- Sulfoxidation of Thioethers using Titanium Silicate Molecular Sieve Catalysts
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Titanium silicate molecular sieves having MEL (TS-2) or MFI (TS-1) topology efficiently catalyse the oxidation of various thioethers to the corresponding sulfoxides and sulfones using dilute hydrogen peroxide (26 wtpercent) as an oxidising agent.
- Reddy, Ravinder S.,Reddy, J. Sudhakar,Kumar, Rajiv,Kumar, Pradeep
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- Asymmetric oxaziridination catalyzed by cinchona alkaloid derivatives containing sulfide
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A new method has been developed for the asymmetric oxaziridination of aryl aldimines with m-chloroperbenzoic acid, involving the use of cinchona alkaloid derivatives containing a sulfide moiety as a catalyst. The new method provided access to optically active oxaziridines in good yields with high enantiomeric excess (ee) values of up to 95%.
- Zhang, Tianyi,He, Wei,Zhao, Xingyu,Jin, Ying
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- CHEMISTRY OF SINGLET OXYGEN - 38. TEMPERATURE EFFECT ON THE PHOTOOXIDATION OF SULFIDES.
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The reactivity of diethyl sulfide with singlet oxygen has been determined at room temperature (23-24 degree C) and at minus 78 degree C in various solvents. Although the consumption of sulfide is much faster at minus 78 degree C, the rate of removal of singlet oxygen by sulfide is relatively independent of solvent and temperature. A comparison of the rate of product formation with the rate of singlet oxygen removal shows that over 97% quenching is observed in aprotic and about 10% in protic solvents at room temperature. At minus 78 degree C, the quenching process is suppressed in both protic and aprotic solvents. Surprisingly, 2,5-diphenylfuran showed a similar but much smaller effect of solvent and temperature.
- Gu,Foote
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- Effect of alcohols on the photooxidative behavior of diethyl sulfide
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The reactions of singlet oxygen with diethyl sulfide (Et2S) in benzene alcohol mixtures have been examined. The salient discoveries include: (1) the rate constants of product formation, kr, in benzene/methanol mixtures are a function of the concentration of methanol, (2) the ability of alcohols to supress physical quenching are a function of their pKa's, and (3) trapping experiments with diphenyl sulfoxide are consistent with two distinct intermediates. A mechanism which involves formation of a persulfoxide followed by reaction with methanol to give a hydroperoxy-methoxy sulfurane is consistent with all of the results.
- Clennan, Edward L.,Greer, Alexander
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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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- A μ-AsO4-Bridging Hexadecanuclear Ni-Substituted Polyoxotungstate
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A novel tetrahedral μ-AsO4-bridging hexadecanuclear Ni-substituted silicotungstate (ST) Na21H10[(AsO4){Ni8(OH)6(H2O)2(CO3)2(A-α-SiW9O34)2}2]·60H2O (1) was made by the reactions of trivacant [A-α-SiW9O34]10- ({SiW9}) units with Ni2+ cations and Na3AsO4·12H2O and characterized by IR spectrometry, elemental analysis, thermogravimetric analysis (TGA), and powder X-ray diffraction (PXRD). 1 contains a novel polyoxoanion [(AsO4){Ni8(OH)6(H2O)2(CO3)2(A-α-SiW9O34)2}2]31- built by four trivacant Keggin [A-α-SiW9O34]10- fragments linked through an unprecedented [(AsO4){Ni8(OH)6(H2O)2(CO3)2}2]9+ cluster, where the tetrahedral AsO4 acts as an exclusively μ2-bridging unit to link multiple Ni centers; such a connection mode appears for the first time in polyoxometalate chemistry. Furthermore, the electrochemical and catalytic oxidation properties of compound 1 have been investigated.
- Lian, Chen,Li, Hai-Lou,Yang, Guo-Yu
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p. 3996 - 4003
(2021/04/07)
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- A {Ti6W4}-Cluster-Substituted Polyoxotungstate: Synthesis, Structure, and Catalytic Oxidation Properties
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A novel Ti-W-O-cluster-substituted tungstoantimonate (TA), [H2N(CH3)2]3Na4H9[{Ti6W4O18(OH)(H2O)3}(B-α-SbW9O33)3]·20H2O (1), has been made by hydrothermal reactions of trivacant [B-α-SbW9O33]9- units, Ti4+ cations, and WO42- anions in the presence of [H2N(CH3)2]·Cl and structurally characterized. Intriguingly, the polyoxoanion of 1 is constructed from three [B-α-SbW9O33]9- units and a previously unobserved decanuclear heterometallic Ti-W-O cluster [Ti6W4O18(OH)(H2O)3]11+ ({Ti6W4}) that is comprised of an octahedral [Ti6WO6(H2O)3]18+ cluster and an edge-sharing [W3O12(OH)]7- fragment via six W-O-Ti/W linkers. Furthermore, studies on the catalytic oxidation properties reveal that 1 possesses good catalytic activity toward the oxidation reactions of various sulfides and cyclooctene based on the environmentally friendly oxidant H2O2.
- Li, Hai-Lou,Lian, Chen,Yang, Guo-Yu
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supporting information
p. 14622 - 14628
(2021/10/01)
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- {Ti6}/{Ti10} Wheel Cluster Substituted Silicotungstate Aggregates
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Two novel Ti-oxo wheel cluster substituted silicotungstates (STs) [H2N(CH3)2]9H9[Ti6O6(SiW10O37)3]·11H2O (1) and [H2N(CH3)2]16H10[Ti10O11(SiW10O37)2(SiW9O35)2]·14H2O (2) have been made by hydrothermal reactions. The polyoxoanion of 1 is a ring-shaped trimer where a Ti6O6 ({Ti6}) wheel cluster is encapsulated by three divacant [SiW10O37]10- (SiW10O37) fragments. However, 2 is built by two divacant SiW10O37 units and two rare trivacant [SiW9O35]12- (SiW9O35) fragments and further installs an unprecedented Ti10O11 ({Ti10}) double-wheel cluster. To the best of our knowledge, 2 is rare in POM chemistry. Studies on the catalytic oxidation properties reveal that 1 exhibits high catalytic activity toward the oxidation of various sulfides using H2O2 as an oxidant. Furthermore, 1 can be facilely recycled and reused for at least five cycles without obvious loss of catalytic activity.
- Li, Hai-Lou,Lian, Chen,Yang, Guo-Yu
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p. 16852 - 16859
(2021/11/13)
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- A novel binuclear iron(III)-salicylaldazine complex; synthesis, X-ray structure and catalytic activity in sulfide oxidation
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A novel binuclear iron(III)-salicylaldazine complex has been synthesized and characterized by various techniques such as IR and UV–Vis spectroscopy and X-ray crystallography. The catalytic oxidation of sulfides in the presence of the aforementioned complex was explored at room temperature using urea hydrogen peroxide (UHP) as an oxidant. Effects of different reaction conditions consisting catalyst and oxidant amount, solvent effect and reaction time on the catalytic activity and selectivity in the reaction of methylphenylsulfide oxidation has been surveyed. Perfect selectivity toward sulfoxide was achieved after 15 min in CH3CN by choice of a properly optimized reaction condition.
- Akbari, Ali,Amini, Mojtaba,Bagherzadeh, Mojtaba,Ellern, Arkady,Mesbahi, Elnaz,Woo, L. Keith
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- Synthesis of Na22[((RE)4(H2O)6Sb6O4)(SbW10O37)2(SbW8O31)2] [(RE)III = Y, Gd, Tb, Dy, Ho, Er, Tm, Yb]: Synthesis, characterization and catalytic application
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A series of eight rare-earth substituted antimony tungstates with the formulae [((RE)4(H2O)6Sb6O4)(SbW10O37)2(SbW8O31)2]22– [(RE)III = Y(1), Gd(2), Tb(3), Dy(4), Ho(5), Er(6), Tm(7), Yb(8)] has been synthesized under ambient conditions. The compounds were isolated using rare-earth salts and Na9[B-α-SbW9O33]?19.5 H2O as precursors along with sodium dihydrogen phosphate in 1 M NaCl solution. The addition of dihydrogen phosphate was found to be a crucial step for the isolation of these polyanions. The polyanions were characterized by various analytical techniques such as single crystal X-ray diffraction (1a – 6a) (SC-XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA). The compounds were found to show efficient heterogeneous catalytic activity for oxidation of thioethers.
- Gupta, Rakesh,Hussain, Firasat,Kaushik, Reetam,Khan, Imran
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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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- Controlled α-mono- and α,α-di-halogenation of alkyl sulfones using reagent-solvent halogen bonding
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The direct and selective α-mono-bromination of alkyl sulfones was achieved through base-mediated electrophilic halogenation. The appropriate combination of solvent and electrophilic bromine source was found to be critical to control the nature of the products formed, where reagent-solvent halogen bonding is proposed to control the selectivity via alteration of the effective size of the electrophilic bromine source. Conversely, the α,α-di-brominated sulfones were selectively obtained in good yields following polyhalogenation followed by selective de-halogenation during workup. Both procedures can be applied on gram scale, and the mono-halogenation was successfully extended to the fully selective α-chlorination, α-iodination and α-fluorination of alkyl sulfones.
- Poteat, Christopher M.,Lindsay, Vincent N. G.
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supporting information
p. 2912 - 2915
(2019/03/17)
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- An Oxalate-Functionalized Tetra-ZrIV-Substituted Sandwich-Type Silicotungstate: Hydrothermal Synthesis, Structural Characterization, and Catalytic Oxidation of Thioethers
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A previously unknown inorganic–organic hybrid polyoxidometalate constructed from oxalate-functionalized tetra-ZrIV-substituted dimeric silicotungstate, (NH4)3Na5K6[Zr4(μ3-O)2(μ-OH)2(ox)2(SiW10O37)2]·23H2O (1, ox = oxalate) has been synthesized under mild hydrothermal conditions and characterized by FTIR spectroscopy, elemental analysis, thermogravimetric analysis, single-crystal and powder X-ray diffraction. Compound 1 contains a centrosymmetric polyoxidoanion structure with two [SiW10O37]10– units sandwiching a [Zr4(μ3-O)2(μ-OH)2(ox)2]6+ cluster. The catalytic performances of 1 involving oxygenation reactions of thioethers by H2O2 were evaluated, showing that 1 is an excellent catalyst for the catalytic oxidation of thioethers to sulfoxides/sulfones.
- Wang, Yue-Lin,Zhang, Zhong,Li, Hai-Lou,Li, Xu-Yan,Yang, Guo-Yu
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p. 417 - 422
(2018/09/06)
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- Fe3O4/PEG-SO3H as a heterogeneous and magnetically-recyclable nanocatalyst for the oxidation of sulfides to sulfones or sulfoxides
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We present below a sulfonated-polyethylene glycol-coated Fe3O4 nanocomposite (Fe3O4/PEG-SO3H) as a greatly effective and ecological nanocatalyst for the selective oxidation of sulfides to sulfoxides or sulfones with brilliant yields under solvent-free conditions by employing 30% hydrogen peroxide as the oxidant. A number of sulfides containing alcohol, ester, and aldehyde functional groups were fruitfully and selectively oxidized without altering the desired characteristics. The magnetic nanocatalyst (Fe3O4/PEG-SO3H) can be conveniently and swiftly retrieved through the utilization of an external magnetic tool and recycled for more than 10 reaction runs without significantly decreasing its catalytic behavior.
- Mirfakhraei, Saeideh,Hekmati, Malak,Eshbala, Fereshteh Hosseini,Veisi, Hojat
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p. 1757 - 1761
(2018/02/09)
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- Green Organocatalytic Oxidation of Sulfides to Sulfoxides and Sulfones
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A highly efficient synthetic methodology towards the selective synthesis of sulfoxides and sulfones is reported using a cheap and green organocatalytic method. Starting from sulfides and using 2,2,2-trifluoroacetophenone as the organocatalyst and H2O2 as the oxidant, the high-yielding preparation of sulfoxides or sulfones is described, being dependent on the reaction conditions.
- Voutyritsa, Errika,Triandafillidi, Ierasia,Kokotos, Christoforos G.
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p. 917 - 924
(2017/02/15)
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- Hydrophilic phase transfer catalyst based on the sulfoacid group and polyoxometalate for the selective oxidation of sulfides in water with hydrogen peroxide
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A hybrid catalyst, based on SO3H-fuctionalized quaternary ammonium and polyoxovanadometalate, was synthesized and used for the selective oxidation of sulfides in water at room temperature. The highest turnover numbers (TON) can reach up to 1536. The organic products with high yields can be easily separated and the catalytic system can be used several times with the retention of catalytic activity.
- Zhao, Wei,Yang, Chunxia,Liu, Kecheng,Yang, Ying,Chang, Tao
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supporting information
p. 447 - 451
(2017/02/05)
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- Generation of VBr? VBi? VO?? defect clusters for 1O2 production for molecular oxygen activation in photocatalysis
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Defect engineering on a semiconductor surface can provide coordinatively unsaturated sites for molecular oxygen activation in photocatalysis. In this work, we demonstrated that the vacancy type was key to modulate the molecular oxygen activation process on BiOBr nanosheets. By regulating the reaction time, an oxygen vacancy (VO??), a double atom defect cluster (VBi? VO??) and triple atom clusters (VBi? VO?? VBi? and VBr? VBi? VO??) were accordingly generated on the surface, subsurface and bulk of BiOBr. More importantly, the newly-discovered VBr? VBi? VO?? defect cluster was highly related to the singlet oxygen (1O2) production ability of BiOBr. Meanwhile, the excellent photocatalytic selective oxidation reactions were successfully realized over BiOBr with the VBr? VBi? VO?? defect cluster. In addition, time-dependent defect cluster generation and the associated molecular oxygen activation were discussed.
- Ding, Jie,Dai, Zan,Tian, Fan,Zhou, Bo,Zhao, Bin,Zhao, Huiping,Chen, Zhiquan,Liu, Yunling,Chen, Rong
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supporting information
p. 23453 - 23459
(2017/11/30)
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- Experimental study on deep desulfurization of MTBE by electrochemical oxidation and distillation
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With the increasing awareness of environmental protection, deep desulfurization of methyl tert-butyl ether (MTBE), which is the most important octane booster in gasoline, is extremely urgent. Herein, a new desulfurization method, involving the combination of electrochemical oxidation and distillation, is proposed to reduce the sulfur content in MTBE. Under optimum operating conditions, the sulfur content of real MTBE decreases from 132.5 μg g-1 to 2.3 μg g-1 and the desulfurization efficiency reaches 98.25%. The oxidation products with high boiling points can be separated by distillation. FTIR analyses prove that electrochemical oxidation has no influence on the main properties of MTBE. Moreover, GC/MS is used to study the conversion of model organic sulfides (dimethyl disulfide, diethyl sulfide and butyl mercaptan) in the electrochemical oxidative desulfurization process. Finally, the possible reaction mechanism of the electrochemical oxidative desulfurization of MTBE is proposed.
- Li, Jing-Jing,Zhou, Fei,Tang, Xiao-Dong,Hu, Tao,Cheng, Jin
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p. 4803 - 4809
(2016/01/29)
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- A reusable catalytic system for sulfide oxidation and epoxidation of allylic alcohols in water catalyzed by poly(dimethyl diallyl) ammonium/polyoxometalate
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An effective catalyst based on a polyoxometalate and a polymer has been developed for the oxidation of sulfides and allylic alcohols under mild conditions in water. The synthetic procedure to form the catalyst and the separation of the products are convenient, and the system is reusable.
- Zhao, Wei,Yang, Chunxia,Cheng, Zhiguo,Zhang, Zhenghui
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supporting information
p. 995 - 998
(2016/02/27)
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- Alkylimidazolium/alkylpyridinium octamolybdates catalyzed oxidation of sulfides to sulfoxides/sulfones with hydrogen peroxide
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β-Mo8O26 based alkyl imidazolium and pyridinium salts of general formula [Bmim]4Mo8O26 (Bmim = 1-butyl-3-methylimidazolium), [Hmim]4Mo8O26 (Hmim = 1-hexyl-3-methylimidazolium), [Dhmim]4Mo8O26 (Dhmim = 1.2-dimethyl-3-hexylimidazolium) and [Hpy]4Mo8O26 (Hpy = 1-hexylpyridinium) have been used as catalysts for the oxidation of sulfides using 30% hydrogen peroxide as oxidant. The examined β-Mo8O26 salts prove to be highly active and are self-separating. A high selectivity towards either sulfoxides or sulfones can be nicely controlled by variation of the reaction conditions. In both cases, the catalysts can be recycled and reused for several times without significant loss of activity, representing a good stability of the catalysts.
- Ye, Jin-Xin,Wang, Jing-Yun,Wang, Xin,Zhou, Ming-Dong
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supporting information
p. 1 - 3
(2016/04/26)
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- Sulfocompound selective catalytic oxidation reaction system in aqueous phase
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The invention provides a sulfocompound selective catalytic oxidation reaction system in an aqueous phase. A catalyst, a sulfocompound and 30% hydrogen peroxide are stirred for 1.5-2 hours under room temperature in the aqueous phase according to the molar ratio of the catalyst to the sulfocompound to the 30% hydrogen peroxide being 1 to 400 to 1200, wherein the conversion rate is greater than 97%, and the selectivity of the product namely sulphone is greater than 94%; the catalyst, the sulfocompound and the 30% hydrogen peroxide are stirred for 6 hours under the room temperature in the aqueous phase according to the molar ratio of the catalyst to the sulfocompound to the 30% hydrogen peroxide being 1 to 1666 to 1666, wherein the conversion rate is greater than 90%, and the selectivity of the product namely sulphoxide is greater than 80%. According to the reaction system disclosed by the invention, after the reaction is completed, extraction is performed with ethyl acetate, after an organic phase is separated, the catalyst dispersed in the aqueous phase can be directly used for the next catalytic reaction, and the catalytic activity, the conversion rate and the selectivity are all kept. The sulfocompound selective catalytic oxidation reaction system disclosed by the invention has the advantages that water is used as a solvent, the reaction condition is mild, the catalytic activity is high, the selectivity of products is good, the consumption of the catalyst is low, and the catalyst can be repeatedly used.
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Paragraph 0029; 0030; 0031; 0032
(2018/02/04)
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- Selective oxidation of sulfurs and oxidation desulfurization of model oil by 12-tungstophosphoric acid on cobalt-ferrite nanoparticles as magnetically recoverable catalyst
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Silica-coated CoFe2O4 nanoparticles were prepared and used as a support for the immobilization of 12-tungstophosphoric acid, to produce a new magnetically separable catalyst. This catalyst was characterized using X-ray diffraction, wavelength-dispersive X-ray spectroscopy, Fourier-transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, laser particle size analysis, and vibrating sample magnetometry. The catalyst showed high activity in the selective oxidation of thioethers and thiophenes to the corresponding sulfones under mild conditions. The catalytic activity of the nanocatalyst in the oxidative desulfurization of model oil was investigated. The effect of nitrogen-containing compounds on sulfur removal from the model oil was also evaluated. The catalyst showed high activity in the oxidative desulfurization of diesel. The catalyst can be readily isolated from the oxidation system using an external magnet and no obvious loss of activity was observed when the catalyst was reused in four consecutive runs.
- Rafiee, Ezzat,Rahpeyma, Nasibeh
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p. 1342 - 1349
(2015/09/01)
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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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- Chemoselective oxidation of sulfides to sulfoxides with urea hydrogen peroxide (UHP) catalyzed by non-, partially and fully β-brominated meso-tetraphenylporphyrinatomanganese(III) acetate
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Selective oxidation of sulfides to sulfoxides with urea hydrogen peroxide in the presence of the manganese complex of non-, partially and fully brominated meso-tetraphenylporphyrin, (MnTPPBrx(OAc) (x = 0, 2, 4, 6 and 8)) is reported. Although, the maximum conversion was achieved in the case of MnTPPBr4(OAc), little difference was found between the catalytic activity of MnTPP(OAc), MnTPPBr2(OAc) and MnTPPBr4(OAc). MnTPPBr8(OAc) showed an unusually very low catalytic efficiency compared to the other manganese porphyrins. The presence of small amounts of acetic acid was shown to have significant effect on the total conversion and the oxidative stability of the catalyst.
- Rayati, Saeed,Nejabat, Fatemeh,Zakavi, Saeed
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- Synthesis and characterization of 3-[N,N′-bis-3-(salicylidenamino) ethyltriamine] Mo(vi)O2@SBA-15: A highly stable and reusable catalyst for epoxidation and sulfoxidation reactions
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The efficient and reusable oxidation catalyst 3-[N,N′-bis-3- (salicylidenamino)ethyltriamine] Mo(vi)O2@SBA-15 has been synthesized by the anchoring of the 3-[N,N-bis-3-(salicylidenamino)ethyltriamine] ligand (L or Salpr) on the inner surfaces of organofunctionalized SBA-15 and subsequent complexation with Mo(vi)O2(acac)2. The physico-chemical properties of the functionalized catalysts were analyzed by elemental analysis, ICP-OES, XRD, N2-sorption measurements, TG & DTA, solid state 13C, 29Si NMR spectroscopy, FT-IR, Raman spectroscopy, XPS, DRS UV-Vis spectroscopy, SEM and TEM. XRD and N2 sorption analyses helped to find out the morphological and textural properties of the synthesized catalysts and confirm that an ordered mesoporous channel structure was retained even after the multistep synthetic procedures. The (100), (110) and (200) reflections in SBA-15 provide hints of a good structural stability, the existence of long range ordering and a high pore wall thickness. TG and DTA results reveal that the thermal stability of (L)Mo(vi)O2@SBA-15 was maintained up to 300°C. The organic moieties anchored over the surface of the SBA-15 support were determined by solid state 13C NMR and FT-IR spectroscopy. Further, solid state 29Si NMR spectroscopy provides the information about the degree of functionalization of the surface silanol groups with the organic moiety. The electronic environment and the oxidation state of the molybdenum site in (L)Mo(vi)O2@SBA-15 were monitored by Raman spectroscopy, XPS and DRS UV-Vis techniques. Moreover, the morphology and topographic information of the synthesized catalysts were confirmed by SEM and TEM imaging. The synthesized catalysts were evaluated in epoxidation and sulfoxidation reactions, and the results show that (L)Mo(vi)O2@SBA-15 exhibits high conversion and selectivity towards epoxidation and sulfoxidation reactions in combination with high stability. The anchored solid catalysts can be recycled effectively and reused several times without major loss in activity. In addition, Sheldon's hot filtration test was also carried out.
- Lazar, Anish,Thiel, Werner R.,Singh
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p. 14063 - 14073
(2014/04/17)
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- Tris(hydroxymethyl)aminomethane modified layered double hydroxides greatly facilitate polyoxometalate intercalation
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Polyoxometalate (POM) intercalation to layered double hydroxides (LDHs) has been greatly restricted by the geometry, charge and size of POMs. We report herein, for the first time, the intercalation of Na3[PW12O40]·15H2O into tris(hydroxymethyl)-aminomethane (Tris) modified layered double hydroxides (Tris-LDH-CO3) using an ion exchange method, resulting in the formation of novel intercalated Tris-LDH-PW12 under ambient conditions without the necessity of degassing CO2. Theoretical calculations show the decreased energy and the slightly distorted LDH layer after Tris modification, indicating that the Tris-modified LDH layers greatly facilitate the intercalation of PW12. Further application of Tris-LDH-PW12 for oxygenation of sulfides shows highly efficient and selective catalytic activities under mild conditions. The Tris-LDH-PW12 can be easily recovered and reused for more than 10 times without any obvious decrease of reactivity. This opens a completely new pathway for engineering POM-LDH advanced functional materials. This journal is
- Chen, Yang,Yan, Dongpeng,Song, Yu-Fei
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p. 14570 - 14576
(2015/02/19)
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- Cellulose supported manganese dioxide nanosheet catalyzed aerobic oxidation of organic compounds
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Cellulose supported manganese dioxide nanosheets, as a heterogeneous bio-supported and green catalyst, were synthesized by soaking porous cellulose in a potassium permanganate solution. The prepared catalyst was used effectively for the oxidation of various types of alkyl arenes, alcohols and sulfides to their corresponding carbonyl and sulfoxide compounds, respectively in high yields using air as the oxidant at ambient pressure. The catalyst can be recycled and reused in five runs without any significant loss of efficiency. The mild reaction conditions for the oxidation of alcohols and sulfides, high yields, recyclability of the catalyst, and very easy workup procedure are other advantages of this catalyst.
- Shaabani, Ahmad,Hezarkhani, Zeinab,Shaabani, Shabnam
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p. 64419 - 64428
(2015/04/27)
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- Selective oxidation of sulfides and olefins by a manganese (III) complex containing an N,O-type bidentate oxazine ligand
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A new manganese(III) complex [(N-O)2Mn(OAc)] was synthesized using 2-(2'-hydroxyphenyl)-5,6-dihydro-1,3-oxazine (N-O) as a bidentate O, N donor. The complex has been characterized by elemental analysis, IR, UV-vis spectroscopy, and X-ray structure analysis. Oxidation of sulfides and epoxidation of olefins, respectively, to their corresponding sulfoxides and epoxides were conducted by this catalyst using urea hydrogen peroxide as oxidant at room temperature under air. The catalyst is efficient in oxidation reactions giving high yields and selectivities.
- Amini, Mojtaba,Bagherzadeh, Mojtaba,Moradi-Shoeili, Zeinab,Boghaei, Davar M.,Ellern, Arkady,Woo, L. Keith
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p. 464 - 472
(2013/08/24)
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- Organic-inorganic polyoxometalate based salts as thermoregulated phase-separable catalysts for selective oxidation of thioethers and thiophenes and deep desulfurization of model fuels
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Synthesis of various organic-inorganic polyoxometalate based salts composed of sulfonated pyridinum cations and the Keggin tungstophosphate anion (PW 12O403-) and their subsequent application in the oxidation of methyl phenyl sulfide with hydrogen peroxide in aqueous media was reported. Special attention was paid to the temperature-dependent solubility of the salts as a function of the organic cation in water. Cyclic voltammetry was further used for the investigation of the redox behavior of these catalysts. Based on these properties, a novel thermoregulated phase-separable catalyst was introduced and successfully used for the selective oxidation of thioethers and thiophenes to the corresponding sulfoxides or sulfones. Catalytic oxidation of the sulfur-containing model oil (methyl phenyl sulfide, dibenzothiophene and thiophene) was also studied under optimized conditions. In both cases, excellent conversion and selectivity were obtained in relatively short reaction times. This novel catalyst showed the characteristic of homogeneous reaction at ambient temperatures and phase-separation at lower temperatures. By simple decantation, the catalyst could be easily separated from the products upon cooling of the reaction mixture and could be reused several times with high recycling efficiency.
- Rafiee, Ezzat,Eavani, Sara
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- Selective oxidation of nonrefractory and refractory sulfides by cyclopentadienyl molybdenum acetylide complexes as efficient catalysts
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The synthesis and catalytic properties of molybdenum acetylide complexes CpMo(CO)3(-C≡CR), R = Ph(1), C6H4-p- CF3 (2) and C6H4-p-CH3 (3) has been studied. The molybdenum acetylide complexes were synthesized from CpMo(CO) 3Cl and aryl acetylenes via Stephens- Castro coupling reaction. These complexes were characterized by single crystal X-ray diffraction analysis, FTIR and 1H NMR spectroscopy. These complexes on treatment with hydrogen peroxide, formed corresponding molybdenum oxo-peroxo species. These in situ formed oxo-peroxo species were found very active (up to 100 % conversion) and selective (up to 100 %) oxidation catalysts for various refractory and nonrefractory sulfides. Interestingly, even though the molybdenum acetylide complexes are homogeneous, they could be recycled very efficiently by extracting the catalytically active molybdenum oxoperoxo species in aqueous phase. Springer Science+Business Media, LLC 2012.
- Chandgude, MacChindra G.,Biradar, Ankush V.,Kotbagi, Trupti V.,Puranik, Vedavati G.,Dongare, Mohan K.,Umbarkar, Shubhangi B.
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p. 1352 - 1360
(2013/01/15)
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- Sulfamic acid-catalyzed oxidation of sulfides to sulfoxides and sulfones using H2O2: Green and chemoselective method
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A mild, efficient, green, and selective oxidation method of sulfides to sulfoxides or sulfones using H2O2 in the presence of catalytic amounts of sulfamic acid has been developed. Various substituted sulfides having functional groups such as alcohol, ester, and aldehyde are successfully and selectively oxidized without affecting the sensitive functionalities in good to excellent yields at room temperature.
- Jafari, Hadi,Rostami, Amin,Ahmad-Jangi, Firoz,Ghorbani-Choghamarani, Arash
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p. 3150 - 3156
(2012/11/07)
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- Efficient oxidation of sulfides catalyzed by a temperature-responsive phase transfer catalyst [(C18H37)2(CH 3)2N]7 PW11O39 with hydrogen peroxide
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A temperature-responsive phase transfer catalyst [(C18H 37)2(CH3)2N]7PW 11O39, could act as an efficient catalyst for selective oxidation of sulfides with 30% aqueous H2O2. Various kinds of sulfides were successfully oxidized to their corresponding sulfones with over 96% yields in a relatively short time and mild conditions. During reaction at 333 K, the catalyst dissolved completely and the oxidation was conducted homogeneously. Before and after reaction, the catalyst was insoluble with cooling, so it is easily recovered and reused. The catalyst was characterized by elemental analysis, FT-IR and 31P NMR.
- Xue, Xiaoling,Zhao, Wei,Ma, Baochun,Ding, Yong
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- Controlled oxidation of organic sulfides to sulfoxides under ambient conditions by a series of titanium isopropoxide complexes using environmentally benign H2O2 as an oxidant
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Controlled oxidation of organic sulfides to sulfoxides under ambient conditions has been achieved by a series of titanium isopropoxide complexes that use environmentally benign H2O2 as a primary oxidant. Specifically, the [N,N′-bis(2-oxo-3-R1-5-R2- phenylmethyl)-N,N′-bis(methylene-R3)-ethylenediamine]Ti(O iPr)2 [R1 = t-Bu, R2 = Me, R 3 = C7H5O2 (1b); R1 = R2 = t-Bu, R3 = C7H5O2 (2b); R1 = R2 = Cl, R3 = C7H 5O2 (3b) and R1 = R2 = Cl, R 3 = C6H5 (4b)] complexes efficiently catalyzed the sulfoxidation reactions of organic sulfides to sulfoxides at room temperature within 30 min of the reaction time using aqueous H2O 2 as an oxidant. A mechanistic pathway, modeled using density functional theory for a representative thioanisole substrate catalyzed by 4b, suggested that the reaction proceeds via a titanium peroxo intermediate 4c′, which displays an activation barrier of 22.5 kcal mol-1 (ΔG?) for the overall catalytic cycle in undergoing an attack by the S atom of the thioanisole substrate at its σ*-orbital of the peroxo moiety. The formation of the titanium peroxo intermediate was experimentally corroborated by a mild ionization atmospheric pressure chemical ionization (APCI) mass spectrometric technique. The Royal Society of Chemistry 2010.
- Panda, Manas K.,Shaikh, Mobin M.,Ghosh, Prasenjit
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experimental part
p. 2428 - 2440
(2010/06/18)
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- Observed and calculated 1Hand 13C chemical shifts induced by the in situ oxidation ofmodel sulfides to sulfoxides and sulfones
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A series of model sulfides was oxidized in the NMR sample tube to sulfoxides and sulfones by the stepwise addition of meta-chloroperbenzoic acid in deuterochloroform. Various methods of quantum chemical calculations have been tested to reproduce the observed 1H and 13C chemical shifts of the starting sulfides and their oxidation products. It has been shown that the determination of the energy-minimized conformation is a very important condition for obtaining realistic data in the subsequent calculation of the NMR chemical shifts. The correlation between calculated and observed chemical shifts is very good for carbon atoms (even for the 'cheap' DFT B3LYP/6-31G* method) and somewhat less satisfactory for hydrogen atoms. The calculated chemical shifts induced by oxidation (the δd values) agree even better with the experimental values and can also be used to determine the oxidation state of the sulfur atom (-S-, -SO-, -SO2 -). Copyright
- Dracinsky, Martin,Pohl, Radek,Slavetinska, Lenka,Budesinsky, Milos
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experimental part
p. 718 - 726
(2011/05/15)
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- A highly efficient, green, rapid, and chemoselective oxidation of sulfides using hydrogen peroxide and boric acid as the catalyst under solvent-free conditions
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We report boric acid as a highly efficient and eco-friendly catalyst for the selective oxidation of sulfides to sulfoxides or sulfones, in excellent yields under solvent-free conditions, using 30% hydrogen peroxide as an oxidant. Various sulfides possessing functional groups such as alcohol, ester, and aldehyde are successfully and selectively oxidized without affecting sensitive functionalities.
- Rostami, Amin,Akradi, Jamal
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experimental part
p. 3501 - 3503
(2010/08/20)
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- Oxidation of organic compounds by sulfonated porous carbon and hydrogen peroxide
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The oxidation of organic compounds by sulfonated porous carbon and H 2O2 was studied at room temperature. Alkyl and aryl sulfides were oxidized to the corresponding sulfoxides or sulfones in excellent yields. Secondary alcohols were also converted to the corresponding esters/lactones and aldehydes to methyl esters in good yields. Moreover, aliphatic tertiary amines and substituted pyridines were oxidized to N-oxides.
- Shokrolahi, Arash,Zali, Abbas,Keshavarz, Mohammad Hossein
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experimental part
p. 1427 - 1432
(2012/04/18)
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- Selective oxidation of sulfides to sulfones using H2O 2 and anderson-type hexamolybdochromate(III) as catalyst
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An Anderson-type hexamolybdochromate(III) is found to be an effective catalyst for the selective oxidation of sulfides to their corresponding sulfones. The reaction was carried out in 60% aq. acetonitrile (v/v) using 30% H2O2 at 60C. Various dialkyl, alkyl-aryl, and diaryl sulfides were selectively oxidized, giving high yields of sulfones after a simple workup procedure.
- Supale, Amit R.,Gokavi, Gavisiddappa S.
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experimental part
p. 725 - 731
(2010/07/05)
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- Oxygen activation on metallic centers and oxidizing abilities of such oxygen
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It was shown that metallcontaining peroxides such as XOOOBu-t [X = (t-BuO)2Al, (t-BuO)3Ti] generate molecular oxygen in the electron-excited singlet state (1O2). These ozonides and η2-peroxocomplex Ph3Bi(η2O2) demonstrate high oxidative activity towards some classes of organic substances under mild conditions (20 °C).
- Zaburdaeva, Elena A.,Dodonov, Viktor A.,Stepovik, Larisa P.
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p. 1265 - 1268
(2008/02/04)
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- Potassium permanganate oxidation of organic compounds
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It has been discovered that potassium permanganate is an effective heterogeneous oxidant, even without resorting to the use of a solid support, if acetonitrile is employed as the solvent. Primary benzylic and secondary alcohols are converted to the corresponding aldehydes and ketones, alkyl arenes are oxidized to the corresponding α-ketones in good yields using this procedure, and both alkyl and aryl sulfides are smoothly converted to the corresponding sulfones, also in excellent yields. When methylene chloride is used as the solvent, instead of acetonitile, the yields of aldehydes, ketones, α-ketones, and sulfones are reduced. However, the oxidation of thiols to disulfides proceeds satisfactorily when methylene chloride is the solvent.
- Shaabani, Ahmad,Tavasoli-Rad, Farahnaz,Lee, Donald G.
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p. 571 - 580
(2007/10/03)
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- Green oxidations. The use of potassium permanganate supported on manganese dioxide
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Permanganate supported on active manganese dioxide can be used effectively for the oxidation of organic compounds under heterogeneous or solvent-free conditions. The residue that remains after extraction of the organic products, manganese dioxide, can be recycled, making the process infinitely sustainable, in theory. The use of this approach for the oxidation of arenes, alcohols and sulfides is described. Graphical Abstract.
- Shaabani, Ahmad,Mirzaei, Peiman,Naderi, Soheila,Lee, Donald G.
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p. 11415 - 11420
(2007/10/03)
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- Oxidation of organic compounds by potassium permanganate supported on montmorillonite K10
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The oxidation of organic compounds by potassium permanganate supported on Montmorillonite K10 has been studied under solvent-free conditions and the results compared with those from corresponding reactions where the reductants are dissolved in methylene chloride. Under both sets of conditions, primary benzylic and secondary alcohols are converted to aldehydes and ketones respectively, sulfides are oxidized to sulfones, and thiols undergo oxidative coupling to give disulfides. Surprisingly, reaction times under solvent-free conditions are shorter than those observed when the reductants are dissolved in a solvent.
- Shaabani, Ahmad,Bazgir, Ayoob,Lee, Donald G.
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p. 3595 - 3607
(2007/10/03)
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- Liquid-phase oxidation of sulfides by an aluminum (and titanium) tert-butoxide - tert-butyl hydroperoxide system
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A system aluminum (and titanium) tert-butoxide-tert-butyl hydroperoxide (1 : 2) under mild conditions (20°C, 1 h) oxidizes aliphatic and alkylaromatic sulfides and diphenyl sulfide to the corresponding sulfones in yields close to ～100%. The oxidation is induced by electron-excited dioxygen formed upon thermal decomposition of intermediate metal-containing peroxy trioxides (ozonides). The latter are formed as a result of the reversible reaction of aluminum or titanium tert-butoxides with tert-butyl hydroperoxide followed by the interaction of di-tert-butoxy-tert-butylperoxyaluminum and tri-tert-butoxy-tert-butylperoxytitanium that formed with another Bu tOOH molecule. Alkminum-containing peroxide (ButO) 2AlOOBut oxidizes sulfides to sulfoxides.
- Dodonov,Zaburdaeva,Stepovik
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p. 1729 - 1734
(2007/10/03)
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- Sulfur-substituted phenylsulfonylureas, processes for their preparation and their use as herbicides and plant growth regulators
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Sulfur-substituted phenylsulfonylureas; processes for their preparation and their use as herbicides and plant growth regulators Compounds of the formula (I) and salts thereof STR1 in which R*, R1, R2, R3, X, Y, Z, W, n and m are defined as in claim 1, and specifically R* is a formyl equivalent of the formula CHO, --CH=NR or CH(X1 R')(X2 R"), are suitable as herbicides and plant growth regulators. They are prepared analogously to known methods, in some cases using novel intermediate products of the formula (XVII) STR2 in which U*=NH2, Cl or (substituted) amino.
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- Efficient oxidation of sulfides catalyzed by transition metal salts with molecular oxygen in the presence of aldehydes
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Oxidation of sulfides to sulfoxides and sulfones was achieved in moderate to high yields with a good selectivity, by using Fe2O3, MnO2, Cu(OH)2 and Cu(OAc)2 as catalyst, with molecular oxygen in the presence of isovaleraldehyde under mild conditions.
- Song, Guoqiang,Wang, Fan,Zhang, Hao,Lu, Xiaoling,Wang, Chen
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p. 2783 - 2787
(2007/10/03)
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- Ruthenium clay catalyzed chemoselective hydrogenation of unsaturated esters, epoxides, sulfones and phosphonates
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Ru-clays were prepared using montmorillonite-PPh2 or montmorillonite-bpy and RuCl3·H2O. The clays obtained were found to be effective catalysts for the reduction of unsaturated esters, epoxides, sulfones and phosphonates.
- Aldea, Raluca,Alper, Howard
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p. 349 - 354
(2007/10/03)
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- Palladium Catalyzed Hydrogenation of α,β-Unsaturated Sulfones and Phosphonates
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The binuclear palladium complex, 2, when treated with oxygen, catalyzes the hydrogenation of the double bond of α,β-unsaturated sulfones and phosphonates in THF at room temperature and 1 atm of hydrogen pressure.Saturated sulfones and phosphonates were isolated in 49-93percent yields.
- Cho, In Sik,Alper, Howard
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p. 4027 - 4028
(2007/10/02)
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- Activation of Superoxide. Facile Oxidation of Sulfoxides into Sulfones with a Peroxysulfur Intermediate Generated in situ from 2-Nitrobenzenesulfonyl Chloride and Superoxide
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Various sulfoxides, such as dialkyl, alkyl-aryl, and diaryl sulfoxides, were readily oxidized into the corresponding sulfones, in excellent yields under mild conditions, by 2-nitrobenzene peroxysulfur intermediate generated in situ from 2-nitrobenzene-sulfonyl chloride and potassium superoxide at -30 deg C, in dry acetonitrile.Chemoselective oxidation of sulfoxides which contain both double bond and sulfinyl moiety to the sulfones, was observed under the same conditions.
- KIM, Yong Hae,LEE, Hyeon Kyu
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p. 1499 - 1502
(2007/10/02)
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- "SODIUM PERCARBONATE" (SPC) AS A HYDROGEN PEROXIDE SOURCE FOR ORGANIC SYNTHESIS
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"Sodium percarbonate" (SPC) is an inexpensive, stable, safe and commercially available material which may be used as a hydrogen peroxide source for organic synthesis.Epoxidation, amine and sulfide oxidation reactions were simply performed with the solid reagent in moderate to excellent yield.
- Ando, Takashi,Cork, David G.,Kimura, Takahide
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p. 665 - 666
(2007/10/02)
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- PHOTOSENSITIZED OXYGENATION OF CYCLIC SULFIDES. SELECTIVE C-S BOND CLEAVAGE
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TPP-Senzitized photooxidation of five-membered ring sulfides in aprotic solvent afforded C-S bond cleavage products, unlike six- and seven-membered ring sulfides which gave only S-oxidation products.The products as well as substitution and concentration effects suggest that C-S bond cleavage depends upon acidity of α-proton of persulfoxide intermediate.
- Takata, Toshikazu,Ishibashi, Koichi,Ando, Wataru
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p. 4609 - 4612
(2007/10/02)
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- Kinetics of the Peroxydisulfate Oxidation of Sulfoxides in Buffered Solution. 2. The Effect of Initial Sulfoxide Concentration with Diethyl and Diphenyl Sulfoxides
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The kinetics of reduction of 0.02 M K2S2O8 by diethyl and diphenyl sulfoxides in buffered aqueous solution were studied, the concentration of R2SO being varied in each run.The stoichiometric equation is S2O82- + 3H2O + R2SO -> 2H3O+ + R2SO2 and the corresponding sulfones were isolated as the reaction products from the runs.The kinetics, measured by the rate of persulfate disappearance, followed iodometrically, were first order in any given run, but the first-order rate constants are a marked function of the initial concentration of sulfoxide.The plots of k vs. 0 are rectangular hyperbolas given by the equation k = kmax0/(b + 0), where kmax is a limiting rate approached at high sulfoxide concentrations, and b is a constant, equal to that concentration of R2SO for which k = kmax/2.For the oxidation of Et2SO, ΔH is 27 kcal/mol and ΔS = -0.4 eu; for Ph2SO, ΔH = 30 kcal/mol and ΔS = +6.6 eu.The high activation energy and lack of ESR signals provide evidence that these are not free-radical chain reactions.Five possible mechanisms are considered, one of which is preferred.
- Levitt, Leonard S.
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p. 1177 - 1181
(2007/10/02)
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