AbstractA new synthesis of 6‐demethoxy‐N‐formyl‐N‐northebaine (1) and its spectacular rearrangement to dibenzazonine 8 are described.N‐Demethylation of codeine (2) gave N‐norcodeine (3) which was converted into the mesyl compound 5 by N‐formylation with ethyl formate, followed by reaction with mesyl chloride in pyridine. A short treatment of 5 with lithium bromide afforded 7 which, upon reaction with potassium tert‐butoxide, yielded 1. Reaction of 7 with zinc in ethanol gave morphinan‐5,7‐diene 9. Prolonged treatment of morphinan 5 with lithium bromide gave dibenzazonine 8, which could also be obtained by reaction of 1 with hydrogen bromide. A mechanism for this rearrangement is proposed.The 1H and 13C NMR spectra of the new compounds are discussed.