Sonication effects on ester hydrolysis in alcohol–water mixtures; 199-206

Piiskop, Sander; Hagu, Hannes; Järv, Jaak; Salmar, Siim; Tuulmets, Ants

doi:10.3176/chem.2007.4.04

Cited by 6 publications

References 15 publications

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Ultrasonic detection of hydrophobic interactions: a quantitative approach

Tuulmets

Järv

Salmar

et al. 2008

J of Physical Organic Chem

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Kinetic effects of sonication on ester hydrolysis and tert-butyl chloride solvolysis, studied in ethanol-water binary solvent, are discussed in terms of quantitative relationships between their magnitude and the hydrophobicity of reagents. A number of conclusions were drawn from the observed linear free-energy (LFE) relationships. Independent of reaction mechanism, the decrease in reaction rates with increasing ethanol content in the solvent is mainly due to hydrophobic stabilization of the ground state. While hydrophobic species can be hidden in the ethanol clusters present in the region X EtOH > 0.15, at lower ethanol contents hydrophobic reagents are weakly solvated and the hydrophobic stabilization can be easily overcome by sonication.

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Ultrasonic detection of hydrophobic interactions: a quantitative approach

Tuulmets

Järv

Salmar

et al. 2008

J of Physical Organic Chem

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Sonochemical protocol for protection and deprotection of functional groups in organic synthesis

Limbani

Mondal

Bera

2020

Green Sustainable Process for Chemical and Environmental Engineering and Science

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Kinetic sonication effects in aqueous acetonitrile solutions. Reaction rate levelling by ultrasound

Piiskop

Salmar

Tuulmets

et al. 2013

Ultrasonics Sonochemistry

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The kinetics of the pH-independent hydrolysis of 4-methoxyphenyl dichloroacetate were investigated with and without ultrasonic irradiation in acetonitrile-water binary mixtures containing 0.008 to 35 wt.% of acetonitrile and the kinetic sonication effects (kson/knon) were calculated. Molecular dynamics (MD) simulations of the structure of the solutions were performed with ethyl acetate as the model ester. The ester is preferentially solvated by acetonitrile. The excess of acetonitrile over water in the solvation shell grows fast with an increase in the co-solvent content in the bulk solution. In parallel, the formation of a second solvation shell rich in acetonitrile takes place. Significant kinetic sonication effects for the hydrolysis were explained with facile destruction of the diffuse second solvation shell followed by a rearrangement of the remaining solvent layer under sonication. The rate levelling effect of ultrasound was discussed. In an aqueous-organic binary solvent, independent of the solvent composition, the ultrasonic irradiation evokes changes in the reaction medium which result in an almost identical solvation state of the reagent thus leading to the reaction rate levelling.

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Sonication effects on ester hydrolysis in alcohol–water mixtures; 199-206

Cited by 6 publications

References 15 publications

Ultrasonic detection of hydrophobic interactions: a quantitative approach

Ultrasonic detection of hydrophobic interactions: a quantitative approach

Sonochemical protocol for protection and deprotection of functional groups in organic synthesis

Kinetic sonication effects in aqueous acetonitrile solutions. Reaction rate levelling by ultrasound

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