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

2008Journal article Restricted access
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dc.contributor.authorKaczor, A.
dc.contributor.authorProniewicz, L. M.
dc.contributor.authorAlmeida, R.
dc.contributor.authorGómez-Zavaglia, A.
dc.contributor.authorCristiano, Maria Lurdes Santos
dc.contributor.authorMatos Beja, A. M.
dc.contributor.authorRamos Silva, M.
dc.contributor.authorFausto, R.
dc.date.accessioned2014-06-09T13:09:06Z
dc.date.available2014-06-09T13:09:06Z
dc.date.issued2008
dc.date.updated2014-06-05T10:50:08Z
dc.description.abstractThe 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 interover intramolecular transfer of the methyl group is predicted for the ‘‘quasi-simultaneous” transfer of the methyl groups model, explaining the potential of MBID towards [1,30]-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.por
dc.identifier.citationKaczor, A.; Proniewicz, L.M.; Almeida, R.; Gómez-Zavaglia, A.; Cristiano, M.L.S.; Matos Beja, A.M.; Ramos Silva, M.; Fausto, R. The Chapman-type rearrangement in pseudosaccharins: The case of 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide, Journal of Molecular Structure, 892, 1-3, 343-352, 2008.por
dc.identifier.doihttp://dx.doi.org/10.1016/j.molstruc.2008.05.054
dc.identifier.issn0022-2860
dc.identifier.otherAUT: MCR00716;
dc.identifier.urihttp://hdl.handle.net/10400.1/4254
dc.language.isoengpor
dc.peerreviewedyespor
dc.publisherElsevierpor
dc.subjectPseudosaccharyl etherpor
dc.subjectMolecular structurepor
dc.subjectReaction pathpor
dc.subjectIR spectrapor
dc.subjectMatrix-isolationpor
dc.subjectDFT calculationspor
dc.titleThe chapman-type rearrangement in pseudosaccharins: the case of 3-(methoxy)-1,2-benzisothiazole 1,1-dioxidepor
dc.typejournal article
dspace.entity.typePublication
oaire.citation.endPage352por
oaire.citation.issue1-3por
oaire.citation.startPage343por
oaire.citation.titleJournal of Molecular Structurepor
oaire.citation.volume892por
person.familyNameCristiano
person.givenNameMaria de Lurdes
person.identifier.ciencia-idE411-6006-5A01
person.identifier.orcid0000-0002-9447-2855
person.identifier.ridG-2345-2012
person.identifier.scopus-author-id9238724800
rcaap.rightsrestrictedAccesspor
rcaap.typearticlepor
relation.isAuthorOfPublicationb16751a6-748e-44b0-9c59-058cbd5b2cc3
relation.isAuthorOfPublication.latestForDiscoveryb16751a6-748e-44b0-9c59-058cbd5b2cc3

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