Chin. J. Org. Chem. ›› 2019, Vol. 39 ›› Issue (6): 1665-1671.DOI: 10.6023/cjoc201903037 Previous Articles     Next Articles

Special Issue: 碳氢活化合辑2018-2019 金属有机化学

Articles

Pd(OAc)2/N-氯-N-氟苯磺酰胺体系下乙酰苯胺的氯化反应

朱晔a, 黄金文b, 杨先金a,c   

  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 200237;
    b 上海应用技术大学化学与环境工程学院 上海 201418;
    c 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 200032
  • 收稿日期:2019-03-20 修回日期:2019-04-25 发布日期:2019-05-10
  • 通讯作者: 黄金文, 杨先金 E-mail:yxj@ecust.edu.cn;goldven@sit.edu.cn
  • 基金资助:

    国家自然科学基金(No.21372077)和低品位磷矿高效利用国家重点实验室(No.WFKF2017-04)资助项目.

Chlorination of Anilide by Pd(OAc)2/N-Chloro-N-fluorobenzene- sulfonylamide

Zhu Yea, Huang Jinwenb, Yang Xianjina,c   

  1. a Key Laboratory for Advanced Materials & Institute of Fine Chemicals, East China University of Science and Technology, Shanghai 200237;
    b School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418;
    c Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Science, Shanghai 200032
  • Received:2019-03-20 Revised:2019-04-25 Published:2019-05-10
  • Contact: 10.6023/cjoc201903037 E-mail:yxj@ecust.edu.cn;goldven@sit.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21372077) and the State Key Laboratory of Efficient Utilization for Low Grade Phosphate Rock and Its Associated Resources (No. WFKF2017-04).

A mild method for palladium-catalyzed halogenation of acetanilide with N-chloro-N-fluorobenzenesulfonylamide (CFBSA) as a chlorinating reagent, oxidant, and novel promoting reagent was achieved. The decomposition of byproduct N-fluoroben-zenesulfonylamine in the presence of Pd(OAc)2 could accelerate the process of chlorination. Preliminary mechanism investigation showed that Pd catalyzed anilide directed C-H activation lead to the ortho chlorination selectivity. A series of ortho-chlorinated anilides were obtained in 28%~82% yields.

Key words: chlorinating reagent, fluorine atom, Pd-catalyzed, synthetic methodology