Jimenez-Rodriguez Cristina, Eastham Graham R, Cole-Hamilton David J
School of Chemistry, University of St. Andrews, St. Andrews, Fife, UK KY16 9ST.
Dalton Trans. 2005 May 21(10):1826-30. doi: 10.1039/b501868d. Epub 2005 Apr 25.
A catalyst system based on palladium-1,2-bis-(di-tert-butylphosphinomethyl)benzene (BDTBPMB) shows good activity for the methoxycarbonylation of strongly activated aryl chlorides, like 4-chloromethylbenzoate or 4-chlorocyanobenzene. Surprisingly, the use of less activated aryl chlorides, like 4-chloroacetophenone, leads to the formation of dimethyl terephthalate amongst other products arising from organic reactions of methoxide ion and/or CO. Less nucleophilic alcohols such as 2,2,2-trifluoroethanol promote the formation of carbonylation products even from 4-chloroacetophenone and chlorobenzene. Labelling studies involving CD3OH, CD3OD or 13CO give information on the origin of many of the products.
一种基于钯-1,2-双（二叔丁基膦甲基）苯（BDTBPMB）的催化体系对强活化芳基氯（如4-氯甲基苯甲酸酯或4-氯氰基苯）的甲氧羰基化反应表现出良好的活性。令人惊讶的是，使用活性较低的芳基氯（如4-氯苯乙酮）会导致在甲醇根离子和/或CO的有机反应产生的其他产物中生成对苯二甲酸二甲酯。亲核性较弱的醇（如2,2,2-三氟乙醇）甚至能促进4-氯苯乙酮和氯苯生成羰基化产物。涉及CD3OH、CD3OD或13CO的标记研究为许多产物的来源提供了信息。
