Month 2018
Hexahydrospiro-pyrazolo[3,4-b]pyridine-4,10-pyrrolo[3,2,1-ij]quinolines Derived
from 5,6-dihydro-4H-pyrrolo[3,2,1-ij]quinoline-1,2-dione
(m, 1H, Ar–H), 3.64–3.78 (bs, 2H, CH2), 2.80–2.94 (bs,
2H, CH2), 1.95–2.25 (bs, 2H, CH2), 1.56 (s, 3H, CH3);
13C NMR (CDCl3, 75 MHz) δ 175.0, 150.7, 146.5,
138.7, 138.5, 137.1, 135.6, 133.1, 131.4, 131.2, 130.8,
129.0, 128.4, 128.3, 127.7, 123.3, 122.9, 120.6, 120.6,
117.6, 99.1, 83.6, 52.2, 39.2, 24.5, 21.32, 11.75; Found:
%C, 71.67; %H, 4.48; %N, 14.03 C30H22ClN5O
NMR (CDCl3, 75 MHz) δ 173.2, 148.6, 144.0, 139.6,
136.6, 135.7, 134.9, 129.7, 128.6, 128.1, 126.4, 126.1,
125.8, 124.1, 121.2, 121.0, 121.0, 118.5, 116.1, 96.7,
81.3, 50.4, 37.3, 22.6, 19.5, 19.4, 9.9; Found: %C, 77.16;
%H, 5.12; %N, 14.62 C31H25N5O requires: %C, 77.00;
%H, 5.21; %N, 14.48.
1-(3-Chlorophenyl)-3-methyl-20-oxo-6-(p-tolyl)-1,50,60,7-
tetraahydro-20H,40H-spiro[pyrazolo[3,4-b]pyridine-4,10-
requires: %C, 71.49; %H, 4.40; %N, 13.90.
1-(4-Chlorophenyl)-3-methyl-20-oxo-6-phenyl-1,50,60,7-
tetrahydro-20H,40H-spiro[pyrazolo[3,4-b]pyridine-4,10-
pyrrolo[3,2,1-ij]quinoline]-5-carbonitrile (9f).
White
crystals, 89%, mp 262–263°C; IR (KBr) υ cmꢀ1 3204,
pyrrolo[3,2,1-ij]quinoline]-5-carbonitrile (9c).
White
3049, 2932, 2200, 1695, 1592, 1531, 1474, 1360, 1238,
1170, 1096, 726; H NMR (300 MHz, CDCl3) δ 10.31
1
crystals, 95%, mp 298–300°C; IR (KBr) υ cmꢀ1: 3201,
3055, 2928, 2871, 2199, 1708, 1619, 1537, 1486,
13337, 1094, 833, 752; H NMR (300 MHz, CDCl3) δ
(bs, 1H, NH, D2O exchangeable), 7.64 (s, 1H, Ar–H),
7.47–7.62 (m, 3H, Ar–H), 7.43(d, 1H, J = 7.2 Hz,
Ar–H), 7.32 (d, 2H, J = 7.5 Hz, Ar–H), 7.13 (d, 2H,
J = 7.5 Hz, Ar–H), 6.93–7.10 (m, 2H, Ar–H), 3.58–3.85
(m, 2H, CH2), 2.80 (bs, 2H, CH2), 2.36 (s, 3H, CH3),
1.87–2.16 (m, 2H, CH2), 1.48 (s, 3H, CH3); 13C NMR
(CDCl3, 75 MHz) δ 174.9, 151.3,146.0, 141.5, 138.4,
137.4, 136.2, 133.0, 131.4, 130.1, 129.8, 129.5, 129.2,
128.3, 128.2, 124.4, 123.3, 122.9, 120.5, 118.1, 99.0,
82.4, 52.3, 39.3, 24.4, 21.4, 21.4, 11.9; Found: %C,
72.12; %H, 4.74; %N, 13.70 C31H24ClN5O requires:
1
7.94 (bs, 1H,NH), 7.52 (d, 2H, J = 7.2 Hz, Ar–H),
7.37–7.48 (m, 7H, Ar–H), 7.11 (d, 2H, J = 6.9 Hz,
Ar–H), 7.02 (t, 1H, J = 7.5 Hz, Ar–H), 3.59–3.75 (m,
2H, CH2), 2.78–2.92 (m, 2H,CH2), 2.08–2.21 (m, 1H,
CH), 1.89–2.08 (m, 1H,CH), 1.50 (s, 3H, CH3); 13C
NMR (CDCl3, 75 MHz) δ 175.7, 162.3, 151.2, 146.1,
138.4, 137.3, 136.2, 133.1, 132.9, 131.4, 131.0, 129.8,
128.9, 128.3, 124.4, 123.4, 122.9, 120.6, 117.8, 98.8,
82.9, 52.3, 39.2, 24.5, 21.4, 20.7, 11.8; Found: %C, 71.
31; %H, 4.54; %N, 14.18 C30H22ClN5O requires: %C,
%C, 71.88; %H, 4.67; %N, 13.52.
1-(4-Chlorophenyl)-3-methyl-20-oxo-6-(p-tolyl)-1,50,60,7-
tetrahydro-20H,40H-spiro[pyrazolo[3,4-b]pyridine-4,10-
71.49; %H, 4.40; %N, 13.90.
4-(5-Cyano-3-methyl-20-oxo-6-phenyl-50,60-dihydro-
20H,40H-spiro[pyrazolo[3,4-b]pyridine-4,10-pyrrolo[3,2,1-ij]
pyrrolo[3,2,1-ij]quinoline]-5-carbonitrile (9g).
White
quinoline]-1(7H)-yl)benzenesulfonamide (9d).
White
crystals, 93%, mp 284–285°C; IR (KBr) υ cmꢀ1 3219,
crystals, 95%, mp 298–300°C; IR (KBr) υ cmꢀ1 3415,
3049, 2929, 2201, 1694, 1621, 1530, 1370, 1240, 1095,
1
3224, 3059, 2933, 2202, 1703, 1617, 1538, 1487,
826, 757; H NMR (300 MHz, CDCl3) δ 7.83–7.99 (m,
1
1335, 1161, 1100, 1016, 831,753; H NMR (300 MHz,
2H, Ar–H), 7.32–7.57 (m, 6H, Ar–H), 7.19–7.31 (m,
2H, Ar–H), 6.94–7.19 (m, 2H,Ar–H), 3.59–3.82 (bs,
2H, CH2), 2.78–2.92 (bs, 2H, CH2), 2.36 (s, 3H, CH3),
1.89–2.21 (m, 2H, CH2), 1.48 (s, 3H, CH3); 13C NMR
(CDCl3, 75 MHz) δ 174.9, 162.3, 151.3, 146.0, 141.4,
138.4, 137.3, 136.2, 133.0, 131.4, 130.0, 129.8, 129.6,
129.3, 128.3, 128.2, 124.3, 123.3, 122.9, 120.6, 118.1,
98.9, 82.5, 52.3, 39.2, 24.5, 21.5, 21.4, 11.8; Found:
%C, 72.07; %H, 4.79; %N, 13.65 C31H24ClN5O
CDCl3) δ 10.42 (bs, 1H, NH), 7.92 (d, 2H, J = 8.1 Hz,
Ar–H), 7.78 (d, 2H, J = 8.1 Hz, Ar–H), 7.66 (d, 2H,
J = 7.8 Hz, Ar–H), 7.50–7.58 (m, 3H, Ar–H), 7.47 (bs,
2H, NH2), 7.18 (d, 1H, J = 7.5 Hz, Ar–H), 7.13 (d,
1H, J = 7.8 Hz, Ar–H), 7.03 (t, 1H, J = 7.5 Hz, Ar–H),
3.75–3.88 (m, 1H,CH), 3.57–3.75 (m, 1H,CH), 2.78–
2.91 (m, 2H, CH2), 1.90–2.11 (m, 2H, CH2), 1.51 (s,
3H, CH3); 13C NMR (CDCl3, 75 MHz) δ 175.0, 152.7,
145.9, 142.7, 140.7, 138.6, 138.5, 133.8, 132.2, 131.1,
129.4, 128.9, 128.6,127.3,123.8, 123.3, 122.9,120.9,
118.9, 99.6, 81.9, 52.1, 24.3, 21.4, 11.8; Found: %C,
65.71; %H, 4.26; %N, 15.54 C30H24N6O3S requires:
requires: %C, 71.88; %H, 4.67; %N, 13.52.
4-(5-Cyano-3-methyl-20-oxo-6-(p-tolyl)-50,60-dihydro-
20H,40H-spiro[pyrazolo[3,4-b]pyridine-4,10-pyrrolo[3,2,1-ij]
quinoline]-1(7H)-yl)benzenesulfonamide (9h).
White
crystals, 93%, mp 301–302°C; IR (KBr) υ cmꢀ1 3442,
%C, 65.68; %H, 4.41; %N, 15.32.
3-Methyl-20-oxo-1-phenyl-6-(p-tolyl)-1,50,60,7-tetraahydro-
20H,40H-spiro[pyrazolo[3,4-b]pyridine-4,10-pyrrolo[3,2,1-ij]
3355, 3207, 2926, 2190, 1678, 1621, 1528, 1345, 1162,
1
1097, 834, 749; H NMR (300 MHz, CDCl3) δ 10.35
quinoline]-5-carbonitrile (9e).
White crystals, 91%, mp
(bs, 1H, NH), 7.93 (d, 2H, J = 8.4 Hz, Ar–H), 7.79 (d,
2H, J = 8.4 Hz, Ar–H), 7.57 (d, 2H, J = 7.8 Hz, Ar–H),
7.48 (bs, 2H, NH2), 7.32 (d, 2H, J = 7.8 Hz, Ar–H),
7.17 (d, 1H, J = 7.5 Hz, Ar–H), 7.12 (d, 1H, J = 6.9 Hz,
Ar–H), 7.02 (t, 1H, J = 7.5 Hz, Ar–H), 3.72–3.84 (m,
1H, CH), 3.58–3.72 (m, 1H, CH), 2.79–2.91 (bs, 2H,
CH2), 2.36 (s, 3H, CH3), 1.88–2.18 (m, 2H, CH2), 1.50
(s, 3H, CH3); 13C NMR (CDCl3, 75 MHz) δ 175.1,
152.7, 145.9, 142.6, 141.0, 140.7, 138.6, 132.2, 130.9,
264–265°C; IR (KBr) υ cmꢀ1 3219, 3049, 2929, 2872,
2201, 1696, 1616, 1553, 1471, 1357, 733; 1H NMR
(300 MHz, CDCl3) δ 7.42–7.58 (m, 6H, Ar–H), 7.31–
7.40 (m, 1H, Ar–H), 7.25 (d, 2H, J = 7.5 Hz, Ar–H),
7.11 (d, 2H, J = 7.5 Hz, Ar–H), 6.98–7.07 (m, 1H,
Ar–H), 6.92 (bs, 1H, NH), 3.80 (bs, 2H, CH2), 2.79–2.89
(bs, 2H, CH2), 2.38 (s, 3H, CH3), 2.23–2.10 (m, 1H,
CH), 2.10–1.92 (m, 1H, CH), 1.63 (s, 3H,CH3); 13C
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet