Silica coated magnetic NiFe2O4 nanoparticle supported phosphomolybdic acid; Synthesis, preparation and its application as a heterogeneous and recyclable catalyst for the one-pot synthesis of tri- and tetra-substituted imidazoles under solvent free conditions

Article abstract of DOI:10.1039/c5ra10534j

In this research, a magnetically-recoverable catalyst (NiFe₂O₄@SiO₂-H₃PMo₁₂O₄₀) was prepared by supporting phosphomolybdic acid (H₃PMo₁₂O₄₀) onto silica-coated NiFe₂O₄ nanoparticles. The prepared sample was characterized by FT-IR, TEM, SEM and VSM techniques and then the catalytic activity of this catalyst was investigated in the synthesis of tri- and tetra-substituted imidazole derivatives. More importantly, the catalyst was easily isolated from the reaction mixture by a magnetic bar and reused at least ten times without significant degradation in its activity.

Full text of DOI:10.1039/c5ra10534j

RSC Advances
View Article Online
View Journal | View Issue
PAPER
Silica coated magnetic NiFe2O4 nanoparticle
supported phosphomolybdic acid; synthesis,
preparation and its application as a heterogeneous
and recyclable catalyst for the one-pot synthesis of
tri- and tetra-substituted imidazoles under solvent
free conditions†
Cite this: RSC Adv., 2015, 5, 64850
a
Behrooz Maleki, Hossein Eshghi,b Amir Khojastehnezhad,b Reza Tayebee,a
*
Samaneh Sedigh Ashrafi,a Golnoosh Esmailian Kahooa and Farid Moeinpourc
In this research, a magnetically-recoverable catalyst (NiFe2O4@SiO2–H3PMo12O40) was prepared by
supporting phosphomolybdic acid (H3PMo12O40) onto silica-coated NiFe2O4 nanoparticles. The prepared
sample was characterized by FT-IR, TEM, SEM and VSM techniques and then the catalytic activity of this
catalyst was investigated in the synthesis of tri- and tetra-substituted imidazole derivatives. More
importantly, the catalyst was easily isolated from the reaction mixture by a magnetic bar and reused at
least ten times without significant degradation in its activity.
Received 3rd June 2015
Accepted 20th July 2015
DOI: 10.1039/c5ra10534j
www.rsc.org/advances
The development of a simple, well-organized, and environ-
mentally synthetic method for broadly used organic
Introduction
compounds from readily available reagents is one of the major
challenges for chemists.7 With a wide range of applications,
imidazoles have been receiving growing attention in recent
years.8 The imidazole core is present in many molecules with
biological activities such as being anti-allergenic,9 anti-inam-
matory,10 analgesic, antifungal, antimycotic, antibiotic, anti-
ulcerative, antibacterial and antitumoral.11 Plus, being known
as inhibitors of p38 MAP kinases12 and therapeutic agents,
various substituted imidazoles also act as plant growth regula-
tors, glucagon receptors,13 photosensitive compounds in
photography, and building blocks for the synthesis of other
classes of compounds.14 Among them, tri- and tetrasubstituted
imidazoles have received much attention recently.15 In the last
decades, many methods have been developed for the synthesis
of tri- and tetrasubstituted imidazoles by the reaction of alde-
hydes, and benzil or benzoin with (i) ammonium acetate, and
(ii) ammonium acetate and amines in the presence of various
reagents or catalysts such as: BF3–SiO2,16 silica gel–NaHSO4,17
HClO4–SiO2,18 K5CoW12O40$3H2O,19 InCl3$3H2O,20 L-proline,21
I2,22 zeolite-HY–Cu(NO3)2,23 MCM-41 or p-TsOH,24 1-butyl-3-
methylimidazolium bromide [Bmim]Br,25 poly(AMPS-co-AA),26
1,3-disulfonic acid imidazolium hydrogen sulfate [Dsim]
[HSO4],27 nano-crystalline sulfated zirconia (SZ),28 1-ethyl-3-
methylimidazolium acetate [Emim][OAc],29 [Et3NSO3H]Cl,30
Magnetic nanoparticles (MNPs) have captured much attention
as attractive solid supports for the immobilization of homoge-
neous catalysts.1 This is because MNPs can be well dispersed in
reaction mixtures without any magnetic eld, providing a large
surface area to be readily accessible to substrate molecules.
Moreover, aer completing the reactions, MNP supported
catalysts can be efficiently isolated from the product solution
through a simple magnetic separation process.2,3
Ni–Fe ferrites are some of the most versatile magnetic
materials as they have a high saturation magnetization, high
Curie temperature, chemical stability and relatively high
permeability.4 Phosphomolybdic acid (PMA) belongs to a class
of heteropolyacids (HPAs). HPAs are commercially cheap and
environmentally friendly catalysts. They exhibit high activities
and selectivities and allow cleaner processes than conventional
catalysts. Supported HPAs on silica-coated Ni–Fe ferrite MNPs
can produce heterogeneous catalytic systems that possess both
a high separation efficiency and a relatively high surface area to
maximize the catalyst loading and activity.5,6
aDepartment of Chemistry, Hakim Sabzevari University, Sabzevar, 96179-76487, Iran.
E-mail: b.maleki@hsu.ac.ir; Fax: +98-514401300; Tel: +98-44013324
bDepartment of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad,
Mashhad, Iran
1,1,3,3-N,N,N0,N0-tetramethylguanidinium
triuoroacetate
cDepartment of Chemistry, Bandar Abbas Branch, Islamic Azad University, Bandar
(TMGT),31 DABCO,32 acetic acid,33 silica-bonded propylpiper-
Abbas 7915893144, Iran
azine N-sulfamic acid (SBPPSA),34 silica chloride,35 europium
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c5ra10534j
64850 | RSC Adv., 2015, 5, 64850–64857
This journal is © The Royal Society of Chemistry 2015

View Article Online
Paper
RSC Advances
triate [Eu(OTf)3],36 p-dodecylbenzenesulfonic acid (DBSA),37
trichloroisocyanuric acid (TCCA),38 tetrabutyl ammonium
bromide (TBABr),39 1-methylimidazolium triuoroacetate
([Hmim]TFA),40 and without any catalyst.41 Many of the
synthetic methods for imidazoles suffer from one or more
disadvantages such as low yields, harsh reaction conditions,
difficult work-up, prolonged time period and the application of
hazardous and expensive catalysts. Hence the development of
clean, high yielding, and environmentally benign approaches is
still desirable and much in demand. In this full paper, we report
our efforts and success in developing an effective one-pot multi-
component reaction of aldehydes and benzil or benzoin with (i)
ammonium acetate, and (ii) ammonium acetate and amines in
the presence of magnetic supported catalyst (NiFe2O4@SiO2–
H3PMo12O40 designed NFS–PMA).
Scheme 2 Synthesis of 2,4,5-trisubstituted imidazoles and 1,2,4,5-
tetrasubstituted imidazoles.
The morphological features and distribution of the NFS
MNPs were investigated by the TEM and SEM techniques
(Fig. 2a and b). The TEM and SEM photographs demonstrate
that the NFS MNPs are narrowly distributed, well dispersed and
are also almost spherical with a regular shape. Also, the particle
size dispersion diagram (Fig. 3) from the NFS NPs shows that
these MNPs have a size between 25 and 97 nm and the mean
diameter is 53 nm.
The great importance of core/shell materials lies within their
sufficient magnetic and superparamagnetic properties.
Magnetic hysteresis measurements for NiFe2O4 were done in an
applied magnetic eld at r.t., with the eld sweeping from
ꢀ10 000 to +10 000 Oersted. As shown in Fig. 4, the M(H)
hysteresis loop of the samples was completely reversible,
showing that the nanoparticles exhibit superparamagnetic
characteristics. The hysteresis loop reached saturation up to the
maximum applied magnetic eld. The magnetic saturation
values of NiFe2O4 are 16.71 emu gꢀ1 at r.t. These MNPs showed
high permeability in magnetization and their magnetization
was sufficient for magnetic separation with a conventional
magnet.
Results and discussion
The heterogenization of HPAs on silica coated nanomagnetic
materials has been an interesting approach during the past
years. This strategy enabled research groups to overcome the
limitations involved in the separation and recycling of homo-
geneous catalysts.42 Thus, in this study, an efficient magnetic
supported acid catalyst (NFS–PMA) was prepared by the chem-
ical supporting of Keggin HPAs onto silica coated NiFe2O4
MNPs (Scheme 1).
In the continuation of our efforts toward the development of
greener methodologies,43 we now report that NiFe2O4@SiO2–
H3PMo12O40 is a green catalyst for the synthesis of 2,4,5-trisub-
stituted and 1,2,4,5-tetrasubstituted imidazoles (Scheme 2).
In order to determine the properties of this acidic supported
nanomagnetic catalyst, it was characterized by various tech-
niques such as FT-IR (Fig. 1), SEM and TEM (Fig. 2), particle size
dispersion (Fig. 3) and VSM (Fig. 4). The FT-IR spectra of NFS,
PMA and NFS–PMA are compared in Fig. 1. The FT-IR spectrum
of NFS (Fig. 1a) exhibits high intense absorption peaks at 1200
cmꢀ1 and 1100 cmꢀ1 and these peaks are assigned to the
longitudinal and transverse stretching vibration modes of the
Si–O–Si asymmetric bond, respectively. Additional bands at 812
cmꢀ1 and 470 cmꢀ1 are also identied as characteristic peaks of
the Si–O–Si bond. The other peak observed at 950 cmꢀ1
assigned to the SiO32ꢀ vibrations indicates the existence of non
bridging oxygen ions.44 The spectrum of PMA (Fig. 1b) shows
Our initial attempt started with the reaction of benzaldehyde
(1 mmol), benzil (1 mmol), and ammonium acetate (7 mmol) in
the presence of NiFe2O4@SiO2–H3PMo12O40 (NFS–PMA) under
determined bands for absorptions at 1064 (P–O), 962 (Mo]O),
882 and 767 (Mo–O–Mo) cmꢀ1
.
The last FT-IR spectrum
45
(Fig. 1c) corresponds to NFS–PMA, the characteristic bands at
963, 880 and 765 cmꢀ1 conrm that the PMA was well supported
on the surface of NFS.
Fig. 1 FT-IR spectra of (a) NiFe2O4@SiO2 (NFS), (b) H3PMo12O40 (PMA)
and (c) NiFe2O4@SiO2–H3PMo12O40 (NFS–PMA).
Scheme 1 Preparation of NiFe2O4@SiO2–H3PMo12O40 (NFS–PMA).
This journal is © The Royal Society of Chemistry 2015
RSC Adv., 2015, 5, 64850–64857 | 64851

View Article Online
RSC Advances
Paper
results, as shown in Table 2. Encouraged by this success, a study
on the synthesis of 1,2,4,5-tetrasubstituted imidazoles from
benzil or benzoin, amine, ammonium acetate and various
aromatic aldehydes was carried out (Table 2).
In order to illustrate the efficiency of our procedure, the
results for the preparation of 2,4,5-trisubstituted and 1,2,4,5-
tetrasubstituted imidazoles previously reported are compared
with our data (Table 3). The present method using NiFe2O4@-
SiO2–H3PMo12O40 (NFS–PMA) as the catalyst offers several
advantages such as excellent yields, a simple procedure, short
reaction times, facile work-up and greener conditions.
A plausible mechanism of the reaction is presented in
Scheme 3.
Fig. 2 (a) TEM and (b) SEM images of NiFe2O4@SiO2 (NFS).
To determine the applicability of catalyst recovery, at the end
of the reaction, with the aid of an external magnet, the catalyst
was held on the side wall of the reaction vessel, while the
solution was decanted. The catalyst was washed with chloro-
form to remove residual product, dried at 100 ꢁC under vacuum
and reused in a subsequent reaction with excellent yields. It
showed the same activity as the fresh catalyst without any
signicant loss of its activity (Fig. 5).
Fig. 3 Particle size dispersion of NiFe2O4@SiO2 (NFS).
Experimental Section
All reagents were purchased from Merck and Sigma-Aldrich and
used without further purication. IR spectra were recorded on a
1
Shimadzu 435-U-04 spectrophotometer (KBr pellets). H NMR
spectra were obtained using Bruker 250 and 300 MHz spec-
trometers in DMSO-d6 or CDCl3 and using TMS as the internal
reference. Melting points were determined in open capillary
tubes in a Stuart BI Branstead Electrothermal cat no. IA9200
apparatus and uncorrected. The particle size and morphology of
the synthesized catalyst were characterized with a transmission
electron microscope (TEM) (Philips CM-200 and Titan Krios)
and scanning electron microscope (SEM) (Philips XL 30 and S-
4160) with gold coating. The size dispersion of the samples
was obtained using a laser particle size analyzer (CORDOUAN,
Vasco3).
Fig. 4 Vibrating sample magnetometer (VSM) curve of NiFe2O4 at
room temperature.
Preparation of the catalyst
The silica coated NiFe2O4 MNPs (NFS, Scheme 1) were synthe-
sized according to our previous reports46–48 and then, for the
immobilization of PMA on NFS, 0.5 g of PMA was dissolved in 5
mL of methanol.49 This solution was added dropwise to a
suspension of 1.0 g NFS in methanol (50 mL) and then the
mixture was heated at 70 ꢁC for 48 h under vacuum while being
mechanically stirred and gave the supported nanomagnetic
catalyst (NFS–PMA). The catalyst was collected by a permanent
magnet and dried under vacuum overnight and aer the rst
ꢁ
solvent free conditions at 120 C (Table 1, entry 1). Then, the
effect of various temperatures were investigated, and 120 ꢁC was
the optimal temperature (entries 2 and 3). Additionally, this
reaction took place using various amounts of catalyst at 120 ꢁC
(entries 4 and 5). The yields were reduced in the presence of
H3PW12O40 and SiO2 under similar conditions (entries 6 and 7).
In the absence of a catalyst, the yield was trace (entry 8).
The optimal conditions were then applied for the prepara-
tion of a series of 2,4,5-trisubstituted imidazoles. The product
yields are shown in Table 2. In each case, no side product
formation was observed, as is normally the case in such reac-
tions under the inuence of strong acids. This method not only
affords the products in excellent yields but also avoids the
problems associated with catalyst cost, handling, safety, and
pollution. The use of benzoin in place of benzil also gave similar
ꢁ
drying, the supported nanocatalyst was calcined at 250 C for
2 h.50,51
General procedure for the synthesis of 2,4,5-trisubstituted
imidazoles (5a–i)
A mixture of benzil or benzoin (1 mmol), aldehyde (1 mmol),
ammonium acetate (7 mmol) and NFS–PMA (0.02 g) was
64852 | RSC Adv., 2015, 5, 64850–64857
This journal is © The Royal Society of Chemistry 2015

View Article Online
Paper
RSC Advances
Table 1 Screening of the reaction conditions for the synthesis of 2,4,5-triphenyl-imidazole (5a)
Entry
Amount of catalyst (g)
Conditions
Time (min)
Yielda (%)
1
2
3
4
5
6
7
8
NFS–PMA (0.02 g)
NFS–PMA (0.02 g)
NFS–PMA (0.02 g)
NFS–PMA (0.03 g)
NFS–PMA (0.01 g)
PMA (0.03 g)
Solvent-free/120 ꢁC
Solvent-free/110 ꢁC
Solvent-free/130 ꢁC
Solvent-free/120 ꢁC
Solvent-free/120 ꢁC
Solvent-free/120 ꢁC
Solvent-free/120 ꢁC
Solvent-free/120 ꢁC
20
20
20
20
30
20
20
20
94
87
92
92
89
72
Trace
Trace
SiO2 (0.03 g)
—
a
Isolated yields.
Table 2 Three and four component synthesis of the 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted imidazoles from the reaction of aldehydes,
and benzil or benzoin with (i) ammonium acetate, and (ii) ammonium acetate and amines in the presence of NiFe2O4@SiO2–H3PMo12O40 (NFS–
PMA)a
Time (min)
Benzil
Yieldsb (%)
Benzil
Products (5,7)
R1
R2
Benzoin
Benzoin
Ref.
5a
5b
5c
5d
5e
5f
5g
5h
5i
7a
7b
7c
7d
7e
7f
7g
7h
7i
C6H5
—
—
—
—
—
—
—
—
20
10
20
10
20
15
20
20
25
25
15
15
15
20
20
10
35
25
30
20
15
20
10
25
15
20
25
30
30
15
15
20
20
25
15
40
30
30
94
96
93
96
90
92
90
91
87
88
87
90
89
88
84
90
84
85
78
90
82
91
94
90
90
90
88
86
86
81
90
87
87
82
86
80
80
75
21
28
21
21
21
21
21
41
41
18
18
18
34
18
15b
15b
16
28
18
4-BrC6H4
3-NO2C6H4
3-OHC6H4
4-NO2C6H4
4-CH3C6H4
4-OCH3C6H4
2-Thienyl
2-Furyl
—
C6H5
PhCH2
PhCH2
PhCH2
PhCH2
PhCH2
2-Thienyl CH2
3,4-OMeC6H4CH2
PhNH2
PhNH2
3-NO2C6H4
4-BrC6H4
4-CH3C6H4
3-OHC6H4
4-OCH3C6H4
2-Thienyl
C6H5
C6H5
4-BrC6H4
4-N(CH3)2C6H4
7j
a
All known products have been reported previously in the literature and were characterized by comparing the IR and NMR spectra with authentic
samples. b Isolated yields.
This journal is © The Royal Society of Chemistry 2015
RSC Adv., 2015, 5, 64850–64857 | 64853

View Article Online
RSC Advances
Paper
Table 3 Comparison of methods for the synthesis of 2,4,5-trisubstituted imidazoles and 1,2,4,5-tetrasubstituted imidazoles
Entry
Compounds
Conditions
Time (min)
Yield (%)
Present work
10
540
75
120
720
30
240
720
480
50
240
20
500
70
70
100
20
720
30
240
720
420
30
240
25
120
120
520
540
115
120
30
96
76
81
87
82
84
75
90
88
91
90
90
76
80
70
92
84
89
78
81
95
83
91
86
88
80
90
51
86
79
90
87
87
74
80
InCl3$3H2O/MeOH/rt20
Nano-crystalline sulfated zirconia (SZ)/EtOH/reux28
[Et3NSO3H]Cl/solvent-free/100 ꢁC30
DABCO/t-BuOH/60–65 ꢁC32
Silica chloride/solvent-free/80 ꢁC35
p-Dodecylbenzenesulfonic acid/H2O/reux37
TCCA/EtOH/reux38
1
TBABr/t-BuOH/80 ꢁC39
[Hmim][TFA]/H2O/80 ꢁC40
Catalyst-free/MeOH/60 ꢁC41
Present work
InCl3$3H2O/MeOH/rt20
Nano-crystalline sulfated zirconia (SZ)/EtOH/reux28
[EMIM]OAc/EtOH/ultrasonic/rt29
[Et3NSO3H]Cl/solvent-free/100 ꢁC30
TMGT/solvent-free/100 ꢁC31
DABCO/t-BuOH/60–65 ꢁC32
Silica chloride/solvent-free/80 ꢁC35
p-Dodecylbenzenesulfonic acid/H2O/reux37
TCCA/EtOH/reux38
2
TBABr/t-BuOH/80 ꢁC39
[Hmim][TFA]/H2O/80 ꢁC40
Catalyst-free/MeOH/60 ꢁC41
Present work
BF3–SiO2/solvent-free/140 ꢁC16
K5CoW12O
40$3H2O/solvent-free/140 ꢁC19
InCl3$3H2O/MeOH/rt20
L-Proline/MeOH/60 ꢁC21
3
p-TsOH/solvent-free/140 ꢁC24
[Bmim]Br/solvent-free/140 ꢁC25
Poly(AMPS-co-AA)/solvent-free/110 ꢁC26
[Dsim][HSO4]/solvent-free/90 ꢁC27
DABCO/t-BuOH/60–65 ꢁC32
TBABr/t-BuOH/80 ꢁC25
10
720
420
stirred at 120 ꢁC in an oil bath for the times shown in Table 2. nanomagnetic catalyst was separated from the reaction mixture
Upon completion of the reaction, as indicated by TLC (hex- by employing an external magnetic eld. Aer that, the reaction
ane : ethyl acetate, 8 : 2), hot EtOH (96%, 1 mL) was added to mixture was poured onto crushed ice and the precipitated solid
the mixture and stirred for 2 min and, then, the nanomagnetic was collected, and recrystallized from ethanol (96%, 3 mL) to
catalyst was separated from the reaction mixture by employing afford the pure 1,2,4,5-tetrasubstituted imidazole derivatives
an external magnetic eld. Aer that, the reaction mixture was (7a–j). All products are known compounds, which were char-
poured onto crushed ice and the precipitated solid was acterized by measuring their m.p., and by IR and 1H-NMR
collected, and recrystallized from ethanol (96%, 3 mL) to spectroscopies.
afford the pure 2,4,5-trisubstituted imidazole derivatives (5a–
i). All products are known compounds, which were charac-
terized by measuring their m.p., and by IR and 1H-NMR
spectroscopies.
Conclusions
In summary, we have demonstrated an efficient and mild
procedure for the synthesis of 2,4,5-trisubstituted and 1,2,4,5-
tetrasubstituted imidazoles in the presence of NiFe2O4@SiO2–
H3PMo12O40 as a reusable, eco-friendly, inexpensive and effi-
General procedure for the synthesis of 1,2,4,5-tetrasubstituted
imidazoles (7a–j)
A mixture of benzil or benzoin (1 mmol), aldehyde (1 mmol), cient nanocatalyst. Moreover, other advantages such as excel-
ammonium acetate (7 mmol), benzylamine (2 mmol) and NFS– lent product yields, very short reaction times, mild reaction
ꢁ
PMA (0.02 g) was stirred at 120 C in an oil bath for the times conditions, and simple work-up procedures make this method
shown in Table 2. Upon completion of the reaction as indicated an interesting alternative to other methodologies. In addition, it
by TLC (hexane : ethyl acetate, 8 : 2), hot EtOH (96%, 1 mL) was is easy to separate and recover the catalyst for another catalytic
added to the mixture and stirred for 2 min and, then, the recycling.
64854 | RSC Adv., 2015, 5, 64850–64857
This journal is © The Royal Society of Chemistry 2015

View Article Online
Paper
RSC Advances
Scheme 3 Proposed mechanism.
21206; (d) Y. H. Liu, J. Deng, J. W. Gao and Z. H. Zhang,
Adv. Synth. Catal., 2012, 354, 441; (e) P. H. Li, B. L. Li,
Z. M. An, L. P. Mo, Z. S. Cui and Z. H. Zhang, Adv. Synth.
Catal., 2013, 355, 2952; (f) J. Lu, X. T. Li, E. Q. Ma, L. P. Mo
and Z. H. Zhang, ChemCatChem, 2014, 6, 2854; (g) F. P. Ma,
P. H. Li, B. L. Li, L. P. Mo, N. Liu, H. J. Kang, Y. N. Liu and
Z. H. Zhang, Appl. Catal., A, 2013, 457, 34; (h) B. L. Li,
M. Zhang, H. C. Hu, X. Du and Z. H. Zhang, New J. Chem.,
2014, 38, 2435; (i) D. Wang and D. Astruc, Chem. Rev.,
2014, 114, 6949.
´
2 P. Riente, C. Mendoza and M. A. Pericas, J. Mater. Chem.,
Fig. 5 Reusability of NiFe2O4@SiO2–H3PMo12O40 (NFS–PMA) for the
2011, 21, 7350.
model reaction.
3 R. Abu-Reziq, H. Alper, D. Wang and M. L. Post, J. Am. Chem.
Soc., 2006, 128, 5279.
4 A. Goldman, Modern ferrite technology, Springer, USA, 2nd
edn, 2006.
Acknowledgements
5 J. Deng, L. P. Mo, F. Y. Zhao, L. L. Hou, L. Yang and
Z. H. Zhang, Green Chem., 2011, 13, 2576.
6 L. Ma’mani, M. Sheykhan, A. Heydari, M. Faraji and
Y. Yamini, Appl. Catal., A, 2010, 377, 64.
This research work was supported by the University of Hakim
Sabzevari. The authors wish to thank the University of Hakim
Sabzevari for their nancial support to carry out this research.
7 A. S. Shapi, C. N. Umesh, S. P. Sanjay, D. Thomas,
J. L. Rajgopal and V. S. Kumar, Tetrahedron, 2005, 61, 3539.
8 G. V. M. Sharma, Y. Jyothi and P. S. Lakshmi, Synth.
Commun., 2006, 36, 2991.
References
1 (a) X. Duan, Y. Liu, Q. Zhao, X. Wang and S. Li, RSC Adv.,
2013, 3, 13748; (b) R. Tayebee, M. M. Amini,
S. Pouyamanesh and A. Aliakbari, Dalton Trans., 2015, 43,
5888; (c) R. Tayebee and M. Jarrahi, RSC Adv., 2015, 5,
9 M. Misono, Chem. Commun., 2001, 1141.
This journal is © The Royal Society of Chemistry 2015
RSC Adv., 2015, 5, 64850–64857 | 64855

View Article Online
RSC Advances
Paper
10 J. W. Black, G. J. Durant, J. C. Emmett and C. R. Ganellin, 31 A. Shaabani, A. Rahmati, B. Aghaaliakbari and J. Safaei-
Nature, 1974, 248, 65. Ghomi, Synth. Commun., 2006, 36, 65.
11 U. Ucucu, N. G. Karaburun and I. Iskdag, Farmaco, 2001, 56, 32 S. N. Murthy, B. Madhav and Y. V. D. Nageswar, Tetrahedron
285.
Lett., 2010, 51, 5252.
12 J. A. Murry, Drug Discovery Dev., 2003, 6, 945.
13 S. E. de Laszlo, C. Hacker, B. Li, D. Kim, M. MacCoss and
N. Mantlo, Bioorg. Med. Chem. Lett., 1999, 9, 641.
14 I. Satoru, Japn Kokkai Tokyo Koho JP 01, 117, 867, 10 May,
1989Chem. Abstr., 1989, 111, 214482.
33 A. Puratchikodya and M. Doble, Bioorg. Med. Chem., 2007,
15, 1083.
34 K. Niknam, A. Deris, F. Naeimi and F. Majleci, Tetrahedron
Lett., 2011, 52, 4642.
35 H. V. Chavan and D. K. Narale, C. R. Chim., 2014, 17, 980.
15 (a) S. Samai, G. C. Nandi, P. Singh and M. S. Singh, 36 C. Yu, M. Lei, W. Su and Y. Xie, Synth. Commun., 2007, 37,
Tetrahedron, 2009, 65, 10155; (b) S. R. Sarkar and 3301.
C. Mukhopadhyay, Eur. J. Org. Chem., 2015, 6, 1246; (c) 37 B. Das, K. Jajula, R. A. Kumar and P. Jangili, Monatsh. Chem.,
D. V. Paone and A. W. Shaw, Tetrahedron Lett., 2008, 49, 2013, 144, 223.
6155; (d) A. Shaabani, A. Rahmati, E. Farhangi and 38 S. F. Hojati, S. A. Nezhadhoseiny and Z. Beykzadeh, Monatsh.
Z. Badri, Catal. Commun., 2007, 8, 1149; (e) B. F. Mirjalili, Chem., 2013, 144, 387.
A. H. Bamonirib and L. Zamania, Sci. Iran., 2012, 19, 565; 39 C. Kurumurthy, G. S. Kumar, G. M. Reddy, P. Nagender,
(f) H. Veisi, A. Khazaei, L. Heshmati and S. Hemmati, Bull.
Korean Chem. Soc., 2012, 33, 1231; (g) A. R. Khosropour,
P. S. Rao and B. Narsaiah, Res. Chem. Intermed., 2012, 38,
359.
Ultrason. Sonochem., 2008, 15, 659; (h) H. Sharghi, M. Aberi 40 D. I. MaGee, M. Bahramnejad and M. Dabiri, Tetrahedron
and M. M. Doroodmand, Mol. Diversity, 2015, 19, 77; (i) Lett., 2013, 54, 2591.
M. Xia and Y. D. Lu, J. Mol. Catal. A: Chem., 2007, 265, 205. 41 N. Azizi, N. Dado and A. Khajeh Amiri, Can. J. Chem., 2012,
16 B. Sadeghi, B. F. Mirjalili and M. M. Hashemi, Tetrahedron
Lett., 2008, 49, 2575.
90, 195.
42 R. Tayebee, M. M. Amini, S. Pouyamanesh and A. Aliakbari,
Dalton Trans., 2015, 43, 5888.
17 A.
R.
Karimi,
Z.
Alimohammadi,
J.
Azizian,
A. A. Mohammadi and M. R. Mohammadizadeh, Catal. 43 (a) B. Maleki, S. Hemmati, A. Sedrpoushan, S. Sedigh Ashra
Commun., 2006, 7, 728.
and H. Veisi, RSC Adv., 2014, 4, 40505; (b) R. Tayebee,
M. Jarrahi, B. Maleki, M. Kargar Razi, Z. B. Mokhtaric and
S. M. Baghbanian, RSC Adv., 2015, 5, 10869; (c) B. Maleki,
S. Hemmati, R. Tayebee, S. Salemi, Y. Farokhzad,
M. Baghayeri, F. Mohammadi Zonoz, E. Akbarzadeh,
R. Moradi, A. Entezari, M. R. Abdi, S. Sedigh Ashra,
F. Taimazi and M. Hashemi, Helv. Chim. Acta, 2013, 96,
2147; (d) B. Maleki, S. Barzegar, Z. Sepehr, M. Kermanian
and R. Tayebee, J. Iran. Chem. Soc., 2012, 9, 757; (e)
B. Maleki and F. Taimazi, Org. Prep. Proced. Int., 2014, 46,
252; (f) B. Maleki, S. Sedigh Ashra and R. Tayebee, RSC
Adv., 2014, 4, 41521; (g) B. Maleki and S. Sedigh Ashra, J.
Mex. Chem. Soc., 2014, 58, 159; (h) H. Veisi, B. Maleki,
F. Hosseini Eshbala, H. Veisi, R. Masti, S. Sedigh Ashra
and M. Baghayeri, RSC Adv., 2014, 4, 30683; (i) B. Maleki
and S. Sedigh Ashra, RSC Adv., 2014, 4, 42873; (j)
M. Baghayeri, H. Veisi, H. Veisi, B. Maleki, H. Karimi-
Maleh and H. Beitollahi, RSC Adv., 2014, 4, 49595; (k)
B. Maleki and S. Sheikh, RSC Adv., 2015, 5, 42997; (l)
H. Veisi, B. Maleki, M. Hamelian and S. Sedigh Ashra,
RSC Adv., 2015, 5, 6365; (m) B. Maleki, S. Barat Nam
Chalaki, S. Sedigh Ashra, E. Rezaee Seresht,
F. Moeinpour, A. Khojastehnezhad and R. Tayebee, Appl.
Organomet. Chem., 2015, 29, 290; (n) B. Maleki, S. Babaee
and R. Tayebee, Appl. Organomet. Chem., 2015, 29, 408; (o)
18 S. Kantevari, S. V. N. Vuppalapati, D. O. Biradar and
L. Nagarapu, J. Mol. Catal. A: Chem., 2007, 266, 109.
19 L. Nagarapu, S. Apuri and S. Kantevari, J. Mol. Catal. A:
Chem., 2007, 266, 104.
20 S. D. Sharma, P. Hazarika and D. Konwar, Tetrahedron Lett.,
2008, 49, 2216.
21 S. Subhasis, C. N. Ganesh, S. Pallavi and M. S. Singh,
Tetrahedron, 2009, 65, 10155.
22 K. Mazaahir, M. Poonam, B. Vikas, K. S. Rishi, S. E. Abdul,
K. Mazaahir and D. Sharmistha, J. Mol. Catal. A: Chem.,
2007, 265, 177.
23 K. Sivakumar, A. Kathirvel and A. Lalitha, Tetrahedron Lett.,
2010, 51, 3018.
24 R. Hekmat Shoar, G. Rahimzadeh, F. Derikvand and
M. Farzaneh, Synth. Commun., 2010, 40, 1270.
25 A. Hassaninejad, A. Zare, M. Shekouhy and J. A. Rad, J. Comb.
Chem., 2010, 12, 844.
26 A. Mohammadi, H. Keshvari, R. Sandaroos, B. Maleki,
H. Rouhi, H. Moradi and Z. Sepehr, Appl. Catal., A, 2012,
429–430, 73.
27 M. A. Zolgol, A. Khazaei, A. R. Moosavi-Zare, A. Zare,
Z. Asgari, V. Khakyzadeh and A. Hasaninejad, J. Ind. Eng.
Chem., 2013, 19, 721.
28 A. Teimouri and A. Naja Chermahini, J. Mol. Catal. A:
Chem., 2011, 346, 39.
B.
Maleki,
M.
Baghayeri,
S.
M.
Vahdat,
29 H. Zang, Q. Su, Y. Mo, B. W. Cheng and S. Jun, Ultrason.
Sonochem., 2010, 17, 749.
A. Mohammadzadeh and S. Akhoondi, RSC Adv., 2015, 5,
46545.
30 A. Zare, F. Bahrami, M. Merajoddin, M. Bandari, 44 A. Chaudhuri, M. Mandal and K. Mandal, J. Alloys Compd.,
A. R. Moosavi-Zare, M. A. Zolgol, A. Hasaninejad, 2009, 487, 698.
M. Shekouhy, M. H. Beyzavi, V. Khakyzadeh, M. Mokhlesi 45 E. Raee and S. Eavani, J. Mol. Catal. A: Chem., 2013, 373, 30.
and Z. Asgari, Org. Prep. Proced. Int., 2013, 45, 211.
64856 | RSC Adv., 2015, 5, 64850–64857
This journal is © The Royal Society of Chemistry 2015

View Article Online
Paper
RSC Advances
46 A. Khojastehnezhad, M. Rahimizadeh, H. Eshghi, 49 H. Eshghi, A. Khojastehnezhad, F. Moeinpour, M. Bakavoli,
F. Moeinpour and M. Bakavoli, Chin. J. Cat., 2014, 35, 376. S. M. Seyadi and M. Abbasi, RSC Adv., 2014, 4, 39782.
47 A. Khojastehnezhad, M. Rahimizadeh, F. Moeinpour, 50 F. Nikbakht, A. Heydari, D. Saberi and K. Azizi, Tetrahedron
H. Eshghi and M. Bakavoli, C. R. Chim., 2014, 17, 459. Lett., 2013, 54, 6520.
48 H. Eshghi, A. Khojastehnezhad, F. Moeinpour, Sh. Rezaeian, 51 E. Raee and S. Eavani, Green Chem., 2011, 13, 2116.
M. Bakavoli, M. Teymouri, A. Rostami and K. Haghbeen,
Tetrahedron, 2015, 71, 436.
This journal is © The Royal Society of Chemistry 2015
RSC Adv., 2015, 5, 64850–64857 | 64857