1410
T. Hafner, D. Kunz
PAPER
IR (KBr): 3156 (w), 2959 (m), 1683 (s), 1516 (s), 1427 (s), 1250 (s),
1038 (m), 919 (m), 834 (m), 692 (m) cm–1.
1H NMR (300 MHz, CD2Cl2): d = 2.38 (s, 3 H, CH3), 3.83 (s, 3 H,
OCH3), 6.67 (d, J = 3.2 Hz, 1 H, H-5), 6.69 (d, J = 3.2 Hz, 1 H, H-
4), 6.97 (d, J = 9.0 Hz, 2 H, H-3¢), 7.26 (d, J = 8.2 Hz, 2 H, H-3¢¢),
7.52 (d, J = 9.0 Hz, 4 H, H-2¢/H-2¢¢).
13C NMR (75 MHz, CD2Cl2): d = 21.0 (CH3), 55.9 (OCH3), 111.0
(C-5), 111.6 (C-4), 114.6 (C-3¢), 122.2 (C-2¢¢), 124.3 (C-2¢), 130.0
(C-3¢¢), 130.8 (C-1¢), 135.3 (C-4¢¢), 136.2 (C-1¢¢), 151.0 (C-2), 158.2
(C-4¢).
References
(1) (a) Muchmore, S. W.; Souers, A. J.; Akritopoulou-Zanze, I.
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Compd. (Engl. Transl.) 1988, 24, 1129.
HRMS (EI): m/z calcd for C17H16N2O2: 280.1215; found (%):
280.1215 (100), 251.1176 (13), 237.1024 (17), 161.9893 (11),
150.9994 (12).
Anal. Calcd for C17H16N2O2: C, 72.84; H, 5.75; N, 9.99. Found: C,
72.36; H, 5.74; N, 9.75.
1,3-Bis(4-methoxyphenyl)-1H-imidazol-2(3H)-one (4h)
Purified by flash chromatography (cyclohexane–acetone, 3:1).
Yield: 63% (isolated yield); off-white crystals; mp 197 °C.
IR (KBr): 3152 (w), 3014 (w), 2954 (m), 2835 (m), 1688 (s), 1613
(m), 1525 (s), 1425 (s), 1257 (s), 1035 (s), 918 (m), 834 (s), 766 (s),
656 (s) cm–1.
1H NMR (300 MHz, CD2Cl2): d = 6.65 (s, 2 H, H-4, 5-H), 6.97 (d,
J = 8.9 Hz, 4 H, H-3¢), 7.51 (d, J = 8.9 Hz, 4 H, H-2¢).
(6) Wendeborn, S.; Winkler, T.; Foisy, I. Tetrahedron Lett.
13C NMR (75 MHz, CD2Cl2): d = 56.1 (OCH3), 111.5 (C-4), 114.8
(C-3¢), 124.3 (C-2¢), 131.0 (C-1¢), 151.3 (C-2), 158.4 (C-4¢).
2000, 41, 6387.
(7) (a) Mann, G.; Hartwig, J. F.; Driver, M. S.; Fernández-
Rivas, C. J. Am. Chem. Soc. 1998, 120, 827. (b) Yang, B.
H.; Buchwald, S. L. J. Organomet. Chem. 1999, 576, 125.
(c) Shekhar, S.; Ryberg, P.; Hartwig, J. F.; Mathew, J. S.;
Blackmond, D. G.; Strieter, E. R.; Buchwald, S. L. J. Am.
Chem. Soc. 2006, 128, 3584.
HRMS (EI): m/z calcd for C17H16N2O3: 296.1161; found (%):
296.1155 (100), 267.1124 (14), 253.0976 (13).
Anal. Calcd for C17H16N2O3: C, 68.91; H, 5.44; N, 9.45. Found: C,
68.92; H, 5.47; N, 9.27.
(8) (a) Ullmann, F. Ber. Dtsch. Chem. Ges. 1903, 36, 2382.
(b) Goldberg, I. Ber. Dtsch. Chem. Ges. 1906, 39, 1691.
(c) Sugahara, M.; Ukita, T. Chem. Pharm. Bull. 1997, 45,
719. (d) Strieter, E. R.; Blackmond, D. G.; Buchwald, S. L.
J. Am. Chem. Soc. 2005, 127, 4120. (e) Haider, J.; Kunz, K.;
Scholz, U. Adv. Synth. Catal. 2004, 346, 717.
1-(4-Methoxyphenyl)-3-(4-nitrophenyl)-1H-imidazol-2(3H)-
one (4i)
Purified by flash chromatography (cyclohexane–acetone, 3:1).
Yield: 74% (isolated yield); yellow crystals; mp 175 °C.
IR (KBr): 3127 (m), 3006 (w), 2966 (w), 2836 (w), 1688 (s), 1604
(m), 1517 (s), 1428 (m), 1341 (s), 1251 (s), 1170 (s), 1115 (m), 1029
(m), 918 (m), 851 (m), 779 (m) cm–1.
1H NMR (300 MHz, CD2Cl2): d = 3.84 (s, 3 H, OCH3), 6.76 (d,
J = 3.2 Hz, 2 H, H-5), 6.85 (d, J = 3.2 Hz, 2 H, H-4), 6.99 (d,
J = 9.0 Hz, 1 H, H-3¢), 7.49 (d, J = 9.0 Hz, 1 H, H-2¢), 7.95 (d,
J = 9.2 Hz, 2 H, H-2¢¢), 8.31 (d, J = 9.2 Hz, 2 H, H-3¢¢).
13C NMR (75 MHz, CD2Cl2): d = 56.1 (OCH3), 109.4 (C-4), 113.9
(C-5), 115.0 (C-3¢), 119.4 (C-2¢¢), 120.8 (C-3¢¢), 124.3 (C-2¢), 130.3
(C-1¢), 142.5 (C-1¢¢), 145.6 (C-4¢¢), 151.3 (C-2), 158.4 (C-4¢).
(f) Beletskaya, I. P.; Cheprakov, A. V. Coord. Chem. Rev.
2004, 248, 2337.
(9) For examples of palladium-catalyzed reactions with urea,
see: (a) Artamkina, G. A.; Sergeev, A. G.; Beletskaya, I. P.
Tetrahedron Lett. 2001, 42, 4381. (b) Sergeev, A. G.;
Artamkina, G. A.; Beletskaya, I. P. Tetrahedron Lett. 2003,
44, 4719. For examples of copper-catalyzed reactions with
urea, see: (c) Buchwald, S. L.; Klapars, A.; Antilla, J. C.;
Job, G. E.; Wolter, M.; Kwong, F. Y.; Nordmann, G.;
Hennessy, E. J. PCT Int. Appl. WO 02085838, 2002; Chem.
Abstr. 2002, 137, 352492. (d) Nandakumar, M. V.
Tetrahedron Lett. 2004, 45, 1989. (e) Trost, B. M.; Styles,
D. T. Org. Lett. 2005, 7, 2117. For examples with
benzimidazolinones, see: (f) Ward, R. E.; Meyer, T. Y.
Macromolecules 2003, 36, 4368.
HRMS (EI): m/z calcd for C16H13N3O4: 311.0906; found (%):
311.0905 (100), 282.0883 (6), 265.0972 (11), 134.0605 (16).
Anal. Calcd for C16H13N3O4: C, 61.73; H, 4.21; N, 13.50. Found: C,
61.53; H, 4.27; N, 13.50.
(10) Yang, G. X.; Chang, L. L.; Truong, Q.; Doherty, G. A.;
Magriotis, P. A.; de Laszlo, S. E.; Li, B.; MacCoss, M.;
Kidambi, U.; Egger, L. A.; McCauley, E.; Van Riper, G.;
Mumford, R. A.; Schmidt, J. A.; Hagmann, W. K. Bioorg.
Med. Chem. Lett. 2002, 12, 1497.
(11) (a) Mann, G.; Hartwig, J. F.; Driver, M. S.; Fernández-
Rivas, C. J. Am. Chem. Soc. 1998, 120, 827. (b) Grasa, G.
A.; Viciu, M. S.; Huang, J.; Nolan, S. P. J. Org. Chem. 2001,
66, 7729. (c) Vargas, V. C.; Rubio, R. J.; Hollis, T. K.;
Salcido, M. E. Org. Lett. 2003, 5, 4847. (d) Klapars, A.;
Antilla, J. C.; Huang, X.; Buchwald, S. L. J. Am. Chem. Soc.
2001, 123, 7727. (e) Antilla, J. C.; Baskin, J. M.; Barder, T.
E.; Buchwald, S. L. J. Org. Chem. 2004, 69, 5578.
Acknowledgment
Financial support for this research by the Deutsche Forschungsge-
meinschaft (KU 1473/2-1) and the Fonds der Chemischen Industrie
is gratefully acknowledged. We thank Prof. Peter Hofmann for his
constant and generous support, Prof. Thomas J. J. Müller for the use
of the SmithCreator microwave and Johnson Matthey for a loan of
Pd-complexes.
Synthesis 2007, No. 9, 1403–1411 © Thieme Stuttgart · New York