新型水溶性膦配体PDBPDS的制备及在氢甲酰化反应中的应用

Synthesis of a New Type Watersoluble Phosphine Ligand PDBPDS and its Application in Hydroformylation Reaction

依据量子化学理论计算 ,设计并优化了 1-苯基二苯并膦 (1- phenydibenzophosphole,简称 PDBP)磺化制备二磺化 1-苯基二苯并膦 (5 H- phenyl- 3,13- disulfonatodibenophosphole,简称 PDBPDS)的工艺 ,重点探讨了 SO3/PDBP比、反应温度、反应时间以及硼膦比对磺化产物收率的影响 .实验结果表明 ,采用 5 0 %发烟硫酸作磺化剂、SO3/ PDBP摩尔比为 3,H3BO3/ PDBP比为 5 ,在 13～ 15℃及无水无氧条件下反应 5 0 h,磺化产物收率可达 85 % .此外 ,还将所得产物用作丙烯氢甲酰化两相反应催化剂的配体 ,大大提高了催化剂的活性和产物正异比 ,且有机相中铑含量仅为 3.6× 10 - 8,有效地控制了铑流失 .实验结果证明了新型水溶性配体 PDBPDS是一个能实现均相反应多相化的、很有开发前景的配体 .

The results of semiempirical AM1 quantum chemistry calculation indicate that in the course of PDBP sulfonation, the reaction releases a large amount of heat. An improved method for PDBPDS synthesis by substituting H\-2SO\-4 with SO\-3 as reactant was suggested. The tri\|iso\|octylamine was used as an extractant. With a SO\-3/PDBP molar ratio of 3, temperature 13~15 ℃ and reation time 50 h, the yield of PDBPDS reaches 85%. PDBPDS was employed as the ligand of rhodium/phosphine cataysts, which were applied to the biphase hydroformylation reactions. The results show that the n/i ratio can be increased significantly, and the lose of Rh can be controlled effectively.