A set of azo dyes were prepared by diazotization of a series of electronically different substituted anilines and subsequent azo coupling of these diazonium salts with ethyl 4,5-dihydro-5-oxo-2-aryl(1H)pyrrole-3-carboxylate as a the coupling component. All of the dyes were confirmed as keto-hydrazone tautomers and were found as a mixtures of E- and Z- isomers with respect to the exocyclic C=N bond by 1H NMR spectroscopy. The absorption spectra are all similar irrespective of substituent and solvent. By comparison the fluorescence is strongly dependent on the electronic character of the substituents. All compounds fluoresce in a low temperature solvent glass and in the solid state except the ortho hydroxyl and ortho nitro derivatives and only the 4-cyanophenyl and 4-nitrophenyl derivatives show fluorescence in solution at room temperature. The spectroscopic behavior is explained in terms of competition between E/Z isomerisation and fluorescence after excitation.
In the second part of this work short series of cobalt and chromium complex dyes based on pyrrolinone ring was prepared; the synthesis of these compounds was based on using pure hydrazone dyes as starting ligand. Multinuclear magnetic resonance spectroscopy (NMR) technique was very useful for proving the structure of prepared compounds. In contrast to the starting compounds existing ligands completely in hydrazone form, cobalt (III) complexes exist in (E)-azo configuration and cobalt atom is six-coordinated being bound to oxygens, which originate in hydroxyl and CONH groups and nitrogens from substituted anilines as starting material from two ligands. Spectral properties of these compounds were studied as well as photochemical isomerisation using absorption spectra.
Anotace v angličtině
A set of azo dyes were prepared by diazotization of a series of electronically different substituted anilines and subsequent azo coupling of these diazonium salts with ethyl 4,5-dihydro-5-oxo-2-aryl(1H)pyrrole-3-carboxylate as a the coupling component. All of the dyes were confirmed as keto-hydrazone tautomers and were found as a mixtures of E- and Z- isomers with respect to the exocyclic C=N bond by 1H NMR spectroscopy. The absorption spectra are all similar irrespective of substituent and solvent. By comparison the fluorescence is strongly dependent on the electronic character of the substituents. All compounds fluoresce in a low temperature solvent glass and in the solid state except the ortho hydroxyl and ortho nitro derivatives and only the 4-cyanophenyl and 4-nitrophenyl derivatives show fluorescence in solution at room temperature. The spectroscopic behavior is explained in terms of competition between E/Z isomerisation and fluorescence after excitation.
In the second part of this work short series of cobalt and chromium complex dyes based on pyrrolinone ring was prepared; the synthesis of these compounds was based on using pure hydrazone dyes as starting ligand. Multinuclear magnetic resonance spectroscopy (NMR) technique was very useful for proving the structure of prepared compounds. In contrast to the starting compounds existing ligands completely in hydrazone form, cobalt (III) complexes exist in (E)-azo configuration and cobalt atom is six-coordinated being bound to oxygens, which originate in hydroxyl and CONH groups and nitrogens from substituted anilines as starting material from two ligands. Spectral properties of these compounds were studied as well as photochemical isomerisation using absorption spectra.
Klíčová slova
Pyrrolinone estery, Ethyl 4,5-dihydro-5-oxo-2-aryl(1H)pyrrole-3-carboxylat, Absorpční a fluorescenční spektra
Klíčová slova v angličtině
Pyrrolinone esters, Ethyl 4,5-dihydro-5-oxo-2-aryl(1H)pyrrole-3-carboxylate, Absorption and fluorescence spectra
Rozsah průvodní práce
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Jazyk
AN
Anotace
A set of azo dyes were prepared by diazotization of a series of electronically different substituted anilines and subsequent azo coupling of these diazonium salts with ethyl 4,5-dihydro-5-oxo-2-aryl(1H)pyrrole-3-carboxylate as a the coupling component. All of the dyes were confirmed as keto-hydrazone tautomers and were found as a mixtures of E- and Z- isomers with respect to the exocyclic C=N bond by 1H NMR spectroscopy. The absorption spectra are all similar irrespective of substituent and solvent. By comparison the fluorescence is strongly dependent on the electronic character of the substituents. All compounds fluoresce in a low temperature solvent glass and in the solid state except the ortho hydroxyl and ortho nitro derivatives and only the 4-cyanophenyl and 4-nitrophenyl derivatives show fluorescence in solution at room temperature. The spectroscopic behavior is explained in terms of competition between E/Z isomerisation and fluorescence after excitation.
In the second part of this work short series of cobalt and chromium complex dyes based on pyrrolinone ring was prepared; the synthesis of these compounds was based on using pure hydrazone dyes as starting ligand. Multinuclear magnetic resonance spectroscopy (NMR) technique was very useful for proving the structure of prepared compounds. In contrast to the starting compounds existing ligands completely in hydrazone form, cobalt (III) complexes exist in (E)-azo configuration and cobalt atom is six-coordinated being bound to oxygens, which originate in hydroxyl and CONH groups and nitrogens from substituted anilines as starting material from two ligands. Spectral properties of these compounds were studied as well as photochemical isomerisation using absorption spectra.
Anotace v angličtině
A set of azo dyes were prepared by diazotization of a series of electronically different substituted anilines and subsequent azo coupling of these diazonium salts with ethyl 4,5-dihydro-5-oxo-2-aryl(1H)pyrrole-3-carboxylate as a the coupling component. All of the dyes were confirmed as keto-hydrazone tautomers and were found as a mixtures of E- and Z- isomers with respect to the exocyclic C=N bond by 1H NMR spectroscopy. The absorption spectra are all similar irrespective of substituent and solvent. By comparison the fluorescence is strongly dependent on the electronic character of the substituents. All compounds fluoresce in a low temperature solvent glass and in the solid state except the ortho hydroxyl and ortho nitro derivatives and only the 4-cyanophenyl and 4-nitrophenyl derivatives show fluorescence in solution at room temperature. The spectroscopic behavior is explained in terms of competition between E/Z isomerisation and fluorescence after excitation.
In the second part of this work short series of cobalt and chromium complex dyes based on pyrrolinone ring was prepared; the synthesis of these compounds was based on using pure hydrazone dyes as starting ligand. Multinuclear magnetic resonance spectroscopy (NMR) technique was very useful for proving the structure of prepared compounds. In contrast to the starting compounds existing ligands completely in hydrazone form, cobalt (III) complexes exist in (E)-azo configuration and cobalt atom is six-coordinated being bound to oxygens, which originate in hydroxyl and CONH groups and nitrogens from substituted anilines as starting material from two ligands. Spectral properties of these compounds were studied as well as photochemical isomerisation using absorption spectra.
Klíčová slova
Pyrrolinone estery, Ethyl 4,5-dihydro-5-oxo-2-aryl(1H)pyrrole-3-carboxylat, Absorpční a fluorescenční spektra
Klíčová slova v angličtině
Pyrrolinone esters, Ethyl 4,5-dihydro-5-oxo-2-aryl(1H)pyrrole-3-carboxylate, Absorption and fluorescence spectra
Zásady pro vypracování
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Zásady pro vypracování
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Seznam doporučené literatury
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Seznam doporučené literatury
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Přílohy volně vložené
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Přílohy vázané v práci
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Převzato z knihovny
Ne
Plný text práce
Přílohy
Posudek(y) oponenta
Hodnocení vedoucího
Záznam průběhu obhajoby
Zápis o obhajobě disertační práce Mgr. Tarek Aysha Syntéza, absorpční a fluorescenční spektra nových kolorantů na bázi pyrrolinonových esterů
14.11.2011 12:00 učebna 02031
Přítomni - viz Prezenční listina obhajoby celkem 7 členů komise
Průběh obhajoby:
prof. Hanika 12:00: představení komise obhajoby a představení Mgr. Tarek Aysha
prof. Hanika 12:15 posudek školitele Mgr. Tarek Aysha
prof. Hanika 12:30 posudek vedoucího pracoviště ÚOCHT závěr: Mgr. Tarek Aysha splnil požadavky na podání disertační práce (dále jen DP) - práce byla doporučena k obhajobě.
Mgr. Tarek Aysha 12:45-13:15 prezentace výsledků DP.
Posudky oponentů:
prof. Hanika : posudek spolu s komentářem, komentář posudku Mgr. Aysha a odpovězení otázek oponenta z posudku DP. Na základě toho práce doporučena k obhajobě.
prof. Nepraš: posudek spolu s komentářem, komentář posudku Mgr. Aysha a odpovězení otázek oponenta z posudku DP. Na základě toho práce doporučena k obhajobě.
Diskuze k DP:
prof. Nepraš Otázka: Jakým způsobem byly identifikovány vybrané deriváty. Odpověď Ayshy: NMR,MS, elementární analýza + vysvětlení spekter.
prof. Hrdina: Vztah mezi strukturou a absorpčním spektrem připravených derivátů.
doc. Burget: Vliv substituce a arozpouštědla na absorpčním spektrum.
Ing. Halama: Syntéza pyrrolinonových esterů.
Souvislost mezi publikacemi a DP:
Výsledky dosažené v disertační práci byly publikovány v impaktovaných časopisech.
Podíl studenta na jednotlivých publikacích:
Podíl disertanta na překládaných publikacích byl významný a rozhodující.
Zapsal Ing. Oldřich Machalický, Dr.