Summary
1. Kinetic studies showed that concurrent oxidation of preformed hydroperoxides may be expected to take place at all stages of the autoxidation of methyl linoleate. The rate of oxidation relative to the rate of autoxidation of unoxidized ester is determined chiefly by the extent of the accumulation of hydroperoxides.
2. Infrared spectral analysis of hydroperoxides oxidized to various degrees indicated thattrans, trans diene conjugation and isolatedtrans double bonds produced in the autoxidation of methyl linoleate are related to the concurrent oxidation of the accumulated hydroperoxides.
3. The low absorptivity observed for diene conjugation, compared to that which may be expected for the exclusive production ofcis, trans diene conjugated hydroperoxide isomers during the autoxidation of methyl linoleate is attributed to the concurrent oxidation of accumulated hydroperoxides.
4. The effect of antioxidants in giving a well-defined induction period in the oxidation of hydroperoxides isolated from autoxidized methyl linoleate indicated that the oxidation proceeds by a chain reaction.
5. The primary reaction products of the oxidation of hydroperoxides isolated from autoxidized methyl linoleate were found to be polymers formed in a sequence of reaction involving the diene conjugation.
6. Studies on the autoxidation of methylcis-9,trans-11-linoleate showed thatcis, trans isomerization of the conjugated diene took place with the concurrent production of isolatedtrans double bonds and loss of diene conjugation.
Similar content being viewed by others
References
Allen, R. R., and Kummerow, F. A., J. Am. Oil Chemists’ Soc.,28, 101 (1951).
Allen, R. R., Jackson, A., and Kummerow, F. A., J. Am. Oil Chemists’ Soc.,26, 395 (1949).
Althouse, P. M., Hunter, G. W., and Triebold, H. O., J. Am. Oil Chemists’ Soc.,24, 257 (1947).
Bateman, L., Quart. Rev. (London),8, 147 (1954).
Bergström, S., Arkiv Mineral. Geol. Bd.,21A, no. 14 (1945).
Bergström, S., Blomstrand, R., and Laurell, S., Acta Chem. Scand.,4, 245–250 (1950).
Bolland, J. L., Proc. Roy. Soc.,A186, 218 (1946).
Bolland, J. L., Quart. Rev., (London),3, 1 (1949).
Bolland, J. L., and Koch, H. P., J. Chem. Soc.,445 (1945).
Bolland, J. L., and Gee, G., Trans. Faraday Soc.,42, 244 (1946).
Brauer, R. W., and Steadman, L. T., J. Am. Chem. Soc.,66, 563 (1954).
Cannon, J. A., Zilch, K. T., Burket, S. C., and Dutton, H. J., J. Am. Oil Chemists’ Soc.,29, 447 (1952).
Coleman, J. E., Knight, H. B., and Swern, Daniel, J. Am. Oil Chemists’ Soc.,32, 135 (1955).
Farmer, E. H., Trans. Faraday Soc.,42, 228 (1946).
Jackson, J. E., Paschke, R. F., Tolberg, W. E., Boyd, H. M., and Wheeler, D. H., J. Am. Oil Chemists’ Soc.,29, 229 (1952).
Lundberg, W. O., Chipault, J. R., and Hendrickson, M. J., J. Am. Oil Chemists’ Soc.,26, 109 (1949).
Lundberg, W. O., and Chipault, J. R., J. Am. Chem. Soc.,69, 833 (1947).
Nichols, P. L., Herb, S. F., and Riemenschneider, R. W., J. Am. Chem. Soc.,73, 247 (1951).
Privett, O. S., Lundberg, W. O., Khan, N. A., Tolberg, W. E., and Wheeler, D. H., J. Am. Oil Chemists’ Soc.,30, 61 (1953).
Privett, O. S., Nickell, Christense, Boyer, P. D., and Lundberg, W. O., J. Am. Oil Chemists’ Soc.,32, 505 (1955).
Privett, O. S., Lundberg, W. O., and Nickell, Christense, J. Am. Oil Chemists’ Soc.,30, 17 (1953).
Sephton, H. H., and Sutton, D. A., Chem. and Ind., 667 (1953).
Sephton, H. H., and Sutton, D. A., paper presented at the 29th fall meeting of the American Oil Chemists’ Society, Philadelphia, Oct. 10–12, 1955.
von Mikusch, J. D., J. Am. Oil Chemists’ Soc.,28, 133 (1954).
Willits, C. O., Ricciuti, C., Knight, H. B., and Swern, Daniel, Anal. Chem.,24, 785 (1952).
Willits, C. O., Ricciuti, C., Ogg, C. L., Morris, S. C., and Riemenschneider, R. W., J. Am. Oil Chemists’ Soc.,30, 420 (1953).
Author information
Authors and Affiliations
Additional information
Hormel Institute publication no. 138. Presented before the American Oil Chemists’ Society, Philadelphia, Pa., Oct. 10–12, 1955.
This work was supported by a grant from the Hormel Foundation.
About this article
Cite this article
Privett, O.S., Nickell, C. Concurrent oxidation of accumulated hydroperoxides in the autoxidation of methyl linoleate. J Am Oil Chem Soc 33, 156–163 (1956). https://doi.org/10.1007/BF02638204
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF02638204