Hydroperoxide

Hydroperoxide refers to compounds containing the hydroperoxy group, -OOH. The simplest member is hydrogen peroxide (HOOH). In organic chemistry, the term usually denotes hydroperoxides of the form ROOH, where R is an alkyl, aryl, or other substituent.

The hydroperoxy group consists of a hydroperoxy moiety attached to R. The O–O bond is relatively weak compared with carbon–heteroatom bonds, contributing to instability and a tendency to decompose under heat, light, or metal catalysis. Decomposition can proceed via homolytic O–O scission to give radicals (RO• and HO•) or via rearrangements, generating alcohols, ketones, or alkanes, depending on the substrate. Hydroperoxides can act as radical initiators in polymerization and in various oxidation reactions.

Formation and occurrence: Hydroperoxides arise by autoxidation of hydrocarbons, by oxidation of alcohols or ethers, and in lipid peroxidation. They are common intermediates in industrial and biological oxidation processes. In biology, lipid hydroperoxides form during oxidative stress and can propagate chain reactions if not reduced.

Examples and applications: Cumene hydroperoxide is a key intermediate in the industrial production of phenol and acetone via the Hock process. Tert-butyl hydroperoxide is used as a radical initiator in polymerization and as an oxidant in organic synthesis. Hydrogen peroxide, the simplest hydroperoxide, is widely used as an oxidant, disinfectant, and bleaching agent.

Safety: Organic hydroperoxides are frequently sensitive to heat, shock, and friction and can be explosive. They require careful storage, temperature control, and avoidance of incompatible materials.