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

作　　者：付晓林 孙岩 赵志刚[1] 郭勇[2] 陈庆云[2] 念保义[3] Fu Xiaolin;Sun Yan;Zhao Zhigang;Guo Yong;Chen Qingyun;Nian Baoyi(College of Chemistry & Environment Protection Engineering, Southwest Minzu University, Chengdu 610041;College of Chemistry & Environment Protection Engineering, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032;Sanming Institute of Fluorochemical Industry, Sanming University, Sanming 365004)

机构地区：[1]西南民族大学化学与环境保护工程学院,成都610041 [2]中国科学院上海有机化学研究所,上海200032 [3]三明学院三明氟化工产业技术研究院,三明365004

出　　处：《有机化学》2019年第1期144-150,共7页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.21737004,21672239,21421002);三明市氟化工产业技术研究院(Nos.FCIT201704GR,FCIT201705GR,FCIT201701BR)资助项目~~

摘　　要：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.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.

关 键 词：三氟甲基 自由基 脱卤亚磺化 烷基硫酸盐 

分 类 号：O621.25[理学—有机化学] O622.7[理学—化学]