8032
J. Kim et al. / Tetrahedron 67 (2011) 8027e8033
1253, 1163, 1036 cmꢂ1; GCeMS m/z (rel intensity) 162 (Mþ, 100),
147 (95), 119 (36), 78 (5), 63 (4), 52 (5).
(d, J¼234.6 Hz), 153.7, 140.7, 137.3, 131.2, 130.8, 129.8, 127.4, 116.6,
111.1 (d, J¼25.5 Hz), 101.9; IR (KBr) 3049, 1466, 1409 cmꢂ1; GCeMS
m/z (rel intensity) 212 (Mþ, 100), 184 (8), 106 (7), 82 (8), 77 (6).
4.2.9. 5-Iodo-2-phenyl-1H-benzimidazole (11). Yield 71%. Yellow
solid, mp 198e201 ꢀC. TLC (50% ethyl acetate/hexane) Rf 0.54; 1H
4.2.16. 5-Fluoro-2-methyl-1H-benzimidazole (18)13. Yield 80%. Pale
yellow solid, mp 177e179 ꢀC. TLC (10% methanol/dichloromethane)
NMR (400 MHz, DMSO-d6)
d
13.04 (br s, 1H) 8.15 (d, 2H, J¼7.3 Hz),
7.94 (br s, 1H), 7.57e7.42 (m, 5H); 13C NMR (100 MHz, acetone-d6)
Rf 0.41; 1H NMR (400 MHz, DMSO-d6)
d
12.30 (br s, 1H), 7.41 (dd,
1H, J¼8.7, 5.0 Hz), 7.24 (dd, 1H, J¼9.5, 2.4 Hz), 6.93 (ddd, 1H, J¼10.5,
8.1, 1.2 Hz), 2.46 (s, 3H); 13C NMR (100 MHz, CDCl3)
159.3 (d,
d
153.2, 142.7, 139.9, 131.8, 131.0, 130.7, 129.7, 127.5, 125.0, 117.8,
85.8; IR (KBr) 3062, 1463, 1395 cmꢂ1; GCeMS m/z (rel intensity)
320 (Mþ, 100), 193 (16), 166 (13), 104 (4), 90 (6), 77 (4), 63 (6);
HRMS (EI) calcd for C13H9IN2 319.9810, found 319.9807.
d
J¼237.5 Hz), 152.3, 138.9, 135.1, 114.9, 110.3 (d, J¼25.2 Hz), 100.8,
15.0; IR (KBr) 3119, 3051, 2924, 1437, 1412 cmꢂ1; GCeMS m/z (rel
intensity) 150 (Mþ, 100), 122 (12), 108 (9), 95 (4), 82 (9), 63 (3).
4.2.10. 5-Iodo-2-methyl-1H-benzimidazole (12)12. Yield 74%. White
solid, mp 240e241 ꢀC (lit.12 mp 219e221 ꢀC). TLC (10% methanol/
4.2.17. 4-Trifluoromethyl-2-phenyl-1H-benzimidazole
82%. Pale yellow solid, mp 175e178 ꢀC. TLC (50% ethyl acetate/
hexane) Rf 0.50; 1H NMR (400 MHz, DMSO-d6)
13.19 (br s, 1H),
(19). Yield
dichloromethane) Rf 0.45; 1H NMR (400 MHz, DMSO-d6)
d
12.36 (br
s, 1H), 7.81 (s, 1H), 7.38 (d, 1H, J¼8.0 Hz), 7.29 (d, 1H, J¼8.0 Hz), 2.48
(s, 3H); 13C NMR (100 MHz, acetone-d6, 40 ꢀC)
153.3, 142.7, 139.3,
d
d
8.23 (d, 2H, J¼7.1 Hz), 7.85 (d, 1H, J¼7.8 Hz), 7.59e7.52 (m, 4H), 7.36
131.0, 124.6, 117.5, 84.7, 14.9; IR (KBr) 3398, 3092, 2964, 2893, 1437,
1394,1275 cmꢂ1; GCeMS m/z (rel intensity) 258 (Mþ,100),131 (37),
104 (13), 90 (11), 77 (3), 63 (11).
(t, 1H, J¼7.7 Hz); 13C NMR (100 MHz, acetone-d6)
d 151.2, 139.6 (br),
139.2 (br), 131.3, 130.7, 129.8, 127.9, 125.3 (q, J¼270.0 Hz), 122.7,
120.1 (q, J¼4.8 Hz), 119.3 (br), 118.3 (br); IR (KBr) 3180, 3066, 1461,
1424 cmꢂ1; GCeMS m/z (rel intensity) 262 (Mþ, 100), 242 (4), 223
(22), 192 (6), 139 (13), 121 (7), 103 (6), 77 (6); HRMS (EI) calcd for
C14H9F3N2 262.0718, found 262.0714.
4.2.11. 5-Bromo-2-phenyl-1H-benzimidazole (13)6c. Yield 80%. Yel-
low solid, mp 204e207 ꢀC. TLC (50% ethyl acetate/hexane) Rf 0.47;
1H NMR (400 MHz, DMSO-d6)
d
13.10 (br s, 1H), 8.17 (d, 2H,
J¼7.1 Hz), 7.79 (br s, 1H), 7.56e7.47 (m, 4H), 7.33 (dd, 1H, J¼8.4,
1.3 Hz); 13C NMR (100 MHz, CDCl3)
152.8, 139.8, 138.3, 130.6,
4.2.18. 4-Trifluoromethyl-2-methyl-1H-benzimidazole (20)7g. Yield
62%. Pale yellow solid, mp 176e177 ꢀC. TLC (10% methanol/
d
129.3, 129.2, 126.7, 126.2, 117.9, 116.4, 116.0; IR (KBr) 3421, 3097,
3049, 1444, 1397 cmꢂ1; GCeMS m/z (rel intensity) 274 (Mþþ2, 95),
272 (Mþ, 100), 192 (14), 166 (14), 137 (5), 104 (5), 90 (8), 77 (6), 63
(10).
dichloromethane) Rf 0.48; 1H NMR (400 MHz, DMSO-d6)
d 12.68 (br
s, 1H), 7.73 (d, 1H, J¼7.8 Hz), 7.42 (d, 1H, J¼7.8 Hz), 7.24 (t, 1H,
J¼7.8 Hz), 2.55 (s, 3H); 13C NMR (100 MHz, CDCl3)
d 153.1, 141.6 (br),
133.3 (br), 124.2 (d, J¼270.2 Hz), 121.6, 119.5, 116.0, 14.7; IR (KBr)
3470, 3177, 3107, 1431, 1333 cmꢂ1; GCeMS m/z (rel intensity) 200
(Mþ, 100), 180 (70), 161 (10), 153 (10), 139 (13), 126 (4), 100 (5), 88
(3), 75 (3), 63 (4).
4.2.12. 5-Bromo-2-methyl-1H-benzimidazole (14)10e,12. Yield 90%.
White solid, mp 223e224 ꢀC (lit.12 mp 214e215 ꢀC, lit.10e mp
232e233 ꢀC). TLC (10% methanol/dichloromethane) Rf 0.45; 1H
NMR (400 MHz, DMSO-d6)
d
12.41 (br s, 1H), 7.64 (s, 1H), 7.40 (d,1H,
4.2.19. 5-Trifluoromethyl-2-phenyl-1H-benzimidazole (21)7e. Yield
62%. White solid, mp 196e197 ꢀC. TLC (50% ethyl acetate/hexane) Rf
J¼7.9 Hz), 7.23 (d, 1H, J¼7.9 Hz), 2.47 (s, 3H); 13C NMR (100 MHz,
acetone-d6)
d
153.6, 142.0, 139.2, 125.0, 118.3, 116.4, 114.6, 14.8; IR
0.57; 1H NMR (400 MHz, DMSO-d6)
d 13.34 (br s, 1H), 8.21 (d, 2H,
(KBr) 3412, 3082, 3011, 2957, 2897, 1454, 1397, 1274 cmꢂ1; GCeMS
m/z (rel intensity) 212 (Mþþ2, 98), 210 (Mþ, 100), 131 (23), 104 (10),
90 (8), 76 (5), 63 (12), 52 (4).
J¼7.6 Hz), 7.95 (s, 1H), 7.77 (d, 1H, J¼8.3 Hz), 7.58e7.50 (m, 4H); 13C
NMR (100 MHz, acetone-d6) d 155.0, 142.2, 141.1, 131.3, 130.7, 129.8,
127.7, 126.1 (q, J¼269.6 Hz), 124.7 (q, J¼31.7 Hz), 119.9 (q, J¼3.6 Hz),
116.0, 114.2; IR (KBr) 3468, 3109, 3059, 1332 cmꢂ1; GCeMS m/z (rel
intensity) 262 (Mþ, 100), 243 (12), 212 (5), 192 (5), 131 (5), 77 (4).
4.2.13. 5-Chloro-2-phenyl-1H-benzimidazole (15)6c,10b. Yield 85%.
White solid, mp 212e214 ꢀC (lit.10b mp 212e213 ꢀC). TLC (50% ethyl
acetate/hexane) Rf 0.49; 1H NMR (400 MHz, DMSO-d6)
d
13.09 (br s,
1H), 8.18 (d, 2H, J¼7.1 Hz), 7.65e7.47 (m, 5H), 7.21 (dd, 1H, J¼8.5,
2.0 Hz); 13C NMR (100 MHz, acetone-d6)
153.8, 141.5, 139.1, 130.9,
4.2.20. 5-Trifluoromethyl-2-methyl-1H-benzimidazole (22)7f. Yield
83%. White solid, mp 194e195 ꢀC. TLC (10% methanol/dichloro-
d
methane) Rf 0.47; 1H NMR (400 MHz, DMSO-d6)
d
12.66 (br s, 1H),
7.81 (s,1H), 7.62 (d,1H, J¼8.3 Hz), 7.41 (d,1H, J¼8.3 Hz), 2.53 (s, 3H);
13C NMR (100 MHz, acetone-d6)
155.2, 141.9, 140.5, 126.2 (q,
130.8, 129.7, 128.1, 127.5, 123.4, 116.9, 115.8; IR (KBr) 3418, 3069,
3049, 1463, 1440, 1399 cmꢂ1; GCeMS m/z (rel intensity) 230
(Mþþ2, 35), 228 (Mþ, 100), 192 (13), 166 (7), 114 (6), 104 (4), 90 (6),
77 (6), 63 (7).
d
J¼269.2 Hz), 124.1 (q, J¼31.2 Hz), 119.1 (q, J¼3.7 Hz), 115.3, 113.3,
14.9; IR (KBr) 3468, 3072, 1421, 1333 cmꢂ1; GCeMS m/z (rel in-
tensity) 200 (Mþ, 100), 181 (18), 172 (8), 140 (5), 131 (20), 113 (3),
100 (5), 75 (3), 63(5).
4.2.14. 5-Chloro-2-methyl-1H-benzimidazole (16)10d. Yield 85%.
White solid, mp 209e210 ꢀC (lit.10d mp 200e201 ꢀC). TLC (10%
methanol/dichloromethane) Rf 0.44; 1H NMR (400 MHz, DMSO-d6)
4.2.21. 2-Phenyl-1H-benzimidazole-5-carbonitrile (23)14. Yield 70%.
White solid, mp 201e202 ꢀC. TLC (50% ethyl acetate/hexane) Rf
d
12.36 (br s, 1H), 7.51 (d, 1H, J¼2.0 Hz), 7.45 (d, 1H, J¼8.5 Hz), 7.13
(dd, 1H, J¼8.5, 2.0 Hz), 2.47 (s, 3H); 13C NMR (100 MHz, CDCl3)
0.34; 1H NMR (400 MHz, DMSO-d6)
d 13.34 (br s, 1H), 8.20 (d, 2H,
d
152.2, 139.4, 137.3, 127.9, 122.8, 115.2, 114.4, 15.0; IR (KBr) 3425,
J¼6.3 Hz), 8.13 (s, 1H), 7.74 (d, 1H, J¼8.3 Hz), 7.60e7.54 (m, 4H); 13C
3020, 2970, 2903, 1464, 1399 cmꢂ1; GCeMS m/z (rel intensity) 168
NMR (100 MHz, acetone-d6) d 155.4, 142.9, 140.9, 131.6, 130.4, 129.9,
(Mþþ2, 34), 166 (Mþ, 100), 131 (25), 104 (5), 90 (6), 76 (3), 63 (9), 52
127.8, 126.6, 121.3, 120.4, 116.7, 106.0; IR (KBr) 3528, 3257, 3066,
2224, 1451 cmꢂ1; GCeMS m/z (rel intensity) 219 (Mþ, 100), 191 (5),
109 (4), 90 (4), 77 (6).
(3).
4.2.15. 5-Fluoro-2-phenyl-1H-benzimidazole (17)10b. Yield 85%.
White solid, mp 245e246 ꢀC (lit.10b mp 242e243 ꢀC). TLC (50% ethyl
4.2.22. 2-Methyl-1H-benzimidazole-5-carbonitrile (24)7f. Yield 74%.
White solid, mp 242e243 ꢀC. TLC (10% methanol/dichloromethane)
acetate/hexane) Rf 0.46; 1H NMR (400 MHz, DMSO-d6)
d
13.05 (br s,
1H), 8.19e8.17 (m, 2H), 7.61e7.47 (m, 4H), 7.41 (dd, 1H, J¼9.4,
1.8 Hz), 7.09e7.04 (m, 1H); 13C NMR (100 MHz, acetone-d6)
160.3
Rf 0.54; 1H NMR (400 MHz, DMSO-d6)
d
12.76 (br s, 1H), 7.97 (br s,
d
1H), 7.58 (d, 1H, J¼8.3 Hz), 7.47 (dd, 1H, J¼8.3, 1.2 Hz), 2.51 (s, 3H);