Vol. 31, No. 7 (2019)
Synthesis of Substituted Coumarin Derivatives 1463
residue with cooled ice water to gives 4-(4-((3-nitro-2-oxo-
(singlet, 2H, -CO-CH -), 6.9 to 7.6 δ ppm (7H aromatic region),
2
-1
2
H-chromen-4-yl)amino)phenyl)morpholine-3-one in good
11.2 δ ppm (singlet, 1H, -NH-), IR (KBr, νmax, cm ): 3271,
3258, 2866, 2282, 1692, 1654, 1545, 1538, 1439, 1315, 1309,
1218, 1139, 1040, 878, 851, 768, 655. Mass spectra m/z: 399.09
yield (Scheme-I). Purification was done by treating solid mass
with dilute hydrochloric acid [20].
(
3
100.0 %), 400.09 (20.9 %), 401.09 (3.5 %), 400.08 (1.1 %),
63. 336. 318. 290. 277. 262. 248. 235. 221. 207, C NMR
Spectral data
13
4
-(4-((3-Nitro-2-oxo-2H-chromen-4-yl)amino)phenyl)-
morpholine-3-one (YS-01): Yield: 70 %; m.p.: 216-218 °C;
, m.w.: 381.34,Appearance: Colourless white,
(100 MHz, chloroform-d) δ: 123.30, 121.53, 120.14, 119.94,
117.45, 117.37, 112.42, 112.22, Elemental analysis (%): C,
57.15; H, 3.53; F, 4.76; N, 10.52; Found (%): C, 57.10; H,
3.50; F, 4.70; N, 10.20.
4-(4-((6-Bromo-3-nitro-2-oxo-2H-chromen-4-yl)-
amino)phenyl)morpholine-3-one (YS-05): Yield: 78 %; m.p.:
m.f.: C19
H N O
15 3 6
1
R
f
value-0.41 (8:2 ethyl acetate:hexane), H NMR spectra in δ
ppm: 3.80 to 3.88 δ ppm (triplet, 2H, -CH -O-), 4.03 to 4.11 δ
ppm (triplet, 2H, -N-CH -), 4.37 δ ppm (singlet, 2H, -CO-CH -),
2
2
2
7
1
1
8
3
.0 to 7.6 δ ppm (8 H aromatic region), 11.2 δ ppm (singlet,
244-246 °C; m.f.: C19
Colourless white, R value-0.40 (8:2 ethyl acetate:hexane), H
NMR spectra in δ ppm: 3.80 to 3.92 δ ppm (triplet, 2H, -CH
O-), 4.03 to 4.17 δ ppm (triplet, 2H, -N-CH -), 4.31 δ ppm
(singlet, 2H, -CO-CH -), 6.7 to 7.4 δ ppm (7H aromatic region),
H
14
N
3
O Br, m.w.: 460.23, Appearance:
6
-1
1
H, -NH-), IR (KBr, νmax, cm ): 3279, 3076, 2864, 1712, 1650,
f
612, 1551, 1513, 1452, 1350, 1307, 1211, 1120, 1061, 996,
2
-
+
53, 753, 692, 626. Mass spectra m/z: 381 (M ), 363, 336,
18, 290, 277, 262, 248, 235, 221, 207, C NMR (100 MHz,
chloroform-d) δ: 132.17, 125.77, 123.30, 122.93, 121.53, 116.19.
Elemental analysis (%): C, 59.84; H, 3.96; N, 11.02; Found
2
13
2
-1
11.2 δ ppm (singlet, 1H, -NH-). IR (KBr, νmax, cm ): 3371,
3358, 2966, 2282, 1692, 1654, 1546, 1510, 1439, 1325, 1310,
1218, 1129, 1062, 870, 851, 761, 655. Mass spectra m/z: 459.01
(100.0 %), 461.00 (97.3 %), 460.01 (20.9 %), 462.01 (20.7
%), 461.01 (3.5 %), 463.01 (3.2 %), 460.00 (1.1 %), 462.00
(
%): C, 59.12; H, 3.92; N, 11.09.
-(4-((8-Chloro-3-nitro-2-oxo-2H-chromen-4-yl)-
amino)phenyl)morpholine-3-one (YS-02): Yield: 60 %; m.p.:
02-204 °C; m.f.: C19 Cl, m.w.: 415.78, Appearance:
Colourless white, R value-0.42 (8:2 ethyl acetate:hexane), H
NMR spectra in δ ppm: 3.79 to 3.89 δ ppm (triplet, 2H, -CH
O-), 4.01 to 4.11 δ ppm (triplet, 2H, -N-CH -), 4.38 δ ppm
singlet, 2H, -CO-CH -), 6.9 to 7.4 δ ppm (7H aromatic region),
4
13
2
H
14
N O
3 6
(1.1 %), 363, 336, 318, 290, 277, 262, 248, 235, 221, 207, C
NMR (100 MHz, chloroform-d) δ: 135.16, 128.23, 123.30,
121.53, 117.49. Elemental analysis (%): C, 49.58; H, 3.07; Br,
17.36; N, 9.13; Found (%): C, 49.34; H, 3.01; Br, 17.10; N, 8.18.
4-(4-((6,8-Dimethyl-3-nitro-2-oxo-2H-chromen-4-yl)-
amino)phenyl)morpholine-3-one (YS-06): Yield: 70 %; m.p.:
1
f
2
-
2
(
2
-1
1
3
1
4
1.1 δ ppm (singlet, 1H, -NH-). IR (KBr, νmax, cm ): 3281,
077, 2865, 1710, 1651, 1615, 1561, 1514, 1438, 1351, 1307,
212, 1121, 1059, 998, 851, 752, 692, 625. Mass spectra m/z:
15 (M ) (100.0 %), 417.05 (32.0 %), 416.06 (20.9 %), 418.06
7.0 %), 417.06 (3.5 %), 416.05 (1.1 %), 419.06 (1.1 %), 363,
36, 318, 290, 277, 262, 248, 235, 221, 207, C NMR (100
MHz, chloroform-d) δ: 133.07, 124.83, 123.91, 123.30, 121.53.
Elemental analysis (%): C, 54.89; H, 3.39; Cl, 8.53; N, 10.11;
Found (%): C, 49.27; H, 3.40; Cl, 8.50; N, 9.11.
216-218 °C; m.f.: C21
white, R value-0.40 (8:2 ethyl acetate:hexane), H NMR spectra
in δ ppm: 2.41 δ ppm (singlet, 6H, -CH ), 3.80 to 3.89 δ ppm
(triplet, 2H, -N-CH -), 4.11 to 4.18 δ ppm (triplet, 2H, -CO-
CH -), 6.89 to 7.88 δ ppm (6H, aromatic region), 11.02 δ ppm
H
19
N
3
O , m.w.: 409.13, Appearance: Off
6
1
f
+
3
(
3
2
13
2
-1
(singlet, 1H, -NH). IR (KBr, νmax, cm ): 3779, 3734, 3663,
3643, 3391, 3268, 2920, 2371, 2354, 2281, 1691, 1656, 1597,
1557, 1521, 1486, 1416, 1367, 1311, 1238, 1193, 1125, 1068,
999, 875, 820, 766, 752, 655. Mass spectra m/z: 409.13 (100.00
%), 410.13 (23.2 %), 411.13 (4.0 %), 410.12 (1.1 %), 395,
378, 365, 361, 349, 332, 306, 289, 275, 262, 249, 223, 278,
4
-(4-((6-Chloro-3-nitro-2-oxo-2H-chromen-4-yl)amino)-
phenyl)morpholine-3-one (YS-03): Yield: 65 %; m.p.: 296-
98 °C; m.f.: C19 Cl, m.w.: 415.78,Appearance: Colour-
less white, R value-0.43 (8:2 ethyl acetate:hexane), H NMR
spectra in δ ppm: 3.80 to 3.89 δ ppm (triplet, 2H, -CH -O-),
-), 4.32 δ ppm (singlet,
-), 6.8 to 7.4 δ ppm (7H aromatic region), 11.3 δ
2
H
14
N O
3 6
1
13
f
205, C NMR (100 MHz, chloroform-d) δ: 135.60, 123.30,
2
121.53, 121.29, 20.69, 15.95. Elemental analysis (%): C,61.61;
H, 4.68; N, 10.26; Found (%): C, 60.02; H, 4.37; N, 9.53.
4-(4-((7,8-Dimethyl-3-nitro-2-oxo-2H-chromen-4-
yl)amino)phenyl)morpholine-3-one (YS-07): Yield: 58 %;
4
.02 to 4.16 δ ppm (triplet, 2H, -N-CH
H, -CO-CH
2
2
2
-1
ppm (singlet, 1H, -NH-). IR (KBr, νmax, cm ): 3280, 3077, 2864,
711, 1650, 1616, 1541, 1539, 1442, 1352, 1307, 1212, 1131,
049, 997, 851, 752, 690, 625. Mass spectra m/z: 415.06 (M )
100.0 %), 417.05 (32.0 %), 416.06 (20.9 %), 418.06 (7.0 %),
17.06 (3.5 %), 416.05 (1.1 %), 419.06 (1.1 %), 363, 336,
18, 290, 277, 262, 248, 235, 221, 207, C NMR (100 MHz,
chloroform-d) δ: 132.85, 125.44, 123.30, 121.53, 117.56.
Elemental analysis (%): C, 54.89; H, 3.39; Cl, 8.53; N, 10.11;
Found (%): C, 49.27; H, 3.40; Cl, 8.50; N, 9.11.
1
1
m.p.: 210-212 °C; m.f.: C21
Off white, R value-0.40 (8:2 ethyl acetate:hexane), H NMR
spectra in δ ppm: 2.42 δ ppm (singlet, 6H, -CH ), 3.78 to 3.89
δ ppm (triplet, 2H, -N-CH -), 4.10 to 4.18 δ ppm (triplet, 2H,
-CO-CH -), 6.89 to 7.89 δ ppm (6H, aromatic region), 11.05 δ
H
19
N O
3
6
, m.w.: 409.13,Appearance:
+
1
f
(
3
4
3
2
13
2
-1
ppm (singlet, 1H, -NH). IR (KBr, νmax, cm ): 3780, 3734, 3663,
3642, 3391, 3268, 2920, 2370, 2354, 2280, 1669, 1657, 1597,
1557, 1521, 1486, 1417, 1367, 1312, 1238, 1193, 1125, 1067,
997, 875, 820, 766, 750, 654. Mass spectra m/z: 409.13 (100.00
%), 410.13 (23.2 %), 411.13 (4.0 %), 410.12 (1.1 %), 395,
378, 365, 361, 349, 332, 306, 289, 275, 262, 249, 223, 278,
4
-(4-((6-Fluoro-3-nitro-2-oxo-2H-chromen-4-yl)-
amino)phenyl)morpholine-3-one (YS-04): Yield: 74 %; m.p.:
34-236 ºC; m.f.: C19 F, m.w.: 399.33, Appearance:
Colourless white, R value-0.42 (8:2 ethyl acetate:hexane), H
NMR spectra in δ ppm: 3.80 to 3.91 δ ppm (triplet, 2H, -CH
O-), 4.02 to 4.16 δ ppm (triplet, 2H, -N-CH -), 4.30 δ ppm
2
H
14
N
3
O
6
1
13
f
205, C NMR (100 MHz, chloroform-d) δ 125.00, 123.30,
2
-
122.67, 121.53, 19.01, 12.44. Elemental analysis (%): C, 61.61;
H, 4.68; N, 10.26; Found (%): C, 60.02; H, 4.37; N, 9.53.
2