The metal ion assisted hydrolysis of organic fluorides

The hydrolysis of CF linkages in many aliphatic fluorides is accelerated in the presence of salts of Th(IV), Al(III), and other typical hard acids. Such acceleration has been noted with benzyl fluoride, fluoroacetate, benzotrifluoride, and its ortho hydroxy and ortho and meta amino derivatives. Two RCF 3 compounds, trifluoroacetate and 3-nitro-4-chlorobenzo-trifluoride did not undergo hydrolysis under the conditions used. Fluorophenols were found to undergo both nitration and fluoride hydrolysis, reactions which probably proceeded through intermediate nitroso compounds. Hydrolysis of fluorophenols occurs only in the presence of nitrate salts. The product isolated from a reaction mixture containing meta fluorophenol and an acidic solution of thorium nitrate is 2,4,6-trinitroresorcinol. Other compounds containing a fluorine atom bonded directly to a carbon in an aromatic ring were unaffected in such reaction media.