Int. J. Mol. Sci. 2012, 13(5), 5789-5800; doi:10.3390/ijms13055789
Article

Relationships Between Base-Catalyzed Hydrolysis Rates or Glutathione Reactivity for Acrylates and Methacrylates and Their NMR Spectra or Heat of Formation

1email and 2,* email
Received: 13 March 2012; in revised form: 26 April 2012 / Accepted: 8 May 2012 / Published: 15 May 2012
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Abstract: The NMR chemical shift, i.e., 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 (k1) or the rate constant with glutathione (GSH) (log kGSH) for acrylates and methacrylates and the 13C NMR chemical shifts of their α,β-unsaturated carbonyl groups (δCα and δCβ) 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 k1 and δCβ, but not δCα, was obtained for methacrylates (r2 = 0.93), but not for acrylates. Also, a significant relationship between k1 and Hf was obtained for both acrylates and methacrylates (r2 = 0.89). By contrast, log kGSH for acrylates and methacrylates was linearly related to their δCβ (r2 = 0.99), but not to Hf. These findings indicate that the 13C 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.
Keywords: acrylate and methacrylate esters; base-catalyzed hydrolysis; GSH reaction rate constants; 13C NMR spectra; heats of formation; QSPRs
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MDPI and ACS Style

Fujisawa, S.; Kadoma, Y. Relationships Between Base-Catalyzed Hydrolysis Rates or Glutathione Reactivity for Acrylates and Methacrylates and Their NMR Spectra or Heat of Formation. Int. J. Mol. Sci. 2012, 13, 5789-5800.

AMA Style

Fujisawa S, Kadoma Y. Relationships Between Base-Catalyzed Hydrolysis Rates or Glutathione Reactivity for Acrylates and Methacrylates and Their NMR Spectra or Heat of Formation. International Journal of Molecular Sciences. 2012; 13(5):5789-5800.

Chicago/Turabian Style

Fujisawa, Seiichiro; Kadoma, Yoshinori. 2012. "Relationships Between Base-Catalyzed Hydrolysis Rates or Glutathione Reactivity for Acrylates and Methacrylates and Their NMR Spectra or Heat of Formation." Int. J. Mol. Sci. 13, no. 5: 5789-5800.

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