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Transformation of fatty acid hydroperoxides by alkali and characterization of products

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Lipids

Abstract

It has previously been determined that (13S,9Z,11E)-13-hydroperoxy-9,11-octadecadienoic acid was mainly converted into (13S,9Z,11E)-13-hydroxy-9,11-octadecadienoic acid by 5 N KHO with preservation of the stereochemistry of the reactant [Simpson, T.D., and Gardner, H.W. (1993)Lipids 28, 325–330]. In addition, about 20–25% of the reactant was converted into several unknown by-products. In the present work it was confirmed that the stereochemistry was conserved during the hydroperoxy-diene to hydroxydiene transformation, but also, novel by-products were identified. It was found that after only 40 min reaction (9Z)-13-oxo-trans-11,12-epoxy-9-octadecenoic acid accumulated to as much as 7% of the total. Later, (9Z)-13-oxo-trans-11,12-epoxy-9-octadecenoic acid began to disappear, and several other compounds continued to increase in yield. Two of these compounds, 2-butyl-3,5-tetradecadienedioic acid and 2-butyl-4-hydroxy-5-tetradecenedioic acid, were shown to originate from (9Z)-13-oxo-trans-11,12-epoxy-9-octadecenoic acid, and they accumulated up to 2–3% each after 4 to 6 h. Some other lesser products included 11-hydroxy-9,12-heptadecadienoic acid, 3-hydroxy-4-tridecenedioic acid, 13-oxo-9,11-octadecadienoic acid and 12,13-epoxy-11-hydroxy-9-octadecenoic acid. Except for the latter two, most or all of the compounds could have originated from Favorskii rearrangement of the early product, (9Z)-13-oxo-trans-11,12-epoxy-9-octadecenoic acid, through a cyclopropanone intermediate.

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Abbreviations

GC/MS:

gas chromatography/mass spectrometry

GLC:

gas-liquid chromatography

13S-HOD:

(13S,9Z,11E)-13-hydroxy-9,11-octadecadienoic acid

13S-HOT:

(13S,9Z,11E,15Z)-13-hydroxy-9,11,15-octadecadienoic acid

13S-HPOD:

(13S,9Z,11E)-13-hydroperoxy-9,11-octadecadienoic acid

13S-HPOT:

(13S,9Z,11E,15Z)-13-hydroperoxy-9,11,15-octadecatrienoic acid

IR:

infrared

LPLC:

low-pressure liquid chromatography

MC:

(−)-menthoxycarbonyl derivative

NMR:

nuclear magnetic resonance

OTMS (or TMSO):

trimethylsilyloxy derivative

Rf :

migration relative to the solvent front

TLC:

thin-layer chromatography

TMS:

trimethylsilyl cation

UV:

ultraviolet

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Authors and Affiliations

  1. Department of Physiological Chemistry, Karolinska Institutet, S-104 01, Stockholm, Sweden

    Mats Hamberg

  2. NCAUR, ARS, USDA, 1815 N. University Street, 61604, Peoria, IL

    Harold W. Gardner & Thomas D. Simpson

Authors
  1. Harold W. Gardner
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  2. Thomas D. Simpson
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  3. Mats Hamberg
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Gardner, H.W., Simpson, T.D. & Hamberg, M. Transformation of fatty acid hydroperoxides by alkali and characterization of products. Lipids 28, 487–495 (1993). https://doi.org/10.1007/BF02536079

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  • DOI: https://doi.org/10.1007/BF02536079

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