β,β-二氰基苯乙烯/酰胺/N-溴代丁二酰亚胺三组分合成相应的邻溴代胺  

Synthesis of Vicinal Bromoamine Compounds via Three Components Reaction of β,β-Dicyanostyrene/Amide/N-Bromo-succinimide

作　　者：康梦 惠文萍 侯丹[1] 陈战国[1] 

机构地区：[1]应用表面与胶体化学教育部重点实验室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

出　　处：《有机化学》2017年第11期2962-2971,共10页Chinese Journal of Organic Chemistry

基　　金：陕西省自然科学基金(No.2009JM2011);陕西师范大学研究生创新基金(No.2008CXB009)资助项目~~

摘　　要：作为重要的双官能团化合物,合成新的邻溴代胺衍生物以及发展其新的合成方法具有重要意义,为此本研究建立了由β,β-二氰基苯乙烯衍生物、酰胺、N-溴代丁二酰亚胺(NBS)三组分一锅法合成相应邻溴代胺的新方法.在K2CO3催化下,β,β-二氰基苯乙烯衍生物与酰胺、NBS在二氯甲烷中、室温下反应(无需惰性气体保护),可高收率地得到邻溴代胺化合物(最高收率可达93%).考察了13种不同结构的β,β-二氰基苯乙烯衍生物与7种酰胺(丙烯酰胺、乙酰胺、戊酰胺、异丁酰胺、苯甲酰胺、对硝基苯甲酰胺、乌来糖)的反应,说明该方法不仅对β,β-二氰基苯乙烯具有广泛的适应性,也适用于不同类型的酰胺.所有产物结构均经核磁共振波谱、红外光谱及质谱确证,并提出了可能的反应机理.Vicinal bromoamine derivative belongs to an important class of difunctionalization compounds.New synthetic method and new vicinal bromoamine derivatives are eagerly desired.Thus,a new one-pot protocol for the synthesis of vicinal bromoamines from β,β-dicyanostyrene derivatives/amides/N-bromo-succinimide was developed.In the presence of anhydrous K2 CO3,β,β-dicyanostyrenes reacted smoothly with amides and N-bromo-succinimide（NBS） to generate the vicinal bromoamine compounds in good to excellent yield（up to 93% yield） at room temperature without the protection of inert gas in CH2 Cl2.13 different structural β,β-dicyanostyrene derivatives reacted with 7 different structural amides（acrylamide,acetamide,valeramide,isobutyramide,benzamide,4-nitrobenzamide,ethylurethanm） and NBS have been investigated in this work.The results indicated that the method is not only widely subjected to β,β-dicyanostyrene,but also suitable for the different type of amide.The structures of all the products were confirmed by their nuclear magnetic resonance spectroscopy（NMR）,infrared spectra（IR） and high resolution mass spectrometry（HRMS）,and the possible reaction mechanism was proposed.

关 键 词：邻溴代胺 β β-二氰基苯乙烯 酰胺 N-溴代丁二酰亚胺 

分 类 号：O623.733[理学—有机化学]