Kinetics of alkaline hydrolysis of mono- and dimethyl esters of 2,3- and 3,4-thiophenedicarboxylic acids, cyanothiophenecarboxylic acids and their dihydroanalogues

1987 ◽  
Vol 52 (8) ◽  
pp. 2005-2018
Author(s):  
Milan Struhárik ◽  
Pavel Hrnčiar ◽  
Dušan Loos
Keyword(s):  
Kinetic Parameters ◽  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Activation Parameters ◽  
Hydrolysis Rate ◽  
Electronic Effects ◽  
Cyclic System ◽  
Kinetics Of ◽  
Hydrolysis Of ◽  
Reactivity Order

Kinetics of alkaline hydrolysis of mono- and dimethyl esters of 2,3- and 3,4-thiophenedicarboxylic acids and their dihydroanalogues have been studied in 70% dioxane. The rate measurements have been carried out by the titrimetric method and the k1, k2 rate constants evaluated by the Frost-Schwemer method. The activation parameters of these reactions have been calculated. The results are compared with kinetic parameters of alkaline hydrolysis of methyl and dimethyl phthalates. The hydrolysis rate is significantly affected by the cyclic system to which the methoxycarbonyl groups are bound, the reactivity order being: Dihydrothiophene > thiophene > benzene. Also measured were the kinetics of alkaline hydrolyses of methyl 4-cyano-3-thiophenecarboxylate and 3-cyano-2-thiophenecarboxylate and of their dihydroanalogues. No meaningful preference of the hydrolysis of the group at the position 2 has been observed in case of 2,3-isomers. However, it has been confirmed that the hyper- and hypo-ortho transfer of electronic effects operates in the thiophene nucleus.

Influence of medium on alkaline hydrolysis of succinic acid monomethyl and monopropyl esters

1980 ◽  
Vol 45 (11) ◽  
pp. 2873-2882
Author(s):  
Vladislav Holba ◽  
Ján Benko
Keyword(s):  
Succinic Acid ◽  
Kinetic Parameters ◽  
Alkaline Hydrolysis ◽  
Specific Interactions ◽  
Nonaqueous Media ◽  
The Media ◽  
Kinetics Of ◽  
Hydrolysis Of

The kinetics of alkaline hydrolysis of succinic acid monomethyl and monopropyl esters were studied in mixed aqueous-nonaqueous media at various temperatures and ionic strengths. The results of measurements are discussed in terms of electrostatic and specific interactions between the reactants and other components of the reaction mixture. The kinetic parameters in the media under study are related to the influence of the cosolvent on the solvation sphere of the reactants.

KINETICS OF THE AQUEOUS ALKALINE HOMOGENOUS HYDROLYSIS OF HIGH EXPLOSIVE 1, 3,5,7-TETRAAZA- 1, 3,5,7-TETRANITROCYCLOOCTANE (HMX)

1994 ◽  
Vol 30 (3) ◽  
pp. 53-61 ◽  
Author(s):  
Harro M. Heilmann ◽  
Michael K. Stenstrom ◽  
Rolf P. X. Hesselmann ◽  
Udo Wiesmann
Keyword(s):  
Temperature Dependence ◽  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Elevated Temperatures ◽  
Second Order ◽  
Order Rate ◽  
Subsequent Calculation ◽  
Kinetics Of ◽  
Hydrolysis Of ◽  
Order Rate Equation

In order to get basic data for the design of a novel treatment scheme for high explosives we investigated the kinetics for the aqueous alkaline hydrolysis of 1,3,5,7-tetraaza-1,3,5,7-tetranitrocyclooctane (HMX) and the temperature dependence of the rate constants. We used an HPLC procedure for the analysis of HMX. All experimental data could be fit accurately to a pseudo first-order rate equation and subsequent calculation of second-order rate constants was also precise. Temperature dependence could be modeled with the Arrhenius equation. An increase of 10°C led to an average increase in the second-order rate constants by the 3.16 fold. The activation energy of the second-order reaction was determined to be 111.9 ±0.76 kJ·moJ‒1. We found the alkaline hydrolysis to be rapid (less than 2.5% of the initial HMX-concentration left after 100 minutes) at base concentrations of 23 mmol oH‒/L and elevated temperatures between 60 and 80°C.

Effect of the α- and γ-Hydroxyls on the Alkaline Hydrolysis Rate of Nonphenolic β-0-4 Lignin Diastereomers

Holzforschung ◽  
2002 ◽  
Vol 56 (1) ◽  
pp. 67-72 ◽  
Author(s):  
Dexter L. Criss ◽  
Thomas Elder ◽  
Thomas H. Fisher ◽  
Tor P. Schultz
Keyword(s):  
Computational Modeling ◽  
Alkaline Hydrolysis ◽  
Rate Ratio ◽  
Electronic Effect ◽  
Activation Parameters ◽  
Hydrolysis Rate ◽  
Significant Extent ◽  
Hydrolysis Rates ◽  
Lignin Model ◽  
Hydrolysis Of

Summary Nonphenolic β-0-4 erythro and threo lignin model diastereomers with various γ-groups (CH3, CH2-O-CH3, and CH2OH) and Cα-substituents (OH, OCH3) were synthesized, and the alkaline hydrolysis rates and activation parameters determined. In addition, two of the diastereomer pairs were computationally modeled and the thermodynamic values for the ionization of the α- or γ-hydroxyl, and subsequent displacement of the phenolate group to form an epoxide intermediate, were determined. The results suggest that the erythro γ-hydroxyl may participate in the hydrolysis to a significant extent, which results in a relatively high erythro/threo rate ratio for the α,γ-di-OH isomers. The influence of the erythro γ-hydroxyl on the hydrolysis rate may be due to the relatively favorable stability of the erythro γ-oxyanion. The electronic effect of the g-substituent appears to influence how fast the α-hydroxyl displaces the phenoxyl. We had previously suggested that the γ-substituent sterically inhibits hydrolysis of the threo isomer, and computational modeling confirmed this.

Influence of the Polarity of the Medium on the Alkaline Hydrolysis of n-Butyl Acetate in Hydroalcoholic Mixtures

1977 ◽  
Vol 32 (5) ◽  
pp. 496-500
Author(s):  
M. S. Celdrán ◽  
M. V. Ramón ◽  
P. Martínez
Keyword(s):  
Reaction Mechanism ◽  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Butyl Acetate ◽  
Activation Energies ◽  
Free Energies ◽  
Kinetics Of ◽  
Hydrolysis Of

Abstract The kinetics of the alkaline hydrolysis of n-butyl acetate have been studied in water and in hydroalcoholic mixtures. The rate constants, activation energies, frequency factors, entropies, Gibbs free energies and enthalpies of activation have been determined. The radii of the activated com­ plexes have been calculated and related to their degree of solvation. A possible reaction mechanism is formulated.

Kinetics of alkaline hydrolysis of 3,4-thiophenedicarboxylic acid monomethyl ester in aqueous-nonaqueous media

1988 ◽  
Vol 53 (6) ◽  
pp. 1268-1273
Author(s):  
Ján Benko ◽  
Oľga Vollárová
Keyword(s):  
Methyl Alcohol ◽  
Alkaline Hydrolysis ◽  
Mixed Solvents ◽  
Activation Parameters ◽  
Butyl Alcohol ◽  
Nonaqueous Media ◽  
Alcohol Water ◽  
Kinetics Of ◽  
Hydrolysis Of ◽  
Monomethyl Ester

The kinetics of alkaline hydrolysis of 3,4-thiophenedicarboxylic acid monomethyl ester has been studied in mixed solvents water-methyl alcohol, water-tert-butyl alcohol, and water-dioxane. The specific effects causing different courses of these dependences have been evaluated. The greatest changes in the thermodynamic activation parameters have been observed in the medium of water-methyl alcohol.

scholarly journals Acidic and alkaline bimolecular hydrolysis of substituted formanilides. Computational analysis and modelling of substitution effects

2017 ◽  
Vol 10 (1) ◽  
pp. 35-40
Author(s):  
Martin Michalík ◽  
Peter Škorňa ◽  
Vladimír Lukeš ◽  
Erik Klein
Keyword(s):  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Quantum Chemical ◽  
Computational Analysis ◽  
Hydrolysis Rate ◽  
Substitution Effects ◽  
Chemical Methods ◽  
Quantum Chemical Methods ◽  
Hydrolysis Of

Abstract In this article, the study of 67 compounds representing various para-, meta- and ortho- substituted formanilides is presented. These molecules and the products of their acidic and alkaline hydrolysis were studied using DFT quantum chemical methods in order to calculate the reaction enthalpies. These enthalpies are correlated with the hydrolysis rate constants, kH, published for the acid-catalysed acyl cleavage bimolecular (AAC2) mechanism and the modified base-catalysed acyl cleavage bimolecular (BAC2) mechanism. The found linear dependences can be used for the prediction of rate constants of non-synthesised formanilide derivatives.

THE EFFECT ON REACTION RATES CAUSED BY THE SUBSTITUTION OF C14 FOR C12: I. THE ALKALINE HYDROLYSIS OF CARBOXYL-LABELED ETHYL BENZOATE

1949 ◽  
Vol 27b (10) ◽  
pp. 807-812 ◽  
Author(s):  
William H. Stevens ◽  
Richard W. Attree
Keyword(s):  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Room Temperature ◽  
Reaction Rates ◽  
Ethyl Benzoate ◽  
Hydrolysis Rate ◽  
Rate Of Hydrolysis ◽  
Hydrolysis Of

A study of the alkaline hydrolysis of C14 carboxyl-labeled ethyl benzoate has shown that the substitution of C14 for C12 changes the rate of hydrolysis of the ester. Ester molecules containing C14 hydrolyze at a slower rate than normal ester molecules. The ratio of the hydrolysis rate constants at room temperature has been found to be 0.86 ± 0.016.

Kinetics of alkaline hydrolysis and correlation studies of m- and p-substituted piperidinoethyl phenylcarbamates

1989 ◽  
Vol 54 (7) ◽  
pp. 1846-1853 ◽  
Author(s):  
Mária Stankovičová ◽  
Jozef Čižmárik
Keyword(s):  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Activation Parameters ◽  
Hammett Equation ◽  
Correlation Studies ◽  
Lipophilicity Parameter ◽  
Substituent Constants ◽  
Kinetics Of

Kinetics of alkaline hydrolysis have been studied with a series of 15 m- and p-substituted piperidinoethyl phenylcarbamates. The rate constants have been determined at 70, 60, 50, and 40 °C and the activation parameters have been calculated. These values have been correlated with the substituent constants σ, F, R, F, R, π. Validity of the Hammett equation and the Swain-Lupton equation has been confirmed in the series studied and for the p-derivatives, respectively. The lipophilicity parameter π does not correlate with the values found.

Kinetics of pyroarsenate hydrolysis in aqueous solution

1977 ◽  
Vol 30 (6) ◽  
pp. 1187 ◽  
Author(s):  
TG Richmond ◽  
JR Johnson ◽  
JO Edwards ◽  
PH Rieger
Keyword(s):  
Aqueous Solution ◽  
Rate Constant ◽  
Activation Parameters ◽  
Hydrolysis Rate ◽  
Associative Mechanism ◽  
Hydrolysis Rate Constant ◽  
Rate Of Hydrolysis ◽  
Ph Stat ◽  
Kinetics Of ◽  
Hydrolysis Of

The rate of hydrolysis of pyroarsenate in 0.1 mol dm-3 NaClO4 solutions, pH 6-9, was measured by a pH-stat technique at temperatures ranging from 278 to 298 K. The pKa of HAs2O73-, found to be the predominant reactant under these conditions, was 7.3 and 7.6 at 283 and 298 K, respectively. The hydrolysis rate constant for HAs2O73- was 0.05 s-1 at 298 K with activation parameters ΔH? = 49 � 9 kJ mol-1 and ΔS? = -107 � 30 J mol-1 K-1. An associative mechanism is indicated.

Kinetics of alkaline hydrolysis of diphenic and terephthalic acid monomethyl esters

1980 ◽  
Vol 45 (1) ◽  
pp. 255-262 ◽  
Author(s):  
Vladislav Holba ◽  
Ján Benko ◽  
Jana Kozánková
Keyword(s):  
Ionic Strength ◽  
Alkaline Hydrolysis ◽  
Terephthalic Acid ◽  
Activation Parameters ◽  
Diphenic Acid ◽  
Temperature Dependences ◽  
Kinetics Of ◽  
Hydrolysis Of ◽  
Specific Influence ◽  
Monomethyl Ester

The dependence of the rate constant of alkaline hydrolysis of diphenic acid monomethyl ester and terephthalic acid monomethyl ester on ionic strength and temperature was studied together with the specific influence of some electrolytes on the reaction rate. Thermodynamic activation parameters extrapolated to zero ionic strength and critical interionic distances of reacting ions were calculated from the temperature dependences of the rate constants.

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