Oxidations of organic compounds by cobaltic salts. Part IX. The oxidations of di-isopropyl ether and di-2-chloroethyl ether

Abstract

The rate of oxidation of di-isopropyl ether by cobaltic perchlorate in methyl cyanide–water mixtures, and the yields of acetone produced, have been measured. The reaction is about ten times slower than the oxidation of dibenzyl ether. There is evidence that the reaction: Prⁱ·+ PrⁱOPrⁱ [graphic omitted] Me₂ĊOPr competes with the main oxidative sequence which appears to be: PrⁱOPrⁱ+ Co^III→ Me₂ĊOPrⁱ+ Co^II+ H⁺ Me₂ĊOPrⁱ→ Me₂CO + Prⁱ Prⁱ·+ Co^IIIaq. [graphic omitted] PrⁱOH + Co^II+ H⁺ and the ratio k_f/k_c is about 3 × 10^–3.

The oxidation of di-2-chloroethyl ether is autocatalytic and liberates chloride ions. A chain reaction involving Cl· atoms is proposed.