Ionic liquid supported on magnetic nanoparticles as a novel reusable nanocatalyst for the efficient synthesis of tetracyclic quinazoline compounds

Article abstract of DOI:10.1007/s11164-018-3510-1

A magnetic ionic liquid supported on γ-Fe₂O₃ nanocatalyst was synthesized successfully and characterized by Fourier transform infrared spectroscopy, vibrating sample magnetometry, thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction and scanning electron microscopy. The resulting nano-Fe₃O₄-supported, ionic liquid was an efficient catalyst for preparation of a series of tetracyclic quinazoline compounds by three components reaction of a mixture of isatoic anhydride and amine with ninhydrin in PEG and the desired products were obtained in good to excellent yields. High efficiency, waste-free, mild reaction conditions, effortless magnetic recovery and reusability up to four continuous cycles are the noteworthy features of the currently employed heterogeneous catalytic system.

Full text of DOI:10.1007/s11164-018-3510-1

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-018-3510-1
Ionic liquid supported on magnetic nanoparticles
as a novel reusable nanocatalyst for the efficient synthesis
of tetracyclic quinazoline compounds
1
Zahra Taherinia1 • Mohsen Nikoorazm1
Arash Ghorbani-Choghamarani
•
Received: 14 April 2018 / Accepted: 12 June 2018
Ó Springer Nature B.V. 2018
Abstract
A magnetic ionic liquid supported on c-Fe O nanocatalyst was synthesized suc-
2
3
cessfully and characterized by Fourier transform infrared spectroscopy, vibrating
sample magnetometry, thermogravimetric analysis, differential scanning calorime-
try, X-ray diffraction and scanning electron microscopy. The resulting nano-Fe O -
3
4
supported, ionic liquid was an efficient catalyst for preparation of a series of
tetracyclic quinazoline compounds by three components reaction of a mixture of
isatoic anhydride and amine with ninhydrin in PEG and the desired products were
obtained in good to excellent yields. High efficiency, waste-free, mild reaction
conditions, effortless magnetic recovery and reusability up to four continuous cycles
are the noteworthy features of the currently employed heterogeneous catalytic
system.
Keywords Tetracyclic quinazoline Á Magnetic ionic liquid Á Recyclable
nanocatalyst Á PEG
Introduction
One of the 12 principles of green chemistry is the design of chemical processes that
reduce or eliminate chemical waste and cost of production [1, 2]. This can be
achieved by developing alternative and sustainable technologies that are non-toxic
to living things and the environment [3]. The ionic liquids (ILs) method can be used
to achieve this aim, because of their unique combination of thermal and chemical
Electronic supplementary material The online version of this article (https://doi.org/10.1007/s11164-
018-3510-1) contains supplementary material, which is available to authorized users.
&
Arash Ghorbani-Choghamarani
a.ghorbani@ilam.ac.ir; arashghch58@yahoo.com
1
Ilam University, Ilam, Islamic Republic of Iran
123

A. Ghorbani-Choghamarani et al.
3 4
Scheme 1 Schematic synthesis of nano-Fe O -supported, ionic liquid
stability, low vapour pressure, low melting point, high conductivity, ability to
dissolve organic and inorganic solutes and catalytic properties [4, 5]. Moreover, the
relationship between the structure of ionic liquids and their specific performance
further extends the scope of application of ILs. Use of heterogeneous catalysts in
organic syntheses has gained more significant attention than that of homogeneous
ones due to their excellent stability, recovery and reusability of the catalyst. On the
basis of this awareness, ILs can modify different support materials, such as
mesoporous silica [6], zeolites [7], polystyrene [8] and magnetic nanoparticles
[
9–15], and in this way the unique physicochemical properties of ILs can be
transferred to substrates. The lack of mass transfer restrictions increase the number
of accessible active sites of the catalyst, which is desirable from an economic and
toxicological point of view [16]. Among these supports, magnetic nanoparticles
(
MNPs) have attracted more attention, because they are readily dispersed and
provide a higher density of active sites available for catalysis. Moreover, magnetic
nanoparticles are widely applied in drug delivery, medical diagnosis, environmental
science, material science and catalysis [17, 18]. Knowing the importance of
supported ionic liquids in catalysis and in continuation of our previous nanostudies
herein, we represent an environmentally friendly approach for the preparation of
magnetically ionic liquid supported on a c-Fe O nanocatalyst with high magnetic
2
3
sensitivity and its application in multicomponent reactions (Scheme 1). Among
fused heterocyclic compounds, tetracyclic quinazoline has recently attracted much
attention due to its wide range of biological and pharmacological activities [19].
Furthermore, the quinazoline skeleton has been widely used as building blocks in
various natural products [20, 21]. Consequently, several methods have been
reported for promoting the preparation of tetracyclic quinazoline: (1) via the
condensation reaction of isatoic anhydride, amine, and ninhydrin in the presence of
HCl (2) utilizing the palladium-catalyzed carbonylation of commercially available
2-bromobenzyl amine and 2-bromoaniline as the starting materials (3) through
radical approach for example using N-acylcyanamides as radical partners in
cyclization cascade processes in the presence of AIBN/n-Bu SnH. Although these
3
methods are suitable for certain synthetic conditions, but there are still some
drawbacks such as, low yield of products, toxic and corrosive. Also the used
1
23

Ionic liquid supported on magnetic nanoparticles as a…
catalysts and solvents are not acceptable in the context of green synthesis. Thus, the
development of a new, efficient and green approach for the synthesis of tetracyclic
quinazoline compounds is highly desirable. Herein, we report the preparation of a
novel heterogeneous catalyst, which proved to be highly efficient for the synthesis
of tetracyclic quinazoline in PEG.
Results and discussion
Scheme 1 illustrated the pathway of synthesis of nano-Fe O -supported, ionic liquid
3
4
as a new magnetic, recyclable heterogeneous catalyst for synthesis of a series of
tetracyclic quinazoline compounds.
Characterization
The synthesized catalyst was characterized on the basis of NMR spectroscopy,
Fourier transform infrared (FT-IR), thermogravimetric analysis, differential
3 4 2 3 4 2 3 4
Fig. 1 (a) FT-IR spectra of Fe O /SiO -Propyl-Cl, (b) Pip-His, (c) Fe O /SiO -Propyl-His, (d) Fe O /
SiO -Propyl-Pip-His-SO H)
2
3
123

A. Ghorbani-Choghamarani et al.
scanning calorimetry (TG/DSC), X-ray diffraction (XRD), vibrating sample
magnetometry (VSM), and scanning electron microscopy (SEM). In the IR
-
spectrum of Fe O /SiO -Propyl-Cl (Fig. 1a) a broad band at 3400 cm that can be
1
3
4
2
attributed to the stretching vibration frequency of the O–H band of Fe O
3
4
1
-
nanoparticles, while the two characteristic absorption bands at 579 and 464 cm
correspond to the Fe–O stretching modes of the Fe O lattice. Also, the peak at
3
4
-
091 cm is due to the Si–O–Si stretching vibrations. Moreover, the bands at 2926
1
1
and 2963 cm
-
1
are attributed to the stretching modes of C–H (Fig. 1b). In
comparison to the IR spectra of Pip-His and Fe O /SiO -Propyl-Pip-His (Fig. 1b, c),
3
4
2
-
1
it is obvious that a band at 1470 cm appears at the same regions in two spectra;
Fig. 1c) characteristic stretching of the C=C band can be assigned to the existence
of Pip-His around the magnetic cores. The presence of a strong broad stretching
(
-
1
band in the 3397 cm region (Fig. 1d) correspons to the O–H band of sulfonic acid
(
Fig. 1d).
The XRD pattern of Fe O /SiO -Propyl-Pip-His shows the typical peaks at
3
4
2
3
the standard Fe O XRD spectrum (Fig. 2) [22]. The stability of sulfamic acid-
0.07°, 35.52°, 43.12°, 53.36°, 57.19°, 62.79°, respectively which is consistent that
3
4
functionalized Fe O was investigated by thermogravimetric analysis (TGA) and
4
3
differential scanning calorimetry (DSC), indicating the formation of bonds between
MNPs and the catalyst. Sulfamic acid-functionalized Fe O shows three-step weight
3
4
loss behaviour. (1) Mass loss below 150 °C was attributed to the loss of adsorbed
solvent or trapped water from the catalyst. (2) Around 300 °C, a large weight
reduction occurred, which can be mainly ascribed to the decomposition of SO H
3
groups (Fig. 3). (3) Above 700 °C, the occurrence of further mass losses at higher
temperature resulted from the decomposition of the silica shell. The DSC
thermogram of sulfamic acid-functionalized Fe O showed an exothermic peak at
3
4
9
8 °C, which is due to dehydration. Also, the DSC thermogram of nanoparticles
showed an endothermic peak at 200–600 °C as a result of oxidation–reduction
reactions. Moreover, it showed an exothermic peak at 680 °C, probably due to the
decomposition of trialkoxysilane moiety (Fig. 4).
Fig. 2 XRD pattern of magnetic ionic liquid
1
23

Ionic liquid supported on magnetic nanoparticles as a…
Fig. 3 TGA and DSC thermograms of magnetic ionic liquid
The magnetization curves of Fe O /SiO -Propyl-His and Fe O were measured at
3
4
2
2 3
room temperature using a vibrating sample magnetometer (VSM). As seen, the
saturation magnetization of the sample decreases in comparison with Fe O [23] due
3
4
to functionalization of magnetic nanoparticles. The morphology of the nanocom-
posite was observed on scanning electron microscopy. Figure 5 displays the SEM
micrograph of Fe O /SiO -Propyl-Pip-His-SO H. As can be seen, the nanocom-
3
4
2
3
posite has spherical morphology.
Catalytic activity of Fe O /SiO -Propyl-His was next evaluated in synthesis of a
series of tetracyclic quinazoline compounds.
3
4
2
Isatoic anhydride with a benzyl amine and ninhydrin was selected as model
reaction and the effect of various parameters such as amount of catalyst, nature of
the solvents, and temperature were studied (Table 1). In order to reduce the
formation of by-products, the isatoic anhydride and benzyl amine were mixed and
stirred at 80 °C. Then, ninhydrin was added to this mixture. First, the effect of
solvents was investigated and it was observed that the desired product was obtained
in the PEG or DMSO solvent (Table 1, entries 1 and 5), while reaction in solvents
such as toluene and water was ineffective. The effect of temperature was also
investigated, and the highest yield was obtained at 80 °C. When the reaction was
conducted at 100 and 130 °C, a low-yield was seen. The control experiment
confirmed that the reaction did not occur in the absence of the catalyst (Table 1,
entry 10). The influence of the amount of catalyst on the yield of the product was
evaluated. It was observed that 30 mg of catalyst was the optimum. When the
reaction conducted under the same conditions in the presence of Fe O , it was
3
4
observed that the desired product was not obtained. We then investigated the
substrate scope of this synthesis by subjecting the series of aliphatic and aromatic
123

A. Ghorbani-Choghamarani et al.
Fig. 4 Magnetization curve of magnetic ionic liquid
amines to the reactions with isatoic anhydride and, ninhydrin, the results are shown
in Table 2. From these results, we observed that all of the reactions produced the
corresponding tetracyclic quinazoline compounds in excellent yields (60–92%). A
synthetic route is outlined in Scheme 2, Based on previous reports [24] carbonyl
group of isatoic anhydride gives nucleophilic addition reaction, leading to ring
opening followed by decarboxylation to compound B. Subsequently, nucleophilic
attack by amines to the keto group of ninhydrin forms imines intermediate C;
cyclization of this product leads to intermediates D; then nucleophilic attack of
amine on the keto group provides a aziridine intermediate E, Finally, desired
product is formed by rearrangement intermediate E.
The possibility of recovering and recycling the catalyst is an important issue from
economic and environmental points of view. After performing the three-component
reaction of a mixture of isatoic anhydride and amine with ninhydrin in PEG under
the optimized conditions, EtOAc was added to the reaction mixture. The catalyst
was separated by an external magnet from the reaction mixture (Fig. 6), washed
three times with acetone and then with doubly distilled water several times. Then
the recovered catalyst was used in the next run. This catalyst was recycled and
reused at least four times without significant loss of its catalytic activity (Fig. 6).
In conclusion, we have developed a facile route to synthesis nano-Fe O –
3
4
supported, ionic liquid and in addition, the excellent performance in synthesis of
tetracyclic quinazoline compounds using isatoic anhydride, a benzyl amine and
1
23

Ionic liquid supported on magnetic nanoparticles as a…
Fig. 5 SEM images of magnetic ionic liquid
ninhydrin were investigated. According to the obtained results, the catalyst is
stable and can be easily separated by magnetic decantation and reused many times
with less deterioration in catalytic activity (Fig. 6).
Experimental
Materials
All reagents and solvents used in this work were purchased from Sigma-Aldrich,
Fluka or Merck Chemical Companies and used without further purification. NMR
spectra were recorded on a Bruker AMX 300 MHz spectrometer and Bruker Avance
123

A. Ghorbani-Choghamarani et al.
Table 1 Optimization of the
reaction conditions for
a
Entry
Solvent
Cat (mg).
Temp. (°C)
Yield
tetracyclic quinazoline using
isatoic anhydride with a benzyl
amine and ninhydrin
1
2
3
4
5
6
7
8
DMSO
DMF
30
30
30
30
30
30
30
20
–
80
80
55
Trace
N.R.
N.R.
92
Toluene
80
H
2
O
80
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
80
100
130
80
60
25
68
9
80
N.R.
N.R.
c
1
0
30
80
Reaction conditions: isatoic anhydride (1.0 equiv), benzyl amine (1.0
equiv), and ninhydrin (1.0 equiv). N.R. No reaction
a
Isolated yield. Reaction time: 5 h (C) the reaction conducted under
the same conditions in the presence of Fe
3 4
O
1 13
III 400 MHz also H NMR, C NMR were recorded on either a Varian Mercury
13
Plus operating at 400 MHz (1 H) or 100.6 MHz ( C), chemical shifts are given in
ppm (d) relative to a TMS internal standard, and the coupling constants J reported in
Hz. Melting points were measured with an Electrothermal 9100 apparatus. VSM
measurements were performed using a vibrating sample magnetometer (VSM)
MDKFD. The nanostructures were characterized using a Holland Philips X’pert
X-ray powder diffractometer (XRD) (CoKa, radiation = 0.154056 nm). IR spectra
were obtained as KBr pellets on a VRTEX 70 model BRUKER FTIR spectropho-
tometer. Thermogravimetric analysis (TGA) curves were recorded using STA
NETZSCH 499 F3 Germany. The particle morphology was examined by SEM using
a FESEM-TESCAN. Elemental analysis was examined by CHNSO COSTECH
England.
Catalyst preparation
Preparation of 1, 1-(piperazine-1, 4-diyl) diethanone
A mixture of piperazine (2 mmol), acetyl chloride (5 mmol) and potassium
carbonate (2 mmol) was stirred in acetonitrile (5 mL), under reflux conditions at
8
temperature, filtered, and the white powder was washed with ethanol. Mp: 143–145
0 °C for 24 h. After completion of the reaction, the mixture was cooled to room
-
1
[
25], FT-IR (KBr): mmax/cm : 580.61, 765.33, 872.31, 959.45, 1006.50, 1068.87,
1
3
252.77, 1321.35, 1362.36, 1444.52, 1551.32, 1621.48, 2420.73, 2595.62, 3017.17,
204.63.
1
23

Ionic liquid supported on magnetic nanoparticles as a…
Scheme 2 Proposed mechanism for the synthesis of tetracyclic quinazoline compounds catalyzed by
magnetic ionic liquid
123

A. Ghorbani-Choghamarani et al.
Table 2 Magnetic ionic liquid catalyzed one-pot synthesis of tetracyclic quinazoline in PEG at 80 °C
Time
h)
Melting
point (°C)
Melting
Yielda
Entry
Amine
Product
(
point (°C)
(
ref.)
1
1
79–182
98–200
183–185
200–202
1
5
92
2
3
4
88
85
5.5
210–213 213–215
2
41–245
–
–
4
5
6.5
66
87
2
1
61–265
5
6
7
5.5
10
60
72
51–155 155–157
195–199 205–208
8
9
12
14
70
78
1
1
61–164
75–180
–
–
Reaction conditions: isatoic anhydride (1.0 equiv), benzyl amine (1.0 equiv), and ninhydrin (1.0 equiv),
magnetic ionic liquid (30 mg) and PEG (2 mL)
a
Isolated yield
1
23

Ionic liquid supported on magnetic nanoparticles as a…
Fig. 6 Catalyst recycling study for the synthesis of quinazoline tetracyclic compounds
Preparation of Pip-His
A mixture of 1,1-(piperazine-1, 4-diyl) diethanone (2.0 mmol), histidine ethyl ester
hydrochloride (4.0 mmol) and 2 mmol carbonate potassium in dry toluene was
heated at 100 °C for 24 h. After completion of the reaction, the reaction mixture
was cooled to room temperature, filtered and washed with ethanol. Finally, a white
1
powder was obtained. H NMR (400 MHz, D O) d 1.09 (t, J = 7, 3H), 1.97 (s, 3H),
2
a
b
2
.71 (s, 1H), 2.83–2.79 (m, 1H, C H), 2.94–2.91 (m, 2H, C H), 6.73–6.85 (m, 1H,
-
ArH), 7.95–7.97 (m, 1H, ArH), FT-IR (KBr): mmax/cm : 697.87, 789.43, 864.13,
034.38, 1415.43, 1658.49, 2880.43, 2928.39, 3415.78.
1
1
Preparation of Fe3O4
A mixture of FeCl Á6H O (5.838 g) and FeCl Á4H O (2.147 g) was dissolved in
3
2
2
2
1
under N atmosphere. Then, 10 mL of aqueous NH solution (32%) was added to
00 mL of deionized water in a three-necked round-bottom flask (250 mL) at 80 °C
2
3
the mixture over 30 min with vigorous mechanical stirring. The resulting black
solid was washed with double-distilled water until neutrality, further washed twice
with ethanol and dried at 80 °C in vacuum.
Preparation of Fe O @SiO
2
3
4
Fe O (0.50 g) was dispersed in a mixture of ethanol (50 mL), deionized water
3
4
(
5 mL) and TEOS (0.20 mL), followed by the addition of 2 mL of concentrated
ammonia solution. This solution was stirred mechanically for 38 h at room
temperature. Then the product, Fe O @SiO , was separated by an external magnet
3
4
2
and washed with deionized water and ethanol three times and dried at 80 °C.
123

A. Ghorbani-Choghamarani et al.
Preparation of Fe O /SiO -Propyl-Cl
3
4
2
The prepared Fe O /SiO (1 g) was sonicated in dry toluene (50 mL) for 30 min.
4
3
2
(
dispersed Fe O /SiO in dry toluene and stirred for 24 h under reflux conditions,
3-chloropropyl) trimethoxysilane (CPTMS) (5 mmol, 1 mL) was added to the
3
4
2
and the obtained chloropropyl-functionalized solid (Fe O /SiO -Propyl-Cl) was
4
3
2
washed with ethanol three times and dried at 80 °C.
Preparation of Fe O /SiO -Propyl-His
3
4
2
Fe O /SiO -Propyl-Cl (1 g) and KOH (2 mmol, 0.112 g) were added to the solution
2
3
4
of Pip-His (2 g) in dry toluene (100 mL). The mixture was sonicated for 0.5 h,
followed by stirring for 28 h under reflux conditions. The obtained solid was
magnetically collected from the solution and washed with water/ethanol (20:10 mL)
three times and dried at 80 °C.
Preparation of Fe O /SiO -Propyl-Pip-His-SO H)
3
4
2
3
To a mixture of piperazine-modified silica-coated Fe O MNPs (Fe O /SiO -
2
3
4
3
4
Propyl-Pip) (0.5 g) in dry CH Cl (3 mL), chlorosulfonic acid (ClSO H, 1 mL) was
2
2
3
added dropwise to a cooled ice-bath over a period of 30 min at room temperature
then the mixture was filtered and washed with dried CH Cl and dried at room
temperature to afford the title compound.
2
2
Synthesis of tetracyclic quinazoline compound derivatives general procedure
A mixture of isatoic anhydride (1.0 mmol), amine (1 mmol) and Fe O /SiO -
3
4
2
Propyl-Pip-SO H (0.03 g) in PEG-400, was stirred at 80 °C. After the reaction was
3
completed, ninhydrin (1 mmol) was added into the resulting mixture. Then the
mixture was heated at 80 °C and the reaction was monitored by TLC (hexane/ethyl
acetate, 4:1) for appropriate time. After completion, the mixture was cooled to room
temperature and 20 mL of ethyl acetate was added to the organic phase and washed
with water, dried over anhydrous Na SO , and filtered. The residue was purified by
2
4
column chromatography (silica gel, hexane/ethyl acetate, 4:1) to afford the
corresponding product.
NMR data
1
Compound 1 (Table 2) Yellow solid; mp: 179–182 °C; H NMR (400 MHz,
DMSO) d 4.43 (s, 2H), 7.41 (t, J = 4.2, 2H), 7.55 (d, J = 8.4, 2H), 7.90–7.81 (m,
1
3
3
1
1
H), 8.07 (s, 1H), 8.14 (t, J = 7.6, 2H). C NMR (100 MHz, CDCl ): d = 34.1,
3
14.2, 117.6, 119.2, 120.0, 124.1, 126.5, 126.6, 127.1, 127.2, 133.1, 133.6, 134.7,
37.4, 137.6, 143.0, 178.0, 180.8.
1
Compound 2 (Table 2) Brown solid; mp: 198–200 °C; H NMR (400 MHz,
DMSO) d 3.3 (s, 2H), 5.0 (s, 3H), 7.38 (d, J = 12, 1H), 7.41 (d, J = 10, 1H), 7.55 (d,
1
23

Ionic liquid supported on magnetic nanoparticles as a…
J = 8.4, 1H), 7.68 (s, 1H), 7.88–7.81 (m, 4H), 8.07 (S, 1h), 8.14 (t, J = 14.8, 2H).
1
3
C NMR (100 MHz, CDCl ): d = 50.9, 114.2, 117.6, 119.2, 120.0, 123.6, 123.8,
3
1
1
24.6, 126.4, 126.5, 127.2, 128.6, 132.5, 133.1, 133.6, 134.6, 137.6, 145.0, 177.9,
80.8.
1
Compound 3 (Table 2) Orange solid; mp: 210–213; H NMR (400 MHz, DMSO)
d 6.67 (d, J = 7.6, 1H), 6.83–6.82 (m, 1H), 6.94 (d, J = 8.4, 2H), 7.24–7.19 (m, 3H),
1
3
7
.36–7.35 (m, 1H), 7.73 (d, J = 7.6), 7.98–7.96 (m, 1H), 8.04–8.02 (m, 4H).
C
NMR (100 MHz, CDCl ): d = 75.1, 114.5, 119.0, 124.5, 128.1, 128.3, 129.2, 134.0,
3
1
37.1, 138.1, 139.2, 146.1, 163.3, 195.
1
Compound 4 (Table 2) White solid; mp: 241–245 °C; H NMR (400 MHz,
DMSO) d 1.5 (t, J = 7.4 3H), 2.52 (q, J = 7.4 3H), 7.23–7.17 (m, 4H), 7.68–7.64
1
3
(
m, 3H), 7.95 (d, J = 8, 3H). C NMR (100 MHz, CDCl ): d = 16.1, 18.6, 112.5,
3
1
1
1
23.7, 126.3, 126.5, 126.8, 128.6, 129.1, 131.8, 132.8, 134.1, 134.3, 144.4, 167.5,
-
1
80.6. FT-IR (KBr) mmax/cm : 462, 527, 680, 726, 1019, 1091, 1161, 1408, 1435,
477, 1652, 1714, 2849, 2926, 3023, 3062. Anal. Calcd for C H N O : C, 75.38;
2
4 18 2 3
H, 4.74; N, 7.33; O, 12.55, Found: C, 74.0; H, 6.19; N, 7.60; O, 12.21%.
1
Compound 5 (Table 2) White solid; mp: 261–265 °C; H NMR (400 MHz,
CDCl ) d 1.3 (d, J = 8, 6H), 2.88 (m, 1H), 7.49 (d, J = 8.8, 2H), 7.79–7.75 (m, 2H),
3
1
3
7
.83–7.81 (m, 3H), 8.0–7.98 (m, 3H), 8.2 (d, J = 7.6, 1H), 8.3 (t, J = 7.2, 1H).
C
NMR (100 MHz, CDCl ): d = 10.2, 30.0, 114.7, 115.0, 123.3, 125.3, 128.3, 129.0,
3
-
1
1
34.9, 138.6, 152.2, 162.4, 200.2. FT-IR (KBr) mmax/cm : 540, 662, 737, 819, 901,
9
C H N O : C, 75.74; H, 5.09; N, 7.07; O, 12.11, Found: C, 75.08; H, 6.19; N,
51, 1033, 1249, 1312, 1408, 1511, 1593, 1630, 1708, 2924, 3024. Anal. Calcd for
2
5 20 2 3
7
.60; O, 11. 13%.
1
Compound 6 (Table 2) Orange solid; mp: 151–155 °C; H NMR (400 MHz,
CDCl ) d 1.1–1.0 (m, 3H), 1.4–1.3 (m, 3H), 1.74–1.70 (m, 3H), 7.17 (d, J = 8, 2H),
3
1
.29 (q, J = 6.8, 2H), 7.66–7.62 (m, 2H), 8.17 (d, J = 7.6, 2H). C NMR
3
7
(
100 MHz, CDCl ): d = 14.1, 20.1, 29.9, 40.6, 114.2, 115.5, 122.9, 127.8, 135.4,
3
1
39.9, 150.6, 162.3, 192.3.
1
Compound 7 (Table 2) Brown solid; mp: 195–199 °C; H NMR (400 MHz,
CDCl ) d 7.95–7.91 (m, 2H), 8.1–8.06 (m, 3H), 8.1 (d, J = 8 2H), 8.2 (d, J = 7.6,
3
2
H).
1
Compound 8 (Table 2) White solid; mp: 161–164 °C; H NMR (300 MHz,
CDCl ) d 1.75–1.59 (m, 10H), 2.51–2.41 (m, 1H), 7.04 (d, J = 8, 2H), 7.26–7.19
3
1
m, 2H), 7.62–7.55 (m, 2H), 8.1. (d, J = 8, 2H). C NMR (75 MHz, CDCl3):
3
(
d = 25.9, 28.3, 28.9, 52.7, 114.1, 114.7, 122.3, 127.4, 134.7, 139.3, 150.2, 162.2,
-
1
1
1
84.7. FT-IR (KBr) mmax/cm :680, 725, 899, 973, 1019, 1075, 1185, 1302, 1374,
429, 1475, 1609, 1655, 1726, 2858, 2927. Anal. Calcd for C H N O : C, 73.32;
2
2 20 2 3
H, 5.59; N, 7.77; O, 13.32, Found: C, 72.14, H, 6.06, N, 9.60; O, 12.2%.
Compound 9 (Table 2) White solid; mp: 175–180 °C; 1H NMR (400 MHz,
DMSO) d 1.31–1.20 (m, 14H), 3.43–3.34 (m, 1H), 7.21–7.14 (q, J = 8.5, 1H), 7.57
123

A. Ghorbani-Choghamarani et al.
(
(
t, J = 7.2, 1H), 7.69–7.62 (m, 1H), 7.84 (q, J = 4.9, 2H), 7.92 (d, J = 8, 1H), 8.17
1
3
d, J = 8, 1H), 8.4 (s, 1H). C NMR (100 MHz, CDCl ): d = 15.9, 26.1, 29.1, 40.3,
3
4
1
1
7
0.6, 115.2, 121.9, 122.8, 126.7, 127.4, 127.5, 134.6, 135.2, 146.6, 147.8, 159.8,
1
-
80.9. FT-IR (KBr) mmax/cm :463, 537, 676, 743, 821, 942, 1022, 1100, 1153,
403, 1609, 1656, 1711, 2846, 2923, 3020, 3056. Anal. Calcd for C H N O C,
.21; H, 6.22; N, 7.21; O, 12.36, Found: C, 75.14, H, 6.26, N, 8; O, 10.6%.
2
4 24 2 3:
Acknowledgements The authors would like to thank the research facilities of Ilam University, Ilam, Iran,
for the financial support of this research project.
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