Local activation and specific reactivity of compounds with a system of conjugation. Communication 14. Thermal decomposition of tertiary butyl hydroperoxide in the presence of certain compounds with a system of conjugation

Abstract

1. The decomposition of tert-butyl hydroperoxide in chlorobenzene and n-octane was studied in the temperature interval 140–180° in the presence of anthracene and the paramagnetic fraction isolated from its pyrolysis products. 2. Anthracene inhibits the chain decomposition of hydroperoxide in both cases, while the paramagnetic fraction inhibits the chain decomposition in nonpolar medium (octane), but accelerates the decomposition in polar medium (chlorobenzene). The latter effect is evidently associated with the formation of a polarized transition complex between the paramagnetic fraction and the hydroperoxide. 3. In the presence both of anthracene and of the paramagnetic fraction, the amount of peroxides accumulated in the oxidized cetane increases sharply. A hypothesis on the possibility of the appearance of synergic effects when the indicated additives are combined with compounds capable of reducing hydroperoxide without the formation of free radicals, was advanced and experimentally confirmed.