2598
D. Hong et al. / Phytochemistry 65 (2004) 2595–2598
and 376.9714 [M + H]+, C14H10O8KS requires 376.9734.
FAB-MS (positive mode, matrix: 3-nitrobenzyl alcohol)
m/z: 415, 399, 377, 345, 286, 231, 192. ESIMS m/z: 791,
Acknowledgement
This work was supported by the National Natural
Science Fund of China (30371679), and the support is
gratefully acknowledged.
EtOH
415, 171. UV k
nm (log e): 206 (4.16), 224 (4.15), 248
max
KBr
max
(4.28), 310 (4.04). IR m
cmꢀ1: 3534, 3473, 1659, 1570,
1
1497, 1424, 1269, 1146. For H and 13C NMR spectral
data, see Table 1.
References
3.3.2. Acidic hydrolysis of 1
1
Charles, J.P., Behnke, L. (Eds.), 1992. Aldrich Library of 13C and H
To a solution of 1 (5 mg) MeOH (2 mL), was added
3% HCl (5 mL), with the whole heated until reflux began
this being maintained for 30 min. After evaporation of
the MeOH, the 1a so formed was extracted with EtOAc
and purified by preparative TLC of silica gel eluted with
CHCl3–MeOH (10:1). The sulfonate was detected in the
water layer as a white precipitate when adding BaCl2.
FT NMR Spectra. Aldrich Chemical Company, vol. 2, p. 1058B,
1116B.
Chen, M.T., Chen, C.M., 1985. Constituents of formosan antitumor
folk medicine. Part I. Xanthones from Hypericum sampsonii.
Heterocycles 23, 2543.
Della Monache, F., Marquina, M., Delle Monache, G., Marini Bettdo,
G.B., Alves De lima, R., 1983. (ꢀ)-(S)-4-Dimethylsulfonio-2-
methoxybutyrate from the red alga Rytiphloea tinctoria. Phyto-
chemistry 22, 227–228.
Glennie, C.W., Jain, S.C., 1980. Flavonol 3,7-diglycosides of Verbesina
encelioides. Phytochemistry 19, 157–158.
3.3.3. 1,3-Dihydroxy-5-methoxyxanthone (1a)
Yellow needles, m.p. 228–229 °C (dec.). HREIMS: m/
Han, Y.X., Bontems, S.L., Hegyes, P., Munson, M.C., Minor, C.A.,
Kates, S.A., Albericio, F., Barany, G., 1996. Preparation and
applications of xanthenylamide (XAL) handles for solid-phase
synthesis of C-terminal peptide amides under particularly mild
conditions. J. Org. Chem. 61, 6326–6339.
z 258.0518 [M]+, C14H10O5 requires 258.0528. EIMS m/
EtOH
z: 258, 243, 229, 215, 187, 129, 57. UV k
207 (4.06), 241 (3.77), 313 (3.33). IR m
nm (log e):
max
KBr
max
cmꢀ1: 3433,
3219, 1645, 1613, 1573, 1508, 1292, 1274. For 1H
NMR spectral data, see Table 1.
Hu, L.H., Sim, K.Y., 1998. Complex caged polyisoprenylated benzo-
phenone derivatives, sampsoniones A and B, from Hypericum
sampsonii. Tetrahedron lett. 39, 7999–8002.
Hu, L.H., Sim, K.Y., 1999a. Sampsoniones C–H, a unique family of
polyprenylated benzophenone derivatives with the novel tetracy-
3.3.4. 1,3-Dihydroxy-5-O-b-
4-sulfonate (2)
D
-glucopyranosylxanthone-
clo[7.3.1.13,11.O3,7
]
tetradecane-2,12,14-trione skeleton, from
Hypericum sampsonii (Guttiferae). Tetrahedron lett. 40, 759–762.
Hu, L.H., Sim, K.Y., 1999b. Cytotoxic polyprenylated benzoylphlo-
roglucinol derivatives with an unusual adamantyl skeleton from
Hypericum sampsonii (Guttiferae). Organic lett. 1, 879–882.
Hu, L.H., Chen, Z.L., Xie, Y.Y., 1996. New triterpenoid saponins
from Gynostemma pentaphyllum. J. Nat. Prod. 59, 1143–1145.
Huang, Y.L., Chen, C.C., Chen, Y.J., Huang, R.L., Shieh, B.J., 2001.
Three xanthones and a benzophenone from Garcinia mangostana.
J. Nat. Prod. 64, 903–906.
31:2
D
Yellow powder, m.p. > 360 °C. ½aꢁ
+ 38.10 (c,
0.033, MeOH). HRFABMS: m/z 562.9658 [M + K]+,
C19H17O13K2S requires 562.9664 and 525.0121
[M + H]+, C14H10O8KS requires 525.0105. FABMS
(positive mode, matrix: thioglycerol) m/z: 563, 547, 525,
475, 433, 401, 325, 295, 253, 187. ESIMS m/z: 1087,
1071, 563, 365, 171. UV k
EtOH
max
nm (log e): 306 (4.15),
KBr
max
246 (4.43), 222 (4.32), 206 (4.28). IR m
cmꢀ1: 3455,
Ishiguro, K., Nakajima, M., Fukumoto, H., Isoi, K., 1995. A xanthone
substituted with an irregular monoterpene in cell suspension
cultures of Hypericum patulum. Phytochemistry 39, 903–905.
Ishiguro, K., Nakajima, M., Fukumoto, H., Suitani, A., Nakajima,
M., Isoi, K., 1996. Neo-clerodane diterpenoids from three species
of Teucrium. Phytochemistry 42, 435–438.
1
1644, 1578, 1065, 1026. For H and 13C NMR spectral
data, see Table 1.
3.3.5. Acid hydrolysis of 2 (Hu et al., 1996)
Ishiguro, K., Nagereya, N., Suitani, A., Fukumoto, H., 1997. A
prenylated xanthone from cell suspension cultures of Hypericum
patulum. Phytochemistry 44, 1065–1066.
A MeOH solution of 2, together with the standard
glucose, was applied at points about 1 cm from the bot-
tom of a HPTLC Si gel plate and hydrolyzed with HCl
vapour for 2 h at 50 °C. The plate was then heated at 60
°C for 2 h to remove residual HCl, and developed using
CHCl3/CH3OH/H2O (8:2:0.1) as the eluent. The plate
was sprayed with 10% H2SO4 (in EtOH), and then
heated at 110 °C.
Mosmann, T., 1983. Rapid colorimetric assay for cellular growth and
survival: application to proliferation and cytotoxicity assays. J.
Immunol. Methods 65, 55–63.
Rath, G., Potterat, O., Mavi, S., Hostettmann, K., 1996. Biologically
active sesquiterpenoid metabolites from the fungus Botrytis cinerea.
Phytochemistry 43, 513–517.
Sanchez-Contreras, S., Diaz-Lanza, A.M., Bartolome, C., Bernabe,
M., 2000. Minor sulfated saikosaponins from the aerial parts of
Bupleurum rigidum L. Phytochemistry 54, 783–789.
3.4. Bioassay
Schaufelberger, D., Hostettmann, K., 1988. Chemistry and pharma-
cology of Gentiana lacteal. Planta Med. 54, 219–221.
The P388 (mouse lymphocytic leukemia) cell line was
used, with cell survival evaluated using the MTT-tetra-
azolium assay as described previously (Mosmann, 1983).
Youssef, D., Frahm, A.W., 1995. Constituents of the Egyptian
Centaurea Scoparia; III. Phenolic constituents of the aerial parts.
Planta Med. 61, 570–573.