An improved method for the fluorination of arylsulfur chlorotetrafluorides to arylsulfur pentafluorides

Lummer, Katrin; Ponomarenko, Maxim V.; Röschenthaler, Gerd‐Volker; Bremer, Matthias; Beier, Petr

doi:10.1016/j.jfluchem.2013.10.009

Cited by 33 publications

(14 citation statements)

References 17 publications

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“…Among X‐SF 4 ‐Y molecules, we were particularly interested in X‐SF 4 Cl compounds, which are important intermediates for the synthesis of X‐SF 5 as well as other X‐SF 4 ‐Y compounds [4–6, 9, 11, 12, 24] . Due to their high reactivity, this compound class resisted structural characterization through X‐ray diffraction thus far.…”

Section: Resultsmentioning

confidence: 99%

The Supramolecular Structural Chemistry of Pentafluorosulfanyl and Tetrafluorosulfanylene Compounds

Liebing

Pitts

Reimann

et al. 2021

Chemistry A European J

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The analysis of crystal structures of SF5‐ or SF4‐containing molecules revealed that these groups are often surrounded by hydrogen or other fluorine atoms. Even though fluorine prefers F⋅⋅⋅H over F⋅⋅⋅F contacts, the latter appeared to be important in many compounds. In a significant number of datasets, the closest F⋅⋅⋅F contacts are below 95 % of the van der Waals distance of two F atoms. Moreover, a number of repeating structural motifs formed by contacts between SF5 groups was identified, including different supramolecular dimers and infinite chains. Among SF4‐containing molecules, the study focused on SF4Cl compounds, including the first solid‐state structure analyses of these reactive species. Additionally, electrostatic potential surfaces of a series of Ph‐SF5 derivatives were calculated, pointing out the substituent influence on the ability of F⋅⋅⋅X contact formation (X=F or other electronegative atom). Interaction energies were calculated for different dimeric arrangements of Ph‐SF5, which were extracted from experimental crystal structure determinations.

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Section: Resultsmentioning

confidence: 99%

The Supramolecular Structural Chemistry of Pentafluorosulfanyl and Tetrafluorosulfanylene Compounds

Liebing

Pitts

Reimann

et al. 2021

Chemistry A European J

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“…Diese aktuelle Methode erlaubt die verlässliche Synthese von neuen Schlüsselintermediaten in der Form von Aryl‐Tetrafluor‐λ 6 ‐Sulfanyl‐Chlorid Zwischenstufen (Aryl‐SF 4 Cl), die anschließend mittels Cl‐F‐Austausch in die entsprechenden Aryl‐SF 5 ‐Verbindungen überführt werden können. Mittlerweile gibt es zahlreiche, milde Methoden für die zweite Stufe (Cl‐F‐Austausch), die vorrangig in den Laboratorien von Umemoto, Dolbier, Shibata und Beier entwickelt wurden. Die erste Stufe (Synthese von Aryl‐SF 4 Cl) benötigt jedoch Chlorgas als Reagenz.…”

Section: Figureunclassified

Die SF₅‐Gruppe zugänglicher gemacht: Eine gasfreie Synthese von Aryl‐Tetrafluor‐λ⁶‐Sulfanyl‐Chloriden

Pitts¹,

Bornemann²,

Liebing³

et al. 2019

Angewandte Chemie

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Moderne Pentafluorosulfanyl(SF5)‐Chemie hat eine entscheidende Schwachstelle: synthetische Zugänglichkeit. In dieser Arbeit präsentieren wir die erste Methode für die Herstellung von Aryl‐SF4Cl‐Verbindungen (Schlüsselintermediate für die Aryl‐SF5‐Synthese), die durch Einsatz von einfach zu handhabender Trichlorisocyanursäure, Kaliumfluorid und katalytischer Mengen an Säure, ohne die Verwendung von gefährlichen Fluorierungsmitteln und oder Gasen als Reaktanden, auskommt. Diese simplen, milden Bedingungen erlauben den direkten Zugang zu Aryl‐SF4Cl‐Intermediaten die mit bisherigen Methoden entweder noch nicht synthetisiert wurden oder nicht synthetisiert werden konnten. Des Weiteren eröffnet diese Methode den Zugang zu Aryl‐SF3‐ und Aryl‐SeF3‐Verbindungen, was die Anwendung dieser Chemie über die Grenzen der SF5‐Funktionalisierung hinaus erweitert und somit eine Lösung zum komplexen Problem der oxidativen Fluorierung anbietet.

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“…The intermediates ArSF 4 Cl are rathers ensitive compounds and the Cl/F exchange reactionn ecessitates the use of anhydrous HF,I F 5 ,o rA g 2 CO 3 or can be accomplished by heatingwith ZnF 2 or AgF. [16][17][18][19][20][21][22] The second practical methodf or the synthesis of arylsulfur pentafluorides is the direct fluorination of diaryl disulfides. [9,12,23] It has been reported only for ni-tro(pentafluorosulfanyl)benzenes (Scheme 1B), which are produced in this way in multikilogramq uantities.…”

Section: Introductionmentioning

confidence: 99%

“…This reaction requires a large excess of chlorine gas (which can be substituted by trichloroisocyanuric acid) and potassium fluoride, and displays a relatively good substrate scope. The intermediates ArSF 4 Cl are rather sensitive compounds and the Cl/F exchange reaction necessitates the use of anhydrous HF, IF 5 , or Ag 2 CO 3 or can be accomplished by heating with ZnF 2 or AgF . The second practical method for the synthesis of arylsulfur pentafluorides is the direct fluorination of diaryl disulfides .…”

Section: Introductionmentioning

confidence: 99%

Preparation of (Pentafluorosulfanyl)benzenes by Direct Fluorination of Diaryldisulfides: Synthetic Approach and Mechanistic Aspects

Ajenjo

Klepetářová

Greenhall³

et al. 2019

Chemistry A European J

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Direct fluorination of ortho-, meta-a nd para-substituteda romatic 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 SF 5 -containing building blocks. Fluorinationsi nb atch and flow modes were compared.Acomprehensive computational study was carried out employingd ensity functional and wave functionm ethods to elucidate the reaction mechanism of the transformation of ArSF 3 into ArSF 5 .E liminating various nonradical pathways, it has been shown that the reaction proceedsb yaradical mechanism,i nitiated by the attack of the FC on the ArSF 3 moiety,p ropagated via an almostb arrierless F 2 + ArSF 4 C!ArSF 5 + FC step and terminated by the ArSF 4 C + FC!ArSF 5 .M ost of the calculated data are in very good agreement with experimental observations concerning the ortho-substituent effect on the reaction rates and yields.

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An improved method for the fluorination of arylsulfur chlorotetrafluorides to arylsulfur pentafluorides

Cited by 33 publications

References 17 publications

The Supramolecular Structural Chemistry of Pentafluorosulfanyl and Tetrafluorosulfanylene Compounds

The Supramolecular Structural Chemistry of Pentafluorosulfanyl and Tetrafluorosulfanylene Compounds

Die SF₅‐Gruppe zugänglicher gemacht: Eine gasfreie Synthese von Aryl‐Tetrafluor‐λ⁶‐Sulfanyl‐Chloriden

Preparation of (Pentafluorosulfanyl)benzenes by Direct Fluorination of Diaryldisulfides: Synthetic Approach and Mechanistic Aspects

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An improved method for the fluorination of arylsulfur chlorotetrafluorides to arylsulfur pentafluorides

Cited by 33 publications

References 17 publications

The Supramolecular Structural Chemistry of Pentafluorosulfanyl and Tetrafluorosulfanylene Compounds

The Supramolecular Structural Chemistry of Pentafluorosulfanyl and Tetrafluorosulfanylene Compounds

Die SF5‐Gruppe zugänglicher gemacht: Eine gasfreie Synthese von Aryl‐Tetrafluor‐λ6‐Sulfanyl‐Chloriden

Preparation of (Pentafluorosulfanyl)benzenes by Direct Fluorination of Diaryldisulfides: Synthetic Approach and Mechanistic Aspects

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Die SF₅‐Gruppe zugänglicher gemacht: Eine gasfreie Synthese von Aryl‐Tetrafluor‐λ⁶‐Sulfanyl‐Chloriden