- 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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- Facile synthesis of diarylsulfones from arenes and 3CdSO4·xH2O via mechanochemistry
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A variety of substituted diarylsulfones could be synthesized by simple arenes and 3CdSO4·xH2O in the presence of P2O5 under high-speed ball milling. It was suggest the aromatic sulfonation was performed by arene and in situ generated H2SO4, following-up by electrophilic substitution with another arene to give diarylsulfone.
- Qin, Shuai,Zhang, Pu,Qin, Yu-Jun,Guo, Zhi-Xin
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supporting information
(2020/01/06)
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- One-pot fluorosulfurylation of Grignard reagents using sulfuryl fluoride
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Herein, we report a new method for the one-pot syntheses of sulfonyl fluorides. Addition of an alkyl, aryl, or heteroaryl Grignard to a solution of sulfuryl fluoride at ambient temperature affords the desired sulfonyl fluorides in 18-78% yield. Furthermore, this method is applicable for in situ sequential reactions, whereby the Grignard reagent can be converted to the corresponding diarylsulfone, sulfonate ester, or sulfonamide in a one-pot process.
- Lee, Cayo,Ball, Nicholas D.,Sammis, Glenn M.
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supporting information
p. 14753 - 14756
(2019/12/23)
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- Synthesis of symmetrical diaryl sulfone by homocoupling of sodium arylsulfinate
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An efficient practical homocoupling reaction of sodium arylsulfinate promoted by Cu(II) is reported whereby symmetrical diaryl sulfone derivatives are obtained with high selectivity and reactivity by intermolecular cross-coupling. This homocoupling reacti
- Peng, Yao
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p. 265 - 268
(2014/06/09)
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- The synthesis of diarylsulfones with simple arenes and K2S2O8 through double C-S bond formation
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An unprecedented double C-S bond formation method has been developed to prepare both symmetric and unsymmetric diarylsulfones with simple arenes in a single step. This represents the first example that K2S2O8 can be employed as a highly effective sulfonating agent to synthesize diarylsulfones. The reaction demonstrates excellent reactivity, good functional group tolerance and high yields.
- Yang, Yiqing,Chen, Zhang,Rao, Yu
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supporting information
p. 15037 - 15040
(2014/12/11)
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- An improved catalyst system for the Pd-catalyzed fluorination of (hetero)aryl triflates
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The stable Pd(0) species [(1,5-cyclooctadiene)(L·Pd)2] (L = AdBrettPhos) has been prepared and successfully evaluated as a precatalyst for the fluorination of aryl triflates derived from biologically active and heteroaryl phenols, challenging substrates for our previously reported catalyst system. Additionally, this precatalyst activates at room temperature under neutral conditions, generates 1,5-cyclooctadiene as the only byproduct, and leads to overall cleaner reaction profiles.
- Lee, Hong Geun,Milner, Phillip J.,Buchwald, Stephen L.
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supporting information
p. 5602 - 5605
(2013/11/19)
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- Pd-catalyzed desulfonylative homocoupling of arenesulfonyl chlorides in the presence of hexamethyldisilane forming biaryls
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Arenesulfonyl chlorides undergo desulfonylative homo-coupling upon heating with hexamethyldisilane in the presence of Pd2(dibenzylideneacetone) 3?CHCl3 as a precatalyst to afford biaryls. Diaryl sulfides are occasionally formed as byproducts.
- Kashiwabara, Taigo,Tanaka, Masato
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p. 7125 - 7128
(2007/10/03)
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- Indium(III)-catalysed aryl sulfonylation reactions
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A rapid, high yielding and regioselective process has been developed for the synthesis of biaryl sulfones via sulfonylation reactions catalysed by indium(III) chloride.
- Garzya, Vincenzo,Forbes, Ian T.,Lauru, Stephanie,Maragni, Paolo
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p. 1499 - 1501
(2007/10/03)
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- Polymer electrolyte and process for producing the same
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A polymer electrolyte having, in a main chain, a structural unit represented by the following formula (1):-[Ar1-(SO2-N-(X+)-SO2-Ar2)m-SO2-N-(X+)-SO2-Ar1-O]- wherein Ar1 and Ar2 independently represent a divalent aromatic groups, m represents an integer of 0 to 3, and X+ represents an ion selected from hydrogen ion, an alkali metal ion and ammonium ion, which is excellent in proton conductivity, thermal resistance and strength. The polymer electrolyte is soluble in solvents and has excellent film forming property and recycling efficiency.
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- Preparation process of fluorine substituted aromatic compound
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A preparation process of a fluorine substituted aromatic compound comprising reacting an alkali metal or alkali earth metal salt of an aromatic compound having a hydroxy group with an organic fluorinating agent is disclosed. As a representative fluorinating agent, a bis-dialkylamino-difluoromethane compound, for example, 2,2′-difluoro-1,3-dimethylimidazolidine, is exemplified. According to the process, an industrially useful fluorinated aromatic compound, for example, a fluorobenzene, a fluorine substituted benzophenone, a fluorine substituted diarylsulfone can be prepared with ease in economy without specific equipment.
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- Mechanism of oxygenation of aryl methyl and diaryl sulphoxides by peroxomonophosphoric acid
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The kinetics of oxygenation of the title sulphoxides by peroxomonophosphoric acid in aqueous acetic acid follows an overall second-order kinetics, first-order in each reactant. An analysis of the influence of [H+] reveals that H3PO5 is the active species in the oxidation. The structure - reactivity studies with different substituents on the phenyl ring give evidence for the formation of an electron deficient sulphonium ion intermediate as the correlation between log k2 and σ gives a negative ρ value (ρ=-0.47±0.09, r=0.988, s=0.03 at 35°C for aryl methyl sulphoxides and ρ=-0.54±0.11, r=0.983, s=0.07 at 35°C for diaryl sulphoxides). It is proposed that the mechanism involves the nucleophilic attack of the sulphoxide sulphur on the peroxo-oxygen of H3PO5 in the rate-limiting step.
- Suthakaran,Rajagopal,Srinivasan
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p. 1369 - 1374
(2007/10/03)
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- Fluorodenitration of activated diphenyl sulphones using tetramethylammonium fluoride
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Fluorodenitration of nitro-substituted diphenyl sulphones occurs readily in dipolar aprotic solvents using tetramethylammonium fluoride as the source of fluoride, although other reactions including fluorodesulphonylation can sometimes occur in competition. - Keywords: Fluorodenitration; Diphenyl sulphones; Tetramethylammonium fluoride; NMR spectroscopy; Mass spectrometry
- Clark, James H.,Wails, David
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p. 201 - 206
(2007/10/02)
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- Differences in the Course of Reactions of N,N-Dichloroamides of Carboxylic and Sulfonic Acids with Diaryl Sulfoxides
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N,N-Dichloroamides of carboxylic acids are donors of oxygen in the reaction with diaryl sulfoxides that results in the formation of diaryl sulfones and the corresponding nitriles (oxidation of sulfoxides).N,N-Dichloroamides of sulfonic acids in the reaction with the same sulfoxides form N-arylsulfonyl-S,S-diarylsulfoxyimines (imination of sulfoxides).Based on the results of the MNDO calculations, probable intermediates responsible for realizing of a certain reaction pathway are suggested.
- Pigin, O. V.,Krasnov, V. L.,Groshev, Yu. G.,Bel'skii, V. K.,Bodrikov, I. V.
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p. 1520 - 1525
(2007/10/03)
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- Preparation of fluoroaromatic compounds in dispersion of potassium fluoride
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An improved process is disclosed for preparing fluoroaromatic compounds (such as fluoronitrobenzene compounds) wherein chloroaromatic compounds (such as chloronitrobenzene compounds) are reacted with potassium fluoride in a solvent dispersion thereof prepared from a mixture including the solvent, the fluoride, methanol and an aromatic compound.
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- NMR Study of Substituent Effects in 4-Substituted and 4,4'-Disubstituted Diphenyl Sulphoxides and Sulphones
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The proton and carbon NMR spectra of nine 4-X-diphenyl sulphoxides, seven 4-X-4'-NO2-diphenyl sulphoxides, eight 4,4'-X2-diphenyl sulphoxides, eight 4-X-diphenyl sulphones, seven 4-X-4'-NO2-diphenyl sulphones and eight 4,4'-X2-diphenyl sulphones have been obtained.Correlation of the 13C chemical shifts with the appropriate substituent chemical shifts (SCS) for monosubstituted benzenes (Lynch plots) does not show the enhancement of substituent effect at C-1 (para to the substituent) that was a feature of the corresponding sulphides studied earlier.Dual substituent parameter (DSP) correlations of the 13C chemical shifts with ?I/?R0 are excellent for carbons meta (C-2,6) and para (C-1) to the substituent.The trends for the series sulphides, sulphoxides, sulphones, where a decreasing response to the change of substituent is the general observation, are discussed.Changes of molecular conformation may also influence the transmission of electronic effects to the ring not carrying the variable substituent X. KEY WORDS 1H NMR 13C NMR Diphenyl sulpoxides Diphenyl sulphones Substituent effects
- Chandrasekaran, R.,Perumal, S.,Wilson, D. A.
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p. 360 - 367
(2007/10/02)
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- Kinetics and mechanism of oxidation of dimethyl, methyl phenyl and diaryl sulphoxides by N-bromocaprolactam
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The oxidation of dimethyl (DMSO) and methyl phenyl (MPSO) sulphoxides by N-bromocaprolactam (NBC) follows zero order kinetics in , but that of diphenyl sulphoxide (DPSO) is first order in .HClO4 accelerates the rate of all the oxidation reactions.However, added caprolactam retards the oxidation of only DPSO.
- Srinivasan, C.,Jegatheesan, P. Pandarakutty
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p. 250 - 252
(2007/10/02)
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- Trimethylsilylesters of Fluorobenzenesulfonic acids
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Fluorobenzenesulfonic acids were prepared by electrophilic sulfonation of fluorobenzenes 1.The acids are obtained as hydrates and converted to their trimethylsilyl esters 2 for characterization.
- Johannsen, Heiner,Sartori, Peter
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p. 674 - 679
(2007/10/02)
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- Substituent effects in cooxidation: Cr(VI) - oxalic acid - sulfoxides systems
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The kinetics of cooxidation of several substituted phenyl methyl sulfoxides and oxalic acid with Cr(VI) have been carried out in the presence of perchloric acid.The reaction is first order each in sulfoxide, oxalic acid, Cr(VI), and H1+.The products of oxidation are sulfones and carbon dioxide.Electron-releasing groups in the phenyl ring accelerate the rate while electron-withdrawing groups retard it.The Hammett correlation yields a reaction constant of -0.927 +/- 0.08 (r = 0.994) at 313 K.Addition of aluminum nitrate prevents the occurence of cooxidation.Based on the kinetic information a suitable mechanism has been proposed.Diaryl sulfoxides behave in an analogous manner in the cooxidation.
- Srinivasan, C.,Jegatheesan, P. Pandarakutty,Rajagopal, S.,Arumugam, N.
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p. 2421 - 2424
(2007/10/02)
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- Mechanism of Oxidation of Aryl Methyl Sulphoxides and Diaryl Sulphoxides by Potassium Bromate
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The oxidation of aryl methyl and diaryl sulphoxides in aqueous acetic acid at constant and ionic strength is first order each in and .An excellent correlation exists between logk2 and the Hammett ? constants (ρ=-2.05, r=0.997, s=0.05, confidence limit on ρ=+/-0.10 in 50percent aq acetic acid (v/v) at 35 deg for aryl methyl sulphoxides and ρ=-1.82, r=0.992, s=0.12, confidence limit on ρ=+/-0.32 in 75percent aq acetic acid (v/v) at 35 deg for diaryl sulphoxides).The high negative ρ-value in the two series indicates considerable charge development in the transition state.
- Srinivasan, C.,Jegatheesan, P. Pandarakutty,Arumugam, N.
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p. 678 - 680
(2007/10/02)
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- Process for preparing halo-substituted diarylsulfones
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A process for preparing diarylsulfone, the process comprising reacting chlorosulfonic acid with a mixture of (i) aromatic hydrocarbon represented by the formula STR1 wherein one of X and Y is a halogen atom and the other is a halogen atom or a hydrogen atom and (ii) aromatic sulfonic acid represented by the formula STR2 wherein X and Y are as defined above.
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- Oxidation of Alkenes and Sulphoxides with a Mixture of Potassium Superoxide and Diethyl Chlorophosphate
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The reaction of potassium superoxide with diethyl chlorophosphate in the presence of 18-crown-6 ether gave at least two oxidizing agents, one of which was electrophilic and used in the oxidation of alkenes, whilst the other, nucleophilic in type, was important in the oxidation of sulphoxides.
- Miura, Masahiro,Nojima, Masatomo,Kusabayashi, Shigekazu
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p. 1352 - 1353
(2007/10/02)
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