Vol. 63, No. 1 (2015)
Chem. Pharm. Bull.
53
J=7Hz, H-1′), 4.58 (1H, dd, J=12, 2Hz, H-6′a), 4.48 (1H, (1H, m, H-4), 3.66 (3H, s, –OCH3), 3.00 (2H, s, H2-7), 2.48
dd, J=12, 5Hz, H-6′b), 3.78 (1H, d, J=11Hz, H-7a), 3.77 (1H, (1H, brd, J=17Hz, H-3a), 2.24 (1H, brd, J=17Hz, H-3b), 2.19
d, J=11Hz, H-7b), 3.54–3.51 (4H, m, H-2′, 3′, 4′, and 5′); (2H, m, H-6a), 2.14 (1H, m, H-6b), 2.01 (1H, dddd, J=9, 6, 3,
13C-NMR (100MHz, CD3OD): Table 1; HR-ESI-MS (positive- 1Hz, H-5a), 1.85 (1H, m, H-5b); 13C-NMR (150MHz, CD3OD):
ion mode) m/z: 486.1000 [M+Na]+ (Calcd for C21H21NO11Na: Table 1; HR-ESI-MS (negative-ion mode) m/z: 249.0434
486.1007).
[M−H]− (Calcd for C9H13O6S: 249.0427).
Compound 2: Off-white amorphous powder; [α]D25 −5.1
Mild Alkaline Hydrolysis of 1 Compound 1 (16mg) was
(c=1.62, MeOH); IR νmax (film) cm−1: 3363, 2925, 2260, 1700, treated in 1mL of 0.1M CH3ONa in MeOH for 3h at 35°C.
1614, 1452, 1230, 1076, 1036; UV λmax (MeOH) nm (logε): 272 The reaction mixture was diluted with 4mL of H2O and then
(4.17), 223 (4.29); H-NMR (400MHz; CD3OD) δ: 7.14 (1H, d, neutralized with Amberlite IR-120B (H+). The aqueous layer
1
J=8Hz, H-6), 7.17 (2H, s, H-2″ and 6″, or H-2‴ and 6‴), 7.10 was extracted with CHCl3 (4mL) and then evaporated to dry-
(2H, s, H-2‴ and 6‴, or H-2″ and 6″), 6.74 (1H, d, J=2Hz, ness. The residue was dissolved in MeOH and the precipitate
H-3), 6.53 (1H, dd, J=8, 2Hz, H-5), 5.26 (1H, dd, J=9, 9Hz, formed was removed by filtration to leave 10mg of 1a (=12).
H-3′), 5.02 (1H, d, J=8Hz, H-1′), 4.60 (1H, dd, J=12, 2Hz, An expected compound, methyl gallate, was not present in the
H-6′a), 4.50 (1H, dd, J=12, 5Hz, H-6′b), 3.84–3.78 (4H, m, CHCl3 layer. Probably it was decomposed in the basic media.
H-2′, 4′, and 5′), 3.77 (1H, d, J=11Hz, H-7a), 3.76 (1H, d,
The NMR spectroscopic data for 1a for pyridine-d5 were
J=11Hz, H-7b); 13C-NMR (100MHz, CD3OD): Table 1; HR- identical with those of ehretioside B (12),7) and those for
ESI-MS (positive-ion mode) m/z: 638.1105 [M+Na]+ (Calcd CD3OD with those of 12 isolated from S. adoxoides8) (Table 1).
for C28H25NO15Na: 638.1116).
Sugar Analysis About 1.0mg aliquots of compounds 1–5
Compound 3: Colorless amorphous powder; [α]D26 −42.9 were hydrolyzed with 1M HCl (0.1mL) at 90°C for 2h. The re-
(c=1.08, MeOH); IR νmax (film) cm−1: 3332, 2959, 2267, 1726, action mixtures were then each washed with an equal amount
1605, 1511, 1234, 1071, 1013; UV λmax (MeOH) nm (logε): 259 of EtOAc and the aqueous layers were analyzed by HPLC,
1
(4.13), 215 (4.12); H-NMR (600MHz; CD3OD) δ: 7.90 (2H, which gave a peak for D-glucose at 15.2min with positive
d, J=9Hz, H-2″ and 6″), 7.13 (1H, d, J=8Hz, H-6), 6.82 (2H, optical rotation signs. [Optical rotation detector: JASCO OR-
d, J=9Hz, H-2″ and 5″), 6.72 (1H, d, J=2Hz, H-3), 6.51 (1H, 2090Plus, column: Shodex Asahipak NH2P-50; Φ=4.5mm,
dd, J=8, 2Hz, H-5), 4.91 (1H, d, J=7Hz, H-1′), 4.69 (1H, dd, L=25cm, solvent: CH3CN–H2O (4:1), 1mL/min]. Peaks were
J=12, 2Hz, H-6′a), 4.31 (1H, dd, J=12, 7Hz, H-6′b), 3.80 (1H, identified by co-chromatography with authentic D-glucose.
d, J=18Hz, H-7a), 3.75 (1H, d, J=18Hz, H-7b), 3.74 (1H, m,
H-5′), 3.54 (1H, dd, J=9, 7Hz, H-2′), 3.51 (1H, dd, J=9, 9Hz,
Acknowledgments The authors are grateful for access to
H-3′), 3.46 (1H, dd, J=9, 9Hz, H-4′); 13C-NMR (150MHz, the superconducting NMR instrument (JEOL JNM α-400) and
CD3OD): Table 1; HR-ESI-MS (positive-ion mode) m/z: an Applied Biosystem QSTAR XL system ESI (Nano Spray)-
454.1108 [M+Na]+ (Calcd for C21H21NO9Na: 454.1109).
MS at the Analysis Center of Life Science of the Graduate
Compound 4: Colorless amorphous powder; [α]D26 −61.8 School of Biomedical Sciences, Hiroshima University. This
(c=0.33, MeOH); IR νmax (film) cm−1: 3363, 2927, 2256, 1726, work was supported in part by Grants-in-Aid from the Min-
1605, 1587, 1517, 1171, 1073, 1020; UV λmax (MeOH) nm istry of Education, Culture, Sports, Science and Technol-
1
(logε): 268 (4.90), 209 (4.30); H-NMR (600MHz; CD3OD) δ: ogy of Japan (Nos. 22590006, 23590130, and 25860078), the
7.15 (1H, d, J=8Hz, H-6), 6.64 (1H, d, J=2Hz, H-3), 6.51 (1H, Japan Society for the Promotion of Science, and the Ministry
dd, J=8, 2Hz, H-5), 5.45 (1H, brs, H-2″), 4.81 (1H, d, J=8Hz, of Health, Labour and Welfare. Thanks are also due to the
H-1′), 4.44 (1H, dd, J=12, 2Hz, H-6′a), 4.25 (1H, dd, J=12, Research Foundation for Pharmaceutical Sciences and the
6Hz, H-6′b), 3.80 (1H, m, H-4″), 3.77 (2H, m, H2-7), 3.61 (1H, Takeda Science Foundation for the financial support.
ddd, J=9, 6, 2Hz, H-5′), 3.49 (1H, dd, J=9, 9Hz, H-2′), 3.46
(1H, dd, J=9, 9Hz, H-3′), 3.38 (1H, dd, J=9, 9Hz, H-4′), 3.02
Conflict of Interest The authors declare no conflict of
(2H, s, H2-7″), 2.28 (1H, brd, J=17Hz, H-3″a), 2.10 (2H, m, interest.
H2-6″), 1.94 (1H, brd, J=17Hz, H-3″b), 1.80 (1H, m, H-5″a),
1.55 (1H, m, H-5″b); 13C-NMR (150MHz, CD3OD): Table
1; HR-ESI-MS (positive-ion mode) m/z: 472.1576 [M+Na]+
(Calcd for C22H27NO9Na: 472.1578).
Compound 5: Colorless amorphous powder; [α]D26 −38.0
(c=0.59, MeOH); IR νmax (film) cm−1: 3367, 2938, 2878, 1726,
1587, 1528, 1227, 1075, 1042, 1014; UV λmax (MeOH) nm
3) Kawakita A., Takimura A., Terachi T., Sota T., Kato M., Evolution,
9) Su Y.-F., Zhang Z.-X., Guo C.-Y., Guo D.Y., J. Asian Nat. Prod.
1
(logε): 266 (2.96), 214 (3.83); H-NMR (600MHz; CD3OD) δ:
7.24 (1H, ddd, J=7, 1, 1Hz, H-4), 7.20–7.18 (2H, m, H-3 and
6), 6.99 (1H, ddd, J=7, 1, 1Hz, H-5), 4.88 (1H, d, J=8Hz,
H-1′), 3.88 (1H, dd, J=12, 2Hz, H-6′a), 3.69 (1H, dd, J=12,
5Hz, H-6′b), 3.46–3.38 (4H, m, H-2′, 3′, 4′, and 5′), 3.67 (3H,
s, –OCH3); 13C-NMR (150MHz, CD3OD): Table 1; HR-ESI-
MS (positive-ion mode) m/z: 351.1055 [M+Na]+ (Calcd for
C15H20O8Na: 351.1050).
Compound 6: Colorless amorphous powder; [α]D26 +3.5
(c=1.36, MeOH); IR νmax (film) cm−1: 3423, 1731, 1718, 1218,
1
1069; H-NMR (600MHz; CD3OD) δ: 5.45 (1H, brs, H-2), 3.80