Perfluorobenzenes reactions with anions

The nature of the transient qiecies formed from the reactitm of Oaq whh perfluorobenzene can be determined frtim electron transfer studies whh a suitable electron acceptor. Based on these studies h was concluded diat the reaction of eaq with perfluoroacett henone or perfluorobenzaldd e formed radical anions whereas the reaction with hexafluorobenzene, pentafluon hmol or pentafluoroaniline resulted in the frxmation of a radical species vtidi fluoride ion eliminatioa Similarly, the reaction of electron with all rl halides (RX) lead to the formation of the allQrl radical and the halide ioa... 

The elimination of only one fluorine of unsubstituted perfluoroarencs yielding monothiolated pentafluorobenzenes and heptafluoronaphthalenes is rather difficult to perforin. The reactivity of the respective perfluoroarenes is not very high and because of enhanced reactivity of fluorine in position 4 (benzene) or 6 (naphthalene) of the mono(alkylsulfanyl) compounds, the reaction tends to proceed further. When perfluorobenzene is reacted with the hydrosulfide anion, the pcrfluorobenzenethiolate anion formed is a very strong competitor to the hydrosulfidc anion ... 

Other well-known reactions are those offluorinated olefins with fluoride ion and negatively substituted aromatic compounds leading to the formation of per-fluoroalkylated aromatic compounds The reaction may be considered an anionic version ot a Friedel Crafts process and can result m introduction of one or several perfluoroalkyl substituents [HI] Aromatic substrates include substituted and unsubstituted perfluorobenzenes [131, 212, 213, 214], fluorinated heterocycles [131, 203, 215, 216, 217, 218, 219, 220, 221, 222, 223], perchlonnated heterocycles [224] (equation 44), and other activated aromatic compounds [225] (equation 45) The fluorinated olefins can be linear or cyclic [208] (equation 46)... 

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