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An LFER study of the protolytic equilibria of 4-aryl-2,4-dioxobutanoic acids in aqueous solutions
Linearne korelacije slobodne energije (LFER) protolitičkih ravnoteža 4-aril-2,4-dioksobutanskih kiselina u vodenim rastvorima
dc.creator | Verbić, Tatjana Ž. | |
dc.creator | Drakulić, Branko | |
dc.creator | Zloh, Mire | |
dc.creator | Pecelj, Jovana R. | |
dc.creator | Popović, Gordana | |
dc.creator | Juranić, Ivan O. | |
dc.date.accessioned | 2019-09-02T11:11:31Z | |
dc.date.available | 2019-09-02T11:11:31Z | |
dc.date.issued | 2007 | |
dc.identifier.issn | 0352-5139 | |
dc.identifier.uri | https://farfar.pharmacy.bg.ac.rs/handle/123456789/997 | |
dc.description.abstract | The protolytic equilibria of 13 4-aryl-2,4-dioxobutanoic acids (ADKs) were spectrophotometrically studied in aqueous solutions in the pH range 1-9 at 25±1 °C and an ionic strength of 0.1 mol l-1 (NaCl), with the exception of the 4-OH-derivative which was also potentiometrically studied in the pH range 7-10 at 25±1 °C and an ionic strength of 0.1 mol l-1 (NaCl). In solution, the compounds simultaneously exist in one diketo and two enolic forms; therefore, the determined acidity constants (pKa1 1.87-2.29, pKa2 6.63-8.13 and pKa3(4-OH-) 9.52) represent system macro constants. The 1H-NMR spectrum of the parent compound (4-phenyl- -2,4-dioxobutanoic acid) (25 °C, pD 5.0) proved the existence of all tautomeric forms. Using the extended Hammett relation, the determined pKa values were correlated with literature σ values. The predicted pKa values were in fair accordance with the experimentally observed ones. Molecular, monoanionic and dianionic forms of the parent compound were optimized by the semi-empirical molecular orbital PM6 method using the implicit water solvation model (COSMO). The obtained geometries were used to explain the quality of the LFER models. | en |
dc.description.abstract | Protolitičke ravnoteže 13 jedinjenja iz klase 4-aril-2,4-dioksobutanskih kiselina (ADK) spektrofotometrijski su proučavane u vodenim rastvorima u pH intervalu 1-9 pri temperaturi 25±1 °C i jonskoj jačini rastvora 0.1 mol l-1 (NaCl), sa izuzetkom 4-OH-derivata koji je proučavan i potenciometrijski u pH intervalu 7-10 pri istim uslovima. Kako ADK u vodenom rastvoru podležu keto-enolnoj tautomeriji i istovremeno postoje u diketo i dva enolna oblika, to određene kiselinske konstante (pKa1 1.87-2.29, pKa2 6.63-8.13 i pKa3(4-OH-) 9.52) predstavljaju makro konstante za dati sistem. 1H-NMR spektar osnovne supstance (4-fenil-2,4-dioksobutanska kiselina) (25 °C, pD 5.0) potvrđuje prisustvo svih tautomernih oblika. Upotrebom proširene Hametove korelacije, određene pKa vrednosti korelisane su sa literaturnim σ vrednostima. Predviđene pKa vrednosti dobro se slažu sa eksperimentalno dobijenim. Molekulski, monoanjonski i dianjonski oblici osnovne supstance su optimizovani semiempirijskom molekulsko-orbitalnom PM6 metodom sa implicitnim modelom solvatacije u vodi (COSMO). Dobijene geometrije su upotrebljene za objašnjenje kvaliteta LFER modela. | sr |
dc.publisher | Srpsko hemijsko društvo, Beograd | |
dc.relation | info:eu-repo/grantAgreement/MESTD/MPN2006-2010/142010/RS// | |
dc.relation | info:eu-repo/grantAgreement/MESTD/MPN2006-2010/142062/RS// | |
dc.rights | openAccess | |
dc.rights.uri | https://creativecommons.org/licenses/by-nc-nd/4.0/ | |
dc.source | Journal of the Serbian Chemical Society | |
dc.subject | acidity constants | en |
dc.subject | 4-aryl-2 | en |
dc.subject | 4-dioxobutanoic acids (ADK) | en |
dc.subject | linear free energy relationship (LFER) | en |
dc.title | An LFER study of the protolytic equilibria of 4-aryl-2,4-dioxobutanoic acids in aqueous solutions | en |
dc.title | Linearne korelacije slobodne energije (LFER) protolitičkih ravnoteža 4-aril-2,4-dioksobutanskih kiselina u vodenim rastvorima | sr |
dc.type | article | |
dc.rights.license | BY-NC-ND | |
dcterms.abstract | Јуранић, Иван О.; Поповић, Гордана; Вербић, Татјана Ж.; Злох, Мире; Пецељ, Јована Р.; Дракулић, Бранко; Линеарне корелације слободне енергије (ЛФЕР) протолитичких равнотежа 4-арил-2,4-диоксобутанских киселина у воденим растворима; Линеарне корелације слободне енергије (ЛФЕР) протолитичких равнотежа 4-арил-2,4-диоксобутанских киселина у воденим растворима; | |
dc.citation.volume | 72 | |
dc.citation.issue | 12 | |
dc.citation.spage | 1201 | |
dc.citation.epage | 1216 | |
dc.citation.other | 72(12): 1201-1216 | |
dc.citation.rank | M23 | |
dc.identifier.wos | 000252412100005 | |
dc.identifier.doi | 10.2298/JSC0712201V | |
dc.identifier.scopus | 2-s2.0-36949036470 | |
dc.identifier.fulltext | https://farfar.pharmacy.bg.ac.rs//bitstream/id/2318/995.pdf | |
dc.type.version | publishedVersion |