ChemInform Abstract: REACTION OF SULFUR(IV) ACID AMIDES WITH FLUOROSULFURANES

Abstract

Aus den Säureamiden (I) entstehen unter der Einwirkung von SP4 (im Autoklaven) Gemische der Amino‐S‐trifluoride (II) mit den Säurefluoriden (III).

Tris(dimethylamino)oxosulfonium Difluorotrimethylsilicate, (Me2N)3SO+Me3SiF2- (TAOS Fluoride)

“…In the reaction of SF 4 with R 2 NSiMe 3 the sulfur-bonded fluorine substituents are exchanged in a stepwise manner for Me 2 N groups [1][2][3][4][5][6][7][8][9][10][11] forming R 2 NSF 3 (DAST) (dialkylaminosulfur trifluoride), (R 2 N) 2 SF 2 , and (R 2 N) 3 S + Me 3 SiF 2 -(TASF) (tris(dialkylamino)sulfonium "fluoride") 7,8,12 Besides SF 4 13 DAST 14 is of great importance in preparative chemistry for the introduction of fluorine into inorganic and organic molecules; the use of (R 2 N) 2 SF 2 is limited because it tends to decompose explosively at higher temperatures. 10,15 TASF is widely used as a reagent containing an almost "naked" fluoride.…”

“…[16][17][18][19] In its reactivity OSF 4 is similar to SF 4 ; an analogous substitution pattern is expected for the reaction with silylamines. Due to its much more limited availability only a few reactions of this type have been described for OSF 4 . R 2 NS(O)F 3 (R 2 N ) Me 2 N, Et 2 N, Pip) 2,20,21 were isolated, and exchange reactions were reported with R 3 -SiNCNSiR 3 and CF 3 CON(SiMe 3 ) 2 to give RNdS(O)FNR′ 2 (R ) NC, CF 3 C(O); R′ ) Me, Et).…”

“…In the reaction of SF 4 with R 2 NSiMe 3 the sulfur-bonded fluorine substituents are exchanged in a stepwise manner for Me 2 N groups − forming R 2 NSF 3 (DAST) ( d i a lkylamino s ulfur t rifluoride), (R 2 N) 2 SF 2 , and (R 2 N) 3 S + Me 3 SiF 2 - (TASF) ( t ris(di a lkylamino) s ulfonium “ f luoride”) 7,8,12 Besides SF 4 13 DAST 14 is of great importance in preparative chemistry for the introduction of fluorine into inorganic and organic molecules; the use of (R 2 N) 2 SF 2 is limited because it tends to decompose explosively at higher temperatures. , TASF is widely used as a reagent containing an almost “naked” fluoride. − In its reactivity OSF 4 is similar to SF 4 ; an analogous substitution pattern is expected for the reaction with silylamines. Due to its much more limited availability only a few reactions of this type have been described for OSF 4 .…”