10.1002/cssc.201900498
ChemSusChem
COMMUNICATION
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In conclusion, a novel earth-abundant catalyst permits the first
direct synthesis of 1H-perimidines from 1,8-dinitronaphthalene
and various benzylic and aliphatic aldehydes. The catalyst is easy
to synthesize by wet impregnation of commercially available
charcoal with a specific cobalt salen complex, which is crucial for
a high catalytic activity. Our methodology permits tolerance
towards a variety of functional groups, including hydrogenation-
sensitive examples (aryl iodides, nitriles, as well as C-C double
and triple bonds). We synthesized six new 1H-perimidine
derivatives and could use a technical grade dinitro derivative
without purification. An up-scaling of the reaction proceeds
smoothly and the catalyst shows stability over several
consecutive runs without any remarkable decrease in catalytic
activity. A number of challenges are associated with our novel
synthesis. The key seems to be that our catalyst can selectively
and consecutively hydrogenate dinitroarenes. The aldehyde must
remain unaffected, even at the higher temperatures, needed for
the condensation step. In addition, formation of the diaminoarene,
as well as the hydrogenation of the 1H-perimidine have to be
avoided. We think that our novel reaction represents an
interesting alternative to the known literature procedures using
“over-hydrogenated” 1,8-diaminonaphthalene.[18]
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Experimental Section
Catalyst synthesis: To
a mixture of 89 mg (M =
439.38 g mol-1,
0.203 mmol) complex I and 3 mL acetonitrile, 300 mg activated charcoal
were added and the suspension was stirred at 95 °C. After evaporation of
the solvent, the sample was pyrolyzed under nitrogen atmosphere at
700 °C followed by reduction at 550 ° (N2/H2, 90/10).
Synthesis of 1-H perimidines – general procedure: A 10 mL reaction vial
was charged with a magnetic stirring bar, 1.5 mmol 1,8-dinitronaphthalene,
1.1 eq. aldehyde, 3 ml toluene and 120 mg catalyst. The vial was placed
in a 300 mL high-pressure autoclave (Parr Instruments) and the autoclave
was flushed three times with 2.0 MPa hydrogen. Afterwards, the final
pressure was applied and the reaction was stirred at 130 °C for 20 h. After
completion of the reaction time, the autoclave was cooled to room
temperature and the hydrogen was released. Quantitative GC analysis
was accomplished using n-dodecane as an internal standard. For an
isolation of the products, the catalyst was removed using a magnet and
washed several times with acetone. The organic phases were combined
and the solvent was removed under reduced pressure. Purification was
accomplished by column chromatography applying pentane/ether as the
eluent. The products were analyzed by NMR spectroscopy. For new
compounds, elemental analysis was carried out.
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Acknowledgements
We thank Prof. Sven Hüttner for XPS analysis and the DFG
KESFB 840, B1 and KE-756/29-1 for financial support.
[9]
Keywords: cobalt • hydrogenation • nitroarene • perimidines
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