Abstract An unusual peri-dimerised product was obtained when subjecting 1, 3, 6, 8- tetramethoxynaphthalene to Vilsmeier–Haack reaction conditions (POCl 3/DMF). The formation of this peri-dimerised naphthalene product suggests that 1, 3, 6, 8- tetramethoxynaphthalene has comparable reactivity to that of Proton Sponge [1, 8-bis (dimethylamino) naphthalene]. The octamethoxy peri-dimer was characterised using NMR ...