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dc.contributor.CRUESPUniversidade Estadual de Campinaspt_BR
dc.typeArtigo de periódicopt_BR
dc.titleCyclization of acylium ions with nitriles: gas-phase synthesis and characterization of 1,3,5-oxadiazinium ionspt_BR
dc.contributor.authorMeurer, ECpt_BR
dc.contributor.authorMoraes, LABpt_BR
dc.contributor.authorEberlin, MNpt_BR
unicamp.authorState Univ Campinas, UNICAMP, Inst Chem, BR-13083970 Campinas, SP, Brazilpt_BR
dc.subjectacylium ionspt_BR
dc.subjectnitrilespt_BR
dc.subjection-molecule reactionspt_BR
dc.subjectpentaquadrupole tandem mass spectrometrypt_BR
dc.subjectcyclization reactionspt_BR
dc.subject.wosMolecule Reactionspt_BR
dc.subject.wosMass-spectrometrypt_BR
dc.subject.wosCationspt_BR
dc.subject.wosTransacetalizationpt_BR
dc.subject.wosSubstitutionpt_BR
dc.subject.wos3dpt_BR
dc.description.abstractGas phase reactions of mass-selected acylium ions [CH3-C+=O (1), CH2=CH-C+=O (2), C6H5-C+=O (3), and (CH3)(2)N-C+=O (4)] with nitriles (CH3CN, C2H5CN, CH2=CHCN, and C6H5CN) were investigated using pentaquadrupole multiple-stage mass spectrometry. In analogy with the solution behavior, the ions were found to react readily with benzonitrile by cyclization via double nitrile addition to form aromatic 1,3,5-oxadiazinium ions. Cyclization with acetonitrile, propionitrile, and acrylonitrile is less general and occurs readily only for 4, by far the most reactive acylium ion tested. In "one-pot" reactions of 4 with two-component nitrile mixtures, cyclization via double nitrile addition occurs readily and forms both equally and differently 4,6-disubstituted isomeric 1,3,5-oxadiazinium ions. Using MS' experiments, the 1,3,5-oxadiazinium ions were mass-selected and then either reacted with nitrogen nucleophiles or dissociated by low-energy collisions with argon. The nucleophiles add readily to the ions, whereas the symmetry of the 1,3,5-oxadiazinium ring allows two competitive dissociation pathways: double retro-addition that re-forms the reactant acylium ion, or an analogous dissociation that, formally and combined with cyclization, promotes group exchange between one nitrile and the acylium ion: RCO+ + 2 (RCN)-C-1 --> cyclic 1,3,5-oxadiazinium ion --> (RCO+)-C-1 (RCN)-C-1 + RCN. Isomeric 4,6-disubstituted 1,3,5-oxadiazinium ions are easily distinguished because the nitrile added second is lost first via the double retro-addition dissociation. (C) 2001 Elsevier Science B.V.pt
dc.relation.ispartofInternational Journal Of Mass Spectrometrypt_BR
dc.relation.ispartofabbreviationInt. J. Mass Spectrom.pt_BR
dc.publisher.cityAmsterdampt_BR
dc.publisher.countryHolandapt_BR
dc.publisherElsevier Science Bvpt_BR
dc.date.issued2001pt_BR
dc.date.monthofcirculationDEC 20pt_BR
dc.identifier.citationInternational Journal Of Mass Spectrometry. Elsevier Science Bv, v. 212, n. 41699, n. 445, n. 454, 2001.pt_BR
dc.language.isoenpt_BR
dc.description.volume212pt_BR
dc.description.issuenumber41699pt_BR
dc.description.firstpage445pt_BR
dc.description.lastpage454pt_BR
dc.rightsfechadopt_BR
dc.rights.licensehttp://www.elsevier.com/about/open-access/open-access-policies/article-posting-policypt_BR
dc.sourceWeb of Sciencept_BR
dc.identifier.issn1387-3806pt_BR
dc.identifier.wosidWOS:000173003600031pt_BR
dc.identifier.doi10.1016/S1387-3806(01)00441-9pt_BR
dc.date.available2014-11-18T11:23:30Z
dc.date.available2015-11-26T16:54:27Z-
dc.date.accessioned2014-11-18T11:23:30Z
dc.date.accessioned2015-11-26T16:54:27Z-
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dc.description.provenanceMade available in DSpace on 2015-11-26T16:54:27Z (GMT). No. of bitstreams: 2 WOS000173003600031.pdf: 149227 bytes, checksum: bcf9ae4623f295b1ca6af0348a460b75 (MD5) WOS000173003600031.pdf.txt: 26380 bytes, checksum: 9d4f71290ac3ef9051981ef11999618d (MD5) Previous issue date: 2001en
dc.identifier.urihttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/57542pt_BR
dc.identifier.urihttp://www.repositorio.unicamp.br/handle/REPOSIP/57542
dc.identifier.urihttp://repositorio.unicamp.br/jspui/handle/REPOSIP/57542-
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