Tribromide ion immobilized on magnetic nanoparticle as a new, efficient and reusable nanocatalyst in multicomponent reactions

Article abstract of DOI:10.1039/c6ra15474c

Tetraethyldiethylenetriamine tribromide magnetic nanoparticles (MNPs-TEDETA tribromide) are synthesised and characterized as an efficient, new, metal free and magnetically reusable nanocatalyst for the synthesis of 2,3-dihydroquinazolin-4(1H)-one and polyhydroquinoline derivatives. The synthesized catalyst was characterized using FT-IR, TGA, XRD, EDX, VSM and SEM analyses.

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ARTICLE
Tribromide
ion
immobilized
on
magnetic
nanoparticle as new, efficient and reusable
nanocatalyst in multicomponent reactions
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Maryam Hajjami* and Fatemeh Gholamian
www.rsc.org/
Tetraethyldiethylenetriamine tribromide magnetic nanoparticles, (MNPsꢀTEDETA tribromide)
synthesise and characterize as an efficient, new, metal free and magnetically reusable
nanocatalyst for synthesis of 2,3ꢀdihydroquinazolinꢀ4(1H)ꢀone and polyhydroquinoline
derivatives. The synthesized catalyst was characterized by FTꢀIR, TGA, XRD, EDX, VSM and
SEM analyses.
antibacterial, antifertility, antitumor, antifibrilatory, vasodilatory,
antifungal, and analgesic efficacy [15, 16]. In addition quinazolines
1
Introduction
are oxidized into quinazolinꢀ4(3H)ꢀones analogs, which are known
as important biologically active heterocyclic compounds [17]. 2,3ꢀ
dihydroquinazolinꢀ4(1H)ꢀone analogues have been synthesized using
There are two main kinds of catalysis systems, heterogeneous and
homogeneous, that each of them has advantages and drawbacks. For
example benefits of heterogeneous catalysts are easy synthesis, easy
separation, efficient recycling, product purification, and
disadvantages including: insufficient catalytic surface, low activity
and leaching. Meanwhile homogeneous catalysts have benefits such
as high activity and high selectivity, but they have disadvantage such
as laborious product purification, difficulty in recycling and recovery
of the catalyst, deactivation of catalyst towards the end of the
reaction [1ꢀ3]. Because of the catalysts are often expensive, the
several catalyst such as: CuCl
2
/Fe3
O4ꢀTEDETA [4], GSA@MNPs
[
14], BiBr [18], MES (2 morpholinoethanesulfonic acid) [19], SiO ꢀ
3
2
FeCl [20], BoehmiteꢀSSA [21], BoehmiteꢀSiꢀDSA[22].
3
some of these methodologies for the synthesis of 2,3ꢀ
dihydroquinazolinꢀ4(1H)ꢀone was previously reported which
suffered from expensive reagents, tedious workꢀup, high reaction
temperature, harsh reaction conditions and low yields. Thus,
development of a versatile and simple procedure is a highly desired
goal in the synthesis of 2,3ꢀdihydroquinazolinꢀ4(1H)ꢀones [23,16].
Although some of the analogue nanoparticles prepared by other
authors were previously reported [24, 25], the main novelty of this
research is the first report of MNPsꢀTEDETA tribromide without
any transitionꢀmetal, used as the catalyst for multicomponent
reactions.
reusing and separation of them are very important To overcome this
.
afore mentioned drawbacks, magnetic nanoparticles which are often
low cost, easy and clean separation from the reaction mixture with
an external magnet [4ꢀ6], unique properties, potential applications in
the variety of field [7], simple synthesis, high surface area, low
toxicity and readily available are preferred [8].
Multicomponent reactions (MCRs) condensations are a chemical
reaction where three or more simple substrates react to give highly
selective products that retain majority of the atoms of the starting
material [9]. MCRs are an important subclass of tandem reactions
which has advantages such as convergent nature, milder reaction
conditions, simplicity, high atom economy, facile execution, shorter
reaction time, environment friendly, lower cost and energy
conservation [10,11]. In the past decade the methodology of MCRs
have emerged as a very efficient way to access heterocycles [12].
Polyhydroquinoline and 2,3ꢀdihydroquinazolinone derivatives are
very famous molecules that including six membered Nꢀheterocyclic
ring. These compounds have been reported to possess a vast range of
biological properties and pharmaceutical activities [8, 13]. 2,3ꢀ
Dihydroquinazolinones are a class of Nꢀheterocycles that have
attracted much attention because of their broad spectrum of
pharmacological, biological [14] and medicinal activities such as
In this work with the aim to develop an efficient synthetic process,
we develop the synthesis of 2,3ꢀdihydroquinazolinꢀ4(1H)ꢀone
derivative by oneꢀpot twoꢀcomponent condensation of
anthranilamide and aldehydes catalyst by MNPsꢀTEDETA
tribromide in EtOH at reflux condition (Scheme 2) and synthesis of
polyhydroquinoline by multiꢀcomponent reactions of aldehyde,
dimedon, ethylacetoacetate, ammonium acetate and MNPsꢀTEDETA
tribromide as catalyst in PEG at 80 ºC (Scheme 4).
2
Results and discussion
2
.1 Catalyst preparation
In this paper we report a new and efficient method for the synthesis
of 2,3ꢀdihydroquinazolinꢀ4(1H)ꢀones and polyhydroquinolines in the
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presence of catalytic amounts of MNPsꢀTEDETA tribromide. As
shown in Scheme 1 the details synthesis procedure of catalyst is
indicated. Initially the black precipitate of magnetic nano particles of
Fe O has been prepared by a mixture of FeCl ·6H O, FeCl ·4H O in
500
450
400
350
300
250
200
150
100
50
catalyst
Fe3o4
3
4
3
2
2
2
recovered catalyst
3
0% NH OH under N atmosphere at 80℃ [4, 13]. Then, Fe O
4
2
3
4
nanoparticles coated by 3ꢀchloropropyltrimethoxysilane (CPTMS)
solution. In the next step, the mixture of N, N, N′, N′ꢀ
tetraethyldiethylenetriamine (TEDETA) and triethylamine was
added to MNPsꢀCPTMS under reflux of dry toluene. Finally, the
obtain TEDETA functionalized magnetic nanoparticles (MNPsꢀ
TEDETA) was reacted with HBr and Br to afford MNPsꢀTEDETA
0
2
tribromide.
0
20
40
02
60
theta
80
100
(
3ꢀChloropropyl) trimethoxysilane
ethanol/wather, N ,40 °C, 8h
NH
4
OH , N
0 °C , 30min
2
Fe
3
O
4
NP
Figure 1. XRD pattern of MNPsꢀTEDETA tribromide and recovered
catalyst
FeCl
3
.6H
2
O + FeCl
2
.4H
2
O
8
2
MNPs
(
2
Et) N
O
O
O
Figure 2 indicates FTꢀIR spectra for the MNPs, MNPsꢀCPTMS,
MNPsꢀTEDETA, and MNPsꢀTEDETA tribromide. The IR spectrum
of the Fe O alone indicates the bond of stretching vibration at 3401
Cl
Fe
3
O
4
NP
Si
NH
Et
3
N ,
3
4
(
Et) N
−1
2
cm belong to OꢀH bonds which are attached to the surface iron
MNPsꢀCPTMS
dry toluene, 24h, reflux
N(Et)
ꢀ1
atoms and a peak appears at 1625 cm belong to the stretching
2
vibrational mode of an adsorbed water layer. Also the peak that
−1
appeared at 579 cm comes from vibrations of FeꢀO bonds [14, 27].
The IR spectrum of MNPsꢀCPTMS (Fig. 2(b)) shows the peak at
1
) HBr ,1h
O
N
2) Br ,CCl ,6ꢀ7h
2
4
−1
Fe
3
O
4
NP
O
Si
577cm which assigned to the FeꢀO vibration. The band formation
between MNPs and 3ꢀchloropropylsilica group is confirmed by Fe–
O
−1
N(Et)2
O–Si absorption band that appears at near 999 cm [28]. The peaks
MNPsꢀTEDETA
−1
−1
at 2880 cm and 2972 cm attribute to CꢀH stretching vibrations
27, 29].
As shown in Fig. 2(c), the presence of bands in 575 cm and 997
+
ꢀ
H Br
N(Et)
3
[
2
−1
−1
cm is assigned to the FeꢀO vibration [14, 27] and Fe–O–Si
O
+
ꢀ
−1
−1
NH Br
3
absorption [28] respectively. The peaks 2947 cm and 2999 cm
Fe
3
O
4
NP
O
Si
regions attribute to the CꢀH stretching vibrations [29].
O
The IR spectrum of the MNPsꢀTEDETA tribromide (Fig. 2(d))
−
1
−1
N(Et)
H Br
2
MNPsꢀTEDETA Tribromide
indicates the bonds in 564 cm and 627 cm is assigned to
+
ꢀ
3
−1
vibrations of FeꢀO bonds. The presences of band 1630 cm belong
to the stretching vibrations of CꢀN [24]. This IR spectrum also
shows the peaks at 1040 cm and 1116 cm which assigned to the
SiO–H and Si–O–Si groups [30]. The presence of bands in 2923
cm and 2981 cm regions is assigned to the CꢀH stretching
+
Scheme 1. Synthesis of MNPsꢀTEDETA tribromide
.2 Catalyst characterization
−1
−1
−1
−1
2
vibrations [27, 29]. For indicated the peak of Br Br, which exhibits
ꢀ
All reagents and solvents were purchased from Merck and Aldrich
chemical companies. The synthesised catalyst was characterized by
Xꢀray diffraction (XRD, GBCꢀDifftech MMA), Fourier transform
infrared (FTꢀIR, Bruker, Germany) spectroscopy, scanning electron
microscopy (SEM, FESEMꢀTESCAN MIRA3), energy dispersive
Xꢀray (EDX, FESEMꢀTESCAN MIRA3), thermogravimetric
−1
below 400 cm , we captured another FTꢀIR spectra in region below
−1
−1
4
00 cm . As shown in Figure 2 the peaks at 197 and 264 cm
assigned to the Br3.
The scanning electron microscopic (SEM) image was investigated
the morphological and size particle of the catalyst. It confirmed that
analysis (TGA, PerkinElmer Pyris Diamond, U.K), and vibrating the catalyst was made up of uniformꢀsized particle with an average
sample magnetometer (VSM, MDKFD) techniques.
diameter less than 10 nm also the shape of the MNPsꢀTEDETA
tribromide is spherical (Figure 3).
The energy dispersive Xꢀray (EDX) spectrum of catalyst indicates
the kinds of elements present (C, N, O, Si, Fe and Br) in the MNPsꢀ
TEDETA tribromide. As shown in Figure 4 (a) indicated the EDX
As seen in Figure 1 the position of all peaks in the XRD pattern of
MNPsꢀTEDETA tribromide and recovered catalyst were in
agreement with standard XRD pattern of Fe O . As it is shown the
3
4
catalyst and the recovered catalyst were identified from the peak
positions at 2θ = 21.33, 35.20, 41.55, 50.65, 63.19, 67.52, 74.53 and
2
θ = 21.32, 35.09, 41.45, 50.53, 63.27. 67.81, 74.58 respectively. spectrum of recovered catalyst and Figure 4 (b) indicated the EDX
These peaks with the corresponding reflections of (111), (220), spectrum of recovered catalyst.
311), (400), (422), (511) and (440) indicated that the surface
modification of the Fe O nanoparticles does not lead to their phase
(
3
4
change, even after recovery and they all match well with the data for
the standard Fe O sample [26]. Also this pattern indicated that the
3
4
crystalline inverse cubic spinel structures are protecting during
functionalization of MNPs.
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Figure 3. SEM images of the MNPsꢀTEDETA tribromide
6000
5000
4000
3000
2000
1000
0
O Kα
N Kα
SiKα
FeKα
FeLα
BrLα
FeKβ
C Kα
keV
10.00
0
a
Figure 2. FTꢀIR spectra for the MNPs (a), MNPsꢀCPTMS (b),
MNPsꢀTEDETA (c), and MNPsꢀTEDETA tribromide (d).
b
Figure 4. EDX spectrum for MNPsꢀTEDETA tribromide (a),
recovered catalyst (b)
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polyhydroquinoline
The bond formation between the nanoparticles and the catalyst can 2,3ꢀdihydroquinazolinꢀ4(1H)ꢀone
and
be inferred from the thermo gravimetric analysis (TGA). The TGA derivatives. First, to optimize the reaction condition for synthesis of
curves of the MNPsꢀTEDETA tribromide and bare Fe O4 2,3ꢀdihydroquinazolinꢀ4(1H)ꢀone, the condensation of 4ꢀ
3
nanoparticles are showed in Figure 5. The mass loss at temperatures chlorobenzaldehyde (1 mmol) with 2ꢀaminobenzamide and MNPsꢀ
below 200 °C is due to the removal of physically adsorbed surface TEDETA tribromide as catalyst was used as a model reaction
hydroxyl groups and solvent. The weight loss of 7% for MNPsꢀ (Scheme 2). The reactions were carried out in the presence of
o
TEDETA tribromide between 205ꢀ636 C associated to the thermal different amounts of catalyst and 2ꢀaminobenzamide and various
decomposition of organic groups grafted to Fe O .
solvents. The best results were obtained with molar ratio of 1: 1.05
for aldehyde: 2ꢀaminobenzamide and 0.05 g of MNPsꢀTEDETA
tribromide in EtOH under reflux condition (Table1, entry 3).
3
4
1
1
1
10
05
00
O
O
NH
NH
R
CHO
NH2
MNPsꢀTEDETA tribromide
Ethanol, Reflux
R
+
NH2
a
Scheme 2. MNPsꢀ TEDETA tribromide catalyzed the oneꢀpot
synthesis of 2,3ꢀdihydroquinazolinꢀ4(1H)ꢀone derivatives.
9
9
8
8
7
7
5
0
5
0
5
0
In generality, the choice of solvent can have a significant effect on
the performance of a reaction. Solvents can have an effect on
solubility and reaction rates. In this light, we monitored the synthesis
of 2,3ꢀdihydroquinazolinꢀ4(1H)ꢀone using different solvent (polar
and nonꢀpolar ) such as: EtOH, H O, PEG, CH Cl , EtOAc, nꢀHex,
b
2
2
2
and aceton. The green solvent of H O applied but no product was
2
obtained (no reaction). Also the yield of product with PEG was
trace. Although CH Cl EtOAc, nꢀHex, and aceton are not safe
2
2,
solvents, we tested them for more investigation. As shown in Table
, these solvents had low yield (15%ꢀ45%) and were not suitable for
1
2
5
225
425
625
this multi component reaction. Among of several used solvent, EtOH
is the best solvent because EtOH significantly improved the yield
and it is safer than of CH Cl , EtOAc, nꢀHex, and aceton. Also in
Temperature °C
2
2
Figure 5. TGA profile of the Fe O (a) and MNPsꢀTEDETA
tribromide (b)
several method that reported for the synthesis of 2,3ꢀ
dihydroquinazolinꢀ4(1H)ꢀone, the solvent of reaction were EtOH
3
4
[14, 19, 21, 31].
Vibrating sample magnetometer (VSM) analysis is employed for
measurement of magnetic property of MNPs and MNPsꢀ TEDETA Table 1. Optimization condition for the condensation of 4ꢀ
a
tribromide. As shown in Figure 6, the bare MNPs and MNPsꢀ chlorobenzaldehyde (1mmol) and 2ꢀaminobenzamide in EtOH
TEDETA tribromide both present excellent paramagnetism but due Entry 2ꢀaminobenzamide Catalyst Solvent Temperature Yield
b
to the coating of silica and the layer of the attached catalyst, the bare
MNPs indicated the higher magnetic value in comparison with
MNPsꢀ TEDETA tribromide.
(mmol)
(g)
(ºC)
80
80
80
80
80
80
80
70
80
80
80
80
80
80
(%)
63
69
95
1
2
3
4
5
6
7
8
9
1.05
1.05
1.05
1.05
1.05
1.1
0.03
0.04
0.05
0
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
1
00
c
N.R
93
80
60
40
20
0
0.06
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
a
b
88
81
70
1
1.05
1.05
1.05
1.05
1.05
1.05
1.05
H O
N.R
37
2
1
0
CH Cl2
2
11
EtOAc
nꢀHex
PEG
45
15
1
1
1
2
3
4
-10000
-5000
0
5000
10000
-20
-40
-60
-80
Trace
32
aceton
a
b
c
80 min
Isolated yield.
No Reaction
The reaction of the various benzaldehyde derivatives was then
investigated. The 2,3ꢀdihydroquinazolinꢀ4(1H)ꢀone derivatives
were obtained in high yields. The results of this study are
summarized in Table 2. As shown, a variety of benzaldehydes
-
100
H (Oe)
Figure 6. VSM analysis of the Fe O (a) and MNPsꢀTEDETA
3
4
bearing
electronꢀdonation
and
electronꢀwithdrawing
tribromide (b)
substituents were successfully employed to prepare the
corresponding 2,3ꢀdihydroquinazolinꢀ4(1H)ꢀone derivatives in
excellent yields.
2
.3 Catalytic study
After characterizing MNPsꢀ TEDETA tribromide, we investigated its
efficiency as nanocatalyst in organic reactions such as synthesis of
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Table 2. Synthesis of 2,3ꢀdihydroquinazolinꢀ4(1H)ꢀones
catalyzed by MNPsꢀ TEDETA tribromide in ethanol and at 80
ºC.
R
O
O
O
O
CHO
OEt
MNPsꢀTEDETA tribromide
R
+
+
+
NH
4
OAc
OEt
PEG, 80 0
C
O
O
N
H
Entry
Product
Time Yield
M. p
(ºC)
Reference
Scheme 4. Synthesis of polyhydroquinoline derivatives
catalyzed by MNPsꢀ TEDETA tribromide.
a
(min)
(%)
O
NH
NH
Cl
To optimize the reaction conditions for oneꢀpot synthesis of
polyhydroquinoline derivatives, 4ꢀchlorobenzaldehyde with
dimedone, ammonium acetate and ethylacetoacetate was used
as a model reaction in the presence of different organic solvents
and different amounts of catalyst and ammonium acetate in
temperature condition (Table 3).
1
80
95
198ꢀ200
[22]
OMe
O
O
NH
NH
2
3
OMe
35
60
99
70
210ꢀ211
174ꢀ177
[22]
[22]
[4]
NH
NH
OMe
Table 3. Optimization the reaction condition for the synthesis of
polyhydroquinoline using of 4ꢀchlorobenzaldehyde, dimedone,
ammonium acetate, ethylacetoacetate and catalyst as a model
reaction.
O
NH
NH
OEt
F
4
120
92 170ꢀ172
95 204ꢀ206
Entry Catalyst Ammonium Solvent Temperature Time Yield
a
O
(g)
acetate (mmol)
(ºC)
(min) (%)
NH
NH
1
2
3
4
5
6
7
8
9
0.04
0.05
0.06
0
0.05
0.05
0.05
0.05
0.05
0.05
0.05
1.2
1.2
1.2
1.2
1.2
1.2
1.1
1
PEG
PEG
PEG
PEG
PEG
PEG
PEG
PEG
80
80
80
80
60
100
80
80
80
80
80
300
120
140
120
120
120
120
120
78
92
93
20
55
67
74
70
5
65
[31]
O
O
NH
NH
Br
6
7
8
90
60
82 189ꢀ191
96 226ꢀ227
80 187ꢀ190
[22]
[22]
[21]
NH
NH
Me
1.2
1.2
1.2
H O
120 trace
120
120
2
O
O
NH
2
N
10
EtOH
EtOAc
61
50
1
1
130
a
NH
Isolated yield
NO
2
O
As shown in entry 2 of Table 3 after the optimization of the
reaction condition, 4ꢀchlorobenzaldehyde (1 mmol), dimedon
(1 mmol), ethylacetoacetate (1 mmol) and ammonium acetate
NH
NH
9
90
99 192ꢀ193
[21]
(
1.2 mmol) in the presence of 0.05 g MNPsꢀ TEDETA
a
Isolated yield.
tribromide in PEG was showed better results in terms of the
reaction yield and rate.
In this reaction, the various benzaldehyde derivatives were
employed. As shown in Table 4 the polyhydroquinoline
derivatives were obtained in high yields.
The plausible mechanism for the formation of 2ꢀarylꢀ2,3ꢀ
dihydroquinazolinoneꢀ4(1H)ꢀone was proposed and shown in
Scheme 3. The carbonyl group in aldehyde activated with catalyst.
Then the anthranilamide reacted with the activated aldehyde and the
intermediate I is formed. After dehydration of intermediate I, the
imine intermediate II is generated. Finally the intramolecular
cyclization of imine intermediate II produced the final product [32].
Table 4. Synthesis of polyhydroquinoline catalyzed by MNPsꢀ
TEDETA tribromide in PEG and at 80 ºC.
O
OH
Time Yield
Br
H
Entry
1
Product
M. p. (ºC) Reference
a
NH
+
2
O
N
(min)
(%)
OH
Ar
Cl
NH
2
Ar
H
N
H
Br
I
O
O
120
92
235ꢀ238
248ꢀ250
[14]
[14]
2
ꢀH O
OEt
O
OH
N
N
H
Br
NH
NH
N
H
Ar
Ar
Br
II
O
O
2
210
89
Scheme 3. The proposed mechanism of synthesis 2ꢀarylꢀ2,3ꢀ
dihydroquinazolinoneꢀ4(1H)ꢀone
OEt
In the second part of our work we were interested in finding a
method for the oneꢀpot synthesis of polyhydroquinoline
derivatives using MNPsꢀ TEDETA tribromide as a recoverable
nanocatalyst in PEG as a green solvent (Scheme 3).
N
H
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Me
unsaturated compound and the Michaelꢀtype addition of the
intermediates produce the polyhydroquinoline.
O
O
R
O
3
250
240
240
86
90
82
250ꢀ252
224ꢀ226
252ꢀ254
[14]
[14]
[14]
O
OEt
OEt
+
N
H
Br
O
2
H N
O
NH
4
OAc.Cat
OH
O
O
H
OEt
O
R
R
O
O
O
4
OEt
O
OEt
N
H
Br
H
O
N
H
O
OMe
R
4
NH OAc. Cat
O
O
O
O
R
5
OEt
+
OEt
NH
2
N
H
O
Scheme 5. The proposed mechanism of synthesis
polyhydroquinoline derivatives by MNPsꢀTEDETA tribromide
OMe
OMe
2
.4 Recyclability of the catalyst
O
O
6
150
90
199ꢀ200
[29]
The recyclability of the catalyst was studied by using a model
reaction between 2ꢀaminobenzamide and 4ꢀchlorobenzaldehyde in
the presence of catalyst in reflux of EtOH under the optimization
conditions. After completion of the reaction, the product was
dissolved in hot ethanol. Then the catalyst was separated from the
product by an external magnet. Then ethanol was removed by
evaporation. Finally, the pure product was obtained by
recrystallization in the EtOH. The recycled catalyst was dried and
used for further runs and its activity did not show any significant
decrease even after 6 runs (Figure 7).
OEt
N
H
OH
O
O
7
200
290
80
75
230ꢀ232
217ꢀ219
[29]
[29]
OEt
N
H
1
00
90
80
O
O
8
OEt
N
H
F
7
0
O
O
60
9
210
300
87
86
189ꢀ191
176ꢀ178
[14]
[14]
OEt
5
0
N
H
1
2
3
4
5
6
Run number
NO
2
O
O
Figure 7. Recovery of the catalyst in the synthesis of 2,3ꢀ
dihydroquinazolinꢀ4(1H)ꢀones
1
0
OEt
N
H
2.5 Hot filtration
We were studied a hot filtration technique for the synthesis of 2,3ꢀ
dihydroquinazolinꢀ4(1H)ꢀones. We investigated hot filtration
technique for the synthesis of 2,3ꢀdihydroquinazolinꢀ4(1H)ꢀones, by
using of 4ꢀchlorobenzaldehyde (1 mmol), 2ꢀaminobenzamide (1.05
mmol) and MNPsꢀTEDETA tribromide (0.05 g) in refluxing of
ethanol. This reaction carried out at 80 min and yield of product was
a
Isolated yield.
As shown in Scheme 5 the mechanism of the synthesis of
polyhydroquinoline derivatives was indicated [14]. The role of the
catalyst comes in the condensation of aldehydes with the active
methylene compounds (Knoevenagel Condensation) to afford α,βꢀ
9
5%. We repeated the reaction and yield of product in half time of
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the reaction that it was 53%. In another reaction we repeat the vigorous mechanical stirring. Nanoparticles of Fe O was collected
3
4
reaction and after 40 min, catalyst was separated by an external
magnet and washed with hot ethanol, then the solution was allowed
to go for the remaining half stirring. After purification, yield of
product was obtained 55%.
and washed with doubly distilled water (five times) [13].
4
.2
Preparation
of
MNPs
coated
by
3-
chloropropyltrimethoxysilane (MNPs-CPTMS)
2
.6 Comparison of the catalyst
1
.5 mL of 3ꢀchloropropyltrimethoxysilane (CPTMS) was added to
the obtained magnetic Fe O4 nanoparticles (0.5 g) in 50 mL
To demonstrate the merit of MNPsꢀTEDETA tribromide, in
3
comparison with other reported catalysts, we compared the results of EtOH/H O (1:1) under N atmosphere at 40℃ about 8 hours. Then,
2
2
the preparation of 2ꢀ(3,4ꢀdimethoxyphenyl)ꢀ2,3ꢀdihydoquinazolinꢀ
(1H)ꢀone from 3,4ꢀdimethoxybenzaldehyde and anthranilamide
with the previous reported in the literature. As shown in Table 5
these results indicated the efficiency of the proposed methodology in
terms of the reaction yield and rate as compared to literature reports,
also the prepared catalyst in this work is metal free catalyst.
the final product was separated by external magnet. For remove the
unattached substrates the product washed with ethanol and dried at
room temperature.
4
4
.3 Preparation of MNPs-TEDETA tribromide
Table 5. Comparison results of MNPsꢀTEDETA tribromide with
other catalysts for the reaction of anthranilamide and 3,4ꢀ
dimethoxybenzaldehyde
2
mmol N, N, N′, N′ꢀtetraethyldiethylenetriamine (TEDETA) was
added to 4 mmol triethylamine at room temperature for 30 minutes.
The obtained MNPsꢀCPTMS was added to the mixture in dry
toluene under reflux conditions for 24 h. TEDETA functionalized
magnetic nanoparticles (MNPsꢀTEDETA) prepared after washing
with deionized water and ethanol and dried overnight. In the next
Entry
Condition
Time
Yield
%
Ref
(min)
1
2
CuCl2/Fe O ꢀTEDETA
30
96
[4]
3
4
(0.005 g), EtOH, Reflux
GSA@MNPs (0.01 g), EtOH,
Reflux
25
30
98
84
[14] step, HBr 47% was added to MNPsꢀTEDETA and stirred for an
hour. Ultimately bromine in CCl was added to the mixture and
4
3
4
BiBr (5mol%), CH CN, R.T
[18]
3
3
stirred for 6ꢀ7 h. Then the MNPsꢀTEDETA tribromide was collected
by an external magnet and washed with doubly distilled water and
ethanol.
2ꢀMorpholino ethanesulfonic
acid (10 mol%), Ethanol, 60
180 /12
86 /88 [19]
0
C / MWI
5
6
7
8
SiO ꢀFeCl (0.005 g), solvent
42h
130
60
90
88
96
99
[20]
2
3
0
free, 80 C
BoehmiteꢀSSA(0.03 g),
EtOH, Reflux
BoehmiteꢀSiꢀDSA (0.03 g),
EtOH, Reflux
4.4 General procedure for the synthesis of 2,3
[21] dihydroquinazolin-4(1H)-ones derivatives
A stirred mixture of aldehyde (1 mmol), 2ꢀaminobenzamide (1.05
mmol) and MNPsꢀTEDETA tribromide (0.05 g), was reacted in
reflux of ethanol. After completion of the reaction, monitored by
TLC, the product was dissolved in hot ethanol, and then catalyst was
separated from the product by an external magnet. Then ethanol was
removed by evaporation. Finally, pure products were obtained by
recrystallization by EtOH.
[22]
a
MNPsꢀTEDETA tribromide
35
0
(0.05 g), EtOH, 80
C
a
this work
3
Conclusions
4
.5 General procedure for the synthesis of polyhydroquinoline
In summary, we have synthesized the MNPsꢀTEDETA tribromide as
a new, reusable and efficient catalyst for the synthesis of 2,3ꢀ
dihydroquinazolinꢀ4(1H)ꢀones by the condensation between various
aldehydes and anthranilamide in presence of MNPsꢀTEDETA
tribromide and EtOH at 80 ºC and synthesis of polyhydroquinoline
via a oneꢀpot, multicomponent condensation reaction between of
aldehyde, dimedon, ethylacetoacetate, ammonium acetate and
MNPsꢀTEDETA tribromide as catalyst in PEG at 80 ºC. The
benefits of the catalyst are the novelty, easy preparation,
functionalization without tedious condition, easy separation by an
external magnet, and low toxicity and price. Also the catalyst can be
reused for 6 times without any significant loss of its activity.
derivatives
A
mixture of aldehyde (1 mmol), dimedon (1 mmol),
ethylacetoacetate (1 mmol), ammonium acetate (1.2 mmol) and
MNPsꢀTEDETA tribromide (0.05 g) was stirred in PEG at 80 ºC.
The progress of the reaction was monitored by TLC. After
completion of the reaction, catalyst was separated by an external
magnet then product extracted with ethylacetate. Finally, the solvent
was evaporated and all products were recrystallized in ethanol,
which the pure products were obtained in good to excellent yields.
4
.6 Characterization data of all compounds
4
Experimental
2
2
5
ꢀ(4ꢀChlorophenyl)ꢀ2,3ꢀdihydoquinazolinꢀ4(1H)ꢀone (entry 1, Table
1
). H NMR (400 MHz, DMSOꢀd ): δ : 8.29 (s, 1H), 7.60–7.41 (m,
6
H
4
.1 Preparation of the magnetic Fe O nanoparticles (MNPs)
3 4
H), 7.25–7.20 (t, J =7.5, 1H), 7.12 (s, 1H), 6.75–6.63 (m, 2H), 5.75
(
2
s, 1H) ppm.
A mixture of FeCl ·6H O (5.858 g) and FeCl ·4H O (2.221 g) were
dissolved in 100 mL deionized water until the salts dissolved
3
2
2
2
ꢀ(3,4ꢀDimethoxyphenyl)ꢀ2,3ꢀdihydoquinazolinꢀ4(1H)ꢀone (entry 2,
1
Table 2). H NMR (400 MHz, DMSOꢀd ): δ : 8.21 (s, 1H), 7.64–
6
H
completely. Then, 10 mL of 30% NH OH was added in to the 7.61 (d, J = 1.6, 1H), 7.29–7.25 (t, J = 8, 1H), 7.15ꢀ 7.14 (d, J = 1.6,
4
reaction mixture under N atmosphere about 30 min at 80℃ under 1H), 7.03–6.97 (m, 2H), 6.95 (s, 1H), 6.78–6.76 (d, J = 8, 1H), 6.72–
2
6
.68 (t, J= 1.2, 1H), 5.71 (s, 1H), 3.77 (s, 3H), 3.76 (s, 3H) ppm.
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ꢀ(4ꢀMethoxyphenyl)ꢀ2,3ꢀdihydoquinazolinꢀ4(1H)ꢀone (entry 3, MHz, DMSOꢀd ): δH : 9.05 (s, 1H), 6.79–6.76 (m, 2H), 6.65–6.63
2
6
1
Table 2). H NMR (400 MHz, DMSOꢀd ): δ : 8.22 (s, 1H), 7.66– (d, J = 8, 1H), 4.81(s, 1H), 4.04–3.99 (q, J = 7.2, 2H), 3.69–3.68 (d, J
6
H
7
1
.63 (m, 1H), 7.46–7.44 (d, J = 8.8, 2H), 7.29ꢀ 7.24 (m, 1H), 7.04 (s, = 4.4, 5H), 2.47–2.42 (d, J = 17.2, 2H), 2.35–2.29 (m, 4H), 2.22–
H), 6.99ꢀ6.69 (d, J=1.2, 2H), 6.78–6.76 (d, J = 8, 1H), 6.70–6.68 (t, 2.18 (d, J = 16, 1H), 2.03–1.99 (d, J = 16, 1H), 1.20–1.16 (t, J = 7.2,
J= 7.2, 1H), 5.74 (s, 1H), 3.77 (s, 3H) ppm.
3H), 1.03 (s, 3H), 0.90 (s, 3H) ppm.
2
2
7
6
1
2
2
1
ꢀ(4ꢀEthoxyphenyl)ꢀ2,3ꢀdihydoquinazolinꢀ4(1H)ꢀone (entry 4, Table Ethylꢀ4ꢀ(4ꢀhydroxyphenyl)ꢀ2,7,7ꢀtrimethylꢀ5ꢀoxoꢀ1,4,5,6,7,8ꢀ
1
1
). H NMR (400 MHz, DMSOꢀd ): δ : 7.95–7.94 (b, 1H), 7.51– hexahydroquinolineꢀ3ꢀcarboxylate (entry 7, Table 4). H NMR (400
6
H
.50 (m, 2H), 7.34 (s, 1H), 7.27 (s, 1H), 6.94–6.90 (m, 3H), 6.68– MHz, DMSOꢀd ): δ : 9.05 (s, 1H), 8.99 (s,1H), 6.95–6.93 (d, j=8.8,
6
H
.67 (m, 1H), 5.85 (s, 1H), 5.75 (s, 1H), 4.08–4.06 (q, J ¼ 4, 2H), 2H), 6.58ꢀ6.55 (m, 2H), 4.75 (s, 1H), 4.02–3.98 (m, 2H), 2.44–2.40
.46– 1.44 (s, 3H) ppm. (d, J = 16.8, 1H), 2.30–2.26 (m, 4H), 2.19–2.15 (d, J = 16, 1H),
ꢀ(4ꢀFluorophenyl)ꢀ2,3ꢀdihydoquinazolinꢀ4(1H)ꢀone (entry 5, Table 2.00–1.96 (d, J = 16, 1H), 1.17–1.14 (t, J = 7.2, 3H), 1.02 (s, 3H),
1
). H NMR (400 MHz, DMSOꢀd ): δ : 8.32 (s, 1H), 7.65–7.63 (m, 0.87 (s, 3H) ppm.
6
H
H), 7.59–7.54 (m, 2H), 7.30ꢀ 7.23 (m, 3H), 7.13 (s, 1H), 6.79ꢀ6.77 Ethylꢀ4ꢀ(phenyl)ꢀ2,7,7ꢀtrimethylꢀ5ꢀoxoꢀ1,4,5,6,7,8
d, J=0.8, 1H), 6.69ꢀ6.67 (t, J=8, 1H) 5.80 (s, 1H) ppm. hexahydroquinolineꢀ3ꢀcarboxylate (entry 8, Table 4). H NMR (400
1
(
2
2
7
1
ꢀ(4ꢀBromophenyl)ꢀ2,3ꢀdihydoquinazolinꢀ4(1H)ꢀone (entry 6, Table MHz, DMSOꢀd ): δH : 9.08 (s, 1H), 7.22–7.17 (m, 4H), 7.10–7.06
6
1
). H NMR (400 MHz, DMSOꢀd ): δ : 8.17–8.14 (m, 1H), 7.79– (m, 1H), 4.88 (s, 1H), 4.02–3.97 (q, J = 7.2, 2H), 2.46–2.42(d, J =
6
H
.77 (m, 1H), 7.63–7.59 (m, 3H), 7.48–7.45 (m, 2H), 7.29–7.23 (m, 17.2 1H), 2.33–2.29 (t, J=8.8, 4H), 2.21–2.17 (d, J = 16, 1H), 2.02–
H), 6.77–6.72 (d, J = 19.2, 1H), 6.70–6.67 (m, 1H), 5.76 (s, 1H) 1.98 (d, J = 16, 1H), 1.16–1.13 (t, J = 7.2, 3H), 1.03 (s, 3H), 0.86 (s,
ppm.
3H) ppm.
2
ꢀ(4ꢀMethylphenyl)ꢀ2,3ꢀdihydroquinazolinꢀ4(1H)ꢀone (entry 7, Ethylꢀ4ꢀ(4ꢀfluorophenyl)ꢀ2,7,7ꢀtrimethylꢀ5ꢀoxoꢀ1,4,5,6,7,8ꢀ
1
1
Table 2). H NMR (400 MHz, DMSOꢀd ): δ : 8.21 (s, 1H), 7.63– hexahydroquinolineꢀ3ꢀcarboxylate (entry 9, Table 4). H NMR (400
6
H
7
7
.60 (d, J = 7.5, 1H), 7.38–7.35 (d, J = 7.5, 2H), 7.25–7.13 (m, 3H), MHz, DMSOꢀd ): δ : 9.11 (s, 1H), 7.20–7.17 (m, 2H), 7.04–7.00 (t,
.03 (s, 1H), 6.74–6.63 (m, 2H), 5.71 (s, 1H), 2.49–2.42 (s, 3H) J = 8.8, 2H), 4.87 (s, 1H), 4.02–3.96 (q, J = 7.2, 2H), 2.46–2.41 (d, J
= 16.8, 1H), 2.32–2.28 (m, 4H), 2.21–2.17 (d, J = 16, 1H), 2.02–1.98
6 H
ppm.
2
2
=
ꢀ(2ꢀNitrophenyl)ꢀ2,3ꢀdihydoquinazolinꢀ4(1H)ꢀone (entry 8, Table (d, J = 16, 1H), 1.15–1.12 (t, J = 7.2, 3H), 1.02 (s, 3H), 0.85 (s, 3H)
1
). H NMR (400 MHz, DMSOꢀd ): δ :8.25 (s, 1H), 8.10–8.08 (d, J ppm.
6
H
8, 1H), 7.90–7.87 (d, J = 8, 1H), 7.83–7.79 (t, J = 0.8, 1H), 7.69– Ethylꢀ4ꢀ(3ꢀnitrophenyl)ꢀ2,7,7ꢀtrimethylꢀ5ꢀoxoꢀ1,4,5,6,7,8ꢀ 1
.63 (m, 2H), 7.30–7.26 (m, 1H), 7.04 (s, 1H), 6.81 (d, J = 1.2, 1H), hexahydroquinolineꢀ3ꢀcarboxylate (entry 10, Table 4). H NMR
.77–6.72 (m, 1H), 6.36 (m, 1H) ppm. (400 MHz, DMSOꢀd ): δ : 9.25 (s, 1H), 8.12–8.10 (d, J = 8.4, 2H),
7
6
2
2
6
H
ꢀ(3ꢀNitrrophenyl)ꢀ2,3ꢀdihydoquinazolinꢀ4(1H)ꢀone (entry 9, Table 7.45–7.43 (d, J = 8.4, 2H), 4.99 (s, 1H), 4.01–3.95 (q, J = 7.2, 2H),
). H NMR (400 MHz, DMSOꢀd ): δ : 8.57 (s, 1H), 8.40–8.39 (t, 2.48–2.44 (d, J = 17.2, 1H), 2.34–2.30(d,J=16.8, 4H), 2.22–2.18 (d, J
1
6
H
J=1.6, 1H), 8.24–8.21 (m, 2H), 7.98ꢀ 7.96 (d, J=7.6, 1H), 7.74ꢀ7.70 = 16, 1H), 2.02–1.98 (d, J = 16, 1H), 1.14–1.11 (t, J = 7.2, 3H), 1.02
t, J=8, 1H), 7.66ꢀ7.64 (m, 1H), 7.38 (s, 1H), 7.32ꢀ7.28 (m, 1H), (s, 3H), 0.84 (s, 3H) ppm.
.83ꢀ6.81 (d, J=8, 1H), 6.74ꢀ6.70 (m, 1H), 5.98 (s, 1H) ppm.
(
6
Ethylꢀ4ꢀ(4ꢀchlorophenyl)ꢀ2,7,7ꢀtrimethylꢀ5ꢀoxoꢀ1,4,5,6,7,8ꢀ
hexahydroquinolineꢀ3ꢀcarboxylate (entry 1, Table 4). H NMR (400
Acknowledgements
1
MHz, DMSOꢀd ): δH : 9.13 (s, 1H), 7.25–7.28 (m, 2H), 7.17–7.19
6
This research work was financially supported by the Ilam University,
Ilam, Iran is gratefully acknowledged.
(
1
(
m, 2H), 4.86 (s, 1H), 4.01–3.96 (q, J = 7.2, 2H), 2.46–2.41 (d, J =
6.8, 1H), 2.31–2.28 (m, 4H), 2.21–2.17 (d, J = 16, 1H), 2.01–1.97
d, J = 16, 1H), 1.15–1.12 (t, J = 7.2, 3H), 1.02 (s, 3H), 0.85 (s, 3H)
References
ppm.
Ethylꢀ4ꢀ(4ꢀbromophenyl)ꢀ2,7,7ꢀtrimethylꢀ5ꢀoxoꢀ1,4,5,6,7,8ꢀ
hexahydroquinolineꢀ3ꢀcarboxylate (entry 2, Table 4). H NMR (400
1
.
J. Govan and Y. K. Gun’ko, Nanomaterials, 2014, 4, 222.
A. Naghipour and A. Fakhri, Catal. Commun, 2016, 73,
1
2
3
4
5
6
7
8
9
1
1
1
.
.
.
.
.
.
.
.
MHz, DMSOꢀd ): δ : 9.14 (s, 1H), 7.41–7.39 (d, J = 8.4, 2H), 7.13–
6
H
3
9.
7
2
2
0
.11 (d, J = 8.4, 2H), 4.84 (s, 1H), 4.01–3.95 (q, J = 6.8, 2H), 2.52–
.46 (d, J = 26.4, 1H), 2.31–2.28 (m, 4H), 2.21–2.17 (d, J = 16, 1H),
.01–1.97 (d, J = 16, 1H), 1.15–1.11 (t, J = 7.2, 3H), 1.02 (s, 3H),
.84 (s, 3H) ppm.
A. GhorbaniꢀChoghamarani and M. Norouzi, Appl.
Organometal. Chem, 2016, 30, 140.
A. GhorbaniꢀChoghamarani and M. Norouzi, J. Mol. Cata.
A: Chem, 2014, 395, 172.
Y. Zhu, L.P. Stubbs, F. Ho, R. Liu, C.P. Ship, J.A.
Maguire and N.S. Hosmane, Chemcatchem, 2010, 2, 365.
A. Rostami, B. Tahmasbi, F. Abedi and Z. Shokri, J. Mol.
Catal. A: Chem, 2013, 378, 200.
M. Ghorbanloo, R. Tarasi, J. Tao and H. Yahiro, Turk. J.
Chem, 2014, 38, 488.
Ethylꢀ4ꢀ(4ꢀmethylphenyl)ꢀ2,7,7ꢀtrimethylꢀ5ꢀoxoꢀ1,4,5,6,7,8ꢀ
1
hexahydroquinolineꢀ 3ꢀcarboxylate (entry 3, Table 4). H NMR (400
MHz, DMSOꢀd ): δ : 9.04 (s, 1H), 7.05–7.03 (d, J = 8, 2H), 7.00–
6
H
6
2
1
3
.97 (d, J = 8, 2H), 4.81 (s, 1H), 4.01–3.95 (q, J = 6.8, 2H), 2.44–
.40 (d, J = 16, 1H), 2.30–2.26 (m, 4H), 2.21–2.15 (m, 4H), 2.10–
.96 (d, J = 16, 1H), 1.17–1.13 (t, J = 6.8, 3H), 1.02 (s, 3H), 0.86 (s,
H) ppm.
A. Rostami, B. Tahmasbi, H. Gholami and H. Taymorian,
Chin. Chem. Lett, 2013, 24, 211.
M. Hajjami, A. GhorbaniꢀChoghamarani and F.
Gholamian, Bulg. Chem. Commun, 2015, 47, 119.
Ethylꢀ4ꢀ(4ꢀmethoxyphenyl)ꢀ2,7,7ꢀtrimethylꢀ5ꢀoxoꢀ1,4,5,6,7,8ꢀ
1
hexahydroquinolineꢀ3ꢀcarboxylate (entry 5, Table 4). H NMR (400
MHz, DMSOꢀd ): δ : 9.04 (s, 1H), 7.08–7.06 (d, J = 8.4, 2H), 6.77–
6
H
6
3
.75 (d, J = 8.4, 2H), 4.81 (s, 1H), 4.01–3.96 (q, J = 7.2, 2H), 3.68 (s,
H), 2.45–2.41 (d, J = 29.2, 1H), 2.31–2.29 (m, 4H), 2.20–2.16 (d, J
0. BꢀH. Chen, JꢀT. Li and GꢀF. Chen, Ultrason. Sonochem,
015, 23 59.
1. J, Safari and S. GandomiꢀRavandi, J. Mol. Struct, 2014,
072, 173.
2. M. Wang, T. T. Zhang, Y. Liang and J. J. Gao, Monatsh.
Chem, 2012, 143, 835.
2
=
16, 1H), 2.01–1.97 (d, J = 16.4, 1H), 1.17–1.14 (t, J = 7.2, 3H),
1
.02 (s, 3H), 0.87 (s, 3H) ppm.
1
Ethylꢀ4ꢀ(3,4ꢀdimethoxyphenyl)ꢀ2,7,7ꢀtrimethylꢀ5ꢀoxoꢀ1,4,5,6,7,8ꢀ
1
hexahydroquinolineꢀ3ꢀcarboxylate (entry 6, Table 4). H NMR (400
This journal is © The Royal Society of Chemistry 2013
J. Name., 2013, 00, 1-3 | 8

Page 9 of 10
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RSC Advances
View Article Online
DOI: 10.1039/C6RA15474C
ARTICLE
1
3. A. GhorbaniꢀChoghamarani and G. Azadi, RSC Adv, 2015,
, 9752.
5
1
1
4. M. Hajjami and B. Tahmasbi, RSC Adv, 2015, 5, 59194.
5. B. Zhang, L. Shi and R. Guo, Catal Lett, 2015, 145,
1
718.
6. A. SaffarꢀTeluri and Sh. Bolouk, Monatsh Chem, 2010,
41, 1113.
7. Z. KarimiꢀJaberi and R. Arjmandi, Monatsh Chem, 2011,
42, 631.
8. K. R. Gopinath, H. S. Shekar, K. J. Rajendraprasad, H.
Nagabhushana and M. Krishnappa, World. J. Pharm.
Pharm. Sci, 2016, 5, 1272
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
9. V. B. Labade, P. V. Shinde and M. S. Shingare,
Tetrahedron Lett., 2013, 54, 5778.
0. M. Ghashang, K. Azizi, H. MoulaviꢀPordanjani and H. R.
Shaterian, Chin. J. Chem., 2011, 29, 1617.
1. A. GhorbaniꢀChoghamarani, and B. Tahmasbi, New
J.Chem, 2016, 40, 1205.
2. M. Hajjami, A. GhorbaniꢀChoghamarani, R. Ghafouriꢀ
Nejad and B. Tahmasbi, New J.Chem, 2016, 40, 3066.
3. A. Davoodnia, S. Allameh, A.R. Fakhari and N. Tavakoliꢀ
Hoseini, Chin. Chem. Lett, 2010, 21, 550.
4. A. Rostami, Y. Navasi, D. Moradi and A. Ghorbaniꢀ
Choghamarani, Catal. Commun, 2014, 43, 16.
5. S. Otokesh, E. Kolvari, A. Amoozadeh and N. Koukabi,
RSC Adv., 2015, 5, 53749.
6. M. Hajjami and S. Kolivand, Appl. Organometal. Chem,
2
016, 30, 282.
7. A. GhorbaniꢀChoghamarani, Z. Darvishnejad and B.
Tahmasbi, Inorganic. Chim. Acta. 2015, 435, 223.
8. B. Atashkar, A. Rostami and B. Tahmasbi, Catal. Sci.
Technol., 2013, 3, 2140.
9. A. GhorbaniꢀChoghamarani, B. Tahmasbi, P. Moradi and
N. Havasi, Appl. Organometal. Chem, 2016 and DOI
1
0.1002/aoc.3478.
0. H. Cao, J. He, L. Deng and X. Gao, Appl. Surf. Sci, 2009,
55, 7974
3
2
3
3
1. M. Singh, N. Raghav, Bioorg. Chem, 2015, 59, 12.
2. F. Havasi, A. GhorbaniꢀChoghamarani and F. Nikpour,
Micropor. Mesopor. Mat., 2016, 224, 26
This journal is © The Royal Society of Chemistry 2013
J. Name., 2013, 00, 1-3 | 9

RSC Advances
Page 10 of 10
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DOI: 10.1039/C6RA15474C
Graphical Abstract
Tribromide ion immobilized on magnetic nanoparticle as new, efficient
and reusable nanocatalyst in multicomponent reactions
Maryam Hajjami* and Fatemeh Gholamian
O
O
CHO
R
NH
NH
NH2
R
+
NH2
Br3-
MNPs
HBr + Br2
Fe O
MNPs-TEDETA tribromide
3
4
TEDETA
3
H C
O
H
3
C
O
Si
Cl
O
MNPs
3
H C
CPTMS
MNPs-TEDETA
MNPs
(
Et) N
2
MNPs-CPTMS
NH + NEt
3
O
(
Et) N
2
CHO
R
+
R
O
O
O
O
OEt
OEt
+
+
NH OAc
4
N
O
H