September 2001
1197
nopyranosyl-(1→2)-a-L-arabinopyranoside (4) White amorphous pow-
which have been reported from Sapindus mukurossi, caused
enhancement of the absorption of sodium ampicillin from rat
intestine and rectum.3) Further investigations of the isolated
compounds are in progress.
1
der. [a]D22 ϩ5.9° (cϭ3.7, MeOH); H-NMR: Table 1; 13C-NMR: Tables 2
and 3; negative HR-FAB-MS, m/z: 923.5028 [MϪH]Ϫ (C48H75O17 requires
923.5003).
23-O-Acetyl-hederagenin 3-O-(4-O-Acetyl-b-D-xylopyranosyl)-(1→3)-
a-L-rhamnopyranosyl-(1→2)-a-L-arabinopyranoside (7) White amor-
phous powder. [a]D22 Ϫ10.4° (cϭ0.7, MeOH); 1H-NMR: Table 1; 13C-NMR:
Tables 2 and 3; negative HR-FAB-MS, m/z: 965.5118 [MϪH]Ϫ (C50H77O18
requires 965.5109).
Experimental
NMR spectra were recorded in C5D5N or CD3OD using a JEOL JNM A-
1
400 spectrometer (400 MHz for H-NMR and 100 MHz for 13C-NMR) with
tetramethylsilane (TMS) as internal standard. MS were recorded on a JEOL
JMS-SX 102 spectrometer. Optical rotations were measured with a Union
PM-1 digital polarimeter. Preparative HPLC was carried out on columns of
Diol-120A (8.0ϫ300 mm i.d., YMC) with a Tosoh refraction index (RI-8)
detector. The flow rate was 3 ml/min. For CC, silica gel G 60 (Merck),
YMC-gel ODS (50 mm, YMC), and highly porous copolymer of styrene and
divinylbenzene (Mitsubishi Chem. Ind. Co. Ltd) were used.
Plant Material The fruit of Sapindus emarginatus Wall. was purchased
from a traditional medicine market in Bangkok, Thailand, in October 2000.
The identification of the plant was confirmed by Professor Vichiara Jira-
wongse, Department of Pharmaceutical Botany and Pharmacognosy, Faculty
of Pharmaceutical Sciences, Khon Kaen University, Thailand. A voucher
sample is kept in the Herbarium of the Faculty of Pharmaceutical Sciences,
Khon Kaen University, Thailand.
Oleanolic Acid 3-O-(4-O-Acetyl-b-D-xylopyranosyl)-(1→3)-a-L-rham-
nopyranosyl-(1→2)-a-L-arabinopyranoside (9) White amorphous pow-
1
der. [a]D22 Ϫ20.2° (cϭ3.8, MeOH); H-NMR: Table 1; 13C-NMR: Tables 2
and 3; negative HR-FAB-MS, m/z: 907.5090 [MϪH]Ϫ (C48H75O16 requires
907.5054).
Alkaline Hydrolysis of Compounds 4, 7 and 9 Compounds 4 (20 mg)
and 7 (18 mg) were refluxed with 2% KOH/MeOH for 30 min. The reaction
mixtures were neutralized with Amberlite MB3 resin and concentrated to
dryness, affording 3 (8 mg from 4, and 5 mg from 7), whose structure were
identified by TLC and spectral analysis. By the same method, 9 (20 mg) pro-
vided 8 (7 mg).
Acknowledgements We would like to thank the Research Center for
Molecular Medicine, Hiroshima University for the use of its NMR facilities.
Extraction and Isolation The pericarps (1.6 kg) of S. emarginatus were
extracted with hot MeOH. After removal of the solvent by evaporation, the
dried residue (660 g) was subjected to a column of highly porous copolymer
of styrene and divinylbenzene and eluted with H2O, MeOH and Me2CO,
successively. The portion eluted with MeOH (90 g from 389 g) was sub-
jected to a column of silica gel using a gradient system [(CH2Cl2–MeOH
(9 : 1 to 1 : 1)] affording eight fractions. Fraction 1 (900 mg) was repeatedly
chromatographed on a column of silica gel [CH2Cl2–MeOH (19 : 1)] to pro-
vide compounds 1 (66 mg) and 6 (288 mg). Fraction 2 (4.9 g) was subjected
to a column of RP-18 [70—100% MeOH], then purified by prep. HPLC-
Diol 120A [MeCN] to give compounds 2 (12 mg), 5 (2.1 g), 7 (45 mg) and 9
(57 mg). Fraction 3 (4.0 g) was separated on a RP-18 column [70—100%
MeOH] to give compounds 4 (54 mg) and 8 (115 mg). Fraction 4 (13.7 g)
was chromatographed on a column of RP-18 [70—100% MeOH] to provide
compound 3 (3.6 g). Finally, fraction 7 (21.8 g) was chromatographed on a
column of RP-18 [60—100% MeOH] to provide compound 10 (6.2 g).
Hederagenin 3-O-(2-O-Acetyl-b-D-xylopyranosyl)-(1→3)-a-L-rham-
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