高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (5): 902.doi: 10.7503/cjcu20150883

• 有机化学 • 上一篇    下一篇

β-硝基苯乙烯衍生物与丙烯酰胺及N-溴代丁二酰亚胺的区域专一性氨溴加成反应

杜曼飞, 侯丹, 惠文萍, 陈战国()   

  1. 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 710119
  • 收稿日期:2015-11-19 出版日期:2016-05-10 发布日期:2016-04-20
  • 作者简介:联系人简介: 陈战国, 男, 博士, 副教授, 主要从事有机合成及天然产物结构改造方面的研究. E-mail:chzhg@snnu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: 20572066)、 陕西省自然科学基金(批准号: 2009JM2011)和陕西师范大学研究生创新基金(批准号: 2008CXB009)资助

Regiospecific Aminobromination of β-Nitrostyrene Derivatives with Acrylamide and N-Bromobutanimide

DU Manfei, HOU Dan, HUI Wenping, CHEN Zhanguo*()   

  1. Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119, China
  • Received:2015-11-19 Online:2016-05-10 Published:2016-04-20
  • Contact: CHEN Zhanguo E-mail:chzhg@snnu.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No.20572066), the Natural Science Foundation of Shaanxi Province, China(No.2009JM2001) and the Innovation Foundation of Postgraduate Cultivation of Shaanxi Normal University, China(No.2008CXB009)

摘要:

β-硝基苯乙烯衍生物为底物, 丙烯酰胺和N-溴代丁二酰亚胺(NBS)为氮源和卤素源, 建立了碳-碳双键上的选择性氨溴加成反应新体系. 以二氯甲烷为溶剂, 在没有惰性气体保护及乙醇钠促进下, β-硝基苯乙烯衍生物与丙烯酰胺和NBS于室温反应即可高收率地获得α-氨基-β,β-二溴加成产物, 最高收率达83%; 以甲醇为溶剂, 在无水碳酸钠作用下, β-甲基-β-硝基苯乙烯衍生物也可高收率地获得相应的邻位氨溴加成产物, 最高收率达97%. 共考察了25种不同结构β-硝基苯乙烯衍生物的氨溴加成反应, 结果表明, 该反应具有广泛的适应性. 采用核磁共振波谱及质谱表征了产物的结构, 并提出了可能的反应机理.

关键词: 氨溴加成反应, β, -硝基苯乙烯, 区域专一性, 丙烯酰胺, N-溴代丁二酰亚胺

Abstract:

A new protocol for the high regioselective aminobromination of β-nitrostyrene derivatives with acrylamide and N-Bromobutanimide(NBS) as nitrogen/bromine sources was developed. β-Nitrostyrene derivatives reacted with acrylamide and NBS promoted by CH3CH2ONa at room temperature(without the protection of an inert gaseous atmosphere) in CH2Cl2, offered vicinal haloamine products in good yields(up to 83%). For the β-methyl-β-nitrostyrene, the good yields(up to 98%) were also achieved in CH3OH promoted by Na2CO3. Although the strong electron-donating substituents(e.g., OCH3) on the 4-position of benzene ring could deactivated the reaction activity of β-nitrostyrenederi-vetives, the vicinal haloamines were also afforded as the sole addition product. Whereas strong electron-withdrawing substituents(e.g., NO2) could activated reaction activity remarkably and the vicinal haloamines were afforded as the sole addition product, too. The result revealed that the addition reaction has a nucleophilic addition feature. The aminobromination of 25 examples of β-nitrostyrenes were investigated and the structure of all products were confirmed by the corresponding nuclear magnetic resonance(NMR) spectra and high resolution mass spectrometer(HRMS). A possible mechanism involving a nucleophilic conjugate addition was proposed.

Key words: Aminobromination, β, -Nitrostyrene, Regiospecific, Acrylamide, N-Bromobutanimide

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