Sulfamic acid supported on Fe3O4@SiO2superpara magnetic nanoparticles as a recyclable heterogeneous catalyst for the synthesis of quinolines

Article abstract of DOI:10.1039/c4ra06699e

In the present study, for the first time the synthesis of sulfamic acid supported on Fe₃O₄@SiO₂superpara magnetic nanoparticles as a solid acid catalyst with large density of sulfamic acid groups was suggested. The structu

Full text of DOI:10.1039/c4ra06699e

RSC Advances
View Article Online
View Journal | View Issue
PAPER
Sulfamic acid supported on Fe3O4@SiO2 superpara
magnetic nanoparticles as a recyclable
heterogeneous catalyst for the synthesis of
quinolines
Cite this: RSC Adv., 2014, 4, 41753
M. A. Nasseri, B. Zakerinasab and M. M. Samieadel
In the present study, for the first time the synthesis of sulfamic acid supported on Fe3O4@SiO2 superpara
magnetic nanoparticles as a solid acid catalyst with large density of sulfamic acid groups was suggested.
The structural and magnetic properties of functionalized Fe3O4@SiO2 nanoparticles are identified by
TEM, IR, VSM, XRD, TGA and elemental analysis. Then, the applicability of the synthesized nanoparticles
was tested as a recyclable acidic catalyst for the synthesis of quinoline derivatives, an important class of
potentially bioactive compounds. The products are obtained in good to high yields (72–98%) from one-
pot reaction procedure involving carbonyl compounds and 2-amino benzophenone under solvent-free
conditions.
Received 30th July 2014
Accepted 19th August 2014
DOI: 10.1039/c4ra06699e
www.rsc.org/advances
RTK inhibiting properties.14–20 For the synthesis of quinolines,
1. Introduction
various methods have been reported including the Skraup,21
Conrad–Limpach–Knorr,22,23 Ptzinger,24,25 Friedlander
and
26,27
¨
In recent years, there has been a rapid growth in the develop-
ment of novel supported compounds such as supported cata-
lysts, reagents and scavengers. Preparing heterogeneous
catalysts by immobilizing the homogenous precursors on a
solid support is one of the important routes for developing
novel heterogeneous catalysts. In most of these cases, the
immobilized catalysts so prepared could provide advantages
over their unsupported counterparts in terms of easy separa-
tion, low toxicity, moisture resistance, air tolerance, easy
handling, reusability.1–3 On a different note, magnetic nano-
particles (MNPs) have gained an increasing interest because of
their potential applications such as their uses for cell separa-
tion,4 magnetic resonance imaging,5 drug delivery systems,6
protein separation7 and cancer treatments through hyper-
thermia.8 Also, magnetic nanoparticles (MNP) can be a good
candidate as a support material for heterogeneous catalysts,
because of easy synthesis, high surface area, facile separation by
magnetic forces, low toxicity and cost.9 According to these
attractive properties, many MNP supported catalysts have been
designed and widely applied as novel magnetically separated
catalysts in traditional metal catalysis,10,11 organocatalysis,12
and even enzyme catalysis.13
Combes.28,29 However, the Friedlander condensation is still
considered as a popular method for the synthesis of quinoline
derivatives.30–34 In this method, 2-amino benzophenone
condenses with ketones or b-diketones to yield quinolines.
Nevertheless the development of new synthetic methods for the
efficient preparation of heterocycles containing quinoline
fragment is therefore an interesting challenge. In this work, for
combining the benets of sulfamic acid and heterogeneous
magnetic catalysts, we reveal a new nanometer scale, magnetic,
supported, acidic catalyst which can be used for different
organic functional group transformations as a catalyst in green
processes. Then, we studied its catalytic activity in the synthesis
of quinoline derivatives by treatment of 2-amino benzophenone
with various carbonyl compounds. Quinoline derivatives were
produced with good to high yields (72–98%) under solvent-free
conditions.
2. Results and discussion
2.1 Catalyst characterization
Due to the reasonable needs to clean and green recovery of the
heterogenous catalyst, we synthesized Fe3O4@SiO2 bonded
N-propyl diethylene tetrasulfamic acid (Fe3O4@SiO2@PDETSA)
as a new nanomagnetic heterogeneous systems. Firstly, Fe3O4
MNPs were prepared by the reaction of FeCl2$4H2O, FeCl3-
$6H2O with sodium hydroxide in deionized water. For coat silica
on Fe3O4 MNPs, to mixture Fe3O4 and tetraethoxysilane (TEOS)
was added NH3 and was stirred mechanically for 6 h at room
The synthesis of quinolines has been of considerable interest
to chemists because their oxygen heterocycles may contribute to
potential antimalarial, antibacterial, antiasthmatic, antihyper-
tensive, antiinammatory, antiplatelet and tyro kinase PDGF-
Department of Chemistry, College of Sciences, University of Birjand, Birjand
97175-615, Iran. E-mail: manaseri@birjand.ac.ir
This journal is © The Royal Society of Chemistry 2014
RSC Adv., 2014, 4, 41753–41762 | 41753

View Article Online
RSC Advances
Paper
temperature to produce Fe3O4@SiO2 MNPs. Then, Fe3O4@SiO2 Fe3O4@SiO2@PDETSA nanoparticles were observed by trans-
propyl chloride was prepared by the reaction of Fe3O4@SiO2 mission electron microscopy (TEM) as shown in Fig. 1.
with (3-chloropropyl) trimethoxy silane in dry toluene for 48 h.
From TEM images (Fig. 1a), it can be seen that Fe3O4 MNPs
Then resulting compound was treated with diethylene triamine are uniformly and the average size of Fe3O4 MNPs is about 5–
in dry toluene for 24 h to give Fe3O4@SiO2 bonded N-propyl 8 nm. Aer being coated with a SiO2, the typical core–shell
diethylene triamine (Fe3O4@SiO2@PDETA). Finally, the reac- structure of the Fe3O4@SiO2 can be observed and the average
tion of Fe3O4@SiO2@PDETA with chlorosulfonic acid at 0 ꢀC size increases to about 8–10 nm (Fig. 1b). Fig. 1c was showed
gave Fe3O4@SiO2-bonded N-propyl diethylene tetrasulfamic TEM of Fe3O4@SiO2@PDETSA and the average size of MNPs is
acid (Fe3O4@SiO2@PDETSA) (Scheme 1).
about 10–12 nm.
The synthesized catalyst was characterized by different
2.1.2 X-ray diffraction (XRD) analysis. The structural
methods such as TEM, IR, VSM, XRD, TGA and elemental properties of synthesized Fe3O4, Fe3O4@SiO2 and Fe3O4@
analysis. SiO2@PDETSA MNPs were analyzed by XRD. As shown in Fig. 2,
2.1.1 Transmission electron microscopy (TEM). The XRD patterns of the synthesized Fe3O4 nanoparticle display
morphology and sizes of (a) Fe3O4 and (b) Fe3O4@SiO2 and (c) several relatively strong reection peaks in the 2 h region of 20–
Scheme 1 Preparation of Fe3O4@SiO2 bonded N-propyl diethylene tetrasulfamic acid MNPs [Fe3O4@SiO2@PDETSA].
41754 | RSC Adv., 2014, 4, 41753–41762
This journal is © The Royal Society of Chemistry 2014

View Article Online
Paper
RSC Advances
Fig. 1 TEM pattern of (a) Fe3O4 MNPs (b) Fe3O4@SiO2 MNPs (c) Fe3O4@SiO2@PDETSA (d) after the five cycles.
According to the result calculated by Scherrer equation, it
was found that the diameter of Fe3O4 nanoparticles obtained
was about 8 nm and Fe3O4@SiO2 microspheres were obtained
with a diameter of about 10 nm due to the agglomeration of
Fe3O4 inside nanospheres and surface growth of silica on the
shell. The average sizes of Fe3O4@SiO2@PDETSA nanoparticles
are calculated to be 12 nm using the Scherrer equation, which
are in good accordance with TEM results.
2.1.3 Thermal gravimetric analysis (TGA). The thermal
behavior of Fe3O4@SiO2@PDETSA MNPs are shown in Fig. 3. A
signicant decrease in the weight percentage of the Fe3O4@
SiO2@PDETSA MNPs at about 185 ꢀC that this was evaluated to
be ꢁ1.5% according to the TGA analysis. In addition, the
analysis showed other decreasing peak appeared at temperature
Fig. 2 XRD pattern of (A) Fe3O4 MNPs (B) Fe3O4@SiO2 MNPs (C)
Fe3O4@SiO2@PDETSA.
ꢀ
around 650 C due to the decomposition of the organic spacer
80 ꢀC, which is quite similar to those of Fe3O4 nanoparticles
reported by other group. The patterns indicate a crystallized
structure at 2q: 30.2, 35.3, 43.2, 53.5, 57 and 62.5, which are
assigned to the (220), (311), (400), (422), (511) and (440)
crystallographic faces of magnetite (reference JCPDS card no.
19-629). It can be seen that the Fe3O4 obtained has highly
crystalline cubic spinel structure which agrees with the stan-
dard Fe3O4 (cubic phase) XRD spectrum (PDF#88-0866). The
¨
XRD pattern of Fe3O4@SiO2 prepared by the Stober process,
shows an obvious diffusion peak at 13–28 that appeared
because of the existence of amorphous silica. For Fe3O4@
SiO2@PDETSA nanoparticles, the broad peak was transferred to
lower angles due to the synergetic effect of amorphous silica
and DETSA.
Fig. 3 TGA pattern of Fe3O4@SiO2@PDETSA MNPs.
RSC Adv., 2014, 4, 41753–41762 | 41755
This journal is © The Royal Society of Chemistry 2014

View Article Online
RSC Advances
Paper
group (decomposition of the catalyst). Therefore, the covalent
bonds in the catalyst endow it with high thermal stability.
2.1.4 IR spectra. The successful conjugation of sulfamic
acid onto the surface of the Fe3O4@SiO2 nanoparticles was
conrmed by the IR spectra (Fig. 4). The peaks at 3415 and 1010
cmꢂ1 appear in IR spectra of compound 4A, which are assigned
to the –OH and Si–O group, respectively (Fig. 4A). In IR spectra
of the Fe3O4@SiO2@PDETSA MNPs, CH2 bending at 1480 cmꢂ1
and Si–C stretching at 1210 cmꢂ1are observed as a broad band
(Fig. 4B and C). broad band at 3150–3500 cmꢂ1, attributed to
hydroxyl group of sulfonic acid group (Fig. 4C). The absence of
this band in the spectrum of 4B indicates the loss of hydroxyl
group of Fe3O4@SiO2.
Fig. 5 VSM pattern of (A) Fe3O4 MNPs (B) Fe3O4@SiO2 MNPs (C)
2.1.5 Vibrating sample magnetometer (VSM). The
magnetic properties of the sample containing a magnetite
component were studied by a vibrating sample magnetometer
(VSM) at 300 K (Fig. 5). Fig. 5 shows the absence of hysteresis
phenomenon and indicates that product has super-
paramagnetism at room temperature. The saturation magneti-
zation values for (A) Fe3O4, (B)Fe3O4@SiO2 and (C)
Fe3O4@SiO2@PDETSA.
the catalytic efficiency of Fe3O4@SiO2@PDETSA MNPs and to
determine the most appropriate reaction conditions; initially a
model study was carried out on the synthesis of quinoline 3
(Scheme 2) by the condensation of 2-aminobenzophenone 1
and 1,3-cyclohexadione
conditions.
In preliminary experiment, this reaction was carried out in
various solvents, with Fe3O4@SiO2@PDETSA MNPs (0.02 g) as a
catalyst. The reaction could be carried out in various solvent and
gave product in low yield (Table 1, entries 1–9). It was very
surprising that the reaction proceeded in excellent yields (78%)
under solvent-free condition (Table 1, entry 10). The reaction
proceeded perfectly in high temperature, but the yields
decreased when the reaction was carried out in low temperature.
To obtain the optimized reaction conditions, we also
changed temperature and the amount of catalyst. The results
are summarized in Fig. 6.
Fe3O4@SiO2@PDETSA were 68.4, 43.2 and 36.8 emu gꢂ1
,
2 in different sets of reaction
respectively. These results indicated that the magnetization of
Fe3O4 decreased considerably with the increase of SiO2 and
propyl diethylene tetrasulfamic acid.
2.1.6 Elemental analysis. Elemental analysis of Fe3O4@
SiO2@PDETSA gave the following results: N and S 1.54 and
4.69%, respectively. Ratio N : S determined from elemental
analysis 3 : 4 was obtained (Fe3O4@SiO2@C7H18N3S4O12). The
content of S obtained from elemental analysis showed that
typically a loading of 1.4 mmol gꢂ1 H+ was obtained.
2.2 Catalytic activity of Fe3O4@SiO2@PDETSA for the
synthesis of quinolines
Consequently, among the tested temperature and the
amount of catalyst, the condensation of 2-aminobenzophenone
and 1,3-cyclohexadione was best catalyzed by 0.02 g Fe3O4@
SiO2@PDETSA MNPs at 110 C.
To evaluate catalytic activity of Fe3O4@SiO2@PDETSA MNPs,
the model reaction was carried out at 110 C for 45 min under
In order to show the merit of synthesized heterogeneous cata-
lyst in organic reactions, Fe3O4@SiO2 bonded N-propyl dieth-
ylene tetrasulfamic acid [Fe3O4@SiO2@PDETSA] was used, for
the synthesis of quinolines by treatment of 2-amino-
benzophenone and carbonyl compounds. In order to evaluate
ꢀ
ꢀ
solvent-free condition in the presence of different catalytic
systems (0.02 g), separately. The results are shown in Table 2. As
it is evident from the results, Fe3O4@SiO2@PDETSA MNP was
the most effective catalyst in terms of yield of the quinolines
(98%) while other catalysts formed the product with the yields
of 22–48% (Table 2, entries 1–9). Control experiments indicate
that in the absence of the catalyst, the reaction at the same
condition gives quinoline in a rather low yield of 20% (Table 2,
entry 10).
Fig. 4 IR spectra of (A) Fe3O4@SiO2 MNPs (B) Fe3O4@SiO2@PDETA (C)
Fe3O4@SiO2@PDETSA.
Scheme 2
41756 | RSC Adv., 2014, 4, 41753–41762
This journal is © The Royal Society of Chemistry 2014

View Article Online
Paper
RSC Advances
Table 1 The effect of various solvent on the synthesis of quinoline 3
was longer than those of 2-aminobenzophenone. The reaction
of cyclic diketones took place faster than open chain analogues.
These reactions also proceeded with ketone derivatives (Table 3,
entries 13–17). In these cases the reaction times are longer. It
may be due to the less activity of ketone derivatives than
dicarbonyl compounds.
At the end of the reaction, the catalyst could be recovered by
an external magnet. The recycled catalyst was washed with
dichloromethane and subjected to a second reaction process.
The results show that the yield of product aer seven runs was
only slightly reduced (Fig. 7).
In Table 4, the efficiency of our method for the synthesis of
quinolines is compared with some other published works in
literature. Each of these methods have their own advantages,
but they oen suffer from some troubles including the use of
organic solvent, necessity of temperature control (entry 2), long
reaction time (entries 3–9) and employ of non-recyclable cata-
lyst (entries 6, 7, 10 and 11).
Entry
Solvent
Yielda %
Yieldb %
1
2
3
4
5
6
7
8
9
10
H2O
MeOH
EtOH
CH3CN
THF
5
10
10
5
—
—
—
5
35
58
58
15
20
45
45
60
76
78
CHCl3
CH2Cl2
Dioxane
Ethylene glycol
Solvent-free
20
25
a
Reaction condition: 2-amino-benzophenone (1 mmol), 1,3-
cyclohexadione (1 mmol), catalyst (0.02 g), solvent (2 mL) at r.t.
Reaction condition: 2-amino-benzophenone (1 mmol), 1,3-
b
cyclohexadione (1 mmol), catalyst (0.02 g), solvent (2 mL) at 80 ꢀC.
3. Experimental
3.1 Chemicals
Reagents and solvents were purchased from Merck or Fluka
chemical companies. Purity determinations of the products
were accomplished by TLC on silica-gel polygram SILG/UV 254
plates. Melting points were measured on an Electro thermal
9100 apparatus. IR spectra were taken on a Perkin Elmer 781
spectrometer in KBr pellets and reported in cmꢂ1.1 H NMR and
13C NMR spectra were measured on a Bruker DPX-250 Avance
instrument at 250 MHz and 62.9 MHz in CDCl3 or DMSO-d6
with chemical shi given in ppm relative to TMS as internal
standard. The morphology of the products were determined by
using CMPhilips10 model Transmission Electron Microscopy
(TEM) at accelerating voltage of 100 kV. Power X-ray diffraction
(XRD) was performed on a Bruker D8-advance X-ray diffrac-
tometer with Cu Ka (l ¼ 0.154 nm) radiation. The thermo-
gravimetric analysis (TGA) curves were recorded under air
atmosphere using TGA/DTA Shimadzu-50 with platinum pan.
The samples were heated in air from 25 to 800 ꢀC with a heating
rate of 10 ꢀC minꢂ1. The weight losses as a function of
temperature were recorded. The magnetic properties were
determined by using vibrating sample magnetometer (VSM)
leak shore 7200 at 300 K Vsm leak shore.
Fig. 6 The effect temperature and the amount of catalyst for the
synthesis of quinoline 3.
Table 2 One-pot synthesis of quinoline 3 in the presence of various
catalytic systemsa
Entry
Catalyst
Yieldb (%)
1
2
3
4
5
6
7
8
9
10
MgO
CaO
CdO
PbO
CuO
As2O3
Fe3O4
SiO2
42
22
45
42
38
45
48
22
98
20
Fe3O4@SiO2@PDETSA MNP
None
a
Reaction conditions: 2-aminobenzophenone (1 mmol), 1,3-
cyclohexadione (1 mmol), catalyst (0.02 g) at 110 ꢀC under solvent-free
condition. b The yield refers to pure isolated product.
3.2 Catalyst preparation
To establish the generality and applicability of this method,
3.2.1 Preparation of Fe3O4 nanoparticles. Firstly, 15 g
2-amino-5-chlorobenzophenone/2-aminobenzophenone
carbonyl compounds were subjected to the same reaction water. Then, the mixture of 2 g FeCl2$4H2O, 5.2 g FeCl3$6H2O,
condition to furnish the corresponding quinolines (Table 3). 25 mL deionized water and 0.85 mL HCl was added drop by
and sodium hydroxide (NaOH) was dissolved into 25 mL deionized
Not only diketones (Table 3, entries 1–12) but also ketones drop with vigorous stirring to make a black solid product. The
(Table 3, entries 13–17) afforded the desired products in good to resultant mixture was heated on water bath for 4 h at 80 ꢀC. The
excellent yields (72–98%) in short reaction time (45–160 min). It black magnetite solid MNPs were isolated by an external
is delighted that the reaction time of 1,3-diphenyl propane-1,3- magnet and washed with deionized water and ethanol three
ꢀ
dione was longer than those of acetylacetone, which is probably times and was then dried at 80 C for 10 h .
due to low reactivity of carbonyl groups. Also, the reaction time
3.2.2 Preparation of Fe3O4@SiO2 core–shell. Fe3O4 (0.50 g,
of 2-amino-5-chlorobenzophenone and dicarbonyl compounds 2.1 mmol) was dispersed in the mixture of ethanol (100 mL) and
This journal is © The Royal Society of Chemistry 2014
RSC Adv., 2014, 4, 41753–41762 | 41757

View Article Online
RSC Advances
Paper
Table 3 Synthesis of quinolinesa
Entry
Substrate 1
Substrate 2
Quinoline 3
Time (min)
45
Yieldb (%)
1
98
2
3
45
95
89
120
4
5
120
120
83
90
6
7
8
9
120
120
120
160
87
98
92
89
10
11
120
90
82
95
41758 | RSC Adv., 2014, 4, 41753–41762
This journal is © The Royal Society of Chemistry 2014

View Article Online
Paper
RSC Advances
Table 3 (Contd.)
Entry
Substrate 1
Substrate 2
Quinoline 3
Time (min)
160
Yieldb (%)
12
13
14
15
88
120
120
120
83
93
75
16
120
160
89
77
17
a
Reaction conditions: 2-amino-5-chlorobenzophenone or 2-amino benzophenone (1 mmol), carbonyl compounds (1 mmol) in the presence of
Fe3O4@SiO2@PDETSA MNPs (0.02 g) at 110 ꢀC under solvent-free condition. b The yield refers to pure isolated product.
separated by an external magnet and was washed with deion-
ized water and ethanol three times and dried at 80 ꢀC for 10 h.
3.2.3 Preparation of Fe3O4@SiO2 bonded propyl chloride
(Fe3O4@SiO2@PC). Fe3O4@SiO2 (1.0 g) was suspended in dry
toluene (30 mL) and then 3-chloropropyl trimethoxy silane
(15.0 mL) was added followed by triethyl amine (1 mL) as a
catalyst. The suspension was mechanically stirred as it was
heated under reux for 48 h. Fe3O4@SiO2 bonded propyl chlo-
ride MNPs were isolated by an external magnet. The collected
Fig. 7 Recycle of catalyst for the synthesis of quinoline 3.
powder was washed using toluene and ethanol and were dried
under vacuum at 80 ꢀC for 4 h to give Fe3O4@SiO2 bonded
N-propyl chloride (Fe3O4@SiO2@PC).
deionized water (20 mL) for 10 min, Then 2.5 mL of NH3 was
3.2.4 Preparation of Fe3O4@SiO2 bonded N-propyldiethy-
added followed by the addition of tetraethoxysilane (TEOS) (1.5
lenetriamine (Fe3O4@SiO2@PDETA). To a mixture of Fe3O4@
mL) drop by drop. This solution was stirred mechanically for 6 h
SiO2 bonded N-propylchloride (1 g) in dry toluene (30 mL),
at room temperature. Then the product Fe3O4@SiO2 was
This journal is © The Royal Society of Chemistry 2014
RSC Adv., 2014, 4, 41753–41762 | 41759

View Article Online
RSC Advances
Paper
Table 4 Comparison of results using Fe3O4@SiO2@PDETSA MNPs with results obtained by other works for the synthesis of quinolines
Entry
Catalyst
Condition
Yield (%)a
Ref.
1
2
3
4
5
6
7
8
9
10
Current
HClO4–SiO2
PMA–SiO2
Zr(DS)4
Zr(HSO4)4
CH3COOH (1 eq.)
p-TsOH (1 eq.)
bmimCl–ZnCl2
H3PO4 (1 eq.)
HCl
Solvent-free, 110 ꢀC, 45 min
CH3CN, 60 ꢀC, 3 h
EtOH, reux, 8 h
98
92
88
90
87
60
62
80
90
68
—
35
36
37
38
39
39
40
39
41
H2O, reux, 6 h
H2O, reux, 13 h
H2O, 60 ꢀC, 6 h
H2O, 60 ꢀC, 6 h
Ionic liquid, r.t., 24 h
H2O, 60 ꢀC, 12 h
H2O, 100–200 ꢀC, 1 h
diethylene triamine (15 mL) was added and the mixture was by recrystallization using ethanol to afford the pure quinoline
heated under reux with stirring for 24 h. The reaction was product in excellent purity and yield. Structural assignments of
1
cooled to room temperature and the Fe3O4@SiO2 bonded the products are based on their H NMR, 13C NMR, MS and IR
N-propyl diethylene triamine MNPs were isolated by an external spectra.
magnet. The collected compound was washed using toluene
and methanol and was dried for 6 h at 80 ꢀC to give
3.4 Selected data
Fe3O4@SiO2@PDETA.
3.4.1 Compound (entry 2). 7-Chloro-9-phenyl-3,4-dihydro-
1-2H-acridinone: yellow solid, m.p. 184–186 ꢀC (lit. [40] 185 ꢀC),
IR (KBr, cmꢂ1) 3025, 2978, 2874, 1695, 1548, 1475, 1385, 1212,
3.2.5 Preparation of Fe3O4@SiO2 bonded N-propyl dieth-
ylene tetrasulfamic acid [Fe3O4@SiO2@PDETSA]. To
a
magnetically stirred mixture of Fe3O4@SiO2@PDETA (0.5 g) in
1
ꢀ
1078, 1009, 970, 838, 697. HNMR (250 MHz, CDCl3) d 2.26 (q,
CH2Cl2 (10 mL) at 0 C, chlorosulfonic acid (1.80 g) was added
2H, J ¼ 6.4 Hz), 2.72 (t, 2H, J ¼ 6.4 Hz), 3.37 (t, 2H, J ¼ 6.4 Hz),
7.17 (t, 2H), 7.42 (s, 1H), 7.53 (m, 3H), 7.69 (d, 1H, J ¼ 8.8 Hz),
8.01 (d, 1H, J ¼ 8.8 Hz), MS (m/z, %): 308((M + 2) ꢂ 1, 34), 306 (M
ꢂ 1, 100), 281(5), 280(29), 278(15), 253(4), 244(10), 215(27),
188(12), 153(17), 120(20), 107(15).
dropwise over 1 h. Aer the addition was complete, the mixture
was stirred for 12 h until all HCl was removed from the reaction
vessel. Fe3O4@SiO2 bonded N-propyl diethylene tetrasulfamic
acid MNPs were isolated by an external magnet and were
washed with methanol and diethyl ether (30 mL) and then dried
at room temperature to give Fe3O4@SiO2@PDETSA.
3.4.2 Compound (entry 6). Methyl-6-chloro-2-methyl-4-
phenyl-3-quinolinecarbaoxylt: yellow solid, m.p. 135 ꢀC, (lit. [40]
135 C), IR (KBr, cmꢂ1): n: 3038, 2958, 2900, 1747, 1560, 1458,
ꢀ
3.3 Catalytic activity
1405, 1298, 1237, 1185, 1075, 872, 767. 1H NMR (250 MHz,
3.3.1 General procedure for the preparation of quinoline CDCl3): d 2.74 (s, 3H), 3.56 (s, 3H), 7.25–8.01 (c, 8H). 13C NMR
derivatives. To a mixture of carbonyl compounds (1.0 mmol) (62.9 MHz, CDCl3) d 23.7, 52.2, 125.2, 125.8, 128.0, 128.5, 128.8,
and 2-amino-5-chlorobenzophenone or 2-aminobenzophenone 129.1, 130.5, 131.2, 132.4, 134.9, 145.5, 146.1, 145.9, 154.9,
(1.0 mmol) was added Fe3O4@SiO2@PDETSA (0.025 g). The 168.6. MS (m/z, %): 313(M + 2, 31), 311(M+, 100), 296(6), 281(50),
mixture was stirred at 110 ꢀC for appropriated reaction time 279(97), 254(14), 251(16), 236(4), 211(10), 189(34), 175(52),
(Table 3). The progress of the reaction was monitored by TLC. 108(37), 94(33), 74(17).
Aer completion of the reaction, the mixture was dissolved in
3.4.3 Compound (entry 17). 2-Chloro-11-phenyl-7,8,9,10-
acetone and Fe3O4@SiO2@PDETSA MNPs were separated by tetrahydro-6H-cyclohepta[b]quinoline: yellow solid, m.p. 196–
external magnet. Then the solvent was removed from solution 198 ꢀC, (lit. [41] 195 ꢀC), IR (KBr, cmꢂ1): n: 3085, 3052, 2934,
under reduced pressure and the resulting product was puried 2855, 1618, 1600, 1510, 1465, 1364, 1185, 990, 870, 825, 685, 1H
41760 | RSC Adv., 2014, 4, 41753–41762
This journal is © The Royal Society of Chemistry 2014

View Article Online
Paper
RSC Advances
NMR (250 MHz, CDCl3): d: 1.60 (s, 2H), 1.84 (s, 4H), 2.68 (c, 2H)
3.26 (c, 2H), 7.22–7.96 (c, 8H). 13C NMR (62.9 MHz,
CASDEADCl3) d 26.9, 28.4, 30.7, 31.8, 40.1, 125.1, 127.7, 127.9,
128.6, 129.0, 129.3, 130.3, 131.3, 134.8, 136.9, 144.2, 144.7,
165.1, MS (m/z, %): 308((M + 2), 33), 306(M ꢂ 1, 100), 292(9),
280(15), 277(12), 252(13), 242(17), 228(18), 215(18), 201(10),
188(10), 127(23), 120(25), 107(15).
Y. N. Liu and Z. H. Zhang, Appl. Catal., A, 2013, 457, 34; (c)
Y. H. Liu, J. Deng, J. W. Gao and Z. H. Zhang, Adv. Synth.
Catal., 2012, 354, 441; (d) R. B. N. Baig and R. S. Varma,
Green Chem., 2013, 15, 398; (e) J. Deng, L. P. Mo,
F. Y. Zhao, L. L. Hou, L. Yang and Z. H. Zhang, Green
Chem., 2011, 13, 2576; (f) D. H. Turkenburg, A. A. Antipov,
M. B. Thathagar, G. Rothenberg, G. B. Sukhorukov and
E. Eiser, Phys. Chem. Chem. Phys., 2005, 7, 2237; (g)
M. Nina Wichner, J. Beckers, G. Rothenberg and H. Koller,
J. Mater. Chem., 2010, 20, 3840.
Conclusion
´
´
In conclusion, the present work provided a new type of 12 (a) C. O. Dalaigh, S. A. Corr, Y. Gun'ko and S. J. Connon,
heterogeneous for potential synthetic application. Fe3O4@-
SiO2@PDETSA MNPs are an efficient and reusable catalyst for
the synthesis of quinoline derivatives and is comparable with
some other applied catalysts. Products have been achieved by a
Angew. Chem., Int. Ed., 2007, 46, 4329; (b) Y. Zhang and
C. G. Xia, Appl. Catal., A, 2009, 366, 141; (c) X. X. Zheng,
S. Z. Luo, L. Zhang and J. P. Cheng, Green Chem., 2009, 11,
455.
one-pot coupling reaction of carbonyl compounds and o-ami- 13 J. Lee, Y. Lee, J. K. Youn, H. B. Na, T. Yu, H. Kim, S. M. Lee,
nobenzophenone at 110 ꢀC in a short period of time under
solvent-free condition. In addition, it is easy to separate and
recover the catalyst for another catalytic recycling.
Y. M. Koo, J. H. Kwak, H. G. Park, H. N. Chang, M. Hwang,
J. G. Park, J. Kim and T. Hyeon, Small, 2008, 4, 143.
14 M. P. Maguire, K. R. Sheets, K. McVety, A. P. Spada and
A. J. Zilberstein, Med. Chem., 1994, 37, 2129.
15 R. D. Larsen, E. G. Corley, A. O. King, J. D. Carrol, P. Davis,
T. R. Verhoeven, P. J. Reider, M. Labelle, J. Y. Gauthier,
Y. B. Xiang and R. J. Zamboni, J. Org. Chem., 1996, 61, 3398.
16 Y. L. Chen, K. C. Fang, J. Y. Sheu, S. L. Hsu and C. C. Tzeng, J.
Med. Chem., 2001, 44, 2374.
Acknowledgements
We gratefully acknowledge the support of this work by the Bir-
jand University Research Council.
17 G. Roma, M. D. Braccio, G. Grossi, F. Mattioli and M. Ghia,
Eur. J. Med. Chem., 2000, 35, 1021.
References
1 R. Yolanda de Miguel, J. Chem. Soc., Perkin Trans. 1, 2000, 1, 18 B. Kalluraya and S. F. Sreenivasa, Farmaco, 1998, 53, 399.
4213.
19 D. Doube, M. Blouin, C. Brideau, C. Chan, S. Desmarais,
D. Eithier, J. P. Fagueyret, R. W. Friesen, M. Girard,
Y. Girard, J. Guay, P. Tagari and R. N. Young, Bioorg. Med.
Chem. Lett., 1998, 8, 1255.
20 T. C. Ko, M. J. Hour, J. C. Lien, C. M. Teng, K. H. Lee,
S. C. Kuo and L. Huang, Bioorg. Med. Chem. Lett., 2001, 11,
279.
2 R. A. Sheldon and H. van Bekkum, Fine Chemicals through
Heterogeneous Catalysis, Wiley-VCH, Weinheim, 2001.
3 J. H. Clark, D. J. Macquarrie, Green Chemistry and Technology,
Blackwell, Abingdon, 2002.
4 J. Ying, R. M. Lee, P. S. Williams, J. C. Jeffrey, S. F. Sherif,
B. Brian and Z. Maciej, Biotechnol. Bioeng., 2007, 96, 1139.
5 J. Lee, Y. Jun, S. Yeon and J. Shin, Angew. Chem., Int. Ed., 21 Z. H. Skraup, Monatsh. Chem., 1880, 1, 316.
2006, 45, 8160.
22 N. D. Heindel, T. A. Brodof and J. E. Kogelschatz, J.
6 N. Tobias, S. Bernhard, H. Heinrich, H. Margarete and
V. R. Brigitte, J. Magn. Magn. Mater., 2005, 293, 483.
7 H. Gu, K. Xu, C. Xu and B. Xu, Chem. Commun., 2006, 941.
Heterocycl. Chem., 1966, 3, 222.
23 I. Hermecz, G. Kereszturi and L. Vasvari-Debreczy, Adv.
Heterocycl. Chem., 1992, 54, 1.
8 I. Akira, T. Kouji, K. Kazuyoshi, S. Masashige, H. Hiroyuki, 24 W. Ptzinger, J. Prakt. Chem., 1886, 33, 100.
M. Kazuhiko, S. Toshiaki and K. Takeshi, Cancer Sci., 2003, 25 P. K. Calaway and H. R. Henze, J. Am. Chem. Soc., 1939, 61,
94, 308.
1355.
¨
9 (a) V. Polshettiwar, R. Luque, A. Fihri, H. Zhu and 26 P. Friedlander, Chem. Ber., 1882, 15, 2572.
M. Bouhrara, Chem. Rev., 2011, 111, 3036; (b) S. Shylesh, 27 E. A. Fehnel, J. Org. Chem., 1966, 31, 2899.
V. Schunemann and W. R. Thiel, Angew. Chem., Int. Ed., 28 R. Long and K. Schoeld, J. Chem. Soc., 1953, 3161.
2010, 49, 3428; (c) V. Roberto Calderone, N. Raveendran 29 E. Roberts and E. E. Turner, J. Chem. Soc., 1927, 1832.
´
Shiju and D. Curulla-Ferre, Angew. Chem., Int. Ed., 2013, 52, 30 J. S. Yadav, P. Rao, D. Sreenu, R. S. Rao, V. N. Kumar,
4397.
K. Nagaiah and A. R. Prasad, Tetrahedron Lett., 2005, 46,
10 (a) R. Abu-Reziq, H. Alper, D. S. Wang and M. L. Post, J. Am.
7249.
Chem. Soc., 2006, 128, 5279; (b) G. Chouhan, D. S. Wang and 31 V. V. Kouznetsov, L. Y. Mendez and C. M. M. Gomez, Curr.
H. Alper, Chem. Commun., 2007, 4809; (c) T. Hara, T. Kaneta,
Org. Chem., 2005, 9, 141.
K. Mori, T. Mitsudome, T. Mizugaki, K. Ebitani and 32 S. J. Song, S. J. Cho, D. K. Park, T. W. Kwan and S. A. Jenekhe,
K. Kaneda, Green Chem., 2007, 9, 1246; (d) M. J. Jin and
D. H. Lee, Angew. Chem., Int. Ed., 2010, 49, 1119.
11 (a) E. Raee and S. Eavani, Green Chem., 2011, 13, 2116; (b)
Tetrahedron Lett., 2003, 44, 255.
33 S. A. Palimkar, S. A. Siddiqui, T. Daniel, R. J. Lahoti and
K. V. Srinivasan, J. Org. Chem., 2003, 68, 9371.
F. P. Ma, P. H. Li, B. L. Li, L. P. Mo, N. Liu, H. J. Kang, 34 S. K. De and R. A. Gibbs, Tetrahedron Lett., 2005, 46, 1647.
This journal is © The Royal Society of Chemistry 2014
RSC Adv., 2014, 4, 41753–41762 | 41761

View Article Online
RSC Advances
Paper
35 M. Narasimhulu, T. Srikanth Reddy, K. Chinni Mahesh, 38 M. A. Zolgol, P. Salehi, A. Ghaderi and M. Shiri, Catal.
P. Prabhakar, C. Bhujanga Rao and Y. Venkateswarlu, J.
Mol. Catal. A: Chem., 2006, 266, 114.
36 B. Das, M. Krishaiah, K. Laxminarayana and
D. Nandankumar, Chem. Pharm. Bull., 2008, 56, 1049.
37 M. A. Zolgol, P. Salehi, A. Ghaderi, M. Shiri and
Z. Tanbakouchian, J. Mol. Catal. A: Chem., 2006, 259, 253.
Commun., 2007, 8, 1214.
39 G. W. Wang, C. S. Jia and Y. W. Dong, Tetrahedron Lett., 2006,
47, 1059.
40 G. Karthikeyan and P. T. Perumal, J. Heterocycl. Chem., 2004,
41, 1039.
41 G. Kempter and P. Z. Klug, Z. Chem., 1971, 11, 61.
41762 | RSC Adv., 2014, 4, 41753–41762
This journal is © The Royal Society of Chemistry 2014