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Y. Liu et al. / Tetrahedron 63 (2007) 2024–2033
1369, 1184, 799, 725 cmꢁ1. 1H NMR (300 MHz, CDCl3) d:
2.91 (s, 3H), 7.14 (d, 1H, J¼7.6 Hz), 7.37 (t, 1H, J¼7.4 Hz),
7.49 (td, 1H, J¼7.6 Hz, 1.3 Hz), 7.71–7.76 (m, 4H), 7.82 (d,
1H, J¼7.7 Hz), 9.48 (d, 1H, J¼7.7 Hz), 9.56–9.59 (m, 1H).
MS m/z (%) 311 (M+, 28), 296 (24), 240 (10), 213 (4), 127
(3), 43 (100). Anal. Calcd for C21H13NO2: C, 81.03; H,
4.18; N, 4.50. Found: C, 81.08; H, 4.15; N, 4.53.
d: 2.14 (d, 1H, J¼10.0 Hz), 2.58 (d, 1H, J¼10.0 Hz), 2.75
(s, 3H), 3.67 (s, 1H), 3.76 (s, 1H), 6.28 (s, 2H), 7.40 (d,
1H, J¼7.6 Hz), 7.72–7.76 (m, 2H), 7.79–7.82 (m, 1H),
9.38 (d, 1H, J¼7.5 Hz), 9.41–9.45 (m, 1H). 13C NMR
(75 MHz, CDCl3) d: 30.3, 45.1, 54.1, 54.6, 78.8, 79.6,
116.0, 119.1, 124.3, 124.7, 124.9, 127.3, 127.4, 129.2,
130.5, 130.9, 134.9, 138.4, 138.7, 184.9, 186.5, 192.1. MS
m/z (%): 423 (M+, 18), 357 (93), 329 (80), 252 (42), 224
(34), 188 (65), 128 (20), 66 (100), 43 (72). Anal. Calcd for
C23H15NO3Cl2: C, 65.25; H, 3.55; N, 3.31. Found: C,
65.21; H, 3.58; N, 3.28.
4.3.4. 8-Cyano-13H-indeno[20,10:3,4]pyrrolo[2,1-a]iso-
quinolin-13-one (11d). Yield: 46%; yellow solid from pe-
troleum ether (bp 60–90 ꢀC)/chloroform; mp 288–290 ꢀC.
IR (KBr) n 3073, 2963, 2210, 1689, 1604, 1573, 1523,
1487, 1360, 1261, 1099, 791, 723 cmꢁ1
.
1H NMR
4.3.8. 8-Cyano-9a,13a-dichloro-9a,10,13,13a-tetrahydro-
10,13-methanobenz[5,6]isoindolo[1,2-a]isoquinoline-
9,14-dione (12d). Yield: 85%; yellow solid from petroleum
ether (bp 60–90 ꢀC)/chloroform; mp >300 ꢀC. IR (KBr)
n 3142, 2950, 2228, 1699, 1671, 1548, 1502, 1465, 1439,
(300 MHz, CDCl3) d: 7.21 (d, 1H, J¼7.5 Hz), 7.38 (t, 1H,
J¼7.5 Hz), 7.51 (t, 1H, J¼7.4 Hz), 7.63 (t, 1H, J¼7.5 Hz),
7.69–7.79 (m, 4H), 8.01 (d, 1H, J¼7.3 Hz), 9.26 (d, 1H,
J¼7.8 Hz). MS m/z (%) 294 (M+, 100), 265 (21), 213 (5),
133 (10), 44 (25). Anal. Calcd for C20H10N2O: C, 81.63;
H, 3.40; N, 9.52. Found: C, 81.66; H, 3.46; N, 9.50.
1
1234, 1146, 793, 697 cmꢁ1. H NMR (300 MHz, CDCl3)
d: 2.12 (d, 1H, J¼10.0 Hz), 2.61 (d, 1H, J¼10.0 Hz), 3.76
(d, 1H, J¼1.7 Hz), 3.80 (d, 1H, J¼1.7 Hz), 6.21–6.23 (m,
2H), 7.56 (d, 1H, J¼7.2 Hz), 7.81–7.91 (m, 3H), 8.29 (d,
1H, J¼7.2 Hz), 9.58–9.61 (m, 1H). MS m/z (%) 406 (M+,
5), 371 (7), 340 (100), 277 (81), 249 (35), 163 (39), 105
(41), 66 (97), 44 (83). Anal. Calcd for C22H12N2O2Cl2: C,
65.02; H, 2.96; N, 6.90. Found: C, 65.06; H, 2.93; N,
6.88.
4.3.5. 8-Benzoyl-9a,13a-dichloro-9a,10,13,13a-tetrahy-
dro-10,13-methanobenz[5,6]isoindolo[1,2-a]isoquino-
line-9,14-dione (12a). CCDC No. 602716. Yield: 82%;
white solid from petroleum ether (bp 60–90 ꢀC)/acetone;
mp >300 ꢀC. IR (KBr) n 3125, 2957, 1698, 1672, 1638,
1596, 1578, 1551, 1503, 1426, 1351, 1248, 1223, 1148,
1
949, 798, 736, 702 cmꢁ1. H NMR (300 MHz, CDCl3) d:
2.01 (d, 1H, J¼10.0 Hz), 2.52 (d, 1H, J¼10.0 Hz), 3.47 (s,
1H), 3.76 (s, 1H), 6.04–6.07 (m, 1H), 6.17–6.20 (m, 1H),
7.37 (d, 1H, J¼7.5 Hz), 7.50 (t, 2H, J¼7.6 Hz), 7.61–7.81
(m, 4H), 8.02 (dd, 2H, J¼7.6 Hz, 1.4 Hz), 8.74 (d, 1H,
J¼7.5 Hz), 9.49–9.53 (m, 1H). 13C NMR (75 MHz,
CDCl3) d: 44.9, 54.5, 55.0, 79.6, 115.3, 119.0, 123.9,
124.7, 125.3, 127.5, 127.6, 129.0, 129.3, 129.8, 130.5,
130.9, 134.0, 135.7, 137.7, 138.3, 138.5, 185.0, 185.4,
187.6. MS m/z (%) 419 (23), 356 (8), 264 (4), 188 (18),
164 (6), 105 (26), 77 (100). Anal. Calcd for C28H17NO3Cl2:
C, 69.28; H, 3.51; N, 2.89. Found: C, 69.27; H, 3.57; N, 2.89.
4.3.9. 8,13-Dihydro-14-benzoylbenz[5,6]indolo[2,1-a]iso-
quinoline-8,13-dione (16a). Yield: 76%; yellow solid
from petroleum ether/chloroform; mp >300 ꢀC (lit.29
307.5–308.5 ꢀC). IR (KBr) n 3126, 3055, 1665, 1657,
1645, 1593, 1505, 1393, 1236, 1221, 957, 792, 706 cmꢁ1
.
1H NMR (300 MHz, CDCl3) d: 7.36 (d, 1H, J¼7.5 Hz),
7.45–7.69 (m, 6H), 7.76 (t, 2H, J¼7.9 Hz), 7.94 (d, 1H,
J¼8.1 Hz), 8.08 (d, 3H, J¼7.5 Hz), 8.29 (d, 1H,
J¼7.5 Hz), 9.54 (d, 1H, J¼7.5 Hz). MS m/z (%) 401 (M+,
50), 372 (6), 324 (100), 240 (22), 149 (9), 105 (8), 77 (21).
Anal. Calcd for C27H15NO3: C, 80.80; H, 3.74; N, 3.49.
Found: C, 80.72; H, 3.78; N, 3.43.
4.3.6. 8-Ethoxycarbonyl-9a,13a-dichloro-9a,10,13,13a-
tetrahydro-10,13-methanobenz[5,6]iso-indolo[1,2-a]iso-
quinoline-9,14-dione (12b). Yield: 83%; yellow solid from
petroleum ether (bp 60–90 ꢀC)/chloroform; mp 228–230 ꢀC.
IR (KBr) n 3131, 2980, 1709, 1677, 1551, 1537, 1504, 1471,
4.3.10. 8,13-Dihydro-14-ethoxycarbonylbenz[5,6]in-
dolo[2,1-a]isoquinoline-8,13-dione (16b). Yield: 78%; yel-
low solid from petroleum ether (bp 60–90 ꢀC)/chloroform;
mp 238–240 ꢀC (lit.29 239–239.5 ꢀC). IR (KBr) n 3149,
3060, 2985, 2950, 1724, 1661, 1644, 1611, 1592, 1571,
1257, 1213, 1103, 804, 699 cmꢁ1 1H NMR (300 MHz,
.
1
CDCl3) d: 1.43 (t, 3H, J¼7.1 Hz), 2.10 (d, 1H, J¼9.8 Hz),
2.58 (d, 1H, J¼9.8 Hz), 3.66 (d, 1H, J¼1.7 Hz), 3.74 (d,
1H, J¼1.7 Hz), 4.43–4.54 (m, 2H), 6.26–6.27 (m, 2H),
7.38 (d, 1H, J¼7.5 Hz), 7.71–7.81 (m, 3H), 9.18 (d, 1H,
J¼7.5 Hz), 9.47 (m, 1H). 13C NMR (75 MHz, CDCl3) d:
14.2, 45.1, 54.2, 54.7, 78.5, 80.0, 115.9, 117.1, 118.5,
123.9, 125.1, 127.2, 127.4, 129.1, 129.9, 130.6, 134.6,
138.1, 138.9, 160.7, 184.8, 185.0. MS m/z (%) 453 (M+,
14), 418 (21), 387 (100), 315 (81), 252 (81), 240 (52), 188
(87), 164 (53), 66 (89). Anal. Calcd for C24H17NO4Cl2: C,
63.58; H, 3.75; N, 3.09. Found: C, 63.55; H, 3.76; N, 3.10.
1506, 1390, 1232, 1224, 1199, 952, 798, 704 cmꢁ1. H
NMR (300 MHz, CDCl3) d: 1.56 (t, 3H, J¼7.1 Hz), 4.70
(q, 2H, J¼7.1 Hz), 7.33 (d, 1H, J¼7.3 Hz), 7.63–7.81 (m,
5H), 8.23 (dd, 1H, J¼7.9 Hz, 1.8 Hz), 8.27–8.32 (m, 2H),
9.49 (d, 1H, J¼7.4 Hz). 13C NMR (CDCl3) d: 14.5, 62.8,
110.6, 117.8, 124.7, 124.8, 126.9, 127.2, 128.0, 129.3,
129.7, 129.9, 133.0, 133.6, 133.9, 134.1, 134.8, 167.0,
175.6, 181.0. MS m/z (%) 369 (M+, 72), 324 (78), 297
(100), 240 (52), 213 (17), 119 (7), 76 (9), 44 (17). Anal.
Calcd for C23H15NO4: C, 74.80; H, 4.07; N, 3.80. Found:
C, 74.79; H, 4.12; N, 3.80.
4.3.7. 8-Acetyl-9a,13a-dichloro-9a,10,13,13a-tetrahydro-
10,13-methanobenz[5,6]isoindolo[1,2-a]isoquinoline-
9,14-dione (12c). Yield: 90%; yellow solid from petroleum
ether (bp 60–90 ꢀC)/chloroform; mp 238–240 ꢀC. IR (KBr)
n 3141, 3003, 2956, 1702, 1686, 1660, 1548, 1502, 1474,
4.3.11. 8,13-Dihydro-14-acetylbenz[5,6]indolo[2,1-a]iso-
quinoline-8,13-dione (16c). CCDC No. 616322. Yield:
85%; yellow solid from petroleum ether (bp 60–90 ꢀC)/chlo-
roform; mp 281–283 ꢀC (lit.29 281–282 ꢀC). IR (KBr)
n 3126, 3068, 2989, 1701, 1658, 1644, 1594, 1574, 1530,
1
1364, 1148, 803, 696 cmꢁ1. H NMR (300 MHz, CDCl3)
1505, 1482, 1393, 1361, 1285, 1233, 1184, 956, 703 cmꢁ1
.