从α-三氟甲基苄溴合成烷基硫酸盐——脱卤亚磺化反应的延伸

doi:10.6023/cjoc201810022

有机化学 ›› 2019, Vol. 39 ›› Issue (1): 144-150.DOI: 10.6023/cjoc201810022 上一篇下一篇

所属专题：庆祝陈庆云院士九十华诞

研究论文

从α-三氟甲基苄溴合成烷基硫酸盐——脱卤亚磺化反应的延伸

付晓林^a, 孙岩^b, 赵志刚^a, 郭勇^b, 陈庆云^b, 念保义^c

a 西南民族大学化学与环境保护工程学院成都 610041;
b 中国科学院上海有机化学研究所上海 200032;
c 三明学院三明氟化工产业技术研究院三明 365004

收稿日期:2018-10-18 修回日期:2018-11-24 发布日期:2018-11-30
通讯作者: 孙岩, 赵志刚 E-mail:sunyan@sioc.ac.cn;zzg63129@163.com
基金资助:
国家自然科学基金（Nos.21737004，21672239，21421002）和三明市氟化工产业技术研究院（Nos.FCIT201704GR，FCIT201705GR，FCIT201701BR）资助项目.

Synthesis of Alkyl Sulfate from α-Trifluoromethylbenzylbromide—An Extension of Sulfinatodehalogenation

Fu Xiaolin^a, Sun Yan^b, Zhao Zhigang^a, Guo Yong^b, Chen Qingyun^b, Nian Baoyi^c

a College of Chemistry & Environment Protection Engineering, Southwest Minzu University, Chengdu 610041;
b College of Chemistry & Environment Protection Engineering, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032;
c Sanming Institute of Fluorochemical Industry, Sanming University, Sanming 365004

Received:2018-10-18 Revised:2018-11-24 Published:2018-11-30
Contact: 10.6023/cjoc201810022 E-mail:sunyan@sioc.ac.cn;zzg63129@163.com
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 21737004, 21672239, 21421002) and the Sanming Institute of Fluorochemical Industry (Nos. FCIT201704GR, FCIT201705GR, FCIT201701BR).

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摘要/Abstract

脱卤亚磺化反应是引入氟烷基基团的一种常用方法.探索了α-三氟甲基苄溴在脱卤亚磺化条件下的反应，发现产物并不是亚磺酸盐[ArCH（CF₃）SO₂Na]，而是烷基硫酸盐[ArCH（CF₃）OSO₃Na].即使在烯烃的存在的条件下，α-三氟甲基苄溴在脱卤亚磺化条件下产生了自由基，也不与烯烃发生加成反应，而是直接生成亚磺酸盐，亚磺酸盐被空气氧化成烷基硫酸盐.

关键词: 三氟甲基, 自由基, 脱卤亚磺化, 烷基硫酸盐

The sulfinatodehalogenation reaction is a common method of introducing a fluoroalkyl group. In this paper, the reaction of α-trifluoromethylbenzyl bromide under sulfinatodehalogenation conditions was investigated. It was found that the product was an sodium alkyl sulfate (ArCH(CF₃)OSO₃Na) instead of an sodium alkyl sulfinate (ArCH(CF₃)SO₂Na) which was normal produced. α-Trifluoromethylbenzyl bromide did not react with the olefin after its generation of a radical intermediate under sulfinatodehalogenation conditions even though an olefin was presented. Instead, the reaction directly gave an alkyl sulfinate, and then oxidized by air to provide a product as an alkyl sulfate.

Key words: Trifiluoromethyl, free radical, sulfinatodehalogenation, alkyl sulfate

引用此文

付晓林, 孙岩, 赵志刚, 郭勇, 陈庆云, 念保义. 从α-三氟甲基苄溴合成烷基硫酸盐——脱卤亚磺化反应的延伸[J]. 有机化学, 2019, 39(1): 144-150.

Fu Xiaolin, Sun Yan, Zhao Zhigang, Guo Yong, Chen Qingyun, Nian Baoyi. Synthesis of Alkyl Sulfate from α-Trifluoromethylbenzylbromide—An Extension of Sulfinatodehalogenation[J]. Chin. J. Org. Chem., 2019, 39(1): 144-150.

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从α-三氟甲基苄溴合成烷基硫酸盐——脱卤亚磺化反应的延伸

Synthesis of Alkyl Sulfate from α-Trifluoromethylbenzylbromide—An Extension of Sulfinatodehalogenation

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