Reactions of sulphate radicals with substituted pyridines: a structure–reactivity correlation analysis
The kinetics of the oxidation of pyridine, 3-chloropyridine, 3-cyanopyridine, 3-methoxypyridine and 3-methylpyridine mediated by SO₄<M>; radicals are studied by flash photolysis of peroxodisulphate, S₂O₈²⁻−, at pH 2.5 and 9. The absolute rate constants for the reactions of both, the basic and...
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| Formato: | Articulo |
| Lenguaje: | Inglés |
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2007
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| Acceso en línea: | http://sedici.unlp.edu.ar/handle/10915/159380 |
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I19-R120-10915-159380 |
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I19-R120-10915-1593802023-10-27T04:06:40Z http://sedici.unlp.edu.ar/handle/10915/159380 Reactions of sulphate radicals with substituted pyridines: a structure–reactivity correlation analysis Dell'Arciprete, María Laura Cobos, Carlos Jorge Furlong, Jorge Javier Pedro Mártire, Daniel Osvaldo González, Mónica Cristina 2007 2023-10-26T12:24:16Z en Química kinetics oxidation pyridine flash photolysis The kinetics of the oxidation of pyridine, 3-chloropyridine, 3-cyanopyridine, 3-methoxypyridine and 3-methylpyridine mediated by SO₄<M>; radicals are studied by flash photolysis of peroxodisulphate, S₂O₈²⁻−, at pH 2.5 and 9. The absolute rate constants for the reactions of both, the basic and acid forms of the pyridines, are determined and discussed in terms of the Hammett correlation. The monosubstituted pyridines react about 10 times faster with sulphate radicals than their protonated forms, the pyridine ions. The organic intermediates are identified as the corresponding hydroxypyridine radical adducts and their absorption spectra compared with those estimated employing the time-dependent density functional theory with explicit account for bulk solvent effects. A reaction mechanism which accounts for the observed intermediates and the pyridinols formed as products is proposed. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas Laboratorio de Estudio de Compuestos Orgánicos Articulo Articulo http://creativecommons.org/licenses/by-nc-sa/4.0/ Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0) application/pdf 2498-2505 |
| institution |
Universidad Nacional de La Plata |
| institution_str |
I-19 |
| repository_str |
R-120 |
| collection |
SEDICI (UNLP) |
| language |
Inglés |
| topic |
Química kinetics oxidation pyridine flash photolysis |
| spellingShingle |
Química kinetics oxidation pyridine flash photolysis Dell'Arciprete, María Laura Cobos, Carlos Jorge Furlong, Jorge Javier Pedro Mártire, Daniel Osvaldo González, Mónica Cristina Reactions of sulphate radicals with substituted pyridines: a structure–reactivity correlation analysis |
| topic_facet |
Química kinetics oxidation pyridine flash photolysis |
| description |
The kinetics of the oxidation of pyridine, 3-chloropyridine, 3-cyanopyridine, 3-methoxypyridine and 3-methylpyridine mediated by SO₄<M>; radicals are studied by flash photolysis of peroxodisulphate, S₂O₈²⁻−, at pH 2.5 and 9. The absolute rate constants for the reactions of both, the basic and acid forms of the pyridines, are determined and discussed in terms of the Hammett correlation. The monosubstituted pyridines react about 10 times faster with sulphate radicals than their protonated forms, the pyridine ions. The organic intermediates are identified as the corresponding hydroxypyridine radical adducts and their absorption spectra compared with those estimated employing the time-dependent density functional theory with explicit account for bulk solvent effects. A reaction mechanism which accounts for the observed intermediates and the pyridinols formed as products is proposed. |
| format |
Articulo Articulo |
| author |
Dell'Arciprete, María Laura Cobos, Carlos Jorge Furlong, Jorge Javier Pedro Mártire, Daniel Osvaldo González, Mónica Cristina |
| author_facet |
Dell'Arciprete, María Laura Cobos, Carlos Jorge Furlong, Jorge Javier Pedro Mártire, Daniel Osvaldo González, Mónica Cristina |
| author_sort |
Dell'Arciprete, María Laura |
| title |
Reactions of sulphate radicals with substituted pyridines: a structure–reactivity correlation analysis |
| title_short |
Reactions of sulphate radicals with substituted pyridines: a structure–reactivity correlation analysis |
| title_full |
Reactions of sulphate radicals with substituted pyridines: a structure–reactivity correlation analysis |
| title_fullStr |
Reactions of sulphate radicals with substituted pyridines: a structure–reactivity correlation analysis |
| title_full_unstemmed |
Reactions of sulphate radicals with substituted pyridines: a structure–reactivity correlation analysis |
| title_sort |
reactions of sulphate radicals with substituted pyridines: a structure–reactivity correlation analysis |
| publishDate |
2007 |
| url |
http://sedici.unlp.edu.ar/handle/10915/159380 |
| work_keys_str_mv |
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| _version_ |
1807221660185526272 |