Showing papers in "Journal of The Chemical Society (resumed) in 1946"

3. The course of autoxidation reactions in polyisoprenes and allied compounds. Part XI. Double bond movement during the autoxidation of a mono-olefin

Abstract: In an earlier part of this investigation it was shown that the autooxidation 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):