Reactions of Ozonides. XI. A ¹⁴C Tracer Study of the Ozonolysis of Ethylidenecyclohexane in Cyclohexanone

Abstract

Using 14C labelling of cyclohexanone or ethylidenecyclohexane, examination of the products of ozonolysis of the alkene in the presence of the ketone reveal 6-hexanolide to be initially formed in < 1% yield. Cyclohexanone peroxides are the major products from ethylidenecyclohexane ozonized in cyclohexanone. Carbonyl-modified alkene ozonolysis is therefore suggested to be explicable by the Criegee mechanism, and it is unnecessary to invoke Baeyer–Villiger interactions. Ozonide formation is not totally suppressed by cyclohexanone.

Reactions of ozonides. XII. Ozonolysis of methylenecyclohexane

“…Story and co-workers (1)(2)(3) invoked BaeyerVilliger oxidation of a ketone solvent as another possible mechanism for diminution of ozonide yield: we have used I4C to demonstrate that cyclohexanone can function this way in ethylidenecyclohexane ozonolysis in no more than 0.02% yield (6). There is no clear relation between effectiveness of suppression of ozonide formation and dielectric constant of solvents of Table 1.…”