Catalytic behavior of perchloric acid on silica mesoporous SBA-15 as a green heterogeneous Bronsted acid in heterocyclic multicomponent reactions
Catalytic behavior of perchloric acid on silica mesoporous SBA‑15 as a green heterogeneous Bronsted acid in heterocyclic multicomponent reactions
Ali Baghban 0
Esmail Doustkhah 0
Sadegh Rostamnia 0
Sadegh Rostamnia 0
0 Organic and Nano Group (ONG), Department of Chemistry, Faculty of Science, University of Maragheh , PO Box 55181-83111, Maragheh , Iran
1 Esmail Doustkhah
Catalytic behavior of perchloric acid when supported to mesoporous silica SBA-15 (SBA-15/HClO4) was investigated as a heterogeneous Bronsted acid. Its reactivity and leaching possibility were studied in cascade ring opening-cyclocondensation sequence of diketene and alcohol with aldehyde in the presence of either of urea or ammonium acetate. Results showed that this catalyst can be highly recyclable for several cycles. Vol.:(011233456789)
SBA-15/HClO4; Bronsted acid; Diketene; cascade reaction
Introduction
Design and synthesis of mesoporous silica materials for
catalytic aims are a highly demanding research area,
nowadays [
1–3
]. High surface area, suitable pore channels
compared to zeolites for small molecules, chemoselectivity over
mesoporosity, feasibility in post-modification, and higher
stability under harsh conditions are some aspects that can
be pointed out why mesoporous silica materials are
popular for catalytic tasks [
1, 4–7
]. Pore channel’s dimensional
array (whether 2D or 3D) thickness of pore wall, synthesis
procedure, surface area, stability over several reuses, and
pore size distribution are some fateful factors in choosing
a specific mesopore for catalyst design [
8
]. Among them,
stability, easy synthetic procedure, and higher surface area
are some reasons that have made SBA-15 as a most common
Department of Chemistry, Faculty of Science, Payame Noor
University, P.O. Box 19395-3697, Tehran, Iran
mesoporous silica which is incorporated for catalyst
designing [
9
].
Synthesis of heterogeneous Bronsted acid is a universal
demand toward greening the chemical processes to
eliminate or reduce the toxic and harmful chemicals release to
environment [
10–12
].
So far, there have been many developments in
post-modification strategies to convert SBA-15 to a mesoporous
supported solid Bronsted acid. Organosiloxane precursors play
a major role among the others. Sulfonic acid [
13
],
carboxylic acid [
14
], and phosphonic acid [
15
]-based precursors
are most common types for conversion of relatively neutral
SBA-15 to Bronsted acid. However, they are generally
timeconsuming, complex, and expensive procedures which can
be replaced by an easier and economical pathway. Herein,
we have supported perchloric acid to SBA-15 through a
proper method. Supporting perchloric acid onto silica gel is
extensively studied as a catalyst in various organic
transformations. Hence, in this paper, we supported perchloric acid
onto SBA-15 to generate a new catalyst based on Bronsted
acidic feature.
The use of SBA-15/HClO4 as a catalyst has been achieved
in the catalysis of two series of multicomponent and
cascade type syntheses of heterocycles including
dihydropyrimidinones (DHPM) and dihydropyridines (DHP). These
compounds exhibit a series of biological activities such as
calcium channel blocking, antihypertensive agents, antiviral,
anti-carcinogenic, antiinflammatory, antibacterial, and
melanin concentrating hormone receptor antagonists [
16–19
].
In detail, we used SBA-15/HClO4 in catalytic
ring-opening reaction of diketene in the presence of alcohols and
aldehydes for the synthesis of DHPMs and DHPs’ heterocycles
via final nucleophilic attack of urea and ammonium acetate,
respectively (Fig. 1).
Experimental
Chemicals and apparatus
All reagents were obtained from Merck (Germany) and
Fluka (Switzerland), and were used without further
purification. Melting point was measured on an Electrothermal
9100 apparatus. Progress of reactions was monitored by
thin-layer chromatography (TLC). 1H and 13C NMR spectra
were measured (CDCl3) with a Bruker DRX-300 AVANCE
spectrometer at 300 and 75 MHz, respectively. All yields
were calculated based on the isolated amount of products.
Ordered mesoporous silica supported perchloric
acid: synthesis of SBA‑15/HClO 4
For synthesis of SBA-15 [
20
], triblock copolymer ethylene
oxide-propylene oxide-ethylene oxide (P123, 4.0 g) as a
structure directing agent was dissolved in mixture solution
containing deionized water (30 mL) and 120 g of 2 M HCl.
Then, TEOS (9 g) was added to reaction mixture to stir for
24 h at 40 °C. Then, the resultant mixture was transferred
into a Teflon-lined stainless steel autoclave and kept for
Fig. 1 SBA-15/HClO4 catalyzed
synthesis of DHPMs and DHPs
24 h at 100 °C to complete aging. After cooling down to
room temperature, the product was filtered, washed with
water, and dried overnight at 70 °C in air. Afterward, the
obtained sample after aging was raised to 600 °C by ramp
of 1 °C/min and kept at that temperature for 6 h to
calcine and remove the template. Then, the calcined
SBA15 (1 g) was treated by perchloric acid (HClO4) in
toluene (2 mmol) under reflux conditions for 24 h. Finally,
to purify SBA-15/HClO4 and eliminate the unsupported
HClO4 was then washed with distilled water for several
times and dried at 55–60 °C. H+ titration analysis was
achieved and the loaded amount of H+ onto SBA-15 was
1.7 mmol g−1. BET analysis showed a surface area of ca.
538 m2 g−1 for the obtained catalyst.
FT-IR spectra of SBA-15/HClO4 exhibit some
characteristic peaks at 800 and ~ 1150 cm−1 which can be
assigned to (Si–O–Si) bond vibrations, with a small band
at ca. 950 cm−1 can be attributed to unfunctionalized
silanol groups. Therefore, it can be judged that silanol
groups are functionalized in post-modification step. –O–H
of silanol groups can be visualized in the very broad IR
absorption band in 3000–3700 cm−1 region (Fig. 2).
Figure 3 shows images of scanning electron microscopy
(SEM) and transmission electron microscopy (TEM) of
the as-synthesized SBA-15/HClO4. The highly ordered
mesoporous structure of SBA-15/HClO4 observed by
small-angle XRD confirms the highly ordered and aligned
mesochannels in TEM image (Fig. 3a, c). Diffraction
peaks at the below 2° corresponding to the (1 0 0), (1 1
0), and (2 0 0) are characteristic from the XRD pattern of
SBA-15 (Fig. 3c).
Fig. 2 FT-IR spectra of SBA-15
(red) and SBA-15/HClO4 (blue)
General procedure for the synthesis of DHPMs
and DHPs under neat condition over SBA‑15/HClO 4
Equivalent amount of pure diketene, alcohol in the
presence of an excess amount of equivalent, and aldehyde in
SBA-15/HClO4 (10 mol%) for 10 min under reflux
conditions at 100 °C, NH4OAc or urea was added, and then
heated under neat and refluxing conditions under
vigorous stirring, during an appropriate time (see Tables 1,
2). The reaction was cooled to room temperature and the
solid was washed with dichloromethane. All the products
are known, and they are previously reported in the
literatures [
21–24
] and characterized by comparing physical
data. In recycle procedure, the model reactions were done
according to optimized conditions in 5 mmol of reaction
scale.
Table 1 SBA-15/HClO4
catalyzed Biginelli-type
condensation
Results and discussion
The use of SBA-15/HClO4 as a heterogeneous and
recyclable solid Bronsted acid is designed in this paper and used as
a promising catalyst for organic transformations. The
reaction schemes are based on the use of diketene for in situ
generation of β-ketoesters for using it in the four-component
synthesis of dihydropyrimidinones and dihydropyridines
(Scheme 1). Solid acid catalyst can be easily prepared from
the readily available ingredients, perchloric acid, and silica
mesostructure.
The reaction of diketene, arylaldehydes 1, and alcohols 2,
with urea in the presence of a catalytic amount of SBA-15/
HClO4 undergoes a Biginelli-type cyclocondensation
reaction under reflux conditions which produces DHPM
derivatives 3 in 86–93% yields (Table 1).
1,4-Dihydropyridine products 4 were generated with
ammonium acetate in high yields. The results are
summarized in Table 2. A possible explanation on the mechanism
Isolated and non-optimized yields during 6h
Table 2 SBA-15/HClO4
catalyzed Hantzsch-type
condensation
Scheme 1 Four-component
synthesis of DHPMs and DHPs
by SBA-15/HClO4 catalyst
Isolated and non-optimized yields during 9h
Scheme 2 Resulting in a mixture of products with tert-butyl alcohol in ring-opening of diketene
of these reactions is proposed in Scheme 2. The in situ
generation of β-dicarbonyl 5 and unsaturated adduct 6 happens
by addition of the alcohol and aldehyde, respectively, to
diketene under acidic and reflux conditions which finally
result in DHPMs and DHPs as Biginelli-type and
Hantzschtype conditions, respectively (Tables 1, 2).
Fig. 4 Recyclability study of
SBA-15/HClO4 in synthesis of
3h and 4g
The possibility of reusing SBA-15/HClO4 catalyst in the
syntheses of the 3h and 4g as model reactions was tested and
studied. During this study, at the end of reaction
completion (Tables 1, 2), the catalyst was easily separated from the
product by centrifugation. As indicated in Fig. 4,
recyclability through several consecutive runs is preserved which
shows that the leaching of perchlorate from modified surface
is insignificant. It also shows that there is a powerful
interaction between silica and perchlorate. This observation is in
agreement with other previous reports about
silica–perchlorate interaction [
25–28
].
As shown in Scheme 2, when the four-component
reactions were performed in the presence of t-butyl alcohol
both as a solvent and one of the components in the
reaction, results showed a mixture of product and by-products. In
addition, in the case of isopropyl alcohol, there was a similar
result like t-butyl alcohol.
Conclusion
In summary, non-covalent functionalization of perchloric
acid onto the ordered mesoporous silica SBA-15/HClO4 as
a simply attainable heterogeneous, green, and reusable
Bronsted acid catalyst for cascade ring-opening and cyclization
towards heterocycles through diketene compound is
successfully achieved. By this method, DHPMs and DHPs are
accessible under ambient conditions, that this solid acidic
catalytic procedure based on neat conditions, is truly
recoverable compared to irrecoverable homogenous methods.
Such an approach avoids the use of expensive catalyst and
solvents or other additives. This rapid, green, and reusable
catalyst in four-component reactions was interesting
alternative to the other either of homogeneous or solid Bronsted
acid catalysts.
Acknowledgements We are thankful from Payame-Noor University for
financial supports on accomplishment of this manuscript.
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