Zur Chemie des (Trifluormethyl)sulfinylamins, CF ₃ NSO, und verwandter Verbindungen

Abstract

CF3NSFz(1) reagiert rnit PCI, zu CF3NSCIz (2) und dieses in bekannter Weise mit AgzO zur Titelverbindung CF3NSO (4). 4 bildet sich auch aus CF3NCIz (3) und SOCl,. Es reagiert rnit XeF2 zu CF3NSOFz (5) und rnit HCI zu CF3NHz (6). Alle Reaktionen wurden auch mit den entsprechenden C2F5-Verbindungen (1 a -6a) durchgefuhrt. Das Hydrochlorid von 6a zersetzt sich uber (CzF&NH . HCI (11) zu CF3CFz-N=CFCF, (13), wogegen 6a CF3CN (14) ergibt.CF3 -NSN -CF3 (8) lsBt sich direkt aus 4 oder aus 2 und 3 bzw. 2 und 6 erhalten. CF3 -NSN -G F S (9) bzw. C2F5 -NSN -CzF5 (10) bilden sich bei der Reaktion von 2a mit 6 . 1 reagiert rnit BBr, zu (Trifluormethyl)irnidoschwefeldibromid (7). On the Chemistry of (Trifluoromethyl)sulfinylamine, CF,NSO, and Related CompoundsCF3NSFz (1) reacts with PCI, to yield CF3NSClz (2) which is converted to the title compound 4 with Ag20 as is well known. 4 can also be obtained from CF3NCIz (3) and SOCl,, and it reacts with XeFz to form CF3NSOF2 (5) and with HCI to yield CF3NHz (6). All reactions were also carried out with the corresponding C2F5 compounds (la-6a). The hydrochloride of 6a decomposes via (C2F5),NH . HCI (11) yielding CF3CFz -N = CFCF3 (13) in contrast to 6 a, which forms CF3CN (14). CF3 -NSN -CF3 (8) can be obtained directly from 4 or from 2 and 3 or 2 and 6, respectively. CF3 -NSN -CzF5 (9) and C2F5 -NSN -CzF5 (10) are formed in the reaction of 2a with 6 . 1 reacts with BBr, to form (trifluoromethy1)imidosulfur dibromide (7).Im Rahmen unserer Untersuchungen iiber das Reaktionsverhalten der NSO-Gruppe, z. B. bei Fluorierungen, zeigten sich -im Gegensatz zu organischen') und anorganischen Sulfinylaminen wie FNSOZ) -die (Perfluoralky1)sulfinylamine als besonders geeignet. Wir setzten (Trifluormethy1)imidoschwefeldifluorid (1)3) abweichend von Lit.4) nicht rnit AICl,, sondern analog Lit.5) rnit PC1, urn. Dabei konnte die Ausbeute an (Trifluormethy1)imidoschwefeldichlorid (2)4) auf 72% gesteigert werden. 2 entsteht fast quantitativ auch bei der Reaktion von (Trifluormethy1)dichloramin (3)6,7) rnit Schwefeldichlorid. Schliealich konnte (Trifluormethy1)sulfinylamin (4)4) praparativ durch Reaktion von 2 mit Silberoxid in Perfluormethyldecalin bei <O"C rnit 77% Ausbeute erhalten werden. Die Bildung von 4 beobachteten wir auch bei der Reaktion von 3 rnit Thionylchlorid.Auch bei der UV-Belichtung einer Losung von Bis(trifluormethyl)quecksilber8) und CINS02) in Methylenchlorid konnten wir die Bildung von 4 beobachten, wahrend bei Belichtung von Trifluormethyliodid mit INS09) in Methylenchlorid nur Iod und Hexafluorethan nachgewiesen wurden. Die Reaktion von 1 mit Spuren Wasser auf Aluminiumoxid fuhrte nur zu CF3NC0, SOFz

Convenient Access to α‐Fluorinated Alkylammonium Salts

“…Since the initial syntheses of CF 3 OH and CF 3 NH 2 , a wealth of computational work has been published relating to α‐fluoroalkyl alcohols and amines5 demonstrating the relevance of these compounds to the scientific community. By comparison, however, there has been a lack of reports relating to the bulk syntheses of these or higher primary, perfluorinated analogues,3,4 6 which is likely due to the cumbersome preparation of the precursor compounds.…”

“…The thermally unstably compounds CF 3 OCl and CF 3 NCl 2 are not readily available and were prepared according to relatively cumbersome procedures starting from COF 2 and ClF or BrCN and SF 4 1b. 2 Small amounts of CF 3 NH 2 and C 2 F 2 NH 2 have also been obtained from the corresponding N‐chloro compounds and Me 3 SiH3 or the corresponding perfluoroalkylsulfinylamines, R f NSO (R f =perfluorated alkyl group) and HCl 4. Since the initial syntheses of CF 3 OH and CF 3 NH 2 , a wealth of computational work has been published relating to α‐fluoroalkyl alcohols and amines5 demonstrating the relevance of these compounds to the scientific community.…”

“…[1b,2] Small amounts of CF 3 NH 2 and C 2 F 2 NH 2 have also been obtained from the corresponding Nchloro compounds and Me 3 SiH [3] or the corresponding perfluoroalkylsulfinylamines,R f NSO (R f = perfluorated alkyl group) and HCl. [4] Since the initial syntheses of CF 3 OH and CF 3 NH 2 ,aw ealth of computational work has been published relating to a-fluoroalkyl alcohols and amines [5] demonstrating the relevance of these compounds to the scientific community.B yc omparison, however, there has been al ack of reports relating to the bulk syntheses of these or higher primary,p erfluorinated analogues, [3,4 6] which is likely due to the cumbersome preparation of the precursor compounds.…”

Functionalization of Organic Molecules by Xenon Fluorides

“…hydrogen fluoride, boron trifluoride and pentafluorothiophenol, resulted in the formation of only sulfoxides and sulfones, their ratio depending on the solvent, the catalyst and the amount of xenon difluoride used 109 . Forster and Downs studied the reactions of xenon difluoride with dimethyl sulfide in detail 110 ; various sulfonyl fluorides were transformed to fluorides in 20-80% yield 111 and (trifluoromethyl)sulfinilamine was fluorinated 112 . Shreeve and coworkers 113 Thiobenzophenone and thiofluorenone are readily transformed with xenon difluoride in to difluoro products 90 , thiobenzoic acid to benzoyl fluoride 90 and dithiobenzoic acid to trifluoromethylbenzene 114 (Scheme 47).…”

CH3N=SF2=NCH3: Structural, Conformational, and Configurational Properties in the Gaseous and in the Condensed Phases

“…In addition to their interesting chemistry (variation of the substituents R, exchange of the sulfur‐bonded fluorines, saturation of the NS bonds to give penta‐ and hexacoordinate species) their structural and bonding aspects are of common interest. Although sulfur nitrogen species with isolated formal double bonds [RN=SX 2 : CF 3 –N=SF 2 ,2 FC(O)–N=SF 2 ,3 C 2 F 5 –N=SF 2 ,4 CF 3 –N=SCl 2 ,5 FC(O)–N=SCl 2 ,6 C 2 F 5 –N=SCl 2 7] and cumulated formal double bonds (RN=S=O: CF 3 –N=S=O,7,8 SF 5 –N=S=O;8,9 RN=S=NR: CH 3 –N=S=N–CH 3 ,10 CF 3 –N=S=N–CF 3 ,11 C 2 F 5 –N=S=N–C 2 F 5 ,11,12 and RN=SF 2 =O: SF 5 N=SF 2 =O13) have been investigated in detail, for RN=SF 2 =NR no reports can be found in the literature.…”