Attempted synthesis of (9Z)-methyl 12-hydroperoxyoctadec-9-enoate

Abstract

The silver trifluoroacetate-assisted reaction of alkyl halides with hydrogen peroxide has been investigated. Methyl 12-bromostearate furnished, for the first time, methyl 12-hydroperoxystearate in 34% yield. Methyl 12-bromo-oleate, however, gave cyclopropane hydroperoxides (via a homoallylic cation rearrangement) and hydroperoxy epidioxides (presumably via methyl 12-hydroperoxyoleate which could not be isolated). Methyl 9-t-butylperoxy-10,11-methyleneheptadecanoate was produced by the reaction of methyl 12-bromo-oleate with t-butyl hydroperoxide in the presence of silver trifluoroacetate. None of these transformations occurred when silver trifluoroacetate was replaced by the acetate.