AROMATIZATION OF ARENE 1,2-OXIDES - 1-CARBOXYBENZENE AND 1-CARBOALKOXYBENZENE OXIDES

The mechanisms for aromatization of arene 1, 2-oxides are discussed. The reaction course for aromatization of 1-car-boxy-and 1-carboalkoxybenzene oxides is established, and the importance of the 1, 2-oxides of benzoic acids as intermediatesin biological hydroxylations is considered in view of the observed results. Acid-catalyzed rearrangement of 1-carbomethoxy-benzene oxide (4a) and the corresponding 2-2H, 2-CH3,4-CH3, and 2-CH3O2C derivatives of 4a occurs exclusively by an NIH shift involving migration of the carbomethoxy group. Aromatization of 1-carboxybenzene oxide (13) affords a mixture of salicylic acid and phenol, the ratio of which is pH dependent. The 2-CH3and 4-CH3derivatives of 13 decarboxylate to o-and p-cresol, respectively, on attempted isolation. © 1979, American Chemical Society. All rights reserved.