KINETIC ASPECT OF INTRAMOLECULAR HOMOLYTI C SUBSTITUTIONS DECOMPOSITIONS OF UNSATURATED PEROXIDES DERIVED FROM PINANE

The decomposition, in dichlormethane, of beta- and gamma-unsaturated p eroxides derived from pinane leads to transient tertiary pinanyl adduc t radicals. The evolution of the reaction depends on the position of t he insaturation. An intramolecular homolytic substitution gives foncti onal pinanic epoxides in the first case; a beta-scission followed by a hydrogen transfert yields on fonctional p-methenic peroxides in the s econd case.