Regioselective mononitration of aromatic compounds using Brnsted acidic

ionic liquids as recoverable catalysts

Dong Fang, Qun-Rong Shi, Jian Cheng, Kai Gong, Zu-Liang Liu*
School of Chemical Engineering, Nanjing University of Science & Technology, Nanjing, PR China
1. Introduction
Electrophilic nitration of aromatics is a fundamental reaction of
great industrial importance, whose products are used as organic
intermediates or energetic materials. It is also among the most
important unit reactions in the chemical industry. The mechanistic
and synthetic aspects of nitration chemistry have been very
thoroughly studied over the years. Depending on the reactivity of
the nucleophile substrates and the desired chemo- and regios-
electivity, many nitrating systems have been developed. These
range from protic nitrating with mixed acids and superacids to
nitryl halides, acyl- and alkyl nitrates, metal nitrates, or nitronium
salts, as well as supported nitration and transfer-nitration reagents
[1,2].
However, the usual commercial process is not environmentally
benign since it results in disposal problems, necessitates regen-
eration of used acids, and often provides poor selectivity for the
desired products. Various nitration approaches have therefore
been explored in order to avoid the problems of the traditional
mixed acid method, which used nitric and sulfuric acids. The new
approaches particularly involve the use of recyclable catalysts
including lanthanide triates [3], peruorinated rare earth metal
salt/uorous solvent [4,5], or solid acid catalysts such as a
peruorinated resin sulfonic acid [6], claycop [7], and zeolites [8,9].
To date, ionic liquids have been used in aromatic nitration: Laali
and Gettwert [9] used a range of nitration agents in the nitration of
mainly activated substrates; Rajagopal and Srinivasan [10] used
iron nitrate in the nitration of phenols, Lancaster and Liopis-Mestre
[11] investigated several nitration systems, and they demonstrated
that HNO
3
/Ac
2
Oin an ionic liquid that contained [bmpy]
+
(1-butyl-
1-methylpyrrolidinium) cation was the best system. Smith et al.
[12] reported regioselective mononitration of simple aromatic
compounds with HNO
3
/Ac
2
O in [bmim]BF
4
, [bmim]PF
6
, and
[bdmim]BF
4
systems.
Brnsted acidic task-specic ionic liquids (TSILs), since they
combine the advantageous characteristics of solid acids and
mineral acids, are designed to replace traditional mineral liquid
acids, such as sulfuric acid and hydrochloric acid, in chemical
processes [13,14]. Recent years, some greener halogen-free ionic
liquids that involve phosphate or octyl sulfate anions have been
reported and the effects of the anion and the toxicology have been
studied [15,16]. Very recently, Qiao et al. [17] reported that a
Brnsted acidic ionic liquid was capable of catalyzing the nitration
of aromatic compounds with medium concentration aqueous
nitric acid. The use of Brnsted acidic TSILs to catalyze organic
reactions is an area of ongoing activity; however, development and
exploring of Brnsted acidic TSILs are currently in the preliminary
stage and the number of published examples of Brnsted acidic
TSILs is limited. As part of our continuing interest in the
development of clean chemical processes, in particular clean
nitration of aromatic compounds [1820], we synthesized some
novel halogen-free SO
3
H-functional Brnsted-acidic TSILs that
bear an alkane sulfonic acid group in an acyclic trialkanylammo-
Applied Catalysis A: General 345 (2008) 158163
A R T I C L E I N F O
Article history:
Received 23 January 2008
Received in revised form 24 April 2008
Accepted 26 April 2008
Available online 3 May 2008
Keywords:
Ionic liquid
Catalyst
Nitration reaction
A B S T R A C T
Some novel acyclic Brnsted acidic task-specic ionic liquids (TSILs) that bear an alkane sulfonic acid
group in an acyclic trialkanylammoniumcation were synthesized and their uses as halogen-free catalysts
for regioselective mononitration of aromatic compounds were investigated. The reactions were carried
out at 6080 8C with reasonable to good yields and improved para-selectivities for halogenobenzenes
compared to those in the absence of the catalysts. In addition, the TSILs could be recovered and reused
without noticeably decreasing the catalytic activity.
2008 Elsevier B.V. All rights reserved.
* Corresponding author. Tel.: +86 25 84318865; fax: +86 25 84318865.
E-mail address: liuzuliang302@163.com (Z.-L. Liu).
Contents lists available at ScienceDirect
Applied Catalysis A: General
j ournal homepage: www. el sevi er. com/ l ocat e/ apcat a
0926-860X/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2008.04.037
nium cation (Fig. 1). Their uses as catalysts for aromatic nitration
(Scheme 1) have also been explored.
2. Results and discussion
2.1. Preparation of SO
3
H-functional Brnsted-acidic TSILs
The synthesis approach is made up of two-step atom economic
reactions. The zwitterionic-type precursors (trialkanylammonium
propane sulfonate and trialkylammonium butane sulfonate) of
these TSILs were prepared according to our previous procedure
[18] through a one-step direct sulfonation reaction of trialk-
anylamine and 1,3-propane or 1,4-butane sulfone. The syntheses
of SO
3
H-functional TSILs with different anions are convenient
when the corresponding acids have more acidity than the alkane
sulfonic acid groups bearing in TSILs cations. The zwitterion
acidication can be accomplished by mixing of zwitterion with
strong acids, such as CF
3
COOH, H
2
SO
4
(98%, aqueous), H
3
PO
4
(85%,
aqueous), and p-TSAH
2
O, to convert the pendant sulfonate group
into an alkane sulfonic acid, trialkanylpropanesulfonic acid
ammonium hydrogen sulfate, or the like. The result is the
transformation of the zwitterion into a cation bearing an appended
sulfonic acid group, with the conjugate base of the exogenous acid
becoming the TSILs anion. Both H
2
SO
4
(98%, aqueous) and H
3
PO
4
(85%, aqueous) can be selected to obtain the greener halogen-free
TSILs; however, in the case of aromatic nitration, the correspond-
ing acids should have at least more acidity than nitric acid in order
that the TSILs anion should not endure protolysis. Hence, H
2
SO
4
(98%, aqueous) should be the suitable acid and the TSILs with
HSO
4

anions were used as the catalysts in the following

experiment. The fresh new TSILs with HSO
4

anion are somewhat

viscous colorless liquids at room temperature. In keeping with the
behavior of other ionic liquids (IL), neither of the new species
fumes or manifests any noticeable degree of vapor pressure, the
treatment of the newTSILs under vacuumat 120 8C for 72 h results
in no loss of mass and veries that these TSILs are stable at high
temperature unlike strong acids dissolved in conventional IL,
which frequently continue to emit noxious vapors and do harm to
the environment. Such stability indicates that the donor acids
being fully incorporated into their respective TSILs structures,
rather than remaining simply mixtures of added strong acids with
dissolved zwitterion, in which case some retention of premixing
characteristics would be expected.
The Brnsted acidities of these TSILs were evaluated for the
determination of the Hammett acidity functions, using UVvis
spectroscopy. For the comparison purposes, the acidities of these
ve TSILs have been examined using 4-nitroanline (Hammett
constant is 0.99) as the indicator (named I) in dichloromethane
(named s), and then the Hammett function (H
0
) could be calculated
(Table 1).
All produced TSILs are miscible with water and soluble in
methanol, ethanol, andacetone, andtheyarepartlysolubleinethers,
alkanes, and aromatic hydrocarbons according to their structure.
The solubility of these ve TSILs in organic solvents decreased
as follows: [TBPSA][HSO
4
] > [TEBSA][HSO
4
] > [TEPSA][HSO
4
] >
[TMBSA][HSO
4
] > [TMPSA][HSO
4
].
2.2. Aromatic nitration with SO
3
H-functional Brnsted-acidic TSILs
The electophilic aromatic nitration is one of the typical classical
acid-promoted organic reactions. From either an industrial or an
environmental standpoint, the ideal nitrationagent is aqueous nitric
acid, which is inexpensive and generates only water as waste.
Unfortunately, few catalytic systems that involved using aqueous
nitric acid as the nitration agent are reported up to now. Our initial
effort aimed to use TSILs as solvent and aqueous nitric acid as the
nitrating reagent so that water would be the only byproduct. The
results of the nitration of aromatic compounds with 68% nitric acid
are listed as below. For the beginning of this study, nitration of
Fig. 1. The halogen-free ionic liquids TSILs.
Scheme 1. Nitration of aromatic compounds.
D. Fang et al. / Applied Catalysis A: General 345 (2008) 158163 159
halogenobenzene with 68% nitric acid in synthesized TSILs as the
catalysts was explored, and the results are listed in Tables 24.
Nitrouorobenzenes were obtained in the yields ranging from62 to
72%, with a para to ortho ratio of 1213. In the presence of TSILs, the
para-selectivity was signicantly higher than that nitrated in the
absence of TSILs (Table 2). In case of chlorobenzene (Table 3) and
bromobenzene (Table 4), the use of all ve TSILs was advantageous
from the points of view of the reaction yield and selectivity in
comparison to the reaction without the catalysts.
As seen from the results of Tables 24, different yields were
obtained in these TSILs. The order of catalytic activity is not
consistent with the sequence of ionic liquid acidity (Table 2) but is
consistent with the sequence of solubility in organic solvents.
Reactions were monitored by GC over a period of time. The results
obtained even with 3 equiv of nitric acid (68%) at 80 8C were not
ideal in the absence of TSILs. This indicated that the catalyst was
absolutely necessary for improved para-selectivities of the
halogenobenzenes nitration.
In view of the success of the new reactions, it was decided to
apply them to a range of simple substrates, and the results are
shown in Table 5.
Table 1
H
0
values of the TSILs in dichloromethane
a
TSILs Absorbance (AU) [I] (%) [IH
+
] (%) H
0
[TMPSA][HSO
4
] 0.37 12.3 87.7 0.14
[TEPSA][HSO
4
] 0.40 13.3 86.7 0.18
[TBPSA][HSO
4
] 0.76 25.3 74.7 0.52
[TMBSA][HSO
4
] 0.39 13.0 87.0 0.16
[TEBSA][HSO
4
] 0.90 30.0 70.0 0.62
H
0
= pK(I)
aq
+ log([I]
s
/[IH
+
]
s
).
a
Concentration: 10 mmol/L; indicator: 4-nitroanline.
Table 2
Result for nitration of uorobenzene with different TSILs
a
Entry TSILs Selectivity (%)
b
Yield (%)
c
Product isomers (%)
d
para/ortho
e
ortho meta para
1 [TMPSA][HSO
4
] 99 62 7.7 0 92.3 12
2 [TEPSA][HSO
4
] 99 67 7.6 0 92.4 12
3 [TBPSA][HSO
4
] 99 72 7.2 0 92.8 13
4 [TMBSA][HSO
4
] 99 70 7.6 0 92.4 12
5 [TEBSA][HSO
4
] 99 71 7.3 0 92.7 13
6 None 99 13 15.7 0 84.3 5.4
a
Reaction conditions: 20 mmol uorobenzy, 60 mmol 68% nitric acid, TSILs 0.4 mmol, 80 8C.
b
Selectivity of mono-nitrating.
c
Based on crude product.
d
By quantitative GC analysis and qualitative GC/MS.
e
Ratio of para/ortho calculated from original GC data.
Table 3
Result for nitration of chlorobenzene with different TSILs
a
Entry TSILs Selectivity (%)
b
Yield (%)
c
Product isomers (%)
d
para/ortho
e
ortho meta para
1 [TMPSA][HSO
4
] 99 46 24.1 0.7 75.2 3.1
2 [TEPSA][HSO
4
] 99 52 23.6 0.7 75.7 3.2
3 [TBPSA][HSO
4
] 99 65 22.2 0.3 77.5 3.5
4 [TMBSA][HSO
4
] 99 53 23.4 0.4 76.2 3.1
5 [TEBSA][HSO
4
] 99 55 23.2 0.6 76.2 3.3
6 None 99 10 35.2 1.0 63.8 1.8
a
Reaction conditions: 20 mmol chlorobenzy, 60 mmol 68% nitric acid, TSILs 0.4 mmol, 80 8C.
b
Selectivity of mono-nitrating.
c
Based on crude product.
d
By quantitative GC analysis and qualitative GC/MS.
e
Ratio of para/ortho calculated from original GC data.
Table 4
Result for nitration of bromobenzene with different TSILs
a
Entry TSILs Selectivity (%)
b
Yield (%)
c
Product isomers (%)
d
para/ortho
e
ortho meta para
1 [TMPSA][HSO
4
] 99 42 25.1 0 74.9 3.0
2 [TEPSA][HSO
4
] 99 50 23.9 0 76.1 3.2
3 [TBPSA][HSO
4
] 99 55 23.8 0 76.2 3.2
4 [TMBSA][HSO
4
] 99 51 25.0 0 75.0 3.0
5 [TEBSA][HSO
4
] 99 52 24.8 0 75.2 3.0
6 None 99 12 47.6 0.4 52.0 1.1
a
Reaction conditions: 20 mmol bromobenzy, 60 mmol 68% nitric acid, TSILs 0.4 mmol, 80 8C.
b
Selectivity of mono-nitrating.
c
Based on crude product.
d
By quantitative Waters 600E/2487 HPLC analysis.
e
Ratio of para/ortho calculated from original HPLC data.
D. Fang et al. / Applied Catalysis A: General 345 (2008) 158163 160
As seen from the results of the above tables, although the
reactions of uorobenzene, chlorobenzene, and bromobenzene
were more para-selective in the presence of TSILs than that in the
absence of TSILs, this trend was not apparent for some activated
aromatic compounds. In the nitration of activated substrates, there
was relatively little difference with or without the TSILs. For
example, in the nitration of toluene, 67% yield could be achieved in
the absence of catalysts with near identical regioselectivity (entry
11). This suggested that a correlation exists between the degree of
para-selectivity and the ability of electron-withdrawing substi-
tuents to induce an electrostatic attraction between substrate and
TSILs, causing greater hindrance at positions ortho to such
substituents [10]. The limit of the system appears to be reached
in the nitration of nitrobenzene. The reaction was sluggish and no
product could be detected by GC analysis.
Generally, the use of these TSILs was advantageous from the
points of view of the reaction yield and selectivity in comparison
the reactions without the catalysts. There appear to be several
possible explanations for the difference between the reaction in
the present of and in the absence of the TSILs. The rst is that the
reagent and the substrate are both charge neutral, but react to
form a charged intermediate. Indeed, the outcomes of both
electrophilic and nucleophilic substitutions can be predicted
using the HughesIngold rules for ionic liquids. The same rules
show that the rate of reaction would be increased by using the
ionic liquids [11].
Second, the nitric acid system can be thought to be a molecular
nitrating agent. We propose that a self-catalytic reaction occurs as
shown (Fig. 2). The compound may be a nitronium ion carrier,
which could not dissociate before reacting with aromatic
compounds. The absorbance of nitronium ion could not be found
by Raman spectroscopy in the mixture of nitric acid and TSILs.
There is an additional consideration, based on the properties of
the ionic liquid cations andanions. The TSILs used in this work have
structures similar to those of tetrabutyl ammonium bromide
(TBAB) or tetrabutyl ammonium chloride (TBAC), so they could be
used as phase transfer catalysts [21]. It should facilitate the better
solvation of a charged intermediate electrophilic species, NO
2
+
-
carrier, in the charged more highly polar TSILs. [TBPSA][HSO
4
] gave
a higher rate enhancement than the others. It is possible that the
lipophilicity of the TSILs increases as the length of alkyl chain
increases; the solubility values of the TSILs in aromatic compounds
would increase as the lipophilicity increases and would prompt the
nitration reaction.
It is important that the TSILs contain no aromatic rings, thus
they are superior to imidazolium cation-based ionic liquids,
because the imidazolium core itself can be nitrated in competition
in some cases. Within the literature, the nitration of imidazolium
salts is often reported [7,9]. Therefore, the concentrated nitric acid
(>68%) and the other nitrating agents (not suitable to imidazolium
salts) might be promising in this procedure, and further work is
underway.
Table 5
Result for nitration of substituted benzenes with different TSILs
a
Entry R TSILs T (8C) Yield (%)
b
Product isomers (%)
c
para/ortho
d
ortho meta para
1 H [TMPSA][HSO
4
] 70 62 n/a
e
2 H [TEPSA][HSO
4
] 70 62 n/a
e
3 H [TBPSA][HSO
4
] 70 66 n/a
e
4 H [TMBSA][HSO
4
] 70 63 n/a
e
5 H [TEBSA][HSO
4
] 70 63 n/a
e
6 Me [TMPSA][HSO
4
] 60 82 57.0 5.5 37.5 0.66
7 Me [TEPSA][HSO
4
] 60 85 56.0 6.0 38.0 0.68
8 Me [TBPSA][HSO
4
] 60 88 55.3 5.5 39.2 0.71
9 Me [TMBSA][HSO
4
] 60 84 56.9 5.6 37.5 0.66
10 Me [TEBSA][HSO
4
] 60 85 56.0 5.5 38.5 0.66
11 Me None 60 67 58.3 5.5 36.2 0.62
12 Et [TMPSA][HSO
4
] 60 65 44.1 2.0 53.9 1.2
13 Et [TEPSA][HSO
4
] 60 67 44.0 2.0 54.0 1.2
14 Et [TBPSA][HSO
4
] 60 72 42.6 2.0 55.4 1.3
15 Et [TMBSA][HSO
4
] 60 70 44.1 2.2 53.7 1.2
16 Et [TEBSA][HSO
4
] 60 75 42.5 2.0 55.5 1.3
17 t-Bu [TMPSA][HSO
4
] 60 82 10.4 6.0 83.6 8.0
18 t-Bu [TEPSA][HSO
4
] 60 82 10.3 6.2 83.5 8.1
19 t-Bu [TBPSA][HSO
4
] 60 85 9.8 6.5 83.7 8.5
20 t-Bu [TMBSA][HSO
4
] 60 82 10.3 6.1 83.6 8.0
21 t-Bu [TEBSA][HSO
4
] 60 86 10.2 6.4 83.4 8.2
22 NO
2
[TBPSA][HSO
4
] 80 0 n/a
d
a
Reaction conditions: 20 mmol aromatic compounds, 60 mmol 68% nitric acid, TSILs 0.4 mmol.
b
Based on crude product.
c
By quantitative GC analysis and qualitative GC/MS.
d
Ratio of para/ortho calculated from original GC data.
e
No isomer was detected.
Fig. 2. Formation of nitronium ion carrier.
D. Fang et al. / Applied Catalysis A: General 345 (2008) 158163 161
The recycling performance of [TBPSA][HSO
4
] was investigated
by the nitration of chlorobenzene with nitric acid under the
identical conditions (Table 3). As the data listed in Table 6 show
that [TBPSA][HSO
4
] could be reused for at least ve times without
noticeable lowering of the catalytic activity. The reaction still
provided a reasonable yield and the same selectivity as initially. It
should be noted that it is very difcult to separate the catalyst from
the reaction system after reaction since it is miscible with nitric
acid. Therefore, if it were reused in the way as described in the
reference, the conversion of aromatic compound should decrease.
Hence, the separation of [TBPSA][HSO
4
] was also explored here. It
was found that there were mainly three methods to recover the
[TBPSA][HSO
4
]: distillation under vacuum; extraction with cyclo-
hexane or ethers; the last and the most efcient, steamdistillation.
For environmental protecting and economic reasons and compar-
ison with recycling of the traditional catalysts used in nitration,
easy recycling performance is an attractive property of the TSILs.
3. Conclusion
In summary, the utility of ionic liquids for electrophilic nitration
of aromatic compounds has been explored. Some novel SO
3
H-
functional Brnsted acidic TSILs that bear an alkane sulfonic acid
group in an acyclic trialkanylammonium cation are quite promis-
ing. The present systems do not require mixed acids, they offer
simple work up procedures and the only by-product is water.
Relatively simple operations have been devised to regenerate and
recycle the ionic liquids.
4. Experimental
4.1. General
Melting points were measured with a X
6
-Data microscopic
apparatus and were reported uncorrected. IR spectra were
obtained with a Nicolete spectrometer and are expressed in
cm
1
(KBr).
1
H NMR spectra were recorded on Bruker DRX300
(300 MHz) and Bruker DRX500 (500 MHz) spectrometers.
13
C NMR
spectra were recorded on a Bruker DRX300 (75.5 MHz) spectro-
meter. All signals were expressed as ppm downeld from
tetramethylsilane, used as an internal standard. Mass spectra
were obtained with an automated FININIGAN Trace Ultra-Trace
DSQ GC/MS spectrometer or a FININIGAN TSQ QUANTUM ULTRA
AM (Thermal) LC/MS spectrometer. The compositions of the
nitration products were analyzed using a gas chromatograph
(Agilent GC-6820) equipped with a 30 m 0.32 mm 0.5 mmHP-
Innowax capillary column and a ame ionization detector or using
a Waters 600E/2487 HPLC. All chemicals (AR grade) were
commercially available and were used without further purica-
tion.
4.2. Synthesis of SO
3
H-functional halogen-free acidic ionic liquids
(TSILs)
All used acyclic SO
3
H-functionalized halogen-free acidic ionic
liquids were synthesized according to our previous methods [18].
The TSILs was analyzed by
1
H NMR,
13
C NMR and MS spectro-
scopes, and the spectral data agreed with their structures (Fig. 1).
4.2.1. N,N,N-Trimethyl-N-propanesulfonic acid ammonium hydrogen
sulfate [TMPSA][HSO
4
]
1
HNMR (300 MHz, D
2
O): d ppm3.22 (t, J = 7.2 Hz, 2H, NCH
2

), 2.90 (s, 9H, CH

3
), 2.73 (t, J = 7.8 Hz, 2H, CH
2
SO
3
), 1.99 (m, 2H,
CH
2
).
13
C NMR (D
2
O): d 65.00, 52.51, 47.89, 18.85. MS (m/z):
279.05 (M
+
), 182.14 (100).
4.2.2. N,N,N-Triethyl-N-propanesulfonic acid ammonium hydrogen
sulfate [TEPSA][HSO
4
]
1
H NMR (300 MHz, D
2
O): d ppm 3.223.05 (m, 8H, (6H + 2H),
N CH
2
CH
3
, NCH
2
C
2
H
4
), 2.85 (t, J = 7.2 Hz, 2H, CH
2
SO
3
),
1.97 (m, 2H, CH
2
), 1.12 (t, 9H, CH
3
).
13
C NMR (75.5 MHz, D
2
O): d
ppm 56.00, 52.95, 48.34, 18.93, 8.04. MS (m/z): 321.05 (M
+
),
322.05, 320.15, 194.05 (100).
4.2.3. N,N,N-Tributhyl-N-propanesulfonic acid ammonium hydrogen
sulfate [TBPSA][HSO
4
]
1
HNMR (500 MHz, D
2
O): d ppm3.28 (t, 2H, J = 4.0 Hz, NCH
2

), 3.13 (t, 6H, J = 8.5 Hz, NCH

2
), 2.85 (t, 2H, J = 7.0 Hz, CH
2

SO
3
), 2.03 (m, 2H, CH
2
CH
2
CH
2
), 1.56 (m, 6H, CH
2
CH
2
CH
3
),
1.27 (m, 6H, CH
2
CH
3
), 0.84 (t, 9H, J = 7.5 Hz, CH
3
).
13
C NMR
(300 MHz, D
2
O): d ppm 58.49, 50.66, 48.42, 23.93, 20.36, 19.16,
14.46. MS (m/z): 405.29 (M
+
), 406.28, 404.28 (100).
4.2.4. N,N,N-Trimethyl-N-butanesulfonic acid ammonium hydrogen
sulfate [TMBSA][HSO
4
]
1
HNMR (300 MHz, D
2
O): d ppm3.24 (t, J = 8.4 Hz, 2H, NCH
2

), 2.99 (s, 9H, CH

3
), 2.85 (t, J = 7.5 Hz, 2H, CH
2
SO
3
), 1.82 (m, 2H,
CH
2
), 1.70 (m, 2H, CH
2
).
13
C NMR (D
2
O): d ppm 66.15, 53.16,
50.31, 21.46, 19.93. MS (m/z): 293.36 (M
+
), 196.39 (100).
4.2.5. N,N,N-Triethyl-N-butanesulfonic acid ammonium hydrogen
sulfate [TEBSA][HSO
4
]
1
HNMR (300 MHz, D
2
O): d ppm3.15 (q, J = 7.2 Hz, 6H, NCH
2

CH
3
), 3.07 (t, J = 8.4 Hz, 2H, NCH
2
C
3
H
6
SO
3
), 2.82 (t, J = 7.2 Hz,
2H, CH
2
SO
3
), 1.68 (m, 4H, C
2
H
4
CH
2
SO
3
), 1.11 (m, J = 7.2 Hz,
9H, CH
3
).
13
C NMR (D
2
O,): d ppm56.21, 52.85, 50.32, 21.50, 20.20,
6.90. MS (m/z): 335.35 (M
+
), 208.36 (100).
4.3. UVvis acidity evaluation
Dichloromethane solutions of these TSILs were prepared from
dried CH
2
Cl
2
and TSILs that have been treated under vacuum at
80 8C for 6 h. All the spectra were recorded with a UVvis
spectrophotometer.
4.4. Typical nitration procedure
Weighed amounts of aromatic compound, 68% nitric acid, and
TSIL were charged successively into a ask with a reex condenser
(Scheme 1). The nitration reaction was typically allowed to
proceed for a length of time with vigorous stirring and heating at
the desired temperature (monitored by GC). After the reaction, the
system became biphasic once the stirring was discontinued. The
Table 6
Reuse of [TBPSA][HSO
4
] in the nitration of chlorobenzene
a
Runs Yield (%)
b
Product isomers (%)
c
para/ortho
d
ortho meta para
Fresh 65 22.2 0.3 77.5 3.5
1 46 24.1 0.7 75.2 3.1
2 52 23.6 0.7 75.7 3.2
3 65 22.2 0.3 77.5 3.5
4 53 23.4 0.4 76.2 3.1
5 55 23.2 0.6 76.2 3.3
a
Reaction conditions: 20 mmol chlorobenzy, 60 mmol 68% nitric acid, TSILs
0.4 mmol, 10 h.
b
Based on crude product.
c
By quantitative GC analysis and qualitative GC/MS.
d
Ratio of para/ortho calculated from original GC data.
D. Fang et al. / Applied Catalysis A: General 345 (2008) 158163 162
organic phase contained the expected product, that was isolated by
simple decantation from the aqueous system, washed with water,
and then analyzed by GC or HPLC. The TSIL could be recovered by
steam distillation.
Acknowledgment
This work was nancially supported by the Chinese Commis-
sion of Science, Technology & Industry for National Defense.
References
[1] G.A. Olah, R. Malhotra, S.C. Narang, Nitration, Methods and Mechanisms, VCH,
New York, 1989.
[2] N. Ono, The Nitro Group in Organic Synthesis, Wiley-VCH, New York, 2001.
[3] A.G.M. Barrett, D.C. Braddock, R. Ducray, R.M. McKinnell, F.J. Waller, Synlett.
(2000) 5758.
[4] M. Shi, S. Cui, Chem. Commun. (2002) 994995.
[5] M. Shi, S. Cui, Adv. Synth. Catal. 345 (2003) 13291333.
[6] G.A. Olah, R. Malhotra, S.C. Narang, J. Org. Chem. 43 (1978) 46284630.
[7] B. Gigante, A.O. Prazeres, M.J. Marcelo-Curto, J. Org. Chem. 60 (1995) 34453447.
[8] S.P. Dagade, S.B. Waghmode, V.S. Kadam, M.K. Dongare, Appl. Catal. A: Gen. 226
(2002) 4961.
[9] K.K. Laali, V.J. Gettwert, J. Org. Chem. 66 (2001) 3540.
[10] R. Rajagopal, K.V. Srinivasan, Synth. Commun. 33 (2003) 961966.
[11] N.L. Lancaster, V. Liopis-Mestre, Chem. Commun. (2003) 28122813.
[12] K. Smith, S. Liu, G.A. El-Hiti, Ind. Eng. Chem. Res. 44 (2005) 86118615.
[13] J.S. Wilkes, J. Mol. Catal. A: Chem. 214 (2004) 1117.
[14] A.C. Cole, J.L. Jensen, I. Ntai, K.L.T. Tran, K.J. Weaver, D.C. Forbes, J.H. Davis Jr., J.
Am. Chem. Soc. 124 (2002) 59625963.
[15] P. Wasserscheid, R. Hal, A. Bo smann, Green Chem. 4 (2002) 400404.
[16] M.T. Garcia, N. Gathergood, P.J. Scammells, Green Chem. 7 (2005) 914.
[17] K. Qiao, H. Hagiwara, C. Yokoyama, J. Mol. Catal. A: Chem. 246 (2006) 6569.
[18] D. Fang, X. Zhou, Z. Ye, Z. Liu, Ind. Eng. Chem. Res. 45 (2006) 79827984.
[19] D. Fang, J. Luo, X. Zhou, Z. Ye, Z. Liu, J. Mol. Catal. A: Chem. 274 (2007) 208211.
[20] D. Fang, Q. Shi, K. Gong, Z. Liu, C.X. Lv, Chin. J. Energetic Mater. 15 (2007) 122124.
[21] J.P. Jayachandran, M.L. Wang, Synth. Commun. 33 (2003) 24632468.
D. Fang et al. / Applied Catalysis A: General 345 (2008) 158163 163