4th EucheMs chemistry congress

Poster Session 2
s1331
chem. Listy 106, s257–s1425 (2012)
Poster session 2 - organic chemistry
P - 0 9 3 7
nitroGen BridGed triAryLCArBeniuM SALtS
AS PLAtforMS for Anion reCoGnition
f. MiLdner 1 , P. reeh 1 , J. SChAtz 1
1 Friedrich-Alexander-University Erlangen-Nuremberg, Chemie
& Pharmazie, Erlangen, Germany
Anions play an important role in many biological and
biochemical processes. Therefore, their recognition and sensing
by artificial receptors is of great interest in the field of
supramolecular chemistry. Despite the special intrinsic properties
of anions, which hamper the design of efficient artificial hosts, a
lot of novel receptors were presented during the last years. [1–3]
Most of them consist of an aromatic platform and at least
one side chain containing hydrogen bond donating functionalities
such as urea and thiourea moieties. Previous results in our group
show that benzene or calixarenes as core molecules for anion
receptors are too small to host larger anions such as carboxylates.
Therefore, larger aromatic platforms are desirable. Furthermore,
the complexation can be improved by the introduction of charged
and/ or electron deficient (poly)aromatics. [4]
In our group these strategies were applied to design
receptors based on nitrogen bridged stable organic
triarylcarbenium ions for the recognition of different mono- and
dicarboxylates. All of them are accessible in a few steps from
tris(2,6-dimethoxyphenyl)carbeniumtetrafluoroborate by stepwise
reaction with particular amines. Their binding affinities to several
organic anions were studied by 1H-NMR titration experiments. [5]
references:
1. P. A. Gale, Chem. Soc. Rev. 2010, 39, 3746–3771.
2. A.-F. Li, J.-H. Wang, F. Wang, Y.-B. Jiang, Chem. Soc.
Rev. 2010, 39, 3729–3745.
3. C. Caltagirone, P. A. Gale, Chem. Soc. Rev. 2009, 38,
520–563.
4. M. Frank, Diplomarbeit,Universität Ulm 2001.
5. P. Reeh, Diplomarbeit, Universität Erlangen-Nürnberg
2008.
Keywords: Supramolecular chemistry; Receptors; Anions;
4 th EucheMs chemistry congress
P - 0 9 3 8
SyntheSiS And ChArACteriSAtion
of PyrAzoLidine By oxidAtion of
1,3-diAMinoProPAne
C. Miro SABAte 1 , A. J. BouGrine 1 , A. eL hAJJ 1 ,
h. deLALu 1
1 University of Lyon, Hydrazines and Polynitrogen Energetic
Compounds, Villeurbanne, France
This work presents a new method for the synthesis of
pyrazolidine (PYRZ), hydrazine used in the pharmaceutical and
cosmetic industries. The new method uses the Raschig process
via oxidation of the amine (1,3-diaminopropane) with sodium
hypochlorite. The advantages of this new protocol are: low
toxicity, low associated cost, high reaction rates, high selectivity
and high feasibility for a continuous transposition. A global
process was developed involving the characterization of the
reaction mechanisms, a kinetic study of all the reactions of
formation and degradation, the modelling and finally, the
optimization of the synthesis parameters. The synthesis part,
which is resting on a kinetic approach, was studied in two steps:
first, the identification of the products, their kinetic evolution
versus time and the knowledge of the associated mechanisms
(products were identified and quantified by UV, HPLC/MS and
GC/MS methods); secondly, a detailed study of all formation and
degradation rates of reactions in order to know the evolution of
the pyrazolidine concentrations as function of the initial reagent
concentrations, the pH and the temperature.
Keywords: hydrazine; Raschig process; Pyrazolidine; kinetics;
AUGUst 26–30, 2012, PrAGUE, cZEcH rEPUbLIc