Investigation of substituent effect on O–C bond dissociation enthalpy of methoxy group in meta- and para-substituted anisoles

Abstract

This paper is focused on the theoretical investigation of O–C Bond Dissociation Enthalpy (BDE) of methoxy OCH3 group in 15 meta- and 15 para-substituted anisoles in gas phase, non-polar environment, and water. Density Functional Theory (DFT) calculations were carried out using M06-2X functional and 6-311++G(d,p) basis set. Obtained BDEs were correlated with Brown and Okamoto σp+ and Hammett σm constants representing commonly used descriptors of electron-donating or electron-withdrawing substituent effect. Obtained linear dependences allow the prediction of substituent effect on BDE using σp+ and σm constants. Calculated reaction enthalpies were also compared with available experimental and theoretical ab initio G4 values. Found results suggest that employed method may provide reliable thermochemistry data for demethylation of naturally occurring (poly)phenolic compounds, as well. In all studied environments, substituent induced changes in O–C BDE can be considered equal to those observed for the dissociation of phenolic O–H bond of substituted phenols.