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Can. J. Chem. Vol. 82, 2004
+
ImH), 3.87 (3H, s, OCH3), 6.80 (1H, d, J = 7.9, ArH), 6.85
(1H, d, J = 7.9, ArH), 7.19 (1H, t, J = 7.9, ArH). 13C NMR
(75 MHz, CDCl3): 10.9, 31.5, 42.3, 42.5, 55.2, 103.1, 108.8,
118.7, 125.2, 129.3, 141.9, 159.9. m/z (CI): 221 (M+, 100%),
207 (87). Anal. calcd. for. C12H16N2O2 (M): 220.121 2;
found (M+): 220.121 0.
297 (MNH4 , 20%), 280 (MH+, 100). Anal. calcd. for.
C16H13N3O2 (M): 279.100 8; found (M+): 279.100 5. Spec-
troscopic data for 9b: IR νmax (film, cm–1): 754, 1234, 1320,
1411, 1443, 1495, 1553, 1601, 1678, 1730. 1H NMR
(300 MHz, CDCl3) δ: 6.59 (1H, d, J = 3.2, ImH,), 7.12
(2H, m, ArH), 7.22 (1H, d, J = 3.2, ImH), 7.35 (5H, m,
ArH), 7.58 (6H, m, ArH), 7.79 (1H, d, J = 7.3, ArH), 8.49
(1H, bs, NH), 10.65 (1H, bs, NH). 13C NMR (75 MHz,
CDCl3) δ: 109.1, 113.9, 119.9, 120.1, 124.5, 124.7, 127.7,
128.3, 129.0, 129.3, 129.4, 131.5, 132.0, 135.0, 136.7,
4,5-Dihydro-1-(4-methoxy-2-methylphenyl)-3-methyl-
imidazol-2(1H)-one (6i) and 4,5-dihydro-1-(4-methoxy-3-
methylphenyl)-3-methylimidazol-2(1H)-one (6j)
+
137.6, 146.7, 151.4, 164.7. m/z (CI): 416 (MNH4 , 5%), 399
4,5-Dihydro-1-(4-methoxy-2-methylphenyl)-3-methylimida-
zol-2(1H)-one (6i) and 4,5-dihydro-1-(4-methoxy-3-methyl-
phenyl)-3-methylimidazol-2(1H)-one (6j) were prepared
from 4,5-dihydro-1-(4-methoxyphenyl)imidazol-2(1H)-one
4d (30 mg, 0.16 mmol) giving firstly from the column 6i
(3 mg, 9%) as a foamy yellow solid, and secondly, 6j (4 mg,
12%) as a yellow oil. Spectroscopic data for 6i: IR νmax
(film, cm–1): 1030, 1106, 1244, 1400, 1433, 1505, 1700,
(MH+, 8), 297 (20), 280 (100). Anal. calcd. for. C23H18N4O3
(M): 398.137 9; found (M+): 398.137 5.
3-(Phenylaminocarbonyl)-1-[6-methoxy-2-(phenylaminocar-
bonyl)phenyl]imidazol-2(1H)-one (9c) and 3-(phenylamino-
carbonyl)-1-[2-methoxy-3-(phenylaminocarbonyl)phenyl]-
imidazol-2(1H)-one (9d)
1
3-(Phenylaminocarbonyl)-1-[6-methoxy-2-(phenylaminocar-
bonyl)phenyl]imidazol-2(1H)-one (9c) and 3-(phenylamino-
carbonyl)-1-[2-methoxy-3-(phenylaminocarbonyl)phenyl]imidazol-
2(1H)-one (9d) were made from a solution of 1-(2-
methoxyphenyl)imidazol-2(1H)-one 3b (0.23 g, 1.2 mmol)
with n-BuLi (1.6 mol L–1, 1.95 mL, 2.5 equiv.), then phenyl
isocyanate (0.34 mL, 3.12 mmol, 2.5 equiv.) was added giv-
ing firstly from chromatography 9c (80 mg, 15%, slightly
contaminated by a phenyl isocyanate derivative), and sec-
ondly, 9d (97 mg, 18%) as low mp yellow solids. Spectro-
scopic data for 9c: IR νmax (film, cm–1): 754, 1055, 1233,
2923. H NMR (300 MHz, CDCl3) δ: 2.22 (3H, s, ArCH3),
2.90 (3H, s, NCH3), 3.45 (2H, apparent t, J = 7.9, ImH),
3.75 (2H, apparent t, J = 7.9, ImH), 3.80 (3H, s, OMe), 6.80
(1H, d, J = 7.7, ArH), 7.25 (1H, s, ArH), 7.57 (1H, m, ArH).
+
m/z (CI): 238 (MNH4 , 20%), 221 (MH+, 100). Anal. calcd.
for C12H16N2O2 (M): 220.121 2; found (M+): 220.121 6.
Spectroscopic data for 6j: IR νmax (film, cm–1): 1046, 1097,
1
1241, 1401, 1433, 1505, 1698, 3424. H NMR (300 MHz,
CDCl3) δ: 2.30 (3H, s, ArCH3), 2.80 (3H, s, NCH3), 3.48
(2H, t, J = 7.9, ImH), 3.65 (2H, t, J = 7.9, ImH), 3.82 (3H, s,
OMe), 6.76 (1H, m, ArH), 6.80 (1H, m, ArH), 7.12 (1H, d,
J = 7.8, ArH). 13C NMR (75 MHz, CDCl3) δ: 18.4, 31.9,
46.8, 46.0, 55.7, 112.4, 116.4, 128.5, 131.7, 138.1, 146.8,
1
1409, 1440, 1492, 1550, 1599, 1680, 1707, 1728. H NMR
(300 MHz, CDCl3) δ: 3.85 (3H, s, OCH3), 6.42 (1H, d, J =
3.2, ImH), 7.01–7.81 (14H, m, ArH + ImH), 8.54 (1H, s,
NH), 10.63 (1H, s, NH). 13C NMR (75 MHz, CDCl3) δ:
56.4, 102.9, 108.7, 113.9, 115.4, 120.0, 120.4, 120.7, 124.8,
124.9, 126.6, 128.6, 129.0, 129.3, 131.4, 138.0, 156.0,
+
158.7. m/z (CI): 238 (MNH4 , 20%), 221 (MH+, 100). Anal.
calcd. for. C12H16N2O2 (M): 220.121 2; found (M+):
220.121 1.
+
163.3, 164.8. m/z (CI): 446 (MNH4 , 25%), 429 (MH+, 40),
Typical procedure for lithiation of imidazolones (3a–3d)
with 2.5 equiv. n-BuLi and then reaction with phenyl
isocyanate
These experiments followed exactly the method described
previously for trapping with iodomethane, but used phenyl
isocyanate as the electrophile.
310 (100). Anal. calcd. for. C24H20N4O4 (M): 428.148 4;
found (M+): 428.149 3. Spectroscopic data for 9d: IR νmax
(film, cm–1): 753, 1441, 1598, 1710, 3329. 1H NMR
(300 MHz, CDCl3) δ: 3.75 (3H, s, OCH3), 6.24 (1H, bs,
ImH), 6.30 (1H, bs, ImH), 7.03 (3H, m, ArH), 7.21 (4H, ap-
parent t, J = 8.0, ArH), 7.29 (2H, apparent d, J = 7.7, ArH),
7.43 (2H, t, J = 8.0, ArH), 7.60 (2H, d, J = 7.7, ArH), 9.60
(1H, s, NH), 9.97 (1H, s, NH). 13C NMR (75 MHz, CDCl3)
δ: 56.3, 109.4, 113.6, 115.0, 115.5, 120.2, 120.6, 121.1,
122.5, 124.5, 128.1, 129.1, 130.9, 131.9, 138.5, 138.7,
1-Phenyl-3-(phenylaminocarbonyl)imidazol-2(1H)-one
(9a) and 3-(phenylaminocarbonyl)-1-[(2-phenylamino-
carbonyl)phenyl]imidazol-2(1H)-one (9b)
+
1-Phenyl-3-(phenylaminocarbonyl)imidazol-2(1H)-one
(9a) and 3-(phenylaminocarbonyl)-1-[(2-phenylaminocar-
bonyl)phenyl]imidazol-2(1H)-one (9b) were made from
1-phenylimidazol-2(1H)-one 3a (0.2 g, 1.25 mmol) with n-
BuLi (1.6 mol L–1, 1.95 mL, 2.5 equiv.), then phenyl
isocyanate (0.34 mL, 3.12 mmol, 2.5 equiv.) was added giv-
ing from chromatography firstly 9a as a yellow solid
(12 mg, 3%), mp 122 °C, lit. value (18) mp 123 °C, and sec-
ondly, 9b as a white solid (300 mg, 86%), mp 150 °C. Spec-
troscopic data for 9a: IR νmax (film, cm–1): 755, 1077, 1236,
1259, 1412, 1502, 1555, 1598, 1690, 1730. 1H NMR
(300 MHz, CDCl3) δ: 6.81 (1H, d, J = 3.2, ImH), 7.20
(1H, m, ArH), 7.28 (1H, d, J = 3.2, ImH), 7.40 (4H, m,
ArH), 7.59 (5H, m, ArH), 10.91 (1H, bs, NH). 13C NMR
(75 MHz, CDCl3) δ: 108.6, 111.7, 120.0, 122.4, 124.4,
127.1, 129.0, 129.4, 136.9, 147.3, 150.3, 162.7. m/z (CI):
142.2, 154.8, 156.0, 165.3. m/z (CI): 446 (MNH4 , 2%), 429
(MH+, 4), 327 (8), 310 (100), 217 (5), 102 (5). Anal. calcd.
for. C24H20N4O4 (M): 428.148 4; found (M+): 428.149 2.
1-[(3-Methoxy-2-phenylaminocarbonyl)phenyl]-3-phenyl-
aminocarbonylimidazol-2(1H)-one (9e) and 1-(3-methoxy-
phenyl)-3-(phenylaminocarbonyl)imidazol-2(1H)-one (9f)
1-[(3-Methoxy-2-phenylaminocarbonyl)phenyl]-3-phenyl-
aminocarbonylimidazol-2(1H)-one (9e) and 1-(3-methoxy-
phenyl)-3-(phenylaminocarbonyl)imidazol-2(1H)-one
(9f)
were made from 1-(3-methoxyphenyl)imidazol-2(1H)-one 3c
(0.27 g, 1.42 mmol) with n-BuLi (1.6 mol L–1, 2.2 mL, 2.5
equiv.) then phenyl isocyanate (0.39 mL, 3.5 mmol,
2.5 equiv.) giving from chromatography firstly 9e as a white
solid (160 mg, 36%), mp 101 °C, and secondly, 9f as a white
solid (95 mg, 21%), mp 180 °C. Spectroscopic data for 9e:
© 2004 NRC Canada