Fries Rearrangement of Naphthyl Benzoates

Abstract

When 1-naphthyl benzoate (1α) was boiled with anhydrous aluminum chloride (AlCl₃) in chlorobenzene, 2-benzoy1-1-naphthol (2) and 4-benzoy1-1-naphthol (3) were obtained as the rearrangement products.
A product 1-benzoy1-2-naphthol (4) was given from 2-naphthyl benzoate (1β) under the same reaction conditions.
It seems that 2 and 3 are formed via intramolecular pathway from la. Other ester lβ may proceed via both inter- and intramolecular pathways to give 4. Retro-Fries rearrangement of 2 and 3 to 1α took place in the presence of AlCl₃ in boiling chlorobenzene. The compound 4 “however” was almost recovered in the reaction of 4 with AlCl₃ in chlorobenzene at refluxed temperature.