Dicyclopentadiene Hydroformylation in an Aqueous/Organic Two Phase System in the Presence of a Cationic Surfactant

Abstract

Dicyclopentadiene (DCPD) hydroformylation catalyzed by the water soluble rhodium complex RhCl(CO)(TPPTS) 2 (TPPTS: P(m-C 6 H 4 SO 3 Na) 3 ) was studied in an aqueous/organic two phase system containing a cationic surfactant. The effects of various reaction parameters such as reaction temperature, catalyst concentration, water soluble phosphine TPPTS or TPPDS (C 6 H 5 P(m-C 6 H 4 SO 3 Na) 2 ), and surfactant structure were examined. The catalytic activity was better with the ligand TPPTS than with TPPDS. The reaction was accelerated by the addition of the cationic surfactant C 16 H 33 N(CH 3 ) 2 C n H 2 n +1 Br( n = 1, 8, 12, 16) but the accelerating effect was attenuated with an increase of the n value. In the presence of the surfactant, the DCPD conversion increased initially and then decreased as the rhodium concentration increased in the range of 0.05–5.00 mmol/L. The catalyst containing aqueous phase was reused four times without significant decrease in activity and regioselectivity. ： 研究了在阳离子表面活性剂存在下水/有机两相中水溶性铑配合物 RhCl(CO)(TPPTS) 2 (TPPTS: P(m-C 6 H 4 SO 3 Na) 3 ) 催化双环戊二烯氢甲酰化反应, 考察了反应温度、催化剂浓度、不同水溶性膦配体 TPPTS 和 TPPDS (C 6 H 5 P(m-C 6 H 4 SO 3 Na) 2 ), 以及表面活性剂结构对催化反应的影响. 结果表明, 配体 TPPTS 比 TPPDS 表现出更好的助催化效果; 阳离子表面活性剂 C 16 H 33 N(CH 3 ) 2 C n H 2 n +1 Br ( n = 1, 8, 12, 16) 的加入可大大加速反应, 但加速作用随着其中 C n H 2 n +1 Br ( n = 1, 8, 12, 16) 链长的增加而减弱; 在阳离子表面活性剂 (0.05-5.00 mmol/L) 存在下, 双环戊二烯的转化率随表面活性剂浓度的增加先增加后降低. 含催化剂的水相循环使用 4 次后, 催化活性和区域选择性没有明显下降. Catalysis system composed of RhCl(CO)(TPPTS) 2 -TPPTS and a cationic surfactant showed good catalytic activity for dicyclopentadiene hydroformylation