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有机化学
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有机化学 ›› 2008, Vol. 28 ›› Issue (04): 705-712. 上一篇    下一篇

研究论文

邻基效应促进的2-芳基硫代芳胺衍生物的简易合成

张慧*,a，曹卫国a，陈杰a，邓红梅b   

  1. (a上海大学化学系 上海 200444)
    (b上海大学分析测试中心 上海 200444)
  • 收稿日期:2007-08-31 修回日期:2007-10-23 发布日期:2008-04-17
  • 通讯作者: 张慧

Ortho Substituent-Promoted Simple Synthesis of the Derivatives of 2-Arylsulfanyl Anilines

ZHANG Hui*,a,CAO Wei-Guoa,CHEN Jiea,DENG Hong-Meib   

  1. (a Department of Chemistry, Shanghai University, Shanghai 200444)
    (b Instrumental Analysis and Research Center, Shanghai University, Shanghai 200444)
  • Received:2007-08-31 Revised:2007-10-23 Published:2008-04-17
  • Contact: yehao7171@shu.edu.cn

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2-芳基硫代芳胺的结构广泛存在于许多具有重要生理、药理活性的天然产物、药物以及材料当中, 研究此类结构的构建对这些化合物的合成路线设计可以提供新的思路. 传统合成2-芳基硫代芳胺, 常需多步骤或高温、强碱条件下进行, 能进行此类反应的反应物有限, 所得产物收率不高. 选用三氟乙酰基作为芳胺氮原子上的保护基, 利用三氟乙酰基的邻位促进效应, 并采用碘化亚铜/L-脯氨酸的催化体系, 在乙二醇二甲醚中, 碳酸钾为碱, 于60 ℃一步实现N-三氟乙酰基邻碘代苯胺与芳基硫酚的偶联, 以高产率获得了N-三氟乙酰基-2-芳基硫代芳胺. 反应条件温和, 催化体系价廉易得, 反应操作简便.

关键词: 2-芳基硫代芳胺, 铜试剂, 催化剂, 偶联, 邻基效应

2-Arylsulfanyl anilines are sub-units in a considerable number of the functional materials, the biologically important natural products and pharmaceuticals. Traditional methods required of such conditions as long steps or high temperature (≥150 ℃) and strong base, which lowered the yield of the products and limited the scope of the starting materials. In this paper, a highly general, experimentally simple, and inexpensive catalyst system was developed for the synthesis of 2-arylsulfanyl anilines by using 10 mol% CuI as catalyst, 20 mol% L-proline as ligand, and K2CO3 as base. And the existence of an ortho substitution effect caused by the NHCOCF3 group promoted the reaction to carry out at the temperature as low as 60 ℃ in good to excellent yields.

Key words: copper reagent, 2-arylsulfanyl aniline, coupling, catalyst, ortho substitution effect