Kinetic study of the oxidation of phenolic derivatives of α,α,α-trifluorotoluene by singlet molecular oxygen [O₂(¹Δg)] and hydrogen phosphate radicals
- Autores
- Rosso, Janina Alejandra; Criado, Susana; Bertolotti, Sonia G.; Allegretti, Patricia Ercilia; Furlong, Jorge Javier Pedro; García, Norman A.; González, Mónica Cristina; Mártire, Daniel Osvaldo
- Año de publicación
- 2003
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- The oxidation kinetics and mechanism of the phenolic derivatives of α,α,α-trifluorotoluene, 2-trifluoromethylphenol, 3-trifluoromethylphenol (3-TFMP), 4-trifluoromethylphenol and 3,5-bis(trifluoromethyl)phenol, mediated by singlet molecular oxygen, O2(¹Δg), and hydrogen phosphate radicals were studied, employing time-resolved O2(¹Δg) phosphorescence detection, polarographic determination of dissolved oxygen and flash photolysis. All the substrates are highly photo-oxidizable through a O2(¹Δg)-mediated mechanism. The phenols show overall quenching constants for O2(¹Δg) of the order of 106 M⁻¹ s⁻¹ in D2O, while the values for the phenoxide ions in water range from 1.2 × 10⁸ to 3.6 × 10⁸ M⁻¹ s⁻¹. The effects of the pH and polarity of the medium on the kinetics of the photo-oxidative process suggest a charge-transfer mechanism. 2-Trifluoromethyl-1,4-benzoquinone is suspected to be the main photo-oxidation product for the substrate 3-TFMP. The absolute rate constants for the reactions of HPO4•− with the substrates range from 4 × 10⁸ to 1 × 10⁹ M⁻¹ s⁻¹. The 3-trifluoromethylphenoxyl radical was observed as the organic intermediate formed after reaction of 3-TFMP with HPO₄•⁻, yielding 2,2’-bis(fluorohydroxymethyl)biphenyl-4,4’-diol as the end product. The observed results indicate that singlet molecular oxygen and hydrogen phosphate radicals not only react at different rates with the phenols of α,α,α-trifluorotoluene, but the reactions also proceed through different reaction channels.
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas
Laboratorio de Estudio de Compuestos Orgánicos - Materia
-
Química
phenolic derivatives
oxidation kinetics - 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:10915/159129
Ver los metadatos del registro completo
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Kinetic study of the oxidation of phenolic derivatives of α,α,α-trifluorotoluene by singlet molecular oxygen [O₂(¹Δg)] and hydrogen phosphate radicalsRosso, Janina AlejandraCriado, SusanaBertolotti, Sonia G.Allegretti, Patricia ErciliaFurlong, Jorge Javier PedroGarcía, Norman A.González, Mónica CristinaMártire, Daniel OsvaldoQuímicaphenolic derivativesoxidation kineticsThe oxidation kinetics and mechanism of the phenolic derivatives of α,α,α-trifluorotoluene, 2-trifluoromethylphenol, 3-trifluoromethylphenol (3-TFMP), 4-trifluoromethylphenol and 3,5-bis(trifluoromethyl)phenol, mediated by singlet molecular oxygen, O2(¹Δg), and hydrogen phosphate radicals were studied, employing time-resolved O2(¹Δg) phosphorescence detection, polarographic determination of dissolved oxygen and flash photolysis. All the substrates are highly photo-oxidizable through a O2(¹Δg)-mediated mechanism. The phenols show overall quenching constants for O2(¹Δg) of the order of 106 M⁻¹ s⁻¹ in D2O, while the values for the phenoxide ions in water range from 1.2 × 10⁸ to 3.6 × 10⁸ M⁻¹ s⁻¹. The effects of the pH and polarity of the medium on the kinetics of the photo-oxidative process suggest a charge-transfer mechanism. 2-Trifluoromethyl-1,4-benzoquinone is suspected to be the main photo-oxidation product for the substrate 3-TFMP. The absolute rate constants for the reactions of HPO4•− with the substrates range from 4 × 10⁸ to 1 × 10⁹ M⁻¹ s⁻¹. The 3-trifluoromethylphenoxyl radical was observed as the organic intermediate formed after reaction of 3-TFMP with HPO₄•⁻, yielding 2,2’-bis(fluorohydroxymethyl)biphenyl-4,4’-diol as the end product. The observed results indicate that singlet molecular oxygen and hydrogen phosphate radicals not only react at different rates with the phenols of α,α,α-trifluorotoluene, but the reactions also proceed through different reaction channels.Instituto de Investigaciones Fisicoquímicas Teóricas y AplicadasLaboratorio de Estudio de Compuestos Orgánicos2003info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf882-887http://sedici.unlp.edu.ar/handle/10915/159129enginfo:eu-repo/semantics/altIdentifier/issn/1474-9092info:eu-repo/semantics/altIdentifier/doi/10.1039/b302502kinfo: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:UNLP2025-09-29T11:41:32Zoai:sedici.unlp.edu.ar:10915/159129Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-29 11:41:32.659SEDICI (UNLP) - Universidad Nacional de La Platafalse |
| dc.title.none.fl_str_mv |
Kinetic study of the oxidation of phenolic derivatives of α,α,α-trifluorotoluene by singlet molecular oxygen [O₂(¹Δg)] and hydrogen phosphate radicals |
| title |
Kinetic study of the oxidation of phenolic derivatives of α,α,α-trifluorotoluene by singlet molecular oxygen [O₂(¹Δg)] and hydrogen phosphate radicals |
| spellingShingle |
Kinetic study of the oxidation of phenolic derivatives of α,α,α-trifluorotoluene by singlet molecular oxygen [O₂(¹Δg)] and hydrogen phosphate radicals Rosso, Janina Alejandra Química phenolic derivatives oxidation kinetics |
| title_short |
Kinetic study of the oxidation of phenolic derivatives of α,α,α-trifluorotoluene by singlet molecular oxygen [O₂(¹Δg)] and hydrogen phosphate radicals |
| title_full |
Kinetic study of the oxidation of phenolic derivatives of α,α,α-trifluorotoluene by singlet molecular oxygen [O₂(¹Δg)] and hydrogen phosphate radicals |
| title_fullStr |
Kinetic study of the oxidation of phenolic derivatives of α,α,α-trifluorotoluene by singlet molecular oxygen [O₂(¹Δg)] and hydrogen phosphate radicals |
| title_full_unstemmed |
Kinetic study of the oxidation of phenolic derivatives of α,α,α-trifluorotoluene by singlet molecular oxygen [O₂(¹Δg)] and hydrogen phosphate radicals |
| title_sort |
Kinetic study of the oxidation of phenolic derivatives of α,α,α-trifluorotoluene by singlet molecular oxygen [O₂(¹Δg)] and hydrogen phosphate radicals |
| dc.creator.none.fl_str_mv |
Rosso, Janina Alejandra Criado, Susana Bertolotti, Sonia G. Allegretti, Patricia Ercilia Furlong, Jorge Javier Pedro García, Norman A. González, Mónica Cristina Mártire, Daniel Osvaldo |
| author |
Rosso, Janina Alejandra |
| author_facet |
Rosso, Janina Alejandra Criado, Susana Bertolotti, Sonia G. Allegretti, Patricia Ercilia Furlong, Jorge Javier Pedro García, Norman A. González, Mónica Cristina Mártire, Daniel Osvaldo |
| author_role |
author |
| author2 |
Criado, Susana Bertolotti, Sonia G. Allegretti, Patricia Ercilia Furlong, Jorge Javier Pedro García, Norman A. González, Mónica Cristina Mártire, Daniel Osvaldo |
| author2_role |
author author author author author author author |
| dc.subject.none.fl_str_mv |
Química phenolic derivatives oxidation kinetics |
| topic |
Química phenolic derivatives oxidation kinetics |
| dc.description.none.fl_txt_mv |
The oxidation kinetics and mechanism of the phenolic derivatives of α,α,α-trifluorotoluene, 2-trifluoromethylphenol, 3-trifluoromethylphenol (3-TFMP), 4-trifluoromethylphenol and 3,5-bis(trifluoromethyl)phenol, mediated by singlet molecular oxygen, O2(¹Δg), and hydrogen phosphate radicals were studied, employing time-resolved O2(¹Δg) phosphorescence detection, polarographic determination of dissolved oxygen and flash photolysis. All the substrates are highly photo-oxidizable through a O2(¹Δg)-mediated mechanism. The phenols show overall quenching constants for O2(¹Δg) of the order of 106 M⁻¹ s⁻¹ in D2O, while the values for the phenoxide ions in water range from 1.2 × 10⁸ to 3.6 × 10⁸ M⁻¹ s⁻¹. The effects of the pH and polarity of the medium on the kinetics of the photo-oxidative process suggest a charge-transfer mechanism. 2-Trifluoromethyl-1,4-benzoquinone is suspected to be the main photo-oxidation product for the substrate 3-TFMP. The absolute rate constants for the reactions of HPO4•− with the substrates range from 4 × 10⁸ to 1 × 10⁹ M⁻¹ s⁻¹. The 3-trifluoromethylphenoxyl radical was observed as the organic intermediate formed after reaction of 3-TFMP with HPO₄•⁻, yielding 2,2’-bis(fluorohydroxymethyl)biphenyl-4,4’-diol as the end product. The observed results indicate that singlet molecular oxygen and hydrogen phosphate radicals not only react at different rates with the phenols of α,α,α-trifluorotoluene, but the reactions also proceed through different reaction channels. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas Laboratorio de Estudio de Compuestos Orgánicos |
| description |
The oxidation kinetics and mechanism of the phenolic derivatives of α,α,α-trifluorotoluene, 2-trifluoromethylphenol, 3-trifluoromethylphenol (3-TFMP), 4-trifluoromethylphenol and 3,5-bis(trifluoromethyl)phenol, mediated by singlet molecular oxygen, O2(¹Δg), and hydrogen phosphate radicals were studied, employing time-resolved O2(¹Δg) phosphorescence detection, polarographic determination of dissolved oxygen and flash photolysis. All the substrates are highly photo-oxidizable through a O2(¹Δg)-mediated mechanism. The phenols show overall quenching constants for O2(¹Δg) of the order of 106 M⁻¹ s⁻¹ in D2O, while the values for the phenoxide ions in water range from 1.2 × 10⁸ to 3.6 × 10⁸ M⁻¹ s⁻¹. The effects of the pH and polarity of the medium on the kinetics of the photo-oxidative process suggest a charge-transfer mechanism. 2-Trifluoromethyl-1,4-benzoquinone is suspected to be the main photo-oxidation product for the substrate 3-TFMP. The absolute rate constants for the reactions of HPO4•− with the substrates range from 4 × 10⁸ to 1 × 10⁹ M⁻¹ s⁻¹. The 3-trifluoromethylphenoxyl radical was observed as the organic intermediate formed after reaction of 3-TFMP with HPO₄•⁻, yielding 2,2’-bis(fluorohydroxymethyl)biphenyl-4,4’-diol as the end product. The observed results indicate that singlet molecular oxygen and hydrogen phosphate radicals not only react at different rates with the phenols of α,α,α-trifluorotoluene, but the reactions also proceed through different reaction channels. |
| publishDate |
2003 |
| dc.date.none.fl_str_mv |
2003 |
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eng |
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eng |
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http://creativecommons.org/licenses/by-nc-sa/4.0/ Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0) |
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