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4.1.2.3.2. 1-(3-Bromophenyl)-4-nitro-1H-imidazole (9). Yield 85%,
yellowish powder, m. p. 113e114 ꢂC (methanol/water); 1H NMR
(300 MHz) 7.53 (t, 1H, J ¼ 8.1 Hz, H-50), 7.68 (ddd, 1H, J ¼ 8.1 Hz,
J ¼ 1.8 Hz, J ¼ 0.9 Hz, AreH), 7.85 (ddd, 1H, J ¼ 8.1 Hz, J ¼ 1.8 Hz,
J ¼ 0.9 Hz, AreH), 8.14 (t, 1H, J ¼ 1.8 Hz, H-20), 8.53 (d, 1H, J ¼ 1.5 Hz,
H-2imid.), 9.06 (d,1H, J ¼ 1.5 Hz, H-5imid.); 13C NMR (75.5 MHz) 119.7,
120.2, 122.5, 124.0, 131.3, 131.6, 135.6, 136.7, 148.1 (s, 1C, C-4imid.);
UVevis lmax ¼ 300 nm; EA: calcd. for C9H6BrN3O2 C 40.32, H 2.26, N
15.68; found C 40.27, H 2.32, N 15.91.
4.1.2.3.3. 4-Nitro-1-(3-nitrophenyl)-1H-imidazole (11). Yield 72%,
dark yellow powder, m. p. 229e231 ꢂC (glacial acetic acid); 1H NMR
(300 MHz) 7.88 (t, 1H, J ¼ 8.1 Hz, H-50), 8.28e8.33 (m, 2H, H-40,
H-60), 8.65 (d, 1H, J ¼ 1.5 Hz, H-2imid.), 8.72 (t, 1H, J ¼ 2.4 Hz, H-20),
9.19 (d, 1H, J ¼ 1.5 Hz, H-5imid.); 13C NMR (75.5 MHz) 116.5, 120.0,
123.1, 127.6, 131.4, 135.9, 136.3 (s, 1C, C-10), 148.24 (s, 1C, C-4imid.),
148.51 (s, 1C, C-30); EA: calcd. for C9H6N4O4 C 46.16, H 2.58, N 23.93;
found C 46.32, H 2.65, N 23.91.
4.1.2.3.9. 1-(3-Methoxyphenyl)-4-nitro-1H-imidazole (19). Yield
87%, bright yellow needels, m. p. 151e151.5 ꢂC (methanol/water);
1H NMR (300 MHz) 3.86 (s, 3H, eOCH3), 7.03e7.08 (m, 1H, H-40),
7.36e7.39 (m, 1H, H-60), 7.40e7.41 (m, 1H, H-20), 7.48 (t, 1H,
J ¼ 8.1 Hz, H-50), 8.51 (d, 1H, J ¼ 1.5 Hz, H-2imid.), 9.03 (d, 1H,
J ¼ 1.5 Hz, H-5imid.); 13C NMR (75.5 MHz) 55.6 (s, 1C, eOCH3), 106.9
(s, C-20), 113.0 (s, C-40), 114.4 (s, C-60), 119.6 (s, C-5imid), 130.8 (s, C-
50), 135.6 (s, C-2imid), 136.5 (s, C-10), 148.0 (s, C-4imid), 160.3 (s, C-60);
UVevis lmax ¼ 303 nm; EA calcd. for C10H9N3O3 C 54.79, H 4.14; N
19.17, found: C 54.6, H 4.20, N 19.35.
4.1.2.3.10. Butyl 4-(4-nitro-1H-imidazol-1-yl)benzoate (21). Yield
53%, bright yellow plates, m. p. 134e135.5 ꢂC (methanol); 1H NMR
(600 MHz) 0.96 (t, 3H, J ¼ 7.5 Hz, eCH3), 1.45 (m, 2H, eCH2eCH3),
1.70e1.75 (m, 2H, eCH2eCH2eCH3), 4.31 (t, 2H, J ¼ 6.6 Hz,
eOeCH2eCH2e), 7.97e7.99 (m, 2H, AreH), 8.09e8.11 (m, 2H,
AreH), 8.59 (d, 1H, J ¼ 1.5 Hz, H-2imid), 9.09 (d,-1H, J ¼ 1.5 Hz, H-
5imid); 13C NMR (150 MHz) 13.5, 18.7, 30.2, 64.7, 119.4, 121.1 (s, 2C),
129.52, 130.73 (s, 2C), 135.59, 138.85, 148.32 (s, 1C, C-4imid), 164.67
(s, 1C, C]O); EA calcd. for C14H15N3O4 C 58.13, H 5.23, N 14.53,
found C 58.45, H 5.18, N 14.49.
4.1.2.3.11. 1-(3-Chloro-4-fluorophenyl)-4-nitro-1H-imidazole
(33). Yield 64%, bright yellow prisms, m. p. 115e116 ꢂC (methanol);
1H NMR (300 MHz) 7.63e7.69 (m, 1H, AreH), 7.86e7.88 (m, 1H,
AreH), 8.19e8.20 (m, 1H, AreH), 8.48 (sb, 1H, H-2imid), 9.02 (sb, 1H,
H-5imid), 13C NMR (75.5 MHz) 117.9 (d, 1C, J ¼ 22.6 Hz, C-50), 119.9 (s,
1C, C-5imid), 120.8 (d, 1C, J ¼ 19.1 Hz, C-30), 122.1 (d, 1C, J ¼ 7.8 Hz,
C-60), 123.8 (sb, 1C, CeAr), 132.5 (d, 1C, J ¼ 3.1 Hz, C-10), 135.8 (s, 1C,
C-2imid), 148.0 (s, 1C, C-4imid), 156.8 (d, 1C, J ¼ 247.7 Hz, C-40);
UVevis lmax ¼ 299 nm; MS: m/z: 241 (Mþ, 38%), 156 (100%), 129
(87%); EA calcd. for C9H5ClFN3O2 C 44.74, H 2.09, N 17.39, found C
44.77, H 2.14, N 18.32.
4.1.2.3.12. 1-(2-Bromo-4-methylphenyl)-4-nitro-1H-imidazole
(34). Yield 56%, yellowish thin plates, m. p.144e145 ꢂC (methanol);
1H NMR (300 MHz) 2.41 (s, 3H, eCH3), 7.41 (dd, 8.0 Hz, J ¼ 0.9 Hz, H-
50), 7.58 (d, 1H, J ¼ 8.0 Hz, H-60), 7.75 (d, 1H, J ¼ 0.9 Hz, H-30), 8.12 (d,
1H, J ¼ 1.5 Hz, H-2imid), 8.73 (d, 1H, J ¼ 1.5 Hz, H-5imid); 13C NMR
(75.5 MHz) 20.3 (s, 1C, eCH3), 119.1 (s, 1C, C-20), 122.8 (s, 1C, C-
5imid), 128.4 (s, 1C, C-60), 129.5 (s, 1C, C-50), 132.3 (s, 1C, C-10), 133.6
(s, 1C, C-30), 138.1 (s, 1C, C-40), 142.2 (s, C-2imid), 147.4 (s, 1C, C-4imid);
EA calcd. for C10H8BrN3O2 C 42.58, H 2.86, N 14.90, found C 42.55, H
2.86, N 14.85.
4.1.2.3.13. 1-(4-Bromo-3-methylphenyl)-4-nitro-1H-imidazole
(35). Yield 88%, yellowish powder, m. p. 161e163 ꢂC (methanol/
water); 1H NMR (300 MHz) 2.42 (s, 3H, CH3), 7.60 (dd,1H, J ¼ 8.7 Hz,
J ¼ 2.4 Hz, H-60), 7.76 (d, 1H, J ¼ 8.7 Hz, H-50), 7.87 (d, 1H, J ¼ 2.4 Hz,
H-20), 8.48 (d, 1H, J ¼ 1.5 Hz, H-2imid), 8.98 (d, 1H, J ¼ 1.5 Hz,
H-5imid); 13C NMR (75.5 MHz) 22.4, 119.4, 120.3, 123.5, 123.7, 133.3,
135.4, 139.3, 148.1; UVevis lmax ¼ 229, 303 nm; EA calcd. for
C10H8BrN3O2 C 42.58, H 2.86, N 14.90, found C 42.59, H 2.91, N
15.24.
4.1.2.3.14. 1-(3-Bromo-4-methylphenyl)-4-nitro-1H-imidazole
(36). Yield 70%, bright yellow powder m. p. 147e148 ꢂC (methanol/
water); 1H NMR (300 MHz) 2.40 (s, 3H, CH3), 7.53 (d, 1H, J ¼ 8.4 Hz,
H-50), 7.74 (dd, 1H, J ¼ 8.4 Hz, J ¼ 2.1 Hz, H-60), 8.12 (d, 1H, J ¼ 2.1 Hz,
H-20), 8.50 (d, 1H, J ¼ 0.9 Hz, H-2imid), 9.02 (d, 1H, J ¼ 0.9 Hz,
H-2imid); 13C NMR (75.5 MHz) 21.9, 119.6, 120.2, 124.5, 124.7, 131.8,
134.3, 135.5, 137.8, 148.0; UVevis lmax ¼ 303 nm; EA calcd. for
C10H8BrN3O2 C 42.58, H 2.86, N 14.90, found C 42.80, H 2.93, N
14.94.
4.1.2.3.4. 4-Nitro-1-{3-(trifluoromethyl)phenyl}-1H-imidazole
(12). Yield 79%, yellowish powder, m. p. 114e116 ꢂC (ethyl acetate/
hexane); 1H NMR (300 MHz) 7.80e7.87 (m, 2H, AreH), 8.14e8.18 (m,
1H, AreH), 8.27e8.28 (m, 1H, AreH), 8.62 (d, 1H, J ¼ 1.6 Hz, H-2imid.),
9.16(d,1H, J¼ 1.6Hz,H-5imid.); 13CNMR(75.5MHz)118.4(q, J¼ 3.9Hz,
C-40),119.9(s, C-2imid.),123.5(q, J¼ 272.8 Hz, eCF3),125.1 (q, J¼ 3.7Hz,
C-20),125.3 (s,1C),130.7 (q,1C, J ¼ 32.6 Hz, C-30),131.1 (s,1C),135.8 (s,
1C), 136.1 (s, 1C), 148.2 (s, C-4imid.); UVevis lmax ¼ 298 nm; MS: m/z:
257 (Mþ, 35%), 172 (70%), 145 (100%); EA calcd. for C10H6F3N3O2
46.70, H 2.35, N 16.34, found C 46.77, H 2.36, N 16.46.
C
4.1.2.3.5. 4-Nitro-1-{4-(trifluoromethyl)phenyl}-1H-imidazole
(13). Yield 69%, white powder, m. p.144e145 ꢂC (methanol/water);
1H NMR (300 MHz) 7.97 (d, 2H, J ¼ 8.4 Hz, AreH), 8.08 (d, 2H,
J ¼ 8.4 Hz, AreH), 8.61 (d, 1H, J ¼ 1.6 Hz, H-2imid), 9.13 (d, 1H,
J ¼ 1.6 Hz, H-5imid); 13C NMR (75.5 MHz) 119.6 (s, C-2imid.), 121.9
(s, C-20, C-60), 123.7 (q, J ¼ 270.6 Hz eCF3), 127.1 (q, J ¼ 3.7 Hz, C-30,
C-50), 128.7 (q, J ¼ 32.3 Hz, C-40) 135.7 (s, C-5imid.), 138.5e138.5 (m,
C-10) 148.3 (s, C-4imid..); UVevis lmax ¼ 307.5 nm (2.4% methanol in
water); MS: m/z: 257 (Mþ, 37%), 172 (69%), 145 (100%); EA calcd. for
C10H6F3N3O2 C 46.70, H 2.35, N 16.34, found C 46.93, H 2.34, N 16.16.
4.1.2.3.6. 4-Nitro-1-{2-(trifluoromethoxy)phenyl}-1H-imidazole
(14). Yield 71%, white plates, m. p. 87e89 ꢂC (ethyl acetate/
hexane), white needles m. p. 90.8e92 ꢂC (diethyl ether); 1H NMR
(300 MHz) 7.62e7.76 (m, 3H, AreH), 7.83e7.86 (m, 1H, AreH), 8.23
(d, 1H, J ¼ 1.5 Hz, H-2imid), 8.81 (d, 1H, J ¼ 1.5 Hz, H-5imid); 13C NMR
(75.5 MHz) 119.7 (q, 1C, J ¼ 259.2 Hz, eOCF3), 122.2, 122.3, 128.1,
128.4, 128.8, 131.4, 137.8, 141.72e141.74 (m, 1C, C-20), 147.7 (s, 1C, C-
4imid); UVevis lmax ¼ 294 nm; MS: m/z: 273 (Mþ, 48%), 188 (64%),
95 (100%). EA calcd for C10H6F3N3O3 C 43.97, H 2.21, N 15.38, found
C 44.01, H 2.21, N 15.36.
4.1.2.3.7. 4-Nitro-1-{3-(trifluoromethoxy)phenyl}-1H-imidazole
(15). Yield 31%, white powder, m. p. 92e94 ꢂC (ethanol); 1H NMR
(600 MHz) 7.49e7.51 (m, 1H, H-40), 7.73 (t, 1H, J ¼ 8.4 Hz, H-50), 7.91
(dd, 1H, J ¼ 8.4 Hz, J ¼ 1.2 Hz, H-20), 7.98 (sB, 1H, H-20), 8.57 (d, 1H,
J ¼ 1.2 Hz, H-2imid), 9.10 (d, 1H, J ¼ 1.2 Hz, H-5imid); 13C NMR
(150 MHz) 114.6, 119.7, 120.0 (q, 1C, J ¼ 257.8 Hz, eOCF3), 120.2,
120.7, 131.7, 135.7, 136.8, 148.2, 149.0; EA calcd for C10H6F3N3O3
43.97, H 2.21, N 15.38, found C 44.18, H 2.19, N 15.34.
C
4.1.2.3.8. 4-Nitro-1-{4-(trifluoromethoxy)phenyl}-1H-imidazole
(16). Yield 84%, light yellow plates, m. p. 129.5e131 ꢂC (methanol/
1
water); H NMR (300 MHz): 7.63 (d, 2H, J ¼ 8.4 Hz, H-20, H-60),
7.95e7.99 (m, 2H, H-30, H-50), 8.51 (d, 1H, J ¼ 1.2 Hz, H-2imid.), 9.05
(d, 1H, J ¼ 1.2 Hz, H-5imid.); 13C NMR (75.5 MHz) 120.0 (s, 1C), 120.0
(q, 1C, J ¼ 257.0 Hz, eOCF3), 122.6 (s, 1C), 123.5 (s, 1C), 134.5 (s, 1C),
135.9 (s, 1C), 147.9 (s, 1C, C-40), 148.2 (s, 1C, C-4imid.); UVevis
lmax ¼ 216, 300 nm; MS: m/z: 273 (Mþ, 47%), 188 (100%), 161 (51%),
95 (91%); EA calcd. for C10H6F3N3O3 C 43.97, H 2.21, N 15.38, found C
43.83, H 2.09, N 14.87.
4.1.2.3.15. 1-(2,4-Dimethylphenyl)-4-nitro-1H-imidazole (37). Yield
78%, yellowish prisms, m. p. 123e124.5 ꢂC (methanol); 1H NMR
(300 MHz) 2.16 (s, 3H, eCH3), 2.36 (s, 3H, eCH3), 7.20 (db, 1H,
J ¼ 7.8 Hz, H-50), 7.27 (sb, 1H, H-30), 7.33 (d, 1H, J ¼ 7.8 Hz, H-60), 8.06
(d, 1H, J ¼ 1.5 Hz, H-2imid), 8.67 (d, 1H, J ¼ 1.5 Hz, H-5imid); 13C NMR
(75.5 MHz) 17.1 (s, eCH3), 20.6 (s, eCH3), 122.5 (s, C-5imid), 126.3