TEDETA@BNPs as a basic and metal free nanocatalyst for Knoevenagel condensation and Hantzsch reaction

Article abstract of DOI:10.1007/s13738-018-1417-9

In this work, Boehmite nanoparticles (BNPs) were synthesized in water using commercially available materials and further N,N,N′,N′-tetraethyldiethylentriamin (TEDETA) was supported on the surface of BNPs, and used as organo-basic catalyst in four-componen

Full text of DOI:10.1007/s13738-018-1417-9

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-018-1417-9
ORIGINAL PAPER
TEDETA@BNPs as a basic and metal free nanocatalyst for Knoevenagel
condensation and Hantzsch reaction
Arash Ghorbani‑Choghamarani1 · Zahra Heidarnezhad · Bahman Tahmasbi · Gouhar Azadi
1
1
1
Received: 12 January 2018 / Accepted: 25 May 2018
©
Iranian Chemical Society 2018
Abstract
In this work, Boehmite nanoparticles (BNPs) were synthesized in water using commercially available materials and further
N,N,N′,N′-tetraethyldiethylentriamin (TEDETA) was supported on the surface of BNPs, and used as organo-basic catalyst in
four-component Hantzsch reaction that provides access to pharmaceutically polyhydroquinoline derivatives and Knoevenagel
reaction to afford α,β-unsaturated compounds. All products were obtained in excellent yields (89–98%) and good reaction
times under green condition such as water and ethanol solvents. This catalyst was characterized using FT-IR, SEM, EDS,
and TGA techniques. This catalyst was reused for several times without the significant loss of their catalytic efficiency. In
addition, stability of catalyst after recycling was confirmed by TGA, SEM, EDS and FT-IR techniques.
Keywords Boehmite nanoparticles · Polyhydroquinolines · Knoevenagel reaction · N,N,N′,N′-Tetraethyldiethylentriamin ·
Organocatalyst
Introduction
for the pharmaceutical and biological materials [16, 17]. In
general, organic bases, Lewis acids or organometallic homo-
geneous catalysts were reported for Knoevenagel condensa-
tion and multi-component Hantzsch condensation [18–22].
However, in green chemistry, metal catalysts (due to their
toxicity) are not eco-friendly. In addition, use of homogene-
ous catalyst is difficult in purity of products or reusability
of catalysts, which leads to their environmental problems.
Recently, to recover and reuse of homogenous catalysts,
insoluble solid supports was employed that provides access
to heterogeneous catalysts [23, 24]. Many insoluble supports
have been reported for the preparation of reusable heteroge-
neous catalysts. Insomuch, nanoparticles have a high surface
area, they have a better catalytic efficiency [25]. Boehmite
nanoparticles are one of these insoluble nanomaterials that
have been rarely used as heterogeneous support [26]. Boe-
hmite nanoparticles have a cubic orthorhombic unites of
oxide hydroxide particles of aluminum (ꢀ-AlOOH), that its
stable in air atmosphere, high temperature or aqueous solu-
tion, therefore, boehmite NPs are interesting support for the
heterogenization of homogeneous catalysts [27, 28]. BNPs
has several advantages, such as non-toxicity, readily avail-
ability form commercial materials, having high-surface-area
Polyhydroquinoline and α,β-unsaturated compounds have
been reported in a wide range of biological properties and
pharmaceutical activities [1–6]. Polyhydroquinoline deriva-
tives are important group of nitrogen-containing heterocycles
that have been used as hepatoprotective, vasodilator, antia-
therosclerotic, antitumor, geroprotective, bronchodilator, and
antidiabetic activity [4, 7]. Polyhydroquinoline derivatives
were commonly synthesized by multicomponent reaction
(
MCR) of aldehyde, dimedone, ethyl acetoacetate, ammo-
nium acetate. MCR is a synthetic methodology in which
three or more starting materials react together in a single
reaction vessel to form a new product, where all or most of
the atoms are present in the final product, Therefore, MCRs
are ideal and green reaction system. Therefore, MCRs have
been emerged much attention in various research fields such
as organic and medicinal chemistry [8–15]. Besides, Knoev-
enagel condensation between a carbonyl group and an acti-
vated methylene group is one of the useful reactions to pre-
pare α,β-unsaturated compounds as important intermediates
*
Arash Ghorbani-Choghamarani
2
arashghch58@yahoo.com; a.ghorbani@ilam.ac.ir
(up to 120 m /g) and ease of surface modification and ther-
mal and mechanical stability [26–30]. Several procedures
1
Department of Chemistry, Faculty of Science, Ilam
University, Ilam, P.O. Box 69315516, Iran
(sol–gel [31], hydrothermal [32] and hydrolysis of aluminum
Vol.:(0
1
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Journal of the Iranian Chemical Society
Scheme 1 Synthesis of TEDETA@BNPs
[
31, 33]) have been employed for the preparation of BNPs;
but, most of them have focused on the effect of parameters
on morphologies, chemical or physical properties of BNPs.
To extend catalytic application of BNPs, herein N,N,N′,N′-
tetraethyldiethylentriamin was immobilized on the surface of
boehmite nanoparticles (TEDETA@BNPs) as organo-basic
catalyst for the synthesis of polyhydroquinoline derivatives
and Knoevenagel reaction.
Experimental
Preparation of catalyst
Initially, boehmite nanoparticles reacted with 3-choloropro-
pyltrietoxysilane to give nPr-Cl@BNPs according to new
reported procedure [25], and further the obtained nPr-Cl@
BNPs (1.0 g) was dispersed in toluene and was mixed with
1
.5 mL of N,N,N′,N′-tetraethyldiethylentriamin (TEDETA).
The mixture was stirred at 90 °C for 24 h. The solid product
(
TEDETA@BNPs) was obtained after washing with ethanol
and drying at 50 °C.
General procedure for the Knoevenagel
condensation
A mixture of aldehyde (1 mmol), malononitrile (1 mmol)
and TEDETA@BNPs (0.024 g) was stirred at room tem-
perature in water and the progress of the reaction was moni-
tored by TLC. After completion of the reaction, catalyst was
separated using filtration and washed with ethyl acetate, and
the product was extracted with ethyl acetate. The organic
layer was dried over anhydrous Na SO (1.5 g). Finally,
2
4
the organic solvents were evaporated, and products were
obtained in good to high yield.
Fig. 1 SEM images of TEDETA@BNPs
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Journal of the Iranian Chemical Society
General procedure for the synthesis
of polyhydroquinoline derivatives
energy-dispersive X-ray spectroscopy (EDS), thermogravi-
metric analysis (TGA), and Fourier transform infrared spec-
troscopy (FT-IR).
A mixture of aldehyde (1 mmol), dimedone (1 mmol), ethyl
acetoacetate (1 mmol), ammonium acetate (1.2 mmol) and
TEDETA@BNPs (0.024 g) was stirred in ethanol at 80 °C and
the progress of the reaction was monitored by TLC. After com-
pletion of the reaction, catalyst was separated and washed with
ethyl acetate. Then, the solvent was evaporated and all products
was recrystallized in ethanol, which the pure polyhydroquino-
line derivatives were obtained in good to excellent yields.
The size of TEDETA@BNPs was evaluated by SEM tech-
nique. As is evidence from the SEM image of TEDETA@
BNPs, the diameter of prepared nanoparticles are about
40–90 nm (Fig. 1).
To indicate that content elements that were supported
on surface of boehmite nanoparticles, EDS analysis of
TEDETA@BNPs was performed (Fig. 2). As depicted, the
EDS spectrum of TEDETA@BNPs shows the presence of
Al, Si, O, C, and N species in the catalyst.
The TGA was used to determine the percentage of
organic groups supported on BNPs (Fig. 3). The TGA curve
of the TEDETA@BNPs shows the mass loss of the func-
tional groups as it decomposes upon heating. The weight
loss at temperatures below 200 °C is due to the removal
of physically adsorbed solvent and surface hydroxyl groups
[34]. The weight loss of about 26% between 200 and 500 °C
is associated to the decomposition of immobilized organic
layers [26].
Result and discussion
Catalyst preparation
The details of the catalyst preparation procedure are pre-
sented in Scheme 1. Initially, the insoluble nano-core
of BNPs has been prepared using commercially avail-
able materials via addition of NaOH (6.490 g) in 50 mL
of distilled water to the solution of Al(NO ) ·9H O (20 g
Figure 4 shows the FT-IR spectra for boehmite nano-
particles, nCl.Pr@BNPs, and TEDETA@BNPs. The Al–O
stretching vibration was observed as strong absorption
3
3
2
Al(NO ) ·9H O in 30 mL of distilled water). Ultimately, the
3
3
2
hydroxyl layer on the surface of BNPs has been modified
by 3-choloropropyltrietoxysilane (CPTES). The N,N,N′,N′-
tetraethyldiethylentriamin was reacted with modified BNPs
to provide TEDETA@BNPs.
−
1
bands at 480, 630 and 740 cm . In addition, symmetrical
and asymmetrical modes of the O-H bonds stretching vibra-
−
1
tion were observed above 3000 cm [34]. Several peaks
−
1
at 1075 and 1635 cm can be attributed to the character-
istic of hydrogen bands and nitrate impurity, respectively.
The presence of organic layers on the surface of BNPs is
Catalyst characterizations
−
1
After the preparation of TEDETA@BNPs, this catalyst
was characterized by scanning electron microscopy (SEM),
confirmed by the bands about 2850 and 2920 cm that
assigned to the C–H stretching vibrations. In addition, in
Fig. 2 EDX spectrum of TEDETA@BNPs
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Journal of the Iranian Chemical Society
Fig. 3 TGA/DTA diagram of
TEDETA@BNPs
Fig. 4 FT-IR spectra of boe-
hmite nanoparticles (a), nCl.
Pr@BNPs (b), and TEDETA@
BNPs (c)
070–1170 cm− spectral region of the FT-IR spectra (spec-
1
this region [23]. In addition, in the 1000–1250 cm spec-
−1
1
trum b and c), an overlap of the stretching vibrations of the
Si–O bonds with hydrogen bands leads to band broading in
tral region of the FT-IR spectra (Fig. 5b, c): an overlap of
the stretching vibration of the C–N bonds with Si–O bonds
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Journal of the Iranian Chemical Society
Table 1 Optimization for the synthesis of polyhydroquinoline via
condensation of 4-chlorobenzaldehyde whit dimedone, ethyl acetoac-
etate, and ammonium acetate
1
00
b
Entry Solvent
Catalyst
mg)
Time (min) Tem-
perature
°C)
Yield (%)a
9
8
7
6
5
4
3
2
1
0
0
0
0
0
0
0
0
0
0
a
(
(
1
2
Water
Ethyl
24
24
60
60
80
80
28
37
acetate
3
4
5
6
7
8
9
PEG
24
24
20
15
10
24
24
60
60
150
285
360
60
80
80
80
80
80
60
40
56
95
95
69
60
64
52
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
60
1
2
3
4
5
aIsolated yield
Run number
in ethanol at 80 °C in the presence of 24 mg of TEDETA@
BNPs.
Fig. 5 The recycling experiment of TEDETA@BNPs in synthesis of
polyhydroquinoline derivatives (a) and Knoevenagel condensation
(
b) using 4-chlorobenzaldehyde
After optimizing of the reaction conditions, the reaction
of a variety of aldehydes with ethyl acetoacetate, dimedone,
and ammonium acetate was then investigated to confirm the
generality of the present method. Polyhydroquinoline deriva-
tives were obtained in high yields. The results of this study
are summarized in Table 2. As shown in this table, a variety
of benzaldehydes bearing electron-donating and electron-
withdrawing substituents were successfully employed to
prepare corresponding polyhydroquinoline derivatives in
excellent yields. Terephthalaldehyde (Table 2, entry 10) also
afforded the desired product in excellent yield. Therefore,
the results revealed that this methodology is effective for a
wide range of aldehydes.
and OH…OH stretching vibration leads to band broaden-
ing [35, 36].
Catalytic activity
After the characterization of nanocatalyst, herein we have
examined the catalytic activity of TEDETA@BNPs in the
synthesis of polyhydroquinoline derivatives (Scheme 2).
Condensation of 4-chlorobenzaldehyde with ethyl acetoac-
etate, dimedone, and ammonium acetate was selected as
model reaction to find the best reaction conditions. The
several parameters were examined in this model reaction,
which the results of these experiments are summarized in
Table 1. As shown in Table 1, the best result was obtained
To extend the scope of our work, we next investigated the
catalytic activity of TEDETA@BNPs for Knoevenagel con-
densation (Scheme 3). To find the best reaction conditions,
condensation of 4-chlorobenzaldehyde with malononitrile
Scheme 2 TEDETA@BNPs catalyzed the synthesis of polyhydroquinoline derivatives
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Journal of the Iranian Chemical Society
Table 2 Synthesis of polyhydroquinoline derivatives catalyzed by TEDETA@BNPs
Time
Yield
(%)
Melting point Reported M.P.
Entry
Aldehyde
Product
a
(
min)
(°C)
[Refs.]
1
60
95
91
96
235–237
235–238 [5]
2
205
435
218–220
251–253
216–218 [37]
3
252–253 [6]
4
250
96
230–232
255–257
246–248
230–232 [37]
254–256 [37]
248–250 [38]
5
165
98
6
12h
90
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Journal of the Iranian Chemical Society
Table 2 (continued)
Time
min)
Yield
(%)
Melting point Reported M.P.
Entry
Aldehyde
Product
a
(
(°C)
[Refs.]
7
120
90
236–239
238–240 [38]
8
510
14h
95
90
184–186
176–178
185–186 [6]
9
176–178 [37]
1
0
420
89
304–306
305–307 [38]
1
1
240
180
91
93
209–211
203–205
–
–
1
2
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Journal of the Iranian Chemical Society
Table 2 (continued)
Entry
Time
Yield
(%)
Melting point Reported M.P.
Aldehyde
Product
a
(
min)
(°C)
[Refs.]
1
3
90
89
239–241
241–244 [39]
1
4
60
95
205–207
227–229
203–205 [5]
1
5
150
92
229–234 [39]
aIsolated yield
Scheme 3 TEDETA@BNPs catalyzed the Knoevenagel condensation
has been studied. The various amount of catalyst was exam-
ined and 24 mg of TEDETA@BNPs was found to ideal
amount of catalyst, meanwhile decrease in amount of cata-
lyst to 20 mg led to significant reducing of product yield to
Table 3 Optimization of Knoevenagel condensation for the reaction
of 4-chlorobenzaldehyde whit malononitrile
Yield (%)a
Entry Solvent
Catalyst (mg) Time (min)
1
2
3
4
5
6
7
Ethyl acetate 24
45
45
65
30
95
95
57
40
5
7%. In addition, among various solvents, the best results
Ethanol
PEG
24
24
24
30
20
10
45
45
45
45
60
60
were obtained in water. All results of optimization for Kno-
evenagel condensation are shown in Table 3.
Water
Water
Water
Water
The reaction of a variety of aldehydes with malononi-
trile was then investigated to confirm the generality of the
present methodology. The products were obtained in high
yields. The results of this study are summarized in Table 4.
As shown in Table 4, a variety of benzaldehydes bearing
electron-donating and electron-withdrawing substituents
were successfully employed to prepare the corresponding
products in excellent yields.
aIsolated yield
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Journal of the Iranian Chemical Society
Table 4 Knoevenagel condensation catalyzed by TEDETA@BNPs
Time
Yield Melting Reported M.P.
Entry
Aldehyde
Product
a
(
min)
(%) point (°C)
[Ref.]
1
45
95
159–161 162–164 [40]
2
3
30
9h
92
98
82–84
82–84 [1]
127–132 127–132 [41]
4
5
6
7
400
25
98
93
89
94
114–116
114 [16]
132–134 133–135 [42]
122–124 125–126 [1]
148–150 150–152 [43]
360
210
8
9
270
210
60
93
89
91
92
159–160 159–161 [43]
105–107 107–109 [44]
152–154 151–152 [45]
103–105 105–106 [42]
1
0
1
1
60
1
61.7–161.9
12
13
14
15
115
65
92
90
92
90
159–161
184–186
93–95
[18]
184 [16]
9
3.6–96.3
75
[46]
150
79–81
–
aIsolated yield
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Journal of the Iranian Chemical Society
conditions. The average isolated yield for five succes-
sive runs was 92.5% (in synthesis of polyhydroquinoline)
and 91.8% (in Knoevenagel condensation), which clearly
demonstrates the practical recyclability of this catalyst
(
Fig. 5).
In addition, to examine the stability of catalyst after
recycling, recycled catalyst has been characterized by
TGA, SEM, EDS and FT-IR techniques. These charac-
terizations were confirmed that recovered catalyst is good
agreement with fresh catalyst. These characterizations are
strong evidence for high stability of TEDETA@BNPs after
recycling.
The SEM image of recycled catalyst is shown in Fig. 6.
As shown in Fig. 6, particles of recovered catalyst were
observed between 50 and 100 nm with homogeneous size
and morphology. SEM image of recycled catalyst (Fig. 6) is
good agreement with SEM image of fresh catalyst (Fig. 1),
therefore, size and shape of catalyst have not been changed
after recycling.
Fig. 6 SEM image of recycled TEDETA@BNPs
TGA/DTG curves of recycled TEDETA@BNPs are
shown in Fig. 7. As shown in Fig. 7, adsorbed solvent
were removed in low temperature as small weight loss
about 4%. Organic layers were also decomposed between
200 and 500 °C as weight loss about 26% which is good
agreement to fresh catalyst (Fig. 3). Final weight loss
(about 2%) above 600 °C, may be due to thermal trans-
formation of boehmite phase [47]. Therefore, stability of
TEDETA@BNPs after recycling was confirmed by TGA
analysis.
Reusability of the catalyst
The TEDETA@BNPs can be easily recycled from the
synthesis of polyhydroquinoline derivatives and Knoev-
enagel condensation. To investigate this issue, the recy-
clability of the TEDETA@BNPs was examined for the
synthesis of polyhydroquinoline derivatives and Knoeve-
nagel condensation using 4-chlorobezaldehyde as a model
substrate. After the end of each reaction, the catalyst was
separated, washed with ethanol, and reused for subsequent
experiments (up to five cycles) under obtained reaction
To indicate the stability of elements of catalyst,
EDS analysis of recycled TEDETA@BNPs was con-
ducted (Fig. 8). As like to fresh catalyst (Fig. 2), the
Fig. 7 TGA/DTG curves of
recycled TEDETA@BNPs
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Journal of the Iranian Chemical Society
Fig. 8 EDS spectrum of recycled TEDETA@BNPs
EDS spectrum of recycled TEDETA@BNPs shows the
presence of Al, Si, O, C, and N species in the recycled
catalyst.
comparable or may be better in terms of price, non-toxicity,
stability and easy separation.
FT-IR spectrums of fresh catalyst and recycled catalyst
were shown in Fig. 9. As shown in Fig. 9, good agreement
was observed for FT-IR of fresh and recycled catalyst.
Therefore, Fig. 9 is shown good stability of TEDETA@
BNPs after recycling.
Conclusions
In conclusion, a reusable and metal-free catalyst has been
introduced for a simple, efficient and environmentally
benign method for the synthesis of polyhydroquinoline
derivatives and α,β-unsaturated compounds. This meth-
odology is effective for a wide range of aldehydes for the
synthesis of polyhydroquinolines and α,β-unsaturated com-
pounds. More importantly, this catalyst can be prepared
from inexpensive and available starting materials. In addi-
tion, nano-boehmite is a new and stable support which was
prepared using a very simple procedure in water without
inert atmosphere, which has several advantages such as high
surface area, high stability, ease of surface modification,
easy and inexpensive procedure of preparation. This cata-
lyst was characterized by FT-IR, SEM, EDS, and TGA tech-
niques and can be reused for several times with little loss
of its activity. Also recovered catalyst was characterized by
FT-IR, SEM, EDS and TGA techniques. The advantages
Comparison study of the catalyst
To compare the catalytic activity of TEDETA@BNPs, we
compared the results of the synthesis of ethyl 2,7,7-tri-
methyl-5-oxo-4-(p-tolyl)-1,4,5,6,7,8-hexahydroquino-
line-3-carboxylate (Table 2, entry 5) in the presence of this
catalyst with the previously reported catalyst in the litera-
tures, which results of this comparison were summarized in
Table 5. This catalyst affords good reaction time and high
product yield in compared to other catalysts. More impor-
tance, in compared with other catalyst, TEDETA@BNPs has
been easily prepared using cheap and commercially avail-
able materials, and can be reused for several times without
any significant loss of its activity. This new catalysts are
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Journal of the Iranian Chemical Society
Fig. 9 FT-IR spectrums of fresh
TEDETA@BNPs (a) and recy-
cled TEDETA@BNPs (b)
Table 5 Comparison of TEDETA@BNPs for the synthesis of ethyl
Acknowledgements Authors thank the research facilities of Ilam Uni-
2
,7,7-trimethyl-5-oxo-4-(p-tolyl)-1,4,5,6,7,8-hexahydroquino-
versity, Ilam, Iran, for financial support of this research project.
line-3-carboxylate with previously reported procedure
a
Entry Catalyst
Time (min)
Yield (%) [Reference]
1
2
3
4
5
6
Cu-SPATB/Fe O
GSA@MNPs
Boehmite-SSA
Ascorbic acid
240
260
250
150
240
165
91 [4]
89 [48]
96 [49]
80 [50]
83 [51]
98 [This work]
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