The Reactivities of the Aromatic Amido- and Oxy-Claisen Rearrangements -The Correlation with the Bond Localization Energy-

Abstract

The amido-Claisen rearrangement of N-allyl-N-mesyl derivatives of aniline, 1- and 2- naphthylamines, and 2-, 3- and 9-aminophenanthrenes was kinetically investigated. A good linear relationship between In K and the bond localization energy (BLE) was observed in the rearrangement. In the corresponding oxy-Claisen rearrangement, the kinetical data described in literature were similarly correlated with BLE. These results may demonstrate that the reactivities of these aromatic Claisen rearrangements depend on the difference of the resonance energy between the reactant and the transition state.
The rearrangement of the N-naphthylamides and N-phenanthrylamides, as well as the corresponding oxy-Claisen rearrangement, gave experimentally no position isomers. The pro- babilities of the isomer formation were calculated from the correlated expressions.