MECHANISM OF REARRANGEMENT OF OXIDES OF TERTIARY-AMINES - BEHAVIOR OFTHE MOLECULAR-ORBITALS

The study of the mechanism of rearrangement of oxide of a tertiary ami ne to the O-substituted hydroxylamine was carried out by the semiempir ical method AM1. The case of the N-oxide of N-(2,4-dinitrophenyl) pipe ridine was taken as a model. The study of the reaction mechanism was p erformed taking into account the presence or lack of an intermolecular hydrogen bond with formic acid, analyzing the behavior of the frontie r molecular orbitals,and their neighbors. We have also made ab initio calculations in the vicinity of the transition state previously calcul ated with AM1 using the basis STO-3G and 3-21G. (C) 1998 Elsevier Sci ence B.V.