- Synthesis of Ethers via Reaction of Carbanions and Monoperoxyacetals
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Although transfer of electrophilic alkoxyl ("RO+") from organic peroxides to organometallics offers a complement to traditional methods for etherification, application has been limited by constraints associated with peroxide reactivity and stability. We now demonstrate that readily prepared tetrahydropyranyl monoperoxyacetals react with sp3 and sp2 organolithium and organomagnesium reagents to furnish moderate to high yields of ethers. The method is successfully applied to the synthesis of alkyl, alkenyl, aryl, heteroaryl, and cyclopropyl ethers, mixed O,O-acetals, and S,S,O-orthoesters. In contrast to reactions of dialkyl and alkyl/silyl peroxides, the displacements of monoperoxyacetals provide no evidence for alkoxy radical intermediates. At the same time, the high yields observed for transfer of primary, secondary, or tertiary alkoxides, the latter involving attack on neopentyl oxygen, are inconsistent with an SN2 mechanism. Theoretical studies suggest a mechanism involving Lewis acid promoted insertion of organometallics into the O-O bond.
- Kyasa, ShivaKumar,Meier, Rebecca N.,Pardini, Ruth A.,Truttmann, Tristan K.,Kuwata, Keith T.,Dussault, Patrick H.
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p. 12100 - 12114
(2016/01/09)
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- Hydrogen peroxide oxygenation of alkanes including methane and ethane catalyzed by iron complexes in acetonitrile
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This paper describes an investigation of the alkane oxidation with hydrogen peroxide in acetonitrile catalyzed by iron(III) perchlorate (1), iron(III) chloride (2), iron(III) acetate (3) and a binuclear iron(III) complex with 1,4,7-triazacyclononane (4). The corresponding alkyl hydroperoxides are the main products. Nevertheless in the kinetic study of cyclohexane oxidation, the concentrations of oxygenates (cyclohexanone and cyclohexanol) were measured after reduction of the reaction solution with triphenylphosphine (which converts the cyclohexyl hydroperoxide to the cyclohexanol). Methane and ethane can be also oxidized with TONs up to 30 and 70, respectively. Chloride anions added to the oxidation solution with 1 activate the perchlorate iron derivative in acetonitrile, whereas the water as additive inactivates 2 in the H 2O2 decomposition process. Pyrazine-2-carboxylic acid (PCA) added to the reaction mixture decreases the oxidation rate if 1 or 2 are used as catalysts, whereas compounds 3 and 4 are active as catalysts only in the presence of small amount of PCA. The investigation of kinetics and selectivities of the oxidations demonstrated that the mechanisms of the reactions are different. Thus, in the oxidations catalyzed by the 1, 3+PCA and 4+ PCA systems the main oxidizing species is hydroxyl radical, and the oxidation in the presence of 2 as a catalyst has been assumed to proceed (partially) with the formation of ferryl ion, (FeIV=O)2+. In the oxidation catalyzed by the 4+PCA system (TONs attain 240) hydroxyl radicals were generated in the rate-determining step of monomolecular decomposition of the iron diperoxo adduct containing one PCA molecule. A kinetic model of the process which satisfactorily describes the whole set of experimental data was suggested. The constants of supposed equilibriums and the rate constant for the decomposition of the iron diperoxo adduct with PCA were estimated.
- Shul'pin, Georgiy B.,Nizova, Galina V.,Kozlov, Yuriy N.,Cuervo, Laura Gonzalez,Su?ss-Fink, Georg
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p. 317 - 332
(2007/10/03)
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- Crystalline MWW-type titanosilicate catalyst for producing oxidized compound, production process for the catalyst, and process for producing oxidized compound by using the catalyst
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A crystalline titanosilicate catalyst which is usable as a catalyst in the oxidation reaction of a compound having a carbon-carbon double bond and at least one other functional group, a process for producing the catalyst, and a process for producing an oxidized compound by an oxidation reaction using the catalyst. It has been found that a crystalline titanosilicate having a structural code of MWW effectively functions as a catalyst in an oxidation reaction of a compound having a carbon-carbon double bond and at least one other functional group, or a compound having a carbon-carbon double bond a functional group and having a total carbon number of not smaller than 2 and not larger than 5, wherein the carbon-carbon double bond of the compound is oxidized by using a peroxide as an oxidizing agent, thereby to highly selectively provide an intended oxidized compound.
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- Mechanism of Methylcyclohexane Ozonolysis
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A mathematical model of selective oxidation of methylcyclohexane with ozone-oxygen mixtures was substantiated.
- Syroezhko,Begak,Proskuryakov
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p. 785 - 790
(2007/10/03)
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- 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
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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.
- Lempers,Van Crey,Sheldon
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p. 542 - 546
(2007/10/03)
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- Studies on the Decomposition of Alkyl Hydroperoxides by Different Catalysts
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The catalytic decomposition of cumene, 1-methylcyclohexyl and cyclohexyl hydroperoxides was studied in cyclohexane, cis- and trans-1,4-dimethylcyclohexane and cis-pinane as the solvents.The stearates and the acetylacetonates of manganese, cobalt and chromium, the acetylacetonates of molybdenum and vanadium, n-butyl orthoborate and n-butyl metaborate were used as the catalysts.The chromium-, vanadium-, molybdenum- and boron-containing catalysts brought about some Hock-type decomposition of cumene hydroperoxide and thus proved to be acidic.Of these more of less acidic catalysts only molybdenyl acetylacetonate effected a partially stereospecific hydroxylation of the tertiary C-H-bonds in cis- and trans-1,4-dimethylcyclohexane.The well-known selectivity of chromium catalysts for the ketone formation during the decomposition of secondary hydroperoxides is caused by the catalytic oxidation of secondary alcohols by hydroperoxides in the presence of chromium compounds.In the presence of all the catalysts used the free-radical pathways of the hydroperoxide decomposition predominated, and the attack of the intermediate radicals on the starting hydroperoxide was more important than the attack on the solvent molecules.
- Lauterbach, Gerlinde,Pritzkow, W.,Tien, Tieu Dung,Voerckel, V.
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p. 933 - 946
(2007/10/02)
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- REACTION OF TERTIARY γ-CHLORO ETHERS WITH HYDROGEN PEROXIDE
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The reaction of 4-chlorotetrahydropyrans with hydrogen peroxide leads to tetrahydropyranols instead of the expected hydroperoxides.It was shown by means of the NMR spectra that substitution takes place with inversion at the reaction center.It was established that the abnormal reactivity of such compounds is due to the presence of the oxygen atom at the γ position to the reaction center.
- Arakelyan, A. S.,Dvoryanchikov, A. I.,Gevorkyan, A. A.
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p. 2047 - 2050
(2007/10/02)
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- Role of Hydroperoxides in the Ozonized Oxidation of Cycloalkanes
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Rate constants have been determined for the action of ozone on cyclohexyl and 1-methylcyclohexyl hydroperoxides, which are formed by the oxidation of of cyclohexane and methylcyclohexane respectively.The reactivity of peroxy-compounds towards ozone diminishes in the sequence-cyclohexylhydroperoxide (I) > peroxydicyclohexane-1,1'-diol (IV) > 1,1'-hydroperoxycyclohexylperoxycyclohexanol (III) > peroxy-1,1'-dicyclohexane dihydroperoxide (V) > 1-methylcyclohexylhydroperoxide (II).
- Vikhorev, A. A.,Syroezhko, A. M.,Proskuryakov, V. A.,Korotkova, N. P.
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p. 251 - 253
(2007/10/02)
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