Chromogenic Reactions of Steroids with Strong Acids. VI. Behavior of Phenolic Steroids in Concentrated Sulfuric Acids

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Behavior of various 3-methoxylated phenolic steroids (I-VII and IX-XI) in conc. H_2SO_4 was studied, in particular relation to the earlier period of the Kober reaction. Alteration of the light-absorptions at the maxima of 432,465,and 515 nm was detected to be varied with the concentrations of H_2SO_4 (Fig. 1). The maximum absorption at 372 nm was observed in the mixture of estradiol-3-methyl ether (II) with 97.2% H_2SO_4 (Fig. 2), which appeared, on the contrary, immediately after mixing III, IV, V, VI, or VII with the same acid (Fig. 3 and 4). Nuclear magnetic resonance study on the solutions of III, IV, or V in the acid (Fig. 5) suggested that the absorption at 372 nm is due to the carbocation χ-372 (VIII) produced. As for the Kober reaction of steroidal estrogens, it was postulated that χ-372 initially formed is oxidized into the characteristic chrommophores χ-465 and χ-515,through which the highly dehydrogenated steroidal olefins are finally produced.
公益社団法人日本薬学会の論文
1974-03-25