有机胺功能化离子液体中离子型铑(Ⅲ)配合物催化的1-辛烯两相氢甲酰化反应  

Biphasic Hydroformylation of 1-Octene Catalyzed by Ionic Rh( Ⅲ)-complex in the Presence of Tertiary Amine Functionalized Ionic Liquid

作　　者：石丁夫[1] 谭忱 王鹏[1] 李永琪[1] 陈胜洁[1] 刘晔[1] 

机构地区：[1]华东师范大学化学与分子工程学院,上海市绿色化学与化工过程绿色化重点实验室,上海200062

出　　处：《高等学校化学学报》2015年第8期1553-1558,共6页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21273077,21076083)资助~~

摘　　要：考察了离子型+3价铑配合物1a和2a作为催化剂前体在1-辛烯氢甲酰化反应中的催化行为.实验结果表明,在无助剂存在下,配合物1a和2a表现出较差的催化性能,而廉价低毒的有机叔胺助剂如三乙胺或N-甲基哌啶可以显著提升配合物1a和2a的催化性能,可获得800 h-1以上的转化频率(TOF).当以哌啶功能化离子液体[PEmim]BF4兼作助剂和溶剂时,不仅可以促进配合物1a和2a对氢甲酰化反应的活性和选择性,还可实现"离子液体-有机"两相氢甲酰化反应,使得锁定在[PEmim]BF4离子液体相中的配合物1a(或2a)催化剂得以简单两相分离和回收循环使用,但在5次循环使用过程中锁定在[PEmim]BF4中的催化剂存在向有机相流失和失活的问题,导致产物壬醛的收率逐渐下降.The ionic Rh（ Ⅲ）-complexes 1a and 2a exhibited poor catalytic performance for hydroformylation of 1-octene without the presence of any auxiliary additive. The involvement of cheap and low-toxic tertiary amines such as Et3 N or N-methylpiperidine could dramatically boost the catalytic performance of compounds 1a and 2a up to turnover frequency（ TOF） of 800 h^-1. When piperidinyl-functionalized ionic liquid of [PEmim]BF4was dually used as the additive and the solvent,not only the positive roles of N-methylpiperidine in spurring up the activity of compounds 1a and 2a were embodied,but also the easy recovery and recycling of compounds 1a（ or 2a） in [PEmim]BF4were fulfilled in biphasic hydroformylation. The TOFs of compounds 1a and2 a in [PEmim]BF4were gradually decreased in the course of the recycling uses due to the leaching and deactivation of the catalysts.

关 键 词：铑配合物 功能化离子液体 氢甲酰化 1-辛烯 叔胺 

分 类 号：O643.32[理学—物理化学]