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M.-G. Liu et al. / Tetrahedron 64 (2008) 9052–9059
4.4.3. 8-Amino-2-di(i-propyl)amino-7-ethoxycarbonyl-3-phenyl-
thieno[30,20:4,5]thieno[3,2-d]pyrimidin-4(3H)-one (10c)
IR (KBr): 3487, 3380, 1684, 1520, 1311, 1249 cmꢀ1. 1H NMR (CDCl3,
400 MHz):
d
7.48–7.30 (m, 4H), 6.43 (br, 2H), 4.33 (q, J¼7.2 Hz, 2H),
Operation as above with di(i-propyl)amine (0.20 g, 2 mmol),
compound 10c (0.73 g, 78%) was isolated as colorless crystals. Mp:
2.73 (s, 6H), 1.38 (t, J¼7.2 Hz, 3H). MS m/z: 448 (Mþ, 100), 358 (36),
277 (22), 125 (30), 44 (47). Anal. Calcd for C19H17ClN4O3S2: C, 50.83;
H, 3.82; N, 12.48. Found: C, 50.97; H, 3.93; N, 12.24.
235–237 ꢁC, IR (KBr): 3477, 3350, 1674, 1514, 1308, 1250 cmꢀ1 1H
.
NMR (CDCl3, 400 MHz):
d 7.50–7.29 (m, 5H), 6.44 (br, 2H), 4.34 (q,
J¼6.8 Hz, 2H), 3.64–3.57 (m, 2H), 1.38 (t, J¼7.2 Hz, 3H), 1.17 (d,
4.4.9. 8-Amino-3-(4-chlorophenyl)-2-(di-n-propyl)amino-7-
ethoxycarbonyl-thieno[30,20:4,5]thieno[3,2-d]pyrimidin-
4(3H)-one (10i)
J¼6.8 Hz, 12H). 13C NMR (CDCl3, 150 MHz):
d 164.0, 158.9, 156.7,
150.2, 148.7, 138.5, 130.9, 129.3, 128.8, 128.0, 117.5, 60.0, 50.1, 21.5,
14.4. MS m/z: 470 (Mþ,100), 427 (86), 381 (95), 367 (20). Anal. Calcd
for C23H26N4O3S2: C, 58.70; H, 5.57; N, 11.90. Found: C, 58.92; H,
5.78; N, 11.77.
Operation as abovewith 4-chlorophenylisocyanate (0.31 g, 2 mmol)
and di(n-propyl)amine (0.20 g, 2 mmol), compound 10i (0.89 g, 88%)
was isolated as colorless crystals. Mp: 190–191 ꢁC, IR (KBr): 3495, 3375,
1668,1521,1315,1250 cmꢀ1.1H NMR (CDCl3, 400 MHz):
d 7.49–7.26 (m,
4.4.4. 8-Amino-2-di(n-butyl)amino-7-ethoxycarbonyl-3-phenyl-
thieno[30,20:4,5]thieno[3,2-d]pyrimidin-4(3H)-one (10d)
4H), 6.41 (br, 2H), 4.33 (q, J¼6.8 Hz, 2H), 3.02 (t, J¼7.2 Hz, 4H),1.40–1.34
(m, 7H), 0.77 (t, J¼7.2 Hz, 6H). MS m/z: 504(Mþ,100), 415 (55), 277 (37),
153 (36), 100 (46), 43 (57). Anal. Calcd for C23H25ClN4O3S2: C, 54.70; H,
4.99; N, 11.09. Found: C, 54.62; H, 4.83; N, 11.15.
Operation as above with di(n-butyl)amine (0.26 g, 2 mmol),
compound 10d (0.81 g, 81%) was isolated as colorless crystals. Mp:
173–175 ꢁC, IR (KBr): 3482, 3379, 1669, 1526, 1312, 1256 cmꢀ1 1H
.
NMR (CDCl3, 400 MHz):
d
7.52–7.30 (m, 5H), 6.44 (br, 2H), 4.34 (q,
4.4.10. 8-Amino-3-(4-chlorophenyl)-2-(di-n-pentyl)amino-7-
ethoxycarbonyl-thieno[30,20:4,5]thieno[3,2-d]pyrimidin-
4(3H)-one (10j)
J¼7.2 Hz, 2H), 3.05 (t, J¼7.6 Hz, 4H), 1.38 (t, J¼7.2 Hz, 3H), 1.30–1.10
(m, 8H), 0.84 (t, J¼7.2 Hz, 6H). MS m/z: 498 (Mþ, 100), 454 (14), 395
(35), 252 (13), 105 (16). Anal. Calcd for C25H30N4O3S2: C, 60.22; H,
6.06; N, 11.24. Found: C, 60.27; H, 6.23; N, 11.07.
Operation as above with 4-chlorophenyl isocyanate (0.31 g,
2 mmol) and di(n-pentyl)amine (0.31 g, 2 mmol), compound 10j
(0.87 g, 78%) was isolated as colorless crystals. Mp: 163–164 ꢁC, IR
4.4.5. 8-Amino-2-di(i-butyl)amino-7-ethoxycarbonyl-3-phenyl-
thieno[30,20:4,5]thieno[3,2-d]pyrimidin-4(3H)-one (10e)
(KBr): 3480, 3367, 1677, 1521, 1314, 1251 cmꢀ1 1H NMR (CDCl3,
.
400 MHz):
d
7.48–7.26 (m, 4H), 6.42 (br, 2H), 4.34 (q, J¼7.2 Hz, 2H),
Operation as above with di(i-butyl)amine (0.26 g, 2 mmol),
compound 10e (0.84 g, 84%) was isolated as colorless crystals. Mp:
3.04 (t, J¼7.6 Hz, 4H), 1.38 (t, J¼7.2 Hz, 3H), 1.31–1.10 (m, 12H), 0.87
(t, J¼7.2 Hz, 6H). MS m/z: 560 (Mþ, 100), 443 (52), 358 (47), 277
(52), 125 (59), 77 (27). Anal. Calcd for C27H33ClN4O3S2: C, 57.79; H,
5.93; N, 9.98. Found: C, 57.71; H, 5.95; N, 9.80.
164–166 ꢁC, IR (KBr): 3479, 3365, 1679, 1516, 1313, 1253 cmꢀ1 1H
.
NMR (CDCl3, 400 MHz):
d 7.53–7.32 (m, 5H), 6.44 (br, 2H), 4.34 (q,
J¼6.8 Hz, 2H), 2.87 (d, J¼7.2 Hz, 4H), 1.92–1.85 (m, 2H), 1.38 (t,
J¼7.2 Hz, 3H), 0.81 (d, J¼6.4 Hz, 12H). MS m/z: 498 (Mþ, 22), 367
(90), 320 (86), 250 (99), 221 (98), 189 (67), 104 (100), 77 (99). Anal.
Calcd for C25H30N4O3S2: C, 60.21; H, 6.06; N, 11.24. Found: C, 60.14;
H, 6.27; N, 11.15.
4.4.11. 8-Amino-3-(4-chlorophenyl)-2-(di-n-hexyl)amino-7-
ethoxycarbonyl-thieno[30,20:4,5]thieno[3,2-d]pyrimidin-
4(3H)-one (10k)
Operation as above with 4-chlorophenyl isocyanate (0.31 g,
2 mmol) and di(n-hexyl)amine (0.37 g, 2 mmol), compound 10k
(0.88 g, 75%) was isolated as colorless crystals. Mp: 127–128 ꢁC, IR
4.4.6. 8-Amino-2-di(n-pentyl)amino-7-ethoxycarbonyl-3-phenyl-
thieno[30,20:4,5]thieno[3,2-d]pyrimidin-4(3H)-one (10f)
(KBr): 3498, 3383, 1667, 1518, 1311, 1251 cmꢀ1 1H NMR (CDCl3,
.
Operation as above with di(n-pentyl)amine (0.31 g, 2 mmol),
compound 10f (0.78 g, 74%) was isolated as colorless crystals. Mp:
400 MHz):
d
7.48–7.25 (m, 4H), 6.41 (br, 2H), 4.33 (q, J¼6.8 Hz, 2H),
3.04 (t, J¼7.6 Hz, 4H), 1.38 (t, J¼7.2 Hz, 3H), 1.30–1.12 (m, 16H), 0.88
156–158 ꢁC, IR (KBr): 3480, 3367, 1665, 1521, 1313, 1249 cmꢀ1
.
1H
(t, J¼6.8 Hz, 6H). 13C NMR (CDCl3, 150 MHz):
d 163.7, 157.8, 157.2,
NMR (CDCl3, 400 MHz):
d
7.52–7.30 (m, 5H), 6.44 (br, 2H), 4.34 (q,
150.4, 148.5, 135.9, 134.0, 130.5, 130.3, 128.9, 116.4, 59.8, 51.3, 31.3,
26.9, 26.5, 22.3,14.2,13.8. MS m/z: 588 (Mþ,100), 457 (42), 277 (35),
125 (31), 43 (66). Anal. Calcd for C29H37ClN4O3S2: C, 59.12; H, 6.33;
N, 9.51. Found: C, 59.37; H, 6.11; N, 9.38.
J¼7.2 Hz, 2H), 3.04 (t, J¼7.6 Hz, 4H), 1.38 (t, J¼7.2 Hz, 3H), 1.31–1.06
(m, 12H), 0.85 (t, J¼7.2 Hz, 6H). 13C NMR (CDCl3, 150 MHz):
d 164.0,
158.2, 157.5, 150.7, 148.8, 137.5, 130.7, 128.9, 128.8, 128.1, 116.7, 59.9,
51.4, 29.0, 26.7, 22.2, 14.3, 13.9. MS m/z: 526 (Mþ, 31), 409 (18), 324
(19), 91 (14), 44 (100). Anal. Calcd for C27H34N4O3S2: C, 61.57; H,
6.51; N, 10.64. Found: C, 61.42; H, 6.52; N, 10.81.
4.4.12. 8-Amino-7-ethoxycarbonyl-3-(4-fluorophenyl)-2-
methyl(phenyl)amino-thieno[30,20:4,5]thieno[3,2-d]pyrimidin-
4(3H)-one (10l)
4.4.7. 8-Amino-2-di(n-hexyl)amino-7-ethoxycarbonyl-3-phenyl-
thieno[30,20:4,5]thieno[3,2-d]pyrimidin-4(3H)-one (10g)
Operation as above with di(n-hexyl)amine (0.37 g, 2 mmol),
compound 10g (0.79 g, 71%) was isolated as colorless crystals. Mp:
>300 ꢁC, IR (KBr): 3497, 3381, 1667, 1519, 1312, 1233 cmꢀ1. 1H NMR
Operation as above with 4-fluorophenyl isocyanate (0.27 g,
2 mmol) and N-methyl-N-phenylamine (0.27 g, 2 mmol), com-
pound 10l (0.86 g, 87%) was isolated as colorless crystals. Mp: 276–
278 ꢁC, IR (KBr): 3481, 3362, 1671, 1509, 1320, 1221 cmꢀ1. 1H NMR
(CDCl3, 400 MHz):
d 7.12–6.63 (m, 9H), 6.50 (br, 2H), 4.35 (q,
(CDCl3, 400 MHz):
d
7.51–7.30 (m, 5H), 6.43 (br, 2H), 4.34 (q,
J¼7.0 Hz, 2H), 3.34 (s, 3H), 1.39 (t, J¼7.2 Hz, 3H). 13C NMR (CDCl3,
J¼6.8 Hz, 2H), 3.04 (t, J¼7.6 Hz, 4H), 1.38 (t, J¼7.2 Hz, 3H), 1.30–1.10
(m, 16H), 0.87 (t, J¼7.2 Hz, 6H). MS m/z: 554 (Mþ, 89), 423 (41), 353
(37), 324 (53), 167 (21), 43 (100). Anal. Calcd for C29H38N4O3S2: C,
62.78; H, 6.90; N, 10.10. Found: C, 62.95; H, 6.86; N, 10.34.
150 MHz): d 164.2, 162.5, 160.8, 158.1, 156.6, 150.6, 149.2, 146.4,
132.2, 131.1, 130.5, 130.4, 129.4, 125.9, 125.3, 118.6, 115.4, 115.2, 60.2,
43.0, 14.5. MS m/z: 494 (Mþ, 100), 447 (22), 342 (33), 224 (16), 109
(13). Anal. Calcd for C24H19FN4O3S2: C, 58.29; H, 3.87; N, 11.33.
Found: C, 58.41; H, 3.72; N, 11.39.
4.4.8. 8-Amino-3-(4-chlorophenyl)-2-dimethylamino-7-
ethoxycarbonyl-thieno[30,20:4,5]thieno[3,2-d]pyrimidin-
4(3H)-one (10h)
Operation as above with 4-chlorophenyl isocyanate (0.31 g,
2 mmol) and dimethylamine (0.25 g, 40%, 0.2 mmol), compound
10h (0.74 g, 83%) was isolated as colorless crystals. Mp: 262–264 ꢁC,
4.4.13. 8-Amino-7-ethoxycarbonyl-3-(4-fluorophenyl)-2-
(pyrrolidin-1-yl)-thieno[30,20:4,5]thieno[3,2-d]pyrimidin-
4(3H)-one (10m)
Operation as above with 4-fluorophenyl isocyanate (0.27 g,
2 mmol) and pyrrolidine (0.14 g, 2 mmol), compound 10m (0.82 g,