Medium Effects, Isotope Rate Factors, and the Mechanism of the Reaction of Diphenyldiazomethane with Carboxylic Acids in the Solvents Ethanol and Toluene

O’Ferrall, Rory A. More; Kwok, W. K.; Miller, Sidney I.

doi:10.1021/ja01078a031

Cited by 44 publications

(21 citation statements)

References 7 publications

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“…A mechanism for such abnormally slow proton transfers has been elucidated in terms of a fast equilibrium between an acid and a dye carbinol base to form an intermediate hydrogen‐bonded complex, followed by a rate‐limiting proton transfer along the hydrogen bond to form a colored ion associate under the combined influence of the monomeric acid catalyst, the nonreactive cyclic dimeric acid inhibitor, and the hyperacidic open chain dimeric and trimeric acid catalysts 16. Another example of such a slow minute‐scale proton transfer is the rate‐determining step in the reactions of aliphatic and aromatic carboxylic acids with diazodiphenylmethane in different classes of solvents 22–30. Further examples of slow proton transfers are the reactions between Bromophenol Blue and substituted pyridines in apolar aprotic solvents; timescales of which, however, are much shorter, in the range of milliseconds 31.…”

Section: Introductionmentioning

confidence: 99%

Kinetics of proton transfer between metasubstituted benzoic acids and the carbinol base of crystal violet in toluene: Specific solvent effect–free metasubstituent effect on the reactivity of benzoic acids

Gupta

Rani

2011

Int J of Chemical Kinetics

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Apolar aprotic solvents are particularly advantageous for investigating the intrinsic metasubstituent effect free from complications of specific solvent effects. A kinetic study for toluene-phase proton transfers between meta-Me, F, Cl, Br, I, OMe, OPh, COPh, CF 3 , CN, NO 2 , H benzoic acids and Crystal Violet carbinol base has shown the forward rate constant (log k 1 ) the most appropriate reactivity parameter in toluene. log k 1 (toluene) as compared to other reported reactivity parameters in benzene or toluene have been found more sensitive to the metasubstituent effect. The regression results of the correlation of log k 1 (toluene) of the acids according to the four dual substituent parameter models are statistically significant, and the best result has been obtained using Taft's model. The overall analysis reveals that a

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Section: Introductionmentioning

confidence: 99%

Kinetics of proton transfer between metasubstituted benzoic acids and the carbinol base of crystal violet in toluene: Specific solvent effect–free metasubstituent effect on the reactivity of benzoic acids

Gupta

Rani

2011

Int J of Chemical Kinetics

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“…S3 in the Supporting Information). This concept was further corroborated by other authors in both protic and aprotic solvents. Different factors of investigated reaction system cause acid reactivity: acid structure/conformation, substituent effect, solvent properties (dipolarity/polarizability and hydrogen bonding ability), presence of tautomers, isomerization, intramolecular hydrogen bonding interaction, temperature, etc.…”

Section: Resultsmentioning

confidence: 99%

A LFER Kinetic Study of The Reaction of 5‐Substituted Orotic Acids with Diazodiphenylmethane

Assaleh

Marinković

Nikolić

et al. 2016

Int J of Chemical Kinetics

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Linear free energy relationships (LFER) were applied to the kinetic data for the reaction of 5‐substituted orotic acids, series 1, with diazodiphenylmethane (DDM) in N,N–dimethylformamide and compared with results obtained for 2‐substituted benzoic acids, series 2. The correlation analysis of the kinetic data with σ substituent parameters was carried out using SSP (single substituent parameter) methods. From the sign and value of proportinality constant ρ, lower sensitivity to the substituent effect was obtained in series 1, 0.876, than in the series 2, 1.877. Evaluation of substituent “ortho‐effect” was performed using the Charton model, which includes the steric substituent parameter, and Fujita and Nishioka's model, which describes the total ortho‐effect as contribution of ordinary polar effect, the ortho‐steric and ortho‐polar effects. Results of correlations, obtained by using the Charton model, showed highest contribution of the polar effect, 0.861 vs. 2.101, whereas the steric effect is of lowest significance, 0.117 vs. 0.055, for series 1 and 2, respectively. Also, a low negative value of coefficient with the steric effect, –0.08, obtained from the Fujita–Nishioka model indicated low steric effect, influencing a decrease of the reaction rate in series 1. The structural and substituent effects were also studied by using the density functional theory method, and together with kinetic data, it gave a better insight into the influence of the effect of both geometry and substituent on the π−electron density shift induced reactivity of investigated acids.

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“…As proof of concept, we selected the well-described reaction of diphenyldiazomethane with carboxylic acids 13,14,15,16,17 . The reaction scheme is shown in Figure 3.…”

Section: Introductionmentioning

confidence: 99%

Continuous Flow Chemistry: Reaction of Diphenyldiazomethane with <em>p</em>-Nitrobenzoic Acid

Fritz

Napoline

et al. 2017

JoVE

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Continuous flow technology has been identified as instrumental for its environmental and economic advantages leveraging superior mixing, heat transfer and cost savings through the "scaling out" strategy as opposed to the traditional "scaling up". Herein, we report the reaction of diphenyldiazomethane with p-nitrobenzoic acid in both batch and flow modes. To effectively transfer the reaction from batch to flow mode, it is essential to first conduct the reaction in batch. As a consequence, the reaction of diphenyldiazomethane was first studied in batch as a function of temperature, reaction time, and concentration to obtain kinetic information and process parameters. The glass flow reactor set-up is described and combines two types of reaction modules with "mixing" and "linear" microstructures. Finally, the reaction of diphenyldiazomethane with p-nitrobenzoic acid was successfully conducted in the flow reactor, with up to 95% conversion of the diphenyldiazomethane in 11 min. This proof of concept reaction aims to provide insight for scientists to consider flow technology's competitiveness, sustainability, and versatility in their research.

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Medium Effects, Isotope Rate Factors, and the Mechanism of the Reaction of Diphenyldiazomethane with Carboxylic Acids in the Solvents Ethanol and Toluene

Cited by 44 publications

References 7 publications

Kinetics of proton transfer between metasubstituted benzoic acids and the carbinol base of crystal violet in toluene: Specific solvent effect–free metasubstituent effect on the reactivity of benzoic acids

Kinetics of proton transfer between metasubstituted benzoic acids and the carbinol base of crystal violet in toluene: Specific solvent effect–free metasubstituent effect on the reactivity of benzoic acids

A LFER Kinetic Study of The Reaction of 5‐Substituted Orotic Acids with Diazodiphenylmethane

Continuous Flow Chemistry: Reaction of Diphenyldiazomethane with <em>p</em>-Nitrobenzoic Acid

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