Abstract5‐Amino‐1H‐imidazole‐4‐carboxamide hydrochloride has been converted into a series of new, potentially biologically activeN6‐substituted 2‐azaadenines5via4‐diazo‐4H‐imidazole‐5‐carbonitrile (1) which was coupled with primary amines to give5in 11 – 78% yield. Further, some 1‐substituted 2‐azahypoxanthines9have been prepared in 17 – 66% yield from ethyl 5‐amino‐1H‐imidazole‐4‐carboxylate (6)viaethyl 4‐diazo‐4H‐imidazole‐5‐ca