Sulfimides amides

Petfiuorotetramethylene sulfimides are synthesized by the reaction of lithium amide and pnmary amines with (perfluorotetramethylene)sulfur difluonde [7(5] (equation 13) (Table 6) The products can be oxidized with m-chloropetoxybenzoic acid to the corresponding sulfoxirmdes (equation 13) or can be treated with chlorme or bromine to yield N-halo derivatives [76] The reaction of CF3Sp3=NCF3 with nucleophiles takes place by attack of the nucleophile at the positive sulfur center [17] (equation 14)... 

The ammonium salt which results from the transformation of sulfuryl amide can be converted to a silver salt, AgNSO ELO, by silver nitrate (64) and this readily gives AgNS02. The silver salt with methyl iodide yields the N-methyl derivative (LXXI) (61). Since molecular weight determinations show the methyl derivative to be a trimer, it may also be assumed that the salts, and particularly that of silver, are also trimeric. Attempts to isolate the hydrogen compound (LXIX) have so far failed, but Heinze and Meuwsen (64) have prepared many salts of (LXIX). They also were able to show that when the silver salt was decomposed with an equivalent quantity of hydrochloric acid a tribasic acid resulted which was to some extent stable in water. It readily lost two protons, but one proton was split off only with difficulty. The ion (LXX) clearly has a high stability. The dipyridinium salt of the trimeric sulfimide, which is derived from the ion (LXX), can be obtained (la) in a yield of 70% by reaction of amido-sulfuric acid chloride with pyridine at 20° ... 

The quantity of trimeric and tetrameric sulfimide recovered from the reaction products of NH3 with excess S03 in nitromethane did not in any way correspond with that expected from the equations given above and only 10% of the quantity of sulfimide expected was isolated. The residue which had the composition (HNS02)reH2S04 proved to be polysulfimide sulfonic acid (LXXIV) (5). This may be regarded as an imido derivative of the polysulfuric acids. Amides of these acids have already been obtained by Ephraim and Michel (30) by decomposing sulfuryl chloride with ammonia. 

Definite sulfimide sulfonic acids are formed from S03 adducts and sulf-amide in a melt the pyrid nium salt of the sulfamide disulfonic acid, H0(02SNH)2—S03H was obtained. The analogous reaction with imido-sulfamide results in the dipyridinium salt of trisulfimide sulfonic acid H0(02SNH)3—S03H. Besides the pyridinium salts, several potassium, ammonium and sodium salts were prepared (92a). 

It is striking that compound (LXXVa) is clearly much more stable than the isomer (LXXVb) and that hydrolysis leads to different products. Whereas sulfimide in an acid medium gives sulfuryl amide, amidosulfonic acid and sulfuric acid, the hydrolysis of sulfanuric acid leads to imidosulfamide (86). 

Several phenyliodonium imides 465 derived from heteroarenesulfonylamides have been synthesized from (diacetoxyiodo)benzene and the respective amides 464 (Scheme 2.134) [630], Imides 465 can be used as sources of the corresponding heterocycle-containing nitrenes in the copper-catalyzed aziridination and sulfimidization reactions. 

Acylsulfonic acid amides 1-Amino-1-sulfurous acid monoesters Sulfimides... 

Sulfimides from sulfonic acid amides SOgNH SO2NAC... 

Carboxylic acid amides from sulfimides via carboxylic acid hydrazides s. 16, 23... 

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