The crucial role of H-bonding in the mechanisms of reactions with diamines in aprotic solvents

Autores
Alvaro, Cecilia Elisabeth Silvana; Sbarbati, Norma Ethel
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In the widely reported mechanistic studies of Aromatic Nucleophilic Substitutions (ANS) most of the discussions are centered in the nature of the halo-nitro-aromatic substrates, the basicity of the nucleophile and the polarity or dipolarity of the solvent. However, in the reactions of monofunctionalized amines with aromatic substrates bearing poor nucleofuges carried out in solvents of low permittivity, weak non-covalent interactions, such as intra- and/or inter-molecular H-bonding, play a significant role. When these special features concur in the reaction system, a mechanism, called the “dimer nucleophile mechanism”, operates in which a third-order in amine kinetic law is obeyed. The mechanism has been properly characterized by abundant evidence, showing the influence of weak non-covalent interactions, due to the nucleophile nature, the substrates used and the reaction medium. In the present paper, we discuss new examples of that mechanism to show the crucial role of H-bonding. Several aspects were studied: the influence of the nucleophile structure (specially its capacity of developing intra- and/or intermolecular hydrogen bond interactions); the “resonance-assisted” H-bond; and the effect of aprotic hydrogen bond acceptor (HBA) co-solvent/additives. A comprehensive further treatment of kinetic results is described including reactions where the first-step or the second-step are rate determining.
Fil: Alvaro, Cecilia Elisabeth Silvana. Universidad Nacional del Comahue. Facultad de Ingeniería. Departamento de Química; Argentina
Fil: Sbarbati, Norma Ethel. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Materia
Hydrogen Bonding
Diamines
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/68468
Acceder
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spelling The crucial role of H-bonding in the mechanisms of reactions with diamines in aprotic solventsAlvaro, Cecilia Elisabeth SilvanaSbarbati, Norma EthelHydrogen BondingDiamineshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1In the widely reported mechanistic studies of Aromatic Nucleophilic Substitutions (ANS) most of the discussions are centered in the nature of the halo-nitro-aromatic substrates, the basicity of the nucleophile and the polarity or dipolarity of the solvent. However, in the reactions of monofunctionalized amines with aromatic substrates bearing poor nucleofuges carried out in solvents of low permittivity, weak non-covalent interactions, such as intra- and/or inter-molecular H-bonding, play a significant role. When these special features concur in the reaction system, a mechanism, called the “dimer nucleophile mechanism”, operates in which a third-order in amine kinetic law is obeyed. The mechanism has been properly characterized by abundant evidence, showing the influence of weak non-covalent interactions, due to the nucleophile nature, the substrates used and the reaction medium. In the present paper, we discuss new examples of that mechanism to show the crucial role of H-bonding. Several aspects were studied: the influence of the nucleophile structure (specially its capacity of developing intra- and/or intermolecular hydrogen bond interactions); the “resonance-assisted” H-bond; and the effect of aprotic hydrogen bond acceptor (HBA) co-solvent/additives. A comprehensive further treatment of kinetic results is described including reactions where the first-step or the second-step are rate determining.Fil: Alvaro, Cecilia Elisabeth Silvana. Universidad Nacional del Comahue. Facultad de Ingeniería. Departamento de Química; ArgentinaFil: Sbarbati, Norma Ethel. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaResearch Trends2011-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/68468Alvaro, Cecilia Elisabeth Silvana; Sbarbati, Norma Ethel; The crucial role of H-bonding in the mechanisms of reactions with diamines in aprotic solvents ; Research Trends; Trends in Organic Chemistry; 15; 7-2011; 95-1070972-4362CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://www.researchtrends.net/tia/abstract.asp?in=0&vn=15&tid=14&aid=3323&pub=2011&type=3info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:08:31Zoai:ri.conicet.gov.ar:11336/68468instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-03 10:08:31.489CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv The crucial role of H-bonding in the mechanisms of reactions with diamines in aprotic solvents
title The crucial role of H-bonding in the mechanisms of reactions with diamines in aprotic solvents
spellingShingle The crucial role of H-bonding in the mechanisms of reactions with diamines in aprotic solvents
Alvaro, Cecilia Elisabeth Silvana
Hydrogen Bonding
Diamines
title_short The crucial role of H-bonding in the mechanisms of reactions with diamines in aprotic solvents
title_full The crucial role of H-bonding in the mechanisms of reactions with diamines in aprotic solvents
title_fullStr The crucial role of H-bonding in the mechanisms of reactions with diamines in aprotic solvents
title_full_unstemmed The crucial role of H-bonding in the mechanisms of reactions with diamines in aprotic solvents
title_sort The crucial role of H-bonding in the mechanisms of reactions with diamines in aprotic solvents
dc.creator.none.fl_str_mv Alvaro, Cecilia Elisabeth Silvana
Sbarbati, Norma Ethel
author Alvaro, Cecilia Elisabeth Silvana
author_facet Alvaro, Cecilia Elisabeth Silvana
Sbarbati, Norma Ethel
author_role author
author2 Sbarbati, Norma Ethel
author2_role author
dc.subject.none.fl_str_mv Hydrogen Bonding
Diamines
topic Hydrogen Bonding
Diamines
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv In the widely reported mechanistic studies of Aromatic Nucleophilic Substitutions (ANS) most of the discussions are centered in the nature of the halo-nitro-aromatic substrates, the basicity of the nucleophile and the polarity or dipolarity of the solvent. However, in the reactions of monofunctionalized amines with aromatic substrates bearing poor nucleofuges carried out in solvents of low permittivity, weak non-covalent interactions, such as intra- and/or inter-molecular H-bonding, play a significant role. When these special features concur in the reaction system, a mechanism, called the “dimer nucleophile mechanism”, operates in which a third-order in amine kinetic law is obeyed. The mechanism has been properly characterized by abundant evidence, showing the influence of weak non-covalent interactions, due to the nucleophile nature, the substrates used and the reaction medium. In the present paper, we discuss new examples of that mechanism to show the crucial role of H-bonding. Several aspects were studied: the influence of the nucleophile structure (specially its capacity of developing intra- and/or intermolecular hydrogen bond interactions); the “resonance-assisted” H-bond; and the effect of aprotic hydrogen bond acceptor (HBA) co-solvent/additives. A comprehensive further treatment of kinetic results is described including reactions where the first-step or the second-step are rate determining.
Fil: Alvaro, Cecilia Elisabeth Silvana. Universidad Nacional del Comahue. Facultad de Ingeniería. Departamento de Química; Argentina
Fil: Sbarbati, Norma Ethel. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
description In the widely reported mechanistic studies of Aromatic Nucleophilic Substitutions (ANS) most of the discussions are centered in the nature of the halo-nitro-aromatic substrates, the basicity of the nucleophile and the polarity or dipolarity of the solvent. However, in the reactions of monofunctionalized amines with aromatic substrates bearing poor nucleofuges carried out in solvents of low permittivity, weak non-covalent interactions, such as intra- and/or inter-molecular H-bonding, play a significant role. When these special features concur in the reaction system, a mechanism, called the “dimer nucleophile mechanism”, operates in which a third-order in amine kinetic law is obeyed. The mechanism has been properly characterized by abundant evidence, showing the influence of weak non-covalent interactions, due to the nucleophile nature, the substrates used and the reaction medium. In the present paper, we discuss new examples of that mechanism to show the crucial role of H-bonding. Several aspects were studied: the influence of the nucleophile structure (specially its capacity of developing intra- and/or intermolecular hydrogen bond interactions); the “resonance-assisted” H-bond; and the effect of aprotic hydrogen bond acceptor (HBA) co-solvent/additives. A comprehensive further treatment of kinetic results is described including reactions where the first-step or the second-step are rate determining.
publishDate 2011
dc.date.none.fl_str_mv 2011-07
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/68468
Alvaro, Cecilia Elisabeth Silvana; Sbarbati, Norma Ethel; The crucial role of H-bonding in the mechanisms of reactions with diamines in aprotic solvents ; Research Trends; Trends in Organic Chemistry; 15; 7-2011; 95-107
0972-4362
CONICET Digital
CONICET
url http://hdl.handle.net/11336/68468
identifier_str_mv Alvaro, Cecilia Elisabeth Silvana; Sbarbati, Norma Ethel; The crucial role of H-bonding in the mechanisms of reactions with diamines in aprotic solvents ; Research Trends; Trends in Organic Chemistry; 15; 7-2011; 95-107
0972-4362
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://www.researchtrends.net/tia/abstract.asp?in=0&vn=15&tid=14&aid=3323&pub=2011&type=3
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Research Trends
publisher.none.fl_str_mv Research Trends
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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