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

doi:10.6023/cjoc201410042

Chin. J. Org. Chem. ›› 2015, Vol. 35 ›› Issue (3): 647-654.DOI: 10.6023/cjoc201410042 Previous Articles Next Articles

ARTICLE

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

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 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

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 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.

1. Orientation Nitration of C—H Bond Using Azo Group as a Removable Directing Group: Regiospecific Synthesis of o-Phenylenediamines.PDF(1537KB)

Abstract

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

Cite this article

Zhang Jian, Zhang Wei, Ren Shaobo, Cui Jianhai, Liu Yunkui. Orientation Nitration of C—H Bond Using Azo Group as a Removable Directing Group: Regiospecific Synthesis of o-Phenylenediamines[J]. Chin. J. Org. Chem., 2015, 35(3): 647-654.

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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

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

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