Parenty et al.
(12), 178.1 (5), 154.1 (2), 136.1 (2). Anal. Calcd for C17H17N2-
OBr: C, 59.14; H, 4.96; N, 8.11. Found: C, 58.67; H, 4.78; N,
7.92.
(22), 137.1 (15). Anal. Calcd for C25H23BrN2O2‚H2O: C, 62.38;
H, 5.23; N, 5.82. Found: C, 62.27; H, 5.32; N, 5.95.
1-P h en yl-2,3-d ih yd r o-1H-im id a zo[1,2-f]p h en a n th r id in -
4-yliu m Br om id e (6g). 6g (260 mg; 0.695 mol) was obtained
2,3-Dih yd r o-1H-im id a zo[1,2-f]p h en a n th r id in -4-yliu m
Br om id e (6c). 6c (250 mg; 0.83 mmol) was obtained as a
yellow powder in a 61% yield: mp 392-394 °C (dec); 1H NMR
(D2O, 400 MHz) δ 7.83 (d, 1H, J ) 8.0 Hz), 7.79 (d, 1H, J )
8.0 Hz), 7.66 (t, 1H, J ) 8.0 Hz), 7.46 (m, 3H), 7.28 (t, 1H, J
) 8.0 Hz), 6.93 (d, 1H, J ) 8.0 Hz), 4.13 (t, 2H, J ) 10.8 Hz),
3.91 (t, 2H, J ) 10.8 Hz); 13C NMR (D2O, 100 MHz) δ 154.69
(C), 135.75 (CH), 133.18 (C), 131.65 (C), 129.56 (CH), 126.26
(CH), 125.65 (CH), 123.40 (CH), 123.01 (CH), 119.25 (C),
115.45 (CH), 113.64 (C), 47.62 (CH2), 43.04 (CH2); IR (KBr,
cm-1) 3435 (s), 3028 (m), 2997 (m), 2950 (m), 2773 (w), 2684
(w), 2050 (w), 1626 (s), 1608 (s), 1585 (s), 1469 (m), 1454 (m),
1358 (m), 1294 (m), 1267 (w), 1169 (w), 1022 (w), 754 (s); MS
(EI+) 220 (M - Br) (10), 219.3 (12), 142.3 (8), 112.2 (5), 100.2
(15), 86.2 (100), 56.1 (50). Anal. Calcd for C15H13N2Br: C, 59.82;
H, 4.35; N, 9.30. Found: C, 59.39; H, 4.23; N, 9.03.
1
as a yellow powder in a 73% yield: mp 355-356 °C (dec); H
NMR (CD3OD, 400 MHz) δ 8.85 (d, 1H, J ) 8.4 Hz), 8.75 (d,
1H, J ) 8.4 Hz), 8.05 (t, 1H, J ) 8.4 Hz), 7.93 (t, 1H, J ) 8.4
Hz), 7.81 (d, 1H, J ) 8.4 Hz), 7.71 (m, 6H), 7.45 (m, 2H), 5.04
(t, 2H, J ) 10.4 Hz), 4.69 (t, 2H, J ) 10.4 Hz); 13C NMR (CD3-
OD, 100 MHz) δ 154.87 (C), 144.05 (C), 141.02 (CH), 137.69
(CH), 137.07 (CH), 134.63 (C), 133.20 (CH), 132.60 (CH),
132.02 (CH), 129.94 (CH), 129.24 (CH), 128.47 (CH), 126.45
(CH), 125.76 (CH), 122.72 (C), 120.46 (C), 117.43 (CH), 117.00
(C), 56.19 (CH2), 48.76 (CH2); IR (KBr, cm-1) 3434 (s), 3047
(w), 1612 (m), 1599 (m), 1575 (s), 1545 (s), 1485 (w), 1440 (m),
1309 (s), 1171 (w), 935(w), 758 (s); MS (FAB) 297 (M - Br)
(100), 269 (2), 230 (8), 219 (4), 178 (4), 154 (6), 136 (5), 107.2
(1), 77.6 (2). Anal. Calcd for C21H17N2Br‚ 0.5H2O: C, 65.30;
H, 4.70; N, 7.25. Found: C, 65.71; H, 4.53; N, 7.11.
1-Isop r op yl-2,3-d ih yd r o-1H-im id a zo[1,2-f]p h en a n th r i-
d in -4-yliu m Br om id e (6d ). 6d (267 mg; 0.78 mmol) was
obtained as a yellow powder in a 82% yield: mp 250-251 °C
(dec); 1H NMR (CD3OD, 400 MHz) δ 8.81 (d, 1H, J ) 8.4 Hz),
8.62 (d, 1H, J ) 8.4 Hz), 8.58 (d, 1H, J ) 8.4 Hz), 8.12 (t, 1H,
J ) 8.4 Hz), 7.90 (t, 1H, J ) 8.4 Hz), 7.82 (t, 1H, J ) 8.4 Hz),
7.62 (m, 2H), 5.23 (q, 1H, J ) 6.6 Hz), 4.76 (t, 2H, J ) 10.5
Hz), 4.38 (t, 2H, J ) 10.5 Hz), 1.62 (d, 6H, J ) 6.6 Hz); 13C
NMR (CD3OD, 100 MHz) δ 155.03 (C), 137.64 (C), 136.76 (CH),
134.96 (C), 133.02 (CH), 130.74 (CH), 129.55 (CH), 126.95
(CH), 125.81 (CH), 125.29 (CH), 122.21 (C), 117.52 (C), 116.98
(CH), 52.50 (CH), 47.51 (CH), 45.16 (CH2), 21.22 (CH3); IR
(KBr, cm-1) 3433 (s), 2981 (w), 2015 (w), 1610 (m), 1597 (m),
1574 (s), 1550 (s), 1556 (w), 1303 (m), 1169 (w), 1126 (w), 1068
(w), 758 (m); MS (FAB) 263.2 (M - Br) (100), 221.1 (6), 154.1
(12), 137.1 (6), 89.6 (2), 77.7 (1). Anal. Calcd for C18H19N2Br‚
0.25 H2O: C, 62.17; H, 5.65; N, 8.90. Found: C, 62.27; H, 6.01;
N, 8.95.
1-Cyclop r op yl-2,3-d ih yd r o-1H -im id a zo[1,2-f]p h en a n -
th r id in -4-yliu m Br om id e (6e). 6e (250 mg; 0.74 mmol) was
obtained as a white off powder in a 78% yield: mp 129-130
°C (dec); 1H NMR (D2O, 400 MHz) δ 8.84 (d, 1H, J ) 8.4 Hz),
8.20 (d, 1H, J ) 8.0 Hz), 8.84 (d, 1H, J ) 8.0 Hz), 8.10 (d, 1H,
J ) 8.0 Hz), 7.85 (t, 1H, J ) 8.0 Hz), 7.64 (m, 2H), 7.42 (t, 1H,
J ) 8.0 Hz), 7.17 (d, 2H, J ) 8.0 Hz), 4.25 (t, 2H, J ) 11 Hz),
4.11 (t, 2H, J ) 11 Hz), 3.26 (qt, 1H, J ) 3.5 Hz), 1.21 (m,
2H), 1.03 (m, 2H); 13C NMR (D2O, 100 MHz) δ 155.05 (C),
155.05 (C), 135.52 (CH), 134.87 (C), 132.43 (C), 131.55 (CH),
129.24 (CH), 128.88 (CH), 125.69 (CH), 123.55 (CH), 123.40
(CH), 119.98 (C), 115.46 (CH), 102.52 (C), 49.95 (CH2), 45.77
(CH2), 31.51(CH), 10.49 (2×CH2); IR (KBr, cm-1) 3427 (s), 3024
(w), 2358 (w), 1610 (m), 1595 (m), 1575 (s), 1548 (s), 1454 (m),
1356 (w), 1307 (m), 1045 (w), 762 (m); MS (FAB) 261.1 (M -
Br) (100), 219.1 (6), 154 (12), 136 (11), 120.1 (2), 89.5 (2), 77.7-
(1). Anal. Calcd for C18H17N2Br: C, 64.35; H, 5.02; N, 8.21.
Found: C, 64.68; H, 5.02; N, 8.09.
1-(4-Met h oxy-p h en yl)-2,3-d ih yd r o-1H -im id a zo[1,2-f]-
p h en a n th r id in -4-yliu m Br om id e (6h ). 6h (285 mg; 0.7
mmol) was obtained as a pale green powder in a 74% yield:
1
mp 368-369 °C (dec); H NMR ((CD3)2SO, 400 MHz) δ 8.90
(d, 1H, J ) 8.0 Hz), 8.80 (d, 1H, J ) 8.0 Hz), 0.05 (t, 1H, J )
8.0 Hz), 7.91 (t, 1H, J ) 8.0 Hz), 7.82 (d, 1H, J ) 8.0 Hz), 7.67
(m, 3H), 7.58 (t, 1H, J ) 8.0 Hz), 7.35 (d, 1H, J ) 8.0 Hz),
7.24 (d, 2H, J ) 8.0 Hz), 4.92 (t, 2H, J ) 9.8 Hz), 4.56 (t, 2H,
J ) 9.8 Hz), 3.88 (s, 3H); 13C NMR ((CD3)2SO, 100 MHz) δ
160.42 (C), 152.98 (C), 135.59 (CH), 135.36 (C), 133.03 (C),
131.90 (CH), 131.88 (CH), 129.02 (CH), 128.51 (CH), 128.50
(CH), 127.29 (CH), 125.98 (CH), 124.64 (CH), 124.43 (CH),
120.63 (C), 120.62 (C), 116.45 (CH), 116.30 (CH), 115.77 (C),
56.02 (CH3), 55.01 (CH2), 47.09 (CH2); IR (KBr, cm-1) 3435
(s), 29232 (w), 2360 (w), 1610 (s), 1577 (s), 1554 (m), 1512 (m),
1456 (w), 1298 (w), 1251 (s), 1028 (m), 764 (m); MS (FAB) 327.1
(M - Br) (100), 307.1 (20), 289.1 (10), 261.1 (2), 219.1 (2), 154
(80), 136 (50), 107.3 (16), 89.5 (14), 77.6 (12), 65.8 (5), 52 (5).
Anal. Calcd for C22H19N2OBr‚ H2O: C, 62.13; H, 4.98; N, 6.59.
Found: C, 62.21; H, 4.46; N, 6.60.
Eth ylen ed ia m in e Der iva tive (6i). 2-Bromo-ethyl-phenan-
thridinium bromide (2) (700 mg; 1.9 mmol) was suspended in
DMF (20 mL). Ethylenediamine (31.8 µL; 0.48 mmol) and TEA
(530 µL; 3.8 mmol) were added successively to the stirred
solution. After stirring for 48 h at room temperature under
nitrogen, the final product and TEA hydrobromide salt were
precipitated from the solution with diethyl ether (100 mL) and
recovered by filtration. The precipitate was washed thoroughly
with diethyl ether and triturated with 1 mL of water to remove
the TEA salt, yielding, 6i (295 mg; 0.47 mmol) as a yellow
powder in a 98% yield: mp > 400 °C; 1H NMR ((CD3)2SO, 400
MHz) δ 8.70 (d, 2H, J ) 8.0 Hz), 8.66 (d, 2H, J ) 8.0 Hz), 8.62
(d, 2H, J ) 8.0 Hz), 8.01 (t, 2H, J ) 8.0 Hz), 7.87 (t, 2H, J )
8.0 Hz), 7.78 (t, 2H, J ) 8.0 Hz), 7.66 (m, 4H), 4.76 (s, 4H),
4.68 (t, 4H, J ) 10.6 Hz), 4.50 (t, 4H, J ) 10.6 Hz); IR (KBr,
cm-1) 3435 (s), 1612 (m), 1597 (m), 1574 (s), 1554 (s), 1456
(w), 1311 (m), 1265 (m), 762 (m); MS (FAB) 234 ((M - 2Br)/2)
(5), 232 (10), 214 (5), 198 (1), 157 (35), 137 (5), 102.4 (2), 79.6
(100), 61.8 (5). Anal. Calcd for C32H28N4Br2‚H2O: C, 59.46; H,
4.68; N, 8.67. Found: C, 59.80; H, 4.42; N, 8.31.
1-(1-Meth oxyca r bon yl-2-p h en yl-eth yl)-2,3-d ih yd r o-1H-
im id a zo[1,2-f]p h en a n t h r id in -4-yliu m Br om id e (6f). 6f
(550 mg; 1.2 mmol) was obtained as a hygroscopic white
1
powder in a 63% yield: mp 137-138 °C; H NMR (D2O, 400
MHz) δ 8.13 (d, 1H, J ) 8.0 Hz), 8.03 (d, 1H, J ) 8.0 Hz), 7.87
(d, 1H, J ) 8.0 Hz), 7.82 (t, 1H, J ) 8.0 Hz), 7.62 (t, 1H, J )
8.0 Hz), 7.59 (t, 1H, J ) 8.0 Hz), 7.44 (t, 1H, J ) 8.0 Hz), 7.22
(d, 1H, J ) 8.0 Hz), 7.05 (d, 2H, J ) 6.4 Hz), 6.82 (m, 3H),
5.90 (dd, 1H, J ) 15.6 and 4 Hz), 4.48 (m, 1H), 4.30 (m, 2H),
4.19 (m, 1H), 3.84 (s, 3H), 3.50 (dd, 1H, J ) 15.6 and 4 Hz),
3.24 (dd, 1H, J ) 15.6 and 11.2 Hz); 13C NMR (D2O, 100 MHz)
δ 135.96 (CH), 135.10 (C), 135.05 (C), 131.72 (CH), 131.5 (C),
129.22 (CH), 129.00 (CH), 127.80 (CH), 127.01 (CH), 126.64
(CH), 124.06 (CH), 123.51 (CH), 121.00 (CH), 120.00 (C),
115.97 (CH), 114.6 (C); IR (KBr, cm-1) 3433 (s), 1739 (s), 1610
(s), 1572 (s), 1534 (s), 1453 (m), 1265 (m), 753 (s); MS (FAB)
383.5 (M - Br) (100), 307.3 (12), 233.2 (5), 219.2 (5), 154.1
Tr is(2-a m in oeth yl)a m in e Der iva tive (6j). 2-Bromo-eth-
yl-phenanthridinium bromide (2) (1 g; 2.72 mmol) was sus-
pended in DMF (50 mL). Tris(2-aminoethyl)amine (68 µL;
0.454 mmol) and TEA (763 µL; 5.44 mmol) were added
successively to the stirred solution. After stirring for 48 h at
room temperature under nitrogen, the final product and TEA
hydrobromide salt were precipitated from the solution with
diethyl ether (100 mL) and recovered by filtration. The
precipitate was washed thoroughly with diethyl ether and
triturated with 1 mL of water to remove the TEA salt, yielding
6j (430 mg; 0.43 mmol) as a yellow powder in a 95% yield:
mp 326-327 °C; 1H NMR ((CD3)2SO, 400 MHz) δ 8.61 (d, 3H,
J ) 8.0 Hz), 8.51 (d, 3H, J ) 8.0 Hz), 8.43 (d, 3H, J ) 8.0 Hz),
5942 J . Org. Chem., Vol. 69, No. 18, 2004