Abstract
The effects of oxygen pressure, substrate concentration and solvent on the rate and products of oxidation of methyl linoleate were studied at 50 C with azobisisobutyronitrile as a radical initiator. The absolute and quantitative numbers for oxygen uptake, substrate disappearance, and formation of conjugated diene and hydroperoxides were measured. Under the present conditions, 4 conjugated diene hydroperoxides, 13-hydroperoxy-9-cis, 11-trans-(2a), 13-hydroperoxy-9-trans, 11-trans-(3a), 9-hydroperoxy-10-trans, 12-cis-(4a), and 9-hydroperoxy-10-trans, 12-trans-(5a) octadecadienoic acid methyl esters, were formed almost quantitatively. The rate of oxidation decreased with decreasing oxygen pressure. However, the ratio ofcis,trans totrans,trans hydroperoxides, (2a+4a)/(3a+5a), was independent of oxygen pressure, and this ratio increased with increasing methyl linoleate concentration, as found recently by Porter. Further, the rate of oxidation and the ratio ofcis,trans/trans,trans hydroperoxides were dependent on solvent and increased with an increase in dielectric constant of solvent. A mechanism of methyl linoleate oxidation consistent with these results is discussed.
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References
Lundberg, W.O. (1962) Autoxidation and Antioxidants, Interscience, New York, NY.
Pryor, W.A., ed. (1976) Free Radicals in Biology, Vol. I, Academic Press, New York, NY.
Simic, H.G., and Karel, M., eds. (1980) Autoxidation in Food and Biological Systems, Plenum Press, New York, NY.
Howard, J.A., and Ingold, K.U. (1967) Can. J. Chem. 45, 793–802.
Chan, H.W.S., and Levett, G. (1977) Lipids 12, 99–104.
Yamamoto, Y., Niki, E., and Kamiya, Y. (1982) Bull. Chem. Soc. Jpn. 55, 1548–1550.
Porter, N.A., Weber, B.A., Weenen, H., and Khan, J.A. (1980) J. Am. Chem. Soc. 102, 5597–5601.
Porter, N.A., Lehman, L.S., Weber, B.A., and Smith, K.J. (1981) J. Am. Chem. Soc. 103, 6447–6455.
Pryor, W.A., Stanley, J.P., Blair, E., and Cullen, G.B. (1976) Arch. Environ. Health 31, 201–210.
Frankel, E.N., Neff, W.E., Rohwedder, W.K., Khambay, B.P.S., Garwood, R.F., and Weedom, B.C.L. (1977) Lipids 12, 908–913.
Chan, H.W.S., Levett, G., and Matthew, J.A. (1978) J. Chem. Soc. Chem. Commun., 756–757.
Chan, H.W.S., Levett, G., and Matthew, J.A. (1979) Chem. Phys. Lipids 24, 245–256.b
Dumelin, E.E., and Tappel, A.L. (1977) Lipids 12, 894–900.
Porter, N.A., Wolf, R.A., and Weenan, H. (1980) Lipids 15, 163–167.
Fatemi, S.H., and Hammond, E.G. (1980) Lipids 15, 379–385.
Boozer, C.E., Hammond, G.S., and Sen, J.N. (1955) J. Am. Chem. Soc. 77, 3233–3237.
Burton, G.W., and Ingold, K.U. (1981) J. Am. Chem. Soc. 103, 6472–6477.
Ingold, K.U. (1973) in Free Radicals I (Kochi, J.K., ed.) pp. 37–112, John Wiley & Sons, New York, NY.
Howard, J.A. (1972) Adv. Free Radical Chem. 4, 49–173.
Zaikov, G.E. (1963) Neftekhimiya 3, 381–389.
Zaikov, G.E., and Maizus, Z.K. (1963) Dokl. Akad. Nauk SSSR 150, 116–119.
Zaikov, G.E. (1968) Kinet. Katal. 9, 511–515.
Hendry, D.G., and Russel, G.A. (1964) J. Am. Chem. Soc. 86, 2368–2371.
Howard, J.A., and Ingold, K.U. (1964) Can. J. Chem. 42, 1044–1056.
Howard, J.A., and Ingold, K.U. (1964) Can. J. Chem. 42, 1250–1253.
Kamiya, Y. (1965) Bull. Chem. Soc. Jpn. 38, 2156–2159.
Niki, E., Kamiya, Y., and Ohta, N. (1969) Bull. Chem. Soc. Jpn. 42, 3224–3229.
Barclay, L.R.C., and Ingold, K.U. (1981) J. Am. Chem. Soc. 103, 6478–6485.
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Yamamoto, Y., Niki, E. & Kamiya, Y. Oxidation of lipids: III. Oxidation of methyl linoleate in solution. Lipids 17, 870–877 (1982). https://doi.org/10.1007/BF02534581
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DOI: https://doi.org/10.1007/BF02534581