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- W4250622600 abstract "The kinetics of methanolysis of acetyl imidazole (1) and acetyl pyrazole (2) have been investigated under anhydrous conditions in the presence of Zn(ClO 4 ) 2 , Co(ClO 4 ) 2 , and HClO 4 at 25°C. In all cases, the plots of the pseudo-first-order rate constant for methanolysis (k obs ) vs. [metal ion] or [HClO 4 ] show saturation behavior indicative of equilibrium binding of the M 2+ or H + to the amide. Relative to the spontaneous methanolysis rate constant (k o ), the catalytic rate constant obtained at saturation, k cat , is larger for metal-ion catalysis than for H + catalysis. The (k cat H+ /k o ) ratio is 10.7 and 1.25 for 1 and 2, respectively, while the (k cat M2+ /k o ) for these divalent metals varies from 150-fold for 1 to between 700 and 5700-fold for 2. By contrast, in water, proton is far more effective at promoting the hydrolysis of 1 than are metals, the aqueous (k cat H+ /k o ) ratio being 560, while the (k cat Zn2+ /k o ) and (k cat Ni2+ /k o ) ratios are 15 and 3.2, respectively.Key words: methanolysis, kinetics, metal-ion catalysis, acetyl imidazole, acetyl pyrazole." @default.
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- W4250622600 date "1999-06-01" @default.
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- W4250622600 title "Strong Zn<sup>2+</sup> and Co<sup>2+</sup> catalysis of the methanolysis of acetyl imidazole and acetyl pyrazole" @default.
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- W4250622600 doi "https://doi.org/10.1139/v99-101" @default.
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