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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.accessioned2018-11-22T00:37:12Z
dc.date.available2018-11-22T00:37:12Z
dc.date.issued2016
dc.identifier.issn1144-0546
dc.identifier.urihttp://cherry.chem.bg.ac.rs/handle/123456789/2336
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 CQC double bond to quantify the push-pull effect in biologically important 2-alkylidene-4-oxothiazolidines. While olefinic proton chemical shifts and differences in C-13 NMR chemical shifts of the two carbons constituting the CQC 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 ( Delta S-double dagger, Delta H-double dagger and Delta G(double dagger)), 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 Delta G(double dagger) 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 CQC bond lengths and corroborate the applicability of Delta G(double dagger) for estimation of the strength of the push-pull effect in these and related systems.en
dc.publisherRoyal Soc Chemistry, Cambridge
dc.relationinfo:eu-repo/grantAgreement/MESTD/Basic Research (BR or ON)/172020/RS//
dc.rightsrestrictedAccess
dc.sourceNew Journal of Chemistry
dc.titleQuantification of the push-pull effect in 2-alkylidene-4-oxothiazolidines by using NMR spectral data and barriers to rotation around the C=C bonden
dc.typearticle
dc.rights.licenseARR
dcterms.abstractМиниц, Драгица М.; Расовиц, Aлександар; Благојевиц, Владимир; Баранац-Стојановић, Марија; Клеинпетер, Ерицх; Марковиц, Раде;
dc.citation.volume40
dc.citation.issue7
dc.citation.spage6364
dc.citation.epage6373
dc.identifier.wos000385869600088
dc.identifier.doi10.1039/c6nj00901h
dc.citation.other40(7): 6364-6373
dc.citation.rankM22
dc.description.otherSupplementary material: [http://cherry.chem.bg.ac.rs/handle/123456789/3602]
dc.type.versionpublishedVersionen
dc.identifier.scopus2-s2.0-84979060401
dc.identifier.rcubKon_3152


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