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T. Asai, Y. Fujimoto / Phytochemistry 71 (2010) 1410–1417
(CDCl3) d: 7.84–7.48 (m), 5.08 (m, H-12), 3.67 (s, COOCH3), 3.46 (s,
OCH3), 2.31, (t, J = 7.5 Hz, H2-2), 1.52–1.19 (m), 0.86 (t, J = 6.9 Hz,
H3-18).
4.11. Gallicaside H (8)
Colorless oil; (+)-HRFABMS m/z: 467.3006 [M+H]+ (calcd for
Compound 2 (3 mg) was treated with Ac2O and pyridine at
room temperature overnight. Extractive workup gave a crude
product, which was purified by PTLC (hexane-EtOAc, 3:1) to afford
per-acetyl derivative (2b) (3.1 mg, 96% yield): Colorless oil; (+)-
FABMS m/z: 570 [M+H]+; 1H NMR (CDCl3) d: 5.21 (t, J = 9.3 Hz, H-
30), 5.08 (t, J = 9.3 Hz, H-40), 5.03 (dd, J = 9.3, 7.9 Hz, H-20), 4.69 (d,
J = 7.9 Hz, H-10), 4.22 (dd, J = 12.2, 5.3 Hz, Ha-60), 4.13 (dd, J = 12.2,
2.1 Hz, Hb-60), 3.89 (m, H-12), 3.66 (m, H-50), 2.28 (t, J = 7.0 Hz,
H2-2), 2.07 (s, Ac), 2.02 (s, Ac), 1.99 (s, Ac), 1.70–1.20 (CH2), 0.90
(t, 6.8 Hz, H3-18); 13C NMR (CDCl3) d: 172.4, 170.6, 170.4, 169.4,
95.6, 75.5, 73.4, 71.8, 71.4, 68.9, 62.3, 33.6, 32.3, 31.8, 31.6, 29.6,
27.3, 26.7, 26.0, 26.0, 25.0, 24.2, 23.8, 22.7, 22.3, 20.7, 20.6, 20.6,
14.1.
C
24H44O7Na, 467.2985); ½a D24
ꢀ51.5 (c = 0.4, CHCl3); IR (CHCl3) mmax
ꢂ
3600, 2910, 2850, 1720, 1440, 1100, 1090 cmꢀ1; for 1H and 13C
NMR spectroscopic data, see Tables 1 and 2, respectively. The ace-
tate derivative that was prepared from 8 was identified as com-
pound 2b. The hydroxy-fatty acid methyl ester that was obtained
from 8 was identified as 2a.
4.12. Pool VI (a mixture of 9 and 10)
Colorless oil; (ꢀ)-HRFABMS m/z: 571.3118 [MꢀH]ꢀ (calcd for
C
29H47O11, 571.3118). The 1H NMR spectrum recorded in CDCl3
gave only broad signals, but the following resonances were ob-
served: d 5.11 (m, H-30), 4.91 (m, H-20), 4.75 (m, H-10), 4.41 (m,
Ha-60), 4.27 (m, Hb-60), 3.88 (m, H-12 or 13), 3.67 (m, H-40), 3.64
(m, H-50), 3.38 (m, Ha-200), 3.28 (m, Hb-200). The 1H NMR spectrum
recorded in CDCl3–CD3OD (9:1) exhibited sharp signals, several
of which resonated as pairs of resonances in a 1:5 ratio. Compound
9: 1H NMR (signals of lower intensities) d: 5.06 (t, J = 9.5 Hz, H-30),
4.89 (dd, J = 9.5, 7.9 Hz, H-20), 4.66 (d, J = 7.9 Hz, H-10), 4.43 (brd,
J = 11.8 Hz, Ha-60), 4.23 (dd, J = 11.8, 6.0 Hz, Hb-60), 3.84 (m, H-
12), 3.64 (t, J = 9.5 Hz, H-40), 3.58 (m, H-50), 3.37 (m, H2-200), 2.30
(m, H2-2), 2.09 (s, Ac), 1.70–1.20 (CH2), 0.89 (t, J = 6.8 Hz, H3-18).
10: 1H NMR (signals of higher intensities) d: 5.09 (t, J = 9.5 Hz, H-
30), 4.93 (dd, J = 9.5, 7.9 Hz, H-20), 4.71 (d, J = 7.9 Hz, H-10), 4.43
(brd, J = 11.8 Hz, Ha-60), 4.23 (dd, J = 11.8, 6.0 Hz, Hb-60), 3.88 (m,
H-12), 3.64 (t, J = 9.5 Hz, H-40), 3.58 (m, H-50), 3.37 (m, H2-200),
2.30 (m, H2-2), 2.09 (s, Ac), 1.70–1.20 (CH2), 0.89 (t, J = 6.8 Hz,
H3-18).
4.6. Gallicaside C (3)
Colorless oil; (+)-HRFABMS m/z: 529.3390 [M+H]+ (calcd for
C
28H49O9, 529.3377); ½a D24
ꢀ51.5 (c = 0.4, CHCl3); IR (CHCl3) mmax
ꢂ
3600, 2910, 2850, 1720, 1440, 1390, 1190, 1090 cmꢀ1; for 1H and
13C NMR spectroscopic data, see Tables 1 and 2, respectively. The
acetate derivative that was prepared from 3 was identified as com-
pound 1b. The hydroxy-fatty acid methyl ester that was obtained
from 3 was identified as 1a.
4.7. Gallicaside D (4)
Colorless oil; (+)-HRFABMS m/z: 529.3380 [M+H]+ (calcd for
C
28H49O9, 529.3377); ½a D24
ꢀ54.0 (c = 1.3, CHCl3); IR (CHCl3) mmax
ꢂ
3600, 2910, 2850, 1720, 1440, 1390, 1190, 1090 cmꢀ1; for 1H and
13C NMR spectroscopic data, see Tables 1 and 2, respectively. The
acetate derivative that was prepared from 4 was identified as com-
pound 2b. The hydroxy-fatty acid methyl ester that was obtained
from 4 was identified as 2a.
A part of Pool VI (30 mg) was treated with ethereal diazometh-
ane, and the resulting methyl ester mixture was separated by HPLC
(solvent, CH3CN–H2O, 8:1; flow rate, 1.0 mL/min) to give 9a
(4.2 mg) and 10a (22.3 mg) at 13.9 and 15.1 min, respectively.
4.13. Methyl ester of gallicaside I (9a)
4.8. Gallicaside E (5)
Colorless oil; (+)-HRFABMS m/z: 609.3291 [M+Na]+ (calcd for
Colorless oil; (+)-HRFABMS m/z: 487.3307 [M+H]+ (calcd for
C30H50O11Na, 609.3251); ½a D24
ꢀ35.0 (c = 0.3, CHCl3); IR (CHCl3)
ꢂ
C26H47O8, 487.3271); ½a D24
ꢀ50.2 (c = 1.5, CHCl3); IR (CHCl3) mmax
ꢂ
3600, 2910, 2850, 1720, 1440, 1390, 1190, 1090 cmꢀ1; for 1H and
13C NMR spectroscopic data, see Tables 1 and 2, respectively. The
acetate derivative that was prepared from 5 was identified as com-
pound 2b. The hydroxy-fatty acid methyl ester that was obtained
from 5 was identified as 2a.
mmax 3600, 2910, 2850, 1720, 1715, 1460, 1440, 1310, 1210,
1170, 1110, 1090 cmꢀ1; for 1H and 13C NMR spectroscopic data,
see Tables 1 and 2, respectively. The hydroxy-fatty acid methyl es-
ter that was obtained from 9a was identified as 1a.
4.14. Methyl ester of gallicaside J (10a)
4.9. Gallicaside F (6)
Colorless oil; (+)-HRFABMS m/z: 587.3466 [M+H]+ (calcd for
Colorless oil; (+)-HRFABMS m/z: 487.3260 [M+H]+ (calcd for
C
30H51O11, 587.3432); ½a D24
ꢀ47.2 (c = 2.4, CHCl3); IR (CHCl3) mmax
ꢂ
C
26H47O8, 487.3271); ½a D24
ꢀ52.5 (c = 0.2, CHCl3); IR (CHCl3) mmax
ꢂ
3600, 2910, 2850, 1720, 1715, 1460, 1440, 1310, 1210, 1170,
1110, 1090 cmꢀ1; for 1H and 13C NMR spectroscopic data, see Ta-
bles 1 and 2, respectively. The hydroxy-fatty acid methyl ester that
was obtained from 10a was identified as 2a.
3600, 2910, 2850, 1720, 1440, 1390, 1190, 1090 cmꢀ1; for 1H and
13C NMR spectroscopic data, see Table 1 and 2, respectively. The
acetate derivative that was prepared from 6 was identified as com-
pound 1b. The hydroxy-fatty acid methyl ester that was obtained
from 6 was identified as 1a.
Acknowledgment
4.10. Gallicaside G (7)
The authors thank Prof. Shiro Kohshima, Department of Biolog-
ical Sciences, Graduate School of Bioscience and Biotechnology, To-
kyo Institute of Technology for botanical identification.
Colorless oil; (+)-HRFABMS m/z: 487.3298 [M+H]+ (calcd for
C
26H47O8, 487.3271); ½a D24
ꢀ66.8 (c = 1.0, CHCl3); IR (CHCl3) mmax
ꢂ
3600, 2910, 2850, 1720, 1440, 1390, 1190, 1090 cmꢀ1; for 1H and
13C NMR spectroscopic data, see Tables 1 and 2, respectively. The
acetate derivative that was prepared from 7 was identified as com-
pound 2b. The hydroxy-fatty acid methyl ester that was obtained
from 7 was identified as 2a.
References
Asai, T., Hara, N., Kobayashi, S., Kohshima, S., Fujimoto, Y., 2008. Geranylated
flavanones from the secretion on the surface of the immature fruits of
Paulownia tomentosa. Phytochemistry 69, 1234–1241.