Electronic structure and conformational flexibility of 1,4-dihydroazines and their 4-ylide derivatives

The conformational flexibility of 1,4-dihydropyridine, 1,4-dihydropyrimidine, 1,4-dihydropyridazine, 1,4-dihydro-1,3,5-triazine, and their 4-oxo, imino, and methylene derivatives was studied by the semiempirical quantum-chemical AM1 method. It was demonstrated that the replacement of the methylene group in the dihydroazine ring by the exocyclic double bond results only in an increase in the rigidity of the heterocycle rather than leading to a loss of its conformational flexibility. It was suggested that nonplanar conformations of rings in ylide derivatives are stabilized by the nonaromatic cyclic -system. Introduction of the exocyclic double bond does not cause a substantial change in the -electronic structure of the heterocycle. The aromaticity indicesI ₆ andI ₆() were calculated. The correlation between these indices and a change in the energy upon bending of the heterocycle was established.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No 8 pp 1938–1941, August, 1996.