The novel acid-base magnetic recyclable catalyst prepared through carbon disulfide trapping process: Applied for green, one-pot, and efficient synthesis of 2,3-dihydroquinazolin-4 (1H) -ones and bis(indolyl)methanes in large-scale

Article abstract of DOI:10.1016/j.mcat.2021.111532

Herein, a nano acid-base catalyst using magnetic core and carbamodithioic acid functional group have been synthesized and characterized. Its efficiency in the synthesis of dihydroquinazolinones and bis(indolyl)methanes derivatives was investigated. This novel metal-free catalyst exhibited significant catalytic activity in both reactions under green and mild reaction conditions (the yield obtained for the first reaction products: 82–98 % and for the second one: 61–97 %). The catalyst displayed good recyclability with no significant loss of catalytic activity after eight runs (the conversion of the eighth run was found as 83 %, the fresh catalyst conversion was 95 %). The introduced approach is attractive due to its applicability in the large-scale synthesis of important medicinal compounds.

Full text of DOI:10.1016/j.mcat.2021.111532

Molecular Catalysis 506 (2021) 111532
Contents lists available at ScienceDirect
Molecular Catalysis
journal homepage: www.journals.elsevier.com/molecular-catalysis
The novel acid-base magnetic recyclable catalyst prepared through carbon
disulfide trapping process: Applied for green, one-pot, and efficient
synthesis of 2,3-dihydroquinazolin-4 (1H) -ones and bis(indolyl)methanes
in large-scale
Fatemeh Mohammadi Metkazini, Zahra Khorsandi, Akbar Heydari*
Department of Chemical, Faculty of Sciences, Tarbiat Modares University, PO Box 14155‑4838, 14117‑13116 Tehran, Iran
A R T I C L E I N F O
A B S T R A C T
Keywords:
Herein, a nano acid-base catalyst using magnetic core and carbamodithioic acid functional group have been
synthesized and characterized. Its efficiency in the synthesis of dihydroquinazolinones and bis(indolyl)methanes
derivatives was investigated. This novel metal-free catalyst exhibited significant catalytic activity in both re-
actions under green and mild reaction conditions (the yield obtained for the first reaction products: 82–98 % and
for the second one: 61–97 %). The catalyst displayed good recyclability with no significant loss of catalytic
activity after eight runs (the conversion of the eighth run was found as 83 %, the fresh catalyst conversion was 95
2
,3-Dihydroquinazolin-4 (1H) -ones and bis
(
indolyl)methanes
Magnetic catalyst
Large-scale synthesis
%
). The introduced approach is attractive due to its applicability in the large-scale synthesis of important me-
dicinal compounds.
1
. Introduction
Dihydroquinazolinones derivatives are extensively found in
dihydroquinazolinones. Available catalytic systems have some limita-
tions such as long manufacturing processes, applying expensive mate-
rials, and creating metal contamination. So, designing efficient,
recyclable, and novel metal-free catalysts seems an interesting strategy.
Another important class of heterocyclic compounds is indoles which
their derivatives present in several natural products, pharmaceuticals,
and agrochemicals [18–20]. Among them, bis(indolyl)methanes (BIMs)
and their derivatives exhibit wide usages in medicinal chemistry,
biochemistry, and pharmacology (Fig. 1) [21]. Due to their unique
pharmacological activities, much attention has been paid to develop
effective methods for the synthesis of bis(indolyl)alkanes; so, numerous
synthetic approaches for their production are available [22]. However,
these protocols suffer from some drawbacks such as the use of poisonous
reagents and volatile organic solvents [23]. Hence, achieve the aims of
green chemistry, founding new efficient, low-cost and environmentally
friendly synthetic methods is valuable.
numerous pharmaceuticals and biologically active molecules [1]. Due to
their significant pharmacological properties and medicinal importance,
their synthesis has been considered in medicinal chemistry [2]. Some
molecules included dihydroquinazolinone unit exhibited diverse bio-
logical and therapeutic properties such as antibacterial and anticancer
activity [3].
A variety of synthetic methods have been reported to obtaining
dihydroquinazolinones by using precursors of o-aminobenzonitrile [4],
isatoic anhydride [5], o-nitrobenzamides [6], and o-aminobenzamides
[
7]. Condensation of alkyl, aryl, and heteroaryl ketones or aldehydes
with anthranilamide in the presence of acidic catalysts is one the most
well-known method for the synthesis of dihydroquinazolinones [8,9].
This reaction has been catalyzed by yttrium nitrate [10], thiamine hy-
drochloride [11], imidazolium Brønsted acid ionic liquid [12], organo-
Among heterogeneous catalysts, magnetic nanoparticles (MNPs) are
known as ideal core support due to their properties such as easy func-
tionalization process, none toxicity, high stability, and simply separa-
tion [24–31]. Moreover, the preparation of heterogeneous catalysts by
consumption of low-cost materials and through easy processes adds
environmental and economic benefits to the catalytic system.
catalyst [13] and Cu (II) supported on Fe
3
O
4
–DETA [14]. Moreover,
application of some efficient, recoverable, and thermally stable nano-
catalysts such as nickel complex immobilized on functionalized nano-
composite [15], platinum nanoparticles tagged on carbon nanotube [16]
and graphene oxide [17] were also reported for the synthesis of
*
Corresponding author.
E-mail address: heydar_a@modares.ac.ir (A. Heydari).
https://doi.org/10.1016/j.mcat.2021.111532
Received 6 November 2020; Received in revised form 12 March 2021; Accepted 16 March 2021
Available online 5 April 2021
2
468-8231/© 2021 Elsevier B.V. All rights reserved.

F. Mohammadi Metkazini et al.
Molecular Catalysis 506 (2021) 111532
◦
3
0–800 C as a function of temperature. The first step of weight loss in
the cases is related to the removal of adsorbed water and the main
weight loss is related to the removal of organic pieces. These observa-
tions confirmed the stability of the catalyst at high temperatures.
The phase of the catalyst was determined by the XRD spectrum. The
◦
◦
characteristic diffraction peaks attributed to Fe
3
O
4
at 21.1 , 35.1 ,
◦
◦
◦
◦
◦
4
1.4 , 50.6 , 63.0 , 67.4 , and 74.1 which can be assigned to diffraction
of the (220), (311), (400), (422), (511), and (440) planes, respectively of
spinal structured magnetite nanoparticles (JCPDS card no. 82e1533).
The XRD pattern of the Fe3O4@SiO2 displays the same set of peaks in
the iron oxide particle but significate reducing in the intensity of the
peak were observed in comparison with iron oxide material. Some of the
new peaks are attributed to silica surfaces on the magnetic material.
Fig. 1. Biologically active bis(indolyl)alkanes.
According to our research group interest in the preparation of nano
heterogeneous catalysts and investigative their catalytic activities in
organic reactions [32,33]; herein, a one-step process for the preparation
of magnetic-based dithionate catalyst have been developed by collecting
carbon disulfide. To the best of our knowledge, this innovative way to
prepare an acid/base catalyst did not report previously. Introduced
catalyst display high activity in the synthesis of dihydroquinazolinones
and bis(indolyl)methane derivatives. Compared to other existing
methods, our presented procedure has some advantages such as
low-cost, good yields, quick reaction, and easy workup. However, the
most important feature of our method was its good efficiency in the
large-scale synthesis of important pharmaceutical compounds.
(
Fig. 2(3)) [34].
The magnetization curve of the catalyst was given in Fig. 2(4). The
reduction of the magnetic behavior of the final catalyst (22.1 emu/g) in
comparison with the magneticity of pure magnetic nanoparticles
(
69.4 emu/g), confirmed its properties and organic coating. To identi-
fied the pore structure and porous materials, the nitrogen adsorption
method (BET analysis) was applied (Fig. 2(5)). A big jump in high
pressure in the graph displays the microporous properties of the mate-
3
rial. The average total pore volume is 0.4 cm /g, and the average surface
2
area is calculated as 34.2 m /g.
The elemental analysis mapping was also used to investigate the
existing elements in the catalytic hybrid (Fig. 3(1)). The images of field
emission scanning electron microscopy (FE-SEM) and EDAX spectra
exhibited surface morphologies and the existing metals of the catalyst
2
. Results and discussion
The synthesis procedure of the catalyst was given in Scheme 1. The
2
silica NH functional group was reacted with carbon disulfide, through a
(
Fig. 3(2)).
Transmission electron microscopy (TEM) was also applied to more
simple and mild strategy. Then, the acid-base bi-functionalized silica
ligand was treated with magnetic nanoparticles to form the final solid
characterization of surface morphology, these images clearly exhibit
spherical nano iron core and surrounded organic species in comparison
with TEM of pure MNPs (Fig. 3(3)). The particle size distribution was
also given in Fig. 3(3), the average size of nanoparticles was found
around 13 nm.
+ ꢀ
catalyst which is named MNPs@Si-NH
given in supporting information.
2
/S . Detailed procedures were
The synthesis steps were checked with the relevant analysis such as
Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric
analysis (TGA), and elemental analysis. The FT-IR spectrum of catalyst
preparation steps was given in Fig. 2(1). In the spectra of pure magnetite
For catalyst studies, the catalyst efficiency was investigated in 2,3-
dihydroquinazolin-4 (1 H) -ones synthesis reaction. Initially, the reac-
tion of 4-nitrobenzaldehyde (1 mmol) and 2-aminobenzamide (2)
ꢀ 1
nanoparticles (Fig. 2(1a)), the broad bands at 3400 cm are related to
ꢀ 1
O-H and the vibration mode of Fe-O appeared as a band at 560 cm . In
(
1.2 mmol) was selected as a model reaction. The results for optimized
ꢀ 1
spectra of b, the 1090 cm band is related to the Si-O group vibrations,
these observations confirm the expected structure (Fig. 2(1b)). The ab-
sorption bands in the spectrum of the final catalyst, vibration mode of
reaction conditions were given in Table 1.
At first, the effect of different amounts of the catalyst was investi-
gated in the model reaction, and 20 mg of catalyst was selected as the
best amounts. The same condensation was then conducted at different
–
ꢀ 1
C S appeared at 1200 cm , these established the structure of the final
–
catalyst (Fig. 2(1c)).
◦
temperatures. Compared with the reaction at 50 C, no considerable
The TGA and elemental analysis were applied to investigate the
number of organic functions in the catalyst. The TGA diagram was
illustrated in Fig. 2(2), the catalyst was lost its weight between
◦
improvement was achieved at 80 C; room temperature was found to be
less effective. Then, different solvents influenced was studied, from the
Scheme 1. Synthesis of catalyst.
2

F. Mohammadi Metkazini et al.
Molecular Catalysis 506 (2021) 111532
Fig. 2. 1) FT-IR spectra: (a) magnetite nanoparticles (MNPs); (b) silica-coated magnetite nanoparticles (MNPs@Si); (c) the catalyst. 2) TGA thermogram of the MNPs
a) and the final catalyst (b). 3) XRD pattern of MNPs (left) final catalyst (right). 4) Room temperature magnetization curve of MNPs (left) and final catalyst (right). 5)
(
Nitrogen adsorption and desorption isotherms (at 77 K) for catalyst.
perspective of green chemistry, solvent-free was chosen as ideal reaction
medium conditions.
also no significant effect in this process (Table 2, entry 2). The catalyst
with oxy-onion instead of thio-anion was synthesis to comparison, the
results indicated the more efficiency of our catalyst (Table 2, entry 3).
The magnetic-free catalyst was also prepared and its efficiency was
examined, no significant difference between the operation of this cata-
lyst, and our main catalyst exhibited an inert effect of the iron element
on improvement of the reaction (Table 3).
After optimization of the reaction conditions, the scope of the cata-
lyst was examined, the results were given in Table 2. The reaction of 4-
nitrobenzaldehyde (1.0 mmol) with 2-aminobenzamide (1.2 mmol) was
performed as a model reaction in presented magnetic nanoparticles
without any ligands and no products were achieved (Table 2, entry 1).
The functionalized magnetic nanoparticle with just an amino group has
After founding the best catalyst, its generality and versatility in the
3

F. Mohammadi Metkazini et al.
Molecular Catalysis 506 (2021) 111532
Fig. 3. 1) Analysis mapping of catalyst. 2) The FE-SEM images and (b) SEM–EDX spectrum of the catalyst. 3) TEM images of MNPs (A) and final catalyst (B) and sized
distribution.
Table 3
Table 1
a
Scope of dihydroquinazolinones derivatives synthesis reaction. .
Optimization of reaction conditions for 2,3-dihydroquinazolin-4 (1 H) -ones
synthesis of 4-nitrobenzaldehyde with 2-aminobenzamide in the presence of the
a
catalyst. .
o
b
Entry
Solvent
Temp ( C)
Time(min`)
cat. (mg)
Yield (%)
1
2
3
4
5
6
7
8
9
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
80
r.t
45
45
45
45
45
45
45
45
45
45
40
30
15
40
40
40
40
40
40
40
40
20
50
20
20
20
80
70
88
80
86
73
76
95
93
97
96
95
95
50
50
50
50
50
50
50
50
50
50
50
b
Entry
Benzaldehydes
Yield (%)
1
2
3
4
5
6
7
8
9
4-Bromobenzaldehyde
4-Chlorobenzaldehyde
4-Hydroxybenzaldehyde
4-Methylbenzaldehyde
4-Methoxybenzaldehyde
Benzaldehyde
90
98
87
82
90
95
96
84
93
94
91
88
82
86
2
H O
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
1
1
1
1
0
1
2
3
4-Nitrobenzaldehyde
Furan-2-carbaldehyde
Thiophene-2-carbaldehyde
Cyclohexanecarbaldehyde
Butyraldehyde
1
0
a
Reaction carried out with 4-nitrobenzaldehyde (1.0 mmol), 2-aminobenza-
11
12
13
mide (1.2 mmol).
b
Acetaldehyde
Isolated.
Formaldehyde
1
4
Cinnamaldehyde
a
Reaction carried out with benzaldehyde (1.0 mmol), 2-aminobenzamide
◦
Table 2
(1.2 mmol), in solvent-free conditions, 20 mg of catalyst at 50 C for 15 min.
b
a
Screening of the catalysts. .
Isolated yield.
b
Entry
1
Catalyst
Time (h)
5
Yield (%)
synthesis of 2,3-dihydroquinazolin-4 (1 H) -ones derivatives was
examined. Using optimized reaction conditions, benzaldehydes contain
substituents with different electronic properties reacted efficiently with
2-aminobenzamide. High yields of products were reached at a short
reaction time besides safe and green reaction conditions. According to
the results, it seems that the electronic properties of the precursors had
no significant influence on the reaction outcomes.
–
2
3
5
1
32
67
95
To confirm the application of our method to prepare important
compounds, the known antitumor agents of Mackinazolinone and
Erlotinib (truncated) were synthesized on a large-scale, their structure
and synthesis steps were given in Scheme 2. To achieve intermediate, an
oxidizer was needed; so, considering one-pot reaction conditions, it was
preferable to use a magnetic heterogeneous oxidizer. Traditionally, ox-
ides of noble metals have been active catalysts, but their scarceness and
cost promoted us to use abundant metal oxidizer. Herein, the green, low-
cost and efficient nanoparticles of cobalt ferrite catalyst without any
additives were applied as oxidizers. The success of this catalyst as a
green oxidizer and efficient catalyst has already been confirmed [35,
36]. In addition to the mentioned benefits, it separated easily alongside
4
0.25
0.25
5
a
94
Reaction carried out with 4-nitrobenzaldehyde (1.0 mmol), 2-aminobenza-
mide (1.2 mmol), 20 mg catalyst, at 50 ℃, in solvent-free conditions.
b
GC yield.
4

F. Mohammadi Metkazini et al.
Molecular Catalysis 506 (2021) 111532
Scheme 2. Synthetic applications of catalyst for the production of important derivatives of dihydroquinazolinones.
Table 4
′
Optimization of 3,3 -(phenylmethylene)bis(1H-indole) synthesis reaction using
a
benzaldehyde and 1H-indole. .
b
Entry
Solvent
T (℃)
Time (h)
Cat. (mg)
Yield (%)
1
2
3
4
5
6
7
8
9
H
H
H
H
H
2
2
2
2
2
O
O
O
O
O
100
80
60
50
r.t.
50
50
50
50
50
50
50
50
r.t.
10
10
10
10
10
10
10
10
10
10
8
40
40
40
40
40
40
40
40
40
20
20
20
20
20
83
72
69
62
60
49
79
96
63
96
67
95
95
94
3
CH CN
MeOH
EtOH
Solvent-free
EtOH
1
1
1
1
1
0
1
2
3
4
EtOH
EtOH
5
EtOH
3
Scheme 3. Synthetic applications of catalyst for the production of important
′
EtOH
3
derivatives of 3,3 -(phenylmethylene)bis(1H-indole).
a
b
Reaction carried out with benzaldehyde (1.0 mmol), 1H-indole (2.2 mmol).
GC yield.
Furthermore, N-(3-ethynylphenyl) quinazolin-4-amine, which is a
main part of Erlotinib, was obtained in 61 % yield through two steps
(
Scheme 2). The synthesis procedures of catalyst and products along
Table 5
Scope of 3,3 -(phenylmethylene)bis(1H-indole) derivatives synthesis. .
with their characterizations were given in supplementally data file.
The excellent results obtained in the dihydroquinazolinones de-
rivatives synthesis reaction excited us to explore the potential activity of
′
a
′
the catalyst in 3,3 -(phenylmethylene)bis(1H-indole) synthesis reaction.
To reach the optimum reaction conditions, the reaction of benzaldehyde
and 1H-indole was selected as a model reaction. Different reaction
conditions were examined such as type of solvent, catalyst amount, and
different temperatures, results were given in Table 4.
b
Entry
Aldehydes
Yield (%)
1
2
3
4
5
6
7
8
9
4-Bromobenzaldehyde
4-Chlorobenzaldehyde
4-Methoxybenzaldehyde
Benzaldehyde
88
91
87
94
96
97
92
83
95
71
53
61
69
Various aldehydes were reacted with 1H-indole to cover the scope of
catalytic performance in this reaction in founding optimized reaction
conditions (Table 5). The catalyst displayed higher activity for benzal-
dehyde in comparison with alkyl aldehydes; moreover, the electronic
properties of substituted benzaldehyde had no significate effect on the
reaction.
4-Nitrobenzaldehyde
Thiophene-2-carbaldehyde
Furan-2-carbaldehyde
4-(Dimethylamino)benzaldehyde
Picolinaldehyde
The experimental procedures for the above reactions are remarkably
facile without the need to use toxic or expensive metal catalysts or re-
agents along with very good results; these results encouraged us to
1
1
1
1
0
1
2
3
2-Phenylacetaldehyde
Anthracene-9-carbaldehyde
Formaldehyde
′
investigate the scale-up synthesis of functional derivatives of 3,3 -
Acetaldehyde
(
phenylmethylene)bis(1H-indole) which known as anti-HIV (HIV-1
a
integrase) and anticancer (FCW81) (Scheme 3 and Fig. 1). With reaction
stoichiometry intact, the scale of the reaction was increased to
10.0 mmol. The reaction proceeded successfully and products were ob-
tained in 76 % and 84 %, respectively.
Reaction carried out with benzaldehydes (1.0 mmol), 1H-indole (2.2 mmol),
in 2.0 mL of EtOH, 20 mg of catalyst at r.t. for 3 h.
b
Isolated yield.
The efficiency of the prepared catalyst for the synthesis of bis
the first catalyst by an external magnet bar from reaction media.
Accordingly, the introduced method was successfully applied to the
synthesis of Mackinazolinone in 76 % overall yield.
(
indolyl)methanes was compared with other similar catalyst used for
this reaction. These results which are presented in Table 6 indicate good
5

F. Mohammadi Metkazini et al.
Molecular Catalysis 506 (2021) 111532
Table 6
3. Conclusion
′
Comparison of recent literature catalysts and this work for the synthesis of 3,3 -
phenylmethylene)bis(1H-indole).
(
Herein, a green method using a recyclable catalyst has successfully
been advanced for the synthesis of 2,3-dihydroquinazolin-4 (1 H) -ones
and bis(indolyl)methanes in mild reaction conditions. A variety of de-
rivatives of both reactions have been readily synthesized with excellent
product yields at a short reaction time (15 min). More importantly,
large-scale synthesis of four biologically active molecules using our
introduced procedure have been reported with excellent yields. In
general, the applied procedure was facile, mild, and environmentally
friendly without any metal pollution. Finally, the heterogeneous prop-
erty of the catalyst was confirmed.
Entry
Catalyst (mol%)
T (℃)
Time (h)
Yield (%)
Ref.
1
2
3
4
5
6
7
8
[Msim][FeCl
MOF-891 (1) (sonication)
[DABCO-H][HSO ] (10)
Cu/MWCNTs-GAA@Fe2O3
4
] (5)
r.t.
r.t.
90
70
80
40
r.t.
r.t.
1.25
1.5
2
98
92
91
88
81
76
65
94
[39]
[40]
4
[41]
1.3
2
[42]
Cu-base-Fe
GO
2
O
3
(0.5)
[43]
3
[44]
Meglumine
Our catalyst (20)
4
[45]
3
This work
CRediT authorship contribution statement
Table 7
Recyclability of catalyst in the model reaction of dihydroquinazolinones
a
Fatemeh Mohammadi Metkazini: Design and performed the ex-
periments. Zahra Khorsandi: Co-design and performed experiments,
analyzed data, and writing original draft preparation. Akbar Heydari:
Supervised the research.
synthesis. .
a
a
Run
Yield (%)
Run
Yield (%)
1
2
3
4
95
93
92
90
5
6
7
8
90
89
83
–
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgements
a
Isolated yield.
We acknowledge Tarbiat Modares University for partial support of
this work.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.mcat.2021.111532.
References
[
[
1] M. Badolato, F. Aiello, N. Neamati, 2,3-Dihydroquinazolin-4(1H)-one as a
privileged scaffold in drug design, RSC Adv. 8 (2018) 20894–20921.
2] I. Khan, S. Zaib, S. Batool, N. Abbas, Z. Ashra, J. Iqbal, A. Saeed, Quinazolines and
quinazolinones as ubiquitous structural fragments in medicinal chemistry: an
update on the development of synthetic methods and pharmacological
diversification, Bioorg. Med. Chem. Lett. 24 (2016) 2361–2381.
[
[
3] L. Ravithej Singh, A. Kumar, A. Upadhyay, S. Gupta, G. Reddy, P. Kamakshi,
S. Mohammad, I. Siddiqi, P.N. Yadav, K.V. Sashidhar, Discovery of coumarin-
dihydroquinazolinone analogs as niacin receptor 1 agonist with in-vivo anti-
obesity efficacy, J. Med. Chem. 152 (2018) 208–222.
4] X.F. Wu, S. Oschatz, A. Block, A. Spannenberg, P. Langer, Base mediated synthesis
of 2-aryl-2,3-dihydroquinazolin-4(1H)-ones from 2-aminobenzonitriles and
aromatic aldehydes in water, Org. Biomol. Chem. 12 (2014) 1865–1870.
Scheme 4. A proposed mechanism for the synthesis of bis(indolyl)methanes.
[5] P.N. Borase, P.B. Thale, G.S. Shankarling, A choline hydroxide catalyzed synthesis
of 2,3-dihydroquinazolin-4(1H)-ones in an aqueous medium, RSC Adv. 6 (2016)
6
3078–63083.
[6] B. Dam, R.A. Patil, Y.R. Ma, A. Kumar Pal, Preparation, characterization and
catalytic application of nano-Fe -DOPA-SnO having high TON and TOF for non-
toxic and sustainable synthesis of dihydroquinazolinone derivatives, New J. Chem.
1 (2017) 6553–6563.
performance of our heterogeneous catalyst in the synthesis of bis
3
O
4
2
(
indolyl)methanes.
One of the serious problems for homogenous catalysts as a conven-
4
tional promoter in these types of synthesis is difficult separation and
product contaminations [37,38]. The recyclability of the catalyst was
studied using the model reaction of dihydroquinazolinones synthesis.
After the complect of the reaction, the catalyst was easily separated by a
magnetic bar and washed with hot ethanol, then dried and applied in the
next catalytic cycle.
[7] V. Sriramoju, S. Kurva, S. Madabhushi, Oxone-mediated annulation of 2-amino-
benzamides and 1,2-diaminobenzenes with sec-amines via imine-N-oxides: new
syntheses of 2,3-dihydroquinazolin-4(1H)-ones and 1H-benzimidazoles, New J.
Chem. 42 (2018) 3188–3191.
[8] B. Majumdar, S. Mandani, T. Bhattacharya, D. Sarma, T.K. Sarma, Probing
carbocatalytic activity of carbon nanodots for the synthesis of biologically active
Dihydro/Spiro/Glyco quinazolinones and aza-michael adducts, J. Org. Chem. 82
(
2017) 2097–2106.
Until the eighth reuse, no important reduction in activity was
detected. The results were given in Table 7. The reused catalyst was
characterized by FT-IR analysis, the spectra are given in supplementally
data.
[
9] L. Cao, H. Huo, H. Zeng, Y. Yu, D. Lu, Y. Gong, One-pot synthesis of Quinazolin-4
(3H)-ones through anodic oxidation and the related mechanistic studies, Adv.
Synth. Catal. 360 (2018) 4764–4773.
[
[
[
10] A.A. Khan, K. Mitra, A. Mandala, N. Baildy, M.A. Mondal, Yttrium nitrate catalyzed
synthesis, photophysical study, and TD-DFT calculation of 2,3-dihydroquinazolin-4
(1H)-ones, Heteroatom Chem. 28 (2017) 21379–21384.
The preparation bis(indolyl)methanes plausible mechanism was
given in Scheme 4.
11] J. Devi, S.J. Kalita, D.C. Deka, Expeditious synthesis of 2,3-dihydroquinazolin-4
(
1H)-ones in aqueous medium using thiamine hydrochloride (VB1) as a mild,
efficient, and reusable organocatalyst, Synth. Commun. 47 (2017) 1601–1609.
12] S. Ayyanar, P.K. Vijaya, M. Mariyappan, V. Ashokkumar, V. Sadhasivam,
S. Balakrishnan, C. Chinnadurai, S. Murugesan, Enantioselective synthesis of
6

F. Mohammadi Metkazini et al.
Molecular Catalysis 506 (2021) 111532
dihydroquinazolinone derivatives catalyzed by a chiral organocatalyst, New J.
[30] R.M. Alia, M.R. Elkatory, H.A. Hamad, Highly active and stable magnetically
recyclable CuFe2O4 as a heterogenous catalyst for efficient conversion of waste
frying oil to biodiesel, Fuel 268 (2020) 117297–117312.
Chem. 41 (2017) 7980–7986.
[
13] S.G. Zhang, Z.B. Xie, L.S. Liu, M. Liang, Z.G. Le, Synthesis of 2,3-dihydroquinazo-
lin-4(1H)-ones catalyzed by
14] H. Batmani, N.N. Pesyana, F. Havasi, Ni-Biurea complex anchored onto MCM-41:
As an efficient and recyclable nanocatalyst for the synthesis of 2,3-
α
-chymotrypsin, Chin. Chem. Lett. 28 (2017) 101–104.
[31] N.A. El Essawy, S.M. Ali, H.A. Farag, A.H. Konsowa, M. Elnoubyd, H.A. Hamade,
Green synthesis of graphene from recycled PET bottle wastes for use in the
adsorption of dyes in aqueous solution, Ecotoxicol. Environ. Saf. 145 (2017)
57–68.
[
dihydroquinazolin-4(1H)-ones, Microporous Mesoporous Mater. 257 (2018)
2
7–34.
[32] A. Salamatmanesh, A. Heydari, H.T. Nahzomi, Stabilizing Pd on magnetic
phosphine-functionalized cellulose: DFT study and catalytic performance under
deep eutectic solvent assisted conditions, Carbohydr. Polym. 235 (2020)
115947–115951.
[
15] J. Safari, S. Gandomi-Ravandi, The combined role of heterogeneous catalysis and
ultrasonic waves on the facile synthesis of 2,3-dihydroquinazolin-4(1H)-ones,
J. Saudi Chem. Soc. 21 (2017) 415–424.
[
[
16] M. Bandini, A. Eichholzer, Catalytic functionalization of indoles in a new
dimension, Angew. Chem. Int. Ed. 48 (2009) 9608–9644.
[33] M. Jadidi Nejad, A. Salamatmanesh, A. Heydari, Copper (II) immobilized on
magnetically separable l-arginine-β-cyclodextrin ligand system as a robust and
green catalyst for direct oxidation of primary alcohols and benzyl halides to acids
in neat conditions, J. Organomet. Chem. 911 (2020) 121128–121132.
[34] M. Elkady, H. Shokry, H. Hamad, Microwave-assisted synthesis of magnetic
hydroxyapatite for removal of heavy metals from groundwater, Chem. Eng.
Technol. 41 (2018) 553–562.
17] A.J. Kochanowska Karamyan, M.T. Hamann, Marine indole alkaloids: potential
new drug leads for the control of depression and anxiety, Chem. Rev. 110 (2010)
4
489–4497.
[
[
18] G.W. Gribble, Top. Heterocycl. Chem. (2010) 433.
19] B. Bao, Q. Sun, X. Yao, J. Hong, C.O. Lee, C.J. Sim, K.S. Im, J.H. Jung, Cytotoxic
bisindole alkaloids from a marine sponge Spongosorites sp, J. Nat. Prod. 68 (2005)
[35] A.R. Hajipour, Z. Khorsandi, F. Fakhari, M. Mortazavi, H. Farrokhpour,
7
11–715.
2 4
A comparative study between Co- and CoFe O -NPs catalytic activities in synthesis
[
[
20] P. Ertl, S. Jelfs, J. Mühlbacher, A. Schuffenhauer, P. Selzer, Quest for the rings. In
silico exploration of ring universe to identify novel bioactive heteroaromatic
scaffolds, J. Med. Chem. 49 (2006) 4568–4573.
of flavone derivatives; study of their interactions with estrogen receptor by
molecular docking, ChemistrySelect 3 (2018) 6279–6286.
[36] M.E.A.A.A. El-Remaily, H.A. Hamad, Synthesis and characterization of highly
stable superparamagnetic CoFe2O4 nanoparticles as a catalyst for novel synthesis
of thiazolo[4,5-b]quinolin-9-one derivatives in aqueous medium, J. Mol. Catal. A
Chem. 404 (2015) 148–155.
21] S.X. Cai, D.H. Li, T.J. Zhu, F.P. Wang, X. Xiao, Q.Q. Gu, An effective green and
ecofriendly catalyst for synthesis of bis(indolyl)methanes as promising
antimicrobial agents, Hel. Chim. Acta 93 (2010) 791–795.
[
[
22] N. Azizi, Z. Manocheri, Eutectic salts promote green synthesis of bis(indolyl)
methanes, Res. Chem. Intermed. 38 (2012) 1495–1500.
[37] P.J. Das, J. Das, Synthesis of aryl/alkyl(2,2’-bis-3- methylindolyl)methanes and
aryl(3,3’-bisindolyl)methanes promoted by secondary amine based ionic liquids
and microwave irradiation, Tetrahedron Lett. 53 (2012) 4718–4720.
[38] N.A. Elessawy, M. Elnouby, M.H. Gouda, H. A.Hamad, N. A.Taha, M. Goudae, M.
S. Mohy Eldin, Ciprofloxacin removal using magnetic fullerene nanocomposite
obtained from sustainable PET bottle wastes: adsorption process optimization,
kinetics, isotherm, regeneration and recycling studies, Chemosphere 239 (2020)
124728.
23] H. Veisi, B. Maleki, F.H. Eshbala, H. Veisi, R. Masti, S.S. Ashrafi, M. Baghayeri, In
situ generation of Iron(iii) dodecyl sulfate as Lewis acid-surfactant catalyst for
synthesis of bis-indolyl, tris-indolyl, Di(bis-indolyl), Tri(bis-indolyl), tetra(bis-
indolyl)methanes and 3-alkylated indole compounds in water, RSC Adv. 4 (2014)
3
0683–30688.
[
[
24] A.R. Hajipour, F. Rezaei, Z. Khorsandi, Pd/Cu-free Heck and Sonogashira cross-
coupling reaction by Co nanoparticles immobilized on magnetic chitosan as
reusable catalyst, Green Chem. 19 (2017) 1353–13688.
[39] N.A. Elessawy, E.M. El-Sayed, S. Ali, M.F. Elkady, M. Elnouby, H.A. Hamad, One-
pot green synthesis of magnetic fullerene nanocomposite for adsorption
characteristics, J. Water. Process. Eng. 34 (2020) 101047.
25] A.R. Hajipour, Z. Khorsandi, S.F.M. Metkazini, Palladium nanoparticles supported
on cysteine-functionalized MNPs as robust recyclable catalysts for fast O- and N-
arylation reactions in green media, J. Organomet. Chem. 899 (2019)
[40] H.T.D. Nguyen, T. Nguyen, P.T.K. Nguyen, P.H. Tran, A highly active copper-based
metal-organic framework catalyst for a friedel–crafts alkylation in the synthesis of
bis(indolyl)methanes under ultrasound irradiation, Arab. J. Chem. 13 (2020)
1377–1385.
1
20793–120800.
[
[
26] M. Elkady, H. Shokry, A. El-Sharkawy, G. El-Subruiti, H. Hamada, New insights
into the activity of green supported nanoscale zero-valent iron composites for
enhanced acid blue-25 dye synergistic decolorization from aqueous medium,
J. Mol. Liq. 294 (2019) 111628–111639.
4
[41] D.Z. Xu, J. Tong, C. Yang, Ionic liquid [DABCO-H][HSO ] as a highly efficient and
recyclable catalyst for Friedel–Crafts alkylation in the synthesis of bis(naphthol)
methane and bis(indolyl)methane derivatives, Synthesis 48 (2016) 3559–3566.
[42] A. Shaabani, R. Afshari, S.E. Hooshmand, A.T. Tabatabaei, F. Hajishaabanha,
27] D. Bassyouni, M. Mohamed, E.S. El-Ashtoukhy, M.A. El-Latif, A. Zaatout,
H. Hamad, Fabrication and characterization of electrospun Fe3O4/o-MWCNTs/
polyamide 6 hybrid nanofibrous membrane composite as an efficient and
recoverable adsorbent for removal of Pb (II), Microchem. J. 149 (2019)
3 4
Copper supported on MWCNT-guanidine acetic acid@Fe O : synthesis,
characterization and application as a novel multi-task nanocatalyst for preparation
of triazoles and bis(indolyl)methanes in water, RSC Adv. 6 (2016) 18113–18135.
[43] S. Sobhani, S. Asadi, M. Salimi, F. Zarifi, Cu-isatin schiff base complex supported on
magnetic nanoparticles as an efficient and recyclable catalyst for the synthesis of
bis(indolyl)methanes and bis(pyrazolyl)methanes in aqueous media, J. Organomet.
Chem. 822 (2016) 154–164.
1
03998–104010.
[
[
28] H.A. Hamada, M.M. Abd El-latifa, A.B. Kashyoutb, W.A. Sadikc, M.Y. Feteha, Study
on synthesis of superparamagnetic spinel cobalt ferrite nanoparticles as layered
double hydroxides by Co-precipitation method, Russ. J. Gen. Chem. 84 (2014)
2
031–2036.
[44] Y. Wang, R. Sang, Y. Zheng, L. Guo, M. Guan, Y. Wu, Graphene oxide: an efficient
recyclable solid acid for the synthesis of bis(indolyl)methanes from aldehydes and
indoles in water, Catal. Commun. 89 (2017) 138–142.
29] H. Hamad, M.A. El-Latif, A.E.H. Kashyout, W. Sadik, M. Feteha, Synthesis and
characterization of core/shell/1 shell magnetic (CoFe2O4/SiO2/TiO2)
nanocomposite and TiO2 nanoparticle for photocatalytic activity under UV and
visible irradiation, New J. Chem. 39 (2015) 3116–3128.
[45] B.R. Nemallapudi, G.V. Zyryanov, Meglumine as a green, efficient and reusable
catalyst for synthesis and molecular docking studies of bis(indolyl)methanes as
antioxidant agents, Bioorg. Chem. 87 (2019) 465–473.
7