Fast and efficient nitration of salicylic acid and some other aromatic compounds over H3PO4/TiO2-ZrO2 using nitric acid

Article abstract of DOI:10.1002/cjoc.201090086

TiO₂-ZrO₂ (1/1)-surf with Ti and Zr molar ratio of 1/1 was prepared with surfactant through a sol-gel method. The optimum experimental condition was investigated for nitration of salicylic acid. Then, a number of nitration reactions were carried out with a variety of aromatic compounds in the optimum condition. The 25 wt% H₃PO₄/TiO₂-ZrO₂ (1/1)-surf catalyst showed good selectivity and yield in a short time for the nitration of salicylic acid and some other aromatic compounds.

Full text of DOI:10.1002/cjoc.201090086

FULL PAPER
Fast and Efficient Nitration of Salicylic Acid and Some Other
Aromatic Compounds over H3PO4/TiO2-ZrO2 Using Nitric Acid
Kalbasi, Roozbeh Javad*,a,b
Massah, Ahmad Reza*,a,b
Zamani, Farzada Javaherian Naghash, Hamidb
a Department of Chemistry, Islamic Azad University, Shahreza Branch, 311-86145, Shahreza, Isfahan, Iran
b Razi Chemistry Research Center, Islamic Azad University, Shahreza Branch, Shahreza, Isfahan, Iran
TiO2-ZrO2 (1/1)-surf with Ti and Zr molar ratio of 1/1 was prepared with surfactant through a sol-gel method.
The optimum experimental condition was investigated for nitration of salicylic acid. Then, a number of nitration
reactions were carried out with a variety of aromatic compounds in the optimum condition. The 25 wt%
H3PO4/TiO2-ZrO2 (1/1)-surf catalyst showed good selectivity and yield in a short time for the nitration of salicylic
acid and some other aromatic compounds.
Keywords nitration, H3PO4/TiO2-ZrO2, nitric acid, salicylic acid, aromatic compound
Introduction
introduced for the nitration of aromatic compounds such
as acetyl nitrate, benzoyl nitrate, trimethylsilyl nitrate,7
N-nitropyridinium salts, nitrogen oxide,8 NaHSO4•H2O,
Mg(HSO4)2, and oxone,9,10 sulfonated polyorganosilox-
anes11,12 and acidic resins.13
Phosphate-based solid acids have already been quite
efficacious in several industrially important acid-dem-
anding reactions.14,15 In addition, phosphate seems to
enhance catalytic properties, to stabilize surface area
and crystal phase, to improve the surface acidity and to
make the impregnated material porous.16
Recently, it has been observed that H3PO4/TiO2-
ZrO2 (1/1)-surf showed high thermal stability, low
catalytic deactivation and very good selectivity for
Beckmann rearrangement,17 acylation of phenol18 and
Fries rearrangement.19 These data showed that H3PO4/
TiO2-ZrO2 (1/1)-surf had a good activity and selectivity
for the acid catalyzed reactions.
In this paper, the efficacy of the H3PO4/TiO2-ZrO2
(1/1)-surf catalyst is presented for the nitration of sali-
cylic acid to 5-nitrosalicylic acid. The activity and regio
selectivity of this catalyst for the nitration of some other
aromatic compounds are also reported.
Nitration of organic compounds is one of the very
important processes in chemical industries. Nitro aro-
matic compounds are utilized extensively as chemical
feed stocks for a wide range of useful materials. Among
the aromatic nitro compounds, 5-nitrosalicylic acid is a
very important intermediate for the pharmaceutical in-
dustry. The derived amine (mesalazine) has been se-
lected as a drug for ulcerative colitis for many years.1
The 5-nitrosalicylic acid is currently obtained through
nitration processes of salicylic acid by means of differ-
ent nitrating systems such as mixed acid (nitric
acid/sulfuric acid, molar ratio＝3) or 70% nitric acid
solutions.2,3 In a previous investigation,4 the authors
have shown that runaway phenomena can occur during
the nitration process of salicylic acid by means of nitric
acid/acetic acid mixtures as a result of polynitration re-
actions, which take place when the thermal control of
the process is lost. In particular, successive nitration of
5-nitrosalicylic acid and by-product (3-nitrosalicylic
acid) leads to the formation of explosive picric acid.5
A major problem associated with the industrial nitra-
tion technology is that the usage of corrosive liquid
phase including nitric acid-sulfuric acid mixture gener-
ates large amounts of waste that is very costly to treat.
Over-nitration, oxidation of by-products and poor selec-
tivity are other problems.6 To overcome these problems,
a considerable effort has been put into developing het-
erogeneously catalyzed reactions for the liquid and va-
por phase nitration using solid acid catalysts. In this
contest, a lot of attempts have been made to find an ef-
ficient catalyst for the nitration of aromatics and substi-
tuted aromatics. Many reagents and catalysts have been
Experimental
Preparation of the catalyst
TiO2-ZrO2 (1/1)-surf was used as the support, which
was prepared by a sol-gel method20,21 and is denoted as
TiO2-ZrO2 (1/1)-surf.17 A series of catalysts with vary-
ing H3PO4 contents were prepared by impregnating
calculated amounts of H3PO4 dissolved in deionized
water on the TiO2-ZrO2 (1/1)-surf support. The impreg-
*
E-mail: rkalbasi@iaush.ac.ir, massahar@iaush.ac.ir; Fax: 0098-321-3293095; Tel.: 0098-321-3292072
Received May 26, 2009; revised October 19, 2009; accepted November 19, 2009.
Chin. J. Chem. 2010, 28, 397— 403
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397

Kalbasi et al.
FULL PAPER
nated catalysts were dried at 110 ℃ for 12 h and then
calcined in air at 500 ℃ for 6 h.17
Typical procedure for the synthesis of nitro aromatic
compounds
To a round-bottomed flask containing a mixture of
25 wt% H3PO4/TiO2-ZrO2 (1/1)-surf catalyst (0.07 g,
0.23 mmol), nitric acid (65%, 1 mmol), dichloro-
methane (5 mL) and salicylic acid (1 mmol) was added,
and the resulting mixture stirred at reflux temperature.
The progress of the reaction was monitored by GC
(Varian CP3800). At the end of the reaction, the catalyst
was separated by filtration and washed with ethyl ace-
tate (10 mL×2). The filtrate was washed sequentially
with 5% aqueous solution of sodium bicarbonate (2.5
mL), and water (5 mL), and then dried with anhydrous
MgSO4. The evaporation of solvent, followed by col-
umn chromatography of the crude mixture on silica gel
using n-hexane and ethyl acetate as eluent, afforded
3-nitrosalicylic acid and 5-nitrosalicylic acid in a 26∶
74 ratio in pure form. The overall yield was 83%. The
conditions of nitration reaction were optimized for sali-
cylic acid, and consequently the nitration of some other
aromatic compounds was performed in the optimum
conditions.
Results and discussion
Figure 1 EDS diagrams of catalyst before and after the loading
of H3PO4: (a) TiO2-ZrO2 (1/1)-surf and (b) 25 wt%
H3PO4/TiO2-ZrO2 (1/1)-surf.
Catalyst characterization
The catalyst was characterized using a variety of
physical methods, including FT-IR (Fourier transform
infrared), XRD (X-ray diffraction), XRF (X-ray fluo-
rescence) and BET (Brunauer-Emmett-Teller) surface
area measurements.17 The acidity of the catalyst was
determined using pyridine adsorption-desorption.18 In
order to verify the presence of minor phases, SEM
(scanning electron microscopy) and EDS (energy dis-
persive spectrum) analyses were carried out on TiO2-
ZrO2 (1/1)-surf before and after the loading of H3PO4
(by SERON, AIS-2100). The EDS data of the calcined
TiO2-ZrO2 (1/1)-surf and 25 wt% H3PO4/TiO2-ZrO2
(1/1)-surf are presented in Figure 1. As can be seen,
Ti/Zr ratio obtained from the corresponding EDS data
for the TiO2-ZrO2 (1/1)-surf and 25 wt% H3PO4/TiO2-
ZrO2 (1/1)-surf samples were approximately similar as
expected. Moreover, the results from EDS analyses are
presented in Table 1. The percentage of P in the loaded
catalyst was 7.27 wt%, which was close to the value set
in the catalyst design.
In addition, SEM images show the external mor-
phology of the calcined catalyst before (Figures 2a, 2b)
and after the loading of phosphoric acid (Figures 2c, 2d),
from which the phosphoric acid layer on TiO2-ZrO2
(1/1)-surf can be seen (Figures 2c, 2d).
XRD patterns for calcined samples at 500 ℃ after
loading of H3PO4 with different concentrations are
shown in Figure 3 (by Bruker D8ADVANCE, Cu Kα
radiation). TiO2-ZrO2 (1/1)-surf before loading H3PO4
shows an amorphous form, but after this loading the
peaks corresponding to the crystalline TiO2 phase and
crystalline ZrO2 phase are observed. In the TiO2 spec-
trum, the peak at 2θ＝25.5° corresponds to the anatase
crystalline phase and in the ZrO2 spectrum the peak at
2θ＝30.0° corresponds to the tetragonal crystalline
phase.22-25
Catalytic activity
One of our major concerns was to examine the activ-
ity and the regio selectivity of this catalyst for the nitra-
tion of salicylic acid and some other aromatic com-
pounds. Accordingly, a number of reactions were car-
ried out with a variety of aromatic compounds, after
ascertaining the optimum experimental conditions. The
results are summarized in Table 2. The catalyst was
very effective towards activated aromatic compounds
(Entries 2—5, Table 2) and the corresponding
Chin. J. Chem. 2010, 28, 397— 403
Table 1 EDS results of TiO2-ZrO2 (1/1)-surf before and after
the loading of H3PO4
Sample
Ti
Zr
O
P
TiO2-ZrO2 (1/1)-surf 41.07%
49.62% 8.7%
—
25 wt% H3PO4/TiO2-
31.79%
40.08% 20.48% 7.27%
ZrO2 (1/1)-surf
398
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Nitration of Salicylic Acid and Some Other Aromatic Compounds
Figure 2 SEM images of samples at different magnifications: (a) TiO2-ZrO2 (1/1)-surf, (b) TiO2-ZrO2 (1/1)-surf, (c) 15 wt%
H3PO4/TiO2-ZrO2 (1/1)-surf, (d) 15 wt% H3PO4/TiO2-ZrO2 (1/1)-surf.
Table 2 Mono-nitration of aromatic compounds
Entry
1
Substrate
Benzene
Productb
Total yielda/ % Time/min Molar ratio (aromatic compound∶nitric acid)
Nitrobenzene
98
96
25
1
1∶1.5
1∶1
(a) 4-Nitrophenol (90%),
(b) 2-Nitrophenol (10%)
2
Phenol
(a) 2-Nitro-p-cresol (95%),
(b) 3-Nitro-p-cresol (5%)
3
4
p-Cresol
90
75
Immediately
1
1∶1
1-Naphthol
4-Nitro-1-naphthol
1∶1.5
5
6
2-Naphthol
Anthracene
Biphenyl
1-Nitro-2-naphthol
9-Nitroanthracene
4-Nitrobiphenyl
65
70
43
30
28
25
36
1
1∶1.5
1∶1.5
1∶1.5
1∶2.8
1∶2.8
1∶2.8
1∶2.8
5
7
15
30
30
30
25
8
Benzoic acid
Benzonitrile
Nitrobenzene
3-Nitrobenzoic acid
3-Nitrobenzonitrile
1,3-Dinitrobenzene
9
10
11
Benzophenone 3-Nitrobenzophenone
(a) 1-Bromo-4-nitrobenzene (90%),
(b) 1-Bromo-2-nitrobenzene (10%)
12
13
14
Bromobenzene
Chlorobenzene
Salicylic acid
70
70
83
15
15
5
1∶2.8
1∶2.8
1∶1
(a) 1-Chloro-4-nitrobenzene (90%),
(b) 1-Chloro-2-nitrobenzene (10%)
(a) 5-Nitrosalicylic acid (74%),
(a) 3-Nitrosalicylic acid (26%)
a Isolated yield. b Isomeric ratio was estimated using 1H NMR and 13C NMR spectra of the crude products [Reaction conditions: catalyst
(0.07 g), dichloromethane (5 mL), reflux temperature].
Chin. J. Chem. 2010, 28, 397— 403
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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399

Kalbasi et al.
FULL PAPER
and (II) contain Lewis acidic and basic sites. So it can
be seen that TiO2-ZrO2 and TiO2-ZrO2-surf just show
Lewis acid sites and Brønsted acid sites are not avail-
able. On the other hand, with loading H3PO4 on these
supports two things happened: Some of loaded H3PO4
removes the adsorbed water on the Lewis sites (struc-
tures I and II), which leads to in＋creasing Lewis acid
＋
sites of the obtained catalyst (Zr4 and Ti4 ).16 Some
other H3PO4 that loaded by esterification of remaining
M-OH groups on the support produces weak Brønsted
acid sites (P-OH) (Schemes 1 and 2). As a result, the 25
wt% H3PO4/TiO2-ZrO2 (1/1)-surf catalyst has the
maximum yield and the best selectivity for
5-nitrosalicylic acid in this condition.
Figure 3 XRD patterns for the calcinated catalysts: (a) TiO2-
ZrO2 (1/1)-surf, (b) 5 wt% H3PO4/TiO2-ZrO2 (1/1)-surf, (c) 15
wt% H3PO4/TiO2-ZrO2 (1/1)-surf, (d) 25 wt% H3PO4/TiO2-ZrO2
(1/1)-surf and (e) 35 wt% H3PO4/TiO2-ZrO2 (1/1)-surf.
In order to investigate effect of the support [TiO2-
ZrO2 (1/1)-surf] on the nitration reaction, we used
H3PO4 (with the same ratio of the optimized catalyst)
without any support as catalyst in the nitration of sali-
cylic acid by keeping other parameters constant. After
35 min, 60% selectivity and about 65% yield were ob-
served. Therefore, TiO2-ZrO2 (1/1)-surf as a support is
very useful for the nitration reaction.
The effect of temperature on the nitration of salicylic
acid was also studied. The reaction was carried out in
the presence of 0.07 g of 25 wt% H3PO4/TiO2-ZrO2
(1/1)-surf using salicylic acid∶nitric acid molar ratio
1∶1 and the reaction temperatures were varied from
room temperature (25 ℃) to 40 ℃. The results are
presented in Table 3. It was observed that with increase
of the reaction temperature from 25 to 40 ℃, the sali-
cylic acid yield was increased from 75% to 83%. In ad-
dition, the selectivity was also raised with increasing
temperature. In general, when the reaction is carried out
at lower temperature, the conversion decreases. We be-
lieve that increasing the temperature is apparently fa-
vorable for accelerating the reaction.
nitro products were readily obtained in good to excellent
yields (65%—96%). Moderately activated aromatic
compounds also underwent nitration in good yields (En-
tries 12—14, Table 2). It is notable that poly aromatic
hydrocarbons, viz., anthracene (Entry 6, Table 2) and
biphenyl (Entry 7, Table 2) underwent regioselective
nitration under the same reaction conditions. Moreover,
the catalyst was effective towards inactivated com-
pounds. Interestingly, for a substrate amenable to facile
oxidation, there were not any oxidation products. Thus,
the reaction of p-cresol (Entry 3, Table 2) led only to
nitration products. It is considerable that these reactions
were carried out in a short time in comparison with
other reported procedures. A preparative scale reaction
was performed using 3 g of salicylic acid, and the reac-
tion worked well with an isolable yield of 83% (Entry
14, Table 2).
The influence of various reaction parameters such as
solvent, reaction temperature, amount of loaded H3PO4
and catalyst, feed ratio of salicylic acid to nitric acid and
recyclability of the catalyst has been studied to optimize
reaction conditions.
Improvement of H3PO4/TiO2-ZrO2 (1/1)-surf cata-
lytic activity was made by optimizing the amount of
loaded H3PO4. The variation of loaded H3PO4 (15—35
wt%) has different effects on the yield and selectivity of
the catalyst (see Figure 4). In the presence of the opti-
mized catalyst (25 wt% H3PO4/TiO2-ZrO2 (1/1)-surf),
over 70% selectivity and about 85% yield were ob-
served. In order to decrease the amount of by-products
caused by oxidation, H3PO4 was used for treating
TiO2-ZrO2 (1/1)-surf. The acidity of H3PO4 is lower
than H2SO4 which has been used in other researches.26,27
In general, the most important role of H3PO4 in this
new catalyst is to destroy the strong Brønsted acid sites
and substitute them with weak Brønsted sites. In this
condition, the weak Brønsted acid sites were increased.
Therefore, it could be expected that we had a milder
catalyst, which shows good yield and selectivity for the
nitration reaction without producing any polynitration
and oxidation products. According to Tanabe’s hy-
pothesis,28 the surface structure of TiO2-ZrO2 can be
represented as I and II in Scheme 1. Both structures (I)
Table 3 Effect of temperature
Selectivity/%
Temperature/℃
Yield/%
Time/min
para
70
ortho
30
Room temperature
40
75
83
60
5
74
26
Reaction conditions: dichloromethane (5 mL), n(salicylic acid)∶
n(nitric acid)＝1∶1, catalyst (0.07 g).
The effect of the amount of 25 wt% H3PO4/TiO2-
ZrO2 (1/1)-surf on salicylic acid conversion and product
selectivity was studied in the range of 0.02 to 0.15 g at
40 ℃ in dichloromethane. The results are presented in
Figure 5, which shows that the yield increases with
raising the amount of catalyst up to 0.07 g. But a further
increase leads to a drop in overall yield. 0.07 g catalyst
was selected for further experimental studies due to its
optimum performance.
The effect of the feed ratio of salicylic acid to nitric
yield and product selectivity was studied from 1∶1 to
400
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Chin. J. Chem. 2010, 28, 397— 403

Nitration of Salicylic Acid and Some Other Aromatic Compounds
Scheme 1 TiO2-ZrO2 structures and interaction with H3PO4
Figure 5 Effect of the catalyst amount. Reaction conditions:
reflux temperature, dichloromethane (5 mL), n(salicylic acid)∶
n(nitric acid)＝1∶1.
Scheme 2 Mechanism for the nitration of aromatic compounds
over H3PO4/TiO2-ZrO2
Figure 6 Effect of salicylic acid∶nitric acid molar ratio. Reac-
tion conditions: catalyst (0.07 g), reflux temperature, dichloro-
methane (5 mL).
cylic acid is more highly adsorbed than nitric acid on
the acid sites of the catalyst. Therefore, the yield was
decreased but the selectivity was increased. Moreover,
at high feed ratios (high percentage of nitric acid),
multi-nitration predominantly occurred. The maximum
selectivity to 5-nitrosalicylic acid was observed for the
1∶1 feed ratio.
The nitration of salicylic acid at reflux temperature
was carried out using various common solvents such as
CH2Cl2, CH3CN, CH3OH and CHCl3. The results are
shown in Table 4. Using 25 wt% H3PO4/TiO2-ZrO2
(1/1)-surf, the highest yield and selectivity for the nitra-
tion of salicylic acid were obtained when the reaction
was carried out in CH2Cl2 as solvent. As can be ex-
pected, the protic solvents such as methanol were not
appropriate for the nitration reaction, because it may
block the active sites of the catalyst. Consequently, the
yield and selectivity were decreased because of the de-
creasing of salicylic acid interaction with the active sur-
face of catalyst.
Figure 4 Effect of loaded H3PO4. Reaction conditions: reflux
temperature, dichloromethane (5 mL), n(salicylic acid)∶n(nitric
acid)＝1∶1, catalyst 0.07 g.
1∶2.8 at 40 ℃ over 25 wt% H3PO4/TiO2-ZrO2
(1/1)-surf. The results are presented in Figure 6. At the
1∶2.8 feed ratio, the yield was about 95%, however,
the 5-nitrosalicylic acid selectivity was about 58%. This
reveals that at a low feed ratio (1∶1 or 1∶1.2), sali-
Our investigations indicate that polar aprotic solvent,
such as dichloromethane, leads to higher selectivity to
5-nitrosalicylic acid than other aprotic solvents. The
most likely reason for this, is that the polar solvents in-
Chin. J. Chem. 2010, 28, 397— 403
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
401

Kalbasi et al.
FULL PAPER
Table 4 Influence of solventa
Table 5 Recyclability of the catalyst
Reaction cycle
Yield/%
Time/min
Selectivity/%
Selectivity/%
Solvent
Yield/%
Time/min
para
74
ortho
26
para
74
ortho
26
1
2
3
83
77
72
5
5
5
CH2Cl2
83
5
5
74
26
CHCl3
70
72
70
30
74
26
CH3CN
CH3OH
Solvent free
67
33
5
No reaction
69
No reaction
65 35
270
15
Table 6 shows the comparison between the catalysts
used in the present study and other solid catalysts re-
ported in the literature for the nitration of salicylic acid
and other aromatic compounds. As can be seen, the 25
wt% H3PO4/TiO2-ZrO2 (1/1)-surf catalyst shows good
selectivity and reasonable yield for the nitration of sali-
cylic acid and some other aromatic compounds in a
short time.
a Reaction conditions: catalyst (0.07 g), reflux temperature, n(sali-
cylic acid)∶n(nitric acid)＝1∶1.
crease the desorption rate of product. Accordingly, its
contact time on the catalyst surface was decreased, and
less poly nitration precursors were obtained. Further-
more, the polarity of dichloromethane may cause the
intermediate species such as nitronium ion to become
more stable.
Conclusion
A heterogeneous solid acid catalyst has been devel-
oped by impregnation of phosphate over TiO2-ZrO2
(1/1)-surf for the nitration of salicylic acid and some
other aromatic compounds using nitric acid. The 25
wt% H3PO4/TiO2-ZrO2 (1/1)-surf catalyst showed good
selectivity and yield at short run for the nitration of ac-
tivated, moderately activated and inactivated aromatic
compounds without producing poly nitration and oxida-
tion by-products. In addition to the short reaction time,
this catalyst showed good activity after the third cycle
of the reaction.
Upon completion of reaction, reusability of the cata-
lyst was examined using 0.07 g of 25 wt% H3PO4/
TiO2-ZrO2 (1/1)-surf. In order to regenerate the catalyst
after 5 min reaction time, it was separated by filtration,
washed with ethyl acetate, calcined at 540 ℃ for 6 h
and reused in the nitration reaction with a fresh reaction
mixture. It was observed that with increase in the num-
ber of usage times of the catalyst, its catalytic activity
was decreased, which could probably be due to the
leaching of the catalyst (Table 5).
Table 6 Comparison with other solid acid catalysts
Selectivity/%
Conversion/
%
Time/
min
Catalyst
Substrate
Phenol
Reagent
Nitric acid
Reference
para
58
8
ortho
42
Phosphate/titania
Sulfate/titania
ZSTA-15
90a
93
2
29
30
31
32
Phenol
Phenol
Phenol
Nitric acid
Nitric acid
90
120
60
95
8
91
Sulfate/titania
Nitric acid
ρ-Toluenesulfonic
acid
85.6
3.9
92.4
120
Nickel(ІІ) nitrate
Phenol
85a
—
85
30
33
25 wt% H3PO4/TiO2-ZrO2 (1/1)-surf
Yb(N(SO2C4F9)2)3/MCM-41
ZSTA-15
Phenol
Nitric acid
96a
97.2
32
90
10
1
This work
Chlorobenzene
Chlorobenzene
Chlorobenzene
Bromobenzene
Bromobenzene
Bromobenzene
Benzene
Nitric acid
Nitric acid
Nitric acid
Nitric acid
Nitric acid
Nitric acid
Nitric acid
Nitric acid
Nitric acid
NaNO3
56.3
52
43.2
28
1440
60
34
31
25 wt% H3PO4/TiO2-ZrO2 (1/1)-surf
Phosphate/titania
70a
70a
97.2
70a
86a
64.3a
98a
—
90
10
15
This work
29
75
25
90
Yb(N(SO2C4F9)2)3/MCM-41
25 wt% H3PO4/TiO2-ZrO2 (1/1)-surf
Phosphate/titania
56.2
90
43.2
10
1440
15
34
This work
29
—
—
5
Yb(N(SO2C4F9)2)3/MCM-41
25 wt% H3PO4/TiO2-ZrO2 (1/1)-surf
Benzene
—
—
480
25
34
Benzene
—
—
This work
35
Benzyltriphenylphosphonium peroxodisulfate Salicylic acid
70
—
390
5
25 wt% H3PO4/TiO2-ZrO2 (1/1)-surf
a Yield.
Salicylic acid
Nitric acid
83a
74
26
This work
402
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© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 397— 403

Nitration of Salicylic Acid and Some Other Aromatic Compounds
Acknowledgements
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18 Ghiaci, M.; Kalbasi, R. J.; Mollahasani, M.; Aghaei, H.
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Special thanks from the authors are given to Islamic
Azad University, Shahreza Branch (IAUSH) Research
Council and Center of Excellence in Chemistry (IAUSH)
to support this work.
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