The search for efficient intramolecular proton transfer from carbon: the kinetically silent intramolecular general base‐catalysed elimination reaction of O‐phenyl 8‐dimethylamino‐1‐naphthaldoximes

The ready elimination of phenol/phenoxide from the O ‐phenyl oxime 10E derived from 8‐dimethylamino‐1‐naphthaldehyde, necessarily involving proton transfer from carbon, is catalysed by the neighbouring NMe 2 group at pH > 9. However, reaction is faster, rather than slower, at lower pH. It is shown that the step involving proton transfer is not cleanly rate determining at any pH: the preferred route involves syn / anti isomerization to form the more reactive Z ‐isomer. The rate constant for the anti elimination cannot be extracted from the available data, so no reliable estimate of effective molarity (EM) is possible.