Abstract: The hydroxylation reaction mechanisms of nitrosodimethylamine, nitrosopyrolidine and nitrosopiperidine by dioxirane were theoretically investigated at the B3LYP/6-31G** level. It is found that there are two paths(separately, syn- and anti-) to the hydroxylation reaction of the three nitrosoamines that have the same hydroxylation reaction mechanisms. The study of the potential surface shows that the hydroxylation of the three nitrosoamines by dioxirane has a relatively low energy barrier. The result of the theoretical study shows that the α-hydroxylation products of these nitrosoamines form easily by dioxirane.

Key words: Nitrosodimethylamine(NDMA), Nitrosopyrotidine(NPYR), Nitrosopiperidine(NPIP), Density functional method, α-hydroxylation