Diels‐alder reaction of thebaine via N‐formylnorthebaine with nitroethene; reduction of the nitro group in 7α‐nitroethenoisomorphinans (chemistry of opium alkaloids, part XX)
- 1 January 1985
- journal article
- research article
- Published by Wiley in Recueil des Travaux Chimiques des Pays-Bas
- Vol. 104 (7-8) , 205-208
- https://doi.org/10.1002/recl.19851040705
Abstract
Thebaine (1) was converted into N‐formylnorthebaine (4) via N‐demethylation using diethyl azodicarboxylate followed by treatment with ethyl formate. Diels‐Alder reaction of 4 with nitroethene yielded 5 exclusively with the 6α,14α‐etheno bridge and the nitro group in the 7α‐position. Hydrolysis of 5 and methylation then gave 7, the nitroethene addition product of thebaine. Reduction of 5 and 7 with aluminium amalgam gave the corresponding 7α‐amines 11 and 8, respectively. Reduction of 7 with formamidinesulfinic acid or with lithium aluminium hydride gave only the oxime 9.Keywords
This publication has 14 references indexed in Scilit:
- Correlation of proton chemical shifts by two-dimensional Fourier transform NMRJournal of Magnetic Resonance (1969), 1981
- (−)-4-Hydroxy-N-formylmorphinan-6-one, a versatile intermediate for the synthesis of 3-deoxyopioidsCanadian Journal of Chemistry, 1980
- Selective removal of phenolic hydroxyl groups of morphinan derivatives synthesis of rac. N‐formyl‐3‐methoxy‐6‐oxomorphinan (1)Recueil des Travaux Chimiques des Pays-Bas, 1976
- Conversion of (-)-N-formylnordihydrothebainone into (-)-dihydrotbebainone and vice versa: (Chemistry of opium alkaloids, Part VII)Recueil des Travaux Chimiques des Pays-Bas, 1976
- Synthesis of 6,7-benzomorphan and related nonquaternary carbon structures with marked analgetic activityJournal of Medicinal Chemistry, 1969
- Total synthesis of natural (levo) and enantiomeric (dextro) forms of prostaglandin E1Journal of the American Chemical Society, 1969
- Novel analgesics and molecular rearrangements in the morphine–thebaine group. Part XII. Derivatives of 7-amino-6,14-endo-etheno-tetrahydrothebaineJournal of the Chemical Society C: Organic, 1969
- Novel analgesics and molecular rearrangements in the morphine-thebaine group. III. Alcohols of the 6,14-endo-ethenotetrahydrooripavine series and derived analogs of N-allylnormorphine and -norcodeineJournal of the American Chemical Society, 1967
- Novel analgesics and molecular rearrangements in the morphine-thebaine group. II. Alcohols derived from 6,14-endo-etheno- and 6,14-endo-ethanotetrahydrothebaineJournal of the American Chemical Society, 1967
- Methylsulfinyl Carbanion (CH3-SO-CH2-). Formation and Applications to Organic SynthesisJournal of the American Chemical Society, 1965