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

• Authors: Vilve Nummert , Mare Piirsalu , Ilmar Koppel
• Languages of publication: EN

Abstracts

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.

Keywords

EN

Ortho effect; Phenyl esters of benzoic acids; Correlation equations; Solvent effect; Substituent effects

• Publisher: De Gruyter Open
• Journal: Open Chemistry
• Year: 2013
• Volume: 11
• Issue: 12
• Pages: 1964-1975

Dates

published

1 - 12 - 2013

online

26 - 9 - 2013

Contributors

author

Vilve Nummert

• Institute of Chemistry, Tartu University, 50411, Tartu, Estonia

author

Mare Piirsalu

• Institute of Chemistry, Tartu University, 50411, Tartu, Estonia

author

Ilmar Koppel

• Institute of Chemistry, Tartu University, 50411, Tartu, Estonia

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Identifiers

DOI

10.2478/s11532-013-0321-5