FeS-NH4Cl-CH3OH-H2O: An efficient and inexpensive system for reduction of nitroarenes to anilines

Article abstract of DOI:10.1081/SCC-100104012

Nitroarenes are reduced to corresponding anilines with FeS-NH₄Cl-CH₃OH-H₂O system in good yields.

Full text of DOI:10.1081/SCC-100104012

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FeS-NH4CL-CH3OH-H2O: AN
EFFICIENT AND INEXPENSIVE
SYSTEM FOR REDUCTION OF
NITROARENES TO ANILINES*
D. G. Desai a , S. S. Swami a , S. K. Dabhade a & M.
G. Ghagare a
a Chemistry Department, Rayat's A. S. C. College,
Sadhana Campus, Hadapsar, Pune, 411 028, India
Published online: 09 Nov 2006.
To cite this article: D. G. Desai , S. S. Swami , S. K. Dabhade & M. G. Ghagare
(2001) FeS-NH4CL-CH3OH-H2O: AN EFFICIENT AND INEXPENSIVE SYSTEM FOR
REDUCTION OF NITROARENES TO ANILINES* , Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry,
31:8, 1249-1251, DOI: 10.1081/SCC-100104012
To link to this article: http://dx.doi.org/10.1081/SCC-100104012
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SYNTHETIC COMMUNICATIONS, 31(8), 1249–1251 (2001)
FeS-NH4Cl-CH3OH-H2O: AN
EFFICIENT AND INEXPENSIVE
SYSTEM FOR REDUCTION
OF NITROARENES TO ANILINES*
D. G. Desai,{ S. S. Swami,S. K. Dabhade,
and M. G. Ghagare
Chemistry Department, Rayat’s A. S. C. College,
Sadhana Campus, Hadapsar, Pune – 411 028, India
ABSTRACT
Nitroarenes are reduced to corresponding anilines with
FeS-NH4Cl-CH3OH-H2O system in good yields.
Although a number of reagents are available in the literature for
reduction of different functional groups, the development of mild, neutral,
and selective reducing systems still attracts a great deal of attention of
organic chemists. In recent years, reagents based on iron find wide applica-
tion in organic synthesis because of their ready availability, ease of handling,
and low cost. Reduction of nitroarenes to anilines is an important reaction
in organic chemistry. We report here the same using FeS-NH4Cl-CH3OH-
H2O system in good yields (Tab.).
Reduction of nitroarenes to anilines mediated by zinc has been
achieved by several systems1–4 such as Zn-HCl, Zn-NaOH, Zn-NH4Cl,
* Work carried out at R. B. N. B. College, Shrirampur – 413 709, India.
{ Corresponding author.
1249
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

1250
DESAI ET AL.
and Zn-CaCl2, but each has drawbacks. For example, Zn-HCl system is not
suitable for nitro compounds with acid-sensitive functionalities like amino
group, and it also produces hazardous chloronitro compounds. Zn-NH4Cl
system gives toxic phenyl hydroxylamines as major products. The other
systems, Zn-NaOH and Zn-CaCl2-H2O, require stringent reaction con-
ditions. Besides zinc-mediated reduction of aromatic nitro compounds, sev-
eral other systems have also been reported using different reagents:5–12
NaBH4; Sn-HCl; Fe-HCl; and catalytic reduction using Pt or Pd/C. The
low yields, costly chemicals, stringent reaction conditions, and tedious
work-up are the major drawbacks of the above systems. This prompted us
to apply FeS-NH4Cl - CH3OH-H2O system (Scheme) for reduction of
nitroarenes to anilines. The chemicals required for this system are easily
available, cheap, and nontoxic. The present system is mild, neutral, eco-
friendly, and a useful addition to the existing systems to convert nitroarenes
to anilines.
Scheme 1.
The following compounds were prepared in the laboratory (Table).
The progress of the reaction was monitered by TLC and products were
characterized by comparison with authentic samples,13 suitable derivati-
zation, and spectral analysis (IR and PMR). The reduction of polynitro-
arenes using the above system is in progress.
Table.
Reduction of Nitroanilines to Anilines
Time Yield M.p./[b.p.]
ꢀC
Entry Nitroarenes
Product
(h)
(%)
1.
2.
Nitrobenzene
p-Nitrotoluene
Aniline
p-Toludine
4
5
6
5
8
5
6
6
5
6
5
81
74
78
76
56
74
76
7264
77
75
80
[184]
44–45
50–51
3.
ꢀ-Nitronaphthalene
p-Nitrobenzoic acid
o-Nitrophenol
ꢀ-naphthylamine
p-Aminobenzoic acid
o-Aminophenol
p-Aminophenol
p-phenylene diamine
m-phenylene diamine
p-Chloroaniline
4.
186–187
173–174
185–186
142
5.
6.
p-Nitrophenol
p-Nitroaniline
7.
8.
m-Nitroaniline
p-Chloronitrobenzene
9.
69–70
57–58
108
10.
11.
N-Benzyl-m-nitro aniline N-Benzyl-m-phenylene diamine
Methyl-p-nitro benzoate Methyl-p-amino benzoate

NITROARENES TO ANILINES
1251
EXPERIMENTAL
General Procedure for Reduction
Nitrocompound (10 mmole) was dissolved in a mixture of methanol
(40 mL) and water (10 mL). To this commercial powdered iron sulphide
(50 mmole) and ammonium chloride (50 mmole) were added. It was refluxed
in a water bath (TLC monitering, see Table). When the reaction was over,
residue was filtered, washed with methanol (2 Â 5 mL), and basified by
adding a saturated solution of sodium carbonate. Solvent was removed by
distillation under reduced pressure, and residue was extracted with methy-
lene chloride (3 Â 30 mL). The combined organic layer was washed with
water (2 Â 25 mL) and dried over potassium hydroxide pellets. Removal
of solvent under reduced pressure furnished aminocompound, which was fur-
ther purified by distillation or crystallization from water or water–alcohol
mixture.
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Accepted July 7, 2000