光促进温和条件下溴代烷烃与甲酸甲酯的羰基化反应

研究了光促进温和条件下,以甲酸甲酯为C1源,非贵金属钴盐、铜盐催化的溴代烷烃的羰基化反应.实验表明,在光促进下,钴盐、铜盐均可催化溴代烷烃与甲酸甲酯的羰基化反应,得到相应的羧酸甲酯.钴盐催化下,碱性添加物NaOAc对反应有很好的促进作用,直链溴代烷烃在反应中除了得到相应的正构酯外,还有少量异构酯生成;铜盐催化下,直链溴代烷烃在反应中主要生成相应的正构酯.机理研究表明,在光照下甲酸甲酯先分解为CO和CH3OH,再与溴代烷烃进行羰基化反应.

Photopromoted Carbonylation of Bromoalkanes with Methyl Formate under Ambient Conditions

The photopromoted carbonylation of bromoalkanes with methyl formate was carried out under ambient conditions catalyzed by cobalt salts or copper salts. The results indicated that the corresponding esters were obtained. Furthermore, the yield of esters could be improved greatly by adding sodium acetate with the cobalt catalysts. Except linear esters, a small amount of isomeric esters were obtained in the carbonylation of the straight chain bromoalkanes with the cobalt catalysts, while the major carbonylation products were linear esters with the copper catalysts. The studies of the reaction mechanism showed that methyl formate can be decomposed into CO and CH3OH under irradiation, and then the carbonylation of bromoalkanes will proceed with the CO.