7583-74-6Relevant academic research and scientific papers
Highly efficient catalysts for epoxidation mediated by iminium salts
Bulman Page, Philip C.,Buckley, Benjamin R.,Appleby, Louise F.,Alsters, Paul A.
, p. 3405 - 3411 (2007/10/03)
A range of substituted dihydroisoquinolinium salts has been tested in the catalytic epoxidation of several alkenes. Catalyst loadings as low as 0.5 mol% have been used in the epoxidation of 1-phenylcyclohexene. Georg Thieme Verlag Stuttgart.
Diverse pathways for the palladium(II)-mediated oxidation of olefins by tert-butylhydroperoxide
Yu, Jin-Quan,Corey
, p. 2727 - 2730 (2007/10/03)
(Matrix presented) New procedures are described for the palladium-catalyzed oxidation of olefins by tert-butylhydroperoxide under slightly basic conditions in CH2Cl2 solution at 0-25°C.
Fluorinated alcohols: Effective solvents for uncatalysed epoxidations with aqueous hydrogen peroxide
Van Vliet,Arends,Sheldon
, p. 248 - 250 (2007/10/03)
Buffered aqueous hydrogen peroxide in combination with fluorinated alcohols (trifluoroethanol at reflux temperature or hexafluoro-2-propanol at room temperature) oxidises a variety of alkenes to the corresponding epoxides in high rates and fairly high yields, without the need for any catalyst.
Molybdenum-catalyzed epoxidations of oct-1-ene and cyclohexene with organic hydroperoxides: Steric effects of the alkyl substituents of the hydroperoxide on the reaction rate
Lempers,Van Crey,Sheldon
, p. 542 - 546 (2007/10/03)
A kinetic study of the epoxidation of oct-1-ene and cyclohexene with alkyl hydroperoxides is reported. The alkyl hydroperoxides were obtained in a moderate to high purity from the corresponding alcohols by acid-catalyzed exchange with hydrogen peroxide. The reaction rates in pseudo first-order experiments of these olefins with various alkyl hydroperoxides strongly depend on the structure of the alkyl group of the alkyl hydroperoxide. When one of the methyl groups in tert-butyl hydroperoxide (TBHP, 4a) is substituted by an alkyl group, R, the reaction rate decreases in the order Et > Pr > Bu > t BuCH2 > tBu. Substitution of two methyl groups of TBHP as in 1-ethyl-1-methylpropyl hydroperoxide (5a) and 1-ethyl-1-methylbutyl hydroperoxide (5b) showed a further decrease in reaction rate of epoxidation. When all three methyl groups are substituted by, for example, three ethyl groups as in 1,1-diethylpropyl hydroperoxide (6a) a decrease of approximately 99% in reaction rate is observed. Introduction of a ring system in the hydroperoxide such as in cyclohexyl hydroperoxide (3), 1-methyl-cyclohexyl hydroperoxide (2) and pinane hydroperoxide (1) also showed a dramatic decrease in reaction rate of epoxidation. An investigation of relative rates of epoxidation in competition experiments of cyclohexene and hex-1-ene with 1-tert-butylcyclohexene with different alkyl hydroperoxides also showed them to depend on the structure of the alkyl group of the alkyl hydroperoxide. These results are rationalized on the basis of a mechanism involving nucleophilic attack of the olefin on an alkylperoxomolybdenum(VI) intermediate. Bulky substituents at the α-position in the alkyl hydroperoxide can seriously impede the approach of the olefin to the O-O bond.
