Phenolic compounds from the roots of Brassica rapa ssp. campestris

Article abstract of DOI:10.1007/s10600-013-0763-1

A new benzyl α-D-fructofuranoside (3), along with six known phenol compounds, benzyl-β-D-glucopyranoside (1), dihydrosyringin (2), syringin (4), triandrin (5), phillyrin (6), and neoolivil-4-O-β-D-glucopyranoside (7), was isolated from the roots of Brassica rapa ssp. campestris L. for the first time. The structures of the compounds were established on the basis of NMR, MS, and IR spectroscopic data.

Full text of DOI:10.1007/s10600-013-0763-1

Chemistry of Natural Compounds, Vol. 49, No. 5, November, 2013 [Russian original No. 5, September–October, 2013]
PHENOLIC COMPOUNDS FROM THE ROOTS
OF Brassica rapa ssp. campestris
1
1
1
Qian Wu, Myun-Ho Bang, Jin-Gyeong Cho,
UDC 547:635.1:604
2
3
4
Dae-Young Lee, Kyung-Tae Lee, Hae-Gon Chung,
Myung-Sook Choi, Tae-Sook Jeong, Eun-Mi Ahn,
Geum-Soog Kim, and Nam-In Baek
5
6
7
2
1*
A new benzyl ꢀ-D-fructofuranoside (3), along with six known phenol compounds, benzyl-ꢁ-D-glucopyranoside
(1), dihydrosyringin (2), syringin (4), triandrin (5), phillyrin (6), and neoolivil-4-O-ꢁ-D-glucopyranoside
(7), was isolated from the roots of Brassica rapa ssp. campestris L. for the first time. The structures of the
compounds were established on the basis of NMR, MS, and IR spectroscopic data.
Keywords: Brassica rapa ssp. campestris, benzyl ꢀ-D-fructofuranoside, benzyl-ꢁ-D-glucopyranoside,
dihydrosyringin, neoolivil-4-O-ꢁ-D-glucoside, phillyrin, syringin, triandrin.
Brassica rapa ssp. campestris L., a turnip, is a vegetable commercially cultivated in the west coast region of Ganghwa
Island in Korea. The plant is an edible root vegetable with a conical shape and deep purple color and is well known for its
ability to alleviate jaundice, combat liver diseases, relieve hangover and chronic constipation, and improve kidney function.
Turnips are included in many food products such as Kimchi, a traditional Korean fermented vegetable dish. Some chemical
constituents such as indole alkaloids [1, 2], sterols [1], and fatty acids [3], as well as ethanolic extracts from the roots of
B. rapa ssp. campestris, have previously been reported to modulate the deleterious effects of diabetes [4], to prevent high-fat
diet-induced obesity [5], and to prevent cisplatin-induced nephrotoxicity [6]. Our continuing research was carried out to
search for other phytochemical constituents from the roots of B. rapa ssp. campestris.
The roots of B. rapa ssp. campestris were extracted with 95% aqueous EtOH, and the concentrated extract was
partitioned with EtOAc, n-BuOH, and H O. From the n-BuOH fraction, seven phenolic compounds were isolated through
2
repeated SiO , ODS, and Sephadex LH-20 column chromatographies. Six known compounds were identified, benzyl
2
–5
–5
–6
ꢁ-D-glucopyranoside (yield: 5.3 ꢂ 10 %, 1) [7], dihydrosyringin (yield: 1.9 ꢂ 10 %, 2) [8], syringin (yield: 9.1 ꢂ 10 %, 4)
[9, 10], triandrin (yield: 1.3 ꢂ 10 %, 5) [9], phillyrin (yield: 1.8 ꢂ 10 %, 6) [11–13], and neoolivil-4-O-ꢁ-D-glucopyranoside
(yield: 1.3 ꢂ 10 %, 7) [14, 15], through comparison of their spectroscopic data with those of the literature.Although they are
–5
–5
–5
known compounds, all of them are reported for the first time from this plant, even the entire Brassicaceae family.
1) Graduate School of Biotechnology, Department of Oriental Medicinal Materials and Processing, Kyung-Hee
University, Yongin 446-701, South Korea, e-mail: nibaek@khu.ac.kr; 2) Department of Herbal Crop Research, National Institute
of Horticultural & Herbal Science, RDA, Eumseong 369-873, South Korea; 3) Department of Biochemistry, College of Pharmacy,
Kyung-Hee University, Seoul 130-701, South Korea; 4) Ganghwa Agricultural Research and Development Center, Incheon
417-833, South Korea; 5) Department of Food Science and Nutrition, Kyung-Pook National University, Daegu 702-701,
South Korea; 6) National Research Laboratory of Lipid Metabolism &Atherosclerosis, Korea Research Institute of Bioscience
and Biotechnology, Daejeon 305-333, South Korea; 7) Department of Herbal Foodceutical Science, Daegu-Haany University,
Gyeongsan 712-715, South Korea. Published in Khimiya Prirodnykh Soedinenii, No. 5, September–October, 2013, pp. 734–737.
Original article submitted September 19, 2012.
852
0009-3130/13/4905-0852 02013 Springer Science+Business Media New York

5
3
1
O
1'
CH OH
2
O
6'
OH
3'
5'
HO
OH
3
Fig. 1. The one-way arrows indicate the long-
range correlations from hydrogen to carbon
signals in the gHMBC spectrum.
–6
20
Compound 3 (yield: 5.4 ꢂ 10 %) is a colorless syrup, mp 88–89ꢃC, [ꢀ] +44.9ꢃ (c 2.0, H O). It showed absorbance
D
2
–1
–1
–
bands due to hydroxy (3360 cm ) and olefine (1550 cm ) groups in the IR spectrum. The molecular ion peak [M – H] was
detected at m/z 269 in the negative FAB-MS spectrum, and the molecular formula C H O was determined by the molecular
13 18
6
–
ion peak m/z 269.1020 [M – H] (calcd for C H O , 269.1025) in the negative HR-FAB-MS. In the PMR (400 MHz,
13 17
6
methanol-d , ꢄ, ppm) spectrum, five olefine methine proton signals at ꢄ 7.38 (2H, dd, J = 8.8, 1.2 Hz, H-2, 6), 7.30 (2H, dd,
4
J = 8.8, 7.2 Hz, H-3, 5), and 7.23 (1H, tt, J = 7.2, 1.2 Hz, H-4) indicating a monosubstituted benzene ring structure, an
oxygenated methylene proton signals at ꢄ 4.71 (1H, d, J = 11.6 Hz, H-7a) and 4.58 (1H, d, J = 11.6 Hz, H-7b), and sugar moiety
proton signals at ꢄ 4.13 (1H, d, J = 4.4 Hz, H-3ꢅ), 3.92 (1H, dd, J = 7.2, 4.4 Hz, H-4ꢅ), 3.90 (1H, ddd, J = 7.2, 4.4, 2.8 Hz,
H-5ꢅ), 3.80 (1H, d, J = 12.0 Hz, H-1ꢅa), 3.77 (1H, dd, J = 12.8, 2.8 Hz, H-6ꢅa), 3.72 (1H, d, J = 12.0 Hz, H-1ꢅb), and 3.64 (1H,
13
dd, J = 12.8, 4.4 Hz, H-6ꢅb) revealed the presence of a fructose. In the C NMR (100 MHz, methanol-d , ꢄ, ppm) spectrum,
4
one olefine quaternary carbon signal at ꢄ 140.2 (C-1), five olefine methine carbon signals at ꢄ 129.2 (C-3 and C-5), 128.8
(C-2 and C-6), and 128.3 (C-4), and an oxygenated methylene carbon signal at ꢄ 64.6 (C-7) confirmed the presence of a benzyl
alcohol moiety. An oxygenated quaternary carbon signal at ꢄ 109.3 (C-2ꢅ), three oxygenated methine carbon signals at ꢄ 84.2
(C-5ꢅ), 83.5 (C-3ꢅ), and 78.7 (C-4ꢅ), and two oxygenated methylene carbon signals at ꢄ 62.7 (C-6ꢅ) and 61.8 (C-1ꢅ) confirmed
the presence of an ꢀ-D-fructose moiety [16]. gHMBC was carried out in order to determine the positions of key signals
(Fig. 1). In the gHMBC spectrum, the oxygenated methylene proton signals at ꢄ 4.71 (H-7a) and 4.58 (H-7b) showed cross
peaks with the olefine quaternary carbon signal at ꢄ 140.2 (C-1), the olefine methine carbon signals at ꢄ 128.8 (C-2, C-6), and
the oxygenated quaternary carbon signal at ꢄ 109.3 (C-2ꢅ), indicating that the oxygenated methylene carbon C-7 was located
between C-1 of the benzene ring and C-2ꢅ of the fructose via an ether bond. The presence of fructose was also confirmed by
TLC comparison with an authenic fructose after acid hydrolysis. Thus, the structure was determined as benzyl-ꢀ-D-
fructofuranoside. Even though it has been previously reported as a synthetic compound, there are no detailed reported NMR
data for benzyl-ꢀ-D-fructoside. This is the first report of the isolation of compound 3 from the natural source and its identification
using spectroscopic analysis.
OH
OCH
3
O
3
HO
HO
OH
O
4
OH 1''
O
1
HO
HO
O
O
9'
H7
9
H
OH
8
OH
8'
1'
OCH
3
3
7'
O
5
3'
6
9
4'
9'
8'
OCH
HO
OH
8
1'
1
3'
H CO
OCH
3
3
4
3
7
OH
7'
O
O
HO
HO
4'
O
OH
7
OH
853

EXPERIMENTAL
General. Optical rotation was measured on a JASCO P-1010 digital polarimeter (Tokyo, Japan). IR spectra were
obtained using a PerkinElmer Spectrum One FT-IR spectrometer (Buckinghamshire, England). EI-MS, FAB-MS, and
1
13
HR-FAB-MS were conducted on a JEOL JMSAX-700 mass spectrometer (Tokyo, Japan). H NMR (400 MHz) and C NMR
(100 MHz) spectra were recorded on a Varian Unity Inova AS-400 FT-NMR spectrometer (Palo Alto, CA, USA). SiO (Kieselgel 60,
2
Merck, Darmstadt, Germany), octadecyl silica gel (ODS) (LiChroprep RP-18, 40–60 m, Merck), Diaion HP-20 (Samchun,
Korea), and Sephadex LH-20 (Amersham Pharmacia Biotech, Uppsala, Sweden) resins were used for column chromatography
(CC). TLC analysis was carried out using Kieselgel 60 F and RP-18 F
(Merck) plates. The compounds were detected
254
254S
using a Spectroline ENF-240 C/F UV lamp (Spectronics Corporation, Westbury, NY, USA).
Plant Material. Roots of B. rapa ssp. campestris were provided by the GanghwaAgricultural R & D Center, Incheon,
Korea, in May 2009 and were positively identified by Dr. Hae-Gon Chung, Ganghwa Agricultural R & D Center. A voucher
specimen (KHU090512) was deposited at the Laboratory of Natural Products Chemistry, Kyung Hee University, Yongin,
Korea.
Isolation of Phenolic Compounds. Fresh turnip roots (77 kg) were chopped and extracted with 95% EtOH (770.0 L ꢂ 2)
at room temperature for 24 hours. The extracts were filtered through filter paper and concentrated in a rotary vacuum evaporator
to yield a dark brown mass (295 g). The extract was suspended in 8 L water and successively partitioned with EtOAc (8.0 L ꢂ 2)
and n-BuOH (6.4 L ꢂ 2), yielding concentrated fractions of EtOAc (BRE, 39 g), n-BuOH (BRB, 117 g), and H O (139 g),
2
sequentially. The n-BuOH fraction (BRB, 117 g) was fractionated into 14 fractions (BRB-1 to BRB-14) using Diaion HP-20
CC (10 ꢂ 45 cm) and eluted with H O (4.0 L)ꢆMeOH (2.0 L)ꢆacetone (4.0 L)ꢆH O (2.0 L). BRB-3 (340 mg, V /V
2
2
elute total
0.12–0.18) was subjected to ODS CC (4.0 ꢂ 7 cm) and eluted with MeOH–H O (1:2, 1.2 L) to get purified compound 1 [BRB-3-3,
2
41 mg, V /V 0.20 to 0.30; TLC (RP-18 F
) R 0.5, MeOH–H O 3:2]. BRB-4 (190 mg, V /V 0.19–0.23) was subjected to
e
t
254s
f 2 e t
ODS CC (3 ꢂ 6 cm) and eluted with MeOH–H O (2:3, 1 L) to yield purified compound 2 [BRB-4-7, 15 mg, V /V 0.67–0.79;
2
e
t
TLC (RP-18 F
) R 0.5, MeOH–H O 1:1]. BRB-6 (6.1 g, V /V 0.39–0.46) was subjected to a SiO CC (6 ꢂ 15 cm) and
254s
f 2 e t 2
eluted with CHCl –MeOH (6:1ꢆ2:1, each 8.0 L) and CHCl –MeOH–H O (6:4:1, 8.0 L) to yield 19 fractions (BRB-6-1 to
3
3
2
BRB-6-19). Fraction BRB-6-2 (282 mg, V /V 0.06–0.08) was further purified by successive chromatography on a Sephadex
e
t
LH-20 column (3 ꢂ 55 cm) and eluted with MeOH–H O (3:5ꢆ4:5, each 0.5 L) to obtain 10 fractions (BRB-6-2-1 to BRB-6-2-10).
2
The BRB-6-2-4 fraction (50 mg, V /V 0.14–0.18) was further purified by ODS CC (3 ꢂ 5 cm) and eluted with MeOH–H O
e
t
2
(1:5, 0.8 L) to yield purified compound 3 [BRB-6-2-4-8, 4 mg, V /V 0.27–0.36; TLC (RP-18 F
) R 0.5, MeOH–H O 1:1].
e
t
254s
f
2
BRB-6-5 (360 mg, V /V 0.11–0.18) was further separated by ODS CC (3 ꢂ 5 cm) and eluted with MeOH–H O (1:2, 2.0 L) to
e
t
2
obtain 10 fractions (BRB-6-5-1 to BRB-6-5-10). The BRB-6-5-3 fraction (51 mg, V /V 0.08–0.10) was further purified by
e
t
SiO CC (3 ꢂ 15 cm) and eluted with CHCl –MeOH–H O (22:3:1, 2.5 L) to yield purified compound 4 [BRB-6-5-3-8, 7 mg,
2
3
2
V /V 0.07–0.10; TLC (RP-18 F
) R 0.5, MeOH–H O 1:2]. The BRB-6-5-4 fraction (40 mg) was also further purified by
e
t
254s
f 2
SiO CC (3 ꢂ 12 cm) and eluted with CHCl –MeOH–H O (20:3:1, 2.0 L) to get purified compound 5 [BRB-6-5-4-12, 10 mg,
2
3
2
V /V 0.10–0.15; TLC (RP-18 F
) R 0.5, MeOH–H O 1:2]. BRB-7 (4.2 g, V /V 0.45–0.51) was separated by SiO CC
e
t
254s
f 2 e t 2
(3 ꢂ 5 cm) and eluted with CHCl –MeOH (14:1ꢆ12:1ꢆ8:1ꢆ5:1ꢆ3:1, each 1.0 L) to obtain 14 fractions (BRB-7-1 to
3
BRB-7-14). BRB-7-11 (61 mg, V /V 0.25–0.29) was further purified by ODS CC (3 ꢂ 5 cm) and eluted with MeOH–H O
e
t
2
(1:2, 2.0 L) to obtain purified compound 6 [BRB-7-11-8, 14 mg, V /V 0.66–0.76; TLC (RP-18 F
) R 0.35, MeOH–H O
e
t
254s
f
2
1:1]. The BRB-7-14 fraction (51 mg, V /V 0.31–0.33) was further purified by ODS CC (3 ꢂ 15 cm) and eluted with MeOH–
e
t
H O (1:3ꢆ2:1, 2 L) to obtain purified compound 7 [BRB-7-14-9, 10 mg, V /V 0.58–0.60; TLC (RP-18 F
) R 0.6,
2
e
t
254s
f
MeOH–H O 3:2].
2
20
D
Benzyl-ꢁ-D-glucopyranoside (1). Yellow crystals (MeOH), mp 176–177ꢃC (H O); [ꢀ]
–24.0ꢃ (c 0.1, H O).
2
2
+
UV (EtOH, ꢇ , nm): 236. Positive FAB-MS m/z 271 [M + H] . PMR (400 MHz, pyridine-d , ꢄ, ppm, J/Hz): 7.61 (2H, dd,
max
5
J = 8.4, 1.2, H-2, 6), 7.35 (2H, dd, J = 8.4, 7.2, H-3, 5), 7.21 (1H, m, H-4),4.62 (1H, d, J = 12.4, H-7a), 4.60 (1H, d, J = 7.6,
H-1ꢅ), 4.38 (1H, dd, J = 12.4, 2.0, H-6ꢅa), 4.28 (1H, d, J = 12.4, H-7b), 3.90 (1H, dd, J = 12.4, 4.8, H-6ꢅb), 4.05–3.55 (4H,
13
overlap, H-2ꢅ, H-3ꢅ, H-4ꢅ, H-5ꢅ). C NMR (100 MHz, pyridine-d , ꢄ, ppm): 138.5 (C-1), 128.1 (C-2, C-6), 127.9 (C-3, C-5),
5
126.3 (C-4), 103.3 (C-1ꢅ), 78.6 (C-3ꢅ), 78.4 (C-5ꢅ), 75.7 (C-2ꢅ), 72.0 (C-7), 71.3 (C-4ꢅ), 62.2 (C-6ꢅ).
20
Dihydrosyringin (2). White needlelike crystals (MeOH), mp 130–132ꢃC (H O); [ꢀ] –52.0ꢃ (c 0.5, MeOH).
2
D
+
–1
UV (MeOH, ꢇ , nm): 276. Positive FAB-MS m/z 375 [M + H] . IR (CaF , ꢈ, cm ): 3501, 1652. PMR (400 MHz, pyridine-d ,
max
2
5
ꢄ, ppm, J/Hz): 6.65 (2H, br.s, H-2, 6), 5.64 (1H, d, J = 7.8, H-1ꢅ), 4.33–4.23 (5H, overlap, sugar moiety), 3.86 (2H, t, J = 7.2,
13
H-9), 3.71 (6H, s, 3-OCH , 5-OCH ), 2.78 (2H, t, J = 6.4, H-7), 1.99 (2H, m, H-8). C NMR (100 MHz, pyridine-d , ꢄ, ppm):
3
3
5
854

153.2 (C-3, C-5), 138.7 (C-4), 133.8 (C-1), 106.8 (C-2, C-6), 104.9 (C-1ꢅ), 78.3 (C-3ꢅ), 78.0 (C-5ꢅ), 75.7 (C-2ꢅ), 71.2 (C-4ꢅ),
62.9 (C-6ꢅ), 61.1 (C-9), 56.3 (3-OCH , 5-OCH ), 35.2 (C-8), 32.8 (C-7).
3
3
20
Benzyl-ꢀ-D-fructofuranoside (3). Colorless syrup, mp 88–89ꢃC; [ꢀ] +44.9ꢃ (c 2.0, H O). Negative FAB-MS m/z
269 [M – H] , HR-FAB-MS m/z 269.1020 (calcd for C H O , 269.1025). IR (CaF , ꢈ, cm ):3360, 1550. PMR (400 MHz,
D
2
–
–1
13 17
6
2
methanol-d , ꢄ, ppm, J/Hz): 7.38 (2H, dd, J = 8.8, 1.2, H-2, H-6), 7.30 (2H, dd, J = 8.8, 7.2, H-3, H-5), 7.23 (1H, tt, J = 7.2, 1.2,
4
H-4), 4.71 (1H, d, J = 11.6, H-7a), 4.58 (1H, d, J = 11.6, H-7b), 4.13 (1H, d, J = 4.4, H-3ꢅ), 3.92 (1H, dd, J = 7.2, 4.4, H-4ꢅ), 3.90
(1H, ddd, J = 7.2, 4.4, 2.8, H-5ꢅ), 3.80 (1H, d, J = 12.0, H-1ꢅa), 3.77 (1H, dd, J = 12.8, 2.8, H-6ꢅa), 3.72 (1H, d, J = 12.0, H-1ꢅb),
13
3.64 (1H, dd, J = 12.8, 4.4, H-6ꢅb). C NMR (100 MHz, methanol-d , ꢄ, ppm): 140.2 (C-1), 129.2 (C-3, C-5), 128.8 (C-2,
4
C-6), 128.3 (C-4), 109.3 (C-2'), 84.2 (C-5ꢅ), 83.54 (C-3ꢅ), 78.7 (C-4ꢅ), 64.6 (C-7), 62.7 (C-6ꢅ), 61.8 (C-1ꢅ).
Hydrolysis of Compound 3. Two milligrams of 3 was refluxed with 1 mL of 1 M HCl for 1 h. The identity of the
sugar was confirmed by TLC (F
D-fructose.
Syringin (4). White needlelike crystals (MeOH), mp 190–192ꢃC (H O); [ꢀ] –18.0ꢃ (c 0.6, H O). UV (EtOH, ꢇ ,
nm): 221, 226. Positive FAB-MS m/z 373 [M + H] . IR (CaF , ꢈ, cm ): 3451, 1660. PMR (400 MHz, methanol-d , ꢄ, ppm,
) analysis (CHCl –MeOH–H O, 6:4:1) of the reaction mixture with an authentic sample of
3 2
254s
20
2
D
2
max
+
–1
2
4
J/Hz): 6.74 (2H, s, H-2, 6), 6.55 (1H, br.d, J = 16.0, 1.6, H-7), 6.33 (1H, dt, J = 16.0, 6.0, H-8), 4.21 (2H, dd, J = 6.0, 1.6,
13
H-9), 3.86 (6H, s, 3-OCH , 5-OCH ), 3.80–3.30 (6H, sugar moiety). C NMR (100 MHz, methanol-d , ꢄ, ppm): 154.3 (C-3,
3
3
4
C-5), 135.5 (C-4), 135.2 (C-1), 131.2 (C-8), 130.0 (C-7), 105.4 (C-2, C-6), 105.3 (C-1ꢅ), 78.3 (C-3ꢅ), 77.8 (C-5ꢅ), 75.7 (C-2ꢅ),
71.3 (C-4ꢅ), 62.5 (C-6ꢅ), 57.0 (3-OCH , 5-OCH ).
3
3
20
Triandrin (5). White needlelike crystals (EtOH), mp 178–180ꢃC (H O); [ꢀ] –62.3ꢃ (c 0.5, H O). UV (EtOH, ꢇ ,
nm): 264. Positive FAB-MS m/z 313 [M + H] . IR (CaF , ꢈ, cm ): 3451, 1660. PMR (400 MHz, methanol-d , ꢄ, ppm, J/Hz):
2
D
2
max
+
–1
2
4
7.24 (2H, d, J = 8.4, H-2, 6), 6.72 (2H, d, J = 8.4, H-3, 5), 6.56 (1H, ddd, J = 16.0, 1.6, 1.6, H-7), 6.17 (1H, ddd, J = 16.0, 6.8,
6.0, H-8), 4.48 (1H, ddd, J = 12.4, 6.0, 1.6, H-9a), 4.35 (1H, d, J = 7.6, H-1ꢅ), 4.26 (1H, ddd, J = 12.4, 6.8, 1.6, H-9b),
13
3.80–3.20 (6H, sugar moiety). C NMR (100 MHz, methanol-d , ꢄ, ppm): 158.4 (C-4), 134.1 (C-7), 129.7 (C-1), 128.8 (C-2,
4
C-6), 123.3 (C-8), 116.3 (C-3, C-5), 103.1 (C-1ꢅ), 78.1 (C-3ꢅ), 77.9 (C-5ꢅ), 75.1 (C-2ꢅ), 71.6 (C-4ꢅ), 71.0 (C-9), 62.5 (C-6ꢅ).
+
Phillyrin (6). White powder (MeOH). UV (MeOH, ꢇ , nm): 207, 230, 278. Positive FAB-MS m/z 535 [M + H] .
max
–1
IR (CaF , ꢈ, cm ): 3451, 1660. PMR (400 MHz, pyridine-d , ꢄ, ppm, J/Hz): 7.60 (1H, d, J = 8.4, H-5), 7.24 (2H, br.s, H-2, 2ꢅ),
2
5
7.13 (1H, d, J = 8.4, H-5ꢅ), 7.03 (1H, d, J = 8.4, H-6), 7.00 (1H, dd, J = 8.4, 1.2, H-6ꢅ), 5.67 (1H, d, J = 6.0, H-1ꢅꢅ), 4.94 (1H,
d, J = 6.0, H-7ꢅ), 4.67 (1H, d, J = 6.8, H-7), 4.49 (1H, dd, J = 12.4, 2.0, H-6ꢅꢅa), 4.35 (1H, dd, J = 12.4, 5.2, H-6ꢅꢅb), 4.35–4.08
(4H, m, H-2ꢅꢅ, 3ꢅꢅ, 4ꢅꢅ, 5ꢅꢅ), 4.24 (1H, m, H-9a), 4.00 (1H, dd, J = 9.2, 8.4, H-9ꢅa), 3.88 (1H, dd, J = 8.0, 6.4, H-9b), 3.78 (3H,
4ꢅ-OCH ), 3.75 (6H, 3-OCH , 3ꢅ-OCH ), 3.56 (1H, dd, J = 10.4, 9.2, H-9ꢅb), 3.37 (1H, m, H-8ꢅ), 2.95 (1H, m, H-8).
3
3
3
13
C NMR (100 MHz, pyridine-d , ꢄ, ppm): 150.3 (C-3), 150.1 (C-3ꢅ), 149.1 (C-4ꢅ), 147.5 (C-4), 136.4 (C-1), 132.2 (C-1ꢅ),
5
119.1 (C-6), 118.5 (C-6ꢅ), 116.6 (C-5), 112.6 (C-5ꢅ), 111.3 (C-2), 110.7 (C-2ꢅ), 102.4 (C-1ꢅꢅ), 87.8 (C-7), 82.3 (C-7ꢅ), 78.8
(C-3ꢅꢅ), 78.5 (C-5ꢅꢅ), 74.9 (C-2ꢅꢅ), 71.3 (C-4ꢅꢅ), 71.3 (C-9), 70.0 (C-9ꢅ), 62.4 (C-6ꢅꢅ), 56.1 (3-OCH ), 56.0 (3ꢅ-OCH ,
3
3
4ꢅ-OCH ), 54.1 (C-8), 50.5 (C-8ꢅ).
3
20
Neoolivil-4-O-ꢁ-D-glucoside (7). Amorphous powder (EtOH); [ꢀ] –6.4ꢃ (c 0.1, MeOH). UV (EtOH, ꢇ , nm):
228, 277. Positive HR-FAB-MS m/z 561.1902 [M + Na] . IR (CaF , ꢈ, cm ): 3451, 2925, 1660, 1100. PMR (400 MHz,
D
max
+
–1
2
methanol-d , ꢄ, ppm, J/Hz): 7.13 (1H, d, J = 8.4, H-5), 7.02 (1H, d, J = 2.0, H-2), 6.93 (1H, d, J = 1.6, H-2ꢅ), 6.91 (1H, dd, J = 8.4,
4
2.0, H-6), 6.79 (1H, dd, J = 8.0, 1.6, H-6ꢅ), 6.75 (1H, d, J = 8.0, H-5ꢅ), 4.87 (1H, d, J = 7.2, H-1ꢅꢅ), 4.75 (1H, d, J = 4.4, H-7),
4.70 (1H, d, J = 4.4, H-7ꢅ), 4.24 (2H, m, H-9a, H-9ꢅa), 3.87 (2H, m, H-9b, 9ꢅb), 3.86–3.38 (6H, sugar moiety), 3.75 (6H,
13
3-OCH , 3ꢅ-OCH ), 3.12 (1H, m, H-8, 8ꢅ). C NMR (100 MHz, methanol-d , ꢄ, ppm): 150.9 (C-3), 149.0 (C-3ꢅ), 147.5 (C-4),
3
3
4
147.2 (C-4ꢅ), 137.5 (C-1), 133.7 (C-1ꢅ), 120.0 (C-6ꢅ), 119.7 (C-6), 118.0 (C-5), 116.0 (C-5ꢅ), 111.6 (C-2), 110.9 (C-2ꢅ), 102.8
(C-1ꢅꢅ), 87.4 (C-7ꢅ), 87.1 (C-7), 78.2 (C-3ꢅꢅ), 77.8 (C-5ꢅꢅ), 74.9 (C-2ꢅꢅ), 72.7 (C-9, C-9ꢅ), 71.3 (C-4ꢅꢅ), 62.5 (C-6ꢅꢅ), 56.7
(3-OCH ), 56.5 (3ꢅ-OCH ), 55.5 (C-8ꢅ), 55.3 (C-8).
3
3
ACKNOWLEDGMENT
This research was funded by the Rural DevelopmentAdministration (20110701-305-656-001-02-00), Republic of Korea.
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REFERENCES
1.
2.
3.
4.
5.
6.
J. S. Kim, Y. H. Choi, J. H. Seo, J. W. Lee, Y. S. Kim, S. Y. Ryu, J. S. Kang, Y. K. Kim, and S. H. Kim,
J. Korean Soc. Appl. Biol. Chem., 35, 260 (2004).
M. H. Bang, D. Y. Lee, Y. J. Oh, M. W. Han, H. J. Yang, H. G. Chung, T. S. Jeong, K. T. Lee, M. S. Choi,
and N. I. Baek, J. Korean Soc. Appl. Biol. Chem., 51, 66 (2008).
M. H. Bang, D. Y. Lee, M. W. Han, Y. J. Oh, H. G. Chung, T. S. Lee, K. T. Lee, M. S. Choi, and N. I. Baek,
J. Korean Soc. Appl. Biol. Chem., 50, 235 (2007).
U. J. Jung, N. I. Baek, H. G. Chung, M. H. Bang, T. S. Jeong, K. T. Lee, Y. J. Kang, M. K. Lee, H. J. Kim, J. Y. Yeo,
and M. S. Choi, Clin. Nutr., 27, 167 (2008).
S. J. An, J. I. Han, M. J. Kim, J. S. Park, J. M. Han, N. I. Baek, H. G. Chung, M. S. Choi, K. T. Lee, and T. S. Jeong,
J. Med. Food, 13, 414 (2010).
Y. H. Kim, Y. W. Kim, Y. J. Oh, N. I. Baek, S. A. Chung, H. G. Chung, T. S. Jeong, M. S. Choi, and K. T. Lee,
Biol. Pharm. Bull., 29, 2441 (2006).
7.
8.
9.
F. Toshiyuki, I. Hideyuki, and Y. Takashi, Nat. Med., 57, 19 (2003).
K. Rie and K. Masao, Ann. Rep. Tohoku Coll. Pharm., 45, 128 (1998).
G. G. Zapesochnaya, V. A. Kurkin, V. B. Braslavskii, and N. V. Fiatova, Chem. Nat. Compd., 39, 317 (2003).
M. C. Song, E. M. Ahn, M. H. Bang, S. Y. Kim, Y. D. Rho, B. M. Kwon, H. S. Lee, and N. I. Baek,
J. Korean Soc. Appl. Biol. Chem., 52, 562 (2009).
10.
11.
12.
H. X. Kuang, Y. G. Xia, B. Y. Yang, J. Liang, Q. B. Zhang, and L. G. Yu, Chin. J. Nat. Med., 7, 281 (2009).
J. H. Park, S. W. Yeon, J. G. Cho, D. Y. Lee, Y. S. Kim, and N. I. Baek, J. Korean Soc. Appl. Biol. Chem.,
53, 736 (2010).
13.
14.
15.
16.
M. Chiba, S. Hisada, S. Nishibe, and H. Theeme, Phytochemistry, 19, 336 (1979).
L. Gongora, S. Manez, R. M. Giner, C. Recio, A. I. Gray, and J. L. Rios, Phytochemistry, 59, 859 (2002).
M. Kikuchi and M. Kikuchi, Chem. Pharm. Bull., 53, 49 (2005).
L. Poncini and G. N. Richards, Carbohydr. Res., 87, 216 (1980).
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