- A PROCESS FOR THE SYNTHESIS OF ARYL SULFONES
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The present patent discloses a novel, efficient and transition-metal-free room temperature single step process for synthesis of aryl sulfones and substituted aryl sulfones starting from aryl substrates.
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Page/Page column 9; 12; 15
(2015/06/25)
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- One-pot synthesis of aryl sulfones from organometallic reagents and iodonium salts
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A transition-metal-free arylation of lithium, magnesium, and zinc sulfinates with diaryliodonium salts is described. The sulfinic acid salts were prepared from the reaction of the corresponding organometallic reagents and sulfur dioxide. Combination of the three single steps (preparation of the organometallic compound, sulfinate formation, and arylation) leads to a one-pot sequence for the synthesis of aryl sulfones from simple starting materials. The chemoselectivity of unsymmetrical diaryliodonium salts has been investigated. Potential and limitations of this method will be discussed.
- Margraf, Natalie,Manolikakes, Georg
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p. 2582 - 2600
(2015/03/18)
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- Transition-metal-free C-S bond formation: A facile access to aryl sulfones from sodium sulfinates via arynes
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Sulfones have been attractive targets for synthetic organic chemists owing to their immense applications in medicinal, material, and synthetic chemistry. In this context, an efficient transition-metal-free process has been demonstrated, wherein a broad range of alkyl/aryl/heteroaryl sodium sulfinates react with varyingly substituted aryne precursors (o-silyl aryl triflates) under mild reaction conditions to afford structurally diverse sulfones in good to excellent yields.
- Pandya, Virat G.,Mhaske, Santosh B.
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supporting information
p. 3836 - 3839
(2014/08/05)
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- Arylation of lithium sulfinates with diaryliodonium salts: A direct and versatile access to arylsulfones
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An efficient, transition-metal-free arylation of lithium sulfinates, which are readily accessible from reactions of organolithium reagents with sulfur dioxide, is described. Based on this method, a practical protocol for the direct transformation of (hetero)arenes and (hetero)aromatic halides into diarylsulfones was developed.
- Umierski, Natalie,Manolikakes, Georg
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p. 4972 - 4975
(2013/10/22)
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- Metal-free synthesis of diaryl sulfones from arylsulfinic acid salts and diaryliodonium salts
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An efficient, high-yielding, and transition-metal-free synthesis of diaryl sulfones from arylsulfinic acid salts and diaryliodonium salts has been developed. The mild reaction conditions tolerate a range of functional groups, and unsymmetrical diaryliodonium salts show high chemoselectivity.
- Umierski, Natalie,Manolikakes, Georg
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supporting information
p. 188 - 191
(2013/03/28)
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- Sulfonylation of aromatic compounds with sulfonic acids using silica gel-supported AlCl3 as a heterogeneous Lewis acid catalyst
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Silica gel-supported aluminum chloride (SiO2-AlCl3) has been shown to be a mild, efficient, and chemoselective heterogeneous Lewis acid catalyst for direct conversion of arenes to sulfones using sulfonic acids as sulfonylating agents. The catalyst can be prepared easily with cheap starting materials and is stable (as a bench-top catalyst) and reusable.
- Parvanak Boroujeni, Kaveh
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experimental part
p. 197 - 203
(2010/11/05)
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- Polystyrene supported Al(OTf)3: A stable, efficient, selective, and reusable catalyst for sulfonylation of arenes with sulfonic acids
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Cross-linked polystyrene supported aluminium triflate (Ps-Al(OTf) 3) was found to be an efficient and chemoselective heterogeneous Lewis acid catalyst for the direct conversion of arenes to sulfones using sulfonic acids as sulfonylating agents. The solid acid catalyst is stable (as a bench top catalyst) and can be easily recovered and reused without appreciable change in its efficiency.
- Boroujeni, Kaveh Parvanak
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experimental part
p. 1887 - 1890
(2010/11/18)
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- Sulfonated polybenzothiazoles: A novel Candidate for proton exchange membranes
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Sulfonated polybenzothiazoles (sPBT) with high molecular weight as well as excellent solubility were synthesized for the first time, which was achieved by attaching the phenylsulfonyl pendant groups or incorporating the hexafiuoroisopropylidene moieties t
- Tan, Ning,Xiao, Guyu,Yan, Deyue
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experimental part
p. 1022 - 1031
(2011/10/08)
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- Sulfonylation of arenes with sulfonamides
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In the presence of triflic anhydride, sulfonylation of arenes with sulfonamides proceeded smoothly in Cl2CHCHCl2 at 80-140 °C, which gave rise to the desired products in good to excellent yields.
- Yao, Bangben,Zhang, Yuhong
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p. 5385 - 5388
(2008/12/21)
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- Highly selective catalytic Friedel-Crafts sulfonylation of aromatic compounds using a FeCl3-based ionic liquid
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Friedel-Crafts sulfonylation of aromatic compounds was carried out using FeCl3-based ionic liquid. These liquids serve as efficient media as well as Lewis acid catalyst.
- Bahrami, Kiumars,Khodei, Mohammad Mehdi,Shahbazi, Fomeida
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p. 3931 - 3934
(2008/09/21)
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- Rapid and mild sulfonylation of aromatic compounds with sulfonic acids via mixed anhydrides using Tf2O
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An efficient and direct sulfonylation of aromatic compounds with sulfonic acids is described via mixed anhydrides in short reaction times using Tf2O in nitromethane at room temperature.
- Alizadeh, Abdolhamid,Khodaei, Mohammd Mehdi,Nazari, Ehsan
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p. 6805 - 6808
(2008/03/12)
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- Direct sulfonylation of aromatic rings with aryl or alkyl sulfonic acid using supported P2O5/Al2O3
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Direct sulfonylation of aromatic rings with aryl or alkyl sulfonic acid supported P2O5/Al2O3 (w/w 50%) under heterogeneous conditions in short reaction time and high yields. Copyright Taylor & Francis Inc.
- Hajipour, Abdol R.,Zarei, Amin,Khazdooz, Leila,Pourmousavi, Seied A.,Mirjalili, Bi Bi F.,Ruoho
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p. 2029 - 2034
(2007/10/03)
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- A practical and efficient method for the preparation of aromatic sulfones by the reaction of aryl sulfonyl chlorides with arenes catalysed by Fe(OH) 3
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Fe (OH)3 catalyses Friedel-Crafts sulfonylation of arenes with aryl sulfonyl chlorides to obtain the corresponding diaryl sulfones in good yields.
- Jin, Tongshou,Zhao, Ying,Ma, Yanran,Li, Tongshuang
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p. 2183 - 2185
(2007/10/03)
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- Antimony(V) chloride-benzyltriethylammonium chloride complex as an efficient catalyst for friedel-crafts acylation reactions
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A novel catalytic system, the complex of antimony(V) chloride (SbCl 5) and benzyltriethylammonium chloride (TEBA), C6H 5CH2NEt3(SbCl5)2Cl complex, is described for Friedel-Crafts acylation reactions of aromatics with acyl and sulfonyl chlorides. The catalyst has a number of useful characteristics, such as ready access, minimal toxicity, reusability, insensitivity to atmosphere and moisture, rapid acylation with high yield, and ease of operation.
- Huang, An-Ping,Liu, Xue-Yuan,Li, Lian-Hua,Wu, Xiao-Li,Liu, Wei-Min,Liang, Yong-Min
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p. 599 - 602
(2007/10/03)
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- An efficient and convenient method for the synthesis of aromatic sulfones catalysed by ZrO2/S2O82- solid superacid
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A manipulatively simple and rapid procedure for the synthesis of diaryl sulfones from arylsulfonyl chlorides with aromatic compounds is described; the reaction is conducted under Friedel-Crafts conditions in the absence of solvent using ZrO2/S2O82- as catalyst in 78-93% yields.
- Jin, Tongshou,Yang, Mina,Feng, Guoliang,Li, Tongshuang
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p. 721 - 723
(2007/10/03)
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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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p. 1696 - 1697
(2007/10/03)
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- An efficient method for aromatic Friedel-Crafts alkylation, acylation, benzoylation, and sulfonylation reactions
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Aromatic electrophilic substitution reactions such as alkylation, acylation, benzoylation, and sulfonylation were studied in the presence of a catalytic amount of Cu(OTf)2 and Sn(OTf)2. Cu(OTf)2 was very efficient for alkylation, acylation, and benzoylation reactions. However, in case of sulfonylation reactions, Sn(OTf)2 gave better results.
- Singh, Ravi P,Kamble, Rajesh M,Chandra, Kusum L,Saravanan,Singh, Vinod K
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p. 241 - 247
(2007/10/03)
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- Acylation and related reactions under microwaves. 4. Sulfonylation reactions of aromatics
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Solvent-free sulfonylation of benzene and its activated or deactivated derivatives were carried out under microwave (MW) irradiation and a catalytic amount of iron(III) chloride, which, under these conditions, is more, active than other metallic salts. With more reactive and/or nonvolatile reagents (anisole, xylenes, mesitylene) expeditious conditions (short reaction time at constant MW power without control of the temperature) were used. With less reactive and/or low-boiling reagents (benzene, toluene, halobenzenes), the rise in temperature and the increase of reaction time were controlled either by sequential MW irradiation or by a temperature order. It was shown that MWs cause preferential interactions with polar species present in the reaction, especially the aryl sulfone and its FeCl3-complexed form. A MW nonthermal effect was not observed when identical temperature gradients were produced by classical heating and MW irradiation, and if reaction temperature was strictly controlled.
- Marquie,Laporterie,Dubac,Roques,Desmurs
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p. 421 - 425
(2007/10/03)
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- An efficient and novel method for the synthesis of aromatic sulfones under solvent - Free conditions
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A manipulative simple and rapid reaction of arensulfonyl chloride with aromatic hydrocarbons is described. The reaction is conducted under Friedel-Crafts conditions in the absences of solvent using aluminium chloride as catalysts.
- Hajipour,Mallakpour,Imanzadch
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p. 237 - 239
(2007/10/03)
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- Organic reactions under solid-state conditions
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Manipulatively simple and rapid methods are described for the synthesis of: chiral sulfinate esters from sulfonyl chlorides and sufonic acids; aldehydes and ketones from oximes, alcohols, hydrozones; sulfoxides from sulfides; and disulfides from thiols. The chemical yields are good to excellent and diastereoselectivity is high.
- Hajipour,Mallakpour
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p. 371 - 387
(2007/10/03)
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- Patterns of soft C - H...O hydrogen bonding in diaryl sulfones
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In bis(4-tolyl) sulfone, C14H14O2S (1), 2,5,4′-trimethyldiphenyl sulfone, C15H16O2S (2), and 4-chlorodiphenyl sulfone, C12H9ClO2S (3), the molecules are lin
- Glidewell, Christopher,Harrison, William T. A.,Low, John N.,Sime, Jamie G.,Wardell, James L.
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p. 190 - 200
(2007/10/03)
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- Electrochemical Reduction of Some o-Bis(phenylsulphonyl)benzene Derivatives. Effect of the Substrate Structure and of the Addition of Bases on the Product Distribution.
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A study of the electrochemical behaviour of the o-bis(phenylsulphonyl)benzene derivatives (1a-e) in dimethyl sulphoxide containing 0.1M-tetrabutylammonium tetrafluoroborate has been undertaken.The results from cyclic voltammetry, controlled-potential electrolysis, and coulometry strongly argue in support of a mechanism involving initial formation of the radical anion (1)-. which fragments into the ? radical (2) and PhSO2-.Competing pathways for (2) are (a) intramolecular homolytic arylation eventually leading to dibenzothiophene (4) together with dihydrodibenzothiophene (5) derivatives and (b) hydrogen-atom transfer leading to monosulphones (6).The fact that compounds (1a,b) undergo mainly cyclization, whereas the hydrogen-atom transfer predominates in the case of compounds (1c,d), indicates that the structure of the starting substrate is a major governing factor for the above competition.An explanation, based on a concomitance of steric effects of the methyl groups ortho to the phenylsulphonyl substituents, is given.Experiments carried out in the presence of different bases show that the intramolecular arylation leading to the cyclized product can occur also through an unprecedented chain mechanism whose efficiency, which increases as the strength and the concentration of the base is increased, is found in turn to be dependent on the substrate structure.Finally, when arenethiolates are used as bases, a third pathways (the nucleophile-radical coupling step of the SRN1 process) is found to compete for the intermediate ? radical (2) eventually leading to sulphides resulting from the overall substitution of an arylthio for a moiety in (1).When the intramolecular cyclization does not compete efficiently almost quantitative yields of sulphides are obtained via an SRN1 route.
- Novi, Marino,Garbarino, Giacomo,Petrillo, Giovanni,Dell'Erba, Carlo
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p. 623 - 632
(2007/10/02)
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- Photostimulated Reactions of o-Bis(phenylsulfonyl)benzene Derivatives with Sodium Arenethiolates in Me2SO. Evidence for Competing Pathways Involving a Common Intermediate ? Radical
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The effects of incremental additions of benzenethiol on the product distribution of the photostimulated reactions of 2,3-bis(phenylsulfonyl)-1,4-dimethyl- (1a) and 1,2-bis(phenylsulfonyl)-3,4,5,6-tetramethylbenzene (1b) with sodium benzenethiolate in Me2S
- Novi, Marino,Garbarino, Giacomo,Dell'Erba, Carlo
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p. 2799 - 2803
(2007/10/02)
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- Electrochemical Evidence for an Unusual Base-Catalysed Chain Mechanism in an Intramolecular Homolytic Arylation
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Cyclic voltammetry and controlled-potential electrolysis of the disulphone (1a) in dimethyl sulphoxide show that its transformation into the dibenzothiophene dioxide (2a), in the presence of a base, is an efficient electrocatalytic process.
- Novi, Marino,Garbarino, Giacomo,Dell'Erba, Carlo,Petrillo, Giovanni
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p. 1205 - 1207
(2007/10/02)
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- SINGLE-ELECTRONIC CLEAVAGE OF A CARBON-SULFUR BOND IN THE CATHODIC REDUCTION OF 2,3-BIS(PHENYLSULPHONYL)-1,4-DIMETHYLBENZENE IN DIMETHYL SULPHOXIDE
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2,3-Bis(phenylsulphonyl)-1,4-dimethylbenzene, dissolved in dimethyl sulphoxide, undergoes a one-electron single reduction wave at -1,6 V respect to Ag-Ag(1+)(0.01M).The reduction was studied by differential pulse polarography, cyclic voltametry, and controlled-potential electrolysis.Fast chemical steps follow the initial reduction and the isolated products are 1,4-dimethyldibenzothiophene 5,5-dioxide and 1,4-dimethyl-2-(phenylsulphonyl)benzene.In some experiments small percentages of 5a,9a-dihydro-1,4-dimethyldibenzothiophene 5,5-dioxide are also obtained.The results argue in support of the electron-transfer mechanism previously proposed for the photoinduced reactions of the same substrate with sodium arenethiolates in dimethyl sulphoxide.
- Novi, Marino,Dell'Erba, Carlo,Garbarino, Giacomo,Scarponi, Giuseppe,Capodaglio, Gabriele
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p. 951 - 954
(2007/10/02)
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- Normal SNAr, Telesubstitution, and Electron-Transfer Pathways in the Reactions of Methyl-Substituted o-Bis(phenylsulfonyl)benzene Derivatives with Sodium Arenethiolates in Dimethyl Sulfoxide
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1,4-Dimethyl-2,3-bis(phenylsulfonyl)-(6a) and 1,2-bis(phenylsulfonyl)-3,4,5,6-tetramethylbenzene (6b) react with sodium benzenethiolate or 2,4,6-trimethylbenzenethiolate in Me2SO at 120 deg C to give mainly products (7a,b,9, and 10a) resulting from the no
- Novi, Marino,Dell'Erba, Carlo,Garbarino, Giacomo,Sancassan, Fernando
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p. 2292 - 2298
(2007/10/02)
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