4284
V. A. Mamedov et al. / Tetrahedron Letters 52 (2011) 4280–4284
Dean, D. K.; Francis, G.; Gaiba, A.; Hird, A. W.; King, F. D.; Lovell, P. J.; Naylor, A.;
analytically pure 2-(4-fluorophenyl)-5-phenyl-1H-imidazole-4-carboxylic acid
2-(4-fluorobenzylidene)aminoanilide (3e) and 1-(4-fluorophenyl)-3-
Reith, A. D.; Steadman, J. G.; Wilson, D. M. Bioorg. Med. Chem. Lett. 2006, 16,
378; (c) Khanna, I. K.; Weier, R. M.; Yu, Y.; Xu, X. D.; Koszyk, F. J.; Collins, P. W.;
Koboldt, C. M.; Veenhuizen, A. W.; Perkins, W. E.; Casler, J. J.; Masferrer, J. L.;
Zhang, Y. Y.; Gregory, S. A.; Seibert, K.; Isakson, P. C. J. Med. Chem. 1997, 40,
1634; (d) Lange, J. H. M.; Van Stuivenberg, H. H.; Coolen, H. K. A. C.; Adolfs, T. J.
P.; McCreary, A. C.; Keizer, H. G.; Wals, H. C.; Veerman, W.; Borst, A. J. M.; de
Loof, W.; Verveer, P. C.; Kruse, C. G. J. Med. Chem. 2005, 48, 1823; (e) Gallagher,
T. F.; Fier-Thompson, S. M.; Garigipati, R. S.; Sorenson, M. E.; Smietana, J. M.;
Lee, D.; Bender, P. E.; Lee, J. C.; Laydon, J. T.; Griswold, D. E.; Chabot-Fletcher, M.
C.; Breton, J. J.; Adams, J. L. Bioorg. Med. Chem. Lett. 1995, 5, 1171.
3. (a) de Laszlo, S. E.; Hacker, C.; Li, B.; Kim, D.; MacCoss, M.; Mantlo, N.;
Pivnichny, J. V.; Colwell, L.; Koch, G. E.; Cascieri, M. A.; Hagmann, W. K. Bioorg.
Med. Chem. Lett. 1999, 9, 641; (b) Eyers, P. A.; Craxton, M.; Morrice, N.; Cohen,
P.; Goedert, M. Chem. Biol. 1998, 5, 321; (c) Newman, M. J.; Rodarte, J. C.;
Benbatoul, K. D.; Romano, S. J.; Zhang, C.; Krane, S.; Moran, E. J.; Uyeda, R. T.;
Dixon, R.; Guns, E. S.; Mayer, L. D. Cancer Res. 2000, 60, 2964; (d) Antolini, M.;
Bozzoli, A.; Ghiron, C.; Kennedy, G.; Rossi, T.; Ursini, A. Bioorg. Med. Chem. Lett.
1999, 9, 1023; (e) Wang, L.; Woods, K. W.; Li, Q.; Barr, K. J.; McCroskey, R. W.;
Hannick, S. M.; Gherke, L.; Credo, R. B.; Hui, Y.-H.; Marsh, K.; Warner, R.; Lee, J.
Y.; Zielinsky-Mozng, N.; Frost, D.; Rosenberg, S. H.; Sham, H. L. J. Med. Chem.
2002, 45, 1697; (f) Maier, T.; Schmierer, R.; Bauer, K.; Bieringer, H.; Buerstell,
H.; Sachse, B. U.S. Patent 4820335, 1989; Chem. Abstr. 1989, 111, 19494w.
4. For reviews, see: (a) Dupont, J.; de Souza, R. F.; Suarez, P. A. Z. Chem. Rev. 2002,
102, 3667; (b) Nara, S. J.; Naik, P. U.; Harjani, J. R.; Salunkhe, M. M. Indian J.
Chem., Sect B 2006, 45, 2257; (c) Chowdhury, S.; Mohan, R. S.; Scott, J. L.
Tetrahedron 2007, 63, 2363.
phenylimidazo[1,5-a]quinoxalin-4(5H)-one (4e). Compound 3e: yield 0.17 g
(45%), yellow powder, mp 261–262 °C. [Found: C, 72.88; H, 4.24; N, 11.67.
C
29H20F2N4O requires C, 72.79; H, 4.21; N, 11.71];
1517, 1495, 1437, 1228, 841, 751 cmꢀ1 1H NMR (600 MHz, DMSO-d6) d 7.11
(1H, dd, J 7.5, 7.1 Hz), 7.27 (1H, dd, J 7.8, 7.5 Hz), 7.37 (2H, dd, JHH 8.9, JHF
mmax (KBr) 3316, 1643, 1587,
;
3
3
3
3
8.9 Hz), 7.39 (2H, dd, JHH 8.9, JHF 8.9 Hz), 7.44–7.52 (4H, m), 7.89 (2H, d, J
3
4
3
4
7.1 Hz), 8.13 (2H, dd, JHH 8.6, JHF 5.4 Hz), 8.22 (2H, dd, JHH 8.4, JHF 5.8 Hz),
8.53 (1H, d, J 7.8 Hz), 8.86 (1H, s), 10.79 (1H, s), 13.01 (1H, br s); 13C{1H} NMR
(150.9 MHz, DMSO-d6) d 116.3 (d, 2JFC 28.8 Hz), 116.49, 116.52 (d, 2JFC 22.4 Hz),
4
116.6, 117.5, 118.5, 122.4, 123.5, 126.5 (d, JFC 2.9 Hz), 127.4, 127.9, 128.1 (d,
3JFC 9.2 Hz), 128.2, 128.3, 128.6, 129.0, 129.6, 130.0, 131.4, 131.5 (d, 3JFC 8.8 Hz),
4
132.5, 132.6, 133.3 (d, JFC 2.7 Hz), 134.4, 136.3, 138.4, 144.6, 158.9, 160.5,
163.1 (d, 1JFC 246.8 Hz), 164.7 (d, 1JFC 250.5 Hz). MS (EI), m/z [I(%)]: 479 (1), 478
(4) [M]+Å, 461 (4), 460 (11), 265 (24), 239 (13), 238 (44), 214 (42), 213 (100),
212 (82), 211 (18), 119 (41), 116 (12), 90 (18), 89 (23). Compound 4e: yield
73 mg (26%), white solid, mp 315–316 °C. [Found: C, 74.59; H, 3.93; N, 11.87.
C
22H14FN3O requires C, 74.36; H, 3.97; N, 11.82];
m
max (KBr) 3031, 2983, 2903,
2868, 1659, 1605, 1488, 1392, 1228, 842, 747, 689 cmꢀ1
;
1H NMR (600 MHz,
DMSO-d6) d 6.92 (1H, dd, J 8.5, 7.3 Hz), 7.02 (1H, d, J 8.1 Hz), 7.27–7.48 (7H, m),
3
4
7.78 (2H, dd, JHH 8.3, JHF 5.4 Hz), 8.19 (2H, d, J 7.3 Hz), 11.43 (1H, s). 13C{1H}
NMR (150.9 MHz, DMSO-d6) d 116.5 (d, 2JFC 22.0 Hz), 117.6, 117.7, 119.4, 122.3,
122.8, 127.9, 128.6, 128.9, 129.2 (d, JFC 3.4 Hz), 130.4, 130.7, 132.4 (d, JFC
4
3
1
8.4 Hz), 133.8, 144.1, 144.4, 156.1, 163.9 (d, JFC 247.9 Hz). MS (EI), m/z [I(%)]:
356 (28), 355 (100) [M]+Å, 354 (11), 327 (4), 252 (27), 206 (25), 205 (32), 103
(4), 89 (9), 77 (7).
5. For reviews, see: (a) Bourissou, D.; Guerret, O.; Gabbai, F. P.; Bertrand, G. Chem.
Rev. 2000, 100, 39; (b) Arnold, P. L.; Liddle, S. T. Chem. Commun. 2006, 3959; (c)
Kuhl, O. Chem. Soc. Rev. 2007, 36, 592.
6. Debus, H. Ann. 1858, 107, 204.
7. Radziszewski, B. Chem. Ber. 1882, 15, 1493.
16. Illustrative experimental procedure for the preparation of compounds 5: A solution
of 3e (0.2 g, 0.42 mmol) and NH4OAc (0.19 g, 2.51 mmol) in AcOH (4 mL) was
refluxed for 6 h. The solvent was concentrated to dryness under reduced
pressure and the solid residue was treated with H2O (5 mL). The resulting
white precipitate was collected, washed with H2O and dried in air to give
0.15 g (98%) of 2-[2-(4-fluorophenyl)-5-phenylimidazol-4-yl]benzimidazole
(5c), mp 264–265 °C. [Found: C, 69.83; H, 4.54; N, 13.47. C22H15FN4ꢁAcOH
8. Japp, F. R.; Robinson, H. H. Ber. 1882, 15, 1268.
9. Nagawade, R. R.; Shinde, D. B. Acta Chim. Slov. 2007, 54, 642.
10. (a) Usyatinsky, A. Y.; Khemelnitsky, Y. L. Tetrahedron Lett. 2000, 41, 5031; (b)
Wolkenberg, S. E.; Wisnoski, D. D.; Leister, W. H.; Wang, Y.; Zhao, Z.; Lindsley,
C. W. Org. Lett. 2004, 6, 1453; (c) Sparks, R. B.; Combs, A. P. Org. Lett. 2004, 6,
2473; (d) Oskooie, H. A.; Alimohammadi, Z.; Heravi, M. M. Heteroat. Chem.
2006, 17, 699; (e) Siddiqui, S. A.; Narkhede, U. C.; Palimkar, S. S.; Daniel, T.;
Lahoti, R. J.; Srinivasan, K. V. Tetrahedron 2005, 61, 3539; (f) Wang, J.; Mason,
R.; Derveer, D. V.; Feng, K.; Bu, X. R. J. Org. Chem. 2003, 68, 5415; (g) Sarshar, S.;
Siev, D.; Mjalli, M. M. Tetrahedron Lett. 1996, 37, 835; (h) Gallagher, T. F.; Seibel,
G. L.; Kassis, S.; Laydon, J. T.; Blumenthal, M. J.; Lee, J. C.; Lee, D.; Boehm, J. C.;
Fier-Thompson, S. M.; Abt, J. W.; Soreson, M. E.; Smietana, J. M.; Hall, R. F.;
Garigipati, R. S.; Bender, P. E.; Erhard, K. F.; Krog, A. J.; Hofmann, G. A.;
Sheldrake, P. L.; McDonnell, P. C.; Kumar, S.; Young, P. R.; Adams, J. L. Bioorg.
Med. Chem. 1997, 5, 49; (i) Shaabani, A.; Rahmati, A. J. Mol. Catal. A: Chem. 2006,
249, 246; (j) Heravi, M. M.; Bakhtiari, K.; Oskooie, H. A.; Taheri, S. J. Mol. Catal. A:
Chem. 2007, 263, 279.
requires C, 69.57; H, 4.59; N, 13.53];
1163 cmꢀ1
mmax (KBr) 1689, 1498, 1289, 1275, 1232,
;
1H NMR (600 MHz, DMSO-d6) d 7.12–7.19 (2H, m), 7.37–7.43 (3H,
m), 7.49–7.56 (4H, m), 8.16 (2H, d, J 6.8 Hz), 8.23 (2H, dd, 3JHH 8.1, 4JHF 5.6 Hz),
12.46 (1H, br s), 12.90 (1H, br s); 13C{1H} NMR (150.9 MHz, DMSO-d6) d 112.1,
116.6 (d, 2JFC 22.0 Hz), 119.4, 122.4, 127.3 (d, 4JFC 2.6 Hz), 128.6 (d, 3JFC 8.4 Hz),
1
128.9, 129.7, 130.5, 132.8, 135.1, 144.6, 149.2, 162.1, 164.3 (d, JFC 246.1 Hz).
MS (EI), m/z [I(%)]: 355 (19), 354 (71) [M]+Å, 353 (100), 205 (21), 177 (12), 103
(10), 60 (8).
17. (a) Mamedov, V. A.; Kalinin, A. A.; Balandina, A. A.; Rizvanov, I. Kh. .; Latypov,
Sh. K. Tetrahedron 2009, 65, 9412; (b) Mamedov, V. A.; Kalinin, A. A.; Rizvanov,
I. Kh.; Bauer, I.; Habicher, V. D. Russ. Chem. Bull. 2009, 58, 1493; (c) Kalinin, A.
A.; Mamedov, V. A. Russ. Chem. Bull. 2008, 57, 219; (d) Kalinin, A. A.; Mamedov,
V. A. Russ. J. Org. Chem. 2008, 44, 736.
18. The X-ray diffraction data for crystals of 3a were collected on a Bruker AXS
Smart Apex II CCD diffractometer at 296 K. Crystallographic data for 3a.
11. (a) Hayes, J. F.; Mitchell, M. B.; Wicks, C. Heterocycles 1994, 38, 575; (b) Revesz,
L.; Bonne, F.; Makavou, P. Tetrahedron Lett. 1998, 39, 5171; (c) Liverton, N. J.;
Butcher, J. W.; Claiborne, C. F.; Claremon, D. A.; Libby, B. E.; Nguyen, K. T.;
Pitzenberger, S. M.; Selnick, H. G.; Smith, G. R.; Tebben, A.; Vacca, J. P.; Varga, S.
L.; Agarwal, L.; Dancheck, K.; Forsyth, A. J.; Fletcher, D. S.; Frantz, B.; Hanlon, W.
A.; Harper, C. F.; Hofsess, S. J.; Kostura, M.; Lin, J.; Luell, S.; O’Neill, E. A.;
Orevillo, C. J.; Pang, M.; Parsons, J.; Rolando, A.; Sahly, Y.; Visco, D. M.; O’Keefe,
S. J. J. Med. Chem. 1999, 42, 2180.
12. (a) Balalaie, S.; Arabanian, A. Green Chem. 2002, 2, 274; (b) Heravi, M. M.;
Derikvand, F.; Bamoharram, F. F. J. Mol. Catal. A: Chem. 2007, 263, 112; (c)
Karimi, A. R.; Alimohammadi, Z.; Azizian, J.; Mohammadi, A. A.;
Mohammadizadeh, M. R. Catal. Commun. 2006, 7, 728; (d) Kantevari, S.;
Vuppalapati, S. V. N.; Biradar, D. O.; Nagarapu, L. J. Mol. Catal. A: Chem. 2007,
266, 109.
13. (a) Balalaie, S.; Hashemi, M. M.; Akhbari, M. Tetrahedron Lett. 2003, 44, 1709;
(b) Lantos, I.; Zhang, W.-Y.; Shui, X.; Eggleston, D. S. J. Org. Chem. 1993, 58,
7092; (c) Consonni, R.; Croce, P. D.; Ferraccioli, R.; Rosa, C. L. J. Chem. Res.,
Synop. 1991, 188.
14. (a) Mamedov, V. A.; Saifina, D. F.; Rizvanov, I. Kh.; Gubaidullin, A. T. Tetrahedron
Lett. 2008, 49, 4644; (b) Mamedov, V. A.; Saifina, D. F.; Gubaidullin, A. T.;
Saifina, A. F.; Rizvanov, I. Kh. Tetrahedron Lett. 2008, 49, 6231; (c) Mamedov, V.
A.; Murtazina, A. M.; Gubaidullin, A. T.; Hafizova, E. A.; Rizvanov, I. Kh.
Tetrahedron Lett. 2009, 50, 5186; (d) Mamedov, V. A.; Saifina, D. F.; Gubaidullin,
A. T.; Ganieva, V. R.; Kadyrova, S. F.; Rakov, D. V.; Rizvanov, I. Kh.; Sinyashin, O.
G. Tetrahedron Lett. 2010, 51, 6503; (e) Mamedov, V. A.; Zhukova, N. A.;
Beschastnova, T. N.; Gubaidullin, A. T.; Balandina, A. A.; Latypov, S. K.
Tetrahedron 2010, 66, 9745.
C
29H22N4OꢁCH3OH, yellow crystalline plates, formula weight 474.55,
orthorhombic, Pbca, a = 7.5316(6) Å, b = 23.637(2) Å, c = 27.950(2) Å,
V = 4975.8(7) Å3, calc = 1.267 g cmꢀ3 (kMoK ) = 0.81 cmꢀ1
Z = 8,
q
,
l
,
a
F(0 0 0) = 2000, reflections collected = 49021, unique = 5924, R(int) = 0.1279,
full-matrix least-squares on F2, parameters = 338, restraints = 0. Final indices
R1 = 0.0594, wR2 = 0.1074 for 2696 reflections with I >2r(I); R1 = 0.1587,
wR2 = 0.1393 for all data, goodness-of-fit on F2 = 0.978, largest difference in
peak and hole (0.178 and ꢀ0.199 eÅꢀ3).
19. The X-ray diffraction data for crystals of 4a were collected on a Bruker AXS
Smart Apex II CCD diffractometer at 296 K. Crystallographic data for 4a.
C
22H15N3O, colorless needles, formula weight 337.37, monoclinic,
P
21/c,
b = 107.785(5)°,
K ) = 0.83 cmꢀ1
a = 15.074(5)
Å,
b = 5.078(2) Å,
c = 23.490(8) Å,
(kMo
V = 1712.2(9) Å3,
Z = 4,
q
calc = 1.309 g cmꢀ3
,
l
,
a
F(000) = 704, reflections collected = 12388, unique = 3677, R(int) = 0.2111, full-
matrix least-squares on F2, parameters = 227, restraints = 1. Final indices
R1 = 0.0731, wR2 = 0.1250 for 1132 reflections with I >2r(I); R1 = 0.2718,
wR2 = 0.1823 for all data, goodness-of-fit on F2 = 0.891, largest difference in
peak and hole (0.172 and ꢀ0.235 eÅꢀ3).
20. The X-ray diffraction data for crystals of 5a were collected on a Bruker AXS
Smart Apex II CCD diffractometer at 296(2) K. Crystallographic data for 5a.
C
22H16N4, C2H6OS, colorless prisms, 0.40 ꢂ 0.13 ꢂ 0.08 mm, formula weight
414.52,
c = 20.1173(13) Å,
(kMoK ) = 1.76 cmꢀ1
orthorhombic,
P212121,
V = 2122.1(2) Å3,
F(000) = 872,
a = 7.8844(5),
Z = 4,
reflections
b = 13.3793(8),
q
calc = 1.297 gꢁcmꢀ3
,
l
,
collected = 16538,
a
unique = 4983,
parameters = 279, restraints = 0. Final indices R1 = 0.0419, wR2 = 0.0921 for
3630 reflections with I >2 (I); R1 = 0.0674, wR2 = 0.1027 for all data, goodness-
2 = 1.028, largest difference in peak and hole (0.158 and
R(int) = 0.0470,
full-matrix
least-squares
on
F2,
r
15. Illustrative experimental procedure for the preparation of compounds 3 and 4: 4-
of-fit on F
Fluorobenzaldehyde 2d (0.2 g, 1.6 mmol) was added to
a
suspension of
ꢀ0.270 eÅꢀ3).
benzoylquinoxalinone 1a (0.2 g, 0.8 mmol) and NH4OAc (0.62 g, 8 mmol) in
MeOH (10 mL). The mixture was stirred at reflux until complete dissolution of
the reagents was observed (ca. 2 h). After ca. 10–15 min the precipitation of
light-yellow crystals occurred gradually and precipitation continued for 5 h.
The mixture was cooled to room temperature and the precipitate filtered and
dried in air, to give 0.29 g (77%) of a mixture of compounds 3e and 4e in the
ratio of 1.7:1. These were separated by fractional crystallization (AcOH) to give
21. Crystallographic data (excluding structure factors) for the structures 3a, 4a and
5a in this paper have been deposited with the Cambridge Crystallographic Data
Centre as supplementary publication numbers CCDC 815371, 815372 and
815373, respectively. Copies of the data can be obtained, free of charge, on
application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK, (fax: +44
(0)1223-336033 or e-mail: deposit@ccdc.cam.ac.uk).