Ni-guanidine@MCM-41 NPs: a new catalyst for the synthesis of 4,4?-(arylmethylene)-bis-(3-methyl-1-phenyl-1H-pyrazol-5-ols) and symmetric di-aryl sulfides

Article abstract of DOI:10.1007/s13738-019-01727-x

In this work, the surface of mesoporous MCM-41 was modified with guanidine, and then, Nickel particles have become immobilized on its surface (Ni-guanidine@MCM-41NPs). This heterogeneous catalyst has been identified by various techniques including: low-angle X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, inductively coupled plasma, thermal gravimetric analysis and N₂ adsorption–desorption measurement isotherms, and its catalytic application was studied in the synthesis of 4,4?-(arylmethylene)-bis-(3-methyl-1-phenyl-1H-pyrazol-5-ol) derivatives and symmetric di-aryl sulfides. The prepared organometallic complex could be isolated, post-reaction, by simple filtration for several consecutive cycles without a notable change in its catalytic activity.

Full text of DOI:10.1007/s13738-019-01727-x

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-019-01727-x
ORIGINAL PAPER
Ni‑guanidine@MCM‑41 NPs: a new catalyst for the synthesis of 4,4ʹ‑(ar
ylmethylene)‑bis‑(3‑methyl‑1‑phenyl‑1H‑pyrazol‑5‑ols) and symmetric
di‑aryl sulfdes
Hossein Filian1,2 · Arash Ghorbani‑Choghamarani3 · Elham Tahanpesar2
Received: 15 December 2018 / Accepted: 28 June 2019
© Iranian Chemical Society 2019
Abstract
In this work, the surface of mesoporous MCM-41 was modifed with guanidine, and then, Nickel particles have become
immobilized on its surface (Ni-guanidine@MCM-41NPs). This heterogeneous catalyst has been identifed by various tech-
niques including: low-angle X-ray difraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, induc-
tively coupled plasma, thermal gravimetric analysis and N2 adsorption–desorption measurement isotherms, and its catalytic
application was studied in the synthesis of 4,4ʹ-(arylmethylene)-bis-(3-methyl-1-phenyl-1H-pyrazol-5-ol) derivatives and
symmetric di-aryl sulfdes. The prepared organometallic complex could be isolated, post-reaction, by simple fltration for
several consecutive cycles without a notable change in its catalytic activity.
Keywords Mesoporous MCM-41 · Nickel · Guanidine · Sulfdes
Introduction
Besides, it is worth mentioning that Carbon–heteroatom
bond formation is the most fundamental reactions in mod-
ern organic synthesis. In this respect, such reactions can
be regarded as powerful tools for the production of sev-
eral important pharmaceutical and biological compounds
[20–22]. Among them, C–S coupling reaction has a great
demand in organic chemistry and pharmacological sciences
[21–24], i.e., sulfde derivatives which are used as potent
drugs for HIV, Alzheimer, cancer and Parkinson diseases
[25, 26]. In addition, sulfde derivatives are used as starting
materials for the preparation of sulfoxides and sulfones [22].
However, C–S coupling and multicomponent reactions will
proceed in the presence of a catalyst in order to achieve a
tolerable selectivity and isolated yields.
Multicomponent reactions are becoming a strategic tool for
the synthesis of biological heterocyclic compounds [1–4].
The major advantages of multicomponent reactions are high
atom economy, time saving and one-pot synthesis without
isolation of generating by-products or intermediates [2–7].
Among the various N-heterocyclic compounds, the bis-
pyrazolones and pyrazolones were paid much attention for
their diferent biological applications, such as antibacterial
[8], antiflarial agents [9], antitumor [10], cytokine inhibitors
[11], selective COX-2 inhibitory [12], pesticides [13], fungi-
cides [14], anti-infammatory [15] and dyes [16]. Moreover,
these compounds were used as extracting agents for some
metal ions in analytical chemistry [17, 18] and ligands in
coordination chemistry [17–19].
Nanoparticles as catalysts or support for catalysts have
become a signifcant feld of organic methodology researches
[27, 28]. The potential advantages of nanoparticles in cataly-
sis applications can be named as simplifed recovery, reus-
ability and efciency activity due to high surface area [28,
29]. Therefore, nanoparticles could lead to novel and envi-
ronment-friendly catalytic applications for industry and aca-
demic researches [30]. In this sense, mesoporous materials
such as MCM-41 have been widely used in catalysis felds
[31], drug delivery systems [32], adsorption [33, 34], extrac-
tion [35] and energy [36]. MCM-41 has unique properties
such as high stability (more than 900 °C), simple preparation
* Arash Ghorbani-Choghamarani
a.ghorbani@ilam.ac.ir; arashghch58@yahoo.com
1
2
3
Department of Chemistry, Khuzestan Science and Research
Branch, Islamic Azad University, Ahvaz, Iran
Department of Chemistry, Ahvaz Branch, Islamic Azad
University, Ahvaz, Iran
Department of Chemistry, Faculty of Science, Ilam
University, P.O. Box 69315516, Ilam, Iran
Vol.:(0123456789)
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Journal of the Iranian Chemical Society
and separation and large specifc surface area (>1000 m2/g),
which leads to ease of its functionalization [37–40]. These
unique properties of mesoporous MCM-41 will make it a
wonderful support for various catalysts [41, 42]. Therefore,
herein, a new complex of nickel on mesoporous MCM-41
was reported as a high efcient catalyst in organic reactions.
was stirred for 20 h under refux conditions. The obtained
Ni-guanidine@MCM-41NPs was fltered and washed with
ethanol for several times and, then, dried under air atmos-
phere (Scheme 1).
General procedure for the synthesis of 4,4ʹ‑(arylme
thylene)‑bis‑(3‑methyl‑1‑phenyl‑1H‑pyrazol‑5‑ols)
derivatives
Experimental
A mixture of 3-methyl-1-phenyl-5-pyrazolone (2 mmol),
aldehyde (1 mmol) and Ni-guanidine@MCM-41NPs nano-
catalyst (0.05 g) in acetonitrile was stirred at 80°C, and the
progress of the reaction was monitored by TLC. Upon the
completion of the reaction, the mixture was cooled down to
room temperature and the catalyst was separated by simple
fltration and washed with hot ethanol. Then, the solvent was
evaporated and, consequently, pure 4,4ʹ-(arylmethylene)-
bis-(3-methyl-1-phenyl-1H-pyrazol-5-ol) derivatives were
obtained in high yields (Scheme 2).
Preparation of guanidine complex of nickel
supported on the surface of MCM‑41
(Ni‑guanidine@MCM‑41NPs)
Initially, mesoporous MCM-41 modifed by 3-chloropro-
pyltrimethoxysilane (nPrCl-MCM-41NPs) was synthe-
sized according to our previous reported method [29]. For
immobilization of the guanidine on the surface of nPrCl-
MCM-41NPs, guanidine nitrate (2 mmol) and Na2CO3
(2 mmol) were added to mixture of nPrCl-MCM-41NPs
(1 g) in toluene (10 ml), and the reaction mixture stirred
for 24 h at 100°C. The obtained guanidine@MCM-41NPs
was fltered and washed with ethanol for several times and,
then, dried under air atmosphere. In the fnal step, immobi-
lization of nickel onto guanidine@MCM-41NPs was per-
formed by mixing the guanidine@MCM-41NPs (1 g) and
Ni(NO3)2·6H2O (2 mmol) in ethanol. The resulted mixture
General procedure for the synthesis of symmetric
di‑aryl sulfdes
A mixture of Ni-guanidine@MCM-41NPs (0.05 g), aryl hal-
ide (1 mmol), sulfur (0.5 mmol) and potassium hydroxide
(0.5 g) was stirred at 110°C in DMSO (3 ml). Upon the com-
pletion of the reaction, the mixture was cooled down to room
Scheme 1 Synthesis of Ni-
NH
guanidine@MCM-41NPs
O
O Si
O
O
O Si
O
guanidine, Na2CO3
Cl
N
H
NH2
Toluene, 24h
100 °C
nPrCl-MCM-41NPs
guanidine@MCM-41NPs
Ni
NH
Ni
H
O
N
Ni(NO3)2.6H2O
HN
H2N
O
O Si
O
Si
O
O
N
H
NH2
Ethanol, reflux
20 h
Ni-guanidine@MCM-41NPs
Scheme 2 Ni-guanidine@
MCM-41NPs catalyzed the syn-
thesis of 4,4ʹ-(arylmethylene)-
bis-(3-methyl-1-phenyl-1H-
pyrazol-5-ol) derivatives
R
Me
Me
O
Ni-guanidine@MCM-41NPs
CHO Me
N
N
N
N
R
N
N
+
CH3CN, 80 oC
Ph
Ph
Ph
OH
HO
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Journal of the Iranian Chemical Society
temperature and the catalyst was separated by simple fltra-
tion, and then, the fltrated solution was extracted with ethyl
acetate. In addition, the organic layer was dried with anhydrous
Na2SO4, and organic solvent was evaporated to aford pure
products (Scheme 3).
Catalyst characterizations
The XRD pattern of Ni-guanidine@MCM-41NPs which is
shown in Fig. 1 consists of an intense peak at 2θ = 2.58
which is allocated to the (100) of mesoporous channels regu-
larity of MCM-41 after immobilization of organic layers
and nickel complex onto MCM-41 channels [30]. However,
upon post-synthetic grafting, the (110) and (200) refections
became weaker and, also, the intensity of d100 decreased.
This is due to the irregular immobilization of Ni complex
onto channels of MCM-41 [30].
Selected spectral data
1
di‑p‑Tolylsulfane (Table 5, Entry 5): H NMR (500 MHz,
DMSO-d6): δH 2.26 (s, 6H), 7.17–7.18 (d, J = 7 Hz, 4H),
7.37–7.39 (d, J = 7 Hz, 4H) ppm; 13C NMR (125 MHz,
DMSO-d6) δ 21.0, 128.6, 130.5, 131.2, 133.1 ppm.
The morphological features of MCM-41 and Ni-guan-
idine@MCM-41NPs were investigated by SEM tech-
nique. The SEM images of MCM-41 and Ni-guanidine@
MCM-41NPs are shown in Fig. 2. As illustrated in
(Fig. 2a), particles of mesoporous MCM-41 were observed
between 60–90 nm with homogeneous size and spherical
morphology.
4,4ʹ‑((2‑Bromophenyl)methylene)bis(3‑methyl‑1‑phe‑
1
nyl‑1H‑pyrazol‑5‑ol) (Table 3, Entry 3): H NMR (500 MHz,
DMSO-d6): δH 2.32 (s, 6H), 5.14 (s, 1H), 7.12–7.15 (t, J =
10 Hz, 1H), 7.22–7.25 (t, J = 5 Hz, 2H), 7.33–7.36 (t, J =
5 Hz, 1H), 7.42–7.45 (t, J = 10 Hz, 4H), 7.56–7.58 (d, J =
10 Hz, 1H), 7.72–7.73 (d, J = 5 Hz, 4H), 7.86–7.88 (d, J =
5 Hz, 1H), 11.68 (br, 1H), 13.82 (br, 1H) ppm; 13C NMR
(125 MHz, DMSO-d6) δ 12.6, 34.8, 104.5, 121.0, 123.3,
126.1, 127.9, 128.8, 129.4, 131.0, 133.3, 137.6, 141.5,
146.5 ppm.
As it is evident from the SEM image of Ni-guanidine@
MCM-41NPs, the diameter of the prepared nanoparticles is
about 60–90 nm with homogeneous size and spherical mor-
phology (Fig. 2b) which is in agreement with SEM images
of MCM-41. Therefore, size and shape of the catalyst have
not been changed after the grafting process.
4,4ʹ‑((3,4‑Dimethoxyphenyl)methylene)bis(3‑methyl‑1‑phe‑
In order to determine the elemental composition of Ni-
guanidine@MCM-41NPs nanocatalyst, the components of
catalyst were analyzed using EDS (Fig. 3). As depicted, the
EDS spectrum of Ni-guanidine@MCM-41NPs all of the ele-
ments: Si, O, C, N and nickel species was observed in the
catalyst composition. Moreover, the exact amount of nickel
in catalyst which was obtained by ICP technique was found
to be 1.6 × 10−3 mol g−1.
1
nyl‑1H‑pyrazol‑5‑ol) (Table 3, Entry 7): H NMR (500 MHz,
DMSO-d6): δH 2.34 (s, 6H), 3.68 (s, 3H), 3.71 (s, 3H), 4.91
(s, 1H), 6.84–6.88 (t, J = 10 Hz, 2H), 6.93 (s, 1H), 7.22–7.25
(t, J = 10 Hz, 2H), 7.43–7.46 (t, J = 10 Hz, 4H), 7.73–7.75
(d, J = 10 Hz, 4H), 11.81 (br, 1H), 14.11 (br, 1H) ppm;
13C NMR (125 MHz, DMSO-d6) δ 12.1, 33.4, 56.0, 105.4,
112.1, 112.2, 119.8, 121.0, 126.0, 129.4, 135.5, 137.9,
146.7, 147.7, 148.9 ppm.
4 , 4 ʹ , 4 ʹ ʹ , 4 ʹ ʹ ʹ ‑ ( 1 , 4 ‑ P h e n y l e n e b i s ( m e t h a n e t r i y l ) )
tetrakis(3‑methyl‑1‑phenyl‑1H‑pyrazol‑5‑ol) (Table 3, Entry
1000
800
600
400
200
0
1
10): H NMR (500 MHz, DMSO-d6): δH 2.28 (s, 12H), 4.87
(s, 2H), 7.17–7.68 (m, 24H), 12.43 (br, 2H), 14.10 (br, 2H)
ppm; 13C NMR (500 MHz, DMSO-d6) δ 12.1, 33.3, 121.1,
126.0, 127.4, 129.3, 140.5, 146.7 ppm.
Result and discussion
The synthesized nanocatalyst (Ni-guanidine@MCM-41NPs)
has been characterized by the XRD, SEM, EDS, ICP, TGA and
N2 adsorption–desorption measurement isotherms techniques.
0
2
4
6
8
10
12
2 Theta
Fig. 1 Low-angle XRD patterns of Ni-guanidine@MCM-41NPs
Scheme 3 Ni-guanidine@
MCM-41NPs catalyzed the
synthesis of symmetric di-aryl
sulfdes
I
Ni-guanidine@MCM-41NPs
DMSO, KOH, 110 oC
S
R
S8
+
R
R
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Journal of the Iranian Chemical Society
Fig. 2 SEM images of a MCM-41 and b Ni-guanidine@MCM-41NPs
Fig. 4 TGA analysis of Ni-guanidine@MCM-41NPs
Fig. 3 EDS image of Ni-guanidine@MCM-41NPs Nano-material
The N2 adsorption and desorption isotherms of Ni-
guanidine@MCM-41NPs are illustrated in Fig. 5, and the
results are summarized in Table 1. This diagram displays
isotherm of type IV according to the IUPAC, which can be
regarded as the mesoporous structure of Ni-guanidine@
MCM-41NPs [43]. Based on Brunauer–Emmett–Teller
(BET), the surface area for Ni-guanidine@MCM-41NPs
is 428 m2/g, which is lower than the surface area of
mesoporous MCM-41 (1372 m2/g) [30]. The average
pore diameter and pore volume of Ni-guanidine@MCM-
41NPs are 1.29 nm and 0.61 cm3 g−1, respectively, which
are lower than MCM-41 (2.45 nm and 1.51 cm3 g−1) [29,
30]. The decrease in surface area, average pore diameter
and pore volume of Ni-guanidine@MCM-41NPs is due to
The immobilization of guanidine-Ni organometallic
complex on the surface of MCM-41NPs was also studied
by TGA analysis. The TGA diagram of the Ni-guanidine@
MCM-41NPs is shown in Fig. 4 which illustrates a three-
step weight loss while increasing the temperature. The frst
step shows a small mass loss (which is about 2%) at below
100 °C may be due to the removal of the physically and
chemically absorbed solvents or surface hydroxyl groups
[29, 30]. The second and third steps between 100–460 °C
and 460–800 °C with 17 and 4% of weight loss are attributed
to the decomposition of organic layers [4] and decomposi-
tion of the silanol groups, respectively [29] (Fig. 4).
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Journal of the Iranian Chemical Society
Table 2 Screening of the reaction parameters for the synthesis of
4,4ʹ-(arylmethylene)-bis-(3-methyl-1-phenyl-1H-pyrazol-5-ol)
400
Entry Catalyst Solvent
(mg)
Tem-
Time (min) Yield (%)a
perature
(°C)
1
2
3
4
5
6
7
8
9
10
20
40
50
60
50
50
50
50
50
50
Acetonitrile
Acetonitrile
Acetonitrile
Acetonitrile
Ethyl acetate
Ethanol
80
80
80
80
80
80
80
120
25
70
30
30
30
30
60
60
60
20
30
30
73
85
92
92
85
80
64
5
200
0
0
0.5
p/p0
1
Acetone
Solvent-free
Acetonitrile
Acetonitrile
10
75
Fig. 5 N2 adsorption–desorption isotherms of Ni-guanidine@MCM-
41NPs
aIsolated yield
Table 1 Texture properties of Ni-guanidine@MCM-41NPs
SBET (m2 g−1) DBJH (nm) V Total (cm3 g−1
)
and electron-withdrawing functional groups) were tested
under optimized reaction conditions (Table 3). As shown
in Table 3, all products were obtained in high yields. Also,
terephthaldehyde was converted to the corresponding prod-
uct in 75% of yield (Table 3, entry 10).
Sample name
Ni-guanidine@
MCM-41NPs
428 1.29 0.61
In the second part of our study, the catalytic ability of
Ni-guanidine@MCM-41NPs for the synthesis of symmet-
ric di-aryl sulfdes from C–S coupling reaction was consid-
ered under various reaction conditions (Scheme 3). For this
purpose, the coupling of iodobenzene with S8 was selected
as the model reaction. In this sense, the model reaction was
examined in various solvents (Table 4, entries 6–9) and in
the presence of diferent amounts of Ni-guanidine@MCM-
41NPs (Table 4, entries 1–6). The reaction did not proceed
in the absence of the catalyst (Table 4, entry 1). As shown
in Table 4, increase in the amount of the Ni-guanidine@
MCM-41NPs led to an increase in the isolated products,
whose best results were obtained with 0.05 g of Ni-guan-
idine@MCM-41NPs in dimethyl sulfoxide (Table 4, entry
5). Then, the model reaction was examined in various bases
(Table 4, entries 9–12) at diferent temperatures (Table 4,
entries 12–17). Among the various bases, the highest yield
has been obtained using KOH at 110 °C (Table 4, entry 5).
After optimization of the reaction conditions, the cata-
lytic activity of Ni-guanidine@MCM-41NPs was extended
to a wide range of aryl halides including aryl iodides, aryl
bromides and aryl chlorides.
the immobilization of organic layers and nickel complex
onto MCM-41.
Study of catalytic property
Catalytic activity of Ni-guanidine@MCM-41NPs was
investigated in the synthesis of 4,4ʹ-(arylmethylene)-bis-(3-
methyl-1H-pyrazol-5-ol) (Scheme 2) and symmetric di-aryl
sulfdes (Scheme 3).
Initially, the reaction conditions for the synthesis of
4,4ʹ-(arylmethylene)-bis-(3-methyl-1H-pyrazol-5-ol) have
been optimized for diferent reaction parameters includ-
ing the amount of catalyst, nature of solvent and tempera-
ture (Table 2). At frst, the condensation of benzaldehyde
and 3-methyl-1-phenyl-5-pyrazolone for the synthesis of
4,4ʹ-(arylmethylene)-bis-(3-methyl-1H-pyrazol-5-ol) has
been selected as model reaction.
At the outset, the effect of different amounts of Ni-
guanidine@MCM-41NPs catalyst in the model reaction
was examined (Table 2, entries 1–4) and diferent solvents
(Table 2, entries 4–8). The best results were obtained in ace-
tonitrile as solvent using 0.05 g of Ni-guanidine@MCM-
41NPs. Also, the efect of temperature was studied (Table 2,
entries 8–10). Accordingly, the best result was obtained at
80 °C (Table 2, entry 3).
The results of this study are summarized in Table 5. As
shown, a wide range of aryl halides bearing electron-donat-
ing and electron-withdrawing functional groups was suc-
cessfully coupled with S8 and all products were obtained in
excellent yields.
In order to explore the generality and scope of this
method, various aldehydes (contenting electron-donating
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Journal of the Iranian Chemical Society
Table 3 Preparation of
Entry
1
Product
Time (min)
30
Yield (%)
92
M.P. (°C)
168–170
M.P. (°C) [Lit.]
170–172 [19]
4,4ʹ-(arylmethylene)-bis-(3-
methyl-1-phenyl-1H-pyrazol-
5-ols) derivatives catalyzed by
Ni-guanidine@MCM-41NPs
e
e
M
M
N
N
N
N
P
h
P
h
H
O
H
O
2
25
90
210–215
213–215 [10]
Cl
e
M
e
M
N
N
N
N
P
h
P
h
H
O
H
O
3
4
20
35
90
90
195–200
202–203
198–200 [18]
202–204 [19]
r
B
e
M
e
M
N
N
N
N
P
h
P
h
H
O
H
O
e
M
e
e
e
e
e
M
M
N
N
N
N
P
P
P
P
h
P
h
h
h
h
H
H
H
H
H
O
O
5
6
7
40
35
60
83
80
87
170–175
150–155
194–196
173–175 [10]
153–155 [10]
194–196 [10]
e
M
O
O
O
e
M
M
N
N
N
N
h
h
h
P
P
P
H
O
O
H
e
M
M
O
N
N
N
N
H
O
e
M
e
M
O
e
M
M
N
N
N
N
H
O
O
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Journal of the Iranian Chemical Society
Table 3 (continued)
Entry
8
Product
Time (min)
15
Yield (%)
85
M.P. (°C)
220–228
M.P. (°C) [Lit.]
225–227 [18]
N
O2
e
M
e
M
N
N
N
N
P
P
h
P
P
h
H
H
H
O
O
9
20
75
83
75
145–150
210–215
151–153 [11]
214–216 [18]
N
O2
e
M
e
M
N
N
N
N
h
h
H
O
O
10
P
P
h
h
H H
O
O
N
N
N
N
e
M
e
M
e
M
e
M
N
N
N
N
P
h
P
h
H
O
H
O
Table 4 Screening of the reaction parameters for the synthesis of
symmetric di-aryl sulfdes in 150 min
Catalyst reusability
The reusability of Ni-guanidine@MCM-41NPs was exam-
ined in the model reaction. After completion of the reac-
tion, the catalyst was recovered by centrifugation and, then,
reused again for 6 more runs without loss of its catalytic
activity (Fig. 6), signifying that the nickel leaching from
Ni-guanidine@MCM-41NPs is very low.
Entry Catalyst (g) Solvent Base
Tempera- Yield (%)a
ture (°C)
b
1
2
3
4
5
6
7
8
–
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
Water
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
110
110
110
110
110
110
110
110
110
–
0.02
0.03
0.04
0.05
0.06
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
35
57
75
94
94
b
–
Conclusion
b
PEG
DMF
–
9
65
30
40
73
In conclusion, we have successfully immobilized the nickel
complex of guanidine onto pores of MCM-41. Then, this
nanocatalyst was characterized by various techniques such
as: XRD, SEM, EDS, ICP, TGA and BET. The catalyst
shows high catalytic activity in 4,4ʹ-(arylmethylene)-bis-
(3-methyl-1-phenyl-1H-pyrazol-5-ol) and C–S coupling
reaction toward preparation of symmetric di-aryl sulfdes.
The remarkable advantages of this procedure include simple
work-up procedure, operational simplicity, high efciency
of catalyst which led to high yields of the products in short
reaction times and its environmentally friendly nature. Also,
10
11
12
13
14
15
16
17
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
Na2CO3 110
K2CO3
NaOH
KOH
KOH
KOH
KOH
KOH
110
110
25
b
–
40
60
80
120
25
47
65
94
aIsolated yield
bNo reaction
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Journal of the Iranian Chemical Society
Table 5 C–S coupling of aryl halides with S8 catalyzed by Ni-guanidine@MCM-41NPs
Entry
1
Aryl halide
Product
Time (h)
2.5
Yield (%)a
94
M.P. (°C)
Oil
M.P. (°C) [Lit.]
Oil [44]
S
S
S
I
2
3
4
6
85
63
80
Oil
Oil
Oil
Oil [44]
Oil [44]
Oil [44]
Br
17
12
Cl
S
S
S
I
Me
Me
Me
5
14
70
Oil
Oil [44]
Br
Me
Me
Me
6
7
F3C
CF3
6
5
83
87
Oil
Oil
Oil [44]
Oil [44]
F3C
I
S
I
MeO
MeO
OMe
MeO
MeO
O2N
S
8
6.5
2
80
60
85
Oil
Oil [44]
Br
OMe
9
150–158
Oil
157–159 [44]
Oil [44]
S
Br
O2N
NO2
OMe
OMe
10
9
I
S
OMe
aIsolated yield
this catalyst can be recovered by simple fltration and reused
for several times without loss of performance.
100
80
60
40
20
0
Acknowledgements This work was supported by the research facilities
of Ahvaz Branch, Islamic Azad University, Ahvaz, Iran.
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