X. Zhou, Z. Jiang, L. Xue, P. Lu, Y. Wang
FULL PAPER
hydrous Na2SO4, and evaporated in vacuo. The residue was subject
to silica gel column chromatography with ethyl acetate/petroleum
ether (1:2, v/v) as eluent to give pure 6.
170.9, 160.3, 153.6, 140.7, 133.1, 128.9 and 127.9, 127.3, 114.6,
61.5, 55.5, 37.7, 15.7, 14.0 ppm. IR (film): ν = 2984, 2939, 2839,
˜
1737, 1682, 1531, 1514, 1470, 1454, 1300, 1252, 1164, 1024,
841 cm–1. HRMS (EI): m/z calcd. for C16H18N2O4 (M+) 302.1267;
found 302.1270.
Ethyl 2-[5-Formyl-1-(p-tolyl)-1H-imidazol-2-yl]propanoate (6a): Yel-
low oil (102 mg, 0.36 mmol, 71%). 1H NMR (400 MHz, CDCl3):
δ = 9.58 (s, 1 H), 7.88 (s, 1 H), 7.32 (d, J = 8.3 Hz, 2 H), 7.26–7.08
Ethyl 2-{5-Formyl-1-[4-(trifluoromethyl)phenyl]-1H-imidazol-2-yl}-
(br., 2 H), 4.16–4.02 (m, 2 H), 3.65 (q, J = 7.2 Hz, 1 H), 2.45 (s, 3 propanoate (6g): Yellow oil (136 mg, 0.2 mmol, 40%). 1H NMR
H), 1.56 (d, J = 7.2 Hz, 3 H), 1.18 (t, J = 7.1 Hz, 3 H) ppm. 13C (400 MHz, CDCl3): δ = 9.65 (s, 1 H), 7.90 (s, 1 H), 7.80 (d, J =
NMR (100 MHz, CDCl3): δ = 178.1, 170.8, 153.3, 140.5, 139.8,
133.0, 132.2, 130.0, 127.5, 126.5, 61.4, 37.6, 21.1, 15.6, 13.9 ppm.
8.6 Hz, 2 H), 7.50–7.37 (br., 2 H), 4.16–4.01 (m, 2 H), 3.60 (q, J =
7.2 Hz, 1 H), 1.59 (d, J = 7.2 Hz, 3 H), 1.18 (t, J = 7.1 Hz, 3
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 177.8, 170.5, 153.4,
142.0, 138.4, 132.8, 131.8 (q, J = 33.1 Hz), 129.6–127.8 (br.), 126.6
(q, J = 3.6 Hz), 123.4 (q, J = 271.7 Hz), 61.7, 37.8, 15.6, 13.9 ppm.
IR (film): ν = 2984, 2939, 1737, 1682, 1531, 1515, 1471, 1451, 1278,
˜
1163, 1084, 1025, 833, 771, 546 cm–1. HRMS (EI): m/z calcd. for
C16H18N2O3 (M+) 286.1317; found 286.1318.
IR (film): ν = 2988, 1738, 1682, 1616, 1533, 1441, 1326, 1166, 1129,
˜
Ethyl 2-[1-(4-Chlorophenyl)-5-formyl-1H-imidazol-2-yl]propanoate
(6b): Pale orange oil (96 mg, 0.32 mmol, 63%). 1H NMR
(400 MHz, CDCl3): δ = 9.63 (s, 1 H), 7.88 (s, 1 H), 7.50–7.49 (m,
1068, 854, 605 cm–1. HRMS (EI): m/z calcd. for C16H15N2O3F3
(M+) 340.1035; found 340.1036.
2 H), 7.32–7.15 (br., 2 H), 4.16–4.02 (m, 2 H), 3.62 (q, J = 7.2 Hz, 2-Benzhydryl-1-(p-tolyl)-1H-imidazole-5-carbaldehyde (6h): Yellow
1 H), 1.58 (d, J = 7.2 Hz, 3 H), 1.19 (t, J = 7.1 Hz, 3 H) ppm. 13C oil (121 mg, 0.35 mmol, 69%). 1H NMR (400 MHz, CDCl3): δ =
NMR (100 MHz, CDCl3): δ = 177.9, 170.6, 153.4, 141.6, 135.7,
133.5, 132.8, 129.7, 129.2, 128.0, 61.6, 37.7, 15.6, 13.9 ppm. IR
9.55 (s, 1 H), 7.92 (s, 1 H), 7.31–7.19 (m, 8 H), 7.16 (d, J = 7.2 Hz,
4 H), 6.97 (d, J = 8.0 Hz, 2 H), 5.19 (s, 1 H), 2.43 (s, 3 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 178.3, 155.9, 141.0, 140.2, 139.7,
132.7, 132.5, 130.0, 128.8, 128.7, 128.5, 127.1, 48.3, 21.3 ppm. IR
(film): ν = 2986, 1738, 1681, 1532, 1496, 1474, 1447, 1164, 1091,
˜
1013, 843 cm–1. HRMS (EI): m/z calcd. for C15H15N2O3Cl (M+)
306.0771; found 306.0763.
(film): ν = 3027, 1682, 1531, 1514, 1494, 1454, 1434, 1157, 821,
˜
725, 701, 542 cm–1. HRMS (EI): m/z calcd. for C24H20N2O (M+)
Ethyl 2-[1-(3-Chlorophenyl)-5-formyl-1H-imidazol-2-yl]propanoate
(6c): Yellow oil (80 mg, 0.26 mmol, 52%). 1H NMR (600 MHz,
CDCl3): δ = 9.64 (s, 1 H), 7.89 (s, 1 H), 7.53 (d, J = 8.2 Hz, 1 H),
352.1576; found 352.1577.
2-Benzhydryl-1-(4-methoxyphenyl)-1H-imidazole-5-carbaldehyde
7.46 (t, J = 8.0 Hz, 1 H), 7.35–7.28 (br., 1 H), 7.22–7.14 (br., 1 H), (6i): Yellow oil (138 mg, 0.38 mmol, 75%). 1H NMR (400 MHz,
4.20–4.39 (m, 2 H), 3.70–3.63 (m, 1 H), 1.61 (d, J = 7.2 Hz, 3 H), CDCl3): δ = 9.57 (s, 1 H), 7.92 (s, 1 H), 7.31–7.20 (m, 6 H), 7.18–
1.20 (t, J = 7.1 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 7.13 (m, 4 H), 7.00–6.98 (m, 2 H), 6.95–6.91 (m, 2 H), 5.20 (s, 1
177.9, 170.6, 153.3, 141.4, 136.1, 135.0, 132.8, 130.4, 130.0, 128.3
H), 3.87 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 178.4,
and 127.1, 126.4 and 125.0, 61.7, 37.7, 15.6, 14.0 ppm. IR (film): ν
160.2, 156.1, 141.1, 140.3, 132.8, 128.8, 128.6, 128.5, 127.6, 127.1,
˜
= 2986, 1738, 1681, 1593, 1533, 1480, 1445, 1163, 1077, 814,
687 cm–1. HRMS (EI): m/z calcd. for C15H15N2O3Cl (M+)
306.0771; found 306.0780.
114.5, 55.5, 48.4 ppm. IR (film): ν = 3025, 1678, 1530, 1513, 1454,
˜
1251, 1157, 1025, 837, 726, 701 cm–1. HRMS (EI): m/z calcd. for
C24H20N2O2 (M+) 368.1525; found 368.1526.
Ethyl 2-[1-(2-Chlorophenyl)-5-formyl-1H-imidazol-2-yl]propanoate 2-Benzhydryl-1-(4-bromophenyl)-1H-imidazole-5-carbaldehyde (6j):
(6d): Pale yellow oil (46 mg, 0.15 mmol, 30%). 1H NMR
(400 MHz, CDCl3): δ = 9.64 (s, 1 H), 7.91 (s, 1 H), 7.58 (dd, J =
8.0, 1.2 Hz, 1 H), 7.52–7.48 (m, 1 H), 7.43–7.38 (m, 2 H), 4.16–
4.03 (m, 2 H), 3.45 (q, J = 7.2 Hz, 1 H), 1.62 (d, J = 7.2 Hz, 3 H),
Yellow oil (135 mg, 0.33 mmol, 65 %). 1H NMR (400 MHz,
CDCl3): δ = 9.60 (s, 1 H), 7.91 (s, 1 H), 7.57–7.54 (m, 2 H), 7.32–
7.20 (m, 6 H), 7.17–7.11 (m, 4 H), 6.95–6.91 (m, 2 H), 5.15 (s, 1
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 178.0, 156.0, 141.9,
1.19 (t, J = 7.1 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 139.9, 134.4, 132.6, 132.5, 128.9, 128.69, 128.66, 127.3, 123.8,
177.9, 170.7, 153.3, 141.6, 133.2, 132.5, 132.1, 131.2, 130.4, 129.8,
48.5 ppm. IR (film): ν = 3061, 1678, 1531, 1493, 1452, 1433, 1158,
˜
127.8, 61.6, 37.9, 15.4, 14.0 ppm. IR (film): ν = 2923, 2850, 1737,
1068, 1006, 834, 732, 702, 540 cm–1. HRMS (EI): m/z calcd. for
˜
1679, 1536, 1489, 1469, 1377, 1162, 1086, 1026, 813 cm–1. MS C23H17N2OBr (M+) 416.0524; found 416.0527.
(MALDI-TOF): m/z = 307.10 [M + H]+. HRMS (EI): m/z calcd.
Ethyl 2-[5-Formyl-1-(p-tolyl)-1H-imidazol-2-yl]-2-phenylacetate
for C15H15N2O3 ([M – Cl]+) 271.1083; found 271.1079.
(6k): Yellow oil (96 mg, 0.28 mmol, 55%). 1H NMR (400 MHz,
CDCl3): δ = 9.56 (s, 1 H), 7.90 (s, 1 H), 7.38–7.11 (m, 8 H), 6.85
(br., 1 H), 4.80 (s, 1 H), 4.19–4.13 (m, 2 H), 2.45 (s, 3 H), 1.19 (t,
Ethyl 2-(5-Formyl-1-phenyl-1H-imidazol-2-yl)propanoate (6e): Yel-
low oil (101 mg, 0.37 mmol, 74%). 1H NMR (400 MHz, CDCl3):
δ = 9.59 (s, 1 H), 7.89 (s, 1 H), 7.57–7.49 (m, 3 H), 7.37–7.23 (br., J = 7.1 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 178.3,
2 H), 4.15–4.03 (m, 2 H), 3.64 (q, J = 7.2 Hz, 1 H), 1.58 (d, J = 169.0, 151.6, 140.6, 140.0, 134.4, 133.0, 132.1, 130.1, 129.2, 128.5,
7.2 Hz, 3 H), 1.18 (t, J = 7.1 Hz, 3 H) ppm. 13C NMR (100 MHz, 128.0, 127.1, 61.9, 49.5, 21.3, 14.0 ppm. IR (film): ν = 2981, 1747,
˜
CDCl3): δ = 178.2, 170.8, 153.3, 140.8, 134.9, 133.0, 129.8, 129.5,
1682, 1530, 1514, 1454, 1191, 1159, 1029, 829, 697, 541 cm–1
.
128.0 and 126.8, 61.5, 37.8, 15.7, 14.0 ppm. IR (film): ν = 2985, HRMS (EI): m/z calcd. for C21H20N2O3 (M+) 348.1474; found
˜
2940, 1737, 1682, 1597, 1532, 1498, 1473, 1450, 1278, 1163, 1076,
1026, 815, 776, 695 cm–1. HRMS (EI): m/z calcd. for C15H16N2O3
(M+) 272.1161; found 272.1163.
348.1473.
Ethyl 2-(4-Bromophenyl)-2-[5-formyl-1-(p-tolyl)-1H-imidazol-2-yl]-
acetate (6l): Brown solid (98 mg, 0.23 mmol, 46%), m.p. 83–87 °C;
1H NMR (400 MHz, CDCl3): δ = 9.48 (s, 1 H), 7.81 (s, 1 H), 7.37–
7.33 (m, 2 H), 7.33–7.28 (m, 2 H), 7.18–7.09 (br., 2 H), 7.06–6.98
Ethyl 2-[5-Formyl-1-(4-methoxyphenyl)-1H-imidazol-2-yl]propano-
ate (6f): Yellow oil (106 mg, 0.35 mmol, 70%). 1H NMR
(400 MHz, CDCl3): δ = 9.58 (s, 1 H), 7.87 (s, 1 H), 7.28–7.13 (br., (br., 1 H), 6.87–6.78 (br., 1 H), 4.38 (s, 1 H), 4.27–4.14 (m, 2 H),
2 H), 7.01 (dd, J = 7.6, 1.5 Hz, 2 H), 4.17–4.02 (m, 2 H), 3.88 (s,
3 H), 3.66 (q, J = 7.2 Hz, 1 H), 1.57 (d, J = 7.2 Hz, 3 H), 1.19 (t,
J = 7.1 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 178.3,
2.37 (s, 3 H), 1.25 (t, J = 7.1 Hz, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 178.9, 171.1, 152.8, 139.6, 137.7, 136.7, 134.3, 131.8,
130.8, 129.1, 128.5, 128.0, 122.6, 76.5, 63.9, 21.2, 13.7 ppm. IR
5796
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Eur. J. Org. Chem. 2015, 5789–5797