4626 J . Org. Chem., Vol. 65, No. 15, 2000
Abarbri et al.
1,3-Diben zyl-2,4-d ioxo-1,2,3,4-tetr a h yd r op yr im id in e-5-
ca r bon itr ile (2n ). The reaction was carried out according to
typical procedure A using 1d (700 mg, 1.67 mmol), i-PrMgBr
(2.51 mL, 2.01 mmol, 0.8 M in THF, exchange at -40 °C, 30
min), and p-toluenesulfonyl cyanide (424 mg, 2.34 mmol) to
give a crude residue, which was then purified by column
chromatography on silica (pentane/Et2O, 3:2) affording the
product 2n (250 mg, 47%) as a white solid, mp 130°C. IR
(KBr): 2232 (s), 1722 (s), 1671 (s), 1629 (m), 1584 (m), 1336
tane/Et2O, 3:7) affording the product 2r (398 mg, 83%) as a
white solid, mp 60 °C. IR (KBr): 1707 (s), 1668 (s), 1653 (s),
1
1336 (s), 1289 (s), 1146 (s) cm-1. H NMR (CDCl3, 300 MHz):
δ 7.27 (s, 1H), 6.28 (s, 1H), 5.8 (s, 1H), 5.41 (s, 2H), 5.15 (s,
2H), 4.2 (q, J ) 7 Hz, 2H), 3.66 (q, J ) 7 Hz, 2H), 3.59 (q, J )
6.8 Hz, 2H), 3.36 (s, 2H), 1.29 (t, J ) 7 Hz, 3H), 1.20 (t, J )
6.8 Hz, 6H). 13C NMR (CDCl3, 75 MHz): δ 165.1, 162.7, 151.1,
139.4, 136.6, 127.6, 111.6, 77.2, 70.6, 65.7, 65, 60.6, 29.3, 15,
14.7, 14. m/z (EI-MS): 340 (5), 296 (6), 295 (25), 294 (66), 237
(13), 208 (10), 207 (13), 59 (100). HRMS: calcd for C16H24N2O6
340.1634, found 340.1636.
1
(s). H NMR (CDCl3, 300 MHz): δ 7.68 (s, 1H), 7.39-7.17 (m,
10H), 5.03 (s, 2H), 4.87 (s, 2H). 13C NMR (CDCl3, 75 MHz): δ
158.9, 149.9, 149.4, 135.3, 133.3, 129.3, 129.2, 128.4, 128,
112.9, 89.7, 53.3, 45.2. m/z (EI-MS): 317 (59), 226 (56), 121
(47), 91 (100). HRMS: calcd for C19H15O2N3 317.1164, found
317.1164.
5-Ben zoyl-1,3-d iben zyl-1H-p yr im id in e-2,4-d ion e (2s).
The reaction was carried out according to typical procedure A
using 1d (700 mg, 1.67 mmol), i-PrMgBr (2.51 mL, 2.01 mmol,
0.8 M in THF, exchange at -40 °C, 30 min), CuCN‚2LiCl (2.17
mL, 2.17 mmol, 1 M in THF), and benzoyl chloride (272 µL,
2.34 mmol) to give a crude residue, which was then purified
by column chromatography on silica (pentane/Et2O, 2:3) af-
fording the product 2s (484 mg, 73%) as a white solid, mp 118
°C. IR (KBr): 1716 (s), 1658 (s), 1645 (m), 1601 (s), 1450 (s),
5-Allyl-1,3-d iben zyl-1H-p yr im id in e-2,4-d ion e (2o). The
reaction was carried out according to typical procedure A using
1d (700 mg, 1.67 mmol), i-PrMgBr (2.51 mL, 2.01 mmol, 0.8
M in THF, exchange at -40 °C, 30 min), CuCN (10% mol, 20
mg), and allyl bromide (203 µL, 2.34 mmol) to give a crude
residue, which was then purified by column chromatography
on silica (pentane/Et2O, 7:3) affording the product 2o (450 mg,
81%) as a white solid, mp 100 °C. IR (KBr): 1695 (s), 1653 (s),
1
1382 (s) cm-1. H NMR (CDCl3, 300 MHz): δ 7.8 (s, 1H), 7.8
(d, J ) 7.2 Hz, 2H), 7.36-7.1 (m, 13H), 5.0 (s, 2H), 4.81 (s,
2H). 13C NMR (CDCl3, 75 MHz): δ 190.7, 160.1, 150,9, 147.9,
137.5, 136.3, 134.6, 132.9, 129.3, 129.2, 129.1, 128.7, 128.4,
128.3, 128, 127.8, 113.3, 53, 44.7. m/z (EI-MS): 396 (62), 200
(37), 105 (100). HRMS: calcd for C25H20N2O3 396.1474, found
396.1479.
1
1638 (s), 1602 (m) cm-1. H NMR (CDCl3, 300 MHz): δ 7.39-
7.15 (s, 10H), 6.83 (s, 1H), 5.68 (m, 1H), 5.05 (s, 2H), 4.98 (d,
J ) 14.7 Hz, 1H), 4.96 (d, J ) 9 Hz, 1H), 4.77 (s, 2H), 2.95 (d,
J ) 5.6 Hz, 2H). 13C NMR (CDCl3, 75 MHz): δ 163, 151.7,
138.7, 137, 135.7, 134.5, 129, 128.9, 128.5, 128.4, 127.8, 127.6,
117.5, 112.9, 52.3, 44.8, 31.3. m/z (EI-MS): 332 (15), 241 (14),
5-Ben zoyl-1,3-biseth oxym eth yl-1H-p yr im id in e-2,4-d i-
on e (2t). The reaction was carried out according to typical
procedure A using 1f (500 mg, 1.41 mmol), i-PrMgBr (2.29 mL,
1.83 mmol, 0.8 M in THF, exchange at -40 °C, 30 min), CuCN‚
2LiCl (1.97 mL, 1.97 mmol, 1 M in THF), and benzoyl chloride
(229 µL, 1.97 mmol) to give a crude residue, which was then
purified by column chromatography on silica (pentane/Et2O/
MeOH, 8:2:1) affording the product 2t (351 mg, 75%) as a
colorless oil. IR (neat): 3055 (s), 2932 (s), 1728 (s), 1682 (s),
1615 (s), 1582 (s) cm-1. 1H NMR (CDCl3, 300 MHz): δ 7.94 (s,
1H), 7.69-7.35 (m, 5H), 5.36 (s, 2H), 5.19 (s, 2H), 3.59 (q, J )
7 Hz, 4H), 1.17 (t, J ) 7 Hz, 3H), 1.12 (t, J ) 7 Hz, 3H). 13C
NMR (CDCl3, 75 MHz): δ 190.5, 160.1, 151, 147.3, 137.3, 133,
129.2, 128.2, 113.9, 78, 70.8, 66, 65.8, 15, 14.8. m/z (EI-MS):
332 (3), 288 (60), 275 (57), 229 (31), 200 (20). HRMS calcd for
91 (100). HRMS: calcd for
332.1521.
C21H20N2O2 332.1525, found
2-(1,3-Diben zyl-2,4-d ioxo-1,2,3,4-tetr a h yd r op yr im id in -
5-ylm eth yl)a cr ylic Eth yl Ester (2p ). The reaction was
carried out according to typical procedure A using 1d (700 mg,
1.67 mmol), i-PrMgBr (2.51 mL, 2.01 mmol, 0.8 M in THF,
exchange at -40 °C, 30 min), CuCN‚2LiCl (2.17 mL, 2.17
mmol, 1 M in THF), and ethyl (2-bromomethyl)acrylate (324
µL, 2.34 mmol) to give a crude residue, which was then purified
by column chromatography on silica (pentane/Et2O, 1:1) af-
fording the product 2p (514 mg, 76%) as a colorless oil. IR
(neat): 1712 (s), 1661 (s), 1651 (m), 1607 (s), 1586 (s), 1209
(s), 1147 (s) cm-1. 1H NMR (CDCl3, 300 MHz): δ 7.4-7.14 (m,
10H), 7.08 (s, 1H), 6.14 (d, J ) 1.1 Hz, 1H), 5.67 (s, J ) 1.1
Hz, 1H), 5.06 (s, 2H), 4.82 (s, 2H), 4.04 (q, J ) 7.1 Hz, 2H),
3.23 (s, 2H), 1.14 (t, J ) 7.1 Hz, 3H). 13C NMR (CDCl3, 75.5
MHz): δ 166.6, 162.9, 151.6, 140.3, 137.1, 137, 135.7, 129,
128.2, 128.1, 127.6, 127.5, 126.9, 112.2, 60.8, 52.3, 44.8, 29.7,
14.2. m/z (EI-MS): 404 (17), 359 (10), 358 (30), 267 (55), 91
(100). HRMS: calcd for C24H24N2O4 404.1736, found 404.1737.
5-Allyl-1,3-(3,5-d im et h oxyb en zyl)-1H -p yr im id in e-2,4-
d ion e (2q). The reaction was carried out according to typical
procedure A using 1e (700 mg, 1.30 mmol), i-PrMgBr (2.11
mL, 1.69 mmol, 0.8 M in THF, exchange at -40 °C, 30 min),
CuCN (10% mol, 12 mg), and allyl bromide (169 µL, 1.95 mmol)
to give a crude residue, which was then purified by column
chromatography on silica (pentane/Et2O, 3:7) affording the
product 2q (476 mg, 81%) as a white solid, mp 62 °C. IR
(KBr): 3062 (s), 2963 (s), 1704 (s), 1664 (m), 1655 (s), 1642
(s), 1596 (s), 1160 (s) cm-1. 1H NMR (CDCl3, 300 MHz): δ 6.86
(t, J ) 1.1 Hz, 1H), 6.53 (s, 1H), 6.52 (s, 1H), 6.30-6.26 (m,
4H), 5.8-5.67 (m, 1H), 5.03 (s, 2H), 5.05-4.99 (m, 2H), 4.76
(s, 2H), 3.67 (s, 12H), 2.99 (dd, J ) 6.6 Hz, J ) 1.1 Hz, 2H).
13C NMR (CDCl3, 75 MHz): δ 162.8, 161.3, 160.7, 151.6, 139.2,
138.5, 138, 134.4, 117.4, 112.9, 106.6, 105.7, 99.9, 99.7, 55.3,
55.2, 52.2, 44.7, 31.2. m/z (EI-MS): 452 (99), 299 (40), 298 (12),
256 (38), 152 (57), 151 (100). HRMS: calcd for C25H28N2O6
452.1947, found 452.1940.
C
17H20N2O5 332.1372, found 332.1371.
1,3-Diben zyl-5-d ia llyla m in om eth yl-1H-p yr im id in e-2,4-
d ion e (2u ). The reaction was carried out according to typical
procedure A using 1d (700 mg, 1.67 mmol), i-PrMgBr (2.51
mL, 2.01 mmol, 0.8 M in THF, exchange at -40 °C, 30 min),
and N,N-diallylmethyleniminium salt (2.18 mmol) to give a
crude residue, which was then purified by column chromatog-
raphy on silica (pentane/Et2O, 1:1) affording the product 2u
(517 mg, 85%) as a colorless oil. IR (neat): 3055 (m), 2986 (s),
1701 (s), 1662 (s), 1643 (s), 1586 (s) cm-1 1H NMR (CDCl3,
.
300 MHz): δ 7.42-7.14 (m, 10H), 7.15 (s, 1H), 5.65 (qt, J )
17 Hz, J ) 10.3 Hz, J ) 6.2 Hz, 2H), 5.06 (s, 2H), 5.05-4.97
(m, 4H), 4.84 (s, 2H), 3.27 (s, 2H), 2.94 (d, J ) 6.2 Hz, 4H). 13
C
NMR (CDCl3, 75 MHz): δ 162.9, 151.5, 139.6, 136.9, 135.6,
135.3, 129, 128.9, 128.3, 128.2, 128, 127.5, 117.3, 111.6, 56.8,
52.2, 49.2, 44.5. m/z (EI-MS): 401 (3), 361 (8), 360 (29), 110
(74), 96 (100). HRMS: calcd. for C25H27O2N3 401.2103, found
401.2097.
5-Dia llyla m in om eth yl-1,3-biseth oxym eth yl-1H-p yr im i-
d in e-2,4-d ion e (2v). The reaction was carried out according
typical procedure A using 1e (500 mg, 1.41 mmol), i-PrMgBr
(2.29 mL, 1.83 mmol, 0.8 M in THF, exchange at -40 °C, 30
min), and N,N-diallylmethyleniminium (1.83 mmol) to give a
crude residue, which was then purified by column chromatog-
raphy on silica (pentane/Et2O/MeOH, 5:5:1) affording the
product 2v (390 mg, 82%) as a colorless oil. IR (neat): 2930
(s), 2816 (s), 1713 (s), 1667 (s), 1153 (s), 1055 (s) cm-1. 1H NMR
(CDCl3, 500 MHz): δ 7.37 (s, 1H), 5.82 (qt, J ) 15 Hz, J ) 8.5
Hz, J ) 7.6 Hz, 2H), 5.4 (s, 2H), 5.17 (d, J ) 15 Hz, 2H), 5.16
(s, 2H), 5.15 (d, J ) 8.5 Hz, 2H), 3.64 (q, J ) 7 Hz, 2H), 3.57
(q, J ) 7 Hz, 2H), 3.38 (s, 2H), 2.95 (d, J ) 7.6 Hz, 4H), 1.20
(t, J ) 7 Hz, 3H), 1.18 (t, J ) 7 Hz, 3H). 13C NMR (CDCl3,
125.7 MHz): δ 163, 151.6, 139.6, 135.2, 117.7, 112, 76.7, 70.6,
2-(1,3-Biseth oxym eth yl-2,4-d ioxo-1,2,3,4-tetr a h yd r op y-
r im id in -5-ylm eth yl)a cr ylic Acid Eth yl Ester (2r ). The
reaction was carried out according to typical procedure A using
1f (500 mg, 1.41 mmol), i-PrMgBr (2.29 mL, 1.83 mmol, 0.8
M in THF, exchange at -40 °C, 30 min), CuCN‚2LiCl (1.97
mL, 1.97 mmol, 1 M in THF), and ethyl (2-bromomethyl)-
acrylate (273 µL, 1.97 mmol) to give a crude residue, which
was then purified by column chromatography on silica (pen-