4th EucheMs chemistry congress

Poster Session 2
s1334
chem. Listy 106, s257–s1425 (2012)
Poster session 2 - organic chemistry
P - 0 9 4 3
APProACheS to the SyntheSiS of ACyCLiC And
MACroCyCLiC MuLtiurACiLS
A. niKoLAev 1 , v. SeMenov 1 , r. GiniyAtuLLin 1 ,
A. MiKhAyLov 1 , d. ShArAfutdinovA 1 , v. rezniK 1
1 A.E. Arbuzov Institute of Organic and Physical Chemistry,
Chemistry of Nucleotide Bases, Kazan, Russia
Earlier we’ve shown that pyrimidinophanes (macrocycles
containing pyrimidine units) do possess high biological activity,
comparable with that of reference drugs, and demonstrate a wide
spectrum of antimycobacterial activity. We suggested that a
compound, consisting of several “monomeric” pyrimidinophanes
linked together in some way, can demonstrate higher activity
and/or selectivity.
Herein we present the results of our investigations in the
area. We’ve developed several routes to nanosized structures
containing pyrimidinophanes. Among them we’ve chosen those
with the highest yield - we used paraformaldehyde to cross-link
the macrocycles containing 6-methyluracil. Another option is to
link macrocycles through the functional substitutents in either
uracil unit or at the heteroatom. Pyrimidinophanes containing
propynyl substituents were cross-linked using azide-alkyne
cycloaddition and coupling of acetylenes with copper acetate, in
some cases the reactions proceed quantitatively.
The same azide-alkyne cycloaddition was used to obtain
another type of oligomeric macrocyclic and acyclic pyrimidine
derivatives - dendrimers containing uracil units. Di- and
oligoazides (i.e. 1,4-diazidomethylbenzene, 1,3,5-triazidomethyl-
-2,4,6-triethylbenzene, 1,3-bis(5-azidopentyl)-6-methyluracil etc.)
were introduced in the reactions with 1,3-bis(w-bromoalkyl)-5-
-propynyl-6-methyluracil to obtain first generation dendrimers.
Subsequent substitution of bromine atoms for azide groups and
consecutive reiteration afforded higher generation dendrimers.
Such synthetic approach gives us the possibility to introduce
various groups and units into the dendrimer molecule by a simple
nucleophilic substitution of terminal bromine atoms, another
option for modification is again a “click” reaction of terminal
azide groups with a wide range of acetylenes, including
5-propynyluracils.
Alkylation of the dimers and oligomers provided the onium
salts which were tested towards a series of bacteria and fungi.
We’ve discovered that the earlier found regularities for the
monomers do not work for the dimers and higher molecular
weight oligomers.
Acknowledgement: Financial support of the Russian
Foundation for Basic Research (project #10-03-00365-a) and
the President’s grant for young Russian researchers (project
MK-5936.2012.3) is acknowledged.
Keywords: uracil; dendrimer; synthesis; pyrimidinophane;
oligomeric macrocycles;
4 th EucheMs chemistry congress
P - 0 9 4 4
the effeCtS of ProtiC SoLventS And
StruCture on the eLeCtroniC ABSorPtion
SPeCtrA of the iSoMeriC Pyridine
CArBoxyLiC ACidS
S. drMAniC 1 , J. niKoLiC 1 , B. JovAnoviC 2
1 Faculty of Technology and Metallurgy University of Belgrade
Karnegijeva 4 Belgrade Serbia, Organic Chemistry, Belgrade,
Serbia
2 2Institute of Chemistry Technology and Metallurgy University
of Belgrade, Organic Chemistry, Belgrade, Serbia
The ultraviolet absorption spectra of the carboxyl group of
three isomeric pyridine carboxylic acids (picolinic acid, nicotinic
acid and isonicotinic acid) were determined in a set of protic
solvents in the wavelength range from 200 to 400 nm. In order to
analyze the solvent effect on the obtained absorption maxima, the
ultraviolet absorption frequencies of the electronic transitions in the
carboxylic group of the examined acids were correlated using a total
solvatochromic equation of the form ν =v +sπ* + aα+ bβ, where
max 0
n is the absorption frequency (1/λ ), π* is a measure of the
max max
solvent polarity, β represents the scale of solvent hydrogen bond
acceptor basicities and α represents the scale of solvent hydrogen
bond donor acidities. The correlation of the spectroscopic data
was carried out by means of multiple linear regression analysis.
The solvent effects on the ultraviolet absorption maximums of the
examined acids were discussed.
Keywords: picolinic acid; nicotinic acid; isonicotinic acid;
ultraviolet absorption maximum; protic solvents;
AUGUst 26–30, 2012, PrAGUE, cZEcH rEPUbLIc