HAMZA ET AL.
11
2
CH of tetrahydronaphthalene), 7.21 to 7.74 (m, 4H, Ar‐
145.5, 157.8, 162.3 (24C, Ar‐C), 158.2 (CH═N); MS:
2
+
+
H), 7.76 to 7.98 (m, 8H, Ar‐H+ pyridine‐H5), 8.93 (s,1H,
N═CH), 13.63 (s,1H, NH, pyrazole, exchangeable with
D O); C NMR (101 MHz, DMSO) δ: 22.1 (2CH ), 28.5
m/z (%): 473 (M +2, 5.06), 471 (M , 12.62), 75 (100),
342 (24.02), 499 (17.22); Analysis calcd. for C H FN
5
30
22
13
(471.54):C, 76.42; H, 4.70; F, 4.03; N, 14.85; found: C,
76.25; H, 4.72; F, 3.93; N, 15.02.
2
2
(2CH ), 105.9, 116.2, 119.1, 122.5, 125.4, 128.8, 129.4,
2
1
1
5
5
6
6
30.8, 131.8, 132.0, 135.1, 144.9, 147.2, 157.8, 158.1,
58.5, 164.1 (24C, Ar‐C),158.96 (CH═N); MS: m/z (%):
4
.16 | 1‐(4‐Fluorophenyl)‐N‐(4‐(4‐
+
26 (M +1, 3.9), 525 (M+, 5.19), 96 (23.48) , 719 (95.57),
fluorophenyl)‐6‐(5,6,7,8‐
7 (100) ; Analysis calcd. for C H BrFN (525.43): C,
29
22
4
tetrahydronaphthalen‐2‐yl)‐1H‐
pyrazolo[3,4‐b]pyridin‐3‐yl)methanimine
6.29; H, 4.22; Br, 15.21; F, 3.62; N, 10.66; found: C,
5.99; H, 4.12; Br, 15.32; F, 3.51; N, 10.96.
(14e)
4
.14 | 1‐(4‐Chlorophenyl)‐N‐(4‐(4‐
Yield (73%); yellow crystals; m.p. 252 to 254°C; IR (KBr,
−
1
cm ): υ 3432 (NH), 2926 (CH, alicyclic), 1605 (C═N),
fluorophenyl)‐6‐(5,6,7,8‐
1
1
230 (C─F); H NMR (400 MHz, DMSO‐d , δ ppm):
tetrahydronaphthalen‐2‐yl)‐1H‐
pyrazolo[3,4‐b]pyridin‐3‐yl)methanimine
6
1.78 (br.s, 4H, 2CH
of tetrahydronaphthalene), 2.82 (br.
2
(14c)
s, 4H, 2CH of tetrahydronaphthalene), 7.21 (d, J = 8.0
2
Hz, 1H, Ar‐H), 7.35 (t, J = 8.4 Hz, 4H, Ar‐H), 7.76 (d, J
= 8.0 Hz, 1H, Ar‐H), 7.83 –8.04 (m, 6H, Ar‐H +
Yield 82%; yellow crystals; m.p. 260 to 262°C; IR (KBr,
cm ): υ 3439 (NH), 2925 (CH, alicyclic), 1600 (C═N),
−
1
pyridine‐H5), 8.94 (s, 1H, N═CH) , 13.62 (s, 1H, NH,
1
13
1
1
2
227 (C─F); H NMR (300 MHz DMSO‐d , δ ppm):
.79 (m, 4H, alicyclic 2CH of tetrahydronaphthalene),
.82 (m, 4H, 2CH of tetrahydronaphthalene), 7.21 (d,
pyrazole, exchangeable with D
DMSO) δ: 22.4 (2CH ), 28.4 (2CH ), 106.0, 115.0, 116.9,
2
2
O); C NMR (101 MHz,
6
2
2
119.5, 122.2, 128.6, 129.3, 130.5, 133.5, 135.1, 136.4,
2
J = 8.7 Hz, 1H, Ar‐H), 7.35 (t, J = 8.8 Hz, 2H, Ar‐H),
.58 (d, J = 8.4 Hz, 2H, Ar‐H), 7.75 (s, 1H, Ar‐H), 7.83
d, J = 8.4 Hz, 2H, Ar‐H), 7.91‐7.97 (m, 4H, Ar‐H +
pyridine‐H5), 8.94 (s, 1H, N═CH), 13.64 (s, 1H, NH,
139.6, 150.2, 150.8, 151.7, 155.4, 163.8, 168.5 (23C, Ar‐
+
7
(
C), 157.1 (CH═N); MS: m/z (%): 464 (M , 84.35), 463
+
(M −1, 30.80), 191 (100), 351 (76.10), 398 (73.39) ; Anal-
ysis calcd. for C29
H F N (464.52): C, 74.98; H, 4.77; F,
22 2 4
13
pyrazole, exchangeable with D O);
C NMR (101
8.18; N, 12.06; found: C, 74.78; H, 4.56; F, 8.27; N, 12.36.
2
MHz, DMSO) δ: 23.1, 23.2 (2CH ), 29.3 (2CH ), 06.3,
2
2
1
1
1
15.0, 115.2, 118.1, 124.8, 128.3, 129.4, 130.8, 132.8,
34.9, 135.2, 136.1, 136.8, 138.9, 144.7, 152.9, 153.8,
55.7, 162.2 (24C, Ar‐C), 159.5 (CH═N); MS: m/z
4
.17 | N‐(4‐(4‐Fluorophenyl)‐6‐(5,6,7,8‐
tetrahydronaphthalen‐2‐yl)‐1H‐
pyrazolo[3,4‐b]pyridin‐3‐yl)‐1‐(4‐
methoxyphenyl)methanimine (14f)
+
+
+
(%):483 (M +3, 10.4), 482 (M +2, 33.4), 481 (M +1,
+
3
9.12), 480 (M , 100) ; Analysis calcd. for C H ClFN
29 22 4
(
480.97): C, 72.42; H, 4.61;Cl, 7.37; F, 3.95; N, 11.65;
Yield (73%); yellow crystals; m.p. 252 to 254°C; IR (KBr,
cmYield 89%; yellow crystals; m.p. 260 to 262°C; IR (KBr,
cm ): υ 3432 (NH), 2925 (CH, alicyclic), 1631 (C═N),
found: C, 72.21; H, 4.89; Cl, 7.22; F, 4.05;N, 11.74.
−
1
1
4
.15 | 4‐(((4‐(4‐Fluorophenyl)‐6‐(5,6,7,8‐
1236 (C─F); H NMR (400 MHz, DMSO‐d
(br.s, 4H, 2CH of tetrahydronaphthalene), 2.80 (m, 4H,
2CH of tetrahydronaphthalene), 3.85 (s, 3H, OCH ), 7.06
(d, J = 8.7 Hz, 2H, Ar‐H), 7.22 (d, J = 8.5 Hz, 1H, Ar‐H),
.36 (t, J = 8.8 Hz, 2H, Ar‐H), 7.68 to 7.82 (m, 3H, Ar‐H),
6
, δ ppm): 1.79
tetrahydronaphthalen‐2‐yl)‐1H‐
pyrazolo[3,4‐b]pyridin‐3‐yl)imino)methyl)
benzonitrile (14d)
2
2
3
7
Yield (88%); pale yellow crystals; m.p. 303 to 305°C; IR
7.88 to 8.01 (m, 4H, Ar−H+ pyridine‐H5), 8.85 (s, 1H,
−
1
(
(
KBr, cm ): υ 3429 (NH), 2925 (CH, alicyclic), 2213
N═CH), 13.60 (s, 1H, NH, pyrazole, exchangeable with
1
13
CN), 1227 (C─F); H NMR (400 MHz, DMSO‐d , δ
D O); C NMR (101 MHz, DMSO) δ: 22.0, 23.1 (2CH2),
6
2
ppm): 1.78 (br. s, 4H, 2CH of tetrahydronaphthalene),
29.2 (2CH ), 55.2 (CH ), 106.0, 113.0, 116.1, 119.3, 123.3,
2
2
3
2
7
1
.78 (m, 4H, 2CH of tetrahydronaphthalene), 7.14 to
127.7, 129.9, 130.6, 132.7, 135.8, 136.3, 139.2, 146.7, 152.4,
2
.9 (m, 12H, Ar‐H + pyridine‐H5), 9.01 (s, 1H, N═CH),
151.3, 156.2, 163.4 164.5, (24C, Ar‐C) 157.3 (CH═N); MS:
13
+
+
3.64 (s, 1H, NH, pyrazole, exchangeable with D O);
C
m/z (%): 478 (M +2, 27.84), 476 (M , 22.03), 358 (100),
2
NMR (101 MHz, DMSO) δ: 22.4 (2CH ), 28.8, 29.8
356 (88.15), 257 (83.03); Analysis calcd. for: C H FN O
2
30 25
4
(
1
2CH ), 118.5 (CN), 105.3, 113.4, 116.2, 119.1, 122.4,
25.4, 128.2, 129.7, 130.6, 133.1, 137.3, 138.9, 142.8,
(476.56):C, 75.61; H, 5.29; F, 3.99; N, 11.76; found: C,
75.41; H, 5.18; F, 3.87; N, 11.98.
2