Hydrogenation of methyl sorbate and soybean esters with polymer-bound metal catalysts

New polymer-bound hydrogenation catalysts were made by complexing PdCl₂, RhCl₃·3H₂O, or NiCl₂ with anthranilic acid anchored to chloromethylated polystyrene. The Pd(II) and Ni(II) polymers were reduced to the corresponding Pd(O) and Ni(O) catalysts with NaBH₄. In the hydrogenation of methyl sorbate, these polymer catalysts were highly selective for the formation of methyl 2-hexenoate. The diene to monoene selectivity decreased in the order: Pd(II), Pd(O), Rh(I), Ni(II), Ni(O). Kinetic studies support 1,2-reduction of the Δ4 double bond of sorbate as the main path of hydrogenation. In the hydrogenation of soybean esters, the Pd(II) polymer catalysts proved superior because they were more active than the Ni(II) polymers and produced lesstrans unsaturation than the Rh(I) polymers. Hydrogenation with Pd(II) polymers at 50~100 C and 50 to 100 psi H₂ decreased the linolenate content below 3% and increasedtrans unsaturation to 10~26%. The linolenate to linoleate selectivity ranged from 1.6 to 3.2. Reaction parameters were analyzed statistically to optimize hydrogenation. Recycling through 2 or 3 hydrogenations of soybean esters was demonstrated with the Pd(II) polymers. In comparison with commercial Pd-on-alumina, the Pd(II) polymers were less active and as selective in the hydrogenation of soybean esters but more selective in the hydrogenation of methyl sorbate. Presented at ISF-AOCS Meeting, New York, April 1980.