Abstract
Transformation of 13(S)-hydroperoxy-9(Z),11(E)-octadecadienoic acid (13S-HPOD) to 13(S)-hydroxy-9(Z),11(E)-octadecadienoic acid (13S-HOD) under alkaline conditions (0.05 to 5 M KOH) occurred first-order with respect to 13S-HPOD concentration. Overall yield was about 80%. The energy of activation at higher concentrations (3.75 to 5 M KOH) was determined to be in the range of 15.3 to 15.6 kcal. Compared to the 13S-HPOD conversion, 13(S)-hydroperoxy-9(Z),11(E),15(Z)-octadecatrienoic acid (13S-HPOT) was converted at a faster rate to the corresponding hydroxy fatty acid (13S-HOT), with the reaction also being first-order. Chiral phase high-performance liquid chromatography demonstrated that in the transformation the stereochemistry of both the 13S-HPOD and 13S-HPOT reactants was preserved. Manometric analyses of the KOH/13S-HPOD reaction showed an uptake of gas, which amounted to 11% of the mols of reactant 13S-HPOD on the assumption that the gas was O2. As there is a theoretical loss of 1 oxygen atom in the reaction, the fate of this oxygen (possiblyvia active oxygen species) may involve reaction with 13S-HPOD/13SHOD to form the 20% by-products.
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Abbreviations
- Ea :
-
energy of activation
- EDTA:
-
ethylenediaminetetraacetic acid
- 13S-HPOD:
-
13(S)-hydroperoxy-9(Z),11(E)-octadecadienoic acid
- 13S-HPOT:
-
13(S)-hydroperoxy-9(Z),11(E),15(Z)-octadecadienoic acid
- 13S-HOT:
-
13(S)-hydroxy-9(Z),11(E),15(Z)-octadecatrienoic acid
- HPLC:
-
high-performance liquid chromatography
- rac-HOD:
-
racemic mixture of 9(R,S)-hydroxy-10(E),12(E,Z)- and 13(R,S)-hydroxy-9(E,Z),11(E)-octadecadienoic acids
- rac-HOT:
-
racemic mixture of 9(R,S)-hydroxy-10(E),12(Z),15(Z)-, 12(R,S)-hydroxy-9(Z),13(E),15(Z),13(R,S)-hydroxy-9(Z), 11(E),15(Z)-, and 16(R,S)-hydroxy-9(Z),12(Z),14(E)-octadecatrienoic acids
- TLC:
-
thin-layer chromatography
Literatur
O'Brien, P.J. (1969)Can. J. Biochem. 47, 485–492.
Gardner, H.W., and Jursinic, P.A. (1981)Biochim. Biophys. Acta 665, 100–112.
Kühn, H., Wiesner, R., Alder, L., and Schewe, T. (1989)Eur. J. Biochem. 186, 155–162.
Garnder, H.W. (1975)Lipids 10, 248–252.
Gardner, H.W., and Newton, J.W. (1987)Phytochemistry 26, 621–626.
Gardner, H.W., Weisleder, D., and Plattner, R.D. (1991)Plant Physiol. 97, 1059–1072.
Kühn, H., Wiesner, R., Lankin, V.Z., Nekrasov, A., Alder, L., and Schewe, T. (1987)Anal. Biochem. 160, 24–34.
Gardner, H.W. (1989)Biochim. Biophys Acta 1001, 274–281.
Umbreit, W.W., Burris, R.H., and Stauffer, J.F. (1949)Manometric Techniques and Tissue Metabolism, Burgess Publishing Co., Minneapolis.
Gardner, H.W. (1989)Free Radical Biol. Med. 7, 65–86.
The Official Methods and Recommended Practices of the American Oil Chemists' Society (1971) (Link, W.E., ed.), 3rd edn., Method Cd 8-53, American Oil Chemists' Society, Champaign.
Denny, D.B., and Rosen, J.D. (1964)Tetrahedron 20, 271–279.
Russell, G.A. (1957)J. Am. Chem. Soc. 79, 3871–3877.
Howard, J.A., and Ingold, K.U. (1968)J. Am. Chem. Soc. 90, 1056–1058.
Nakano, M., Noguchi, T., Sugioka, K., Fukuyama, H., Sato, M., Shimizu, Y., Tsuji, Y., and Inaba, H. (1975)J. Biol. Chem. 250, 2404–2406.
Nakano, M., Takayama, K., Shimizu, Y., Tsuji, Y., Inaba, H., and Migita, T. (1976)J. Am. Chem. Soc. 98, 1974–1975.
Buchanan, M.R., Haas, T.A., Lagarde, M., and Guichardant, M. (1985)J. Biol. Chem. 260, 16056–16059.
Kato, T., Yamaguchi, Y., Hirano, T., Yokoyama, T., Uyehara, T., Namai, T., Yamanaka, S., and Harada, N. (1984)Chem. Letters, 409–412.
Tranchepain, I., Le Berre, F., Dureault, A., Le Merrer, Y., and Depezay, J.C. (1989)Tetrahedron 45, 2057–2065.
Bloch, R., and Perfetti, M-T. (1990)Tetrahedron Lett. 31, 2577–2580.
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Simpson, T.D., Gardner, H.W. Conversion of 13(S)-hydroperoxy-9(Z),11(E)-octadecadienoic acid to the corresponding hydroxy fatty acid by KOH: A kinetic study. Lipids 28, 325–330 (1993). https://doi.org/10.1007/BF02536318
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DOI: https://doi.org/10.1007/BF02536318