DECOMPOSITION DU PERCARBONATE DE O,O-t-BUTYLE ET O-ISOPROPENYLE EN SOLUTION-2. ACETONYLATION DE CYCLANONES ET OXACYCLANES.

Article abstract of DOI:10.1016/S0040-4020(01)88563-X

The decomposition of O,O-tert-butyl and O-isopropenyl peroxycarbonate in cyclanones and oxycyclanes leads to acetonylated derivatives of these solvents.Although the reaction mechanism involves in both cases the addition of free radicals derived from solvent to the double bond of the peroxycarbonate, the orientation of the whole process depends on the solvent.In the case of oxacyclanes the relative ratios of α-,β-and γ-(with regard to the heteroatom) acetonylated products are likely to express the reactivity of t-butoxy radicals towards the differenet carbon atoms of the solvent.On the contrary, in the case of cyclanones transfer reactions occur from β- or γ-radicals (with regard to the carbonyl group) to α-carbon atoms of other solvent molecules and the relative ratios of α-, β- and γ-acetonylated products depend on on the peroxycarbonate concentration: when it is high, about 25percent β and γ isomers are formed; when it is low, only the α isomer is obtained.