Highly Selective Route for Producing Unsymmetrically Substituted Monomers toward Synthesis of Conjugated Polymers Derived from Poly(p-phenylene vinylene)

Albert J. J. M. van Breemen; Dirk J. M. Vanderzande; Peter J. Adriaensens; Jan M. J. V. Gelan

doi:10.1021/jo9821022

Highly Selective Route for Producing Unsymmetrically Substituted Monomers toward Synthesis of Conjugated Polymers Derived from Poly(p-phenylene vinylene)

J Org Chem. 1999 Apr 30;64(9):3106-3112. doi: 10.1021/jo9821022.

Authors

Albert J. J. M. van Breemen¹, Dirk J. M. Vanderzande, Peter J. Adriaensens, Jan M. J. V. Gelan

Affiliation

¹ Institute for Materials Research, Universitaire Campus Gebouw D, Department SBG, Chemistry Division, Limburg University, B-3590 Diepenbeek, Belgium.

PMID: 11674409
DOI: 10.1021/jo9821022

Abstract

A new convenient route for producing unsymmetrically substituted sulfinyl monomers of precursor polymers toward poly(p-phenylene vinylene) is described. Upon treating a symmetrical bissulfonium salt with a thiolate anion, an unexpected high selectivity for the monosubstituted thioethers (90%) is obtained. Optimization of the reaction conditions showed that the stoichiometry of the reactants in this reaction is important to ensure the high selectivity and to prevent unwanted side reactions. Reaction of equimolar amounts of reagents at ambient temperature gave the best results. A mechanism consistent with these results, supported by UV-vis experiments, is presented. Selective oxidation of the thioethers yielded the sulfinyl monomers. By using this new route, it was possible to increase the overall yield by a factor of 2, as compared to the route previously used to obtain these compounds.