Catalysis and mechanism of the isomerization of a .DELTA.5-3-keto steroid.
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概要
- 論文の詳細を見る
The acid- and base-catalyzed isomerizations of <I>Δ</I><SUP>5</SUP>- to <I>Δ</I><SUP>4</SUP>-testosterone have been kinetically studied in aqueous solution. Solvent isotope effects of <I>k</I><SUB>H<SUB>3</SUB>O<SUP>+</SUP></SUB>⁄<I>k</I><SUB>D<SUB>3</SUB>O<SUP>+</SUP></SUB>=0.69 and <I>k</I><SUB>OH<SUP>−</SUP></SUB>⁄<I>k</I><SUB>OD<SUP>−</SUP></SUB>=3.1 were obtained. It was thus concluded that the acid-catalyzed isomerization proceeds through rate-determining enolization but the base-catalyzed reaction through rate-determining protonation of an enolate ion. It was found that primary amines efficiently catalyze the isomerization <I>via</I> an iminium ion intermediate. Possible bifunctional catalysis was suggested for the high catalytic activity of polyfunctional primary amines.
- 公益社団法人 日本化学会の論文
著者
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Okuyama Tadashi
Department Of Mechatronics Shonai College Of Industry And Technology
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Fueno Takayuki
Department of Synthetic Chemistry Kyoto University
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Kitada Akira
Department of Chemistry, Faculty of Engineering Science, Osaka University
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Okuyama Tadashi
Department of Chemistry, Faculty of Engineering Science, Osaka University
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Fueno Takayuki
Department of Chemistry, Faculty of Engineering Science, Osaka University
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