Reactions of saturated perfluorinated heterocycles

PREPRATION AND REACTIONS OF SATURATED PERFLUORINATED HETEROCYCLES CONTAINING OXYGEN, NITROGEN, SULFUR, SELENIUM, AND PHOSPHOROUS... 

Reactions of Saturated Perfluorinated Heterocycles Due to the strong electron withdrawing effect of perfluorinated framework, saturated ethers or amines are extremely week bases and they do not form stable compounds as a result of protonation or alkylation of heteroatom. Unshared electron pair(s) of heteroatom, however, manifests itself in different manner—through the activation of a-fluorine substituents. 

Simons process — Electrochemical polyfluorination reactions of organic compounds are the only efficient way to industrial production of perfluorinated compounds. The reaction proceeds in the solution of KF in liquid HF (b.p. 19.5 °C), where the starting substances as alcohols, amines, ethers, esters, aliphatic hydrocarbons and halo-hydrocarbons, aromatic and heterocyclic compounds, sulfo- or carboxylic acids are dissolved. During anodic oxidation, splitting of the C-H bonds and saturation of the C=C bonds occur and fluorine atoms are introduced. 

The products of the electrochemical perfluorination of aromatic and heteroaromatic compounds are the corresponding perfluorinated cyclic and heterocyclic alkanes.28 and also per-fluorinated derivatives of the heteroaromatic compounds. Perfluorocyclohexane is the principal product from the electrochemical fluorination of benzene and fluorobenzene. Chloro derivatives of perfluorocyclohexane are produced from chlorobenzenes. Anisoles give fully saturated per-fluoro ethers, together with cleavage products. Extensive cleavage is observed in the fluorination of benzenethiols. Chloropyridines, fluorocarbons and sulfur hexafluoride or nitrogen trifluoride are characteristic byproducts from the above scries of reactions. 

---