Propylsulfonic Acid-Anchored Isocyanurate-Based Periodic Mesoporous Organosilica (PMO-ICS-PrSO3H): A Highly Efficient and Recoverable Nanoporous Catalyst for the One-Pot Synthesis of Substituted Polyhydroquinolines

Article abstract of DOI:10.1007/s10562-017-2159-5

Abstract: Propylsulfonic acid-anchored isocyanurate bridging periodic mesoporous organosilica (PMO-ICS-PrSO₃H) was shown to be a highly active and efficient recyclable catalyst for the four-component synthesis of polyhydroquinoline derivatives from dimedone, different aldehydes, ethyl acetoacetate and ammonium acetate under mild reaction conditions in short reaction times and good to excellent yields in EtOH. Moreover, the catalyst was also recovered and reused at least four times without significant decrease in its activity. The PMO-ICS-PrSO₃H catalyst was characterized by FTIR spectroscopy, TGA, nitrogen adsorption–desorption isotherms as well as FESEM. Compared to the classical methodologies, this method illustrated significant advantages including low loading of the catalyst, avoiding the use of toxic transition metals or reactive reagents for modification of the catalytic activity, short reaction times, high to excellent yields, easy separation and purification of the products, and reusability of the catalyst. Graphical Abstract: [Figure not available: see fulltext.].

Full text of DOI:10.1007/s10562-017-2159-5

Catal Lett
DOI 10.1007/s10562-017-2159-5
Propylsulfonic Acid-Anchored Isocyanurate-Based Periodic
Mesoporous Organosilica (PMO-ICS-PrSO3H): A Highly
Efficient and Recoverable Nanoporous Catalyst for the One-Pot
Synthesis of Substituted Polyhydroquinolines
Amene Yaghoubi1 · Mohammad G. Dekamin1 · Babak Karimi2
Received: 3 June 2017 / Accepted: 30 July 2017
© Springer Science+Business Media, LLC 2017
Abstract Propylsulfonic acid-anchored isocyanurate
bridging periodic mesoporous organosilica (PMO-ICS-
PrSO3H) was shown to be a highly active and efficient recy-
clable catalyst for the four-component synthesis of polyhyd-
roquinoline derivatives from dimedone, different aldehydes,
ethyl acetoacetate and ammonium acetate under mild reac-
tion conditions in short reaction times and good to excellent
yields in EtOH. Moreover, the catalyst was also recovered
and reused at least four times without significant decrease
in its activity. The PMO-ICS-PrSO3H catalyst was charac-
terized by FTIR spectroscopy, TGA, nitrogen adsorption–
desorption isotherms as well as FESEM. Compared to the
classical methodologies, this method illustrated significant
advantages including low loading of the catalyst, avoiding
the use of toxic transition metals or reactive reagents for
modification of the catalytic activity, short reaction times,
high to excellent yields, easy separation and purification of
the products, and reusability of the catalyst.
Graphical Abstract
Keywords Heterocycles · Periodic mesoporous
organosilicas (PMOs) · Solid acids · Multicomponent
reactions (MCRs) · Green chemistry
1 Introduction
Polyhydroquinolines are one of the most important groups of
nitrogen heterocycles that have attracted considerable inter-
est because of various important pharmacological and thera-
peutic properties. Some pharmacological activities of poly-
hydroquinolines are calcium channel blockers, vasodilator,
bronchodilator, antiatherosclerotic, antitumor, geroprotective,
hepatoprotective, and antidiabetic agents. Furthermore, some
polyhydroquinolines exhibit other medicinal applications
which include platelet antiaggregatory activity, neuropro-
tectant, and cerebral antischemic activity in the treatment of
Alzheimer’s disease. Hantzsch synthesis of polyhydroqui-
nolines is one of the most significant multi-component reac-
tions due to its key role in the production of these pharmaco-
logically useful compounds. This method generally involves
one-pot condensation of aldehydes with β-dicarbonyls and
amine sources under acidic conditions [1–6]. In view of the
importance of polyhydroquinolines, many catalytic systems
Electronic supplementary material The online version of this
article (doi:10.1007/s10562-017-2159-5) contains supplementary
material, which is available to authorized users.
* Mohammad G. Dekamin
mdekamin@iust.ac.ir
1
Pharmaceutical and Heterocyclic Compounds Research
Laboratory, Department of Chemistry, Iran University
of Science and Technology, Tehran 16846-13114, Iran
2
Department of Chemistry, Institute for Advanced Studies
in Basic Sciences (IASBS), P.O. Box 45195-1159, Gavazang,
Zanjan, Iran
Vol.:(0123456789)
1 3

A. Yaghoubi et al.
have been successfully reported for their synthesis using con-
ventional heating and refluxing methods in the presence of
acid catalysts mainly under homogeneous conditions. Some
of these developing catalysts include TMS-I [7], TMS-Cl
[7], hafnium(IV) bis(perfluorooctanesulfonyl)imide com-
from bridged organosilane precursors have been classified
as periodic mesoporous organosilicas (PMOs). PMOs are
very attractive as support for heterogeneous catalysts in
fine chemicals synthesis among others. The large and tun-
able pore sizes (between 2 and 30 nm) and pore volumes,
well-defined pore morphology, and high surface areas of
PMOs allow facile diffusion of bulky reactants and prod-
ucts that are often involved in such reactions. In addition,
other unique properties of PMOs such as high loading of
uniform distribution of organic functional groups in their
framework, superior thermal stability, non-toxicity, reus-
ability, and stability against air and moisture make them
an attractive candidate for the widespread applications in
catalysis, chromatography, solid-phase extraction, elec-
tronic, sensor technology, gas storage, etc [21–32]. Among
different organic moieties used for fabrication of PMOs, the
heteroaromatic isocyanurate ring having three nonpolar pro-
pyl groups shows unique properties such as its high thermal
stability [33–36], binding ability to transition metals [29, 37]
and appropriate modification of the silica surface polarity
−
plex [Hf(NPf2)4] [8], Yb(OTf)3 [9], Bu4N+HSO4 [10],
K7[PW11CoO40] [11], ionic liquids [12], metal triflates [13],
cerium (IV) ammonium nitrate [14], iodine [15], PTSA-SDS
[16], tris(pentafluorophenyl)borane [17], boronic acids [18],
HClO4/SiO2 [19] and BINOL-phosphoric acids [20]. How-
ever, these methods suffer from drawbacks such as a long
reaction time, the use of large amount of volatile organic
solvents, catalyst recovery, product separation and harsh
refluxing conditions.
The use of heterogeneous catalysts has become highly
desirable in recent years, because they incorporate many
green chemistry principles. In 1999, mesoporous organo-
silica hybrids were prepared from bridged organosilane
precursors ((ŔO)3Si–R–Si(OŔ)3; R: organic bridging group,
Ŕ: methyl or ethyl). Such mesoporous hybrids prepared
Scheme 1 The one-pot
O
four-component synthesis of
polyhydroquinoline derivatives
catalyzed by PMO-ICS-PrSO3H
(1)
MeO
MeO
OMe
OMe
Si
N
N
Si
OMe
MeO
O
N
O
(3-Mercaptopropyl)
trimethoxysilane
MeO
MeO
Si
OMe
1) H2O, pluronic P123, HCl, H2O2
2) Surfactant removal
O
N
O
O
O
O
O
O
Si
Si
N
O
Si
OH
Si
O
N
O
OH
HO
O
SO3H
Si
Si
SO3H
SO3H
HO
PMO-ICS-PrSO3H (1)
R1
CHO
O
O
O
O
O
PMO-ICS-PrSO3H (1)
COOEt
NH4OAc
OEt
EtOH, Reflux
N
H
R1
6
4
5
3
2
1 3

Propylsulfonic Acid-Anchored Isocyanurate-Based Periodic Mesoporous Organosilica…
[38–41]. Therefore, isocyanurate-based periodic mesoporous
organosilica (PMO-ICS) is a promising support or catalyst
depending on the used conditions compared to modified
mesoporous silica materials (M41S family) or even other
members of PMOs family having two aryl or alkyl groups
in their structures. On the other hand, multicomponent reac-
tions (MCRs) offer high atom economy and bond-forming
efficiency for the synthesis of diverse and complex mole-
cules especially heterocyclic compounds in fast and often
experimentally simple procedures [3, 4, 41–50].
of (3-mercaptopropyl) trimethoxysilane were added to the
solution. The resulting mixture was agitated for 2 h at 40 °C
and thereafter aged for 24 h at 100 °C. The resulting solid
material was filtered and air-dried. To extract the residual
block co-polymer, the solid material (0.5 g) was stirred in
acetone (60 ml) for 10 h at 56 °C, followed by washing with
deionized water. The final products were obtained after dry-
ing the samples in an oven for 1 day at 100 °C [60].
In continuation of our interest to develop mild and effi-
cient catalysts for different MCRs [21, 51–59], we herein
wish to report the catalytic application of propylsulfonic
acid-anchored periodic mesoporous organosilica (PMO-
ICS-PrSO3H, 1) nanomaterial with active Bronsted acid
centers, as a new, efficient and recoverable catalyst, for the
synthesis of polyhydroquinoline derivatives (6) in EtOH
under reflux conditions. To the best of our knowledge, there
is no report on the use of acidic-anchored PMOs for the
synthesis of polyhydroquinoline derivatives (Scheme 1).
2.3 General Procedure for the Synthesis
of Polyhydroquinoline Derivatives (6a–o)
In a 5 mL round-bottomed flask, aldehyde (2a–o, 1 mmol),
dimedone (3, 1 mmol), ethyl acetoacetate (4, 1 mmol) and
NH4OAc (5, 1 mmol) and PMO-ICS-PrSO3H (1, 20 mg,
3 mol%) were added to EtOH 96% (2 mL). The obtained
mixture was stirred at reflux conditions for times indicated
in Table 2. After completion of the reaction monitored by
TLC (eluent: EtOAc: n-hexane), EtOH (3 mL) was added
to the mixture and the catalyst was easily isolated from the
reaction mixture by simple filtration during recrystalliza-
tion of the products.
2 Materials and Methods
2.1 Materials
3 Results and Discussion
All chemicals were purchased from Merck or Aldrich and
used as received except for benzaldehyde which a fresh dis-
tilled sample was used. Field emission scanning electron
microscopy (FESEM) images were obtained using Sigma
instrument of Zeiss Company, Germany. The BET specific
surface area of the catalyst was obtained using an equip-
ment ASAP 2020™ micromeritics. Thermal gravimetric
analysis (TGA) was performed by means of Bahr company
STA 504 instrument. FTIR spectra were recorded as KBr
pellets on a Shimadzu FT IR-8400S spectrometer. Melting
points were determined using an Electrothermal 9100 appa-
ratus and are uncorrected. 1H NMR (500 MHz) spectra were
obtained using a Bruker DRX-500 AVANCE spectrometer in
CDCl3 at ambient temperature. Analytical TLC was carried
out using Merck 0.2 mm silica gel 60 F-254 Al-plates. All
the products are known compounds and were identified by
comparison of their physical and spectroscopic and analyti-
cal data with authentic samples.
3.1 Characterization of the Catalysts
PMO-ICS-PrSO3H (1) was prepared analogous to the pro-
cedure described by Kim et al. [60, 61] by starting from tris
[(3-trimethoxysilyl) propyl] isocyanurate (ICS). The tex-
tural properties of the functionalized isocyanurate bridging
containing mesoporous organosilica (1) were determined
by nitrogen adsorption–desorption isotherms. The surface
area and pore size distribution were calculated with the
BET and BJH methods, respectively. The N2-sorption iso-
therm indicate that the pore sizes of PMO-ICS-PrSO3H are
in the mesoporous range (Fig. 1). The material exhibited
2.2 General Procedure for Synthesis
of PMO-ICS-PrSO3H (1)
In a typical one-step preparation, 0.66 g of pluronic P123
was dissolved in 23.6 g of deionized water, 0.57 g of
H2O2 (30 wt%), and 0.13 g of HCl (37 wt%). Then 0.47 g
of tris[3-(trimethoxysilyl)propyl] isocyanurate (ICS,
Aldrich) and 0.109 g (30 mol% in total silica precursors)
Fig. 1 BET analysis of the PMO-ICS-PrSO3H nanoporous catalyst
(1)
1 3

A. Yaghoubi et al.
a type IV isotherm pattern, which is characteristics of the
mesoporous structure with relatively broad pore size dis-
tributions. The calculated Brunauer–Emmet–Teller (BET)
specific surface area is close to 290.86 m2/g, and total pore
volume≈0.25 cm3/g (Fig. 1). On the other hand, energy-dis-
persive X-ray (EDX) spectroscopy showed the presence of C,
O, Si, N and S atoms, in the structure of PMO-ICS-PrSO3H
nanoporous catalyst (1). The elemental distribution mapping
of this analysis shows signals of carbon: oxygen: silicon:
nitrogen: sulfur in the ratio of 44.1:26.4:8.6:19.0:1.9 wt%,
respectively. These findings also confirm successful incor-
poration of expected isocyanurate group in the material net-
work. The organic composition of the modified mesoporous
materials was also determined by thermogravimetric analysis
(TGA) and differential thermoanalysis (DTA), with heating
from room temperature to 800 °C under an air flow. Thermo-
gravimetric analysis (TGA) of PMO-ICS-PrSO3H (1) showed
the thermal stability about 480 °C for the isocyanurate bridg-
ing containing organics which have been incorporated into
the silica framework (See ESI). Quantitative determination of
the SO3H functional group covalently anchored onto the sur-
face of the isocyanurate based on periodic mesoporous orga-
nosilica were calculated by acid–base titration (1.5 mmol of
sulfonic acid/g of catalyst 1). Furthermore, the catalyst was
characterized using other techniques including Fourier trans-
form infrared (FTIR) spectroscopy, and field emission scan-
ning electron microscopy (FESEM, Fig. 2).
isocyanurate-based periodic mesoporous organosilica
(PMO-ICS-PrSO3H, 1) for the synthesis of polyhydro-
quinolines derivatives (6), the reaction of 4-chloroben-
zaldehyde (2a, 1 mmol), dimedone (3, 1 mmol), ethyl
acetoacetate (4, 1 mmol) and NH4OAc (5, 1 mmol) was
investigated as the model reaction. The reaction conditions
were optimized in order to determine appropriate catalyst
loading, different solvents and temperature for the synthe-
sis of polyhydroquinolines derivatives. The results have
been summarized in Table 1. It was observed that only
30% of the desired product 6a was obtained in the absence
of the catalyst (1) under reflux conditions after 2 h in
EtOH (Table 2, entry 1,2). Interestingly, after addition of
10 mg of PMO-ICS-PrSO3H (1) as the catalyst, the yield
of the desired product 6a was increased significantly under
similar reaction conditions in refluxing EtOH compared
to catalyst-free conditions (Table 1, entry 3). Further-
more, 20 mg (3 mol%) loading of PMO-ICS-PrSO3H (1)
afforded higher yield of the desired product 6a in shorter
reaction time in refluxing EtOH (Table 1, entry 4). In the
next step, the effect of other solvents such as H2O, CH2Cl2
Table 1 Optimization of conditions in the reaction of 4-chloroben-
zaldehyde (2a), dimedone (3), ethyl acetoacetate (4) and NH4OAc (5)
under different conditions
3.2 Examination of the Catalytic Activity
of PMO-ICS-PrSO3H Nanoporous Catalyst (1)
for the Hantzsch MCR
After characterization of the catalyst, to examine efficiency
and catalytic activity of the propylsulfonic acid-anchored
Entry Catalyst
1 loading
(mg)
Solvent
Temp (°C) Time
(min)
Yielda (%)
1
2
3
4
5
6
7
8
9
–
–
EtOH
EtOH
EtOH
EtOH
CH2Cl2
CH3CN
H2O
r.t
120
120
35
20
70
80
60
20
30
Trace
30
80
96
40
45
60
96
89
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
80 °C
10
20
20
20
20
30
20
EtOH
Solvent-
free
10
11
20b
20c
EtOH
EtOH
Reflux
Reflux
3 h
1 h
40
90
Reaction conditions 4-Chlorobenzaldehyde (2a, 1 mmol), dimedone
(3, 1 mmol), ethyl acetoacetate (4, 1 mmol) and NH4OAc (5, 1 mmol)
aIsolated yields
bSBA-15
Fig. 2 FESEM image of the PMO-ICS-PrSO3H nanoporous catalyst
(1)
cSBA-15-Pr-SO3H
1 3

Propylsulfonic Acid-Anchored Isocyanurate-Based Periodic Mesoporous Organosilica…
Table 2 Propylsulfonic acid-anchored isocyanurate bridging periodic mesoporous organosilica (PMO-ICS-PrSO3H, 1) catalyzed one-pot syn-
thesis of polyhydroquinolines 6 from different aldehydes (2), dimedone (3), ethyl acetoacetate (4) and NH4OAc (5) under the optimized condi-
tions
Entry
Aldehyde 2
Product 6
Time (min)
Yielda,b (%)
1
2
3
4
5
6
7
8
4-Chlorobenzaldehyde (2a)
2-Chlorobenzaldehyde (2b)
2-Nitrobenzaldehyde (2c)
4-Nitrobenzaldehyde (2d)
3-Nitrobenzaldehyde (2e)
4-Cyanobenzaldehyde (2f)
2,4-Dichlorobenzaldehyde (2g)
4-Boromobenzaldehyde (2h)
Benzaldehyde (2i)
4-Methylbenzaldehyde (2j)
4-Methoxybenzaldehyde (2k)
4-Hydroxybenzaldehyde (2l)
Furfural (2m)
6a
6b
6c
6d
6e
6f
6g
6h
6i
6j
6k
6l
6m
6n
6o
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
96
94
89
92
93
97
94
96
95
95
95
88
92
92
94
9
10
11
12
13
14
15
Thiophene-2-carbaldehyde (2n)
4-Pyridincarbaldehyde (2o)
Reaction conditions Aldehyde 2a, (1 mmol), dimedone (3, 1 mmol), ethyl acetoacetate (4, 1 mmol) and NH4OAc (5, 1 mmol) in the presence of
20 mg (3 mol%) PMO-ICS-PrSO3H (1) and EtOH (2 mL)
aIsolated yields
bAll products are known compounds and were identified by comparison of their physical and spectroscopic data with authentic samples [7, 51,
52]
and CH3CN on the model reaction was investigated. These
solvents afforded lower yield of the desired product 6a
(Table 2, entries 5–7). On the other hand, increasing of
the catalyst loading to 30 mg had no significant effect on
the yield of the desired product 6a under similar reaction
conditions in refluxing EtOH. (Table 1, entry 8). Finally,
the desired product 6a was obtained in lower yield and
longer reaction time at 80 °C under solvent-free condi-
tions compared to reflux conditions in EtOH (Table 1,
entry 9). Moreover, lower yields of the desired product
6a obtained in the presence of SBA-15, SBA-15-Pr-SO3H
under similar reaction conditions (Table 2, entries 10,11)
that indicates significant effect of the isocyanurate bridg-
ing organic group within the framework of silica com-
pared to pure silanol or siloxane groups of SBA-15 and
SBA-15-Pr-SO3H.
The optimized conditions were further developed to other
aromatic or heterocyclic aldehydes (2a–o). The results are
summarized in Table 2. As it can be seen, in all studied
cases, good to excellent yields of the desired products (6a–o)
were obtained under the optimized reaction conditions
within short reaction times. Both aromatic carbocyclic and
heterocyclic aldehydes containing electron-withdrawing or
electron-donating groups involved in the optimized reaction
conditions to afford corresponding products. Furthermore,
furfural (2m) and thiophene-2-carbaldehyde (2n), which are
susceptible to polymerization under acidic conditions, sur-
vived under optimal reaction conditions to afford the corre-
sponding products. Moreover, the rate of reactions was sig-
nificantly influenced by the nature of the substituents on the
aromatic ring of the aldehyde component. Hence, aromatic
aldehydes having electron-withdrawing groups afforded the
1 3

A. Yaghoubi et al.
O
Ar
O
OR
O
N
H
Ar
H
(6)
(2)
SO3H
(1)
O3S
H
O
O
Ar
O
H
H
O3S
Ar
OR
H
(I)
N
O
OH
O
O
HO
H
(V)
SO3H
(3)
(3')
H2O
O3S
H2O
H
O
Ar
H
O
Ar
O
O
(ΙΙ)
OR
O
NH3OAc (5)
O
H2N
O
H
H
OR
O
O
OR
(IV)
H2N
SO3H
HN
OR
NH3
H2O
HOAc
(ΙΙΙ)
O
O
N
O
O
O
O
Si
OH
N
O
N
Si
Si
Si
HO
O
O
O
O
=
SO3H
SO3H
HO
O
O
HO3S
Si
Si
PMO-ICS-PrSO3H (1)
O
O
SO3H
Scheme 2 Plausible mechanism for the one-pot synthesis of polyhydroquinoline derivatives 6 catalyzed by the PMO-ICS-PrSO3H nanoporous
catalyst (1)
corresponding products in higher yields and shorter reaction
times compared to electron-donating groups under similar
conditions (Table 2).
A probable mechanistic pathway for the formation of
polyhydroquinoline derivatives 6 is outlined in Scheme 2.
According to the suggested mechanism, it can be proposed
that the PrSO3H groups on the surface of PMO-ICS-PrSO3H
(1) are responsible for initial activation of the carbonyl group
of aldehydes 2 to facilitate nucleophilic addition of the enol
form of dimedone (3’) on the carbonyl group of aldehydes
2 to afford intermediate (I) with elimination of a water mol-
ecule. Simultaneously, carbonyl group of ethyl acetoacetate
(4) can be activated by the proton of NH4OAc (5) for sub-
Fig. 3 Reusability of PMO-ICS-PrSO3H nanoporous catalyst (1) for
sequent nucleophilic addition of NH3 on its carbonyl group
the synthesis of 6a
1 3

Propylsulfonic Acid-Anchored Isocyanurate-Based Periodic Mesoporous Organosilica…
Table 3 Comparison of the catalytic efficiency of PMO-ICS-PrSO3H (1) with other heterogeneous or homogeneous catalysts for the synthesis
of 6a
Entry
Catalyst
Catalyst loading
Solvent
Temp (°C)
Time (min)
Yield (%)
Ref
1
2
3
4
Mn@PMO-IL
(NS-C4(DABCO-SO3H)2·4Cl)
Co3O4–CNTs
1 mol%
5 mol%
30 mg
–
–
80 °C
100 °C
Reflux
90 °C/micro-
wave irradia-
tion
20
18
35
20
87
92
97
84
[63]
[64]
[65]
[66]
EtOH
EtOH
Glycine nitrate (GlyNO3) ionic liquid
50 mol%
5
PMO-ICS-PrSO3H
20 mg (3 mol%)
EtOH
Reflux
20
96
This work
to produce enamine intermediate (II) and with elimination
of second water molecule. Then, the desired products 6 are
obtained by Michael addition of enamine (II) to the activated
intermediate (I) and subsequent ring closure step with third
water molecule elimination [51–53, 62]. Water molecules
are mainly the byproducts of this MCR reaction which can
be sorbed on the surface of PMO-ICS-PrSO3H (1) physically
by the silanols or chemically by siloxane functional groups.
Another important aspect of this active, efficient, and
eco-friendly heterogeneous nanoporous catalyst is its recy-
clability. In this part of our study, it has been presented that
the PMO-ICS-PrSO3H (1) could be recovered and reused at
least four times in the subsequent runs for the model reac-
tion using the same recovered catalyst without a consider-
able loss of its catalytic activity (Fig. 3).
of toxic transition metals or reactive reagents for modifi-
cation of the catalytic activity, short reaction times, high
yields, elimination of toxic organic solvents, reusability of
the catalyst and simple procedure.
Acknowledgements We are grateful for the financial support from
The Research Council of Iran University of Science and Technol-
ogy (IUST), Tehran, Iran (Grant No. 160/347). We would also like to
acknowledge the support of Iran Nanotechnology Initiative Council
(INIC), Iran.
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by catalyst loading, reaction temperature and solvent. The
catalyst illustrated high efficiency for the one-pot synthesis
of polyhydroquinoline derivatives using different aldehydes,
dimedone, ethyl acetoacetate and NH4OAc in EtOH under
reflux conditions. In addition, the catalyst could be recovered
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