Unexpected Substituent Effects in the Iso-Heterocyclic Boulton-Katritzky Rearrangement of 3-Aroylamino-5-Methyl-1,2,4-Oxadiazoles: a Mechanistic Study

The kinetics of the iso-heterocyclic mononuclear rearrangement of some 3-aroylamino-5-methyl-1,2,4-ozadiazoles was carefully examined under largely variable acidic or alkaline conditions. This reaction may proceed via two different mechanistic pathways (an uncatalyzed and a base-catalyzed one), as accounted for also by evaluation of the relevant activation parameters. Substituent effects, as quantified by means of Hammett's equation, appear relatively modest; however, they reveal some interesting anomalies, which enabled us to draw a very precise picture of the intimate reaction course.