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Issue 7, 2000
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Ketene-forming eliminations from aryl phenylacetates promoted by R2NH in MeCN. Origin of the curved Hammett plot

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Abstract

Elimination reactions of YC6H4CH2C(O)OC6H3-2-X-4-NO2 promoted by R2NH in MeCN have been studied kinetically. The reactions are second-order and exhibit Brønsted β = 0.52–0.87, |βlg| = 0.37–0.65, and ρH = 1.9–4.1. The β and ρH values decrease as the leaving group becomes less basic and the |βlg| values decrease with a stronger base. The results are interpreted in terms of an E1cb-like transition state with extensive Cβ–H bond cleavage, significant negative charge development at the β-carbon, and limited Cα–OAr bond cleavage. For all reactions, the Hammett plots are curvilinear and show downward curvature. The curvature is more pronounced as the leaving group becomes poorer. The results have been attributed to the highly carbanionic transition state, which is moved towards the reactant on the horizontal reaction coordinate by a stronger electron-withdrawing substituent.

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Publication details

The article was received on 09 Mar 2000, accepted on 14 Apr 2000 and first published on 23 May 2000


Article type: Paper
DOI: 10.1039/B001929L
J. Chem. Soc., Perkin Trans. 2, 2000, 1419-1423

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    Ketene-forming eliminations from aryl phenylacetates promoted by R2NH in MeCN. Origin of the curved Hammett plot

    B. R. Cho, N. S. Kim, Y. K. Kim and K. H. Son, J. Chem. Soc., Perkin Trans. 2, 2000, 1419
    DOI: 10.1039/B001929L

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