Induktive und sterische Effekte bei der BECKMANN‐CHAPMAN‐Umlagerung von Alkyl‐ketoxim‐pikryläthern
- 1 January 1969
- journal article
- research article
- Published by Wiley in Helvetica Chimica Acta
- Vol. 52 (4) , 913-933
- https://doi.org/10.1002/hlca.19690520408
Abstract
The rates of the BECKMANN‐CHAPMAN rearrangement of the ketoximpicryl‐ethers 1a–1k in 1, 4‐dichlorobutane are correlated with parameters describing the bulk of the substituted groups R and R′. From regression analyses it is concluded that the relative rate constants are mainly controlled by steric contributions in the ground state, such as geminal interactions of R with R′ and vicinal interactions of R′ with OX, and less by inductive effects.Conformational equilibria between (Z)‐ and (E)‐isomers of N‐alkyl‐N‐picryl‐amids have been studied by NMR. in several solvents.Keywords
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