FSM-16-SO3H nanoparticles as a novel heterogeneous catalyst: Preparation, characterization, and catalytic application in the synthesis of polyhydroquinolines

Article abstract of DOI:10.1515/mgmc-2018-0006

FSM-16-SO₃H nanoparticles were prepared using a sol-gel method at room temperature. The prepared FSM-16-SO₃H was used to catalyze the synthesis of polyhydroquinolines through a one-pot, four-component reaction of aldehydes, dimedone, ethyl cyanoacetate, and ammonium acetate under reflux condition in EtOH as a green solvent. To investigate the textural properties of the prepared catalyst, various techniques were applied such as X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscope, and Brunauer-Emmett-Teller. High catalytic activity, easy handling, and thermal stability are the superior properties that could be denoted after successive investigations of this catalyst. In addition, the catalyst can be recovered easily and reused effectively for several cycles.

Full text of DOI:10.1515/mgmc-2018-0006

Main Group Met. Chem. 2018; 41(3–4): 91–101
Somayeh Hashemi-Uderji, Mohammad Abdollahi-Alibeik* and Reza Ranjbar-Karimi
FSM-16-SO H nanoparticles as a novel heterogeneous catalyst:
3
preparation, characterization, and catalytic application in the
synthesis of polyhydroquinolines
https://doi.org/10.1515/mgmc-2018-0006
1987). Moreover, these compounds can be used for their
antioxidant protective effect in addition to their pharmaco-
logical activities (Mason et al., 1999). Thus, the synthesis of
these heterocyclic compounds is of much importance.
Received February 1, 2018; accepted July 4, 2018
Abstract: FSM-16-SO H nanoparticles were prepared using
3
a sol-gel method at room temperature. The prepared FSM-
1
,4-DHPs are generally achieved using the classic
1
6-SO H was used to catalyze the synthesis of polyhydro-
3
Hantzsch method, which involves the condensation of an
aldehyde with ethyl acetoacetate and ammonia in acetic
acid or by refluxing in alcohol (Hantzsch, 1882). This
method, however, involves long reaction times and the use
of a large quantity of volatile organic solvents and gener-
ally gives low yields. Several catalysts such as ionic liquid
quinolines through a one-pot, four-component reaction
of aldehydes, dimedone, ethyl cyanoacetate, and ammo-
nium acetate under reflux condition in EtOH as a green
solvent. To investigate the textural properties of the pre-
pared catalyst, various techniques were applied such as
X-ray diffraction, Fourier transform infrared spectroscopy,
scanning electron microscope, and Brunauer–Emmett–
Teller. High catalytic activity, easy handling, and thermal
stability are the superior properties that could be denoted
after successive investigations of this catalyst. In addition,
the catalyst can be recovered easily and reused effectively
for several cycles.
(
Khaligh, 2016), Baker’s yeast (Kumar and Maurya, 2007),
silica gel/NaHSO (Adharvana Chari and Syamasundar,
4
2
005), Yb(OTf) (Wang et al., 2005), Sc(OTf) (Donelson
3
3
et al., 2006), ZnO (Moghaddam et al., 2009), MgO (Ran-
jbar-Karimi et al., 2011), ceric ammonium nitrate (Ko and
Yao, 2006), polymers (Dondoni et al., 2004), HClO -SiO2
(
4
Maheswara et al., 2006), HY-zeolites (Das et al., 2006),
Keywords: FSM-16-SO H; Hantzsch reaction; nanoparti- montmorillonite K-10 (Song et al., 2005), p-TSA (Kumar
3
cle; polyhydroquinoline; sol-gel.
and Maurya, 2008), ꢀ-proline (Karade et al., 2007), ZrCl4
Reddy and Raghu, 2008), MCM-41 (Nagarapu et al.,
007), Hf(NPf ) (Hong et al., 2010), Cu(OTf) (Pasunooti
(
2
2
4
2
Introduction
et al., 2010), Fe O @B-MCM-41 (Abdollahi-Alibeik and
3 4
Rezaeipoor-Anari, 2016), and MCM-41-OBF2 (Abdollahi-
Polyhydroquinoline and 1,4-dihydropyridine (1,4-DHP) Alibeik and Rezaeipoor-Anari, 2015) have been used to
derivatives have attracted noticeable concern because improve Hantzsch reaction conditions. Also, several energy
they have diverse biological activities such as geroprotec- sources such as microwaves (Tu et al., 2006), grinding tech-
tive, vasodilator, antitumor, bronchodilator, hepatopro- niques (Kumar et al., 2008), ultrasound (Guo and Yuan,
tective, antiatherosclerotic, calcium channel blocker, and 2010), and solar heat (Mekheimer et al., 2008) have been
antidiabetic activity (Davis and Davis, 1979; Bretzel et al., reported for this purpose. Furthermore, the development of
1
992, 1993; Boer and Gekeler, 1995; Klusa, 1995). Recently, an efficient and versatile method for the preparation of 1,4-
research has shown that 1,4-DHPs exhibit diverse medicinal DHPs and polyhydroquinoline is an active ongoing research
usage, which includes neuroprotectant and platelet antiag- area and there is scope for further improvement toward
gregatory activity, in addition to cerebral anti-ischemic milder reaction conditions and to access higher yields.
activity in the treatment of Alzheimer’s disease and as a
Recently, heterogeneous catalysts have become attrac-
chemosensitizer in tumor therapy (Pastan and Gottesman, tive from both economic and industrial points of view
as compared with homogeneous catalysts. In general,
*
Corresponding author: Mohammad Abdollahi-Alibeik, Department
nanoscale heterogeneous catalysts offer higher surface
area and lower coordinating sites, which are responsible
for the higher catalytic activity.
Mesoporous silica as a nanostructured material with
highly ordered pores and high surface area, such as
FSM-16 and MCM-41, have attracted considerable interest
in the fields of adsorption science and catalysis chemistry
of Chemistry, Yazd University, Yazd 89158-13149, Iran,
Tel.: +98-35-31232659, Fax: +98-35-38210644,
e-mail: abdollahi@yazd.ac.ir, moabdollahi@gmail.com
Somayeh Hashemi-Uderji: Department of Chemistry, Yazd
University, Yazd 89158-13149, Iran
Reza Ranjbar-Karimi: Department of Chemistry, Faculty of Science,
Vali-e-Asr University, Rafsanjan 77176, Iran
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2ꢀꢀꢀꢀꢁꢀS. Hashemi-Uderji et al.: FSM-16-SO H nanoparticles as a novel heterogeneous catalyst
3
(
Yanagisawa et al., 1990; Inagaki et al., 1993; Inagaki et al., inner surface of the mesopores to enhance the catalytic
996; Abdollahi-Alibeik and Pouriayevali, 2011; Abdollahi- activity and the acidic or basic characteristics of organic
1
Alibeik and Rezaeipoor-Anari, 2014). Mesoporous silica of transformations.
the FSM type, which is composed of siliceous sheets, was
synthesized by Inagaki and co-workers (Inagaki et al., acterization of FSM-16-SO H as a novel heterogeneous
In this research, we report the preparation and char-
3
1
993). Folded sheet silicate mesoporous material (FSM-16) acid catalyst by functionalization of silanol groups on the
was first synthesized by ion exchange of interlayer Na ions surface of FSM-16 with -SO H groups (Scheme 1).
3
of the layered polysilicate kanemite (NaHSi O ·ꢁ3H O) with
surfactant (Yanagisawa et al., 1990; Inagaki et al., 1993).
The catalytic activity of FSM-16-SO H was also studied
2
5
2
3
in the reaction of various types of aldehydes, dimedone,
Considering the fact that FSM-16 offers high surface ethyl cyanoacetate, and ammonium acetate for the syn-
area, many functional groups can be anchored on the thesis of polyhydroquinolines (Scheme 2).
Kanemite
Ion-exchange
CTAB
Hexagonal array
Calcination
Si
OSO H
3
O
ClSO H
Si
OSO H
3
3
O
OSO H
3
Si
FSM-16-SO H
Si
3
FSM-16
OH
O
Si OH
O
OH
CTAB: n-cetyltrimethylammonium bromide
Scheme 1:ꢀSchematic representation for the preparation of FSM-16-SO H.
Si
3
O
H
O
O
O
O
FSM-16-SO3H
CN
+ NH4OAc
+
+
OEt
EtO
O
N
H
NH2
Scheme 2:ꢀSynthesis of polyhydroquinolines using a one-pot, four-component reaction in the presence of FSM-16-SO H.
3
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S. Hashemi-Uderji et al.: FSM-16-SO3H nanoparticles as a novel heterogeneous catalystꢂꢁꢀꢀꢀꢂ93
Results and discussion
B
The catalyst characterization
A
FSM-16 and FSM-16-SO H were characterized using Fourier
3
transform infrared spectroscopy (FT-IR), scanning elec-
tron microscope (SEM), Brunauer–Emmett–Teller (BET),
and X-ray diffraction (XRD) techniques. The SEM micro-
graphs of FSM-16 and FSM-16-SO H are shown in Figure 1A
3
and B, respectively. SEM micrographs show spherical
nanoparticles with sizes of approximately 100 nm. Both
materials have similar texture and there is no significant
difference.
1084
The FT-IR spectra of FSM-16 and FSM-16-SO H are
3
1082
shown in Figure 2. The spectrum of FSM-16 (Figure 2A)
shows characteristic peaks at 1216, 1082, and 804 cm−
due to symmetric and asymmetric stretching vibrations of
2
000
1600
1200
800
400
1
Wavenumber (cm–1
)
−1
Si-O-Si and also the peak of 966 cm due to Si-OH groups. Figure 2:ꢀFT-IR spectra of (A) FSM-16 and (B) FSM-16-SO H.
3
−1
The peak at 463 cm is assigned to the bending vibration
of Si-O-Si. For FSM-16-SO H (Figure 2B), the FT-IR bands of
3
−
1
the O=S=O asymmetric and symmetric stretching modes lie in 1120–1230 and 1010–1080 cm , respectively, and that
−1
of the S-O stretching mode lies in 600 cm . The FT-IR spec-
trum of FSM-16-SO H shows the overlap of asymmetric and
3
symmetric stretching bands of SO with Si-O-Si stretching
2
−1
bands in the region of 1000–1250 cm , which results in an
increase of intensity of this peak.
The low angle XRD patterns of FSM-16 and FSM-16-
SO H are shown in Figure 3. The characteristic peaks
3
A
B
2
3
4
5
6
7
2θ (°)
Figure 1:ꢀSEM images of (A) FSM-16 and (B) FSM-16-SO H.
Figure 3:ꢀLow angle XRD patterns of (A) FSM-16 and (B) FSM-16-SO H.
3
3
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4ꢀꢀꢀꢀꢁꢀS. Hashemi-Uderji et al.: FSM-16-SO H nanoparticles as a novel heterogeneous catalyst
3
of FSM-16 (Figure 3A) appeared at 2θꢁ=ꢁ2.38°, 4.11°, and FSM-16 shows only peaks of pyridine-bonded Lewis acid
−
1
4
.73° in accordance with the literature (Araki et al., sites at 1446 and 1598 cm (Figure 4B). The spectrum of
2
003). As shown in Figure 3B, after surface modifica- pyridine-adsorbed FSM-16-SO H before heat treatment
tion with SO H groups, the intensity of the main peak (Figure 4C) shows the contribution of the pyridine adducts
3
3
−1
−1
(
(
2θꢁ=ꢁ2.38°) decreased and shifted to the higher angle in the region of 1400–1650 cm . The peak at 1487 cm is
2θꢁ=ꢁ2.76°). Any increase in the width of the main peak attributed to the combination of pyridine bonded to Lewis
−1
of the FSM-16-SO H is due to a decrease in the long-range and Brønsted acid sites. The peak appearing at 1530 cm
3
order of the hexagonal mesostructure of FSM-16 after is assigned to Brønsted acid sites (pyridinum ion). The
the incorporation of -SO H groups into the channels of peak at 1603 cm− is attributed to the pyridine-bonded
1
3
−1
FSM-16. The shift in the main peak of FSM-16-SO H to a Lewis acid sites of the catalyst. The peak at 1633 cm in
3
higher angle is due to a decrease in the pore diameter the spectrum of the catalyst before treatment with pyri-
because of the insertion of sulfonic acid groups on the dine (Figure 4A) is due to the presence of water during the
inner surface of mesopores.
preparation of the pellet sample. This sharp peak over-
The distribution of both Brønsted and Lewis acid lapped with another weak peak from the Brønsted acid site
−1
sites of FSM-16-SO H was detected using FT-IR spectro- at 1642 cm . However, these results confirm the distribu-
3
scopy by means of pyridine absorption. Figure 4 shows tion of both Brønsted and Lewis acid sites on the surface
the pyridine adsorbed spectra of FSM-16-SO H heated at of the catalyst. As shown in Figure 4B–E, with increasing
3
various temperatures. The spectrum of pyridine adsorbed temperature, the characteristic peak of Lewis acid sites at
−
1
−1
1
603 cm and the peak of Brønsted acid sites at 1530 cm
still remained. These results confirm that -SO H function-
3
alization has strengthened both Brønsted and Lewis acid
sites on the catalyst.
The strength and number of acid sites of the cata-
lysts were determined by potentiometric titration of
samples with 0.02 N solution of n-butylamine in ace-
tonitrile. According to this method, the initial electrode
A
B
potential (E ) indicates the strength of the acid sites, and
i
the meq of the consumed base indicates the number
of acid sites (Pizzio et al., 2003). As shown in Figure 5,
the very low initial potential of FSM-16 shows that the
acid strength of these samples is very low. By placing
the -SO H groups on the surface of FSM-16, FSM-16-SO H
C
3
3
displays higher strength than that of FSM-16. Because of
the higher meq of the used base per gram of the FSM-
D
1
6-SO H, this sample also has a higher number of acidic
3
sites than FSM-16.
E
6
4
2
00
00
00
0
B
A
1800
1600
1400
1200
1000
–
1
–200
Wavenumbers (cm )
0
.0
0.5
1.0
1.5
meq (g)
2.0
2.5
Figure 4:ꢀFT-IR spectra of (A) FSM-16-SO H, (B) pyridine adsorbed
3
FSM-16, and (C) FSM-16-SO H at ambient temperature; pyridine-
3
adsorbed FSM-16-SO H heated at (D) 100°C and (E) 200°C.
Figure 5:ꢀPotentiometric titration of (A) FSM-16 and (B) FSM-16-SO H.
3
3
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S. Hashemi-Uderji et al.: FSM-16-SO3H nanoparticles as a novel heterogeneous catalystꢂꢁꢀꢀꢀꢂ95
To investigate the number of -SO H acidic sites sup-
Figure 7 shows the N adsorption–desorption iso-
2
3
ported on the FSM-16, the elemental composition of the therms of the FSM-16 and FSM-16-SO H catalysts. In
3
FSM-16-SO H was determined using energy dispersive the isotherms of FSM-16, a mesoporous inflection was
3
X-ray (EDX) analysis, and the results are shown in Figure 6 observed at the medium p/p° partial pressure region
and Table 1. Based on these results, the amount of sulfur (p/p°ꢁ=ꢁ0.1–0.3) due to the capillary condensation of N2
in the FSM-16-SO H was 7.08 wt.%, and thus the number in the mesopores. A sharper hysteresis was observed at
3
of -SO H on the catalyst was 0.87 mmol per gram of higher p/p° (p/p°ꢁ>ꢁ0.8) for both catalysts. The hysteresis
3
FSM-16-SO H.
in this region is because of the condensation of N within
3
2
the voids formed by nanoparticles. In the isotherms of
FSM-16-SO H, the curvature of the mesoporous struc-
3
1000
ture in the area of P/P°ꢁ=ꢁ0.2–0.4 decreased because the
9
8
7
6
5
4
3
2
1
00
00
00
00
00
00
00
00
00
0
hexagonal cavities were occupied by -SO H groups. The
3
textural properties of FSM-16-SO H were also studied by
3
N adsorption–desorption isotherms. According to the
2
obtained results, the BET surface area for FSM-16-SO H
3
2
was measured to be 634 m /g and the average pore diam-
eter using the Barret–Joyner–Halenda desorption method
was calculated to be 5.97 nm.
0
10.00 Catalytic activity of FSM-16-SO H
3
keV
After the catalyst characterization was done success-
Figure 6:ꢀEnergy-dispersive X-ray spectrum of FSM-16-SO H.
3
fully, the catalytic activity of FSM-16-SO H nanoparticles
3
was investigated in the synthesis of polyhydroquinolines.
Initially, the reaction of benzaldehyde, dimedone, ethyl
cyanoacetate, and ammonium acetate was selected as the
Table 1:ꢀElemental composition of FSM-16-SO H.
3
Element
O
Si
S
model reaction and the results are summarized in Table 2.
wt.%
ꢃꢄ.ꢅꢄ
ꢅꢄ.ꢃꢆ
ꢇ.ꢆꢈ
The effect of solvent and temperature was investi-
gated by performing the model reaction in the presence
of 40 mg of catalyst in various solvents and temperatures
(
Table 2, entries 1–6). Among them, ethanol was found to
6
5
0
0
be the best solvent at reflux condition in terms of the reac-
tion time and yield of product (Table 2, entry 6). The lower
yield and longer reaction time was achieved by perform-
ing the model reaction in the presence of ethanol as the
solvent at r.t. condition (Table 2, entry 5).
To optimize the required catalyst amount, the model
reaction was also performed in the presence of various
amounts of catalyst, and according to the obtained results
(Table 2, entries 6 and 9–11), 40 mg of the catalyst was
chosen as the best amount. Clearly, the FSM-16 support
strongly affected the efficiency of the heterogeneous cata-
lyst. To show this, the model reaction in the presence of
40 mg FSM-16 was performed under the same reaction
conditions and lower yield of the product was obtained
after 90 min (Table 2, entry 8).
2
2
1
1
50
00
50
00
A
Desorption
Adsorption
0.8
4
3
2
1
0
0
0
0
0.2
0.4
0.6
Relative pressure (p/p°)
0
.8
Desorption
B
Adsorption
0.8
0.2
0.4
0.6
The scope and generality of this methodology has
been illustrated with respect to the reaction of different
types of benzaldehydes that have electron-withdrawing
and electron-donating groups with dimedone, ammonium
Relative pressure (p/p°)
Figure 7:ꢀN adsorption–desorption isotherms of (A) FSM-16 and (B)
FSM-16-SO H.
2
3
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6ꢀꢀꢀꢀꢁꢀS. Hashemi-Uderji et al.: FSM-16-SO H nanoparticles as a novel heterogeneous catalyst
3
Table 2:ꢀOptimization of the reaction conditions for the synthesis of polyhydroquinoline in the presence of FSM-16-SO H.a
3
O
H
O
O
O
O
FSM-16-SO H
3
CN
NH OAc
4
+
OEt
NH2
+
+ EtO
O
N
H
Entry
Catalyst
Catalyst amount (mg)
Solvent
Time (min)
Yield (%)b
ꢄ
ꢊ
ꢅ
ꢉ
ꢋ
FSM-ꢄꢃ-SO H
ꢉꢆ
ꢉꢆ
ꢉꢆ
ꢉꢆ
ꢉꢆ
ꢄ0
ꢆ
ꢉꢆ
ꢊꢆ
ꢅꢆ
ꢋꢆ
CHClꢅ
ꢄꢈꢆ
ꢊꢉꢆ
ꢅꢆ
ꢇꢃ
ꢇꢄ
ꢈꢈ
ꢈꢊ
ꢈꢄ
ꢅꢃ
ꢅꢆ
ꢇꢌ
ꢈꢇ
ꢈꢉ
ꢈꢈ
ꢅ
FSM-ꢄꢃ-SO H
CH Cl
ꢅ
ꢊ
ꢊ
FSM-ꢄꢃ-SO H
MeOH
ꢅ
FSM-ꢄꢃ-SO H
CH CN
ꢃꢆ
ꢅ
ꢅ
c
FSM-ꢄꢃ-SO H
EtOH
ꢊꢉꢆ
ꢃ0
ꢅ
d
ꢁ
FSM-ꢂꢁ-SO H
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
ꢃ
ꢇ
–
ꢊꢉꢆ
ꢌꢆ
ꢈ
FSM-ꢄꢃ
ꢌ
FSM-ꢄꢃ-SO H
ꢅꢋ
ꢅ
ꢄꢆ
ꢄꢄ
FSM-ꢄꢃ-SO H
ꢅꢆ
ꢅ
FSM-ꢄꢃ-SO H
ꢉꢋ
ꢅ
aReaction condition: benzaldehyde (1 mmol), dimedone (1 mmol), ethyl cyanoacetate (1.1 mmol), and ammonium acetate (1.2 mmol) at reflux
condition.
b
Isolated yield.
c
Reaction was carried out at room temperature.
d
Bolded row represent optimized condition.
acetate, and ethyl cyanoacetate and the results are sum-
marized in Table 3.
Conclusion
The reaction of various types of aryl aldehydes with In summary, we have developed a novel, mild, and effi-
both electron-donating and electron-withdrawing substit- cient strategy for the synthesis of polyhydroquinoline
uents were carried out under optimal conditions and the from dimedone, aryl aldehydes, ammonium acetate, and
corresponding polyhydroquinolines were obtained in high ethyl cyanoacetate through Knoevenagel condensation
to excellent yields (Table 3, entries 2–11). As exemplified in followed by Michael addition reaction in the presence
Table 3, this protocol is rather general for a wide variety of of FSM-16-SO H as a heterogeneous solid acid catalyst.
3
electron-rich as well as electron-deficient aromatic alde- The catalyst was texturally investigated using various
hydes. Although a regular trend was not observed based techniques such as SEM, XRD, FT-IR, and BET, and the
on the activity of aldehyde derivatives, the results in Table results show that the mesoporous structure of the bare
3
show that aldehydes with electron-withdrawing groups support (FSM-16) was maintained during sulfonic acid
such as -NO , Cl, Br, and -F have maximum rates of reaction. functionalization. In addition, the characteristic acidity
2
To investigate the reusability of FSM-16-SO H, it was of the obtained catalyst was proved by pyridine adsorp-
3
separated from the reaction mixture and washed with tion and potentiometric titration techniques. After suc-
ethanol. The catalyst was dried in an oven at 120°C for 2 h. cessful characterization of the catalyst, catalytic activity
The recycled catalyst was reused in the model reaction. was investigated in the synthesis of polyhydroquinolines
The catalyst was found to be reusable for at least three and optimal reaction conditions were obtained. The
cycles without considerable loss of activity (Table 4).
generality of the catalytic process was confirmed using
Table 5 shows a comparison between the activity of various precursors and the corresponding products were
the FSM-16-SO H and the other reported catalysts for the obtained in good to excellent yields and characterized
3
polyhydroquinoline synthesis through reaction of benza- by NMR and FT-IR. A reusability test shows that the
ldehyde, dimedone, ethyl cyanoacetate, and ammonium mesoporous FSM-16-SO H catalyst is reusable with mod-
3
acetate. Results show that FSM-16-SO H is comparable erate decrease in activity. High yields of the products,
3
with other catalytic systems in terms of reaction time very simple workup, and ease of the catalyst recovery are
and/or yield.
some of the advantages of using this catalyst.
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S. Hashemi-Uderji et al.: FSM-16-SO3H nanoparticles as a novel heterogeneous catalystꢂꢁꢀꢀꢀꢂ97
Table 3:ꢀSynthesis of polyhydroquinolines in the presence of FSM-16-SO H.
3
O
H
O
O
O
O
FSM-16-SO3H (40 mg)
CN
+
+
+ NH4OAc
OEt
NH2
EtO
EtOH, reflux
O
N
H
1
2
3
4
5
a
Entryꢆ
Aldehyde (ꢂ)
ꢆ
Polyhydroquinoline (ꢇ)ꢆ
Timeꢆ
Yield ꢆ
mp (°C)
(
min)
(%)ꢆ
Foundꢆ
Lit. [ref]
O
H
a
ꢍ
ꢍ
ꢍ
ꢅꢆꢍ
ꢌꢅꢍ
ꢄꢋꢇ–ꢄꢃꢆꢍ
ꢄꢋꢆ–ꢄꢋꢋ (Kumar et al., ꢊꢆꢆꢈ)
O
O
OEt
N
NH2
H
O
Cl
b
ꢍ
ꢍ
ꢍ
ꢍ
ꢍ
ꢊꢆꢍ
ꢊꢆꢍ
ꢈꢈꢍ
ꢌꢉꢍ
ꢄꢋꢋ–ꢄꢋꢇꢍ
ꢄꢌꢆ–ꢄꢌꢋꢍ
ꢄꢋꢆ–ꢄꢋꢅ (Abdollahi-Alibeik
and Rezaeipoor-Anari, ꢊꢆꢄꢃ)
H
Cl
O
O
OEt
NH2
N
H
O
NO2
c
ꢍ
ꢄꢌꢆ–ꢄꢌꢋ (Abdollahi-Alibeik
and Rezaeipoor-Anari, ꢊꢆꢄꢃ)
H
O2N
O
O
OEt
NH2
N
H
O
Me
d
e
ꢍ
ꢍ
ꢍ
ꢍ
ꢍ
ꢍ
ꢉꢆꢍ
ꢄꢋꢍ
ꢌꢆꢍ
ꢈꢈꢍ
ꢄꢅꢌ–ꢄꢉꢄꢍ
ꢄꢅꢋ–ꢄꢅꢃꢍ
ꢄꢅꢋ–ꢄꢅꢇ (Kumar et al., ꢊꢆꢆꢈ)
H
Me
O
O
OEt
N
H
NH2
O
Br
ꢄꢉꢆ–ꢄꢉꢅ (Abdollahi-Alibeik
and Rezaeipoor-Anari, ꢊꢆꢄꢃ)
Br
H
O
O
OEt
N
H
NH2
O
NO2
O
f
ꢍ
ꢍ
ꢍ
ꢍ
ꢍ
ꢍ
ꢄꢆꢍ
ꢃꢆꢍ
ꢈꢌꢍ
ꢈꢆꢍ
ꢄꢈꢅ–ꢄꢈꢉꢍ
ꢄꢇꢊ–ꢄꢇꢋꢍ
–
O2N
H
O
OEt
N
H
NH2
O
N
g
ꢄꢇꢌ–ꢄꢈꢄ (Abdollahi-Alibeik
and Rezaeipoor-Anari, ꢊꢆꢄꢃ)
N
H
O
O
OEt
NH2
N
H
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9
8ꢀꢀꢀꢀꢁꢀS. Hashemi-Uderji et al.: FSM-16-SO H nanoparticles as a novel heterogeneous catalyst
3
Table 3ꢈ(continued)
Entryꢆ Aldehyde (ꢂ)
a
ꢆ
Polyhydroquinoline (ꢇ)ꢆ
Timeꢆ
Yield ꢆ
mp (°C)
Foundꢆ
(
min)
(%)ꢆ
Lit. [ref]
Cl
O
h
ꢍ
ꢍ
ꢍ
ꢋꢍ
ꢌꢉꢍ
ꢄꢈꢊ–ꢄꢈꢅꢍ
ꢄꢈꢅ–ꢄꢈꢋ (Abdollahi-Alibeik
and Rezaeipoor-Anari, ꢊꢆꢄꢃ)
Cl
O
H
O
OEt
N
H
NH2
O
OMe
i
ꢍ
ꢍ
ꢍ
ꢍ
ꢍ
ꢍ
ꢍ
ꢋꢋꢍ
ꢊꢋꢍ
ꢄꢋꢍ
ꢈꢅꢍ
ꢌꢅꢍ
ꢌꢄꢍ
ꢄꢊꢈ–ꢄꢅꢆꢍ
ꢄꢊꢊ–ꢄꢊꢋ (Kumar et al., ꢊꢆꢆꢈ)
H
MeO
O
O
OEt
N
H
NH2
O
F
j
ꢍ
ꢍ
ꢄꢋꢋ–ꢄꢋꢈꢍ
ꢊꢊꢊ–ꢊꢊꢃꢍ
–
–
H
F
O
O
OEt
N
H
NH2
OMe
O
O
MeO
O
k
MeO
H
OEt
NH2
OMe
N
H
aIsolated yield.
Table 4:ꢀRecycling of FSM-16-SO H nanoparticles.
3
Experimental
Materials and methods
Run
Yield (%)a
Time
ꢄ
ꢊ
ꢅ
ꢌꢅ
ꢌꢆ
ꢈꢇ
ꢅꢆ
ꢉꢆ
ꢉꢋ
All chemicals were commercial grade and were used as-received. The
reactions were monitored using thin layer chromatography (TLC).
The yields of products refer to isolated compounds. Melting points
aIsolated yields.
Table 5:ꢀThe comparative study of the activity of FSM-16-SO H with other catalysts.
3
Entry Catalyst
Solvent
Temperature (°C) Time (min) Yielda Ref.
ꢄ
ꢊ
ꢅ
ꢉ
ꢋ
ꢃ
ꢇ
ꢈ
FSM-ꢄꢃ-SO H
Ethanol
THF
Reflux
Reflux
ꢅꢆ
ꢊꢉꢆ
ꢅꢆ
ꢋꢆ
ꢉꢆ
ꢉꢆ
ꢊꢆ
ꢋ
ꢌꢅ This work
ꢅ
PdClꢊ
ꢈꢇ (Saha and Pal, ꢊꢆꢄꢄ)
ZnO NPs
Solvent free r.t.
ꢈꢈ (Kassaee et al., ꢊꢆꢄꢆ)
MCM-ꢉꢄ-OBFꢊ
Ethanol
Ethanol
Ethanol
Solvent free r.t.
ꢋꢆ
Reflux
Reflux
Reflux
ꢌꢄ.ꢋ (Abdollahi-Alibeik and Rezaeipoor-Anari, ꢊꢆꢄꢋ)
ꢌꢆ (Abdollahi-Alibeik and Rezaeipoor-Anari, ꢊꢆꢄꢃ)
ꢌꢉ (Abdollahi-Alibeik and Hoseinikhah, ꢊꢆꢄꢃ)
ꢇꢊ (Kumar et al., ꢊꢆꢆꢈ)
Fe O @B-MCM-ꢉꢄ
ꢅ
ꢉ
ꢉ−
ClO /Zr-MCM-ꢉꢄ
(Grinding)
(Microwave irradiation) Ethanol
ꢌꢄ (Saha et al., ꢊꢆꢄꢅ)
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S. Hashemi-Uderji et al.: FSM-16-SO3H nanoparticles as a novel heterogeneous catalystꢂꢁꢀꢀꢀꢂ99
were obtained with a Buchi B-540 apparatus and are uncorrected. amount of FSM-16-SO H (40 mg) was stirred in ethanol (1.5 mL) under
3
1
13
H NMR and C NMR spectra of polyhydroquinolines were recorded reflux conditions. After completion of the reaction (monitored by
in DMSO-d on a Bruker DRX-500 AVANCE spectrometer (500 MHz TLC, eluent; n-hexane: ethyl acetate, 1:1), the catalyst was separated
for H and 125.72 MHz for C). Infrared spectra of the reaction prod- from the reaction mixture using a centrifuge and washed with etha-
ucts and catalysts were recorded on a Bruker FT-IR Equinax-55 in KBr nol (2ꢁ×ꢁ3 mL). After evaporation of solvent, the crude products were
disks. The XRD patterns were recorded on a Bruker D8 ADVANCE crystallized from ethanol to give pure polyhydroquinolines.
X-ray diffractometer using Ni-filtered CuKa radiation. The morphol-
6
1
13
ogy was studied using a KYKY-EM3200 SEM. The BET surface area
was measured using a micromeritics model ASAP2020 from the
Physical and spectroscopic data for selected compounds
nitrogen adsorption–desorption isotherms at 77 K. All samples were
degassed at 120°C under flowing nitrogen for 2 h. The specific sur-
Ethyl
2-amino-1,4,5,6,7,8-hexahydro-7,7-dimethyl-5-oxo-4-phe-
face area (SBET) was calculated from the adsorption data using the
BET equation, and the pore volume (Vpore) was estimated from the
nylquinoline-3-carboxylate (5a):ꢂLight yellow solid, mp 157°C–160°C
−
1
[
150°C–155°C Lit. (Kumar et al., 2008)]. IR (KBr) υ
(cm ): 3402
volume of adsorbed N at relative pressure (p/p°) of 0.99. The pore
size distribution was calculated using the Barret–Joyner–Halenda
method.
max
2
(
NH ), 3289 (NH ), 3204 (NH), 1692 (C=O), 1659 (C=O), 1610 (C=C), 1291
2
2
1
(
C-O), 1029 (C-N). H NMR (500 MHz, CDCl ): δ (ppm)ꢁ=ꢁ1.01 (s, 3H),
3
1
.14 (s, 3H), 1.21 (t, 3H, Jꢀ=ꢀ5.3 Hz), 2.19 (d, 1H, Jꢀ=ꢀ16.5 Hz), 2.26 (d, 1H,
Jꢀ=ꢀ16.5 Hz), 2.47 (s, 2H), 4.02–4.12 (m, 2H), 4.74 (s, 1H), 6.22 (s, 2H, NH ),
2
13
7
.14 (t, 1H, Jꢀ=ꢀ6.6 Hz), 7.24 (t, 2H, Jꢀ=ꢀ7.2 Hz), 7.30 (d, 2H, Jꢀ=ꢀ6.7 Hz).
C
Preparation of FSM-16 nanoparticles
NMR (125.72 MHz, CDCl ): δ (ppm)ꢁ=ꢁ14.6, 27.8, 29.5, 32.7, 34.3, 41.1, 51.2,
3
6
0.1, 81.2, 117.3, 126.4, 128.2, 128.6, 146.2, 158.8, 161.8, 169.5, 196.9.
A typical procedure for the preparation of kanemite was as follows: to
a solution of NaOH (3 g) dissolved in deionized water (30 mL), tetra-
ethylortosilicate (16.6 mL) was added dropwise and then the mixture
was stirred for another 12 h at room temperature. The solution was
transferred into an oven and heated at 355 K for 4 h. The resultant
product was calcined at 923 K for 5 h to obtain δ-Na Si O (kanemite).
The kanemite was deliquescent and immediately used for further
treatment. Kanemite (5 g) was dispersed in deionized water (50 mL)
and then stirred for 3 h at 300 K. Then, the suspension was filtered
out to obtain wet kanemite paste. All of the kanemite paste was dis-
persed in an aqueous solution (40 mL) of cetyltrimethylammonium
Ethyl
methyl-5-oxoquinoline-3-carboxylate (5b):ꢂLight yellow solid, mp
55°C–157°C [150°C–153°C Lit. (Abdollahi-Alibeik and Rezaeipoor-
2-amino-4-(4-chlorophenyl)-1,4,5,6,7,8-hexahydro-7,7-di-
1
−
1
Anari, 2016)]. IR (KBr) υmax (cm ): 3479 (NH ), 3327 (NH ), 3204 (NH),
2
2
2
2
5
1
1
(
689 (C=O), 1659 (C=O), 1620 (C=C), 1295 (C-O), 1038 (C-N). H NMR
500 MHz, CDCl ): δ (ppm)ꢁ=ꢁ1.00 (s, 3H), 1.14 (s, 3H), 1.18 (t, 3H,
3
Jꢁ=ꢁ8.8 Hz), 2.19 (d, 1H, Jꢁ=ꢁ16.5 Hz), 2.27 (d, 1H, Jꢁ=ꢁ16.5 Hz), 2.46 (s, 2H),
.02–4.12 (m, 2H), 4.71 (s, 1H), 6.22 (s, 2H, NH ), 7.21 (d, 2H, Jꢁ=ꢁ4.0 Hz),
4
2
1
3
7
.24 (d, 2H, Jꢁ=ꢁ4.0 Hz). C NMR (125.72 MHz, CDCl ): δ (ppm)ꢁ=ꢁ14.6,
3
2
7.8, 29.5, 32.7, 33.8, 41.1, 51.1, 60.2, 80.8, 116.8, 128.3, 130.1, 144.8,
−1
bromide (0.125 mol L ) and then stirred at 343 K for 3 h. The pH value
of the suspension was 11.5–12.5 at this stage. Afterward, the pH value
was adjusted carefully to 8.5 by adding 2 mol L of hydrochloric acid
with stirring. The suspension was continuously stirred at 343 K for
1
58.7, 161.9, 169.3, 196.7.
−1
Ethyl 2-amino-1,4,5,6,7,8-hexahydro-7,7-dimethyl-4-(4-nitrophenyl)-
5
-oxoquinoline-3-carboxylate(5c):ꢂLightyellowsolid,mp190°C–195°C
3
h while keeping the pH value at 8–9. After cooling to r.t., the solids
were separated using a centrifuge and washed with distilled water
20 mL) and dried in an oven at 393 K for 2 h to yield mesoporous sili-
[
190°C–195°C Lit. (Abdollahi-Alibeik and Rezaeipoor-Anari, 2016)]. IR
−1
(
KBr) υmax (cm ): 3474 (NH ), 3337 (NH ), 3201 (NH), 1689 (C=O), 1658
(
2
2
1
(
C=O), 1621 (C=C), 1296 (C-O), 1039 (C-N). H NMR (500 MHz, CDCl ):
cate, FSM-16, while retaining the template. The product was calcined
at 823 K to burn off the surfactant to obtain the final FSM-16.
3
δ (ppm)ꢁ=ꢁ0.99 (s, 3H), 1.15 (s, 3H), 1.66 (t, 3H, Jꢁ=ꢁ7.1 Hz), 2.17 (d, 1H,
Jꢁ=ꢁ16.5 Hz), 2.27 (d, 1H, Jꢁ=ꢁ16.5 Hz), 2.49 (s, 2H), 3.99–4.10 (m, 2H), 4.83
13
(
s, 1H), 6.31 (s, 2H, NH ), 7.47 (d, 2H, Jꢁ=ꢁ8.7 Hz), 8.12 (d, 2H, Jꢁ=ꢁ8.7 Hz). C
2
NMR (125.72 MHz, CDCl ): δ (ppm)ꢁ=ꢁ14.6, 27.7, 29.5, 32.7, 34.7, 41.1, 51.0,
3
Preparation of FSM-16-SO H nanoparticles
3
60.3, 79.8, 116.0, 123.6, 129.6, 153.9, 158.8, 162.4, 169.0, 196.6.
FSM-16 (0.278 g) was added to dry CH Cl (3 mL) in a 5 mL round-bot-
2
2
Ethyl
2-amino-1,4,5,6,7,8-hexahydro-7,7-dimethyl-5-oxo-4-p-tol-
tomed flask equipped with a gas outlet tube and a dropping funnel con-
taining a solution of chlorosulfonic acid (0.6 mL) in dry CH Cl (4.5 mL).
ylquinoline-3-carboxylate (5d):ꢂLight yellow solid, mp 139°C–141°C
−1
2
2
[135°C–137°C Lit. (Kumar et al., 2008)]. IR (KBr) υ
(cm ): 3407
max
The chlorosulfonic acid solution was added dropwise to the obtained
suspension over a period of 30 min at room temperature. After comple-
tion of the reaction, the sediment was separated using a centrifuge and
then washed with deionized water (2ꢁ×ꢁ3 mL). The obtained solid was
(
NH ), 3293 (NH ), 3222 (NH), 1691 (C=O), 1656 (C=O), 1622 (C=C), 1288
2
2
1
(
C-O), 1034 (C-N). H NMR (500 MHz, CDCl ): δ (ppm)ꢁ=ꢁ1.20 (s, 3H),
3
1
.13 (s, 3H), 1.22 (t, 3H, Jꢀ=ꢀ7.1 Hz), 2.19 (d, 1H, Jꢀ=ꢀ16.0 Hz), 2.26 (d, 1H,
Jꢀ=ꢀ16.0 Hz), 2.33 (s, 3H), 2.46 (s, 2H), 4.04–4.12 (m, 2H), 4.71 (s, 1H),
dried in an oven at 120°C for 2 h to obtain FSM-16-SO H.
13
3
6.22 (s, 2H, NH ), 7.05 (d, 2H, Jꢀ=ꢀ7.8 Hz), 7.18 (d, 2H, Jꢀ=ꢀ8.0 Hz). C NMR
2
(
125.72 MHz, CDCl ): δ (ppm)ꢁ=ꢁ14.7, 21.5, 27.9, 29.5, 32.7, 33.8, 41.1, 51.2,
3
6
0.1, 81.4, 117.4, 128.5, 128.9, 135.8, 143.3, 158.8, 161.7, 169.6, 196.8.
General procedure for the synthesis of polyhydroquino-
line derivatives in the presence of FSM-16-SO H
3
Ethyl
methyl-5-oxoquinoline-3-carboxylate (5e):ꢂLight yellow solid, mp
A mixture of dimedone (1 mmol), aldehyde (1 mmol), ethyl cyanoac- 135°C–136°C [140°C–143°C Lit. (Abdollahi-Alibeik and Rezaeipoor-
2-amino-4-(3-bromophenyl)-1,4,5,6,7,8-hexahydro-7,7-di-
−1
etate (1.1 mmol), ammonium acetate (1.2 mmol), and a catalytic Anari, 2016)]. IR (KBr) υmax (cm ): 3409 (NH ), 3296 (NH ), 3227 (NH),
2
2
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ꢉꢉꢀꢀꢀꢀꢁꢀS. Hashemi-Uderji et al.: FSM-16-SO H nanoparticles as a novel heterogeneous catalyst
3
1
1
1
692 (C=O), 1657 (C=O), 1620 (C=C), 1288 (C-O), 1035 (C-N). H NMR 1693 (C=O), 1659 (C=O), 1611 (C=C), 1290 (C-O), 1039 (C-N). H NMR
(
500 MHz, CDCl ): δ (ppm)ꢁ=ꢁ1.02 (s, 3H), 1.13 (s, 3H), 1.20 (t, 3H, (500 MHz, CDCl ): δ (ppm)ꢁ=ꢁ0.87 (s, 3H), 1.01 (s, 3H), 1.06 (t, 3H,
3
3
Jꢁ=ꢁ7.0 Hz), 2.20 (d, 1H, Jꢁ=ꢁ16.0 Hz), 2.26 (d, 1H, Jꢁ=ꢁ16.0 Hz), 2.46 (s, 2H), Jꢁ=ꢁ7.05 Hz), 2.05 (d, 1H, Jꢁ=ꢁ16.05 Hz), 2.24 (d, 1H, Jꢁ=ꢁ16.05 Hz), 2.49
.06–4.09 (m, 2H), 4.70 (s, 1H), 6.28 (s, 2H, NH ), 7.10 (t, 1H, Jꢁ=ꢁ7.6 Hz), (s, 2H), 3.93 (q, 2H, Jꢁ=ꢁ7.05 Hz), 4.49 (s, 1H), 7.00 (t, 2H, Jꢁ=ꢁ3.05 Hz),
4
2
13
13
7
.23 (d, 1H, Jꢁ=ꢁ7.7 Hz), 7.26 (d, 1H, Jꢁ=ꢁ7.8 Hz), 7.42 (s, 1H). C NMR 7.13–7.16 (m, 2H), 7.57 (s, 2H, NH ). C NMR (125.72 MHz, CDCl ): δ
2
3
(
125.72 MHz, CDCl ): δ (ppm)ꢁ=ꢁ14.6, 27.9, 29.5, 32.7, 34.2, 41.1, 51.1, 60.2, (ppm)ꢁ=ꢁ14.6, 26.9, 29.0, 32.3, 33.1, 40.0, 50.39, 59.2, 78.1, 114.8, 115.8,
3
8
0.5, 116.5, 122.3, 127.5, 129.6, 129.7, 131.8, 148.6, 158.7, 162.1, 169.3, 196.7. 129.9, 143.0, 159.6, 160.9, 162.5, 168.3, 196.2.
Ethyl
2-amino-1,4,5,6,7,8-hexahydro-7,7-dimethyl-4-(3- Ethyl
2-amino-1,4,5,6,7,8-hexahydro-4-(3,5-dimethoxyphenyl)-
nitrophenyl)-5-oxoquinoline-3-carboxylate (5f):ꢂLight yellow solid, 7,7-dimethyl-5-oxoquinoline-3-carboxylate (5k):ꢂLight yellow solid,
−1
−1
mp 183°C–184°C. IR (KBr) υ (cm ): 3440 (NH ), 3300 (NH ), 3208 mp 222°C–226°C. IR (KBr) υ (cm ): 3436 (NH ), 3304 (NH ), 3197
max
2
2
max
2
2
1
1
(
NH), 1692 (C=O), 1671 (C=O), 1622 (C=C), 1251 (C-O), 1038 (C-N). H (NH), 1690 (C=O), 1663 (C=O), 1592 (C=C), 1285 (C-O), 1038 (C-N). H
NMR (500 MHz, CDCl ): δ (ppm)ꢁ=ꢁ1.00 (s, 3H), 1.13 (s, 3H), 1.17 (t, 3H, NMR (500 MHz, CDCl ): δ (ppm)ꢁ=ꢁ1.03 (s, 3H), 1.10 (s, 3H), 1.22 (t, 3H,
3
3
Jꢁ=ꢁ7.1 Hz), 2.17 (d, 1H, Jꢁ=ꢁ16.0 Hz), 2.27 (d, 1H, Jꢁ=ꢁ16.0 Hz), 2.50 (s, 2H), J =7.2 Hz), 2.22 (d, 1H, Jꢁ=ꢁ16.2 Hz), 2.26 (d, 1H, Jꢁ=ꢁ16.2 Hz), 2.40 (s,
.03–4.07 (m, 2H), 4.81 (s, 1H), 6.40 (s, 2H, NH ), 7.40 (t, 1H, Jꢀ=ꢀ7.9 Hz), 2H), 3.78 (s, 6H), 4.06–4.13 (m, 2H), 4.70 (s, 1H), 6.23 (s, 2H, NH ) 6.27
4
2
2
1
3
13
7
.67 (d, 1H, Jꢀ=ꢀ7.9 Hz), 8.00 (d, 1H, Jꢁ=ꢁ7.9 Hz), 8.13 (s, 1H). C NMR (t, 1H, Jꢁ=ꢁ1.6 Hz), 6.48 (d, 2H, Jꢁ=ꢁ2.0 Hz). C NMR (125.72 MHz, CDCl ):
3
(
1
125.72 MHz, CDCl ): δꢁ=ꢁ14.6, 27.7, 29.4, 32.6, 34.6, 41.0, 51.0, 60.3, 79.9, δ (ppm)ꢁ=ꢁ14.0, 26.9, 29.1, 32.0, 34.2, 41.0, 51.0, 55.3, 60.1, 80.1, 98.0,
16.0, 121.7, 123.6, 128.9, 135.3, 148.5, 148.6, 158.8, 162.5, 169.0, 196.7.
3
117.0, 148.0, 158.1, 160.0, 161.0, 169.2, 196.0. Anal. Calcd. for C H N O :
22 28 2 5
C, 65.98; H, 7.05; N, 7.00. Found: C, 65.88; H, 7.03; N, 7.20.
Ethyl
hexahydroquinoline-3-carboxylate (5g):ꢂLight yellow solid, mp
72°C–175°C [179°C–181°C Lit. (Abdollahi-Alibeik and Rezaeipoor-
2-amino-7,7-dimethyl-5-oxo-4-(pyridin-3-yl)-1,4,5,6,7,8-
Acknowledgment: We are thankful to the Yazd University
Research Council for partial support of this work.
1
−1
Anari, 2016)]. IR (KBr) υmax (cm ): 3440 (NH ), 3335 (NH ), 3200 (NH),
2
2
1
1
690 (C=O), 1663 (C=O), 1622 (C=C), 1279 (C-O), 1040 (C-N). H NMR
(
400MHz, (CDCl ): δ (ppm)ꢁ=ꢁ0.99 (s, 3H), 1.12 (s, 3H), 1.16 (t, 3H,
3
Jꢁ=ꢁ7.0 Hz), 2.17 (d, 1H, Jꢁ=ꢁ16.2 Hz), 2.25 (d, 1H, Jꢀ=ꢀ16.2 Hz), 2.46 (s, 2H),
4
.03–4.04 (m, 2H), 4.71 (s, 1H), 6.29 (s, 2H, NH ), 7.14–7.17 (m, 1H), References
2
13
7
.58–7.61 (m, 1H), 8.36–8.37 (m, 1H), 8.53 (s, 1H). C NMR (100 MHz,
(CDCl ): δ (ppm)ꢁ=ꢁ14, 27, 29, 31, 40, 50, 51, 60, 79, 116, 123, 136, 141, 147,
−
3
Abdollahi-Alibeik, M.; Hoseinikhah, S. S. ClO4 /Zr-MCM-41
1
1
50, 159, 162, 169, 196. Anal. Calcd. for C H N O : C, 66.84; H, 6.79; N,
2.31. Found: C, 66.73; H, 6.61; N, 12.37.
19
23
3
3
nanoparticles prepared at mild conditions: a novel solid acid
catalyst for the synthesis of polyhydroquinolines. J. Iran Chem.
Soc. 2ꢉ16, 13, 1339–1347.
Ethyl-2-amino-4-(2-chlorophenyl)-7,7-dimethyl-5-oxo-
,4,5,6,7,8-hexahydroquinoline-3-carboxylate (5h):ꢂWhite solid,
mp 182°C–183°C [183°C–185°C Lit. (Abdollahi-Alibeik and Rezaeipoor-
Abdollahi-Alibeik, M.; Pouriayevali, M. 12-Tungstophosphoric acid
supported on nano sized MCM-41 as an efficient and reusable
solid acid catalyst for the three-component imino Diels–Alder
reaction. React. Kinet. Mech. Cat. 2ꢉ11, 104, 235–248.
Abdollahi-Alibeik, M.; Rezaeipoor-Anari, A. BF3/MCM-41 as nano
structured solid acid catalyst for the synthesis of 3-iminoaryl-
imidazo[1,2-a]pyridines. Cat. Sci. Tech. 2ꢉ14, 4, 1151–1159.
Abdollahi-Alibeik, M.; Rezaeipoor-Anari, A. MCM-41 functionalized
with B-F bond: preparation, characterization and catalytic appli-
cation in the synthesis of polyhydroquinolines. Lett. Org. Chem.
2ꢉ15, 12, 651–658.
1
−1
Anari, 2016)]. IR (KBr) υmax (cm ): 3420 (NH ), 3309 (NH ), 3215 (NH),
2
2
1
1
693 (C=O), 1655 (C=O), 1613 (C=C), 1294 (C-O), 1038 (C-N). H NMR
400 MHz, DMSO-d6): δ (ppm)ꢁ=ꢁ0.93 (s, 3H), 1.02 (t, 3H, Jꢁ=ꢁ7.2 Hz),
.03 (s, 3H), 2.02 (d, 1H, Jꢁ=ꢁ16.1 Hz), 2.25 (d, 1H, Jꢁ=ꢁ16.1 Hz), 2.39–2.59
m, 2H), 3.91 (q, 2H, Jꢁ=ꢁ7.0 Hz), 4.83 (s, 1H), 7.21–7.25 (m, 4H), 7.65
(
1
(
(
1
3
s, 2H, NH ). C NMR (100 MHz, DMSO-d6): δ (ppm)ꢁ=ꢁ14.1, 26.4, 28.6,
2
3
1.7, 32.2, 49.9, 55.7, 76.3, 113.9, 126.3, 127.3, 129.2, 131.8, 132.6, 142.7,
1
6
59.2, 162.2, 168.1, 195.6. Anal. Calcd. for C H ClN O : C, 64.08; H,
2
0
23
2
3
.18; N, 7.47. Found: C, 63.96; H, 5.98; N, 7.53.
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new magnetically recoverable nanostructured catalyst for the
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Ethyl 2-amino-1,4,5,6,7,8-hexahydro-4-(4-methoxyphenyl)-7,7-di-
methyl-5-oxoquinoline-3-carboxylate (5i):ꢂLight yellow solid, mp
1
28°C–130°C. [122°C–125°C Lit. (Kumar et al., 2008)]. IR (KBr) υ
Adharvana Chari, M.; Syamasundar, K. Silica gel/NaHSO catalyzed
max
4
−1
(
cm ): 3413 (NH ), 3304 (NH ), 3226 (NH), 1690 (C=O), 1668 (C=O),
one-pot synthesis of Hantzsch 1,4-dihydropyridines at ambient
2
2
1
1
621 (C=C), 1288 (C-O), 1036 (C-N). H NMR (500 MHz, CDCl ): δ
temperature. Catal. Commun. 2ꢉꢉ5, 6, 624–626.
3
(
ppm)ꢁ=ꢁ0.89 (s, 3H), 1.02 (s, 3H), 1.09 (t, 3H, Jꢁ=ꢁ7.0 Hz), 2.04 (d, 1H, Araki, H.; Fukuoka, A.; Sakamoto, Y.; Inagaki, S.; Sugimoto, N.; Fuku-
Jꢁ=ꢁ20.0 Hz), 2.24 (d, 1H, Jꢁ=ꢁ20.0 Hz), 2.46 (s, 2H), 3.66 (s, 3H), 3.90–3.97
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(
m, 2H), 4.44 (s, 1H), 6.75 (d, 2H, Jꢁ=ꢁ5.0 Hz), 7.02 (d, 2H, Jꢁ=ꢁ5.0 Hz), 7.49
1
3
(
s, 2H, NH ). C NMR (125.72 MHz, CDCl ): δ (ppm)ꢁ=ꢁ14.7, 26.9, 29.1,
2
3
3
2.3, 32.8, 40.5, 50.5, 55.3, 59.2, 78.5, 113.5, 116.2, 129.0, 138.9, 157.7, Boer, R.; Gekeler, V. Chemosensitizers in tumor therapy: new
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4
Ethyl
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−1
155°C–158°C. IR (KBr) υ (cm ): 3402 (NH ), 3289 (NH ), 3212 (NH),
max 2 2
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