Imidazole Catalyses in Aqueous Systems. IV. Bimolecular and Michaelis-Menten-Type Catalyses of a Phenyl Ester Hydrolysis by Some Hydrophobic Imidazole Derivatives
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概要
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Catalytic hydrolyses of <I>p</I>-acetoxybenzoic acid by several imidazole derivatives were conducted at 15–40°C in aqueous systems using a pH-stat. Imidazole compounds containing the naphthalene ring catalyzed the hydrolysis following the Michaelis-Menten kinetics as in enzymatic reactions, while catalysis by less hydrophobic imidazoles followed the second-order kinetics. Enhancement of the overall catalytic efficiency in the Michaelis-Menten pathway was estimated to be ten times at most as compared with the bimolecular pathway. The thermodynamic and activation parameters were obtained at 15–40°C for the Michaelis-Menten pathway. The binding of catalyst and substrate was characterized by small positive enthalpy changes (<I>ΔH</I>≅+3.5 kcal/ mol) and large positive entropy changes (<I>ΔS<SUB>u</SUB></I>≅+28 eu), indicating that the complex formation was ascribable to hydrophobic interactions. The intra-complex product formation was characterized by not unreasonable <I>ΔH</I><SUP>≠</SUP> values and extraordinarily large negative <I>ΔS</I><SUP>≠</SUP> (≅−50 eu) values. The unexpectedly small rate enhancement in the Michaelis-Menten pathway was attributed to the unfavorable <I>ΔS</I><SUP>≠</SUP> term, which suggested that the structure of the Michaelis complex was quite different from that of the transition state of the product formation.
- 公益社団法人 日本化学会の論文
著者
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Kunitake Toyoki
Department Of Chemical Engineering & Technology Faculty Of Engineering Kyushu University
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Shinkai Seiji
Department Of Applied Chemistry Faculty Of Engineering Kyushu University
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