Sulfonamide-functionalized covalent organic framework (COF-SO3H): an efficient heterogeneous acidic catalyst for the one-pot preparation of polyhydroquinoline and 1,4-dihydropyridine derivatives

Article abstract of DOI:10.1007/s11164-020-04322-5

Herein, we report the sulfonamide-functionalized covalent organic framework (COF-SO₃H) prepared from melamine and terephthalaldehyde and subsequent sulfonation, as an acidic porous catalyst for the one-pot preparation of polyhydroquinoline and

Full text of DOI:10.1007/s11164-020-04322-5

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-020-04322-5
Sulfonamide‑functionalized covalent organic framework
(COF‑SO3H): an efcient heterogeneous acidic catalyst
for the one‑pot preparation of polyhydroquinoline
and 1,4‑dihydropyridine derivatives
Razieh Farsi1 · Mohammad Kazem Mohammadi1 ·
Seyyed Jafar Saghanezhad2
Received: 9 July 2020 / Accepted: 2 November 2020
© Springer Nature B.V. 2020
Abstract
Herein, we report the sulfonamide-functionalized covalent organic framework
(COF-SO3H) prepared from melamine and terephthalaldehyde and subsequent sul-
fonation, as an acidic porous catalyst for the one-pot preparation of polyhydroquino-
line and 1,4-dihydropyridine derivatives. COF-SO3H was characterized by FT-IR,
EDX, TGA, SEM, XRD, and BET. This methodology ofers several advantages
including high yield, short reaction time, simple workup procedure, solvent-free
conditions, ease of separation, and recyclability.
Electronic supplementary material The online version of this article (https://doi.org/10.1007/s1116
4-020-04322-5) contains supplementary material, which is available to authorized users.
*
Mohammad Kazem Mohammadi
mkmohamadi@gmail.com
1
2
Department of Chemistry, Islamic Azad University, Ahvaz Branch, Ahvaz, Iran
ACECR-Production Technology Research Institute, Ahvaz, Iran
Vol.:(0123456789)
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R. Farsi et al.
Graphic abstract
One-pot preparation of polyhydroquinoline and 1, 4-dihydropyridinederivatives
Keywords Covalent organic framework (COF) · Nanoporous · Melamine ·
Terephthalaldehyde · Acidic catalyst · Chlorosulfonic acid
Introduction
Over the past decade, interest in the feld of nanoporous materials as regular organic
or inorganic frameworks has grown tremendously because of their excellent porous
properties and broad applications [1]. As an emerging kind of crystalline porous
materials, covalent organic frameworks (COFs) pioneered by Yaghi and co-workers
in 2005 are composed of two organic moieties via strong covalent bonds between
light atoms (e.g., H, B, C, N, O, Si) to generate long-range ordered two-dimensional
(2D) or three-dimensional (3D) network structures [2–5]. A wide range of porous
organic polymers (POPs), which are also called porous organic materials [6], have
been introduced in the past two decades, such as COFs and various amorphous net-
works, such as hypercrosslinked polymers (HCPs), covalent triazine frameworks
(CTFs), porous aromatic frameworks (PAFs), and conjugated microporous polymers
(CMPs) [7–9]. Due to their fascinating properties, such as high surface area, vis-
cous cavities, and high porosity, low-density economical materials are obtained due
to the low-cost starting materials and the easy way of synthesis. High thermal and
chemical stability endows COFs with a wide application potential in the felds of
energy storage, gas adsorption, drug delivery, catalysis, sensing, and optoelectronics
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Sulfonamide‑functionalized covalent organic framework…
[10–15]. Functionalization in the course of synthesis and/or post-functionalization
of COFs endows their framework with specifc active sites, which could further
improve their catalytic activity or enhance their dispersion stability. Thus, it is of
great applicability to prepare a functionalized COF and to further investigate its cat-
alytic potential [16, 17].
Heterocyclic compounds containing nitrogen have attracted considerable atten-
tion due to their wide pharmaceutical activity range acting as antitumour, antiath-
erosclerotic, vasodilator, hepatoprotective, bronchodilator, antidiabetic activity.
1,4-Dihydropyridine (DHP) and polyhydroquinoline (PHQ) as nitrogen heterocy-
cles occupy a unique position in medicinal chemistry according to their widespread
range of biological applications [18–22]. Therefore, the development of facile syn-
thetic methodologies for preparation of these nitrogen-containing heterocycles is
of much importance. Experimentally the straightforward route for this goal was
frst reported by Hantzsch in 1882 via the reaction of an aldehyde, β-ketoester, and
ammonia in acetic acid or by refuxing ethanol for long reaction times, which typi-
cally leads to low yields [23–25].
Several more efcient and alternative methods have been introduced due to the
biological importance of DHP and PHQ derivatives for the synthesis of various drug
sources. Several catalysts have been reported for the synthesis of these compounds
such as cyanuric chloride [26], ionic liquids [27, 28], Yb(OTf)3 [29], silica gel/
NaHSO4 [30], PSA [31], L-proline [32], Sc(OTf)3 [33], p-TSA [34], ZnO [35], and
TMSCl [18].
However, most of these methods sufer from certain drawbacks such as long reac-
tion time, low yields of product, hard operation, high reaction temperatures, toxic
solvents, and utilization of expensive or unavailable catalysts. Furthermore, catalysts
are destroyed and cannot be recovered or reused in the majority of the proposed
methodologies.
Therefore, considering the above-mentioned weaknesses, and in continuation of
our pioneering research on preparation and application of new catalysts in the feld
of organic methodology [36, 37], we wish to report a facile and efcient synthesis
of DHP and PHQ derivatives through one-pot Hantzsch condensation reaction in the
presence of COF-SO3H under solvent-free neat conditions (Scheme 1).
Experimental
General
Chemicals were purchased from Chemical Companies with at least for synthe-
sis grade and were used without further purifcation. All yields refer to isolated
products. Products were characterized by comparison of their physical data such
1
as IR, H NMR and 13C NMR spectra with authentic samples. By using TMS as
an internal standard, NMR spectra were recorded in CDCl3 on a Bruker Advance
DPX 250 MHz spectrometer. Determination of the products’ purity in the course
of the reaction was monitored by TLC on silica gel polygram SILG/UV 254 plates.
IR spectra were recorded on a BOMEM MB-Series 1998 FT-IR spectrophotometer
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R. Farsi et al.
Scheme 1 One-pot preparation of 1,4-dihydropyridine (DHP) and polyhydroquinoline (PHQ) derivatives
via Hantzsch reaction
as KBr disks. The melting points were recorded in open capillary tubes and were
uncorrected. The SEM images and EDX-Map were recorded by TESCAN MIRA III
FESEM. The BET diagrams were recorded via BELSORP MINI II.
A general procedure for the synthesis of 1,4 ‑dihydropyridines derivatives catalyzed
by COF‑SO3H nanoparticles under solvent‑free conditions
A mixture of ethyl acetoacetate (0.26 g, 2 mmol), ammonium acetate (0.154 g,
2 mmol), aryl aldehyde (1 mmol) in the presence of COF-SO3H (0.02 g) as acid cat-
alyst was mixed in a test tube on the oil bath at 90 °C for adequate times under sol-
vent-free conditions as embedded in Table 3. The reaction monitoring was checked
by TLC. After the completion of the reaction as witnessed by TLC, ethanol was
added to the reaction mixture and the catalyst was fltered. The fltrate was collected
as crude product after cooling to room temperature. The product was recrystallized
from water–ethanol mixtures.
General procedure for synthesis of polyhydroquinoline derivatives catalyzed
by COF‑SO3H nanoparticles under solvent‑free conditions
A mixture of aryl aldehyde (1 mmol), dimedone (0.14 g, 1 mmol), ethyl acetoacetate
(0.13 g, 1 mmol), ammonium acetate (0.115 g, 1.5 mmol), in the presence of COF
(0.02 g) as acid catalyst was heated on the oil bath at 90 °C for adequate times under
solvent-free conditions as embedded in Table 4. The reaction mixture was checked
1 3

Sulfonamide‑functionalized covalent organic framework…
by TLC. After the completion of the reaction as witnessed by TLC, ethanol was
added to the reaction mixture and the catalyst was fltered. The fltrate was collected
as crude product after cooling to room temperature. The product was recrystallized
from water–ethanol mixtures.
Synthesis of melamine‑based covalent organic framework (COF)
Via a typical solvothermal method, according to a recent literature [1], melamine
(470 mg, 3.73 mmol) and terephthalaldehyde (750 mg, 5.59 mmol) were dis-
solved in DMSO (23 mL) in a Tefon-lined laboratory autoclave, which was heated
at 180 °C for 14 h. Subsequently, the product was washed thoroughly, with excess
acetone (30 mL×2) and dichloromethane (30 mL×2). Finally, a white powder was
obtained, which was dried in an oven at 60 °C for 12 h.
Synthesis of COF‑SO3H
Sulfonation of the COF was carried out using chlorosulfonic acid. In a typical syn-
thesis, 0.5 g of the COF was suspended in 20 ml chloroform in a 25-mL round-bot-
tomed fask. Then, 5 ml of chlorosulfonic in CH2Cl2 (10 mL) was added dropwise
over a period of 2 h at room temperature. Finally, the prepared catalyst was washed
several times with chloroform and dried in oven for 24 h at 60 °C. The acidity of
catalyst was determined by adding 0.02 g of the catalyst to 25 mL of NaCl (1 M)
which the pH of the solution was decreased from 6.5 to 2.48 after 1 h of stirring.
Accordingly, the acidity of the catalyst was determined to be 4.1 mmol H+/g.
Spectral data for selected compounds
4‑(3‑nitro‑phenyl)‑2,6‑dimethyl‑1,4‑dihydro‑pyridine‑3,5‑dicarboxylic acid diethyl
ester(5j). (Table 3 entry 10): Yield: 94%; m.p 166–168 °C (Lit. 166–168 °C) 45; IR
(KBr) νmax: 3342, 2988, 1705, 1645, 1207, 1109, 774. 1H NMR (250 MHz, CDCl3):
δ 1.21 (t, 6H, J 7 Hz), 2.35(s, 6H, 2CH3), 4.07 (q, 4H, J 3.3 Hz), 5.08 (s, 1H), 5.98
(s, 1H, NH), 7.26–8.11 (Aromatic). 13C NMR (62.5 MHz, CDCl3): δ 15.22, 20.57,
40.95, 60.95, 104.29, 109.7, 117.6, 128.8, 131.8, 146.6, 150.9, 168.1.
2,7,7‑Trimethyl‑5‑oxo‑4‑(4‑Boromophenyl)‑1,4,5,6,7,8‑hexahydroquinoline‑3‑car‑
boxylic acid ethyl ester (6e) (Table 4 entry 5): Yield: 95%; m.p 249–251 °C (Lit.
252–254 °C)48;IR (KBr) νmax: 3273, 3203, 3074, 1703, 1648, 1279, 1213.; 1HNMR
(250 MHz, CDCl3) δ 0.91 (s, 3H), 1.05 (s, 3H), 1.18 (t, J 7 Hz, 3H), 2.09–2.26 (m,
4H), 2.34 (m, 3H), 4.06 (q, J6.9 Hz, 2H), 5.00 (s, 1H), 6.54 (s, 1H), 7.15 (d, J 8 Hz,
2H),7.33 (d, J 8 Hz, 2H). 13C NMR (62.5 MHz, CDCl3): 15.2, 20.3, 28.0, 30.4, 33.6,
37.3, 41.9, 51.6, 60.9, 106.6, 112.6, 120.8, 130.8, 131.9, 144.8, 147.1, 149.6, 168.2,
196.6.
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R. Farsi et al.
Catalyst recycling and reuse
The acidic catalyst, COF-SO3H, was recycled and reused as follows: After the com-
pletion of the reaction as witnessed with TLC, the catalyst was separated from the
reaction mixture, and after washing thoroughly with hot ethanol, it was reused for
the next run. The recycling efciency of the COF-SO3H catalyst was determined by
using benzaldehyde, dimedone, and ethyl acetoacetate as the representative reactant
molecules. Following this recycling procedure, COF-SO3H catalyst was reused for
fve consecutive cycles.
Results and discussion
COF-SO3H was easily prepared in two steps by using melamine and terephthalalde-
hyde through aminal formation reaction, which enables outstanding properties such
as high surface area, good thermal stability, low density, and acidifcation in the next
step (Scheme 2).
The Fourier transformed infrared (FTIR) spectra of the synthesized COF and
its COF-SO3H are shown in Fig. 1. In the IR spectrum of the COF (Fig. 1a), the
stretching vibration of N–H bond is observed at 3408 cm−1, which is wide due to the
presence of numerous N–H bonds in the COF. The characteristic aromatic rings are
observed at 1548 and 1474 cm−1 (C=C and also C=N vibration).
In COF-SO3H spectrum, bands around 1018–1200 cm−1 can be attributed to
–SO3H stretching vibrations. These results suggest the successful introduction of
–SO3H groups onto the main polymeric framework of COF. It is also noteworthy
Scheme 2 Synthesis of COF and COF-SO3H
1 3

Sulfonamide‑functionalized covalent organic framework…
120
100
80
60
40
20
0
4000
3600
3200
2800
2400
2000
1600
1200
800
400
Wavenumber,cm-1
Fig. 1 FTIR spectra of a COF (blue) and b COF-SO3H (green). (Color fgure online)
that the successful functionalization of COF with –SO3H groups can be con-
frmed via EDX analysis.
The thermal stability for the synthesized COF polymers and sulfonated mate-
rials COF-SO3H has been determined by TGA measurement in the temperature
range of 0 to 1000 °C. The TG plots of the samples are shown in Fig. 2. For COF,
there is no structural decomposition up to 432 °C, but afterwards the cleavages of
polymeric framework of the COF get started. In the COF-SO3H therogravimetric
diagram, below 200 °C a 20% weight loss was observed, which is attributed to
intercalated and adsorbed water molecules in the sample. Afterward, COF-SO3H
structure was stable up to 294 °C which the weight loss gradually occurs subse-
quently due to the breaking of sulfonic acid group frst and fnally for the decom-
position of organic structure of the COF.
Fig. 2 The TGA curve of COF (a); and COF-SO3H (b)
1 3

R. Farsi et al.
Table 1 Surface area, average
pore width, and total pore
volume (Vtotal) of COF and
COF-SO3H
Sample
BET surface
Vtotal (cm3 g−1
)
Pore size (nm)
area (m2 g−1
)
COF
COF-SO3H
166.11
79.327
0.4352
0.4474
10.48
22.562
Fig. 3 The BET curve of COF (a); and COF-SO3H (b)
The Brunauer–Emmett–Teller (BET) surface area of COF was 166.11 m2g−1
with total pore volume of around 0.4352 cm3g−1 (Table 1 and Fig. 3). Upon sul-
fonation of the sufonated polymer, COF-SO3H, the BET surface area is decreased
to 79.327 m2g1 with a total pore volume of 0.4474 cm3g−1. Surprisingly, although
the surface area has decreased, the pore volume and pore size were increased. It
can be attributed to the fexible bonds, which can be broken and reformed in the
acidic medium (e.g., aminal bonds) so that the pore can breathe. And also, it is an
indication of more external functionalization than internal.
The morphological and structural properties of the COF and COF-SO3H mate-
rials were carried out using SEM analysis (Fig. 4). It can be visualized that the
COF and COF-SO3H have nano-sized structure with an average size of about
10 nm.
Figure 5 shows the results of energy-dispersive X-ray spectroscopy (EDX). The
presence of, O, N, C and S species in the obtained COF-SO3H is confrmed. The
EDS mapping images of COF-SO3H (Fig. 6) revealed the homogeneous disper-
sion of C, N, O, and S within the polymer network. The loading content of sulfur is
5.56 wt%, and this can be used as a verifcation criteria for the successful sulfonic
acid functionalization of the catalyst.
The catalytic application of COF-SO3H was studied in Hantzsch condensa-
tion reaction for the preparation of polyhydroquinoline and 1,4-dihydropyridine
derivatives. The reaction of benzaldehyde, ethyl acetoacetate and ammonium
1 3

Sulfonamide‑functionalized covalent organic framework…
Fig. 4 SEM images of COF (a) and COF-SO3H (b)
Fig. 5 SEM image of COF-SO3H and corresponding quantitative EDX element mapping of O, C, N, and
S
Fig. 6 SEM image of COF-SO3H and corresponding quantitative EDX element mapping of O, C, N, and
S
1 3

R. Farsi et al.
acetate (1, 2, 2) was chosen as the model reaction to optimize the reaction condi-
tion in the presence of diferent amounts of the catalyst in a range of temperatures
(Table 2).
Using this optimized condition, we probed the generality of our methodology
by reacting with various other aldehydes, ammonium acetate, and ethyl acetoac-
etate (1, 2, 2) under solvent-free conditions at 90 °C (Scheme1). It is noteworthy
to mention that the structural variation relating to the aldehyde and substituents
on the aromatic ring had no signifcant impact on this change, as 1,4-dihydropyri-
dine derivatives were obtained in high-to-excellent efciencies with rather short
reaction times (Table 3).
It can be postulated that the reaction is proceeded via a hydrogen abstraction
and a Knoevenagel condensation reaction. After nucleophilic attack of another
ethylacetoacetate molecule, the subsequent imine formation occurs with the liber-
ated ammonia from ammonium acetate. After dehydration, the target 1,4-dihydro-
pyridine will be prepared (Scheme 3).
After successful preparation of Hantzsch 1,4-dihydropyridine derivatives in
good-to-excellent yields and also as a next step to benchmark the catalyst, we
decided to synthesize polyhydroquinoline derivatives (PHQs) via Hantzsch reac-
tion under optimal reaction conditions (Scheme 1). The products were acquired
with high yields (87–96%). The obtained outcomes are summarized in Table 4.
It can be proposed that the reaction proceeds as 1,4-dihydropyridines with the
diference that in the frst step, the Knoevenagel condensation occurs with dime-
done and aromatic aldehyde; afterward, a Michael addition occurs and after cycli-
zation, the target polyhydroquinolines are prepared (Scheme 4).
The wide-angle powder X-ray difraction (PXRD) of COF, fresh COF-SO3H,
and reused COF-SO3H was obtained (Fig. 7). The appearance of broad peaks
between 2θ value of 15 to 30 degree in the PXRD pattern could be attributed to
the amorphous nature of this porous organic polymer.
The FT-IR spectrum of the reused catalyst was obtained and was compared with
the fresh catalyst (Fig. 8). There was no considerable change in the spectrum, which
is an indication of the stability of the catalyst structure in the reaction medium.
Table 2 Optimization of conditions for the condensation reaction of benzaldehyde (1 mmol), ethyl ace-
toacetate (2 mmol) and ammonium acetate under solvent-free conditions
Entry
NH4OAc
(mmol)
Catalyst (gr)
Temp (°C)
Time (min)
Yield (%)
1
2
3
5
6
7
8
9
2
1.5
2
2
2
1
1.5
2
0.02
0.02
0.01
0.02
0.02
0.02
0.02
0.03
80
80
80
90
100
80
90
90
15
20
30
10
10
45
15
10
91
89
76
93
91
62
90
86
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Sulfonamide‑functionalized covalent organic framework…
Table 3 Synthesis of 1,4-dihydropyridine derivatives catalyzed by COF-SO3H under solvent-free ther-
mal conditions
Melting point
(°C )
Found
Melting point
(°C )
Lit
Time
(min)
Yeild
(%)
Entry
R
Product
1
10
93
157-159
158-16038
2
3
4
5
6
10
95
136-138
135-13738
5
95
95
96
92
92
128-130
142-144
162-164
155-157
123-125
130-13239
144-14539
160-16240
153-15640
122-12441
5
5
10
10
7
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R. Farsi et al.
Table 3 (continued)
Melting point
(°C )
Found
Melting point
(°C )
Lit
Time
(min)
Yeild
(%)
Entry
R
Product
8
10
87
214-216
216-21842
9
10
90
108-110
108-11042
10
5
94
165-167
166-16843
Scheme 3 Proposed mechanism of COF-SO3H-catalyzed synthesis of 1,4-dihydropyridine
1 3

Sulfonamide‑functionalized covalent organic framework…
Table 4 Synthesis of polyhydroquinoline derivatives catalyzed by COF-SO3H under solvent-free thermal
conditions
Melting point Melting point
(°C )
Lit
Time
(min)
Yeild
(%)
Entry
R
Product
(°C )
Found
1
202-20444
5
96
201-203
2
5
95
242-244
244-24644
3
5
96
262-264
260-26245
4
5
96
95
88
186-188
249-251
234-236
185-18745
252–25446
5
5
6
10
232-23446
According to the green chemistry principles and also sustainable chemistry
remarks, the catalyst reusability in the reaction of ethyl acetoacetate, benzaldehyde,
and ammonium acetate was evaluated. In this case, after the completion of reaction,
the reaction mixture was cooled to room temperature and the catalyst was removed,
1 3

R. Farsi et al.
Table 4 (continued)
Melting point Melting point
(°C )
Lit
Time
(min)
Yeild
(%)
Entry
R
Product
(°C )
Found
7
10
87
251-253
257-259
254-25547
8
5
90
256-25847
9
10
5
92
94
207-209
242-244
208-21048
240-24248
10
11
5
92
204-206
204-20649
242-24549
12
10
93
241-243
washed with ethanol and dried; subsequently, it was reused for the similar reaction.
The results illustrated in Fig. 9 indicate that the catalyst could be reused at least for
fve cycles with only slight reduction in catalytic activity.
With the same method, the reusability of the catalyst in the reaction of benzalde-
hyde, ethyl acetoacetate, dimedone and ammonium acetate at 90 °C under solvent-
free conditions was evaluated. As it is shown in Fig. 10 that the catalyst could be
reused at least fve times without signifcant decrease in this nanoporous catalyst.
1 3

Sulfonamide‑functionalized covalent organic framework…
Scheme 4 Proposed mechanism of COF-SO3H-catalyzed polyhydroquinolines synthesis
400
350
a:Reused COF-SO3H
b:Fresh COF-SO3H
c: COF
300
250
200
150
100
50
0
0
20
40
60
80
100
2 ( )
Fig. 7 Powder X-ray difraction (PXRD) of COF, fresh COF-SO3H, and reused COF-SO3H
1 3

R. Farsi et al.
a
b
100
90
80
70
60
50
40
30
20
4000
3600
3200
2800
2400
2000
1600
1200
800
400
Wavenumber, cm-1
Fig. 8 FT-IR spectra of fresh (a) and reused (b) catalyst
At last, to show the superiority of the present approach in comparison with
other catalysts, we compared our results with the reported results in the literature
for the synthesis of DHP and PHQ (Table 5). Results showed that while in most
of these cases comparative yields of the desired product were obtained following
the COF-SO3H-catalyzed procedure, some of the previous procedures required
1 3

Sulfonamide‑functionalized covalent organic framework…
93
90
90
88
84
100
50
0
15
15
10
10
10
Yield (%)
Time (min)
1
2
3
Time (min)
4
Yield (%)
5
Fig. 9 Reusability of the catalyst in the reaction of benzaldehyde, ethyl acetoacetate, and ammonium ace-
tate at 90 °C under solvent-free conditions
96
94
92
90
90
100
50
0
10
10
Yield
Time
5
5
5
1
2
3
4
5
Time
Yield
Fig. 10 Catalyst reusability in the reaction of benzaldehyde, dimedone, ethyl acetoacetate, and ammo-
nium acetate
Table 5 Comparison of catalytic activity of COF-SO3H nanostructures with some other catalysts
Entry
Catalyst
Conditions
Solvent
Time
(min)
Yield
(%)
Catalyst
loading
(mol %)
Ref
T/°C
25
1
2,4,6-Trichloro
(1,3,5)triazine
Solvent-free
30
94
10
[26]
2
3
4
5
6
7
8
InCl3
[bmim]Cl
EtOH
Solvent-free
EtOH
EtOH
EtOH
Refux
r.t
r.t
Refux
r.t
80
240–360
300
360
360–420
120–360
60
92
90
85
81–92
86–95
92
5
5
5
10
5
10
8.2
[27]
[29]
[30]
[32]
[33]
[35]
This work
Yb(OTf)3
Silica gel/NaHSO4
L-proline
Sc(OTf)3
ZnO
COF-SO3H
Solvent-free
90
5–10
87–96
long reaction time (Entries 2, 3, 4, 5, 6), or high catalyst loading (Entry 1, 5, 7).
These results clearly demonstrate that the presented procedure can be utilized as a
useful acidic catalyst in organic methodology.
1 3

R. Farsi et al.
Conclusion
In conclusion, we have prepared an efcient organic solid acid catalyst by post-
modifcation of the COF, which was prepared via reaction of melamine and tere-
phthalaldehyde. The COF-SO3H was shown to be porous with a surface area of
79.327 m2 g−1. After characterization of the catalyst, it was used as an efective solid
acid catalyst for the synthesis of various 1,4-dihydropyridine and polyhydroquino-
line derivatives via an one-pot multicomponent Hantzsch reaction in the presence of
COF-SO3H as the catalyst with high isolated yields. This methodology ofers sev-
eral advantages including high yield, short reaction time, simple workup procedure,
solvent-free conditions, and recyclability of the catalyst.
Acknowledgements The fnancial support of this work by the research council of Islamic Azad Univer-
sity of Ahvaz is greatly acknowledged.
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