β-硝基苯乙烯衍生物与丙烯酰胺及N-溴代丁二酰亚胺的区域专一性氨溴加成反应  

Regiospecific Aminobromination of β-Nitrostyrene Derivatives with Acrylamide and N-Bromobutanimide

作　　者：杜曼飞 侯丹[1] 惠文萍 陈战国[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》2016年第5期902-911,共10页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20572066);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：以β-硝基苯乙烯衍生物为底物,丙烯酰胺和N-溴代丁二酰亚胺(NBS)为氮源和卤素源,建立了碳-碳双键上的选择性氨溴加成反应新体系.以二氯甲烷为溶剂,在没有惰性气体保护及乙醇钠促进下,β-硝基苯乙烯衍生物与丙烯酰胺和NBS于室温反应即可高收率地获得α-氨基-β,β-二溴加成产物,最高收率达83%;以甲醇为溶剂,在无水碳酸钠作用下,β-甲基-β-硝基苯乙烯衍生物也可高收率地获得相应的邻位氨溴加成产物,最高收率达97%.共考察了25种不同结构β-硝基苯乙烯衍生物的氨溴加成反应,结果表明,该反应具有广泛的适应性.采用核磁共振波谱及质谱表征了产物的结构,并提出了可能的反应机理.A new protocol for the high regioselective aminobromination of β-nitrostyrene derivatives with acrylamide and N-Bromobutanimide（ NBS） as nitrogen/bromine sources was developed. β-Nitrostyrene derivatives reacted with acrylamide and NBS promoted by CH_3CH_2 ONa at room temperature（ without the protection of an inert gaseous atmosphere） in CH_2Cl_2,offered vicinal haloamine products in good yields（ up to 83%）. For the β-methyl-β-nitrostyrene,the good yields（ up to 98%） were also achieved in CH_3 OH promoted by Na_2CO_3.Although the strong electron-donating substituents（ e.g.,OCH_3） on the 4-position of benzene ring could deactivated the reaction activity of β-nitrostyrenederi-vetives,the vicinal haloamines were also afforded as the sole addition product. Whereas strong electron-withdrawing substituents（ e.g.,NO_2） could activated reaction activity remarkably and the vicinal haloamines were afforded as the sole addition product,too. The result revealed that the addition reaction has a nucleophilic addition feature. The aminobromination of 25 examples of β-nitrostyrenes were investigated and the structure of all products were confirmed by the corresponding nuclear magnetic resonance（ NMR） spectra and high resolution mass spectrometer（ HRMS）. A possible mechanism involving a nucleophilic conjugate addition was proposed.

关 键 词：氨溴加成反应 β-硝基苯乙烯 区域专一性 丙烯酰胺 N-溴代丁二酰亚胺 

分 类 号：O626.3[理学—有机化学]