May-Jun 2005
Fused Quinoline Heterocycles VI
571
was triturated with EtOH. The resulting solid product was col-
lected by filtration, washed with EtOH, dried and recrystallized
from EtOH to give 8a-c.
This compound was obtained as yellow crystals; yield: 0.385 g
(81%), mp: 280-282 °C; IR (KBr): ν = 2950 (aliph. CH), 1700
-1
1
(CO, ester) cm ; H NMR (DMSO-d ): δ = 0.93 (t, 3H, J = 7Hz,
6
CH ), 1.31 (t, 3H, J = 7Hz, CH ), 1.36 (m, 2H, CH ) 1.78 (m,
3
3
2
Ethyl 3-Amino-4-(butylamino)thieno[3,2-c]quinoline-2-car-
boxylate (8a) .
2H, CH ), 4.12 (t, 2H, J = Hz, CH ), 4.30 (q, 2H, J = 7Hz, CH ),
2
2
2
7.46 (t, 1H
, J = 8Hz), 7.68 (t, 1H
, J = 8Hz), 7.83 (d,
arom
arom
This compound was obtained as yellow crystals, yield: 0.390 g
1H
, J = 8Hz), 8.01 (d, 1H
, J = 8Hz), 8.21 (s, 1H, pyrimi-
arom
arom
+
(70%); mp: 123-124 °C; IR (KBr): ν = 3400, 3350 (NH, NH ),
dine CH); MS: m/z (%) = 352 (M -1, 71), 323 (15), 310 (57), 296
(54), 280 (37), 251 (55), 238 (66), 224 (100), 196 (60), 169 (21),
41 (11), 29 (25).
2
-1
1
2950, 2850 (aliph. CH), 1670 (CO, ester) cm ; H NMR
(DMSO-d ): δ = 0.94 (t, 3H, J = 7Hz, CH ), 1.30 (t, 3H, J = 7Hz,
6
3
CH ), 1.39 (m, 2H, CH ), 1.66 (m, 2H, CH ), 3.53 (q, 2H, J =
Anal. Calcd. for C H N O S (353.42): C, 64.57; H, 5.42; N,
3
2
2
19 19
3 2
7Hz, CH ), 4.28 (q, 2H, J = 7Hz, CH ), 6.57 (t, 1H, J = 5Hz,
11.89; S, 9.07. Found: C, 64.49; H, 5.32; N, 12.02; S, 9.23.
2
2
NH), 6.92 (s, 2H, NH ), 7.22 (t, 1H
, J = 8Hz), 7.51-7.57 (m,
2
arom
Ethyl 5-Cyclohexyl-5H-1-thia-3,5,6-triazaaceanthrylene-2-car-
boxylate (9b).
2H
), 7.83 (d, 1H
, J = 8Hz).
arom
arom
Anal. Calcd. for C H N O S (343.43): C, 62.95; H, 6.16; N,
18 21
3 2
This compound was obtained as yellow crystals, yield:
[0.370 g (72%) (route A) and 0.023 g (9%) (route B)], mp: 212-
213 °C; IR (KBr): ν = 2950, 2850 (aliph. CH), 1700 (CO, ester)
12.24; S, 9.34. Found: C, 63.09; H, 6.23; N, 12.39; S, 9.19.
Ethyl 3-Amino-4-(cyclohexylamino)thieno[3,2-c]quinoline-2-
carboxylate (8b).
-1
1
cm ; H NMR (DMSO-d ): δ = 1.30 (t, 3H, J = 7Hz, CH ) 1.47
6
3
(m, 3H, H
), 1.69-1.93 (m, 7H, H
), 4.28 (q, 2H, J = 7Hz,
This compound was obtained as yellow crystals; yield: 0.450 g
aliph
aliph
CH ), 4.84 (br t, 1H, J = 12Hz, H
), 7.41 (t, 1H
, J =
(75%), mp: 179-180 °C; IR (KBr): ν = 3450, 3350 (NH, NH ),
2
aliph
arom
2
-1
1
8Hz), 7.63 (t, 1H
, J = 8Hz), 7.79 (d, 1H
, J = 8Hz), 7.92
2950, 2850 (aliph. CH), 1670 (CO, ester) cm ; H NMR
arom
arom
(d, 1H
, J = 8Hz), 8.30 (s, 1H, pyrimidine CH); MS: m/z (%)
(DMSO-d ): δ = 1.30 (t, 3H, J = 7Hz, CH ), 1.34-1.44 (m, 5H,
arom
6
3
+
+
= 379 (M , 1), 378 (M -1, 46), 348 (8), 305 (20), 296 (86), 251
(74), 224 (100), 196 (72), 195 (43), 169 (29), 152 (43), 83 (7),
55 (44), 41 (45), 29 (21).
H
), 1.61-1.75 (m, 3H, H
), 2.04 (br, 2H, H
), 4.20 (br,
aliph
aliph
aliph
1H, H
), 4.28 (q, 2H, J = 7Hz, CH ), 6.23 (d, 1H, J = 7Hz,
aliph
2
NH), 6.80 (s, 2H, NH ), 7.21 (t, 1H
, J = 8Hz), 7.49-7.56 (m,
2
arom
Anal. Calcd. for C H N O S (379.46): C, 66.47; H, 5.58; N,
11.07; S, 8.45. Found: C, 66.29; H, 5.49; N, 11.13; S, 8.63.
2H
), 7.81 (d, 1H
, J = 8Hz).
21 21
3 2
arom
arom
Anal. Calcd. for C H N O S (369.46): C, 65.01; H, 6.27; N,
20 23
3 2
11.37; S, 8.68. Found: C, 65.19; H, 6.22; N, 11.49; S, 8.91.
Ethyl 5-iso-Butyl-5H-1-thia-3,5,6-triazaaceanthrylene-2-car-
boxylate (9c).
Ethyl 3-Amino-4-(iso-butylamino)thieno[3,2-c]quinoline-2-car-
boxylate (8c) .
This compound was obtained as yellow crystals, yield: 0.420 g
(88%), mp: 274-276 °C; IR (KBr): ν = 2950 (aliph. CH), 1700
This compound was obtained as yellow crystals; yield: 0.410 g
-1 1
(CO, ester) cm ; H NMR (DMSO-d ): δ = 1.05 (d, 6H, J = 7Hz,
6
(73%), mp: 148-150 °C.; IR (KBr): ν = 3450, 3300 (NH, NH ),
2
2 x CH ), 1.47 (t, 3H, J = 7Hz, CH ), 2.51 (m, 1H, CH), 4.37 (d,
-1
1
3
3
2950 (aliph. CH), 1670 (CO, ester) cm ; H NMR (DMSO-d ):
6
2H, J = 7Hz, CH ), 4.51 (q, 2H, J = 7Hz, CH ), 7.39 (t, 1H
, J
2
2
arom
δ = 0.95 (d, 6H, J = 7Hz, 2 x CH ), 1.30 (t , 3H, J = 7Hz, CH ),
3
3
= 8Hz), 7.61 (t, 1H
, J = 8Hz), 7.83 (d, 1H
, J = 8Hz), 7.90
arom
arom
2.07 (m, 1H, CH), 3.49 (d, 2H, J = 6Hz, CH ), 4.28 (q, 2H, J =
2
(d, 1H
, J = 8Hz), 8.25 (s, 1H, pyrimidine CH); MS: m/z (%)
arom
7Hz, CH ), 6.60 (t, 1H, J = 5Hz, NH), 6.90 (s, 2H, NH ), 7.22 (t,
2
2
+
= 353 (M , 13), 297 (18), 282 (4), 252 (7), 239 (6), 225 (100),
197 (17), 153 (7), 57 (3).
1H
, J = 8Hz), 7.54 (m, 2H
), 7.84 (d, 1H , J = 8Hz).
arom
arom
arom
Anal. Calcd. for C H N O S (343.43): C, 62.95; H, 6.16; N,
18 21
3 2
Anal. Calcd. for C H N O S (353.42): C, 64.57; H, 5.42; N,
19 19
3 2
12.24; S, 9.34. Found: C, 63.13; H, 6.28; N, 12.36; S, 9.17.
11.89; S, 9.07. Found: C, 64.73; H, 5.29; N, 11.99; S, 8.89.
Ethyl 5-alkyl-5H-1-thia-3,5,6-triazaaceanthrylene-2-carboxyl-
ates (9a-c); General procedure (Route A).
5-Benzyl-5H-1-thia-3,5,6-triazaaceanthrylene-2-carboxylic Acid
Benzylamide (11).
A mixture of aminothienoquinolines 8a-c (1.35 mmol) and tri-
ethyl orthoformate (15 mL) was heated under reflux for 3 h.
After concentration and cooling to ambient temperature, the
resulting precipitate was collected by filtration, washed with
MeOH, dried and recrystallized from DMF.
A solution of 4 (1.53 g, 5 mmol) in excess of benzylamine (7d,
15 mL) was heated at reflux for 4 h. The mixture was evaporated
to dryness in vacuo to give 10, as a clear oil. Triethyl orthofor-
mate (15 mL) was added to 10, and the mixture was refluxed for
24 h (monitored by TLC). After concentration and cooling to
ambient temperature, the resulting solid product was collected by
filtration, washed with a small amount of EtOH, dried and recrys-
tallized from DMF to afford 1.43 g (64%) of 11 as colorless crys-
tals, mp: 239-240 °C; IR (KBr): ν = 3350 (NH), 3050 (arom.
Ethyl 5-Cyclohexyl-5H-1-thia-3,5,6-triazaaceanthrylene-2-car-
boxylate (9b) (Route B).
A solution of 8b (0.250 g, 0.68 mmol) in acetic anhydride (5
mL) was refluxed for 5 h. After concentration and cooling to
ambient temperature, the resulting solid product was chro-
matographed on a preparative TLC using (toluene:ethyl acetate,
8:2) as eluent to give 9b after extraction with acetone followed by
recrystallization form EtOH.
–1
1
CH), 1680 (CO, amide) cm ; H NMR (DMSO-d ): δ = 4.81 (d,
6
2H, J = 5Hz, CH ), 5.32 (s, 2H, CH ), 6.98 (d, 1H
, J = 8Hz),
2
2
arom
7.21-7.73 (m, 13H, 12H
+ pyrimidine CH), 8.09 (d, 1H
, J
arom
arom
+
= 8Hz), 8.32 (t, 1H, J = 5Hz, NH); MS: m/z (%) = 447 (M -1, 3),
432 (100), 329 (88), 301 (11), 199 (11), 106 (7), 91 (93), 77 (8).
Anal. Calcd. for C H N OS (448.54): C, 72.30; H, 4.49; N,
Ethyl 5-Butyl-5H-1-thia-3,5,6-triazaaceanthrylene-2-carboxylate
(9a).
27 20
4
12.49; S, 7.15. Found: C, 72.25; H, 4.65; N, 12.31; S, 7.24.