新型表面活性膦在长链烯烃氢甲酰化反应中的助催化作用

 考察了新型表面活性膦配体DPPTS(对-十二烷基苯基二苯基膦的磺酸钠盐)和OPPTS(对-辛基苯基二苯基膦的磺酸钠盐)在铑络合物催化的水/有机两相长链烯烃氢甲酰化反应中的助催化作用. 在催化烯烃氢甲酰化反应时,观察到烯烃与膦配体之间有一定的链长匹配效应; 含DPPTS的催化剂体系在低膦/铑比条件下表现出比含表面活性剂十六烷基三甲基溴化铵和水溶性配体三苯基膦三磺酸钠的催化剂体系高得多的催化活性,而且铑流失到有机相极少,仅为加入总铑量的0.8%. 这种亲水基团和磷原子处于碳链同一端的表面活性膦配体比文献报道的亲水基团和磷原子分别处于碳链两端的表面活性膦配体具有更好的助催化活性.

Cocatalytic Effect of New Surface-Active Phosphine in Long-Chain Olefin Hydroformylation

The co-catalysis properties of new surface-active phosphines DPPTS (sodium salt of sulfonated C_ 12 H_ 25 PhPPh_2 ) and OPPTS (sodium salt of sulfonated C_8H_ 17 PhPPh_2) for long-chain olefin hydroformylation in an aqueous/organic biphasic system have been investigated. The catalytic systems containing the surface-active phosphine show a clear matching relation between the length of olefin chain and hydrophobic chain of the surface-active phosphine. The catalytic system containing DPPTS exhibit stronger acceleration effect on olefin hydroformylation than the system containing surfactant CTAB (cetyltrimethyl ammonium bromide) and TPPTS (P(m-C_6H_4SO_3Na)_3) when the molar ratio of phosphine/rhodium is low. Moreover, the leaching of rhodium into the organic phase is only 0.8% of the total rhodium added. DPPTS with the hydrophilic group and P atom at the same end of the carbon chain shows better co-catalysis effect than reported phopsine with the hydrophilic group and P atom at the two ends of the carbon chain.