全 文 ： 26 Chin J Nat Med Jan. 2011 Vol. 9 No. 1 2011 年 1 月 第 9 卷 第 1 期

Chinese Journal of Natural Medicines 2011, 9(1): 0026−0029
doi: 10.3724/SP.J.1009.2011.00026
Chinese
Journal of
Natural
Medicines







Five Lignans and an Iridoid from Sambucus williamsii

OUYANG Fu1, LIU Yuan1, LI Rong1, LI Ling2, WANG Nai-Li1, 2*, YAO Xin-Sheng1
1School of Traditional Chinese Materia Medica, Shenyang Pharmaceutical University, Shenyang 110016, China;
2Shenzhen Traditional Chinese Medicines and Natural Products Research Center, Research Institute of Tsinghua University in Shenzhen,
Shenzhen 518057, China
Available online 20 Jan. 2011
[ABSTRACT] AIM: To study the chemical constituents of the 60% ethanol extract of the stems of Sambucus williamsii Hance.
METHODS: Compounds were isolated and purified by macroporous adsorptive resin D101, silica gel, and ODS column chroma-
tographies and preparative HPLC. Their structures were identified by spectroscopic methods. RESULTS: Five lignans and one iridoid
were isolated from the stems of Sambucus williamsii Hance. and their structures were identified as dehydrodiconiferyl alco-
hol-4-O-β-D-glucopyranoside (1), dihydrodehydrodiconiferyl alcohol-4-O-β-D-glucopyranoside (2), (7S, 8R)-dihydro-3-hydroxy-
8-hydroxy-methyl-7-(4-hydroxy-3-methoxy-phenyl)-1-benzofuranpropanol (3), erythro-1-(4-hydroxy-3-methoxyphenyl)-2-[2-hydro-
xy-4-(3-hydroxypropyl) phenoxy]-1, 3-propanediol (4), threo-1-(4-hydroxy-3-methoxyphenyl)-2-[2-hydroxy-4-(3-hydroxypropyl)
phenoxy]-1, 3-propanediol (5), and morroniside (6) with about 70% α-morroniside and 30% β-morroniside. CONCLUSION: Com-
pounds 1, 4 and 5 were isolated from this genus for the first time, and compounds 2, 3 and 6 were obtained from the plant for the first
time.
[KEY WORDS] Sambucus williamsii; Lignan; Iridoid; Morroniside
[CLC Number] R284.1 [Document code] A [Article ID] 1672-3651(2011)01-0026-04

1 Introduction
Sambucus williamsii Hance, a tree widely distributed in
China, has been used for treatment of bone fracture and os-
teoporosis [1]. Previous studies have indicated that lignans are
the main constituents and have effects on osteoblastic
UMR106 cells [2-4]. In this paper, five lignans and one iridoid
were isolated and identified as dehydrodiconiferyl alco-
hol-4-O-β-D-glucopyranoside (1), dihydrodehydrodiconiferyl
alcohol-4-O-β-D-glucopyranoside (2), (7S, 8R)-dihydro-3- hy-
droxy-8-hydroxy-methyl-7-(4-hydroxy-3-methoxy-phenyl)-
1-benzofuranpropanol (3), erythro-1-(4-hydroxy-3-methoxy-
phenyl)-2-[2-hydroxy-4-(3-hydroxypropyl)phenoxy]-1, 3-
propanediol (4), threo-1-(4-hydroxy-3-methoxyphenyl)-2-
[2-hydroxy-4-(3-hydroxypropyl) phenoxy]-1, 3-propanediol
(5), and morroniside (6) with about 70% α-morroniside and
30% β-morroniside. Compounds 1, 4 and 5 were isolated

[Received on] 15-Jan-2010
[Research Funding] This project was supported by the NSFC/RGC
Joint Research Scheme (No. 30418007).
[*Corresponding author] WANG Nai-Li: Prof., Tel: 86-755-
26957800, E-mail: wangnl@tsinghua-sz.org
These authors have no any conflict of interest to declare.
from this genus for the first time, and compounds 2, 3 and 6
were obtained from the plant for the first time. Their struc-
tures are shown in Fig. 1.
2 Experimental
2.1 General experimental procedures
Macroporous adsorptive resin D101 was purchased from
Tianjin Pesticide Factory (Tianjin, China). Silica gel (45-75
µm) was purchased from Qingdao Marine Chemical Group
Co. (Qingdao, China). ODS was purchased from YMC Co.,
Ltd., Japan. Preparative HPLC was performed using a C-18
column (C-18, 250 mm × 20 mm, SHIMADZU Pak; detector:
UV). The 1H NMR (400 MHz) and 13C NMR (100 MHz)
spectra were obtained on a Bruker spectrometer. Mass spectra
were determined on a Bruker Esquire 2000 spectrometer.
2.2 Plant material
Sambucus williamsii Hance was collected in Shenyang,
China and was identified by Prof. JIANG Ze-Rong, Shen-
yang Pharmaceutical University, Shenyang, China. A voucher
specimen (No.YYXJSW-2003) was kept in Shenzhen Tradi-
tional Chinese Medicines and Natural Products Research
Center, Shenzhen, China.
2.3 Extraction and isolation
Dry stems of the plant (28.9 kg) were cut into pieces and
OUYANG Fu, et al. /Chinese Journal of Natural Medicines 2011, 9(1): 26−29
2011 年 1 月 第 9 卷 第 1 期 Chin J Nat Med Jan. 2011 Vol. 9 No. 1 27


Fig. 1 Structures of compounds 1-6
extracted for 3 hours with 60 % ethanol two times. The etha-
nol extract was separated by macroporous adsorptive resin
D101 and eluted with a gradient of ethanol/water (0, 30 %,
50 % and 95 %). The extract (120 g) from the 50 % ethanol
elution was dried under reduced pressure, and then subjected
to silica gel column chromatography with CHCl3-MeOH
elution to obtain 9 fractions. Fractions 3 and 4 were further
separated by silica gel, ODS column chromatography and
purified by preparative HPLC to yield compounds 1 (65.4
mg), 2 (62.1 mg), 3 (66.0 mg), 4 (57.2 mg), 5 (117.5 mg) and
6 (34.1 mg).
3 Identification
Compound 1 Yellow powder, C26H32O11, ESI-MS m/z:
543 [M + Na]+, 381 [M + Na − 162]+, 555 [M + Cl]−. 1H
NMR (CD3OD, 400 MHz) δ: 7.02 (1H, d, J = 1.9 Hz, H-2),
7.13 (1H, d, J = 8.4 Hz, H-5), 6.92 (1H, dd, J = 1.9, 8.4 Hz,
H-6), 5.57 (1H, d, J = 5.9 Hz, H-7), 3.50 (1H, over lap, H-8),
3.84 (1H, over lap, H-9a), 3.76 (1H, over lap, H-9b), 6.93
(2H, s, H-2′, 6′), 6.53 (1H, d, J = 15.9 Hz, H-7′), 6.21 (1H, dt,
J = 15.9, 5.9 Hz, H-8′), 4.19 (2H, dd, J = 5.9, 1.3 Hz, H-9′),
3.81 (3H, s, 3-OCH3), 3.86 (3H, s, 3′-OCH3), 4.88 (1H, d, J =
7.4 Hz, H-Glc-1), 3.38-3.90 (5H, over lap, H-Glc). The 13C
NMR data are shown in Table 1. All data were identical with
those of dehydrodiconiferyl alcohol-4-O-β-D-glucopyranoside [5].
Compound 2 Yellow powder, C26H34O11, ESI-MS m/z:
545 [M + Na]+, 383 [M + Na − 162]+, 557 [M+Cl]−. 1H NMR
(CD3OD, 400 MHz) δ: 7.02 (1H, d, J = 1.8 Hz, H-2), 7.13
(1H, d, J = 8.4 Hz, H-5), 6.92 (1H, dd, J = 1.8, 8.4 Hz, H-6),
5.54 (1H, d, J = 5.9 Hz, H-7), 3.50 (1H, over lap, H-8), 3.85
(1H, over lap, H-9a), 3.78 (1H, over lap, H-9b), 6.70 (1H, s,
H-2′), 6.72 (1H, s, H-6′), 2.61 (2H, t, J = 7.4 Hz, H-7′), 1.80
(2H, m, H-8′), 3.55 (2H, t, J = 6.5 Hz, H-9′), 3.81 (3H, s,
3-OCH3), 3.85 (3H, s, 3′-OCH3), 4.88 (1H, d, J = 7.6 Hz,
H-Glc-1), 3.38-3.90 (5H, over lap, Glc). The 13C NMR data
are shown in Table 1. All data were identical with those of
dihydrodehydrodiconiferyl alcohol-4-O-β-D-glucopyranoside [6].
Compound 3 Yellow powder, C20H24O5, ESI-MS m/z:
369 [M + Na]+, 381 [M + Cl]−. 1H NMR (CD3OD, 400 MHz)
δ: 6.97 (1H, d, J = 1.8 Hz, H-2), 6.76 (1H, d, J = 8.2 Hz, H-5),
6.83 (1H, dd, J = 1.8, 8.2 Hz, H-6), 5.49 (1H, d, J = 6.1 Hz,
H-7), 3.45 (1H, ddd, J = 5.5, 7.3, 6.1 Hz, H-8), 3.74 (1H, dd,
J = 11.0, 7.3 Hz, H-9a), 3.82 (1H, dd, J = 11.0, 5.5 Hz, H-9b),
6.59 (1H, s, H-2′), 6.58 (1H, s, H-6′), 2.54 (2H, t, J = 7.3 Hz,
H-7′), 1.77 (2H, m, H-8′), 3.55 (2H, t, J = 6.5 Hz, H-9′), 3.79
(3H, s, 3-OCH3). The 13C NMR data are shown in Table 1.
All data were identical with those of (7S, 8R)-dihydro-3-
hydroxy-8-hydroxy-methyl-7-(4-hydroxy-3-methoxy-phenyl)-
1-benzofuranpropanol [7].
Compound 4 Yellow powder, C19H24O7, ESI-MS m/z:
387 [M + Na]+, 363 [M − H]−. 1H NMR (CD3OD, 400 MHz)
δ: 7.00 (1H, d, J = 1.5 Hz, H-2), 6.75 (1H, d, J = 8.1 Hz, H-5),
6.83 (1H, dd, J = 1.5, 8.1 Hz, H-6), 4.86 (1H, d, J = 4.8 Hz,
H-7), 4.14 (1H, m, H-8), 3.74 (1H, dd, J = 3.4, 11.7 Hz,
H-9a), 3.84 (1H, dd, J = 6.4, 11.7 Hz, H-9b), 6.66 (1H, d, J =
1.8 Hz, H-2′), 6.71 (1H, d, J = 8.2 Hz, H-5′), 6.52 (1H, dd, J
= 1.8, 8.2 Hz, H-6′), 2.52 (2H, t, J = 7.3 Hz, H-7′), 1.76 (2H,
m, H-8′), 3.53 (2H, t, J = 6.5 Hz, H-9′), 3.79 (3H, s, 3-OCH3).
The 13C NMR data are shown in Table 1. All data were iden-
tical with those of erythro-1-(4-hydroxy-3-methoxyphenyl)-2-
[2-hydroxy-4-(3-hydroxypropyl)phenoxy]-1,3-propanediol [8-9].
Compound 5 Yellow powder, C19H24O7, ESI-MS m/z:
387 [M + Na]+, 363 [M − H]−. 1H NMR (CD3OD, 400 MHz)
δ: 7.00 (1H, s, H-2), 6.77 (1H, d, J = 7.9 Hz, H-5), 6.84 (1H,
d, J = 7.9 Hz, H-6), 4.92 (1H, d, J = 5.6 Hz, H-7), 4.13 (1H,
m, H-8), 3.74 (1H, over lap, H-9a), 3.53 (1H, over lap, H-9b),
6.70 (1H, s, H-2′), 6.89 (1H, d, J = 8.1 Hz, H-5′), 6.54 (1H, d,
J = 8.1 Hz, H-6′), 2.52 (2H, t, J = 7.3 Hz, H-7′), 1.76 (2H, m,
H-8′), 3.53 (2H, over lap, H-9′), 3.77 (3H, s, 3-OCH3). The
13C NMR data are shown in Table 1. All data were identical
with those of threo-1-(4-hydroxy-3-methoxyphenyl)-2-[2-
hydroxy-4-(3- hydroxypropyl)phenoxy]-1,3-propanediol [9-10].
Compound 6 White powder, C17H26O11, ESI-MS m/z:
429 [M + Na]+, 267 [M + Na − 162]+, 441 [M + Cl]−, 405 [M
− H]−. 1H NMR (CD3OD, 400 MHz) α-morroniside δ: 5.82
OUYANG Fu, et al. /Chinese Journal of Natural Medicines 2011, 9(1): 26−29
28 Chin J Nat Med Jan. 2011 Vol. 9 No. 1 2011 年 1 月 第 9 卷 第 1 期

Table 1 13C NMR (CD3OD, 100 MHz) data for compounds 1-6
6
No. 1 2 3 4 5
α β
1 138.1 138.3 129.7 133.7 133.9 095.90 095.60
2 111.3 111.2 110.5 111.7 111.4
3 150.9 150.9 148.9 148.8 148.8 154.46
4 147.7 147.5 147.2 147.0 147.0 110.80 111.67
5 118.1 118.0 116.1 115.8 115.9 031.93 027.41
6 119.4 119.4 119.6 120.7 120.6 037.19 034.53
7 088.8 088.5 088.6 074.0 074.1 096.99 092.33
8 055.3 055.6 055.5 087.5 078.3 074.06 065.88
9 064.9 065.0 065.0 061.9 061.7 039.79 040.46
10 019.82 019.78
11 168.66 168.72
1′ 130.1 137.1 136.7 138.7 138.4
2′ 112.2 117.9 116.7 117.2 117.1
3′ 145.5 145.2 141.7 149.3 149.0
4′ 149.2 147.4 146.3 145.5 145.8
5′ 132.7 129.6 134.9 120.0 119.1
6′ 116.5 114.2 116.9 120.6 120.6
7′ 131.9 032.9 032.6 032.4 032.3
8′ 127.7 035.7 035.6 035.4 035.4
9′ 063.8 062.2 062.3 062.2 062.2
3-OCH3 056.8 056.8 056.4 056.4 056.3
3′-OCH3 056.7 056.7
95.6 051.82 051.76
Glc-1 102.8 102.7 99.99 100.03
2 074.9 074.9 74.96
3 077.8 078.1 78.35
4 071.3 071.3 071.55 071.60
5 078.1 077.8 77.87
6 062.5 062.5 062.72 062.79

(1H, d, J = 9.3 Hz, H-1), 7.51 (1H, s, H-3), 2.81 (1H, dt, J =
4.5, 12.9 Hz, H-5), 2.02 (1H, dt, J = 2.4, 12.9 Hz, H-6a), 1.18
(1H, dt, J = 9.8, 12.9 Hz, H-6b), 4.80 (1H, over lap, H-7),
3.95 (1H, dq, J = 2.0, 6.8 Hz, H-8), 1.76(1H, ddd, J = 2.0, 4.5,
9.3 Hz, H-9), 1.38 (3H, d, J = 6.8 Hz, H-10), 3.70 (3H, s,
OCH3), 4.78 (1H, d, J = 7.9 Hz, H-Glc-1), 3.15-3.90 (5H,
over lap, H-Glc). β-morroniside δ: 5.86 (1H, d, J = 9.3 Hz,
H-1), 7.50 (1H, s, H-3), 3.12 (1H, dt, J = 4.5, 12.9 Hz, H-5),
1.89 (1H, dt, J = 4.6, 12.9 Hz, H-6a), 1.49 (1H, dt, J = 3.2,
12.9 Hz, H-6b), 5.24 (1H, br d, J = 3.2 Hz, H-7), 4.54 (1H,
dq, J = 2.2, 6.8 Hz, H-8), 1.80 (1H, m, H-9), 1.31 (3H, d, J =
6.8 Hz, H-10), 3.69 (3H, s, OCH3), 4.78 (1H, d, J = 7.9 Hz,
H-Glc-1), 3.15-3.90 (5H, over lap, H-Glc). The 13C NMR
data are shown in Table 1. All data were identical with those
of morroniside with about 70% α-morroniside and 30%
β-morroniside according to the integration of 1H and the
height of 13C [11].
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接骨木中的五个木脂素和一个环烯醚萜
欧阳富 1, 刘 远 1, 李 荣 1, 李 玲 2, 王乃利 1, 2*, 姚新生 1
1沈阳药科大学中药学院, 沈阳 110016;
2深圳清华大学研究院 深圳中药及天然药物研究中心, 深圳 518057
【摘 要】 目的：研究接骨木 Sambucus williamsii Hance 茎枝的化学成分。方法：采用 60%乙醇提取, 经 D101 大孔吸附树
脂、硅胶和 ODS 等柱色谱以及制备型 HPLC 等各种现代分离手段, 对接骨木茎枝中的化学成分进行分离纯化, 并用光谱学方法
对得到的化合物进行结构鉴定。结果：分离得到了 5 个木脂素类和 1 个环烯醚萜类化合物, 分别是 dehydrodiconiferyl alco-
hol-4-O-β-D-glucopyranoside (1), dihydrodehydrodiconiferyl alcohol-4-O-β-D-glucopyranoside (2), (7S, 8R)-dihydro-3-hydroxy-8-
hydroxy-methyl-7-(4-hydroxy-3-methoxy-phenyl)-1-benzofuranpropanol (3), erythro-1-(4-hydroxy-3-methoxyphenyl)-2-[2-hydroxy-4-
(3-hydroxypropyl)phenoxy]-1, 3-propanediol (4), threo-1-(4-hydroxy-3-methoxyphenyl)-2-[2-hydroxy-4-(3-hydroxypropyl)phenoxy]-1,
3-propanediol (5), 莫诺苷(6)(其中 α-莫诺苷大约占 70%, β-莫诺苷占 30%)。结论：化合物 1、4、5 为首次从该属植物中分离得到,
化合物 2、3、6 为首次从该植物中分离得到。
【关键词】 接骨木; 木脂素; 环烯醚萜; 莫诺苷

【基金项目】 国家自然科学基金委员会与香港研究资助局联合基金(No. 30418007)

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