A Theoretical Study of Aromatic Claisen rearrangements.

摘要

Claisen rearrangement reactions are used for one of latent epoxy curing systems.In this work,the reaction mechanism and subsutituent effects for aromatic Claisen rearrangements are investigated by molecular orbital method in order to control those latent epoxy curing systems.A reaction for allyl phenyl ether is examined .First,on the allyl group rearrangement,a chair-type transition state is generated.,From the intermediate ,in the second step ,a hydrogen atom is moved intermolecularly to form the product,0-allyl phenol .The N-allylaniline reaction is found to be less favorable than the allyl phenyl ether reaction .boty kinetically and thermodynamically .For condensed-ring allyl ether compounds , it is supposed that more intensive orbital interaction between the condensed-rings and the allyl group gives a smaller activation energy.