室温离子液体反应介质中叔丁醇氢酯基化反应的研究  

Hydroesterification of tert-Butyl Alcohol in Room Temperature Ionic Liquids

作　　者：乔焜[1] 邓友全[1] 

机构地区：[1]中国科学院兰州化学物理研究所,生态与绿色化学研究发展中心,兰州730000

出　　处：《化学学报》2002年第6期996-1000,共5页Acta Chimica Sinica

摘　　要：反应温度为 10 0～ 140℃ ,CO初始压力为 2～ 6MPa条件下 ,研究了室温离子液体与过渡金属三苯基膦配合物构成的催化反应体系中 ,叔丁醇与乙醇的氢酯基化反应 .同有机溶剂作为反应介质相比 ,室温离子液体中具有更好的催化活性 ,并且叔丁醇可经羰化反应直接生成特戊酸乙酯 ,产物与催化体系不溶 ,可以容易地实现分离 .详细考察了金属配合物、离子液体、温度。Chloroaluminate ionic liquids consisted of anhydrous AlCl 3 with 1 alkylpyridinium or 1 methyl 3 alkylimidazolium quaternary ammonium salts (QAS), such as 1 methyl 3 ethylimidazolium bromide, 1 methyl 3 butylimidazolium chloride, 1 butylpyridinium chloride and trimethylamine hydrochloride, are used as reaction media and catalysts for etherification of tert butanol (TBA) with methanol, ethanol, propanol, butanol or pentanol. In a typical experiment, the chloroaluminate ionic liquid with n (AlCl 3) =0 01 mol, n (AlCl 3) / n (QAS) =2～0 5, n (TBA) =0 05 mol and n (ROH) / n (TBA) =1 2～1 5 were successively added into a stainless autoclave with magic stirring. Kept the reaction at 80～140 ℃ for 6～12 h, the higher conversion and selectivity were achieved, especially in Lewis neutral or basic chloroaluminate ionic liquid. However, the selectivity for by products, including tert butyl chloride and dimer of tert butylene, was relative higher in Lewis acidic chloroaluminate ionic liquid owing to its sensitivity to water, one of the products of etherification of tert butanol. Since tert butyl ether is immiscible with Lewis neutral or basic chloroaluminate ionic liquid, the product can be easily separated from ionic liquid by decantation.

关 键 词：室温离子液体 反应介质 叔丁醇 氢酯基化反应 催化羰化 戊酸乙酯 催化剂 乙醇 过渡金属三苯基膦配合物 

分 类 号：O621.25[理学—有机化学]