This paper is the first of a series in which will be reported the results of an extensive study of the reactions of cyanogen with organic compounds. On the basis of its inorganic reactions cyanogen has repeatedly been compared to the halogens (1,2). Some early work even indicated that a similar comparison could be made in the field of organic chemistry. Merz (3), for example, reported that a mixture of benzene vapor and cyanogen passed through a red hot tube gave benzonitrile, terephthalic acid nitrile, and hydrogen cyanide. Desgrez (4) studied the effect of aluminum chloride and cyanogen on boiling benzene. Decomposition of the reaction products with concentrated hydrochloric acid yielded benzonitrile, benzoyl cyanide, benzil, and unidentified compounds. Vorlander (5) claimed that toluene, diphenyl, ethylbenzene, and phenetole behaved in a similar manner.However, Machek's report (6) that catechol in aqueous solution reacted with cyanogen to give a 52% yield of 2,3-dihydroxybenzonitrile did not stand up on reexamination, and Hahn and Leopold (7) concluded later that the reaction consisted of condensation between the phenolic and cyano groups and that no nuclear substitution had taken place. Even aniline, which brominates with such extreme ease, produced symmetrical N , N-diphenyloxamidine (8) instead of aminocyanobenzene.Brief investigation of alcohols, aldehydes, phenylhydrazine, semicarbazide, diphenylguanidine, and benzylamine (9) also showed that comparison with halogens was a poor premise on which to base predictions regarding cyanogen chemistry.The behavior of each of the amino compounds above could be described as an aminolysis of cyanogen. Under such circumstances the absence from the literature of reactions between cyanogen and aliphatic amines was particularly intriguing. A series of preliminary experiments, consisting in the saturation of a large number of organic liquids and solutions, was, therefore, undertaken and it was quickly indicated that reactions with primary aliphatic amines, secondary aliphatic amines, aliphatic diamines, and mercaptans could be expected once the proper conditions were discovered. The investigation of these reactions has since been actively pursued and the results of one such study are reported in this paper.
