1
98
Can. J. Chem. Vol. 81, 2003
Table 1. Reduction of nitroarenes with Raney nickel alloy with NH Cl in water.
4
Entry
Substrate
Time (h)
Products
Isolated yield (%)a
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
PhNO2
2.1
1.5
1.5
1.5
1.5
2
2.1
2.1
2
2
2
2.1
3
3
PhNH2
92
95
96
96
90
92
86
91
91
90
2-CH -C H -NO
2-CH -C H -NH
3
6
4
2
2
3
6
4
2
2
4-CH -C H -NO
4-CH -C H -NH
3 6 4
4-Isopropyl-C H -NH
6 4 2
4-Isobutyl-C H -NH
6 4 2
3-NH -C H -NH
2 6 4 2
2-CH -4-NH -C H -NH
3 2 6 3 2
2-CH CONH-C H -NH
3 6 4 2
2-OH-C H -NH
6 4
4-OH-C H -NH
6 4
3
6
4
4-Isopropyl-C H -NO
4-Isobutyl-C H -NO
6
4
2
6
4
2
3-NH -C H -NO
2
6
4
2
2-CH -4-NH -C H -NO
3
2
6
3
2
2-CH CONH-C H -NO
3
6
4
2
2-OH-C H -NO
4-OH-C H -NO
6
4
2
2
2
2
0
1
2
3
4
5
6
4
b
2-Cl-C H -NO
2-Cl-C H -NH
2
80 (20)
6
4
2
6
4
2-CH -4-Cl-C H -NO
2-CH -4-Cl-C H -NH
2
80
60
66
57
3
6
3
2
3
6
3
3-EtO C-C H -NO
3-EtO C-C H -NH
2 6 4 2
3-CHO-C H -NH
6 4 2
3-NH CO-C H -NH
2 6 4 2
2
6
4
2
3-CHO-C H -NO
6
4
2
3-NH CO-C H -NO
3
2
6
4
2
a
All product anilines are known compounds and characterized by comparing with the authentic sample.
Dehaloganated product (20%) was formed.
b
tions were carried out by refluxing a mixture of substrate,
Raney nickel alloy, and ammonium chloride in water. There
was no vigorous reaction, nor foaming, and also no vigorous
evolution of hydrogen gas and the pH of the medium was
neutral. The method is very simple to adopt in the labora-
tory. However, it has low chemoselectivity towards alde-
hydes, esters, amides, and halogenated nitroarenes (Table 1,
entries 11–15). This lack of chemoselectivity is very similar
to that of Raney nickel alloy in an alkali system.
In conclusion, we have demonstrated a mild user-friendly
method for reduction of nitroarenes to aminoarenes that can
be used for laboratory synthesis. The method is valuable be-
cause of its simplicity.
3. (a) A.M. Tafesh and J. Weiguny. Chem. Rev. 96, 2035 (1996);
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(
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Acknowledgments
KB thanks the University Grants Commission of India
UGC) for the Senior Research Fellowship.
(
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