Imidazole-functionalized magnetic Fe3O4 nanoparticles: an efficient, green, recyclable catalyst for one-pot Friedl?nder quinoline synthesis

Article abstract of DOI:10.1007/s11164-015-2411-9

An efficient and cost-effective procedure for preparation of Fe₃O₄ nanoparticles and supported Br?nsted acidic ionic liquid 1-methyl-3-(3-trimethoxysilylpropyl)imidazolium hydrogen sulfate (Fe₃O₄-IL-HSO₄

Full text of DOI:10.1007/s11164-015-2411-9

Res Chem Intermed
DOI 10.1007/s11164-015-2411-9
Imidazole-functionalized magnetic Fe3O4
nanoparticles: an efficient, green, recyclable catalyst
¨
for one-pot Friedlander quinoline synthesis
Sobhan Rezayati1 Mogharab Torabi Jafroudi2
•
•
Eshagh Rezaee Nezhad1 Rahimeh Hajinasiri3
•
•
Sima Abbaspour2
Received: 11 November 2015 / Accepted: 23 December 2015
Ó Springer Science+Business Media Dordrecht 2016
Abstract An efficient and cost-effective procedure for preparation of Fe3O4
nanoparticles and supported Brønsted acidic ionic liquid 1-methyl-3-(3-
trimethoxysilylpropyl)imidazolium hydrogen sulfate (Fe3O4-IL-HSO4) as a Brøns-
ted acidic ionic liquid and efficient magnetic catalyst is described, together with its
¨
use for one-pot synthesis of polysubstituted quinolines through Friedlander con-
densation of 2-aminoaryl ketones with 1,3-dicarbonyl compounds under solvent-
free conditions. The most noteworthy aspects of this methodology are its environ-
mental friendliness, simplicity of operation, excellent yield within short reaction
time, easy product isolation, and excellent reusability potential of the catalyst.
¨
Keywords Friedlander quinoline synthesis Á Magnetic nanoparticles Á Fe3O4-IL-
HSO4 Á Solvent-free Á Brønsted acid ionic liquid
Introduction
Quinolines and their derivatives are an important class of nitrogen-containing
heterocycles and have recently received great attention because of their wide range
of therapeutic and biological properties such as antiasthmatic (chloroquine and
Electronic supplementary material The online version of this article (doi:10.1007/s11164-015-2411-9)
contains supplementary material, which is available to authorized users.
&
Sobhan Rezayati
sobhan.rezayati@yahoo.com
1
2
Department of Chemistry, Payame Noor University, P.O. Box 19395-4697, Tehran, Iran
Department of Chemistry, Faculty of Science, Islamic Azad University, Rasht Branch, Rasht,
Iran
3
Chemistry Department, Islamic Azad University, Qaemshahr Branch,
P.O. Box 163, Qaemshahr, Iran
123

S. Rezayati et al.
mefloquine), tyrosine kinase inhibitory [luotonin A and 20(S)-camptothecin],
cytotoxic (e.g., benzo[5,6]pyrrolizino[1,2-b]quinolines), antiinflammatory, anti-
malarial, antihypertensive, and antibacterial activities (Fig. 1) [1–5]. In addition
to medicinal properties, the quinoline nucleus is frequently found in various natural
products [6]; for example, aminoquinolines are found to inhibit acetylcholinesterase
[7] and the butyrylcholinesterase family of enzymes [8] (Fig. 1). Also, quinoline
derivatives are utilized for synthesis of nano- and mesostructures having enhanced
electronic and photonic properties [9–11].
Various procedures for preparation of quinoline derivatives have been developed,
such as the Skraup [12], Pfitzinger [13, 14], Conrad–Limpach–Knorr [15, 16],
¨
Friedlander [17, 18], and Combes methods [19, 20]. However, among the various
methods for quinoline synthesis, Friedlander condensation is the most simple,
¨
¨
versatile, and useful method for synthesis of polysubstituted quinolines. Friedlander
condensation involves base- or acid-catalyzed or thermal condensation between a
2-aminoaryl ketone and a carbonyl compound having a reactive a-methylene group
followed by cyclodehydration. Therefore, it is important to develop more
convenient methods for preparation of quinoline derivatives. Several catalysts
(Brønsted acids and Lewis acids) have been used to promote this reaction, such as
hydrochloric acid [21], sulfamic acid [22], magnetic-nanoparticle-supported
organocatalysts [23], oxalic acid [24], CeCl3Á7H2O [25], Y(OTf)3 [26], SnCl2 and
ZnCl2 [27], organocatalysts [28], 1-butylimidazolium tetrafluoroborate [Hbim]BF4
[29], sulfonic-acid-functionalized ionic liquid [30], phosphotungstic acid [31], silver
phosphotungstate [32], and neodymium(III) nitrate hexahydrate [33], and an
¨
important review in the Friedlander reaction field has been published [34].
However, many of these methods suffer from one or more disadvantages, such as
low product yield, long reaction time, harsh reaction conditions, difficulties in
HO
N
O
N
H
HN
N
H
N
N
N
N
CF3
Cl
CF3
II: Mefloquine
III: Luotonin A
I: Chloroquine
O
N
N
O
HO
IV: 20-(S)-Camptothecin
O
Fig. 1 Examples of biologically active quinoline derivatives
123

Imidazole-functionalized magnetic Fe3O4 nanoparticles: an…
workup, tedious workup procedures, need for excess reagents and catalysts, and/or
relatively expensive reagents, with no agreement regarding green chemistry
protocols, high temperatures, and use of toxic organic solvents. Moreover, the
main disadvantage of almost all existing methods is that the catalysts are destroyed
in the workup procedure and cannot be recovered or reused. Therefore, introduction
of a new and inexpensive catalyst that can be easily separated and reused, and does
not become contaminated by the products is of prime importance. Recently, use of
nanoparticles (NPs) in organic synthesis and industrial manufacture of materials has
become of increasing importance because of their high surface area and unique
magnetic properties. Also, magnetic nanoparticles have been investigated due to
their potential biomedical applications in various fields, such as bioseparation [35,
36], magnetothermal therapy [37, 38], magnetic resonance imaging [39], drug
delivery [40, 41], data storage [42], environmental remediation [43], and
biomolecular sensing [44, 45]. In continuation of our studies toward development
of new and cleaner methods for organic transformations [46–54], in this work we
prepared Fe3O4 nanoparticles and supported Brønsted acidic ionic liquid 1-methyl-
3-(3-trimethoxysilylpropyl)imidazolium hydrogen sulfate (Fe3O4-IL-HSO4) for
¨
one-pot synthesis of polysubstituted quinolines through Friedlander condensation
of 2-aminoaryl ketones with 1,3-dicarbonyl compounds in absence of solvent
(Scheme 1). The mean size and surface morphology of the nanoparticles were
characterized by transmission electron microscopy (TEM), scanning electron
microscopy (SEM), vibrating-sample magnetometry (VSM), X-ray diffraction
(XRD), and Fourier-transform infrared (FTIR) techniques.
Materials and methods
General
FeCl2Á4H2O (99 %), FeCl3Á6H2O (98 %), 2-aminoaryl ketones, 1,3-diketones or
ketones, and other chemical materials were purchased from Fluka and Merck and
used without further purification. All compounds are known, and their structures
were identified by comparing their melting points and 1H and 13C nuclear magnetic
1
resonance (NMR) data with those reported in literature. H and 13C NMR spectra
were obtained in CDCl3 at 500 and 125 MHz, respectively. Chemical shifts are
given in ppm with respect to internal tetramethylsilane (TMS), and J values are
O
Ph
O
O
O
MNP-IL-HSO4
solvent-free, 90 oC
Ph
NH2
OEt
OEt
N
3
1
2
¨
Scheme 1 Modified Friedlander reaction
123

S. Rezayati et al.
quoted in Hz. IR spectra of the compounds were obtained on a PerkinElmer
spectrometer version 10.03.06 using a KBr disk. Melting points were taken on an
Electrothermal capillary melting point apparatus and are uncorrected. The phases
present in the magnetic materials were analyzed using powder XRD (X’Pert model,
˚
Philips, The Netherlands), with Cu Ka1 radiation (k = 1.5401 A) generated at
40 kV and 30 mA. Diffraction patterns were collected from 2h = 20° to 80°.
Substrate purity assessment and reaction monitoring were carried out by TLC on
Polygram SILG/UV254 silica gel plates.
Preparation of Fe3O4-IL-HSO4
Magnetite nanoparticles were prepared by the conventional coprecipitation method
[55]. A schematic representation of the synthesis of magnetic nanoparticles
supporting ionic liquid is shown in Scheme 1. 1-Methyl-3-(3-trimethoxysilyl-
propyl)imidazolium chloride (IL) prepared from reaction of imidazole with (3-
chloropropyl)trimethoxysilane was heated at 110 °C for 17 h with continuous
stirring under N2 atmosphere [56]. Then, excess amount of KHSO4 was added into
deionized water and stirred for 24 h at room temperature. KCl was prepared by
exchange of chloride anions with HSO4 [57], and MNP-IL-HSO4 was separated by
magnetic decantation, washed with acetonitrile and dichloromethane, and left to dry
in a desiccator.
General procedure for one-pot synthesis of quinoline derivatives 3a–n
A mixture of 2-aminoaryl ketone (1 mmol), carbonyl compounds (1 mmol), and
Fe3O4-IL-HSO4 (20 mg) was stirred at 90 °C for the specified time (see Table 4).
The reaction was monitored by TLC. After completion of the reaction, as monitored
by TLC, the reaction mixture was cooled to room temperature, and extracted by
EtOAc (10 mL) to separate the catalyst (the product is soluble in EtOAc). EtOAc
was removed, and the crude product was recrystallized from aqueous ethanol
(90 %) to afford pure product which required no further purification. The recovered
catalyst was washed with EtOAc (2 9 10 mL), dried, and reused for the next run.
The catalyst was reused for four times without any significant change in yield or
1
reaction time. All products were identified by melting point determination and H
NMR and 13C NMR spectroscopy.
1
Table 4, entry 1: M.p.: 103–105 °C (lit. 102–103 °C) [31]; H NMR (CDCl3,
500 MHz) d: 0.97 (t, J = 7.2 Hz, 3H), 2.82 (s, 3H), 4.10 (q, J = 7.2 Hz, 2H),
7.37–7.42 (m, 2H), 7.45–7.54 (m, 4H), 7.62 (dd, J = 8.4, 1.0 Hz, 1H), 7.75 (td,
J = 8.3, 1.5 Hz, 1H), 8.11 (d, J = 8.5 Hz, 1H); 13C NMR (CDCl3, 125 MHz) d:
14.1, 24.3, 61.8, 125.5, 126.8, 126.9, 127.8, 128.7, 128.9, 129.3, 129.8, 130.7,
136.1, 146.7, 148.1, 155.0, 168.9.
1
Table 4, entry 2: M.p.: 102–104 °C (lit. 99–100 °C) [31]; H NMR (CDCl3,
500 MHz) d: 2.78 (s, 3H), 3.55 (s, 3H), 7.41–8.03 (m, 9H); 13C NMR (CDCl3,
125 MHz) d: 24.19, 52.59, 126.92, 126.97, 127.72, 128.71,128.94, 129.66, 130.81,
136.08, 154.97.
123

Imidazole-functionalized magnetic Fe3O4 nanoparticles: an…
1
Table 4, entry 4: M.p.: 150–152 °C (lit. 153–154 °C) [31]; H NMR (CDCl3,
500 MHz) d: 1.64–1.66 (m, 2H), 1.88–1.89 (m, 4H), 2.70–2.75 (m, 2H), 3.31–3.33
(m, 2H), 7.24–7.38 (m, 4H), 7.48–7.65 (m, 4H), 8.06 (d, J = 8.4 Hz, 1H); 13C NMR
(CDCl3, 125 MHz) d: 27.5, 28.9, 31.1, 32.4, 40.6, 126.0, 126.8, 127.3, 128.0, 128.6,
128.9, 129.0, 129.9, 134.2, 138.1, 145.9, 146.2, 165.2.
1
Table 4, entry 11: M.p.: 151–154 °C (lit. 150–152 °C) [31]; H NMR (CDCl3,
500 MHz) d: 2.00 (s, 3H), 2.68 (s, 3H), 7.35–7.95 (m, 8H); 13C NMR (CDCl3,
125 MHz) d: 23.6, 31.6, 124.7, 125.8, 128.8, 129.1, 129.8, 130.8, 132.3, 134.5,
135.4, 142.9, 145.8, 153.8, 204.9.
Results and discussion
Preparation and characterization of Fe3O4-IL-HSO4
A schematic representation of the synthesis of magnetic nanoparticles supporting
ionic liquid is shown in Scheme 2. Firstly, imidazole was reacted with (3-
chloropropyl)trimethoxysilane by heating at 110 °C for 17 h with continuous
stirring under N2 atmosphere to afford 1-methyl-3-(3-trimethoxysilylpropyl)imida-
zolium chloride. In the next step, excess amount of KHSO4 was added into
deionized water and stirred for 24 h at room temperature. Finally, KCl was prepared
by exchange of chloride anions with HSO4 [57], and MNP-IL-HSO4 was separated
by magnetic decantation, washed with acetonitrile and dichloromethane, and left to
dry in a desiccator [55–57] (see Electronic Supplementary Information for
experimental procedures for synthesis of Fe3O4-IL-HSO4 as well as TEM, SEM,
VSM, XRD, and FTIR results).
Optimization of reaction conditions
After preparation of Fe3O4-IL-HSO4, condensation of 2-aminoaryl ketones with 1,3-
dicarbonyl compounds in presence of Fe3O4-IL-HSO4 for preparation of polysub-
stituted quinolines was studied (Scheme 1). To standardize the conditions, a model
reaction using 2-aminobenzophenone 1 (1 mmol) and ethyl acetoacetate 2 (1 mmol)
was carried out using different amounts of Fe3O4-IL-HSO4 under solvent-free
condition to provide ethyl 2-methyl-4-phenylquinoline-3-carboxylate; the results
are presented in Table 1, from which it can be seen that this reaction was strongly
influenced by the amount of catalyst. The best results were obtained using 20 mg
Fe3O4-IL-HSO4, giving ethyl 2-methyl-4-phenylquinoline-3-carboxylate in excel-
lent yield and short reaction time (Table 1, entry 6).
In the next part of the study, we carried out the reaction of 2-aminobenzophenone
1 (1 mmol) and ethyl acetoacetate 2 (1 mmol) in presence of 20 mg Fe3O4-IL-
HSO4 at various temperatures under solvent-free conditions (Table 2). As shown in
Table 2, different temperatures resulted in different yields, with shorter reaction
time and excellent yield being obtained when the reaction was carried out in
presence of 20 mg Fe3O4-IL-HSO4 at 90 °C.
123

S. Rezayati et al.
H
+
FeCl3 6H2O
+
FeCl2 4H2O
N
N
(MeO)3Si
Cl
80 oC,
NH3
110 oC,
17h
1h
OH
HO
HO
OH
OH
H
N
Fe3O4
NP
N
HO
HO
OH
OH
+
Cl-
Si(OMe)3
HO
OH
HO
ethanol
Si
Si
Si
Si
O
O
O
O
O
O
O
O
O
O
Si
O
Si
Si
O
Si
O
O
Si
O
O
O
O
Fe3O4
NP
KHSO4
Water
Fe3O4
NP
O
O
H
H
N
N
Si
N
N
O
O
O
O
Si
O
Si
Cl
O
O
Si
HSO4
O
Si
O
O
O
O
MNP-IL-HSO4
MNP-IL-Cl
Scheme 2 Synthesis of magnetic-nanoparticle-supported ionic liquid (MNP-IL-HSO4)
Table 1 Optimization of catalyst loading in model reaction
Entry
Catalyst
Catalyst amount (mg)
Time (min)
Yield (%)a
1
2
3
4
5
6
7
a
Fe3O4-IL-HSO4
Fe3O4-IL-HSO4
Fe3O4-IL-HSO4
Fe3O4-IL-HSO4
Fe3O4-IL-HSO4
Fe3O4-IL-HSO4
Fe3O4-IL-HSO4
None
1
12 h
120
90
Trace
41
5
54
10
15
20
30
80
65
65
78
40
85
40
71
Isolated yields
In another study, the reaction was examined in presence of different catalysts
(Lewis and Brønsted acids) such as Fe2? supported on hydroxyapatite core–shell
c-Fe2O3 nanoparticles (Table 3, entry 1), Ni2? supported on hydroxyapatite core–
123

Imidazole-functionalized magnetic Fe3O4 nanoparticles: an…
Table 2 Optimization of
Entry
Temperature (°C)
Time (min)
Yield (%)a
temperature in presence of
20 mg Fe3O4-IL-HSO4
1
2
3
4
5
80
90
30
25
25
35
40
88
96
91
88
84
100
120
130
a
Isolated yields
Table 3 Synthesis of compound 3a using different catalysts
Entry
Catalyst
Time (min)
Yield (%)f
1
2
3
4
5
6
a
c-Fe2O3–HAp-Fe2?a
c-Fe2O3–HAp-Ni2?b
Citric acidc
Cyanuric chlorided
SESAe
45
45
91
89
60
55
87
96
120
150
30
Fe3O4-IL-HSO4
25
20 mg c-Fe2O3-HAp-Fe2? was used
20 mg c-Fe2O3-HAp-Ni2? was used
b
c
d
e
f
7 mol % citric acid was used
5 mol % cyanuric chloride was used
10 mol % SESA was used
Isolated yields
shell c-Fe2O3 nanoparticles (Table 3, entry 2), citric acid (Table 3, entry 3),
cyanuric chloride (Table 3, entry 4), and silica-supported [2-(sulfooxy)ethyl]sul-
famic acid (Table 3, entry 5). The results are summarized in Table 1. Excellent
yield of ethyl 2-methyl-4-phenylquinoline-3-carboxylate was obtained in short
reaction time when Fe3O4-IL-HSO4 was utilized as catalyst (Table 3, entry 6).
Subsequently, we used 20 mg Fe3O4-IL-HSO4 for one-pot synthesis of polysub-
¨
stituted quinolines by Friedlander condensation of 2-aminoaryl ketones with 1,3-
dicarbonyl compounds under solvent-free conditions at 90 °C. The results are
summarized in Table 3.
Scope of reaction
As can be seen from Table 4, to assess the efficiency and scope of Fe3O4-IL-HSO4
for one-pot synthesis of polysubstituted quinolines, various 1,3-dicarbonyl com-
pounds (acyclic 1,3-diketone, cyclic 1,3-diketones, and b-ketoesters) were reacted
with 2-aminoaryl ketones or 2-amino-5-chloroaryl ketones using the optimal
reaction conditions to produce the desired products in good to high yield (85–96 %)
and short reaction time (20–60 min). Carbonyl compounds including b-ketoesters
(methyl and ethyl acetoacetate), cyclic ketones (cyclohexanone, cyclopentanone,
123

S. Rezayati et al.
Table 4 Synthesis of quinoline derivatives catalyzed by Fe3O4-IL-HSO4
Entry 2-aminoaryl ketones 1
Ketone 2
Product 3
Time (min) Yield (%)a
O
Ph
CO2Et
O
O
1
25
96
Ph
NH2
OEt
N
O
Ph
CO2Me
COMe
O
O
Ph
2
3
20
20
94
90
OMe
NH2
O
N
Ph
O
O
Ph
N
NH2
O
O
Ph
4
5
15
25
95
93
Ph
NH2
O
N
O
Ph
Ph
NH2
O
N
Ph
N
O
O
O
O
6
7
40
45
88
85
Ph
NH2
O
Ph
O
O
Ph
NH2
O
N
Ph
O
8
40
89
Ph
N
NH2
O
O
Ph
9
25
45
91
95
Ph
NH2
O
N
Ph
Ph
O
O
Cl
CO2Me
Cl
10
OMe
Ph
NH2
N
123

Imidazole-functionalized magnetic Fe3O4 nanoparticles: an…
Table 4 continued
Entry 2-aminoaryl ketones 1
Ketone 2
Product 3
Time (min) Yield (%)a
Ph
O
O
O
Cl
COMe
Cl
11
12
13
14
15
35
35
20
60
60
93
91
92
87
86
Ph
NH2
N
O
O
O
Ph
Cl
Cl
Cl
Cl
Cl
Ph
NH2
O
N
Ph
Cl
Ph
N
NH2
O
Ph
O
Cl
O
O
Ph
N
NH2
O
Ph
O
O
O
Cl
Ph
NH2
N
Reaction conditions: 2-aminoaryl ketones (1 mmol), carbonyl compounds (1 mmol), catalyst Fe3O4-IL-
HSO4 (20 mg); 90 °C, solvent-free
a
Isolated yields
and acetophenone), and pentane-2,4-dione were reacted with 2-aminoaryl ketones to
afford excellent yields in short reaction times (Table 1, entries 1–5, 9). Also, cyclic
1,3-diketones (1,3-cyclohexanedione and 5,5-dimethylcyclohexanedione), cyclic
ketones (cyclohexanone and cyclopentanone), b-ketoester (methyl acetoacetate),
and 2,3-dihydroinden-1-one were reacted with 2-aminoaryl ketones or 2-amino-5-
chloroaryl ketones, giving good yields in slightly longer reaction times (Table 4,
entries 6–8, 10–15). All synthesized compounds were characterized by melting
1
point and H and 13C NMR spectral techniques.
Catalyst reusability is of major importance in heterogeneous catalysis. The
recovery and reusability of the catalyst were studied using the reaction of
2-aminobenzophenone 1 (1 mmol) and ethyl acetoacetate 2 (1 mmol) performed in
presence of 20 mg Fe3O4-IL-HSO4 at 90 °C. After completion of the reaction, as
monitored by TLC, the reaction mixture was cooled to room temperature and
extracted with warm EtOAc to separate the catalyst (the product is soluble in
EtOAc). EtOAc was removed, and the recovered catalyst was washed with EtOAc,
dried, and reused for synthesis of ethyl 2-methyl-4-phenylquinoline-3-carboxylate
according to the mentioned procedure. The catalyst was consecutively reused six
times without noticeable loss of catalytic activity (Fig. 2).
123

S. Rezayati et al.
100
80
60
40
20
6
0
5
4
3
Run
2
1
Time (min) Yield (%)
Fig. 2 Recyclability of Fe3O4-IL-HSO4 for synthesis of ethyl 2-methyl-4-phenylquinoline-3-carboxylate
after 10 min
To show the merit of the present work in comparison with results reported in
literature, we compare the results of Fe3O4-IL-HSO4 catalyst with reported catalysts
for synthesis of quinoline derivatives in Table 5. As can be seen from this table,
several of these methods suffer from one or more drawbacks such as long reaction
time, harsh reaction conditions, use of hazardous catalyst, low product yield, or use
Table 5 Comparison of Fe3O4-IL-HSO4 with other acid catalysts for preparation of quinoline
derivatives
Reaction conditions
Catalyst loading
(mol%)
Time
(min)
Yield
(%)a
Ref.
Hydrochloric acid, H2O, 60 °C
Sulfamic acid, solvent-free, 70 °C
Oxalic acid, solvent-free, 80 °C
CeCl3Á7H2O, CH3CN, room temperature
Yb(OTf)3, CH2Cl2, room temperature
SnCl2ÁZnCl2, EtOH, 70 °C
CuO nanoparticles, solvent-free, 60 °C
PMAÁSiO2, EtOH, reflux
Chitosan-SO3H, EtOH, reflux
0.1b
5
0.1b
30–360
30–90
120
85–96
82–95
88–95
65–95
75–95
70–98
85–98
80–95
79–92
91–97
[21]
[22]
[24]
[25]
[26]
[27]
[58]
[59]
[60]
[61]
25
90–300
60–120
180
5
16.55b
5
60–480
45–100
20–40
90–210
100c
100c
0.7
c-Fe2O3@HAp-Si-(CH2)3-NHSO3H, room
temperature, neat
d
–
Fe3O4-IL-HSO4, solvent-free, 80 °C
20c
20–60
85–96
a
Isolated yields
b
In mmol
c
In mg
d
This work
123

Imidazole-functionalized magnetic Fe3O4 nanoparticles: an…
of nonrecyclable catalyst. So, Fe3O4-IL-HSO4 acts as an effective catalyst with
respect to reaction time, yield, and products. In general, the reaction is very clean,
rapid, efficient, and free from side-reactions, such as self-condensation of ketones as
normally observed under basic conditions.
Conclusions
We have developed a simple, cost-effective, green methodology for one-pot
¨
synthesis of polysubstituted quinolines through Friedlander condensation of
2-aminoaryl ketones with 1,3-dicarbonyl compounds using Fe3O4-IL-HSO4 as
Brønsted acidic ionic liquid and efficient magnetic catalyst under solvent-free
conditions at 90 °C. The advantages of this method include experimental
operational ease, avoidance of hazardous organic solvents and use of nontoxic
reagents, short reaction time and high product yield in comparison with other
procedures, inexpensive reagents, reusability of catalyst, and nonchromatographic
purification of products, i.e., simple recrystallization from aqueous ethanol.
Acknowledgments The authors gratefully acknowledge partial support of this work by Ilam Payame
Noor University, I.R. of Iran.
References
1. R.D. Larsen, E.G. Corley, A.Q. King, J.D. Carrol, P. Davis, T.R. Verhoeven, P.J. Reider, M. Labelle,
J.Y. Gauthier, Y.B. Xiang, R.J. Zamboni, J. Org. Chem. 61, 3398 (1996)
2. Y.L. Chen, K.C. Fang, J.Y. Sheu, S.L. Hsu, C.C. Tzeng, J. Med. Chem. 44, 2374 (2001)
3. G. Roma, M.D. Braccio, G. Grossi, F. Mattioli, M. Ghia, Eur. J. Med. Chem. 35, 1021 (2000)
4. B. Kalluraya, S. Sreenivasa, Farmaco 53, 399 (1998)
5. D. Doube, M. Blouin, C. Brideau, C. Chan, S. Desmarais, D. Eithier, J.P. Falgueyret, R.W. Friesen,
M. Girard, Y. Girard, J. Guay, P. Tagari, R.N. Young, Bioorg. Med. Chem. Lett. 8, 1255 (1998)
6. Z.Z. Ma, Y. Hano, T. Nomura, Y.J. Chen, Heterocycles 46, 541 (1997)
7. F.H. Shaw, G. Bentley, J. Aust. Exp. Biol. Med. Sci. 31, 573 (1953)
8. S. Maayani, H. Weinstein, N. Ben-Zvi, S. Cohen, M. Sokolovsky, Biochem. Pharmacol. 23, 1263
(1974)
9. A.K. Agarwal, S.A. Jenekhe, Macromolecules 24, 6806 (1991)
10. X. Zhang, A.S. Shetty, S.A. Jenekhe, Macromolecules 33, 2069 (2000)
11. S.A. Jenekhe, L. Lu, M.M. Alam, Macromolecules 34, 7315 (2001)
12. Z.H. Scrap, Monatsh. Chem. 1, 316 (1880)
13. W. Pfitzinger, J. Prakt. Chem. 33, 100 (1886)
14. P.K. Calaway, H.R. Henze, J. Am. Chem. Soc. 61, 1355 (1939)
15. N.D. Heindel, T.A. Brodof, J.E. Kogelschatz, J. Heterocycl. Chem. 3, 222 (1966)
16. I. Hermecz, G. Kereszturi, L. Vasvari-Debreczy, Adv. Heterocycl. Chem. 54, 1 (1992)
17. P. Friedlander, Chem. Ber. 15, 2572 (1882)
18. E.A. Fehnel, J. Org. Chem. 31, 2899 (1966)
19. R. Long, K. Schofield, J. Chem. Soc. 3161 (1953). doi:10.1039/JR9530003161
20. E. Roberts, E.E. Turner, J. Chem. Soc. 1832 (1927). doi:10.1039/JR9270001832
21. G.W. Wang, C.S. Jia, Y.W. Dong, Tetrahedron Lett. 47, 1059 (2006)
123

S. Rezayati et al.
22. L.S. Yadav, P.P. Rao, D. Sreenu, R.S. Rao, V.N. Kumar, K. Nagaiah, A.R. Prasad, Tetrahedron Lett.
46, 7249 (2005)
23. R. Mrowczynski, A. Nan, J. Liebscher, RSC Adv. 4, 5927 (2014)
24. M. Dabiri, M. Baghbanzadeh, M.S. Nikcheh, Monatsh. Chem. 138, 1249 (2007)
25. D.S. Bose, R.K. Kumar, Tetrahedron Lett. 47, 813 (2006)
26. S.K. De, R. Gibbs, Tetrahedron Lett. 46, 1647 (2005)
27. B.R. Mcnaughton, B.L. Miller, Org. Lett. 5, 4257 (2003)
28. B. List, Chem. Rev. 107, 5413 (2007)
29. S.S. Palimkar, S.A. Siddiqui, T. Daniel, R.J. Lahoti, K.V. Srinivasan, J. Org. Chem. 68, 9371 (2003)
30. J. Akbari, A. Heydari, H.R. Kalhor, S. Azizian Kohan, J. Comb. Chem. 12, 137 (2010)
31. M. Dabiri, S. Bashiribod, Molecules 14, 1126 (2009)
32. J.S. Yadav, B.V.S. Reddy, P. Sreedhar, R. Srinivasa Rao, K. Nagaiah, Synthesis 2381 (2004). doi:10.
1055/s-2004-831185
33. R. Varala, R. Enugala, S.R. Adapa, Synthesis 3825 (2006). doi:10.1055/s-2006-950296
´
34. J. Marco-Contelles, E. Perez-Mayoral, A. Samadi, M. do Carmo Carreiras, E. Soriano, Chem. Rev.
109, 2652 (2009)
35. D. Wang, J. He, N. Rosenzweig, Z. Rosenzweig, Nano Lett. 4, 409 (2004)
36. C. Xu, K. Xu, H. Gu, R. Zheng, H. Liu, X. Zhang, Z. Guo, B. Xu, J. Am. Chem. Soc. 126, 9938
(2004)
37. R. Hiergeist, W. Andra, N. Buske, R. Hergt, I. Hilger, U. Richter, W. Kaiser, J. Magn. Magn. Mater.
201, 420 (1999)
38. A. Jordan, R. Scholz, P. Wust, H. Fahling, R. Felix, J. Magn. Magn. Mater. 201, 413 (1999)
39. Q.A. Pankhurst, J. Connolly, S.K. Jones, J. Dob-son, J. Phys. D Appl. Phys. 36, 167 (2003)
40. A.K. Gupta, A.S.G. Curtis, J. Mater. Sci. Mater. Med. 15, 493 (2004)
41. T. Neuberger, B. Schoepf, H. Hofmann, M. Hofmann, J. Magn. Magn. Mater. 293, 483 (2005)
42. T. Hyeon, Chem. Commun. 927 (2003). doi:10.1039/B207789B
43. A. Lu, W. Schmidt, N. Matoussevitch, H. Bonnemann, B. Spliethoff, B. Tesche, E. Bill, W. Kiefer, F.
Schuth, Angew. Chem. 116, 4403 (2004)
44. J.M. Perez, F.J. Simeone, Y. Saeki, L. Josephson, R. Weissleder, J. Am. Chem. Soc. 125, 10192
(2003)
45. D.L. Graham, H.A. Ferreira, P.P. Freitas, Trends Biotechnol. 22, 455 (2004)
46. S. Sajjadifar, S. Rezayati, Chem. Pap. 68, 531 (2014)
47. S. Rezayati, Z. Erfani, R. Hajinasiri, Chem. Pap. 69, 536 (2015)
48. S. Rezayati, F. Sheikholeslami-Farahani, F. Rostami-Charati, S.A.S. Abad, Res. Chem. Intermed.
(2015). doi:10.1007/s11164-015-2261-5
49. S. Rezayati, R. Hajinasiri, Z. Erfani, Res. Chem. Intermed. (2015). doi:10.1007/s11164-015-2168-1
50. H.S. Haeri, S. Rezayati, E.R. Nezhad, H. Darvishi, Res. Chem. Intermed. (2015). doi:10.1007/
s11164-015-2318-5
51. S. Sajjadifar, Z. Abbasi, E.R. Nezhad, M. Rahimi Moghaddam, S. Karimian, S. Miri, J. Iran. Chem.
Soc. 11, 335 (2013)
52. E.R. Nezhad, Z. Abbasi, S. Sajjadifar, Sci. Iran. C 22, 903 (2015)
53. S. Rezayati, S. Sajjadifar, J. Sci. I. R. Iran 25, 329 (2014)
54. E.R. Nezhad, Z. Abbasi, S. Sajjadifar, S. Rezayati, J. Sci. I. R. Iran 25, 127 (2014)
55. M.H. Valkenberg, C. Decastro, W.F. Holderich, Green Chem. 4, 88 (2002)
56. S. Nazari, Sh Saadat, P. Kazemian Fard, M. Gorjizadeh, E.R. Nezhad, M. Afshari, Monatsh. Chem.
144, 1877 (2013)
57. E.R. Nezhad, S. Karimian, S. Sajjadifar, J. Sci. I. R. Iran 26, 233 (2015)
58. J. Mohammad Nezhad, J. Akbari, A. Heydari, B. Alirezapour, Bull. Korean Chem. Soc. 32, 3853
(2011)
59. B. Das, M. Krishnaih, K. Laxminarayana, D. Nandankumar, Chem. Pharm. Bull. 56, 1049 (2008)
60. B.V. Subba Reddy, A. Venkateswarlu, G. Niranjan Reddy, Y.V. Rami Reddy, Tetrahedron Lett. 54,
5767 (2013)
61. M. Sheykhan, L. Ma’mani, A. Ebrahimi, A. Heydari, J. Mol. Catal. A Chem. 335, 253 (2011)
123