全 文 ： 425 Journal of Chinese Pharmaceutical Sciences http://www.jcps.ac.cn
Lignans from Pilea cavaleriei Levl subsp. cavaleriei
Yong Zhou, Hengchun Ren, Ridong Qin, Qingying Zhang*, Hong Liang*
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University Health Science
Center, Beijing 100191, China
Abstract: A new lignan glycoside, named (7S,8R,8′R)-(−)-lariciresinol-9-O-α-L-rhamnopyranosyl (1→2) β-D-glucopyranoside (1),
was isolated from the ethanol extract of Pilea cavaleriei Levl subsp. cavaleriei, together with 17 known lignans (2−18). The structures
of these compounds were elucidated by extensive spectroscopic analysis, including 1D NMR, 2D NMR and HR-ESI-MS.
All the compounds were obtained from the genus Pilea for the first time.
Keywords: Pilea cavaleriei Levl subsp. cavaleriei, Urticaceae, Lignan glycosides, Lignans
CLC number: R931.5 Document code: A Article ID: 1003–1057(2014)6–425–04
Received: 2014-03-12, Revised: 2014-03-21, Accepted: 2014-03-30.
Foundation item: Beijing Natural Science Foundation (Grant No.
7132129).
*Corresponding author. Tel.: 86-10-82801592,
E-mail: lianghong@bjmu.edu.cn, qyzhang@bjmu.edu.cn
http://dx.doi.org/10.5246/jcps.2014.06.057
1. Introduction
Pilea cavaleriei Levl subsp. cavaleriei, belonging to
the genus Pilea of the family Urticaceae, is widely
distributed in Hunan, Guangdong, Guangxi, and
Guizhou provinces of China. Its whole plants have
been used as a folk medicine in some local areas for
the treatment of cough with lung heat, tuberculosis,
and traumatic injuries[1]. Previous phytochemical
investigations on the plant have led to the isolation and
identification of nine triterpenoids, seven phenolic
acids, and six nitrogen compounds[2,3]. Herein, we
report the isolation and structural identification of a new
lignan glycoside, named (7S,8R,8′R)-(−)-lariciresinol-9-
O-α-L-rhamnopyranosyl (1→2) β-D-glucopyranoside (1),
and 17 known lignans (2−18) (Fig. 1). All the compounds
were obtained from the genus Pilea for the first time.
2. Experimental
2.1. General experimental procedures
Optical rotations were measured on a Rudolph
Autopol III automatic polarimeter (Rudolph Research
Analytical, Hackettstown, NJ, USA). UV spectra were
measured on a Cary-300 spectrophotometer (Varian,
















Palo Alto, CA, USA). IR spectra were taken on a Nicolet
Nexus 470 FT-IR spectrometer (Nicolet, Austin, TX,
USA). CD spectra were recorded on a Jasco J-810
spectropolarimeter (Jasco Co., Tokyo, Japan). ESI-MS
were recorded on a QSTAR mass spectrometer (AB Sciex,
Framingham, MA, USA). HR-ESI-MS were recorded
on a Waters Xevo G2 Q-TOF mass spectrometer (Waters,
Milford, MA, USA). 1D and 2D NMR spectra were
acquired on Bruker Avance 400 or 600 spectrometer
(Bruker, Fllanden, Switzerland) with tetramethylsilane
(TMS) as an internal standard. Thin layer chromatography
(TLC) analysis was carried out using precoated silica
gel GF254 plates (Qingdao Marine Chemical Inc., Qingdao,
China). Column chromatography (CC) was performed
on silica gel (200−300 mesh, Qingdao Marine Chemical
Inc., Qingdao, China), RP-C18 silica gel (100−200 mesh,
YMC Co., Kyoto, Japan), Diaion HP-20 (Mitsubishi
Chemical Co., Kyoto, Japan), and Sephadex LH-20
(GE Healthcare, Uppsala, Sweden). Semi-preparative
HPLC was performed on a Grace Allsphere C18 column
(10 mm×250 mm, 5 μm, GRACE Co., MA, USA) using
Figure 1. Chemical structure of compound 1.
1
1
3
7
4
3
5
6
62 8
2
4
5
7
8
91
9
O
H3CO
HO
OCH3
OH
H H
O
13
6
3
5
O
OHHO
HO
OHO
HO
O
HO
426 Zhou, Y. et al. / J. Chin. Pharm. Sci. 2014, 23 (6), 425–428
a Waters 600 series system (Waters, Milford, MA, USA)
equipped with Waters 600 Pump, 600 Controller, and
486 Tunable Absorbance Detector. Analytical grade
solvents were purchased from Beijing Chemical Factory
(Beijing, China).
2.2. Plant materials
The whole plants of Pilea cavaleriei Levl subsp.
cavaleriei were collected in July 2009 at Liuzhou,
Guangxi Zhuang Autonomous Region of China. The
identification of the plants was performed by Prof.
Dehai Qin of Guangxi Institute of Traditional Chinese
Medicine. A voucher specimen (No. NME20090701)
was deposited at the Department of Natural Medicines,
School of Pharmaceutical Sciences, Peking University
Health Science Center.
2.3. Extraction and isolation
The air-dried and powdered whole plants of Pilea
cavaleriei Levl subsp. cavaleriei (10.0 kg) were perco-
lated exhaustively with 95% EtOH and 50% EtOH at
room temperature. After evaporation of the solvent under
reduced pressure, the residues were combined and
suspended in water and then partitioned successively
with petroleum ether, EtOAc and n-BuOH. The n-BuOH
extract (172.0 g) was subjected to column chromatography
on Diaion HP-20 eluting with a gradient solvent
system of H2O–EtOH (100:0, 90:10, 70:30, 50:50, 30:70,
10:90, 0:100, v/v) to yield seven fractions (Fr. 1–Fr. 7).
Fr. 3 (17.6 g) was chromatographed on a silica gel
column eluted with EtOAc–MeOH (50:1 to 1:50, v/v)
to give six subfractions (Fr. 3A–Fr. 3F). Fr. 3D (4.21 g)
and Fr. 3E (2.57 g) were further subjected to RP-C18
silica gel column eluted with a gradient MeOH–H2O
(20:80 to 60:40, v/v) to yield six subfractions (Fr. 3D1–
Fr. 3D6) and (Fr. 3E1–Fr. 3E6), respectively. Fr. 3D2
(0.95 g) was separated over Sephadex LH-20 eluted with
MeOH–H2O (35:65, v/v) and purified by semi-preparative
HPLC eluted with CH3CN–H2O (11:89, v/v) to afford
2 (3.0 mg), 7 (3.0 mg), 8 (4.0 mg), 10 (1.0 mg), 11
(5.0 mg), 12 (18.0 mg), 13 (80.0 mg), and 16 (3.0 mg).
Fr. 3D3 (0.60 g) was purified by Sephadex LH-20 eluted
with MeOH–H2O (35:65, v/v) and semi-preparative
HPLC eluted with CH3CN–H2O (12:88, v/v) to afford
3 (1.0 mg), 4 (2.0 mg), 5 (4.0 mg), 14 (1.0 mg), and 15
(4.0 mg). Further purification of Fr. 3D5 (0.40 g) by
Sephadex LH-20 eluted with MeOH–H2O (35:65, v/v)
and semi-preparative HPLC eluted with CH3CN–H2O
(12:88, v/v) yielded 1 (2.0 mg), 6 (1.0 mg) and 9
(6.0 mg). Compounds 17 (15.0 mg) and 18 (2.0 mg) were
obtained from Fr. 3E3 (0.70 g) by Sephadex LH-20 using
a MeOH–H2O (35:65, v/v) system and semi-preparative
HPLC using a CH3CN–H2O (11:89, v/v) system.
2.3.1. (7S,8R,8′R)-(−)-Lariciresinol-9-O-α-L-rhamnopy-
ranosyl (1→2) β-D-glucopyranoside (1)
White amorphous powder; −33.0 (c 0.20, MeOH);
CD (MeOH) nm: 206 (+1.3), 299 (−2.6); UV (MeOH)
λmax nm: 206, 279; IR (film) νmax: 3383, 2934, 2255,
2127, 1602, 1517, 1454, 1428, 1377, 1274, 1125, 1029, 820,
764, 631 cm−1; ESI-MS m/z 667.4 [M−H]¯; HR-ESI-MS
m/z 667.2620 [M−H]¯ (calcd. for C32H43O15, 667.2602);
1H NMR and 13C NMR data see Table 1.
No. δH (J in Hz) δC, DEPT Key HMBC
Aglycone
1 133.5, s
2 6.83 d (1.8) 110.1, d C-1, 3, 4, 6, 7
3 147.4, s
4 145.8, s
5 6.71 d (7.8) 115.0, d C-1, 3, 4
6 6.69 dd (7.8, 1.8) 118.7, d C-1, 2, 4, 7
7 4.55 d (7.8) 81.1, d C-1, 2, 6, 8, 9, 9′
8 2.43 m 50.4, d C-1, 7, 9, 7′
9a 4.05 dd (16.2, 6.6)
66.6, t C-7, 8, 8′
9b 3.34 (overlapped)
1′ 131.6, s
2′ 6.73 d (1.8) 112.7, d C-1′, 3′, 4′, 6′, 7′
3′ 147.4, s
4′ 144.5, s
5′ 6.66 d (7.8) 115.4, d C-1′, 3′, 4′
6′ 6.58 dd (7.8, 1.8) 120.7, d C-2′, 4′, 7′
7′a 2.89 dd (13.2, 4.2)
32.2, t C-1′, 2′, 6′, 8′, 9′
7′b 2.37 m
8′ 2.62 m 41.9, d
9′a 3.83 dd (8.4, 6.6)
71.5, t C-7, 8, 7′
9′b 3.55 dd (8.4, 4.8)
3-OMe 3.75 s 55.5, q C-3
3′-OMe 3.74 s 55.5, q C-3′
Glucose
1′′ 4.22 d (7.2) 101.8, d C-9
2′′ 3.26 t-like (7.8) 76.2, d C-1′′, 1′′′
3′′ 3.30 (overlapped) 77.6, d C-2′′, 4′′
4′′ 3.42 m 70.5, d
5′′ 3.10 m 76.8, d C-4′′
6′′a 3.65 m
61.0, t
6′′b 3.42 m
Rhamnose
1′′′ 5.11 d (1.2) 100.0, d C-2′′, 2′′′, 5′′′
2′′′ 3.64 m 70.4, d
3′′′ 3.05 m 70.3, d
4′′′ 3.17 td (9.0, 4.8) 72.0, d
5′′′ 3.85 (overlapped) 68.1, d C-4′′′
6′′′ 1.08 d (6.0) 18.1, q C-4′′′, 5′′′
3′′-OH 5.14 d (6.0) C-3′′
4′′-OH 4.98 d (5.4) C-3′′, 4′′, 5′′
6′′-OH 4.48 t (6.0) C-5′′, 6′′
2′′′-OH 4.60 d (4.2) C-1′′′, 2′′′, 3′′′
3′′′-OH 4.38 d (6.0) C-3′′′, 4′′′
4′′′-OH 4.69 d (4.2) C-3′′′, 4′′′, 5′′′
Table 1. 1H NMR (600 MHz) and 13C NMR (150 MHz) data of 1
(DMSO-d6, δ in ppm, J in Hz)
20
D[α]
427 Zhou, Y. et al. / J. Chin. Pharm. Sci. 2014, 23 (6), 425–428
3. Results and discussion
Compound 1 was isolated as a white amorphous
powder with negative optical rotation ( −33.0, c 0.20,
MeOH). The molecular formula of C32H44O15 was
derived from its quasi-molecular ion peak at m/z 667.2620
[M−H]¯ (calcd. for C32H43O15, 667.2602) in HR-ESI-MS
spectrum. The IR spectrum showed the presence of
hydroxyl groups (3383 cm−1) and phenyl groups (1602,
1517, 1454 cm−1). The 1H and 13C NMR spectra (Table 1)
showed the presence of two 1,3,4-trisubstituted
benzene rings [δH 6.83 (1H, d, J 1.8 Hz, H-2), 6.71 (1H,
d, J 7.8 Hz, H-5), 6.69 (1H, dd, J1 7.8 Hz, J2 1.8 Hz,
H-6), 6.73 (1H, d, J 1.8 Hz, H-2′), 6.66 (1H, d, J 7.8 Hz,
H-5′), 6.58 (1H, dd, J1 7.8 Hz, J2 1.8 Hz, H-6′); δC 147.4,
147.4, 145.8, 144.5, 133.5, 131.6, 120.7, 118.7, 115.4,
115.0, 112.7, 110.1], two methoxyl groups [δH 3.75
(3H, s, 3-OMe), 3.74 (3H, s, 3′-OMe); δC 55.5, 55.5],
and two hexose moieties [δH 4.22 (1H, d, J 7.2 Hz,
H-1′′), 5.11 (1H, d, J 1.2 Hz, H-1′′′), 1.08 (3H, d, J 6.0 Hz,
H-6′′′); δC 101.8, 100.0, 77.6, 76.8, 76.2, 72.0, 70.5,
70.4, 70.3, 68.1, 61.0, 18.1]. The two hexose units were
identified as β-D-glucopyranose and α-L-rhamnopyranose
respectively by comparing the 1H and 13C NMR data
with those published[4,5]. The remaining 1H and 13C NMR
signals [δH 4.55 (1H, d, J 7.8 Hz, H-7), 2.43 (1H, m,
H-8), 4.05 (1H, dd, J1 16.2 Hz, J2 6.6 Hz, H-9a),
3.34 (1H, overlapped, H-9b), 2.89 (1H, dd, J1 13.2 Hz,
J2 4.2 Hz, H-7′a), 2.37 (1H, m, H-7′b), 2.62 (1H, m,
H-8′), 3.83 (1H, dd, J1 8.4 Hz, J2 6.6 Hz, H-9′a), 3.55
(1H, dd, J1 8.4 Hz, J2 4.8 Hz, H-9′b); δC 81.1, 71.5,
66.6, 50.4, 41.9, 32.2] together with the above signals
suggested compound 1 was a 7,9′-monoepoxy type
lignan glycoside. The presence of 7, 9′-monoepoxy lignan
skeleton was further confirmed by the significant
1H-1H COSY cross peaks of H-7/H-8, H-8/H-9, H-7′/H-8′,
H-8′/H-9′ and the HMBC correlations of H-7/C-2, C-6;
H-2, H-6/C-7; H-8/C-1; H-7′/C-2′, C-6′; H-2′, H-6′/C-7′;
H-7/C-9′; H-8/C-7′; H-9′/C-7, C-8 (Fig. 2). The dispo-
sition of the two methoxyl groups at C-3 and C-3′ were
indicated by the NOESY correlations of 3-OMe/H-2
and 3′-OMe/H-2′, as well as the HMBC correlations of
3-OMe/C-3 and 3′-OMe/C-3′. Then, the linkage of
glucose at C-9 was established by the HMBC correlation
between the anomeric proton H-1′′ (δH 4.22) and C-9
(δC 66.6), while the rhamnose was placed at C-2′′ of
glucose by the marked downfield shift of C-2′′ (δC 76.2)
and the HMBC correlations between the anomeric
proton H-1′′′ (δH 5.11) and C-2′′ (δC 76.2), and between
H-2′′ (δH 3.26) and C-1′′′ (δC 100.0) (Fig. 2). Subsequently,














the coplanar configuration of H-8 and H-8′ and the anti-
periplanar orientation of H-7 and H-8 were characterized
by the NOESY correlation of H-8/H-8′ and the absence
of the NOESY correlation of H-7/H-8. The (7S,8R,8′R)
absolute configuration was determined by its CD
spectrum, which displays a positive Cotton effect at
206 nm and a negative Cotton effect at 299 nm[6].
Thus, compound 1 was elucidated unambiguously as
(7S,8R,8′R)-(−)-lariciresinol-9-O-α-L-rhamnopyranosyl
(1→2) β-D-glucopyranoside.
In addition, 17 known compounds, armandiside (2)[7],
lariciresinol-4-O-β-D-glucopyranoside (3)[8], isolariciresinol-
4-O-β-D-glucopyranoside (4)[9], dehydrodiconiferyl alcohol
4-O-β-D-glucopyranoside (5)[10], dihydrodiconiferyl alcohol
4-O-β-D-glucopyranoside (6)[11], citrusin A (7)[12],
alaschanioside A (8)[12], citrusin B (9)[13], (7R,8R)-threo-
7,9,9-trihydroxy-3,3-dimethoxy-8-O-4-neolignan-4-
O-β-D-glucopyranoside (10)[14], (7R,8S)-erythro-7,9,9-
trihydroxy-3,3-dimethoxy-8-O-4-neolignan-4-O-β-D-
glucopyranoside (11)[14], (7S,8S)-threo-7,9,9-trihydroxy-
3,3-dimethoxy-8-O-4-neolignan-4-O-β-D-glucopyranoside
(12)[14], (7S,8R)-erythro-7,9,9-trihydroxy-3,3-dimethoxy-
8-O-4-neolignan-4-O-β-D-glucopyranoside (13)[14],
(7S,8R)-erythro-7,9,9-trihydroxy-3,3-dimethoxy-8-O-
4-neolignan (14)[14], (7R,8S)-erythro-7,9,9-trihydroxy-
3,3-dimethoxy-8-O-4-neolignan (15)[14], (7R,8R)-threo-
4,7,9-trihydroxy-3,3-dimethoxy-8-O-4-neolignan-9-
O-β-D-glucopyranoside (16)[15], (7R,8S)-erythro-4,9,9-
trihydroxy-3,3-dimethoxy-8-O-4-neolignan-7-O-β-D-
glucopyranoside (17)[16], (7S,8R)-erythro-7,9,9-trihydroxy-
3,3,5-trimethoxy-8-O-4-neolignan-4-O-β-D-glucopy-
ranoside (18)[17], were also obtained and their structures
were identified based on the comprehensive analyses of
the NMR, MS, CD, and specific optical rotation data.
All these compounds were isolated from the genus Pilea
for the first time.
20
D[α]
1H-1H COSY
HMBC
NOESY
O
H3CO
HO
OCH3
OH
H H
O
O
OHHO
HO
OHO
HO
O
HO
H
H
Figure 2. 1H-1H COSY, key HMBC and NOESY correlations of
compound 1.
428 Zhou, Y. et al. / J. Chin. Pharm. Sci. 2014, 23 (6), 425–428
Acknowledgements
This work was financially supported by the grant
from Beijing Natural Science Foundation (Grant No.
7132129).
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石油菜中木脂素类化合物研究
周勇, 任恒春, 覃日懂, 张庆英*, 梁鸿*
北京大学医学部 药学院 天然药物及仿生药物国家重点实验室, 北京 100191 

摘要: 从石油菜全草的乙醇提取物中分离得到一个新的木脂素苷类化合物, (7S,8R,8′R)-(−)-lariciresinol-9-O-α-L-
rhamnopyranosyl(1→2) β-D-glucopyranoside (1), 以及17个已知木脂素类化合物 (2–18), 并采用波谱学方法鉴定了它们的结
构。所有化合物均为首次从冷水花属植物中分离得到。
关键词: 石油菜; 荨麻科; 木脂素苷; 木脂素