Amination of 5-azacinnoline with aromatic amines

Abstract

The 5-azacinnoline molecule was subjected to quantum-mechanical calculation by the Hückel method. The formation of 4-amino derivatives in the case of the reaction of 5-azacinnoline with aliphatic amines in the presence of an oxidizing agent and of 4,4′-bis(5-azacinnolinyl) in the case of dimerization in an oxygenfree medium was substantiated theoretically. The possibility of reactions with anions of aromatic amines was predicted by means of the Klopman method. It is shown that, in practice, the reaction is actually accelerated and that, in conformity with theory, the reaction center is the nitrogen atom of the aromatic amine. Possible products involving reaction with the participation of the pcarbon atom of the arylamine were not recorded. As in the case of aliphatic amines, the formation of a dimer was observed in an oxygen-free medium. The structures of the compounds obtained were proved by means of a combination of physicochemical methods.