一种新型双膦亚磷酸酯配体的合成及在1-己烯氢甲酰化反应中的应用

Synthesis of a New Bisphosphite Ligand and its Application in the Hydroformylation of 1-Hexene

以4,4'-二羟基二苯丙烷和2,4-二叔丁基苯酚为原料合成了一种新型双膦亚磷酸酯配体,并用此配体和Rh(acac)(CO)2原位形成的催化体系催化1-己烯的氢甲酰化反应.系统考察了反应温度、压力、P/Rh和溶剂四种反应参数对催化体系的催化性能影响.选择了最佳的反应条件,在铑浓度为0.75×10-3mol/L、P/Rh比为10、温度100℃、压力(H2/CO=1)2.0MPa的条件下反应1.0h,在溶剂甲苯中1-己烯的转化率可达到100%,醛选择性为98.7%,TOF为3498.6h-1.在相同的条件下与以三苯基膦和单膦亚磷酸三(2,4-二叔丁基苯基)酯为配体的铑催化剂相比较,以新型双膦亚磷酸酯为配体的铑催化剂的催化活性是PPh3的1.6倍,而与亚磷酸三(2,4-二叔丁基苯基)酯的催化活性相当.

A new bisphosphite ligand has been prepared from 2,2′-Di (4-hydroxyphenyl) propane and 2,4-Di-tert-butylphenol in two steps. Catalytic system composed by Rh(acac)(CO)2 and the new ligand in situ was used as homogeneous catalyst for hydroformylation of 1-hexene. The effects of reaction temperature, pressure, P/Rh and solvent on 1-hexene hydroformylation have been studied. Under the best reaction conditions of 0.75×10-3mol/L、 P/Rh=10、 100 ℃、 2.0 MPa and 1.0 h., the conversion of 1-hexene is 100%, the selectivity of aldehyde is 98.7%, TOF is 3498.6 h-1. Compared with the Triphenylphosphine and Tri(2,4-Di-tert-butylphenyl) phosphite under the same conditions, the activity is 1.6 times of PPh3 , and is similar to Tri(2,4-Di-tert-butylphenyl) phosphite.