单波长光照射下Co(OAc)_2催化溴代烃与CO的羰基化反应  

Carbonylation of Bromohydrocarbons with CO Catalyzed by Co(OAc)_2 under Single Wavelength Irradiation

作　　者：贾颖萍[1,2] 尹静梅[2] 崔颖娜[2] 李慎敏[2] 高大彬[2] 王祥生[1] 

机构地区：[1]大连理工大学精细化工国家重点实验室,大连116012 [2]大连大学生物有机辽宁省重点实验室,大连116622

出　　处：《化学通报》2011年第11期1058-1061,共4页Chemistry

摘　　要：对以Co(OAc)2为催化剂,在3种单波长(254、365、380nm)光照射下,溴代烃与CO的羰基化反应的研究结果表明,以溴代烷烃(溴代环己烷、1-溴己烷、1-溴辛烷)为底物,只有254nm的高能光对羰基化反应是有效的,碱性添加物对反应有明显的促进作用;以溴代环己烷为底物,加入NaOAc,环己基甲酸甲酯的产率可由34%提高到78%,选择性则由37%提高到78%;以溴苯为底物,添加CH3ONa后,在3种单波长光照下均可进行羰基化反应,但在能量较低的365nm和380nm光照下,反应活性很低,添加光敏剂二苯甲酮可显著提高羰基化反应的活性,如380nm光照下,苯甲酸甲酯的产率能由7%提高到79%,选择性达100%。The carbonylation of bromohydrocarbons with CO catalyzed by Co（OAc）2 was investigated under three single wavelengths（254,365,380nm） irradiation.With bromoalkanes（bromocyclohexane,1-bromohexane,1-bromooctane） as substrates,the corresponding esters could be obtained only with the high energy 254nm lamp.Furthermore,basic additives could apparently promote the reaction,e.g.the yield of methyl cyclohexanecarboxylate from bromocyclohexane was increased from 34% to 78% and the selectivity improved from 37% to 78% by addition of NaOAc.With bromobenzene as substrate,the reaction could occur in the presence of CH3ONa under above three single wavelengths irradiation.However,the activity of the reaction was very low with the 365nm and 380nm lamps.The activity of the reaction was improved dramatically by addition of sensitizer benzophenone,e.g.the yield of methyl benzoate was increased from 7% to 79% and the selectivity was achieved 100% with the 380nm lamp.

关 键 词：羰基化反应 单波长光照 溴代烃 Co(OAc)2 

分 类 号：O621.25[理学—有机化学]