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B ECKMANN ‐Umlagerung und Fragmentierung. 1. Teil. Mechanismus sowie Nachweis der Zwischenstufen Fragmentierungsreaktionen. 7. Mitteilung
Author(s) -
Grob C. A.,
Fischer H. P.,
Raudenbusch W.,
Zergenyi J.
Publication year - 1964
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19640470411
Subject(s) - chemistry , carbonium ion , solvolysis , fragmentation (computing) , medicinal chemistry , alkyl , amide , ethanol , stereochemistry , ion , organic chemistry , hydrolysis , operating system , computer science
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 RC1. Fragmentation to nitriles, therefore, occurs after the rate‐deter‐ mining migration step.