scholarly journals XVIII.—Diortho-substituted benzoic acids. Part III. Hydrolysis of substituted benzamides

1897 ◽  
Vol 71 (0) ◽  
pp. 229-234 ◽  
Author(s):  
John J. Sudborough ◽  
Percy G. Jackson ◽  
Lorenzo L. Lloyd
Keyword(s):  
Benzoic Acids ◽  
Substituted Benzamides ◽  
Substituted Benzoic Acids ◽  
Hydrolysis Of

Kinetic study of hydrolysis of benzoates. part xxvii. ortho substituent effect in alkaline hydrolysis of phenyl esters of substituted benzoic acids in aqueous Bu4NBr

2009 ◽  
Vol 74 (1) ◽  
pp. 29-42 ◽  
Author(s):  
Vilve Nummert ◽  
Mare Piirsalu ◽  
Signe Vahur ◽  
Oksana Travnikova ◽  
Ilmar A. Koppel
Keyword(s):  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Pure Water ◽  
Substituent Effects ◽  
Benzoic Acids ◽  
Resonance Effects ◽  
The Media ◽  
Substituted Benzoic Acids ◽  
Hydrolysis Of ◽  
Ortho Substituent

The second-order rate constants k (in dm3 mol–1 s–1) for alkaline hydrolysis of phenyl esters of meta-, para- and ortho-substituted benzoic acids, X-C6H4CO2C6H5, have been measured spectrophotometrically in aqueous 0.5 and 2.25 M Bu4NBr at 25 °C. The substituent effects for para and meta derivatives were described using the Hammett relationship. For the ortho derivatives the Charton equation was used. For ortho-substituted esters two steric scales were involved: the EsB and the Charton steric (υ) constants. When going from pure water to aqueous 0.5 and 2.25 M Bu4NBr, the meta and para polar effects, the ortho inductive and resonance effects in alkaline hydrolysis of phenyl esters of substituted benzoic acids, became stronger nearly to the same extent as found for alkaline hydrolysis of C6H5CO2C6H4-X. The steric term of ortho-substituted esters was almost independent of the media considered. The rate constants of alkaline hydrolysis of ortho-, meta- and para-substituted phenyl benzoates (X-C6H4CO2C6H5, C6H5CO2C6H4-X) and alkyl benzoates, C6H5CO2R, in water, 0.5 and 2.25 M Bu4NBr were correlated with the corresponding IR stretching frequencies of carbonyl group, (ΔνCO)X.

Kinetic Study of Hydrolysis of Benzoates. Part XXV. Ortho Substituent Effect in Alkaline Hydrolysis of Phenyl Esters of Substituted Benzoic Acids in Water

2006 ◽  
Vol 71 (1) ◽  
pp. 107-128 ◽  
Author(s):  
Vilve Nummert ◽  
Mare Piirsalu ◽  
Vahur Mäemets ◽  
Ilmar Koppel
Keyword(s):  
Acid Hydrolysis ◽  
Alkaline Hydrolysis ◽  
Substituent Effect ◽  
Ethyl Esters ◽  
Benzoic Acids ◽  
Neat Water ◽  
Substituted Benzoic Acids ◽  
Hydrolysis Of Esters ◽  
Hydrolysis Of

The second-order rate constants k2 for alkaline hydrolysis of phenyl esters of meta-, para- and ortho-substituted benzoic acids, X-C6H4CO2C6H5 (X = H, 3-Cl, 3-NO2, 3-CH3, 4-NO2, 4-Cl, 4-F, 4-CH3, 4-OCH3, 4-NH2, 2-NO2, 2-CN, 2-F, 2-Cl, 2-Br, 2-I, 2-CH3, 2-OCH3, 2-CF3, 2-NH2), and of substituted phenyl esters of benzoic acid, C6H5CO2C6H4-X (X = 2-I, 2-CF3, 2-C(CH3)3, 4-Cl, 4-CH3, 4-OCH3, 4-NH2), have been measured spectrophotometrically in water at 25 °C. The substituent effect in alkaline hydrolysis of phenyl esters of para-substituted benzoic acids, similar to that for ethyl esters of para-substituted benzoic acids, was found to be precisely described by the Hammett relationship (ρ = 1.7 in water). The log k value for alkaline hydrolysis of phenyl and ethyl esters of meta-, para- and ortho-substituted benzoic acids, X-C6H4CO2R, was nicely correlated with log km,p,ortho = log ko + (ρ)m,pσ + (ρI)orthoσI + (ρ°R)orthoσ°R + δorthoEsB where σ, σI, σ°R are the Hammett polar, Taft inductive and Taft resonance (σ°R = σ° - σI) substituent constants, respectively. EsB is the steric scale for ortho substituents calculated on the basis of the log k values for the acid hydrolysis of ortho- substituted phenyl benzoates in water owing to the ortho substituent in the phenyl of phenyl benzoates. In water, the main factors responsible for changes in the ortho substituent effect in alkaline hydrolysis of phenyl and ethyl esters of ortho-substituted benzoic acids, X-C6H4CO2R, were found to be the inductive and steric factors while the role of the resonance term was negligible ((ρ°R)ortho ca. 0.3). In alkaline hydrolysis of substituted benzoates in neat water, the ortho inductive effect appeared to be 1.5 times and steric influence 2.7 times higher than the corresponding influences from the ortho position in the phenyl of phenyl benzoates. The contributions of the steric effects in alkaline hydrolysis of esters of ortho-substituted benzoic acids was found to be approximately the same as in acid hydrolysis of esters of ortho-substituted benzoic and acid esterification of ortho-substituted benzoic acids.

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

2013 ◽  
Vol 11 (12) ◽  
pp. 1964-1975 ◽  
Author(s):  
Vilve Nummert ◽  
Mare Piirsalu ◽  
Ilmar Koppel
Keyword(s):  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Substituent Effect ◽  
Substituent Effects ◽  
Benzoic Acids ◽  
Aqueous Acetonitrile ◽  
Substituent Constants ◽  
Substituted Benzoic Acids ◽  
Hydrolysis Of ◽  
Ortho Substituent

AbstractThe 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.

Substituent Effects on the Base-Catalysed Hydrolysis of Phenyl Esters of ortho-Substituted Benzoic Acids

2001 ◽  
Vol 66 (5) ◽  
pp. 770-784 ◽  
Author(s):  
Ingrid Bauerová ◽  
Miroslav Ludwig
Keyword(s):  
Substituent Effects ◽  
Uv Spectrophotometry ◽  
Reaction Centre ◽  
Benzoic Acids ◽  
Model Compounds ◽  
Pseudo First Order Reaction ◽  
Reaction Conditions ◽  
Substituted Benzoic Acids ◽  
Kinetics Of ◽  
Hydrolysis Of

Fourteen model phenyl esters of 2-substituted benzoic acids were synthesised. Structures and purity of model compounds were confirmed by 1H and 13C NMR spectroscopy, as well as by HPLC and elemental analysis. Kinetics of base-catalysed hydrolysis of model phenyl esters occurring by the BAc2 mechanism were measured by UV spectrophotometry in 50% (v/v) aqueous dimethyl sulfoxide solutions at 25 °C under pseudo-first-order reaction conditions (c(NaOH) = 0.001-1.0 mol l-1). Linear relation between J-E and log kobs with the slope close to unity was found for all model compounds. Neither one-parameter nor multiparameter Hammett-type description of variability of experimental data obtained for phenyl esters of 2-substituted benzoic acids was found. Two groups (conjugating and non-conjugating) were created by division of ortho-substituents in ortho-position using the AISE theory, based on their interaction with the reaction centre.

Substituent Effects on the Base-Catalysed Hydrolysis of Phenyl Esters of para-Substituted Benzoic Acids

2000 ◽  
Vol 65 (11) ◽  
pp. 1777-1790 ◽  
Author(s):  
Ingrid Bauerová ◽  
Miroslav Ludwig
Keyword(s):  
Phosphorus Oxychloride ◽  
Substituent Effects ◽  
Alternative Interpretation ◽  
Alkaline Solutions ◽  
Uv Spectrophotometry ◽  
Benzoic Acids ◽  
Model Compounds ◽  
Substituted Benzoic Acids ◽  
Benzoyl Chlorides ◽  
Hydrolysis Of

Seventeen model phenyl esters of 4-substituted benzoic acids were synthesised by the reaction of substituted benzoyl chlorides with phenol in aqueous alkaline solutions (Schotten-Baumann reaction), in pyridine (Einhorn reaction), or by the reaction of substituted benzoic acids with phosphorus oxychloride. Structures and purity of the model compounds were confirmed by 1H NMR and 13C NMR spectroscopy as well as by HPLC and elemental analysis. Phenyl 4-aminobenzoate was synthesised by reduction of phenyl 4-nitrobenzoate in methanol on palladium. Kinetics of base-catalysed hydrolysis of model phenyl esters occurring by the BAc2 mechanism were measured by UV spectrophotometry in 50% (v/v) aqueous dimethyl sulfoxide solutions at 25 °C under pseudo-first-order conditions, (c[NaOH] = 0.001-1.0 mol l-1). The addition of OH- to phenyl benzoates was used to establish the kinetic J-E acidity scale. Linear relation between J-E and log kobs with the slope near unity was found for all the model compounds. The kinetic constants of hydrolysis of phenyl esters of 4-substituted benzoic acids precisely obey the Hammett relationship (σp) with ρ = 2.44. Quantitatively comparable results have been obtained by application of Alternative Interpretation of Substituent Effects theory (AISE) using the σi set of substituent constants.

Thermochemistry of Substituted Benzamides and Substituted Benzoic Acids: Like Tree, Like Fruit?

ChemPhysChem ◽  
2018 ◽  
Vol 19 (5) ◽  
pp. 619-630 ◽  
Author(s):  
Sergey P. Verevkin ◽  
Vladimir N. Emel'yanenko ◽  
Dzmitry H. Zaitsau
Keyword(s):  
Benzoic Acids ◽  
Substituted Benzamides ◽  
Substituted Benzoic Acids
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