Peracids, Prilezhaev reaction

The Prilezhaev reaction is a rarely used name for the epoxidation of an alkene 1 by reaction with a peracid 2 to yield an oxirane 3. The epoxidation of alkenes has been further developed into an enantioselective method, that is named after Sharpless. 

Peracids react heterolytically with olefins with the formation of epoxides by the Prilezhaev reaction. So, the co-oxidation of aldehydes with olefins has technological importance. Peracids react with ketones with formation of lactones. These reactions will be discussed in Section 8.2. The oxidation of aldehydes are discussed in monographs [4-8]. 

The Prilezhaev reaction is the formation of epoxides by the reaction of alkenes with peracids. 

The reaction of olefin epoxidation by peracids was discovered by Prilezhaev [235]. The first observation concerning catalytic olefin epoxidation was made in 1950 by Hawkins [236]. He discovered oxide formation from cyclohexene and 1-octane during the decomposition of cumyl hydroperoxide in the medium of these hydrocarbons in the presence of vanadium pentaoxide. From 1963 to 1965, the Halcon Co. developed and patented the process of preparation of propylene oxide and styrene from propylene and ethylbenzene in which the key stage is the catalytic epoxidation of propylene by ethylbenzene hydroperoxide [237,238]. In 1965, Indictor and Brill [239] published studies on the epoxidation of several olefins by 1,1-dimethylethyl hydroperoxide catalyzed by acetylacetonates of several metals. They observed the high yield of oxide (close to 100% with respect to hydroperoxide) for catalysis by molybdenum, vanadium, and chromium acetylacetonates. The low yield of oxide (15-28%) was observed in the case of catalysis by manganese, cobalt, iron, and copper acetylacetonates. The further studies showed that molybdenum, vanadium, and... 

Direct Oxidation with Stoichiometric Oxidants. Discovered by Prilezhaev in 1909,211 the typical epoxidation reaction of alkenes is their oxidation with organic peracids. Of the large number of different peroxycarboxylic acids used in... 

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