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Hydrogenation using iron oxide–based nanocatalysts for the synthesis of amines

Nature Protocols volume 10, pages 548–557 (2015)Cite this article

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Abstract

In this protocol, we describe the preparation of nanoscale iron oxide–based materials and their use in the catalysis of different hydrogenation reactions. Pyrolysis of a Fe(OAc)2-phenanthroline complex on carbon at 800 °C under argon atmosphere results in the formation of nanoscale Fe2O3 particles surrounded by nitrogen-doped graphene layers. By applying these catalysts, the hydrogenation of structurally diverse and functionalized nitroarenes to anilines proceeds with excellent selectivity. Furthermore, we have shown that one-pot reductive amination of carbonyl compounds with nitroarenes is also possible in the presence of these iron oxide catalysts. We report herein the synthesis of more than 40 amines, which are important feedstocks and key intermediates for pharmaceuticals, agrochemicals and polymers. The detailed preparation of the catalysts and the procedures for the hydrogenation processes are presented. The overall time required for the catalyst preparation and for the hydrogenation reactions are 35 h and 20–35 h, respectively.

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Figure 1
Figure 2: Fe2O3/NGr@C-catalyzed hydrogenation of functionalized nitroarenes and heterocyclic nitro compounds.
Figure 3: Recycling of the catalyst for the hydrogenation of nitrobenzene.
Figure 4: Fe2O3/NGr@C-catalyzed hydrogenation of nitroarenes in gram scales.
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Acknowledgements

The German Federal Ministry of Education and Research (BMBF) and the State of Mecklenburg-Vorpommern are gratefully acknowledged for their general support. We are grateful to A. Brückner, J. Radnik and M.-M. Pohl for the characterization of catalysts. We thank the analytical department of Leibniz-Institute for Catalysis, for their excellent service.

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Author notes

  1. Rajenahally V Jagadeesh and Tobias Stemmler: These authors contributed equally to this work.

Authors and Affiliations

  1. Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Rostock, Germany

    Rajenahally V Jagadeesh, Tobias Stemmler, Annette-Enrica Surkus, Henrik Junge, Kathrin Junge & Matthias Beller

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  1. Rajenahally V Jagadeesh
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  2. Tobias Stemmler
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Contributions

R.V.J., T.S. and M.B. planned the project and wrote the paper. R.V.J. and T.S. developed and prepared the catalysts. A.-E.S., H.J., K.J. and M.B. were involved in the development of this class of catalysts.

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Correspondence to Matthias Beller.

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The authors declare no competing financial interests.

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Jagadeesh, R., Stemmler, T., Surkus, AE. et al. Hydrogenation using iron oxide–based nanocatalysts for the synthesis of amines. Nat Protoc 10, 548–557 (2015). https://doi.org/10.1038/nprot.2015.025

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  1. Bronwen Dekker

    Editors note: The author has noticed that on page 548 the term Fe2O3 shell should be replaced by Fe2O3 core

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