Synthesis of MCM-41 supported cobalt (II) complex for the formation of polyhydroquinoline derivatives

Article abstract of DOI:10.1016/j.poly.2021.115102

A new and green heterogeneous MCM-41@PDCA-Co catalyst has been prepared via immobilization of cobalt (II) complex onto the surface of MCM-41. This was characterized by different techniques such as FT-IR, TEM, TGA, low angle Powder XRD, MP-AES and nitrogen

Full text of DOI:10.1016/j.poly.2021.115102

Polyhedron 199 (2021) 115102
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Polyhedron
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Synthesis of MCM-41 supported cobalt (II) complex for the formation of
polyhydroquinoline derivatives
b
Saurabh Sharma a, Udai P. Singh a, , A.P. Singh
⇑
a Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247 667, India
b Department of Applied Sciences, National Institute of Technology, Delhi 110 040, India
a r t i c l e i n f o
a b s t r a c t
Article history:
A new and green heterogeneous MCM-41@PDCA-Co catalyst has been prepared via immobilization of
cobalt (II) complex onto the surface of MCM-41. This was characterized by different techniques such
as FT-IR, TEM, TGA, low angle Powder XRD, MP-AES and nitrogen sorption. The MCM-41@PDCA-Co has
been applied in the synthesis of polyhydroquinoline (PHQs) and its derivatives in 98% yield which is four
component reaction under solvent free condition at 100 °C. The synthesized catalyst can be easily recov-
ered from the reaction mixture by simple filtration method. This can be reused several times without any
significant loss in stability and activity.
Received 18 December 2020
Accepted 10 February 2021
Available online 20 February 2021
Keywords:
Mesoporous material
Cobalt (II) complex
MCM-41
Ó 2021 Published by Elsevier Ltd.
Catalyst
Polyhydroquinoline
1. Introduction
In recent years, researchers have paid considerable attention
toward nanomaterials because they show excellent applications
Polyhydroquinoline and its derivatives are important com-
pounds due to their pharmaceutical properties such as hepatopro-
tective, geroprotective, bronchodilator, antitumour, vasodilator,
cardiovascular and antiartherosclerotic etc [1,2]. Moreover, poly-
hydroquinoline is used for the treatment of Alzheimer’s disease
and in the form of chemosensitizer in tumor therapy [3]. Polyhy-
droquinoline and related compound are generally prepared via
condensation of aldehydes, 1,3-cyclohexanedione derivatives,
ethyl acetoacetate and ammonium acetate using one-pot four-
component Hantzsch reaction [4].
A variety of catalysts like lewis acid, base and nanomaterial
such as Sc(OTf)3 [5], GuHCl [6], Al2(SO4)3 [7], Yb(OTf)3 [8], HClO4–
SiO2 [9], P(4-VPH)HSO4 [10], Mn(III) complex [11], Hf(NPf2)4 [12],
K7[PW11CoO40] [13], ceric ammonium nitrate [14], alumina sulfu-
ric acid [15], nickel nanoparticles [16], MgO nanoparticles [17],
and palladium (0) nanoparticles [18], have been used. The syn-
thetic methods for above catalytic reaction suffer from various dis-
advantages such as expensive reagents, harsh reaction conditions,
long reaction times, low-product yields and the use of large quan-
tity of volatile, toxic organic solvents. Besides, larger amount of
catalyst loading is the main disadvantage, the used catalyst is
destroyed during the reaction and cannot be reused [19].
in modern synthetic chemistry and industrial chemistry as sensors,
adsorbents, CO2 capture or transformation and energy production
[20,21]. The metal catalyst immobilized on solid support materials
to incorporate the preponderances of both heterogeneous and
homogeneous catalysis has emerged as an efficient catalytic strat-
egy in organic synthesis [22]. Various types of inorganic, organic
and metal mix materials for instance mesoporous silica, molecular
sieves, magnetic iron oxide, ionic liquids, graphene oxide, poly-
mers, nanocomposite have been reported in the literature [23].
More recently in the material community, interest has been devel-
oped towards nanocarrier mesoporous silica nanoparticles (MSNs)
with the exposed surface area due to the increasing demands for
environmental friendly and economically viable synthetic pro-
cesses [24]. The development of heterogeneous catalysts that pro-
mote one-pot multicomponent reactions (MCRs) for the formation
of desired products in the most efficient manner is highly impor-
tant [25]. For this purpose, Different approaches have been
reported time to time for the preparation of heterogeneous cata-
lysts with multiple active sites on various support scaffolds. Hence,
mesoporous silica-based materials (MCM) with pore radius of
approximately 2–50 nm and very large surface areas (up to
2000 m2 gÀ1) as well as mechanically stable structure have become
a new possible candidate for solid supports to immobilize homoge-
neous catalysts [26] or directly use them alone as heterogeneous
catalyst [27]. Dawood Elhamifar et al. developed MCM-41 sup-
ported tungstic acid for one-pot synthesis of new pyrrolo[2,1–a]
⇑
Corresponding author.
E-mail address: udaipfcy@iitr.ac.in (U.P. Singh).
https://doi.org/10.1016/j.poly.2021.115102
0277-5387/Ó 2021 Published by Elsevier Ltd.

S. Sharma, U.P. Singh and A.P. Singh
Polyhedron 199 (2021) 115102
isoquinolines [28]. Ghorbani-Choghamarani et. al. discovered a
new cobalt (II) complex immobilised on the surface of SBA-15 as
an efficient catalyst for the oxidation of sulphide and preparation
of polyhydroquinoline [29]. Ehsan Valiey et al. prepared hydro-
2.2.2. Synthesis of MCM-41@PDCA
1.00 g of MCM-41 was dispersed in 30 ml of dry chloroform for
30 min with vigorous stirring. Then the solution of 0.50 g
(0.87 mmol) of PDCA in 20 ml of dry chloroform was added and
the reaction mixture was stirred at room temperature under nitro-
gen atmosphere for 24 h. After completion of reaction, the reaction
mixture was centrifuged to get the white solid, which was washed
with chloroform and ethanol several times. The resulting white
solid was dried in a hot air oven at 60 °C for 8 h.
gen-bond-enriched
1,3,5-tris(2-hydroxyethyl)isocyanurate
covalently functionalized MCM-41 for synthesis of acridinedione
derivatives [30]. Khanmoradi et al. reported zirconium@gua-
nine@MCM-41
nanoparticles
that
catalysed
one-pot,
multicomponent tandem Knoevenagel condensation Michael
addition-cyclization reactions [31].
The present paper reports a green approach for the synthesis of
polyhydroquinoline via multicomponent reactions using an inex-
pensive, eco-friendly and recyclable MCM-41 supported cobalt
(II) catalyst under the solvent-free condition in less reaction time.
2.2.3. Preparation of MCM-41@PDCA-Co
0.50 g of MCM-41@PDCA was dispersed in 40 ml ethanol for
30 min with constant stirring. Then an ethanolic solution (10 ml)
of cobalt chloride (0.10 g, 0.7 mmol) was added. The resulting solu-
tion was refluxed for 24 h under nitrogen atmosphere and cooled
to room temperature. The bluish solid was separated, washed with
ethanol (4 Â 5 ml) and dried at 70 °C for 5 h (Scheme 1).
2. Experimental
2.1. Materials and instrumentation
2.2.4. General method for the synthesis of polyhydroquinoline
Aldehyde (1.00 mmol), 1,3-cyclohexanedione or dimedone
(1.00 mmol), ethylacetoacetate (1.00 mmol), ammonium acetate
(1.20 mmol) and MCM-41@PDCA-Co (10.00 mg) were taken in a
25 ml round bottom flask and the reaction mixture was stirred at
100 °C for 10 min. The formation of the product was monitored
by TLC using ethyl acetate:n-hexane (3:7 ratio) solvent. After com-
pletion of reaction as indicated by TLC, the solid product was dis-
solved in 10 ml ethanol by refluxing, filtered and cooled. The
yellow precipitate was obtained by adding ice to the filtrate and
washing with cold ethanol.
All reagents and solvents were of analytical grade and used
without further purification. Co(Cl)2 anhydrous was purchased
from Merck. The MCM-41 mesoporous nanoparticle was synthe-
sized by Juarez method [32]. Melting points were determined with
a capillary point apparatus equipped with a digital thermometer.
IR spectra were recorded as KBr pellets with Perkin Elmer FT-IR
spectrometer in the range of 4000–400 cmÀ1. MP-AES (Agilent
Technologies 4210) was used to measure the metal content of
the catalyst. Powder X-ray diffraction (PXRD) data were collected
on Bruker AXS D8 Advance diffractometer. The thermogravimetric
analysis was performed with EXSTAR TG/DTA 6300 instrument
under air atmosphere. The surface morphology of the synthesized
material was analysed with the help of transmission electron
microscope (Technai G2 20 S-TWIN). BET surface area, pore volume
and pore diameter were analysed using Autosorb IQ2 (Quan-
tachrome Instrument). NMR spectra were recorded with Jeol ECX
400 MHz and Bruker spectrospin DPX 500 MHz spectrometers.
Chemical shifts (d) are reported in parts per million (ppm) and cou-
pling constants are expressed in Hz. 1H NMR chemical shifts are
given relative to residual chloroform or DMSO in deuteriated sol-
vent or with tetramethylsilane (TMS, d = 0.00 ppm) as internal
standard. 13C NMR spectra are referenced to CDCl3 and [D6] DMSO.
The following abbreviations denote the multiplicities: s = singlet,
d = doublet, t = triplet, m = multiplet. HRMS were recorded with
a micro TOF-Q II mass spectrometer in ESI mode.
3. Results and discussion
3.1. Characterization of complex
3.1.1. FT-IR spectroscopy
The FT-IR spectra of MCM-41, MCM-41@PDCA and MCM-
41@PDCA-Co are shown in Fig. 1. The FT-IR spectrum of MCM-41
shows bands at 3400 and 1634 cmÀ1 which are associated with
OAH stretching and bending vibration of surface hydroxyl groups
and physisorbed water. The spectrum also shows bands at 1230
and 1080 cmÀ1 due to SiAOASi asymmetric stretching mode,
800 cmÀ1 due to SiAOASi symmetric stretching mode, 463 cmÀ1
due to SiAOASi bending vibration and the peak at 960 cmÀ1 due
to the SiAO stretching of SiAOH (Fig. 1a). After grafting of PDCA
on to MCM-41, new peaks appeared at 2940 and 1454 cmÀ1 due
to CAH stretching and bending vibration, 1650 cmÀ1 due to C@O
stretch, 1549 cmÀ1 due to NH bending of amide (Fig. 1b). The char-
acteristic band for amide carbonyl group at 1650 cmÀ1 shifted to
lower wave number upon the coordination of cobalt chloride with
PDCA immobilized on MCM-41, confirms the coordination of
cobalt (II) ion with the carbonyl oxygen of PDCA (Fig. 1c) in resul-
tant catalyst, MCM-41@PDCA-Co.
2.2. Synthesis of MCM-41@PDCA-Co catalyst
2.2.1. Synthesis of N2, N6-bis(3-(triethoxysilyl)propyl)pyridine-2,6-
dicarboxamide (PDCA)
3-aminopropyltriethoxysilane (1.32 g, 6.00 mmol) and triethyl
amine (0.65 g, 6.50 mmol) was dissolved in 20 ml of dry THF and
degassed under nitrogen. Then a solution of 2,6-pyridinedicar-
boxylic acid chloride (0.61 g, 3.00 mmol) in 30 ml of dry THF
was added drop wise with constant stirring and the resulting solu-
tion was further stirred for 2 h at room temperature under nitro-
gen. The white precipitate was obtained and separated by
filtration. The filtrate was evaporated and the ligand was obtained
as yellow oil with yield 97.73% (1.68 g, 2.93 mmol). 1H NMR
(400 MHz, CDCl3): d 8.27 (d, J = 7.7 Hz, 2H), 8.02 (m, 2H), 7.94 (t,
J = 7.2 Hz,1H), 3.45 (q, J = 6.8 Hz, 4H), 3.76 (t, J = 7.0 Hz, 12H),
1.72 (m, J = 7.6 Hz, 4H), 1.15 (t, J = 6.9 Hz, 18H), 0.66 (t,
J = 8.0 Hz, 4H), 13C NMR (100 MHz, CDCl3): 163.65 (s), 149.06 (s),
138.56 (s), 124.88 (s), 58.52 (s), 42.80 (s), 23.33 (s), 18.29 (s),
7.95 (s).
3.1.2. Powder XRD studies
The XRD patterns of MCM-41, MCM-41@PDCA and MCM-
41@PDCA-Co are shown in the Fig. 2. The XRD pattern of MCM-
41 showed one intense peak at 2h = 2.68° assigned to 100 reflection
plane of MCM-41 structure and three weak peaks at 2h = 4.48°,
5.12° and 6.64° assigned to 110, 200 and 210 planes respectively.
This demonstrated the well-ordered hexagonal mesoporous struc-
ture of MCM-41 (Fig. 2a) [33,34]. The intensity of the peaks corre-
sponding to 100, 110 and 200 planes decreased while the peak
corresponding to 210 reflection plane disappeared in the XRD pat-
tern of MCM-41@PDCA-Co (Fig. 2c). Besides, all the peaks slightly
shifted towards higher angle from their position. All these changes
2

S. Sharma, U.P. Singh and A.P. Singh
Polyhedron 199 (2021) 115102
Scheme 1. Synthesis of MCM-41@PDCA-Co.
Fig. 3. XRD patterns of (a) MCM-41@PDCA-Co and (b) Recovered MCM-41@PDCA-
Fig. 1. IR spectra of (a) MCM-41; (b) MCM-41@PDCA and (c) MCM-41@PDCA-Co.
Co.
Fig. 2. XRD patterns of (a) MCM-41; (b) MCM-41@PDCA and (c) MCM-41@PDCA-
Co.
Fig. 4. TGA patterns of (a) MCM-41; (b) MCM-41@PDCA-Co.
indicated that cobalt (II) complex of PDCA was successfully immo-
bilized on the surface of mesoporous MCM-41 and the mesoporous
structure of MCM-41 was intact. The PXRD gives no information
about the catalyst degradation (physical damage) (Fig. 3).
MCM-41@PDCA-Co (Fig. 4b) showed a significant weight loss by
22.5 wt - % between 25 and 125 °C besides a weight loss by
7.9 wt - % between 300 and 450 due to loss of organic group in
ligand. This suggested that cobalt (II) complex was successfully
immobilized onto the mesopores of MCM-41.
3.1.3. Thermo gravimetric analysis (TGA)
TGA study of MCM-41 (Fig. 4a) revealed 10–11 wt - % weight
loss in the region of 25–100 °C due to the removal of adsorbed
water. A further weight loss by 1 wt - % in the region of 100–
300 °C was observed due to the desorption of the chemisorbed
water on the silica surface [35]. In comparison with MCM-41,
3.1.4. N2 sorption
The nitrogen sorption isotherms for MCM-41 and MCM-
41@PDCA-Co are shown in the Fig. 5. The MCM-41 exhibited a
type-IV isotherm with hysteresis loop, which is the characteristic
3

S. Sharma, U.P. Singh and A.P. Singh
Polyhedron 199 (2021) 115102
and 2.049 nm respectively (Fig. 5b). This decrease in surface area,
pore volume and pore diameter demonstrated that cobalt (II) com-
plex has been immobilized of onto the mesopores of MCM-41.
3.1.5. SEM
SEM images of MCM-41, MCM-41@PDCA-Co catalyst and spent
catalyst are all shown in Fig. 6. This illustrates that there is no sig-
nificant change in the morphology of mesoporous material MCM-
41 and MCM-41@PDCA-Co and used catalyst. However, minor
agglomeration of particles is observed in the spent catalyst which
may lead to a little decrease in the surface area. This might be the
reason for the gradual decrease in the catalytic efficiency from 98%
to 91% after six successive runs.
3.1.6. TEM
The mesoporosity of MCM-41 and MCM-41@PDCA-Co was eval-
uated by transmission electron microscopy (TEM) (Fig. 7). It was
observed that both materials exhibited an arrangement of well-
ordered mesopores with a narrow pore size distribution suggesting
no significant change in the meso structure of MCM-41 after the
loading of cobalt (II) complex
Fig. 5. N2 adsorption–desorption isotherms of (a) MCM-41; (b) MCM 41@PDCA-Co.
on MCM-41.
of mesoporous structure [36]. BET (Brunauer-Emmett-Teller) sur-
face area and pore volume of MCM-41 were found to be
788 m2 gÀ1 and 0.569 cm3 gÀ1 respectively (Fig. 5a). The pore
diameter of MCM-41 is 3.55 nm, calculated by DFT (density func-
tional theory). The BET surface area, pore volume and the pore
diameter of MCM-41@PDCA-Co are 542 m2 gÀ1, 0.264 cm3 gÀ1
3.1.7. MP-AES analysis
The cobalt loading in catalyst was measured by microwave
plasma atomic emission spectroscopy MP-AES analysis. The exper-
iment revealed that the cobalt content of the catalyst is 0.22 mmol
per gram of MCM-41@PDCA-Co.
Fig. 6. SEM image of (a) MCM-41; (b) MCM-41@PDCA-Co; (c) recovered catalyst MCM-41@PDCA-Co.
4

S. Sharma, U.P. Singh and A.P. Singh
Polyhedron 199 (2021) 115102
Fig. 7. TEM micrographs of (a) MCM-41; (b) MCM-41@PDCA-Co.
Table 1
Optimization of the reaction condition for the synthesis of ethyl 2,7,7-trimethyl-5-oxo-4-phenyl-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate catalysed by MCM-41@PDCA-Co
under various conditions with 10.00 mg of the catalyst, the product yield increased to 94% within 10 min (Table 1, entry 6) at 100 °C but further increase in catalyst amount (i.e.
12.00 mg) did not affect the yield of the product (Table 1, entry 7). The experiment was tried with other solvents system, such as ethanol, 2-ethoxy ethanol, glycol, glycerol, THF,
water, DMF and DMSO but the yields of polyhydroquinoline was not very encouraging.
Entry
Solvent
Temp.
Catalyst
(mg)
Time
Yieldb
1
2
3
4
5
6
7
8
Solvent free
Solvent free
Solvent free
Solvent free
Solvent free
Solvent free
Solvent free
Ethanol
2-ethoxy ethanol
Glycol
Glycerol
THF
H2O
rt & 100 °C
rt
–
3
3
5
24 h
24 h
12 h
4 h
NR
Trace
42
57
78
94
94
82
86
79
76
46
76
35
32
90
100 °C
100 °C
100 °C
100 °C
100 °C
reflux
reflux
reflux
reflux
reflux
reflux
reflux
reflux
130 °C
8
30 min
10 min
10 min
10 min
10 min
10 min
10 min
10 min
10 min
10 min
10 min
10 min
10
12
10
10
10
10
10
10
10
10
10
9
10
11
12
13
14
15
16
DMF
DMSO
Solvent free
Reaction condition: demidone (1.00 mmol), benzaldehyde (1.00 mmol), ethylacetoacetate (1.00 mmol), NH4OAc (1.20 mmol) and catalyst (10.00 mg) at 100 °C for 10 min,
neat. bfinal yield.
3.1.8. Catalytic performance of MCM-41@PDCA-Co in the synthesis of
polyhydroquinoline
tested. We performed our reaction as proposed in the experimental
section.
In order to optimize the reaction condition, various factors such
as amount of catalyst, solvent and effect of temperature have been
According to the optimized result, it has been found that in the
absence of catalyst at room temperature to 100 °C, the reaction
5

S. Sharma, U.P. Singh and A.P. Singh
Polyhedron 199 (2021) 115102
Table 2
Synthesis of different polyhydroquinolines using optimized conditions.
Entry
1.
Aldehyde
Active methylene compound
Product
Yield
94
2.
90
3.
88
4.
88
5.
96
6

S. Sharma, U.P. Singh and A.P. Singh
Polyhedron 199 (2021) 115102
Table 2 (continued)
Entry
6.
Aldehyde
Active methylene compound
Product
Yield
98
7.
8.
9.
98
97
98
10.
94
11.
92
(continued on next page)
7

S. Sharma, U.P. Singh and A.P. Singh
Polyhedron 199 (2021) 115102
Table 2 (continued)
Entry
12.
Aldehyde
Active methylene compound
Product
Yield
88
13.
89
14.
94
15.
96
16.
96
17.
94
8

S. Sharma, U.P. Singh and A.P. Singh
Polyhedron 199 (2021) 115102
Table 2 (continued)
Entry
18.
Aldehyde
Active methylene compound
Product
Yield
85
19.
97
Reaction condition: active methylene compound (1.00 mmol), benzaldehyde (1.00 mmol), ethylacetoacetate (1.00 mmol), NH4OAc (1.20 mmol) and catalyst (10.00 mg) at
100 °C for 10 min, neat.
Table 3
Comparison of Co-catalyst with other reported catalysts for the synthesis of polyhydroquinolines.
Entry
1
Substrate
Catalyst
Catalyst (mg)
50
Time(min)
145
Yield%
96
Reference
[37]
p-chloro
Fe3O4-Adenine-Ni
benzaldehyde
p-chloro
benzaldehyde
p-chloro
benzaldehyde
p-choloro
benzaldehyde
p-chloro
benzaldehyde
p-chloro
benzaldehyde
p-chloro
benzaldehyde
p-chloro
2
3
4
5
6
7
8
Fe3-xTixO4-SO3H
20
20
8
5
87
95
96
96
97
96
98
[38]
TEDETA@BNPs
60
[39]
MCM-41@Serine@Cu(II)
Ni-dithiazone@boehmite
SBA-15@AMPD-Co
170
280
35
[40]
25
7
[41]
[29]
Fe3O4@MCM-41@Cu-P2C
MCM-41@PDCA-Co
20
10
180
10
[42]
This work
benzaldehyde
failed to give the product (2j) and the starting materials were
recovered quantitatively (Table 1, entry 1). Furthermore, it was
found that the use of catalyst (3.00 mg) at room temperature
was also inactive for the production of polyhydroquinoline (Table 1,
entry 2). Even an increase in reaction temperature with 3.00 mg
catalyst loading produced only 42% yield of the desired product
(2j) in 12 h (Table 1, entry 3). When the catalyst amount was
increased to 5.00 mg and 8.00 mg, the product yield was enhanced
by 57% and 78% respectively in a short time (Table 1, entry 4, 5).
In other set of experiment, we tried the reaction with a wide
range of benzaldehyde and active methylene compound to deter-
mine the effect of electronic and steric factors on the efficiency
of the catalyst. It is noteworthy that the reaction tolerated diverse
substituent on the benzaldehyde and the electronic properties of
aryl substituent bearing either electron- withdrawing or electron
releasing groups have a negligible effect on the reaction efficiency
(Table 2). It was observed that the presence of electron-donating
groups like methyl and methoxy slightly lowers the yield of the
product but the electron-withdrawing groups such as nitro, fluoro
and chloro slightly increase the yields of the product. In the case of
2, 6 dichloro benzaldehyde, the product yield slightly decreases
due to steric hindrance (see Table 3).
3.1.9. Mechanism
The suggested mechanism for the synthesis of polyhydroquino-
line is shown in Scheme 2. According to literature, the formation of
product goes by two different paths. In the mechanism, MCM-
41@PDCA-Co acts as a Bronsted acid that activates carbonyl com-
pounds (1a, 1b and 1c) for amine formation (B, F) and Knoevenagel
condensation product (A, G) as a key intermediate. According to
path I, demidone 1a react with ammonia (NH3) to form amine F.
The resulting amine reacts with adduct G in a conjugate manner
to produce adduct H. The adduct H tautomarizes into adduct I
which converts into the final product polyhydroquinoline 2j by
intramolecular cyclization followed by dehydration. In the path II
all steps are same as path I except the formation of Knoevenagel
adduct A and amine B.
3.1.10. Catalyst reusability
The reusability and stability are the most important properties
of any new prepared heterogeneous catalyst. These properties
were investigated in the synthesis of polyhydroquinoline. After
the reaction, ethanol was added in the reaction vessel and refluxed
till the suspension was formed. The catalyst was filtered, washed
with DCM (4 Â 10) and ether (3 Â 10), dried in a hot air oven at
9

S. Sharma, U.P. Singh and A.P. Singh
Polyhedron 199 (2021) 115102
Scheme 2. Proposed mechanism.
occurred, MP-AES analysis was carried out for the catalyst recov-
ered from the six successive runs and it was found that cobalt con-
tent in the recovered catalyst was 0.217 mmol/g which is very
close to 0.22 mmol/g, a cobalt loading on the fresh catalyst. This
indicates that no significant leaching of cobalt occurred during
the reaction.
4. Conclusion
In summary, an efficient heterogeneous MCM-41@PDCA-Co cat-
alyst was prepared via a simple method. The catalyst revealed very
high activity for the synthesis of polyhydroquinolene (98%)
through one-pot multi-component reaction under solvent free
condition. Low catalyst loading, very short reaction time, high
yield, easy separation by simple filtration and reusability for at
least six successive runs are among the main advantages of the
catalyst.
Fig. 8. Recovery of the catalyst in the synthesis of polyhydroquinoline.
CRediT authorship contribution statement
60 °C for 3 h. The separated catalyst was reused for 6 successive
runs in the synthesis of polyhydroquinoline as shown in Fig. 8. It
showed that catalyst worked efficiently without loss of catalytic
activity. Moreover, in order to confirm that no cobalt leaching
Saurabh Sharma: Conceptualization, Investigation, Methodol-
ogy, Original draft preparation. Udai P. Singh: Formal analysis,
Funding acquisition, Supervision, Writing - Reviewing and Editing.
A.P. Singh: Reviewing and editing.
10

S. Sharma, U.P. Singh and A.P. Singh
Polyhedron 199 (2021) 115102
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(2009) 1754–1756.
Declaration of Competing Interest
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The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgment
The authors are grateful to the Board of Research in Nuclear
Sciences, India, Grant No. 37018 (DAE), Mumbai, India for financial
assistance. S. Sharma is thankful to UGC for fellowship.
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Appendix A. Supplementary data
Supplementary data to this article can be found online at
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