Cu(II) complex-decorated hybrid nanomaterial: a retrievable catalyst for green synthesis of 2,3-dihydroquinazolin-4(1H)-ones

Article abstract of DOI:10.1080/00958972.2021.1905803

The significant stability of magnetic core and ? OH functional groups on the surface of silica-coated cobalt ferrite (CoFe₂O₄@SiO₂) nanoparticles make it a good candidate for functionalization and catalytic application. In

Full text of DOI:10.1080/00958972.2021.1905803

Journal of Coordination Chemistry
ISSN: (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/gcoo20
Cu(II) complex-decorated hybrid nanomaterial:
a retrievable catalyst for green synthesis of 2,3-
dihydroquinazolin-4(1H)-ones
Mohammad Ali Bodaghifard & Somayeh Safari
To cite this article: Mohammad Ali Bodaghifard & Somayeh Safari (2021): Cu(II)
complex-decorated hybrid nanomaterial: a retrievable catalyst for green synthesis
of 2,3-dihydroquinazolin-4(1H)-ones, Journal of Coordination Chemistry, DOI:
10.1080/00958972.2021.1905803
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JOURNAL OF COORDINATION CHEMISTRY
https://doi.org/10.1080/00958972.2021.1905803
Cu(II) complex-decorated hybrid nanomaterial:
a retrievable catalyst for green synthesis
of 2,3-dihydroquinazolin-4(1H)-ones
Mohammad Ali Bodaghifarda,b and Somayeh Safaria
b
aDepartment of Chemistry, Faculty of Science, Arak University, Arak, Iran; Institute of Nanosciences
and Nanotechnology, Arak University, Arak, Iran
ABSTRACT
ARTICLE HISTORY
Received 11 August 2020
Accepted 18 February 2021
The significant stability of magnetic core andꢀ OH functional
groups on the surface of silica-coated cobalt ferrite
(CoFe2O4@SiO2) nanoparticles make it a good candidate for func-
tionalization and catalytic application. In this work, a surface-
modified magnetic solid support with Cu(II) complex was
prepared. The structure of the new nanostructure was character-
ized by Fourier-transform infrared spectroscopy (FT-IR), X-ray pow-
der diffraction (XRD), thermogravimetric analysis (TGA/DTG),
vibrating sample magnetometer (VSM), the field emission scan-
ning electron microscopy (FE-SEM), the electron-dispersive X-ray
spectroscopy (EDS), and inductively coupled plasma optical emis-
sion spectrometry (ICP/OES) techniques. The catalytic activity of
the prepared hybrid nanomaterial was evaluated in the synthesis
of 2,3-dihydroquinazolin-4(1H)-ones and high yields of desired
products were obtained with green media. Some advantages of
this method are high yields, short reaction times, green solvent
and conditions, easy workup procedure, negligible copper leach-
ing, reusability without a significant diminish in catalytic efficiency
and simple separation of nanocatalyst by using an external
magnet alongside the environmental compatibility and
sustainability.
KEYWORDS
Hybrid nanostructure;
magnetic nanoparticles;
heterogeneous catalysis;
cobalt ferrite; 2,3-
Dihydroquinazolin-
4(1H)-one
CONTACT Mohammad Ali Bodaghifard
mbodaghi2007@yahoo.com, m-bodaghifard@araku.ac.ir
Department
of Chemistry, Faculty of Science, Arak University, Arak, 38156-88138, Iran
ß 2021 Informa UK Limited, trading as Taylor & Francis Group

2
M. A. BODAGHIFARD AND S. SAFARI
1. Introduction
According to the principals of green chemistry, designing green reaction conditions
have become an important subject for elimination of pollution from the environment.
Use of solvent-free conditions or green solvents, especially water in organic reactions
instead of hazardous solvents has developed in organic synthesis [1, 2].
Multicomponent reactions (MCRs) are a good way to produce complex and diverse
combinations of interest [3–5]. MCRs have many advantages such as low reaction
times, diminished work-up procedures, high efficiency, low cost, high selectivity and
low environmental impact compared to methods of classical chemistry [5, 6]. MCRs
are experimentally simple to perform, often without the need of dry conditions and
inert atmosphere and provide huge chemical diversity; currently hundreds of different
structurally varied chemical scaffolds have been described [7–9].
Mono- and disubstituted 2,3-dihydroquinazoline-4(1H)-ones have a broad range of
biological and pharmacological properties such as analgesic, antitumor, anticancer,
diuretic and herbicide activities [10–13]. These compounds can be easily oxidized to
their quinazolin-4(3H)-one analogues [14], which also include important pharmaco-
logically active compounds [15, 16]. Several methods have been reported for synthesis
of 2,3-dihydroquinazolinones [17–30]. A general synthesis of 2,3-dihydroquinazolin-
4(1H)-one derivatives involves three-component condensation reaction between aryl
aldehydes, isatoic anhydride and amines [26–31]. However, these methods suffer from
lengthy procedures and/or low yields, use of volatile and harmful solvents, and vigor-
ous reaction conditions. So, the development of simple, high yield approaches and
milder reaction conditions toward these valuable derivatives is desirable.
Magnetic nanoparticles (MNPs) have high surface area and can be easily separated
by using an external magnetic field and do not have tedious separation procedures
which result from small nanoparticles [32]. However, magnetic nanoparticles can easily
aggregate into larger clusters because of their anisotropic dipolar attraction. In add-
ition, they have other deficiencies such as leaching under acidic conditions and being
susceptible to autoxidation and toxicity. Therefore, it is necessary to protect the sur-
face of MNPs in order to reduce these undesirable features. For this purpose, MNPs
are usually coated with a polymeric or inorganic matrix [33]. Among inorganic com-
pounds, SiO2 can be a suitable candidate for protecting the surface of MNPs due to its
high chemical and thermal stability and most importantly its easy modification by a
wide range of functional groups, which increase chemical and colloidal stability of
these compounds [34–40]. Using magnetic nanoparticles as catalysts is associated with
other advantages including easy synthesis and functionalization, low toxicity and low
cost [34–37].
Metal complexes have been used as homogenous catalysts in a wide range of reac-
tions. However, most are precious and expensive and have drawbacks such as tedious
separation and decreasing of catalytic activities with time. To overcome some of these
issues, several metal complexes have been immobilized onto inorganic supports with
many reports for grafting and immobilization of metal complexes on magnetic nano-
sized inorganic supports that benefit from excellent catalytic activities, high selectivity
and easy separation [34].

JOURNAL OF COORDINATION CHEMISTRY
3
As part of our continuous effort to develop efficient heterogeneous magnetic nano-
catalysts and green organic reactions to prepare valuable heterocyclic compounds [31,
34, 41–44], herein we report the preparation of a heterogeneous copper complex-sup-
ported hybrid nanostructure [CoFe2O4@SiO2@BIMA@Cu] as a catalyst for synthesis of
2,3-dihydroquinazolin-4(1H)-one derivatives.
2. Experimental
All reagents were purchased from chemical companies (Merck, Acros, Fluka) and were
used without further purification. Melting points were measured by using an electro-
thermal digital apparatus and are uncorrected. Obtained products were identified with
comparison of their melting points and spectral data reported in the literature. FT-IR
spectra were recorded in a Unicom Galaxy Series. The 1H and 13C NMR spectra for
obtained products were reported on a Bruker DRX-300 spectrometer operating at 300
and 75 MHz, respectively, in DMSO-d6 with TMS as an internal standard. The crystal
was examined on a Philips Xpert Xray powder diffraction (XRD) diffractometer (Cu-Ka
radiation and k ¼ 0.15406) in range of Bragg angle 10–80 using 0.05ꢁ as the step
length. The thermal stability of CoFe2O4@SiO2@PAF-IL was investigated by a thermog-
ravimetric analyzer Mettler TA4000 System under an N2 atmosphere at a heating rate
of 10 ꢁCminꢀ1. The surface morphology and elemental content of CoFe2O4@SiO2@PAF-
IL were investigated on a Hitachi S-4160. Elemental chemical analysis [energy disper-
sive X-ray spectroscopy (EDS)] coupled with SEM was reported for characterization of
chemical elements of the prepared hybrid nanomaterial. The magnetization and hys-
teresis loop for the synthesized magnetic nanoparticles were measured at room tem-
perature using a 7300 VSM system with a maximum field of 10 kOe. The loading
amount of Cu on [CoFe2O4@SiO2@BIMA@Cu] was determined with an inductively
coupled plasma optical emission spectrometer (SPECTRO ARCOS).
2.1. Preparation of cobalt ferrite nanoparticles (CoFe2O4)
Magnetic cobalt ferrite nanoparticles were prepared by co-precipitation method
according to procedure reported in the literature [37]. First, CoCl2ꢂ6H2O (5 mmol, 1.8 g)
and FeCl3ꢂ6H2O (10 mmol, 2.7 g) were added to 50 mL of deionized water in a round
bottom flask (100 mL) and the mixture was stirred at room temperature for 10 minutes.
The pH was adjusted to 11 and 12 using NaOH (0.3 M) solution. The reaction mixture
was stirred at 80 ꢁC for 1 h. After cooling to room temperature, the precipitate was
separated by magnet and washed with deionized water several times and finally
washed with ethanol and dried in an oven at 80 ꢁC.
2.2. Synthesis of silica-coated MNPs (CoFe2O4@SiO2)
The silica shell was coated onto CoFe2O4 nanoparticles via hydrolysis of TEOS in basic
solution [37]. Magnetic cobalt ferrite nanoparticles (1 g), ethanol (40 mL), deionized
water (6 mL) and ammonia 25% (1.5 mL) were introduced in a 100 mL flask and soni-
cated for 20 min. Then, tetraethylorthosilicate (TEOS) (1.4 mL) was added. The reaction

4
M. A. BODAGHIFARD AND S. SAFARI
Scheme 1. Synthesis of (1H-benzo[d]imidazol-2-yl)methanamine (BIMA).
mixture was stirred at room temperature for 12 h. Finally, the precipitate was sepa-
rated by magnet and washed with deionized water several times and ethanol, and
dried in an oven at 80 ꢁC.
2.3. Synthesis of 3-chloropropyl-funactionalized magnetic nanoparticles
(CoFe2O4@SiO2-PrCl)
CoFe2O4@SiO2 nanoparticles (1 g) were dispersed in 50 ml toluene for 10 minutes
under sonication. Then, (3-chloropropyl)triethoxysilane (CPTES) (2 g) was added and
refluxed for 24 h at 110 ꢁC. Finally, the precipitate was separated by external magnet
and washed with toluene several times and dried in an oven at 80 ꢁC.
2.4. Synthesis of (1H-benzo[d]imidazol-2-yl)methanamine (BIMA, Scheme 1)
A mixture of 1,2-phenylenediamine (10 mmol, 1.08 g) and glycine (10 mmol, 0.75 g) in
20 mL toluene in a 100 mL round-bottomed flask was refluxed for 10 h at 110 ꢁC
[45–47]. Excess solvent was evaporated and the mixture diluted with ethyl acetate.
The solid product was extracted using n-hexane and dried in a vacuum oven at 50 ꢁC.
2.5. Preparation of CoFe2O4@SiO2@BIMA
To synthesize the CoFe2O4@SiO2@BIMA nanocomposite, a mixture of (1H-benzo[d]imi-
dazol-2-yl)methanamine, (0.5 g), triethylamine (0.5 g) and CoFe2O4@SiO2-PrCl (1 g) in
20 mL of DMF in a 100 mL round-bottomed flask was stirred under sonication. Then,
the mixture was stirred with a magnetic stirrer for 24 h at 100 ꢁC. After the reaction
was complete, the precipitate was washed several times with hot ethanol and dried in
an oven at 80 ꢁC.
2.6. Stabilization of Cu complex on magnetic nanoparticles
[CoFe2O4@SiO2@BIMA@Cu]
In a 50 mL round-bottomed flask, 1 g of CoFe2O4@SiO2@BIMA in 20 mL EtOH (99%)
and Cu(OAc)2ꢂH2O (0.1 mmol, 0.2 gr) was refluxed under N2 for 12 h. The resulting mix-
ture was washed with deionized water and ethanol. The resulting hybrid nanomaterial
[CoFe2O4@SiO2@BIMA@Cu] was separated using a magnet and dried in a vacuum
oven at 80 ꢁC.

JOURNAL OF COORDINATION CHEMISTRY
5
2.7. General procedure for one-pot synthesis of 2,3-dihydroquinazolin-
4(1H)-ones
In a 25 mL round-bottomed flask, [CoFe2O4@SiO2@BIMA@Cu] (20 mg) was added to a
mixture of aromatic aldehyde (1 mmol), isatoic anhydrides (1 mmol), ammonium acet-
ate (2 mmol) or primary amine (1 mmol) in water (5 mL) and refluxed for an appropri-
ate time. After completion, the resulting mixture was diluted with hot ethanol (10 mL)
and the catalyst was separated by an external magnet. The reaction mixture was
cooled to room temperature and filtered to afford the crude products. The purified
products were obtained by recrystallization from ethanol-water (4:1).
2.8. Selected spectroscopic data
2-(4-Bromophenyl)-2,3-dihydroquinazolin-4(1H)-one (4 b)
1
FT-IR (KBr), mmax ¼ 3307, 3187, 3058, 1659, 1609, 1385, 752 cmꢀ1; H NMR (DMSO-d6):
d ¼ 8.35 (1H, s, NH), 7.60 (1H, d, J ¼ 7.8 Hz, ArH), 7.44-7.52 (4H, m, ArH), 7.27 (1H, t,
J ¼ 7.8 Hz, ArH), 7.15 (1H, s, NH), 6.72 (1H, d, J ¼ 8.2 Hz,ArH), 6.66 (1H, t, J ¼ 7.8 Hz, ArH),
5.76 (1H, s, CH) ppm. Anal. Calcd. for C14H11BrN2O: C, 55.47; H, 3.66; N, 9.24. Found: C,
55.55; H, 3.73; N, 9.32.
2-(4-(Dimethylamino)phenyl)-2,3-dihydroquinazolin-4(1H)-one (4j)
FT-IR (KBr), mmax ¼ 3291, 3191, 3052, 2890, 2805, 1655, 1612, 1512, 1354, 1161, 818,
1
752, 520 cmꢀ1. H NMR (DMSO-d6): d ¼ 8.13 (1H, s, NH), 7.63 (1H, d, J ¼ 7.5 Hz, HAr),
7.23-7.34 (3H, m, HAr), 6.96 (1H, s, NH), 6.66-6.76 (4H, m, HAr), 5.66 (1H, s, CH), 2.91 (6H,
s, 2CH3) ppm.; 13C NMR (DMSO-d6): d ¼ 164.3, 151.1, 148.6, 133.6, 131.8, 129.1, 128.2,
127.8, 117.4, 115.5, 114.8, 112.4, 67.1, 40.6 ppm. Anal. Calcd. for C16H17N3O: C, 71.89; H,
6.41; N, 15.72. Found: C, 71.78; H, 6.49; N, 15.81.
2,3-Diphenyl-2,3-dihydroquinazolin-4(1H)-one (5a)
1
FT-IR (KBr), mmax ¼ 3296, 3059, 1633, 1508, 1390, 1159, 752, 696 cmꢀ1. H NMR (DMSO-
d6): d ¼ 7.75 (1H, d, J ¼ 7.5 Hz, ArH), 7.70 (1H, s, NH), 7.19-7.42 (11H, m, ArH), 6.75 (2H,
m, ArH), 6.32 (1H, s, CH) ppm. Anal. Calcd. for C20H16N2O: C, 79.98; H, 5.37; N, 9.33.
Found: C, 79.89; H, 5.44; N, 9.45.
2-(4-Bromophenyl)-3-(p-tolyl)-2,3-dihydroquinazolin-4(1H)-one (5 l)
1
FT-IR (KBr), mmax ¼ 3302, 1636, 1609, 1512, 1389, 1087, 822, 755, 512 cmꢀ1. H NMR
(300 DMSO-d6): d ¼ 8.45 (1H, s, NH), 6.54-7.77 (12H, m, HAr), 6.07 (1H, s, CH), 2.13 (3H,
s, CH3) ppm. Anal. Calcd. for C21H17BrN2O: C, 64.13; H, 4.36; N, 7.12. Found: C, 64.27; H,
4.41; N, 7.17.
3-Benzyl-2-(4-chlorophenyl)-2,3-dihydroquinazolin-4(1H)-one (5n)
1
FT-IR (KBr), mmax ¼ 3472, 3358, 3302, 1630, 1539, 1449, 1269, 752, 727, 696 cmꢀ1. H
NMR (300 DMSO-d6): d ¼ 8.5 (1H, s, NH), 7.36 (1H, s, CH), 6.22-7.12 (13H, m, HAr), 4.23
(2H, s, CH2). Anal. Calcd. for C21H17ClN2O: C, 72.31; H, 4.91; N, 8.03. Found: C, 72.23; H,
4.97; N, 8.11.

6
M. A. BODAGHIFARD AND S. SAFARI
Scheme 2. Schematic steps for construction of CoFe2O4@SiO2@BIMA@Cu hybrid nanostructure.
2-(4-Chlorophenyl)-3-propyl-2,3-dihydroquinazolin-4(1H)-one (5o)
FT-IR (KBr), mmax ¼ 3303, 2963, 2870, 1628, 1508, 1304, 1088, 852, 744, 517 cmꢀ1. H
NMR (DMSO-d6): d ¼ 7.67 (1H, d, J ¼ 7.7 Hz, ArH), 7.35-7.46 (5 H, m, ArH and NH), 7.22
(1H, t, J ¼ 7.3 Hz, ArH), 6.64-6.71 (2 H, m, ArH), 5.90 (1H, s, CH), 3.83-3.92 (1H, m, CH2),
2.70-2.80 (1H, m, CH2), 1.45-1.62 (2H, m, CH2), 0.86 (3H, t, J ¼ 7.3 Hz, CH3) ppm. 13C
NMR (DMSO-d6): d ¼ 162.6, 146.5, 140.7, 133.6, 133.3, 128.9, 128.4, 127.9, 117.7, 115.5,
114.8, 69.7, 46.6, 21.3, 11.6 ppm. Anal. Calcd. for C17H17ClN2O: C, 67.88; H, 5.70; N, 9.31.
Found: C, 67.73; H, 5.81; N, 9.41.
1
3. Results and discussion
3.1. Preparation and characterization of the hybrid nanostructure
The magnetic hybrid nanoparticles were prepared sequentially as depicted in Scheme
2. First, CoFe2O4 prepared easily by the co-precipitation method from reaction of Co2þ
and Fe3þ ions in basic conditions [37]. Then, CoFe2O4 nanoparticles were coated with
€
silica layer using the Stober method [37]. The chloropropyl-modified silica-coated
CoFe2O4 nanoparticles were prepared by reaction of CoFe2O4@SiO2 with (3-chloropro-
pyl)triethoxisilane (CPTES) which can bind covalently to free-OH groups at the particles
surface and afforded the Fe3O4@SiO2-PrCl. The reaction of (1H-benzo[d]imidazol-2-
yl)methanamine
with
CoFe2O4@SiO2-PrCl
resulted
in
construction
of
CoFe2O4@SiO2@BIMA nanostructure. Finally, Cu(OAc)2 was stabilized on the modified
magnetic nanoparticles. The resulting precipitate was washed with ethanol and dried
in the vacuum oven to gain [CoFe2O4@SiO2@BIMA@Cu]. Fourier transform infrared
(FT-IR) spectroscopy, X-ray powder diffraction (XRD), field emission scanning electron
microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDS), thermogravimetric
analysis (TGA/DTG), vibrating sample magnetometry (VSM) and inductively coupled
plasma optical emission spectrometry (ICP/OES) were employed to characterize the
prepared hybrid nanostructure.

JOURNAL OF COORDINATION CHEMISTRY
7
Figure 1. FT-IR spectra of CoFe2O4 (a), CoFe2O4@SiO2 (b), CoFe2O4@SiO2-PrCl (c),
CoFe2O4@SiO2@BIMA (d) and CoFe2O4@SiO2@BIMA@Cu (e).
The FT-IR spectra of CoFe2O4 (a), CoFe2O4@SiO2 (b), CoFe2O4@SiO2@Pr-Cl (c),
CoFe2O4@SiO2@BIMA (d) and CoFe2O4@SiO2@BIMA@Cu (e) are shown in Figure 1. The
FT-IR spectrum of magnetic CoFe2O4 nanoparticles show the characteristic Fe-O and
Co-O absorption bands at 594 and 389 cmꢀ1 (Figure 1(a)). Also, a broad band at
3380 cmꢀ1 refers to stretching vibrations of H-O-H groups on the surface of nanopar-
ticles. CoFe2O4@SiO2 shows characteristic FT-IR bands at 1084 cmꢀ1, 798 cmꢀ1 and
457 cmꢀ1 which are attributed to the asymmetric stretch, symmetric stretch, in plane
bending and rocking mode of the Si–O–Si group, respectively, that confirm the forma-
tion of the SiO2 shell (Figure 1(b)). The absorption band at 1620 cmꢀ1 is from stretch
of Si-OH groups. The weak absorptions at 2850 and 2980 cmꢀ1 are attributed to sym-
metric and asymmetric stretching modes of the attached alkyl groups (Figure 1(c)–(e)).
Thus, the results confirm that the functional groups were grafted on the surface of
CoFe2O4 nanoparticles.
The X-ray powder diffraction (XRD) patterns were used to study the crystallinity of
the prepared nanostructure (Figure 2). The XRD patterns of CoFe2O4 (a) and
CoFe2O4@SiO2@BIMA@Cu (b) show characteristic peaks at 74.5, 63.0, 57.3, 53.9, 43.3,
35.8 and 30.4ꢁ, attributed to the 533, 440, 511, 422, 400, 311 and 220 planes of
CoFe2O4, respectively (Figure 2(a)). These data are according to the standard CoFe2O4
sample (standard JCPDS no. 22-1086) and confirm a cubic spinel structure for CoFe2O4
nanoparticles [37]. The broad peak at 2h ¼ 20-27ꢁ can be attributed to the amorphous
SiO2 coated on the surface of CoFe2O4 core in CoFe2O4@SiO2@BIMA@Cu nanostructure
(Figure 2(b)). The average crystallite sizes were estimated using Scherrer’s equation
(D ¼ 0.9 k/bcosh) with CoFe2O4@SiO2@BIMA@Cu calculated from the width of the
peak at 2h ¼ 35.8ꢁ (311) is 35 nm, which is in the range determined using FE-SEM ana-
lysis (Figure 3).

8
M. A. BODAGHIFARD AND S. SAFARI
Figure 2. XRD patterns of CoFe2O4 (a) and CoFe2O4@SiO2@BIMA@Cu (b).
Figure 3. FE-SEM image of CoFe2O4@SiO2@BIMA@Cu nanomaterial.
Figure 4. TGA/DTG thermogram of CoFe2O4@SiO2@BIMA@Cu.

JOURNAL OF COORDINATION CHEMISTRY
9
Figure 5. EDX analysis of CoFe2O4@SiO2@BIMA@Cu.
The thermal stability of CoFe2O4@SiO2@BIMA@Cu was determined by thermal ana-
lysis (TGA/DTG) from 50 ꢁC to 950 ꢁC (Figure 4). The magnetic nanomaterial shows
three weight loss steps and total weight loss of MNPs in three steps was 19% wt. The
first stage, including a small (4%) weight loss at T < 200 ꢁC, was due to the removal of
physically adsorbed solvent, water and surface hydroxyl groups. The second step at
200 ꢁC to nearly 500 ꢁC is attributed to decomposition of the organic layer in the
nanocomposite. Therefore, the weight loss between 200 and 500 ꢁC gives the organic
moiety ratio grafted on the prepared nanomaterial. The organic moiety grafted on the
CoFe2O4@SiO2@BIMA@Cu was approximately 10% wt. The third step shows weight
loss 5% at T > 500 ꢁC attributed to destruction and deformation of silica layer. The
exact amount of copper in CoFe2O4@SiO2@BIMA@Cu was measured using the ICP/OES
technique and the amount of copper in the hybrid nanocatalyst is
1.87 ꢃ 10ꢀ3 mol gꢀ1
.
The size and morphology of the CoFe2O4@SiO2@BIMA@Cu particles were investi-
gated by field emission scanning electron microscopy (Figure 3). The SEM image
shows CoFe2O4@SiO2@BIMA@Cu particles are nearly spherical shapes with mean diam-
eter 30 nm. The electron dispersive X-ray spectrum (EDS) confirms the presence of car-
bon (C), silicon (Si), nitrogen (N), oxygen (O), cobalt (Co), iron (Fe), and copper (Cu) in
CoFe2O4@SiO2@BIMA@Cu nanostructure (Figure 5). The higher intensity of the Si peak
compared to the Fe and Co peaks exhibits the CoFe2O4 nanoparticles have been
trapped by the SiO2 layer. So, based on the results, the CoFe2O4@SiO2@BIMA@Cu
nanocomposite has been fabricated.
The magnetic properties for CoFe2O4 (a) and CoFe2O4@SiO2@BIMA@Cu (b) nanopar-
ticles are measured by a vibrating sample magnetometer (VSM) in ꢀ12000 to
12000 Oe range at room temperature (Figure 6). The hysteresis loops show
Superparamagnetic behavior in two samples and no hysteresis phenomenon was
observed. The obtained saturation magnetizations (Ms) for CoFe2O4 and
CoFe2O4@SiO2@BIMA@Cu were observed at 45 and 20 Oe, respectively. These results
show the functionalization led to decrease in the magnetic properties of the
nanostructure.

10
M. A. BODAGHIFARD AND S. SAFARI
Figure 6. VSM analysis of CoFe2O4 (a) and CoFe2O4@SiO2@BIMA@Cu (b).
Scheme 3. The synthesis of 2,3-dihydroquinazolin-4(1H)-ones in the presence of
CoFe2O4@SiO2@BIMA@Cu as a catalyst.
Table 1. Optimization of the reaction conditions for synthesis of 2,3-dihydroquinazolin-
4(1H)-ones.a
Entry
Catalyst (mg)
Solvent
EtOH
EtOH
Temperature (ꢁC)
Time (min)
Yield (%)
1
2
3
4
5
6
7
8
CoFe2O4@SiO2@BIMA@Cu (10)
CoFe2O4@SiO2@BIMA@Cu (10)
CoFe2O4@SiO2@BIMA@Cu (10)
CoFe2O4@SiO2@BIMA@Cu (10)
CoFe2O4@SiO2@BIMA@Cu (10)
CoFe2O4@SiO2@BIMA@Cu (10)
CoFe2O4@SiO2@BIMA@Cu (10)
CoFe2O4@SiO2@BIMA@Cu (10)
CoFe2O4@SiO2@BIMA@Cu (10)
CoFe2O4@SiO2@BIMA@Cu (5)
CoFe2O4@SiO2@BIMA@Cu (20)
CoFe2O4 (20)
70
80
60
60
60
60
80
90
60
40
40
30
90
90
90
120
80
85
43
41
85
67
40
87
93
81
95
81
73
79
25
Reflux
Reflux
Reflux
Reflux
100
r.t
70
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
DMF
CH3CN
EtOH:H2O
Solvent-free
H2O
H2O
H2O
H2O
H2O
H2O
H2O
9
10
11
12
13
14
15
CoFe2O4@SiO2 (20)
CoFe2O4@SiO2@BIMA (20)
–
H2O
H2O
a4-chlorobenzaldehyde, isatoic anhydride, ammonium acetate, catalyst.
3.2. Synthesis of 2,3-dihydroquinazolin-4(1H)-ones using
CoFe2O4@SiO2@BIMA@Cu as a catalyst
After preparation and characterization of CoFe2O4@SiO2@BIMA@Cu, its catalytic activ-
ity was considered in the synthesis of 2,3-dihydroquinazolin-4(1H)-one derivatives. The

JOURNAL OF COORDINATION CHEMISTRY
11
Table 2. Synthesis of 2,3-dihydroquinazolin-4(1H)-ones using CoFe2O4@SiO2@BIMA@Cu as
a catalyst.
M.p.(ꢁC)
[26–31]
Entry
R1
NH4OAc or R2NH2 Product Time (min) Yield (%)a Foundb
Reported
1
2
3
4
5
6
7
8
C6H5
4-Br-C6H4
4-OCH3-C6H4
3,4-(OCH3)2-C6H3 NH4OAc
4-CH3-C6H4
3-NO2-C6H4
4-NO2-C6H4
4-Cl-C6H4
4-OH-C6H4
4-(N(CH3)2)-C6H4
2-pyridyl
NH4OAc
NH4OAc
NH4OAc
4a
4b
4c
4d
4e
4f
4g
4h
4i
30
30
35
40
30
35
35
30
35
30
45
40
30
30
30
40
40
30
35
40
50
50
35
50
30
50
93
91
90
91
93
92
90
95
90
90
87
93
95
90
92
87
90
95
90
92
85
92
93
95
94
93
290–293
269–271
226–227
273–275
274–275
223–224
>300
285–287
265–267
218–221
274–277
105–107
84–85
120–121
269–271
230-232
253–255
140–142
221–223
284–286
209–212
273–275
251–253
272–275
126–128
175–177
290–292
275–276
224–226
271–273
274–276
221–224
318–320
288–290
264–265
227–229
275–278
113–115
88–89
120–121
275–278
231–233
261–262
144–146
225–227
284–286
211–213
270–274
–
NH4OAc
NH4OAc
NH4OAc
NH4OAc
NH4OAc
NH4OAc
NH4OAc
PhNH2
PhNH2
PhNH2
PhNH2
PhNH2
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
4j
4k
5a
5b
5c
5d
5e
5f
5g
5h
5i
5j
5k
5l
5m
5n
5o
C6H5
4-Cl-C6H4
2-Cl-C6H4
4-Br-C6H4
4-OH-C6H4
4-OCH3-C6H4
4-CH3-C6H4
4-NO2C6H4
3-NO2C6H4
2-pyridyl
4-Cl-C6H4
4-Br-C6H4
Isatine
4-Cl-C6H4
4-Cl-C6H4
PhNH2
PhNH2
PhNH2
PhNH2
PhNH2
4-MePhNH2
4-MePhNH2
4-MePhNH2
PhCH2NH2
PrNH2
271–273
122–124
173–174
aIsolated yield.
bThe melting points are not corrected.
reaction of 4-chlorobenzaldehyde, isatoic anhydride, and ammonium acetate was
selected as model substrates and the reaction was carried out in various conditions to
optimize the reaction (Scheme 3). The different solvents as well as solvent-free
medium, temperatures and catalyst amounts were examined on the model reaction
and the results are shown in Table 1. The refluxing aqueous condition, and use of
20 mg of CoFe2O4@SiO2@BIMA@Cu as a catalyst, serves as the best condition with
respect to green nature and clean workup procedure for this synthesis (Table 1, entry
11). To define the role of CoFe2O4@SiO2@BIMA@Cu as the catalyst, the model reaction
was performed under the same conditions with CoFe2O4, CoFe2O4@SiO2,
CoFe2O4@SiO2@BIMA, and without any catalyst. With respect to reaction time and
yield of product, the best result is achieved using CoFe2O4@SiO2@BIMA@Cu as the
catalyst (Table 1, entries 11–15).
After optimization of reaction conditions, in order to determine the generality and
efficacy of the hybrid nanocatalyst, various aldehydes carrying either electron-donating
or electron-withdrawing groups were reacted under the optimized reaction conditions
(Scheme 3). Reactions for all of the various substrates proceed efficiently to obtain the
corresponding 2,3-dihydroquinazolin-4(1H)-ones in good to excellent yields without
formation of side products (Table 2). Arylaldehydes with electron-withdrawing sub-
stituents produced higher yields of desired products compared to arylaldehydes bear-
ing electron-donating substituents (Table 2).

12
M. A. BODAGHIFARD AND S. SAFARI
Figure 7. (a) The recyclability of hybrid nanocatalyst (CoFe2O4@SiO2@BIMA@Cu) in the model reac-
tion during six runs, (b) FT-IR spectrum, and (c) XRD patterns for fresh and reused catalyst.
The recovery and reusability of the catalyst are very important for commercial and
industrial applications as well as green aspects. Recovery and reusability of
CoFe2O4@SiO2@BIMA@Cu was investigated in the model reaction (benzaldehyde,
ammonium acetate and isatoic anhydride, Figure 7). After completion of the reaction,
the resulting solid mixture was diluted with hot EtOH (15 mL). Then, the catalyst was
easily separated, washed with hot EtOH, dried under vacuum and reused in a subse-
quent reaction. Nearly, quantitative recovery of catalyst (up to 95%) could be obtained
from each run. As seen in Figure 7a, the recycled catalyst could be reused six times
without additional treatment or appreciable reduction in catalytic activity. In Figures
7b and c, the FT-IR spectra and XRD patterns of the fresh (a) and reused (b) catalyst
are compared. Potential Cu leaching into the reaction mixture was also analyzed with
ICP/OES analysis after six runs. The amount of copper in the catalyst is found to be
1.81 ꢃ 10ꢀ3 molgꢀ1 after six cycles based on ICP/OES measurement. The copper con-
tent in CoFe2O4@SiO2@BIMA@Cu after six runs is comparable to that of fresh catalyst,
confirming that the leaching of copper in the reaction mixture is negligible. The con-
sistent structure and activity of recovered and reused CoFe2O4@SiO2@BIMA@Cu cata-
lyst confirms its stability, recyclability and performance for the synthesis of
desired products.
Based on a literature survey, a tentative mechanism for the synthesis of 2,3-dihydro-
quinazolin-4(1H)-ones in the presence of CoFe2O4@SiO2@BIMA@Cu is depicted in
Scheme 4. The reaction may proceed via carbonyl group activation (1) by hybrid cata-
lyst. The subsequent condensation with amine (2) leads to the ring opened intermedi-
ate (IN 1). The intermediate IN
1 undergoes decarboxylation to form the
antranilamide (IN 2). The condensation of amine group with aldehyde (3) produces

JOURNAL OF COORDINATION CHEMISTRY
13
Scheme 4. The proposed path for synthesis of 2,3-dihydroquinazolin-4(1H)-ones using
CoFe2O4@SiO2@BIMA-Cu as a hybrid catalyst.
Table 3. The comparison of CoFe2O4@SiO2@BIMA@Cu as a catalyst in the synthesis of 2,3-dihy-
droquinazolin-4(1H)-ones with some other reported catalysts.
Entry
Catalyst
Condition
Time (min)
Yield (%)
80[36]
1
2
3
4
5
6
7
8
Nano Fe3O4
H2O, Reflux
120
130
180
30
180
60
120
25
15
[51]
SBSSA
Nano ZnO
TBAB
Nano-CuO
EtOH, 80 ꢁC
90
92
90
85
90
82
94
[52]
Solvent-free, 70 ꢁC
H2O, 70 ꢁC
[31]
[53]
H2O:EtOH, Reflux
[54]
b-Cyclodextrin-SO3H
Fe3O4@SiO2-imid-PMAn
Co-Am-benzamid@Al-SBA-15
[PyPS]3PW12O40
CoFe2O4@SiO2@BIMA@Cu
H2O, 80 ꢁC
[55]
H2O:EtOH, Reflux
EtOH, Reflux
[56]
[57]
9
10
Solvent-free, MW, 80 ꢁC
H2O, Reflux
90
[This work]
30
93
the imine intermediate IN 3. The nucleophilic attack of second amino group on acti-
vated imine double bond affords the corresponding 2,3-dihydroquinazolin-4(1H)-ones
[36]. So, it is proposed that the Cu(II) ions act as Lewis acids and activate the carbonyl
functional groups and facilitate the condensation reactions [48–50]. The porosity and
high surface area of nanostructure (CoFe2O4@SiO2@BIMA@Cu) provide suitable sup-
port for the chemical reactions and increase the catalytic performance of the prepared
hybrid nanomaterial.
Comparison of the CoFe2O4@SiO2@BIMA@Cu nanostructure as catalyst with some
previously reported catalysts for synthesis of 2,3-dihydroquinazolin-4(1H)-one

14
M. A. BODAGHIFARD AND S. SAFARI
derivatives is shown in Table 3. The data confirm that the CoFe2O4@SiO2@BIMA@Cu is
a comparable, suitable and efficient catalyst for the synthesis of desired 2,3-dihydro-
quinazolin-4(1H)-ones.
4. Conclusion
Surface-modified magnetic nanoparticles were functionalized with Cu(II) complex tags.
The Cu-complex decorated hybrid nanostructure (CoFe2O4@SiO2@BIMA@Cu) was char-
acterized using various techniques and its catalytic activity was considered in the syn-
thesis of 2,3-dihydroquinazolin-4(1H)-one derivatives. The desired products were
synthesized by three component reaction of isatoiac anhydride, amine, and aldehyde
in high yields within short reaction times. This strategy offers several key characteris-
tics such as using a green solvent, high yield and purity, easy work-up and eco-
friendly process, simple separation of catalyst by an external magnetic field. Cu graft-
ing with organic functional groups on the inorganic support limit Cu leaching and par-
ticle growth, which permitted this hybrid nanocatalyst to be reused several times with
only a slight diminish in its activity.
Funding
The authors acknowledge the financial support of the Research Council of Arak University.
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