| 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 |
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| 引用本文： | 李澜,滕国凤,孙淑娟,李宗和.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[J].化学学报,2007,65(15):1459-1463. |
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| 作者姓名： | 李澜 滕国凤 孙淑娟 李宗和 |
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| 作者单位： | 1. 北京师范大学化学学院,北京,100875;上海应用技术学院,上海,200235
2. 北京师范大学化学学院,北京,100875 |
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| 摘 要： | 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.
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| 关 键 词： | α-乙酰氧基-N-亚硝基吡咯烷 解离 致癌 |
| 收稿时间： | 2006-6-12 |
| 修稿时间： | 2006-06-122007-04-31 |
Theoretical Study of Decomposition and Carcinogenic Metabolic Mechanism for α-Acetoxy-N-nitrosopyrrolidine |
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| LI Lan,TENG Guo-Feng,SUN Shu-Juan,LI Zong-He.Theoretical Study of Decomposition and Carcinogenic Metabolic Mechanism for α-Acetoxy-N-nitrosopyrrolidine[J].Acta Chimica Sinica,2007,65(15):1459-1463. |
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| Authors: | LI Lan TENG Guo-Feng SUN Shu-Juan LI Zong-He |
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| Institution: | a Department of Chemistry, Beijing Normal University, Beijing 100875;b Shanghai Institute of Technology, Shanghai 200235 |
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| Abstract: | 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. |
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| Keywords: | α-acetoxy-N-nitrosopyrrolidine decomposition carcinogen |
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