Abstract The reaction between octafluoronaphthalene and dimethylamine, pyrrolidine or piperidine in DMF, dimethyl (ethylene) urea (DMEU) or without solvent leads to the exclusive substitution of β-fluorine atoms giving naphthalene derivatives with four NR 2 groups. This was proved by 19 F NMR of the products and a crystal structure determination for 1, 4, 5, 8- tetrafluoro-2, 3, 6, 7-tetrakis (piperidin-1-yl) naphthalene. The main feature of the reaction ...