Preparation and study of the catalytic application in the synthesis of xanthenedione pharmaceuticals of a hybrid nano-system based on copper, zinc and iron nanoparticles

Article abstract of DOI:10.1007/s11164-020-04311-8

A novel efficiently mixed transition metal oxides catalytic system with high catalytic activity and heterogeneity constructed of copper and zinc oxide nanoparticles is presented. For preparation of this hybrid catalytic system, carrageenan as a natural polymeric matrix has been chosen to add biocompatibility to the heterogeneous catalyst. Then, the carrageenan textures have been magnetized through the composition with iron oxide nanoparticles. Copper and zinc metallic sites are employed as the main catalytic sites for catalyzing the synthesis of xanthenedione pharmaceutical derivatives from aldehyde and dimedone. Due to the magnetic behavior of the catalyst, the purification process is carried out with high convenience. Herein, a plausible mechanism for the catalytic process is suggested and reusability of the presented catalyst is also investigated. In this report, it has been well-proven that high reaction yields are obtained for xanthenedione derivatives under mild conditions, through applying the presented hybrid catalytic system.

Full text of DOI:10.1007/s11164-020-04311-8

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-020-04311-8
Preparation and study of the catalytic application
in the synthesis of xanthenedione pharmaceuticals
of a hybrid nano‑system based on copper, zinc and iron
nanoparticles
Mir Saeed Esmaeili1 · Zahra Varzi1 · Reza Taheri‑Ledari1 · Ali Maleki1
Received: 30 June 2020 / Accepted: 23 October 2020
© Springer Nature B.V. 2020
Abstract
A novel efciently mixed transition metal oxides catalytic system with high cata-
lytic activity and heterogeneity constructed of copper and zinc oxide nanoparticles
is presented. For preparation of this hybrid catalytic system, carrageenan as a natu-
ral polymeric matrix has been chosen to add biocompatibility to the heterogeneous
catalyst. Then, the carrageenan textures have been magnetized through the composi-
tion with iron oxide nanoparticles. Copper and zinc metallic sites are employed as
the main catalytic sites for catalyzing the synthesis of xanthenedione pharmaceutical
derivatives from aldehyde and dimedone. Due to the magnetic behavior of the cata-
lyst, the purifcation process is carried out with high convenience. Herein, a plausi-
ble mechanism for the catalytic process is suggested and reusability of the presented
catalyst is also investigated. In this report, it has been well-proven that high reaction
yields are obtained for xanthenedione derivatives under mild conditions, through
applying the presented hybrid catalytic system.
Keywords Metal oxides · Solid-phase catalyst · Copper nanoparticle ·
Pharmaceutical compounds · Zinc ferrite
Zahra Varzi is a Co-frst author.
Electronic supplementary material The online version of this article (https://doi.org/10.1007/s1116
4-020-04311-8) contains supplementary material, which is available to authorized users.
*
Ali Maleki
maleki@iust.ac.ir
1
Catalysts and Organic Synthesis Research Laboratory, Department of Chemistry, Iran University
of Science and Technology (IUST), 16846-13114 Tehran, Iran
Vol.:(0123456789)
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M. S. Esmaeili et al.
Introduction
Active pharmaceutical ingredients (APIs) typically include complex chemical
structures that are difcult to be synthesized. Besides, they include several heter-
oatoms such as nitrogen and oxygen at their structures, which provide a suitable
situation for catalytic activations [1, 2]. Metals are usually used in the structure
of the heterogeneous catalytic systems that create efective electronic interac-
tions with the lone pair electrons and lead to the facile synthesis processes [3–7].
Recently, several works have been reported about the preparation and applica-
tion of the metallic nanocatalysts for facilitating the synthesis of the APIs with
complex structures [8–10]. For instance, palladium-decorated hybrid nanocata-
lysts have been widely reported for this purpose [11–15]. Transition metals such
as copper, palladium, zinc, manganese, silver, gold, iron, and metal oxides have
also been used for catalyzing the chemical synthesis reactions and other purposes
[16–23]. In this regard, we intended to design a novel transition metal-containing
heterogeneous catalytic system, and suitably apply that for facilitating the syn-
thesis of xanthenedione pharmaceutical derivatives [24, 25]. In this way, we use
zinc, copper, and iron metals for preparation of a nanosized hybrid system. In
fact, zinc ferrite is used as the magnetic agent in the composite and provides a
substantial property for the catalyst to be conveniently isolated from the reac-
tion mixture and reused again for the several times [26], whereas copper(I) oxide
nanoparticles are the main catalytic active sites and play the key role in the cata-
lytic process [27]. From pharmacological aspect, xanthenedione is considered as
a substantial antioxidant and also as an appropriate inhibitor for acetylcholinest-
erase (AChE) enzyme [28]. The chemical structure of xanthenedione includes
oxygen atoms coming from the aldehyde and dimedone (5,5-dimethylcyclohex-
ane-1,3-dione), as the initial structural units. So, metal atoms could catalyze the
synthetic process of xanthenedione through forming efective electronic interac-
tions with these oxygen atoms. In this regard, several metallic systems including
iron, lead, zirconium, zinc, and natural structures have been prepared and used
[29–31].
Heterogeneous catalytic systems are generally preferred due to their conveni-
ent separation from the reaction mixture [32–34]. Recently, the magnetic prop-
erty of the catalytic systems has attracted so much attentions because they could
be separated by using an external magnet and also the catalyst is recycled and
reused for several times [35, 36]. For magnetization of the catalytic systems, zinc
ferrite and iron oxide nanoparticles (Fe2O3, Fe2O4, and Fe3O4 NPs) are usually
used [37, 38]. Super-paramagnetic behavior of the zinc ferrite and iron oxide
NPs has led researchers to extensively use that for catalytic applications [39–41].
Previously, we have reported several novel catalytic systems made of iron oxide
NPs [42–50]. For this aim, a combination of the zinc ferrite and iron oxide NPs
with other materials is prepared. As a well-known strategy, a polymeric matrix
is chosen for the composition with magnetic NPs and also immobilization of
the metallic NPs [51–57]. In this study, we chose “carrageenan” as a natural
basis, which is made of a linear sulfated polysaccharides and is extracted from
1 3

Preparation and study of the catalytic application in the…
OH
OH
O
-
OSO3
O
O
O
-
OSO3
HO
-
OSO
3O
carrageenan
seaweed
Scheme 1 Structure of the carrageenan
red edible seaweeds [57]. Since, there are several sulfates and hydroxyl groups
in the structure of carrageenan, metallic NPs could be well-immobilized in this
natural matrix (Scheme 1). In 2015, Rostamnia and co-workers have reported a
magnetic catalytic system based on carrageenan, and used that for clean synthesis
of rhodanines [58]. They made a combination of carrageenan and Fe3O4 NPs and
used the hydroxyl groups of the mentioned composite as the catalytic sites. Here,
we intend to use numerous hydroxyl sites of the carrageenan for the formation
of the strong H-binding interactions with the metallic sites. These interactions
enhance the total stability of the composite. Then, copper(I) ions are distributed
onto the surfaces and act as the main catalytic sites, which are more active than
the hydroxyl groups. As a desirable result, it is observed that our trimetallic com-
posite results in higher reaction yields in a short time, under green conditions. In
this study, frstly, we try to present a convenient preparation route for our hybrid
metallic nanocatalyst, including zinc ferrite and copper NPs stabilized in the car-
rageenan (Cu-ZnFe2O4@carrageenan nanocomposite). Then, the presented cata-
lytic system is suitably applied for facilitating the synthesis reactions of xanthen-
edione pharmaceutical derivatives. In this work, this is demonstrated that high
reaction yields (98%) are obtained in short reaction time (10 min), under mild
reaction conditions, through applying the presented method.
Results and discussion
Preparation of Cu‑ZnFe2O4@carrageenan nanocatalyst
In our designed catalytic system, zinc ferrite has been used as the magnetic agent
in the composite and provides a substantial property for catalyst to be conveni-
ently isolated with high convenience. The copper(I) oxide nanoparticles are the
main catalytic active sites and play the key role in the catalytic process. In order
to prepare the catalytic system, nitrate salts of iron and zinc were co-precipitated
in the presence of carrageenan via ultrasonication in a cleaner ultrasound bath, at
50 °C. After well-mixing, the environment of the reaction was gradually alkalinized
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M. S. Esmaeili et al.
using a concentrated solution of sodium hydroxide until the color of the mixture
was changed to brown, meaning that ZnFe2O4 NPs have been well-formed [59]. In
our case, sodium hydroxide (0.1 M, 10 mL) was used until pH~12 was obtained.
In the next stage, copper(II) chloride was dissolved in a solution of ascorbic acid to
form the target Cu-ZnFe2O4@carrageenan nanocomposite, under refux conditions
(Fig. 1). Here, ascorbic acid plays the role of a reducing agent for Cu2+ ions to form
Cu2O NPs, in which Cu is in chemical state Cu+.
Characterization of cu‑znfe2o4@carrageenan nanocomposite
To investigate the structure of the prepared Cu-ZnFe2O4@carrageenan nanocata-
lyst, Fourier-transform infrared (FT-IR) spectroscopy was used as the frst step of
characterization. As shown in Fig. 2a, the peak intensity related to hydroxyl groups
at~3400 cm−1 in carrageenan structure has been reduced after the composition of
the Zn/Fe2O4 and Cu NPs. It means that the oxygen atoms of the carrageenan have
participated in the formation of Cu-ZnFe2O4@carrageenan composite. Sharp peaks
at~1000 and 1200 cm−1 coming from the sulfonic acid groups are present in the
structure of carrageenan. The intensity of the distinguished peak at~2900 cm−1 was
also reduced. This peak is related to C–H bonds with hybridation sp3. Most likely,
due to the composition of the metallic NPs with the textures of carrageenan, the
vibration of this bond has been a bit lost [60]. Further, the presence of the elements
in the structure of ZnFe2O4@carrageenan and Cu-ZnFe2O4@carrageenan compos-
ites were investigated. For this purpose, energy-dispersive X-ray (EDX) spectros-
copy was used (Fig. 2b,c). As can be seen, the presence of all the essential atoms
is confrmed by the EDX spectra. In addition, a quantitative analysis has been per-
formed showing the weight percentages of the present elements.
The thermal stability and assembly process of the fabricated Cu-ZnFe2O4@car-
rageenan composite was studied by thermogravimetric analysis (TGA), in a ther-
mal range of 25–800 °C (Fig. 3a). For the neat carrageenan, proportional to increase
Fig. 1 Schematic of the convenient preparation route of Cu-ZnFe2O4@carrageenan nanocomposite
1 3

Preparation and study of the catalytic application in the…
Fig. 2 a FT-IR spectra of the neat carrageenan, ZnFe2O4@carrageenan, and Cu-ZnFe2O4@carrageenan
nanocomposite, b EDX spectra of ZnFe2O4@carrageenan and Cu-ZnFe2O4@carrageenan nanocompos-
ite, and c EDX quantitative table of the present elements in the structure of Cu-ZnFe2O4@carrageenan
nanocomposite
the temperature, a partial increase in the weight ratio was observed (ca. 5 wt%) and
gradually lost till 100 °C. This fuctuation is likely due to the capability of the carra-
geenan substrate to adsorb the moisture in the air. During 100–200 °C, about 8% of
the total weight has been lost that can be attributed to the removal of the entrapped
water molecules in the polymeric matrix [62–64]. Then, the frst shoulder has been
appeared until ca. 400 °C. According to the literature, in this range, the carrageenan
loses its hydroxyl groups via dehydration process and separation of the organic
structures like sulfonic acid groups [64]. During this stage, ca. 40% of the weight
has been lost [65]. Then, descending trend has been continued to 800 °C. During
this stage (400–800 °C), ca. 7% weight loss is observed that is likely coming from
1 3

M. S. Esmaeili et al.
Fig. 3 a TGA curves of the neat carrageenan, ZnFe2O4@carrageenan, and Cu-ZnFe2O4@carrageenan
nanocomposite, and b VSM M-H curves of ZnFe2O4@carrageenan and Cu-ZnFe2O4@carrageenan nano-
composite at room temperature
the main decomposition of carrageenan, whereas for both ZnFe2O4@carrageenan
and Cu-ZnFe2O4@carrageenan metal composition forms, this is observed that the
thermal stability has been increased and the observed degradation in the case of
the individual carrageenan (in particular at 300–800 °C) is not observed. The mag-
netic behavior of the Cu-ZnFe2O4@carrageenan composite has been investigated
and compared with the ZnFe2O4@carrageenan as well (Fig. 3b). As can be seen
in the M-H curves, the magnetic property was signifcantly decreased (8.0 emu/g)
after copperation of the ZnFe2O4@carrageenan composite. As a possible reason, a
slight distortion in cubic structure of ZnFe2O4 by the Cu ion substitution could be
mentioned for the reduced magnetic property. This substitution by the Cu ions may
change the magnetization, coercivity and magnetic anisotropy of the ZnFe2O4 crys-
talline structure [66]. However, from this analysis, it was revealed that the particles
of the catalyst could be magnetically separated through applying a magnetic feld,
recycled, and reused.
X-ray difraction (XRD) pattern of the prepared Cu-ZnFe2O4@carrageenan
composite was also provided and compared with the reference patterns of ZnFe2O4
(JCPDS #001-1109) and Cu2O (JCPDS #005-0667) (Fig. 4a). As seen in the pattern,
a broad peak has been appeared until 2θ=20° that is attributed to the amorphous
structure of carrageenan [67, 68]. Then, the peaks related to the ZnFe2O4·NPs,
which have been indicated by pink circles, are observed at 2θ=30.19°, 35.47°,
42.94°, 57.12°, and 62.75°. They have been marked in the pattern with Miller indi-
ces as (4 0 0), (4 2 2), (6 2 0), (8 0 0), and (7 5 1), respectively. Also, the existence
of Cu2O·NPs has been proven by the peaks that appeared at 2θ=22.59°, 32.48°,
42.41°, and 61.36°. These peaks have been highlighted by blue triangles in the pat-
tern, and also with Miller indices (1 1 1), (2 1 1), (3 1 1), and (4 2 0), respectively.
The main indicative peak of Cu2O·NPs is a sharp peak at ca. 32°. Moreover, to
1 3

Preparation and study of the catalytic application in the…
Fig. 4 a XRD pattern of the prepared Cu-ZnFe2O4@carrageenan nanocomposite, b XPS spectrum of the
prepared Cu-ZnFe2O4@carrageenan, and c expanded XPS spectrum in the range of 925–950 eV
prove successful reduction of Cu from chemical state Cu2+–Cu+, X-ray photoelec-
tron spectroscopy (XPS) was performed [69, 70]. As shown in Fig. 4b, c, a sole peak
appeared at 933 eV proves the formation of Cu2O·NPs, in which Cu in chemical
state Cu+ has been participated.
Scanning electron microscopy (SEM) and transmission electron micros-
copy (TEM) were used to investigate the size, morphology, and composition
1 3

M. S. Esmaeili et al.
Fig. 5 a–c SEM image and d TEM image of the prepared Cu-ZnFe2O4@carrageenan nanocomposite
attitude of the prepared Cu-ZnFe2O4@carrageenan. As illustrated in the SEM image
(Fig. 5a–c), the polymeric texture of the carrageenan substrate has been well-modi-
fed by the metallic NPs. Bright areas in the image (a) indicate that the metallic NPs
have been successfully incorporated into the carrageenan matrix. Images (b and c)
illustrate well-distribution of the metallic NPs onto the carrageenan textures with
high magnifcation. As is observed in the image (c), the mean size of the formed
NPs is ca. 47 nm. The same sample was investigated by TEM as well (Fig. 5d), and
it was revealed that the ZnFe2O4 and Cu2O·NPs have been well-distributed between
the carrageenan textures. From the TEM image, it was also disclosed that the spher-
ical-shaped NPs have been well-synthesized because high uniformity in size and
morphology is observed for the particles. From these analyses, this is observed that
well-dispersion of the metallic particles have been obtained despite of high magnetic
behavior of Fe2O4·NPs. In fact, no agglomeration is observed for the ZnFe2O4 and
Cu2O·NPs, which is considered as a great point especially in catalytic applications.
As shown in Fig. 5d, the mean size of the metallic particles is ca. 28 nm diameter,
meaning that an extreme active surface area is provided by using a small amount of
the particles. As is observed in TEM image, some of the heterogeneous particles
have been formed of two sections, which are distinguished by light gray and dark
gray colors. In this case, light and dark areas are attributed to Fe2O4 and Zn·NPs,
respectively. The reason is related to more electronic density around the core of Zn
atom that inhibits transmission of the electron beam of TEM instrument.
1 3

Preparation and study of the catalytic application in the…
Catalytic application of Cu‑ZnFe2O4@carrageenan nanocatalyst in xanthenedione
derivatives
Optimization
To obtain the most appropriate conditions, various catalytic ratios of Cu-ZnFe2O4@
carrageenan in diferent media and temperatures have been experimented for the
catalyzed synthesis of 2,2′-(4-chlorophenyl methylene)bis(3-hydroxycyclohex-2-en-
1-one) as a model reaction. The control reactions were tested in diferent times as
well. Moreover, the efciency of the individual carrageenan and ZnFe2O4 was com-
pared with Cu-ZnFe2O4@carrageenan composite. As given in Table 1, the highest
reaction yield is obtained when 0.01 g of the catalytic system has been applied in
water medium during 10 min stirring under refux conditions. Also, a gram-scale
experiment was carried out to investigate the catalytic performance of the fabricated
Cu-ZnFe2O4@carrageenan nanocatalyst in high scales. For this purpose, 10 mmol
of each reactant and 0.1 g of the catalytic system were considered for doing the reac-
tion, under optimal conditions. As can be observed in Table 1 (entry 12), 86% yield
was obtained in totally 10 min, which is quite satisfying at this scale.
Table 1 Optimization of the catalytic process of the synthesis of 2,2′-(4-chlorophenyl methylene)bis(3-
hydroxycyclohex-2-en-1-one)
Entry Catalyst
Cat. W. (g) Solvent
Temp. (°C) Time (min) Yielda (%)
1
2
3
4
5
6
7
8
–
–
–
–
0.01
0.01
H2O
H2O
H2O
H2O
H2O
H2O
H2O
EtOH
THF
CH2Cl2
r.t
480
300
180
180
10
10
10
15
90
150
10
10
10
10
10
10
Trace
47
55
70
72
98*
98
91
73
60
Refux
Refux
Refux
Refux
Refux
Refux
Refux
Refux
Refux
ZnFe2O4
Carrageenan
Cu-ZnFe2O4@carrageenan 0.005
Cu-ZnFe2O4@carrageenan 0.01
Cu-ZnFe2O4@carrageenan 0.02
Cu-ZnFe2O4@carrageenan 0.01
Cu-ZnFe2O4@carrageenan 0.01
Cu-ZnFe2O4@carrageenan 0.01
Cu-ZnFe2O4@carrageenan 0.01
Cu-ZnFe2O4@carrageenan 0.01
Cu-ZnFe2O4@carrageenan 0.01
Cu-ZnFe2O4@carrageenan 0.01
Cu-ZnFe2O4@carrageenan 0.01
Cu-ZnFe2O4@carrageenan 0.1
9
10
11
12
13
14
15
16
H2O/EtOH Refux
98
78
82
80
DMSO
DMF
CH3CN
H2O
Refux
Refux
Refux
40
74
H2O
Refux
86b
*optimal conditions
aIsolated yields. The conditions were monitored for the synthesis of 2,2′-(4-chlorophenyl methylene)
bis(3-hydroxycyclohex-2-en-1-one), using 4-chlorobenzaldehyde (1.0 mmol), 1,3-cyclohexanedione or
dimedone (2.0 mmol), and 2.0 mL solvent. The reaction progress was screened by thin-layer chromatog-
raphy (elusion solvent: a mixture of EtOAc and n-hexane [1:8])
bgram-scale experiment
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M. S. Esmaeili et al.
The catalytic activity of Cu‑ZnFe2O4@carrageenan nanocatalyst
The capability of the prepared catalytic system was more investigated using vari-
ous derivatives of aldehyde to synthesize diferent derivatives of xanthenedione.
All of the reactions were carried out in the obtained optimal conditions. As given
in Table 2, high reaction yields were obtained through applying a small amount of
Cu-ZnFe2O4@carrageenan nanocatalyst. As the frst and foremost excellence of our
novel designed catalytic system well-applicability in the aqueous medium could be
mentioned. In the other words, using this natural-based catalytic system is in great
correspondence with the green chemistry principles. However, after obtaining the
pure xanthenedione compounds, FT-IR and NMR spectroscopy were used to iden-
tify the structures [71]. Actually, the presence of the electron-withdrawing groups
(EWG) onto the benzene ring accelerates the reaction because they make the alde-
hyde more activated and ready for reception of the nucleophiles. According to the
literature and the obtained results in our study (Table 2), higher reaction yields are
obtained for EWG-containing structures than the electron-donor groups like meth-
oxy group [52, 53].
Proposed mechanism
Scheme 2 presents a plausible mechanism for catalyzed synthesis of xanthenedi-
one derivatives. According to the literature, Cu and Zn present in the structure of
catalyst activate the aldehyde component at the frst stage [80]. Next, dimedone or
1,3-cyclohexanedione attacks to the activated aldehyde [81, 82]. At third stage, a
dehydration process is performed to provide a conjugated unsaturated structure [83,
84]. Finally, a 1,4-addition is performed by another dimedone or 1,3-cyclohexanedi-
one and the desired xanthenedione structure is formed [85, 86]. After completion
of the process, the magnetic particles of the catalyst are regenerated and could be
reused.
Recyclability of Cu‑ZnFe2O4@carrageenan nanocomposite
To investigate recyclability of the catalytic system, the particles were separated after
completion of the reaction of the synthesis of 2,2′-(4-chlorophenyl methylene)bis(3-
hydroxycyclohex-2-en-1-one) 3u and reused for additional fve times. As shown in
Fig. 6, the obtained reaction yield has been 10% reduced after fve times recycling
but is acceptable yet. For this purpose, the particles were conveniently collected
using an external magnet, washed, and dried in oven. The FT-IR and EDX spectra
of the recovered NPs have been prepared and illustrated in the supporting informa-
tion section (Figs. S1 and S2). To investigate physisorption isotherms of the struc-
ture of Cu-ZnFe2O4@carrageenan nanocomposite, Brunauer–Emmett–Teller (BET)
surface area analysis was carried out on the fresh catalyst and after recovering, via
adsorption/desorption of N2 gas (Fig. 7). The reversible isotherm of both and recov-
ered catalyst is a typical type II, which is related to macroporous materials. The pre-
pared Cu-ZnFe2O4@carrageenan nanocomposite has shown the type IV isotherm of
mesoporous materials (pore size 2–50 nm) (Fig. 7b) with a hysteretic loop in the
1 3

Preparation and study of the catalytic application in the…
Table 2 Xanthenedione derivatives produced via the catalyzed synthetic process by Cu-ZnFe2O4@car-
rageenan nanocatalyst
Entry Product structure
1
Product No Yielda (%)
Ref
MP (°C)
Found
Lit
3a
93
226–229 229–231 [72]
2
3b
94
205–207 204
[73]
3
4
3c
93
90
202–204 199–200 [74]
3d
210–213 213
[73]
1 3

M. S. Esmaeili et al.
Table 2 (continued)
Entry Product structure
5
Product No Yielda (%)
Ref
MP (°C)
Found
Lit
3e
87
229–231 231–232 [74]
6
7
3f
85
93
193–194 190–191 [74]
3 g
204–206 207
194–197 197
[73]
[73]
8
3 h
89
1 3

Preparation and study of the catalytic application in the…
Table 2 (continued)
Entry Product structure
9
Product No Yielda (%)
Ref
MP (°C)
Found
Lit
3i
90
218–220 219
[73]
10
3j
90
196–198 199–200 [74]
11
12
3 k
90
94
194–197 196
200–202 200
[73]
[73]
3 l
13
3 m
94
188–190 191–193 [75]
1 3

M. S. Esmaeili et al.
Table 2 (continued)
Entry Product structure
14
Product No Yielda (%)
Ref
MP (°C)
Found
Lit
3n
88
186–187 185
[73]
15
3o
92
201–203 203–205 [76]
16
17
3p
3q
95
92
183–185 184–186 [77]
190–191 190
[78]
1 3

Preparation and study of the catalytic application in the…
Table 2 (continued)
Entry Product structure
18
Product No Yielda (%)
Ref
MP (°C)
Found
Lit
3r
88
198–201 199–201 [74]
19
20
21
3 s
90
145–146 145
[73]
3t
98
98
190–192 190–192 [79]
3u
142–144 145
[73]
aIsolated yields
*All reactions were carried out in the optimum conditions (10 min)
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M. S. Esmaeili et al.
Scheme 2 Plausible mechanism for the synthesis of xanthenedione derivatives, catalyzed by Cu-
ZnFe2O4@carrageenan nanocomposite
Fig. 6 Recycling diagram of Cu-ZnFe2O4@carrageenan nanocomposite in the synthesis reaction of 3u
1 3

Preparation and study of the catalytic application in the…
Fig. 7 a Isotherm linear plot, and b adsorption cumulative pore volume of Cu-ZnFe2O4@carrageenan
nanocomposite before (blue) and after (red) the recycling process (circle-spotted curve: fresh catalyst,
and square-spotted curve: recovered catalyst). (Color fgure online)
range from 0.0 to 1.0 P/P0 (Fig. 7a). From the curves, this is observed that the capac-
ity of the pore sizes has been partially decreased after several times recycling, and as
a result it can be expresses that the six times recovering has no signifcant efect on
the porosity of the Cu-ZnFe2O4@carrageenan catalyst.
Comparison of catalyst
The efciency of the Cu-ZnFe2O4@carrageenan nanocomposite was compared with
previously reported catalytic systems in the literature. In Table 3, the synthesis of
2,2′-(4-chlorophenyl methylene)bis(3-hydroxycyclohex-2-en-1-one) 3u in the pres-
ence of the Cu-ZnFe2O4@carrageenan nanocomposite is compared with other cata-
lysts based on the reaction time (entries 1, 2 and 3) and the obtained yields (entries 1
and 2). As can be seen, the presented Cu-ZnFe2O4@carrageenan system well-works
in a shorter time and results in higher yields than the previous catalysts.
Table 3 Comparison of Cu-ZnFe2O4@carragenan nanocomposite with other previous systems
Entry Cat. system
Conditions
Time (min) Yield (%) Ref
1
2
3
4
5
6
7
8
9
ZnO
CH3CN/refux
480
60
70
840
10
10
80
5
90
93
98
79
90
92
83
90
98
[87]
[88]
[89]
[76]
[77]
[78]
[90]
[91]
Copper (0) nanoparticles onto silica EtOH/80 °C
Nano Fe/NaY Zeolite
CaCl2 (20% mmol)
Nanostructured Na2CaP2O7
PVPa-Ni
EtOH/78 °C
CH3Cl3/r.t
H2O/refux
Ethylene glycol/r.t
H2O/r.t
Microwave irradiation
Fe3O4@SiO2-SO3H
AOTb
Cu-ZnFe2O4@carragenan
H2O/refux
10
This work
apolyvinyl pyrrolidone
bsodiumbis -2-ethyl hexyl sulfosuccinate
1 3

M. S. Esmaeili et al.
Experimental
Materials and equipment
All of the applied materials and apparatuses are reported in Table S1 (SI section).
Methods
Preparation of ZnFe2O4@carrageenan nanocomposite
In a glass round-bottom fask (50 mL), Zn(NO3)2·6H2O (0.6 g, 3.0 mmol) and
Fe(NO3)3·9H2O (1.6 g, 4.0 mmol) were mixed in deionized water (10 mL) via stir-
ring at room temperature. Then, carrageenan (0.5 g) was added and the mixture was
ultrasonicated for 40 min at 50 °C. Next, NaOH solution (0.1 M, 10 mL) was dropwise
added into the fask until the mixture color was changed to dark brown that indicates
formation of the ZnFe2O4 NPs successfully (pH~12 is obtained). In continue, the reac-
tion mixture was refuxed for 2 h. Finally, the obtained precipitation was magnetically
separated, washed two times with water and ethanol, and dried at 78 °C [18, 47].
Preparation of Cu‑ZnFe2O4@carrageenan nanocomposite
In a glass fask (100 mL), ZnFe2O4@carrageenan nanocomposite (0.5 g) was dispersed
in ethanol (25 mL) and ascorbic acid (25 ml, 0.05 M, in deionized water), via ultrasoni-
cation for 30 min. Then, CuCl2⋅2H2O (0.5 mmol, 0.09 g) was added and the mixture
was refuxed for 48 h. Finally, the obtained precipitation was prepared according to the
procedure explained in the previous section [92, 93].
General procedure for catalysis of the synthesis reactions of xanthenedione
derivatives 3a‑u
In a glass round-bottom fask (25 mL), aldehyde derivative (1.0 mmol) and dimedone
(or 1,3-cyclohexanedione) (2.0 mmol) were dissolved in deionized water (2.0 mL), and
0.01 g of Cu-ZnFe2O4@carrageenan nanocomposite was then added. Next, the mix-
ture was exposed to ultrasound waves (50 kHz, 100 W L−1) using a cleaner ultrasound
bath, at room temperature (for 2 min). Afterward, the reaction mixture was refuxed
for 10 min. Then, the catalyst particles were magnetically separated and 3.0 mL
of deionized water was added. Afterward, DCM (5.0 mL) was added and extrac-
tion was carried out by using decanter. Finally, desired products were purifed using
fash-chromatography.
Spectral data for selected compounds
Product 3a (2,2′‑((2‑chlorophenyl)methylene)bis(3‑hydroxycyclohex‑2‑en‑1‑one))
13CNMR (75 MHz, CDCl3): δ (ppm)=20.6, 28.9, 32.4, 37.2, 101.6, 123.6, 126.7,
127.7, 131.8, 132.2, 142.7, 196.2, 198.4. EI-MS [M]: m/z 348.
1 3

Preparation and study of the catalytic application in the…
Product 3b (2,2′‑((4‑chlorophenyl)methylene)bis(3‑hydroxycyclohex‑2‑en‑1‑one))
13CNMR (75 MHz, CDCl3): δ (ppm)=20.0, 32.6, 33.0, 33.5, 116.1, 119.6, 128.4,
131.2, 137.0, 190.9, 192.2. EI-MS [M]: m/z 348.
Product 3c (2,2′‑((3‑chlorophenyl)methylene)bis(3‑hydroxycyclohex‑2‑en‑1‑one))
13CNMR (75 MHz, CDCl3): δ (ppm)=20.1, 32.8, 33.0, 33.5, 115.9, 122.5, 125.2,
129.0, 129.6, 129.7, 140.6,190.9, 192.2. EI-MS [M]: m/z 348.
Product
3d
(2,2′‑((2‑nitrophenyl)methylene)bis(3‑hydroxycyclohex‑2‑en‑1‑one))
13CNMR (75 MHz, CDCl3): δ (ppm)=21.1, 30.4, 34.1, 37.2, 108.1, 124.8, 129.1,
130.4, 134.5, 149.7, 190.1, 194.2. EI-MS [M]: m/z 357.
Product 3e (2,2′‑((3,4,5‑trimethoxyphenyl)methylene)bis(3‑hydroxycyclohex‑2‑en‑1‑one))
13CNMR (75 MHz, CDCl3): δ (ppm)=20.7, 33.2, 34.8, 36.7, 55.4, 59.2, 107.8, 109.5,
136.2, 136.5, 152.0, 180.2, 189.2. EI-MS [M]: m/z 402.
Product 3f (2,2′‑((2‑methoxyphenyl)methylene)bis(3‑hydroxycyclohex‑2‑en‑1‑one))
13CNMR (75 MHz, CDCl3): δ (ppm)=23.1, 29.6, 30.4, 33.8, 37.2, 50.4, 114.8
121.9, 123.3, 125.4, 129.7, 147.1, 188.6, 193.2. EI-MS [M]: m/z 342.
Product
3
g
(2,2′‑((3‑nitrophenyl)methylene)bis(3‑hydroxycyclohex‑2‑en‑1‑one))
13CNMR (75 MHz, CDCl3): δ (ppm)=19.7, 20.3, 28.6, 32.8, 34.6, 36.4, 58.8,
100.1, 114.6, 120.4, 123.0, 128.7, 135.6, 147.1, 147.4, 168.5, 195.5, 199.1. EI-MS
[M]: m/z 357.
Product 3 h (2,2′‑((4‑methoxyphenyl)methylene)bis(3‑hydroxycyclohex‑2‑en‑1‑one))
13CNMR (75 MHz, CDCl3): δ (ppm)=20.1, 32.2, 33.0, 33.5, 55.2, 113.6, 116.6,
127.5, 129.7, 157.6, 190.8, 192.0. EI-MS [M]: m/z 342.
Product 3i (2,2′‑(phenylmethylene)bis(3‑hydroxycyclohex‑2‑en‑1‑one)) 13CNMR
(75 MHz, CDCl3): δ (ppm)=20.13, 32.92, 32.99, 33.51, 116.45, 125.85, 126.48,
128.16, 128.50, 130.18, 133.70, 138.18, 189.79, 191.82; EI-MS [M]: m/z 312.
Product 3j (2,2′‑((2‑bromophenyl)methylene)bis(3‑hydroxycyclohex‑2‑en‑1‑one))
13CNMR (75 MHz, CDCl3): δ (ppm)=21.2, 31.9, 33.7, 36.2, 112.4, 124.1, 127.3,
128.6, 130.9, 133.3, 146.3, 193.1, 195.7; EI-MS [M]: m/z 393.
Product 3 k (2,2′‑(phenylmethylene)bis(3‑hydroxy‑5,5‑dimethylcyclohex‑2‑en‑1‑one))
1HNMR (300 MHz, CDCl3): δ (ppm)=1.12 (s, 6H, 2CH3), 1.25 (s, 6H, 2CH3),
2.30–2.50 (m, 8H, 4CH2), 5.56 (s, 1H, CH), 7.10–7.30 (m, 4H, H-Ar), 11.92 (s,
1H, OH). 13CNMR (75 MHz, CDCl3): δ (ppm)=27.2, 29.6, 31.4, 32.74, 46.5, 47.0,
115.6, 125.5, 126.7, 128.2, 138.5, 189.4, 190.8. EI-MS [M]: m/z 368.
Product3l(2,2′‑((2‑chlorophenyl)methylene)bis(3‑hydroxy‑5,5‑dimethylcyclohex‑2‑en‑1‑one))
1HNMR (300 MHz, CDCl3): δ (ppm)=1.06 (s, 6H, 2CH3), 1.33 (s, 6H, 2CH3), 2.06–2.50
1 3

M. S. Esmaeili et al.
(m, 8H, 4CH2), 5.57 (s, 1H, CH), 7.00–7.52 (m, 4H, H-Ar), 11.90 (s, 1H, OH). 13C NMR
(75 MHz, CDCl3): δ (ppm)=27.4, 28.9, 29.5, 31.3, 46.4, 46.2, 115.5, 115.5, 115.7, 125.1,
125.5, 127.9, 127.9, 129.1, 129.2, 159.1, 162.6, 189.5. EI-MS [M]: m/z 404.
Product 3 m (2,2′‑((2‑nitrophenyl)methylene)bis(3‑hydroxy‑5,5‑dimethylcyclohex‑2‑en‑
1
1‑one)) HNMR (300 MHz, CDCl3): δ (ppm)=1.02 (s, 6H, 2CH3), 1.17 (s, 6H,
2CH3), 2.25–2.54 (m, 8H, 4CH2), 6.05 (s, 1H, CH), 7.27 (d, 1H, H-Ar), 7.28 (t, 1H,
H-Ar), 7.47 (t, 1H, HAr), 7.57 (d, 1H, H-Ar), 11.60 (s, 1H, OH). 13CNMR (75 MHz,
CDCl3): δ (ppm)=28.4, 28.3, 30.5, 31.9, 46.3, 46.4, 114.4, 124.3, 127.7, 129.5,
131.3, 132.1, 149.2, 189.0, 191.2. EI-MS [M]: m/z 413.
Product 3n1 (2,2′‑((2‑methoxyphenyl)methylene)bis(3‑hydroxy‑5,5‑dimethylcyclohex‑2‑
en‑1‑one)) HNMR (300 MHz, CDCl3): δ (ppm)=1.12 (s, 6H, 2CH3), 1.35 (s, 6H,
2CH3), 3.73–3.79 (m, 8H, 4CH2), 5.59 (s, 1H, CH), 6.80–7.28 (m, 4H, H-Ar), 11.86
(s, 1H, OH). 13CNMR (75 MHz, CDCl3): δ (ppm)=29.2, 31.2, 46.2, 55.8, 116.4,
119.9, 126.1, 127.0, 128.5, 157.1, 189.2. EI-MS [M]: m/z 398.
Product 3o (2,2′‑((3, 4, 5‑ tri methoxyphenyl)methylene)bis(3‑hydroxy‑5,5‑dimethylcy‑
clohex‑2‑en‑1‑one)) 13CNMR (75 MHz, CDCl3): δ (ppm)=27.2, 32.9, 35.6, 38.9,
51.3, 57.2, 60.7, 106.8, 108.2, 136.4, 137.3, 151.2, 182.0, 190.8. EI-MS [M]: m/z
458.
Product 3p (2,2′‑((3‑chlorophenyl)methylene)bis(3‑hydroxy‑5,5‑dimethylcyclohex‑2‑
1
en‑1‑one)) HNMR (300 MHz, CDCl3): δ (ppm)=0.89 (s, 6H, 2CH3), 1.09 (s, 6H,
2CH3), 2.10–2.39 (m, 8H, 4CH2), 5.59 (s, 1H, CH), 7.20–7.40 (m, 4H, H-Ar), 11.89
(s, 1H, OH). 13CNMR (75 MHz, CDCl3): δ (ppm)=27.7, 29.13, 32.1, 34.1, 47.8,
50.9, 111.9, 124.7, 128.7, 131.4, 135.4, 144.3, 189.9, 191.7. EI-MS [M]: m/z 404.
Product 3q (2,2′‑((3‑nitrophenyl)methylene)bis(3‑hydroxy‑5,5‑dimethylcyclohex‑2‑
1
en‑1‑one)) HNMR (300 MHz, CDCl3): δ (ppm)=1.12 (s, 6H, 2CH3), 1.28 (s, 6H,
2CH3), 2.32–2.53 (m, 8H, 4CH2), 5.54 (s, 1H, CH), 7.26–8.05 (m, 4H, H-Ar), 11.87
(s, 1H, OH). 13CNMR (75 MHz, CDCl3): δ (ppm)=27.3, 29.7, 31.4, 32.9, 46.4,
47.0, 114.8, 121.0, 122.2, 129.1,132.9, 140.7, 148.4, 189.6, 191.1. EI-MS [M]: m/z
413.
Product 3r (2,2′‑((3‑methoxyphenyl)methylene)bis(3‑hydroxy‑5,5‑dimethylcyclohex‑2‑
en‑1‑one)) 13CNMR (75 MHz, CDCl3): δ (ppm)=27.8, 29.9, 32.5, 34.6, 47.5, 51.2,
55.8, 114.7, 121.1, 123.8, 129.6, 148.6, 160.4, 187.9, 192.1. EI-MS [M]: m/z 398.
Product 3 s (2,2′‑((4‑methoxyphenyl)methylene)bis(3‑hydroxy‑5,5‑dimethylcyclohex‑2‑
en‑1‑one)) 13CNMR (75 MHz, CDCl3): δ (ppm)=27.0, 29.3, 31.1, 31.8, 40.5,
46.2, 46.8, 50.5, 54.9, 113.4, 115.5, 127.5, 129.0, 130.2, 157.3, 161.8, 189.0, 190.0.
EI-MS [M]: m/z 398.
1 3

Preparation and study of the catalytic application in the…
Product 3t1 (2,2′‑((2,4‑dicholorophenyl)methylene)bis(3‑hydroxy‑5,5‑dimethylcyclohex‑2‑
en‑1‑one)) HNMR (300 MHz, CDCl3): δ (ppm)=1.01 (s, 6H, 2CH3), 1.38 (s, 6H,
2CH3), 2.22–2.44 (m, 8H, 4CH2), 5.49 (s, 1H, CH), 6.58–7.27 (m, 4H, H-Ar), 11.95
(s, 1H, OH). 13CNMR (75 MHz, CDCl3): δ (ppm)=27.8, 29.4, 31.6, 32.7, 46.2, 47.4,
114.2, 126.9, 129.0, 129.8, 130.0, 132.3, 138.7, 189.4, 190.7. EI-MS [M]: m/z 436.
Product 3u (2,2′‑((4‑chlorophenyl)methylene)bis(3‑hydroxy‑5,5‑dimethylcyclohex‑2‑
1
en‑1‑one)) HNMR (300 MHz, CDCl3): δ (ppm)=1.11 (s, 6H, 2CH3), 1.32 (s, 6H,
2CH3), 2.19–2.50 (m, 8H, 4CH2), 5.48 (s, 1H, CH), 7.01–7.28 (m, 4H, H-Ar), 11.88
(s, 1H, OH). 13CNMR (75 MHz, CDCl3): δ (ppm)=27.2, 29.5, 31.4, 32.4, 46.4,
47.0, 115.3, 128.2, 128.3, 131.5, 136.7, 189.4, 190.6. EI-MS [M]: m/z 404.
Conclusions
In summary, a novel hybrid heterogeneous catalytic system has been prepared from
carrageenan as a natural polymeric matrix for immobilization of the ZnFe2O4 and
Cu2O NPs, and applied for convenient synthesis of xanthenedione pharmaceutical
derivatives. Herein, the chemical structure and physical properties of the prepared
mixed transition metal oxides catalytic system (Cu-ZnFe2O4@carrageenan) have
been studied by various analyses. Briefy, well-composition of three components has
been confrmed by FT-IR and EDX spectroscopy. From EDX, it has been revealed
that 4.45 wt% Cu is incorporated into the structure of the composite, which are the
main active catalytic sites. Moreover, high heterogeneity and structural stability of
the fabricated Cu-ZnFe2O4@carrageenan have been proven by TGA. Besides, great
magnetic property of the catalyst has been shown by magnetic hysteresis (M-H)
curves. These substantial features make the presented catalytic system as an instru-
mental recoverable tool for organic catalysis. In this report, it has been revealed that
a six-time successive recycling and reuse does not negatively infuence on the cata-
lytic performance and no structural deterioration is observed. Furthermore, uniform
distribution of the Cu2O NPs (in ca. 28 nm mean size) onto the carrageenan textures
has been demonstrated by SEM and TEM methods. X-ray-based analytical meth-
ods such as XRD and XPS have revealed the successful formation of Cu(I), as well.
However, the catalytic activity of this nanoscale catalyst has been investigated in the
synthesis of the various derivatives of xanthenedione. In this work, it has been dem-
onstrated that high reaction yields (above 90%) are obtained in short time (10 min)
through using Cu-ZnFe2O4@carrageenan heterogeneous catalytic system. In addi-
tion, due to high convenience in the separation and purifcation process (through the
magnetic property) and great recyclability of Cu-ZnFe2O4@carrageenan, this novel
designed catalytic system is suggested for industrial applications.
1 3

M. S. Esmaeili et al.
Supplementary data
The SI fle includes the NMR of selected xanthenedione products. The brand and
purity of the used materials have also been listed in this section. This section can be
found in the online version.
Acknowledgements The authors gratefully acknowledge the partial support from the Research Council
of the Iran University of Science and Technology (IUST).
Compliance with ethical standards
Confict of interest The authors declare no confict of interest.
References
1. J.C. Garrison, C.A. Tessier, W.J. Youngs, J. Organomet. Chem. 690, 6008 (2005)
2. R. Taheri-Ledari, S.M. Hashemi, A. Maleki, RSC Adv. 9, 40348 (2019)
3. M. Peng, C. Hong, Y. Huang, P. Cheng, H. Yuan, J. Organomet. Chem. 909, 121110 (2016)
4. L.V. Gelderen, G. Rothenberg, V.R. Calderone, K. Wilson, N.R. Shiju, Appl. Organomet. Chem. 27,
23 (2013)
5. R.K. Mondal, S. Riyajuddin, A. Ghosh, S. Ghosh, K. Ghosh, S.M. Islam, J. Organomet. Chem. 880,
322 (2018)
6. M.J. Alcón, A. Corma, M. Iglesias, F. Sánchez, J. Organomet. Chem. 655, 134 (2002)
7. J. Xu, H. Shimakoshi, Y. Hisaeda, J. Organomet. Chem. 2015, 89 (2013)
8. A. Bahuguna, A. Kumar, V. Krishnan, Asian. J. Org. Chem. 8, 1263 (2019)
9. M.B. Gawande, A. Goswami, F. Felpin, T. Asefa, X. Huang, R. Silva, X. Zou, R. Zboril, R.S.
Varma, Chem. Rev. 116, 3722 (2016)
10. M.R. Khodabakhshi, M. Kiamehr, F.M. Moghaddam, A. Villinger, P. Langer, ChemistrySelect 3,
1167 (2018)
11. A. Maleki, R. Taheri-Ledari, R. Ghalavand, R. Firouzi-Haji, J. Phys. Chem. Solids 136, 109200
(2020)
12. J. Huang, S. Liu, Y. Ma, J. Cai, J. Organomet. Chem. 886, 27 (2019)
13. S. Layek, B. Agrahari, S. Dey, R. Ganguly, D.D. Pathak, J. Organomet. Chem. 896, 194 (2019)
14. H. Karimi, M.A. Heidari, H.B.M. Emrooz, M. Shokouhimehr, Diam. Relat. Mater. 108, 107999
(2020)
15. P. Nazari, M. Hekmati, Appl. Organomet. Chem. 33, e4729 (2019)
16. A. Maleki, M. Niksefat, J. Rahimi, R. Taheri-Ledari, Mater. Today Chem. 13, 110 (2019)
17. C. Boztepe, A. Künkül, S. Yaşar, N. Gürbüz, J. Organomet. Chem. 872, 123 (2018)
18. Z. Varzi, A. Maleki, Appl. Organomet. Chem. 32, e5008 (2019)
19. A. Martinez, C. Hemmert, H. Gornitzka, B. Meunier, J. Organomet. Chem. 690, 2163 (2005)
20. Y.A. Attia, Y.M.A. Mohamed, M.M. Awad, S. Alexeree, J. Organomet. Chem. 919, 121320 (2020)
21. J. Li, Y. Wang, S. Jiang, H. Zhang, J. Organomet. Chem. 878, 84 (2018)
22. J. Rahimi, R. Taheri-Ledari, M. Niksefat, A. Maleki, Catal. Commun. 134, 105850 (2020)
23. R. Taheri-Ledari, W. Zhang, M. Radmanesh, S.S. Mirmohammadi, A. Maleki, N. Cathcart, V.
Kitaev, Small 16, 2002733 (2020)
24. N. Hazeri, A. Masoumnia, M.T. Mghsoodlou, S. Salahi, M. Kangani, S. Kianpour, S. Kiaee, J.
Abonajmi, Res. Chem. Intermed. 41, 4123 (2015)
25. S.E.S. Sorkhi, M.M. Hashemi, A. Ezabadi, Res. Chem. Intermed. 46, 2229 (2020)
26. T.R.R. Naik, S.A. Shivashankar, Tetrahedron Lett. 57, 4046 (2016)
27. A. Habibi, M.H. Baghersad, M. Bilabary, Y. Valizadeh, Tetrahedron Lett. 57, 559 (2016)
28. S. Parvaz, R. Taheri-Ledari, M.S. Esmaeili, M. Rabbani, A. Maleki, Life Sci. 240, 117099 (2020)
29. H.Y. Lü, J.J. Li, Z.H. Zhang, Appl. Organomet. Chem. 23, 165 (2009)
30. M. Kidwai, A. Jain, Appl. Organomet. Chem. 26, 528 (2012)
1 3

Preparation and study of the catalytic application in the…
31. K. Valadi, S. Gharibi, R. Taheri-Ledari, A. Maleki, Solid State Sci. 101, 106141 (2020)
32. V. Vatanpour, H. Karimi, S.I. Ghazanlou, Y. Mansourpanah, M.R. Ganjali, A. Badiei, E. Pourbashir,
M.R. Saeb, J. Environ. Chem. Eng. 8, 104454 (2020)
33. J. Akbari, A. Heydari, H.R. Kalhor, S.A. Kohan, J. Comb. Chem. 12, 137 (2010)
34. R. Taheri-Ledari, A. Maleki, J. Pept. Sci. 26, e3277 (2020)
35. H.S. Far, M. Hasanzadeh, M.S. Nashtaei, M. Rabbani, A. Haji, B.H. Moghadam, A.C.S. Appl,
Mater. Interfaces 12, 25294 (2020)
36. M.J. Iqbal, Z. Ahmad, Y. Melikho, I.C. Nlebedim, J. Magn. Magn. Mater. 324, 1018 (2012)
37. A. Maleki, K. Valadi, S. Gharibi, R. Taheri-Ledari, Res. Chem. Intermed. 46, 4113 (2020)
38. M. Mehdipour, M.R. Khodabakhshi, Curr. Chem. Lett. 9, 9 (2020)
39. M.H. Baghersad, S. Jamshidi, A. Habibi, A. Salimi, ChemistrySelect 4, 810 (2019)
40. N. Elahi, M. Kamali, M.H. Baghersad, B. Amini, Mater. Sci. Eng. C 105, 110113 (2019)
41. A. Maleki, R. Taheri-Ledari, M. Soroushnejad, ChemistrySelect 3, 13057 (2018)
42. A. Maleki, R. Taheri-Ledari, J. Rahimi, M. Soroushnejad, Z. Hajizadeh, ACS Omega 4, 10629
(2019)
43. R. Taheri-Ledari, J. Rahimi, A. Maleki, Mater. Res. Express. 7, 015067 (2020)
44. R. Taheri-Ledari, A. Maleki, E. Zolfaghari, M. Radmanesh, H. Rabbani, A. Salimi, R. Fazel, Ultra-
son. Sonochem. 61, 104824 (2020)
45. M.S. Esmaeili, M.R. Khodabakhshi, A. Maleki, Z. Varzi, Polycycl. Aromat. Compd. (2020). https://
doi.org/10.1080/10406638.2019.1708418
46. A. Maleki, F. Hassanzadeh-Afruzi, Z. Varzi, M.S. Esmaeili, Mater. Sci. Eng. C. 109, 110502 (2020)
47. A. Maleki, Z. Varzi, F. Hassanzadeh-Afruzi, Polyhedron 171, 193 (2019)
48. R. Taheri-Ledari, J. Rahimi, A. Maleki, Ultrason. Sonochem. 59, 104737 (2019)
49. R. Eyvazzadeh-Keihan, N. Bahrami, R. Taheri-Ledari, A. Maleki, Diam. Relat. Mater. 102, 107661
(2020)
50. H. Xie, H. Liu, M. Wang, H. Pan, C. Gao, Appl. Organomet. Chem. 34, e5256 (2020)
51. M.J. Nejad, A. Salamatmanesh, A. Heydari, J. Organomet. Chem. 911, 121128 (2020)
52. F.M. Moghaddam, A. Jarahiyan, M. Eslami, A. Pourjavadi, J. Organomet. Chem. 916, 121266
(2020)
53. F. Rafee, P. Khavari, Z. Payami, N. Ansari, J. Organomet. Chem. 883, 78 (2019)
54. I. Yavari, A. Mobaraki, Z. Hosseinzadeh, N. Sakhaee, J. Organomet. Chem. 897, 236 (2019)
55. M. Kumari, R. Gupta, Y. Jain, Appl. Organomet. Chem. 33, e5223 (2019)
56. X. Meng, G. Li, H. Hou, H. Han, Y. Fan, Y. Zhu, C. Du, J. Organomet. Chem. 679, 153 (2003)
57. C.J. Cheng, O.G. Jones, Food Hydrocoll. 69, 28 (2017)
58. S. Rostamnia, B. Zeynizadeh, E. Doustkhah, A. Baghban, K.O. Aghbash, Catal. Commun. 68, 77
(2015)
59. C. Cai, Z. Zhang, J. Liu, N. Shan, H. Zhang, D.D. Dionysiou, Appl. Catal. B. 182, 456 (2006)
60. S. Soltani, U. Rashid, I. Arbi Nehdi, S.I. Al-Resayes, Chem. Eng. Technol. 40, 1931 (2007)
61. W. Zhang, R. Taheri-Ledari, Z. Hajizadeh, E. Zolfaghari, M.R. Ahghari, A. Maleki, M.R. Hamblin,
Y. Tian, Nanoscale 12, 3855 (2020)
62. A. Maleki, S. Gharibi, K. Valadi, R. Taheri-Ledari, J. Phys. Chem. Solids 142, 109443 (2020)
63. A. Maleki, R. Taheri-Ledari, R. Ghalavand, Comb. Chem. High T. Scr. 23, 119 (2020)
64. A. Rasool, S. Ata, A. Islam, M. Rizwan, M.K. Azeem, A. Mehmood, R.U. Khan, A. Ur Rehman
Qureshi, H. Arshad Mahmood, Int. J. Biol. Macromol. 147, 67 (2020)
65. Y.Y. Tye, A.K. HPS, C.Y. Kok, C.K. Saurabh, IOP Conference Series: Materials Science and Engi-
neering, WOBIC, Selangor, Malaysia. 368, 21 (2017)
66. N. Ahmadpour, M.H. Sayadi, S. Sobhani, M. Hajiani, J. Clean. Prod. 268, 122023 (2020)
67. G.R. Mahdavinia, H. Etemadi, Arab. J. Chem. 12, 3692 (2019)
68. P. Sangeetha, T.M. Selvakumari, S. Selvasekarapandian, S.R. Srikumar, R. Manjuladevi, M.
Mahalakshmi, Ionics 26, 233 (2020)
69. P. Duan, R. Su, X. Xu, Q. Li, B. Gao, J. Taiwan Inst. Chem. Eng. 102, 456 (2019)
70. S. Ghosh, S. Saha, D. Sengupta, S. Chattopadhyay, G. De, B. Basu, Ind. Eng. Chem. Res. 56,
11726–11733 (2017)
71. C. Shen, H. Li, Y. Wen, F. Zhao, Y. Zhang, D. Wu, Y. Liu, F. Li, Chem. Eng. J. 383, 123105 (2020)
72. J.K. Rajput, G. Kaur, Catal. Sci. Technol. 4, 142 (2014)
73. S.H. Banakar, M.G. Dekamin, A. Yaghoubi, New J. Chem. 42, 14246 (2018)
74. K.M. Khan, G.M. Maharvi, M.T.H. Khan, A.J. Shaikh, S. Perveen, S. Begum, M.I. Choudhary,
Med. Chem. 14, 344 (2006)
1 3

M. S. Esmaeili et al.
75. Y. Ren, B. Yang, X. Liao, RSC Adv. 6, 22034 (2016)
76. A. Ilangovan, S. Muralidharan, P. Sakthivel, S. Malayappasamy, S. Karuppusamy, M.P. Kaushik,
Tetrahedron Lett. 54, 491 (2013)
77. B. Maleki, M. Raei, H. Alinezhad, R. Tayebee, A. Sedrpoushan, Org. Prep. Proced. Int. 50, 288
(2018)
78. J.M. Khurana, K. Vij, J. Nickel, Chem. Sci. 124, 907 (2012)
79. M.T. Maghsoodlou, S.M. Habibi-Khorassani, Z. Shahkarami, N. Maleki, M. Rostamizadeh, Chin.
Chem. Lett. 21, 7413 (2017)
80. R.G. Chaudhary, V.N. Sonkusare, G.S. Bhusari, A. Mondal, D.P. Shaik, H.D. Juneja, Res. Chem.
Intermed. 44, 2039 (2018)
81. M. Salami, A. Ezabadi, Res. Chem. Intermed. 46, 4611 (2020)
82. N.G. Khaligh, Res. Chem. Intermed. 44, 4045 (2018)
83. S. Karhale, M. Patil, G. Rashinkar, V. Helavi, Res. Chem. Intermed. 43, 7073 (2017)
84. N. Mohammadian, B. Akhlaghinia, Res. Chem. Intermed. 44, 1085 (2018)
85. M. Rahimifard, G.M. Ziarani, A. Badiei, S. Asadi, A.A. Soorki, Res. Chem. Intermed. 42, 3847
(2016)
86. A. Fallah, M. Tajbakhsh, H. Vahedi, A. Bekhradnia, Res. Chem. Intermed. 43, 29 (2017)
87. M.T. Maghsoodlou, S.M. Habibi-khorassani, Z. Shahkarami, N. Maleki, M. Rostamizadeh, Chin.
Chem. Lett. 21, 686 (2010)
88. M. Gupta, M. Gupta, J. Chem. Sci. 128, 849 (2016)
89. M. Tajbakhsh, M. Heidary, Res. Chem. Intermed. 42, 1425 (2016)
90. F. Nemati, M.M. Heravi, R.S. Rad, Chin. J. Catal. 33, 1825 (2012)
91. M. Saha, J. Dey, K. Ismail, A.K. Pal, Lett. Org. Chem. 8, 554 (2011)
92. M.S. Esmaeili, Z. Varzi, R. Eivazzadeh-Keihan, A. Maleki, H. Ghafuri, Mol. Catal. 492, 111037
(2020)
93. S. Shaabani, A.T. Tabatabaei, A. Shaabani, Appl. Organomet. Chem. 31, e3559 (2017)
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