Electron impact induced rearrangements of organic ions. Part 111. A Beckmann-like aryl migration in substituted isoxazol-5(4H)-one molecular ions
- 1 January 1973
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Perkin Transactions 2
- No. 15,p. 2038-2041
- https://doi.org/10.1039/p29730002038
Abstract
A novel unimolecular reaction leading to primary amine radical ions occurs in the gas phase decomposition of ions generated from substituted isoxazol-5(4H)-ones, upon electron impact. The proposed mechanism implies aryl migration as the first step, and this is unambiguously demonstrated by 15N and 2H labelling experiments, metastable transition studies, and exact mass measurements. This [1,2] sigmatropic shift is a fast process, as evidenced by a primary kinetic isotope effect on competing metastable transitions. Energetic and electronic factors involved in the process suggest striking similarities to the Beckmann rearrangement in the condensed phase.Keywords
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