四正丁基溴化铵催化的氮杂环丙烷与水合羧酸铜的开环反应  

Efficient ring-opening reactions of N-tosylaziridines with hydrous cupric carboxylate mediated by tetra-n-butyl ammonium bromide

作　　者：张万轩[1] 周洁[1] 黄巍[1] 苏莉[1] 汤从国[1] 

机构地区：[1]湖北大学化学化工学院,湖北武汉430062

出　　处：《湖北大学学报（自然科学版）》2012年第4期482-486,共5页Journal of Hubei University：Natural Science

基　　金：国家自然科学基金(20872031)资助

摘　　要：氮杂环丙烷与水合羧酸铜在溴化四丁基铵的催化下可以合成β-胺基醇酯,首先通过条件优化,分别对不同水合羧酸盐、溶剂、反应温度、季铵盐催化剂、反应物料配比对该反应的影响进行研究,得到最优条件:溶剂为1,4-二氧六环,反应条件为回流,氮杂环丙烷、一水乙酸铜、四正丁基溴化铵的摩尔比为1∶0.6∶0.2.然后在此条件下拓展不同反应底物,反应时间短,产物的产率高(85%～99%),产物的区域选择性也高(83%～95%).这种方法对于N-Ts活化的环状氮杂环丙烷,开环产物的立体结构为反式;对芳基和烷基取代的N-Ts活化的氮杂环丙烷,主要开环产物为端位开环产物.对反应条件和Cu2+的作用进行了讨论.β-amino alcohol esters could be obtained from the reactions of aziridines with hydrated cupric acetate which were catalysed by tetra-n-butyl ammonium bromide.Firstly,condition was optimized,such as using different hydration carboxylic acid salts,solvents,reaction temperatures,catalyst of quaternary ammonium salts and the ratios of reaction raw materials to the reaction.1,4-dioxane was the best solvent and the preferential molar ratio of aziridine,hydrated cupric acetate and tetrabutyl ammonium bromide was 1∶0.6∶0.2.Finally,we expanded the substrate of aziridine and hydrated cupric carboxylates for an excellent yields(85%—99%) in a short time.The regioselectivities were 83%—95% for the major products.In the case of cycloalkyl aziridines,the stereochemistry of the ring product was found to be trans-form.Alkyl N-tosyl aziridines and aryl N-tosyl aziridines both mainly underwent cleavage at the terminal carbon atom.A new convenient method for the preparation of β-amino alcohol esters was developed and the role of cation Cu2+ was discussed.

关 键 词：羧酸铜 氮杂环丙烷 β-胺基醇酯 溴化四丁基铵 开环反应 

分 类 号：O62[理学—有机化学]