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A bulky phosphite‐modified rhodium catalyst for the hydroformylation of unsaturated fatty acid esters
Author(s) -
Muilwijk Koen F.,
Kamer Paul C. J.,
Leeuwen Piet W. N. M.
Publication year - 1997
Publication title -
journal of the american oil chemists' society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.512
H-Index - 117
eISSN - 1558-9331
pISSN - 0003-021X
DOI - 10.1007/s11746-997-0127-8
Subject(s) - hydroformylation , isomerization , chemistry , catalysis , toluene , rhodium , methyl oleate , triphenylphosphine , medicinal chemistry , allylic rearrangement , organic chemistry , solvent
Abstract A series of hydroformylation experiments was performed with a high‐grade and a technical‐grade‐derived methyl oleate (MO) and a rhodium catalyst modified by the bulky tris(2‐ tert ‐butyl‐4‐methylphenyl)phosphite. In the hydroformylation of pure methyl oleate, relatively high turnover numbers were obtained (400–500 mol/mol/h) under mild conditions (molar ratio MO/Rh=910, 80–100°C and 20 bar; CO/H 2 =1:1, solvent toluene), leading to about 95% conversion in 3 h. Fast isomerization occurs under these conditions to produce the trans oleate. Trans oleate reacts more slowly than cis oleate. At temperatures below 50°C, isomerization does not occur. The use of technical‐grade methyl oleate, containing 14% 9,12 diene, methyl linoleate (ML), results in lower reaction rates because dienes form stable π‐allylic intermediates, which slowly undergo hydroformylation. More severe conditions were applied to obtain higher rates. The rate varied from 50 to 400 mol/mol/h, depending on conditions (molar ratio MO/Rh=910, T=50–120°C, P = 50–80 bar; CO/H 2 =1:1–1:6, solvent, toluene). Several isomers of ML were formed during the reaction. Subsequent hydroformylation of these isomers results in a complicated mixture of products. The product mixture consists predominantly of methyl formylstearate, methyl formyloleate, methyl diformylstearate, and some yet unidentified side products. A comparison of the classic triphenylphosphine‐modified catalyst and the bulky phosphite‐modified catalyst has shown that the latter is several times more active.