Reactions of sulphate radicals with substituted pyridines: a structure–reactivity correlation analysis
- Autores
- Dell'Arciprete, María Laura; Cobos, Carlos Jorge; Furlong, Jorge Javier Pedro; Mártire, Daniel Osvaldo; González, Mónica Cristina
- Año de publicación
- 2007
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- The kinetics of the oxidation of pyridine, 3-chloropyridine, 3-cyanopyridine, 3-methoxypyridine and 3-methylpyridine mediated by SO₄
; 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 - Materia
-
Química
kinetics
oxidation
pyridine
flash photolysis - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- http://creativecommons.org/licenses/by-nc-sa/4.0/
- Repositorio
.jpg)
- Institución
- Universidad Nacional de La Plata
- OAI Identificador
- oai:sedici.unlp.edu.ar:10915/159380
Ver los metadatos del registro completo
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Reactions of sulphate radicals with substituted pyridines: a structure–reactivity correlation analysisDell'Arciprete, María LauraCobos, Carlos JorgeFurlong, Jorge Javier PedroMártire, Daniel OsvaldoGonzález, Mónica CristinaQuímicakineticsoxidationpyridineflash photolysisThe 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 AplicadasLaboratorio de Estudio de Compuestos Orgánicos2007info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf2498-2505http://sedici.unlp.edu.ar/handle/10915/159380enginfo:eu-repo/semantics/altIdentifier/issn/1439-4235info:eu-repo/semantics/altIdentifier/issn/1439-7641info:eu-repo/semantics/altIdentifier/doi/10.1002/cphc.200700456info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-sa/4.0/Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-09-29T11:41:37Zoai:sedici.unlp.edu.ar:10915/159380Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-29 11:41:37.606SEDICI (UNLP) - Universidad Nacional de La Platafalse |
| dc.title.none.fl_str_mv |
Reactions of sulphate radicals with substituted pyridines: a structure–reactivity correlation analysis |
| title |
Reactions of sulphate radicals with substituted pyridines: a structure–reactivity correlation analysis |
| spellingShingle |
Reactions of sulphate radicals with substituted pyridines: a structure–reactivity correlation analysis Dell'Arciprete, María Laura Química kinetics oxidation pyridine flash photolysis |
| 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 |
| dc.creator.none.fl_str_mv |
Dell'Arciprete, María Laura Cobos, Carlos Jorge Furlong, Jorge Javier Pedro Mártire, Daniel Osvaldo González, Mónica Cristina |
| author |
Dell'Arciprete, María Laura |
| author_facet |
Dell'Arciprete, María Laura Cobos, Carlos Jorge Furlong, Jorge Javier Pedro Mártire, Daniel Osvaldo González, Mónica Cristina |
| author_role |
author |
| author2 |
Cobos, Carlos Jorge Furlong, Jorge Javier Pedro Mártire, Daniel Osvaldo González, Mónica Cristina |
| author2_role |
author author author author |
| dc.subject.none.fl_str_mv |
Química kinetics oxidation pyridine flash photolysis |
| topic |
Química kinetics oxidation pyridine flash photolysis |
| dc.description.none.fl_txt_mv |
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 |
| 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. |
| publishDate |
2007 |
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2007 |
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info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Articulo http://purl.org/coar/resource_type/c_6501 info:ar-repo/semantics/articulo |
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article |
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publishedVersion |
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http://sedici.unlp.edu.ar/handle/10915/159380 |
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http://sedici.unlp.edu.ar/handle/10915/159380 |
| dc.language.none.fl_str_mv |
eng |
| language |
eng |
| dc.relation.none.fl_str_mv |
info:eu-repo/semantics/altIdentifier/issn/1439-4235 info:eu-repo/semantics/altIdentifier/issn/1439-7641 info:eu-repo/semantics/altIdentifier/doi/10.1002/cphc.200700456 |
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