Selective reduction of nitroarenes with molybdenum disulfide

Article abstract of DOI:10.1002/cjoc.201300310

Commercial MoS₂ was found to be a highly selective catalyst for the reduction of nitrobenzenes to the corresponding anilines with hydrazine under mild conditions. MoS₂ is not only much cheaper, but also more selective than noble metal catalysts for the reduction of functional nitrobenzenes to the corresponding anilines. Nitrobenzenes with halides (F, Cl, Br and I) were reduced selectively, and the corresponding anilines were obtained in excellent yields, and no dehalogenation was detected. Functional groups such as NH₂, OH, alkene groups were tolerated during the reduction of the nitro compounds. The reduction of p-chloronitrobenzene was studied over MoS₂ and Pd/C respectively with hydrazine. The yield of p-chloroaniline was much higher with MoS₂ than that with Pd/C at full conversion. MoS₂ was used as a catalyst for the reduction of nitrobenzene under mild conditions. Nitroarenes with halides (F, Cl, Br and I) were reduced selectively without dehaloganation, and functional groups such as NH₂, OH, alkene groups were tolerated during the reduction of the nitro compounds. The reduction of p-chloronitrobenzene was studied over MoS ₂ and Pd/C respectively with hydrazine. p-Chloroaniline was obtained quantitively with MoS₂, but some aniline formed by dehaloganation with Pd/C. Copyright

Full text of DOI:10.1002/cjoc.201300310

COMMUNICATION
DOI: 10.1002/cjoc.201300310
Selective Reduction of Nitroarenes with Molybdenum Disulfide
Lei Huang, Pingfei Luo, Man Xiong, Rizhi Chen, Yong Wang, Weihong Xing, and Jun Huang*
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineer-
ing, Nanjing University of Technology, Nanjing, Jiangsu 210009, China
Commercial MoS
sponding anilines with hydrazine under mild conditions. MoS
2
was found to be a highly selective catalyst for the reduction of nitrobenzenes to the corre-
is not only much cheaper, but also more selective
2
than noble metal catalysts for the reduction of functional nitrobenzenes to the corresponding anilines. Nitrobenzenes
with halides (F, Cl, Br and I) were reduced selectively, and the corresponding anilines were obtained in excellent
yields, and no dehalogenation was detected. Functional groups such as NH , OH, alkene groups were tolerated dur-
2
ing the reduction of the nitro compounds. The reduction of p-chloronitrobenzene was studied over MoS and Pd/C
2
respectively with hydrazine. The yield of p-chloroaniline was much higher with MoS than that with Pd/C at full
2
conversion.
Keywords anilines, reduction, molybdenum disulfide, nitrobenzenes
[
10]
Introduction
respectively.
Molybdenum disulfide was used widely as hydro-
treating catalyst in the early twentieth century, as it was
Aromatic amines are important intermediates for the
production of fine chemicals, pharmaceutical and agri-
[11]
much cheaper than noble metal catalysts. Afterwards,
[
1]
cultural products. The traditional synthesis routes
based on iron and hydrogen chloride (Bechamp reaction)
are not environmental benign because of the low selec-
tivity of the target amine and the emission of large
[12]
it was studied extensively in CO reduction and the
[13]
hydrodesulfurization processes for the production of
clean fuels. Molybdenum disulfide used as catalyst for
the reduction nitrobenzenes is rare. Sun et al. reported
[2]
amount of toxic waste. The alternative approach was
Zr-intercalated MoS for the reduction of nitrobenzene,
2
[
3]
the catalytic hydrogenation by transition metal (Pt,
[14]
but the activity was not high enough. Recently, Ruiz
[
4]
[5]
[6]
[7]
2
Pd, Ru, Au, Ni ) catalysts with H , which shows
reported the reduction of 2-methoxyphenol based on
[
15]
high activity and good selectivity for the reduction of
the nitrobenzene. However, the selectivity of the corre-
sponding amine was not high enough, especially when
other reducible groups are present in the same mole-
cules. For example, when halides such as F, Cl, Br and I
were in the nitroarenes, dehalogenation was always the
side-reaction for the reduction of nitroarenes with tran-
sition metal catalysts. Moreover, the selective reduction
of a nitro group is also a challenge when alkene groups
are present in the same molecules. Cardenas-Lizana
et al. reported the hydrogenation of functional nitro-
benzenes over supported Au and Ag, and excellent se-
lectivity was achieved at a continuous gas phase reac-
MoS2.
Moreover, Beller group reported a homoge-
neous catalyst based on Mo S cluster, which was
3
4
[
16]
highly selective for the reduction of nitrobenzenes.
Herein, we reported that MoS was used as a highly
2
selective catalyst for the reduction of nitrobenzenes with
hydrazine under mild conditions. When halides such as
F, Cl, Br and I were present in the nitrobenzenes, the
corresponding anilines were obtained in quantitative
yield and no dehalogenation happened. Functional
groups such as NH , OH and alkene groups were toler-
2
ated during the reduction of the nitrobenzenes. It is
highly favourable to use MoS instead of the noble
2
metal catalysts, as MoS is much cheaper than noble
2
[8]
tor. In addition, other hydrogen sources (such as
HCOOH, HCOONH , PhSiH , H NNH , H O) were
applied for the catalytic hydrogenation of nitro com-
metal catalysts. Furthermore the selectivity was much
higher than noble metal catalysts for the reduction of
NO group to NH group, especially for the reduction of
4
3
2
2
2
2
2
[9]
pounds, and high selectivity was obtained. Recently,
we have reported Pt and Rh nanocatalysts for the selec-
nitrobenzenes with halides, since the dehalogenation
side-reaction was hard to avoid with noble metal cata-
lysts.
2
tive reduction of nitrobenzenes with H and hydrazine
*
E-mail: junhuang@njut.edu.cn; Tel.: 0086-025-83172276; Fax: 0086-025-83172261
Received April 14, 2013; accepted June 5, 2013; published online XXXX, 2013.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201300310 or from the author.
Chin. J. Chem. 2013, XX, 1—5
© 2013 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1

Huang et al.
COMMUNICATION
Experimental
reaction required longer time (Table 1, Entry 10).
Reagents and analytical methods
All reagents were purchased from Aladdin Reagent
Company, Sigma-Aldrich Company and Alfa-Aesar
Company without further purification.
Gas chromatography analyses were performed on a
Hewlett Packard 5890 instrument with a FID detector
and Hewlett Packard 24 m×0.2 mm i.d. HP-5 capillary
column. The specific surface areas and the average pore
sizes of the materials were measured on a Belsorp II
physical adsorption apparatus by BET and BJH meth-
ods.
ADS
DES
2
1
0
0
0
0
.0
0.2
0.4
0.6
0.8
1.0
Relative pressure (p/p0)
Reduction of nitrobenzenes
Typical procedure for the reduction of nitrobenzenes
with hydrazine: The schlenk tube with a stir bar was
flushed with Ar more than three times to remove the air,
and filled with Ar. Then, nitrobenzene (1.0 mmol), hy-
Figure 1 Nitrogen adsorption-desorption isotherms of MoS2.
Table 1 MoS
2
catalyzed reduction of nitrobenzene to aniline
a
with hydrazine
2
drazine monohydrate (3.0 mmol), MoS (0.1 mmol, 16
mg) and toluene (2.0 mL) were added into the tube. Af-
NO2
NH2
ter the tube was closed, the reaction was kept at 25－80
℃
for a desired time with continuously stirring. After
the reaction was completed, 100 μL of C16
added to the reaction mixture. The MoS catalyst was
Entry
Solvent
Toluene
THF
(Conv./Yield)/%
100/＞99
100/95
H34 was
1
2
3
4
5
6
7
2
filtrated off and washed with ethanol (2.0 mL×3). The
products (in the filtrate mixture) were analyzed by GC.
All prepared anilines are commercially available and
identified by comparison (GC/MS) with authentic sam-
ples (purchased from Aladdin Reagent, Alfa-Aesar and
Sigma-Aldrich Company). The Pd/C (16 mg, Pd: 5
wt%)catalysed hydrogenation of nitrochlorobenzene
with hydrazine was performed in a similar way.
H
2
O
97/88
Cyclohexane
Ethanol
100/＞99
100/75
1,4-Dioxane
Solvent free
Toluene
100/42
100/96
b
8
0/0
c
9
Toluene
0/0
Reusability of the MoS
2
d
1
0
Toluene
100/＞99
When the reaction was completed and the reaction
mixture was cooled, the catalyst was collected by filtra-
tion. The catalyst was washed by ethanol (2.0 mL×3)
and dried under vacuum at 25 ℃ for 12 h, and then
used again for the next reaction cycle.
a
Reaction conditions: nitrobenzene, 1.0 mmol; MoS
2
, 0.1 mmol,
1
6 mg; N H •H O, 3.0 mmol; 60 ℃; in 3 h; 2.0 mL solvent. The
2
4
2
conversions and yields were determined by GC (C H used as
internal standard). 1.0 atm H was used as reducer. Without
catalyst. Nitrobenzene, 10 mmol; MoS , 0.1 mmol, 16 mg;
1
6
34
c
b
2
d
2
N H •H O, 30 mmol; 60 ℃; 12 h.
2
4
2
Results and Discussion
The reusability of the MoS
the results are shown in Table 2. The MoS
easily recycled by filtration and reused for the next re-
action cycle. The MoS can be reused at least 8 times
2
catalyst was tested and
On the basis of the nitrogen adsorption-desorption
2
catalyst was
analysis, the BET surface areas of MoS
Figure 1).
The reduction of nitrobenzene with hydrazine was
performed as a model reaction, and the results are listed
in Table 1. Toluene, THF, H O, cyclohexane (Table 1,
2
was 4 m /g
2
(
2
without loss of activity (Table 2).
2
Entry 1－4) were good solvents, and aniline could be
obtained in good yield. But, ethanol and 1,4-dioxane
Table 2 The reusability of the MoS for the reduction of nitro-
benzene
2
a
(
Table 1, Entry 5－6) were less effective solvents for
Recycled
1
2
3
4
5
6
7
8
the transformation. The reduction of nitrobenzene af-
forded aniline in good yield also without solvent (Table
Conv./% 100 100 100 100 100 100 100 100
Yield/%
＞99 ＞99 ＞99 ＞99 ＞99 ＞99 ＞99 ＞99
, 0.1 mmol,
O, 3.0 mmol; 60 ℃; in 3 h; 2.0 mL toluene as
solvent. The conversions and yields were determined by GC
34 used as internal standard).
1
, Entry 7). No aniline was obtained when H
as reducer or without MoS catalyst (Table 1, Entry 8,
). When the reaction was scaled up to 10 times (10
mmol nitrobenzene) with low catalyst loading (1 mol%
2
was used
a
Reaction conditions: nitrobenzene, 1.0 mmol; MoS
•H
2
2
9
16 mg; N
2
H
4
2
MoS
2
), aniline was obtained quantitatively also, but the
(C16
H
2
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© 2013 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2013, XX, 1—5

Selective Reduction of Nitroarenes with Molybdenum Disulfide
The reduction of various functional nitroarenes was
studied with hydrazine, and the results are summarized
in Table 3. For the hydrogenation of nitro aromatics
14), which facilitated the industrial design of the selec-
tive hydrogenation processes.
2
with halides (F, Cl, Br and I), the MoS catalyst showed
1
0
0
0
.0
.8
.6
.4
excellent activity and selectivity. The corresponding
anilines were obtained in excellent yield, and no aniline
was observed, which indicated no dehalogenation oc-
p-chloroaniline
p-chloronitrobenzene
curred (Table 3, Entries 1－7). OH and NH
2
groups
were also tolerated during the hydrogenation of NO
2
,
and the corresponding anilines were obtained in good
yields (Table 3, Entries 8－11). The 2,6-dimethylnitro-
benzene was hydrogenated to 2,6-dimethylaniline in
good yield also (Table 3, Entry 12). Moreover, the hy-
drogenation of 3-nitrostyrene gave 3-aminestyrene
quantitatively (Table 3, Entry 13).
0.2
0.0
0
20 40 60 80 100 120 140 160 180
Time/min
Table 3 MoS
with hydrazine
2
catalyzed reduction of substituted nitroarenes
a
Figure 2 MoS catalyzed hydrogenation of p-chloronitroben-
2
zene with N H •H O. Reaction conditions: p-chloronitrobenzene,
2
4
2
H NNH2
2
NO2
NH2
1.0 mmol; MoS catalyst, 16 mg; N H •H O, 3.0 mmol; at 25 ℃;
2
2
4
2
R
R
2
.0 mL toluene as solvent.
Entry
R
Time/h
(Conv./Yield)/%
100/＞99
1
2
3
4
5
6
2-F
4-F
2-Cl
3-Cl
4-Cl
2-Br
3-I
3
2
To compare MoS catalyst with the commercial
3
100/＞99
catalyst (Pd/C Pd: 5.0 wt%), we performed the Pd/C
catalyzed hydrogenation of p-chloronitrobenzene with
hydrazine monohydrate under similar reaction condi-
tions, and the results are shown in Figure 3. From Fig-
ure 3, we can see that the comsumption of p-chloro-
3
100/＞99
3
100/＞99
f
3
100/＞99 (98 )
3
100/＞99
100/＞99
100/＞99
100/＞99
100/＞99
nitrobenzene was faster with Pd/C than that with MoS
but the selectivity of p-chloroaniline was low, and the
hydrogenation of the NO was always accompanied
2
,
b
7
24
10
10
6
8
9
2-NH2
4-NH2
3-OH
2
with the dechlorination during the reaction process. In
the end, p-chloroaniline and aniline were obtained in
1
1
1
1
0
1
2
3
4
7
5% yield and 25% yield respectively at full conversion
f
4-OH
6
100/＞99 (＞99 )
of p-chloronitrobenzene with Pd/C catalyst. The selec-
b
c
d
2,6-CH3
3-C＝C
4-Cl
24
6
100/＞99
100/＞99
100/＞99
tivity with MoS was much better than that with Pd/C
2
catalyst. High selectivity was highly desirable for mod-
ern chemical industry, which may simplify the product
separation, avoid waste disposal and develop greener
processes.
1
10
a
Reaction conditions: nitrobenzene, 1.0 mmol; MoS
2
, 0.1 mmol,
1
6 mg; 60 ℃; N H •H O, 3.0 mmol. The conversions and yields
2
4
2
b
were determined by GC (C H used as internal standard). 80
℃
f
1
6
34
c
d
1.0
, N H •H O, 5.0 mmol used. 3-Vinylaniline yield. At 25 ℃.
2
4
2
Isolated yield.
0.8
2
In addition, the MoS catalysed hydrogenation proc-
ess of p-chloronitrobenzene with hydrazine monohy-
drate was investigated, and the results are shown in
0.6
0.4
aniline
Figure 2. The NO
2
was reduced smoothly to NH
2
with
p-Chloroaniline
p-chloronitrobenzene
MoS catalyst, and no side-reaction (dechlorination)
2
was found. All the p-chloronitrobenzene was converted
to p-chloroaniline in 100% yield in 3 h, and no aniline
was observed. It is important to test the selectivity of
catalysts under harsher conditions (longer reaction time
and higher reaction temperature), as it is not easy to
control the reaction conditions in large scale processes.
It is found that the dechlorination will not occur with
0
.2
.0
0
0
20 40 60 80 100 120 140 160 180
Time/min
Figure 3 Pd/C catalyzed hydrogenation of p-chloronitroben-
zene with N H •H O. Reaction conditions: p-chloronitrobenzene,
2
4
2
MoS
2
catalyst even in longer reaction time (10 h) or at
1.0 mmol; Pd/C catalyst (Pd: 5.0 wt%), 16 mg; N H •H O, 3.0
2 4 2
higher reaction temperature (60 ℃) (Table 3, Entries 5,
mmol; at 25 ℃; 2.0 mL toluene as solvent.
Chin. J. Chem. 2013, XX, 1—5
© 2013 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
3

Huang et al.
COMMUNICATION
Hydrazine is a good reducer, but H
2
gas is nearly not
Development Program of China (No. 2012AA03A606),
Foundation from State Key Laboratory of Materi-
als-Oriented Chemical Engineering (Nos. ZK201003,
ZK201011), and Graduate Education Innovation Project
in Jiangsu Province (No. CXZZ12_0447).
an effective reducer for the reduction of nitrobenzene to
aniline (Table 1, Entry 8), which indicated that the con-
densation of nitro group with hydrazine is preferentially
happened. Mo is the key element of nitrogenase in
[
17]
plants for the fixation of N2 and the important cata-
[
18]
lytic center for the synthesis of NH from N and H .
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2
2
N N
MoS2
O
H2NNH2
N
N
N
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O
O
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N N
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Conclusions
In summary, we demonstrated MoS
2
catalyst re-
duced nitroarenes efficiently and selectively into corre-
sponding anilines with hydrazine monohydrate under
mild conditions. To the hydrogenation of substituted
nitrobenzenes, nitroarenes with halides (F, Cl, Br and I)
were reduced selectively, and the corresponding anilines
were obtained in excellent yields, none of aniline was
observed. Functional groups such as NH , OH, alkene
2
groups were tolerated during the hydrogenation of the
nitro compounds, and the corresponding anilines were
obtained in good yields. The MoS
lyst in the hydrogenation of p-chloronitrobenzene, and
00% selective reduction of NO group was achieved at
complete conversion of the nitroarene. In contrast, Pd/C
5 wt%), used as a benchmark catalyst, was nonselective
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Acknowledgement
This work was supported by the National Natural
Science of Foundation of China (Nos. 21136005,
1125629), the National High Technology Research and
2
4
www.cjc.wiley-vch.de
© 2013 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2013, XX, 1—5

Selective Reduction of Nitroarenes with Molybdenum Disulfide
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