meso-TETRAPHENYLIRONPORPHYRIN(III) CHLORIDE CATALYZED OXIDATION OF ANILINE AND ITS SUBSTITUENTS BY m-CHLOROPERBENZOIC ACID

The most fascinating feature of heme-enzymes such as cytochromes P450 is their ability to carry out oxidations with high selectivity. Metalloporphyrin complexes are used as replicate compounds for cytochrome P450. A kinetic analysis has been carried out with the aim of understanding the mechanistic...

Descripción completa

Guardado en:

Detalles Bibliográficos
Autores principales:	RAJA,M, KARUNAKARAN,K
Lenguaje:	English
Publicado:	Sociedad Chilena de Química 2012
Materias:	Aniline oxidation m-chloroperbenzoic acid meso-tetraphenylporphyriniron(III) chloride
Acceso en línea:	http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072012000400005
Etiquetas:	Agregar Etiqueta Sin Etiquetas, Sea el primero en etiquetar este registro!

id	oai:scielo:S0717-97072012000400005
record_format	dspace
spelling	oai:scielo:S0717-970720120004000052013-04-04meso-TETRAPHENYLIRONPORPHYRIN(III) CHLORIDE CATALYZED OXIDATION OF ANILINE AND ITS SUBSTITUENTS BY m-CHLOROPERBENZOIC ACIDRAJA,MKARUNAKARAN,K Aniline oxidation m-chloroperbenzoic acid meso-tetraphenylporphyriniron(III) chloride The most fascinating feature of heme-enzymes such as cytochromes P450 is their ability to carry out oxidations with high selectivity. Metalloporphyrin complexes are used as replicate compounds for cytochrome P450. A kinetic analysis has been carried out with the aim of understanding the mechanistic studies on oxidation of anilines by m-chloroperbenzoic acid catalyzed by meso-tetraphenylironporphyrin(III) chloride in aqueous acetic acid medium. The order of the reaction is found to be second order with respect to the substrate and first order with respect to the catalyst and oxidant. Product analysis proves that azobenzene is the sole product in the catalytic oxidation. The increase of [H+] in this oxidation retards the rate of the reaction. The effects of substituents on the oxidation rate are studied with 19 ortho-, meta- and para- substituted anilines at five different temperatures. The thermodynamic parameters for the oxidation have been determined and discussed. The catalysed m-chloroperbenzoic acid oxidation with substituted anilines fulfills the isokinetic relationship and Exner correlation but not to any of the linear free energy relationships. The solvent interaction also plays a major role in leading the reactivity. Based on the kinetic results and product analysis a probable mechanism is proposed.info:eu-repo/semantics/openAccessSociedad Chilena de QuímicaJournal of the Chilean Chemical Society v.57 n.4 20122012-01-01text/htmlhttp://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072012000400005en10.4067/S0717-97072012000400005
institution	Scielo Chile
collection	Scielo Chile
language	English
topic	Aniline oxidation m-chloroperbenzoic acid meso-tetraphenylporphyriniron(III) chloride
spellingShingle	Aniline oxidation m-chloroperbenzoic acid meso-tetraphenylporphyriniron(III) chloride RAJA,M KARUNAKARAN,K meso-TETRAPHENYLIRONPORPHYRIN(III) CHLORIDE CATALYZED OXIDATION OF ANILINE AND ITS SUBSTITUENTS BY m-CHLOROPERBENZOIC ACID
description	The most fascinating feature of heme-enzymes such as cytochromes P450 is their ability to carry out oxidations with high selectivity. Metalloporphyrin complexes are used as replicate compounds for cytochrome P450. A kinetic analysis has been carried out with the aim of understanding the mechanistic studies on oxidation of anilines by m-chloroperbenzoic acid catalyzed by meso-tetraphenylironporphyrin(III) chloride in aqueous acetic acid medium. The order of the reaction is found to be second order with respect to the substrate and first order with respect to the catalyst and oxidant. Product analysis proves that azobenzene is the sole product in the catalytic oxidation. The increase of [H+] in this oxidation retards the rate of the reaction. The effects of substituents on the oxidation rate are studied with 19 ortho-, meta- and para- substituted anilines at five different temperatures. The thermodynamic parameters for the oxidation have been determined and discussed. The catalysed m-chloroperbenzoic acid oxidation with substituted anilines fulfills the isokinetic relationship and Exner correlation but not to any of the linear free energy relationships. The solvent interaction also plays a major role in leading the reactivity. Based on the kinetic results and product analysis a probable mechanism is proposed.
author	RAJA,M KARUNAKARAN,K
author_facet	RAJA,M KARUNAKARAN,K
author_sort	RAJA,M
title	meso-TETRAPHENYLIRONPORPHYRIN(III) CHLORIDE CATALYZED OXIDATION OF ANILINE AND ITS SUBSTITUENTS BY m-CHLOROPERBENZOIC ACID
title_short	meso-TETRAPHENYLIRONPORPHYRIN(III) CHLORIDE CATALYZED OXIDATION OF ANILINE AND ITS SUBSTITUENTS BY m-CHLOROPERBENZOIC ACID
title_full	meso-TETRAPHENYLIRONPORPHYRIN(III) CHLORIDE CATALYZED OXIDATION OF ANILINE AND ITS SUBSTITUENTS BY m-CHLOROPERBENZOIC ACID
title_fullStr	meso-TETRAPHENYLIRONPORPHYRIN(III) CHLORIDE CATALYZED OXIDATION OF ANILINE AND ITS SUBSTITUENTS BY m-CHLOROPERBENZOIC ACID
title_full_unstemmed	meso-TETRAPHENYLIRONPORPHYRIN(III) CHLORIDE CATALYZED OXIDATION OF ANILINE AND ITS SUBSTITUENTS BY m-CHLOROPERBENZOIC ACID
title_sort	meso-tetraphenylironporphyrin(iii) chloride catalyzed oxidation of aniline and its substituents by m-chloroperbenzoic acid
publisher	Sociedad Chilena de Química
publishDate	2012
url	http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072012000400005
work_keys_str_mv	AT rajam mesotetraphenylironporphyriniiichloridecatalyzedoxidationofanilineanditssubstituentsbymchloroperbenzoicacid AT karunakarank mesotetraphenylironporphyriniiichloridecatalyzedoxidationofanilineanditssubstituentsbymchloroperbenzoicacid
_version_	1718445473669316608

meso-TETRAPHENYLIRONPORPHYRIN(III) CHLORIDE CATALYZED OXIDATION OF ANILINE AND ITS SUBSTITUENTS BY m-CHLOROPERBENZOIC ACID

Ejemplares similares