/||\ /||\ /||\ / || \ / || \ / || \ H / N·Cl \ H H / N·Cl \ H H / N·Cl \ H |\ || || ---> || || | ---> || || /| | \ || || <--- || || | <--- || || / | | \N || || N | || N | H\\ / H H\\ | / H H \ //H \\ / \\ | / \ // \\ / \\| / \ // H H H
_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.