Summary
1. The geometrical forms obtained during autoxidation of methyl linoleate at ordinary temperatures are largely conjugatedcis-trans andtrans-trans as shown by previous workers; there is a possibility that conjugatedcis-cis forms are also produced.
2. Thetrans-trans molecules arise partly, at least, by thermal rearrangement of already formedcis-trans peroxide.
3. Some proportion, at least, of thecis-trans molecules have theirtrans double bonds nearest to the hydroperoxide group.
4. A partial separation of the geometrical forms can be accomplished by reversed phase partition chromatography both on methyl linoleate hydroperoxides and on the corresponding mixed hydroxy compounds; isolation of thetrans-trans forms can be accomplished in the latter case by urea complex fractionation.
5. No position isomers except the known 9- and 13-isomers have been positively identified; there is a possibility that very minor amounts of the 2-isomer are formed; the 9- and 13-isomers are present in about equal amounts; the 11-isomer was not detected by the methods applied.
6. Various ways in which the linoleate autoxidation problem might be advanced further are suggested.
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References
Barnard, D., and Hargrave, K. R., Anal. Chim. Acta,5, 476 (1951).
Benton, J. L., and Wirth, M. M., Nature,171, 269 (1953).
Bergström, S., Arkiv. Kemi., Mineral. Geol.,21A, No. 14, 1 (1945).
Bolland, J. L., and Koch, H. P., J. Chem. Soc. 445 (1945).
Bolland, J. L., Sundralingam, A., Sutton, D. A., and Tristram, G. R., Trans. Inst. Rubber Ind.,17, 29 (1941).
Bourne, E. J., McSweeney, G. P., and Wiggins, L. F., J. Chem. Soc., 1408, 2542 (1952).
Braude, E. A., and Timmons, C. J., J. Chem. Soc., 2004 (1950).
Brockmann, H., and Schodder, H., Ber.,74B, 73 (1941).
Cannon, J. A., Zilch, K. T., Burket, S. C., and Dutton, H. J., J. Am. Oil Chemists’ Soc.,29, 447 (1952).
Farmer, E. H., Koch, H. P., and Sutton, D. A., J. Chem. Soc., 541 (1943).
Haupt, G. W., J. Research Natl. Bur. Standards,48, No. 6, 414 (1952).
Howard, G. A., and Martin, A. J. P., Biochem. J.,46, 532 (1950).
Karnovsky, M. L., and Rapson, W. S., J. Soc. Chem. Ind.,65, 138 (1946).
Khan, N. A., Lundberg, W. O., and Holman, R. T., J. Am. Chem. Soc.,76, 1779 (1954).
Lindqvist, B., and Storgärds, T., Acta Chem. Scand.,7, 87 (1953).
Lunde, K., and Zechmeister, L., Acta Chem. Scand.,8, 1421 (1954).
Markley, K. S., “Fatty Acids,” Interscience, New York, p. 391 (1947).
Matic, M., unpublished.
Matic, M., and Sutton, D. A., Chemistry and Industry, 666 (1953).
Micheel, F., and Schweppe, H., Mikrochim. Acta,53 (1954).
Nichols, P. L. Jr., Herb, S. F., and Riemenschneider, R. W., J. Am. Chem. Soc.,73, 247 (1951).
Oroshnik, W., and Mebane, A. D., J. Am. Chem. Soc.,76, 5719 (1954).
Paschke, R. F., Tolberg, W. E., and Wheeler, D. H., J. Am. Oil Chemists’ Soc.,30, 97 (1953).
Privett, O. S., Lundberg, W. O., and Niekell, C., J. Am. Oil Chemists’ Soc.,30, 17 (1953).
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, C., Boyer, P. D., and Lundberg, W. O., presented at the 28th Fall Meeting of the American Oil Chemists’ Society (1954).
Sephton, H. H., and Sutton, D. A., Chemistry and Industry 667 (1953).
Silk, M. H., and Hahn, H. H., Biochem. J.,57, 582 (1954).
Sutton, D. A., S. African Ind. Chemist,7, 196 (1953).
Zechmeister, L., Chem. Rev.,34, 267 (1944).
Zilch, K. T., Dutton, H. J., and Cowan, J. C., J. Am. Oil Chemists’ Soc.,29, 244 (1952).
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Sephton, H.H., Sutton, D.A. The chemistry of polymerized oils. V. The autoxidation of methyl linoleate. J Am Oil Chem Soc 33, 263–272 (1956). https://doi.org/10.1007/BF02630858
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DOI: https://doi.org/10.1007/BF02630858