The Course of Autoöxidation Reactions in Polyisoprenes and Allied Compounds. XI. Double-Bond Movement during the Autoöxidation of a Monoölefin

In an earlier part of this investigation it was shown that the autoöxidation of Δ1,4-diene8 and Δ1,4,7-, etc., polyene compounds produces peroxido derivatives containing conjugated units, and to explain the formation of the latter a reaction-mechanism was proposed which postulated the detachment of hydrogen atoms from the reactive methylene groups under the action of molecular oxygen, and subsequent rearrangement of the resonating radical residues before oxygen and, finally, hydrogen combine therewith to give hydroperoxides: (see PDF for diagram) It was recognized that, if this mechanism is valid for methylene-interrupted diene or polyene systems, it might reasonably be expected to apply also to the formation of hydroperoxides by the action of oxygen either on simple olefins or on polyolefins containing two or more methylene groups between the double bonds. To demonstrate successfully that even the simplest olefin system capable of hydroperoxidation can give both of the oxygenated forms (A) and (B):