Sulfimides chlorides

In addition to sulfimides, the nitrogen analogs of sulfinates and sulfinamides are chiral and have been obtained as optically active compounds. For instance, the synthesis of diastereomeric menthyl p-toluenesulfinimidoates 90 mentioned above was effected by Cram and his collaborators (18,137) on two ways. The first comprised the reaction of racemic A -tosyl-p-tolueneiminosulfinyl chloride 92 with menthol, followed by separation of the diastereomers of 90, whereas in the second method the reaction of the ester (->45 with chloramine T was utilized. 

Special cases of this reaction are the syntheses of TP betaines (53, see below) from pyrimidin-2-ylcarbamoyl chlorides and trimethylsilyl azide [89JCS(P1)1727] and of TP-1-oxides (31, see below) form pyrimidin-2-yl sulfimides and nitrile oxides [76JCS(P1)2166]. 

A silver ion-mediated desulfurization of thiocarbonyl compounds 163 or 164 followed by condensation with benzohydroxamic acid in the presence of excess triethylamine affords, respectively, dioxazole derivatives 165 or 166 (Scheme 25) <2002H(57)143>. Other reports concern the synthesis of l,4-(oxa/thia)-2-azoles 170-173 from unusual four-atom components such as the sulfur diimides 167, the thietan sulfimide 168, and the carbimidoyl chloride 169 <1996CHEC-II(4)530>. 

For the preparation of this compound the reaction between ammonia and disulfur dichloride, S2CI2, is employed. Besides tetrasulfur tetranitride, sulfimide, S7NH, some sulfur, and ammonium chloride also are formed. 

The l,2-diamino-4-methylthiazole 73 with phosgeniminium chloride gives the thiazolo[3,2-A [l,2,4]triazole derivative 74 (Scheme 45) <1973AGE806>. Reaction of the sulfimide 75 with nitrile oxides forms [l,2,4]triazolo[l,5- ] pyridine 3-oxides 76 in good yields (Scheme 46). This method is applicable to analogous pyrimidines and pyrazines <1976J(P1)2166, 1978BCJ563>. 

Imidation and 3 -methylation were also investigated. Hoping to obtain five-membered cyclic sulfimide 37, imida-tion was carried in methylene chloride but afforded only silanol 38 as the major product. Finally, sulfonium salt 39 was prepared by treatment of sulfide 32 with methyl iodide in dry ethanol, and was found to be fairly stable under dry conditions. 

A ,2,4-Benzothiadiazines (168) are obtained as minor products, along with open-chain sulfimides (167), by treating iV-arylbenzamidines (166) with A -phenylthiomorpholine (Scheme 25 route a). The yields of benzothiadiazine are improved (43-60%) with 4,4 -thiobismorpholine as the sulfur carrier, and are optimized (30-86%) by using sulfenyl chlorides (Scheme 25 route b) in place of the sulfenamides. Corroborative evidence for the structure of 1,3-diphenyl-1 A, 2,4-benzothiadiazine (170 R = Ph, X = H) was obtained by an alternative synthesis (in 98% yield) involving successive treatment of the amidine (169) with A -chlorosuccinimide and sodium hydroxide <83JCS(P1)49). 

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. 

As Hantzsch and Stuer (62) suggested, trimeric sulfimide (LXXVa) should have an isomer (LXXVb), to which the name sulfanuric acid has been given. However, this acid, like sulfimide, cannot be isolated as the hydrogen compound itself, though the acid chloride (LXXVI) is readily accessible. It can be made by the reaction of amidosulfonic acid with PCI5 and thermal decomposition of the product (73, 74)-... 

N-Aryl sulfimides. N-Aryl sulfimides can be prepared in satisfactory yields by reaction of anilines with sulfides and N-chlorosuccinimide, /-butyl hypochlorite, or sulfuryl chloride. ... 

During the Second World War a number of triorganolead-substituted sulfonamides, phthalimides, and a sulfimide were prepared and tested as potential sternutators 111, 112,113). The methods of preparation included the reaction of triethyl- or tripropyllead chloride with the sodium derivative of a sulfonamide, and the reaction between triethyl- or tripropyllead hydroxide and a sulfonamide. Both reactions were generally carried out in ethanol, and the product was precipitated by the addition of water. This demonstrates the hydrolytic stability of these compounds. The phthalimides and the sulfimide were prepared from the organolead hydroxides. They show the same high hydrol)rtic stability. 

---