氨基酸型两性膦配体-铑催化剂催化高碳烯烃均相氢甲酰化反应规律的研究

摘要

报道了氨基酸型两性膦配体-铑催化剂催化的高碳烯烃的均相氢甲酰化反应,系统研究了氨基酸型两性膦配体的结构、溶剂、相转移催化剂、反应温度、反应压力和反应时间对烯烃氢甲酰化反应规律性的影响.结果表明,对位有氨基酸取代的膦配体表现出较高的催化活性.在甲苯溶剂中,添加碱性相转移催化剂能够有效提高氨基酸型两性膦配体的溶解性和催化活性.反应温度、压力和反应时间对烯烃转化率和醛选择性的影响被优化,在优化的条件下烯烃的转化率达到98%以上,醛选择性达到99%.此外,氨基酸两性配体对不同的烯烃底物也表现出较好的适用性.与三苯基膦配体相比,氨基酸型两性膦配体的耐酸碱性较强,在较宽的pH值范围内均表现出较高的催化活性,表明氨基酸型两性膦配体是一类性能优异的新型配体.%Here we reported a Rh-catalysed homogeneous hydroformylation of higher olefins using the zwitterionic phosphine ligands with amino acid moieties.The effects of the structure of phosphines lig-ands,solvents,phase transfer catalysts and reaction conditions on hydroformylation were studied sys-tematically.The zwitterionic phosphines ligand showed higher catalytic activity than 4-(diphenyl-phos-phino)phenylglycine.In toluene,the addition of basic phase transfer catalyst can effectively improve the solubility and catalytic activity of zwitterionic phosphines ligands.The effects of reaction tempera-ture,pressure and reaction time on the conversion of olefin and selectivity of aldehyde were optimized. The conversion of olefins reached 98%,and aldehyde selectivity reached 99% under optimized condi-tions.In addition,the zwitterionic phosphines ligand presented good adaptability to different olefin sub-strates.Compared with the triphenyl phosphine ligand,the zwitterionic phosphine ligands showed higher catalytic activity in a wide range of pH,suggesting that zwitterionic phosphine ligands with amino acid moieties is a kind of excellent ligands.