Hydroformylation of Methyl Linoleate and Linolenate with Rhodium-Triphenylphosphine Catalyst

Abstract

Hydroformylation of methyl linoleate and linolenate with a rhodium-triphenylphosphine catalyst yields 1,4diformyl esters as major products and 1,3-diformyl esters as minor products. Unsaturated and saturated monoformyl esters are also produced from both substrates and triformyl esters from methyl linolenate. Conjugated methyl linoleate produces mainly monoformyl esters, whereas methyl c/s-9,c/s-l 5-octadecadienoate produces diformyl esters. The mechanism postulated for dihydroformylation involves cyclic unsaturated acyl-rhodium-triphenylphosphine complexes controlling the position of the second formyl group. These intermediates are also implicated in double-bond hydrogenation and isomerization which accompany dihydroformylation. The polyformyl ester products formed contrast with the monoformyl ester products obtained when cobalt carbonyl catalysts are used.

Chemical transformations of renewable lubricant feedstocks

“…Hydroformylation of unsaturated fatty compounds leads to the introduction of an aldehyde group in the FA chains with formation of fatty formyl esters. Frankel and coworkers [37,40,41] [212]. Hydroformylation of methyl oleate forms approximately 60% of the isomeric mixture of formyl stearic acid methyl esters, but also the undesired hydrogenation byproduct methyl stearate.…”

Hidroformilação do oleato de metila catalisada por complexos de ródio

“…6 A reação produziu 1,4-diformil ésteres como produtos majoritários e 1,3-diformil ésteres como produtos minoritários. Monoformil ésteres insaturados e saturados também foram produzidos para ambos os substratos, bem como triformil ésteres para o linolenato de metila.…”

“…5 O mesmo autor relatou a hidroformilação do linoleato e do linolenato de metila com catalisador de ródio (5% Rh suportado em Al 2 O 3 ) na presença de trifenilfosfina. 6 A reação produziu 1,4-diformil ésteres como produtos majoritários e 1,3-diformil ésteres como produtos minoritários. Monoformil ésteres insaturados e saturados também foram produzidos para ambos os substratos, bem como triformil ésteres para o linolenato de metila.…”

Kinetics of the hydroformylation of soybean oil by ligand‐modified homogeneous rhodium catalysis

“…Hydroformylation, commonly known as the oxo process, is an environmentally friendly process by which those TG can be converted to polyaldehydes (1-4). Whereas the kinetics and mechanism of simple olefin hydroformylation over phosphine-or phosphitemodified rhodium catalysts have been reported (5-16), the effects of reaction parameters on the reaction rates of unsaturated FA esters, TG, or vegetable oils have not been extensively investigated (17)(18)(19).We now report the results of a kinetic investigation of the conversion of soybean oil to polyaldehydes by the hydroformylation reaction using homogeneous rhodium catalysis under the reaction conditions relevant to industrial processes. Scheme 1 shows the hydroformulations of a model TG ester having one (oleic) and two (linoleic) double bonds.…”

“…Hydroformylation, commonly known as the oxo process, is an environmentally friendly process by which those TG can be converted to polyaldehydes (1)(2)(3)(4). Whereas the kinetics and mechanism of simple olefin hydroformylation over phosphine-or phosphitemodified rhodium catalysts have been reported (5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16), the effects of reaction parameters on the reaction rates of unsaturated FA esters, TG, or vegetable oils have not been extensively investigated (17)(18)(19).…”