A new flavonol glycoside from Hylomecon vernalis

Article abstract of DOI:10.1007/s12272-012-0303-8

Purification of a MeOH extract from the aerial parts of Hylomecon vernalis Maxim. (Papaveraceae) using column chromatography furnished a new acetylated flavonol glycoside (1), together with twenty known phenolic compounds (2-21). Structural elucidation of 1 was based on 1D- and 2D-NMR spectroscopy data analysis to be quercetin 3-O-[4′→O-acetyl-α-L-arabinopyranosyl] -( 1′→6′)-β-D-galactopyranoside (1). The structures of compounds 2-21 were elucidated by spectroscopy and confirmed by comparison with reported data; quercetin 3-O- [2′→O-acetyl-α-L- arabinopyranosyl]-(1′→6′)-β-D-galactopyranoside (2), quercetin 3-O-α-L-arabinopyranosyl-( 1′→6′)-β-D- galactopyranoside (3), quercetin 3-O-β-D-galactopyranoside (4), kaempferol 3,7-O-α-L-dirhamnopyranoside (5), diosmetin 7-O-β-D-glucopyranoside (6), diosmetin 7-O-β-D-xylopyranosyl-(1′→6′)-β-D- glucopyranoside (7), p-hydroxybenzoic acid (8), protocatechuic acid (9), caffeic acid (10), 6-hydroxy-3,4-dihydro-1-oxo-β-carboline (11), (Z)-3- hexenyl-β-D-glucopyranoside (12), (E)-2-hexenyl-β-D-glucopyranoside (13), (Z)-3-hexenyl-α-Larabinopyranosyl-( 1′→6')-β-D- glucopyranoside (14), oct-1-en-3-yl-α-L-arabinopyranosyl- (1′→6')- β-D-glucopyranoside (15), benzyl-β-D- apiofuranosyl-(1′→6')-β-D-glucopyranoside (16), benzyl- α-L-arabinopyranosyl-(1′→6')-β-D-glucopyranoside (17), benzyl-β-D-xylopyranosyl-(1′→6')-β-Dglucopyranoside (18), 2-phenylethyl-α-L-arabinopyranosyl-(1′→6')-β-D- glucopyranoside (19), 2-phenylethyl-β-D-apiofuranosyl-(1′→6')- β-D-glucopyranoside (20), and aryl-β-D-glucopyranoside (21). Compounds 2-21 were isolated for the first time from this plant. The isolated compounds were tested for cytotoxicity against four human tumor cell lines in vitro using a Sulforhodamin B bioassay.

Full text of DOI:10.1007/s12272-012-0303-8

Arch Pharm Res Vol 35, No 3, 415-421, 2012
DOI 10.1007/s12272-012-0303-8
A New Flavonol Glycoside from Hylomecon vernalis
Seung Young Lee1, Ki Hyun Kim1, Il Kyun Lee1, Kyu Ha Lee1, Sang Un Choi2, and Kang Ro Lee1
1Natural Products Laboratory, School of Pharmacy, Sungkyunkwan University, Suwon 440-746, Korea and 2Korea
Research Institute of Chemical Technology, Teajeon 305-600, Korea
(Received January 27, 2011/Revised April 14, 2011/Accepted May 3, 2011)
Purification of a MeOH extract from the aerial parts of Hylomecon vernalis Maxim. (Papaver-
aceae) using column chromatography furnished a new acetylated flavonol glycoside (
1
),
was based
-acetyl- -L-ara-
). The structures of compounds 2-21 were
elucidated by spectroscopy and confirmed by comparison with reported data; quercetin 3-
[2'''- -acetyl- -L-arabinopyranosyl]-(1''' 6'')- -D-galactopyranoside ( ), quercetin 3- -L-ara-
binopyranosyl-(1''' 6'')- -D-galactopyranoside ( ), quercetin 3- -D-galactopyranoside ( ),
kaempferol 3,7- -L-dirhamnopyranoside ( ), diosmetin 7- -D-glucopyranoside ( ), dios-
metin 7- -D-xylopyranosyl-(1''' 6'')- -D-glucopyranoside ( -hydroxybenzoic acid ( ), pro-
tocatechuic acid ( ), caffeic acid (10), 6-hydroxy-3,4-dihydro-1-oxo- -carboline (11), ( )-3-
hexenyl- -D-glucopyranoside (12), ( )-2-hexenyl- -D-glucopyranoside (13), ( )-3-hexenyl-
arabinopyranosyl-(1'' 6')- -D-glucopyranoside (14), oct-1-en-3-yl- -L-arabinopyranosyl-(1''
-D-glucopyranoside (15), benzyl- -D-apiofuranosyl-(1'' 6')-
-L-arabinopyranosyl-(1'' 6')- -D-glucopyranoside (17), benzyl-
glucopyranoside (18), 2-phenylethyl- -L-arabinopyranosyl-(1''
2-phenylethyl- -D-apiofuranosyl-(1'' 6')- -D-glucopyranoside (20), and aryl-
side (21). Compounds 21 were isolated for the first time from this plant. The isolated com-
together with twenty known phenolic compounds (
on 1D- and 2D-NMR spectroscopy data analysis to be quercetin 3-
binopyranosyl]-(1''' 6'')- -D-galactopyranoside (
2
-21). Structural elucidation of
1
O-[4'''-
O
α
→
β
1
O
-
O
α
→
β
2
β
O-α
→
β
3
O
β
p
-
4
O-
α
5
O
-
6
8
O
-β
→
β
7
),
9
β
Z
α
→
β
E
β
Z
-L-
6')-
→
β
α
β
α
β
→
β
-D-glucopyranoside (16), benzyl-
-D-xylopyranosyl-(1'' 6')- -D-
6')- -D-glucopyranoside (19),
-D-glucopyrano-
→
β
β
→
→
β
α
β
β
→
β
β
2
-
pounds were tested for cytotoxicity against four human tumor cell lines in vitro using a
Sulforhodamin B bioassay.
Key words: Hylomecon vernalis, Papaveraceae, Acetylated flavonol glycoside
on this plant reported the isolation of several alkaloids
Selected by Editors
and reported to have anti-inflammatory, antispasmodic,
antimicrobial, and anti-tumoral activities (Kang et al.,
2003). We have investigated constituents from the
aerial parts of vernalis as part of our continuing
INTRODUCTION
H.
Hylomecon vernalis Maxim. is an east Asian herba- study on the constituents of Korean medicinal plant
ceous medicinal plant belonging to the Papaveraceae. sources. Column chromatography separation of consti-
H
.
vernalis is widely distributed in the mountainous tuents in the MeOH extract of
regions of Korea and China (Lee, 1996). vernalis has the isolation of twenty one compounds, including a
been used in Chinese folk medicine for the treatment new acetylated flavonol glycoside ( ). Their structures
of arthritis, neuralgia, and eczema (Kim et al., 2003). were determined by spectroscopic methods. Compound
H. vernalis resulted in
H.
1
Previous phytochemical and pharmacological studies
1
was newly isolated from natural sources, and com-
pounds 21 were isolated for the first time from this
2
-
particular plant. The isolated compounds were tested
for cytotoxicity against four human tumor cells in
vitro using a Sulforhodamin B bioassay.
Correspondence to: Kang Ro Lee, Natural Products Laboratory,
School of Pharmacy, Sungkyunkwan University, Suwon 440-
746, Korea
Tel: 82-31-290-7710, Fax: 82-31-292-8800
E-mail: krlee@skku.ac.kr
415

416
S. Y. Lee et al.
compound
9
(4 mg, Rt = 13 min), 10 (4 mg, Rt = 15
MATERIALS AND METHODS
General experimental procedure
min) and 11 (5 mg, Rt = 16 min). Fraction E8 was
subjected to Sephadex LH-20 column chromatography
Melting points were determined on a Gallenkamp (80% MeOH) as the eluant to give five subfractions
melting point apparatus and are uncorrected. Optical (E81-E85). Subfraction E82 (40 mg) was purified with
rotations were measured on a JASCO P-1020 Polari- an RP-C18 prep HPLC (50% MeOH) to yield compound
meter. IR spectra were recorded on a Bruker IFS-66/S
FT-IR spectrometer. UV spectra were recorded with a purified with an RP-C18 prep HPLC (55% MeOH) to
Shimadzu UV-1601 UV-Visible spectrophotometer. yield compound (17 mg, Rt = 11 min). Subfraction
NMR spectra were recorded on a Varian UNITY E84 (40 mg) was purified with an RP-C18 prep HPLC
INOVA 500 NMR spectrometer. ESI and HR-ESI mass (50% MeOH) to yield compound (15 mg, Rt = 11 min)
4 (17 mg, Rt = 12 min). Subfraction E83 (40 mg) was
5
1
spectra were obtained on a VG BIOTECH platform LC- and
6 (12 mg, Rt = 15 min). Fraction E13 was separ-
mass spectrometer. Preparative HPLC was performed ated over a RP-C18 Lobar A®-column with a solvent
using a Gilson 306 pump with a Shodex refractive system of 40% MeOH as the eluant to give four sub-
index detector and an Apollo Silica 5
22 mm) or an Econosil® RP-18 10
column (250 × 22 purified with an RP-C18 prep HPLC (50% MeOH) to
mm). Silica gel 60 (Merck, 70~230 mesh and 230~400 yield compound (9 mg, Rt = 12 min). The n-BuOH
µ column (250 × fractions (E131-E134). Subfraction E133 (20 mg) was
µ
3
mesh) was used for column chromatography. TLC was soluble fraction (30 g) was chromatographed on a
performed using Merck precoated Silica gel F254 plates diaion HP-20, and eluted using a gradient solvent
and RP-18 F254s plates. The packing material for mole- system that varied from 100% water to 100% MeOH.
cular sieve column chromatography was Sephadex This gave two subfraction. Fraction B (8 g) was separ-
LH-20 (Pharmacia Co.). Low-pressure liquid chroma- ated over a silica gel column with a solvent system of
tography was performed over Merck LiChroprep Lobar®- (CHCl3-MeOH-Water = 10:5:1 – 6:4:1) as the eluant to
A Si 60 (240 × 10 mm) or LiChroprep Lobar®-A RP-18 give thirteen fractions (B1-B13). Fraction B3 was sep-
(240 × 10 mm) columns with a FMI QSY-0 pump arated over an RP-C18 Lobar A®-column with a solvent
(ISCO).
system of 40% MeOH as the eluant to give three
subfractions (B31-B33). Subfraction B32 (80 mg) was
purified with an RP-C18 prep HPLC (50% MeOH) to
Plant materials
The aerial parts of Hylomecon vernalis Maxim. were yield compound 12 (8 mg, Rt = 15 min) and 13 (5 mg,
collected at Taebaek mountain in Ganawon-Do pro- Rt = 16 min). Fraction B4 was separated over an RP-
vince, Korea in May 2009. A voucher specimen (SKKU- C18 Lobar A®-column with a solvent system of 45%
2009-002) was deposited at the School of Pharmacy in MeOH as the eluant to give four subfractions (B41-
Sungkyunkwan University.
B44). Subfraction B44 (17 mg) was purified with a
silica gel prep HPLC (CH2Cl2-MeOH = 5:1) to yield
compound 21 (5 mg, Rt = 12 min). Fraction B5 was
Extraction and isolation
The half dried aerial parts of H. vernalis (2.6 kg) separated over an RP-C18 Lobar A®-column with a
were extracted at room temperature with 80% MeOH solvent system of 45% MeOH as the eluant to give five
and evaporated under reduced pressure to give a subfractions (B51-B55). Subfraction B53 (50 mg) was
residue (240 g), that was dissolved in water (800 mL purified with an RP-C18 prep HPLC (45% MeOH) to
three times) and then partitioned into a series of other yield compound 20 (10 mg, Rt = 17 min). Subfraction
solvents. These solvents, and the residues found in B55 (15 mg) was purified with a RP-C18 prep HPLC
each were as follows;
EtOAc (3 g), and -BuOH (30 g). The EtOAc fraction min). Fraction B6 was was separated over an RP-C18
(3 g) was separated over a silica gel column with a silica gel column with a solvent system of 45% MeOH
solvent system of ( -hexane-CHCl3-MeOH = 10:5:1 – as the eluant to give three subfractions (B61-B63).
n-hexane (40 g), CH2Cl2 (1 g), (50% MeOH) to yield compound 15 (5 mg, Rt = 15
n
n
CHCl3-MeOH = 1:1) as the eluant to give fifteen frac- Subfraction B61 (60 mg) was purified with a silica gel
tions (E1-E15). Fraction E3 was purified with a silica prep HPLC (CHCl3-MeOH-H2O = 9:4:0.5) to yield com-
gel prep HPLC (CHCl3-MeOH = 12:1) to yield com- pounds 16 (5 mg, Rt = 13 min), 17 (5 mg, Rt = 14 min),
pound
8 (5 mg, Rt = 12 min). Fraction E6 was sub- and 18 (8 mg, Rt = 16 min). Subfraction B62 (30 mg)
jected to Sephadex LH-20 column chromatography was purified with an RP-C18 prep HPLC (50% MeOH)
(80% MeOH) as the eluant to give three subfractions to yield compound 19 (13 mg, Rt = 13 min). Subfrac-
(E61-E63). Subfraction E63 (60 mg) was purified with tion B63 (35 mg) was purified with an RP-C18 prep
a silica gel prep HPLC (CHCl3-MeOH = 12:1) to yield HPLC (50% MeOH) to yield compound 14 (12 mg, Rt
=

A New Flavonol Glycoside from Hylomecon vernalis
417
15 min). Fraction B7 was was separated over an RP- MeOH); FAB-MS m/z: 597 [M+H]+; 1H-NMR (CD3OD,
C18 silica gel column with a solvent system of 50% 500 MHz): 7.67 (1H, dd, = 8.2, 2.3 Hz, H-6'), 7.57
MeOH as the eluant to give four subfractions (B71- (1H, d, = 2.3 Hz, H-2'), 6.86 (1H, d, = 8.2 Hz, H-5'),
B74). Subfraction B71 (35 mg) was purified with an 6.37 (1H, brs, H-8), 6.17 (1H, brs, H-6), 5.30 (1H, d,
RP-C18 prep HPLC (30% MeCN) to yield compound = 7.6 Hz, H-1''), 3.99 (1H, d,
= 6.4 Hz, H-1'''); 13C-
(15 mg, Rt = 11 min). Fraction B8 was separated over NMR (CD3OD, 125 MHz): 178.1 (C-4), 164.9 (C-7),
δ
J
J
J
J
7
J
δ
an RP-C18 Lobar A®-column with a solvent system of 161.9 (C-5), 157.0 (C-2, 9), 149.2 (C-4'), 145.5 (C-3'),
35% MeOH as the eluant to give four subfractions 134.2 (C-3), 122.7 (C-6'), 121.8 (C-1'), 116.6 (C-5'),
(B81-B84). Subfraction B84 (100 mg) was subjected to 115.9 (C-2'), 104.6 (C-10), 103.3 (C-1'''), 102.5 (C-1''),
Sephadex LH-20 column chromatography (90% MeOH) 99.4 (C-6), 94.2 (C-8), 75.0 (C-5''), 73.7 (C-3''), 73.1 (C-
as the eluant to give fractions purified with an RP-C18 3'''), 71.1 (C-2''), 71.1 (C-2'''), 68.9 (C-4''), 68.0 (C-4'''),
prep HPLC (20% MeCN) to yield compound
2
(15 mg, 67.2 (C-6''), 65.6 (C-5''').
Rt = 15 min).
Quercetin 3-
-L-arabinopyranosyl]- (4)
-D-galactopyranoside (1)
Yellow powder; mp 253-254oC; FAB-MS m/z: 465
0.08, MeOH); IR (KBr) νmax [M+H]+; 1H-NMR (CD3OD, 500 MHz):
7.68 (1H, dd,
cm−1: 3401, 1646, 1528, 1366, 1021, 672; UV [MeOH)
= 8.2, 2.3 Hz, H-6'), 7.57 (1H, d, = 2.3 Hz, H-2'),
nm (log ): 258 (4.91), 362 (4.84); HR-ESI-MS (rel. 6.93 (1H, d, = 8.2 Hz, H-5'), 6.40 (1H, brs, H-8), 6.20
int.): 661.1375 [M + Na]+ (calcd for: 661.1375); H- (1H, brs, H-6), 5.37 (1H, d, = 7.6 Hz, H-1''); 13C-NMR
NMR (500 MHz, DMSO-d6): 12.61 (C5-OH), 7.77 (1H, (CD3OD, 125 MHz): 178.2 (C-4), 164.9 (C-7), 161.9
dd, = 8.8, 2.3 Hz, H-6'), 7.62 (1H, d, = 2.3 Hz, H- (C-5), 156.9 (C-2, 9), 149.2 (C-4'), 145.5 (C-3'), 134.2
2'), 6.83 (1H, d, = 8.8 Hz, H-5'), 6.42 (1H, s, H-8), (C-3), 122.7 (C-6'), 121.8 (C-1'), 116.6 (C-5'), 115.9 (C-
6.20 (1H, s, H-6), 5.26 (1H, d, = 7.6 Hz, H-1''), 4.06 2'), 104.6 (C-10), 102.5 (C-1''), 99.4 (C-6), 94.2 (C-8),
(1H,
= 6.4 Hz, H-1'''), 1.98 (3H, s, COCH3) and 13C- 76.5 (C-5''), 73.9 (C-3''), 71.9 (C-2''), 68.6 (C-4''), 60.8
O-β
-D-galactopyranoside (Hyperin)
Quercetin 3-
(1''' 6'')-
Yellow gum, [
O
-[4'''-
O-acetyl-α
→
β
25
α
]
−
80o (
c
δ
D
J
J
ε
m/z
J
1
J
δ
J
J
J
J
J
NMR (125 MHz, DMSO-d6): 178.1 (C-4), 170.6 (C=O), (C-6'').
164.3 (C-7), 161.9 (C-5), 157.0 (C-2, 9), 149.2 (C-4'), 145.5
(C-3'), 134.2 (C-3), 122.78 (C-6'), 121.7 (C-1'), 116.6 (C- Kaempferol 3,7-O-α-L-dirhamnopyranoside (5)
5'), 115.9 (C-2'), 104.6 (C-10), 103.5 (C-1'''), 102.6 (C-1''), Yellow powder; mp 209-213oC; FAB-MS m/z: 579
99.4 (C-6), 94.2 (C-8), 75.0 (C-5''), 73.7 (C-3''), 71.7 (C- [M+H]+; 1H-NMR (CD3OD, 500 MHz):
2'''), 71.5 (C-4'''), 71.4 (C-2''), 71.2 (C-3'''), 68.9 (C-4''), = 8.5 Hz, H-2', 6'), 6.94 (2H, d, = 8.0 Hz, H-3', 5'),
67.6 (C-6''), 63.4 (C-5'''), 21.6(COCH3). 6.72 (1H, brs, H-8), 6.46 (1H, brs, H-6), 5.57 (1H, d,
= 1.5 Hz, H-1'''), 5.40 (1H, d, = 1.5 Hz, H-1''), 1.26
-L-arabinopyranosyl]- (1H, d, = 6.0 Hz, H-6'''), 0.93 (1H, d, = 6.0 Hz, H-
-D-galactopyranoside (2) 178.6 (C-4), 162.3
6''); 13C-NMR (CD3OD, 125 MHz):
Yellow gum; FAB-MS m/z: 639 [M+H]+; 1H-NMR (C-7), 161.8 (C-5), 160.6 (C-4'), 158.6 (C-2), 156.9 (C-9),
(DMSO-d6, 500 MHz): 12.65 (1H, brs, 5-OH), 7.77 135.3 (C-3), 130.8 (C-2', 6'), 121.2 (C-1'), 115.4 (C-3',
(1H, dd, = 8.5, 2.5 Hz, H-6'), 7.63 (1H, d, = 2.5 Hz, 5'), 106.4 (C-10), 102.3 (C-1''), 99.4 (C-1'''), 98.7 (C-6),
H-2'), 6.83 (1H, d, = 8.5 Hz, H-5'), 6.42 (1H, brs, H- 94.4 (C-8), 72.4 (C-4''), 72.0 (C-4'''), 70.9 (C-3''), 70.8 (C-
8), 6.20 (1H, brs, H-6), 5.26 (1H, d, = 7.5 Hz, H-1''), 3'''), 70.5 (C-2'''), 70.4 (C-2''), 70.1 (C-5''), 70.0 (C-5'''),
4.06 (1H, d, = 8.0 Hz, H-1'''), 1.65 (3H, s, COCH3); 16.8 (C-6'''), 16.5 (C-6'').
13C-NMR (DMSO-d6, 125 MHz):
177.9 (C-4), 169.7
(C=O), 164.8 (C-7), 161.7 (C-5), 156.8 (C-9), 156.6 (C- Diosmetin-7-
2), 149.1 (C-4'), 145.4 (C-3'), 134.0 (C-3), 122.5 (C-6'), Yellow solid; FAB-MS m/z: 463 [M+H]+; 1H-NMR
121.4 (C-1'), 116.3 (C-5'), 115.7 (C-2'), 104.4 (C-10), (DMSO-d6, 500 MHz): 12.94 (1H, brs, 5-OH), 7.58
102.5 (C-1''), 100.9 (C-1'''), 99.2 (C-6), 94.1 (C-8), 76.1 (1H, dd, = 8.2, 2.3 Hz, H-6'), 7.46 (1H, d, = 2.3 Hz,
(C-5''), 73.2 (C-3''), 72.5 (C-2'''), 71.4 (C-2''), 70.8 (C-3'''), H-2'), 7.11 (1H, d, = 8.2 Hz, H-5'), 6.83 (1H, s, H-3),
69.2 (C-4''), 68.4 (C-4'''), 67.4 (C-6''), 66.1 (C-5'''), 20.7 6.82 (1H, d, = 2.3 Hz, H-8), 6.45 (1H, d, = 2.3 Hz,
H-6), 5.08 (1H, d, = 7.6 Hz, H-1''), 3.88 (1H, s, -
OCH3); 13C-NMR (DMSO-d6, 125 MHz):
182.6 (C-4),
δ 7.79 (2H, d, J
J
J
J
Quercetin 3-
O
-[2'''-
O
-acetyl-
α
J
J
(1''' 6'')-
→
β
δ
δ
J
J
J
J
J
δ
O-β-D-glucopyranoside (6)
δ
J
J
J
J
J
(CH3).
J
δ
Quercetin 3-
O
-
α
-L-arabinopyranosyl-(1'''
→6'')-β-
164.8 (C-7), 163.7 (C-2), 161.8 (C-5), 157.7 (C-9), 152.0
(C-4'), 147.5 (C-3'), 123.6 (C-1'), 119.6 (C-6'), 113.9 (C-
D-galactopyranoside (3)
25
Yellow solid; mp 252-253oC; [α D
]
− c 0.44 in 2'), 112.9 (C-5'), 106.1 (C-3), 104.5 (C-10), 100.6 (C-1''),
87o (

418
S. Y. Lee et al.
100.2 (C-8), 95.5 (C-6), 77.8 (C-5''), 77.1 (C-3''), 73.8 (C- 103.1 (C-5), 41.6 (C-3), 20.4 (C-4).
2''), 70.3 (C-4''), 61.3 (C-6''), 56.6 (OCH3).
(
Z
)-3-Hexenyl-
-D-glu- Colorless amorphous solid; [α D −
38.0o (c 0.48 in
1
β-D-glucopyranoisde (12)
25
Diosmetin-7-
copyranoside (7)
Yellow solid; mp 262-264oC; FAB-MS m/z: 595 [M+H]+; 500 MHz):
1H-NMR (DMSO-d6, 500 MHz):
12.94 (1H, brs, 5- (1H, d, = 7.5 Hz, H-1'), 2.38 (1H, q,
OH), 7.60 (1H, dd, = 8.2, 2.3 Hz, H-6'), 7.53 (1H, d, 2.08 (1H, quintet, = 7.0 Hz, H-5), 0.97 (1H, t,
= 2.3 Hz, H-2'), 7.15 (1H, d, 133.3 (C-3),
= 8.2 Hz, H-5'), 6.82 (1H, Hz, H-6); 13C-NMR (CD3OD, 125 MHz):
s, H-3), 6.81 (1H, d, = 2.3 Hz, H-8), 6.48 (1H, d, 124.7 (C-4), 103.2 (C-1'), 76.9 (C-5'), 76.8 (C-3'), 73.9
2.3 Hz, H-6), 5.05 (1H, d, = 7.0 Hz, H-1''), 4.17 (1H, (C-2'), 70.5 (C-4'), 69.3 (C-1), 61.6 (C-6'), 27.6 (C-2),
d,
= 7.6 Hz, H-1'''), 3.88 (1H, s, -OCH3); 13C-NMR 20.3 (C-5), 13.4 (C-6).
(DMSO-d6, 125 MHz): 182.6 (C-4), 164.9 (C-7), 163.7
(C-2), 161.8 (C-5), 157.7 (C-9), 152.0 (C-4'), 147.5 (C-
3'), 123.6 (C-1'), 119.6 (C-6'), 113.9 (C-2'), 112.9 (C-5'), Colorless amorphous solid; [α D
106.1 (C-3), 104.8 (C-10), 104.5 (C-1'''), 100.6 (C-1''), EtOH); FAB-MS m/z: 261 [M-H]−; H-NMR (CD3OD,
100.4 (C-8), 95.5 (C-6), 77.2 (C-5''), 76.9 (C-3''), 76.3 (C- 500 MHz): 5.75 (1H, m, H-4), 5.60 (1H, m, H-3), 4.29
3'''), 74.1 (C-2'''), 73.8 (C-2''), 70.2 (C-4''), 70.1 (C-4'''), (1H, d, = 7.5 Hz, H-1'), 2.04 (1H, q, = 7.0 Hz, H-2),
69.1 (C-6''), 66.3 (C-5'''), 56.6 (OCH3). 1.42 (1H, quintet, = 7.0 Hz, H-5), 0.92 (1H, t, = 7.6
Hz, H-6); 13C-NMR (CD3OD, 125 MHz):
134.7 (C-3),
O
-
β
-D-xylopyranosyl-(1'''
→
6'')-β
]
EtOH); FAB-MS m/z: 261 [M-H]−; H-NMR (CD3OD,
5.45 (1H, m, H-4), 5.37 (1H, m, H-3), 4.26
= 7.0 Hz, H-2),
= 7.6
δ
δ
J
J
J
J
J
J
J
δ
J
J =
J
J
δ
(E)-3-Hexenyl-β-D-glucopyranoisde (13)
25
]
−
28.3o (c 0.48 in
1
δ
J
J
J
J
δ
p
-Hydroxybenzoic acid (8)
126.2 (C-4), 101.8 (C-1'), 76.9 (C-5'), 76.8 (C-3'), 73.9
White amorphous powder; mp 211-212oC; EI-MS m/z: (C-2'), 70.5 (C-4'), 69.3 (C-1), 61.6 (C-6'), 34.3 (C-2),
138 [M]+; H-NMR (CD3OD, 500 MHz):
δ
7.87 (2H, d, 22.2 (C-5), 12.8 (C-6).
= 8.8 Hz, H-3, 5);
170.1 (C=O), 162.1 (C-
1
J
= 8.8 Hz, H-2, 6), 6.82 (2H, d,
J
13C-NMR (CD3OD, 125 MHz):
δ
(Z
)-3-Hexenyl-
glucopyranoisde (14)
Colorless amorphous solid; [α D
EtOH); FAB-MS m/z: 395 [M-H]−; H-NMR (CD3OD,
α
-L-arabinopyranosyl-(1''
→6')-β-D-
4), 131.8 (C-2, 6), 122.9 (C-1), 5), 115.6 (C-3, 5).
38.0o (c 0.48 in
25
]
−
1
Protocatechuic acid (9)
White amorphous powder; mp 211-212oC; EI-MS m/z: 500 MHz):
δ
5.45 (1H, m, H-4), 5.37 (1H, m, H-3), 4.31
= 7.0 Hz, H-1''), 4.26 (1H, d, = 7.6 Hz, H-1'),
= 8.0, 1.8 Hz, H-6), 2.38 (1H, q, = 7.0 Hz, H-2), 2.08 (1H, quintet, = 7.0
= 8.0 Hz, H-5); 13C-NMR (CD3OD, 125 Hz, H-5), 0.97 (1H, t, = 7.6 Hz, H-6); 13C-NMR (CD3OD,
169.1 (C=O), 150.3 (C-4), 144.9 (C-3), 122.7 125 MHz): 133.3 (C-3), 124.7 (C-4), 103.9 (C-1''),
154 [M]+; H-NMR (CD3OD, 500 MHz):
δ
7.43 (1H, d, (1H, d,
J
J
1
J
= 1.8 Hz, H-2), 7.40 (1H, dd,
6.79 (1H, d,
MHz):
J
J
J
J
J
δ
δ
(C-6), 122.1 (C-1), 116.6 (C-2), 114.6 (C-5).
103.2 (C-1'), 76.7 (C-5'), 75.7 (C-3'), 73.9 (C-2'), 73.0 (C-
3''), 71.2 (C-2''), 70.4 (C-4'), 69.4 (C-1), 68.2 (C-6', 4''),
65.5 (C-5''), 27.6 (C-2), 20.3 (C-5), 13.4 (C-6).
Caffeic acid (10)
White amorphous powder; mp 193-194oC; EI-MS m/z:
180 [M]+; H-NMR (CD3OD, 500 MHz):
δ
7.52 (1H, d, Oct-1-en-3-yl-
α
-L-arabinopyranosyl-(1''
→
6')-
J = 8.2 Hz, Colorless gum; [α] −
27.0o (c 0.3 in MeOH); FAB-MS
D
β-D-glu-
1
J
= 15.8 Hz, H-7), 7.03 (1H, d,
(1H, dd, = 8.2, 2.3 Hz, H-6), 6.78 (1H, d,
H-5), 6.23 (1H, d,
125 MHz):
J = 2.3 Hz, H-2), 6.93 copyranoisde (15)
25
J
J
= 15.8 Hz, H-8); 13C-NMR (CD3OD, m/z: 445 [M+Na]+; 1H-NMR (CD3OD, 500 MHz):
5.86
169.8 (C-9), 148.2 (C-4), 145.6 (C-7), 145.6 (1H, m, H-2), 5.22 (1H, brd, = 17.6 Hz, H-1a), 5.10
(C-3), 126.7 (C-1), 121.6 (C-6), 115.3 (C-5), 114.5 (C-8), (1H, d, = 10.5 Hz, H-1b), 4.33 (1H, d, = 6.4 Hz, H-
1''), 4.32 (1H, d, = 8.2 Hz, H-1'), 4.12 (1H, q, = 7.0
δ
δ
J
J
J
113.9 (C-2).
J
J
Hz, H-3), 1.66 (1H, m, H-4), 1.52 (1H, m, H-4), 1.30-
6-Hydroxy-3,4-dihydro-1-oxo-β-carboline (11)
1.40 (3H, m, H-5, 6, 7); 13C-NMR (CD3OD, 125 MHz):
δ
Colorless gum; mp 182-184oC; FAB-MS m/z: 203
139.7 (C-2), 114.9 (C-1), 103.7 (C-1''), 102.2 (C-1'),
76.7 (C-3'), 75.7 (C-5'), 74.1 (C-2'), 73.0 (C-3''), 71.2 (C-
= 2.5 Hz, H-5), 6.84 (1H, 2''), 70.4 (C-4'), 68.1 (C-6'), 68.0 (C-6', 4''), 65.2 (C-5'')
= 9.0, 2.5 Hz, H-7), 3.61 (1H, t, = 7.0 Hz, H-3),
2.94 (1H, t,
= 7.0 Hz, H-4); 13C-NMR (CD3OD, 125 Benzyl-
MHz): 163.9 (C-1), 151.0 (C-6), 133.1 (C-8a) 126.8 (C- noside (16)
[M+H]+; 1H-NMR (CD3OD, 500 MHz):
= 9.0 Hz, H-8), 6.90 (1H, d,
d,
δ 7.27 (1H, d, J
J
J
J
J
β-D-apiofuranosyl-(1''→6')-β-D-glucopyra-
δ
9a), 125.9 (C-4b), 119.1 (C-4a), 115.7 (C-7), 112.9 (C-8), Colorless gum; FAB-MS m/z: 425 [M+Na]+; H-NMR
1

A New Flavonol Glycoside from Hylomecon vernalis
419
(CD3OD, 500 MHz):
(1H, d, = 2.3 Hz, H-1''), 4.88 (1H, d,
7a), 4.65 (1H, d, = 11.7 Hz, H-7b), 4.32 (1H, d,
8.2 Hz, H-1'); 13C-NMR (CD3OD, 125 MHz):
137.8,
128.1, 128.0, 127.5 (phenyl), 109.9 (C-1''), 102.0 (C-1), Aryl-
79.4 (C-3''), 76.8 (C-3', 2''), 75.8 (C-5'), 73.9 (C-4''), 73.8 Colorless gum; FAB-MS m/z: 301 [M+H]+; H-NMR
(C-2'), 70.6 (C-7, 4'), 67.5 (C-6'), 64.4 (C-5''). (CD3OD, 500 MHz): 7.06 (2H, d, = 8.2 Hz, H-2, 6),
6.70 (1H, d, = 8.2 Hz, H-3, 5), 4.28 (1H, d, = 8.2
-D-gluco- Hz, H-1'); 13C-NMR (CD3OD, 125 MHz):
155.6(C-4),
129.7 (C-2, 6), 129.6 (C-1), 114.9 (C-3, 5), 103.2(C-1'),
Colorless gum; FAB-MS m/z: 403 [M+H]+; H-NMR 76.9 (C-3'), 76.8 (C-5'), 73.9 (C-2'), 70.9 (C-7), 70.5 (C-
(CD3OD, 500 MHz): 7.26-7.43 (5H, m, phenyl), 4.90 4'), 61.6 (C-6').
(1H, d, = 11.7 Hz, H-7a), 4.66 (1H, d, = 11.7 Hz, H-
7b), 4.36 (1H, d, = 8.2 Hz, H-1'), 4.34 (1H, d, = 6.4
Hz, H-1''); 13C-NMR (CD3OD, 125 MHz):
137.9,
δ
7.25-7.43 (5H, m, phenyl), 5.05 75.8 (C-5'), 73.8 (C-2'), 73.0 (C-3''), 71.2 (C-2''), 70.6
= 11.7 Hz, H- (OCH2CH2Ph), 70.3 (C-2''), 68.3 (C-4''), 68.2 (C-6'), 65.7
(C-5''), 36.1 (CH2CH2Ph).
J
J
J
J =
δ
β-D-glucopyranoside (21)
1
δ
J
J
J
Benzyl-
pyranoside (17)
α
-L-arabinopyranosyl-(1''
→6')-β
δ
1
δ
J
J
J
J
O-deacetylation of compound 1
δ
A clear stock solution of the G/GHNO3 reagent was
128.1, 128.0, 127.5 (phenyl), 104.0 (C-1''), 102.2 (C-1'), prepared by dissolving guanidinium nitrate (6 mg) in
76.8 (C-3'), 75.8 (C-5'), 73.9 (C-2'), 73.0 (C-3''), 71.2 (C- MeOH/CH2Cl2 (10 mL, 9:1) and adding MeONa (1 mL,
2''), 70.7 (C-7), 70.6 (C-2''), 68.3 (C-4''), 68.2 (C-6'), 1 M). Compound
65.5(C-5''). was treated and the solution was stirred at room
temperature for 1 h. When the -deacetylation was
1 (5 mg) in the stock solution (1 mL)
O
Benzyl-
noside (18)
β
-D-xylopyranosyl-(1''
→
6')-
β
-D-glucopyra- complete, the mixture was neutralized by addition of
Amberlite IR 120 H+ and the solvent was removed.
Colorless gum; FAB-MS m/z: 403 [M+H]+; H-NMR The residue was purified by HPLC [MeOH-H2O (45:55,
1
(CD3OD, 500 MHz):
(1H, d, = 11.5 Hz, H-7a), 4.66 (1H, d,
7b), 4.35 (1H, d,
= 8.0 Hz, H-1', 1''); 13C-NMR (CD3OD,
125 MHz): 137.9, 128.1, 128.0, 127.5 (phenyl), 104.4
(C-1''), 102.2 (C-1'), 76.8 (C-3'), 76.6 (C-5'), 75.9 (C-3''), d6):
73.9 (C-2''), 73.8 (C-2'), 70.7 (C-7), 70.4 (C-4''), 70.0 (C- Hz, H-6'), 7.54 (1H, d,
4'), 68.7 (C-6'), 65.7 (C-5''). = 8.8 Hz, H-5'), 6.38 (1H, s, H-8), 6.18 (1H, s, H-6), 5.26
(1H, d, = 7.6 Hz, H-1''), 4.06 (1H, = 6.4 Hz, H-1''').
δ
7.24-7.43 (5H, m, phenyl), 4.90 v/v)] to give 1a (2 mg). The structure was identified by
= 11.5 Hz, H- 1H-NMR and MS spectral analysis.
Compound 1a: Yellow solid; mp 252-253oC; ESI-MS
(rel. int.): 595 [M – H]−;1H-NMR (500 MHz, DMSO-
12.45 (1H, brs, 5-OH), 7.68 (1H, dd, = 8.8, 2.3
= 2.3 Hz, H-2'), 6.82 (1H, d,
J
J
J
δ
m/z
δ
J
J
J
J
J
2-Phenylethyl-
β
-D-apiofuranosyl-(1''
→
6')-
β
-D-glu-
copyranoside (19)
Acid hydrolysis of compound 1
Compound 1a (1 mg) was heated in an ampoule with
Colorless gum; FAB-MS m/z: 439 [M+Na]+; H-NMR
1
(CD3OD, 500 MHz):
(1H, d, = 2.3 Hz, H-1'), 4.24 (1H, d,
4.03 (1H, dt, = 9.9, 7.6 Hz, OCHbHCH2Ph), 3.76 (1H, EtOAc solvent was removed under reduced pressur
dd, = 11.1, 5.8 Hz, OCHHaCH2Ph), 2.93 (2H, t,
7.6 Hz, CH2CH2Ph); 13C-NMR (CD3OD, 125 MHz):
δ
7.16-7.24 (5H, m, phenyl), 5.00 1 mL of aq. 1.5 M HCl at 80oC for 2 h. After cooling, the
= 7.6 Hz, H-1), reaction mixture was extracted with EtOAc. The
J
J
J
J
J
=
and the residue was purified by HPLC [MeOH-H2O
δ
(50:50, v/v) to give 1b. The structure was identified by
138.9, 128.8, 128.3, 126.0 (phenyl), 109.8 (C-1''), 103.3 1H-NMR and MS spectral analysis. The aqueous layer
(C-1'), 79.3 (C-3''), 76.8, (C-3', 2''), 76.8 (C-1), 75.7 (C- of compound 1a were subjected to HPLC analysis
5'), 73.9 (C-4''), 73.8 (C-2'), 70.6 (OCH2CH2Ph), 70.6 [CH3CN-H2O (85:15, v/v), 0.8 mL/min] and the sugar
(C-4'), 67.5 (C-6'), 64.5 (C-5''), 36.1 (CH2CH2Ph).
was confirmed as D-galactose and L-arabinose by
comparison of their retention time and optical rotation
-D- with those of authentic samples. [Rt : 10.2 min (L-
arabinose, positive optical rotation), 12.8 (D-galactose,
2-Phenylethyl-
α
-L-arabinopyranosyl-(1''
→
6')-
β
glucopyranoside (20)
Colorless gum; FAB-MS m/z: 417 [M+H]+; H-NMR positive optical rotation)]
1
(CD3OD, 500 MHz):
(1H, d, = 7.6 Hz, H-1'), 4.30 (1H, d,
4.08 (1H, dt, = 9.9, 7.6 Hz, OCHbHCH2Ph), 3.77 (1H, (1H, dd,
m, OCHHaCH2Ph), 2.93 (2H, t, = 7.6 Hz, CH2CH2Ph); H-6'), 6.90 (1H, d,
13C-NMR (CD3OD, 125 MHz):
138.9, 128.8, 128.2, 6.18 (1H, s, H-6).
126.0 (phenyl), 103.9 (C-1''), 103.2 (C-1'), 76.8 (C-3'),
δ
7.14-7.26 (5H, m, phenyl), 4.36
Compound 1b: Yellow solid; mp 312-313oC; ESI-MS
: 303 [M+H]+; 1H-NMR (500 MHz, CD3OD):
7.66
= 8.2, 2.0 Hz, H-2'), 7.58 (1H, d, = 2.0 Hz,
= 8.2 Hz, H-5'), 6.38 (1H, s, H-8),
J
J
= 7.6 Hz, H-1),
m
/z
δ
J
J
J
J
δ
J

420
S. Y. Lee et al.
8.8, 2.3 Hz), 7.62 (d,
J = 2.3 Hz) and 6.83 (d, J = 8.8
Test for cytotoxicity in vitro
Sulforhodamin B bioassays (SRB) were used as Hz) were assigned to three aromatic protons of the
cytotoxicity screening methods (Skehan et al., 1990). ABX system of the B ring, with two meta-coupled
Cytotoxicity assays for each compound were perform- doublets at
ed in vitro against four cultured human tumor cell ring. The 13C-NMR spectra of
lines at the Korea Research Institute of Chemical 178.1. The aglycone of was identified as quercetin
Technology. The cell lines used were A549 (non-small (Young et al., 1991). In addition, in the H-NMR
δ
H 6.42, and 6.20 (d,
J
= 2.0 Hz) for the A
1
showed a C=O at δC
1
1
cell lung adenocarcinoma), SK-OV-3 (ovarian cancer spectrum of
cells), SK-MEL-2 (skin melanoma), and HCT15 (colon appeared at
1
the signals of the two anomeric proton
δH 5.26 (d, = 7.6 Hz), and at H 4.06 (d,
J
δ
cancer cells). Doxorubicin was used as a positive control.
J
= 6.4 Hz) with characteristic coupling constants of a
- and
-configuration, respectively. In the 13C-NMR
spectrum of , the signals at C 102.6 and 103.5 corres-
ponded to the galatosyl and arabinosyl anomeric
β
α
1
δ
RESULTS AND DISCUSSION
Compounds
1H-, 13C-NMR, and MS spectra of these compounds HMBC experiment, in which the long-range correla-
with the literatures. They were identified as quercetin tions were observed between the H-1'' ( 5.26) of D-
3- -[2'''- -acetyl- -L-arabinopyranosyl]- (1''' 6'')- -D- galatose and the C-3 ( 134.2) of aglycone, and H-1''' (
galactopyranoside ( ) (Yoshitama et al., 1997), querce- 4.06) of L-arabinose and C-6'' of D-galatose (Takemura
tin 3- -L-arabinopyranosyl-(1''' 6'')- showed
-D-galacto- et al., 2002). The 1H- and 13C-NMR spectra of
pyranoside ( ) (Takemura et al., 2002), quercetin 3- also acetyl group signals at H 1.98 (3H, s) and C 21.6
-D-galactopyranoside ( ) (Lee et al., 2002), kaemp- and 170.6, respectively. The H-4''' ( 4.54) and C-4''' (
ferol 3,7- -L-dirhamnopyranoside ( ) (Mulinacci et 71.5) signals of appeared more downfield than those
al., 1995), diosmetin 7- -D-glucopyranoside ( ) (Son of , H-4''', 3.49; C-4''', 68.0). The acetyl group
et al., 1994), diosmetin 7- -D-xylopyranosyl-(1''' 6'')- linkage was confirmed by HMBC data, where a correla-
-D-glucopyranoside ( ) (Park et al., 2009), -hydroxy- tion was observed between the H-4''' ( 4.54) of L-
benzoic acid ( ) (Lee et al., 2008), protocatechuic acid arabinose and the C=O ( 170.6) of the acetyl group as
) (Sun et al., 2006), caffeic acid (10) (Lee et al., 2009), shown in Fig. 1. This indicated the presence of an
6-hydroxy-3,4-dihydro-1-oxo- -carboline (11) (Julia et acetyl group at C-4''' in . The -deacetylation of
al, 1973), ( )-3-hexenyl- -D-glucopyranoside (12), ( )- afforded quercetin 3- -L-arabinopyranosyl-(1 6)-
2-hexenyl- -D-glucopyranoside (13) (Mizutani et al., D-galactopyranoside (1a), which was identified by co-
1988), ( )-3-hexenyl- -L-arabinopyranosyl-(1'' 6')- TLC (Rf, 0.25, CHCl3-MeOH-H2O = 9:4:0.5) with and
D-glucopyranoside (14) (Kishida et al., 2005), oct-1- by its 1H-NMR (Takemura et al., 2002). Acid hydroly-
en3yl- -L-arabinopyranosyl-(1'' 6')- -D-glucopyrano- sis of quercetin 3- -L-arabinopyranosyl-(1 6)- -D-
side (15) (Wang et al., 1998), benzyl- -D-apiofuranosyl- galactopyranoside yielded the aglycone, quercetin and
(1'' 6')- -D-glucopyranoside (16) (Wang et al., 1998), a sugar (Takemura et al., 2002). The aglycone was
benzyl- -L-arabinopyranosyl-(1'' 6')- -D-glucopyra-
confirmed by comparison of its 1H-NMR, and ESI-MS
noside (17) (Rosa et al., 1996), benzyl- -D-xylopyrano- data with literature values (Young et al., 1991), and
syl-(1'' 6')- -D-glucopyranoside (18) (Otsuka et al., the sugar was identified by co-TLC with authentic
1990), 2-phenylethyl- -D-apiofuranosyl-(1'' 6')- -D-glu- sugars (CHCl3-MeOH-H2O = 6:4:1, Rf value D-galatose
copyranoside (19), 2-phenylethyl- -L-arabinopyrano- 0.29, L-arabinose 0.55), and HPLC analysis (Takemura
syl-(1'' 6')- -D-glucopyranoside (20) (Ma et al., 2001), et al., 2002). Thus, the structure of 1 was determined
and aryl- -D-glucopyranoside (21) (Schwab et al., as Quercetin 3- -[4'''- -acetyl- -L-arabinopyranosyl]-
2-21 were identified by comparing the carbon. The glycosidic position was established by an
δ
O
O
α
→
β
δ
δ
2
O
-
α
→
β
1
3
O-
δ
δ
β
4
δ
δ
O
-
α
5
1
δ
O
-
β
6
3
(3
δ
O
-β
→
β
7
p
δ
8
δ
(9
β
1
O
1
β-
Z
β
E
O-α
→
β
Z
α
→
β-
3
α
→
β
O
-
α
→
β
β
→
β
α
→
β
β
→
β
β
→
β
α
→
β
β
O
O
α
1988). Compounds
from this plant.
2-21 were isolated for the first time
25
Compound
1 was isolated as a yellow solid, [α]
D
−
80o (c 0.08, MeOH). The molecular formula C28H30O17
was determined by the HR-ESI-MS m/z 661.1375
[M+Na]+ (calcd. 661.1375). The IR spectrum showed
the bands of a hydroxyl group at 3401 cm−1 and
α,β-
1
unsaturated carbonyl group at 1646 cm−1. In the H-
NMR spectra of , the typical flavonoid signals were
observed. The proton signal at δH 12.61 showed an
aromatic C5-OH. The proton signals at H 7.77 (dd,
1
Fig. 1. Key HMBC correlations (H
→ C) of 1
δ
J =

A New Flavonol Glycoside from Hylomecon vernalis
421
Ma, S. J., Mizutani, M., Hiratake, J., Hayashi, K. Yagi, K.,
Watanabe, N., and Sakata, K., Substrate specificity of β-
(1'''
→
6'')-
β
-D-galactopyranoside.
The isolated compounds,
2
-
21 were tested for cyto-
primeverosidase, a key enzyme in aroma formation dur-
ing oolong tea and black tea manufacturing. Biosci.
Biothechnol. Biochem., 65, 2719-2729 (2001).
Mizutani, K., Yuda, M., Tanaka, O., Saruwatari, Y. I., Fuwa,
T., Jia, M. R., Ling, Y. K., and Pu, X. F., Chemical studies
on chinese traditional medicine, Dangshen. I. isolation of
toxicity against four human tumor cells in vitro using
the SRB assay. Of them the compound 11 exhibited
weak cytotoxicity against A549, SK-OV-3, SK-MEL-2,
and HCT15 cell lines with the IC50 values of 62.95,
60.04, 62.56, and 48.02
other compounds showed little cytotoxicity (IC50 > 100
M). IC50 values for the cytotoxicity of the control
µM, respectively, and the
(Z)-3- and (E)-2-Hexenyl β-D-Glucosides. Chem. Pharm.
µ
Bull., 36, 2689-2690 (1988).
Mulinacci, N., Vincieri, F. F., Baldi, A., Bambagiotti-Alberti,
M., Sendl, A., Wagner, H., Flavonol glycoside from Sedum
compound, doxorubicin, against A549, SK-OV-3, SK-
MEL-2, and HCT15 cell lines were 0.039, 0.081, 0.074,
and 0.076 µM, respectively.
telephium subspecies maximum leaves. Phytochemistry
,
38, 531-533 (1995).
Otsuka, H. Takeda, Y., and Yamasaki, K., Xyloglucosides of
benzyl and phenethyl alcohols and -hex-3-en-1-ol from
ACKNOWLEDGEMENTS
Z
This study was supported by the Basic Science
Research Program through the National Research
Foundation of Korea (NRF) funded by the Ministry of
Education, Science and Technology (20110028285).
The authors would like to thank Mr. Do Kyun Kim,
Dr. Eun Jung Bang, and Dr. Jung Ju Seo at the Korea
Basic Science Institute for the NMR and MS spectra
measurements.
leaves of Alangium plataniforium Var. Trilobum. Phyto-
chemistry, 29, 3681-3683 (1990).
Park, H. Y., Kim, H. K., Jeon, S. H., Kim, S. H., Chun, W. J.,
Lim, S. S., Kim, M. J., and Kwon Y. S., Alodse reductase
inhibitor from the leaves of Salix hulteni. J. Korean Soc.
Appl. Biol. Chem., 52, 493-497 (2009).
Rosa, S. D., Giulio, A. D., and Tommonaro, G., Aliphatic and
aromatic glycosides from the cell cultures of Lycopersicon
esculentum
Schwab, W. and Schreier, P., Aryl
.
Phytochemistry, 42(4), 1031-1034 (1996).
-D-glucosides from
β
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