A Theoretical Analysis of the Contributions to the Internal Rotation Barrier in N-Benzylideneanilines

Abstract

Abstract An analysis, using CNDO wave functions, has been carried out on the different contributions to the internal rotation barrier in N-benzylideneaniline (1) and p-dimethylaminobenzylidene-p-nitro-aniline (2) in several conformations. The stability of the different structures has been expressed in terms of a partition of the total energy into electronic, net charges and steric hindrance contributions. Based on the shape of the total energy surface it appears that the barrier composition may be reasonably well described without approaching the absolute minimum. Rotation of the aniline group in both molecules is mainly governed by steric hindrance. Rotation of the benzylidene group shows a prevalent destabilizing electronic effect. The donor strength of the substituent in the benzylidene ring seems to play an important role in stabilizing a less nonplanar structure.