Anodic Oxidation of Sulfur Compounds

Industrial work has been concentrating on the search for alternative processes for the production of tetraalkylthiuram disulfides 325). 

Their synthesis can also be carried out as a two-phase electrolysis, using ammonium salts 326). Sulfenamides can be produced by oxidizing tetraalkylthiuram disulfides in the presence of amines 321  

Tetraalkylthiuram disulfides are used as vulcanization enhancers, fungicides, and seed treatment agents. Commercial production is still performed by means of oxidation with Cl2. Although their electrochemical synthesis avoids the production of NaCl, which is inevitable in the other processes, it is currently not being employed in industry. 

The above reaction principle can be extended to the synthesis of dibenzothiazyl disulfide 328) and benzothiazolylsulfenamides 329). 

The anodic cleavage of disulfides was used on the laboratory scale for the synthesis of other vulcanization enhancers 330 331), for the production of phenyl sulfinates 332), and for the synthesis of intermediates for penicillins and cephalosporins 333). 

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