Configurational Analysis of Thebaine, Codeine and 14β-Hydroxycodeinone N-Oxides

• Published in: Magnetic resonance in chemistry Vol. 34; no. 7; pp. 505 - 511
• Main Authors: Caldwell, Gary W., Diane Gauthier, A., Mills, John E.
• Format: Journal Article
• Language: English
• Published: Chichester, UK John Wiley & Sons, Ltd 01.07.1996
• Subjects: 14β-hydroxycodeinoneN-oxide; 1H and13C NMR; 2D NMR; codeineN-oxide; spectral assignment; thebaineN-oxide
• ISSN: 0749-1581; 1097-458X
• DOI: 10.1002/(SICI)1097-458X(199607)34:7<505::AID-OMR913>3.0.CO;2-Y

The 1H (400 MHz) and 13C (100 MHz) NMR peak assignments of thebaine derivatives [free base (1), hydrochloride (2 and 3), methiodide (4) and N‐oxides (5 and 6)], codeine N‐oxide (7) and 14β‐hydroxycodeinone N‐oxide (8) were performed using various one‐ and two‐dimensional techniques. The configurations of the quaternary nitrogen‐substituted alkaloids were determined. The reaction of thebaine, codeine and 14β‐hydroxycodeinone with H2O2 produced thebaine N‐oxide with the major product (6; Rf 0.62) having an N‐CH3 axial configuration and both codeine N‐oxide (7; Rf 0.40) and 14β‐hydroxycodeinone N‐oxide (8; Rf 0.73) with the major product having an N‐CH3 equatorial configuration.