全 文 ： 2010 年 7 月 第 8 卷 第 4 期 Chin J Nat Med July 2010 Vol. 8 No. 4 257








Flavonoids from the Aerial Parts of Inula japonica

QIN Jiang-Jiang1, ZHU Jia-Xian1, ZHU Yan1, JIN Hui-Zi1*, LV Yong-Hai2,
ZHANG Wei-Dong1, 2*
1School of Pharmacy, Shanghai Jiaotong University, Shanghai 200240;
2Department of Phytochemistry, Second Military Medical University, Shanghai 200433, China
[ABSTRACT] AIM: To investigate the chemical constituents of the aerial parts of Inula japonica Thunb.. METHODS:
Compounds were isolated and purified by column chromatography with silica gel, Sephadex LH-20 and preparative
HPLC. Their structures were identified on the basis of physicochemical properties and spectroscopic data. RESULTS:
Nine flavonoids were isolated and elucidated as quercetin (1), 5, 7-dihydroxy-3, 3, 4-trimethoxyflavone (2), spinacetin
(3), axillarin (4), eupatin (5), casticine (6), apigenin (7), luteolin (8), and 6-hydroxyapigenin (9). CONCLUSION:
Compounds 2, 6 and 9 were isolated from this genus for the first time, and compounds 3-5 were isolated from this plant
for the first time.
[KEY WORDS] Inula Genus; Inula japonica; Flavonoids
[CLC Number] R284.1 [Document code] A [Article ID] 1672-3651(2010)04-0257-03
doi: 10.3724/SP. J. 1009.2010.00257
1 Introduction
As one of the most-popular traditional Chinese medi-
cines, Inula japonica Thunb. has been reported to possess
diverse biological activities, such as anti-tumor[1-3], an-
ti-diabetic[4], and hypolipidemic[4] activities. In order to
search for the effective constituents of this plant, continu-
ous research has been carried out in recent years. Our pre-
vious investigation on the aerial parts of I. japonica led to
the isolation of anthranilic acid derivatives[5] and sesquiter-
penes[1]. In this paper, we described the isolation and struc-
tural elucidation of nine flavonoids, quercetin (1), 5,
7-dihydroxy-3, 3, 4-trimethoxyflavone (2), spinacetin (3),
axillarin (4), eupatin (5), casticine (6), apigenin (7), luteolin
(8), and 6-hydroxyapigenin (9). Compounds 2, 6 and 9 were
isolated from this genus for the first time, and compounds
3-5 were isolated from this plant for the first time.
2 Apparatus and Reagents
1H and 13C NMR spectra were recorded on Bruker
DRX-500 spectrometers at 500 and 125 MHz, respectively.
ESIMS spectra were recorded on Varian MAT-212 mass
spectrometer. A preparative column (Shimadzu PRC-ODS

[Received on] 02-Mar-2010
[Research Funding] This project was supported by Scientific
Foundation of Shanghai China (No. 08DZ1971302).
[*Corresponding author] ZHANG Wei-Dong: Prof., Tel/Fax:
86-21-34205989, E-mail: wdzhangy@hotmail.com; JIN Hui-Zi:
Associate Prof., E-mail: kimhz@sjtu.edu.cn
EV0233) was used for preparative HPLC (Shimadzu
LC-6AD). All solvents used were of analytical grade
(Shanghai Chemical Co., Ltd.). TLC analysis was run on
HS-GF254 silica gel plates (10-40 μm, Yantai, China). Col-
umn chromatography was performed on silica gel (100-200,
200-300 mesh, Yantai, China), silica gel H (10-40 μm,
Qingdao, China) and Sephadex LH-20 (Pharmacia Co.,
Ltd.).
3 Plant Material
The aerial parts of I. japonica were collected in Anhui
province, China, in October, 2006, and were authenticated
by Professor Huang Bao-Kang, Department of Pharmacog-
nosy, School of Pharmacy, Second Military Medical Uni-
versity. A voucher specimen (No. 2007XFH1) was depos-
ited at the School of Pharmacy, Shanghai Jiaotong Univer-
sity.
4 Extraction and Isolation
The dried aerial parts of I. japonica (20.0 kg) were
powdered and extracted with 95% ethanol for three times at
room temperature. The ethanolic extract was successively
partitioned with petroleum ether (PE), CH2Cl2, EtOAc, and
n-BuOH, respectively. The CH2Cl2 fraction (84.5 g) was
chromatographed on a silica gel column eluting with a step
gradient of CH2Cl2−MeOH (100 : 0, 50 : 1 , 20 : 1, 10 : 1,
5 : 1, 2 : 1, 1 : 1) to give subfractions, respectively. Then
the subfractions were isolated and purified in a combination
of silica gel, Sephadex LH-20 and preparative HPLC to
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258 Chin J Nat Med July 2010 Vol. 8 No. 4 2010 年 7 月 第 8 卷 第 4 期

afford compounds 2 (3.5 mg), 3 (59.0 mg), 5 (60.0 mg), and
6 (18.2 mg). And from EtOAc fraction (30.1 g), 1 (51.9 mg),
4 (37.9 mg), 7 (52.7 mg), 8 (50.8 mg) and 9 (76.2 mg) were
obtained.
5 Identification
Compound 1 yellow amorphous powder, ESI-MS
m/z 325 [M + Na]+, 301 [M − H]−; 1H NMR (CD3OD, 500
MHz) δ: 7.73 (1H, d, J = 2.0 Hz, H-2), 7.63 (1H, dd, J =
8.0, 2.0 Hz, H-6), 6.88 (1H, d, J = 8.0 Hz, H-5), 6.38 (1H,
d, J = 2.0 Hz, H-8), 6.18 (1H, d, J = 2.0 Hz, H-6); 13C NMR
(CD3OD, 125 MHz) δ: 148.8 (C-2), 137.2 (C-3), 177.3
(C-4), 162.5 (C-5), 99.2 (C-6), 165.6 (C-7), 94.5 (C-8),
158.2 (C-9), 104.5 (C-10), 124.1 (C-1), 116.0 (C-2), 146.2
(C-3), 148.0 (C-4), 116.2 (C-5), 121.7 (C-6). Compound 1
was characterized as quercetin by comparison of the physi-
cal and spectral data with the literature[6].
Compound 2 yellow amorphous powder, ESI-MS
m/z 345 [M + H]+, 367 [M + Na]+. 1H NMR (DMSO-d6, 500
MHz) δ: 12.92 (1H, br s, 5-OH), 10.83 (1H, br s, 7-OH),
7.68 (1H, dd, J = 8.0, 2.0 Hz, H-6), 7.63 (1H, d, J = 2.0 Hz,
H-2), 7.16 (1H, d, J = 8.0 Hz, H-5), 6.49 (1H, d, J = 2.0 Hz,
H-8), 6.21 (1H, d, J = 2.0 Hz, H-6), 3.86, 3.86, 3.81 (each
3H, s, 3, 3,4,-OCH3); 13C NMR (DMSO-d6, 125 MHz) δ:
155.1 (C-2), 138.0 (C-3), 177.9 (C-4), 161.2 (C-5), 98.6
(C-6), 164.1 (C-7), 93.8 (C-8), 156.3 (C-9), 104.2 (C-10),
122.1 (C-1), 111.6 (C-2), 148.4 (C-3), 151.2 (C-4), 111.2
(C-5), 121.9 (C-6), 59.7 (3H, s, 3-OCH3), 55.6 (3H, s,
3-OCH3), 55.6 (3H, s, 4-OCH3). Compound 2 was charac-
terized as 5, 7-dihydroxy-3, 3, 4- trimethoxyflavone by
comparison of the physical and spectral data with the lit-
erature[7].
Compound 3 yellow amorphous powder, ESI-MS
m/z 369 [M + Na]+, 345 [M − H]−. 1H NMR (DMSO-d6, 500
MHz) δ: 12.35 (1H, brs, 5-OH), 9.73 (1H, br s, 7-OH), 9.33
(1H, br s, 4-OH), 8.66 (1H, br s, 3-OH), 7.57 (1H, d, J =
2.0 Hz, H-2), 7.46 (1H, dd, J = 8.0, 2.0 Hz, H-6), 6.89 (1H,
d, J = 8.0 Hz, H-5), 6.80 (1H, s, H-8), 3.88, 3.77 (each 3H,
s, 6, 3-OCH3); 13C NMR (DMSO-d6, 125 MHz) δ: 148.8
(C-2), 137.5 (C-3), 178.1 (C-4), 148.6 (C-5), 129.6 (C-6),
155.7 (C-7), 90.8 (C-8), 154.5 (C-9), 105.5 (C-10), 121.0
(C-1), 115.7 (C-2), 145.2 (C-3), 145.7 (C-4), 115.5 (C-5),
120.8 (C-6), 59.6 (3H, s, 6-OCH3), 56.6 (3H, s, 3-OCH3).
Compound 3 was characterized as spinacetin by comparison
of the physical and spectral data with the literature[8].
Compound 4 yellow amorphous powder, ESI-MS
m/z 347 [M + H]+, 369 [M + Na]+. 1H NMR (CD3OD, 500
MHz) δ: 7.62 (1H, d, J = 2.5 Hz, H-2), 7.52 (1H, dd, J =
8.5, 2.5 Hz, H-6), 6.90 (1H, d, J = 8.5 Hz, H-5), 6.69 (1H,
s, H-8), 3.96, 3.79 (each 3H, s, 3, 6, -OCH3); 13C NMR
(CD3OD, 125 MHz) δ: 150.4 (C-2), 140.1 (C-3), 180.7
(C-4), 151.7 (C-5), 131.6 (C-6), 158.8 (C-7), 92.2 (C-8),
156.4 (C-9), 107.8 (C-10), 123.8 (C-1), 116.7 (C-2), 146.9
(C-3), 147.4 (C-4), 117.2 (C-5), 122.9 (C-6), 61.0 (3H, s,
3-OCH3), 57.5 (3H, s, 7-OCH3). Compound 4 was charac-
terized as axillarin by comparison of the physical and spec-
tral data with the literature[9].
Compound 5 yellow amorphous powder, ESI-MS
m/z 383 [M + Na]+, 359 [M − H]−. 1H NMR (DMSO-d6, 500
MHz) δ: 12.34 (1H, s, 5-OH), 9.41 (1H, s, 3-OH), 8.73 (1H,
s, 3-OH), 7.59 (1H, dd, J = 9.0, 3.0 Hz, H-6), 7.58 (1H, d, J
= 3.0 Hz, H-2), 7.11 (1H, d, J = 9.0 Hz, H-5), 6.86 (1H, s,
H-8), 3.92, 3.88, 3.81 (each 3H, s, 6, 7, 4-OCH3); 13C NMR
(DMSO-d6, 125 MHz) δ: 152.0 (C-2), 139.6 (C-3), 179.9
(C-4), 150.6 (C-5), 131.4 (C-6), 157.2 (C-7), 92.6 (C-8),
156.4 (C-9), 107.4 (C-10), 124.3 (C-1), 116.8 (C-2), 147.5
(C-3), 148.1 (C-4), 113.7 (C-5), 122.1 (C-6), 61.5 (3H, s,
6-OCH3), 58.1 (3H, s, 7-OCH3), 57.4 (3H, s, 4-OCH3).
Compound 5 was characterized as eupatin by comparison of
the physical and spectral data with the literature[8].
Compound 6 yellow amorphous powder, ESI-MS
m/z 373 [M − H]−, 747 [2M −  H]−. 1H NMR (CDCl3, 500
MHz) δ: 12.59 (1H, br s, 5-OH), 7.72 (1H, dd, J = 8.5, 2.5
Hz, H-6), 7.68 (1H, d, J = 2.5 Hz, H-2), 6.97 (1H, d, J =
8.5 Hz, H-5), 6.50 (1H, s, H-8), 3.99, 3.96, 3.92, 3.81 (each
3H, s, 3, 6, 7, 4-OCH3); 13C NMR (CDCl3, 125 MHz) δ:
152.3 (C-2), 139.0 (C-3), 179.0 (C-4), 152.7 (C-5), 132.3
(C-6), 158.8 (C-7), 90.3 (C-8), 155.6 (C-9), 106.6 (C-10),
123.6 (C-1), 110.4 (C-2), 145.6 (C-3), 148.8 (C-4), 114.3
(C-5), 121.6 (C-6), 60.9 (3H, s, 3-OCH3), 60.0 (3H, s,
6-OCH3), 56.2 (3H, s, 7-OCH3), 55.9 (3H, s, 4-OCH3).
Compound 6 was characterized as casticin by comparison
of the physical and spectral data with the literature[10].
Compound 7 yellow amorphous powder, ESI-MS
m/z 271 [M + H]+, 269 [M − H]−. 1H NMR (CD3OD, 500
MHz) δ: 7.92 (2H, d, J = 8.5 Hz, H-2, 6), 6.93 (2H, d, J =
8.5 Hz, H-3, 5), 6.77 (1H, s, H-3), 6.48 (1H, d, J = 2.0 Hz,
H-8), 6.19 (1H, d, J = 2.0 Hz, H-6); 13C NMR (CD3OD, 125
MHz) δ: 164.3 (C-2), 102.9 (C-3), 181.8 (C-4), 163.8 (C-5),
98.9 (C-6), 164.3 (C-7), 94.0 (C-8), 161.5 (C-9), 103.7
(C-10), 121.2 (C-1), 128.5 (C-2, 6), 116.0 (C-3, 5), 157.4
(C-4). Compound 7 was characterized as apigenin by com-
parison of the physical and spectral data with the litera-
ture[6].
Compound 8 yellow amorphous powder, ESI-MS

Fig. 1 Structures of compounds 1−9
QIN Jiang-Jiang, et al. /Chinese Journal of Natural Medicines 2010, 8(4): 257−259
2010 年 7 月 第 8 卷 第 4 期 Chin J Nat Med July 2010 Vol. 8 No. 4 259

m/z 309 [M + Na]+, 285 [M − H]−. 1H NMR (DMSO-d6, 500
MHz) δ: 12.98 (1H, s, 5-OH), 10.82 (1H, s, 7-OH), 9.90
(1H, s, 4-OH), 9.41 (1H, s, 3-OH), 7.43 (1H, d, J = 2.0 Hz,
H-2), 7.41 (1H, dd, J = 8.5, 2.0 Hz, H-6), 6.90 (1H, d, J =
8.5 Hz, H-5), 6.68 (1H, s, H-3), 6.45 (1H, d, J = 2.0 Hz,
H-8), 6.20 (1H, d, J = 2.0 Hz, H-6); 13C NMR (DMSO-d6,
125 MHz) δ: 164.1 (C-2), 102.9 (C-3), 181.62 (C-4), 161.46
(C-5), 98.8 (C-6), 163.9 (C-7), 93.8 (C-8), 157.3 (C-9),
103.7 (C-10), 121.5 (C-1), 113.4 (C-2), 145.7 (C-3), 149.7
(C-4), 116.0 (C-5), 119.0 (C-6). Compound 8 was charac-
terized as luteolin by comparison of the physical and spec-
tral data with the literature[6].
Compound 9 yellow amorphous powder, ESI-MS
m/z 287 [M + H]+, 285 [M − H]−. 1H NMR (DMSO-d6, 500
MHz) δ: 7.94 (2H, d, J = 8.5 Hz, H-2, 6), 7.12 (2H, d, J =
8.5 Hz, H-3, 5), 6.59 (1H, s, H-8), 6.21 (1H, s, H-3); 13C
NMR (DMSO-d6, 125 MHz) δ: 162.8 (C-2), 104.4 (C-3),
181.2 (C-4), 158.9 (C-5), 132.5 (C-6), 162.4 (C-7), 101.5
(C-8), 159.8 (C-9), 107.4 (C-10), 123.0 (C-1), 128.5 (C-2,
6’), 117.5 (C-3, 5), 159.5 (C-4). Compound 9 was char-
acterized as 6-hydroxyapigenin by comparison of the
physical and spectral data with the literature[11].
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旋覆花地上部分中的黄酮类化合物
覃江江 1, 朱佳娴 1, 朱 燕 1, 金慧子 1*, 吕永海 2, 张卫东 1, 2*
1 上海交通大学药学院, 上海 200240;
2 第二军医大学药学院, 上海 200433
【摘 要】 目的：研究旋覆花地上部分中的化学成分。方法：应用硅胶柱色谱, Sephadex LH-20 柱色谱, 以及高效液
相制备色谱等手段分离和纯化化合物, 通过光谱学方法,并结合化合物的理化性质鉴定它们的结构。结果：从旋覆花地上
部分中分离得到 9 个黄酮类化合物, 分别鉴定为槲皮素(1)、5, 7-二羟基-3, 3, 4-三甲氧基黄酮(2)、3, 5, 7, 4-四羟基-3’, 6-
二甲氧基黄酮(3)、5, 7, 3, 4-四羟基-3, 6-二甲氧基黄酮(4)、异泽兰黄素(5)、紫花牡荆素(6)、芹菜素(7)、木犀草素(8)、黄
芩素(9)。结论：化合物 2、6、和 9 为首次从旋覆花属中分得, 化合物 3~5 为首次从该旋覆花中分离得到。
【关键词】 旋覆花属; 旋覆花; 黄酮类化合物

【基金项目】 上海市科委中药现代化专项重大项目(No. 08DZ1971302)