Acta Chim. Slov. 2015, 62, 136–151
1
47
5
,7-Diamino-3-methyl-4-phenyl-1,4-dihydropyrazo-
4.53 (s, 1H, pyran H- 4), 6.78, 6.80 (2s, 2H, 2NH, D O
2
lo[4’,3’:5,6]pyrano[2,3-b]pyridine-6-carbonitrile
exchangeable), 6.88–7.08 (m, 9H, Ar-H), 12.04 (s, 1H,
–
1
+
(
10a). Yield: 80%; m.p.: >300 °C; IR (KBr, cm ) ν: 3379,
NH, D O exchangeable); MS (m/z,%): 417 (M , 25).
2
3
213, 2922 (2NH , NH), 3070 (CH aromatic), 2960, 2922
Anal. calcd. for C H N O S: C, 63.29; H, 4.59; N,
2
22 19
5
2
1
(CH aliphatic), 2199 (CN); H NMR (DMSO-d ) δ: 2.49
16.78. Found: C, 63.09; H, 4.68; N, 16.90.
6
(
s, 3H, CH ), 4.58 (s, 1H, pyran H-4), 7.10 (s, 2H, NH ,
3
2
D O exchangeable), 7.06–7.95 (m, 5H, Ar-H), 8.02 (s,
2
3
. 1. 4. General Procedure for Synthesis
2
H, NH , D O exchangeable), 11.01 (s, 1H, NH, D O exc-
2
2
2
of Compounds 13 and 14
1
3
hangeable); C NMR (DMSO-d , 400 MHz): 14.4, 36.9,
6
6
1
6
2
8.3, 91.4, 114.1, 127.1, 128.3, 129.1, 137.3, 144.9,
46.8, 148.4, 150.6, 154.3, 154.9; MS (m/z,%): 318 (M ,
To a solution of compound 1 (0.98 g, 0.01 mol) and
+
salicylaldehyde (1.23 g, 0.01mol) in ethanol (30 mL) con-
taining triethylamine (1.0 mL), either malononitrile (0.66
g, 0.01 mol) or ethyl cyanoacetate (1.13 g, 0.01 mol) were
added. The whole reaction mixture, in each case, was hea-
ted under reflux for 2 h, left to cool then poured onto
ice/water mixture containing few drops of hydrochloric
acid. The formed solid product, in each case, was collec-
ted by filtration and crystallized from ethanol.
3). Anal. calcd. for C H N O: C, 64.14; H, 4.43; N,
1
7
14
6
6.40. Found: C, 63.90; H, 4.68; N, 26.15.
5
,7-Diamino-4-(4-methoxyphenyl)-3-methyl-1,4-dihy-
dropyrazolo-[4’,3’:5,6]pyrano[2,3-b]pyridine-6-carbo-
nitrile (10b). Yield: 85%; m.p.: 203–205 °C; IR (KBr,
cm ) ν: 3354, 3263, 3130 (2NH , NH), 3050 (CH aroma-
tic), 2957, 2912 (CH aliphatic), 2206 (CN); H NMR
–
1
2
1
(
(
7
DMSO-d ) δ: 2.49 (s, 3H, CH ), 3.83 (s, 3H, OCH ), 4.86
5-Amino-1-methyl-3H-chromeno[4’,3’:4,5]pyrano
[2,3-c]pyrazol-6(11bH)-one (13). Yield: 78%; m.p.:
6
3
3
s, 1H, pyran H-4), 6.80 (s, 2H, NH , D O exchangeable),
2 2
–
1
.06–7.95 (m, 4H, Ar-H), 7.95 (s, 2H, NH , D O exchan-
>300 °C; IR (KBr, cm ) ν: 3340, 3242 (NH , NH), 3050
2
2
2
1
3
1
geable), 11.01 (s, 1H, NH, D O exchangeable); C NMR
(CH aromatic), 2999, 2958 (CH aliphatic); H NMR
2
(
1
1
DMSO-d , 400 MHz): 10.5, 39.3, 55.5, 105.4, 114.1,
(DMSO-d ) δ: 2.48 (s, 3H, CH ), 4.10 (s, 1H, pyran H),
6
6
3
14.8, 128.6, 130.4, 133.1, 143.8, 146.9, 148.3, 152.0,
4.14 (s, 2H, NH , D O exchangeable), 7.29–7.57 (m, 4H,
2 2
+
13
60.7, 161.1, 162.1; MS (m/z,%): 348 (M , 83.91). Anal.
Ar-H), 11.01 (s, 1H, NH, D O exchangeable); C NMR
2
calcd. for C H N O : C, 62.06; H, 4.63; N, 24.12.
(DMSO-d , 400 MHz): 10.6, 26.3, 115.6, 119.1, 125.3,
1
8
16
6
2
6
Found: C, 62.39; H, 4.71; N, 23.98.
125.7, 126.0, 134.9, 142.3,152.4, 159.3, 162.0, 162.5,
+
1
63.0; MS (m/z,%): 269 (M , 21). Anal. calcd. for
5
,7-Diamino-4-(4-chlorophenyl)-3-methyl-1,4-dihy-
C H N O : C, 62.45; H, 4.12; N, 15.61. Found: C,
14 11 3 3
dropyrazolo-[4’,3’:5,6]pyrano[2,3-b]pyridine-6-carbo-
62.39; H, 4.18; N, 15.88.
–1
nitrile (10c).Yield: 82%; m.p.: >300 °C; IR (KBr, cm ) ν:
406, 3290 (NH , NH), 3050 (CH aromatic), 2927, 2912
3
1-Methyl-3H-chromeno[4’,3’:4,5]pyrano[2,3-c]pyra-
zole-5,6-dione (14). Yield: 82%; m.p.: >300 °C; IR (KBr,
2
1
(CH aliphatic), 1681, 1662 (C=O); H NMR (DMSO-d )
6
–
1
δ: 2.50 (s, 3H, CH ), 4.57 (s, 1H, pyran H-4), 7.15 (s, 2H,
cm ) ν: 3350 (NH), 3050 (CH aromatic), 2927, 2912 (CH
3
1
NH , D O exchangeable), 7.17–7.92 (m, 4H, Ar-H), 8.72
aliphatic), 1722 (C=O); H NMR (DMSO-d ) δ: 2.48 (s,
2
2
6
(
s, 2H, NH , D O exchangeable), 11.03 (s, 1H, NH, D O
3H, CH ), 6.93-7.60 (m, 4H, Ar-H), 11.01 (s, 1H, NH,
2
2
2
3
1
3
+
exchangeable); C NMR (DMSO-d , 400 MHz): 10.5,
D O exchangeable); MS (m/z,%): 268 (M , 29). Anal. cal-
6
2
3
1
5
2
9.3, 67.2 105.4, 116.7, 128.4, 130.5, 130.7, 134.0, 143.9,
46.8, 150.6, 158.2, 160.7, 161.3; MS (m/z,%): 353 (M ,
cd. for C H N O : C, 62.69; H, 3.01; N, 10.44. Found: C,
62.90; H, 3.20; N, 10.64.
1
4
8
2
4
+
9). Anal. calcd. for C H ClN O: C, 57.88; H, 3.71; N,
17
13
6
3.82. Found: C, 57.58; H, 3.88; N 23.56.
3
. 1. 5. General Procedure for Synthesis
of Compounds 17a–c
3
. 1. 3. 1-(5-Cyano-4-(4-methoxyphenyl)-3-
To a solution of compound 1 (0.98 g, 0.01 mol) in
methyl-1,4-dihydropyrano[2,3-c]pyrazol-
ethanol (30 mL) containing triethylamine (1.0 mL), the
appropriate aldehyde (0.01 mol) and thiourea (0.76 g,
0.01 mol) were added. The whole reaction mixture, in
each case was heated under reflux for 1 h, left to cool then
poured onto ice/water mixture containing few drops of
hydrochloric acid. The formed solid product, in each case,
was collected by filtration and crystallized from ethanol.
6-yl)-3-phenylthiourea (12)
To a solution of compound 6b (2.66 g, 0.01 mol) in
dioxane (40 mL) containing triethylamine (1.0 mL),
phenylisothiocyanate (1.30 g, 0.01 mol) was added. The
reaction mixture was heated under reflux for 2 h. The for-
med solid product was collected by filtration and crystalli-
zed from ethanol. Yield: 90%; m.p.: 192–194 °C; IR (KB-
–
1
r, cm ) ν: 3360, 3315 (2 NH), 3068 (CH aromatic), 2962,
3-Methyl-4-phenyl-1H-pyrazolo[3,4-d]pyrimidine-6
(7H)-thione (17a). Yield: 92%; m.p.: 148–150 °C; IR
1
2926 (CH aliphatic), 2191 (CN), 1170 (C=S); H NMR
–
1
(
DMSO-d ) δ: 1.76 (s, 3H, CH ), 3.72 (s, 3H, OCH3),
(KBr, cm ) ν: 3348, 3310 (2 NH), 3050 (CH aromatic),
6
3
Kamel: Convenient Synthesis, Characterization, ...