The Béchamp reduction (or Béchamp process) is a chemical reaction that converts aromatic nitro compounds to their corresponding anilines using iron as the reductant:[1]
| Bechamp reduction | |
|---|---|
| Named after | Antoine Béchamp |
| Reaction type | Organic redox reaction |
| Identifiers | |
| RSC ontology ID | RXNO:0000498 |
- 4 C6H5NO2 + 9 Fe + 4 H2O → 4 C6H5NH2 + 3 Fe3O4
This reaction was once a major route to aniline, but catalytic hydrogenation is the preferred method.[2]
Reaction history and scope
editThe reaction was first used by Antoine Béchamp to reduce nitronaphthalene and nitrobenzene to naphthylamine and aniline, respectively.[3] The Béchamp reduction is broadly applicable to aromatic nitro compounds.[4][5] Aliphatic nitro compounds are however more difficult to reduce, often remaining as the hydroxylamine. Tertiary aliphatic nitro compounds, however, are converted in good yield to the amine using the Béchamp reduction.[6]
The reduction proceeds in a multistep manner. First, the nitro group is reduced to nitroso, which undergoes hydrogenation to a hydroxylamino group prior to further reduction to the amine.[7]
Laux process
editThe traditional Béchamp reduction cogenerates gray-black iron oxides. The Laux process is based on the finding that the oxide coproduct is strongly affected by various additives, such as ferrous chloride, aluminium chloride, and even simply sulfuric acid, which are added before heating the iron-nitrobenzene mixture. The innovations from Laux have shifted the emphasis of the Béchamp reduction for the manufacture of anilines to the production of valuable iron oxide pigments.[8] The method is still effective for reduction of nitroaromatics.[9]
Further reading
edit- Organic Reactions 2, 428 (1944)
References
edit- ^ .Kahl, Thomas; Schröder, Kai-Wilfrid; Lawrence, F. R.; Marshall, W. J.; Höke, Hartmut; Jäckh, Rudolf (2011). "Aniline". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a02_303.pub2. ISBN 978-3527306732.
- ^ McKetta, John J. (1989). "Nitrobenzene and Nitrotoluene". Encyclopedia of Chemical Processing and Design: Volume 31 - Natural Gas Liquids and Natural Gasoline to Offshore Process Piping: High Performance Alloys. CRC Press. pp. 166–167. ISBN 978-0-8247-2481-8.
- ^ Béchamp, Antoine (1854). "De l'action des protosels de fer sur la nitronaphtaline et la nitrobenzine. nouvelle méthode de formation des bases organiques artificielles de Zinin". Annales de chimie et de physique. 42: 186–196.
- ^ Bavin, G. David (1960). "2-Aminofluorene". Org. Synth. 40: 5. doi:10.15227/orgsyn.040.0005.
- ^ Mendenhall, P. M. G.; Smith, Peter A. S. (1966). "2-Nitrocarbazole". Org. Synth. 46: 85. doi:10.15227/orgsyn.046.0085.
- ^ M. J. Leonard; A. R. Lingham; J. O. Niere; N. R. C. Jackson; P. G. McKay; H. M. Hϋgel (6 Mar 2014). "Alternative synthesis of the anti-baldness compound RU58841" (PDF). RSC Advances. 4 (27): 14143–14148. Bibcode:2014RSCAd...414143L. doi:10.1039/c4ra00332b. Archived from the original (PDF) on 12 February 2023. Retrieved 29 April 2022.
- ^ Wang, Zerong (2010). "Béchamp Reduction". Comprehensive Organic Name Reactions and Reagents. pp. 284–287. doi:10.1002/9780470638859.conrr063. ISBN 9780470638859.
- ^ Buxbaum, Gunter; Printzen, Helmut; Mansmann, Manfred; Räde, Dieter; Trenczek, Gerhard; Wilhelm, Volker; Schwarz, Stefanie; Wienand, Henning; Adel, Jörg; Adrian, Gerhard; Brandt, Karl; Cork, William B.; Winkeler, Heinrich; Mayer, Wielfried; Schneider, Klaus (2009). "Pigments, Inorganic, 3. Colored Pigments". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.n20_n02. ISBN 978-3527306732.
- ^ Mahood, S. A.; Schaffner, P. V. L. (1931). "2,4-Diaminotoluene". Org. Synth. 11: 32. doi:10.15227/orgsyn.011.0032.