Synthesis Of Amphoteric Ligands With Amino Acid Moieties Based On Triphosphine And The Application Of 1-Octene′Hydroformation

In this study, the amphoteric ligands with amino acid moieties based on triphosphine were designed and synthesized for the hydroformation of high olefins. Derivative 1 and 2 were synthesized by nucleophilic phosphination of the sodium salt of o,p-chlorobenzoric acid with sodium phosphides Ph₂PNa under ultrasonic irradiation, and synthesized the amphoteric ligands 4,6,8 and 10. A novel catalytic system denoted homogeneous catalysis-immobilization separation was developed based on zwitterionic diphosphines ligands. This reaction system which achieves both the homogeneous reaction high catalytic activity, result reproducible and mild conditions, and solves the expensive catalyst separation and recycling problem.The relationship between structure and catalytic activities was studied by model reaction of hydroformation of 1-octene. Influences of reaction conditions such as solvent, additives, ionic liquid types and ligands structure on the catalytic activities and selectivities were examined. In the acidic conditions cycle effect is good in neutral, or alkaline conditions cycle effect; Homogeneous conditions cycle effect is good in ionic liquid two-phase system. Recycling experiments with 12 as ligand , in the case of [BMIM] BF₄ and CH₃OH as solvent, catalyst recycle 16 times response activity and selectivity,showed no obvious decline,this has not reported in relevant literature. This work enriches the variety of phosphines ligands and provides a new methology for separation and recycling of the expensive catalysts.