GB700546A - Hydroperoxides - Google Patents

Abstract

Hydroperoxides are obtained from the liquid phase oxidation of cycloaliphatic or aromatic hydrocarbons, e.g. cyclohexane, cyclohexene, methylcyclohexane methylcyclopentane and alkyl benzenes, by injecting a gas containing molecular oxygen into the liquid being oxidized, removing hydroperoxide from the reaction mixture by adsorption on a surface active solid adsorbent and recovering the hydroperoxide by elution from the adsorbent. Preferably the process is carried out by injecting air into the hydrocarbon at a temperature in the range 30-200 DEG C. under a pressure of 50 to 750 pounds/sq. inch until from 1.0 per cent - 20 per cent. of the hydrocarbon is oxidized, removing the hydroperoxide by adsorption on active alumina, recycling the unoxidized reactant to the oxidation vessel and eluting the peroxide from the active alumina with a hydroxyalkane such as methanol. In examples (1) cyclohexane is oxidised by air at 130 DEG C. and 200 lbs./sq. inch until 1.7 per cent is converted to hydroperoxide at which point a separate water phase appears, the hydroperoxide is adsorbed on active alumina, eluted with methanol, separated by evaporating the methanol and oxidized by nitric acid in the presence of ammonium vanadate to adipic acid; (2) cyclohexene is oxidized at 30 DEG C. to cyclohexenyl hydroperoxide, and is separated and converted to adipic acid as in (1); (3) methylcycohexane is oxidized to the hydroperoxide as in (1) and the methanolic solution obtained is treated with ferrous sulphate to give a ketonic product which is oxidized to dibasic acids; (4) cyclohexane is oxidised as in (1) with variation in the conditions of temperature and time. Specification 633,354 is referred to.