全 文 ：Chemical constituents from the roots of Polygala wattersii Hance
Yuhong Zhou 1a , Qiang Guo 2a , Yong Jiang 1 , Pengfei Tu 1,2*
1. State Key Laboratory of Natural and Biomimetic Drugs, Peking University Health Science Center, Beijing 100191, China
2. Modern Research Center for Traditional Chinese Medicine, Beijing University of Chinese Medicine, Beijing 100029, China
Abstract: To investigate the chemical constituents of the roots of Polygala wattersii Hance, the separation and purification
were performed by solvent extraction and repeated column chromatography (CC) on silica gel, Sephadex LH20 and macroporous
resin D101, preparative TLC and semipreparative HPLC. The structures were identified by spectroscopic analysis and comparison
of their 1 H and 13 C NMR data with those reported in literatures. Twentythree known compounds, including eleven xanthones (1–11),
nine sugar esters (12–20), two triterpenoid saponins (21 and 22) and one phenylpropanoid (23) were isolated and their structures were
identified as 1,3dihydroxyxanthone (1), 1hydroxy3methoxyxanthone (2), 1,3dihydroxy2methoxyxanthone (3), 1,3,7trihydroxy2
methoxyxanthone (4), 1,3,6trihydroxy2,7dimethoxyxanthone (5), 1,6,7trihydroxy2,3dimethoxyxanthone (6), 1,7dihydroxy
2,3methylenedioxyxanthone (7), 1,7dimethoxyxanthone (8), 1,2,3trimethoxyxanthone (9), 1methoxy2,3methylenedioxyxanthone (10),
6hydroxy1methoxy2,3methylenedioxyxanthone (11), 3Oferuloyl6Oacetyl sucrose (12), arillatose B (13), sibricose A5 (14),
sibricose A6 (15), 3,6diOsinapoyl sucrose (16), tenufoliside A (17), 3O3,4,5trimethoxycinnamoyl6Opmethoxybenzoyl
sucrose (18), glomeratose A (19), 1OpcoumaroylDglucopyranose (20), bayogenin3Oglucoside (21), tenufolin (22), and
sinapic acid (23). Among them, compounds 2 and 12 were obtained from genus Polygala for the first time, and except compound
16, all others were isolated from this species for the first time.
Keywords: Polygalaceae, Polygala wattersii Hance, Chemical constituents, Xanthones, Sugar esters
CLC number: R284 Document code: A Article ID: 1003–1057(2014)10–723–08
Received: 20140113, Revised: 20140210, Accepted: 20140215.
Foundation items: The National Key Technology R&D Program
“New Drug Innovation” of China (Grant No. 2012ZX09301002002002,
2012ZX09304005), special funds for scientific research on traditional
Chinese medicine (Grant No. 201307002), and National Science Fund
for Excellent Young Scholars (Grant No. 81222051).
a These authors contribute to the paper equally.
* Corresponding author. Tel.: 861082802750, Fax: 861082802859,
Email: pengfeitu@vip.163.com
http://dx.doi.org/10.5246/jcps.2014.10.092
1. Introduction
Polygala wattersii Hance is distributed in southwestern
China. It is used in folk medicines as tonics, antipyretic,
promoting blood circulation to detoxicate, as well as
tendon relaxation and activation of blood circulation [1] .
Up to now, there is only one paper reported that oligo
saccharide esters and xanthone glycosides were contained
in this plant [2] . As part of our systematic investigation
on bioactive constituents from Polygalaceae plants [3–12] ,
the roots of P. wattersii were systematically investigated.
We report herein the isolation and structure elucidation of
23 known compounds, including eleven xanthones (1–11),
nine sugar esters (12–20), two triterpenoid saponins (21 and
22) and one phenylpropanoid (23) (Fig. 1). By spectroscopic
analysis and comparison of their 1 H and 13 C NMR data
with those reported in literatures, these compounds were
identified as 1,3dihydroxyxanthone (1), 1hydroxy3
methoxyxanthone (2), 1,3dihydroxy2methoxyxanthone (3),
1,3,7trihydroxy2methoxyxanthone (4), 1,3,6trihydroxy
2,7dimethoxyxanthone (5), 1,6,7trihydroxy2,3dimethoxy
xanthone (6), 1,7dihydroxy2,3methylenedioxyxanthone (7),
1,7dimethoxyxanthone (8), 1,2,3trimethoxyxanthone (9),
1methoxy2,3methylenedioxyxanthone (10), 6hydroxy1
methoxy2,3methylenedioxyxanthone (11), 3Oferuloyl
6Oacetyl sucrose (12), arillatose B (13), sibricose A5
(14), sibricose A6 (15), 3,6diOsinapoyl sucrose (16),
tenufoliside A (17), 3O3,4,5trimethoxycinnamoyl6
Opmethoxybenzoyl sucrose (18), glomeratose A (19),
1OpcoumaroylDglucopyranose (20), bayogenin3
Oglucoside (21), tenufolin (22), and sinapic acid (23).
Among them, compounds 2 and 12 were obtained
from genus Polygala for the first time, and except
compound 16, all others were isolated from this species
for the first time.
2. Experimental
2.1. General procedures
NMR spectra were performed on a Varian INOVA500
723 Journal of Chinese Pharmaceutical Sciences http://www.jcps.ac.cn
网络出版时间：2014-10-29 16:47
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724 Zhou, Y.H. et al. / J. Chin. Pharm. Sci. 2014, 23 (10), 723–730
spectrometer or a Jeol JNMA300 spectrometer. ESITOF
MS spectra were obtained on a QSTAR mass spectrometer.
Semipreparative HPLC system consisted of a Waters600E
multisolvent delivery pump with a Waters 2487 dual λ
absorbance detector. The reversedphase chromatography
was carried out on a Waters Preparative NovaPak HR
C18 column (300 mm×10 mm) or a Kromasil C18 column
(250 mm×4.6 mm). Silica gel (100–200, 200–300 mesh)
used in column chromatography (CC) and GF254 TLC
silica gel are products of Qingdao Haiyang Chem. Co.
Ltd. D101 macroporous resin is product of Tianjin Chem.
Co. Ltd. Sephadex LH20 is product of Pharmacia.
Solvents of analytical grade are products of Beijing
Chemical Factory.
2.2. Plant materials
The roots of P. wattersii were collected from
Daweishan, Pingbian County of Yunnan Province,
China, in Aug 2006, and identified by Shukun Chen,
researcher of Kunming Institute of Botany, Chinese
Academy of Science. A voucher specimen (No.
PW20060816) is deposited in the herbarium of the
Modern Research Center for Traditional Chinese
Medicine, Peking University Health Science Center.
2.3. Extraction and isolation
The airdried roots of P. wattersii (4 kg) were refluxed
three times with 95% EtOH and 50% EtOH successively
for 2 h each time. The extracts were combined and
evaporated in vacuo. The residue (650 g) was suspended
in H2O and partitioned successively with petroleum
ether (PE), CHCl3, and nBuOH to obtain the PEsoluble
extract (57.5 g), CHCl3–soluble extract (16.3 g), and
nBuOHsoluble extract (64.2 g), respectively.
The PEsoluble extract (46 g) was subjected to silica
gel (100–200 mesh, 450 g) CC, eluting with a gradient
of PE–acetone (15:1–1:1, v/v) to afford 54 fractions.
Compound 2 (12 mg) was obtained as needle crystals
from fraction 5. Fractions 8–11 were further subjected
to silica gel CC, eluting with PE–EtOAc (7:1, v/v).
Among them, subfractions 25–30 were purified by
preparative TLC to yield compounds 3 (8 mg), and
compound 9 (14 mg) was obtained as needle crystals
from subfractions 39. Compound 10 (10 mg) was
obtained as needle crystals from fraction 13. Fractions
20–26 were further subjected to silica gel CC, eluting
with a gradient of PE–acetone (7:1–3:1, v/v). Among
them, subfraction 6 was purified by preparative TLC to
yield compound 8 (4 mg), and compound 1 (5 mg) was
obtained from subfractions 8–13 by silica gel CC,
eluting with PE–acetone (3:1, v/v).
The CHCl3–soluble extract (15 g) was subjected to
silica gel CC (100–200 mesh), eluting with a gradient of
CHCl3–CH3OH (100:1–1:1, v/v) to afford 40 fractions.
Fractions 11–15 were further subjected to silica gel CC,
eluting with CHCl3–MeOH (20:1, v/v). Among them,
subfractions 2–8 were further subjected to silica gel
CC, eluting with cyclohexane–EtOAc (1:1, v/v) to give
fractions 1–10. Compound 4 (12 mg) was obtained as
needle crystals from the fraction 1, compound 7 (8 mg)
was obtained from the fractions 4–7 by Sephaxdex
LH20 CC (CHCl3–MeOH, 1:1, v/v), and compound 6
(10 mg) was obtained as powder from the fractions 9–10.
O 4
1
R 1
R 2
R 3 R 4
R 5
O O
OH
HO
COOH
O
OH
MeO
HO
MeO
4a 4b
5
8 9
8a 8b
20
23
O
OH
OH
OH
O
O
HO
OH
R 1 O
OH
R 2 O
O
OH
OH
O
HO
OH
1
2
5
6
1
2
3
5
6
1
3
6
7 9
1
3
6
7
9
O
OH
OH
O
HO
OH
1
3 5 7
9
10
11
12
13
14 15
18
19
22
23 24
25 26
27
28
29 30
HO
COOH
COOH
O
OH
OH
O
HO
OH
OH
OH
21 22
No. R1 R2 R3 R4 R5
1 OH H OH H H
2 OH H OMe H H
3 OH OMe OH H H
4 OH OMe OH H OH
5 OH OMe OH OH OMe
6 OH OMe OMe OH OH
7 OH OCH2O H OH
8 OMe H H H OMe
9 OMe OMe OMe H H
10 OMe OCH2O H H
11 OMe OH H OCH2O
A: Acetyl
B: Feruloyl
C: Sinapoyl
D: pHydroxybenzoyl
E: pMethoxybenzoyl
F: 3,4,5Trimethoxycinnamoyl
No. R1 R2
12 A B
13 B H
14 H B
15 H C
16 C C
17 D F
18 E F
19 H F
725 Zhou, Y.H. et al. / J. Chin. Pharm. Sci. 2014, 23 (10), 723–730
Fractions 28–36 were further subjected to silica gel CC,
eluting with cyclohexane–EtOAc (3:1, v/v). Among them,
subfractions 18–23 were purified by Sephaxdex LH20
CC (CHCl3–MeOH, 1:1, v/v) to yield compound 11
(6 mg). Compound 5 (15 mg) was obtained as powder
from fraction 40.
The nBuOH–soluble extract (60 g) was dissolved
in H2O and then filtered, the filtrate was subjected to
macroporous resin D101 CC, and successively eluted
with H2O (6 L), 10% EtOH (8 L), 30% EtOH (10 L),
50% EtOH (8 L). The 10% EtOH eluate (6 g) was
subjected to Sephadex LH20 CC (MeOH–H2O) to afford
18 fractions. Fractions 7–10 were subjected to silica
gel CC, eluting with a gradient of CHCl3–MeOH–H2O
(7:1:0.1–7:3:0.3, v/v/v). Among them, subfractions 21–24
were purified by semipreparative HPLC (MeOH–H2O,
16:84, v/v) to yield compounds 14 (4 mg, tR = 32.4 min)
and 15 (6 mg, tR = 38.0 min), and subfractions 30–32
were purified by semipreparative HPLC (MeOH–H2O,
35:65, v/v) to yield compound 16 (4 mg, tR = 35.3 min).
Fractions 11–18 were subjected to silica gel CC,
eluting with a gradient of CHCl3–MeOH–H2O (7:1:0.1–
7:3:0.3, v/v/v). Among them, subfractions 11–15 were
recrystallized in MeOH to yield compound 20 (8 mg).
The 30% EtOH eluate (18 g) was subjected to Sephadex
LH20 CC, eluting with CH3OH–H2O to afford 8
fractions. Fractions 5–8 were subjected to silica gel
CC, eluting with CHCl3–MeOH–H2O (7:1:0.1, v/v/v).
Among them, subfractions 15–23 were purified by semi
preparative HPLC (MeOH–H2O, 45:55, v/v) to yield
compound 18 (7 mg, tR = 28.6 min), subfractions 24–43
were purified by semipreparative HPLC (MeOH–H2O,
32:68, v/v) to yield compounds 13 (5 mg, tR = 25.6 min),
19 (4 mg, tR = 30.1 min) and 12 (5 mg, tR = 36.8 min),
and subfractions 60–64 were purified by semipreparative
HPLC (MeOH–H2O, 25:75, v/v) to yield compound 17
(5 mg, tR = 40.2 min). The 50% EtOH eluate (5 g) was
subjected to silica gel CC, eluting with CHCl3–MeOH
to afford 66 fractions. Fractions 21–23 were recrystallized
in MeOH to yield compound 23 (14 mg). Fraction 48
was recrystallized in MeOH to yield compound 22
(11 mg). Fraction 66 was recrystallized in MeOH to
yield compound 21 (8 mg).
3. Identification
3.1. 1,3Dihydroxyxanthone (1)
Yellow needle crystal. ESIMS: m/z 229.0 [M+H] + ;
1 H NMR (CD3COCD3, 300 MHz) δ: 12.87 (1H, s,
OH), 8.19 (1H, dd, J1 7.8 Hz, J2 1.8 Hz, H8), 7.82 (1H, dt,
J1 6.6 Hz, J2 2.1 Hz, H7), 7.54 (1H, dd, J1 9.0 Hz,
J2 1.8 Hz, H5), 7.46 (1H, dt, J1 9.0 Hz, J2 1.8 Hz, H6),
6.52 (1H, d, J 2.1 Hz, H4), 6.38 (1H, d, J 2.1 Hz, H2);
13 C NMR (CD3COCD3, 75 MHz) data see Table 1.
All above data were in good agreement with those of
1,3dihydroxyxanthone [13] .
3.2. 1Hydroxy3methoxyxanthone (2)
Yellow needle crystal. ESIMS: m/z 243.1 [M+H] + ;
1 H NMR (CDCl3, 300 MHz) δ: 13.11 (1H, s, OH), 8.24
(1H, dd, J1 8.5 Hz, J2 2.0 Hz, H8), 7.71 (1H, td, J1 7.2 Hz,
J2 1.8 Hz, H6), 7.43 (1H, d, J 8.4 Hz, H5), 7.36 (1H, t,
J 7.8 Hz, H7), 6.64 (1H, s, H4), 6.54 (1H, s, H2),
4.05 (3H, s, OMe). All above data were in good agreement
with those of 1hydroxy3methoxyxanthone [14] .
3.3. 1,3Dihydroxy2methoxyxanthone (3)
Yellow needle crystal. ESIMS: m/z 259.1 [M+H] + ;
1 H NMR (CDCl3, 500 MHz) δ: 13.12 (1H, s, OH), 8.24
(1H, dd, J1 8.0 Hz, J2 2.0 Hz, H8), 7.70 (1H, td, J1 7.5 Hz,
J2 2.0 Hz, H6), 7.46 (1H, d, J 9.0 Hz, H5), 7.37 (1H,
t, J 7.5 Hz, H7), 6.54 (1H, s, H4), 4.02 (3H, s, OMe);
13 C NMR (CDCl3, 125 MHz) data see Table 1. All above
data were in good agreement with those of 1,3dihydroxy
2methoxyxanthone [15] .
3.4. 1,3,7Trihydroxy2methoxyxanthone (4)
Yellow needle crystal. ESIMS: 297.0 [M+Na] + , 275.0
[M+H] + ; 1 H NMR (DMSOd6, 500 MHz) δ: 12.94 (1H,
s, OH1), 10.94 (1H, br s, OH3), 9.98 (1H, s, OH7),
7.46 (1H, d, J 8.5 Hz, H5), 7.39 (1H, d, J 3.0 Hz,
H8), 7.27 (1H, dd, J1 9.0 Hz, J2 3.0 Hz, H6), 6.46
(1H, s, H4), 3.74 (3H, s, OMe); 13 C NMR (DMSOd6,
125 MHz) data see Table 1. All above data were in
good agreement with those of 1,3,7trihydroxy2
methoxyxanthone [16] .
3.5. 1,3,6Trihydroxy2,7dimethoxyxanthone (5)
Yellow powder. ESIMS m/z: 305.1 [M+H] + ; 1 H NMR
(DMSOd6, 500 MHz) δ: 7.81 (1H, s, H8), 6.89 (1H,
s, H5), 6.43 (1H, s, H4), 3.87 (OMe2), 3.73 (OMe7);
13 C NMR (DMSOd6, 125 MHz) data see Table 1.
All above data were in good agreement with those of
1,3,6trihydroxy2,7dimethoxyxanthone [17] .
726 Zhou, Y.H. et al. / J. Chin. Pharm. Sci. 2014, 23 (10), 723–730
3.6. 1,6,7Trihydroxy2,3dimethoxyxanthone (6)
Yellow powder. ESIMS: m/z 305.1 [M+H] + ; 1 H
NMR (CD3COCD3, 500 MHz) δ: 13.34 (1H, s, OH),
7.53 (1H, s, H8), 6.92 (1H, s, H5), 6.44 (1H, s, H4),
3.97 (3H, s, OMe2), 3.86 (3H, s, OMe3); 13 C NMR
(CD3COCD3, 125 MHz) data see Table 1. All above data
were in good agreement with those of 1,6,7trihydroxy
2,3dimethoxyxanthone [18] .
3.7. 1,7Dihydroxy2,3methylenedioxyxanthone (7)
Yellow needle crystal. ESIMS: m/z 273.0 [M+H] + ;
1 H NMR (CD3COCD3, 500 MHz) δ: 12.87 (1H, s, OH),
7.56 (1H, d, J 3.0 Hz, H8), 7.47 (1H, d, J 9.0 Hz, H5),
7.38 (1H, dd, J1 9.0 Hz, J2 3.0 Hz, H6), 6.64 (1H, s,
H4), 6.16 (2H, s, OCH2O); 13 C NMR (DMSOd6,
125 MHz) data see Table 1. All above data were in good
agreement with those of 1,7dihydroxy2,3methylene
dioxyxanthone [18] .
3.8. 1,7Dimethoxyxanthone (8)
White needle crystal. ESIMS: m/z 257.1 [M+H] + ;
1 H NMR (CD3COCD3, 300 MHz) δ: 7.72 (1H, t, J 7.8 Hz,
H3), 7.61 (1H, d, J 3.0 Hz, H8), 7.47 (1H, d, J 8.4 Hz,
H5), 7.35 (1H, dd, J1 8.4 Hz, J2 3.0 Hz, H6), 7.11 (1H, d,
J 7.8 Hz, H4), 6.95 (1H, d, J 7.8 Hz, H2), 3.98 (3H, s,
OMe1), 3.94 (3H, s, OMe7); 13 C NMR (CD3COCD3,
75 MHz) data see Table 1. All above data were in good
agreement with those of 1,7dimethoxyxanthone [19] .
3.9. 1,2,3Trimethoxyxanthone (9)
White needle crystal, bluegreen fluorescence under
UV light. ESIMS: m/z 287.1 [M+H] + ; 1 H NMR (CDCl3,
300 MHz) δ: 8.30 (1H, dd, J1 7.8 Hz, J2 1.5 Hz, H8),
7.67 (1H, td, J1 7.8 Hz, J2 1.8 Hz, H6), 7.39 (1H, d,
J 7.8 Hz, H5), 7.33 (1H, t, J 7.8 Hz, H7), 6.75 (1H, s,
H4), 4.04 (3H, s, OMe1), 3.99 (3H, s, OMe3), 3.92
(3H, s, OMe2); 13 C NMR (CDCl3, 75 MHz) data see
Table 1. All above data were in good agreement with
those of 1,2,3trimethoxyxanthone [20] .
3.10. 1Methoxy2,3methylenedioxyxanthone (10)
White needle crystal, blue fluorescence under UV
light. ESIMS: m/z 271.1 [M+H] + ; 1 H NMR (CDCl3,
300 MHz) δ: 8.27 (1H, dd, J1 8.1 Hz, J2 1.8 Hz, H8),
7.63 (1H, td, J1 7.2 Hz, J2 1.8 Hz, H6), 7.36 (1H, d,
J 7.8 Hz, H5), 7.30 (1H, t, J 7.8 Hz, H7), 6.65 (1H, s,
H4), 6.06 (2H, s, OCH2O), 4.17 (3H, s, OMe); 13 C NMR
(CD3COCD3, 75 MHz) data see Table 1. All above
data were in good agreement with those of 1methoxy
2,3methylenedioxyxanthone [6] .
3.11. 6Hydroxy1methoxy2,3methylenedioxy
xanthone (11)
Yellow powder. ESIMS: m/z 309.0 [M+Na] + , 287.1
[M+H] + ; 1 H NMR (DMSOd6, 500 MHz) δ: 9.82 (1H,
s, OH), 7.41 (1H, m, H7), 7.39 (1H, m, H8), 7.22
(1H, dd, J1 3.0 Hz, J2 9.0 Hz, H5), 6.92 (1H, s, H4),
Position 1 a,d 3 b,e 4 c,e 5 c,e 6 a,e 7 c,e 8 a,d 9 b,d 10 a,d 11 a,e
1 164.5 152.8 153.2 151.8 152.4 141.7 164.3 153.6 142.8 142.0
2 98.5 129.4 129.2 129.9 130.5 128.6 111.1 139.6 136.1 134.4
3 166.8 153.2 158.3 153.3 157.9 155.1 137.1 158.7 155.4 155.6
4 94.3 93.7 93.3 93.3 93.5 89.4 107.7 96.0 94.1 93.9
4a 158.6 155.9 152.1 157.4 153.9 154.1 158.8 154.6 154.9 152.6
4b 156.3 156.1 148.4 154.1 151.9 149.1 151.2 155.2 155.8 147.4
5 119.1 117.5 118.4 102.1 102.7 119.0 120.2 117.1 118.0 121.7
6 136.8 134.7 124.0 151.3 154.6 124.8 125.3 133.9 134.8 153.6
7 125.7 124.0 153.3 145.4 146.0 153.1 157.3 123.8 124.7 108.0
8 126.9 125.6 107.2 104.0 104.5 107.5 108.3 126.7 126.9 117.9
8a 122.2 120.0 119.3 110.5 111.1 119.8 124.1 122.4 123.1 122.7
8b 103.8 104.3 101.6 101.2 101.6 104.3 113.3 110.9 111.6 109.0
9 181.1 181.2 179.5 178.6 179.1 180.6 177.4 175.4 174.9 173.4
OMe1 56.8 62.0 61.2 60.2
OMe2 60.8 59.4 59.4 60.1 61.6
OMe3 55.7 56.3
OMe7 55.3 56.4
OCH2O 102.8 103.5 103.2
Table 1. 13 C NMR data of compounds 1 and 3–12, δ in ppm
a Measured in CD3COCD3, b in CDCl3 and c in DMSOd6, d Recorded at 75 MHz and e at 125 MHz.
727 Zhou, Y.H. et al. / J. Chin. Pharm. Sci. 2014, 23 (10), 723–730
6.20 (2H, s, OCH2O), 3.97 (3H, s, OMe); 13 C NMR
(CD3COCD3, 125 MHz) data see Table 1. All above
data were in good agreement with those of 6hydroxy
1methoxy2,3methylenedioxyxanthone [20] .
3.12. 3OFeruloyl6Oacetyl sucrose (12)
Yellow amorphous powder, skyblue fluorescence
under UV light. ESIMS: m/z 583.3 [M+Na] + , 561.3
[M+H] + ; 1 H NMR (CD3OD, 500 MHz) δ: 7.69 (1H, d,
J 16.0 Hz, Hγ of feruloyl), 7.23 (1H, d, J 2.0 Hz, H2
of feruloyl), 7.12 (1H, dd, J1 8.5 Hz, J2 2.0 Hz, H6 of
feruloyl), 6.80 (1H, d, J 8.0 Hz, H5 of feruloyl), 6.42
(1H, d, J 16.0 Hz, Hβ of feruloyl), 5.45 (1H, d, J 8.0 Hz,
H3 of Fru), 5.43 (1H, d, J 4.0 Hz, H1 of Glc), 4.32
(1H, t, J 8.0 Hz, H4 of Fru), 3.89 (3H, s, OMe), 2.07
(CH3COO); 13 C NMR (CD3OD, 125 MHz) δ: 172.8
(CO of Ac), 168.3 (C9), 150.7 (C3), 149.3 (C4),
147.7 (C7), 127.6 (C1), 124.2 (C6), 116.4 (C5),
114.9 (C8), 112.1 (C2), 104.8 (C2 of Fru), 92.8 (C1
of Glc), 84.3 (C5 of Fru), 79.6 (C3 of Fru), 74.9 (C4
of Fru), 74.1 (C3 of Glc), 72.2 (C2 of Glc), 72.0 (C5
of Glc), 71.7 (C4 of Glc), 65.3 (C1 of Fru), 65.1 (C6
of Glc), 63.6 (C6 of Fru), 56.5 (OMe), 20.8. All above
data were in good agreement with those of 3O
feruloyl6Oacetyl sucrose [21] .
3.13. Arillatose B (13)
Yellow powder. ESIMS: m/z 541.2 [M+Na] + , 519.2
[M+H] + ; 1 H NMR (CD3OD, 500 MHz) δ: 7.69 (1H, d,
J 16.0 Hz, Hγ of feruloyl), 7.22 (1H, d, J 2.0 Hz, H2
of feruloyl), 7.13 (1H, dd, J1 8.5 Hz, J2 2.0 Hz, H6 of
feruloyl), 6.80 (1H, d, J 8.0 Hz, H5 of feruloyl), 6.42
(1H, d, J 16.0 Hz, Hβ of feruloyl), 5.42 (1H, d, J 4.0 Hz,
H1 of Glc), 3.89 (3H, s, OMe); 13 C NMR (CD3OD,
125 MHz) δ: 168.3 (C9), 150.7 (C3), 149.3 (C4),
147.7 (C7), 127.7 (C1), 124.2 (C6), 116.5 (C5),
115.0 (C8), 112.1 (C2), 104.8 (C2 of Fru), 93.3 (C1
of Glc), 84.3 (C5 of Fru), 79.7 (C3 of Fru), 75.7 (C4
of Fru), 74.9 (C3 of Glc), 73.1 (C2 of Glc), 72.2 (C5
of Glc), 71.7 (C4 of Glc), 65.3 (C6 of Glc), 64.3 (C1
of Fru), 56.5 (OMe). All above data were in good
agreement with those of arillatose B [22] .
3.14. Sibricose A5 (14)
Yellow powder. ESIMS: m/z 519.2 [M+H] + ; 1 H NMR
(CD3OD, 300 MHz) δ: 7.70 (1H, d, J 15.9 Hz, Hγ of
feruloyl), 7.22 (1H, d, J 1.8 Hz, H2 of feruloyl), 7.13
(1H, dd, J1 8.4 Hz, J2 2.1 Hz, H6 of feruloyl), 6.80
(1H, d, J 8.1 Hz, H5 of feruloyl), 6.43 (1H, d, J 15.9 Hz,
Hβ of feruloyl), 5.46 (1H, d, J 8.1 Hz, H3 of Fru),
5.43 (1H, d, J 3.9 Hz, H1 of Glc), 4.37 (1H, t, J 7.8 Hz,
H4 of Fru), 3.89 (3H, s, OMe); 13 C NMR (CD3OD,
75 MHz) δ: 168.3 (C9), 150.7 (C3), 149.3 (C4),
147.7 (C7), 127.7 (C1), 124.2 (C6), 116.5 (C5),
115.0 (C8), 112.1 (C2), 104.8 (C2 of Fru), 93.3 (C1
of Glc), 84.3 (C5 of Fru), 79.7 (C3 of Fru), 74.9 (C3
of Glc), 74.2 (C4 of Fru), 73.1 (C2 of Glc), 73.8 (C5
of Glc), 71.7 (C4 of Glc), 65.3 (C1 of Fru), 62.3 (C6
of Glc), 56.5 (OMe). All above data were in good
agreement with those of sibricose A5 [23] .
3.15. Sibricose A6 (15)
Yellow powder, skyblue fluorescence under UV
light. ESIMS: m/z 549.2 [M+H] + ; 1 H NMR (CD3OD,
300 MHz) δ: 7.70 (1H, d, J 15.9 Hz, Hγ of sinapoyl),
6.95 (2H, s, H2,6 of sinapoyl), 6.40 (1H, d, J 15.9 Hz,
Hβ of sinapoyl), 5.46 (1H, d, J 8.1 Hz, H3 of Fru),
5.43 (1H, d, J 3.9 Hz, H1 of Glc), 4.37 (1H, t, J 7.8 Hz,
H4 of Fru), 3.82 (6H, s, OMe3,5); 13 C NMR (CD3OD,
125 MHz) δ: 168.1(C9), 149.4 (C3,5), 147.8 (C7),
139.6 (C4), 126.6 (C1), 115.4 (C8), 106.9 (C2,6),
105.3 (C2 of Fru), 93.6 (C1 of Glc), 83.8 (C5 of
Fru), 79.3 (C3 of Fru), 75.7 (C3 of Glc), 74.6 (C4 of
Fru), 74.4 (C5 of Glc), 73.2 (C2 of Glc), 71.3 (C4 of
Glc), 64.0 (C1 of Fru), 63.4 (C6 of Fru), 62.2 (C6 of
Glc), 56.8 (OMe). All above data were in good agreement
with those of sibricose A6 [23] .
3.16. 3,6DiOsinapoyl sucrose (16)
Yellow amorphous powder, skyblue fluorescence
under UV light. ESIMS: m/z 755.2 [M+H] + ; 1 H NMR
(CD3OD, 500 MHz) δ: 7.62, 7.53 (each 1H, d, J 16.0 Hz,
Hγ of two sinapoyl), 6.41, 6.38 (each 1H, d, J 16.0 Hz,
Hβ of two sinapoyl), 6.87, 6.83 (each 2H, s, H2,6 of
two sinapoyl), 5.45 (1H, d, J 8.0 Hz, H3 of Fru), 5.44
(1H, d, J 4.0 Hz, H1 of Glc), 4.45 (1H, t, J 8.0 Hz,
H4 of Fru), 3.82, 3.79 (each 6H, s, OMe3,5 of two
sinapoyl); 13 C NMR (CD3OD, 125 MHz) δ: 169.0 (C9),
168.2 (C9), 149.4 (C3,5,3,5), 147.9 (C7), 147.2
(C7), 126.6 (C1), 126.5 (C1), 115.8 (C8), 115.5
(C8), 107.1 (C2,6), 106.9 (C2,6), 104.8 (C2 of Fru),
92.6 (C1 of Glc), 84.3 (C5 of Fru), 79.2 (C3 of Fru),
75.1 (C3 of Glc), 74.2 (C4 of Fru), 73.1 (C2 of Glc),
728 Zhou, Y.H. et al. / J. Chin. Pharm. Sci. 2014, 23 (10), 723–730
72.5 (C5 of Glc), 71.9 (C4 of Glc), 65.7 (C1 of
Fru1), 65.6 (C6 of Glc), 63.8 (C6 of Fru), 56.9 (OMe),
56.8 (OMe). All above data were in good agreement
with those of 3,6diOsinapoyl sucrose [24] .
3.17. Tenufoliside A (17)
Yellow powder, skyblue fluorescence under UV
light. ESIMS: m/z 705.2 [M+Na] + , 700.3 [M+NH4] + ;
1 H NMR (CD3OD, 500 MHz) δ: 7.85 (2H, d, J 7.0 Hz,
H2,6 of phydroxybenzoyl), 7.66 (1H, d, J 16.0 Hz,
Hγ of 3,4,5trimethoxycinnamoyl), 6.89 (2H, s, H2,6
of 3,4,5trimethoxycinnamoyl), 6.76 (2H, d, J 7.0 Hz,
H3,5 of phydroxybenzoyl), 6.48 (1H, d, J 16.0 Hz, Hβ
of 3,4,5trimethoxycinnamoyl), 5.44 (1H, d, J 8.0 Hz,
H3 of Fru), 5.42 (1H, d, J 3.5 Hz, H1 of Glc), 4.32
(1H, t, J 8.0 Hz, H4 of Fru), 3.80 (6H, s, OMe3,5 of
3,4,5trimethoxycinnamoyl), 3.72 (3H, s, OMe4 of
3,4,5trimethoxycinnamoyl); 13 C NMR (CD3OD,125 MHz)
δ: 168.2 (C9),149.4 (C3,5), 147.8 (C6), 139.5 (C4),
126.5 (C1), 115.8 (C7), 107.0 (C2),104.8 (C2 of
Fru), 92.6 (C1 of Glc), 84.3 (C5 of Fru), 79.2 (C3 of
Fru), 75.1 (C3 of Glc), 74.1 (C4 of Fru), 73.1 (C2 of
Glc), 72.5 (C5 of Glc), 71.9 (C4 of Glc), 65.7 (C1 of
Fru), 65.6 (C6 of Glc), 63.8 (C6 of Fru), 56.8 (OMe).
All above data were in good agreement with those of
tenufoliside A [25] .
3.18. 3O3,4,5Trimethoxycinnamoyl6Opmethoxy
benzoyl sucrose (18)
Yellow powder. ESIMS: m/z 697.2 [M+H] + ; 1 H NMR
(CD3OD, 500 MHz) δ: 7.93 (2H, dd, J1 7.0 Hz, J2 2.0 Hz,
H2,6 of pmethoxybenzoyl), 7.64 (1H, d, J 16.0 Hz, Hγ
of 3,4,5trimethoxycinnamoyl), 6.90 (2H, dd, J1 7.0 Hz,
J2 2.0 Hz, H3,5 of pmethoxybenzoyl), 6.89 (2H, s,
H2,6 of 3,4,5trimethoxycinnamoyl), 6.48 (1H, d,
J 16.0 Hz, Hβ of 3,4,5trimethoxycinnamoyl), 5.44 (1H,
d, J 3.5 Hz, H1 of Glc), 5.43 (1H, d, J 7.5 Hz, H3 of Fru),
3.80 (6H, s, OMe3,5 of 3,4,5trimethoxycinnamoyl), 3.72
(3H, s, OMe4 of 3,4,5trimethoxycinnamoyl); 13 C NMR
(CD3OD, 125 MHz) δ: 167.8 (C7), 167.7 (C9), 165.1
(C4), 155.0 (C3,5), 147.5 (C7), 141.2 (C4), 132.6
(C2,6), 131.2 (C1), 123.3 (C1), 117.5 (C8), 114.8
(C3,5), 107.2 (C2,6), 104.8 (C2 of Fru), 93.2 (C1
of Glc), 84.3 (C5 of Fru), 79.8 (C3 of Fru), 74.8 (C3
of Glc), 74.0 (C4 of Fru), 73.2 (C2 of Glc), 72.4 (C4
of Glc), 65.5 (C6 of Glc), 65.2 (C1 of Fru), 63.3 (C6
of Fru), 61.6(OMe4), 56.7 (OMe3,5), 55.9 (OMe4).
All above data were in good agreement with those of
3O3,4,5trimethoxycinnamoyl6Opmethoxybenzoyl
sucrose [26] .
3.19. Glomeratose A (19)
Yellow powder, skyblue fluorescence under UV light.
ESIMS: m/z 585.2 [M+Na] + , 563.3 [M+H] + ; 1 H NMR
(CD3OD, 500 MHz) δ: 7.71 (1H, d, J 16.0 Hz, Hγ of
3,4,5trimethoxycinnamoyl), 6.97 (2H, s, H2,6 of
3,4,5trimethoxycinnamoyl), 6.54 (1H, d, J 16.0 Hz, Hβ
of 3,4,5trimethoxycinnamoyl), 5.47 (1H, d, J 8.0 Hz,
H3 of Fru), 5.43 (1H, d, J 4.5 Hz, H1 of Glc), 4.38
(1H, t, J 8.0 Hz, H4 of Fru), 3.87 (6H, s, OMe3,5 of
3,4,5trimethoxycinnamoyl), 3.78 (3H, s, OMe4 of
3,4,5trimethoxycinnamoyl); 13 C NMR (CD3OD, 125
MHz) δ: 167.7 (C9), 154.8 (C3,5), 147.2 (C7), 141.3
(C4), 131.5 (C1), 117.9 (C8), 106.9 (C2,6), 104.8
(C2 of Fru), 93.3 (C1 of Glc), 84.2 (C5 of Fru), 79.8
(C3 of Fru), 74.9 (C3 of Glc), 74.6 (C4 of Fru), 73.8
(C5 of Glc), 73.1 (C2 of Glc), 71.2 (C4 of Glc), 65.3
(C1 of Fru), 62.8 (C6 of Fru), 62.3 (C6 of Glc), 61.2
(OMe4), 56.8 (OMe3,5). All above data were in good
agreement with those of glomeratose A [24] .
3.20. 1OpCoumaroylDglucopyranose (20)
White granule, ianthinus fluorescence under UV light.
ESIMS: m/z 327.1 [M+H] + ; 1 H NMR (CD3OD,300 MHz)
δ: 7.72 (1H, d, J 15.9 Hz, H7), 7.48 (2H, d, J 8.7 Hz,
H2,6), 6.81 (2H, d, J 8.7 Hz, H3,5), 6.36 (1H, d, J 15.9 Hz,
H8), 5.56 (1H, d, J 7.8 Hz, H1 of Glc), 3.84 (1H,
dd, J1 10.4 Hz, J2 1.5 Hz, H6a of Glc), 3.68 (1H,
dd, J1 12.0 Hz, J2 4.5 Hz, H6b of Glc); 13 C NMR
(CD3OD, 75 MHz) δ: 167.5 (C9), 162.1 (C4), 147.8
(C7), 131.2 (C2,6), 126.7 (C1), 117.1 (C3,5), 115.2
(C8), 95.4 (C1 of Glc), 78.3 (C3 of Glc), 77.8 (C5
of Glc), 73.8 (C2 of Glc), 71.3 (C4 of Glc), 62.4 (C6
of Glc). All above data were in good agreement with
those of 1Opmethoxybenzoyl sucrose [27] .
3.21. Bayogenin3Oglucoside (21)
White flaky crystal. ESIMS: m/z 651.4 [M+H] + ;
1 H NMR (CD3OD, 500 MHz) δ: 5.62 (1H, m, H12),
4.33 (1H, d, J 8.0 Hz, H1 of Glc), 1.37, 1.25, 0.96,
0.90, 0.77 (each 3H, s, 5×CH3); 13 C NMR (CD3OD,
125 MHz) δ: 181.7 (C28), 139.7 (C13), 128.8 (C12),
104.8 (C1 of Glc), 85.8 (C3), 77.7 (C3,5 of Glc),
729 Zhou, Y.H. et al. / J. Chin. Pharm. Sci. 2014, 23 (10), 723–730
75.1 (C3 of Glc), 71.1 (C4 of Glc), 70.1 (C2), 65.0
(C27), 62.2 (C6 of Glc), 53.2 (C4), 52.8 (C5), 50.1
(C9), 47.3 (C17), 46.0 (C19), 44.4 (C1), 43.2 (C14),
42.4 (C18), 41.4 (C8), 37.5 (C10), 34.7 (C7), 33.8
(C21), 33.7 (C30), 33.5 (C22), 31.6 (C20), 25.0
(C15), 24.4 (C16), 24.0 (C11), 23.9 (C29), 21.6
(C6), 18.8 (C26), 17.4 (C25), 13.6 (C24). All above
data were in good agreement with those of bayogenin
3Oglucoside [28] .
3.22. Tenufolin (22)
White powder. ESIMS: m/z 681.4 [M+H] + ; 1 H NMR
(C5D5N, 500 MHz) δ: 5.85 (1H, m, H12), 5.08 (1H, d,
J 8.0 Hz, H1 of Glc), 1.98, 1.52, 1.05, 0.99, 0.86 (each
3H, s, 5×CH3); 13 C NMR (C5D5N, 125 MHz) δ: 180.5
(C23), 180.1 (C28), 139.7 (C13), 127.5 (C12), 105.4
(C1 of Glc), 84.0 (C3), 78.4 (C3,5 of Glc), 75.2 (C2
of Glc), 71.6 (C4 of Glc), 70.3 (C2), 64.4 (C27),
62.8 (C6 of Glc), 52.9 (C4), 52.5(C5), 49.4 (C9),
48.0 (C17), 46.5 (C14), 45.0 (C1), 41.8 (C18), 40.9
(C8), 37.0 (C10), 34.1 (C7), 33.2 (C21), 33.1 (C29),
33.1 (C22), 31.0 (C20), 24.5 (C15), 24.0 (C16),
23.9 (C11), 23.6 (C30), 21.6 (C6), 18.8 (C26), 17.3
(C25), 14.2 (C24). All above data were in good agree
ment with those of tenufolin [29] .
3.23. Sinapic acid (23)
White flaky crystal, skyblue fluorescence under UV
light. ESIMS: m/z 225.1 [M+H] + ; 1 H NMR (CD3OD,
300 MHz) δ: 7.65 (1H, d, J 15.9 Hz, H7), 6.92 (2H, s,
H2,6), 6.38 (1H, d, J 16.0 Hz, H8), 3.82 (6H, s,
OMe3,5); 13 C NMR (CD3OD, 75 MHz) δ: 167.7 (C9),
148.6 (C3,5), 147.2 (C7), 139.3 (C4), 126.1 (C1),
115.2 (C8), 106.5 (C2,6), 56.6 (OMe). All above data
were in good agreement with those of sinapic acid [30] .
4. Results and discussion
In continuation of our studies on the bioactive compounds
of Polygalaceae plants, we investigated the chemical
constituents of the roots of P. wattersii. Twentythree
known compounds, including eleven xanthones, nine
sugar esters, two triterpenoid saponins and one phenyl
propanoid were isolated, and their structures were
identified. Among them, compounds 2 and 12 were
reported from genus Polygala for the first time, and all
other compounds except 16 were isolated from this species
for the first time. The chemical investigation provides a
substantial foundation for its further pharmacological
and quality evaluation researches, and even its advanced
medicinal development of P. wattersii.
Acknowledgements
This project was financially supported by the National
Key Technology R & D Program “New Drug Innovation”
of China (Grant No. 2012ZX09301002002002,
2012ZX09304005), special funds for scientific research
on traditional Chinese medicine (Grant No. 201307002),
and National Science Fund for Excellent Young
Scholars (Grant No. 81222051).
References
[1] Chen, S.K. Acta Phytotaxon. Sin. 1991, 29, 193–229.
[2] Kobayashi, W.; Miyase, T.; Suzuki, S.; Noguchi, H.;
Chen, X.M. J. Nat. Prod. 2000, 63, 1121–1126.
[3] Jiang, Y.; Tu, P.F. Phytochemistry. 2002, 60, 813–816.
[4] Jiang, Y.; Tu, P.F. Chin. Tradit. Herb. Drugs. 2002, 22,
875–877.
[5] Jiang, Y.; Tu, P.F. Chem. Pharm. Bull. 2005, 53, 1164–
1166.
[6] Li, J.; Wang, J.; Jiang, Y.; Tu, P.F. Chin. Tradit. Herb.
Drugs. 2005, 36, 1124–1126.
[7] Li, J.; Jiang, Y.; Tu, P.F. J. Nat. Prod. 2005, 68, 739–744.
[8] Jiang, Y.; Zhang, W.; Tu, P.F.; Xu, X.J. J. Nat. Prod.
2005, 68, 875–879.
[9] Li, J.; Jiang, Y.; Tu, P.F. J. Nat. Prod. 2005, 68, 1802–
1804.
[10] Chang, H.T.; Tu, P.F.Helv. Chim. Acta. 2007, 90, 944–950.
[11] Zhou, Y.H.; Jiang, Y. Wen, J.; Chen, Y.P.; Tu, P.F. J.
Chin. Pharm. Sci. 2008, 17, 148–152.
[12] Song, Y.L; Zhou, S.X.; Wei, H.L.; Jiang, Y.; Tu, P.F.
Nat. Prod. Commun. 2012, 7, 1165–1168.
[13] Yu, D.Q.; Yang, J.S. Handbook of Analytical Chemistry.
Vol.7. Beijing: Chemical Industry Press. 1999, 839–840.
[14] Gnerre, C.; Thull, U.; Gaillard, P.; Carrupt, P.A.; Testa, B.;
Fernandes, E.; Silva, F.; Pinto, M.; Pinto, M.M.M.;
Wolfender, J.L.; Hostettmann, K.; Cruciani, G. Helv. Chim.
Acta. 2001, 84, 552–570.
[15] Mao, S.L.; Liao, S.X.; Wu, J.H.; Ling, N.; Chen, H.;
Ling, H.Q.; Lin, M.Z. Acta Pharm. Sin. 1997, 32, 360–362.
[16] Lin, L.L.; Huang, F.; Chen, S.B.; Yang, D.J.; Chen, S.L.;
Yang, J.S.; Xiao, P.G. Chin. J. Chin. Mater. Med. 2005,
30, 827–830.
730 Zhou, Y.H. et al. / J. Chin. Pharm. Sci. 2014, 23 (10), 723–730
[17] Ikeya, Y.; Sugama, K.; Okada, M.; Mitsuh, H. Phyto
chemistry. 1991, 30, 2061–2065.
[18] Mao, S.L.; Liao, S.X.; Wu, J.H.; Ling, H.Q.; Chen, H.S.;
Zhang, C.K. Acta Pharm. Sin. 1996, 31, 118–121.
[19] Fujita, T.; Liu, D.Y.; Ueda, S.; Takeda, Y. Phytochemistry.
1992, 31, 3997–4000.
[20] Zhu, D.N.; Li, L.; Zhu, Y.J.; Yan, Y.Q. J. Chin. Pharm.
Univ. 2003, 34, 222–224.
[21] Nakano, K.; Murakami, K.; Takaishi, Y.; Tominatsu, T.
Chem. Pharm. Bull. 1986, 34, 5005–5010.
[22] Kobayashi, W.; Miyase, T.; Suzuki, S.; Noguchi, H.;
Chen, X.M. J. Nat. Prod. 2000, 63, 1066–1069.
[23] Miyase, T.; Noguchi, H.; Chen, X.M. J. Nat. Prod. 1999,
62, 993–996.
[24] Zhang, D.M.; Miyase, T.; Kuroyanagi, M.; Umehara, K.;
Noguchi, H. Phytochemistry. 1998, 47, 45–52.
[25] Ikeya, Y.; Sugama, K.; Minoru, O.; Mitsuhashi, H. Chem.
Pharm. Bull. 1991, 39, 2600–2605.
[26] Miyase, T.; Ueno, A. Shoyakugaku Zasshi. 1993, 47,
267–278.
[27] Moriguchi, T.; Villegas, R.J.A.; Kondo, T.; Kojima, M.
Plant Cell Physiol. 1988, 29, 1221–1226.
[28] Zhang, D.M.; Miyase, T.; Kuroyanagi, M.; Umehara, K.;
Ueno, A. Chem. Pharm. Bull. 1995, 43, 115–120.
[29] Sakuma, S.; Shoji, J. Chem. Pharm. Bull. 1982, 30,
810–821.
[30] Zhao, X.H.; Chen, D.H.; Si, J.Y.; Pan, R.L.; Shen, L.G.
Acta Pharm. Sin. 2002, 37, 535–538.
长毛籽远志根的化学成分研究
周雨虹 1a , 郭强 2a , 姜勇 1 , 屠鹏飞 1,2*
1.北京大学医学部 天然药物及仿生药物国家重点实验室,北京 100191
2.北京中医药大学 中药现代研究中心, 北京 100029
摘要: 为长毛籽远志 Polygala wattersii 的质量控制和进一步的开发提供科学依据, 我们对它的根进行了系统的化学
成分研究。利用硅胶、Sephadex LH20、制备薄层色谱及半制备液相等多种色谱分离技术进行分离和纯化, 应用EIMS、
ESIMS、 1 H NMR及 13 C NMR等现代波谱技术并与文献相对照等方法鉴定化合物的结构。共从长毛籽远志根中分离鉴定了
23个化合物, 包括11个口山酮类: 1,3二羟基口山酮 (1), 1羟基3甲氧基口山酮 (2), 1,3二羟基2甲氧基口山酮 (3), 1,3,7三羟基2
甲氧基口山酮 (4), 1,3,6三羟基2,7二甲氧基口山酮 (5), 1,6,7三羟基2,3二甲氧基口山酮 (6), 1,7二羟基2,3亚甲二氧基口山酮 (7),
1,7二甲氧基口山酮 (8), 1,2,3三甲氧基口山酮 (9), 1甲氧基2,3亚甲二氧基口山酮 (10), 6羟基1甲氧基2,3亚甲二氧基口山酮 (11);
9个糖酯类: 3O阿魏酰基6O乙酰蔗糖 (12), arillatose B (13), sibricose A5 (14), sibricose A6 (15), 3,6二O芥子酰基蔗糖 (16),
tenufoliside A (17), 3O3,4,5三甲氧基肉桂酰基6O对甲氧基苯甲酰基蔗糖 (18), glomeratose A (19), 1O对香豆酰基
葡萄糖 (20); 两个三萜皂苷类: bayogenin3Oglucoside (21) 和 tenufolin (22)及1个苯丙素类: 芥子酸 (23)。其中, 化合物2
和12为首次从远志属中分离得到, 除化合物16外其它所有化合物均为首次从该种植物中分离得到。
关键词: 远志科; 长毛籽远志;化学成分; 口山酮; 糖酯