Photolysis of unsaturated fatty acid hydroperoxides. 2. Products from the anaerobic decomposition of methyl 13(S)-hydroperoxy-9(Z),11(E)-octadecadienoate dissolved in methanol

✍ Scribed by Peter Schieberle; Yezid Trebert; Joachim Firl; Werner Grosch

• Publisher: Elsevier Science
• Year: 1985
• Tongue: English
• Weight: 764 KB
• Volume: 37
• Category: Article
• ISSN: 0009-3084
• DOI: 10.1016/0009-3084(85)90077-5

✦ Synopsis

A solution of methyl 13(S)-hydroperoxy-9(Z),ll(E)-octadecadienoate (13-HPOD)in methanol was irradiated under anaerobic conditions at 15°C with light at wavelengths greater than 230 nm. After 2 h the 13-HPOD was completely degraded and four major products were formed. Three of them were identified as mixtures of diastereomers: methyl 13-hydroxy-12methoxy-9-hydroxymethyl-10(E)-octadecenoate, methyl trans-12,13-epoxy-11-hydroxymethyl-9(Z)-octadecenoate and methyl trans-12,13-epoxy-9daydroxymethyl-10(E)-octadecenoate. The formation of these products indicates that hydroxy radicals liberated by photolysis of the 13-HPOD react with the solvent methanol producing mainly hydroxymethyl radicals, which become part of the reacting system. The fourth product, methyl trans-12,13-epoxy-threo-11hydroxy-9 (Z)-octadecenoate, was formed stereospecifically.