Oleic acid methyl ester systems

Johnson-Matthey Co. has reported that oleic acid methyl ester or linoleic acid methyl ester can be hydroformylated in micellar media using a water-soluble rhodium complex of monocarboxylated triphenylphosphine 45 as catalyst. As a further example, polyunsaturated linolenic acid methyl ester can be hydroformylated to the triformyl derivative with a selectivity of 55% with a Rh/TPPTS catalytic system in the presence of CTAB (Scheme 1.23). ... 

Figure 10.4 Phase diagrams of the systems h O/NaCI-rape oleic acid methyl ester/suet-Lutensol AP9 at <(> = 0.50 and e = 0.10. The parameter 0 corresponds to the mass fraction of suet in the mixture of suet and rape oleic acid methyl ester. With increasing 0, the phase behaviour is shifted to higher temperatures and surfactant mass fractions. Because of the dominance of the Lc,-phase a phase diagram at 0 = 1.00 could not be obtained.

Nagesha et al. [71] evaluated the selectivity of membranes with dense silica and PI as the active layer and support, respectively, on the permeation of tocopherols. They used samples of deodorized distillate of soybean oil (DDOS), diluted or not in hexane and DDOS oil ester, without dilution. For comparison, model systems consisting of mixtures of oleic acid and tocopherols in different proportions (80 20 and 50 50), diluted or not in hexane, were selected. In a standard model, (free of hexane) was added to a mixture of fatty acids methyl esters (FAMEs) from soybean oil and tocopherols (90 10). Experiments were conducted on a pressurized filtration unit with nitrogen at 30 bar, 30 C, and 800 rpm. The study revealed that preferential permeation of tocopherols in relation to other constituents of low molecular weight (fatty acids and FAMEs) occurs. The selectivity of the membrane to tocopherols increased with the esterifled DDOS. 

Unsaturated fatty acid esters and oils are very promising and cheap feedstocks for metathesis, which makes the metathesis reaction of interest for the oleochemical industry. The first successful metathesis conversion in this area was the selective transformation of the methyl ester of oleic acid (methyl oleate, methyl cw-9-octadecenoate), a readily accessible unsaturated ester, into equimolar amounts of 9-octadecene and dimethyl 9-octadecene-l,18-dioate, equation (1), using 1-2 mol% of a WCl6/(CH3)4Sn catalyst system at 70°C [3]. 

Anyway, it is well known that micellar effects are common in hydroformylation conducted in all varieties of aqueous systems. The addition of surfactants often helps the reactions in biphasic media, possibly due to solubilization of hydrophobic reagents in micelles, which thus function like cooperative phase-transfer agents. For example, the hydroformylation of unsaturated fats or methyl esters of unsaturated long-chain natural fatty acids (oleic, linolenic acids) can be successfully done using biphasic tech-... 

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