Oxidation, basic conditions epoxide formation

In this oxidative degradation, MTO decomposes into catalytically inert perrhenate and methanol. The decomposition reaction is accelerated at higher pH, presumably through the reaction between the more potent nucleophile H02- and MTO. The decomposition of MTO under basic conditions is rather problematic, since the selectivity for epoxide formation certainly profits from the use of nonacidic conditions. 

It is noticed that when Fe3+OOR is formed in aprotic diluters (under strongly basic conditions) at low temperature, degradation products are synthesized by reaction (7.4) [29], However, in hydroxide diluters oxidants dissociate heterolytically by reaction (7.3) [30, 31], which is proved by the formation of the following products epoxides from alkenes and alcohols from ROOH. 

Acid-catalyzed oxidation of epoxides with HBp4-OMe2/ DMSO results in the formation of a-hydroxy ketones (eq 6). This procedure in an acidic medium complements the a-hydroxylation of ketone enolates under strongly basic conditions. 

Under the same conditions, the reactivity of three-membered cyclic ethers in anionic copolymerization with cychc anhydrides is higher than that of four-membered ethers Higher membered cyclic ethers can polymerize or copolymerize with anhydrides only by a cationic mechanism whereby not only alternating copolymer but also a great number of polyether sequences are formed. This difference in reactivity is evidently associated with the basicity of cychc ethers, three-membered ethers having the lowest basicity The lower basicity causes a lower reactivity of the epoxide (cychc ether) in competitive reactions or in copolymerization with other cychc monomers compared with the expected reactivity which follows from the strain in the ring. The strain energy, taken as the difference between the experimental and calculated heats of formation was found to be 54.4kJ/mol for ethylene oxide... 

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