ANWER AND SAYED
9
was refluxed for 7 hours. The reaction mixture leaved to
cool, and then poured into crushed ice water (50 mL).
The solid precipitated was collected by filtration and crys-
tallized from methanol forming 10.
3.13 | Ethyl-4-amino-5-((4-cyano-
3-(4-(dimethylamino)phenyl)-1-phenyl-1H-
pyrazol-5-yl)carbamoyl)-2-methyl-
3-oxaspiro[5.5]undeca-1,4-diene-
1-carboxylate (12)
ꢀ
ꢀ
−1
m.p. 240 C to 242 C. IR (KBr) ν cm :3176 (NH),
1
2
212, 2195 (CN), 1728 (C O), 1611 (C N). H-NMR
ꢀ
ꢀ
−1
(
DMSO-d ) δ: 3.03 (s, 6H, N(CH ) ), 3.88 (s, 2H,
m.p. 192 C to 194 C. IR (KBr) ν cm :3452, 3304 (NH ),
6
3 2
2
COCH CN), 6.67 to 8.08 (m, 9H, Ar-H), 10.9 (s, 1H, NH,
3192 (NH), 2208 (CN), 1774, 1646 (C O), 1597 (C N).
2
13
1
D O exchangeable). C NMR (DMSO-d ) δ (ppm): 26.9,
H-NMR (DMSO-d ) δ: 1.41 (t, 3H, OCH CH ), 1.50 (m,
2
6
6
2
3
4
1
3
6
5
0.1, 70.1, 111.5, 112.0, 112.2, 121.9, 125.1, 125.7, 126.2,
6H, 3CH ), 2.16 (t, 4H, 2CH ), 2.33 (s, 3H, CH ), 3.08 (s,
2 2 3
31.2, 138.0, 147.6, 149.2, 149.8 and 164.2. MS: m/z
6H, N(CH ) ), 4.31 (q, 2H, OCH CH ), 5.21 (s, 1H, NH,
3
2
2
3
+
70 [M ] (100%). Anal. Calcd for C H N O (370): C,
D O exchangeable), 6.65 to 7.59 (m, 9H, Ar-H), 9.97 (s,
2
21
18
6
13
8.09; H, 4.90; N, 22.69. Found: C, 68.24; H,
.01; N, 22.54%.
2H, NH , D O exchangeable). C NMR (DMSO-d ) δ
2 2 6
(ppm): 15.3, 20.2, 20.4, 20.6, 22.1, 31.8, 40.4, 63.2, 70.3,
8
1
7.2, 100.5, 110.6, 113.2, 122.7, 125.6, 125.9, 126.8, 131.6,
38.8, 142.4, 147.8, 150.2, 151.2, 152.8, 165.6 and 169.2.
+
3
3
.11 | 2-Cyano-N-(4-cyano-
-(4-(dimethylamino)phenyl)-1-phenyl-1H-
MS: m/z 580 [M ] (1.2%). Anal. Calcd for C H N O
33
36
6
4
(580): C, 68.26; H, 6.25; N, 14.47. Found: C, 67.91; H,
6.32; N, 14.54%.
pyrazol-5-yl)-
-cyclohexylideneacetamide (11)
2
A mixture of 10 (0.01 mol, 3.70 g), cyclohexanone
3.14 | 5-Acetyl-2-amino-N-(4-cyano-
3-(4-(dimethylamino)phenyl)-1-phenyl-1H-
pyrazol-5-yl)-4-methyl-3-oxaspiro[5.5]
undeca-1,4-diene-1-carboxamide (13)
(
(
0.01 mol, 0.98 mL) with TEA (0.5 mL) in ethanol
25 mL) was refluxed for 5 hours. The solid precipitated
after cooling was filtrated, washed with ethanol, and
crystallized from methanol forming 11.
ꢀ
ꢀ
−1
ꢀ
ꢀ
−1
m.p. 276 C to 278 C. IR (KBr) ν cm :3214 (NH),
m.p. 168 C to 170 C. IR (KBr) ν cm :3409, 3343 (NH ),
2
2
261, 2209 (CN), 1681 (C O), 1618 (C N), 1601 (C C).
3234 (NH), 2210 (CN), 1776, 1648 (C O), 1598 (C N).
1
1
H-NMR (DMSO-d ) δ: 1.50 (m, 6H, 3CH ), 2.16 (t, 4H,
H-NMR (DMSO-d ) δ: 2.25 (s, 3H, COCH ), 1.52 (m, 6H,
6
2
6
3
2
CH ), 3.08 (s, 6H, N(CH ) ), 4.48 (s, 1H, NH, D O
3CH ), 2.12 (t, 4H, 2CH ), 2.33 (s, 3H, CH ), 3.08 (s, 6H,
2 2 3
N(CH ) ), 5.19 (s, 1H, NH, D O exchangeable), 6.61 to
3 2 2
2
3 2
2
13
exchangeable), 6.67 to 7.63 (m, 9H, Ar-H). C NMR
DMSO-d ) δ (ppm): 23.2, 26.1, 29.3, 40.2, 70.4, 88.2,
(
7.68 (m, 9H, Ar-H) 10.09 (s, 2H, NH , D O exchange-
2 2
6
13
1
1
4
7
5
11.9, 112.3, 112.6, 122.8, 125.2, 125.7, 126.9, 131.2, 138.7,
42.3, 147.5, 149.7, 157.9, 158.7 and 160.1. MS: m/z
able). C NMR (DMSO-d ) δ (ppm): 17.2, 20.2, 21.2, 23.5,
6
26.3, 31.2, 40.2, 70.1, 82.9, 110.6, 113.4, 120.4, 121.9,
125.5, 125.7, 126.8, 131.4, 138.6, 142.6, 147.9, 150.6, 153.2,
+
50 [M ] (0.9%). Anal. Calcd for C H N O (450): C,
27
26 6
+
1.98; H, 5.82; N, 18.65. Found: C, 71.67; H,
.71; N, 18.64%.
158.1, 160.9 and 166.9. MS: m/z 550 [M ] (1.4%). Anal.
Calcd for C H N O (550): C, 69.80; H, 6.22; N, 15.26.
32
34 6 3
Found: C, 69.68; H, 6.19; N, 15.41%.
3
.12 | Reaction of 11 with different
nucleophiles: general procedure
3.15 | 2-Amino-5-((4-cyano-
3
-(4-(dimethylamino)phenyl)-1-phenyl-1H-
A solution of 11 (0.01 mol, 4.50 g) in ethanol (25 mL) and
equimolar amounts of ethyl acetoacetate, acetyl acetone,
and/or malononitrile was added and the mixture was
refluxed for 4 to 8 hours according to (TLC). While (2-3)
drops of TEA was added in case of reaction with ethyl
acetoacetate and acetyl acetone and sodium ethoxide in
case of reaction with malononitrile. The crude material
obtained after cooling was filtered off and crystallized
from methanol in case of ethyl acetoacetate and acetyl
acetone and from acetone in case of malononitrile to give
compound 12 to 14, respectively.
pyrazol-5-yl)amino)-3-oxaspiro[5.5]undeca-
1,4-diene-1,4-dicarbonitrile (14)
ꢀ
−1
m.p. > 300 C. IR (KBr) ν cm :3471, 3351 (NH ), 3233
(NH), 2214, 2200 (CN), 1632 (C N). H-NMR (DMSO-d )
δ: 1.54 (m, 6H, 3CH ), 2.09 (t, 4H, 2CH ), 3.02 (s, 6H,
N(CH ) ), 6.18 (s, 1H, NH, D O exchangeable), 6.57 to
7.66 (m, 9H, Ar-H), 10.63 (s, 2H, NH , D O exchange-
able). C NMR (DMSO-d ) δ (ppm): 16.2, 23.5, 26.7, 40.1,
57.7, 70.4, 111.6, 113.2, 114.1, 115.4, 122.0, 125.3, 126.0,
126.7, 131.4, 137.9, 142.8, 148.9, 151.2, 152.2 and 159.3.
2
1
6
2
2
3
2
2
2
2
13
6