J IRAN CHEM SOC
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The new derivatives were identified by their IR, H NMR,
13C NMR. The melting points were measured using capil-
lary tubes with the electrothermal 9200 apparatus. IR was
(4H, m, CH of Ar), 7.81–7.85 (1H, m, CH of Ar), 7.91(1H,
d, J = 8.0 Hz, CH of Ar), 7.91 (1H, d, J = 8.4 Hz, CH
of Ar), 8.07 (1H, d, J = 8.4 Hz, CH of Ar), 8.30 (1H, d,
J = 8.4 Hz, CH of Ar), 8.48 (2H, s, NH2) ppm, 13C NMR
(100 MHz, DMSO-d6): δ = 54.38 (Benzyl-CH), 108.36,
115.67, 118.93, 120.66, 121.32, 122.32, 123.01, 124.65,
125.14, 125.84, 126.65, 126.89, 127.41, 127.55, 127.61,
127.86, 127.21, 128.25, 128.46, 131.62, 133.29, 133.44,
135.71, 140.72, 143.66 (C-19), 146.61 (C-21), 149.66
(C-9), 160.88 (C-12) ppm.
recorded on FT-IR Bruker Tensor 27. H NMR, 13C NMR
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spectra were recorded on a Bruker AQS AVANCE 400
and 100 MHz spectrometers, respectively, using TMS as
an internal standard and DMSO-d6 as solvent. Thin-layer
chromatography (TLC, silica gel, 60 F254) was used to
monitor the progress of reactions.
General procedures
2‑Amino‑4‑(2‑chloro‑7‑methylquinolin‑3‑yl)‑4H‑benzo[h]
chromene‑3 carbonitrile (C24H16ClN3O) (6b): White pow-
der (85%); m.p.: 283–285 °C; FT-IR (KBr): νmax = 3411,
Preparation of 2-chloroquinoline-3-carbaldehyde derivatives
(1a/b) [57] POCl3 (5.8 ml, 60 mmol) was added dropwise to
a stirring solution of the N-phenylacetamide (5 mmol) in ice-
cooled DMF (1.15 ml, 15 mmol). The resulted mixture was
heated at 80–90 °C for 7 h. The solution was then cooled and
poured onto ice water (150 ml). The precipitated solid was
filtered off and washed with water to give the corresponding
chloroquinoline carbaldehydes.
Preparation of 2-amino-4-H-chromenes (3a–g, 4a–d):
a typical procedure: Benzaldehyde (1 mmol), malononi-
trile (1 mmol), α- or β-naphthol (1 mmol) and morpholine
(30 mol %) were mixed in water (5 ml). This mixture was
stirred under heating conditions. The progress of reaction
was monitored by TLC using as eluent. Upon completion
of the reaction observed by TLC (3:7 ethyl acetate/petro-
leum ether), the reaction mixture was cooled to room tem-
perature to precipitate. The precipitate solid was separated
by filtration, washed with petroleum ether and crystallized
from EtOH (Table 1). When 2-chloroquinoline-3-carbalde-
hydes were employed as aromatic aldehydes, the reaction
mixture was refluxed for 1 h.
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3315, 2188, 1653, 1625, 1569 cm−1, H NMR (400 MHz,
DMSO-d6): δ = 2.48 (3H, s, CH3), 5.54 (1H, s, Benzyl-
CH), 7.07 (1H, d, J = 8.4 Hz, CH of Ar), 7.33 (1H, s, CH
of Ar), 7.59–7.63 (4H), 7.820(1H, s, CH of Ar), 7.86 (1H, d,
J = 8.8 Hz, CH of Ar), 7.92 (1H, d, J = 8.0 Hz, CH of Ar),
8.29 (1H, d, J = 8.4 Hz, CH of Ar), 8.34 (2H, s, NH2) ppm,
13C NMR (100 MHz, DMSO-d6): δ = 21.58 (CH3), 54.60
(Benzyl-CH), 116.02, 120.65, 121.29 123.11, 124.57, 125.93,
127.13, 127.29, 127.49, 127.68, 128.23, 133.45, 133.54,
136.02, 137.80, 139.99, 143.72 (C-19), 145.30 (C-21), 148.75
(C-9), 160.89 (C-12) ppm.
3‑Amino‑1‑(2‑chloroquinolin‑3‑yl)‑1H‑benzo[f]chromene‑
2‑carbonitrile (C23H14ClN3O) (6c): White powder (84%),
m.p.: 300 °C, FT-IR (KBr): νmax = 3485, 3337, 2191, 1653,
1625, 1569 cm−1;1H NMR (400 MHz, DMSO-d6): δ = 5.89
(1H, s, CH- Benzyl), 7.21 (1H, s, CH of Ar), 7.40- 7.47 (3H,
m, CH of Ar), 7.55–7.59 (1H, m, CH of Ar), 7.66–7.68 (1H,
m, CH of Ar), 7.77–7.79 (1H, m, CH of Ar), 7.95–8.04 (4H,
m, CH of Ar), 8.23 (2H, s, NH2) ppm, 13C NMR (100 MHz,
DMSO-d6): δ = 55.97 (CH-Benzyl), 114.03, 117.48, 120.33,
123.18, 125.53, 127.81, 127.92, 128.01, 128.07, 128.40,
129.31, 130.43, 130.75, 131.34, 131.45, 139.52, 146.49
(C-19), 147.82 (C-21), 148.99 (C-9), 160.37 (C-12) ppm.
Selected spectroscopic data
2‑Amino‑4‑(naphthalen‑3‑yl)‑4H‑benzoh]chromene‑3‑car-
bonitrile (C24H16N2O) (3g): White powder (87%), m.p.:
147–150 °C; FT-IR (KBr): νmax = 3464, 3323, 2191, 1655,
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1598 cm−1, H NMR (400 MHz, CDCl3): δ = 4.8 (2H, s,
3‑Amino‑1‑(2‑chloro‑7‑methylquinolin‑3‑yl)‑1H‑benzo[f]
chromene‑2‑carbonitrile (C24H16ClN3O) (6d): White pow-
der (80%), m.p.: 300–302 °C, FT-IR (KBr): νmax = 3433,
NH2), 5.8 (1H, s, CH-Benzyl), 6.97 (1H, d, J = 8.4 Hz, CH
of Ar), 7.35–7.36 (1H, m, CH of Ar), 7.41–7.45 (2H, m,
CH of Ar), 7.49–7.53 (2H, m, CH of Ar), 7.60–7.64 (1H,
m, CH of Ar), 7.60–7.64 (1H, m, CH of Ar), 7.79 (2H, t,
J = 7.2 Hz, CH of Ar), 7.99–7.92 (1H, m, CH of Ar), 8.25
(1H, d, J = 8.4 Hz, CH of Ar), 8.29 (1H, s, CH of Ar) ppm.
3322, 2189, 1651, 1585 cm−1 1H NMR (400 MHz,
,
DMSO-d6): δ = 2.42 (3H, s, CH3), 5.78 (1H, s, Benzyl-
CH), 7.19 (1H, s, CH of Ar), 7.39–7.48 (3H, m, CH of Ar),
7.61–7.72 (3H, m, CH of Ar), 7.82 (1H, d, J = 8.8 Hz, CH
of Ar), 7.95 (1H, d, J = 8.4 Hz, CH of Ar), 8.02 (1H, d,
J = 9.2 Hz, CH of Ar), 8.11 (2H, s, NH2) ppm, 13C NMR
(100 MHz, DMSO-d6): δ = 21.49 (CH3), 55.93 (Benzyl-
CH), 114.09, 117.44, 120.33, 123.21, 125.51, 127.05,
127.62, 127.77, 128.02, 129.28, 130.44, 130.70, 131.34,
133.52, 137.73, 138.79, 145.10 (C-19), 147.81 (C-21),
148.04 (C-9), 160.39 (C-12) ppm.
2‑Amino‑4‑(2‑chloroquinolin‑3‑yl)‑4Hbenzo[h]chromene‑
3‑carbonitrile (C23H14ClN3O) (6a): White powder
(88%); m.p.: 280–283 °C, FT-IR (KBr): νmax = 3410,
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3315, 2188, 1653, 1625, 1569 cm−1, H NMR (400 MHz,
DMSO-d6): δ = 5.58 (1H, s, Benzyl-CH), 7.08 (1H, d,
J = 8.4 Hz, CH of Ar), 7.36 (1H, s, CH of Ar), 7.60–7.70
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