Summary
-
1.
It has been confirmed that the principal products formed in the oxidation of methyl oleate by oxygen under a variety of conditions are predominantlytrans hydroperoxides. However no inversion of the double bond occurs in unoxidized oleate. Hence the conversion ofcis totrans double bonds and peroxide formation occur together in the same molecules.
-
2
The autoxidation of methyl linoleate at low temperature yields predominantlycis,trans conjugated hydroperoxides. Autoxidation at 25°C., oxidation catalyzed by visible light, or ultraviolet light and copper soap catalyzed oxidation at temperatures appreciably above 0°C., lead to the formation primarily oftrans,trans conjugated hydroperoxides. The inversion of the second double bond in this case appears to be independent of the peroxide-forming reactions.
-
3
The photochlorophyll oxidation of methyl linoleate leads to the formation of some unconjugated hydroperoxides, some of which containtrans double bonds.
-
4
Under all of the conditions employed in the present investigation, the oxidation of methyl oleate and linoleate led primarily to the formation of monomeric peroxides which retained most of the unsaturation of the parent compound.
Similar content being viewed by others
References
Adams, K., and Auxier, R. W., Official Digest,322, 669 (1951).
Adams, R., Vorhees, V., and Shriner, R. L., “Organic Syntheses,” Col. Vol. I, 2nd ed., John Wiley and Sons Inc., New York, p. 463 (1948).
Bateman, L., and Gee, G., Trans. Faraday Soc.,47, 155, 274 (1951).
Bergström, S., Arkiv för Kemi, Mineralogi och Geologi, Bd. 21A, no. 14 and 15 (1945).
Bergström, S., Nature,156, 717 (1945).
Bergström, S., and Holman, R. T., Nature,161, 55 (1948).
Bolland, J. L., Proc. Royal Soc.,A186, 218 (1946).
Bolland, J. L., and Gee, G., Trans. Faraday Soc.,42, 236, 244 (1946).
Bolland, J. L., and Koch, H. P., J. Chem. Soc., p. 445 (1945).
Cannon, J. A., Zilch, K. T., Burket, S. C., and Dutton, H. J., J. Am. Oil Chemists’ Soc.,29, 447 (1952).
Dugan, L. R., Beadle, R. W., and Henick, A. S., J. Am. Oil Chemists’ Soc.,26, 681 (1949).
Farmer, E. H., Trans. Faraday Soc.,42, 228 (1946).
Farmer, E. H., Koch, H. P., and Sutton, D. A., J. Chem. Soc., p. 541 (1943).
Farmer, E. H., Bloomfield, G. F., Sundralingam, A., and Sutton, D. A., Trans. Faraday Soc.,38, 348 (1942).
Farmer, E. H., and Sundralingam, A., J. Chem. Soc., p. 121 (1942).
Farmer, E. H., and Sutton, D. A., J. Chem. Soc., p. 119 (1943).
Fieser, L. F., “Experiments in Organic Chemistry,” D. C. Heath and Company, p. 369 (1941).
Hendrickson, M. J., Ph.D. Thesis, University of Minnesota, 1948.
Holman, R. T., Archives of Biochem.,15, 403 (1947).
Holman, R. T., Lundberg, W. O., and Burr, G. O., J. Am. Chem. Soc.,67, 1386 (1945).
Honn, F. J., Bezman, I. I., and Daubert, B. F., J. Am. Chem. Soc.,71, 812 (1949).
Jackson, J. E., Paschke, R. F., Tolberg, W., Boyd, H. M., and Wheeler, D. H., J. Am. Oil Chemists’ Soc.,29, 229 (1952).
Joshel, L. H., Ind. Eng. Chem., Anal. ed.,15, 590 (1943).
Khan, N. A., J. Am. Oil Chemists’ Soc.,30, 273 (1953).
Khan, N. A., and Lundberg, W. O., J. Am. Oil Chemists’ Soc., in preparation.
Khan, N. A., Lundberg, W. O., and Holman, R. T., J. Am. Chem. Soc.,76, 1779 (1954).
Knight, H. B., Eddy, C. R., and Swern, Daniel, J. Am. Oil Chemists’ Soc.,28, (1951).
Lundberg, W. O., Oleagineux,4, 85 (1949).
Lundberg, W. O., U. S. Patent 2,636,890.
Lundberg, W. O., and Chipault, J. R., J. Am. Chem. Soc.,69, 833 (1947).
Lundberg, W. O., Chipault, J. R., and Hendrickson, M. J., J. Am. Oil Chemists’ Soc.,26, 109 (1949).
Nichols, P. L., Herb, S. F., and Riemenschneider, R. W., J. Am. Chem. Soc.,73, 247 (1951).
Ogg, C. L., Porter, W. L., and Willits, C. O., Ind. Eng. Chem., Anal. Ed.,17, 394 (1945).
Paschke, R. F., Kerns, J. R., and Wheeler, D. H., J. Am. Oil Chemists’ Soc.,31, 5 (1954).
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., Lundberg, W. O., and Nickell, Christense, J. Am. Oil Chemists’ Soc.,30, 17 (1953).
Sinclair, R. G., McKay, A. F., Myers, G. S., and Jones, R. N., J. Am. Chem. Soc.,74, 2578 (1952).
Sutherland, C. B. M., Trans. Faraday Soc.,41, 286 (1945).
Swern, D., Coleman, J. E., Knight, H. B., Ricciati, C., Willits, C. O., and Eddy, C. R., 123rd National Meeting, American Chemical Society, Los Angeles, 1953.
Tolberg, W., and Boyd, H. M., Anal. Chem.,24, 1836 (1952).
von Mikusch, J. D., and Frazier, C., Ind. Eng. Chem., Anal. Ed.,13, 782 (1941).
Author information
Authors and Affiliations
Additional information
This work was supported by a contract between the Office of Naval Research, Department of the Navy, and the University of Minnesota.
Hormel Institute publication no. 104 and paper no. 150 Journal Series, General Mills Research Laboratories.
About this article
Cite this article
Khan, N.A., Tolberg, W.E., Wheeler, D.H. et al. Photochemical oxidation of fatty acid esters with and without chlorophyll. J Am Oil Chem Soc 31, 460–466 (1954). https://doi.org/10.1007/BF02638551
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF02638551