- Validation of Arylphosphorothiolates as Convergent Substrates for Ar-SF 4Cl and Ar-SF 5Synthesis
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In this manuscript we describe the oxidative fluorination of aryl phosphorothiolates to access Ar-SF4Cl compounds. These compounds serve as precursors for the highly coveted Ar-SF5 compounds. The use of phosphorothiolates as starting materials permits access to Ar-SF4Cl from a wide variety of available starting materials, namely boronic acids, diazonium salts, aryl iodides, thiophenols, or simple arenes. The protocol has been demonstrated for 10 examples and showed good tolerance to various functional groups. Finally, we demonstrated that AgBF4 can be used as a fluorinating agent, affording good yields of an Ar-SF5.
- Wang, Lin,Ni, Shengyang,Cornella, Josep
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p. 4308 - 4312
(2021/06/02)
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- 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 0049-0050; 0055-0056
(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 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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- Pyridine-promoted dediazoniation of aryldiazonium tetrafluoroborates: Application to the synthesis of SF5-substituted phenylboronic esters and iodobenzenes
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Pyridine promotes dediazoniation of aryldiazonium tetrafluoroborates. The formed aryl radicals were trapped with B2pin2, iodine, or tetrahydrofuran to afford boronic esters, iodobenzenes and benzenes, respectively. The application to the synthesis of (pentafluorosulfanyl) phenylboronic esters, iodo(pentafluorosulfanyl)benzenes and (pentafluorosulfanyl)benzene is shown.
- Iakobson, George,Du, Junyi,Slawin, Alexandra M. Z.,Beier, Petr
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p. 1494 - 1502
(2016/04/09)
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- 4-(Pentafluorosulfanyl)benzenediazonium Tetrafluoroborate: A Versatile Launch Pad for the Synthesis of Aromatic SF5 Compounds via Cross Coupling, Azo Coupling, Homocoupling, Dediazoniation, and Click Chemistry
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The reagent 4-(pentafluorosulfanyl)benzenediazonium tetrafluoroborate (1) was synthesized and isolated as a stable salt for the first time; its application in a wide assortment of transformations was subsequently investigated. A series of novel SF5-bearing alkenes, alkynes, and biaryl derivatives were synthesized by employing Heck-Matsuda, Sonogashira, and Suzuki coupling protocols. Dediazoniation with TMSX (X = Hal; N3; and CN) and NH4SCN in [BMIM][BF4] as solvent furnished the corresponding p-SF5-C6H4X derivatives. The azide derivative p-SF5-C6H4N3 entered into click chemistry with phenylacetylenes to furnish the corresponding triazoles. The 4,4′-bis(pentafluorosulfanyl)biphenyl was synthesized by homo-coupling using Pd(OAc)2. The corresponding azo compounds were obtained through azo-coupling with reactive aromatic nucleophiles (1,3-dimethoxybenzene, 1,3,5-trimethoxybenzene, 1,2,4-trimethoxybenzene, aniline and phenol). Fluorodediazoniation in [BMIM][PF6] and [BMIM][BF 4] selectively furnished the fluoro derivative p-SF 5-C6H4F. Dediazoniation in [BMIM][NTf 2] gave p-SF5-C6H4OS(O)(CF 3)=NSO2CF3 as the major and p-SF 5-C6H4-NTf2 as the minor products. Homolytic dediazoniation in MeCN/NaI gave the unsymmetrical biaryls p-SF 5-C6H4-Ar (ArH = mesitylene and p-xylene) along with p-SF5-C6H4I. Analysis of the dediazoniation product mixtures indicated that dediazoniation of p-SF 5-C6H4N2+ BF 4- in low nucleophilicity, highly ionizing, solvents (TfOH, TFE, HFIP, TFAH) is mainly heterolytic, while in MeOH it is mainly homolytic. The isodesmic reaction p-SF5-C6H 4+ + R-C6H5 → SF 5-C6H5 + p-R-C6H4 + (with R = NO2, CF3, H) was gauged by DFT at various levels and by PCM. Copyright
- Okazaki, Takao,Laali, Kenneth K.,Bunge, Scott D.,Adas, Sonya K.
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p. 1630 - 1644
(2014/03/21)
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- 4-(Pentafluorosulfanyl)benzenediazonium Tetrafluoroborate: A Versatile Launch Pad for the Synthesis of Aromatic SF5 Compounds via Cross Coupling, Azo Coupling, Homocoupling, Dediazoniation, and Click Chemistry
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The reagent 4-(pentafluorosulfanyl)benzenediazonium tetrafluoroborate (1) was synthesized and isolated as a stable salt for the first time; its application in a wide assortment of transformations was subsequently investigated. A series of novel SF5-bearing alkenes, alkynes, and biaryl derivatives were synthesized by employing Heck-Matsuda, Sonogashira, and Suzuki coupling protocols. Dediazoniation with TMSX (X = Hal; N3; and CN) and NH4SCN in [BMIM][BF4] as solvent furnished the corresponding p-SF5-C6H4X derivatives. The azide derivative p-SF5-C6H4N3 entered into click chemistry with phenylacetylenes to furnish the corresponding triazoles. The 4,4′-bis(pentafluorosulfanyl)biphenyl was synthesized by homo-coupling using Pd(OAc)2. The corresponding azo compounds were obtained through azo-coupling with reactive aromatic nucleophiles (1,3-dimethoxybenzene, 1,3,5-trimethoxybenzene, 1,2,4-trimethoxybenzene, aniline and phenol). Fluorodediazoniation in [BMIM][PF6] and [BMIM][BF4] selectively furnished the fluoro derivative p-SF5-C6H4F. Dediazoniation in [BMIM][NTf2] gave p-SF5-C6H4OS(O)(CF3)=NSO2CF3 as the major and p-SF5-C6H4-NTf2 as the minor products. Homolytic dediazoniation in MeCN/NaI gave the unsymmetrical biaryls p-SF5-C6H4-Ar (ArH = mesitylene and p-xylene) along with p-SF5-C6H4I. Analysis of the dediazoniation product mixtures indicated that dediazoniation of p-SF5-C6H4N2+ BF4- in low nucleophilicity, highly ionizing, solvents (TfOH, TFE, HFIP, TFAH) is mainly heterolytic, while in MeOH it is mainly homolytic. The isodesmic reaction p-SF5-C6H4+ + R-C6H5 → SF5-C6H5 + p-R-C6H4+ (with R = NO2, CF3, H) was gauged by DFT at various levels and by PCM.
- Okazaki, Takao,Laali, Kenneth K.,Bunge, Scott D.,Adas, Sonya K.
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p. 1630 - 1644
(2015/10/05)
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- Pd-catalyzed direct arylation of nitro(pentafluorosulfanyl)benzenes with aryl bromides
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Limited methods for the synthesis of SF5-substituted compounds significantly restrict their widespread application. A Pd-catalyzed direct arylation of nitro(pentafluorosulfanyl)benzenes with aryl bromides is reported. This protocol provides a facile and straightforward access to diversified SF5-containing aryl derivatives. The notable features of this reaction are its synthetic simplicity, high reaction efficiency, and good regioselectivity.
- Wang, Chao,Yu, Yan-Bo,Fan, Shilu,Zhang, Xingang
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supporting information
p. 5004 - 5007
(2013/10/22)
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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; experimental part
p. 461 - 471
(2012/07/01)
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- INDUSTRIAL METHODS FOR PRODUCING ARYLSULFUR PENTAFLUORIDES
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Industrial methods for producing arylsulfur pentafluorides are disclosed. Methods include reacting arylsulfur halotetrafluoride with hydrogen fluoride in the absence or presence of one or more additives selected from a group of fluoride salts, non-fluoride salts, and unsaturated organic compounds to form arylsulfur pentafluorides.
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Page/Page column 21-24
(2012/09/10)
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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 16
(2008/12/07)
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- Synthesis and characterisation of 3- and 4-(pentafluorosulfanyl)benzoic acid derivatives. X-ray structure of 3-SF5-C6H4-COOH
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The high yield synthesis of 3- and 4-(pentafluorosulfanyl)benzoic acid derivatives is described starting from the NO2-derivatives, which are reduced to the corresponding anilines. Then the NH2- group is converted to bromide and subsequently to the HC{double bond, long}O moiety. The benzaldeydes are then oxidised to the corresponding benzoic acids. The X-ray structure of 3-SF5-C6H4-COOH is also reported.
- Zarantonello,Guerrato,Ugel,Bertani,Benetollo,Milani,Venzo,Zaggia
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p. 1449 - 1453
(2008/09/18)
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- The synthesis and biological activity of pentafluorosulfanyl analogs of fluoxetine, fenfluramine, and norfenfluramine
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The trifluoromethyl group of fluoxetine 1 and fenfluramine and norfenfluramine, 2 and 3, was substituted by the pentafluorosulfanyl group. On examination of the efficacy of the pentafluorosulfanyl containing compounds as inhibitors of 5-hydroxytryptamine receptors, it was found that substitution could lead to enhanced selectivity and in the case of the pentafluorosulfanyl analog of fenfluramine, 18, it significantly enhanced potency against the 5-HT2b, 5-HT2c, and 5-HT6 receptors.
- Welch, John T.,Lim, Dong Sung
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p. 6659 - 6666
(2008/03/28)
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- ORGANOBORON COMPOUND COMPRISING SULPHUR PENTAFLUORIDE
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The invention provides organoboron compounds which comprise at least one sulphur pentafluoride group, and which display improved properties when compared with known organoboron compounds, and show particular promise for application in liquid crystal technology. Most preferably, the organoboron compounds comprise pentafluorosulphuryl phenyl boronic acid derivatives. Methods for the preparation of such compounds from organic precursors comprising at least one sulphur pentafluoride group, via intermediate bromo compounds, are also disclosed.
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Page/Page column 9
(2008/06/13)
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- Pentafluorosulfanylphenyl-substituted benzoylguanidines, processes for their preparation, their use as medicament or diagnostic aid, and medicament comprising them
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Pentafluorosulfanylphenyl-substituted benzoylguanidines of the formulae I and II in which R1, R1′, R2, R2′, R3, R3′, R4 and X have the meanings indicated in the claims, are suitable as antiarrhythmic medicaments with a cardioprotective component for the prophylaxis of infarction and treatment of infarction and for the treatment of angina pectoris. They also inhibit preventively the pathophysiological processes associated with the development of ischemia-induced damage, especially in the triggering of ischemia-induced cardiac arrhythmias.
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Page/Page column 22
(2010/02/10)
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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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- Liquid crystals based on hypervalent sulfur fluorides: Pentafluorosulfuranyl as polar terminal group
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The somewhat 'exotic' pentafluorosulfuranyl functionality is one of the strongest electron-withdrawing groups with a purely inductive effect owing to its chemical stability and the resulting high dipole moment of its aromatic derivatives, this group was crucial to the design and synthesis of a new class of highly polar liquid crystals (such as 1) for application in active matrix displays. A computational model was developed with the aim to understand and predict the electrooptic properties of liquid crystals based on hypervalent sulfur fluorides.
- Kirsch, Peer,Bremer, Matthias,Heckmeier, Michael,Tarumi, Kazuaki
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p. 1989 - 1992
(2007/10/03)
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- Herbicidal isoxazole and 2-cyano-1,3-dione compounds
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The invention relates to compounds of formulae (Ia), (Ib) or (Ic): STR1 and to their use as herbicides.
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