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CH

CPr.C.CH: CH

-NH.C.CH:CH

+ 2H2O. The product of the reaction had

no odour of indole, but yielded a base which, when heated with zinc chloride, gave small quantities of an indole, probably of the above formula. Besides this indole, the author obtained from the zinc chloride melt two isomeric bases, C1HN, and a base, C1H1N. The bases, C1HN, the author believes to be dimethylquinolines. The one is solid, melts at 63-65°, and boils at 274-275°; the other is liquid, and boils about 265-275°. The base, CiH15N, boils about 300°. All are being investigated. L. T. T.

Diphenylenedihydrazine. By R. ARHEIDT (Annalen, 239, 206 -215).-Diphenylenedihydrazine, C12H(N2H3)2, is prepared by reducing the diazo-compound of diamidodiphenyl with sodium sulphite or stannous chloride. The salts of the base are crystalline; the nitrate is freely soluble in hot water; the sulphate and hydrochloride are sparingly soluble. The base is precipitated from solutions of its salts by alkalis and also by sodium acetate. It melts with decomposition at 165-167°, and dissolves sparingly in alcohol, ether, and chloroform. The addition of the theoretical quantity of an aqueous solution of potassium cyanate converts diphenylenedihydrazine hydrochloride into diphenylenedisemicarbazide, CH,(NH-NH-CONH2)2. This compound is soluble in glacial acetic acid. It melts with decomposition between 306° and 308°. The sulphate and hydrochloride are crystal line. Diphenylenedinitrosohydrazine, C12H(N2H2 NO), melts with decomposition at 112-113°. It is soluble in acetone, chloroform, and acetic acid, but the solutions are unstable. Diphenylenedihydrazinepyruvic acid, C12H.(N2H: CMe-COOH)2, is freely soluble in acetone and in alkalis. It melts at 197-198° with decomposition. phenylenediacetonehydrazine, C12Hs (N2H: CMe2)2, is very unstable. It is freely soluble in alcohol, chloroform, and acetic acid, and melts with decomposition at 197-199°. It is converted into diphenyldiCH methylindole, CH5 C&H NH CMe, and diphenyl by the action of zinc chloride at 215°. Diphendimethylindole melts at 270°, and boils without decomposition. It is freely soluble in alcohol and acetic acid and exhibits the characteristic indole reaction. W. C. W.

8

Di

Orthodibenzyldicarboxylic Acid. By N. DOBREFF (Annalen, 239, 65-71). In addition to the salts of orthodibenzyldicarboxylic acid, which have been previously described by Graebe, the author has prepared the following salts:-The ammonium salt, CeH2O.(NH4)2, is very soluble in water; the calcium and barium salts are also very soluble, and crystallise with difficulty. The ammonium salt precipitates basic salts from solutions of lead, copper, and zinc acetates. The methyl salt, C16H12O,Me2, melts at 100-101° and is freely soluble in methyl alcohol, alcohol, chloroform, and carbon bisulphide. The ethyl salt, Č16H12O,Et2, crystallises in needles or prisms and melts at 69-71°. It is best recrystallised from hot amyl alcohol. On saturating the alcoholic solution with ammonia gas, crystals of ethyl dibenzyldicarb

6

oxylaminate, COOЕt C&H ̧•CH2 CH2 C&H, CONH2, are slowly deposited. The compound melts between 65° and 68°.

Dibenzyldicarboxylic acid yields diphthalylic acid when oxidised with potassium permanganate, and stilbene when distilled with sodalime. Fuming nitric acid converts diphenyldicarboxylic acid into a dinitro-product which is soluble in hot water and in hot alcohol. The calcium and barium salts are amorphous, and explode when heated. The ethyl salt, C16H11(NO2)2O,Et, melts at 60°.

On oxidation with potassium permanganate, dinitrobenzyldicarboxylic acid yields B-nitrophthalic acid. W. C. W.

So-called Carbonylcarbazole (Carbazole-blue). By E. BAMBERGER and R. MÜLLER (Ber., 20, 1903—1907).-Suida first described this compound (Abstr., 1880, 245) as an anhydride of orthamido-CH.NH, phenylbenzoic acid, giving it the formula <CH CO> The authors have re-examined it, and find it to belong to the class of triphenylmethane colouring matters, and to have the constitution

[blocks in formation]

The authors consider the blue colour of the free base to be only superficial and due to impurities, and on the addition of strong hydrochloric acid it is very much intensified owing to the formation of the true dehydrated colouring matter. When treated with acetic acid and zinc, the leuco-base is obtained, which crystallises in microscopic needles, dissolves in ether to a bluish-violet fluorescent liquid, and is reconverted into the colour-base by oxidation. When heated alone or with zinc-dust, the colouring matter yields carbazole. A very similar substance was also prepared by fusing carbon hexachloride with carbazole. The authors therefore propose the name carbazole-blue for this substance. L. T. T.

The Hydrocarbon C1H12 from Styrolene Alcohol. By T. ZINCKE (Annalen, 240, 137-147).-In the light of the formation of naphthalene-derivatives by condensation lately observed, and especially of the formation of a-naphthol from phenylisocrotonic acid (Fittig and Erdmann, Abstr., 1885, 545), the author believes the hydrocarbon obtained from styrolene alcohol (phenylglycol) to be B-phenylnaphthaCPh: CH. lene [Ph=2], and not to have the formula

CH: CPh

previously

(Abstr., 1885, 269) ascribed to it. The derivatives will thus be B-phenylnaphthaquinone, B-phenylamidonaphthaquinone, &c., the constitution of the last-named, for instance, being [O: Ph: NH2 : 0 = 12:34]. This constitution will more fully explain the reactions of this hydrocarbon than the one previously given. The one piece of evidence that seems to be antagonistic to the naphthalene formulathat is, the formation of 0.9 gram of benzoic acid from 1 gram of the hydrocarbon-is probably due to an error in weighing, 2 grams having most likely been really taken. A repetition of the experiment yielded the lower percentage of benzoic acid. The formation (loc. cit.) of

phthalic acid and the acid C,H,Os (probably COOH·C2H, CO-COOH) points to the correctness of the naphthalene formula.

All attempts to synthesise B-phenylnaphthalene by other methods for comparison with the above hydrocarbon gave negative results. Graebe has described (Ber., 7, 792) a phenylnaphthalene which is probably the a-naphthalene. Watson Smith has described a ẞ-phenylnaphthalene obtained by the action of bromobenzene on naphthalene (Abstr., 1880, 125, 261; see also Smith and Takamatsu, Trans., 1881, 546). The author questions the correctness of Smith's view and believes the compound rather to be the (perhaps impure) a-derivative. L. T. T.

Action of Chlorine on Phenols. By T. ZINCKE (Ber., 20, 2058 -2061).-In certain cases, chlorinated ketones are formed when phenols dissolved in acetic acid are treated with chlorine. Definite results have been obtained with the two naphthols, but so far the attempts made to isolate the products of the action of chlorine on hydroxyquinoline, thymoquinone, catechol, and resorcinol have not met with success.

When a-naphthol is treated with chlorine in acetic acid solution, a compound is obtained, which appears to be a chloride of dichloro-ßCO.CCI2 naphthaquinone, C.H.<CCCC>. It crystallises in large, colourless, rectangular tables, melts at 156-157°, is not decomposed on heating, and is sparingly soluble in ether and light petroleum, readily soluble in benzene and hot alcohol. Although insoluble in dilute alkali it dissolves slowly in concentrated alkali on addition of alcohol, and is converted into phenylenedichloracetyleneglycollic acid (this vol., pp. 54, 728). When the ketone chloride is dissolved in hot alcohol and treated with dilute aqueous soda until the reaction is feebly alkaline, a compound is formed which, on the addition of an acid, separates in slender, orange needles melting at 146°. This is probably a hydroxy-derivative obtained by the substitution of hydroxyl for chlorine in the ketone chloride; it dissolves without decomposition in cold dilute alkali with a yellow colour, but on heating the solution it becomes dark red, and yields chlorhydroxy-a-naphthaquinone (m. p. = 215°) when treated with an acid. Dichloro-ß-naphthaquinone and its chloride, therefore, exhibit a similar series of reactions, inasmuch as it is converted into chlorhydroxy-a-naphthaquinone by prolonged treatment with sodium carbonate, or by heating with concentrated hydrochloric acid.

The ketone chloride obtained from B-naphthol under similar conditions crystallises from the acetic acid solution in broad lustrous laminæ, melts at 85°, and is readily soluble in alcohol and acetic acid, but quickly resinifies in these solutions. From benzene and light petroleum, however, it crystallises in small, glistening scales, which melt at 100° to a turbid liquid which becomes clear at 140°. Dilute alkali converts the ketone chloride into black resinous products, but on treating its solution in aqueous alcohol with sodium carbonate, it yields a compound which crystallises in thick, glistening, red needles, melts at 174°, and is soluble in benzene and acetic acid. The investigation will be continued. W. P. W.

Action of Chlorine on Aceto-ß-Naphthylamine. By P. T. CLEVE (Ber., 20, 1989-1992).-Acetochloro-B-naphthylamine, CH,CI-NHAC, is prepared by passing chlorine (1 mol.) into a solution of aceto-Bnaphthylamine in dilute acetic acid, and precipitating with water. It crystallises from alcohol in very slender colourless needles, which melt at 147°; it is sparingly soluble in boiling water, readily in alcohol.

Chloro-B-naphthylamine, C10HCl, NH2, is obtained by treating an alcoholic solution of the above acetyl-derivative with hydrochloric acid. It crystallises from dilute alcohol in slender colourless needles, melting at 59°. The hydrochloride crystallises (with 1 mol. H2O) in lustrous colourless needles, rather soluble in boiling water containing hydrochloric acid. When the base is treated with nitrogen trioxide in presence of sulphuric acid, a-chloronaphthalene is formed; when boiled with nitric acid, it is oxidised to phthalic acid.

Dichloronaphthalene, CHeCl2, is formed when 10 grams of chloroB-naphthylamine hydrochloride dissolved in boiling hydrochloric acid is treated with 5 grams of cuprous chloride, and 4 grams of potassium nitrate dissolved in 20 c.c. of water added by drops. The product is steam distilled, and the yellow oil so obtained, which solidifies in a few days, crystallised from alcohol; it separates in tabular monoclinic crystals; ab: c = 1·5196 : 1 : ? ; ß = 76° 46'; it melts at 34—-35° ; Widman's a-dichloronaphthalene melts at 38°, and crystallises in pointed needles.

When monochloronaphthylamine is heated with soda-lime, a-3-naphthazine (Witt, Ber., 19, 2791) is formed. The dichloronaphthalene described above is therefore an a-ß-derivative.

N. H. M.

Orthoamidated Aromatic Mercaptans. By P. JACOBSON (Ber., 20, 1895-1903).—The author has previously shown (Abstr., 1886, 700 and 876) that the anhydro-compounds of orthamidophenyl mercaptan are easily formed by the oxidation of thioanilides. He has now extended this reaction to the naphthalene series.

N

a-Thioacetonaphthalide described by Bernthsen and Trompetter (Abstr., 1879, 146) is best obtained by acting on acetonaphthalide with phosphoric sulphide; it melts at 110-111° (Bernthsen and Trompetter give 95–96°). When oxidised with potassium ferricyanide, this yields ethenylamidonaphthyl mercaptan, C1oHe< CMe, probably identical with that recently obtained by Hofmann (this vol., p. 839). The hydrochloride crystallises in needles. Benzenylamidonaphthyl mercaptan, also described by Hofmann (loc. cit.,) was similarly obtained from a-thiobenzonaphthalide. The picrate yields characteristic orange needles, melting at 130-131°. Attempts to prepare amidonaphthyl mercaptan by heating the benzyl base with alcoholic potash were unsuccessful, but a slightly basic oxidation derivative crystallising in yellow scales and melting at 131-132° was obtained. The author is unable at present to decide whether this is a diamidodinaphthyl bisulphide, S. (CH, NH2)2, or a thionaphthoquinonimide, C1H< the percentage composition of which are very similar. When treated

NH.

6 -S

with acetic anhydride, this substance yields diacetylamidonaphthyl mercaptan, NHAC CH, SAc, crystallising in long needles, and melting at 173-5-175°. When heated with hydrochloric acid at 200-220°, this acetyl-derivative is decomposed, ethenylamidonaphthyl mercaptan being formed.

Orthamidophenyl mercaptan bisulphide, when heated with acetic anhydride, yields diacetylamidophenyl mercaptan, NHAC CH¡SAc, crystallising in prisms melting at 135°. Phenyl bisulphide and benzyl bisulphide are, however, not attacked by acetic chloride, so that this is not a general reaction for bisulphides, and does not decide which of the two formulæ proposed for the new compound is the correct one. L. T. T.

Action of Aldehydes on Amidosulphonic Acids. By E. CAHN and M. LANGE (Ber., 20, 2001-2002).-When sodium naphthionate (1 mol.) dissolved in a little water is treated with benzaldehyde (1 mol.) and shaken, the condensation product SO,Na CH, N: CHPh separates in straw-coloured plates. This is decomposed into its original constituents by prolonged boiling with water. The corresponding condensation product from a-naphthylaminesulphonic acid and benzaldehyde is prepared by adding the aldehyde to an alcoholic solution of the sodium salt of the sulphonic acid, and crystallises in concentrically grouped needles. The analogous compound from ßß-naphthylaminesulphonic acid and benzaldehyde crystallises in well-formed, long, pale-yellow prisms.

Benzidinesulphonic acid and the sulphonic acid of amido-azo-compounds yield analogous compounds. N. H. M.

B-Naphthylaminesulphonic Acids. By S. FORSLING (Ber., 20, 2099-2106). Further examination has shown that the B-naphthylaminesulphonic acid obtained by heating B-naphthylamine with sulphuric acid at 140° (Abstr., 1886, 890), is not pure, but contains three isomerides, of which one is identical with Brönner's acid (this vol., p. 375), and a second, produced in small quantity only, is perhaps identical with the d-acid (loc. cit., p. 732), whilst the remaining two, designated as 1 and 2, are respectively identical with the acids termed a and y in a patent specification of Dahl's. A separation of the acids was effected by fractional crystallisation of the calcium salts.

B-Naphthylaminesulphonic acid, 1, dissolves in about 1700 parts of cold water, and is almost insoluble in alcohol. Its salts generally are readily soluble in water, yielding solutions fluorescing blue, and, with the exception of the silver and copper salts, can be heated at 180° without decomposition. The potassium salt with mol. H2O, forms six-sided tables; the sodium salt is anhydrous, and crystallises in thin four-sided scales; the barium salt, with 4 mols. HO, forms long prisms, and dissolves in about 23 parts of cold water; the calcium salt, with 6 mols. H2O, forms large, thick tables, which become coloured red on crystallisation from an aqueous solution, and dissolve in about 11 parts of cold water; the magnesium salt, with 3 mols. H2O, forms small crystalline aggregates; the zinc salt, with 6 mols. H2O, crystallises in prisms; and the lead salt crystallises in small needles, and is anhydrous. The corresponding diazonaphtha

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