Convenient Synthesis of New Boric Acid Catalyzed 1,2,4-Triazolopyridinone Derivatives and an Investigation of their Optical Properties

Article abstract of DOI:10.1002/jhet.3501

Syntheses of fused heterobicyclic systems containing 1,2,4-triazolopyridinone moieties were accomplished by heterocyclization of 1,6-diamino-2-oxo-4-phenyl-1,2-dihydropyridine-3,5-dicarbonitriles and ninhydrin in ethanol and in the presence of boric acid as a catalyst in 30?min at room temperature. All compounds have been screened for their photophysical properties. Results showed that all compounds exhibit near infrared emissions at 876?nm.

Full text of DOI:10.1002/jhet.3501

Month 2019
Convenient Synthesis of New Boric Acid Catalyzed 1,2,4-
Triazolopyridinone Derivatives and an Investigation of their Optical
Properties
*
Ali Darehkordi,
Maryam Hosseini, and Fariba Rahmani
Department of Chemistry, Faculty of Science, Vali-e-Asr University of Rafsanjan, Rafsanjan 77176, Iran
*E-mail: adarehkordi@yahoo.com; darehkordi@vru.ac.ir
Received August 12, 2018
DOI 10.1002/jhet.3501
Published online 00 Month 2019 in Wiley Online Library (wileyonlinelibrary.com).
Syntheses of fused heterobicyclic systems containing 1,2,4-triazolopyridinone moieties were accom-
plished by heterocyclization of 1,6-diamino-2-oxo-4-phenyl-1,2-dihydropyridine-3,5-dicarbonitriles and
ninhydrin in ethanol and in the presence of boric acid as a catalyst in 30 min at room temperature. All com-
pounds have been screened for their photophysical properties. Results showed that all compounds exhibit
near infrared emissions at 876 nm.
J. Heterocyclic Chem., 00, 00 (2019).
INTRODUCTION
are readily available and have been successfully used in
different spectral region. Nearly 50% of solar energy falls
in the NIR spectral region, which calls for NIR
photovoltaic materials in solar energy conversion [19].
The chromogenic properties of NIR organic materials
[20] are expected to receive growing attention for some
unique applications, such as NIR variable optical
attenuators based on NIR electrochromic organic
materials [21], NIR chiral materials for optical switching
[22], NIR chemochromic organic materials for chemical
sensing [23], and NIR liquid crystalline materials for
liquid crystal devices [24]. NIR absorbing pigments are
used in laser printers and digital copy machines as the
charge-generation material [25] and in optical disks
(e.g., CD-R) as the information-storage material [26].
Significant advances in the research and development of
NIR organic materials for these existing and emerging
applications are certainly expected in the near future. So
it was thought worthwhile to incorporate 1,2,4-triazine
into the pyridinone ring using 1,6-diaminopyridinone
derivatives as starting materials for the building of newly
fused heterobicyclic systems.
1,2,4-Triazine derivatives are important classes of
heterocyclic compounds which have various biological
properties such as anticancer, muscle relaxant, hypnotic,
anti-inflammatory, diuretic, and antihypertensive activities
[1–4]. In particular, literature studies on 1,2,4-triazoles
have shown that the fused 1,2,4-triazoles have a great
potential as antifungal [5], antibactericidal [5,6],
anxiolytic [7,8], anticonvulsant [9], or herbicidal [10]
activities and can act as “antidepressant” reagents [11].
The most widely applicable routes to the synthesis of
fused 1,2,4-triazoles mainly involve hydrazones as
precursors. However, this method has some limitations
on their use, such as toxic reagents like lead tetraacetate
[12,13] and bromine [13,14]. Also, the products were
isolated in low yield and isolated as salts [15,16].
Recently, fused heterobicyclic systems containing the
1,2,4-triazinopyridinone moiety have been prepared by the
heterocyclization of N-amino-2-pyridones with different
reagents [17]. Meanwhile, reactions of some active
carbonyl compounds with 4-aryl-1,6-diamino-2-oxo-1,2-
dihydro-pyridine-3,5-dicarbonitrile
derivatives
have
been documented in recent years [18]. Therefore, the
development of efficient, clean, and environmentally
friendly approaches using new catalysts for the synthesis
of 1,6-diamino-2-oxo-4-phenyl-1,2-dihydropyridine-3,5-
dicarbonitrile derivatives is an important task for organic
chemists.
RESULTS AND DISCUSSION
The starting material 4-(aryl)-1,6-diamino-2-oxo-1,2-
dihydropyridine-3,5-dicarbonitrile derivatives were obtained
[27] from cyclocondensation of cyanoacetohydrazide
with p-benzilidenemalononitriles under refluxing in
absolute ethanol in the presence of piperidine. These 1,2-
Small molecules with the absorption and fluorescence in
the near infrared (NIR) spectral region (e.g., 800–1500 nm)
© 2019 Wiley Periodicals, Inc.

A. Darehkordi, M. Hosseini, and F. Rahmani
Vol 000
biamino compounds are more favored to the ring
closure reactions.
carbon. Also, two signals at δ = 91.81 ppm and
δ = 99.64 ppm correspond to CN groups.
Dihydroindeno[1,2-e]pyrido[1,2-b][1,2,4]triazine-1,3-
dicarbonitrile derivatives (3a–k) were easily prepared from
the readily available 1,6-diamino-2-oxo-4-phenyl-1,2-
dihydropyridine-3,5-dicarbonitrile derivatives by reaction
with ninhydrin in the presence of boric acid as a catalyst
and acetic acid as a solvent (Scheme 1, Table 1).
Structure assignments of new products have been
established on the basis of elemental analysis and spectral
data. For example, the IR spectrum of compound 3b
showed absorption bands at 1689 and 1740 cmÀ1
assigned to C=O groups and bands at 2216 cmÀ1
assigned to CN groups. The 1H-NMR spectrum of 3b
showed a singlet signal for the methyl protons at
δ = 2.47 ppm. In addition, doublets at δ = 7.50 ppm and
δ = 7.62 ppm and multiples at δ = 8.09–8.16 ppm and
δ = 8.20–8.24 ppm and δ = 8.35–8.39 ppm correspond to
nine protons present in the molecule. The 13C-NMR
The pathway to the products can be explained by firstly
the activation of ninhydrin and then the formation of
intermediate A. Formation of target compounds occur via
a
nucleophilic addition–elimination reaction of the
6-position -NH2 group. It is plausible that the amino
group in the 6-position is more reactive than that attached
to the ring nitrogen in the 1-position. Attack of the
primary 6-position amino group on the hydrate form of
the central carbon of the ninhydrin molecule can account
for the formation of intermediate A, and this is followed
by nucleophilic attack of the second -NH2 present in the
system on the carbonyl group to yield the final products
(Scheme 2).
The photophysical properties of compounds 3a–k
were studied by ultraviolet–visible and fluorescence
spectroscopies. Absorption and emission spectra of
3 × 10À6 M solutions (solvent: dimethylformamide) of
compounds are shown in Figures 1 and 2 , respectively.
The absorption behaviors of all the samples were quite
similar to each other meaning that the optical band gap
spectrum of 3b displayed
a downfield signal at
δ = 172.53 ppm and δ = 183.68 ppm for the two
carbonyl groups and at δ = 21.58 ppm for the methyl
Scheme 1. Synthesis of dihydroindeno[1,2-e]pyrido[1,2-b][1,2,4]triazine-1,3-dicarbonitrile derivatives.
Table 1
Synthesis of dihydroindeno[1,2-e]pyrido[1,2-b][1,2,4]triazine-1,3-dicarbonitrile derivatives (3a–k).
Entry
Products
R
Melting point
1
2
3
4
5
6
7
8
3a
3b
3c
3d
3e
3f
3g
3h
3i
H
4-Me
4-OMe
4-Cl
3-NO2
4-N (Me)2
4-F
2-Cl
4-Br
3-Cl
324–327
325–328
326–330
326–329
310–314
330–334
319–322
327–330
320–324
320–324
324–329
9
10
11
3j
3k
2,4-dimethyl
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2019
Synthesis of New 1,2,4-Triazolopyridinone Derivatives
Scheme 2. A possible mechanism for the synthesis of dihydroindeno[1,2-e]pyrido[1,2-b][1,2,4]triazine-1,3-dicarbonitrile derivatives.
Figure 2. Fluorescence emission spectra of the synthesized compounds
(3a–k). [Color figure can be viewed at wileyonlinelibrary.com]
Figure 1. Absorption spectra of the synthesized compounds (1–11).
[Color figure can be viewed at wileyonlinelibrary.com]
EXPERIMENTAL
of the molecules originates from a unit structure. Also,
emission maxima and molar extinction coefficient are
reported (Table 2). According to Table 2, the maximum
absorption of all the 3a–k compounds was located at
350–353 nm. The emission spectra of all the 3a–k
compounds were very similar, with their emission
General information. All chemicals and solvents were
purchased from commercial sources and used without
further purification unless otherwise stated. Melting
points were determined on a Melt-Tem II melting point
apparatus and are uncorrected. IR spectra were obtained
on a Matson-1000 FTIR spectrometer. Peaks are reported
in wave numbers (cmÀ1) All of the NMR spectra were
recorded on a Bruker model DRX-400 AVANCE (4H:
300, 13C: 100 MHz) and on a Varian model (1H: 500,
13C: 125 MHz) NMR spectrometer. Chemical shifts of
1H and 13C-NMR are reported in parts per million (ppm)
from tetramethylsilane as an internal standard in
DMSO-d6 as a solvent and. Ultraviolet–visible and
fluorescence (PL) spectra were measured using a Perkin
Elmer and Avantes spectrometer (AvaSpec-2048 TEC),
respectively.
maxima within
(Figure 2).
a narrow range around 876 nm
In conclusion, an efficient, general, and simple
methodology for the synthesis of dihydroindeno[1,2-e]
pyrido[1,2-b][1,2,4]triazine-1,3-dicarbonitrile derivatives
from
1,6-diamino-2-oxo-4-phenyl-1,2-dihydropyridine-
3,5-dicarbonitrile and ninhydrin in the presence of boric
acid is reported. In this way, the procedure offers several
advantages including cleaner reaction profiles, excellent
yields, shorter reaction time, and higher purity products.
Also, according to their emission spectra, they exhibit
NIR emissions at 876 nm.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

A. Darehkordi, M. Hosseini, and F. Rahmani
Vol 000
1
Table 2
(C-O), 1462 (C=C), 1689, 1741 (C=O), 2217(CN). H-
NMR (500 MHz, DMSO-d6) δ = 3.88 (S, 3H, OMe),
7.22 (d, 2H, J = 10 Hz), 7.68 (d, 2H, J = 10 Hz),
8.07–8.12 (m, 2H, HAr), 8.17–8.20 (m, 1H, HAr), 8.33–
8.35 (m, 1H, HAr) ppm. 13C-NMR (125 MHz,
DMSO-d6) δ = 55.97 (O-CH3), 91.78, 99.34 (CN),
114.65, 114.77, 115.60, 125.55, 125.64, 125.89, 130.96,
137.22, 138.01, 138.51, 140.97, 148.18, 151.20 (Ar),
156.22, 160.37 (C=N), 162.02, 183.64 (C=O) ppm.
Elemental analysis: Value calculated for C23H11N5O3:
C, 68.15; H, 2.74; N, 17.28%, Value found: C, 68.07;
Ultraviolet–visible absorption data compounds 3a–k.
λmax
(nm)
λmax
(nm)
Compound
εmax
Compound
εmax
3a
3b
3c
3d
3e
3f
350
350
351
351
351
353
33441
40573
39959
19425
28315
60619
3g
3h
3j
3i
3k
351
350
351
351
351
23048
22409
21930
21698
25249
H, 2.71; N, 17.19%.
General procedure for the synthesis of compounds 3a–k.
In a typical experimental procedure, 50 mL of round
bottomed flask was charged with 15 mL of acetic
acid, 0.2 mmol of boric acid, 2 mmol of ninhydrin,
2-(4-Chlorophenyl)-4,7-dioxo-4,7-dihydroindeno[1,2-e]
pyrido[1,2-b][1,2,4]triazine-1,3-dicarbonitrile (3d). Prepared
according to the general procedure, Orange solid, M.
P = 326–329°C, Yield = 87%, IR (KBr, cmÀ1): 1478
(C=C), 1592, 1642 (C=N), 1711, 1733 (C=O), 2220
and
2
mmol of 1,6-diamino-2-oxo-4-phenyl-1,2-
derivatives. The
dihydropyridine-3,5-dicarbonitrile
1
(CN). H-NMR (500 MHz, DMSO-d6) δ = 7.72–7.77 (m,
mixture was stirred at room temperature for 30 min. After
completing the reaction (30 min, indicated by thin-layer
chromatography), the solid formed was filtered and
washed with water to obtain pure product.
4,7-Dioxo-2-phenyl-4,7-dihydroindeno[1,2-e]pyrido[1,2-b]
4H, HAr), 8.09–8.12 (m, 2H, HAr), 8.17–8.20 (m, 1H,
HAr), 8.35 (S, 1H, HAr) ppm. 13C-NMR (125 MHz,
DMSO-d6) δ = 91.65, 99.90 (CN), 114.31, 115.15,
125.65, 125.96, 129.57, 130.81, 132.58, 136.60, 137.19,
138.11, 138.50, 141.03 (Ar), 156.02, 159.59 (C=N),
160.56, 183.54 (C=O) ppm. Elemental analysis: Value
calculated for C22H8ClN5O2: C, 64.48; H, 1.97; N,
[1,2,4]triazine-1,3-dicarbonitrile (3a).
Prepared according
to the general procedure, Orange solid, M. P = 324–
327°C, Yield = 88%, IR (KBr, cmÀ1):1467 (C=C),
1700, 1735. (C=O), 2222 (CN). 1H-NMR (400 MHz,
DMSO-d6) δ = 7.68–7.75 (m, 5H, HAr), 8.10–8.16 (m,
2H, HAr), 8.21–8.24 (m, 1H. HAr), 8.36–8.40 (m, 1H,
HAr) ppm. 13C-NMR (100 MHz, DMSO-d6) δ = 91.80,
99.83 (CN), 114.90, 115.37, 124.89, 125.71,
125.99, 128.67, 129.42, 131.67, 137.22, 137.78, 138.13,
138.96, 141.04, 148.40, 151.30 (Ar), 156.22,
160.52 (C=N), 160.76, 183.67 (C=O) ppm. Elemental
analysis: Value calculated for C22H9N5O2: C, 70.40; H,
2.42; N, 18.66%, Value found: C, 70.33; H, 2.39; N,
17.09%, Value found: C, 64.39; H, 1.93; N, 17.16%.
2-(3-Nitrophenyl)-4,7-dioxo-4,7-dihydroindeno[1,2-e]
pyrido[1,2-b][1,2,4]triazine-1,3-dicarbonitrile (3e). Prepared
according to the general procedure, Orange solid, M.
P = 310–314°C, Yield = 93%, IR (KBr, cmÀ1): 1352,
1467 (C-NO2), 1700, 1735 (C=O), 2219 (C=N). 1H-
NMR (500 MHz, DMSO-d6) δ = 7.98–8.02 (m, 1H,
HAr), 8.10–8.13 (m, 2H, HAr), 8.17–8.21 (m, 2H, HAr),
8.37 (S, 1H, HAr), 8.51–8.54 (m, 1H, HAr), 8.64 (d.d, 1H,
J = 2.5, 2.5 HZ) ppm. 13C-NMR (125 MHz, DMSO-d6)
δ = 91.72, 100.34 (CN), 109.99, 114.23, 115.00, 123.93,
125.66, 126.01, 126.27, 131.43, 135.21, 135.43, 138.18,
138.50, 141.07, 148.17 (Ar), 151.26, 155.91 (C=N),
158.39, 183.50 (C=O) ppm. Elemental analysis: Value
calculated for C22H8N6O4: C, 62.86; H, 1.92; N, 19.99%,
18.61%.
4,7-Dioxo-2-(p-tolyl)-4,7-dihydroindeno[1,2-e]pyrido[1,2-b]
[1,2,4]triazine-1,3-dicarbonitrile (3b).
Prepared according
to the general procedure, Orange solid, M. P = 325–
328°C, Yield = 86%, IR (KBr, cmÀ1):1465 (C=C), 1689,
1740 (C=O), 2216 (CN). 1H-NMR (400 MHz,
DMSO-d6) δ = 2.47 (S, 3H, Me), 7.50 (d, 2H, J = 8 Hz),
7.62 (d, 2H, J = 8 Hz), 8.09–8.16 (m, 2H, HAr), 8.20–
8.24 (m, 1H, HAr), 8.35–8.39 (m, 1H, HAr) ppm. 13C-
NMR (100 MHz, DMSO-d6) δ = 2158 (CH3), 91.81,
99.64 (CN), 114.60, 115.59, 125.71, 125.96, 128.93,
129.96, 130.85, 137.22, 138.10, 138.56, 141.02, 141.83,
148.32, 151.28, 156.25, 160.46, 160.81 (C=N), 172.53,
183.68 (C=O) ppm. Elemental analysis: Value calculated
for C23H11N5O2: C, 70.95; H, 2.85; N, 17.99%, Value
Value found: C, 62.79; H, 1.89; N, 19.91%.
2-(4-(Dimethylamino)phenyl)-4,7-dioxo-4,7-
dihydroindeno[1,2-e]pyrido[1,2-b][1,2,4]triazine-1,3-
dicarbonitrile (3f).
Prepared according to the general
procedure, Orange solid, M.
P
=
330–334°C,
Yield = 85%, IR (KBr, cmÀ1): 1151, 1381 (N-CH3),
1
1525, 1603 (C=N), 1698, 1733 (C=O), 2210 (CN). H-
NMR (500 MHz, DMSO-d6) δ = 3.06 (S, 6H, N-
CH3), 6.09 (d, 2H, J = 10 Hz), 7.60(d, 2H, J = 5 Hz),
8.06–8.12 (m, 2H, HAr), 8.17–8.19 (m, 1H, HAr), 8.32–
8.34 (m, 1H, HAr) ppm. 13C-NMR (125 MHz,
DMSO-d6) δ = 91.41, 97.61 (CN), 111.03, 115.03,
116.25, 119.23, 125.60, 125.79, 130.93, 137.23, 137.83,
138.49, 140.90, 147.73 (Ar), 151.23, 152.67 (CN),
156.44, 160.14 (N-CH3), 160.26, 183.73 (C=O) ppm.
found: C, 70.78; H, 2.80; N, 17.89%.
2-(4-Methoxyphenyl)-4,7-dioxo-4,7-dihydroindeno[1,2-e]
pyrido[1,2-b][1,2,4]triazine-1,3-dicarbonitrile (3c). Prepared
according to the general procedure, Orange solid, M.
P = 326–330°C, Yield = 90%, IR (KBr, cmÀ1): 1157
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2019
Synthesis of New 1,2,4-Triazolopyridinone Derivatives
Elemental analysis: Value calculated for C24H14N6O2: C,
68.89; H, 3.37; N, 20.09%, Value found: C, 68.79; H,
3.32; N, 19.97%.
2-(4-Fluorophenyl)-4,7-dioxo-4,7-dihydroindeno[1,2-e]
pyrido[1,2-b][1,2,4]triazine-1,3-dicarbonitrile (3g). Prepared
(125 MHz, DMSO-d6) δ = 91.66, 100.04 (CN), 114.25,
115.06, 125.67, 126.00, 127.61, 128.53, 131.47, 133.93,
135.70, 137.20, 138.14, 138.52, 141.04, 148.58, 151.20
(Ar), 155.98, 159.10 (C=N), 160.64, 183.55 (C=O) ppm.
Elemental analysis: Value calculated for C22H8ClN5O2:
C, 64.48; H, 1.97; N, 17.09%, Value found: C, 64.43; H,
according to the general procedure, Orange solid, M.
P = 319–323°C, Yield = 76%, IR (KBr, cmÀ1): 1238 (C-
F), 1466 (C=C), 1560, 1605 (C=N), 1695, 1739 (C=O),
1.95; N, 17.01%.
2-(2,4-Dimethoxyphenyl)-4,7-dioxo-4,7-dihydroindeno[1,2-
1
2218 (CN). H-NMR (500 MHz, DMSO-d6) δ = 7.50–
e]pyrido[1,2-b][1,2,4]triazine-1,3-dicarbonitrile
(3k).
7.54 (m, 2H, HAr), 7.76–7.80 (m, 2H, HAr), 8.08–8.13
(m, 2H, HAr), 8.17–8.20 (m, 1H, HAr), 8.33–8.36 (m, 1H,
HAr) ppm. 13C-NMR (125 MHz, DMSO-d6) δ = 91.82,
99.98 (CN), 114.39, 115.25, 116.51, 116.69, 125.65,
125.95, 130.15, 1313.58, 131.65, 137.20, 138.09, 138.51,
141.02, 148.41, 151.19 (Ar), 156.06, 159.78 (C=N),
160.53, 183.58 (C=O) ppm. Elemental analysis: Value
calculated for C22H8FN5O2: C, 67.18; H, 2.05; N,
Prepared according to the general procedure, Orange
solid, M. P = 324–329°C, Yield = 77%, IR (KBr, cmÀ1):
1211, 1233 (O-CH3), 1469 (C=C), 1554, 1609 (C=N),
1686, 1749 (C=O), 2219 (CN). 1H-NMR (500 MHz,
DMSO-d6) δ = 3.87 (S, 3H, OMe), 3.89 (S, 3H, OMe),
6.78 (d. d, 1H, J = 5, 2.5 Hz), 6.83 (d, 1H, J = 2.5 Hz),
7.45 (d, 1H, J = 8.5 Hz), 8.07–8.12 (m, 2H, HAr), 8.17–
8.19 (m, 1H, HAr), 8.32–8.34 (m, 1H, HAr) ppm. 13C-NMR
(125 MHz, DMSO-d6) δ = 56.07, 56.35 (OCH3), 92.99,
99.54 (CN), 100.62, 106.51, 109.99, 114.47, 114.86,
115.31, 125.65, 125.86, 131.46, 137.26, 137.96, 138.59,
140.84, 148.01, 150.79, 156.12, 157.83 (Ar), 158.71,
160.14 (C=N), 163.74, 183.72 (C=O) ppm. Elemental
analysis: Value calculated for C24H13N5O4: C, 66.21; H,
3.01; N, 16.09%, Value found: C, 66.25; H, 2.97; N, 16.15%.
17.81%, Value found: C, 67.12; H, 1.98; N, 17.87%.
2-(2-Chlorophenyl)-4,7-dioxo-4,7-dihydroindeno[1,2-e]
pyrido[1,2-b][1,2,4]triazine-1,3-dicarbonitrile (3h). Prepared
according to the general procedure, Orange solid, M.
P = 327–330°C, Yield = 69%, IR (KBr, cmÀ1): 668 (C-
Cl), 1694, 1731 (C=O), 2232, 2353 (CN). 1H-NMR
(500 MHz, DMSO-d6) δ = 7.63–7.71 (m, 3H, HAr), 7.78–
7.80 (m, 1H, HAr), 8.09–8.13 (m, 2H, HAr), 8.19–8.22
(m, 1H, HAr), 8.35–8.37 (m, 1H, HAr) ppm. 13C-NMR
(125 MHz, DMSO-d6) δ = 91.99, 109.98 (CN), 113.76,
125.74, 128.60, 130.40, 130.53, 131.04, 132.89, 133.11,
137.14, 138.64 (Ar), 140.98, 151.38 (C=N), 183.53,
220.11 (C=O) ppm. Elemental analysis: Value calculated
for C22H8ClN5O2: C, 64.48; H, 1.97; N, 17.09%, Value
Acknowledgment. We gratefully acknowledge the Vail-e-Asr
University of Rafsanjan Faculty Research grant for financial
support.
found: C, 64.35; H, 1.93; N, 17.15%.
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according to the general procedure, Orange solid, M.
P = 320–334°C, Yield = 73%, IR (KBr, cmÀ1): 1478
1
(C=C), 1711, 1732 (C=O), 2219, 2237 (CN). H-NMR
(500 MHz, DMSO-d6) δ = 7.67 (d, 2H, J = 5 HZ), 7.9
(d, 2H, J = 10), 8.08–8.13 (m, 2H, HAr), 8.18–8.21 (m,
1H, HAr), 8.34–8.37 (m, 1H, HAr) ppm. 13C-NMR
(125 MHz, DMSO-d6) δ = 91.58, 99.81 (CN), 114.34,
115.18, 125.44, 125.66, 125.98, 130.95, 132.51, 132.96,
137.19, 138.12, 138.51, 141.04, 148.56, 151.26 (Ar),
156.03, 159.63 (C=N), 160.58, 183.56 (C=O) ppm.
Elemental analysis: Value calculated for C22H8BrN5O2:
C, 58.17; H, 1.78; N, 15.42%, Value found: C, 58.05; H,
1.69; N, 15.44%.
2-(3-Chlorophenyl)-4,7-dioxo-4,7-dihydroindeno[1,2-e]
pyrido[1,2-b][1,2,4]triazine-1,3-dicarbonitrile (3i). Prepared
according to the general procedure, Orange solid, M.
P = 320–324°C, Yield = 80%, IR (KBr, cmÀ1): 1467
(C=C), 1697, 1741 (C=O), 2218 (CN). 1H-NMR
(500 MHz, DMSO-d6) δ = 7.66–7.77 (m, 3H, HAr), 7.82–
7.83 (m, 1H, HAr), 8.03–8.13 (m, 2H, HAr), 8.18–8.22
(m, 1H, HAr), 8.35–8.38 (m, 1H, HAr) ppm. 13C-NMR
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