- Synthesis, characterization, Co-S bond reactivity of a vitamin B 12 model complex having pentafluorophenylthiolate as an axial ligand
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Heptamethyl (aquo)(pentafluorophenylthiolate)cobyrinate perchlorate, [(H2O)(C6F5S)Cob(iii)7C1ester] ClO4, was synthesized as a B12 model complex having a thiolate ligand in the axial position. The axial ligand change in heptamethyl (diaquo)cobyrinate diperchlorate, [(H2O)2Cob(iii)7C 1ester](ClO4)2, from H2O to C 6F5S- afforded the B12-thiolate complex. The B12-thiolate model complex was characterized by UV-vis, NMR and ESI-mass spectroscopies. The coordination of C6F 5S- to the cobalt center affected the spectroscopic properties of the corrin ring through the electronic interaction between the axial ligand (C6F5S-) and the equatorial ligand (corrin). The photolysis of the B12-thiolate model complex led to the homolytic cleavage of the Co(iii)-S bond to form the Co(ii) complex and the phenyl thiyl radical. The thermolysis of the B12-thiolate model complex also led to the homolytic cleavage of the Co(iii)-S bond. Furthermore, the reactivity of the Co(iii)-S bond of the B12-thiolate model complex was applied to the catalytic oxidation of C6F5SH to C6F5S-SC6F5.
- Tahara, Keishiro,Matsuzaki, Ayaka,Masuko, Takahiro,Kikuchi, Jun-Ichi,Hisaeda, Yoshio
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Read Online
- Convenient Synthesis of Symmetrical Polyfluorinated Diphenyl Sulfides
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Abstract: Thermal properties of decafluorodiphenyl disulfide in the pure state and in the presence of copper and iron metals have been studied. A procedure has been proposed for the synthesis of symmetrical poly-fluorinated diaryl sulfides from diaryl dis
- Bredikhin, R. A.,Maksimov, A. M.,Nikul’shin, P. V.,Platonov, V. E.
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p. 1921 - 1930
(2022/01/24)
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- Interaction of 1,3λ4δ2,2,4-benzodithiadiazines with neutral and charged S-electrophiles: SCl2, C6F5SCl, and NS2+
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[Figure not available: see fulltext.] Reactions of 1,3λ4δ2,2,4-benzothiadiazines with SCl2, C6F5SCl, and [NS2][SbF6] leading to 1,2,3-benzodithiazolium salts (Herz salts) were in
- Makarov, Alexander Yu.,Bagryanskaya, Irina Yu.,Zhivonitko, Vladimir V.
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p. 968 - 972
(2020/08/26)
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- Making the SF5 Group More Accessible: A Gas-Reagent-Free Approach to Aryl Tetrafluoro-λ6-sulfanyl Chlorides
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Modern pentafluorosulfanyl (SF5) chemistry has an Achilles heel: synthetic accessibility. Herein, we present the first approach to aryl-SF4Cl compounds (key intermediates in state-of-the-art aryl-SF5 synthesis) that overco
- Pitts, Cody Ross,Bornemann, Dustin,Liebing, Phil,Santschi, Nico,Togni, Antonio
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supporting information
p. 1950 - 1954
(2019/01/25)
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- Synthesis of chloropolyfluoroarenes from polyfluoroarenethiols and PCl5
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Replacement of the thiol group in polyfluoroarenethiols with chlorine was performed by treating with PCl5 as chlorinating agent. By heating in ampules at 200-220°C polyfluoro- and polyfluorochloroarenethiols with PCl5 mono- and dichloropolyfluoroarenes and also 1,2,4-trifluorotrichlorobenzene were synthesized. Dichloropolyfluoroarenes contain chlorine atoms in ortho- and para-positions.
- Nikul'shin,Maksimov,Platonov
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p. 200 - 205
(2016/04/19)
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- Aerobic oxidation of thiols to disulfides under ball-milling in the absence of any catalyst, solvent, or base
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An efficient aerobic chemoselective oxidation of thiols to disulfides has been achieved under ball-milling over neutral aluminium oxide (grinding auxiliary) in the absence of any catalyst, co-oxidant, solvent, or base. A wide variety of functionalized diaryl, diheteroaryl and dialkyl disulfides have been obtained in high yields. The Royal Society of Chemistry 2013.
- Chatterjee, Tanmay,Ranu, Brindaban C.
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p. 10680 - 10686
(2013/09/02)
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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; scheme or table
p. 461 - 471
(2012/07/01)
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- CARBOCATALYSTS FOR CHEMICAL TRANSFORMATIONS
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The disclosure relates to catalytically active carbocatalysts, e.g., a graphene oxide or graphite oxide catalyst suitable for use in a variety of chemical transformations. In one embodiment, it relates to a method of catalyzing a chemical reaction of an organic molecule by reacting the organic molecule in the presence of a sufficient amount of graphene oxide or graphite oxide for a time and at a temperature sufficient to allow catalysis of a chemical reaction. According to other embodiments, the reaction may be an oxidation reaction, a hydration reaction, a dehydrogenation reaction, a condensation reaction, or a polymerization reaction. Some reactions may include auto-tandem reactions. The disclosure further provides reaction mixtures containing an organic molecule and graphene oxide or graphite oxide in an amount sufficient to catalyze a reaction of the organic molecule.
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Page/Page column 56-57
(2011/12/14)
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- A novel and efficient method for the synthesis of polyfluoroarenesulfonyl bromides from polyfluoroarenethiols
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The first general methodology has been developed for the synthesis of polyfluoroarenesulfonyl bromides from polyfluoroarenethiols. At heating of polyfluoroarenethiols with a mixture of Br2 and fuming HNO3 or Br2, HNO3 and H2SO4 polyfluoroarenesulfonyl bromides were obtained in good yields.
- Platonov, Vyacheslav E.,Bredikhin, Roman A.,Maksimov, Alexander M.,Kireenkov, Victor V.
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experimental part
p. 13 - 16
(2010/06/11)
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- Organofluorine sulfur-containing compounds: V. Joint pyrolysis with chlorine or bromine of polyfluoroarenethioles, polyfluorohetarenethioles, and their derivatives
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Joint pyrolysis with chlorine and bromine of polyfluoroarenethiols, -hetarenethiols, and their derivatives at 300-650°C furnished polyfluorocompounds containing chlorine and bromine. 2005 Pleiades Publishing, Inc.
- Platonov,Maksimov,Dvornikova,Nikul'shin
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p. 1647 - 1653
(2007/10/03)
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- Efficient synthesis of thioesters and amides from aldehydes by using an intermolecular radical reaction in water
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The combination of the water-soluble radical initiator, 2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (VA-044) and the surfactant, cetyltrimethyl-ammonium bromide (CTAB), was found to be the most suitable condition for the effective and direct synthesis of useful active thioesters (pentafluorophenyl thioesters) in water. In addition, the direct amidation of aldehydes was achieved by the addition of the amines to the thioesterification reaction mixture in water.
- Nambu, Hisanori,Hata, Kayoko,Matsugi, Masato,Kita, Yasuyuki
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p. 719 - 727
(2007/10/03)
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- Optical spectroscopy of perfluorothiophenyl, perfluorothionaphthyl, xanthate and dithiophosphinate radicals
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Laser flash photolysis has been used to record the optical spectra of sulfur-containing radicals forming from photodissociation of diphenyl disulfide, perfluorodiphenyl disulfide, perfluoro-2,2′-dinaphthyl disulfide, diisopropyldixantogene and bis(diisobutylthio-phosphoryl-disulfane). The extinction coefficients of absorption bands were determined from the reaction of S-radicals with a stable nitroxyl radical. The rate constant of this reaction was for all radicals close to 109 M-1 s-1 and successfully competes with the reaction of recombination. The presence of a narrow and strong absorption band in the optical spectrum of a nitroxyl radical and the absence of absorption in the reaction products allows one to accurately determine the extinction coefficients of the absorption bands of S-radicals.
- Plyusnin,Ivanov, Yu.V.,Grivin,Vorobjev, D.Yu.,Larionov,Maksimov,Platonov,Tkachenko,Lemmetyinen
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p. 153 - 162
(2007/10/03)
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- Fluoro-organic sulphur-containing compounds. IV. Haloalkylation reactions of polyfluorinated thiophenols with CHal3R compounds in the presence of AlCl3: Synthesis and some reactions of polyfluorophenylthio derivatives of halomethanes
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The haloalkylation of polyfluorothiophenols with CHal3R compounds (Hal=Cl, F; R=Cl, H, C6H5, C6F5) in the presence of AlCl3 has been investigated. The reactions of polyfluorothiophenols 4-XC6F4SH (X=F, H, CH3) with CCl4 and AlCl3 lead to dichloromethane derivatives (4-XC6F4S)2CCl2. The reaction of pentafluorothiophenol with CHCl3 in the presence of AlCl3 gave (C6F5S)2CHCl and (C6F5S)3CH (ratio by GLC 8:1). In the reaction of pentafluorothiophenol with ArCX3 (Ar=C6H5, C6F5; X=Cl, F) compounds (C6F5S)2CClAr (Ar=C6H5, C6F5) together with C6F5SCCl2Ar (Ar=C6H5, C6F5) are formed. Peculiarities of these processes are considered. The hydrolysis of (C6F5S)2CCl2 and C6F5SCCl2C6H5 leads to bis(pentafluorophenyl)dithiocarbonate and the S-(pentafluorophenyl) ester of thiobenzoic acid, respectively. Compounds (C6F5S)2CF2 and (C6F5S)2CClF were obtained from (C6F5S)2CCl2 by the action of caesium fluoride. An attempt to produce these compounds through the action of antimony fluorides was unsuccessful. The compounds (C6F5S)2CCl2, (C6F5S)2CClF and (C6F5S)2CF2 are stable to oxidation. The reactions of (C6F5S)2CF2 and (C6F5S)2CClF with CrO3 in acetic acid proceeded only with the formation of mono-sulphoxide. The conversion is low in the former case.
- Petrova,Platonov,Maksimov
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- Reactions of polyfluoroaromatic imidoyl chloride derivatives with S-nucleophilic reagents
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The interactions of N-pentafluorophenylcarbonimidoyl dichloride, N-pentafluorophenylbenzimidoyl chloride and N-pentafluorophenyl (C-pentafluorophenyl) imidoyl chloride with the S-nucleophilic reagents thiourea, sodium N,N-diethyldithiocarbamate, thiocarbonyl difluoride and bis(trifluoromethyl) trithiocarbonate in the presence of CsF or AgSCF3, or thiophenol and polyfluorinated thiophenols in the presence of anhydrous K2CO3, were studied. Reactions with charged S-nucleophiles and with S-nucleophiles in the presence of a base proceeded with preservation of the N=C multiple bond in the reaction products. By varying the reaction conditions in the case of N-pentafluorophenylcarbonimidoyl dichloride it was possible to substitute one or two chlorines and obtain mono- or di-thioimidates. When C6F5 or SC6F5 groups were present at the C atom of the N=C multiple bond, preferential substitution of the para-fluorine atom occurred. Semiempirical PM3 calculation data were used to explain the direction of these reactions. N-Pentafluorophenylcarbonimidoyl dichloride reacted with sodium N,N-diethyldithiocarbamate or thiourea to give pentafluorophenylisothiocyanate. Depending on the conditions of the reactions of polyfluorinated benzimidoyl chlorides with thiourea, N-pentafluorophenylthioamides and 2-aryl-4,5,6,7-tetrafluorobenzothiazoles were formed. An attempt to produce SCF3 derivatives from AgSCF3 was unsuccessful.
- Petrova,Platonov,Shchegoleva,Maksimov,Haas,Schelvis,Lieb
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- Photochemical Induced Cyclisation of β-Keto Sulfides to Cycloalkanones
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On UV irradiation, β-keto sulfides ArSCH2COPh (Ar = C6F5, C6CL5) cleaved to radicals ArS* and PhCOCH2* which, in one case (Ar = C6F5), were trapped by 1,1-diphenylethylene as the adduct PhCOCH2CH2C(Ph)2SC6F5.With diethyl ether as the solvent the major product was the monothioacetal ArSCH(Me)OEt.The keto sulfide 4-MeSO2C6H4SCH2COPh behaved similarly on irradiation in tetrahydrofuran.Irradiation of the unsaturated β-keto sulfides CH2=CH2COCH2SAr resulted in homolysis of the CH2-S bond to give a 2-oxohex-5-enyl radical, which subsequently cyclised; 4-(pentafluorophenylsulfanyl)cyclohexanone (when Ar = C6F5) and cyclohexanone (when Ar = p-tolyl) were the major products.With β-keto sulfides containing an aryl substituent, ethyl 2-benzyl-2-methyl-3-oxo-4-(pentafluorophenylsulfanyl)butanoate and 1,3-bis(p-tolylsulfanyl)propanone, irradiation resulted in cyclisation with loss of the sulfanyl substituent (probably involving electron transfer) to give 3-ethoxycarbonyl-3-methyl-1,2,3,4-tetrahydronaphthalen-2-one and 6-methylthiochroman-3-one, respectively, in high yield.
- Bahari, Kamarudin B.,Deodhar, Dinker J.,Hesabi, Masoud-M.,Hill, John,Kosmirak, Mario,et al.
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p. 2393 - 2398
(2007/10/02)
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- Perfluororganochalkogeno-ketene. III. Bis(pentafluorphenylsulfanyl)keten (C6F5S)2C=C=O; Synthesen und Charakterisierung
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Bis(pentafluorophenylsulfanyl)ketene (1) may be prepared in good yield by the dehydration of the corresponding substituted acetic acid (C6F5S)2CHC(O)OH (4b) with P4O10 or by the reaction of C6F5SCl with Ag2CCO.The starting material 4b is prepared from CH3C(OCH2CH3)3 and C6F5SCl.Acidolysis of the C6F5S-substituted orthoesters 2 provided the ethyl esters CH3-n(SC6F5)nC(O)OCH2CH3 (3) and acetic acids CH3-n(SC6F5)nC(O)OH (4).
- Haas, Alois,Praas, Hans-Walter,Radau, Godehard
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p. 257 - 260
(2007/10/02)
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- Efficient, high yield oxidation of thiols and selenols to disulphides and diselenides
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Thiols and selenols are smoothly oxidised in high yield to disulphides and diselenides by sodium perborate at room temperature.
- McKillop,Koyuncu,Krief,Dumont,Renier,Trabelsi
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p. 5007 - 5010
(2007/10/02)
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- REACTION OF TELLURIUM CHLORIDE PENTAFLUORIDE, TeF5Cl, WITH NITROGEN NUCLEOPHILES, PREPARATION AND CHARACTERIZATION OF THE ADDUCT (TeF4)2*NR2Cl, WHERE R=CH3, C2H5
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Reactions of TeF5Cl with the nitrogen nucleophiles LiN=C(CF3)2, ((CH3)3Si)2NH, and (CH3)3SiNR2, where R=CH3, C2H5, result in the reduction of the tellurium to Te(IV) and chlorination of the respective nucleophile.Analogous results are obtained in the reaction of TeF5Cl with (CH3)3SiCN, C6F5Li, and C6F5SLi.In the case of (CH3)3SiNR2, the new adducts (TeF4)2*NR2Cl are obtained in high yield.These compounds have been identified through their infrared, 1H, 19F, and 125Te NMR, and mass spectra as well as by elemental analysis.
- Thrasher, Joseph S.,Clark, Matthew,Morken, Peter A.
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p. 235 - 244
(2007/10/02)
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- An Investigation of Potential -Sigmatropic Rearrangements of Pentafluorophenyl-aza-, -thio-, and -methylene-sulphonium Ylides
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The reactions of pentafluoroaniline and pentafluorothiophenol with dimethyl sulphoxide-trifluoroacetic anhydride at low temperatures followed by triethylamine give the N-trifluoroacetyl compound (6) along with the N-trifluoroacetyl-N-methylthiomethyl compound (7) and decafluorodiphenyl disulphide, respectively; no molecular rearrangements occur.Under similar conditions 2,3,4,5,6-pentafluoro-N-methylaniline gives the cyclohexa-2,5-dienone derivative (8) via hydrolysis of the -sigmatropic rearrangement intermediate (9). 2,3,4,5,6-Pentafluorobenzyl bromide and dimethyl sulphide give the sulphonium compound (10) which with butyl-lithium in tetrahydrofuran gives four products derived from the highly reactive -rearrangement intermediate (17): (11) (32percent), (12) (2.5percent), (13) (5percent), and (14) (11percent).One product only (21) (6percent) derived from (17), could be isolated from the reaction in ether.Dimethylsulphonium methylide reacts with hexafluorobenzene to give a much simpler product consisting of (13) (5percent) and (14) (45percent).
- Brooke, Gerald M.,Ferguson, J. A. K. Jamie
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p. 2023 - 2026
(2007/10/02)
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- ATTEMPTED PREPARATIONS OF PHOSPHORANES CONTAINING PERFLUOROPHENYL GROUPS
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The reaction of perfluorophenol with phosphorus pentachloride in the presence of triethylamine or χ-collidine yielded perfluoropentaphenoxyphosphorane, 5, along with perfluorotriphenylphosphate, 6, and perfluorodiphenyl ether, 7.Attempts to prepare penta(perfluorobenzyloxy)phosphorane, 12, by a number of methods failed.Similarly attempts to prepare perfluorothiophenylphosphorane, 19, always resulted in perfluorothiophenyl phosphite, 20, and perfluorodiphenyl disulfide, 21.
- Denney, Donald B.,Denney, Dorothy Z.,Liu, Lun-Tsu
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- Free-Radical Reactions of Fluoroalkanesulfenyl Halides. 4. Reactions of Perfluoroalkane- and Pentafluorobenzenesulfenyl Chlorides with Hydrocarbons in the Presence of Fluorinated Disulfides
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Free-radical reactions of perfluoroalkanesulfenyl chlorides and pentafluorobenzenesulfenyl chloride with cyclohexane and toluene were carried out in the presence of bis(perfluoroalkyl) disulfides and bis(pentaflurophenyl)disulfide to assess the competition between the disulfide and the sulfenyl chloride for reaction with hydrocarbon radicals.With added bis(perfluoroalkyl) disulfides, radical attack occurs only on the sulfenyl chloride, but with added bis(pentafluorophenyl) disulfide, attack occurs on both sulfenyl chloride and disulfide.
- Harris, J. F.
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p. 268 - 271
(2007/10/02)
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