~~ ~The 'H NMR and I3C NMR spectra of N-formylated morphinans were compared with those of the N-methyl and N-demethyl analogues. The magnitude of the changes in chemical shift of C-9, C-16 and C-10 depended crucially on the nature of the substituent at nitrogen. For the 6a,l4aethenoisomorphinans and 6~,14/?-ethenomorphinans, the proton chemical shifts of the 6,14-etheno bridge across ring C are differently affected by the nitrogen atom. In the 6a,14a-ethenoisomorphinans, the vinylic proton shifts are found between 65.3 and 5.9, whereas in the 68,148-ethenomorphinans these proton signals are found downfield from 66.0. A similar, but opposite, anisotropy effect of the nitrogen is observed for the 88-proton. These results are important for the elucidation of the structures of these types of compounds.