Sulfamic Acid Catalyzed Atom Economic, Eco-friendly Synthesis of Novel 7-(Aryl)-10-thioxo-7,9,10,11-tetrahedro-6H-pyrimido-[5′4′:5,6]pyrano[3,2-c]quinoline-6,8(5H)-dione and its Derivatives

Article abstract of DOI:10.1002/jhet.2807

A series of novel 7-(3-chloro-phenyl)-10-thioxo-7,9,10,11-tetrahedro-6H-pyrimido-[5′4′:5,6] pyrano[3,2-c]quinoline-6,8(5H)-dione derivatives have been synthesized through the multi-component condensation of aromatic aldehydes, barbituric acid, and 2,4-dih

Full text of DOI:10.1002/jhet.2807

Month 2017
Sulfamic Acid Catalyzed Atom Economic, Eco-friendly Synthesis of
Novel 7-(Aryl)-10-thioxo-7,9,10,11-tetrahedro-6H-pyrimido-[5′4′:5,6]
pyrano[3,2-c]quinoline-6,8(5H)-dione and its Derivatives
Sunetra J. Jadhav,a Reshma B. Patil,a Digambar R. Kumbhar,a Ajinkya A. Patravale,b,c Dattatraya R. Chandam,b and
Madhukar B. Deshmukha,b
*
aDepartment of Agrochemicals and Pest Management, Shivaji University, Kolhapur 416004, India
bMedicinal Chemistry Research Laboratory, Department of Chemistry, Shivaji University, Kolhapur 416004 M.S., India
cDepartment of Chemistry, Vivekanand College, Kolhapur M. S., India
*
E-mail: shubhlaxmi111@gmail.com
Additional Supporting Information may be found in the online version of this article.
Received May 7, 2016
DOI 10.1002/jhet.2807
Published online 00 Month 2017 in Wiley Online Library (wileyonlinelibrary.com).
A series of novel 7-(3-chloro-phenyl)-10-thioxo-7,9,10,11-tetrahedro-6H-pyrimido-[5′4′:5,6] pyrano
[3,2-c]quinoline-6,8(5H)-dione derivatives have been synthesized through the multi-component condensa-
tion of aromatic aldehydes, barbituric acid, and 2,4-dihydroxy quinoline, using heterogeneous sulfamic acid
catalyst in water-ethanol (4:1) solvent system under reflux condition. The present protocol is endowed with
charming description such as green synthetic procedure, short reaction time, easy work-up procedure, and
excellent yield and high atom economy of pyranoquinoline derivatives. In this study, sulfamic acid is used
as a heterogeneous catalyst that is easily recoverable and recyclable. The proposed multi-component reaction
has been studied with detail mechanism and spectroscopic data. This is one of the potential greener synthetic
approaches to build up the series of pyranoquinoline heterocycles.
J. Heterocyclic Chem., 00, 00 (2017).
INTRODUCTION
single synthetic operational techniques are widely used in
chemical and pharmaceutical combinatorial synthesis [5],
which are enviro-economically advantageous because of
their productivity, simple procedures, convergence, atom
economy, use of non-toxic greener solvents for reaction,
and facile execution. Moreover, under an umbrella of
green chemistry, organic processes should be designed
Multi-component reactions (MCRs) involve use of two
or more simple and flexible building components to be
combined; hence, it is considered as automated synthesis
(Fig. 1) [1]. MCRs have fascinated interest owing to their
outstanding synthetic effectiveness, high-bond forming
efficiency, brevity, and molecular diversity [2]. MCRs
play an important role in heterocyclic synthesis because
of the ability to construct the new C–C and C-hetero
bonds [3]. Thus, MCRs have attracted considerable
interest owing to their exceptional synthetic efficiency.
The development of current heterocyclic synthesis
is considerably dependent on further advances in
heterocyclic MCRs methodology. According to current
synthetic needs, ecologically pure multi-component
procedures are particularly welcomed [4]. Thus, these
using water as
a
solvent or under solvent-free
conditions [6]. Furthermore, water is referred as “the
universal solvent.” From economical and environmental
point of view, water is accompanying with some
interesting features like easy availability, ease of
handling, non-toxicity, and non-volatility. In recent years,
water has been employed as a solvent in many organic
transformations even though the solubility is prerequisite
for any heterocyclic compounds synthesis [7]. With
growing consciousness of research community,
© 2017 Wiley Periodicals, Inc.

S. J. Jadhav, R. B. Patil, D. R. Kumbhar, A. A. Patravale, D. R. Chandam, and M. B. Deshmukh Vol 000
Figure 1. Multi-component reaction strategies. [Color figure can be viewed at wileyonlinelibrary.com]
researchers use water as a solvent for the MCRs [8].
Recently, using water as a solvent, 32% of pharmaceutical
heterocyclic products have been synthesized [9].
It is well known that the nitrogen and oxygen containing
heterocyclic compounds are important nuclei in various
natural product syntheses [10,11]. Geibalasine (Fig. 2a),
ribalinine (Fig. 2b), and findersine (Fig. 2c) are the few
examples of natural products [12–15]. The nitrogen
containing linomide (Fig. 2d) derivative is a well-known
immunomodulator (Fig. 2) [16].
Thus, pyranoquinoline is one of the significant nitrogen
and oxygen containing heterocyclic compounds having
diverse significant biochemical processes [17–22].
Naturally, pyranoquinoline motifs are present in leaves
and roots of Toddalia asiatica (L) Lam (Rutaceae)
[23,24]. Pyranoquinolines are associated with a variety of
pharmacological properties such as estrogenic [25,26],
anti-inflammatory [27], antiproliferative, anti-tubulin
activities [28], anti-microbial [29], and anti-viral [30].
Owing to the pharmacological significance of this class
of compounds, several researchers have paid considerable
attention towards the synthesis of pyranoquinoline
derivatives [31–33]. Moreover, the literature designates
that nitrogen and oxygen containing fused pyranoquinoline
derivatives have been carried out by diverse catalyst such
as ionic liquids [34], ammonium acetate [20], Et3N [28],
CAN [35], KF-Al2O3 [36], pyridine [37], sodium
ethoxide [38], laccase [39], acetic acid [40], PPA [41],
FeCl3NaI [42], Au-TiO2 [43], Yb(OTf)3 [44], and phase
transfer catalyst [45]. These methods have their own
limitations such as tedious workup procedures, use of
toxic reagents, carcinogenic solvents, and cost of reactant
and catalyst. However, heterogeneous acid catalysts are
more useful and act as an alternative for the conventional
homogeneous acid catalysts. Sulfamic acid (H2NSO3H) is
relatively stable, commercially available, non-volatile,
and non-corrosive green heterogeneous catalysis [46]. It
has been widely used as an effective catalyst in organic
synthesis [46,47], owing to their properties and to outwit
demerits of the previous reports with elevated interest in
the heterocycle synthesis via greener method and
efficient starting ingredients with economically chipper
catalyst [48]. Herein, we successfully demonstrate an
inexpensive, atom economic and eco-friendly way for
synthesis of pyranoquinolines using water-ethanol (4:1)
as a green non-toxic solvent system and reusable
sulfamic acid catalyst in one-pot three-component
condensation.
Figure 2. Nitrogen and oxygen containing fused heterocyclic natural product. [Color figure can be viewed at wileyonlinelibrary.com]
Scheme 1. Synthesis of pyranoquinoline derivatives. [Color figure can be viewed at wileyonlinelibrary.com]
Journal of Heterocyclic Chemistry
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Month 2017
Sulfamic Acid Catalyzed Synthesis of Novel Pyrano [3,2-c]quinoline Derivative
RESULTS AND DISCUSSION same compound exhibited a signal at δ 33.18 for benzylic
carbon, and the remaining aromatic carbons appeared
between the ranges at δ 95.65–137.55 ppm. The carbonyl
carbon in the product was observed at δ 165.73 and
173.87 ppm (Supporting Information), which confirmed
the formation of the desired compound. These initial
results inspired us to optimize the reaction and study the
scope of reaction in detail.
A model reaction (Scheme 1), 3-chlorobenzaldehyde
(1a, 1 mmol) and thiobarbituric acid (2a, 1 mmol), was
taken in 50 mL round-bottomed flask containing 5 mL of
water-ethanol (4:1). The resultant reaction mixture was
stirred at room temperature to complete the Knoevenagel
reaction monitored by thin-layer chromatography (TLC).
After the formation of Knoevenagel product, 2,4-
dihydroxyquinoline (3a, 1 mmol) and sulfamic acid
were introduced and reaction refluxed in an oil bath
until completion of the reaction. Then reaction mixture
was poured slowly on the crushed ice–water mixture
with constant stirring. The product was recrystallized
using ethanol. The IR spectrum of 7-(3-chloro-phenyl)-
10-thioxo-7,9,10,11-tetrahedro-6H-pyrimido-[5′4′:5,6]
pyrano[3,2-c]quinoline-6,8(5H)-dione shows aromatic
C–H stretching band at 2929 cmÀ1, and C═O and C═S
group appeared at 1678 and 1636 cmÀ1(see Supporting
Optimization of reaction.
For the optimization of
reaction, it is essential to study the effect of solvent and
amount of catalyst on the said MCR; the same reaction
was carried out in various solvents and amount of
catalysts included in the table (Table 1). In the trial case,
when reactions were carried out at an uncatalyzed
condition with variation of solvent (Table 1, entry 1–8),
expected products were not obtained; however, the
reaction proceeded up to the Knoevenagel condensation.
Later on, the same reaction was performed using catalytic
amount of acetic acid and sulfamic acid at room
temperature as well as under reflux conditions up to 12 h
(Table 1, entry 9–17). The catalytic efficiency of sulfamic
acid was studied with respect to quantity used. The same
reaction was extended with a varying amount of sulfamic
acid in water-ethanol (Table 1, entry 18–22). It has been
observed that 20 mol% of catalyst is sufficient for this
1
Information data). The H NMR of the same compound
showed a singlet for benzylic (ÀCH) proton at δ 6.19 ppm,
and the remaining eight aromatic protons encountered
between the aromatic region at δ 7.05–8.05 ppm. The
characteristic ÀNH proton signals appeared as a singlet at
δ 12.37 and 12.44 ppm. The 13C NMR spectrum of the
Table 1
Optimization of reactiona conditions for the synthesis of 7-(3-chloro-phenyl)-10-thioxo-7,9,10,11-tetrahedro-6H-pyrimido-[5′4′:5,6] pyrano[3,2-c]quin-
oline-6,8(5H)-dione derivatives.
Entry
Solvent
Temperature
RT
RT
RT
Catalyst (20 mol%)
Time (h)
Yield (%)b
1
2
3
4
5
6
7
8
Water
–
–
–
–
–
–
–
–
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
–
c
Acetonitrile
Methanol
–
–
–
–
–
–
–
–
c
c
Ethanol
Water
RT
c
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
c
Acetonitrile
Methanol
c
c
Ethanol
DMF
Water
c
9
Acetic acidd
c
10
11
12
13
14
15
16
17
18
19
20
21
22
Acetic acidd
–
–
c
Acetonitrile
Methanol
Acetic acidd
Acetic acidd
Trace
36
47
42
41
64
92
62
75
Ethanol
Water
Acetic acidd
Sulfamic acidd
Acetonitrile
Methanol
Sulfamic acidd
Sulfamic acidd
Ethanol
Sulfamic acidd
12
Water:ethanol (4:1)
Water:ethanol (4:1)
Water:ethanol (4:1)
Water:ethanol (4:1)
Water:ethanol (4:1)
Sulfamic acidd
1.30
1.30
1.30
1.30
1.30
5 mol% Sulfamic acid
10 mol% Sulfamic acid
15 mol% Sulfamic acid
25 mol% Sulfamic acid
85
88
aReaction of 3-chlorobenzaldehyde (1 mmol), thiobarbituric acid (1 mmol), and 2,4-dihydroxyquinoline (1 mmol) was carried out at different reaction
conditions and solvents.
bObtained yield.
cKnoevenagel condensation product.
dAmount of catalyst is 20 mol%.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

S. J. Jadhav, R. B. Patil, D. R. Kumbhar, A. A. Patravale, D. R. Chandam, and M. B. Deshmukh Vol 000
conversion (Table 1, entry 18). These results indicated that
the water-ethanol (4:1) solvent system and 20 mol% of
sulfamic acid are a good combination for the said MCRs.
These optimistic results inspired us to check the
applicability of the present protocol to get a new library
dione derivatives using experimentally designed optimum
conditions with various substituted aldehydes and
dicarbonyl compounds (Fig. 3) with electron-donating or
electron-withdrawing substituent. Electronic effect was
not observed on the said protocol with electron
withdrawing and donating groups of aromatic aldehydes,
but in case aliphatic aldehydes (butanal and 2-methyl
of
7-(3-chloro-phenyl)-10-thioxo-7,9,10,11-tetrahedro-
6H-pyrimido-[5′4′:5,6] pyrano[3,2-c]quinoline-6,8(5H)-
Figure 3. Synthesis of 7-(3-chloro-phenyl)-10-thioxo-7,9,10,11-tetrahedro-6H-pyrimido-[5′4′:5,6] pyrano[3,2-c]quinoline-6,8(5H)-dione derivatives.
[Color figure can be viewed at wileyonlinelibrary.com]
Journal of Heterocyclic Chemistry
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Month 2017
Sulfamic Acid Catalyzed Synthesis of Novel Pyrano [3,2-c]quinoline Derivative
propanal) failed to obtain the targeted compound. These
results showed that this new methodology is very useful
for the synthesis of the said compound. All the aromatic
aldehyde precursors gave a good yield irrespective of
their substitution pattern. Furthermore, the greener
approach of this protocol was proved by its atom
economy. Superior atom economy values and yields
showed the greenness of this methodology (Fig. 4).
Overall good to excellent yields of the desired
pyranoquinoline derivatives were obtained.
Figure 4. Atom economy and yield of a synthesized product. [Color figure can be viewed at wileyonlinelibrary.com]
Scheme 2. Plausible mechanism of the reaction.
Figure 5. Recyclability of catalyst. [Color figure can be viewed at wileyonlinelibrary.com]
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

S. J. Jadhav, R. B. Patil, D. R. Kumbhar, A. A. Patravale, D. R. Chandam, and M. B. Deshmukh Vol 000
The plausible mechanism for the formation of 7-(3-
chloro-phenyl)-10-thioxo-7,9,10,11-tetrahedro-6H-pyrimido-
[5′4′:5,6] pyrano[3,2-c]quinoline-6,8(5H)-dione is depicted
in Scheme 2. Initially, Knoevenagel condensation was
carried out between aromatic aldehyde (1a) and
thiobarbituric acid (2a) to form a Knoevenagel product
(5-(3-chlorobenzylidene)-2-thioxodihydropyrimidine-4,6
(1H,5H)-dione). The Knoevenagel product (5) was
subjected to Michael addition with the 2,4-
dihydroxyquinoline (3a) that gave an intermediate (6),
which subsequently cyclized followed by intramolecular
dehydration to form a desired product (4a).
The reusability of catalyst (sulfamic acid) is one of the
inspiring approaches of this methodology. The catalyst
was present in the aqueous layer. This aqueous layer was
evaporated under the reduced pressure and formed a solid
sulfamic acid, which is further washed with diethyl ether
(2 × 20 mL), dried at 80°C, and subjected to check the
efficiency. Recyclability of catalyst was checked to fourth
run having yield 92–77% (Fig. 5). Thus, the catalyst
showed excellent recyclability.
internal standard using DMSO-d6 as a solvent. The
chemical shift values are expressed in δ ppm.
General synthetic procedure. Aromatic aldehyde (1a,
1 mmol) and thiobarbituric acid/barbituric acid (2a,
1 mmol) were mixed together in a 50 mL round-
bottomed flask at a room temperature to get the
Knoevenagel product monitored by TLC. Then 2,4-
dihydroxyquinoline (3a, 1 mmol) and sulfamic acid
(20 mol%) were added, and the same reaction mixture
was refluxed using water-ethanol (4:1) as a solvent
(5 mL) for 1.30 h. The progress of the reaction was
monitored by TLC using ethyl acetate-petroleum ether
(8:2 v/v). After completion, the reaction mixture was then
poured slowly on crushed ice–water mixture with
constant stirring. The desired product was isolated,
filtered, and washed with ethanol (20 mL). Finally, the
crude product was recrystallized using ethanol. The
aqueous layer was evaporated under the reduced pressure
and recovered sulfamic acid, which is further washed
with diethyl ether (2 × 20 mL), dried at 80°C, and reused.
Spectral data of synthesized compounds. 7-(3-Chloro-
phenyl)-10-thioxo-7,9,10,11-tetrahedro-6H-pyrimido-[5′4′:5,6]
pyrano[3,2-c]quinoline-6,8(5H)-dione (4a).
White solid,
CONCLUSION
yield: 92%: 0.377 gm, m.p. > 300°C (decompose). IR
(KBr), ν max; 3074, 2929, 2767, 1720, 1676, 1636,
1
1604 cmÀ1; H NMR (300 MHz, DMSO-d6): δ, 6.19 (s,
In conclusion, we have developed an environmentally
benign, simple, and cost-efficient method for the
synthesis of a novel heterocyclic compounds 7-(3-chloro-
phenyl)-10-thioxo-7,9,10,11-tetrahedro-6H-pyrimido-[5′
4′:5,6] pyrano[3,2-c]quinoline-6,8(5H)-dione and its
derivatives using sulfamic acid in water-ethanol (4:1) as
a recyclable green catalyst and greener solvent system.
The developed methodology has major advantages
including its simplicity of operation, greener approach,
easy workup procedure, selectivity, higher yields, and
high-atom economic. Furthermore, the purification of
the product is simple; there is no need to use a column
chromatography technique, and moreover, the catalyst
collected could be reused for the subsequent reactions.
1H, ÀCH), 7.05–7.08 (d, J = 6 Hz, 2H, Ar-H), 7.22–7.37
(m, 4H, Ar-H), 7.46–7.67 (m, 1H, Ar-H), 8.03–8.05 (d,
J = 9 Hz 1H, Ar-H), 12.37 (br.s, 2H, ÀNH), 12.44 (br.s,
1H, ÀNH) ppm. 13C NMR (75 MHz, DMSO-d6): δ,
33.18, 95.65, 11.23, 116.56, 116.79, 123.51, 123.75,
125.77, 126.26, 126.65, 130.37, 131.99, 133.36, 137.28,
142.29, 162.69, 165.73, 173.87 ppm. 13C-DEPT 90 NMR
(75 MHz, DMSO-d6): 33.15, 116.79, 123.52, 123.75,
125.77, 126.26, 126.64, 130.38, 131.99 ppm. Anal.
Calcd. for C20H12 ClN3O5S: C, 58.61; H, 2.95; N,
10.25%. Found: C, 58.57; H, 2.88; N, 10.19%.
7-(4-Chloro-phenyl)-10-thioxo-7,9,10,11-tetrahedro-6H-
pyrimido-[5′4′:5,6] pyrano [3]quinoline-6,8(5H)-dione (4b).
White solid, yield: 91%: 0.374 gm, m.p. 280–284°C
(melt), IR (KBr), ν max: 3107, 2930, 1733, 1634,
1
1603 cmÀ1; H NMR (300 MHz, DMSO-d6): δ, 5.87 (s,
EXPERIMENTAL
1H, ÀCH), 7.05 (s, 2H, Ar-H), 7.01–7.02 (m, 2H, Ar-H),
7.44–7.53 (m, 2H, Ar-H), 7.98 (m, 2H, Ar-H), 12.50 (br.
s, 2H, ÀNH), 12.51 (br.s, 1H, ÀNH) ppm. 13C NMR
(75 MHz, DMSO-d6): δ, 33.08, 95.87, 111.25, 116.73,
123.59 (2C), 128.25 (2C), 128.56 (2C), 131.02 (2C),
131.76 (2C), 137.13, 137.55, 165.69, 173.79 (2C) ppm.
Anal. Calcd. for C20H12 ClN3O3S: C, 58.61; H, 2.95; N,
10.25%. Found: C, 58.69; H, 3.00; N, 10.29%.
All the chemicals were purchased from Sigma-Aldrich
and used without purification. The reaction was
monitored by TLC. The melting points were determined
in open-glass capillary tubes and were uncorrected. The
1
structures of compounds have been confirmed by IR, H
NMR, and 13C NMR. The IR spectra were recorded on a
JASCO FT-IR 4600 spectrophotometer, and the values
are expressed as ν max cmÀ1. The 1H NMR and
13C-DEPT NMR spectra were recorded on Bruker
7-(4-Bromo-phenyl)-10-thioxo-7,9,10,11-tetrahedro-6H-
pyrimido-[5′4′:5,6]
pyrano[3,2-c]quinoline-6,8(5H)-dione
Spectrospin
Avance
II-300
and
75
MHz
(4c). White solid, yield: 89%: 0404 gm, m.p. > 300°C
spectrophotometer relative to tetramethylsilane as an
(decompose), IR (KBr), ν max: 3070, 2929, 1725, 1682,
Journal of Heterocyclic Chemistry
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Month 2017
Sulfamic Acid Catalyzed Synthesis of Novel Pyrano [3,2-c]quinoline Derivative
1636, 1605 cmÀ1; 1H NMR (300 MHz, DMSO-d6): δ, 6.13
(s, 1H, ÀCH), 7.03–7.06 (d, J = 9 Hz, 2H, Ar-H), 7.32–
7.37 (t, 1H, Ar-H), 7.40–7.49 (m, 3H, Ar-H) 7.62–7.67
(t, 1H, Ar-H), 8.02–8.04 (d, J = 6 Hz, 1H, Ar-H), 12.37
(br.s, 3H, ÀNH) ppm. 13C NMR (75 MHz, DMSO-d6):
δ, 33.01, 95.80, 111.36, 116.55, 116.76 (2C), 119.17,
123.51, 123.71, 129.28 (2C), 131.31 (2C), 131.97 (2C),
137.24, 138.95, 162.60, 165.75, 173.84 ppm. Anal.
Calcd. for C20H12 BrN3O3S: C, 52.88; H, 2.66; N,
52.88; H, 2.66; N, 09.25. Found: C, 52.95; H, 2.71; N,
09.32%.
7-(3-Methoxy-phenyl)-10-thioxo-7,9,10,11-tetrahedro-6H-
pyrimido-[5′4′:5,6] pyrano [3,2-c]quinoline-6,8(5H)-dione
(4g). Yellow solid, yield: 78%: 0.316 gm, m.p. > 300°C
(decompose), IR (KBr), ν max: 3070, 2929, 1725, 1682,
1
1636, 1605 cmÀ1; H NMR (300 MHz, DMSO-d6): δ,
3.66 (s, 3H, ÀOCH3), 6.11 (s, 1H, ÀCH), 6.66–6.68 (d,
J = 6 Hz, 2H, Ar-H), 6.75–6.77 (d, J = 6 Hz, 1H, Ar-H),
7.14–7.20 (t, 1H, Ar-H), 7.33–7.38 (t, 1H, Ar-H), 7.47–
7.50 (m, 1H, Ar-H), 7.62–7.67 (t, 1H, Ar-H), 8.03–8.05
(s, 1H, Ar-H), 12.47 (br.s, 3H, ÀNH) ppm. 13C NMR
(75 MHz, DMSO-d6): δ, 33.29, 55.36, 60.21, 95.08,
110.79, 111.73, 113.40, 116.80, 119.26, 123.53, 123.67,
126.43, 127.00, 127.19, 129.59, 131.92, 131.19, 159.68,
165.88, 168.78, 173.81 ppm. Anal. Calcd. for C21H15
N3O4S; C, 62.21; H, 3.73; N, 10.36%. Found: C, 62.16;
H, 3.68; N, 10.31%.
09.25%. Found: C, 52.79; H, 2.59; N, 09.21%.
7-(3-Nitro-phenyl)-10-thioxo-7,9,10,11-tetrahedro-6H-
pyrimido-[5′4′:5,6]
pyrano[3,2-c]quinoline-6,8(5H)-dione
(4d). Yellow solid, yield: 88%: 0.369 gm, m.p. > 300°C
(decompose). IR (KBr), ν max: 3084, 2981, 1700, 1683,
1643, 1524, 1387 cmÀ1
;
1H NMR (300 MHz,
DMSO-d6): δ, 6.32 (s, 1H, ÀCH), 7.35–7.38 (t, 1H,
Ar-H), 7.47–7.68 (m, 4H, Ar-H), 7.85 ( s, 1H, Ar-H),
8.05–8.07 (d, 2H, Ar-H), 12.36 (br.s, 2H, ÀNH), 12.45
(br.s, 1H, ÀNH) ppm. 13C NMR (75 MHz, DMSO-d6):
δ, 33.37, 95.47, 110.87, 116.57, 116.84, 121.46, 123.59,
123.80, 130.08, 132.11, 134.09, 137.33, 142.30, 148.27,
162.96, 163.90, 165.68, 173.99 ppm. Anal. Calcd. for
C20H12 N4O5S: C, 57.14; H, 2.88; N, 13.33%. Found: C,
7-(4-Methoxy-phenyl)-10-thioxo-7,9,10,11-tetrahedro-6H-
pyrimido-5′4′:5,6]
pyrano[3,2-c]quinoline-6,8(5H)-dione
(4h). Yellow solid, yield: 79%: 0.319 gm, m.p. > 300°C
(decompose), IR (KBr), ν max: 3069, 2902, 1637,
1
1604 cmÀ1; H NMR (300 MHz, DMSO-d6): δ, 3.88 (s,
3H, ÀOCH3), 5.87 (s, 1H, ÀCH), 7.06–7.09 (d,
J = 9 Hz, 2H, Ar-H), 7.25 (s, 1H, Ar-H), 7.46–7.52 (t,
1H, Ar-H), 7.73–7.79 (s, 1H, Ar-H), 8.02 (s, 1H, Ar-H),
8.40–8.43 (d, J = 9 Hz, 2H, Ar-H), 11.27 (s, 1H, ÀNH),
12.30 (br.s, 1H, ÀNH), 12.39 (br.s, 1H, ÀNH) ppm. 13C
NMR (75 MHz, DMSO-d6): δ, 55.42, 98.18, 113.93,
114.54, 115.59, 115.85, 116.01, 121.90, 123.17 (2C),
127.00 (2C), 127.89, 131.55, 135.34, 138.41, 160.41,
163.48, 164.02, 164.45, 178.14 ppm. Anal. Calcd. for
C21H15 rN3O4S: C, 62.21; H, 3.73; N, 10.36%. Found:
C, 62.19; H, 3.71; N, 10.40%.
57.18; H, 2.81; N, 13.26%.
7-(Phenyl)-10-thioxo-7,9,10,11-tetrahedro-6H-pyrimido-[5′
4′:5,6] pyrano[3,2-c]quinoline-6,8(5H)-dione (4e).
White
solid, yield: 81%: 0.304 gm, m.p. 280–283°C. IR (KBr),
ν max: 3064, 2930, 1676, 1635, 1604 cmÀ1; H NMR
1
(300 MHz, DMSO-d6): δ, 6.14 (s, 1H, ÀCH), 7.07–7.27
(m, 5H, Ar-H), 7.33–7.38 (t, 1H, Ar-H), 7.47–7.50 (d,
J = 9 Hz, 1H, Ar-H), 7.62–7.67 (t, 1H, Ar-H), 8.03–8.05
(d, J = 6 Hz, 1H, Ar-H), 12.47, (3H, ÀNH) ppm. 13C
NMR (75 MHz, DMSO-d6): δ, 33.32, 96.16, 111.72,
116.56, 116.79 (2C), 123.56, 123.67, 126.22 (2C),
126.80, 128.54 (2C), 131.92, 137.18 (2C), 138.94,
162.53, 165.90, 173.82 ppm. 13C-DEPT 135 NMR
(75 MHz, DMSO-d6): 33.30, 116.79, 123.56, 123.66,
126.22, 126.79, 128.55, 131.93 ppm. 13C-DEPT 90 NMR
(75 MHz, DMSO-d6): 33.29, 116.79, 123.56, 123.66,
126.22, 128.55, 131.93, 126.79 ppm. Anal. Calcd. for
C20H13 N3O3S: C, 63.99; H, 3.49; N, 11.19%. Found: C,
7-(4-Nitro-phenyl)-10-thioxo-7,9,10,11-tetrahedro-6H-
pyrimido-[5′4′:5,6]
pyrano[3,2-c]quinoline-6,8(5H)-dione
(4i). Yellow solid, yield: 89%: 0.374 gm, m.p. > 300°C
(decompose), IR (KBr), ν max: 3071, 2930, 1733, 1634,
;
1604, 1560, 1391 cmÀ1 1H NMR (300 MHz,
DMSO-d6): δ, 6.13 (s, 1H, ÀCH), 7.35–7.47 (m, 4H,
Ar-H), 7.61–7.65 (m, 1H, Ar-H), 8.01–8.12 (m, 3H, Ar-
H), 12.22 (br.s, 3H, ÀNH) ppm. 13C NMR (75 MHz,
DMSO-d6): 33.76, 95.44, 108.99, 110.99, 116.56,
116.79, 119.46, 123.52, 123.77 (2C), 128.13 (2C),
132.04, 132.45, 137.33, 146.09, 147.29, 162.84, 165.69,
173.93 ppm. Anal. Calcd. for C20H12 N4O5S: C, 57.14;
H, 2.88; N, 13.33%. Found: C, 57.20; H, 2.82; N 13.37%.
7-(4-Cyno-phenyl)-10-thioxo-7,9,10,11-tetrahedro-6H-
64.04; H, 3.54; N, 11.25%.
7-(3-Bromo-phenyl)-10-thioxo-7,9,10,11-tetrahedro-6H-
pyrimido-[5′4′:5,6]
pyrano[3,2-c]quinoline-6,8(5H)-dione
(4f). White solid, yield: 88%: 0399 gm, m.p. > 300°C
(decompose), IR (KBr), ν max: 3100, 2978, 2858, 1725,
1
1644, 1605 cmÀ1; H NMR (300 MHz, DMSO-d6): δ,
6.20 (s, 1H, ÀCH), 7.06 (s, 1H, Ar-H), 7.09–7.23 (m,
2H, Ar-H), 7.30–7.36 (m, 2H, Ar-H), 7.43–7.46 (m, 1H,
Ar-H), 7.60–7.65 (m, 1H, Ar-H), 7.99–8.03 (m, 1H,
Ar-H), 12.25 (br.s, 3H, ÀNH) ppm. 13C NMR
(75 MHz, DMSO-d6): δ, 33.08, 60.28, 95.49, 111.22,
116.65, 122.01, 123.45, 123.75, 126.14, 129.11, 129.43,
130.71, 131.96, 137.27, 142.82, 158.54, 162.66, 165.62,
170.94, 173.79. Anal. Calcd. for C20H12 BrN3O3S: C,
pyrimido-[5′4′:5,6]
pyrano[3,2-c]quinoline-6,8(5H)-dione
(4j). White solid, yield: 88%: 0.352 gm, m.p. 273–276°C
(decompose), IR (KBr), ν max: 3070, 2929, 2225, 1682,
1
1636, 1604 cmÀ1; H NMR (300 MHz, DMSO-d6): δ,
6.28 (s, 1H, ÀCH), 7.27–7.30 (d, 3H, Ar-H), 7.46 (s, 1H,
Ar-H), 7.63–7.70 (m, 3H, Ar-H), 8.02 (s, 1H, Ar-H),
12.23 (br.s, 1H, ÀNH), 12.27 (br.s, 2H, ÀNH) ppm. 13C
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

S. J. Jadhav, R. B. Patil, D. R. Kumbhar, A. A. Patravale, D. R. Chandam, and M. B. Deshmukh Vol 000
NMR (75 MHz, DMSO-d6): δ, 33.74, 95.43, 111.07,
116.58, 116.72, 123.44 (2C), 123.69 (2C), 123.80 (2C),
128.33 (2C), 132.02, 137.38, 146.17, 148.73, 162.76,
165.64, 173.94 ppm. Anal. Calcd. for C21H12 N4O3S: C,
62.99; H, 3.02; N, 13.99%. Found: C, 63.03; H, 3.09; N,
13.91%.
(300 MHz, DMSO-d6): δ, 2.25 (s, 3H, ÀCH3), 7.01 (s,
4H, ÀAr-H), 7.27 (s, 1H, Ar-H), 7.43–7.45 (d, 1H, Ar-
H), 7.55 (s, 1H, Ar-H), 7.86–7.98 (m, 2H, Ar-H), 11.18
(br.s, 1H, ÀNH), 12.28 (br.s, 1H, ÀNH), 12.34 (br.s, 1H,
ÀNH) ppm. 13C NMR (75 MHz, DMSO-d6): δ, 20.98,
32.44, 112.75, 116.56 (2C), 123.11, 123.46, 126.56 (2C),
128.91, 131.24, 135.01 (2C), 137.13 (2C), 150.26,
162.25, 165.53, 167.07 ppm. Anal. Calcd. for C21H15
N3O4: C, 67.56; H, 4.05; N, 11.25%. Found: C, 67.61;
H, 3.97; N, 11.31%.
7-(1,3-Benzodioxol-5-yl)-10-thioxo-7,9,10,11-tetrahedro-6H-
pyrimido-[5′4′:5,6]
pyrano[3,2-c]quinoline-6,8(5H)-dione
(4k). Orange solid, yield: 83%: 0.348 gm, m.p. > 300°C
(decompose), IR (KBr), ν max: 3126, 2921, 1706, 1689,
1
1653; H NMR (300 MHz, DMSO-d6): δ, 5.77 (s, 1H,
7-(Furan-2-yl)-7,11-dihydro-6H-pyrimido-[5′4′:5,6] pyrano
Ar-H), 6.20 (s, 2H, ÀAr-H), 7.08–7.13 (m, 2H, Ar-H),
7.20 (s, 1H, Ar-H), 7.64–7.81 (m, 2H, Ar-H), 8.22 (s,
1H, Ar-H), 8.29 (s, 1H, Ar-H), 1130. (s, 1H, ÀNH),
12.31 (br.s, 1H, ÀNH), 12.40 (br.s, 1H, ÀNH) ppm. 13C
NMR (75 MHz, DMSO-d6): δ, 33.06, 98.51, 107.61,
108.19, 115.49, 115.67, 116.41, 121.63, 123.11 (2C),
127.36 (2C), 131.37, 134.86, 143.60, 147.87, 162.57,
163.07, 163.95, 173.75, 178.70 ppm. Anal. Calcd. for
C21H13 N3O5S: C, 60.14; H, 3.12; N, 10.02%. Found: C,
60.18; H, 3.17; N, 10.09%.
[3,2-c]quinoline-6,8,10(5H,9H)-trione (4o).
yield: 78%: 0.272 gm, m.p. 280–283°C, IR (KBr), ν
Gray solid,
max: 3613, 3321, 2851, 1762, 1745,1704,1647, 1564,
1
1540 cmÀ1; H NMR (300 MHz, DMSO-d6): δ, 5.75 (s,
1H, ÀCH), 6.85 (s, 1H, Ar-H), 7.10 (s, 1H, Ar-H), 7.42
(s, 1H, Ar-H), 7.75–7.77 (d, J = 6 Hz, 1H, Ar-H), 8.06–
8.08 (d, J = 6 Hz, 1H, Ar-H), 8.19 (s, 1H, Ar-H), 8.50 (s,
1H, Ar-H), 11.18 (br.s, 1H, ÀNH), 11.27 (br.s, 1H,
ÀNH), 11.36 (br.s, 1H, ÀNH) ppm. 13C NMR (75 MHz,
DMSO-d6): δ, 98.47, 112.73, 115.47, 115.56 (2C),
115.63, 123.04, 127.23, 138.05 (2C), 139.42, 150.58
(2C), 150.73, 151.39, 162.40, 163.13, 163.68 ppm. Anal.
Calcd. for C18H11 N3O5: C, 61.89; H, 3.17; N, 12.03%.
Found: C, 61.79; H, 3.32; N, 12.09%.
7-(4-Methyl-phenyl)-10-thioxo-7,9,10,11-tetrahedro-6H-
pyrimido-[5′4′:5,6]
pyrano[3,2-c]quinoline-6,8(5H)-dione
(4l). White solid, yield: 87%: 0.338 gm, m.p. > 300°C
(decompose), IR (KBr), ν max: 3069, 2902, 1637, 1604,
1574 cmÀ1; 1H NMR (300 MHz, DMSO-d6): 2.39 (s, 3H,
ÀCH3), 5.75 (s, 1H, ÀCH), 6.95–6.97 (d, J = 9.0 Hz, 1H,
Ar-H), 7.03–06 (d, J = 9.0 Hz, 1H, Ar-H), 7.25–7.33 (m,
2H, Ar-H), 7.77–7.97 (d, J = 9.0 Hz, 1H, Ar-H), 8.13–
8.16 (d, J = 9.0 Hz, 1H, Ar-H), 8.26 (s, 1H, Ar-H), 11.27
(br.s, 1H, ÀNH), 12.33 (br.s, 1H, ÀNH), 12.44 (br.s, 1H,
ÀNH) ppm. 13C NMR (75 MHz, DMSO-d6): δ, 25.89,
37.14, 95.43, 101.12, 119.45, 123.78, 125.09, 126.08,
127.32 (2C), 127.83, 130.94 (2C), 135.00 (2C), 137.17,
156.64, 161.00, 163.16, 165.86, 173.90. Anal. Calcd. for
C21H15 N3O5S: C, 64.77; H, 3.88; N, 10.79%. Found: C,
7-(3-Chloro-phenyl)-7,11-dihydro-6H-pyrimido-[5′4′:5,6]
pyrano[3,2-c]quinoline-6,8,10(5H,9H)-trione (4p).
White
solid, yield: 86%: 0.338 gm, m.p. > 300°C (decompose),
IR (KBr), ν max: 3221, 2909, 2767, 1713, 1634, 1610,
1
1568 cmÀ1; H NMR (300 MHz, DMSO-d6): δ, 5.97 (s,
1H, ÀCH), 7.07–7.10 (d, J = 9.0 Hz, 2H, Ar-H), 7.21–
7.29 (m, 2H, Ar-H), 7.44–7.47 (m, 1H, Ar-H), 7.57–7.59
(d, J = 6 Hz, 1H, Ar-H), 7.93 (s, 2H, Ar-H), 11.30 (br.s,
2H, ÀNH), 12.41 (s, 1H, ÀNH) ppm. 13C NMR (75 MHz,
DMSO-d6): δ, 36.32, 87.17, 92.05, 116.65, 123.57, 125.50
(2C), 126.11, 126.15, 127.81 (2C), 129.00, 129.42,
129.99, 131.54, 133.49, 137.23, 148.52, 150.24,
162.63 ppm. Anal. Calcd. for C20H12 ClN3O4: C, 61.00;
H, 3.07; N, 10.67%. Found: C, 61.07; H, 3.12; N, 10.69%.
7-(4-Chloro-phenyl)-7,11-dihydro-6H-pyrimido-[5′4′:5,6]
64.69; H, 3.81; N, 10.69%.
7-(Phenyl)-7,11-dihydro-6H-pyrimido-[5′4′:5,6] pyrano[3,2-
c]quinoline-6,8,10(5H,9H)-trione (4m). White solid, yield:
91%: 0.329 gm, m.p. 288–291°C, IR (KBr), ν max: 3573,
3306, 3062, 2880, 1714, 1629, 1592, 1519 cmÀ1 1H
;
pyrano[3,2-c]quinoline-6,8,10(5H,9H)-trione (4q).
White
NMR (300 MHz, DMSO-d6): δ, 5.76 (s, 1H, ÀCH), 7.11–
7.14 (d, J = 9.0 Hz, 3H, Ar-H), 7.25 (s, 1H, Ar-H), 42–
7.55 (m, 3H, Ar-H), 7.5–7.77 (d, J = 9.0 Hz, 1H, Ar-H),
7.93 (s, 1H, Ar-H), 11.17 (br.s, 1H, ÀNH), 11.28 (br.s,
1H, ÀNH), 12.35 (br.s, 1H, ÀNH) ppm. 13C NMR
(75 MHz, DMSO-d6): δ, 36.34, 98.53, 115.60 (2C),
121.32, 123.03 (2C), 123.49 (2C), 128.27 (2C), 130.92,
137.15, 139.45 (2C), 162.54, 163.10, 164.42 ppm. Anal.
Calcd. for C20H13 N3O4: C, 66.85; H, 3.65; N, 11.69%.
solid, yield: 88%: 0.346 gm, m.p. > 300°C (decompose),
IR (KBr), ν max: 3154, 2907, 1715, 1635, 1607, 1557,
1
1520 cmÀ1; H NMR (300 MHz, DMSO-d6): δ, 5.87 (s,
1H, ÀCH), 7.14 (s, 1H, Ar-H), 7.17 (t, 1H, Ar-H), 7.23–
7.25 (d, J = 6 Hz, 2H, Ar-H), 7.29–7.31 (t, 1H, Ar-H),
7.44–7.46 (d, J = 6.0 Hz, 2H, Ar-H), 7.55 (s, 1H, Ar-H),
11.31 (br.s, 2H, ÀNH), 12.38 (br.s, 1H, ÀNH) ppm. 13C
NMR (75 MHz, DMSO-d6): δ, 48.80, 81.08, 98.58,
115.59, 121.33, 123.03, 126.28 (2C), 128.03 (2C),
130.05, 130.96 (2C), 137.42, 139.49, 158.90, 163.02,
164.37, 168.11, 168.53 ppm. Anal. Calcd. for C20H12
ClN3O4: C, 61.00; H, 3.07; N, 10.67%. Found: C, 61.08;
H, 3.14; N, 10.71%.
Found: C, 66.83; H, 3.67; N, 11.71%.
7-(4-Methyl-phenyl)-7,11-dihydro-6H-pyrimido-[5′4′:5,6]
pyrano[3,2-c]quinoline-6,8,10(5H,9H)-trione (4n).
White
solid, yield: 85%: 0.317 gm, m.p. 278–280°C, IR (KBr),
1
ν max: 3192, 3074, 1713, 1636, 1607 cmÀ1; H NMR
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2017
Sulfamic Acid Catalyzed Synthesis of Novel Pyrano [3,2-c]quinoline Derivative
7-(3-Bromo-phenyl)-7,11-dihydro-6H-pyrimido-[5′4′:5,6]
137.24, 148.26, 150.08, 152.13, 157.82, 161.71, 164.16,
170.08 ppm. Anal. Calcd. for C20H12 N4O6: C, 59.41;
H, 2.99; N, 13.86%. Found: C, 59.54; H, 3.04; N,
13.92%.
pyrano[3,2-c]quinoline-6,8,10(5H,9H)-trione (4r).
White
solid, yield: 86%: 0.376 gm, m.p. 290–294°C, IR (KBr),
ν max: 3193, 3071, 2920, 1715, 1634, 1610 cmÀ1; H
1
NMR (300 MHz, DMSO-d6): δ, 5.88 (s, 1H, ÀCH),
7.13–7.28 (m, 2H, Ar-H), 7.43–7.45 (d, J = 6 Hz, 3H,
Ar-H), 7.52–7.54 (d, J = 6 Hz, 1H, Ar-H), 7.97 (s, 1H,
Ar-H), 8.07 (s, 1H, Ar-H), 11.20 (br.s, 1H, ÀNH), 11.32
(br.s, 1H, ÀNH), 12.38 (br.s, 1H, ÀNH) ppm. 13C NMR
(75 MHz, DMSO-d6): δ, 33.50, 116.63, 118.91, 120.22,
122.06, 123.19, 123.55, 124.73 (2C), 125.80, 129.03
(2C), 129.48, 130.18, 131.44, 137.18, 150.26, 157.27,
162.44, 162.53 ppm. Anal. Calcd. for C20H12 BrN3O4: C,
54.81; H, 2.76; N, 9.59%. Found: C, 54.69; H, 2.73; N,
9.52%.
7-(4-Cyno–pheny)l-7,11-dihydro-6H-pyrimido-[5′4′:5,6]
pyrano[3,2-c]quinoline-6,8,10(5H,9H)-trione (4v).
White
solid, yield: 87%: 0.334 gm, m.p. 288–290°C, IR (KBr),
ν max: 3072, 2900, 2572, 2234, 1733, 1634, 1604,
1
1559 cmÀ1; H NMR (300 MHz, DMSO-d6): δ, 5.79 (s,
1H, ÀCH), 7.26–7.34 (t, 3H, Ar-H), 7.46–7.48 (d,
J = 6.0 Hz, 2H, Ar-H), 7.62–7.31 (m, 2H, Ar-H), 8.00 (s,
1H, Ar-H), 10.43 (s, 1H, ÀNH), 11.26 (br.s, 1H, ÀNH),
12.47 (s, 1H, ÀNH) ppm. 13C NMR (75 MHz,
DMSO-d6): δ, 40.29, 87.86, 101.41, 108.53, 112.31,
120.37, 123.83, 126.76 (2C), 128.32, 130.37 (2C),
132.46 (2C), 138.85, 141.20, 147.86, 152.05, 158.40,
163.43, 170.02 ppm. Anal. Calcd. for C21H12 N4O4: C,
65.62; H, 3.15; N, 14.58. Found: C, 65.68; H, 3.19; N,
14.61%.
7-(4-Bromo-phenyl)-7,11-dihydro-6H-pyrimido-[5′4′:5,6]
pyrano[3,2-c]quinoline-6,8,10(5H,9H)-trione (4s).
White
solid, yield: 86%: 0.376 gm, m.p. > 300°C (decompose),
IR (KBr), ν max: 3573, 3306, 3062, 2880, 1714, 1629,
1
1592, 1519 cmÀ1; H NMR (300 MHz, DMSO-d6): δ,
7-(Pyridin-3-yl)-7,11-dihydro-6H-pyrimido-[5′4′:5,6] pyrano
[3,2-c]quinoline-6,8,10(5H,9H)-trione (4w).
White solid,
5.82 (s, 1H, ÀCH), 7.05–7.08 (d, J = 9.0 Hz, 2H, Ar-H),
7.26 (s, 1H, Ar-H), 7.34–7.37 (d, J = 9.0 Hz, 3H, Ar-H),
7.42–7.45 (d, J = 9.0 Hz, 1H, Ar-H), 7.51–7.54 (d,
J = 9.0 Hz, 1H, Ar-H), 11.19 (br.s, 1H, ÀNH), 11.30 (br.
s, 1H, ÀNH), 12.36 (br.s, 1H, ÀNH) ppm. 13C NMR
(75 MHz, DMSO-d6): δ, 33.01, 116.60, 119.31, 120.69,
123.12, 123.51, 126.48 (2C), 127.12, 128.96 (2C),
131.07, 131.37, 135.76, 137.17, 150.25, 158.62, 163.37,
164.13, 165.41 ppm. Anal. Calcd. for C20H12 BrN3O4: C,
54.81; H, 2.76; N, 9.59%. Found: C, 54.87; H, 2.79; N,
9.61%.
yield: 83%: 0.299 gm, m.p. 282–285°C, IR (KBr), ν
max: 3567, 3285, 3062, 2880, 2136, 1714, 1628,
1
1591,1519, 1501 cmÀ1; H NMR (300 MHz, DMSO-d6):
δ, 6.56 (s, 1H, ÀCH), 7.09–7.14 (t, 1H, Ar-H), 7.25–7.27
(d, J = 6 Hz, 1H, Ar-H), 7.43–7.48 (t, 1H, Ar-H), 7.57–
7.61 (t, 2H, Ar-H), 7.89–7.81 (t, 1H, Ar-H), 8.59–8.61
(d, J = 6 Hz, 2H, Ar-H), 9.92 (br.s, 1H, ÀNH), 10.29 (br.
s, 1H, ÀNH), 11.30 (br.s, 1H, ÀNH) ppm. 13C NMR
(75 MHz, DMSO-d6): δ, 43.07, 100.87, 103.76, 117.75,
122.68, 124.67 (2C), 125.04 (2C), 129.54, 131.46,
137.45, 140.00, 148.94 (2C), 156.63, 161.19, 165.07,
168.00 ppm. Anal. Calcd for C19H12 N4O4: C, 63.33; H,
3.36; N, 15.55%. Found: C, 63.32; H, 3.29; N, 15.48%.
7-(4-Nitro-phenyl)-7,11-dihydro-6H-pyrimido-[5′4′:5,6]
pyrano[3,2-c]quinoline-6,8,10(5H,9H)-trione (4t).
White
solid, yield: 84%: 0.331 gm, m.p. 280–282°C, IR (KBr),
1
ν max: 3196, 2906, 1719, 1637, 1573, 1353 cmÀ1; H
7-(3,4-Dimethoxy-phenyl)-7,11-dihydro-6H-pyrimido-[5′
4′:5,6] pyrano[3,2-c]quinoline-6,8,10(5H,9H)-trione (4x).
NMR (300 MHz, DMSO-d6): δ, 5.93 (s, 1H, ÀCH), 7.26
(s, 1H, Ar-H), 7.36–7.53 (m, 3H, Ar-H), 7.99 (s, 1H, Ar-
H), 8.05–8.08 (d, J = 9.0 Hz, 3HAr-H), 11.35 (br.s, 2H,
ÀNH), 12.40 (br.s, 1H, ÀNH) ppm. 13C NMR (75 MHz,
DMSO-d6): δ, 33.40, 98.61, 104.93, 116.68, 120.31,
123.38, 123.59, 126.27 (2C), 128.03, 131.55 (2C),
137.24, 143.39, 146.18, 150.28, 151.90, 160.62, 165.65,
171.72 ppm. Anal. Calcd. for C20H12 N4O6: C, 59.41; H,
2.99; N, 13.86%. Found: C, 59.45; H, 2.92; N, 13.84%.
7-(3-Nitro-phenyl)-7,11-dihydro-6H-pyrimido-[5′4′:5,6]
Yellow solid, yield: 80%: 0.335 gm, m.p. 284–287°C, IR
(KBr), ν max: 3213, 3069, 1737, 1693, 1647, 1591,1570,
1
1540 cmÀ1; H NMR (300 MHz, DMSO-d6): δ, 3.80 (s,
3H, ÀOCH3), 3.88 (s, 3H, ÀOCH3), 5.73(s, 1H, ÀCH),
7.10–7.16 (t, 2H, Ar-H), 7.46–7.51 (t, 1H, Ar-H), 7.75–
7.78 (d, J = 9.1 Hz, Ar-H), 7.89–7.91 (d, 1H, Ar-H), 8.25
(s, 1H, Ar-H), 8.41 (s, 1H, Ar-H), 11.21 (br.s, 2H,
ÀNH), 11.33 (br.s, 1H, ÀNH) ppm. 13C NMR (75 MHz,
DMSO-d6): δ, 45.00, 57.65, 58.00, 93.67, 101.74,
114.93, 115.00, 117.46, 121.08, 123.64, 125.89 (2C),
130.38, 132.49, 134.04, 142.37, 145.46, 149.29, 157.89,
160.69, 164.68, 168.94 ppm. Anal. Calcd. for C22H17
N3O6: C, 63.01; H, 4.09; N, 10.02%. Found: C, 63.08;
H, 3.99; N 10.00.
pyrano[3,2-c]quinoline-6,8,10(5H,9H)-trione (4u).
White
solid, yield: 82%: 0.339 gm, m.p. 284–287°C, IR (KBr),
1
ν max: 2947, 2776, 1712, 1635, 1523, 1339 cmÀ1; H
NMR (300 MHz, DMSO-d6): δ, 5.97 (s, 1H, ÀCH), 7.28
(s, 1H, Ar-H), 7.47–7.56 (m, 4H, Ar-H), 7.92 (s, 1H, Ar-
H), 8.01–8.03 (d, J = 6.0 Hz, 2H, Ar-H), 11.36 (s, 2H,
ÀNH), 12.45 (s, 1H, ÀNH) ppm. 13C NMR (75 MHz,
DMSO-d6): δ, 33.37, 95.47, 106.72, 116.57, 116.84,
121.27, 123.60, 123.79, 126.84 (2C), 131.65, 135.05,
Acknowledgments. One of the author thanks UGC-New Delhi
for the award of BSR faculty fellowship of Professor M. B.
Deshmukh, Department of Chemistry, Shivaji University,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

S. J. Jadhav, R. B. Patil, D. R. Kumbhar, A. A. Patravale, D. R. Chandam, and M. B. Deshmukh Vol 000
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet