Synthesis of copper (II)-supported magnetic nanoparticle and study of its catalytic activity for the synthesis of 2,3-dihydroquinazolin-4(1H)-ones

Article abstract of DOI:10.1016/j.molcata.2014.08.013

A magnetic nanoparticle supported efficiently catalyzes for condensation 2-aminobenzamide with aldehydes to afford the corresponding 2,3- dihydroquinazolin-4(1H)-one derivatives successfully in high yield. The reactions were carried out in ethanol under reflux conditions. The protocol proves to be efficient and versatile benign in terms of very easy work-up and reused seven times without significant loss of catalytic activity. The heterogeneous catalyst was characterized by FT-IR spectroscopy, thermogravimetric (TGA) analysis, powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscope (TEM).

Full text of DOI:10.1016/j.molcata.2014.08.013

Journal of Molecular Catalysis A: Chemical 395 (2014) 172–179
Contents lists available at ScienceDirect
Journal of Molecular Catalysis A: Chemical
journal homepage: www.elsevier.com/locate/molcata
Synthesis of copper (II)-supported magnetic nanoparticle
and study of its catalytic activity for the synthesis of
2
,3-dihydroquinazolin-4(1H)-ones
∗
Arash Ghorbani-Choghamarani , Masoomeh Norouzi.
Department of Chemistry, Faculty of Science, Ilam University, P.O. Box 69315516, Ilam, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 19 June 2014
Received in revised form 4 August 2014
Accepted 5 August 2014
Available online 15 August 2014
A magnetic nanoparticle supported efficiently catalyzes for condensation 2-aminobenzamide with alde-
hydes to afford the corresponding 2,3-dihydroquinazolin-4(1H)-one derivatives successfully in high
yield. The reactions were carried out in ethanol under reflux conditions. The protocol proves to be efficient
and versatile benign in terms of very easy work-up and reused seven times without significant loss of cat-
alytic activity. The heterogeneous catalyst was characterized by FT-IR spectroscopy, thermogravimetric
(
TGA) analysis, powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission
Keywords:
Magnetic nanoparticle
electron microscope (TEM).
©
2014 Elsevier B.V. All rights reserved.
2
;3-Dihydroquinazolin-4(1H)-ones
Catalyst
Copper
1
. Introduction
In recent years, the design of efficient and recoverable cat-
over other supporting materials, various catalysts and ligands have
been immobilized on these particles [8]. The various types of tran-
sition metal-catalyzed reactions using catalytic sites grafted on
MNPs that have emerged recently include olefin hydroformylation
[9], alcohol hydrogenation [10], olefin hydrogenation [11], asym-
metric hydrogenation [12], aldol reaction [13], Suzuki and Heck
reactions [14,15], Sonogashira and Carbonylative Sonogashira reac-
tions [16], Knoevenagel condensation [17], ring-closing metathesis
[18], cycloaddition reaction [19], and as supports for biocatalysts
[20].
Over the past decade, the synthesis of heterocyclic com-
pounds has become the cornerstone of synthetic organic chemistry
as a result of a wide variety of their application in medicinal
and pharmaceutical chemistry [21]. 2,3-Dihydroquinazolin-4(1H)-
ones, an important class of heterocyclic compounds influence
numerous cellular processes [22]. These exhibit a wide range of
biological activities, such as antitumor, antibiotic, antidefibrilla-
tory, antipyretic, analgesic, antihypertonic, diuretic, antihistamine,
antidepressant, and vasodilating behaviour [23]. Furthermore,
quinazolinone skeleton is frequently found in various natural
products. Some examples include the anticancer compound trime-
trexate, the sedative methaqualone, the alpha adrenergic receptor
antagonist such as doxazosin and the antihypertensive agent
ketanserin [24].
alysts has become an important issue for reasons of economic
and environmental impact. One strategy has focused on com-
bining the advantages of different types of catalyst; for example
the high activity and selectivity of homogeneous species with
the ease of separation and recycling of heterogeneous catalysts
[
1]. Nanoparticles have emerged as efficient alternative support
materials for homogeneous catalyst immobilization [2,3]. These
nanoparticles, because of their high surface area and unique mag-
netic properties, have a broad range of potential uses in disciplines,
including physics, biomedicine, biotechnology, material science
and catalysis support applications [4–6]. In this regard, the use of
magnetic nanoparticles (MNPs) supported catalyst has been effi-
ciently employed as heterogeneous catalysts. The main advantage
of a catalytic system based on magnetic nanoparticles is that the
nanoparticles can be efficiently isolated from the product solution
through a simple magnetic separation process after completing
the reactions [7]. Additionally, the MNP-supported catalysts also
show high dispersion and reactivity with a high degree of chemical
stability. By utilizing these advantages of magnetic nanoparticles
Several strategies for their synthesis were already developed:
condensation of anthranilamide with an aldehyde or ketone
using p-toluenesulfonic acid as a catalyst [25]; desulfurization of
∗ Corresponding author. Tel.: +98 841 2227022; fax: +98 841 2227022.
E-mail addresses: a.ghorbani@mail.ilam.ac.ir, arashghch58@yahoo.com
A. Ghorbani-Choghamarani).
(
http://dx.doi.org/10.1016/j.molcata.2014.08.013
381-1169/© 2014 Elsevier B.V. All rights reserved.
1

A. Ghorbani-Choghamarani, M. Norouzi. / Journal of Molecular Catalysis A: Chemical 395 (2014) 172–179
173
100
a
90
80
70
60
50
40
b
c
d
e
0
100
200
300
400
500
600
700
800
Temperature (°C)
Fig. 2. TGA curves of Fe3O4 (a), amino-functionalized (b), MNP-acryloxyl (c), MNP-
TEDETA (d), and CuCl2/Fe3O4-TEDETA (e).
X-ray powder diffraction (XRD) diffractometer (Co K␣, radia-
◦
−1
◦
tion = 0.154056 nm), at a scanning speed of 2 min from 10 to
1
◦
00 . The particle size and morphology were investigated by a JEOL
JEM-2010 scanning electron microscopy (SEM), on an accelerat-
ing voltage of 200 kV. The infrared spectra (IR) of samples were
recorded in KBr disks using a NICOLET impact 410 spectrometer.
The thermogravimetric analysis (TGA) curves are recorded using a
PL-STA 1500 device manufactured by Thermal Sciences. The par-
ticle size and morphology were investigated by a Zeiss-EM10C
transmission electron microscope (TEM) on an accelerating voltage
of 80 kV.
Fig. 1. FT-IR spectra of Fe3O4 nanoparticles (a), amino-functionalized (b), MNP-
acryloxyl (c), MNP-TEDETA (d), and CuCl2/Fe3O4-TEDETA (e).
The 1H and 13C spectra were measured using a Bruker Avance
III 400.
2
-thioxo-4(3H)-quinazolinones [26]; reaction of isatoic anhydride
with Schiff-bases [27]; one-step conversion of 2-nitrobenzamides
to 2,3-dihydro-4(1H)-quinazolinones [28]; condensation of
anthranilamide with benzil [29]; two-step synthesis starting from
isatoic anhydride and amines, then annulated with ketones [30]; a
one-pot three-component condensation of isatoic anhydride, alde-
hydes and amines [31]. More attractive and convenient method
for synthesis of such significant heterocycles is three-component
condensation of isatoic anhydride, aldehydes, and amines.
2.2. Preparation of the magnetic Fe3O4-nanoparticles (MNPs)
The mixture of FeCl3·6H2O (5.838 g, 0.0216 mol) and FeCl2·4H2O
(2.147 g, 0.0108 mol) were dissolved in 100 mL of deionized water
in a three-necked bottom (250 mL) under N2 atmosphere. After
that, under rapid mechanical stirring, 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
The catalysts reported for the above stated one-pot procedure
include inorganic catalysts like aluminium tris(dihydrogen phos-
phate) [32], silica sulfuric acid [33], magnetic Fe O particles [34],
◦
heated to 80 C for 30 min. The black precipitate formed was iso-
lated by magnetic decantation, washed with double-distilled water
until neutrality, and further washed twice with ethanol and dried
3
4
reaction media like acidic ionic liquid [35] and Brønsted acid [36].
Some of these methodologies involve strongly acidic conditions,
toxic catalysts, hazardous organic solvents and long reaction times.
Thus, there is a need for a non-acidic and novel catalyst that could
overcome the above drawbacks.
◦
at 80 C in vacuum.
2.3. Preparation of Fe O -(3-aminopropyl)-trimethoxysilane
3
4
Here, we report the magnetic nanoparticle-supported copper
II) as a catalyst for synthesis of 2,3-dihydroquinazolin-4(1H)-ones
derivatives. The magnetic catalyst could be readily separated from
the media by simple magnetic decantation, and could be reused
without significant degradation in activity and minimize the envi-
ronmental damages.
The obtained magnetic nanoparticles (MNPs) powder (1.5 g)
was dispersed in a mixture of ethanol and water (250 mL, 1:1 by
volume) and solution by sonication for 30 min. Then 3-aminopropyl
(triethoxy) silane (99%, 3 mL) was added to the mixture. After
mechanical stirring under N2 atmosphere at room temperature for
8 h. The settled product was redispersed in ethanol by sonication.
The final the product was washed with copious amounts of deion-
ized water and ethanol by magnetic decantation, and dried under
vacuum at room temperature overnight.
(
2
. Experimental
2.1. Materials
2
.4. Preparation of Fe O -TEDETA
3 4
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.
Nanostructures were characterized using a Holland Philips X pert
The amino-functionalized MNPs (1 g) were dispersed in dry
CH Cl (3 mL) by ultrasonic bath for 10 min, and the flask was
cooled in an ice-water bath. Triethylamine (3.2 mL) was added
2
2
,

1
74
A. Ghorbani-Choghamarani, M. Norouzi. / Journal of Molecular Catalysis A: Chemical 395 (2014) 172–179
O
OH
OH
OH
O
O
O
O
O
O
(
EtO) SiCH CH CH NH
CH CHCOCl
2
3
2
2
2
2
Si
NH2
Si
N
H
EtOH/H O
Et N
3
2
CH CH3
2
CH CH N CH CH3
O
2
2
2
HN(CH CH N(Et) )
2 2
O
2
2
O
O
Si
N
H
N
CH CH N CH CH3
2
2
2
CH CH3
2
CuCl2
O
CH CH3
2
CH CH3
CH CH N
2
2
2
O
O
Cl
Cl
Si
N
N
Cu
H
O
CH CH N CH
CH
2
2
2
3
CH CH3
2
Scheme 1. Synthesis of CuCl2/Fe3O4-TEDETA.
and stirred for 30 min. Subsequently, acryloyl chloride (0.8 mL,
.84 mmol) was added drop wise over a period of 30 min at room
temperature. The mixture was stirred at room temperature for
8 h. Then, the as prepared functionalized MNPs nanoparticles
temperature for 5 h. The solid was separated by magnetic decanta-
tion. The magnetic catalyst was washed with copious amounts of
ethanol and dried under vacuum at room temperature.
9
4
were separated by magnetic decantation and washed three times
with acetone and deionized water to remove the unattached sub-
strates. The resulting product was dispersed in methanol (10.0 mL),
2.6. Catalytic studies
ꢀ
ꢀ
ꢀꢀ
and stirred with N,N,N ,N -tetraethyldiethylenetriamine (TEDETA)
1.0 mL, 3.8 mmol) at room temperature for 1 week. The solids were
2.6.1. General synthesis for the preparation of
2,3-dihydroquinazolin-4(1H)-ones
(
separated by a magnetic field and washed with acetone. The result-
ing product was dried under vacuum for 12 h.
A mixture of aldehydes 1 (1 mmol), 2-aminobenzamide 2
(1 mmol) and CuCl2/Fe3O4-TEDETA (5 mg) in ethanol (10 mL) was
stirred and heated at 80 C. Reaction progress was monitored by TLC
◦
(acetone:n-hexane, 2:8). After the TLC indicates the disappearance
2.5. Magnetic nanoparticle-supported catalyst
of starting materials, the reaction was cooled to room temperature.
The catalyst was separated by an external magnet and reused as
such for the next experiment. The filtrate was evaporated to remove
solvent, the resultant solid was then washed with ethanol to obtain
pure 2,3-dihydroquinazolin-4(1H)-ones in 95–98% yields.
CuCl /Fe O -TEDETA
2
3
4
The Fe O -TEDETA (0.2864 g), was added to the round-bottom
3
4
flask containing a solution of CuCl2 anhydrous (0.134 g, 1 mmol) in
ethanol (280 mL). The mixture was then stirred vigorously at room
Fig. 3. XRD patterns CuCl2/Fe3O4-TEDETA.

A. Ghorbani-Choghamarani, M. Norouzi. / Journal of Molecular Catalysis A: Chemical 395 (2014) 172–179
175
Fig. 4. SEM images of CuCl2/Fe3O4-TEDETA at different magnification.
2.7. Spectral data for new compounds
(KBr): V¯ = 3299, 3248, 3181, 2961, 2831, 1698, 1639, 1808, 1515,
−
1
1
481, 1297, 1151, 742 cm
.
2
.7.1. 2-(4-Ethoxyphenyl)-2,3-dihydroquinazolin-4(1H)-one (3g)
◦
1
White solid, m.p. 161–162 C, H NMR (400 MHz, CDCl ): ı = 7.98
3
(
6
4
brs, 1H), 7.6 (d, J = 6 Hz, 2H), 7.34 (s, 1H), 7.26 (d, J = 2 Hz, 1H),
3
. Results and discussion
.87–7.03 (m, 3H), 6.65 (d, J = 5.6 Hz, 1H), 5.87 (s, 1H), 5.75 (s, 1H),
.12 (t, J = 4 Hz, 2H) 1.45 (q, J = 6.4 Hz, 3H). 13C NMR (100 MHz,
3.1. Catalyst synthesis and characterization
CDCl ): ı = 161.4, 148.9, 147.5, 131.5, 129.9, 120.7, 116.8, 116.0,
1
1
3
¯
15.7, 69.8, 64. 8, 15.9; IR (KBr): V = 3300, 3060, 3000, 2930, 1666,
−
1
Magnetic nanoparticles (MNPs) were prepared by copre-
650, 1610, 1487, 1387 cm
.
cipitation from Fe2+ and Fe3+ using NH3 solution. Then, the
3
-aminopropyltriethoxysilane added was adsorbed onto the sur-
2
.7.2. 2-(2-hydroxy-4-methoxyphenyl)-2,3-dihydroquinazolin-
face of the Fe O4 nanoparticles and form coordination bond
with hydroxyl group, obtained amino-coated Fe O4 nanoparti-
cles. The reaction of amino groups with acryloyl chloride led
to acryloxyl groups-functionalized magnetic Fe O4 nanoparti-
cles. Subsequent, the (TEDETA)-functioned magnetic nanoparticles
were prepared by the Michael reaction of the acryloxyl groups
with tetraethyldiethylenetriamine (TEDETA). Ultimately, the com-
3
4(1H)-one (3j)
3
White solid, m.p. 262–263 C, 1H NMR (400 MHz, DMSO):
◦
ı = 9.35 (s, 1H), 7.68 (d, J = 6.8 Hz, 1H), 7.57 (s, 1H), 7.22 (d, J = 8.4 Hz,
H), 7.14 (s, 1H), 6.98 (s, 1H), 6.67 (d, J = 8 Hz, 2H), 6.36 (s, 1H), 6.28
3
1
¯
(
d, J = 6 Hz, 1H), 5.96 (s, 1H), 3.68 (s, 3H) ppm; IR (KBr): V = 3389,
−
1
3
223, 2924, 1643, 1614, 1505, 1451, 1394, 1247, 754 cm
.
plexes CuCl /Fe O -TEDETA were prepared by reactions of copper
2
3
4
ꢀ
2
(
.7.3. 2,2 -(1,2-phenylene)bis(2,3-dihydroquinazolin-4(1H)-one)
(II) chloride with the individual ligands MNP-TEDETA ethanol.
Scheme 1 illustrates the detail synthetic procedure for functioned
Fe O nanoparticles.
12l)
White solid, m.p. 272–273 C, 1H NMR (400 MHz, DMSO):
ı = 7.87 (d, J = 8.4 Hz, 4H), 7.64 (s, 2H), 7.46 (s, 2H), 7.32 (d, J = 6 Hz,
H), 7.15 (s, 2H), 6.69 (s, 3H), 6.63 (s, 2H), 5.75 (s, 2H) ppm; IR
◦
3
4
The prepared catalyst was characterized by FT-IR spectroscopy,
the thermo gravimetric analysis (TGA), the X-ray diffraction (XRD),
2
Fig. 5. TEM images of CuCl2/Fe3O4-TEDETA at (a) 63,000 and (b) 125,000 magnification.

1
76
A. Ghorbani-Choghamarani, M. Norouzi. / Journal of Molecular Catalysis A: Chemical 395 (2014) 172–179
scanning electron microscopy (SEM) and transmission electron
microscope (TEM).
size 25 nm in diameter. The surface morphology of the supported
TEDETA was practically identical to that of molecular sieves sup-
ports and was composed of relatively well formed, spherical
particles having rather uniform coating of the organic layers.
FTIR spectroscopy (Fig. 1a–e) represents the IR spectra obtained
for Fe O nanoparticles, amino-functionalized, MNP-acryloxyl,
3
4
MNP-TEDETA and CuCl /Fe O -TEDETA respectively. The strong
Morphology of synthesized of CuCl /Fe O -TEDETA nanoparti-
2
3
4
2 3 4
−1
absorption at 580 cm was characteristic of the Fe–O stretching
cles were investigated by TEM and few micrographs along with the
size distribution diagram obtained thereof are presented in Fig. 5.
Particles are observed to have spherical morphology from Fig. 5.
Average particle size is estimated at 19 nm from the TEM micro-
graphs (Fig. 5). This is an indication of nearly single crystalline
character of CuCl /Fe O -TEDETA nanoparticles. These nanoparti-
−
1
vibration but for Fe O nanoparticles at 572 cm as a blue shift,
3
4
−
1
due to the size reduction. The broad feature at 3500–3000 cm
for MNP corresponds to the absorption of –OH stretching of
hydroxyl groups. The amino-functional groups of Fe O4 and the
3
corresponding infrared absorption frequency are shown in Fig. 1b.
The spectra display a number of absorption peaks, indicating
the 3-aminopropyl (triethoxy) silane. The absorption around at
2
3
4
cles consist of irregular CuCl /Fe O -TEDETA and have a narrows
2
3
4
size distribution (mostly between 10 and 19 nm) with an average
diameter of 25 nm, much smaller than the sizes obtained from the
SEM measurements.
−
1
1
111 and 1001 cm corresponds to Si–O stretching vibration. The
−
1
FT-IR spectroscopic analysis indicated broad band at 3394 cm
,
representing bonded –NH groups. The band observed at about
2
−1
2
922–2854 cm could be assigned to the aliphatic C–H group.
The spectrum of Fe O -acryloxyl (Fig. 1c) at wave number
3.2. Catalytic studies
3
4
−
1
1
710 cm is observed, which due to the carbonyl stretch of car-
boxyl. The trough at 1642 cm represents the C C stretching mode
conjugate with the C O (amide 1 band). The peak observed at
020 cm corresponds to the secondary amide group. The peak
observed at 1245 and 1164 cm could be assigned to C–N stretch-
ing and C–O stretching of ether groups, respectively.
As a part of our ongoing project devoted towards the develop-
−
1
ment of a practical synthesis of biologically interesting heterocyclic
molecules [38–42], herein we had the opportunity to further
explore the catalytic activity of CuCl /Fe O -TEDETA in the synthe-
−
1
3
2
3
4
−
1
sis of 2,3-dihydroquinazolin-4(1H)-ones derivatives, via one-pot
and the condensation reaction of 2-aminobenzamide with alde-
hydes in ethanol under reflux conditions to excellent yields
When comparing the two spectra in Fig. 1c and d, Fig. 1d shows
that there were various functional groups detected on the surface
of Fe O -TEDETA. There are some peaks that were shifted, disap-
(Scheme 2).
3
4
In order to establish the optimum conditions, for our
peared and new peaks were produced. Significant band decrease
of functional group on the Fe O -TEDETA were detected at bands
initial screening experiments, the optimal catalyst loading
were examined. The synthesis of 2-(4-chlorophenyl)-2,3-
dihydroquinazolin-4(1H)-one 3a was used as a model. A mixture
of 4-chlorobenzaldehyde 1a (1 mmol), and 2-aminobenzamide 1
3
4
1
701 and 1155, which corresponded to the bonded C O stretch-
ing and –C–C– groups, respectively. These two significant bands in
the spectrum indicate the possible involvement of those functional
(1 mmol) reaction in the absence of any catalyst and observed that
groups on the surface of Fe O -TEDETA process. Thus, it seems that
3
4
there was no formation of product after 12 h. To improve the yield
and optimize the reaction conditions, the same reaction was carried
out in the presence of a catalytic amount of CuCl/Fe O -TEDETA
this type of functional group is likely to participate in metal binding.
Fig. 1e shows the FTIR spectrum after adsorption of Cu (II) ions
3
4
onto Fe O -TEDETA.
3
4
under similar conditions. Surprisingly, a significant improvement
was observed and the yield of 3a was dramatically increased to
To obtain more quantitative information about extent of func-
tionalization and contents of CuCl /Fe O -TEDETA, the thermo
2
3
4
2
3% after stirring; the mixture was stirred for only 45 min (Table 1,
gravimetric analysis (TGA) was performed and the profiles obtained
are exhibited in Fig. 2. The profile of MNPs showed a minute
Entry 2). An increase in the quantity of CuCl/Fe O -TEDETA from
3
4
1
to 5 mg increased the product yield slightly from 23% to 98%
◦
weight loss of about 126 C owing to the removal of physically
(
Table 1, Entry 3). Using more than 5 mg CuCl/Fe O -TEDETA has
3
4
adsorbed solvent and surface hydroxyl groups (Fig. 2a). In addi-
tion, there is a weight loss of about 3.5% displayed for MNPs in
less effect on the yield and time of the reaction.
◦
the temperature range of between 200 and 474 C is attributed to
dehydration of the surface –OH group. From the TG data (Fig. 2b–e),
we calculate that the organic chemicals concentration sin sam-
ples amino-functionalized, MNP-acryloxyl and MNP-TEDETA are
CHO
O
CONH2 Fe3O4 Magnetic
Nanoparticles
NH
+
1
1.0, 23.79 and 28.94 wt% respectively. While CuCl /MNPs-TEDETA
2
EtOH, Reflux
exhibited a weight loss of 36.08% in the temperature range from
NH2
N
H
x
◦
2
00 to 488 C due to the thermal decomposition of the functional-
ized groups, which indicates the amount of functionalized grafted
1
2
3
x
to MNP was 36.08 wt% (Fig. 2e).
S
The CuCl /Fe O -TEDETA catalyst was characterized using var-
2
3
4
Scheme 2. Synthesis of 2,3-dihydroquinazolin-4(1H)-ones.
ious methods. X-ray diffraction (XRD) of the bare MNP displayed
patterns consistent with the patterns of spinel ferrites described
in the literature (Fig. 3). A series of characteristic peaks in pattern
A at (2ꢀ= 21.2 , 35.2 , 41.5 , 50.6 , 63.1 , 67.5 and 74.4 ), marked
by their indices ((1 1 1), (2 2 0), (3 1 1), (4 0 0), (4 2 2), (5 1 1), and
Table 1
a
Optimization of the amount of CuCl/Fe3O4-TEDETA.
◦
◦
◦
◦
◦
◦
◦
Entry
Catalyst (mg)
Yieldb (%)
1
2
3
4
5
–
1
3
5
8
Tracec
23
50
98
98
(
4 4 0)), agree with the standard Fe O4 XRD spectrum [37]. This
3
revealed that the surface modification and conjugation of the Fe O4
3
nanoparticles do not lead to their phase change. The sample show
very broad peaks, indicating the ultra-fine nature and small crys-
tallite size of the particles.
a
Reaction conditions: 4-chlorobenzaldehyde (1 mmol), 2-aminobenzamide
1 mmol) and ethanol (10 mL) at reflux temperature.
SEM images of CuCl /Fe O -TEDETA at different magnification
2
3
4
(
are shown in Fig. 4. According to Fig. 4, the CuCl /Fe O -TEDETA
exhibited a cluster of aggregated spherical particles with an average
b
Isolated yields.
2
3
4
c
Reaction proceeds in the absence of the catalyst.

A. Ghorbani-Choghamarani, M. Norouzi. / Journal of Molecular Catalysis A: Chemical 395 (2014) 172–179
177
Table 2
Synthesis of 2,3-dihydroquinazolin-4(1H)-one derivatives.
◦
Entry
Compound
Aldehyde (1)
Product (3)
Time (min)
45
Yieldb (%)
Mp ( C) [Ref.]
1
A
98
202–203 [24]
2
3
4
B
C
D
60
55
25
95
98
97
225–226 [31]
197–200 [34]
182–183 [31]
5
E
30
96
211–212 [24]
6
7
F
30
40
97
97
223–224 [24]
167–168
G
8
9
H
20
50
40
96
94
192–193 [34]
184–185 [36]
I
1
0
1
J
97
98
262–263
1
K
100
244–245 [34]

1
78
Table 2 (Continued)
Entry Compound
A. Ghorbani-Choghamarani, M. Norouzi. / Journal of Molecular Catalysis A: Chemical 395 (2014) 172–179
Yieldb (%)
Mp ( C) [Ref.]
◦
Aldehyde (1)
Product (3)
Time (min)
1
2
L
70
97
272–273
1
3
4
M
N
30
45
95
96
157–159 [23]
209–210 [23]
1
a
Reaction conditions: aldehyde (1 mmol), 2-aminobenzamide (1 mmol), catalyst (5 mg) and ethanol solvent (10 mL) at reflux temperature.
Isolated yields.
b
100
80
60
40
20
0
25
40
60
80
100
T °C
Fig. 7. CuCl/Fe O -TEDETA in the reaction mixture (a) and its recovery using an
external magnet (b).
3
4
Fig. 6. Effect of temperature in the preparation of 2-(4-chlorophenyl)-2,3-
dihydroquinazolin-4(1H)-one.
In the next step, the effect of temperature was investigated by
carrying out the model reaction in the presence of CuCl/Fe O -
3
4
◦
◦
TEDETA (5 mg) at room temperature (25 C), 40, 60 and 80 C. It was
observed that the yield was increased as the reaction temperature
was raised (Fig. 6).
Based on above observations, we conducted the same reac-
tions using 2-aminobenzamide, variety of different substituted
aldehydes 1a–n in the presence of 5 mg of CuCl/Fe O -TEDETA
3
4
under similar conditions. As expected, satisfactory results were
observed, and the results are summarized in Table 2. It is shown
that in general a wide range of aldehydes could react with 2-
aminobenzamide smoothly and give 3a–n in good to excellent
yields (Table 2, entries 1–12). It is also notable that the electronic
property of the aromatic ring of aldehydes has some effects on
the rate of the condensation process. The use of aliphatic alde-
hydes derivative, such as butyraldehyde and cinnamaldehyde also
afforded the desired products in excellent yield (Table 2, entries 13
and 14).
After completion of the reaction, the reaction solution was
then easily removed from the reaction vessel by decantation
while the magnet held the magnetic nanoparticles inside the ves-
sel. The magnetic catalyst was washed with ethanol and water
Fig. 8. Reuse of the nanocatalyst for conversion of 4-chloroaldehyde to the corre-
sponding 2,3-dihydroquinazolin-4(1H)-ones.
(Fig. 7).

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mg CuCl/Fe O -TEDETA as the catalyst. After completion of the
3 4
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a heterogeneous catalyst for synthesis of 2,3-dihydroquinazolin-
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2
3
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morphology of CuCl /Fe O -TEDETA does not change after reac-
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Authors thank the research facilities of Ilam University, Ilam,
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