The Chapman-type rearrangement in pseudosaccharins: The case of 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide

Autores
Kaczor, A.; Proniewicz, L.M.; Almeida, R.; Gomez Zavaglia, Andrea; Cristiano, M.L.S.; Matos Beja, A.M.; Ramos Silva, M.; Fausto, Rui
Año de publicación
2008
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The thermal Chapman-type rearrangement of the pseudosaccharin 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide (MBID) into 2-methyl-1,2-benzisothiazol-3(2H)-one 1,1-dioxide (MBIOD) was investigated on the basis of computational models and knowledge of the structure of the reactant and product in the isolated and solid phases. X-ray diffraction was used to obtain the structure of the substrate in the crystalline phase, providing fundamental structural data for the development of the theoretical models used to investigate the reaction mechanism in the condensed phase. The intra- and different intermolecular mechanisms were compared on energetic grounds, based on the various developed theoretical models of the rearrangement reactions. The energetic preference (ca. 3.2 kJ mol-1, B3LYP/6-31+G(d,p)) of inter- over intramolecular transfer of the methyl group is predicted for the "quasi-simultaneous" transfer of the methyl groups model, explaining the potential of MBID towards [1,3′]-isomerization to MBIOD in the condensed phases. The predicted lower energy of MBIOD relative to MBID (ca. 60 kJ mol-1), due to the lower steric hindrance in the MBIOD molecule, acts as a molecular motor for the observed thermal rearrangement.
Fil: Kaczor, A.. Universidad de Coimbra; Portugal
Fil: Proniewicz, L.M.. Jagiellonian University; Polonia
Fil: Almeida, R.. Universidad de Algarve; Portugal. Universidad de Coimbra; Portugal
Fil: Gomez Zavaglia, Andrea. Universidad de Buenos Aires; Argentina. Universidad de Coimbra; Portugal. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; Argentina
Fil: Cristiano, M.L.S.. Universidad de Algarve; Portugal
Fil: Matos Beja, A.M.. Universidad de Coimbra; Portugal
Fil: Ramos Silva, M.. Universidad de Coimbra; Portugal
Fil: Fausto, Rui. Universidad de Coimbra; Portugal
Materia
DFT CALCULATIONS
IR SPECTRA
MATRIX-ISOLATION
MOLECULAR STRUCTURE
PSEUDOSACCHARYL ETHER
REACTION PATH
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:11336/152309
Acceder
id CONICETDig_23da97a68d72e3637ff96a38d707567d
oai_identifier_str oai:ri.conicet.gov.ar:11336/152309
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling The Chapman-type rearrangement in pseudosaccharins: The case of 3-(methoxy)-1,2-benzisothiazole 1,1-dioxideKaczor, A.Proniewicz, L.M.Almeida, R.Gomez Zavaglia, AndreaCristiano, M.L.S.Matos Beja, A.M.Ramos Silva, M.Fausto, RuiDFT CALCULATIONSIR SPECTRAMATRIX-ISOLATIONMOLECULAR STRUCTUREPSEUDOSACCHARYL ETHERREACTION PATHhttps://purl.org/becyt/ford/2.11https://purl.org/becyt/ford/2The thermal Chapman-type rearrangement of the pseudosaccharin 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide (MBID) into 2-methyl-1,2-benzisothiazol-3(2H)-one 1,1-dioxide (MBIOD) was investigated on the basis of computational models and knowledge of the structure of the reactant and product in the isolated and solid phases. X-ray diffraction was used to obtain the structure of the substrate in the crystalline phase, providing fundamental structural data for the development of the theoretical models used to investigate the reaction mechanism in the condensed phase. The intra- and different intermolecular mechanisms were compared on energetic grounds, based on the various developed theoretical models of the rearrangement reactions. The energetic preference (ca. 3.2 kJ mol-1, B3LYP/6-31+G(d,p)) of inter- over intramolecular transfer of the methyl group is predicted for the "quasi-simultaneous" transfer of the methyl groups model, explaining the potential of MBID towards [1,3′]-isomerization to MBIOD in the condensed phases. The predicted lower energy of MBIOD relative to MBID (ca. 60 kJ mol-1), due to the lower steric hindrance in the MBIOD molecule, acts as a molecular motor for the observed thermal rearrangement.Fil: Kaczor, A.. Universidad de Coimbra; PortugalFil: Proniewicz, L.M.. Jagiellonian University; PoloniaFil: Almeida, R.. Universidad de Algarve; Portugal. Universidad de Coimbra; PortugalFil: Gomez Zavaglia, Andrea. Universidad de Buenos Aires; Argentina. Universidad de Coimbra; Portugal. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; ArgentinaFil: Cristiano, M.L.S.. Universidad de Algarve; PortugalFil: Matos Beja, A.M.. Universidad de Coimbra; PortugalFil: Ramos Silva, M.. Universidad de Coimbra; PortugalFil: Fausto, Rui. Universidad de Coimbra; PortugalElsevier Science2008-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/152309Kaczor, A.; Proniewicz, L.M.; Almeida, R.; Gomez Zavaglia, Andrea; Cristiano, M.L.S.; et al.; The Chapman-type rearrangement in pseudosaccharins: The case of 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide; Elsevier Science; Journal of Molecular Structure; 892; 1-3; 12-2008; 343-3520022-2860CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.molstruc.2008.05.054info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0022286008004389info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:24:26Zoai:ri.conicet.gov.ar:11336/152309instacron: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:34982025-10-15 14:24:26.4CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv The Chapman-type rearrangement in pseudosaccharins: The case of 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide
title The Chapman-type rearrangement in pseudosaccharins: The case of 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide
spellingShingle The Chapman-type rearrangement in pseudosaccharins: The case of 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide
Kaczor, A.
DFT CALCULATIONS
IR SPECTRA
MATRIX-ISOLATION
MOLECULAR STRUCTURE
PSEUDOSACCHARYL ETHER
REACTION PATH
title_short The Chapman-type rearrangement in pseudosaccharins: The case of 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide
title_full The Chapman-type rearrangement in pseudosaccharins: The case of 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide
title_fullStr The Chapman-type rearrangement in pseudosaccharins: The case of 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide
title_full_unstemmed The Chapman-type rearrangement in pseudosaccharins: The case of 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide
title_sort The Chapman-type rearrangement in pseudosaccharins: The case of 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide
dc.creator.none.fl_str_mv Kaczor, A.
Proniewicz, L.M.
Almeida, R.
Gomez Zavaglia, Andrea
Cristiano, M.L.S.
Matos Beja, A.M.
Ramos Silva, M.
Fausto, Rui
author Kaczor, A.
author_facet Kaczor, A.
Proniewicz, L.M.
Almeida, R.
Gomez Zavaglia, Andrea
Cristiano, M.L.S.
Matos Beja, A.M.
Ramos Silva, M.
Fausto, Rui
author_role author
author2 Proniewicz, L.M.
Almeida, R.
Gomez Zavaglia, Andrea
Cristiano, M.L.S.
Matos Beja, A.M.
Ramos Silva, M.
Fausto, Rui
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv DFT CALCULATIONS
IR SPECTRA
MATRIX-ISOLATION
MOLECULAR STRUCTURE
PSEUDOSACCHARYL ETHER
REACTION PATH
topic DFT CALCULATIONS
IR SPECTRA
MATRIX-ISOLATION
MOLECULAR STRUCTURE
PSEUDOSACCHARYL ETHER
REACTION PATH
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.11
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv The thermal Chapman-type rearrangement of the pseudosaccharin 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide (MBID) into 2-methyl-1,2-benzisothiazol-3(2H)-one 1,1-dioxide (MBIOD) was investigated on the basis of computational models and knowledge of the structure of the reactant and product in the isolated and solid phases. X-ray diffraction was used to obtain the structure of the substrate in the crystalline phase, providing fundamental structural data for the development of the theoretical models used to investigate the reaction mechanism in the condensed phase. The intra- and different intermolecular mechanisms were compared on energetic grounds, based on the various developed theoretical models of the rearrangement reactions. The energetic preference (ca. 3.2 kJ mol-1, B3LYP/6-31+G(d,p)) of inter- over intramolecular transfer of the methyl group is predicted for the "quasi-simultaneous" transfer of the methyl groups model, explaining the potential of MBID towards [1,3′]-isomerization to MBIOD in the condensed phases. The predicted lower energy of MBIOD relative to MBID (ca. 60 kJ mol-1), due to the lower steric hindrance in the MBIOD molecule, acts as a molecular motor for the observed thermal rearrangement.
Fil: Kaczor, A.. Universidad de Coimbra; Portugal
Fil: Proniewicz, L.M.. Jagiellonian University; Polonia
Fil: Almeida, R.. Universidad de Algarve; Portugal. Universidad de Coimbra; Portugal
Fil: Gomez Zavaglia, Andrea. Universidad de Buenos Aires; Argentina. Universidad de Coimbra; Portugal. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; Argentina
Fil: Cristiano, M.L.S.. Universidad de Algarve; Portugal
Fil: Matos Beja, A.M.. Universidad de Coimbra; Portugal
Fil: Ramos Silva, M.. Universidad de Coimbra; Portugal
Fil: Fausto, Rui. Universidad de Coimbra; Portugal
description The thermal Chapman-type rearrangement of the pseudosaccharin 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide (MBID) into 2-methyl-1,2-benzisothiazol-3(2H)-one 1,1-dioxide (MBIOD) was investigated on the basis of computational models and knowledge of the structure of the reactant and product in the isolated and solid phases. X-ray diffraction was used to obtain the structure of the substrate in the crystalline phase, providing fundamental structural data for the development of the theoretical models used to investigate the reaction mechanism in the condensed phase. The intra- and different intermolecular mechanisms were compared on energetic grounds, based on the various developed theoretical models of the rearrangement reactions. The energetic preference (ca. 3.2 kJ mol-1, B3LYP/6-31+G(d,p)) of inter- over intramolecular transfer of the methyl group is predicted for the "quasi-simultaneous" transfer of the methyl groups model, explaining the potential of MBID towards [1,3′]-isomerization to MBIOD in the condensed phases. The predicted lower energy of MBIOD relative to MBID (ca. 60 kJ mol-1), due to the lower steric hindrance in the MBIOD molecule, acts as a molecular motor for the observed thermal rearrangement.
publishDate 2008
dc.date.none.fl_str_mv 2008-12
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/11336/152309
Kaczor, A.; Proniewicz, L.M.; Almeida, R.; Gomez Zavaglia, Andrea; Cristiano, M.L.S.; et al.; The Chapman-type rearrangement in pseudosaccharins: The case of 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide; Elsevier Science; Journal of Molecular Structure; 892; 1-3; 12-2008; 343-352
0022-2860
CONICET Digital
CONICET
url http://hdl.handle.net/11336/152309
identifier_str_mv Kaczor, A.; Proniewicz, L.M.; Almeida, R.; Gomez Zavaglia, Andrea; Cristiano, M.L.S.; et al.; The Chapman-type rearrangement in pseudosaccharins: The case of 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide; Elsevier Science; Journal of Molecular Structure; 892; 1-3; 12-2008; 343-352
0022-2860
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.molstruc.2008.05.054
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0022286008004389
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 Elsevier Science
publisher.none.fl_str_mv Elsevier Science
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 13.22299

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