全 文 ：应用与环境生物学报 2009，15 ( 5 ): 615~620
Chin J Appl Environ Biol=ISSN 1006-687X
2009-10-25
DOI: 10.3724/SP.J.1145.2009.00615
The traditional Chinese medicinal herb ‘Gangbangui’
is the dried whole plant of Polygonum perfoliatum L., which
widely distributes in the valleys, bushes and the side of the
drain in Jiangsu, Zhejiang, Fujian, Jiangxi, Guangdong,
Guangxi, Sichuan, Hunan and Guizhou provinces, China [1]. It
is used to relieve cough, and possesses anti-inflammatory and
detumescence actuvutt [1, 2]. Flavonoids from this plant have been
reported so far [3]. During our study on bioactive entities from
the indigenous herbs in Jiangxi, we investigated the plants of P.
perfoliatum. Twenty one compounds (Fig. 1) were isolated and
identified as α-tocopherolquinone (1), 7′-dihydroxymatairesinol
(2), (24S)-24-ethylcholesta-3β,5α,6α-triol (3), 4-dihydroxy-
5,7-dihydroxy-4-(4-hydroxyphenyl) coumarin (4), quercetin
(5), cucurbitacin IIa (6), cucurbitacin U (7), iotroridoside A
(8), pokeweedcerebroside 5 (9), bonaroside (10), helonioside A
(11), helonioside B (12), lapathoside D (13), vanicoside B (14),
vanicoside C (15), vanicoside F (16), asteryunnanoside F (17),
saikosaponin M (18), hydropiperoside (19), quercetin-3-O-
β-D-glucuronide-6′′-butyl ester (20) and quercetin-3-O-β-D-
glucuronide-6′′-methyl ester (21) by spectral data. Compounds
1~19 (except 4, 12) were isolated from this plant for the fi rst time.
Some natural products isolated from P. perfoliatum commonly
exist in other plants of this genus. Compounds 1~11 (except 4 and
5) and 17~19 were obtained from this genus for the fi rst time.
1 Material & Methods
1.1 General
Column chromatography: silica gel (200~300 mesh; H,
Qingdao Marine Chemical Inc., Qingdao, China); Sephadex
LH-20 (Amershan Bioscience). Melting points were determined
on an XRC-1 apparatus and uncorrected. Optical rotations were
杠板归的化学成分*
李红芳1, 2 马青云3 刘玉清1 钱金栿2 周 俊1 赵友兴1**
（1中国科学院昆明植物研究所植物化学与西部植物资源国家重点实验室 昆明 650204）
（2大理学院药学院 大理 671001）
（3云南科技信息职业学院 昆明 650224）
Chemical Constituents from Polygonum perfoliatum*
LI Hongfang1, 2, MA Qingyun3, LIU Yuqing1, QIAN Jinfu2, ZHOU Jun1 & ZHAO Youxing1**
(1State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinses Academy of Sciences, Kunming 650204, China)
(2College of Pharmacy, Dali University, Dali 671000, Yunnan, China)
(3Yunnan Institute of Technology & Information, Kunming 650224, China)
Abstract Twenty one compounds were isolated from the ethanol extract of Polygonum perfoliatum. They were identifi ed
as α-tocopherolquinone (1), 7′-dihydroxymatairesinol (2), (24S)-24-ethylcholesta-3β,5α,6α-triol (3), 4-dihydroxy-5,7-
dihydroxy-4-(4-hydroxyphenyl) coumarin (4), quercetin (5), cucurbitacin IIa (6), cucurbitacin U (7), iotroridoside A (8),
pokeweedcerebroside 5 (9), bonaroside (10), helonioside A (11), helonioside B (12), lapathoside D (13), vanicoside B (14),
vanicoside C (15), vanicoside F (16), asteryunnanoside F (17), saikosaponin M (18), hydropiperoside (19), quercetin-3-O-β-D-
glucuronide-6′′-butyl ester (20) and quercetin-3-O-β-D-glucuronide-6′′-methyl ester (21) on the basis of spectral data. Among
them, compounds 1~19 (except 4, 5 and 12) were isolated from this plant for the fi rst time, and compounds 1~11 (except 4 and 5)
and 17~19 were obtained from this genus for the fi rst time. Fig 1, Ref 22
Keywords Polygonum perfoliatum; cucurbitacin U; helonioside B; hydropiperoside
CLC Q949.744.06
摘 要 采用柱层析方法从蓼科药用植物杠板归（Polygonum Perfoliatum）分离了21个化合物（1~21），通过MS与
NMR数据鉴定这些化合物为α-tocopherolquinone (1), 7′-dihydroxymatairesinol (2), (24S)-24-ethylcholesta-3β,5α,6α-triol
(3), 4-dihydroxy-5,7-dihydroxy-4-(4-hydroxyphenyl) coumarin (4), quercetin (5), cucurbitacin IIa (6), cucurbitacin U (7),
iotroridoside A (8), pokeweedcerebroside 5 (9), bonaroside (10), helonioside A (11), helonioside B (12), lapathoside D (13),
vanicoside B (14), vanicoside C (15), vanicoside F (16), asteryunnanoside F (17), saikosaponin M (18), hydropiperoside (19),
quercetin-3-O-β-D-glucuronide-6′′-butyl ester (20), quercetin-3-O-β-D-glucuronide-6′′-methyl ester (21). 化合物1~19（除4, 5,
12）为首次从该植物中分离得到，化合物1~11（除4, 5）和17~19为首次从该属植物中分离得到. 图1 参22
关键词 杠板归；cucurbitacin U；helonioside B；hypdropiperoside
CLC Q949.744.06
Received: 2008-12-08 Accepted: 2008-12-22
*Supported by the Natural Science Foundation of Yunnan, China (No.
2008CD159) and the Fund of the State Key Laboratory of Phytochemistry and
Plant Resources in West China
**Corressponding author (E-mai: yxzhao@mail.kib.ac.cn)
616 15 卷应 用 与 环 境 生 物 学 报 Chin J Appl Environ Biol
carried out on a Jsaco P-1020 plarimeter, and MS spectra on a
VG Auto spec-3000. NMR spectra were recorded on a Bruker
AM-400 spectrometer and chemical shifts were given in δ with
TMS as internal reference.
1.2 Plant material
The whole plants of P. perfoliatum were collected in Le′an
County, Jiangxi, China. The plant material was authenticated
by Prof. Zhou Jun of Kunming Institute of Botany, Chinese
Academy of Sciences (CAS). The specimen (ZYX 2007-07-1)
was deposited at the State Key Laboratory of Phytochemistry and
Plant Resources in West China, Kunming Institute of Botany,
CAS.
1.3 Extraction and isolation
The dried whole plants of P. perfoliatum (5.0 kg) were
powered and ref luxed in 90% EtOH for 3 times (each time
with 10 L ethanol for 3 hours). After removing the solvent by
evaporation, the concentrated extract was suspended in water,
and extracted successively with chloroform and n-butanol. The
chloroform extract (180 g) was divided into two fractions A and B
by dry column chromatography (DCC) eluted with EtOAc-EtOH
(5 : 1) on silica gel. Fraction A (90 g) was submitted to DCC on
silica gel with petrol-Me2CO (4 : 1) to give four subfractions
A1- A5. Subfraction A1 (15 g) was repeatedly subjected to CC
on silica gel with petrol-Me2CO (5 : 1) to yield compounds 1
(9 mg), 2 (8 mg) and 3 (37 mg). Compounds 4 (4 mg) and 6 (24
mg) were obtained from A2 (13 g) in CC with CHCl3-MeOH (8
: 1). Subfraction A3 (2 g) was separated over Sephadex LH-20
eluted with CHCl3-MeOH (1 : 1) to give compound 5 (30 mg).
Subfraction A4 (12 g) was subjected to silica gel DCC eluted
with CHCl3-MeOH (6 : 1) to afford compound 7 (14 mg) and
compound 8 (5 mg) . Subfraction A5 (17 g) was subjected to silica
gel CC with CHCl3-MeOH (5 : 1) as solvents to give compounds
9 (12 mg) and 10 (41 mg). Fraction B was submitted to silica gel
DCC eluted with CHCl3-MeOH (4 : 1) and then separated over
Sephadex LH-20 column eluted MeOH to give compounds 11
(38 mg), 12 (67 mg) and 13 (5 mg). Compound 14 (154 mg) was
obtained from crystallization (CHCl3-MeOH) of fraction B.
The n-butanol extract (250 g) was divided into three fractions
C-E by DCC on silica gel eluted with CHCl3-MeOH-H2O (7 : 3 :
0.5) . Compound 15 (154 mg) was obtained by crystallization of
Fig. 1 Compounds 1~21 from Polygonum perfoliatum
6175 期 LI Hongfang, et al.: Chemical Constituents from Polygonum perfoliatum
fraction C (15 g) from CHCl3-MeOH (1: 1). Fraction D (40 g) was
submitted to silica gel CC with CHCl3-MeOH-H2O (7 : 3 : 0.5) as
solvents to afford compounds 16 (28 mg), 17 (25 mg) and 19 (137
mg). The separation of fraction E (33 g) over Sephadex LH-20
column eluted with MeOH gave compounds 18 (12 mg), 20 (78
mg) and 21 (41 mg).
2 Structure identifi cation
α-tocopherolquinone (1): Viscous yellow oil, [α]2D5 +22.3°
(c, 1.20, CHCl3); EI-MS m/z (%): 446 [M
+] (15); 1H NMR (400
MHz, CDCl3) δ: 2.51 (2H, m, H-1′), 2.03 (3H, s, Me-6), 2.00 (6H,
s, Me-3, 4), 1.24 (3H, s, Me-3′), 0.86 (6H, d, J = 6.6 Hz, Me-15′,
H-16′), 0.83~0.85 (6H, Me-7′,11′); 13C NMR (100 MHz, CDCl3) δ:
187.6, 187.2 (s, C-2, 5), 144.4 (s, C-1), 140.5, 140.4, 140.1 (s, C-3, 4,
6), 72.6 (s, C-3′), 42.3 (t, C-4′), 40.2 (t, C-14′), 39.3 (t, C-2′), 37.5,
37.4, 37.2 (each t, C-8′, 10′, 12′), 32.8 ,32.7 (each d, C-7′, 11′), 29.7 (t,
C-6), 27.9 (d, C-15′), 26.6 (q, Me-3′), 24.8 (t, C-9′), 26.6 (q, Me-3′),
24.8 (t, C-9′), 24.5 (t, C-13′), 22.7, 22.6 (each q, Me-15′, C-16′),
21.3 (t, C-5′), 19.6 (each q, Me-7′, 11′), 12.5 (each q, Me-3, 4, 6),
12,4 (t, C-1′). The MS and NMR spectral data were in consistent
with those reported [4].
7,7′-dihydroxymatairesinol (2): Viscous yellow oil, EI-
MS m/z (%): 390[M]+ (2), 85 (68), 71 (97) , 57 (100) ; 1H NMR
(400 MHz, CDCl3) δ: 6.78`~6.94 (6H, H-2, 5, 6, 2′, 5′, 6′), 5.36,
5.34 (each 1H, d, J = 8.3, 8.5 Hz, H-7, 7′), 4.32 (1H, d, J = 9.3,
2.5 Hz, H-9a), 4.05 (1H, d, J = 9.3, 4.6 Hz, H-9b), 3.90, 3.92 (6H,
s, 3, 3′-OCH3), 3.46~3.51 (2H, m, H-8, 8′);
13C NMR (100 MHz,
CDCl3) δ: 176.9 (s, C-9′), 146.9, 146.7 (s, C-3, 3′), 146.0, 145.3 (s,
C-4, 4′), 132.2, 131.0 (s, C-1, 1′), 118.4, 118.0 (d, C-6, 6′), 114.7,
114.4 (d, C-5, 5′), 108.1, 107.9 (d, C-2, 2′), 84.6, 83.4 (d, C-7,
7′), 72.7 (t, C-9), 56.1, 56.0 (q, 3, 3′-OCH3), 53.3, 50.0 (C-8, 8′).
The MS and NMR spectral data were in consistent with those
reported [5].
(24S ) -24 -ethylcholesta-3β, 5α ,6α- tr iol (3): White
amorphous powder, [α]2D5 +35.6° (c, 0.247, MeOH); EI-MS m/z
(%): 430 [M-H2O]
+ (23), 412 (31), 397 (15), 289 (65), 271 (89), 253
(77); 1H NMR (100 MHz, CDCl3) δ: 4.15 (1H, m, H-3), 3.75 (1H,
m, H-6), 0.85 (3H, t, J = 7.5 Hz, Me-29), 0.81 (3H, d, J = 7.1 Hz,
Me-26), 0.78 (3H, d, J = 6.7 Hz, Me-27), 0.71 (3H, s, Me-18), 0.95
(3H, d, J = 6.4 Hz, Me-21), 1.26 (3H, s, Me-19); 13C NMR (100
MHz, CDCl3) δ: 76.3 (s, C-6), 75.9 (d, C-5), 67.4 (d, C-3), 56.6 (d,
C-14), 56.6 (d, C-17), 46.1 (d, C-24), 45.9 (d, C-9), 43.1 (s, C-13),
42.9 (t, C-4), 40.7 (t, C-12), 39.2 (t, C-7), 36.6 (s, C-10), 35.8 (d,
C-20), 33.5 (t, C-22), 33.4 (t, C-2), 32.6 (t, C-2), 31.3 (d, C-1), 29.5
(d, C-8), 28.5 (t, C-23), 26.6 (t, C-16), 25.5 (t, C-15), 23.4 (t, C-28),
21.8 (t, C-11), 20.0 (q, C-27), 19.3 (q, C-26), 19.0 (q, C-21), 17.3 (q,
C-19), 12.4 (q, C-29), 12.2 (q, C-18). The MS and NMR spectral
data were in consistent with those reported [6].
3,4 -dihydro-5,7-dihydroxy- 4 - (4 -hydroxyphenyl)
coumarin (4): Yellow amorphous powder, [α]eqD +11° (c, 0.004,
EtOH); EI-MS m/z (%): 272 [M]+ (17), 229 (31), 179 (14), 71 (100);
1H NMR (500 MHz, MeOD) δ: 6.85 (2H, d, J = 8.6 Hz, H-2′, 6′),
6.62 (2H, d, J = 8.6 Hz, H-3′, 5′), 6.15 (1H, d, J = 2.0 Hz, H-8), 6.07
(1H, d, J = 2.0 Hz, H-6), 4.46 (1H, d, J = 6.1 Hz, H-4), 3.03, 2.84
(2H, m, H-3); 13C NMR (100 MHz, CDCl3) δ: 170.7 (s, C-2), 159.3
(s, C-4′), 157.2 (s, C-5), 156.8 (s, C-7), 154.6 (s, C-10), 134.3 (s,
C-1′), 128.9 (d, C-2′, 6′), 116.3 (d, C-3′, 5′), 105, 6 (s, C-9), 99.9 (d,
C-8), 96.1 (d, C-6), 38.7 (t, C-3), 34.9 (d, C-4). The MS and NMR
spectral data were in consistent with those reported [7].
Quercetin (5): Yellow powder, EI-MS m/z (%): 302 [M+]
(100); 1H NMR (400 MHz, MeOD) δ: 7.73 (1H, d, J = 2.0 Hz,
H-2′), 7.62 (1H, dd, J = 2.0, 8.5 Hz, H-6′), 6.91 ((1H, d, J = 8.5
Hz, H-5′), 6.40, 6.19 (each 1H, d, J = 1.7 Hz, H-6, 8); 13C NMR (100
MHz, MeOD) δ: 177.3 (s, C-4), 165.5 (s, C-7), 162.4 (s, C-9), 158.1
(s, C-5), 148.8 (s, C-4′), 147.9 (s, C-2), 146.3 (d, C-3′), 137.3 (s,
C-3), 124.1 (s, C-1′), 121.7 (d, C-6′), 116.4 (d, C-5′), 116.1 (s, C-2′),
104.5 (s, C-10), 99.3 (d, C-6), 94.5 (d, C-8). The MS and 13C NMR
spectral data were in consistent with those reported [8].
Cucurbitacin IIa (6): Colorless prisms crystals (CHCl3),
mp. 266~268 °C; FAB-MS m/z (%): 563 [M+H]+ (1), 484 (4), 387
(4), 143 (3), 114 (3), 95 (23); 1H NMR (400 MHz, CDCl3) δ: 5.71
(1H, m, H-6), 4.26 (1H, m, H-3), 1.95 (3H, s, —COCH3), 0.94~1.45
(8 × 3H, s, H-9, 20, 21, 22, 23, 24, 29, 30); 13C NMR (100 MHz,
CDCl3) δ: 214.0 (s, C-22), 212.9 (s, C-11), 170.5 (s, —COCH3),
140.5 (s, C-5), 119.1 (d, C-6), 81.2 (s, C-25), 80.8 (s, C-3), 78.9 (d,
C-20), 76.9 (d, C-2), 70.8 (d, C-16), 57.7 (d, C-17), 50.6 (t, C-9),
48.2 (t, C-12), 48.2 (s, C-14), 47.7 (s, C-13), 45.4 (t, C-15), 42.4 (d,
C-8), 41.8 (s, C-4), 34.5 (t, C-1), 33.8 (d, C-10), 32.9 (t, C-24), 30.6
(t, C-23), 26.1, 25.8 (each q, C-26, 27), 24.6, 24.2 (each q, C-28,
29), 23.6 (t, C-7), 22.4 (q, C-21), 21.5 (q, —COCH3), 20.2, 19.7,
18.8 (each q, C-18, 19, 30). The MS and NMR spectral data were
in consistent with those reported [9].
Cucurbitacin U (7): Amorphous powder; FAB-MS m/z (%):
505 [M+H]+ (54), 488 (45); 1H NMR (400 MHz, CDCl3) δ: 1.37
(3H, s, H-21), 1.31 (3H, s, H-18), 1.18 (6H, s, H-28, 29), 1.16, 1.02
(each3H, s, H-26, 27), 0.95, 0.89 (each 3H, s, H-19, 30); 13C NMR
(100 MHz, CDCl3) δ: 217.2 (s, C-22), 216.1 (s, C-11), 142.7 (s, C-5),
119.9 (d, C-6), 81.9 (d, C-3), 80.8 (s, C-20), 71.6 (d, C-16), 70.8 (s,
C-25), 59.3 (d, C-17), 51.8 (s, C-13), 49.8 (s, C-9), 49.3 (t, C-12),
49.0 (s, C-14), 48.4 (t, C-15), 43.7 (d, C-8), 42.5 (s, C-4), 37.5 (t,
C-24), 34.9 (d, C-10), 34.8 (t, C-23), 33.2 (t, C-1), 29.4 (t, C-2),
29.4, 29.2 (each q, C-28, 29), 25.3, 25.1 (each q, C-26, 27), 24.7 (t,
C-7), 22.3 (q, C-21), 20.5, 20.4 (each q, C-18, 19), 19.7 (q, C-30).
Its MS and NMR were in consistent with those reported [10].
Iotroridoside A (8): Colorless amorphous powder, [α]2D5
-7.2° (c, 0.003, C5D5N); FAB-MS m/z (%): 844 [M+H]
+ (15); 1H
NMR (400 MHz, C5D5N) δ: 5.59 (1H, m, H-4′), 5.40 (1H, m, H-5′),
4.26 (1H, m, H-3), 0.87 (6H, t, J = 7.0 Hz, H-18, 24′); 13C NMR
(100 MHz, C5D5N) δ: 177.1 (s, C-1′), 134.4 (d, C-5′), 132.4 (d,
C-4′), 104.6 (d, C-1′′), 78.0 (d, C-3′′), 77.8 (d, C-5′′), 75.8 (d, C-3),
75.0 (d, C-2′′), 73.6 (d, C-4′′), 72.9 (d, C-2′), 71.5 (d, C-4), 69.8 (t,
618 15 卷应 用 与 环 境 生 物 学 报 Chin J Appl Environ Biol
C-1), 62.6 (t, C-6′′), 51.6 (d, C-2), 35.7 (t, C-5), 33.4 (t, C-3′), 33.1
(t, C-22′), 30.4-30.8 (t, C-7~16, 7′~21′), 27.8 (t, C-6′), 26.2 (t, C-6),
23.7 (each t, C-17, 23′), 14.4 (each q, C-18, 24′). Its MS and NMR
were in consistent with those reported [11].
Pokeweedcerebroside 5 (9): Colorless amorphous powder,
FAB-MS m/z (%): 842 [M-H]+ (100); 1H NMR (400 MHz, C5D5N)
δ: 8.57 (1H, d, J = 9.1 Hz, N-H), 5.44~5.55 (2H, m, H-8, 9), 4.96
(1H, d, J = 7.6 Hz, H-1′′), 2.23 (2H, m, H-7), 2.04 (2H, m, H-10),
0.83 (6H, t, J = 6.0 Hz, H-18, 24′); 13C NMR (100 MHz, C5D5N) δ:
175.3 (s, C-1′), 130.5, 130.3 (each d, C-8, 9), 105.2 (d, C-1′′), 78.2
(d, C-3′′), 78.1 (d, C-5′′), 75.5 (d, C-3), 74.8 (d, C-2′′), 72.1 (each d,
C-2′, 4), 71.5 (d, C-4′′), 70.1 (t, C-1), 62.2 (t, C-6′′), 51.4 (d, C-2),
13.9 (each q, C-18, 24′). Its MS and NMR were in consistent with
those reported [12].
Bonaroside (10): White amorphous powder, [α]eqD +178.6°
(c, 0.140, MeOH); FAB-MS m/z (%): 730 [M-H]+ (100); 1H NMR
(500 MHz, C5D5N) δ: 5.42 (1H, br dt, J = 16.7, 6.5 Hz, H-9′), 5.36
(1H, br dt, J = 16.7, 6.5Hz, H-10′), 4.95 (1H, d, J = 7.5 Hz, H-1′′),
4.29 (1H, m, H-3), 0.86 (6H, t, H-18, 16′) ; 13C NMR (100 MHz,
C5D5N) δ: 175.1 (s, C-1′), 130.2 (d, C-10′), 130.0 (d, C-9′), 104.9 (d,
C-1′′), 77.9 (d, C-5′′), 77.8 (d, C-3′′), 75.2 (d, C-3), 74.5 (d, C-2′′),
71.8 (each d, C-4, 12), 70.8 (d, C-4′′), 69.8 (d, C-1), 62.0 (t, C-6′′),
51.1 (t, C-2), 34.9 (t, C-2′), 26.0 (t, C-3′), 13.6 (q, C-18, 16′). Its MS
and NMR were in consistent with those reported [13].
Helonioside A (11): Yellow amorphous powder, [α]eqD
+15.7°(c, 0.950, MeOH); FAB-MS m/z (%): 693 [M-H]+ ; 1H NMR
(500 MHz, MeOD) δ: 7.65, 7.72 (each 1H, d, J = 16.0 Hz, H-7′′,
7′′′), 6.39, 6.44 (each 1H, d, J = 16.0 Hz, H-8′′, 8′′′), 6.79~7.21 (6H,
Ar-H), 3 .88 (6H, s, 2×OCH3); 13C NMR (100 MHz, MeOD) δ:
169.0 (s, C-9′′), 168.2 (s, C-9′′′), 150.6 (s, C-3′′, 3′′′), 149.3 (s, C-4′′,
4′′′), 147.7 (d, C-7′′′), 147.2 (d, C-7′′), 127.6 (s, C-1′′, 1′′′), 124.2 (d,
C-6′′, 6′′′), 116.4 (d, C-5′′, 5′′′), 115.1 (d, C-8′′′), 114.9 (d, C-8′′),
112.0, 111.6 (d, C-2′′, 2′′′), 105,1 (s, C-2), 93.1 (d, C-1′), 81.2 (d, C-5),
79.2 (d, C-3), 74.9 (d, C-4, 5′), 74.3 (d, C-3′), 73.5 (d, C-2′), 71.4 (d,
C-4′), 66.2 (t, C-6), 65.1 (t, C-1), 62.6 (t, C-6′), 56.5 (q, OCH3). Its
MS and NMR were in consistent with those reported [14].
Helonioside B (12): Yellow amorphous powder; [α]eqD
+16.9°(c, 1.02, MeOH); FAB-MS m/z (%): 735 [M-H]+ (100) ; 1H
NMR (500 MHz, MeOD) δ: 7.69, 7.62 (2H, d, J = 15.8 Hz, H-7′′,
7′′′), 6.80-7.24 (6H, Ar-H), 6.42, 6.36 (2H, d, J = 15.8 Hz, H- 8′′,
8′′′), 3.88 (6H, s, 2×OCH3), 2.06 (3H, s, COCH3);
13C NMR (100
MHz, MeOD) δ: 172.9 (s, COCH3), 168.8, 168.2 (s, C-9′′, 9′′′),
150.7, 150.6 (s, C-3′′, 3′′′), 149.4, 149.3 (s, C-4′′, 4′′′), 147.8, 147.1
(s, C-7′′, 7′′′), 127.7, 127.6 (s, C-1′′, 1′′′), 124.3, 124.2 (d, C-6′′, 6′′′),
116.5, 116.4 (d, C-5′′, 5′′′), 115.2, 114.8 (d, C-8′′, 8′′′), 112.0, 111.7 (d,
C-2′′, 2′′′), 104.9 (s, C-2), 92.6 (d, C-1′), 81.3 (d, C-5), 79.1(d, C-3),
74.9 (d, C-4), 74.4 (d, C-3′), 73.1 (d, C-2′), 72.1 (d, C-5′), 71.9 (d, C-4),
65.7, 65.6, 65.5 (each t, C-1, 6, 6′), 56.5 (q, OCH3), 20.9 (q, COCH3).
Its MS and NMR were in consistent with those reported [15].
Lapathoside D (13): Yellow amorphous powder, [α]eqD
+10.3°(c, 0.150, MeOH); FAB-MS m/z (%): 633 [M-H]+ (5); 1H
NMR (500 MHz, MeOD) δ: 7.66 (2H, d, J = 16.0 Hz, H-7′′, 7′′′),
7.48, 7.42 (4H, d, J = 8.6 Hz, H-2′′, 2′′′, 6′′, 6′′′), 6.79, 6.73 (4H,ｄ, J
= 8.6 Hz, H-3′′, 3′′′, 5′′, 5′′′), 6.41 (1H, d, J = 16.0 Hz, H = 8′′, 8′′′),
5.64 (1H, m, H-3), 5.52 (1H, d, J = 4.0, H-1′), 4.64 (2H, m, H-6),
4.52 (1H, m, H-4), 4.30 (1H, m, H-5), 4.19 (1H, m, H-5′), 3.92, 3.82
(2H, m, H-6′), 3.67 (2H, m, H-1), 3.45 (1H, m, H-4′). Its MS and
1H NMR were in consistent with those reported [16].
Vanicoside B (14): Yellow amorphous powder; FAB-MS
m/z (%): 955 [M-H]+ (26) ; 1H NMR (500 MHz, CDCl3) δ: 7.75~7.59
(4H, m, H-7′′, 7′′′, 7′′′′, 7′′′′′), 7.49~7.31 (6H, m, H-2′′′, 2′′′′, 2′′′′′, 6′′′,
6′′′′′, 6′′′′′), 7.31 (1H, d, J = 1.4 Hz, H-2′′), 7.01 (1H, dd, J = 1.4, 8.7
Hz, H-6′′), 6.8~6.74 (6H, m, H-3′′′, 3′′′′, 3′′′′′, 5′′′, 5′′′′, 5′′′′′), 6.77
(1H, d, J = 8.7 Hz, H-5′′), 6.50~6.27 (4H, m, H-8′′, 8′′′, 8′′′′, 8′′′′′),
5.64 (1H, d, J = 8.7 Hz, H-3), 5.56 (1H, d, J = 3.8 Hz, H-1′), 4.73
(1H, m, H-4), 4.20~4.73 (3H, m, H-1, 5), 4.55 (2H, m, H-6), 4.31
(1H, m, H-5′), 4.25 (2H, m, H-6′), 3.82 (3H, s, -OCH3), 3.61 (1H,
dd, J = 9.5, 9.8 Hz, H-3′), 3.34 (1H, dd, J = 9.6, 9.7 Hz, H-4′); 13C
NMR (100 MHz, CDCl3) δ: 169.3, 168.9, 168.5, 168.4 (s, C-9′′, 9′′′,
9′′′′, 9′′′′′), 150.5 (s, C-3′′), 149.3 (s, C-4′′), 147.9, 147.2, 146.8 (d,
C-7′′, 7′′′, 7′′′′, 7′′′′′), 131.6, 131.3, 131.2 (d, C-2′′′, 2′′′′, 2′′′′′, 6′′′, 6′′′′,
6′′′′′), 127.7, 127.0 (s, C-1′′, 1′′′, 1′′′′, 1′′′′′), 124.6 (d, C-6′′), 116.8 (d,
C-3′′′, 3′′′′, 3′′′′′, 5′′′, 5′′′′, 5′′′′′), 116.3, 114.8, 114.7, 114.3 (d, C-8′′, 8′′′,
8′′′′, 8′′′′′), 115.3 (d, C-5′′), 111.4 (d, C-2′′), 103.3 (s, C-2), 92.9(d,
C-1′), 80.9 (d, C-5), 79.0 (d, C-3), 74.9 (d, C-4′), 73.9 (d, C-4), 72.8
(d, C-2′), 72.4 (d, C-5′), 72.2 (d, C-3′), 66.3 (t, C-6), 65.8 (t, C-6′),
65.5 (t, C-1). The MS and NMR spectral data were in consistent
with those reported [17].
Vanicoside C (15): Yellow amorphous powder; FAB-MS
m/z (%): 821[M-H] + (13); 1H NMR (400 MHz, CDCl3) δ: 7.37~7.61
(3H, m, H-7′′, 7′′′, 7′′′′), 6.80~6.73 (12H, m, H-2′′, 2′′′, 2′′′′, 3′′, 3′′′,
3′′′′, 5′′, 5′′′, 5′′′′, 6′′, 6′′′, 6′′′′), 6.31~6.45 (3H, m, H-8′′, 8′′′, 8′′′′), 5.62
(1H, d, J = 3.6 Hz, H-3), 2.07 (3H, s, OCH3). Its MS and 1H NMR
were in consistent with those reported [18].
Vanicoside F (16): Yellow amorphous powder, FAB-MS
m/z (%): 997 [M-H]+; 1H NMR (400 MHz, CDCl3) δ: 7.78~7.62
(4H, m, H-7′′, 7′′′, 7′′′′, 7′′′′′), 7.50~7.33 (6H, m, H-2′′′, 2′′′′, 2′′′′′,
6′′′, 6′′′′′, 6′′′′′), 7.18 (1H, d, J = 2.1Hz, H-2′′), 7.10 (1H, dd, J = 2.1,
8.5Hz, H-6′′), 6.80~6.73 (6H, m, H-3′′′, 3′′′′, 3′′′′′, 5′′′, 5′′′′, 5′′′′′),
6.49~6.29 (4H, m, H-8′′, 8′′′, 8′′′′, 8′′′′′), 5.74~5.57 (2H, m, H-3,
1′), 3.83 (s, OCH3), 2.08 (s, 3H, COCH3);
13C NMR (100 MHz,
CDCl3) δ: 172.4 (s, CH3CO), 169.2, 168.9, 168.3 (s, C-9′′, 9′′′, 9′′′′,
9′′′′′), 161.5, 161.3, 161.2 (s, C-4′′′, 4′′′′, 4′′′′′), 150.5 (s, C-3′′), 149.3
(s, C-4′′), 149.3, 148.0, 147.2, 146.9 (d, C-7′′, 7′′′, 7′′′′, 7′′′′′), 131.6,
131.3, 131.2 (d, C-2′′′, 2′′′′, 2′′′′′, 6′′′, 6′′′′, 6′′′′′), 127.7, 127.1, 126.9
(s, C-1′′, 1′′′, 1′′′′, 1′′′′′), 124.5 (d, C-6′′), 116.8, 116.7, 116.3, 116.2 (d,
C-3′′′, 3′′′′, 3′′′′′, 5′′′, 5′′′′, 5′′′′′), 114.7, 114.5, 114.1 (d, C-8′′, 8′′′, 8′′′′,
8′′′′′), 115.2 (d, C-5′′), 111.4 (d, C-2′′), 103.5 (s, C-2), 90.5 (s, C-1′),
80.9 (d, C-5), 79.3 (d, C-3), 74.2 (d, C-4′), 72.3 (d, C-4), 72.2 (d,
C-2′, 5′), 72.0 (d, C-3′), 66.3 (t, C-6), 65.5 (t, C-6′), 65.4 (t, C-1),
6195 期 LI Hongfang, et al.: Chemical Constituents from Polygonum perfoliatum
56.4 (q, C—CH3O), 21.0 (q, CH3—CO). Its MS and 1H NMR
were in consistent with those reported [18].
Asteryunnanoside F (17): Yellow amorphous powder,
[α]eqD +16.7° (c, 0.220, C5D5N); FAB-MS m/z (%): 779 [M-H]
+;
1H NMR (500 MHz,CD3OD) δ: 5.35 (1H, d, J = 8.1 Hz, H-1′), 5.24
(1H, br s, H-12), 4.33 (1H, d, J = 7.8 Hz, H-1′′), 0.76, 0.79, 0.90,
0.92, 0.93, 0.95, 1.15 (each 3H, s, H-23, 24, 25, 26, 27, 29, 30); 13C
NMR (100 MHz, CDCl3) δ: 177.9 (s, C-28), 144.9 (s, C-13), 123.7
(d, C-12), 104.8 (d, C-1′′), 95.8 (d, C-1′), 79.6 (d, C-3′), 78.3, 78.2,
78.1 (d, C-3, 3′′, 5′, 5′′), 75.2 (d, C-2′′), 73.9 (d, C-2′), 71.6 (d, C-4′′),
71.2 (d, C-4′), 69.5 (t, C-6′), 62.5 (t, C-6′′), 42.9 (s, C-14), 42.4 (d,
C-18), 40.2 (s, C-8), 40.7 (s, C-4), 40.3 (t, C-1), 38.2 (s, C-10), 35.0
(t, C-21), 33.7 (t, C-7), 32.9 (t, C-22), 31.6 (s, C-20), 28,7 (t, C-15),
28.5 (t, C-2), 24.3 (t, C-11), , 19.2 (t, C-6), 33.6, 28.9, 26.5, 24.2,
17.9, 16.5, 16.2 (q, C-23, 24, 25, 26, 27, 29, 30). The MS and NMR
spectral data were in consistent with those reported [19].
Saikosaponin M (18): White powder, [α]2D1-117.6° (c, 0.030,
EtOH); FAB-MS m/z (%): 763 [M-H]+ (100) ; 1H NMR (500 MHz,
Pyridine) δ: 5.32 (2H, s, H-11, 12), 1.03, 0.99, 0.98, 0.87, 0.86, 0.80
(18H, s, H-24, 25, 26, 27, 29, 30), 5.31~5.49 (2H, m, H-11, 12).
The MS and 1H NMR spectral data were in consistent with those
reported [20].
Hydropiperoside (19): Colorless amorphous powder, [α]eqD
+61.9° (c, 0.310, MeOH); FAB-MS m/z (%): 779 [M-H]- (20);
1H NMR (400 MHz, CDCl3) δ: 7.61~7.65 (3H, m, H-7′′, 7′′′, 7′′′′),
7.37~7.48 (6H, m, H-2′′, 2′′′, 2′′′′, 6′′, 6′′′, 6′′′′), 6.73~6.80 (6H, m,
H-3′′, 3′′′, 3′′′′, 5′′, 5′′′, 5′′′′), 6.31~6.48 (3H, m, H-8′′, 8′′′, 8′′′′), 5. 61
(1H, d, J = 8.5 Hz, H-3), 5.52 (1H, d, J = 3.6 Hz, H-1′). Its MS and
1H NMR were in consistent with those reported [21].
Quercetin-3-O-β-D-glucuronide-6′′-butyl ester (20):
Yellow amorphous powder, [α]eqD+61.9° (c, 0.310, MeOH); FAB-
MS m/z (%): 547 [M-H]+ (92) ; 1H NMR (400 MHz, CD3OD) δ: 7.64
(1H, dd, J = 2.0, 9.2 Hz, H-6′), 7.62 (1H, J = 2.0 Hz, H-2′), 6.84 (1H,
d, J = 9.2 Hz, H-5′), 6.38 (1H, d, J = 1.6 Hz, H-8), 6.19 (1H, d, J
= 1.6 Hz, H-6), 5.34 (1H, d, J = 7.6 Hz, H-1′′), 0.83 (3H, t, J = 6.8
Hz, H-4′′′); 13C NMR (100 MHz, CD3OD) δ: 179.1 (s, C-4), 170.3
(s, C-6′′), 165.9 (s, C-7), 162.9 (s, C-5), 159.1 (s, C-9), 158.3 (s, C-2),
149.8 (s, C-4′), 145.9 (s, C-3′), 135.3 (s, C-3), 123.5 (d, C-6′), 122.8
(s, C-1′), 117.2 (d, C-5′), 115.9 (d, C-2′), 105.6 (s, C-10), 104.4 (d,
C-1′′), 99.9 (d, C-6), 94.7 (d, C-8), 77.4 (d, C-5′′), 77.2 (d, C-4′′),
75.3 (d, C-3′′), 72.7 (d, C-2′′), 66.5 (t, C-1′′′), 29.1 (t, C-2′′′), 23.2 (t,
C-3′′′), 14.3 (q, C-4′′′). The MS and NMR spectral data were in
consistent with those reported [22].
Quercetin-3-O-β-D-glucuronide-6′′-methyl ester (21):
Yellow amorphous powder, FAB-MS m/z (%): 491 [M-H]+ (87);
1H NMR (400 MHz, CD3OD) δ: 7.60 (1H, dd, J = 2.0, 8.5 Hz, H-6′),
7.58 (1H, J = 2.0 Hz, H-2′), 6.85 (1H, d, J = 8.5 Hz, H-5′), 6.38 (1H,
d, J = 1.6 Hz, H-8), 6.20 (1H, d, J = 1.6 Hz, H-6), 5.27 (1H, d, J =
7.6 Hz, H-1′′), 3.68 (3H, s, OCH3);
13C NMR (100 MHz, CD3OD)
δ: 178.1 (s, C-4), 169.5 (s, C-6′′), 165.2 (s, C-7), 162.0 (s, C-5),
157.4 (s, C-9), 156.8 (s, C-2), 149.1 (s, C-4′), 145.3 (s, C-3′), 134.2
(s, C-3), 122.0 (d, C-6′), 121.1 (s, C-1′), 117.2 (d, C-5′), 114.9 (d,
C-2′), 104.5 (s, C-10), 103.3 (d, C-1′′), 99.1 (d, C-6), 93.8 (d, C-8),
75.8 (d, C-5′′), 75.7 (d, C-4′′), 74.1 (d, C-3′′), 72.0 (d, C-2′′), 52.1 (q,
OCH3). The MS and NMR spectral data were in consistent with
those reported [22].
Acknowledgements All spectra were recorded by the Analytical
Group of the State Key Laboratory of Phytochemistry and Plant
Resources in West China, Kunming Institute of Botany, CAS.
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