Y. Aoki et al. / Bioorg. Med. Chem. 15 (2007) 7108–7115
7113
4
.2.14. Compound 2e. The synthesis was performed using
(0.139 g, 0.313 mmol). R : 0.35 (CH Cl /MeOH, 9:1).
f 2 2
lumazine 2a (0.164 g, 1.00 mmol) and hexaethylene gly-
col diiodide (0.602 g, 1.20 mmol). The crude compound
was purified by silica gel column chromatography
Mp 205–207 ꢁC. IR (KBr): 1720, 1681, 1557, 1483,
À1
1
1362, 1230, 1118, 912, 743, 651 cm
.
H NMR
(400 MHz, CDCl ): d 2.50 (s, 3H), 2.53 (s, 3H), 3.42–
3
(
acetone to give a colorless solid. Yield: 68% (0.280 g,
CH Cl /MeOH, 9:1) followed by recrystallization from
3.47 (m, 2H), 3.52–3.54 (m, 2H), 3.58–3.62 (m, 2H),
3.63–3.66 (m, 6H), 3.90 (t, 2H, J = 5.2 Hz), 3.98 (t,
2H, J = 5.2 Hz), 4.46 (t, 2H, J = 5.2 Hz), 4.71 (t, 2H,
2
2
0
.683 mmol). R : 0.42 (CH Cl /MeOH, 9:1). Mp 69–
f 2 2
1
3
7
0 ꢁC. IR (KBr): 1722, 1678, 1548, 1490, 1348, 1231,
J = 5.2 Hz), 7.78 (s, 1H), 8.06 (s, 1H). C NMR
(125 MHz, CDCl ): d 20.31, 20.86, 41.61, 41.67, 67.80,
À1
1
1
116, 916, 730 cm . H NMR (400 MHz, CDCl ): d
3
3
3
4
2
.36–3.38 (m, 2H), 3.42–3.48 (m, 4H), 3.53–3.57 (m,
H), 3.60–3.66 (m, 6H), 3.85–3.90 (m, 4H), 4.39 (t,
H, J = 5.6 Hz), 4.60 (t, 2H, J = 5.6 Hz), 8.55 (d, 1H,
68.01, 70.54, 70.60, 70.84, 70.99, 71.10, 126.82, 128.81,
129.45, 139.17, 139.86, 142.28, 144.94, 145.45, 150.66,
+
+
160.05. FAB-MS: 445 m/z [M+H] , 467 [M+Na] . Anal.
Calcd For C H N O Æ1/2CH Cl : C, 55.49; H, 6.01; N,
11.51. Found: C, 55.65; H, 6.06; N, 11.39.
1
3
J = 2.4 Hz), 8.60 (d, 1H, J = 2.4 Hz). C NMR
(125 MHz, CDCl ): d 41.47, 41.65, 67.61, 67.82, 70.59,
2
2
28
4
6
2
2
3
7
1
0.67, 70.71, 70.77, 70.81, 70.85, 128.30, 140.08,
47.10, 148.51, 150.36, 160.02. EI-MS: 410 m/z [M] .
+
4.2.18. Compound 3e. The synthesis was performed using
lumichrome 3a (0.242 g, 1.00 mmol) and hexaethylene
glycol diiodide (0.602 g, 1.20 mmol). The crude com-
pound was purified by silica gel column chromatogra-
phy (CH Cl /MeOH, 9:1) followed by recrystallization
+
HRMS (ESI-FTMS) Calcd for [M+Na] (C H N O
26
Na): 433.1694. Found: 433.1688.
1
8
4
7-
4
.2.15. Compound 3b. The synthesis was performed
2
2
using lumichrome 3a (0.242 g, 1.00 mmol) and triethyl-
ene glycol diiodide (0.444 g, 1.20 mmol). The crude com-
pound was purified by silica gel column
chromatography (CH Cl /MeOH, 9:1) followed by
from CH Cl to give a yellow solid. Yield: 42%
2 2
(0.204 g, 0.418 mmol). R : 0.35 (CH Cl /MeOH, 9:1).
2
f
2
Mp 125–127 ꢁC. IR (KBr): 1718, 1681, 1557, 1458,
1363, 1107, 912, 742, 651 cm . H NMR (400 MHz,
À1
1
2
2
recrystallization from CH Cl to give a yellow solid.
2
CDCl ): d 2.51 (s, 3H), 2.53 (s, 3H), 3.48–3.50 (m,
2
3
Yield: 28% (0.100 g, 0.281 mmol). R : 0.42 (CH Cl /
2
4H), 3.57–3.61 (m, 4H), 3.62–3.74 (m, 8H), 3.89 (t,
2H, J = 5.6 Hz), 3.96 (t, 2H, J = 5.6 Hz), 4.44 (t, 2H,
J = 5.6 Hz), 4.70 (t, 2H, J = 5.6 Hz), 7.78 (s, 1H), 8.06
f
2
MeOH, 9:1). Mp 280–281 ꢁC. IR (KBr): 1720, 1679,
À1
553, 1388, 1102 cm . H NMR (400 MHz, CDCl ):
3
1
1
1
3
d 2.51 (s, 3H), 2.53 (s, 3H), 3.21–3.26 (m, 2H), 3.53–
(s, 1H). C NMR (125 MHz, CDCl ): d 20.30, 20.85,
3
3
4
1
.69 (m, 4H), 4.03–4.11 (m, 2H), 4.38–4.34 (m, 1H),
.53–4.55 (m, 1H), 4.64–4.69 (m, 1H), 5.06–5.11 (m,
41.47, 41.65, 67.81, 70.53, 70.60, 70.63, 70.72, 70.75,
70.79, 126.83, 128.89, 129.42, 139.23, 139.85, 142.30,
1
3
H), 7.75 (s, 1H), 8.06 (s, 1H). C NMR (125 MHz,
+
145.04, 145.41, 150.66, 160.09. EI-MS: 488 m/z [M] .
+
HRMS (ESI-FTMS) Calcd for [M+Na] (C H N O
Na): 511.2163. Found: 511.2159.
CDCl ): d 20.28, 20.85, 42.27, 42.54, 68.01, 68.44,
3
24 32
4
7-
7
2.42, 72.81, 126.77 129.00, 129.46, 139.31, 139.78,
42.46, 145.31, 145.47, 151.87, 160.05. FAB-MS: 357
1
m/z [M+H] . HRMS (ESI-FTMS) Calcd for [M+Na]
+
+
4.2.19. Compound 4b. The synthesis was performed
using phenobarbital (4a) sodium salt (0.254 g,
(
C H N O Na): 379.1377. Found: 379.1386.
18 20 4 4
1.00 mmol) and triethylene glycol diiodide (0.444 g,
4
.2.16. Compound 3c. The synthesis was performed using
1.20 mmol). The crude compound was purified by silica
gel column chromatography (CH Cl /MeOH, 19:1) fol-
lowed by recrystallization from CH Cl to give a color-
lumichrome 3a (0.242 g, 1.00 mmol) and tetraethylene
glycol diiodide (0.497 g, 1.20 mmol). The crude com-
pound was purified by silica gel column chromatogra-
phy (CH Cl /MeOH, 9:1) followed by recrystallization
2
2
2
2
less solid. Yield: 30% (0.105 g, 0.303 mmol). R : 0.60
f
(CH Cl /MeOH, 19:1). Mp 164–165 ꢁC. IR (KBr):
2
2
2
2
from CH Cl to give a yellow solid. Yield: 40%
2
1693, 1439, 1399, 1281, 1200, 1137, 1107, 1060, 903,
2
À1
1
(
0.160 g, 0.400 mmol). R : 0.38 (CH Cl /MeOH, 9:1).
f
767 cm . H NMR (400 MHz, CDCl ): d 1.01 (t, 3H,
2
2
3
Mp 219 ꢁC. IR (KBr): 1718, 1677, 1555, 1480, 1459,
J = 7.2 Hz), 2.37 (q, 2H, J = 7.2, 14 Hz), 3.40–3.45 (m,
2H), 3.57–3.66 (m, 4H), 3.89–3.93 (m, 2H), 4.01–4.06
À1
1
1
389, 1361, 1229, 1130, 752 cm
.
H
NMR
1
3
(
400 MHz, CDCl ): d 2.50 (s, 3H), 2.52 (s, 3H), 3.37–
(m, 2H), 4.36–4.40 (m, 2H), 7.29–7.33 (m, 5H).
C
3
3
4
1
.56 (m, 5H), 3.62–3.70 (m, 4H), 3.85–4.00 (m, 4H),
.36–4.40 (m, 1H), 4.57–4.64 (m, 1H), 4.72–4.78 (m,
H), 7.75 (s, 1H), 8.06 (s, 1H). C NMR (125 MHz,
NMR (125 MHz, CDCl ): d 10.77, 30.71, 42.40, 62.79,
3
68.45, 72.62, 125.49, 128.46, 129.22, 152.29, 169.23.
FAB-MS: 347 m/z [M+H] . Anal. Calcd for
1
3
+
CDCl ): d 20.08, 20.82, 41.65, 41.73, 67.22, 67.37,
C H N O : C, 62.42; H, 6.40; N, 8.09. Found: C,
18 22
62.06; H, 6.39; N, 8.14.
3
2
5
7
0.07, 70.29, 70.35, 126.79, 128.94, 129.47, 139.15,
39.69, 142.30, 145.03, 145.31, 150.83, 160.04. FAB-
1
MS: 401 m/z [M+H] . HRMS (ESI-FTMS) Calcd for
+
4.2.20. Compound 4c. The synthesis was performed using
phenobarbital (4a) sodium salt (0.254 g, 1.00 mmol) and
tetraethylene glycol diiodide (0.497 g, 1.20 mmol). The
crude compound was purified by silica gel column chro-
matography (CH Cl /MeOH, 19:1) followed by recrys-
+
[
M+Na] (C H N O Na): 423.1639. Found: 423.1638.
20 24 4 5
4
.2.17. Compound 3d. The synthesis was performed
using lumichrome 3a (0.242 g, 1.00 mmol) and pentaeth-
ylene glycol diiodide (0.550 g, 1.20 mmol). The crude
compound was purified by silica gel column chromatog-
raphy (CH Cl /MeOH, 9:1) followed by recrystalliza-
2
2
tallization from CH Cl to give a colorless solid.
2
2
Yield: 62% (0.242 g, 0.621 mmol). R : 0.46 (CH Cl /
f
2
2
MeOH, 19:1). Mp 109–110 ꢁC. IR (KBr): 1751, 1681,
1435, 1399, 1361, 1291, 1197, 1136, 1097, 918, 752,
2
2
tion from CH Cl to give a yellow solid. Yield: 31%
2
2