Sulfur Chains Terminated by Sulfonyl Groups

These compounds, disulfonyl mono-, di-, and polysulfides, are intermediates between organic mono-, di-, and polysulfides and the polythio-nates, in the sense that they are formally derived from the polythionic acids by substitution of alkyl or aryl groups for the hydroxyl groups of the acids. The monosulfides, like the trithionate ion, contain three sulfur atoms in a chain, but only the middle one is divalent. There is thus no real structural problem with regard to branching or nonbranching in disulfonyl monosulfides and trithionates. 

The first representative, di-p-toluenesulfonyl trisulfide, was discovered by Blomstrand 81) in 1870. On treatment of sodium p-toluenethiosuIf onate with iodine in ethanol, he obtained the trisulfide instead of the expected disulfide. Otto and Troeger 182) in 1891 showed that the disulfide is initially formed but rearranges easily into mono- and trisulfide. By the action of iodine or chlorine on potassium benzene- and p-tolucuethiosulfo-nate they prepared the complete series of mono-, di-, and trisulfides. Troeger and Hornung (217) extended the benzene- and p-tol uenesulfonyl series to include the tetrasulfides all members were obtained from mono- or disulfur dichloride by reaction with an excess of the appropriate sodium or potassium sulfinate or thiosulfonate in an inert solvent. 

The compounds are solids at room temperature, the melting points being 133°, 76-77°, 103°, and 84-85° for dibenzenesulfonyl mono-, di-, tri-, and tetrasulfides, respectively, and 138°, 114°, 183°, and 90° for the p-toluene compounds. Christiansen 89) observed an unstable form, mp 160°, of di-p-toluenesulfonyl trisulfide. 

The only aliphatic derivatives reported are dimethanesulfonyl disulfide 86) and trisulfide 88), and diethanesulfonyl tri- and tetrasulfides (82). The first two are solids with mp 61° and 70°, respectively, the last two were obtained as oils. 

Disulfonyl disulfides possess pseudohalogen properties (86), and the tri-and tetrasulfides in reactions with nucleophilic reagents behave as sulfur 

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