Skip to main content
SpringerLink
Log in

Methyl 9(10)-carboxystearate by catalytic oxidation of hydroformylated oleate

  • Technical
  • Published:
Journal of the American Oil Chemists’ Society

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Frankel, E.N., JAOCS 48:248 (1971).

    CAS  Google Scholar 

  2. Twigg, G.H., Chem. Ind. 1966:476.

  3. Allen, G.C., and A. Aguillo, Advan. Chem. Ser. 76:363 (1968).

    Article  Google Scholar 

  4. 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.

    Google Scholar 

  5. Horner, L., in “Autoxidation and Antioxidants,” Edited by W.O. Lundberg, Interscience Publishers, New York, p. 197–202.

  6. Cooper, H.R., and M.W. Melville, J. Chem. Soc. 1984 (1951); 1994 (1951).

  7. 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.

    Google Scholar 

  8. Thuring, P., and A. Peret, Helv. Chim. Acta 36:13 (1953).

    Article  CAS  Google Scholar 

  9. Gould, E.S., “Mechanism and Structure in Organic Chemistry,” Holt, Rinehart and Winston, New York, 1959, p. 748.

    Google Scholar 

  10. Misono, A., T. Osa and Y. Ohkatsu, Advan. Chem. Ser. 75:120 (1968).

    Google Scholar 

  11. Ladhabhoy, M.E., and M.M. Sharma, J. Appl. Chem. 20:274 (1970).

    Article  CAS  Google Scholar 

  12. AOCS Official and Tentative Methods, Third Edition, American Oil Chemists’ Society, Chicago, 1969, Cd 8-53.

  13. Frankel, E.N., S. Metlin, W.K. Rohwedder and I. Wender, JAOCS 46:133 (1969).

    CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Northern Regional Research Laboratory, 61604, Peoria, Illinois

    A. W. Schwab, E. N. Frankel, E. J. Dufek & J. C. Cowan

Authors
  1. A. W. Schwab
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. E. N. Frankel
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. E. J. Dufek
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. J. C. Cowan
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

No. Market. Nutr. Res. Div., ARS, USDA.

About this article

Cite this article

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

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF02545144

Keywords

Search

Navigation