有机化学 ›› 2015, Vol. 35 ›› Issue (3): 647-654.DOI: 10.6023/cjoc201410042 上一篇    下一篇

研究论文

偶氮基作为可离去导向基团辅助的C—H键定向硝化反应:区域专一性地合成邻苯二胺类化合物

张剑, 张巍, 任少波, 崔建海, 刘运奎   

  1. 浙江工业大学化学工程学院 绿色化学与技术国家重点实验室培育基地 杭州 310014
  • 收稿日期:2014-10-30 修回日期:2015-01-07 出版日期:2015-03-25 发布日期:2015-01-13
  • 通讯作者: 刘运奎 E-mail:ykuiliu@zjut.edu.cn
  • 基金资助:

    国家自然科学基金(Nos. 21172197, 21372201)、浙江工业大学"省重中之重一级学科"开放基金资助项目.

Orientation Nitration of C—H Bond Using Azo Group as a Removable Directing Group: Regiospecific Synthesis of o-Phenylenediamines

Zhang Jian, Zhang Wei, Ren Shaobo, Cui Jianhai, Liu Yunkui   

  1. State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014
  • Received:2014-10-30 Revised:2015-01-07 Online:2015-03-25 Published:2015-01-13
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21172197, 21372201) and the Opening Foundation of Zhejiang Key Course of Chemical Engineering and Technology, Zhejiang University of Technology.

由苯胺类化合物经传统硝化反应难以区域专一性地制备邻苯二胺类化合物. 介绍一种由苯胺类化合物区域专一性地合成邻苯二胺类化合物的方法. 即首先由苯胺类化合物制得偶氮类化合物, 再经钯催化的偶氮基导向的邻位C—H键定向硝化反应合成邻硝基偶氮类化合物, 最后经Zn/HCOOH体系还原制得邻苯二胺类化合物. 在该过程中, 钯催化的偶氮基导向的邻位C—H键硝化反应是获得高区域选择性的关键.

关键词: 偶氮化合物, 邻苯二胺, 硝化, 钯催化, C—H活化

It is a difficult task to regiospecifically synthesize o-phenylenediamines from anilines via traditional elelectrophilic nitration process. This article described a method for the regiospecific synthesis of o-phenylenediamines from anilines. The procedure consisted of three steps, namely, the synthesis of azo compounds from anilines, the palladium-catalyzed azo group-directed ortho-orientation nitration of C—H bond, and the final reduction of the resulting o-nitro azo compounds to give o-phenylenediamines by the Zn/HCOOH system. In the process, the palladium-catalyzed azo group-assisted ortho-nitration of C—H bond is the key step for gaining the whole high regioselectivity.

Key words: azo compounds, o-phenylenediamines, nitration, palladium catalysis, C—H bond activation