Chromogenic Reactions of Steroids with Strong Acids. VIII. Mechanism of the First Stage in the Kober Reaction
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概要
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Dissolution of 3-methoxy-17β-methyl-18-norestra-1,3,5 (10), 13-tetraene into 77.3% sulfuric acid gave the chromophore χ-372 (I) which changed gradually to χ-465 (II). This change was faster and its acceleration with oxidant was greater in the systems of lower acid strength. In 97.2% sulfuric acid, 3-methoxyestra-1,3,5 (10), 9 (11)-tetraen-17-one and 3-methoxyestra-1,3,5 (10), 8,14-pentaen-17-one showed maximum absorptions at 363 and 467 nm, respectively, and were then recovered almost quantitatively from the solution. Thus, the conjugate base of I was assumed to give II through an oxidative process. 13ξ, 14ξ-Epoxy-3-methoxy-17β-methyl-18-norestra-1,3,5 (10)-triene (III) immediately showed a stable maximum absorption at 465 nm in 97.2% sulfuric acid, from which the estrapentaene (IV) was then isolated. Compared with the chemical shifts of I, NMR spectra of III as well as IV in sulfuric acid suggested II to be the carbocation. The same experiments were also made on related compounds and corresponding results were obtained. Consequently, it is proposed, for the mechanism of the Kober reaction in its first stage, that the conjugate base of the initially formed carbocation χ-372 (I) is oxidized by sulfuric acid into the chromophoric cation χ-465 (II).
- 社団法人日本薬学会の論文
- 1977-05-25
著者
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三浦 敏明
Faculty Of Pharmaceutical Sciences Hokkaido University
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木村 道也
Faculty of Pharmaceutical Sciences, Hokkaido University
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木村 道也
Faculty Of Pharmaceutical Sciences Hokkaido University
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