- 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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supporting information
p. 1682 - 1684
(2021/07/19)
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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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- 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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supporting information
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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supporting information
p. 12738 - 12741
(2017/12/06)
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- Synthesis and nucleophilic aromatic substitution of 3-fluoro-5-nitro-1-(pentafluorosulfanyl)benzene
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3-Fluoro-5-nitro-1-(pentafluorosulfanyl)benzene was prepared by three different ways: as a byproduct of direct fluorination of 1,2-bis(3-nitrophenyl)disulfane, by direct fluorination of 4-nitro-1-(pentafluorosulfanyl)benzene, and by fluorodenitration of 3,5-dinitro-1-(pentafluorosulfanyl)benzene. The title compound was subjected to a nucleophilic aromatic substitution of the fluorine atom with oxygen, sulfur and nitrogen nucleophiles affording novel (pentafluorosulfanyl)benzenes with 3,5-disubstitution pattern. Vicarious nucleophilic substitution of the title compound with carbon, oxygen, and nitrogen nucleophiles provided 3-fluoro-5-nitro-1-(pentafluorosulfanyl)benzenes substituted in position four.
- Ajenjo, Javier,Greenhall, Martin,Zarantonello, Camillo,Beier, Petr
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supporting information
p. 192 - 197
(2016/04/05)
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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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- Mono- and dinitration of pentafluorosulfanylbenzenes with [NO 2][BF4], and substrate selectivity (PhSF5 vs PhCF3 and PhSF5 vs PhNO2) in competitive nitration
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PhSF5 1 reacts with NO2+BF 4-/TfOH in CH2Cl2 (DCM) at room temperature to give 1-nitro-3-(pentafluorosulfanyl)benzene 2 in near quantitative yield. The dinitro derivative 4 is synthesized from 2 by reaction with NO2+BF4-/TfOH at 70 °C. The p-MeC6H4SF5 is mononitrated at room temperature with NO2+BF4-/DCM and dinitrated with NO2+BF4-/TfOH. Substrate selectivity (kPhSF5kRPh) in competitive nitration for PhSF5/PhCF3 and PhSF5/PhNO 2 with NO2+BF4- in DCM at room temperature was determined at 21.3 and ~1 respectively. Relative stability of the corresponding benzenium ions were gauged by DFT from the isodesmic proton transfer reaction SF5-C6H 6+ + R-C6H5 → SF 5-C6H5 + R-C6H6 + (R = CF3 and NO2). These studies indicate that reactivity of ArSF5 in SEAr is similar to ArNO 2.
- Okazaki, Takao,Laali, Kenneth K.
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- Processes for Preparing 1,3-Dinitro-5-(Pentafluorosulfanyl)Benzene and its Intermediates
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New processes for preparing 1,3-dinitro-5-(pentafluorosulfanyl)benzene starting from 4-(pentafluorosulfanyl)toluene or (pentafluorosulfanyl)benzene are disclosed. The useful intermediates are also disclosed.
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Page/Page column 9
(2011/12/14)
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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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- New 4-pentafluorosulfanyl and 4-perfluoroalkylthio derivatives of 1-chloro-2-nitro- and 1-chloro-2,6-dinitrobenzenes
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New 4-pentafluorosulfanyl and 4-perfluoroalkylthio derivatives of 1-chloro-2-nitrobenzene and 1-chloro-2,6-dinitrobenzene were prepared from the corresponding bis(4-chloro-3-nitrophenyl)disulfide and bis(4-chloro-3,5-dinitrophenyl)disulfide, respectively. The SF5 derivatives were obtained by fluorination of the disulfides with AgF2 according to Sheppard's method, while perfluoroalkylation was carried out by means of thermolytic reactions with xenon(II) bis(perfluoroalkylcarboxylates). The introduction of fluorine-containing, electron-withdrawing substituents into the aromatic ring (in the presence of other deactivating groups) reinforces the activation of the halogen substituent towards nucleophilic attack. Several nucleophilic substitution reactions have been carried out with these compounds, and as a result, some N- and S-containing groups were introduced in the benzene ring. For example, the previously unknown SF5, CF3S, and C2F5S analogues of trifluralin (Treflan) were prepared and characterized. Additional synthetic possibilities for heterocyclic chemistry are presented on the basis of reactions of the new 1-chloro-2,6-dinitrobenzene derivatives with ethyl thioglycolate wherein fluorine-containing derivatives of benzothiazole N-oxide were obtained as the main products.
- Sipyagin, Alexey M.,Enshov, Vyacheslav S.,Kashtanov, Sergei A.,Bateman, Colin P.,Mullen, Brian D.,Tan, Ying-Teck,Thrasher, Joseph S.
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p. 1305 - 1316
(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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- 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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- 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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