全 文 ： O
OH
OH
OR1
OH
RO
O
1 R = H, R1 = H
2 R = Rha, R1 = H
3 R = H, R1 = Rha
4 R = H, R1 = CH3
O
O OH
OH
O
Me
Me
8
O
O OR
OH
5 R = R1 = H
6 R = H, R1 = OGlc
7 R = CH3, R1 = H
R1
Journal of Chinese Pharmaceutical Sciences http://www.jcps.ac.cn 286
Flavanoids and xanthones isolated from Arenaria serpyllifolia L.
Guanshen Zhou, Xiaojuan Yang, Yong Jiang*, Pengfei Tu
State Key Laboratory of Natural and Biomimetic Drugs, Peking University Health Science Center, Beijing 100191, China
Abstract: Eight known compounds were isolated from the whole plants of Arenaria serpyllifolia L. by solvent fractionation and
subsequent separations with silica gel, ODS, Sephadex LH-20 and semi-preparative HPLC chromatography. Their structures
were determined by spectroscopic analysis and identified as quercetin (1), quercetin 7-O-α-L-rhamnoside (2), quercetin 3-O-α-L-
rhamnoside (3), 3-O-methyl quercetin (4), 1,5-dihydroxyxanthone (5), 1,5-dihydroxyxanthone-6-O-β-D-glucoside (6), 5-hydroxy-
1-methoxyxanthone (7) and 6-deoxyisojacareubin (8). All these compounds were isolated from this title plant for the first time,
and compounds 5–8 were obtained from genus Arenaria for the first time.
Keywords: Arenaria serpyllifolia L.; Chemical constituents; Flavonoids; Xanthones
CLC number: R284.2 Document code: A Article ID: 1003–1057(2013)3–286–03
Received date: 2012-10-20.
Foundation items: National Key Technology R&D Program “New
Drug Innovation” of China (Grant No. 2012ZX09301002-002-002,
2012ZX09304-005).
*Corresponding author. Tel.: 86-10-82802719;
E-mail: yongjiang@bjmu.edu.cn
doi:10.5246/jcps.2013.03.042
1. Introduction
Arenaria serpyllifolia L. (Xiaowuxincai in Chinese) is
an annual or biennial herbaceous plant belonging to
Caryophyllaceae family. It has been used as a traditional
Chinese medicine for clearing heat, improving eyesight
and relieving cough in southeast provinces of China[1].
The chemical ingredient of A. serpyllifolia has never been
reported, but five other Arenaria species were previously
reported to mainly contain flavonoids, triterpenoidsaponins,
steroids, alkaloids, phenylpropanoids and cyclic peptides[2–6].
To further study the chemical constituents from plants of
Arenaria genus and to find new bioactive natural products,
a systematic phytochemical investigation was carried out on
A. serpyllifolia. Herein, we report the isolation and structural
elucidation of eight known compounds from the whole plants
of A. serpyllifolia. All these compounds were isolated from
this title plant for the first time and compounds 5–8 were
obtained from genus Arenaria for the first time.
2. Experimental
2.1. General procedures
NMR spectra were recorded on a Varian UNITY
INOVA 500 spectrometer, operating at 500 MHz for
1H NMR and 125 MHz for 13C NMR. The chemical shifts
and coupling constants were given in δ (ppm) and J in Hz,
respectively. Column chromatography was performed
on silica gel (200–300 mesh, Qingdao Haiyang Chemical



























Co. Ltd.) and ODS (Merck) on an Agela Technologies
Cheetah Flash System (Tianjin, China), and Sephadex LH-20
(Pharmacia) was used for open column chromatography.
Semi-preparative HPLC was carried out on a Waters 600
instrument with GRACE Prevail C18 (10 mm×250 mm,
5 μm) and Agela Venusil XBP RP-8 (10 mm×250 mm,
5 μm) columns, with a Waters 2487 Dual λ Absorbance
Detector.
2.2. Plant material
The whole plants of A. serpyllifolia were collected in
Pingnan, Fujian Province, China, in October 2009. The
plant material was authenticated by Prof. Pengfei Tu. A
voucher specimen (No. GS20091008) is deposited at the
Herbarium of Peking University Modern Research Center
for Traditional Chinese Medicine.
Figure 1. Structures of compounds 1–8.
Note
287 Zhou, G.S. et al. / J. Chin. Pharm. Sci. 2013, 22 (3), 286–288
2.3. Extraction and isolation
Dried whole plants of A. serpyllifolia (4.5 kg) were
cut and extracted three times with 70% aqueous ethanol.
After evaporation of the solvent under reduced pressure,
the residue (950 g) was suspended in water and extracted
with petroleum ether and ethyl acetate successively, each
for three times.
The extract of ethyl acetate (280 g) was fractionated by
silica gel column chromatography eluted with chloroform–
methanol (19:1 to 7:3, v/v) to give 4 fractions (A–D).
Fraction A was subjected to silica gel column chromatog-
raphy eluted with petroleum ether–ethyl acetate (2:1 to 1:1,
v/v) to give 25 subfractions. Compounds 5 (8 mg) and 8
(5 mg) were obtained by Sephadex LH-20 (CHCl3–MeOH,
1:1, v/v) and ODS (MeOH–H2O, 7:3, v/v) chromatography
from subfractions 3–4. Compound 7 (5 mg) was obtained
by Sephadex LH-20 (CHCl3–MeOH, 1:1, v/v) and semi-
preparation HPLC using GRACE Prevail C18 column
(CH3CN–H2O, 67:33, v/v) from subfractions 10–15.
Fraction B was subjected to silica gel column chroma-
tography eluted with petroleum ether–ethyl acetate (1:1 to
0:1, v/v) to give 10 subfractions. Compound 1 (50 mg)
was separated from subfraction 6 as crystals; compound 6
(2 mg) was purified by silica gel (CHCl3–MeOH, 10:1
to 4:1, v/v) and ODS (MeOH–H2O, 2:8 to 5:5, v/v)
column chromatography from subfraction 1. Compounds 2
(15 mg) and 3 (5 mg) were obtained by silica gel (CHCl3–
MeOH, 9:1 to 7:3, v/v) and ODS (MeOH–H2O, 1:1, v/v)
column chromatography from fraction C.
The residue of water layer (500 g) was separated using
a macroporous adsorption resin D101 and eluted with
aqueous EtOH in gradient (0–95%, v/v). The fractions
eluted with 50% aqueous EtOH (70 g) were combined
and subjected to silica gel column chromatography eluted
with CHCl3–MeOH–HAc (9:1:0.1 to 7:3:0.3, v/v) to give
7 subfractions (Fr. 50-1 to Fr. 50-7). Compound 4 (8 mg)
was obtained by ODS column chromatography (MeOH–
H2O, 3:7 to 1:0, v/v) and semi-preparation HPLC using
Agela Venusil XBP RP-8 column (CH3CN–H2O, 67:33,
v/v) from Fr. 50-2.
3. Identification
3.1. Quercetin (1)
Yellow needle (MeOH); 1H NMR (500 MHz, DMSO-d6)
δ: 12.49 (s, 1H, 5-OH), 10.77 (s, 1H, 7-OH), 9.29–9.58 (s,
3H, 3×-OH), 7.67 (d, 1H, J 2 Hz, H-2), 7.53 (dd, 1H, J1 2 Hz,
J2 8.5 Hz, H-6), 6.88 (d, 1H, J 8.5 Hz, H-5), 6.40 (d, 1H,
J 2.5 Hz, H-8), 6.18 (d, 1H, J 2.5 Hz, H-6). All these data
were in good agreement with those of quercetin[7].
3.2. Quercetin 7-O-α-L-rhamnoside (2)
Yellow amorphous powder (MeOH); 1H NMR (500 MHz,
DMSO-d6) δ: 12.48 (s, 1H, 5-OH), 9.29–9.62 (s, 3H,
3×-OH), 7.71 (d, 1H, J 2.5 Hz, H-2), 7.57 (dd, 1H, J1 8.5 Hz,
J2 2 Hz, H-6), 6.88 (d, 1H, J 8.5 Hz, H-5), 6.78 (d, 1H,
J 2 Hz, H-8), 6.40 (d, 1H, J 2 Hz, H-6), 5.53 (d, 1H, J 1 Hz,
H-1), 3.20–3.90 (sugar protons, 4H), 1.12 (d, 3H, J 6 Hz,
H-6); 13C NMR (125 MHz, DMSO-d6) δ: 175.9 (C-4),
161.4 (C-7), 160.4 (C-5), 155.7 (C-8a), 147.9 (C-2), 147.5
(C-4), 145.1 (C-3), 136.1 (C-3), 121.8 (C-1), 120.1 (C-6),
115.6 (C-2), 115.2 (C-5), 104.6 (C-4a), 98.8 (C-6), 98.4
(C-1), 94.2 (C-8), 71.6 (C-4), 70.2 (C-3), 70.1 (C-2),
69.8 (C-5), 17.9 (C-6). All these data were in good agree-
ment with those of quercetin 7-O-α-L-rhamnoside[8,9].
3.3. Quercetin 3-O-α-L-rhamnoside (3)
Yellow amorphous powder (MeOH); 1H NMR (500 MHz,
DMSO-d6) δ: 12.66 (s, 1H, 5-OH), 10.86 (s, 1H, 7-OH),
9.33–9.70 (s, 2H, 2×-OH), 7.29 (d, 1H, J 2 Hz, H-2), 7.24
(dd, 1H, J1 8.5 Hz, J2 2 Hz, H-6), 6.86 (d, 1H, J 8.5 Hz,
H-5), 6.39 (d, 1H, J 2 Hz, H-8), 6.20 (d, 1H, J 2 Hz, H-6),
5.25 (s, 1H, H-1), 3.20–4.10 (sugar protons, 4H), 0.81 (d,
3H, J 6 Hz, H-6); 13C NMR (125 MHz, DMSO-d6) δ: 177.7
(C-4), 164.2 (C-7), 161.3 (C-5), 157.3 (C-8a), 156.4 (C-2),
148.4 (C-4), 145.2 (C-3), 134.2 (C-3), 121.1 (C-1), 120.7
(C-6), 115.6 (C-5), 115.4 (C-2), 104.1 (C-4a), 101.8 (C-1),
98.6 (C-6), 93.6 (C-8), 71.1 (C-4), 70.6 (C-3), 70.3 (C-2),
70.0 (C-5), 17.5 (C-6). All these data were in good agree-
ment with those of quercetin 3-O-α-L-rhamnoside[10,11].
3.4. 3-O-methyl quercetin (4)
Yellow needle (MeOH); 1H NMR (500 MHz, DMSO-d6)
δ: 12.70 (s, 1H, 5-OH), 9.00–11.00 (wide, 3H, -3×OH),
7.54 (d, 1H, J 2.5 Hz, H-2), 7.44 (dd, 1H, J1 2.5 Hz,
J2 8.5 Hz, H-6), 6.90 (d, 1H, J 8.5 Hz, H-5), 6.40 (d, 1H,
J 1.5 Hz, H-8), 6.19 (d, 1H, J 1.5 Hz, H-6), 3.78 (s,
3H, -OCH3); 13C NMR (125 MHz, DMSO-d6) δ: 177.9
(C-4), 164.2 (C-7), 161.3 (C-5), 156.3 (C-8a), 155.6 (C-2),
148.7 (C-4), 145.2 (C-3), 137.6 (C-3), 120.8 (C-1), 120.6
(C-6), 115.8 (C-5), 115.4 (C-2), 104.1 (C-4a), 98.5 (C-6),
93.6 (C-8), 59.7 (-OCH3). All these data were in good
agreement with those of 3-O-methyl quercetin[12].
3.5. 1,5-Dihydroxyxanthone (5)
Yellow needle (MeOH); 1H NMR (500 MHz, DMSO-d6)
δ: 12.62 (s, 1H, 1-OH), 10.55 (s, 1H, 5-OH), 7.74 (t, 1H,
J 8 Hz, H-3), 7.60 (dd, 1H, J1 8 Hz, J2 1 Hz, H-8), 7.36 (dd,
1H, J1 8 Hz, J2 1 Hz, H-6), 7.29 (t, 1H, J 8 Hz, H-7), 7.10
(d, 1H, J 8 Hz, H-4), 6.82 (d, 1H, J 8 Hz, H-2); 13C NMR
(125 MHz, DMSO-d6) δ: 182.1 (C-9), 161.0 (C-1), 155.6
(C-4a), 146.4 (C-5), 145.2 (C-4b), 137.4 (C-3), 124.4 (C-7),
121.1 (C-6), 120.9 (C-8a), 114.6 (C-8), 110.0 (C-2), 108.2
(C-9a), 107.4 (C-4). All these data were in good agreement
with those of 1,5-dihydroxyxanthone[13,14].
3.6. 1,5-Dihydroxyxanthone-6-O-β-D-glucoside (6)
Yellow powder (MeOH); 1H NMR (500 MHz, DMSO-d6)
δ: 12.75 (s, 1H, 1-OH), 7.72 (t, 1H, J 8.3 Hz, H-3), 7.62
(d, 1H, J 9 Hz, H-8), 7.30 (d, 1H, J 9 Hz, H-7), 7.10 (d, 1H,
Zhou, G.S. et al. / J. Chin. Pharm. Sci. 2013, 22 (3), 286–288 288
J 8.3 Hz, H-4), 6.81 (d, 1H, J 8.3 Hz, H-2), 5.14, 5.08
(each 1H, 2×-OH), 5.00 (d, 1H, J 7.6 Hz, H-1), 4.62
(1H, -OH), 3.10–3.80 (4H, sugar protons, overlapped with
water peak); 13C NMR (125 MHz, DMSO-d6) δ: 181.4
(C-9), 161.1 (C-1), 155.9 (C-4a), 150.7 (C-6), 145.6 (C-4b),
137.1 (C-3, 5), 115.4 (C-8, 8a), 112.6 (C-7), 110.0 (C-2),
107.8 (C-9a), 107.2 (C-4), 101.3 (C-1), 77.3 (C-5), 75.8
(C-3), 73.2 (C-2), 69.6 (C-4), 60.6 (C-6). All these data
were in good agreement with those of 1,5-dihydroxyxanthone-
6-O-β-D-glucoside[15].
3.7. 5-Hydroxy-1-methoxyxanthone (7)
Light yellow amorphous powder (MeOH); 1H NMR
(500 MHz, DMSO-d6) δ: 7.74 (t, 1H, J 8 Hz, H-3), 7.51
(dd, 1H, J1 8 Hz, J2 1.5 Hz, H-8), 7.25 (dd, 1H, J1 8 Hz,
J2 1.5 Hz, H-6), 7.19 (t, 1H, J 8 Hz, H-7), 7.16 (d, 1H,
J 8.5 Hz, H-4), 6.98 (d, 1H, J 8 Hz, H-2), 3.90 (s, 3H,
1-OCH3); 13C NMR (125 MHz, DMSO-d6) δ: 174.9 (C-9),
160.1 (C-1), 157.2 (C-4a), 146.1 (C-5), 143.9 (C-10a), 135.4
(C-3), 123.7 (C-7), 123.5 (C-8a), 119.5 (C-6), 115.2 (C-8),
111.5 (C-9a), 109.7 (C-2), 106.2 (C-4), 56.2 (1-OCH3). All
these data were in good agreement with those of 5-hydroxyl-
1-methoxyxanthone[16].
3.8. 6-Deoxyisojacareubin (8)
Light yellow powder (MeOH); 1H NMR (500 MHz,
DMSO-d6) δ: 13.00 (s, 1H, 1-OH), 10.39 (s, 1H, 5-OH),
7.56 (dd, 1H, J1 8 Hz, J2 1.5 Hz, H-8), 7.34 (dd, 1H, J1 8 Hz,
J2 1.5 Hz, H-6), 7.28 (t, 1H, J 8 Hz, H-7), 6.99 (d, 1H,
J 10 Hz, H-4), 6.24 (s, 1H, H-2), 5.80 (d, 1H, J 10 Hz,
H-3), 1.45 (s, 6H, 2×-CH3);13C NMR (125 MHz, DMSO-d6)
δ: 180.6 (C-9), 162.2 (C-1), 160.2 (C-3), 151.1 (C-4a),
146.2 (C-4b), 144.8 (C-5), 127.6 (C-3), 124.4 (C-8),
121.2 (C-7), 120.8 (C-6), 114.7 (C-4), 114.6 (C-8a),
103.0 (C-4), 100.9 (C-9a), 98.5 (C-2), 78.4 (C-2), 27.9
(2×-CH3). All these data were in good agreement with
those of 6-deoxyisojacareubin[17,18].
Acknowledgements
This work was financially supported by National Key
Technology R&D Program “New Drug Innovation” of
China (Grant No. 2012ZX09301002-002-002, 2012ZX-
09304-005).
References
[1] State Administration of Traditional Chinese Medicine. China
Herbal. Vol 2. Shanghai: Shanghai Scientific and Technical
Publishers. 1999, 765–766.
[2] Lei, N.; Zhang, W.S.; Du, S.S. Chin. J. Inform. Tradit. Chin.
Med. 2004, 11, 929–931.
[3] Cheng, L.; Wu, X.X.; Huang, H.; Wu, W.B. Chin. Tradit.
Herb. Drug. 2004, 35, 1076–1079.
[4] Lei, N.; Du, S.S.; Li, L.; Zheng, Y.F.; Zhang, W.S.; Wang,
Y.Y. China J. Chin. Mater. Med. 2007, 32, 918–920.
[5] Chang, Z.Y.; Gong, W.H. Guihaia. 2005, 25, 278–280.
[6] Liu, J.; Qin, M.J. China J. Nat. Med. 2007, 5, 235–236.
[7] Miyazawa, M.; Hisama, M. Biosci. Biotechnol. Biochem.
2003, 67, 2091–2099.
[8] Zhang, L.; Jin, Y.Y.; Tian, J.K. Chin. Pharm. J. 2007, 42,
341–344.
[9] Zheng, S.Z.; Wang, D.Y.; Liu, W.X.; Wang, J.X.; Shen, X.W.
J. Northwest Norm. Univ. Nat. Sci.1999, 35, 37–41.
[10] Ye, G.; Huang, C.G. Chem. Nat. Compd. 2006, 42, 232–234.
[11] Sun, L.; Yu, J.G.; Zhou, L.D.; Luo, X.Z.; Ding, W.;
Yang, S.L. China J. Chin. Mater. Med. 2002, 27, 36–38.
[12] Boers, F.; Deng, B.L.; Lemière, G.; Lepoivre, J.; Groot, A.D.;
Dommisse, R. Arch. Pharm. 1997, 330, 313–316.
[13] Westerman, P.W.; Gnasekera, S.P.; Uvais, M.; Sultanbawa, S.;
Kazlauskas, R. Org. Magn. Resonance. 1977, 9, 631–636.
[14] Li, Y.Z.; Li, Z.L.; Hua, H.M.; Li, Z.G.; Liu, M.S. China J.
Chin. Mater. Med. 2007, 32, 692–694.
[15] Wu, Q.L.; Wang, S.P.; Liao, Y.H.; Wang, L.W.; Feng, Y.X.;
Yang, J.S.; Xiao, P.G. Chin. Chem. Lett. 1996, 7, 1011–
1012.
[16] Rocha, L.; Marston, A.; Auxiliadora, M.; Kaplan, C.; Stoeckli-
Evans, H.; Thull, U.; Testa, B.; Hostettmann, K. Phyto-
chemistry. 1994, 36, 1381–1385.
[17] Fu, P.; Li, T.Z.; Liu, R.H.; Zhang, W.; Zhang, W.D.;
Chen, H.S. Nat. Prod. Res. Dev. 2004, 16, 511–513.
[18] Chen, Y.; Yang, G.Z.; Zhong, F.F.; He, H.W. Bull. Korean
Chem. Soc. 2010, 31, 3418–3420.
小无心菜中黄酮与口山酮类成分研究
周观　, 杨晓娟, 姜勇*, 屠鹏飞
北京大学医学部 天然药物及仿生药物国家重点实验室; 药学院, 北京 100191  
摘要: 运用溶剂萃取结合硅胶、Sephadex LH-20、ODS及半制备液相等色谱方法从小无心菜 (Arenaria serpyllifolia L.)
的全草中分离得到8个已知化合物。应用光谱技术鉴定其结构分别为槲皮素(1), 槲皮素-7-O-α-L-鼠李糖苷(2), 槲皮素-3-O-
α-L-鼠李糖苷(3), 3-O-甲基槲皮素(4), 1,5-二羟基口山酮(5), 1,5-二羟基口山酮-6-O-β-D-葡萄糖苷(6), 5-羟基-1-甲氧基口山酮(7) 和
6-deoxyisojacareubin (8)。以上化合物均为首次从小无心菜中分离得到, 化合物5–8为首次从蚤缀属植物中分离得到。
关键词: 小无心菜; 化学成分; 黄酮; 口山酮
燊