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dc.contributor.CRUESPUNIVERSIDADE ESTADUAL DE CAMPINASpt_BR
dc.contributor.authorunicampTormena, Cláudio Francisco-
dc.contributor.authorunicampRittner Neto, Roberto-
dc.typeArtigopt_BR
dc.titleSpectroscopic and theoretical studies of some N-methoxy-N-methyl-2-[(4′-substituted) phenylthio]propanamidespt_BR
dc.contributor.authorOlivato, Paulo R.-
dc.contributor.authorDomingues, Nelson L.C.-
dc.contributor.authorMondino, Mirta G.-
dc.contributor.authorTormena, Cláudio F.-
dc.contributor.authorRittner, Roberto-
dc.contributor.authorColle, Maurizio Dal-
dc.subjectAnálise conformacionalpt_BR
dc.subject.otherlanguageConformational analysispt_BR
dc.description.abstractThe analysis of the IR carbonyl band of the N-methoxy-N-methyl-2-[(4'-substituted)phenylthio]propanamides Y-PhSCH(Me)C(O)N(OMe)Me (Y=OMe 1, Me 2, H 3, Cl 4, NO2 5), supported by B3LYP/cc-pVDZ calculations of 3, indicated the existence of two gauche conformers (g(1) and g(2)), the g(1) conformer being the more stable and the less polar one (in gas phase and in solution). Both conformers are present in solution of the polar solvents (CH2Cl2 and CH3CN) for 1-5 and in solution of the less polar solvent (CHCl3) for 1-4, while only the g(1) conformer is present in solution of non polar solvents (n-C6H14 and CCl4) and in solution of CHCl3 for 5. NBO analysis shows that both the sigma(C-S) -> pi*(C=O) (hyperconjugative) and the pi(C=O) -> sigma*(C-S) orbital interactions contribute almost to the same extent for the stabilization of g(1) and g(2) conformers. The pi*(C=O) -> sigma*(C-S), n(S) -> pi*(C=O) and the n(S) -> pi*(C=O) orbital interactions stabilize more the g(1) conformer than the g(2) one. Moreover, the suitable geometry of the g(1) conformer leads to its stabilization through the LPO2 -> sigma*(C8-H11) orbital interaction (hydrogen bond) along with the strong O-[CO](delta-) center dot center dot center dot H-[O-Ph](delta+) electrostatic interaction. On the other hand, the appropriate geometry of the g(2) conformer leads to its stabilization by the LPO22 -> sigma*(C9-H13) orbital interaction (hydrogen bond) along with the weak O-[OMe](delta-) center dot center dot center dot H-[o'-Ph](delta+) electrostatic static interaction. As for the 4'-nitro derivative 5 the ortho-phenyl hydrogen atom becomes more acidic, leading to a stronger O-[CO](delta-) center dot center dot center dot H-[o-Ph](delta+) interaction and, thus, into a larger stabilization of the g(1) conformer in the whole series. This trend is responsible for the unique IR carbonyl band in CHCl3 solution of 5. The larger occupancy of the pi*(C=O) orbital of the g(1) conformer relative to that of the g(2) conformer, along with the O-[CO](delta-) center dot center dot center dot H-[o-Ph](delta+) electrostatic interaction (hydrogen bond) justifies the lower carbonyl frequency of the g(1) conformer with respect to the g(2) one, in gas phase and in solutionpt_BR
dc.relation.ispartofJournal of molecular structurept_BR
dc.publisher.cityAmsterdampt_BR
dc.publisher.countryPaíses Baixospt_BR
dc.publisherElsevierpt_BR
dc.date.issued2009-
dc.date.monthofcirculationFeb.pt_BR
dc.language.isoengpt_BR
dc.description.volume920pt_BR
dc.description.issuenumber1/3pt_BR
dc.description.firstpage393pt_BR
dc.description.lastpage400pt_BR
dc.rightsFechadopt_BR
dc.sourceWOSpt_BR
dc.identifier.issn0022-2860pt_BR
dc.identifier.eissn1872-8014pt_BR
dc.identifier.doi10.1016/j.molstruc.2008.11.040pt_BR
dc.identifier.urlhttps://www.sciencedirect.com/science/article/pii/S0022286008007874pt_BR
dc.description.sponsorshipCONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQpt_BR
dc.description.sponsorshipFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPpt_BR
dc.description.sponsordocumentnumberSem informaçãopt_BR
dc.description.sponsordocumentnumberSem informaçãopt_BR
dc.date.available2020-09-02T19:55:27Z-
dc.date.accessioned2020-09-02T19:55:27Z-
dc.description.provenanceSubmitted by Thais de Brito Barroso (tbrito@unicamp.br) on 2020-09-02T19:55:27Z No. of bitstreams: 0. Added 1 bitstream(s) on 2021-01-04T15:12:26Z : No. of bitstreams: 1 000264251400059.pdf: 592152 bytes, checksum: 6f60a26b2fa3dcc90cc8d90bfed64185 (MD5)en
dc.description.provenanceMade available in DSpace on 2020-09-02T19:55:27Z (GMT). No. of bitstreams: 0 Previous issue date: 2009en
dc.identifier.urihttp://repositorio.unicamp.br/jspui/handle/REPOSIP/348587-
dc.contributor.departmentDepartamento de Química Orgânicapt_BR
dc.contributor.departmentDepartamento de Química Orgânicapt_BR
dc.contributor.unidadeInstituto de Químicapt_BR
dc.contributor.unidadeInstituto de Químicapt_BR
dc.subject.keywordInfrared spectroscopypt_BR
dc.subject.keywordTheoretical calculationspt_BR
dc.subject.keywordN-Methoxy-N-methyl-2-[(40substituted)phenylthio]propanamidespt_BR
dc.identifier.source000264251400059pt_BR
dc.creator.orcid0000-0002-1508-0694pt_BR
dc.creator.orcid0000-0002-4715-6139pt_BR
dc.type.formArtigopt_BR
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