- Selective oxidation of sulfides to sulfoxides catalyzed by ruthenium (III) meso-tetraphenylporphyrin chloride in the presence of molecular oxygen
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Highly efficient selective oxidation of sulfides to sulfoxides by molecular oxygen catalyzed by ruthenium (III) meso-tetraphenylporphyrin chloride (Ru(TPP)Cl) with isobutyraldehyde as oxygen acceptor has been reported. In large-scale experiment of thioanisole oxidation, the isolated yield of sulfoxide of 92% was obtained and the turnover number reached up to 92,000.
- Zhou, Xian-Tai,Ji, Hong-Bing,Cheng, Zhao,Xu, Jian-Chang,Pei, Li-Xia,Wang, Le-Fu
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- Calorimetric and computational study of 1,3-and 1,4-oxathiane sulfones
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(Chemical Equation Presented) The enthalpies of formation in the condensed and gas states, ΔfH°m(cd) and ΔfH°m(g), of 1,3- and 1,4-oxathiane sulfones were derived from their respective enthalpies of combustion in oxygen, measured by a rotating bomb calorimeter and the variation of vapor pressures with temperatures determined by the Knudsen effusion technique. Standard ab initio molecular orbital calculations at the G2(MP2) and G3 levels were performed, and a theoretical study on molecular and electronic structure of the compounds has been carried out. Calculated ΔfH°m(g) values at the G3 level using atomization reactions agree well with the experimental ones. These experimental and theoretical studies support that the destabilization found in 1,3-oxathiane sulfone, 11.2 kJ mol-1 respecting to 1,4-oxathiane sulfone, is due to the electrostatic repulsion between the negative charges of the axial oxygen of the sulfone and the oxygen of the ring and apparently masks any stabilization originating from the hyperconjugative nO → σ*C-SO2 stereoelectronic interaction.
- Roux, Maria Victoria,Temprado, Manuel,Jimenez, Pilar,Notario, Rafael,Guzman-Mejia, Ramon,Juaristi, Eusebio
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- Chemoselective catalytic oxidation of sulfides to sulfones with tetrapropylammonium perruthenate (TPAP)
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Tetrapropylammonium perruthenate has been found to be an efficient catalyst for the conversion of sulfides to sulfones. The method is highly chemoselective and isolated double bonds are generally unaffected.
- Guertin,Kende
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- Chemoselective oxidation of sulfides to sulfones with magnesium monoperoxyphthalate (MMPP) on silica gel support in methylene chloride solvent
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A simple, efficient and chemoselective, non-aqueous procedure for oxidation of sulfides to the corresponding sulfones with magnesium monoperoxyphthalate on hydrated silica gel has been developed.
- Ali, Mohammed Hashmat,Bohnert, Gary J.
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- Study on the Kinetics and Transformation Products of Sulfur Mustard Sulfoxide and Sulfur Mustard Sulfone in Various Reaction Media
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Considering postulates of the Chemical Weapons Convention, this article is an attempt to improve the decontamination methods of mustard gas (HD) and studying its products of decontamination. It is widely known that mustard gas sulfoxide (HDO; O═S(CH2CH2Cl)2) and sulfone (HDO2; O2═S(CH2CH2Cl)2) undergo further transformations to another compounds, but so far kinetics of these processes have not yet been investigated neither carefully nor thoroughly. This study is focused on determination of kinetics and mechanisms of transformation of HD oxidation products. The primary objective of this study is to assess the impact of selected factors on the kinetics of the HCl elimination reaction and to determine the conditions in which cyclization reactions of divinyl sulfoxide and sulfone proceed. The HDO and HDO2 decay kinetics were monitored in an aqueous solution of the desired pH. The rate of HCl elimination from HDO and HDO2 is strongly dependent on pH. For example, with pH increasing from 9 to 12 the rate of HCl elimination from HDO increased over 1200 times. In solutions of pH 9, HDO loses hydrogen chloride at approximately 100 times slower compared to HDO2, and the difference is reduced with increasing pH. In pH 12 solutions, the rate of hydrogen chloride loss from HDO2 is only 20 times higher than the HCl loss from HDO. Divinyl sulfoxide and sulfone undergo a further transformation in a strongly alkaline environment, leading to cyclization and formation of 1,4-thioxane sulfoxide and sulfone, respectively. Elimination of HCl from HDO and HDO2 goes with a rapidly increasing rate with increasing pH if alkalinity of the reaction medium is relatively very high (the range of pH 9–12). Furthermore, the conversion of divinyl sulfone and sulfoxide to sulfoxide and sulfone thioxane, respectively, occurs at a measurable rate when the pH of the solution is in the range of 12–14.
- Popiel, Stanis?aw,Nawa?a, Jakub,Dziedzic, Daniel,Gordon, Diana,Dawidziuk, Barbara
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- Flow Electrosynthesis of Sulfoxides, Sulfones, and Sulfoximines without Supporting Electrolytes
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An efficient electrochemical flow process for the selective oxidation of sulfides to sulfoxides and sulfones and of sulfoxides toN-cyanosulfoximines has been developed. In total, 69 examples of sulfoxides, sulfones, andN-cyanosulfoximines have been synthesized in good to excellent yields and with high current efficiencies. The synthesis was assisted and facilitated through a supporting electrolyte-free, fully automated electrochemical protocol that highlights the advantages of flow electrolysis.
- Amri, Nasser,Wirth, Thomas
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p. 15961 - 15972
(2021/07/20)
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- Synthesis, Characterization and Catalytic Activity of a Tungsten(VI) Amino Triphenolate Complex
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Abstract: Synthesis, characterization and catalytic activity of a novel tungsten(VI) amino triphenolate complex have been investigated. In particular, a tungsten(VI) amino triphenolate complex has been synthesized and tested in the oxidation of sulfides and cyclooctene, using hydrogen peroxide as terminal oxidant. The catalyst has proved to be air and water tolerant, also showing a good efficiency in terms of yields and selectivity. Moreover, an upgrade of our previous ligand synthesis is herein reported. The new developed procedure allows to obtain the triphenolamine in large scale without the use of chromatography for the intermediates purification. Graphical Abstract: [Figure not available: see fulltext.].
- Badetti, Elena,Bonetto, Alessandro,Romano, Francesco,Marchiò, Luciano,Zonta, Cristiano,Licini, Giulia
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p. 2313 - 2318
(2017/08/22)
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- Double (2-haloethyl) ether synthesis method
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The invention relates to the synthesis of fine chemical intermediates, in particular to a synthesis method of di(2-halogenated ethyl) ether. According to the synthesis method, 1,4-thioxane-1,1-dioxo and a hydrogen halide water solution react with each other to obtain the target product, namely di(2-halogenated ethyl) ether. The synthesis method is simple and convenient in technical route, good in selectivity, high in yield, less in pollution and simple in post-processing, conforms to the tendency of the green chemical industry nowadays, and has great industrial value.
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Paragraph 0013-0014
(2017/02/24)
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- Sulfoxidation with hydrogen peroxide catalyzed by [SeO 4{WO(O2)2}2]2-
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The selenium-containing dinuclear peroxotungstate, [(n-C4H 9)4N]2[SeO4{WO(O2) 2}2] (I), acts as a homogeneous catalyst for the selective oxidation of various kinds of cyclic mono- and disulfides with 30% aqueous H2O2. The cyclic disulfides were selectively oxidized to the corresponding monosulfoxides with one equivalent of H2O 2 with respect to the sulfides. In the presence of two equivalents of H2O2, the oxidation of dibenzothiophene gave the corresponding sulfone in 98% yield under the mild conditions. The negative Hammett ρ value (-0.62) for the competitive oxidation of p-substituted thioanisoles and the low XSO (XSO = (nucleophilic oxidation)/(total oxidation)) value of 0.14 for the I-catalyzed oxidation of thianthrene 5-oxide (SSO) revealed that I is a strong electrophilic oxidant. The reactivities of the di- and tetranuclear peroxotungstates with XO 4n- ligands (X = Se(vi), As(v), P(v), S(vi), and Si(iv)) were strongly dependent on the kinds of hetero atoms. The reaction rates for the sulfoxidation decreased with an increase in the XSO values and a peroxotungstate with a stronger electrophilicity was more active for the sulfoxidation. The kinetic and mechanistic investigations showed that the electrophilic attack of the peroxo oxygen at the sulfur atom is a key step in the sulfoxidation. The computational investigation supported the high chemoselectivitiy for the sulfoxidation of diallyl sulfide.
- Kamata, Keigo,Hirano, Tomohisa,Ishimoto, Ryo,Mizuno, Noritaka
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experimental part
p. 5509 - 5518
(2010/08/04)
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- Divinyl Sulfoxide. X. Reaction of Divinyl Sulfoxide with Water
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High yield of etoxy sulfoxides with terminal vinyl and/or hydroxy groups was obtained in the reaction of divinyl sulfoxide with water in the presence of catalytic amounts of alkali metals hydroxides.
- Chernysheva,Gusarova,Tatarinova,Al'pert,Trofimov
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p. 796 - 799
(2007/10/03)
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- Sulfur Heterocycles. 3. Heterogeneous, Phase-Transfer, and Acid-Catalyzed Potassium Permanganate Oxidation of Sulfides to Sulfones and a Survey of their Carbon-13 Nuclear Magnetic Resonance Spectra
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Although numerous oxidation methods are available for the transformation of sulfides into sulfones, low-molecular-weight, heterocyclic sulfides are often not amenable to this oxidation techniques.The method presented here is a general and economical oxidation using potassium permanganate and various catalysts.Nineteen low-molecular-weight and heterocyclic sulfides were successfully oxidized by variations of this technique, and the results are presented here.In addition, the carbon-13 NMR spectra of these compounds and about two dozen others are reported.General chemical shift trends are reported for selected compounds, and details can be found in the supplementary material.
- Gokel, George W.,Gerdes, Harold M.,Dishong, Dennis M.
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p. 3634 - 3639
(2007/10/02)
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