Base-catalyzed Formation of Enamines from β,β-Dicyanostyrene Derivatives with N-Bromosaccharin

doi:10.1007/s40242-018-8055-8

Chemical Research in Chinese Universities ›› 2018, Vol. 34 ›› Issue (5): 751-757.doi: 10.1007/s40242-018-8055-8

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Base-catalyzed Formation of Enamines from β,β-Dicyanostyrene Derivatives with N-Bromosaccharin

KANG Nan, CHEN Zhanguo

Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119, R. P. China

Received:2018-02-09 Revised:2018-03-14 Online:2018-10-01 Published:2018-05-21
Contact: CHEN Zhanguo,Email:chzhg@snnu.edu.cn E-mail:chzhg@snnu.edu.cn
Supported by:
Supported by the Natural Science Foundation of Shaanxi Province of China(No. 2009JM2011), and the Innovation Foundation of Postgraduate Cultivation of Shaanxi Normal University of China(No. 2008CXB009).

Abstract

Abstract: A new method for the synthesis of functional enamines from β,β-dicyanostyrene derivatives and N-bromosaccharin(NBSA) was developed. In the presence of Na₂CO₃, the the reaction of β,β-dicyanostyrene derivatives with NBSA can generate the corresponding enamines smoothly in a mixed solvent of dichloromethane and N,N-dimethylformamide (DMF)(volume ratio 1:1) at 50℃. The reaction of 14 kinds of β,β-dicyanostyrene derivatives with NBSA was investigated. Screened olefins afforded the corresponding enamines in good to excellent yields(up to 94%), indicating that the method has a wide adaptability for the substrate. The catalyst used is inexpensive and stable for storage. The amino groups of all products in their structures are on the α-position of products, revealing the reaction has an excellent regioselectivity. The possible pathway involving aminobromination of β,β-dicyanostyrene derivative with NBSA first and then elimination of HBr process in one pot has been proposed. The structures of all products were confirmed by ¹H NMR, ¹³C NMR and HRMS analysis.

Key words: β,β-Dicyanostyrene derivative, Functional enamine, Sodium carbonate, N-Bromosaccharin

KANG Nan, CHEN Zhanguo. Base-catalyzed Formation of Enamines from β,β-Dicyanostyrene Derivatives with N-Bromosaccharin[J]. Chemical Research in Chinese Universities, 2018, 34(5): 751-757.

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Base-catalyzed Formation of Enamines from β,β-Dicyanostyrene Derivatives with N-Bromosaccharin

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