Critical compilation of scales of solvent parameters. Part I. Pure, non-hydrogen bond donor solvents

Abboud, José‐Luis M.; Notari, Robert E.

doi:10.1351/pac199971040645

Cited by 395 publications

(300 citation statements)

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“…Consistently with this interpretation, although both dipolar aprotic solvent has similar dipolarity/polarity values, the reaction is much faster in DMSO (as shown in Table 1), the solvent that exhibits the greater HBA capacity. 11,12 In accordance with our proposal of mixed aggregates between aniline and Ac and DMSO, and their effect on reaction rates, DMSO has been shown to increase the nitrogen electron density of primary and secondary amines. In all the reactions studied in the present work, DNFB reacts faster than DNClB.…”

Section: Resultssupporting

confidence: 84%

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Unusual solvent effects in the reactions of 1-halo-2,4-dinitrobenzenes and aniline in aprotic and dipolar-aprotic solvents. Effects of aggregates

Alvaro¹,

Nudelman²

2003

Arkivoc

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The kinetics of reactions between 1-halogeno-2,4-dinitrobenzene (halogen = F, Cl) and aniline were studied in toluene, acetone, dimethylsulfoxide and in toluene-acetone mixtures. Unexpectedly, when chlorine is the nucleofugue, the second rate coefficients, k A , in toluene shows a parabolic dependence on the amine concentration which indicates a third order in amine kinetic law, while in the dipolar aprotic solvent the dependence is linear. Small additions of acetone to the solvent produce an important increase in rate, much greater then the increase in the permittivity, which is surprising on the basis of the classical effect of a dipolar medium on a dipolar transition state. The reactions with fluorine as the nucleofugue show similar behaviours. All these results are well explained in the frame of the "dimer nucleophile" mechanism.

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Section: Resultssupporting

confidence: 84%

“…On the other hand, several attempts to establish empirical scale of microscopic parameters able to provide a quantitative description of solvent characteristic have been currently reported. 11,12,13 Most of the previous studies on solvent effects in S N Ar have been performed in pure solvents. 1,2 .…”

Section: Introductionmentioning

confidence: 99%

Unusual solvent effects in the reactions of 1-halo-2,4-dinitrobenzenes and aniline in aprotic and dipolar-aprotic solvents. Effects of aggregates

Alvaro¹,

Nudelman²

2003

Arkivoc

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“…c) At 22 . 11.6 52) 10.2 54) 25.2 55) 0.642 56) 0.99 59) 0.61 59) 0.230 59) 21.2 c) 50) 0.644 57) [ 11.4 53) 27.7 55) 0.667 56) 1.04 59) 0.63 59) 0.19 59) 0.669 57) [ 25.6 54) 0.629 56) 0.96 59) 0.60 59) 0.29 59) [OMIm][BF 4 ] 255.6 25.0 c) 50) 0.65 58) 0.98 58) 0.62 58) 0.41 58) [BMPyr][NTf 2 ] 302.6 22.5 b) 32) 11.9 52) 0.544 57) 0.95 59) 0.43 59) 0.24 59) 22 30.4 65) 0.537 66) 0.40 67) 0.77 67) 0.81 67) Et 2 O 104.7 15.4 60) 4.42 60) 19.2 64) 3.9 64) 0.117 66) 0.27 68) 0.00 68) 0.47 68) CHCl 3 80.7 18.9 60) 4.89 60) 4.0 60) 23.1 64) 0.259 …”

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Distribution Behavior of Neutral and Anionic Compounds in Ionic Liquid/Water Biphasic Systems

Katsuta¹

2013

BUNSEKI KAGAKU

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“…More discussion on the subject can be found in specialized books, and review articles. [2][3][4][5][6][7][8][9][10][11] The reason for the multi-parameter dependence of chemical phenomena on solvent properties, point (i) above, is that several solutesolvent interactions come into play; their effects should be taken into account. These include both specific and non-specific interactions, e.g., hydrogen-bonding, dipolar-interactions (ion-dipole, dipoledipole, dipole-induced dipole), and dispersion or London interactions.…”

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Solvation simplified

Seoud¹

2010

Quím. Nova

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Recebido em 24/5/10; aceito em 28/9/10; publicado na web em 16/11/10The effects of solvents on chemical phenomena is complex because there are various solute-solvent interaction mechanisms. Solvatochromism refers to the effects of solvents on the spectra of probes. The study of this phenomenon sheds light on the relative importance of the solvation mechanisms. Solvation in pure solvents is quantitatively analyzed in terms of a multi-parameter equation. In binary solvent mixtures, solvation is analyzed by considering the organic solvent, S, water, W, and a 1:1 hydrogen bonded species (S-W). The applications of solvatochromism to understand distinct chemical phenomena, reactivity and swelling of cellulose, is briefly discussed.Keywords: solvation ; solvatochromism; solute-solvent interactions.The need for understanding solvation is clear: most reactions are carried out in the liquid phase; the solvent is not a "spectator". It acts as a heat-and mass-transfer agent; it participates in proton transfers (for acid/base catalyzed reactions) and in the solvation of ions, dipolar species, etc. Consider the decomposition of 6-nitro-3-carboxybenzisoxazole, whose reaction scheme is depicted in Figure 1. This example is particularly illustrative of the effects of solvents on reactivity because it is a simple, spontaneous decomposition reaction. Therefore, effects of changing the solvent on the observed rate constant, k obs , can be unequivocally attributed to differences in solvation between the reactant state-where the negative charge is concentrated on the carboxylate anion-and the transition state, where the charge is dispersed over several atoms. The half-lives of this reaction in hexamethylphosphotriamide, acetonitrile, and water, are 0.001 s, 11.6 min, and one day, respectively! 1Can these large differences in k obs be correlated with solvent properties? The results of such attempt is shown in Table 1, where the subscript (S) refers to solvent, e r , E T (30), a S , b S refer to the solvent relative permittivity, its empirical polarity, hydrogen-bond donation capacity or "acidity", and hydrogen-bond acceptance capacity or "basicity", respectively (vide infra for more discussion of the last three solvent descriptors). Table 1 reveals that there is no correlation between log k obs and any single solvent property. Inclusion of a second descriptor leads to a noticeable improvement in the regression analysis; a four-descriptor equation gives the best correlation coefficient. The conclusion from Table 1 is obvious: solvent effects on chemical reactivity, and presumably other phenomena, e.g., chemical equilibria and spectroscopic data, are complex; any successful correlation with a single solvent descriptor is, most certainly, fortuitous.The following questions now arise: (i) What is the reason for this complex dependence of chemical phenomena on solvent properties?(ii) Can the relative importance of each solute-solvent interaction be identified and quantified? (iii) How can we treat solvation in solvent mixtures? The object...

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Critical compilation of scales of solvent parameters. Part I. Pure, non-hydrogen bond donor solvents

Cited by 395 publications

References 47 publications

Unusual solvent effects in the reactions of 1-halo-2,4-dinitrobenzenes and aniline in aprotic and dipolar-aprotic solvents. Effects of aggregates

Unusual solvent effects in the reactions of 1-halo-2,4-dinitrobenzenes and aniline in aprotic and dipolar-aprotic solvents. Effects of aggregates

Distribution Behavior of Neutral and Anionic Compounds in Ionic Liquid/Water Biphasic Systems

Solvation simplified

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