Convenient oxidation of alkylated phenols and methoxytoluenes to antifungal 1,4-benzoquinones with hydrogen peroxide (H2O2)/methyltrioxorhenium (CH3ReO3) catalytic system in neutral ionic liquid

Alkylated phenol and methoxytoluene derivatives were catalytically and selectively oxidized to the corresponding 1,4-benzoquinones in good conversions and yields. Reactions were performed with hydrogen peroxide (H₂O₂)/methyltrioxorhenium (CH₃ReO₃) in 1-butyl-3-methylimidazolium tetrafluoroborate [bmim]BF₄, a neutral ionic liquid. Compounds were tested in vitro for their antifungal activity against the growth of several widespread soil fungi. Some of them were proved to be potent inhibitors of Fusarium sp. than ketoconazole, a commercially available and expensive antifungal agent.     

CH3ReO3/H2O2 in room temperature ionic liquids: an homogeneous recyclable catalytic system for the Baeyer-Villiger reaction

The Baeyer-Villiger oxidation of cyclic ketones can be effected by methyltrioxorhenium/hydrogen peroxide in the ionic liquid [bmim]BF₄. After simple extraction of the lactone with diethyl ether, the catalyst can be repeatedly recycled and efficiently reused for the lactonisation process in the same reaction medium.     

Selective oxidation reactions of diaryl- and dialkyldisulfides to sulfonic acids by CH3ReO3/hydrogen peroxide

Diaryl- and dialkyl disulfides were oxidized in acetonitrile at 20 °C by CH₃ReO₃/H₂O₂ oxidant system to yield selectively the corresponding sulfonic acids in short reaction times and in high yields.     

Dimethyl carbonate: an environmentally friendly solvent for hydrogen peroxide (H2O2)/methyltrioxorhenium (CH3ReO3, MTO) catalytic oxidations

Environmentally friendly oxidations of various organic compounds with the hydrogen peroxide (H₂O₂)/methyltrioxorhenium (CH₃ReO₃, MTO) catalytic system have been described in dimethyl carbonate (DMC), a cheap commercially available and benign chemical having interesting solvating properties, low toxicity and high biodegradability. Oxidations proceeded with good conversions and in good yields. Spectrophotometric analysis demonstrated that the [CH₃ReO(O-O)₂] complex was formed in DMC and that it was stable for several days at room temperature.     

Osmium-catalyzed dihydroxylation of alkenes by H2O2 in room temperature ionic liquid co-catalyzed by VO(acac)2 or MeReO3

Room temperature ionic liquid [bmim]PF₆ was used to immobilize a bimetallic catalytic system for H₂O₂-based dihydroxylation of alkenes. Osmium tetroxide was used as the substrate-selective catalyst with either VO(acac)₂ or MeReO₃ as co-catalyst. The latter serve as an electron transfer mediator (ETM) and activates H₂O₂. For an increased efficiency N-methylmorpholine is required as an additional ETM in most cases. A range of alkenes were dihydroxylated using this robust bimetallic system and it was demonstrated that for some of the alkenes the catalytic system can be recycled and used up to five times.     

离子液体/H_2O_2体系脱硫实验研究

选取四种不同种类离子液体(ILs),1-丁基-3-甲基咪唑溴化物([Bmim]Br)、1-丁基-3-甲基咪唑四氟硼酸盐([Bmim]BF_4)、1-丁基-3-甲基咪唑硫酸氢盐([Bmim]HSO_4)、1-丁基-3-甲基咪唑磷酸二氢盐([Bmim]H_2PO_4)与30%H_2O_2溶液在温和条件下对两种高硫脱灰煤样(LS、QX)进行脱硫实验研究。用化学法测定脱硫前后煤样形态硫含量,并利用傅里叶变换红外光谱(FT-IR)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)及热重(TG)对脱硫前后的煤样进行表征。结果表明,离子液体的加入使H_2O_2氧化脱硫能力增强,煤中硫铁矿硫和有机硫化物硫被显著脱除;经ILs/H_2O_2体系作用后的煤样中小粒径的颗粒减少,颗粒间的缝隙增大,煤表面的凹坑明显,热重实验结果表明,ILs/H_2O_2体系作用后的煤样相对于原煤热失重增大,部分挥发性物质释放峰温提前。     

Efficient and convenient oxidation of organic halides to carbonyl compounds by H2O2 in ethanol

Various primary and secondary organic bromides were oxidized by hydrogen peroxide in refluxing ethanol to give the corresponding aldehydes/and ketones in high yield up to 94%; organic chlorides were oxidized to the corresponding aldehydes/and ketones by the same oxidant in ethanol in the presence of 10 mol % of KBr as the catalyst.     

N,N-Ethylene-bridged flavinium salts derived from l-valinol: synthesis and catalytic activity in H2O2 oxidations

Three chiral N¹,N¹⁰-ethylene-bridged flavinium salts with a stereogenic centre derived from l-valinol are prepared and investigated as oxidation catalysts. These salts efficiently catalyse chemoselective H₂O₂ oxidation of sulfides to sulfoxides and the oxidation of 3-phenylcyclobutanone to the corresponding lactone at room temperature. The flavinium salts react with hydrogen peroxide to form flavin-10a-hydroperoxide, which is the agent responsible for oxidation of the substrate.     

Ionic liquids/H2O systems for the reaction of epoxides with NaN3: a new protocol for the synthesis of 2-azidoalcohols

Oxiranes undergo ring opening rapidly with sodium azide in a [bmim]BF₄/H₂O or [bmim]PF₆/H₂O (2:1) solvent system, under mild and neutral reaction conditions to afford the corresponding 2-azidoalcohols in high to quantitative yields. The remarkable features of this procedure are improved yields, enhanced reaction rates, high regioselectivity and ease of recyclability of ionic liquids (ILs). The recovered ionic liquid can be reused for four to five times but with gradual decrease in activity.     

Chemoselective sulfoxidation by H2O2 or HNO3 using a phosphate impregnated titania catalyst

A variety of organosulfur compounds have been selectively oxidized to the corresponding sulfoxides by either H₂O₂ or HNO₃ using a newly developed solid acid catalyst composed of 84.5% of TiO₂ and 15.5% of [Ti₄H₁₁(PO₄)₉]·nH₂O (n = 1-4). The chemoselective oxidation of sulfides in the presence of vulnerable groups such as -CN, -CC-, -CHO, or -OH, as well as sulfoxidation of substrates like benzothiazole, glycosyl sulfide, and dibenzothiophenes is some of the important attribute of the protocol. Nitric acid, under the present experimental conditions, brings about relatively better selectivity than hydrogen peroxide.     

Alkane oxidation by the H2O2-NaVO3-H2SO4 system in acetonitrile and water

A simple system is described, which oxidizes saturated hydrocarbons either in acetonitrile or (less efficiently) in water. The system consists of 50% aqueous hydrogen peroxide as an oxidant, sodium metavanadate, NaVO₃, as a catalyst and sulfuric (or oxalic) acid as a co-catalyst. The reactions were carried out at 20-50 °C. In the oxidation of cyclohexane in acetonitrile, the highest yield (37% based on cyclohexane) and turnover number (TON=1700) were attained after 3 h at 50 °C. The corresponding parameters were 16% and 1090 for n-heptane oxidation under the same conditions. The oxidation of higher alkanes, RH, in acetonitrile gives almost exclusively the corresponding alkyl hydroperoxides, ROOH. Light alkanes (n-butane, propane, ethane, and methane) have been also oxygenated by the system under consideration. The highest TON (200) was attained for ethane and the highest yield (19%) was obtained in the case of n-butane. The selectivity parameters measured for the oxidation of linear and branched alkanes are low, the reaction with cis- and trans-1,2-dimethylcyclohexanes is not stereoselective. These facts lead us to conclude that the oxidation occurs with the formation of hydroxyl radicals in the crucial step.     

TEMPO-catalyzed oxidation of benzylic alcohols to aldehydes with the H2O2/HBr/ionic liquid [bmim]PF6 system

A selective oxidation of benzylic alcohols to the corresponding aldehydes in room temperature ionic liquid was achieved by using TEMPO/HBr/H₂O₂ system, and both ether-insoluble acetamido-TEMPO and ionic liquid [bmim]PF₆ can be successfully recovered and reused for the oxidation of the same (different) substrate.     

A green and efficient deoximation using H202 catalyzed by montmorillonite-K10 supported COC12

Oximes were oxidized to the corresponding carbonyl compounds in good to high yields by environmentally friendly and green oxidant, H202 catalyzed by montmorillonite K-10 supported cobalt（Ⅱ） chloride.     

Selective and efficient oxidation of ethylene to ethylene glycol acetates with H2O2 catalyzed by Pd(OAc)2-di(2-pyridyl)ketone-di(2-pyridyl)methanesulfonate system

Novel systems for palladium-catalyzed selective oxidation of ethylene to a mixture of ethylene glycol mono- and di-acetates as the major reaction products (90-95% selectivity) with H₂O₂ in acetic acid solution at ambient pressure and 20 °C were developed. The catalytic reaction is very efficient with up to 90% combined yield of glycol acetates with H₂O₂ as a limiting reagent and 1 mol% catalyst loading. The catalytic systems developed are comprised of a mixture of Pd(OAc)₂, and 6-methyl substituted (2-pyridyl)methanesulfonate and/or di(6-pyridyl)ketone ligands. Compositions of the binary, Pd(OAc)₂-dpk, Pd(OAc)₂-Me-dpms, and ternary, Pd(OAc)₂-dpk-Me-dpms, systems have been studied by means of ¹H NMR spectroscopy and ESI mass spectrometry. Kinetics studies were performed as well and plausible reaction mechanism was suggested, which features facially chelating ligand-enabled facile oxidation of Pd^IIC₂H₄OAc intermediates with H₂O₂ to form Pd^IVC₂H₄OAc transients.     

Kinetic study of the reaction H2O2+H→H2O+OH by ab initio and density functional theory calculations

Theoretical investigations on the kinetics of the elementary reaction H₂O₂+H→H₂O+OH were performed using the transition state theory (TST). Ab initio (MP2//CASSCF) and density functional theory (B3LYP) methods were used with large basis set to predict the kinetic parameters; the classical barrier height and the pre-exponential factor. The ZPE and BSSE corrected value of the classical barrier height was predicted to be 4.1 kcal mol⁻¹ for MP2//CASSCF and 4.3 kcal mol⁻¹ for B3LYP calculations. The experimental value fitted from Arrhenius expressions ranges from 3.6 to 3.9 kcal mol⁻¹. Thermal rate constants of the title reaction, based on the ab initio and DFT calculations, was evaluated for temperature ranging from 200 to 2500 K assuming a direct reaction mechanism. The modeled ab initio-TST and DFT–TST rate constants calculated without tunneling were found to be in reasonable agreement with the observed ones indicating that the contribution of the tunneling effect to the reaction was predicted to be unimportant at ambient temperature.     

Selective oxidation of alcohols with H2O2 catalyzed by zinc polyoxometalate immobilized on multi-wall carbon nanotubes modified with ionic liquid

In this work, acid functionalized multi-wall carbon nanotubes (MWCNTs) were modified with imidazolium-based ionic liquids. The selective oxidation of various alcohols with hydrogen peroxide catalyzed by[PZnMo₂W₉O₃₉]^5-, ZnPOM, supported on ionic liquids-modified with MWCNTs, MWCNTAPIB, is reported. This catalyst[ZnPOM@APIB-MWCNT], was characterized by X-ray diffraction, scanning electron microscopy (SEM) and FT-IR spectroscopic methods. This heterogeneous catalyst exhibited high stability and reusability in the oxidation reaction without loss of its catalytic performance.     

Silver nitrate-catalyzed oxidation of aldehydes to carboxylic acids by H2O2

A variety of aromatic, aliphatic and conjugated aldehydes were converted to the corresponding carboxylic acid derivatives with 30% H₂O₂ as the oxidant in the presence of catalytic amounts of AgNO₃. The method described has wide range of applicabilities, does not involve cumbersome work-up, exhibits chemoselectivity and proceeds under mild reaction conditions, and the resulting products are obtained in good yields within reasonable time.     

A unique rate-accelerating effect of certain amino acids in the H2O2 oxidation of alkanes catalyzed by a dinuclear manganese complex containing 1,4,7-trimethyl-1,4,7-triazacyclononane

Certain amino acids used in small amounts (10 catalyst equiv) strongly accelerate the H₂O₂ oxidation of cyclohexane catalyzed by a dinuclear manganese(IV) complex with 1,4,7-trimethyl-1,4,7-triazacyclononane. The efficiency of the co-catalyst dramatically depends on the nature and structure of the acid. Pyrazine-2,3-dicarboxylic acid (2,3-PDCA) has been found to be the most efficient co-catalyst whereas picolinic acid is almost inactive in this oxidation. The highest rate has been attained when 2,3-PDCA was used in combination with trifluoroacetic acid.     

Fe3O4 nanoparticles/ethyl acetoacetate system for the efficient catalytic oxidation of aldehydes to carboxylic acids

A new methodology for the oxidation of aldehydes promoted by commercially available Fe₃O₄ nanoparticles (Fe₃O₄ NPs) activated by ethyl acetoacetate was developed. The use of ethyl acetoacetate as additive was crucial to achieve high reactivities. All reactions were realized under solvent free conditions, using air or tBuOOH as oxidants. Finally, the separation and reuse of the magnetically recoverable nanoparticles make this methodology very practical, simple and economical.