Hydrogen Peroxide Reactions with Olefins

Abstract

The osmium tetroxide-catalyzed addition of hydrogen peroxide to olefins has been reinvestigated with innovations of reagents, catalyst, and procedures to obtain product analyses and material balances for the hydrogen peroxide consumption. Significant amounts of carbonyl by-products-acetol, organic acids, peracids, and possibly pyruvaldehyde-are formed under the range of conditions studied. Experimental design studies of the effects of reaction variables upon yields of the various products under batch and continuous addition conditions have been completed. The nature of the catalytic complex involved in the initiation of the reaction is reviewed. The order and rate of product appearance does not support a simple oxidation sequence. A branching reaction sequence consistent with experimental results is proposed.uydrogen peroxide is becoming less expensive and has been used for the " liquid-phase oxidation of olefins (7,21,22,23,24,26,34,38,39); but its use in oxidizing gaseous olefins has not received much attention. We have investigated its use in oxidizing gaseous olefins, especially propylene, noting in particular the glycol and by-product yields obtained.A review of the chemical literature (1,2,5,16,20,30,40) and laboratory experiments confirmed that the Milas reagent ( 14,19,21,22,23,24,26,28 ), osmium tetroxide in f erf-butyl alcohol, is one of the more effective catalysts for liquid-phase oxidation.