全 文 ： 2009 年 1 月 第 7 卷 第 1 期 Chin J Nat Med Jan. 2009 Vol. 7 No. 1 31








Triterpenes from the Fruits of Phellodendron chinense
Schneid var. glabriusculum Schneid

YAN Chen, WANG Ye*, HAO Xiao-Jiang
Key Laboratory of Chemistry for Natural Products of Guizhou Province and Chinese Academy of Science, Guiyang 550002, China
【ABSTRACT】 AIM: To investigate the chemical constituents from the fruits of Phellodendron chinense Schneid var.
glabriusculum Schneid. METHODS: The constituents of ethyl acetate-soluble portions in the 95% ethanol extract were iso-
lated and purified by various chromatographic methods. Their structures were identified by their physicochemical characteris-
tics and spectral data. RESULTS: Eight known compounds were isolated and identified as piscidinol A(1), phellochin(2),
niloticin (3), dihydroniloticin (4), 21, 23-epoxy-21α, 24, 25-trihydroxytirucalla-7-en-3-one (5), 2α, 25-dimethylmeliano-
diol-[(21R, 23R)-epoxy-24-hydroxy-21α, 25-methoxy]tirucalla-7-en-3-one (6), boujotinolone A (7), 3-ketooleanane(8).
CONCLUSION: Compounds 5~8 are isolated from Phellodendron chinense Schneid var. glabriusculum Schneid. for the first
time.
【KEY WORDS】 Phellodendron chinense Schneid var. glabriusculum Schneid; Triterpene; Chemical constituents
【CLC Number】 R284.1 【Document code】 A 【Article ID】1672-3651(2009)01-0031-03
doi: 10.3724/SP. J. 1009.2009.00031
The genus of Phellodendron has three species in
China, Phellodendron amurense and P. chinense were
commonly in traditional Chinese medicine used to remove
damp heat, quench fire, counteract toxicity, relieve con-
sumptive fever and cure heat accumulating in the intestines
and stomach, icterus, perianal abscess, dysentery, diarrhoea
and other syndromes as traditional Chinese medicine [1,2]. P.
chinense Schneid var. glabriusculum Schneid has received
less attention. Our previous research has led to the isolation
of two terpenoids from the fruits of P. chinense Schneid var.
glabriusculum Schneid [3,4]. As a continuation of our inves-
tigation on chemical constituents of non-alkaloids from this
plant, eight compounds were obtained and identified as
piscidinol A(1), phellochin(2), niloticin(3), dihydroni-
loticin(4), 21, 23-epoxy-21α, 24, 25-trihy-droxytirucalla-
7-en-3-one (5), 2α, 25-dimethylmeli-anodiol-[(21R, 23R)-
epoxy-24-hydroxyl-21α, 25-methoxy] tirucalla-7-en-3-
one(6), boujotinolone A(7), and 3-ketooleanane(8) were
obtained. Compounds 5~8 were isolated from this plant for
the first time.
1 Apparatus and Reagents
Melting points were measured on an X-4 micromelt-

【Received on】 2008-05-28
【Foundation Item】 This project was supported by a grant from
Sciences and Technology Commission of Guizhou Province
[NY(2006)3049, NY(2006)3003] and Sciences and Technology
Bureau of Guiyang Municipality[(2006)55-2]
【 *Corresponding author 】 WANG Ye: Prof., Tel:
86-851-3809439, E-mail: wangye.cn@gmail.com
ing point apparatus and were uncorrected. IR spectra were
recorded using a Vector 22 spectrophotometer. NMR ex-
periments were performed on an INOVA-400 MHz spec-
trometer with TMS as internal standard. EI-MS was meas-
ured on an HP-5973 mass spectrometer. Column chroma-
tography was performed on silica gel (200-300 mesh, H-60)
and Sephadex LH-20 (25-100 μm, Pharmacia Company).
TLC was performed on GF254 plates (Qingdao Marine
Chemical Company, Qingdao, China); Spots of TLC were
detected by spraying with 5% H2SO4followed by heating.
2 Plant Material
The fruits of P. chinense var. glabriusculum Schneid.
were collected in Guiyang City, Guizhou province, People’s
Republic of China, in September, 2005 and authenticated by
Prof. Chen De-Yuan (Guiyang College of Traditional Chi-
nese Medicine).
3 Extraction and Isolation
The fresh fruits of P. chinense var. glabriusculum
Schneid. were extracted three times with 95% EtOH under
reflux. The extracts were condensed in vacuo to afford
crude residue which was suspended in H2O. The aqueous
suspension was acidified to pH 2 with 5% HCl and filtered.
Then the filtrate was extracted with EtOAc to afford EtOAc
extract (1.8 kg). EtOAc fraction was chromatographed on a
silica gel column (5000 g, 200-300 mesh), using a mixture
of petroleum ether-EtOAc (3:1) to yield subfractions 1-9
based on TLC analysis. Subfraction 8 (450 g) was further
separated on a silica gel column chromatography (2 000 g,
YAN Chen, et al. /Chinese Journal of Natural Medicines 2009, 7(1): 31−33
32 Chin J Nat Med Jan. 2009 Vol. 7 No. 1 2009 年 1 月 第 7 卷 第 1 期

200-300 mesh) eluted by petroleum ether-EtOAc (20:1→
1:1) and purified by Sephadex LH-20 column chromatog-
raphy eluted with (CHCl3:MeOH=1:1) to yield compounds
1 (2.5 g), 2 (150 mg), 4 (124 mg), 7(89 mg), 8 (218 mg).
Subfraction 4 (450 g) was further purified by repeated
column chromatography over silica gel H eluting with pe-
troleum ether-Me2CO (20:1→10:1) and Sephadex LH-20
(CHCl3:MeOH= 1:1) to provide compounds 5 (7 mg) and 6
(42 mg).
4 Identification
Compound 1 Colorless needles, mp: 195°C,
C30H50O4, EI-MS m/z: 474 [M]+. 1H NMR (CDCl3, 400
MHz) δ: 2.27 (1H, m, H-9), 2.75 (1H, ddd, J = 5.7, 14.5,
20.2 Hz, H-2A). 13C NMR data see Table 1. Compound 1
was identified as Piscidinol A by comparison of the physi-
cal and spectral data with the lit erature[5].
Compound 2 Colorless needles, mp: 173-175°C,
EI-MS m/z: 488 [M]+. 1H NMR(400 MHz, CDCl3)δ: 4.09
(1H, ddd, J = 4.2, 3.2, 8.4 Hz, H-23), 3.13 (1H, d, J = 10 Hz,
H-23), 3.25 (3H, s, H-OMe). 13C NMR data see Table 1.
Compound 2 was identified as Phellochin by comparison of
the physical and spectral data with the literature[6].
Compound 3 Colorless needles, mp: 139-141°C,
EI-MS m/z: 456 [M]+, 441, 369, 325, 143, 138, 71. 13C
NMR data see Table 1. Compound 3 was identified as
Niloticin by comparison of the physical and spectral data
with the literature[7].
Compound 4 Colorless needles, mp: 178-179°C,
EI-MS m/z: 458 [M]+, 371. 13C NMR data see Table 1.
Compound 4 was identified as Dihydroniloticin by com-
parison of the physical and spectral data with the litera-
ture[7].
Compound 5 Colorless needles, 130-132°C, EI-MS
m/z: 488 [M]+. 1H NMR (400 MHz, CDCl3) δ: 5.28(1H, m,

Table 1 13C NMR data(100 MHz, in CDCl3) of compounds 1-7 (100 MHz, in CDCl3)
Position 1 2 3 4 5 6 7
1 38.5 38.5 38.5 37.3 38.5 38.5 38.5
2 34.9 34.9 34.9 28.2 34.9 35.1 34.9
3 217.0 217.0 216.9 79.3 216.9 216.9 216.9
4 47.9 47.8 47.9 39.1 47.9 47.9 47.9
5 52.3 52.2 52.3 53.4 52.3 52.3 52.3
6 24.4 24.3 24.4 24.0 24.3 24.3 24.3
7 118.0 117.8 118.0 118.0 118.0 118.1 118.0
8 145.7 145.8 145.7 145.7 145.7 145.6 145.6
9 48.4 48.4 48.5 49.0 48.3 48.3 48.3
10 35.0 35.0 35.0 35.0 35.1 35.1 35.0
11 18.3 18.2 18.3 18.2 17.6 17.7 18.1
12 33.8 33.7 34.0 34.1 31.4 31.1 33.8
13 43.5 43.4 43.6 43.7 43.5 43.6 43.2
14 51.2 51.1 51.2 51.3 50.7 50.9 51.2
15 34.0 33.9 33.6 33.8 34.2 33.8 32.9
16 28.5 28.4 28.8 27.8 27.2 29.7 27.3
17 53.8 53.7 53.3 50.8 50.4 50.4 44.7
18 22.0 24.4 21.8 19.9 21.5 21.5 23.9
19 12.8 12.7 12.8 13.2 12.7 12.7 12.8
20 33.7 33.6 33.5 33.7 46.2 47.8 37.4
21 18.9 18.8 19.8 20.0 96.7 108.7 70.0
22 40.5 39.6 40.7 40.9 30.1 31.7 36.4
23 69.7 68.6 69.2 69.4 78.7 74.8 64.6
24 74.9 76.2 68.4 68.6 74.7 76.2 86.4
25 74.3 79.7 60.3 60.3 73.8 76.7 74.2
26 26.2 21.6 19.9 21.8 26.7 20.1 24.0
27 27.5 21.5 24.9 24.9 27.2 21.5 28.6
28 24.5 22.0 24.6 27.7 24.5 24.4 24.5
29 21.5 21.4 21.6 14.8 21.5 21.4 21.6
30 27.4 27.3 27.4 27.3 26.7 27.2 27.4
21-OMe 55.5
25-OMe 49.3 49.1

YAN Chen, et al. /Chinese Journal of Natural Medicines 2009, 7(1): 31−33
2009 年 1 月 第 7 卷 第 1 期 Chin J Nat Med Jan. 2009 Vol. 7 No. 1 33

H-21), 5.32 (1H, m, H-7), 4.53 (1H, m, H-23), 3.14 (1H, d,
8.8 Hz, H-24 ). 13C NMR data see Table 1. Compound 5
was identified as 21, 23-epoxy-21α, 24, 25-trihydroxy-
tirucalla-7-en-3-one by comparison of the physical and
spectral data with the literature[8].
Compound 6 Jelly, EI-MS m/z: 516 [M]+. 1H NMR
(400 MHz, CDCl3) δ: 5.32 (1H, m, H-7), 4.78 (1H, d, 3.2Hz,
H-21), 4.17 (1H, m, H-23), 3.39 (1H, d, 4.8Hz, H-24 ), 3.24
(3H, S, OMe-25), 3.34 (3H, S, OMe-21). 13C NMR data see
Table 1. Compound 6 was identified as 21α,
25-dimethylmelianodiol-[(21R, 23R)-epoxy-24-hydroxy-
21α, 25-methoxy]tirucalla- 7-en-3- one by comparison of
the physical and spectral data with the literature[9].
Compound 7 Colorless needles, mp: 110-111°C,
EI-MS m/z, 472 [M]+. the 13C NMR data see Table 1.
Compound 7 was identified as Boujotinolone A by com-
parison of the physical and spectral data with the litera-
ture[5].
Compound 8 Colorless needles(MeOH), mp:
233-235°C. 1H NMR (400 MHz, CDCl3) δ: 1.41 (1H,
s, H-22), 1.35 (1H, m, H-5 ), 1.25 (3H, s, H-23).13C NMR
(100MHz, CDCl3) δ: 35.1(C-1), 27.5(C-2), 201.8(C-3),
36.9(C-4), 51.1(C-5), 40.8(C-6), 18.0(C-7), 49.9(C-9),
37.2(C-10), 33.5(C-11), 30.1(C-12), 37.8(C-13), 38.9(C-14),
31.1(C-15), 28.9(C-16), 32.5(C-17), 39.3(C-18), 34.2(C-19),
28.0(C-20), 31.5(C-21), 34.5(C-22), 28.0(C-23), 21.7(C-24),
19.1(C-25), 17.4(C-26), 19.2(C-27), 20.0(C-28), 34.1(C-29),
33.1(C-30), EI-MS m/z: 426[M]+, 302, 205, 125, 97, 69, 55.
Compound 8 was identified as 3-Ketooleanane by com-
parison of the physical and spectral data with the litera-
ture[10].
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秃叶黄皮树果实中的三萜化学成分
晏 晨, 汪 冶*, 郝小江
贵州省、中国科学院天然产物化学重点实验室, 贵阳 550002
【摘 要】 目的：研究秃叶黄皮树(Phellodendron chinense var. glabriusculum Schneid)果实中的化学成分。方法：对
秃叶黄皮树果实 95%乙醇提取物的乙酸乙酯部分进行色谱分离, 根据光谱数据和理化性质确定各化合物的结构。结果：分
离得到 8 个已知化合物, 分别为 piscidinol A (1), phellochin (2), niloticin (3), dihydroniloticin (4), 21, 23-epoxy-21α, 24,
25-trihydroxytirucalla-7-en-3-one (5), 2α, 25-dimethylmelianodiol-[(21R, 23R)-epoxy-24-hydroxy-21α, 25-methoxy]tirucalla-
7-en-3-one (6), boujotinolone A (7), 3-ketooleanane (8)。结论：化合物 5~8 为首次从秃叶黄皮树分离得到。
【关键词】 秃叶黄皮树; 三萜; 化学成分

【基金项目】 贵州省科技攻关项目[黔科合 NY 字(2006)3049 号], [黔科合 NY 字(2006)3003 号], 贵阳市科学技术计划
项目[筑科合同字第(2006)55-2 号]