Thioethers with active hydrogen

In fluid-solution systems, the plain hydrogenation of thiophenes to thioether products has been found to be catalyzed by various transition metal complexes surprisingly, none of these catalysts contains either molybdenum or tungsten, which are essential components of heterogeneous HDS catalysts [1 b]. Unpromoted M0S2, on the other hand, is quite active for the HDS of thioethers with no need of assistance by a late transition metal promoter [lb]. 

The addition of a phenylsulfoxide moiety to the end of the side chain markedly changes the activity of this class of compounds. This product, sulfinpyrazone (97-11), stimulates uric acid excretion, making it a valuable dmg for dealing with the elevated serum uric acid levels associated with gout. The compound is stiU one of the more important uricosuric agents available today. The starting ester (96-9) is available by alkylation of the dianion from ethyl malonate with 2-chloroethylphenyl thioether. Condensation with diphenylhydrazine (97-3) in the presence of a base then affords the pyrrazolodione (97-10). Oxidation of sulfur with a controlled amount of hydrogen peroxide leads to the sulfoxide and thus sulfinpyrazone (97-11) [107]. 

H atoms (H ) tend to abstract hydrogen atoms from C-H bonds, particularly if these are activated by neighboring functionalities such as sulfur atoms. The sulfur atom in thioethers was not usually considered as the primary target of H atom despite some, mostly recent, reports showing that bimolecular homolytic substitutions with H atom might occur with thioethers. Because these sulfur atoms are hypervalent, they can form adducts with H atoms. Radical chemistry studies on 1,3,5-trithiane (1,3,5-TT), performed by pulse radiolysis,... 

A Cr(VI) sulfoxide complex has been postulated after interaction of [CrOjtClj] with MejSO (385), but the complex was uncharacterized as it was excessively unstable. It was observed that hydrolysis of the product led to the formation of dimethyl sulfone. The action of hydrogen peroxide on mesityl ferrocencyl sulfide in basic media yields both mesityl ferrocenyl sulfoxide (21%) and the corresponding sulfone (62%) via a reaction similar to the Smiles rearrangement (165). Catalytic air oxidation of sulfoxides by rhodium and iridium complexes has been observed. Rhodium(III) and iridium(III) chlorides are catalyst percursors for this reaction, but ruthenium(III), osmium(III), and palladium(II) chlorides are not (273). The metal complex and sulfoxide are dissolved in hot propan-2-ol/water (9 1) and the solution purged with air to achieve oxidation. The metal is recovered as a noncrystalline, but still catalytically active, material after reaction (272). The most active precursor was [IrHClj(S-Me2SO)3], and it was observed that alkyl sulfoxides oxidize more readily than aryl sulfoxides, while thioethers are not oxidized as complex formation occurs. 

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