The separation of polar and steric effects. Part VIII. The influence of the solvent on the kinetics of the reactions of benzoic acid and meta- or para-substituted benzoic acid with diazodiphenylmethane

Buckley, A.; Chapman, N. B.; Dack, Michael R. J.; Shorter, J.; Wall, H. M.

doi:10.1039/j29680000631

Cited by 35 publications

(32 citation statements)

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“…The results obtained show that the rate constants increase with solvent polarity. This is in accordance with the supposed mechanism of the reaction [6][7][8][9]. The exceptionally high value of the reaction rate constant in chloroform could be explained by the low polarity of this solvent (π * = 0.58) and a complete lack of proton acceptor effects, because of which the carboxylic acid dissolved in it exists in form of dimers [9].…”

Section: Resultssupporting

confidence: 78%

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Solvent and structural effects on the kinetics of the reactions of cycloalkenylcarboxylic and cycloalkenylacetic acids with diazodiphenylmethane

Nikolić

Ušćumlić

Krstic

2005

Int J of Chemical Kinetics

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The rate constants for the reaction of different cycloalkenylcarboxylic, cycloalkenylacetic acids, and phenylacetic acid with diazodiphenylmethane were determined in 12 aprotic solvents at 30 • C. In order to explain the kinetic results through solvent effects, the secondorder rate constant of the examined acids was correlated using the Kamlet-Taft solvatochromic equation. The correlations of the kinetic data were carried out by means of multiple linear regression analysis, and the solvent effects on the reaction rates were analyzed in terms of initial and transition state contributions. The opposite signs of the electrophilic and the nucleophilic parameters are in agreement with the well-known mechanism of the reaction of carboxylic acids with diazodiphenylmethane. The quantitative relationship between the molecular structure and the chemical reactivity is also discussed. C 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: [361][362][363][364][365][366][367] 2005

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Section: Resultssupporting

confidence: 78%

“…Diazodiphenylmethane was prepared by the method of Smith et al [20], and stock solutions were stored in a refrigerator and diluted before use. Solvents were purified as described in previous papers [6,21]. All the solvents used in kinetic studies were analytical grade.…”

Section: Methodsmentioning

confidence: 99%

Solvent and structural effects on the kinetics of the reactions of cycloalkenylcarboxylic and cycloalkenylacetic acids with diazodiphenylmethane

Nikolić

Ušćumlić

Krstic

2005

Int J of Chemical Kinetics

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“…I n the ionization of 2,6-di-substituted phenols (15,16) and benzoic acids (ll), this effect is apparent in increasing the reaction constants observed from those of the parent systems. The medium effect on the benzoic acid system in this reaction has been studied by Chapman, and co-workers (17) and ourselves (18). The reaction constants, p and p, (see Tables IV and V), available for both systems show a reasonably linear relationship, except for dimethyl sulfoxide.…”

Section: Ddm Reactiorzmentioning

confidence: 99%

The transmission of polar effects. Part V. The kinetics of esterification with diazodiphenylmethane and the ionization of substituted acetic and propionic acids in several solvents

Bowden¹,

Hardy²,

Parkin³

1968

Can. J. Chem.

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The rate coefficients for the reaction with diazodiphenylmethane in methanol, ethanol, isopropyl alcohol, t-butyl alcohol, 2-methoxyethanol, 2-n-butoxyethanol, dimethyl sulfoxide, ethyl acetate, and toluene at 30" and the pK, values in water, 50% ethanol-water, and 80% 2-methoxyethanol-water of 18 substituted acetic and propionic acids have been determined. A further 14 acids have been studied to a more limited extent. The effect of substitution has been estimated by linear free energy relations. The reaction constants for the ionization reaction are almost independent of the medium. This is interpreted as being due to the field effect of the proximate polar substituents passing through the molecular cavity almost alone. The occurrence of steric inhibition of solvation causing acid weakening for bulky multisubstitution is confirmed. The reaction constants for the esterification reaction are affected by the solvent. This is attributed to dependence on solvation of the transition state.Canadian Journal of Chemistry, 46, 2929 (1968) IntroductionAs part of our examination of the mode of the transmission of polar effects, it was considered important that transmission in aliphatic systems and their dependence on the medium should be studied. Suitable reactions were considered to be the esterification of carboxylic acids with diazodiphenylmethane (DDM) and their ionization. The system chosen for this study was a series of singly substituted acetic and 3-substituted propionic acids, together with a number of more highly substituted acids. The intention was to obtain a comprehensive series of results for the esterification and ionization reactions for this model system in order to be able to discuss the influence of the substituents on reactivity in aliphatic systems.Taft in his pioneering studies (1) made a distinct advance in understanding polar substituent effects in aliphatic systems. The aliphatic polar substituent constants, a*, which had been separated from the accompanying steric effects in ester hydrolysis, were found to correlate, among other reactions, the ionization of aliphatic carboxylic acids in water at 25" (1) and the esterification of the acids with DDM in ethanol at 25" (2). Hoefelmeyer and Hancock (3) and Bowden, Chapman, and Shorter (4) have extended these correlations to the esterification of aliphatic

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“…Diazodiphenylmethane was prepared by the method described by Smith and Howard [15], and stock solutions were stored in a refrigerator and diluted before use. Solvents were puriÞed as described in previous papers [16,17]. All the solvents used in kinetic studies were analytical grade.…”

Section: Methodsmentioning

confidence: 99%

A linear solvation energy relationship study for the reactivity of 2‐(4‐substituted phenyl)‐cyclohex‐1‐enecarboxylic, 2‐(4‐substituted phenyl)‐benzoic, and 2‐(4‐substituted phenyl)‐acrylic acids with diazodiphenylmethane in various solvents

Nikolić

Ušćumlić

Juranić

2010

Int J of Chemical Kinetics

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The reactivities of 2-(4-substituted phenyl)-cyclohex-1-enecarboxylic acids, 2-(4-substituted phenyl)-benzoic acids, and 2-(4-substituted phenyl)-acrylic acids with diazodiphenylmethane in various solvents were investigated. To explain the kinetic results through solvent effects, the second-order rate constants of the examined acids were correlated using the Kamlet-Taft solvatochromic equation. The correlations of the kinetic data were carried out by means of multiple linear regression analysis, and the solvent effects on the reaction rates were analyzed in terms of initial and transition state contributions. The signs of the equation coefficients support the proposed reaction mechanism. The solvation models for all investigated carboxylic acids are suggested. The quantitative relationship between the molecular structure and the chemical reactivity is discussed, as well as the effect of geometry on the reactivity of the examined molecules. C

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The separation of polar and steric effects. Part VIII. The influence of the solvent on the kinetics of the reactions of benzoic acid and meta- or para-substituted benzoic acid with diazodiphenylmethane

Abstract: Dr. K. Bowden (personal communication) and his co-workers have also observed a similar effect for phenylacetic acid reacting with diazodiphenylmethane in ethyl acetate, but not in dimethyl sulphoxide.

Cited by 35 publications

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Solvent and structural effects on the kinetics of the reactions of cycloalkenylcarboxylic and cycloalkenylacetic acids with diazodiphenylmethane

Solvent and structural effects on the kinetics of the reactions of cycloalkenylcarboxylic and cycloalkenylacetic acids with diazodiphenylmethane

The transmission of polar effects. Part V. The kinetics of esterification with diazodiphenylmethane and the ionization of substituted acetic and propionic acids in several solvents

A linear solvation energy relationship study for the reactivity of 2‐(4‐substituted phenyl)‐cyclohex‐1‐enecarboxylic, 2‐(4‐substituted phenyl)‐benzoic, and 2‐(4‐substituted phenyl)‐acrylic acids with diazodiphenylmethane in various solvents

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