4th EucheMs chemistry congress

Poster Session 2
s1300
chem. Listy 106, s257–s1425 (2012)
Poster session 2 - organic chemistry
P - 0 8 7 4
SyntheSiS of noveL ene-yne CoMPoundS
derived froM SeLeniuM heteroCyCLeS
B. hoLzer 1 , d. LuMPi 1 , e. horKeL 1 , C. hAMetner 1 ,
J. frÖhLiCh 1
1 Technische Universität Wien, IAS, Vienna, Austria
Organoselenium compounds have become attractive
synthetic targets in material synthesis, ligand chemistry and
biologically relevant processes. Among organoselenium
compounds, selenophene derivatives are widely studied because
of their potential application in organic electronics. [1] Despite
structural similarities, however, sulfur and selenium compounds
are often strikingly different with respect to their stability,
properties, and ease of formation.
The topic of this contribution will be the presentation of
organoselenium-based functional organic materials. On the one
hand the structural focus will be on novel annealed selenophene
scaffolds; on the other hand an investigation of selenophene ringopening
moieties towards ene-yne compounds will be presented.
Based on various 2-bromoselenophene derivatives, bearing
different substituents (H, alkyl, aryl) in α- respectively β-position,
the Halogen-Dance (HD) reaction [2] proves to be a versatile
synthetic route to multisubstituted selenophenes. Subsequent
controlled selenophene ring fragmentation reaction selectively
leads to the Z-isomer of ene-yne compounds. Further modification
by microwave-assisted Cu-catalyzed Huisgen cycloaddition [3, 4]
affords the corresponding triazoles as 1,4-adducts. The
applicability of these triazoles in organic electronics
references:
will be discussed.
1. Patra, A., Bendikov, M., J. Mater. Chem., 2010, 20, 422–433.
2. Fröhlich, J., Prog. Heterocycl. Chem., 1994, 6, 1-35.
3. Tornoe, C. W., Christensen, C., Meldal, M., J. Org. Chem.,
2002, 67, 3057.
4. Rostovtsev, V. V., Green, L. G., Fokin, V. V., Sharpless, K. B.,
Angew. Chem., Int. Ed., 2002, 41, 2596.
Keywords: Organic Electronics; Selenophene; Selenophene
Ring Fragmentation; Halogen Dance Reaction; Huisgen
cycloaddition;
4 th EucheMs chemistry congress
P - 0 8 7 5
direCt CouPLinG of Cox with ePoxideS:
CAtALytiC ProduCtion of BiodeGrAdABLe
PoLyMerS
z. hoStALeK 1 , J. MernA 1
1 Institute of Chemical Technology in Prague, Department of
Polymers, Prague 6, Czech Republic
The development of catalysts for activation and use of
carbon oxides (CO and CO ) as a feed-stock for synthesis of new
2
materials is an attractive research target in last 20 years. One of
the most promising strategies of carbon oxides utilization is direct
coupling/copolymerization of CO and CO with epoxides.
2
Depending on catalytic system (catalyst/cocatalyst ratio) and
experimental conditions either cyclic esters/carbonates or
polymers susceptible towards biological or hydrolytical
degradation can be obtained.
The aim of this work is to develop effective catalytic system
for direct conversion of carbon monoxide and carbon dioxide and
epoxides to biodegradable polymers or to their cyclic esters
precursors, which can be easily polymerized via metal-catalyzed
ring-opening polymerization. For this purpose chromium and
cobalt SALEN complexes were synthesized and tested as catalysts
for direct high-pressure epoxide/CO copolymerization. The effect
2
of cocatalyst and experimental conditions (temperature, pressure
of CO and epoxide/catalyst/cocatalyst ratio) was also
x
investigated. Similar catalytic complexes (combination of SALEN
complexes with Co(CO) salt) were also tested for direct coupling
4
of epoxides with CO.
Keywords: Polymerization; Chromium; Cobalt;
Carbonylation; Carbon dioxide fixation;
AUGUst 26–30, 2012, PrAGUE, cZEcH rEPUbLIc