| Summary: | The NMR chemical shift, <em>i.e</em>., the π-electron density of the double bond, of acrylates and methacrylates is related to the reactivity of their monomers. We investigated quantitative structure-property relationships (QSPRs) between the base-catalyzed hydrolysis rate constants (<em>k</em>1) or the rate constant with glutathione (GSH) (log <em>k</em><sub>GSH</sub>) for acrylates and methacrylates and the <sup>13</sup>C NMR chemical shifts of their α,β-unsaturated carbonyl groups (δC<sub>α</sub> and δC<sub>β</sub>) or heat of formation (Hf) calculated by the semi-empirical MO method. Reported data for the independent variables were employed. A significant linear relationship between <em>k</em>1 and δC<sub>β</sub>, but not δC<sub>α</sub>, was obtained for methacrylates (<em>r</em><sup>2</sup> = 0.93), but not for acrylates. Also, a significant relationship between <em>k</em>1 and Hf was obtained for both acrylates and methacrylates (<em>r</em><sup>2</sup> = 0.89). By contrast, log <em>k</em><sub>GSH</sub> for acrylates and methacrylates was linearly related to their δC<sub>β</sub> (<em>r</em><sup>2</sup> = 0.99), but not to Hf. These findings indicate that the <sup>13</sup>C NMR chemical shifts and calculated Hf values for acrylates and methacrylates could be valuable for estimating the hydrolysis rate constants and GSH reactivity of these compounds. Also, these data for monomers may be an important tool for examining mechanisms of reactivity.
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