The Autoxidation of Acetylenic Hydrocarbons

Abstract

AbstractAcetylenic hydrocarbons react with molecular oxygen at temperatures of 70–120°C both by attack at the CH bonds in α‐position to the triple bond (formation of acetylenic hydroperoxides) and by attack at the CC triple bond (or the corresponding ketocarbenes) are very instable intermediates which react either under H‐shift to α,β‐unsaturated ketones or under alkyl‐ or aryl‐shift to ketenes. Further oxidation of the α‐diketones proceeds easily corresponding to a free radical chain mechanism with acyl radicals as chain carriers, and gives the corresponding carboxylic acid anhydrides as final products.