Hydrogen peroxide hydroperoxide synthesis

Synthesis. Dialkyl peroxides are prepared by the reaction of various substrates with hydrogen peroxide, hydroperoxides, or oxygen (69). They also have been obtained from reactions with other organic peroxides. For example, dialkyl peroxides have been prepared by the reaction of hydrogen peroxide and alkyl hydroperoxides with alMating agents, eg, RX and olefins (33,66,97) (eqs. 24—27). 

Synthesis. Dialkyl peroxides are prepared by the reaction of various substrates with hydrogen peroxide, hydroperoxides, 01 oxygeu. They also have been obtained from reactions with other organic peroxides. 

The heme peroxidases oxidize a variety of structurally diverse substrates by using hydrogen peroxide or hydroperoxides as oxidants, whereby the oxidants are reduced to water or alcohol. In the following, the present state of such peroxidase-catalyzed reactions in organic synthesis is described, which unquestionably is important for preparative work. 

Literature procedures for the synthesis of hydroperoxides include the preparation from hydrogen peroxide (via reaction with alkyl halides, -phosphites, -suEonates, alkenes. 

Hydrogen peroxide and alkyl hydroperoxides are important oxidants in organic synthesis, but they usually need to be activated by catalysts such as tungsten, molybdenum, and titanium oxides. Heteropoly compounds are good catalysts for oxygenation of olefins or paraffins and oxidative cleavage of vic-diols. 

Iodine-catalysed hydroperoxidation of cyclic and acyclic ketones with aqueous hydrogen peroxide in acetonitrile is an efficient and eco-friendly method for the synthesis of gem -dihydroperoxides and the reaction is conducted in a neutral medium with a readily available low-cost oxidant and catalyst.218 Aryl benzyl selenoxides, particularly benzyl 3,5-bis(trifluoromethyl)phenyl selenoxide, are excellent catalysts for the epoxidation of alkenes and Baeyer-Villiger oxidation of aldehydes and ketones with hydrogen peroxide.219 Efficient, eco-friendly, and selective oxidation of secondary alcohols is achieved with hydrogen peroxide using aqueous hydrogen bromide as a catalyst. Other peroxides such as i-butyl hydroperoxide (TBHP), sodium... 

When primary alkyl phenyl tellurium or secondary alkyl phenyl tellurium compounds in methanol were treated with an excess of 3-chloroperoxybenzoic acid at 20, the phenyltelluro group was eliminated and replaced by a methoxy group. This reaction, which converts alkyl halides used in the synthesis of alkyl phenyl telluriums to alkyl methyl ethers, produced the ethers in yields as high as 90%3-4 Olefins are by-products in these reactions4 With ethanol as the solvent, ethyl ethers were formed. Other oxidizing agents (hydrogen peroxide, ozone, (ert.-butyl hydroperoxide, sodium periodate) did not produce alkyl methyl ethers. 

A direct, but mechanistically obscure, synthesis of trifluoromethyl hydroperoxide has been developed, involving the decomposition of the adduct formed between hexafluoro-acetone and hydrogen peroxide [107] (Figure 8.67). 

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