Reaction of tertiary formamides with sulphur tetrafluoride. Direct synthesis of (trifluoromethyl)amines

Dmowski, Wojciech; Kamiński, Maciej

doi:10.1016/s0022-1139(00)85127-1

Cited by 62 publications

(28 citation statements)

References 11 publications

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“…[458] Bei Stickstoffnucleophilen mit weniger nucleophilen freien Elektronenpaaren am Stickstoffatom, z. Die Amine werden zunächst als Thiuramidsulfide (Schema 124) [107c] ), [107c, 490] N-Alkyldithiocarbamate (Schema 125) [491] oder Formamide [458,492] derivatisiert und danach nucleophil fluoriert. [459,489] Zu den wichtigsten Synthesemethoden für Trifluormethylamine gehçren die nucleophile Fluorierung von Thiocar-bonyl-funktionalisierten Aminen und die N-Trifluormethylierung von Aminen.…”

Section: Synthese Von Trifluormethylaminenunclassified

“…[459,489] Zu den wichtigsten Synthesemethoden für Trifluormethylamine gehçren die nucleophile Fluorierung von Thiocar-bonyl-funktionalisierten Aminen und die N-Trifluormethylierung von Aminen. Die Amine werden zunächst als Thiuramidsulfide (Schema 124) [107c] ), [107c, 490] N-Alkyldithiocarbamate (Schema 125) [491] oder Formamide [458,492] derivatisiert und danach nucleophil fluoriert. Die Formamidmethode liefert die Trifluormethylamine im Allgemeinen in hohen Ausbeuten, erfordert aber die Verwendung von gasfçrmigem und giftigem SF 4 .…”

Section: Synthese Von Trifluormethylaminenunclassified

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Einführung von Fluor und fluorhaltigen funktionellen Gruppen

2013

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Die wichtigsten konzeptionellen Fortschritt auf dem Gebiet der Fluorierungen der letzten zehn Jahre wurden durch die Organo‐ und Übergangsmetallkatalyse ermöglicht. Die schwierigste Umwandlung ist weiterhin die Bildung der C‐F‐Stammbindung, was in erster Linie eine Folge der hohen Hydratationsenergie von Fluorid, starker Metall‐Fluor‐Bindungen und der hoch polarisierten Bindungen zu Fluor ist. Den meisten Fluorierungen fehlt es immer noch an Allgemeingültigkeit, Vorhersagbarkeit und Kosteneffizienz. Trotz der Einschränkungen sind fluorierte Verbindungen mit modernen Fluorierungsmethoden leichter zugänglich als je zuvor. Vor allem beginnen sich die modernen Methoden auf Forschungsgebiete auszuwirken, die keine großen Materialmengen benötigen, z. B. die Wirkstoffentwicklung und die Positronenemissionstomographie. Diese Entwicklungen werden in diesem Aufsatz zusammengefasst und vor dem Hintergrund konventioneller Fluorierungsmethoden diskutiert.

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Section: Synthese Von Trifluormethylaminenunclassified

Einführung von Fluor und fluorhaltigen funktionellen Gruppen

2013

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“…N-Trifluoromethyl substituted amines can be prepared by chlorine/fluorine exchange with hydrogen fluoride or antimony trifluoride applied to N-(trichloromethyl)amines [158], thiuram disulphides and sulphur tetrafluoride [159,160] or silver fluoride [161], N,N-dialkylformamides and sulphur tetrafluoride in the presence of potassium fluoride [160] and arylisocyanates or phosgene arylimines with hydrogen fluoride (Scheme 53) [162].…”

Section: A-trifluoromethyl Aminesmentioning

confidence: 99%

New trends in the chemistry of α-fluorinated ethers, thioethers, amines and phosphines

Manteau

Pazenok

Vors

et al. 2010

Journal of Fluorine Chemistry

360

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“…In fact, the NCF 3 unit is usually constructed by the interconversion of suitable functional groups. Thus, fluorination of N-formylamines, [2] thiuram sulfides, [3] isocyanates, [4] and trichloromethylamines, [5] the reaction of secondary amines with CBr 2 F 2 and tetrakis(dimethylamino)ethylene, [6] and the electrochemical fluorination of alkylamines [7] constitute the still relatively modest set of methods. Of these, the most frequently used approach is the oxidative desulfurization-fluorination of dithiocarbamates first described for the generation of NCF 3 groups by Hiyama and Kuroboshi.…”

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A Ritter‐Type Reaction: Direct Electrophilic Trifluoromethylation at Nitrogen Atoms Using Hypervalent Iodine Reagents

et al. 2010

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The unique features the trifluoromethyl group imparts to pharmaceuticals, crop-protection agents, and functional materials emphasize the necessity to design and develop new reagents and methods for the direct trifluoromethylation of a wide range of organic substrates. Electrophilic trifluoromethylation, that is, the reaction of a suitable reagent capable of formally transferring an intact CF 3 + unit, has been shown to be one of these methods.[1] However, despite the availability of several such effective reagents, the electrophilic trifluoromethylation of hard nucleophiles, for example, oxygen-or nitrogen-centered ones, remains challenging. In particular, the formation of a N À CF 3 bond by such a reaction is still extremely rare. In fact, the NCF 3 unit is usually constructed by the interconversion of suitable functional groups. Thus, fluorination of N-formylamines, [2] thiuram sulfides, [3] isocyanates, [4] and trichloromethylamines, [5] the reaction of secondary amines with CBr 2 F 2 and tetrakis(dimethylamino)ethylene, [6] and the electrochemical fluorination of alkylamines [7] constitute the still relatively modest set of methods. Of these, the most frequently used approach is the oxidative desulfurization-fluorination of dithiocarbamates first described for the generation of NCF 3 groups by Hiyama and Kuroboshi.[8]The single, still very recent report of a direct trifluoromethylation at nitrogen is due to Umemoto and co-workers.[9] They describe the direct N-trifluoromethylation of amines, anilines, and pyridines under very mild conditions achieved with in situ generated and thermally unstable O-(trifluoromethyl)dibenzofuranium salts (corresponding reactions of alcohols and phenols are also known). However, this type of reagent suffers from several shortcomings. The active CF 3 source is obtained by photochemical decomposition of diazonium salts at very low temperature, and the synthesis requires several steps including the construction of a CF 3 O-aryl moiety. It is therefore likely that this methodology will not replace the corresponding functional-group interconversions in the near future.We have shown that a new generation of readily accessible trifluoromethylation reagents based on hypervalent iodine, such as compounds 1 and 2 (Scheme 1), display the desired reactivity towards a number of C-, S-, P-, and O-centered nucleophiles. Despite their purported soft nature, reagents 1 and 2 do trifluoromethylate alcohols and sulfonic acids upon activation with Lewis [10] and Brønsted acids, [11] respectively, thus significantly expanding their application range.During a recent investigation of the direct electrophilic trifluoromethylation of heteroarenes [12] using reagent 1 and catalytic amounts of bis(trifluoromethanesulfonyl)imide (HNTf 2 ) in acetonitrile, we surprisingly found that benzotriazole (3) is converted to the corresponding N-substituted N-trifluoroimidoyl derivative 4, as shown in Scheme 2. The generation of compound 4 corresponds to a novel Rittertype [13] reaction during which a new NÀCF 3 bond...

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Reaction of tertiary formamides with sulphur tetrafluoride. Direct synthesis of (trifluoromethyl)amines

Cited by 62 publications

References 11 publications

Einführung von Fluor und fluorhaltigen funktionellen Gruppen

Einführung von Fluor und fluorhaltigen funktionellen Gruppen

New trends in the chemistry of α-fluorinated ethers, thioethers, amines and phosphines

A Ritter‐Type Reaction: Direct Electrophilic Trifluoromethylation at Nitrogen Atoms Using Hypervalent Iodine Reagents

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