Electrochemistry of α, α'-dibromoketones: Reduction of 2,4-dibromo-1,5-diphenyl-1,4-pentadien-3-one (α,α'-dibromo-dibenzylidene acetone) at the mercury electrode

Abstract

2,4-Dibromo-1,5-diphenyl-1,4-pentadien-3-one (VIII (PhCH=CBrCOCBr=CHPh, α, ga'-dibromodibenzylidene acetone) is electroreduced in “aprotic” dimethylformamide at the mercury electrode; E 1/2 of the first step is −0.97 V vs. SCE; two electrons/molecule of VIII were transferred (c.p.e.) and two Br −/molecule of VIII were released. The product was identified as cis-1,5-diphenyl-1-penten-4-yn-3-one(PhCH=CHCOC=CPh), which is the rearrangement product of an unstable dimethylenecyclopropanone. In MeOH solutions, electroreduction of VIII follows a different path, the first two-electron step being substituted by a four-electron step (c.p.e.), which furnishes 3,4-diphenyl-cyclopent-2-enone, XIII. XIII seems to be a rearrangement product of a cyclic precursor. Subsequent two-step reduction of this intermediate in MeOH affords finally 1,5-diphenylpentan-3-one(α, α'-dibenzylacetone).