Abstract
A previous study of autoxidation products by high pressure liquid chromatography (HPLC) of methyl oleate and linoleate was extended to methyl linolenate. Autoxidized methyl linolenate was fractionated by HPLC either after reduction to allylic alcohols on a reverse phase system, or directly on a micro silica column. Isolated oxidation products were characterized by thin layer and gas liquid chromatography and by ultraviolet, infrared, nuclear magnetic resonance and mass spectrometry. Secondary products from the autoxidation mixtures (containing 3.5–8.5% monohydroperoxides) included epoxy unsaturated compounds (0.2–0.3%), hydroxy or hydroperoxy-cyclic peroxides (3.8–7.7%), epoxy-hydroxy dienes (<0.1%), dihydroxy or dihydroperoxides with conjugated diene-triene and conjugated triene systems (0.9–2.9%). Cyclization of the 12- and 13-hydroperoxides of linolenate would account for their lower relative concentration than the 9- and 16-hydroperoxides. Dihydroperoxides may be derived from the 9- and 16-linolenate hydroperoxides. Cyclic peroxides and dihydroperoxides are suggested as important flavor precursors in oxidized fats.
Similar content being viewed by others
References
Chan, H.W.S., and G. Levett, Lipids 12:837 (1977).
Funk, M.O., R. Isaac and N.A. Porter, Lipids 11:113 (1976).
Frankel, E.N., W.E. Neff, W.K. Rohwedder, B.P.S. Khambay, R.F. Garwood and B.C.L. Weedon, Lipids 12:1055 (1977).
Haverkamp Begemann, P., W.J. Woesterburg and S. Leer, J. Agric. Food Chem. 16:679 (1968).
Roza, M., and A. Francke, Biochim. Biophys. Acta 528:119 (1978).
Neff, W.E., E.N. Frankel, C.R. Scholfield and D. Weisleder, Lipids 13:415 (1978).
Chan, H.W.S., J.A. Matthew and D.T. Coxon, J. Chem. Soc. Chem. Commun. 235 (1980).
O'Connor, D.E., E.D. Mihelich and M.C. Coleman, J. Am. Chem. Soc. 103:223 (1981).
Butterfield, R.O., H.J. Dutton and C.R. Scholfield, Anal. Chem. 38:86 (1966).
Dommes, V., F. Wirtz-Peitz and W-H. Kunau, J. Chromatogr. Sci. 14:360 (1976).
Porter, N.A., J. Logan and U. Kontoyiannidou, J. Org. Chem. 44:3177 (1979).
Chan, H.W.S., and G. Levett, Chem. Ind. 692 (1977).
Gardner, H.W., J. Lipid Res. 11:311 (1970).
Aplin, R.T., and L. Coles, J. Chem. Soc. Chem. Commun. 858 (1967).
Porter, N.A., M.O. Funk, D. Gilmore, R. Isaac and J. Nixon, J. Am. Chem. Soc. 98:6000 (1976).
Silverstein, R.M., and G.C. Bassler, “Spectrometric Identification of Organic Compounds,” 1st Edn., John Wiley and Sons, Inc., New York, NY, 1964, p. 62.
Bus, J., J. Seis and M.S.F. Lie Ken Jie, Chem. Phys. Lipids 18:130 (1977).
Vioque, E., and R.T. Holman, Arch. Biochem. Biophys. 99:522 (1962).
Frankel, E.N., Prog. Lipid Res. 19:1 (1980).
Frankel, E.N., in “Autoxidation in Foods and Biological Systems,” edited by M.G. Simic and M. Karel, Plenum Press, New York, NY, 1980, p. 141.
Frankel, E.N., W.E. Neff and E. Selke, Lipids 16:279 (1981).
Frankel, E.N., C.D. Evans, D.G. McConnel, E. Selke and H.J. Dutton, J. Org. Chem. 26:4663 (1961).
Neff, W.E., and E.N. Frankel, Lipids 15:587 (1980).
Pryor, W.A., J.P. Stanley and E. Blair, Lipids 11:370 (1976).
Baldwin, J.E., J. Chem. Soc. Chem. Commun. 734 (1976).
Gardner, H.W., J. Agric. Food Chem. 23:129 (1975).
Swoboda, P.A.T., and K.E. Peters, J. Sci. Food Agric. 29:803 (1978).
Selke, E., W.K. Rohwedder and H.J. Dutton, J. Am. Oil Chem. Soc. 57:25 (1980).
Gardner, H.W., D. Weisleder and R. Kleiman, Lipids 13:246 (1978).
Selke, E., E.N. Frankel and W.E. Neff, Lipids 13:511 (1978).
Author information
Authors and Affiliations
About this article
Cite this article
Neff, W.E., Frankel, E.N. & Weisleder, D. High pressure liquid chromatography of autoxidized lipids: II. Hydroperoxy-cyclic peroxides and other secondary products from methyl linolenate. Lipids 16, 439–448 (1981). https://doi.org/10.1007/BF02535012
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF02535012