Sulfonyl diimide,

O. E. Geiculescu, Y. Xie, R. Rajagopal, S. E. Creager, D. D. DesMarteau, J. Huor. Chem. 2004, 125, 1179-1185. Dflithium bis[(perfluoroalkyl)sulfonyl]diimide salts as electrolytes for rechargeable lithium batteries. 

The carbon-carbon double bond can be reduced by diimide prepared in solution in a number of ways.34 183,184 Oxidation of hydrazine with oxygen (air) or H202 in the presence of a catalytic amount of Cu(II) ion was the first method to generate and use diimide in hydrogenation.183-185 Acid-catalyzed decomposition of alkali azido-dicarboxylates,185,186 as well as thermal or base-catalyzed decomposition of aromatic sulfonyl hydrazides,183,184 are also useful methods for preparing the diimide reducing agent. 

Carbodiimides are a unique class of reactive organic compounds having the heterocumu-lene structure R—N=C=N—R. They can be formally considered to be the diimides of carbon dioxide or the anhydrides of 1,3-substituted ureas, and they are closely related to the monoimides of carbon dioxide, the isocyanates. The substituent R can be alkyl, aryl, acyl, aroyl, imidoyl or sulfonyl, but nitrogen, silicon, phosphorous and metal substituted carbodiimides are also known. The unsubstituted carbodiimide HN=C=NH is isomeric with cyanamide, H2NCN. Mono substituted carbodiimides, generated in the thermolysis of 1-substituted tetrazoles, can be isolated at liquid nitrogen temperature but isomerize to the cyanamides at higher temperatures. ... 

Diimide is also formed in the thermal and base-catalyzed decomposition of benzene-, 4-methylben-zene-," 4-nitrobenzene-, and 2,4,6-triisopropylbenzene-sulfonyl hydrazide. ... 

Diimide occurs only as an unstable intermediate in the hydrolysis of azodi-carboxylic acid, in the alkaline cleavage of benzene sulfonyl hydrazide, hydroxyl-amine-O-sulfonic acid and chloramine, in the oxidation of hydrazine, and in several other organic decomposition reactions . At room temperature it readily undergoes decomposition, disproportionation, and in the presence of symmetrical multiple bonds (like the ones in olefins) hydrogen transfer reactions ... 

The thermal instability of sulfonyl hydrazides allows them to be used for the reduction of carbon-carbon double bonds the reaction depends on the in situ formation of the highly reactive diimide intermediate (86), which is a good reducing agent for alkenes. Tosylhydrazide can be used for this reduction, but triisopropylbenzenesulfonyl hydrazide (87) is preferred because it decomposes to the diimide at low temperature. In the final step, the diimide reduces the alkene to the alkane, as indicated in Scheme 56. 

It has been shown that A(-acyl- and fV-sulfonyl-fV -cyanoimidoyl S,5-dialkylsulfur diimides (160 X = COR, or SO2R R = R = Me, and R = Me, R = Et), formed by the condensation of S,S-dialkylsulfur diimides with A(-cyanoimidates followed by A -acylation or fV-sulfonylation at the free sulfimide group, under strong basic conditions, cyclize to li, 2,4-thiadiazines (161 R = Me or Et) albeit in poor yields (Scheme 23) <88CB1689). However, when R = R = trimethylene, the corresponding tetrahydrothieno[2,l-/][l/l, 2,4]thiadiazines (162) are formed in improved yields (20-55%). 

Levchenko and Balon" have examined the regiochemistry of cycloaddition of several symmetrical bis(aryl)sulfonyl sulfur diimides with ( )-piperylene and isoprene which afforded the C-3 and C-5 substituted adducts, respectively (Scheme l-III). These results were confirmed by Wucherpfennig and Kresze, who also found that chloroprene gave the 5-substituted product. ... 

Mock and Nugent investigated the, reaction of N,A( -bis(p-toluene-sulfonyl)sulfur diimide (18) and the isomeric 2,4-hexadienes 10,11, and 12 in an attempt to elucidate the mechanism of sulfur diimide cycloadditions (Scheme 1-IV)." The cycloaddition of 18 and 10 afforded two adducts epimeric at sulfur in a 43 1 ratio, while only one adduct of indeterminate stereochemistry was obtained from the cycloaddition of 18 and 11. No reaction was observed with (Z,Z)-diene 12. Unfortunately, not enough information resulted from these experiments to draw any mechanistic conclusions with regard to the cycloaddition. 

Unsymmetrical sulfur diimides are commonly prepared by two methods. Treatment of a N, N -hw(arylsulfonyl)sulfur diimide with an equivalent of an amine leads to the displacement of one sulfonyl group [Eq. (6)].3... 

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