研究论文

K3PO4-催化的β-硝基苯乙烯衍生物与乙酰胺、NBS的区域专一性氨溴加成反应研究

  • 陈战国 ,
  • 周继梅 ,
  • 王芸 ,
  • 李文丽
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  • (陕西省大分子科学重点实验室   陕西师范大学化学化工学院  西安710062)

收稿日期: 2011-03-22

  修回日期: 2011-06-23

  网络出版日期: 2011-08-16

基金资助

烯键上的区域选择和立体选择性氨卤加成反应研究;碳碳双键上的不对称氨卤加成反应研究

K3PO4-Catalyzed Regiospecific Aminobromination of β-Nitrostyrene Derivatives with acetamide and NBS

  • CHEN Zhan-Guo ,
  • ZHOU Ji-Mei ,
  • WANG Yun ,
  • LI Wen-Li
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Received date: 2011-03-22

  Revised date: 2011-06-23

  Online published: 2011-08-16

摘要

摘要 在无水磷酸钾催化下,以乙酰胺(CH3CONH2)和N-溴代丁二酰亚胺(NBS)为氮源和卤素源,丙酮作溶剂,建立了β-硝基苯乙烯双键上的区域专一性氨溴加成反应新体系。该法在室温下,无需惰性气体保护可高收率的获得邻位氨卤加成产物,最高收率可达79 % 。实验证明,当β-硝基苯乙烯中苯环4-位具有强供电子基团时(如CH3O),该反应的活性较低,同时得到唯一的α-氨基-β-二溴加成产物;当β-硝基苯乙烯中苯环4-位有强吸电子基团(如NO2)时,该反应的活性较高,同时也得到唯一的α-氨基-β-二溴加成产物。这一实验结果证明了β-硝基苯乙烯衍生物(缺电子烯键)在该条件下的氨溴加成反应是一个亲核加成反应。本文共考察了14种不同结构的β-硝基苯乙烯的氨溴加成反应情况,其产物结构经核磁共振氢谱、碳谱、及元素分析确证,并提出了可能的反应机理。

本文引用格式

陈战国 , 周继梅 , 王芸 , 李文丽 . K3PO4-催化的β-硝基苯乙烯衍生物与乙酰胺、NBS的区域专一性氨溴加成反应研究[J]. 化学学报, 2011 , 69(23) : 2851 -2858 . DOI: 10.6023/A1103229

Abstract

A regiospecific method for the aminobromination of β-nitrostyrene derivatives with acetamide and NBS as aminobrominating agent catalyzed by K3PO4 has been developed in acetone. The method can conveniently and efficiently convert β-nitrostyrenes into vicinal haloamines at room temperature in good yields up to 79 % and without the protection of an inert gaseous atmosphere. Strong electron-donating substituents(e.g.,OCH3) on the 4-position of benzene ring deactivated the reaction activity of β-nitrostyrenes and afforded a sole vicinal haloamine compound. Whereas strong electron-withdrawing substituents(e.g., NO2) activated reaction activity of them remarkably and afforded a sole vicinal haloamine compound, too. The result revealed that the addition reaction has an nucleophilic addition feature. The aminobromination of 14 examples of β-nitrostyrenes have been investigated in this work and the structure of all products were confirmed by their corresponding 1H NMR, 13C NMR spectra and their elemental analysis. A possible mechanism involving a nucleophilic conjugate addition was proposed.
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