三苯基膦及其衍生物在双环戊二烯氢甲酰化反应中的配体效应研究  

Ligand effects of triphenylphosphine and its derivatives on hydroformylation of dicyclopentadiene

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

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830026 [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：《天然气化工—C1化学与化工》2013年第6期34-37,共4页Natural Gas Chemical Industry

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：以三苯基膦及其衍生物作为配体在双环戊二烯(DCPD)氢甲酰化合成三环癸烷不饱和单醛和三环癸烷二醛的配体效应进行了探索研究。结果表明对于三环癸烷不饱和单醛的合成,配体上的取代基对催化活性和目标产物的选择性有显著影响,吸电子取代基会提高催化活性,加快反应速率,但选择性有所降低,斥电子取代基则会降低反应速率;从催化活性和目标产物选择性综合考虑,三苯基膦作为配体催化效果最好。两步合成法比一步合成法更有利于双环戊二烯成醛,醛选择性可达99%以上。采用两步合成法,以三苯基膦为配体可获得达60%的较高二醛选择性,其它两种配体的二醛选择性则比一步合成法差。The ligand effects of triphenylphosphine and its derivatives in the synthesis of monoformyltricyclo[5.2.1.02,6]dec-3- ene （MI;TD） and diformyltricyclodecane by hydroformylation of dicyclopentadiene （DCPD） were studied. The results showed that the substituents on the ligand have significant influences on the catalytic activity and the selectivity to MTD. The electron withdrawing substituent increased catalytic activity, but decreased the selectivity slightly, and the electron-donating substituent decreased catalytic activity. Considering both of catalytic activity and target product selectivity, tfiphenylphosphine may be the best choice. Comparing with the one-step synthesis, the two-step synthesis could increase the total selectivity of MFTD and DFTD, which could be over 99%. In the two-step synthesis, triphenylphosphine ligand obtained a high DFTD selectivity of up to 60%, however the other two ligands still gave lower DFTD selectivitie.

关 键 词：双环戊二烯 三环癸烷不饱和单醛 三环癸烷二醛 氢甲酰化 三苯基膦及其衍生物 配体效应 

分 类 号：TQ231.22[化学工程—有机化工]