Substituent Effects in Hydrolysis of Diaryl Carbonates

1965 ◽  
Vol 30 (11) ◽  
pp. 3989-3991 ◽  
Author(s):  
Glenn D. Cooper ◽  
Harry T. Johnson ◽  
Barry Williams
Keyword(s):  
Substituent Effects ◽  
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 XXVI. Variation of the Substituent Effect with Solvent in Alkaline Hydrolysis of Substituted Alkyl Benzoates

2006 ◽  
Vol 71 (11-12) ◽  
pp. 1557-1570 ◽  
Author(s):  
Vilve Nummert ◽  
Mare Piirsalu ◽  
Ilmar A. Koppel
Keyword(s):  
Kinetic Study ◽  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Substituent Effect ◽  
Substituent Effects ◽  
Alkyl Substituent ◽  
Solvent Parameters ◽  
Substituent Constants ◽  
Hydrolysis Of ◽  
Main Factor

The second-order rate constants k2 (dm3 mol-1 s-1) for the alkaline hydrolysis of substituted alkyl benzoates C6H5CO2R have been measured spectrophotometrically in aqueous 0.5 M Bu4NBr at 50 and 25 °C (R = CH3, CH2Cl, CH2CN, CH2C≡CH, CH2C6H5, CH2CH2Cl, CH2CH2OCH3, CH2CH3) and in aqueous 5.3 M NaClO4 at 25 °C (R = CH3, CH2Cl, CH2CN, CH2C≡CH). The dependence of the alkyl substituent effects on different solvent parameters was studied using the following equations:      ∆ log k = c0 + c1σI + c2EsB + c3∆E + c4∆Y + c5∆P + c6∆EσI + c7∆YσI + c8∆PσI     ∆ log k = c0 + c1σ* + c2EsB + c3∆E + c4∆Y + c5∆P + c6∆Eσ* + c7∆Yσ* + c8∆Pσ* .  ∆ log k = log kR - log kCH3. σI and σ* are the Taft inductive and polar substituent constants. E, Y and P are the solvent electrophilicity, polarity and polarizability parameters, respectively. In the data treatment ∆E = ES - EH2O , ∆Y = YS - YH2O , ∆P = PS - PH2O were used. The solvent electrophilicity, E, was found to be the main factor responsible for changes in alkyl substituent effects with medium. When σI constants were used, variation of the polar term of alkyl substituents with the solvent electrophilicity E was found to be similar to that observed earlier for meta and para substituents, but twice less when σ* constants were used. The steric term for alkyl substituents was approximately independent of the solvent parameters.

Substituent Effects in the Carboxypeptidase A Catalyzed Hydrolysis of Substituted L,.beta.-Phenyllactate Esters

Biochemistry ◽  
1994 ◽  
Vol 33 (49) ◽  
pp. 14750-14757 ◽  
Author(s):  
Alan Osumi ◽  
Abdulkader Rahmo ◽  
Stephen W. King ◽  
Theodore J. Przystas ◽  
Thomas H. Fife
Keyword(s):  
Substituent Effects ◽  
Carboxypeptidase A ◽  
Hydrolysis Of

Substituent Effects on the Hydrolysis of p-Substituted Benzonitriles in Sulfuric Acid Solutions at (25.0± 0.1) °C

2008 ◽  
Vol 63 (9) ◽  
pp. 603-608 ◽  
Author(s):  
Khamis A. Abbas
Keyword(s):  
Sulfuric Acid ◽  
Rate Constants ◽  
Inductive Effect ◽  
Substituent Effects ◽  
Acid Solutions ◽  
Rate Determining Step ◽  
Inductive Effects ◽  
High Concentrations ◽  
Sulfuric Acid Solutions ◽  
Hydrolysis Of

The rate constants of the hydrolysis of p-substituted benzonitriles with sulfuric acid solutions (18.2 M to 10 M) have been determined spectrophotometrically at (25.1±0.1) °C. It was found that the catalytic activity of sulfuric acid was strongly inhibited by water. The logarithms of the observed rate constants were correlated with different substituent inductive (localized) and resonance (delocalized) constants. The results of the correlation studies indicated that the rate-determining step of the hydrolysis of benzonitriles in 18.2 M sulfuric acid was the addition of a nucleophile, and the hydrolysis was clearly enhanced by the electron-withdrawing inductive effect, while the rate-determining step of the hydrolysis of p-substituted benzonitriles in 10.0 M sulfuric acid was most probably the protonation of benzonitriles, and the rate constants increased by both electron-donating resonance and inductive effects. A mixture of the two mechanisms most probably occurred in 15.3 to 17.0 M sulfuric acid. HSO4 − rather thanwater most probably acted as nucleophile in the hydrolysis of benzonitriles especially at high concentrations of sulfuric acid solutions.

Acid catalysed hydrolysis of orthoesters: mechanism of hydrolysis of 2,4,10-trioxaadamantanes substituted in position 3

1980 ◽  
Vol 58 (6) ◽  
pp. 567-573 ◽  
Author(s):  
Otmane Bouab ◽  
Gérard Lamaty ◽  
Claude Moreau ◽  
Odile Pomares ◽  
Pierre Deslongchamps ◽  
...  
Keyword(s):  
Substituent Effects ◽  
Rate Determining Step ◽  
Mechanism Of Hydrolysis ◽  
Volume Substitution ◽  
Hydrolysis Of

The rates of hydrolysis of orthoesters, 2,4,10-trioxaadamantanes, substituted in position 3 (R = H, CH3, C2H5, C6H5) have been determined at 25 and 40 °C in dioxane/water (60:40 by volume). Substitution of hydrogen by the groups CH3, C2H5, and C6H5 shows clearly a decrease in rate: 0.018 (CH3), 0.014 (C2H5), and 0.003 (C6H5). This decrease, in accord with substituent effects, plus the strongly negative entropies of activation observed, suggests that the rate-determining step is the addition of water to the carboxonium ion intermediate.

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.

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