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doctoral thesis
Sinteza 3,4-dihidropirimidinonskih spojeva i njihovo kiralno prepoznavanje na polisaharidnim kiralnim nepokretnim fazama
Zagreb: University of Zagreb, Faculty of Science, 2015. urn:nbn:hr:217:902561
Večenaj, Ivana
University of Zagreb
Faculty of Science
Department of Chemistry

Institutional repository: Repository of the Faculty of Science

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Večenaj, I. (2015). Sinteza 3,4-dihidropirimidinonskih spojeva i njihovo kiralno prepoznavanje na polisaharidnim kiralnim nepokretnim fazama (Doctoral thesis). Zagreb: University of Zagreb, Faculty of Science. Retrieved from https://urn.nsk.hr/urn:nbn:hr:217:902561

Večenaj, Ivana. "Sinteza 3,4-dihidropirimidinonskih spojeva i njihovo kiralno prepoznavanje na polisaharidnim kiralnim nepokretnim fazama." Doctoral thesis, University of Zagreb, Faculty of Science, 2015. https://urn.nsk.hr/urn:nbn:hr:217:902561

Večenaj, Ivana. "Sinteza 3,4-dihidropirimidinonskih spojeva i njihovo kiralno prepoznavanje na polisaharidnim kiralnim nepokretnim fazama." Doctoral thesis, University of Zagreb, Faculty of Science, 2015. https://urn.nsk.hr/urn:nbn:hr:217:902561

Večenaj, I. (2015). 'Sinteza 3,4-dihidropirimidinonskih spojeva i njihovo kiralno prepoznavanje na polisaharidnim kiralnim nepokretnim fazama', Doctoral thesis, University of Zagreb, Faculty of Science, accessed 21 December 2024, https://urn.nsk.hr/urn:nbn:hr:217:902561

Večenaj I. Sinteza 3,4-dihidropirimidinonskih spojeva i njihovo kiralno prepoznavanje na polisaharidnim kiralnim nepokretnim fazama [Doctoral thesis]. Zagreb: University of Zagreb, Faculty of Science; 2015 [cited 2024 December 21] Available at: https://urn.nsk.hr/urn:nbn:hr:217:902561

I. Večenaj, "Sinteza 3,4-dihidropirimidinonskih spojeva i njihovo kiralno prepoznavanje na polisaharidnim kiralnim nepokretnim fazama", Doctoral thesis, University of Zagreb, Faculty of Science, Zagreb, 2015. Available at: https://urn.nsk.hr/urn:nbn:hr:217:902561

Metadata
TitleSinteza 3,4-dihidropirimidinonskih spojeva i njihovo kiralno prepoznavanje na polisaharidnim kiralnim nepokretnim fazama
Title (english)Synthesis of 3,4-dihydropyrimidinone compounds and their chiral recognition on polysaccharide chiral stationary phases
AuthorIvana Večenaj
MentorVladimir Vinković (mentor)
MBZ: 71214
MentorMladen Litvić (komentor)
MBZ: 249464
Committee memberVlasta Drevenkar (predsjednik povjerenstva)
Committee memberVladimir Vinković (član povjerenstva)
MBZ: 71214
Committee memberMladen Litvić (član povjerenstva)
MBZ: 249464
Committee memberNives Galić (član povjerenstva)
Committee memberInes Primožič (član povjerenstva)
GranterUniversity of Zagreb
Faculty of Science
(Department of Chemistry)
Zagreb
Defense date and country2015-12-16, Croatia
Scientific / art field,
discipline and subdiscipline		NATURAL SCIENCES
Chemistry
Universal decimal classification
(UDC)		54 - Chemistry. Crystallography. Mineralogy
Abstract
Optimirana su dva reakcijska protokola za sintezu 3,4-dihidropirimidinonskih spojeva (3,4-DHPM) temeljena na primjeni aluminijevog(III) tetrafluorborata heksahidrata i bakrovog(II) besilata tetrahidrata. Neovisno o karakteristikama reaktanata, postignuta su vrlo dobra reakcijska iskorištenja. Utvrđeno je kako se reakcija katalizirana s [Al(H2O)6](BF4)3 odvija preko takozvanog ureido-krotonata, dok mehanizam reakcije katalizirane s [Cu(C6H5SO3)2]×4H2O uključuje nastajanje N-aciliminijevog iona. Enantioselektivnom kromatografskom analizom 3,4-DHPM spojeva na polisaharidnim kiralnim nepokretnim fazama (KNF), uz pokretne faze različitih polarnosti, najbolja odjeljivanja postignuta su na 3,5-dimetilfenilkarbamoil amiloznoj KNF te je određen različit mehanizam kiralnog prepoznavanja uz etanol ili propan-2-ol kao modifikatore. Uz etanol kao modifikator kiralnom prepoznavanju doprinosi para-supstitucija arilnog prstena 3,4-DHPM-a, neovisno da li je riječ o elektron odvlačećoj ili elektron donirajućoj skupini, vodikova veza između NH skupine u DHPM prstenu i C=O skupine na KNF te vodikova veza između C=O skupine DHPM prstena i NH skupine na KNF. - interakcije analita i KNF su ključni mehanizam zadržavanja samo za drugoizlazeće enantiomere. Uz propan-2-ol utvrđeno je kako se najbolje kiralno prepoznavanje postiže za para-metoksi supstituirani 3,4-DHPM te da je vodikova veza u kojoj sudjeluje NH skupina DHPM prstena slabija od one u kojoj sudjeluje C=O skupina. S propan-2-olom - interakcije analita i KNF ne doprinose kiralnom prepoznavanju.
Abstract (english)
Abstract Two reaction protocols based on use of hexaaquaaluminium(III) tetrafluoroborate and copper(II) benzensulphonate tetrahydrate are optimized for synthesis of 3,4-dihydropyrimidinone (3,4-DHPM). Regardless the characteristics of reactants, high yields were achieved. While reaction catalyzed by [Al(H2O)6](BF4)3 includes formation of ureido-crotonate, reaction catalyzed by [Cu(C6H5SO3)2]×4H2O includes formation of acylimino intermediate. According to results obtained by enantioselective chromatographic analysis of 3,4-DHPM compounds on different polysaccharide chiral stationary phases (CSPs), the best resolutions are achieved using 3,5-dimethylphenyl carbamoyl amylose CSPs. Also, different mechanism of chiral recognition is established while using ethanol or propan-2-ol as modifier. With ethanol as modifier, chiral recognition is contributed by para-substitution of aryl ring of 3,4-DHPM, with both electron-withdrawing and electron-donating substituents, by hydrogen bond between NH group of DHPM ring and C=O group of CSP and by hydrogen bond between C=O group of DHPM ring and NH group of CSP. - interactions of analyte and CSP play significant role in retention mechanism of second elution enantiomers. With propan-2-ol, the best chiral recognitions are achieved for para-methoxy substituted 3,4-DHPM. In case of this modifier, hydrogen bond which involves NH group of DHPM ring is weaker than one that includes C=O group. With propan-2-ol - interactions of analyte and CSP do not contribute to chiral recognition.
Keywords
Keywords (english)
Languagecroatian
URN:NBNurn:nbn:hr:217:902561
Study programmeTitle: Doctoral study in chemistry
Study programme type: university
Study level: postgraduate
Academic / professional title: doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija (doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija)
Type of resourceText
Extent252 str. ; 30 cm
File originBorn digital
Access conditionsOpen access
Terms of useLicence In copyright icon
Created on2017-02-13 13:19:33