AbstractA much improved synthesis of the heretofore difficultly obtainable 2,6‐diaminopyrazine(4)was afforded by the low‐pressure catalytic hydrogenation (palladium on carbon) of 2,6‐diazido‐pyrazine(2); reaction of 2,6‐dichloropyrazine(1)and sodium azide gave2in 84% yield. The outcome of the reduction was found to be solvent dependent: 1,2‐dimethoxyethane containing aqueous ammonia gave4in 83% yield; 1,2‐dimethoxyethane alone gave 5‐aminotetrazolo[1,5‐a]‐pyrazine(3)in 26% yield. Additional alternative syntheses of3and4are described. A number of acyl and azo derivatives of4were prepared. Reactions of2with dimethyl acetylenedicarboxylate and ethyl acetate (base catalyzed) leading tovic‐triazole derivativ