Bildung von Enolether‐Epoxiden durch Einwirkung von (9S,10E,12Z)‐Hydroperoxyoctadecadiensäure auf Plasmalogene

Abstract

Formation of Enol Ether Epoxides by Reaction of (9S,10E,12Z)‐Hydroperoxyoctadecadienoic Acid with Plasmalogens(9S,10E,12Z)‐Hydroperoxyoctadecadienoic acid (8a) oxidizes enol ethers (e.g. 2 and neutral plasmalogens 3) under physiological conditions (pH = 6.6, room temperature). The reaction products, unstable enol ether epoxides 9a and 10a, react as recently demonstrated with methanol to α‐hydroxyaldehyde dialkyl acetals 11a or with 1,2‐ethanedithiol to 2‐(α‐hydroxyalkyl)dithiolans 13a which can be detected by GC/MS after trimethylsilylation. If [18O2]‐(9S,10E,12Z)‐hydroperoxy‐octadecadienoic acid (8b) is used instead of 8a one atom of 18O is incorporated into the enol ether epoxide and found in the α‐hydroxy group of the aldehyde derivatives 11 and 13.