5-Aminopyrido[3´,2´:4,5]thieno[3,2-c]isoquinolines Russ. Chem. Bull., Int. Ed., Vol. 67, No. 5, May, 2018
909
(9-Me), 116.10 (CPTI(4a)), 118.91 (CPTI(11a)), 122.43 (CPTI(4)),
125.47 (CPTI(3)), 126.53 (CPTI(6b)), 126.76 (CPTI(1)), 128.26
(CPTI(8)), 132.51 (CPTI(2)), 133.83 (CPTI(11b)), 146.01
(CPTI(6a)), 151.20 (CPTI(7)), 158.58 (CPTI(5)), 160.75 (CPTI(9)),
166.06 (CPTI(10a)).
δ: 23.46 (9-Мe), 116.50 (CPTI(4a)), 119.37 (CPTI(11a)),
122.49 (CPTI(4)), 125.12 (CPTI(6b)), 125.41 (CPTI(3)), 126.80
(CPTI(1)), 127.54 (C7-Ph(3), C7-Ph(5)), 127.85 (CPTI(8)),
128.72 (C7-Ph(4)), 129.85 (C7-Ph(2), C7-Ph(6)), 132.31 (CPTI(2)),
133.73 (CPTI(11b)), 136.10 (C7-Ph(1)), 147.32 (CPTI(6a)),
149.89 (CPTI(7)), 158.78 (CPTI(9)), 159.83 (CPTI(5)), 167.33
(CPTI(10a)).
5-Amino-8,9,10,11-tetrahydroisoquinolino[3΄,4΄:4,5]thieno-
[2,3-b]quinoline 13-oxide (6b). The yield was 0.39 g (63%); m.p.
288—290 °C (DMF—MeOH). Found (%): C, 67.45; H, 4.77;
N, 12.88; S, 9.83. C18H15N3OS. Calculated (%): C, 67.27;
H, 4.70; N, 13.07; S, 9.98. IR, ν/cm–1: 3328, 3264, 3216 (NH2),
2920, 2952, 1640, 1616, 1568, 1536, 1504, 1432, 1388, 1000
(S=O), 768. 1H NMR (DMSO-d6), δ: 1.70—1.80 (m, 2 H,
9-(CH2)THQ); 1.80—1.90 (m, 2 H, 10-(CH2)THQ); 2.83—2.98
5-Amino-7,9-diphenylpyrido[3΄,2΄:4,5]thieno[3,2-c]isoquino-
line 11-oxide (6e). The yield was 0.23 g (27%); m.p. 182—186 °C
(DMF—MeOH). Found (%): C, 74.58; H, 4.01; N, 9.91; S, 7.77.
C26H17N3OS. Calculated (%): C, 74.44; H, 4.08; N, 10.02;
S, 7.64. IR, ν/cm–1: 3444, 3426, 3319 (NH2), 3207, 3057, 2906,
1640, 1615, 1588, 1576, 1542, 1502, 1417, 1359, 1027, 1015 (S=O),
759, 696. 1H NMR (DMSO-d6), δ: 7.36 (br.s, 1 H, NH2);
(m, 4 H, 8-(CH2)THQ, 11-(CH2)THQ); 7.58 (t, 1 H, C(3)HTHIQTQ
,
J = 8.1 Hz); 7.76—7.83 (m, 2 H, C(2)HTHIQTQ, C(7)HTHIQTQ);
7.95 (s, 2 H, NH2); 8.00 (d, 1 H, C(1)HTHIQTQ, J = 8.1 Hz);
8.44 (d, 1 H, C(4)HTHIQTQ, J = 8.8 Hz). 13C NMR (DMSO-d6),
δ: 21.91 (9-(CH2)THIQTQ), 22.34 (10-(CH2)THIQTQ), 28.58
(8-(CH2)THIQTQ), 32.18 (11-(CH2)THIQTQ), 117.02 (CTHIQTQ(4a)),
119.86 (CTHIQTQ(13a)), 122.49 (CTHIQTQ(4)), 125.59 (CTHIQTQ(3)),
126.86 (CTHIQTQ(1)), 129.33 (CTHIQTQ(6b)), 130.54 (CTHIQTQ(7)),
132.62 (CTHIQTQ(2)), 133.76 (CTHIQTQ(13b)), 135.82 (CTHIQTQ(7a)),
149.04 (CTHIQTQ(6a)), 158.73 (CTHIQTQ(5)), 161.31 (CTHIQTQ(11a)),
163.14 (CTHIQTQ(12a)).
7.51—7.63 (m, 7 H, C(3)H9-Ph,C(4)H9-Ph, C(5)H9-Ph, C(3)H7-Ph,
C(4)H7-Ph, C(5)H7-Ph and HPTI(3)); 7.74—7.81 (m, 2 H, C(2)
H7-Ph, C(6)H7-Ph); 7.85 (t, 1 H, C(2)HPTI, J = 7.3 Hz); 8.05
(s, 1 H, C(8)HPTI); 8.11 (d, 1 H, C(1)HPTI, J = 7.3 Hz); 8.26—8.34
(m, 2 H, C(2)H9-Ph, C(6)H9-Ph); 8.38 (d, 1 H, C(4)HPTI
,
J = 7.3 Hz). 13C NMR (DMSO-d6), δ: 116.62 (CPTI(4a)),
120.10 (CPTI(11a)), 122.59 (CPTI(4)), 124.61 (CPTI(8)), 125.40
(CPTI(3)), 126.30 (CPTI(6b)), 126.89 (CPTI(1)), 127.00
(C9-Ph(3), C9-Ph(5)), 127.52 (C7-Ph(3), C7-Ph(5)), 128.84
(C7-Ph(4)), 128.94 (C7-Ph(2), C7-Ph(6)), 129.97 (C9-Ph(4)),
130.05 (C9-Ph(2), C9-Ph(6)), 132.33 (CPTI(2)), 133.63 (CPTI(11b)),
136.07 (C7-Ph(1)), 136.80 (C9-Ph(1) 6-Ph), 148.09 (CPTI(6a)),
149.69 (CPTI(7)), 155.94 (CPTI(9)), 159.82 (CPTI(5)), 168.12
(CPTI(10a)).
5-Amino-7-phenyl-8,9,10,11-tetrahydroisoquinolino-
[3΄,4΄:4,5]thieno[2,3-b]quinoline 13-oxide (6c). The yield was
0.51 g (64%); m.p. 277—279 °C (DMF—MeOH). Found (%):
C, 72.41; H, 4.94; N, 10.42; S, 8.23. C24H19N3OS. Calculat-
ed (%): C, 72.52; H, 4.82; N, 10.57; S, 8.07. IR, ν/cm–1: 3468,
3308, 3357, 3211 (NH2), 3051, 2941, 1630, 1613, 1573, 1543, 1502,
1428, 1415, 1371, 1007 (S=O), 770, 699. 1H NMR (DMSO-d6),
δ: 1.60—1.73 (m, 2 H, 9-(CH2)THIQTQ); 1.80—1.92 (m, 2 H,
10-(CH2)THIQTQ); 2.41 (t, 2 H, 8-(CH2)THIQTQ, J = 5.9 Hz);
3.02 (t, 2 H, 11-(CH2)THIQTQ, J = 5.9 Hz); 6.80 (br.s, 2 H, NH2);
7.16—7,32 (m, 2 H, C(2)H7-Ph, C(6)H7-Ph); 7.42—7.52 (m, 3 H,
Substituted 5-aminopyrido[3΄,2΄:4,5]thieno[3,2-c]isoquino-
line-11,11-dioxides (8a—f) were obtained according to the pro-
cedure described for the synthesis of compounds 4a—f.
5-Amino-7,9-dimethylpyrido[3΄,2΄:4,5]thieno[3,2-c]isoquino-
line-11,11-dioxide (8a). The yield was 0.54 g (87%); m.p.
340—342 °C (DMF—MeOH). Found (%): C, 61.88; H, 4.16;
N, 13.50; S, 10.21. C16H13N3O2S. Calculated (%): C, 61.72; H, 4.21;
N, 13.50; S, 10.30. IR, ν/cm–1: 3472, 3416, 3376 (NH2), 2928,
1616, 1544, 1504, 1424, 1280 (SO2), 1152 (SO2), 1116, 752.
1H NMR (DMSO-d6), δ: 2.57 (s, 3 H, 7-Me); 2.91 (s, 3 H, 9-Me);
7.43 (s, 1 H, C(8)HPTI); 7.64 (t, 1 H, C(3)HPTI, J = 8.1 Hz);
7.86—7.93 (m, 2 H, C(1)HPTI, C(2)HPTI); 8.18 (s, 2 H, NH2);
8.41 (d, 1 H, C(4)HPTI, J = 8.8 Hz). 13C NMR (DMSO-d6), δ:
19.38 (7-Me), 23.56 (9-Me), 111.63 (CPTI(11a)), 115.77 (CPTI(4a)),
121.73 (CPTI(4)), 122.35 (CPTI(6b)), 125.69 (CPTI(3)), 127.43
(CPTI(1)), 129.84 (CPTI(11b)), 129.87 (CPTI(8)), 133.25 (CPTI(2)),
146.72 (CPTI(6a)), 147.05 (CPTI(7)), 157.56 (CPTI(10a)), 160.03
(CPTI(5)), 161.46 (CPTI(9)).
C(3)H7-Ph, C(4)H7-Ph, C(5)H7-Ph); 7.54 (t, 1 H, C(3)HTHIQTQ
J = 8.1 Hz); 7.79 (t, 1 H, C(2)HTHIQTQ, J = 8.1 Hz); 8.05 (d, 1 H,
C(1)HTHIQTQ, J = 8.1 Hz); 8.28 (d, 1 H, C(4)HTHIQTQ
,
,
J = 8.8 Hz). 13C NMR (DMSO-d6), δ: 21.90 (9-(CH2)THIQTQ),
21.98 (10-(CH2)THIQTQ), 27.07 (8-(CH2)THIQTQ), 32.63
(11-(CH2)THIQTQ), 116.05 (CTHIQTQ(4a)), 119.63 (CTHIQTQ(13a)),
122.36 (CTHIQTQ(4)), 125.33 (CTHIQTQ(3)), 125.81 (CTHIQTQ(6b)),
126.68 (CTHIQTQ(1)), 127.77 (d, C7-Ph(3), C7-Ph(5), J = 5.5 Hz),
127.81 (C7-Ph(2), C7-Ph(6)), 128.34 (d, C4-Ph(4), J = 22.1 Hz),
132.22 (CTHIQTQ(2)), 133.66 (CTHIQTQ(13b)), 133.90 (C7-Ph(1)),
135.16 (CTHIQTQ(7a)), 146.67 (CTHIQTQ(6a)), 149.98
(CTHIQTQ(7)), 158.09 (CTHIQTQ(5)), 159.61 (CTHIQTQ(11a)),
163.65 (CTHIQTQ(12a)).
5-Amino-8,9,10,11-tetrahydroisoquinolino[3΄,4΄:4,5]thieno-
[2,3-b]quinoline 13,13-dioxide (8b). The yield was 0.42 g (62%);
m.p. 322—324 °C (DMF—MeOH). Found (%): C, 64.31;
H, 4.39; N, 12.33; S, 9.61. C18H15N3O2S. Calculated (%):
C, 64.08; H, 4.48; N, 12.45; S, 9.90. IR, ν/cm–1: 3456, 3408,
3320, 3248 (NH2), 3216, 2952, 1640, 1624, 1616, 1584, 1564,
1544, 1512, 1432, 1384, 1292 (SO2), 1136 (SO2), 1024, 768.
1H NMR (DMSO-d6), δ: 1.70—1.80 (m, 2 H, 9-(CH2)THIQTQ);
1.82—1.92 (m, 2 H, 10-(CH2)THIQTQ); 2.86—3.00 (m, 4 H,
5-Amino-9-methyl-7-phenylpyrido[3΄,2΄:4,5]thieno[3,2-c]-
isoquinoline 11-oxide (6d). The yield was 0.25 g (35%); m.p.
252—256 °C (DMF—MeOH). Found (%): C, 70.41; H, 4.31;
N, 11.60; S, 9.03. C21H15N3OS. Calculated (%): C, 70.57; H, 4.23;
N, 11.76; S, 8.97. IR, ν/cm–1: 3434, 3322, 3288, 3204 (NH2),
3056, 1618, 1589, 1544, 1501, 1419, 1009 (S=O), 761, 696, 683.
1H NMR (DMSO-d6), δ: 2.65 (s, 3 H, 9-Me); 7.31 (br.s, 2 H,
NH2); 7.43 (s, 1 H, C(8)HPTI); 7.49—7.52 (m, 3 H, C(3)H7-Ph
,
8-(CH2)THIQTQ, 11-(CH2)THIQTQ); 7.65 (t, 1 H, C(3)HTHIQTQ,
C(4)H7-Ph, C(5)H7-Ph); 7.57 (t, 1 H, C(3)HPTI, J = 7.3 Hz);
7.63—7.67 (m, 2 H, C(2)H7-Ph,C(6)H7-Ph); 7.82 (t, 1 H,
C(2)HPTI, J = 7.3 Hz); 8.07 (d, 1 H, C(1)HPTI, J = 7.9 Hz);
8.35 (d, 1 H, C(4)HPTI, J = 8.5 Hz). 13C NMR (DMSO-d6),
J = 8.1 Hz); 7.87—7.93 (m, 2 H, C(1)HTHIQTQ, C(2)HTHIQTQ);
7.96 (s, 1 H, C(8)HTHIQTQ); 8.25 (br.s, 2 H, NH2); 8.44 (d, 1 H,
C(4)HTHIQTQ, J = 8.8 Hz). 13C NMR (DMSO-d6), δ: 21.75
(9-(CH2)THIQTQ), 22.21 (10-(CH2)THIQTQ), 28.79 (8-(CH2)THIQTQ),