功能化烯胺的合成(Ⅳ): 醋酸钠快速促进β, β-二氰基苯乙烯衍生物与NBS反应转变成相应的烯胺

doi:10.7503/cjcu20140218

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (11): 2360.doi: 10.7503/cjcu20140218

功能化烯胺的合成(Ⅳ): 醋酸钠快速促进β, β-二氰基苯乙烯衍生物与NBS反应转变成相应的烯胺

陈战国(), 刘德娥, 李文丽, 刘亚丽

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:2014-03-17 出版日期:2014-11-10 发布日期:2014-10-15
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研究. E-mail:chzhg@snnu.edu.cn
基金资助:
中央高校基本科研业务费专项资金(批准号: GK261001095)、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

Synthesis of Functionalized Enamines(Ⅳ): β,β-Dicyanostyrene Derivatives Reacted with NBS Converted into Corresponding Enamines Promoted by NaOAc^†

CHEN Zhanguo^*(), LIU De’e, LI Wenli, LIU Yali

Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119, China

Received:2014-03-17 Online:2014-11-10 Published:2014-10-15
Contact: CHEN Zhanguo E-mail:chzhg@snnu.edu.cn
Supported by:
† Supported by the Fundamental Research Funds for the Central Universities, China(No.GK261001095), the Natural Science Foundation of Shaanxi Province, China(No.2009JM2011) and the Innovation Foundation of Postgraduate Cultivation of Shaanxi Normal University, China(No.2008CXB009)

摘要/Abstract

摘要：

建立了由缺电子烯烃(β,β-二氰基苯乙烯衍生物)与N-溴代丁二酰亚胺(NBS)反应快速转变成功能化烯胺的新方法. 缺电子烯烃在N,N-二甲基酰胺(DMF)溶剂中, 在NaOAc促进下与NBS反应, 可快速转变成相应的烯胺. 在优化的条件下, 考察了12种β,β-二氰基苯乙烯衍生物与NBS的反应情况, 各种β,β-二氰基苯乙烯衍生物均能转变成相应的烯胺, 证明该方法具有广泛的适应性. 该方法操作简单, 反应条件温和, 反应收率高(最高收率可达98%). 所用催化剂易得、稳定, 价格低廉, 并且反应具有高度的区域选择性, 为合成功能化烯胺提供了一个有效途径. 所有产物结构均经过核磁共振波谱和高分辨率质谱确证.

关键词: β,β-二氰基苯乙烯衍生物, 功能化烯胺, 醋酸钠

Abstract:

An easy and efficient new method for the expeditious synthesis of functionalized enamines from β,β-dicyanostyrene derivatives reacted with N-bromosuccinimide(NBS) was developed. The β,β-dicyanostyrene derivatives were smoothly converted into corresponding functionalized enamines promoted by NaOAc(200%, molar fraction) in DMF at room temperature in good to excellent yield within 80 min. This new method has many advantages such as mild conditions, easy handling, nearly quantitative yields 12 substrates with different structures were investigated. The results indicated that the protocol has applicability in a large scope of the electron-deficient olefins. A possible addition-elimination pathway was proposed and it explained well the full regiospecificity of the reaction. The structures of all products were confirmed by their ¹H NMR, ¹³C NMR and HRMS analysis.

Key words: β,β-Dicyanostyrene derivative, Functionalized enamine, NaOAc

中图分类号:

O626.3

TrendMD:

陈战国, 刘德娥, 李文丽, 刘亚丽. 功能化烯胺的合成(Ⅳ): 醋酸钠快速促进β, β-二氰基苯乙烯衍生物与NBS反应转变成相应的烯胺. 高等学校化学学报, 2014, 35(11): 2360.

CHEN Zhanguo, LIU De’e, LI Wenli, LIU Yali. Synthesis of Functionalized Enamines(Ⅳ): β,β-Dicyanostyrene Derivatives Reacted with NBS Converted into Corresponding Enamines Promoted by NaOAc^†. Chem. J. Chinese Universities, 2014, 35(11): 2360.

图/表 6

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Compd.	m.p./℃	Compd.	m.p./℃
1a	167—168 (167—168^[24])	1g	115—116.8 (110—112^[25])
1b	128.3 (125—127^[25])	1h	93—94 (102—104^[25])
1c	164.3—164.7 (166—168^[26])	1i	93.4—94.2 (85^[28], 100^[29] )
1d	152—153 (153—154^[24])	1j	143.2—114.5 (140^[30])
1e	132.8—133.8 (132—134^[24])	1k	167.2—167.7 (168—169^[31])
1f	82.5—83.6 (82—84^[27])	1l	69.8—71 (70—72^[25])

Compd.	m.p./℃	Compd.	m.p./℃
1a	167—168 (167—168^[24])	1g	115—116.8 (110—112^[25])
1b	128.3 (125—127^[25])	1h	93—94 (102—104^[25])
1c	164.3—164.7 (166—168^[26])	1i	93.4—94.2 (85^[28], 100^[29] )
1d	152—153 (153—154^[24])	1j	143.2—114.5 (140^[30])
1e	132.8—133.8 (132—134^[24])	1k	167.2—167.7 (168—169^[31])
1f	82.5—83.6 (82—84^[27])	1l	69.8—71 (70—72^[25])

功能化烯胺的合成(Ⅳ): 醋酸钠快速促进β, β-二氰基苯乙烯衍生物与NBS反应转变成相应的烯胺

Synthesis of Functionalized Enamines(Ⅳ): β,β-Dicyanostyrene Derivatives Reacted with NBS Converted into Corresponding Enamines Promoted by NaOAc^†

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