Methyl oleate selective hydrogenation

Albright, L. and Wisniak, J., J. Amer. Oil Chem. Soc. 39, 14, 1962. Selectivity and Isomerization during Partial hydrogenation of cottonsead oil and methyl oleate Effect of operating variables. ... 

To elucidate the mechanism of homogeneous hydrogenation catalyzed by Fe(CO)s, kinetic studies were carried out with mixtures of unsaturated fatty esters containing a radioactive label. A C-labeled methyl octadecadienoate-Fe(CO)3 complex was prepared to serve as a catalytic intermediate. Hydrogenation of methyl oleate (m-9-octa-decenoate) and palmitoleate (cis-9-hexadecenoate) and of their mixtures with methyl linoleate was also studied to determine the selectivity of this system, the function of the diene-Fe(CO)3 complex, and the mechanism of homogeneous isomerization. Mixtures of reaction intermediates with a label helped achieve unique simulation of the kinetic data with an analog computer. 

The Fe(CO)4 intermediates of types III and VIII in Scheme IV explain the direct reduction paths evidenced in the hydrogenation of mono- and diunsaturated fatty esters. Competition between monoene and diene hydrogenation can be related to the stability of the Fe(CO)3-and Fe(CO)4-complexes. At a low concentration of Fe(CO)5, the formation of Fe(CO)a complexes is favored because they are more stable. At a high concentration of Fe(CO)s, formation of mono- and di-Fe(CO)4 complexes becomes important, and selectivity for diene hydrogenation is decreased. Although the occurrence of olefin-Fe(CO)4 complexes has precedence in the literature (i9), no such species has yet been identified with either methyl oleate or linoleate. 

Y. Pouilloux, A. Piccirilli and J. Barrault, "Selective hydrogenation into oleyl alcohol of methyl oleate in the presence of Ru-Sn/ALOi catalysts" J. Mot. Catal A Chemical, 108,161 (1996). 

Barrault and co-workers studied the selective hydrogenation of methyl oleate into oleyl alcohol over RuSnB/alumina catalysts. The yield of oleyl alcohol was 75 % at 90 % methyl oleate conversion over a RuSnB/AbOa catalyst for a bulk atomic ratio Sn/Ru of 4. Over such catalysts the reaction involves three steps (1) the hydrogenation of the methyl oleate into the oleyl alcohol, (2) the transesterification between the methyl oleate and the oleyl alcohol with the formation of the heavy oleyl oleate ester, (3) the hydrogenolysis of this heavy ester into oleyl alcohol. The first and the third steps could involve mixed ruthenium-tin sites with two SnOx (x = 2) species, while the second could require tin species without... 

J. C. Bailar, Jr., and Hiroshi Itatani, Homogeneous Catalysis in the Reactions of Olefinic Substances. VI. Selective Hydrogenation of Methyl Linoleate and Isomerization of Methyl Oleate by Homogeneous Catalysis with Platinum Complexes Containing Triphenylphosphine, Arsine or Stibine, J. Am. Chem. Soc. 89 1592 (1967). 

Shape-selective hydrogenation of methyl oleate cis isomer) and methyl elaidate trans isomer) over Pt/ZSM-5. Reprinted with permission from Wiley-VCH Verlag(From Philippaerts A, Jacobs PA, Sets BF. Is there still a future for hydrogenated vegetable oils Angew Chem Int Ed 2013 52 5220—6). 

Philippaerts A, Paulussen S, Turner S, Lebedev OI, Van Tendeloo G, Poehnan H, et al. Selectivity in sorption and hydrogenation of methyl oleate and elaidate on MFI zeolites. J Catal 2010 270 172-84. 

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