40938-45-2Relevant academic research and scientific papers
THERMAL Z,E-ISOMERIZATION OF IMINES. IV. ANILS OF ACETONE
Prosyanik, A. V.,Kol'tsov, N. Yu.,Romanchenko, V. A.
, p. 1330 - 1337 (2007/10/02)
It has been established by the correlation between the values of log k298 and the ? constants that the degenerate thermal Z,E-isomerization of anils of acetone takes place according to an inversion mechanism, with the exception of acetone p-dimethylaminophenylimine, which isomerizes predominantly according to a rotation mechanism.The increase in the steric stresses upon the introduction of ortho substituents into the aryl ring of anils of acetone results in significant lowering of the barriers to the inversion of the nitrogen atom.The raising of the barriers to inversion in phenylimines as the electron-acceptor properties of the substituents on the imino carbon atom are enhanced is due to the weakening of the n?N-?*Ph interaction as a consequence of the increase in the energy gap between the interacting orbitals as a result of the lowering of the energy of the n?N orbital.
