考察了不同取代基团在三苯基膦(PPh₃)中一个苯环的邻位或者对位上进行单取代后配体的1-己烯氢甲酰化反应性能。结果表明,邻位基团会显著增强膦配体的位阻效应,一方面大概率弱化了催化活性,另一方面则提升了氢甲酰化产物醛的区域选择性;对位取代的基团在不影响活性的基础上会大概率对配体的化学选择性(主产物醛的选择性)有正向的提升。综合评价表明,最好的配体是对位醛基单取代的PPh₃配体,转化率为99%,醛选择性高达80%,正异比达到2.48,对位基团的存在优化了配体的电子和空间性质。

The performance of the 1-hexene hydroformylation reaction is investigated over the ligands that are formed through monosubstitution of different substituent groups at the ortho or para position of one of the benzene rings of triphenylphosphine.The results show that ortho-substituted group significantly enhances the steric effect of phosphine ligand,which on the one hand weakens the catalytic activity and on the other hand enhances the regioselectivity of the hydroformylation product aldehyde.Para-substituted group positively enhances the chemoselectivity of the ligand (selectivity of main product aldehyde) without affecting the activity.It is identified through overall evaluation that the best ligand is the triphenylphosphine ligand with monosubstituted aldehyde group at the para position,which leads to a 99% of conversion,an 80% of aldehyde selectivity and a 2.48 ratio of linear to branch.It is believed that the presence of group at para position optimizes the electronic and steric properties of the ligand.

卢锦龙(1997-),男,硕士生,研究方向为有机催化,ljl06168@126.com