74231-54-2Relevant academic research and scientific papers
Non-linear Broensted Correlations: Evidence for a Levelling Off in the Reactivity of Oximate Ions in Aqueous Solution
Terrier, Francois,MacCormack, Patricio,Kizilian, Elyane,Halle, Jean-Claude,Demerseman, Pierre,et al.
, p. 153 - 158 (2007/10/02)
A kinetic study of the reactivity of a series of pyridinium carbaldoximate ions (pKa = 7.13-9.02), which are all potential reactivators of acetylcholinesterase inhibited by organophosphorus poisons, towards p-nitrophenyl acetate in aqueous solution is reported.The corresponding Broensted plot is nonlinear, defining a plateau at pKa 8 which fits very well the data previously obtained for a number of structurally different oximate ions.This phenomenon appears to be typical for the behaviour of these bases since Broensted plots for reactions of oximate ions with other electrophiles show a similar levelling off.These observations support an explanation in terms of a requirement for desolvation of the oximate ion prior to nucleophilic attack which becomes more difficult with increasing basicity.Possible implications of the rapid levelling off in reactivity of oximate ions on their chemical ability to act as efficient reactivators are discussed.
EFFETS MICELLAIRES SUR LA BASICITE ET LA REACTIVITE DE NUCLEOPHILES α AROMATIQUES
Meyer, G.,Viout, P.
, p. 2269 - 2272 (2007/10/02)
The oximation of p-nitrophenylacetate by benzaldoximates in aqueous solution is catalyzed by CTAB micelles.The catalysis is more effective when the base strength of the oximate decreases; the reactivity of benzaldoximates is not dependent on their basicity.Our data may be interpreted in terms of orbital-controlled reactions, with interactions between both the n and ? occupied orbitals of the oximates and the LUMO of the acetate.
