Chemistry of Heterocyclic Compounds 2017, 53(2), 210–215
vibrations of NH2). 1H NMR spectrum, δ, ppm: 2.15 (3Н, s,
H Ar); 7.52 (2Н, t, J = 7.8, H Ar); 8.23 (2H, d, J = 7.9, о-H Ph);
8.56 (1H, s, Н-3); 8.60 (1H, d, J = 3.0, NH2); 9.50 (1H, d,
J = 3.1, NH2). 13C NMR spectrum, δ, ppm: 38.0 (СН); 40.9
(СН2); 45.3 (СОСН2); 101.8, 102.0 and 102.2 (С-4 Ar),
105.0 (C-3a); 105.1 (C-4a); 110.0, 110.1, 110.2 and 110.3
(С-2,6 Ar); 120.8; 125.9; 128.9; 135.0; 139.1; 148.0, 148.1
and 148.2 (С-1 Ar); 150.4; 151.8 (C-9a); 161.4 and 163.4 (2C
СF); 165.3 (C-8a); 198.7 (СО). Found, m/z: 391.1360 [M+H]+.
C22H16F2N4O. Calculated, m/z: 391.1366.
СН3); 7.09 (2Н, br. s, NH2); 7.29–7.33 (1H, m, H Ph); 7.53–
7.57 (4H, m, H Ph); 7.66–7.68 (1H, m, H Ph); 7.77–7.80 (2H,
m, H Ph); 8.30–8.32 (2H, m, H Ph); 8.50 (1Н, s, Н-3).
13C NMR spectrum, δ, ppm: 24.6 (СН3); 104.7 (С-3a); 111.0
(C-5); 120.3; 125.4; 128.9 (2С Ph); 129.0; 134.0; 138.2;
139.5; 147.7 (C-9); 150.7 (С-6); 156.5 (С-7a); 197.6 (CO).
Found, m/z: 329.1407 [M+H]+. C20H16N4O. Calculated,
m/z: 329.1398.
5-Methanesulfonyl-6-(4-methoxyphenyl)-1-phenyl-
1H-pyrazolo[3,4-b]pyridin-4-amine (4a). Yield 0.89 g
(75%). Mp 287–289°С. IR spectrum, ν, cm–1: 3423, 3325
(NH2), 1581 (deformation vibrations of NH2). 1H NMR
spectrum, δ, ppm (J, Hz): 3.01 (3Н, s, CH3SO2); 3.82 (3Н,
s, СН3O); 6.96 (2Н, d, J = 8.7, H Ar); 7.31–7.33 (1H, m,
H Ph); 7.39 (2H, d, J = 8.7, H Ar); 7.50–7.52 (2Н, m,
H Ph); 7.8 (1Н, br. s, NH2); 8.12–8.14 (2Н, m, H Ph); 8.3
(1Н, br. s, NH2); 8.69 (1Н, s, Н-3). 13C NMR spectrum,
δ, ppm: 44.9 (SO2СН3); 55.0 (CH3O); 105.5 (С-3a); 110.2;
112.4; 120.8; 126.1; 129.0; 130.3; 133.6; 134.6; 138.8;
149.4 (C-4); 149.7 (С-7a); 159.0 (COCH3); 160.6 (С-6).
Found, m/z: 395.1171 [M+H]+. C20H18N4O3S. Calculated,
m/z: 395.1173.
4-Amino-7-(4-isopropylphenyl)-1-phenyl-1,6,7,8-tetra-
hydro-5H-pyrazolo[3,4-b]quinolin-5-one (8c). Yield 0.88 g
(74%). Mp 239–241°С. IR spectrum, ν, cm–1: 3421, 3303
(NH2), 1629 (stretching vibrations of С=О), 1612
(deformation vibrations of NH2). 1H NMR spectrum, δ, ppm
(J, Hz): 1.19 (6Н, d, J = 6.9, СН(СН3)2); 2.74–2.80 (1H, m,
CH2); 2.83–2.90 (1Н, m, СН(СН3)2); 2.96 (1H, dd,
J = 16.5, J = 11.8, CH2); 3.15–3.20 (1H, m, CH2); 3.30
(1H, dd, J = 16.2, J = 11.5, CH2); 3.45 (1Н, tt, J = 11.4,
J = 3.9, СН); 7.20 (2H, d, J = 8.0, H Ar); 7.27–7.35 (3H, m,
H Ar); 7.52 (2H, t, J = 7.8, H Ph); 8.23 (2H, d, J = 8.1,
H Ph); 8.54–8.57 (2H, m, Н-3, NH2); 9.51 (1H, d, J = 3.2,
NH2). 13C NMR spectrum, δ, ppm: 27.3 (CH(СН3)2); 33.4
(СН(СН3)2); 38.26 (СН); 42.0 (СН2); 46.4 (СОСН2); 105.6
(C-3a); 105.7 (C-4a); 121.2; 126.3; 126.7; 127.1; 129.4;
135.4; 139.5; 141.2; 146.9; 150.9; 152.2 (C-9a); 166.2
(C-8a); 199.8 (СО). Found, m/z: 397.2019 [M+H]+.
C25H24N4O. Calculated, m/z: 397.2024.
5-Methanesulfonyl-1-(4-methylphenyl)-6-phenyl-1H-
pyrazolo[3,4-b]pyridin-4-amine (4b). Yield 0.87 g (77%).
Mp 254–256°С. IR spectrum, ν, cm–1: 3416, 3348 (NH2),
1
1587 (deformation vibrations of NH2). H NMR spectrum,
δ, ppm (J, Hz): 2.32 (3Н, s, СН3); 3.04 (3Н, s, CH3SO2);
7.30 (2Н, d, J = 8.7, H Ar); 7.38–7.43 (5H, m, H Ph,
H Ar); 7.8 (1Н, br. s, NH2); 7.93–7.95 (2H, d, J = 8.7,
H Ar); 8.3 (1Н, br. s, NH2); 8.68 (1Н, s, Н-3). 13C NMR
spectrum, δ, ppm: 20.6 (CH3); 45.0 (SO2СН3); 105.5
(С-3a); 110.0; 127.1; 127.8; 128.7; 129.5; 134.4; 135.7;
136.5; 141.6; 149.3 (C-4); 149.8 (С-7a); 160.9 (С-6).
Found, m/z: 379.1219 [M+H]+. C20H18N4O2S. Calculated,
m/z: 379.1224.
4-Amino-7-(3-chlorophenyl)-1-phenyl-1,6,7,8-tetrahydro-
5H-pyrazolo[3,4-b]quinolin-5-one (8d). Yield 0.93 g
(80%). Mp 241–243°С. IR spectrum, ν, cm–1: 3477, 3292
(NH2), 1633 (stretching vibrations of С=О), 1593 (deformation
vibrations of NH2). 1H NMR spectrum, δ, ppm (J, Hz): 2.73–
2.79 (1H, m, CH2); 3.01 (1H, dd, J = 16.5, J = 12.3, CH2);
3.13–3.18 (1H, m, CH2); 3.30–3.36 (1H, m, CH2); 3.49–
3.56 (1Н, m, СН); 7.30–7.39 (4H, m, H Ar); 7.48–7.54
(3H, m, H Ar); 8.23 (2Н, d, J = 7.6, H Ar); 8.56 (1H, s,
Н-3); 8.58 (1H, d, J = 3.0, NH2); 9.50 (1H, br. s, NH2).
13C NMR spectrum, δ, ppm: 38.1 (СН); 41.3 (СН2); 45.7
(СОСН2); 105.2 (C-3a); 105.3 (C-4a); 120.9; 125.7; 126.0;
126.7; 127.0; 129.1; 130.4; 133.2; 135.1; 139.2; 146.1; 150.5;
151.9 (C-9a); 165.6 (C-8a); 199.1 (СО). Found, m/z:
389.1165 [M+H]+. C22H17ClN4O. Calculated, m/z: 389.1164.
4-Amino-1-(4-methoxyphenyl)-1,6,7,8-tetrahydro-
5H-pyrazolo[3,4-b]quinolin-5-one (8e). Yield 0.76 g
(82%). Mp 228–230°С. IR spectrum, ν, cm–1: 3355, 3278
(NH2), 1610 (stretching vibrations of С=О), 1606
(deformation vibrations of NH2). 1H NMR spectrum, δ, ppm
(J, Hz): 2.00 (2H, quin, J = 6.6, СН2CH2СН2); 2.59 (2H, t,
J = 6.0, CH2); 2.97 (2H, t, J = 6.0, CH2); 3.82 (3Н, s,
ОСН3); 7.10 (2H, d, J = 8.9, H Ar); 8.04 (2H, d, J = 8.9,
H Ar); 8.45 (1H, d, J = 3.6, NH2); 8.48 (1H, s, Н-3); 9.51
(1H, d, J = 3.9, NH2). 13C NMR spectrum, δ, ppm: 21.4
(СН2СН2СН2); 34.4 (СН2); 39.2 (СОСН2); 55.4 (ОСН3);
104.8 (C-3a); 105.5 (C-4a); 114.2; 122.7; 132.4; 134.4;
150.0; 152.0 (C-9a); 157.4 (COCH3); 166.6 (C-8a); 200.3
(СО). Found, m/z: 309.1346 [M+H]+. C17H16N4O2.
Calculated, m/z: 309.1346.
4-Amino-7,7-dimethyl-1-phenyl-1,6,7,8-tetrahydro-
5H-pyrazolo[3,4-b]quinolin-5-one (8a). Yield 0.66 g
(72%). Mp 201–203°С. IR spectrum, ν, cm–1: 3384, 3288
(NH2), 1631 (stretching vibrations of С=О), 1622 (deformation
1
vibrations of NH2). H NMR spectrum, δ, ppm (J, Hz): 1.03
(6Н, s, 2СН3); 2.49 (2H, s, CH2); 2.90 (2H, s, CH2); 7.34
(1H, tt, J = 7.4, J = 1.1, p-H Ph); 7.52–7.56 (2H, m, m-H
Ph); 8.23 (2H, dd, J = 8.6, J = 1.1, о-H Ph); 8.52 (1H, d,
J = 3.3, NH2); 8.54 (1H, s, Н-3); 9.47 (1H, d, J = 3.6, NH2).
13C NMR spectrum, δ, ppm: 27.6 ((СН3)2); 31.8 (С(СН3)2);
47.7 (СН2); 52.5 (СОСН2); 104.7 (C-3a); 105.2 (C-4a);
120.9; 126.0; 129.0; 135.0; 139.2; 150.8 (C-4); 151.6 (C-9a);
165.5 (C-8a); 199.9 (СО). Found, m/z: 307.1546 [M+H]+.
C18H18N4O. Calculated, m/z: 307.1554.
4-Amino-7-(3,5-difluorophenyl)-1-phenyl-1,6,7,8-tetra-
hydro-5H-pyrazolo[3,4-b]quinolin-5-one (8b). Yield
0.95 g (81%). Mp 246–248°С. IR spectrum, ν, cm–1: 3488,
3299 (NH2), 1633 (stretching vibrations of С=О), 1622
1
(deformation vibrations of NH2). H NMR spectrum, δ, ppm
(J, Hz): 2.73–2.80 (1H, m, CH2); 3.01 (1H, dd, J = 16.5,
J = 12.5, CH2); 3.13–3.17 (1H, m, CH2); 3.30–3.37 (1H, m,
CH2); 3.55 (1Н, tt, J = 12.2, J = 3.6, СН); 7.07–7.11 (1H,
m, H Ph); 7.15–7.20 (2H, m, H Ar); 7.33 (1Н, t, J = 7.4,
4-Amino-1-(4-methoxyphenyl)-7,7-dimethyl-1,6,7,8-
tetrahydro-5H-pyrazolo[3,4-b]quinolin-5-one (8f). Yield
211