Spectroscopy and Other Physical Measurements

Jacobson and others(390) analyzed the H-nmr spectra at 100 MHz of codeine and isocodeine derivatives, previously reported at 60 MHz,(391) in order to establish the conformation of the spiro-oxirane derived from codeinone. 200) Double irradiation and NOE experiments confirmed the structure illustrated (91). 

A comparison has been made(392) between the solution, solid-state, and theoretical conformations of morphine in D20 (+DC1) employing H nmr at 100 MHz and 600 MHz and 13Cnmr at 25.2 MHz. Because of the increased chemical shift separation that occurred at very high field, the proton signals for C-15 and C-16H could be assigned and examined. This, together with data from N-CH3 and NH, and 13C (C-15 and C-16), facilitated a close 

Morphine alkaloids have been used as model compounds in a study of double bond and nitrogen and nonbonding electron anisotropic effects/391,394 The ABC system of protons at 9, 10a, and 10/ of several alkaloids of the morphine group has been the subject of theoretical analysis/395  

An extensive account1396 of H-nmr studies of 6,14-endo-ethenotetrahy-drothebaines is available relating shift data to stereochemistry throughout and making comparisons with calculated spectra. 

Extensive assignments of 13C bands for 4,5-epoxymorphinans have been published/397 398 Carroll and co-workers(298) examined 25 derivatives of morphine, 14-hydroxymorphine, and 6,14-endo-etheno- and 6,14-endo-ethanotetrahydrothebaines. Assignments were aided by off-resonance decoupled spectra and by deuterium labeling. These reports have been reviewed/399 Thebaine Diels-Alder adducts were found to have A-, B-, and D-rings with spatial orientations similar to morphine. The C-ring, however, differed in conformation in agreement with the distortion seen in X-ray structures/400  

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These and related salts were characterized by Raman spectroscopy and other physical measurements. 

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