Reactions of thiols with phenylglyoxal to give thiomandelic S-esters. Formation of hemithioacetals and their rearrangement.
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概要
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Equilibrium constants <I>K</I><SUB>h</SUB> for the addition of 2-mercaptoethanol and glutathione to phenylglyoxal to form hemithioacetals were determined spectrophotometrically over the pH range 7–10. The observed <I>K</I><SUB>h</SUB> values decrease sigmoidally with pH as the thiol ionizes. Rearrangement of hemithioacetals formed from phenylglyoxal and various thiols was kinetically investigated. The rates increase with thiol concentration following a saturation curve to give <I>K</I><SUB>h</SUB> identical with the spectrophotometric value. The rearrangement is subject to general base catalysis. The solvent isotope effect on the rate of the rearrangement, <I>k</I><SUP>H<SUB>2</SUB>O</SUP>/<I>k</I><SUP>D<SUB>2</SUB>O</SUP>, is nearly 1.0; that on the equilibrium, <I>K</I><SUB>h</SUB><SUP>H<SUB>2</SUB>O</SUP>/<I>K</I><SUB>h</SUB><SUP>D<SUB>2</SUB>O</SUP>, is 0.38. The results strongly support the mechanism involving proton transfers through an enediol intermediate.
- 公益社団法人 日本化学会の論文
著者
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FUENO Takayuki
Faculty of Engineering Science, Osaka University
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Fueno Takayuki
Faculty Of Engineering Science Osaka University
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Okuyama Tadashi
Faculty Of Engineering Science Osaka University
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Kimura Kazumasa
Faculty of Engineering Science, Osaka University
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