ACCEPTED MANUSCRIPT
0
Characteristic: White solid; Mp: 178-180 C; IR (KBr): 1406, 1489, 1590, 1617, 1649, 2181, 3165, 3372
-
1 1
cm ; H NMR (300 MHz, DMSO-d ): δ 1.78 (3H, s), 4.60 (1H, s), 6.90 (2H, s), 7.12 (2H, d, J = 8.4 Hz),
6
1
3
7
1
1
6
.50 (2H, d, J = 8.4 Hz), 12.12 (1H, s); C NMR (75 MHz, DMSO-d ): δ 10.2, 36.1, 57.2, 97.6, 120.2,
6
21.1, 130.2, 131.8, 136.1, 144.3, 155.2, 161.4; Anal. Calcd for C H BrN O: C 50.78, H 3.35, N
1
4
11
4
6.92%. Found: C 50.75, H 3.37, N 16.90%.
-amino-4-(4-methoxyphenyl)-3-methyl-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5j):
0
Characteristic: White solid; Mp: 210-212 C; IR (KBr): 1412, 1493, 1596, 1611, 1651, 2192, 3173, 3372
-
1 1
cm ; H NMR (300 MHz, CDCl +DMSO-d ): δ 1.70 (3H, s), 3.65 (3H, s), 4.39 (1H, s), 5.72 (2H, s), 6.69
3
6
1
3
(
2H, d, J = 8.7 Hz), 6.97 (2H, d, J = 8.4 Hz); C NMR (75 MHz, CDCl +DMSO-d ): δ 14.9, 40.8, 59.9,
3 6
6
4.1, 102.7, 118.6, 125.8, 133.5, 133.6, 140.9, 160.0, 163.1, 165.6; Anal. Calcd for C H N O : C 63.82,
15 14 4 2
H 5.00, N 19.85%. Found: C 63.85, H 5.03, N 19.82%.
6
-amino-3-methyl-4-(m-tolyl)-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5k):
0
Characteristic: White solid; Mp: 170-172 C; IR (KBr): 1406, 1484, 1592, 1611, 1649, 2182, 3179, 3372
-
1 1
cm ; H NMR (300 MHz, DMSO-d ): δ 1.69 (3H, s), 2.18 (3H, s), 4.45 (1H, s), 6.76 (2H, s), 6.87 (2H, d,
6
1
3
J = 7.2 Hz), 6.94 (1H, d, J = 7.5 Hz), 7.09 (1H, d, J = 7.5 Hz), 11.99 (1H, s); C NMR (75 MHz, DMSO-
d6): δ 10.2, 21.5, 36.6, 57.7, 98.1, 121.2, 125.1, 127.9, 128.3, 128.7, 136.0, 137.9, 144.9, 155.2, 161.3;
Anal. Calcd for C H N O: C 67.65, H 5.30, N 21.04%. Found: C 67.68, H 5.32, N 21.00%.
1
5
14
4
6
-amino-3-methyl-4-(thiophen-2-yl)-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5l):
0
Characteristic: White solid; Mp: 192-194 C; IR (KBr): 1401, 1484, 1596, 1614, 1649, 2197, 3175, 3372
-
1 1
cm ; H NMR (300 MHz, DMSO-d ): δ 1.90 (3H, s), 4.97 (1H, s), 6.92 (3H, t, J = 3.9 Hz), 6.99 (1H, d, J
6
13
=
3.3 Hz), 7.36 (1H, d, J = 4.8 Hz), 12.15 (1H, s); C NMR (75 MHz, DMSO-d ): δ 10.2, 31.9, 58.1,
6
9
3
6
8.0, 121.1, 124.8, 125.4, 127.0, 136.5, 150.2, 154.8, 161.1; Anal. Calcd for C H N OS: C 55.80, H
12 10 4
.90, N 21.69%. Found: C 55.83, H 3.88, N 21.73%.
-amino-4-isopropyl-3-methyl-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5m):
0
Characteristic: White solid; Mp: 166-168 C; IR (KBr): 1395, 1479, 1588, 1602, 1649, 2182, 3169, 3372
-
1 1
cm ; H NMR (300 MHz, CDCl +DMSO-d ): δ 0.68 (3H, d, J = 6.9 Hz), 0.77 (3H, d, J = 6.9 Hz), 1.76-
3
6
1
3
7
.78 (1H, m), 2.07 (3H, s), 3.27 (1H, d, J = 3.0 Hz), 5.69 (2H, s); C NMR (75 MHz, CDCl +DMSO-d ):
3 6
δ 10.0, 17.8, 17.9, 34.4, 36.2, 54.8, 96.6, 121.3, 134.2, 155.9, 162.3; Anal. Calcd for C H N O: C 60.53,
1
1
14
4
H 6.47, N 25.67%. Found: C 60.55, H 6.44, N 25.70%.
Ethyl 6-amino-3-methyl-4-(3-nitrophenyl)-1,4-dihydropyrano[2,3-c]pyrazole-5-carboxylate (5n):
0
Characteristic: White solid; Mp: 180-182 C; IR (KBr): 1077, 1160, 1356, 1402, 1520, 1602, 1654, 2932,
-1 1
3
217, 3468cm ; H NMR (300 MHz, CDCl +DMSO-d ): δ 1.08 (3H, t, J = 7.2 Hz), 1.96 (3H, s), 4.01
3 6
(
2H, q, J = 7.2 Hz), 4.93 (1H, s), 6.61 (2H, s), 7.40 (1H, t, J = 7.8 Hz), 7.51 (1H, dd, J = 7.8 Hz, J = 1.2
1 2
1
3
Hz), 8.00-8.03 (1H, m), 8.10 (1H, t, J = 1.9 Hz); C NMR (75 MHz, CDCl +DMSO-d ): δ 9.8, 13.8,
3
6