铑-膦配位催化烯烃氢甲酰化反应研究

摘要

本文研究了由Rh2(CO)4Cl2分别与两种膦配体4-正丁苯基二苯基膦(1)和4-正辛苯基二苯基膦(2)形成的原位催化剂体系对烯烃氢甲酰化反应的催化性能。对影响反应的各种因素，如P/Rh物质的量比、反应温度、反应压力，不同烯烃等的影响作了探讨。结果表明，配体1、2与Rh2(CO)4Cl2形成的原位催化剂体系的催化活性与选择性均高于结构相似的PPh3，在相同的条件下，不同烯烃的氢甲酰化反应活性依直链烯烃＞苯乙烯＞直链内烯＞环己烯的顺序递增。%This paper studied the catalytic propesties of the catalysts in situformed by Rh2(CO)4Cl2 and 4-butylphenyl-diphenylphosphine (1) and/or 4-octyl phenyl-diphenylphosphine (2) for the hydroformylation of 1-hexene.The influence of various parameters,such as the molar ratio of rhodium to phosphine,the reaction temperature and pressure on the hydroformylation were investigated.As ligand,phosphine 1 and 2 exhibited higher activity and selectivity than triphenylphosphine.This may be attributed to the electronic and steric effects of alkyl group on the aromatic ring.When using Rh2(CO)4Cl2 as catalytic precursor and 1 as ligand,the rate of hydroformylation of various olefins decreased in following order:terminal olefin＞styrene＞internal olefin＞Cyclohexene.