Synthesis of Ethyl 2-Amino-4-benzoyl-5-oxo-5,6-dihydro-4H-pyrano[3,2-c]quinoline-3-carboxylates by a One-pot, Three-Component Reaction in the Presence of TPAB

Article abstract of DOI:10.1002/jhet.3404

In this research, in order to synthesize a series of ethyl 2-amino-4-benzoyl-5-oxo-5,6-dihydro-4H-pyrano[3,2-c]quinoline-3-carboxylates, a green and an efficient method is proposed through one-pot three-component reaction of substituted arylglyoxals, ethyl cyanoacetate, and 4-hydroxyquinolin-2(1H)-one in the presence of terapropylammonium bromide as a catalyst in good yields. All synthesized new substances were characterized by FTIR, ¹H-NMR, and ¹³C-NMR spectral data and elemental analysis.

Full text of DOI:10.1002/jhet.3404

Month 2018 Synthesis of Ethyl 2-Amino-4-benzoyl-5-oxo-5,6-dihydro-4H-pyrano[3,2-
c]quinoline-3-carboxylates by a One-pot, Three-Component Reaction in
the Presence of TPAB
Ahmad Poursattar Marjani,*
Jabbar Khalafy,
and Ayda Farajollahi
Department of Organic Chemistry, Faculty of Chemistry, Urmia University, Urmia, Iran
*
E-mail: a.poursattar@gmail.com; a.poursattar@urmia.ac.ir
Received July 17, 2018
DOI 10.1002/jhet.3404
Published online 00 Month 2018 in Wiley Online Library (wileyonlinelibrary.com).
In this research, in order to synthesize a series of ethyl 2-amino-4-benzoyl-5-oxo-5,6-dihydro-4H-
pyrano[3,2-c]quinoline-3-carboxylates, a green and an efficient method is proposed through one-pot three-
component reaction of substituted arylglyoxals, ethyl cyanoacetate, and 4-hydroxyquinolin-2(1H)-one in
the presence of terapropylammonium bromide as a catalyst in good yields. All synthesized new substances
1
13
were characterized by FTIR, H-NMR, and C-NMR spectral data and elemental analysis.
J. Heterocyclic Chem., 00, 00 (2018).
INTRODUCTION
[21], and Src kinase inhibitory activities [22] in addition
to its presence in nature, making pyran derivatives
specific structures.
Multicomponent reactions has gained remarkable attention
in the field of chemical biology and organic synthesis in as
much as numerous advantages such as possibility of several
bonds formation in one-step process in addition to significant
benefits like convergent nature, extraction, and purification
steps and reducing waste production, the superior atom
economy, fast, efficient, and time-saving manner without the
isolation of any intermediate reduction of work ups, and
easy automation and straightforward experimental techniques
that resulted in the green transformations [1–6].
The presence of pyranoquinoline moiety in many alkaloids
has attracted serious attention. For instance, antitumor
[23,24], antimicrobial [25], anti-inflammatory [26],
antiallergic [27], antimalarial [28] inhibition of calcium
signaling [29], and platelet aggregation [30] are some of the
unique properties, in behalf of this attraction (Fig. 1).
Moreover, some intermediates of pyranoquinolines are used
in manufacturing of azo dyes which are applied in dyeing
of natural and synthetic fibers [31].
Tetrapropylammonium bromide (TPAB) is a phase-
transfer catalyst that has been used in the preparation of
high-silica zeolites of the ZSM type such as ZSM-5 and
has many other applications in various catalytic processes
In continuation of our interest in the synthesis of new
and various heterocyclic compounds [32–40], an efficient
protocol for the synthesis of pyrano[3,2-c]quinolines by
multicomponent condensation of arylglyoxals, ethyl
cyanoacetate, and 4-hydroxyquinolin-2(1H)-one in the
presence of TPAB under reflux conditions was reported.
[7,8]. TPAB is low in price, easily accessible catalyst,
environmentally friendly, simple utilization, noncorrosive,
and reusable.
Water isthe ideal natural green solvent and an alternate for
organic solvents, due to its nonflammable, nontoxic, and
uniquely redox-stable and inexpensive characteristics [9].
Pyran derivatives are widely used as agrochemical and
drug as a result of their unique chemical [10], biological
RESULTS AND DISCUSSION
According to our initial studies, the reaction of 3,4-
dimethoxyphenylglyoxal monohydrate (1g), ethyl
cyanoacetate (2), and 4-hydroxyquinolin-2(1H)-one (3)
was chosen as a model reaction (Scheme 1) by stirring
the mixture at 50°C; however, the expected product
formation was not achieved even after 12 h. The reaction
was carried out using different amounts of catalysts and
also solvent systems as mentioned in Table 1.
[11], and physical properties [12].
Substantial characteristics of pyran such as
antimicrobial [13], anticancer [14], antidyslipidemic
[
[
15], antihyperglycemic [16], anti-HIV [17], antioxidant
18], antiallergic [19], xanthine oxidase inhibitory [20],
acetylcholinesterase and butyrylcholinesterase inhibitory
©
2018 Wiley Periodicals, Inc.

A. Poursattar Marjani, J. Khalafy, and A. Farajollahi
Vol 000
Figure 1. Drug molecules having pyranoquinoline moieties.
Scheme 1. The model reaction for synthesis of 4g. [Color figure can be viewed at wileyonlinelibrary.com]
Table 1
Optimization of the reaction conditions.
Entry
Solvent
Conditions
Catalyst (mol%)
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
9
H
2
O/EtOH (1:1)
40–50
Reflux
Reflux
Reflux
Reflux
Reflux
60
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
TPAB (20)
TPAB (20)
TPAB (20)
TPAB (20)
TPAB (15)
TPAB (25)
TPAB (20)
TPAB (20)
TPAB (20)
12
24
24
5
10
8
10
14
15
24
15
12
24
10
12
18
-
H
2
O
40
35
91
85
88
25
-
EtOH
O/EtOH (1:1)
O/EtOH (1:1)
O/EtOH (1:2)
Acetone
H
H
H
2
2
2
DMF
AcOH
-
-
10
11
12
13
14
15
16
H
2
H
2
H
2
H
2
H
2
H
2
H
2
O/EtOH (1:1)
O/EtOH (1:1)
O/EtOH (1:1)
O/EtOH (1:1)
O/EtOH (1:1)
O/EtOH (1:1)
O/EtOH (1:1)
Sulfanilic acid (20)
E
3
N (20)
-
20
25
58
67
-
TEACB (20)
L-proline (20)
L-cysteine (20)
p-TSA (20)
-
Bold values show the best reaction conditions in terms of yield. DMF, dimethylformamide; TPAB, tetrapropylammonium bromide.
The highest yield of 91% was obtained using 20 mol% of
In the next step and after optimization of the reaction
conditions, the scope of the reaction was verified with
different arylglyoxals to form the desired pyranoquinoline
derivatives 4a–h. The reaction conditions and the yields
of products are listed in Table 2.
TPAB as a catalyst in H O/EtOH (1:1) at 5 h reaction time
2
(
Table 1, entry 4). In order to find out the best solvent
system for this reaction, we accomplished the trail reaction
using various solvents such as EtOH, H O, H O/EtOH
2
2
(
1:1), H O/EtOH (1:2), acetone, dimethylformamide, and
All arylglyoxal monohydrates 1a–h were prepared from
the corresponding acetophenones by oxidation procedure
with selenium dioxide via the literature procedure as
shown in Scheme 2 [41].
2
AcOH as shown in Table 1. Among all these solvents,
H O/EtOH (1:1) was proved to be the best solvent system
in terms of yield (Table 1, entry 4).
2
Furthermore, the effect of different catalysts on the
reaction was conducted through different catalytic
systems including sulfanilic acid, p-toluenesulfonic acid,
L-proline, L-cysteine, triethylamine, and different
amounts of TPAB ranging from 15 to 25 mol%. The best
The one-pot three-component reaction of arylglyoxal
monohydrates 1a–h, ethyl cyanoacetate (2), and 4-
hydroxyquinolin-2(1H)-one (3) in H O/EtOH (1:1) in the
2
presence of TPAB (20 mol%) as a catalyst afforded the
corresponding 2-amino-pyrano[3,2-c]quinolines in 80–
91% yield as shown in Scheme 3.
results were obtained using 20 mol% of catalyst in H O/
2
EtOH (1:1). Also, increase in the amount of catalyst did
not improve the yield.
The proposed mechanism of the reaction is shown in
Scheme 4. Mechanism includes dehydration of the
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2018
Synthesis of Ethyl 2-Amino-4-benzoyl-5-oxo-5,6-dihydro-4H-
pyrano[3,2-c]quinoline-3-carboxylates
Table 2
Synthesis of pyranoquinoline derivatives.
Entry
1
Pyrano[3,2-c]quinoline
Reaction time (h)
6
Yield (%)
88
Mp (°C)
Color
White
227–229
2
3
4
5
6
5
83
86
87
239–241
244–246
245–247
Yellow
White
White
5
5
85
240–242
White
6
7
6
5
80
91
228–230
232–234
White
Cream
8
4
81
225–227
Brown
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

A. Poursattar Marjani, J. Khalafy, and A. Farajollahi
Vol 000
Scheme 2. Preparation of arylglyoxal monohydrates. [Color figure can be
viewed at wileyonlinelibrary.com]
the NH group and NH of the pyranoquinoline moiety,
2
respectively, which were present in all new products. In
13
the C-NMR spectra of the products 4a–h, signals
located around δ = 161.4–198.6 ppm were attributed to
different carbonyl groups. In the obtained FTIR spectra,
the characteristic bonds at 3387–3407, 3288–3302, and
À1
1
669–1682 cm could be assigned to the vibrations of
NH, NH , and different carbonyl groups, respectively.
2
arylglyoxal 1a–h by the catalyst following by a
Knoevenagel condensation occurring between ethyl
cyanoacetate (2) and arylglyoxal that is facilitated by
TPAB via C–H activation on ethyl cyanoacetate which
reacts with 4-hydroxyquinolin-2(1H)-one (3) to give the
intermediate [A] that undergoes heterocyclization and
tautomerization to obtain the desired products.
In another study, reusability of the catalyst was
investigated
upon
the
reaction
of
3,4-
dimethoxyphenylglyoxal
monohydrate
and
ethyl
cyanoacetate with 4-hydroxyquinolin-2(1H)-one under
reflux condition to provide compound 4g. After
completion of the reaction, the obtained product 4g was
filtered out, followed by rising them with water,
eventually, the filtrate was extracted with CHCl3 and
aqueous phase was separated. The water was evaporated
to give TPAB as white crystals, which may be
The structures of ethyl-2-amino-4-benzoyl-5-oxo-5,6-
dihydro-4H-pyrano[3,2-c]quinoline-3-carboxylate 4a–h
1
13
were characterized by FTIR, H-NMR, and C-NMR
spectral data. The characteristic singlet peaks at around
δ = 11.65–11.78 and δ = 7.86–7.96 ppm are related to
recrystallized from Et O. It was observed that the
2
catalytic activity of TPAB was restored for four runs.
Scheme 3. One-pot synthesis of substituted 2-amino-pyrano[3,2-c]quinolines. [Color figure can be viewed at wileyonlinelibrary.com]
Scheme 4. Proposed mechanism for the synthesis of 2-amino-pyrano[3,2-c]quinolines. [Color figure can be viewed at wileyonlinelibrary.com]
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2018
Synthesis of Ethyl 2-Amino-4-benzoyl-5-oxo-5,6-dihydro-4H-
pyrano[3,2-c]quinoline-3-carboxylates
CONCLUSION
Ethyl 2-amino-4-(4-bromobenzoyl)-5-oxo-5,6-dihydro-4H-
pyrano[3,2-c]quinoline-3-carboxylate (4b).
Yield, 83%;
À1
yellow powder; mp 239–241°C. FTIR (νmax, cm ):
3401, 3292, 2964, 2847, 1667, 1525, 1377, 1271, 1081,
In brief, we have reported a new one-pot three-
component synthesis of a series of ethyl 2-amino-4-
benzoyl-5-oxo-5,6-dihydro-4H-pyrano[3,2-c]quinoline-3-
carboxylate derivatives 4a–h in the presence of TPAB as a
catalyst. The proposed method has got some considerable
advantages such as using an inexpensive and recoverable
catalyst, a simple workup process, using water as a green
solvent, short reaction times, and high yields.
À1
1
7
55 cm . H-NMR δ (ppm): 11.74 (s, exchanged by
D O addition, 1H, NH), 7.94 (d, J = 8.4 Hz, 2H, ArH),
2
7.93–7.90 (m, 1H, ArH), 7.92 (s, exchanged by D
addition, 2H, NH ), 7.75 (d, J = 8.4 Hz, 2H, ArH), 7.66
O
2
2
(
d, J = 8.4 Hz, 1H, ArH), 7.59 (t, J = 8.1 Hz, 1H, ArH),
7.47 (d, J = 8.1 Hz, 1H, ArH), 5.57 (s, 1H, CH), 3.79 (q,
J = 6.6 Hz, 2H, CH ), 0.71 (t, J = 6.9 Hz, 3H, CH ).
2
3
13
C-NMR δ (ppm): 197.7, 176.1, 167.9, 161.5, 160.5,
52.7, 140.5, 139.9, 138.2, 137.1, 132.7, 132.5, 130.4,
27.1, 123.6, 112.4, 109.6, 105.9, 73.7, 14.7. Anal. Calcd
1
1
EXPERIMENTAL
for C H BrN O : C, 56.31; H, 3.65; N, 5.97. Found: C,
22
17
2 5
Melting points were determined on a digital melting
5
6.20; H, 3.74; N, 5.87%.
Ethyl 2-amino-4-(4-chlorobenzoyl)-5-oxo-5,6-dihydro-4H-
point
apparatus
(Electrothermal,
Cole-Parmer,
Staffordshire, UK) and reported uncorrected. Infrared
spectra were recorded on a Thermo Nicolet (Nexus
pyrano[3,2-c]quinoline-3-carboxylate (4c).
white powder; mp 244–246°C. FTIR (νmax, cm ):
Yield, 86%;
À1
6
70) FTIR spectrometer (Thermo Fisher Scientific,
3
1
404, 3294, 2957, 2839, 1670, 1593, 1526, 1378,
1
13
Waltham, MA), using KBr disks. H and C nuclear
magnetic resonance (NMR) spectra were recorded with
a Bruker spectrometer at 300 and 75 MHz, respectively
1
271, 1083, 757. H-NMR
δ
(ppm): 11.75 (s,
exchanged by D O addition, 1H, NH), 8.18 (d,
2
J = 7.8 Hz, 2H, ArH), 7.95–7.92 (m, 1H, ArH), 7.92
(
Bruker, Billerica, MA). The spectra were measured in
(
s, exchanged by D O addition, 2H, NH ), 7.60 (d,
2 2
DMSO-d6 using tetramethylsilane as the internal
standard. Elemental analyses were performed using a
Leco Analyzer 932 (Leco Corp., St. Joseph, MI).
General procedure for synthesis of new pyranoquinoline
J = 8.7 Hz, 2H, ArH), 7.59–7.52 (m, 1H, ArH), 7.35
d, J = 9.3 Hz, 1H, ArH), 7.31 (t, J = 7.2 Hz, 1H,
ArH), 5.58 (s, 1H, CH), 3.78 (q, J = 6.6 Hz, 2H,
(
13
CH ), 0.70 (t, J = 6.6 Hz, 3H, CH ). C-NMR δ
2
3
derivatives 4a–h.
The arylglyoxal monohydrates
(ppm): 196.6, 167.9, 161.5, 160.5, 152.7, 138.2, 136.7,
(
1 mmol) was dissolved in H O/EtOH (1:1) (6 mL),
2
1
1
32.4, 129.7, 127.5, 123.5, 121.6, 121.5, 116.9, 115.0,
14.8, 112.4, 109.6, 73.7, 14.8. Anal. Calcd for
and then, ethyl cyanoacetate (1 mmol), catalyst (TPAB)
20 mol%), and 4-hydroxyquinolin-2(1H)-one (1 mmol)
(
C H ClN O : C, 62.20; H, 4.03; N, 6.59. Found: C,
22
17
2 5
were added to the reaction mixture. The reaction
mixture was heated at reflux for the appropriate time as
indicated in Table 2. The reaction completion was
monitored by thin-layer chromatography using (EtOAc/
hexane/MeOH, 1:1:1) as eluent. The precipitate was
filtered and washed with (chloroform/hexane 1:2) to
give the desired products as white to brown powders in
6
2.33; H, 3.91; N, 6.41%.
Ethyl
2-amino-4-(4-fluorobenzoyl)-5-oxo-5,6-dihydro-4H-
pyrano[3,2-c]quinoline-3-carboxylate (4d).
white powder; mp 245–247°C. FTIR (νmax, cm ): 3407,
3302, 2971, 2850, 1670, 1513, 1378, 1273, 1221, 1083,
757. H-NMR δ (ppm): 11.65 (s, exchanged by D O
Yield, 87%;
À1
1
2
addition, 1H, NH), 8.24 (d, J = 7.8 Hz, 2H, ArH), 7.91
8
0–91% yields.
Ethyl 2-amino-4-benzoyl-5-oxo-5,6-dihydro-4H-pyrano[3,2-
(s, exchanged by D O addition, 2H, NH ), 7.70 (d,
2
2
J = 8.7 Hz, 2H, ArH), 7.57 (d, J = 7.2 Hz, 1H, ArH),
.47 (d, J = 8.1 Hz, 1H, ArH), 7.36 (t, J = 7.2 Hz, 1H,
ArH), 7.31–7.12 (m, 1H, ArH), 5.60 (s, 1H, CH), 3.79
q, J = 7.2 Hz, 2H, CH ), 0.70 (t, J = 8.7 Hz, 3H, CH ).
c]quinoline-3-carboxylate (4a).
powder; mp 227–229°C. FTIR (νmax, cm ): 3408, 3300,
Yield, 88%; white
7
À1
2
971, 2843, 1676, 1523, 1375, 1272, 1218, 1084, 747.
(
2
3
1
H-NMR δ (ppm): 11.73 (s, exchanged by D O addition,
13
2
C-NMR δ (ppm): 194.2, 167.9, 163.9, 162.8, 161.5,
1H, NH), 8.16 (d, J = 6.6 Hz, 2H, ArH), 7.94 (t,
1
1
60.6, 152.7, 139.7, 138.2, 134.7, 131.4, 123.2, 122.0,
21.9, 116.3, 114.6, 112.4, 109.6, 73.8, 14.7. Anal. Calcd
J = 7.8 Hz, 1H, ArH), 7.93 (s, exchanged by D O
addition, 2H, NH ), 7.60–7.54 (m, 3H, ArH), 7.58 (d,
J = 7.8 Hz, 2H, ArH), 7.37–7.30 (m, 1H, ArH), 5.63 (s,
CH, 1H), 3.75 (bs, 2H, CH ), 0.68 (bs, 3H, CH ). C-
2
2
for C H FN O : C, 64.70; H, 4.20; N, 6.86. Found: C,
22
17
2 5
6
4.85; H, 4.11; N, 6.70%.
Ethyl 2-amino-4-(4-methylbenzoyl)-5-oxo-5,6-dihydro-4H-
13
2
3
NMR δ (ppm): 193.8, 167.9, 161.5, 160.6, 152.8, 138.2,
pyrano[3,2-c]quinoline-3-carboxylate (4e).
white powder; mp 240–242°C. FTIR (νmax, cm ): 3387,
Yield, 85%;
À1
137.9, 132.8, 130.7, 130.6, 129.5, 128.4, 123.5, 116.8,
1
15.0, 114.9, 112.5, 109.9, 73.8, 14.7. Anal. Calcd for
3288, 2947, 2843, 1666, 1532, 1377, 1268, 1179, 1082,
1022, 748. H-NMR δ (ppm): 11.72 (s, exchanged by
1
C H N O : C, 67.69; H, 4.65; N, 7.18. Found: C,
2
2 18 2 5
67.58; H, 4.79; N, 7.01%.
D
O addition, 1H, NH), 8.07 (d, J = 8.4 Hz, 2H, ArH),
2
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

A. Poursattar Marjani, J. Khalafy, and A. Farajollahi
Vol 000
7
.93 (t, J = 6.9 Hz, 1H, ArH), 7.89 (s, exchanged by D O
114.6, 112.4, 109.6, 73.8, 14.9. Anal. Calcd for
2
addition, 2H, NH ), 7.58 (t, J = 8.1 Hz, 1H, ArH), 7.35 (d,
C H N O : C, 60.69; H, 3.94; N, 9.65. Found: C,
22 17 3 7
2
J = 8.1 Hz, 1H, ArH), 7.32 (d, J = 7.2 Hz, 2H, ArH), 7.31–
60.83; H, 4.09; N, 9.55%.
7
.27 (m, 1H, ArH), 5.60 (s, 1H, CH), 3.79 (q, J = 7.2 Hz,
1
3
2H, CH ), 0.75 (t, J = 6.9 Hz, 3H, CH ). C-NMR δ
2
3
Acknowledgment. The authors gratefully acknowledge the
financial support from Urmia University.
(
1
1
ppm): 192.0, 167.9, 161.4, 160.7, 152.8, 143.5, 138.2,
38.1, 135.2, 130.9, 130.8, 128.7, 128.1, 123.5, 116.9,
14.9, 112.5, 109.9, 73.9, 21.6, 14.7. Anal. Calcd for
C H N O : C, 68.31; H, 4.98; N, 6.93. Found: C,
2
3
20
2
5
REFERENCES AND NOTES
6
8.52; H, 4.83; N, 6.87%.
Ethyl 2-amino-4-(3-methoxybenzoyl)-5-oxo-5,6-dihydro-4H-
[1] Li, M.; Zuo, Z.; Wen, L.; Wang, S. J Comb Chem 2008,
1
2
3
0, 436.
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pyrano[3,2-c]quinoline-3-carboxylate (4f).
white powder; mp 228–230°C. FTIR (νmax, cm ): 3409,
Yield, 80%;
À1
3
300, 2960, 2837, 1682, 1592, 1522, 1374, 1260, 1085,
1
759. H-NMR δ (ppm): 11.75 (s, exchanged by D O
2
[
addition, 1H, NH), 7.94 (t, J = 7.8 Hz, 1H, ArH), 7.91 (s,
exchanged by D O addition, 2H, NH ), 7.79 (d,
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2
2
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J = 7.8 Hz, 1H, ArH), 7.61 (s, 1H, ArH), 7.57 (t,
J = 7.6 Hz, 1H, ArH), 7.47 (t, J = 7.8 Hz, 1H, ArH),
[
[
7] Argauer, R. J.; Landolt, G. R. US Patent 3 702 886 1972.
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7.38–7.28 (m, 2H, ArH), 7.24–7.19 (m, 1H, ArH), 5.59
(
s, 1H, CH), 3.82 (s, 3H, OCH ), 3.80 (q, J = 6.9 Hz,
1173.
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2756.
3
1
3
2
H, CH ), 0.73 (t, J = 6.9 Hz, 3H, CH ). C-NMR δ
2
3
(ppm): 198.6, 167.9, 161.5, 160.6, 159.4, 152.8, 139.3,
2
1
1
39.2, 138.2, 132.8, 130.6, 128.5, 123.2, 121.0, 119.8,
14.9, 112.5, 109.8, 73.9, 54.9, 14.7. Anal. Calcd for
[
[11] Dar, A. M.; Shams, Uzzaman. Eur Chem Bull 2015, 4, 249.
C H N O : C, 65.71; H, 4.80; N, 6.66. Found: C,
2
3 20 2 6
[12] Kaur, C.; Dhiman, S.; Singh, H.; Kaur, M.; Bhagat, S.;
6
5.66; H, 4.70; N, 6.53%.
Gupta, M.; Sharma, S.; Bedi, P. M. S. Asian J Biochem Pharm Res
2015, 7, 127.
Ethyl 2-amino-4-(3,4-dimethoxybenzoyl)-5-oxo-5,6-dihydro-
4
H-pyrano[3,2-c]quinoline-3-carboxylate (4g). Yield, 91%;
[13] Murray, R. D. H. Fortchemie 1991, 35, 1.
[14] Makawana, J. A.; Patel, M. P.; Patel, R. G. Arch Pharm Chem
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A. B.; Bhatia, G.; Srivastava, A. K. Bioorg Med Chem Lett 2009, 19,
6447.
À1
cream powder; mp 232–234°C. FTIR (νmax, cm ): 3390,
3
1
D O addition, 1H, NH), 7.93–7.87 (m, 2H, ArH) 7.86 (s,
exchanged by D O addition, 2H, NH ), 7.63 (s, 1H,
293, 2946, 2843, 1669, 1517, 1377, 1250, 1160, 1083,
1
025, 763. H-NMR δ (ppm): 11.71 (s, exchanged by
2
2
2
ArH), 7.58–7.55 (m, 1H, ArH), 7.36–7.28 (m, 2H, ArH),
.13–7.10 (m, 2H, ArH), 5.61 (s, 1H, CH), 3.86 (s, 3H,
OCH ), 3.85 (q, J = 8.1 Hz, 2H, CH ), 3.80 (s, 3H,
[
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7
1
3
2
[
1
3
OCH ), 0.82 (t, J = 8.1 Hz, 3H, CH ). C-NMR δ
3
3
(ppm): 193.6, 167.9, 161.4, 160.8, 152.9, 148.4, 138.2,
[
1
1
30.3, 126.1, 123.4, 123.2, 116.8, 114.8, 113.1, 112.6,
10.9, 110.0, 109.9, 74.1, 55.3, 55.1, 14.9. Anal. Calcd
[
for C H N O : C, 64.00; H, 4.92; N, 6.22. Found: C,
6
24 22 2 7
[
4.20; H, 4.89; N, 6.12%.
Ethyl
2-amino-4-(4-nitrobenzoyl)-5-oxo-5,6-dihydro-4H-
[
pyrano[3,2-c]quinoline-3-carboxylate (4h).
brown powder; mp 225–227°C. FTIR (νmax, cm ):
3
1
Yield, 81%;
Moradi, A.; Emami, S.; Foroumadi, A.; Shafiee, A. Eur J Med Chem
2013, 68, 260.
À1
[23] Rafinejad, A.; Fallah-Tafti, A.; Tiwari, R.; Shirazi, A. N.;
405, 3299, 2975, 2856, 1520, 1681, 1345, 1281,
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DARU J Pharm Sci 2012, 20, 1.
1
223, 1090, 756. H-NMR
δ
(ppm): 11.78 (s,
exchanged by D O addition, 1H, NH), 8.39 (d,
J = 7.5 Hz, 2H, ArH), 8.38–8.33 (m, 1H, ArH), 7.96
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2
[25] Abu-Hashem, A. A.; Aly, A. S. Arch Pharm Res 2012, 35,
(
s, exchanged by D O addition, 2H, NH ), 7.94–7.90
2 2
4
3
2
37.
(
2
m, 1H, ArH), 7.62–7.56 (m, 2H, ArH), 7.38–7.28 (m,
H, ArH), 5.62 (s, CH, 1H), 3.74 (q, J = 7.8 Hz, 2H,
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28] Cairns, H.; Cox, D.; Gould, K.; Ingall, A.; Suschitzky, J. J Med
Chem 1985, 28, 1832.
1
3
CH ), 0.64 (t, J = 7.2 Hz, 3H, CH ). C-NMR δ
2
3
(ppm): 194.2, 167.9, 163.9, 162.8, 161.5, 160.6, 152.7,
[
139.7, 138.2, 134.7, 131.4, 123.2, 122.0, 121.9, 116.3,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2018
Synthesis of Ethyl 2-Amino-4-benzoyl-5-oxo-5,6-dihydro-4H-
pyrano[3,2-c]quinoline-3-carboxylates
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4
[
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[
2
[
[
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet