Efficient one-pot synthesis of polyhydroquinoline derivatives through the Hantzsch condensation using IRMOF-3 as heterogeneous and reusable catalyst

Article abstract of DOI:10.1002/jccs.202000303

A mesoporous Zn-based 2-amino terephthalate metal organic framework (IRMOF-3) catalyst was prepared using the solvothermal method. The synthesized catalyst was characterized by powder X-ray diffraction (XRD), thermogravimetric analysis (TGA), Fourier tran

Full text of DOI:10.1002/jccs.202000303

Received: 14 July 2020
Revised: 18 September 2020
Accepted: 22 October 2020
DOI: 10.1002/jccs.202000303
A R T I C L E
Efficient one-pot synthesis of polyhydroquinoline
derivatives through the Hantzsch condensation using
IRMOF-3 as heterogeneous and reusable catalyst
Vaishali N. Rathod | Nilam D. Bansode | Premkumar B. Thombre |
Machhindra K. Lande
Department of Chemistry, Dr. Babasaheb
Abstract
Ambedkar Marathwada University,
Aurangabad, Maharashtra, India
A mesoporous Zn-based 2-amino terephthalate metal organic framework
(IRMOF-3) catalyst was prepared using the solvothermal method. The synthe-
sized catalyst was characterized by powder X-ray diffraction (XRD), ther-
mogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-
IR), scanning electron microscopy (SEM), energy-dispersive spectroscopy
(EDAX), and Brunauer–Emmett–Teller surface area analysis (BET). It was
applied as an effective heterogeneous catalyst for the synthesis of one-pot four-
component polyhydroquinoline derivatives via the Hantzsch condensation.
The present method offers several advantages over other reported methods
such as easy separation, mild reaction condition, and excellent yield of desired
product. Furthermore, the catalyst can be reused without loss in activity.
Correspondence
Machhindra K. Lande, Department of
Chemistry, Dr. Babasaheb Ambedkar
Marathwada University, Aurangabad,
Maharashtra 431004, India.
Email: mkl_chem@yahoo.com
K E Y W O R D S
heterogeneous, metal organic framework, polyhydroquinoline, solvothermal
1 | INTRODUCTION
for the synthesis of polyhydroquinoline derivatives
(Scheme 1).
A metal organic framework (MOF) is a crystalline, meso-
porous, designable material; these are building blocks of
metal ions linked by organic linker binding with a strong
bond.1 They have extensive applications in gas storage,2
gas separation,3 and catalytic reaction4 due to their tun-
able pore size, good thermal stability, large surface area,
good chemical stability, intact catalytic properties, and
multiple catalytic sites—either metal cluster, organic
linker, or both.5 Considering this view, we have success-
fully synthesized a zinc-based 2-amino terephthalate
metal organic framework (IRMOF-3) catalyst. It was
characterized by Fourier transform infrared spectroscopy
(FT-IR), energy-dispersive spectroscopy (EDAX), scan-
ning electron microscopy (SEM), Brunauer–Emmett–
Teller surface area analysis (BET), and powder X-ray dif-
fraction (XRD) and was used as a heterogeneous catalyst
In recent years, much attention has been focused on
the synthesis of 1,4 dihydropyridine (1,4 DHP) because of
their significant pharmacological and biological proper-
ties.64-substituted 1,4 DHP compounds are well known
as Ca+2 channel modulators7 and have emerged as one of
the most elevated classes of drugs for the treatment of
cardiovascular disease, including effective treatment of
hypertension.7b,8,9 1,4 DHP compounds are found in a
variety of biological activities such as hepatoprotective,
antidiabetic, geroprotective, hepatoprotective bronchodi-
lator, vasodilator, atherosclerotic, antitumor agent, and
antidiabetic activities.8d,10,11 For this reason, the synthe-
ses of the polyhydroquinoline compound has not only
captivated attention but also represents an interesting
research challenge to chemists.12 Numerous methods
have been reported for the structurally related synthesis
J Chin Chem Soc. 2021;68:601–609.
http://www.jccs.wiley-vch.de
© 2021 The Chemical Society Located in Taipei & Wiley-VCH GmbH
601

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RATHOD ET AL.
SCHEME 1 IRMOF-3
catalyzed unsymmetrical
Hantzschreaction
of polyhydroquinoline derivatives and of the biologically
importance associated with these compound, and there are
many classical methods, as well as various catalysts, such as
silica per chloric acid (HClO4-SiO2)13, ionic liquid14,
heteropoly acid,15 iron (II) trifluoro acetate16, trimethyl silyl
and 2-amino terephthalic acid was mixed drop wise with
constant stirring. The resulting mixture was transferred
in a Teflon-lined stainless steel 100-ml autoclave, treated
solvothermally under a static condition and autogenous
pressure at 130ꢀC for 24 hr, and then, the solvothermal
reaction product was cooled naturally. The obtained com-
pound was dried under vacuum in vacuum desiccators.
The synthesized IRMOF-3 heterogeneous catalyst was
characterized and catalyzed for synthesis of poly-
hydroquinoline derivatives (5a–j).
chloride (TMSCl),17 HY-zeolite,18 Sc(OTf)3, Yb (OTf)3
19
montmorillonite K-10,20 and silica-supported sulfuric acid
(SSA); each of the methods offers different advantages for
the Hantzsch condensation but, at the same time, suffer
from certain drawbacks such as longer reaction time, unsat-
isfactory yields, toxic catalysts, expensive catalysts, harsh
reaction conditions, difficult workup, and nonreusable cata-
lysts. Hence, in order to overcome these limitations, it is
necessary to develop an efficient, cost-effective, and eco-
friendly protocol synthesis of polyquinoline derivatives.
Here, we report a facile nonsymmetric Hantzsch con-
densation in the presence of an IRMOF-3 heterogeneous
catalyst under the reflux condition using substituted alde-
hyde (1), 5,5- dimethyl-1,3-cyclohexanedione (2), ethyl
acetoacetate (3), and ammonium acetate (4) to frame
polyhydroquinoline derivatives (5a–j) in excellent yield.
2.2 | General procedure for preparation
of polyhydroquinoline
A mixture of aldehyde (1 mmol), 5,5-dimethyl-1,3-
cyclohexanedione (1 mmol),ethyl acetoacetate (1 mmol),
and ammonium acetate (1 mmol) with
a catalyst
IRMOF-3 (40 mg) was refluxed in ethanol with constant
stirring for 2–3 hr, and the reaction was monitored by
using thin layer chromatography (TLC) (pet ether: ethyl
acetate (8:2) as the solvent system. After completion of
the reaction, the mixture was poured into crushed ice.
The precipitate reaction mass was filtered and was puri-
fied by recrystallization from ethanol to afford the desired
compound in pure form (5a–j).
2 | CHEMICAL AND
INSTRUMENTATION
All solvents and chemicals were of analytical grade and
were purchased from Merck, Spectrochem, HPLC, and
absolute and were used as such. FT-IR analysis was
recorded by using attenuated total reflection (ATR) on a
Bruker instrument. Powder XRD patterns were recorded
by a D8 advance Bruker X-ray diffractometer using mono-
2.3 | Spectral data of representative
sample
2.3.1 | Ethyl-1, 4, 7, 8-tetrahydro-2, 7,
trimetyl-4-(phenyl)-5(6H)-oxoquinolin-3
carboxylate (5a)
1
chromatic Cu-Kα radiation (λ = 1.5405 Ao). H and 13C
NMR spectra were recorded on a 400 MHZ FT-NMR spec-
trometer with dimethyl sulfoxide (DMSO) as the solvent.
1HNMR (DMSO-d6): 0.84 δ (s, 3H CH3), 1.01 δ (s, 3H
CH3), 1.11–1.14 δ (t, 3H CH3), 2.27–2.31 δ (m, 4H
2xCH2), 2.40 δ (s, 3H CH3), 3.95–4.00 δ (q, 2H CH2), 4.86
δ (s, 1H CH), 9.08 δ (s, 1H NH), 7.05–7.08 δ (m, 1H Ar-
H), 7.15–7.20 δ (m, 4H Ar-H). 13C NMR (DMSO-d6):
14.11, 18.26, 26.40, 29.11, 32.10, 50.19, 59.00, 103.56,
109.93, 125.65, 144.65, 166.81, 194.24. FT-IR (ATR, ν
cm−1): 3,280, 1,693, 1,605, 1,202. HRMS: m/z = 340.19.
2.1 | Synthesis of IRMOF-3
Zinc nitrate hexahydrate (3.75 g) and 2-amino ter-
ephthalic acid (H2ATA) (0.75 g) were dissolved separately
in 30 ml of dimethylformamide (DMF) and 10 ml of etha-
nol with mild stirring. The clear solution of zinc nitrate

RATHOD ET AL.
603
FIGURE 2 IR Spectrum of ligand
FIGURE 1 XRD pattern of IRMOF-3. (a) Newly prepared
(black). (b) Used four times for 5b (red)
TABLE 1 Selected FT-IR frequencies (cm−1) of the ligand and
IRMOF-3
Ligand/MOF
Ligand
ν(C=O)
1,713
1,586
ν(C=N)
1,315
1,311
ν(C=C)
1,553
1,538
FIGURE 3 FT-IR spectrum of IRMOF-3 catalyst
IRMOF-3
2xCH2), 2.43 δ (s, 3H CH3), 3.93–3.99 δ (q, 2H CH2), 4.97
δ (s, 1H CH), 9.28 δ (s, 1H NH),7.50–7.56 δ (m, 2H Ar-H),
7.96–7.99 δ (m, 2H Ar-H). 13C NMR (DMSO-d6): 13.98,
18.33, 26.27, 32.17, 49.95, 102.58, 109.17, 129.41, 146.13,
166.35, 194.32. FT-IR (ATR, ν cm−1): 3,204, 1,699,
1,602, 1,527, 1,348.
2.3.2 | Ethyl-1, 4, 7, 8-tetrahydro-2, 7,
trimetyl-4-(4 Chloro phenyl)-5(6H)-
oxoquinolin-3 carboxylate (5b)
1HNMR (DMSO-d6): 0.83 δ (s, 3H CH3), 1.01 δ (s, 3H CH3),
1.10–1.14 δ (t, 3H CH3), 2.26–2.29 δ (m, 4H 2xCH2), 2.40 δ
(s, 3H CH3), 3.94–3.99 δ (q, 2H CH2), 4.84 δ (s, 1H CH),
9.13 δ (s, 1H NH), 7.14–7.17 δ (m, 2H Ar-H), 7.23–7.26 δ
(m, 2H Ar-H). 13C NMR (DMSO-d6): 14.09, 18.27, 26.38,
32.11, 35.55, 40.08, 50.10, 59.09, 103.05, 109.61, 127.67,
129.29, 145.40, 166.61, 194.25. FT-IR (ATR, ν cm−1):
3,270, 1,700, 1,641, 1,204. HRMS: m/z = 374.15.
2.3.4 | Ethyl-1, 4, 7, 8-tetrahydro-2, 7,
trimetyl-4-(4 hydroxy phenyl)-5(6H)-
oxoquinolin-3 carboxylate (5d)
1HNMR (DMSO-d6): 0.85 δ (s, 3H CH3), 1.06 δ (s,3H
CH3), 1.12–1.15 δ (t,3H CH3), 2.25–2.29 δ (m, 4H 2xCH2),
2.38 δ (s, 3H CH3), 3.96–3.98 δ (q, 2H CH2), 4.74 δ (s, 1H
CH), 9.06 δ (s, 1H NH), 6.54–6.57 δ (m, 2H Ar-H), 6.92–
6.94 δ (m, 2H Ar-H), 8.99 δ (s, 1H Ar-OH). 13C NMR
(DMSO-d6): 14.15, 18.23, 29.15, 32.10, 50.25, 58.42,
104.06, 110.28, 114.39, 138.38, 144.37, 166.98. FT-IR
(ATR, ν cm−1): 3,273, 1,680, 1,605, 1,213. HRMS: m/
z = 356.18.
2.3.3 | Ethyl-1, 4, 7, 8-tetrahydro-2, 7,
trimetyl-4-(3 nitro phenyl)-5(6H)-
oxoquinolin-3 carboxylate (5c)
1HNMR (DMSO-d6): 0.83 δ (s, 3H CH3), 1.05 δ (s, 3H
CH3), 1.09–1.13 δ (t, 3H CH3), 2.29–2.35 δ (m, 4H

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RATHOD ET AL.
FIGURE 4 SEM image of IRMOF-3 catalyst
2.3.5 | Ethyl-1, 4, 7, 8-tetrahydro-2, 7,
trimetyl-4-(4 fluoro phenyl)-5(6H)-
oxoquinolin-3 carboxylate (5j)
1HNMR (DMSO-d6): 0.83δ(s, 3H CH3), 1.00 δ (s, 3H
CH3), 1.10–1.13 δ (t,3H CH3), 2.26–2.30 δ (m, 4H 2xCH2),
2.39 δ (s, 3H CH3), 3.94–3.99 δ (q, 2H CH2), 4.84 δ (s, 1H
CH), 9.11 δ (s, 1H NH), 6.98–7.02 δ (m, 2H Ar-H), 7.14–
7.18 δ (m, 2H Ar-H). 13C NMR (DMSO-d6):14.09, 18.26,
26.38, 32.11, 35.24, 40.07, 50.12, 59.04, 103.37, 109.86,
114.43, 129.15, 143.81, 166.69, 194.27. FT-IR (ATR, ν
cm−1): 3,270, 1,702, 1,641, 1,212.
3 | RESULT AND DISCUSSION
3.1 | Powder X-ray diffraction
Powder XRD patterns of IRMOF-3 are given in Figure 1.
According to the calculation (JCPDS Id No. 47-2088 PDF#
472088, wavelength = 1.5418, volume [CD]- 1,467.47),
which indicates an intense peak at 2θο = 19.436, 34.680,
31.433, and 50.723 with corresponding planes of (300),
(501), (421), and (304), respectively, the presence of planes
is found in the tetragonal phase of IRMOF-3 material. The
XRD patterns of IRMOF-3 show that the crystallinity and
integrity were intact after the organic transformations, as
shown Figure 1a,b. Therefore, IRMOF-3 is a thermally and
chemically stable heterogeneous catalyst.
FIGURE 5 EDAX spectrum of IRMOF-3 catalyst
FIGURE 6 TGA analysis of IRMOF-3 catalyst
3.2 | Infrared spectroscopy analysis
ions. The IR spectrum of IRMOF-3 shows two peaks in
3,453 and 3,340 cm−1 due to the existence of the amino
group of the NH2-terephthalic acid ligand.20 The selected
spectrum data of the 2-amino terephthalic acid and IRMOF-
The infrared spectroscopy (IR Spectroscopy) spectrum
indicated valuable information concerning the nature of
the function group of the ligand coordinated to the metal

RATHOD ET AL.
605
TABLE 2 Optimization of IRMOF-
3 catalyst and solvent effect on the
synthesis of 5b
Entry
Solvent
THF
Catalyst (mg)
Time (hr)
Yield (%)a
1
2
3
4
5
6
7
8
9
40
40
40
40
30
—
10
20
40
2
72
70
71
70
69
40
65
80
95
Toluene
DCM
1.5
2
Chloroform
Acetonitrile
Ethanol
Ethanol
Ethanol
Ethanol
1.5
2
8
2
2
2
aIsolated yield.
3-based MOF are given in Table 1.The absorption band is in
the range of 1,713–1,590 cm−1 due to the presence of C=O
group in the 2-amino terephthalic acid ligand (Figure 2). The
absorption band of IRMOF-3 was found to be in the range of
1,586–1,538 cm−1, the results of which confirmed the coordi-
nation of the C=O group of 2-amino terephthalic acid ligand
with Zn metal salts (Figure 2). C=N and C=C stretching fre-
quency was observed in the range of 1,315–1,224 and 1,553–
1,416 cm−1, respectively, but it decreased in IRMOF—1,311–
1,221 and 1,520–1,412 cm−1. Thus, this result confirms that
the organic acid coordinated to the metal ion to form the tar-
get compound (Figure 3).
The TGA curve shows two weight losses. The first weight
loss (7.304%) was found in the range between 80 and
200ꢀC; it indicates the loss of moisture. The second
weight loss (54.309%) started in the range 450–800ꢀC,
temperatures at which the structure of the IRMOF-3 col-
lapsed and the 2-amino terephthalate was fractured. It
found that the synthesized IRMOF-3 was stable up to
450ꢀC (Figure 6).
3.6 | Optimization of reaction condition
We aimed to find the optimal condition by examining the
mixture of 4-chloro benzaldehyde (1 mmol), dimedone
(1 mmol), ethyl acetoacetate (1 mmol), and ammonium
acetate (1 mmol) as a model reaction with different
amounts of the heterogeneous catalyst IRMOF-3 under
the reflux condition for the synthesis of poly-
hydroquinoline derivatives in high yields. We also stud-
ied the efficiency of model reaction carried out under the
different polar and non polar solvent chooses as the
medium shown Table 2. We found that the reaction
proceeded faster in a polar solvent, such as ethanol and
acetonitrile, and these solvents were much better than
nonpolar solvents.
3.3 | Scanning electron microscopy
SEM used to study the surface morphology of IRMOF-3 is
shown in Figure 4. The SEM image observed crystalline and
irregular duab shape particle morpholog.
The element compositions of the IRMOF-3 catalyst are
given in Figure 5, which includes elements of zinc (14.24%),
carbon (46.12%), and oxygen (26.28%) (F(0.80%), Cu (0.65%)
trace amount analyzed impurity). The EDS study found that
the elements zinc, carbon and oxygen are present, which
confirms the successful synthesis of IRMOF-3.
We then continued to optimize the conditions elec-
tronically to test diverse different aromatic aldehydes,
and results are summarized in Table 3. Aldehydes having
an electron-withdrawing group such as 4-Cl, 4-NO2, 3-
NO2, and 4-F were found to be highly reactive and gave
maximum yield of the product compared to aldehydes
with an electron-releasing group such as 4-OH, 3-OH,
and 4-Ome. After optimizing the reaction conditions,
efforts were made toward the recovery and reusability of
the IRMOF-3 catalyst. The catalyst was removed after the
completion of the reaction by dissolving the reaction mix-
ture in hot ethanol and filtration. The recovered catalyst
was washed four to five times with DMF and then
immersed in methanol for 24 hr and dried at 130ꢀC for
3.4 | BET surface area and porosity
The BET surface area, average pore diameter, and pore vol-
ume of IRMOF-3 were found to be 130.69 m2/g, 48.53 Aꢀ,
and 0.436 cm2/g, respectively, calculated by the N2 absorp-
tion desorption barrett-joyner-halenda (BJH) isotherm.
3.5 | Thermogravimetric analysis of
IRMOF-3 catalyst
Thermo gravimetric analysis (TGA) was performed to
determine the thermal stability of synthesized IRMOF-3.

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RATHOD ET AL.
TABLE 3 IRMOF-3-catalyzed
synthesis of polyhydroquinoline
derivatives
Melting point (ꢀC)
Sr.no.
Product
Entry
Yield (%)a
Observed
Reported
1
2
3
4
5a
91
203–204
202–20419
245–24621
177–17822
232–23419
5b
5c
5d
95
92
91
244–245
176–177
233–234
5
6
7
5e
5f
89
88
91
225–230
255–256
241–243
—
256–25719
242–24421
5g
8
5h
5i
86
87
92
254–256
239–241
184–186
253–25519
238–24022
184–18619
9
10
5j
Note: Reaction condition: aldehyde (1 mmol), dimedone (1 mmol), ethyl acetoacetate (1 mmol) and
ammonium acetate (1 mmol), Catalyst (40 mg) and ethanol (10 ml).
aIsolated yield.

RATHOD ET AL.
607
TABLE 4 Recyclability studies of IRMOF-3 catalyst for the
synthesis of 5b
3 hr before the next catalytic run, which could be subse-
quently performed several times,as shown in Table 4, for
compound 5b. Reusability of the catalyst was investigated
four times, and it was found that the catalyst has intact,
almost consistent activity.
The plausible reaction mechanism shows the prepara-
tion of the polyhydroquinoline derivatives. The IRMOF-3
catalyst enhances the electrophilicity of the carbonyl of
aldehyde, and then, the dimedone reacts with the
Entry
Cycle
Fresh
First
Yield (%)a
1
2
3
4
95
94
91
90
Second
Third
aIsolated yield.
SCHEME 2 Proposed reaction mechanism for IRMOF-3-catalyzed polyhydroquinoline synthesis
TABLE 5 Comparison of the
Entry
Catalyst
Yb(DTF)3
AlCl3
Temp
25
Time (hr)
Yield (%)a
Literature
catalytic performance of different
reported catalysts used in synthesis
of 5b
23
1
5
90
48
42
93
92
93
93
92
93
93
95
23
23
24
25
23
18
26
27
29
2
25
24
24
1.5
1
3
ZnCl2
25
4
I2
25
5
ZnO
80
6
Sc(OTf)3
Hy-zeolite
L-proline
Nano-γ-Fe2O3-SO3H
60
5
7
25
2
8
RT
6
9
60
1.5
1
2
10
11
SO4 /TiO2NPs
Reflux
Reflux
IRMOF-3
1–2
Our results
aIsolated yield.

608
RATHOD ET AL.
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acetoacetate and ammonium acetate to form intermediate
(II). Intermediates I and II undergo cyclocondensation to
obtain the final desired product (Scheme 2).
To specify the advantage of the defined methodology,
the results of different reported methods are compared
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4 | CONCLUSIONS
In summary, we have synthesized a mesoporous IRMOF-3
MOF catalyst using the solvothermal method. Efficient
catalytic activity has been developed for the synthesis
of polyhydroquinoline derivatives via the Hantzsch
condensation reaction. In the IRMOF-3 catalyst, there is
organization between the Lewis acidic site and rigid NH2-
benzenedicarboxylate linking in the zinc-based MOF
cluster. XRD, IR, BET, SEM analysis confirm the tetra-
gonal phase, greater porediameter, morphology observed
crystalline and irregular duab shape and it has no signifi-
cance loss of catalytic activity when used in organic trans-
formation for three to four run. This method offers
remarkable benefits over other reported methods, for
example, easy to separate, reusable catalytic characters,
nontoxic, short reaction time, large pore size, and provided
excellent yield of polyhydroquinoline derivatives (5a–j).
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ACKNOWLEDGMENTS
We are thankful to the head of the chemistry department,
Dr. Babashaheb Marathwada, University Aurangabad
(MS)-431004, India for providing necessary laboratory
facilities and to SAIF Chandigarh, SAIF STIC Cochin,
and SAIF Lucknow for characterization facilities. One of
the authors, VNR, is thankful to UGC Delhi for providing
faculty improvement programmers (FIP).
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How to cite this article: Rathod VN,
Bansode ND, Thombre PB, Lande MK. Efficient
one-pot synthesis of polyhydroquinoline
derivatives through the Hantzsch condensation
using IRMOF-3 as heterogeneous and reusable
catalyst. J Chin Chem Soc. 2021;68:601–609.
https://doi.org/10.1002/jccs.202000303
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