Zusammenfassung
Die Teilstruktur I für Delphinin wurde eindeutig bestätigt. Eswurde gezeigt, dass die Pyro-Isopyro-Umwandlung von Delphininderivaten in der Allylumlagerung einer Methoxylgruppe besteht. Biogenetisch einleuchtende Gesamtstrukturen für Delphinin werden kurz diskutiert.
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References
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Footnote added to proof. — The ‘Hofmann degradation’ of delphinine in aqueous potassium hydroxide has now been clarified. It is initiated by a 1,3 cleavage in which the quaternary nitrogen and the hydroxyl, which formerly carried the acetyl group, participate. The endproduct is a monosubstituted 1–4 cycloheptane dione formed by loss of a methoxyl and two dealdolisations. Thus the modified structure XVII may be dismissed and the choice is merely between XIV and XIII.
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Wiesner, K., Bickelhaupt, F. & Babin, D.R. Rigorous proof of an allylic rearrangement in the pyro-isopyro change in delphinine. Experientia 15, 93–95 (1959). https://doi.org/10.1007/BF02166690
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DOI: https://doi.org/10.1007/BF02166690