文献类型：期刊文献

中文题名：Decomposition of 2-Mercaptoethyl O-Ester:S_(N)2 Displacement or Acyl Transfer?A Theoretical Study

作者：Shenshen Zhang[1];Chenze Qi[1];Chen Wang[1]

机构：[1]Zhejiang Key Laboratory of Alternative Technologies for Fine Chemicals Process,Shaoxing University,Shaoxing,Zhejiang 312000,China

年份：2014

卷号：32

期号：4

起止页码：335

中文期刊名：中国化学:英文版

外文期刊名：Chinese Journal of Chemistry

收录：CSTPCD、、Scopus、CSCD、PubMed、CSCD2013_2014

基金：We thank the National Natural Science Foundation of China(No.21202102)for the financial support.

语种：英文

中文关键词：2-mercaptoethyl O-ester;mechanism;S_(N)2 displacement;acyl transfer;theoretical calculations

中文摘要：The mechanism for the decomposition of 2-mercaptoethyl O-ester was theoretically investigated.The mecha-nism that 2-mercaptoethyl O-ester undergoes an S_(N)2 displacement of the O atom by the S atom onα-C is much fa-vored over the mechanism of N-to-S acyl transfer.The length of the alcohol moiety has large effects on the decom-position efficiency of thiol-substituted alkyl O-esters.The reactivities of these esters are controlled by distortion en-ergies.Only 2-mercaptoethyl O-ester can undergo the decomposition at room temperature due to the low distortion energy to achieve the transition state geometry.If the thiol group of 2-mercaptoethyl O-ester is replaced by an amino group,the N-to-N acyl transfer mechanism is more favored than the S_(N)2 displacement mechanism.