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benzene in needles melting at 136-137°; it is readily soluble in warm water, sparingly in ether.

Orthocyanobenzylphthalimide, C.H‚O2 N·CH2·C2H CN, is prepared by slowly heating an intimate mixture of orthocyanobenzoic chloride (7 parts) and potassium phthalimide (9 parts) from 100° up to 120° for half an hour. The product is extracted with boiling water, and the undissolved portion dissolved in boiling glacial acetic acid, from which it separates in long prisms melting at 181-182°.

Orthocyanobenzylamine, CN-CH, CH, NH,, is formed when the above phthalimide compound is digested with fuming hydrochloric acid. It is a colourless oil, which crystallises when rubbed, and dissolves readily in water. The hydrochloride (with 1 mol. H2O) crystallises in lustrous needles; the picrate is obtained as a sparingly soluble, yellow, crystalline precipitate. When the acid solution of the hydrochloride is treated with sodium nitrite, nitrosophthalimidine is formed.

Orthochloromethylbenzamide, CH2CI-CH, CONH2, is obtained by heating a solution of orthocyanobenzoic chloride in strong sulphuric acid at 80° to 90°; the product is poured into water and filtered; the crystals are then washed and dried over sulphuric acid. It is insoluble in cold water, and is decomposed by boiling with water or alcohol with formation of phthalide and ammonium chloride. When slowly heated until a temperature of 150° to 160° is reached, dissolved in warm water and treated with potash, pseudophthalimidine, CH-NO, is obtained as a brownish oil, having a peculiar odour. The picrate forms a sparingly soluble, yellow, crystalline powder; the platinochloride crystallises in orange-coloured, flat needles (with 2 mols. H2O). When distilled, the base decomposes with evolution of ammonia; and if boiled with a mixture of phosphorus oxychloride and pentachloride, orthochlorobenzoic cyanide is formed.

N. H. M.

Action of Dilute Nitric Acid on Substituted Amido-compounds. By L. M. NORTON and W. D. LIVERMORE (Ber., 50, 22682274).-Trinitromethylparatoluidine is prepared by boiling acetylmethylparatoluidine for 2 to 3 hours with 5 per cent. nitric acid, or for 1 to 2 hours with 10 per cent. nitric acid. It is crystallised several times from alcohol; it melts at 129-130°. When boiled with 4 per cent. aqueous potash, it is converted into Martius' dinitrocresol (Ber., 2, 207), melting at 82-83°. The constitution of the trinitro-compound is therefore probably [Me: NO2: NMe(NO2): NO2 = 1:3:4:5]; the compound is possibly identical with that obtained by van Romburgh (Rec. Trav. Chim., 1884, 392), by the action of nitric acid on dimethylparatoluidine. It is also obtained by the action of dilute nitric acid on acetylmethylpropionylparatoluide.

Dinitromethylaniline (m. p. 174.5°) is formed when methylformanilide is boiled with 12 per cent. nitric acid for 30 minutes. Methylformanilide is prepared by heating sodium formanilide with methyl iodide; it melts at 12:5° and boils at 250°.

Methyloxanilide is prepared by adding a concentrated alcoholic solution of oxalic acid to methylaniline mixed with a little alcohol; the precipitate is separated and heated at 160-180° until no more

gas is evolved. It is liquid and boils at 249-251°. When boiled with nitric acid, it is converted into dinitromethylaniline, melting at 176-177°. This, when boiled with aqueous potash, is converted into dinitrophenol [1:2:4]. (Compare also Abstr., 1885, 1213.)

N. H. M.

Phenyl-derivatives of Ethane. By K. HEUMANN and J. WIERNIK (Ber., 20, 2421-2427).—When glycol is heated with dimethylaniline and zinc chloride for some days at 100-120°, dimethamidophenylethane, CH,Et NMe2 [Et: NMe, 1: 4], is formed together = 1:4], with small quantities of hexamethylparaleucaniline. The former crystallises in greyish-blue scales or prisms, easily soluble in alcohol and ether, and melting at 89°. It is soluble in acids, but its salts crystallise with difficulty. Nitrous acid yields nitrosomethamidophenylethane, CH,Et NMe NO, which crystallises in needles and melts at 162°. When reduced with acetic acid and zinc, the nitrosamine yielded an oil boiling at about 260°, probably a hydrazine base, CH.Et NMe NH2, which gave an acetyl-derivative melting at 68°. Monochlorethylene chloride and dimethylaniline, under like conditions, yield dichlorethylene, hexamethyltriamidotriphenylethane, NMe2 CH, CH, CH(CH, NMe2)2, and another crystalline compound melting at 84°, the constitution of which has not yet been determined. The former compound is easily soluble in ether, benzene, and acetic acid, sparingly in alcohol, and insoluble in water. With many oxidising agents, it gives greenish colouring matters.

Carbon hexachloride, dimethylaniline, and zinc chloride when heated together yield perchlorethylene and tetramethyldiamidodiphenylmethane; the latter is also formed when perchlorethylene is substituted for carbon hexachloride in this reaction. L. T. T.

Cumylamine. By H. GOLDSCHMIDT and A. GESSNER (Ber., 20, 2413-2416).-Cumylamine was prepared by the reduction of cuminaldoxime with sodium amalgam. It is a colourless, limpid liquid boiling at 225-227° under 724 mm. pressure, and not at 280°, as usually stated. Acetocumylamine, C,H, CH, CH, NHAC, forms micaceous scales soluble in alcohol, ether, and benzene, sparingly in boiling water it melts at 65°.

Cumylthiocarbamide, CH, CH, CH2 NH·CS·NH2, prepared from cumylamine hydrochloride and potassium thiocyanate, forms colourless scales melting at 110°. It is easily soluble in benzene and in cold water. Phenylcumylthiocarbamide, CH, CH, CH2 NH·CS NHPh, from cumylamine and phenyl thiocyanate, forms microscopic plates soluble in alcohol, benzene, and boiling water, and melting at 106°.

L. T. T.

Orthamidophenyl Mercaptan and its Derivatives. By A. W. HOFMANN (Ber., 20, 2251-2265).-When a small quantity of phenyl mercaptan is dissolved in a strong alcoholic solution of cyanogen, the liquid becomes coloured, and after 10 to 15 minutes a separation of almost colourless, lustrous needles takes place, and in an hour the reaction is finished. Analyses show that the new compound is

formed by simple addition of the elements of cyanogen; it probably


has the constitution C,H,<S>CC(NH) NH2. It melts at 150°, with evolution of gas, and dissolves in benzene, ether, and alcohol. The aurochloride, C,H,N,S,HAuCl, crystallising in slender needles, and the platinochloride, C,H,N,S,H,PtCl, were prepared.

Monophenylamidine, C.H.<>C-C(NH)-NHPh, is formed together with the diphenyl-derivative when the amidine is heated with aniline. The reaction is accompanied by an evolution of ammonia, and afterwards of hydrogen cyanide. The product is steam-distilled to remove the excess of aniline; the monophenylamidine remains as a yellow oil which solidifies on cooling, whilst the diphenyl compound is contained in the aqueous solution. Monophenylamidine crystallises in paleyellow plates which melt at 118° and dissolve in alcohol and ether. The hydrochloride forms long needles; the platinochloride separates from its solution in small, concentrically-grouped needles; the aurochloride crystallises in bright-yellow, rhombic plates.

Diphenylamidine, C,H,NS C(NPh) NHPh, separates in part from the aqueous solution on cooling; the rest is extracted with ether. It crystallises from water in white plates of a silvery lustre which melt at 129°; it dissolves readily in alcohol and ether. The platinochloride, C20H15N3S, H2PtCle, crystallises in dark-yellow plates; the aurochloride, C20 H15N3(HAuCl)2, forms gold-coloured, hair-like needles. Both salts are sparingly soluble.


When the amidine, dissolved in alcohol, is warmed with a few drops of mercaptan, ammonia is evolved and crystals of the oxalyl-compound, CH,N2S2 (Ber., 13, 1228), separate. Alcoholic potash solution decomposes the amidine with evolution of ammonia and formation of the potassium salt of an acid, C.H.<>C-COOH. The free acid crystallises in groups of needles readily soluble in alcohol, less soluble in water and in hydrochloric acid. It melts at 108°, with evolution of carbonic anhydride. When the aqueous solution is boiled, the acid decomposes into the methenyl base, C.H.<>CH, and carbonic anhydride.


The preparation of aniidophenyl mercaptan is described in detail. The vapour of amidophenyl mercaptan or its solution is a powerful irritant, causing blisters when in contact with the skin; all its derivatives appear to have this property.

When the aqueous solution of the amyl iodide of the methenyl base, C,H,NS, is treated with ammonia, no dye is formed; the same result is obtained with the ethenyl base. When both solutions are mixed and then boiled, a dark-red, resinous mass is obtained which yields splendid, well-formed plates of a green metallic lustre, violet-red in transmitted light; analyses of it point to the formula C25HN2S2I. It dissolves in alcohol yielding a deep-red solution which is decolorised by acids; the colour returns on the addition of alcohol or water. In a similar manner, dyes can be prepared from the corresponding naphthyl base (this vol., p. 839), and from a mixture of the phenyl and naphthyl

bases. Experiments with the amyl iodides of quinoline bases and with those of mercaptan-derivatives also gave dyes; these could not be obtained in a crystalline form. N. H. M.

Anisamine. By H. GOLDSCHMIDT and N. POLONOWSKA (Ber., 20, 2407-2413).-Anisamine, OMe CH, CH, NH2, is easily obtained by the reduction of anisaldoxime by sodium amalgam. The free base is a colourless oil, soluble in water, and boils at 234-235°. When exposed to the air, it absorbs carbonic anhydride and forms white needles melting at 110°. This substance, which is probably anisylamine anisylcarbamate, is what Cannizzaro described (Annalen, 117, 240) as the free base. The hydrochloride, CHNO, HCI, yields transparent prisms melting at 231°, the mercurochloride, CH1NO,HHgCl, + H2O, in silvery scales which lose water at 130° and melt with decomposition at 200°.

Acetanisamine (anisylacetamide), OMe CH, CH, NH C2H,O, crystallises in needles melting at 96°; anisylcarbamide,

[blocks in formation]

in long thin needles melting at 167°; anisylthiocarbamide,


in transparent needles melting at 95°. Dianisylthiocarbamide,


is formed by mixing together anisamine and carbon bisulphide, and boiling the resulting product with alcohol as long as hydrogen sulphide is evolved. It is soluble in alcohol, crystallises in colourless needles, and melts at 149-150°.




When acetanisamine is gradually added to well-cooled strong nitric acid, metanitracetanisamine, OMe•C,H,(NO,)CH,NHẠC [CH, NHAC NO, OMe 1: 3: 4], is formed. This dissolves in alcohol, crystallises in pale-yellow prisms, and melts at 137°. When oxidised with chromic mixture, it yields metanitranisic acid, and small quantities of paranitranisol, OMe C.H, NH2.

When metanitracetanisamine is treated with tin and hydrochloric acid, metamidanisamine, OMe C&H2(NH2)·CH2 NH2, is formed. This is a basic oil which absorbs carbonic acid from the air and becomes solid. It is sparingly soluble in ether, and almost non-volatile in steam. The hydrochloride forms unstable, colourless needles; the platinochloride has the formula

[OMe C,H,(NH2,HCI)·CH2 NH2]2,H2PtCl ̧. Diacetometamidanisamine, OMe C&H, (NHAc) CH, NHAC, forms white needles melting at 185°.

Anisaldoxime melts at 61°, and not at 45°, as stated by Westenberger. L. T. T.

Behaviour of Tertiary Amines towards Nitrous Acid. By E. KOCH (Ber., 20, 2459—2461).-Heidlberg has recently described

a compound, believed by him to be a nitroso-derivative of parachlorodimethylaniline (this vol. p. 475). This view, however, is improbable, as in the action of nitrous acid on the tertiary amines the nitrosogrouping takes up the 4 position, which in this case is already occupied. On repeating the experiments, the course of the reaction was found to be different from that described by Heidlberg, in that a nitro-derivative is formed as shown by analysis and the non-production of Liebermann's reaction. Further, the diamine obtained on reduction gives the reaction of a meta-compound. From the mother-liquor of the nitro-compound, a nitrosamine, CH,Cl·N(NO)Me, is obtained crystallising in light-brown needles which melt at 51°; this gives Liebermann's reaction.

V. H. V.

Preparation of Phenylhydrazine. By A. REYCHLER (Ber., 20, 2463-2464). In order to avoid the production of diazobenzene chloride in the preparation of phenylhydrazine, the following plan is recommended. Aniline (1 mol.) and potassium carbonate (mol.) are mixed with water and brought into solution by passing in the quantity of sulphurous anhydride required to form aniline sulphite and hydrogen potassium sulphite. The solution thus obtained is added gradually to an aqueous solution of potassium nitrite (1 mol.), carefully neutralised with acetic acid. If the operation is successful, no gas is evolved. The whole is then allowed to remain for two hours, and the precipitate formed is brought into solution by heating on a water-bath; the liquid is acidified with dilute acetic acid, and decolorised by careful addition of dilute hydrochloric acid and zinc-dust. After filtering, adding hydrochloric acid and evaporating the liquid to half its bulk, the phenylhydrazine hydrochloride may be precipitated by concentrated hydrochloric acid. The yield of the crude precipitate is 85.90 per cent. of that required by theory; this is reduced to 65.70 per cent. on purification. V. H. V.

Preparation of Iodobenzene from Phenylhydrazine and Titration of the Latter. By E. v. MEYER (J. pr. Chem. [2], 36, 115-116).-E. Fischer has shown (Ber., 10, 1335) that hydriodic acid, diazobenzimide, and aniline hydriodide are formed when iodine acts on an excess of phenylhydrazine. The author finds that if the iodine is kept in excess the decomposition takes place according to the equation N2H,Ph + 211⁄2 = 3HI + N2+ PhI. This reaction may be employed to prepare iodobenzene and to titrate phenylhydrazine. In the latter case, the phenylhydrazine is added to a titrated solution of iodine, and the excess of iodine determined by hyposulphite. The titration of phenylhydrazine may also be effected by iodic acid in the presence of dilute sulphuric acid. L. T. T.

Action of Carbamide on Phenylhydrazine. By A. PINNER (Ber., 20, 2358-2360).—If carbamide (1 mol.) is heated with two molecular proportions of phenylhydrazine hydrochloride, phenylsemicarbazide, NHPh NH·CO NH2 (E. Fischer, Abstr., 1878, 307), is formed. If, however, three or more molecular proportions of the hydrazide are

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