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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

2009Journal article Restricted
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dc.contributor.authorAlmeida, R.
dc.contributor.authorGómez-Zavaglia, A.
dc.contributor.authorKaczor, A.
dc.contributor.authorIsmael, Amin
dc.contributor.authorCristiano, Maria Lurdes Santos
dc.contributor.authorFausto, R.
dc.date.accessioned2014-06-11T12:14:59Z
dc.date.available2014-06-11T12:14:59Z
dc.date.issued2009
dc.date.updated2014-06-05T11:03:55Z
dc.description.abstractIn 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 mol 1) 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.por
dc.identifier.citationAlmeida, R.; Gómez-Zavaglia, A.; Kaczor, A.; Ismael, A.; Cristiano, M.L.S.; Fausto, R. 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, Journal of Molecular Structure, 938, 1-3, 198-206, 2009.por
dc.identifier.doihttp://dx.doi.org/10.1016/j.molstruc.2009.09.027
dc.identifier.issn0022-2860
dc.identifier.otherAUT: MCR00716;
dc.identifier.urihttp://hdl.handle.net/10400.1/4262
dc.language.isoengpor
dc.peerreviewedyespor
dc.publisherElsevierpor
dc.subjectAmino-substituted benzisothiazolespor
dc.subjectMolecular structurepor
dc.subjectQuantum chemical calculationspor
dc.subjectMatrix-isolation infrared spectroscopypor
dc.subjectC–N bond lengthspor
dc.subjectReactivitypor
dc.titleMatrix-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 aminepor
dc.typejournal article
dspace.entity.typePublication
oaire.citation.endPage206por
oaire.citation.issue1-3por
oaire.citation.startPage198por
oaire.citation.titleJournal of Molecular Structurepor
oaire.citation.volume938por
person.familyNameIsmael
person.familyNameCristiano
person.givenNameAmin
person.givenNameMaria de Lurdes
person.identifier.ciencia-idE411-6006-5A01
person.identifier.orcid0000-0002-7346-5998
person.identifier.orcid0000-0002-9447-2855
person.identifier.ridA-8153-2013
person.identifier.ridG-2345-2012
person.identifier.scopus-author-id35203489500
person.identifier.scopus-author-id9238724800
rcaap.rightsrestrictedAccesspor
rcaap.typearticlepor
relation.isAuthorOfPublicationfa01ef7f-7a2a-4f74-a405-714360b862f3
relation.isAuthorOfPublicationb16751a6-748e-44b0-9c59-058cbd5b2cc3
relation.isAuthorOfPublication.latestForDiscoveryfa01ef7f-7a2a-4f74-a405-714360b862f3

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