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Yang P, et al. Sci China Chem October (2011) Vol.54 No.10
8.37 Hz), 7.63 (3H, m), 7.03 (1H, s), 5.71 (1H, d, J = 7.82
Hz), 5.52 (1H, dd, J = 9.63 Hz, J = 9.63 Hz), 5.18 (1H, dd,
J = 7.81 Hz, J = 9.52 Hz), 5.08 (1H, dd, J = 9.68 Hz, J =
9.68 Hz), 4.58 (1H, d, J = 9.90 Hz), 3.62 (3H, s), 2.34 (3H,
s), 2.34 (3H, s), 2.06 (3H, s), 1.99 (6H, s). 13C NMR (150
MHz, DMSO-d6): δ 19.6, 20.2, 29.0, 52.6, 68.7, 69.6, 70.5,
71.1, 96.4, 101.1, 110.9, 117.3, 128.5, 129.1, 130.2, 130.8,
131.4, 141.3, 152.5, 154.2, 160.2, 166.8, 168.1, 169.4,
169.7. ESI-MS: 727.5 (M+23)+. HRMS (ESI) for
C32H30O16Cl (M+H), 705.12169 (calcd), found 705.12153.
20.5, 20.9, 52.6, 71.0, 71.4, 98.0, 100.4, 106.4, 122.8, 128.0,
151.3, 153.5, 159.5, 161.2, 163.0, 167.7, 168.0, 168.9,
169.1, 172.0. ESI-MS: 829.7, 831.2 (M+23)+. HRMS (ESI)
for C34H32O18Br (M+H), 807.07721 (calcd), found
807.07716.
5,6-Diacetoxy-3-bromo-7-hydroxyflavon-7-o-(2,3,4-tri-o-acetyl-
beta-D-glucopyranosiduronsauremethylester) (2c)
This compound was prepared employing the general proce-
dure with compound 2a as the starting material. Yield:
31.2 %, white solid. Mp 254–255 °C. IR: ν 3490, 3068,
2958, 2856, 1759, 1650, 1608, 1578, 1563, 1496, 1436,
1366, 1219, 1169, 1072, 1035, 976, 935, 886, 852, 803, 775,
5,6,7,4′-Tetraacetoxy-8-chloro-flavone (3b)
This compound was prepared employing the general proce-
dure with compound 3a as the starting material. Yield:
36.8%, white solid. Mp 206–207 °C. IR: ν 3539, 3043, 2994,
2942, 1796, 1651, 1626, 1605, 1568, 1508, 1456, 1438,
1417, 1374, 1351, 1309, 1293, 1195, 1110, 1083, 1037,
1
691 cm-1. H NMR (300 MHz, DMSO-d6): 7.86 (2H, m),
7.62 (3H, m), 7.51 (1H, s), 5.85 (1H, d, J = 7.62 Hz), 5.43
(1H, dd, J = 9.69 Hz, J = 9.69 Hz), 5.21 (1H, J = 8.67 Hz, J
= 8.67 Hz), 5.09 (1H, dd, J = 9.79 Hz, J = 9.79 Hz), 4.82
(1H, d, J = 10.15 Hz), 3.62 (3H, s), 2.39 (3H, s), 2.29 (3H,
s), 2.01 (6H, s), 2.00 (3H, s). 13C NMR (150 MHz,
DMSO-d6): δ 20.2, 20.3, 20.5, 52.6, 68.9, 71.0, 71.4, 100.4,
107.5, 114.8, 126.4, 129.2, 130.3, 132.3, 140.8, 149.8,
151.1, 161.9, 166.7, 167.2, 169.1, 169.2, 169.5, 175.1.
ESI-MS: 771.5, 773.3 (M+23)+. HRMS (ESI) for
C32H30O16Br (M+H), 749.07117 (calcd), found 749.07176.
1
1016, 944, 929, 909, 874, 841, 820, 727, 685, 673 cm-1. H
NMR (300 MHz, DMSO-d6): 8.15 (2H, d, J = 8.35 Hz),
7.39 (2H, d, J = 8.35 Hz), 7.05 (1H, s), 2.48 (3H, s), 2.40
(3H, s), 2.37 (3H, s), 2.32 (3H, s). 13C NMR (150 MHz,
DMSO-d6): δ 20.4, 20.5, 20.9, 106.8, 113.5, 122.8, 128.0,
128.9, 130.9, 136.0, 139.7, 155.7, 167.4, 168.9, 169.5,
174.7, 180.5. ESI-MS: 511.4 (M + 23)+. HRMS (ESI) for
C23H18O10Cl (M+H), 489.05830 (calcd), found 489.05908.
5,6,7,4′-Tetraacetoxy-8-bromo-flavone (3c)
5,6,7-Triacetoxy-8-chloro-flavone(4b)
This compound was prepared employing the general proce-
dure with compound 3a as the starting material. Yield:
28.6 %, white solid. Mp 171–172 °C. IR: ν 3532, 3285,
3073, 2992, 2938, 1783, 1651, 1626, 1609, 1558, 1504,
1455, 1373, 1327, 1285, 1171, 1092, 1061, 1016, 960, 911,
This compound was prepared employing the general proce-
dure with compound 4a as the starting material. Yield:
32.6%, white solid. Mp 232–234 °C. IR: ν 3474, 3061, 3016,
2936, 2853, 1791, 1651, 1606, 1586, 1571, 1496, 1458,
1438, 1373, 1354, 1202, 1175, 1118, 1088, 1040, 1029,
1014, 945, 932, 880, 847, 771, 744, 687 cm-1. 1H NMR (300
MHz, DMSO-d6): 8.10 (2H, d, J = 8.08 Hz), 7.62 (3H, m),
7.06 (1H, s), 2.48 (3H, s), 2.40 (3H, s), 2.37 (3H, s). 13C
NMR (150 MHz, DMSO-d6): δ 19.7, 19.9, 20.5, 107.8,
115.7, 126.2, 126.4, 129.1, 129.2, 130.2, 144.4, 145.7,
150.5, 161.9, 166.7, 168.2, 180.1, 182.1. ESI-MS: 453.2
(M+23)+. HRMS (ESI) for C21H16O8Cl (M+H), 431.05285
(calcd), found 431.05339.
1
853, 831, 781, 735, 688, 666 cm–1. H NMR (300 MHz,
DMSO-d6): 8.17 (2H, d, J = 8.60 Hz), 7.40 (2H, d, J = 8.60
Hz), 7.05 (1H, s), 2.47 (3H, s), 2.39 (3H, s), 2.36 (3H, s),
2.32 (3H, s). 13C NMR (150 MHz, DMSO-d6): δ 19.7, 20.0,
20.5, 20.9, 107.2, 107.7, 122.8, 124.8, 127.0, 127.8, 128.0,
133.6, 135.4, 141.3, 145.8, 167.7, 168.9, 171.5, 171.6,
175.1. ESI-MS: 533.2, 535.1 (M+1)+. HRMS (ESI) for
C23H18O10Br (M+H), 533.00779 (calcd), found 533.00760.
5,6,7,4′-Tetraacetoxy-3-bromo-flavone (3c′)
5,6,4′-Triacetoxy-8-bromo-7-hydroxyflavon-7-o-(2,3,4-tri-o-
acetyl-beta-D-glucopyranosiduronsauremethylester) (1c)
This compound was prepared employing the general proce-
dure with compound 3a as the starting material. Yield:
18.2%, white solid. Mp 258–259 °C. IR: ν 3043, 2993,
2941, 1796, 1651, 1625, 1603, 1561, 1508, 1455, 1434,
1417, 1374, 1348, 1309, 1292, 1166, 1107, 1080, 1034,
1015, 938, 907, 866, 840, 804, 744, 726, 681 cm-1.1H NMR
(300 MHz, DMSO-d6): 7.92 (2H, d, J = 8.61 Hz), 7.75 (1H,
s), 7.37 (2H, d, J = 8.61 Hz), 2.39 (3H, s), 2.38 (3H, s), 2.35
(3H, s), 2.32 (3H, s). 13C NMR (150 MHz, DMSO-d6): δ
20.4, 20.5, 20.9, 108.9, 109.2, 111.1, 113.2, 122.0, 129.6,
130.8, 130.9, 133.0, 141.2, 147.2, 152.3, 152.5, 153.2,
161.0, 167.4, 167.5, 169.0, 170.2. ESI-MS: 555.2, 557.1
(M+23)+. HRMS (ESI) for C23H18O10Br (M+H), 533.00779
(calcd), found 533.00781.
This compound was prepared employing the general proce-
dure with compound 1a as the starting material. Yield:
27.0 %, white solid. Mp 236–237 °C. IR: ν 3491, 3060,
2998, 2960, 1757, 1643, 1622, 1564, 1509, 1493, 1438,
1371, 1293, 1200, 1172, 1147, 1072, 1034, 972, 933, 910,
1
884, 851, 806, 784, 729, 681 cm–1. H NMR (300 MHz,
DMSO- d6): 8.18 (2H, d, J = 8.69 Hz), 7.40 (2H, d, J = 8.69
Hz), 7.03 (1H, s), 5.71 (1H, d, J = 7.77 Hz), 5.53 (1H, dd, J
= 9.66 Hz, J = 9.66 Hz), 5.19 (1H, dd, J = 7.97 Hz, J = 9.36
Hz), 5.08 (1H, dd, J = 9.99 Hz, J = 9.99 Hz), 4.59 (1H, d, J
= 9.92 Hz), 6.63 (3H, s), 2.34 (3H, s), 2.32 (3H, s), 2.07 (3H,
s), 1.99 (6H, s). 13C NMR (150 MHz, DMSO-d6): δ 20.3,