Studies on Digitalis Glycosides. XII. Structures of Digipronin and Digiprogenin.

概要

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Digipronin, a digitanol glycoside, and its aglycone, γ-digiprogenin, were respectively converted to isodigipronin and its aglycone, α-digiprogenin, by treatment with dilute alkali or acid. On refluxing with acid, α-digiprogenin lost an element of water and formed β-digiprogenin. The structure of the ⊿^4-3-oxo compound, obtained from β-digiprogenin by reduction with acetic acid and zinc dust followed by Oppenauer oxidation, was established as 14β, 17α-pregn-4-ene-3,11,15,20-tetrone by comparison with the product of isomerization of pregn-4-ene-3,11,15,20-tetrone with alkali or acid. Consequently, the structure of β-digiprogenin was presumed as 3β-hydroxy-14β-pregna-5,16-diene-11,15,20-trione and the tertiary hydroxyl group in α-and γ-digiprogenin would be located at 17-position. In view of the stability of α-digiprogenin to dilute alkali or acid and its negative contribution to optical rotation compared to γ-digiprogenin, it would be appropriate to give the structure of 3β, 17α-dihydroxy-14β-pregn-5-ene-11,15,20-trione and 3β, 17α-dihydroxypregn-5-ene-11,15,20-trione to α-and γ-digiprogenin, respectively. Digipronin is a monodigitaloside of γ-digiprogenin.
公益社団法人日本薬学会の論文
1962-01-25