- Visible-light-promoted aerobic oxidation of sulfides and sulfoxides in ketone solvents
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Simple and readily available ketones have been identified to promote the visible-light-promoted aerobic oxidation of sulfides and sulfoxides to sulfones. We report a simple and environmental-friendly oxidation protocol of sulfides to sulfones. Various sulfides were efficiently oxidized into sulfones with O2 as sustainable terminate oxidant, readily available thioxanthone as the photocatalyst and 3-pentanone (DEK) as the solvent. The protocol tolerates diverse functional groups, including halogens, ketone, ester, cyano, heterocycle and even cyclopropyl groups. The detection of the aerobic oxidation reaction in DEK by GC and HRMS disclosed that the key active intermediates were generated.
- Li, Xiaotong,Wang, Yu,Xie, Xiaomin,Yang, Liqun,Zhang, Zhaoguo
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- A sustainable approach towards solventless organic oxidations catalyzed by polymer immobilized Nb(V)-peroxido compounds with H2O2 as oxidant
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New heterogeneous catalysts comprising of peroxidoniobium(V) complexes immobilized on amino acid grafted cross-linked poly(styrene-divinylbenzene) resin has been developed. Results of FTIR, Raman, NMR, XPS, XRD, EDX, SEM, BET, TGA, and elemental analysis confirmed the successful anchoring of triperoxidoniobium(V), [Nb(O2)3]? species to the host polymer via the pendant amino acid groups. The supported catalysts exhibited excellent performance in epoxidation of styrene and a range of cyclic and terpenic compounds under environmentally acceptable solvent-free condition, with aqueous H2O2 as oxidant. The catalytic protocols provided excellent conversion to the desired epoxide (up to 100%) with selectivity > 99%, TON as high as 1000, and high H2O2 utilization efficiency (92–97%). Moreover, the catalysts efficiently facilitated chemoselective solvent-free oxidation of a variety of thioethers to sulfones at room temperature. Simple operational strategy, easy recyclability for multiple reaction cycles with the consistent activity-selectivity profile are the additional significant attributes of the developed catalytic processes.
- Ahmed, Kabirun,Gogoi, Sandhya Rani,Islam, Nashreen S.,Saikia, Gangutri,Sultana, Sazida Yasmin,Talukdar, Hiya
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- Synthesis, spectral characterization, SC-XRD, HSA, DFT and catalytic activity of novel dioxovanadium(V) complex with aminobenzohydrazone Schiff base ligand: An experimental and theoretical approach
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A new dioxovanadium(V) complex was prepared by the reaction of VO(acac)2 with a tridentate ONO donor Schiff base, derived by condensing 3-ethoxysalicylaldehyde and 4-aminobenzohydrazide. The structures of synthesized products were characterized spectroscopically through FT-IR, 1H & 13C NMR and by elemental composition through combustion analysis. The structure of the complex was determined with the help of single crystal X-ray crystallography. It was inferred from the diffraction data that the geometry around the central metal ion in the complex is distorted square pyramidal. The tridentate Schiff base ligand is bonded to the central metal through the oxygen of the carbonyl group, the deprotonated phenolic oxygen atom and the azomethine nitrogen. The pyramid base is completed by other oxo ligands that are in cis positions. The theoretical calculations, performed by DFT using B3LYP/Def2-TZVP level of theory, determined that the intended outcomes are in compliance with the actual consequences. Furthermore, the catalytic potential of the vanadium complex was explored for the selective oxidation of the aryl and alkyl sulfides to the corresponding sulfones in the presence of 30% aqueous H2O2 in ethanol. In this work, rPBE and B3LYP methods are used to locate transition structures and to compare free energies of reactants, transition structures and the products involved in the reaction. Analyzing nudge elastic band data shows that the barrier free energy for the oxidation of sulfide to sulfoxide and sulfone are 13 and 83 kcal.mol?1, respectively. The main advantages of the present catalytic study are high yields of the products, less time required for the completion of the reaction and simple work-out procedure.
- Ashfaq, Muhammad,Behjatmanesh-Ardakani, Reza,Fallah-Mehrjardi, Mehdi,Kargar, Hadi,Munawar, Khurram Shahzad,Tahir, Muhammad Nawaz
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- Method for preparing sulfone and N-oxygen compound by using green and efficient oxidation system
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The invention discloses a method for preparing sulfone and N-oxygen compound by using a green and efficient oxidation system. The method comprises the following steps of: by using a tertiary amine compound or aromatic thioether or fatty thioether compound as a raw material, H2O2 as an oxidant, methanol as a reaction solvent and potassium carbonate as an alkali, introducing sulfuryl fluoride 5O2F2gas as an accelerator; performing stirring at room temperature under a sealed condition for oxidation reaction; and after finishing the reaction, filtering to remove solid potassium carbonate, dryingto remove water, filtering to obtain a crude product, and finally carrying out column chromatography separation to obtain a pure product. Tertiary amine is oxidized into an N-oxygen compound, and thethioether is oxidized into sulfone. According to the method, the sulfuryl fluoride (SO2F2) which is very cheap and easy to obtain is used as the reaction promoter, green and environment-friendly hydrogen peroxide (H2O2) is used as an oxidizing agent, and so that the yield of the reaction is generally high; after the reaction, byproducts are only water and inorganic salts (SO4 and F) whichare easy to remove and free of pollution, and the green and efficient oxidation system can be realized, and therefore, the method is suitable for large-scale industrial production.
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Paragraph 0060-0062
(2021/01/29)
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- Flow Electrosynthesis of Sulfoxides, Sulfones, and Sulfoximines without Supporting Electrolytes
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An efficient electrochemical flow process for the selective oxidation of sulfides to sulfoxides and sulfones and of sulfoxides toN-cyanosulfoximines has been developed. In total, 69 examples of sulfoxides, sulfones, andN-cyanosulfoximines have been synthesized in good to excellent yields and with high current efficiencies. The synthesis was assisted and facilitated through a supporting electrolyte-free, fully automated electrochemical protocol that highlights the advantages of flow electrolysis.
- Amri, Nasser,Wirth, Thomas
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p. 15961 - 15972
(2021/07/20)
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- A mild and chemoselective CALB biocatalysed synthesis of sulfoxides exploiting the dual role of AcOEt as solvent and reagent
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A mild, chemoselective and sustainable biocatalysed synthesis of sulfoxides has been developed exploiting CALB and using AcOEt with a dual role of more environmentally friendly reaction solvent and enzyme substrate. A series of sulfoxides, including the drug omeprazole, have been synthesised in high yields and with excellent E-factors.
- Anselmi, Silvia,Liu, Siyu,Kim, Seong-Heun,Barry, Sarah M.,Moody, Thomas S.,Castagnolo, Daniele
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supporting information
p. 156 - 161
(2021/01/14)
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- Air atmospheric photocatalytic oxidation by ultrathin C,N-TiO2nanosheets
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Herein, we demonstrate the highly efficient photocatalytic sulfide oxidation reaction under mild conditions,i.e.in air, at room temperature and in the absence of a sacrificial reagent, co-catalyst or redox mediator, by using ultrathin C,N-TiO2nanosheets as a photocatalyst.
- Cheng, Xiuyan,Zhang, Jianling,Liu, Lifei,Zheng, Lirong,Zhang, Fanyu,Duan, Ran,Sha, Yufei,Su, Zhuizhui,Xie, Fei
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supporting information
p. 1165 - 1170
(2021/02/26)
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- Modulation of photochemical oxidation of thioethers to sulfoxides or sulfones using an aromatic ketone as the photocatalyst
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We have developed an eco-friendly and chemo-selective photocatalytic synthesis of sulfoxides or sulfones via oxidation of sulfides (thioethers) at ambient temperature using air or O2 as the oxidant. An inexpensive thioxanthone was used as the photocatalyst. Our method offers excellent chemical yields and good functional group tolerance. The hydrogen bonding between hexafluoro-2-propanol (HFIP) and sulfoxides may play an important role in minimizing the over-oxidization of sulfoxides.
- Zhao, Bin,Hammond, Gerald B.,Xu, Bo
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supporting information
(2021/09/13)
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- Multicomponent Reductive Cross-Coupling of an Inorganic Sulfur Dioxide Surrogate: Straightforward Construction of Diversely Functionalized Sulfones
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Conventionally, sulfones are prepared by oxidation of sulfides with strong oxidants. Now, a multicomponent reductive cross-coupling involving an inorganic salt (sodium metabisulfite) for the straightforward construction of sulfones is disclosed. Both intramolecular and intermolecular reductive cross-couplings were comprehensively explored, and diverse sulfones were accessible from the corresponding alkyl and aryl halides. Intramolecular cyclic sulfones were systematically obtained from five- to twelve-membered rings. Naturally occurring aliphatic systems, such as steroids, saccharides, and amino acids, were highly compatible with the SO2-insertion reductive cross-coupling. Four clinically applied drug molecules, which include multiple heteroatoms and functional groups with active hydrogens, were successfully prepared via a late-stage SO2 insertion. Mechanistic studies show that alkyl radicals and sulfonyl radicals were both involved as intermediates in this transformation.
- Meng, Yingying,Wang, Ming,Jiang, Xuefeng
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supporting information
p. 1346 - 1353
(2019/12/11)
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- Copper(ii)-containing tungstotellurates(vi): Syntheses, structures and their catalytic performances in selective oxidation of thioethers
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We report the syntheses and structures of two new copper(ii)-containing tungstotellurates(vi) Na12[TeVI2W8O38Cu2(H2O)2]·7H2O (Te2W8Cu2) and Na6[TeVIW6O24Cu(NH2CH2CO2)2]·6H2O (TeW6Cu). The two compounds were synthesized by a simple one-pot method and characterized by single-crystal X-ray diffraction (XRD), powder XRD, FT-IR spectroscopy, elemental analysis, and thermogravimetric analysis in the solid state. Furthermore, their catalytic properties for the selective oxidation of thioethers were also studied systematically. The catalytic experiment results indicate that the tungstotellurate(vi) Te2W8Cu2 is an effective heterogeneous catalyst for the selective oxidation of thioethers to sulfoxides or sulfones by an H2O2 oxidant at room temperature. Under the ambient conditions, Te2W8Cu2 can convert 99percent of methyl(phenyl)sulfane to sulfoxides or sulfones with 96percent or 99percent selectivity, respectively, and the utilization rate of H2O2 is up to 80percent. Furthermore, Te2W8Cu2 as a heterogeneous catalyst is stable in the reaction and could be reused at least five cycles with conserved activity.
- Hu, Changwen,Li, Peihe,Li, Xuanyao,Lin, Zhengguo,Liu, Jinghai
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p. 22515 - 22521
(2020/07/03)
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- Ag?CeO2 nanoparticles with “rice ball” configuration as an efficient and heterogeneous nanocatalyst for the selective oxidation of sulfides to sulfones with 30% H2O2
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Abstract: Ag?CeO2 with a rice-ball configuration as a heterogeneous and highly efficient catalyst was described for activation of H2O2 in the selective oxidation of aromatic and aliphatic sulfides to their corresponding sulfones. Ag nanoparticles in the CeO2–Ag interface increase the oxygen vacancy defects on the surface of CeO2 and oxygen vacancy defects promote the reduction of Ce4+ to Ce3+ to keep the electroneutrality. Generated Ce3+ species act as the active sites in the interface of CeO2–Ag to promote the oxidation of sulfides to sulfones. Compatibility with various aromatic and aliphatic sulfides, excellent selectivity, high yield of product, simple experimental procedure, and mild reaction conditions are some of the precious advantages of Ag?CeO2/H2O2 catalyst system. Graphic abstract: [Figure not available: see fulltext.]
- Bahrami, Kiumars,Ghorbani, Somayeh,Parnian, Rouhallah,Soleimani, Ebrahim
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- Solid-state rearrangement of sandwich-type polyoxometalate-dopamine nanohybrid to the nanoflower Keggin polyoxometalate: synthesis, characterization, and catalytic efficiency
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Sponge-like inorganic-organic nanohybrid consisting of sandwich-type polyoxometalate of [P2W18Ce3(H2O)2O71]12? (P2W18Ce3) and dopamine (DA) was fabricated by a simple procedure. The DA/P2W18Ce3 sponge-like nanohybrid is turned into a nanoflower by calcination at 300 °C. The results showed a structure rearrangement of sandwich-type polyoxometalate to the Keggin-type polyoxometalate along with this morphology change. The nanomaterials were fully characterized by scanning electron microscopy (FE-SEM), energy dispersive X-ray analysis (EDX), thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR) spectroscopy, texture analysis (BET), and X-ray powder diffraction (XPRD). The DA/P2W18Ce3 sponge-like nanohybrid and the Keggin nanoflower showed efficiency toward degradation of methylene blue (MB) and rhodamine B (RhB). Moreover, the catalytic activity of the Keggin nanoflower was examined in the oxidation of sulfides to sulfones with H2O2 as oxidant in water at room temperature. The catalyst was reused at least four times without loss of its catalytic activity.
- Pirdosti, Soleiman Fazeli,Khoshnavazi, Roushan,Naseri, Elham
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p. 723 - 736
(2020/04/28)
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- Selectivity switch in the aerobic oxygenation of sulfides photocatalysed by visible-light-responsive decavanadate
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Nanometre-sized metal oxides are promising species for the development of visible-light-responsive photocatalysts for the selective transformation of organic functional groups. In this article, we report that decavanadate ([V10O28]6-, V10) behaved as an efficient visible-light-responsive photocatalyst in the product-selective oxygenation of sulfides achieved using O2 (1 atm) as the green oxidant. In particular, we revealed that visible-light-responsive photocatalysis of V10 showed remarkable activity for the oxygenation of structurally diverse sulfides to form the corresponding sulfones using O2 in methyl ethyl ketone (MEK). Furthermore, by simply adding water to the reaction mixture, the product selectivity of sulfide oxygenation can be significantly switched toward the production of sulfoxides, without concomitant loss of photocatalytic activity. Based on experimental evidence, we inferred the following mechanistic steps for this photocatalytic system: the aerobic oxygenation of sulfides to form the corresponding sulfoxides initiated by a visible-light-induced photoredox reaction of V10. As for the formation of sulfones, MEK-derived peroxide species as the co-catalysts are probably involved in the oxygenation of sulfoxides to sulfones. The selectivity switch of the V10-photocatalysed reaction brought about by water addition is most likely achieved by suppressing the formation of MEK-derived peroxide species. This journal is
- Li, Chifeng,Mizuno, Noritaka,Murata, Kei,Ishii, Kazuyuki,Suenobu, Tomoyoshi,Yamaguchi, Kazuya,Suzuki, Kosuke
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supporting information
p. 3896 - 3905
(2020/07/09)
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- Fe(III)-salen complex supported on dendrimer functionalized magnetite nanoparticles as a highly active and selective catalyst for the green oxidation of sulfides
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In this study, we reported the preparation of polyamidoamine-modified magnetite nanoparticles and their use for the immobilization of Fe(III)-salen complex to form a novel magnetic catalyst. The prepared catalyst was characterized by some modern techniques i.e. Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), N2 adsorption-desorption analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), vibrating sample magnetometry (VSM), and inductively couple plasma atomic emission spectroscopy (ICP-AES). The catalyst showed excellent activity and selectivity for the oxidation of sulfides to sulfoxides (conversion 87–100percent, selectivity 82–100percent) using H2O2 (30percent w/w) as oxidant in aqueous medium at 50 °C. Furthermore, the catalyst could be recovered in a facile manner from the reaction mixture by using a magnet and reused for five cycles with high catalytic stability.
- Asadi, Zahra,Masteri-Farahani, Majid,Niakan, Mahsa
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- Effect of Organic Solvents on the Rate of Oxidation of Sulfoxides with Peroxy Acids
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Abstract: The reaction of sulfoxides with peroxy acids in various organic media was studied. The reaction mechanism involves the rapid formation of a sulfoxide-–peroxy acid intermediate which decomposes in the second stage to form carboxylic acid and the corresponding sulfone. The second stage is the rate-limiting step. The reaction medium significantly affects the rate of oxidation. The calculated activation parameters of the oxidation process indicate a compensation effect in the investigated reaction. Correlations between the main physicochemical parameters of solvents and the effective rate constants (k) of dimethyl sulfoxide oxidation with peroxy acids were found. Depending on the reaction conditions, the main factors affecting the k values are specific and nonspecific solvation of the reactants and structural factors.
- Dutka, V. S.,Dutka, Yu. V.,Midyana, G. G.,Pal’chikova, E. Ya.
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p. 329 - 334
(2020/04/27)
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- Water-soluble polymer anchored peroxotitanates as environmentally clean and recyclable catalysts for mild and selective oxidation of sulfides with H2O2 in water
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Anchoring of peroxotitanium (pTi) species to linear water-soluble acrylic acid based polymers, poly(sodium acrylate) (PA) and poly(sodium methacrylate) (PMA) led to the successful synthesis of a pair of new, water-tolerant and recyclable catalysts of the type [Ti2(O2)2O2(OH)2]4-—L (L = PA or PMA), highly effective in chemoselective sulfoxidation of organic sulfides with 30% H2O2 in aqueous medium at ambient temperature. The catalytic protocol is high yielding (TOF up to 11,280 h?1), operationally simple as well as environmentally clean and safe, being free from halide, or any other toxic auxiliaries. The catalysts are sufficiently stable to afford easy recyclability for at least 10 consecutive reaction cycles of sulfoxidation with consistent activity selectivity profile. Oxidation of dibenzothiophene (DBT) to respective high purity sulfoxide or sulfone could also be accomplished using the same catalysts by variation of reaction conditions.
- Ahmed, Kabirun,Saikia, Gangutri,Paul, Sivangi,Baruah, Satyajit Dey,Talukdar, Hiya,Sharma, Mitu,Islam, Nashreen S.
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- Fe3O4?BNPs?SiO2-SO3H as a highly chemoselective heterogeneous magnetic nanocatalyst for the oxidation of sulfides to sulfoxides or sulfones
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To achieve green chemistry goals and also to reduce the cost of catalysts as well as to avoid producing toxic wastes and show the importance of separation and recycling of catalysts from the reaction medium, in this work, we describe the preparation and characterization of magnetic acidic boehmite nanoparticles as a heterogeneous catalyst, which is called Fe3O4?BNPs?SiO2-SO3H. This catalyst works efficiently in the selective oxidation of sulfides to sulfoxides or sulfones in the presence of H2O2 as a green oxidant. It can easily be separated from the reaction medium by using an external magnet and it was recycled 6 times without loss of magnetic catalytic properties.
- Ghanbari Kermanshahi, Mohammad,Bahrami, Kiumars
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p. 36103 - 36112
(2019/11/20)
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- Electrochemical oxidations of thioethers: Modulation of oxidation potential using a hydrogen bonding network
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A highly efficient chemo-selective electrochemical oxidation of thioethers to sulfoxides and sulfones was developed. The hydrogen bonding network generated from hexafluoro-2-propanol (HFIP) and acetic acid (AcOH) plays an important role in the modulation of oxidation potential. The hydrogen bonding network complexes strongly with the sulfoxide, making it less prone to further oxidation. Therefore, thioethers can be selectively electrochemically oxidized to sulfoxides and over-oxidization could be minimized. Moreover, this modulation of oxidization via hydrogen bonding was supported by density functional theory (DFT) calculations and cyclic voltammetry experiments.
- Liu, Shiwen,Chen, Bocheng,Yang, Yi,Yang, Yuhao,Chen, Qianjin,Zeng, Xiaojun,Xu, Bo
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- Selective catalytic oxidation of sulfides to sulfoxides or sulfones over amorphous Nb2O5/AC catalysts in aqueous phase at room temperature
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Selective oxidation of sulfides into sulfoxides or sulfones is an important transformation in organic synthesis. Activated carbon supported Nb-based catalysts were prepared by the impregnation method and then characterized by the XRD, TEM and XPS. The characterization results indicate Nb species is amorphous Nb2O5. The catalysts were applied for the catalytic oxidation of sulfides in aqueous phase with H2O2 as the oxidant. Sulfides could be converted into the corresponding sulfoxides or sulfones with high conversion and selectivity at room temperature. The recycling experiments showed the Nb2O5/AC catalysts exhibited good reusability. They could be recycled for 10 times without obvious loss of activity and selectivity.
- Zhang, Junjie,Jiang, Tingting,Mai, Yuliang,Wang, Xi,Chen, Jiazhi,Liao, Bing
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- Sandwich type polyoxometalates encapsulated into the mesoporous material: Synthesis, characterization and catalytic application in the selective oxidation of sulfides
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The A-type sandwich polyoxometalates of [(HOSnIVOH)3(PW9O34)2]12- (P2W18Sn3) and [(OCeIVO)3(PW9O34)2]12- (P2W18Ce3) were immobilized for the first time into the porous metal-organic framework MIL-101(Cr). FT-IR, powder X-ray diffraction, SEM-EDX, ICP analysis, N2 adsorption and thermogravimetric analysis collectively confirmed immobilization and good distribution of polyoxometalates into cages of MIL-101(Cr). The catalytic activities of the homogeneous P2W18Sn3 and P2W18Ce3 and the corresponding heterogeneous catalysts were examined in the oxidation of sulfides to sulfones with H2O2 as the oxidant at room temperature. The effects of different dosages of polyoxometalates, type of solvent, reaction time, amount of catalyst and oxidant in this catalytic system were investigated. The new P2W18Sn3@MIL-101 and P2W18Ce3@MIL-101 nanocomposites exhibited good recyclability and reusability in at least five consecutive reaction cycles without significant loss of activity or selectivity.
- Naseri, Elham,Khoshnavazi, Roushan
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p. 28249 - 28260
(2018/08/16)
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- Method for preparing sulfoxide and sulfone through water phase oxidation of thioether
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The invention discloses a method for preparing sulfoxide and sulfone through water phase oxidation of thioether. According to the method, H2O2 and a supported metal oxide catalyst are added to a thioether aqueous solution, and a reaction is performed to obtain sulfoxide and sulfone. According to the present invention, the reaction for preparing sulfoxide or sulfone is performed in the water phaseby using H2O2 as the oxidant without the organic solvent, wherein the product yield is high, the reaction conditions are mild, the reaction process is environmentally friendly, and the production costis low.
- -
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Paragraph 0048; 0049; 0050
(2018/10/11)
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- Efficient molybdenum catalyzed chemoselective, solvent-free oxidation of sulfides to sulfones at room temperature
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An effcient and reusable molybdenum-based catalyst has been prepared by tethering dioxomolybdenumacetylacetonate complex, MoO2(acac)2, via postsynthesis modifcation of zeolite beta. The catalyst has been characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX) and inductively coupled plasma (ICP). The catalyst exhibited very high activity for the selective oxidation of sulfdes to sulfones at room temperature. The catalyst can be recycled and reused four times without signifcant loss of activity.
- Hadigavabar, Ali Dadashi,Tabatabaeian, Khalil,Zanjanchi, Mohammad Ali,Mamaghani, Manouchehr
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p. 3829 - 3833
(2018/05/24)
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- METHOD OF PRODUCING SULFONE COMPOUND
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PROBLEM TO BE SOLVED: To provide a method of producing a sulfone compound from a sulfide compound efficiently with a high yield. SOLUTION: A sulfone compound represented by general formula (2) is produced by optical oxygen oxidation of a sulfide compound represented by general formula (1) at at least 40°C in the presence of a secondary alcohol, a gas containing at least 25 vol.% of oxygen, and anthracene or a derivative thereof. (In the formulas, R1 and R2 are each independently a C1-6 organic group, or S, R1 and R2 may form a ring.) SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2019,JPOandINPIT
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-
Paragraph 0041; 0043; 0045
(2019/01/25)
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- An isotetramolybdate-supported rhenium carbonyl derivative: Synthesis, characterization, and use as a catalyst for sulfoxidation
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A novel isotetramolybdate-supported rhenium carbonyl derivative, [(CH3)4N]4[{Re(CO)3}4(Mo4O16)]·H2O (1), has been successfully synthesized and characterized by single crystal X-ray diffraction crystallography, IR and UV spectroscopy, etc. Results showed that, compound 1 is an efficient catalyst for the oxidation of thioanisole into the corresponding sulfoxide in the presence of hydrogen peroxide with good to excellent conversion (99%) and excellent selectivity (93%). Highly efficient oxygenation of thioanisole can also be achieved with 100% selectivity of sulfone and >99% conversion. Furthermore, optimized conditions were applied to a range of sulfides to obtain the corresponding sulfoxides and sulfones.
- Lu, Jingkun,Ma, Xinyi,Singh, Vikram,Zhang, Yujiao,Ma, Pengtao,Zhang, Chao,Niu, Jingyang,Wang, Jingping
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p. 5279 - 5285
(2018/04/23)
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- Polyoxometalate LUMO engineering: A strategy for visible-light-responsive aerobic oxygenation photocatalysts
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We report the efficient visible-light-responsive photocatalysis of polyoxometalates (POMs) by engineering the lowest unoccupied molecular orbitals (LUMOs). By the introduction of vanadium atoms into the γ-Keggin-type phosphotungstate, a new V3d/W5d mixed LUMO appeared to afford a visible-light-responsive catalyst (I), which showed high photocatalytic activity for aerobic oxygenation of sulfides to sulfoxides.
- Li, Chifeng,Suzuki, Kosuke,Mizuno, Noritaka,Yamaguchi, Kazuya
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supporting information
p. 7127 - 7130
(2018/07/05)
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- 1,1,2,2-Tetrahydroperoxy-1,2-diphenylethane as new oxidant for chemoselective and catalyst free oxidation of sulfides to sulfoxides and sulfones
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A catalyst free and chemoselective oxidation of sulfides to sulfoxides or sulfones was developed using 1,1,2,2-tetrahydroperoxy-1,2-diphenylethane as a new oxidant. This scope has shown the achievement of various sulfoxides and sulfones which were obtained selectively in high yields at room temperature.
- Khosravi, Kaveh,Naserifar, Shirin,Mahmoudi, Boshra,Khalaji, Kobra
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p. 316 - 321
(2017/02/18)
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- A Simple Metal Free Oxidation of Sulfide Compounds
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Abstract: This work reports simple, efficient, selective protocol for the oxidation of sulfide compounds. Various sulfides were selectively and completely converted into their corresponding sulfoxides and sulfones using H2O2as an oxidant in presence of catalytic amount of caprylic acid. The reaction proceeds at room temperature to give sulfoxide and by increasing the reaction temperature to 50 °C, this system provides selective formation of sulfone with high conversion and excellent yields. Green, convenient, easy work-up, chemoselectivity, broad substrate scope and regeneration of catalyst are the important highlights of this protocol. Graphical Abstract: [Figure not available: see fulltext.] Using H2O2as an oxidant in presence of catalytic amount of caprylic acid various sulfides were selectively and completely converted into their corresponding sulfoxides and sulfones.
- Wagh, Ravindra B.,Nagarkar, Jayashree M.
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p. 181 - 187
(2017/02/18)
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- Catalytic Activity of Crystallographically Characterized Organic–Inorganic Hybrid Containing 1,5-Di-amino-pentane Tetrachloro Manganate with Perovskite Type Structure
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Abstract: Layered 2D organic–inorganic hybrid perovskite (OIHS) of the diammonium series, 1,5 di-aminepentane tetrachloro mangenate ([NH3–(CH2)5–NH3] MnCl4) was prepared by slow evaporation and reducing temperature method and characterized by single crystal X-ray diffraction analysis. Its structure consists of organic cation, [NH3(CH2)5NH3]+2 extended in a zigzag fashion and inorganic anion, [MnCl6]?2 where Mn2+ is coordinated by six Cl? ion in octahedral fashion. The organic and inorganic segments are alternately stacked along c-axis where inorganic layer is extended through corner-shared octahedra sandwiched by the di-aminopentane molecules. The layers (organic and inorganic) were connected to each other through N–HCl hydrogen bonds and van-der Waals interaction to build cation–anion–cation cohesion. The hybrid crystal had orthorhombic non-centrosymetric system having I212121 space group with unit cell parameters a = 7.1742(3) ?, b = 7.3817(3) ?, c = 23.9650(10) ?, V = 1269.13 ?3 and Z = 4. The hybrid exhibited excellent catalytic activity towards sulphide and alkene oxidation using aqueous H2O2 as an oxidant. Graphical Abstract: OIHS of the diammonium series [NH3–(CH2)5–NH3] MnCl4; 1,5 di-aminepentane tetrachloro mangenate were prepared by slow evaporation and temperature decrease method, characterized by single crystal X-ray diffraction. This complex exhibits excellent catalytic activity towards sulphide oxidation and alkene oxidation using aqueous H2O2 as an oxidant. [Figure not available: see fulltext.].
- Mondal, Paramita,Abdel-Aal, Seham Kamal,Das, Debasis,Islam, Sk Manirul
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p. 2332 - 2339
(2017/08/22)
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- The Polyoxovanadate-Based Carboxylate Derivative K6H[VV17VIV12(OH)4O60(OOC(CH2)4COO)8]·nH2O: Synthesis, Crystal Structure, and Catalysis for Oxidation of Sulfides
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The high-nuclearity polyoxovanadate-based carboxylate derivative K6H[VV17VIV12(OH)4O60(OOC(CH2)4COO)8]·nH2O (1) has been successfully synthesized by conventional aqueous methods and structurally characterized. The [VV17VIV12(OH)4O60(OOC(CH2)4COO)8]7- polyanion is built up from three cages: one {VV17(OH)4O44} cage and two identical [(VIV3O6)2(OOC(CH2)4COO)4]8- cages. Of the three cages, the {VV17(OH)4O44} is a purely inorganic polyoxovanadate cluster, whereas each of the [(VIV3O6)2(OOC(CH2)4COO)4]8- cages is a vanadium-based organic-inorganic hybrid cluster framed via four adipate ligands linking simultaneously to two triangular {V3} units. The two [(VIV3O6)2(OOC(CH2)4COO)4]8- cages are covalently attached to the central {VV17(OH)4O44} cage via V-O-V bonds in a linear arrangement, resulting in a {V29}-based hybrid cluster skeleton. The catalytic properties of compound 1 for the oxidation of sulfides by tert-butyl hydroperoxide were investigated, and the result indicates that 1 exhibits excellent catalytic activity for the oxidation of sulfides under mild conditions.
- Wang, Ke,Niu, Yanjun,Zhao, Dongyan,Zhao, Yanxin,Ma, Pengtao,Zhang, Dongdi,Wang, Jingping,Niu, Jingyang
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p. 14053 - 14059
(2017/11/27)
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- Application of sodium titanate nanotubes doped with vanadium (VNaTNT) as a heterogeneous catalyst for oxidation of sulfides at room temperature
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A heterogeneous titanate nanotube (TNT) catalyst containing TiO2, Na, and V has been synthesized and used in the chemoselective oxidation of sulfides to the corresponding sulfoxides in the presence of 30% H2O2 in water. Some of the advantages of our method include excellent yields, heterogeneous conditions, simplicity, compatibility with a variety of functionalities, and ease of isolation of the products. Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and N2 adsorption were used for structural and textural characterization of the catalyst (VNaTNT).
- Dadvar, Mohammad Ali,Fazaeli, Razieh
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p. 494 - 501
(2016/04/20)
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- A chemoselective oxidation of sulfides to sulfoxides and sulfones using urea-2,2-dihydroperoxypropane as a novel oxidant
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Background: Sulfoxides and sulfones have been in the center of attention due to their wide range of promises in various approaches. The functional groups presented in these compounds serve as important building blocks in numerous natural, pharmeceutical and agricultural compounds. These deriatives have been prepared through a multitude of routes which were accompanied by several drawbacks. Therefore, there has been an ever-increasing interest to find a new methodology that leads to the production of these compounds via an environmentally benign path bringing about high yields. Recently, gem-dihydroperoxides have attracted much attention due to their oxidizing power and they have been utilized in several oxidation processes. Methods: We carried out a chemoselective oxidation of sulfides to sulfoxides and sulfones on treatment with urea-2,2-dihydroperoxypropane, a solid oxidant composed of equal amounts of 2,2-dihydroperoxypropane and urea, using THF as the solvent under catalyst-free conditions at room temprature. Results: Sulfides possessing a variety of substitutions namely dialkyl, diaryl, ally l and alkyl-aryl were subjected to the optimized reaction conditions and they could successfully afford different amounts of sulfoxides and sulfones depending on the amount of the oxidant utilized. Based on the results, electron-donating groups accelerated the reaction while electron-withdrawing substituents lowered the reactivity. Conclusion: Urea-2,2-dihydroperoxypropane as a solid oxidant which can be stored for several months without any loss in its activity has proved its capability to oxidize sulfides to sulfoxides and sulfones under catalyst-free and mild conditions. This approach is a cost-effective and environmentally benign methodology via which the products have been synthesized in high yields and short reaction times.
- Khosravi, Kaveh,Naserifar, Shirin,Asgari, Atefeh
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p. 749 - 756
(2017/02/05)
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- Enhanced aqueous oxidation activity and durability of simple manganese(III) salen complex axially anchored to maghemite nanoparticles
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Simple Mn-salen complex was anchored coordinatively to γ-Fe2O3 nanoparticles through amine functionality which provide a new magnetically recoverable nanocatalyst with high oxidation activity and stability. Catalyst characterization was performed using FT-IR, UV-Vis, XRD, EDS, TGA and ICP-AES. TEM image revealed a quasi-spherical structure with size smaller than 20 nm for nanocatalyst. A thermal stability up to around 300 °C was verified for prepared nanocatalyst based on thermogravimetric analysis. Finally, the catalytic performance of magnetically recoverable Mn-catalyst was exploited in the green oxidation of different types of functional groups including olefins, alcohols, saturated hydrocarbons and sulfur containing compounds with n-Bu4NHSO5 (TBAOX) in water under heterogeneous conditions. The salen catalyst proved to be reusable for at least eight times and the oxidant's by-product (n-Bu4NHSO4) could also be recycled.
- Rezaeifard, Abdolreza,Jafarpour, Maasoumeh,Farrokhi, Alireza,Parvin, Sousan,Feizpour, Fahimeh
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p. 64640 - 64650
(2016/07/21)
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- Selective hydrogen peroxide oxidation of sulfides to sulfones with carboxylated multi-walled carbon nano tubes (MWCNTs-COOH) as heterogeneous and recyclable nanocatalysts under organic solvent-free conditions
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This study deals with oxidation of sulfides to sulfones by using a heterogeneous and recyclable nanocatalyst. Alkyl and aryl sulfides were directly oxidized to the corresponding sulfones in excellent yields with 30% H2O2 under organic solvent-free conditions, in the presence of carboxylated multi-walled carbon nano tubes (MWCNTs-COOH) as the efficient and heterogeneous nanocatalyst. The oxidation of alkyl and aryl sulfides proceeded at room temperature, and the corresponding sulfones were selectively obtained. The catalyst is recyclable for at least 8 cycles, and the only byproduct is water.
- Veisi, Hojat,Eshbala, Fereshteh Hosseini,Hemmati, Saba,Baghayeri, Mehdi
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p. 10152 - 10158
(2015/02/05)
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- Selective sulfoxidation with hydrogen peroxide catalysed by a titanium catalyst
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A moisture-tolerant cyclopentadienyl-silsesquioxane titanium complex efficiently catalyses the selective oxidation of various types of sulfides to either sulfoxides (TOFs up to 32 530 h-1) or sulfones with H2O2 (30% in water) under mild conditions.
- Postigo, Lorena,Ventura, Maria,Cuenca, Toms,Jimnez, Gerardo,Royo, Beatriz
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p. 320 - 324
(2015/02/02)
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- Peroxoniobium(v)-catalyzed selective oxidation of sulfides with hydrogen peroxide in water: A sustainable approach
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An efficient and eco-compatible route for the selective oxidation of a variety of thioethers to the corresponding sulfoxide or sulfone with 30% aqueous H2O2 in water, using newly synthesized peroxoniobium (pNb) complexes as catalysts, is described. The catalysts with formulas Na2[Nb(O2)3(arg)]·2H2O (arg = arginate) (NbA) and Na2[Nb(O2)3(nic)(H2O)]·H2O (nic = nicotinate) (NbN) have been synthesized from the reaction of sodium tetraperoxoniobate with 30% H2O2 and the respective organic ligand in an aqueous medium, and these have been comprehensively characterized by elemental analysis, spectral studies (FTIR, Raman, 1H NMR, 13C NMR and UV-vis), EDX analysis and TGA-DTG analysis. The density functional theory (DFT) method has been used to investigate the structure of the synthesized pNb complexes. The catalysts are physiologically safe and can be reused for at least six reaction cycles without losing their activity or selectivity. The oxidation is chemoselective for sulfides or sulfoxides leaving the C=C or alcoholic moiety unaffected. The developed methodologies, apart from being high yielding and straightforward, are completely free from halogen, organic co-solvent, or co-catalysts.
- Gogoi, Sandhya Rani,Boruah, Jeena Jyoti,Sengupta, Gargi,Saikia, Gangutri,Ahmed, Kabirun,Bania, Kusum K.,Islam, Nashreen S.
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p. 595 - 610
(2015/02/02)
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- Carbon-supported metal-modified lacunary tungstosilicic polyoxometallates used as catalysts in the selective oxidation of sulfides
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Lacunary tungstosilicic polyoxometallates modified with transition metal ions [SiW11O39M(H2O)]6-, where M = Mn2+, Fe2+, Co2+or Cu2+, were synthesized and supported on activated carbon to obtain the SiW11MC catalysts. The samples were characterized by FT-IR, XRD, N2 adsorption-desorption measurements, and the acidic properties were determined using the isopropanol dehydration test reaction. The activity and selectivity of the catalysts were evaluated in the selective oxidation of a series of sulfides to sulfoxides or sulfone. The reaction was carried out in acetonitrile as solvent using H2O2 35% p/V as a clean oxidant. The conversion values decreased in the following order: SiW11MnC > SiW11FeC > SiW11CuC > SiW11CoC. The catalysts were reused without appreciable loss of their catalytic activity. It was found that the activity of the catalysts decreases in parallel with the increment in the reduction temperature values. The most easily reducible catalyst displayed the highest conversion values. We found a convenient and selective procedure for oxidizing sulfides to sulfoxides or sulfones using aqueous hydrogen peroxide and a catalytic amount of lacunary tungstosilicic polyoxometallates supported on carbon at low temperatures (20-50 °C) in a reasonably short reaction time
- Frenzel, Romina,Sathicq, ángel G.,Blanco, Mirta N.,Romanelli, Gustavo P.,Pizzio, Luis R.
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- Effect of irradiation intensity on rate and selectivity of photosensitized oxidation of dibutyl sulfide over C70 fullerene
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Photoinitiated oxidation of dibutyl sulfide (DBS) with air oxygen in a toluene solution of C70 fullerene during irradiation with visible light at a wavelength of 500-700 nm results in the formation of dibutyl sulfone as a main detected product, dibutyl sulfoxide, and butanal. A change in the intensity of radiation incident on the reaction mixture from 2.2 to 44 mW/cm2 insignificantly increases the quantum efficiency of the DBS consumption from 4.5 to 5.9%. The selectivity for sulfoxide increases during the process, while selectivity for sulfone decreases.
- Arsentyev,Vorontsov,Parmon
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p. 167 - 172
(2015/05/20)
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- Epoxidation of alkenes and oxidation of sulfides catalyzed by a new binuclear vanadium bis-oxazoline complex
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Bis(oxazoline) ligand, [2,2′-(1,3-phenylene)bis(oxazole-4,2-diyl)]-dimethanol, derived from dicyanobenzene was applied as ligand for complexation with vanadium.The catalyst was characterized by FT-IR, UV-Vis, 1H NMR spectroscopic methods, CHNS, ICP and thermal analyses, and magnetic susceptibility. The catalytic activity of this complex was then studied in the epoxidation of alkenes with TBHP (tert-butyl hydroperoxide), in acetonitrile. The effect of reaction parameters such as kind of solvent and oxygen donors was studied in the epoxidation of cyclooctene. The catalytic activity of this catalyst was also investigated in the oxidation of sulfides with H2O2 in ethanol and the corresponding sulfoxides and sulfones were produced.
- Javadi, Maedeh Moshref,Moghadam, Majid,Mohammadpoor-Baltork, Iraj,Tangestaninejad, Shahram,Mirkhani, Valiollah
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p. 477 - 485
(2015/02/05)
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- Nb and Zr modified MWW zeolites-characterisation and catalytic activity
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Hydrogen forms of MCM-22 and delaminated MCM-56 zeolites were modified with niobium and zirconium species. The structure/texture and surface properties, as well as the catalytic activity for dibutyl sulfide oxidation, of the two types of modified zeolites were compared. The presence of Br?nsted (BAS) and Lewis (LAS) acid sites was detected after pyridine adsorption in all the prepared materials. The highest number of BAS and LAS was observed for HMCM-22. The number of BAS significantly decreased after metal modification because of the interaction between the metal sources and the BAS. External silanol groups of zeolites also participate in metal anchoring. The catalysts obtained were tested for liquid phase dibutyl sulfide oxidation with hydrogen peroxide. The texture of the zeolites and the nature of the metal modifier have a crucial effect on the oxidation of dibutyl sulfide. MCM-56 zeolites are more active than their counterparts of MCM-22 type. Application of niobium containing zeolites significantly increases the reaction rate, leading to 95% conversion after 3 h. The remarkable role of the Nb species is due to its interaction with H2O2 towards peroxo/superoxo species. Modification of both zeolites with zirconium does not increase their activity because of the strong interaction of zirconium species with sulfur compounds. This journal is
- Wojtaszek-Gurdak, Anna,Ziolek, Maria
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p. 22326 - 22333
(2015/03/14)
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- Oxidation of alkenes and sulfides catalyzed by a new binuclear molybdenum bis-oxazoline complex
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A novel bis(oxazoline) ligand derived from 1,3-dicyanobenzene was prepared and applied as a ligand for the preparation of a new binuclear molybdenyl complex. This ligand was characterized by UV-Vis, mass, 1H NMR, and FT-IR spectroscopic methods, thermal and elemental analysis and X-ray diffraction. The molybdenum complex was prepared by the reaction of this ligand with MoO2(acac)2. The catalyst was also characterized by FT-IR, UV-Vis, and ICP spectroscopy, elemental and thermal analysis. This catalytic system was efficiently used for the oxidation of alkenes and sulfides in the presence of TBHP. The effect of different solvents and kind of oxygen donor was also studied in the oxidation reactions.
- Moshref Javadi, Maedeh,Moghadam, Majid,Mohammadpoor-Baltork, Iraj,Tangestaninejad, Shahram,Mirkhani, Valiollah,Kargar, Hadi,Tahir, Muhammad Nawaz
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- Efficient and convenient oxidation of sulfides to sulfones using H 2O2 catalyzed by V2O5 in ionic liquid [C12mim][HSO4]
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A simple, efficient, and eco-friendly procedure for the oxidation of sulfides to sulfones using H2O2 catalyzed by V 2O5 in ionic liquid [C12mim][HSO4] has been developed. This atom-economical protocol affords the target products in good to high yields. The products can be separated by a simple extraction with organic solvent, and the catalytic system can be recycled and reused without loss of catalytic activity.
- Hu, Yu-Lin,Liu, Xiao-Bing,Fang, Dong
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- The catalytic efficiency of Fe-porphyrins supported on multi-walled carbon nanotubes in the heterogeneous oxidation of hydrocarbons and sulfides in water
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Novel recoverable biomimetic catalysts were prepared by the coordinative anchoring of an iron(iii) meso-tetraphenyl porphyrin complex [Fe(TPP)Cl] and some derivatives on the activated multi-walled carbon nanotube (AMWCNT) via hydroxyl functionality (Fe-Por-AMWCNT). The simple heterogeneous catalyst [Fe(TPP)Cl-MWCNT] was characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Raman, FT-IR and UV-vis spectroscopy. The amount of catalyst loading on the nanotubes, was determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES). The thermogravimetric analysis (TGA) demonstrated that the nanocatalyst was thermally stable up to almost 400 °C, exhibiting high thermostability. The epoxidation of olefins and the oxidation of saturated hydrocarbons to the related ketones and also sulfides to the sulfones by aqueous solution of tetra-n-butylammonium peroxomonosulfate (n-Bu4NHSO 5, TBAOX) were efficiently enhanced with excellent selectivity under the influence of the separable nanocatalyst with very low catalyst loading. Sulfoxides could also be selectively produced in ethanol, which makes the title methodology a good alternative for both sulfoxide and sulfone production. The separation and recycling of the catalyst and oxidant by-products were simple, effective and economical in this clean oxidation method. The FT-IR, UV-vis and leaching experiments after ten successive cycles showed that the catalyst was most strongly anchored to the MWCNT support. The Royal Society of Chemistry 2014.
- Rezaeifard, Abdolreza,Jafarpour, Maasoumeh
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p. 1960 - 1969
(2014/06/24)
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- Selective synthesis of sulfoxides and sulfones from sulfides using silica bromide as the heterogeneous promoter and hydrogen peroxide as the terminal oxidant
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Silica bromide as a heterogeneous promoter and reagent is prepared from the reaction of silica gel with PBr3as a non-hydroscopic, filterable, cheap, and stable yellowish powder that can be stored for months. The results show that silica bromide is a suitable and efficient promoter for the chemoselective oxidation of sulfides to the corresponding sulfoxides or sulfones in the presence of 30% H2O2in acetonitrile. The excellent yields, heterogeneous conditions, simplicity, compatibility with a variety of functionalities, and ease of isolation of the products make our procedure a practical alternative.
- Maleki, Behrooz,Hemmati, Saba,Sedrpoushan, Alireza,Ashrafi, Samaneh Sedigh,Veisi, Hojat
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p. 40505 - 40510
(2015/02/03)
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- Metal-free chemoselective oxidation of sulfides by in situ generated Koser's reagent in aqueous media
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Selective oxidation of sulfides was successfully performed by employing phenyliodine diacetate as an oxidant with the catalysis of TsOH in aqueous solution under mild conditions. Sulfoxides were formed with 1.1 equiv of PhI(OAc)2 at room temperature; whereas sulfones were obtained in the presence of 2.1 equiv of PhI(OAc)2 at 80 C under otherwise identical conditions. Notably, various sulfides were converted to corresponding sulfoxides or sulfones in good to high yields by this metal-free protocol.
- Yu, Bing,Guo, Chun-Xiang,Zhong, Chun-Lai,Diao, Zhen-Feng,He, Liang-Nian
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supporting information
p. 1818 - 1821
(2014/03/21)
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- Selective hydrogen peroxide oxidation of sulfides to sulfoxides or sulfones with MWW-type titanosilicate zeolite catalyst under organic solvent-free conditions
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Selective oxidation of sulfides to sulfoxides and sulfones with hydrogen peroxide under organic solvent-free conditions was demonstrated by the MWW-type titanosilicate zeolite catalyst. Sulfides were oxidized smoothly to give sulfoxides with good selectivities at ambient temperature using 1.0-1.2 equiv of hydrogen peroxide with the MWW-type titanosilicate zeolite catalyst. Especially, the Ti-MWW with an interlayer-expanded structure (Ti-IEZ-MWW) catalyst showed high activity with good chemoselectivity for the oxidation of various sulfides. The catalyst is recyclable for at least five cycles, and the only byproduct is water. Sulfides were directly oxidized to give sulfones in high yields by 2.5 equiv of hydrogen peroxide with the MWW-type titanosilicate zeolite catalyst under organic solvent-free conditions.
- Kon, Yoshihiro,Yokoi, Toshiyuki,Yoshioka, Masato,Tanaka, Shinji,Uesaka, Yumiko,Mochizuki, Takehisa,Sato, Kazuhiko,Tatsumi, Takashi
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p. 7584 - 7592
(2014/12/10)
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- Highly efficient selective oxidation of sulfides to sulfoxides by montmorillonite-immobilized metalloporphyrins in the presence of molecular oxygen
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Highly efficient and selective oxidation of sulfides to sulfoxides with dioxygen catalyzed by cationic meso-tetrakis (1-methyl-4-pyridyl) (TM4PyP) metalloporphyrins immobilized into montmorillonite (MT) interlayer was achieved. Manganese (II) porphyrin (MnTM4PyP-MT) presented excellent activity for the oxidation of sulfides under ambient conditions. In the model oxidation, thioanisole was converted completely and the selectivity towards sulfoxide was up to 95%. This catalyst also showed high activity and selectivity for the most sulfides. The catalyst could be reused consecutively five times without significant loss of activity.
- Zhou, Xian-Tai,Ji, Hong-Bing
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- Merrifield resin supported peroxomolybdenum(vi) compounds: Recoverable heterogeneous catalysts for the efficient, selective and mild oxidation of organic sulfides with H2O2
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We have generated new heterogeneous catalysts by immobilizing dioxomonoperoxomolybdenum(vi) on amino acid functionalized Merrifield resin, which exhibit excellent activity, stability and selectivity for the oxidation of thioethers and dibenzothiophene (DBT) to the corresponding sulfoxides or sulfones by H2O2 at ambient temperature. The synthetic protocols are high-yielding, halogen-free, environmentally clean and safe, and operationally simple. The catalysts, [MoO2(O2)(L) 2]2--MR [L = valine (MRVMo) or alanine (MRAMo) and MR = Merrifield resin] were prepared by reacting H2MoO4 with 30% H2O2 and the respective amino acid functionalized resin, at near neutral pH. The compounds were characterized by elemental analysis, spectral studies (FTIR, Raman, 13C NMR and 95Mo NMR, diffuse reflectance UV-Vis and XPS), SEM, EDX, XRD, Brunauer-Emmett-Teller (BET) and TGA-DTG analysis. The easy recyclability of the catalysts for several catalytic cycles without change in activity and selectivity, their complete chemoselectivity towards the sulfur group of substrates bearing other oxidation prone functional groups, are important "green" attributes of these catalysts.
- Boruah, Jeena Jyoti,Das, Siva Prasad,Ankireddy, Seshadri Reddy,Gogoi, Sandhya Rani,Islam, Nashreen S.
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p. 2944 - 2959
(2013/10/08)
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- Imidazolium perrhenate ionic liquids as efficient catalysts for the selective oxidation of sulfides to sulfones
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A series of imidazolium perrhenate ionic liquids (IPILs) have been synthesized and used as efficient catalysts for the oxidation of sulfides to sulfones with aqueous hydrogen peroxide under mild conditions. Various sulfones are obtained in good to excellent yields. IPILs are stable and can be reused at least ten times without detectable activity loss. Furthermore, this system provides a reasonably environmentally benign chemical process in terms of potential industrial application.
- Zhang, Bo,Li, Su,Yue, Shuang,Cokoja, Mirza,Zhou, Ming-Dong,Zang, Shu-Liang,Kühn, Fritz E.
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p. 108 - 112
(2013/10/01)
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- Nano-rod catalysts: Building MOF bottles (MIL-101 family as heterogeneous single-site catalysts) around vanadium oxide ships
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Porous materials based on chromium (III) terephthalate metal organic frameworks (Cr-MIL(101)) and their new composites with vanadium oxide has emerged as a potential catalyst because of its high specific surface area, tunable pore size, and unique structure. The structural and textural characterization of V@MIL(101) were done using FTIR, X-ray diffraction, N 2 adsorption-desorption, and TEM. XRD and adsorption-desorption analysis shows that the mesostructure of MIL-101 remains intact after vanadium oxide modifications, while spectral technique show the successful immobilizing of the neat vanadium oxide inside the MIL-101 cavities. These new catalysts were found to be highly effective for selective oxidation of sulfides to sulfoxides and sulfones with H2O2 at room temperature and the 4.2% V@MIL(101) catalyst showed the highest activity. The PW12@MCF im heterogeneous system showed high catalytic oxidative activity in the treatment of commodity gasoline.
- Fazaeli, Razieh,Aliyan, Hamid,Moghadam, Majid,Masoudinia, Mona
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- Acidic three-liquid-phase microemulsion systems based on balanced catalytic surfactant for epoxidation and sulfide oxidation under mild conditions
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Didecyldimethylammonium tungstate has been designed as a balanced catalytic surfactant to form acidic three-liquid-phase microemulsion systems at room temperature in the presence of water, a non-chlorinated solvent and dimethyldioctylammonium salts (hydrogen sulfate and dihydrogen phosphate). The triphasic system is efficient for the oxidation of olefins, sulfides and thiophenes under mild conditions. Moreover, the recovery and reusability of the catalyst, the straightforward separation of products and catalysts in two distinct phases as well as the possible use of environmentally friendly solvents such as tert-butyl acetate, make this system particularly attractive for catalytic oxidation reactions involving hydrogen peroxide as the primary oxidant under acidic or neutral conditions.
- Fressancourt-Collinet, Marion,Hong, Bing,Leclercq, Loic,Alsters, Paul L.,Aubry, Jean-Marie,Nardello-Rataj, Veronique
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supporting information
p. 409 - 420
(2013/05/22)
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