TAMIMI ET AL.
5 of 11
ppm): 1.98 (s, 3H), 4.71 (s, 1H), 6.94 (s, 2H), 7.49 (d,
14. 2‐Amino‐5‐oxo‐4‐(thiophen‐2‐yl)‐5,6,7,8‐tetrahydro‐
4H‐chromene‐3‐carbonitrile (4o): FT‐IR (KBr, νmax,
13
2H), 8.14 (d, 2H), 11.65 (s, 1H). C NMR (500 MHz,
−
1
DMSO‐d , δ, ppm): 11.4, 23.5, 70.8, 112.8, 128, 129,
cm ): 3363,3323, 3178, 2956, 2374, 2192, 1679,
6
[55]
1
30.1, 135.5, 141.8, 150.2, 154.2, 160.8.
. 6‐ Amino‐ 3‐methyl‐ 4‐(4‐methoxyphenyl) ‐1,4‐
dihydropyrano[2,3‐c]pyrazole‐5‐carbonitrile (4i):
FT‐IR (KBr, ν , cm ): 3480, 3259, 2181, 1610,
1664, 1650, 1608,1409, 1359,1209, 1135, 1000, 709,
1
9
626, 536, 501. H NMR (500 MHz, CDCl , δ, ppm):
3
2.03 (m, 2H), 2.36 (m, 1H), 2.44 (m, 1H), 2.56 (m,
2H), 4.56 (s, 2H, NH), 4.8 (s, 1H), 6.89 (dd,
J = 5.1 Hz, J = 1.2 Hz,1H), 6.98 (d, J = 3.2 Hz,
−
1
max
1
1
442. H NMR (300 MHz, DMSO‐d , δ, ppm): 1.78
6
[
51]
(
(
(
s, 3H), 3.85 (s, 3H), 4.60 (s, 1H), 6.88 (d, 2H), 6.89
d, 2H), 7.20 (s, 2H), 12.08 (s, 1H). C NMR
1H), 7.12 (d, J = 5.1 Hz, 1H).
13
15. 2‐Amino‐3‐ethylacetato‐4‐(phenyl)‐7,7‐ dimethyl‐5‐
oxo‐4H‐5,6,7,8‐tetrahydrobenzo[b]pyran (4p): FT‐
500 MHz, CDCl , δ, ppm): 10.1, 36.3, 55, 57.6,
3
−
1
1
07.7, 113.5, 114.3, 119, 136.8, 144.4, 156, 156.2,
IR (KBr, νmax, cm ): 3423, 3265, 3020, 2980, 1667,
[55]
1
160.5.
1614, 1520, 1462, 1378. H NMR (300 MHz, CDCl ,
3
1
1
1
1
0. 2‐Amino‐3‐cyano‐7,7‐dimethyl‐4‐ phenyl‐5‐oxo‐5,6,
,8‐tetra‐4H‐chromene (4k): FT‐IR (KBr, νmax, cm
δ, ppm): 1.01 (s, 3H), 1.08 (s, 3H), 1.24 (t, 3H),
2.16–2.25 (m, 2H), 2.34 (s, 2H), 4.24 (q, 2H), 4.37
7
−
1
)
: 733, 1027, 1065, 1125, 1264, 1385, 1444, 1515,
(s, 1H), 5.52 (brs, 2H, D O exchangeable), 7.12–
2
1
13
1
592, 2198, 3324, 3471. H NMR (300 MHz,
7.42 (m, 5H). C NMR (75 MHz, CDCl , δ, ppm):
3
DMSO‐d , δ, ppm): 7.30–7.10 (m, 5H), 5.85 (br, 2H,
19.12, 26.52, 27.65, 31.44, 35.56, 39.68, 50.15, 60.63,
71.47, 113.09, 126.42, 126.86, 127.03, 142.54, 156.68,
6
NH ), 4.32 (s, 1H), 2.48 (br s, 2H), 2.25 (H‐6a,
2
[
58]
J = 16.0 Hz), 2.15 (H‐6b, J = 16.0 Hz), 1.10 (s, 3H),
161.87, 172.42, 196.01.
1
3
1
1
6
.03 (s, 3H). C NMR (CDCl , δ, ppm): 195.1,
16. Ethyl‐2‐amino‐4‐ (4‐chlorophenyl)‐7,7‐ dimethyl‐5‐
3
61.3, 157.7, 143.3, 127.6, 126.7, 126.0, 118.8, 113.0,
0.0, 49.9, 39.9, 35.0, 31.3, 28.1, 26.8.
oxo‐5,6,7,8‐ tetrahydro‐4H‐chromene‐3‐carboxylate
[56]
−1
(4q): FT‐IR (KBr, ν , cm ): 3480, 3327, 1688,
max
1
1. 2‐Amino‐3‐cyano‐7,7‐dimethyl‐4 ‐(4‐chlorophenyl)‐
‐oxo‐5,6,7,8‐tetra‐4H‐chromene (4l): FT‐IR (KBr,
1660, 1525, 1206. H NMR (400 MHz, CDCl , δ,
3
5
ppm): 0.96 (s, 3H, CH ), 1.09 (s, 3H, CH ), 1.17 (t,
3
3
−
1
νmax, cm ): 3380, 3323, 3183, 2959, 2188, 1675,
1
J = 7.32, 3H, CH ), 2.17 and 2.25 (J = 16.04 Hz,
3
1
635, 1603, 1365. H NMR (300 MHz, DMSO‐d , δ,
2H), 2.41 (s, 2H); 4.02–4.04 (m, 2H), 4.46 (s, 1H),
6
13
ppm): 7.30–7.10 (m, 4H), 6.30 (br s, 2H, NH ), 4.28
6.20 (s, br, 2H, NH ), 7.15–7.20 (m, 4H). C NMR
2
2
(s, 1H), 2.46 (br s, 2H), 2.24 (H‐6a, J = 16.0 Hz),
(400 MHz, CDCl , δ, ppm): 14.18, 27.31, 29.09,
3
2
.14 (H‐6b, J = 16.0 Hz), 1.12 (s, 3H), 1.03 (s, 3H).
32.21, 33.39, 40.58, 50.62, 59.74, 81.04, 116.33,
127.86, 129.62, 131.6, 144.38, 158.26, 161.46, 168.92,
1
3
C NMR (CDCl , δ, ppm): 194.6, 161.1, 157.5,
3
[
59]
1
41.9, 130.9, 127.9, 127.2, 118.4, 112.1, 58.1, 49.4,
196.40.
[56]
38.9, 34.2, 30.9, 27.6, 26.3.
17. Ethyl‐2‐amino‐4‐(4‐nitrophenyl)‐7,7‐dimethyl‐5‐oxo
‐5,6,7,8‐tetrahydro‐4H‐chromene‐3‐carboxylate (4r):
2. 2‐Amino‐3‐cyano‐7,7‐dimethyl‐4‐ (4‐nitrophenyl)‐5‐
oxo‐5,6,7,8‐tetra‐4H‐chromene (4m): FT‐IR (KBr,
−
1
FT‐IR (KBr, νmax, cm ): 3471, 3335, 2996, 1685,
−
1
1
νmax, cm ): 3314, 1043, 2191, 1514, 1603, 1112,
1654, 1508, 1341, 1204. H NMR (CDCl , δ, ppm):
3
1
2
971. H NMR (300 MHz, DMSO‐d , δ, ppm): 8.14
0.93 (3H, s), 1.07 (3H, s), 1.11 (3H, t, J = 7 Hz),
2.11 (1H, d, J = 16.3 Hz), 2.23 (1H, d,
J = 16.3 Hz), 2.43 (2H, br s), 4.06 (2H, q,
6
(
(
cd, 2H), 7.42 (cd, 2H), 6.50 (br s, 2H, NH ), 4.48
s, 1H), 2.52 (br s, 2H), 2.26 (H‐6a, J = 16.0 Hz),
2
2
.16 (H‐6b, J = 16.0 Hz), 1.14 (s, 3H), 1.03 (s, 3H).
J = 7 Hz), 4.76 (1H, s), 6.32 (2H, br s, NH ), 7.42
2
1
3
13
C NMR (CDCl , δ, ppm): 195.2, 162.1, 158.1,
(2H, d, J = 8.7 Hz), 8.06 (2H, d, J = 8.7 Hz).
C
3
1
50.9, 146.2, 128.1, 123.1, 118.1, 112.2, 58.5, 49.9,
NMR (CDCl , δ, ppm): 14.23, 27.29, 29.07, 32.25,
3
[56]
40.1, 35.4, 31.6, 28.2, 27.0.
34.30, 40.61, 50.57, 59.87, 79.24, 115.52, 123.19,
129.24, 146.28, 153.56, 158.46, 162.08, 168.59,
3. 2‐Amino‐4‐ (4‐methoxyphenyl)‐7,7‐ dimethyl‐5‐oxo‐
,6,7,8‐tetrahydro‐4H‐chromene‐3‐carbonitrile (4n):
[
60]
5
196.32.
−
1
FT‐IR (KBr, νmax, cm ): 3276, 3206, 3070, 2956,
18. Ethyl‐2‐amino‐7,7‐ dimethyl‐5‐oxo‐4‐(p‐tolyl)‐5,6,7,8
‐tetrahydro‐4H‐chromene‐3‐carboxylate (4s): FT‐IR
1
2183, 1702, 1644, 1608, 1482, 1223. H NMR
−
1
(
300 MHz, DMSO‐d , δ, ppm): 7.04–7.07 (d, 2H),
(KBr, νmax, cm ): 3408, 3293, 2980, 1689, 1668,
6
1
6.83 (s, 2H), 6.79–6.82 (d, 2H), 4.14 (s, 2H), 3.72
1623, 1523, 1472, 1366. H NMR (400 MHz,
(
0
s, 3H), 2.22 (d, 2H), 2.08 (d, 1H), 1.08 (s, 3H),
.97 (s, 3H). C NMR (100 MHz, DMSO, δ,
DMSO‐d , δ, ppm): 7.52 (s, 2H), 7.02–6.98 (m, 4H),
6
13
4.45 (s, 1H), 3.97–3.90 (m, 2H), 2.56–2.42 (m, 2H),
2.25 (d, 1H, J = 16.8 Hz), 2.20 (s, 3H), 2.04 (d, 1H,
J = 16 Hz), 1.10 (t, 3H, J = 8 Hz), 1.03 (s, 3H),
ppm): 196.1, 162.5, 158.8, 158.3, 137.2, 128.6,
1
[57]
20.2, 114.0.