三苯基膦和亚磷酸酯类配体在双环戊二烯氢甲酰化反应中的对比研究

Comparative studies of triphenylphosphine and phosphite in the hydroformylation of dicyclopentadiene

以具有不同取代基的三苯基膦和亚磷酸酯为配体,铁磁性的钴铑双金属为催化剂,考察双环戊二烯氢甲酰化合成三环癸烷不饱和单醛的反应。结果表明,反应存在一定的诱导期,诱导期越短,反应速率越快;配体上的取代基对反应活性和产物选择性具有显著影响,吸电子取代基催化活性较高,诱导期较短,反应速率较快,但选择性较低。亚磷酸酯配体中以亚磷酸三苯酯效果最好,与三苯基膦相比,转化率和选择性均相对较低。在考察的配体中,三苯基膦作为配体,三环癸烷不饱和单醛选择性最高,达97%。

The synthesis of monoformyltricyclodecanes through the hydroformylation of dicyclopentadiene was investigated on Co-Rh/Fe3O4 catalyst by using different substituent groups of triphenylphosphine and phosphite as the ligand. The results showed that there was a certain induction time;the shorter the induc- tion time was,the faster the reaction rate was;dicyclopentadiene conversion and the selectivity to mono- formyltricyelodecanes were significantly affected by different substitute groups of the ligand. It was found that faster reaction rate, shorter induction time and lower selectivity were obtained over the electron with- drawing substituents with higher catalytic activity. Triphenyl phosphite exhibited the best performance a- mong the phosphite, but compared with triphenylphosphine, dicyclopentadiene conversion and the selectiv- ity to monoformyltricyclodecanes were lower. tion of dicyclopentadiene on Co-Rh/Fe3O4 97% was achieved. Triphenylphosphine was the best ligand for the hydroformyla- catalyst, and the selectivity to monoformyltricyclodecanes of