Some Studies in Molecular Orbital Theory II. Ionization Constants in Heteroaromatic Amines and Related Compounds

Abstract

The relative basicities of a series of mono‐aza‐aromatic amines are calculated by a very simple application of LCAO molecular orbital theory. Rough quantitative agreement between theory and experiment is obtained if the heterocyclic nitrogen atom is supposed to take up the proton; on the other hand, if the amine group is assumed to add the proton in the first ionization, the observed basicities are negatively correlated with theory. It is also shown how the qualitative differences in reactivity between methyl‐aza‐hydrocarbons and between heteroaromatic phenols may be understood in similar very simple terms.