2613-27-6Relevant academic research and scientific papers
AgBF4-Mediated Chlorine-Fluorine Exchange Fluorination for the Synthesis of Pentafluorosulfanyl (Hetero)arenes
Tanagawa, Kazuhiro,Zhao, Zhengyu,Saito, Norimichi,Shibata, Norio
supporting information, p. 1682 - 1684 (2021/07/19)
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.
METHOD OF PRODUCING PENTAFLUOROSULFANYL AROMATIC COMPOUND
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Paragraph 0049-0052, (2020/03/09)
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.
Enhanced preparation of aryl and heteryl sulfur pentafluorides using mercury (II) oxide - hydrogen fluoride media as a fluorinating reagent
Fetyukhin, Volodymyr N.,Guzyr, Olexandr I.,Kozel, Volodymyr N.,Rozhenko, Olexandr B.,Rusanov, Eduard B.,Shermolovich, Yuriy G.
, (2020/09/18)
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.
Preparation of (Pentafluorosulfanyl)benzenes by Direct Fluorination of Diaryldisulfides: Synthetic Approach and Mechanistic Aspects
Ajenjo, Javier,Klepetá?ová, Blanka,Greenhall, Martin,Bím, Daniel,Culka, Martin,Rulí?ek, Lubomír,Beier, Petr
supporting information, p. 11375 - 11382 (2019/08/20)
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.
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
Cui, Benqiang,Kosobokov, Mikhail,Matsuzaki, Kohei,Tokunaga, Etsuko,Shibata, Norio
, p. 5997 - 6000 (2017/07/10)
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.
Silver-induced self-immolative Cl-F exchange fluorination of arylsulfur chlorotetrafluorides: Synthesis of arylsulfur pentafluorides
Cui, Benqiang,Jia, Shichong,Tokunaga, Etsuko,Saito, Norimichi,Shibata, Norio
, p. 12738 - 12741 (2017/12/06)
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.
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
Sipyagin, Alexey M.,Bateman, Colin P.,Matsev, Andrej V.,Waterfeld, Alfred,Jilek, Robert E.,Key, Christopher D.,Szulczewski, Gregory J.,Thrasher, Joseph S.
, p. 203 - 210 (2015/03/05)
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
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
Umemoto, Teruo,Garrick, Lloyd M.,Saito, Norimichi
, p. 461 - 471 (2012/07/01)
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.
METHODS FOR PRODUCING ARYLSULFUR PENTAFLUORIDES
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Page/Page column 42, (2010/04/03)
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.
PROCESS FOR PRODUCING ARYLSULFUR PENTAFLUORIDES
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Page/Page column 17; 19, (2008/12/07)
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.
