A convenient synthetic route to 2,4,6-tris(chlorosulfonyl)- and 2,4,6-tris(fluorosulfonyl)phenol, aniline and chlorobenzene

Boiko, V. N.; Filatov, Andrey A.; Yagupolskii, Yurii L.; Tyrra, Wieland; Naumann, Dieter; Pantenburg, Ingo; Fischer, Hanno; Schulz, Frank

doi:10.1016/j.jfluchem.2011.06.045

Cited by 14 publications

(14 citation statements)

References 28 publications

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“…As we showed earlier [2], boiling of chlorobenzene 1 alcoholic solution gave phenol 2 (Scheme 1). The reaction presumably proceeded via s-complex A formation followed by destruction that may occur in two different ways (Scheme 1) both leading to the formation of phenol 2.…”

Section: Reactions With O-nucleophilessupporting

confidence: 55%

“…This conditions for aniline 3 synthesis are more convenient and productive than the method described by us earlier [2] starting with 2,4,6-tris(chlorosulfonyl)aniline.…”

Section: Reactions With N-nucleophilesmentioning

confidence: 87%

“…In the frame of our continuous interest to aromatic systems modified by fluorine containing electron withdrawing substituents we would like to attract attention to the accessible, stable and intriguing system of symmetric tris(fluorosulfonyl)benzenes [1,2] as a flat platform for three general pathway designs of various molecules (Picture 1):…”

Section: Introductionmentioning

confidence: 99%

“…Simple and effective preparative synthetic procedures for the syntheses of 2,4,6-tris(fluorosulfonyl)chlorobenzene (1), corresponding phenol 2 and aniline 3 have been elaborated and presented in our previous publications [1,2] that made these compounds available for thorough investigations.…”

Section: Introductionmentioning

confidence: 99%

“…Some comparison of fluorosulfonyl aromatic moiety and activated aromatic halogen atom reactivity towards various nucleophilic agents [2,[14][15][16] did not give exact predictions about 2,4,6-tris(fluorosulfonyl)chlorobenzene 1 regioselective behavior in the basic conditions. The later has different electrophilic centers and its reactions with nucleophiles may cause to unexpected but important results.…”

Section: Introductionmentioning

confidence: 99%

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Interaction of 2,4,6-tris(fluorosulfonyl)chlorobenzene with O-, N-, S-, C-nucleophiles and F-anion

Filatov

Boiko

Yagupolskii

2012

Journal of Fluorine Chemistry

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Section: Reactions With O-nucleophilessupporting

confidence: 55%

“…This conditions for aniline 3 synthesis are more convenient and productive than the method described by us earlier [2] starting with 2,4,6-tris(chlorosulfonyl)aniline.…”

Section: Reactions With N-nucleophilesmentioning

confidence: 87%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Interaction of 2,4,6-tris(fluorosulfonyl)chlorobenzene with O-, N-, S-, C-nucleophiles and F-anion

Filatov

Boiko

Yagupolskii

2012

Journal of Fluorine Chemistry

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Schwefel(VI)‐fluorid‐Austausch (SuFEx): Eine weitere gute Anwendung für die Click‐Chemie

et al. 2014

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Arylsulfonylchloride (z. B. Ts‐Cl) sind die am häufigsten eingesetzten SVI‐Elektrophile in der organischen Synthesechemie, und auch die Stammverbindung, das Sulfurylchlorid (O2SVICl2), wurde zur Synthese von Sulfaten und Sulfamiden genutzt. Allerdings wird die gewünschte Halogenidsubstitution oftmals durch die Zersetzung des Schwefelelektrophils in SIV‐Spezies und Cl− verhindert, denn die SVI‐Cl‐Bindung ist äußerst reduktionsanfällig. Mit Schwefel(VI)‐fluoriden (z. B. R‐SO2‐F und SO2F2) verläuft die Umsetzung hingegen ausschließlich über den Substitutionsweg. Wie es bei der Click‐Chemie zumeist der Fall ist, wurden viele entscheidende Aspekte der Reaktivität von Schwefel(VI)‐fluoriden vor langer Zeit in Deutschland entdeckt.6a Überraschenderweise gerieten diese außerordentlichen Arbeiten in der Mitte des 20. Jahrhunderts ziemlich abrupt aus dem Blickfeld. In diesem Aufsatz versuchen wir, dieser Chemie neues Leben einzuhauchen. Insbesondere stützen wir uns dabei auch auf John Hyatts unbeachtet gebliebene Veröffentlichung über CH2CH‐SO2‐F aus dem Jahr 1979.98 Wir tragen mehrere neue Beobachtungen bei, einschließlich dem Befund, dass das ansonsten sehr stabile Gas SO2F2 eine exzellente Reaktivität unter den richtigen Umständen aufweist. Wir zeigen auch, dass Protonen oder Siliciumzentren den Austausch von S‐F‐Bindungen gegen S‐O‐Bindungen aktivieren können und dass der Sulfat‐Konnektor überraschend hydrolysestabil ist. Anwendungen dieser kontrollierbaren Ligationschemie auf kleine Moleküle, Polymere und Biomoleküle werden diskutiert.

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Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

et al. 2014

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Aryl sulfonyl chlorides (e.g. Ts-Cl) are beloved of organic chemists as the most commonly used S(VI) electrophiles, and the parent sulfuryl chloride, O2 S(VI) Cl2 , has also been relied on to create sulfates and sulfamides. However, the desired halide substitution event is often defeated by destruction of the sulfur electrophile because the S(VI) Cl bond is exceedingly sensitive to reductive collapse yielding S(IV) species and Cl(-) . Fortunately, the use of sulfur(VI) fluorides (e.g., R-SO2 -F and SO2 F2 ) leaves only the substitution pathway open. As with most of click chemistry, many essential features of sulfur(VI) fluoride reactivity were discovered long ago in Germany.6a Surprisingly, this extraordinary work faded from view rather abruptly in the mid-20th century. Here we seek to revive it, along with John Hyatt's unnoticed 1979 full paper exposition on CH2 CH-SO2 -F, the most perfect Michael acceptor ever found.98 To this history we add several new observations, including that the otherwise very stable gas SO2 F2 has excellent reactivity under the right circumstances. We also show that proton or silicon centers can activate the exchange of SF bonds for SO bonds to make functional products, and that the sulfate connector is surprisingly stable toward hydrolysis. Applications of this controllable ligation chemistry to small molecules, polymers, and biomolecules are discussed.

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A convenient synthetic route to 2,4,6-tris(chlorosulfonyl)- and 2,4,6-tris(fluorosulfonyl)phenol, aniline and chlorobenzene

Cited by 14 publications

References 28 publications

Interaction of 2,4,6-tris(fluorosulfonyl)chlorobenzene with O-, N-, S-, C-nucleophiles and F-anion

Interaction of 2,4,6-tris(fluorosulfonyl)chlorobenzene with O-, N-, S-, C-nucleophiles and F-anion

Schwefel(VI)‐fluorid‐Austausch (SuFEx): Eine weitere gute Anwendung für die Click‐Chemie

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

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