- AgBF4-Mediated Chlorine-Fluorine Exchange Fluorination for the Synthesis of Pentafluorosulfanyl (Hetero)arenes
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We report a new protocol to form pentafluorosulfanyl (hetero)arenes via chlorine-fluorine exchange of (hetero)aryl tetrafluorosulfanyl chlorides by AgBF4. The method enables access to electron-deficient pentafluorosulfanyl(hetero)arenes, which are targets that are difficult to synthesize. Two advantages of AgBF4 are its ease of handling and stability. This would be a general transformation protocol.
- Tanagawa, Kazuhiro,Zhao, Zhengyu,Saito, Norimichi,Shibata, Norio
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p. 1682 - 1684
(2021/07/19)
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- 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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- METHOD OF PRODUCING PENTAFLUOROSULFANYL AROMATIC COMPOUND
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A method of producing a pentafluorosulfanyl aromatic compound is provided. A method of producing a pentafluorosulfanyl aromatic compound represented by general formula (3): [in-line-formulae]Ar—(SF5)k??(3)[/in-line-formulae]where Ar is a substituted or an unsubstituted aryl group or heteroaryl group, and k is an integer of 1 to 3;the method includes reacting IF5 with a halotetrafluorosulfanyl aromatic compound represented by general formula (2): [in-line-formulae]Ar—(SF4Hal)k??(2)[/in-line-formulae]where Ar and k are defined as above; and Hal is a Cl group, a Br group, or an I group.
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Paragraph 0049-0052
(2020/03/09)
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- Preparation of (Pentafluorosulfanyl)benzenes by Direct Fluorination of Diaryldisulfides: Synthetic Approach and Mechanistic Aspects
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Direct fluorination of ortho-, meta- and para-substituted aromatic thiols and disulfides using elemental fluorine afforded substituted (pentafluorosulfanyl)benzenes. This work thus represents the first study of the scope and limitation of direct fluorination for the synthesis of new SF5-containing building blocks. Fluorinations in batch and flow modes were compared. A comprehensive computational study was carried out employing density functional and wave function methods to elucidate the reaction mechanism of the transformation of ArSF3 into ArSF5. Eliminating various nonradical pathways, it has been shown that the reaction proceeds by a radical mechanism, initiated by the attack of the F. on the ArSF3 moiety, propagated via an almost barrierless F2+ArSF4 .→ArSF5+F. step and terminated by the ArSF4 .+F.→ArSF5. Most of the calculated data are in very good agreement with experimental observations concerning the ortho-substituent effect on the reaction rates and yields.
- Ajenjo, Javier,Klepetá?ová, Blanka,Greenhall, Martin,Bím, Daniel,Culka, Martin,Rulí?ek, Lubomír,Beier, Petr
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supporting information
p. 11375 - 11382
(2019/08/20)
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- IF5 affects the final stage of the Cl-F exchange fluorination in the synthesis of pentafluoro-λ6-sulfanyl-pyridines, pyrimidines and benzenes with electron-withdrawing substituents
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A difficult chlorine-fluorine (Cl-F) exchange fluorination reaction in the final stage of the preparation of pentafluoro-λ6-sulfanyl-(hetero)arenes having electron-withdrawing substituents has now been elucidated through the use of iodine pentafluoride. A major side-reaction of C-S bond cleavage was sufficiently inhibited by the potential interaction between F and I with a halogen bonding.
- Cui, Benqiang,Kosobokov, Mikhail,Matsuzaki, Kohei,Tokunaga, Etsuko,Shibata, Norio
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p. 5997 - 6000
(2017/07/10)
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- Silver-induced self-immolative Cl-F exchange fluorination of arylsulfur chlorotetrafluorides: Synthesis of arylsulfur pentafluorides
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A novel strategy for the synthesis of arylsulfur pentafluorides by silver carbonate-induced Cl-F exchange fluorination of arylsulfur chlorotetrafluorides is reported. This fluorination does not require any exogenous fluoride sources. Rather, the reaction proceeds via the self-immolation of the substrate Ar-SF4Cl.
- Cui, Benqiang,Jia, Shichong,Tokunaga, Etsuko,Saito, Norimichi,Shibata, Norio
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p. 12738 - 12741
(2017/12/06)
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- Pentafluorosulfanylbenzene chemistry: Role of copper in the Sheppard reaction, direct fluorination of aromatic sulfenyl chlorides, and several potentially energetic SF5-benzenes Dedicated to Teruo Umemoto in recognition of his being awarded the
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In honor of the awardee Dr. Teruo Umemoto and his significant advances in the preparation of pentafluorosulfanylbenzenes [1], we will first overview our results aimed at understanding the importance of copper (and other coinage metals) in W.A. Sheppard's
- Sipyagin, Alexey M.,Bateman, Colin P.,Matsev, Andrej V.,Waterfeld, Alfred,Jilek, Robert E.,Key, Christopher D.,Szulczewski, Gregory J.,Thrasher, Joseph S.
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p. 203 - 210
(2015/03/05)
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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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p. 461 - 471
(2012/07/01)
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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 42
(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 17; 19
(2008/12/07)
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- Process for the synthesis of aryl sulfurpentafluorides
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A process is described for the synthesis of an aryl sulfur pentafluoride compound. In one embodiment of the present invention, there is provided a process for preparing an aryl sulfurpentafluoride compound comprising: combining an at least one aryl sulfur compound with a fluorinating agent to at least partially react and form an intermediate aryl sulfurtrifluoride product; and exposing the intermediate aryl sulfurtrifluoride product to the fluorinating agent and optionally a fluoride source to at least partially react and form the aryl sulfurpentafluoride compound.
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- Synthesis of some arylsulfur pentafluoride pesticides and their relative activities compared to the trifluoromethyl analogues
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Examples of pesticides containing an arylsulfur pentafluoride group were made and their biological activities compared to the corresponding trifluoromethyl analogues. A phenylsulfur pentafluoride analogue of the insecticide fipronil, screened against a resistant strain of Musca domestica, showed higher activity than the corresponding trifluoromethyl analogue.
- Crowley, Patrick J.,Mitchell, Glynn,Salmon, Roger,Worthington, Paul A.
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p. 138 - 142
(2007/10/03)
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- Method of performing a chemical reaction
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According to the present invention there is provided a method of carrying out a chemical reaction between at least two fluids, the method comprising providing respective flow paths for the at least two fluids, said flow paths communicating with each other in a region in which the at least two fluids may contact each other, and flowing the at least two fluids along said flow paths such that in said region the at least two fluids contact each other and a chemical reaction occurs between them, said region having a width perpendicular to the direction of flow in the range 10-10,000 micrometers. It has been found that using a so-called “microreactor”, that is a reactor having dimensions perpendicular to the flow direction of less than 10,000 micrometers, according to the present method, improved control over a fluid chemical reaction can be achieved, which can result in significant improvements in reaction product yield and/or purity, as well as other benefits. The present method has been found to be particularly beneficial for fluorination reactions.
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Page column 6
(2008/06/13)
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- A new method for the synthesis of aromatic sulfurpentafluorides and studies of the stability of the sulfurpentafluoride group in common synthetic transformations
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A new synthesis of aromatic sulfurpentafluoride compounds is described. Subsequent elaboration of the aromatic rings in the presence of the sulfurpentafluoride group is also discussed for a variety of common synthetic methods. This paper also describes ab initio electronic structure calculations of 3- and 4-aminophenylsulfurpentafluoride, compared with 3- and 4-aminobenzotrifluoride, and presents X-ray crystal structures of two aromatic sulfurpentafluoride derivatives. (C) 2000 Elsevier Science Ltd.
- Bowden, Roy D.,Comina, Paul J.,Greenhall, Martin P.,Kariuki, Benson M.,Loveday, Amanda,Philp, Douglas
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p. 3399 - 3408
(2007/10/03)
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- Microreactors for elemental fluorine
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A microreactor has been designed for use with elemental fluorine, both for selective fluorination and for perfluorination of organic compounds.
- Chambers, Richard D.,Spink, Robert C.H.
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p. 883 - 884
(2007/10/03)
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- Preparation of organic pentafluorosulphur compounds
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A process for the preparation of organic pentafluorosulphur compounds which comprises reacting an organic disulphide in a substantially inert solvent with elemental fluorine.
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- Heterocyclic compounds and insecticidal use
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Compounds with insecticidal activity have the formula (I): STR1 wherein R1 is hydrogen, halogen, or a group NR4 R5 wherein R4 and R5 are independently selected from hydrogen or alkyl; R2 is a group --S(O)n R6 wherein n is 0, 1 or 2 and R6 is a haloalkyl group; R3 is --CN or is a group CX--NY1 Y2 for example --CS--NH2 ; and R7 and R8 , which may be the same or different, are halogen.
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