δ 8.98 (d, 1H, J = 6.8 Hz), δ 8.91 (d, 1H, J = 6.4 Hz), δ 8.71 (d,
1H, J = 2 Hz), δ 8.26 (dd, 1H), δ 8.15 (t, 1H, J = 5.8 Hz), δ 7.96
(m, 2H), δ 7.80 (t, 1H, J = 6 Hz), δ 7.74 (d, 1H, J = 7.2 Hz), δ
7.68 (t, 1H, J = 6 Hz), δ 7.55 (d, 1H, J = 6.8 Hz), δ 5.05 (d, 2H,
J = 8 Hz), δ 4.73 (d, 2H, J = 8 Hz); 13C NMR (DMSO,
100 MHz): δ 152.6 (C), δ 150.8 (C), δ 148.0 (CH), δ 139.7
(CH), δ 135.9 (CH), δ 135.3 (C), δ 132.2 (C), δ 131.7 (CH),
δ 130.9 (C), δ 128.8 (CH), δ 128.2 (CH), δ 126.6 (CH),
δ 124.3 (CH), δ 124.2 (CH), δ 121.2 (C), δ 121.0 (CH),
δ 116.9 (CH), δ 115.1 (C), δ 52.1 (CH2), δ 47.7 (CH2); IR (KBr,
cm−1): 3440 (m), 3393 (m), 2975 (m), 2935 (m), 2736 (m),
2674 (m), 2491 (m), 1573 (s), 1304 (s), 1112 (m), 857 (m); MS
(FAB) for (C20H15N3Cl) (M+) 332 (28), 107 (100); HRMS
(FAB) for (C20H15N3Cl) (M+) calculated 332.0955, found
332.0952.
(CH), δ 140.2 (CH), δ 135.8 (CH), δ 135.2 (C), δ 132.2 (C), δ
131.7 (CH), δ 128.6 (CH), δ 127.9 (CH), δ 126.4 (CH), δ 124.7
(CH), δ 124.3 (CH), δ 124.2 (CH), δ 121.04 (C), δ 120.0 (CH),
δ 116.8 (CH), δ 115.2 (C), δ 52.2 (CH2), δ 47.5 (CH2); IR
(Goldengate, cm−1): 3415 (w), 3061 (w), 1647 (w), 1580 (m),
1309 (m), 1172 (w), 1038 (w), 753 (s); MS (FAB) for
(C20H16N3) (M+) 298 (100), 179 (14), 107 (27); HRMS (FAB)
for (C20H16N3) (M+) calculated 298.1344, found 298.1339.
1-(2-Hydroxy-phenyl)-2,3-dihydro-1H-imidazo[1,2-f]
phenanthridin-4-ylium bromide (14)
To a round bottomed flask a solution of BEP (500 mg, 1 eq) and
2-aminophenol (149 mg, 1 eq) with triethylamine (570 μL, 3 eq)
and chloroform (40 mL) was added and stirred at room tempera-
ture for 2.5 h. This created a creamy suspension which was
filtered and collected to yield the product as a white powder
(210 mg, 49%). 1H NMR (DMSO, 400 MHz): δ 10.52 (s, 1H), δ
8.94 (d, 1H, J = 8.4 Hz), δ 8.83 (d, 1H, J = 8.0 Hz), δ 8.09 (t,
1H, J = 7.6 Hz), δ 7.94 (t, 1H, J = 7.6 Hz), δ 7.85 (d, 1H, J =
8.4 Hz), δ 7.73 (t, 1H, J = 7.8 Hz), δ 7.64 (d, 1H, J = 8.4 Hz), δ
7.60 (d, 1H, J = 7.6 Hz), δ 7.50 (t, 2H, J = 9.4 Hz), δ 7.17 (d,
1H, J = 8.0 Hz), δ 7.11 (t, 1H, J = 7.6 Hz), δ 5.05 (q, 1H, J =
10.8 Hz), δ 4.94 (q, 1H, J = 10.8 Hz), δ 4.53 (t, 2H, J = 10.4
Hz); 13C NMR (DMSO, 100 MHz): δ 153.0 (C), δ 152.9 (C), δ
135.5 (CH), δ 134.7 (C), δ 132.5 (C), δ 131.7 (CH), δ 131.6
(CH), δ 129.0 (CH), δ 128.2 (CH), δ 126.0 (CH), δ 125.8 (CH),
δ 125.6 (C), δ 124.3 (CH), δ 124.1 (CH), δ 120.7 (CH), δ 120.2
(C), δ 117.7 (CH), δ 116.3 (CH), δ 115.6 (C), δ 52.9 (CH2), δ
46.7 (CH2); IR (Goldengate, cm−1): 2947 (w), 1613 (w), 1577
(m), 1486 (m), 1449 (w), 1393 (w), 1313 (m), 1240 (w), 1171
(w), 1153 (w), 1118 (w), 993 (w), 872 (w), 785 (w), 747 (s); MS
(FAB): 313 (M+) (15), 157 (60), 80 (100).
1-(6-Chloro-pyridin-3-yl)-2,3-dihydro-1H-imidazo[1,2-f]
phenanthridin-4-ylium bromide (12)
To a round bottomed flask a solution of BEP (286 mg, 1 eq) and
5-amino-2-chloropyridine (100 mg, 1 eq) with triethylamine
(325 μL, 3 eq) and chloroform (25 mL) was added and stirred at
room temperature for 4 h. The resulting solution was washed
with water and brine and was then concentrated under vacuum to
form a red/brown residue. The residue was then triturated in
1
acetone to yield the product as a yellow solid (40 mg, 15%). H
NMR (DMSO, 400 MHz): δ 8.97 (d, 1H, J = 6.8 Hz), δ 8.88 (d,
1H, J = 6.8 Hz), δ 8.80 (d, 1H, J = 2.4 Hz), δ 8.23 (dd, 1H, J =
2.4,7.2 Hz), δ 8.12 (t, 1H, J = 6.0 Hz), δ 7.96 (t, 1H, J = 6.2
Hz), δ 7.88 (t, 2H, J = 8.4 Hz), δ 7.77 (t, 1H, J = 6.0 Hz), δ 7.67
(t, 1H, J = 6.0 Hz), δ 7.49 (d, 1H, J = 6.8 Hz), δ 4.99 (t, 2H, J =
8.2 Hz), δ 4.66 (t, 2H, J = 8.0 Hz); 13C NMR (DMSO,
100 MHz): δ 153.0 (C), δ 150.4 (C), δ 148.0 (CH), δ 138.0
(CH), δ 136.2 (C), δ 135.6 (CH), δ 135.1 (C), δ 132.3 (C), δ
131.6 (CH), δ 129.1 (CH), δ 127.3 (CH), δ 126.2 (CH), δ 126.1
(CH), δ 124.5 (CH), δ 124.1 (CH), δ 120.8 (C), δ 116.5 (CH), δ
114.9 (C), δ 54.2 (CH2), δ 47.4 (CH2); IR (Goldengate, cm−1):
3019 (w), 1615 (w), 1577 (s), 1544 (m), 1527 (m), 1458 (m),
1451 (m), 1375 (w), 1311 (s), 1176 (w), 1108 (s), 935 (w), 844
(w), 761 (s); MS (FAB): 332 (M+) (20), 179 (30), 157 (30), 80
(100).
1-(4-Hydroxy-pyridin-3-yl)-2,3-dihydro-1H-imidazo[1,2-f]
phenanthridin-4-ylium bromide (15)
To a suspension of BEP (850 mg, 2.32 eq) in chloroform
(70 mL) was added 3-amino-4-hydroxypyridine (150 mg, 1 eq)
and triethylamine (570 μL, 3 eq) and stirred for 2.5 h. The sus-
pension was filtered and washed with acetone (278 mg, 56%).
1H NMR (DMSO, 400 MHz): δ 8.90 (d, 1H, J = 6.4 Hz), δ 8.82
(d, 1H, J = 6.4 Hz), δ 8.48 (s, 1H), δ 8.09 (t, 1H, J = 6.4 Hz), δ
8.06 (d, 1H, J = 6.8 Hz), δ 7.94 (t, 1H, J = 5.4 Hz), δ 7.92 (d,
1H, J = 6 Hz), δ 7.83 (d, 1H, J = 6 Hz), δ 7.73 (t, 1H, J = 6 Hz),
δ 7.68 (t, 1H, J = 6.2 Hz), δ 6.40 (d, 1H, J = 9 Hz), δ 5.10 (m,
1H), δ 4.83 (m, 1H), δ 4.59 (m, 1H), δ 4.23 (q, 1H); 13C NMR
(DMSO, 100 MHz): δ 171.7 (C), δ 154.0 (C), δ 139.2 (CH), δ
137.9 (CH), δ 135.5 (CH), δ 134.1 (C), δ 132.3 (C), δ 131.5
(CH), δ 129.3 (C), δ 129.1 (CH), δ 126.0 (CH), δ 126.0 (CH), δ
124.1 (CH), δ 124.0 (CH), δ 120.5 (C), δ 117.8 (CH), δ 116.5
(CH), δ 116.1 (C), δ 53.4 (CH2), δ 46.6 (CH2); IR (Goldengate,
cm−1): 3494 (w), 3056 (w), 2817 (w), 1642 (m), 1579 (s), 1312
(m), 784 (m), 717 (s); MS (FAB) for (C20H16N3O) (M+) 314
(100), 78 (10), 36 (24); HRMS (FAB) for (C20H16N3O) (M+)
calculated 314.1293, found 314.1289.
1-Pyridin-2-yl-2,3-dihydro-1H-imidazo[1,2-f]phenanthridin-4-
ylium bromide (13)
To a suspension of BEP (500 mg, 1 eq) in chloroform (50 mL)
was added 2-aminopyridine (94 mg, 1 eq) and triethylamine
(570 μL, 3 eq) and stirred at room temperature for 4 h, when a
solution had formed. It was washed with water, brine and con-
centrated under vacuum to an orange residue, then an acetone tri-
turation yielded a yellow powder (150 mg, 29%). 1H NMR
(DMSO, 400 MHz): δ 8.97 (d, 1H, J = 6.4 Hz), δ 8.89 (d, 1H, J
= 6 Hz), δ 8.65 (d, 1H, J = 4 Hz), δ 8.14 (t, 1H, J = 6.6 Hz), δ
8.12 (t, 1H, J = 6.2 Hz), δ 7.97 (q, 1H), δ 7.94 (t, 1H, J = 6 Hz),
δ 7.79 (t, 1H, J = 5.6 Hz), δ 7.72 (d, 1H, J = 6.4 Hz), δ 7.64 (d,
1H, J = 4.4 Hz), δ 7.63 (t, 1H, J = 2.8 Hz), δ 7.37 (d, 1H, J =
6.4 Hz), δ 5.04 (t, 2H, J = 8 Hz), δ 4.73 (t, 2H, J = 8 Hz); 13C
NMR (DMSO, 100 MHz): δ 152.7 (C), δ 152.1 (C), δ 149.7
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Org. Biomol. Chem., 2012, 10, 2026–2034 | 2033