Abstract
Secondary oxidation products are important sources of volatiles because of their susceptibility to further decomposition. Volatiles from the thermal decomposition of hydroperoxy cyclic peroxides have been identified by capillary gas chromatography followed by mass spectrometry (GC-MS). By using a saturated hydroperoxy cyclic peroxide as a synthetic model, the thermal decomposition pathways have been elucidated. Main cleavage occurs between the peroxide ring and the carbon-bearing hydroperoxide group. Volatiles produced were generally similar to those from corresponding monohydroperoxides. New volatiles identified included methyl furan octanoate, methyl ketones, and conjugated diunsaturated aldehyde esters. The general fragmentation observed between the peroxide ring and the hydroperoxide-bearing carbons is sufficiently predictable that it can be used as a tool for the structural characterization of hydroperoxy cyclic peroxides. Hydroperoxy cyclic peroxides from autoxidized and photosensitized oxidized methyl linolenate are suggested as important precursors of volatiles that may affect flavor quality of lipid-containing foods.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Schultz, M. W., Day, E. A. and Sinnhuber, R. O., eds. (1961) Symposium on Foods: Lipids and Their Oxidation, pp. 51–78, 79–89, 215–225, The AVI Publishing Co., Westport, CT.
Forss, D. A. (1972) Prog. Lipid Res. 13, 177–258.
Frankel, E. N. (1980) Prog. Lipid Res. 19, 1–22.
Frankel, E. N. (1983) Prog. Lipid Res. 22, 1–33.
Selke, E., Frankel, E. N., and Neff, W. E. (1978) Lipids 13, 511–513.
Frankel, E. N., Neff, W. E., and Selke, E. (1981) Lipids, 16, 279–285.
Nawar, W. W., and Witchwoot, A. (1980) in Autoxidation in Food and Biological Systems (Simic, M. G., and Karel, M., eds.) pp. 207–221, Plenum Press, New York.
Schiberle, P., and Grosch, W. (1981) J. Am. Oil Chem. Soc. 58, 602–607.
Frankel, E. N., Neff, W. E., Selke, E., and Weisleder, D. (1982) Lipids 17, 11–18.
Frankel, E. N., Weisleder, D., and Neff, W. E. (1981) J. Chem. Soc. Chem. Commun., 766–767.
Neff, W. E., Frankel, E. N., and Weisleder, D. (1981) Lipids 16, 439–448.
Neff, W. E., Frankel, E. N., and Weisleder, D. (1982) Lipids 17, 780–790.
Frankel, E. N., Neff, W. E., and Weisleder, D. (1982) J. Chem. Soc. Chem. Commun., 599–600.
Selke, E., Rohwedder, W. K., and Dutton, H. J. (1977) J. Am. Oil Chem. Soc. 54, 62–67.
Morris, L. J., Marshall, M. O., and Kelly, W. (1966) Tetrahedron Lett., 4249–4253.
Gould, E. S. (1959) Mechanism and Structure in Organic Chemistry, pp. 627–629, Henry Holt and Co., New York.
Beckwith, A. L. J., and Ingold, K. U. (1980) in Rearrangements in Ground and Excited States (de Mayo, P., ed.) Vol. 1, pp. 161–310, Academic Press, Inc., New York.
Itzel, H., and Fischer, H. (1976) Helv. Chim. Acta 59, 880–901.
Author information
Authors and Affiliations
Additional information
The mention of firm names or trade products does not imply that they are endorsed or recommended by the US Department of Agriculture over other firms or similar products not mentioned.
About this article
Cite this article
Frankel, E.N., Neff, W.E. & Selke, E. Analysis of autoxidized fats by gas chromatography-mass spectrometry: VIII. Volatile thermal decomposition products of hydroperoxy cyclic peroxides. Lipids 18, 353–357 (1983). https://doi.org/10.1007/BF02537231
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF02537231