Hydroperoxide

Organic hydroperoxides can either intentionally or unintentionally initiate explosive polymerisation in materials with unsaturated chemical bonds.

[4] Hydroperoxides can be reduced to alcohols with lithium aluminium hydride, as described in this idealized equation: This reaction is the basis of methods for analysis of organic peroxides.

[6] The phosphite esters and tertiary phosphines also effect reduction: "The single most important synthetic application of alkyl hydroperoxides is without doubt the metal-catalysed epoxidation of alkenes."

For example, the cobalt catalyzed oxidation of cyclohexane to cyclohexanone:[9] Drying oils, as found in many paints and varnishes, function via the formation of hydroperoxides.

[11] Such reactions rely on radical initiators that reacts with oxygen to form an intermediate that abstracts a hydrogen atom from a weak C-H bond.

Specific reactions include addition of hydrogen peroxide across the C=O double bond: In some cases, these hydroperoxides convert to give cyclic diperoxides: Addition of this initial adduct to a second equivalent of the carbonyl: Further replacement of alcohol groups: Triphenylmethanol reacts with hydrogen peroxide gives the unusually stable hydroperoxide, Ph3COOH.

One example involves sodium perborate, a commercially important bleaching agent with the formula Na2[(HO)2B]2(OO)2)].

The general structure of an organic hydroperoxide with the blue marked functional group, where R stands for any group, typically organic
The Sharpless epoxidation
The Sharpless epoxidation
Synthesis of cumene hydroperoxide
Synthesis of hydroperoxides of alkene and singlet oxygen in an Schenck ene reaction
Illustrative biosynthetic transformation involving a hydroperoxide. Here cis-3-hexenal is generated by conversion of linolenic acid to the hydroperoxide by the action of a lipoxygenase followed by the lyase-induced formation of the hemiacetal. [ 15 ]
Structure of a square planar palladium hydroperoxide complex