4th EucheMs chemistry congress

wednesday, 29-Aug 2012
s770
chem. Listy 106, s587–s1425 (2012)
organic Chemistry, Polymers – i
General synthetic methods – iV
o - 3 6 5
the SyntheSiS of GiAnt CALixAreneS
C. MArtini 1 , M. roLLet 2 , d. GiGMeS 2 , S. vieL 3 ,
B. LePoittevin 4 , v. huC 4
1 University Pierre and Marie Curie, Laboratoire de Chimie de
la Matiere Condensée, PARIS, France
2 Laboratoire Chimie Provence, Chimie Radicalaire Organique
et Polymeres de Spécialité, Marseille, France
3 Laboratoire Chimie Provence, Spectrométries Appliquées a la
Chimie Structurale, Marseille, France
4Universite Paris-Sud 11, Institut de Chimie Moléculaire et des
Matériaux d’Orsay, Orsay, France
Calixarenes are a versatile class of cyclic oligomers
successfully applied to ions recognition, for example, thanks to
their tunable cavity and their ability to be readily functionalized.
Their synthesis involves a reaction between formaldehyde and
positions ortho to the hydroxyl group of phenol derivatives under
basic or acidic catalysis. The ring shape of calixarenes is induced
by intramolecular H-bonding as oligomers grow. Among
calixarenes family, the most studied are those including 4 to 8
monomer units since they are easily accessible from standard
synthesis methods. Very few examples of larger calixarenes are
available in the literature and the larger one, synthesized in very
small amount, doesn’t exceed 20 units. We propose here the
synthesis of “giant calixarenes” with a size well above the current
state of art. These macrocycles are obtained easily in one step and
can be purified by simple selective precipitation processes. We
found that, depending mainly on the choice of para group and
catalyst, and on reaction time, calixarenes are able to reach
unsuspected size. In contrast with the classic synthesis of
macrocyclic polymers, needing a high dilution to prevent an
intermolecular linkage, the giant calixarenes are obtained using a
high concentration and produced in very large scale (above 50 g
in a 1L-flask). Furthermore, taking advantage of the chemical
versatility of calixarenes, we successfully performed the
functionalization of giant calixarenes lower rims with different
reactants. These new compounds represent a very promising
platform for the design and the production of functional
macrocyclic polymers, and will probably open new perspectives
in material science.
Keywords: Calixarenes; polymers; macrocycles;
General synthetic methods – iV
4 th EucheMs chemistry congress
o - 3 6 6
froM iMidAzoquinoLineS to
iMidAzoquinoLineS throuGh triCyCLiC
quinoLineS
v. MiLAtA 1 , J. SALon 1 , M. BeLLA 2
1 Slovak University of Technology FCHPT, Organic Chemistry
Catalysis and Petrochemistry, Bratislava, Slovak Republic
2 FCHPT STU and SAS, OCCP and IC, Bratislava,
Slovak Republic
2-Aminoimidazoquinoline, compounds with interesting
biological properties, was found, like similar pyrazinoquinolines,
in thermally treated meats (HCA, heterocyclic amines). [1, 2] The
synthetic strategy leading to them is based on closing the
quinoline or the azole/pyrazine ring.
Aminobenzimidazoles/triazoles/selenadiazoles/
/quinoxalines we prepared mainly from the corresponding
nitroderivatives. After reduction to corresponding amine and
applying the Gould-Jacobs protocol with activated enolethers
under S V conditions we obtained aminoethylene derivatives
N
– precursors of target compounds. Thermal cyclization of the
aminoethylenes gave exclusively the angularly annelated
azolo/pyrazinoquinolines, which could be converted to parent,
non-substituted heterocycles by following reactions: hydrolysis,
decarboxylation, chlorination/aromatization and dechlorination.
During reductive dechlorination of the 7-chloropyrido[2,3-
-f]quinoxaline we found that an unknown coupled ring contraction
of the fused pyrazine ring into a condensed imidazole ring takes
place. The ring transformation of condensed selenadiazole ring
gave us a tool to prepare various selectively alkylated tricyclic
heterocycles. Another approach afforded food borne carcinogen,
2-amino-3-methylimidazo[4,5-f]quinoline (IQ) obtained in total
20% yield using unique strategy.
Acknowledgements: The authors are grateful to the Slovak
Grant Agency for Science (contract No. 1/0660/11) and to
Slovak Research and Development Agency (contracts No.
APVV-0339-10 and APVV-0038-11) for the financial support.
references:
1. Milata V.: Tricyclic Azoloquinolines, Advances in
Heterocyclic Chemistry, ed. A. R. Katritzky, vol. 78,
189–268, Academic Press, San Diego, 2001.
2. Nagao, M.; Sugimura, T. Food Borne Carcinogens;
John Wiley & Sons: Chichester, 2000.
Keywords: imidazoquinoline; selediazoloquinoline;
pyrazinoquinoline; nucleophilic vinylic substitution;
Gould-Jacobs reaction;
AUGUst 26–30, 2012, PrAGUE, cZEcH rEPUbLIc