Singlet Oxygenation of a Conjugated Diallene: Attempt to Prepare a Stable Divinyl Peroxide

Article abstract of DOI:10.1021/jo00154a011

A conjugated diallene, 2,3-divinylidenebicyclo<2.2.1>heptane, was prepared and isolated.Photosensitized oxygenation of this allene leads to two isolated oxygenated products in 50percent yield.Detection of these products is interpreted to implicate an unstable cyclic divinyl peroxide intermediate.Attempts to detect this intermediate by low temperature NMR spectroscopy and by chemiluminescence were unsuccessful.The instability of this compound is attributed to the destabilizing lone-pair interaction of the peroxide oxygen atoms.