On the Mechanism of Color and Fluorescence Reaction of 17α-Hydroxyprogesterone with Sulfuric Acid

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The mechanism of the color and fluorescence reaction of 17α-hydroxyprogesterone (1) with sulfuric acid was elucidated. When a 97% sulfuric acid solution of 1 was heated at 60℃ for 45 min and then diluted two-fold with ethanol, a chromo- and fluorophoric species (λ_<max>=592nm, λ_<em>=614nm, abbreviated as χ-592) was produced. From this reaction mixture, 17ξ, 17a-dimethyl-18-nor-D-homoandrosta-4,6,8 (14), 13 (17a)-tetraen-3-one (4a) was isolated in 13% yield. Dissolution of the tetraenone (4a) in a 1 : 2 mixture of sulfuric acid and ethanol immediately gave an absorption maximum at 592nm (ε=35200) with fluorescence at 614nm. The proton nuclear magnetic resonance spectrum of 4a in a 1 : 2 mixture of D_2SO_4 and CD_3OD indicated that the chromo- and fluorophoric χ-592 is a hydroxyalkatetraenyl cation (4b), the protonated form of 4a. χ-592 (4b) was shown to be formed from 1 via an intermediary species (λ_<max>=427nm, λ_<em>=472nm). The structure of the intermediary species was also assumed to be a steroidal dication (9) having both a hydroxyalkenyl cation in ring A and an alkadienyl cation across rings C and D.
社団法人日本薬学会の論文
1985-08-25