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 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.

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.

Kinetics of hydrolysis of peroxodisulphate ions in acidic medium to peroxomonosulphuric acid

1981 ◽  
Vol 46 (5) ◽  
pp. 1229-1236 ◽  
Author(s):  
Jan Balej ◽  
Milada Thumová
Keyword(s):  
Ionic Strength ◽  
Rate Constants ◽  
Acidic Medium ◽  
Measured Data ◽  
Molar Ratios ◽  
Starting Solution ◽  
Kinetics Of Hydrolysis ◽  
Rate Of Hydrolysis ◽  
Kinetics Of ◽  
Hydrolysis Of

The rate of hydrolysis of S2O82- ions in acidic medium to peroxomonosulphuric acid was measured at 20 and 30 °C. The composition of the starting solution corresponded to the anolyte flowing out from an electrolyser for production of this acid or its ammonium salt at various degrees of conversion and starting molar ratios of sulphuric acid to ammonium sulphate. The measured data served to calculate the rate constants at both temperatures on the basis of the earlier proposed mechanism of the hydrolysis, and their dependence on the ionic strength was studied.

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.

Effect of Medium on Reactivity for Alkaline Hydrolysis of p-Nitrophenyl Acetate and S-p-Nitrophenyl Thioacetate in DMSO-H2O Mixtures of Varying Compositions: Ground State and Transition State Contributions

2021 ◽  
Author(s):  
Ik-Hwan Um ◽  
Seungjae Kim
Keyword(s):  
Transition State ◽  
Alkaline Hydrolysis ◽  
Ground State ◽  
Rate Constants ◽  
Kinetic Data ◽  
Reaction Medium ◽  
Stepwise Mechanism ◽  
Rate Determining Step ◽  
Leaving Group ◽  
Hydrolysis Of

Second-order rate constants (kN) for reactions of p-nitrophenyl acetate (1) and S-p-nitrophenyl thioacetate (2) with OH‒ have been measured spectrophotometrically in DMSO-H2O mixtures of varying compositions at 25.0 ± 0.1 oC. The kN value increases from 11.6 to 32,800 M‒1s‒1 for the reactions of 1 and from 5.90 to 190,000 M‒1s‒1 for those of 2 as the reaction medium changes from H2O to 80 mol % DMSO, indicating that the effect of medium on reactivity is more remarkable for the reactions of 2 than for those of 1. Although 2 possesses a better leaving group than 1, the former is less reactive than the latter by a factor of 2 in H2O. This implies that expulsion of the leaving group is not advanced in the rate-determining transition state (TS), i.e., the reactions of 1 and 2 with OH‒ proceed through a stepwise mechanism, in which expulsion of the leaving group from the addition intermediate occurs after the rate-determining step (RDS). Addition of DMSO to H2O would destabilize OH‒ through electronic repulsion between the anion and the negative-dipole end in DMSO. However, destabilization of OH‒ in the ground state (GS) is not solely responsible for the remarkably enhanced reactivity upon addition of DMSO to the medium. The effect of medium on reactivity has been dissected into the GS and TS contributions through combination of the kinetic data with the transfer enthalpies (ΔΔHtr) from H2O to DMSO-H2O mixtures for OH‒ ion.

The Chemical Evolution of a Nitrogenase Model, 20 Alkyl Molybdates(VI) and the Mechanism of Hydrocarbon Production by Nitrogenase [1]

1982 ◽  
Vol 37 (3) ◽  
pp. 380-385 ◽  
Author(s):  
G. N. Schrauzer ◽  
Laura A. Hughes ◽  
Norman Strampach
Keyword(s):  
Aqueous Solution ◽  
Alkaline Hydrolysis ◽  
Room Temperature ◽  
Bond Cleavage ◽  
Model Compounds ◽  
Hydrocarbon Production ◽  
Acidic Solutions ◽  
Reducing Conditions ◽  
Hydrolysis Of ◽  
Derivatives Of

Abstract Colorless alkylmolybdates(VI) of composition R-MoO3-are generated in aqueous solutions by the alkaline hydrolysis of complexes R-Mo(Bpy)(0)2Br(Bpy = 2,2′-bipyridyl, R = CH3 and higher alkyl). At room temperature in alkaline aqueous solution, the new organometallic derivatives of oxomolybdate(VI) are remarkably resistant against Mo-C bond hydrolysis. Decomposition occurs more rapidly on heating, affording unrearranged alkanes according to the eq.: R-MoO3- + OH-→RH + Mo04=. In acidic solutions, the methylmolybdate(VI) species decomposes with the formation of a mixture of methane and ethane while higher alkylmolybdates carrying hydrogen in the β-position relative to molybdenum undergo Mo-C bond heterolysis by way of β-elimina-tion: R-CH2CH2-MoO3 → Mo+4 (aq) + H+ + R-CH = CH2. The Mo-C bond of alkylmolybdates is resistant to oxidants but is very sensitive to cleavage under reducing conditions. Reductive Mo-C bond cleavage occurs particularly rapidly in the presence of thiols and reduced ferredoxin model compounds. The latter reactions simulate the terminal steps of hydrocarbon producing reactions of nitrogenase with alternate substrates such as CN-, R-CN or R-NC, confirming previous mechanistic conclusions concerning the mechanism of nitrogenase action.

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