Rationale for the acidity of Meldrum's acid. Consistent relation of C-H acidities to the properties of localized reactive orbital

Abstract

Detailed investigation on the origin of the acidity of the alpha-protons of a set of the carbonyl molecules was carried out on the basis of properties of the localized molecular orbital. An anomalously high acidity of Meldrum's acid, as compared with those of dimedone and dimethyl malonate, is one of the well-known but unresolved issues. The well-localized sigma orbitals of the C-H bonds at the alpha-position of the carbonyl groups can be obtained with the reactive hybrid orbital (RHO) theory. We found that the energy levels of the unoccupied RHOs of the C-H moiety of Meldrum's acid and other carbonyl compounds showed a good linear correlation with the experimental deprotonation energies. This is probably because the deprotonation reaction to form the proposed naked anions in a polar solvent is a highly endothermic process, in which the thermodynamic energy differences between the neutral molecules and the corresponding anions approximately coincide with the activation energies. We also investigated the effect of the conformational change upon deprotonation on the electron-accepting energy level of the relevant C-H bonds of cyclic/acyclic and monocarbonyl/dicarbonyl compounds. A conformational change occurs in the cases of cyclic six-membered compounds, but its influence on the reactivity of the C-H bond is small. The acidity of dicarbonyl compounds, including Meldrum's acid, showed a good correlation with the deviations from the perpendicular position of the dihedral angles of the relevant C-H bond with respect to the adjacent carbonyl C=O bond. This angle parameter can be related to the magnitude of the in-phase orbital interaction between the sigma(CH) and pi(C)(=)(O) orbitals, which facilitate electron acceptance. These results indicated that the acidity of the alpha-proton of carbonyl compounds can be represented in terms of the electron-accepting orbital levels of the unoccupied RHO of the C-H moiety. All the linear relationships found in the present work strongly suggested that the acidity of Meldrum's acid, which is conventionally regarded as an anomaly, is consistent with those of the other carbonyl compounds.