E-Z isomerization and aggregation Phenomena of Dithiafulvenes in CHCl3

Autores
Fracaroli, Alejandro Matías; Granados, Alejandro Manuel; Hoyos, Maria Rita Micaela
Año de publicación
2009
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The physical-chemical properties of several 1,3-dithiafulvene (DTF) derivatives having a donor and acceptor group in the molecule were studied. The synthesis of these compounds produces selectively the E isomer, but when the compound is dissolved in CHCl3 isomerization to the Z isomer takes place with a rate that depends on the substituents. The interconversion rate is slow on the NMR time scale; therefore, two separated signals are observed, and they are used to measure the rate constant of isomerization. The equilibrium constant is, in all cases, very close to 1, and this is coincident with the fact that theoretical calculations of the energy of the two isomers in the gas phase differ by less than 0.1 kcal/mol. The isomerization reaction is completely reversible, and the E isomer can be obtained in pure form by selective crystallization. The derivatives with fhioalkyl groups have a strong tendency to aggregate in CDCl3. The formation of the aggregates is evidenced from the changes in ID 1H NMR and DOSY spectra as a function of concentration. The compounds are highly delocalized, and this is reflected by the low activation energy for the isomerization
Fil: Fracaroli, Alejandro Matías. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Granados, Alejandro Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Hoyos, Maria Rita Micaela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Materia
Isomerizacion de Ditiafulvenos
Rmn Dinamica (Dosy)
Agregados Moleculares
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:11336/113765
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/113765
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling E-Z isomerization and aggregation Phenomena of Dithiafulvenes in CHCl3Fracaroli, Alejandro MatíasGranados, Alejandro ManuelHoyos, Maria Rita MicaelaIsomerizacion de DitiafulvenosRmn Dinamica (Dosy)Agregados Moleculareshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The physical-chemical properties of several 1,3-dithiafulvene (DTF) derivatives having a donor and acceptor group in the molecule were studied. The synthesis of these compounds produces selectively the E isomer, but when the compound is dissolved in CHCl3 isomerization to the Z isomer takes place with a rate that depends on the substituents. The interconversion rate is slow on the NMR time scale; therefore, two separated signals are observed, and they are used to measure the rate constant of isomerization. The equilibrium constant is, in all cases, very close to 1, and this is coincident with the fact that theoretical calculations of the energy of the two isomers in the gas phase differ by less than 0.1 kcal/mol. The isomerization reaction is completely reversible, and the E isomer can be obtained in pure form by selective crystallization. The derivatives with fhioalkyl groups have a strong tendency to aggregate in CDCl3. The formation of the aggregates is evidenced from the changes in ID 1H NMR and DOSY spectra as a function of concentration. The compounds are highly delocalized, and this is reflected by the low activation energy for the isomerizationFil: Fracaroli, Alejandro Matías. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Granados, Alejandro Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Hoyos, Maria Rita Micaela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaAmerican Chemical Society2009-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/113765Fracaroli, Alejandro Matías; Granados, Alejandro Manuel; Hoyos, Maria Rita Micaela; E-Z isomerization and aggregation Phenomena of Dithiafulvenes in CHCl3; American Chemical Society; Journal of Organic Chemistry; 74; 5; 3-2009; 2114-21190022-32631520-6904CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jo802681hinfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jo802681hinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-11-12T09:33:08Zoai:ri.conicet.gov.ar:11336/113765instacron: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:34982025-11-12 09:33:08.823CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv E-Z isomerization and aggregation Phenomena of Dithiafulvenes in CHCl3
title E-Z isomerization and aggregation Phenomena of Dithiafulvenes in CHCl3
spellingShingle E-Z isomerization and aggregation Phenomena of Dithiafulvenes in CHCl3
Fracaroli, Alejandro Matías
Isomerizacion de Ditiafulvenos
Rmn Dinamica (Dosy)
Agregados Moleculares
title_short E-Z isomerization and aggregation Phenomena of Dithiafulvenes in CHCl3
title_full E-Z isomerization and aggregation Phenomena of Dithiafulvenes in CHCl3
title_fullStr E-Z isomerization and aggregation Phenomena of Dithiafulvenes in CHCl3
title_full_unstemmed E-Z isomerization and aggregation Phenomena of Dithiafulvenes in CHCl3
title_sort E-Z isomerization and aggregation Phenomena of Dithiafulvenes in CHCl3
dc.creator.none.fl_str_mv Fracaroli, Alejandro Matías
Granados, Alejandro Manuel
Hoyos, Maria Rita Micaela
author Fracaroli, Alejandro Matías
author_facet Fracaroli, Alejandro Matías
Granados, Alejandro Manuel
Hoyos, Maria Rita Micaela
author_role author
author2 Granados, Alejandro Manuel
Hoyos, Maria Rita Micaela
author2_role author
author
dc.subject.none.fl_str_mv Isomerizacion de Ditiafulvenos
Rmn Dinamica (Dosy)
Agregados Moleculares
topic Isomerizacion de Ditiafulvenos
Rmn Dinamica (Dosy)
Agregados Moleculares
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The physical-chemical properties of several 1,3-dithiafulvene (DTF) derivatives having a donor and acceptor group in the molecule were studied. The synthesis of these compounds produces selectively the E isomer, but when the compound is dissolved in CHCl3 isomerization to the Z isomer takes place with a rate that depends on the substituents. The interconversion rate is slow on the NMR time scale; therefore, two separated signals are observed, and they are used to measure the rate constant of isomerization. The equilibrium constant is, in all cases, very close to 1, and this is coincident with the fact that theoretical calculations of the energy of the two isomers in the gas phase differ by less than 0.1 kcal/mol. The isomerization reaction is completely reversible, and the E isomer can be obtained in pure form by selective crystallization. The derivatives with fhioalkyl groups have a strong tendency to aggregate in CDCl3. The formation of the aggregates is evidenced from the changes in ID 1H NMR and DOSY spectra as a function of concentration. The compounds are highly delocalized, and this is reflected by the low activation energy for the isomerization
Fil: Fracaroli, Alejandro Matías. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Granados, Alejandro Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Hoyos, Maria Rita Micaela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
description The physical-chemical properties of several 1,3-dithiafulvene (DTF) derivatives having a donor and acceptor group in the molecule were studied. The synthesis of these compounds produces selectively the E isomer, but when the compound is dissolved in CHCl3 isomerization to the Z isomer takes place with a rate that depends on the substituents. The interconversion rate is slow on the NMR time scale; therefore, two separated signals are observed, and they are used to measure the rate constant of isomerization. The equilibrium constant is, in all cases, very close to 1, and this is coincident with the fact that theoretical calculations of the energy of the two isomers in the gas phase differ by less than 0.1 kcal/mol. The isomerization reaction is completely reversible, and the E isomer can be obtained in pure form by selective crystallization. The derivatives with fhioalkyl groups have a strong tendency to aggregate in CDCl3. The formation of the aggregates is evidenced from the changes in ID 1H NMR and DOSY spectra as a function of concentration. The compounds are highly delocalized, and this is reflected by the low activation energy for the isomerization
publishDate 2009
dc.date.none.fl_str_mv 2009-03
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/11336/113765
Fracaroli, Alejandro Matías; Granados, Alejandro Manuel; Hoyos, Maria Rita Micaela; E-Z isomerization and aggregation Phenomena of Dithiafulvenes in CHCl3; American Chemical Society; Journal of Organic Chemistry; 74; 5; 3-2009; 2114-2119
0022-3263
1520-6904
CONICET Digital
CONICET
url http://hdl.handle.net/11336/113765
identifier_str_mv Fracaroli, Alejandro Matías; Granados, Alejandro Manuel; Hoyos, Maria Rita Micaela; E-Z isomerization and aggregation Phenomena of Dithiafulvenes in CHCl3; American Chemical Society; Journal of Organic Chemistry; 74; 5; 3-2009; 2114-2119
0022-3263
1520-6904
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/jo802681h
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jo802681h
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
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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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score 13.25334

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