两相体系中长链烯烃氢甲酰化反应研究——膦配体对活性和选择性的影响

Hydroformylation of High Olefin in Two-phase Catalytic System-Influence of Phosphines on the Activity and Selectivity

在温和条件下合成了两种水溶性膦配体:三(4 甲氧基3 磺酸钠苯基)膦(简称:4 MOTPPTS)和三(2 甲氧基3 磺酸钠苯基)膦(简称:2 MOTPPTS).在水/有机两相体系中,以RhCl(CO)(TPPTS)2为催化剂前体,考察了4 MOTPPTS和2 MOTPPTS作为配体时,膦/铑摩尔比、反应温度和压力变化对1 十二烯氢甲酰化反应催化性能的影响.结果表明,与三(3 磺酸钠苯基)膦(简称TPPTS)相比,在苯环上引入甲氧基后,其供电特性使催化剂对烯烃氢甲酰化反应的活性和生成醛的选择性不利,而邻位甲氧基的引入所造成的空间位阻,使2 MOTPPTS表现出较4 MOTPPTS更低的催化活性和选择性.但与相应的油溶性膦配体相比,对生成醛的选择性明显增加.

Two water-soluble ligands,sodium salt of tri(p-methoxyl-m-sulfonato phenyl)phosphine (4-MOTPPTS) and sodium salt of tri(o-methoxyl-m-sulfonato phenyl)phosphine (2-MOTPPTS) were synthesized. The catalytic properties of 4-MOTPPTS and 2-MOTPPTS were investigated for the hydroformylation of 1-dodecene in aqueous-organic two-phase catalytic system in the presence of cetyltrimethylammonium bromide (CTAB). The results indicated that the donated methoxyl of aromatic ring induced the decrease of the activity and the selectivity to the formation of aldehyde and the more steric 2-MOTPPTS showed lower activity and less selectivity than 4-MOTPPTS.However, compared with the homogeneous analogues, the selectivity for aldehydes was markedly increased in the aqueous two-phase system.