1136
Q.-J. Liu et al. / Tetrahedron 62 (2006) 1131–1138
dH: 8.09 (1H, dd, JZ7.5, 1.4 Hz), 7.31–7.47 (2H, m), 7.32
2H, d, JZ8.5 Hz), 6.77–6.87 (3H, m), 6.47 (1H, d, JZ
4.3.5. Irradiation of 1 with 2e. A solution of 1 (633 mg,
3.0 mmol) and 2e (1.068 g, 6.0 mmol) in benzene (100 mL)
was irradiated for 15 h to afford 7e (373 mg, 40%), 9e
(492 mg, 53%) and unreacted 1 (127 mg, 80% conversion).
(
9
4
8
.9 Hz), 6.21 (1H, dd, JZ9.9, 4.2 Hz), 4.12 (1H, d, JZ
.1 Hz), 3.32 (3H, s). n : 1719, 1665, 1422, 1361, 1291,
max
K1 C
30, 764 cm . m/z 393 (M C2, 10.5), 392 (M, 11.4), 391
C
(
M , 10.8), 211 (100), 182 (22). Found: C 64.52, H 4.11, N
.68. C H BrNO requires C 64.30, H 3.60, N 3.57. X-ray
4
.3.5.1. 4-Methyl-1,2-diphenyl-3H,10aH-benzo[de]-
3
2
1
14
2
cyclobut[i]isoquinoline-3,5-dione (7e). Colorless crystals
from petroleum ether–ethyl acetate, mp 170–171 8C. dH:
structure analysis: C H BrNO , MZ327.37. Triclinic,
2
1
14
2
space group P-1, aZ11.327(2), bZ9.2270(18), cZ
7
.97 (1H, dd, JZ7.2, 1.9 Hz), 7.37–7.46 (4H, m), 7.19–7.32
6H, m), 6.81–6.85 (2H, m), 6.49 (1H, d, JZ10.1 Hz), 6.40
(1H, dd, JZ10.0, 4.3 Hz), 4.77 (1H, d, JZ4.3 Hz), 3.16
˚
˚
1
6.397(3) A, aZ90.00, bZ97.95(3), gZ90.008, VZ
(
3 K3
1
absorption coefficient 2.461 mm , scan range for data
697.2(6) A , ZZ4, D Z1.281 g cm , F(000)Z688,
c
K1
13
(
3H, s). C NMR (CDCl , 100 MHz) d : 27.1, 41.4, 55.0,
3 c
collection 1.82%q%25.008, 3150 measured reflections,
1
1
25.4, 126.4, 126.8, 126.9, 127.4, 127.5, 128.2, 128.5,
28.8, 128.9, 130.4, 131.2, 131.5, 131.8, 132.3, 132.6,
2
991 independent reflections, 1734 reflections with
IO2s(I), R Z0.0473, 227 refinable parameters,
int
134.0, 142.6, 149.1, 164.6, 173.0. n : 1715, 1670, 1418,
max
2
2
2
R[F O2s(F )]Z0.0562, wR (F )Z0.1579.
K1
C
2
1360, 1295, 827, 757 cm . m/z: 388 (M K1, 3), 211 (1),
78 (100). Found: C 83.10, H 5.18, N 4.03. C H NO
2
1
2
7
19
requires C 83.27, H 4.92, N 3.60. X-ray structural analysis:
C H NO , MZ389.43. Monoclinic, space group P2(1)/n,
4
3
.3.3. Irradiation of 1 with 2c. A solution of 1 (633 mg,
.0 mmol) and 2c (792 mg, 6.0 mmol) in benzene (100 mL)
27 19
2
˚
aZ8.258(1), bZ0.465(2), cZ23.942(6) A, aZ90, bZ
was irradiated for 10 h to furnish 3c (595 mg, 68%), 4c
217 mg, 25%) and unreacted 1 (95 mg, 85% conversion).
3
˚
9
1
0
1
3.32(1), gZ908, VZ2065.6(7) A , ZZ4, D Z
c
K3
(
.252 g cm
,
F(000)Z816, absorption coefficient
scan range for data collection
.70%q%25.208, 3987 measured reflections, 3710 inde-
K1
.079 mm
,
4.3.3.1. 4-Methyl-2-(4-methoxyphenyl)-3H,10aH-
benzo[de]cyclobut[i]isoquinoline-3,5-dione (3c). Color-
less crystals from petroleum ether–ethyl acetate, mp 168–
1
7
6
9
4
1
pendent reflections, 1649 reflections with IO2s(I), R Z
int
2
2
0
.0221, 273 refinable parameters, R[F O2s(F )]Z0.0434,
69.5 8C. d : 8.09 (1H, dd, JZ7.2, 1.9 Hz), 7.41 (1H, t, JZ
2
H
wR (F )Z0.1002.
2
.4 Hz), 7.38 (1H, dd, JZ7.5, 1.9 Hz), 6.88–6.92 (2H, m),
.70–6.74 (2H, m), 6.65 (1H, d, JZ1.0 Hz), 6.45 (1H, d, JZ
.9 Hz), 6.22 (1H, dd, JZ9.9, 4.2 Hz), 4.10 (1H, d, JZ
.2 Hz), 3.74 (3H, s), 3.32 (3H, s). nmax: 1713, 1666, 1421,
4
.3.5.2. 4,5-Dihydro-5-methyl-6-benzoyl-4-benzo
a]thebenidinone (9e). Pale yellow powder from chloro-
form–petroleum ether, mp 206–208 8C. d : 8.95 (1H, d, JZ
[
K1
C
H
359, 1290, 833, 764 cm . m/z: 343 (M , 14), 211 (4),
9
1
9
.2 Hz), 8.91 (1H, d, JZ8.4 Hz), 8.81 (1H, dd, JZ7.5,
.1 Hz), 8.40 (1H, dd, JZ7.9, 0.8 Hz), 8.31 (1H, d, JZ
.1 Hz), 7.99 (1H, t, JZ7.7 Hz), 7.86–7.90 (3H, m), 7.72
1
requires C 76.95, H 4.99, N 4.08.
32 (100). Found: C 76.74, H 5.43, N 4.35. C H NO
3
2
2
17
(
7
1
1H, td, JZ7.6, 1.2 Hz), 7.57–7.64 (2H, m), 7.44 (2H, t, JZ
.9 Hz), 3.82 (3H, s). C NMR (CDCl , 100 MHz) d : 36.3,
3 c
16.0, 120.2, 122.0, 123.1, 124.0, 125.7, 125.8, 126.0,
4.3.3.2. 4,5-Dihydro-5-methyl-6-formyl-9-methoxy-4-
benzo[a]thebenidinone (4c). Orange powder from chloro-
form–petroleum ether, mp 227–229 8C. d : 10.9 (1H, s),
H
13
126.8, 126.9, 127.1, 127.7, 127.8, 128.2, 128.9, 129.2,
9
(
.20 (1H, d, JZ9.4 Hz), 8.84 (1H, dd, JZ7.5, 1.1 Hz), 8.74
1H, d, JZ9.2 Hz), 8.38 (1H, dd, JZ7.5, 1.1 Hz), 8.29 (1H,
d, JZ9.2 Hz), 8.13 (1H, d, JZ2.6 Hz), 8.00 (1H, t, JZ
1
1
1
29.7, 130.5, 131.7, 133.9, 134.1, 134.5, 138.8, 163.1,
99.4. nmax: 1660 (C]O), 1229, 757 cm . m/z: 387 (M ,
00), 370 (73), 310 (51), 282 (22), 252 (34), 226 (11), 193
K1
C
7
4
7
.7 Hz), 7.51 (1H, dd, JZ9.4, 2.6 Hz), 4.10 (3H, s),
(8), 105 (23). Found: C 84.06, H 5.03, N 4.17. C H NO
requires C 83.70, H 4.42, N 3.61.
27 17 2
.02 (3H, s). n : 1657 (C]O), 1620, 1246, 823,
max
K1 C
53 cm . m/z: 341 (M , 100), 324 (73), 298 (23), 270
(20), 240 (21), 149 (19). Found: C 81.42, H 4.41, N 4.48.
C H NO requires C 81.21, H 4.65, N 4.30.
4
3
.3.6. Irradiation of 1 with 2f. A solution of 1 (633 mg,
.0 mmol) and 2f (1.272 g, 6.0 mmol) in benzene (100 mL)
was irradiated for 15 h to give an isomeric mixture of 7f and
2
2
15
3
4
3
.3.4. Irradiation of 1 with 2d. A solution of 1 (633 mg,
.0 mmol) and 2d (3.963 g, 60 mmol) in benzene (100 mL)
8
1
f (376 mg, 40%, 59:41) and an isomeric mixture of 9f and
0f (496 mg, 53%, 46:54), and unreacted 1 (165 mg, 74%
was irradiated for 48 h to give 3d (335 mg, 84%), and
unreacted 1 (329 mg, 48% conversion).
conversion).
4
.3.6.1. 4-Methyl-1-(4-chlorophenyl)-3H,10aH-2-
4.3.4.1. 2-Cyclopropyl-4-methyl-3H,10aH-benzo[de]-
cyclobut[i]isoquinoline-3,5-dione (3d). White solid from
phenylbenzo[de]cyclobut[i]isoquinoline-3,5-dione (7f).
Colorless crystals from petroleum ether–ethyl acetate, mp
petroleum ether–ethyl acetate, mp 103–105 8C. d : 8.03
H
186–188 8C. d : 7.93 (1H, dd, JZ7.4, 1.7 Hz), 7.22–7.39
H
(
1
1H, d, JZ6.0 Hz), 7.37–7.42 (2H, m), 6.41 (1H, d, JZ
2.0 Hz), 6.14 (1H, dd, JZ9.1, 0.8 Hz), 5.99 (1H, s), 3.99
(7H, m), 7.14–7.18 (2H, m), 6.71–6.74 (2H, m), 6.44 (1H, d,
JZ10.1 Hz), 6.32 (1H, dd, JZ10.1, 4.3 Hz), 4.71 (1H, d,
(
(
1
1H, d, JZ4.0 Hz), 3.41 (3H, s), 0.88 (1H, s), 0.53–0.59
JZ4.2 Hz), 3.13 (3H, s). n : 1717, 1671, 1418, 1357,
max
K1
C
C
2H, m), 0.26–0.33 (2H, m). n : 3035, 2925, 1713, 1669,
1287, 829, 761 cm . m/z: 425 (M C2, 1.5), 423 (M ,
4.8), 214 (56), 213 (32), 212 (100), 176 (17), 151 (11).
Found: C 76.82, H 4.61, N 3.10. C H ClNO requires C
max
C
K1
476, 1286 cm . m/z: 277 (M , 8.4), 211 (100), 183 (19),
167 (16), 127 (14). Found: C, 77.76, H 5.58, N 5.10.
C H NO requires C 77.96, H 5.45, N 5.05.
2
7
18
2
76.50, H 4.28, N 3.34.
1
8
15
2