title: Linoleate hydroperoxides are cleaved heterolytically into aldehydes by a Lewis acid in aprotic solvent.
abstract: Treatment of isomeric methyl linoleate hydroperoxides with a Lewis acid, BF3, in anhydrous ether led to a carbon-to-oxygen rearrangement that caused cleavage into shorter-chain aldehydes. Methyl (9Z,11E)-13-hydroperoxy-9,11-octadecadienoate afforded mainly hexanal and methyl (E)-12-oxo-10-dodecenoate, whereas methyl (10E,12Z)-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.
authors: Northern Regional Research Center, Agricultural Research Service, USDA, 61604, Peoria, IL.
authors: H W
authors: HW
authors: Gardner
authors: Northern Regional Research Center, Agricultural Research Service, USDA, 61604, Peoria, IL.
authors: R D
authors: RD
authors: Plattner