Abstract: A new simple and efficient method for the synthesis of polyfluoroarenesulfonyl bromides by reaction of polyfluoroarenethiols with a mixture of bromine and fuming nitric acid is developed (Scheme 1) . Scheme 1. Synthesis of polyfluoroarenesulfonyl bromides The reaction of polyfluoroarenesulfonyl bromides with allyl bromide proceeds with loss of bromine and leads to allyl polyfluoroaryl sulfones in good yields (Scheme 2). Scheme 2. Synthesis of allyl polyfluoroaryl sulfones However, the reaction of pentafluorobenzenesulfonyl bromide with allyl chloride yielded no allyl pentafluorophenyl sulfone. In this case, addition of C6F5SO2Br to the double bond of allyl chloride took place. Allyl and benzyl polyfluoroaryl sulfides are easily obtained by reaction of the corresponding arenethiols with allyl chloride or bromide in MeCN or with benzyl chloride in MeCN or DMF in the presence of K2CO3 (Scheme 3). Scheme 3. Synthesis of allyl and benzylpolyfluoroaryl sulfides Polyfluoroarenethiols react with CHFCl2 in the presence of NaOH to give mixtures of the corresponding fluorochloromethyl polyfluoroaryl sulfides and hydropolyfluoroarenes. The reaction with CHCl3 under analogous conditions gives mainly hydropolyfluoroarenes (Scheme 4). Scheme 4. Reactions of polyfluoroarenethiols with CHFCl2 and CHCl3 Possible mechanisms of the reactions will be discussed. V.E. Platonov et al. J.Fluorine Chem. 2010, 131(1), 13-16.

Cite: Bredikhin R.A. , Maksimov A.M. , Platonov V.E.
Reactions of polyfluoroarenethiols with electrophiles. Synthesis and some transformations of allyl polyfluoroaryl sulfides and sulfones
VIII Regular German-Russian-Ukrainian Symposium on Fluorine Chemistry, Звенигород, 11.10.2010-15.10.2010 11-15 Oct 2010