Extension of our studies of the generic Wallach rearrangement (of azoxybenzene to 4-hydroxyazobenzene) to the heteroaromatic series (azoxypyridines and axoxypyridine N-oxides) has revealed some dramatic reactivity differences, particularly for the α and β compounds. We have studied the 3-isomers and the 4-isomers in each series, each with α and β forms, eight compounds in all, in the 100 wt% sulfuric acid region of acidity. In those cases in which a product could be observed, the α and β isomers both give the same one, the corresponding 4′-hydroxyazo compounds. All the compounds react much more slowly than does azoxybenzene itself, presumably because of the extra positive charge present in the substrates, but the β isomers have half-lives of seconds and the α isomers half-lives of hundreds of hours in the 100 wt% H2SO4 acidity region. The α compounds have measurable pKBH+ values, but the β compounds do not, exhibiting only a medium effect in the acidity region in which the α compounds protonate. This means that for the β compounds, the protonated intermediates must be much less stable and the postulated reaction intermediates must be much more stable than for the α compounds. To clarify this, we have obtained Mulliken charge distributions for the various species concerned, calculating the charge carried by each half of the molecule, larger charge separations being taken to indicate lesser stability. As far as we can establish, this is the first time that this technique has been used to indicate the stabilities of carbocationic species.Key words: azoxypyridines, azoxypyridine N-oxides, Wallach rearrangement, excess acidity, basicities, theoretical calculations, charge distributions, reactivities.
Insights on forming N,O-coordinated Cu single-atom catalysts for electrochemical reduction CO2 to methane
