Reaction Pathway and Rate-Determining Step of the Schmidt Rearrangement/Fragmentation: A Kinetic Study

…, T Tokugawa, Y Yamamoto, H Yamataka

Index: Akimoto, Ryo; Tokugawa, Takehiro; Yamamoto, Yutaro; Yamataka, Hiroshi Journal of Organic Chemistry, 2012 , vol. 77, # 8 p. 4073 - 4078

Full Text: HTML

Citation Number: 13

Abstract

The Schmidt rearrangement of substituted 3-phenyl-2-butanone with trimethylsilyl azide in 90%(v/v) aqueous TFA gave two types of product, fragmentation and rearrangement, the ratio of which depends on the substituent: more fragmentation for a more electron-donating substituent. Rate measurements by azotometry indicated the presence of an induction period, and the pseudo-first-order rate constants showed saturation kinetics with respect ...