V. Sorokin, A. Pozharskii, V. Ozeryanskii
Oct 1, 2013
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0
Influential Citations
3
Citations
Journal
Journal of Fluorine Chemistry
Abstract
Abstract Reaction of N , N -dimethylaniline, N , N -dimethylnaphthalen-1-amine and 1,8-bis(dimethylamino)naphthalene (proton sponge) with 1-chloromethyl-4-fluorodiazonia-bicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor) and N -fluorobenzenesulfonimide (NFSI) has been studied under various conditions. Unlike the proton sponge, which is fluorinated rather selectively at the ortho -position to NMe 2 group, producing 2-fluoro derivatives in moderate yield, two other amines react with Selectfluor and NFSI with strong tarring and the formation of complex mixtures of the corresponding biaryls, biarylmethanes and N -demethylated products. 2-Fluoro and 4-fluoro derivatives are also formed in minor quantities with the former isomer being predominant. Using the NFSI–ZrCl 4 system results in competitive chlorination of the aromatic ring.