有机化学 ›› 2015, Vol. 35 ›› Issue (12): 2604-2609.DOI: 10.6023/cjoc201506014 上一篇    下一篇

研究论文

合成取代的N—F双苯磺酰亚胺及其与烯醇硅醚的反应比较

李青巍a, 陈福利a, 杨先金a,b   

  1. a 华东理工大学精细化工研究所结构可控先进功能材料及其制备教育部重点实验室 上海 200327;
    b 中国科学院上海有机化学研究所有机氟化学重点实验室 上海 200327
  • 收稿日期:2015-06-12 修回日期:2015-07-13 发布日期:2015-08-17
  • 通讯作者: 杨先金 E-mail:yxj@ecust.edu.cn
  • 基金资助:

    国家自然科学基金(No. 2132077)资助项目.

Synthesis of Substituted N—F Benzenesulfonimides and Comparison of Their Fluorination Reactivity via Their Reactions with Silylenol Ethers

Li Qingweia, Chen Fulia, Yang Xianjina,b   

  1. a Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science and Technology, Shanghai 200237;
    b Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • Received:2015-06-12 Revised:2015-07-13 Published:2015-08-17
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 2132077).

N—F双苯磺酰胺作为一种常用的氟化试剂, 会因为苯环上修饰不同的官能团而影响试剂本身的电子效应, 这些改变会影响到试剂中N—F键的强弱, 也就是试剂的氟化活性, 进而对氟化反应产生比较大的影响. 主要合成了不同取代基的N—F苯磺酰胺试剂, 并且用这些试剂与几种烯醇硅醚进行氟化反应, 以期望找到活性更高的氟化试剂. 从实验结果可以看出, 在众多的不同取代基的N—F苯磺酰胺试剂中, N-氟-4-硝基-4'-氟双苯磺酰胺与N-氟-4-叔丁基-4'-氟双苯磺酰胺的氟化效果优于N-氟双苯磺酰胺(NFSI). 对这两种试剂进行了一系列的底物的拓展, 并且与N-氟苯磺酰胺(NFSI)进行了比较. 实验结果表明, 对于某些底物论这两种试剂的氟化性能比未经修饰的N-氟苯磺酰胺(NFSI)要好.

关键词: 取代基的N—F双苯磺酰胺, 氟化反应, 烯醇硅醚

The fluorination reactivity of N—F benzenesulfonimides depended on the strength of N—F bond and was easily affected by substituents on the phenyl of substituted N—F benzenesulfonimides via electronic or steric effect. In this work, N—F benzenesulfonimides with different substituents were synthesized and reacted with silylenol ethers, and the results indicated that utilizing N-fluoro-4-fluoro-4'-nitrobenzenesulfonimide and N-fluoro-4-tert-butyl-4'-fluorobenzenesulfonimide could improve the reactivity or selectivity of fluorination than using N—F benzenesulfonimide in lots of selected experiments.

Key words: substituted N—F benzenesulfonimide, fluorination, silylenol ether