Solvatochromic study on nitroanilines. Preferential solvation vs dielectric enrichment in binary solvent mixtures

Boggetti, Héctor; Anunziata, Jorge D.; Cattana, Rosa; Silber, Juana J.

doi:10.1016/0584-8539(94)80009-x

Cited by 34 publications

(30 citation statements)

References 29 publications

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“…Hence, in general, solvation of the nitroanilines is dominated by dipole ± dipole and NH´´´O HB interactions between the amino group and THF, whereas cyclohexane can only solvate by dispersion. These results agree with the UV data of Anunziata et al [14] (this further confirms the validity of the NMR method). The reduced PS activity of o-nitroaniline is probably a result of its smaller dipole moment, and of the engagement of the NH hydrogen in an intramolecular HB with a nitro oxygen (as is also reflected in its lower enthalpy of vaporization [66] ).…”

Section: Preferential Solvation Of the Solutes Investigatedsupporting

confidence: 94%

“…Literature data on systems analogous to those we studied are sparse and have been obtained with different techniques; hence comparisons are narrow in scope. Results obtained in this study are compared with those recently obtained by Matteoli [33] with Kirkwood ± Buff integrals, by Anunziata [14] with UV spectroscopy, and by Wakisaka [45,46] with mass spectrometry. We will also attempt an analysis of the preferred solute ± solvent interaction in terms of molecular properties by means of Abrahams equation, [62] and for ions by means of single-ion transfer activity coefficients.…”

Section: Preferential Solvation Of the Solutes Investigatedmentioning

confidence: 64%

“…The PS of nitroanilines in THF/cyclohexane was also investigated for comparison purposes, as this system has previously been studied by UV spectroscopy. [14] Finally, the solvation of dioxane in EtOH/CHCl 3 was examined, as it could be compared with thermodynamic studies carried out by Matteoli and Lepori, who used the KBI method.…”

Section: Resultsmentioning

confidence: 99%

“…The reduced PS activity of o-nitroaniline is probably a result of its smaller dipole moment, and of the engagement of the NH hydrogen in an intramolecular HB with a nitro oxygen (as is also reflected in its lower enthalpy of vaporization [66] ). However, it was not possible to extend the measurements to other solvent pairs [14] because of solubility problems.…”

Section: Preferential Solvation Of the Solutes Investigatedmentioning

confidence: 98%

“…[14] For m-and p-nitroaniline the solvation shell is depleted in cyclohexane (x ' B 0.4); thus THF is the preferred solvent. However, for o-nitroaniline this difference is smaller, indicating that the preference for THF is less marked [in fact, no preference according to Eq.…”

Section: Phenolmentioning

confidence: 99%

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Preferential Solvation of Organic Species in Binary Solvent Mixtures Probed by Intermolecular1H NOESY NMR Spectroscopy

et al. 1999

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The preferential solvation of neutral and ionic organic species (phenol, nitroanilines, N-methylbutyramide, 1,4-dioxane, acetate and tetraalkylammonium ions) in binary solvent mixtures (aqueous CH 3 CN, DMSO, EtOH, 1-PrOH, CH 3 CON(CH 3 ) 2 ; CH 2 Cl 2 /Et 2 O; 1,4-dioxane/benzene; cyclohexane/THF) has been investigated through the analysis of the relative intensities of intermolecular 1 H NOESY cross-peaks according to Macura ± Ernst theory. Observed preferential solvation is discussed in terms of the strength of individual solute ± solvent interactions, hydrophobic interactions in water-rich mixtures, and microheterogeneity in the mixed medium.

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Section: Preferential Solvation Of the Solutes Investigatedsupporting

confidence: 94%

Section: Preferential Solvation Of the Solutes Investigatedmentioning

confidence: 64%

Section: Resultsmentioning

confidence: 99%

Section: Preferential Solvation Of the Solutes Investigatedmentioning

confidence: 98%

Section: Phenolmentioning

confidence: 99%

See 3 more Smart Citations

Preferential Solvation of Organic Species in Binary Solvent Mixtures Probed by Intermolecular1H NOESY NMR Spectroscopy

et al. 1999

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Solvatochronism and preferential solvation of aryliminomethylpyridinium iodines in binary mixtures

Machado

Nascimento

et al. 1997

J. Phys. Org. Chem.

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Solvatochromism in pure and binary solvent mixtures: effects of the molecular structure of the zwitterionic probe

Tada¹,

Novaki²,

Seoud³

2000

J. Phys. Org. Chem.

102

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The solvatochromic behavior of 2,6‐dichloro‐4‐(2,4,6‐triphenyl‐1‐pyridinio)phenolate (WB) was studied by UV–visible spectrophotometry in 32 pure solvents, in binary mixtures of 1‐butanol–cyclohexane (BuOH–Cyhx), and of water with methanol, ethanol, 1‐propanol, 2‐butoxyethanol (2‐BE), acetonitrile, 1,4‐dioxane and THF. The solvent polarity, ET(33) in kcal mol−1, was calculated from the position of the longest‐wavelength intramolecular charge‐transfer absorption band of WB and the results were compared with those for 2,6‐diphenyl‐4‐(2,4,6‐triphenyl‐1‐pyridinio)phenolate [RB, ET(30)] and of 1‐methyl‐8‐oxyquinolinium betaine [QB, ET(QB)]. For pure solvents, ET(33) is a linear function of ET(30), with a slope of practically unity. Steric crowding from the two ortho phenyl rings of RB hinders the formation of H‐bonds with solvents, which results in similar susceptibilities of WB and RB to solvent acidity. For binary solvent mixtures, all plots of ET versus the mole fraction of 1‐butanol or water are non‐linear owing to preferential solvation of the probe by one component of the mixed solvent and, when applicable, to solvent micro‐heterogeneity. Preferential solvation due to non‐specific and specific probe–solvent interactions was calculated for BuOH–Cyhx and water–acetonitrile. Both solvation mechanisms contribute to the non‐ideal behavior in the former binary mixture, whereas probe–solvent specific interactions dominate the solvatochromic behavior in the latter. The composition of the probe solvation shell was calculated. In aqueous alcohols, preferential solvation is by the alcohol. In water–aprotic solvent mixtures, preferential solvation of RB and WB is by the solvent which is present in lower concentration, whereas QB seems to form its own, water‐rich solvation shell over a wide range of water concentration. Copyright © 2000 John Wiley & Sons, Ltd.

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Solvatochromic study on nitroanilines. Preferential solvation vs dielectric enrichment in binary solvent mixtures

Cited by 34 publications

References 29 publications

Preferential Solvation of Organic Species in Binary Solvent Mixtures Probed by Intermolecular1H NOESY NMR Spectroscopy

Preferential Solvation of Organic Species in Binary Solvent Mixtures Probed by Intermolecular1H NOESY NMR Spectroscopy

Solvatochronism and preferential solvation of aryliminomethylpyridinium iodines in binary mixtures

Solvatochromism in pure and binary solvent mixtures: effects of the molecular structure of the zwitterionic probe

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