Communication
ChemComm
addition of water, N-phenyl hydroxylamine 3g was further
converted into aniline 2g. It is to be noted that no self-
condensation products (e.g. azoxy-, azo- or hydrazo-benzene)
were detected under our reaction conditions.
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Although the exact effect of the solvents on the RuCNT-mediated
selective reduction is not fully understood yet, one can hypothesize
that specific solvents could affect the adsorbed state of the
substrates, hydrogen concentration, and surface concentration
of the reactants. Water can also lower the activation energy of
50, 10871; For a recent review on platinum-based systems, see; (d) P. Lara
and K. Philippot, Catal. Sci. Technol., 2014, 4, 2445.
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the catalytic process, leading to full reduction of the nitro
group. It is however difficult to establish which of these factors
predominantly contributes to the observed selectivity.
9
In summary, a new heterogeneous catalyst was assembled by 10 D. Cantillo, M. Baghbanzadeh and C. O. Kappe, Angew. Chem., Int.
2
0
Ed., 2012, 51, 10190.
stabilization of ruthenium nanoparticles on carbon nanotubes.
The nanohybrid was used for the catalytic hydrogenation of
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1 X. Gu, Z. Sun, S. Wu, W. Qi, H. Wang, X. Xu and D. Su, Chem.
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various nitroarenes in the presence of hydrazine monohydrate, 12 S. K. Singh and Q. Xu, Catal. Sci. Technol., 2013, 3, 1889.
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3 (a) J. John, E. Gravel, A. Hag `e ge, H. Li, T. Gacoin and E. Doris,
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at room temperature. The system proved very efficient on all the
investigated substrates and demonstrated complete selectivity
towards the nitro group. Another interesting feature is that the
reported catalyst can selectively convert nitroarenes either into
the corresponding anilines or N-aryl hydroxylamines, depending
on the solvent. Both processes are operative under mild condi-
tions and provide excellent yields of the desired products.
Support from the Indo-French Centre for the Promotion of
Advanced Research (IFCPAR)/Centre Franco-Indien pour la
Promotion de la Recherche Avanc ´e e (CEFIPRA) is gratefully
acknowledged (Project no. 4705-1). The TEM-team platform
2013, 5, 3571; (d) D. V. Jawale, E. Gravel, V. Geertsen, H. Li, N. Shah,
R. Kumar, J. John, I. N. N. Namboothiri and E. Doris, Tetrahedron,
2014, 70, 6140; (e) N. Shah, E. Gravel, D. V. Jawale, E. Doris and
I. N. N. Namboothiri, ChemCatChem, 2014, 6, 2201; ( f ) D. V. Jawale,
E. Gravel, V. Geertsen, H. Li, N. Shah, I. N. N. Namboothiri and
E. Doris, ChemCatChem, 2014, 6, 719; (g) N. Shah, E. Gravel,
D. V. Jawale, E. Doris and I. N. N. Namboothiri, ChemCatChem,
DOI: 10.1002/cctc.201402782.
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(CEA, iBiTec-S) is acknowledged for help with TEM images.
The ‘‘Service de Chimie Bioorganique et de Marquage’’ belongs
to the Laboratory of Excellence in Research on Medication and
Innovative Therapeutics (ANR-10-LABX-0033-LERMIT).
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Notes and references
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H.-U. Blaser, H. Steiner and M. Studer, ChemCatChem, 2009, 1, 210.
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Chem. Soc., 1919, 41, 276. For a modified NH
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Cl-free protocol, see:
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J. A. Zeitler and D. W. Rooney, J. Catal., 2012, 289, 30.
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(a) K. Yanada, H. Yamaguchi, H. Meguri and S. Uchida, J. Chem. 20 For a recent review on CNT-supported catalysts, see: J. John, E. Gravel,
Soc., Chem. Commun., 1986, 1655; (b) P. Ren, T. Dong and S. Wu,
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Chem. Commun.
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