双环氧乙烷对三类亚硝胺的羟基化过程的理论研究

采用量子化学密度泛函(DFT)方法, 在B3LYP/6-31G**水平下研究了双环氧乙烷(Dioxirane)、氧化二甲基亚硝胺(NDMA)、吡咯烷亚硝胺(NPYR)和哌啶烷亚硝胺(NPIP)中的C—H键, 三类亚硝胺化合物均形成α-羟基化产物的反应机理. 得到三类分子的羟基化反应有syn-和anti-两种进攻方式, 在气相和溶剂(CH2Cl2)中, Dioxirane氧化三类亚硝胺分子有相对低的能垒, 均容易进行α-羟基化.

Theoretical Study of Hydroxylation of Nitrosodimethylamine,Nitrosopyrolidine,and Nitrosopiperidine by Dioxirane

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.