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

作　　者：陈战国[1] 刘德娥 李文丽[1] 刘亚丽[1] 

机构地区：[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

出　　处：《高等学校化学学报》2014年第11期2360-2365,共6页Chemical Journal of Chinese Universities

基　　金：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);陕西师范大学研究生创新基金(批准号:2008CXB009)资助~~

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.An easy and efficient new method for the expeditious synthesis of functionalized enamines fromβ,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 their1 H NMR,13 C NMR and HRMS analysis.

关 键 词：β β-二氰基苯乙烯衍生物 功能化烯胺 醋酸钠 

分 类 号：O626.3[理学—有机化学]