Synthesis of novel 3-(α-arylhydrazono-1,3,4-oxadiazol-2-ylmethyl)-2-oxo-1,2-dihydroquinoxalines and their characteristic tautomerism between the hydrazone imine and diazenyl enamine forms

The reactions of 3-(α-arylhydrazono)hydrazinocarbonylmethyl-2-oxo-1,2-dihydroquinoxalines 1a,b with triethyl orthoesters resulted in the intramolecular cyclization to give the 3-(α-arylhydrazono-1,3,4-oxadiazol-2-ylmethyl)-2-oxo-1,2-dihydroquinoxalines 4a–d , but not the 1,2,4,5-tetrazepinylquinoxalines 5a–d . The cyclization mode into the 1,3,4-oxadiazole ring was confirmed by the alternate syntheses of 4a,c from the reactions of 3-(1,3,4-oxadiazol-2-ylmethylene)-2-oxo-1,2,3,4-tetrahydroquinoxalines 6a,b with o-chlorophenyl diazonium salts, respectively. Moreover, 4a–d exhibited an interesting tautomerism between the hydrazone imine form A and diazenyl enamine form B.