9922
S. Grosjean et al. / Tetrahedron 66 (2010) 9912e9924
HRMS (MALDI): calcd for C15H11F3N3O2 [MþH]þ 322.0803; found
1692 (s), 1640 (m), 1571 (s), 1505 (s), 1452 (m), 1372 (m), 1348 (w)
cmꢁ1. 1H NMR (300 MHz, CDCl3):
322.0808.
d¼2.46 (s, 3H, PhCH3), 3.91 (s, 3H,
CO2CH3), 7.17 and 7.40 (AB system, 4H, J¼8.4 Hz, Har), 7.47 and 7.69
4.10.9. 7-Methoxy-1-p-tolyl-3-trifluoromethyl-1H-pyrimido[1,2-a]
pyrimidine-2,6-dione (9i). Yellow solid (53 mg, 95%). Mp
(m, 5H, Har), 8.67 (s, 1H, H4), 9.00 (s, 1H, H8) ppm. 13C NMR (75 MHz,
CDCl3):
d
¼21.5 (PhCH3), 52.5 (CO2CH3), 107.4 (C7), 123.8 (C3),
164e165 ꢀC. IR (KBr):
n
¼3049 (w), 2959 (w), 2854 (w), 1721 (s),
1705 (s), 1660 (m), 1595 (s), 1513 (s), 1458 (w), 1384 (w), 1367
(m), 1268 (s), 1040 (m) cmꢁ1 1H NMR (300 MHz, CDCl3):
127.8e130.7 (9CHar), 129.7 (C4), 131.0, 132.2, and 140.0 (3Car), 151.6
(C9a), 154.3 (C8), 159.4 (C6), 161.0 (C2), 164.2 (CO2CH3) ppm. MS (EI,
70 eV): m/z (%)¼388 (10), 387 (45) [M]þ, 386 (68),175 (15),132 (19),
116 (100),102 (30), 91 (35), 89 (55), 77 (17), 65 (25). HRMS (MALDI):
calcd for C22H18N3O4 [MþH]þ 388.1292; found 388.1284.
.
d¼2.44
(s, 3H, PhCH3), 3.83 (s, 3H, OCH3), 7.12 and 7.36 (AB system, 4H,
J¼8.0 Hz, Har), 7.41 (s, 1H, H8), 9.12 (s, 1H, H4) ppm. 13C NMR
(75 MHz, CDCl3):
d
¼21.4 (PhCH3), 57.2 (OCH3), 112.9 (q, J¼33.3 Hz,
C3), 121.1 (q, J¼195.8 Hz, CF3), 128.0 and 130.6 (4CHar), 131.5 (Car),
4.10.14. 3-Phenyl-1-p-tolyl-1H-pyrimido[1,2-a]pyrimidine-2,6-dione
131.9 (C8), 133.7 (C4), 139.8 (C7), 140.4 (Car), 142.5 (C9a), 153.5 and
(9n). White solid (38 mg, 86%). Mp 239e240 ꢀC. IR (KBr):
(w), 3069 (w), 3035 (w), 2950 (w), 2923 (w), 1710 (s), 1701 (s), 1635
(w), 1571 (m), 1504 (s), 1488 (s), 1444 (m), 1351 (m), 815 (m), 786
n
¼3099
155.2 (C2 and C6) ppm. 19F NMR (300 MHz, CDCl3):
d
¼ꢁ64.8 (CF3)
ppm. MS (EI, 70 eV): m/z (%)¼352 (19), 351 (100) [M]þ, 350 (73),
260 (35), 163 (38), 117 (33), 91 (74), 65 (26), 53 (26). HRMS
(MALDI): calcd for C16H12F3N3NaO3 [MþNa]þ 374.0728; found
374.0725.
(m) cmꢁ1. 1H NMR (300 MHz, CDCl3):
d
¼2.45 (s, 3H, PhCH3), 6.22 (d,
1H, J¼6.6 Hz, H7), 7.19 and 7.39 (AB system, 4H, J¼8.1 Hz, Har), 7.45
and 7.70 (m, 5H, Har), 7.83 (d, 1H, J¼6.6 Hz, H8), 8.93 (s, 1H, H4) ppm.
13C NMR (75 MHz, CDCl3):
d
¼21.5 (PhCH3), 105.8 (C7), 123.0 (C3),
4.10.10. 7-Methoxycarbonyl-1-p-tolyl-1H-pyrimido[1,2-a]pyrimi-
dine-2,6-dione (9j). White solid (35 mg, 72%). Mp 246e248 ꢀC. IR
128.0e130.7 (9CHar), 129.6 (C4), 131.4, 132.8, and 139.6 (3 Car), 149.6
(C9a), 154.8 (C8), 157.6 (C6), 159.7 (C2) ppm. MS (EI, 70 eV): m/z (%)¼
330 (10), 329 (69) [M]þ, 328 (100), 300 (10), 185 (13), 117 (17), 116
(46), 91 (13), 77 (5). HRMS (MALDI): calcd for C20H16N3O2 [MþH]þ
330.1237; found 330.1234.
(KBr):
(w), 1754 (s), 1722 (s), 1687 (m), 1646 (m), 1567 (m), 1519 (s), 1500
(s), 1455 (s), 1387 (m), 1352 (w), 865 (w), 814 (m) cmꢁ1 1H NMR
n
¼3092 (w), 3066 (w), 3040 (w), 2956 (w), 2924 (w), 2850
.
(300 MHz, CDCl3):
d
¼2.46 (s, 3H, PhCH3), 3.90 (s, 3H, CO2CH3), 6.56
(d, 1H, J¼8.3 Hz, H3), 7.12 and 7.39 (AB system, 4H, J¼7.5 Hz, Har),
8.65 (s, 1H, H8), 8.86 (d, 1H, J¼8.3 Hz, H4) ppm. 13C NMR (75 MHz,
4.10.15. 7-Methoxy-3-phenyl-1-p-tolyl-1H-pyrimido[1,2-a]pyrimi-
dine-2,6-dione (9o). Yellow solid (36 mg, 89%). Mp 215e216 ꢀC. IR
CDCl3):
d
¼21.6 (PhCH3), 52.5 (CO2CH3), 107.7 (C7), 111.5 (C3), 127.7
(KBr):
(s), 1701 (s), 1633 (w), 1584 (s), 1543 (s), 1494 (m), 1446 (m),
1385 (m), 1071 (m), 808 (w), 786 (m) cmꢁ1 1H NMR (300 MHz,
CDCl3):
¼2.45 (s, 3H, PhCH3), 3.84 (s, 3H, OCH3), 7.16 and 7.37
(AB system, 4H, J¼8.3 Hz, Har), 7.44 and 7.70 (m, 5H, Har), 7.48 (s,
1H, H8), 8.86 (s, 1H, H4) ppm. 13C NMR (75 MHz, CDCl3):
n
¼3056 (w), 3033 (w), 2965 (w), 2932 (w), 2852 (w), 1711
and 130.8 (4CHar), 131.7 (Car), 133.4 (C4), 140.1 (Car), 152.2 (C8), 154.2
(C9a), 159.4 (C6), 161.3 (C2), 164.0 (CO2CH3) ppm. MS (EI, 70 eV): m/z
(%)¼312 (7), 311 (30) [M]þ, 310 (65), 185 (19), 179 (28), 151 (23), 132
(16), 107 (22), 105 (30), 91 (49), 78 (17), 57 (100), 53 (18). HRMS
(MALDI): calcd for C16H13N3NaO4 [MþNa]þ 334.0804; found
334.0804.
.
d
d¼21.5
(PhCH3), 57.2 (OCH3), 122.8 (C3), 128.1e130.6 (9CHar), 129.5 (C4),
131.4 (Car), 132.1 (C8), 132.8 and 139.4 (2Car), 140.2 (C7), 143.4
(C9a), 154.0 (C6), 159.6 (C2) ppm. MS (EI, 70 eV): m/z (%)¼360 (24),
359 (100) [M]þ, 358 (42), 316 (15), 288 (19), 117 (20), 116 (90), 91
(9). HRMS (MALDI): calcd for C21H18N3O3 [MþH]þ 360.1343;
found 360.1353.
4.10.11. 1-p-Tolyl-1H-pyrimido[1,2-a]pyrimidine-2,6-dione
(9k). White solid (30 mg, 77%). Mp 226e227 ꢀC. IR (KBr):
n
¼3078
(w), 3042 (w), 2951 (w), 2920 (w), 1690 (s), 1646 (m), 1576 (m),
1492 (s), 1423 (m), 1378 (m), 820 (m) cmꢁ1 1H NMR (300 MHz,
.
CDCl3):
d
¼2.44 (s, 3H, PhCH3), 6.19 (d, 1H, J¼6.6 Hz, H7), 6.47 (d, 1H,
J¼8.3 Hz, H3), 7.13 and 7.37 (AB system, 4H, J¼8.4 Hz, Har), 7.80 (d,
1H, J¼6.6 Hz, H8), 8.76 (d, 1H, J¼8.3 Hz, H4) ppm. 13C NMR (75 MHz,
4.10.16. 3-Methoxy-7-methoxycarbonyl-1-p-tolyl-1H-pyrimido[1,2-
a]pyrimidine-2,6-dione (9p). White solid (22 mg, 99%). Mp
CDCl3):
d
¼21.5 (PhCH3), 106.2 (C7), 110.8 (C3), 127.9 and 130.7 (4
241e243 ꢀC. IR (KBr):
n
¼3030 (w), 2956 (w), 2925 (w), 2853 (w),
1751 (s), 1732 (s), 1651 (m), 1565 (w), 1518 (s), 1503 (s), 1443 (m),
1384 (m), 1286 (s), 818 (m) cmꢁ1 1H NMR (300 MHz, CDCl3):
CHar), 132.4 (Car), 133.1 (C4), 139.7 (Car), 150.1 (C9a), 155.0 (C8), 157.4
(C2), 159.9 (C6) ppm. MS (EI, 70 eV): m/z (%)¼254 (8), 253 (38) [M]þ,
252 (100), 185 (12), 117 (12), 91 (20), 84 (12). HRMS (MALDI): calcd
for C14H12N3O2 [MþH]þ 254.0930; found 254.0927.
.
d
¼2.46 (s, 3H, PhCH3), 3.90 (s, 3H, CO2CH3), 3.99 (s, 3H, OCH3), 7.11
and 7.38 (AB system, 4H, J¼8.3 Hz, Har), 8.38 (s, 1H, H4), 8.63 (s, 1H,
H8) ppm. 13C NMR (75 MHz, CDCl3):
d¼21.5 (PhCH3), 52.4 (CO2CH3),
4.10.12. 7-Methoxy-1-p-tolyl-1H-pyrimido[1,2-a]pyrimidine-2,6-di-
one (9l). White solid (37 mg, 84%). Mp 278e279 ꢀC. IR (KBr):
57.1 (OCH3),106.9 (C7),109.4 (C3),127.8 and 130.8 (4 CHar), 131.8 and
140.1 (2Car),142.9 (C4),149.6 (C9a),154.2 and 156.4 (C2 and C6),159.8
(C8), 164.3 (CO2CH3) ppm. MS (EI, 70 eV): m/z (%)¼342 (9), 341 (55)
[M]þ, 340 (100), 310 (15), 175 (10), 132 (22), 117 (15), 91 (23), 59
(16), 53 (14). HRMS (MALDI): calcd for C17H16N3O5 [MþH]þ
342.1084; found 342.1075.
n
¼3092 (w), 3066 (w), 3040 (w), 2956 (w), 2924 (w), 2850 (w),
1754 (s), 1722 (s), 1687 (m), 1646 (m), 1567 (m), 1519 (s), 1500 (s),
1455 (s), 1387 (m), 1352 (w), 865 (w), 814 (m) cmꢁ1 1H NMR
.
(300 MHz, CDCl3):
d
¼2.44 (s, 3H, PhCH3), 3.82 (s, 3H, OCH3), 6.43 (d,
1H, J¼8.3 Hz, H3), 7.12 and 7.37 (AB system, 4H, J¼8.3 Hz, Har), 7.43
(s,1H, H8), 8.72 (d,1H, J¼8.3 Hz, H4) ppm. 13C NMR (75 MHz, CDCl3):
4.10.17. 3-Methoxy-1-p-tolyl-1H-pyrimido[1,2-a]pyrimidine-2,6-di-
one (9q). White solid (45 mg, 99%). Mp 253e254 ꢀC. IR (KBr):
d
¼21.5 (PhCH3), 57.2 (OCH3), 110.7 (C3), 128.1 and 130.7 (4 CHar),
131.9 (C8), 132.4 and 139.6 (2Car), 132.8 (C4), 140.3 (C7), 143.3 (C9a),
153.9 (C6), 159.7 (C2) ppm. MS (EI, 70 eV): m/z (%)¼284 (24), 283
(100) [M]þ, 282 (93), 240 (31), 212 (95), 185 (79), 117 (77), 91 (99),
77 (43), 65 (21). HRMS (MALDI): calcd for C15H14N3O3 [MþH]þ
284.1035; found 284.1031.
n
¼3076 (w), 3034 (w), 2973 (w), 1716 (s), 1691 (s), 1649 (m), 1575
(m), 1516 (s), 1497 (s), 1456 (w), 1360 (w), 1169 (m) cmꢁ1. 1H NMR
(300 MHz, CDCl3):
d
¼2.44 (s, 3H, PhCH3), 3.95 (s, 3H, OCH3), 6.21 (d,
1H, J¼6.3 Hz, H7), 7.12 and 7.37 (AB system, 4H, J¼8.3 Hz, Har), 7.80
(d, 1H, J¼6.3 Hz, H8), 8.28 (s, 1H, H4) ppm. 13C NMR (75 MHz,
CDCl3):
d
¼21.5 (PhCH3), 57.1 (OCH3), 105.3 (C7), 109.2 (C4), 127.9 and
4.10.13. 7-Methoxycarbonyl-3-phenyl-1-p-tolyl-1H-pyrimido[1,2-a]
130.6 (4 CHar), 132.3 and 139.7 (2Car), 142.2 (C3), 147.7 (C9a), 153.7
(C8), 156.7 and 157.4 (C2 and C6) ppm. MS (EI, 70 eV): m/z (%)¼283
(62) [M]þ, 282 (100), 185 (35), 117 (15), 91 (28), 65 (14). HRMS
pyrimidine-2,6-dione (9m). White solid (40 mg, 86%). Mp
264e265 ꢀC. IR (KBr):
n
¼3095 (w), 3064 (w), 2957 (w), 1726 (s),