942
K. Yamauchi et al. / Bioorg. Med. Chem. 22 (2014) 937–944
(C-6), 102.8 (C-A1), 103.2 (C-B1), 104.3 (C-4a), 114.7 (C-50), 116.2
(C-20), 121.7 (C-10), 121.9 (C-60), 134.2 (C-3), 144.6 (C-30), 148.5
(C-40), 157.1 (C-2), 157.6 (C-8a), 161.7 (C-5), 164.6 (C-7), 178.1
(C-4); UPLC–TOFMS ESꢂ m/z 625.1404 [Mꢂ1]ꢂ.
(C-B1, D1), 104.4 (C-4a), 115.9 (C-50), 116.7 (C-20), 121.6 (C-10),
125.2 (C-60), 134.7 (C-3), 146.3 (C-30), 147.6 (C-40), 156.8 (C-2),
157.1 (C-8a), 161.7 (C-5), 164.8 (C-7), 178.1 (C-4); MALDI-TOFMS
m/z 973.1037 [M+Na]+.
4.2.6. 40-O-b-
D
-Glucopyranosyl-quercetin-3-O-b-
D
-
4.2.9. 7-O-b-
D
-Glucopyranosyl-(1?4)-b-
D-glucopyranosyl-
glucopyranosyl-(1?4)-b-
D
-glucopyranoside (3)
quercetin-3-O-b-
D
-glucopyranosyl-(1?4)-b- -glucopyranoside
D
Yellow powder; UV kmax 207, 265, 345 nm; ½a D20
ꢁ
ꢂ34.4° (c 0.32,
(6)
MeOH/H2O = 1:1 v/v); IR (KBr)
m
max 3416, 1655, 1612, 1498, 1433,
Yellow powder; UV kmax 204, 255, 353 nm; ½a D20
ꢂ30.7° (c 0.46,
ꢁ
1366, 1258, 1204, 1074 cmꢂ1
;
1H NMR (CD3OD, 600 MHz) dH 3.19
MeOH/H2O = 1:4 v/v); IR (KBr) mmax 3409, 1656, 1601, 1496, 1342,
(1H, t, J = 8.22 Hz, H-B2), 3.29–3.33 (5H, m, H-A4, A5, B3, B4, B5),
3.49 (1H, t, J = 7.6 Hz, H-A2), 3.52 (1H, m, H-C4), 3.56 (1H, t,
J = 8.3 Hz, H-C2), 3.58–3.59 (2H, m, H-A3, C5), 3.70 (1H, m, H-C3),
3.71 (2H, m, H-A6), 3.86–3.90 (2H, m, H-C6), 4.38 (1H, d,
J = 8.3 Hz, H-B1), 4.92 (1H, d, J = 7.6 Hz, H-C1), 5.32 (1H, d,
J = 7.6 Hz, H-A1), 6.19 (1H, d, J = 1.4 Hz, H-6), 6.38 (1H, br s, H-8),
7.25 (1H, d, J = 8.9 Hz, H-50), 7.63 (1H, dd, J = 8.9, 2.0 Hz, H-60),
7.68 (1H, d, J = 2.0 Hz, H-20); 13C NMR (CD3OD, 150 MHz) dC 60.5
(C-A6), 61.1 (C-B6, C6), 69.9 (C-B4), 70.1 (C-C4), 73.5 (C-B2, C2),
74.1 (C-C3), 75.0 (C-A2), 75.6 (C-A5), 76.5 (C-A3, B5), 76.8 (C-B3,
C5), 79.0 (C-A4), 93.4 (C-8), 98.7 (C-6), 101.9 (C-C1), 102.5 (C-
A1), 103.2 (C-B1), 104.5 (C-4a), 115.9 (C-50), 116.7 (C-20), 121.6
(C-10), 125.2 (C-60), 134.7 (C-3), 146.3 (C-30), 147.7 (C-40), 156.9
(C-2), 157.2 (C-8a), 161.8 (C-5), 164.8 (C-7), 178.2 (C-4); UPLC–
TOFMS ESꢂ m/z 787.1973 [Mꢂ1]ꢂ.
1204, 1072 cmꢂ1 1H NMR (CD3OD, 600 MHz) dH 3.19 (1H, t,
;
J = 8.9 Hz, H-B2), 3.24 (1H, t, J = 7.6 Hz, H-F2), 3.27–3.30 (2H, m,
H-B4, F4), 3.30–3.39 (6H, m, H-A5, B3, B5, E5, F3, F5), 3.53 (1H, t,
J = 8.9 Hz, H-A2), 3.56–3.68 (6H, m, H-A3, A4, E2, E3, one of B6,
F6), 3.70 (1H, m, H-E4), 3.70–3.73 (2H, m, one of the H-A6, E6),
3.83–3.91 (2H, m, one of the H-B6, F6), 3.92–3.94 (2H, m, one of
the H-A6, E6), 4.37 (1H, d, J = 8.2 Hz, H-B1), 4.43 (1H, d,
J = 8.2 Hz, H-F1), 5.09 (1H, d, J = 7.6 Hz, H-C1), 5.36 (1H, d,
J = 7.6 Hz, H-A1), 6.47 (1H, d, J = 2.0 Hz, H-6), 6.73 (1H, d,
J = 1.4 Hz,H-8), 6.85 (1H, d, J = 8.3 Hz, H-50), 7.59 (1H, br d,
J = 8.9 Hz, H-60), 7.69 (1H, d, J = 2.0 Hz, H-20); 13C NMR (DMSO-d6,
150 MHz) dC 60.5 (C-E6), 60.9 (C-A6), 61.6 (C-B6, F6), 70.6 (C-B4,
F4), 73.3 (C-E2), 73.8 (C-B2, F2), 74.3 (C-A2), 75.3 (C-E3), 75.4
(C-A3), 75.6 (C-B3), 76.0 (C-F3), 77.0 (C-B5, F5), 77.3 (C-A5,
C-E5), 80.3 (C-E4), 80.9 (C-A4), 94.9 (C-8), 99.7 (C-6), 100.1 (C-
E1), 103.7 (C-A1), 103.7 (C-B1, F1), 106.2 (C-4a), 115.6 (C-50),
116.9 (C-20), 121.4 (C-10), 122.2 (C-60), 134.0 (C-3), 145.4 (C-30),
149.4 (C-40), 156.5 (C-2), 157.5 (C-8a), 161.4 (C-5), 163.2 (C-7),
178.0 (C-4); MALDI-TOFMS m/z 973.1037 [M+Na]+.
4.2.7. 7-O-b-D-Glucopyranosyl-quercetin-3-O-b-D-
glucopyranosyl-(1?4)-b-D-glucopyranoside (4)
Yellow powder; UV kmax 204, 255, 353 (nm); ½a D20
ꢂ41.4° (c
ꢁ
0.17, MeOH/H2O = 1:4 v/v); IR (KBr) mmax 3447, 1651, 1494, 1338,
1202, 1073 cmꢂ1
;
1H NMR (CD3OD, 600 MHz,) dH 3.19 (1H, t,
4.2.10. 40-O-b-
D
-glucopyranosyl-quercetin-3-O-b-
D
-
J = 8.3 Hz, H-B2), 3.28–3.33 (6H, m, H-A4, A5, B3, B4, B5, E3), 3.46
(1H, m, H-E4), 3.47 (1H, m, H-E2) 3.55–3.59 (3H, m, H-A2, A3,
E5), 3.71 (2H, m, H-A6), 3.86–3.89 (2H, m, H-E6), 4.38 (1H, d,
J = 6.9 Hz, H-B1), 5.04 (1H, d, J = 6.2 Hz, H-E1), 5.35 (1H, d,
J = 7.6 Hz, H-A1), 6.47 (1H, br s, H-6), 6.74 (1H, br s, H-8), 6.84
(1H, d, J = 8.3 Hz, H-50), 7.56 (1H, br d, J = 7.6 Hz, H-60), 7.69 (1H,
br s, H-20); 13C NMR (CD3OD, 150 MHz) dC 60.4 (C-A6), 60.8
(C-E6), 61.1 (C-B6), 69.9 (C-B4), 70.0 (C-E4), 73.5 (C-B2, C2), 74.1
(C-E3), 75.1 (C-A2), 75.6 (C-A5), 76.5 (C-A3, B5), 76.8 (C-B3), 77.0
(C-E5), 79.0 (C-A4), 94.3 (C-8), 100.3 (C-6), 101.9 (C-E1), 102.4
(C-A1), 103.2 (C-B1), 106.1 (C-4a), 114.7 (C-50), 116.2 (C-20),
121.5 (C-10), 122.0 (C-60), 134.4 (C-3), 144.6 (C-30), 148.7 (C-40),
156.6 (C-2), 158.2 (C-8a), 161.4 (C-5), 163.5 (C-7), 177.1 (C-4);
UPLC–TOFMS ESꢂ m/z 787.1978 [Mꢂ1]ꢂ.
glucopyranoside (7)
Yellow powder; UV kmax 206, 265, 344 nm; ½a D20
ꢁ
ꢂ31.3° (c 0.60,
MeOH); IR (KBr) m
max 3430, 1656, 1498, 1364, 1204, 1076 cmꢂ1; 1H
NMR (CD3OD, 600 MHz) dH 3.20 (1H, m, H-A5), 3.30 (1H, t,
J = 9.7 Hz, H-A4), 3.38–3.43 (2H, m, H-C4, C5), 3.46–3.55 (3H, m,
H-A2, A3, C2, C3), 3.69–3.73 (3H, m, H-A6, one of the C6), 3.91
(1H, br d, J = 10.3 Hz, one of the H-C6), 4.91 (1H, d, J = 7.6 Hz,
H-C1), 5.29 (1H, d, J = 7.6 Hz, H-A1), 6.19 (1H, br s, H-6), 6.38
(1H, br s, H-8), 7.26 (1H, d, J = 8.9 Hz, H-50), 7.63 (1H, br d,
J = 8.9 Hz, H-60), 7.69 (1H, br s, H-20); 13C NMR (CD3OD, 150 MHz)
dC 61.1 (C-C6), 61.2 (C-A6), 70.0 (C-A4, C4), 73.4 (C-C2), 74.3 (C-
A2), 76.2 (C-A3), 76.7 (C-C3), 77.1 (C-A5, C5), 89.5 (C-8), 93.4 (C-
6), 101.9 (C-C1), 102.6 (C-A1), 103.3 (C-4a), 115.9 (C-50), 116.7
(C-20), 121.5 (C-10), 125.3 (C-60), 134.7 (C-3), 146.3 (C-30), 147.7
(C-40), 153.4 (C-2), 157.2 (C-8a), 161.8 (C-5), 165.3 (C-7), 178.2
(C-4); MALDI-TOFMS m/z 649.1273 [M+Na]+.
4.2.8. 40-O-b-
D
-Glucopyranosyl-(1?4)-b-
D
-glucopyranosyl-
quercetin-3-O-b-
D
-glucopyranosyl-(1?4)-b- -glucopyranoside
D
(5)
4.2.11. 7-O-b-D-Glucopyranosyl-quercetin-3-O-b-D-
Yellow powder; UV kmax 205, 264, 345 nm; ½a D20
ꢁ
ꢂ35.9° (c 0.55,
glucopyranoside (8)
MeOH/H2O = 1:4 v/v); IR (KBr) mmax 3437, 1655, 1498, 1204,
Yellow powder; UV kmax 204, 255, 354 nm; ½a D20
ꢂ14.4° (c 0.10,
ꢁ
1076 cmꢂ1
;
1H NMR (CD3OD, 600 MHz) dH 3.19 (1H, t, J = 8.2 Hz,
MeOH); IR (KBr) mmax 3402, 1656, 1608, 1498, 1304, 1203,
H-B2), 3.25 (1H, t, J = 8.2 Hz, H-D2), 3.27–3.30 (2H, m, H-B4, D4),
3.30–3.37 (6H, m, H-A5, B3, B5, C5, D3, D5), 3.51 (1H, t,
J = 8.3 Hz, H-A2), 3.58-3.68 (6H, m, H-A3, A4, C2, C3, one of B6,
D6), 3.69 (1H, m, H-C4), 3.69–3.73 (2H, m, one of the H-A6, C6),
3.85–3.90 (2H, m, one of the H-B6, D6), 3.92–3.94 (2H, m, one of
the H-A6, C6), 4.37 (1H, d, J = 9.4 Hz, H-B1), 4.45 (1H, d,
J = 7.6 Hz, H-D1), 4.95 (1H, d, J = 7.6 Hz, H-C1), 5.30 (1H, d,
J = 7.6 Hz, H-A1), 6.17 (1H, br s, H-6), 6.35 (1H, br s, H-8), 7.21
(1H, d, J = 8.2 Hz, H-50), 7.62 (1H, br d, J = 8.9 Hz, H-60), 7.66 (1H,
br s, H-20); 13C NMR (CD3OD, 150 MHz) dC 60.2 (C-C6), 60.4
(C-A6), 61.1 (C-B6, D6), 70.0 (C-B4, D4), 73.2 (C-C2), 73.5 (C-B2),
73.6 (C-D2), 74.0 (C-A2), 74.5 (C-C3), 75.0 (C-A3), 75.5 (C-B3),
75.6 (C-D3), 76.5 (C-B5, D5), 76.8 (C-A5, C5), 78.8 (C-C4), 78.9
(C-A4), 93.5 (C-8), 98.7 (C-6), 101.6 (C-C1), 102.6 (C-A1), 103.3
1071 cmꢂ1 1H NMR (CD3OD, 600 MHz) dH 3.20 (1H, m, H-A5),
;
3.32–3.42 (3H, m, H-A4, E4, E5), 3.46 (2H, m, H-A2, E2), 3.49–
3.57 (2H, m, H-A3, E3), 3.83–3.91 (2H, m, one of the H-A6, E6),
4.19–4.21 (2H, m, one of the H-A6, E6), 5.04 (1H, d, J = 7.6 Hz,
H-E1), 5.32 (1H, d, J = 7.6 Hz, H-A1), 6.48 (1H, d, J = 2.0 Hz, H-6),
6.74 (1H, d, J = 1.4 Hz,H-8), 6.85 (1H, d, J = 8.9 Hz, H-50), 7.60 (1H,
dd, J = 8.2, 1.4 Hz, H-60), 7.70 (1H, d, J = 2.1 Hz, H-20); 13C NMR
(CD3OD, 150 MHz) dC 61.1 (C-E6), 61.2 (C-A6), 70.0 (C-A4, E4),
73.4 (C-E2), 74.4 (C-A2), 76.5 (C-A3), 76.7 (C-E3), 77.0 (C-E5),
77.1 (C-A5), 94.4 (C-8), 99.5 (C-6), 100.3 (C-C1), 102.5 (C-A1),
106.1 (C-4a), 114.7 (C-50), 116.2 (C-20), 121.6 (C-10), 122.0 (C-60),
134.4 (C-3), 144.6 (C-30), 148.7 (C-40), 155.7 (C-2), 158.2 (C-8a),
161.4 (C-5), 163.4 (C-7), 178.4 (C-4); MALDI-TOFMS m/z
649.3783 [M+Na]+.