Conformational equilibrium of the thermal unimolecular decomposition reactions of substituted 4-fluorophenyl 1,2,4-trioxanes

The unimolecular fragmentations of two fluorine substituted 1,2,4-trioxanes molecules had been interpreted considering the experimental activation parameters of the thermal decomposition reactions in solution. The kinetic data can be rationalized through the postulation of conformational equilibrium...

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Autores principales: Cafferata, Lázaro F. R., Rimada, Rubén Sergio, Jubert, Alicia Haydeé
Formato: Articulo
Lenguaje:Inglés
Publicado: 2005
Materias:
Química
Acceso en línea:http://sedici.unlp.edu.ar/handle/10915/176056
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SEDICI (UNLP) de Universidad Nacional de La Plata
id I19-R120-10915-176056
record_format dspace
spelling I19-R120-10915-1760562025-02-04T04:15:17Z http://sedici.unlp.edu.ar/handle/10915/176056 Conformational equilibrium of the thermal unimolecular decomposition reactions of substituted 4-fluorophenyl 1,2,4-trioxanes Cafferata, Lázaro F. R. Rimada, Rubén Sergio Jubert, Alicia Haydeé 2005 2025-02-03T17:29:49Z en Química The unimolecular fragmentations of two fluorine substituted 1,2,4-trioxanes molecules had been interpreted considering the experimental activation parameters of the thermal decomposition reactions in solution. The kinetic data can be rationalized through the postulation of conformational equilibrium of each of the cis-6-(4-fluorophenyl)-5,6-[2-(4- fluorophenyl)-propyliden-3,3-tetramethylene-1,2,4-trioxacyclohexane (I) and cis-6-(4- fluorophenyl)-5,6-[2-(4-fluorophenyl)]-3-hydroxipropyliden-3,3-tetramethylene-1,2,4- trioxacyclohexane (II) molecules, which would originate intermediate diradicals in their thermolysis in methanol and in n-hexane solutions. The kinetics data and spectroscopic (UV) studies already reported are in close agreement with an ab-initio DFT level calculation performed on those molecules. Las fragmentaciones moleculares de dos 1,2,4-trioxanos flúor-sustituídos han sido interpretadas considerando los valores experimentales de los parámetros de activación obtenidos en sus reacciones de descomposición térmica unimolecular en solución. Los datos cinéticos correspondientes pueden racionalizarse a través de la postulación de equilibrios conformacionales de las moléculas del cis-6-(4-fluorfenil)-5,6-[2-(4-fluorfenil)- propiliden-3,3-tetrametilen-1,2,4-trioxaciclohexano (I) y cis-6-(4-fluorfenil)-5,6-[2-(4- fluorfenil)]-3-hidroxipropiliden-3,3-tetrametilen-1,2,4-trioxaciclohexano (II), que originarían el biradical intermediario correspondiente en sus termólisis en soluciones de metanol y de n-hexano. Los datos de la cinética de las reacciones estudiadas y de estudios espectroscópicos (UV) ya informados están perfectamente de acuerdo con los de un cálculo ab-initio (DFT) realizado en esas moléculas. Laboratorio de Estudio de Compuestos Orgánicos Centro de Química Inorgánica 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 155-162
institution Universidad Nacional de La Plata
institution_str I-19
repository_str R-120
collection SEDICI (UNLP)
language Inglés
topic Química
spellingShingle Química
Cafferata, Lázaro F. R.
Rimada, Rubén Sergio
Jubert, Alicia Haydeé
Conformational equilibrium of the thermal unimolecular decomposition reactions of substituted 4-fluorophenyl 1,2,4-trioxanes
topic_facet Química
description The unimolecular fragmentations of two fluorine substituted 1,2,4-trioxanes molecules had been interpreted considering the experimental activation parameters of the thermal decomposition reactions in solution. The kinetic data can be rationalized through the postulation of conformational equilibrium of each of the cis-6-(4-fluorophenyl)-5,6-[2-(4- fluorophenyl)-propyliden-3,3-tetramethylene-1,2,4-trioxacyclohexane (I) and cis-6-(4- fluorophenyl)-5,6-[2-(4-fluorophenyl)]-3-hydroxipropyliden-3,3-tetramethylene-1,2,4- trioxacyclohexane (II) molecules, which would originate intermediate diradicals in their thermolysis in methanol and in n-hexane solutions. The kinetics data and spectroscopic (UV) studies already reported are in close agreement with an ab-initio DFT level calculation performed on those molecules.
format Articulo
Articulo
author Cafferata, Lázaro F. R.
Rimada, Rubén Sergio
Jubert, Alicia Haydeé
author_facet Cafferata, Lázaro F. R.
Rimada, Rubén Sergio
Jubert, Alicia Haydeé
author_sort Cafferata, Lázaro F. R.
title Conformational equilibrium of the thermal unimolecular decomposition reactions of substituted 4-fluorophenyl 1,2,4-trioxanes
title_short Conformational equilibrium of the thermal unimolecular decomposition reactions of substituted 4-fluorophenyl 1,2,4-trioxanes
title_full Conformational equilibrium of the thermal unimolecular decomposition reactions of substituted 4-fluorophenyl 1,2,4-trioxanes
title_fullStr Conformational equilibrium of the thermal unimolecular decomposition reactions of substituted 4-fluorophenyl 1,2,4-trioxanes
title_full_unstemmed Conformational equilibrium of the thermal unimolecular decomposition reactions of substituted 4-fluorophenyl 1,2,4-trioxanes
title_sort conformational equilibrium of the thermal unimolecular decomposition reactions of substituted 4-fluorophenyl 1,2,4-trioxanes
publishDate 2005
url http://sedici.unlp.edu.ar/handle/10915/176056
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AT rimadarubensergio conformationalequilibriumofthethermalunimoleculardecompositionreactionsofsubstituted4fluorophenyl124trioxanes
AT jubertaliciahaydee conformationalequilibriumofthethermalunimoleculardecompositionreactionsofsubstituted4fluorophenyl124trioxanes
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