论文部分内容阅读
建立了一锅法由缺电子烯烃合成相应α-脱氢氨的新方法.缺电子烯烃(包括α,β-不饱和酯和α,β-不饱和酮)与对甲基苯磺酰胺/NBS在二氯甲烷中,室温下铝粉催化,首先发生双键上的氨溴加成反应,得到邻位氨基溴化合物.氨溴加成产物不经分离,再在二氯甲烷/DMF(V∶V=1∶1)的混合溶剂中,在碳酸钾/硫脲的催化下,各种邻位氨基溴的酯和邻位氨基溴的酮均能被顺利地转化成相应的α-脱氢氨.共考察了27种缺电子烯烃的反应行为,最高收率可达97%,证明该方法具有广泛的适应性.对所有产物的结构分析证明(1H NMR),所得到的脱氢氨,其氨基均处在羰基的α-位,证明该反应具有区域专一性.
A new method for synthesizing the corresponding α-dehydroamines from electron-deficient olefins was established.The one-pot method for the synthesis of the corresponding α-dehydroamines from electron-deficient olefins was studied.Electron-deficient olefins including α, β- unsaturated esters and α, β- unsaturated ketones were reacted with p-methylbenzenesulfonamide / NBS In dichloromethane, aluminum powder catalyzed at room temperature, the first occurrence of an ammonia bromide on the double bond addition reaction to obtain the adjacent amino bromine compound. Amino bromide addition product without isolation, and then in methylene chloride / DMF (V: V = 1: 1) in the mixed solvent, potassium carbonate / thiourea catalysis, various ortho-amino bromine ester and ortho-amino bromine ketone can be successfully converted into the corresponding α-dehydro ammonia A total of 27 kinds of electron-deficient olefins were investigated, with the highest yield up to 97%, which shows that the method has a wide range of adaptability.It has been proved by structural analysis of all the products (1H NMR) The amino groups are all in the alpha position of the carbonyl group, demonstrating that the reaction is regionally specific.