Halogenated six-membered rings: a theoretical approach for substituent effects in conformational analysis

dc.creatorFreitas, MP
dc.creatorTormena, CF
dc.creatorOliveira, PR
dc.creatorRittner, R
dc.date2002
dc.dateAUG 16
dc.date2014-11-13T13:49:20Z
dc.date2015-11-26T17:09:49Z
dc.date2014-11-13T13:49:20Z
dc.date2015-11-26T17:09:49Z
dc.date.accessioned2018-03-28T23:58:26Z
dc.date.available2018-03-28T23:58:26Z
dc.identifierJournal Of Molecular Structure-theochem. Elsevier Science Bv, v. 589, n. 147, n. 151, 2002.
dc.identifier0166-1280
dc.identifierWOS:000177453900016
dc.identifier10.1016/S0166-1280(02)00256-7
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/68560
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/68560
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/68560
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1280714
dc.descriptionStudies on the conformational equilibria of a series of dihalosubstituted cyclohexanes (I) and halocyclohexanones (II) are reported. Theoretical calculations using the B3LYP method and the 6-311 + g(d,p) basis set were applied to determine the energy differences (DeltaE) between the conformers of I and II, as well DeltaE between the conformers of monohalocyclohexanes, in order to obtain the intramolecular interaction energies, which govern the conformational equilibria of I and II. It is shown that while the intramolecular interactions for 1,3- and 1,4-disubstituted cyclohexanes, as well as for 3- and 4-halocyclohexanones, are due to classical effects (steric and electrostatic), for the 2-halocyclohexanones it becomes evident that orbital interactions between n(halo) and pi(CO)(*) drive the equilibria towards the axial conformers. Moreover, the gauche effect seems to be irrelevant for the trans-1,2-dihalocyclohexane equilibria, opposite to several reports from the literature on other trans-1,2-disubstituted cyclohexanes bearing electronegative substituents. (C) 2002 Elsevier Science B.V. All rights reserved.
dc.description589
dc.description147
dc.description151
dc.languageen
dc.publisherElsevier Science Bv
dc.publisherAmsterdam
dc.publisherHolanda
dc.relationJournal Of Molecular Structure-theochem
dc.relationTheochem-J. Mol. Struct.
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.subjecthalocyclohexanones
dc.subjectsubstituent effects
dc.subjectAttractive Nonbonded Interactions
dc.subjectOrganic-molecules
dc.subjectConsequences
dc.subjectCyclohexanes
dc.titleHalogenated six-membered rings: a theoretical approach for substituent effects in conformational analysis
dc.typeArtículos de revistas


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