10.1002/ejoc.201800583
European Journal of Organic Chemistry
FULL PAPER
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Recycling of the Catalysts
The nanoparticle solution, the internal standard mesitylene (6.9 µL,
50 µmol, 1.0 equiv.) and ethyl 3-phenylpropiolate (8.3 µL, 50 µmol,
1.0 equiv.) were dissolved in DMF. The reaction mixture was stirred at
40 °C under H2 atmosphere (balloon) and monitored by GC analysis. Upon
completion of the reaction, the reaction mixture was transferred to a
Grainer tube. Diethyl ether (3.5 mL) and pentane (5 mL) were added and
the solution was centrifuged at 5300 revolutions per minute for 15 minutes.
The supernatant was decanted and the residue washed with pentane in a
subsequent centrifugation–washing cycle. The black residue was
redissolved in DMF (1.5 mL), added to a new reaction vessel equipped
with mesitylene (6.9 µL, 50 µmol, 1.0 equiv.) and ethyl 3-phenylpropiolate
(8.3 µL, 50 µmol, 1.0 equiv.), stirred at 40 °C under H2 atmosphere
(balloon) and monitored by GC analysis. This cycle was repeated until
reduced reaction rates were observed. Notably, parts of the catalysts are
steadily removed from the reaction mixture for GC-analysis and not
returned.
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Scale-up
The nanoparticle solution (3.2 mL, 1.1 µmol, 0.10 mol-%) and ethyl 3-
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1H-NMR (300 MHz, CDCl3, 300K): δ(ppm) = 7.62-7.52 (m, 2H, CHar), 7.40-
7.31 (m, 2H, CHar), 6.95 (d, J = 12.6 Hz, 1H, CH), 5.96 (d, J = 12.6 Hz, 1H,
CH), 4.18 (q, J = 7.1 Hz, 2H, CH2), 1.25 (t, J = 7.1 Hz, 3H, CH3). 13C-NMR
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129.8 (CH), 129.1 (CH), 128.1 (CH), 120.1 (CH), 60.4 (CH2), 14.2 (CH3).
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199.0729. IR (neat): 3029w, 2981w, 2938w, 1718s, 1631m, 1577w,
1495m, 1450w, 1424w, 1388w, 1258w, 1177s, 1163s, 1095w, 1028m,
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Acknowledgements
Sebastian Lamping (Organic Chemistry Institute, University of
Mꢀnster) is acknowledged for performing XPS measurements. Dr.
Uta Rodehorst and Dr. Richard Schmuch (Münster
Electrochemical Energy Technology Institute, University of
Mꢀnster) are acknowledged for performing the XRD
measurements. Joshua Fuchs is acknowledged for performing
the TXRF measurements. We thank the Deutsche
Forschungsgemeinschaft DFG (SFB858) for supporting our work.
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Keywords: Semihydrogenation • AuPd-nanoparticles •
Photochemistry• Catalysis • Nanoalloys
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