7426
H.-S. Huang et al. / Bioorg. Med. Chem. 17 (2009) 7418–7428
8.03 (d, J = 8.4 Hz, 1H), 8.08 (d, J = 8.4 Hz, 1H), 8.16 (m, 2H), 8.40
(dd, J = 6.3 Hz, 2H). 13C NMR (75 MHz, CDCl3): d ppm 119.62,
121.72, 125.06, 126.85, 127.42, 128.79, 128.86, 129.41, 129.50,
131.72, 133.72, 133.77, 134.92, 135.07, 149.26, 158.25, 183.06
(CO), 183.79 (CO). HR-MS (ESI-TOF) m/z calcd, [M+H]+ 325.0971;
found, 325.0973. EI-MS m/z 324 (M+, 100), 325 (19).
(300 MHz, CDCl3): d ppm 7.72 (d, J = 8.7 Hz, 2H), 7.80–7.83 (m,
2H), 8.06 (d, J = 8.7 Hz, 2H), 8.13 (d, J = 8.4 Hz, 1H), 8.25 (d,
J = 8.4 Hz, 1H), 8.27–8.36 (m, 2H), 11.29 (s, 1H). 13C NMR
(75 MHz, CDCl3): d ppm 122.18, 125.86, 126.11, 126.57, 127.64,
127.69, 128.50, 128.89, 132.61, 133.20, 133.35, 133.87, 134.01,
134.57, 149.40, 155.62, 182.63 (CO), 185.25 (CO). HR-MS (ESI-
TOF) m/z calcd, [M+H]+ 403.0085; found, 403.0073. Calcd, [MÀH]À
400.9939; found, 400.9923. EI-MS m/z 402 (M+, 100), 404 (97).
4.3.9. 2-(4-N,N-Dimethylamino)phenyl-1(3)H-anthra[1,2-d
]imidazole-6,11-dione (12)
Product 12 was obtained as dark brown powder (yield 79%): mp
4.3.14. 2-(4-Cyanophenyl)-1H-anthra[1,2-d]imidazole-6,11-
dione (17)
239–240 °C (EtOH) (Rf = 0.60 at ethyl acetate/dichlorometh-
ane = 1:4). FT-IR (KBr;
m
cmÀ1) 3404 (NH),1659 (CO). 1H NMR
Product 17 was obtained as yellowish brown powder (yield
(300 MHz, CDCl3): d ppm 3.09 (s, 6H), 6.81 (d, 2H), 7.79–7.82 (m,
3H), 8.03–8.22 (m, 3H), 8.27–8.36 (m, 2H), 11.10 (br, 1H). 13C
NMR (75 MHz, CDCl3): d ppm 39.95, 111.65, 115.23, 117.13,
121.83, 124.24, 126.33, 127.37, 127.44, 128.27, 133.27, 133.45,
133.54, 134.12, 150.11, 152.10, 157.59, 182.47 (CO), 185.09 (CO).
HR-MS (ESI-TOF) m/z calcd, [M+H]+ 368.1393; found, 368.1393.
EI-MS m/z 366 (27), 367 (M+, 100), 368 (20).
77%): mp 353–354 °C (EtOH) (Rf = 0.65 at ethyl acetate/dichloro-
methane = 1:4). FT-IR (KBr;
m
cmÀ1) 3341 (NH), 2229 (CN), 1667
(CO). 1H NMR (300 MHz, CDCl3): d ppm 7.80–7.85 (m, 2H), 8.06
(d, J = 8.1 Hz, 2H), 8.18 (d, J = 8.4 Hz, 1H), 8.27–8.32 (m, 4H),
8.35–8.38 (m, 1H), 11.46 (s, 1H). 13C NMR (75 MHz, CDCl3): d
ppm 114.71, 118.04, 118.52, 122.39, 126.39, 126.63, 127.57,
127.75, 129.45, 132.76, 133.04, 133.11, 133.34, 133.93, 133.99,
134.70, 149.17, 154.25, 182.56 (CO), 185.21 (CO). HR-MS (ESI-
TOF) m/z calcd, [M+H]+ 350.0924; found, 350.0925.
4.3.10. 2-(4-Nitrophenyl)-1(3)H-anthra[1,2-d]imidazole-6,11-
dione (13)
Product 13 was obtained as red brown powder (yield 89%): mp
4.3.15. 2-(2,5-Dimethoxyphenyl)-1H-anthra[1,2-d]imidazole-
6,11-dione (18)
342–343 °C (EtOH) (Rf = 0.60 at ethyl acetate/dichlorometh-
ane = 1:4). FT-IR (KBr;
m
cmÀ1) 3460 (NH),1657 (CO), 1517, 1345
Product 18 was obtained as red brown powder (yield 74%): mp
(NO2). 1H NMR (300 MHz, DMSO-d6): d ppm 7.79–7.82 (m, 3H),
7.14 (d, J = 8.1 Hz, 1H), 8.23 (d, J = 8.1 Hz, 1H), 8.23–8.32 (m, 2H),
8.39 (d, J = 8.1 Hz, 2H), 8.58 (d, J = 8.1 Hz, 2H), 10.15 (br, 1H). 13C
NMR (75 MHz, DMSO-d6): d ppm 117.81, 122.43, 123.62, 125.24,
125.88, 126.10, 127.92, 133.22, 133.36, 134.53, 143.08, 146.39,
146.77, 155.89, 172.18, 178.35, 179.40, 183.20 (CO), 185.56 (CO).
HR-MS (ESI-TOF) m/z calcd, [M+H]+ 370.0822; found, 370.0823.
EI-MS m/z 249 (100), 369 (M+, 35).
251–252 °C (EtOH) (Rf = 0.40 at ethyl acetate/dichlorometh-
ane = 1:4). FT-IR (KBr;
m
cmÀ1) 3417 (NH), 1660 (C@O), 1226 (C–
O). 1H NMR (300 MHz, CDCl3): d ppm 3.93 (s, 3H), 4.21 (s, H),
7.09 (d, J = 1.2 Hz, 2H), 7.79–7.82 (m, 2H), 8.13 (d, J = 8.1 Hz, 1H),
8.13 (s, 1H), 8.25 (d, J = 8.1 Hz, 1H), 8.29–8.36 (m, 2H), 12.37 (s,
1H). 13C NMR (75 MHz, CDCl3): d ppm 56.08, 56.69, 113.13,
113.36, 116.86, 118.14, 119.98, 121.92, 124.92, 126.46, 127.54,
129.92, 132.57, 133.43, 133.70, 134.06, 134.24, 135.39, 152.20,
154.23, 155.18, 182.82 (CO), 184.88 (CO). HR-MS (ESI-TOF) m/z
calcd, [M+H]+ 385.1183; found, 385.1181.
4.3.11. 2-(4-Hydroxy-3-methoxyphenyl)-1H-anthra[1,2-
d]imidazole-6,11-dione (14)
Product 14 was obtained as brown powder (yield 47%): mp
4.3.16. 2-(Benzo[d][1,3]dioxol-5-yl)-1H-anthra[1,2-
d]imidazole-6,11-dione (19)
230–231 °C (EtOH) (Rf = 0.20 at ethyl acetate/dichlorometh-
ane = 1:4). FT-IR (KBr;
m
cmÀ1) 3411 (NH), 1664 (CO). 1H NMR
Product 19 was obtained as red brown powder (yield 81%): mp
(300 MHz, DMSO-d6): d ppm 3.91 (s, 3H), 6.90 (d, J = 8.4 Hz, 1H),
7.81–7.88 (m, 3H), 7.92–7.96 (m, 3H), 7.99 (s, 1H), 8.11 (d,
J = 8.4 Hz, 2H), 9.78 (br, 1H). 13C NMR (75 MHz, DMSO-d6): d ppm
56.57, 112.72, 116.37, 119.21, 119.65, 122.05, 122.95, 123.88,
126.81, 127.41, 128.42, 133.50, 133.64, 134.87, 135.09, 148.48,
150.87, 158.33, 182.85 (CO), 183.79 (CO). HR-MS (ESI-TOF) m/z
calcd, [M+H]+ 370.1026; found, 370.1025. EI-MS m/z 369 (57),
370 (M+, 100).
300–301 °C (EtOH) (Rf = 0.45 at ethyl acetate/dichlorometh-
ane = 1:4). FT-IR (KBr;
m
cmÀ1) 3444 (NH), 1670 (C@O), 1257 (C–
O), 1210 (C–O). 1H NMR (300 MHz, CDCl3): d ppm 6.11 (s, 2H),
7.00 (d, J = 7.8 Hz, 1H), 7.67 (s, 1H), 7.79–7.82 (m, 2H), 8.13 (d,
J = 8.1 Hz, 1H), 8.24 (d, J = 7.8 Hz, 1H), 8.25 (d, J = 8.1 Hz, 1H),
8.29–8.36 (m, 2H), 11.18 (s, 1H). 13C NMR (75 MHz, CDCl3): d
ppm 101.93, 107.37, 108.96, 117.86, 121.83, 122.05, 122.78,
125.35, 126.52, 127.62, 128.40, 133.27, 133.43, 133.76, 134.08,
134.44, 148.71, 149.62, 150.56, 156.55, 182.66 (CO), 185.27 (CO).
HR-MS (ESI-TOF) m/z calcd, [M+H]+ 369.0867; found, 369.0887.
4.3.12. 2-p-Tolyl-1H-anthra[1,2-d]imidazole-6,11-dione (15)
Product 15 was obtained as yellowish brown powder (yield
76%): mp 256–257 °C (EtOH) (Rf = 0.65 at ethyl acetate/dichloro-
4.3.17. 2,2-Dimethyl-2,3-dihydro-1H-anthra[1,2-d]imidazole-
6,11-dione (20)
methane = 1:4). FT-IR (KBr;
m
cmÀ1) 3397 (NH), 1659 (CO). 1H
NMR (300 MHz, CDCl3): d ppm 2.46 (s, 3H), 7.37 (d, J = 8.1 Hz,
2H), 7.79 (t, J = 3.6 Hz, 2H), 8.03 (d, J = 7.8 Hz, 2H), 8.08 (d,
J = 8.4 Hz, 1H), 8.21 (d, J = 8.4 Hz, 1H), 8.24–8.34 (m, 2H), 11.21
(s, 1H). 13C NMR (75 MHz, CDCl3): d ppm 21.58, 117.89, 121.96,
125.44, 125.75, 126.46, 127.00, 127.58, 128.43, 130.00, 133.20,
133.26, 133.72, 133.99, 134.38, 142.05, 149.50, 156.86, 182.60
(CO), 185.16 (CO). HR-MS (ESI-TOF) m/z calcd, [M+H]+ 339.1128;
found, 339.1128. EI-MS m/z 338 (M+, 100), 339 (24).
1,2-Diaminoanthraquinone (1.19 g, 5 mmol) was dissolved in
dry acetone (100 mL) and concd sulfuric acid (0.1 mL) was added
dropwise. The reaction mixture was stirred for 48 h at room tem-
perature. The mixture was purified by column chromatography
using potassium carbonate and crystallization from methanol to
yield the pure compound as a purple solid in 31% yield (Rf = 0.5
at ethyl acetate/dichloromethane = 1:4). Mp 235–237 °C (MeOH)
(lit: 234–237 °C).19 FT-IR (KBr;
m ) 3419 (NH), 3239
cmÀ1
(NH),1639 (CO). 1H NMR (300 MHz, DMSO-d6): d (ppm) 1.48 (s,
6H), 6.26 (d, J = 7.8 Hz, 1H), 7.37 (d, J = 7.8 Hz, 1H), 7.73–7.76 (m,
2H), 8.05 (1H, s), 8.08–8.12 (m, 2H), 8.79 (s, 1H). 13C NMR
4.3.13. 2-(4-Bromophenyl)-1H-anthra[1,2-d]imidazole-6,11-
dione (16)
Product 16 was obtained as red brown powder (yield 75%): mp
(75 MHz, DMSO-d6): d (ppm) 30.18, 81.70, 104.02, 108.04,
302–303 °C (EtOH) (Rf = 0.40 at ethyl acetate/dichlorometh-
120.99, 123.54, 126.32, 127.07, 133.41, 133.54, 134.79, 135.46,
143.05, 148.12, 179.89 (CO), 182.47 (CO). HR-MS (ESI-TOF) m/z
ane = 1:4). FT-IR (KBr;
m
cmÀ1) 3391 (NH), 1658 (CO). 1H NMR