Acid-catalyzed hydrolysis of methoxymethyl phenyl sulfoxide without concomitant racemization.
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概要
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Methoxymethyl phenyl sulfoxide <B>1</B> undergoes acid-catalyzed hydrolysis to give <I>S</I>-phenyl benzenethiosulfinate <B>5</B>, which is formed rapidly from a primary product, benzenesulfenic acid <B>3</B>. Formation of <B>5</B> follows pseudo-first-order kinetics. Rate constants obtained spectrophotometrically in perchloric acid show that the reaction is dependent on the protonated substrate with the Bunnett–Olsen φ=−0.15. Rate constants for the loss of optical activity of the enantiomeric <B>1</B> measured in 80 vol% aqueous dioxane are identical with those obtained spectrophotometrically for the formation of <B>5</B>. Racemization of the substrate does not take place more rapidly than the fragmentation. The reaction is accelerated by chloride and bromide ions. The halide reaction is first order in acid concentration.
- 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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Okuyama Tadashi
Faculty Of Engineering Science Osaka University
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Toyoda Masayoshi
Faculty of Engineering Science, Osaka University
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