3734
E. Colacino et al. / Tetrahedron 66 (2010) 3730–3735
122.2, 121.1, 120.2, 110.5, 103.8, 21.7; Q-TOF MS ES(þ): m/z 208.2
[MþH]þ.
chromatography: AcOEt/cyclohexane (10/90 to 80/20 v/v) as de-
veloping solvents. 1H NMR (CDCl3):
¼8.05 (s, 1H), 7.90–7.84 (m,
1H), 7.50–7.35 (m, 3H), 7.35–7.27 (m, 2H), 7.10–7.05 (m, 2H), 3.83
d
4.2.8. 1-Phenyl-1H-benzimidazole (11)44. Following the general
procedure (150 ꢀC, 1 h), benzimidazole 10 (27.2 mg, 0.23 mmol)
was coupled with iodobenzene (51.3 mL, 0.46 mmol), by using Cu2O
(3.3 mg, 0.023 mmol), PEG3400–OH (250 mg), and Cs2CO3 (150 mg,
0.46 mmol), to afford the title compound 11 in 77% yield. An ana-
lytical sample was purified by silica gel column chromatography:
AcOEt/cyclohexane (2/98 to 4/96) as developing solvents. 1H NMR
(s, 3H); 13C NMR (CDCl3):
d
¼159.4, 138.1, 129.1, 125.2, 123.5, 122.6,
120.4, 115.1, 110.5, 55.6; ESI-MS: m/z 224.9 [MþH]þ.
4.2.13. 1-(2-Methoxyphenyl)-1H-benzimidazole(16)45,49,46,47. Following
the general procedure (150 ꢀC, 1 h), benzimidazole 10 (27.2 mg,
0.23 mmol) was coupled with 2-iodoanisole (30 mL, 0.23 mmol), by
using Cu2O (3.3 mg, 0.023 mmol), PEG3400–OH (250 mg), and
Cs2CO3 (150 mg, 0.46 mmol), to afford the title compound 16 in 46%
yield. An analytical sample was purified by silica gel column
chromatography: AcOEt/cyclohexane (2/98 to 12/88 v/v) as
(CDCl3):
d
¼8.2 (s, 1H), 7.93–7.78 (m, 1H), 7.77–7.50 (m, 6H),
7.45–7.35 (m, 2H); 13C NMR (CDCl3):
d
¼144.0, 142.3, 136.4, 133.7,
128.1, 124.1, 123.7, 122.8, 120.6, 110.5; ESI-MS: m/z 195.0 [MþH]þ.
developing solvents. 1H NMR (CDCl3):
d
¼8.12 (br s, 1H), 7.88
4.2.9. 1-(4-Cyanophenyl)-1H-benzimidazole (12)45–47. Following the
general procedure (150 ꢀC, 1 h), benzimidazole 10 (27.2 mg,
0.23 mmol) was coupled with 4-iodobenzonitrile (52.7 mg,
0.23 mmol), by using Cu2O (3.3 mg, 0.023 mmol), PEG3400–OH
(250 mg), and Cs2CO3 (150 mg, 0.46 mmol), to afford the title
compound 12 in 44% yield. An analytical sample was purified by
silica gel column chromatography: AcOEt/cyclohexane (10/90
(d, J¼6.5 Hz, 1H), 7.50–7.43 (m, 3H), 7.36–7.28 (m, 2H), 7.14
(d, J¼7.9 Hz, 2H), 3.88 (s, 3H); 13C NMR (CDCl3):
¼153.9, 129.8,
d
127.3, 123.3, 122.9, 122.5, 120.2, 120.1, 115.7, 112.5, 110.8, 56.7;
ESI-MS: m/z 225.1 [MþH]þ.
4.2.14. 1-(4-Methylphenyl)-1H-benzimidazole (17)34. Following the
general procedure (150 ꢀC, 1 h), benzimidazole 10 (27.2 mg,
0.23 mmol) was coupled with 4-iodotoluene (50.1 mg, 0.23 mmol),
by using Cu2O (3.3 mg, 0.023 mmol), PEG3400–OH (250 mg), and
Cs2CO3 (150 mg, 0.46 mmol), to afford the title compound 17 in 35%
yield. An analytical sample was purified by silica gel column
chromatography: AcOEt/cyclohexane (10/90 to 60/40 v/v) as de-
to 20/80 v/v) as developing solvents. 1H NMR [(CD3)2SO]
d
¼8.70
(s, 1H), 8.13 (d, J¼8.9 Hz, 2H), 7.97 (d, J¼8.9 Hz, 2H), 7.81
(d, J¼6.7 Hz, 1H), 7.74 (d, J¼6.7 Hz, 1H), 7.46–7.18 (m, 2H); 1H
NMR (CDCl3)
d
¼8.22 (s, 1H), 7.90 (d, J¼8.5 Hz, 3H), 7.69
(d, J¼8.5 Hz, 2H), 7.39 (m, 3H); 13C NMR [(CD3)2SO]:
¼144.0,
d
143.2, 139.8, 134.3, 133.55, 123.9, 123.8, 123.9, 120.1, 118.4, 110.8,
veloping solvents. 1H NMR [(CD3)2SO]:
7.41–7.31 (m, 2H), 7.62–7.51 (m, 3H), 7.38–7.28 (m, 2H), 2.5 (s, 3H);
1H NMR CDCl3:
¼8.07 (s, 1H), 7.87 (m, 1H), 7.53 (m, 1H), 7.43–7.28
(m, 6H), 2.5 (s, 3H); 13C NMR [(CD3)2SO]:
d
¼8.6 (s, 1H), 7.8 (m, 1H),
109.8; ESI-MS: m/z 220.1 [MþH]þ.
d
4.2.10. 1-(4-Nitrophenyl)-1H-benzimidazole (13)47. Following the
general procedure (150 ꢀC, 1 h), benzimidazole 10 (27.2 mg,
0.23 mmol) was coupled with 1-iodo-4-nitrobenzene (114.6 mg,
0.46 mmol), by using Cu2O (3.3 mg, 0.023 mmol), PEG3400–OH
(250 mg), and Cs2CO3 (150 mg, 0.46 mmol), to afford the title
compound 13 in 39% yield. An analytical sample was purified by
silica gel column chromatography: AcOEt/cyclohexane (1/99 to
d¼137.2, 136.8, 133.4,
131.4, 130.4, 123.5, 123.3, 122.2, 121.6, 119.9, 110.6, 22.9; ESI-MS: m/z
209.2 [MþH]þ.
Acknowledgements
We thank Geoffrey Doulsier for some experiments, the CNRS,
and the Ligue Contre le Cancer for financial support.
8/92 v/v) as developing solvents. 1H NMR [(CD3)2SO]:
(s, 1H), 8.47 (d, J¼9.0 Hz, 2H), 8.04 (d, J¼9.0 Hz, 2H), 7.80 (m, 2H),
7.48–7.32 (m, 2H); 1H NMR (CDCl3):
¼8.47 (d, J¼8.9 Hz, 2H), 8.22
(s, 1H), 7.89 (m, 1H), 7.73 (d, J¼8.9 Hz, 1H), 7.61 (m, 2H), 7.41–7.35
d¼8.76
d
Supplementary data
(m, 2H); 13C NMR [(CD3)2SO]:
d
¼145.7, 144.2, 143.7, 141.3, 135.2,
Supplementary data associated with this article can be found in
125.8, 125.5, 123.7, 120.2 110.9; ESI-MS: m/z 240.0 [MþH]þ.
4.2.11. 1-(2-Nitrophenyl)-1H-benzimidazole (14)45,46. Following the
general procedure (150 ꢀC, 1 h), benzimidazole 10 (27.2 mg,
0.23 mmol) was coupled with 1-iodo-2-nitrobenzene (114.6 mg,
0.46 mmol), by using Cu2O (3.3 mg, 0.023 mmol), PEG3400–OH
(250 mg), and Cs2CO3 (150 mg, 0.46 mmol), to afford the title
compound 14 in 69% yield. An analytical sample was purified by
silica gel column chromatography: AcOEt/cyclohexane (2/98 to
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d¼8.50
(s, 1H), 8.32 (dd, J¼8.2 and 1.4 Hz, 1H), 8.00 (ddd, J¼16.5, 6.5, and
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by using Cu2O (3.3 mg, 0.023 mmol), PEG3400–OH (250 mg), and
Cs2CO3 (150 mg, 0.46 mmol), to afford the title compound 15 in 53%
yield. An analytical sample was purified by silica gel column
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