全 文 ：【Received date】　2003-01-12
【＊Correponding author】　LUO Shi-De:Prof.Kunming Institute of
Botany , Chinese Academy of Sciences , Tel:0871-5223097　E-mail:shideluo
@hotmail.com
·Orginal Papers·
Chemical Constituents of Maesa indica CJNM
LAI Guo-Fang , WANG Yi-Fen , CAO Jian-Xin , LUO Shi-De＊
StateKey Laboratory of Phytochemistry and Plant Resource in West China , Kunming Institute of Botany , Chinese Academy of Sciences , Kun-
ming , 650204
【ABSTRACT】　AIM:To study the chemical constituents of Maesa .indica .METHOD:Compounds were separated by col-
umn chromatography on silica gel , Sephadex LH-20 and their structures were elucidated based on the spectral analyses includ-
ing 1D NMR(1HNMR , 13CNMR)and 2D NMR(COSY , HMQC , HMBC).RESULT:Two triterpenoids aglycone and other four
compounds were isolated from M.indica and identified as 22-O-(2-methylbutyryl)-28-al-12-en-olean-3β , 16α-diol(1), 22-O-
hexanoyl-28-al-12-en-olean-3β , 16α-diol(2), 1 , 12-bis(3 , 3′-dihydroxy-4 , 4′-dimethyl-5 , 5′-dimethoxyphenyl)dodecane
(3)] , 3β , 16α, 22α, 28β-tetrahydroxy-13β , 28-epoxy-olean(4),(24R)-stigmast-7 , 22(E)-dien-3α-ol(5),(24R)-stigmast-
7 , 22(E)-dien-3β-D-glucopyranoside(6).CONCLUSIONS:Compound 1 was a new compound , and other compounds were
obtained from M.indica for the first time.
【KEY WORDS】　Maesa indica;Maesa L.;Olean triterpenoids.
【CLCNumber】　R284　　【Document code】　A　　【Article ID】　1672-3651(2003)02-0076-03
1　Introduction
Maesa indica(Roxb.)A.DC.is distributed in
Yunnan province.It has been reported to exert antiviral
activity against Rhaniket disease and Vaccinia viruses
and was also used against the jaundise hepatitis in Chi-
nese folk medicine[ 1] .Except that quercitin-3-rhamno-
side has been reported from the leaves of M.indica ,
this plant has not systematically been studied.For this
reason , chemical studies of this plant were undertaken.
This paper mainly discussed the structure elucidation of
compound(1).
2　Materials and apparatus
2.1　Plant Material.
The aerial of Maesa indica was collected at
Xishuangbanna , Yunnan , P.R.China , inMarch 2002.
The plant identity was established by Dr.Gao Xin-fen ,
and a voucher(No.0547746)was deposited in the
herbarium of Kunming Institute of Botany , Kunming , P.
R.China.
2.2　Apparatus and Material
Column chromatography(CC):Qingdao silica gel
(200-300 mesh), Sephadex LH-20 and TLC:Qingdao
precoated plates , silica GF254 plates and mp:XPC-1 ap-
paratus.IR Spectra:Bio-rad FTS spectrometer:in
cm-1.NMR Spectra:Bruker AM-400 or DRX-500
spectrometer , C5D5N and CDCl3 solns;δvalues(with
ref.to the signal in C5D5N and CDCl3with TMS as in-
ternal standard;MS:Autospec 3000 spectrometer in m/
z(rel.%).
2.3　Extraction and Isolation
The air-dried aerial parts(5 kg)were extracted
thrice with 95%EtOH/H2O at r.t.The solvent was e-
vaporated at <50°to give a deep-brown waxy residue ,
which was suspended in H2O and partitioned with AcOEt
(3×1000 ml), and BuOH(3×1000 ml)respectively.
The AcOEt extract (38 g) was repeatedly chro-
matographed by silica gel(200 ～ 300 mesh) and
Sephadex LH-20 to afford pure compounds 3(32 mg), 4
(53 mg), 5(106 mg), 6(28 mg).The BuOH extract
(20 g)was hydrolyzed with 5%HCl for 2 h , then parti-
tioned with AcOEt , finally processed with NaHCO3 , Na-
Cl , Na2SO4 to obtain the AcOEt extraction.Concentra-
tion of AcOEt solution was repeatedly chromatographed
by silica gel(200 ～ 300 mesh)and Sephadex LH-20 to
afford pure compounds 1(24 mg), 2(153 mg).
3　Results and Discussion
Compound(1), an amorphous powder.It was de-
duced to have a molecular formula of C35H56O5 by high
resolution positive FABMS(found [ M+1] + 557.4190 ,
calcd 557.4206).Its prominent fragment ions occurred
at m/z 455 [M-101] , corresponding to the independent
loss of a 2-methylbutyryloxy group , other fragment ions
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中国天然药物　2003年 7月　第 1卷　第 2期
appeared at m/z 190 ,247 , corresponding to the charac-
teristic of the olean-type cleavage.Its IR spectrum
showed absorption bands at 3465 br , 1731 , 1462
cm
-1 , which corresponded to hydroxyl groups , carboxyl
group and olefinic bonds respectively.Its 1HNMR spec-
trum exhibited the presence of three angular methyl
group signals at δ0.92 , 1.01 and 1.49(each 3H , s),
four geminal tertiary methyl group signals at δ0.81 ,
1.12 ,1.14 and 1.26(each 3H , s), another methyl group
signals atδ0.99 and1.24 and one olefinic proton signal
atδ5.53(1H ,brs).The 13CNMR spectral data of com-
pound 1 showed the presence of aldehyde carbon signal
atδ204.3 , one ester carbonyl signal at δ175.5 , two
olefinic carbon signals atδ124.9 and 141.4 , and three
oxygenated methine signals at δ78.7 , 71.0 , 66.9.
1
HNMR and
13
CNMR spectral data of compound 1(see
Table 1)were very similar to those of compound 2 ,
which indicated that compound 1 had the similar skele-
ton with that of compound 2.However , in comparison of
the 13CNMR spectral data of 1 and those of 2 , the substi-
tuting group of 1 was one 2-methylbutyryl unit , which
was also confirmed by two dimensional NMR techniques.
HMQC and HMBC experiments showed the correlation
between H-22 of the skeleton and C-1′of 2 methylbu-
tyryl unit.Based on the above evidence , the structure of
compound 1 was established to be 22-O-(2-methylbu-
tyryl)-28-al-12-en-olean-3β ,16α-diol.
Tab 1　13CNMR data of compounds 1-2 , 4-6
1 2 4 5 6
1 39.1 39.1 39.6 37.0 37.1
2 28.1 28.1 28.3 26.7 29.7
3 78.7 78.1 78.2 74.1 79.5
4 39.4 39.4 39.6 33.8 34.1
5 55.8 55.8 55.5 40.5 40.7
6 18.7 18.8 18.3 29.4 29.6
7 32.2 31.2 34.5 117.1 117.2
8 42.0 42.1 42.3 139.5 139.2
9 47.1 47.1 50.5 49.0 49.4
10 37.3 37.3 33.1 34.4 34.3
11 23.7 23.8 19.3 21.4 21.5
12 124.9 124.5 33.4 39.5 39.5
13 141.4 142.3 87.5 43.0 43.1
14 40.1 40.2 44.1 55.6 55.8
15 33.2 33.4 36.8 23.1 23.0
16 66.9 67.8 70.1 28.5 28.4
17 56.3 55.2 52.9 55.9 56.6
18 40.5 41.7 47.4 12.1 12.0
19 45.9 46.0 38.7 12.5 12.9
20 31.5 31.8 37.3 40.1 40.2
21 44.0 44.1 46.8 21.0 21.0
22 71.0 70.3 68.1 138.2 138.3
23 28.8 28.8 28.8 129.5 129.4
24 16.5 16.6 16.5 51.3 51.2
25 15.6 15.7 16.6 31.6 31.9
26 17.4 17.5 18.9 19.2 19.0
27 27.3 27.4 19.5 21.3 21.5
28 204.3 204.3 98.6 25.5 25.4
29 33.6 33.2 33.4 13.1 13.0
30 25.1 24.9 26.1
1 175.5 165.9 99.6
2 41.9 120.2 75.3
3 27.1 152.6 76.4
4 11.9 31.1 70.2
5 16.6 22.5 77.0
6 13.9 62.3
4　Structures Identification
Compound 1　(22-O-(2-methylbutyryl)-28-al-12-en-olean-
3β , 16α-diol)was obtained as white powder(Me2CO).mp 105 ～
108℃;EI-MS:m/ z 556 [ M +] ;Molecular formula:C35H56O5 ,
IR(KBr)ν3465 , 2954 , 1731 , 1654 , 1462 , 1383 , 1260 , 1190 ,
1155 , 1105 , 1067 , 1040 , 997 cm-1.1HNMR(500 MHz , pyridine-
d5)(δ):0.81(3H , s , C24-H), 0.92(3H , s , C26-H), 0.99(3H , t , J
=7.4 , C4′-H), 1.01(3H , s , C25-H), 1.12(3H , s , C30-H), 1.14
(3H , s , C29-H), 1.24(3H , d , J =7.4 , C5′-H), 1.26(1H , 3H , s ,
C23-H), 1.49(3H , s , C27-H), 3.46(1H ,m , C3-H), 4.37(1H , brs ,
C16-H), 6.59(1H , brs , C22-H).13CNMR(100 MHz , pyridine-d5)
spectral data(see Table).
Compound 2 　(22-O-hexanoyl-28-al-12-en-olean-3α, 16β-
diol)was obtained as white powder(Me2CO).mp 100 ～ 102℃;
[α] 25D-3.64°(CHCl3 0.55);IR(KBr)ν3519 , 2954 , 2869 , 1724 ,
1641 , 1464 , 1179 , 995 cm-1.EI-MS:m/z 568[ M +] ;Molecular
formula:C36H56O5 , 1HNMR(500 MHz , pyridine-d5)(δ):0.86
(3H , t , J =12.0 , C6′-H), 0.81 , 0.93 , 1.03 , 1.03 , 1.22 , 1.69 ,
1.77(each 3H , s), 3.45(1H , dd , J =10.8 , 5.2 , C3-H), 5.01
(1H , brs , C22-H), 5.51(1H , brs , C12-H), 5.66(1H , dd , J =
11.96 , 5.40 , C16-H), 5.85(1H , d , J =11.5 , C2′-H), 6.15(1H ,
m , C3′-H).13CNMR(100 MHz , pyridine-d5) spectral data(see
Table 1):The spectral data of compound 2 was in accordance with
those of the literature[ 2] .
Compound 3　(1 , 12-bis(3 , 3′-dihydroxy-4 , 4′-dimethyl-5 ,
5′-dimethoxyphenyl)dodecane was obtained as white solid.mp 76
～ 78℃;EI-MS:m/ z 442 [ M+] ;Molecular formula:C28H42O4 ,
IR(KBr)ν3325 , 2926 , 2948 , 1620 , 1595 , 1462 , 1227 , 824 , 662
中国天然药物　2003年 7月　第 1卷　第 2期
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Chin J Nat Med　July 2003　Vol.1　No.2　77　
cm-1.1HNMR(400 MHz , pyridine-d5)(δ):2.56(2-Me), 3.80
(5-OMe), 6.52(1H , s , C6-H), 6.84(1H , s , C2-H).13CNMR(100
MHz , pyridine-d5)(δ):9.1(4 , 4′-Me×2), 30.1(2 , 11-CH2×2),
32.1(3-10 , CH2×8), 36.6(1 , 12-CH2×2), 55.6(5 , 5′-OMe×
2), 102.8(C-6 , 6′), 109.2(C-2 , 2′), 110.5(C-4 , 4′), 141.8(C-
1 , 1′), 157.5(C-3 , 3′), 159.5(C-5 , 5′).The spectral data of
compound 3 was in accordance with those of the literature[ 3] .
Compound 4 　(3β , 16α, 22α, 28β-tetrahydroxy-13β , 28-e-
poxy-olean)was obtained as white powder(MeOH).mp 179 ～
182℃;IR(KBr)ν3411 , 2850 , 1078 , 1052 , 998 cm-1.EI-MS:
m/ z 490;Molecular formula:C30 H50 O5;1 HNMR(400 MHz ,
pyridine-d5)(δ):0.94 , 1.04 , 1.14 , 1.15 , 1.23 , 1.40 , 1.65(each
3H), 3.47(1H , dd , J =10.4 , 5.5 , C3-H), 5.06(1H , dd , J =
12.4 , 5.5 , C22-H), 5.10(1H , d , J =6.1 , C16-H), 5.48(1H , s ,
C28-H).13 CNMR(100 MHz , pyridine-d5) spectral data(see
Table):The spectral data of compound 4 was in accordance with
those of the literature[ 4] .
Compound 5 　((24R)-stigmast-7 , 22(E)-dien-3α-ol)was
obtained as needle crystallis(Me2CO).mp 161 ～ 162℃;IR
(KBr)ν3394 , 2985 , 2887 , 1645 , 1449 , 1155 , 1026 , 846 cm-1.
EI-MS:m/ z 412 [ M+] , Molecular formula:C29H48O;1HNMR
(400 MHz , CDCl3)(δ):0.54(3H , s , C18-H), 0.78(3H , d , J =
7.1 , C26-H), 0.82(3H , t , J=7.2 , C29-H), 0.85(3H , d , J =6.5 ,
C27-H), 1.03(3H , d , J =6.5 , C21-H), 3.35(1H ,m , C3-H), 5.18
(1H ,m , C7-7), 5.22(1H , ddd , J =16.1 , 7.0 , 7.0 , C23-H), 5.31
(1H , dd , J =16.1 , 7.0 , C22-H).13CNMR(100 MHz , CDCl3)
spectral data(see Table):The spectral data of compound 5 was in
accordance with those of the literature[ 5] .
Compound 6 　((24R)-stigmast-7 , 22(E)-dien-3β-D-glu-
copyranoside)was obtained as white powder(Me2CO).mp 287～
288℃;EI-MS:574[ M+] ;Molecular formula:C35H58O6;IR
(KBr)ν3400 , 1639 , 1023 , 970 cm-1.1HNMR(400MHz , CDCl3)
(δ):0.54(3H , s , C18-H), 0.79(3H , d , J =7.1 , C26-H), 0.82
(3H , t , J =7.2 , C29-H), 0.85(3H , d , J =6.5 , C27-H), 1.02
(3H , d , J =6.5 , C21-H), 3.15(1H , dd , J =7.9 , 8.0 , C2′-H),
3.27(1H , dd , J =8.7 , 9.1 , C4′-H), 3.34(1H , d , J =9.0 , C5′-
H), 3.35(1H , m , C3-H), 3.40(1H , dd , J =8.0 , 8.7 , C3′-H),
3.80(1H , dd , J=12.1 , 5.0 , C6′β-H), 3.81(1H , dd , J = 12.1 ,
2.3 , C6′α-H), 4.52(1H , d , J =7.9 , C1′-H), 5.16(1H ,m , C7-7),
5.21(1H , ddd , J =16.1 , 7.0 , 7.0 , C23-H), 5.31(1H , dd , J =
16.1 , 7.0 , C22-H).13CNMR(100 MHz , CDCl3)spectral data(see
Table).The spectral data of compound 6 was in accordance with
those of the literature[ 5] .
References
[ 1] 　Koike K , Kudo M , Jia ZH , et al.New triterpenoid saponins from
Maesa japonica[ J] .J Nat Prod , 1999, 62:228-232.
[ 2] 　Monroe EW , Mansukh CW , Kevan G , et al.Plant antimutagenic a-
gents , i solation and structure elucidation of maeeol , an inactive con-
stituent of Maesa Spp[ J] .J Nat Prod , 1988 , 51(6):1226-1231.
[ 3] 　Giovanni A , Lorenzo DN , Federico G , et al.An Oleanane triterpene
from Anagallis arvensis[ J] .Phytochemistry , 1992 , 31(3):929-933.
[ 4] 　Nusrat J ,Wasim A , Abdul M.New steroidal glycosides from Mimu-
sops elengi[ J] .J Nat Prod , 1995, 58(8):1244-1247.
[ 5] 　Sindambiwe JB , Balde AM , Bruyne TD.Triterpenoid saponins from
Maesa lanceolata[ J].Phytochemistry , 1996, 41(1):269-277.
包疮叶的化学成分研究
来国防 ,王易芬 ,曹建新 ,罗士德＊
中国科学院昆明植物研究所 植物化学与西部植物资源持续利用国家重点实验室 , 昆明 650204
【摘　要】　目的:研究包疮叶的化学成分。方法:采用硅胶柱层析法进行分离 , 根据光谱数据鉴定结构。结果:从中分
得 6个化合物 , 分别为:22-O-(2-methylbutyryl)-28-al-12-en-olean-3β , 16α-diol(1), 22-O-hexanoyl-28-al-12-en-olean-3β , 16α-diol(2),
1 ,12-bis(3 , 3′-dihydroxy-4 , 4′-dimethyl-5 , 5′-dimethoxyphenyl)dodecane(3)] , 3β , 16α, 22α, 28β-tetrahydroxy-13β , 28-epoxy-olean
(4),(24R)-stigmast-7 , 22(E)-dien-3α-ol(5),(24R)-stigmast-7 , 22(E)-dien-3β-D-glucopyranoside(6)。结论:化合物 1 为一新的
齐墩果烷型甙元 ,其它 5 个化合物均为首次从该植物中得到。
【关键词】　包疮叶;杜茎山属;齐墩果烷型三萜
78　　Chin J Nat Med　July 2003　Vol.1　No.2
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