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Lack of regioselectivity in formation of oxohydroxyoctadecenoic acids from the 9‐ or 13‐hydroperoxide of linoleic acid
Author(s) -
Gardner H. W.,
Kleiman R.
Publication year - 1979
Publication title -
lipids
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.601
H-Index - 120
eISSN - 1558-9307
pISSN - 0024-4201
DOI - 10.1007/bf02534127
Subject(s) - regioselectivity , chemistry , linoleic acid , catalysis , decomposition , lewis acids and bases , medicinal chemistry , cis–trans isomerism , organic chemistry , stereochemistry , fatty acid
Abstract Either 9‐hydroperoxy‐ trans ‐10, cis ‐12‐octadecadienoic acid or 13‐hydroperoxy‐ cis ‐9, trans ‐11‐octadecadienoic acid was treated with the catalyst, cysteine‐FeCl 3 , in the presence of oxygen. Oxohydroxyoctadecenoic acids were among the many products formed as a result of hydroperoxide decomposition. A mixture of 9(13)‐oxo‐13(9)‐hydroxy‐ trans ‐11(10)‐octadecenoic acids (δ‐ketols) was produced from either isomeric hydroperoxide. The formation of isomeric δ‐ketols from 9‐hydroxy‐ trans ‐12,13‐epoxy‐ trans ‐10‐octadecenoic acid (epoxyol), a known product of 13‐hydroperoxy‐ cis ‐9, trans ‐11‐octadecadienoic acid decomposition, implies that the epoxyol is an intermediate. The mechanism was elucidated by the facile conversion of the epoxyol (methyl ester_ to methyl 9(13)‐oxo‐13(9)‐hydroxy‐ trans ‐11(10)‐octadecenoates with a Lewis acid, BF 3 ‐etherate.