A quest for new acyclic sulfur(IV) fluorides

Synthesis of Trifluoromethanesulfinamidines and -sulfanylamides

“…Such considerations led us to envisage the preparation of 1a starting from Ruppert’s reagent ( 4a ) and DAST derivatives ( 3 ), via a trifluoromethyl difluorosulfur intermediate ( 2a ) (Scheme ). To our knowledge, preparation of the later type of compounds has only been reported once: compound 2 (R 1 = R 2 = Me) was prepared very inconveniently by reaction of CF 3 SF 3 and TMS−NMe 2 between −196 and −78 °C.…”

Azoltrifluormethylschwefeldifluoride

“…Als zweite Mo È glichkeit ist in der Literatur die CsF-katalysierte Addition von SF 4 an perfluorierte Alkene (CF 3 ±CF=CF 2 ) [11] beschrieben. Im Vergleich zum SF 4 wird die Reaktivita È t der schwefelgebundenen Fluorsubstituenten kaum gea È ndert, mit N-Trimethylsilylaminen R 2 NSiMe 3 erfolgt bereits unter milden Bedingungen die Substitution eines Fluors unter Bildung von R F SF 2 NR 2 (R F = i-C 3 F 7 , R = Me [12], R F = CF 3 , R = Me [13] ± u È berfu È hrt [14]. Als weitere Mo È glichkeit, zu R 2 N±SF 2 ±R F -Derivaten zu gelangen, haben russische Arbeitsgruppen die Addition von Aminoschwefeltrifluoriden an Perfluoralkene beschrieben [15].…”

Reactions of (Carbonylimido)sulfur(IV) Derivatives with TAS-Fluoride, (Me2N)3S+Me3SiF2-

“…Another indication of ψ-pentacoordination with axially bonded fluorines and equatorial CF 3 groups is a 3 J (CF 3 −SF) value of approximately 18 Hz. For the neutral species CF 3 SF 3 (21.7 Hz), (CF 3 ) 2 SF 2 (19.5 Hz), azole-SF 2 CF 3 (19.6−19.9 Hz) (azole = triazole, pyrazole, imidazole), and Me 2 NSF 2 CF 3 (12.4 Hz), this coupling constant is found in the same range.…”