Mechanism of linoleic acid hydroperoxide reaction with alkali.
Treatment of (13S,9Z,11E)-13-hydroperoxy-9,11-octadecadienoic acid (13S-HPODE) with strong alkali resulted in the formation of about 75% of the corresponding hydroxy acid, (13S,9Z,11E)-13-hydroxy-9,11-octadecadienoic acid (13S-HODE), and the remaining 25% of products was a mixture of several oxidized fatty acids, the majority of which was formed from (9Z,11R,S,12S,R)-13-oxo-11,12-epoxy-9-octadecenoic acid by Favorskii rearrangement (Gardner, H.W., et al. (1993) Lipids 28, 487-495). In the present work, isotope experiments were completed in order to get further information about the initial steps of the alkali-promoted decomposition of 13S-HPODE. 1. Reaction of [hydroperoxy-18O2] 13S-HPODE with 5 M KOH resulted in the formation of [hydroxy-18O] 13S-HODE and [epoxy-18O](9Z,11R,S,12S,R)-13-oxo-11,12-epoxy-9-octadecenoi c acid; 2. treatment of a mixture of [U-14C] 13S-HODE and [hydroperoxy-18O2] 13S-HPODE with KOH and analysis of the reaction product by radio-TLC showed that 13S-HODE was stable under the reaction conditions and did not serve as precursor of other products; 3. reaction of a mixture of [U-14C] 13-oxo-9,11-octadecadienoic acid (13-OODE) and [hydroperoxy-18O2] 13S-HPODE with KOH resulted in the formation of [U-14C-epoxy-18O]99Z,11R,S,12S,R)-13-oxo-11,12-epoxy-9-octad ecenoic acid; 4. treatment of a mixture of [hydroperoxy-18O2] 13S-HPODE and [carboxyl-18O1] 13S-HPODE with KOH afforded (9Z,11R,S,12S,R)-13-oxo-11,12-epoxy-9-octadecenoic acid having an 18O-labeling pattern which was in agreement with its formation by intermolecular epoxidation. It was concluded that (9Z,11R,S,12S,R)-13-oxo-11,12-epoxy-9-octadecenoic acid is formed from 13S-HPODE by a sequence involving initial dehydration into the alpha, beta-unsaturated ketone, 13-OODE, followed by epoxidation of the delta 11 double bond of this compound by the peroxyl anion of a second molecule of 13S-HPODE. Rapid conversion of hydroperoxides by alkali appeared to require the presence of an alpha, beta-unsaturated ketone intermediate as an oxygen acceptor. This was supported by experiments with a saturated hydroperoxide, methyl 12-hydroperoxyoctadecanoate, which was found to be much more resistant to alkali-promoted conversion than 13S-HPODE.
Gardner
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National Center for Agricultural Utilization Research, ARS, USDA, Peoria, Illinois 61604, USA.
Simpson
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TD
Hamberg
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D000468:Alkalies / Q000737:chemistry*; D000818:Animals; D002374:Catalase / Q000737:chemistry; D002417:Cattle; D008041:Linoleic Acids / Q000737:chemistry*; D008054:Lipid Peroxides / Q000737:chemistry*; D008099:Liver / Q000201:enzymology
D000468:Alkalies; D008041:Linoleic Acids; D008054:Lipid Peroxides; C008285:linoleic acid hydroperoxide; D002374:Catalase