光促进温和条件下溴代烷烃与甲酸甲酯的羰基化反应.pdfVIP

《化学通报》在线预览版 光促进温和条件下溴代烷烃与甲酸甲酯的羰基化反应 胡耀云 尹静梅* 高大彬 贾颖萍 周广运 崔颖娜 李慎敏 (大连大学生物有机省重点实验室 大连 116622) 摘 要 研究了光促进温和条件下，以甲酸甲酯为 C 源，非贵金属钴盐、铜盐催化的溴代烷烃的羰基化 1 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 CH 3OH，再与溴代烷烃进行羰基化反应。 关键词 光促进羰基化反应 溴代烷烃 甲酸甲酯 钴盐 铜盐 Photopromoted Carbonylation of Bromoalkanes with Methyl Formate under Ambient Conditions * Hu Yaoyun, Yin Jingmei , Gao Dabin, Jia Yingping, Zhou Guangyun, Cui Yingna, Li Shenmin (Liaoning Key Laboratory of Bio-organic Chemistry, Dalian University, Dalian 116622) Abstract The photopromoted carbonylation of bromoalkanes with methyl formate was carried out under ambient conditions catalyzed by cobalt and copper salts. The results indicated that the corresponding esters were produced. 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. Methyl formate can be decomposed into CO and CH3OH under irradiation, and then the carbonylation of bromoalkanes will proceed with the CO. Keywords Photopromoted carbonylation, Bromoalkanes, Methyl formate, C