8156
W.-J. Li et al. / Tetrahedron 66 (2010) 8151e8159
d
7.69e6.97 (m, 15H, AreH and NH), 5.68 (s, 1H, CH), 4.24 (q,
75 (16), 56 (95). Anal. Calcd for C22H21ClN4O3:, C, 62.19; H, 4.98; N,
13.19. Found: C, 62.16; H, 4.73; N, 13.28.
J¼7.2 Hz, 2H, OCH2), 2.20 (s, 3H, CH3), 1.21 (t, J¼7.2 Hz, 3H, CH3). 13
C
NMR (CDCl3, 100 MHz):
d 165.6, 150.6, 149.5, 145.1, 143.3, 138.8,
136.6, 129.2, 129.1, 129.0, 128.6, 128.4, 127.2, 123.4, 123.0, 122.9,
122.4, 119.7, 101.1, 60.6, 53.1, 18.5, 14.1. MS m/z: 452 (Mþꢀ1, 26), 423
(13), 378 (12), 258 (10), 145 (21), 118 (66), 77 (100). Anal. Calcd for
C27H24N4O3: C, 71.67; H, 5.35; N, 12.38. Found: C, 71.72; H, 5.30;
N, 12.24.
4.4.13. 6-(4-Chlorophenylamino)-2-methyl-3-phenyl-1-ethoxy-
carbonyl-3,11b-dihydro-4H-pyrimido[1,6-c]quinazolin-4-one
(4m). Operation as above with iminophosphorane 2e (0.61 g,
1 mmol) and 4-chlorophenylisocyanate (0.15 g, 1 mmol) at room
temperature for 2 h, compound 4m (0.34 g, 69%) was also isolated
as white solid. Mp: 153e155 ꢁC. IR (KBr): 3304, 1675, 1631 cmꢀ1. 1H
4.4.9. 1-Ethoxycarbonyl-6-isopropylamino-2-methyl-3-phenyl-
3,11b-dihydro-4H-pyrimido[1,6-c]quinazolin-4-one (4i). Operation
as above with iminophosphorane 2e (0.61 g, 1 mmol) and iso-
propylisocyanate (0.09 g, 1 mmol) at refluxing temperature for 4 h,
compound 4i (0.27 g, 64%) was also isolated as white solid. Mp:
200e202 ꢁC. IR (KBr): 3340, 2972, 1693, 1629 cmꢀ1. 1H NMR (CDCl3,
NMR (CDCl3, 400 MHz): d 7.64e7.00 (m, 14H), 5.66 (s, 1H), 4.26 (q,
J¼7.2 Hz, 2H), 2.21 (s, 3H), 1.23 (t, J¼7.2 Hz, 3H). MS m/z: 486 (Mþ,
100), 457 (69), 412 (31), 275 (22), 118 (59), 77 (35). Anal. Calcd for
C27H23ClN4O3: C, 66.60; H, 4.76; N, 11.51. Found: C, 66.75; H, 4.54;
N, 11.78.
400 MHz):
d
7.38e6.92 (m, 9H, AreH), 5.55 (s, 1H, CH), 5.16 (d,
4.4.14. 2,3-Dimethyl-1-ethoxycarbonyl-6-(4-fluorophenylamino)-
3,11b-dihydro-4H-pyrimido[1,6-c]quinazolin-4-one (4n). Operation
as above with iminophosphorane 2d (0.55 g, 1 mmol) and 4-fluo-
rophenylisocyanate (0.14 g, 1 mmol) at room temperature for 1 h,
compound 4n (0.25 g, 62%) was also isolatedꢀa1s white solid. Mp:
J¼8.0 Hz, 1H, NH), 4.30e4.19 (m, 3H, OCH2 and NCH), 2.18 (s, 3H,
CH3), 1.27 (d, J¼6.8 Hz, 6H, 2CH3), 1.20 (t, J¼7.2 Hz, 3H, CH3). 13C
NMR (CDCl3, 100 MHz):
d 165.7, 150.4, 149.2, 148.1, 144.2, 136.9,
129.2, 128.7, 128.5, 128.4, 127.0, 122.4, 122.3, 122.2, 100.7, 60.4, 53.0,
43.5, 22.5, 21.9, 18.4, 14.0. MS m/z: 418 (Mþ, 100), 389 (56), 344 (36),
304 (30), 274 (29), 118 (87). Anal. Calcd for C24H26N4O3: C, 68.88; H,
6.26; N, 13.39. Found: C, 68.63; H, 6.12; N, 13.57.
203e204 ꢁC. IR (KBr): 3309, 1676, 1634 cm
.
1H NMR (CDCl3,
400 MHz):
d 7.72e6.87 (m, 9H), 5.52 (s, 1H), 4.25e4.21 (m, 2H),
3.16 (s, 3H), 2.62 (s, 3H), 1.20 (t, J¼7.2 Hz, 3H). MS m/z: 408 (Mþ,
100), 379 (67), 334 (48), 242 (30), 213 (22), 56 (41). Anal. Calcd for
C22H21FN4O3: C, 64.70; H, 5.18; N, 13.72. Found: C, 64.78; H, 5.33;
N, 13.57.
4.4.10. 2,3-Dimethyl-1-ethoxycarbonyl-6-isopropylamino-3,11b-
dihydro-4H-pyrimido[1,6-c]quinazolin-4-one (4j). Operation as
above with iminophosphorane 2d (0.55 g, 1 mmol) and iso-
propylisocyanate (0.09 g, 1 mmol) at refluxing temperature for
4 h, compound 4j (0.28 g, 78%) was also isolated as white solid.
4.4.15. 1-Ethoxycarbonyl-6-(4-fluorophenylamino)-2-methyl-3-phe-
nyl-3,11b-dihydro-4H-pyrimido[1,6-c]quinazolin-4-one
(4o). Operation as above with iminophosphorane 2e (0.61 g,
1 mmol) and 4-fluorophenylisocyanate (0.14 g, 1 mmol) at room
temperature for 2 h, compound 4o (0.32 g, 69%) was also isolatedꢀa1s
Mp: 154e156 ꢁC. IR (KBr): 3366, 2974, 1685, 1631 cmꢀ1
(CDCl3, 400 MHz):
.
1H NMR
7.25e6.81 (m, 4H, AreH), 5.41 (s, 1H, CH),
d
5.02 (d, J¼8.0 Hz, 1H, NH), 4.31e4.17 (m, 3H, OCH2 and NCH), 3.13
(s, 3H, NCH3), 2.59 (s, 3H, CH3), 1.33 (d, J¼6.4 Hz, 3H, CH3), 1.29 (d,
J¼6.4 Hz, 3H, CH3), 1.18 (t, J¼7.2 Hz, 3H, CH3). 13C NMR (CDCl3,
white solid. Mp: 126e128 ꢁC. IR (KBr): 3312, 2981, 1677, 1635 cm
.
1H NMR (CDCl3, 400 MHz):
d 6.95e7.66 (m, 14H, AreH and NH),
100 MHz):
d
165.9, 151.2, 149.8, 148.4, 144.2, 128.4, 127.0, 122.5,
5.67 (s, 1H, CH), 4.25 (q, J¼7.2 Hz, 2H, OCH2), 2.21 (s, 3H, CH3), 1.22
122.4, 122.2, 100.2, 60.4, 52.4, 43.6, 30.7, 22.7, 22.1, 16.6, 14.1. MS
m/z: 355 (Mþꢀ1, 100), 326 (27), 286 (9), 240 (11), 44 (9). Anal.
Calcd for C19H24N4O3: C, 64.03; H, 6.79; N, 15.72. Found: C, 64.27;
H, 6.78; N, 15.53.
(t, J¼7.2 Hz, 3H, CH3). 13C NMR (CDCl3, 100 MHz):
d 165.6, 159.8,
157.4, 150.9, 149.5, 145.1, 143.2, 136.7, 134.9, 129.5, 128.8, 128.7,
127.2, 123.6, 123.1, 122.5, 121.3, 121.2, 115.1, 114.9, 101.4, 60.8, 53.2,
18.5, 14.2. MS m/z: 470 (Mþ, 100), 441 (64), 396 (39), 304 (18), 275
(20), 118 (43), 77 (34). Anal. Calcd for C27H23FN4O3: C, 68.93; H,
4.93; N, 11.91. Found: C, 68.68; H, 4.74; N, 11.95.
4.4.11. 1-Ethoxycarbonyl-2-methyl-6-(3-methylphenylamino)-3,11b-
dihydro-4H-pyrimido[1,6-c]quinazoline-4-thione (4k). Operation as
above with 3-methylphenylisocyanate (0.13 g, 1 mmol) at room
temperature for 4 h, compound 4k (0.29 g, 72%) was also isolatedꢀa1s
4.4.16. 1-Ethoxycarbonyl-3-ethyl-6-isopropylamino-2-methyl-3,11b-
dihydro-4H-pyrimido[1,6-c]quinazolin-4-one (4p). Operation as
above with iminophosphorane 2c (0.56 g, 1 mmol) and iso-
propylisocyanate (0.09 g, 1 mmol) at refluxing temperature for 4 h,
compound 4p (0.27 g, 73%) was also isolated as white solid. Mp:
white solid. Mp: 136e138 ꢁC. IR (KBr): 3393, 2979, 1635, 1588 cm
.
1H NMR (CDCl3, 400 MHz):
d 8.02 (s, 1H, NH), 7.59e6.84 (m, 9H,
AreH and NH), 5.64 (s, 1H, CH), 4.26e4.23 (m, 2H, OCH2), 2.42 (s,
3H, CH3), 2.39 (s, 3H, CH3), 1.23 (t, J¼7.2 Hz, 3H, CH3). 13C NMR
94e96 ꢁC. IR (KBr): 3350, 2977, 1685, 1630 cmꢀ1
.
1H NMR (CDCl3,
d 7.24e6.81 (m, 4H, AreH), 5.37 (s, 1H, CH), 5.01 (d,
(CDCl3, 100 MHz):
d
175.5, 165.3, 145.1, 143.8, 142.6, 138.8, 137.9,
400 MHz):
128.9, 128.8, 127.5, 124.6, 123.7, 123.4, 122.8, 120.4, 117.1, 99.7, 60.8,
54.4, 21.6, 17.8, 14.2. MS m/z: 406 (Mþ, 1), 376 (7), 275 (86), 216 (34),
170 (40), 128 (86), 76 (100). Anal. Calcd for C22H22N4O2S: C, 65.00;
H, 5.46; N, 13.78. Found: C, 65.24; H, 5.32; N, 13.85.
J¼7.6 Hz, 1H, NH), 4.31e4.16 (m, 3H, OCH2 and NCH), 3.70e3.63 (m,
2H, NCH2), 2.61 (s, 3H, CH3), 1.37e1.09 (m, 12H, 4CH3). 13C NMR
(CDCl3, 100 MHz):
d 166.0, 150.6, 149.2, 148.6, 144.1, 128.3, 127.1,
122.4, 122.3, 122.2, 100.4, 60.3, 52.4, 43.5, 38.6, 22.7, 22.1, 15.9, 14.6,
14.1. MS m/z: 370 (Mþ, 20), 341 (6), 299 (8), 227 (16), 69 (100). Anal.
Calcd for C20H26N4O3: C, 64.84; H, 7.07; N, 15.12. Found: C, 64.93; H,
7.21; N, 15.04.
4.4.12. 6-(4-Chlorophenylamino)-2,3-dimethyl-1-ethoxycarbonyl-
3,11b-dihydro-4H-pyrimido[1,6-c]quinazolin-4-one (4l). Operation
as above with iminophosphorane 2d (0.55 g, 1 mmol) and
4-chlorophenylisocyanate (0.15 g, 1 mmol) at room temperature for
1 h, compound 4l (0.25 g, 60%) was also isolateꢀd1as white solid. Mp:
4.4.17. 1-Ethoxycarbonyl-2-methyl-3-phenyl-6-phenyl amino-3,11b-
dihydro-4H-pyrimido[1,6-c]quinazoline-4-thione (4q). Operation as
above with iminophosphorane 2f (0.63 g, 1 mmol) at room tem-
perature for 2 h, compound 4q (0.34 g, 72%) was also isolated ꢀa1s
white solid. Mp: 224e225 ꢁC. IR (KBr): 3410, 2982, 1681, 1637 cm
.
204e205 ꢁC. IR (KBr): 3328, 1680, 1634 cm
.
1H NMR (CDCl3,
400 MHz):
d
7.70 (d, J¼8.8 Hz, 2H, AreH), 7.38 (s, 1H, NH),
7.30e6.87 (m, 6H, AreH), 5.52 (s, 1H, CH), 4.24e4.21 (m, 2H, OCH2),
3.16 (s, 3H, NCH3), 2.62 (s, 3H, CH3), 1.20 (t, J¼7.2 Hz, 3H, CH3). 13
C
1H NMR (CDCl3, 400 MHz):
d 7.75e6.73 (m, 15H, AreH and NH),
NMR (CDCl3, 100 MHz):
d
165.7, 151.3, 149.8, 144.9, 142.9, 137.6,
5.64 (s, 1H, CH), 4.30e4.24 (m, 2H, OCH2), 2.21 (s, 3H, CH3), 1.24 (t,
128.7, 128.6, 127.8, 127.2, 123.6, 123.1, 122.7, 120.6, 100.4, 60.7, 52.5,
J¼7.2 Hz, 3H, CH3). 13C NMR (CDCl3, 100 MHz):
d 179.8, 165.6, 147.4,
147.0,143.1,140.5,138.5,130.7,129.6,128.9,128.7,128.4,127.4,123.7,
30.9, 16.7, 14.2. MS m/z: 424 (Mþ, 100), 395 (56), 350 (48), 242 (28),