有机化学 ›› 2019, Vol. 39 ›› Issue (11): 3162-3168.DOI: 10.6023/cjoc201905031 上一篇    下一篇

研究论文

γ-硝基腈合成4, 5-二氢吡咯衍生物

文婷, 康梦, 陈战国*()   

  1. 陕西师范大学化学化工学院 陕西省大分子科学重点实验室 西安 710119
  • 收稿日期:2019-05-14 出版日期:2019-11-25 发布日期:2019-07-17
  • 通讯作者: 陈战国 E-mail:chzhg@snnu.edu.cn
  • 基金资助:
    陕西省自然科学基金(2009JM2011)

Synthesis of 4, 5-Dihydropyrrole from γ-Nitro-nitrile

Wen Ting, Kang Meng, Chen Zhanguo*()   

  1. Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119
  • Received:2019-05-14 Online:2019-11-25 Published:2019-07-17
  • Contact: Chen Zhanguo E-mail:chzhg@snnu.edu.cn
  • Supported by:
    the Natural Science Foundation of Shaanxi Province(2009JM2011)

建立了由γ-硝基腈合成4,5-二氢吡咯衍生物的新方法.用还原铁粉和浓盐酸混合体系作为还原剂,以甲醇为溶剂,γ-硝基腈在30℃下其硝基被还原成氨基,该氨基与分子内的氰基自发地发生亲核加成反应和重排反应,形成一系列4,5-二氢吡咯杂环化合物.在优化条件下,不同结构的γ-硝基腈均能以满意的收率转变成4,5-二氢吡咯衍生物,说明该反应具有较好的普适性.根据实验结果,提出了可能的反应机理.

关键词: 4, 5-二氢吡咯衍生物, γ-硝基腈, 丙二腈, 氰基乙酸乙酯

A new method for the synthesis of 4, 5-dihydropyrrole derivatives from γ-nitro-nitriles is described. In this procedure, the nitro groups of nitro-nitriles were reduced into aminoes under Fe+HCl systerm in methanol at 30℃ firstly. And then the amino-groups reacted with cyano groups to form target compounds via intramolecular nucleophilic addition reaction and rearrangement reaction. Under the optimized conditions, all γ-nitro-nitriles can be easily converted into 4, 5-dihydropyrrole derivatives in satisfactory yield. It shows that the reaction has better universality. Based on the experimental results, the possible reaction mechanism was proposed.

Key words: 4, 5-dihydropyrrole derivative, γ-nitro-nitrile, malonitrile, ethyl cyanoacetate