2613-26-5Relevant 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
, 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
-
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.
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.
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
supporting information, 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.
Synthesis of 4-(pentafluorosulfanyl)benzenediazonium tetrafluoroborate and analogs and their application for the preparation of SF5-aromatics
-
Page/Page column 10; 11, (2016/02/05)
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.
Synthesis and nucleophilic aromatic substitution of 3-fluoro-5-nitro-1-(pentafluorosulfanyl)benzene
Ajenjo, Javier,Greenhall, Martin,Zarantonello, Camillo,Beier, Petr
supporting information, p. 192 - 197 (2016/04/05)
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.
Mono- and dinitration of pentafluorosulfanylbenzenes with [NO 2][BF4], and substrate selectivity (PhSF5 vs PhCF3 and PhSF5 vs PhNO2) in competitive nitration
Okazaki, Takao,Laali, Kenneth K.
, p. 96 - 100 (2014/08/05)
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.
Processes for Preparing 1,3-Dinitro-5-(Pentafluorosulfanyl)Benzene and its Intermediates
-
Page/Page column 9, (2011/12/14)
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.
A new synthesis of pentafluorosulfanylbenzene
Sergeeva, Tatiana A.,Dolbier Jr., William R.
, p. 2417 - 2419 (2007/10/03)
(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.
New 4-pentafluorosulfanyl and 4-perfluoroalkylthio derivatives of 1-chloro-2-nitro- and 1-chloro-2,6-dinitrobenzenes
Sipyagin, Alexey M.,Enshov, Vyacheslav S.,Kashtanov, Sergei A.,Bateman, Colin P.,Mullen, Brian D.,Tan, Ying-Teck,Thrasher, Joseph S.
, p. 1305 - 1316 (2007/10/03)
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.
