ORGANIC CHEMISTRY

Organic Chemistry. 167

chines are described in U. S. Patents 674,169 and 674,269, of May 14, 1901. J. W. RICHARDS.

ORGANIC CHEnlSTRY. On the Action of Aniline upon Tetrabrom-o.Benzoquinone.

BY C. LORING JACKSON AND H. C. PORTER. Bey. d. chem. Ges., 35, 385 1-3854.-By adding an alcoholic solution of tetrabrom-o- benzoquinone to an alcoholic solution of aniline, aniline and alcohol addition-products of dianilinodibrom-o-benzoquinone result. The filtrate from these precipitates when boiled gives dianilinobrom-p-benzoquinoneanil, and the latter by Ioug boiling with aniline changes to dianilino-p-benzoquinoneanil. Dianilinodi- bvom-o-benzoquinone, C,Br,O,(NHC,H,),, was separated from its aniline addition-product by heating at 50' with a mixture of benzene and ligroin, and recrystallizing from the same mixed solvents until the melting-point remained constant at 160'. Reddish- purple needles. Aniline dianilinodibvom-o-benzoquinone, C,Br,O, ( NHC6H5),, C,H,NH,, is the first product of the action of aniline upon the tetrabrom quinone, and may also be prepared by boiling the dianilinodibrom quinone with benzene and some aniline. Fine light-brown needles, m. p. 123O, decomposed by heating dry or in solution to 5oo-6o0, or by the action of acids. Loses its aniline when warmed with benzene. Dianilinodibrom-o-benzo- guiizonemonoeih-vlhemiacetufe, C,Br,O, (NHC,H,),,C,H,OH, is produced by the action of alcohol upon the dianilinodibrom quinone at ordinary temperature. Rectangular yellow plates, from benzene ; heated dry or in solution to 60' , it slowly loses its alcohol ; rapidly heated, it liquefies at about 143' with simultaneous decomposition. With methyl alcohol, a similar addition-product is obtained, whose decomposition point lies a t about 144'-145'. Dianilinobrom-p- benzoquinoneanil is obtained from the preceding substances by boiling them with aniline bromide and alcohol ; if the reaction is continued too long, dianilino-p-benzoquinoneanil is formed. The bromine derivative is purified by crystallization from a mixture of benzene and methyl alcohol and forms rhombic glistening black plates, m. p. 173'. It is probably a para derivative, since by the action of a dry ether solution of SO,, even at the ordinary temperature, it is changed to the paraquinoneanil, m. p. 202'-203'. M. T. BOGERT.

On Tetrachlordinitrobenzene. BY C. LORING JACKSON AND H. A. CARLTON (Preliminary communication). Bey. d. chem. Ges., 35, 3855-3857::1 ,2,~,~-Tetrachlorbenzene was prepared from 2,4,6- trichloraniline by the Sandmeyer reaction, and yielded the mononitro derivative when boiled for half an hour with fuming nitric acid. The dinitro derivative was produced from the latter by boiling it with a mixture of concentrated sulphuric

168 Review of American Chemical Researck.

and fuming nitric acids. r,z,3,5- TetrachZor-g,6-dinitrobenzene, as thus prepared, and recrystallized from 90 per cent. acetic acid, forms large white rhombic crystals, m. p. 161'-162~, little soluble in alcohol or cold glacial acetic acid, easily soluble in other organic solvents. Dissolved in benzene and treated with an absolute alcohol solution of sodium ethylate, cooling with ice, it yields what are probably the cklordinitrophloroglun'ntrieflylether and the chZordinitropkloroglucindiethyletker. The former crystallizes from alcohol in long white needles, ni. p. 76'. The latter crystallizes from ligroin or from dilute alcohol in thin yellow needles, m. p. 102~-103, and forms salts, of which the barium and lead compounds precipitate in aqueous solutions. The barium salt crystallizes from water in small yellow needles, being nearly insoluble in cold water. The combined amount of these two phloroglucin ethers present in the crude reaction product is only about I O per cent. of the whole, the chief constituent being apparently an oil , volatile with steam, which decomposes when distilled at ordinary pressure, and which is formed in still larger ainount when the reaction is conducted at the boiling-point of the alcohol. The nature of this oil has not as yet been determined.

M. T. BOGERT.

On Triphenylmethyl. Condensation to Hexaphenylethane. (Sixth Paper.) Bey. d. chem. Ges., 35, 3914- 3g2o.-The author observed this hydrocarbon first in the preparation of triphenylchlormethane, and later obtained small amounts of the same substance on treating triphenylmethyl with acetic and nitrous acids. The pursuit of this latter reaction led to the study of the action of metals upon triphenylchlormethane in glacial acetic solution, as a result of which the methods for the preparation of the hexaphenylethane were worked out. Subse- quently, catalytic agents were discovered by which triphenylmethyl was directly condensed to hexaphenylethane. I. Fovma- tion from carbon tetrachloride and benzene. It was repeatedly observed in the preparation of triphenylchlormethane by the author's method that small amounts of a hydrocarbon were formed, melting at 22.5' and insoluble in ether, and which is now identi- fied as hexaphenylethane. 11. Action o f metals zipon fr@kenyl- cklormethane in glacial acetic acz'd. Since triphenylmethyl is but slightly soluble in glacial acetic acid, the effect of acids upon nascent triphenylmethyl was investigated by acting upon glacial acetic acid solutions of triphenylchlormethane with molecular silver, granulated tin or zinc strips. In the cold, the effect of these various metals was simply to produce triphenylmethyl, while at higher temperatures hexaphenylethane was produced. The latter is but little soluble in hot glacial acetic acid, scarcely soluble in alcohol or ether, moderately soluble in cold benzene and rather more so in chloroform ; it is saturated and very stable

BY M. GOMBERG.

Organic Chem is fry. 169

towards oxidizing agents. Its formation from triphenylchlormethane is believed to be due to the condensing action of the hot glacial acetic acid upon the nascent triphenylmethyl, although the same result could not be accomplished by the direct action of acetic acid upon triphenylmethyl. 111. Condensation of fm2henyl- methyl to hexaphenylethane. The chlorethers, especially the monochlor derivatives of ethyl and methylethyl ethers, possess the power of condensing triphenylmethyl to hexaphenylethane. The polymerization by these reagents is accomplished very rapidly and the yield of hexaphenylethane is nearly quantitative. Purified hexaphenylethane, as thus obtained, shows a melting- point of 2 ~ 6 ~ - - 2 2 7 ~ (uncorr.). The important bearing of this condensation upon the constitution of triphenylniethyl is evident.

M. T. BOGERT.

On the 4‘ Beckmann Rearrangement.” 11. BY JULIUS STIEG- LITZ. Am. Chenz. I., 29, 4g-68.-This paper contains a critical review of the various interpretations which have been suggested for the Beckmann rearrangement, together with additional deduc- tions in support of the explanation advanced by the author in 1896. This explanation is briefly as follows : The parallel classes of derivatives, RCONHBr(I), RCONH(OCOR)(II) , R,C(NOH) (111) and RCON(N,)(IV), may all readily yield identical or closely similar intermediate derivatives, with univalent nitrogen, e. g. , (RC0)N : . Such a derivative would result from ( I ) by loss of HBr, from (11) by loss of RCOOH, from ( IV) by loss of N,, while the loss of water from the chloride of (111), R,CClNHOH, would give R,CClN : . The reagents used to effect the rearrangement agree with this conception-alkalies for (I) and ( I I ) , heat for ( IV) , and acid dehydrating agents for (111). It is the intermediate product, in this case RCON : , which actually suffers the rearrangement, owing to the potency of the free valences of univalent nitrogen,

OC-N OC-NR OC : N R I A, R

I I ? an isocyanate being the first tangible product in this case. Where the structure of the substances is such as to preclude the formation of these hypothetical intermediate bodies, no rearrangement occurs. Many observed facts are cited in support of this hy- pothesis. For instance, f3-phenylhydroxylamine, when heated, yields azobenzene and water, a reaction which may be expressed as follows : C,H,NHOH=C,H,N : + H,O, and zC,H,N : = C,H,N : NC,H,. At the same time, a strong carbylamine odor appears, and the author suggests that this odor may not be due to a carbylamine at all, but to small quantities of the analogous phenylimide, C,H,N : , or its isomeric imidophenylenes, which have escaped instantaneous condensation. He believes it to be

1 7 0 Review of American Chemical Research.

likely that the phenylimide as soon as formed suffers partial iso- merization to imidophenylenes :

H H

! I 1 8

N H === N H and explains the change of phenylhydroxylamine to $-oxydi- phenylamine and other reactions by applying this conception : : C,H, : N H + H,O = : C,H, : 0 + NH,, and : C,H, : 0 + H,SC,H, = C,H,NH(HjC,H, : 0 = C,H,NHC,H,OH. Also, C,H,NHNHC,H, + HX = C,H,N : + CeH,NH,X, and C,H,N : = : C,H, : “(3- and 0-), then P-HN : C,H, : + C,H,NH, = H N : C,H,(H )C,H,NH, =$-H,NC,H,C,H,NH, (“benzidine rearrangement’’). I n similar manner, o-”: C,H,: + C,H,NH,== o-H,NC,H,C,H,NH, ( $) ( ‘ ‘diphenyline rearrangement” j , and H N : C,H, : + H,NC,H, = H N : C,H,(H)NHC,H, == H,KC,H, NHC,H, (“semidine rearrangement” j . The structure of the salts of the acid chloramides was determined as RC(0Me) (NHal). Benzchloramide can be titrated quantitatively with standard alkali, using phenolphthalein as indicator. Further data will appear in a subsequent article. RI. T. BOGERT. On the Action of Phenylhydrazine on Benzoylpseudothio-

ureas : 1,s- Diphenyl-3-Arninopyrro-cu,f3’- Diazole Derivatives. BY HENRY L. WHEELER AND ALLING P. BEARDSLEY. Am. Chem. J . , 29, 73-S2.-The authors have shown already that acylpseudothioureas readily react with phenylhydrazine to form aminotriazoles. In the case of the benzoylpseudothioureas, the structure of the products is now proved to be that of I ,s-diphenyl- 3-aminotriazoles, and the reaction by which they are formed is therefore as follows : C,H,CON : C(SCH,)NRR’

- - + C,H,NH-NH,

C,H,C=N-C-NRR‘

C,H,N-- I N + CH,SH + H1O.

So far as this reaction has been examined, the NH, group of the phenylhydrazine invariably attacks the mercaptan group in pref- erence to the CO. E~~~~~~~~~~~.--Benzoylthiolbenzyl’se~dothiourea, C,H,CON:C(SCH,C,H,)NH,, prepared by the action of dilute potassium hydroxide and benzyl chloride upon benzoyl- thiourea, crystallizes from alcohol in glistening white plates,

Organic Chemistry. 17'

m. p. 161', insoluble in ether or benzene, soluble in hydrochloric acid. r,5-Dz;bhenyl-~-aminotriazole.-Equal molecules of phenylhydrazine and the above pseudothiourea, or benzoylthiolmethyl- pseudothiourea, were heated on the water-bath for three or four hours in benzene solution, the solvent evaporated, residue washed with ether and crystallized from alcohol. Colorless prisms, or striated plates, m. p. 154.5', very difficultly soluble in water or cold benzene, readily in hot benzene or alcohol, not attacked by strong boiling sulphuric acid or potassium hydroxide. Dissolved in hydrochloric acid and treated with sodium nitrite at o', crystals are obtained apparently identical with I ,~-diphenyl-g-chlor- triazole of Cleve (Ber. d. &em. Ges., 29, 2672 (1896)). The picrate of the aminotriazole forms yellow lozenge-shaped plates, m. p. 183' ; the chloride, small, colorless plates, melting at 205' without effervescence. r,5-Dz;bhenyl-3-benzoylaminoiriazole, prepared by the action of benzoyl chloride upon the foregoing aminotriazole in warm benzene solution, can also be obtained from the benzoyl chloride addition product by shaking with alkali and dis- solving out the product with benzene, or by heating the substance to its melting-point, whereby HC1 is driven off. It crystallizes from dilute alcohol or from benzene and ligroin, m. p. 159'-160~, and is readily soluble in benzene or alcohol. I ts alcoholic solutions are precipitated by water. Hydrochloric acid changes it to a chloride, identical with the benzoyl chloride addition product. The su&hafe melts at 195'. Chloridt. or benzoyl chloride addition product. When the aminotriazole is warmed on the water-bath with an excess of benzoyl chloride, in absence of a solvent, the triazole dissolves and then suddenly precipitates as a solid cake of this addition product, which crystallizes from alcohol in bunches of small colorless plates, melting at 205' with effervescence, and insoluble in benzene. r,~-Dz;bhenyl-3-acefylaminofri- azole chloride is produced by the action of acetyl chloride upon the aminotriazole. White powder, m. p. 156'-157'. The constitution of these triazole derivatives was settled by the two following syntheses : I. a,c-Dibenzoyl-a-phe?~ylaminoguanidine, C,H,N(COCeH,)NH.C(NH)NHCOC,H,. By shaking phenyl- aminoguanidine, in ether, with benzoyl chloride and alkali, this benzoyl derivative may be produced. I t melts, with effervescence, at 156'. Boiled with absolute alcohol, it is dehydrated, yielding I ,5-diphenyl-3-benzoylaminotriazole, and if the benzoyl group is split off by boiling with strong hydrochloric acid, the resulting aminotriazole is identical with the condensation product, already described, of phenylhydrazine and benzoylpseudothioureas : c,a,cio ...............

H,iN-C=NCOC,H, ................... I

H,N-C=NH , : Y

C6H6N " I

C,H,NH-NH 11. a- Phenyl-a, c-dibenzoylfhiolet~ylseudotitiosemicarbazi~e, C,H,N

172

(COC,H,)NH.C(SC,H,) :NCOC,H,, produced by the action of unsymmetrical benzoylphenylhydrazine upon benzoyliminodi- ethyldithiocarbonate, forms square plates (from benzene), ni. p. I ~ O ~ - I ~ I O , difficultly soluble in alcohol were pure. Boiled with alcoholic ammonia, this carbazide passes into a-phenyl-a,c-di- benzoylaminoguanidine, which then loses water and condenses to I , ~-diphenyl-3-benzoylaminotriazole :

Review of American Chemical Research.

C,H,CO C, H,S-C N C 0 C, H,

C,H,N-NH,H SC,H, .......................... I + N H , = I ..................................

C,H,C=N-C=NCOC,H, I I + 2C,H,SH + H,O.

C,H,N-- S H r,5-Diphenyl;j-p/ienylaininotriazole, prepared from equal molecules of benzoylphenylthiolethylpseudothiourea, C,H,CONHC (SC2H5) :NC,H,, and phenylhydrazine, crystallizes from alcohol in fine white needles, m. p. 202'. I t does not form a chloride, and is unattacked by boiling with strong alkali. r ~ - D + h e n y l - ~ - b e n z o y ~ ~ e ~ z y Z a m ~ n o t ~ i a z o l e is obtained from the latter by the action of benzoyl chloride. I t crystallizes from alcohol in com- pact ill-formed prisms, ni. p. r48'-149', insoluble in ligroin, very soluble in benzene. r,~-D+/ie~zyl;j-~arato~laminotriazole, By warming together, in alcoholic solution, equal molecules of a-benzoyl-a-phenylhydrazine and benzoylparatolylthiolethylpseu- dothiourea, a,c-dibenzoyl-c'-para~oyl n-pkenyla7ninoguanidine is produced. I t forms long colorless needles, melting at 279' with effervescence, and is difficultly soluble in alcohol. When this substance is boiled with dilute alcoholic potash, it is converted, by the splitting off of one benzoyl group and the loss of water, into the paratolylaminotriazole, which forms beautiful, colorless, minute, stout crystals, m. p. 227'-228' :

C,H,CON=C--NHC,H,CH, ...................................................

M

I C,H,N-NH H SC,H,

C,H,CO I

...................................

C,H,C=N-C-NHC,H,CH,

C,H,X--N I ' I

This triazole is identical with the substance previously obtained by Wheeler and Johnson (Am. Chem. J., 26, 414 (1901)) fromben- zoylparatolylthiolethylpseudothiourea and phenylhydrazine. Ben- zoylmethy~henylthiilmethy~seudothio~rea, C,H,CON : C (SCH,) N (CH,) C,H,, is produced by heating together, in benzene solution, equal molecules of benzoyliminodithiodimethylcarbonate and methylaniline. It crystallizes from alcohol in colorless prisms,

Organic Chemistry. I73

m. p. I 13'. r,5-D~henyl;j-methy~henylaminotriazole, from equal molecules of benzoylmethylphenylthiolmethylpseudothiourea and phenylhydrazine left for several days in a cold mixture of benzene and alcohol, forms lozenge-shaped plates, very insoluble in alcohol, and melting with effervescence a t 202'-203', after showing signs of melting about 5' lower. M. T. BOGERT.

The Decomposition of Diazonium Salts with Phenols. BY JAS. F. NORRIS, B. G. MACINTIRE AND W. M. CORSE. Tech. Quart., 15, 326-334 ; A m . Chem. I., 29, 120-129.-In study- ing the preparation of phenol from aniline, the authors were led to the view that when a diazonium salt decomposes in presence of water and a phenol, it reacts to a much larger extent with the phenol than with the water, and it was found that when this decomposition took place at 75°-~oo0, good yields of diphenyl derivatives were obtained. With phenol, the main product is P-oxydiphenyl, with smaller amounts of phenyl ether and what appears to be o-oxydiphenyl. With pyrocatechin, it is a dioxydiphenyl, with smaller amounts of o-oxyphenylether and what is evidently an isomer of the dioxydiphenyl. Resorcin, rather strangely, gave no diphenyl derivatives, and only the azo-compound was isolated. Preliminary experiments with hydroquinone indicate that a p-oxyphenylether is the main product of the reaction, while a diphenyl derivative is produced to a less extent. The introduction of a phenyl group into the ring of pyrocatechin or hydroquinone modifies their properties and considerably increases their reactivity. The phenyl derivative of hydroquinone is oxidized by atmospheric oxygen to a dark blue compound, which can be reduced by SO, to a colorless substance. The ethers produced in these reactions are stable and do not reduce ammoniacal silver nitrate solution. The number of OH groups present in the compounds was determined by prepar- ing their acetyl derivatives. In some cases, methyl ethers also were made. A description of the compounds prepared from hydroquinone will appear in a later paper. EXPERIMENTAL. -De- composition of benzene diazonium su@hate with phenol.--Phenol, mixed with small quantities of water and heated on a boiling water-bath, was treated gradually with a cold aqueous solution of the diazonium sulphate, and the heavy black oil obtained distilled with superheated steam ( 140'-160'), unchanged phenol coming over first, then a mixture of 0- and$-oxydiphenyls, and finally almost pure p-oxydiphenyl. The separation of the 0- and $-oxydiphenyls was secured by crystallization from petroleum ether (b. p. 5oo-8o0), in which the para compound is the less soluble. 40 grams of aniline yielded 2 0 grams of the P-oxydiphenyl and 1 . 5 grams of its isomer. This isomer crystallizes in colorless needles, m. p. 67.5', and is probably the o-oxydiphenyl. Decom- position of benzene diuzonium chloride wifh pyrocatechin.-The reac-

= 7 4 Review of American Chemical Research.

tion between these substances was conducted at 75', and the crude product subjected to steam distillation. The solid which came over with the steam proved to be a-oxydiphenyl ether. The aqueous solution remaining in the flask, decanted from the non- volatile oil, contained dioxydiphenyl, more of which was extracted from the non-volatile oil by boiling with water. From the insoluble non-volatile oil there was separated a small amount of a compound, ni. p. 147.5'-148.5", evidently a pyrocatechin derivative, and probably an isomer of the dioxydiphenyl. From 40 grams of aniline, 4.6 grams of o-oxydiphenj lether and g grams of dioxydiphenyl were obtained. 0- Oxydzj5Aenylether crystallizes from dilute alcohol in flat needles, and from petroleum ether in well-formed six-sided needles terminated by domes, ni. p. 105'- 106'. I t has an aromatic odor. is very soluble in carbon bisulphide, benzene or glacial acetic acid, less 5oluhle in toluene, and only slightly soluble in petroleuni ether or hot mater. I t gives no color with ferric chloride, and shows none of the reactions characteristic of pyrocatechin. I ts ace481 derivative is a thick oil, soluble in the usual organic solvents, and distils without decomposition at 358'-360" (uncorr. 2 . I ts i m f k y l ether crystallizes from methyl alcohol in long, flat, six sided crystals, 111. p. 77' , and is soluble in the ordinary solvents. Dioxydiphenyl, recrystallized from petroleum ether, melts at 136'-136. j', and boils without decomposition above 360'. I t is very soluble in alcohol, chloroform or ether, less so in carbon bisulphide, p.etroleuni ether or hot water. I t gives color reactions with ferric chloride, reduces silver nitrate solution, and gives precipitates with lead nitrate or bromine water. I ts dincehl deriz~ative crystallizes from alcohol in long, six-sided crystals, m. p. 77"-77.5'. Attempts to determine the structure of this dioxydiphenyl by oxidation of its dimethyl ether (to veratric acid, etc.) were unsuccessful.

?VI. T. BOGERT.

The Action of Zinc on Triphenylchlormethane. BY JAMES F. NORRIS AND LLORA R. CULVER. Am. Chem. I., 29, 129- 14o.-The highly unsaturated compound obtained by Gornberg by the action of zinc upon triphenylchlormethane possesses such unusual interest that the authors have continued the experiments in this field begun by one of them (Norris) four years ago, the object of the present investigation being to discover whether any explanation of this remarkable reaction, other than that of trivalent carbon, can be found. An attempt was, therefore, made to determine quantitatively the substances which entered into the reaction and the products formed, and i t was found that the state- ment of Gomberg that when zinc and triphenylchlormethane react, in benzene solution, quantitative results are obtained accord- ingtothefollowingequation: 2(C6H5),CC1 + Zn = 2(CbH5)7C- + ZnCl,, was not correct. Part of the triphenylchlormethane

Organic Chemistry. I75

escapes the action of the metal. When a solution of tnphenyl- chlormethane in ethyl acetate is treated with zinc, in absence of moisture and oxygen, a highly unsaturated substance is formed, which readily absorbs oxygen with formation of an insoluble peroxide, (C,H,),C.O.O.C(C,H,),. I n the filtrate from this peroxide, triphenylmethane, triphenylcarbinol and an oil are at times present. Nef explained the formation of triphenylmethane from zinc and triphenylbrommethane by the assumption of an unstable intermediate compound, (C,H,),C-C,H,, which was partly reduced

to triphenylmethane, and partly polymerized to a red tar, and the authors believe it highly probable that a similar explanation applies to the presence of triphenylmethane and an oil among the products of the action of zinc upon triphenylchlormethane. An attempt to prepare a compound of the formula, (C,H,),C:C,H,, by the action of pyridine upon triphenylchlormethane at ordinary temperatures, gave only a Pyridine addition product, (C,H,),CCl. C,H,N, which separated in large pink crystals, m. p. 167'-167.5'. To explain the formation of the triphenylcarbinol, the amount of oxygen absorbed by the unsaturated compound (triphenylmethyl), the weight of zinc consumed, etc., were determined quantitatively in a special apparatus. The results of this quantitative exami- natiou show that the reaction between zinc and triphenylchlormethane is very complicated ; much more zinc is used up than is called for in Gomberg's equation, much more oxygen is absorbed than is contained in the peroxide, and the percentage of the latter obtained is less than that found by Gomberg. The authors sug- gest that a zinc alkyl compound may be formed in the reaction, which yields the triphenylcarbinol by absorption of oxygen, and in support of this assumption call attention to the fact that zinc hydroxide was shown to be present in some of the experiments. The formation of the peroxide, however, cannot be referred to a hypothetical zinc alkyl, and the authors conclude that the facts observed by them do not prove or disprove the conception of a trivalent carbon.

The Action .of Zinc on Benzoyl Chloride. BY JAMES F. "ORRIS AND D. R. FRANKLIN. Am. Chent. J . , 29, 141-149.- In connection with their investigation of the action of zinc upon triphenylchlormethane in ethyl acetate solution (see preceding review), the authors have studied the action of zinc on benzoyl chloride under similar conditions. The reaction is completed much more slowly than in the case of triphenylchlormethane. From a series of experiments, in which the conditions were con- stantly varied, the following conclusions are drawn : ( I ) At room temperature, zinc removes chlorine from benzoyl chloride without the formation of hydrogen chloride. ( 2 ) The molecular quantities of the two substances which react are approximately

I I

176 Review of American Ckemical Research.

those represented by the equation : 2C6H,COC1 + Zn = 2C6H5CO- + ZnC1,. (3) When the reaction is carried out in the presence of oxygen, only a small quantity of the gas is absorbed. (4 ) When the reaction product, after the removal of zinc chloride, is subjected to crystallization, benzoic acid and an amorphous solid are obtained. When distilled, the products obtained are benzoic acid, benzoic anhydride, and a small undistillable residue. i 5 ) When the reaction is carried out either in the presence of, or in the absence of, oxygen, no dibenzoyl is formed. (6) In some of the experiments, more zinc Eas used than is required by the equation given above and zinc hydroxide wa5 formed when a solution of the reaction product was treated with water. These ob- servations indicate that to some extent an organo-metallic compound was formed. ( 7 ) The reaction between zinc and benzoyl chloride is such a complicated one that it cannot be interpreted by use of the facts so far discovered. In the course of the experiments it was found that when benzoyl chloride and zinc chloride are heated together with ethyl acetate under a return condenser, a very reactive compound is formed apparently niade up of a combination of the two chlorides.

&I. T. BOGERT. On Certain Colored Substances Derived from Nitro Com-

pounds. BY C. LORING JACKSON AND R. €3. EARLE. Am. Chem. I., 29, 89-120.--The authors have continued the study of the colored addition-compounds obtained from the nitro derivatives of benzene with sodium alcoholates, or with other alkaline bodies. The work of other investigators in this field is discussed, and the name ( ( quinolnitro acids,” suggested for these substances by Meisenheimer, is adopted. Experimental data are given in support of the quinoid formula previously proposed by Jackson and Gazzolo. Thus, the addition of sodium isoamylate to trinitroanisol gives a substance of the following structure :

0 : X.ONa KO, / I I /\ /\

/ \ / \ 0

- N// 0,N- OP--\ /- \

CH,O/\O. c,H,, CH,. o/\o. C,H,

or,

v \/ 0-Ka

which, when treated with dilute hydrochloric acid, breaks down into about equal molecules of trinitroanisol and isoamyl picrate. Substances were also prepared containing two molecules of the alkaline body to one of the nitro compound. ExPERIMENT-~L- Pyeparaiion of frinif)*oazisol. -Anisic acid was nitrated by a mixture of equal volumes of fuming nitric and fuming sulphuric

Organic Chemistry . '77

acids at 7 0 ° , the yield of trinitroanisol being 60 per cent. of the theory, 24ddition-compound of trinitroanisol with sodium isoamylate (sodium salt of dinitromethoxyisoamyloxyquinol?~itro acid ) , C,H,( NO,),OCH,( NaOC,H,,) .-Prepared by the action of sodium isoamylate upon an excess of trinitroanisol, in dry benzene solution. Bright crimson powder, stable in vacuo, but instantly decomposed by dilute acids with formation of trinitroanisol and isoamyl picrate. Conversion of the addition-compound of trinitroanisol a z d soditim methylate into the isoamjd compound.-C,H,( NO,), OCH,.NaOCH,, mixed with isoamyl alcohol and warmed to 7 0 ° , yielded C,H,(NO,),OC,H,,.NaOC,H,,. Other experiments on the constitution of the addition-compounds (qzsinolnitro acids). -C,H, (NO,~yOCHQ,NaOCH, reacts with aniline to give a red salt, which is evidently the sodium salt of picryl anilide, C,H,(NO,), NNaC,H,, while, with an alcoholic solution of hydroxylamine, it gives the sodium salt of picryl hydroxylamine ; with phenylhydrazine, the reaction is too violent to give good results, at 100' the mixture takes fire in a few minutes, and, even in the cold, tarry products result ; with dimethylsulphate, methyl iodide, acetyl or benzoyl chlorides, no products could be isolated containing the organic radical instead of the sodium. Addition-compound from trinitrobenzene and sodium methylate (sodium salt of ~zill~~~I~methoxydiqui~tolnitro acid ) , C,H,( NO,),( CH,ONa),.-Red, amorphous substance, decomposing in a few hours, even in vacuo. Heated suddenly to roo', it explodes with great violence, but by raising the temperature gradually it may be heated to 150' without apparent change (except darkening) and without giving off any alcohol. Its decomposition appears to follow two lines : one consists essentially in the oxidation of one or more of the methoxy groups to formaldehyde, with compensating reduction of nitro groups to tetranitroazoxybenzene, while another reaction is indicated by the formation of nitrite and probably of some nitro phenol. Addition-comjound of triitifroan isol with two molecules of sodium methylute (sodium salt of nitrotrimethoxydipuinolnitro acid ) , C,H,(NO,),OCH,( NaOCH,),.-Prepared by the action of a large excess of sodium methylate upon a dry benzene solution of trinitroanisol. Amorphous orange powder, much less stable than the similar compound with only one molecule of methylate. I t decomposes in a manner resembling the foregoing trinitrobenzene compound, and is freely soluble in water. Addition-compound of trinitroanisol and potassium cyanide (potassium salt of nitrocyandipuinolnitro a d ) , C,H,( NO,),OCH,( KCN),.-Dark, reddish brown amorphous substance, freely soluble in water or alcohol, and very unstable. Addition-compound of h-initrobenzene and sodium Phenylate (sodium salt of nitrodiPhenoxydipuinolnitro acid ) , C,H,( NO,),( NaOC,H,),.-Bright brick-red amorphous powder, decomposed immediately by water, and one of the least stable of the compounds analyzed. Addition-compound of barium

178

dinitrobenzeneszi~konate and sodium methylate (barium S O ~ ~ U W Z salt of nitvosu~homethoxypuinolnifro acid ) , (C,H,( XO,),NaOCH,. SO,),Ba. -Amorphous, pale salmon powder when dry, but turns red when moistened with benzene, chloroform or ligroin. It is soluble in water, methyl or ethyl alcohol, but insoluble in the other common solvents. It appears to be one of the most stable compounds of this class. M. T. BOGERT.

On Azoxybenzylidene Bases. BY FRIEDXICH J. XLTVAY. Ber. d. chem. Ges., 35, 2434-2438.-j-Azoxybe~izvlideizanilzne, C,,H,,ON,( : NC,H,),, may be prepared by adding solid sodium hydroxide or potassium hydroxide to a boiling alcoholic solution of f-nitrobenzylaniline, the yield being about 70 per cent. of the theory. More convenient methods, and giving better yields, are those in which the base is prepared direct from p-nitrobenzyl chloride, aniline and sodium hydroxide, in alcoholic solution. Starting with p-nitrobenzylaniline, absolute alcohol may be used as the solvent, but with j-nitrobenzyl chloride some water must be added to the alcohol. p-Azoxybenzylidenanilirie forms glistening golden-yellow leaflets, m. p. 185' (uncorr. ), very difficultly soluble in ether or alcohol, easily solublein hot benzene. p-Azoxy- 6enzyl idene-o-toluie , C,,H,,ONl( : NCiHJ,, from p-azoxybenzaldehyde and o-toluidine, or from p-nitrobenzyl chloride, o-toluidine and sodium hydroxide, forms glistening orange leaflets, m. p. 182'-183' (uncorr.), very difficultly soluble in alcohol ; quite easily in cold, very easily in hot benzene. p-L4zox~~benzyl- idine-m-tol~iidiiie.-Orange leaflets, in. p. 133' (uncorr. ) , very easily soluble in cold benzene, very difficultly soluble in hot, absolute alcohol. p-nzoxybenzylideile-~-toluidine resembles the 0- atid m-toluidine isomers in appearance, but is much less soluble in benzene. I t melts at 188'-190' (uncorr.). p-Azoxybenzalde- hya'e, (ON,) (C,H, COH) ,.-The azoxybeuzylidetie bases ju s t described, decompose with dilute (about 27 per cent.) nitric acid, yielding p-azoxybenzaldehyde, which crystallizes from hot glacial acetic acid in yellowish needles, 1 - 2 cm. long, melting without decomposition at 1Sg'-190.5' (uncorr.), or 194'-195.5'(corr. ) . This aldehyde dissolves in concentrated sulphuric acid with an orange color, and by heating this solution for an hour at 110'- 120' an oxyazo color is produced.

Review of Amevicaa Ckemical Research

M. T. BOGERT.

BIOLOGICAL CHEnISTRY. On the Nucleoproteids of the Pancreas, Thymus, and Supra-

renal Gland, with Especial Reference to Their Optical Activity. B Y ARTHUR GAMGEE AND WALTER JONES. Am. J . physiol., 8, 447-455.-Six preparations obtained from the various glands are described with the methods of isolation employed. All of these sub3tances yield, on hydrolysis, phosphoric acid and purin

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