ortho-Disubstituted F-Benzenes. V. Intramolecular Heteroatom-facilitated ortho-Substitution of F-Benzene Derivatives with Oxazolinyl and Oxazinyl Groups

The oxazinyl and oxazolinyl substituents on an F-benzene ring facilitated the substitution of fluorine ortho to the heterocyclic functional groups by carbon and nitrogen nucleophiles. Alkylmagnesium halides and alkyllithium compounds were employed as the carbon nucleophile, and lithium N-methylanilide and N-methylanilinomagnesium halide as the nitrogen nucleophile. The selective ortho-substitution was accomplished by the complexing interaction between the ring-membered nitrogen on the functional substituents and the anionic nucleophile through the interposing metal cation. Effects of the substituents in the orientations and rates of the reactions depended upon the polarity of the reaction solvent and the kinds of anionic nucleophile and counter metal cation.