全 文 ：Chemical Constituents of Garcinia maingayii
Sri Hartati
1 , 2 , WANG Hong-Bing3 , L.B.S.Kardono1 , Soleh Kosela2 , QIN Guo-Wei3＊
1 Research Center for Chemistry , Indonesia Institute of Sciences , Komplek Puspiptek Serpong 15314 , Indonesia;
2 Faculty of Science , University of Indonesia , Kampus Depok , Indonesia;
3 Shanghai Institute of Materia Medica , Shanghai Institutes for Biological Sciences , Chinese Academy of Sciences , Shanghai 201203 , China
【ABSTRACT】　AIM:To study the bioactive chemical constituents of Garcinia maingayii Hook.METHODS:Repeated
column chromatography was used for separation of compounds and spectroscopic techniques and X-ray analysis were used for
structure determination.RESULTS:Five known compounds , isoxanthochymol(1), camboginol(2)5 , 7 , 2′, 5′-tetra-
hydroxy flavan-3-ol(3), stigmasterol(4)and griffipavixanthone(5)were obtained from hexane and acetone extracts of stem
barks of the plant.Compounds 1 , 2 and 5 showed high potential in vitro cytotoxicity against in P388 murine leukemia cells
with IC50 1.47 , 4.90 and 0.42μg·mL-1 , respectively.CONCLUSION:Compounds 1-5 were first reported from this plant.
【KEY WORDS】　Garcinia maingayii;Isoxanthochymol;Camboginol;Cytoxicity
【CLCNumber】　R284.1　　【Document code】　A　　【Ariticle ID】　1672-3651(2007)04-0272-05
【Received on】　2007-03-18
【＊Corresponding authors】　QinGuo-Wei:Tel:+62-21-78888880 +
86-21-50805853;Fax:+62-21-7863432 +86-21-50807088;E-mail:
s2kimui@mail.cso.ui.ac.id solehkosela@ui.edu(S.Kosela) gwqin
@mail.shcnc.ac.cn
　　Garcinia (Cluciaceae)consists of roughly 300 spe-
cies of dioecious trees and shrubs distributed in South
America, Africa and Southeast Asia.Among the most
well-known and economically important species is man-
gosteen(G.mangostana), a widely consumed fruit that
is considered as the “Queen of Fruits”.However , other
species are gaining in economic importance , especially
for their purported pharmacological utility.Recent study
showed that Garcinia species contain constituents with
various structural types including isoprenyl xanthones and
benzophenones , triterpenoids , flavonoids[ 1 ,2] , of which
some exhibited a wide range of biological and pharmaco-
logical activities including antimalarial
[ 3] , growth inhi-
bition of human leukemia cells , cytopathic inhibition of
in vitro HIV infection , and cytotoxicities[ 2, 4 , 5] .The
biological significance and structural novelties of such
compounds have attracted our great interests for investi-
gating the species G.maingayii , which have never
been chemically studied before.In this paper we
describe the isolation and structural elucidation of five
known compounds , two polyisoprenyl benzophenones:
isoxanthochymol(1), camboginol(2)and 5 , 7 , 2′, 5′
- tetrahydroxy flavan-3-ol (3), stigmasterol (4), and
griffipavixanthone (5)which are all first reported from
this plant.The structure of 1 was confirmed by X-ray
diffraction.
1　Results and discussion
Compound 1　white powder or colourless crystal
mp.242 ～ 243 ℃, showed molecular formula C38H50O6
by its ESI-MS and NMR data.The IR spectrum re-
vealed the presence of hydroxyl group(3 466 and 3 364
cm
-1), conjugated and non-conjugated carbonyl(1 720
and 1 676 cm
-1)groups.1H NMR spectrum(see Table
1)showed the signals for ten methyl(four aliphatic atδ
0.89 , 0.98 , 1.14 , 1.25;six vinylic atδ1.57 , 1.58 ,
1.63 , 1.66 , 1.68 , 1.78), three olefinic protons (δ
4.92 , 4.92 , 5.20 , each 1H), three aromatic protons
(ABX- type atδ6.73 , 7.03 , 7.24 , each 1H)and two
hydroxyl protons(δ8.06 , 8.72).The 13C NMR spec-
trum(see Table 1)revealed 38 carbons for ten methyl ,
five methylene , eight methine (three olefinic , three ar-
omatic), and fifteen quaternary carbons(five olefinic ,
three aromatic , two carbonyl).The above spectral fea-
tures suggested that 1 should be a polyisoprenyl benzo-
phenone derivative , which is a special structural class
found in Garcinia species.Further study on comparison
of its
1
H and
13
C NMR data with literature values of re-
lated compounds suggested that 1 should be 30-epi-cam-
272　　Chin J Nat Med　July 2007　Vol.5　No.4 　2007年 7月　第 5卷　第 4期
bogin or isoxanthochymol
[ 6 , 7] , which differ at configura-
tion of C6-isoprenyl chain , α-form in the former and β-
form in the latter.To clarify the structure of 1 an X-ray
crystallographic analysis was preformed and the results
indicated 1 as isoxanthochymol(Figure 1).
Table 1　1H and 13C NMR of compounds 1 and 2(400 MHz)
No. Compound 1 in CD3OD Compound 2 in CDCl3
13C DEPT 1H 13C DEPT 1H
1 174.1 C 193.01 C 17.85, s(OH)
2 88.70 C 132.46 C
3 194.7 C 193.84 C
4 69.9 C 69.73 C
5 47.5 C 49.60 C
6 45.06 CH 1.50 , m 46.80 CH 6.98 , d , 2.06 Hz
7 27.55 CH2 2.42 , d＊ , 2.46 , d＊ 42.58 CH 1.88 , d , 3.71 Hz , 1.92 , d, 3.85 Hz
8 53.09 C 57.90 C
9 200.41 C 209.08 C
10 196.78 C 198.94 C
11 131.64 C 131.98 C
12 116.12 CH 7.24, d , 2 1 Hz 115.84 CH 6.91, d , 2.0
13 123 44 CH 148.04 C 6.53 , s , OH
14 29.69 CH2 149.73 C 6.88 , s , OH
15 116.69 CH 6.73 , d , 8.3 Hz 114.31 CH 6.66 , d , 8.4
16 123.44 CH 7.03 , dd , 8.3 , 2.1 124.05 CH 6.70 , dd , 8.4 , 2.0
17 29.69 CH2 2.28 , d , 14.6 Hz 26.36 CH2 2.57(b), 2.61(b)
18 121.68 CH 4.92 , m 120.06 CH 4.94(t)
19 134.48 C 127.71 C
20 26.49 CH3 1.78 , s 26.05 CH3 1.72 , s
21 18.54 CH3 1.63 , s 22.73 CH3 1.60 , s
22 22.07 CH3 1.25 , s 22.73 CH3 1.17 , s
23 26.62 CH3 0.98 , s 27.00 CH3 1.01 , s
24 31.02 CH2 2.15 , b 28.90 CH2 1.88 , d , 3.71 Hz , 1.92, d , 3.85 Hz
25 126.85 CH 5.20, t 123.78 CH 5.04, t
26 135.41 C 135.26 C
27 26.99 CH3 1.68 , s 25.59 CH3 1.74 , s
28 18.74 CH3 1.57 , s 17.94 CH3 1.55 , s
29 27.12 CH2 3.01, d , 3.8 Hz , 3.04 , d , 3.8 Hz 36.18 CH2 2.34-2.40
30 47.97 CH 1.56 , m 43.56 CH 1.8-2.2 m
31 127.03 C 143.60 C
32 27.55 CH3 0.89 , s 146.60 CH2 4.37 , d , 1.8, 4.42 , d , 18
33 29.52 CH3 1.14 , s 17.94 CH3 1.80 , s
34 40.55 CH2 2.02 , d , 2.2 Hz 32.59 CH2 2.35.b
35 124.08 CH 4.92(t) 122.59 CH 4.85, t
36 135.4 C 132.78C
37 23.36 CH3 1.58 , s 25.82 CH3 1.53 , s
38 19.12 CH3 1.66 , s 17.59 CH3 1.66 , s
　2007年 7月　第 5卷　第 4期 Chin J Nat Med　July 2007　Vol.5　No.4　273　
Fig 1　Structures of Compounds 1 , 2 and 5
　　Compound 2　yellow needles , showed molecular
formula C38H50O6 by its ESI-MS and NMR data.FTIR
spectrum(KBr)νmax exhibited the presence of phenolic
hydroxyl(3 376 cm-1), conjugated and non-conjugated
carbonyl(1 728 and 1 638 cm-1)groups.The 1H NMR
spectra(see Table 1)showed the presence of three aro-
matic proton characteristic of 3 ,4-dihydroxy benzoyl [ δ
6.91(d , J =2.0 Hz), 6.66(d , J =8.4 Hz), 6.70
(dd , J = 8.4 , 2.0 Hz)] , three isoprenyl [ three
olefinic proton atδ4.85 , 4.94 and 5.04 (each 1H ,
t);six olefinic methyl atδ1.53 , 1.55 , 1.60 , 1.66 ,
1.72 and 1.74(each 3H , s)] , one isopropenyl [ eth-
ylene proton at δ4.37 and 4.42 (each 1H , d , J =
1.8 Hz );methyl at δ1.80 , s] and two saturated
methyl(δ1.01 , 1.17 , each 3H , s)groups.The above
data revealed that 2 should be an isoprenyl benzophenone
like 1.A sharp singlet at lower fieldδ17.85(1H)was
the characteristic signal of C1-OH proton associated with
C10-carbonyl group , indicating that 2 seems to be cam-
boginol , the isomer of 1 with free C1-hydroxyl group ,
isolated from another Garcinia species
[ 8] .The 13C NMR
of 2(see Table 1)showed 38 signals for 9 methyl(seven
olefinic), 6 methylene (one olefinic), 8 methine (three
aromatic and three olefinic)and 15 quaternary carbons
(three aromatic and three carbonyl).Further studies
revealed that the
13
C NMR data of 2 are in good agree-
ment with those of camboginol , determining 2 as cambog-
inol , which has been reported to exhibit chemotherapeu-
tical activity against gram-positive and gram-negative
cocci , mycobacteria and fungi[ 8 , 9] .
Compounds 3 and 4were identified by spectroscop-
ic analysis as 5 , 7 , 2′, 5′-tetrahydroxy flavan-3-ol[ 10]
and stigmasterol
[ 11] , respectively.The 1H and 13C NMR
data (see Table 2)of compound 5 is identical with that
of griffipavixanthone
[ 1] .The HMBC data(see Table 2)
further supported above identification that 5 as griffipa-
vixanthone.It was a bixanthone with cyclized prenyl
groups providing the xanthone-xanthone linkage , report-
ed from other Gardenia species , G.griffithii and G.
pavifolia.In our study compounds 1 , 2 and 5 showed
high potential in vitro cytotoxicity against in P388
murine leukemia cells with IC50 1.47 , 4.90 and 0.42
μg·mL-1 , respectively (see Table 3).
Table 2　1 H , 13 C NMR and HMBC data of compound 5
(acetone-d6)
No. δH δC HMBC(H※C)
1-OH 13.66(1H , s) 164.66
2 6.22(1H , s) 98.37 1 , 3 , 4 , 9a
3-OH 8.01(b) 165.28
4 6.43(1H , s) 93.46 2 , 3 , 4a , 9a
4a 157.41
5-OH 8.83(b) 132.20
6-OH 8.62(b) 147.07
7 138.50
8 143.41
8a 109.53
9 184.07
9a 103.42
10a′ 146.33
11 6.70(1H , d , J = 9.74) 42.47 7 , 8 , 13 , 12 , 7′8′
12 2.70(1H , m) 61.62 8, 13 , 14 , 16 , 17, 19
13 33.34
14 1.60(1H , d , J = 17.0)
2.58(1H , d , J = 17.0)
40.62 13 , 15 , 16,
18 , 19 , 20
15 131.39
16 5.51(1H , , b) 122.15 14 , 17 , 20
17 4.86(1H , b) 45.66 -
18 0.77(3H , s) 28.93 12 , 13 , 14, 19
19 1.08(3H , s) 29.12 12 , 13 , 14, 19
20 1.66(3H , s) 23.99 12 , 14 , 15, 16
1′-OH 13.49(1H , s) 164.88 -
2′ 6.24(1H , d , J = 2 , 01) 98.51 1′, 4′, 9a′
3′-OH 9.66(s) 165.12
4′ 6.38(1H , d.J = 2.18) 93.61 2′, 3′, 4a′, 9a′
4a′ 157.46
5′ 130.92
6′ 150.67
7′ 6.81(1H , s) 113.91 11 , 5′, 6′, 8a′
8′ 132.30
8a′ 113.02
9′ 182.09
9a′ 103.59
10a′ 148.78
274　　Chin J Nat Med　July 2007　Vol.5　No.4 　2007年 7月　第 5卷　第 4期
Table 3 　Cytotoxicity of compouds 1 , 2 , 3 and 5 in P388
murine leukemia cells
Compounds IC50(μg·mL-1)
1 1.47
2 4.90
3 >100
5 0.42
2　Experimental
2.1　General experimental procedures
Melting point was determined on a SGW X-4 micro
melting point apparatus and uncorrected.IR spectrum
was measured on a Nicolt-Magna 750 spectro-
photometer.Mass spectrum was recorded using a MAT-
241 mass spectrometer.NMR spectra were recorded on
Bruker AM-400 spectrometers.X-ray analysis was run
on Bruker SMART CCD area-detector diffractometer.
Silica gel was purchased from Qingdao Marine Chemical
Group Co..
2.2　Plant material
The stem barks of G.mangayii were collected
from Riau islands forest , Indonesia in July 2003 and
identification at Herbarium Bogoriences.Voucher speci-
men is deposited in Herbarium Bogoriences Bogor , In-
donesia.
2.3　Extraction and isolation
The dried stem barks (1.5 kg)of G.maingayii
were extracted with n-hexane and then with acetone at
room temperature , successively , to yield n-hexane ex-
tracts(44.1 g)and acetone extracts(127 g).The hex-
ane extract(18 g)was separated by repeated flash col-
umn chromatography to afford 250 mg of camboginol
(2), and 16 mg of stigmasterol (4).The acetone ex-
tract (20 g)was separated by repeated flash column
chromatography to afford 400mg of isoxanthochymol(1)
and 30 mg of 5 , 7 , 2′, 5′-tetrahydroxy-flavan-3-ol(3)
and 65 mg of griffipavixanthone(5).
2.4　Cytotoxic Testing
The cytotoxic assay was performed using 3-(4 , 5-
dimethylthiazol-2-yl)-2 , 5-diphenylteterazolium bromide
(MTT)assay modification method[ 12] .The murine P388
leukemia cells were pre-cultured in RPMI 1 640 medium
(Nissui Co.Ltd., Japan)supplemented with heat-in-
activated fetal bovine serum(FBS)and kanamycin(5.3
mL·L-1)in a humidified atmosphere of 95% air and
5%CO2 at 37 ℃.The cell suspension(3 ×104 cells
mL , 10 μL)was added to each well (3 × 103 cells
well)and incubated for 24 hours.Test compound solu-
tion in DMSO in various concentrations (100 , 30 , 10 ,
3 , 1 , 03 , 01μg·mL-1)was prepared and 10μL of the
test solution or DMSO (control)was added to each
well.The plates were kept in an incubator for 48 hours.
After terminating the cell culture by adding 5%MTT in
PBS(20 μL)to each well , the plate was kept in the
incubator for 4 h.Using microplate reader (MPR A4i ,
Toso)with spectrophotometric method at 550 nm , a
dose-response curve was plotted for compound and
calculated concentration giving 50% inhibition of the
cell growth(IC50).
Isoxanthochymol(1)　Colorless crystal , mp 242
～ 243 ℃, ESI-MS m z 602(M+), molecular formula
C38H50O6 ;IR(KBr)νmax(cm-1):3 466 , 3 364(OH),
1 720 , 1 676(C=O);1H and 13C NMR , see Table 1.
Crystallographic data of (1)　A colorless crystal
with dimensions 0.295×0.273×0.201 mm3;empiri-
cal formula C38H50O6;molecular weight 602.78;crystal
system orthorhombic;space group P2;unit cell dimen-
sion:a = 11.158 (3), b = 14.667 (4), c =
20.556(6)A°, α=90°, β =90°, γ=90°;volume
3 363.8(17)A 3;Z =4;F(000)= 1 304.The
intensity data within θrange of 1.40 ～ 25.50°were
collected at 273 K and the completeness to θ(26.50)
is 100%.A total of 17808 reflections were collected ,
of which 6 951 were judged and observed on the basis of
I > 2σ(I).The final R and Rw were 0.057 8 and
0.159 9 , respectively , with goodness-of-fit =0.749.
The structure was solved using Fourier transformation
techniques and refined by a full-matrix least-squares
calculation on F
2.
Camboginol (2)　A yellow needles , mp 130 ～
132 ℃, ESI-MS m z 602 (M +), molecular formula
C38H50O6 .IR(KBr)νmax(cm-1):broad band at 3 376
(phenolic OH), 1 728 and 1 638 cm-1(six members
cyclic C=O and conjugated C =O respectively), 1H
and
13
C NMR , see Table 1.
5 , 7 , 2′, 5′- Tetrahydroxy flavan-3-ol (3)　
White powder , mp >300 ℃, ESI-MS m z 291(M+
H)+ , molecular formula C15H14 O6;IR (KBr)νmax
(cm-1)3 564 , 3 464 , 3 403 and 3 376 (phenolic
OH).1H NMR(acetone-d6):δ2.74(dd , 4.6 , 16.0
Hz , H-4a), 2.86(dd , 4.6 , 16.0 Hz , H-4b), 3.60
(d , 5.6 Hz , H-2), 4.21 (m , H-3), 4.88(s , OH-
　2007年 7月　第 5卷　第 4期 Chin J Nat Med　July 2007　Vol.5　No.4　275　
2), 5.91(d , 2.4 Hz , H-6), 6.02(d , 2.4Hz , H-
8), 6.79(d , 8.0 , H-3′), 6.84(dd , 2.0 , 8.0 Hz
, H-4′), 7.05(d , 2.0 Hz , H-6′), 4.88 , 7.83 , 7.
87 , 8.02 and 8.18(each 1H , s , OH×5).13C NMR
(acetone-d6):δ28.6(C-4), 66.6(C-3), 79.1(C-
2), 95.5(C-8), 95.8(C-6), 99.4 (C-10), 114.4
(C-3′), 115.1 (C-4′), 118.4 (C-6′), 131.9 (C-
1′), 144.9 (C-2′), 145.1 (C-5′), 156.8 (C-9),
157.2(2хC , C-5 , C-7).
Stigmasterol (4)　White needles , mp 170 ～
171 ℃, EI-MS m z 412 (M+), molecular formula
C29H48O;1 H NMR (CDCl3):δ2.29 (m , H-1a),
2.01(m , H-1b), 1.30(m , H-2), 3.56(m , H-3),
1.65 , 1.10(m , H-4), 5.36(br s , H-6), 1.40(m ,
H-7), 1.42 (m , H-8), 0.90 (m , H-9), 1.15(m ,
H-11), 1.07 (m , H-14), 1.03 (m , H-15), 1.70 ,
1.61(m , H-16), 1.04(m , H-17), 0.67(s , H-18),
1.00(s , H-19), 1.31(m , H-20), 0.91(m , H-21),
5.12(m , H-22), 5.01(m , H-23), 0.93(s , H-24),
1.43(m , H-25), 0.88(m , H-26), 0.81(m , H-27),
1.05(br s , H-28), 0.85(m , H-29).
Griffipavixanthone(5)　Red-brown powder , EI-MS
m z 651 [M+H] + , molecular formula C36H28O12 , IR
(KBr)νmax (cm-1):3 663-3 039 (phenolic OH),
2953 , 2873(aromatic , CH)and 1649(conjugated C=
O).1H and13C NMR data(see Table 2).
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藤黄科植物 Garcinia maingayii 的化学成分
Sri Hartati
1 , 2 , 王红兵3 , L.B.S Kardono1 , Soleh Kosela2 , 秦国伟3＊
1印度尼西亚科学院化学研究中心 , Serpong , 印度尼西亚;
2印度尼西亚大学理学院 , Depok , 印度尼西亚;
3中国科学院上海药物研究所 , 上海 201203
【摘　要】　目的:研究藤黄科植物 Garcinia maingayii 的化学成分。方法:采用柱层析方法分离和纯化化合物 ,根据各
种波谱和 X-衍射分析鉴定化合物结构。结果:从该植物的茎皮中分离并鉴定出 5种化合物:isoxanthochymol(1), camboginol
(2)5 , 7 , 2′, 5′-tetrahydroxy flavan-3-ol(3), stigmasterol(4)和 griffipavixanthone(5), 其中 1 和 2 为 polyisoprenyl benzophenones
类化合物 , 5为 bixanthone 类化合物。结论:以上 5 种化合物都是首次从该植物中分得 , 其中化合物 1、2 和 5对小鼠 P388 白
血病细胞有细胞毒活性 ,其 IC50分别为 1.47 , 4.90 和 0.42μg·mL-1 。
【关键词】　藤黄科植物;多异戊烯基二苯甲酮类;双酮类;细胞毒活性
276　　Chin J Nat Med　July 2007　Vol.5　No.4 　2007年 7月　第 5卷　第 4期