Title
Synthesis, structure and solvatochromism of new 5-(4-substituted phenylazo)-4-(4-substituted phenyl)-6-hydroxy-3-cyano-2-pyridones
Creator
Alimmari, Adel S.
Copyright date
2012
Object Links
Select license
Autorstvo 3.0 Srbija (CC BY 3.0)
License description
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Language
English
Cobiss-ID
Theses Type
Doktorska disertacija
description
Datum odbrane: 19.06.2013.
Other responsibilities
mentor
Ušćumlić, Gordana, 1951-
član komisije
Mijin, Dušan
član komisije
Valentić, Nataša, 1967-
član komisije
Vitnik, Vesna
Academic Expertise
Tehničko-tehnološke nauke
University
Univerzitet u Beogradu
Faculty
Tehnološko-metalurški fakultet
Alternative title
Sinteza, struktura i solvatohromizam novih 5-(4-supstituisanih fenilazo)-4-(4-supstituisanih fenil)-6-hidroksi-3-cijano-2-piridona
Publisher
[A. Alimmari]
Format
PDF/A (143 lista)
description
Chemistry - Organic Chemistry / Hemija - Organska hemija
Abstract (en)
Three series of some novel arylazo pyridone dyes, 5-arylazo-6-hydroxy-4-phenyl-
3-cyano-2-pyridone dyes, 5-arylazo-6-hydroxy-4-(4-metoxyphenyl)-3-cyano-2-pyridone
dyes and 5-arylazo-6-hydroxy-4-(4-nitrophenyl)-3-cyano-2-pyridone dyes have been
synthetized. The structure of the dyes was confirmed by UV-Vis, FTIR, 1H NMR and
13C NMR spectroscopy and elemental analysis. The solvatochromic behavior of the dyes
was evaluated with respect to their visible absorption properties in various solvents. The
azo-hydrazone tautomeric equilibration was found to depend on the substituents as well
as on the solvent. These dyes exist in the hydrazone form in the solid state and in solvent
DMSO-d6 and there was an equilibrium between hydrazone form and azo form in the
different solvents.
The Kamlet-Taft and Catalan parameters were used for describing the solutesolvent
interactions and solvatochromic shifts of the visible absorption band. It was found
that the solute dipolarity / polarizability (especially polarizability by Catalan equation)
play an important role in the description of the pronounced solvatochromism in the
studied solutions.
The Catalan solvent scales were found to be more suitable for describing the
solvatochromic shifts.
The geometry data of the investigated dyes were obtained using DFT quantumchemical
calculations. The obtained calculational results are in very good agreement with
the experimental data
Abstract (sr)
U okviru proučavanja strukture i karakteristika azo piridonskih boja, u čvrstom
stanju i u rastvoru, su sintetisane tri nove serije arilazo piridonskih boja koje do sada nisu
poznate u literaturi: 5-arilazo-6-hidroksi-4-fenil-6-cijano-2-piridonske boje, 5-arilazo-6-
hidroksi-4-(4-metoksifenil)-6-cijano-2-piridonske boje i 5-arilazo-6-hidroksi-4-(4-
nitrofenil)-6-cijano-2-piridonske boje. Sve azo boje su sintetisane diazotovanjem
odgovarajućih 4-supstituisanih anilina i kuplovanjem dobijenih diazo soli sa
odgovarajućim piridonima, prethodno dobijenim iz odgovarajućih etil-4-supstituisanih
benzoilacetata i cijanoacetamida. Struktura sintetisanih azo boja je potrvđena na osnovu
podataka iz UV-vis, FTIR, 1H NMR i 13C NMR spektara. Solvatohromna svojstva su
određena u odnosu na njihovu apsorpciju u vidljivom delu UV-Vis spektra u različitim
rastvaračima. Efekti polarnosti rastvarača, proton-donorske i proton-akceptorske
karakteristike interakcije rastvarač-rastvorena supstanca su kvantitativno procenjene
Kamlet-Taft-ovim i Catalan-ovim solvatohromnim modelima. Proučavanje uticaja
supstituenata na arilazo komponenti na azo-hidrazon tautomeriju sintetisanih boja
izvršeno je korelacijom UV-Vis apsorpcionih frekvenci Hammett-ovom jednačinom.
Azo boje sintetizovane u ovoj disertaciji mogu postojati u azo i hidrazon
tautomernim oblicima. Na azo-hidrazon ravnotežu veliki uticaj imaju rastvarači i
supstituenti prisutni u arilazo komponenti. Rezultati ostvareni u ovom radu ukazuju na
dominantan hidrazonski tautomerni oblik, kako u čvrstom stanju tako i u rastvorima azo
boja u ratsvaračima različitih svojstava. Hidrazonska struktura proučavanih azo boja je
potvrđena kvantno-hemijskim izračunavanjima korištenjem DFT/B3LYP metode.
Authors Key words
Arylazo pyridone dyes, Tautomerism, Solvent Effects, Substituent Effects,
Solvatochromism
Authors Key words
Arilazo piridonske boje, Tautomerija, Uticaj rastvarača, Uticaj
supstituenata, Solvatohromizam
Classification
667
Subject
Azo boje
Type
Tekst
Abstract (en)
Three series of some novel arylazo pyridone dyes, 5-arylazo-6-hydroxy-4-phenyl-
3-cyano-2-pyridone dyes, 5-arylazo-6-hydroxy-4-(4-metoxyphenyl)-3-cyano-2-pyridone
dyes and 5-arylazo-6-hydroxy-4-(4-nitrophenyl)-3-cyano-2-pyridone dyes have been
synthetized. The structure of the dyes was confirmed by UV-Vis, FTIR, 1H NMR and
13C NMR spectroscopy and elemental analysis. The solvatochromic behavior of the dyes
was evaluated with respect to their visible absorption properties in various solvents. The
azo-hydrazone tautomeric equilibration was found to depend on the substituents as well
as on the solvent. These dyes exist in the hydrazone form in the solid state and in solvent
DMSO-d6 and there was an equilibrium between hydrazone form and azo form in the
different solvents.
The Kamlet-Taft and Catalan parameters were used for describing the solutesolvent
interactions and solvatochromic shifts of the visible absorption band. It was found
that the solute dipolarity / polarizability (especially polarizability by Catalan equation)
play an important role in the description of the pronounced solvatochromism in the
studied solutions.
The Catalan solvent scales were found to be more suitable for describing the
solvatochromic shifts.
The geometry data of the investigated dyes were obtained using DFT quantumchemical
calculations. The obtained calculational results are in very good agreement with
the experimental data
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