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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (15): 1459-1463. 上一篇    下一篇

研究论文

α-乙酰氧基-N-亚硝基吡咯烷的解离及其致癌代谢机理的理论研究

李澜1,2, 滕国凤1, 孙淑娟1, 李宗和*,1   

  1. (1北京师范大学化学学院 北京 100875)
    (2上海应用技术学院 上海 200235)
  • 投稿日期:2006-06-12 修回日期:2007-01-15 发布日期:2007-08-14
  • 通讯作者: 李宗和

Theoretical Study of Decomposition and Carcinogenic Metabolic Mechanism for α-Acetoxy-N-nitrosopyrrolidine

LI Lan1,2; TENG Guo-Feng1; SUN Shu-Juan1; LI Zong-He*,1   

  1. (1 Department of Chemistry, Beijing Normal University, Beijing 100875)
    (2 Shanghai Institute of Technology, Shanghai 200235)
  • Received:2006-06-12 Revised:2007-01-15 Published:2007-08-14
  • Contact: LI Zong-He

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用ab initio方法, 在MP2/6-31G**水平下讨论了α-乙酰氧基-亚硝基吡咯烷(α-Acetoxy-NPYR)在各种条件下的解离反应机理, 并对形成终致癌物B, C, D的代谢机理进行研究. 发现在OH－和H2O作用下的解离都遵循羟基进攻羰基机理, OH－作用下是一个经四面体中间体阴离子的无位垒过程, H2O作用下有相对高的活化能(165.36 kJ/mol). H3O＋作用下是先形成阳离子产物的SN1过程, 并没有发现遵循两种综合的解离情形. 同时, 羟基化产物异构化为终致癌物B, C, D是一个相对容易进行的过程.

关键词: α-乙酰氧基-N-亚硝基吡咯烷, 解离, 致癌

The decomposition mechanism of α-acetoxy-N-nitrosopyrrolidine has been theoretically investigated at the MP2/6-31G** level in various environments (OH－, H2O, H3O＋). It was found that the decomposition mediated by OH－ and H2O was a “typical” carbonyl attack mechanism of ester hydrolysis. In the presence of H3O＋, the decomposition is an SN1 process via an intermediate of N-nitrosiminium ion. A mixture of the carbonyl attack mechanism and SN1 process was found. The unstable decomposed product of α-hydroxy-nitrosopyrrolidine can be metabolized into active carcinogenic metabolites of B, C, and D, and the process involving isomerization and protonation is easy to occur.

Key words: α-acetoxy-N-nitrosopyrrolidine, decomposition, carcinogen