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2013 | 11 | 12 | 1964-1975
Tytuł artykułu

Prediction of ortho substituent effect in alkaline hydrolysis of phenyl esters of substituted benzoic acids in aqueous acetonitrile

Treść / Zawartość
Warianty tytułu
Języki publikacji
EN
Abstrakty
EN
The second-order rate constants k for the alkaline hydrolysis of phenyl esters of meta-, para- and ortho-substituted benzoic acids, X-C6H4CO2C6H5, in aqueous 50.9% acetonitrile have been measured spectrophotometrically at 25°C. The log k values for meta and para derivatives correlated well with the Hammett σm,p substituent constants. The log k values for ortho-substituted phenyl benzoates showed good correlations with the Charton equation, containing the inductive, σI, resonance, σ○ R, and steric, E s B, and Charton υ substituent constants. For ortho derivatives the predicted (log k X)calc values were calculated with equation (log k ortho)calc = (log k H AN)exp + 0.059 + 2.19σI + 0.304σ○ R + 2.79E s B − 0.0164ΔEσI - 0.0854ΔEσ○ R, where DE is the solvent electrophilicity, ΔE = E AN - E H20 = −5.84 for aqueous 50.9% acetonitrile. The predicted (log k X)calc values for phenyl ortho-, meta- and para-substituted benzoates in aqueous 50.9% acetonitrile at 25°C precisely coincided with the experimental log k values determined in the present work. The substituent effects from the benzoyl moiety and aryl moiety were compared by correlating the log k values for the alkaline hydrolysis of phenyl esters of substituted benzoic acids, X-C6H4CO2C6H5, in various media with the corresponding log k values for substituted phenyl benzoates, C6H5CO2C6H4-X.
Wydawca

Czasopismo
Rocznik
Tom
11
Numer
12
Strony
1964-1975
Opis fizyczny
Daty
wydano
2013-12-01
online
2013-09-26
Twórcy
  • Institute of Chemistry, Tartu University, 50411, Tartu, Estonia
  • Institute of Chemistry, Tartu University, 50411, Tartu, Estonia
autor
Bibliografia
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Typ dokumentu
Bibliografia
Identyfikatory
Identyfikator YADDA
bwmeta1.element.-psjd-doi-10_2478_s11532-013-0321-5
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