and readily in alcohol. It dyes cotton a somewhat bluer 
green than malachite-green, whilst wool is dyed only very faintly in 
neutral solution, but more strongly in presence of borax or ammonia. 
The first portions of wool immersed are coloured green with a slight 
blue tinge, but if successive portions are introduced into the same 
bath, the colour approaches more and more nearly to blue; this is found 
to be a result of the presence of alkali. 

Tetramethyldiaminodiphenylacridylmethane (leuco-base of acridyl- 

malachite - green), N<S''^4>C-CH(C6H4-NMe2)2, forms yellow, 

6 4 

acicular crystals, m. p. 171 — 172°, insoluble in water, but readily 
soluble in acids or organic solvents. 

The quinonoid base, ^<^^>0'Q<^^^'^^^^'^^ , forms 

greenish-golden plates. 

In neutral aqueous solution the maximum intensity of the absorp- 
tion band of acridyl malachite-green lies at X = 642 /x/x, whilst, according 
to Formanek, that for malachite-green is at X = 618*5 /x/x; the displace- 
ment caused by the substitution of an acridine nucleus for a benzene 
ring is hence 23'5 /x/x. 

AcTidylpyronine, ^<q'^>^'^<P^'^^^^^ obtained by 

condensing 5-aldehydoacridine with wt-diethylaminophenol in presence 
of sulphuric acid, dissolves in very dilute acids, giving a violet-red 
colour, changing to cherry-red on addition of concentrated acid. It 
dyes silk and wool reddish-violet, and cotton blue with a red tinge, no 
mordant being necessary. The absorption bands are almost identical 
in aqueous and in alcoholic solution, and in both cases little change 
is produced by acidification with nitric acid or addition of potassium 
hydroxide ; this behaviour is characteristic of all colouring matters 
of the pyronine series. The absorption spectrum of acridine lies in 
the ultra-violet, close to the visible part of the spectrum, and the 
introduction of the pyronine residue results in the displacement of 
this absorption into the violet. The maximum intensities of the 
absorption bands lie at 580 /x/x and 534*8 /x/x, whilst Biehringer 
(Abstr., 1897, i, 73) found for tetra-ethylrosamine, 563*5 and 
527*5 /x/x; the displacements caused by the replacement of the benzene 
ring by an acridine residue are hence 16*5 /x/x and 7*3 /x/x. T. II. P. 

^P Relation between Constitution and Phototropy. Maurizio 
^ABOA and F. Bovini {Atti K. Accad. Lincei, 1911, [v], 20, ii, 
712—717. Compare Padoa and Graziani, Abstr., 1910, i, 778 ; Padoa 
and Santi, Abstr., 1911, i, 693, 1029).— The phototropy of the com- 
pounds described in the present paper follows the regularities 
previously discovered. 

^-Benzil-a-naphthylosazone^ Q^\{\^'1^^'Q^^^)^, obtained by 



i. 224 ABSTRACTS OP CHEMICAL PAPERS. 

Purgotti's method (Abatr., 1893, i, 354), forms lemon-yellow crystals, 
m. p. 175°, and is not phototropic. 

P-Piperil-a-naphthylosazone, C2(CgHgI02lCHj)2(*N'NH*CiQH7)2, pre- 
pared by MacN air's method (Abstr., 1890, 1245), crystallises in yellow 
needles, m. p. 189", and is prototropic. 

^-Anisil-a-naphthylosazone, C2(CgH4'OMe)2(IN*NH'CjoHy)2, prepared 
like the preceding compound, crystallises in golden-yellow needles, 
m. p. 155°, and is prototropic. 

Fiperoiialdehyde-a-naphthylhydrazone, 

ch2:02:c6H3-ch:n-nh-CioH^, 

crystallises in greenish-yellow needles, m. p. 147°, and is not 
phototropic. 

Salicylaldehyde - a - naphthylhydrazone, HO'CgH^'CHIN'NH'CjoH^, 
forms lustrous, golden-yellow needles, m. p. 134°, and is not 
phototropic. 

Vanillin-a-naphthylhydrazone, OMe'CgH8(OH)'CHIN'NH'CjoH7, is 
an unstable, yellow, crystalline powder, which is not phototropic. 

p - Tolucddehyde - a - naphthylhydrazone, CgH^Me'CHIN'NII'CjQH,., 
crystallises in greenish-yellow needles, m. p. 152°, and is not 
phototropic. 

^-Benzil-l : 3 : i-xylylosazone^ C2Ph2(*.N'NH'CgH3Me2)2, is an orange- 
yellow, crystalline substance, m. p. 71 — 72°, and is phototropic. 

Piperil-Y : 3 : 4-xylylosazone, C2(CgH3:02:CH2)2(:N-NH-C6H3Me2)2, 
forms lemon-yellow prisms, m. p. 187°, and is phototropic. 

Anisil-i : 3 : i-xylylosazone, C2(CgH3*OMe)2(*N*NH-C(.H3Me2)2, is an 
orange-yellow, crystalline substance, m. p. 75°, and is phototropic. 

Cuminil-1 : 3 . A-xylylosazone, C2(CgH4Pr^)2(!N'NH'CgH3Me2)2, is a 
yellow, crystalline substance, m. p. 64 — 70°, and is not phototropic. 

R. V. S. 

Researches on Purines. IV. 2-Oxypurine and 2-Oxy-8- 
methylpurine. Carl O. Johns (/. jBioL Chem., 1912, 11, 67—72).— 
6-Oxypurine (hypoxan thine) was first isolated by Scherer in 1850, and 
nearly fifty years later was synthesised by Fischer. 8-Oxypurine was 
prepared by Fischer and Ach. 2-Oxypuririe was prepared by Tafel 
and Ach from guanine, but they did not offer any proof of its 
structure. In the present research it was prepared from 5 : 6-di- 
amino-2-pyrimidone, and the product agrees in all respects with that of 
Tafel and Ach. When 5 : 6-diamino-2-pyrimidone is heated with 
formic acid, a monoformyl derivative is obtained ; this yields a 
potassium salt, which when heated gives off water, and changes to the 
potassium salt of 2-oxypurine ; 2-oxypurine crystallises with IHgO, 
and does not lose it until heated to 120°. The picrate, nitrate, and 
hydrochloride were prepared. 

When 5 : 6-diamino-2-pyrimidone is boiled with acetic anhydride 
it forms chiefly a monoacetyl compound, together with some of the 
diacetyl compound. When the potassium salt of the former is heated, 
it yields the potassium salt of 2-oxy-S-methylpurine ; this substance 
forms a picrate, decomp. 250°, and a nitrate, decomp. 205°, which 
may be used for its identification. W. D. H. 



ORGANIC CHEMISTRY. i. 225 

Preparation and Reactions of Azo-aoyl Compounds. 
Robert Stolle [with J. Mampel, J. Holzapfel, and K. C. Leverkus] 
(Ber., 1912, 45, 273— 289).— Azodlacyls of the type R-CO-NIN-CO-R 
(where R = H, Me, CHEtg, Ph, CfiH^Cl, and a-CioH^) have been pre- 
pared by the action of iodine or bromine in ethereal solution on the 
mercury or silver salts of symiAetrical diacylhydrazides, 

R-CO-NH-NH-COR. 
The azodiacyls prepared from hydrazides of aromatic acids are com- 
paratively stable, whilst those derived from aliphatic acids are 
unstable, and could only be obtained in ethereal solution or in an 
impure condition as red oils. They are converted by reducing agents, 
such as hydriodic acid, hydrogen sulphide, and phenylhydrazine, into 
the original hydrazides. When treated with water they yield tri- 
acylhydrazides, the decomposition taking place according to the 
following scheme : 

2N2(CO-R)2 + H2O = R-COaH + Ng -t- R-C0-NH-N(C0-R)2. 

It is supposed that the first stage in the reaction consists in the 
partial hydrolysis of the azodiacyl to the compound (I), which instantly 
decomposes, thus : (I) NHIN-CO-R -> H -}- Ng + -CO-R ; this is 
followed by addition of M and 'OOR to a second molecule of the 
azodiacyl with the formation of a triacylhydrazide. Evidence in 
support of this view is furnished by the production of triacyl- 
hydrazides by the reaction of azodibenzoyl and azodi-a-ethylbutyryl 
with benzaldehyde : 

Ph-CHO + R-CO-NIN-CO-R -^ R-CO-NBz-NH-CO-R, 
and also by the formation of benzoylhydrazobenzene. NPhBz'NHPh, 
by heating azobenzene with benzaldehyde for fifteen hours at 110°. 

The decomposition of the azodiacyls by heat has not yet been 
thoroughly investigated, but with azodibenzoyl and azodi-a-naphthoyl 
the decomposition occurs to a small extent as follows : 
C0R-N:N-C0-R -^ COR-COR + Ng. 

Azodicarboxylimide and several of its derivatives of the formula 
(I) below (where R = H, Ph, NHg, NICHPh) have also been prepared 
by the action of iodine in ethereal solution on the silver salts of the 
corresponding hydrazo-compounds (II); they are decomposed by water 
as follows : 

(I.) (II.) 

^^N N"^ 

The mercury salt of s-dibenzoylhydrazide, CPh'^^.Tj- ^^^CPh, 

obtained by the action of mercuric chloride on the hydrazide and 
sodium ethoxide in alcoholic solution, is converted by bromine in 
ethereal solution into azodibenzoyl (Stolle and Benrath, Abstr., 1900, 
i, 531 ; 1904, i, 935). When heated at 270° in an atmosphere of 
carbon dioxide, this decomposes, yielding small quantities of benzil 
and 2 : 5-diphenyl-l : 3 : 4-oxadiazole. It combines with benzaldehyde 
it 110° to form tribenzoylhydrazide, a small amount of the above- 



i. 226 ABSTRACTS OF CHEMICAL PAPERS. 

mentioned oxadiazole being produced simultaneously. It reacts with 
aniline, yielding benzanilide and «-dibenzoylhydrazide, thus : 

(1) NBz:NBz + NH2Ph = NHPhBz + N2 + 2H 

(2) 2H + NBz:NBz = NHBz-NHBz, 

and with dimethylaniline to form s-diljenzoylhydrazide, the dimethyl- 
aniline being oxidised to tetramethyldiphenylmethane and other 
products not yet investigated. 

H-Bi-Y^-chlorobenzoi/Uiydrazide, prepared from hydrazine sulphate, 
;o-chlorobenzoyl chloride, and aqueous sodium hydroxide, crystallises 
in felted needles, m. p. 289°, and reacts with sodium hydroxide in 
aqueous alcoholic solution to form the sodium salt, 

C6H4Cl-C(ONa):N-NH-CO-C6H4Cl, 
which crystallises in lustrous, pale yellow leaflets, and is oxidised by 
iodine in ethereal solution to azodi-^-chlorohemoyl, 1^ ^{QO'C^fiX)^^ 
yellow needles, m. p. 147° (decomp.). 

?^-Di-a-naphihoylhydrazide, prepared in a similar manner, has m. p. 
260° and forms a silver salt, CioH7-C(OAg):N-NH-CO-CioH^. which 
is oxidised to azodi-a-naphtlwyly N2(CO*CjqHi7)2. This crystallises in 
orange-red needles, m. p. 148°, and when heated at 140 — 150° loses 
nitrogen, yielding di-anapkthyldiketone, CioH,^*CO*CO*CjqH,j,, m. p. 
187°; it reacts with water to form a-naphthoic acid, s-di-a-naphthoyl- 
hydrazide, and tri-a-naphthoylhydrazide, CjqH7'CO*NH'N(CO'CjqHy)2, 
which has m. p. 188°, and has also been prepared by the action of 
o-naphthoyl chloride on the silver salt of s-di-a-naphthoylhydrazide. 

The sodium salt of s-benzoylacetylhydrazide, C9H[902N'2Na, is 
converted by mercuric chloride in alcoholic solution into the mercury 
salt, C9H802N2Hg. 

Benzoylazoacetylj NAcINBz, obtained in an impure condition as 
a red oil by the interaction of iodine and the preceding mercury salt in 
ethereal solution, is decomposed by water, yielding benzoic acid, 
s-dibenzoylhydrazide, and dihenzoylacetylhydrazide, NAcBz'NHBz, 
m. p. 171°. 

2-Phenyl-5-niethyl-l : 3 : 4:-oxadiazole, CMe<^_^-v_^CPh, prepared by 

heating s-benzoylacetylhydrazide with phosphoryl chloride, crystallises 
in lustrous plates, m. p. 67° ; it forms with silver nitrate an additive 
compound crystallising in lustrous needles, m. p. 185°; an additive 
compound with mercuric chloride is also described. 

Dihenzoyldiacetylhydrazide, NAcBz'NAcBz, prepared either from 
acetyl chloride and the mercury salt of s-dibenzoylhydrazide or from 
benzoyl chloride and the mercury salt of «-diacetylhydrazide, 
crystallises in leaBets, m. p. 109°. 

s-Diformylhydrazide yields a crystalline silver salt, C2H202N2Ag2, 
which explodes when heated, and a mercury salt, 

Azodiformyl^ N2(CHO)2, prepared from the preceding mercury salt, 
could not be isolated on account of its instability ; its ethereal 
solutions have a raspberry -red co our. 

The mercury salt of s-diacetylhydrazide, C4Hg02N2Hg, prepared from 



ORGANIC CHEMISTRY. i. 227 

the hydr.izide, sodium ethoxide, and aqueous mercuric chloride, reacts 
with iodine in ethereal solution in the presence of magnesium or 
barium oxides, yielding azodiacetyl^ NAcINAc, in an impure condition 
as a dark red oil. 

8-Di-a-ethylhutyrylhydrazide, N2H2(CO*CHEt2)2, prepared from the 
corresponding acid chloride and hydrazine hydrate in the presence of 
sodium carbonate, crystallises in white needles, m. p. 230°. 

Azndi-a-ethylbutyrylj N2(CO'CHEt2)2, obtained from the mercury 
salt, Cj2H2202N2Hg, of the preceding compound as a red oil, is 
decomposed by water into a-ethylbutyric acid and tri-a-ethylbutyryl- 
hydrazide, CHEt2-CO-NH-N(CO-CHEt2)2, which crystallises in colour- 
less prisms, m. p. 95°, and has also been prepared by the interaction of 
a-ethylbutyryl chloride and s-a-diethylbutyrylhydrazide in pyridine solu- 
tion at 100°. It combines with benzaldehyde, yielding henzoyldi-a-ethyl- 
hutyrylhydrazide, CHEt2-CO-NBz-]SrH-CO-CHEt2, crystallising in 
small prisms, m. p. 123°. The latter compound may also be prepared 
from benzoyl chloride and «-di-a-ethylbutyrylhydrazide in pyridine 
solution. 

Azodicarhoxylimide [diketodihydro-l : 3 : i-triazole\ M ^NH, ob- 

tained as a violet oil by the action of ethereal iodine on the silver salt 
of hydrazodicarboxylimide in the presence of barium and magnesium 
oxides, is instantly decomposed by water, yielding nitrogen, carbon 
dioxide, and hydrazodicarboxylimide. 

Hydrazodicarboxylphenylimide yields the silver salts, CgHgOgNgAg 
and C3H302N3Ag2, of which the latter is converted in the usual 
manner into azodicarboxylphenylimide. This forms carmine-red crystals 
(compare Thieleand Stange, Abstr., 1895, i, 251), gives violet solutions 
in ether, and decomposes when heated into phenylcarbimide and 

hydrazotetracarhoxyldiphenyldi-imide, NPh<^ i _^NPh, which 

crystallises from glacial acetic acid in lustrous, white leaflets, subliming 
in needles without melting. 

Azodicarhoxylaminoimide (azodicarhoxylhydrazide) \\- amino -2 : 5- 

diketodihydro-l : 3 : i-triazole\ ''•^N'NHg, prepared from the silver 

salt of aminourazole (Curtius and Heidenreich, Abstr., 1896, i, 143), 
C2H202N4Ag2, is an unstable, violet powder ; it explodes at 72°, and is 
slowly converted by water into aminourazole. 

Azodicarhoxylhenzylidenehydrazide, M >>N'NICHPh, obtained 

-IN *00 

from the silver salt of benzylideneaminourazole (hydrazodicarboxyl- 
benzylidenehydrazide), C9Hg02N4Ag2, forms carmine-red crystals, 
which become colourless when heated (at 135 — 138°), owing to loss of 
nitrogen and conversion into hydrazotetracarhoxyldihenzylidenedihydr- 

azide, CHPh:N-N<^^'^*^^>N-N:CHPh, m. p. 285°. 

The mercury salts of ethyl hydrazodicarboxylate yields, with iodine 
in ethereal solution, ethyl azodicarboxylate (Curtius and Heidenreich, 



i. 228 ABSTRACTS OF CHEMICAL PAPERS. 

loc. cit.)f and, when heated with benzoyl chloride in carbon tetra- 
chloride solution at 100° forms ethyl dihenzoylhydrazodicarhoxylate, 
^20^20^6^2» which forms white crystals, m. p. 83°. F. B. 

Enzymic Decomposition of Hydrogen Peroxide. II. Percy 
Waentig and Otto Steche (^ei«sc/i. ;?%sio^. Chem.^ 1912,76, 177 — 213. 
Compare Abstr., 1911, i, 759). — The behaviour of both animal and 
vegetable extracts in decomposing hydrogen peroxide is very similar, 
and in far closer agreement with Senter's hsemase than is generally 
stated. This is illustrated particularly by the influence of hydrogen 
and hydroxyl ions on the rate of reaction — any shift in equilibrium 
from that prevailing in distilled water, free from carbon dioxide, 
causes a retardation. The reaction is, however, less sensitive when 
relatively large amounts of impurity are present in the extracts ; this 
may be due to the amphoteric character of the proteins in retaining 
acids or bases, or to a definite protective action of the impurities 
analogous to that of the so-called " protective colloids." This insensi- 
tive character is specially marked in catalase solutions prepared 
from the alcohol precipitate of an aqueous extract of germinating 
barley. 

The enzyme extracts behave similarly at 0° and at 30° ; at the higher 
temperature the hydrogen ion has less, the hydroxyl ion more, influence 
on the rate of change. The influence of temperature on the rate is 
very small. The course of change does not quite correspond with the 
simple mass-action law ; the value of K falls off even in very dilute 
hydrogen peroxide solutions at 0°. Dialysis yields weaker extracts, 
but with these a more constant value of K is obtained. The amount 
of enzyme is roughly proportional to the rate of change. 

Exposure to ultra-violet light weakens the enzyme activity ; the 
effect is greater in alkaline than in neutral or acid solution. 

Complete precipitation of the enzyme from extracts of liver, fat, 
barley, etc., requires an alcohol concentration of 55%. Animal 
extracts show a decline in activity when the concentration of hydrogen 
peroxide exceeds a certain point; this is not the case with plant 
extracts. 

It would appear that the active substance which brings about the 
decomposition of hydrogen peroxide is the same irrespective of origin. 

E. F. A. 

Preparation of Mercury p- A m inophenylarsinates. Aktien- 
Gesellschaft fur Anilin-Fabrikation (D.R.-P. 237787). — Mercury 
hydrogen Tp-aminophenylarsinatej [NH2*CgH4'AsO(OH)*0]2Hg, a colour- 
less powder, sparingly soluble in water, is»prepared by stirring together 
an aqueous paste of p-aminophenylarsinic acid (2 mols.) and mercuric 
oxide (1 mol.). The basic salt, NH2-CgH4-AsO(OH)-0-Hg-OH, is 
obtained when equimolecular proportions of the amino-acid and 
mercuric chloride in the presence of alkali (2 mols.) are employed. 

F. M. G. M. 



i. 229 



Organic Chemistry. 



The Autoxidation of Organic Compounds. Hermann 

Staudingee {Verh. Ges. deut. Naturforsch. Aerzte, 1912, ii, [1], 

216 — 219). — The autoxidation of compounds containing a double 

linking involves the formation of two oxides, one of which is 

CPh • O 
symmetrical, as in the case of diphenylethylene, i ^ i , and the other 

CCl ~v^ 

unsymmetrical, as with trichloroethylene, Att?i,-^0:0, which then 

CJExGl 

breaks up into ^jj^^O and oxygen. It is assumed that the first 

product is always the un symmetrical compound, which may then 
undergo rearrangement. C. H. D. 

Action of the Grignard Reagent on Methylethylacraldehyde 
and the Preparation of Some Diolejanes, defines, and 
Saturated Secondary Alcohols. E. Bjelouss {£er., 1912, 45, 
625—632. Compare Abstr., 1910, i, 70Q).—8-Met/wl-A^-octen-€-ol, 
CH2Me-CH:OMe-CH(OH)-CH2-CH2Me, prepared from propyl chloride 
and methylethylacraldehyde, is a colourless, mobile, strongly smelling 
liquid, m. p. 79— 8I7IO mm., Df 0-8468, 01^ 1-4445. The acetate is a 
colourless, mobile liquid, b. p. 87—89714 mm.: the chloride has b. p. 
59—62711 mm. ^ 

y- Methyl- A^y-hexadieney CHgMe-CHrCMe-CHICHg, is a very mobile, 
colourless liquid, b. p. 101—103°, Df 0*7407, w^M-452. 

S - Methyl - Ay^ - octadiene, CH2Me-CH:CMe-CH:CH-CH2Me, is a 
colourless liquid of characteristic odour, b. p. 148—151° Df 0*764. 
w'f 1-4628. > 4 , 

y-Methylhexan-p-ol, CH2Me-OH2-CHMe-CHMe-OH, is a colourless, 
mobile liquid with an odour of peppermint, b. p. 79— 81°/52 mm., 
Df 0-822, nf 1*4207; the acetate is a pleasant smelling liquid, b. p 
84—87° ; the chloride has b. p. 53— 58°/36 mm. 

B-Methylheptan-y-ol, CH2Me-CH2-CHMe-CH(OH)-CH2Me, is an 
agreeable smelling liquid, b. p. 98—99775 mm., Df 0-8268, n^ 1*4261 ; 
the acetate has b. p. 103—104775 mm.; the chloo-ide, b. p. 83—867 
79 mm. ' 

S-Methyloctan-€-ol is a colourless, strongly smelling liquid, b. p 
74— 76°/9 mm., Df 0*8156, wif 1-4262. 5 4, f 

pe-Dimethyloctan-Ul, CH2Me-CH,-CHMe-CH(OH)-CH,-CHMe2, is 
similarly a colourless, mobile liquid, b. p. 102—104734 mm., 
D4 0-8125, n^ 1-4259; the phenylurethane crystallises in bunches of 
needles, m. p. 39 — 40°. 

^P^'^^^^^^y^'^'^'^^'^-^-ol has b. p. 98—99711 mm., Df 0*8126, 
Wd 1-4295 ; the crystalline phenylurethane has m. p. 43—44°. 

yMethyl-Mexene, CH2Me-CH2-CMe:CHMe, prepared by elimina- 
U^ of hydrogen bromide from methylhexanyl bromide, is an exceed- 
i^^OL. CII. i. 



r 



i. 230 ABSTRACTS OF CHEMICAL PAPERS. 

ingly volatile liquid of pleasant odour, b. p. 85—90° Df 0-7301, 
n^ 1-4132. 

h-Methyl-Ly-heptene is very similar; it has b. p. 115—120°, Df 07411, 
<1-4171. 

8-Methyl-A^-octene has a penetrating odour, b. p. 133 — 138°, 
Df 0-7388, nf 1-4178. 

fie-Dimetkyl-A^-oclem has b. p. 152—157°, Df 0-746, w*^M-4189. 

hS-Dimethyl^^-nonene has b. p. 165—169°, Df 0-753, n':[f 1-4278. 

By the action of magnesium phenyl bromide on methylethyl- 
acraldehyde an alcohol is at first formed, but on distillation in a 
vacuum water is eliminated and a hydrocarbon, a-phenyl-j^-methyl- 
A'^-pentcidiene (1), obtained ; this is a yellow, mobile, strong smelling 
liquid, b. p. 228— 231°/753 mm., Df 0-8986, nj^ 1-5257. 

a-Phenyl-P-methylpentane^ obtained on reducing phenyl methyl- 
pentenol, is a colourless, mobile, pleasant smelling liquid, b. p. 
203—207°, Df 0-8584, < 1-4827. 

a-Naphthyl-ji- methyl - A<*y - pentadiene (?) is a yellow liquid of 
characteristic odour, b. p. 178— 181°/12 mm., Df 0-9801, nfy' 1-5697. 

E. F. A. 

Compounds -with Triple Linkings. Wilhelm Manchot [with 
John C. Withers and Heinrich Oltrogge] (Aniialeiif 1912, 387, 
257 — 293). — Various observers have described additive compounds of 
acetylene and cuprous chloride, but have been unable to show that their 
substances are initial products of the reaction. The authors, using a 
modified form of the apparatus described previously (Abstr., 1910, i, 85), 
now show that the initial product is the white substance^ CgHgjCuCl. 
On account of its solubility and of the secondary reaction which 
occurs in concentrated solutions, this substance cannot:,be isolated from 
aqueous solutions; it is obtained, however, by working in absolute 
alcoholic solution at 0°. At 0° and atmospheric pressure, experiments 
with solutions containing 0-034 gram-molecule of cuprous chloride per 
litre and varying quantities of hydrochloric acid yield the following 
results. With 0-61 gram-molecule of hydrochloric acid per litre, 
a clear, colourless solution is obtained, and 22-44 litres of acetylene 
(per 1 gram atom of copper) are absorbed. With greater concentra- 
tions of hydrochloric acid, the absorption of acetylene diminishes 
owing to the concurrent reaction: CuCl4-HCl = CuCl,HCl. When 
the concentration of the hydrochloric acid is less than 061 mol. per 
litre, the absorption of acetylene also diminishes, owing to the 
formation of a dark violet substance, C<,Cu2,CuCl,H20. 

When the concentration of the cuprous chloride in a solution of 
61 mol. of hydrochloric acid per litre is increased, the absorption of 
acetylene diminishes, owing to the formation of a sparingly soluble white 
substance, 2CuCI,C2H2 ; thus : 2(CuCl,C2H2)^C2H2 + 2CuCl,C2H2. For 
example, the absorption of acetylene is 22*4 litres (per 1 gram atom of 
copper) when the concentration of the cuprous chloride is 0-00561 mol. 
of cuprous chloride, and only 11-43 litres when the concentration is 
increased to 0-5035 mol. 

In its ability to form a compound of the type 2CuCl,C2H2, acetylene 
differs from carbon monoxide and ethylene, and resembles nitric oxide 



ORGANIC CHEMISTRY. i. 231 

which can form a compound 2FeS04,NO (Abstr., 1907, ii, 93 ; 1908, ii, 
375; 1910, i, 85; ii, 414, 956). The additive capacity of acetylene 
towards cuprous chloride also differs from those of carbon monoxide 
and ethylene in the following respect. The latter two gases only form 
additive compounds in the presence of water, ammonia, or organic 
bases ; the presence of alcohol not only retards the addition, but causes 
decomposition of the additive compound when formed. In the case of 
acetylene the presence of water is unnecessary for the formation of the 
additive compound CuCJjCgHg ; the additive compound is formed, as 
in the case of nitric oxide and ferrous chloride, in absolute alcohol. 

Substituted acetylenes, such as phenylacetylene, ^-anisylacetylene, 
methylenedioxyphenylacetylene, behave like acetylene itself towards 
cuprous chloride. By direct addition of the components, colourless 
additive compounds of the type Ci:l;CH,CuCl are obtained, which are 
converted by water or ammonia into coloured copper derivatives, 
CR:CCu. Hence the equation CE:CH + CuCl = CKiCOu + HCl 
expresses only the initial and the final states ; the first phase of the 
process, that is, the condition for the subsequent substitution, is the 
formation of an additive compound of the two components. These 
experiments, therefore, support the views on processes of substitution 
recently advanced by Werner and by E. Fischer. 

The presence of the group ;CH is not the condition for the forma- 
tion of additive compounds of acetylenes and metallic salts, because, 
although many substances of the type CK:CR' do not form additive 
compounds, bromophenylacetylene, iodophenylacetylene, phenylpro- 
piolonitrile, and phenylpropiolamide react readily with cuprous- chloride 
to form such substances. 

The authors are of opinion that the degree of unsaturation of 
substances containing a triple linking varies from case to case with 
the nature of the groups attached to the C:C group. Even if a 
group E, is itself unsaturated, it does not necessarily increase the 
unsaturation of the whole molecule CRiCE,' ; thus, diphenyldiacetylene, 
di-/>-anisyldiacetylene, and bis-3 : 4-methylenedioxyphenyldiacebylene 
do not form additive compounds with cuprous chloride. 

The following new compounds are described : jo-Anisylacetylene 
forms a canary-yellow copper derivative, OMe'CgH^'CiCCu, and a 
colourless additive compound^ OMe'CgH^'C.'CHjCuCi, and yields by 
treatment in ether with sodium and subsequently with benzoyl 
chloride, henzoyl-^-anisylacetylene, OMe'CgH^'CiCBz, m. p. 81°, which 
does not react with cuprous chloride and forms a dibromide, 
OMe-CgH/CBr-CBrBz, m. p. 90°. Di-^-cmisyldiacetylene, 

m. p. 144 , white needles, is obtained almost quantitatively by shaking 
the copper derivative of /)-anisylacetylene with alcoholic ammonia 
and oxygen for four days. Bis-Z : 4:-methylenedioxyphenyldiacetyle7ie, 
^i8Hio^4> ^' P« 197°, and diphenyldiacetylene are prepared in a similar 
manner. C. S. 

Derivatives of Acetylene. Hugo Noerdlinger {Kleine Mitt. Chem. 
Fabrik. Florsheim, No. 37).— The physical constants and properties of 
the following derivatives of acetylene are given : Heptinene (?t-amyl- 
r 2 



i. 232 ABSTRACTS OF CHEMICAL PAPERS. 

acetylene, b. p. 108—1107745 mm., 26710 mm., m. p. below -70°, 
D>» 0-7546, D-"" 0-7470. Octinene (n-hexylacetylene), b. p. 130—1327 
746 mm., 3178 mm., m. p. below -70°, D^^ 0-7680. Noninene 
{ii-heptylacetyleiie\ b. p. 160°/745 mm., 51°/8 mm., m. p. -65°, 
D^' 0-7799. Decinene (n-octij/ acetylene), b. p. 181— 182°/745 mm., 
69— 70°/10 mm., m. p. -36°, D^"^ 0-7924. Uiidecinene {n-nonyl- 
acetyleiie), b. p. 202—2047745 mm., 9178 mm., m. p. -33°, 
D^' 0-8024. 

All these compounds are colourless liquids, practically insoluble in 
water, soluble in organic solvents. They possess a high refractive 
index, and a characteristic odour which is particularly marked in the 
cases of heptinene and undecinene. With ammoniacal cuprous 
chloride and silver nitrate solutions, they yield yellow and white 
precipitates respectively. When dissolved in ether and treated with 
sodium, they evolve hydrogen and form highly reactive sodium 
compounds. H. W. 

Density and Thermal Expansion of Ethyl Alcohol and its 
Mixtures with Water. N. S. Osborne, E. C. McKelvy, and 
H. W. Bearce (/. Washington Acad. Set., 1912, 2, 95— 98).— The 
densities of twelve mixtures of ethyl alcohol and water were determined 
at 10°, ]5°, 20°, 25°, 30°, 35°, and 40° by the method of hydrostatic 
weighing. For each mixture the constants a, p, and y in the equation 
r)^ = D250 + a(<-25°) + ^(<-25°)" + y(i-25y, and these values are 
tabulated together with D^^. 

The values of a, p, and y for each integral % of alcohol between 
and 100 have been obtained by interpolation. The mean of fifteen 
determinations of the density of the purest alcohol at 25° was found 
to be 0-78506. H. M. D. 

Action of the Chlorides of a-Alkyloxy-acids on Organo- 
metallic Derivatives of Zinc. Edmond E. Blaise and L. Picard 
{Ann. Chirn. Phya., 1912, [viii], 25, 253— 276).— For the most part 
a resume of work already published (Abstr., 1911, i, 175, 260). The 
following new data are recorded regarding substances obtained in the 
general reaction. 

Ethyl n-amyl ether, b. p. 119 — 120°, is a mobile, pleasant smelling 
liquid, insoluble in water, which on heating with hydriodic acid yields 
7i-amyl iodide, from which ?i-amyl ether, b. p. 70°/12 mm., and n-amyl 
alcohol were prepared. The phenylurethane of the latter has m. p. 
46°, and crystallises in tablets, and the henzoate boils at 137 — 138°/ 
15 mm. Etfioxymethyl n-butyl ketone, OEfCHg-CO'C^Hg, b. p. 79°/ 
18 mm., is a pleabant-smelling liquid ; the oxime, h. p. 125°/17 mm., is a 
colourless liquid ; the semicarbazone, m. p. 99°, forms brilliant, colourless 
spangles. 

Condensation of ethoxyacetyl chloride with zinc isoannyl iodide 
furnished ethyl isohexyl ether, OEfCHg'CHgPr^, b. p. 68°/67 mm., 
or 137°/760 mm., and ethoxymethylhexanone (Sommelet, Abstr., 
1907, i, 107). 

i^-Tolylethoxymethylethylcarhinol, OH-CEt(CH2-OEt)-CgH4Me, b. p. 
130°/9 mm., obtained by the action of magnesium ethyl bromide on 



ORGANIC CHEMISTRY. i. 233 

jo-tolylethoxy methyl ketone already described (Abstr., 1911, i, 175), 
gives by the application of Sommelet's method {loc. cit.), /S-ip-tolyl- 
butaldehyde, CfiH^Me-CHEt-CHO, b. p. 10478 mm. The latter 
furnishes an azine, m. p. 63° (decomp.), a semicarbazone, T^-nitrophenyl- 
hydrazone^ m. p. 104°, and an oximey m. p. 70°, all of which are 
crystalline. T. A. H. 

Action of Alkyloxides on Esters of Inorganic Acids. 
I. L. R-ABTSEViTSCH-ZuBKOvsKY (J. Russ. PJiys. Chem. Soc, 1911, 44, 
151 — 154). — Methyl sulphate reacts with magnesium methoxide accord- 
ing to the equation: 2Me2S04 + Mg(OMe)2 = 2Me20 + Mg(S04Me)2, 
and with sodium isobutoxide according to : 

MogSO^ + CHMeg-CHg-ONa = NaMeSO^ + CHMeg-CHg-OMe. 
Magnesium methoxide and methyl phosphate yield methyl ether, and 
magnesium dimethyl phosphate: P0(0Me)3 + Mg(0Me)2 = 2Me20 + 
Mg[0'PO(OMe)2]2 ; so that when alkyloxides react with alkyl salts of 
polybasic inorganic acids, only one of the alkyloxy-groups of the salt is 
replaced by the metal of the alkyloxide. T. H. P. 

Preparation of Aminoethyl Alcohol from Egg Lecithin. 
Georg Trier (Zeitsch. physiol. Ghem., 1912, 76, 496 — 498. Compare 
Abstr., 1911, i, 771). — /S-Aminoethyl alcohol is obtained as a product 
of the hydrolysis of egg lecithin by dilute sulphuric acid in not 
inconsiderable quantity, and identified by means of the aurichloride. 

E. F. A. 

Should the Term Protagon be Retained ? Waldemar Koch 
(Proc. Amer. Soc. Biol. C hem. , 1911, xl ; /. Biol. Ghem.^ 11). — The 
term protagon has no longer any chemical significance ; the substance 
so described contains at least three materials, namely, a phosphatide, 
which contains choline, a cerebroside, and a combination of a choline- 
free phosphatide and a cerebroside to which an ethereal sulphuric acid 
group is attached. W. D. H. 

New Compounds of Samarium and Neodymium. Charles 
James, F. M. Hoben, and C. H. Robinson (J. Amer. Ghem. Soc, 1912, 
34, 276—281 ; Ghem. News, 1912, 105, 121— 122).— In the course of 
a search for salts which might be of value for fractionally separating 
the rare earths, the following compounds were prepared and are described. 

Samarium ethyl sulphonate, (C2H5'S03)gSa2,6H20, inethylsulphonatey 
(CH3*S03)gSa2,7H20, propyl sulphonate, (C3H.7'S03)gSa2,9H20, isobutyl- 
sulphonate, (C4Hg*S03)gSi2,7H20, camphor sulphonate, 

(C,oH,50-S03)gSa2,10H20, 
methanetrisulphonate, [CH (lS03)3]2Sa2,16H20, va-xyleneA'Sulphonate^ 
(CgH3Me2-S03)6Sa2,7H2(), glycoUate, (OH*CH2-C02)gSa2, cacodylate, 
(Me2As02)6Sa2, 1 6U2O, ethanedisulphonate, [C2H4(IS03)2]3Sa2,4H20, 
ethylgly collate, (OEfCH2-C02)2Sa2,l8H20, citraconate, 

(C5HA)B.Sa2,12H20, 
sulphoacetate, (C2H205S)3Sa2,and hydroxyethanesulphonate. Neodymium 
methylsulphonate, (CH3-S03)(jNd2,7H20, ethylsulphonate, 
(C2H5-S03)gNd2,6H20, 



i. 234 ABSTRACTS OF CHEMICAL PAPERS. 

j)ropylsulphonate, {C^'H.^-SO^)(^l!Jd^,^'Hfi, i^ohuiyhulphonate^ 

(C,Hp-S03)eNd„8H20, 
ethayiedtsulphonale, [C^y^i{^0^)2]i'i^(^2> 1 OHgO, methanetrisulphonatef 

" [CH(SO,)j2Nd2.UH20, 
camphorsulphonate, {C^qH^^0'S0^)^N6^, 1 7H2O, m-xyUm-i-sulphonate, 
(CgHgMe2'SOg)QNd2,2H20, m-sulphohenzoate, 

(C,H,0,S)«Nd2,9H20, 
quinate, [0^n^{Ol^)^'QO2\^A2,\mf), anisate, {OUe-O^B^^'^^O^)^!^^^, 
oxanilate, (NHPlrCO-C02)fiNd2,5H20, cacodylcUe, (Me2Ab02)eNd2, 
and hydroxyethaneaulphonate, E. G. 

Reduction of Higher Unsaturated Aliphatic Acids to 
Saturated Acids by the Action of Zinc and Water on 
their Halogen Derivatives ; Grignard Reaction Applied to 
the Latter. Sergius Fokin (/. Russ. Phys. Chem, Soc, 1912, 44, 
155 — 165). — Experiments with oleic, elaidic, erucic, undecenoic, 
ricinoleic, linoleic, and linolenic acids show that by addition of 
hydrogen bromide to these acids and treatment of the monobromo- 
saturated acids thus obtained with zinc and water in a sealed tube, 
the corresponding saturated aliphatic acids themselves are obtained ; 
for example, (Cj^H3^Br-C02)2Zn + 2Zn + H2O = {C^^Yi ^^-00^)^11 + 
(ZnBrg 4- ZnH)2. Unsaturated hydroxy-acids may be converted into 
saturated hydroxy-acids in a similar manner. With monochloro- 
derivatives of saturated aliphatic acids, the reaction with zinc and 
water proceeds partly in tho direction indicated by the above equation, 
but about one-third of the acid formed consists of the original 
unsaturated acid, from which the chloro- derivative of the saturated 
acid was obtained. As stated by Lewkowitsch (" Oils, Fats, and 
Waxes "), neither dichloro- nor dibromo-stearic acid gives the non- 
substituted stearic acid when heated with various metals in presence 
or absence of water or an organic solvent. 

The following temperatures are those at which fused mixtures of 
oleic and stearic acid solidify: 10% stearic acid (90% oleic), 29-5°; 
20%, 40-2°; 30%, 47-7°; 40%, 52-9°; 50%, 56-8°; 60%, 59-8°; 
70%, 62-3°; 80%, 645° ; 90%, 66-3°, and pure stearic acid, 68-0°. 

T. H. P. 

An Anomaly in the Reduction of Ethyl Acetoacetate. 
Julius Tafel [with Franz Andre] {Ber., 1912, 45, 437—452. 
Compare Tafel and Hahl, Abstr., 19u7, i, 765; Tafel and Jiirgens, 
Abstr., 1909, i, 545). — The electrolytic reduction of derivatives ofj 
acetoacetic esters has been interpreted to take place according to the 
scheme: CH3-CO-CHR-C02Et — > CH8-CH2-CHR-OH3. Whilst,] 
however, the range of the b. p. of the products obtained points toj 
their uniformity, the actual b. p.'s do not in all cases agree with those 
recorded for the expected hydrocarbons, and in the cases where 
R = Et, nPr, or wC^Hg, lie close to those of the isomeric normal hydro- 
carbons ; similarly, Tafel and Jiirgens (loc. cit.) found for the reduction- 
product of ethyl taobutylacetoacetate a b. p. 7° higher than that given 
by Clarke (Abstr., 1908, i, 593) for ^8-dimethylhexane. The present 
work was undertaken with the object of explaining these differences, 



ORGANIC CHEMISTRY. 1. 235 

and has led to the conclusion that the methyl group formed in 
the complete reduction of derivatives of acetoacetic esters is transposed 
and occurs, not as a side-chain, but as part of the main chain. 

The reduction of ethyl isobutylacetoacetate, whether with lead or 
cadmium electrodes, gave results precisely similar to those obtained by 
Tafel and Jiirgens {loc. cit.) The product, which is now regarded as 
/5-methylheptane or y-methylheptane (instead of /3S-dimethylhexane), 
appears to undergo slight decomposition when shaken with concentrated 
sulphuric acid according to the method previously used for its 
purification. 

By the reduction of ethyl sec. -butylacetoacetate with lead electrodes, 
a hydrocarbon, b. p. 117*8 — 118*2°/746 mm., was obtained. This is 
regarded as y-methylheptane or, possibly, a mixture of 8-methylheptane 
and y-ethylhexane. 

Methyl methyl propylacetoacetate, reduced at a cadmium electrode, 
yielded an octane of b. p. 116'1 — 118-2°/752 mm. This is probably 
8-methylheptane, possibly y-methylheptane or y-ethylhexane, or a 
mixture of the latter with 8-methylheptane. 

Methyl methyk'sopropylacetoacetate when similarly reduced gave 
an octane of b. p. 110 — 118°/756 mm., which is presumably a mixture 
of hydrocarbons. 

By the reduction of ethyl zsopropylacetoacetate, a heptane of b. p. 
91 — 92*6°/747 mm., probably slightly impure /3-methylhexane, or 
possibly y-methylhexane, was obtained. 

Ethyl ethylacetoacetate when reduced at cadmium or lead electrodes 
yielded a hydrocarbon which, after purification by means of con- 
centrated sulphuric acid, had b. p. 68'2 — 69*l°/742 mm. This was 
unaffected by cold potassium permanganate, thereby differing from 
y-methylheptane, which, according to Zelinsky and Zelikoff, is rapidly 
oxidised by this reagent — a statement, however, which the authors 
could not confirm experimentally. 

An explanation of certain of these reactions may be found in the 
hypothesis that a tetramethylene ring is formed as an intermediate 
step in the reduction, and then broken in the manner indicated by the 
scheme : 

4CH3 4 3 ICH3 

3 CO C-C 4CH, . 

2CHR C— C-R "^ 3CW 

ICOgEt ^ ^ 2CH2R 

To explain the formation of y-methyl derivatives from ethyl iso- 
butyl- and tsopropyl-acetoacetates, it is necessary to assume that the 
carbon atom of the carbethoxy -group of the ester becomes detached 
from the a-carbon atom (*) and attached to a terminal C-atom of the 
alkyl group : 



CHg-CO-CH — CH-CHg CH3-CH2-CH2-CH-CH2-CH8 

COoEtCH, "^ 



•CHH 
CH3 

This leads to the same result as the above hypothesis in the cases of 
w-alkyl derivatives of ethyl acetoacetate and of ethyl diethylaceto- 



i. 236 ABSTRACTS OF CHEMICAL PAPERS. 



1 



acetate. In the cases of sec-butyl, methylpropyl, and methylisopropyl 
derivatives, however, two products might be expected, whilst only one 
has been obtained, possibly owing to the proximity of their respective 
b. p.'s. On the whole, the second hypothesis explains the fact better 
than the first, but is advanced with caution on account of the difficulty 
of interpreting the mechanism involved. 

A third possibility lies in the assumption of a new formulation for 
the substitution products of ethyl acetoacetate as shown in the following 
scheme : 

CH.-CO CH„-CO CHo-CO 

I I I 

CH CH CRi 

|>0 |>0 |>0 

H-C-OEt R-C-OEt R-C-OEt 

Possibly in ethyl acetoacetate this form may be in equilibrium with 
the forms generally assumed, and may also be the form mainly 
attacked during alkylation. According to this hypothesis, the same 
hydrocarbons should be obtained from monoalkyl derivatives of ethyl 
acetoacetate and from ethyl diethylacetoacetate as would be expected 
from the first hypothesis (see above). Ethyl methylpropylacetoacetate 
(from ethyl methylacetoacetate) should yield y-ethylhexane, whilst 
ethyl methyltsopropylacetoacetate (from ethyl methylacetoacetate) an( 
ethyl methylbenzylacetoacetate (from ethyl benzylacetoacetate) should] 
yield /? - methyl - y - ethylpentane and a - phenyl - y - methylpentanc 
respectively. H. W. 

A New Salt of ^-Hydroxybutyric Acid. Phillip A. Shaffei 
(Proc. Amer. Soc. Biol. Chem., 1911, xi; J. Biol. Chem.^ 11). — H 
equivalent parts of zinc and calcium ^-hydroxy butyrates (made b] 
treating the free acid with zinc and calcium carbonate respectively) 
are poured together, a double salt, 7inOB,{QjJ1^0^^^ is formed, which oi 
the addition to the warmed solution of an equal volume of alcoholj 
crystallises out in needles or long, narrow plates. It is useful for th« 
purification of the acid, which may be obtained from the double sail 
by removing the zinc with hydrogen sulphide, and the calcium with^ 
oxalic acid ; or a solution of the salt acidified with sulphuric acid and 
dehydrated by plaster or anhydrous sodium sulphate may be extracted 
with dry ether. The salt prepared from the Z-acid has a specific 
rotation, [a]f?= - 15-1° (5% solution). W. D. H. 

Syntheses by means of Mixed Organo-metallic Derivatives. 
Mixed cyc/o Acetals. Edmond E. Blaise {Compt. rend., 1912, 164, 
596—598. Compare Abstr., 1911, i, 175, 260).— The action of organo- 
zinc halides on acid chlorides of the type C0C1*CHR*0*C0*R is 
abnormal, and leads to the production of cyclic compounds which the 
author proposes to term c^c/oacetals. An intermediate compound is 
probably decomposed in the following manner : 

Znl-O-CRg-O-CHR-COCl = ZnlCl + CHR<^_q'_^CR2. 

The following new substances have been prepared ; their use in the 



ORGANIC CHEMISTRY. i. 237 

synthesis of aldehydes, a-ketonic acids, and a-halogen ketones will be 
described in a subsequent communication. 

CHMe<^.Q^CMePr-, b. p. 90722 mm. 

CMe2<^Q.^CMeEt, b. p. 64°/13 mm. 

CH2Me-[CH2]2-CH<^Q.^CMeEt, b. p. 103712 mm. 

CH2Me-[CH2]3-CH<£^'^>CMeEt, b. p. 115712 mm. 

Acetylsalicoyl chloride gives the compound, CgH4<^__^_^CMeEt, 
whilst acetyl jo-hydroxy benzoyl chloride behaves normally. 

W. 0. w. 

Formation of Cork. Simon Zeisel {J. pr. Chem.^ 1912, [ii], 
85, 226— 230).— Polemical with Schmidt (this vol., i, 72). F. B. 

Oxidation Products of Sebacic Acid. Eyvind Bodtker 
(/. pr. Chem., 1912, [ii], 85, 221— 225).— Succinic, glutaric, and 
adipic acids, together with a small quantity of y-heptanone-ai;- 
dicarboxylic acid (Tonnies, Abstr., 1879, 915), are the only products 
formed when sebacic acid is boiled with concentrated nitric acid until 
it completely disappears. For details of the separation of the acids, 
the original should be consulted. F. B. 

Dissociation of Tartrates, Malates, and Camphorates of 
Amines as Revealed by their Rotatory Power. Jules Minguin 
{Ann. Chim. Phys., 1912, [viii], 25, 145— 159).— The work on 
tartrates has been published already, and the general conclusions then 
drawn apply to the other salts now dealt with (Minguin and 
Wohlgemuth, Abstr., 1909, i, 11). The malates and camphorates of 
the aliphatic amines exist undissociated in solution, but in the case of 
the aromatic amines neutral malates are not formed and the hydrogen 
malates are dissociated in solution. Camphorates of the aromatic 
amines do not exist in solution. The hydrogen malates of aniline and 
of diethylaniline melt at 132" and 67° respectively. T. A. H. 

Lactonisation of a-Ketonic Esters. Ethyl Pyruvate. Henri 
Gault {Gompt. rend., 1912, 154, 439—441. Compare Abstr., 1911, 
i,709 j de Jong, Abstr., 1904, i, 550). — When the lactonisation of ethyl 
pyruvate is effected by saturating the ester with hydrogen chloride in 
the cold, the ethyl a-keto-y-valerolactone-y-carboxylate first formed 
undergoes further change, and a neutral substance, b. p. 176 — 1777 
13 mm., is obtained; this is probably the ethyl ether of the enolic 

form of the above ketone, C02Et'CMe<^ i , and appears to be 

Cxl.C'OEt 
identical with the compound prepared by Genvresse (Abstr., 1893, 
i, 552), which he supposed to be ethyl a-keto-A/^-butene-ay-dicarboxylate. 
It unites with hydrazine (2 mols.) to form a compound, m. p. 180° 
(decomp.), the constitution of which has not yet been elucidated. 

w. o. w. 



1. 238 ABSTRACTS OF CHEMICAL PAPERS. 

Oitrophosphate Solutions. Antonio Quartarolt {Atti R. Accad. 
Lincei, 1912, [v], 21, i, 130— 135).—- The author criticises the work of 
Pratolongo (Abstr., 1911, ii, 865) on this subject. The supposed 
solutions of dianimonium citrate used by that author are shown to 
have contained a mixture of difimmonium and triammonium citrates 
with an excess of the latter. The differences between the cryoscopic 
depressions observed by Pratolongo and the calculated values are not 
due to hydrolysis, because they would require, for instance, that not 
only the diammonium citrate, but also three-quarters of the mon- 
ammonium citrate present should suffer hydrolysis. The present 
author's calculations (from the dissociation constants of ammonium 
hydroxide and citric acid) show that even triammonium citrate can be 
but little hydrolysed. The abnormal values obtained for i in the case 
of the ammonium citrates are therefore due, not to hydrolysis, but to 
electrolytic dissociation. It is further shown that the cryoscopic data 
do, in fact, support the hypothesis of the formation of complex salts, 
and exclude the possibility of the occurrence of double decomposition. 

The paper records cryoscopic measurements for various solutions of 
citric acid, monoammonium citrate, triammonium citrate (and four 
intermediate solutions between the two last named), monopotassium 
citrate, dipotassium citrate, tripotassium citrate, monoammonium 
phosphate, diammonium phosphate, triammonium phosphate, tri- 
ammonium citrate -f calcium hydrogen phosphate, and triammonium 
citrate -f barium hydrogen phosphate. R, V. S. 

The Synthetic Application of Ethyl Methanetricarboxylate. 
PiOLAND ScHOLL (Verli. Ge.s. deut. Naiurforsch. Aerzte, 1912, ii, [1], 
213 — 214). — The usual ethyl acetoacetate and ethyl malonate 
syntheses may be performed with ethyl methanetricarboxylate if 
alcohol is excluded. The reaction takes place at or above 100°, and a 
pure product is obtained. Ethyl methanetetracarhoxylate, prepared 
from ethyl sodiomethanetricarboxylate and ethyl chloroform ate, is a 
stable compound, b. p. above 290° undecomposed, and yielding malonic 
acid with dilute sulphuric acid. C. H. D. 

New Method for the Catalytic Preparation of Aldehydes 
ft*om Acids. Paul Sabatier and Alphonse Mailhe {Compt. rend., 
1912, 154, 561—564. Compare this vol., i, 156, 157).— The reduction 
of aliphatic acids by means of formic acid furnishes a convenient 
method for preparing the corresponding aldehydes with satisfactory 
yields. The vapour of the acid, mixed with excess of formic acid, is 
passed over titanium oxide at 250 — 300°. Under these conditions, no 
ketone is formed, but the formic acid decomposes into carbon monoxide 
and water, thus effecting reduction of the acid. The following acids 
readily give aldehydes, the numbers indicating the yield in percentages : 
acetic 50, phenylacetic 75, propionic 40, butyric 55, i^obutyric 65, 
isovaleric 75, y-methylvaleric 80, octoic 95, and nonoic acid 85%. In 
the last case, a small amount of the corresponding ketone, pelargone, 
is also formed. Crotonic acid gives the aldehyde. 

When thoria is substituted for titanium oxide, the yields of aldehyde 
are lower. W. O. W. 



HPP ORGANIC CHEMISTRY. i. 239 

i™Alfalfone, a Ketone of the Formula C21H42O, obtained from 
Alfalfa. ^ Alfalfa Investigation. II. C. A. Jacobson (J. Amer. 
Chem. Soc, 1912, 34, 300— 302).— In an earlier paper (this vol., 
ii, 80) it was shown that myristone is present in alfalfa meal. Another 
ketone, CgiH^gO, m. p. 88*5 — 88-8°, has nowbecD isolated in the form of 
a white, amorphous powder, and has been termed alfalfone. On 
reducing this ketone with sodium and alcohol, the corresponding 
carbinol, CgjH^g'OH, m. p. 86*3 — 86*5°, is produced as a white, 
amorphous powder. E. G. 

New Anhydrides of Dextrose and Glucosides. Emil Fischer 
and Kakl Zach (Ber., 1912, 45, 456 — 465). — By the action of barium 
hydroxide on triacetylmethylglucoside bromohydrin (Fischer and 
Armstrong, Abstr., 1902, i, 263), the authors have isolated a substance, 
C^HjgOg, which they provisionally name anhydromethylglucoside. It 
forms a crystalline hydrate, and is not converted into sugar by emulsin. 
Warm dilute acids convert it into anhydrodextrose, CqK-j^qO^, which 
strongly resembles the hexoses, differing from them, however, in 
its much greater ability to restore the colour to Schiff's reagent. It 
yields a hydrazone and an osazone. 

The transformation of acetyldibromodextrose into triacetyldextrose 
bromohydrin and into triacetylmentholglucoside bromohydrin is also 
described together with the formation of anhydromentholglucoside from 
the latter substance. 

Anhydromethylglucoside was prepared by warming triacetylmethyl- 
glucoside bromohydrin with barium hydroxide in aqueous alcoholic 
solution. After filtration and evaporation, the residue was distilled 
under a pressure of 0*2 — 0*3 mm., when the anhydride passed over 
between 160° and 165° (temp of bath) as a colourless syrup. In aqueous 
solution it had [a]^ - 136*95°. Under suitable conditions it formed a 
hydrate which was not obtained free from syrup. At 5 6°/ 12 mm. it 
still retained water. When dried over phosphoric oxide at 
100°/ 12 mm., it melted, lost all its water, and left a residue of 
anhydromethylglucoside. 

Anhydrodextrose was formed by hydrolysing anhydromethyl- 
glucoside with 4*5% sulphuric acid. It crystallised in long needles, 
m. p. 118° (corr.) after slight softening. In aqueous solution it had 
[a]p + 53-89°. It dissolved readily in water and alcohol, with difficulty 
in ethyl acetate. 

Anbydrodextrosephenylhydrazone was best prepared by mixing 
anhydrodextrose with pure phenylhydrazine. The solid mass obtained 
by gently warming the mixture was washed with ether and crystal- 
lised from water, from which the phenylhydrazone separated in faintly 
yellow leaflets, m. p. 157 — 158° (corr.). 

Anhydrodextrosephenylosazone, prepared in the same manner as 
dextrosephenylosazone, crystallised in slender needles. It darkened 
when heated, and had m. p. about 180° (corr. decomp.). 

Triacetylmenthol - d - glucoside bromohydrin was formed when 
ethereal solutions of acetyldibromodextrose and menthol were shaken 
with silver carbonate. It separated from alcohol in long needles, 
m. p. 140° (corr.), and had [a]b° -49-62° in chloroform solution. Treat- 



i. 240 ABSTRACTS OF CHEMICAL PAPERS. 

ment with sodium hydroxide in alcoholic solution transformed it into 
anhydromentholglucoside, m. p. IIS'^ (corr.), [aj'i'f -96*73° in alcoholic 
solution. 

Triacetylhenzylglucoside hromohydrin was obtained in the same 
manner as the above menthol compound. It had m. p. 141° (corr.) 
after previous softening, [a]?j -46-76° in chloroform solution. 

Acetyldibromodextrose when shaken in acetone solution with silver 
carbonate yielded triacetyldextrose hromohydrin, m. p. 119° (corr.), 
[a]i? + 23*33® in acetone solution. Mutarotation has not yet been 
observed with this compound. H. W. 

Dextrinisation of Starch by Desiccation. Giovanni 
Malfitano and (Mile.) A. Moschkoff {Compt. rend., 1912, 154, 
443 — 446). — The conversion of starch into dextrin is attributed to 
progressive dehydration of the substance, and not to the ordinary 
hydrolytic action of water. Starch was dehydrated over phosphoric 
oxide at the ordinary temperature and at higher temperatures up to 
150°, the loss of water, percentage of carbon and hydrogen, and 
amount of soluble matter formed being determined from time to time. 
In a vacuum, at 25°, 28*1% of soluble matter was formed after twenty 
days ; this rose to 90% when the material was heated for four hours 
at 120°. Some decomposition occurs, even at 50°, before dehydration 
is complete, as is shown by the starch turning brown. This, however, 
is not the cause of increased solubility, for at 150° solubility is less, 
and analysis shows that no oxidation has occurred. 

These experiments lead to the suggestion that the starch micro-cells 
are composed of molecules of CgHjoO^, linked together by water, in a 
manner represented by the formula 

{[(C6H,„0,-OH)H](C,H,<,05-OH)}H . . ., 
or more accurately as 

{[(CeH,„0,-0H)H]4(CeHiA-0H)]„H„.i}H . . . 

Soluble starch, amylodextrin, erythrodextrin, etc., may be regarded 
as arising by successive removals of CgHjoO^ groups. When dextrinisa- 
tion occurs in the ordinary way by heating starch with water, the 
effect is the same, but the mechanism is different, water between the 
complexes being removed by ionisation. W. 0. W. 

Lintner Soluble Starch. Ernest D. Clark (Biochem. Bulletin, 
1911, 1, 194 — 206). — A study of the reducing power and erythro- 
dextrin reaction with iodine on Lintner soluble starch prepared from 
potato starch. The product can only be purified with the greatest 
difficulty, if at all, from the dextrin to which these reactions aie due. 

W. D. H. 

ActioD of Tetrabromoethane on Organic Bases. William 
M. Dehn (/. Amer. Cfiem. Soc, 1912, 34, 286— 290).— When tetra- 
bromoethane is added to a solution of an organic base in dry ether, 
the hydrobromide of the base is precipitated and tribromoethylene is 
produced and remains in the solution. The reaction takes place more 
easily with aliphatic amines than with aromatic bases, and more 
easily with primary than with secondary or tertiary amines. It is 



ORGANIC CHEMISTRY. i. 241 



accelerated by direct sunlight. The hydrobromides of various amines 
have been obtained in the pure state by this method, and their 
mercuribromides and auribromides prepared. 

When piperidine is added to an ethereal solution of tetrabromo- 
ethane, the hydrobromide is instantaneously and quantitatively 
precipitated, and this constitutes a convenient aud inexpensive method 
for the preparation of tribromoethylene. 

The following salts are described : Ethylamine viercuribromide, 
NH2Et,HBr,HgBr2, m. p. 91°. Diethylamine hydrobromide, m.. p. 205°, 
auribromidey NHEtgjHBr, AuBrg, m. p. 162°, and mercurihromide, 
m. p. 120°. Triethylamine awibromide, m. -p. 14:0°, 3ind mercuribromides 
m. p. 109°. Dipropylamine hydrobromide^ m. p. 271°, auribromide, 
m. p. 119°, and mercuribromide, m. p. 109°. Tripropylamine hydro- 
bromide, m. p. 180°, auribromide, m. p. 149°, and mercuribromide, 
m. p. 104°. isojButylamine hydrobromide, m. p. 138°, auribromida 
m. p. 154°, and mercuribromide, m. p, 164°. Di-isobutylamine 
hydi'obromide, m. p. 313°, auribromide, m. p. 245°, and mercuribromide, 
m. p. 60°. Amylamine hydrobromide, m. p. 243°, auribromide, m. p. 
105°, and mercuribromide, m. p. 213°. JDi-isoamylamine hydrobromide, 
m. p. about 315°, auribromide, m. p. 220°, and mercurihromide, m. p. 
97°. Allylamine hydrobromide, m. p. 91°, and mercuribromide, m. p. 
115°. Benzylamine mercuribrom,ide, m. p. 211°. Dibenzylamine 
auribromide, m. p. 165°, and mercuribromide, m. p. 145°. Pyridine 
mercuribromide, m. p. 152°. Ficoline mercuribromide, m. p. 88°. 
Fiperidiiie mercuribromide, m. p. 143°. E. G. 

Hexabromoselenates [Selenibromides]. Alexander Gutbier and 
W. Grunewald {J. p\ Ghem., 1912, [ii], 85, 321— 330).— An account 
of the preparation and properties of the selenibromides of the alkali 
metals and a number of aliphatic amines of the general formula 
Il2SeBrg, The general method of preparation consists in the addition 
of an aqueous solution of the alkali bromide or of the amine in 
hydrobromic acid to an excess of a solution of the compound 
H2SeBr^, in hydrobromic acid. The latter solution was prepared by 
adding bromine to a mixture of finely divided selenium and strong 
hydrobromic acid. The selenibromides are stable towards air, but are 
decomposed by water; those of the alkali metals crystallise in 
octahedra or cubes, belonging to the regular system [Lenk.]. In 
addition to the selenibromides of sodium, potassium, caesium, rubidium, 
ammonium and of methylamine, dimethylamine, trimethylamine and 
ethylamine, all of which have been previously isolated (Muthmann and 
Schafer, Abstr., 1893, ii, 318; Norris, Abstr., 1898, i, 510; Lenher, 
Abstr., 1899, ii, 18), the following new compounds are described : 
Diethylammo7iium selenibromide, (NH2Et2)2SeBrg, lustrous, brownish- 
red needles of monoclinic habit ; the corresponding propylamine com- 
pound, (NH3Pr*)2SeBrg, ruby-red plates of a metallic lustre and 
rhombic habit ; butylammonium selenibromide, (NH3*C4Hg)2SeBrg, 
forms lustrous, orange-red leaflets ; the isobutylamine compound, vivid 
red, hexagonal platelets. Ethylenediammonium selenibromide, 

(C,Hi,N,)SeBr„ 
forms garnet-red crystals of a metallic lustre, belonging to the 



i. 242 ABSTRACTS OP CHEMICAL PAPEllS. 

triclinic system ; the jrropyhne compound, (C3Hj2N2)SeBrg, garnet-red 
crystals of rhombic habit. F. B. 

Action of Tetraiodoethylene on Organic Bases. William 
M. Deun {J. Amer. Chem. Soc, 1!)12, 34, 290—293).— In earlier 
papers (Dehn, Abstr., 1911, i, 829 ; Dehn and Dewey, 1911, i, 914) it 
was staled that carbon tetrabromide and di-iodoacetylene combine with 
organic bases, dissolved in dry ether, to form molecular compounds. It 
is now shown that tetraiodoethylene behaves in a similar manner. 
Sunlight is generally necessary to promote the reactions. The com- 
pounds are decomposed by water ; in the case of the diethylanfine 
compound the main reaction is NHEt2,C2l4 — >■ NHEtg -t- C.^I^, 
but a large proportion decomposes, thus : 3NHEt2,C2l4 + SHgO — ^ 
3NHEt2,HI-i-3C2l2 + 2HI-i-HI03. Although the normal course of 
the reaction between tetraiodoethylene and organic bases is that 
indicated, secondary reactions take place involving the production of 
di-iodoacetylene, thus: 3NHEt2 + 2C2l4 — > 2NHEt2,HI + 2C2l2 + 
NHEtoJa, and 3NHEt2 + 3C2I4 — ^ NHEt2,HI + NHEt2,l2 + 
NHEtgjHI.Ig + SCgla- The crystalline mass precipitated from the 
ethereal solution is, therefore, usually a mixture of two or more 
substances which are sometimes very difficult to separate. The 
following compounds are described. 

The ethylamine coj7ipounda, NH2Et,C2l4, m. p. 155°, and 
NH2Et,2C2l4, m. p. 133^; ethylamine hydriodide, m. p. 167°, and 
niercuH-iodide, m. p. 136°. The diethylamine compound, NHEtg.Cgl^, 
m. p. 158°; diethylamine hydriodide, m. p. 165°, and 'msixuri-iodide, 
m. p. 115°. The triethylamine compound, NEt8,2C2l4, m. p. 132°; 
trieihylamine hydriodide, m. p. 173° (decomp.), and mercuri-iodide, 
m. p. 84°. The wopropylamine compound, ^yi^i:^,2(u^^, m. p. 160°. 
The dipropylamine compound, NHPr*2,2C2l4, m. p. 130°; dip'opyl- 
amine hydriodide, m. p. 229° (decomp.), and mercuri-iodide, m. p. 81°. 
The di-woamylamine compound, NH(C5H^^)2,C2l4, m. p. 150° ; di-iso- 
aanylaviine mercuri-iodide, m. p. 110°. The benzylamine compound, 
OH2Ph'NH2,C2l4, m. p. 115°; benzylamine hydriodide, m. p. 162°, 
and mercuri-iodide, m. p. 134°. The w-phenylethylamine compound, 
C2H^Ph-NH2,C2l4,C2l2, m. p. 138° (decomp.) ; in-phenylethylamirie 
hydriodide, m. p. 267°, and mercuri-iodide, m. p. 131°. The piperidine 
compound, C5H^iN,2C2l4, m. p. 147°; piperidine hydriodide, softening 
at 172°, and mercuri-iodide, m. p. 104°. The quinoline compound, 
C^^^,i^^^, m. p. 132°. The acetamide compound, NH2Ac,C2l4,I, 
m. p. 175°. 

Precipitates were also obtained with pyridine, triphenylphosphine, 
triethylstibine, ;j-phenylenediamine, collidine, and picoline. E. G. 

New Compound of Hexamethylenetetramine with Ortho- 
arsenic Acid. GuiDO Rossi {Giomi. Farm. Chim., 1911, 60. 
Reprint 8 pp.) — On mixing saturated alcoholic solutions of ortho- 
arsenic acid and hexamethylenetetramine, the compound, 

(CeH,,N,)„(H3AsO^)2. 
is obtained. It crystallises in transparent needles, m. p. 173 — 174°, 
and (from experiments with a rabbit) is much less toxic than arsenic 
acid. R. V. S. 



ORGANIC CHEMISTRY. i. 243 

Stereoisomerism of Internally Complex Salts : Stereo- 
isomeric Cobaltio Salts of a-Amino-acids. Heinrich Ley and 
H. Winkler {Ber., 1912, 45, 372— 377).— The electrical conductivity 
of solutions of the stereoisomeric cobaltiglycines (Abstr., 1909, i, 886) 
is extremely small, but still capable of being measured. The 
results show that the dissociation of these compounds is hardly 
appreciable. When dissolved in O'OliV^-sulphuric acid the conductivity 
of the solution is practically identical with that of the pure acid, 
indicating that the amino-group is completely saturated by the 
internal complex formation. 

Experiments in which the rate of dehydration of the red and violet 
isomeric cobaltiglycines has been measured show that the violet 
isomeride loses its water of crystallisation the more readily. 

Using a method similar to that described for the cobaltiglycines 
{Joe. cit.), isomeric cohalti-a-alanines^ Co(C3Hg02N)3, have been 
prepared from alanine and cobaltic hydroxide. The violet isomeride 
crystallises in prisms, whilst the red isomeride forms microscopic 
needles. Both forms are very stable, dissolving in acids, for example, 
in concentrated sulphuric acid, without decomposition. The absorption 
spectra of the solutions are practically identical with those of the 
cobaltiglycines. 

The isomeric dinitrotctramminecobaltic salts (flavo- and croceo- 
salts) cannot be transformed directly one into the other, as is also the 
case with the above complex compounds. The absorption spectra of 
dilute solutions of the chloride and nitrate are also practically 
identical, the only difference being that the croceo-salt gives an 
additional band in the extreme ultra-violet. T. S. P. 

|l Internally Complex Salts of Platinum and Chromium. 
Heinrich Ley and K. Ficken {Ber., 1912, 45, 377— 382).— When a 
solution of potassium platinochloride is boiled with an excess of 
glycine, colourless crystals of platinoglycine, Pt(C2H402N)2, are 
obtained ; they are sparingly soluble in hot water, and soluble in 
concentrated sulphuric acid. The stability of this compound points 
to the formation of an internally complex salt, namely, 

Platino-a-alanine, Pt(C3Hg02N)2, is similarly prepared from alanine, 
and forms glistening, white leaflets, If, however, an excess of alanine 
is not used (1 mol. of potassium platinochloride to 2 mols. of alanine), 
a yellow solution is obtained after heating for several hours, which, on 
precipitation with alcohol, gives yellow needles of potassium platino- 

chloroalanine, K Qj^I^t^;^^ ^CgH^ , which are fairly readily 

soluble in water. An analogous glycine compound can also be 
obtained. 

If 1 mol. of the green or violet chromium chloride is heated in 
aqueous solution with 3 mols. of glycine, and 3 mols. of sodium 
hydroxide gradually added, a dark red solution is obtained, from which 
violet crystals of chromiglycine, Cr(C2H402N)2-OH,JH20, separate, 
these are collected from the hot solution, and the" filtrate concen- 



i 



L 244 ABSTRACTS OF CHEMICAL PAPERS. 

trated in a vacuum over sulphuric acid, a further quantity of violet 
crystals is deposited, together with larger, red crystals, having the 
composition Cr(C2H^02N)3,H20. The red are heavier than the violet 
crystals, from which they are readily separated by levigation with 
alcohol. Chromium-pentammine chloride can be used instead of 
cbi'omium chloride in the above preparation. Both the red and violet 
salts are sparingly soluble in water and the usual organic solvents. 
On prolonged boiling with water, the red salt apparently changes into 
the violet salt. With concentrated sulphuric acid, they give red 
solutions, which, in contradistinction to those of the cobaltiglycines, 
gradually decompose with the formation of chromic sulphate. The 
violet salt is either an hydroxoaquo-salt, Cr(C2H402N)2*OH*OH2, or, 
more probably, an internally complex salt, 

(C,HAN)2Cr<^{^>Cr(C2HAN)2. 

Similar compounds are obtained when a-alanine is used in place of 
glycine, the red salt being Cr(C3Hg02N)3, and the violet salt, 
Cr(C3H,02N)20H,H,0. 

Other amino-acids give similar compounds, which are to be described 
in another paper. T. S. P. 

Adaline. Karl W. Rosenmund and F. Herrmann {Ber. deut. 
pharni. Ges., 1912, 21, 96—103. Compare Abstr., 1911, i, 118; ii, 
1120). — It is shown that, on treatment with boiling water, hot alkaline 
solution or pyridine, adaline (a-bromo-a-ethylbutyrylcarbamide), 

OEt 'CO 
CBrEt2-CO-NH-CO-NH2, yields diethylhydantoin, NH< J_ i , 

coloiu'less crystals, m. p. 181 — 182°, and that when alkaline solutions are 
used some ethylcrotonylcarbamide, CHg'CHICEfCO'NH-CO'NHg, m. p. 
91°, is also formed, together with a high-boiling oil, Ci3H2oOgN2, b. p. 
283 — 286°, which probably contains two adaline residues. 

T. A. H. 

Reduction of Aliphatic Amides and Esters by the Metal- 
Ammonias. E. Chablay (Compt. rend., 1912, 164, 364—366).— 
Aliphatic amides decolorise solutions of sodium in liquid ammonia at 
— 50°, forming a mixture of sodium alkyloxide and the sodium derivative 
of the amide. A similar reaction occurs with esters, the same products 
being formed. The reaction in the latter case is represented by the 
equations (1) R-C02R' + 2Na,NH3 = R-CO-NHNa + R'ONa + NH3 + 
H. ; (2) R-CO-OR' + 2Na,NH3 + H^ = R-CH2-0Na + R'ONa + 2HN3. 

W. O. W. 

Ureabromin. Arthur Biltz {Pliarm. Zentr.-h., 1912, 53, 245—246). 
— This name is applied to a molecular combination of carbamide and 
calcium bromide, CaBr2,4CO(NH2)2,prepared by mixing the two com- 
ponents in solution. It is readily soluble in alcohol or water, 
insoluble in ether, light petroleum or benzene, and melts at 186°. It 
gives all the ordinary reactions of its components when dissolved in 
water. It is proposed to use it in medicine as a substitute for alkali 
bromides. T. A. H. 



ORGANIC CHEMISTRY. i. 245 

Reactions of Methylene. III. Diazomethane. Hermann 
Staudinger and Otto Kupfer {Ber.y 1912, 45, 501 — 509. Compare 
Abstr., 1911, i, 702, 751). — During the course of some unsuccessful 
experiments for the preparation of cyano-isonitrile and of di-iso- 
cyanogen, diazomethane has been obtained in 25% yield by the slow 
addition of chloroform (1-| mol.) in absolute alcohol to a hot alcoholic 
solution of potassium hydroxide (4 mols.) and hydrazine (1 mol.). A 
slow stream of nitrogen is passed through the apparatus during the 
preparation, whereby the diazomethane is removed and absorbed 
in ether. Methylhydrazine is a by-product of the reaction. 

Pure diazomethane has b. p. - 24° to - 2_3° and m. p. - 145°, and is 
extremely dangerously explosive, spontaneously or by contact with 
iodine, grease, etc. In dilute ethereal solution, however, it can be 
ignited without exploding. When carbon monoxide is passed through 
ethereal diazomethane and the gaseous mixture is heated at 400 — 500° 
in a quartz tube, the methylene produced by the decomposition of the 
diazomethane reacts with the carbon monoxide to form keten, which 
is detected by passing the issuing gases into ethereal aniline, whereby 
acetanilide is produced. 

Benzoylhydrazine, potassium hydroxide, and chloroform react in 
hot alcohol to form about 3% of diazomethane, the main product being 
benzoic acid, obtained from the intermediately formed phenylketen. 
Phenylhydrazine is scarcely attacked by potassium hydroxide and 
chloroform in hot alcohol, but as-diphenylhydrazine is converted into 
benzophenone in 60% yield. C. S. 

Urethane and Mercuric Acetate. A. Pieroni {Gazzetta, 1911, 
41, ii, 754 — 756). — Mercurimethylurethane hydroxide 

COgMe-NH-Hg-OH, 
is obtained by treating an alcoholic solution of equimolecular 
quantities of methylurethane and mercuric acetate with a slight excess 
of alcoholic potassium hydroxide. Mercurimethylur ethane acetate^ 
COgMe'NH'Hg'CgHgOg, is prepared by dissolving equimolecular 
quantities of methylurethane and mercuric acetate in a little water at 
60°. On keeping the solution over calcium oxide the substance 
separates out in crusts of microscopic needles. When treated with 
alcoholic potassium hydroxide, it decomposes almost quactitatively 
according to the equation: C02Me-NH-Hg-C2H302 + 2KI + H20 = 
Hgl2 + CO.^Me-NHg + CgHgOgK + KOH. 

Meo'curiethylur ethane, COgEt'NHg, is deposited from a solution 
of ethylurethane and mercuric acetate in water ; it forms crusts of 
microscopic needles, containing 1 mol. HgO, which it loses in a vacuum 
over sulphuric acid. 

Mercuri-isoamylurethaney C0(0C5H^^)'NHg, is obtained by keeping 
an alcoholic solution of equimolecular quantities of isoamyl urethane 
and mercuric acetate; it forms crystalline crusts, m. p. about 165° 
(decomp.). With sodium iodide, it decomposes in the same way as 
mercurimethylurethane acetate. R. V. S. 

Decomposition of Pyrazoline Bases as a means of Obtaining 
Derivatives of cyc^oPropane. Nicglai M. Kijner {J. Buss. Phys. 
Ghem. Soc, 1912, 44, 165— 180).— The conversion into the 
VOL. Cll. i. s 



i. 246 ABSTRACTS OF CHEMICAL PAPERS. 

dicyclic hydrocarbon, carane, of the base obtained by the action of 
hydrazine on tanacetone (compare Abstr., 1911, i, 1028) seemed to 
indicate that the formation of the trimethylene ring was related to the 
formation of the base. Since meaityl oxide, a compound structurally 
very similar to pulegone, also reacts with hydrazine to form a com- 
pound which gives 1:1: 2-trimethylcyc^opropane on decomposition, it 
was at first thought that the product of the interaction of mesityl 
oxide and hydrazine was not a pyrazoline derivative, as Curtius 
supposed, but a compound having the structure : 

^-CMe2-\ 

Further investigation has shown, however, that this compound is 
really a pyrazoline derivative, as also is the base formed by 
pulegone with hydrazine, this having the constitution : 
(^H— CH^.^H-CMe 

CHMe-CH2-C==N^ ' 
and not that previously given {loc. cit). The decomposition of this 
compound into carane and nitrogen is exactly similar to that of 
3:5: 5-trimethylpyrazoline (from mesityl oxide and hydrazine) into 
1:1: 2-trimethylc?/c^opropane and nitrogen, the two nitrogen atoms 
being eliminated from the pyrazole nucleus and the residue closing up 
to a three carbon-atom ring. Similar decompositions take place with 
1-methyl-l :2-diethylpyrazoline, which yields 1-methyl-l : 2-diethyl- 
C7/c^opropane, and with esters of pyrazoline-3 : 4 : 5 -tricarboxylic acid, 
which yield esters of c?/c?opropanetricarboxylic acids (compare 
Buchner, Abstr., 1888, 1274; 1890, 736). 

The author intends to ascertain whether derivatives of cyclo- 
propanone can be obtained in a similar manner from pyrazolone 
compounds. 

1:1: 2-Trimethylc2/cZopropane, CgHjg, obtained by heating 3:5:5- 
trimethylpyrazoline in a sealed tube with potassium hydroxide and 
platinised porous tile, is a liquid, b. p. 52-5°/752 mm., 52-6°/753 mm., 
52-87756 mm., D^ 0-6949, tij, 1-3866. The compound described under 
this name by Zelinsky and Zelikoff (Abstr., 1901, i, 657) was 
apparently not pure, the high value of the molecular refraction 
indicating considerable admixture of ethylene hydrocarbon. The 
action of alkaline permanganate on 1:1: 2-trimethylc2/cZopropane is 
very slow, but much more rapid than with the dicyclic trimethylene 
hydrocarbons, thujane and carane, or with the 1-methyl-l : 2-diethyl- 
cyc^opropane described below. Fuming nitric acid readily reacts with 
the hydrocarbon with development of heat, whilst concentrated 
sulphuric acid polymerises it. 

The action of bromine on 1:1: 2-trimethylcyc^opropane in acetic 
acid solution yields: (1) a small proportion of ^-hromo- ^-methyl- 
pentane, CMegBr-CHg-CHgMe, b. p. 135—1387752 mm., D^*' 1-1806, 
Wu 1-4517, which is the result of a secondary reaction of the hydrogen 
bromide liberated on the hydrocarbon; (2) pS-dibromo-^-methylpentanet 
CMegBr-CHg-CHMeBr, b. p. 87—89723 mm., D^ 1-6242, U^ 1-5979, 
Tiiy 1*5097, which yields yS-methylpentane when reduced with hydrogen 



ORGANIC CHEMISTRY. i. 247 

iodide ; thus combination of bromine with 1:1: 2-trimethylcyc^o- 
propane takes place at the least hydrogenated carbon atom. 

Reduction of 1:1: 2-trimethylc2/c^opropane by Sabatier's method 
gives ^|S-di methyl butane, so that hydrogen combines with this hydro- 
carbon at the most highly hydrogenated carbon atom. 

The action of fuming hydriodic acid on 1:1: 2-trimethylc?/cZo- 
propane yields : (1) y8-iodo-/3y-dimethyl butane, CMegl'CHMeg, b. p. 
83—84777 mm., 1417755 mm. (slight decomp.), Bf 1-4436, Uj, 1-5035, 
which seems to be accompanied by a small proportion of another 
iodo-compound, probably )8-iodo-^-methylpentane. The action of 
fuming hydrobromic acid on 1:1: 2-trimethylc2/c^opropane yields 
^-bromo-^-methylpentane (see above). 

1-Methyl-l : 2-diethylcjclo2)7'opane, CH2<^ I ^ , obtained by heat- 
ing 5-methyl-3 :5-diethylpyrazoline (compare Curtius and Zinkeisen, 
Abstr., 1899, i, 165) in a sealed tube at 240°, has b. p. 108—109°/ 
742 mm., D^" 07382, ti^ 1-4102. It combines slowly with bromiae, 
whilst with hydrobromic acid it gives y-hromo-y-methylheptane (?), 
b. p. 101— 102753 mm., jy^ 1-1406, n^ 1-4613, which, when distilled 
with aniline, yields an unsaturated hydrocarbon^ ClgHj^,, b. p. 117 — 1197 
742 mm., DJ^'^ 0-7426, n^ 1-4210, this forming a liquid bromide. 

T. H. P. 

Loschmidt's Graphic Formulae: History of the Benzene 
Theory. Richard Anschutz {Ber., 1912, 45, 539 — 553). — Historical. 
The author gives an account of the graphic formula developed by 
» Loschmidt in his " Chemische Studien " (Yienna, 1861). It is pointed 
out that the latter ascribed a ring structure to the benzene nucleus 
four years before Kekule published his benzene theory. F. B. 

Stereochemistry of the Aromatic Series. Roman Oasares 
(Anal. Fis. Quim., 1912, 10, 14 — 18). — The author proposes a three 
dimensional formula for benzene based on an alternate arrangement of 
tetrahedra, in such a way that the projection on a plane is a regular 
hexagon. The difference from Ladenburg's prism formula is slight, 
and the same difficulty would be experienced in explaining the 
mechanism of reduction. Naphthalene, anthracene, phenanthrene, 
and chrysene are formulated on the same principle. G. D. L. 

Hydrogenation and Dehydrogenation. Heinrich Wieland 
(Ber., 19] 2, 45, 484— 493).— The researches of Sabatier, Ipatieff, 
Knoevenagel, and others show that the addition of hydrogen to an 
unsaturated organic compound in the presence of finely divided nickel, 
copper, palladium, etc., at a definite temperature is reversed at a higher 
temperature. It is to be anticipated, therefore, that Paal's method of 
reducing substances containing double linkings by hydrogen in the 
presence of colloidal palladium at the ordinary temperature is reversible, 
and that, under definite conditions, the same state of equilibrium must 
be reached whether the unsaturated or the hydrogenised substance is 
employed initially. The author finds that by shaking with palladium 

s 2 



i. 248 ABSTRACTS OF CHEMICAL PAPERS. 

black (carefully prepnred free from oxygen), aqueous quinol is partly 
converted into ^^-benzoquinone and quinhydrone, hydrazobenzene 
diesolved in benzene is changed into azobenzene and aniline, dihydro- 
naphthalene dissolved in benzene yields naphthalene and tetrahydro- 
naphthalene, and dihydroaiithracene in benzene is slowly transformed 
into anthracene ; acenaphtbene and bisdiphenylene-ethane are un- 
changed under the preceding conditions. 

In these reactions the palladium plays the part, not of a catalyst, 
but of a substance of active mass ; by increasing the amount of the 
metal, the equilibrium of the system is shifted in the direction whereby 
the yield of the dehydrogenised substance is increased. 

Unsaturated substances which decolorise potassium permanganate 
can, in general, be catalytically hydrogenised, but are not necessarily 
attacked by nascent hydrogen ; naphthalene is unaffected by hydrogen 
and palladium, but is reduced to dihydronaphthalene by sodium and 
alcohol, whereas dihydronaphthalene is unaffected by sodium and 
alcohol, but is easily converted into tetrahydronaphthalene by hydrogen 
and palladium. It appears, therefore, that the activation of hydrogen in 
the presence of a finely divided metal is not due to the production of 
nascent (atomic) hydrogen, but more probably to the formation of a 
metallic hydride which additively reacts with the unsaturated substance: 
R:R + PdHg :i: RH-R-PdH zr RH-RH + Pd. The probability of the 
formation of such intermediate additive compounds is supported by 
the facts that methyl or ethyl alcohol is absorbed by palladium black 
with development of heat, and the alcohol can only be recovered by 
long keeping in a vacuum ; it then contains a certain amount of the 
aldehyde. Under such conditions, propyl alcohol is much more readily 
converted into propaldehyde, whilst benzyl alcohol yields benzaldehyde 
at once. C. S. 

The Addition of Chlorine to Dichlorobenzenes. T. van der 
Linden {Ber., 1912, 45, 411—418. Compare this vol., i, 174).— The 
author hoped by the removal of two molecules of hydrogen chloride 
from any dichlorobenzene hexachloride [octachlorocycZohexane] to 
obtain a substance of the composition C^HgClg which might be 
considered as identical with the assumed intermediate product in the 
substitution of a chlorine atom into tetrachlorobenzone. 

The additive compound of p-dichloro benzene and chlorine was obtained 
by passing chlorine into a solution of the substance in carbon tetra- 
chloride under strong sodium hydroxide solution in sunlight, also by 
exposing to sunlight a mixture of the theoretical quantities of p-dichJoro- 
benzene and chlorine in a closed tube. The main product (from its 
resemblance to ^-benzenehexachloride) is designated /3-;?-dichloro benzene 
hexachloride, and after recry stall isation from nitrobenzene has m. p. 
262°; it has already been obtained by Jungfleisch {Bull. Soc. chim.f 1888, 
[2], 9, 352). On treatment with alcoholic potash, three molecules of 
hydrogen chloride are eliminated with formation of pentachloro- 
benzene ; the same behaviour is exhibited by all the isomerides 
described below. 

The carbon tetrachloride mother liquors of the above substance 
contained an isomeric hexachloride, which, on account of its low m. p. 



ORGANIC CHEMISTRY. i. 249 

and considerable solubility, is termed a-ip-dichlorobenzene hexachloride ; 
the m. p. is 89*6°. Indications of a third isomeride, m. p. 110 — 120°, 
were also observed. o-Dichlorohenzene hexachloi'ide, obtained by the 
sealed tube method, has m. p. 147°. 

m- Dichlorobenzene hexachloride was obtained by the action of 
chlorine on the dichloro-compound under a layer of dilute sodium 
hydroxide solution ; it has m. p. 81-8°. 

As the above substances, even when treated with an insufficiency of 
alcoholic potash, yield only pentachlorobenzene and unchanged 
substance, a- and )8-chlorobenzene hexachlorides were prepared by the 
sealed tube method, but alcoholic potash again removes simultaneously 
three molecules of hydrogen chloride from each molecule of 
hexachloride. D. F. T. 

Reduction of Nitrobenzene by means of Ferrous Hydroxide. 
Herman Camp Allen {J. Physical Chem., 1912, 16, 131— 169).— The 
products of reduction of nitrobenzene by ferrous sulphate with slight 
excess of sodium hydroxide depend on the temperature, concentration, 
and order of mixing of the reacting substances. 

When nitrobenzene is run into a well stirred mixture of ferrous 
sulphate and sodium hydroxide solutions or when nitrobenzene and 
ferrous sulphate are stirred together and sodium hydroxide is slowly 
introduced, the reduction takes place in a neutral or slightly alkaline 
medium, and the product is mainly aniline. The yield of aniline varies 
from 100% at room temperature to 80% at the boiling point. A high 
yield of aniline is also obtained when the ferrous sulphate is added 
last, if it is run in quickly and in excess. 

When, however, sodium hydroxide and. nitrobenzene are 
stirred together, and ferrous sulphate is added very slowly, the 
reduction takes place in a strongly alkaline medium, and the product 
is mainly hydrazobenzene. At 75° the yields were : aniline 21%, 
hydrazobenzene 60%, azoxybenzene 14%. At the boiling point the 
yields were : aniline 33%, hydrazobenzene 58%. When the ferrous 
sulphate was restricted to the amount required to reduce to azoxy- 
benzene only, the yields were : aniline 18%, azoxybenzene 76%. 

Both azoxybenzene and azobenzene are reduced by excess of 
alkaline ferrous sulphate at the boiling point, the product being 
hydrazobenzene with some aniline. Aniline seems to be formed in this 
way in the alkaline reduction of nitrobenzene at 100°, whereas at the 
ordinary temperature it is formed by the nitrosobenzene-phenyl- 
hydroxylamine route. There is a minimum production of aniline at 
about 75°, and the utility of alcohol in the electrolytic production of 
hydrazobenzene and azobenzene is partly due to its solvent action, and 
partly to its favourable boiling point. 

According to Haber's scheme for the reduction of nitrobenzene 
(Abstr., 1900, i, 281), azoxybenzene is the immediate forerunner of 
hydrazobenzene, as the above results suggest, and the oxidation of 
hydrazobenzene by nitrobenzene gives azobenzene, the nitrobenzene 
being reduced to azoxybenzene at the same time. The author finds 
that the production of azobenzene from hydrazobenzene on boiling for 
twenty minutes with excess of nitrobenzene is almost quantitative, and 



i. 250 ABSTRACTS OP CHEMICAL PAPERS. 

azoxybenzene is formed simultaneouHly, in accordance with Haber'fi 
view. In the Elba method of electrolytic preparation of azobenzene, 
the intermediate stage is probably azoxybenzene, since with a low 
current density in well stirred solutions, azoxybenzene is the principal 
product. 

In the author's experiments, 1*2 gram of nitrobenzene was reduced 
and the filtered liquid was extracted with benzene. It was assumed 
that the extract contained only aniline, hydrazobenzene, azobenzene, 
azoxybenzene, and unaltered nitrobenzene. The aniline was extracted 
with dilute sulphuric acid and titrated with bromate. The residue was 
estimated by evaporating until a more or less sharp bend in the time- 
weight curve indicated that the last traces of benzene had been 
removed. A similar procedure gave the residue after aniline and 
hydrazobenzene had been extracted together by 1 : 3 sulphuric acid ; 
hence hydrazobenzene was calculated by difference. Azobenzene was 
estimated colorimetrically in the above residue, and nitrobenzene was 
reduced to aniline and titrated. Azoxybenzene was then calculated by 
difference. Phenylhydroxylamine was present in traces only. 

In neutral or slightly alkaline reductions at the boiling point, about 
15% of the nitrobenzene remained unaccounted for. It is suggested 
that decomposition of the intermediate product, phenylhydroxylamine, 
may have given rise to substances not extracted by benzene from the 
aqueous solution. In strongly alkaline reductions at the boiling point, 
the nitrobenzene could all be accounted for. R. J. C. 

Fission of Phenylethyltrimethylammonium [Chloride]. 
Hermann Emde {Apoth. ZeiL, 1912, 27, 18 — 19). — The reduction of 
phenylethyltrimethylammonium chloride by means of sodium amalgam 
(compare Abstr., 1909, i, 708; this vol., i, 20) results in the formation 
of trimethylamine and styrene instead of ethylbenzene as previously 
assumed. In this case, the action of sodium amalgam is precisely 
similar to that of sodium hydroxide. 

Explicit directions are given for the reduction of crude benzyl 
cyanide to phenylethylamine, and for the transformation of the latter 
into phenylethyltrimethylammonium chloride by means of methyl 
sulphate. H. W. 

New Derivatives of Indene. Victor Grignard and Charles 
CouRTOT (Compt. rend., 1912, 154, 361—364. Compare Abstr., 
1911, i, 193, 292). — The action of bromine on magnesium indenyl 
bromide gives rise to the formation of 1:2: 3-tribroinoindane, 
CgHn-Brg, m. p. 133 — 134°, together with an oily substance containing 
l-bromohideTie, C^H^Br. The latter is best prepared by adding the 
organo-magnesium derivative to cyanogen bromide, when it is obtained 
as a yellow liquid, b. p. 126722 mm. The compound resembles allyl 
bromide in its reactions. If cyanogen chloride is used instead of the 
bromide, 1-cyanoindene, Ci^HyN, b. p. 140 — 142714 mm., is formed. 
When treated by Pinner's method, this yields ethyl indene- 1- 
carboxylate, b. p. 14078 mm. (compare Weissgerber, Abstr., 1911, 
i, 1442). 

Di-indmyl, CH<^^^CH-CH<^|^>CH, prepared by the 



i 



ORGANIC CHEMISTRY. i. 251 

action of iodine on magnesium indenyl bromide in toluene, occurs as 
colourless crystals, m. p. 99—100°; when treated with bromine it 
forms two tetrabromides. One of these is soluble in chloroform and 
has m. p. 138 — 139°, whilst the other is insoluble and has m. p. 
222—224°. W. O. W. 

The Influence of the Nitro-group on the Sulphonation of 
Diphenylmethane. Alfred Kliegl (Verh. Ges. deut. Naturforacli. 
Aerzte, 1912, ii, [1], 225-226).— Wedekind and Schenk (Abstr., 1911, 
i, 190) found it impossible to sulphonate the methylene group of 
diphenylmethane with chlorosulphonic acid. An attempt has there- 
fore been made to lessen the liability of the nuclei to sulphonation, 
and at the same time to increase the reactivity of the methylene group 
by the introduction of substituents. It is found, however, that 
nitro-groups increase the readiness with which diphenylmethane is 
sulphonated. In all three nitrodiphenylmethanesulphonic acids, the 
sulpho-group occupies the para-position in the un-nitrated nucleus. 
Triphenylmethane behaves in a similar manner, and o-nitrotriphenyl- 
methane gives a disulphonic acid with concentrated sulphuric acid on 
the water-bath. 

^-Aminodiphenylmethane-jp-sulphonic acid yields a sparingly soluble 
diazosulphonic acid, which behaves as an internal salt, although the 
two salt-forming groups are attached to different nuclei. C. H. D. 

Sulphonation of )8-Nitronaphthalene. Hans Kappeler (Ber.^ 
1912,45, 633— 635).— The sulphonation of ;8-nitronaphthalene with 
fuming sulphuric acid is completely analogous to that of y8-naphthyl- 
amine. A mixture of two monosulphonic acids is obtained, which were 
identified by reduction to the corresponding j8-naphthylaminesulphonic 
acids. 

2-N^itronaphthalene-5 -sulphonyl chloride forms large, pale yellow prisms, 
m. p. 127° ; the corresponding amide crystallises in yellow, four-and six- 
sided plates, m. p. 223—224°. 

2'N'itronaphthalene-8-sulphonyl chloride separates in tiny, almost 
colourless needles, m. p. 169 — 170°; the amide forms colourless, 
crystalline tablets, m. p. 261 — 262°. 

The free sulphonic acids were obtained as colourless, microcrystalline 
precipitates. E. F. A. 

Action of Sulphurous Acid on Aldehydoaminic Bases. 
Mario Mayer {Gazzetta, 1912, 42, i, 50—56. Compare Abstr., 
1911, i, 223). — Benzylideneaniline anhydrosulphite, 

(CHPh:NPh)2,S02, 
is an orange-yellow powder, m. p. 115 — 120° (decomp.), which is 
obtained when dry sulphur dioxide acts on dry benzylideneaniline, 
and also (more easily) when a benzene solution of benzylidene- 
aniline is saturated with sulphur dioxide. The substance loses 
sulphur dioxide when kept, leaving benzylideneaniline as the only 
product. 

Aniline benzylideneaniline sulphite, already obtained by Knoe- 
venagel, can also be prepared by saturating an ethereal solution of 
benzylideneaniline with sulphur dioxide. When it is heated in a 



i. 252 ABSTRACTS OF CHEMICAL PAPERS. 

sealed tube for some hours at 105 — 110°, aniline and aniline sulphite 
are formed, and, in addition, henzylideneaniline hydrogen sulphite^ 
CiglljgOgNS. This decomposition renders improbable Eibner's 
supposition (Abstr., 1901, i, 376) that the original compound is 
dianilinophenylmethane anhydrosulphite, CHPh(NHPh)2,S02. Benzyl- 
ideneaniline hydrogen sulphite is best prepared by passing sulphur 
dioxide through a very dilute aqueous-alcoholic solution of henzyl- 
ideneaniline ; it forms tufts of acicular crystals, m. p. 145°. If the 
solution is more concentrated, the salt of m. p. 125° is obtained, but 
when this is removed, the liquid slightly warmed, and treated with 
more sulphur dioxide, a substance separates in the form of long, flat 
needles, m. p. 147°, which are identical in behaviour with those 
above mentioned, m. p. 145°. Benzylideneaniline hydrogen sulphite 
yields the above-mentioned salt of m. p. 125° when treated with 
aniline. 

Speroni (Abstr., 1903, i, 246) obtained the neutral anhydrosulphite 
of aniline and benzaldehyde, giving the m. p. 138 — 140°. On 
repeating this preparation the author obtains a substance, m. p. 
125°, which is identical with Knoevenagel's salt previously referred 
to. If, however, this compound is treated with warm alcohol, the 
greater part of it then has m. p. 140° (decomp.) and gives the same 
analytical figures as the salt of m. p. 125° and it is suggested that 
the two substances are the aniline salts of two isomeric forms of the 
sulphurous acid. Speroni, by treating a neutral aqueous solution of 
aniline sulphite with benzaldehyde, obtained a substance, m. p. 130°, 
but the author, working under the same conditions, always obtains a 
product, m. p. 125 — 127°, identical with the salt of m. p. 125° already 
mentioned. 

When the three compounds above described (of m. p. 115 — 120°, 
145° and 125° respectively) are treated with a cold, saturated, alcoholic 
solution of picric acid, the first two yield benzylideneaniline picrate, 
whilst the third gives also aniline picrate. 

In regard to the constitution of the sulphites described in this and 
in the earlier paper, the author rejects Eibner's view {loc. cit.) that 
all compounds formed from aldehydes, amines, and sulphurous acid 
are sulphites of aldehydoaminic bases. Such substances as the 
additive products from benzylideneaniline and sulphur dioxide or 
sulphurous acid do belong to that type, but the other compounds 
described in the present paper and the aldehyde- and keto-sulphites 
of the alkaloids do not. The aldehydoaminic bases which are 
obtained when some of these decompose are not present in the 
compounds themselves, but are formed by the interaction of the 
aldehyde and amine first formed in the decomposition. 

K. V. S. 

Electrolysis of Phenyldialkylhydroxyethylammonium 
Iodides and Some Derivatives of Choline. Bruno Emmert {Ber., 
1912, 45, 430 — 433). — The electrolysis of quaternary phenylammo- 
nium salts at lead cathodes leads to the formation of tertiary aliphatic 
amines (Abstr., 1909, i, 376, 602). An attempt has been made to 
extend this method to those cases in which unsaturated aliphatic and 



ORGANIC CHEMISTRY. i. 253 

hydroxyalkyl groups are attached to the iV^-atom. By the electrolysis 
of phenyldimethylallylammonium iodide, however, propylene and 
dimethylaniline were obtained in good yield, the allyl instead of 
the phenyl group being eliminated. Electrolysis of phenyldimethyl- 
hydroxyethylammonium iodide and of phenylmethylethylhydroxy- 
ethylammonium iodide yielded dimethyl-y3-hydroxyethylamine and 
methylethyl-/3-hydroxyethylamine, whilst, at the same time, a certain 
amount of a tertiary aniline was formed, one aliphatic group being 
split off. 

Dimethyl/S-hydroxyethylamine was dried over potassium hydroxide 
and barium oxide, and, whilst still somewhat moist, had b. p. 129 — 133°. 
Ladenburg (Abstr., 1882, 166) found 130—134°, and Knorr (Abstr., 
1889, 905) 128—130°. The gold salt was analysed. 

MethylethyI-j8-hydroxyethylamine, isolated through its hydrochlorids^ 
had b. p. 149 — 150°. The aurichloride was analysed. When treated 
with methyl iodide in ethereal solution, it formed dimethylethyl- 
P-hydroxyethylammonium iodide^ which, on treatment with moist silver 
oxide, yielded the corresponding base. The latter was identified by 
conversion into its aurichloride, m. p. 276 — 277° (decomp.). Methyl- 
ethyl-^-hydroxyethylamine and ethyl iodide reacted to form an iodide, 
from which methyldiethyl-j8-hydroxyethylammonium hydroxide was 
prepared. The aurichloride obtained from the latter had m. p. 
246—247° (decomp.). 

A similar series of compounds was obtained from methylethyl- 
)3-hydroxyethylamine and propyl iodide. In this case the corresponding 
aurichloride could not be obtained in a crystalline state. The platini- 
chloride, CjgH^QOgNgCigPt, was analysed. H. W. 

Diphenylhydroxylamine. Heinrich Wieland and Alexander 
RosEEU [Ber., 1912, 45, 494 — 499). — The interaction of nitrosobenzene 
and magnesium phenyl bromide in ether at —15° under carefully 
regulated conditions leads to the formation of ^/3-diphenylhydroxyl- 
amine, NPhg'OH, m. p. 60° (decomp.), colourless crystals. The 
substance, when pure, can be kept for eight days without decomposi- 
tion, develops a deep blue coloration with concentrated sulphuric acid, 
is neutral in character, reduces ammoniacal silver solutions in the 
cold, and yields diphenylamine by reduction. It reacts with diphenyl- 
hydrazine hydrochloride (0 5 mol.) in slightly acidified alcohol to form 
the hydrochloride of quinoneanildiphenylhydrazone (Abstr., 1911, 
i, 82), the constitution of which is thus definitely settled. C. S. 

Action of Bromine in Presence of Aluminium Bromide on 
the Methylcyc^ohexanols. Fernand Bodroux and Felix Taboury 
(CompL rend., 1912, 154, 521. Compare Abstr., 1911, i, 779).— The 
three methylc^/c^ohexanols behave similarly to cyc/ohexanol in their 
behaviour towards bromine in presence of aluminium bromide. In 
each case the solid pentabromotoluene is formed, together with a 
yellow oil. The latter is a mixture of bromo-derivatives, and is 
capable of undergoing further bromination, giving gummy products in 
the case of methylc2/c^ohexan-2- and -4-ol. The third isomeride, however, 
gave a small quantity of hexabromomethylcyclohexane, CyHgBrg, in the 
form of long, colourless needles, m. p. 295°. W. O. W. 



i. 254 ABSTRACTS OF OHEMIOAL PAPERS. 

Halogen Derivatives of Phenolic Ethers. Alphonse Matlhe 
and Marcel Murat (Compt. rend., 1912, 154, 601—604*) — The 
catalytic method, in which thorium oxide is employed, is very 
advantageous for the preparation of diphenyl ether and its homologues, 
which are obtained with difficulty by the ordinary processes. 

pChlorodipfieni/l ether, OPh-CgH^Ol, prepared by the action of 
chlorine in presence of iodine on diphenyl ether in carbon tetrachloride 
solution, has b. p. 284°/760 mm., D^^ 1-2026, Wp 1-599; di-p-cMoro- 
diphenyl eiliAr, 0(CgH4Cl)2, formed at the same time has b. p. 312 — 315°. 
i^-Bromodiphenyl ether has b. p. 305°, and the dibromo-derivative, 
m. p. 54°, b. p. 338 — 340°. Di-o-tolyl ether gave the following com- 
pounds : a mo7ioc/i^oro-derivative, b. p. 308 — 310°, a c^icA^oro- derivative, 
b. p. 338— 340°, a ww>wo6romo-derivative, b. p. 330°/670 mm., D^o 1-4162. 
Di-p-tolyl ether gave a TworiocA^oro-derivative, b. p. 315°/760 mm,, a 
dicA^o-derivative, b. p. 240— 245°/20 mm., D^o 1-1800, a monolyromo- 
derivative, b. p. 330— 333°/760 mm., D^o 1-417, and a di6romo-deriv- 
ative, m. p. 131°. W. O. W. 

Action of Bromine and Chlorine on Dehydrodicarvacrol. 
Henri Cousin {Compt. rend., 1912, 154, 441 — 443; J. Pharm. Chim., 
1912, [vii], 5, 236— 240.t Compare Abstr., 1910, i, 4=7 6).—Dibromo- 
deliydrodicarvacrol, CgoHg^OgBrg, prepared by the action of bromine on 
dehydrodicarvacrol in chloroform solution, occurs in pale yellow 
prisms, m. p. 179 — 180°(corr.). The corresponding (£icA^oro-derivative, 
obtained by using the calculated amount of chlorine, crystallises in 
pale yellow prisms. When excess of chlorine is employed, dichloro- 
dehydrodicarvacroquinone tetrachloride, CgoHjgOgCl , is formed as a 
yellow resin, slowly changing to crystals, m. p. 155 — 156° (decomp.). 
When treated with reducing agents, this substance yields dichloro- 
dehydrodicarvacrol ; the corresponding quinone has not been isolated. 

W. 0. W. 

Colour of Alkaline Solutions of Quinol and of Their 
Oxidation Products. Robert Luther and A. Leubner {J. pr. 
Chem., 1912, [ii], 85, 233 — 234). — On treatment with aqueous alkalis, 
quinone gives yellowish-green solutions, which become brownish-black 
on exposure to air. Addition of sodium sulphite to solutions of 
quinone produces an intensely greenish-blue coloration, which gradually 
changes to light yellow. When shaken with air, the yellow solutions 
become green and then light yellow. If the traces of oxidation- 
products formed by dissolving the quinone are destroyed by potassium 
hydrogen sulphite or quinol, the addition of sodium sulphite produces 
a brown coloration. The blue coloration is probably due to the 
formation of an alkali salt of an oxidation product of quinone. 

According to Euler and Bolin (Abstr., 1909, ii, 374) quinol 
dissolves in alkalis, yielding yellow solutions, owing to the formation 
of quinonoid salts. The authors find, however, that solutions of 
potassium carbonate or potassium hydroxide and of quinol, to which 
small quantities of sodium hydrogen sulphite have been added in 

• and Bull. Soc. chim., 1912, [iv], 11, 328—332. 
t and Bull. Soc. chim., 1912, [iv], 11, 332—336. 



ORGANIC CHEMISTRY. i. 255 

order to destroy dissolved oxygen and traces of quinone, do not yield 
yellow colorations when mixed, but gradually acquire a dark brown 
colour on exposure to air. From these observations the conclusion 
is drawn that salts of quinol, quinone, hydroxyquinol, and 
dihydroxyquinol are respectively colourless, yellow, bluish-green, and 
reddish-brown. F. B. 

Isomerism Among the Ethers of Diisoeugenol. Ernesto 
PuxEDDU (Atti R. Accad. Lincei, 1912, [v], 21, i, 124 — 129. Compare 
Abstr., 1909, i, 225). — The author considers it probable that the 
polymerisation of eugenol ethyl ether observed by Wassermann is 
preceded by an isomerisation, so that Wassermann's polymeride is a 
diisoeugenol diethyl ether, stereoisomeric with the dizsoeugenol diethyl 
ether described by the author {loc. cit.). They differ not only in 
solubility and in m. p., but also give different bromine derivatives. 
Eugenol ethyl ether was prepared by the action of ethyl sulphate on 
eugenol dissolved in potassium hydroxide (10%), and also by Wasser- 
mann's method. When it was distilled, the residue which did not 
distil at 260° consisted of Wassermann's polymeride, but had 
m. p. 140° (Wassermann gave 125°). It is obtained in better yield 
by heating eugenol ethyl ether for fifteen hours in a bath at about 
270°. In chloroform solution, it absorbs bromine, but no individual 
substance could be isolated from the product. The diisoeugenol diethyl 
ether previously described by the author, when treated with bromine 
in ethereal solution cooled with ice and salt, yields monobromodiiso- 
eugenol diethyl ether^ C24H3j04Br, which forms yellowish-green, 
rhombohedral crystals, m. p. 118°. H. V. S. 

lodothio-ethers, lodosulphones, lodosulphonic Esters, and 
their Derivatives with Multivalent Iodine. Conrad Will- 
GERODT and Max Klinger {J. pr. Chem., 1912, [ii], 85, 189 — 198). — 
^-lodothiophenetole {^-iodophenyl ethyl sulphide), CgH^I'SEt, prepared 
by reducing p-nitrothiophenetole (jt?-nitrophenyl ethyl sulphide) with 
tin and hydrochloric acid and replacing the amino-group of the result- 
ing p-aminothiophenetole {^-aminophenyl ethyl sulphide) by iodine by 
means of the diazo- reaction, is a yellow oil, b. p. 146 — 147°/11 mm. 
When treated with chlorine in chloroform solution, it yields an unstable 
iododichloride, which rapidly decomposes into p-iodothiophenetole and 
^-iodohenzenesulphonyl chloride. The formation of the latter compound 
is considered to be due to the decomposition of the iododichloride into 
ethyl chloride and the compound (I), which then reacts with the 
iodoso-compound (II), produced by the action of moisture on the 
iododichloride : 

(I) C,H4l-SCl + (II) 2SEt-CoH4-IO = 2C6HJ-SEt + C«H4l-S02Cl. 

Methyl ^-iodobenzenesulphonate, prepared from the sulphonyl 
chloride and methyl alcohol, crystallises in rhombohedra, m. p. 74°. It 
yields a yellow, crystalline iododichloride, ICl2*CgH4'S03Me, which is 
converted by aqueous sodium carbonate into methyl -p-iodosobenzene- 
sulphonate, lO-CgH^-SOgMe (decomp. 176—178°); the iodosoacetate, 
I(OAc)2-CgH4'S03Me, forms rhombic prisms, m. p. 174°. Methyl 
p-iodoxybenzenesulphonate is prepared by the action of sodium 
hypochlorite and acetic acid on the iododichloride. 



i. 266 ABSTRACTS OF CHEMICAL PAPERS. 

p-Iodophenylethylsulphone, C^H^I'SOgEt, obtained as a white powder, 
m. p. 83°, by oxidising /?-iodothiophenetole with chromium trioxide 
in glacial acetic acid solution, yields an iododichloridey IClg'CgH^'SOgEt 
(decomp. 118°), which is converted by the usual methods into p-iodoso- 
pJvenyhthylsulphone (decomp. 235°), the iodosoacetate^ 

I(OAc)2-CeH4-S02Et, 
monoclinic needles, m. p. 167 — 170°, and p-iodoxyphenylethyhulphone, 
lOg'C^H^'SOgEt, which crystallises in small octahedra, exploding 
at 220°. 

p-Iododiphenyl sulphide, C^H^I'SPh, prepared from ;?-aminodiphenyl 
sulphide (Kehrmann and Bauer, Abstr., 1897, i, 27) by means of the 
diazo-reaction, crystallises in lustrous, white leaflets, m. p. 35°, 
b. p. 230°/ll mm. Attempts to prepare the iododichloride by the action 
of chlorine in chloroform solution yielded a yellow oil, which on 
exposure to air is transformed into p-iododiphenyl sulphoxide, 

CgHJ-SOPh, 
and i^-iododiphenyhulphone, CgH^I'SOgPh. The last-mentioned com- 
pound has also been prepared (1) by oxidation of jo-iododiphenyl 
sulphide with chromium trioxide in glacial acetic acid solution, and (2) 
by the interaction of /?-iodobenzenesulphonyl chloride and benzene in 
the presence of aluminium chloride. It crystallises in white needles, 
m. p. 141°, and forms an iododichloride, IClg'CgH^'SOgPh, rhombic 
crystals (decomp. 130°). n-Iodosodiphenylsulphone is a pale yellow 
powder (decomp. 210^); the iodosoacetate, I(OAc)2'CgH^'S02Ph, forms 
white needles (decomp. 195°) ; p-iodoxydiphenylsulphonej 

lOg-CgH^-SOgPh, 
crystallises in white leaflets, which explode at 220 — 223°. 

/?-Iododiphenylsulphoxide, prepared by oxidising a cold glacial acetic 
acid solution of jt?-iododiphenyl sulphide with aqueous chromic acid, 
forms large, white, rhombic crystals, m. p. 106°. F. B. 



lodosulphones and Their Derivatives with Multivalent 
Iodine. Conrad Willqerodt and Max Plocksties (/. pr. Ghem., 
1912, [ii], 85, 198—207). — p-Iodophenyl-p-tolyhulphone {i-iodoA'- 
methyldiphenylsulpJwne), CgH^Me'SOg'CgH^I, is prepared by the 
interaction of />iodobenzenesulphonyl . chloride and toluene in 
carbon disulphide solution in presence of aluminium chloride ; it 
crystallises in rhombs, m. p. 162°, and yields an iododichloride, which 
crystallises in slender, sulphur-yellow needles (decomp. 120°), and 
forms with pyridine an additive compound, 

CgH,Me-S02-CgH4-ICl2,2C5H6N, 
decomposing at 118—120°. 

4:-Iodo8ophenyl-p-tolylsulphone is a pale yellow powder (decomp. 
197°); the iodosoacetate, CgH4Me-S02-CgH^-I(OAc)2, crystallises in 
lustrous needles, decomposing at 180°. i-Iodoxyphenyl-p-tolylsiUphone, 
CgH^Me-SOg'CgH^-IOg, forms a white powder (decomp. 320°), and 
reacts with 4-iodosophenyl-/^tolylsulphone and silver oxide in the 
presence of water, yielding di-p-ii-toluenesulphonylphenyliodinium 
hydroxide, OH*I(CgH^*S02"CgH4Me)2, which was obtained only in 
aqueous solution, and forms a yellow iodide. 



i 



I 



ORGANIC CHEMISTRY. i. 257 



^-i-Toluenesulphonyldiphenyliodinium chloride, 
CgH^Me-SOg-CgH^-IPhCl, 
is obtained in aqueous solution by heating phenyl-f)-tolylsulphone- 
4'-iododichloride with mercury diphenyl and water at 50° ; the iodide 
(decomp. 132°) and platinichloride, slender, yellow needles (decomp. 
178°), are described. 

4:-Iododiphenylsulphone-i'-carhoxyliG acid, CgH^I •SOg'CgH^'COgH, 
prepared by the oxidation of 4-iodophenyl-/)-tolylsulphone with 
chromium trioxide in glacial acetic acid solution, crystallises in 
colourless, slender needles, m. p. 293°, and yields crystalline sodium 
and silver salts ; the iododichloride could not be obtained in a pure 
condition. 

Ethyl 4:-iododiphenylsulphone-4:'-carhoxylate, prepared by esterifying 
the preceding acid, crystallises in slender needles, m. p. 140° ; it yields 
a yellow, crystalline iododichloride, IClg'CgH^-SOg'CgH^'COgEt 
(decomp. 110°), which is converted by aqueous sodium carbonate into 
ethyl ^-iodosodiphenylsulphone-^'-carhoxylate, 

lO-CgH^-SOg-CgH^-COgEt, 
a pale yellow powder, decomposing at 235°. 

4:-Iodophenyl-''2-^-xylylsulphone, CgH^I'SOg'CgHgMcg, is obtained in 
quadrilateral prisms, m. p. 115°, by the interaction of jo-iodobenzene- 
sulphonyl chloride and ;?-xjlene in the presence of aluminium chloride. 
The iododichloride, iClg'CgH^'SOg'CgHgMeg, forms short, yellow 
needles (decomp. 138°) ; 4:-iodosophenyl-2-^-xylylsulphone is a pale 
yellow powder (decomp. 134°). 

2-^-Xylenesulphonyldiphenyliodinium, (2 : 5 - dimetliyldiphenylsulphone- 
i' -phenyliodinium) chloride, CgH3Me2*S02*CgH^'IPh*Cl, is obtained by 
the action of mercury diphenyl on the preceding iododichloride in 
chloroform solution ; the platinichloride (decomp. 182°) and iodide 
(decomp. 135°) are also described. F. B. 

4-Amino-l-naphthyl Mercaptan. Theodor Zincke and Feanz 
ScHUTz {Ber., 1912, 45, 471 — 483). — 4:-Amino-l-naphthyl mercaptan, 
NHg'OjQHg'SH, m. p. 91 — 93°, yellow needles, is obtained by reducing 
4-acetylamino-l-naphthalenesulphonyl chloride by alcohol, concentrated 
hydrochloric acid and zinc, and hydrolysing the resulting acetylamino- 
naphthyl mercaptan by alcohol and hydrochloric acid. The hydro- 
chloride, sulphate, acetyl derivative, m. p. 173°, and diacetyl derivative, 
m. p. 152°, are described. With alcoholic benzaldehyde, it forms the 
henzylidene derivative, CHPh(S-CioHg-N:CHPh)2, m. p. 68°, yellow 
powder, in which the benzylidene group attached to the sulphur atoms 
is hydrolysed by alkalis, and those attached to nitrogen by acids. The 
disulphide, ^^[G-^^QRQ'l^'H.^lif ^- P- 168°, is obtained by oxidisiug the 
amino-mercaptan with 30% hydrogen peroxide in alcoholic or alkaline 
solution. It forms a diacetyl derivative, m. p. 265°, yellow needles, 
which is also obtained by the oxidation of the acetylaminonaphthyl 
mercaptan. 

When a suspension of 4-acetylamino-l-naphthyl mercaptan in chloro- 
form or carbon disulphide is treated in a freezing mixture with chlorine 
(1 mol.), the preceding disulphide is first formed, and then changes 
to i-acetylamino-l-chlorothiolnaphthaleney NHAcCioHg'SCl, a yellow 



i. 268 ABSTRACTS OF CHEMICAL PAPERS. 

powder, which forms intensely yellow solutions, and is very reactive 
(compare Abstr., 1911, i, 368), yielding the diBulphide with alcohol 
or formic or acetic acid, and 4:-acetylaminol-acetoiiyUhiolnaphthalene, 
NHAc-CioH^'S-CHg-COMe, m. p. 155—160° white crystals, with 
acetone ; the last compound is also obtained from chloroacetone and 
acetylaminoDaphthyl mercaptan in dilute sodium hydroxide. 4:-Acett/l- 
aviino-l-bromothiolnaphthalene, NHAc*CjoHg*SBr, is obtained in a 
similar manner ; it can only be isolated in the form of the hydrobrojuide, 
a yellow powder. An excess of bromine converts 4-acetylamino- 
1-naphthyl mercaptan in chloroform into \-hromo-^-acetylaminonaphtJia- 
lene hydroh'omide, CioHgBr»NHAc,HBr, m. p. 205° (decomp.), 
straw-yellow needles. 

4rAcetylaniino-l-7iaphthyl methyl stUphidef NHAcCjoHg'SMe, m. p. 
193°, yellow needles, is obtained by shaking methyl sulphate and 
4-acetylamino-l-naphthyl mercaptan in a slight excess of 10% sodium 
hydroxide. By hydrolysis with alcohol and concentrated hydrochloric 
acid, it yields ^-amino-\-naphthyl methyl sulphide hydrochloride^ 

NH2-CioH6-SMe,HCl, 
white needles, from which the free base, CnHj^NS, m. p. 54°, is 
obtained. The base is sensitive to oxidising agents, forms solutions 
with blue fluorescence, reacts with beczaldehyde in alcohol to give 
^-benzylideneamino-a-naphthyl methyl sulphide, SMe'CjQHR'NiC-H-Ph, 
m. p. 56°, yellow needles (which forms an intensely red salt with 
hydrogen chloride in ether), and yields by methylation 4i-dimethyl- 
amino-l-naphthyl methyl sulphide, NMeg'CjoHg'SMe, b. p. 199°/ 
16 — 17 mm. {hydriodide, decomp. 171 — 173°). 

4-Acetylamino-l-naphthyl methyl sulphide reacts with bromine in 
acetic acid to form a dibromide (impure), CigHjgONSBrg, m. p. 157° 
(decomp.), a dark red, crystalline powder, which is converted by 
boiling glacial acetic acid into the acetyl derivative, m. p. 232°, white 
needles, of 3-brom^-i-amino-l-naphthyl methyl sulphide, 

NHg-CioH^Br-SMe, 
m. p. 138°, colourlegs needles. By oxidation in glacial acetic acid 
with 30% hydrogen peroxide and hydrolysis of the product by alcoholic 
potassium hydroxide at 100°, 4-acetylamino-l-naphthyl methyl sulphide 
yields the sulphoxide, NHg'CjoHg'SO'CHg, m. p. 171 — 172°, colourless 
crystals {acetyl derivative, m. p. 183 — 184°; a hydrate^ 

Ci3Hj302NS,iH20, 
m. p. 109 — 111°, has also been obtained), the salts of which, unlike 
those of the parent sulphide, are only slightly hydiolytically dis- 
sociated. The sulphoxide reacts with hydrogen bromide in chloroform 
to form the preceding red dibromide, and its acetyl derivative is 
oxidised by an excess of hydrogen peroxide to the corresponding 
aW/^/ionejJSHAc'C^QHg'SOgMe, m. p. 236°, the hydrolysis of which yields 
4:-amino-l-naphthylmethylsulphone, NHg'CjoHg'SOgMe, m. p. 175° 
(hydrochloride, decomp. about 247°). By warming its solution in 
acetic acid with a little concentrated hydrochloric acid, 4-amino-l- 
naphthylmethylsulphoxide is converted into the hydrochloride of 
3-diloro-iamino-l-?iaphthyl methyl sulphide, NHo'CjoHgCl'SMe, m. p. 
71°. C. S. 



ORGANIC CHEMISTRY. i. 259 

Trimethylene [cycZoPropane] Derivatives of the Type 

^29>CHX. Louis Michiels {BvZl. Acad, roy. Belg., 1912, 10—34. 

Compare Abstr., 1901, 1,581; 1902,1, 525; 1911,1,62, 459).— A number 
of ketones, containing the c?/c?opropyl group, have been prepared, and 
from these the corresponding secondary alcohols have been obtained. 
Methylisopropylcarbinol has, In particular, been studied with regard 
to its behaviour towards hydrogen bromide. In the second half of the 
paper the author considers the physical properties of the c?/c^opropane 
derivatives as compared with those of the corresponding aliphatic 
compounds. 

cjcloPropylmethylcarbinol, ^ i^CH-CHMe'OH, is obtained by 

the reduction of cyc^opropylmethyl ketone with sodium and dry alcohol 
as a viscous, colourless liquid, b. p. 119—120°, Df 0-88045, < 1-42461. 
With hydrogen chloride it readily yields the corresponding chloride^ 
b. p. 105 — IO6775O mm., and with hydrogen bromide, in the cold, the 
bromide, a colourless, mobile liquid, b. p. 118—1207751 mm., Df M552. 
From the bromide by the further action of hydrogen bromide, or from 
the original carbinol by the action of concentrated hydrobromic acid, 
a dibromlde is obtained, the trimethylene ring being opened, which is 
probably y-pentylene dibromlde (compare Llpp, Abstr., 1890, 20). 

cycloProp2/^isoam2/ZZ;e«one,CHMe2-[CH2]2-CO-CH<^ I ^, a colourless 

liquid with an odour of mint, is obtained by the action of magnesium 
^soamyl bromide on C2/c?opropanecarboxylonitrile, the additive product 
being decomposed by water and acid. It has b. p. 183 — 185°/755 mm., 
Df 0-87408, wg* 1-44064 ; and yields & semicarbazone, m. p. 140—141°. 
On reduction with sodium and alcohol, cyciopo'opylisoamylcarbinol is 
formed as a colourless, viscous liquid with a citron-like odour, b. p. 
188— 189°/766 mm., Df 0-8631, n^' 1'44405. 

OH 
cycloPropyl isohexyl ketone, CHMeg-rCHglg'CO'CH^i^, results 

from the interaction of magnesium isohexyl bromide and ethylene- 
acetonitrile. It is a colourless, mobile liquid, with an odour of mint, 
b. p. 200—2027739 mm., Df 0-8631, n^ 1-44325; on reduction it 
yields the carbinol^ a colourless, viscous liquid, with a citron-like 
odour, b. p. 206— 2077747 mm., Df 0-8603, < 1-44345. 

H C CH 

cycloFropylacetylcyclopropanef ^ i '>CH*C0*CH2*CH<^ i ^ is pre- 

pared by the interaction of magnesium c^/cZopropylcarbinyl bromide and 
c^/cZopropanecarboxylonltrlle as a colourless, mobile liquid, b. p. 
175— 177°/759 mm., Df 0-9149, n^ 1-45787, which yields a semi- 
carbazone, m. p. 82 — 83°. On reduction it gives the corresponding 
dicyclopropylethanol, C3H./CH(OH)-CH./C3H5, b. p. 179—1807 
770 mm., Df 0-9054, < 1-46036. This with hydrogen bromide 
gives a bromide, Df 1*585, in which only one of the c'2/c?opropane 
groups has been opened. 



i. 260 ABSTRACTS OP CHEMICAL PAPERS. 

The following secondary alcohols were prepared for comparison as 
regard their physical properties. 

ISO Propi/lii<obuti/lcarbinolf CHMe2*CH(OH)'CH2'CHMe2, is formed 
by the interaction of magnesium isobutyl bromide and i iao- 
butaldehyde, and subsequent treatment with water and acid. It 
is a colourless, viscous liquid, smelling of thyme, b. p. 157 — 158°, 
Df 0-8212, n^ 1-42461. 

isoPropylisoamylcarhinoly CHMe2'CH(OH)*[CH2]2*CHMe2, is simi- 
larly prepared, and is a colourless, viscous liquid with an odour of 
balm, b. p. 175°, Df 0-8212, < 1-42461. 

isoPropylisoIiexi/lcarbinol is a similar substance, b. p. 193 — 194/ 
756 mm., Df 0-8152, 7ir" 1-43021. 

A comparison of the boiling points of the ketones indicates that 

the loss of two hydrogen atoms accompanying the conversion of 

CH CH 

p^^^C into y ^^C produces in the case of the methyl-, ethyl-, 

and w-propyl- an increase of 19 — 20°, and for the isopropyl-, iso- 

butyl-, and isoamyl- an increase of 13 — 15°. The replacement of a 

CH CH 

second ^>CH- by i ^>CH- brings about a further rise of 14°. 

. ? 2 

Similar differences are shown by the alcohols. 

A study of the densities of the alcohols of the two series shows that, 
on an average, the density of an alcohol of the cyc^opropyl series is 
higher than that of the corresponding aliphatic alcohol by 0-043, and 
that this value is doubled by the introduction of another c^c^opropyl 
group. The molecular refractions of the numerous c?/c^opropane 
derivatives containing one cyc^opropyl group show on an average 
that the value found is higher than that calculated by 74 (compare 
Demjanoff, Abstr., 1907, i, 1032, who gave 66). W. G. 

Method for Preparing Aromatic Alcohols. Gustave Vavon 
CompL rend., 1912, 164, 359— 361).— The reduction of aldehydes to 
alcohols by the ordinary method, employing sodium amalgam, gives 
yields not exceeding 50%. A theoretical yield is secured, however, by 
dissolving the aldehyde in a suitable solvent, adding a few grams of 
platinum black (prepared by the action of formaldehyde in alkaline 
solution on platinic chloride), and submitting it to the action of 
hydrogen under a pressure of about one atmosphere. Successful 
application to a number of aromatic aldehydes of varied types shows 
that the reaction is a general one. W. 0. W. 

Betuhn. I. K. Traubenbeeg (/. Euss. Phys. Chem. Soc, 1912, 
44, 132 — 138). — The author's investigations on betulin (compare 
Hausmann, Abstr., 1877, i, 94 ; Franchimont and Wigman, Abstr., 
1879, 468), which include the determination of the molecular weight 
in boiling chloroform by Landsberger's method and in freezing 
benzene and also the preparation and analysis of the diacetyl and 
dibenzoyl derivatives, indicate that betulin has the formula 

^24^33(^^)2' 
and that it belongs, together with onocol, arnidiol, and faradiol to a 

group of dextrorotatory dihydric phytosterols. 



ORGANIC CHEMISTRY. i. 261 

Betulin, m. p. 251°, [a]i, +15*68°, gives a number of colour reactions 
similar to those for cholesterol. Its diacetyl compound has 
[aju + 14*26°, and its dibenzoyl derivative, C24H38O2BZ2, has m. p. 
145 — 147°. When oxidised by means of alkaline permanganate, 
betulin yields acetic acid and a solid acid which was not investigated, 
whilst with chromic acid it gives a ketone^ Gg^HggOg, crystallising in 
prisms, m. p. 177°, and yielding a phenylhydrazone^ 024^380* NgHPh, 
m. p. 130°. T. H. P. 

Preparation and Estimation of Tyrosine and Glutamic 
Acid. Emil Abderhalden {Zeitsch. physiol. Ghem., 1912, 77, 
75 — 76). — Tyrosine can be prep^ared from silk by the simple method 
of hydrolysing with hydrochloric acid ; the acid is removed by 
evaporation, and then by the addition of sodium hydroxide ; tyrosine 
then crystallises out from the hot aqueous solution. The yield, 
however, is not quantitative, and the mother liquor is not available 
for the separation of other amino-acids. These two disadvantages can 
be overcome in the following way. After hydrolysing with hydro- 
chloric acid, the product is evaporated under reduced pressure to 
dryness ; the residue is dissolved in water, and a stream of ammonia 
passed through the solution. It is then again evaporated to dryness, 
and the residue treated with cold water; tyrosine is left undissolved, 
or the whole residue may be boiled with water and animal charcoal j 
from the filtrate pure tyrosine crystallises out quantitatively. The 
mother liquor is again evaporated to dryness, and the residue treated 
by the ester method for the other mono-amino-acids. The method 
serves for the estimation of tyrosine, etc., in like products of hydrolysis. 

Glutamic acid may be prepared from its hydrochloride by passing 
ammonia through the solution and then evaporating to dryness. 
The deposit is dissolved in hot water and recrystallised ; the main 
amount of glutamic acid can be separated by fractional crystallisation, 
and the remainder can be obtained by precipitation with alcohol. 

W. D. H. 

[Di-iodotyrosine.] A Correction. Adolf Oswald {Zeitsch. 
physiol Chem.y 1912, 76, 499— 500).— Polemical (compare Abder- 
halden and Hirscb, Abstr., 1911, ii, 1119). E. F. A. 

Melting Point of 3 : 5- Di-iodotyrosine. Emil Abderhalden 
{Zeitsch, physiol. Chem., 1912, 77, 183— 184).— Polemical. A reply to 
Oswald (preceding abstract). W. D. H. 

Action of Hydrogen Sulphide on Imino-ethers. II. 
Formation of Tiaion Esters and Acids. Motooki Matsui 
{Mem. Roll. Sci. Eng. Kyoto, 1912, 3, 247—255. Compare Abstr., 
1909, i, 463). — When hydrogen sulphide is passed into an ethereal 
solution of an imino-ether, a thion ester is produced, which ulti- 
mately reacts with the liberated ammonia with the formation of a 
thioamide. In alcoholic solution, however, ammonia decomposes 
thion esters with the formation of imino-ethers, hydroxylamine 
having a similar action. 

VOL. CII. i. t 



i. 262 ABSTRACTS OF CHEMICAL PAPERS. 

By saponifying thion esters with cold alkali, it has been found 
possible to prepare the corresponding acids. Thion-fatty acids are 
volatile, pale yellow liquids, having a strong penetrating odour 
resembling that of acetic acid and a very acidic reaction ; thion- 
arouiatic acids are yellow, solid substances of characteristic odour. 
All are unstable, decomposing even in ethereal solution in the course 
of a few days. They show a marked difference from ordinary mono- 
carboxylic acids, in that their silver and lead salts remain in the 
ethereal layer when an ethereal solution of the acid is shaken with an 
aqueous solution of silver nitrate or lead acetate. Silver salts of 
thion-fatty acids are very unstable, readily changing into silver 
sulphide, whilst those of the aromatic acids are comparatively stable 
at the ordinary temperature. 

Ethyl thionbenzoate {loc. cit.) is a yellow liquid of b. p. 181°/ 
360 mm. When its alcoholic solution is treated with ammonia, it 
yields ethyl iminobenzoate, whilst in ethereal solution, thiobenzamide 
is formed. Hydroxy lamine reacts with an alcoholic solution of the 
ester, yielding a mixture of a- and /J-ethylbenzhydroxamic acids. 

Methyl thionbenzoate resembles the ethyl ester. It has b. p. 
195—1977320 mm. 

Methyl thionacetate has b. p. 85 — 90^; methyl thionp'opionate has 
b. p. 110—115°. 

Mhyl thion-p-toluate is a yellow oil, b. p. 205— 207°/260 mm., 
m. p. about 1°. 

Thionhenzoic acid was prepared by hydrolysing ethyl thion- 
benzoate with cold sodium hydroxide. Its silver^ lead, and barium 
salts were examined. Thion-p-toluic acid was similarly prepared, but 
in quantity insufficient for complete characterisation. IVtionacetic 
acid could not be obtained free from ether, but has b. p. about 37°. 
The similar thionpropionic acid was also prepared, and its lead salt 
was investigated. H. W. 

Terpenes and Ethereal Oils. CVIII. Otto Wallach 
{AniuUen^ 1912f 388, 49 — 62). — Semmler's method of preparing 
tanacetophorone by the di^tillation of salts of tauacetonedicarboxylic 
acid is unsatisfactory with regard to yield and purity of product. 
A very convenient process is the following : Methyl a-tanacetonedi- 

cario^ylau, CH.<9™^r^^^^^, b. p. 244-247° or 126-127°/ 

13 mm., D20 1-0535, n^ 1-4506, [a]i> 142-5°, obtained from the acid, 
methyl alcohol, and hydrogen chloride, forms with sodium in methyl 
alcohol a yellow, crystalline compound, CjoHj303Na,H20, which 
develops a violet coloration with ferric chloride, yields impure 
tanacetophoronesemicarbazone with aqueous semicarbazide hydro- 
chloride, and is converted into tanacetophorone by the successive 
operations of boiling its aqueous solution, acidifying with sulphuric 
acid, and distillation with steam. The transformations in the 
preparation of the ketone are probably as follows. Methyl a-tan- 
acetonedicarboxylate — > methyl /3-tanacetonedicarboxylate, 

p„ ^CHg-CO^Me _^ 

^"a^cPr^ICH-COaMe* ~^ 



ORGANIC CHEMISTRY. i. ^63 

methyl l-wopropyl-A'-ci/c?openten-3-one-2-carboxylate, 

CH^-CO 

^,, .CH=C-ONa ^ ^ 

sodium derivative, CH2<^pp o.A.p/-v T^r > — > tanacetophorone, 

OH ^CH=C-OH _^ ' ^CH,-90 

The preceding constitution of the sodium compound is supported 
by the fact that the substance, dissolved in water saturated with 
carbon dioxide, is converted into dihydrotanacetophorone (l-iso- 
propylc2/c^opentan-3-one) by treatment with hydrogen and colloidal 
palladium, and subsequent acidification and distillation with steam. 

[With Frederik Challenger]. — l-isoPropylc?/c^opentan-3-one, b. p. 
188—189°, D21 0-90U0, < 1-4428 (compare Abstr., 1911, i, 472), 
forms a dihenzylidene derivative, m. p. 134 — 135°, yellow needles, 
and reacts with magnesium methyl iodide to yield ultimately 
i-l-methyl-S-isopropylcyclopsntan-l-oly CgHjgO, b. p. 185 — 186°, m. p. 
43 — 44°, which apparently is the inactive modification of the tertiary 
alcohol obtained by the action of nitrous acid on fenchylamine (Abstr., 
1911, i, 311); by dehydration with oxalic acid, it yields a hydro- 
carbon, CgH^g, b. p. 142—144°, D20 0'7970, n^ 1-4418, which is almost 
identical in chemical and physical properties with that described 
previously (loc. cit). C. S. 

The Ethyl Ester of Naphthalic Acid. Wilhelm Wisltcenus 
and Otto Penndorf {Be7\, 1912, 46, 410 — 411). — Naphthalic acid 
cannot be esterified directly. The diethyl ester described recently by 
Errera (Abstr., 1911, i, 465) had already been prepared by the authors 
by the action of ethyl iodide on silver naphthalate ; it has m. p. 59 — 60° 
and b. p. 238 — 239°/ 19 mm. ; the solution in strong sulphuric acid shows 
a blue fluorescence. D. F. T. 

Methylamino- and Other Derivatives of Terephthalic Acid. 
Rudolf Wegscheider, Franz Faltis, Siegmund Black, and Oskar 
HupPERT {Monatsh.y 1912,93, 141 — 168). — The object of the investiga- 
tion was a convenient method for the preparation of meth 1- and 
dimethyl-ammoterephthalic acids. 

Aminoterephthalic acid was obtained by successive nitration and 
reduction of terephthalic acid ; the corresponding methyl ester was 
obtained by esterification of the acid, and also by the reduction of the 
methyl ester of nitroterephthalic acid ; the last-named substance can 
be prepared by careful nitration of the methyl terephthalate, as well 
as by esterification of nitroterephthalic acid. 

The methyl ester of acetylaminoterephthalic acid (compare Cahn- 
Speyer, Abstr., 1907, i, 849) is obtained by simple acetylation with 
acetic anhydride ; the alcoholic mother liquors from the recrystallisation 
of this substance contain methyl diacetyiaminoterephthalate, which is 
also obtainable by the further acetylation of the monoacetyl compound ; 
the crystals of the substance, m. p. 74 — 76°, belong to the triclinic 
system [a: 6: = 0-5240:1:0-7912; a = 91°12, )8 = 85°22', y = 96°19'] ; 
water hydrolyses the substance into the monoacetyl compound. 

1^^ t 2 



i. 264 ABSTRACTS OF CHEMICAL PAPERS. 

Methylaminoterephthalic acid is best prepared by the action of 
methyl sulphate on aminoterephthalic acid in the presence of barium 
carbonate ; it has m. p. 2? 3*5 — 274*5° (corr.) (compare Cahn-Speyer, 
loc. cil.) ; the solutions show a blue fluorescence. When the methyl- 
alcoholic solution is treated with hydrogen chloride at room tempera- 
ture, i-melhyl \-hydrogen 2-vielhylaminoterephthalale separates, m. p. 
186'5 — 187° (corr.). The corresponding dhnethyl ester was also obtained 
by esterification as an impure, dark yellow solid, m. p. 86*5 — 90° 

Acetylmethylaminoterephthalic acid was not obtainable by methyl- 
ating the acetylamino-acid with methyl sulphate, but was successfully 
prepared by acetylating the methylamino-acid ; it crystallises in crusts, 
the m. p. of which, 216 — 2165°, is much below that given by Cahn- 
Speyer ; it is colourless and does not give fluorescent solutions. The 
acetyl group is removed by the action of dilute potassium hydroxide 
solution. 

Methyl acetylmethylaminotere^Mialate, obtained by the action of 
potassium and methyl iodide on a benzene solution of the methyl 
acetylaminoterephthalate, has m. p. 78 — 80°; the acetyl group is 
hydrolyfcd off by heating with water. 

Dimethylaminoterephthalic acid is best prepared by energetic methyl- 
ation of aminoterephthalic acid with methyl sulphate in the presence of 
barium carbonate ; it is a white, crystalline solid, m. p. 281° (corr. ; 
decomp.). The dimethyl ester, obtained from the acid by esterification in 
the usual way, crystallises in needles belonging to the triclinic system 
[a'.h'.c=^ 0-7920 : 1 : 08327 ; a = 82°21', p = 94°14', y = 104°50'], 
m. p. 68—69°. D. F. T. 

Reduction of Acids with Several Double Bonds by Paal's 
Method. Waltheu Borsche {Ber., 1912,45, 620— 625).— Unsaturated 
acids when shaken with hydrogen and colloidal platinum are readily 
converted into the saturated substances. 

Cinnamylideneacetic acid, CHPhlCH-CHICH-COgH, yields phenyl- 
valeric acid. Cinnamylidenemalonic acid, CHPhICH*CHIC(C02H)2, 
gives (o-phenyl-n-propylmaloiiic acid, crystallising in colourless platelets, 
m. p. 98°. When heated, carbon dioxide is eliminated and 8-phenyl- 
valeric acid obtained ; this is the most convenient method for its 
preparation. 

Methyl ui-phenylpropylmalonate, formed by reduction of methyl 
cinnamylidenemalonate, is a colourless oil, b. p. 183 — 184°/10mm. 

a-Cyano-h-phenylvaleric acid, prepared by reduction of a-cyano- 
cinnamylideneacetic acid, is obtained as an oil, which on distillation is 
converted into 8-phenylvaleronitrile. 

The ethyl ester of a-cyano-8-phenylvaleric acid is a colourless oil, 
b. p. 192— 193°/11 mm. 

a8 - Diphenylvaleric acid, CH2Ph-CH2-CH2-CHPh-C02H, from 
a-phenylcinnamylideneacetic acid, crystallises in bunches of colourless 
needles, m. p. 80 — 81° (compare Rupe and Liechtenhan, Abstr., 1909, 
i, 927). 

ah-Diphenylvaleronitrile from cinnamylidenephenylacetonitrile forms 
large, transparent crystals with lustrotis faces, m. p. 79°; it distils 
without decomposition. E. F. A. 



ORGANIC CHEMISTRY. i. 265 



r 

m Syntheses in the Fatty Aromatic Series. III. [Amino- 
■acids, Nitrocompounds, Aldehydes.] Julius von Braun and 
0. Kruber {JBer., 1912, 46, 384—402. Compare Abstr., 1911, 
i, 968 ; 1910, i, 843). — The authors have attempted in several ways to 
prepare the series of aldehydes corresponding with the series of 
alcohols already described in the earlier papers ; the most satisfactory 
source for the aldehydes proves to be the primary nitro-compounds. 

Various phenyl substituted amino-acids were obtained by applying 
the malonio ester synthesis as described by the series of changes : 
CHoPh-[CH2]^-Br — > CH2Ph-[CH2]^-CH-(C02H)2 -> 

CH2Ph-[CH2]a;-CHBr-CO,H -^ CH2Ph-[CH2]a,-CH(NH2)-C02H. 
S-Fhenylpropylmalonic acid, CH2Ph*[CH2]2*CH(C02H)2, m. p. 94° is 
obtained by hydrolysis of the ethyl ester, a colourless oil, b. p. 
189 — 194°/13 mm. On distillation under reduced pressure, it loses 
carbon dioxide with the formation of 8-phenylvaleric acid. Bromina- 
tion in ethereal solution yields a-bromo-8-phenylpropylmalonic acid, 
m. p. 135 — 136°; this when heated above its m. p. loses carbon 
dioxide and forms a-hromo-8-phenylvaleric acid, 

CH2Ph-[CH2]2-CHBr-C02H, 
m. p. 85°, b. p. 195 — 210°/15 mm. ; the same substance is obtained in 
a less pure condition by brominating 8-phenylvaleric acid. If the 
bromo-acid is heated with a concentrated aqueous solution of ammonia, 
there is obtained a-amino-h-phenylvaleric acid, m. p. 203 — 206°; the 
copper salt was prepared, also the P-naphthalenesulphonyl derivative, 
m. p. 83°. 

e-Phenylhutylmalonic acid, CH2Ph'[CH2]3*CH(C02H)2, needles, 
m. p. 111°, is obtained by hydrolysis of the ethyl ester, b. p. 
215 — 218°/11 mm.; bromination gives a-bromo-e-phenylhutylmalonic acid, 
m. p. 123 — 124° (decomp.), which on heating yields a-bromo-e-phenyl- 
hexoic acid, a yellow oil, b. p. 210 — 230°/12 mm., which would not 
crystallise ; the preparation of this last substance by bromination of 
€-phenylhexoic acid is again unsatisfactory. When heated with 
aqueous solution of ammonia, the bromo-acid is converted into 
a-amino-i-phenylhexoic acidy white, leafy crystals, m. p. 237 — 242° 
(decomp.) ; the copper salt and the ^-naphthalenesulphonyl derivative, 
m. p. 112 — 113°, were prepared. 

The above amino-acids failed to supply the desired easy passage to 
the required aldehydes. 

Phenylbutyronitrile, CH2Ph*[CH2]2*CN, when treated in alcoholic 
solution with dry hydrogen chloride yields the hydrochloride of 
phenylbutyrimido-ether, CH2Ph-[CH2]2-C(:NH)-OEt,HCl, which by the 
action of aniline in alcoholic solution is converted into the correspond- 
ing diphenylamidine compound, CH2Ph-[CH2]2-C(:NPh)-NHPh, a white, 
crystaUine solid, m. p. 81 — 82°. Reduction of this compound by 
sodium and alcohol yields a non-volatile, viscous oil, probably 
diS-anilino-a-phenylbutane, CH2Ph-[CH2]2*CH(NHPh)2, which on 
hydrolysis yields only a few drops of 8-phenylbutaldehyde (compare 
Merhng, Abstr., 1908, i, 653). 

If phenylpropyl bromide is allowed to react with magnesium and 
then with ethyl orthoformate, the expected phenylbutaldehyde 
diethyl acetaly CH2Ph-[CH2]2-CH(OEt)2, is obtained ; it is, however, 



i. 266 ABSTRACTS OF CHEMICAL PAPERS. 

much decomposed during distillation (b. p. about 200°/20 mm.) ; 
hydrolysis gives a very poor yield of the aldehyde. Phenyl butyl 
bromide, magnesium and ethyl orthoformate yield no better result 
(compare Tsuhitschibabin, Abstr., 1904, i, 221 ; Bodroux, Abstr., 
1904, i, 421). 

The reaction of magnesium phenyl propyl bromide and formomethyl- 
anilide gives no trace of phenylbutaldehyde (compare Houben and 
Diischer, Abstr., 1908, i, 27), whilst the action of sodium hypochlorite 
on a hot aqueous solution of a-amino-8- phenyl valeric acid or a-amino-€- 
phenylhexoic acid yields small quantities of 8-phenylbutaldehyde and 
€-phenylvaleraldehyde respectively (compare Langheld, Abstr., 1909, 
i, 138). 

The desired aldehydes were satisfactorily obtained by starting with 
the primary nitro-compounds, which by reduction are convertible into 
the aldoximes (Konowaloff, Abstr., 1899, i, 733). 

The interaction of y-phenylpropyl iodide and silver nitrite produced 
y-phenylpropyl nitrite, b. p. 115 — 125°/14 mm., and y-nitro-a-phenyl- 
pi'opane, a colourless, inodoi'ous oil, b. p. 147 — 148°/ll mm. ; the latter 
on treatment with bromine in aqueous solution gives oily di-y-bromo- 
ynitro-a-phenylp'opane, CHgPh'CHglCBrg'NOg, whilst witb a diazonium 
.salt it yields anitro-yphenylpropald'ihydephenylhydrazone^ small, red 
needle crystals, m. p. 133 — 134° ; the a-phenylpropanenitrolic acid has 
m. p. 75°. If the sodium compound of nitrophenylpropane is reduced 
in aqueous solution by stannous chloride, there is obtained y-phenyl- 
propaldoxime, m. p. 93 — 94° ; this on hydrolysis yields -y-phenylprop- 
aldehyde, Ph-[CH2]2-CHO, b.p. 110—1 13°/16 mm. (compare Fischer and 
Hoffa, Abstr., 1898, i, 659); the diphenylmetJianedimethyldihydrazone, 
CH2[C6H,-NMe-N:CH-CH2-CH2Ph]2, has m. p. 99—100° 

h-Nitro-a-phenylbutane (together with S-phenylbutyl nitrite, b. p. 
125 — 130°/ 15 mm.) is obtained similarly to the corresponding propane 
derivative as a colourless oil of feeble odour, b. p. 160 — 165°/15 mm. ; 
reduction of the sodium salt in aqueous solution and subsequent 
hydrolysis yields S-phenylbutaldehyde, CH2Ph'[CH2]2'CHO, b. p. 
129 — 131°/17 mm.; the semicarbazone has m. p. 104 — 105°; the 
phenylhydrazo'iie is an oil ; the diphenylmethanedi7n*'.thyldihydrazone 
crystallises very slowly; the methyl acetal has b. p. 121 — 124°/9 mm. 

€-Nitro-aphe7iylpentane is a colourless, inodorous liquid, b. p. 
161 — 166°/9 mm., whilst the isomeric e-phenylamyl nitrite has b. p. 
130 — 135°/10 mm. The c^iirowio-derivative of the phenylnitropentane is 
a yellow oil ; the nitrolic acid derivative and the product of coupling 
with a diazonium salt also show little tendency to crystallise. 
Reduction and subsequent hydrolysis of the nitrocompound yield 
e-phenyln-valeraldehyde, CH2Ph*[CH2]3'CHO, as an oil, b. p. 
129 — 131°/10 mm., strongly resembling citral in odour; the methyl 
acetal, b. p. 136 — 139°/ 11 mm., has only a faint ethereal odour. The 
oxime, semicarbazone, phenyihydrazone, and diphenylmethanedimethyl- 
dihydrazone are oily ; the p-nitrophenylhydrazone slowly gives a solid, 
m. p. 82—84°. 

i^-Nitro-a-phenylhexane has b. p. 174 — 178°/11 mm., whilst the 
isomeric j^-phenylhexyl nitrite has b. p. 143 — 148°/11 mm. The nitro- 



r 



ORGANIC CHEMISTRY. i. 267 



compound is easily converted into S^-phenylhexaldehydej 

CH2Ph-[CH2]4-CHO, 
b. p. 141 — 144°/9 mm., of feeble and not unpleasant odour; the 
substance offers considerable resistance to satisfactory analysis by 
combustion. 

-q-Nitro-a-phenylheptane has b. p. 182 — 186°/10 mm., and the isomeric 
•q-phenylheptyl nitrite, b. p. 164 — 166°/13 mm. The nitro-compound is 
convertible by the general process into -q-phenylheptaldehydey 

CH2Ph-[CH2]5-CHO, 
b. p. 155 — 159°/9 mm., which like the lower aldehyde offers resistance 
to satisfactory combustion ; it has a feeble odour. The ^-nitrophenyl- 
hydrazone is a brown powder, m. p. 68 — 70°. 

The above series of aldehydes, with the striking exception of 
8-phenylvaleraldehyde, show a gradual weakening of the odour with 
increase in the length of the carbon chain ; this is io marked contrast 
to the oscillatory effect observed with the corresponding series of 
alcohols. D. F. T. 

Combination of Phenolcarboxylic Acids. Ferdinand Mauthner 
(/. pr. Ghent., 1912, [ii], 85, 308— 314).— An isomeride of the 
previously- described 3:4:5:2': 6'-pentamethyl ether of methyl 
digallate (Abstr., 1911, i, 725) has been synthesised by condensing 
3 : 4 :5-triraethoxybeDzoyl chloride with methyl 5-hydroxy-3 : 4- 
dimethoxybenzoate. The condensation was effected by shaking the 
ester in aqueous sodium hydroxide solution with an ethereal solution 
of the acid chloride. 

Methyl 5 -(3' : 4' : b')-trimethoxybenzoyloxy-S : 4:-dimethoxybenzoate, 
CgH2(6Me)3-C02-CgH2(OMe)2-C02Me, thus obtained crystallises in 
colourless needles, m. p. 127 — 128°, and is the completely methylated 
derivative of the digallic acid isolated by Nierenstein (Abstr., 1910, 
i, 265) from tannin. 

The following compounds were prepared in a similar manner : 

Methyl p-3 : 4 : b-trirmthoxyhenzoyloxyhenzoate, CjgH^gO^, obtained 
from 3:4: 5 -trimethoxy benzoyl chloride and methyl jt?-hydroxy- 
benzoate, has m. p. 109 — 110°. 

Methyl 4:-{3' -A' •.b')-trimethoxyhenzoyloxy-Z-methoxyhenzoate, Q^^H^fi^, 
prepared from 3:4: 5 -trimethoxy benzoyl chloride and methyl 
vanillate, forms colourless needles, m. p. 131 — 132°. 

Methyl ^-i-methoxyhenzoyloxyhenzoate, CjgHj^Og, obtained from 
anisoyl chloride and methyl ;?-hydroxybenzoate, crystallises in 
colourless needles, m. p. 146 — 147°. 

Methyl 4:-veratroyloxy'3-methoxybenzoate, Cj^HjgO^, from veratroyl 
chloride and methyl vanillate, has m. p. 128 — 129°. 

Methyl ip-vtratroyloxybenzoate, C^^H-^fi^, forms colourless needles, 
m. p. 148—149°. F. B. 

Mechanism of Cannizzaro's Reaction. VetcheslIv E. 
TisTSHENKO, I. F. Veltsa, and I. L. Rabtsevitsch-Zubkovsky (J. Russ. 
Phys. Chem. Soc, 1912,44, 138— 151).--According to Claisen (Abstr., 
1887, 574), when a sodium alkyioxide is heated in alcoholic solution 



i 



i. 268 ABSTRACTS OF CHEMICAL PAPERS. 

with benzaldehyde, a voluminous, white precipitate is formed, which is 
decomposed by water into benzyl alcohol and sodium benzoate, or by 
acetic acid into benzyl benzoate and alkyl benzoate ; he regarded this 
precipitate as an intermediate compound formed according to the 
equation : 

/O-CHgPh 
2Ph-CH0 + R-ONa = CPh^OR 

\ONa 
The authors have investigated this reaction under various con- 
ditions, and in all cases find the precipitate formed to consist simply 
of sodium benzoate. As has been previously asserted (Abstr., 1907, 
i, 282), Claisen's explanation must be abandoned. T. H. P. 

The Action of Solutions of Ethoxides on m-Nitrobenzylidene 
Chloride. Alfred Kliegl (Verh. Ges. deut. NaiurforscU. Aerzte, 1912, 
ii, [1], 226—228. Compare Kliegl and Haas, Abstr,, 1911, i, 433).— 
m-Nitrobenzylidene chloride yields with solutions of ethoxides the 
acetal of 7?i-nitrober)Zdldehyde, but this is accompanied into two 
compounds of the same composition and molecular weight, but higher 
boiling point. They are unchanged by boiling with dilute sulphuric 
acid. Heating with hydrogen bromide in acetic acid forms bromo- 
derivatives, from which the alcohols may be obtained. Oxidation with 
permanganate then yields compounds which are identified as ethers of 
5-nitrosalicylic acid and 3-nitro-4-hydroxy benzoic acid respectively. The 
original compounds are therefore derived from ?7i-nitrobenzylidene 
chloride by the wandering of a chlorine atom into the nucleus, 
followed by the replacement of chlorine by alkyloxy-groups. 

C. H. D. 

Action of Benzaldehyde on Polyhydric Alcohols Derived 
from Sugars. Jean Meunier (Ann. Chim. Phys., 1912, [viii], 26, 
286 — 288). — The author points out that the condensation of polyhydric 
alcohols with benzaldehyde to form acetals was first noticed by him in 
1888 (Abstr., 1888, 950, 1265; 1889, 233, 479; 1890, 730), and is 
wrongly attributed to E. Fischer in a recent paper {Ann. Chim. Fhys., 
1911, [viii], 24, 398). 

The sorbitol derivative described already (Abstr., 1889, 479) may be 
prepared by mixing the components at 0°, concentrating to a syrup of 
33°Be., and adding 60% sulphuric acid. The crystalline product which 
deposits is separated and washed, and can be used for the production of 
pure sorbitol by hydrolysing with 0002% sulphuric acid at 100° and 
distilling under reduced pressure, when the benzaldehyde passes over 
in the steam, leaving pure sorbitol. T. A. H. 

Aromatic Amino-ketones. Franz Kunckell {Ber. deut. pharm. 
Ges., 1912, 22. 103—114. Compare Abstr., 1900, i, 663; 1911, 
i, 990). — The methods described in the preceding paper of this series 
{loc. cit.) have been applied to /^acetotoluidide and the products 
obtained are described. 

[With Carl Blumenreuter.] — w-Chloro 2-acetylamino-5-methylaceto 



V 



ORGANIC CHEMISTRY. i. 269 



phenone, CHgCl-CO'CeHgMe-NHAc, already described (Abstr., 1900, 
i, 663) reacts with potassium acetate to form an acetate, 

O-Ac-CHg-CO-CgHgMe-NHAc, 
m. p. 94°, and with bromine to give oi-chloro-(o-bromo-2-acetylamino- 
b-methylacetophenone, m. p. 138°, and this on hydrolysis with 20% 
hydrochloric acid loses 1 mol. of acetic acid and forms the correspond- 
ing amine, m. p. 123°, bright yellow needles. On treatment with 
warm dilute sodium hydroxide solution, the chlorobromo-ketone yields • 
dimethylindigotin. 

On nitration of (o-chloro-2-acetylamino-6-methylacetophenone, one 
nitro-group enters, probably in the unoccupied o-position to the acetyl- 
amino-group; the m^ro-derivative, m. p. 167°, forms glancing, yellow 
needles, and on* treatment with alkalis does not yield a substituted 
indigotin. With aniline the chlorine atom in the parent substance is 
replaced, and the substance, NHPh'CHg'CO'CgHgMe'NHAc, m. p. 
146°, formed, crystallising in yellow needles. 

w-Chloro-3-acetylamino-6-methylacetophenone, formed along with its 
isomeride (see above), yields (l)on bromination oi-chloro-io-bromo 3-acetyl- 
amino-Q-methylacetophenone, m. p. 112°, colourless leaflets, from which 
the corresponding amine, m. p. 88°, yellow needles, is produced on 
hydrolysis ; (2) by nitration, indefinite products ; (3) by treatment 
with aniline, the corresponding aniline derivative, 

NHPh-CH2-CO-C6H3Me-NHAc, 
m. p. 184°, colourless needles; (4) with potassium acetate in dilute 
alcohol, the corresponding acetate, OAcCHg'GO'CgHgMe'NHAc, m. p. 
94°, hard, colourless needles. 

m-Bromo-/?-acetotoluidide reacts with chloroacetyl chloride to form 
oi-chlo7'o-2(or 4:)-bromo-3-acetylamino-6-methylacetophenone, m. p. 134°, 
glancing, colourless leaflets, which on hydrolysis yields the correspond- 
ing amine, m. p. 116°, glancing, yellow needles, giving a hydrochloi'ide, 
m. p. 206° (decomp.), colourless needles. T. A. H. 

Interesting Decomposition of Some Oximes. Angelo Angeli 
{Atti R. Accad. Lincei, 1912, [v], 21, i, 83 — 84). — Benzophenone- 
oxime decomposes at about 180° according to the equation : 

3CPh2:N-OH = 3COPh2 -i- N2 + NH,. 
If it is supposed that the nitrogen and ammonia are produced accord- 
icgtothe equation: 3NH = N2 + NH3, the Beckmann rearrangement 
becomes explicable on the hypothesis that a similar decomposition of 
the oxime first occurs, but the NHI group takes up another position in 
the molecule instead of giving rise to nitrogen and ammonia. 
Analogous decompositions are those of some nitronic acids (Nef), and 
of phthalylphenylhydrazide (compare Chattaway, Gumming, and 
Wilsdon, Trans., 1911, 09, 1950). R. V. S. 

Preparation of ac-Diphenyl-jS^SSS-tetramethylpentan-y-one 
and of a-Phenyl-/3/SSS-tetramethylpentan-y-one, Derivatives of 
Dibenzylacetone (a€-Diphenylpentan-y-one) and of a-Phenyl- 
pentan-y-one. Albin Haller {Compt. rend., 1912, 154, 555—559). 
— ae-Diphenylpentanone was repeatedly methylated by means of 
sodamide and methyl iodide, The final product was ae-diphenyl- 



i. 270 ABSTRACl'S or CHEMICAL PAPERS. 

PfiBStetraviethylpentan-y-miey CH2Ph'CMe2-CO-CMe2'CH2Ph, an oily 
liquid, b. p. 203 — 208°/ 10 mm. ; when heated with sodamide it under- 
goes scission in the normal way. The same method of niethylation 
applied to a-phenylpentan-y-one leads to the formation of a-p/ieni/l- 
13/iSStetrameth^lpentan-yone, CHgPh-CMeg'CO-CMeg, b. p. 139—144°/ 
16 mm. The new tetra -alkyl ketones do not react with hydroxylamine, 
semicarbazide, or phenylhydrazine. W. O. W. 

Dihalogenoindones. Hugo Simonis and Curt Kirschten (Ber.y 
1912, 45, 567 — 579). — From his investigations on the condensation of 
2 : 3-dibromo-l-indone and dibromo-derivatives of quiuones with ethyl 
malonate and other substances containing a reactive methylene group, 
Liebermann (Abstr., 1899, i, 219, 373, 522; 1900, i, 310, 666) has 
drawn the conclusion that the mobility of the halogen atoms in these 
compounds is due to the group CBrlCBr'CO being contained in a 
closed ring. 

It is now shown that the mobility is connected with the presence of 
the carbonyl group, for compounds in which this group is lacking 
have their halogen atoms firmly attached ; thus, 2 : 3-dibromo- 

l-methyl-l-indenol, CgH4<[p,.j ,^-g5^CBr, does not condense with 

substances containing a reactive methylene group, and undergoes no 
change on treatment with potassium iodide or benzylamine. 

The reaction between magnesium methyl bromide and 2 : 3-dibromo- 
l-indone yields 3-bromo-2-iodo-l-indone, which crystallises in brown 
prisms, subliming above 80° with partial decomposition, m. p. 158° 
(compare Roser and HaseihofP, Abstr., 1888, 1317), and 2 : 'Z-dibromo- 
l-methyl-X-iiidenol. The latter compound crystallises in white platelets, 
m. p. 126*5 — 127°, combines with bromine to form 2:2:3: 3-dibromo- 

PRr 

\-methyl-\-hydrindenol, C6^4'\cMe^OH^'^^^''^2» ^^^ ^^ converted by 

hydrogen bromide in glacial acetic acid solution into 1 : 2 : Z-trihromo- 

\-methylindene, CgH^^pT, t> .^CBr, pale yellow prisms, m. p. 78°; 

the acetyl derivative crystallises in lustrous, white needles, m. p. 82°. 

2-Iodo-Z-henzylamino-\ indone^ CO<C *^pj^^C*NH*C>.Hy. prepared 

either by heating 3bromo-2-iodo-l-iud«)ne with benzylamine in alcoholic 
solution or from potassium iodi<le and 2-bromo-3-benzylamino-l-indone 
(Schlossberg, Abstr., 1900, i, 665), crystallises in long, red needles, 
m. p. 138° (decomp.). The action of ethylamine and aniline on 
3-bromo-2-iodo-l-indone yields orange-red compounds of a similar 
constitution. 

Attempts to prepare 2-bromo-3-benzylauiino-l-indone by brominating 
3-benzylamino-l-indone (Schlossberg, loc. cit.) resulted in the removal 
of the benzylamino-group and the formation of a dih'omo-l-indone, 

CgH3Br<^ ^^_^CH, which crystallises in reddish-brown needles, m. p. 

177°, and contains one of the bromine atoms in the benzene nucleus. 

'i^t Bromo-^-iodo-l-indoneoxime, C^HgONBrl, exists in two stereo- 
isomeric forms, one crystallising in yellow needles, m. p. 206°, the 



ORGANIC CHEMISTRY. i. 271 

other in yellow, quadratic plates, m. p. 195 — 197°; the i^-nitrophenyl- 
hydrazone forms brownish-red, microscopic nepdles, m. p. 212 — 214°. 

On treatment with bromine, 3-bromo-2-iodo-l-indone is converted 
into 2:2:3: 3-tetrabromohydrindene (Roser and HaselhofF, loc. cit.) ; 
with magnesium methyl iodide it forms 3-bromo-2-iodo-l-methyl' 

1-indenol, ^e^i^rt^T /OH^^^"^' which crystallises in almost white 

leaflets, m. p. 137°. 

2 : 3-Dibromo-l-ethyl-l-indenol^ CuH^oOBrg, prepared from mag- 
nesium ethyl bromide and 2 : 3-dibromo-l-indone, crystallises in colour- 
less prisms, belonging to the rhombic system, m. p. 77 — 78°, and yields 
an acetyl derivative, m. p. 91° 

2 : 3-Dibromo-l-phenyl-l-indenol could not be obtained in a pure con- 
dition, and was therefore characterised by means of its acetyl derivative, 
Cj^HjgOgBrg, which forms pale grey, prismatic needles, m. p. 138 — 140°. 

F. B. 



Catalytic Elimination of Hydrogen from Aromatic Nuclei 

and the Synthesis of Condensed Systems by means of 

Aluminium Chloride. Boland Scholl and Christian Seer 

(Monatsh.j 1912, 33, 1 — 8). — When aromatic compounds are heated 

with anhydrous aluminium chloride at from 80° to 140°, hydrogen is 

eliminated and a new ring formed. Previous examples of this are 

y^ the conversion of naphthalene and a-dinaphthyl into peryl- 

CO/^I ene (Scholl, Seer, and Weitzenboch, Abstr., 1910, i, 616), 

Jv 1^ and the conversion of meso-benzdianthrone into meso- 

\ I] \ naphthadianthrone (Scholl and Mans>feld, Abstr., 1910, 

L ii J i, 494). The method has been extended to the following cases. 

^/ ^^ Phenyl a-naphthyl ketone is converted at 140° into 

/J vL JCO benzanthrone. Similarly, 6 : 7-phthaloylbenzanthrone is 

^ ''^Z obtained from 2-anihraquinonyl a-naphthyl ketone. 

Dibenzoylpyrene is converted into pyranthrone, a synthesis which 

proves the benzoyl groups to occupy positions 3 and 8 in pyrene. 

Presumably oxidising agents act at these positions, so that pyrene- 

quinone is 3 ; 8-diketopyrene (formula 1) and not 3 : 10-diketopyrene, 

(^ p^ as supposed by Bamberger and Philip (Abstr., 

/\ /\ /\ l^^*^' ^^^) ^^^ ^y Goldschmiedt (Abstr., 

^iX] 1907, i, 310). 

^mh — !v Jk Jv Dibenzpyranthrones are obtained on heat- 

^K ^j^ l"^ I ing di-a- or di-)8-naphthoylpyrenes. These 

^H.' I Jk Jv dyes give in blue vats much redder shades 

^^K ^^ \^ \ ^1 than pyranthrone. 

I^P I Jv 1 J 4 :4'-Dibenzoyl-l:r-dinaphthyl when heated 

/jj v m S ^* ^^ — 100° with aluminium chloride yields 

^ '' violanthrone. 

Heterocyclic rings are condensed in similar manner ; thus from 
3 : 8-di-a-thenoyl pyrene, a thiophen analogue of pyranthrone (formulall) 
is obtained ; this is a brownish-red product, which behaves like the 
vat dyes of the anthraquinone series. Benzil is converted into 
phenanthraquinone below 100°. E. F. A. 



i. 272 ABSTRACTS OF CHEMICAL PAPERS. 

Synthesis of a Ketone Derived from Cineole. Guido Cusmano 
and Arrioo Linari {Gazzetta, 1912, 42, i, 1 — 10). — The action of 
hydroxylamine on a-terpineol nitrosochloride yields the hydroxylamine- 
oxirae (I). From this by means of nitrous acid, the o-wonitroamine- 
oxime (II) is obtained. The o isonitroamineoxime when heated with 
water yields an oxime, CjQHj^OgN, which when oxidiFed or treated 
with ethyl nitrite and subsequently with ammonia gives a ketone, 
CiqHjj,02» ^^ ^'^® constitution indicated in formula (III). 

CMe-NH-OH CMe-NO(:N-OH) CMe 

cHgf^crN-OH ch2|/Nc:n-oh QB./^£0 i 

CH^I^^CH, CH^I^^CH^ CHgl^yCH^ | 

CH-CMe2-0H CH-CMe2-0H CH-CMe2-' 

(I.) (II.) (III.) 

a-Terpineol-o-hydroxylamineoxime, Q^^^fiz^i^ ^^ prepared in the 
same way as the other hydroxylamineoximes previously described 
(compare Cusmano, Abstr., 1910, i, 685, 863). It forms tufts of 
colourless, acicular crystals, m. p. 183° (deoomp.). It condenses with 
jo-nitrobenzaldehyde, yielding a yellow, crystalline com;?owncZ, m. p. 183°. 
When treated with dilute hydrochloric acid and sodium nitrite in the 
cold, it yields the o-\sonitroamineoximey CjoH^^O^Ng, which forms 
colourless, prismatic crystals, which decompose at 156 — 157°. The 
substance yields a blood-red coloration with ferric chloride, and gives 
Liebermann's reaction. It dissolves in alkali carbonates, and forms 
crystalline brucine salts. When it is treated with an aqueous solution 
of an alkali hydroxide, nitrous oxide is evolved, and hydroxydihydro- 
carvoneoxime is formed quantitatively. When the isonitroamine- 
oxime is heated with water alone, however, two other oximes are 
produced. One has the composition CjQHjgOgNjHgO, and m. p. 95°, 
the other has the composition CjoHj^OgN, and m. p. 139 — 140°. In 
the presence of small quantities of mineral acids the isonitroamine- 
oxime decomposes, yielding the oxime of m. p. 139 — 140°, hydroxy- 
dihydrocarvone, and the methyl ketone of homoterpenylic acid. 

The oxime, Cj^Hj^OgN, when treated with hydrobromic acid at the 
ordinary temperature yields the methyl ketone of homoterpenylic acid. 
Hydrochloric acid gives the hydrochloride, CioH^w02N,HCl, and a 
product, which is decomposed by water with the formation of ammonium 
chloride and the methyl ketone of homoterpenylic acid. When the 
oxime, CjoHj^OgN, is dissolved in ethyl nitrite, a pernitrosyl derivative, 
CjoHjgOgNg, is obtained ; it forms large crystals, m. p. 68 — 70°. The 
ketone^ CioH^^Og, is produced in small quantity by oxidising the oxime, 
CjqHj702N, with acid permanganate, but is best prepared by decomposing 
the pernitrosyl derivative with concentrated ammonia. It crystallises 
in sliining, colourless leaflets, and has a slight odour reminiscent of 
cineol. Its semicarbazone, Cj^H^gOgNg, has m. p. about 220°. When 
oxidised with acid permanganate (1%), the ketone yields the methyl 
ketone of homoterpenylic acid almost quantitatively. Alkaline 
permanganate attacks it much less readily, the products being the 
above methyl ketone and cineolic acid. R. V. S. 



ORGANIC CHEMISTRY. i. 27,3 

Hydroxy ketopermapbthindene {peri - Naphthindandione). 
Giorgio Ereera and A. Cuffaro ifiazzattay 1911, 41, ii, 807 — 814. 
Compare Errera, Abstr., 1911, i, 465). — Since the substance previously 
described under the name of joeri-naphthindandione always behaves as 
a keto-enol containing the grouping -CO'CHIC(OH)-, and since no 
derivative of the corresponding diketonic form is known, and, moreover, 
the free substance contains an hydroxyl group, the authors propose to 
substitute for their original name that of hydroxyketo/?ermaphthindene. 
When the substance is oxidised with potassium dichromate and acetic 
acid (allowing one atom of oxygen per molecule), anhydrobishydroxy- 
keto^Qvinaphthindene (annexed formula) is obtained ; it crystallises in 

yellowish-brown needles, which, on heating, 

CO CO blacken at 360° and melt with decom- 

p TT /\p__p/\p XT position at a higher temperature. The 

10 6\^^ %/ ^^ ^ oxidation of hydroxyketopert'naphthindene 

C C by means of alkaline permanganate pro- 

\ / ceeds quite differently. Even when less 

\/ than the theoretical quantity of per- 

O manganate is taken, a vigorous reaction 

occurs, and the following substances are 

obtained : (1) unaltered hydroxy ketojoeWnaphthindene ; (2) naphthalic 

acid, and (3) a substance, CjgHgOg, which crystallises in tufts of very 

small, colourless needles, m. p. about 225° (decomp.). To this 

substance is assigned the constitution COgH'CioHg'CO'COgH, and it 

is termed naphthalonic acid. 

It is decomposed by heat in the same manner as is phthalonic acid 
(compare Graebe and Triimpy, Abstr., 1898, i, 3l8), naphthalic 
anhydride being formed, and also a substance, Cg^Hj^Og, which is to 
be regarded as the anhydride of naphthalaldehydic acid ; it has 
m. p. 310 — 313° (rapid heating), and is identical with a product 
obtained by Graebe and Gfeller (Abstr., 1893, i, 656). 

When hydroxyketopeWnaphthindene is boiled with benzaldehyde 
in alcoholic solution in presence of a trace of pyridine, dihydroxy- 
keto^QTinaphthindenilphenylmethane, 

.CO— . /^^— \ 

CioH6< >C-CHPh~c4 >C,oH6, 

^0{OBY ^C(OH)^ 

is obtained ; it is a golden-yellow, crystalline powder (from alcohol), 
or forms red crystals (from xylene), m. p. 295 — 297° (decomp.). The 
substance can give metallic derivatives, but both the sodium and 
potassium salts are very sparingly soluble in water. The mono-sodium 

salt, C33Hj904Na, is a yellow, crystalline 
substance. 

When dihydroxyketojoerinaphthindenil- 
phenylmethane is boiled with an alcoholic 
solution of sulphuric acid, a substance is 
precipitated to which the constitution of 
phenytdiketoperinaphthindenexanthene (a n - 
nexed formula) is ascribed ; it crystallises in 
yellow needles, melts with decomposition at 




i, 274 ABSTRACTS OF CHEMICAL PAPERS. 

some temperature above 365°, and does nat contain ethozy-groupg or 
form salts. R. V. S. 



Transformation of a Phloroglucinol Derivative into One of 
c.vc/oHexantrione. II. Gustav Heller {Ber., 1912, 45, 418 — 427. 
Compare Abstr., 1909, i, 656). — The author gives a summary of 
reactions in which the ester of a phenol has been observed to suffer 
rearrangement into a hydroxy- ketone, and indicates that in the pre- 
paration of hydroxy-ketones by the condensation of acyl chlorides with 
phenols, the phenolic esters must be intermediate products. 

In extension of the previous investigation {loc. cit.), it is observed 
that tribromophloroglucinyl triacetate, trichlorophloroglucinyl tri- 
acetate, and 1:3: 5-triacetyltriaminobenzene when heated with zinc 
chloride show no sign of molecular rearrangement. 

[With Georg Kretzschmar.] — Phloroglucinol diacetate, m. p. 104°, 
is obtainable by the action of phloroglucinol with sodium acetate and 
the theoretical quantity of acetic anhydride. 

Triacetylc^/c/ohexantrione is so resistant to complete hydrolysis that 
this does not occur without rearrangement. If it is dissolved in dilute 
sodium hydroxide solution, slow hydrolysis occurs ; the precipitate 
obtained on acidifying is treated with boilir)g water, when the 
undissolved residue consists of diacetylcyclohexantrione ; this crystal- 
lises from benzene in needles, m. p. 168°. This substance is also 
obtained as a by-product in the transformation of phloroglucinyl 
triacetate into the triacetylcj/c^ohexantrione. I'ribenzoyldiacetylcycXo- 

hexanirione, CAcBz\p^j.p . p. ]^C0, obtained by benzoylation, crys- 
tallises in needles, m. p. 137 — 138°; it dissolves slowly in sodium 
hydroxide solution, but gives no coloration with ferric chloride. The 
action of a diazonium solution yields benzeneazodiacetylcyclohexan- 

trionSy CHAc<CQQ,nLx./>j p. v^CO, orange-coloured needle crystals, 
m. p. 209°. The action of nitrous acid gives oximinodiacetylcjclo- 
hexantrione, ^^-^^''^qO-CVNOH^^^^' gulden leaflets, m. p. 149°, 
which by reduction gives a colourless substance, decomposing at 200°. 
The hot aqueous filtrate from the diacetylcyc/ohexantrione (above) 
on cooling deposits monoacetylcyclohexantrione ; this gives pale rose- 
coloured crystals of a monohydrate, but when anhydrous it is colour- 
less, m. p. 209 — 210°. Its tribenzoyl derivative, 

forms colourless needles, m. p. 116 — 117°; it reacts with a diazonium 
solution, forming a 6i«-ai5o-compound, NgPh^dK^p/^.z-iTT/ii^ Ph\^^^' 

purple needles, m. p. 241 — '242° (decomp.). With nitrous acid a bis- 
oximmo-compound is obtained, which decomposes at 115 — 120°. 

Di- and mono-ace tylcycZohexautrione resemble the triacetyl com- 
pound in dissolving in sodium hydroxide solution, giving a coloration 



ORGANIC CHEMISTRY. i. 275 

with ferric chloride, and in forming copper salts ; the acid character is 
more marked the fewer the acetyl groups present. All three sub- 
stances react with benzaldehyde in alkaline alcoholic solution, pro- 
ducing yellow, amorphous substances. Towards phenylhydrazine and 
hydroxylamine they are inert, whilst bromine attacks them all, the 
monoacetyl compound most readily. D. F. T. 

Certain Derivatives of Tetrachloro-o-benzoquinone. C. Lorixg 
Jackson and George Leslie Kelley {Amer. Ghem. J., 1912, 47, 
197 — 221). — A continuation has been made of the study of three 
substances prepared from tetrachloro-o-benzoquinone (Jackson and 
MacLaurin, Abstr., 1907, i, 856). 

The compound, m. p. 215°, obtained by the action of benzyl alcohol 
on tetrachloro-o-benzoquinone, has proved to be the heptachloro-o- 
quinocatechol hemiether described by Jackson and Carleton (Abstr., 
1908, i, 428). This was con6rmed by analyses of its acetyl derivative, 
m. p. 195°, its reduction product (heptachlorodihydroxycatechol 
hemiether), m. p. about 188 — 190°, and the triacetyl derivative, 

OAc-C6Cl4-0-CgCl3(OAc)2, 
m. p. 144°, which forms white, hexagonal prisms. 

The other two compounds investigated were those, m. p. 198° and 
210°, which were respectively obtained by the action of methyl and 
ethyl alcohol on tetrachloro-o-benzoquinone. They can also be pre- 
pared by the action of the alcohols on heptachloro- or hexachloro-o- 
quinocatechol hemiether. 

The methyl compound was originally regarded as hexachloro-o- 
benzoquinomethylhemiacetalcatechol ether, CgCl402lCgCl20(OH)(OMe)^ 
on account of its being produced by the action of methyl alcohol on 
the ether, CgCl^OglCgClgOg, but has now been found to be hexachloro- 
methoxy-o-quinocatechol heinkther, OH*CgCl4*0*CgCl202(OMe). On re- 
ducing the compound with zinc dust and sulphurous acid, it was con- 
verted into hexachlororriethoxy-o-dihydroxycatechol hemiether^ 

OH-GgCl4-0-C6Cl2(OH)2(OMe), 
m. p. 191°, which crystallises in long, colourless needles, and yields a 
triacetyl derivative, m. p. 128 — 129°, and a monoace^?/^ derivative, m. p. 
186 — 188°. In the course of preparing these acetyl compounds 
another compound was obtained, m. p. 122°. 

The compound, m. p. 210°, obtained by the action of ethyl alcohol on 
tetrachloro-o-benzoquinone, has been found to be hexachloroethoxy-o- 
quinocatechol hemiether, OH-CgCl4'0*CgCl202(OEt) ; its acetyl derivative 
has mc p. 195°. On reducing the compound with sulphurous acid, it is 
converted into hexachloroethoxy-o-dihydroxycatechol hemiether^ 

OH-CgCl4-0-CgCl2(OH)2(OEt), 
m. p. 173°, which forms white needles, and yields a triacetyl derivative, 
m. p. 165°. If, however, the reduction is effected by zinc and acetic 
acid, a compound, m. p. 249°, is produced, and readily undergoes 
decomposition with formation of hexachloro-o-dihydroxycatechol ether, 
which furnishes an acetyl derivative, CgCl402'.CgCl2(OAc)(OH), m. p. 
251°, as well as the diacetyl derivative described previously. 

E. G. 



I 




i. 276 ABSTRACTS OP CHEMICAL PAPERS. 

Method of Formation of Alkylated Anthraquinones from 
Alkylated Benzoyl Chlorides and Aluminium Chloride. II. 
Christian Seer [with Egon Ehrenzweig] {Monatsh., 1912, 33, 
33__34. Compare Abstr., 1911, i, 386).— Mesitylenyl chloride, 
C^BLgMe^'COCl, reactd when heated with aluminium chloride at 
115—120° to give 1 : 3 : 5 : T-tetramethylanthraquinone. The com- 
pound so obtained differs from all other 
PW CO anthraquinone derivatives in that it is not 

8 .V yv reduced by alkaline sodium hyposulphite or by 

zinc dust and sodium hydroxide. It is not 
attacked by acetyl or benzoyl chloride or by 
phosphorus pentachloride, and when distilled 
with zinc dust, tetramethylanthracene is 
obtained. 

The structure is confirmed by the synthesis from m-xyXyl mesityl 
ketone, which was heatpd for some days, the tetramethylanthracene 
formed separated by distillation, and oxidised with acetic and chromic 
acids to the quinone. 

1:3. 5 :7-Tetramethylanthraquinone is not identical with the substance 
obtained by Dewar and Jones (Trans., 1904, 85, 212) by the action of 
nickel carbonyl on 7/i-xylene, to which they ascribe the same con- 
stitution. It is, however, the same a.s the oxidation product of the tetra- 
methylnnthracene obtainpd by Friedel and Crafts (Abstr., 1887, 1102) 
from the reaction of methylene chloride and ?7i-xylene in presence of 
aluminium chloride. It is now found that a little of the isomeride 
described by Dewar and Jones is produced at the same time ; 
the constitution of 1:3:6: 8-tetramethylanthraquinone is ascribed 
to this. 

1:3:5: 7-Tetramethylanthraquinone forms yellow needles, m. p. 
235°; it dissolves in concentrated sulphuric acid with a dark red 
coloration. The corresponding 1 : 3 : 5 : 7-tetramethylanthracene forms 
yellowish-white platelets, m. p. 155 — 157°, or when purified by 
regeneration from the picrate, m. p. 163 — 164°. The picrate has 
m. p. 189—190°. 

Anthraquinone-1 : 3 :5 : 7-tetracarboxylic acid and its salts were 
obtained amorphous, m. p. above 300°. 

4 : S-Dinitro-1 : 3 : 5 : T -tetramethylanthraquinone, prepared by the 
action of potassium nitrate and concentrated sulphuric acid on the 
quinone, separates in greyish-brown needles, m. p. 296°. 2:4:6:8- 
Teiraniiro-\ : 3 : 5 : 7-tetrametkylanthraquinone crystallises in yellow, 
microscopic plates. E. F. A. 

Action of Ammonia on Chrysophanic Acid Methyl Ether. 
Otto A. Oesterle {J. pr. Chem., 1912, [ii], 85, 230—232. Compare 
Abstr., 1910, i, 860). — It is pointed out that Fischer and Gross 
(Abstr., 1911, i, 886) have erroneously attributed to the author the 
view that the action of ammonia on chrysophanic acid monomelhyl 
ether leads to the replacement of the hydroxyl by an amino-group. 
The product of the action crystallises in long, glistening, brownish-red 
needles, m. p. 237 — 239°, and has the constitution of a l-hydroxy-8- 
methoxymethylanthraquinoneimide. F. B. 



ORGANIC CHEMISTRY. i. 277 

Commercial Chrysarobin. Oswald Hesse (Annalen, 1912, 388, 
65—96. Compare Tutin and Clewer, Trans., 1912, 101, 290).— Com- 
mercial chrysarobin is demethylated by hydriodic acid, D 1*7, at 
120 — 125°, or by equal volumes of hydrochloric acid, D 1 '19, and glacial 
acetic acid at 130 — 140°, and the dried product is boiled with petro- 
leum (which extracts a portion of the chrysophanol) and then with 
chloroform, in which chrysophanol in much more soluble than emodinol. 

Chrysophanol, CjgH^g^g (previously called chrysarobin by the author 
and by Jowett and Potter, Trans., 1902, 81, 1575), has m. p. 204° 
(not 205 — 210°, as stated previously). The presence of a small 
amount of the methyl ether lowers the m. p. by 6 — 8°, and of emodinol 
raises it by about the same amount (compare Fischer, Falco, and Gross, 
Abstr., 1911, i, 886). It is insoluble in alkali hydroxides or carbon- 
ates in the absence of air. By the admission of air, chrysophanol 
dissolves with the formation of chrysophanic acid; the latter is also 
formed by oxidising the anthranol with chromic and acetic acids at 
60—70° When heated with acetic anhydride at 90—100° for four 
hours, with occasional boiling for periods of ten minutes, chrysophanol 
yields a triacetate, m. p. 238 — 240° (Jowett and Potter's diacetate, 
loG. cit.), which is converted into diacetylchrysophanic acid, m. p. 208° 
(Liebermann and Seidler's "acetylchrysarobin") by acetic and chromic 
acids at 60 — 70°. Triacetylchrysophanol, like diacetylchrysophanic 
acid, yields diacetylrhein by oxidation with chromic acid in a hot 
solution of equal volumes of acetic acid and acetic anhydride (compare 
Fischer, Falco, and Gross, loc. cit.). Hexa-acetyldichrysophanol, m. p. 
125°, is a by-product of the acetylation of chrysophanol. 

Emodinol, Cj^H^^^^, isolated as described above, has m. p. 230 — 240° 
(decomp.), and yields acetylemodinol, C^gHj^O^Ac, m. p. 199°, yellow 
leaflets, by heating with acetic anhydride at 90 — 100° for two hours. 
Emodinol and acetylemodinol yield emodin and acetylemodin respec- 
tively by oxidation with chromic and acetic acids. The acetylation of 
emodinol by acetic anhydride and sodium acetate at 90 — 100° for two 
hours yields tetra-acetylemodinol, CjgHgO^Ac^, m. p. 197°, yellow prisms, 
octa-acetyldiemodinol, CgoH^gOgAcg, m. p. 125°, yellow powder, being 
formed as a by-product. The tetra-acetate is oxidised by chromic 
(calculated quantity) and acetic acids at 50 — 60° to triacetylemodin, 
which is converted into triacetylemodic acid by chromic acid, acetic 
acid, and acetic anhydride at 60 — 70°. Octa-acetyldiemodinol is 
converted into triacetylemodin by chromic and acetic acids at 60 — 70°. 

Chrysarohol, C15HJ2O4, m. p. 250 — 252°, almost colourless needles, is 
obtained from the portion of commercial chrysarobin which is 
insoluble in ethyl acetate at 55°. It is unattacked by boiliog, 
concentrated nitric acid, does not yield methyl iodide with hydriodic 
acid, dissolves in aqueous potassium hydroxide with a yellow colour, 
and in concentrated sulphuric acid with a purple-red colour changing 
to reddish-brown. It is insoluble in alcohol, and therefore does not 
develop a coloration with alcoholic ferric chloride. It yields /8- 
methylanthracene by reduction with zinc dust. It is converted into 
acetylchrysarohol, G^^H^fi^Kc, m. p. about 245°, yellow needles, by 
hot acetic anhydride, and into tetra-acetylchrysarohol, C15H8O4AC4, 
m. p. about 190° greenish-yellow flocks, by acetic anhydride and 

VOL. CII. 1. u 




i. 278 ABSTRACTS OP CHEMICAL PAPERS. 

sodium acetate at 90 — 100°. The tetra-acetate is oxidised by chromic 
and acetic acids at 50° to a red, amorphous substance, which does not 
yield emodin by hydrolysis. The substance, which crystallises from 
the ethyl acetate extracts of commercial chrysarobin (obtained in the 
isolation of chrysarobol), consists essentially of emodinol methyl 
ether. 

It is seen from the preceding that commercial chrysarobin contains 
chrysophanol and its methyl ether, emodinol and its methyl ether, and 
chrysarobol. Of these, only the first and the last can be isolated 
directly and pure. These results are confirmed by the direct 
oxidation of chrysarobin, with and without previous acetylation or 
demethylation. By direct oxidation, by oxygen in alkaline solution, 
or by chromic and acetic acids, chrysarobin yields chrysophanic acid 
and emodin and their methyl ethers. When acetylated and sub- 
sequently oxidised by chromic acid, chrysarobin yields diacetyl- 
chrysophanic acid, diacetylemodin methyl ether, acetylchrysophanic 
OH OR OTT ^^^^ methyl ether, and a small quantity of a 

substance, m. p. 202°, orange-yellow needles, which 
|Me is probably chrysarobic acid. 

The paper closes with a discussion of the 

constitutions of some of the preceding anthranols. 
Chrysophanol has probably the annexed formula, not that previously 
given (compare Oesterle, Abstr., 1911, i, 887). C. S. 

Derivatives of Menthone. Ey vind Bodtker (Comjoi. rewo? 1912, 
154, 437—439. Compare Abstr., 1907, i, 857).— The constitution 
previously ascribed to the compounds obtained by acting on benzyl- 
idenementhone with magnesium alkyl bromides is confirmed by an 
examination of their oxidation products. 

When benzylidenementhone is treated with magnesium methyl 
iodide and benzoyl chloride added before the addition of water, 

phenylmenthylmethylmethane benzoate, CgH^g^C^M , is formed, 

having m. p. 152—153°, [ajjl'-' 145°40'; on hydrolysis it yields 

plienylmenthylmethylnvethane, CgHig<^i , m. p. Ill — 112°, 

[a]u +95°16'. PJienylmenthyli^oamyl'niethane, CgiHggO, is a viscous 
liquid, b. p. 215°/15 mm., [a]S'^ -I- 13°45', wf = 1'50568 ; the benzoate 
has m. p. 93—94°, [a]l»' + 186°29'. Benzoylmenthone, Q^^^^jd^, was 
obtained as a yellow liquid by treating a toluene solution of menthone 
successively with sodamide and benzoyl chloride; it has b. p. 185°/ 
12 mm., [a]r +32°11', n^ 1-51745. 

The rotations given are for benzene solutions. W. 0. W. 

The Camphenilone Group. II. isoCamphenilone and Con- 
stitution of Camphenilene and of apoBornylene. S. V. 
HiNTiKKA and Gustav Komppa (Antialeny 1912, 387, 293 — 316. Com- 
pare Abstr., 1909, i, 500). — The generally accepted view that cam- 
phenilone and fenchone are homologous is further strengthened by the 
conversion of the former into isocamphenilone through the following 



ORaANIC CHEMISTRY. i. 279 

series of compounds, the change being quite analogous to that whereby 
fenchone has been converted into tsofenchone. 

Camphenilone, the preparation of which from camphene by a very 
simple process is described, is reduced to camphenilol, a camphenilone 
pinacone, m. p. 146°, being obtained as a by-product. Camphenilol, 
which forms a benzoate, CgHjg'OBz, b. p. 172°/15 mm., is converted 
into camphenilene by phosphoric oxide at 140 — 150°. Cam- 
phenilene has also been prepared by converting camphenilol into 
camphenilyl chloride and heating this with aniline at 175 — 180°, 
with diethylaniline at 180 — 185°, with alcoholic potassium hydroxide, 
or, most frequently, by direct distillation with aniline after the 
mixture has been boiled under reflux for five hours. The hydrocarbon 
obtained by these processes has b. p. 140 — 141°, Df 0*8693, 
< i -46848, nf 1-47850, nf 1-47425, and nf 1-46507. Camphenilene 
forms B, hydrochloride, CgHjgCl, m. p. 60 — 61°, needles or plates (which 
is probably identical with camphenilyl chloride, since mixtures of the 
two substances show no depression of the m. p.), and a nitrosite^ 
CgHj^OgNg, m. p. 122° (decomp.), bluish-green prisms^and is converted 
by the Bertram- Walbaum mixture of acetic and sulphuric acids at 
50 — 55° into an acetate, CgHjg'OAc, b. p. 195°, the hydrolysis of which 
by alcoholic potassium hydroxide yields isocamphenilol, CgHj^'OH, 
b. p. 196°, m. p. 78°. This alcohol forms a benzoate, m. p. 79°, phenyl- 
carbamate, m. p. 65°, and hydrogen phthalate, m. p. 118 — 119°, and 
is oxidised by potassium dichromate and dilute sulphuric acid to 
isocamphenilone, CgHj^O, m. p. 55 — 57°, large, white plates (semi- 
carbazone, m. p. 225 — 226°, clusters of short, monoclinic prisms). 

Camphenilene in glacial acetic acid yields with 17% ozone an ozonide, 
by the distillation of which in a vacuum is obtained a heto-aldehyde, 
C9H14O2, b. p. 123— 125°/15 mm., Df 1-0325, nf 1-46571, < 1*46867, 
nf 1-47969, which reduces Fehling's and ammoniacal silver solutions, 
forms a disemicarbazone, m. p. 205 — 206°, and by further oxida- 
tion with ozone yields a keto-acid, C^Hj3(CO)*C02H. These results 
prove that camphenilene must have the constitution (I), assuming 
that Wagner's camphenilone formula is correct. Moreover, it 
follows that isocamphenilone probably has the constitution (II). 

CHo-CH— CMe, CH,-CH— CMe, CHo'CH— CH 

1' I 1' I 1' II 

• I CH2 I I CH^ I I CMe^ll 

CH2-C=CH CO--CH— CH2 CHg-CH— CH 

(I.) (II.) (III.) 

Finally, since a;?obornylene, which is also derived from campheni- 
lone, yields by ozonisation an ozonide by the decomposition of which 
is obtained a di-aldehyde which oxidises to opocamphoric acid in the 
air, it follows that ajoobornylene has the constitution (III) ; the 
formation of a substance of this constitution from camphenilone 
(Wagner's formula) is readily explicable. C. S. 

Rotatory Power of Camphor in Carbon Tetrachloride 
Solution. A. Faucon (Compt. rend., 1912, 154, 652— 655).— The 
specific rotatory power of camphor in solutions of carbon tetrachloride 
of dilferent concentrations is given, together with empirical formulae 



1. 280 ABSTRACTS OF CHEMICAL PAPERS. 

expressing the connexion between rotation and concentration. For solu- 
tions containing 25 — 55 grams per 100 c.c. of solvent, [aj^ =43•56°-^- 
0•1148°c. The variation in rotatory power with temperature depends 
on concentration, especially when this is high. The increase for a 
rise of 1° is greater at 12° than at 40°. W. O. W. 

The Principal Constituents of Labdanum Oil. Ketonic 
Compounds. Henri Masson {Compt. rend., 1912, 154, 517 — 519). 
— Gum labdanum from Cistus creticus or C. ladaniferus gave 07 — 0*9% 
of a yellow oil when distilled in steam. The oil had b. p. 
50 — 185°/ 15 mm., and contained alcohols, phenols, esters, terpenes, and 
ketones. The latter were removed, and on fractionation yielded 
acetophenone and a fraction, b. p. 70 — 78°/15 mm., containing 1:1:5- 
triinethylcyiAohexanone, CgHjgO. When regenerated from the oxime 
(m. p. 106°, b. p. 126— 127°/17 mm.) this was obtained as a liquid, 
b. p. 66— 67°/10 mm., 178— 179°/760 mm., D 0-922, li^ 1-4494. It 
does not form a bisulphite compound, but yields a semicarhazone, 
m. p. 220 — 221°, and a ??iono6romo-derivatLve, m. p. 41°. Reduction 
with sodium and alcohol gives 1:1: b-trimethylcjc\ohexanol, m. p. 51°, 
b. p. 87°/28 mm. Oxidation with potassium permanganate leads to 
the formation of €-keto-aa-dimethylhexoic acid, 

COMe-[CH2]3-CMe2-C02H, 
b. p. 190 — 191°/31 mm. {semicarhazone^ m. p. 164°). The constitution 
of the acid was established by convening it into aa-dimethyladipic acid 
by means of sodium hypobromite. W. O. W. 

Bee Resin (Propolis). Karl Deiterich {Verh. Ges. deut. Natur- 
forsch. Aerzte^ 1912, ii, [1], 315 — 318. Compare Kiistenmacher, Abstr., 
1911, ii, 127). — Extraction of propolis with light petroleum removes 
wax and balsam, and these are separated by means of 70% alcohol. 
Resin, m. p. 90 — 106°, is extracted from the residue by absolute alcohol, 
and tannin is then extracted from the resin by water. The resin is 
then extracted with cold absolute alcohol, when an insoluble residue, 
proporesen, remains. Ether precipitates a-proporesen from the 
solution, and the filtrate after evaporation is separated by chloro- 
form into a soluble part, the " pure resin," and an insoluble part, 
^-proporesen. 

Propolis balsam is free from cinnamic acid, but contains vanillin. 
Proporesen is chemically indifferent, fluoresces in concentrated 
sulphuric acid, sinters at 76° and has m. p. 83°, and is insoluble in 
chloral hydrate solution. a-Proporesin has m. p. 187°, and is not 
fluorescent in sulphuric acid. )3-Proporesin is completely soluble in 
chloral hydrate solution, fluoresces in sulphuric acid, and yields an 
alcohol on hydrolysis. The acid sublimes in needles, sinters at 
88—90°, and melts at 124—125°. The " pure resin " fraction is also 
fluorescent, and yields an acid and a resinotannol on hydrolysis. 

C. H. D. 

Structure of Polymerised Vinyl Bromide and Caoutchouc. 
IwAN I. OsTROMissLENSKY {J. Russ. Phys. Cliem. Soc, 1912, 44, 
204 — 240). — The author shows that polymerised vinyl bromide (com- 
pare Hofmann, Annaleii^ 1860, 115, 271 ; Baumann, Annalen^ 1872, 



ORGANIC CHEMISTRY. i. 281 

163, 315), to which he gives the name caouprene bromide, exists in 
three modifications possessing identical chemical but different physical 
properties, and readily convertible one into the others. Caouprene 
bromide is a simpler homologue of the bromide of natural Para 
caoutchouc, which contains methyl groups ; further, it is either 
identical with butadiene-caoutchouc bromide (compare Harries, Abstr., 
1911, i, 798) or isomeric with it, the isomerism being due to a 
difference in the distribution of the halogen atoms in the molecule. 
The compounds obtained by the action of aniline or phenols on these 
bromides and the hydrocarbon resulting from the removal of hydrogen 
bromide from them are also discussed. 

a-Cnouprene bromide is alone formed by the action of sunlight on 
vinyl bromide, the velocity of the polymerisation being dependent in 
high degree on the presence of traces of contact substances, which may 
either retard or accelerate the change ; hydrocarbons of low boiling 
point, such as light petroleum, retard or even arrest completely the 
reaction. The a-bromide dissolves readily in carbon disulphide and a 
number of other solvents, from some of which it may be precipitated 
in the form of asbestos-like threads, from others in an amorphous 
state, and from others as a milky emulsion. It resists the action of 
energetic oxidising agents, concentrated alcoholic potassium hydroxide, 
and concentrated mineral acids. 

P' and y-Caouprene bromides are obtained by the action of the 
ultraviolet light of a quartz-mercury lamp on vinyl bromide, best in 
the gaseous state. The ^-compound is soluble in carbon disulphide, 
but the y-btomide is quite insoluble, and merely swells up in this 
solvent and forms two layers, the upper one of pure carbon disulphide 
and the lower, which shows intense violet fluorescence, of the gelatinous 
bromide retaining a considerable proportion of the solvent. 

On prolonged heating at 50° of the a-bromide or boiling of its 
carbon disulphide solution, isomeric change into the /S-form takes 
place. The change a- — >■ jB- — >■ -/-modification is readily brought 
about by ultraviolet light or by protracted boiling with anhydrous 
acetic acid. The y- may be changed completely into the /8-bromide by 
dissolving in boiling chlorobenzene and precipitating with light 
petroleum. 

The compound 'described by Harries {loc. cit.) as butadiene- 
caoutchouc tetrabromide is also found to exist in three modifications, 
one of which does not dissolve, but swells, in carbon disulphide, form- 
ing a fluorescent jelly. The other two forms are soluble in carbon 
disulphide, in which one gives a fluorescent and the other a 
non-fluorescent solution. 

The tetrabromide of neutral Para caoutchouc, which is homologous 
with caouprene bromide, also exists in certain analogous modifications 
(compare Weber, Abstr., 1900, i, 353). Free Para caoutchouc is like- 
wise obtainable in three forms (Harries, loc. cit.)y which are probably 
due to the same cause as the three caouprene bromides and the three 
butadiene-caoutchouc bromides, since in all three cases the inter- 
conversions take place under similar conditious. The differences 
between the three modifications of any one of these compounds are 
probably due to differences in the physical structures of their mole- 



i. 282 ABSTRACTS OP CHEMICAL PAPERS. 

cules, for example, such differences as exist between sodium chloride 
in the ordinary and colloidal states. In some instances, however, the 
variation in properties seems to depend on the absence or presence, in 
the surface layers, of oxidation products. 

/? find y-Caouprene bromides give exclusively colloidal solutions, as is 
shown by the boiling and freezing points of their solutions. Cryo- 
Bcopic measuiements in ethylene dibromide indicate for o-caouprene 
bromide the molecular weight 1809, corresponding with 

(•CH,-CHBr-)i,. 

Each of the three caouprene bromides, and also butadiene caoutchouc 
bromide, react with phenol at 150° (compare Weber, loc. cit.)^ giving a 
reddish-violet, elastic, amorphous compound, (CHg'CH'OPh)^. 

When an aniline solution of caouprene bromide is heated, it assumes 
a cherry-red colour, the quaternary ammonium salt, 

being formed. Rapid cooling of the solution results in the deposition 
of a spongy mass, to which the name metsi- caouprene bromide is given : 
(CH2-CH)n(NH2Ph)„;.,Br„ 2 = meta-(CH2-CH)nBr^ 2 + n/^NHaPh. The 
meta-bromide dissolves readily in carbon disulphide at the ordinary 
temperature giving an intensely fluorescent, violet solution, and, unlike 
the normal bromide, dissolves readily in fused phenol with formation 
of a pale brown solution, from which benzene precipitates a brown 
powder ; normal caouprene bromide gives an intense violet solution 
with phenol, the compound (CH2'CH),i(0Ph)n/o being formed. The 
rearrangement of halogen atoms, to which the formation of the meta- 
bromide is due, is not effected by quinoline, caouprene bromide 
precipitated from this solvent retaining its original chemical and 
physical characters. 

When a 10% solution of caouprene bromide in aniline is heated for 
thirty minutes at 120 — 130° out of contact with air, subsequent 
precipitation with alcohol or ether yields a new bromo-compound which 
does not give Weber's reaction with phenol. This compound, which 
has not yet been obtained pure and is apparently non-homogeneous, 
dissolves in fused phenol to a pale, reddish-yellow solution not pre- 
cipitated by benzene ; when heated in nitrobenzene it gives up 
hydrogen bromide. 

The removal of hydrogen bromide from caouprene bromide, its meta- 
modification, butadiene-caoutchouc bromide, and the bromide of natural 
caoutchouc leads to the formation of a hydrocarbon, (CH)n, and may 
be effected in various ways : (1) by prolonged heating with water in 
sealed tubes at 150° ; (2) by heating solutions of the bromides in 
various solvents, such as aniline, quinoline, dichloroacetic acid, 
aromatic nitro-derivatives, etc., best in absence of air ; the influence 
of these organic compounds on the removal of hydrogen bromide from 
the molecule of the complex bromide depends, not entirely on their 
power of dissolving the latter or the hydrocarbon formed, but also on 
their ability to absorb the hydrogen bromide. 

From a consideration of the above results, of the possible compounds 
obtainable by the polymerisation of vinyl bromide and of the fact that 
Weber's colour reaction with phenol is given by bromides of the terpene 
series in which the number of halogen atoms is a multiple of four, the 



I 



ORGANIC CHEMISTRY. i. 288 



conclusion is drawn that the formation of caouprene bromide takes 
place according to the scheme : 
w(CH2:CHBr) = (-CH2-CHBr-)n -^ 

CHg-CHBr-CH^-CHBr-CHg-CHBr-CHg-CHBr 

CHBr-CHg CHBr-CHg 

(the dotted line representing an unknown number of •CHg'^HBr* 
groups), the value of n beiDg not less than 12. The alternate dis- 
tribution of the bromine atoms is rendered probable by the fact that 
the autopolymerisation of halogen derivatives of ethylene or acetylene 
yields exclusively symmetrical trihalogen compounds of benzene ; 
bromoacetylene, for example, gives 1:3: 5-tribromobenzene. 

The hydrocarbon, dehydrocaouprene, obtained by the removal of 
hydrogen bromide from caouprene bromide and its isomerides, is 
regarded as a higher homologue of benzene of the formula : 

ch:ch-ch:ch-ch:ch-ch:ch 
ch: :cH* 

The action of aniline on caouprene bromide and the subsequent 
decomposition of the quaternary ammonium compound thus obtained 
into aniline and me^a-caouprene bromide are represented as follows : 
CH^-CHBr-CH^- CHBr ^^^ ^^ 

6HBr .6h, +^H,Ph-> 

CH2-CH(NH2PhBr)-CH2-CH-NH2PhBr _ 
CH(]SrH2PhBr) CH2 "^ 

NH2Ph+^jjg^ ch; 

In view of the results of Hinrichsen and Kindscher (Abstr., 1911, 
ii, 445) and of Pickles (Trans., 1910, 97, 1085), the statement made 
by Harries that caoutchouc must be regarded as an associated 
dimethylcyc^ooctadiene of the form : 

CMe-CH2-CH-CH-CMe-CH2-CH2-CH CMe-CHg-CHa-CH 

CH-CHg-CHg-CMe-CH-CHg-OHa-CMe CH-CHg-CHg-CMe 

is admissible only on the assumption that, when caoutchouc is 
brominated, it undergoes preliminary splitting with formation of 
dimethylc^/c^ooctadiene. The author hence regards this formula as 
discordant with the facts. 

The most probable structure for caoutchouc bromide is : 
CH2-CHBr-GMeBr-CH2-CH2-CHBr-CMeBr-CH2 

CHg-CHBr-CMeBr CHg-CMeBr-CHa' 

which is similar to the formula given by Pickles. 

The polymerisation of isoprene to caoutchouc is best represented thus : 
»z(CH2:CMe-CH:CH2) = (•CH2-CMe:CH-CH2-)n = 

CH2-CMe:CH-CH2-CH2-CH:CMe-CH2-CH2-CH2-CH ^ 

CH2-CH:OMe-CH2-CH2-CH:OMe CHg-CMe' 

The positions of the double linkings are here fixed, and isomerism 
is possible only in so far as the positions of the methyl groups are 
concerned. 

The name caoutchouc tetrabromide is irrational, this compound 



i. 284 ABSTRACTS OF CHEMICAL PAPERS. 

being at the least a hexabromide of the formula CjgH.^^Brg ; for the 
present it is best termed simply caoutchouc bromide. 

The various properties of caouprene bromide, synthetic butadiene- 
caoutchouc bromide, and natural Para caoutchouc bromide are collected 
in tabular form. 

"WilUtatter and Waser's results (this vol., i, 17), published after the 
author's paper was in the press, compel the assumption that dehydro- 
caouprene is not a higher homologue of benzene, but that it has the 
following structure, or one similar to it : 

CH-CH-CH-CH-CH CH* 

T. H. P. 

Regeneration of Caoutchouc from its Bromide. Synthesis 
of Butadiene -caoutchouc. Iwan I. Ostromisslensky (J. Ruse. 
Phys. Chem. Soc, 1912, 44, 240 — 244. Compare preceding abstract). 
— The action of zinc dust on caouprene bromide or butadiene-caoutchouc 
bromide dissolved in either naphthalene or chlorobenzene yields free 
caoutchouc, possessing identical chemical and physical properties in the 
two cases. The action of sodium on these bromides, especially in 
presence of ether, proceeds to some extent in the same direction, but 
is complicated by secondary processes, such as the formation of dehydro- 
caouprene, (CH)7i. The action of sodium on a 2*3% solution of 
caouprene bromide in chlorobenzene containing a little ether is accom- 
panied by sudden heating, the solvent boiling vigorously, and the 
chlorobenzene (which alone is quite inactive towards sodium) as well 
as the caouprene bromide being acted on by the sodium. 

The solution of caouprene bromide or butadiene caoutchouc bromide 
in naphthalene or chlorobenzene shows a violet-red fluorescence. 

As caouprene bromide is readily obtainable from alcohol, the above 
reaction leads to a new synthesis of butadiene caoutchouc : 
CHg-CH^-OH + AlgOg — ^ CHalCHg -^ CH2Br-CH2Br + KOH— > 

CH -CHBr —>■ V^2*CHBr-CH2-(j)HBr 2n_._^butadiene-caoutchouc. 

' CHBr CH„ 

T. H. P. 

Sphingosine. Phcebus A. Levene and Waltee G. Jacobs (Proc. 
Amer. Soc. Biol. Chem., 1911, xxixj J. Biol. Chem., 11). — Sphingosine, 
obtained originally from phrenosin by Thudichum, appears to be an 
unsaturated amino-alcohol of the define series. The substance 
obtained later by Thierfelder in the filtrate from sphingosine sulphate 
and described by him as a nameless base is dimethylsphingosine. Full 
data will be published later. W. D. H. 

Physcion. Oswald Hesse (Annalen, 1912, 388, 97—102).— 
Physcion (parietin) yields emodin by demethylation by concentrated 
sulphuric acid at 160°. It is demethylated and also reduced by 
hydriodic acid, D 1*7, yielding a substance (protophyscihydron), m. p. 
230 — 240°, which is shown to be emodinol by its conversion by 
acetylation into tetra-acetylemodinol, m. p. 198°, which yields 



ORGANIC CHEMISTRY. i. 285 

triacetylemodin by oxidation by chromic and acetic acids. The further 
proof that physcion is emodin methyl ether (compare Oesterle and 
Johann, Abstr., 1910, i, 860) is given by its methylation, whereby 
emodio trimethyl ether, m. p. 226°, is obtained. Physcihydron, the 
product of the reduction of physcion by zinc and acetic acid, is proved 
to be emodinol methyl ether by its conversion into triacetylemodinol 
methyl ether. C. S. 

Duality of Chlorophyll. C. A. Jacobson and Leon Marchlewski 
(Bull. Acad. Sci. Cracow, 1912, A, 28—40; Amer. Chem. J., 1912, 
47, 221 — 231). — Evidence is given to support the contention that the 
ratio of chlorophyll to a^^ochlorophyll varies with different species of 
plants, and also with changing conditions of growth of the same 
species. The actual amount of a//ochlorophyllan, the nearest acid 
derivative of a^^ochlorophyll, isolated from a given weight of chloro- 
phyllan from Acer platanoides of different years is very different. 
The absorption bands in the visible spectrum of the chlorophyllans 
obtained by identical methods from different species differ consider- 
ably. The same applies to the chlorophyllan bands in the ultra-violet 
part of the spectrum. The extinction coefficient?, in monochromatic 
light, of equally concentrated solutions of chlorophyllans from different 
species vary considerably. The variable ratio between the two 
constituents of chlorophyll ranges from almost pure aZ/ochlorophyll in 
Acer negundo to a product very rich in weochlorophyll in the nettle. 

E. F. A. 

Chlorophyll. XIX. Chlorophyllides. Richard Willstatter 
and Arthur Stoll (Annalen, 1912, 387, 317 — 386). — The isolation 
of pure chlorophyll is difficult on account of its solubility, decom- 
posibility, and chemical indifference. So far as the degradation of 
chlorophyll is concerned, the phytyl group is without signiticance. 
Hence for working out; the early steps of the degradation of 
chlorophyll, it is convenient to use the substance in the iovvlL»foi the 
sparingly soluble, crystalline alkylchlorophyllides. Hitherto, no 
description and analyses of an individual chlorophyll derivative have 
been given, the crystallised ethylchlorophyllide previously described 
(Abstr., 1911, i, 659) being a mixture of the a and h compounds. 
The authors have now succeeded in separating methylchlorophyllides 
a and h from one another, and also in the separation of the 
chlorophyllides a and h, the methylphseophorbides a and 5, 
and the phseophorbides a and h. The mixture of methylchloro- 
phyllides a and b has been obtained by the methanolysis of the 
fresh leaves of the acanthus (Ileracleum spondylium) by Willstatter 
and Isler's process (Abstr., 1911, i, 392). The separation of the 
two components has been effected by the partition method, the b 
compound being much less soluble in ether than the a compound. 
For practical purposes, the two partition liquids consist of 66% 
aqueous methyl alcohol, and a mixture of ether and petroleum, b. p. 
30 — 50°. The method of procedure varies somewhat, according as the 
methylchlorophyllide mixture is rich or not in the b compound, but in 
principle the process consists in shaking the ether-petroleum solution 
of the methylchlorophyllides with successive quantities of 66% methyl 



i. 286 ABSTRACTS OF CHEMICAL PAPERS. 

alcohol until the b compound, together with Bome of the a compound, 
has passed into the aqueous alcoholic layer. The ether-petroleum 
layer is then frequently shaken with water to remove the bulk of the 
ether, whereby methylchlorophyllide-a, which is insoluble in petroleum, 
is precipitated. The methylchlorophyllide-6 is isolated from the 
aqueous alcoholic extracts by a somewhat complicated process, and is 
finally purified by the fractional precipitation of its ethereal solution 
by petroleum and talc. 

Meifiylchlwophyllide - a, C82H3„ON4Mg(C02Me)2, JHgO, crystallises 
from ether in bluish- green, rhombic leaflets, yields bluish-green 
solutions with red fluorescence, exhibits the " brown phase " reaction, 
and is converted, when quite pure, only into phytochlorin-6 by treat- 
ment with methyl-alcoholic potassium hydroxide under definite 
conditions. MethylcJdorophyllide - b, C32H280.^N4Mg(C02Me)2,2H20, 
crystallises in olive-green or brown, rhombic plates, and forms in abso- 
lute alcohol a greenish-yellow solution with brownish-red fluorescence, 
is more stable than the a compound towards dilute hydrochloric acid, 
develops in the pliase tests initially a red coloration which changes to 
brownish-red and finally to yellowish-green, and yields phytorhodin-gr 
by proper treatment with methyl-alcoholic potassium hydroxide. 

The enzymatic hydrolysis of chlorophyll by chlorophyllase yields a 
mixture of the free chlorophyllides a and h ; the hydrolysis is effected 
best by extracting fresh leaves (of Heracleum or Stachys) with 60 — 80% 
aqueous acetone (also the enzymatic hydrolysis of the preceding 
methylchlorophyllides a and h in aqueous acetone yields the corre- 
sponding free chlorophyllides ; the process, however, is more diflficult 
than is the case with crude chlorophyll). The separation of the 
chlorophyllides a and h is effected, as in the case of the methyl esters, by 
the partition method with aqueous methyl alcohol and ether-petroleum. 
Chlorophyllide-&, C02H'C32H3oON4Mg*C02Me,JH20, crystallises from 
aqueoui* ether or acetone |^in six-sided plates, which are bluish- 
black by reflected and green to bluish-green by transmitted light. Its 
solutions are bluish-green with red fluorescence. By treatment with 
dry ammonia, the substance absorbs 2NH3, one of which is easily lost, 
the other only with difficulty. In consequence of its acid nature, 
chlorophyllide-a is extracted from its ethereal solution by iT/lOOO- 
potassium hydroxide. The separation of chlorophyllide from alkyl- 
chlorophyllides is conveniently effected by leading ammonia into the 
ethereal solution, whereby the former is precipitated as the ammonium 
salt. By prolonged warming in a vacuum or by keeping in the solid 
state or in dilute solution, the chlorophyllide changes to magnesium 
phseophorbide, which is insoluble in ether. Ohlorophyllide-h, 
C02H*C32H2802N4Mg'C02Me, crystallises from acetone in yellow to 
olive-green, six-sided leaflets, forms yellowish -green solutions with 
brownish-red fluorescence, absorbs 2NH3, one of which is retained even 
in a vacuum, and is more strongly acidic than the a compound, being 
extracted from ethereal solution by 372000-potassium hydroxide. 

Methylchlorophyllide-a is easily and quantitatively converted into 
methylphaeophorbide-B. by treating its ethereal solution with 10% 
hydrochloric acid for two minutes; the pure, crystalline methyl- 
phseophorbide-a is then obtained by concentrating the ethereal 



ORGANIC CHEMISTRY. i. 287 

solution. In a similar manner, methylchlorophyllide-6 is converted 
into methylphaeophorhide b by 15% hydrochloric acid. On account of 
their difference in basicity, mixtures of methylphaeophorbides a and h 
are separated much more conveniently by hydrochloric acid than 
by the partition method. The a compound is extracted completely 
from its ethereal solution by 18% hydrochloric acid, whilst the h 
compound requires the use of 23% acid. The ethylphseophor bides 
a and h (Abstr., 1911, i, 659) can be separated in a similar manner. 
Methylphaeophorhide-a., C32H320N4(G02Me)2, crystallises in rhombic 
leaflets or twinned prisms, which have a violet-black lustre, appear 
brownish-yellow or brownish-red under the microscope, and form a 
dark violet powder. The ester dissolves in formic or hydrochloric acid 
with a blue colour, and in ether or other indifferent solvents with an 
olive-green colour, similar to that of phytochlorin-e, but differing by 
exhibiting a red fluorescence. Methylphseophorbide-a has acid number 
16. When heated slowly it softens at about 150° and has m. p. 
210 — 220°(decomp.); at 220° it still yields mainly phytochlorin-e after 
hydrolysis. Methylphaeophorhide-h^ C82HgQ02N4(002Me)2, forms large, 
olive-green or brown, rhombic crystals, and yields a reddish-brown, 
fluorescent solution in ether and a green solution in hydrochloric acid. 
The ester, which has acid number 21, softens at 200° and begins 
to decompose at about 250°; after being heated at this temperature it 
still yields nearly pure phytorhodin-^r by hydrolysis with potassium 
hydroxide. 

Excluding phytochlorin-e and phytorhodin-^, the free phseophor bides 
a and b are the most easily obtainable chlorophyll derivatives. They 
can be prepared by three methods : (1) By shaking an ethereal solution 
of the chlorophyllides a and h with 16% hydrochloric acid, the 
magnesium compounds are decomposed and the phseophorbide-a passes 
entirely into the acid solution, the h compound remaining in the 
ethereal layer ; (2) an ethereal solution of the methylchlorophy Hides a 
and h is treated for two hours with 25% hydrochloric a<5id, whereby 
the magnesium compounds are decomposed and the carbomethoxy- 
group a is hydrolysed. The mixture of phseophor bides a and h is then 
isolated, and is separated as in method (1). The best process is (3), in 
which phseophytin (phytylphseophorbide a and h) in ethereal solution is 
treated with 34 — 35% hydrochloric acid for three-quarters to one hour. 
The solution is diluted with water, the phytol removed by ether, and 
the solution is further diluted with water ; the phseophorbides are 
extracted by an excess of ether, and the ethereal solution is con- 
centrated and treated with 16% hydrochloric acid, whereby phseo- 
phorbide a is removed. 

Fhaeophorbide-Sif C02H'C32Hg20N4*C09Me, crystallises in bluish- 
black, rhombic plates, which appear olive-green or olive-brown under 
the microscope. The colours of its solutions in different solvents are 
like those of methylphaeophorbide-a. The substance absorbs 2NH3, 
one of which is lost only in a vacuum. The acid number is 15. 
Phseophorbide-a is extracted from its ethereal solution by ^/lOO- 
ammonia or potassium hydroxide, by 0*1% sodium carbonate, and by 
1% sodium hydrogen carbonate or phosphate. Phaeophorhide-h, 
COgH'CagHg^^OgN^'OOgMe, crystallises from ether in small, rhombic 



i. 288 ABSTRACTS OP CHEMICAL PAPERS. 

plates and needles, which appear olive-green or brown under the 
microscope. The substance absorbs approximately 2NHg, which is 
almost entirely lost at the ordinary pressure. It forms a reddish- 
brown, fluorescent solution in ether, and a green solution, in hydro- 
chloric acid. Ph8eophorbide-6 is more acidic than the a compound ; its 
acid number is 19 — 20, and it is extracted from ethereal solution by 
0-2% sodium hydrogen carbonate or by 0*25% disodium hydrogen 
phosphate. By treatment with methyl-alcoholic potassium hydroxide 
it gives a " red phase." 

The term *' allomerism " is employed to denote the changes which 
the chlorophyllides and the alkylchlorophyllides undergo in alcoholic 
solution (A^istr., 1911, i, 660). Allomerism in alcoholic solution 
is catalytically accelerated by the presence of glass, but not of platinum 
or silver ; it is prevented by the presence of a trace of acid. Allomeric 
changes are to be explained probably by the rupture of the lactam 
group in the chlorophyll derivative, and the formation of a new lactam 
group. 

The degradation of chlorophyll (for example, chlorophyll-a, 

annexed formula) can now be 
y y effected in three ways, in each of 

NH CO * which the reagent attacks the 

P ' . ' ^ a chlorophyll molecule at a different 

C02Me-[C3iH29N3Mg]-C02-C2oH39 point. (1) By the enzymatic 

action of chlorophyllase, changes 
only occur at the a-group ; in methyl or ethyl alcohol the phytyl 
group is replaced by methyl or ethyl, whilst in aqueous 
acetone it is replaced by hydrogen, this being the only method by 
which the free chlorophyllides can be obtained. (2) By gentle treat- 
ment with acids, the magnesium is replaced by hydrogen and 
phseophytin is obtained. By more energetic treatment, hydrolysis 
occurs at the a-group, and the free phseophorides are produced ; since 
these still exhibit the " brown phase," the y-lactam group is still 
intact. (3) Alkalis first attack the y-lactam group in the " brown 
phase " ; subsequently a new lactam group is formed. Then follows 
hydrolysis at the a-group, and, finally, with difficulty at the ^-group. 
At higher temperatures, alkalis cause an elimination of carbon dioxide, 
and degradation to di- and mgno-basic phyllins and porphyrins ensues. 
A diagrammatic representation of these changes is given. 

The formulae of the compounds in this paper are to replace those 
previously recorded (Abstr., 1911, i, 659). C. S. 

Phylloporphyrins. Leon Marchlewski (Annalen, 1912, 388, 
63—65). — WiUstatter and Fritzsche (Abstr., 1910, i, 136) state that 
Schunck and Marchlewski's phylloporphyrin is a mixture of two 
substances of different basicity. The author, therefore, has heated 
a^/ophyilotaonin (Abstr., 1907, i, 866) with 10% alcoholic potassium 
hydroxide at 200°, whereby only Schunck and Marchlewski's phyllo- 
porphyrin together with feebly basic by-products is obtained. 
Chlorophyllanic acid, however, by the same treatment, yields two 
markedly basic products, which are separated by 0*25% hydrochloric 
acid. One of these products, called phylloporphyrin-a, is identical 



ORGANIC CHEMISTRY. i. 289 

with Schunck and Marchlewski's phylloporphyrin ; the other more 
basic product is called pbyIloporphyrin-;8. By treatment with 
alcoholic potassium hydroxide at 200°, phyllocyanin and a^Zochloro- 
phyllanic acid each yield mainly phylloporphyrin-^, very little of the 
a-compound being produced (compare following abstracts). C. S. 

The Chlorophyll Group. XII. ^S-Phylloporphyrin. Leon 
Marchlewski and J. Robel {Biochem. Zeitsch., 1912, 39, 6 — 11 ; Bull. 
Acad, Set. Cracow, 1912, A, 41 — 46). — The authors believe that the 
so-called pyrroporphyrin of Willstatter and Fritzsche is essentially the 
phylloporphyrin of Schunck and Marchlewski, which had not" been 
sufficiently purified, in that the former investigators had under- 
estimated the basicity of the less basic product in the mixture. When 
these porphyrins are prepared from crude chlorophyllanic acid (from 
maple chlorophyll) by the method described in detail by the authors, two 
products are formed simultaneously, namely, a strongly basic ^- 
phylloporphyrin, which can be dissolved out from its solution in ether 
by ^% hydrochloric acid, and the phylloporphyrin of Schunck and 
Marchlewski. If ^% acid be used instead, appreciable quantities of 
the last-named porphyrin are also dissolved. A comparison of the 
spectra of the two substances is given. S. B. S. 

The Chlorophyll Group. XIII. Porphyrins from Phyllocyanin 
and Phylloxanthin. Leon Marchlewski and B.Zurkowski {Biochem. 
Zeiisch., 1912, 39, 59 — 63). — In view of the possibility of separating 
a- and jS-phylloporphyrius (see Marchlewski and Kobel, preceding 
abstract), investigations were made with the object of finding the 
parent substance of these two derivatives. The yS-derivative is not 
obtained at all from the phyllotaonin of Schunck and Marchlewski, or 
from the pure a^^phyllotaonin of Marchlewski and Kobel. These 
yield the a-substance. On the other hand, phyllocyanin and phyllo- 
xanthin, which stand in near relationship to weochlorophyll and allo- 
chlorophyll, yield chiefly the /8-derivative. The previously-expressed 
views on the subject are not correct, owing at the time to the want of 
a satisfactory method for separating the two porphyrins. The experi- 
mental details of the method of preparing the ^-substapce from 
phyllocyanin and phylloxanthin are given in full. S. B. S. 

The Red and Blue Pigments of the Algae. Harald Kylin 

{Zeitsch. physiol. Chem., 1912, 76, 396—425. Compare Abstr., 1910, 

i, 866). — The occurrence of phycoerythrin and phycocyanin in a number 

^of varieties of Fioridece and Cyanophycece has been investigated. 

^H In addition to the properties previously given {loc. cit.). phycoerythrin 

^Hferystallises in hexagonal prisms usually without pyramidal faces ; 

^Hthese are optically negative. The same modification has been isolated 

^Tfrom twenty species of Fioridece ; from three species, Folysiphonia 

P Brodiceij P. nigrescens, and Rhodomda subfusca, a modification was 

obtained which lacked the fluorescent properties. So far, phycoerythrin 

has only been obtained from the Fioridece. 

t Three modifications of phycocyanin have been identified. 
Bluish-green phycocyanin shows a remarkable dark carmine-red 
uorescence, and has an absorption band in the orange between C and D 



290 ABSTRACTS OF CHEMICAL PAPERS. 

with a maximum at X = 624 — 618. It crystallises in hexagonal 
rliombobedra. 

Blue plnjcocyanin also gives a splendid dark carmine-red fluorescence, 
and has two absorption bands, one in the oranga» between C and D 
with a maximum at \ = 615 — 610, and the other in the yellow-green 
between D and E, but nearer to D, with a maximum at A, = 577 — 573 ; 
it was not obtained crystalline. This modification is widely distributed 
amongst the Cyanophyceae. 

Bluish-violet phycocyanin has the same fluorescence, and shows 
absorption bands in the orange between C and D with a maximum atX = 
618 — 613, and in the green between D and E, but nearer E, with the 
maximum at A = 553 — 549. It crystallises in rhombic plates, which are 
blue across the shorter diagonal, violet across the longer. This 
modification occurs in Geramium rubrum. 

Phycocyanin is characteristic of the Gyanophycece^ but occurs in a 
few FloridecB. E. F. A. 

Melanin. Ross Aiken Gortner (Biochem. Bulletin, 1911, 1, 
207 — 215. Compare Abstr., 1911, ii, 908). — Melanins are probably 
formed by the interaction of an oxydase and an oxydisable chromogen. 
They differ in solubility in dilute acids ; those which are soluble 
contain a protein complex ; those which are insoluble are the granules 
seen in hairs and tissues. Tyrosine, lysine, and arginine are obtained 
as hydrolytic products from the former class (melano-proteins). 

W. D. H. 

Formation of Gallamide from Acetyltannin. Maximilian 
NiERENSTEiN (Ber., 1912, 46, 533—534. Compare Abstr., 1910, 
i, 487). — The formation of gallamide from acetyltannin by heating 
with alcoholic ammonia is regarded as doubtful ; the former analytical 
values were calculated incorrectly. E. F. A. 

Hydroxyhydrofurans. Georges Dupont {Compt. rend., 1912, 
154, 599—601. Compare Abstr., 1911, i, 554, 804).— Ketohydro- 
furans are not reduced by zinc and alkalis, by sodium amalgam, or by 
hydrogen in presence of platinum. Sodium ethoxide at 120°, however, 
gives red compounds, which on treatment with water yield the 
corresponding hydroxyhydrofurans, together with viscous, high-boiling 
liquids. 

Z-Uydroxy-2 : 2 : 5 : 5-tetra7nethyltetrahydro/uran, i .piir" -^^^ 

has b. D. 84715 mm., D^' 0-9483, w^ 1-4435; the acetate'^ has 
b. p. 181—182°, D15 0-9587, nj, 1-4256, and the acid pkthalate, m. p. 
139 — 141°. 3 - Hydroxy - 2 : b -dimethyl -2 : b - diethyltetrahydrofuran 
has b. p. 107°/19 mm., D^^ 0-9539, n^ 1-4547; the acetate has b. p. 
97— 98°/15 mm., D^^ 0-9589, n^ 1-4382. 

Ketodimethylhydrofuran reacts with organo-magnesium halides, 
giving derivatives of hydroxyhydrofurans, whereas the ketotetra- 
alkylhydrofurans react in the enolic form, yielding hydrocarbons. 
The following compounds have been obtained : 

S-irydroxy-2 :3 :5-ti'imethyltetrahydrofuran, b. p'. 71 — 73°/16 mm., 



ORGANIC CHEMISTRY. i. 291 

171— 1737755 mm., D21 0*9719, tij, 1*4420; 3-hydroxy-2 : 5-dimethyl- 
S-ethyltetrahi/drofaran, b. p. 79—81716 mm., D2i 09693, n^, 1*4485; 
3-hydroxy-3-phenyl-2 : 5-dimethyltetrahydro/uran, b. p. 138 — 1407 
16 mm., D20 1-0827, Wp 1'5310 ; 3-hydroxy-3-benzyl-2 : b-dimethyltetra- 
hydrofuran, b. p. 146—147715 mm., D^^ 1-0598, n^ 1*5251 ; 3-hydroxy- 
3-p-tolyl-2 : 5-dimethyUetrahydrofuran, b. p. 149 — 150715 mm., 
D15 1-0456, fijy 1*5288 ; 3-hydroxy-3-henzyl-2 : 2 : 5 : 6-tetramethyltetra- 
hydrofuran, m. p. 89°. W. 0. W. 

Action of Sodium Hydroxide on 5-Methylfurfuraldehyde. 
Jan J. Blanksma {Ghem. Weekblad, 1912, 9, 186— 187).— Sodium 
hydroxide converts 5-methylfurfuraldehyde into the corresponding 
alcohol, ^-methyl-2-hydroxymethylfuran, and acid, 5-methylpyromucic 
acid. The alcohol is a colourless, mobile liquid of fruit-like odour. 
It has b. p. 100711 mm. Exposure to light and air converts it into 
a yellow syrup, which gradually becomes brown and viscous, and 
ultimately changes to a dark-coloured resin, A. J. W. 

Synthesis of Pyronieconic Acid. Alberto Peratoner {Gazzetta^ 
1911, 41, ii, 686—697). — The author has effected the synthesis of 
pyromeconic acid by direct oxidation of 4-pyrone, after unsuccessful 
attempts to obtain derivatives of meconic acid from the substance 
C02EfCO-CH2-CO-CH(OEt)-CO-C02Et by dehydration. 

When ethyl acetol ether is condensed with one molecule of ethyl 
oxalate in the presence of sodium ethoxide, the vessel being cooled 
externally with ice, and the solvent subsequently evaporated in a 
vacuum below 40°, a sodium salt is produced, which, on treatment 
with concentrated acetic acid and distillation in a vacuum, yields 
ethyl a-ethoxybutane-pS-dione-8-carboxylate, 

OEfCHg-CO-CHg-CO-COgEt, 
which is a slightly yellow oil, b. p. 135 — 140720 mm. Its aqueous 
solution gives a cherry-red coloration with ferric chloride, and with 
copper acetate it yields a green salt, CjgHggOjQCu. By the action of 
a second molecule of ethyl oxalate on the sodium salt above described, 
and proceeding as suggested by Willstatter and Pummerer in the case 
of xanthochelidonic acid (Abstr., 1904, i, 1043), diethyl p-ethoxypentane- 
ay^-trione-a€-dicarhoxylate, C02Et-CO-CH(OEt)-CO-CH2-CO-C02Et, is 
obtained. The triketone is purified by sublimation at 20 mm., 
treatment with water and resublimation, and then forms colourless, 
acicular crystals or scales, m. p. 124 — 125°. With alkalis it yields 
yellow, amorphous a;aw^Ao-salts, but with ferric chloride it gives a 
dirty green coloration which becomes reddish-brown, whilst copper 
acetate yields a green copper salt. It was not found possible to 
eliminate the elements of water from the triketone in any way, but 
when it is boiled for half an hour with hydriodic acid (D 1*7) 
w-pimelic acid is produced. 

Pyromeconic acid is formed when one molecule of hydrogen peroxide 
(3% solution) is added slowly to a solution of one molecule of 4-pyrone, 
one molecule of ferrous sulphate, and sulphuric acid, the mixture being 
cooled in ice. The isolation of the acid may be effected either by 
treating the liquid at its boiling point with ammonia and air until the 




1. 292 ABSTRACTS OF CHEMICAL PAPERS. m 

pyrone is converted into pyridone and the iron is precipitated, or by 
prolonged extraction of the liquid with chloroform, the product in 
either case being purified by sublimation in a vacuum below 100° and 
by recrystallisation. R. V. S. 

Anthocyanins. II. An An thocy an in-like Oxidation Product 

of Chryein. Maximilian Nierenstein {Bar., 1912, 45, 499 — 501. 

Compare this vol., i, 42). — By oxidation with chromic and acetic acids 

in the cold, chrysin yields chryaone (annexed 

formula), m. p. above 360°, dark red needles. 

It exhibits the blue and the red colour reactions 

HOj^ Y ^i-P^ ^^ anthocyanin with alkalis and concentrated 

sulphuric acid respectively. Jt forms an acetyl 

derivative, Cj^HjoOg, m. p. 324 — 326° (decomp.), 

red needles, and when heated with acetic anhydride 

and zinc dust yields an acetylated hydroxychrysin, 

by the hydrolysis of which 1:3: i-trihydroxyjlavone, m. p. 304 — 305° 

is obtained {triacetyl derivative, m. p. 214 — 217°, colourless needles). 

Fisetin is not oxidised by chromic and acetic acids. C. S. 

Some Derivatives of Hydroxyquinol. VII. Guido Bargel- 
LiNi and Ermanno Martegiani {Gazzetta, 1911, 41, ii, 612 —618). — 
The paper deals with two coumarins obtained by condensation of 
hydroxyquinol with ethyl acetoacetate and ethyl benzoylacetate 
respectively. When hydroxyquinol triacetate and ethyl acetoacetate 
are heated together for half an hour on the water- bath with 73% 
sulphuric acid, /S-methylsesculetin is obtained, identical with that 
prepared by von Pechmann and von Krafft (Abstr., 1901, i, 285). 
Its diacetyl derivative, Cj^HigOg, has m. p. 149 — 151°; it dissolves in 
concentrated sulphuric acid, giving a yellowish-green coloration. The 
dibenzoyl derivative, C24HjgOg, crystallises in colourless needles, m. p. 
152°; it dissolves in concentrated sulphuric acid, giving a slight 
yellow coloration. The dimethyl ether crystallises in colourless needles, 
m. p. 130 — 134°. The monomethyl ether, Cj^HjqO^, formed in its 
preparation, crystallises in slightly yellow needles, m. p. 173 — 175°. 

fS-Phenylaesculetin^ G-^^H^qO^, is a yellow, crystalline powder, obtained 
by condensation of hydroxyquinol triacetate with ethyl benzoylacetate 
in the presence of 73% sulphuric acid. It dissolves in concentrated 
sulphuric acid, giving a yellow coloration, and with ferric chloride in 
alcoholic solution it gives a green coloration. The diacetyl derivative, 
CjgHj^Og, crystallises in colourless needles, m. p. 156°. The benzoyl 
derivative crystallises in colourless needles, m. p. 162 — 164°. The 
dimethyl ether was not obtained in crystalline form, but crystals of a 
substance, m. p. 122 — 124°, were obtained, which was probably the 
monomethyl ether. R. V. S. 

New Method for the Preparation of Thiophen. Wilhelm 
Steinkopf {Verh. Ges. deut. Naturjorach. Aerzte, 1912, ii, [1], 
220 — 221). — Acetylene is passed through an iron tube containing 
pyrites at a temperature of 300°. The tube is provided with a 
transporting screw for the removal of spent pyrites. The liquid 



ORGANIC CHEMISTRY. i. 293 

|)l'0^ilct obtained in the condensing vessel contains 40% of thiophen. 
In seven or eight hours, 800 grams of distillate may be obtained, 
using 8 kilograms of pyrites. The thiophen is easily obtained with 
a purity of 95 — 96%, tbe impurities being sulphur compounds with 
traces of benzene. Larger quantities of benzene are not obtained in 
the process. The remainder of the distillate is a complex mixture, 
from which only a single compound, C^HgSg, b. p. 36 — 38°, with a very 
penetrating odour of garlic, has been isolated. C* H. D. 

s-Dioxythionaphthen. Maurice Lanfry {Compt, rend., 1912, 
154, 519—521. Compare Abstr., 1911, i, 555, 740, 1009).— 
^-Dioxythinnaphthen, C8Hg02S, is prepared by the action of hydrogen 
peroxide on thionaphthen (Gattermann, Abstr., 1894, i, 92), employing 
0*5 — 0*8 gram of active oxygen per gram of thionaphthen. The 
compound crystallises in colourless needles, m. p. 142 — 143°; it does 
not give the Laubenheimer reaction, and does not show the properties 
of a phenol, a ketone, or a quinone. It follows, therefore, that the 
oxygen is attached directly to sulphur, as indicated by the name the 
author suggests for the compound. 

Dioxythionaphthen unites with bromine to form a dihromide^ 
CgHg02SBr2, occurring in slender needles, m. p. 168 — 170°. When 
treated with fuming nitric acid, it yields a moTiom^ro-derivative, 
CgHgOgS'NOg, crystallising in yellow rhombohedra, m. p. 187 — 188°. 

W. O. W. 

"Thio indigo" Dyes of the Naphthalene Series. Paul 
Frtedlander and N. Woroshzow {Annalen, 1912, 388, 1 — 23). — The 
series of reactions whereby anthranilic acid has been converted into 
" thio-indigo " (Abstr., 1906, i, 378 ; 1907, i, 334), is applicable in the 
naphthalene series to the preparation of " bis-2 : 3-naphthathiophen- 
indigo" [bis-2 : 3-naphthathiophe7i] and bis-1 : 8-naphthapenthiophen- 
indigo " [bis-l : S-naphthathiop/ien] (formulae I and II respectively). 






CO CO 

C:::=rc- 

(II.) 

[With E. Eckstein.] — The sodium salt which is precipitated by 
the addition of sodium chloride to the not too dilute, diazotised 
solution of 2-amino-3-naphthoic acid is added to a hot solution of 
potassium xanthate. When the oil which separates has become solid, 
it is dissolved in sodium hydroxide and warmed with chloroacetic 
acid. By acidification, (3-3-carboxi/naphthylthiolacetic acid^ 

C02H-OioHg-S-CH2-C02H, 

m. p. 224° (decomp.), white needles, is obtained. Its sodium salt is 

boiled with acetic anhydride and sodium acetate, the resulting 

acetoxynaphthathiophen is hydrolysed by dilute sodium hydroxide, 

VOL. cii. i. X 



i. 294 ABSTRACTS OF CHEMICAL PAPERS. 

and the hydroxynaphthathiophen is oxidised by alkaline potassium 
ferricyanide, whereby 6is-2 : Z-naphthathiophen is obtained. The dye 
crystallises in almost black needles, sublimes without decomposition, 
yields an orange-red vat with alkaline hyposulphite, and develops an 
olive-green coloration with fuming sulphuric or chlorosulphonic acid. 
Naphthastyril (Abstr., 1910, i, 201) is converted by boiling 10% 
sodium hydroxide into sodium 8-amino-l-naphthoate, the diazotised 
solution of which is converted by reactions similar to the preceding 
into his-\ : 8-naphthapenthiophe7i, which crystallises in long needles 
with a copper lustre and sublimes with decomposition. The inter- 
mediate products isolated in its preparation are the anhydride of 

8-thiol-l -naphthoic acid, CioHg<^ i , m. p. 144*5 — 145*5°, yellow 

needles, a-%-carhoxynaphthylthiolacetic acid, COgH'CioHQ'S'CHg'COgH, 

m. p. 177°, and hydroxy-\ : B-naphthapenthiopIien, CjQHg<^ol___i^CH, 

m. p. 84*5 — 85*5°, yellow prisms (acetyl derivative, m. p. 130*5°, 
yellow leaflets), which is oxidised to the dye best by atmospheric 
oxygen. 

** Bis-l :2-7iaphthathiopIienind{go^' [bis-l : 2-naphthathiophen] and 
bis-2 : l-naphthathiophen [bis-'2 : l-napfdJiathiopJien] (formulae i and 
II respectively) cannot be prepared by the preceding method 





(I.) 

because the necessary aminonaphthoic acids are unknown. The latter 
dye has been prepared in three ways : (1) a-Naphthylamine-2- 
sulphonic acid is converted in the usual way into 1-cyanonaphthalene- 
2-sul phonic acid, the potassium salt of which yields the chloride^ 
CN-CioHg'SOgCl, m. p. 141 — 142°, by heating with phosphorus penta- 
chloride. The chloride is reduced by zinc and hydrochloric acid to the 
mercaptan, which reacts with sodium chloroacetate in alkaline solution 
to form, after acidification, ^ - 1 - carhoxynaphthylthiolacetic acid, 
C02H-C,oHc-S-CH2-C02H,H20, m. p. 69° (134*5° when anhydrous), 
colourless needles. By prolonged boiling with concentrated sodium 
hydroxide and acidification of the hot solution, this acid yields hydroxy- 

2 :l-naphthathiop/ien, CiQHg<^_j.g__J^CH, m. p. 121°, colourless 

needles, which reacts with benzaldehyde and ^nitrobenzaldehyde 

to form the thioindogenides, Cu)Hg"<J^>C:CHPh, m. p. 159°, yellow 

needles, and CioH6<P^^C:CH-C6H4-N02, m. p. 287° yellow needles, 
res pe ctively, and with )S-naphthisatin chloride in hot xylene to form 




ORGANIC CHEMISTRY. 295 

naphthindole-2 : 1-naphihathiophen (annexed formula), dark violet 

crystals, which develops a bluish-violet 
/\ coloration in concentrated sulphuric acid. 
I (2) 2-Thiol-a-naphthylamine and potassium 
chloroacetate are heated with concentrated 
j I CIC I I potassium hydroxide, whereby, after acidi- 
\/\/ \/\/ ficatioD, the lactam of /3-1-aminonaphthyl- 

thiolacetic acid, CioHg<-s. • , m. p. 

to UHg 

203°, is obtained. ^'l-Gyanonaphthylthiolacetic acid, 

CN-CioHg-S-CHg-COaH, 
m. p. 173°, which is prepared from the preceding compound, is con- 
verted by hot potassium hydroxide into potassium 3-aminonaphtha- 
thiophen-2-carhoxylate, an acidified solution of which yields hydroxy- 
2 : 1-naphthathiophen by boiling. (3) ji-Naphthylthiolacetic acid, 
CjQH^'S'CHg'COgH, m. p. 91°, obtained by heating ^-naphthyl 
mercaptan and chloroacetic acid in alkaline solution, is converted 
directly into hydroxy-2 : 1-naphthathiophen by 10% chlorosulphuric 
acid in chloroform at the ordinary temperature. 

Bi8-2 : \-naphthathiophen, which is obtained by the oxidation of 
hydroxy-2 : 1-naphthathiophen, best by alkaline potassium ferricyanide, 
crystallises in reddish-brown needles with a bronze lustre, develops a 
dark blue coloration with concentrated sulphuric acid, and yields a 
yellow vat with alkaline hyposulphite. 

Bis-1 :2-naphthathiophenf which can be obtained by methods analogous 
to the preceding, forms dark red needles, develops a brownish-red 
coloration with concentrated and an intense blue with fuming 
sulphuric acid, and yields a yellow vat. The lactam of a-2-amino- 

g QtT 

naphthylthiolacetic acid, ^loH6<CAJ^^^.Q/^^ ^- P- 210°, a'2-cyano- 
naphthylthiolacetic acid, CN-CioHg-S-CHg-COgH, m. p. 137-— 138°, and 
hydroxy-1 :2-naphthathiophen, C^^Hg<f ^^ ^^ CH. m. p. 142° {henzyl- 
idene derivative, m. p. 181°, yellow leaflets), are also described. 

Organic Syntheses by means of Sunlight. VII. Photo- 
synthesis of a New Alkaloid from Acetophenone and 
Ammonia. Emanuele Paterno and Concetto Maselli {Gazzetta, 
1912, 42, i, 65—75; Atti R. Accad. Lincei, 1912, [v], 21, i, 
235 — 243). — -When acetophenone dissolved in saturated alcoholic 
ammonia is exposed to sunlight for several months, a substance is 
produced which, from its properties, is to be regarded as an alkaloid. 
The yield does not exceed 20%. The new alkaloid, CjgHjgNg, forms 
large, transparent crystals [Zambonini : the crystals belong to the 
triclinic system: a/6.c = 1*5017 : 1 :l-5993; a 91° 21-5', jS 106° 14', 
y 79^ 50'], which have m. p. 227° and dissolve in alcohol, giving a 
strongly alkaline solution. The substance has about the normal 
molecular weight in freezing acetic acid. The nitrate is a white, 
crystalline powder, m. p. 258°. The hydrochloride, CigHigN^jHCl^ 

X 2 



i. 296 ABSTRACTS OF CHEMICAL PAPERS. 

crystallines in tufts of long, colourless needles, and does not change 
when heated in a current of dry hydrogen chloride in a bath at 350°. 
The platinichloride, (Ci8H^8N2)2iH2PtClfl, forms silky, flesh-colourerl 
laminae, which begin to bl token at 260°. The silver salt is a white, 
amorphous powder. The base yields a monom<ro«o-derivative, 

when warmed with potassium nitrite in solution in glacial acetic acid 
and alcohol ; the substance crystallises in lustrous laminro, m. p. 218° 
(decomp.). 

Negative results wei*e obtained in attempts to oxidise the alkaloid 
with permanganate and to determine its alkyloxy-groups. When the 
substance is heated in a sealed tube for three hours at 370°, a portion 
of it is converted into a reddish-brown oil, but the greater part remains 
unchanged. When the alkaloid was heated with hydriodic acid and 
phosphorus for six days, the product consisted of the hydriodide of the 
base, together with a small quantity of a yellow oil. R. V. S. 

RearraDgement of Cinchonine and Quinine into Their 
Poisonous Isomerides Cincbotoxine and Quinotoxine. Henry 
C. BiDDLE {Ber., 1912, 45, 526—528. Compare R^be, 1911, ii, 33).— 
Salts of cinchoDine and quinine when heated at 95 — 98° in aqueous 
solution with or without excess of acid undergo rearrangement into 
their poisonous ii^omerides cincbotoxine and quinotoxine. The velocity 
of the reaction is iiicreased when the dissociation constant of the acid 
used is lessened ; this applies to the action of acids both on salts and 
on free alkaloid. With acetic or propionic acid the change is practically 
complete after forty-eight hours' heating ; under the same conditions, 
using an excess of hydrocr.loric acid, practically no rearrangement 
takes place. The same chaLge also takes place slowly when the salts 
are heated at 36^, or when the salt solutions are exposed to direct 
sunlight at the ordinary temperature; in this case much resinous 
matter is also formed, which colours the solution brown. 

It is possible that cincbotoxine and quinotoxine are formed similarly 
in the human organism. E. F. A. 

The Symmetry of Sparteine. Charles Moureu and Amand 
Valeur {Cowpi. rend., 1912, 164, 309—312. Compare this vol., i, 
210). — The action of methyl iodide on tsosparteine hydriodide at 135° 
leads to the formation of isosparteine a-methiodide. The action of 
methyl iodide on sparteine has already been described ; since it leads 
to analogous results, it follows that both bases are symmetrical. As 
this is impossible owing to the mode of formation of isosparteine, 
it follows that the action of methyl iodide on the hydriodides is not 
purely one of simple addition, but involves displacement of the halogen 
hydride by the .alkyl iodide and direct addition of the displaced 
hydrogen iodide. There is therefore no absolute proof of the symmetry 
of the sparteine molecule. 

Reasons are adduced in support of the view that stereoisomerism 
of the groups about the nitrogen atom is sufficient to explain the 
etxistence of two isomeric methylspjirteine methiodides. W. 0. W. 



ORGANIC CHEMISTRY. i. 297 

Methylation of Brucine. Gustav Mossler (Monatsh., 1912, 33, 
19 — 32). — Methylhrucine acetate^ C24H3q05N2,C2H402,5H20, prepared 
by the cautious additiou in portions of silver acetate to a finely 
divided suspension of brucine methiodide in water, crystallises in 
rhombic plates, m. p. (anhydrous) 208—209° (decomp.), [a^^ - 9-97°. 
The same substance was obtained by the action of acetic acid on 
methylhrucine. When warmed with hydrochloric acid, brucine 
methochloride is obtained. 

On treatment with methyl iodide in methyl-alcoholic solution, 
dimethylbrucine iodide , C55Hg305N2l,2|H20, is obtained in flat, right- 
angled plates, m. p. 268° (decomp.). 

Dimethylbrucine acetate^ G^^YL^fi^^ ^,^^fi, is very similar to the 
monomethyl compound, m. p. 205— 206°, [a] i5- 7-14°. With hydro- 
chloric acid the salt, CggKg^OgNgClg, is obtained, m. p. 261°. 

Crystalline products could not be obtained by the oxidation of 
methyl brucine. 

Methyl- and dimethyl-brucine are considered to have the structure 
of betaines, whereas dimethylbrucine iodide is a quaternary iodide. 

E. F. A. 

Hsemopyrrole. J. Grabowski and Leon Marchlewski {Ber.^ 
1912, 45, 453— 456).— The authors have subjected 2 : 4-dimethyl- 
3-ethylpyrrole (Knorr and Hess, Abstr., 1911, i, 1019) to the action 
of benzenediazonium chloride, and find that its behaviour differs from 
that of hsemopyrrole obtained from haemin, since it yields orange 
needles of henzeneazo-'i '.A-dimethyl-^-ethylpyrrole hydrochloride, 

C8Hi2N-N2C6H5,HCl. 
This substance has no definite m. p., but begins to decompose at 120°, 
and evolves gas at about 155°. Attempts to convert it into a disazo- 
derivative were unsuccessful. The authors draw the conclusion that 
trisubstituted derivatives of pyrrole are incapable of reacting with 
more than one molecule of a diazonium salt, and doubt the view that 
one -NgCgHg group of the hsemopyrrole derivative, C8Hi^N(N2CgH5)2, 
is attached to the nitrogen atom. The stability of the hsemopyrrole 
dyes towards hydrochloric acid and the so-called //-acid is a further 
argument against an azo-diazoamino-constitution. 

The reduction of methyl-w-propyimaleinimide (Marchlewski and 
Buraczewski, Abstr., 1905, i, 399; 1906, i, 779) has been repeated 
with larger quantities of material. From the product of the reduction, 
two crystalline dyes were isolated in the form of hydrochlorides, but in 
quantity insufficient for analysis. In hydrochloric acid and in neutral 
solution, however, their spectra are identical with those of the dyes 
prepared from hsemopyrrole. H. W. 

Syntheses of Phyllopyrrole. Chemistry of Hsemopyrrole. 
Hans Fischer and E. Bartholomaus {Btr., 1912, 45, 466 — 471). — 
When substituted pyrroles are heated with alcoholic solutions of 
sodium methoxide or ethoxide, alkylation occurs at a carbon atom. 
In this manner the authors have syuthesised phyllopyrrole, 

. ^«<CMe:6Et 



i. 298 ABSTRACTS OF CHEMICAL PAPERS. 

(compare Willstiitter and Asahina, Abatr., 1912, i, 42), from 2 : 4-di- 
methyl-3-ethylpyrrole and sodium methoxide, from 2:4: 5-trimethyl- 
pyrrole and sodium ethoxide, and from heemopyrrole and sodium 
methoxide. The highest m. p. observed for phyllopyrrole was 69°. 
Phyllopyrrole picrate has m. p. 104 — 106°. 

Similarly, 2 : 4-dimethyl-3-ethylpyrrole was converted by means of 
sodium ethoxide into 2 : 4-dimethyl-3 : 5 -diethyl pyrrole. 

When haemopyrrole is heated with sodium ethoxide, it yields a 

dimethyldiethylpyrrole (isolated in the form of its picrate, m. p. 

102 — 103°) differing from that described above. Since the relative 

positions of the methyl and ethyl groups in hsemopyrrole have been 

determined by its oxidation to methylethylmaleinimide, the authors 

, I. 1 -..TTT ^CMelCMe . , , , 

are led to propose the formula NH<" • for hsemopyrrole, and 

regard its product of its ethylation as 2 : 3-dimethyl-4 : 5-diethyl- 
pyrrole. 

By coupling 2:4: 5-trimethyl pyrrole with diazobenzenesulphonic 
acid, a red dye, C13HJ5O3N3S, was obtained. 

The preparation of phyllopyrrole from hsemin is fully described. 

H. W. 

Mirror Image Isomerism with Iron Compounds. Alfred 
Werner {Ber., 1912, 45, 433— 436).— In order to show that ethylene- 
diamine is not a necessary cause of optical activity in complex metal 
ammonias, the author has investigated the tri-a-dipyridylferrous com- 
pounds, [(Dipyr)3Fe]X2, and has succeeded in obtaining the optically 
active laevo-isomerides by means of cZ-ammonium tartrate. The 
observed specific rotations are very great (>500°), but racemisation 
takes place very quickly in aqueous solution, the rotation falling to 
half its original value in half-an-hour. 

The compounds obtained belong to the class of molecular asymmetry 
II (this vol., i, 166); they prove that optical activity does not depend 
on the presence of ethylenediamine, and also, that it can occur with 
co-ordination compounds of a divalent element. 

Tri-a-dipyridylferrous bromide was prepared in a manner described 
previously (Blau, Abstr., 1889, 1212; 1899, i, 387), and resolved as 
follows : 2*5 grams were dissolved in 112 c.c. of water and 60 grams 
of rf-ammonium tartrate added to the filtered solution, which was 
then cooled to -4°. After some time, intense red crystals of 
\-tri-a-dip7jridylferrou8-di-tartrate separate, which cannot be recrys- 
tallised without loss of activity. A 0*125% solution gave a -0*35° 
in a decimetre tube at 16° ; after three and a-half hours the rotation 
had fallen to zero. 

\- Tri-a-dipyridylferrous bromide, [Fe(Dipyr)3]Br2,6H20, was obtained 
from the tartrate by double decomposition with potassium bromide ; 
it could not be recrystallised, owing to rapid racemisation. It forms 
dark red, flat crystals, and has [a] - 520° and [M]- 4117-8°, 
although these values are probably too low, because of racemisation. 
The iodide, [Fe(Dipyr)8]l2,5H20, was similarly prepared from the 
tartrate and sodium iodide, and forms glistening, dark red, flat 
leaflets ; it has [a] - 440° and [M] - 3818-7°. T. S. P. 



ORGANIC CHEMISTRY. i. 299 

The Preparation of Nitropyridine. Franz Friedl {Ber.^ 1912, 
45, 428 — 430). — The direct nitration of pyridine has been accomplished 
by gradually adding potassium nitrate to a solution of pyridine in 1 8% 
fuming sulphuric acid heated at 330°. p- Nitropyridine crystallises in 
long, colourless needles, m. p. 41°, b, p. 216°. p- Nitropyridine nitrate 
hasm. p. 150—151° 

The position of the nitro-group in the molecule was determined by 
reducing nitropyridine by means of stannous chloride to )8-amino- 
pyridine (Pollak, Abstr., 1895, i, 391), and, further, by the trans- 
formation of this compound into )8-hydroxypyridine (Fischer and 
Kenouf, Abstr., 1884, 1370). 

Nitropyridine is also formed in small quantity by the action of 
concentrated nitric acid on a solution of pyridine in fuming 
sulphuric acid at 330° and atmospheric pressure. H. W. 

4-Oxypyrone and Some of its Derivatives. Alberto Peratoner 
{Gazzetta, 1911, 41, ii, 619—685. Compare Ost, Abstr., 1879, 708; 
1882, 601; 1883, 791; 1884, 1302; 1886, 48; Peratoner, Abstr., 
1902, i, 421, 493 ; Peratoner and others, Abstr., 1905, i, 806, 807 ; 
Palazzo, Abstr., 1905, i, 458; Palazzo and Onorato, Abstr., 1905, i, 
459). — The paper deals with Ost's nitrosopyromeconic acid, and with 
some of its transformation products and their derivatives. The author 
discusses fully the constitution of the substances concerned, in the 
light of the previous work of himself and others and of the new 
experimental data now obtained. 

Further details are given as to the preparation of Ost's nitrosodipyro- 
meconic acid by the action of ethyl nitrite on pyromeconic acid. The 
author also finds that phenol, catechol, resorcinol, pyrogallol, a-naphthol, 
and thymol yield traces of the corresponding nitroso-derivatives when 
they are treated with alkyl nitrites at a low temperature. Benzoyl- 
acetone and ethyl benzoylacetate yield nitroso-derivatives in this way at 
the ordinary temperature. 

When nitrosodipyromeconic acid, C^HgO^NjCgH^Og, is treated with 
rather more than two molecules of phenylhydrazine in glacial acetic 
acid, two products are obtained : (1) a substance crystallising in yellow 
needles, m. p. 165°; (2) a greyish- white, crystalline substance, which 
by treatment with hot benzene is converted into a substance crystal- 
lising in yellow needles, m. p. 199 — 200°. Both compounds have the 

. , , , , , 0-C(N:OH)-C:N-NHPh 
composition required by the formula: ' . — n'l^.-NTWPVi' ^ 

are to be regarded as stereoisomerides. Both yield the same oso- 
tetrazone, CjijrHjgOgNg, when treated with warm alcoholic ferric chloride 
solution. The osotetrazone crystallises in red needles, m. p. 137 — 138°, 
which appear black with a metallic lustre when viewed by reflected 
light. Both hydrazo-oximes when kept at 210° lose one molecule of 
water, yielding a substance, C^>jH^fi'N^, which forms white needles, 
m. p. 242°. 

Ost's nitrosodipyromeconic acid also yields a quinoxaline, C^^H^OgNg, 
when treated with o-phenylenediamine hydrochloride in glacial acetic 
acid in the presence of sodium acetate. The substance forms lemon- 



i. 300 ABSTRACTS OP CHEMICAL PAPERS. 

yellow crystals, gives a green coloration with sulphuric acid, and 
dissolves in alkali hydroxides, forming yellow solutions, from which 
the original substance is precipitated by carbon dioxide. 

[With A. Tamburello.] — In proof of the constitution previously 
given for Ost's pyromecazonic acid (2 : 3-dihydroxy-4-pyridone), it is 
found that the product of the reaction of its diacetyl derivative with 
diazomethane yields about the same figures for -OMe and INMe groups 
when analysed by the methods of Zeisel and of Herzig and Meyer 
respectively. The pyromecazonic acid does not react with ethyl 
nitrate, and therefore does not contain a ketom ethyl en ic grouping. 

Ost's pyromecazone (obtained by oxidation of pyromecazonic acid) 
behaves in the same way when treated with diazomethane, for the 
yellow oil which is obtained contains only half the calculated amount 
of -OMe group. The action of diazoethane is different : the product, 
both from the free quinone and from its additive product with ethyl 
alcohol, contains almost the amount of -OEt group corresponding with 
the formula C^HgOgN'OEt. To the quinone the constitution 

ch:n CO 

6h-C(0H)-C0 
is assigned. It gives the reddish-violet coloration with potassium 
hydroxide described by Bamberger as characteristic of o-quinones, and 
with o-phenylenediamine it forms a quinoxaline, Q^^ll>jO^^, which 
crystallises in canary-yellow needles, and for which the formula 
CH'NH'CIN 

nTT-rtn-n'xr^^fi"^* ^® suggested. The acetyl derivative of the quin- 
oxaline, CjgHpOgNg, forms greenish-yellow needles. 

In support of the conclusion that Ost's oxypyromecazonic acid is 
1:2: 3-trihydroxy-4-pyridone, the author finds that when a saturated 
aqueous solution of the substance is treated with ferric chloride, a red 
iron salt is precipitated, having the composition Fe(C5H^04N)3,3H20. 
The acid also forms a triacetyl derivative, C^HgO^NAcg, which crystal- 
lises in aggregates of minute needles, m. p. 123 — 124°, and a trihenzoyl 
derivative, C^HgO^NBzg, crystallising in colourless needles, m. p. 
162 — 163° The position of the third hydroxyl group (attached to 
nitrogen) follows from the fact that it is readily reduced by tin and 
hydrochloric acid or by hydriodic acid, and from the production of the 
iron salt above mentioned. 

[With A. Tamburello.] — By the action of hydroxylamine on the 
ethers of comenic acid, derivatives of 1-hydroxypyridone can be 
obtained. When ethylcomenic acid is treated with hydroxylamine, an 
acid, CgHgOgN, is obtained, m. p. 174 — 175° (with evolution of carbon 
dioxide). The substance gives a red coloration with ferric chloride. 
Its ethyl ester, OEt*C^H20(C02Et):N-OH, forms colourless needles, 
m. p. 156°. The acetyl derivative, OEfC5H20(C02Et):N-OAc, 
forms rosettes of colourless needles, m. p. 81 — 82°. The action of 
hydroxylamine on ethyl ethylcomenate yields the above ethyl ester of 
m. p. 156°. To the acid of m. p. 174 — 175° the structure of l-hydroxy- 
2-ethoxy-4:-pyridone-6-car boxy lie acid is ascribed. When it is reduced 
with tin and hydrochloric acid, it yields a substance, CgHgO^N, which 
crystallises with IHgO in rosettes of colourless needles, m. p. 224 — 225°, 




ORGANIC CHEMISTRY. i. 301 

but when dehydrated (at 150°) it melts at 235° (decomp.). It 
gives an orange-yellow coloration with ferric chloride, and to it is 
assigned the constitution of Z-ethoxyA-pyridone~^-carhoxylic acid. It 
is identical with the product of the action of ammonia on ethylcomenic 
acid, and is also obtained by reduction of the ethyl ester above 
mentioned (m. p. 156°), since the ester is saponified at the same time. 
3-Ethoxy-4-pyridone-6-carboxylic acid is hydrolysed when boiled for 
two hours with hydriodic acid (D 1 '74), yielding '^ -hydroxy -^-pyridone- 
Q-carboxylic acid (Ost's comenamic acid). When l-hydroxy-3-ethoxy-4- 
pyridone-6-carboxylic acid is kept at 190° for some time, l-hydroxy-3- 
ethoxy-i-pyridone is obtained ; it crystallises in colourless needles, m. p. 
156°, and gives a brownish-red coloration with ferric chloride. 

[With E. Carapelle.] — The phenylhydrazones of pyromeconic acid 
and some of their derivatives have also been investigated. When 
a solution of phenyldiazonium acetate is treated with a solution of 
pyromeconic acid at 0°, the monophenylhydrazone, Cj^HgOgNg, is pro- 
duced ; it forms dark red or purple crystals, which decompose at 176°. 
When it is treated with two molecules of phenylhydrazine, it yields two 
triphenylhydrazones, C5H20(!N'NHPh)3, which are apparently stereo- 
isomeric. One of these has m. p. 161 — 162°, the other has m. p. 
212 — 214°. The former is converted into the latter if hydrogen 
chloride is passed through its alcoholic solution for half an hour. The 
monohydrazone reacts with o-phenylenediamine, yielding a quinoxalinej 
Cj^HjgON^. The monohydrazone is also readily converted into an 
hydroxy pyridone derivative, and this indicates the analogy between its 
structure and that of oximinopyromeconic acid. When it is mixed with 
a little water and treated with sulphur dioxide at 0°, a substance, 
C^^HjoOgNg. is obtained, which forms crystalline scales, m. p. 220°, and 
is assigned the constitution of \-anilino-2 : S-dihydroxy-4:-pyrido7ie. Its 
hydrocfdoride, CijHjQOgNg.HCl, crystallises in colourless needles. Its 
diacetyl derivative, CjiHgOgNgAcg, crystallises in lustrous scales, 
m. p. 155 — 156°. l-Anilino-2 : 3-dihydroxy-4-pyridone gives with 
ferric chloride a deep blue coloration, which disappears when excess 
of ferric chloride has been added. The quinone thus produced 
reacts with o-phenylenediamine, yielding a quinoxaline, Oj^HjgON^, 
which forms golden-yellow scales, m. p. 181 — 182°. The quinone is 
best obtained by oxidising the pyridone with silver oxide, but it has 
been isolated only in the form of its additive product with methyl 
alcohol, Ci^Hg03N2,MeOH, which dissociates and melts (forming a red 
liquid) at tt7— 88°. 

[With A. D'Angblo.] — The authors have also prepared some 
derivatives of dibromocomenic acid. Dibromocomenic acid (compare 
Mennei, Abstr., 1883, 656) reacts with basic lead acetate, losing both 
atoms of bromine, and the corresponding quinone is formed, but could 
not be isolated. Both dibromocomenic acid and this quinone react 
with o-phenylenediaoiine, yielding a quinoxaiinet to which the formula 

C02H-C— o— c:n. ^ „ 

rH'PO'P'N^ 6"-4 ^s ascribed. It dissolves in alkalis, giving a 

yellowish-red coloration, and in concentrated sulphuric acid, giving a 
red coloration. When heated it decomposes above 200°. It yields a 
phenylhydrazonct which decomposes about 170°, to which the formula 



i. 302 ABSTRACTS OF CHEMICAL PAPERS. 

CH-C(:N-NHPh)-6:N'^ ^^^ '^ assigned. Ihe phenylhydrazone 
yields the corresponding xantho-ioilt when treated with potassium 
hydroxide. The constitution of these substances is an argument in 
favour of the ketomethylenic formula for comenic acid. R. V. S. 

4 : 6-Dinitrophenyl-l : 3 - dipy ridinium Chloride and 4:6- 
Dinitro-3 aminopyridinium Chloride. Theodor Zincke and G. 
Weisspfenning {J. p\ Chem., 1912, [ii], 85, 207—210. Compare 
Abstr., 1910, i, 585). — When 4: 6-dinitro-l : 3-dipy ridinium chloride 
is heated for five minutes with aniline in alcoholic solution, it is 
converted into 4 : 6-dinitro-3-aminophenylpyridinium chloride and the 
previously-described dianilide, NPhlCH-CHICH-CHICH-NHPh, only 
one of the pyridine groups being removed. The further action of 
aniline on 4 : 6-dinitro-.3-aminophenylpyridinium chloride results in 
the removal of the second pyridine group with the formation of the 
dianilide, together with 4:6- dinitro - m - pJienylenediamine^ which 
separates from glacial acetic acid in brownish-yellow crystals, m. p. 
300°. If the action is continued for three to four hours, the dianilide 
disappears, and on the addition of hydrochloric acid, 4 : G-dinitrol : 3- 
diaminobenzene hydrochloride and phenylpyridinium chloride (Abstr., 
1904, i, 921) are obtained. 

The successive action of excess of 2A^-sodium hydroxide and hydro- 
chloric acid on an aqueous solution of dinitroaminophenylpy ridinium 
chloride yields a red, crystalline substance, C^jH^qO^N^, the constitu- 
tion of which is represented by one of the following formulae. 

/\ ^ CH-OH /\ ' CHO 

NOI 1 ^ 9H NO I I ^ ?^ . 

^\j/ CH ^\/ CH 

N=CH-CH NH— CH:6h 

This substance decomposes when heated, gives a reddish-violet 
coloration with alcoholic potassium hydroxide, and is reconverted by 
warm concentrated hydrochloric acid into dinitroaminophenyl- 
pyridinium chloride. 

The interaction of dinitrophenyldipyridinium chloride and phenyl- 
hydrazine in alcoholic solution yields a deep black, crystalline «tfc6s<anc«, 
the composition of which is represented by one of the following 
formulae : 

C6H2(N02)2(N:CH-CH:CH-CH:CH-NH-]SrHPh)2. 
C6H2(N02)2(NH-CH:CH-CH:CH-CH:N-NHPh)2. 
The same compound is produced by the action of phenylhydrazine 
on the blackish-green substance, CjgHj^OgN^, formed from dinitro- 
phenyldipyridinium chloride and alkalis (Abstr., 1910, i, 585). 

F. B. 

Action of Hydrogen Sulphide on Dinitrophenylpy ridinium 
and Dinitrophenyldipyridinium Chlorides. Theodor Zincke 
and G. Weisspfenning {J. 'pi\ Chem., 1912, [ii], 85, 211—217).— 
The action of hydrogen sulphide on 4 : 6-dinitrophenyl-l : 3-dipyri- 



ORGANIC CHEMISTRY. i. 303 

dinium chloride leads to the removal of one of the pyridine groups 
and the formation of a thioheiaine anhydride (I), similar in constitution 
to the anhydride previously described (Abstr., 1910, i, 585). The 
thiobetaine anhydride exists in two forms, an orange-red modification, 

containing IHgO, obtained by passing 
j^Oo NOo hydrogen sulphide into an aqueous 

/\ /\aTT solution of the pyridinium chloride, 

^ I ry ^^ I I aiid a dark red form, which crystallises 

■'^^2\ / ! ^^2\ / in leaflets and explodes on heating. 

I I I The latter modification is produced by 

C^6^5^ CJgHgNCl ^2^ ^jjg action of hydrogen sulphide on 

(I.) (11.) a 90% alcoholic solution of the pyridi- 

nium chloride, and (2) by dissolving 
the orange- red variety in concentrated hydrochloric acid and diluting 
the solution with water. The anhydride forms salts, which are 
instantly decomposed by water ; the hydrochloride (II), prepared from 
the anhydride and hydrogen chloride in alcoholic solution, crystallises 
in white needles ; the platinichloride is also described. The anhydride 
is converted by successive treatment with aqueous alkalis and acetic 
acid into an orange, crystalline substance, probably 

sh-C6H2(N02)2-n:ch-ch:ch-ch:ch-oii. 

A similar removal of the pyridine group takes place by the action 
of hydrogen sulphide on 2 : 4-dinitrophenylpyridinium chloride in 
aqueous solution, the product in this case consisting of 2 : 4-dinitro- 
phenylmercaptan, accompanied by a small amount of 2 : 2' : 4 : 4'('?)-tetra- 
nitrodiphenyl sulphide. The latter compound forms the main product 
when tbe hydrogen sulphide is replaced by sodium sulphide, or the 
action carried out in alcoholic solution. F. B. 

Trinitrophenylpyridinium Chloride. Theodor Zincke (J. ^r, 
Chem., 1912, [iij, 86, 217—221. Compare Busch and Kcigel, this vol., 
i, 50), — 2 : 4 : 6-Trinitrophenylpyridinium chloride is best prepared by 
the interaction of picryl chloride and pyridine in ethereal solution. 
It has m. p. 128 — 129° (decomp.), and is resolved by alcoholic 
hydrogen chloride at 100" into its components ; the yellow, crystalline 
platinichloride i {Q-^^]l>j0^fi\)^tQ\Q^ has ra. p. 255° (decomp.). 

On successive treatment with hydrogen sulphide and hydrochloric 
acid, it yields a substance, which crystallises in dark violet leaflets of 
a metallic lustre. It reacts with aniline, forming the dianilide, 
CiH-HjgN'g, previously described (Abstr., 1904, i, 921). 

The {fz-base, C^j^HgO^N^, obtained by the action of alkalis, forms 
brown crystals, m. p. 190 — 193° (decomp.), yields a sodium salt, and 
is converted by acetic and hydrochloric acids into picramide and the 
original pyridinium salt. F. B. 

Conversion of Oxindole into Coumaran-1-one. Charles 
Marschalk (Ber., 1912, 85, 582 — 585). — Oxindole has been trans- 
formed into coumaran-1-one by heating it with barium hydroxide in 
aqueous solution at 150°, converting the resulting barium o-amino- 
phenylacetate (Baeyer and Comstock, Abstr., 1883, 1130) by means of 



i. 804 ABSTRACTS OF CHEMICAL PAPERS. 

the diazo-reaction into o-hydroxyphenylacetic acid, and removing 
water from the latter compound by distillation. The diazotiaation is 
accomplished by the addition of an aqueous solution of the barium salt 
and sodium nitrite to cold dilute sulphuric acid. 

Oxindole is readily prepared by the reduction of isatin with sodium 
hyposulphite to dioxindole and subsequently reducing this by means 
of sodium amalgam in aqueous alcoholic solution. Dioxindole has 
m. p. 167 — 168°, and not 180° as given by Baeyer and Knop (Anncderif 
1866, 140, 11). When di>solved in aqueous sodium hydroxide and 
the solution treated with alcohol, it yields a crystalline sodium salt, 
which, however, is two unstable to be isolated, is converted by dilute 
sulphuric acid into dioxindole, but is apparently different from the 
sodium salt obtained by Baeyer and Knop by reducing isatin with 
sodium amalgam. F. B. 

Some New Derivatives of Carbazole. Bruno Levy [Monatsh.y 
1912,33, 177 — 184). — It has been discovered that the high temperature 
(170—190°) used byGraebe and von Adlerskron (Abstr., 1880, 660) in 
the preparation of methyl- and ethyl-carbazole was unnecessary, and 
that potassium carbazole reacts with methyl iodide almost quantita- 
tively at the ordinary temperature. In extending the reaction to other 
alkyl halides, it is found that the velocity of the reaction decreases as 
the series is ascended, and also that the normal alkyl halides give a 
greater reaction velocity than the branched ones. Although no 
exact measurements were made, allyl iodide and benzyl chloride were 
found to react much more readily than ethyl iodide. 

n-Propylcarhazole was obtained by the reaction of the iodide with 
potassium carbazole on the water-bath ; it forms needle crystals, m. p. 
50°, and gives sl pier ate ^ m. p. 98°. 

ISO Propylcarlazole, obtained similarly, has m. p. 120°, and gives a 
picratej m. p. 143°. 

n-Butylcarbazole forms needles, m. p. 58°, and gives a ^jJtcrafe, 
m. p. 89° sec- Butylcarbazole is an oil, which gives a picrate^ m. p. 
64°. ISO Butylcarhazole is also an oil ; the picrate has m. p. 177°. 

180 Amy Icarbazole is an oil ; the picrate has m. p. 85°. &ec.-Amyl- 
carhazole is also an oil ; m. p. of picrate^ 93°. 

AUylcarhazole, obtained by reaction at room temperature, crystallises 
in colourless rhombs, m. p. 56° ; the picrate has m. p. 86°. 

Benzylcarbazole, also prepared at the ordinary temperature, forms 
colourless needle.^, m. p. 114°; m. p. of picrate, 105°. 

Triphenylmeihylcarhazole, obtained by reaction of triphenylmethyl 
chloride and potassium carbazole in boiling benzene, forms rhombic 
crystals, m. p. 245°. D. F. T. * 

Thioamides. IV. Action of Hydrogen Sulphide on 
Nitrogen-bubstituted Aminoacetonitriles. Treat B. Johnson 
and Gerald Burnham (Amer. Chem. J., 1912, 47, 232 — 242). — In an 
earlier paper (Abstr., 191 1, i, 712) it has been shown that aminoaceto- 
nitrile reacts with hydrogen sulphide to form the corresponding 
thioamide, which is unstable and undergoes condensation in alcoholic 



ORGANIC CHEMISTRY. 1. S05 

solution with production of thioglycylglycinethioamide. This thio- 
polypeptide is also unstable, and becomes converted into dithio- 
piperazine. The present investigation was undertaken in order to 
ascertain whether thioamides of iV^-substituted amino-acids of the type 
R'NH'CHg'CS'NHg would undergo similar transformations. It has 
been found that phenylaminoacetonitrile, />-tolylaminoacetonitrile, 
anisoy laminoacetonitrile, hippuronitrile, carbethoxy aminoacetonitrile, 
and carbamidoacetonitrile all combine smoothly with hydrogen 
sulphide at the ordinary temperature to form the corresponding 
thioamides, which are stable compounds, and can be heated with 
alcohol without undergoing any change. When these thioamides are 
heated above their m. p.'s they suffer decomposition, but without 
producing a thiopolypepfcide derivative or dithiopiperazine. 

Hippurothioamide, 06H^-CO-NH-CH2-OS-NH2, m. p. 150°(decomp.), 
crystallises in transparent blocks, and reacts with bromoacetophenone 
with production of A:-phenyl2-henzoylaminomethylthiazole, 

m. p. 148°, which forms rosettes of needles. 

Garhethoxyaminoacetothioamide, COgEt'NH'CHg'CS'NHg, m. p. 118°, 
crystallises in rectangular blocks, and condenses with bromoaceto- 
phenone to form 4:-phenyl-2-ca7'bethoxyaminomethylthiazole, 

m. p. 59 — 61°, which crystallises in prisms, and yields an unstable 
hydrohromide. When this hydrobromide is heated with hydrobromic 
acid, it is converted into i-phenyl-2-aminomethylthiazole hydrobromide, 

Np^^-^>C-CH2-NH2,2HBr, m. p. 253° (decomp.). 

Anisoylaminoacetonitrilei OMe-CgH^'CO'NH'CHg'CN, m. p. 
153 — 154°, prepared by treating an aqueous solution of aminoaceto- 
nitrile sulphate with anisoyl chloride and potassium hydroxide, forms 
thin, transparent plates. Anisoy la minoacetothioamidef 

OMe-OgH^-OO-NH-CHg-CS-NHg, 
m. p. 189° (decomp.), crystallises in slender prisms. 

Anilinoacetothioamide, NHPh'CHg'CS'NHg, m. p. 166° (decomp.), 
forms stout blocks. 

^-Toluidinoacetothioamide, C6H4Me-NH-CH2-CS-NH2, m. p. 152°, 
crystallises in rhombic plates or tabular prisms, and reacts with 
bromoacetophenone to form 4:-phenyl-2-p-toluidinomethyltkiazole, 

CPh-N^^'^^^'^H-CgH^Me, m. p. 110—111°, which crystallises in 

prisms. When ^-toluidinoacetonitrile is heated with phenylthio- 
carbimide, 2-thio - 5 - phenylthiocarhamido - 1 - phenyl - 3 - Tp-tolyldihydro- 

N Ph • C ^ 
glyoxaline, NHPh-CS-NH-C<^^ i ^ ^^ ^^ , m. p. 201^isproduced, 

Oil JN 'Ogtl^Me 
which crystallises in bright yellow needles. 

Carbamidoacetothioamide, NHg'CO-NH-CHg'CS'NHg, m. p. 
190 — 191° (decomp.), forms colourless prisms, and condenses with 
bromoacetophenone with formation of 4:-phenyl-2-carbamidomethyl-' 



I. 306 ABSTRACTS OF CHEMICAL PAPERS. 

r*TT ra 
thiazoh, Hp, >C-CH2-NH«C0»NH.^, m. p. 190", which crystallises 

in slender needles, and yields a hydroln'omide, m. p. 214° (decomp.). 

E. G. 

Formation of 1 : S-Thiazines from Thiocarbamide. 
William J. Hale and Harvey C. Brill (/. Amer. Chem. Soc, 1912, 
34, 295 — 300). — In an earlier paper (this vol., i, 216) it has been 
shown that carbamide condenses with nitromalonaldehyde with 
formation of 5-nitro-2-hydroxypyrimidine. It has now been found 
that the condensation of thiocarbamidejwith nitromalonaldehyde takes 
place in an entirely different manner. 

When thiocarbamide and nitromalonaldehyde are allowed to react 
in aqueous solution in presence of a very small quantity of sodium 
hydroxide or diethylamine, the monothioureide of the aldehyde is 
produced. If piperidine is used as the condensing agent, however, 
5 nitro-2-imino-l : 3-thiazine separates, whilst a small amount of the 
thioureide remains in the mother liquor. 

Nitromalonaldehyde monothioureidej 

nh:c(sh)-n:ch-ch(no2)-cho, 

m. p. 206 — 207° (corr.), crystallises in lustrous, yellow leaflets, and is 
readily desulphurised by treatment with basic lead acetate solution or 
mercuric oxide ; its potassium salt forms reddish-brown crystals ; the 
lead salt was also prepared. The methyl ether, m. p. 78 — 79° (corr.), 
obtained by the action of methyl sulphate on an aqueous solution of 
the potassium salt, forms yellow plates. Phenylhydrazine acetate 
reacts with the thioureide with formation of the phenylhydrazone. 
When the thioureide is suspended in alcohol and piperidine added, it 
is transformed into 5-nitro-2-imino-l : 3-thiazine. 

f>-Nitro-%%mi'ao-\\^-thiavi'M, N02-C<^^.*^>C:NH, m. p. 

151 — 152° (corr.), crystallises in long, yellow needles, and is not 
affected when boiled with an alkaline solution of lead acetate or with 
mercuric oxide. Phenylhydrazine and aniline do not have any effect 
on the compound, but benzonesulphonyl chloride reacts with it to 
form a yellow mass, thus establishing the presence of the imino-group. 
By the action of acetic anhydride, it is converted into the acetyl 

derivative, N02-C<^j^.*^>C:NAc, m. p. 141° (corr.). E. G. 

A Peculiar Auxochrome Action. Walter Konig {Jerh. Ges. 
deut. Naturforsch. Aerzte, 1912, ii, [I], 221— 223).— The colour of 
the pyridine dyes, obtained from pyridine and primary or secondary 
amines, is not satisfactorily accounted for by the usual formula : 
NRR'-CHICH-CHICH-CHINCIRR'. The yellow colour of the 
simplest representative, obtained from methylaniline, becomes more 
green when the side-chain is lengthened by saturated alkyl groups, or 
when an ortho-substituent is introduced into the benzene ring. On 
the other hand, cyclic secondary amines, such as tetrahydroquinoline 
or dihydroindole, change the colour to red. These changes are 



ORGANIC CHEMISTRY. i. 807 

accounted for if one 'or other of the following formulae is used, 
involving subsidiary valencies : 

CI H 

\/ 
C CH 

/i\ /\ 

fi^ , (II.) ^fi 9^ 



(I.) ^fi 



CH-NRR' ' ' HC CH-NRR' 



N 01 

/\, 
R R R R 

In accordance with Kaufmann's hypothesis, the subsidiary valency 
indicated by the dotted line should shift the colour more towards red 
the stronger it is. This is explained by a comparison with Kaufmann's 
views on benzene compounds. C. H. D. 

Optically Active Hydrazino-acids. August Darapsky {Verh. 
Ges. deut. Naturforsch. Aerzte, 1912, ii, [1], 215 — 216). — Hydrazino- 
acids of the formula NHg'NH^CHR'COgH have only been obtained 
in the racemic form by Traube (Abstr., 1896, i, 340) and Thiele 
(ibid., 341) The author's simpler method of preparation (Gkem. Zeit., 
1910, 34, 1280) allows of the preparation of the active modifications. 

\-Hydrazinophenylacetic acid, NHg'NH'CHPh'COgH, prepared from 
the c?-chloro-acid and hydrazine hydrate, [has [aj^- 157*8° in 2*7% 
solution in iV/1 -hydrochloric acid ; the <i-acid, prepared from the 
^■chloro-acid, has [ajo -f- 158 0°. The rotation is nearly the same as 
that of the analogous amino-acid (±157*9°) and of the hydroxy-acid 
(mandelic acid, ± 157°). d- and ^-Hydrazinophenylacetic acids crystallise 
from water in silvery leaflets, m. p. 183 — 184° (racemic compound, 
188 — 189°). Condensation with benzaldehyde yields active 6en«?/^2c^ene 
compounds, crystallising from dilute alcohol in slender needles, m. p. 
136 — 138°, whilst the racemic compound has m. p. 150°. The 
rotatory power is [a]?? ±166*5° in acetone, 2*5% solution. It has not 
been found possible to resolve the racemic compounds. C. H. D. 

Reduction of Aromatic Aldazines. Theodor Curtius {J. p\ 
Chem., 1912, 85, [ii], 137 — 188). — A continuation of previous work 
(this vol., i, 137). 

[With Fritz Mayer. J — 2 : ^-Dimethylhemylhydrazine, 
CeHgMeg-CH^-NH-NHg, 
is obtained as a colourless, viscid liquid, b. p. 136 — 137°/ 13 mm., by 
distilling the monohydrochloride (Abstr., 1900, i, 610) with calcium 
oxide under diminished pressure. It is very unstable, giving off 
nitrogen when kept, and is much less basic than the lower homologues 
previously described (Abstr., 1901, i, 573) ; its dihydrochloride, m. p. 
164°, loses hydrogen chloride very readily, and is almost completely 
resolved into the monohydrochloride by crystallisation from alcohol. 
The sulphate, microscopic crystals, m. p. 163°, oxalate, m. p. 192°, and 
picrate, lustrous, yellow needles, m. p. 148°, are described. 



i. 308 ABSTRACTS OF OHEMICAL i>APERS. 

On exposure to air, it is oxidised to 2 : 4dimethylbenzaldehyde- 
2 : 4-dimethylbenzylliydrazone, m. p. 78° (Abstr., 1900, i, 610); the 
oxidation may also be effected by heating the hydrochloride with 
mercuric oxide and alcoholic sodium hydroxide. When heated with 
dilute hydrochloric acid, it yields 2 : i-dimethi/lbenzyl chloride, 
CgHgMeg-CH.Cl, a colourless, viscid liquid, b. p. 103—104719 mm., 
having a pleasant aromatic odour. The dibenzoyl derivative, 
CgHgMeg'CHg'NgHBzg, crystallises in short, colourless columns, 
m. p. 169 — 170°; the diacetyl derivative, C^gH^gOgNg, forms colourless 
leaflets, m. p. 129°. 

2 : 4-Dimethylbenzylhydrazine hydrochloride reacts with potassium 
cyanate in aqueous solution, yields 2 : ^-dimetht/lbenzylsemicarbazide, 
C6H3Me2-CH2-N(NH2);CO-NH2, columnar crystals, m. p. 162°, and 
with phenylthiocarbimide and alcoholic potassium hydroxide, yielding 
phenyt-2 : Ai-dimethylhenzylthiosemicarbazide, 

C6H8Me2-CH2-N(NH2)-CS-NHPh, 
which crystallises in short, colourless columns, m. p. 138-5°. 

a-2 : i-Dimethylbenzylhydrazonopropionic acid is obtained as a yellow 
oil by the interaction of the hydrochloride, sodium acetate, and pyruvic 
acid in aqueous solution. 

a-Nitroso-a-2 : A-dimethylbenzylhydrazine, CgH3Me2*CH2'N(NO)*NH'2, 
prepared from the hydrochloride and sodium nitrite, crystallises in 
colourless leaflets or needles, m. p. 60*5°; it reacts with 2 : 4-dimethyl- 
benzaldehyde, yielding 2 : 4-dimethylbenzaldehyde-2 : 4-dimethylbenzyl- 
nitrosohydrazone {loc. cit.), and when heated at 80° with 10% sulphuric 
acid is converted into 2 : 4:-dimethylbenzylazoim.ide, CgH3Me2*CH2*N3. 
This forms a colourless liquid, b. p. 114°/15 mm., and is stable 
towards alkalis ; it is hydrolysed by 20% sulphuric acid to hydrazoic acid 
and 2 : 4-dimethylbenzyl alcohol, small quantities of ammonia, 2 : 4- 
dimethylbenzaldehyde, 2 : 4-dimethylbenzylamine, and m-4-xylidine 
being produced simultaneously. 

When heated with ethyl acetoacetate, 2 ; 4-dimethylbenzylhydrazine 
yields etJiyl /3-2 : A-dimethylbenzylaminocrotonate, 

CeH3Me2-CH2-NH •CMe:CH-C02Et, 
colourless leaflets, m. p. 85°, together with an oil, consisting probably 
of ethyl /3-aminocrotonate. The formation of these two substances is 
considered to be due to the reduction of the hydrazine base by ethyl 
acetoacetate to ammonia and 2 : 4-dimethylbenzylamine, which then 
react with the ester to form ethyl ^-amiuocrotonate and ethyl 
j3-2 : 4-dimethylbenzylaminocrotonate respectively. 
^-Phenyl- 1 -oT^dimethylbemyl-b-pyrazolonet 

pTT .p() 

prepared by heating the hydrazine base with ethyl benzoyl acetate, 
crystallises in colourless needles, m. p. 162°, dissolves in both acids 
and alkalis, and combines with jo-toluenediazonium sulphate to form a 
scarlet-red azo-dye ; its solution in aqueous ammonia gives sparingly 
soluble, crystalline precipitates with nickel, cobalt, copper, and silver 
salts. 

A'Oximino-3-pIienyl-l -op - diniethylbenzyl-5 -pyrazolone, CjgHiyOgNg, 
obtained by the action of sodium nitrite on the preceding coujpound in 



ORGANIC CHEMISTRY. i. 309 

acetic aci i solution, crystallises in slender, red needles, m. p. 128° 
(decomp.). On treatment with silver nitrate it forms a brownish- 
yellow silver salt, which becomes green when warmed with glacial acetic 
acid, nd then has the composition CjgHjgOgNgAg. The latter com- 
pound decomposes at 236°, and is probably the silver salt of 4:-nitro- 
3-phenyl-l-op-dimethylbenzyl-6-pyrazolone. 

3- Phenyl-l-o]^-dimetkylbenzyl-2-met?iyl-6 -pyrazolone, prepared from 
methyl iodide and the above-mentioned phenyldimethylb enzyl- 
pyrazolone, is a brown oil. 

d-Phenyl-l-op-dimethylbenzyl-'Z-methyl-Q-pyridazinone, 

CH,<^«|_^0>N-CH,-C,H3Me2, 

is obtained by the interaction of dimethylbenzylhydrazine hydro- 
chloride, sodium acetate, and Isevulic acid in aqueous solution ; it has 
m. p. 79-5°. 

[With Hartwig Franzen.] — aa-Di-2 : 4 •.^-trimethylhenzylhydrazine, 
NH2*N(CH2*CgH2Me3)2, prepared from the hydrochloride (Abstr., 
1901, i, 293) and sodium hydroxide in aqueous alcoholic solution, 
crystallises in white needles, m. p. 75°, and forms a sulphate, needles, 
m. p. 151°; nitrate, leaflets or needles, m. p. 118° (decomp.), and 
platinichloride, m. p. 95° (decomp.). It reacts with acetone, yielding 
acetonedi-2 : 4 :b-tri7nethylbenzylhydrazone, 

CMe2:N-N(CH2-C6H2Me3)2, 
crystallising in small needles, m. p. 132°, and with isobutaldebyde to 
form isobutaldehydedi-2 : 4 : ^-trimethylbenzylhydrazone, 024X13^^2, m. p. 
112°. When heated with acetic anhydride, it yields a diacetyl 
derivative, C24H32O2N2, m. p. 126°; the monobenzoyl derivative, 
C27H32ON2, has m. p. 129°. 

Di-2 : 4 : b-triniethylbenzylsemicarhazide, 

NH2-CO-NH-N(CH2-C6H2Me2)2, 
prepared from the hydrochloride and potassium cyanate in aqueous 
solution, crystallises in needles or leaflets, m. p. 173°. 

aa-Di-2 : 4 : 5-trimethylbenzylhydrazine forms an ethiodide, 

white needles, m. p. 160°, and is oxidised by mercuric oxide in chloro- 
form solution to di-2 : 4 : 5-trimethylbenzyltetrazone, 

N(CH,-0,H2Me,)2-N:N-N(CH2-CeH2Me3)2, 
which forms white needles or leaflets. 

[With Reinhold Korte.] — p - Cuminaldazine, prepared from 
cuminaldehyde and hydrazine sulphate, has m. p. 111° (compare 
Gattermann, Abstr., 1906, i, 592). On reduction with sodium 
amalgam in alcoholic solution it yields ^ cuminaldehyde-^-cuminyl- 
hydrazone, C6H4Pr/3-CH:N-NH-OH2-CgH;Pr^, which crystallises 
in small, lustrous, strongly refractive, yellowish-green columns 
of a rhombic habit, m. p. 75° (decomp.). The hydrazone is 
unstable, becoming oily when kept. It forms a benzoyl derivative, 
C27II3QON2, m. p. 78°, and a ntiro^o-compound, 

C6H4Pr/^-CH:N(NO)-CH2-06H4Pr^, 
crystallising in light yellow, felted needles, m. p. 59°. When heated 
in alcoholic solution, the nitroso-compound is converted into 
cuminaldazine. 
VOL. CXI. i. y 



i rjlO ABSTRACTS OF CHEMICAL PAPERS. 

B-Dip-€uminylhydrazine, N2H2(CgH^Pr/^)2, obtained by the pro- 
longed reduction of cuminaldazine with sodium amalgam and alcohol, 
forms a white, wax-like mass, which rapidly decomposes ; the hydro- 
chloride crystallises in hexagonal plates, m. p. 217° (decomp.J, the 
diacetyl derivative, C24Hg202N2, in large, rhombic columns, m. p. 71°. 
The (itnt^-oso- derivative, N2(NO)2(CQH4Pr^)2, forms small tufts of 
yellow needles, m. p. 59°, and when heated in alcoholic solution 
yields the above-mentioned jo-cuminaldehydenitroso-jo-i«opropylbenzyl- 
hydrazone, together with cuminaldazine and di-^cuminylidene- 
di'p-^uminyldihydrotetrazone, 

N2(CH2-CeH,Pr^)^N:CH-CeH,Pr^)2, 
m. p. 194°. The formation of the latter compound is considered to be 
due to the intermediate formation of p-cuminaldehyde-jt>-cuminyl- 
hydrazone, which is then oxidised by the nitrous acid, produced 
by the hydrolysis of the corresponding nitrosohydrazone, but 
all attempts to prepare the tetrazone by oxidising j9-cnminyl- 
hydrazone with mercuric oxide in alcoholic or benzene solution proved un- 
successful, the sole product of the oxidation consisting of cuminaldazine. 

^ - Cuminylhydrazine, CgH^Pr^^'CHg'NH'NHg, obtained in the 
form of its hydrochloride (slender needles, m. p. 199°, with previous 
sintering at 143°) by hydrolysing ;)-cuminaldehyde - /? - cuminyl- 
hydrazone with dilute hydrochloric acid, has m. p. 46° ; it is very 
unstable, and rapidly loses nitrogen at the ordinary temperature. The 
niiroso-compound, CgH4Pr/'*CH2'N(NO)*NH2, forms very slender, felted 
needles, m. p. 63°, and when heated with 10% sulphuric acid is converted 
into p-cuminylazoimide, CgH^Pr^'CHg'Ng, a pale yellow oil, b. p. 
118°/23 mm., which is stable towards alkalis, but is decomposed by 
40% sulphuric acid with the evolution of nitrogen ; hydrazoic acid is 
not produced. 

[With Hermann Wewer]. — m-Chlorobenzaldazine, m. p. 141°(compare 
Curtius and Melsbach, Abstr., 1910, i, 508), is reduced by zinc dust 
and glacial acetic acid in alcoholic solution to di-7?i-chlorobenzylamine. 
This crystallises from alcohol in small needles, m. p. 112°, and is 
identical with Berlin's " ^-gechlortes Bibenzylamin " (Annalen, 1869, 
151, 141). The following salts of the amine are described : the hydro- 
chloride, m. p. 227° ; nitrate, m. p. 203° ; platinichloride, brown needles, 
m. p. 222° (decomp.), and nitrite, lustrous, white needles, m. p. 133°. 

Di-m-chlorohenzylnitro8oamine, NO*N(CH2'CgH4Cl)2, prepared by 
boiling an alcoholic solution of the nitrite, forms clusters of yellowish- 
white needles, m. p. 53°, and is reduced by zinc and acetic acid in 
alcoholic solution to di-m-chlorobenzylamine and aa-di-m-chlorobenzyl- 
hydrazine, NH2*N(CH2*CgH4Cl)2, which reacts with benzaldehyde, 
yielding henzaldehyde-di- m-chlorobenzylhydrazone, 
CHPh:N-N(CH2-C6H4Gl)2. 
This crystallises in small, yellow needles, m. p. 66°, and is hydrolysed 
by hydrochloric acid to benzaldehyde and aa-di-m-chlorobenzylhydrazine 
hydrochloride, white leaflets, m. p. 200°. On treatment with sodium 
nitrite the preceding hydrochloride yields di-m-chlorobenzylamine 
nitrite. 

s-Di-m-chlorobenzylhydrazine, N2H2(CH2'C0H4C1)2, prepared by 
reducing m-chlorobenzaldazine with sodium amalgam and alcohol, 



ORGANIC CHEMISTRY. i. 311 

crystallises in small, white needles, m. p. 43°; the hydrochloride^ 
yellowish- white needles, m. p. 191", the dihenzoyl derivative, m. p. 88°, 
and the diacetyl derivative, m. p. 73°, are described. The yellow 
miroso-derivative, ]S'2(NO)2(CH2*OgH^Cl)2, m. p. 48°, when heated in 
alcoholic solution is converted into TH-chlorohenzaldehydenitroso-vOi- 
chlorohenzylhydrazone^ CgH4Cl'CH.*N*N(NO)*CH2*CgH4Cl, which forms 
yellow needles, m. p. 98°, and is hydrolysed by hydrochloric acid to 
m.-chlorohenzylhydrazine hydrochloride^ CgH^Cl'NH'NHgjHCl, colourless 
needles, m. p. 134°. F. B. 

iV-Aminonaphthaliniide and its Derivatives. Adriano 

OsTROGOviCH and M. Mihailescu (Gazzetta, 1911, 41, ii, 757 — 807). 

— By the action of hydrazine sulphate on naphthalic anhydride the 

authors have obtained i\r-aminonaphthalimide, 

y — for which the annexed symmetrical formula is 

<^ \-COv to be adopted in view of the reactions of the 

\ — /^ ^N'NHg substance described below. The same sub- 

<^ J)-CO'^ stance is obtained when naphthalimide, or even 

\ — '^ naphthalic acid, is taken instead of naphthalic 

anhydride. 

N-Aminonaphthalimide is obtained by treating a boiling solution of 
naphthalic anhydride in glacial acetic acid with a boiling aqueous 
solution of hydrazine sulphate and sodium acetate. Ebullition is 
continued for a few minutes, and, on cooling, the imide, CjgHgOgNg, is 
deposited in long, lemon-yellow needles, m. p. 262° after recrystallisa- 
tion. The same substance is obtained by heating hydrazine sulphate 
and sodium acetate with a solution of naphthalimide in aqueous glacial 
acetic acid for some hours in a sealed tube at 200 — 220°. The imide 
can also be prepared by boiling hydrazine sulphate (or, belter, hydro- 
chloride) with a solution of naphthalic acid in aqueous potassium 
hydroxide. iV-Aminonaphthalimide is a stable substance, .which sub- 
limes unchanged and is not attacked by boiling concentrated acids 
or alkalis. It dissolves in boiling concentrated alkalis, however, and 
is reprecipitated by carbon dioxide, but the solution is not to be 
ascribed to the production of a metallic derivative. The sulphate is 
obtained in tabular, colourless crystals by adding concentrated 
sulphuric acid to a solution of the base in glacial acetic acid ; it is 
stable only in the presence of sulphuric acid of sufficient concentration. 
The hydrochloride forms small, colourless needles, and is immediately 
hydrolysed by traces of moisture. The platinichloride, 

(Ci,H30,N2)2.H2PtCl„ 
is an orauge-yellow, crystalline powder. The picrate, 

Ci,H,0,N,-C«H30,N3, 
forms orange-yellow needles, m. p. 192°. When treated with sodium 
nitrite in the presence of glacial acetic acid, iV-aminonaphthalimide 
yields naphthalimide, identical with that of Jaubert (Abstr., 1895, 
i, 239), and nitrous oxide is evolved. With sodium hypobromite, 
iV-aminonaphthalimide yields naphthalimide according to the equation: 
^CigHgOgNg + NaOBr = NaBr + HgO + N2 -h 2C12H7O2N. 

iV-Aminonaphthalimide yields acyl derivatives, for the convenient 
naming of which the author proposes the term naphthalimyl to denote 
VOL. Cll. i. Z 



i. 812 ABSTRACTS OF CHEMICAL PAPERS. 

the group CioHg<Cp^~J>N-. For these derivatives the two tautomeric 

forms R«NH-CO»R' and R*N:C(0H)'R' are possible, but the enolic 
formula is excluded, because the substances give no coloration with 
ferric chloride. FormylN-ammonaphthalimidef 

CigHfiOglN-NH-CHO, 
is obtained by heating iV-aminonaphthalimide with formamide at 1 40° 
for about an hour ; it forms almost colourless, prismatic crystals, 
m. p. 245 — 246°. It is a very stable substance, which dissolves 
unchanged in cold, strong acids or alkalis, and is hydrolysed 
only when these solutions are boiled. Acetyl-^ -aminonaphthalimide^ 
CjgHgOgNgH'Ac, obtained by boiling i\^-aminonaphthalimide with an 
excess of acetic anhydride, crystallises in colourless needles, m. p. 
260 — 261°; in stability it resembles the formyl derivative. Benzoyl- 
^'aminonaphthalimide, CjgH^OgNgHBz (from benzoic anhydride), 
forms colourless needles, which begin to soften at 280° and melt at 
290 — 291°, and is also very stable towards acids and alkalis. 

iV^-Aminonaphthalimide reacts with the anhydrides of dibasic acids, 
giving, in the case of phthalic and naphthalic anhydrides, the corre- 
sponding imide, one molecule of water being eliminated ; succinic, 
maleic, and citraconic anhydrides yield amic acids, from which the 
imides may be obtained by dehydration. "N-JVaphthalimidosuccinamic 
acid (termed J^-naphthalimylsuccinamic acid by the author), 

Ci2H602:n-nh-co-ch2-ch2-co2H, 

obtained by the interaction of iV-aminonaphthalimide and succinic 
anhydride, either in the warm or at the ordinary temperature, forms 
acicular crystals, m. p. 213° (with evolution of gas, presumably steam). 
When it is boiled with glacial acetic acid or heated at 180° in a 
current of dry air, ^-naphthalimidosuccinimide, 

Ci2H602:n-n:o,h,02, 

is produced ; it is a white, crystalline powder, which begins to ball 
together towards 260°, and melts at 272—273°. This imide may be 
reconverted into the acid by dissolving it in dilute potassium hydroxide 
and adding a slight excess of dilute acetic acid or hydrochloric acid. 

^-Naphthalimidomaleinamicacid,Q^^'B.fi^,^'^B.'QO'GW,QB.'CO^n, 
is a white, microcrystalline powder, m. p. 205° (decomp.). It is 
probably the cw-form, because it does not absorb bromine, and it does 
yield an imide. The ammonium salt and the silver salt, OigH905N2Ag, 
were prepared. '^-Naphthalimidomaleinimide, Ci2lIg02'.N'NI04H202, 
is obtained with &ome difficulty ; it is necessary to boil the acid for 
some minutes with a large excess of acetyl chloride. It forms minute, 
acicular, colourless crystals, m. p. 118 — 120°; if the heating is con- 

tinned, it resolidifies at 1 50° and melts again at 

CH— (j3H 215°. The authors suppose that the treatment 

CjgHgOglN'NIC CO with acetyl chloride yields the unsymmetrical 

\/ imide (annexed formula), which when heated 

O above its melting point is transformed into the 

symmetrical imide; in one preparation this 

isomeride was obtained direct, crystallising in small, colourless needles, 

m. p. 240°. iT-Naphthalimidomaieinimide gives Piutti's reaction (with 

sodium methoxide or ethoxide) for substituted unsaturated imides. 



ORGANIC CHEMISTRY. i. 313 

'N-JSl'apkthalimidocitraconamic acid, CigHgOgiN'NH'CgH^Og, forms 
colourless, prismatic crystals. Like the corresponding malfeinamic acid, 
it dissolves in alkalis, and is reprecipitated by dilute hydrochloric acid 
or sulphuric acid, but not by acetic acid. The ammonium and silver 
salts were prepared. '^-Naphthalimidocitraconimide, 

Ci,h,o,:n-n:c,h,o„ 

is obtained by heating the acid for some time at 140°, or by boiling it 
with glacial acetic acid. On heating it begins to soften at 250°, and 
melts at 254 — 255°. The imide can also be obtained by boiling 
xV-aminonaphthalimide with an excess of citraconic anhydride. It 
gives Piutti's reaction. 

^-Naphthalimidophthcdimide, Q-^^fic>\^'W.Q^fi<^, is obtained by 
the interaction of ^-aminonaphthalimide and phthalio anhydride in 
presence of glacial acetic acid or chloroform in the cold. It crystal- 
lises in colourless scales, m. p. about 320°. It dissolves readily in 
alkali hydroxides, and is reprecipitated by carbon dioxide. 

'N-^aphthalimidonaphthalimide, CjgH^^O^IN'NICigHeOg, is prepared 
by heating together equimolecular quantities of N-aminonaphthalimide 
and naphthalic anhydride at 240 — 260°. After cooling, the reaction 
product is dissolved in concentrated sulphuric acid, and the solution 
poured into an excess of water. It is a white, crystalline powder, 
m. p. about 330°. It dissolves in alkali hydroxides, and is reprecipi- 
tated by carbon dioxide. Neither this nor the preceding imide is 
attacked by hydrochloric acid ; concentrated sulphuric acid hydrolyses 
them in the warm, yielding N-aminonaphthalimide. 

Aldehydes react with iV^-aminonaphthalimide, giving in general the 
Schiff's bases resulting from the elimination of the elements of water. 
In the case of the aromatic aldehydes containing a />-hydroxy-group 
{/?-hydroxybenzaldehyde, protocatechualdehyde, and vanillin) an inter- 
mediate additive product is formed, which can then be dehydrated. 
When the jt>-hydroxy-group is substituted, however (as in animal dehyde, 
veratraldehyde, and piperonaldehyde), the condensation product is 
obtained direct. It was not possible to isolate a formaldehyde 
derivative. 

Ethylidene-^-aminonaphthalimide^ CjgHgO^iN'NICHMe, is obtained 
on mixing acetaldehyde with iV-aminonaphthalimide ; it forms small, 
colourless needles, m. p. 172°, and is readily hydrolysed. 

Benzylidene-'^-aminonaphthaUmidey CigH^OqiN'N ICHPh (obtained 
in presence of acetic acid or on warming with an excess of benz- 
aldehyde), crystallises in colourless needles, m. p. 206 — 207°. 

Cinnamylidene-N-aminonaphthalimide, CjgHgOglN'NICH'CHICHPh, 
prepared in the same manner as the preceding derivative, forms small, 
colourless needles, m. p. 195 — 196°. 
sKf-Hydroxybenzylidene-^-aminonaphthalimide, 
■ Ci^HgOglN-NICH-CelT^-OH, 

crystallises in thin, colourless needles, m. p. 230—231°. 

When a mixture of iV-aminonaphthalimide and ;7-hydroxybenz 
aldehyde is kept in the presence of glacial acetic acid, the additive 
product, CjgHgOgNg-C^HgOg, is obtained in the form of thin, colourless 
needles. If it is boiled with glacial acetic acid, ^-hydroxyhenzylideiie- 
^-aminonaphthalimide, CigHgOjIN-NICH-Cj^H^-OH, is obtained; it 
\ % 2 



i. 314 ABSTRACTS OF CHEMICAL PAPERS. 

crystallises in slightly yellow prisms, which begin to soften at 270°, 
and melt at 283—284° (decomp.). 

^•Methoxyhenzylidene-^-aininonaphihalimidej CijHgOg'N'NICgHgO, 
crystallises in colourless needles, which begin to ball together at 210°, 
and melt at 216—217°. 

When 1 esorcilaldehyde reacts with i\^-amiDonaphthalimide, a mixture 
of the additive product and the imide is formed, which, on boiling with 
glacial acetic acid, yields 2 : A:-dihydroxyhenzylidene-^-aminonaphthal- 
imid«j Ci2Hg02lN'NICH*C6H3(OH)2, which crystallises in slightly 
yellow prisms, which become red about 180°, and then almost black, 
and melt at 289 — 290° (with slow heating) ; when placed in a bath at 
285°, the substance becomes reddish-purple, balls together, and melts 
at 288—289° (decomp.). 

-A^-Amiuonaphthalimide and protocatechualdehyde, in presence of 
glacial acetic acid, yield an additive product, Ci2Hg02lN*^JIC7Hg03, 
a slightly yellow, microcrystalline powder, which, on heating, 
becomes brown at 260° and black at 280°. When it is boiled wiih 
glacial acetic acid, 3 : i-dihydo'Oxybenzylidene-N-aminonaphthalimide, 
Ci,Hg02lN*NICH*CgH3(OH)2, is obtained ; it crystallises in small, 
pale yellow prisms. 

iV^-Aminonaphthalimide and vanillin in presence of glacial acetic 
acid yield the additive product, 

Ci2Hg02:N-NH-CH(OH)-CgH3(OH)-0]VIe; 
it crystallises in tufts of yellow needles, which soften and ball together 
about 220°, and melt at 226—227°. When it is heated at 130—140° 
(or at 160°), or boiled with glacial acetic acid, it yields 4:-hydroxy- 
^methoxyhenzylidene-l^-aminonaphthalimide^ 

Ci2Hg02:N-N:CH-CgH3(OH)-OMe, 
which crystallises in long, colourless needles, softens about 228°, and 
melts at 231—232°. 

3 : 4- Dimethoxybenzylidene-'N-aminonaphthalimidey 
G,2Hg02:N-N:CH-CgH3(OMe)2, 
is obtained by keeping an alcoholic solution of iV^-aminonaphthalimide 
and veratraldehyde for two days ; it forms colourless needles, m. p. 
229—230°. 

IHpe7'07iylidene-'N-aminonaphthalimidey 

CijHgOglN-NICH-CgHglOgtCHg, 
obtained from piperonaldehyde in glacial acetic acid at the ordinary 
temperature, forms small, colourless needles, m. p. 256 — 257°. 

When iV-aminonaphthalimide is boiled with an excess of ;3-beDzo- 
quinonein glacial acetic acid, ^-naphtJialimido-^-henzoquinonemonoiniine, 
CjgHgOoIN'NICgH^IO, is obtained as a slightly brown, microcrystalline 
precipitate. The compound is soluble in alkali hydroxides, giving an 
orange or red coloration, and is reprecipitated by dilute hydrochloric 
acid or carbon dioxide. The substance dissolves in concentrated 
sulphuric acid, giving a red solution with a violet tinge, and is 
precipitated unaltered on addition of water. R. Y. S. 

CondeDsation of 5(4)-Methylglyoxaline with Chloral. 
Otto Geengboss (Ber., 1912, 46, 509—526. Compare Abstr., 1909, 
i, 189). — The condensation of 4-methylgly«xaline with chloral is 



^«<n: 



ORGANIC CHEMISTRY. i. 316 

analogous to that with formaldehyde (Windaus, Abstr., 1909, i, 258), 
the chloral becoming attached to the ring in position 5 (or 4), namely, 
.NH-CMe 

■C-CH(0H)-CCl3. 

The ester hydrochloride, HC1,CH<^__M^^®^^^^^^ ^^ , and the 

hydrochloride of the corresponding acid contain an extremely labile 
chlorine atom. In aqueous solution at 0° the chlorine is precipitated 
completely by silver nitrate ; when the aqueous solution is evaporated 
the hydrochloride of the hydroxy-acid is formed quantitatively. This 
chlorine atom reacts with sodium methoxide with the formation of 

the methoxy-compound, HCI,CH<^^n;j"jj^Qj^^^.^^^^^. 

When the hydroxy-acid is warmed with dilute nitric acid, a mixture 
of two nitrates is obtained, which are separated by boiling with 
90% alcohol. The faintly basic nitrate of the a-ketonic acid is 
hydrolysed, whereas the more basic nitrate of 4-methylglyoxaline-5- 
carboxylic acid remains in solution. 

The ketonic acid, CH<^ M , forms a crystalline oxime 

N L/*C0*C02li 
with a characteristic sodium salt. When heated with aniline, carbon 

dioxide is eliminated, and the base, CH<^ n ^tt-xtdu' ^<^'"^6^- 

W 0*011. rixh 

When reduced with aluminium amalgam the hydroxy-acid is 

reformed. 

5(4)-Methylglyoxaline-4(6)-carboxylicacid, CH«^ M is the 

JN O'0L)2ii 

main product of the oxidation of methylglyoxalineglycoUic acid with 

concentrated nitric acid. The ethyl ester of this acid is obtained 

synthetically on boiling thioglyoxaline with 10% nitric acid. 

The hydrohromide of b{i)-'methylglyoxalinegly collie acid crystallises 
in short, pointed needles, m. p. 184 — 185° (decomp.). The hydro- 
hromide of the ester is obtained in lancet-shaped crystals pointed at 
both sides, which sinter at 160°, m. p. 166° (decomp.); the hydrochloride 
of the acid crystallises in four-sided prisms, m. p. 183 — 184° (decomp); 
that of the ester forms rhombic and lancet-shaped platelets, which 
sinter at 147°, m. p. 150-5°. 

5(4:)-Methylglyoxaline-i(5yglycollic acid crystallises in well-formed, 
lustrous plates and stunted prisms, which become brown at 205°, 
m. p. 215°, to a reddish-brown foam. The nitrate crystallises in long, 
six-sided plates, decomp. 150° ; the phosphotung state separates in 
microscopic needles ; the sodium salt forms plates. The copper salt 
yields narrow, four-sided rods of a pale blue colour. 

5(4:)- Methylglyoxaline-i{5)-chloroacetic acid hydrochloride, prepared by 
the action of acetyl chloride on methyl methylglyoxalineglycollate 
hydrochloride, and isolated first in the form of the methyl ester hydro- 
chloride, which crystallises in crossed needles sintering at 165°, ui. p. 
167° (decomp.), crystallises in stout, lustrous, four-sided, rhombic plates, 
Fhich becomes yellow at 190°, m. p. 204° (decomp.). 



I 



i. 31 fi ABSTRACTS OF CHEMICAL PAPERS. 

5(iyMethylglyoxaline-i{b)-glyoxylic acid crystallises in short rods 
and needles, which becorae brown at 230° and begin to decompose at 
1240°. The sodium salt forms transparent, four-sided plates with 
oblique ends ; the nitrate has pointed crystals, which begin to decompose 
at 200°; the hydrochloride crystallises in six-sided plates, which become 
brown at 236° and decomp. at 242°. The oa;i?ne crystallises in needles, 
which sinter at 225°, m. p. 228° (decomp.) ; it forms a characteristic 
sodium salt, crystallising in thin, flat needles, m. p. 210° (decomp. to a 
black mass). 

Methylglyoxalineglyoxylic acid, when reduced byaluminium amalgam 
in alcoholic aqueous sodium hydroxide solution, is converted into 
methylglyoxalineglycollic acid. 

The anil of 5(4^)-methylglyoxalineA{5)-aldehyde crystallises in sharp 
needles, m. p. 224° (decomp. to blackish-brown drops). 

b{i)-Methylglyoxaline-^{6)-carhoxylic acid, prepared by oxidation of 
methylglyoxalineglycollic acid with concentrated nitric acid, crystallises 
in long, thin, matted needles, m. p. 223° (decomp.), and sublimes in 
flat needles when heated above 200°. At the melting point carbon 
dioxide is eliminated, and methylglyoxaline formed. The ammonium 
salt is not stable ; the potassium salt has decomp. 238°. The hydro- 
chloride crystallises in lustrous platelets, m. p. 230° (decomp.) ; the 
phosphotung state is obtained in small, thin, four-sided plates. The 
ethyl ester, prepared by heating the potassium salt with ethyl alcohol 
and ethyliodide, crystallises in long rods with oblique ends, m. p. 
205 — 206°, and is identical with the product obtained synthetically 
from ethyl 2-thiol-4(5)-methylglyoxaline-5(4)-carboxylate, 
^xx r. /NH-CMe 

The sodium salt crystallises in long, slender needles, m. p. 240°; 
the nitrate forms four-sided plates, m. p. 167° (decomp.); the hydro- 
chloride has m. p. 183° (some decomp.). The ester is hydrolysed on 
prolonged boiling with concentrated hydrochloric acid to 5(4)-methyl- 
glyoxaline-4(5)-carboxylic acid. E. F. A. 

CoDstitution of the Supposed Pyrazolinecarboxylic Acid. 
Carl BOlow {Ber., 1912, 46, 528—533. Compare Bulow, this vol., i, 
134). — Polemical. A reply to Buchner (this vol., i, 213). Pyrazoline 
compounds which contain no carboxyl group distil without decom- 
position, whereas Buchner's compound very readily loses nitrogen when 
heated ; it is not believed possible for the carboxyl group to make this 
difl^erence. Buchner's pyrazolidine from ethyl phenylpyrazolinedicarb- 
oxylate boils without decomposition, whereas the known pyrazolidines 
are very unstable. These and other reasons are quoted against 
assigning a pyrazoline structure to Buchner's compound. E. F. A. 

Hydantoins. X. Action of Potassium Thiocyanate on 
Pyrrolidonecarboxylic Acid. 2 -Thiohydantoin-4- propionic 
Acid. Treat B. Johnson and Herbert H. Guest (Amer. Chem. J., 
1912, 47, 242— 251).— Johnson and Nicolet (this vol., i, 63) have 



T " r ^CH-CHg-CHg-COgH, 



ORGANIC CHEMISTRY. i. 317 

shown that by the action of potassium thiocyanate on either glycine or 
acetylglycine in presence of acetic anhydride, the same 2-thio-3-acetyl- 
hydantoin is produced, and Johnson (/. Biol. Ghem., 1912, 11, 97) 
has found that, under similar conditions, alanine and acetylalanine 
both yield the same 2-thio-3-acetyl-4-methylhydantoin. A study has 
now been made of the behaviour of potassium thiocyanate towards 
pyrrolidonecarboxylic acid in presence of acetic anhydride, and it has 
been found that the corresponding cyclic thiohydantoin is produced. 
The thiohydantoin of pyrrolidonecarhoxylic acid, 

CH,-CH-0O 

m. p. 206° (decomp.), forms long, prismatic crystals, and is hydrolysed 
by dilute hydrochloric acid with production of 2-thiohydantoin-i- 
propionic acid (thiohydantoin of glutamic acid), 
NIT'PO 

m. p. 122°, which crystallises in rhombic plates. The latter thio- 
hydantoin is readily desulphurised by chloroacetic acid with formation 
of hydantoin-4-propionic acid (hydantoin of glutamic acid), 
NH-CO. 

m. p. 165°, which crystallises in hexagonal, tabular prisms ; this com- 
pound is also produced, but in smaller yield, by the action of chloro- 
acetic acid on pyrrolidonecarboxylic acid thiohydantoin. 

Attempts were made to synthesise 2-thiohydantoin-4-propionic acid 
by the action of potassium thiocyanate on glutamic acid dissolved in 
water, alcohol, or acetic anhydride, but without success. E. G. 

Theory of the Indigo Vat. Arthur Binz and Kurt Schadel 
(Ber., 1912, 45, 586—597. Compare Abstr., 1911, i, 497).— The 
authors summarise the results of previous work in support of the 
view that in the formation of the indigo-vat, the indigotin is not 
directly reduced to indigo-white, but first combines with one or two 
molecules of sodium hydroxide (or other alkali hydroxide) to form an 
additive compound (compare Abstr., 1906, i, 749), from which oxygen 
is then removed by the reducing agent (for example, zinc) employed in 
the preparation of the vat : 

C^gHioOgNg + NaOH = C.^HioOgNg.NaOH 

• CioHioOaNgjNaOH + Zn = Ci6Hi,02N2Na + ZnO. 

If this interpretation is correct, the velocity of vat formation should 
be increased by replacing the free indigotin by the above-mentioned 
additive compound, and this is found to be the case. Zinc, iron, and 
magnesium react much more rapidly on the additive compound with 
sodium hydroxide than on indigotin in the presence of the same amount 
of free alkali. 

Bromoindigotin and dibromoindigotin react with sodium ethoxide in 
alcoholic solution, yielding the compounds, C^oK^gO^^ J^rf'^a.OIl and 
CjgHg02N2Br2,NaOH, which are decomposed by washing with alcohol 
more readily than the corresponding compound of indigotin. The 



L 318 ABSTRACTS OF CHEMICAL PAPERS. 

alkali derivatives of the tetrahalogenoindigotins, on the other hand, are 
very stable. 

With respect to the fixation of indigotin in the fibre, the authors 
consider that the first stage consists in the chemical union of the 
fibre with the indigo-white, and that this union remains intact during 
the subsequent oxidation. It is very improbable that a colloidal 
complex with the fibre is first produced, since it is found that colloidal 
indigotin cannot be fixed on the fibre. F. B. 

Bromo- and Methoxy-derivatives of Indigotin. Paul Fried- 
lander, S. Bruckner, and G. Deutsch (Annalen, 1912, 388, 23 — 49). 
— Dibromo- and dimethoxy-indigotins containing the substituents in 
positions 4 : 4', 5 : 5', 7 : 7', and 6 : 6' have been synthesised from the 
corresponding o-nitrobenzaldehydes or anthranilic acids with the 
object of ascertaining the influence of the substituents on the colours 
of the dyes. The colours of the first three dyes, in solution or on the 
fibre, do not markedly differ from that of indigotin itself ; 6 : 6'-di- 
chloro-, 6 : 6'-dibromo-, and 6 : 6'-dimethoxy-indigotin, however, exhibit 
a very different, reddish-violet shade. 

Q-Bromo-2-nitrotoluene, m. p. 38°, obtained from 2-nitro-o-toluidine 
by the Gattermann method in the cold, is reduced by tin, stannous 
chloride, and hydrochloric acid to Q-bromo-o-toluidine, a yellow oil, the 
acetyl derivative, m. p. 163°, of which is oxidised to bromoacetyl- 
anthranilic acid, NHAc'CgH3Br'C02H, m. p. 224°, by potassium per- 
manganate at 80° in the presence of magnesium sulphate. This acid is 
converted by boiling sulphuric acid (1:1) into m-bromoaniliue {acetyl 
derivative, m. p. 84°), but when hydrolysed by 10% sodium hydroxide 
yields Q-bromoanthrayiilic acid, m. p. 136°. The latter is boiled with 
an excess of chloroacetic acid in aqueous sodium carbonate, and the 
resulting 3-bromophenylglycine-2-carboxylic acid is converted in the 
usual manner into 4 : i'-dibromoindigotin, which crystallises from 
chloroform in blue needles with a copper lustre, exhibits pronounced 
dichroism in solution, and yields a normal vat with alkaline 
hyposulphite. 

5 : 5'-Dibromoindigotin has already been prepared by Baeyer (Ber., 
1879, 12, 1315). It is obtained by the direct bromination of indigotin 
in anhydrous solvents, and can also be produced from 5-bromo- 
anthranilic acid. ^Bromophenylylycine-l-carboxylic acid has m. p. 
227—228° (decomp.). 

6 : 6'-Dibromoiudigotin, a constituent of the antique purple dye 
obtained from Murex brandaris (Abstr., 1909, ii, 262), has been 
prepared by Sachs from jt?-bromo-o-nitrobenzaldehyde (Abstr,, 1904, 
i, 593). The authors prepare it in larger quantity from the bromo- 
anthranilic acid {a/)etyl derivative, m. p. 217°). b-Bromophenylglycine- 
2-carboxylic acid, m. p. about 236°, is a yellow, crystalline powder, and 
yields ^-bromoacetylindoxyl, m. p. 118*5°, by boiling with acetic 
anhydride and sodium acetate. Attempts to prepare 7 : 7' dibromo- 
indigotin from the bromoanthranilic acid have been unsuccessful. It 
has been obtained in very small yield by an application of Bauer's 
isatin synthesis (Abstr., 1907, i, 603). o-Bromo-oxanilide, m. p. 205°, is 



ORGANIC CHEMISTRY. 1*. 319 

boiled with phosphorus pentachloride in toluene, and the resulting di-o- 

r y 7. . ,7 .7 CCKN-C.H.Br ,,^„ 

bromofhenyCoxaliminochloride^ ri/^i'vr r^ tt t» ' "™- P* H^ > yellow 

COLrJ 'Cgri^jSr 

needles, is heated at 100° with 100% sulphuric acid, whereby 1-hromo- 

isatin, C^HgBr^C^p^J^CO, m. p. 192° reddish-yellow needles, is 

obtained. 7-Bromoisatin responds to the indophenin test, and by warm- 
ing in benzene with phosphorus pentachloride ai)d subsequently treat- 
ing the solution with hydrogen sulphide, yields 7 : 1'-dibromoindigotin, 
which crystallises in needles with a copper lustre. 

Indoxyl condenses with 5 : 7-dibromoisatin chloride in benzene to 
form 5 : 1-dibromoindigoiin, blue needles, and with 5 : 7-dibromoisatin 
in acetic acid to yield red needles of dibromoindirubin, . 

2-Amino-Q-methoxybenzonitrile, m. p. 141°, colourless needles, obtained 
by the reduction of 2-nitro-6-methoxybenzonitrile by tin, stannous 
chloride, and hydrochloric acid, forms an acetyl derivative, m. p. 176°, 
and is not hydrolysed by acids or alkalis, dilute or concentrated, hot 
or cold, but is slowly attacked by very concentrated sodium hydroxide 
at 160 — 170°, yielding 2-amino-6-'methoxybenzamide, m. p. 150°. This 
substance, unlike the nitrile, reacts readily with chloroacetic acid in 
boiling, concentrated sodium carbonate, yielding 3-methoxyphenyl- 
glycine-2-carboxyla'mide, NH2'CO*CgH3(OMe)*NH*CH2'C02H, m. p. 
208° (decomp.), yellow crystals, from which sodium hydroxide at 
170 — 190° or boiling acetic anhydride and sodium acetate (and 
atmospheric oxygen) produce 4 : ^'-dimethoxyindigotin^ needles with a 
copper lustre. 

b •.b'-Dimethoxyindigotin, blue needles with a copper lustre, is 
obtained from 2-nitro 5-methoxybenzaldehyde, acetone, and dilute 
sodium hydroxide in the usual manner. 

2-Acetylamino-jo-cresol and methyl sulphate in alkaline solution yield 
the methyl ether, OMe-O^HgMe'NHAc, m. p. 95° (the corresponding ethyl 
ether has m. p. 126°). These ethers are oxidised to the corresponding 
acids by boiling aqueous potassium permanganate and magnesium 
sulphate, i-Methoxyacetylanthranilic acid, m. p. 199° (decomp.), and 
i-ethoxyacetylanthranilic acidf m. p. 182 — 183°, yield by hydrolysis with 
dilute sulphuric acid (1 : 1) A:-methoxyanthranilic acid, m. p. 166° 
(decomp.) {methyl ester, m. p. 75°), and ^-ethoxyanthranilic acid, 
m. p. 174° respectively. These acids react with chloroacetic acid in 
boiling 10% sodium hydroxide, the products yielding, after acidifica- 
tion, b~methoxypheny/glycine-2-carboxylic acid, 

C02H-C6H3(OMe)-NH-CH2-C02H, 
m. p. 159 — 161° (decomp.), brown, microscopic needles, and 5-ethoxy- 
phenylglycine-2-Garboxylic acid, m. p. 166 — 167°, red, microscopic 
needles respectively, from which the 6 : 6'-dialkyloxyindigotins are 
obtained in the usual manner. 

7 : T-Dimethoxyindigotin, needles with a copper lustre, is prepared 
from the nitromethoxybenzaldehyde, acetone, and sodium hydroxide. 

C. S. 



i. 320 ABSTRACTS OF CHEMICAL PAPERS. 

Action of Thioaoetio Acid on Cyanoguanidine (Synthesis of 
Thioliminoniethyltriazine). Adriano Ostrogovich {Atti R. Accad 
Liiicei, 1912, [v], 21, i, 213—217. Compare Abstr., 1911, i, 1036).— 
When cyanoguanidine is heated with an ethereal solution of thio- 
acetic acid for about two hours until the evolution of hydrogen 
sulphide cea,seB, ^6-thtol-2-imino-i-methyl-\ : 3 :5triazine, C^H^N^S, is 
precipitated. A further portion can be obtained from the solution, so 
that the total yield is 93%. The pure substance forms small, colourless 
crystals, which decompose without melting ; for it the formula : 

N'^p/cTT\.jTo^CINH, or the tautomeric thionic form, is suggested. 

The compound is soluble in acids, in alkali hydroxides, and in ammonia. 

R. Y. S. 

Researches on Purines. V. 2-Oxy-l-methylpurine. Carl 0. 
Johns {J. Biol. C/iein., 1912, 11, 73 — 79). — Five of the six isomerides 
of 2-oxymethylpurine have been already described. The sixth, 2-oxy- 
1-methylpurine, can be obtained from 5 : 6-diamino-3-methyldihydro- 
2-pyrimidone. The potassium salt of nitrocytosine (5-nitro-6-amino- 
dihydro-2-pyrimidone) is methylated by methyl iodide, and the product is 
found to be 5-nitro-6-amino-3-methyldihydrO'2-pyrimidone, crystallising 
in slender prisms, m. p. 274° (decomp.). When this is reduced with 
freshly precipitated ferrous hydroxide, it gives a good yield of 
5 : 6-diam{no-3-'methyldihydro-2-pyrimidone, which in turn reacts with 
formic acid to give a fminyl derivative, the potassium salt of which 
when heated lost water and so formed the potassium salt of 2-oxy- 
1-methylpurine. This purine crystallises in flat prisms containing 
2H2O ; decomp. 280°. They effloresce in the air and become anhydrous 
over sulphuric acid. An aqueous solution gives sparingly soluble 
precipitates with platinum chloride and picric acid. The picrate 
has m. p. 214° (decomp.). W. D. H. 

A Purine-Hexose Compound. John A. Mandel and Edward 
K. Dunham {J. Biol. Chem., 1912, 11, 85 — 86). — A preliminary note 
on a compound of adenine and hexose separated from an extract 
of yeast. It forms sheaves of delicate acicular crystals, and melts at 
206°. Analysis shows close agreement with the figures calculated 
from the formula CjjHj^OgNg. A phenylosazone obtained from it 
yielded 15*3% nitrogen. The hexose has not yet been identified. 

W. D. H. 

Existence of Complexes between Purine Substances and 
Sodium Salicylate. Giovanni Pellini and Mario Amadori (Atti 
R. Accad. Lincei., 1912, [v], 21, i, 290—295. Compare Abstr., 1910, 
i, 525). — By measurements of the depression of the freezing point of 
aqueous solutions of sodium salicylate to which caffeine and theo- 
bromine, respectively, are added, the authors establish the existence of 
complexes similar to those formerly described. The tendency to their 
formation is more marked than in the case of sodium benzoate, and it 
is greater for caffeine than for theobromine. 

Measurements of the solubility in water at 25° and at 40° of 



ORGANIC CHEMISTRY. i. 321 

pharmaceutical " sodium salicylate and caffeine " show that the product 
is not a mixture, as in the case of ** sodium benzoate and caffeine," 
but on this point further experiments are needed. R. V. S. 

Xanthine Derivatives from Uric Acid. IV. Preparation of 
Xanthine and Hypoxanthine. Ernst E. Sundwik {Zeitsch. 
physiol Ghem., 1912, 76, 486—488. Compare Abstr., 1911, i, 684).— 
Xanthine is formed to the extent of 30 — 33% when uric acid is 
heated at 200° with oxalic acid in presence of much glycerol. 

Xanthine is converted into hypoxanthine by dissolving in excess of 
sodium hydroxide and shaking with chloroform at 60 — 70° during two 
hours. E. F. A. 

Azoxy compounds. Angelo Angeli and Bruno Yalori {Atti 
R. Accad. Lincei, 1912, [v], 21, i, 155 — 165. Compare Angeli and 
Alessandri, Abstr., 1911, i, 1045). — In the present paper two more 
pairs of isomeric azoxy-compounds are described, namely, a- and 
j8-p-bromoazoxybenzene and a- and /3-4-bromo-4'-nitroazoxybenzene. 

When azoxy benzene is treated with bromine without a solvent, 
a-;?-bromoazoxybenzene, C^2^9^^2-^''j ^^ obtained ; it forms straw- 
yellow crystals, m. p. 73° (previously given as 75°). Oxidation of 
^-bromoazobenzene with hydrogen peroxide in glacial acetic acid 
solution, the mixture being kept at 40 — 50° for some days, yields 
a-jo-bromoazoxy benzene, m. p. 73°, identical with that above described, 
and, in addition, P-^-hromoazoxyhenzene, which forms yellow crystals, 
m. p. 92°. It is not possible to convert the two />-bromoazoxy benzenes 
into each other directly, and therefore they do not resemble the 
stereoisomeric azoxy-compounds of Reissert (Abstr., 1909, i, 435), but 
both the isomerides now described yield />-bromoazobenzene again on 
reduction with aluminium amalgam. a-jo-Bromoazoxybenzene is not 
acted on by bromine, but /8-^-bromoazoxy benzene when treated with 
bromine yields 4 : 4'-dibromoazoxy benzene. The constitutions of the 
two substances may be derived from this fact, because it is probable (in 
view of the formation of the bromo-derivatives about to be described, 
and of others already known) that a bromine atom attaches itself in 
the para-position in the nucleus in every NPhI group. The authors 
therefore ascribe to a-p-bromoazoxybenzene the formula 

Ph-NOIN-CgH^Br, 
whilst /8-jo-bromoazoxybenzene is NPhlNO'CgH^Br. 

When bromine is added to p-nitroazobenzene in the presence of 
traces of iodine, A:-hromo-^' -nitroazohenz&m^ CjjHgO.^NgBr, is obtained ; 
it forms dark red crystals, m. p. 203°. The bromination cannot be 
effected in glacial acetic acid even in sunlight. The action of nitric 
acid (D 1-45) on jo-bromoazobenzene yields the same 4-bromo-4'- 
nitroazobenzene. 

When a-jo-bromoazoxybenzene is greatly warmed with nitric acid 
(D 1-45) a compound, Ci2Hg03N3Br, m. p. 99°, is obtained ; in this 
substance the bromine and the nitro-group are probably attached to 
the same benzene nucleus. Treatment of a-jo-bromoazoxy benzene with 
concentrated sulphuric acid for an hour on the water-bath leads to the 
production of jo-bromoazobenzene and 4-bromo-4'-hydroxyazobenzene. 



i. 822 ABSTRACTS OF CHEMICAL PAPERS. 

The addition of bromine to jo-bromoazobenzene yields 4 : i'-dibromo- 
azobenzene, C^gHgN^Brg, which forms dark orange-yellow cryst Is, 
m. p. 204°. If this Rubstance is kept at 100° for twelve hours with 
hydrogen peroxide, 4 : 4'-dibroinoazoxybenzene is obtained, identical 
with that prepared by brominating )8-;o-bromoazoxybenzene. 

a-i-Bromo-i'-nitroazoxyb'inzene, C^H^Br'NOIN'OgH^'NOg, m. p. 
194°, is obtained by keeping 4-bromo-4'-nitroazobenzene in glacial 
acetic acid solution with hydrogen peroxide at 100° for a day. 
pi-Bromoi'-nitroazoxybenzene, CgH^Br'NINO'CgH^'NOg, is formed 
by treating /S-;?-nitroazoxy benzene, NPhlNO'OgH^'NUg (compare 
Angelo and Alessandri, loc. cit.)^ with bromine in the presence of iodine 
in the warm ; it crystallises in minute, pale yellow prisms, m. p. 203°. 
Nitric acid (D 1'45) reacts with /3-jo-bromoazoxybenzene, yielding 
o-4-bromo-4'-nitroazoxy benzene, identical with that above described. 

R. V. S. 

Scission of Azo dyes by Halogens. Maximilian P. Schmidt 
(/. pr. Chem., 1912, [ii], 85, 235— 240).— ;?-Hydroxyazobenzene is 
converted by the action of chlorine or hypochlorous acid in aqueous 
solution into benzenediazonium chloride and 2:4: 6-trichlorophenol, 
and by bromine into benzenediazonium bromide and 2:4: 6-tri- 
bromophenol. 

Sodium diazobenzenesulphonate when subjected to the same treat- 
ment also yields benzenediazonium salts (compare Fischer, Abstr., 
1878, 302), and a similar decomposition has been observed in the 
case of a large number of azo-dyes. 

With respect to the mechanism of the reaction, it is imagined that 
an additive compound with the halogen is first produced, which then 
undergoes decomposition as shown in the following scheme : 

R-N R-N-Cl R-N-Cl 

II -^ I _^ Ijl + HO-R'-CI. 

OH-R'-N OH-R'-N-Cl N 

F. B. 

Aromatic Substances Containing Multivalent Iodine. Luigi 
Mascarelli and B. Toschi {Aui R. Accad. Lincei, 1912, [v], 21, 
i, 145 — 151. Compare Mascarelli and Cerasoli, Abstr., 1910, i, 725; 
Mascarelli, Toschi, and Zambonini, ibid., 831). — Attempts to prepare 
six-membered rings containing iodine have not been successful. Only 
in one case, namely, from the tetrazo-compound from 2 : 2'-diamino- 
4 : 4'-tetramethyldiaminodiphenylmethane, was a small quantity^of a 
yellow powder obtained, which had m. p. 220 — 225°, and showed the 
properties of an iodonium base. In the present paper some endo- 
bisazo-derivatives (compare Duval, Abstr., 1910, i, 703, 781) are 
described, which were obtained during the course of the work. 

When 2 : 2'-diamino-4 : 4'-dichlorodiphenylmethane is treated with 
nitrous acid, the tetrazo-compound is obtained. This reacts with 
potassium iodide, yielding 4 : 4'-dichloro-2 : 2'-di-iododiphenylmethane 
and a substance, CigHgN^Clg, which crystallises in golden-yellow 
scales decomposing at 260 — 265°. To it is assigned the constitution 




ORGANIC CHEMISTRY. i. 323 

C H CI C H CI 

of pip'-dichloroendobisazodiphenylinethane, I ^ ^ ^ ^<C^^ ^ • '^^i& 

compound when treated with sulphuric acid yields a crystalline 
substance (not analysed) which decomposes at 249 — 252°. Its alcoholic 
solution gives an intense green coloration with ferric chloride, and to 

it the constitution of 4 : ^'-dichloro-2-hydroxy6ndoazodiphenylmefhane 

n XT ni 
0H-C6H3C1-CH< I ^ ^ , is ascribed. 

2 

4 : 4:'-Dichloro-2 : 2' -di-iododiphenylmethane tetrachloride, 
IClg-CeHgCl-CHg-CeHgCMClg, 
is obtained in yellow crystals, m. p. about 102° (evolving chlorine), 
when chlorine is passed through a chloroform solution of 4 : 4'-di- 
chloro-2 : 2'-di-iododiphenylmethane. It is a very stable substance, and 
does not form iodoso- and iodoxy-derivatives when treated with the 
reagents which usually effect that change, and it was also impossible 
to obtain the di-iodoxy-derivative by oxidation with chlorine or with 
Caro's acid. R. V. S. 

Azo -dyes from Substituted Pyrroles. Hans Fischer and E. 
Bartholomaus (Zeiisch. physiol. Chem., 1912, 76, 478 — 485). — In view 
of their importance for recognising and characterising blood and bile 
pigments, the azo-dyes from a number of substituted pyrroles have 
been prepared by interaction with diazobenzenesulphonic acid. 
Monoazo-compounds were obtained in all cases. 

The compound, SOgH-CgH^-Ng-C^NHMeg-COMe, from 2 : 4-dimethyl- 
3 -acetyl pyrrole crystallises in long, lustrous, red needles. 

The compound, CigH^^OgNgS, from ethyl 2 : 5-dimethylpyrrole-3- 
carboxylate crystallises in long, greenish-olive, rhombic needles. 

The compound, CjgHjgOgNgS, from 2 : 5-dimethylpyrrole-3-carboxylic 
acid separates in yellowish-brown needles. 

A The compound, Q^^^fi^^, from 2 : 5-dimethyl pyrrole is obtained 
in tiny, microscopic, orange needles. The corresponding dye from 
2 : 4-dimethylpyrrole crystallises in yellowish-brown needles. 

Haemopyrrole picrate has m. p. 125° (corr.); it does not readily 
condense with diazobenzenesulphonic acid. The free haemopyrrole 
couples very readily, however, forming orange-yellow needles of the 
compound, Cj^Hji^-OgNgS ; it dissolves in concentrated sulphuric acid 
with a greenish-yellow coloration, and is totally different from the 
azo-dye obtained from 2 : 4-dimethyl-3-ethylpyrrole. E. F. A. 

Losses in the Isolation of the Monoamino-acids [from 
Proteins] by the Ester Method. II. Emil Abderhalden and 
Arthur Weil (Zeitach. physiol. Chem., 1912, 77, 59 — 74. Compare 
Abstr., 1911, i, 1049). — The pure amino-acids either singly or mixed 
were esterified, distilled, and hydrolysed, tlie amount recovered and the 
losses at each stage of the operation being determined. In this way 
the proportion recovered was from glycine 62*5%, from ci-alanino 70%, 
and dl-\eucine 80%. From a mixture of all five amino-acids there was 
obtained 50% of the glycine, 57% of the alanine, 66% of the leucine, 
58% of the glutamic acid, and 40% of the ^aspartic acid. <i- Valine is 



i. 824 ABSTRACTS OF CHEMICAL PAPERS. 

recovered to the extent of 68%, /-phenylalaDine only to the extent of 
54%. In presence of protein the yields are still less. 

It is considered that if these losses by the isolation of the monoamino- 
acids are taken into account, the proteins are almost entirely composed 
of the already known constituents. E. F. A. 

Introduction of Iodine into Protein Derivatives. Hermann 
Pauly {Zeitsch. physioL Chem., 1912, 76, 291— 292).— Basic 
nitrogenous substances exposed to the action of excess of iodine form 
brown periodides, in which the iodine is only loosely attached. lodo- 
protein compounds must be colourless, and retain their iodine after 
treatment for a short time with sulphurous acid. The iodotryptophan 
described by Neuberg (Abstr., 1907, i, 955) is considered to be a 
periodide ; it is not possible to introduce iodine into tryptophan or 
monobenzoyltryptophan. E. F. A. 

Estimation of Amino-groups in the Oxyproteic Acids of 
Normal Urines. J6zef Browinski and Stephane Dabrowski {Bull. 
Acad. Set. Cracow, 1911, A, 587 — 595 ; Zeitsch. j^hysiol. Chem., 1912, 
77, 92 — 106). — Determinations have been made of the ammonia and 
amino-nitrogen in the oxyproteic acids both before and after hydrolysis, 
using Sorensen's method of titration with formaldehyde. 

Urochrome and a?^ooxyproteic acid before hydrolysis contain about 
2*7% of ammonia nitrogen and 2*4%, and 6 4% respectively of amino- 
nitrogen. aw^'Oxyproteic and oxyproteic acids, which are not pre- 
cipitated by basic lead acetate, contain no ammonia, but 11*2% 
and 38 '8% respectively of amino-nitrogen. It is believed that the 
last two acids constitute the greater proportion of the oxyproteic 
acids of urine. 

Hydrolysis with boiling hydrochloric acid leads to the formation of 
melanins and secondary products ; hydrofluoric acid can be used to 
effect hydrolysis at the temperature of a boiling water-bath, and with 
it a much larger proportion of amino-acid nitrogen is obtained. 

Melanin is formed from urochrome when hydrolysis with hydrofluoric 
acid is prolonged, but not from any other of the oxyproteic acids. 
Tiiis is taken to indicate that the oxyproteic acids are not to be 
regarded as the mother substances of the urinary pigment. 

The proportions of ammonia and amino-nitrogen given by the four 
acids when decomposed with hydrofluoric acid for twenty-four hours 
are as follows: urochrome, NH^ 8*7%, NHg 26'4%; a/Zooxyproteic acid, 
NH3 4-2%, NHg 76-9%, an^ioxyproteic acid, NHg 3-2%, NHg 33-9% ; 
oxyproteic acid, NHg 8*3%, NHg 80-5%. E. F. A. 

HsBmoglobin. Eugen Letsche {Zeitsch. physiol. Chem., 1912, 
76, 243—257. Compare Abstr., 1910, i, 599).— The absorption 
number {A) of haemoglobin solutions, that is, the ratio of concentra- 
tion (c) to the extinction coeflicient (e), should be a constant independent 
of the apparatus used and the observer, if the method is to be used to 
measure the concentration of bajmoglobin solutions. Measurements 
made to test this indicate the value 2'081 x 10"^ for A, in agreement 
with Hiifner's original determinations, but differing from the value 



« 



ORGANIC CHEMISTRY. i. 325 

rSTxlO"^ determined by Butterfield, and previously used by the 
writer (Abstr., 1910, i, 599), whose values must be corrected 
accordingly. The amount of carbon monoxide fixed per gram of 
haemoglobin is 1"36 c.c, which is in excellent agreement with the 
value 1*34 determined by HUfner and by Butterfield. E. F. A. 

The Behaviour of Carbon Monoxide Blood to Certain Pre- 
cipitating Agents. Kurt Gestewitz (Zeitsch. exp. Path. T/ier., 1911, 
Reprint 15 pp.). — Vegetable agglutinins, such as ricin and phasin, 
precipitate from carbon monoxide blood, the carboxyhsemoglobin in the 
corpuscles ; zinc and copper salts precipitate it free from the corpuscles. 
The copper precipitate (produced by adding 1% copper sulphate solu- 
tion) in normal blood is brown in colour, in carbon monoxide blood 
red, which is quite characteristic to the eye ; no spectroscopic 
investigation is necessary. The colour difference with zinc salts is 
not so striking. The zinc carboxyhsemoglobin can be readily dried, and 
then remains undecomposed for weeks. W. D. H. 

The Cleavage of Nucleic Acid by Organ Enzymes. Alfred 
ScHiTTENHELM and Karl Wiener {Zeitsch. physiol. Ghem., 1912, 77, 
77 — 85). — The experiments confirm on the whole the results of Levene 
and Medigreceanu, and relate to the enzymes concerned in nucleic 
acid cleavage in various tissue extracts; the products of cleavage 
inhibit the activity of the enzymes concerned. W. D. H. 

Yeast Nucleic Acids. V. Structure of Pyrimidine 
Nucleosides. Phcebus A. Levene and Frederick B. La Forge 
{Ber., 1912, 45, 608—620. Compare Levene and Jacobs, Abstr., 1911, 
i, 96, 510). — The pyrimidine complexes in nucleic acid are very resistant 
towards the hydrolytic action of dilute mineral acids. When distilled 
with hydrochloric acid (D 1-06) for thirty-six hours, furfuraldehyde 
is liberated slowly, corresponding in amount with equimolecular propor- 
tions of ribose and base in the complex. When hydrolysed by hydro 
bromic acid in presence of bromine, cytidine is converted into 5-bromo- 
uracil and cZ-ribonic acid. Uridine or cytidine when treated with 
bromine in aqueous solution yields a solution which reduces Fehling's 
solution and forms a crystalline precipitate when heated with phenyl- 
hydrazine ; this behaviour indicates that the double bond has remained 
intact. 

When uridine is evaporated with concentrated nitric acid, an 
anhydride of two molecules of nitrouridinecar boxy lie acid is obtained, 
which is ^readily converted into its ethyl or butyl esters, and when 
hydrolysed gives nitrouracil. 

Alkyl derivatives of uridine or cytidine could not be obtained. 

Both compounds are fairly easily reduced to dihydro-compounds, 
which are very easily hydrolysed by mineral acids, giving ribose and 
dihydro-derivatives of the bases. It is assumed that the glucoside 
formation between ribose and the base involves position 5 in the 
base, and that the contiguity of this to the double bond conditions 
the resistance to hydrolysis. 

KThe preparation of uridine has been simplified by conversion of the 



i. 326 ABSTRACTS OF CHEMICAL PAPERS. 

ribose into glucoside, which prevents its precipitation together with the 
base with lead acetate or barium hydroxide. 

Cytidine is conveniently isolated as the sparingly soluble nitrate, 
m. p. 197°. The free base crystallises in long needles, which sinter at 
220°, m. p. 230° (decomp.), [af^ + 29-63". 

b- Bromouridine is very similar to uridine ; it has m. p. 181 — 184°, 
[aK-15-4°. 

iJydroxyuridine (corresponding with 5-bromo-4-hydroxydihydro- 
uracil) has m. p. 222 — 223°; the phenylhydrazide forms long, citron- 
yellow needles, m. p. 209°. 

The anhydride of nitrouridinecarhoxylic acid^ ^i8^i«^i7^6' 
crystallises in short, thick prisms, decomp. above 200° ; the silver salt is 
amorphous. The ethyl ester forms slender needles, decomp. above 200° ; 
the n-hutyl ester sinters at 185°, m. p. 190—192°. 

Diliydrouridine is a colourless syrup, [aju +39 1°. E. F. A. 

Free Amino-groups of the Simplest Proteins. Albrecht 
KossEL and Alexander T. Cameron {Zeitsch. physiol. Chem., 1912, 76, 
457 — 463. Compare Kossel and Kennaway, Abstr., 1911, i, 667). — 
Nitroclupeine, obtained by nitration of clupeine, yields a nitroarginine 
on hydrolysis. This nitroarginine when treated with nitrous acid by 
van Slyke's process yields nitrogen corresponding with^the decomposition 
of one amino-gronp. Since the amino-groups of guanidine and nitro- 
guanidine are Bnob decomposed by this reagent, the reactive amino- 
group can only be that of the ornithine residue, and the arginine 
groups of clupeine are linked in the following manner : 

— CO-NH CO NH CH CO NH— 

C3Hg-NH-C(NH)-NH2 03H,;NH-C(NH)-NH2 
In further support of this formula it is shown that clupeine behaves 
similarly to guanidine when nitrated, it has the same acid-fixing power 
as the guanidine-groups in the molecule, and, lastly, unchanged clupeine 
gives no nitrogen by van Slyke's process. 

Cyprinine, the protamine of carp sperm, contains at least 30*3% of 
its total nitrogen in the form of lysine ; 23 "6% of the total nitrogen 
is set free by nitrous acid. 

In sturine about 6*9% of the total nitrogen is liberated ; this roughly 
corresponds to the total amount of lysine present, but this quantity is 
not enough to make up all the acid-fixing groups of sturin. 

E. F. A. 

Electrical Transport of Colloids. Leonor Michaelis and Hein- 
RicH Davidsoun {Zeitsch. physiol. Chem., 1912, 76, 385 — 387. Compare 
Pekelharing and Kinger, Abstr., 1911, i, 1051). — A criticism of the 
arrangement adopted by Pekelharing and Kinger in measuring the 
electrical transport of pepsin. It is regarded as important that 
the middle and side vessels should have exactly the same hydrogen ion 
concentration. E. F. A. 

Compounds of Ammo-acids and Ammonia. VII. Peter 
Bergell aud Paul Boll {Zeitsch. physiol. CViewt., 1912, 76, 464 — 467). 
— To establish whether the asymmetric hydrolysis of leucinamide was 



I 



ORGANIC CHEMISTRY. 1. 327 

brought about by a special enzyme or by the usual protein- or peptide- 
splitting enzymes, the effect of the addition of iV^-hydrochloric acid to 
the enzyme solution has been studied. The enzyme hydrolysing silk 
peptone was but little affected, those digesting casein and fibrin were 
only partly destroyed, but that acting on leucinamide was entirely 
killed, unchanged optically inactive leucinamide being recovered. 
Accordingly, the last change is attributed to a specific enzyme. 

E. F. A. 

Comparative Hydrolysis of Sucrose by Various Acids In 
Presence of Invertase. Gabriel Bertrand, M. Rosenblatt, and 
(Mme.) M. Rosenblatt {Bull, Soc. chim., 1912, [iv], 11, 176—186. 
Compare Abstr., 1898, ii, 128; 1909, i, 272 ;Sorensen, Abstr., 1910, i, 
147; Euler and XJgglas, Abstr., 1910, i, 345, 796; Michaelis and 
Davidsohn, Abstr., 1911, i, 1051, 1052). — Previous investigations 
beginning with those of Kjeldahlin 1881 have shown that the activity 
of invertase and other enzymes is modified by the presence of acids or 
alkalis, but the conclusions arrived at as to the quantities of acids or 
alkalis that are most effective and as to the general laws governing 
these actions have been very variable. 

In the present investigation account has been taken of the alkalinity 
of the yeast extract and of the sucrose solutions employed and 
disturbing influences due to these causes, and to variation in the yeast 
and the sucrose employed have been avoided. The results are summarised 
and tabulated in the original. They show that the acids, grouped 
according to their basicity, arrange themselves for activity at optimum 
concentrations, taking hydrochloric acid as 100, in the same order as for 
their catalytic activity on sucrose. Among the monobasic acids, 
trichloroacetic, dichloroacetic, and lactic acids are exceptional in 
their behaviour. The monobasic acids become more active as catalysts 
in presence of invertase, and this is also true, but to a less extent, 
for dibasic acids, whilst for tribasic acid the inverse holds. No 
explanation can be given at present of the exceptional behaviour of 
the three acids referred to already, or of the great increase in catalytic 
activity shown by aromatic sulphonic acids in presence of invertase. 

T. A. H. 

I^Cellulase. Hans von Euler {Zeitsch. angew. Chem., 1912, 26, 
1^) — 251). — A brief account of the work of earlier investigators on 
^rae action of bacteria and fungi on cellulose is given, and the con- 
clusion is drawn that the hydrolysis of pure cellulose by enzymes 
derived from fungi or higher forms of plant life has not yet been 
demonstrated. 

It is shown in the present communication that cellulose-dextrins, 
1 obtained by the action of strong sulphuric acid on cellulose, are 
I converted under the influence of an enzyme (cellulose- dextrinase) 
occurring in the extract obtained by pressing Merulius lacrimana 
into substances having a greater reducing action on Fehling solution ; 
that the change is brought about by an enzyme is demonstrated by 
the fact that very little change takes place if the extract is heated 
before being added to the cellulose-dextrin solution. W. H. G. 



i. 828 ABSTRACTS OF CHEMICAL PAPERS. 

Synthetic Action of Enzymes. William M. Bayliss {Proc. 
physiol. Soc, 1911-12, xl-xli ; J. Physiol., 43). — Using glycerol to 
reduce the water content, the synthesis by emulsin of quinol and 
dextrose to form arbutin can readily be observed in a week or less. 
A small degree of synthesis can readily be detected polarimetrically. 
This experiment lends itself well to class work. W. D. H. 

The Nature of Enzyme Action. II. The Synthetic Pro- 
perties of Anti-Bmulsin. William M. Bayliss {J: Physiol, 1912, 
43, 455 — 466). — Intraperitoneal injection of emulsin does not give 
rise to any true anti-enzyme, although precipitins for the proteins con- 
tained in the solution are produced. The inhibitory action of serum 
so obtained on emulsin is no greater than that of normal serum, and 
is merely due to diminution of optimal acidity. Neither normal serum 
nor the immune serum has any synthetic action. Emulsin, on the 
other hand, will synthesise lactose and also the glucoside of glycerol. 
This synthesis is retarded by serum, probably owing to diminution of 
acidity. Emulsin is not a protein. W. D. H. 

Influence of Protoplasmic Poisons on Reductase. D. Eraser 

Harris (Bio-Chem. J., 1912, 6, 200— 202).— The activity of this 

intracellular enzyme is not affected by reagents, such as chloroform, 

sodium fluoride, etc., which lessen the activity of, or destroy, 

p rotoplasm. W. D. H. 

The Nitration of Arsanilic Acid. Ludwig Benda (Ber., 1912, 
46, 53 — 58). — The brownish-yellow substance obtained in addition to 
diazoarsanilic acid, mononitroarsanilic acid, and s-trinitroaniline in the 
nitration of arsanilic acid has the composition CgHgO^NgA-S. 

As the action of bromine in alkaline solution gives 4-bromo-2:6-di- 
nitroaniline (m. p. 158°, compare Austen, this Journ., 1876, ii, 513), and 
the action of potassium hydroxide yields 3 : 5-dinitro-4-hydroxyphenyl- 
arsinic acid (Benda and Bertheim, this vol., i, 63), the compound must 
be 3 : b-dinitro-i-aminophenylarsinic acid. In the fact that it resists 
diazotisation, it resembles s-trinitroaniline. D. F. T. 

Preparation of Aromatic Stibines. Ludwig Kaufmann 
(D.R.-P. 240316).— Triphenylstibine can be obtained in 80— 90% yield 
and m. p. 53°(Michaelis andKeose give m. p. 48°) by boiling triphenyl- 
stibine sulphide (100 parts) with absolute alcohol (450 parts) and benzene 
(50 parts) during half an hour, adding copper powder, and continuing 
the heating during three hours ; on cooling, the product separates in a 
pure condition. The copper can be replaced by iron in the presence of 
ferric chloride, or the mixture left at the ordinary temperature during 
about fifteen hours, and Anally boiled for one hour. E. M. G. M. 




i. 329 



Organic Chemistry. 



Asphalt Theory of Naphtha-formation : New Work on the 
Genesis of Naphtha. K. W. Charitschkoff (/. Russ. Phys. Gliem. 
Soc, 1912, 44, 354—359. Compare Abstr., 1904, ii, 180 j 1905, ii, 
43; 1907, i, 269 ; ii, 361 ; 1909, i, 39).— The naphtha synthesised by 
the method of Sabatier and Senderens (Abstr., 1907 i, 269) consists of 
unsaturated liquid hydrocarbons which have a high iodine number, and 
readily oxidise and become tarry. If, however, the catalytic substance is 
insufficiently heated, instead of a liquid product, a black, polymerised 
tarry substance resembling natural asphalt is obtained. The qualita- 
tive and quantitative resemblance between some of the fractions 
obtained on distilling naphtha and natural asphalt has already been 
pointed out by the author, and a similar resemblance is now found 
with the distillation products of this artificial asphalt. 

The conclusion is drawn that the formation of naphtha is a more 
complex process than is assumed by the theories of Mendeleeff, 
Berthelot, and Cloez, these only dealing with the initial stage of the 
process, namely, the formation of unsaturated hydrocarbons from 
carbides. These hydrocarbons, by a process of polymerisation, give 
solid natural bitumen (asphalt), which, on decomposition by heat or on 
spontaneous decomposition occupying countless years, yield liquid 
naphtha. This process is probably reversible, since naphtha, by oxida- 
tion or other processes, may be converted into more complex products 
similar to asphalt, and undoubtedly possessing a cyclic structure. 
Destructive distillation of the tarry matter formed by the condensa- 
tion of naphtha gives a naphtha rich in paraffins. The author regards 
the asphalt theory of the formation of naphtha as definitely established. 

T. H. P. 

Preparation of Hydrocarbons with Two Double and One 
Triple Linking. Farbenfabriken vorm. Friedr. Bayer & Co. 
(D.R.-P. 241424). — ySc- DimefJiylhexa-^'^''-dien-^y-inen6t 

CHalCMe-CiC-CMelCHg, 
a colourless oil, b. p. 3 2°/ 17 mm., was obtained by distilling the tetra- 
methylglycol, OH*CMe2*C:0-CMe2'OH (142 parts), with potassium 
hydrogen sulphate (50 parts) at 140 — 150° under atmospheric pressure, 
whilst yy-dimethyl-I^s.octinm-yyj-diol, OH-CMeEfC:C-CMeEfOH, 
colourless crystals, m. p. 53°, b. p. 126°/20 mm., when distilled with 
anhydrous oxalic acid furnished yTq-dimethylocta-^^Jl-dieii-t^^-inene, 
CHMe:CMe-C:C-CMe:CHMe, an oil, b. p. 71°/20-5 mm. 

F. M. G. M. 

The Inflammable Capacity of Mixtures of Methyl Chloride 
and Air. Saposhnikoff {Zeitsch. ges. Schiess. Sprengstoffwesen^ 1911, 6, 
384). — A study of the combustion of mixtures of methyl chloride and 
air in varying proportions and at different temperatures. The heat 
of combustion of one kilo, of methyl chloride is 3099 calories, whereas 

VOL. cii. i. a a 



i. 330 ABSTRACTS OF CHEMICAL PAPERS. 

the corresponding figure for methane is 13,000; the conditions under 
which methyl chloride explodes are also considered in the original. 

F. M. G. M. 

Thermal Analysis of Hexachloroethane and of its Binary 
Mixtures. Paul Pascal (Covipt. reml, 1912, 154, 883—886).— 
The ordinary cooling curve for hexachloroethane reveals the existence 
of three modifications, the a- variety stable above 125°, the /3-variety 
existing between 71*6° and 125°, and the y-form, stable below 71*6°. 
The transition point 125° being ill defined on the curve, the accurate 
value was found from the curves for mixtures of the hexachloride with 
naphthalene and phenanthrene. Mixtures containing not more than 
8% of naphthalene or 13% of phenanthrene show the unusual property 
of remaining solid at 71*6°, but undergoing partial liquefaction when 
the temperature falls slightly. The curves are reproduced and fully 
discussed in the original. 

The cryoscopic constant for hexachloroethane is 560. W. 0. W. 

Autoxidation of Trichloroethylene. Hermann Staudinger 
{J. pr. Chem., 1912, [ii], 86, 330— 333).— Remarks on Erdmann's 
paper on this subject (this vol., i, 65). From investigations on the 
autoxidation of the ketens, the author has come to the conclusion that 
the addition of oxygen to an autoxidisable substance. A, takes place 
unsymmetrically, thus : A+ >0!0 — >■ AIOIO, and not symmetrically, 

A<[^ I , as hitherto imagined. 

The autoxidation products of ketens consist of oxides of the 
type (I), which, in some cases, may be isolated, but readily decom- 
pose into ketones and carbon dioxide, together with oxides of the 
type (III), produced by the decomposition of the initial product (II), 
as shown in the following scheme : 

(I.) (II.) (III.) 

The author agrees on the whole with the views expressed by 
Erdmann on the autoxidation of trichloroethylene, but represents the 
formation of carbon monoxide, carbonyl chloride, and hydrogen 
chloride as follows : 

CClj-CHCl CCL-CHCl CCL CHCl 

\/ -^11 -> II + il . 

O O o o 

b F. B. 

Bthylenio Isomerism of Acetylene Dichloride. Georges 
Chavanne {Compt. rend., 1912, 154, 776 — 777).— Commercial 
acetylene dichloride consists of a mixture of two isomerides which can 
be separated by fractional distillation. The two compounds have 
b. p. 49°/760 mm. and 60"2°/760 mm. respectively. Both unite with 
bromine, yielding the same dibromide, m. p. - 26° b. p. 195°/760 mm. 

w. o. w. 



I 



ORGANIC CHEMISTRY. L 331 



Action of Potassium Hydroxide on Tertiary Alcohols : New 
Method for the Diagnosis of Alcohols. Marcel Guerbet {Compt. 
rend., 1912, 154, 713—715. Compare this vol., i, 67, 154).— Tertiary 
alcohols are scarcely attacked by potassium hydroxide below 230°. 
Above this temperature, oxidation slowly occurs, and the acids 
produced contain fewer carbon atoms than the original alcohol. 
Formic and propionic acids were recognised amongst the products from 
dimethylethylcarbinol, whilst a small amount of butyric acid was 
obtained from /8-methylpentan-;8-ol. W. O. W. 

Catalytic Dehydration of Aliphatic Alcohols in the Wet 
Way by Sulphuric Acid. Jean B. Senderens {Compt. rend., 1912, 
154, 777—779. Compare Abstr., 1910, i, 649 ; 1911, i, 600—637).— 
Tertiary alcohols, even the lowest in the series, readily yield the 
corresponding ethylenic hydrocarbons when boiled with 3 to 4% of 
their volume of sulphuric acid. In the case of the secondary alcohols, 
this decomposition does not occur below the C5 term, whilst with 
primary alcohols dehydration is inappreciable below the Cg term. 
The function of the sulphuric acid appears to be purely catalytic, and 
not to depend merely on its capacity to absorb water. Its efficiency 
as a catalyst depends on the boiling point of the mixture, the low 
boiling alcohols only undergoing decomposition in presence of a 
relatively large amount of acid, whilst the high boiling, tertiary 
alcohols lose water equally readily in the presence of a much smaller 
proportion of acid. W. 0. W. 

A'^-Penten-8-ol, CHglCH-CHg-CHMe-OH. Henri Pariselle 
(Compt. rend., 1912, 154, 710 — 712). — Magnesium turnings (24 grams) 
are treated successively with allyl bromide (10 grams) and acetalde- 
hyde (4 grams). On treating the product in the usual way, A<*-penten- 
8-0I is obtained as a colourless liquid, b. p. 115—116^, D20 0-840, 
n^ 1-425; the acetyl derivative has b. p. 132 — 135°. Phosphorus 
pentachloride converts it into a mixture of /8S-dichloropentane and 
B-chloro-^'^-pentene, b. p. 97—100° W. 0. W. 

a€-Dimethoxy-A^-pentinene and its Hydrogenation. Egbert 
Lespieau {Compt. rend., 1912, 154, 8SQ—S8S).—-ae-I)imethoxy-A^- 
pentinene, OMe'CHg'CiC'CHg'CHg'OMe, prepared from the magnesium 
derivative of 8-methoxy-A«-butinene (Abstr., 1907, i, 581), has b. p. 
176— 177°/760 mm.. Die 0-9385, < 1-442. By addition of bromine it 
yields Py-dihromo-a€-dimethoxy-^^-pentene, b. p, 132 — 133°/15 mm. 
Hydrogenation in presence of platinum black leads to the formation 
of ae-dimethoxypentane and a-methoxypentane, the latter being formed 
with loss of methyl alcohol. W. O. W. 

Hydrolysis and Constitution of Lecithin. Fernand Malen- 
GREAU and Georges Prigent {Zeitsch. physiol, Chem., 1912, 77, 
107—120. Compare Abstr., 1911, ii, 795).— Lecithin is hydrolysed 
by acids in the same manner as glycerolphosphoric acid ; fatty acid and 
phosphoric acid are eliminated simultaneously, although the fatty acid 
is split off much more quickly, the difference being the more marked 
as the catalytic activity of the acid increases. 

^ a a 2 



i. 332 ABSTRAC'l-S OF CHEMICAL PAPERS. 

The choline group in lecithin does not behave as if it were an ester 
group attached to phosphoric acid. It is rapidly eliminated at the 
same rate as the fatty acids. 

After two hours' heating of lecithin-cadmium chloride with NjlO- 
sulphuric acid, hydrolysis is incomplete ; nearly all the choline has been 
eliminated, but only 3*9% of the glycerol phosphoric acid has been 
resolved. As heating is continued, the glycerolphosphoric acid is 
progressively hydrolysed, and after seventy-two hours' heating this has 
occurred to about the extent of three-fourths. 

With iV/10-hydrochloric acid, the fatty acids are completely 
eliminated from lecithin iu eight hours, but only 12*8% of the glycerol- 
phosphoric acid is hydrolysed. E. F. A. 



Action of Phosphorus Trichloride on Organic Acids : 
Monoacetylphosphorous Acid. Benjamin T. Brooke (/. Armr. 
Clvem. Soc., 11)12, 34, 492 — 499). — The reaction between phosphorus 
trichloride and acetic acid is represented in certain text-books by the 
equation (1) SCHg-COgH-f 2PCI3 — > 3aH3-COCl + P203 4- 3HC1, and 
in others by the equation (2) 3CH3-C02H + PC13 — > SCHg-COCl-l- 
P(OH.)g. A study of this reaction has now been made, and has shown 
that equation (2) is correct, whilst equation (1), indicating the 
formation of phosphorous oxide, is entirely wrong. 
' Two secondary reactions take place, the more important of which is 
expressed thus: OH3-C02H + CH3-COC1 Zi: (CH3-CO)20 -f HCI. It 
has been found that when the preparation is carried out in the usual 
way under a reflux condenser, the hydrogen chloride required to 
convert the acetic anhydride into the chloride escapes from the 
reaction mixture. If, however, the mixture of glacial acetic acid and 
phosphorus trichloride is left at 18° for six hours under a slight 
pressure (equivalent to 10 cm. of concentrated sulphuric acid), only a 
small amount of hydrogen chloride escapes, and the formation of acetic 
anhydride is almost completely obviated. 

jLv.The other secondary reaction results in the formation of acetyl- 
phosphorous acid, thus: P(OH)8-f-CH8-C001 = P(OH)2-OAc + HCl. 
Acetylphoaphorous dcid can be prepared in a pure state by adding 40 c.c. 
of acetic anhydride to 5 grams of phosphorous acid at the ordinary 
temperature, treating the mixture with 10 c.c. of acetyl chloride, and 
warming to 50°. The compound separates in white crystals, and, after 
the supernatant liquid has been decanted, is washed with ether and 
dried under a pre.^sure of 10 mm. 

When acetyl chloride is prepared by using the quantities of acetic 
acid and phosphorus trichloride indicated by equation (1), phosphorous 
oxide is not produced, but the residue consists of phosphorous 
acid and a small amount of the acetyl derivative. The phosphorus 
trichloride in excess of that required by equation (2) can be 
recovered. 

The quantity of hydrogen chloride evolved by the action of acetyl 
chloride on phosphorous acid has been estimated, and the results 
indicate that a diacetyl derivative may possibly be formed, although 
it could not be isolated. E. G. 



ORGANIC CHEMISTRY. i. 333 

Ethyl Dinitroacetate. Andrii: Wahl (Ann, Chim. Phys.\ 1912, 
[viii], 26, 421 — 430). — A more detailed account of work already 
published (Abstr., 1903, i, 225 ; 1904, i, 795). In the action of 
nitric acid on ethyl hydrogen malonate there is formed, in addition 
to ethyl dinitroacetate, some ethyl furoxandicarboxylate. In general, 
ethyl dinitroacetate is formed by the action of nitric acid on com- 
pounds of the following types : CHRrCH-COaEt ; CRIi:CH-C02Et ; 
CHR!C(C0Me)*C02Et. Ethyl dinitroacetate decomposes slowly 
when kept, or at once when heated, forming nitric acid and ethyl 
furoxandicarboxylate (compare Jovitachitsch, Abstr., 1902, i, 202). 

T. A. H. 



Action of Concentrated Sulphuric Acid On Trilaurin. B. W. 
VAN Eldik Thieme {J. pr. Chem., 1912, [ii], 85, 284— 307).— The 
preparation of mono- and di-glycerides by the action of alkali salts of 
aliphatic acids on glycerol mono- and di-chlorohydrins (Guth, Diss.., 
Rostock, 1902 j Krafft, Abstr., 1904, i, 136) is not recommended by 
the author, as it is found that a mixture of glycerides is produced ; 
thus, sodium laurate and glycerol a-monochlorohydrin yield a mixture 
of monolaurin, dilauric, and trilaurin, whilst with glycerol ay-dichloro- 
hydrin the product consists mainly of dilaurin and trilaurin. An 
explanation of these results was obtaioed from the behaviour of 
glycerol towards sodium laurate ; when heated at 100°, a mixture of 
these substances becomes alkaline, owing to the formation of sodium 
hydroxide, partial esterification taking place simultaneously : 

C3H5(OH)3 + Ci^H^g-COgNa = 0^^^,sCO^'Q^B.^(f)B.\ -h NaOH. 

A similar esterification, resulting in the formation of a mixture of 
glycerides, occurs with the glycerol chlorohydrins ; the production of 
monolaurin, a/3- and ay-dilaurin, and trilaurin from glycerol ay-di- 
chlorohydrin is represented in the following scheme (R = C^^Hg^'CO). 

2NaOR NaOR 

0H-CH(CH2C1)2 --> 0H-CH(CH2-0R)o — ^ C3H,(OR)8-hNaOH 

NaOH " NaOR 

0H-CH(CH,C1)2 -- > 0H-CH2-CH(0H)-CH,C1 — > 

0H'CH2-CH(0H)-CH-0R and OH-CH2-CH(OR)-CH2-OR. 

These results also afford an explanation of the widely divergent 
values given in the literature for the m. p.'s of mono- and di-glycerides. 
jS-Monolaurin (compare Griin and Skopnik, Abstr., 1910, i, 356) is 
obtained in a pure condition as follows : glycerol ay-dichlorohydrin is 
converted by means of chlorosulphonic acid into S03H*0'CH(CH2C1)2, 
which reacts with lauric acid at 45°, yielding piauro-ay-dichloro- 
hydrin, CiiH23-C02-CH(CH2Cl)2, a pale yellow liquid, b. p. 180— 181°/ 
4 mm. ; this is transformed into the corresponding iodohydrin by 
means of sodium iodide in alcoholic solution, the iodohydrin heated 
with silver nitrite, and the resulting ester of nitrous acid hydrolysed 
with hydrochloric acid. ^-Monolaurin has m. p. 60-5°. a-Monolaurin, 
prepared from aj8-dibromohydrin in a similar manner, has m. p. 58*9°; 
Griin and Skopnik {loo. cit.) give 52°. 

a-Zauro-Py-dibromohydrin has b. p. 197 — 198°/3 mm. 

a^-Dilauro-y-chlorohydrin, prepared by the successive action of 
chlorosulphonic acid and lauric acid on glycerol a-chlorohydrin, has 



i. 334 ABSTRACTS OF CHEMICAL PAPERS. 

b. p. 185—19576 mm., m. p. 30°; Griin and Schacht (Abstr., 1907, i, 
462) give 24°. It is converted by the method described above into 
aP-dilaurin, OH-C8H,(0'CO-CiiH23)2, m. p. 56-3°. 

aa-Dilaurin, obtained together with a^-dilaurin by heating glycerol 
with lauric acid, is an oil ; the product obtained by Griin and Schacht 
{loc. cit) by the interaction of sodium laurate and aa-dichlorohydrin, 
and described by them as aa-dilaurin, consists mainly of a^-dilaurin 
and trilaurin. 

Lauric acid forms with sulphuric acid a crystalline compound of the 
composition CuHg^'COgH,! JHgSO^ ; a similar compound is also formed 
from /8-lauro-ay-dichlorohydrin. 

The action of strong sulphuric acid on trilaurin has also been 
studied. It is found that an additive compound is first produced, 
which then undergoes decomposition, the lauryl groups being replaced 
by SO3H. By partly hydrolysing the product, jS-monolaurin and 
aJ8-dilaurin, together with a small amount of aa-dilaurin, were obtained. 
For complete decomposition of trilaurin into glyceryltrisulphuric acid, 
a large excess of sulphuric acid and a low temperature are necessary. 

The first product of the decomposition, a^-dilawosulphuric acid, has 
been isolated in the form of its potassium salt, 

S03K.O-C3H,(0-COCi,H23)2. 

Glyceroltrisulphuric acid is not readily hydrolysed by water to 
glycerol and sulphuric acid as stated by Klasou {J. pr. Ghem.^ 1879, 
[ii], 20, 1) ; glycerolmonosulphuric acid is produced, which is readily 
isolated in the form of its barium salt, and is hydrolysed by water 
only after prolonged boiling. F. B. 

Ethyl y-Bthoxyacetoacetate. Marcel Sommelet (Compt. o'end., 
1912, 164, 706 — 708). — Although ethyl acetate reacts with ethyl 
bromoacetate in presence of zinc to give only a trace of ketone, yet 
ethyl ethoxyacetate under the same conditions readily forms ethyl 
y-ethoxyacetoacetate, OEt-CHg-CO-CHg-COaEt, b. p. 105—106°/ 
11 mm., 116 — 117°/20 mm. When freshly prepared, this substance 
is colourless, but rapidly alters on exposure to air. An alcoholic 
solution gives a bright red coloration with ferric chloride. The copper 
salt crystallises in green needles, m. p. 145 — 146^ Hydrazine hydrate 
forms ^-ethoxymethylpyrazolone, 0^11^002^2, m. p. 148 — 149 '5°. The 
sodium salt reacts with benzyl chloride, giving a mixture of mono- and 
di-benzyl derivatives. 

Ethyl y-eihoxyabenzylacetoacetate, OEfCH2-CO-CH(CH2Ph)-C02Et, 
b. p. 185 — 187°/ 14 mm., forms a pyrazolone, m. p. 119 — 120°, and on 
hydrolysis yields 8-ethoxy-a-phenylbutan-y-one, 

CHgPh-CHg-CO-CHg-OEt, 
b. p. 157°/19— 20 mm. (semicarbazone, m. p. 103—105°). Mhyl 
y-ethoxy-aa-dibenzylacetoacetate is an oil, b. p. 243 — 247°/14 mm. 

w. o. w. 

The Action of Ammonium Cyanide (Potassium Cyanide and 
Ammonium Chloride) on Chlorinated Aldehydes. Karl Raske 
(Ber., 1912, 45, 725—734). — When an ethereal solution of chloroacet- 
aldehyde is shaken with an aqueous solution of ammonium chloride 



ORGANIC CHEMISTRY. i. 335 

and potassium cyanide and the product treated with hydrochloric acid, 
^-chlorolactic acid is formed. When /8-chloropropaldehyde is similarly 
treated, y-chloro-a-hydroxyhutyric acid, m. p. 58°, is obtained. Its 
ammonium and silver salts were examined. When its aqueous solution 
is boiled, or the solid acid preserved at the ordinary temperature, the 
lactone of ay-dihydroxy butyric acid is formed. The ammonium and 
calcium salts of the latter acid were investigated. 

Chloralacetamide, when acted on successively by hydrocyanic and 
hydrochloric acids, yielded a product^ the analyses of which agreed with 
the formula CCl3-CH(NHAc)-CO-NH2,H20, m. p. 88—89°. This 
appears, however, to be a compound of trichlorolactamide and acetamide, 
since it is readily resolved into these substances by the action of 
hydrochloric acid, and it can also be obtained by crystallising a mixture 
of these substances from chloroform or benzene. Attempts to obtain 
pure crystalline compounds of trichlorolactamide with beozamide, 
formamide, and pyridine respectively were unsuccessful. H. W. 

Cystine. Julius Mauthner {Zeitsch. physiol. Ghem.j 1912, 78, 
28 — 36). — The cystine obtained from a case of cystinuria had 
[ajo- 205*28°. By treatment with ammonia and zinc dust at the 
ordinary temperature the sulphur was removed and about half the 
theoretical quantity of alanine was obtained. This proved to be 
c?/-alanine. 

Cystine interacts with potassium cyanide, forming a-amino-^- 
thiocyanopropionic acid, SCN'CH2*CH(NH2)'0O2H ; this crystallises 
in short, stout, lustrous prisms, also in flat prisms aodsix-sided platelets. 
On heating it becomes brown at 180°, m. p. 220° (decomp.), [a]'^ - 83*17°. 
The copper salt separates in rosettes of microscopic platelets, or when 
quickly precipitated in tiny needles; the hydrochloride forms long prisms 
and needles. E. F. A. 

Dichloroacetaldehyde and the Formation of Vinyl 
Acetates from Bromoacetaldehydes. Bruno Mylo {Ber., 1912, 
45, Q4:5—Q5l).—(S-Bromovi7iyl acetate, CHBrlCH-OAc, b. p. 146—149°, 
is obtained by treating dibromoacetaldehyde (1 mol.) and acetyl 
bromide (about 5 mols.) with finely divided copper (1 atom) and 
heating the mixture at the b. p. for sixteen hours. ajS/S-Tribromoethyl 
acetate, CHBrg'CHBr'OAc, b. p. 114 — 117°/15*5 mm., is prepared by 
heating equal molecular quantities of dibromoacetaldehyde and acetyl 
bromide. ^j^-Dibromovinyl acetate, CBrglCH'OAc, b. p. 70 — 71*5°/ 
7 mm., is prepared from bromal, acetyl bromide, and finely divided 
copper. Equal molecular quantities of dichloroacetaldehyde and 
acetaldehyde are converted, after the addition of a little aqueous zinc 

chloride, into dichlorotrimethylirioxin, CHCl2'CH<^-^v*prTjyr^!!>0, 

m. p. 73 — 74*5°, colourless prisms, and bisdichlorotrimethyltrioxin, 

CHMe<2;^^(^^^}2)>0, m. p. 53—54*5°, tufted needles ; both 

have an intense odour, somewhat resembling that of paraldehyde. 

as. 



i. 336 ABSTRACTS OF OHKMICAL PAPERS. 

Hydrolysis of Carbohydratephosphoric Acid Esters. Hans 
VON EdLER and Yngvk Funke (Zeitsch. physioJ. Chem.j 1912, 77, 
488 — 496). — Sodium hexosephosphate is not hydrolyfled by trypsin, 
pepsin, defibrinated blood, or by a kidney extract. When fed to a 
rabbit, three-quarters of the hexosephosphate were hydrolysed. 

E. F. A. 

Specific Rotatory Power of Lsevulose. Bernhahd Tollens 
(Zeitsch. Ver. dmt. Zuckerind., 1912, 360— 361).— Herzfeld and Winter 
(Abstr., 1886, 438) have found values between - 71° and - 77° for the 
rotatory power of leevulose. It is pointed out that both observers 
used leevulose syrups, and omitted to allow for the moisture in these 
when calculating the experimental results. When recalculated a 
value of - 92° to - 93° is obtained in each case, agreeing with that 
generally accepted. E. F. A. 

Sacchariflcation of Starch by Dilute Acids. Auguste 
Fernbach and Ma