Adsorption effects on the selective electrofluorination of alpha-(phenylthio)acetamides and alpha-(phenylthio)acetates in Et3N center dot 3HF/CH3CN

Cyclic voltammetric behaviour of alpha-(phenylthio)acetamides and alpha-(ph enylthio)acetates were compared in CH3CN/tetrabutylammonium perchlorate (TB AP) and CH3CN/Et3N . 3HF to assess the influence of fluoride ion on the oxi dative pathway. These studies support the Pummerer mechanistic pathway invo lving an initial attack at sulfur in selective electrofluorination (SEF). A linear correlation between the peak current values in cyclic voltammetry a nd overall synthetic yield in preparative electrolysis was obtained suggest ing the importance of weak blocking or a reactive adsorption effect on the overall synthetic processes. Other factors influencing the adsorption and i nsulation of electrode surfaces during the SEF are also discussed. (C) 1999 Elsevier Science S.A. All rights reserved.