Electrochemical Synthesis of Organic Polysulfides from Disulfides by Sulfur Insertion from S(8) and an Unexpected Solvent Effect on the Product Distribution

An electrochemical synthesis of organic polysulfides through sulfur insertion from elemental sulfur to disulfides or thiols is introduced. The highly economic, low‐sensitive and low‐priced reaction gives a mixture of polysulfides, whose distribution can be influenced by the addition of different amounts of carbon disulfide as co‐solvent. To describe the variable distribution function of the polysulfides, a novel parameter, the “absorbance average sulfur amount in polysulfides” (SAP) was introduced and defined on the basis of the “number average molar mass” used in polymer chemistry. Various organic polysulfides were synthesized with variable volume fractions of carbon disulfide, and the yield of each polysulfide was determined by quantitative (13)C NMR. Moreover, by using two symmetrical disulfides or a disulfide and a thiol as starting materials, a mixture of symmetrical and asymmetrical polysulfides could be obtained.