对烷氧苯基二苯基膦的合成及其在烯烃氢甲酰化反应中的催化性能研究  

Synthesis of p-Alkoxylphenyldibenylphosphines and Their Application in Rhodium Catalyzed Hydroformylation of 1-Decene

作　　者：李诚[1] 袁茂林[1] 付海燕[1] 陈华[1] 李贤均[1] 

机构地区：[1]绿色化学与技术教育部重点实验室四川大学化学学院,四川成都610064

出　　处：《四川大学学报（工程科学版）》2006年第5期102-106,共5页Journal of Sichuan University (Engineering Science Edition)

基　　金：国家重大基础研究计划资助项目(G2000048008)

摘　　要：合成了4种不同链长的对烷氧苯基二苯基膦,研究了其与Rh(CO)2(acac)原位形成的催化剂对烯烃氢甲酰化反应的催化性能。考察了反应温度、反应压力和膦/铑比等因素对催化性能的影响。结果表明:在铑浓度为1.2×10-3mo1/L,膦/铑比为20,100℃,2.0 MPa的条件下,1-癸烯转化率可达89%以上,生成醛的正/异比达到3.8,并且随着膦配体中烷氧基碳链的增长,生成醛的正/异比呈增加的趋势。p - Alkoxylphenyldibenylphosphines, p - CH3 （ CH2 ）nOC6H4PPh2 （ n = 3, 7, 11, 15）, were synthesized from chlorodiphenylphosphine and p -alkoxyphenylmagnizium bromide, and characterized by ^1H and ^31p NMR spectroscopy. The catalytic performance of catalysts in situ formed by p - alkoxyphenyldiphenylphosphines and Rh（CO）2（acac） （ acac ： acetylacetone） was examined in the hydroformylation of 1 - decene. The influence of various parameters, such as the molar ratio of rhodium to phosphine, the reaction temperature and pressure, on the hydroformylation were investigated in the homogeneous conditions. Under the conditions of 100℃, 2.0 MPa and Rh concentration of 1.2 × 10^-3mol/L, [ P]/[ Rh] =20, the conversion of 1 -decene to undecaldehydes is about 89%, and the molar ration of normal to iso-undecaldehyde is 3.8. The selectivity of linear aldehyde increased with the increased of the length of alkyl long-chain on the benzene ring of phosphines.

关 键 词：对烷氧苯基二苯基膦 氢甲酰化反应 1-癸烯 膦配合物 

分 类 号：O623.627[理学—有机化学]