Conformational analysis of fluoroacetoxime and of its O-methyl ether by H-1, C-13 and N-15 NMR and theoretical calculations

dc.creatorTormena, CF
dc.creatorRittner, R
dc.creatorAbraham, RJ
dc.creatorBasso, EA
dc.creatorFiorin, BC
dc.date2004
dc.dateJAN
dc.date2014-07-30T14:00:38Z
dc.date2015-11-26T16:33:34Z
dc.date2014-07-30T14:00:38Z
dc.date2015-11-26T16:33:34Z
dc.date.accessioned2018-03-28T23:15:28Z
dc.date.available2018-03-28T23:15:28Z
dc.identifierJournal Of Physical Organic Chemistry. John Wiley & Sons Ltd, v. 17, n. 1, n. 42, n. 48, 2004.
dc.identifier0894-3230
dc.identifierWOS:000187952200004
dc.identifier10.1002/poc.682
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/56506
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/56506
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1270899
dc.descriptionThe solvent dependence of the H-1, C-13 and N-15 NMR spectra of (E)-fluoroacetoxime [(E)-FAO] and of (E)-fluoroacetoxime O-methyl ether [(E)-FAOME], was examined and the HF, CF and NF couplings are reported. Density functional theory (DFT) at the B3LYP/6-311++g(2df,2p) level with ZPE (zero point energy) correction was used to obtain the rotamer geometries. In both (E)-FAO and (E)-FAOME the DFT method gave two energy minima corresponding to the cis (F-C-C = N, 0degrees) and gauche (F-C-C = N, 124.1degrees) rotamers. In contrast, in (Z)-FAO the DFT method gave only one energy minimum corrsponding to the trans rotamer. The (4)J(HF) and (1)J(CF) couplings in (E)-FAO were analyzed by solvation theory assuming the cis and gauche forms to give E-cis - E-gauche = 3.3 kcal mol(-1) in the vapor phase, decreasing to 1.54 kcal mol(-1) in CCl4 and -1.19 kcal mol(-1) in DMSO (1 kcal = 4.184 kJ. In (E)-FAOME the observed couplings, when analysed similarly by solvation theory, gave E-cis - E-gauche = 2.2 kcal mol(-1) in the vapor phase, 0.91 kcal mol(-1) in CCl4 and -1.18 kcal mol(-1) in DMSO. The (3)J(NF) coupling was independent of the molecular conformation, as it did not change with the solvent polarity. Copyright (C) 2003 John Wiley Sons, Ltd.
dc.description17
dc.description1
dc.description42
dc.description48
dc.languageen
dc.publisherJohn Wiley & Sons Ltd
dc.publisherChichester
dc.publisherInglaterra
dc.relationJournal Of Physical Organic Chemistry
dc.relationJ. Phys. Org. Chem.
dc.rightsfechado
dc.rightshttp://olabout.wiley.com/WileyCDA/Section/id-406071.html
dc.sourceWeb of Science
dc.subjectH-1
dc.subjectC-13
dc.subjectN-15 NMR
dc.subjectconformations
dc.subjectfluoroacetoximes
dc.subjectsolvation theory
dc.subjecttheoretical calculation
dc.subjectSpin Coupling-constants
dc.subjectRotational-isomerism
dc.subjectMicrowave Spectrum
dc.subjectAcetone Oximes
dc.subjectSolvation
dc.subjectIr
dc.subjectSpectroscopy
dc.subjectDft
dc.titleConformational analysis of fluoroacetoxime and of its O-methyl ether by H-1, C-13 and N-15 NMR and theoretical calculations
dc.typeArtículos de revistas


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