Intra- i intermolekulske vodikove veze u derivatima acetilacetona i benzoilacetona

doctoral thesis

• Title (english): Intra- and intermolecular hydrogen bonding in acetylacetone and benzoylacetone derivatives
• Author: Vedrana Lazić
• Mentor: Marina Cindrić (mentor)
• Mentor: Predrag Novak (komentor)
• Committee member: Tomica Hrenar (predsjednik povjerenstva)
• Committee member: Predrag Novak (član povjerenstva)
• Committee member: Ivo Piantanida (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2017-02-03, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry
• Universal decimal classification (UDC): 54 - Chemistry. Crystallography. Mineralogy

Abstract

Enaminoni (enamini β-dikarbonilnih spojeva) pripadaju skupini organskih molekula
koje posjeduju zanimljiva biološka i farmakološka svojstva, a mogu postojati u tri tautomerne
forme, s mogućnošću stvaranja intra- i intermolekulskih vodikovih veza. Detaljna strukturna
karakterizacija ove skupine organskih molekula nužna je kako bi se što bolje objasnila i
povezala svojstva s molekulskom strukturom i vodikovim vezama prisutnim u otopini i
čvrstom stanju.
U ovom radu određena je struktura derivata pentan-2,4-diona i 1-fenil-but-2-en-1-ona
u otopini, pomoću različitih spektroskopskih i računskih metoda. Korištenjem
jednodimenzijskih i dvodimenzijskih tehnika spektroskopije NMR, te spektroskopije UV,
spektroskopije IR i Ramanove spektroskopije proučavan je utjecaj supstituenata (2-amino-3-
nitrofenola i derivata 2-amino-2-metilfenola), prirode otapala (različita polarnost, različita
proton-donorska odnosno proton-akceptorska svojstava) i temperature na vodikove veze
(intra- i intermolekulske) i molekulsku strukturu derivata pentan-2,4-diona i 1-fenil-but-2-en1-ona.
Eksperimentalni rezulatati upotpunjeni su podacima konformacijske analize pri čemu
su korištene računske metode na semiempirijskoj razini (PM6) i metode funkcionala gustoće
(DFT). Vodikove veze su okarakterizirane u vakuumu, kloroformu i dimetilsulfoksidu
(DMSO-u).
Ova istraživanja su pokazala da su svi derivati pentan-2,4-diona i 1-fenil-but-2-en-1-
ona u otopini prisutni u keto-aminskoj formi, neovisno o otapalu i temperaturi. Dokazano je
postojanje jakih intramolekulskih vodikovih veza tipa N–H
...O, te slabih intermolekulskih
interakcija između dvije molekule spoja i/ili između molekule spoja i otapala.

Abstract (english)

Enaminones (enamines of β-dicarbonyl compounds) belongs to a group of organic
molecules with interesting biological and farmaceutical properties, and might exist in three
tautomeric forms, with the possibility of forming intra- and intermolecular hydrogen bonds.
Detailed structural characterization of this group of organic molecules is needed to establish
structure acitivity ralationships with special emphasis on hydrogen bonding.
In this doctoral thesis structures of pentane-2,4-dione and 1-phenyl-but-2-en-1-one
derivatives has been determined in solution, by using different spectroscopic (one and two
dimensional NMR spectroscopy, UV, IR and Raman spectroscopy) and computational
methods.
Special attention has been devoted to the influence of the substituents (2-amino-3-
nitrophenol i derivatives of 2-amino-2-methylphenols), nature of the solvent (different
polarity and different proton-donor and proton-acceptor abbilites) and temperature on
hydrogen bonding (intra- and intermolecular) structure of pentane-2,4-dione and 1-phenylbut-2-en-1-one derivatives.
The experimental results were complemented with those obtained by computational
methods, performed at the semiempirical PM6 level and by using density functional theory
(DFT). Hydrogen bonding were characterized in vacuum, chloroforme and dimethyl sulfoxide
(DMSO).
All investigated pentane-2,4-dione and 1-phenyl-but-2-en-1-one derivatives have been
found to exist in the ketoamine form in solution, irrespective of the solvent and the
temperature. Results showed presence of strong intramolecular hydrogen bonds of the N–
H
...O type as well as weaker intermolecular interactions between two molecules or between
the molecule and the solvent.

• Keywords: enaminoni; pentan-2; 4-dion; 1-fenil-but-2-en-1-on; vodikove veze; spektrosokopija NMR
• Keywords (english): enaminones; pentane-2; 4-dione; 1-phenyl-but-2-en-1-one; hydrogen bonding; NMR spectroscopy
• Language: croatian
• URN:NBN: urn:nbn:hr:217:747997
• Promotion: 2023
• Study programme: Title: 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 resource: Text
• Extent: 92, XLIX str. ; 30 cm
• File origin: Born digital
• Access conditions: Open access
• Created on: 2023-07-03 08:58:01