COMPARATIVE STUDY OF TRIPHENYLAMINE, TRIPHENYLPHOSPHINE, TRIPHENYLARSINE, TRIPHENYLANTIMONY AND TRIPHENYLBISMUTH AS LIGANDS IN THE RHODIUM-CATALYZED HYDROFORMYLATION OF 1-DODECENE

Article abstract of DOI:10.1016/0040-4020(84)85118-2

Triphenylamine, triphenylphosphine, triphenylarsine, triphenylantimony and triphenylbismuth were evaluated on the basis of olefin to aldehyde converion, and also on the basis of the normal/iso (n/i) product ratio, as ligands in the rhodium-catalyzed hydroformylation of 1-dodecene.Two series of reactions were conducted which differed only in total reaction time (120 minutes vs 135 minutes) and in the ligand/rhodium ratio (60:1 vs 300:1).Both reactions series employed 35 grams of 1-dodecene, a 176 ppm rhodium charge, 100 psig of 1:1 H2/CO, and a reaction temperature of 90 deg C.In the 60:1 vs 330:1 reaction series, triphenylamine gave olefin conversion and n/i ratios of 2.0 percent, 2.0 vs 5.8 percent, 1.8; triphenylphosphine gave 95 percent, 4.4 vs 86.9 percent, 8.7; triphenylarsine gave 58 percent, 3.1 vs 85.8 percent, 3.5; triphenylantimony gave13.0 percent, 6.1 vs 3.5 percent, 9.1 respectively.Triphenylbismuth failed to promote hydroformylation in both reaction series.These data demonstrate that regiospecificity, as measured by the n/i product ratio, varies inversly to increased ligand basicity.