Synthesis and characterization of magnetically nanoparticles of Fe3O4@APTMS@ZrCp2 as a novel and reusable catalyst for convenient reduction of nitro compounds with glycerol

Article abstract of DOI:10.1007/s13738-017-1199-5

The present paper describes the synthesis of magnetically nanoparticles of zirconocene-modified magnetite, Fe₃O₄@APTMS@ZrCp₂, as a new generation in heterogeneous and reusable type nanocatalysts. The prepared zirconocene nanocomposite was characterized using FT-IR, SEM, XRD, EDX, AGFM, ICP–OES, TGA and BET analyses. The core–shell nanocatalyst exhibited an excellent catalytic activity towards glycerol reduction of various nitro compounds to the corresponding amines. All reactions were carried out in H₂O at room temperature (40–90?min) to afford amines in high to excellent yields. Reusability of the core–shell zirconocene was examined 5 times without significant loss of its catalytic activity.

Full text of DOI:10.1007/s13738-017-1199-5

J IRAN CHEM SOC
DOI 10.1007/s13738-017-1199-5
ORIGINAL PAPER
Synthesis and characterization of magnetically nanoparticles
of Fe3O4@APTMS@ZrCp2 as a novel and reusable catalyst
for convenient reduction of nitro compounds with glycerol
Behzad Zeynizadeh1 · Farhad Sepehraddin1
Received: 5 March 2017 / Accepted: 12 September 2017
© Iranian Chemical Society 2017
Abstract The present paper describes the synthesis of
magnetically nanoparticles of zirconocene-modifed mag-
netite, Fe3O4@APTMS@ZrCp2, as a new generation in
heterogeneous and reusable type nanocatalysts. The pre-
pared zirconocene nanocomposite was characterized using
FT-IR, SEM, XRD, EDX, AGFM, ICP–OES, TGA and BET
analyses. The core–shell nanocatalyst exhibited an excel-
lent catalytic activity towards glycerol reduction of various
nitro compounds to the corresponding amines. All reactions
were carried out in H2O at room temperature (40–90 min)
to aford amines in high to excellent yields. Reusability of
the core–shell zirconocene was examined 5 times without
signifcant loss of its catalytic activity.
reducing agents such as NaBH4, H2, hydrazine, formic acid
(formats), alcohols and the others, reduction with hydrogen
transferring agents is safer, highly selective and eco-friendly
[9].
Recently, glycerol because of the signifcant physical
and chemical properties such as polarity, low toxicity, high
boiling point, biodegradability, non-fammability [10] and
ability to dissolve inorganic salts, acids, bases and metal
complexes as well as organic compounds is considered as
an important biomass derived material [11, 12]. It is easily
prepared as a by-product of biodiesel manufactures [13] and
also is derived from sugars or sugar alcohols [14]. Nowa-
days, using glycerol as a green hydrogen transferring agent
has attracted a great deal of attention in organic synthesis
[15–18].
Keywords Amines · Cp2ZrCl2 · Fe3O4 · Glycerol · Nitro
compounds · Reduction
There is also an ever increasing interest in synthesis,
characterization, surface modifcation and application of
magnetically nanoparticles (MNPs). They have large sur-
face area, and are easily prepared or functionalized. Simple
separation and the frequent reusability as well as low toxicity
are the prominent characteristics of magnetically nanoparti-
cles [19–21]. In addition, MNPs because of many hydroxyl
groups on their surfaces have emerged as efcient alternative
supports for deposition of homogeneous catalysts [22].
In line with the outlined strategies and continuation of
our research program directed to the preparation and appli-
cation of deposited copper hydroxide on magnetite [23],
herein, we wish to report the synthesis and characterization
of Fe3O4@APTMS@ZrCp2 as a novel, heterogeneous and
reusable magnetically nanoparticles for the efcient reduc-
tion of aromatic and aliphatic nitro compounds to the cor-
responding amines with glycerol in H2O.
Introduction
Reduction of nitro compounds is one of the most useful and
straightforward methods for the preparation of amines. The
amine synthesis is important from academic and industrial
points of view. They are used frequently in the preparation
of dyes, biologically active compounds, pharmaceuticals,
rubber chemicals and photographic/agricultural chemicals
[1–4]. During the last decades, numerous methods as well
as reducing agents have been documented for reduction of
nitro compounds to amines [5–8]. In this context and among
* Behzad Zeynizadeh
bzeynizadeh@gmail.com
1
Faculty of Chemistry, Urmia University, Urmia 5756151818,
Iran
Vol.:(0123456789)
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J IRAN CHEM SOC
difraction (XRD), energy-dispersive X-ray spectroscopy
(EDX), alternating gradient force magnetometry (AGFM),
inductively coupled plasma-optical emission spectrom-
etry (ICP–OES), thermogravimetric analysis (TGA) and
Brunauer–Emmett–Teller (BET) analyses.
Results and discussion
Synthesis and characterization of Fe3O4@APTMS@
ZrCp2 MNPs
Figure 1 shows the recorded FT-IR spectra for (a)
Fe3O4, (b) Fe3O4@APTMS and (c) Fe3O4@APTMS@
ZrCp2 MNPs. The spectrum for bare Fe3O4 shows the
bands of 440 and 590 cm−1 for stretching vibration of FeO,
and a broad band at 3370 cm−1 for surface OH groups.
In the case of Fe3O4@APTMS, the peaks at 1040, 3450
and 2900 cm−1 are attributed to stretching vibration of
SiO, NH and CH (aliphatic), respectively. In addition,
the peak at 1616 cm−1 (spectrum c) belongs to C=C
stretching vibration of Cp groups. All these indicated that
Synthesis of zirconocene-modifed magnetite was carried
out in a three-steps procedure: (a) preparation of nanomag-
netite Fe3O4 by a chemical co-precipitation of FeCl3·6H2O
and FeCl2·4H2O in aqueous ammonia, (b) coating of Fe3O4
NPs with 3-aminopropyltrimethoxysilane (APTMS) and
(c) deposition of Cp2ZrCl2 on Fe3O4@APTMS to aford
Fe3O4@APTMS@ZrCp2 nanoparticles (Scheme 1).
The prepared core–shell nanocomposite was then char-
acterized by Fourier transform infrared spectroscopy
(FT-IR), scanning electron microscopy (SEM), X-ray
OH
OH
HO
HO
HO
HO
OH
NH2OH
N2, 80 oC, 30 min
(a)
+
FeCl2.4H2O
FeCl3.6H2O
OH
OH
Fe3O4
OH
HO
OH
NH2
Si
H2N
Cl Zr Cl
O
O
O
O
Si
(MeO)3Si(CH2)3NH2
O
O
O
O
O
Si
Fe3O4
reflux, n-Hexane, 24 h
NH2
reflux, EtOH, 10 h
O
O
(b)
O
(c)
O
O
O
Si
Si
H2N
H2N
N
H
Zr
Cl
Si
O
O
O
OH
OH
HO
OH
OH
OH
OH
OH
OH
HO
HO
O
O
O
O
H
N
H
N
Fe3O4
Si
O
O
Fe3O4
HO
HO
HO
Si
Zr
HO
O
OH
HO
HO
O
O
Cl
Si
Zr
N
H
Scheme 1 Synthesis of Fe3O4@APTMS@ZrCp2 MNPs
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J IRAN CHEM SOC
The core–shell concept for the prepared nanocomposite
is also demonstrated by TGA analysis. Thermogravimetric
analysis for (a) Fe3O4, (b) Fe3O4@APTMS and (c) Fe3O4@
APTMS@ZrCp2 MNPs shows two weight-losing stages via
heating of nanocomposites (Fig. 5). The frst stage appears at
25–200 °C showing the elimination of crystallization water
or residual solvent, and the second stage (200–800 °C) repre-
sents releasing of silylpropylamine and zirconocene groups.
Physical parameters of nitrogen absorption–desorption
isotherms such as BET surface area (SBET) and total pore
volumes (Vtotal) for Fe3O4 and Fe3O4@APTMS@ZrCp2
MNPs are summarized in Table 1. A comparison shows
that the specifc surface area (SBET) of zirconocene nano-
composite in respect to Fe3O4 was deceased 8.3%. These
results show that the shell capacity of APTMS@ZrCp2 for
absorption of N2 gas is lower than Fe3O4. The plots for N2
absorption–desorption of Fe3O4 and Fe3O4@APTMS@
ZrCp2 MNPs are shown in Fig. 6.
Magnetically nanoparticles are more desirable for mag-
netic separation. Magnetic property of Fe3O4 and Fe3O4@
APTMS@ZrCp2 NPs was investigated at room temperature
by alternating gradient force magnetometer (AGFM). Ms
value (saturation magnetization) for Fe3O4 and Fe3O4@
APTMS@ZrCp2 was 0.13 and 0.095 a.u., respectively. Fig-
ure 7 shows that though Ms value for Fe3O4@APTMS@
ZrCp2 in respect to Fe3O4 was decreased 27%, however, it
was still large enough for magnetic separation.
Fig. 1 FT-IR spectrum of a Fe3O4 b Fe3O4@APTMS and c Fe3O4@
APTMS@ZrCp2 MNPs
silylpropylamine and Cp2Zr fragments were successfully
incorporated into the core of magnetite.
The morphology and size distribution of zirconocene-
modifed magnetite was determined using scanning elec-
tron microscopy (SEM). Figure 2 represents SEM images
of Fe3O4, Fe3O4@APTMS and Fe3O4@APTMS@ZrCp2
MNPs. Image C shows that the zirconocene nanocompos-
ite was made up uniform nanometer particles with diam-
eter of 5–10 nm.
Reduction of nitro compounds with glycerol/Fe3O4@
APTMS@ZrCp2 system
Elemental (Zr, Fe, N, Si, Cl, C and O) composition
of Fe3O4@APTMS@ZrCp2 MNPs was also determined
by energy dispersive X-ray spectroscopy (EDX). Figure 3
shows that all the titled elements are exited in the fnal
nanocomposite. Through the inductively coupled plasma-
optical emission spectrometry (ICP–OES), the amounts of
Fe and Zr in Fe3O4@APTMS@ZrCp2 MNPs were deter-
mined 52.75 and 3.72%, respectively.
After synthesis and characterization of Fe3O4@APTMS@
ZrCp2 MNPs, the catalytic activity of the prepared nanocom-
posite on reducing capability of glycerol towards reduction
of nitroarenes was investigated. In order to optimize reac-
tion conditions, reduction of nitrobenzene with glycerol as a
model reaction was examined under diferent reaction con-
ditions. The illustrated results in Table 2 show that reduc-
tion of nitrobenzene with glycerol in the absence of Fe3O4@
APTMS@ZrCp2 MNPs was not efcient (entry 1). However,
the addition of little amounts of zirconocene-modifed mag-
netite dramatically accelerated the rate of reduction (entries
2‒11). Performing of the titled reaction in various protic
and aprotic solvents exhibited that H2O was the best sol-
vent of choice and using the molar equivalents of 1:2 for
PhNO2:glycerol in the presence of 7 mg Fe3O4@APTMS@
ZrCp2 MNPs is the requirements to complete reduction of
nitrobenzene. Subsequently, aniline was obtained as a sole
product within 40 min at room temperature (Scheme 2)
(entry 3). To discover the potentiality of Fe3O4@APTMS@
ZrCp2 MNPs versus ZrCp2Cl2, we also examined the pro-
moter activity of ZrCp2Cl2 in glycerol reduction of nitroben-
zene in H2O (entry 12). Comparison of the results showed
X-ray diffraction patterns of Fe3O4 and Fe3O4@
APTMS@ZrCp2 MNPs are also shown in Fig. 4. In XRD
pattern of Fe3O4, the peaks at 30.2°, 35.5°, 43.3°, 53.7°,
57.2° and 62.9° are attributed to (220), (311), (400), (422),
(511) and (440) crystal planes of cubic spinal structure
in pure Fe3O4 (JCPDS: 65-3107) [24, 25]. In XRD of
Fe3O4@APTMS@ZrCp2, though the peaks at 35.1°, 41.5°,
50.9°, 63.2°, 67.5° and 74.6° represent the characteristic
pattern of XRD in pure Fe3O4, however, diferences about
4.9°, 6°, 7.6°, 9.5°, 10.3° and 11.7° (2θ angle) in respect
to pure Fe3O4 are observed. It was also reported that the
pattern of XRD in pure Zr has two characteristic peaks at
35.1° and 36.5° (2θ angle) [26]. These peaks in XRD of
zirconocene-modifed magnetite were overlapped with the
peaks of Fe3O4.
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J IRAN CHEM SOC
Fig. 2 SEM image of a Fe3O4 b Fe3O4@APTMS and c Fe3O4@ ▸
APTMS@ZrCp2 MNPs
that ziroconocene-modifed magnetite exhibited a prominent
and reliable activity versus zirconocene dichloride.
The scope and generality of this synthetic protocol was
more studied with the reduction of various aromatic nitro
compounds at the optimized reaction conditions. The sum-
marized results in Table 3 show that reduction of nitroarenes
possessing electron-releasing or withdrawing groups was
successfully carried out with 2 molar equivalents of glycerol
and 7 mg Fe3O4@APTMS@ZrCp2 MNPs within 40–90 min
at room temperature. It is noteworthy that in the case of
nitroarenes having formyl and keto groups, both of nitro and
carbonyl moieties were reduced with the same reactivity.
Subsequently, higher molar equivalents of glycerol and the
nanocomposite were required to complete the reductions.
Capability of glycerol/Fe3O4@APTMS@ZrCp2 system
towards reduction of aliphatic nitro compounds was also
examined by reduction of 1-nitrohexane and 2-nitrohep-
tane with 2 molar equivalents of glycerol and 7 mg Fe3O4@
APTMS@ZrCp2 MNPs in H2O at room temperature. The
results showed that as aromatic nitro compounds, this pro-
tocol was also efcient and the corresponding aliphatic
amines were obtained successfully in 90–92% yields within
45–50 min (Table 2, entries 17 and 18).
The reducing capability of glycerol/Fe3O4@APTMS@
ZrCp2 system for reduction of nitro compounds was high-
lighted by a comparison of the obtained results for current
protocol with those of reported for other systems (Table 4).
Observation of the results shows that in view points of green
reaction conditions, efciency, availability, the kind and
amounts of reducing agent or nanaocatalyst as well as reus-
ability of the catalyst, the present protocol is more efcient
or has a comparable potentiality.
Recycling of Fe3O4@APTMS@ZrCp2 MNPs
For practical purposes, the ability for easy recycling of the
catalyst is highly desirable. This issue was investigated by
examining the reusability of Fe3O4@APTMS@ZrCp2 MNPs
in glycerol reduction of nitrobenzene. After completion of
the reaction, nanoparticles of zirconocene-modifed magnet-
ite were separated from the reaction mixture by an external
magnet and were then washed with EtOAc to remove resid-
ual contaminants. The vessel of reaction was again charged
with fresh nitrobenzene, glycerol and H2O to run the reduc-
tion reaction for a second time. The examinations resulted
that the core–shell MNPs can be reused 5 times without
signifcant loss of its catalytic activity (Fig. 8).
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J IRAN CHEM SOC
Fig. 3 EDX spectrum of Fe3O4@APTMS@ZrCp2 MNPs
Fig. 5 TGA spectrum for a Fe3O4, b Fe3O4@APTMS and c Fe3O4@
APTMS@ZrCp2 MNPs
Table 1 Physical parameters for N2 absorption–desorption isotherms
of Fe3O4 and Fe3O4@APTMS@ZrCp2 MNPs
Sample
SBET (m2/g)
Vtotal (cm3/g)
Fe3O4
88.65
81.32
0.3
0.26
Fe3O4@APTMS@ZrCp2
Fig. 6 N2 absorption–desorption isotherms for Fe3O4 and Fe3O4@
Fig. 4 XRD spectra of a Fe3O4 and b Fe3O4@APTMS@ZrCp2
APTMS@ZrCp2 MNPs
MNPs
XRD, EDX, AGFM, ICP–OES, TGA and BET analyses.
The core–shell zirconocene exhibited an excellent catalytic
activity towards glycerol reduction of various aromatic and
aliphatic nitro compounds. All reactions were carried out in
H2O at room temperature within 40–90 min to aford amines
Conclusions
In this paper, the synthesis of zirconocene-modifed mag-
netite, Fe3O4@APTMS@ZrCp2, was introduced. The pre-
pared nanocomposite was characterized by FT-IR, SEM,
1 3

J IRAN CHEM SOC
further purifcation. 1H, 13C NMR and FT-IR spectra were
recorded on Bruker Avance 300 MHz and Bruker VRTEX
70 model FT-IR spectrophotometer. The products are
known and they were characterized by their 1H, 13C NMR
and FT-IR spectra followed by a comparison with authen-
tic data. TLC was applied for the purity determination of
substrates, products and reaction monitoring over silica gel
60 F254 aluminum sheet. XRD spectra were obtained by
PANalytical X’PertPro difractometer (Holland) in 40 kV
and 30 mA with a CuKα radiation (λ = 1.5418 Å). Dif-
fraction patterns were also recorded in 2θ range (10°–80°).
Morphology of particles was determined by measuring SEM
images using FESEM–TESCAN MIRA3 instrument. Mag-
netic properties of the samples were measured on alternating
gradient force magnetometer (AGFM, Meghnatis Daghigh
Caviar Co., Iran) at room temperature. Thermogravimetric
curves were recorded using Shimadzu DTG-60 instrument.
The contents of Fe and Zr were measured by inductively
coupled plasma-optical emission spectrometry (ICP–OES).
N2 absorption–desorption was examined on Belsorp-Max
instrument (Japan). The specifc surface area was determined
using Brunauer–Emmett–Teller (BET) method. The pore
volume and pore size distribution were determined from des-
orption profle of isotherms using Barrett–Joyner–Halanda
method. Melting points were measured on Electrothermal
9100 apparatus.
Fig. 7 Magnetization curve for a Fe3O4 and b Fe3O4@APTMS@
ZrCp2 MNPs
in high to excellent yields. The nanocomposite can be reused
for 5 times without signifcant loss of its catalytic activity.
Easy separation of the catalyst, remarkable reusability, high
yields and mild reaction conditions as well as the benefts
of using water as a green solvent are the advantages which
make this protocol a prominent choice for reduction of nitro
compounds.
Experimental
General
NO2
NH2
Glycerol, Fe3O4@APTMS@ZrCp2
H2O, rt, 40 min
All reagents and substrates were purchased from com-
mercial sources in high purity and they were used without
Scheme 2 Reduction of nitrobenzene with glycerol/Fe3O4@
APTMS@ZrCp2 system
Table 2 Optimization
Entry
Glycerol
(mmol)
Fe3O4@
Solvent (2 mL)
Tempera- Time (min)
ture (°C)
Conversion (%)
experiments for reduction of
nitrobenzene with glycerol/
Fe3O4@APTMS@ZrCp2
system
APTMS@ZrCp2
(mg)
1
2
3
4
5
6
7
8
2
2
2
2
2
1
2
2
2
2
2
2
–
4
7
10
7
7
7
7
H2O
H2O
H2O
H2O
H2O
H2O
EtOH
MeOH
PEG-400
THF
CH3CN
H2O
rt
rt
rt
rt
60
rt
rt
rt
rt
rt
rt
rt
360
120
40
40
35
360
120
120
60
120
120
360
15
80
100
100
100
65
70
70
93
55
9
7
7
7
10
11
12
50
45
7 (ZrCp2Cl2)
All reactions were carried out with 1 mmol of nitrobenzene
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J IRAN CHEM SOC
Table 3 Reduction of nitro
compounds with glycerol/
Fe3O4@APTMS@ZrCp2
system
Yield (%)a
96
Mp/Bp ( C) [27]
°
Entry
1
Substrate
NO2
Product
NH2
Time (min)
40
184–185/760
mmHg
NO2
NH2
2
3
50
85
95
85
138–142
100–102
H2N
H2N
NO2
NH2
NH2
NH2
NO2
N
H
2
4
5
6
60
45
45
90
93
87
64–66
43–44
NH2
NH2
NO2
NH2
H
3C
H
3C
NO2
N
H
2
203–204/
760mmHg
H
H
CH3
C
C
3
H
C
3
3
H
H
C
C
3
3
221–222/
760mmHg
7
90
95
NO2
NO2
NH2
NH2
8
9
60
55
60
98
96
88
60–62
67–70
60–63
r
r
B
B
NO2
NH2
Cl
Cl
NH2
NO2
10
H
H
H
O 2C
H
O
C
C
NH2
NO2
11
75
90
81–83
H
H
2O
C
H
O
C
NH2
NO2
12
13
14
60
65
40
90
78
87
92–93
97–98
70–73
H
H
2O
C
2C
H
C
O
H
NO2
H
O
NH2
O
Cl
NO2
Cl
NH2
H
H
O
O
O
O
NO2
NH2
15
16
40
65
92
88
66–69
55–58
NO2
NH2
N
N
131–132/
760mmHg
142–144/
760mmHg
17
18
1-Nitrohexane
2-Nitroheptane
1-Hexylamine
2-Aminoheptane
45
50
90
92
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J IRAN CHEM SOC
Table 3 (continued)
All reactions were carried out in H2O (2 mL) at room temperature
aYields refer to isolated pure products
Table 4 Comparison of reduction of nitroarenes with diferent reducing systems
Entry
Substrate
Catalytic system
Reaction conditions
Yield (%)
References
a
1
2
3
4
5
6
7
8
Nitrobenzene
Nitrobenzene
Nitrobenzene
p-Nitroaniline
Nitrobenzene
p-Nitroaniline
m-Nitroaniline
p-Nitrophenol
Fe3O4@APTMS@ZrCp2
Nano Ni
Nano Co
Glycerol, H2O, rt, 40 min
N2H4, 75 min, rt
N2H4, 300 min, rt
96
99
50
84
96
95
98
92
[28]
[28]
[29]
[30]
[31]
[32]
[33]
CuBr2
NaBH4, EtOH, 14 h
Co3O4–NGr/C
Ni–Boride–Silica
Au/MgO NPs
rGO@Pd
HCO2H, 15 h, 100 °C
NaBH4, MeOH, 10 min
NaBH4, H2O, 20 min
NaBH4, H2O–EtOH, rt, 120 min
aCurrent protocol
atmosphere afords the pure nanoparticles of Fe3O4 (size:
4–8 nm).
Synthesis of Fe3O4@APTMS MNPs
Functionalization of magnetite nanoparticles was carried
out by refuxing Fe3O4 (1.5 g) with 3-aminopropyltrimeth-
oxysilane (APTMS) (2 g) in n-hexane (100 mL) under N2
atmosphere for 24 h. At the end of reaction, the resulting
Fe3O4@APTMS MNPs was washed with ethanol and then
dried under vacuum at room temperature.
Synthesis of Fe3O4@APTMS@ZrCp2 MNPs
Fig. 8 Reusability of Fe3O4@APTMS@ZrCp2 MNPs in glycerol
The prepared Fe3O4@APTMS MNPs (1 g) were dispersed
in ethanol by ultrasonic bath for 15 min. Subsequently,
Cp2ZrCl2 (1 g) was then added and the resulting mixture
was stirred mechanically at refux for 10 h. After comple-
tion of the reaction, the mixture was cooled to the room
temperature. Fe3O4@APTMS@ZrCp2 MNPs were collected
by an external magnet and washed with acetone and then
deionized water. The obtained MNPs were then dried under
vacuum for 6 h (size: 5–10 nm).
reduction of nitrobenzene
Preparation of Fe3O4@APTMS@ZrCp2 NPs
Preparation of Fe3O4 NPs
Magnetically nanoparticles of Fe3O4 were prepared by
a chemical co-precipitation protocol [23]. In a two-neck
round-bottom fask, a solution of FeCl3·6H2O (5.838 g,
0.022 mol) and FeCl2·4H2O (2.147 g, 0.011 mol) in distilled
water (100 mL) was prepared. The solution was stirred vig-
orously by a mechanical stirrer for 5 min (85 °C) under N2
atmosphere. To the prepared solution, aqueous NH3 (25%,
10 mL) was quickly added. Upon the addition, the black
nanoparticles of Fe3O4 were precipitated. The resulting mix-
ture was continued to stirring for 30 min at 85 °C followed
by cooling to the room temperature. The nanoparticles were
collected by an external magnet, washed with distilled water
and then with a solution of NaCl (0.02 M). Drying under air
A typical procedure for reduction of nitrobenzene
with glycerol/Fe3O4@APTMS@ZrCp2 system
In a round-bottom fask (10 mL) equipped with a magnetic
stirrer, a mixture of nitrobenzene (1 mmol, 0.123 g) and
H2O (2 mL) was prepared. Fe3O4@APTMS@ZrCp2 (7 mg)
was then added and the resulting mixture was stirred for
3 min. Next, glycerol (2 mmol) was added and the reaction
mixture was stirred for 40 min at room temperature. TLC
monitored the progress of the reaction (eluent, n-hexane/
EtOAc: 5/2). After completion of the reaction, the catalyst
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J IRAN CHEM SOC
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ture was extracted with EtOAc (2 × 5 mL). Drying organic
layer over anhydrous Na2SO4 followed by evaporation of
the solvent afords pure liquid aniline in 96% yield (0.089 g,
Table 3, entry 1).
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