Dialkyl sulfone diimines. Synthesis, Raman spectra, chemical and physical properties

Abstract

An improved synthesis of the recently described dialkyl sulfone diimines1•2 in acetonitrile is described. Reaction of chloramine-ammonia with dialkyl sulfides in 2-propanol has been shown to yield sulfoxide and sulfone imine by-products, as well as sulfone diimines. Their formation is best accounted for by assuming that displacement of sulfur on chloramine occurs to some extent on chlorine, as well as on nitrogen. The crystalline and aqueous solution Raman spectra of dimethyl, diethyl, and methyl dodecyl sulfone diimine have been measured and are shown to be consistent with tetrahedral bonding for sulfur (C2v local symmetry). Tentative band assignments are presented based on comparison with analogous compounds and the Raman spectra of dimethyl sulfide, diethyl sulfide, and dimethyl sulfone imine. Characteristic vibrational bands for R2S(NH)2 are tabulated and the spectral evidence for hydrogen bonding of this new semipolar group is discussed. The sulfone diimines were shown to be considerably more stable thermally than sulfimines but less stable than sulfoxides. Hydrolysis by acid or base catalysis could not be effected, although decomposition via other routes occurred in acid.2 The basicity and metal complexing abilities 436 m 506 r(SN2), rock 460 w 486 t(SN«), twist 679 vs, P 691 vs, P 700 vs, P rs(CS), sym stretch 720 r(NH2), NH2 rock 741 m 742 s 770 s yaa(CS), asym stretch 947 s, P 902 vs(SN), sym stretch (975 vw)' 929 ras(SN), asym stretch 1162 w 1131 r(NHi), NH2 rock 1026 w,P

Sulfonimidamides and Imidosulfuric Diamides: Compounds from an Underexplored Part of Biologically Relevant Chemical Space

“…It should be noted that according to the spectral data, the N‐H moieties did not participate in hydrogen bonding to a significant extent under these conditions. Stretching of the N=S=O moieties appeared as two bands at 1220–1270 cm −1 and approximately 1025 cm −1 ; these values are in agreement with the literature data for 22 and show that these fragments have similar properties in all the three compounds …”

“…It was found that all three compounds 20 – 22 bearing S=NH moieties were weak bases (p K a values for the corresponding conjugated acids are 3.78, 3.06, and 3.48, respectively; for 22⋅ HCl, lit . p K a =3.24±0.02).…”

Synthesis of Pseudopeptides with Sulfoximines as Chiral Backbone Modifying Elements

“…[25] In 1989 Mock et al introduced sulfoximines [26] and sulfodiimine as analogous transition-state inhibitors for carboxypeptidase A. [27] Those functional groups are chemically stable, and with their sp 3 -hybridized [28,29] sulfur atom they successfully mimic the tetrahedral intermediate in carboxamide addition reactions. [27b] We postulate that the use of such units for backbone modifications could lead to new pseudopeptides with higher stability against enzymatic degradation and thus give rise to potential new enzyme inhibitors.…”

Synthese von neuen 1,2,6‐Thiadiazinen und 1,3,2,4‐Dithiadiazinen

“…Die Umsetzung des Sulfonylchlorids 6 ' ) mit 1 ad zu den N-Sulfonylschwefeldiimiden 8ad fiihrt in verdiinnter Natronlauge zu den blangelben, an der Luft stabilen 3,3-Dialkyl-l, 3 Charakterisiert wurden die Substanzen 4a -c, 9a -f und 10a -d elementaranalytisch und IRspektroskopisch anhand der gegeniiber den ringoffenen Verbindungen 3a -c, 7a -f und 8a -d fehlenden NH-Valenzschwingung im Bereich 3300 -3200 cm -' . Die Carbonylabsorption von 4 a -c und 9 a -f tritt bei 1620-1630 c m -' in Erscheincng.…”