colourless leaflets, often twinned, and melts at 275° (uncorr.); its hydrochloride crystallises in white needles, and the platinochloride is a yellow, crystalline precipitate. This substance seems to be isomeric with the two triphenylammelines described by Hofmann.

If the mercaptide above mentioned is heated with alcoholic ammonia, a triphenylmelamine is obtained, which crystallises in minute needles melting at 185-188°, and is moderately soluble in alcohol. This substance is isomeric with the three known triphenylmelamines; its probable constitution is discussed. V. H. V.

Primary and Secondary Xylylamines from Xylenols. By P. MÜLLER (Ber., 20, 1039–1042).-When ammonio-zinc bromide (1 part), ammonium bromide (3 parts), and a-orthoxylenol [Me: Me: OH =1:2:4] (1 part), are heated for 40 hours at 300°, xylidine boiling at 215-220° (the acetyl-derivative melts at 134°), and dixylylamine are obtained. The latter boils, with partial decomposition, at 330--345°; it solidifies to a glassy mass when cooled by means of a mixture of ether and carbonic anhydride.

a-Metaxylidine was prepared from a-metaxylenol in a manner similar to the ortho-compound. It is colourless, but soon becomes brown; it boils at 210-215°. The acetyl-derivative melts at 129.5°. The di-a-metaxylylamine, obtained in the same reaction, is an oil which boils at 305-310o. Like the diortho-derivative, it solidifies when treated with ether and calcium anhydride. N. H. M.

Aromatic Hydroxylamines. By A. MICHAEL and G. M. BROWNE (J. pr. Chem. [2], 35, 358-359).-When an alcoholic solution of picric chloride is treated with aqueous hydroxylamine, dipicrylhydrorylamine, [C2H2(NO2)3]2N•OH, is obtained. This forms yellow needles soluble in alcohol. If ethyl picrate is substituted for the chloride, picrylhydroxylamine, CH2(NO2)3 NH-OH, is produced; this forms silky, yellow needles, is soluble in alcohol, ether, and glacial acetic acid, and melts at 99-100°. L. T. T.

Azo-compounds. By J. V. JANOVSKY (Monatsh. Chem., 8, 49—63 ; compare Abstr., 1886, 794 and 1024).—The bromazobenzene melting at 187°, and formerly described (loc. cit.) as monobromazobenzene, is the dibromide. Parabromazobenzene (N: Br=1: 4) melts at 82°, and crystallises in brilliant orange plates. It is easily soluble in hot and cold alcohol, ether, &c. When treated with nitric acid in glacial acetic acid solution, it yields two substances-(a) a bromonitroazobenzene (N: Br = 1:4) melting at 107-108° (uncorr.), and crystallising in yellow needles; when boiled with ammonium sulphide this gives amidobromazobenzene crystallising in brilliant plates; (b) a paradinitroazobenzene, melting at 190° and crystallising in woolly needles; when boiled with ammonium sulphide, this yields an amido-compound possessing strong tinctorial powers. When parabromazobenzene is treated with fuming sulphuric acid, a bromazobenzenesulphonic acid, C12H,BrN2 SO,H + 3H2O, is formed; it crystallises in orange-brown needles with a golden lustre; it gives well-defined, crystalline sodium, potassium, and zinc salts. The sodium salt is very insoluble in water.

The acid appears to be identical with the parazobenzeneparasulphonic acid previously described by the author (Abstr., 1884, 1146).

The metabromazobenzene previously described (loc. cit.), when treated with fuming sulphuric acid, yields metabromazobenzenesulphonic acid, C12H,BrN2 SOH + 1H2O, which gives very insoluble alkaline salts. The potassium salt is precipitated from a 1 per cent. solution of the chloride in the form of pearly needles; the sodium salt is also thrown down from a 1 per cent, solution of sodium chloride in yellow, nacreous needles.

When orthodibromazobenzene (loc. cit.) is treated with nitric acid in acetic acid solution, it yields a trinitrodibromazobenzene, melting at 135° and crystallising in red needles.

When orthonitroazobenzene, previously described (loc. cit.), is treated with bromine, it yields a monobromonitroazobenzene, melting at 132°.

Orthonitroazobenzene behaves towards reducing agents in a manner entirely different from paranitroazobenzene (loc. cit.). The substance with strong tinctorial powers previously described is now considered N–CHN:NCH

by the author to be hexa-azoxybenzene, O

an inN-CH,N NCH, termediate reduction product. It is an orange-yellow powder consisting of microscopic scales, and melts at 206° without decomposition. The mononitrosulphonic acids of azobenzene have been previously described by the author (Abstr., 1882, 834, and 1883, 867).

Orthoamidoazobenzene, the preparation of which has been previously described (loc. cit.), melts at 123°, and forms yellow needles with a brilliant lustre. Its salts are distinguished from those of ordinary amidoazobenzene by their form.

Another substance formed by the nitration of azobenzene in glacial acetic acid seems to be a nitroazoxybenzene; it melts at 122°, and forms red, pearly tables, often twinned like muscovite. When treated with bromine, it yields a bromine-compound, melting at 126°.

G. H. M.

Reaction of Diazoamido-compounds with Phenols. By K. HEUMANN and L. ECONOMIDES (Ber., 20, 904-909).-Further investigation has shown that the formation of a hydroxyazo-compound by the action of diazoamidobenzene on phenol (this vol., p. 480) is also brought about when other diazoamido-compounds are employed. Diazoamidobenzene, when added to fused resorcinol and carefully heated, yields aniline and benzeneazoresorcinol (Abstr., 1878, 219). Diazoamidoparatoluene yields paratoluidine and paratolueneazophenol (this Journ., 1876, i, 268) when heated with phenol on a water-bath, and when added to fused resorcinol it forms paratoluidine and paratolueneazoresorcinol, C,H, N2 CH(OH). This crystallises in yellowishred needles, melts at 184°, and is readily soluble in alcohol, ether, benzene, and chloroform, yielding orange-coloured solutions. From diazoamidoparachlorobenzene and phenol, when heated on a waterbath, parachloraniline is obtained together with chlorobenzeneazophenol,

2

CH.Cl·N, CH, OH; this crystallises from chloroform in reddishyellow needles, and melts at 151-152°. The action of phenol on diazoamidometabenzoic acid takes place more slowly than is the case with the foregoing diazoamido-compounds, but proceeds similarly, inasmuch as metamidobenzoic acid and phenolazobenzoic acid are obtained.

Hydroxyazo-compounds are also formed by the action of phenols on mixed diazoamido-compounds, and the results of the experiments are given in quantitative form. When diazoamidobenzeneparatoluene is heated with phenol at 100°, approximately equal weights of aniline and paratoluidine are obtained together with a compound melting at 122°, and consisting of two hydroxyazo-compounds which have not yet been separated. Diazoamidobenzeneparatoluene and resorcinol heated on a water-bath yield aniline, paratoluidine, and a hydroxyazocompound. On heating diazoamidoparachlorobenzenebenzene and phenol at 90°, parachloraniline and hydroxyazobenzene were obtained, whilst diazoamidoparachlorobenzeneparatoluene and phenol heated first at 80-90° and afterwards at 110°, yield parachloraniline and paratolueneazophenol.

W. P. W.

Cinnamyl Hydrazine. By L. KNORR (Ber., 20, 1107–1108).— In order to examine whether the formation of pyrazoline-derivatives from phenylhydrazine and acids of the acrylic series is analogous to the formation of pyrazole-derivatives from unsaturated ketones, cinnamyl hydrazine was prepared and its products of decomposition investigated. The hydrazide, C13H1N2O, prepared from cinnamic acid or its ethereal salt, crystallises in minute needles which melt at 183°. On dry distiliation, an oil passes over which solidifies in the crystalline form; its composition is expressed by the formula CHINO; it melts at 251°, is insoluble in water, sparingly soluble in alcohol and ether, readily in alkalis and acids. It is proposed to carry on further investigations on homologous compounds.

NH.

V. H. V. Phenazoxine-a New Chromogen. By A. BERNTHSEN (Ber., 20, 942–944).—Phenazoxine, C.H.<>C.H1, is obtained when equimolecular proportions of catechol and orthamidophenol are heated at 260-280° for 40 hours, and after treating the residue with water and aqueous soda, can be extracted from it by ether. It crystallises in bright, colourless scales, melts at 148°, distils with slight decomposition, and is readily soluble in alcohol, ether, benzene, and chloroform, sparingly soluble in light petroleum. When treated with concentrated nitric acid, it yields a crystalline nitro-derivative, which on reduction with tin and hydrochloric acid, and subsequent oxidation with ferric chloride, is converted into a reddish-violet dye; the reaction corresponding with the formation of Lauth's violet (thionine) from thiodiphenylamine. Phenazoxine dissolves in concentrated sulphuric acid with a violet-red colour, and its alcoholic solution yields a dark bluish-green coloration with ferric chloride, and a deep blue with bromine-water. W. P. W.

Action of Dehydrating Agents on Benzylideneacetoxime. By N. ZELINSKY (Ber., 20, 922-924).-Benzylideneacetoxime,

CHPh: CH CMe: NOH,

is obtained when benzylideneacetone (1 mol.) dissolved in alcohol is added to a solution of hydroxylamine hydrochloride (1 mol.) and sodium hydroxide (1 mol.) in aqueous alcohol, and the whole heated for some hours on the water-bath. It is crystalline, melts at 115— 116°, boils without decomposition at 220° under 100 mm. pressure, and with bromine yields an additive compound, melting at 144—145° with decomposition.

With acetic chloride, an acetyl-derivative, CHPh: CH CMe: NOAc, is obtained, melting at 90-91°. Sulphuric acid does not effect a condensation, but phosphoric anhydride, or still better, phosphorus oxychloride reacts with benzylideneacetoxime yielding an oil having basic properties. W. P. W.

2

Methyl- and Ethyl-orange, and the Derived Dimethyl- and Diethyl-thionines. By A. BERNTHSEN and A.. GOSKE (Ber., 20, 924 -934).-Methyl-orange (sodium methylamidoazobenzenesulphonate), SO,Na CH, N, CH, NHMe, is obtained by diazotising sulphanilic acid and gradually adding the product to an aqueous solution of pure methylaniline hydrochloride heated at 30°; reddish-violet needles separate in large quantity, and when filtered off are dissolved in aqueous soda. It crystallises in large, orange-red lamine, and is readily soluble in hot, but only sparingly soluble in cold water. The yield amounts to 30 per cent. of the theoretical quantity.

Sodium diazomethylamidobenzenesulphonate, SO,Na C&H, N2 NMePh, is formed together with methyl-orange in the process just mentioned if dilute solutions are employed, and the product is kept nearly neutral throughout by the continued addition either of aqueous soda or of sodium acetate; the methyl-orange is decomposed by heating with concentrated ammonium sulphide at 100° the product obtained on addition of salt to the solution, the diazoamido-compound remaining unaffected. It crystallises in white or very pale-yellow scales, is readily soluble in hot water, insoluble in alcohol, and is not affected by boiling with dilute alkali. Although colourless, it shows all the properties of a diazoamido-compound: thus, dilute acids convert it into the corresponding amidoazo-acid; when heated with concentrated hydrochloric acid, it yields methylaniline and paraphenolsulphonic acid, and when warmed with an acetic acid solution of resorcinol it yields the yellowish-brown coloration characteristic of diazoamido-compounds. The authors find, moreover, that paradiazoamidotoluene, when heated with ammonium sulphide at 100°, is obtained on cooling in large, transparent, thin prisms of a paleyellow colour, although diazoamidobenzene does not lose its yellow colour when similarly treated.

Ethyl-orange (sodium ethylamidoazobenzenesulphonate) is prepared by a method similar to that used to obtain the methyl-compound, with the exception that the mixed solutions are kept nearly neutral throughout with aqueous soda. It crystallises in orange-red lamina.

The acid crystallises in glistening, bluish-violet needles, melts at about 244° with decomposition, and is insoluble in cold water and hot alcohol.

Methylparaphenylenediamine [NH, NHMe = 1 : 4] is obtained to: 1:4] gether with sodium sulphanilate when methyl-orange is warmed with ammonium sulphide. It boils at 257-259-5°, does not solidify in a freezing mixture, and is readily soluble in water, alcohol, and ether. The sulphate, (C,H10N2)2, H2SO4, crystallises in needles. The corresponding ethylparaphenylenediamine (this vol., p. 244) can be obtained similarly from ethyl-orange; its sulphate, CH2N2, H2SO4, crystallises in long, colourless needles or thin prisms.

CH3

Dimethylthionine, NMe |

N.C2H,(NHMe)

is obtained by the action

of ferric chloride and hydrogen sulphide on methylparaphenylenediamine in acid solution; at the same time, a red compound analogous to methylene-red is also formed. The base is sparingly soluble in ether and alcohol, and the alcoholic solution shows a red fluorescence. The hydrochloride dissolves in water with a beautiful blue colour, and shows a reddish-brown fluorescence; the hydriodide is a dark-blue powder, soluble in hot water and hot alcohol; it dyes silk an almost pure blue. When the base is boiled with much water, it is C6H3

O

S

converted into methylthionoline, NC.H.(NHMe)

and when

further saponified with 70 per cent. sulphuric acid yields thionol (Abstr., 1886, 53).

Diethylthionine obtained in a similar manner from ethylparaphenylenediamine, very closely resembles dimethylthionine in the colour of solutions, and the positions of the absorption-bands of the two compounds are almost identical. The maximum absorption of the darker band lies between C and D and near X' = 625, that of the lighter band near X" = 580 to 585.

W. P. W.

Action of Nitrous Acid on Orthoamidobenzamide. By A. WEDDIGE and H. FINGER (J. pr. Chem. [2], 35, 262-264).-Equimolecular proportions of sodium nitrite and a salt of orthoamidobenzamide are mixed in aqueous solution, when a yellowish-brown crystalline substance separates. Its composition is represented by the formula C,H,N2O, it melts at 213°, and is easily soluble in alkalis. The following derivatives are described: the sodium salt, C,H,NaN ̧O; the ammonium and silver salts; and the methyl salt, C,H1MeN ̧O, which can also be obtained by the action of nitrous acid on orthoamidobenzomethylamide; the constitution of the substance C,H,N,O is thus determined to be CH-N:N.CONH, H. B.

Oximes of Paraxyloquinone. By J. SULKOWSKI (Ber., 20, 977 -981).-Paraxyloquinoneoxime, C,H,Me,O: NOH [Me: O: Me: NOH 12:45], is obtained, together with a small quantity of the dioxime, when 10 grams of paraxyloquinone dissolved in 300 cc. of