Prediction of solvent effect on the reaction rate and endo/exo selectivity of a Diels–Alder reaction using molecular surface electrostatic potential

Abstract

Molecular surface electrostatic potential was used to predict the solvent effect on the reaction rate, endo/exo selectivity and diastereomeric excess of a Diels-Alder reaction. It is shown that these quantities can be expressed in terms of molecular surface electrostatic potentials of solvents which are obtained computationally by the HF/6-31þþG* procedure. Regression analyses and an experimental database are used to obtain analytical representation of rate constant, endo/exo selectivity and diastereomeric excess. The models obtained show that the hydrogen bond donor ability of solvents on the above mentioned properties is substantial, whereas solvophobicity only affects the reaction rate and endo/exo selectivity of the reaction.

Solvatochromic absorbance probe behavior within 1-butyl-3-methylimidazolium hexafluorophosphate+propylene carbonate: Preferential solvation or solvent–solvent interaction?

“…Empirical solvatochromic parameters are shown to be useful in correlating a wide range of physicochemical properties [49][50][51][52][53][54][55]. The prediction of solvatochromic parameters of mixtures, using a minimum number of experiments may provide a useful computational tool.…”

Investigation of Solvent Effects on the Reaction of 1-Fluoro-2,4-Dinitrobenzene with Aniline in Molecular-Molecular and Ionic Liquid–Molecular Solvent Mixtures

“…Both the formation of the intermediate and its decomposition to products can be a rate-limiting step [8][9][10][11][12][13][14][15][16][17]. www.prkm.co.uk water content up to a maximum at mole fraction of 0.9 with respect to water and then decreases to pure water; however, it decreases smoothly with the ethyl acetate content in methanol-ethyl acetate mixtures (rate coefficient data are summarised in Tables ESI1 and ESI2).…”

“…Therefore, there is a continuing challenge to understand the role of ionic liquids in such reactions. In continuing our studies on solvent effects [10][11][12][13][14][15][16][17][19][20], we report here a kinetic study of the reaction between 1-fluoro-2,4-dinitrobenzene (FDNB) and aniline performed in various compositions of several molecular solvent mixtures and molecular solvents mixed with 2-hydroxyethylammonium formate as an ionic liquid at 25°C. The correlation between the kinetic data and the molecular-microscopic solvent parameters has been investigated and discussed using the general linear free energy relationship (LFER) model.…”

“…Solvent properties such as polarity, polarisability, and hydrogen bonding ability are usually determined from the solvatochromic shifts of selected chemical solutes that reflect the molecularmicroscopic properties of a solvent [6][7][8][9]. The same interactions in reaction media can affect the rate and mechanism of the reactions [8][9][10][11][12][13][14][15][16][17]. The solvent effect as a typical property is described by general correlation models, which give a simultaneous calculation of the contributions of nonspecific solute-solvent interactions such as normalised polarity (E T N ) and polarity-polarisability (π*) and specific solutesolvent interactions such as hydrogen-bond acceptor (HBA) and hydrogen-bond donor (HBD) abilities [1,7].…”

Solvents Design on the Basis of Molecular-Microscopic Properties of Binary Mixtures for Lycopene Extraction

“…Solute-solvent interactions developed in solvation shell of the solutes, cause physical and chemical effects in many processes. These effects of the medium are originated from changes in its polarity, solvophibicity and hydrogen bonding [11][12][13][14].…”