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Journal

2013 | 11 | 12 | 1964-1975

Article title

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

Content

Title variants

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.

Publisher

Journal

Year

Volume

11

Issue

12

Pages

1964-1975

Physical description

Dates

published
1 - 12 - 2013
online
26 - 9 - 2013

Contributors

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

References

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Document Type

Publication order reference

Identifiers

YADDA identifier

bwmeta1.element.-psjd-doi-10_2478_s11532-013-0321-5
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