Formation of a new Polycyclic Heteroring System by the Acid-Catalyzed Rearrangement of Thebaine in the Presence of Thiosalicyclic Acid

摘要

The methanesulfonic acid-catalyzed rearrangement of thebaine (1) in the presence of thiophenol resulted in 2-phenylthioapocodeine (7), whose O-demethylation gave 2-phenylthioapomorphine (8). An analogous transformation of 1 with thiosalicyclic acid furnished the ethers (6) and (11) together with a polycyclic ketone (12) and a polyclic acetal (15). Upon treatment of the acetal (15) with acid the thioxanthylium salt (16) was prepared.