Color and Fluorescence Reaction Mechanism of Progesterone with Sulfuric Acid

概要

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The ^1H-and ^<13>C-nuclear magnetic resonance spectra of progesterone (VII) in 97% H_2SO_4 indicated the formation of a dication (VIII), which was transformed to another dication χ-301 (X) consisting of a hydroxyalkenyl cation moiety in ring A and a cyclopentenyl one in ring D, when the acid solution was heated at 80℃ for 2h. At a reduced acid-strength of the reaction system, X was converted to the hydroxyalkatrienyl cation χ-482 (XIV) through an acid-base equilibrium on the one hand, and to the hydroxyalkatetraenyl cation χ-600 (XV) by an oxidative process on the other. The structures of these cations were confirmed by isolating the corresponding conjugate bases, 17ζ-isopropyl-18-nor-13ζ-androsta-4,6,8 (14)-trien-3-one (XII) and 17-isopropyl-18-norandrosta-4,6,8 (14), 13 (17)-tetraen-3-one (XIII), from the colored solutions. The pK_a values of the cations XIV and XV were-4.6 and -3.8,respectively. On the basis of these results, a mechanism is proposed for the title reaction.
社団法人日本薬学会の論文
1984-07-25