Prostaglandin-like substances formed during autoxidation of methyl linolenate

Prostaglandin-like substances other than 3-(2-ethyl-5-hydroxy-3-oxo)-cyclopentanyl-2-propenal (compound I), which upon reacting with amino acids form reddish pigments, were purified, and their chemical structures were determined. Three red pigment-forming substances (RPS) in autoxidized methyl linolenate were purified successively by gel chromatography on Sephadex LH-20, column chromatography and thin layer chromatography on Silica Gel 60, and by high performance liquid chromatography on μ-Porasil. IR spectra of the RPS showed the absorption of an ester group (νC=O 1730 cm⁻¹ in CHCl₃) and of a longer branched chain (νC-H 2800–3100 cm⁻¹), in addition to the absorption bands observed in compound I. Electron impact mass spectra of the trimethylsilyl ethers obtained after reduction with NaBH₄ and NaBD₄ were analyzed in detail and compared with those of compound I. The structures of the RPS were identified as stereoisomeric methyl 8-2-(2-formylvinyl)-3-hydroxy-5-oxo-cyclopentanyl]-octanoates derived from methyl 12-hydroperoxy-linolenate. Presented at the general meeting of the Japanese Society of Scientific Fisheries, held at Tohoku University, Sendai, Japan, October 1984.