Advances in the Chemistry of Sulfimides and Related Compounds

Abstract

The present review deals with the chemistry of sulfimides and related compounds. Some problems concerning the nature of the S=N bond, methods of synthesis, spectral and chemical properties of sulfimides and iminosulfinic acid derivatives (chlorides, amides, esters) are considered.

Mechanism for the reactions of sulfides with hypochlorous acid and N‐chlorosulfon‐amides: Formation of solvated chlorosulfonium cation and λ4‐sulfane intermediates

“…N ‐chloroamides are widely used chlorinating agents; the chlorine transfer reactions to sulfides and amines have been thoroughly investigated. The chlorine potential of N ‐chlorosulfonamides increases with the increasing acidity of the protons of parent amides (MsNH − << MsNH 2 < < MsNHCl) .…”

“…Therefore, one can conclude that, in contrast with the reactions of sulfides with HOCl, [25] the reactions of sulfides with N-chlorosulfonamides do not proceed with the S N 2 mechanism, presented on Scheme 4. N-chloroamides are widely used chlorinating agents [11,35,36] ; the chlorine transfer reactions to sulfides [1,[9][10][11][12][13][14] and amines [37][38][39][40] have been thoroughly investigated. The chlorine potential of N-chlorosulfonamides increases with the increasing acidity of the protons of parent amides (MsNH − << MsNH 2 < < MsNHCl).…”

“…[35,[41][42][43] While the N-chlorosulfonamidate anions (12, Q = Me or 4-Me-C 6 H 4 ) cannot transfer chlorine cation at all, the N-chlorosulfonamides (15) are good, and the N,Ndichlorosulfonamides (18) are extremely strong reactants. N-chlorosulfonamides (15) can also chlorinate the N-chlorosulfonamidate anions (12) to form N,Ndichlorosulfonamides (18) in disproportionation (Scheme 5). N,N-dichlorosulfonamides (18) chlorinate sulfonamidate anions (21) in the backward step of the equilibrium.…”

“…The mechanism of the reactions of sulfides with hypochlorites [1][2][3][4][5][6][7][8] and N-chloroamides [9][10][11][12][13][14] has been widely investigated by kinetic and nonkinetic methods. The reactions have been proposed to proceed by a polar mechanism, via the formation of chlorosulfonium cation [1][2][3][4][5][6][7][8][9][10][11][12][13][14] (R 2 SCl + ) and oxychloro-or aminochloro-λ 4sulfane [4,5,7,15] intermediates (earlier sulfuranes, R 2 SClNu, Nu = R'O or ArSO 2 NH, Equation (1)).…”

Imination of Sulfur-Containing Compounds: XXXVI. A New Method of Synthesis and Oxidative Arylsulfonylimination of Sulfenamides

“…It is known that N-(arylsulfenyl)-N,N'-bis(arylsulfonyl)sulfinimidamides react with an equimolar amount of sodium thiolate to give 1 equiv of the corresponding disulfide and 1 equiv of N,N'-bis(phenylsulfonyl)sulfinimidamide. Presumably, the latter are formed as intermediate products in reactions of sodium thiolates with N,N-dichloro sulfonamides at a ratio of 5 : 2; these reactions underlie a number of preparative procedures for the synthesis of N,N'-disubstituted sulfinimidamides [18]. Another equally important reaction leading to sulfinimidamides is oxidative imination of sulfenamides with N-halo derivatives [4,5].…”