Selective synthesis of 2,6-naphthalenedicarboxylic acid by use of cyclodextrin as catalyst

The selective synthesis of 2,6-naphthalenedicarboxylic acid from 2-naphthalenecarboxylic acid with carbon tetrachloride, copper powder, and aqueous alkali was achieved by using of β-cyclodextrin (β-CyD) as a catalyst at 60°C under nitrogen, producing 2,6-naphthalenedicarboxylic acid in 67 mol% yield with 84% selectivity. The one-pot preparation of 2,6-naphthalenedicarboxylic acid from naphthalene was attained at 84°C by using of β-CyD, producing 2,6-naphthalenedicarboxylic acid in 65 mol% yield with 79% selectivity. When α-CyD or γ-CyD was used instead of β-CyD on the carboxylation of 2-naphthalenecarboxylic acid and naphthalene, respectively, the reaction hardly proceeded. The conformation of β-CyD–2-naphthalenecarboxylate inclusion complex in aqueous alkaline solution was determined by the nuclear magnetic resonance spectroscopy using 1H homonuclear Overhauser enhancement on the rotating frame. The 2-naphthalenecarboxylate anion was axially included in the cavity of β-CyD with an orientation which directed the 5-, 6-, and 7-positions of 2-naphthalenecarboxylate anion to the secondary hydroxyl side of β-CyD. It was concluded that the high selectivity of the carboxylation of 2-naphthalenecarboxylic acid was ascribed to the conformation of the β-CyD–2-naphthalenecarboxylate inclusion complex. The selective carboxylation of naphthalene was attributed to the formations of the β-CyD–naphthalene and β-CyD–2-naphthalenecarboxylate inclusion complexes.