Paratriazobenzenesulphonic acid, <N>N.C.H.SO,H, is prepared from the barium salt, and forms white, deliquescent needles, very soluble in alcohol. The barium salt, with 2 mols. H2O, is obtained from the phenylhydrazine-compound by boiling with barium carbonate. It crystallises in almost white, hexagonal plates.

Triazonaphthalenesulphonic acid, NCH, SO3H, is obtained from its phenylhydrazine-compound in a manner similar to triazobenzenesulphonic acid, and crystallises in white needles, very soluble in alcohol and in water. The barium salt forms white plates of a silvery Instre, very sparingly soluble. The phenylhydrazine compound resembles the corresponding triazobenzene-derivative in its chemical and physical behaviour. N. H. M.

Constitution of Diazoamido-compounds. By R. MELDOLA (Phil. Mag. [5], 32, 513-529).-Only one diazoamido-compound of the constitution X N, NHY is known, whichever radicle has been first diazotised, whilst three ethyl-derivatives are known: (1) prepared by diazotising X-NH, and combining with Y-NHEt; (2) by diazotising Y⚫NH2 and combining with X-NHEt; and (3) by directly replacing the H in the compound X.N,HY by ethyl. These facts cannot be reconciled with the usual formula of Kekulé. The conditions to be fulfilled by any formula are: (1) that it should be symmetrical so as to represent the identity of the mixed diazoamido-compounds; (2) that it should be capable of representing more than two isomeric alkyl-derivatives of mixed compounds. Griess' formula, CH, NH: NH: NH: CH1, is objected to, since it represents diazoamido-benzene as a phenylenederivative, and contains three replaceable hydrogens, whilst the dinitrodiazoamido-compounds point to only one being present, and it does not represent the easy resolution of diazoamido-compounds by acids. NX Victor Meyer's abandoned formula, NH<>, fails to represent the N of the NH as being directly attached to either of the radicles. The N formulæ >NHXY and N N NHXY, due to the author, are also discarded, as they do not represent the decomposition by acids or the existence of isomeric alkyl-derivatives. Finally the formula X-N NH >, in which the phenyl of the radicles X and Y is regarded Y.N as triatomic, is considered best to represent the reactions of the mixed diazoamido-compounds, the phenyl having the constitution CH: CH = C<CH: CH>CH—in accordance with Fittig's theory of the constitution of quinone. The third ethyl-derivative of the mixed diazoamido-compounds can now be considered to be formed by the replacement of the nitrogen-attached hydrogen of the above formula, whilst, owing to the symmetry of the formula, the same mixed diazoamido-compound will be formed irrespective of the order of combination. Again, by supposing the NN to be eliminated with the radicles X and Y in turn, the production of two diazo- and two diamido-compounds by means of hydrochloric acid is explained. On

the other hand, this formula does not satisfactorily represent the normal compounds. In representing the compound obtained from diazotised paranitraniline or para-ethylnitraniline as

_C2H1(NO2)·N2 NH<CH.(NO2).N

the ethyl-derivatives from diazotised paranitraniline and meta-ethylaniline and from diazotised metanitraniline and para-ethylaniline should have a similar constitution, but the formula being symmetrical the compounds would be identical, whereas they are undoubtedly isomeric. Although Kekulé's formula accurately represents the reactions of the normal compounds, their stability is at variance with such a chain formula, no other instance of which is known amongst nitrogen compounds, the author therefore prefers the formula N NHX, the compound splitting when decomposed, so as to leave the NN in combination with the lower X, and thus giving only two products. The para-position is chosen for the free bonds in the radicle C,H,"", in accordance with the conversion of diazoamidobenzene into amidazobenzene, in which the substituents hold the paraposition. H. K. T.

Diazoamido-compounds. By B. FISCHER and H. WIMMER (Ber., 20, 1581—1583).—A comparison of the methods proposed by Fischer (Abstr., 1854, 1014), and by Staedel and Bauer (Abstr., 1886, 943), for the preparation of diazoamidobenzene shows that they are equally satisfactory in this particular, but that the former is to be preferred when mixed diazoamido-compounds are required. The melting point of the diazoamidobenzene prepared by either method is 98°, and the product obtained by Fischer's method is free from amidoazobenzene. Diazoamidoparatoluene can also be readily prepared from paratoluidine under the same conditions.

Diazoamido-orthotoluene is formed when orthotoluidine (2 mols.) is dissolved in hydrochloric acid (3 mols.) and water (3 mols.), the solution cooled to -5°, and treated with a solution of sodium nitrite (1 mol.), sodium acetate being added as required to remove the hydrochloric acid set free. The temperature is maintained at -5° for six hours; the crystals of diazoamido-orthotoluene are then separated, drained on a tile, dissolved in cooled alcohol, and thrown out of solution in the crystalline form by addition of ice. It is an orange-yellow, crystalline powder, melts at about 50°, and decomposes even during the spontaneous evaporation of its solutions in various media, such as alcohol, ether, &c.

Diazoamidoxylene, prepared from xylidine by a similar method, separated as an oil, and could not be obtained in a crystalline state. W. P. W. Hydroxyazo-compounds. By B. FISCHER and H. WIMMER (Ber., 20, 1577-1581).-The authors, working on similar lines to Heumann and Economides (this vol., pp. 480, 684), have independently obtained hydroxyazo-compounds by the addition of a diazoamido-derivative (1 mol.) to a phenol (1 mol.) in the fused state. In this way crtho

tolueneazoresorcinol is formed from diazoamido-orthotoluene and

resorcinol, and a xyleneazoresorcinol, C ̧H„N,CH,(OH)2, from diazoamidoxylene and resorcinol; the latter compound crystallises from alcohol in fiery-red needles, and melts at 205-206°; it is identical with the azo-compound prepared by the action of diazoxylene chloride on resorcinol.

Under similar conditions diazoamidobenzene, diazoamído-orthotoluene, and diazoamidoparatoluene when added to fused ß-naphthol yield benzeneazo-6-naphthol, orthotolueneazo-ß-naphthol, and paratolueneazo-ẞ-naphthol respectively (this vol., p. 55). W. P. W.

Unsymmetrical Benzoylphenylhydrazine. By A. MICHAELIS and F. SCHMIDT (Ber., 20, 1713-1718).-The doubt expressed in the author's first communication (this vol., p. 365) as to the constitution of this compound has now been removed, as it has been found that it unites readily with benzaldehyde and with acetone, with elimination of water; it must therefore contain a nitrogen-atom in union with two hydrogen-atoms, that is, have the formula NPhBz-NH,. The author suggests that phenylhydrazine-derivatives, where substitution occurs in the NH-group, shall be termed z-compounds, the term B-compounds being applied to the symmetrical derivatives in which substitution has occurred in the NH-group. The statement (loc. cit.) as to the difference in behaviour of the authors' dibenzoylphenylhydrazine with that described by Fischer was due to a misprint in Fischer's paper; the substances are identical.

The following salts of a-benzoylphenylhydrazine are described: the hydrobromide melts at 191°; the sulphate crystallises in groups of slender needles and melts at 191°. The nitrate forms long, lustrous plates and melts at 145°; the picrate melts at 122°.

When treated with nitrous acid in strongly acid solution, a-benzoylphenylhydrazine is converted into benzoylaniline and nitrous oxide, in neutral solution, on the other hand, it yields diazobenzenimide and benzoic acid.

a-Benzoyl-B-acetylphenylhydrazine, NPhBz-NHAc, obtained by the action of acetic anhydride on the base, crystallises in long needles and melts at 152-153°; it is also obtained by the action of benzoic chloride on ẞ-acetylphenylhydrazine.

Benzoylphenylsemicarbazide, NPhBz NH.CO.NH2, is obtained by the action of potassium cyanide on a feebly acid solution of a salt of the base. It forms crystalline crusts, melts at 202-203°, and is sparingly soluble in benzene, readily in alcohol. Diphenylbenzoylthiosemicarbazide, NPhBz-NH·CS⋅NHPh, is prepared by the action of phenylthiocarbimide on the base. It is crystalline, melts at 310°, and is sparingly soluble in ether, benzene, chloroform, and hot alcohol.

Benzylidenebenzoylphenylhydrazide, NPhBzN: CHPh, is prepared by gently heating a mixture of benzaldehyde and benzoylphenylhydrazine; it crystallises in very thin needles of silky lustre, melts at 122°, is nearly insoluble in water, readily in alcohol, and only reduces Fehling's solution after long boiling.

Acetonebenzoylphenylhydrazide, NPhBzN: CMe, separates after a time from a hot solution of benzoylphenylhydrazine in acetone, after dilution with water. It forms lustrous prisms, melts at 115.5°, and

is very soluble in acetone and alcohol, more sparingly in ether, scarcely soluble in water. Acetophenone benzoylphenylhydrazide, NPhBz N CMePh, is obtained after a long time from a mixed alcoholic solution of its constituents; it crystallises in colourless needles, melts at 124°, and is readily soluble in alcohol, insoluble in water.

Acetylbenzylidenephenylhydrazine, NPhAc-N: CHPh, is mentioned. A. J. G.

but not described.

Manufacture of Methyl-violet. By O. MÜHLHÄUSER (Dingl. polyt. J., 264, 37-45). For the production of this dye 20 kilos. of methylaniline and 8 kilos. of phenol are heated at 55° with 175 kilos. of rock salt and 10 kilos. of copper sulphate. The operation is conducted in cast-iron cylinders provided with agitators. The oxidationproduct is then washed with water and treated with milk of lime when the salt and phenol are dissolved, whilst the methyl-violet, copper hydroxide, and calcium sulphate are precipitated. The mixture is filtered and washed, and the precipitate saturated with hydrogen sulphide. The copper is thereby converted into the sulphide, and the dye separated from it by means of hydrochloric acid. The violet solution is then treated with a filtered solution of salt, which precipitates the colouring matter as a green tarry mass. This is purified by solution in hot water and reprecipitation with salt solution. purified product is washed with water, dried and ground. made up into the different brands (violet 3 B, 4 B, and 5 B) by the addition of benzyl-violet. The methyl-violet obtained by this method consists of a mixture of tetra- and penta-methylpararosaniline.

The

It is then

D. B.

Induline and Azophenine. By O. N. WITT (Ber., 20, 15381541).-Azophenine (Thomas and Witt, Trans., 1883, 117) is best prepared by heating amidoazobenzene (2 parts), aniline hydrochloride (1 part), and aniline (4 parts) for 24 hours at 80-90°; it is washed with alcohol and crystallised from alcohol. When the heating is continued for 12 to 20 hours at 125-130°, the product consists of induline, CiH15N3, together with the higher induline, CH23N, and its phenyl-derivative, C6H2N5. Azophenine is also formed by the action of free nitrosodimethylaniline and nitrosodiethylaniline on aniline. If the aniline is replaced by toluidine, azoparatoline (Nölting and Witt, Abstr., 1884, 742) is obtained.

When azophenine is heated at 360°, it is decomposed into aniline, fluorindine, and a violet dye. When reduced with tin and hydrochloric acid, it yields aniline and a sparingly soluble hydrochloride of an unstable base. It is concluded that azophenine is an azo-dye, formed by the dehydrogenation of aniline, and that it contains on the one side of one or several azo-groups, the radicle phenyl, on the other side, an unknown radicle.

When induline is distilled with lime, the greater part is carbonised and a distillate is obtained containing carbazole, together with aniline, benzene, and diphenylamine; induline is therefore a diphenylamine-derivative.

N. H. M.

Roshydrazine and a New Class of Dyes. By J. H. ZIEgler (Ber., 20, 1557-1558).--When 5 grams of rosaniline dissolved in 30 c.c. of strong hydrochloric acid and 70 c.c. of water is treated with 35 grams of sodium nitrite, and the whole then added to a solution of 12 grams of tin in 30 c.c. of hydrochloric acid, the hydrazine salt separates in green crystals, readily soluble in water, almost insoluble in strong hydrochloric acid. The yield is 13 grams. The shade of the salt of the new hydrazine, which is called roshydrazine, is somewhat more blue than that of magenta. The solution reduces Fehling's solution in the cold. It readily forms condensation-products with ketones and aldehydes. Formic acid yields a red compound, acetone, aldehyde, pyruvic acid, and benzophene, red to blue-violet compounds, benzaldehyde and ethyl acetoacetate, blue dyes. The dyes dissolve readily in alcohol, sparingly or not at all in water.

N. H. M. Aniline Sebate and Diphenyl-sebacamide. By G. GEHRING (Compt. rend., 104, 1451-1452).-When aniline (2 mols.) is mixed with sebacic acid (1 mol.), dissolved in alcohol, complete combination takes place without separation of water, and with formation of aniline sebate, (C,H,N)CH3O4, which is obtained by evaporation in a vacuum, and is purified by recrystallisation from hot water. It then forms thin, colourless, highly lustrous, rhomboidal lamellæ, which are only slightly soluble in cold, but more soluble in hot water, very soluble in cold alcohol, and somewhat soluble in boiling ether or chloroform. Aniline sebate melts at 134°, and sublimes without decomposition. It dissolves in concentrated sulphuric acid, and the solution gives the colour reactions for aniline with oxidising agents.

Aniline sebate does not lose water and form an anilide even at 250°. If, however, equal parts of aniline and sebacic acid are heated together, the temperature being gradually raised to 215°, diphenylsebacamide, (PhNH),C10H16O2, is obtained, and is purified by recrystallisation from alcohol. It forms colourless, odourless, tasteless, rhombic scales, which melt at 198° and distil without decomposition above 360°. It is insoluble in water and light petroleum, and only very slightly soluble in boiling ether, but dissolves in alcohol, chloroform, and benzene. Phenyl sebacamide is not attacked by alcoholic potash, but when fused with potash it yields aniline. It dissolves in concentrated nitric and sulphuric acids, but is precipitated unchanged on addition of water. When heated with concentrated nitric acid in sealed tubes, it yields a nitro-derivative which crystallises in needles. C. H. B.

Action of Thiocarbonyl Chloride on Secondary Amines. By O. BILLETER (Ber., 20, 1629-1632).-Ethylphenylthiocarbamine chloride, CSCI-NPhEt, is obtained when ethylaniline (1 mol.) is shaken with thiocarbonyl chloride (1 mol.) dissolved in chloroform. It crystallises in long prisms, melts at 565-57°, and is extremely soluble in chloroform, readily soluble in light petroleum and ether. Alcohol at first dissolves the compound without change, but decomposes it slowly in the cold or quickly on heating into ethylaniline hydrochloride, an oil containing sulphur, ethyl chloride, and ethylphenylthiocarbamine oxide, (CS-NPhEt),O. This crystallises in com