Eksperimentalna i kvantno-hemijska proučavanja hinolonskih azo boja i njihovih prekursora

Abstract

Predmet istraživanja ove doktorske disertacije bila je eksperimentalna i teorijska analiza strukture hinolonskih azo boja i njihovih prekursora. U okviru disertacije, izvršena je sinteza azo boja kod kojih je ulogu kuplujuće komponente imao 4-hidroksi- -2-hinolon, dok je diazo komponenta bila odgovarajući p-supstituisan anilin. Najpre je izvršena sinteza serije N,N’-bisarilmalonamida (prekursora hinolona) čija je detaljna analiza (eksperimentalna i teorijska) dala odgovore u vezi sa geometrijom i reaktivnošću ispitivanih prekursora. Proučavan je uticaj supstituenata fenilnog jezgra, na azo-hidrazon tautomeriju u rastvorima (kod azo boja), kao i na geometriju i reaktivnost prekursora (kod N,N’-bisarilmalonamida). Takođe, proučavan je uticaj i rastvarača na formiranje intra- i intermolekulske vodonične veze kod N,N’-bisarilmalonamida. Izvršena je analiza uticaja rastvarača na apsorpcione spektre ispitivanih jedinjenja primenom linearne korelacije energije solvatacije (LSER) uz korišćenje Kamlet-Taftove (Kamlet-Taft) i Katalanove (Catalán) jednačine. Urađena je i optimizacija geometrije ispitivanih jedinjenja i proučeno je prenošenje elektronskih efekata primenom kvantno-hemijskih proračuna (DFT). Sva jedinjenja sintetisana su prema originalnim ili modifikovanim metodama iz literature. Jedinjenja su okarakterisana temperaturama topljenja, UV-Vis, FT-IR, 1H i 13C NMR spektrima i elementarnom analizom. Na osnovu spektralnih podataka utvrđena je struktura tautomernih oblika boja. UV-Vis apsorpcioni maksimumi određeni su u različitim rastvaračima (spektroskopske čistoće). Uticaj supstituenata na prenošenje elektronskih efekata kod N,N’-bisarilmalonamida ispitan je primenom jednoparametarske i dvoparametarske Hametove (Hammett) jednačine, kao i primenom Svain-Luptonove (Swain-Lupton) jednačine. Rezultati dobijeni UV-spektroskopskim merenjima (kod N,N'-bisarilmalonamida) pokazuju, da na položaj UV-apsorpcionih frekvencija mnogo više utiče prisutni supstituent na fenilnom prstenu, nego svojstva rastvarača. Kamlet-Taft analiza je pokazala da solvatohromizam nastaje najvećim delom zbog dipolarnosti/polarizabilnosti rastvarača. Rezultati dobijeni Hametovom jednačinom ukazuju na postojanje proširene delokalizacije. Kvantno mehanički poračuni ukazuju da u zavisnosti od okolnog medijuma molekuli N,N'-bisarilmalonamida mogu imati različitu geometriju. Rezultati dobijeni FT-IR i UV-Vis analizom hinolonskih boja pokazuju postojanje tautomerije kao i dominantnost hidrazo-keto oblika u odnosu na druge. Uticaj supstituenata na fenilnom jezgru na UV-Vis apsorpcione spektre takođe je veći nego uticaj rastvarača. NBO analize daju jasnu sliku o intramolekulskom prenosu naelektrisanja kod ispitivanih jedinjenja u zavisnosti od prisutnih supstituenata...

Subject of this doctoral dissertation is the experimental and theoretical analysis of quinolone azo dyes and their precursors structure. Within the theses, the synthesis of azo dyes in which the role of the coupling components had the 4-hydroxy-2-quinolone while the diazo component was the corresponding p-substituted aniline, was carried out. First the synthesis of a series of N,N'-bisarylmalonamides (precursor) was performed. In-depth analysis (experimental and theoretical) of the prepared amides afforded the answers regarding the geometry and the reactivity of the tested precursors. The impact of the nature of the substituents on the phenyl nucleus, on the azo-hydrazone tautomerism in solution (with azo dyes), as well as the geometry and the reactivity of the precursor (N,N'-bisarilmalonamida) was studied. Also, the influence of solvents on the azo-hydrazone tautomerism of azo dyes as well as the solvent effect on the formation of intra- and intermolecular hydrogen bonds in N,N'-bisarylmalonamides was investigated. The analysis was performed using linear correlation free energy of solvation (LSER) using Kamlet-Taft and Catalan equations. Has been done the optimization of the tested compounds and examined the transmission of electronic effects of the application of quantum-chemical calculations (DFT). All compounds were synthesized according to the original or modified methods from the literature. The compounds were characterized by melting point, UV-Vis, FT-IR, 1H and 13C NMR spectra and elemental analysis. Determination of UV-Vis absorption maximum in a variety of solvents (spectroscopic grade) was carried out using a UV-Vis spectrophotometer. The effect of substituents on the transmission of electronic effects in N,N’-bisarylmalonamides was tested using simple and extended Hammett equations, as well as by Swain-Lupton equation. The results obtained by UV spectroscopic measurements (the N,N'-bisarilmalonamida) shows that the position of a UV absorption frequency much more affects the nature of substituents present on the phenyl ring than the properties of the solvent. Kamlet-Taft analysis showed that solvatochromism occurs mainly due dipolarity/polarizability solvent. Results obtained using the Hammett equation, indicate the existence of extended delocalization. The quantum mechanical calculations indicate that depending on the surrounding medium molecule N,N'-bisarilmalonamida can have various geometry. The results obtained by FT-IR and UV-Vis analysis of quinolone azo dyes indicate the existence of tautomerism and dominance of hydrazo-keto form. The influence of nature of the substituents on the phenyl nucleus in UV-Vis absorption spectra is also higher than the effect of the solvent. NBO analysis results give a clear picture of intramolecular charge transfer of the tested compounds according to the substituents present compounds...