Triterpenoidal glycosides from Justicia betonica

Article abstract of DOI:10.1016/j.phytochem.2004.06.029

Four triterpenoidal glycosides, justiciosides A-D, were isolated from the aerial portion of Justicia betonica. From the aerial portion of Justicia betonica L., four triterpenoidal glycosides (justiciosides A-D) were isolated. Their structures were established through chemical and NMR spectroscopic analyses as olean-12-ene-1β,3β,1α,28-tetraol 28-O-β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranoside, olean-12-ene-1β,3β,11α,28-tetraol 28-O-β-d-glucopyranosyl- (1 → 2)-β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranoside, 11α-methoxy-olean-12-ene-1β,3β,28-triol 28-O-β-d- glucopyranosyl-(1 → 2)-β-d-glucopyranoside, 11α-methoxy-olean- 12-ene-1β,3β,28-triol 28-O-β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranoside, respectively.

Full text of DOI:10.1016/j.phytochem.2004.06.029

PHYTOCHEMISTRY
Phytochemistry 65 (2004) 2613–2618
www.elsevier.com/locate/phytochem
Triterpenoidal glycosides from Justicia betonica
a,
a
b
Tripetch Kanchanapoom *, Pawadee Noiarsa , Somsak Ruchirawat ,
c
Ryoji Kasai , Hideaki Otsuka
c
a
Department of Pharmaceutical Botany and Pharmacognosy, Faculty of Pharmaceutical Sciences, Khon Kaen University, Khon Kaen 40002, Thailand
b
Chulabhorn Research Institute, Vipavadee Rangsit Highway, Bangkok 10210, Thailand
c
Department of Pharmacognosy, Division of Biomedical Sciences, Hiroshima University, Hiroshima 734-8551, Japan
Received 15 January 2004; received in revised form 16 April 2004
Available online 31 July 2004
Abstract
From the aerial portion of Justicia betonica L., four triterpenoidal glycosides (justiciosides A–D) were isolated. Their structures
were established through chemical and NMR spectroscopic analyses as olean-12-ene-1b,3b,11a,28-tetraol 28-O-b- -glucopyrano-
syl-(1!2)-b- -glucopyranoside, olean-12-ene-1b,3b,11a,28-tetraol 28-O-b- -glucopyranosyl-(1!2)-b- -glucopyranosyl-(1!
2)-b- -glucopyranoside, 11a-methoxy-olean-12-ene-1b,3b,28-triol 28-O-b- -glucopyranoside, 11a-
-glucopyranosyl-(1!2)-b-
-glucopyranosyl-(1!2)-b- -glucopyranoside, respectively.
D
D
D
D
D
D
D
methoxy-olean-12-ene-1b,3b,28-triol 28-O-b-
ꢀ 2004 Elsevier Ltd. All rights reserved.
D
-glucopyranosyl-(1!2)-b-
D
D
Keywords: Justicia betonica; Acanthaceae; Justiciosides A–D; Triterpenoidal glycoside; Olean-12-ene-1b; 3b; 11a; 28-tetraol; 11a-Methoxy-olean-12-
ene-1b, 3b; 28-triol
1. Introduction
glycosides of Justicia species, although a number of trit-
erpenoidal glycosides were isolated from other genera in
the family Acanthaceae. In our continuing studies on
the chemical constituents of Acanthaceous plants (Kan-
chanapoom et al., 2001, 2002), we isolated four new trit-
erpenoidal glycosides, justiciosides A–D (1–4, Scheme
1), from the aerial portion of this plant. The present pa-
per deals with the isolation and structural elucidation of
these compounds.
Justicia betonica L. (Acanthaceae; Thai name: Tri-
Cha-Va, Hang-Kra-Rok) is an ornamental plant, com-
monly grown in Northeast of Thailand, but for which
there is no ethnopharmacological use in Thai traditional
medicine. However, its aerial parts are used in Indian
traditional medicine as an anti-diarrhea medicine as well
as an anti-inflammatory agent. Preliminary studies on
plants in the genus Justicia have led to the isolation of
several compounds such as lignans (Okigawa et al.,
1970; Ghosal et al., 1979, 1980; Trujillo et al., 1990; As-
ano et al., 1996; Rajasekhar et al., 1998; Rajasekhar and
Subbaraju, 2000) and an amide (Lorenz et al., 1999).
However, there have been no reports on triterpenoidal
2. Results and discussion
Justicioside A (1) was obtained as an amorphous
powder and determined as C42H70O14 by HR-FAB mass
spectrometry. Inspection of the 13C NMR spectral data
revealed the presence of two sugar units (anomeric car-
bons at d 103.5 and 105.9) in addition to 30 carbon sig-
nals for the aglycone moiety. The appearance of seven
tertiary methyl groups (d 0.79, 0.80, 1.01, 1.05, 1.21,
*
Corresponding author. Tel.: +66-43-202378; fax: +66-43-202379.
E-mail address: trikan@kku.ac.th (T. Kanchanapoom).
0031-9422/$ - see front matter ꢀ 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.phytochem.2004.06.029

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T. Kanchanapoom et al. / Phytochemistry 65 (2004) 2613–2618
Table 1
1H and 13C NMR spectral data for aglycone (1a, in C5D5N)
1.26 and 1.33) and one trisubstituted olefinic proton (d
5.51) of the aglycone moiety in the H NMR spectrum,
1
together with information from the 13C NMR spectrum
(seven sp3 carbon at d 13.6, 16.0, 18.2, 23.7, 25.7, 28.6
and 33.2, and two sp2 olefinic carbons at d 126.1 and
147.0) indicated that the aglycone has an olean-12-ene
skeleton (Doddrell et al., 1974). Enzymatic hydrolysis
of 1 with crude hesperidinase afforded a new aglycone
Position
DEPT
dC
77.7
dH
1
2
CH
CH2
3.94 (1H, dd, J=11.5, 4.4 Hz)
2.40 (1H, ddd, J=12.9, 4.4, 4.4 Hz)
2.34 (1H, m)
37.3
3
4
5
6
CH
C
CH
CH2
75.4
39.6
52.9
18.3
3.58 (1H, dd, J=12.9, 4.4 Hz)
0.86 (1H, m)
1.65 (1H, m)
1.55 (1H, m)
1.94 (1H, m)
1.65 (1H, m)
(1a) with a molecular formula C30H50O4, and D-glucose
which was identified by TLC and comparison of its op-
tical rotation with an authentic sample. The structure of
1a was established by analyzing the 1D- and 2D-NMR
spectra (including HSQC and HMBC) in addition to
7
CH2
31.7
8
9
C
CH
C
CH
CH
C
41.9
57.3
44.8
2.05 (1H, d, J=8.1 Hz)
1
the coupling constants in the H NMR spectrum. In
1
the H NMR spectrum of 1a, the signals due to seven
10
11
12
13
14
15
66.3
4.56 (1H, dd, J=8.1, 3.7 Hz)
5.58 (1H, d, J=3.7 Hz)
126.1
147.4
44.1
methyls, three oxymethine protons, two oxymethylene
protons, and one olefinic proton were clearly observed.
The 13C NMR spectrum coupled with the DEPT exper-
iments indicated the presence of seven methyls, nine
methylenes, seven methines and seven quaternary car-
bons. All protonated carbons were determined by
HSQC spectral analyses (Table 1). The oxymethylene
protons at d 3.56 and 3.81 (each d, J=10.7 Hz) were as-
signed to H-28 on the basis of correlations with C-16 (d
22.7), C-17 (d 37.3) and C-18 (d 41.8) in the HMBC
spectrum (Fig. 1). The oxymethine proton at d 3.94,
which showed long-range correlations to C-25 (d 13.6)
and C-9 (d 57.3) could be assigned to H-1. The proton
signal at d 3.58 was diagnostic for H-3, deducing from
an HMBC correlation between H-23 (d 1.24), H-24 (d
1.08) and C-3 (d 75.4). The methine proton signal at
d 4.56, which had the significant correlations to C-9 (d
57.3), C-12 (d 126.1) and C-13 (d 147.4), was assigned
to H-11. The occurrence of H-1 as a doublet of doublets
having coupling constants with H-2ax (J=11.5 Hz) and
H-2eq (J=4.4 Hz), indicated that H-1 was in the axial
position; this in turn suggested a b-configuration of
the hydroxyl group at C-1. For the same reason, the
hydroxyl group at C-3 was also determined to have a
b-configuration, this being supported by the splitting
pattern of H-3 (dd, J=12.9, 4.4 Hz). The hydroxyl group
at C-11 was concluded to be in the a-configuration from
the coupling constant between H-11 (d 4.56) and H-9 (d
2.05) with J=8.1 Hz, and also from H-11 (d 4.56) and
H-12 (d 5.58) with J=3.7 Hz (Calis et al., 1993).
Therefore, structure 1a was assigned as olean-12-ene-
1b,3b,11a,28-tetraol. Comparison of the 13C NMR
spectral data of 1 with those of 1a revealed glycosylation
shifts for C-28 (Dd+7.8) and C-17 (Ddꢀ0.6) on going
from 1a to 1, demonstrating that the sugar moiety was
linked to C-28. The sugar sequence was identified to
C
CH2
26.3
1.88 (1H, m)
1.01 (1H, m)
1.99 (1H, m)
1.51 (1H, m)
16
CH2
22.7
17
18
19
C
CH
CH2
37.3
41.8
46.4
2.31 (1H, br d, J=12.4 Hz)
1.75 (1H, dd, J=13.6, 12.4 Hz)
1.14 (1H, dd, J=13.6, 4.2 Hz)
20
21
C
CH2
31.1
34.5
1.44 (1H, m)
1.22 (1H, m)
1.53 (1H, m)
1.22 (1H, m)
1.24 (3H, s)
1.08 (3H, s)
1.29 (3H, s)
1.04 (3H, s)
22
CH2
33.4
23
24
25
26
27
28
CH3
CH3
CH3
CH3
CH3
CH2
28.8
16.0
13.6
18.2
25.8
68.7
1.39 (3H, s)
3.81 (1H, d, J=10.7 Hz)
3.56 (1H, d, J=10.7 Hz)
0.83 (3H, s)
29
30
CH3
CH3
33.2
23.6
0.88 (3H, s)
be
a
b-
D
-glucopyranosyl-(1!2)-b-
D-glucopyranosyl
Fig. 1. Significant HMBC correlations for aglycone (1a).
unit by comparison of the chemical shifts with that of
reported data (Kasai et al., 1988). Moreover,
negative FAB-MS of 1 exhibited significant fragment
ions at m/z 635 [M–162]ꢀ and 473 [M–162–162]ꢀ. Con-
sequently, structure 1 was olean-12-ene-1b,3b,11a,28-
tetraol28-O-b-
oside.
D
-glucopyranosyl-(1!2)-b-D-glucopyran-

T. Kanchanapoom et al. / Phytochemistry 65 (2004) 2613–2618
2615
Justicioside B (2) was isolated as an amorphous pow-
der. Its molecular formula was determined as C48H80O19
by HR-FAB mass spectrometric analyses. The H and
and 13C NMR spectral data revealed that 3 contains
the same sugar moiety as justicioside A (1) with a differ-
ent aglycone. Enzymatic hydrolysis of 3 provided D-
1
13C NMR spectra showed the presence of three sugar
units from the anomeric proton signals at d 4.48 (d,
J=7.6 Hz), 5.27 (d, J=7.6 Hz) and 5.43 (d, J=7.6
Hz), and from carbon signals at d 103.0, 103.4 and
106.1. Enzymatic hydrolysis of 2 with crude hesperidin-
glucose and an aglycone (3a) with a molecular formula
C31H52O4. The structure of 3a was established by com-
parison of its chemical shifts to those of 1a, in which
the additional signal due to a methoxyl group was ob-
1
served in the spectra (d 3.27 in the H NMR spectrum
ase gave 1a and
D
-glucose. The negative FAB-MS dis-
and d 51.3 in the 13C NMR spectrum). This additional
group was located at C-11 of the aglycone since the
chemical shifts of C-9, C-11, C-12 and C-13 were signif-
icantly changed by ꢀ7.1, +8.0, ꢀ4.2 and +4.6, respec-
tively, when compared to 1a (Calis et al., 1993). Thus,
3a was concluded to be an 11a-methoxy derivative of
1a. Accordingly, 3 was elucidated as 11a-methoxy-ole-
played characteristic fragment ions of a linear sugar
unit at m/z 797 [M–162]ꢀ, 635 [M–162–162]ꢀ, 473 [M–
162–162–162]ꢀ. The chemical shifts of 2 were closely
related to those of justicioside A (1), except for a set
of additional signals arising from a b-D-glucopyranosyl
unit. This additional unit was assigned to be attached
to C-200 of the inner sugar because the chemical shifts
of C-200 (d 85.3), C-100 (d 103.0) and C-300 (d 77.6) chan-
ged by +8.4, ꢀ2.9 and ꢀ0.6, respectively. Thus, 2 was
elucidated as olean-12-ene-1b,3b,11a,28-tetraol 28-O-b-
an-12-ene-1b,3b,28-triol 28-O-b-
2)-b- -glucopyranoside.
Justicioside D (4) was obtained as an amorphous
D
-glucopyranosyl-(1!
D
powder and determined as C49H82O19 by HR-FAB mass
1
D
-glucopyran osyl-(1!2)-b-
b- -glucopyranoside.
Justicioside C (3) was obtained as an amorphous
D
-glucopyranosyl-(1!2)-
spectrometric analyses. The H and 13C NMR spectra
D
indicated the presence of three sugar units, one methoxyl
group and signals for the aglycone moiety. The chemical
shifts of the aglycone moiety were superimposable with
those of 3, as well as the chemical shifts of three sugar
units were the same as those of 2. Enzymatic hydrolysis
powder. Its molecular formula, C43H72O14, was deter-
mined by HR-FAB mass spectrometric analyses. Nega-
tive FAB-MS exhibited fragment ions at m/z 811
[M–H]ꢀ, 649 [M–162]ꢀ, 487 [M–162–162]ꢀ. The 1H
of 4 afforded 3a and
D-glucose. Besides, negative
Scheme 1.

2616
T. Kanchanapoom et al. / Phytochemistry 65 (2004) 2613–2618
FAB-MS showed the significant fragment ions at m/z
973 [M–H]ꢀ, 811 [M–162]ꢀ, 649 [M–162–162]ꢀ, 487
[M–162–162–162]ꢀ. Consequently, 4 was identified to
was similarly applied to a column of ODS using a gradi-
ent system [MeOH–H2O (2:3, 1 l) to MeOH (1 l)] to give
eight fractions. Fraction 7-2 was purified by prep.
HPLC-ODS (33% MeCN in H2O) to afford compound
2 (589 mg) and 4 (330 mg).
11a-methoxy-olean-12-ene-1b, 3b, 28-triol 28-O-b-
glucopyranosyl-(1!2)-b- -glucopyranosyl-(1!2)-b-
-glucopyranoside (see Scheme 1).
D-
D
D
3.4. Justicioside A (1)
27
D
3. Experimental
Amorphous powder, ½aꢁ ꢀ 1:9ꢂ (MeOH, c 2.65); 1H
NMR (C5D5N): aglycone moiety d 5.51 (1H, d, J=3.0
Hz, H-12), 4.53 (1H, dd, J=8.1, 3.0 Hz, H-11), 3.80
(1H, d, J=9.3 Hz, H-28a), 3.71 (1H, d, J=9.3 Hz, H-
28b), 3.55 (1H, dd, J=11.7, 3.9 Hz, H-3), 1.33 (3H, s,
H-27), 1.26 (3H, s, H-25), 1.21 (3H, s, H-23), 1.05
(3H, s, H-26), 1.01 (3H, s, H-24), 0.80 (3H, s, H-30),
0.79 (3H, s, H-29), sugar moiety d 5.37 (1H, d, J=7.6
Hz, H-100), 4.89 (1H, d, J=7.3 Hz, H-10); 13C NMR
(C5D5N): Table 3; Negative FAB-MS m/z 797 [M–
H]ꢀ, 635 [M–Glc]ꢀ, 473 [M–Glc–Glc]ꢀ; Negative HR-
FAB-MS, m/z: 797.4681 [M–H]ꢀ (calcd for C42H69O14,
797.4687).
3.1. General
NMR spectra were recorded in C5D5N using a JEOL
1
JNM a-400 spectrometer (400 MHz for H NMR and
100 MHz for 13C NMR) with tetramethylsilane (TMS)
as internal standard, whereas MS obtained using a
JEOL JMS-SX 102 spectrometer. Optical rotations were
measured with a Union PM-1 digital polarimeter. For
CC, silica gel G (Scharlau GE0049, 70-230 mesh
ASTM), YMC-gel ODS (50 lm, YMC) and highly po-
rous copolymer resin of styrene and divinylbenzene
(Mitsubishi Chem. Ind. Co. Ltd.) were used. HPLC
(Waters 515 HPLC pump) was carried on a column of
ODS (150·20 mm i.d., YMC) with a Shimadzu refrac-
tive index (RID-6A) detector.
3.5. Olean-12-ene-1b,3b,11a,28-tetraol (1a)
27
Amorphous powder, ½aꢁ þ 37:5ꢂ (MeOH, c 0.13); 1H
D
and 13C NMR (CD3OD): Table 1; Negative HR-FAB-
MS, m/z : 476.3639 [M–H]ꢀ (calcd for C30H49O4,
473.3630).
3.2. Plant material
The aerial portion of J. betonica L. was collected
from Kalasin Province, Thailand, in November, 2002,
and identified by Mr. Bamrung Tavinchiua of the De-
partment of Pharmaceutical Botany and Pharmacog-
nosy, Faculty of Pharmaceutical Sciences, Khon Kaen
University, Thailand. A voucher sample (KKU-0045)
is kept in the Herbarium of the Faculty of Pharmaceuti-
cal Sciences, Khon Kaen University, Thailand.
3.6. Justicioside B (2)
27
D
Amorphous powder, ½aꢁ ꢀ 4:2ꢂ (MeOH, c 2.61); 1H
NMR (C5D5N): aglycone moiety d 5.54 (1H, d, J=3.2
Hz, H-12), 4.51 (1H, dd, J=8.1, 3.2 Hz, H-11), 3.76
(1H, d, J=9.5 Hz, H-28a), 3.71 (1H, d, J=9.5 Hz, H-
28b), 3.51 (1H, dd, J=11.7, 3.9 Hz, H-3), 2.15 (1H, dd,
J=12.9, 2.9 Hz, H-18), 1.99 (1H, d, J=8.1 Hz, H-9),
1.33 (3H, s, H-27), 1.29 (3H, s, H-25), 1.15 (3H, s, H-
23), 1.08 (3H, s, H-26), 1.02 (3H, s, H-24), 0.78 (3H, s,
H-30), 0.75 (3H, s, H-29), sugar moiety d 5.43 (1H, d,
J=7.6 Hz, H-100), 5.27 (1H, d, J=7.6 Hz, H-100), 4.48
(1H, d, J=7.6 Hz, H-10); 13C NMR (C5D5N): Table 3;
Negative FAB-MS m/z 959 [M–H]ꢀ, 797 [M–Glc]ꢀ,
635 [M–Glc–Glc]ꢀ, 473 [M–Glc–Glc–Glc]ꢀ ; Negative
HR-FAB-MS, m/z: 959.5224 [M–H]ꢀ (calcd for
C48H79O19, 959.5215).
3.3. Extraction and isolation
The dried aerial portion (1.8 kg) of J. betonica was ex-
tracted with hot EtOH-H2O (95:5,v/v) under reflux 4
times (each 8 l, 3 h, 70 ꢁC). The EtOH extract was con-
centrated to dryness (256.6 g) and partitioned between
Et2O and H2O, with the aqueous soluble applied to a
column of highly porous copolymer resin of styrene
and divinylbenzene, and eluted with H2O, MeOH–
H2O (3:2), MeOH and Me2CO, successively. The frac-
tion eluted with MeOH (17.5 g) was applied to a silica
gel column using solvent systems EtOAc–MeOH (9:1,
5 l), EtOAc–MeOH–H2O (40:10:1, 5 l) and EtOAc–
MeOH–H2O (70:30:3, 3.5 l) to give ten fractions. Frac-
tion 6 (2.9 g) was applied to a column of ODS using a
gradient system [MeOH–H2O (2:3, 1 l) to MeOH (1 l)]
to afford six fractions. Fraction 6-3 was purified by prep.
HPLC-ODS (37% MeCN in H2O) to provide com-
pounds 1 (113 mg) and 3 (42 mg). Fraction 7 (3.8 g)
3.7. Justicioside C (3)
27
D
Amorphous powder, ½aꢁ þ 10:1ꢂ (MeOH, c 3.57); 1H
NMR (C5D5N): aglycone moiety d 5.27 (1H, d, J=3.2
Hz, H-12), 3.82 (1H, d, J=10.0 Hz, H-28a), 3.63 (1H,
d, J=10.0 Hz, H-28b), 3.52 (1H, dd, J=11.7, 3.4 Hz,
H-3), 1.95 (1H, d, J=9.0 Hz, H-9), 1.26 (3H, s, H-27),
1.20 (3H, s, H-23), 1.16 (3H, s, H-25), 1.02 (3H, s, H-
24), 0.94 (3H, s, H-26), 0.89 (6H, s, H-29, 30), sugar

T. Kanchanapoom et al. / Phytochemistry 65 (2004) 2613–2618
2617
moiety d 5.38 (1H, d, J=7.6 Hz, H-100), 4.88 (1H, d,
J=7.6 Hz, H-10); 13C NMR (C5D5N): Table 3; Negative
FAB-MS m/z 811 [M–H]ꢀ, 649 [M–Glc]ꢀ, 487 [M–Glc–
Glc]ꢀ; Negative HR-FAB-MS, m/z: 811.4851 [M–H]ꢀ
(calcd for C43H71O14, 811.4843).
d, J=9.5 Hz, H-28b), 3.49 (1H, dd, J=12.0, 3.8 Hz,
H-3), 1.94 (1H, d, J=803 Hz, H-9), 1.26 (3H, s, H-27),
1.16 (3H, s, H-23), 1.15 (3H, s, H-25), 1.00 (3H, s, H-
24), 0.99 (3H, s, H-26), 0.86 (6H, s, H-30), 0.82 (3H, s,
H-29), sugar moiety d 5.42 (1H, d, J=7.6 Hz, H-100),
5.32 (1H, d, J=7.6 Hz, H-1000), 4.88 (1H, d, J=7.6 Hz,
H-10); 13C NMR (CD3OD) spectra: Table 1; Negative
FAB-MS m/z 973 [M–H]ꢀ, 811 [M–Glc]ꢀ, 649 [M–
Glc–Glc]ꢀ, 487[M–Glc–Glc–Glc]ꢀ; Negative HR-FAB-
MS, m/z: 973.5267 [M–H]ꢀ (calcd for C49H81O19,
973.5371).
3.8. 11a-Methoxy-olean-12-ene-1b,3b,28-triol (3a)
27
Amorphous powder, ½aꢁ þ 46:7ꢂ (MeOH, c 0.71); 1H
D
and 13C NMR (CD3OD): Table 2; Negative HR-FAB-
MS, m/z: 487.3796 [M–H]ꢀ (calcd for C31H51O4,
487.3787).
Table 3
13C NMR spectral data for justiciosides A–D (1–4, in C5D5N)
3.9. Justicioside D (4)
Position
1
2
3
4
27
Amorphous powder, ½aꢁ þ 13:6ꢂ (MeOH, c 7.79); 1H
1
2
3
4
5
6
7
8
9
77.8
37.3
75.4
39.6
52.9
18.2
32.3
41.8
57.2
44.8
66.2
126.1
147.0
44.1
26.6
21.8
36.7
42.2
46.0
30.9
34.3
33.2
28.6
16.0
13.6
18.2
25.7
76.5
33.2
23.7
77.8
37.0
75.3
39.4
52.9
18.2
32.0
41.7
57.1
44.6
66.2
126.1
147.0
44.1
26.5
22.0
36.6
41.9
45.9
30.8
34.2
33.2
28.5
15.9
13.5
18.2
25.8
76.8
33.1
23.7
77.2
37.1
75.2
39.5
52.8
18.1
32.2
41.5
50.2
45.0
74.3
77.1
36.8
75.1
39.4
52.7
18.1
31.8
41.2
50.1
44.9
74.2
D
NMR (C5D5N): aglycone moiety d 5.27 (1H, d, J=3.2
Hz, H-12), 3.77 (1H, d, J=9.5 Hz, H-28a), 3.65 (1H,
Table 2
1H and 13C NMR spectral data for aglycone (3a, in C5D5N)
Position DEPT dC
dH
1
2
CH
CH2
77.2 3.63 (1H, dd, J=11.6, 4.4 Hz)
37.2 2.34 (1H, ddd, J=14.2, 4.4, 4.4 Hz)
2.23 (1H, ddd, J=14.2, 12.2, 11.6 Hz)
75.2 3.56 (1H, dd, J=12.2, 4.4 Hz)
39.6
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
MeO-11
Glc-10
20
122.0
151.6
44.2
26.9
21.9
36.7
42.7
46.6
31.1
34.3
33.1
28.6
15.9
13.5
18.2
24.6
76.4
33.2
23.8
51.2
103.5
82.7
77.9
71.6
78.1
62.6
105.9
76.9
78.2
71.5
78.4
62.7
121.9
151.5
44.1
26.7
22.0
36.6
42.3
46.5
31.0
34.2
33.2
28.5
15.8
13.4
18.2
24.5
76.6
33.2
23.8
51.2
103.3
82.6
77.5
71.0
77.8
62.4
103.0
85.2
77.6
70.6
77.8
62.3
106.1
76.2
78.2
71.3
78.9
62.7
3
4
5
6
CH
C
CH
CH2
52.8 0.78 (1H, br d, J=9.7 Hz)
18.2 1.67 (1H, m)
1.50 (1H, m)
7
CH2
31.6 1.99 (1H, m)
1.67 (1H, br d, J=15.4 Hz)
41.7
8
9
C
CH
C
50.2 2.00 (1H, d, J=8.5 Hz)
45.1
10
11
12
13
14
15
CH
CH
C
74.3 4.41 (1H, dd, J=8.5, 3.7 Hz)
121.9 5.31 (1H, d, J=3.7 Hz)
152.0
C
44.1
CH2
26.5 1.86 (1H, br d, J=13.2 Hz)
1.01 (1H, m)
16
CH2
22.7 2.01 (1H, m)
1.50 (1H, m)
17
18
19
C
37.3
CH
CH2
42.4 2.40 (1H, dd, J=14.1, 4.4 Hz)
47.0 1.88 (1H, dd, J=13.7, 13.2 Hz)
1.14 (1H, dd, J=13.7, 4.2 Hz)
31.3
103.5
82.7
77.6
71.6
78.1
62.6
105.9
76.9
78.2
71.5
78.4
62.6
103.4
82.6
77.5
71.0
77.8
62.4
103.0
85.3
77.6
70.6
77.6
62.3
106.1
76.2
78.7
71.3
78.9
62.7
30
40
20
21
C
50
CH2
34.5 1.41 (1H, br dd, J=13.7, 3.7 Hz)
1.26 (1H, m)
60
Glc-100
200
22
CH2
33.3 1.48 (1H, br dd, J=12.7, 3.2 Hz)
1.25 (1H, m)
300
23
24
25
26
27
28
CH3
CH3
CH3
CH3
CH3
CH2
28.6 1.23 (3H, s)
15.9 1.05 (3H, s)
13.5 1.18 (3H, s)
18.2 0.96 (3H, s)
400
500
600
Glc-1000
2000
3000
4000
5000
6000
24.5 1.33 (3H, s)
68.6 3.76 (1H, d, J=10.5 Hz)
3.55 (1H, d, J=10.5 Hz)
33.3 0.94 (3H, s)
29
30
CH3
CH3
23.7 0.97 (3H, s)
MeO-11 CH3
51.3 3.27 (3H, s)

2618
T. Kanchanapoom et al. / Phytochemistry 65 (2004) 2613–2618
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Phytochemistry
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The authors thank the Thailand Research Fund
(TRF) for financial support of this work. Also, we are
grateful to the Research Center for Molecular Medicine,
Hiroshima University, Japan for the provision of NMR
used in this investigation.
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