全 文 ：1. Introduction
Croton crassifolius Geisel (Euphorbiaceae) grows
widely in Hainan, Guangdong, Guangxi, Fujian and other
southern regions of China as well as Vietnam, Laos and
Thailand. The roots of croton crassifolius have been
used in traditional Chinese medicine for the treatment
of rheumatic arthralgia[1], pain in waist and lower
extremities, straining muscle pain[2], gastric and duodenal
ulcer[3] and HBV[5]. The recent pharmacological studies
have shown that medicinal croton plants have multiple
bioactivities, especially antibacterial, antivirus, anti-
tumor[6] and antiangiogenic activities, which have attracted
more and more attention. However, few researches
have investigated the activities of compounds which
are isolated from Croton crassifolius Geisel. In order to
supplement and enrich the research content of this plant
and to provide the theoretical basis for its medicinal value,
we carried out a systematic separation of the chemical





constituents from the plant, and nine diterpens were
isolated. Compound 1 was a new compound among all
these nine compounds.
2. Experimental
2.1. General procedure
NMR spectra were recorded on a Bruker AM-400
spectrometer, operating at 400 MHz for 1H NMR and
100 MHz for 13C NMR with tetramethylsilane (TMS)
as the internal standard. Silica gel (200–300 mesh,
Anhui Liangchen Chemical Factory), Sephadex LH-20
(18–111 μm, Pharmacia), and YMC C18 semi-preparative
column (YMC-pack ODS-A, 300 mm×10 mm, 5 μm,
YMC Co., Ltd.) were used for separation.
2.2. Plant materials
The roots of Croton crassifolius Geisel were collected
from Guang Dong Province, China, in November 2010,
and they were identified by Prof. Hongzheng Fu. A
voucher specimen was deposited at the State Key
Laboratory of Natural and Biomimetic Drugs, Peking
University Health Science Center.
Chemical constituents from Croton crassifolius Geisel
Junli Liu1,2, Yanping Hao1, Jianbin Wang2, Wentong Dou1, Chen Chen2, Yan Guo1, Dan Yuan1*,
Hongzheng Fu2*
1. College of Traditional Chinese Medicine, Shenyang Pharmaceutical University, Shenyang, Liaoning, 110016, China
2. State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University Health Science Center,
Beijing 100191, China
Abstract: Croton crassifolius Geisel belongs to the genus croton of the family euphorbiaceae. By means of solvent extraction
and repeated chromatorgraphy on silica gel, Sephadex LH-20 and HPLC, the ethanol extract of the roots of Croton crassifolius
Geisel was chemically investigated, which led to the isolation of nine diterpenoids. By using spectroscopic analysis, their structures
were identified as follows: Crassifolin P (1), Crassifolin J (2), 1,5,6-trimethyl-5-(2-(5-oxo-2,5-dihydrofuran-3-yl)ethyl)-
1,2,3,4,5,6,7,8-octahydronaphthalene-1-carboxylate (3), Penduliflaworosin (4), isoteucvin (5), Crassifolin G (6), teucvin (7),
Chettaphanin I (8), mallotucin D (9). Among of them compound 1 was a new compound.
Keywords: Croton crassifolius Geisel; Chemical constituents; Structural identification
CLC number: R284 Document code: A Article ID: 1003–1057(2016)11–826–06
Received: 2016-04-18, Revised: 2016-05-04, Accepted: 2016-06-03.
Foundation item: National Natural Science Foundation of China (Grant
No. 81172943).
*Corresponding author. Tel.: +86-010-82805212,
E-mail: drhzfu@sina.com
http://dx.doi.org/10.5246/jcps.2016.11.092
826 Journal of Chinese Pharmaceutical Sciences http://www.jcps.ac.cn
827 Liu, J.L. et al. / J. Chin. Pharm. Sci. 2016, 25 (11), 826–831
Position δH (J in Hz) δC
1
1.78 (1H, m)
1.2 (1H, m)
24.9
2 1.55 (2H, m) 20.2
3
1.9 (1H, m)
1.4 (1H, m)
36.3
4 — 47.3
5 — 133.2
6
1.95 (1H, m)
1.78 (1H, m)
27.7
7 1.22 (2H, m) 21.9
8 1.50 (1H, m) 42.1
9 — 40.3
10 — 134.5
11
1.78 (1H, m)
1.6 (1H, m)
33.6
12
1.99 (1H, m)
2.38 (1H, m)
23.5
13 — 173.8
14 5.95 (1H, s) 114.0
15 — 174.3
16 4.86 (2H, s) 73.6
17
3.58 (1H, dd, 10.5, 3.8)
3.14 (1H, dd, 12.8, 3.4)
62.2
18 — 178.8
19 1.17 (3H, s) 24.5
20 0.85 (3H, s) 21.5
Table 1. 1H and 13C NMR (MeOD) spectral data of compound 1.
2.3. Extraction and isolation
The EtOH extracts (5 kg) were suspended in methanol
and extracted with petroleum ether. The dried methanol
layer was dissolved in water and then extracted with
EtOAc. The EtOAc layer (600 g) was chromatographed
on a silica gel column with gradient mixtures of CHCl3–
CH3OH (100:0→0:100, v/v). Seven sections were collected
and examined by TLC on silica gel. The section 3
(CHCl3–CH3OH, 30:1, v/v) was purified by Sephadex
LH-20 (CH3OH) to obtain S3-1–S3-3. The section S3-2 was
separated by semi-preparative HPLC (MeOH–H2O–TFA,
60:40: 0.01%, v/v/v) to give compound 1 (60 mg). The
CHCl3 fraction (156.0 g) was subjected to column
chromatography (CC) over silica gel eluting with a
gradient of PE–EtOAc (60:1 to 0:1, v/v) to yield 10
fractions (A–O). The fraction A (8 g) was subjected to
silica gel CC, eluting with a PE–EtOAC (30:1–2:1, v/v).
So compound 2 (10 mg), compound 3 (500 mg) and
compound 4 (367 mg) were obtained from fraction A.
The fraction E (27 g) was fractionated bygsilica gel
column chromatography using a mobile phase consisting
of CHCl3 and MeOH to yield FrE1–FrE10. FrE1 was
washed by MeOH for five times to obtain compound 9
(2.23 g). FrE2, FrE3, FrE6 and FrE8 were separated
by semi-preparative HPLC (MeOH–H2O, 50:50, v/v)
to give compound 5 (8 mg) , compound 6 (32 mg),
compound 7 (7 mg) and compound 8 (673 mg).
3. Identification
3.1. Crassifolin P
Compound 1 was a yellow solid with the specific
rotation of +0.0978 (c 0.1, MeOH). It was assigned
with the molecular formula C20H28O5 on the basis of
its HR-ESI-MS (m/z 348.1854 [M]+). The IR spectrum
showed the presence of hydroxy (3422 cm–1) and
carbonyl (1730 cm–1) groups. The 1H NMR spectrum
exhibited signals for two methyl groups (δH 1.77 (3H, s)
and 0.85 (3H, s)), two oxygenated methylenes (δH 4.86
(2H, s) and δH 3.58 (1H, dd, J1 10.4 Hz, J2 3.8 Hz),
3.14 (1H, dd, J1 12.8 Hz, J2 3.4 Hz)), and an olefinic
proton (δH 5.95 (1H, s)). The
13C NMR spectra indicated
20 carbon signals, including two methyl, nine methylene,
two methine and seven quaternary carbons. The 1H and
13C NMR spectral data of 1 (Table 1) were similar to
those of 9-[2-(2(5H)-furanone-4-yl)ethyl]-4,8,9-trimethyl-
1,2,3,4,5,6,7,8-octahydronaphthalene-4-carboxylic acid[6].
The only difference was the presence of hydroxy methyl
instead of methyl (δC 33.8). The structure was confirmed
by 1H-1H COSY correlations from H-17 to C-8. HMBC
correlations from H-17 to C-7 and C-8 indicated that
the OH group was attached to C-17. Therefore, we could
confirm the site of hydroxy methyl (Fig. 1).
The NOESY showed correlation between H-8 and
H-12, H-7 and H-20, H-17 and H-20. A simulation of
the stereo-structures of P-a (11β, 20α, 17α) revealed
that H-8 and H-12, H-7 and H-20, H-17 and H-20 were
sufficiently close to produce an NOE effect. The spatial
22
D[α]
828 Liu, J.L. et al. / J. Chin. Pharm. Sci. 2016, 25 (11), 826–831
distances between H-8 and H-12, H-7 and H-20, H-17
and H-20 in P-a were 2.0 Å, 2.1 Å, 2.6 Å, respectively.
In contrast, the spatial distance between H-7 and H-20
in P-b was 4.8 Å. The spatial distance between H-8 and
H-12 in P-b was 4.3 Å. P-b was difficult to produce
an NOE effect. The spatial distance between H-17 and
H-20 in P-c was 4.5 Å. The spatial distance between
H-17 and H-20 in P-c was 4.5 Å. P-c was difficult to
produce an NOE effect. The spatial distance between
H-17 and H-20 in P-c was 4.5 Å. The spatial distance
between H-17 and H-20 in P-d was 4.5 Å. P-d was
difficult to produce an NOE effect. Therefore, this
compound was identified as clerodane diterpenoids,
not neo-clerodane diterpenoids (Fig. 2).
The NOESY showed correlation between H-12 and
H-19. A simulation of the stereo-structures of Pa-1
revealed that H-12 and H-19 in Pa-1 were sufficiently
close to produce an NOE effect. The spatial distance
between H-12 and H-19 in Pa-1 was 3.5 Å. In contrast,
the spatial distance between H-12 and H-19 in Pa-2 was
6.3 Å. Pa-2 was difficult to produce an NOE effect. To
confirm the structure of compound 1, the key issue was
the definition of the configuration of the C-4 stereogenic
centers. The ECD spectrum of (19β)-Pa-1 and its
(19α)-Pa-2 were calculated using the TDDFT method
at the B3 LYP/6-31+g (d) level. The calculated ECD
spectrum of Pa-1 showed the same pattern as the
experimental ECD spectrum of compound 1, and it was
generally opposite to that of Pa-2 (Fig. 3). Therefore,
the structure of compound 1 was established as shown.
Figure 1. The key HMBC and 1H-1H COSY correlations of compound 1.
HMBC 1H-1H COSY
CH2OH
HOOC
O
O
1
2
3
4
5
6
7
8
9
10
11
12
1314
15
16
20
18 19
17
Figure 2. (A) Low-energy conformers of Pa-d and the key NOESY
correlations of Pa-d; (B) Low-energy conformers of Pa-1, Pa-2 and
the key NOESY correlations of Pa-1, Pa-2.
Figure 3. Comparison between calculated and experimental ECD
spectra of compound 1.
14
12
10
8
6
4
2
0
–2
–4
–6
–8
–10
–12
Calcd. for P2
Calcd. for P1
Exptl. for 1
200 250 300 350 400
Wavelength (nm)
Δ
ε
[M
–
1
cm
–
1
]
(A)
H-12a
2.0Å
2.6Å
H-20b
H-17a
H-20a
2.1Å
H-8
H-7a
P-a
H-12a
4.3Å
H-20a
4.8Å
H-8 H-7a
P-b
H-20b
H-17a
4.5Å
P-c P-d
H-20b
H-7a
4.5Å
NOE no NOE
(B)
H-12a
3.5Å
H-19a
Pa-1 Pa-2
NOE no NOE
H-12a
6.3Å
H-19a
829 Liu, J.L. et al. / J. Chin. Pharm. Sci. 2016, 25 (11), 826–831
3.2. Crassifolin J (2)
Compound 2 was assigned with the molecular formula
C20H20O5 on the basis of its EI-MS m/z 340.4 [M]
+. The
1H NMR spectrum exhibited signals from two methyl
groups (δH 1.08 (3H, s)) and 0.81 (3H, d, J 3.29 Hz).
The 13C NMR spectrum showed 20 carbon signals,
including two methyl groups (δc 16.3 and 16.2) and
two carbonyl (δc 177.0 and 177.7). The structure of
compound 2 was similar to that of penduliflaworosin.
But the difference between compound 2 and pendu-
liflaworosin was the presence of methine carbon bearing
oxygen (δC 73.5) in compound 2 instead of OCH3 (δC 51.9).
The HMBC of H-2 and C-18 had correlation. A lactone
ring was produced between C-2 and C-4. Two carbons
(δC 108.0 and 146.1) formed a double bond. Furthermore,
a single crystal X-ray crystallography determined the
stereochemistry of compound 2 (Fig. 4).
X-ray Crystallographic analysis of Compound 2:
X-ray crystallo graphic analysis of compound of 2. Colorless
blocks, C20H20O5, Mr = 340.36, orthorhombic, space group
P212121, a = 10.126(5) Å, b = 11.275(5) Å, c = 14.731(7) Å,
V = 1681.8(14) Å3, Z = 4, dx = 1.344 Mg/m
3, F(000) = 720,
μ (Cu Ka) = 0.990 mm–1. Graphitemonochromated
radiation (λ = 1.54187 Å) was used on a Gemini S
Ultra when collecting data; 2324 unique reflections
were collected to θmax = 68.1°. The crystal size was
0.30 mm3×0.17 mm3×0.10 mm3. The methold (SHELXL-
2014) was used to determine the structure.
3.3. 1,5,6-Trimethyl-5-(2-(5-oxo-2,5-dihydrofuran-
3-yl)ethyl)-1,2,3,4,5,6,7,8-octahydronaphthalene-1-
carboxylate (3)
Colorless block crystals; HR-EI-MS m/z: 346.213 [M]+;
1H NMR (400 MHz, CDCl3) δ: 1.69 (1H, m, H-1a),
2.12 (1H, m, H-1b), 1.63 (1H, m, H-2), 1.43 (1H, m,
H-3a), 2.02 (1H, m, H-3b), 1.73 (1H, brd, J 16.9 Hz,
H-6a), 2.04 (1H, m, H-6b), 1.47 (2H, m, H-7), 1.55 (1H,
m, H-8), 1.67 (1H, m, H-11), 2.00 (1H, m, H-12a), 2.32
(1H, t, J1 16.7 Hz, J2 7.8 Hz, H-12b), 5.83 (1H, t, J 1.7 Hz,
H-14), 4.75 (2H, d, J 1.3 Hz, H-16), 0.90 (3H, d, J 6.8 Hz,
































H-17), 1.27 (3H, s, H-19), 0.94 (3H, s, H-20), 3.65
(3H, s, -OMe). 13C NMR (100 MHz, CDCl3) δ: 25.2
(C-1), 20.0 (C-2), 36.4 (C-3), 47.7 (C-4), 133.0 (C-5),
27.6 (C-6), 26.8 (C-7), 33.8 (C-8), 41.0 (C-9), 134.5
(C-10), 33.7 (C-11), 23.6 (C-12), 171.1 (C-13), 115.0
(C-14), 174.0 (C-15), 73.1 (C-16), 16.1 (C-17), 177.9
(C-18), 24.4 (C-19), 20.7 (C-20), 51.9 (-OCH3). The
1H and 13C NMR data were in agreement with those in
the literature[6].
Position δH (J in Hz) δC
1
2.25 (1H, m)
2.11 (1H, m)
33.2
2 4.76 (1H, m) 73.5
3
2.16 (1H, dd, J1 11.3 Hz, J2 11.1 Hz)
1.87 (1H, d, J 11.4 Hz)
40.1
4 — 43.1
5 — 137.0
6
2.32 (1H, m)
1.98 (1H, m)
23.8
7
1.80 (1H, m)
1.64 (1H, m)
24.7
8 1.80 (1H, m) 34.6
9 — 56.8
10 — 125.0
11 5.85 (1H, s) 108.0
12 — 146.1
13 — 115.3
14 5.84 (1H, s) 107.7
15 7.99 (1H, s) 140.8
16 7.79 (1H, t) 144.9
17 0.81 (3H, d, J 5.96 Hz) 16.1
18 — 177.7
19 1.25 (3H, s) 16.3
20 — 177.0
Table 2. 1H and 13C NMR (MeOD) spectral data of compound 2.
Figure 4. Perspective drawings of the X-ray structures of compound 2.
830 Liu, J.L. et al. / J. Chin. Pharm. Sci. 2016, 25 (11), 826–831
3.4. Penduliflaworosin (4)
White needle crystal; ESI-MS m/z: 359 [M+H]+;
1H NMR (400 MHz, CDCl3) δ: 2.06 (1H, m, H-1a),
1.80 (1H, m, H-1b), 1.70 (2H, m, H-2), 2.19 (1H, dd
J1 13.4 Hz , J2 7.6 Hz, H-3a) 1.93 (1H, m, H-3b), 1.54
(1H, m, H-6b), 1.82 (1H, m, H-6b), 1.61 (1H, m, H-7a),
1.94 (1H, m, H-7b), 1.69 (1H, m, H-8), 1.70 (1H, m,
H-9), 2.78 (1H, dd, J1 13.3 Hz, J2 9.6 Hz, H-11a),
2.20 (1H, dd, J1 13.5 Hz, J2 7.6 Hz, H-11b), 5.42 (1H, t,
J 8.4 Hz, H-12), 6.38 (1H, brs, H-14), 7.42 (1H, s, H-15),
7.41 (1H, s, H-16), 1.02 (3H, d, J 6.9 Hz, H-17), 1.31
(3H, s, H-18), 3.65 (3H, s, OMe). 13C NMR (100 MHz,
CDCl3) δ: 24.6 (C-1), 18.9 (C-2), 26.5 (C-3), 47.3 (C-4),
134.8 (C-5), 26.5 (C-6), 34.9 (C-7), 37.7 (C-8), 53.2
(C-9), 128.6 (C-10), 41.3 (C-11), 72.2 (C-12), 125.8
(C-13), 108.2 (C-14), 144.1 (C-15), 139.2 (C-16), 16.2
(C-17), 22.8 (C-18), 178.1 (C-19), 177.4 (C-20), 51.9
(-OCH3). The
1H NMR and 13C NMR data were in
agreement with those in the literature[7].
3.5. Isoteucvin (5)
Colorless block crystals; ESI-MS m/z: 329 [M+H]+;
1H NMR (400 MHz, CDCl3) δ: 1.85 (1H, m, H-1a),
2.20 (1H, m, H-1b), 1.45 (1H, m, H-2a), 1.85 (1H, m,
H-2b), 2.20 (1H, m, H-3a), 2.40 (1H, m, H-3b), 4.83
(1H, d, J 12.7 Hz, H-6), 1.20 (1H, m, H-7a), 2.40 (1H,
m, H-7b), 2.00 (1H, m, H-8), 2.70 (1H, dd, J1 13.2 Hz,
J2 9.1 Hz, H-10), 2.00 (1H, m, H-11a), 2.66 (1H, m,
H-11b), 5.50 (1H, dd, J1 9.3 Hz, J2 2.6 Hz, H-12), 6.37
(1H, br, s, H-14), 7.48 (1H, brs, H-15), 7.45 (1H, brs,
H-16), 1.08 (3H, d, J 7.0 Hz, H-17). 13C NMR (100 MHz,
CDCl3) δ: 22.9 (C-1), 22.4 (C-2), 19.0 (C-3), 125.0 (C-4),
166.0 (C-5), 77.2 (C-6), 34.0 (C-7), 38.9 (C-8), 47.2 (C-9),
37.7 (C-10), 40.6 (C-11), 71.6 (C-12), 126.1 (C-13),
107.8 (C-14), 144.5 (C-15), 138.7 (C-16), 19.1 (C-17),
173.0 (C-18), 176.8 (C-20). The 1H NMR and 13C NMR
data were in agreement with those in the literature[8].
3.6. Crassifolin G (6)
Colorless block crystals; ESI-MS m/z: 345.1 [M+H]+;
1H NMR (400 MHz, MEOD) δ: 1.63 (1H, m, H-1a),
2.26 (1H, m, H-1b), 2.32 (1H, m, H-2a), 1.94 (1H, m,
H-2b), 2.28 (1H, m, H-3a), 1.78 (1H, m, H-3b), 5.14
(1H, m, H-6), 1.48 (1H, m, H-7a), 2.07 (1H, m, H-7b),
2.2 (1H, m, H-8), 3.27 (1H, m, H-11a), 2.26 (1H, H-11b),
5.57 (1H, t, J 7.8 Hz, H-12), 6.52 (1H, s, H-14), 7.56
(1H, s, H-15), 7.63 (1H, s, H-16), 1.00 (3H, d, J 6.6 Hz
H-17). 13C NMR (100 MHz, MeOD) δ: 33.5 (C-1),
19.5 (C-2), 19.0 (C-3), 121.0 (C-4), 162.9 (C-5), 77.9
(C-6), 35.3 (C-7), 32.2 (C-8), 59.6 (C-9), 69.0 (C-10),
34.3 (C-11), 72.8 (C-12), 125.6 (C-13), 107.8 (C-14),
144.6 (C-15), 140.3 (C-16), 16.3 (C-17), 173.3 (C-18),
176.8 (C-19). The 1H NMR and 13C NMR data were in
agreement with those in the literature[10].
3.7. Teucvidin (7)
Colorless block crystals; ESI-MS m/z: 329; 1H NMR
(400 MHz, DMSO-d6) δ: 1.78 (1H, m, H-1a), 1.50 (1H,
m, H-1b), 1.86 (1H, m, H-2a), 1.50 (1H, m, H-2b),
2.18 (1H, m, H-3a), 2.34 (1H, m, H-3b), 5.10 (1H, ddd,
H-6), 1.48 (1H, m, H-7a), 2.30 (1H, m, H-7b), 2.18 (1H,
m, H-8), 3.14 (1H, m, H-10), 2.56 (1H, dd, J1 14.2 Hz,
J2 8.2 Hz, H-11a), 1.95 (1H, dd, J1 13.7 Hz, J2 8.4 Hz,
H-11b), 5.39 (1H, t, J 8.0 Hz, H-12), 6.63 (1H, s, H-14),
7.68 (1H, s, H-15), 7.78 (1H, s, H-16), 1.28 (3H, d,
J 7.3 Hz, H-17).
13C NMR (100 MHz, CDCl3) δ: 22.9
(C-1), 21.5 (C-2), 19.9 (C-3), 126.5 (C-4), 163.8 (C-5),
76.5 (C-6), 35.7 (C-7), 38.2 (C-8), 52.3 (C-9), 35.9
(C-10), 38.3 (C-11), 71.9 (C-12), 125.6 (C-13), 109.4
(C-14), 144.8 (C-15), 141.3 (C-16), 14.3 (C-17), 172.7
(C-18), 172.2 (C-20). The 1H and 13C NMR data were
in agreement with those in the literature[9].
3.8. Chettaphanin I (8)
Colorless block crystals; ESI-MS m/z: 397 [M+Na]+;
1H NMR (400 MHz, DMSO-d6) δ: 5.77 (1H, s, H-1),
2.64 (1H, s, H-3a), 2.60 (1H, s, H-3b), 2.23 (1H, m, H-6),
1.35 (1H, m, H-7a), 2.07 (1H, m, H-7b), 2.2 (1H, m,
H-8), 3.27 (1H, m, H-11a), 3.26 (1H, m, H-11b), 6.52
(1H, s, H-14), 7.56 (1H, s, H-15), 7.63 (1H, s, H-16),
831 Liu, J.L. et al. / J. Chin. Pharm. Sci. 2016, 25 (11), 826–831
0.84 (3H, d, J 6.7 Hz, H-17), 1.11 (3H, s, H-18), 1.22
(3H, s, H-20), 3.56 (3H, s, OMe). 13C NMR (100 MHz,
DMSO-d6) δ: 125.1 (C-1), 192.6 (C-2), 53.2 (C-3), 43.5
(C-4), 71.5 (C-5), 31.5 (C-6), 26.3 (C-7), 35.2 (C-8),
41.4 (C-9), 167.5 (C-10), 47.3 (C-11), 197.5 (C-12),
128.4 (C-13), 108.6 (C-14), 145.2 (C-15), 148.9 (C-16),
17.1 (C-17), 19.6 (C-18), 175.1 (C-19), 26.3 (C-20), 52.3
(OMe). The 1H and 13C NMR data were in agreement
with those in the literature[11].
3.9. Mallotucin D (9)
Colorless block crystals; ESI-MS m/z: 411 [M+Na]+;
1H NMR (400 MHz, CDCl3) δ: 2.25 (1H, m, H-1a), 1.82
(1H, m, H-1b), 1.90 (1H, m, H-2 ), 1.95 (1H, m, H-3a),
1.50 (1H, m, H-3b), 4.56 (1H, m, H-6), 1.90 (1H, m,
H-7a), 2.20 (1H, m, H-7b), 2.0 (1H, m, H-8), 2.81 (1H,
dd, J1 13.8 Hz, J2 8.4 Hz, H-11a), 2.30 (1H, m, H-11b),
5.49 (1H, m, H-12), 6.45 (1H, m, H-14), 7.48 (1H, m,
H-15), 7.51 (1H, m, H-16), 1.13 (3H, d, J 6.6 Hz, H-19),
3.77 (OMe). 13C NMR (400 MHz, CDCl3) δ: 24.7 (C-1),
19.7 (C-2), 25.7 (C-3), 58.4 (C-4), 134.6 (C-5), 75.5
(C-6), 36.2 (C-7), 36.3 (C-8), 52.9 (C-9), 133.2 (C-10),
39.4 (C-11), 72.7 (C-12), 124.7 (C-13), 108.1 (C-14),
144.2 (C-15), 139.6 (C-16), 16.4 (C-17), 173.5 (C-18),
100.2 (C-19), 177.8 (C-20), 52.9 (OMe). The 1H and
13C NMR data were in agreement with those in the
literature[12].
Acknowledgements
This study was supported by National Natural Science
Foundation of China (Grant No. 81172943). We are
grateful to Prof. Hongzheng Fu for the technical support,
Xulin Sun for the NMR running, Fuling Yin for the X-ray
running and Weiqing Zhang for running the MS samples.
References
[1] Guo, Z.G. Guangxi Hygiene, 1977, 3, 33.
[2] Pan, Z.W. New Rural Tech. 2013, 1, 46−46.
[3] Zheng, Y.H. Res. Prac. Chin. Med. 2001, 15, 33−33.
[4] Bu, H.J. CN 102614447A 20120801.
[5] Laddawan, B.; Che, C.T.; Harry, H.S. Planta Med. 1988,
1, 61.
[6] Hu, Y.; Zhang, L.; Wen, X.Q. J. Asian Nat. Prod. 2012,
14, 785−788.
[7] Zakaria, H.M.; Kenne, F.; Musa, C.C. Planta Med. 2009,
75, 262−267.
[8] Wang, G.C.; Li, J.G. J. Nat. Prod. 2012, 75, 2188−2192.
[9] Chen, S.H.; Ren, F.Z.; Li, L.H. J. Chin. Pharm. 2010, 45,
1907−1909.
[10] Wang, G.C.; Li, J.G. J. Nat. Prod. 2012, 75, 2188−2192.
[11] Kanlayavattanakul, M. ; Ruangrungsi, N.T.; Kawahata, M.
J. Nat. Prod. 2005, 68, 7−10.
[12] Itô, S.; Nakatsu, T.; Kawashima, T. Heterocycles. 1981,
15, 1.
鸡骨香的化学成分研究
刘俊丽1,2, 郝艳平1,王建斌2, 窦文彤1, 陈晨2, 郭妍1, 袁丹1*, 付宏征2*
1. 沈阳药科大学 中药学院, 辽宁 沈阳 110016
2. 北京大学医学部 药学院 天然药物及仿生药物国家重点实验室, 北京 100191
摘要: 本文对大戟科巴豆属植物鸡骨香根部的化学成分进行研究。采用硅胶、葡聚糖凝胶以及制备型高效液相色谱
技术从其乙醇提取物的乙酸乙酯萃取部位分离得到9个二萜类化合物, 其中一个为新化合物。采用波谱等手段对其结构进
行了鉴定, 分别为Crassifolin P (1), Crassifolin J (2), 9-[2-(2(5H)-呋喃酮-4-)乙基]-4,8,9-三甲基-1,2,3,4,5,6,7,8-八氢奈环-1-
甲酯 (3), Penduliflaworosin (4), 异山藿香定 (5), Crassifolin G (6), 山藿香定 (7), Chettaphanin I (8), 石岩枫二萜内酯 (9)。其中,
化合物1是一个新化合物。
关键词: 鸡骨香; 化学成分; 结构鉴定