Morphine Alkaloids, CXVII: Investigation of the Azidolysis of Tertiary Alcohols of Thebaine Derivatives with Bridged Ring C
✍ Scribed by Ágnes Sepsi; Sándor Berényi; Sándor Makleit; Zoltán Tóth
- Publisher
- John Wiley and Sons
- Year
- 1993
- Tongue
- English
- Weight
- 401 KB
- Volume
- 326
- Category
- Article
- ISSN
- 0365-6233
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✦ Synopsis
Replacement of the C-19 tertiary hydroxyl group of some thebdine and oripavine derivatives with bridged ring C (so-called Benfley's compounds) for an azido group has been performed with hydrazoic acid. In case the hydroxyl group was connected to a centre of chirality, substitution resulted in the formation of diastereomeric mixture of azides and elimination took place a5 well, the extent of which was dependent mainly on steric factors. Configuration of the C-19 has been determined by 'H-NMR spectra and calculated proton-proton distances of amines 13a and 13b obtained by the reduction of JOc followed by separation.
Tertiary alcohols, e.g. ethorphine and buprenorphine, obtained from the Diels-Alder-adducts of thebaine (J), possess considerable analgesic activity. According to our experiences, azidolysis of the secondary hydroxyl group (C-6-OH) of morphine derivatives resulted in favourable alteration of the analgesic, antitussive'), antagonistic2), and anorexogenic3) activities.