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Ethyl amyl bisulphide, prepared in a similar way, is a thin, colourless liquid of very strong and unpleasant garlic-like odour. It is insoluble in water, soluble in ether and alcohol, lighter than water, and volatile in steam.

Ethyl phenyl bisulphide.-The authors attempted to obtain this compound by the above method, but it was only formed in very small quantity, the principal products being diethyl and diphenyl bisulphides. But by modifying Schiller and Otto's method for the preparation of organic bisulphides (this Journal, 1877, i, 306), the authors were successful. 10 grams of phenylsulphinic acid (1 mol.) and 15 grams of ethyl mercaptan (3 mols.) in alcoholic solution were heated in sealed tubes at 100°. The action took place according to the equation PhSO2H + 3EtSH = PhS2 Et + Et2S2 + 2H2O. Ethyl phenyl bisulphide is a thick, oily, strongly refractive liquid, heavier than water, and only very slightly volatile in steam. It is insoluble in water, soluble in ether and alcohol. Phenyl paratolyl bisulphide was also prepared by the action of phenyl hydrosulphide on paratolylsulphinic acid.

When the ethyl salts of the thiosulphonic acids are heated with mercaptans reactions similar to the above occur; these are not, however, of so simple a kind, but take place simultaneously according to the two equations :

I. R.SO, SR + 4R'SH R2S2 + 2R'2S2 + 2H2O.
II. R·SO, SR + 4R'SH = 2R·S2·R' + R'2S2.

Phenyl disulphoxide (Ph.S2O2 Ph) and ethyl mercaptan thus yield ethyl bisulphide, phenyl bisulphide, and ethyl phenyl bisulphide.

L. T. T.

Action of Silicon Fluoride on Organic Bases. By C. L. JACKSON and A. M. COMEY (Ber., 19, 3194-3195).-The authors intend studying these reactions. When silicon fluoride is passed over aniline, a compound of the formula 3NH,Ph,2SiF, is formed. This compound was obtained by Laurent and Delbos (Ann. Chim. Phys., 22, 101), but its composition was not established. It forms white, microscopic needles, and sublimes without fusion. It is insoluble in ether, benzene, and light petroleum. With water or alcohol, it forms aniline hydrosilicofluoride.

Ortho- and para-toluidine, diphenylamine, and dibenzylamine form similar compounds. L. T. T.

Aniline and Diphenylamine from Phenol. By V. MERZ and P. MÜLLER (Ber., 19, 2901—2917).—In this paper, the various methods used, and the conditions required for the conversion of phenol into aniline and diphenylamine are fully described. Thus when phenol and ammonium zinc chloride or simply ammonium chloride are heated at 330°, 70 to 80 per cent. of the phenol is converted into the amine, the yield of which is dependent on an excess of the ammonium salt, the temperature, and the time of heating. The same change may also be effected with zinc oxide or magnesia and ammonium chloride, the presence of an excess of the latter preventing the formation of diphenylamine. Experiments in an autoclave were not so satisfactory;

the pressure when the mixture was heated at 320°, was 20 to 25 atmospheres. V. H. V.

Action of Alcoholic Hydrogen Chloride on Nitrosamines. By O. FISCHER and E. HEPP (Ber., 19, 2991-2995).-The authors find that certain nitrosamines undergo intramolecular change by the action of alcoholic hydrogen chloride thus; for example, methylphenylnitrosamine is converted into 1 : 4 nitrosomethylaniline.

14 Nitrosmethylaniline is prepared by adding alcoholic hydrogen chloride to an ethereal solution of methylphenylnitrosamine; a vigorous action takes place after some time, and small yellow needles of the 1: 4 nitrosomethylaniline hydrochloride separate in an almost pure state. The base is obtained by precipitation with sodium carbonate or ammonia, either in yellowish-green laminæ, or from very dilute solutions in large, steel-blue prisms; it is readily soluble in alcohol, ether, and chloroform, sparingly soluble in benzene, and only slightly soluble in light petroleum and in water. It melts at 118° and suffers decomposition when more strongly heated. When heated with solution of sodium hydroxide, it is decomposed into 1 : 4 nitrosophenol and methylamine; whilst by reduction methylparaphenylenediamine is obtained. Paranitrosomethylaniline is a secondary base, and by the action of nitrous acid yields 1 : 4 nitrosomethylphenylnitrosamine, NO CH, NMe NO; this compound crystallises from alcohol in nodules, and melts at 101°. Careful oxidation with nitric acid of sp. gr. = = 1·13 converts it into 1 : 4 nitromethylphenylnitrosamine; this forms yellow needles melting at 104°.

When methylaniline, dissolved in alcoholic hydrogen chloride, is treated in the cold with one molecular proportion of sodium nitrite, there separate after long standing two compounds, 1 : 4 nitrosomethylaniline hydrochloride and 1: 4 nitrosomethylphenylnitrosamine, the latter being formed in the greater quantity, and a corresponding proportion of the methylaniline remaining unacted on.


14 Nitrosoethylaniline, obtained in a manner similar to the methylderivative, crystallises in green laminæ, melts at 78°, and is readily soluble in alcohol, ether and benzene, sparingly soluble in water. hydrochloride crystallises in stellate groups of needles. By reduction, ethylparaphenylendiamine is obtained; this base is a thick oil and distils at 270°. Its hydrochloride forms colourless, narrow scales readily soluble in water, less soluble in alcohol. From 1 : 4 nitrosoethylaniline, 70 per cent. of the nitrosophenol and 80 per cent. of the ethylamine hydrochloride required by theory were obtained by heating it with sodium hydroxide solution.

1: 4 Nitrosoethylorthotoluidine melts at 140° and crystallises in green scales, frequently exhibiting a bluish shimmer.

1:4 Nitrosodiphenylamine, obtained from Witt's diphenylnitrosamine, crystallises in green tables showing a bluish shimmer, melts at 143°, and dissolves readily in alcohol, ether, and chloroform, giving brown solutions, and in sulphuric acid with a red colour, which at once changes to violet on warming. The hydrochloride crystallises in brown tables having a bronze lustre, or in dark reddish-brown needles, and is decomposed by water with liberation of the base. W. P. W.

Preparation of Benzylamine and Phenethylamine. By S. HOOGEWERFF and W. A. VAN DORP (Rec. Trav. Chim., 5, 252-254). -Hofmann has suggested the action of bromine on phenylacetamide in presence of dilute alkali as a convenient method for the preparation of benzylamine (Abstr., 1886, 45). It is here shown that the yield is considerably increased by preparing the alkaline hypobromite first and then adding it subsequently to the amide.

The preparation of benzylamine and phenethylamine by this method is described. V. H. V.

Isodinitrodimethylaniline. By P. v. ROMBURGH (Rec. Trav. Chim., 5, 240-245).-According to Mertens, when dinitrophenylnitramine is heated with phenol, tetranitrodimethylazobenzene, a red compound is produced, reconvertible into the nitramine by treatment with nitric acid (Abstr., 1885, 1022). As, however, trinitrophenylmethylnitramine yields a similar red substance, reconvertible into the nitramine, which has been shown to be trinitrophenylmethylaniline, it is probable that the red substance obtained by Mertens is a dinitromethylaniline. The analytical results support this view quite as well as that of Mertens. As a confirmation, the author by acting on tetramethylbenzidine with nitric acid, obtained a product resembling the isodinitrodimethylaniline of Mertens, which when boiled with nitric acid yielded the corresponding nitramine; from this, the red substance was obtained, the analysis of which showed that it was a tetranitrodimethylbenzidine. When treated with nitric acid, this

yielded the theoretical quantity of the nitramine.

V. H. V.

New Synthesis of Thiodiphenylamine. By A. BERNTHSEN (Ber., 19, 3255-3256).-Thiodiphenylamine is obtained by heating orthamidophenyl mercaptan and catechol at 220-240° for about 30 hours. The product is extracted with alkali and acid, and crystallised from ether and light petroleum. This synthesis forms an important support in favour of thiodiphenylamine being a di-ortho-compound (compare Bernthsen, Abstr., 1886, 53, and Möhlau, Ber., 19, 2013).

N. H. M.

Ethereal Carbonates. By G. BENDER (Ber., 19, 2950-2952). -Oxycarbimidophenol, described by Kalckhoff (Abstr., 1883, 1169) and previously by Groenvik (Bull. Soc. Chim., 25, 177), and hydroxymethenylamidophenol, prepared by Sandmeyer (this vol., p. 135), are identical with the author's anhydro-orthamidophenyl carbonate (Abstr., 1887, 37) which melts at 137-138°. Kalckhoff's compound on further purification becomes white, and its acetyl-derivative is soluble in water like the corresponding substance obtained by the author. The ethyl salt prepared by Sandmeyer has the formula C.H.<>COEt, that of the salt obtained by the author is


CH.<>CO. In the existence of these two isomerides, the parent substance exhibits a remarkable analogy to carbostyril and isatin; it also has a pseudo-form in addition to its ordinary

one, although whether the latter is a lactim or lactam cannot yet be decided.

The author's ethyl salt melts at 29° and has a bitter taste. Concentrated hydrochloric acid is without action on it at 100°, but dissolves it in the cold forming a highly unstable hydrochloride.

W. P. W.

Benzyl-derivatives of Hydroxylamine. By F. WALDER (Ber., 19, 3287--3294).-Further investigation has shown that the conclusions respecting the composition of these compounds arrived at in the author's previous paper (Abstr., 1886, 796) are erroneous. A complete analysis of the compound obtained by the action of methyl iodide and sodium on dibenzylhydroxylamine and described as tribenzylbenzoxyammonium iodide, shows that it has the formula N2(C,H,),O,HI. The hydriodide can be decomposed by alkalis, but, since the base is soluble in water and only sparingly soluble in ether, a separation is better effected by employing moist silver oxide. The base crystallises over sulphuric acid, distils with decomposition at high temperatures, and is very deliquescent; when heated with water, it yields dibenzylhydroxylamine, whilst by the action of acetic anhy dride acetyldibenzylhydroxylamine is obtained. The platinochloride, N2(C,H,),O,H2PtCl, crystallises in slender, yellow needles, melts at 153°, and is insoluble in cold water and ether. The sulphate, N2(C,H,),O,H2SO4, forms transparent prisms, melts at 152°, and is insoluble in alcohol and ether, readily soluble in water containing acid. The nitrate, N2(C,H,),O,2HNO3, crystallises in white, feathery, flat needles, melts at 159°, and is sparingly soluble in water. The hydrochloride, N2(C,H,),O,2HCl, forms thick prisms showing a nacreous lustre, is insoluble in ether, and only sparingly soluble in water after it has once separated from solution. A second hydriodide, N2(C,H),O,2HI, crystallises in bright yellow aggregates, melts at 27°, and is soluble in alcohol.

From a black, resinous mass formed in the preparation of the hydriodide, N.(C,H,),O,HI, a black, crystalline compound may be obtained; it appears to be a periodide of the formula N.(C,H,),O,MeI,I2.

The base previously described as benzylbenzenylamine proves to be dibenzylamine, NH(C,H,)2. It is found that when dibenzylhydroxylamine is heated with phosphorus trichloride and the product extracted with dry ether, an unstable, bright-yellow viscid oil containing phosphorus and chlorine is obtained, which on addition of water yields dibenzylamine. The nitrosamine, (C,H,),N.NO, forms brittle, curved, white crystals, melts at 61°, and is readily soluble in alcohol, ether and light petroleum, insoluble in water. The platinochloride, N(C,H,),H,H,PtCl, crystallises in golden-yellow needles; the nitrate, N(C,H,)2H,HNO,, crystallises in slender glistening needles, melts at 186°, and is sparingly soluble in water. When heated with benzyl chloride at 100°, the base is converted into tribenzylamine.

When dibenzylhydroxylamine hydrochloride is treated with potassium nitrite in the cold, nitrosodibenzylhydroxylamine, N(C,H,),O.NO, is obtained; this crystallises in flat, white needles, melts at 82-84°,

and is soluble in alcohol and ether, sparingly soluble in light petroleum, insoluble in water. If, however, cooling be omitted, and the nitrate be added rapidly to the hydrochloride, nitrosodibenzylamine is obtained, N(C,H)2OH + 2HNO, = HÑO, + H2O + N(C,H2), NO.

The author finds that mono-, di-, and tri-benzylamine are also formed when dibenzylhydroxylamine is prepared by Schramm's method (Abstr., 1884, 51). W. P. W.

Correction. By L. KNORR (Ber., 19, 3303).--In a previous paper (Abstr., 1884, 1198), a compound, CH6N2O4, was stated to have been obtained by the action of ethyl acetoacetate on orthophenylenediamine, instead of on paraphenylenediamine. Sulphuric acid is without action on the compound in the cold, but at 100° paraphenylenediamine is eliminated.

W. P. W.

Action of Ethyl Acetoacetate on Aromatic Diamines. By O. N. WITT (Ber., 19, 2977-2978 and 3299).-By the action of ethyl acetoacetate on orthotoluylenediamine, ethenyltoluylenediamidine is formed. This confirms the results obtained by Ladenburg and Rügheimer (Abstr., 1879, 915), the priority of whose work is acknowledged by the author in the second communication.

Condensation Products from Carbo-imides and Orthodiamines. By C. DAHM and K. GASIOROWSKI (Ber., 19, 3057-3060). —Carborthotoluylenediphenyltetramine, C,H,<NH>C(NHPh)2, is prepared by beating carbodiphenylimide and orthotoluylenediamine (molecular weights) for four hours at 130-140°. It crystallises from benzene in needles melting at 161°, and is readily soluble in alcohol and ether. It does not react with an excess of imide. The hydrochloride, 2CH20N4,3HCl, crystallises in white needles melting at 173-174°; it is very soluble in alcohol and ether, rather sparingly in water. The sulphate was also prepared.

Carborthotoluylenediparatolyltetramine, CHUN, is prepared in a manner similarly to the above-mentioned compound. The product is extracted with boiling benzene, and the white powder dissolved in alcohol, from which it separates in needles melting at 196°. The hydrochloride, 2C2H2N1,3HCl, crystallises from the strong acid solution in needles melting at 143°.

N. H. M.

Derivatives of Parachlorazobenzene. By E. MENTHA and K. HEUMANN (Ber., 19, 2970-2974; comp. Abstr., 1886, 874).Chlorodiamidodiphenyl, NH, CH, C2H2C1·ÑH2.—When parachlorazobenzene in alcoholic solution is treated with zinc chloride and sulphuric acid, and the solution, after precipitating the zinc with hydrogen sulphide, is made alkaline with caustic soda, chlorodiamidodiphenyl is obtained and can be extracted with ether. It is a bright yellow powder, which very readily becomes oxidised. The hydrochloride, C12H1N2C1,2HCl, crystallises in tufts of white needles.

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