Homogeneous Liquid-Phase Oxidation of Ethylbenzene to Acetophenone in Continuous Flow Mode

Abstract

The oxidation of ethylbenzene with hydrogen peroxide and molecular oxygen catalyzed by cobalt and bromide ions in acetic acid as solvent was studied. The oxidation of ethylbenzene with hydrogen peroxide provided a mixture of ethylbenzene hydroperoxide, acetophenone, 1-phenylethanol, and 1-phenylethyl acetate. After rapid initial oxidation, the reaction rate decreased steadily so that full conversion of ethylbenzene and reaction intermediates to acetophenone could not be achieved. In contrast, no catalyst deactivation was observed for oxidations using atmospheric oxygen. Ethylbenzene was oxidized to acetophenone in 74% selectivity after a reaction time of 150 min at 80 °C. The reaction conditions were translated to a continuous flow process using a tubular gas–liquid reactor. At temperatures of 110 to 120 °C and an oxygen pressure of ∼12 bar, the reaction time necessary for complete oxidation of ethylbenzene was reduced to 6 to 7 min. The acetophenone was formed in 80 to 84% selectivity, and virtually pure acetophenone was isolated in 66% product yield without the need for chromatography. Increasing the reaction time to 16 min at a reaction temperature of 150 °C led to benzoic acid as the final product in 71% yield.