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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 results of the carbonylation of brominated hydrocarbons with CO under the irradiation of three kinds of single-wavelength (254,365,380 nm) light with Co (OAc) 2 as catalyst show that the brominated hydrocarbons (brominated cyclohexane , 1-bromohexane, 1-bromooctane) as the substrate, only 254nm high energy light carbonylation reaction is effective, alkaline additives significantly promote the reaction; brominated cyclohexane as the bottom , The yield of methyl cyclohexyl carboxylate increased from 34% to 78% and the selectivity increased from 37% to 78% with the addition of NaOAc. After CH3ONa was added with bromobenzene as substrate, Can be carbonylation reaction, but at lower energy 365nm and 380nm light, the reaction activity is very low, the addition of photosensitizer benzophenone can significantly increase the activity of the carbonylation reaction, such as 380nm light irradiation, methyl benzoate The yield can be increased from 7% to 79% with a selectivity of 100%.