Synthesis of a new Pd(0)-complex supported on magnetic nanoparticles and study of its catalytic activity for Suzuki and Stille reactions and synthesis of 2,3-dihydroquinazolin-4(1H)-one derivatives

Article abstract of DOI:10.1016/j.poly.2018.01.016

In the present work, we report synthesis of anchored palladium complex on functionalized Fe₃O₄ nanoparticles via simple and inexpensive procedure. The final nanohybrid compound was characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), inductively coupled plasma optical emission spectroscopy (ICP-OES), X-ray Diffraction (XRD), thermal gravimetric analysis (TGA) and vibrating sample magnetometer (VSM) measurements. The catalytic activity of Fe₃O₄-Serine-Pd as an efficient and reusable catalyst was investigated for Suzuki and Stille reactions and synthesis of 2,3-dihydroquinazolin-4(1H)-one derivatives. The heterogeneous catalyst could be easily separated by applying a simple magnet and reused several consecutive runs without appreciable change in its catalytic activity.

Full text of DOI:10.1016/j.poly.2018.01.016

Accepted Manuscript
Synthesis of a new Pd(0)-complex supported on magnetic nanoparticles and
study of its catalytic activity for Suzuki and Stille reactions and synthesis of 2,3-
dihydroquinazolin-4(1H)-one derivatives
Taiebeh Tamoradi, Arash Ghorbani-Choghamarani, Mohammad Ghadermazi
PII:
S0277-5387(18)30045-7
https://doi.org/10.1016/j.poly.2018.01.016
POLY 13013
DOI:
Reference:
Polyhedron
To appear in:
Received Date:
Revised Date:
Accepted Date:
5 December 2017
12 January 2018
17 January 2018
Please cite this article as: T. Tamoradi, A. Ghorbani-Choghamarani, M. Ghadermazi, Synthesis of a new Pd(0)-
complex supported on magnetic nanoparticles and study of its catalytic activity for Suzuki and Stille reactions and
synthesis of 2,3-dihydroquinazolin-4(1H)-one derivatives, Polyhedron (2018), doi: https://doi.org/10.1016/j.poly.
2018.01.016
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Synthesis of a new Pd(0)-complex supported on magnetic nanoparticles and
study of its catalytic activity for Suzuki and Stille reactions and synthesis of
2,3-dihydroquinazolin-4(1H)-one derivatives
Taiebeh Tamoradi,a Arash Ghorbani-Choghamarani,b,∗ Mohammad Ghadermazia,∗
a University of Kurdistan, Department of Chemistry, Faculty of Science, Sanandaj, Iran
e-mail: mghadermazi@yahoo.com
b Department of Chemistry, Faculty of Science, Ilam University, P.O. Box, 69315516, Ilam, Iran
e-mail: arashghch58@yahoo.com or a.ghorbani@ilam.ac.ir
Abstract
In the present work, we report synthesis of anchored palladium complex on functionalized
Fe3O4 nanoparticles via simple and inexpensive procedure. The final nanohybrid compound
was characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron
microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), inductively coupled plasma
optical emission spectroscopy (ICP-OES), X-ray Diffraction(XRD), thermal gravimetric
analysis (TGA) and vibrating sample magnetometer (VSM) measurements. The catalytic
activity of Fe3O4-Serine-Pd as an efficient and reusable catalyst was investigated for Suzuki
and Stille reactions and synthesis of 2,3-dihydroquinazolin-4(1H)-one derivatives. The
heterogeneous catalyst could be easily separated by applying a simple magnet and reused
several consecutive runs without appreciable change in its catalytic activity.
Keywords Magnetic nanoparticle, Palladium, 2,3-dihydroquinazolin-4(1H)-one, Suzuki,
Stille.
∗
Address correspondence to University of Kurdistan, Department of Chemistry, Faculty of Science,
Sanandaj, Iran.; e-mail: mghadermazi@yahoo.com (M. Ghadermazi) or Department of Chemistry,
Faculty of Science , Ilam University, P.O. Box 69315516, Ilam, Iran; Tel/Fax: +98 841 2227022; E-
mail address: arashghch58@yahoo.com or a.ghorbani@ilam.ac.ir (A. Ghorbani-Choghamarani).

1. Introduction
The simplified recovery, reusability and the potential for incorporation in continuous reactors
and microreactors are unique properties in organic synthesis, thus the major area of research
is recently shifted toward more environment friendly catalysts [1-3]. In homogeneous
systems it is complicated to recover the catalyst from the final reaction mixture; thus
heterogeneous catalysts are used as supports. Heterogeneous catalysts have attracted a
considerable attention in synthesis of organic compounds, because of their recovery by
conventional filtration or centrifugation techniques. However, recovery and recycling of the
heterogeneous catalysts are difficult because they require a tedious workup via filtration and
the inevitable loss of solid in the recovery process [4-10]. Magnetic nanoparticles have
recently proposed as ideal supports because of their multifunctional physical and chemical
properties such as easy preparation and functionalization, high chemical activity, long
catalytic life, large surface area ratio, excellent thermal and chemical stability, low price, less
toxicity, high dispersion and easy separation via external magnet [11-22]. Furthermore,
magnetic nanoparticles can be used as recoverable and reusable heterogeneous catalysts in
Suzuki and Stille reactions and synthesis of 2,3-dihydroquinazolin-4(1H)-one derivatives [23-
28]. 2,3-dihydroquinazolin-4(1H)-one derivatives are an important class of heterocyclic
compounds in the production of industrially important chemicals and biological activities
such as antitumor, antibiotic, antidefibrillatory, antipyretic, antihistamine, vasodilating
behavior, analgesic, antihypertonic, diuretic and antidepressant [29,30]. Furthermore, the C-C
coupling reactions are widely applied for the synthesis of the sartan family of hypertensive
drugs, antimicrobial, fungicide boscalid, anti-proliferative, anti-inflammatory, anti-diabetic
and analgesic applications [31-34]. In the present study, we prepared and characterized
efficient and novel Fe3O4-Serine-Pd nanoparticles via simple work-up procedure and
commercially available materials. Also, we will focus on the investigation of the catalytic

activity of this heterogeneous nanocatalyst in Suzuki and Stille reactions and synthesis of 2,3-
dihydroquinazolin-4(1H)-one derivatives.
2. Experimental
2.1. General remarks
All reactants used in this work are commercially available from Sigma-Aldrich and Merck
chemical companies and used without further purification. The particle size and morphology
of the samples were taken using SEM with a FESEM-TESCAN MIRA3, and also using TEM
with a Zeiss-EM10C transmission electron microscope. VSM measurements were carried out
in an external field up to 15kOe at several temperatures by a Vibrating Sample Magnetometer
(VSM) MDKFD. The thermogravimetric analysis (TGA) curves were obtained on Shimadzu
DTG-60 instrument. Powder X-ray diffraction (XRD) of Fe3O4-Serin-Pd(0) catalyst was
collected using Co Kα radiation (λ= 1.78897 Å nm) with operating at 40 keV, and a cathode
current of 40 Ma. IR spectra were recorded by KBr disc using a VRTEX 70 model BRUKER
FT-IR spectrophotometer. The content of metal in the catalyst was measured by inductively
coupled plasma-optical emission spectrometry (ICP-OES). Melting points were recorded by
an Electrothermal 9100 apparatus.
2.2. Preparation of Fe3O4-Serine-Pd(0) nanocatalyst
Superparamagnetic nanoparticles were prepared by stirring 2.35 g of FeCl3.6H2O and 0.86 g
of FeCl2.4H2O in 40 ml deionized distilled water under nitrogen gas at 80 ̊C and then adding
5 mL of NH4OH solution into the reaction mixture. After stirring the mixture for 30 min,
black precipitate was immediately formed. The black magnetite nanoparticles were separated
by magnetic decantation, washed several times with deionized hot water and ethanol and
dried in vacuum at 60 C̊ . To prepare Fe3O4-Serine, 1 g of MNPs powder and 1.5 g of serine

ligand were suspended in distilled water (30 mL) and refluxed for 20 h. Finally, Fe3O4-Serine
was separated by an external magnet and washed with ethanol/water and dried in vacuum at
80 C̊ . In the last step, Fe3O4-Serine-Pd(0) nanoparticles were afforded by mixing the Fe3O4-
Serine (1 g) and Pd(OAc)2 (0.5 g) in absolute ethanol (30 mL) and stirring under reflux for 16
h. Then Pd(II) ions reduced with NaBH4 to give the Fe3O4-Serine-Pd(0).
2.3. General procedure for the synthesis of 2,3-dihydroquinazolin-4(1H)-ones
In a typical procedure, a mixture of aldehyde (1 mmol), 2-aminobenzamide (1 mmol) and
Fe3O4-Serine-Pd(0) catalyst (0.007 g) in water (2 mL) was magnetically stirred in the reaction
flask at room temperature. After the completion of the reaction indicated by TLC, the catalyst
was separated by an external magnet and solvent was evaporated at 70 °C for reuse. Finally, a
crude solid was obtained followed by crystallization from hot ethanol which prepared the
pure product with excellent yield.
2.4. General procedure for synthesis of biphenyl derivatives
In a 5 ml round-bottom flask, to a mixture of arylhalide (1 mmol), phenylboronic acid (1
mmol)or triphenyltin chloride (0.5 mmol), Na2CO3 (3 mmol) and 2 ml of PEG, Fe3O4-Serine-
Pd(0) (0.007 g) as catalyst was added; and the obtained mixture was heated at 100 °C for an
appropriate time under stirring conditions. After the reaction was completed (monitored by
TLC), the catalyst separated by an external magnet. Finally, the obtained organic layer was
extracted with ethyl acetate to afford the pure biphenyl derivatives by removing solvent in
good to high yield.

3. Results and discussion
In order to design and synthesize of a new and highly efficient catalyst system, the
superparamagnetic nanoparticles (MNPs) were synthesized with chemical coprecipitation
method [35-37]. Then, Fe3O4-Serine nanoparticles were obtained by the immobilization of
serine on the surface of the synthesized magnetite nanoparticles via coordination bonding
through hydroxyl group interaction. Afterward, Fe3O4-Serine-Pd(0) nanocatalyst was
successfully achievedby reaction of Pd(OAc)2 with the obtained Fe3O4-Serine ligand in
ethanol under reflux condition (Scheme 1).
Scheme 1 General route for the fabrication of Fe3O4-Serine-Pd(0).
3.1. Catalyst characterization
The obtained Fe3O4-Serine-Pd(0) catalyst has been characterized by XRD, FT-IR, TEM,
SEM, TGA, EDS, ICP and VSM techniques.
As shown in Fig. 1, the particle shape, the size distribution, surface morphology and
fundamental physical properties of the Fe3O4 and Fe3O4-Serine-Pd(0) were investigated by
Scanning Electron Microscopy (SEM). Therefore, it can be concluded that the synthesized

materials are with uniform nanometer-sized particles. More importantly, no noticeable
change in the surface morphology occurs upon the formation of Fe3O4-Serine-Pd(0)
nanocatalyst.
Fig. 1 SEM images of Fe3O4 (a) and Fe3O4-Serine-Pd(0) catalyst (b).
The presence of the kinds of elements in the synthesized Fe3O4-Serine-Pd(0) was investigated
by the energy-dispersive X-ray spectroscopy (EDX) analysis. According to the database of
the EDX pattern in Fig. 2, the presence of Fe, O, N, C and Pd specie in the obtained catalyst
were verified. Also, the loading of Pd on the surface of the synthesized nanocatalyst was
calculated by the ICP atomic emission spectroscopy technique. The exact amount of Pd
loaded on modified magnetic nanoparticles is found to be 1.55mmol g−1.

1500
1000
500
0
FeKα
O Kα
N Kα
PdLβ
PdLα
FeLα
FeKβ
C Kα
keV
10.00
0
Fig.2 EDX pattern of Fe3O4-Serine-Pd(0).
TEM micrograph has been a suitable tool for determining the particle shape and size
distribution. As it can be seen in Fig. 3, the magnetic cores of the nanoparticles were uniform
in both shape and in size. It should be mentioned that the size of the Fe3O4-Serine-Pd(0)
catalyst is around 15–25 nm.
Fig. 3 TEM images of Fe3O4-Serine-Pd(0).

Also, to extend the scope of catalyst characterization, the X-ray diffraction analysis (XRD)
pattern of Fe3O4-Serine-Pd(0) was investigated (Fig. 4). The XRD pattern of a standard Fe3O4
crystal indicated six characteristic peaks at (2 2 0), (3 1 1), (4 0 0), (4 2 2), (5 1 1), and (4 4 0)
[38]. According to the Fig. 4, these peaks (2θ=30.17°, 35.5, 43.2°, 53.7°, 57.1° and 62.9°) can
be assigned to the pure Fe3O4 nanoparticles. Also, a sequence of particular diffraction peaks
(39.3°, 45.1° and 66.1°) confirmed the presence of Pd(0) in the prepared nanostructure.
Fig. 4 XRD pattern of Fe3O4-Serine-Pd(0).
The existence of palladium complex on the surface of Fe3O4 nanoparticles was verified by
FTIR studies. FTIR spectra for the pure Fe3O4 nanoparticles, Fe3O4-Serine and Fe3O4-Serine-
Pd(0) are shown in Fig.5 in the 400–4000 cm−1.The strong absorption at approximately 580
cm−1 in the Fe3O4, Fe3O4-Serine and Fe3O4-Serine-Pd(0) was exhibited which was attributed
to the presence of Fe–O stretching vibration [39]. Absorption peaks at approximately 2840–
2970cm−1 (C–H stretching vibration), absorption band at nearly 1390 cm-1 (C–N stretching
vibration) and absorption peak at approximately 1690cm−1 (C=O stretching vibration) in the
Fe3O4-Serine spectra is due to the coating of serine ligand on the surface of the synthesized
magnetite nanoparticle. More importantly, the band near 1425 cm-1 of the Fe3O4-Serine is
attributed to ν(NH2) bending; this band is shifted to lower wavenumber in the spectrum of the

Fe3O4-Serine-Pd(0) due to the coordination of the amino group nitrogen atom to the metal ion
[38]. Alo, FT-IR spectrum of Fe3O4-Serine exhibits a stretching band at 3489 cm-1 while in
the Fe3O4-Serine-Pd(0) spectrum this band is shifted to lower frequency and appears at 3475
cm-1 indicating the formation of Pd–ligand bond [40].
Fig. 5 FTIR spectrum for bare Fe3O4 nanoparticles (a), Fe3O4-Serine (b) and Fe3O4-Serine-Pd(0) (c).
The thermal stability of Fe3O4 and Fe3O4-Serine-Pd was studied by thermo-gravimetric
analysis (TGA) (Fig. 6). In all samples the TGA curve shows the small amount of weight loss
below 200 °C that is due to removal of the adsorbed water as well as dehydration of the
surface OH groups [41]. The 28% weight loss in the range of 200-550 °C can be due to the
decomposition of the organic layers on the surface of the synthesized magnetite
nanoparticles. On the basis of this result, the well grafting of organic groups including Pd
complex on the Fe3O4 is verified.

Fig. 6 The TGA diagrams of Fe3O4 (a) and Fe3O4-Serine-Pd(0) (b).
Vibrating sample magnetometer curves of the uncoated magnetic iron oxide (Fe3O4) and
palladium complex coated Fe3O4 nanoparticles at room temperature were shown in Fig. 7.
The saturation magnetization value (Ms) of the Fe3O4 and Fe3O4-Serine-Pd(0) nanoparticles
were 73 and 45.6 emu g−1, respectively. The magnetic saturation for Fe3O4 nanoparticles is
higher than Fe3O4-Serine-Pd(0) that is due to the existence of nonmagnetic materials
(palladium complex) on the surface of nanoparticles [36].
Fig. 7. Magnetization curves of Fe3O4 (a) and Fe3O4-Serine-Pd(0) (b) at room temperature.
3.2. Catalytic studies
After characterizing the Fe3O4-Serine-Pd(0), the catalytic activity of this nanocatalyst in
organic reactions such as the preparation of 2,3-dihydroquinazolin-4(1H)-ones derivatives

(Scheme 2) and carbon–carbon bond formation using triphenyltin chloride or phenylboronic
acid to obtain biphenyl derivatives (Scheme 4) was investigated. In search of the optimized
reaction conditions for the synthesis of 2,3-dihydroquinazolin-4(1H)-ones, the condensation
of 4-chlorobenzaldehyde (1 mmol) with 2-aminobenzamide in in presence of Fe3O4-Serine-
Pd(0) as catalyst was used as a model reaction. For assessing the generality of optimized
reaction condition, the effect of various parameters such as solvent and catalyst concentration
was investigated for the model reaction. During optimization of solvent, among solvents
tested, the best results are obtained with water based on product yield (Table 1, entries 2–4).
To investigate the effect of the catalyst concentration, different amounts of Fe3O4-Serine-
Pd(0) were used (Table 1, entries 1–5). It should be mentioned that the reaction possess no
desirable conversion in the absence of catalyst after 5 h (Table 1, entry 1). According to these
results, 7 mg of Fe3O4-Serine-Pd(0) seems appropriate as the optimum amount of catalyst
(Table 1, entry 3). The results of optimization were summarized using designed experiments
in Table 1.
Scheme 2. Synthesis of 2,3-dihydroquinazolin-4(1H)-ones.
Table 1
Optimization of various parameters for the synthesis of 2,3-dihydroquinazolin
-4(1H)-ones by Fe3O4-Serine-Pd(0) a.
Entry
Solvent
Catalyst
Time
(min)
5h
Yieldb
(%)
Treac
97
(mg)
1
2
3
4
5
H2O
H2O
H2O
H2O
H2O
0
8
7
6
5
25
25
96
25
88
25
81

6
7
8
9
EtOH
7
7
7
7
25
25
25
25
70
81
89
61
EtOH/reflux
PEG
DMF
a Reaction conditions: 4-chlorobenzaldehyde (1 mmol) and 2-aminobenzamide
(1 mmol) as a model reaction at room temperature.
b Yields refertoisolatedpureproduct.
As shown in Table 2, under the optimized reaction conditions, different aldehydes were
tested for the synthesis of 2,3-dihydroquinazolin-4(1H)-ones to give the products in good to
excellent yields.
Table 2
Synthesis of 2,3-dihydroquinazolin-4(1H)-ones catalyzed by Fe3O4-Serine-Pd(0)a.
Time Yieldb
(min) (%)
Entry
Aldehyde
Product
Mp (°C) [Ref.]
202-204 [42]
1
25
50
35
55
40
96
98
93
94
96
2
3
4
5
228-232 [25]
197-200 [42]
190-1191 [25]
218-222 [43]

6
7
35
15
92
94
228-230 [44]
193-195 [42]
8
9
30
97
184-187 [16]
35
40
94
96
278-280 [43]
191–194 [43]
O
NH
10
N
H
O2N
aReaction conditions: aldehyde (1 mmol), 2-aminobenzamide (1 mmol), catalyst (0.007 g) in
H2O solvent (2 mL) at room temperature.
b Isolated yield.
A plausible reaction mechanism for the synthesis of 2,3-dihydroquinazolin-4(1H)-ones derivatives in the
presence of Fe3O4-Serine-Pd(0) as catalyst is shown in Scheme 3. As shown in this scheme, anhydride is
activated. Then, an intermediate (I) is formed by the N-nucleophilic attacks of amine on the carbonyl. In
following, the imine intermediate II is obtained. Also, after activation of imine in this intermediate by metal,
intermediate III could be generated by intramolecular nucleophilic attack of the amide nitrogen on activated
imine group. Finally, 1,5-proton transfer occurred to yield the final product [45].

Scheme 3 Proposed mechanism for the synthesis of quinazolinones.
In continuation of this research work, the catalytic activity of Fe3O4-Serine-Pd(0) was
evaluated in the synthesis of biphenyl compounds through the reaction of aryl halides with
phenylboronic acid or triphenyltin chloride. In the preliminary stage of investigation, the
Suzuki cross-coupling reaction was done between iodobenzene (1mmol) and phenylboronic
acid (1mmol) to optimize the reaction conditions, including catalyst amount, solvent, base
and temperature. Initially, our studies focused on the effects of various solvents such as
DMF, PEG, EtOH, DMSO and H2O (Table 3, entries 1–5). Finally, among the tested
solvents, PEG was obtained as the best solvent based on product yield. Subsequently, we
investigated the effect of various bases such as K2CO3, Na2CO3, KOH, NaOH and Et3N in the
model reaction (Table 3, entries 6–10). Among the examined bases, the best result is obtained
for Na2CO3 as an excellent base for this reaction. The reported result in Table 3 showed that
the amount of base was also important in the synthesis of biphenyls. Subsequently, we

explored the effect of the amount of catalyst to obtain the best operative experimental
conditions. It should be mentioned that 0.007 g of Fe3O4-Serine-Pd(0) catalyst and 3 mmol of
Na2CO3 as the base were evaluated in the selection of an optimized conditions for the C-C
coupling reaction (Table 3, entries 6). The results of this investigation are summarized in
Table 3.
Scheme 4 General scheme for the Suzuki and Stille reactions catalysed by Fe3O4-Serine-Pd(0).
Table 3
Optimization of various parameters for synthesis of biphenyl catalysed by Fe3O4-Serine-Pd(0).
Entry
Solvent
Base
Time
(min)
20
Catalyst
(mg)
Base
Temp.
(°C)
Yielda
(%)
(mmol)
1
DMSO
EtOH
H2O
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
K2CO3
KOH
7
3
3
3
3
3
3
3
3
3
3
3
3
3
80
43
2
20
7
7
7
7
7
7
7
7
7
6
5
8
80
34
42
63
84
97
74
61
53
58
85
80
98
3
20
80
4
DMF
PEG
PEG
PEG
PEG
PEG
PEG
PEG
PEG
PEG
20
80
5
20
80
6
20
100
100
100
100
100
100
100
100
7
20
8
20
9
NaOH
20
10
11
12
13
Et3N
20
Na2CO3
Na2CO3
Na2CO3
20
20
20
14
PEG
PEG
PEG
Na2CO3
Na2CO3
Na2CO3
20
20
24 h
7
7
-
2
4
3
100
100
100
86
98
N.R
15
16
aIsolated yield.
In continuation of this work on the applications of Fe3O4-Serine-Pd(0), we also explored the
catalytic activity of Fe3O4-Serine-Pd(0) for the Suzuki cross-coupling reaction of

phenylboronic acid with a wide range of aryl halides under the optimized reaction condition
in high to excellent yields in a short reaction time. The results are summarized in Table 4.
Table 4
C–C coupling of aryl halides with phenylboronic acid in the presence of Pd Fe3O4-Serine-Pd(0) a.
Yieldb
(%)
Entry
1
Aldehyde
Product
Time (min)
20
Mp (°C) [Ref.]
66-69 [18]
98
2
3
95
40
94
96
68-71 [18]
69 [18]
4
5
15
30
93
98
45 [46]
46-48[46]
6
7
60
75
97
96
113-116[46]
115-118 [18]
8
90
93
78-81 [46]

9
70
95
96
92
97
97
78 [46]
10
11
12
13
90
Oil [43]
84–86 [46]
Oil [43]
Oil [43]
100
120
30
a Reaction conditions: iodobenzene (1 mmol), phenylboronic acid (1 mmol), base (3 mmol), Fe3O4-Serine-Pd(0) (0.007
g), solvent (2 mL) at 110 °C.
b Isolated yield.
Catalytic cycle for this C–C bond formation reaction in the presence of Fe3O4-Serine-Pd(0)
was shown in Scheme 5 [47].

Scheme 5 Mechanism of the palladium-catalyzed Suzuki reaction.
Also in order to investigate the behavior of the catalyst in the Stille reaction, under the
optimized reaction condition, the biphenyl compounds were successfully synthesized through
the reaction of the different aryl halides with triphenyltin chloride in high to excellent yields
in a short reaction time. The results are shown in Table 5.
Table 5
C–C coupling of aryl halides with phenylboronic acid in the presence of Pd-Fe3O4-Serine-Pd(0) a.
Time
(min)
Mp (°C)
[Ref.]
Entry
1
Aldehyde
Product
Yieldb (%)
35
95
68 [18]
2
110
93
66-69 [18]

3
4
45
30
94
98
71 [18]
45-48 [46]
5
6
7
8
45
65
80
85
96
96
97
98
47 [46]
110-112 [18]
113-115 [46]
80-83 [46]
9
60
80
93
92
76-79 [46]
10
Oil [43]

11
12
13
90
94
98
93
85–87 [46]
Oil [43]
110
45
Oil [43]
aReaction conditions: iodobenzene (1 mmol), triphenyltin chloride (0.5 mmol), base (3 mmol), Fe3O4-Serine-Pd(0) (0.007
g), solvent (2 mL) at 110 °C.
bIsolated yield.
In order to examine the efficiency of the procedures presented, we compared the results of
synthesis of 2-Phenyl-2,3-dihydroquinazolin-4(1H)-one (entries 1-9) and Suzuki reaction
(entries 10-14) in the presence of new catalyst with previously reported catalysts in the
literature. The results of this comparison indicated shorter reaction time and higher yield of
the Fe3O4-Serine-Pd(0) catalyst than the well-known catalyst from the literature. Noticeably,
the Fe3O4-Serine-Pd(0) catalyst is superior in terms of stability, commercially available
materials, ease of operation and easy separation than the previously reported ones.
Table 6 Comparison of Fe3O4-Serine-Pd(0) catalyst with reported catalysts for Suzuki reaction and
synthesize of 2-Phenyl-2,3-dihydroquinazolin-4(1H)-one.
Entry
Catalyst
Substrate
Time Condition
(min)
Yield (%)a
1
2
GSA@MNPs
2-(N-
4-Chlorobenzaldehyde
4-Chlorobenzaldehyde
50
180
Ethanol, reflux
Ethanol, 60˚C
87 [48]
89 [49]
Morpholino)ethanesulfo

nic acid
3
[Bmim]PF6
4-Chlorobenzaldehyde
4-Chlorobenzaldehyde
4-Chlorobenzaldehyde
4-Chlorobenzaldehyde
4-Chlorobenzaldehyde
4-Chlorobenzaldehyde
4-Chlorobenzaldehyde
Iodobenzene
40
Ionic liquid, 75 ˚C
EtOH, r.t
90 [50]
4
Yb(OTf)3
120
50
94 [51]
5
Boehmite-SSA
PdCl2
EtOH, 80 ˚C
THF, reflux
EtOH, 50 ˚C
EtOH, reflux
H2O, r.t
98 [52]
6
270
110
60
86 [53]
7
Fe3O4-SA-PPCA
CuCl2/Fe3O4-TEDETA
Fe3O4-Serine-Pd(0)
PANI–Pd
91 [25]
8
95 [20]
9
25
96 [this work]
10
240
K2CO3, 1,4-dioxane– 91 [54]
H2O (1:1), 95°C
11
Pd-MPTAT-1
Iodobenzene
480
NaOH,
DMF–H2O 95 [55]
(1:5), 85°C
12
13
14
Pd NPs
Iodobenzene
Iodobenzene
Iodobenzene
720
720
20
H2O, KOH, 100°C
THF, Cs2CO3, 80°C
PEG, Na2CO3, 100,
95 [56]
NHC–Pd(II) complex
Fe3O4-Serine-Pd(0)
88 [57]
98 [this work]
aIsolated yields.
To investigate the activity constancy of the catalyst, catalytic reusability of Fe3O4-Serine-
Pd(0) was investigated for Suzuki reaction and synthesis of 2,3-dihydroquinazolin-4(1H)-one
under the optimized reaction conditions in the model reaction (Fig.8). In this procedure, the
catalyst successfully reused several continuous cycles without noticeable change in its
catalytic activity, which clearly demonstrates the practical recyclability of this catalyst. After
completion of the reaction, the catalyst was magnetically recovered, washed with ethyl
acetate several times and dried at 60 °C and reused for the next run. The weight loss of
catalyst in the operation for recovery and/or deactivation of the catalyst may have led to
decrease in the product yield.

Fig. 8 Reusability of Fe3O4-Serine-Pd(0) in the synthesis of 2-(4-chlorophenyl)-2,3-dihydroquinazolin-4(1H)-
one (blue column) and 4-nitro-1,1-biphenyl (red column).
4. Conclusions
In summary, a magnetically recoverable palladium catalyst was prepared by simple and
versatile procedure as a novel catalyst and characterized using several techniques such as
FTIR, XRD, SEM, EDX, ICP-OES, TEM, VSM and TGA, and then investigated its catalytic
performance in Suzuki and Stille reactions and synthesis of 2,3-dihydroquinazolin-4(1H)-one
derivatives. In these reactions, this nanohybrid compound represents the attractive features
including high yield , operational simplicity, short reaction time, environmental friendliness,
and recyclability of the magnetic catalyst, as well as the ability to tolerate a wide variety of
substitutions in the reagents.
Acknowledgment
We are grateful to the Research Council of Kurdistan and Ilam University for financial
support.
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Graphical Abstract - Synopsis
The present work describes the synthesis of a new palladium complex immobilized on Fe3O4
nanostructure as efficient catalyst for Suzuki and Stille reactions and synthesis of 2,3-
dihydroquinazolin-4(1H)-one derivatives. Characterization of the prepared nanostructure was
performed by FT-IR, SEM, TEM, EDX, ICP-OES, XRD, TGA and VSM. Use of green
medium, easy separation, excellent reusability of the nanocatalyst, and short reaction time are
outstanding advantages of this method.
Graphical abstract
Synthesis of a new Pd(0)-complex supported on magnetic nanoparticles and
study of its catalytic activity for Suzuki and Stille reactions and synthesis of
2,3-dihydroquinazolin-4(1H)-one derivatives
Taiebeh Tamoradi,a Arash Ghorbani-Choghamarani, b,∗ Mohammad Ghadermazia,∗
∗
Address correspondence to University of Kurdistan, Department of Chemistry, Faculty of Science,
Sanandaj, Iran.; e-mail: mghadermazi@yahoo.com (M. Ghadermazi) or Department of Chemistry,
Faculty of Science , Ilam University, P.O. Box 69315516, Ilam, Iran; Tel/Fax: +98 841 2227022; E-
mail address: arashghch58@yahoo.com or a.ghorbani@ilam.ac.ir (A. Ghorbani-Choghamarani).