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Conversion of 13(S)-hydroperoxy-9(Z),11(E)-octadecadienoic acid to the corresponding hydroxy fatty acid by KOH: A kinetic study

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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

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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

Keywords

  • Hydroperoxide
  • Hydroxy Fatty Acid
  • Hydroperoxy
  • Octadecadienoic Acid
  • Octadecatrienoic Acid