Acid treatment of the p-quinol acetate (23), obtained from the phenolic amine (14) gave (±)-2-hydroxy-3-methoxyhomoproaporphine (20) in excellent yield. However, similar treatment of other p-quinol acetates (24 and 25) afforded no cyclized products. Reaction of 24 or 25 with Ac₂O-conc. H₂SO₄ gave two diastereoisomeric 4, 7-diacetates (36a and 36b or 38a and 38b). The stereostructures of 36a and 36b were decided by nuclear magnetic resonance study, while those of 38a and 38b were determined by chemical transformations and X-ray analyses. The stereoselectivity of acetoxylation is discussed.