Kinetics of the catalytic reduction of organic peroxides and hydroperoxides Communication 1. hydrogenation of ?, ?-dimethylbenzyl hydroperoxide, ?, ?-dimethylbenzyl ethyl peroxide, and 1, 2, 3, 4-tetrahydro-1-naphthyl hydroperoxide

Abstract

1. It was shown that organic peroxides and hydroperoxides are rapidly hydrogenated to the corresponding alcohols over Raney nickel, which is in accord with calculations based on the multiplet theory. 2. The kinetics of these reactions were investigated. It was found that the nature and structure of the substituents affect the rate of reduction, and as a consequence di-tert-butyl peroxide is not hydrogenated at all at temperatures ranging up to 50°. 3. The actions of Raney nickel and palladium catalysts were investigated. The peroxy compounds were hydrogenated over both catalysts, mainly in accordance with a zero-order law. The apparent activation energies for the reduction of peroxides and hydroperoxides were close in value, being 5.4 and 5 kcal/ mole respectively. The hydrogenation of a, α-dimethylbenzyl ethyl peroxide was retarded by the reaction products. 4. The rate of catalytic reduction depends on the nature of the solvent. In alcoholic solution reaction proceeds more rapidly than in cyclohexane, benzene, or decahydronaphthalene.