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

作　　者：李娜娜[1,2] 马昱博[1] 沈鑫权[1,2] 高志贤[1,3] 吾满江.艾力 

机构地区：[1]中国科学院新疆理化技术研究所精细化工工程中心,新疆乌鲁木齐830011 [2]中国科学院大学,北京100049 [3]中国科学院山西煤炭化学研究所,山西太原030001

出　　处：《工业催化》2013年第8期66-69,共4页Industrial Catalysis

基　　金：国家基金委-新疆联合基金重点项目(U1139302);中国科学院西部之光项目(XBBS201114);乌鲁木齐市科技局重点项目(Y121120006)

摘　　要：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

关 键 词：有机合成化学 双环戊二烯 三环癸烷不饱和单醛 氢甲酰化 三苯基膦 亚磷酸酯 诱导期 

分 类 号：O621.256.1[理学—有机化学] O643.36[理学—化学]