Matrix-isolation FTIR, theoretical structural analysis and reactivity of amino-saccharins: N-(1,1-dioxo-1,2-benzisothiazol-3-yl)-N-methyl amine and -N,N-dimethyl amine

Autores
Almeida, R.; Gomez Zavaglia, Andrea; Kaczor, A.; Ismael, A.; Cristiano, M.L.S.; Fausto, R.
Año de publicación
2009
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In this work, two novel amino-substituted derivatives of saccharin, N-(1,1-dioxo-1,2-benzisothiazol-3- yl)-N-methyl amine (MBAD) and N-(1,1-dioxo-1,2-benzisothiazol-3-yl)-N,N-dimethyl amine (DMBAD), were synthesized and characterized, and their molecular structure and vibrational properties were investigated by matrix-isolation FTIR spectroscopy and theoretical calculations undertaken using different levels of approximation. The calculations predicted the existence of two conformers of MBAD. The lowest energy form was predicted to be considerably more stable than the second conformer (DE > ca. 20 kJ mol1) and was the sole form contributing to the infrared spectrum of the compound isolated in solid xenon. Both conformers have planar amine moieties. In the case of DMBAD, only one doubly-degenerated- by-symmetry conformer exists, with the amine nitrogen atom considerably pyramidalized. The effect of the electron-withdrawing saccharyl ring on the C–N bond lengths is discussed. The different structural preferences around the amine nitrogen atom in the two molecules were explained in terms of repulsive interactions involving the additional methyl group of DMBAD. Observed structural features are correlated with the reactivity exhibited by the two compounds towards nucleophiles. The experimentally obtained spectra of the matrix-isolated monomers of MBAD and DMBAD were fully assigned by comparison with the corresponding calculated spectra.
Fil: Almeida, R.. Universidad de Coimbra; Portugal
Fil: Gomez Zavaglia, Andrea. 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: Kaczor, A.. Universidad de Coimbra; Portugal
Fil: Ismael, A.. Universidad de Algarve; Portugal
Fil: Cristiano, M.L.S.. Universidad de Algarve; Portugal
Fil: Fausto, R.. Universidad de Coimbra; Portugal
Materia
AMINO-SUBSTITUTED BENZISOTHIAZOLES
C-N BOND LENGTHS
MATRIX-ISOLATION INFRARED SPECTROSCOPY
MOLECULAR STRUCTURE
QUANTUM CHEMICAL CALCULATIONS
REACTIVITY
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:11336/161667
Acceder
id CONICETDig_df19b128add33770245cee5afb3ebab0
oai_identifier_str oai:ri.conicet.gov.ar:11336/161667
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Matrix-isolation FTIR, theoretical structural analysis and reactivity of amino-saccharins: N-(1,1-dioxo-1,2-benzisothiazol-3-yl)-N-methyl amine and -N,N-dimethyl amineAlmeida, R.Gomez Zavaglia, AndreaKaczor, A.Ismael, A.Cristiano, M.L.S.Fausto, R.AMINO-SUBSTITUTED BENZISOTHIAZOLESC-N BOND LENGTHSMATRIX-ISOLATION INFRARED SPECTROSCOPYMOLECULAR STRUCTUREQUANTUM CHEMICAL CALCULATIONSREACTIVITYhttps://purl.org/becyt/ford/2.11https://purl.org/becyt/ford/2In this work, two novel amino-substituted derivatives of saccharin, N-(1,1-dioxo-1,2-benzisothiazol-3- yl)-N-methyl amine (MBAD) and N-(1,1-dioxo-1,2-benzisothiazol-3-yl)-N,N-dimethyl amine (DMBAD), were synthesized and characterized, and their molecular structure and vibrational properties were investigated by matrix-isolation FTIR spectroscopy and theoretical calculations undertaken using different levels of approximation. The calculations predicted the existence of two conformers of MBAD. The lowest energy form was predicted to be considerably more stable than the second conformer (DE > ca. 20 kJ mol1) and was the sole form contributing to the infrared spectrum of the compound isolated in solid xenon. Both conformers have planar amine moieties. In the case of DMBAD, only one doubly-degenerated- by-symmetry conformer exists, with the amine nitrogen atom considerably pyramidalized. The effect of the electron-withdrawing saccharyl ring on the C–N bond lengths is discussed. The different structural preferences around the amine nitrogen atom in the two molecules were explained in terms of repulsive interactions involving the additional methyl group of DMBAD. Observed structural features are correlated with the reactivity exhibited by the two compounds towards nucleophiles. The experimentally obtained spectra of the matrix-isolated monomers of MBAD and DMBAD were fully assigned by comparison with the corresponding calculated spectra.Fil: Almeida, R.. Universidad de Coimbra; PortugalFil: Gomez Zavaglia, Andrea. 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: Kaczor, A.. Universidad de Coimbra; PortugalFil: Ismael, A.. Universidad de Algarve; PortugalFil: Cristiano, M.L.S.. Universidad de Algarve; PortugalFil: Fausto, R.. Universidad de Coimbra; PortugalElsevier Science2009-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/161667Almeida, R.; Gomez Zavaglia, Andrea; Kaczor, A.; Ismael, A.; Cristiano, M.L.S.; et al.; Matrix-isolation FTIR, theoretical structural analysis and reactivity of amino-saccharins: N-(1,1-dioxo-1,2-benzisothiazol-3-yl)-N-methyl amine and -N,N-dimethyl amine; Elsevier Science; Journal of Molecular Structure; 938; 1-3; 12-2009; 198-2060022-28601872-8014CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0022286009006048info:eu-repo/semantics/altIdentifier/doi/10.1016/j.molstruc.2009.09.027info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:57:33Zoai:ri.conicet.gov.ar:11336/161667instacron: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 09:57:34.241CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Matrix-isolation FTIR, theoretical structural analysis and reactivity of amino-saccharins: N-(1,1-dioxo-1,2-benzisothiazol-3-yl)-N-methyl amine and -N,N-dimethyl amine
title Matrix-isolation FTIR, theoretical structural analysis and reactivity of amino-saccharins: N-(1,1-dioxo-1,2-benzisothiazol-3-yl)-N-methyl amine and -N,N-dimethyl amine
spellingShingle Matrix-isolation FTIR, theoretical structural analysis and reactivity of amino-saccharins: N-(1,1-dioxo-1,2-benzisothiazol-3-yl)-N-methyl amine and -N,N-dimethyl amine
Almeida, R.
AMINO-SUBSTITUTED BENZISOTHIAZOLES
C-N BOND LENGTHS
MATRIX-ISOLATION INFRARED SPECTROSCOPY
MOLECULAR STRUCTURE
QUANTUM CHEMICAL CALCULATIONS
REACTIVITY
title_short Matrix-isolation FTIR, theoretical structural analysis and reactivity of amino-saccharins: N-(1,1-dioxo-1,2-benzisothiazol-3-yl)-N-methyl amine and -N,N-dimethyl amine
title_full Matrix-isolation FTIR, theoretical structural analysis and reactivity of amino-saccharins: N-(1,1-dioxo-1,2-benzisothiazol-3-yl)-N-methyl amine and -N,N-dimethyl amine
title_fullStr Matrix-isolation FTIR, theoretical structural analysis and reactivity of amino-saccharins: N-(1,1-dioxo-1,2-benzisothiazol-3-yl)-N-methyl amine and -N,N-dimethyl amine
title_full_unstemmed Matrix-isolation FTIR, theoretical structural analysis and reactivity of amino-saccharins: N-(1,1-dioxo-1,2-benzisothiazol-3-yl)-N-methyl amine and -N,N-dimethyl amine
title_sort Matrix-isolation FTIR, theoretical structural analysis and reactivity of amino-saccharins: N-(1,1-dioxo-1,2-benzisothiazol-3-yl)-N-methyl amine and -N,N-dimethyl amine
dc.creator.none.fl_str_mv Almeida, R.
Gomez Zavaglia, Andrea
Kaczor, A.
Ismael, A.
Cristiano, M.L.S.
Fausto, R.
author Almeida, R.
author_facet Almeida, R.
Gomez Zavaglia, Andrea
Kaczor, A.
Ismael, A.
Cristiano, M.L.S.
Fausto, R.
author_role author
author2 Gomez Zavaglia, Andrea
Kaczor, A.
Ismael, A.
Cristiano, M.L.S.
Fausto, R.
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv AMINO-SUBSTITUTED BENZISOTHIAZOLES
C-N BOND LENGTHS
MATRIX-ISOLATION INFRARED SPECTROSCOPY
MOLECULAR STRUCTURE
QUANTUM CHEMICAL CALCULATIONS
REACTIVITY
topic AMINO-SUBSTITUTED BENZISOTHIAZOLES
C-N BOND LENGTHS
MATRIX-ISOLATION INFRARED SPECTROSCOPY
MOLECULAR STRUCTURE
QUANTUM CHEMICAL CALCULATIONS
REACTIVITY
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.11
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv In this work, two novel amino-substituted derivatives of saccharin, N-(1,1-dioxo-1,2-benzisothiazol-3- yl)-N-methyl amine (MBAD) and N-(1,1-dioxo-1,2-benzisothiazol-3-yl)-N,N-dimethyl amine (DMBAD), were synthesized and characterized, and their molecular structure and vibrational properties were investigated by matrix-isolation FTIR spectroscopy and theoretical calculations undertaken using different levels of approximation. The calculations predicted the existence of two conformers of MBAD. The lowest energy form was predicted to be considerably more stable than the second conformer (DE > ca. 20 kJ mol1) and was the sole form contributing to the infrared spectrum of the compound isolated in solid xenon. Both conformers have planar amine moieties. In the case of DMBAD, only one doubly-degenerated- by-symmetry conformer exists, with the amine nitrogen atom considerably pyramidalized. The effect of the electron-withdrawing saccharyl ring on the C–N bond lengths is discussed. The different structural preferences around the amine nitrogen atom in the two molecules were explained in terms of repulsive interactions involving the additional methyl group of DMBAD. Observed structural features are correlated with the reactivity exhibited by the two compounds towards nucleophiles. The experimentally obtained spectra of the matrix-isolated monomers of MBAD and DMBAD were fully assigned by comparison with the corresponding calculated spectra.
Fil: Almeida, R.. Universidad de Coimbra; Portugal
Fil: Gomez Zavaglia, Andrea. 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: Kaczor, A.. Universidad de Coimbra; Portugal
Fil: Ismael, A.. Universidad de Algarve; Portugal
Fil: Cristiano, M.L.S.. Universidad de Algarve; Portugal
Fil: Fausto, R.. Universidad de Coimbra; Portugal
description In this work, two novel amino-substituted derivatives of saccharin, N-(1,1-dioxo-1,2-benzisothiazol-3- yl)-N-methyl amine (MBAD) and N-(1,1-dioxo-1,2-benzisothiazol-3-yl)-N,N-dimethyl amine (DMBAD), were synthesized and characterized, and their molecular structure and vibrational properties were investigated by matrix-isolation FTIR spectroscopy and theoretical calculations undertaken using different levels of approximation. The calculations predicted the existence of two conformers of MBAD. The lowest energy form was predicted to be considerably more stable than the second conformer (DE > ca. 20 kJ mol1) and was the sole form contributing to the infrared spectrum of the compound isolated in solid xenon. Both conformers have planar amine moieties. In the case of DMBAD, only one doubly-degenerated- by-symmetry conformer exists, with the amine nitrogen atom considerably pyramidalized. The effect of the electron-withdrawing saccharyl ring on the C–N bond lengths is discussed. The different structural preferences around the amine nitrogen atom in the two molecules were explained in terms of repulsive interactions involving the additional methyl group of DMBAD. Observed structural features are correlated with the reactivity exhibited by the two compounds towards nucleophiles. The experimentally obtained spectra of the matrix-isolated monomers of MBAD and DMBAD were fully assigned by comparison with the corresponding calculated spectra.
publishDate 2009
dc.date.none.fl_str_mv 2009-12
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/11336/161667
Almeida, R.; Gomez Zavaglia, Andrea; Kaczor, A.; Ismael, A.; Cristiano, M.L.S.; et al.; Matrix-isolation FTIR, theoretical structural analysis and reactivity of amino-saccharins: N-(1,1-dioxo-1,2-benzisothiazol-3-yl)-N-methyl amine and -N,N-dimethyl amine; Elsevier Science; Journal of Molecular Structure; 938; 1-3; 12-2009; 198-206
0022-2860
1872-8014
CONICET Digital
CONICET
url http://hdl.handle.net/11336/161667
identifier_str_mv Almeida, R.; Gomez Zavaglia, Andrea; Kaczor, A.; Ismael, A.; Cristiano, M.L.S.; et al.; Matrix-isolation FTIR, theoretical structural analysis and reactivity of amino-saccharins: N-(1,1-dioxo-1,2-benzisothiazol-3-yl)-N-methyl amine and -N,N-dimethyl amine; Elsevier Science; Journal of Molecular Structure; 938; 1-3; 12-2009; 198-206
0022-2860
1872-8014
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0022286009006048
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.molstruc.2009.09.027
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
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 13.070432

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