Abstract
Methyl 9(10)-formylstearate from hydroformylated oleate is autoxidized effectively to the corresponding carboxystearate in the presence of metal naphthenates at 20 C. Up to 95% conversion is obtained by treatment with Ca naphthenate for 24 hr. Catalyst activity based on disappearance of formylstearate approximates the following order: Co>Pb>Mn>Ce>Fe>Zr>Ca. Decreasing yields of carboxyester obtained with different catalysts follow the approximate order: Ca>Pb≈Fe≈Zr≈Mn>Co>Ce. The active redox metal catalysts such as Co, Ce and Mn produce varying amounts of methyl stearate, epoxy-, keto- and hydroxystearate as side products. Ca naphthenate minimizes free radical decarbonylation and other side reactions. Mechanisms are proposed for the formation of side products.
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References
Frankel, E.N., JAOCS 48:248 (1971).
Twigg, G.H., Chem. Ind. 1966:476.
Allen, G.C., and A. Aguillo, Advan. Chem. Ser. 76:363 (1968).
Hassall, C.H., “The Baeyer-Villiger Oxidation of Aldehydes and Ketones,” in “Organic Reactions,” Vol. 9, Third Edition, Edited by R. Adams et al., John Wiley and Sons, Inc., New York, 1966, p. 73.
Horner, L., in “Autoxidation and Antioxidants,” Edited by W.O. Lundberg, Interscience Publishers, New York, p. 197–202.
Cooper, H.R., and M.W. Melville, J. Chem. Soc. 1984 (1951); 1994 (1951).
Ingold, K.V., in “Symposium on Foods: Lipids and Their Oxidation,” Edited by M.W. Schultz, E.A. Day and R.O. Sinnhuber, Avi Publishing Co., Westport, Conn., 1962, p. 98.
Thuring, P., and A. Peret, Helv. Chim. Acta 36:13 (1953).
Gould, E.S., “Mechanism and Structure in Organic Chemistry,” Holt, Rinehart and Winston, New York, 1959, p. 748.
Misono, A., T. Osa and Y. Ohkatsu, Advan. Chem. Ser. 75:120 (1968).
Ladhabhoy, M.E., and M.M. Sharma, J. Appl. Chem. 20:274 (1970).
AOCS Official and Tentative Methods, Third Edition, American Oil Chemists’ Society, Chicago, 1969, Cd 8-53.
Frankel, E.N., S. Metlin, W.K. Rohwedder and I. Wender, JAOCS 46:133 (1969).
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No. Market. Nutr. Res. Div., ARS, USDA.
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Schwab, A.W., Frankel, E.N., Dufek, E.J. et al. Methyl 9(10)-carboxystearate by catalytic oxidation of hydroformylated oleate. J Am Oil Chem Soc 49, 75–79 (1972). https://doi.org/10.1007/BF02545144
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DOI: https://doi.org/10.1007/BF02545144