Ab-initio molecular orbital studies on a new mechanism for the interconversion of monomethylnitrosamine and methyldiazohydroxide

Monomethylnitrosamine and methyldiazohydroxide are two proposed N-nitrosamine metabolites, which are formally related by an N → O 1,3-proton shift. Their possible interconversion is an important reaction to investigate in elucidating the pathways involved in the decomposition of carcinogenic N-nitrosamines. Self-consistent field molecular orbital studies using a 4-21G basis set, in which solvation is treated using the supermolcule approach, have led to the proposal of a new low energy pathway for their interconversion; this mechanism involves protonation and the implicit involvement of at least two molecules of water.