Diazoamines.—The diazoamines, R·N2·NHR, may be prepared by the action of the primary and secondary amines on the diazonium salts, or by the action of nitrous acid on the free primary amine. In the latter reaction it is assumed that the isodiazohydroxide first formed is immediately attacked by a second molecule of the amine. They are yellow crystalline solids, which do not unite with acids. Nitrous acid converts them, in acid solution, into diazonium salts.
C6H5N2·NHC6H5 + 2HCl + HNO2 = 2C6H5N2Cl + 2H2O.
They are readily converted into the isomeric aminoazo compounds, either by standing in alcoholic solution, or by warming with a mixture of the parent base and its hydrochloride; the diazo group preferably going into the para-position to the amino group. When the para-position is occupied, the diazo group takes the ortho-position. H. Goldschmidt and R. U. Reinders (Ber., 1896, 29, p. 1369, 1899) have shown that the transformation is a monomolecular reaction, the velocity of transformation in moderately dilute solution being independent of the concentration, but proportional to the amount of the catalyst present (amine hydrochloride) and to the temperature. It has also been shown that when different salts of the amine are used, their catalytic influence varies in amount and is almost proportional to their degree of ionization in aqueous solution. Diazoaminobenzene, C6H5N2·NHC6H5, crystallizes in golden yellow laminae, which melt at 96° C. and explode at a slightly higher temperature. It is readily soluble in alcohol, ether and benzene. Concentrated hydrochloric acid converts it into chlorbenzene, aniline and nitrogen. Zinc dust and alcoholic acetic acid reduce it to aniline and phenylhydrazine.
Diazoimino compounds, R·N3, may be regarded as derivatives of azoimide (q.v.); they are formed by the action of ammonia on the diazoperbromides, or by the action of hydroxylamine on the diazonium sulphates (J. Mai, Ber., 1892, 25, p. 372; T. Curtius, Ber., 1893, 26, p. 1271). Diazobenzeneimide, C6H5N3, is a yellowish oil of stupefying odour. It boils at 59° C. (12 mm.), and explodes when heated. Concentrated hydrochloric acid decomposes it with formation of chloranilines and elimination of nitrogen, whilst on boiling with sulphuric acid it is converted into aminophenols.
Aliphatic Diazo Compounds.—The esters of the aliphatic amino acids may be diazotized in a manner similar to the primary aromatic amines, a fact discovered by T. Curtius (Ber., 1833, 16, p. 2230). The first aliphatic diazo compound to be isolated was diazoacetic ester, CH·N2·CO2C2H5, which is prepared by the action of potassium nitrite on the ethyl ester of glycocoll hydrochloride, HCl·NH2·CH2·CO2C2H5 + KNO2 = CHN2·CO2C2H5 + KCl + 2H2O. It is a yellowish oil which melts at -24° C.; it boils at 143-144° C., but cannot be distilled safely as it decomposes violently, giving nitrogen and ethyl fumarate. It explodes in contact with concentrated sulphuric acid. On reduction it yields ammonia and glycocoll (aminoacetic acid). When heated with water it forms ethyl hydroxy-acetate; with alcohol it yields ethyl ethoxyacetate. Halogen acids convert it into monohalogen fatty acids, and the halogens themselves convert it into dihalogen fatty acids. It unites with aldehydes to form esters of ketonic acids, and with aniline yields anilido-acetic acid. It forms an addition product with acrylic ester, which on heating loses nitrogen and leaves trimethylene dicarboxylic ester. Concentrated ammonia converts it into diazoacetamide, CHN2·CONH2, which crystallizes in golden yellow plates which melt at 114° C. For other reactions see [Hydrazine]. The constitution of the diazo fatty esters is inferred from the fact that the two nitrogen atoms, when split off, are replaced by two monovalent elements or groups, thus leading to the formula
for diazoacetic ester.
Diazosuccinic ester, N2·C(CO2C2H5)2, is similarly prepared by the action of nitrous acid on the hydrochloride of aspartic ester. It is decomposed by boiling water and yields fumaric ester.
Diazomethane, CH2N2, was first obtained in 1894 by H. v. Pechmann (Ber., 1894, 27, p. 1888; 1895, 28, p. 855). It is prepared by the action of aqueous or alcoholic solutions of the caustic alkalis on the nitroso-acidyl derivatives of methylamine (such, for example, as nitrosomethyl urethane, NO·N(CH3)·CO2C2H5, which is formed on passing nitrous fumes into an ethereal solution of methyl urethane). E. Bamberger (Ber., 1895, 28, p. 1682) regards it as the anhydride of iso-diazomethane, CH3·N:N·OH, and has prepared it by a method similar to that used for the preparation of iso-diazobenzene. By the action of bleaching powder on methylamine hydrochloride, there is obtained a volatile liquid (methyldichloramine, CH3·N·Cl2), boiling at 58-60° C., which explodes violently when heated with water, yielding hydrocyanic acid (CH3NCl2 = HCN + 2HCl). Well-dried hydroxylamine hydrochloride is dissolved in methyl alcohol and mixed with sodium methylate; a solution of methyldichloramine in absolute ether is then added and an ethereal solution of diazomethane distils over. Diazomethane is a yellow inodorous gas, very poisonous and corrosive. It may be condensed to a liquid, which boils at about 0° C. It is a powerful methylating agent, reacting with water to form methyl alcohol, and converting acetic acid into methylacetate, hydrochloric acid into methyl chloride, hydrocyanic acid into acetonitrile, and phenol into anisol, nitrogen being eliminated in each case. It is reduced by sodium amalgam (in alcoholic solution) to methylhydrazine, CH3·NH·NH2. It unites directly with acetylene to form pyrazole (H. v. Pechmann, Ber., 1898, 31, p. 2950) and with fumaric methyl ester it forms pyrazolin dicarboxylic ester.
(F. G. P.*)