Interesting Acid-Catalyzed O-N-Type Smiles Rearrangement Reactions of 2-Pyrimidinyloxy-N-Arylbenzylamine Derivatives

Abstract: The acid-catalyzed O–N-type Smiles rearrangement re-actions of 2-pyrimidinyloxy- N -arylbenzylamine derivatives wereinvestigated. The results show most 2-pyrimidinyloxy- N -aryl-benzylamine derivatives can also undergo the Smiles rearrangementto the corresponding phenol derivatives in good yields at 25 °C inacetic acid–acetone (1:1). Key words: Smiles rearrangement, acidic conditions, 2-pyrimidi-nyloxy- N -arylbenzylamine The Smiles rearrangement, with its many creative and ef-fective variations, has an important place among the manysynthetic tools available in the preparation of heterocycliccompounds and substituted nitro-aryl compounds. Thisrearrangement is one of the best base-catalyzed rearrange-ments. The mechanism, which involves a Meisenheimercomplex, is summarized in Scheme 1. 1–4 This reactionnormally requires an electron-withdrawing group (e.g. ni-tro, sulfonyl or halogen) on the aromatic ring; generally Xis a leaving group and Y is a nucleophile. 3 Scheme 1 2-Pyrimidinyloxy-