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Two New Triterpenes from Metadina trichotoma (Rubiaceae)

黄棉木中两个新的三萜类化合物



全 文 :黄棉木中两个新的三萜类化合物?
张玉梅 , 谭宁华??
(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 , 云南 昆明 650204 )
摘要 : 从黄棉木 ( Metadina trichotoma (Zoll . et . Mor .) Bakn .) 树皮中分离得到 2 个新的三萜类化合物 : 3-
oxo-29-hydroxy-urs-12-en-27 , 28-dioic acid (黄棉木素 A , 1) 和 3-oxo-21β-hydroxy-urs-12-en-27 , 28-dioic acid (黄
棉木素 B , 2 )。其结构主要通过 MS, 1D 以及 2D NMR 等波谱方法鉴定。
关键词 : 黄棉木 ; 茜草科 ; 三萜 ; 黄棉木素 A ; 黄棉木素 B
中图分类号 : Q 946 文献标识码 : A 文章编号 : 0253 - 2700(2006)06 - 673 - 03
Two New Triterpenes from Metadina trichotoma (Rubiaceae)
ZHANG Yu-Mei , TAN Ning-Hua
* *
( State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany,
ChineseAcademy of Sciences, Kunming 650204 , China)
Abstract: Two new triterpenes, 3-oxo-29-hydroxy-urs-12-en-27 , 28-dioic acid (Metatrichosin A , 1 ) and 3-oxo-21β-
hydroxy-urs-12-en-27 , 28-dioic acid (Metatrichosin B , 2) , were isolated from the barks of Metadina trichotoma (Zoll .
et . Mor .) Bakn . Their structures were mainly determined byMS, 1D and 2D NMR spectroscopic methods .
Key words: Metadina trichotoma; Rubiaceae; Triterpenes; Metatrichosin A ; Metatrichosin B
Metadina trichotoma ( Zoll . et . Mor .) Bakn .
belongs to the Rubiaceae and is auniquespecies in the
genus Metadina, which is distributed in Southwest of
China, Vietnam, and India etc . ( Delectis Florae
Reipublicae Popularis SinicaeAgendae AcademiaeSin-
icae Edita, 1999 ) . Up to now, there is no any report
on its chemical constituents . We found its methanol
extracts showed inhibitory activity on cathepsin B ( IC50
= 0 .77μg?ml ) in our random screening on the crude
extracts of some plants in Yunnan province . In order
to seek more novel bioactive compounds, we carried
out extensive chemical and biological studies on the
barks of M. trichotoma . In this paper, we described
the isolation and structural elucidation of two new trit-
erpenes (Figure 1) fromthis plant .
Fig . 1 Structures of compound 1 and 2
云 南 植 物 研 究 2006 , 28 (6) : 673~675
Acta Botanica Yunnanica

?
?? ?To whom correspondence should be addressed . Tel : + 86 - 871 - 5223800 , Fax: + 86 - 871 - 5223800 . E - mail : nhtan@ mail. kib. ac. cn
Received date: 2006 - 06 - 20 , Accepted date: 2006 - 09 - 18
作者简介 : 张玉梅 (1973 - ) 女 , 博士 , 主要从事植物化学与活性成分研究。 ?
基金项目 : 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基金、中国科学院“西部之光” 联合
学者项目以及国家自然科学基金 ( 30572258)
Results and Discussion
Compound 1 was assigned the molecular formula
C30 H44 O6 by HR + TOF-MS at m?z 523 .3025 [ M +
Na] + ( calcd . 523 .3035 ) , which was confirmed by
13
C and DEPT NMR spectra . The
13
C and DEPT
13
C
NMR spectra indicated that 1 may beone triterpene .
The 13 C-NMR spectra showed the presenceof five
Me [δ27 .3 ( C - 24) , 21 .7 ( C - 23 ) , 18 .9 ( C -
30) , 17 .7 ( C - 26) , 16 .6 ( C - 25 ) ] , ten CH2 [δ
66 .2 (C - 29) , 40 .5 ( C - 1 ) , 37 .3 ( C - 7 ) , 37 .2
( C - 22) , 35 .0 ( C - 2) , 26 .4 (C - 15) , 25 .7 ( C -
21) , 25 .5 ( C - 16 ) , 24 .0 ( C - 11 ) , 20 .7 ( C -
6) ] , and six CH [δ130 .5 (C - 12) , 56.1 ( C - 5 ) ,
55 .5 (C - 18) , 47 .8 ( C - 19) , 47 .1 ( C - 9) , 32 .8
(C - 20 ) ] , as well as nine quaternary C-atoms [δ
220 .7 ( C - 3 ) , 181 .5 ( C - 28) , 178 .8 ( C - 27 ) ,
133 .9 (C - 13 ) , 57 .2 ( C - 14 ) , 49 .2 ( C - 17 ) ,
48 .3 ( C - 4 ) , 40 .5 ( C - 8 ) , 37 .8 ( C - 10 ) ] .
These data indicated that compound 1 has a urs-12-ene
skeletonwith aketo groupon ringA , and also has five
Me and a hydroxymethyl group (Aquino et al , 1997) .
The HMBC spectrum ( Figure 2 ) showed correlations
betweenδC 220 .7 ( C - 3 ) andδH 1 .02 (3H, s, H -
23) , which indicated that the C = O was located at C
- 3 . And also the correlations between: δC 47 .8 (C -
19) andδH 3 .32 (1H, dd, J = 7 .07 , 10 .88 Hz, H
- 29a) , δC 32 .8 ( C - 20) andδH 3 .65 (1H , dd, J
= 3 .08 , 10 .84 Hz, H - 29b) , which indicated that
theOH was located at C - 29 . So the structure of 1
was determined to be 3-oxo-29-hydroxy-urs-12-en-27 ,
28-dioic acid, named Metatrichosin A .
Compound 2 was assigned the molecular formula
C30 H44 O6 by HR + TOF-MS at m?z 523 .3025 [ M +
Na] + ( calcd . 523 .3035 ) , which was confirmed by
13
C and DEPT NMR spectra . The
13
C and DEPT
13
C
NMR spectra also indicated that it may be one triter-
pene . Compared with 1 , compound 2 has one more
Me (δC 19 .1) and CH (δC 75 .2) , and two CH2 (δC
66 .2 , 25 .7 ) in 1 disappeared, which indicated that
the hydroxyl was located at a different position . The
HMBC spectrum showed correlations betweenδC 75 .2
(C - 21 ) andδH 0 .86 ( 3H, d, J = 5.96 Hz, H -
30) , 1 . 47 (1H, m, H - 22a) ( Figure 2 ) , which
indicated that the hydroxyl was located at C - 21 . And
the ROESY spectrum showed correlation betweenδH
2 .22 ( 1H, d, J = 9 .15 Hz, H - 18 ) andδH 3 .73
(1H, dd, J = 4 .31 , 11.96 Hz, H - 21 ) , which
indicated the OH on C - 21 wasβ configuration ( Es-
cudero et al , 1985; Piozzi et al , 1986 ) . So the
structure of 2 was determined to be 3-oxo-21β-hydroxy-
urs-12-en-27, 28-dioic acid, named Metatrichosin B .
Fig . 2 HMBC correlation of compound 1 and 2
Experimental
General 1 H , 13 C NMR and 2D NMR spectra were
recordedon a Bruker AM-400 or a DRX-500 NMR spectrometer
with TMS as internal standard . MS data were obtained on a VG
Autospec-3000 spectrometer .
Plant material The barks of Metadina trichotoma (Zoll .
et . Mor .) Bakn . were collected fromXishuangbanna, Yunnan
Province, China in September 2002 and identified by Associate
Prof . Wang Hong at XishuangbannaTropical Botanical Garden,
theChinese Academy of Sciences .
Extraction and Isolation The dried and powdered barks
(9 . 0 kg) of M. trichotoma were extracted with MeOH for three
times under room temperature and then concentrated under re-
duced pressure . The concentrated MeOH extract (1668 g) was
dissolved in hot water and extracted with petroleumether, AcOEt
and n-BuOH step by step, and obtained 19 g petroleumether ex-
tract, 85 gAcOEt extract, 780 gn-BuOH extract and884 gwater
extract respectively . The AcOEt part was subjected to silica gel
column chromatography with CHCl3 -MeOH-H2 O (1∶0∶0 to 8∶
2 .0 .2 V?V) and obtained fractions (Fr .) 1 - 8 . Fr . 2 was re-
peatedly subjected to silica gel column chromatography and eluted
with CHCl3?MeOH?H2 O 9∶1∶0.1 to afford subfractions 1 - 4 , and
subfraction 2 wassubjectedtoSephadex LH-20 columnchromatog-
raphy withCHCl3 -MeOH (1∶1) to afford1 (6 mg) and2 (4 mg) .
476 云 南 植 物 研 究 28 卷
Metatrichosin A (1) , C30 H44 O6 , white solids . [α] 24D =
105 .8 ( c = 0 .20 , Acetone) . HR + TOF-MS m?z 523 .3025
[M + Na] + (calcd . 523 .3035 ) . EI MS m?z500 [M] + . 13 C
NMR data see Table 1 . 1 H NMR data: 5 . 61 (1H, brs, H -
12) , 3 . 65 (1H, dd, J = 3 .08 , 10 .84 Hz, H - 29b) , 3 . 32
(1H , dd, J = 7.07 , 10.88 Hz, H - 29a) , 2 .26 (1H, d, J
= 11 .38 Hz, H - 18 ) , 1 . 02 ( 3H, s, H - 23 ) , 1 . 02 ( 3H,
s, H - 25 ) , 1 .00 (3H , s, H - 24 ) , 0 . 90 ( 3H , d, J =
9 .12 Hz, H - 30) , 0. 87 ( 3H , s, H - 26) .
Table 1 13 C-NMR dataof compound 1 and 2 in CD3 OD
(13C : 100 MHz; δ: ppm)
No . 1 X2 ?No . 1 2
1 ?40 .5 ( t) 40 . 5 ( t) 16 25 .5 (t) 19 .. 9 ( t)
2 ?35 .0 ( t) 35 . 0 ( t) 17 49 |. 2 (s) 55 +. 2 (s)
3 ?220 .7 ( s) 220 .7 (s) 18 55 x. 5 ( d) 56 &. 7 ( d)
4 ?48 .3 (s) 48 .3 ( s) 19 47 x. 8 ( d) 37 &. 7 ( d)
5 ?56 .1 ( d) 56 . 1 ( d) 20 32 x. 8 ( d) 38 &. 6 ( d)
6 ?20 .7 ( t) 20 . 7 ( t) 21 25 .7 (t) 75 &. 2 ( d)
7 ?37 .3 ( t) 37 . 3 ( t) 22 37 .2 (t) 39 .. 4 ( t)
8 ?40 .5 (s) 40 .7 ( s) 23 21 x. 7 ( q) 21 &. 7 ( q)
9 ?47 .1 ( d) 47 . 0 ( d) 24 27 x. 3 ( q) 27 &. 3 ( q)
10 #37 .8 (s) 37 ?. 7 ( s) 25 16 x. 6 ( q) 16 &. 6 ( q)
11 #24 ?. 0 ( t) 24 . 0 ( t) 26 17 x. 7 ( q) 18 &. 0 ( q)
12 #130 ?. 5 (d) 130 .2 ( d) 27 178 . 8 (s) 178 =. 9 ( s)
13 #133 ?. 9 ( s) 133 .9 (s) 28 181 . 5 (s) 179 =. 9 ( s)
14 #57 .2 (s) 57 ?. 5 ( s) 29 66 .2 (t) 19 &. 1 ( q)
15 #26 ?. 4 ( t) 24 . 7 ( t) 30 18 x. 9 ( q) 21 &. 3 ( q)
Metatrichosin B (2 ) , C30 H44 O6 , white solids . [α] 24D =
129 .7 ( c = 0 .41 , Acetone) . HR + TOF-MS m?z 523 .3025
[M + Na] + (calcd . 523 .3035 ) . EI MS m?z500 [M] + . 13 C
NMR data see Table 1 . 1 H NMR data: 5 . 62 (1H, brs, H -
12) , 3 . 73 (1H, dd, J = 4 .31 , 11 .96 Hz, H - 21 ) , 2 . 22
(1H , d, J = 11 .15 Hz, H - 18) , 1. 47 ( 1H , m, H - 22a) ,
1 . 39 ( 1H, m, H - 22b) , 1 . 04 ( 3H , s, H - 23 ) , 1 . 04
(3H , s, H - 25 ) , 1 . 02 (3H, s, H - 24) , 0. 95 (3H, d, J
= 6 .11 Hz, H - 29) , 0 . 87 (3H, s, H - 26) , 0. 86 (3H, d,
J = 5 .96 Hz, H - 30) .
Acknowledgements : The authors aregrateful to members of the
analytical group in the State Key Laboratory of Phytochemistry
and Plant Resouces in West China, Kunming Institute of Bota-
ny, the ChineseAcademyof Sciences, for the spectral measure-
ments . And wealso grateful to Miss JiaRuirui for thebioactivity
assay of the crudeextract in our group .
References:
Aqui ?no R , Tommasi ND, Simone FD, et al , 1997 . Triterpenes and
quinovic acid glycosides from Uncaria tomentosa [ J ] . Phytochemis-
try, 45 ( 5) : 1035—1040
Dele ?ctis Florae Reipublicae Popularis SinicaeAgendae Academiae Sinicae
Edita, 1999 . Florae Reipublicae Popularis Sinicae [ M ] . Beijing:
Science Press, 71 : 267—268
Escu ?dero J , Lopez C, Rabanal RM , et al , 1985 . Secondary metabo-
lites from Satureja species . New triterpenoid from Satureja acinoz
[ J ] . J Nat Prod, 48 (1 ) : 128—131
Pioz ?zi F , Paternostro M , Passannanti S, et al , 1986 . Triterpenesfrom
Amaracus dictamnus [ J ] . Phytochemistry, 25 ( 2) : 539—541
5766 期 ZHANG Yu-Mei et al: Two NewTriterpenes from Metadina trichotoma ( Rubiaceae)