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dc.creatorRašović, Aleksandar
dc.creatorBlagojević, Vladimir A.
dc.creatorBaranac Stojanović, Marija
dc.creatorKleinpeter, Erich
dc.creatorMarković, Rade
dc.creatorMinić, Dragica M.
dc.date.accessioned2018-04-11T10:12:05Z
dc.date.available2018-04-11T10:12:05Z
dc.date.issued2016
dc.identifier.issn1144-0546 (Print)
dc.identifier.issn1369-9261 (Online)
dc.identifier.urihttp://dais.sanu.ac.rs/123456789/2324
dc.description.abstractInformation about the strength of donor–acceptor interactions in push–pull alkenes is valuable, as this so-called “push–pull effect” influences their chemical reactivity and dynamic behaviour. In this paper, we discuss the applicability of NMR spectral data and barriers to rotation around the C[double bond, length as m-dash]C double bond to quantify the push–pull effect in biologically important 2-alkylidene-4-oxothiazolidines. While olefinic proton chemical shifts and differences in 13C NMR chemical shifts of the two carbons constituting the C[double bond, length as m-dash]C double bond fail to give the correct trend in the electron withdrawing ability of the substituents attached to the exocyclic carbon of the double bond, barriers to rotation prove to be a reliable quantity in providing information about the extent of donor–acceptor interactions in the push–pull systems studied. In particular all relevant kinetic data, that is the Arrhenius parameters (apparent activation energy Ea and frequency factor A) and activation parameters (ΔS‡, ΔH‡ and ΔG‡), were determined from the data of the experimentally studied configurational isomerization of (E)-9a. These results were compared to previously published related data for other two compounds, (Z)-1b and (2E,5Z)-7, showing that experimentally determined ΔG‡ values are a good indicator of the strength of push–pull character. Theoretical calculations of the rotational barriers of eight selected derivatives excellently correlate with the calculated C[double bond, length as m-dash]C bond lengths and corroborate the applicability of ΔG‡ for estimation of the strength of the push–pull effect in these and related systems.en
dc.format40 (2016) 6364-6373
dc.languageen
dc.publisherRoyal Society of Chemistry
dc.relationinfo:eu-repo/grantAgreement/MESTD/Basic Research (BR or ON)/172020/RS//
dc.rightsrestrictedAccess
dc.sourceNew Journal of Chemistryen
dc.subject2-alkylidene-4-oxothiazolidines
dc.subjectNMR
dc.subjectC-C bond
dc.subjectpush-pull effect
dc.titleQuantification of the push–pull effect in 2-alkylidene-4-oxothiazolidines by using NMR spectral data and barriers to rotation around the C[double bond, length as m-dash]C bonden
dc.typearticle
dc.rights.licenseARR
dcterms.abstractБаранац Стојановић, Марија; Благојевић, Владимир A.; Клеинпетер, Ерицх; Марковић, Раде; Минић, Драгица; Рашовић, Aлександар;
dc.citation.spage6364
dc.citation.epage6373
dc.citation.volume40
dc.identifier.wos000385869600088
dc.identifier.doi10.1039/c6nj00901h
dc.identifier.scopus2-s2.0-84979060401
dc.type.versionpublishedVersion


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