Abstract
4-(3-Cyano-1-triazeno) pyridines (III, IX) were synthesized by treating azides (I, VII) with potassium cyanide, followed by acidification with hydrochloric acid. Cyanotriazene potassium salts (II, VIII) gave 4-[3-(N2-hydroxyamidino)-1-triazeno]-pyridines (IVa, Xa) and 4-(3-thiocarbamoyl-1-triazeno) pyridines (IVb, Xb) on reaction with hydroxylamine hydrochloride and with hydrogen sulfide in the presence of ammonia, respectively. The reactions of II and VIII with dialkyl sulfates gave 4-(3-cyano-1-triazene)-1, 4-dihydropyridines (Va, Vb, XIIa, XIIb), which were also derived from the quaternary azides (VIa, VIb, XIIIa, XIIIb). An azourethan (XI) was obtained by treating VIII with ethanol containing a small amount of hydrochloric acid. The arylazo derivatives (XVa, XVb, XVc) were synthesized by treating VIII with a mixture of 2-naphthol or diphenylamine and ethanol containing hydrochloric acid. The reaction of Va and XIIa with hydroxylamine hydrochloride gave 4-[3-(N2-hydroxyamidino)-1-triazeno]-1, 4-dihydropyridine hydrochlorides (XVI, XVII).
