Abstract
Thermal decomposition of 1-apocamphoryl peroxide has been investigated in CCl 4 using the 18O-labelled peroxide. 1-Apocamphoryl peroxide is the first example which undergoes radical decomposition, carboxy-inversion and oxygen scrambling reaction between carbonyl and peroxidic O atoms in the peroxide in comparable rates. The major product of the decomposition was the inversion product, 1-apocamphoryl 1-apocamphyl carbonate (52·5%), and only a minute amount of 1-apocamphyl 1-apocamphorate (2·2%) was formed. The rates of oxygen scrambling were found to be 2·70±0·21 × 10 −6 (55°), 1·85±0·12 × 10 −1 sec −1 (70°) and 9·33±0·18 × 10 −5 sec −1 (84·3°) (E a, 27·5 Kcal/mol, ΔS‡, −2·3 e.u.). The cage recombination mechanism was suggested for the oxygen scrambling and the amounts of cage recombination of 1-apocamphoryloxy radical pair were calculated as 65% (55°), 60% (70°) and 52% (84·3°). The yield of the ester and the amount of cage recombination of geminate acyloxy radical pair were rationalized in terms of the stability of acyloxy radicals formed in the cage.
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