全 文 ：热带亚热带植物学报　2013， 21(5)： 466 ~ 470
Journal of Tropical and Subtropical Botany
鸦胆子果实的化学成分研究
苏志维1,2, 邱声祥1*
(1. 中国科学院华南植物园，中国科学院植物资源保护与可持续利用重点实验室， 广州 510650; 2. 中国科学院大学， 北京 100049)
摘要： 为了解鸦胆子(Brucea javanica)的化学成分，从鸦胆子果实中分离得到 13 个已知化合物，经波谱学分析鉴定为：对羟基苯
甲醛 (1)，对羟基苯甲酸 (2)，3,4-二羟基苯甲酸 (3)，3,4-二羟基苯甲酸甲酯 (4)，没食子酸 (5)，丁香酸 (6)，二氢阿魏酸 (7)，毛地黄
黄酮 (8)，angophorol (9)，2β,6β,9β-trihydroxyclovane (10)，硬脂酸 (11), β-谷甾醇 (12)和 β-胡萝卜苷 (13)。化合物 2, 4, 6 ~ 10 均
系从鸦胆子果实中首次分离得到。
关键词： 鸦胆子； 酚性化合物； 倍半萜； 脂肪酸
doi: 10.3969/j.issn.1005–3395.2013.05.014
Chemical Constituents of Fruits from Brucea javanica
SU Zhi-wei1,2, QIU Sheng-xiang1*
(1. Key Laboratory of Plant Resources Conservation and Sustainable Utilization, South China Botanical Garden, Chinese Academy of Sciences,
Guangzhou 510650, China; 2. University of Chinese Academy of Sciences, Beijing 100049, China)
Abstract: The aim was to understand the chemical constituents of Brucea javanica, thirteen known compounds
were isolated from the fruits of B. javanica by using solvent fractionation and column chromatography. On the
basis of spectral data, they were identified as para-hydroxybenzaldehyde (1), para-hydroxybenzoic acid (2),
3,4-dihydroxybenzoic acid (3), methyl 3,4-dihydroxybenzoate (4), gallic acid (5), syringic acid (6), dihydroferulic
acid (7), luteolin (8), angophorol (9), 2β,6β,9β-trihydroxyclovane (10), stearic acid (11), β-sitosterol (12),
β-daucosterol (13). The compounds 2, 4, and 6 – 10 were obtained from the fruits of B. javanica for the first time.
Key words: Brucea javanica; Phenolic compound; Sesquiterpene; Fatty acid
The genus Brucea of the family Simaroubaceae
comprises ca. 6 species, mainly distributed in Africa,
tropical regions of Asia and northern Oceania, only
with two spices (B. mollis and B. javanica) in China[1].
Its characteristic components are quassinoids[2],
which possess various biological activities including
anti-tumor[3], anthelmintic[4–7], anti-viral[8], anti-bacterial[9]
and hyperglycemic[10] activities. Brucea javanica
(L.) Merr., called ‘Yadanzi’, distributes in south of
China (mainly Guangxi and Guangdong Provinces)
and shows significantly antitumor and other activity
mostly due to quassinoids, triterpenoids and alkaloids[2].
As a continuation of our search for naturally occurring
bioactive substances from herb medicine in China,
we investigated the constituents of the air-dried fruits
of B. javanica purchased from Qingping Traditional
Chinese Medicine Market and isolated a series of
structurally diverse compounds, including nine
phenolic constituents (1 – 9), two sterides (12 – 13),
one sesquiterpenes (10), one fatty acid (11).
Received: 2012–12–24　　　　Accepted: 2013–02–28
This study was supported by grants from National and Guangzhou Science Technology Major Project (2014ZX10005-002, 2010ul-E00531), and the
Natural Science Foundation of China (30973635).
SU Zhi-wei, Ph D. Mainly study about natural product chemistry. E-mail: szw@scib.ac.cn
* Corresponding author. E-mail: sxqiu@scbg.ac.cn
第5期 467
1 Experiment
1.1 Instrument
Optical rotations were measured on a Perkin-
Elmer 343 Polarimeter. NMR spectra were recorded
on a Bruker DRX-400 spectrometer using solvent
residual peaks (CD3OD: δH 3.31 and δC 49.0 ppm;
DMSO: δH 2.50 and δC 39.52 ppm; CDCl3: δH 7.26
and δC 77.16 ppm) as references. ESIMS was taken
on a MDS SCIEX API 2000 LC/MS/MS apparatus. For
column chromatography, silica gel (200 – 300 mesh,
Qingdao Haiyang Chemical Co. Ltd., Shandong, China),
and MCI gel (75 – 150 μm, Mitsubishi Chemical
Co. Ltd., Japan) were used. TLC was performed on
precoated silica gel HSGF254 plates (Yantai Jiangyou
Silica Gel Development Co. Ltd., Shandong, China)
and RP-18 F254S plates (Merck Japan Ltd., Tokyo,
Japan), and the spots were detected first under UV
light (λ = 254 and 365 nm, respectively), and then by
spraying 10% H2SO4 in EtOH and heating.
1.2 Plant material
Air-dried mature fruits of Brucea javanica were
purchased from Qingping Traditional Chinese Medicine
Market, Guangzhou, China, in January 2008. They
were botanically authenticated by Prof. Yun-fei DENG
of South China Botanical Garden, Chinese Academy
of Sciences (SCGB), and a voucher specimen (No.
MZH0173) was deposited in the Laboratory of SCBG,
Guangzhou.
1.3 Extraction and isolation
The air-dried fruits (10 kg) were powdered and
extracted three times with 95% ethanol (50 L, each)
at room temperature. The pooled solvents were
evaporated in vacuo to give a crude extract (ca. 2 L),
which was defatted with petroleum ether and then
sequentially fractionated with EtOAc and n-BuOH
to yield EtOAc-soluble (200 g) and n-BuOH-soluble
(185 g) fractions, respectively.
The petroleum ether-soluble extract was subjected
to silica gel column chromatography (CC) and eluted
with gradient mixtures of petroleum ether-ethyl
acetate (1 : 0 – 0 : 1, V/V) to afford fractions P1 – P8.
Compounds 11 (167 mg) and 12 (632 mg) were obtained
by recrystallization from P3 and P5, respectively. The
EtOAc-soluble fraction was subjected to silica gel
CC eluted with CHCl3-MeOH (10 : 0 – 4 : 6, V/V) to
afford fractions E1 – E10. Fraction E4 was separated
by Sephadex LH-20 CC eluted with MeOH followed
by silica gel CC to yield compounds 1 (41 mg) and
4 (70 mg). Compound 13 (765 mg) was obtained by
Fig.1 Chemical structures of the isolates from the fruits of Brucea javanica
苏志维等：鸦胆子果实的化学成分研究
468 第21卷热带亚热带植物学报
recrystallization from Fraction E5 in CHCl3/MeOH
and the mother liquor was subjected to silica gel CC
eluted with CHCl3-MeOH (95 : 5 – 80 : 20, V/V)
to furnish fractions E51 – E57. Fraction E53 was
purified by Sephadex LH-20 CC eluted with MeOH
to give compounds 6 (16 mg) and 7 (8 mg). Fraction
E7 was purified by silica gel CC to give compound
2 (430.8 mg). Fraction E9 was passed through a
MCI column for depigmentation, and the resultant
MeOH elution was further separated by repetitive CC
over silica gel and Sephadex LH-20 and purified by
HPLC with MeOH-H2O as a mobile phase to furnish
compounds 10 (12 mg) and 9 (5 mg). The n-BuOH-
soluble fraction was subjected to silica gel CC to yield
fractions B1 – B8. Fraction B4 was separated by
Sephadex LH-20 CC, silica gel CC and preparative
TLC to afford compound 8 (36 mg).
2 Structure identification
para-Hydroxybenzaldehyde (1)[11]　　C7H6O2;
colorless needles; ESIMS m/z (%): 122 (M+, 100); 1H
NMR (400 MHz, CD3OD): δ 9.76 (1H, s, CHO), 7.80
(2H, d, J = 8.4, H-2, 6), 6.91 (2H, d, J = 8.5 Hz, H-3,
5).
para-Hydroxybenzoic acid (2)[12]　　C7H6O3;
white amorphous powder; ESIMS m/z (%): 138 (M+,
100); 1H NMR (400 MHz, DMSO): δ 12.42 (1H, s,
COOH), 10.23 (1H, s, OH), 7.81 – 7.76 (2H, m, H-2,
6), 6.84 – 6.80 (2H, m, H-3, 5); 13C NMR (100 MHz,
DMSO): δ 167.2 (s, -COOH), 161.6 (s, C-1), 131.6
(d × 2, C-2, 6), 121.4 (d × 2, C-3, 5), 115.2 (s, C-4).
3,4-Dihydroxybenzoic acid (3)[12]　　C7H6O4;
colorless needles; ESIMS m/z (%): 146 (M+, 100); 1H
NMR (400 MHz, CD3OD): δ 7.42 – 7.36 (2H, m, H-2,
6), 6.80 – 6.73 (1H, d, J = 8.1 Hz, H-5); 13C NMR
(100 MHz, CD3OD): δ 170.2 (s, -COOH), 151.5 (s,
C-4), 146.0 (s, C-3), 123.9 (d, C-6), 123.1 (s, C-1),
117.7 (d, C-5), 115.7 (d, C-2).
Methyl 3,4-dihydroxybenzoate (4)[13]　　C8H8O3;
colorless needles; ESIMS m/z (%): 168 (M+, 100); 1H
NMR (400 MHz, CD3OD): δ 7.59 – 7.53 (2H, m, H-2,
6), 6.87 – 6.80 (1H, d, J = 8.0 Hz, H-5), 3.93 (3H, s,
-OMe); 13C NMR (100 MHz, CD3OD): δ 170.2 (s,
-C=O), 152.6 (s, C-4), 148.6 (s, C-3), 125.3 (d, C-6),
123.1 (s, C-1), 115.9 (d, C-2), 113.8 (d, C-5), 56.4 (q,
-OMe).
Gallic acid (5)[12]　　C7H6O5; colorless needles;
ESIMS m/z (%): 170 (M+, 100); 1H NMR (400 MHz,
DMSO): δ 12.22 (1H, s, COOH), 9.04 (3H, m, OH-3,
4, 5), 6.98 – 6.73 (2H, s, H-2, 6); 13C NMR (100 MHz,
DMSO): δ 167.5 (s, COOH), 145.4 (s × 2, C-3, 5),
138.0 (s, C-4), 120.5 (s, C-1), 108.7 (d × 2, C-2, 6).
Syringic acid (6)[14]　　C9H10O5; colorless needles;
ESIMS m/z (%): 198 (M+, 100); 1H NMR (400 MHz,
CD3OD): δ 7.33 (2H, s, H-2, 6), 3.88 (6H, s, OMe-
3,5); 13C NMR (100 MHz, CD3OD): δ 170.0 (s,
-COOH), 148.8 (s × 2, C-3, 5), 141.7 (s, C-4), 121.9
(s, C-1), 108.3 (d × 2, C-2, 6), 56.8 (q × 2, 3, 5-OMe).
Dihydroferulic acid (7)[15]　　C9H10O4; white
amorphous powder, ESIMS m/z (%): 196 (M+, 100);
1H NMR (400 MHz, DMSO): δ 12.10 (1H, s, COOH),
8.71 (1H, s, OH), 6.78 (1H, d, J = 1.7 Hz, H-2), 6.65
(1H, d, J = 8.0 Hz, H-5), 6.58 (1H, dd, J = 8.0, 1.7 Hz,
H-6), 3.73 (3H, s, 3-OMe), 2.70 (2H, t, J = 7.7 Hz,
H-1′), 2.49 (2H, m, H-2′).
Luteolin (8)[16]　　C15H10O6; yellow amorphous
powder; ESIMS m/z (%): 286 (M+, 100); 1H NMR
(400 MHz, DMSO): δ 12.98 (s, 1H, 5-OH), 7.43 (1H,
d, J = 2.2 Hz, H-2′), 7.40 (2H, s, H-6′), 6.89 (1H, d,
J = 8.1 Hz, H-5′), 6.67 (1H, s, H-3), 6.45 (1H, d, J =
2.0 Hz, H-8), 6.19 (1H, d, J = 2.0 Hz, H-6); 13C NMR
(100 MHz, DMSO): δ 181.6 (s, C-4), 164.2 (s, C-7),
163.9 (s, C-2), 161.4 (s, C-5), 157.3 (s, C-9), 149.7 (s,
C-4′), 145.7 (s, C-3′), 121.4 (s, C-1′), 118.9 (d, C-6′),
116.0 (d, C-5′), 113.3 (d, C-2′), 103.6 (s, C-10), 102.8
(d, C-3), 98.8 (d, C-6), 93.8 (d, C-8).
Angophorol (9)[17]　　C16H14O5; white amorphous
powder; ESIMS m/z (%): 286 (M+, 100); 1H NMR
(400 MHz, C5D5N): δ 12.32 (1H, s, 5-OH), 11.53 (1H,
s, 7-OH), 7.20 (2H, m, H-2′, 6′), 6.92 (2H, m, H-3′,
5′), 5.99 (1H, d, J = 2.2 Hz, H-8), 5.90 (1H, d, J =
2.2 Hz, H-6), 5.15 (1H, dd, J = 12.9, 2.8 Hz, H-2), 2.95
(1H, dd, J = 17.1, 12.9 Hz, H-3ax), 2.56 (1H, dd, J =
17.1, 3.0 Hz, H-3eq); 13C NMR (100 MHz, C5D5N):
δ 197.5 (s, C-4), 168.7 (s, C-7), 165.1 (s, C-5), 164.1
第5期 469
(s, C-9), 160.1 (s, C-4′), 130.1 (s, C-1′), 129.3 (d × 2,
C-2′, 6′), 116.9 (d × 2, C-3′, 5′), 104.2 (s, C-10), 95.9
(d, C-8), 94.9 (d, C-6), 80.2 (d, C-2), 56.2 (q, 4′-OMe),
43.7 (t, C-3).
2β,6β,9β-Trihydroxyclovane (10)[18]　　C15H26O3;
colorless needles; ESIMS m/z (%): 256 (M+, 100); 1H
NMR (400 MHz, CD3OD): δ 3.85 – 3.71 (2H, m, H-2,
6), 3.26 (1H, s, H-9), 2.11 – 1.99 (1H, m, H-10α), 1.72
(1H, dd, J = 13.4, 4.6 Hz, H-10β), 1.69 – 1.63 (1H, m,
H-7α), 1.62 – 1.54 (4H, m, H-7β, 3α, 3β, 11α), 1.35
(1H, d, J = 11.2 Hz, H-5), 1.16 (3H, s, 14-CH3), 1.09
(2H, m, H-12A, 11β), 1.03 (3H, s, 15-CH3), 0.98 (3H,
s, 13-CH3), 0.83 (1H, d, J = 12.8 Hz, H-12B);
13C
NMR (100 MHz, CD3OD): δ 80.8 (d, C-2), 75.6 (d,
C-9), 69.1 (d, C-6), 57.6 (d, C-5), 48.6 (t, C-3), 46.7 (s,
C-1), 44.3 (t, C-12), 37.5 (s × 2, C-4, 8), 36.6 (t, C-7),
33.1 (q, C-14), 29.0 (q, C-15), 27.8 (t, C-11), 26.6 (t,
C-10), 24.7 (q, C-13).
Stearic acid (11)[12]　　C18H36O2; white amorphous
powder; ESIMS m/z (%): 284 (M+, 100); 1H NMR
(400 MHz, CDCl3): δ 12.32 (s, 1H, 5-OH), 11.53 (s,
1H, 7-OH), 11.20 (1H, br s, COOH), 2.35 (2H, t, J =
7.6 Hz, H-17), 5.99 (2H, m, H-16), 1.25 (28H, m,
H-15 ~ 2), 0.88 (1H, t, J = 6.8 Hz, CH3-1).
3 Results and discussion
The phytochemical study on the fruits of Brucea
javanica have led to the isolation of 13 structurally
diversified compounds, through an analysis of spectral
data (EI-MS, NMR), which be identified as para-
hydroxybenzaldehyde (1), para-hydroxybenzoic acid
(2), 3,4-dihydroxybenzoic acid (3), methyl 3,4-dihy-
droxybenzoate (4), gallic acid (5), syringic acid (6),
dihydroferulic acid (7), luteolin (8), angophorol (9),
2β,6β,9β-trihydroxyclovane (10), stearic acid (11),
β-sitosterol (12), β-daucosterol (13) (compounds 12
and 13 were identified by direct TLC comparison with
authentic samples). The compounds (2, 4, 6 – 10)
were obtained from the fruits of B. javanica for the
first time.
According to the literatures, the compounds
isolated in this study were shown to have broad-spectrum
biological activities, with emphasis on the phenolic
acids for their in vitro antiviral, antibacterial,
and antifungal activities and cytotoxicity[19]. Para-
hydroxybenzaldehyde (1) and para-hydroxybenzoic
acid (2) derivatives were reported as antibacterial
agents[20–21]. Luteolin (8) was determined to be
an emerging anti-cancer and anti-inflammation
flavonoid[22–23]. Scientific knowledge on quassinoids
and the biological properties of B. javanica has
accumulated rapidly in recent years, however, less
progress had made on the presence and biological
activities on other components rather than quassinoids.
Our current investigation revealed the existence of
many other constituents in addition to quassinoids,
whose bioactivities may account for the diversified
bioactivities and the traditional medical use of B.
javanica passed through generations. Moreover, these
chemical entities from the fruits of B. javanica could
certainly play an important role in the discovery of
new and effective therapeutic agents.
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