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Journal of the American Oil Chemists' Society

, Volume 77, Issue 3, pp 243–248 | Cite as

Synthesis of δ-stearolactone from oleic acid

  • Steven C. CermakEmail author
  • Terry A. Isbell
Article

Abstract

δ-Stearolactone was prepared from oleic acid using concentrated sulfuric acid under various conditions in the presence of polar, nonparticipating solvents. δ-Stearolactone was formed in as high as 15∶1 ratios over the thermodynamic product, ψ-lactone, in the presence of methylene chloride, 100% wt/vol, at room temperature with two equivalents of sulfuric acid for 24 h. This procedure is applicable to other olefinic fatty acids such as estolides and fatty acid methyl esters. Temperature plays a role in the regioselectivity of the cyclization for δ-lactone, as lower temperatures (20°C) gave higher σ/ψ ratios. At higher temperatures (50°C) in the presence of sulfuric acid and methylene chloride the yield of lactone was 75% but with a σ/ψ ratio of only 0.3∶1. Cyclization of oleic acid to lactone also occurred with other acids. Oleic acid underwent reaction with perchloric acid, one equivalent, in the absence of solvent at 50°C, which yielded σ-lactone in a modest yield with a 3.1 σ/ψ ratio. The same temperature effect was observed with perchloric acid that was observed in the case of sulfiric acid. Because σ-stearolactone is much more reactive than the corresponding fatty acid, fatty acid ester, or ψ-lactone, we believe that it will be a useful synthon for many new industrial products including new biodegradable detergents.

Key Words

Acid catalyzed lactone oleic acid perchloric acid regioselective σ-stearolactone sulfuric acid 

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References

  1. 1.
    Ansell, M.F., and M.H. Palmer, The Lactonisation of Olefinic Acids: The Use of Sulphuric and Trifluoacetic Acids, J. Chem. Soc.: 2640–2644 (1963).Google Scholar
  2. 2.
    Isbell, T.A., and B.A. Plattner, A Highly Regioselective Synthesis of σ-Lactones from Meadowfoam Fatty Acids, J. Am. Oil Chem. Soc. 74:153–158 (1997).Google Scholar
  3. 3.
    Monsanto Co. Jpn., Lactones, U.S. Patent 222,199 (1981).Google Scholar
  4. 4.
    Nakano, Y., and T.A. Foglia, Methanesulfonic Acid Catalyzed Addition of Aromatic Compounds to Oleic Acid, J. Am. Oil Chem. Soc. 61:569–573 (1984).Google Scholar
  5. 5.
    Clutterbuck, P.W., ψ-Hydroxystearic Acid, J. Chem. Soc. 125: 2330–2333 (1924).Google Scholar
  6. 6.
    Showell, J.S., D. Swern, and W.R. Noble, Perchloric Acid Isomerization of Oleic Acid, J. Org. Chem. 88:2697–2704 (1968).Google Scholar
  7. 7.
    Shepherd, I.S., and J.S. Showell, The Mechanism of the Aqueous Perchloric Acid Isomerization of Oleic Acid to ψ-Stearolactone, J. Am. Oil Chem. Soc. 46:479–481 (1969).Google Scholar
  8. 8.
    Fujita, T., S. Watanabe, K.S. Miura, and H. Kikuchi, Syntheses of Dihydrolavandulol and Its Related Compounds from Carboxylic Acids and Conjugated Dienes, J. Chem. Tech. Biotechnol. 32:476–484 (1982).Google Scholar
  9. 9.
    Brown, H.C., J.H. Brewster, and H. Shechter, An Interpretation of the Chemical Behavior of Five-and Six-Membered Ring Compounds, J. Am. Chem. Soc. 76:467–474 (1954).CrossRefGoogle Scholar
  10. 10.
    Ansell, M.P., and M.H. Palmer, The Cyclisation of Olefinic Acids to Ketones and Lactones, Q. Rev. 18:211–225 (1964).CrossRefGoogle Scholar
  11. 11.
    Isbell, T.A., and B.A. Steiner, The Rate of Ring Opening of ψ-and σ-Lactones Derived from Meadowfoam Fatty acids, J. Am. Oil Chem. Soc. 75:63–66 (1998).Google Scholar
  12. 12.
    Frykman, F.B., T.A. Isbell, and S.C. Cermak, 5-Hydroxy Fatty Acids from σ-Lactones and Alkyl Glucamines. J. Surfact. Deterg. in press.Google Scholar
  13. 13.
    Vermeer, R., and B. Harichian, Hydroxy Containing Alkyl Glycamides, Low Foaming Detergent Compositions Comprising Such and a Process for Their Manufacture, U.S. Patent 5,750,733 (1998).Google Scholar
  14. 14.
    Isbell, T.A., and S.C. Cermak, Method for the Development of Delta-Lactones and Hydroxy Acids from Unsaturated Fatty Acids and Their Glycerides, U.S. Patent 6,022,982 (2000).Google Scholar
  15. 15.
    Isbell, T.A., H.B. Frykman, T.P. Abbott, J.E. Lohr, and J.C. Drozd, Optimization of the Sulfuric Acid-Catalyzed Estolide Synthesis from Oleic Acid, J. Am. Oil Chem. Soc. 74:473–476 (1997).Google Scholar
  16. 16.
    Isbell, T.A., R. Kleiman, and B.A. Plattner, Acid-Catalyzed Condensation of Oleic Acid into Estolides and Polyestolides, ——Ibid. 71:169–174 (1994).Google Scholar
  17. 17.
    Isbell, T.A., and R. Kleiman, Characterization of Estolides Produced from the Acid-Catalyzed Condensation of Oleic Acid, ——Ibid 71:379–383 (1994).Google Scholar
  18. 18.
    Erhan, S.M., and R. Kleiman, Meadowfoam and Rapeseed Oil as Accelerators in Factice Production, INFORM 3:482 (1992).Google Scholar
  19. 19.
    Tulloch, A.P., Gas Liquid Chromatography of the Hydroxy-,Acetoxy- and Oxo-Stearic Acid Methyl Esters, J. Am. Oil Chem. Soc. 41:833–836 (1964).Google Scholar

Copyright information

© AOCS Press 2000

Authors and Affiliations

  1. 1.New Crops ResearchNCAUR, ARS, USDAPeoria

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