Quantitative structure-property relationships for the chemical reactivity of acrylates and methacrylates

Abstract

Abstract Reactivity towards three different nucleophiles was measured for a training set of six acrylates and seven methacrylates. The reactions studied were neutral and base-catalyzed hydrolysis and Michael addition of reduced glutathione (GSH). A linear free energy relationship (LFER) was established for the base-catalyzed hydrolysis rate constants of methacrylates, with the Taft parameter σ* as single descriptor. The GSH reactivity could be modeled with a partial least square regression (PLS) using four quantum chemical ground state parameters describing the difference in frontier orbital interaction and coulombic forces within the training set. Literature data for GSH reactivity was used to test the applicability of the PLS model. Differences in acute fish toxicity for structurally similar acrylates and methacrylates could be explained by their different potency as Michael-type acceptors.