The Journal of Organic Chemistry
Note
CDCl3) δ 1.52 (t, J = 7.2 Hz, 3H), 2.50 (s, 3H), 4.53 (q, J = 7.2 Hz,
2H), 7.01 (dd, J = 7.2, 1.2 Hz, 1H), 7.70−7.75 (m, 2H), 8.10 (s, 1 H),
8.20−8.23 (m, 2H), 9.72 (d, J = 7.2 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 180.4, 174.9, 163.7, 140.2, 139.6, 134.2, 133.8, 133.4, 133.0,
128.9, 127.6, 127.3, 125.9, 122.2, 120.0, 119.4, 104.8, 61.0, 21.8, 14.4;
IR (KBr) 3057, 2976, 2921, 1698, 1671, 1633, 1591, 1541, 1507, 1488,
1475, 1400, 1387, 1365, 1286, 1228, 1172, 1121, 1019, 789, 712 cm−1.
HRMS (ESI) m/z [M + Na]+ calcd for C20H15NO4Na: 356.0899.
Found: 356.0908.
δ 1.37 (t, J = 7.2 Hz, 3H), 1.53 (t, J = 7.2 Hz, 3H), 2.80 (q, J = 7.2 Hz,
2H), 4.53 (q, J = 7.2 Hz, 2H), 7.06 (d, J = 7.2 Hz, 1H), 7.71−7.76 (m.
2H), 8.15 (s, 1H), 8.23 (d, J = 6.4 Hz, 2H), 9.76 (d, J = 7.2 Hz, 1H);
13C NMR (100 MHz, CDCl3) δ 180.5, 174.9, 163.7, 145.5, 140.3,
134.3, 133.8, 133.4, 133.0, 130.7, 129.0, 127.8, 127.3, 126.0, 119.0,
118.0, 105.0, 61.0, 28.8, 14.4, 14.1; IR (KBr) 2964, 2926, 1687, 1676,
1626, 1573, 1524, 1491, 1474, 1438, 1363, 1293, 1228, 1168, 1020,
895, 823, 795, 712 cm−1. HRMS (ESI) m/z [M + Na]+ calcd for
C21H17NO4Na: 370.1055. Found: 370.1054.
12-Methoxycarbonyl-2-methylbenzo[f ]pyrido[1,2-a]indole-6,11-
dione (5n). Red solid: mp 217−218 °C; 1H NMR (400 MHz, CDCl3)
δ 2.51 (s, 3H), 4.06 (s, 3H), 7.03 (d, J = 6.8 Hz, 1H), 7.72 (s, 2H),
8.13 (s, 1H), 8.22 (d, J = 4.8 Hz, 2H), 9.73 (d, J = 6.8 Hz, 1H); 13C
NMR (100 MHz, CDCl3) δ 180.6, 174.9, 164.1, 140.3, 139.8, 134.2,
133.8, 133.5, 133.1, 128.8, 127.6, 127.3, 126.0, 122.3, 120.1, 119.5,
104.2, 52.0, 21.8; IR (KBr) 2953, 1699, 1682, 1634, 1591, 1525, 1502,
1483, 1393, 1357, 1291, 1230, 1162, 1059, 1016, 841, 791, 711 cm−1.
HRMS (ESI) m/z [M + Na]+ calcd for C19H13NO4Na: 342.0742.
Found: 342.0721.
12-Methoxycarbonyl-2-ethylbenzo[f ]pyrido[1,2-a]indole-6,11-
dione (5t). Red solid: mp 236−237 °C; 1H NMR (400 MHz, CDCl3)
δ 1.35 (t, J = 7.6 Hz, 3H), 2.78 (q, J = 7.6 Hz, 2H), 4.06 (s, 3H), 7.05
(d, J = 7.2 Hz, 1H), 7.70−7.73 (m, 2H), 8.13 (s, 1H), 8.20−8.22 (m,
2H), 9.74 (d, J = 7.2 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 180.5,
174.9, 164.2, 145.7, 140.4, 134.2, 133.8, 133.4, 133.1, 128.9, 127.8,
127.3, 126.0, 122.3, 119.0, 118.1, 104.4, 52.0, 28.9, 14.2; IR (KBr)
2966, 1693, 1678, 1632, 1590, 1575, 1525, 1498, 1474, 1395, 1288,
1230, 1164, 1122, 1052, 1011, 891, 821, 791, 709 cm−1. HRMS (ESI)
m/z [M + Na]+ calcd for C20H15NO4Na: 356.0899. Found: 356.0883.
General Procedure for the Preparation of Benz[5,6]indolo-
[2,1-a]isoquinoline-8,13-dione 6. Isoquinoline 2 (3.0 mmol), acyl
bromide 3 (1.0 mmol), 1,4-naphthaquionone 4 (1.0 mmol), and
hydrated copper chloride (0.1 mmol) were mixed in 15 mL of CH3CN
and heated to reflux for 12 h. After completion of the reaction, the
reaction mixture was separated by silica gel column chromatography to
afford the compound 6.
12-Benzoyl-2-ethylbenzo[f ]pyrido[1,2-a]indole-6,11-dione (5o).
1
Red solid: mp 205−207 °C; H NMR (400 MHz, CDCl3) δ 1.32
(td, J = 7.2, 0.4 Hz, 3H), 2.76 (qd, J = 7.2, 0.4 Hz, 2H), 7.09 (dd, J =
7.2, 1.2 Hz, 1H), 7.47 (t, J = 7.6 Hz, 2H), 7.61 (t, J = 7.2 Hz, 1H), 7.65
(dd, J = 7.6, 0.8 Hz, 1H), 7.74 (td, J = 7.6, 0.8 Hz, 1H), 7.81 (s, 1 H),
7.92 (d, J = 7.2 Hz, 2 H), 8.02 (d, J = 7.2 Hz, 1H), 8.26 (d, J = 7.2 Hz,
1H), 9.73 (d, J = 7.2 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 191.9,
180.9, 174.5, 145.4, 139.9, 139.2, 134.6, 134.4, 133.7, 132.9, 132.8,
129.2, 128.6, 128.3, 127.8, 127.1, 126.2, 121.0, 119.3, 117.5, 112.7,
28.7, 14.1; IR (KBr) 3058, 2917, 1666, 1632, 1591, 1558, 1506, 1489,
1436, 1396, 1357, 1288, 1231, 1171, 1117, 1062, 1019, 922, 788, 710
cm−1. HRMS (ESI) m/z [M + Na]+ calcd for C25H17NO3Na:
402.1106. Found: 402.1125.
14-Benzoylbenz[5,6]indolo[2,1-a]isoquinoline-8,13-dione (6a).
Yellow solid: mp >300 °C (lit.11 307.5−308.5 °C); H NMR (400
1
MHz, CDCl3) δ 7.36 (d, J = 7.6 Hz, 1H), 7.45−7.69 (m, 6H), 7.76 (t,
J = 8.4 Hz, 2H), 7.94 (d, J = 8.0 Hz, 1H), 8.08 (d, J = 7.6 Hz, 3H),
8.29 (d, J = 7.6 Hz, 1 H), 9.54 (d, J = 7.2 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ 194.8, 180.7, 175.3, 137.5, 134.6, 134.0, 133.8, 133.7,
133.3, 133.2, 133.0, 129.5, 129.2, 129.1, 128.9, 127.8, 127.7, 126.9,
126.6, 124.8, 124.5, 122.6, 117.6, 116.9; IR (KBr) 3126, 3055, 1665,
1657, 1645, 1593, 1505, 1393, 1236, 1221, 957, 792, 706 cm−1. HRMS
(ESI) m/z [M + Na]+ calcd for C27H15NO3Na: 424.0950. Found:
424.0969.
12-(4-Chlorobenzoyl)-2-ethylbenzo[f ]pyrido[1,2-a]indole-6,11-
dione (5p). Red solid: mp 278−280 °C; 1H NMR (400 MHz, CDCl3)
δ 1.24 (t, J = 7.6 Hz, 3H), 2.68 (q, J = 7.6 Hz, 2H), 7.01 (d, J = 7.2 Hz,
1H), 7.34 (d, J = 8.4 Hz, 2H), 7.57 (t, J = 7.6 Hz, 1H), 7.66 (t, J = 7.6
Hz, 1H), 7.74−7.77 (m, 3 H), 7.93 (d, J = 7.6 Hz, 1H), 8.17 (d, J = 7.6
Hz, 1H), 9.64 (d, J = 7.2 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ
190.7, 181.1, 174.7, 145.9, 140.0, 139.1, 137.7, 134.3, 133.9, 133.5,
133.0, 130.6, 128.7, 128.5, 127.8, 127.1, 126.3, 121.1, 119.5, 117.5,
112.1, 28.8, 14.1; IR (KBr) 3067, 2966, 2920, 1667, 1630, 1585, 1527,
1485, 1391, 1356, 1283, 1230, 1170, 1085, 1061, 1033, 1010, 921, 854,
805, 713 cm−1. HRMS (ESI) m/z [M + Na]+ calcd for
C25H16ClNO3Na: 436.0716. Found: 436.0728.
12-(4-Methoxybenzoyl)-2-ethylbenzo[f ]pyrido[1,2-a]indole-6,11-
dione (5q). Red solid: mp 236−237 °C; 1H NMR (400 MHz, CDCl3)
δ 1.32 (t, J = 7.6 Hz, 3H), 2.77 (q, J = 7.6 Hz, 2H), 3.90 (s, 3H), 6.95
(d, J = 8.4 Hz, 2H), 7.07 (d, J = 7.2 Hz, 1H), 7.65 (td, J = 7.2, 1.2 Hz,
1H), 7.73 (s, 1H), 7.76 (d, J = 7.6 Hz, 1H), 7.93 (d, J = 8.4 Hz, 2H),
8.06 (d, J = 7.6 Hz, 1H), 8.27 (d, J = 8.0 Hz, 1H), 9.72 (d, J = 7.2 Hz,
1H); 13C NMR (100 MHz, CDCl3) δ 190.4, 181.1, 177.5, 163.6,
152.5, 145.0, 134.6, 133.7, 132.8, 131.9, 131.7, 128.3, 127.7, 127.1,
126.2, 122.5, 120.9, 119.2, 117.5, 113.7, 113.3, 55.4, 28.7; IR (KBr)
2956, 1667, 1634, 1600, 1575, 1505, 1495, 1395, 1358, 1287, 1256,
1231, 1169, 1063, 1033, 928, 850, 792, 714 cm−1. HRMS (ESI) m/z
[M + Na]+ calcd for C26H19NO4Na: 432.1212. Found: 432.1203.
12-(Biphenylcarbonyl)-2-ethylbenzo[f ]pyrido[1,2-a]indole-6,11-
dione (5r). Red solid: mp 240−241 °C; 1H NMR (400 MHz, CDCl3)
δ 1.32 (t, J = 7.6 Hz, 3H), 2.77 (q, J = 7.6 Hz, 2H), 7.10 (d, J = 7.2 Hz,
1H), 7.41 (d, J = 7.2 Hz, 1H), 7.48 (t, J = 7.6 Hz, 2H), 7.63−7.76 (m,
6H), 7.80 (s, 1H), 8.00 (d, J = 8.0 Hz, 2H), 8.03 (d, J = 8.0 Hz, 1H),
8.27 (d, J = 7.6 Hz, 1H), 9.74 (d, J = 7.2 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ 191.5, 181.1, 174.6, 145.5, 140.1, 139.8, 137.8, 134.5,
133.8, 133.6, 132.9, 129.9, 128.9, 128.6, 128.1, 127.8, 127.4, 127.1,
127.0, 126.3, 121.2, 121.0, 119.4, 117.5, 112.9, 28.8, 14.1; IR (KBr)
2960, 2924, 1665, 1628, 1601, 1523, 1491, 1395, 1359, 1287, 1232,
1174, 1063, 1006, 922, 852, 811, 757 cm−1. HRMS (ESI) m/z [M +
Na]+ calcd for C31H21NO3Na: 478.1419. Found: 478.1423.
14-(4-Chlorobenzoyl)benz[5,6]indolo[2,1-a]isoquinoline-8,13-
dione (6b). Yellow solid: mp >300 °C; 1H NMR (400 MHz, CDCl3) δ
7.37 (d, J = 7.6 Hz, 1H), 7.48 (t, J = 8.4 Hz, 3H), 7.60 (t, J = 7.6 Hz,
1H), 7.69 (t, J = 7.6 Hz, 1H), 7.75−7.80 (m, 2H), 7.92 (d, J = 8.0 Hz,
1H), 8.01 (d, J = 8.4 Hz, 2H), 8.08 (d, J = 7.2 Hz, 1H), 8.29 (d, J = 7.6
Hz, 1H), 9.54 (d, J = 7.6 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ
193.7, 181.0, 175.1, 136.5, 135.8, 134.6, 133.9, 133.7, 133.2, 132.7,
131.3, 129.8, 128.5, 128.4, 128.3, 128.0, 127.7, 127.3, 126.7, 126.5,
125.1, 120.5, 117.8, 114.2; IR (KBr) 3057, 1673, 1659, 1643, 1585,
1547, 1530, 1508, 1480, 1456, 1392, 1358, 1285, 1268, 1234, 1220,
1093, 989, 956, 795 cm−1. HRMS (ESI) m/z [M + Na]+ calcd for
C27H14ClNO3Na: 458.0560. Found: 458.0551.
14-(4-Methoxybenzoyl)benz[5,6]indolo[2,1-a]isoquinoline-8,13-
dione (6c). Yellow solid: mp 273−275 °C; 1H NMR (400 MHz,
CDCl3) δ 3.88 (s, 3H), 6.96 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 7.2 Hz,
1H), 7.46 (t, J = 7.6 Hz, 1H), 7.58 (t, J = 7.2 Hz, 1H), 7.68 (t, J = 7.6
Hz, 1H), 7.76 (t, J = 7.2 Hz, 2H), 7.96 (d, J = 8.4 Hz, 1H), 8.05 (d, J =
8.0 Hz, 2H), 8.09 (d, J = 7.6 Hz, 1H), 8.29 (d, J = 7.2 Hz, 1H), 9.53
(d, J = 7.2 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 193.2, 180.8,
175.2, 164.4, 134.6, 133.7, 133.3, 133.2, 132.0, 130.7, 129.5, 129.1,
129.0, 127.6, 126.9, 126.6, 124.9, 124.6, 124.5, 117.5, 117.3, 114.2,
55.5; IR (KBr) 3063, 2919, 1656, 1644, 1598, 1575, 1526, 1504, 1478,
1457, 1409, 1393, 1358, 1307, 1257, 1238, 1219, 1164, 990, 962, 847,
807 cm−1. HRMS (ESI) m/z [M + Na]+ calcd for C28H17NO4Na:
454.1055. Found: 454.1068.
14-Ethoxycarbonylbenz[5,6]indolo[2,1-a]isoquinoline-8,13-dione
(6d). Yellow solid: mp 238−240 °C (lit.11 239−239.5 °C); H NMR
1
(400 MHz, CDCl3) δ 1.55 (t, J = 7.2 Hz, 3H), 4.69 (q, J = 7.2 Hz,
2H), 7.27 (d, J = 7.2 Hz, 1H), 7.60 (t, J = 7..6 Hz, 2H), 7.68−7.75 (m,
3H), 8.21 (dd, J = 8.0, 1.6 Hz, 1H), 8.23−8.27 (m, 2H), 9.41 (d, J =
7.6 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 180.5, 175.1, 166.5,
134.4, 133.6, 133.4, 133.1, 132.5, 129.4, 129.3, 128.9, 127.6, 126.8,
126.7, 126.5, 124.4, 124.3, 124.2, 122.4, 117.3, 110.2, 62.4, 14.1; IR
12-Ethoxycarbonyl-2-ethylbenzo[f ]pyrido[1,2-a]indole-6,11-
dione (5s). Red solid: mp 142−143 °C; 1H NMR (400 MHz, CDCl3)
1196
dx.doi.org/10.1021/jo2023312 | J. Org. Chem. 2012, 77, 1191−1197