A simple and convenient method for the reduction of nitroarenes

Article abstract of DOI:10.1081/SCC-120006470

A variety of nitroarenes such as simple, electron rich and electron poor were reduced on A1₂O₃ support in presence of sodium hydrogen sulphide under microwave condition to give the corresponding aromatic amines in high yields. It is found that the substituents at different positions on nitrobenzene have no influence except 2d on the rate of reaction and yields of product.

Full text of DOI:10.1081/SCC-120006470

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A SIMPLE AND CONVENIENT METHOD FOR THE
REDUCTION OF NITROARENES*
a
a
a
a
a
S. Ravi Kanth , G. Venkat Reddy , V. V. V. N. S. Rama Rao , D. Maitraie , B. Narsaiah
&
b
P. Shanthan Rao
a
Organic Chemistry Division-II, Indian Institute of Chemical Technology, Hyderabad, 500 007,
India
b
Organic Chemistry Division-II, Indian Institute of Chemical Technology, Hyderabad, 500 007,
India
Version of record first published: 18 Oct 2011.
To cite this article: S. Ravi Kanth , G. Venkat Reddy , V. V. V. N. S. Rama Rao , D. Maitraie , B. Narsaiah & P. Shanthan
Rao (2002): A SIMPLE AND CONVENIENT METHOD FOR THE REDUCTION OF NITROARENES*, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:18, 2849-2853
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 18, pp. 2849–2853, 2002
A SIMPLE AND CONVENIENT METHOD
FOR THE REDUCTION OF
NITROARENES*
S. Ravi Kanth, G. Venkat Reddy,
V. V. V. N. S. Rama Rao, D. Maitraie,
y
B. Narsaiah, and P. Shanthan Rao
Organic Chemistry Division-II, Indian Institute of
Chemical Technology, Hyderabad 500 007, India
ABSTRACT
Avariety of nitroarenes such as simple, electron rich and
electron poor were reduced on Al O support in presence of
2
3
sodium hydrogen sulphide under microwave condition to give
the corresponding aromatic amines in high yields. It is found
that the substituents at different positions on nitrobenzene
have no influence except 2d on the rate of reaction and
yields of product.
In general the aromatic amines are considered to be important inter-
mediates in the synthesis of a number of nitrogen heterocycles. Some of
[
1]
[2]
[3]
[4]
them are used in dyes, drugs, pharmaceuticals, pesticides and so on.
The synthesis of these compounds is mainly from nitroarenes by way of
*
IICT Communication No: 4843.
Corresponding author. E-mail: shanthan@123india.com
y
2
849
DOI: 10.1081/SCC-120006470
Copyright & 2002 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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2
850
RAVI KANTH ET AL.
reduction, however a few examples are from other precursors. Earlier
[
methods on the reduction of nitro compounds using sodium sulphide,
5]
[
hydrogen sulphide on Fe O /Al O , sodium hydrogen sulphide, phase
6]
[7]
2
3
2
3
[8]
[9]
[10]
transfer catalyst, heterogenous catalyst, Mg salts have been reported.
However all the methods are of specific in nature. The development of an
efficient and universally applicable method for the synthesis of aromatic
amines is of current interest. We wish to report here for the first time a
simple and convenient method for the reduction of variety of aromatic
amines.
[
11]
In continuation of our interest
on the development of new and
efficient methodology for important products, we have further developed
that in a typical experiment, the nitrobenzene was reduced on alumina
support in presence of sodium hydrogen sulphide under microwave irra-
[
12]
diation conditions and obtained aniline. It is learned from literature
that the reduction of nitrobenzene with sodium hydrogen sulphide results
in phenyl hydroxylamine and further reduction to aniline. The initial
reduction to phenyl hydroxylamine seems to be faster than followed reac-
tion. In order to see the effect of substituent on the rate of reaction,
a number of substituted nitrobenzenes have been chosen for study. Thus
the method was applied to the reduction of substituted nitrobenzenes
having electron donating groups (CH , NH , OH) and electron withdraw-
3
2
ing groups (CHO, Cl, F, CF ) to result in the corresponding anilines. We
3
found that the substituents have no effect except 2d on the rate of reaction
and yields of product. In addition, the developed method has advantage of
shorter reaction times, with high yields and neat isolation of products.
Alternately the same reaction in case of 2b and 2e were carried out in
thermal conditions for 10 h and yields were found to be low. The products
1
have been characterized based on their IR, H NMR and mass spectra and
comparing with the data available in literature. The reaction has been
formulated in the Scheme 1 below.
Scheme 1.

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REDUCTION OF NITROARENES
Table 1.
2851
ꢀ
M.P.( C)
Compound
No
Reaction Time Yield
(%)
1
2
Entry
R R
R
(min)
Rec. Lit.
1
2
3
4
5
6
7
8
2a
2b
2c
2d
2e
2f
H H
H H
H H
H H
H H
H Cl
H Cl
H
CH
NH2
OH
CHO
Cl
4
4
4
2
4
4
4
4
95
90
–
43–45
–
44–46
[
13]
3
[
[
14]
95 138–140 141–143
70 192–194 190–192
85
80
75
90
15]
[
[
[
16]
17]
18]
76–78
66–68
46–48
–
74–75
68–70
45–47
–
2g
2h
F
3
Cl H H(R ¼ CF
3
)
The number of products synthesized have been tabulated in Table 1.
EXPERIMENTAL
Melting points were determined in open glass capillaries on a Fisher-
Johns melting point apparatus and are uncorrected. IR spectra were recorded
on FT-IR Schimadzu Perkin–Elmer 1310 infrared spectrophotometer.
1
H NMR spectra were recorded on Varian Gemini (200 MHz) spectrometer
and TMS was used as internal standard. Mass spectra were recorded on a
VG-micromass 7070H instrument at 70 eV.
GENERAL PROCEDURE
(a) Preparation of the Reagent: Dissolved 0.01 moles of crystallised
sodium sulphide (Na S 9H O) in 10 mL of water and added 0.01 moles of
2
2
finely powdered NaHCO in small portions with constant stirring. When the
3
carbonate has dissolved completely, added 10 mL methanol and cooled
ꢀ
below 20 C. Filtered off the precipitated sodium carbonate using Buchner
filter, washed the precipitate with methanol. The resulted filtrate was
adsorbed on alumina and dried.
(
b) Reaction Procedure: Dissolved 0.004 moles of nitro compound in
ether and adsorbed on the above prepared reagent and after drying sub-
jected to microwave irradiation (600 W, BPL BMO 700T) for 2–4 min. Then
it is cooled to room temperature and purified through a silica gel column.
The product aniline is eluted with 50% hexane–chloroform.

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852
RAVI KANTH ET AL.
ACKNOWLEDGMENT
Authors are thankful to Dr. K. V. Raghavan, Director, IICT,
Hyderabad for constant encouragement. SRK, GVR, VVNS, and DM are
thankful to CSIR and IICT for financial support in the form of Junior
Research Fellowship.
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REDUCTION OF NITROARENES
2853
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Received in the UK July 12, 2001