Kinetics of Hydroperoxide Epoxidation of 1-Octene in the Presence of MoB2

We have studied the kinetics of the process of epoxidation of 1-octene by tert-butyl hydroperoxide in the presence of molybdenum boride MoB₂. We have studied the effect of the concentrations of starting materials and reaction products on the process. We suggest a kinetic scheme and we calculate the kinetic parameters of the process.     

Micellar effects of surfactants in cleavage of 4-nitro-phenyl diethyl phosphonate by hydroperoxide anion

We have studied the nucleophilicity of the hydroperoxide anion relative to 4-nitrophenyl diethyl phosphonate (NPDEPS) in the presence of cetyltrimethylammonium bromide (water, 25 °C) while varying the acidity of the medium and the hydroperoxide anion concentration over a broad range. The increase in the reaction rate when the reaction is transferred to a micellar pseudophase is as high as ∼10-fold, which is explained by concentration effects. In CTAB micelles, as in water, the hydroperoxide ion is one of the most effective α-nucleophiles, and the size of the α-effect, characterized by the ratio of the second-order rate constants for reactions of HOO⁻ and OH⁻ anions with NPDEPS, remains practically constant and reaches a value of ∼50-fold. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 6, pp. 357–363, November–December, 2006.     

Sulfide oxygenation by tert-butyl hydroperoxide with mononuclear (Me3TACN)Mn catalysts

Mononuclear (Me₃TACN)MnX₃ compounds, where X is Cl⁻, Br⁻, or N₃⁻, and Me₃TACN is 1,4,7-N,N′,N″-trimethyl-1,4,7-triazacyclononane, have been tested for catalyzing both sulfide oxygenation and styrene epoxidation by tert-butyl hydroperoxide (TBHP) and display turnover frequencies (TOF) up to 200 h⁻¹ at room temperature. Sulfoxides or sulfones may be produced selectively by varying reaction conditions. Product distribution from the oxygenation reactions of ethyl phenyl sulfide, 2-chloroethyl phenyl sulfide, and styrene is consistent with a mechanism involving an early single-electron transfer (SET) step.     

氯化血红素/热解石墨电极对单加氧酶的模拟——Ⅱ.苯在氯化血红素/热解石墨电极上的电催化羟基化作用

实验结果支持了血红素(Ha.)的单体(monomer)吸附态对分子氧起电催化还原作用的观点;并表明,H_2O_2的电催化还原主要是在Ha.的二聚体(dimer)吸附态上进行。Ha./电极对苯一步羟基化生成苯酚有电催化作用。     

Epoxidation and oxidation reactions using 1,4-butanediol dimethacrylate crosslinked polystyrene-supported tertiary butyl hydroperoxide

1,4-Butanediol dimethacrylate (1,4-BDDMA) crosslinked polystyrene-supported t-butyl hydroperoxide was employed in the epoxidation of olefins and oxidation of alcohols to carbonyl compounds. The reagent proved to be successful as a recyclable solid phase organic reagent with as much or more efficiency when compared to its monomeric counterpart. The extent of reaction was found to be dependent on various reaction parameters like solvent, temperature, molar concentration and presence of catalyst.     

Bismuth-catalyzed allylic oxidation using t-butyl hydroperoxide

Bismuth(III) salts are efficient catalysts for the selective allylic oxidation using tert-butyl hydroperoxide. BiCl₃ is especially effective and can be easily recovered and reused as BiOCl. Using BiCl₃/K-10 as catalyst, an increase in the reaction rate was observed.     

Synthesis of model linear tetrablock quaterpolymers and pentablock quintopolymers of ethylene oxide

Multiblock copolymers of ethylene oxide, with four and five different blocks, were synthesized by the sequential anionic polymerization of styrene, isoprene, 2-vinyl pyridine, t-butyl methacrylate, and ethylene oxide with benzyl potassium as an initiator. The monomer sequence was based on the relative nucleophilicity of the active centers. Characterization of the multiblock copolymers by size exclusion chromatography (with refractive-index and UV detectors), membrane osmometry, and NMR spectroscopy confirmed that benzyl potassium is an efficient initiator for the synthesis of well-defined multiblock multicomponent copolymers of ethylene oxide. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2166–2170, 2002     

An unprecedented highly efficient solvent-free oxidation of alkynes to α,β-acetylenic ketones with tert-butyl hydroperoxide catalyzed by water-soluble copper complex

The catalytic system composed of CuCl₂ and 2,2′-biquinoline-4,4′-dicarboxylic acid dipotassium salt (BQC) was found to be highly efficient for the selective α-oxidation of internal alkynes to the corresponding α,β-acetylenic ketones, with aqueous tert-butyl hydroperoxide under mild conditions. For the first time, full conversions of alkynes were reached with excellent selectivities, and propargylic tert-butylperoxy ethers were observed and suggested as the reaction intermediates. In the case of terminal alkynes, the oxidations are sluggish and low yields ranging from 32% to 40% were obtained.     

叔丁醇溶剂中TS-1催化丙烯环氧化的动力学研究

研究了叔丁醇溶剂中TS-1催化丙烯环氧化反应的本征动力学，反应条件为:温度303.15K～323.15K，丙稀压力0.3 MPa～0.6 MPa。根据反应机理及组分在TS-1上的吸附特点建立了如下的机理模型方程式： 根据实验数据，我们对机理模型进行了参数估值。检验结果表明拟合效果较好，反应符合Eley-Rideal机理，丙烯环氧化反应发生在吸附态的过氧化氢与游离态的丙烯之间。