of the known facts regarding the formation and reactions of this type of compound.

R. W. WEST.

Halogen derivatives of diphenylmethane. A. E. TSCHITSCHIBABIN and A. A. SCHESLER (J. Russ. Phys. Chem. Soc., 1925, 56, 149-152). The method previously used for the reduction of alcohols of the diphenyl- and triphenyl-methane series (A., 1911, i, 277) serves for the preparation of various halogenated diphenylmethane derivatives (cf. also A., 1911, i, 278).

Phenyl-p-chlorophenylcarbinol,

CH,Cl-CHPh-OH, m. p. 61°, prepared from p-chlorobenzaldehyde and magnesium phenyl bromide, is reduced by means of hydriodic acid in glacial acetic acid to phenyl-pchlorophenylmethane. Phenyl-o-chlorophenylcarbinol, m. p. 65-65-5°, similarly obtained, yields phenylo-chlorophenylmethane, m. p. 13.2°, b. p. 164.5°/19 mm., do 1.1530. Phenyl-m-chlorophenylcarbinol, similarly obtained, has m. p. 38°. T. H. POPE.

Derivatives of toluene. R. POGGI (Atti R. Accad. Lincei, 1925, [vi], 2, 423-427).-m-Nitrobenzyl iodide, m. p. 84.5-86°, and 2: 4-dinitrobenzyl iodide, m. p. 75.5-76°, are obtained by boiling the alcoholic solutions of the corresponding chlorides with a slight excess of potassium iodide. By boiling p-nitrobenzyl thiocyanate with concentrated sulphuric acid, p-nitrobenzyl thiocarbamate,

NO, CH, CH2S.CO•NH2,

6

m. p. 140-141°, is obtained. By prolonged boiling of this compound with 20% hydrochloric acid, hydrogen sulphide, carbon dioxide, and ammonia are eliminated, giving p-nitrobenzyl mercaptan. m-Cyanobenzyl bromide, m. p. 94-95.5°, is prepared by the Sandmeyer reaction from m-toluonitrile. m-Cyanobenzyl iodide, m. p. 113-114°, and o-cyanobenzyl iodide, m. p. 77-78°, were prepared by boiling the corresponding chloro-derivatives in alcoholic solution with potassium iodide. By boiling an alcoholic solution of p-cyanobenzyl chloride with sodium thiosulphate for an hour, sodium p-cyanobenzyl thiosulphate, CN-CH, CH2 S2O,Na, was obtained, which on prolonged heating at 70° with concentrated sulphuric acid gave p-cyanobenzyl mercaptan, m. p. 43°. Oxidation of this compound in the cold by alcoholic iodine solution gave pp'-dicyanobenzyl disulphide, m. p. 147.5°.

F. G. TRYHORN.

Two forms of o-nitrotoluene. R. H. CLARK and

R. N. CROZIER (Trans. Roy. Soc. Canada, 1925, [iii], 19, III, 157–158).—The α- and ẞ-forms of o-nitrotoluene (Knoevenagel, A., 1907, i, 202) have practically the same refractive index and density and the same M as determined by the f. p. method. It is, however, claimed that the assumption of the existence of two electronic forms, CH,Me NO, and CH,Me NO2, as an explanation for the existence of the two modifications is supported by the results of chemical tests. J. S. CARTER.

+

+

2-Nitro-3: 4-dimethoxy-1-methylbenzene (2nitrohomoveratrole). E. MERCK CHEM. FABR.See B., 1926, 30.

H. B.

Reactions of organic thiosulphates. FOOTNER and S. SMILES (J.C.S., 1925, 127, 28872891). The organic sodium thiosulphates, RS.SO, ONa

(cf. Price and Twiss, ibid., 1907, 91, 2021) share with the disulphoxides (A., 1925, i, 391) certain characteristic reactions of the thiol-sulphone group, due to instability of the dithio-system in substances of the type RS ŠO,X; this group is readily split by alkali mercaptides and with varying ease by other reagents, the activity depending on the character of the group X. The organic thiosulphates are readily decomposed in aqueous solution by sodium mercaptides: R.S.SO,Na+NaSR'→RS SR'+Na2SO3. When R and R' are the same, a single symmetrical disulphide is produced; when they are dissimilar, a mixture of the two possible symmetrical disulphides is usually obtained, probably because of secondary reaction of the mercaptide with the disulphide (Lecher, A., 1920, i, 433), RS-SR'+NaSRRS•SR+ R'SNa. The organic thiosulphates are quickly and almost quantitatively decomposed by aqueous alkali cyanide, giving the corresponding thiocyanates in excellent yield, RS.SO,Na+NaCN R.SCN+ Na,SO. The disulphoxides behave similarly but are much less reactive, RS-SO,R+NaCNRSO2Na+ R.SCN.

Di-p-toluenesulphonyl sulphide (Tröger, A., 1899, i, 905) behaves similarly towards the mercaptans, the sulphur chain being ruptured with formation of sulphinate and thiosulphonate together with the disulphide corresponding with the mercaptan used, (C,H,SO2)2S+2RSNa C2H, SO2 SNa+C2H, SO2Na +(RS). Whilst sodium dithionate is not attacked by alkali mercaptides, the tri- and tetra-thionates are rapidly decomposed, giving the disulphide Na2SO+2R SNa → (RS)2+Na2SO3+Na2S2O3; Na SO+2R-SNa→ (RS)2+2Na2S2O3. This result is, in the authors' opinion, adequately explained by the structures proposed by Mendeleev for the polythionates. o-Nitrophenyl benzyl disulphide has m. p. 54°; benzyl 9-anthryl disulphide, m. p. 128°; p-nitrobenzyl thiocyanate, m. p. 79°, and 9-anthryl thiocyanate, p. 181°.

m.

6

M. JOHNSON.

of

Dependence of rotatory power on chemical constitution. XXVII. Optical properties n-alkyl p-toluenesulphinates. H. PHILLIPS (J.C.S., 1925, 127, 2552-2587).—When an optically inactive n-alkyl ester of p-toluenesulphinic acid is rotatory n-alkyl p-toluenesulphinate and a lævoheated gently with l-B-octanol a mixture of a lævorotatory B-octyl p-toluenesulphinate is produced which can be separated by fractional distillation p-toluenesulphinate thus produced yields an opticunder very low pressures. Alcoholysis of the l-ẞ-octyl ally active n-alkyl ester of opposite sign. By these methods, using l-B-octanol, n-alkyl p-toluenesulphinates have been prepared with a-6-72° and +0.92° and n-butyl esters with 1 -3.46° and +16.52° (l=1 dm. in each case). The asymmetry must be attributed to the sulphur, and since only three groups are attached to this atom, the reason for this asymmetry is sought in the electronic structure. According to Lowry's theory, the oxygen should be

25

5461

attached to the sulphur atom through a semipolar linking, the oxygen atom being negatively and the sulphur atom positively charged. The parachor (A., 1924, ii, 662) of ethyl p-toluenesulphinate has been determined by S. Sugden, and this confirms the presence of a semipolar linking (A., 1925, ii, 936). The observed asymmetry might have been attributed to the tetrahedral arrangement of three different groups and one lone pair of electrons, but the view that the asymmetry is due to the three groups not being coplanar with the positively charged sulphur atom is shown to be more in accordance with cognate facts. The existence of a positive charge is regarded as the essential factor making optical activity possible for a ter-covalent atom containing three different groups. The corresponding sulphonic acid and its n-alkyl esters do not give any indication that they can exist in optically active forms.

It is suggested that carboxylic esters contain a small proportion of an isodynamic form possessing a semipolar linking, the constitution of which is analogous to that of the sulphinic esters. The additional centre of asymmetry thus introduced would explain the complex dispersion of these esters.

Optically active p-toluenesulphinic esters undergo changes analogous to the Walden inversion. Thus if l-B-octanol is heated with ethyl p-toluenesulphinate, a lævorotatory ethyl ester remains. If this in turn is heated with n-butyl alcohol, a dextrorotatory n-butyl p-toluenesulphinate is obtained. On the other hand, if the inactive butyl ester is heated with l-ẞ-octanol, a lævorotatory n-butyl p-toluenesulphinate is produced.

By means of a cycle of changes involving the oxidation of p-toluenesulphinic esters to the corresponding sulphonic esters, l-B-octanol has been converted into d-ß-octanol and l-menthol into d-neomenthol. It is shown that when the p-toluenesulphinate of an optically active carbinol (such as 7-B-octanol) is treated with potassium acetate and ethyl alcohol the optically active alcohol is regenerated without inversion, but when the sulphinate is oxidised to the sulphonate and this then treated with potassium acetate and ethyl alcohol the acetate of d-ßoctanol is produced, showing that inversion has taken place. The slow mutarotation of p-toluenesulphinic esters of l-B-octanol and of l-menthol caused by the labile nature of the rotation due to the sulphinic acid group has been studied. An equilibrium value of a5893 -35.1° is obtained after about 1000 hrs.

25

primary formation of the aldol,

CH,Ph•CH(OH)-CHPh•CHO, which passes into the corresponding, unsaturated aldehyde by loss of water and subsequently loses the aldehydic group as formic acid, thus giving ay-diphenylpropene. The hydrocarbon, b. p. 178— 179° (corr.)/14 mm., m. p. 15-16°, may be conveniently prepared in 67% yield by heating phenylacetaldehyde with alcoholic potassium hydroxide under reflux. It is identical with the compound obtained from a-benzylcinnamic acid by Dieckmann and Kämmerer (A., 1906, i, 820) and yields the same dibromide, m. p. 109°, and pseudonitrosite, m. p. between 142° and 150°, according to the manner of heating; the latter compound is converted by diethylamine in boiling alcoholic solution into the substance, C19H24O2N2, m. p. 93°. The nitrosochloride has m. p. 166° (decomp.). xy-Diphenylpropene is readily converted into ay-diphenylpropane, b. p. 301-303° (corr.), 166-168°/16 mm., by sodium and boiling alcohol or hydrogen in the presence of palladised calcium carbonate. Oxidation of ay-diphenylpropene by permanganate in alkaline solution yields only benzaldehyde, benzoic and phenylacetic acids; in acetone solution, particularly in the presence of sulphuric acid, benzaldehyde and By-diphenylpropaldehyde hydrate, CH2Ph⚫CHPh⚫CHO‚Í‚O, m. p. 116-117° (semicarbazone, m. p. 189°), are produced. Ozonisation of ay-diphenylpropene and subsequent decomposition of the ozonide yields only benzaldehyde, and benzoic and phenylacetic acids.

Under the modified conditions of preparation of ay-diphenylpropene, three isomeric B-benzyl-ay-diphenyl-8-valerolactones, m. p. 109°, 133°, and 165°, respectively, are obtained as by-products. A fourth isomeride, m. p. 135°, was prepared during attempts to obtain the methyl ester from the dry sodium salt from the lactone, m. p. 109°, and methyl sulphate. Further, the lactone, m. p. 109°, exists in a dimorphous form, m. p. 122°. Apparently, the primary aldol passes into the corresponding unsaturated aldehyde which unites with a further molecule of phenylacetaldehyde, yielding the dialdehyde,

CH,Ph•CH(CHPh CHO),

this is transformed by Cannizzaro's reaction into the compound,

CH2Ph.CH(CHPh⚫CH, OH) CHPh⚫CO2H, from which four isomeric B-benzyl-ay-diphenyl-dvalerolactones are derived by loss of water.

Composition of rubicene. K. DZIEVOŃSKI and J. SUSZKO (Ber., 1925, 58, [B], 2544-2546).-New analyses of rubicene confirm the composition, CH 12, assigned to it by Dzievoński and Suszko (A., 1922, i, 730) in place of the formula, C6H14, suggested by Pummerer and Ulrich (A., 1925, i, 1259; cf. also Pummerer, A., 1912, i, 182). H. WREN.

Action of amines on di- and tri-chloroacetic acids. A. S. WHEELER and E. DE W. JENNINGS (J. Elisha Mitchell Sci. Soc., 1924, 40, 112).—When substituted amines are used, the di- and tri-chloroacetates are formed, respectively. However, with such amines as aniline and o-toluidine the dichloroacid produces trichloroacetates.

CHEMICAL ABSTRACTS.

Action of aromatic amines on semicarbazide hydrochloride. I. MACUREVITSCH (J. Russ. Phys. Chem. Soc., 1925, 56, 55-60).-When semicarbazide hydrochloride is boiled with a primary aromatic amine, such as aniline, o- or p-toluidine, 2 : 3-xylidine, or benzylamine, the corresponding substituted carbamides are obtained: NH2R+ÑH2·NH·CO·NH2= NH,NH CO NHR+NH, and NH NH CONHR+ NH.R=NHR CONHR+N,Hạ (cf. A., 1925, i, 984).

2

T. H. POPE.

Action of magnesium butyl bromide on aromatic thiocarbimides. D. E. WORRALL (J. Amer. Chem. Soc., 1925, 47, 2974—2976).—The following substituted amides of thiovaleric acid were obtained by the action of magnesium butyl bromide on the appropriate thiocarbimides (cf. Sachs and Loevy, A., 1903, i, 334; 1904, i, 307; Gilman, A., 1924, i, 382); thiovaleryl-anilide, m. p. 38—39°; -p-toluidide, m. p. 69-70°; -p-anisidide, m. p. 6263°;-p-chloroanilide, m. p. 101-5-102°; -p-bromoanilide, m. p. 112°; -diphenylamide, m. p. 147— 148°; -8-naphthylamide, m. p. 79-80°; and bisthiovaleryl-p-phenylenediamide, m. p. 198-199°. The action of hydroxylamine on these derivatives affords oximes, hydrogen sulphide and some ammonia being

liberated.

F. G. WILLSON.

Isomeric change in aromatic compounds. I. Conversion of diacylanilides into acylaminoketones. A. W. CHAPMAN (J.C.S., 1925, 127, 28182820).—When a current of dry hydrogen chloride is passed through fused diacetanilide or dibenzanilide, the acyl chloride and monoacylanilide result. Diacylanilides, when heated in presence of either hydrogen chloride or zinc chloride, are converted into the corresponding acylamino-ketones. The The catalytic activity of the zinc chloride, which is ineffective when absolutely dry, is ascribed to the presence of a little free hydrogen chloride, without which rearrangement does not occur. Since the necessary conditions

are exactly those under which hydrogen chloride decomposes the diacylanilides, it is suggested that this change, previously regarded as intramolecular (Chattaway, J.C.S., 1904, 85, 386), is, in reality, a decomposition followed by recondensation, thus: NPhAc2+HCl → NHPhAc+AcCl M. JOHNSON. Ac-C.HNHAc+HCl.

Preparation of p-bromophenylhydroxylamine by the emulsification process. R. D. HAWORTH and A. LAPWORTH (J.C.S., 1925, 127, 2970).-Reduction of p-bromonitrobenzene by the method previously described (ibid., 1921, 119, 770) is frequently unsuccessful. Good results are obtained by the use of more solvent benzene and more reducing solution. p-Bromonitrobenzene (5 g.), benzene (40 c.c.), hydrosulphide solution (120 g., loc. cit., p. 769), and calcium chloride (5 g., in a little water) are emulsified. After 1 hrs., solid ammonium chloride (5 g.) is added. After shaking, the precipitated p-bromophenylhydroxylamine (about 2.9 g.) is collected. A further yield (0.5 g.) can be obtained from the benzene layer by precipitation with petroleum (b. p. 40-60°). The sodium sulphide crystals used in making the reducing solution must be of good quality.

M. JOHNSON.

Dibromination of aceto-m-toluidide. S. C. J. OLIVIER (Rec. trav. chim., 1925, 44, 1109-1112).– By the action of 2 mols. of bromine on an acetic acid solution of aceto-m-toluidide, a mixture is obtained which after hydrolysis consists of 73% of 4: 6-dibromo-m-toluidine and 27% of 2: 6-dibromo-m-toluidine, m. p. 66-5-67°. It is shown that the 2: 6-dibromo-compound, m. p. 33-35°, previously described (Neville and Winther, J.C.S., 1880, 37, 440) is a eutectic mixture of the two isomerides.

R. W. WEST. Trinitrophenylnitroaminoethyl nitrate. R. C. MORAN.-See B., 1926, 78.

Preparation of some primary amines by the catalytic reduction of nitriles. W. H. CAROTHERS and G. A. JONES (J. Amer. Chem. Soc., 1925, 47, 3051-3057).-p-Toluonitrile is reduced smoothly in acetic anhydride solution by hydrogen in presence of platinum oxide, with formation of p-methylbenzylacetamide, m. p. 110-111° (cf. Lustig, A., 1895, i, 162), in 88% yield. The reduction requires over 5 hrs. with hydrogen under 3 atm. pressure. In glacial acetic acid, a 71% yield of pp'-dimethyldibenzylamine, together with small proportions of the corresponding primary and tertiary amines, was obtained similarly in 6 hrs. In absolute alcohol, reduction proceeds more slowly, and both primary and secondary amines are produced. In n-butyric anhydride, a 74% yield of p-methylbenzyl-n-butyramide, m. p. 71-72°, was obtained. Benzonitrile affords similarly, in acetic anhydride solution, benzylacetamide; in glacial acetic acid, benzylamine and dibenzylamine, the former predominating; and in absolute alcohol, ammonia and the primary and secondary amines. o-Toluonitrile is reduced similarly in acetic anhydride solution to o-methylbenzylacetamide, m. p. 76-76-5° (cf. Strassmann, A., 1888, 474), whilst phenylacetonitrile affords ẞ-phenylethyl

acetamide, in 63% yield. The above acetyl derivatives of primary amines are soluble in cold dilute hydrochloric acid, from which they are precipitated unchanged on addition of alkali; the corresponding aromatic sulphonyl derivatives are only slightly soluble in dilute alkali. The following acyl-derivatives of the above amines are described: p-methylbenzyl-phenylcarbamide, m. p. 188-188-2°, -p-toluenesulphonamide, m. p. 94.7—95.5°, and p-bromobenzenesulphonamide, m. p. 126.5-127-5°; o-methylbenzylphenylcarbamide, m. p. 167-5-168°, -benzenesulphonamide, m. p. 128-3-129.1°, p-toluenesulphonamide, m. p. 118-7-119.2°, and -p-bromobenzenesulphonamide, m. p. 106-5-107°; B-phenylethyl-p-bromobenzenesulphonamide, m. p. 88.5-89.5°, and -phenylcarbamide, m. p. 153-5-154-5° (cf. Forster and Stötter, J.C.S., 1911, 99, 1338). The success of the preparation of primary amines by reduction of nitriles in acid anhydride solution is ascribed to prevention of hydrolysis of the imine usually assumed to be formed intermediately, and to prevention of its condensation with the primary amine by the prior acylation of the latter. F. G. WILLSON.

Benzidine derivatives of thiocarbamide and azo dyes therefrom. L. PINTO.-See B., 1926, 43.

Action of sulphites on aromatic amino- and hydroxy-compounds. XII. Products of the action of sulphites on 1: 8-dinitronaphthalene. H. T. BUCHERER and H. BARSCH (J. pr. Chem., 1925, [ii], 111, 313-339; cf. A., 1925, i, 1338). When 18-dinitronaphthalene is boiled with aqueous sodium hydrogen sulphite solution (8.3 mols. per mol. of dinitro-compound), and the cooled, filtered solution acidified, a naphthylenediaminetrisulphonic acid separates (cf. Fischesser, D.R.-P. 79577) in a yield of 8.8% of the theoretical, calculated on the dinitronaphthalene used, whilst the mother-liquor contains a further 15.4% yield of the acid, together with the sulphurous ester of an aminonaphtholtrisulphonic acid. The latter is hydrolysed by boiling hydrolysed by boiling with alkali, after which the above mother-liquor contains active material (evaluated by titration with diazo-solution) corresponding with 31.9% of the applied dinitronaphthalene. When the naphthylenediaminetrisulphonic acid is boiled with aqueous sodium hydrogen sulphite, it is converted into the sulphurous ester of an aminonaphtholtrisulphonic acid. As this reaction is hindered by a sulphonic a sulphonic group ortho or meta to the amino-group, it is concluded that the trisulphonic acid is actually 1:8naphthylenediamine-2: 4: 5-trisulphonic acid, both of the alternative constitutions suggested by Fischesser (loc. cit.) being untenable. When the trisulphonic acid is boiled with cyclohexanone in presence of concentrated hydrochloric acid, a condensation product, probably (I), is formed, which is not attacked by boiling sodium hydrogen sulphite solution.

with sodium hydrogen sulphite solution in presence of ammonia (cf. D.R.-P. 215338), the cooled, filtered solution deposits, on acidification, a small proportion of a-naphthylamine-4 : 7-disulphonic acid, containing traces of the corresponding aminonaphtholdisulphonic acid and naphthylenediaminedisulphonic acid. The total yield of disulphonic acids corresponds with 6.9% of the dinitronaphthalene used, whilst the mother-liquor contains further an approximately equal proportion of the sulphurous ester of the aminonaphtholdisulphonic acid. When boiled with aqueous sodium hydrogen sulphite, a-naphthylamine4:7-disulphonic acid is converted into the sulphurous ester of the corresponding naphtholdisulphonic acid.

Treatment of 1: 8-naphthylenediamine with 11 pts. of 2% fuming sulphuric acid at 95-100° for several hrs. affords 1 : 8-naphthylenediamine-4-sulphonic acid, which, when warmed with 5 pts. of 20% fuming sulphuric acid, yields a disulphonic acid, probably 1:8-naphthylenediamine-4: 5-disulphonic acid (cf. D.R.-P. 72584). F. G. WILLSON.

Reactions of azoxy-compounds. I. Action of light. W. M. CUMMING and G. S. FERRIER (J.C.S., 1925, 127, 2374-2379).-o-Hydroxyazo-compounds result when solutions of certain azoxy-compounds are exposed to the light of a mercury-vapour lamp. The yields are highest in alcohol and lowest in benzene. Azobenzene in 85% alcohol gives a 63.3% yield of o-hydroxyazobenzene, m. p. 82-83°, in 200 hrs. (44% in 100 hrs.). The same transformation occurs under the influence of sunlight or electric light. (filament lamp). 2:2, 3:3, and 4:4'-Azoxytoluene, 4:4'-dichloroazoxybenzene, 2: 2'-diamino4: 4'-azoxytoluene, and 4: 4'-azoxyanisole react similarly. 2-Hydroxy-3: 3'-azotoluene has m. p. 61-562.5°. 4:4'-Azoxyphenetole and 4: 4'-dinitroazoxybenzene are unchanged.

The existence of an isomeric 4: 4'-azoxytoluene, m. p. 75° (Janovsky and Reimann, A., 1889, 392), is unconfirmed, and a setting-point curve shows that it cannot be a solid solution of p-azo- in p-azoxytoluene. C. HOLLINS.

Azo dyes. BRITISH DYESTUFFS CORP., LTD., K. H. SAUNDERS, and H. GOODWIN.-See B., 1926, 7. o-Hydroxyazo dyes. A.-G. F. ANILIN-FABR.— See B., 1926, 7.

Azo dyes. Soc. OF CHEM. IND. IN BASLE.-See B., 1926, 43.

Azo dyes. G. KALISCHER, K. KELLER, and L. CASSELLA U. Co.-See B., 1926, 44.

Phenylhydrazine and factors affecting hydrazone formation. E. G. R. ARDAGH and J. G. WILLIAMS (Trans. Roy. Soc. Canada, 1925, [iii], 19, III, 75, and J. Amer. Chem. Soc., 1925, 47, 29762983). The iodometric method (Ardagh and Williams, this vol., 189) for the determination of phenylhydrazine gives low results when a buffer solution is present. Correct results are obtained when the solution is just acid to methyl-orange. Aqueous solutions of phenylhydrazine and its salts oxidise fairly rapidly on exposure to air, the solutions being stable when prepared with water free from oxygen and preserved in an atmosphere of nitrogen.

Hydrazone formation is a reversible process, the equilibrium being greatly influenced by the acidity of the medium. Acetonephenylhydrazone formation is almost complete over the pH range 5-7, provided the hydrazone is at the same time salted out. If the hydrazone be extracted with some suitable solvent, immiscible with water, the reaction is quantitative. The rôle of sodium acetate in hydrazone formation is solely that of a buffer. J. S. CARTER.

Action of hydrazine on nitro- and chloronitroderivatives of benzene and naphthalene. I. E. MÜLLER (J. pr. Chem., 1925, [ii], 111, 273-276).A summary of previous researches in this field, introductory to the following three papers. F. G. WILLSON.

Action of hydrazine on nitro- and chloronitroderivatives of benzene and naphthalene. II. Action of hydrazine hydrate on some nitro- and chloronitro-compounds. E. MÜLLER and G. ZIMMERMANN (J. pr. Chem., 1925, [ii], 111, 277292). Whilst the action of hydrazine hydrate on m-nitrobenzoic acid in alcoholic solution affords only the corresponding hydrazine m-nitrobenzoate, m. p. 182°, in absence of solvent the nitrobenzoic acid is reduced at water-bath temperature in 30 min. with formation of m-aminobenzoic acid. p-Nitrobenzoic acid behaves similarly (cf. Curtius and Bollenbach, A., 1907, i, 1078). p-Nitrotoluene is reduced to p-toluidine when heated with hydrazine hydrate for 4 hrs. at 130° in a sealed tube, o- and m-toluidines

being also analogously produced. At 150°, hydrazine hydrate reduces o-, m-, and p-nitroanilines to the corresponding phenylenediamines. 2:4-Dinitrotoluene is reduced by alcoholic hydrazine hydrate at water-bath temperature to o-nitro-p-toluidine, and this is further reduced to 2:4-tolylenediamine when heated with hydrazine hydrate at 140°. Reduction of m-chloronitrobenzene to m-chloroaniline by the action of hydrazine hydrate proceeds at waterbath temperature, but o-chloronitrobenzene, when boiled with hydrazine hydrate, yields hydroxybenzotriazole as the hydrazine salt, m. p. 110-120° with loss of hydrazine; o-nitrophenylhydrazine is probably the primary product. 2: 4-Dichloronitrobenzene reacts with hydrazine hydrate in hot alcoholic solution with formation of the hydrazine salt, m. p. 182-183° (decomp.), of the corresponding 4-chlorohydroxybenzotriazole, exploding at 204-205° (potassium salt, explodes above 300°; ethyl ether, m. p. 59-60°; benzoyl derivative, m. p. 126°). The 5-chloro-2: 4-dinitrophenylhydrazones of benzaldehyde, orange, m. p. 242°, acetone, yellow, m. p. 123°, ethyl acetoacetate, m. p. 115°, and formaldehyde, yellow, m. p. 124°, are described. Benzoyl-5-chloro-2: 4-dinitrophenylhydrazine, reddish-yellow, has m. p. 219°. When treated with sodium nitrite in suspension in cold aqueous-alcoholic hydrochloric acid, 5-chloro2: 4-dinitrophenylhydrazine affords an unstable nitrosoamine, yellow, decomp. at 85°, which, when heated, loses water and nitrogen with formation of 5: 5′-dichloro-2:4 : 2′ : 4′-tetranitroazobenzene, yellow, m. p. 93°, exploding at higher temperatures with evolution of a yellow, irritant vapour. 5-Chloro2: 4-dinitrophenylhydrazine dissolves in alkali with

darkening and evolution of gas. Acidification of the solution affords brown flocks which could not be purified, but which did not appear to represent a hydroxytriazole derivative. The dihydrochloride, pale yellow, readily hydrolysed, the sulphate, pale yellow, decomp. at 213°, and the dibenzoyl derivative, pale orange-yellow, m. p. above 300°, of 2: 4-dinitro-l: 5 dihydrazinobenzene, are described. F. G. WILLSON.

Action of hydrazine on nitro- and chloronitroderivatives of benzene and naphthalene. III. Action of hydrazine hydrate on 2:4: 5-trichloronitrobenzene. E. MÜLLER and W. HOFFMANN (J. pr. Chem., 1925, [ii], 111, 293–306).— Hydrazine hydrate reacts with 2:4: 5-trichloronitrobenzene in boiling alcoholic solution with formation of 34-dichloro-6-nitrophenylhydrazine, orangeyellow, m. p. 194.5°, and 4: 5-dichlorohydroxybenzotriazole, CH,C,N(OH)N, exploding at 194– 196° after becoming brown at 190° [hydrazine salt, m. p. 205° (decomp.); potassium salt, explodes at salts; aniline salt, m. p. 168° (decomp.); methyl 230-250°; barium, magnesium, copper, and silver ether, m. p. 129°; ethyl ether, m. p. 90°; benzoyl derivative, m. p. 152°; acetyl derivative, m. p. 150°; carbethoxymethyl derivative, m. p. 109°; carbethoxyderivative, m. p. 123°]. Formation of the triazole is favoured by the application of excess of hydrazine hydrate, and by the action of hydrazine or of alkalis on the dichloronitrophenylhydrazine. The following benzaldehyde-, yellowish-red, m. p. 184°; salicylalde3: 5-dichloro-6-nitrophenylhydrazones are described : hyde-, yellowish-green, m. p. 207°; resorcylaldeyellow, m. p. 157°; and benzophenone-3: 5-dichlorohyde-, orange-red, m. p. 251°; acetone-, lemon6-nitrophenylhydrazone, pale yellow, m. p. 162°. Treatment with nitrous acid converts the dichloroazoimide, yellowish-brown, m. p. 56°, which is decomnitrophenylhydrazine into 3: 4-dichloro-6-nitrophenylposed by alkalis into azoimide and a compound, m. p. 34, possessing phenolic properties. anhydrous hydrazine on 2: 4: 5-trichloronitrobenzene chloro-6-nitrophenylhydrazine, red, m. p. 172° [hydroaffords, together with the above triazole, 2: 3-dichloride, m. p. 195° (decomp.); benzylidene derivative, red, m. p. 225°].

The action of

F. G. WILLSON.

Action of hydrazine on nitro- and chloronitroderivatives of benzene and naphthalene. IV. Action of hydrazine on 1-chloro-2:4-dinitronaphthalene. E. MÜLLER and K. WEISBROD (J. pr. Chem., 1925, [ii], 111, 307-312). When treated with hydrazine hydrate in hot alcoholic solution, 1-chloro-2: 4-dinitronaphthalene affords 2: 4-dinitronaphthalene, the hydrazine salt of 2:4-dinitro-anaphthol, m. p. 203–205°, 5-nitro-3-hydroxynaphthotriazole, (I), yellow, m. p. 215° (decomp.), and 4 : 4'-dinitro-2: 2'-azonaphthalene. The primary product

NO2

is probably 2: 4-dinitronaphthylhydrazine, from which the triazole derivative is derived by reduction and condensation with the ad(I.) N(OH) jacent nitro-group, but which also loses nitrogen and hydrogen with formation of