The relevant effect of an intramolecular hydrogen bond on the conformational equilibrium of cis-3-methoxycyclohexanol compared to trans-3-methoxycyclohexanol and cis-1,3-dimethoxycyclohexane

dc.creatorde Oliveira, PR
dc.creatorRittner, R
dc.date2005
dc.dateJUN
dc.date2014-11-16T13:43:55Z
dc.date2015-11-26T16:23:08Z
dc.date2014-11-16T13:43:55Z
dc.date2015-11-26T16:23:08Z
dc.date.accessioned2018-03-28T23:04:29Z
dc.date.available2018-03-28T23:04:29Z
dc.identifierSpectrochimica Acta Part A-molecular And Biomolecular Spectroscopy. Pergamon-elsevier Science Ltd, v. 61, n. 8, n. 1737, n. 1745, 2005.
dc.identifier1386-1425
dc.identifierWOS:000229376000004
dc.identifier10.1016/j.saa.2004.07.004
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/72341
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/72341
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/72341
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1268213
dc.descriptionH-1 NMR data show that an increase in the concentration of cis-3-methoxycyclohexanol (cis-3-MCH) shifts the conformational equilibrium from the 1aa conformer, stabilized by an intramolecular hydrogen bond (IAHB), to the fee conformer [X-ee = 44% (at 0.05 mol L-1) to 59% (at 0.40 mol L-1), in CCl4], which forms intermolecular hydrogen bonds (IEHB), as confirmed by IR data. The percentage of lee conformer increases with the solvent polarity, from 33% (Delta G(ee-aa) = 1.72 kJ mol(-1)) in cyclohexane (C6D12) to 97% (Delta G(ee-aa) = -8.41 kJ mol(-1)) in DMSO. For trans-3-methoxycyclohexanol (trans-3-MCH), lae and lea conformers are almost equally present in the studied solvents, lae increasing from 41%, in C6D12 (Delta G(ae-ea) = 0.84 kJ mol(-1)), to 49%, in DMSO (Delta G(ae-ea), = 0.13 kJ mol-1). A value of 18.4 kJ mol(-1) for the strength of IAHB in cis-3-MCH was obtained, from the theoretical data, through the CBS-4M method. (c) 2004 Elsevier B.V. All rights reserved.
dc.description61
dc.description8
dc.description1737
dc.description1745
dc.languageen
dc.publisherPergamon-elsevier Science Ltd
dc.publisherOxford
dc.publisherInglaterra
dc.relationSpectrochimica Acta Part A-molecular And Biomolecular Spectroscopy
dc.relationSpectroc. Acta Pt. A-Molec. Biomolec. Spectr.
dc.rightsfechado
dc.rightshttp://www.elsevier.com/about/open-access/open-access-policies/article-posting-policy
dc.sourceWeb of Science
dc.subjectconformational analysis
dc.subjecttheoretical calculations
dc.subjectintramolecular hydrogen bond
dc.subjectNMR spectroscopy
dc.subjectIR spectroscopy
dc.subjectSet Model Chemistry
dc.subjectNmr
dc.subjectEnergies
dc.subjectDensity
dc.subjectThioxoketones
dc.subjectCyclohexanes
dc.subjectExchange
dc.subjectSystems
dc.titleThe relevant effect of an intramolecular hydrogen bond on the conformational equilibrium of cis-3-methoxycyclohexanol compared to trans-3-methoxycyclohexanol and cis-1,3-dimethoxycyclohexane
dc.typeArtículos de revistas


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