Ammonium nickel sulphate mediated nitration of aromatic compounds with nitric acid

Article abstract of DOI:10.1081/SCC-100103545

Aromatic compounds were efficiently nitrated under mild conditions employing ammonium nickel sulphate and nitric acid as a reagent. This procedure works efficiently at room temperature yielding mononitro derivative in fair to good yield with high regioselectivity.

Full text of DOI:10.1081/SCC-100103545

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AMMONIUM NICKEL SULPHATE
MEDIATED NITRATION OF
AROMATIC COMPOUNDS WITH
NITRIC ACID
Tasneem a , M. M. Ali a , K. C. Rajanna b & P. K.
Saiparakash c
a Department of Chemistry, Anwarul Uloom
College, Nawab Shah AlamKhan Centre for Post
Graduate Studies & Research, New Mallepally,
Hyderabad, 500 001, India
b Post Graduate College, Osmania University,
Mirzapur, (SGD)-502 249, India
c Department of Chemistry, Osmania University,
Hyderabad, 500 007, India
Available online: 09 Nov 2006
To cite this article: Tasneem, M. M. Ali, K. C. Rajanna & P. K. Saiparakash (2001):
AMMONIUM NICKEL SULPHATE MEDIATED NITRATION OF AROMATIC COMPOUNDS
WITH NITRIC ACID, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 31:7, 1123-1127
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SYNTHETIC COMMUNICATIONS, 31(7), 1123–1127 (2001)
AMMONIUM NICKEL SULPHATE
MEDIATED NITRATION OF AROMATIC
COMPOUNDS WITH NITRIC ACID
Tasneem,1 M. M. Ali,1 K. C. Rajanna,2, and
*
P. K. Saiparakash3
1Department of Chemistry, Nawab Shah AlamKhan
Centre for Post Graduate Studies & Research,
Anwarul Uloom College, New Mallepally,
Hyderabad – 500 001, India
2Post Graduate College, Osmania University, Mirzapur
(SGD) – 502 249, India
3Department of Chemistry, Osmania University,
Hyderabad – 500 007, India
ABSTRACT
Aromaticocmpounds were effiicently nitrated under
mild conditions employing ammonium nickel sulphate and
nitric acid as a reagent. This procedure works efficiently at
room temperature yielding mononitro derivative in fair to
good yield with high regioselectivity.
Nitration of aromatioccmpounds is an important industrial
process.1–4 The nitroaromatic compounds so produced are widely utilized
for the synthesis of dyes, pharmaceuticals, perfumes, and plastics. Usually
the nitration of aromatic compounds is catalyzed by concentrated
* Corresponding author.
1123
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

1124
TASNEEM ET AL.
strong acids.5–9 Unfortunately, nitrations of aromatic compounds typically
require a mixture of concentrated fuming nitric acid with sulfuric acid,
leading to excessive acid waste. Alternatively, nitration of aromatic com-
pounds has been studied by various nitrating agents under different
conditions.10–15 Among these, most of the methods have some drawbacks,
such as regioselectivity, over-nitration, and competitive oxidation of
substrates.16–18 Therefore, there is still a need for the development of new
methods for the nitration of aromaticcompounds.
For a long time nitric acid has been used as such or with other reagents
19–21
for the nitration of aromaticcompounds.
Recently, we have reported
that ammonium molybdate and nitric acid can act as good catalysts for the
nitration of aromatic compounds under reflux conditions, giving the corre-
sponding nitro derivatives in good yields with high selectivity.22–24 The
results obtained in our earlier investigation prompted us to search for
more efficient and operationally simple catalysts. In view of this, it was
thought worthwhile to use a metal complex or salt in combination with
nitric acid for nitration of aromatic compounds with a hope (a) to increase
the rate and yield of the reactions; (b) to improve ortho/para ratio of
the nitrated aromatic compounds; and (c) to run the reactions under
nonaqueous conditions.
Ammonium nickel sulphate was selected as the most promising candi-
date for the proposed nitration reactions. Accordingly, a range of aromatic
compounds were treated with 1 equiv. of 69% nitric acid in chloroform at
room temperature in the presence of 1 equiv. of ammonium nickel sulfate
(Scheme). The results are shown in Table 1. Dinitrated products were
not observed in any case. In the case of benzene, nitration did not take
place even after 24 h under reflux. However, chlorobenzene underwent nitra-
tion smoothly, probably because of the presence of an activating chloro
group.
Scheme.
Nitration of aromatic compounds in the presence of ammonium nickel
sulfate proceeds rapidly, affording high yields (85–95%) of the correspond-
ing mononitro derivatives with high regioselectivity. In the absence of
catalyst, a sluggish reaction occurred and the yield of nitrated product
was less than 20%. Progress of the reaction is monitored by a visible

NITRATED AROMATIC COMPOUNDS
1125
Table 1. Nitration of Aromatic Compounds in the Presence of Ammonium Nickel
Sulfate (NH4)2SO4ÁNiSO4Á6H2O
Yield %
Reaction
Entry No.
Substrate
Phenol
o-aminophenol
p-chlorophenol
p-nitrophenol
p-cresol
Time/h
Para
Ortho
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
3
3
4
4
3
4
3
3
3
3
4
3
3
4
3
3
3
3
3
4
85
92
—
—
—
86
93
—
—
—
84
—
—
88
—
—
93
—
86
88
15
—
94
92
93
14
—
94
93
94
16
92
94
12
93
92
—
90
14
12
Acetanilide
o-chloroacetanilide
p-nitroacetanilide
p-chloroacetanilide
p-bromoacetanilide
Benzanilide
p-nitrobenzanilide
p-chlorobenzanilide
Aniline
p-nitroaniline
p-chloroaniline
o-ethylaniline
p-anisidine
Chlorobenzene
Toluene
change in the color of the reaction mixture and also from TLC during
the course of reaction. To check the generality of the reaction, it is
carried out with naphthalene, anthracene to give ꢀ-nitronaphthalene
(85%) and 9-nitro anthracene (95%), respectively, which proved to be
quite satisfactory. The regioselectivity was higher compared with those
observed for classical nitration.
To shed light on the reaction mechanism, further work is in progress.
However, based on the results obtained so far, it is believed that the reaction
occurred by nitronium ion-bound metal species, which is thought to be a key
intermediate. The nitrated products were characterized by comparison of
their spectral and physical data with authentic samples. The ratio of o- and
p-products was determined by HPLC and isolated by chromatography.
The foregoing results thus substantiate a new, mild, operationally
simple, and efficient method for the nitration of aromatic compounds
using ammonium nickel sulfate resulting in corresponding nitro derivatives

1126
TASNEEM ET AL.
in fair to good yield with high regioselectivity. Therefore, the present
method is believed to be a good method for the synthesis of nitro
compounds in organic synthesis.
EXPERIMENTAL
All chemicals and solvents were obtained from commercial sources
and used without further purification. 1H NMR were recorded are
90 MHz in CDCl3 solvent. IR spectra were obtained on G.C. FTIR using
a Vartan Nicolet USA apparatus. EI mass spectra were determined by using
_
a V.G. Micromass 7070 and Finnigan mal 1020 apparatus. Melting points
were determined on a Veego digital automaticmelting point apparatus and
are uncorrected.
Typical Procedure
The following procedure is
a representative reaction. Phenol
(0.094 mL, 1 mmol) and ammonium nickel sulfate (394 mg, 1 mmol) were
taken in chloroform (10 mL). Then 69% HNO3 (0.063 mL, 1 mmol) was
added and the reaction mixture was stirred at room temperature for 3 h.
After the completion of the reaction as indicated by TLC, the reaction
mixture was filtered off and washed with water, the organiclayer was sepa-
rated out, dried over sodium sulfate, and evaporated under vacuum. The
crude product (yield 92%) was purified by silica gel (100–200 mesh) chro-
matography using ethyl acetate : hexane (3:7) as eluent to get p-nitrophenol
(108 mg 85%) m.p. 113ꢀC (lit. m.p. 114ꢀC) and o-nitrophenol (19 mg 15%)
m.p. 44ꢀ–45ꢀC (lit. m.p. 45ꢀC).
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Received in Japan April 17, 2000