Carbonyl compounds uncatalyzed hydration

Fig. 12 Mechanisms for base-catalyzed, uncatalyzed, and acid-catalyzed hydration of carbonyl compounds.

Fig. 14 Uncatalyzed hydration ofa carbonyl compound by a cyclic mechanism. Reproduced with permission from ref. 105. Copyright 2000. American Chemical Society. 

Table 8 AG1 for hydration of carbonyl compounds by acid-catalyzed, base-catalyzed, and uncatalyzed mechanisms ...

There are abundant kinetic data for addition of water to carbonyl compounds either uncatalyzed, acid catalyzed, or base catalyzed. For a considerable number of these reactions the equilibrium constant for hydration is also available and thus an extensive test of NBT is possible [73]. Over the entire range of reactivity for which data are available (from formaldehyde plus hydroxide to NA -dimethylacetamide plus water), the calculated AG values were in good agreement with experiment. At the time this paper was published [73], the rate of uncatalyzed hydrolysis of dimethylacetamide had not been reported. Since then Wolfenden and coworkers [74] have reported a rate constant at elevated temperatures extrapolating to a AG of 32kcal/mol in good agreement with our prediction of 31.11 kcal/mol. 

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