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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/152309
Ver los metadatos del registro completo
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 Técnicas2025-09-29T09:35:50Zoai: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:34982025-09-29 09:35:50.868CONICET 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 |
_version_ |
1844613120009437184 |
score |
13.070432 |