Structurally Diagnostic Ion-molecule Reactions: Acylium Ions With α-, β- And γ-hydroxy Ketones

dc.creatorMoraes L.A.B.
dc.creatorEberlin M.N.
dc.date2002
dc.date2015-06-30T16:42:52Z
dc.date2015-11-26T14:59:34Z
dc.date2015-06-30T16:42:52Z
dc.date2015-11-26T14:59:34Z
dc.date.accessioned2018-03-28T22:11:07Z
dc.date.available2018-03-28T22:11:07Z
dc.identifier
dc.identifierJournal Of Mass Spectrometry. , v. 37, n. 2, p. 162 - 168, 2002.
dc.identifier10765174
dc.identifier10.1002/jms.270
dc.identifierhttp://www.scopus.com/inward/record.url?eid=2-s2.0-0036180844&partnerID=40&md5=3d99cefcdab237cfb6e3ba4d270105c9
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/101706
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/101706
dc.identifier2-s2.0-0036180844
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1256077
dc.descriptionGas-phase reactions of four acylium ions and a thioacylium ion with three isomeric α-, β- and γ-hydroxy ketones are performed by pentaquadrupole mass spectrometric experiments. Novel structurally diagnostic reactions are observed, and found to correlate directly with interfunctional group separation. All five ions tested (CH3CO+, CH2=CHCO+, PhCO+, (CH3)2NCO+ and (CH3)2NCS+) react with the γ-hydroxy ketone (5-hydroxy-2-pentanone) to form nearly exclusively a cyclic oxonium ion of m/z 85 that formally arises from hydroxy anion abstraction. With the β-hydroxy ketone (4-hydroxy-2-pentanone), CH2=CHCO+, PhCO+ and (CH3)2NCO+ form adducts that undergo fast cyclization via intramolecular water displacement, yielding resonance-stabilized cyclic dioxinylium ions. With the α-hydroxy ketone (3-hydroxy-3-methyl-2-butanone), PhCO+, (CH3)2NCO+ and (CH3)2NCS+ form stable adducts. Evidence that these adducts display cyclic structures is provided by the triple-stage mass spectra of the (CH3)2NCS+ adduct; it dissociates to (CH3)2NCO+ via a characteristic reaction-dissociation pathway that promotes sulfur-by-oxygen replacement. If cyclizations are assumed to occur with intramolecular anchimeric assistance, relationships between structure and reactivity are easily recognized. Copyright © 2001 John Wiley & Sons, Ltd.
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dc.languageen
dc.publisher
dc.relationJournal of Mass Spectrometry
dc.rightsfechado
dc.sourceScopus
dc.titleStructurally Diagnostic Ion-molecule Reactions: Acylium Ions With α-, β- And γ-hydroxy Ketones
dc.typeArtículos de revistas


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