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Characterization of solvent mixtures. Part 8 — preferential solvation of chemical probes in binary solvent systems of a polar aprotic hydrogen-bond acceptor solvent with acetonitrile or nitromethane. Solvent effects on aromatic nucleophilic substitution reactions

1999; Wiley; Volume: 12; Issue: 3 Linguagem: Inglês

10.1002/(sici)1099-1395(199903)12

1099-1395

Paolo Mancini, A. Terenzani, Claudia G. Adam, Adriana del C. Pérez, L. R. Vottero,

Chemistry and Chemical Engineering

Journal of Physical Organic ChemistryVolume 12, Issue 3 p. 207-220 Research Article Characterization of solvent mixtures. Part 8 — preferential solvation of chemical probes in binary solvent systems of a polar aprotic hydrogen-bond acceptor solvent with acetonitrile or nitromethane. Solvent effects on aromatic nucleophilic substitution reactions P. M. E. Mancini, Corresponding Author P. M. E. Mancini pmancini@figus.unl.edu.ar Departamento de Química Orgánica, Facultad de Ingeniería Química, Universidad Nacional del Litoral, Santiago del Estero 2829, (3000) Santa Fe, República ArgentinaDepartmento de Química Orgánica, Facultad de Ingeniería Química, Universidad Nacional del Litoral, Santiago del Estero 2829, (3000) Santa Fe, República Argentina.===Search for more papers by this authorA. Terenzani, A. Terenzani Departamento de Química Orgánica, Facultad de Ingeniería Química, Universidad Nacional del Litoral, Santiago del Estero 2829, (3000) Santa Fe, República ArgentinaSearch for more papers by this authorC. Adam, C. Adam Departamento de Química Orgánica, Facultad de Ingeniería Química, Universidad Nacional del Litoral, Santiago del Estero 2829, (3000) Santa Fe, República ArgentinaSearch for more papers by this authorA. Pérez, A. Pérez Departamento de Química Orgánica, Facultad de Ingeniería Química, Universidad Nacional del Litoral, Santiago del Estero 2829, (3000) Santa Fe, República ArgentinaSearch for more papers by this authorL. R. Vottero, L. R. Vottero Departamento de Química Orgánica, Facultad de Ingeniería Química, Universidad Nacional del Litoral, Santiago del Estero 2829, (3000) Santa Fe, República ArgentinaSearch for more papers by this author P. M. E. Mancini, Corresponding Author P. M. E. Mancini pmancini@figus.unl.edu.ar Departamento de Química Orgánica, Facultad de Ingeniería Química, Universidad Nacional del Litoral, Santiago del Estero 2829, (3000) Santa Fe, República ArgentinaDepartmento de Química Orgánica, Facultad de Ingeniería Química, Universidad Nacional del Litoral, Santiago del Estero 2829, (3000) Santa Fe, República Argentina.===Search for more papers by this authorA. Terenzani, A. Terenzani Departamento de Química Orgánica, Facultad de Ingeniería Química, Universidad Nacional del Litoral, Santiago del Estero 2829, (3000) Santa Fe, República ArgentinaSearch for more papers by this authorC. Adam, C. Adam Departamento de Química Orgánica, Facultad de Ingeniería Química, Universidad Nacional del Litoral, Santiago del Estero 2829, (3000) Santa Fe, República ArgentinaSearch for more papers by this authorA. Pérez, A. Pérez Departamento de Química Orgánica, Facultad de Ingeniería Química, Universidad Nacional del Litoral, Santiago del Estero 2829, (3000) Santa Fe, República ArgentinaSearch for more papers by this authorL. R. Vottero, L. R. Vottero Departamento de Química Orgánica, Facultad de Ingeniería Química, Universidad Nacional del Litoral, Santiago del Estero 2829, (3000) Santa Fe, República ArgentinaSearch for more papers by this author First published: 05 March 1999 https://doi.org/10.1002/(SICI)1099-1395(199903)12:3 3.0.CO;2-WCitations: 40AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Abstract The use of chemical probes for the characterization of chemical properties was explored for completely non-aqueous aprotic binary solvent mixtures. The Dimroth–Reichardt ET(30) betaine dye, 4-nitrophenol, 4-nitroanisole, 4-nitroaniline and N,N-diethyl-4-nitroaniline were used to study preferential solvation in binary mixtures of a polar aprotic hydrogen bond-acceptor solvent (DMSO, DMF, acetone, butanone and ethyl acetate) with acetonitrile or nitromethane at 25 °C over the whole range of solvent composition. The indicators were employed to determine ET(30), π*, α and β solvatochromic parameters of the mixtures. Each solvent system was analysed according to its deviation from ideal behaviour due to the preferential solvation of the indicators and also from the complicated intermolecular interactions of the mixed solvent. The validity of the concept of an intrinsic, absolute property of a solvent mixture and whether such a property can be defined by means of chemical probes is discussed. These results were related to the solvent effects on some aromatic nucleophilic substitution reactions. The kinetics of the reactions between 1-fluoro-2,4-dinitrobenzene and primary or secondary amines were studied in ethyl acetate– acetonitrile and N,N-dimethylformamide–acetonitrile mixtures, respectively, taken as representatives of two clearly different solvation models. Copyright © 1999 John Wiley & Sons, Ltd. Citing Literature Volume12, Issue3March 1999Pages 207-220 RelatedInformation