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Linoleate hydroperoxides are cleaved heterolytically into aldehydes by a Lewis acid in aprotic solvent
Author(s) -
Gardner H. W.,
Plattner R. D.
Publication year - 1984
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/bf02534458
Subject(s) - chemistry , homolysis , lewis acids and bases , anhydrous , solvent , ether , radical , hexanal , organic chemistry , bond cleavage , medicinal chemistry , methyl oleate , oxygen , heterolysis , catalysis
Treatment of isomeric methyl linoleate hydroperoxides with a Lewis acid, BF 3 , in anhydrous ether led to a carbon‐to‐oxygen rearrangement that caused cleavage into shorter‐chain aldehydes. Methyl (9 Z ,11 E )‐13‐hydroperoxy‐9,11‐octadecadienoate afforded mainly hexanal and methyl ( E )‐12‐oxo‐10‐dodecenoate, whereas methyl (10 E ,12 Z )‐9‐hydroperoxy‐10,12‐octadecadienoate cleaved into 2‐nonenal and methyl 9‐oxononanoate. The 2 aldehydes obtained from each hydroperoxide isomer were uncharacteristic of the complex volatile profile usually obtained by β‐scission of oxy radicals derived from homolysis of the hydroperoxide group. Rather, the reaction resembled the one catalyzed by the plant enzyme, hydroperoxide lyase.