Phytochemistry Letters xxx (xxxx) xxx–xxx

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Phytochemistry Letters
journal homepage: www.elsevier.com/locate/phytol

Phenolic glycosides from Magnolia figo

Chutima Srinrocha, Poolsak Sahakitpichana, Nitirat Chimnoia, Somsak Ruchirawata,
Tripetch Kanchanapooma,b,*
a
Chulabhorn Research Institute, Kamphaeng Phet 6, Talat Bang Khen, Lak Si, Bangkok 10210, Thailand
b
Faculty of Pharmaceutical Sciences, Khon Kaen University, Khon Kaen 40002, Thailand

ARTICLE INFO ABSTRACT

Keywords: Three new phenolic glycosides were isolated from the leaves and twigs of Magnolia figo, and identitified to be
Magnolia figo 3,4-dihydroxy-β-phenylethoxyl-O-[β-D-glucopyranosyl-(1"→2')-α-L-rhamnopyranosyl-(1'"→3')-(4'-O-trans-caf-
Magnoliaceae feoyl)-β-D-glucopyranosyl-(1'""→6')]-β-D-glucopyranoside (champikhaekoside, 8), 4-hydroxybenzyl O-β-D-
Phenethanoid glycoside apiofuranosyl-(1"→2')-[β-D-glucopyranosyl-(1'"→3')]-β-D-glucopyranoside (17) and (+)-(7S,8S)-guaiacylgly-
Champikhaekoside
cerol 8-(6'-O-vanilloyl)-O-β-D-glucopyranoside (26). Additionally, 41 known compounds were identified. The
4-Hydroxybenzyl glycoside
structure elucidation of these compounds was based on analyses of physical and spectroscopic data including 1D
Guaiacylglycerol glycoside
and 2D NMR experiments.

1. Introduction (Yoshizawa et al., 1990; He et al., 1994), 2-(3,4-dihydroxyphenyl)ethyl

Magnolia figo (Syn. Michelia figo, M. fuscata; Thai name: Cham-Pi-
Khaek; Family Magnoliaceae) is an evergreen shrub up to 3 m high,
native to China. This species is widely cultivated as an ornamental plant
in many parts of Thailand for its fragrant flowers. Previous phyto-
chemical study of this species reported the presence of alkaloids, ses-
quiterpenes, and phenolic compounds (Iida and Ito, 1982; Lin et al.,
2016; Li et al., 2017; Chen et al., 2018; Huang et al., 2019). In the
framework of our phytochemical studies on Asian Magnoliaceous plants
(Sahakitpichan et al., 2017; Kanchanapoom et al., 2018; Srinroch et al.,
2019a, 2019b, 2019c), we investigated the secondary metabolites from
this plant, collected from Prachinburi Province. This present study deals
with the isolation and structure elucidation of 44 compounds, of which
compounds 8, 17 and 26 were new, from the water soluble fraction of
the MeOH extract of the leaves and twigs of this plant.
2. Results and discussion
The methanolic extract of the leaves and twigs of M. figo was par-
titioned between Et2O and H2O. The water soluble fraction was sepa-
rated by combination of chromatographic methods to provide three
new glycosides (8, 17 and 26) (Fig. 1) along with 41 known com-
pounds. The known compounds were identified as dec-
affeoylverbascoside (1) (Kanchanapoom et al., 2002a), kankanoside F
(2) (Yoshikawa et al., 2006), verbascoside (3) (Kanchanapoom et al.,
2002b), isosyringalide 3'-α-L-rhamnopyranoside (lipedoside A–I, 4)
3-O-(6-α-L-rhamnopyranosyl)-4-[(2Z)-3-(4-hydroxyphenyl)-2-pro-
penoate]-β-D-glucopyranoside (cis-lipedoside A–I, 5) (He et al., 1992),
crassoside (6) (Zaghloul and Zaghloul, 2002), echinacoside (7)
(Kobayashi et al., 1984), (7R)-campneoside I (9) (Srinroch et al., 2019a,
b, c), icariside D2 (10) (Miyase et al., 1989), tyrosol 4-O-β-D-xylopyr-
anosyl-(1→6)-β-D-glucopyranoside (11) (Sawasdee et al., 2010), sali-
droside (12) (Miyase et al., 1987), thalictricoside (13) (Erdemgil et al.,
2003), benzyl O-β-D-glucopyranoside (14), zizybeoside II (15)
(Okamura et al., 1981), benzyl O-β-D-apiofuranosyl-(1→2)-[β-D-glu-
copyranosyl-(1→3)]-β-D-glucopyranoside (16) (Kijima et al., 1997),
vanillic acid β-D-glucopyranosyl ester (18) (Klick and Herrmann,
1998), canthoside A (19) (Kanchanapoom et al., 2002b), 3,4,5-tri-
methoxyphenyl-β-D-glucopyranoside (20) (Achenbach and Benirschke,
1997), 3,4,5-trimethoxyphenyl-α-L-rhamnopyranosyl-(1→6)-β-D-glu-
copyranoside (21) (Andrianaivoravelona et al., 1999), sachaliside I (22)
(Jeon et al., 2008), carthamoside B5 (23) (Zhou et al., 2008),
(+)-(7S,8S)-syringylglycerol 8-O-β-D-glucopyranoside (24) (Kijima
et al., 1997; Gan et al., 2008), (+)-(7S,8S)-guaiacylglycerol 8-O-β-D-
glucopyranoside (25) (Ishimaru et al., 1987; Gan et al., 2008), coniferin
(27) (Sano et al., 1991), syringin (28) (Yang et al., 2007), iso-
syringinoside (29) (Sugiyama et al., 1993), syringinoside (30) (Niwa
et al., 1988), (R)-1-O-(β-D-glucopyranosyl)-2-[2-methoxy-4-(⌉-hydro-
xypropyl)-phenoxy]-propan-3-ol (31), (7R,8R)-threo-7,9,9'-trihydroxy-
3,3'-dimethoxy-8-O-4'-neolignan-4-O-β-glucopyranoside (32), (7S,8R)-
erythro-7,9,9'-trihydroxy-3,3'-dimethoxy-8-O-4'-neolignan-4-O-β-gluco-
pyranoside (33) (Huo et al., 2008), (7R,8S)-dihydrodehydrodiconiferyl

⁎
Corresponding author at: Faculty of Pharmaceutical Sciences, Khon Kaen University, Khon Kaen 40002, Thailand.
E-mail address: trikan@kku.ac.th (T. Kanchanapoom).

https://doi.org/10.1016/j.phytol.2019.09.008
Received 4 July 2019; Received in revised form 5 September 2019; Accepted 6 September 2019
1874-3900/ © 2019 Phytochemical Society of Europe. Published by Elsevier Ltd. All rights reserved.

Please cite this article as: Chutima Srinroch, et al., Phytochemistry Letters, https://doi.org/10.1016/j.phytol.2019.09.008
C. Srinroch, et al.
Fig. 1. Structures of compounds 1–9, 16, 17 and 24-26.
4-O-β-D-glucopyranoside (34) (Matsuda et al., 1996), (+)-pinoresinol-
β-D-glucopyranoside (35) (Tsukamoto et al., 1984), eucommin A (36)
(Deyama et al., 1985), (+)-syringaresinol O-β-D-glucopyranoside (37)
(Kobayashi et al., 1985), (+)-pinoresinol-4,4'-di-O-β-D-glucopyrano-
side (38) (Deyama, 1983), rutin (39), kaempferol 3-O-α-L-rhamnopyr-
anosyl-(1→6)-β-D-galactopyranoside (40), kaempferol 3-O-rutinoside
(41) (Agrawal and Bansal, 1989), quercetin 3-O-α-L-rhamnopyranosyl-
(1→2)-α-L-arabinofuranoside (arapetaloside A, 42), kaempferol 3-O-α-
L-rhamnopyranosyl-(1→2)-α-L-arabinofuranoside (arapetaloside B, 43)
(Li et al., 1997) and (6S,9R)-roseoside (44) (Yamano and Ito, 2005). All
known compounds were identified by comparison of physical data with
literature values and from spectroscopic evidence.
Compound 8 was obtained as a brown amorphous powder. The
molecular formula was determined to be C41H56O25 high resolution
electrospray time-of-flight (HR-ESI-TOF) mass spectrometric analysis.
The 1H NMR spectrum showed the presence of two sets of ABX aromatic
ring systems [δH 6.74 (d, J =1.5 Hz), 6.71 (d, J =8.0 Hz) and 6.59 (dd,
J = 8.0, 1.2 Hz) for the 3,4-dihydroxy-β-phenylethoxyl moiety; and δH
6.80 (d, J =8.2 Hz), 6.96 (dd, J = 8.2, 1.2 Hz) and 7.08 (d, J =1.2 Hz)
for the caffeoyl moiety], two trans-olefinic protons [δH 7.59 and 6.29
(each d, J =15.8 Hz)], together with four anomeric protons of sugar
moieties at δH 5.18 (br s), 4.65 (d, J =7.9 Hz), 4.62 (d, J =7.7 Hz), and
4.29 (d, J =7.7 Hz). This compound is an analogue of phenylethanoid
2
Phytochemistry Letters xxx (xxxx) xxx–xxx
glycosides, related to compounds 1-7. The chemical shifts of this
compound were similar to those of crassoside (6) (Table 1). The sig-
nificant difference due to the additional resonances of a β-D-gluco-
pyranosyl unit was observed in the NMR spectra. This unit was sug-
gested to be located at C-6' of a core β-D-glucopyranosyl part because of
the downfield shift of this carbon atom at δC 69.4. The assignments
were supported by the results from COSY, HSQC, and HMBC experi-
ments. In the HMBC spectrum, the significant correlations were found
from i) H-1' (δH 4.62, d, J =7.7 Hz) to C-8 (δC 72.0); ii) H-1" (δH 4.65, d,
J =7.9 Hz) to C-2' (δC 81.8); iii) H-1'" (δH 5.18, br s) to C-3' (δC 81.2);
iv) H-4' (δH 5.06, dd, J = 9.6, 9.5 Hz) to C-9"", (δC 168.5); and H-1'"" (δH
4.29, d, J =7.7 Hz) to C-6' (δC 69.4), as shown in Fig. 2. Therefore, the
structure of this compound was elucidated to be 3,4-dihydroxy-β-phe-
nylethoxyl-O-[β-D-glucopyranosyl-(1"→2')-α-L-rhamnopyranosyl-(1'"→
3')-(4'-O-trans-caffeoyl)-β-D-glucopyranosyl-(1'""→6')]-β-D-glucopyr-
anoside, namely champikhaekoside.
Compound 17 was isolated as an amorphous powder. Its molecular
formula was determined to be C24H36O16 by high resolution electro-
spray time-of-flight (HR-ESI-TOF) mass spectrometric analysis. The 1H-
NMR spectrum revealed the presence of the signals of a para-dis-
ubstituted aromatic ring system [δH 7.25 and 6.75 (each 2H, J
=8.4 Hz)], two methylene protons [δH 4.80 and 4.55 (each 1H, J
=11.1 Hz) for the aglycone moiety in addition to three anomeric
C. Srinroch, et al. Phytochemistry Letters xxx (xxxx) xxx–xxx

Table 1
NMR spectroscopic data of compounds 6 and 8 (400 MHz for 1H NMR and
100 MHz for 13C NMR, in CD3OD).
Position 6 8
δC δC δH

Aglycone
1 131.7 131.7
2 117.3 117.4 6.74 (1H, d, J =1.5 Hz)
3 146.0 145.9
4 144.5 144.5
5 116.5 116.5 6.71 (1H, d, J =8.0 Hz)
6 121.4 121.5 6.59 (1H, dd, J = 8.0, 1.5 Hz)
7 36.5 36.4 2.78 (2H, t, J =7.5 Hz)
8 71.9 72.0 4.07 (1H, m)
3.74 (1H, m)
Glc
1' 102.7 102.6 4.62 (1H, J =7.7 Hz)
2' 81.8 81.8 3.76 (1H, dd, J = 8.9, 7.7)
3' 81.4 81.2 4.01 (1H, dd, J = 9.5, 8.9 Hz)
4' 70.9 70.7 5.06 (1H, dd, J = 9.6, 9.5 Hz)
5' 75.8 74.4 3.75 (1H, m)
6' 62.4 69.4 3.92 (1H, br d, J =10.2 Hz)
3.60 (1 H)a
Glc
1" 103.1 103.1 4.65 (1H, J =7.9 Hz)
2" 75.5 75.5 3.22 (1 H)a
3" 78.2 77.7 3.36 (1 H)a
4" 71.2 71.8 3.32 (1 H)a
5" 77.8 77.6 3.13 (1 H)a
6" 62.6 62.5 3.83 (1 H)a
3.66 (1 H)a
Rha
1'" 103.1 103.0 5.18 (1H, br s)
2'" 71.9 71.9 4.09 (1 H)a
3'" 71.9 71.8 3.59 (1 H)a
4'" 73.7 73.6 3.31 (1 H)a
5'" 70.6 70.6 3.54 (1H, dd, J = 9.3, 6.2 Hz)
Fig. 2. HMBC correlations of compounds 8, 17 and 26.
6'" 18.4 18.4 1.01 (3H, d, J =6.2 Hz)
Caffeoyl
1"" 127.6 127.5 electrospray time-of-flight (HR-ESI-TOF) mass spectrometric analysis.
2"" 115.2 115.3 7.08 (1H, d, J =1.2 Hz)
3"" 146.7 146.7
Inspection of the 1H and 13C NMR spectroscopic data indicated that this
4"" 149.7 149.7 compound is an analogue of (+)-(7S,8S)-guaiacylglycerol 8-O-β-D-
5"" 116.4 116.5 6.80 (1H, d, J =8.2 Hz) glucopyranoside (25) (Table 3), having the same aglycone moiety and
6"" 123.2 123.3 6.96 (1H, dd, J = 8.2, 1.2 Hz) one β-D-glucopyranosyl unit. In addition the signal of a vanilloyl
7"" 147.9 148.2 7.59 (1H, d, J =15.8 Hz)
moiety was observed from the spectra. The additional group was placed
8"" 114.8 114.7 6.29 (1H, d, J =15.8 Hz)
9"" 168.3 168.5 at C-6' of the sugar moiety due to the downfield shift of this carbon
Glc atom as compared to that of compound 25. The large coupling constant
1"'" 104.5 4.29 (1H, J =7.7 Hz) between H-7 and H-8 with J =7.4 Hz, demonstrated a 7,8-threo con-
2"'" 75.0 3.22 (1 H)a figuration. A positive cotton effect at 236 nm in the CD spectrum sug-
3"'" 78.1 3.36 (1 H)a
4"'" 71.9 3.32 (1 H)a
gested the 8S configuration, and in turn to the 7S-configuration (Wang
5"'" 77.7 3.22 (1 H)a et al., 2017; Xiong et al., 2011). The structure assignment was con-
6"'" 62.5 3.83 (1 H)a firmed by the significant HMBC correlations from i) H-6' (δH 4.74, dd,
3.66 (1 H)a J = 12.0, 1.0 Hz and 4.31, dd, J = 12.0, 6.6 Hz) to C-7" (δC 167.9); ii)
H-1' (δH 4.50, d, J =7.7 Hz) to C-8 (δC 88.0); and iii) H-7 (δH 4.69, d, J
a
Chemical shifts were assigned by HMQC. =7.4 Hz) to C-2 (δC 111.5), C-6 (δC 120.8), C-8 (δC 88.0) and C-9 (δC
63.0). Thus, the structure of compound 26 was identified to be
protons [δH 5.43 (1H, d, J =2.5 Hz), 4.58 (1H, d, J =7.7 Hz) and 4.41 (+)-(7S,8S)-guaiacylglycerol 8-(6'-O-vanilloyl)-O-β-D-glucopyranoside.
(1H, d, J =7.8 Hz)]. The sugar part was identical with of benzyl O-β-D- In conclusion, the present work reported 44 compounds from the
apiofuranosyl-(1→2)-[β-D-glucopyranosyl-(1→3)]-β-D-glucopyrano- water soluble part of the MeOH extract of M. figo, including glycosides
side (16). This compound showed one more oxygen atom than com- of phenylethanoid (1-13), simple aromatic (14-21), phenylpropanoid
pound 16, therefore the aglycone moiety was identified to be 4-hy- (22-31), lignan and neolignan (32-38), flavonoid (39-43) and mega-
droxybenzyl alcohol. The structure was further confirmed by the HMBC stigmane (44). The presence of these compounds from this species in-
spectrum (Fig. 2), in which the significant correlations were observed dicated that there are no significant differences in the chemical patterns
from i) H-2,6 (δH 7.25, d. J =8.4 Hz) to C-7 (δC71.8); ii) H-1' (δH 4.41, among member of this genus. However, it provides further confirmation
d, J =7.8 Hz) to C-7 (δC 71.8); iii) H-1" (δH 5.43, d, J =2.5 Hz) to C-2' of the typical profile of secondary metabolites found in this family.
(δC 79.6); and iv) H-1'" (δH 4.58, d, J =7.7 Hz) to C-3' (δC 87.0). Con-
sequently, the structure of compound 17 was elucidated as 4-hydro- 3. Experimental
xybenzyl O-β-D-apiofuranosyl-(1"→2')-[β-D-glucopyranosyl-(1'"→3')]-
β-D-glucopyranoside. 3.1. General procedures
Compound 26 was isolated as an amorphous powder, and its mo-
lecular formula was determined to be C24H30O13 high resolution NMR spectra were recorded in CD3OD or DMSO-d6 using a Bruker

3
C. Srinroch, et al. Phytochemistry Letters xxx (xxxx) xxx–xxx

AV-400 (400 MHz for 1H-NMR and 100 MHz for 13C-NMR) spectro- Table 2
meter. The MS data was obtained on a Bruker Micro TOF-LC mass NMR spectroscopic data of compound 17 (400 MHz for 1H NMR and 100 MHz
spectrometer. Optical rotations were measured with a Jasco P-1020 for 13C NMR, in CD3OD).
digital polarimeter. Circular dichroism spectra were recorded on a Position 17
Jasco J-815 spectropolarimeter. For column chromatography, Diaion
HP-20 (Mitsubishi Chemical Industries Co. Ltd.), silica gel 60 (230–400 δC δH
mesh, Merck), and RP-18 (50 μm, YMC) were used. HPLC (Shimadzu
Aglycone
LC-10AT pump) was carried out on an ODS column (21.2 x 250 mm i.d., 1 129.6
Vertisep™UPS) with a Jasco UV-970 detector at 210 nm. The flow rates 2, 6 131.2 7.25 (2H, d, J =8.4 Hz)
were 6 ml/min. The spraying reagent used for TLC was 10% H2SO4 in 3, 5 116.0 6.75 (2H, d, J =8.4 Hz)
4 158.3
H2O-EtOH (1:1, v/v).
7 71.8 4.80 (1H, d, J =11.1 Hz)
4.55 (1H, d, J =11.1 Hz)
3.2. Plant material Glc
1' 101.7 4.41 (1H, d, J =7.8 Hz)
The leaves and twigs of Magnolia figo (Lour.) DC. were collected 2' 79.6 3.53 (1H, dd, J = 8.1, 7.8 Hz)
3' 87.0 3.67 (1H, dd, J = 9.4, 8.1 Hz)
from Prachinburi Province, Thailand, in September 2017 (Voucher
4' 70.1 3.41 (1H, dd, J = 9.4, 9.2 Hz)
specimens: TK-PSKKU-0085). Plant specimens were identified by Mr. 5' 77.5 3.26 (1H, m)
Thinakorn Komkris and deposited in the Herbarium of the Faculty of 6' 62.7 3.90 (1H, dd, J = 12.1, 1.9 Hz)
Pharmaceutical Sciences, Khon Kaen University. 3.69 (1H, dd, J = 12.1, 5.3 Hz)
Api
1" 110.9 5.43 (1H, d, J =2.5 Hz)
3.3. Extraction and isolation 2" 78.0 3.95 (1H, dd, J =2.5 Hz)
3" 80.4
The air dried leaves and twigs of M. figo (1.2 kg) were extracted 4" 75.1 3.98 (1H, d, J =9.4 Hz)
three times with MeOH, and concentrated to dryness. The brown- 3.65 (1H, d, J =9.4 Hz)
5" 65.5 3.54 (1H, d, J =11.3 Hz)
greenish residue (187.0 g) was suspended in H2O and partitioned with
3.52 (1H, d, J =11.3 Hz)
Et2O. The water soluble part (121.7 g) was subjected to a Diaion HP-20 Glc
column, and eluted with H2O, and MeOH, successively. The fraction 1'" 104.5 4.58 (1H, d, J =7.7 Hz)
eluted with MeOH (45.4 g) was applied to a silica gel column using 2'" 75.3 3.25 (1H, dd, J = 9.3, 7.7 Hz)
3'" 78.1 3.36 (1H, dd, J = 9.3, 9.1 Hz)
solvent systems EtOAc-MeOH (9:1, 8.0 L), EtOAc-MeOH-H2O (40:10:1,
4'" 71.5 3.28 (1 H)a
12.0 L), EtOAc-MeOH-H2O (70:30:3, 12.0 L) and EtOAc-MeOH-H2O 5'" 78.0 3.29 (1 H)a
(6:4:1, 14.0 L), respectively to provide five fractions (A to E). 6'" 62.6 3.88 (1H, dd, J = 12.2, 2.0 Hz)
Fraction A (2.8 g) was applies to a RP-18 column using a gradient 3.63 (1H, dd, J = 12.2, 6.3 Hz)
solvent system, H2O-MeOH (90:10 → 20:80, v/v) to provide 12 sub-
fractions. Sub-fraction A-1 was purified by preparative HPLC-ODS using a
Chemical shifts were assigned by HMQC.
solvent system H2O-MeCN (93:7, v/v) to give compound 10 (4.0 mg).
Sub-fraction A-2 was purified by preparative HPLC-ODS with solvent
system H2O-MeCN (90:10, v/v) to provide compounds 1 (21.6 mg) and
18 (19.2 mg). Sub-fractions A-3 and A-4 were purified by preparative system H2O-MeCN (75:25, v/v) to give compound 43 (271.5 mg).
HPLC-ODS with solvent system H2O-MeCN (85:15, v/v) to provide Fraction C (5.3 g) was applied to a RP-18 column using solvent
compounds 12 (6.8 mg), 20 (36.1 mg) and 27 (48.6 mg), 14 (13.9 mg), system, H2O-MeOH (90:10 → 20:80, v/v) to give ten sub-fractions. Sub-
22 (19.5 mg) and 44 (71.1 mg). Sub-fraction A-6 was purified by pre- fraction C-3 was purified by preparative HPLC-ODS with solvent system
parative HPLC-ODS with solvent system H2O-MeCN (83:17, v/v) to H2O-MeCN (90:10, v/v) to obtain compounds 29 (80.6 mg) and 30
yield compound 26 (11.0 mg). Sub-fraction A-7 was purified by pre- (21.9 mg). Sub-fraction C-4 was purified by preparative HPLC-ODS with
parative HPLC-ODS with solvent system H2O-MeCN (80:20, v/v) to solvent system H2O-MeCN (88:12, v/v) to provide compounds 17
afford compounds 3 (194.8 mg), 35 (156.4 mg) and 36 (16.0 mg). Sub- (16.3 mg) and 21 (18.1 mg). Sub-fraction C-5 was purified by pre-
fraction A-9 was purified by preparative HPLC-ODS with solvent system parative HPLC-ODS with solvent system H2O-MeCN (85:15, v/v) to give
H2O-MeCN (75:25, v/v) to give compound 4 (214.0 mg). Sub-fraction compounds 15 (41.3 mg) and 33 (22.0 mg). Sub-fraction C-6 was pur-
A-11 was purified by preparative HPLC-ODS with solvent system H2O- ified by preparative HPLC-ODS with solvent system H2O-MeCN (85:15,
MeCN (75:25, v/v) to obtain compound 5 (54.9 mg). v/v) to provide compounds 7 (95.1 mg), 16 (104.7 mg) and 38
Fraction B (13.9 g) was separated on a RP-18 column using solvent (51.2 mg). Sub-fraction C-7 was purified by preparative HPLC-ODS with
system, H2O-MeOH (90:10 → 20:80, v/v) to provide 11 sub-fractions. solvent system H2O-MeCN (83:17, v/v) to obtain compound 6
Sub-fraction B-1 was purified by preparative HPLC-ODS with solvent (77.7 mg).
system H2O-MeCN (93:7, v/v) to give compounds 11 (97.1 mg), 23 Fraction D (4.4 g) was applied to a RP-18 column using solvent
(20.8 mg), 24 (22.4 mg) and 25 (10.3 mg). Sub-fraction B-2 was pur- system, H2O-MeOH (90:10 → 20:80, v/v) to give 12 sub-fractions. Sub-
ified by preparative HPLC-ODS with solvent system H2O-MeCN (90:10, fraction D-5 was purified by preparative HPLC-ODS with solvent system
v/v) to provide compounds 2 (13.2 mg) and 28 (80.2 mg). Sub-fraction H2O-MeCN (85:15, v/v) to provide compound 8 (209.7 mg). Finally,
B-3 was purified by preparative HPLC-ODS with solvent system H2O- sub-fraction D-10 was purified by preparative HPLC-ODS with solvent
MeCN (88:12, v/v) to yield compound 13 (8.7 mg). Sub-fraction B-4 system H2O-MeCN (80:20, v/v) to obtain compound 39 (52.3 mg).
was purified by preparative HPLC-ODS with solvent system H2O-MeCN
(88:12, v/v) to afford compounds 19 (31.8 mg), 31 (77.1 mg) and 32
(103.0 mg). Sub-fraction B-6 was purified by preparative HPLC-ODS 3.4. Champikhaekoside (8)
with solvent system H2O-MeCN (83:17, v/v) to obtain compound 34
(111.9 mg). Sub-fractions B-7 and B-8 were purified by preparative Amorphous powder, [α]D23 −37.5 (MeOH, c 0.15); 1H and 13C
HPLC-ODS with solvent system H2O-MeCN (80:20, v/v) to give com- NMR (CD3OD): Table 1; Negative HRESITOFMS, m/z: 947.3020
pounds 37 (32.4 mg), 40 (35.0 mg), 41 (37.8 mg), and 42 (75.5 mg). [M−H]− (C41H55O25 required 947.3037).
Sub-fraction B-9 was purified by preparative HPLC-ODS with solvent

4
C. Srinroch, et al. Phytochemistry Letters xxx (xxxx) xxx–xxx

Table 3 Deyama, T., 1983. The constituents of Eucommia ulmoides Oliv. I. Isolation of (+)-med-
NMR spectroscopic data of compounds 25 and 26 (400 MHz for 1H NMR and ioresinol di-O-β-D-glucopyranoside. Chem. Pharm. Bull. 31, 2993–2997.
100 MHz for 13C NMR, in CD3OD). Deyama, T., Ikawa, T., Nishibe, S., 1985. The constituents of Eucommia ulmiudes Oliv. II.
Isolation and structures of three new lignan glycosides. Chem. Pharm. Bull. 33,
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