The Journal of Organic Chemistry
ARTICLE
1-Benzyl-2-(4-fluorophenyl)-1H-benzo[d]imidazole 10e.
Analytical TLC on silica gel, 1:9 ethyl acetate/hexane Rf = 0.20; colorless
Anal. Calcd for C21H18N2O: C, 80.23; H, 5.77; N, 8.91. Found: C, 80.30;
H, 5.75; N, 8.87.
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1-Benzyl-5-methyl-2-phenyl-1H-benzo[d]imidazole 10k30d
.
solid; yield 75%; mp 115ꢀ116 °C; H NMR (400 MHz, CDCl3) δ
7.88ꢀ7.86 (m, 1H), 7.68ꢀ7.65 (m, 2H), 7.34ꢀ7.31 (m, 3H),
7.26ꢀ7.23 (m, 3H), 7.17ꢀ7.09 (m, 4H), 5.44 (s, 2H); 13C NMR
(100 MHz, CDCl3) δ 165.2, 162.7, 153.3, 142.9, 136.3, 136.1, 131.6,
131.5, 129.3, 128.1, 126.1, 123.5, 123.1, 120.1, 116.2, 116.0, 110.7, 48.5;
FT-IR (KBr) 3033, 2926, 2854, 1717, 1607, 1534, 1462, 1450, 1418,
1391, 1361, 1329, 1279, 1258, 1231, 1162, 1102, 1027 cmꢀ1; (ESI-MS)
m/z 303.14 [M þ H]þ. Anal. Calcd for C20H15FN2: C, 79.45; H, 5.00;
N, 9.27. Found: C, 79.52; H, 4.97; N, 9.23.
Analytical TLC on silica gel, 1:4 ethyl acetate/hexane Rf = 0.30; colorless
1
solid; yield 64%; mp 147ꢀ148 °C; H NMR (400 MHz, CDCl3) δ
7.67ꢀ7.64 (m, 3H), 7.44 (d, J = 6.8 Hz, 3H), 7.31ꢀ7.27 (m, 3H),
7.09ꢀ7.05 (m, 4H), 5.41 (s, 2H), 2.48 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 154.1, 143.3, 136.6, 134.2, 132.6, 130.1, 130.0, 129.4, 129.1,
128.8, 127.9, 126.1, 124.7, 119.8, 110.2, 48.5, 21.7; FT-IR (KBr) 3029,
2963, 1699, 1603, 1493, 1471, 1449, 1421, 1392, 1364, 1326, 1312, 1261,
1172, 1096, 1027 cmꢀ1; (ESI-MS) m/z 299.17 [M þ H]þ. Anal. Calcd
for C21H18N2: C, 84.53; H, 6.08; N, 9.39. Found: C, 84.46; H, 6.10;
N, 9.44.
1-Benzyl-2-(2-methoxyphenyl)-1H-benzo[d]imidazole 10f.
Analytical TLC on silica gel, 1:4 ethyl acetate/hexane Rf = 0.20; colorless
liquid;yield 62%;1H NMR (400 MHz, CDCl3) δ 7.86 (d, J = 7.2 Hz, 1H),
7.54 (d, J = 6.0 Hz, 2H), 7.50ꢀ7.45 (m, 1H), 7.27ꢀ7.15 (m, 5H),
7.08ꢀ7.03 (m, 2H), 6.98 (d, J = 8.4 Hz, 2H), 5.23 (s, 2H), 3.62 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 157.7, 152.3, 143.2, 136.5, 135.3, 132.7,
131.9, 128.7, 127.6, 126.8, 122.9, 122.4, 121.2, 120.0, 119.4, 111.1, 110.8,
55.4, 48.6; FT-IR (KBr) 2962, 2931, 2857, 1608, 1519, 1462, 1455, 1394,
1331, 1287, 1258, 1181, 1162, 1076, 1023 cmꢀ1; (ESI-MS) m/z 315.15
[M þ H]þ. Anal. Calcd for C21H18N2O: C, 80.23; H, 5.77; N, 8.91.
Found: C, 80.17; H, 5.79; N, 8.96.
1-Benzyl-2-(4-methoxyphenyl)-1H-benzo[d]imidazole 10g.
Analytical TLC on silica gel, 1:4 ethyl acetate/hexane Rf = 0.20; colorless
liquid; yield 60%; 1H NMR (400 MHz, CDCl3) δ 7.86 (d, J = 7.6 Hz, 1H),
7.64 (d, J = 8.4 Hz, 2H), 7.34ꢀ7.20 (m, 6H), 7.12 (d, J = 6.0 Hz, 2H), 6.97
(d, J = 8.4 Hz, 2H), 5.44 (s, 2H), 3.84 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 161.2, 154.3, 143.2, 136.7, 136.2, 130.9, 130.3, 129.3, 127.9,
126.1, 123.0, 122.8, 119.9, 114.4, 110.6, 55.5, 48.6; FT-IR (KBr) 3031,
2997, 2961, 2927, 2854, 1718, 1610, 1575, 1509, 1495, 1453, 1442, 1420,
1389, 1362, 1329, 1302, 1260, 1179, 1163, 1097, 1033 cmꢀ1; (ESI-MS) m/
z 315.16 [M þ H]þ. Anal. Calcd for C21H18N2O: C, 80.23; H, 5.77; N,
8.91. Found: C, 80.28; H, 5.79; N, 8.86.
1-Benzyl-2-p-tolyl-1H-benzo[d]imidazole 10h. Analytical
TLC on silica gel, 1:4 ethyl acetate/hexane Rf = 0.30; colorless solid;
yield 65%; mp 122ꢀ123 °C; 1H NMR (400 MHz, CDCl3) δ 7.87 (d, J
= 7.2 Hz, 1H), 7.59 (d, J = 8.0 Hz, 2H), 7.31ꢀ7.21 (m, 8H), 7.12 (d, J
= 6.4 Hz, 2H), 5.45 (s, 2H), 2.40 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 154.5, 143.1, 140.3, 136.6, 136.1, 129.6, 129.3, 129.2,
127.9, 127.1, 126.1, 123.1, 122.8, 120.0, 110.6, 48.5, 21.6; FT-IR
(KBr) 3032, 2939, 2925, 2855, 1611, 1448, 1416, 1392, 1362, 1331,
1279, 1251, 1190, 1163, 1115, 1027 cmꢀ1; (ESI-MS) m/z 299.16 [M
þ H]þ. Anal. Calcd for C21H18N2: C, 84.53; H, 6.08; N, 9.39. Found:
C, 84.59; H, 6.06; N, 9.35.
1-Benzyl-5-chloro-2-phenyl-1H-benzo[d]imidazole 10i.
Analytical TLC on silica gel, 1:9 ethyl acetate/hexane Rf = 0.30; colorless
solid; yield 68%; mp 145ꢀ146 °C; 1H NMR (400 MHz, CDCl3) δ 7.82
(d, J = 1.6 Hz, 1H), 7.66ꢀ7.64 (m, 2H), 7.46 (d, J = 6.8 Hz, 2H),
7.32ꢀ7.29 (m, 2H), 7.19ꢀ7.16 (m, 2H), 7.10ꢀ7.05 (m, 4H), 5.42 (s,
2H); 13C NMR (100 MHz, CDCl3) δ 155.6, 144.2, 136.1, 134.8, 130.4,
129.8, 129.4, 129.3, 129.0, 128.5, 128.2, 126.1, 123.6, 119.9, 111.5, 48.7;
FT-IR (KBr) 3046, 2957, 2928, 1608, 1496, 1470, 1453, 1426, 1390,
1362, 1321, 1312, 1258, 1179, 1162, 1076, 1057, 1027 cmꢀ1; (ESI-MS)
m/z 319.11 [M þ H]þ. Anal. Calcd for C20H15ClN2: C, 75.35; H, 4.74;
N, 8.79. Found: C, 75.28; H, 4.76; N, 8.74.
1-Benzyl-2-(3,4-dimethoxyphenyl)-1H-benzo[d]imidazole
10l. Analytical TLC on silica gel, 2:3 ethyl acetate/hexane Rf = 0.20;
colorless liquid; yield 65%;1H NMR (400 MHz, CDCl3) δ 7.90 (d, J = 7.2
Hz, 1H), 7.45 (s, 1H) 7.35ꢀ7.22 (m, 7H), 7.15ꢀ7.09 (m, 2H), 6.92 (d, J
= 8.0 Hz, 1H), 5.47 (s, 2H), 3.91 (s, 3H), 3.71 (s, 3H); 13C NMR (100
MHz, CDCl3) δ 154.3, 150.8, 149.3, 142.7, 136.8, 136.2, 129.6, 129.3,
128.0, 126.0, 123.3, 123.1, 122.1, 119.8, 112.6, 111.3, 110.5, 56.1, 55.9,
48.6; FT-IR (KBr) 2961, 2935, 2034, 1707, 1638, 1605, 1495, 1456, 1439,
1355, 1325, 1266, 1225, 1178, 1140, 1024 cmꢀ1; (ESI-MS) m/z 345.17
[M þ H]þ. Anal. Calcd for C22H20N2O2: C, 76.72; H, 5.85; N, 8.13.
Found: C, 76.78 H, 5.87; N, 8.08.
1-Benzyl-2-(4-chlorophenyl)-5-methyl-1H-benzo[d]imida-
zole 10m. Analytical TLC on silica gel, 1:4 ethyl acetate/hexane Rf =
0.50; colorless solid; yield 41%; mp 129ꢀ130 °C; 1H NMR (400 MHz,
CDCl3) δ 7.63ꢀ7.58 (m, 3H), 7.41 (d, J = 8.4 Hz, 2H), 7.32ꢀ7.28 (m,
4H), 7.08ꢀ7.06 (m, 3H), 5.39 (s, 2H), 2.48 (s, 3H);13C NMR(100 MHz,
CDCl3) δ 158.0, 152.9, 143.5, 136.4, 136.2, 132.7, 130.6, 130.0, 129.2,
129.1, 128.7, 128.0, 126.0, 124.9, 119.9, 110.1, 48.4, 21.7; FT-IR (KBr)
3028, 2922, 2854, 1624, 1599, 1569, 1496, 1489, 1468, 1452, 1430, 1408,
1386, 1359, 1325, 1298, 1279, 1259, 1171, 1143, 1092, 1028, 1012 cmꢀ1
;
(ESI-MS) m/z 333.12 [M þ H]þ. Anal. Calcd for C21H17ClN2: C, 75.78;
H, 5.15; N, 8.42. Found: C, 75.70; H, 5.18; N, 8.47.
1-Benzyl-2-(4-methoxyphenyl)-5-methyl-1H-benzo[d]imida-
zole 10n. Analytical TLC on silica gel, 1:4 ethyl acetate/hexane Rf =
1
0.20; colorless solid; yield 48%; mp 73ꢀ74 °C; H NMR (400 MHz,
CDCl3) δ 7.61ꢀ7.58 (m, 3H), 7.31ꢀ7.27 (m, 3H), 7.10ꢀ7.03 (m, 4H),
6.94 (d, J = 8.8 Hz, 2H), 5.39 (s, 2H), 3.82 (s, 3H), 2.47 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ 160.9, 154.1, 143.4, 136.7, 134.2, 132.3,
130.7, 129.1, 127.7, 126.0, 124.3, 122.4, 119.5, 114.2, 110.0, 55.4, 48.4,
21.6; FT-IR (KBr) 3028, 2924, 2855, 1610, 1578, 1536, 1479, 1465,
1450, 1417, 1391, 1353, 1324, 1295, 1254, 1175, 1113, 1025 cmꢀ1; (ESI-
MS) m/z 329.17 [M þ H]þ. Anal. Calcd for C22H20N2O: C, 80.46; H,
6.14; N, 8.53. Found: C, 80.54; H, 6.12; N, 8.48.
1-Benzyl-5-methyl-2-p-tolyl-1H-benzo[d]imidazole 10o.
Analytical TLC on silica gel, 1:4 ethyl acetate/hexane Rf = 0.40; colorless
solid; yield 52%; mp 122ꢀ123 °C; 1H NMR (400 MHz, CDCl3) δ 7.64
(s, 1H), 7.57 (d, J = 8.0 Hz, 2H), 7.32ꢀ7.23 (m, 5H), 7.10ꢀ7.04 (m,
4H), 5.41 (s, 2H), 2.49 (s, 3H), 2.39 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 154.3, 143.5, 140.0, 136.7, 134.3, 132.3, 129.5, 129.2, 129.1,
127.7, 127.3, 126.0, 124.4, 119.7, 110.1, 48.4, 21.7, 21.5; FT-IR (KBr)
3028, 2956, 2923, 2854, 1606, 1503, 1467, 1452, 1416, 1386, 1364, 1323,
1280, 1259, 1171, 1141, 1104, 1027 cmꢀ1; (ESI-MS) m/z 313.18 [M þ
H]þ. Anal. Calcd for C22H20N2: C, 84.58; H, 6.45; N, 8.97. Found: C,
84.51; H, 6.47; N, 9.02.
1-Benzyl-4,6-dimethyl-2-phenyl-1H-benzo[d]imidazole
10p. Analytical TLC on silica gel, 1:9 ethyl acetate/hexane Rf = 0.30;
colorless liquid; yield 67%; 1H NMR (400 MHz, CDCl3) δ 7.63 (dd, J =
6.8, 1.6 Hz, 2H), 7.41 (d, J = 6.4 Hz, 3H), 7.34ꢀ7.26 (m, 3H), 7.07 (d, J
= 7.2 Hz, 2H), 6.93 (s, 1H), 6.81 (s, 1H), 5.35 (s, 2H), 2.68 (s, 3H), 2.37
(s, 3H); 13C NMR (100 MHz, CDCl3) δ 153.2, 140.8, 136.9, 136.1,
133.1, 130.6, 129.8, 129.5, 129.1, 128.8, 127.8, 126.1, 124.9, 120.2, 120.0,
1-Benzyl-5-methoxy-2-phenyl-1H-benzo[d]imidazole 10j.
Analytical TLC on silica gel, 1:4 ethyl acetate/hexane Rf = 0.20; colorless
liquid; yield 70%; 1H NMR (400 MHz, CDCl3) δ 7.67ꢀ7.64 (m, 2H),
7.44 (d, J = 6.4 Hz, 3H) 7.33ꢀ7.27 (m, 4H), 7.09ꢀ7.04 (m, 3H), 6.87
(dd, J = 8.8 Hz, 2.4 Hz, 1H) 5.41 (s, 2H), 3.86 (s, 3H); 13C NMR (100
MHz, CDCl3) δ 156.8, 154.5, 144.1, 136.6, 130.9, 130.4, 130.0, 129.4,
129.2, 128.9, 128.0, 126.2, 113.3, 111.1, 102.3, 56.0, 48.7; FT-IR (KBr)
3063, 2933, 2834, 1621, 1514, 1488, 1472, 1453, 1435, 1392, 1342, 1277,
1199, 1154, 1116, 1075, 1028 cmꢀ1; (ESI-MS) m/z 315.16 [M þ H]þ.
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dx.doi.org/10.1021/jo2005632 |J. Org. Chem. 2011, 76, 5295–5308