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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

N. Asaad

J.E. Davies

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.