B<scp>ECKMANN</scp>‐Umlagerung und Fragmentierung. 1. Teil. Mechanismus sowie Nachweis der Zwischenstufen Fragmentierungsreaktionen. 7. Mitteilung

Abstract

Abstract The mechanism of the B ECKMANN rearrangement and the fragmentation of ketoximes 1 has been studied by determining rate constants and products in «80%» ethanol of several anti ‐alkyl‐, ‐cycloalkyl‐, ‐aralkyl‐ and ‐phenyl‐ketoxime tosylates with stationary syn ‐methyl and ‐phenyl substituents. The ratio of fragmentation to amide formation is not related to reaction rate, but increases with the stability of the carbonium ion R + formed, as reflected by the solvolysis rates of the corresponding alkyl chlorides RC1. Fragmentation to nitriles, therefore, occurs after the rate‐deter‐ mining migration step.