N. Asaad
The search for efficient intramolecular proton transfer from carbon: the kinetically silent intramolecular general base-catalysed elimination reaction of O-phenyl 8-dimethylamino-1-naphthaldoximes
Asaad, N.; Davies, J.E.; Hodgson, D.R.W.; Kirby, A.J.; van Vliet, L.; Ottavi, L.
Authors
J.E. Davies
Professor David Hodgson d.r.w.hodgson@durham.ac.uk
Professor
A.J. Kirby
L. van Vliet
L. Ottavi
Abstract
The ready elimination of phenol/phenoxide from the O-phenyl oxime 10E derived from 8-dimethylamino-1-naphthaldehyde, necessarily involving proton transfer from carbon, is catalysed by the neighbouring NMe2 group at pH > 9. However, reaction is faster, rather than slower, at lower pH. It is shown that the step involving proton transfer is not cleanly rate determining at any pH: the preferred route involves syn/anti isomerization to form the more reactive Z-isomer. The rate constant for the anti elimination cannot be extracted from the available data, so no reliable estimate of effective molarity (EM) is possible.
Citation
Asaad, N., Davies, J., Hodgson, D., Kirby, A., van Vliet, L., & Ottavi, L. (2005). The search for efficient intramolecular proton transfer from carbon: the kinetically silent intramolecular general base-catalysed elimination reaction of O-phenyl 8-dimethylamino-1-naphthaldoximes. Journal of Physical Organic Chemistry, 18(2), 101-109. https://doi.org/10.1002/poc.858
Journal Article Type | Article |
---|---|
Publication Date | 2005-02 |
Deposit Date | Apr 12, 2007 |
Journal | Journal of Physical Organic Chemistry |
Print ISSN | 0894-3230 |
Electronic ISSN | 1099-1395 |
Publisher | Wiley |
Peer Reviewed | Peer Reviewed |
Volume | 18 |
Issue | 2 |
Pages | 101-109 |
DOI | https://doi.org/10.1002/poc.858 |
Keywords | Proton transfer, Intramolecular general base catalysis, Elimination, Oxime. |
Public URL | https://durham-repository.worktribe.com/output/1574432 |
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