- Diruthenium(II,III) tetramidates as a new class of oxygenation catalysts
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Two new diruthenium(II,III) tetramidate compounds, Ru 2(NHOCC(CH3)2)4Cl (1) and Ru 2(NHOCCH2CH3)4Cl (2) have been prepared and structurally characterized by X-ray crys
- Villalobos, Leslie,Cao, Zhi,Fanwick, Phillip E.,Ren, Tong
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- Active site design in a core-shell nanostructured catalyst for a one-pot oxidation reaction
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Designing an active site: A new type of core-shell structured catalyst was prepared, with a uniform SiO2 core supporting Pd nanoparticles (NPs) covered with a Ti-containing mesoporous silica shell. Generated H 2O2 on the i
- Okada, Shusuke,Mori, Kohsuke,Kamegawa, Takashi,Che, Michel,Yamashita, Hiromi
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- A novel method for the synthesis of aryl sulfones
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New sulfones were produced from aryl trifluoromethyl sulfones and Grignard reagents in good to high yields. The advantage of this transformation over a previous method by which sulfones were prepared from sulfonyl fluorides and organometallic reagents is discussed.
- Steensma, Ruo W.,Galabi, Sharen,Tagat, Jayaram R.,McCombie, Stuart W.
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- Factors influencing the catalytic activity of β-tetrabrominated meso-tetra(para-tolyl)porphyrinatomanganese(III) for oxidation of sulfides and olefins with Oxone
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Effect of different reaction parameters on the catalytic activity of β-tetrabrominated meso-tetra(para-tolyl)porphyrinatomanganese(III), MnT(4-CH3P)PBr4(OAc), for oxidation of different sulfides and hydrocarbons with tetra-n-butylammonium hydrogen monopersulfate (TBAHS) has been studied. In oxidation of sulfides, the chemoselectivity of reaction has been significantly changed in THF as the solvent compared with the common organic solvents. Also, using nitrogenous bases bearing electron-withdrawing groups (-Cl or -CN) clearly increased the ratio of sulfoxide to sulfone relative to the electron-donating ones. Catalytic oxidation of olefins with TBAHS was conducted in protic and aprotic solvents and acetonitrile has been found as the best solvent. A significantly large difference was found between the co-catalytic activity of imidazole (ImH) and pyridine in comparison with that observed in dichloromethane. The competitive oxidation of cis- and trans-stilbene suggests the presence of a high valent manganese oxo as well as a six coordinate (ImH)MnT(4-CH3P)PBr4(HSO5) species as the active oxidants in acetonitrile.
- Rayati, Saeed,Zakavi, Saeed,Kalantari, Hossein
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- Metal Catalysis in Oxidation by Peroxides. 30. Electrophilic Oxygen Transfer from Anionic, Coordinatively Saturated Molybdenum Peroxo Complexes
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Two anionic and coordinatively saturated oxodiperoxomolybdenum complexes, -Bu4N+ (L=C5H4NCO2- or C5H4N(O)CO2-), have been used as oxidants for a series of organic sulfides and sulfoxides in DCE.Quantitative yields of sulfoxides and sulfones, respectively, have been obtained.Spectroscopic (1H and 13C NMR) and kinetic evidence rule out any coordination process between the substrate and the oxidant requiring the formation of an unsaturated site on the metal.The data collected point to an oxidation mechanism involving a bimolecular reaction.This, at least for sulfide oxidation, appears to proceed through an electrophilic oxygen transfer from the peroxo complex to the substrate.
- Campestrini, S.,Conte, V.,Furia, F. Di,Modena, G.,Bortolini, O.
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- Mo-based Keggin heteropolyacids as catalysts in the green and selective oxidation of diphenyl sulfide
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Heteropolyacids are used as redox catalysts due to their bifunctional properties. Some advantages over conventional catalysts, such as selectivity, easy isolation and reuse, are worth noting. In homogeneous conditions their isolation and recycling can be
- Palermo, Valeria,Romanelli, Gustavo P.,Vázquez, Patricia G.
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- Oxidation of sulfides with a silica-supported peracid in supercritical carbon dioxide under flow conditions: Tuning chemoselectivity with pressure
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Supercritical carbon dioxide is a convenient medium for performing the selective oxidation of sulfides 1 to either sulfoxides 2 or sulfones 3 with [2-percarboxyethyl]-functionalized silica (4) under flow conditions. The chemoselectivity of the reaction, which results from the different diffusion rates of sulfide and sulfoxide over the reagent bed, can be controlled by adjusting the pressure and the hydration of the silica surface as both the solvating power of the mobile phase and the surface activity of the stationary phase determine the migration rates of sulfide 1 and sulfoxide 2 over the supported peroxide. The results elucidate the impact of surface phenomena on the course of chemical reactions carried out under flow conditions. The oxidation of sulfides 1 with hydrated [2-percarboxyethyl]-functionalized silica (4) in scCO2 under flow conditions can be tuned to give either sulfoxides 2 or sulfones 3 by adjusting the pressure.
- Mello, Rossella,Olmos, Andrea,Alcalde-Aragones, Ana,Diaz-Rodriguez, Alba,Gonzalez Nunez, Maria Elena,Asensio, Gregorio
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- A Metal-Free and Microwave-Assisted Efficient Synthesis of Diaryl Sulfones
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An efficient and general protocol for the synthesis of diaryl sulfones via the metal-free coupling of readily available diaryliodonium salts and arenesulfinates in PEG-400 under microwave irradiation has been developed. Utilizing this metal-free and eco-friendly protocol, we have prepared various diaryl sulfones in high yields and shorter reaction times under mild conditions. Furthermore, the coupling of diaryliodonium with arenesulfinate salts with and without copper iodide provides a convenient access to various diaryl sulfones with high selectivity. Georg Thieme Verlag Stuttgart · New York.
- Kumar, Dalip,Arun,Pilania, Meenakshi,Shekar, K.P. Chandra
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- Selectivity in Oxidation of Sulfides with Hydrogen Peroxide by +(CH2)15CH3>PM12O403- and +(CH2)15CH3>34>3- (M=Mo or W)
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Dramatical difference in selectivity was observed in the hydrogen peroxide oxidation of sulfides by +(CH2)15CH3>3PW12O403- (CWP) and +(CH2)15CH3>34>3- (PCWP) under the two-phase sy
- Ishii, Yasutaka,Tanaka, Hiroyuki,Nishiyama, Yutaka
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- TURNING THE REACTIVITY OF CARBONYL OXIDES FROM NUCLEOPHILIC TO ELECTROPHILIC. A NOVEL DEOXYGENATION OF SULFOXIDES BY ELECTROPHILIC α,α,α-TRIFLUOROACETOPHENONE O-OXIDE
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The well-known nucleophilic reactivity of carbonyl oxides could be turned into electrophilic by a potent electron-attracting group.Thus α,α,α-trifluoroacetophenone O-oxide oxidizes both sulfides and sulfoxides electrophilically, and the most characteristic reaction is the deoxyganation of sulfoxides.
- Ishiguro, Katsuya,Hirano, Yukimichi,Sawaki, Yasuhiko
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- Synthesis, crystal structure and catalytic activity of a new Mo Schiff base complex with Mo histidine immobilized on Al-MCM-41 for oxidation of sulfides
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A cis-dioxomolybdenum(VI) complex with Schiff base ligand derived from salicylaldehyde and l-histidine was prepared and designated as MoO 2(Sal-His). Characterization of MoO2(Sal-His) was accomplished with elemental analysis, FT-IR, UV-Vis and TGA. X-ray crystallography studies revealed that the coordination of Mo in MoO 2(Sal-His) is a distorted octahedron formed by tetradentate histidine Schiff base ligand and two binding oxygen atoms. MoO2(Sal-His) was used either alone or immobilized within Al-MCM-41 as sulfoxidation catalyst for a variety of sulfides with H2O2 as oxidant. The latter proved to be a very active and reusable heterogeneous sulfoxidation catalyst, providing 70-99% conversion and 80-95% selectivity.
- Zamanifar, Elham,Farzaneh, Faezeh,Simpson, Jim,Maghami, Mahboobeh
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- New niobium heteropolyacid included in a silica/alumina matrix: Application in selective sulfoxidation
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A new heteropolyacid, derived from phosphomolybdic acid containing niobium (PNbMo), was synthesized and included in silica, alumina, and silica/alumina matrixes by sol-gel technique, in order to use it as heterogeneous catalyst. The matrixes confer stability to the active phase, good textural and morphological properties. PNbMo and included materials were characterized by 31P-NMR, FT-IR, UV–vis, TGA, SEM, TEM, XRD, N2 physisorption, and potentiometric titration, and tested as catalyst in the sulfoxidation of diphenyl sulfide under suitable conditions. The redox activity was compared with phospomolybdic acid and correlated with the edge energy obtained from UV–vis absorption spectra. The best results in diphenyl sulfide sulfoxidation were obtained with PNbMo-SiAl-4:1 (92% conversion and 95% selectivity at 3 h) and with PNbMo-Si (92% conversion and 94% selectivity at 4 h). The reuse of these catalysts was evaluated.
- Colombo Migliorero, María B.,Palermo, Valeria,Romanelli, Gustavo P.,Vázquez, Patricia G.
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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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- Metal-Free Synthesis of Sulfones and Sulfoxides through Aldehyde-Promoted Aerobic Oxidation of Sulfides
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Metal-free aerobic oxidation of aryl sulfides to sulfoxides and sulfones has been developed in the presence of aliphatic aldehydes with excellent selectivity and yields. The reaction proceeded under mild conditions with the catalysis of N-hydroxyphthalimide (NHPI). Control experiments indicated that the reaction underwent a free radical pathway with the acylperoxyl radicals generated from aldehydes in situ as the key intermediates. The aromatic aldehydes were less efficient in the sulfide oxidation, which might be explained by the fact that the aromatic ring dispersed the electrons of free radicals and thus weakened the attacking ability of peroxy free radicals. Graphic Abstract: [Figure not available: see fulltext.]
- Li, Haoran,Wang, Lingyao,Yao, Jia,Zhang, Yuanbin
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- Biomimetic oxidation of diphenyl sulfide with metalloporphyrin-O2-NaBH4 system
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A P-450 model system consisting of metallo-meso-tetraphenylporphyrins, O2 and NaBH4 in basic solution is described. It has three remarkable features; 1) dioxygen is activated on a metalloporphyrin; 2) the reductant is used effectivel
- Michida,Kasuya,Sayo
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- Reactions on solid supports: Oxidation of sulfides to sulfoxides catalyzed by metalloporphyrins supported on silicagel
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The use of metalloporphyrins immobilized on silica, with iodosylbenzene as oxidant, leads to a selective oxidation of sulfides to sulfoxides.
- Pautet,Daudon
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- Nafion-H catalysed sulfonylation of aromatics with arene/alkenesulfonic acids for the preparation of sulfones
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Synthesis of both symmetric and unsymmetric diaryl/aryl alkyl sulfones is easily achieved by Friedel-Crafts type sulfonylation of aromatics with suitable arene- or alkanesulfonic acids in the presence of Nafion-H, a perfluorinated resinsulfonic acid catalyst.
- Olah,Mathew,Prakash
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- Heteropolymetallic complexes containing ReO4-: Catalytic oxidation of sulfide
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Heteropolymetallic complexes [(salen)Ti(ReO4)2] (1) and [{(salen)Ti(ReO4)}2(μ-O)] (2) are easily obtained in high yields via reaction of [(salen)TiCl2] and [{(salen)TiCl 2}2(μ-O)] with (Me3SiO)ReO3, respectively (where, salen = (S,S)-N,N′-bis(3,5-di-tert-butylsalicylidene) cyclohexane-1,2-diamine dianion). The structure of complex 2 was established by single-crystal X-ray diffraction. The tetrahedral geometry of the ReO 4- anion links the dititanium unit of {(salen)Ti} 2(μ-O) in the axial positions. The Re-O-Ti bridge angles range from 146.1(2) to 162.6(2) with a Re?Ti separation of 3.780 A?. Complexes 1 and 2 are capable of catalytic oxidation of sulfides with tBuOOH.
- Li, Chen,Peng, Xiao,Zhang, Shou-Chun,Chai, Li-Yuan,Yi, Xiao-Yi
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- Metal Catalysis in Oxidation by Peroxides. Kinetics and Mechanism of the Molybdenum-Catalyzed Oxidation of Sulfoxides to Sulfones with Hydrogen Peroxide
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The rates of oxidation to sulfones of three model sulfoxides, di-n-butyl, phenyl methyl, and diphenyl, with hydrogen peroxide, in the presence of catalytic amounts of MoO2(acac)2, have been measured in ethanol solvent, at 40 deg C, both in acid and basic solutions.The comparison of the behavior observed with those of the m-chloroperbenzoic oxidation of the same substrates, either in acid or basic solutions, and of the oxidation of the parent sulfoxides provides an useful mechanistic tool for differentiating electrophilic oxygen transfers from the nucleophilic ones.
- Bortolini, O.,Campestrini, S.,Furia, F. Di,Modena, G.
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- An improved high yielding immobilization of vanadium Schiff base complexes on mesoporous silica via azide-alkyne cycloaddition for the oxidation of sulfides
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Azide-alkyne [3+2] cycloaddition "click reaction" was found to be a simple yet improved approach for the efficient immobilization of oxo-vanadium(iv) tridentate Schiff base complexes to mesoporous silica via covalent attachment as it occurred under mild reaction conditions and provided high catalyst loading compared to the direct immobilization of oxo-vanadium(iv) tridentate Schiff base complex to 3-chloropropylsilyl functionalized silica support.
- Jain, Suman L.,Rana, Bharat S.,Singh, Bhawan,Sinha, Anil K.,Bhaumik, Asim,Nandi, Mahasweta,Sain, Bir
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- Controllable oxidation of sulfides to sulfoxides and sulfones with aqueous hydrogen peroxide in the presence of β-cyclodextrin
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A facile procedure has been developed for the transition metal-free oxidation of sulfides to sulfoxides and sulfones and of sulfoxides to sulfones with hydrogen peroxide in aqueous medium in the presence of β-cyclodextrin as catalyst. The procedure allows formation of sulfoxide or sulfone to be controlled. Pleiades Publishing, Inc., 2006.
- Ji, Hong-Bing,Hu, Xiao-Fang,Shi, Dong-Po,Zhong, Li
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- Fe-pillared bentonite-an efficient catalyst for sulfonylation of arenes using aryl and alkyl sulfonyl chlorides
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Fe-pillared bentonite (Fe-PILC) was shown to be an extremely efficient catalyst for the sulfonylation of activated as well as unactivated carbocyclic aromatic compounds and heterocyclic aromatic compounds. The catalyst was also found to be recyclable.
- Singh, Devendrapratap U.,Singh, Pankajkumar R.,Samant, Shriniwas D.
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- Dimethyl carbonate: an environmentally friendly solvent for hydrogen peroxide (H2O2)/methyltrioxorhenium (CH3ReO3, MTO) catalytic oxidations
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Environmentally friendly oxidations of various organic compounds with the hydrogen peroxide (H2O2)/methyltrioxorhenium (CH3ReO3, MTO) catalytic system have been described in dimethyl carbonate (DMC), a cheap commercially available and benign chemical having interesting solvating properties, low toxicity and high biodegradability. Oxidations proceeded with good conversions and in good yields. Spectrophotometric analysis demonstrated that the [CH3ReO(O-O)2] complex was formed in DMC and that it was stable for several days at room temperature.
- Bernini, Roberta,Mincione, Enrico,Barontini, Maurizio,Crisante, Fernanda,Fabrizi, Giancarlo,Gambacorta, Augusto
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- Evidence for a higher oxidation state of manganese in the reaction of dinuclear manganese complexes with oxidants. Comparison with iron based gif chemistry
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Binuclear manganese complexes mimic the catalase enzyme by converting hydrogen peroxide rapidly and efficiently to oxygen and water. The complex (1) may he activated by either periodic acid or Oxone and can oxidize selected organic substrates. Potassium manganate gave similar oxidation products suggesting that the manganese is transformed to a higher oxidation state. Kinetic studies with the Mn(IV)-Mn(IV) complex show an induction period indicating that it is not the active catalyst. Further studies suggested that the actual catalytic species is a Mn(III)-Mn(IV) complex. These complexes show similar properties to the activation of FeCl3 with hydrogen peroxide. This is particularly evident by the formation of a new and unusual peroxide from argosterol acetate.
- Barton, Derek H.R.,Choi, Seung-Yong,Hu, Bin,Smith, Jason A.
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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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- 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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- 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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- 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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- 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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- Fe(III) exchanged montmorillonite: A mild and ecofriendly catalyst for sulfonylation of aromatics
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Fe(III) exchanged montmorillonite clay catalyses Friedel-Crafts sulfonylation of arenes with arylsulfonyl chlorides to obtain the corresponding sulfones in excellent yields.
- Choudary,Chowdari, N. Sreenivasa,Kantam, M. Lakshmi,Kannan
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- Selective oxidation of sulfides to sulfoxides with molecular oxygen catalyzed by N-hydroxyphthalimide (NHPI) in the presence of alcohols
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Aerobic oxidation of various sulfides using N-hydroxyphthalimide (NHPI) in the presence of alcohols was examined. For instance, the oxidation of diphenyl sulfide in the presence of cyclohexanol and a catalytic amount of NHPI in benzonitrile gave diphenyl
- Iwahama, Takahiro,Sakaguchi, Satoshi,Ishii, Yasutaka
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- New recoverable organoselenium catalyst for hydroperoxide oxidation of organic substrates
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New benzisoselenazol-3(2H)-one covalently bounded to a silica support was synthesized and characterized. It was used as an effective, selective, and easy-to-regenerate catalyst for t-BuOOH and H2O2 oxidation of alkyl arenes to alkyl aryl ketones, aromatic aldehydes to arene carboxylic acids, and sulfoxides and/or sulfones. Copyright Taylor & Francis Group, LLC.
- Wojtowicz, Halina,Soroko, Grazyna,Mlochowski, Jacek
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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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- Catalytic oxidation of aryl alkyl sulfides using immobilized vanadyl ions within nanoreactors of Al-MCM-41
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VOSO4 immobilized within nanoreactors of Al-MCM-41 (VO 2+/Al-MCM-41) was synthesized and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, nitrogen adsorption-desorption, and chemical analysis techniques. The prepared VO2+/Al-MCM-41 successfully catalyzes the oxidation of aryl alkyl sulfides and up to 99 conversion and 90 selectivity for the corresponding sulfoxides were obtained with H2O2 as oxidant in acetonitrile at room temperature in 30 min.
- Elham, Zamanifar,Faezeh, Farzaneh
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- Factors affecting the reactivity and selectivity in the oxidation of sulfides with tetra-n-butylammonium peroxomonosulfate catalyzed by Mn(III) porphyrins: Significant nitrogen donor effects
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The oxidation of aryl sulfides by tetra-n-butylammonium peroxomonosulfate (n-Bu4NHSO5) was carried out in the presence of six different manganese (III) tetraarylporphyrins [Mn(Por)s] as biomimetic catalysts and a number of nitrogen donors as co-catalysts. There is no noticeable difference between the reactivity of sulfides, in the presence of electron-rich Mn(por)s, whereas, for electron-deficient catalysts, conversion rates are different. Nevertheless, the over-oxidation of sulfoxide is more sensitive to both the nature of substituents attached to the sulfur atom in substrates as well as porphyrin complex structure. The degree of catalytic activity of Mn(Por)s for the formation of sulfone product increases as the following order: Mn(TPFPP)OAc 2P)P]OAc 4] complex.
- Rezaeifard, Abdolreza,Jafarpour, Maasoumeh,Raissi, Heidar,Ghiamati, Ebrahim,Tootoonchi, Aida
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- New oxovanadium and dioxomolybdenum complexes as catalysts for sulfoxidation: experimental and theoretical investigations of E and Z isomers of ONO tridentate Schiff base ligand
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A new ONO-tridentate Schiff base ligand (H2L) derived by the condensation of nicotinic hydrazide with 5-chlorosalicylaldehyde has been prepared and characterized by combustion analysis (CHN), FT-IR and multinuclear (1H and 13C) NMR spectroscopy. The crystalline nature and molecular structure of the ligand were confirmed by single-crystal X-ray diffraction analysis. Furthermore, the optimized structural parameters of the four possible configurations of the ligand including Z and E stereoisomers each containing two tautomeric forms (enol and keto) have also been investigated. The theoretical parameters were calculated by performing the DFT method using the B3LYP/Def2-TZVP level of theory. In addition to this, dioxomolybdenum(VI) (MoO2L) and oxovanadium(V) (VOL) complexes with the entitled Schiff base ligand have also been prepared and characterized by different techniques. Then, the catalytic efficiencies of synthesized VOL and MoO2L complexes were also explored for the oxidation of sulfides using 30% aqueous H2O2 as a source of oxygen. These homogeneous catalysts showed excellent catalytic activities in the oxidation of both aromatic and aliphatic sulfides.
- Kargar, Hadi,Moghimi, Atefeh,Fallah-Mehrjardi, Mehdi,Behjatmanesh-Ardakani, Reza,Rudbari, Hadi Amiri,Munawar, Khurram Shahzad
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- Visible-Light-Mediated Late-Stage Sulfonylation of Boronic Acids via N-S Bond Activation of Sulfonamides
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A visible-light-mediated late-stage arylation of N-S bonds in sulfonamides has been developed with using readily available imines as sulfonyl radical source. Diverse complex sulfones could be synthesized by prefunctionalizaiton and subsequent N-S bond ary
- Zhen, Jingsong,Du, Xian,Xu, Xiaohong,Li, Yihui,Yuan, Han,Xu, Dejing,Xue, Can,Luo, Yong
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p. 1986 - 1991
(2022/02/07)
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- Metal-free sulfonylation of arenes with: N -fluorobenzenesulfonimide via cleavage of S-N bonds: expeditious synthesis of diarylsulfones
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A novel metal-free sulfonylation of arenes with N-fluorobenzenesulfonimide (NFSI) toward the synthesis of diarylsulfones has been developed. The reaction represents a rare example of sulfonylation reaction using NFSI as an efficient sulfonyl donor and the first example of acid-mediated sulfonylation of unactivated arenes with NFSI via selective cleavage of S-N bonds. This protocol provides a concise approach for the construction of pharmaceutically and biologically important diarylsulfones. Applications in the functionalization of natural products (e.g., β-estradiol) and in the synthesis of a key intermediate to an inhibitor of farnesyl-protein transferase, as well as in the gram-scale synthesis of the EPAC2 antagonist, are demonstrated. This journal is
- Feng, Yueji,Tuo, Yanyan,Zhang, Xiaohui,Zheng, Qing-Zhong
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supporting information
p. 768 - 772
(2022/02/03)
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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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- Redox-Neutral Organometallic Elementary Steps at Bismuth: Catalytic Synthesis of Aryl Sulfonyl Fluorides
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A Bi-catalyzed synthesis of sulfonyl fluorides from the corresponding (hetero)aryl boronic acids is presented. We demonstrate that the organobismuth(III) catalysts bearing a bis-aryl sulfone ligand backbone revolve through different canonical organometallic steps within the catalytic cycle without modifying the oxidation state. All steps have been validated, including the catalytic insertion of SO2 into Bi-C bonds, leading to a structurally unique O-bound bismuth sulfinate complex. The catalytic protocol affords excellent yields for a wide range of aryl and heteroaryl boronic acids, displaying a wide functional group tolerance.
- Cornella, Josep,Magre, Marc
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p. 21497 - 21502
(2022/01/03)
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- COMPOSITES, METHODS AND USES THEREOF
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The present invention relates, in general terms, to methods of catalysing a reaction, including the steps of contacting a chemical entity comprising a sulphide moiety with a composite and an oxidant. The composite acts as a heterogeneous catalyst to oxidise the sulphide moiety. The present invention also relates to composites, methods of synthesising the composites and its use as a catalyst thereof.
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Page/Page column 26
(2021/06/04)
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- On the important transition of sugar-based surfactant as a microreactor for C-S coupling in water: From micelle to vesicle
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A reversible, temperature-induced micelle-to-vesicle transition of a sugar-based pseudogemini surfactant (C11D12) was employed for copper-catalyzed C-S coupling in water. The phase behavior and morphology of the C11D12 aqueous solution were investigated by DLS and cryo-TEM. The aggregates undergo a series of transitions upon increasing the temperature: spherical micelles were initially transformed into large vesicles, but they eventually transformed into smaller vesicles. The vesicular catalytic protocol accommodates an excellent substrate scope with moderate to high yields. The mechanisms of temperature-induced aggregate transition and vesicular catalysis were elucidated by experimental results and DFT calculations. It was revealed that the charge layer of the vesicle grants stronger nucleophilicity to the PhSO2-Cu-D12Ga intermediate. Furthermore, the aqueous reaction medium can be recycled and reused several times after easily separating the precipitated product.
- Ge, Xin,Lei, Qiuyun,Liao, Xiong,Liu, Xuemin,Song, Weili,Wu, Lei,Wu, Siyuan,Zhou, Shaodong
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- Interfacing sugar-based surfactant micelles and Cu nanoparticles: A nanoreactor for C-S coupling reactions in water
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A simple and sustainable synergistic catalytic protocol by interfacing nanomicelles and metal nanoparticles (MNPs) is reported for C-S coupling reactions in water. The sugar-based surfactant GluM was synthesized by introducing a PEG chain to stabilize MNPs and self-assembled to form nanomicelles. Cu2O nanoparticles were generated via in situ reduction of copper salt in an aqueous solution of the sugar-based surfactant. The nature of the interaction between nanomicelles and Cu2O nanoparticles was revealed by XPS, XRD, in situ IR, TEM, and 1H NMR. A broad substrate scope with moderate to excellent yields was documented and the recycling of the GluM/Cu aqueous mixture was surprising.
- Ge, Xin,He, Xi,Liu, Xuemin,Qian, Chao,Song, Weili,Yang, Jinguo,Zhou, Shaodong
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supporting information
p. 6322 - 6329
(2021/09/10)
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- Ceramic boron carbonitrides for unlocking organic halides with visible light
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Photochemistry provides a sustainable pathway for organic transformations by inducing radical intermediates from substrates through electron transfer process. However, progress is limited by heterogeneous photocatalysts that are required to be efficient, stable, and inexpensive for long-term operation with easy recyclability and product separation. Here, we report that boron carbonitride (BCN) ceramics are such a system and can reduce organic halides, including (het)aryl and alkyl halides, with visible light irradiation. Cross-coupling of halides to afford new C-H, C-C, and C-S bonds can proceed at ambient reaction conditions. Hydrogen, (het)aryl, and sulfonyl groups were introduced into the arenes and heteroarenes at the designed positions by means of mesolytic C-X (carbon-halogen) bond cleavage in the absence of any metal-based catalysts or ligands. BCN can be used not only for half reactions, like reduction reactions with a sacrificial agent, but also redox reactions through oxidative and reductive interfacial electron transfer. The BCN photocatalyst shows tolerance to different substituents and conserved activity after five recycles. The apparent metal-free system opens new opportunities for a wide range of organic catalysts using light energy and sustainable materials, which are metal-free, inexpensive and stable. This journal is
- Yuan, Tao,Zheng, Meifang,Antonietti, Markus,Wang, Xinchen
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p. 6323 - 6332
(2021/05/19)
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- Oxovanadium and dioxomolybdenum complexes: synthesis, crystal structure, spectroscopic characterization and applications as homogeneous catalysts in sulfoxidation
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New oxovanadium and dioxomolybdenum Schiff base complexes, [VO(L)(OCH3)] n and [MoO2(L)(CH3OH)], were synthesized by treating an ONO donor Schiff base (H2L) derived by condensation of 3-ethoxysalicylaldehyde and nicotinic hydrazide with oxo and dioxo acetylacetonate salts of vanadium and molybdenum (VO(acac)2 and MoO2(acac)2), respectively. The synthesized ligand and complexes were characterized by FTIR, multinuclear (1H, 13C) NMR, elemental and single crystal X-ray diffraction analysis. In both complexes, the geometry around the central metal ions was distorted octahedral as revealed by diffraction studies. Theoretical calculations of the synthesized compounds were carried out by DFT at B3LYP/Def2-TZVP level of theory, which showed good correlation with the experimental results. Moreover, the catalytic efficiency of both complexes was investigated by oxidizing aryl and alkyl sulfides in the presence of 30% H2O2 in ethanol.
- Kargar, Hadi,Kaka-Naeini, Azar,Fallah-Mehrjardi, Mehdi,Behjatmanesh-Ardakani, Reza,Amiri Rudbari, Hadi,Munawar, Khurram Shahzad
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p. 1563 - 1583
(2021/05/11)
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- Sulfoxide and Sulfone Synthesis via Electrochemical Oxidation of Sulfides
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The oxidation of diaryl sulfides and aryl alkyl sulfides to the corresponding sulfoxides and sulfones under electrochemical conditions is reported. Sulfoxides are selectively obtained in good yield under a constant current of 5 mA for 10 h in DMF, while sulfones are formed as the major product under a constant current of 10 or 20 mA for 10 h in MeOH. The oxygen of both the sulfoxide and sulfone function is derived from water.
- Lee, Sunwoo,Park, Jin Kyu
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p. 13790 - 13799
(2021/10/12)
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- Selective synthesis of sulfoxides and sulfonesviacontrollable oxidation of sulfides withN-fluorobenzenesulfonimide
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A practical and mild method for the switchable synthesis of sulfoxides or sulfonesviaselective oxidation of sulfides using cheapN-fluorobenzenesulfonimide (NFSI) as the oxidant has been developed. These highly chemoselective transformations were simply achieved by varying the NFSI loading with H2O as the green solvent and oxygen source without any additives. The good functional group tolerance makes the strategy valuable.
- Cao, Zhong-Yan,Li, Xiaolong,Lu, Hao,Wang, Panpan,Wang, Shengqiang,Xu, Xiaobo,Yan, Leyu,Yang, A-Xiu
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supporting information
p. 8691 - 8695
(2021/10/22)
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- Electrochemical Scalable Sulfoxidation of Sulfides with Molecular Oxygen and Water
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An efficient and chemoselective synthesis of sulfoxides through the electrooxidation of sulfides has been well developed. This protocol takes advantage of electricity as the terminal oxidant and of molecular oxygen and water as the oxygen atom sources. A variety of structurally diverse sulfoxide compounds are assembled in moderate to excellent yields. The scaled-up reactions at 6–20 mmol show the good practicability and application potential of this methodology. A possible free radical mechanism has been proposed to rationalize the reaction procedure.
- Cheng, Zhen,Gao, Xinglian,Yao, Lingling,Wei, Zhaoxin,Qin, Guohui,Zhang, Yonghong,Wang, Bin,Xia, Yu,Abdukader, Ablimit,Xue, Fei,Jin, Weiwei,Liu, Chenjiang
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p. 3743 - 3747
(2021/07/26)
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- Method for synthesizing diaryl sulfone compound by photocatalytic oxidation of diaryl sulfide
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The invention discloses a method for synthesizing a diaryl sulfone compound by photocatalytic oxidation of diaryl sulfide, which comprises the following steps: in an oxygen-containing atmosphere and under the condition of 370-375nm ultraviolet irradiation, carrying out one-pot reaction on the diaryl sulfide compound and sodium difluoromethanesulfinate in a dioxane solution system to generate the diaryl sulfone compound. The method has the advantages of mild conditions, simple operation, environmental protection, easily available raw materials, excellent compatibility of substrate functional groups, high reaction yield and the like.
- -
-
Paragraph 0037-0057
(2021/02/20)
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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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- 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.
- -
-
Paragraph 0057-0059
(2021/01/29)
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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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-
- Electrochemical oxygenation of sulfides with molecular oxygen or water: Switchable preparation of sulfoxides and sulfones
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A practical and eco-friendly method for the controllable aerobic oxygenation of sulfides by electrochemical catalysis was developed. The switchable preparation of sulfoxides and sulfones was effectively controlled by reaction time, in which both molecular oxygen and water can be used as the oxygen source under catalyst and external oxidant-free conditions. The electrochemical protocol features a broad substrate scope and excellent site selectivity and is successfully applied to the modification of some sulfide-containing pharmaceuticals and their derivatives. This journal is
- Li, Jin-Heng,Li, Yang,Sun, Qing,Xue, Qi,Zhang, Ting-Ting
-
supporting information
p. 10314 - 10318
(2021/12/17)
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- A Copper(I)-Catalyzed Sulfonylative Hiyama Cross-Coupling
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An air-tolerant Cu-catalyzed sulfonylative Hiyama cross-coupling reaction enabling the formation of diaryl sulfones is described. Starting from aryl silanes, DABSO and aryliodides, the reaction tolerates a large variety of polar functional groups (amines, ketones, esters, aldehydes). Control experiments coupled with DFT calculations shed light on the mechanism, characterized by the formation of a Cu(I)-sulfinate intermediate via fast insertion of a SO2 molecule.
- Adenot, Aurélien,Anthore-Dalion, Lucile,Nicolas, Emmanuel,Berthet, Jean-Claude,Thuéry, Pierre,Cantat, Thibault
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supporting information
p. 18047 - 18053
(2021/11/16)
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- Mechanochemical synthesis of aromatic sulfonamides
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A three-component Pd-catalysed aminosulfonylation reaction of K2S2O5 and amine with aryl bromides or aromatic carboxylic acids was developed. This strategy was developed to utilise mechanical energy and accommodate primary as well as secondary aliphatic and aromatic amines to provide a new shortcut to a wide range of sulfonamides. Studies on the scope and limitations of the reaction indicated its tolerance of a vast range of functional groups and many structural patterns. The reactions were scaled up to gram quantities.
- Mkrtchyan, Satenik,Iaroshenko, Viktor O.
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supporting information
p. 11029 - 11032
(2021/11/03)
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- Sulfonylation of Bismuth Reagents with Sulfinates or SO2through BiIII/BiV Intermediates
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Studies to explore the catalytic activities of main-group elements are attractive. We report here our study of sulfonylation of bismuth reagents with sulfinates or SO2 surrogates. Under oxidative conditions, triarylbismuthines and sulfinates were transformed into diaryl sulfones. A transition-metal-like two-electron redox process at the Bi center was achieved in this reaction. Sulfur dioxide generated in situ can also replace sulfinates to deliver the corresponding symmetric diaryl sulfones. A rational mechanism for this reaction was also proposed that involves a Bi(III)-Bi(V) manifold.
- Zhao, Fengqian,Wu, Xiao-Feng
-
supporting information
p. 2400 - 2404
(2021/07/28)
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- Method for synthesizing sulfone compounds under photocatalysis condition
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The invention belongs to the technical field of compound preparation, and particularly relates to a method for synthesizing sulfone compounds under a photocatalysis condition. Aromatic hydrazine and sulfinate are used as raw materials, and under the action of alkali and a solvent, a sulfone compound is generated through reaction under the condition of air or oxygen under the illumination of visible light. According to the method disclosed by the invention, aryl hydrazine is used as an arylation reagent, polyacid salt is used as a catalyst or an organic photosensitizer is used as a catalyst, and the sulfones compound can be efficiently synthesized by coupling with sulfinate under the condition of room temperature through visible light irradiation. The method has good substrate universalityand relatively mild reaction conditions, is not only a substitute for synthesizing sulfone compounds by coupling from simple substrates reported at present, but also broadens the new application of the polyacid salt in the field of photocatalysis.
- -
-
Paragraph 0039-0045
(2021/03/31)
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- Pd/NHC-catalyzed arylsulfonylation of boronic acids: A general and direct protocol to access diarylsulfones
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For the first time, robust NHC-Pd complexes have been demonstrated as highly efficient catalysts in the direct arylsulfonylation of boronic acids. Remarkably, a broad number of diaryliodonium salts as powerful electrophilic arylation reagents are well compatible to form functional ortho-substituted diarylsulfones in satisfactory yields. Owing to the stronger σ-donor and weaker π-acceptor properties, the acenaphthoimidazolylidene ligands exhibit higher catalytic activities towards this challenging one-step arylsulfonylation reaction.
- Zhu, Haibo,Yang, Liu,Meng, Jia,Xie, Zongbo,Le, Zhang-Gao,Tu, Tao
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supporting information
(2020/12/29)
-
- A Unified Strategy for Arylsulfur(VI) Fluorides from Aryl Halides: Access to Ar-SOF3 Compounds
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A convenient protocol to selectively access various arylsulfur(VI) fluorides from commercially available aryl halides in a divergent fashion is presented. Firstly, a novel sulfenylation reaction with the electrophilic N-(chlorothio)phthalimide (Cl-S-Phth) and arylzinc reagents afforded the corresponding Ar-S-Phth compounds. Subsequently, the S(II) atom was selectively oxidized to distinct fluorinated sulfur(VI) compounds under mild conditions. Slight modifications on the oxidation protocol permit the chemoselective installation of 1, 3, or 4 fluorine atoms at the S(VI) center, affording the corresponding Ar-SO2F, Ar-SOF3, and Ar-SF4Cl. Of notice, this strategy enables the effective introduction of the rare and underexplored -SOF3 moiety into various (hetero)aryl groups. Reactivity studies demonstrate that such elusive Ar-SOF3 can be utilized as a linchpin for the synthesis of highly coveted aryl sulfonimidoyl fluorides (Ar-SO(NR)F).
- Cornella, Josep,Wang, Lin
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supporting information
p. 23510 - 23515
(2020/10/29)
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- Micelle catalysis and extraction separation coupling method based on nonionic surfactant (by machine translation)
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The invention discloses a micelle catalysis and extraction separation coupling method based on a nonionic surfactant, and belongs to the technical field of chemical synthesis. M 202070 is used as a reaction medium, the Ullmann C-S coupling reaction is catalyzed, and the product is separated by directly heating to a cloud point after the reaction is completed. The method provided by the invention is mild in condition, convenient to operate, less in organic matter content in the reaction waste liquid, small in environmental pollution, green and environment-friendly; meanwhile, the yield of the aromatic sulfone can reach 75% or above, the extraction yield reaches 100%, and the method is suitable for industrial mass production. (by machine translation)
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Paragraph 0047-0051
(2020/08/18)
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- Production method of high-purity diphenyl sulfone
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The invention discloses a production method of high-purity diphenyl sulfone. The method comprises the following steps: taking a certain amount of benzene, adding an ionic liquid, adding chlorosulfonicacid at a certain temperature, and reacting benzene with chlorosulfonic acid while stirring; with hydrogen chloride enriched by ionic liquid as a catalyst, carrying out a one-pot reaction on benzeneand chlorosulfonic acid to obtain a crude product diphenyl sulfone; after the reaction is completed, quenching the reaction with cold water or crushed ice, and carrying out suction filtration or centrifugation to obtain a crude product diphenyl sulfone; dissolving the crude product diphenyl sulfone by using an organic solvent, and then washing by using alkali liquor and an aqueous ethylenediaminetetraacetic acid tetrasodium salt solution respectively to obtain an organic diphenyl sulfone solution; and decolorizing the organic diphenyl sulfone solution by using activated carbon, filtering to remove the activated carbon, and carrying out cooling crystallization, suction filtration or centrifugation and drying on the obtained filtrate to obtain the diphenyl sulfone product. The method has the advantages of mild reaction conditions, excellent yield, simple and convenient production process, safety, reliability, environmental protection and high impurity removal efficiency, and the purityof the obtained product can reach 99.9%.
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Paragraph 0030-0041
(2020/12/14)
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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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- Synthetic method of diarylsulfone compound
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The invention relates to a synthetic method of a diarylsulfone compound. The method is characterized in that a copper complex and aryl sulfonyl hydrazide are dissolved in an organic solvent, air serves as an oxidizing agent, a reaction is conducted at the room temperature, separation and purification are conducted to obtain the corresponding diarylsulfone compound, the molar ratio of the copper complex to the aryl sulfonyl hydrazide is (0.01-0.03):1.0, and the reaction time is 2-5 h. Compared with the prior art, the synthesis process provided by the invention has excellent selectivity and highyield, the catalyst copper complex in the reaction can catalyze the self-coupling of aryl sulfonyl hydrazide to synthesize the diarylsulfone compound at room temperature, and the reaction has the characteristics of mild and simple conditions, wide substrate range, convenient product separation, high reaction efficiency and the like.
- -
-
Paragraph 0029; 0033-0036; 0050-0055
(2020/10/04)
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- Multicomponent Synthesis of Sulfones and Sulfides from Triarylbismuthines and Sodium Metabisulfite in Deep Eutectic Solvents
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This study describes a novel and catalyst-free methodology for the multicomponent synthesis of a broad range of sulfones, disulfides, and sulfides from non-toxic triarylbismuthines (Ar3Bi) and sodium metabisulfite (Na2S2O5) in deep eutectic solvents (DESs). The fine tuning of the DESs properties allowed the solubility of all reagents, enhancing their reactivity, as well as, the recyclability of the reaction medium for at least 5 consecutive cycles. Thus, this versatile strategy uses non-toxic reagents without the need of metal catalysts in a sustainable solvent, being an interesting alternative to traditional hazardous protocols.
- Saavedra, Beatriz,Marset, Xavier,Guillena, Gabriela,Ramón, Diego J.
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supporting information
p. 3462 - 3467
(2020/06/04)
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- Palladium-catalyzed one-step synthesis of symmetrical diaryl sulfones from aryl halides and a sulfur dioxide surrogate
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A convenient method for the one-step synthesis of symmetrical diaryl sulfones from aryl halides has been developed. A keystone of the method is the use of K2S2O5, which can be easily and safely handled, as a sulfur dioxide surrogate. The palladium catalyst bearing P(t-Bu)3 as a ligand enables formation of the desired sulfones without significant formation of byproducts.
- Tanaka, Hiromichi,Konishi, Hideyuki,Manabe, Kei
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supporting information
p. 760 - 763
(2019/08/02)
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- Organic photoredox catalysis enabled cross-coupling of arenediazonium and sulfinate salts: Synthesis of (un)symmetrical diaryl/alkyl aryl sulfones
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We disclose herein the first transition-metal-and external oxidant/reductant-free visible-light-mediated synthesis of (un)symmetrical diaryl/alkyl aryl sulfones from arenediazonium tetrafluoroborates and sodium sulfinates using eosin Y as an organic photoredox catalyst. The utilization of visible light as an inexpensive and ecosustainable energy source, operational simplicity, ambient temperature and clean reaction in aqueous acetonitrile are the salient features of the developed protocol. The desired sulfones were also synthesized via a one-pot, two-step process directly from anilines and sulfinate salts in good to excellent yields.
- Chawla, Ruchi,Yadav, Lal Dhar S.
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supporting information
p. 4761 - 4766
(2019/05/24)
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- An efficient heterogeneous copper fluorapatite (CuFAP)-catalysed oxidative synthesis of diaryl sulfone under mild ligand- and base-free conditions
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A simple, eco-friendly and efficient method for the synthesis of unsymmetrical diaryl sulfones using heterogeneous copper fluorapatite (CuFAP)-catalysed coupling of aryl sulfonic acid and phenyl boronic acid has been developed with good to excellent yields without use of any ligand, base or co-catalyst. Broad substrate scope and gram scale operations are the important features of this method.
- Kamble, Rohit B.,Chavan, Santosh S.,Suryavanshi, Gurunath
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p. 1632 - 1636
(2019/01/21)
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- Synthesis method of diaryl sulfone compound (by machine translation)
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The invention discloses a synthesis method of a diaryl sulfone compound, wherein the, reaction equation of the series of N - diarylsulfone compounds is prepared by (NFSI) sulfonylating the aromatic hydrocarbon under the non-metal condition with the source of the, benzenesulfonyl group as the benzenesulfonyl group, and: the reaction equation is as follows. STR3, #, STR2, #, STR2, #, #, #, # STR2. # STR2# STR2# STR2, , STR2 STR2 STR2 N - # (NFSI) STR2# STR2 STR2 STR2, #, # STR1 STR8# STR2 STR1 STR8. AlCl R3 , FeCl3 The other precious, and metals of, other metals such as the precious metals of, the other noble metals not cause the environment, to pollute, the environment and are suitable for the concise and high-efficiency synthesis of. the diarylsulfone compounds, and have good application prospects in the fields of organic synthesis, drug research and development and the like. (by machine translation)
- -
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Paragraph 0007; 0017-0018; 0029-0031
(2019/12/31)
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- A designed bi-functional sugar-based surfactant: Micellar catalysis for C-X coupling reaction in water
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A bi-functional sugar-based surfactant ALA14 was designed as the ligand and micelle constructor and demonstrated to promote the copper-catalyzed C-X coupling reaction in water. The nature of this micelle, formed by sugar-based surfactants, was investigated with CMC, DLS, and TEM, by which encapsulation and aggregation of the substrates in micelles were verified. Additionally, it was addressed by 1H-NMR analysis that the enrichment position of the substrates is in the lipophilic alkyl chain. Finally, moderate to excellent yields of the aimed products were obtained in this work. This remarkably simple strategy expanded the scope of C-X coupling reaction in water; most notably, both water and ALA14 can be recycled and reused.
- Ge, Xin,Zhang, Shihui,Chen, Xinzhi,Liu, Xuemin,Qian, Chao
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supporting information
p. 2771 - 2776
(2019/06/13)
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- Generation of Aryl Radicals from Aryl Halides: Rongalite-Promoted Transition-Metal-Free Arylation
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A new and practical method for the generation of aryl radicals from aryl halides is reported. Rongalite as a novel precursor of super electron donors was used to initiate a series of electron-catalyzed reactions under mild conditions. These transition-metal-free radical chain reactions enable the efficient formation of C-C, C-S, and C-P bonds through homolytic aromatic substitution or SRN1 reactions. Moreover, the synthesis of antipsychotic drug Quetiapine was performed on gram scale through the described method. This protocol demonstrated its potential as a promising arylation method in organic synthesis.
- Yu, Fazhi,Mao, Runyu,Yu, Mingcheng,Gu, Xianfeng,Wang, Yonghui
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p. 9946 - 9956
(2019/09/04)
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- Switchable Synthesis of Aryl Sulfones and Sulfoxides through Solvent-Promoted Oxidation of Sulfides with O2/Air
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A practical and switchable method for the synthesis of aryl sulfones and sulfoxides via sulfide oxidation was developed. The chemoselectivities of products were simply controlled by reaction temperature using O2/air as the terminal oxidant and oxygen source. The broad substrate scope, easy realization of gram-scale production, and the simplification of a sulfide oxidation system render the strategy attractive and valuable.
- Cheng, Zhen,Sun, Pengchao,Tang, Ailing,Jin, Weiwei,Liu, Chenjiang
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supporting information
p. 8925 - 8929
(2019/11/14)
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- Reactions between 5-Nitroso-1,3-diphenyltetrazolium salts and electron-rich arenes, amines, thiophenol, sulfoxides, and thioanisole
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A series of reactions between 5-nitroso-1,3-diphenyltetrazo-lium tetrafluoroborate and methoxybenzenes, amines, thiols, sulfoxides, and sulfides, most of which are generally accepted as being inert to nitroso groups, is reported here. The tetrazolium-activated nitroso functionality is capable of oxidizing the aforementioned substrates to give the corresponding oxidized products, and the nitroso tetrazolium itself is transformed into the corresponding amide or hydroxyamide, depending on the nature of the reaction partners. In the case of thioanisole, an addition product was obtained.
- Matsukawa, Yuta,Hirashita, Tsunehisa,Araki, Shuki
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supporting information
p. 540 - 544
(2019/04/05)
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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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- Synthesis and nano-Pd catalyzed chemoselective oxidation of symmetrical and unsymmetrical sulfides
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A highly chemoselective, efficient and nano-Pd catalyzed protocol for the rapid construction of sulfoxides and sulfones via the oxidation of symmetrical and unsymmetrical sulfides using H2O2 as an oxidant has been developed, respectively. The ready availability of starting materials, easy recovery and reutilization of the catalyst, wide substrate scope, and high yields make this protocol an attractive alternative. The process also involves the metal-free and microwave-promoted synthesis of symmetrical diarylsulfides, and FeCl3-mediated preparation of symmetrical diaryldisulfides through the reaction of arenediazonium tetrafluoroborates with Na2S·9H2O as a sulfur source. In addition, unsymmetrical sulfides were generated via the K2CO3-mediated reaction of arenediazonium tetrafluoroborates with symmetrical disulfides.
- Li, Xing,Du, Jia,Zhang, Yongli,Chang, Honghong,Gao, Wenchao,Wei, Wenlong
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p. 3048 - 3055
(2019/03/21)
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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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- Method for preparing aryl sulfone compound as well as method for extracting catalyst and aryl sulfone compound
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The invention provides a preparation method of an aryl sulfone compound, which is characterized in that in an organic solvent and under an aerobic atmosphere, a catalytic system composed of a metal-ligand-TEMPO is used for catalytic oxidation of a thioether compound to obtain the aryl sulfone compound. The preparation method is simple, green, and efficient, the reaction condition is mild, and theapplication range is wide; the invention also provides a method for extracting a catalyst and the product aryl sulfone compound used in the preparation process. The ethyl acetate is added to a reaction mixture, steps of filtering and condensation under reduced pressure are carried out to obtain a filtrate and the catalyst, and silica gel column chromatography and concentration extraction are carried out to obtain the aryl sulfone compound. The extraction method is simple, and the extracted catalyst has high activity and good cycle stability, and the extraction rate of the product aryl sulfonecompound is high.
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Paragraph 0048-0051; 0141; 0146
(2019/02/13)
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- Method for photocatalytic synthesis of sulfur sulfone compounds
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The invention discloses a method for photocatalytic synthesis of sulfur sulfone compounds, and belongs to the technical field of catalysis. The invention provides a novel green environmentally-friendly method to efficiently synthesize the sulfur sulfone derivatives, and one thioether compound and an oxidizing agent are subjected to direct oxidization to form one corresponding sulfur sulfone compound under illumination by utilizing cercosporin as a catalyst. The method provided by the invention adopts the cercosporin as the catalyst, the catalytic conditions are milder, the reaction can be performed at room temperature under visible light irradiation, the catalyst has high catalytic activity and can be used for high-selectivity catalytic synthesis of the sulfur sulfone compounds, and the micro catalyst can make a yield higher, wherein the yield can reach 90% or more; and the photocatalyst and substrate raw materials used in the method are simple and easy to obtain, have low costs and can be produced on a large scale, and the method has very good application prospects.
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Paragraph 0042-0043
(2019/05/15)
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- Dual Photoredox/Nickel-Catalyzed Three-Component Carbofunctionalization of Alkenes
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The potential of merging photoredox and nickel catalysis to perform multicomponent alkene difunctionalizations under visible-light irradiation is demonstrated here. Secondary and tertiary alkyl groups, as well as sulfonyl moieties can be added to the terminal position of the double bond with simultaneous arylation of the internal carbon atom in a single step under mild reaction conditions. The process, devoid of stoichiometric additives, benefits from the use of bench-stable and easy-to-handle reagents, is operationally simple, and tolerates a wide variety of functional groups.
- García-Domínguez, Andrés,Mondal, Rahul,Nevado, Cristina
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supporting information
p. 12286 - 12290
(2019/08/01)
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- Regiospecific Cleavage of S-N Bonds in Sulfonyl Azides: Sulfonyl Donors
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Sulfonyl azides have been widely used as sulfonamido, diazo, and azido donors, as well as all-nitrogen 1,3-dipoles donors in synthetic chemistry. Here, the sulfonyl azides were used as efficient sulfonyl donors, which is very unusual. Trifluoromethanesulfonic acid-induced formation of the sulfonyl cation reactive species from sulfonyl azides was developed and used for the first time to couple various inactivated arenes to prepare sulfones at ambient temperature.
- Zhang, Zhiguo,Wang, Songnan,Zhang, Yong,Zhang, Guisheng
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p. 3919 - 3926
(2019/03/29)
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- Selective Synthesis of ortho-Substituted Diarylsulfones by Using NHC-Au Catalysts under Mild Conditions
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A single-step gold(I)-catalyzed chemoselective protocol to access ortho-substituted diarylsulfones has been established. Acenaphthoimidazolylidene gold complexes are effective catalysts for the arylsulfonylation of boronic acids by potassium metabisulfite (K2S2O5) and diaryliodonium salts to access (poly-)ortho-substituted diarylsulfones even in gram scale. Unlike the transition metal-catalyzed two-component coupling systems, the sterically hindered aryl groups in diaryliodonium salts are preferentially transferred over less bulky ones to form synthetically difficult targets, including those of pharmaceutical importance.
- Zhu, Haibo,Shen, Yajing,Wen, Daheng,Le, Zhang-Gao,Tu, Tao
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supporting information
p. 974 - 979
(2019/02/14)
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- MANUFACTURING METHOD OF COMPOUND HAVING SULFONYL GROUP
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The present invention relates to a method for manufacturing a compound having a sulfonyl group, which includes a step for reacting thiosulfonates in a solvent comprising nucleophilic bases with an electrophilic agent. Accordingly, the present invention can manufacture the compound having the sulfonyl group with a variety of structures with high efficiency and high yield through more simplified processes than conventional methods.COPYRIGHT KIPO 2018
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Paragraph 0108; 0109; 0121-0124
(2018/10/03)
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