Nucleophilic Substitution in the Allylic System of Codeine and Pseudocodeine: Reactions with lithium cyano(methyl)-and (aryl)cyanocuprates. Crystal and molecular structure of 8α-phenyl-6,7-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan and 6α-phenyl-7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan
✍ Scribed by Valery N. Kalinin; Irina L. Belyakova; Vladimir V. Derunov; Pavel V. Petrovskii; Aleksandr I. Yanovski; Yurii T. Struchkov; Helmut Schmidhammer; Jin K. Park
- Publisher
- John Wiley and Sons
- Year
- 1994
- Tongue
- German
- Weight
- 363 KB
- Volume
- 77
- Category
- Article
- ISSN
- 0018-019X
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✦ Synopsis
9. VIII.93)
Nucleophilic substitution of 6p-chloro-7,8-didehydro-4,5~ -epoxy-3-methoxy-17-rnethylmorphinan (1) and 8a -brom0-6,7-didehydro-4,5~ -epoxy-3-methoxy-17-methylmorphinan (2) with lithium cyano(methy1)-and (aryl)cyanocuprates(I) (5a-c) was accompanied by allylic rearrangement with both change and retention of orientation of the substituting group (Scheme I, Table ) . Nucleophilic substitution in 7,8-didehydro-4,5a-epoxy-3-methoxy-17-methyImorphinan-6a -yl methanesulfonate (3) and 7,8-didehydro-4,5~ -epoxy-3-methoxy-17methylmorphinan-6p-yl methanesulfonate (4) proceeded without allylic rearrangement with both change and retention of the orientation of the substituting group (Scheme2, Table ) . X-Ray diffraction studies of the products 6,7-didehydro-4,5~ -epoxy-3-methoxy-l7-methyl-8a -phenylmorphinan (6b) and 7,8-didehydro-4,5~ -epoxy-3methoxy-l7-methyl-6~-phenylmorphinan (7b) were carried out (Figs. and ) .