A DFT and experimental study of the spectroscopic and hydrolytic degradation behaviour of some benzylideneanilines

•-N-benzylideneanilines undergo relatively fast hydrolysis under neutral conditions, at room temperature, via two possible pathways.•-Hydrolysis of N-benzylideneanilines occurs via two cyclic transition states.•-The hydrolytic evolution, vibrational and optical behaviour of N-benzylideneanilines is a function of ring substitution.•-N-benzylideneanilines derived from o-hydroy-aniline are hydrolytically labile where aniline derivatives are inert.•-Accurate mapping of all elementary steps in the evolution process was afforded by high quality DFT modelling.