Convenient synthesis and isolation of trifluoromethylthio-substituted building blocks

Trifluoromethylthiolation of aromatic compounds with different electrophilic reagents of the type ArNHSCF3 was studied in the presence of triflic acid as an activator. The effect of the reagent structure on the reactivity was studied with three different reagents: PhNHSCF3 (H/SCF3, 1a), 4‐ClC6H4NHSCF3 (Cl/SCF3, 1b) and C6F5NHSCF3 (F5/SCF3, 1c). p‐Chloro substituted reagent 1b was more stable than the unsubstituted 1a and was the most effective because it could not react by trifluoromethylthiolation of itself. This reaction was the most important side reaction of 1a. The pentafluoro derivative 1c was less reactive. Solvent played an important role in the transformation and, depending on the substrate, dichloromethane, hexane or trifluoroacetic acid gave the best yield of various trifluoromethylthiolated aromatic molecules (63–98 %).

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“…p ‐Tolyl(trifluoromethyl)sulfane and o ‐Tolyl(trifluoromethyl)sulfane (3o): , Colorless oil. 61 mg (63 %, o/p 45:55).…”

Section: Methodsmentioning

confidence: 99%

“…13 C NMR (126 MHz,CDCl 3 ,25°C): δ = 148.2,145.3,140.9,129.5 (q,J = 309 Hz),126.2,117.2,115.1,36.2,31.4 ppm. 19 [21] Colorless liquid. 102 mg (93 %).…”

Section: -(Tert-butyl)-3-[(trifluoromethyl)thio]benzene-12-diol (3i)mentioning

confidence: 99%

Diversification of Trifluoromethylthiolation of Aromatic Molecules with Derivatives of Trifluoromethanesulfenamide

2018

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“…Elimination proceeds readily at room temperature with the alkyl groups n ‐decyl and benzyl; in the case of the aryl groups C 6 H 5 and C 6 F 5 , it was greatly accelerated by gentle warming (40 °C). Trifluoromethylation of thiols (or thiolate anions) can be accomplished by various existing procedures, which include the use of CF 3 I or convenient surrogates thereof, CF 3 I⋅D, as well as different electrophilic trifluoromethylating reagents . It is worth noting, however, that with our system even the “deactivated” thiol C 6 F 5 SH is efficiently trifluoromethylated.…”

Section: Methodsmentioning

confidence: 99%

The First Organosilver(III) Fluoride, [PPh₄][(CF₃)₃AgF]

Joven-Sancho

Baya

Martín

et al. 2020

Chemistry A European J

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Organosilver(III) fluoride complexes have been assigned a key role in different fluorination processes. To the best of our knowledge, however, none of them seem to have been isolated or even detected thus far. Here we report on the successful synthesis of the trifluoromethyl derivative [PPh4][(CF3)3AgF], which has been isolated in high yield. The thermodynamic stability of the Ag−F bond is shown by calculation and demonstrated by multistage mass spectrometry (MSn) under collision‐induced dissociation (CID) conditions. Nevertheless, the substantial elongation found in the Ag−F bond (X‐ray) is correlated with a marked nucleophilic character of the terminal F ligand. This Ag−F bond is, in fact, quite reactive: it suffers hydrolysis and is also solvolyzed by thiols.

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“…The indirect methods include halogen-fluorine exchange 10 and trifluoromethylation of sulfur-containing compounds. 11 However, both of the indirect methods require harsh conditions and have a narrow substrate scope. The direct trifluoromethylthiolation methods are based on either electrophilic or nucleophilic pathways.…”

Section: Introductionmentioning

confidence: 99%

A facile trifluoromethylthiolation of 3-chloro-1H-inden-1-ones employing AgSCF3 and KI

Dong¹,

Zhang²,

Liu³

et al. 2016

Arkivoc

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Convenient synthesis and isolation of trifluoromethylthio-substituted building blocks

Cited by 57 publications

References 32 publications

Diversification of Trifluoromethylthiolation of Aromatic Molecules with Derivatives of Trifluoromethanesulfenamide

Diversification of Trifluoromethylthiolation of Aromatic Molecules with Derivatives of Trifluoromethanesulfenamide

The First Organosilver(III) Fluoride, [PPh₄][(CF₃)₃AgF]

A facile trifluoromethylthiolation of 3-chloro-1H-inden-1-ones employing AgSCF3 and KI

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Convenient synthesis and isolation of trifluoromethylthio-substituted building blocks

Cited by 57 publications

References 32 publications

Diversification of Trifluoromethylthiolation of Aromatic Molecules with Derivatives of Trifluoromethanesulfenamide

Diversification of Trifluoromethylthiolation of Aromatic Molecules with Derivatives of Trifluoromethanesulfenamide

The First Organosilver(III) Fluoride, [PPh4][(CF3)3AgF]

A facile trifluoromethylthiolation of 3-chloro-1H-inden-1-ones employing AgSCF3 and KI

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The First Organosilver(III) Fluoride, [PPh₄][(CF₃)₃AgF]