- Enhanced preparation of aryl and heteryl sulfur pentafluorides using mercury (II) oxide - hydrogen fluoride media as a fluorinating reagent
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We developed enhanced method for low temperature and good yield preparation of aryl and heteryl sulfur pentafluorides from chlorotetrafluorides using mercury oxide - hydrogen fluoride and mercury oxide - pyridinium poly(hydrogen fluoride) media as the fluorinating reagents.
- Fetyukhin, Volodymyr N.,Guzyr, Olexandr I.,Kozel, Volodymyr N.,Rozhenko, Olexandr B.,Rusanov, Eduard B.,Shermolovich, Yuriy G.
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- Improved Access to Organo-Soluble Di- and Tetrafluoridochlorate(I)/(III) Salts
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A facile one-pot gram-scale synthesis of tetraalkylammonium tetrafluoridochlorate(III) [cat][ClF4] ([cat]=[NEt3Me]+, [NEt4]+) is described. An acetonitrile solution of the corresponding alkylammonium chloride salt is fluorinated with diluted fluorine at low temperatures. The reaction proceeds via the [ClF2]? anion which is structurally characterized for the first time. The potential application of [ClF4]? salts as fluorinating agents is evaluated by the reaction with diphenyl disulfide, Ph2S2, to pentafluorosulfanyl benzene, PhSF5. The CN moieties in acetonitrile and [B(CN)4]? are transferred in CF3 groups. Exposure of carbon monoxide, CO, leads to the formation of carbonyl fluoride, COF2, and elemental gold is dissolved under the formation of tetrafluoridoaurate [AuF4]?.
- Kaupp, M.,Müller, R.,Pr?hm, P.,Riedel, S.,Schattenberg, C. J.,Schmid, J. R.,Sonnenberg, K.,Steinhauer, S.,Vo?nacker, P.
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supporting information
p. 16002 - 16006
(2020/07/20)
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- Synthesis of 4-(pentafluorosulfanyl)benzenediazonium tetrafluoroborate and analogs and their application for the preparation of SF5-aromatics
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4-(pentafluorosulfanyl)benzenediazonium tetrafluoroborate salt was synthesized and isolated. The pentafluorosulfanyl salt was examined in a wide assortment of reactions to form novel SF5-bearing alkenes, alkynes, and biaryl derivatives using Heck-Matsuda, Sonogashira, and Suzuki coupling protocols. Dediazoniation of the salt furnished the corresponding p-SF5—C6H4X,C6H4OS(O)(CF3)═NSO2CF3, and p-SF5—C6H4-NTf2 derivatives. The azide derivative p-SF5—C6H4N3 entered into click chemistry with phenylacetylenes to furnish the corresponding triazoles. Various SF5-bearing alkenes were synthesized by coupling reactions using a metal catalyst. Fluorodediazoniation selectively furnished the fluoro derivative p-SF5—C6H4F. Homolytic dediazoniation gave the unsymmetrical biaryls, thus demonstrating the broad utility of pentafluorosulfanyl diazonium salts as building blocks of SF5-aromatics that are in high demand in many branches of chemistry including biomedicine and materials chemistry.
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Page/Page column 16; 31
(2016/02/05)
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- Pyridine-promoted dediazoniation of aryldiazonium tetrafluoroborates: Application to the synthesis of SF5-substituted phenylboronic esters and iodobenzenes
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Pyridine promotes dediazoniation of aryldiazonium tetrafluoroborates. The formed aryl radicals were trapped with B2pin2, iodine, or tetrahydrofuran to afford boronic esters, iodobenzenes and benzenes, respectively. The application to the synthesis of (pentafluorosulfanyl) phenylboronic esters, iodo(pentafluorosulfanyl)benzenes and (pentafluorosulfanyl)benzene is shown.
- Iakobson, George,Du, Junyi,Slawin, Alexandra M. Z.,Beier, Petr
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p. 1494 - 1502
(2016/04/09)
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- An improved method for the fluorination of arylsulfur chlorotetrafluorides to arylsulfur pentafluorides
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A new method for the fluorination of arylsulfur chlorotetrafluorides to arylsulfur pentafluorides is described. The reaction is promoted by hydrogen fluoride generated from potassium hydrogen fluoride and trifluoroacetic acid which also serves as a solvent. The reaction is performed under mild conditions and uses substochiometric amounts of potassium hydrogen fluorides in certain cases. Recovery and reuse of trifluoroacetic acid was successfully demonstrated which makes this method safe, simple to use, and atom- and cost-effective.
- Lummer, Katrin,Ponomarenko, Maxim V.,R?schenthaler, Gerd-Volker,Bremer, Matthias,Beier, Petr
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- 4-(Pentafluorosulfanyl)benzenediazonium Tetrafluoroborate: A Versatile Launch Pad for the Synthesis of Aromatic SF5 Compounds via Cross Coupling, Azo Coupling, Homocoupling, Dediazoniation, and Click Chemistry
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The reagent 4-(pentafluorosulfanyl)benzenediazonium tetrafluoroborate (1) was synthesized and isolated as a stable salt for the first time; its application in a wide assortment of transformations was subsequently investigated. A series of novel SF5-bearing alkenes, alkynes, and biaryl derivatives were synthesized by employing Heck-Matsuda, Sonogashira, and Suzuki coupling protocols. Dediazoniation with TMSX (X = Hal; N3; and CN) and NH4SCN in [BMIM][BF4] as solvent furnished the corresponding p-SF5-C6H4X derivatives. The azide derivative p-SF5-C6H4N3 entered into click chemistry with phenylacetylenes to furnish the corresponding triazoles. The 4,4′-bis(pentafluorosulfanyl)biphenyl was synthesized by homo-coupling using Pd(OAc)2. The corresponding azo compounds were obtained through azo-coupling with reactive aromatic nucleophiles (1,3-dimethoxybenzene, 1,3,5-trimethoxybenzene, 1,2,4-trimethoxybenzene, aniline and phenol). Fluorodediazoniation in [BMIM][PF6] and [BMIM][BF 4] selectively furnished the fluoro derivative p-SF 5-C6H4F. Dediazoniation in [BMIM][NTf 2] gave p-SF5-C6H4OS(O)(CF 3)=NSO2CF3 as the major and p-SF 5-C6H4-NTf2 as the minor products. Homolytic dediazoniation in MeCN/NaI gave the unsymmetrical biaryls p-SF 5-C6H4-Ar (ArH = mesitylene and p-xylene) along with p-SF5-C6H4I. Analysis of the dediazoniation product mixtures indicated that dediazoniation of p-SF 5-C6H4N2+ BF 4- in low nucleophilicity, highly ionizing, solvents (TfOH, TFE, HFIP, TFAH) is mainly heterolytic, while in MeOH it is mainly homolytic. The isodesmic reaction p-SF5-C6H 4+ + R-C6H5 → SF 5-C6H5 + p-R-C6H4 + (with R = NO2, CF3, H) was gauged by DFT at various levels and by PCM. Copyright
- Okazaki, Takao,Laali, Kenneth K.,Bunge, Scott D.,Adas, Sonya K.
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p. 1630 - 1644
(2014/03/21)
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- 4-(Pentafluorosulfanyl)benzenediazonium Tetrafluoroborate: A Versatile Launch Pad for the Synthesis of Aromatic SF5 Compounds via Cross Coupling, Azo Coupling, Homocoupling, Dediazoniation, and Click Chemistry
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The reagent 4-(pentafluorosulfanyl)benzenediazonium tetrafluoroborate (1) was synthesized and isolated as a stable salt for the first time; its application in a wide assortment of transformations was subsequently investigated. A series of novel SF5-bearing alkenes, alkynes, and biaryl derivatives were synthesized by employing Heck-Matsuda, Sonogashira, and Suzuki coupling protocols. Dediazoniation with TMSX (X = Hal; N3; and CN) and NH4SCN in [BMIM][BF4] as solvent furnished the corresponding p-SF5-C6H4X derivatives. The azide derivative p-SF5-C6H4N3 entered into click chemistry with phenylacetylenes to furnish the corresponding triazoles. The 4,4′-bis(pentafluorosulfanyl)biphenyl was synthesized by homo-coupling using Pd(OAc)2. The corresponding azo compounds were obtained through azo-coupling with reactive aromatic nucleophiles (1,3-dimethoxybenzene, 1,3,5-trimethoxybenzene, 1,2,4-trimethoxybenzene, aniline and phenol). Fluorodediazoniation in [BMIM][PF6] and [BMIM][BF4] selectively furnished the fluoro derivative p-SF5-C6H4F. Dediazoniation in [BMIM][NTf2] gave p-SF5-C6H4OS(O)(CF3)=NSO2CF3 as the major and p-SF5-C6H4-NTf2 as the minor products. Homolytic dediazoniation in MeCN/NaI gave the unsymmetrical biaryls p-SF5-C6H4-Ar (ArH = mesitylene and p-xylene) along with p-SF5-C6H4I. Analysis of the dediazoniation product mixtures indicated that dediazoniation of p-SF5-C6H4N2+ BF4- in low nucleophilicity, highly ionizing, solvents (TfOH, TFE, HFIP, TFAH) is mainly heterolytic, while in MeOH it is mainly homolytic. The isodesmic reaction p-SF5-C6H4+ + R-C6H5 → SF5-C6H5 + p-R-C6H4+ (with R = NO2, CF3, H) was gauged by DFT at various levels and by PCM.
- Okazaki, Takao,Laali, Kenneth K.,Bunge, Scott D.,Adas, Sonya K.
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p. 1630 - 1644
(2015/10/05)
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- Discovery of practical production processes for arylsulfur pentafluorides and their higher homologues, bis- and tris(sulfur pentafluorides): Beginning of a new era of "super-trifluoromethyl" arene chemistry and its industry
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Various arylsulfur pentafluorides, ArSF5, have long been desired in both academic and industrial areas, and ArSF5 compounds have attracted considerable interest in many areas such as medicines, agrochemicals, and other new materials, since the highly stable SF5 group is considered a "super-trifluoromethyl group" due to its significantly higher electronegativity and lipophilicity. This article describes the first practical method for the production of various arylsulfur pentafluorides and their higher homologues, bis- and tris(sulfur pentafluorides), from the corresponding diaryl disulfides or aryl thiols. The method consists of two steps: (Step 1) treatment of a diaryl disulfide or an aryl thiol with chlorine in the presence of an alkali metal fluoride, and (step 2) treatment of the resulting arylsulfur chlorotetrafluoride with a fluoride source, such as ZnF2, HF, and Sb(III/V) fluorides. The intermediate arylsulfur chlorotetrafluorides were isolated by distillation or recrystallization and characterized. The aspects of these new reactions are revealed and reaction mechanisms are discussed. As the method offers considerable improvement over previous methods in cost, yield, practicality, applicability, and large-scale production, the new processes described here can be employed as the first practical methods for the economical production of various arylsulfur pentafluorides and their higher homologues, which could then open up a new era of "super-trifluoromethyl" arene chemistry and its applications in many areas.
- Umemoto, Teruo,Garrick, Lloyd M.,Saito, Norimichi
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supporting information; experimental part
p. 461 - 471
(2012/07/01)
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- INDUSTRIAL METHODS FOR PRODUCING ARYLSULFUR PENTAFLUORIDES
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Industrial methods for producing arylsulfur pentafluorides are disclosed. Methods include reacting arylsulfur halotetrafluoride with hydrogen fluoride in the absence or presence of one or more additives selected from a group of fluoride salts, non-fluoride salts, and unsaturated organic compounds to form arylsulfur pentafluorides.
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Page/Page column 25; 27
(2012/09/10)
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- PROCESSES FOR PREPARING POLY(PENTAFLUOROSULFANYL)AROMATIC COMPOUNDS
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Novel processes for preparing poly(pentafluorosulfanyl)aromatic compounds are disclosed. Processes include reacting an aryl sulfur compound with a halogen and a fluoro salt to form a poly(halotetrafluorosulfanyl)aromatic compound. The poly(halotetrafluoro
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Page/Page column 36-38
(2010/04/25)
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- METHODS FOR PRODUCING ARYLSULFUR PENTAFLUORIDES
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Novel methods for preparing arylsulfur pentafluorides are disclosed. Arylsulfur halotetrafluoride is reacted with a fluoride source under hydrous conditions to form an arylsulfur pentafluoride. The purification method is also disclosed.
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Page/Page column 33-34
(2010/04/03)
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- PROCESS FOR PRODUCING ARYLSULFUR PENTAFLUORIDES
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Novel processes for preparing arylsulfur pentafluorides are disclosed. Processes include reacting at least one aryl sulfur compound with a halogen and a fluoro salt to form an arylsulfur halotetrafluoride. The arylsulfur halotetrafluoride is reacted with a fluoride source to form a target arylsulfur pentafluoride.
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Page/Page column 24
(2008/12/07)
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- Synthesis of pentafluorosulfuranyl arylenes
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A new route has been found leading to the formation of pentafluorosulfuranyl arylenes. In its broadest aspect the process comprises: effecting dehydrohalogenation or dehydrogenation of a pentafluorosulfuranyl compound represented by either of the structur
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Page/Page column 4
(2008/06/13)
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- A new synthesis of pentafluorosulfanylbenzene
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(Equation Presented) A new and convenient three-step synthesis of pentafluorosulfanylbenzene from 1,4-cyclohexadiene with an overall yield of >70% is reported along with a number of derivatization reactions.
- Sergeeva, Tatiana A.,Dolbier Jr., William R.
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p. 2417 - 2419
(2007/10/03)
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- Synthesis of SF5-benzene (SF5C6 H5 by the SF5-halide method
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Several significant and useful syntheses of pentafluorothiobenzene (SF5C6H5) from SF5-halides (SF5X, X=Cl, Br) and cyclohexene or derivatives of cyclohexene are presented.
- Winter, Rolf W.,Gard, Gary L.
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p. 549 - 552
(2007/10/03)
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- METHOD FOR INCORPORATION OF PENTAFLUOROSULFANYL (SF5) SUBSTITUENTS INTO ALIPHATIC AND AROMATIC COMPOUNDS
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The subject invention provides convenient, regiospecific and highly stereoselective addition of SF5Cl in high yield to a variety of alkenes and alkynes.
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- Oxidative fluorination of S, Se and Te compounds
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The synthesis and mechanism of formation of cis- and trans-Ph2SF4 is described. Starting compounds are Ph2S or Ph2SF2 and the oxidizing agent is XeF2 in the presence of Et4NCl. Also described is the synthesis of related chalcogen(IV and VI) fluorides such as t-butylSF3, difluorodibenzothiophene, PhSeF3, Ph2SeF2, PhSF5, p-MeC6H4SF5, PhSeF5, and PhTeF5. The reactions of Ph2S(O)F2 with alcohols and with the H2O-HF-glass system are briefly described.
- Ou, Xiaobo,Janzen, Alexander F.
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p. 279 - 283
(2007/10/03)
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- Oxidative addition and isomarization reactions. the synthesis of cis- and trans-ArSF4Cl and cis- and trans-PHTeF4Cl
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The stereoselective synthesis and isomerization of cis- and trans-ArSF4Cl is described, where Ar = Ph, p-MeC6H4, and p-O2NC6H4. Also briefly described is the synthesis of ArSF5,
- Ou, Xiaobo,Bernard, Guy M.,Janzen, Alexander F.
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p. 1878 - 1884
(2007/10/03)
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