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compound, and on treatment with an acid yields a compound of the formula C12H10O5. This crystallises from ether in small, slender needles and from alcohol in glistening scales, melts at 121-122°, and is insoluble in water. Its solution in alkalis very readily reduces Fehling's solution at the ordinary temperature, whilst the alcoholic solution is coloured a dark violet-red by ferric chloride.

The foregoing reaction is probably of general application, inasmuch as phthalide and ethyl benzoate yield a yellow compound which reduces Fehling's solution, and valerolactone and ethyl oxalate form a colourless sodium compound under similar conditions. W. P. W.

Nitro-y-cumidinesulphonic Acid. By F. MAYER (Ber., 20, 2066-2068). Further investigation has shown that the acid obtained when trinitro-y-cumene is reduced with hydrogen sulphide can be diazotised without displacement of the sulphonic group; the author, therefore, considers it to be a nitro-y-cumidinesulphonic acid (compare this vol., p. 659).

Diazonitro-y-cumenesulphonic acid, NO2C,Me,<

N:N.

-SO3

obtained

as a colourless precipitate on diazotising sodium nitro-y-cumidinesulphonate, is a comparatively stable compound which does not evolve nitrogen when boiled with alcohol under 250 mm. pressure, and decomposes extremely slowly when boiled with water. On treatment with B-naphthol dissolved in dilute aqueous potash, it yields B-naph tholazonitro-y-cumenesulphonic acid, C19H17N3SO, + 2H2O, which crystallises in orange scales showing a metallic lustre, and sparingly soluble in water. The alkaline salts are dark-red in colour, and moderately soluble. The calcium salt crystallises in red scales showing a metallic lustre. W. P. W.

Aromatic Thiosulphonates containing Bivalent Alkylradicles. By R. OTTо and A. ROSSING (Ber., 20, 2079-2088).― Ethylene thiobenzenesulphonate, CH4: S2(SO,Ph), is obtained when an alcoholic solution of potassium thiobenzenesulphonate (2 mols.) is heated with ethylene dibromide (1 mol.) at 100° for some hours in a reflux apparatus, until all odour of the dibromide has disappeared. It crystallises in small, slender, transparent, silky needles, is destitute of odour and taste, melts at 84-85°, and is readily soluble in benzene and hot alcohol, insoluble in water. On treatment in alcoholic solution with potassium hydroxide at 100°, until permanent alkalinity is produced, ethylene thiobenzenesulphonate yields a mixture of potassium benzenesulphinate, potassium ethylenedisulphinate, and diethylene tetrasulphide; and inasmuch as the addition of ethylene mercaptan to a warm alcoholic solution of ethylene thiobenzenesulphonate brings about the production of benzenesulphinic acid and diethylene tetrasulphide, the authors regard this reaction as taking place in two stages:-I. C2H, S2(SO2Ph), + 4H,O= 4PhSO,H+ C2H‚(SO2H)1⁄2 + C2H1(SH)2; II. C2H1: S2(SO2Ph)2 + C2H1(SH)2 = 2Ph SO2H+ (C2H,S2)2. The salt is also readily saponified by barium hydroxide, or when heated with aqueous ammonia at 110° in sealed tubes. If the hydrolysis is effected by means of potas3 s

VOL. LII.

sium sulphide, potassium thiobenzenesulphonate and potassium mercaptide are obtained, and the reaction corresponds with that occurring when monovalent alkyl salts are similarly treated (this vol., p. 226). When reduced with zinc and hydrochloric acid, ethylene thiobenzenesulphonate yields diethylene tetrasulphide and thiophenol, the latter doubtless resulting from the reduction of benzenesulphinic acid; if it is heated in alcoholic solution with zinc-dust at 110° for two hours, it is converted into zinc benzenesulphinate and zinc mercaptide. Ethylene thioparatoluenesulphonate is obtained in like manner by heating equivalent quantities of ethylene bromide and potassium thioparatoluenesulphonate in alcoholic solution. It crystallises in colourless, transparent needles having pyramidal terminations, and showing a vitreous lustre, melts at 76-77°, has neither odour nor taste, and is readily soluble in benzene and hot alcohol, soluble in ether, insoluble in water. When saponified with potassium hydroxide, it yields diethylene tetrasulphide and potassium paratoluenesulphinate.

The following details are given in various footnotes:-Potassium thiobenzenesulphonate, with 2 mols. H2O; the sodium salt, with 1 mols. H2O; potassium benzenesulphinate, with 2 mols. H2O; and the sodium salt, with 2 mols. H2O, are described; and the optical properties of the crystals of the first and last salts are given. Ethylene mercaptan, when treated with ammonia and exposed to the air for some time, is converted into a compound melting between 86° and 90°.

Mixed alkyl tetrasulphides can be obtained from sulphinic acids and mercaptans containing bivalent radicles: thus, to judge from its decomposition products, ethylene diphenyltetrasulphide,

Ph S2 C2H S2 Ph,

appears to be formed by the action of ethylene mercaptan (1 mol.) on benzenesulphinic acid (2 mols.) in alcoholic solution (compare this vol., p. 242).

Pure diethylene tetrasulphide melts at 148-151° without carbonisation (compare this vol., p. 463). W. P. W.

Reduction of Aromatic Thiosulphonates containing Univalent and Bivalent Alkyl-radicles with Hydrogen Sulphide. By R. OTTO and A. RöSSING (Ber., 20, 2090-2092).-When phenyl thiobenzenesulphonate in dilute alcoholic solution is reduced with hydrogen sulphide, thiophenol and sodium benzenesulphonate are obtained, together with a viscous oil of unpleasant odour; this is a phenyl polysulphide, probably the tetrasulphide (compare preceding Abstract), inasmuch as it is reduced to phenyl bisulphide on treatment with colourless ammonium sulphide. Tolyl parathiotoluenesulphonate when similarly treated yields paratolyl bisulphide, tolyl tetrasulphide, and paratoluenesulphinic acid; thiocresol is probably formed in the reaction, but is not found among the products, owing to the readiness with which it reacts with toluenesulphinic acid to form tolyl bisulphide. Ethyl thiobenzenesulphonate under these conditions is converted into ethyl mercaptan, benzenesulphinic acid, and a phenyl polysulphide, which is reduced to phenyl bisulphide on

treatment with colourless ammonium sulphide. Ethylene thiobenzenesulphonate when suddenly reduced yields ethylene mercaptan, phenyl tetrasulphide, and a substance insoluble in hot alcohol, which most probably consists of the products obtained by the action of ethylene mercaptan on benzenesulphinic acid (see p. 954).

W. P. W. Halogen-derivatives of Phenylene Dichloracetylene Ketone. By T. ZINCKE and C. FRÖLICH (Ber., 20, 2053-2057).-Phenylene tetrachlorethylene ketone (tetrachlorhydrindonaphthene ketone),

CO-.

is formed when an acetic acid solution of phenylene dichloracetylene ketone is treated with chlorine until the yellow colour is no longer visible; the solution after remaining some time in a closed vessel is then allowed to evaporate at the ordinary temperature. It crystallises in large, colourless, transparent, monoclinic forms, or in thick, white, striated needles, melts at 107-108°, but sublimes at a lower temperature with an odour resembling that of hexachlorethane, and is soluble in alcohol and acetic acid. Sulphurous acid and potassium iodide are without action on the tetrachloro-ketone, but stannous chloride converts it into the dichloro-derivative, whilst hydroxylamine hydrochloride does not combine with it until the two compounds are heated at 120-160°, when the oxime of the dichloro-ketone is obtained.

Orthotrichlorovinylbenzoic acid, CCl2: CC1-C,H,COOH, is obtained if the tetrachloro-ketone is carefully heated with aqueous soda and a small quantity of alcohol, or if the warm alcoholic solution is added to cold aqueous soda. It crystallises in colourless needles or broad scales, melts at 163°, sublimes at higher temperatures without decomposition, and is soluble in alcohol and acetic acid. The methyl salt forms large, colourless, monoclinic (?) tables or prisms, and melts at 68°. Neither chlorine nor bromine additive compounds of the acid have been obtained, but 1: 2 ethylbenzoic acid, melting at 68°, is formed on treating it with sodium amalgam in the presence of water.

CO

Phenylene dibromodichlorethylene ketone, CH<CCIBT>CCIBr, is prepared from the dichloro-ketone in a similar manner to the tetrachloro-ketone, bromine being used instead of chlorine, and is crystallised from acetic acid, inasmuch as partial decomposition into bromine and dichloro-ketone occurs if alcohol and ether are employed as solvents. It resembles the tetrachloro-ketone in crystalline form, melts at 125-128° when rapidly heated, but when cooled and reheated, or when heated slowly, the melting point is 113-114°. Sulphurous acid and stannous chloride convert it into the dichloroketone, hydroxylamine hydrochloride and aniline in alcoholic solution. convert it on boiling into the oxime and anilide of the dichloroketone respectively, whilst iodine is liberated from alcoholic potassium iodide by its action.

Orthodichlorobromovinylbenzoic acid, CCIBr: CCI-C,H,COOH, prepared similarly to the trichloro-compound, forms colourless needles,

melts at 173-174°, and is readily soluble in alcohol. The methyl salt crystallises like the trichloro-salt, and melts at 82°. Neither chlorine nor bromine additive compounds of the acid have been obtained, but sodium amalgam readily reduces it to 1 : 2 ethylbenzoic acid. W. P. W.

Indoles. By A. PrÜLF (Annalen, 239, 220–223).-Fischer and Hess (Abstr., 1884, 1181) have pointed out that phenylindolecarboxylic acid decomposes at 200° into phenylindole and carbonic anhydride. The indole is a pale-yellow oil boiling at 326-327°, soluble in alcohol, ether, and benzene. It does not form a compound with picric acid.

Sodium hypochlorite precipitates from a cold neutral solution of phenylindolecarboxylic acid, [Ph: COOH = 1' 2'], a red, resinous mass which after a time becomes crystalline.

Phenylpseudoisatin, C.H.<>, is extracted from the alco-NPhholic solution of this crude product by boiling it with alcoholic soda, removing the alcohol by evaporation, dissolving the residue in water, and precipitating the isatin by hydrochloric acid. Phenylpseudoisatin is deposited from ethereal solutions in red plates. It melts at 134°, and dissolves freely in alcohol, ether, and benzene.

This

Acetophenonephenylhydrazine melts at 97-98°, and is converted into diphenylindole [1': 2'] by the action of zinc chloride. indole boils above 360°, and has not yet been obtained in the crystalline state. It is soluble in alcohol, ether, and benzene, and does not combine with picric acid. W. C. W.

Indoles from Tolylhydrazines. By J. RASCHEN (Annalen, 239, 223-229).-Paratolylhydrazinepyruvic acid separates as a yellow, crystalline precipitate on adding an aqueous solution of paratolylhydrazine hydrochloride to pyruvic acid. The acid melts with decomposition at 158-160°. It is soluble in alcohol, chloroform, and acetic acid. The ethylic salt crystallises in needles of a pale-yellow colour. It is converted into the ethylic salt of methylindolecarboxylic acid by the action of zinc chloride at 220°. 3: 2' Methylindolecarboxylic acid melts at 227-228° with evolution of carbonic anhydride and formation of methylindole [Me = 3] and other products. The acid is freely soluble in alcohol, ether, chloroform, and acetic acid. The ethylic salt forms colourless needles or plates melting at 158-160°. 3-Methylindole is soluble in alcohol, ether, benzene, light petroleum, and in hot water. It melts at 58.5°, and closely resembles indole in its reactions with pine-wood, and with nitrous and picric acids. The picrate, C,H,N,C6H2(NO2)3°OH, is deposited from a hot aqueous solution as it cools in red needles melting at 151°.

Paratolylhydrazine-acetone melts at 50-52°. On exposure to the air, it deliquesces and forms a resinous mass.

3: 2'-Dimethylindole melts at 114-115°, and boils without decomposition. It is freely soluble in warm alcohol, benzene, ether, and glacial acetic acid. The picrate, C10H1N CH2(NO2),OH, is deposited from benzene in dark-red needles. This salt melts at 155°.

Orthotolylhydrazinepyruvic acid melts at 158-159° with decomposition. The ethyl salts melts at 61-62°, and is deposited from hot alcoholic solutions in slender needles of a pale-yellow colour. 1:2′ Methylindolecarboxylic acid melts at 170-171° with decomposition, yielding a very small quantity of methylindole. The acid is soluble in alcohol, ether, acetic acid, and in hot water.

W. C. W. Methylindoles. By M. WENZING (Annalen, 239, 239-247).– The preparation of skatole from propylidenephenylhydrazine has been previously described by E. Fischer (Abstr., 1886, 806). The hydrochloride, (C,H,N)2, HCI, is precipitated from its alcoholic solution by ether in white, needle-shaped crystals. It melts at 167-168°. The picrate contains picric acid and skatole in molecular proportion. Benzylidenediskatole is formed by the action of zinc chloride on benzaldehyde and skatole. It melts at 140-142°, and dissolves in hot alcohol, chloroform, ether, and acetic acid. It does not yield benzaldehyde when boiled with hydrochloric or sulphuric acids. Hydroskatole formed by reducing an alcoholic solution of skatole with zincdust and hydrochloric acid, is a colourless oil resembling quinoline and piperidine in odour. It boils at 231-232° under 744 mm. pressure (thermometer immersed in vapour). It dissolves freely in alcohol, ether, and light petroleum, and the alcoholic solution stains pine-wood of an orange colour. The hydrochloride is soluble in water and alcohol, but insoluble in ether. The oxalate melts at 126° with decomposition, and is insoluble in ether. The picrate is deposited from benzene in yellow granular crystals melting at 149-150°. The platinochloride, (CHN), H2PtCl, forms yellow needles and is sparingly soluble in water. It is decomposed by hot water. Hydroskatole yields a nitroso-derivative. It is an oily liquid, and yields a hydrazine on reduction which forms a crystalline sulphate.

Hydromethylketole and the nitrosamine have been described by Jackson (Abstr., 1881, 734). Hydromethylketole boils at 227-228° under 742 mm. pressure. The oxalate and picrate are crystalline, and melt at 130° and 150° respectively. The hydrazine forms colourless prisms soluble in alcohol, ether, and light petroleum. It melts at 40—41°, and yields a crystalline sulphate and hydrochloride soluble in alcohol. Hydromethylketole forms a crystalline compound, C16H16N2S, with phenyl thiocyanate. It is soluble in ether, and melts at 100-101°.

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Hydromethylindole [Me 1'] boils at 216° under 728 mm. pressure, and is volatile in a current of steam. It is soluble in alcohol and ether. Most of its salts are soluble in alcohol and water. The platinochloride, (C,H,N)2,H,PtCle, is decomposed by boiling in water. The oxalate melts at 103-105°, and the picrate at 155°.

W. C. W.

Condensation of Isobutaldehyde and Methylal with Aniline. By W. v. MILLER and F. KINKELIN (Ber., 20, 1934-1942). -The author investigated this reaction in the hope of obtaining an indole according to the reactions: CH Me2COH + CH2O = CHMe CH(OH) COH and CHMe, CH(OH) COH + CH, NH2 =

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