Sulfamic acid immobilized on amino-functionalized magnetic nanoparticles: A new and active magnetically recoverable catalyst for the synthesis of N-heterocyclic compounds

Article abstract of DOI:10.1002/aoc.3999

Sulfamic acid immobilized on amino-functionalized magnetic nanoparticles (MNPs/DETA-SA) was successfully fabricated and characterized using various techniques. Diameters of approximately 15?nm for the MNPs/DETA-SA were observed from scanning electron microscopy images. The as-fabricated nanocomposite was applied as an efficient and magnetically reusable catalyst for the synthesis of 2,3-dihydroquinazoline-4(1H)-one and polyhydroquinoline derivatives. All products were obtained in good to excellent yields. Recovery tests confirm that the catalyst can be readily recovered using an external magnet and reused many times without significant loss of its catalytic activity.

Full text of DOI:10.1002/aoc.3999

Received: 10 May 2017
DOI: 10.1002/aoc.3999
Revised: 27 June 2017
Accepted: 29 June 2017
F U L L P A P E R
Sulfamic acid immobilized on amino‐functionalized
magnetic nanoparticles: A new and active magnetically
recoverable catalyst for the synthesis of N‐heterocyclic
compounds
Lotfi Shiri | Hojatollah Narimani | Mosstafa Kazemi
Department of Chemistry, Faculty of Basic
Sulfamic acid immobilized on amino‐functionalized magnetic nanoparticles
(MNPs/DETA‐SA) was successfully fabricated and characterized using various
techniques. Diameters of approximately 15 nm for the MNPs/DETA‐SA were
observed from scanning electron microscopy images. The as‐fabricated nano-
composite was applied as an efficient and magnetically reusable catalyst for
the synthesis of 2,3‐dihydroquinazoline‐4(1H)‐one and polyhydroquinoline
derivatives. All products were obtained in good to excellent yields. Recovery
tests confirm that the catalyst can be readily recovered using an external mag-
net and reused many times without significant loss of its catalytic activity.
Sciences, Ilam University, PO Box 69315‐
516, Ilam, Iran
Correspondence
Lotfi Shiri, Department of Chemistry,
Faculty of Basic Sciences, Ilam University,
PO Box 69315‐516, Ilam, Iran.
Email: lshiri47@gmail.com
KEYWORDS
2,3‐dihydroquinazoline‐4(1H)‐one, magnetically reusable catalyst, MNPs/DETA‐SA,
polyhydroquinolines
The development of new and efficient nanomaterials as
catalyst supports is a real challenge in modern research
in catalysis. The immobilization of homogeneous catalysts
on supporting materials (such as inorganic silica, organic
polymers and other metalliferous oxides) for incorporat-
ing the advantages of both heterogeneous and homoge-
neous catalysis has received much attention as an
efficient strategy in catalysis research.[1] In recent times,
much regard has been paid to the fabrication and use of
magnetic nanoparticles (MNPs) because of a broad range
of possible applications.[2] In fact, magnetically separable
catalysts are a well‐favoured and fascinating strategy for
bridging the divide between heterogeneous and homoge-
nous catalysis.[3] The marked advantages of MNPs are
easy preparation, large readily available surface area,
low toxicity, low cost and operational simplicity.[4] The
simple separation of MNP‐supported catalysts from prod-
ucts or reaction mixture using an external magnet is the
most notable advantage of MNPs.[5] According to these
advantages, MNPs can be considered as a promising
alternative to other catalyst supports (such as porous/
mesoporous catalyst supports).[6]
Catalysis in aqueous media or under solvent‐free con-
ditions has recently received special attention in both aca-
demic and industrial research.[7]
2,3‐Dihydroquinazolin‐4(1H)‐one‐based compounds
continue to attract significant attention in biosynthesis
because of their valuable pharmacological and biological
activities.[8,9] They have a vast range of pharmacological
and biological activities, such as antitumour, anticancer,
analgesic, diuretic and herbicidal activities.[10–12] The
general method applicable for the preparation of 2,3‐
dihydroquinazolin‐4(1H)‐ones is the condensation
reaction of 2‐aminobenzamide with aldehydes or ketones
in the presence of acidic catalysts.[13] In recent times, a
range of catalysts for the synthesis of 2,3‐
dihydroquinazolin‐4(1H)‐ones have been reported in the
literature.[14–16]
Catalysis of synthetic reactions by acids is always a
fascinating research target in organic synthesis. Since
Appl Organometal Chem. 2017;e3999.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.3999

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SHIRI ET AL.
SCHEME 1 General route for the
synthesis of MNPs/DETA‐SA
the acids used are often liquid and expensive, their separa-
tion from reaction media is the most important concern of
organic chemists.[17] Therefore, the design and fabrication
of strong solid acids and their application as catalyst in
organic reactions is of interest for future organic synthe-
sis, in particular from the green synthetic chemistry point
of view.[18,19] The immobilization of acidic functional
groups on MNPs can be considered as an ideal and
fascinating solution to overcome this drawback, because
the catalyst can be readily separated from reaction media
using an external magnet. In this paper, we report
sulfamic acid immobilized on amino‐functionalized
magnetic nanoparticles (MNPs/DETA‐SA) as a new,
efficient and recyclable catalyst for the synthesis of 2,3‐
dihydroquinazolin‐4(1H)‐one derivatives.
The FT‐IR spectra of MNPs, MNPs/CPTMS, MNPs/
DETA and MNPs/DETA‐SA are displayed in Figure 1.
The FT‐IR spectrum of MNPs exhibits a stretching vibra-
tion at 3401 cm−1 which incorporates the contributions
from both symmetric and asymmetric modes of the
O─H bonds which are attached to the surface of iron
atoms (Figure 1a). The presence of MNPs is shown by a
strong absorption band at around 570 cm−1, which is
attributed to the Fe─O bond of MNPs. The anchoring of
CPTMS on MNPs is confirmed by C─H stretching vibra-
tions that appear at 2854 –2922 cm−1 (Figure 1b). Also
the absorption band at around at 996 cm−1 is attributed
to Si─O stretching vibration. As shown in Figure 1(c),
the functionalization with DETA replacing Cl is con-
firmed by N─H stretching vibrations that appear at
1 | RESULTS AND DISCUSSION
1.1 | Catalyst preparation
The details of the strategy applied for the preparation of
sulfamic acid loaded on amino‐functionalized MNPs are
presented in Scheme 1. The MNPs were prepared by a
chemical co‐precipitation procedure[5] and covered with
3‐chloropropyltrimethoxysilane (CPTMS) by covalent
bonds.[1] The reaction of the supported CPTMS with
diethylenetriamine (DETA) in toluene under reflux
conditions for 42 h produced DETA‐functionalized MNPs
(MNPs/DETA).[5] Ultimately, the reaction of MNPs/
DETA with chlorosulfonic acid in CH2Cl2 at room
temperature led to MNPs/DETA‐SA.
1.2 | Catalyst characterization
The prepared nanosolid catalyst was characterized using
Fourier transform infrared (FT‐IR) spectroscopy, scan-
ning electron microscopy (SEM), vibrating sample mag-
netometry (VSM), X‐ray diffraction (XRD) and
thermogravimetric analysis (TGA).
FIGURE 1 FT‐IR spectra of MNPs (a), MNPs/CPTMS (b). MNPs/
DETA (c) and MNPs/DETA‐SA (d)

SHIRI ET AL.
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FIGURE 2 SEM images of MNPs/DETA‐SA
3399 cm−1. Reaction of MNPs/DETA with chlorosufonic
acid produces MNPs/DETA‐SA (Figure 1d), in which the
presence of SO3H moiety is evidenced with bands at
1080, 1131 and 1212 cm−1. All of those bands reveal that
the surface of MNPs is successfully modified with
sulfamic acid.
The morphology and size of the nanocatalyst were
evaluated using SEM (Figure 2). The SEM images
show that the MNPs/DETA‐SA nanoparticles are
approximately spherical in shape and tend to agglomerate
into larger aggregates. According to Figure 2, the average
diameter of the MNPs/DETA‐SA nanoparticles is about
15 nm.
The magnetic properties of MNPs and MNPs/DETA‐
SA were characterized using VSM at ambient
temperature. The room temperature magnetization
curves of MNPs and MNPs/DETA‐SA are shown in
Figure 3. The magnetic measurement shows that
the MNPs and MNPs/DETA‐SA have saturated
FIGURE 3 Magnetization curves for MNPs (blue) and MNPs/
DETA‐SA (green) at room temperature
FIGURE 4 XRD pattern of MNPs/DETA‐SA

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SHIRI ET AL.
SCHEME 2 MNPs/DETA‐SA‐catalysed cyclocondensation of
anthranilamide with aldehydes/ketones
MNPs/DETA‐SA shows several characteristic peaks at 2θ
values of 35.2°, 41.3°, 50.5°, 63.2°, 67.4° and 74.5°, in good
agreement with the standard XRD pattern of MNPs
reported in the literature.[11]
One indication of bond formation between the MNPs
and the catalyst can be inferred from TGA. Figure 5 shows
the TGA curves for bare MNPs, MNPs/CPTMS, MNPs/
DETA and MNPs/DETA‐SA. The TGA curves of all
samples show a small amount of weight loss below
200 °C, due to desorption of physically adsorbed solvents
and surface hydroxyl groups. Organic groups have been
reported to desorb at temperatures above 260 °C. The
TGA curves of MNPS/CPTMS and MNPS/DETA
show mass losses of 5 and 9%, respectively. For MNPs/
DETA‐SA, there is a well‐defined mass loss of 27%
between 370 and 520 °C which is related to the
breakdown of the DETA‐SA moieties. As a result of this
FIGURE 5 TGA curves of bare MNPs (black), MNPs/CPTMS
(blue), MNPs/DETA (red) and MNPs/DETA‐SA (green)
magnetization values of 55.1 and 33.2 emu g−1, respec-
tively. The decrease of the saturation magnetization can
be related to the presence of sulfamic acid groups on the
surface of the MNP supports.
In order to investigate the crystal structure of
the obtained nanocatalyst (MNPs/DETA‐SA), XRD
analysis was performed, and the resultant pattern of the
as‐prepared sample is shown in Figure 4. As can be seen,
TABLE 1 Optimization of reaction conditionsa
Entry
Amount of catalyst (mg)
Solvent (temp., °C)
Time (min)
Yield (%)b
1
3
H2O (70)
200
85
2
5
H2O (70)
105
85
88
3
10
15
20
15
15
15
15
15
15
—
H2O (70)
93
4
H2O (70)
65
97
5
H2O (70)
65
96
6
CH3CN (reflux)
EtOH (reflux)
THF (reflux)
PhMe (reflux)
H2O (60)
100
160
230
150
90
91
7
89
8
87
9
94
10
11
12
89
H2O (80)
65
95
H2O (70)
120
Trace
aReaction conditions: anthranilamide (1.05 mmol) and 4‐chlorobenzaldehyde (1 mmol) in the presence of catalyst and solvent (2 ml).
bIsolated yield.

SHIRI ET AL.
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TABLE 2 MNPs/DETA‐SA‐catalysed synthesis of 2,3‐dihydroquinazolin‐4(1H)‐ones at 90 °C under solvent‐free conditions
Entry
R
R′
Product
2a
Time (min)
Yield(%)a
M.p. (°C)
1
4‐ClC6H5
H
65
97
199–201[20]
184–185[20]
223–224[20]
197–199[20]
200–202[20]
201–203[20]
265–267[13]
208–209[20]
218–220[20]
230–232[21]
193–194[20]
185–187[20]
190–192[20]
190–191[20]
173–174[20]
175–176[20]
209–212[20]
218–222[20]
222–224[20]
2
4‐OMeC6H5
4‐MeC6H5
4‐FC6H5
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
—
Me
2b
2c
60
95
93
92
88
97
91
96
94
87
92
86
94
84
85
91
90
83
80
3
50
4
2d
2e
30
5
4‐NO2C6H5
4‐BrC6H5
110
55
6
2f
7
4‐OHC6H5
4‐(Me2)NC6H5
C6H5
2 g
2 h
2i
70
8
70
9
40
10
11
12
13
14
15
16
17
18
19
3‐OHC6H5
3‐NO2C6H5
3‐BrC6H5
2j
90
2 k
2 l
2 m
2n
2o
2p
2q
2r
135
80
3‐ClC6H5
90
2‐NO2C6H5
2‐BrC6H5
160
115
80
2‐OMeC6H5
3,4‐(OMe)2C6H5CHO
Cyclohexanone
Ph
55
185
270
2 s
aIsolated yield.
TABLE 3 Optimization of reaction conditionsa
Entry
Catalyst (mg)
Solvent
Temperature (°C)
Time (min)
Yield (%)b
1
5
Solvent‐free
90
85
86
2
10
15
20
25
30
20
20
20
20
20
20
20
20
20
—
Solvent‐free
Solvent‐free
Solvent‐free
Solvent‐free
Solvent‐free
CH3CN
90
60
89
93
97
97
96
79
87
50
84
91
83
91
94
96
Trace
3
90
35
4
90
20
5
90
20
6
90
20
7
Reflux
Reflux
Reflux
Reflux
Reflux
80
155
180
230
200
145
160
45
8
THF
9
Acetone
10
11
12
13
14
15
15
H2O
EtOH
H2O–EtOH (1:1)
Solvent‐free
Solvent‐free
Solvent‐free
Solvent‐free
70
80
30
100
90
20
120
aReaction conditions: aldehyde (1 mmol), dimedone (1 mmol), ethyl acetoacetate (1 mmol) and ammonium acetate (1.2 mmol).
bIsolated yield.

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SHIRI ET AL.
analysis, the grafting of DETA and SA groups on the
MNPs is verified.
pose, the reaction of 4‐chlorobenzaldehyde and
anthranilamide was chosen as a simple model reaction
to investigate the possibility of the strategy and optimize
the reaction conditions. To evaluate the effect of catalyst
loading, systematic studies were carried out in the pres-
ence of different amounts of the catalyst (3, 5, 10, 15,
20 mg) in water, affording 2,3‐dihydroquinazolin‐
4(1H)‐ones in 85, 88, 93, 97 and 97% isolated yields,
respectively (Table 1, entries 1–5). As evident from
Table 1, the best yield is found in the presence of just
15 mg of MNPs/DETA‐SA, and the use of higher
amounts of catalyst (20 mg) does not improve the result
to an appreciable extent (Table 1, entry 5). Next, under
the optimal catalyst amount, the effect of several sol-
vents (such as CH3CN, EtOH, tetrahydrofuran (THF)
and toluene) at reflux temperature was studied
(Table 1, entries 4 and 6–9). The best results were
obtained in water as solvent. Then, the effect of temper-
ature (60 and 80 °C), under the optimal reaction condi-
tions, on the model reaction was studied, but the
obtained results were not satisfactory (Table 1, entries
10 and 11). Finally, the model reaction was conducted
in the absence of the catalyst, but only a trace amount
of product was observed on TLC plate after 120 min
(Table 1, entry 12). Therefore, 15 mg of MNPs/DETA‐
The loading of sulfamic acid on the surface of the
nanocomposite was determined by back titration analysis.
The data obtained by back titration show that the amount
of sulfamic acid loaded is 1.1 mmol g−1
.
1.3 | Catalytic studies
1.3.1 | 2,3‐Dihydroquinazolin‐4(1H)‐ones
After characterization of the catalyst, the activity of
MNPs/DETA‐SA in the one‐pot synthesis of 2,3‐
dihydroquinazolin‐4(1H)‐ones was studied. For this pur-
SCHEME
3
MNPs/DETA‐SA‐catalysed
synthesis
of
polyhydroquinolines
TABLE 4 MNPs/DETA‐SA‐catalysed synthesis of polyhydroquinolines at 90 °C under solvent‐free conditions
Entry
Aldehyde
Product
4a
Time (min)
Yield (%)a
M.p. (°C)
236–238[28]
1
4‐ClC6H5CHO
20
97
2
4‐OMeC6H5CHO
4‐MeC6H5CHO
4‐FC6H5CHO
4b
4c
30
25
20
35
40
35
25
35
50
30
40
35
65
55
35
30
25
45
93
95
94
90
95
90
97
95
96
94
90
91
85
87
92
93
94
89
248–250[28]
251–253[28]
180–182[28]
239–241[29]
247–251[28]
230–233[28]
232–234[29]
178–180[28]
216–218[28]
232–234[30]
175–177[29]
233–235[29]
217–219[29]
209–211[29]
207–209[29]
255–257[31]
203–205[28]
240–243[32]
3
4
4d
4e
5
4‐NO2C6H5CHO
4‐BrC6H5CHO
4‐OHC6H5CHO
4‐(me)2NC6H5CHO
4‐OEtC6H5CHO
C6H5CHO
6
4f
7
4 g
4 h
4i
8
9
10
11
12
13
14
15
16
17
18
19
4j
3‐ClC6H5CHO
4 k
4 l
4 m
4n
4o
4p
4q
4r
3‐NO2C6H5CHO
3‐BrC6H5CHO
3‐OHC6H5CHO
2‐NO2C6H5CHO
2‐ClC6H5CHO
2‐OMeC6H5CHO
3,4‐(OMe)2C6H5CHO
2,4‐(cl)2C6H5CHO
4 s
aIsolated yield.

SHIRI ET AL.
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TABLE 5 Comparison of activity of various catalysts in the synthesis of products 2a (entries 1–5) and 4a (entries 6–10)
Entry
Catalyst
Condition
Time (min)
Yield (%)
Ref.
[33]
1
KAl(SO4)2.E12H2O
EtOH, reflux
300
80
[34]
[35]
[36]
2
Glycerosulfonic acid
Silica sulfuric acid
SBNPSA
Glycerol, 80 °C
H2O,80 °C
360
180
150
65
97
81
87
97
87
80
98
95
97
3
4
EtOH, reflux
5
MNPs/DETA‐SA
PdCl2
H2O, 70 °C
This work
[24]
6
THF, reflux
240
30
[37]
[28]
[38]
7
K7[PW11CoO40]
Cu‐SPATB/Fe3O4
[TBA]2[W6O19]
MNPs/DETA‐SA
CH3CN, reflux
Peg‐400, 80 °C
Solvent‐free, 110 °C
Solvent‐free, 90 °C
8
65
9
20
10
20
This work
SA in water at 70 °C were selected as the optimal reac-
tion conditions (Table 1, entry 4).
20 mg of MNPs/DETA‐SA was used at 90 °C under sol-
vent‐free conditions (Table 3, entry 4).
After the optimization of the reaction conditions,
various aldehydes were reacted under the optimum
conditions and the corresponding 2,3‐dihydroquinazolin‐
4(1H)‐one compounds were obtained in good to excel-
lent yields (Scheme 2). The results of these studies are
summarized in Table 2. A variety of benzaldehydes
bearing electron‐donating and electron‐withdrawing
substituents were successfully employed to prepare the
corresponding 2,3‐dihydroquinazolin‐4(1H)‐one deriva-
tives in excellent yields. The experimental procedure is
very simple and convenient, and has the ability to
tolerate a variety of other functional groups (such as
hydroxyl, halide, nitro, alkyl and alkoxyl) under the
reaction conditions.
Based on the observations discussed above, we
conducted the same reactions using dimedone,
ethylacetoacatate, ammonium acetate and variety of
substituted aldehydes under the optimized conditions
(Scheme 3). As expected, satisfactory results were
obtained, and the results are summarized in Table 4. A
wide range of aldehydes was successfully reacted with
dimedone, ethylacetoacatate and ammonium acetate to
give the polyhydroquinoline derivatives. It is noteworthy
that the products were obtained in high yields.
To show the superiority of the present strategy in
comparison with other reported procedures, we sum-
marize results for the synthesis of products 2a and 4a
in Table 5. It is clear that reaction time and product
yield are better than those for other protocols reported
in the literature. Also the new catalyst is comparable in
terms of price, stability, non‐toxicity and ease of
separation.
1.3.2 | Polyhydroquinolines
Polyhydroquinoline scaffolds are key structural motifs in
a diverse range of natural products and pharmaceutically
active molecules.[22] Polyhydroquinoline and related
derivatives have received great attention in recent times
due to their diverse biological activities such as broncho-
dilator vasodilator, antitumour, anti‐atherosclerotic, anti-
diabetic and geroprotective activities.[23–26] Furthermore,
polyhydroquinolines can act as reducing agents for the
straight reductive amination of aldehydes and ketones.[27]
Considering these valuable applications, we decided to
study the catalytic activity of MNPs/DETA‐SA in the syn-
thesis of polyhydroquinolines. In this respect, the reaction
of 4‐chlorobenzaldehyde with dimedone, ammonium ace-
tate and ethylacetoacetate was chosen as a simple model
reaction to investigate the possibility of the strategy and
optimize the reaction conditions (Table 3). In the synthe-
sis of product 4a, the best results were obtained when
FIGURE 6 Reusability of MNPs/DETA‐SA in the synthesis of
products 2a and 4a

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SHIRI ET AL.
performed with an FEI Quanta 200 SEM operated at a
20 kV accelerating voltage. TGA curves were recorded
using a PL‐STA 1500 device manufactured by Thermal
Sciences. The magnetic measurements were carried out
using VSM (BHV‐55, Riken, Japan) at room
temperature.
1.4 | Reusability of MNPs/DETA‐SA
The recovery and reusability of catalysts is an important
aspect in catalytic processes. In this respect, the reus-
ability of MNPs/DETA‐SA was investigated in the syn-
thesis of products 2a and 4a. In these experiments,
after completion of the reaction, the catalyst was easily
and rapidly separated from the product using an exter-
nal magnet. The separated magnetic nanocatalyst was
further washed with ethanol to remove residual prod-
uct. Then, the reaction vessel was charged with fresh
substrate and subjected to the next reaction run. As
shown in Figure 6, the catalyst can be recycled for up
to seven runs without any significant loss of its catalytic
activity. In addition, one of the attractive features of this
novel catalyst system is the rapid and efficient separa-
tion of the catalyst using an appropriate external mag-
net, which minimizes the loss of catalyst during
separation.
3.2 | Preparation of Fe3O4 MNPs
A mixture of FeCl3⋅6H2O (5.838 g, 0.0216 mol) and
FeCl2⋅4H2O (2.147 g, 0.0108 mol) was dissolved in
100 ml of deionized water in a three‐necked flask
(250 ml) under nitrogen atmosphere. After that, 10 ml of
NH3 was added into the solution within 30 min with
vigorous mechanical stirring. After being rapidly
stirred for 30 min, the resultant black dispersion was
heated to 80 °C for 30 min. The black precipitate formed
was isolated by magnetic decantation, washed with
double‐distilled water until neutrality, and further
washed twice with ethanol and dried at room
temperature.[5]
2 | CONCLUSIONS
In summary, the preparation of sulfamic acid supported
on functionalized MNPs as a versatile and active
magnetically recoverable catalyst was described. The pre-
pared acidic nanocatalyst was characterized using FT‐IR
spectroscopy, TGA, XRD, SEM and VSM. As‐fabricated
nanosolid showed high catalytic activity in the
synthesis of 2,3‐dihydroquinazoline‐4(1H)‐one and
polyhydroquinoline derivatives. All products were
obtained in good to excellent yields. From the
environmental point of view, the performance of
reactions in water and under solvent‐free conditions is a
fascinating aspect of this protocol. Reusability studies
revealed that the acidic catalyst can be reused many times
without significant loss in catalytic efficiency.
3.3 | Preparation of MNPs/CPTMS
The obtained MNPs (1.5 g) were dispersed in 250 ml of
ethanol–water (1:1 v/v) by sonication for 30 min, and then
CPTMS (2.5 ml) was added to the reaction mixture. The
reaction mixture was stirred using mechanical stirring
under nitrogen atmosphere at 40 °C for 8 h. The nanopar-
ticles were then redispersed in ethanol by sonication five
times and separated through magnetic decantation. The
nanoparticle product (MNPs/CPTMS) was dried at room
temperature.[1]
3.4 | Preparation of MNPs/DETA
MNPs/CPTMS (1.5 g) was dispersed in toluene (50 ml)
using an ultrasonic bath for 10 min. DETA (2 ml) was
added and stirred at 100 °C for 30 h under nitrogen
atmosphere. Then, the prepared functionalized MNPs
were separated by magnetic decantation and washed
three times with ethanol to remove the unattached sub-
strates. The resulting product was dried at room
temperature.[5]
3 | EXPERIMENTAL
3.1 | Materials
Chemicals were purchased from Fisher and Merck. The
reagents and solvents used in this work were obtained
from Sigma‐Aldrich, Fluka or Merck and used without
further purification. FT‐IR spectra of samples were
recorded in KBr discs using a Nicolet Impact 410
spectrometer. 1H NMR and 13C NMR spectra were
recorded with a Bruker DRX‐400 spectrometer at 400
and 100 MHz, respectively. Nanostructures were
characterized using a Philips X'pert powder X‐ray
diffractometer (Co Kα radiation = 0.154056 nm), at a
scanning speed of 2° min−1 from 10° to 80°. SEM was
3.5 | Preparation of MNPs/DETA‐SA
MNPs/DETA (0.5 g) was dispersed in CH2Cl2 (10 ml) using
an ultrasonic bath for 20 min. Then, chlorosulfonic acid
(1.5 ml) was added dropwise over a period of 20 min, and
the mixture was stirred for 3 h at room temperature. Func-
tionalized MNPs (MNPs/DETA‐SA) were separated by

SHIRI ET AL.
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[3] M. Sheykhan, L. Mamani, A. Ebrahimi, A. Heydari, J. Mol.
Catal. A 2011, 335, 253.
magnetic decantation, washed four times with dry CH2Cl2
and two times with EtOH, and dried at room temperature.
[4] A. Ghorbani‐Choghamarani, M. Norouzi, J. Mol. Catal. A 2014,
395, 172.
3.6 | General procedure for synthesis of
2,3‐Dihydroquinazolin‐4(1H)‐ones
[5] L. Shiri, A. Ghorbani‐Choghamarani, M. Kazemi, Monatsh.
Chem. 2017, 148, 1131.
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A mixture of anthranilamide (1.05 mmol, 142 mg),
aldehyde or ketone and MNPs/DETA‐SA (15 mg) in
water (2 ml) was stirred at 70 °C. Reaction progress was
monitored by TLC (acetone–n‐hexane, 2:8). After the time
specified in Table 2, reaction mass was allowed to cool to
room temperature. CH2Cl2 (3 × 5 ml) was added to the
reaction mixture and the catalyst was separated using an
external magnet. CH2Cl2 was evaporated under reduced
pressure to afford the crude products. The obtained crude
products were further recrystallized from ethanol
to afford the pure 2,3‐dihydroquinazolin‐4(1H)‐ones
(80–97%).
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A mixture of aldehyde (1 mmol), dimedon (1 mmol),
ethylacetoacetate (1 mmol), ammonium acetate
(1.2 mmol) and MNPs/DETA‐SA (20 mg) was stirred
at 90 °C under solvent‐free conditions. Reaction prog-
ress was monitored by TLC (acetone–n‐hexane, 3:7).
After completion of the reaction, the catalyst was sepa-
rated using an external magnet and washed with ethyl
acetate. Then, the solvent was evaporated and all prod-
ucts were recrystallized from ethanol. The pure
polyhydroquinoline derivatives were obtained in excel-
lent yields (85–97%).
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All the products reported here are known compounds
and the spectroscopic data matched literature values.
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ACKNOWLEDGEMENT
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This work was supported by the research facilities of Ilam
University, Ilam, Iran.
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Havasi, Appl. Organomet. Chem. 2016, 30, 619.
ORCID
[29] M. Tajbakhsh, H. Alinezhad, M. Norouzi, S. Baghery, M.
Mosstafa Kazemi http://orcid.org/0000-0003-4676-720X
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Kazemi M. Sulfamic acid immobilized on amino‐
functionalized magnetic nanoparticles: A new and
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