Preparation and Reactivities of S,S-Diaryl-S-aminothiazynes, Ar2S(NR2)(N)

Abstract

Reaction of S,S-diaryl-S-fluorothiazynes6) with cyclic secondary amines gave novel thiazynes, the corresponding S-aminothiazynes in good yields. Spectroscopic studies, measurement of pKa values, pyrolysis and alkylation reactions of the aminothiazynes were carried out.

Ex situ Generation of Thiazyl Trifluoride (NSF3) as a Gaseous SuFEx Hub**

“…Building on these features and their Lewis‐basic nature, fluorinated thiazynes are expected to exhibit unique reactivity compared with their sulfonyl counterparts. However contrasting to the number of reports related to the sulfonyl group, literature on the thiazyl group has remained virtually absent since the 1980s [14, 17, 18] . This discrepancy may be related to the unavailability of the NSF 3 gas.…”

“…[13] The lone pair electron density focuses the highest HOMO orbital coefficient at the thiazyl nitrogen and endows it with several distinct features, such as a nucleophilic character and a pK a of up to 7.7 (Scheme 1C). [14] In addition, the insulating strength of NSF 3 is 1.35 times that of SF 6 , and its Global Warming Potential (GWP) is about one-twentieth that of SF 6 , leading some to investigate it as an alternative for electric insulation. [15,16] Building on these features and their Lewis-basic nature, fluorinated thiazynes are expected to exhibit unique reactivity compared with their sulfonyl counterparts.…”

“…However contrasting to the number of reports related to the sulfonyl group, literature on the thiazyl group has remained virtually absent since the 1980s. [14,17,18] This discrepancy may be related to the unavailability of the NSF 3 gas.…”

“…−27.1±0.1 °C) [11] with a dipole moment of 1.91 D, [12] is significantly more polar than its sulfonyl counterpart SO 2 F 2 (1.11 D) [13] . The lone pair electron density focuses the highest HOMO orbital coefficient at the thiazyl nitrogen and endows it with several distinct features, such as a nucleophilic character and a p K a of up to 7.7 (Scheme 1C) [14] . In addition, the insulating strength of NSF 3 is 1.35 times that of SF 6 , and its Global Warming Potential (GWP) is about one‐twentieth that of SF 6 , leading some to investigate it as an alternative for electric insulation [15, 16] …”

Sulfondiimines: synthesis, derivatisation and application

“…In 1992 the chemistry was extended by Yoshimura, who obtained S -fluorothiazynes 17 in 90% yield after treatment of N -bromo sulfilimine 16b with TBAF in THF (Scheme 5, bottom). 18 Of interest here, 17 were highly versatile intermediates for the syntheses of S , S -diaryl sulfoximines or sulfondiimines 18 . For example, sulfondiimines 18a were obtained from 17 by the addition of primary amines in presence of TFA in yields ranging from 79% to 98%.…”