全 文 ：川赤芍的化学成分研究?
李 鲜1 , 2 , 黎胜红1 , 普建新1 , 黄胜雄1 , 孙汉董1
??
(1 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;
2 昆明医学院药学院 , 云南 昆明 650031)
摘要 : 从川赤芍 Paeonia anomala subsp. veitchii 根皮的 70%丙酮提取物中 , 分离鉴定了 22 个化合物 , 其中包
括一个新的 24 , 30 位降常春藤皂苷三萜衍生物 , 命名为 paeonenolide H ( 1)。化合物 2 , 4 , 9 , 10 为首次从
该植物中分离得到。
关键词 : 芍药科 ; 川赤芍 ; 三萜化合物
中图分类号 : Q 946 文献标识码 : A 文章编号 : 0253 - 2700 (2007) 02 - 259 - 04
Chemical Constituents from Paeonia anomala
subsp. veitchii (Paeoniaceae)
LI Xian1 , 2 , LI Sheng-Hong1 , PU Jian-Xin1 , HUANG Sheng-Xiong1 , SUN Han-Dong1 *
( 1 State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Instituteof Botany, ChineseAcademy of
Sciences, Kunming 650204 , China; 2 College of Pharmacology, Kunming Medical College, Kunming 650031 , China)
Abstract: A new triterpenoid derivative, paeonenolide H (1 ) together with twenty-one known compounds, were isolated
from the root cortex of Paeonia anomala subsp. Veitchii (Lynch) . Their structureswereelucidatedon thebasis of spectro-
scopic evidences . Compounds 2 , 4 , 9 , 10 were isolated fromthis plant for thefirst time .
Key words: Paeoniaceae; Paeonia anomala subsp. Veitchii ; Triterpenoids
Paeonia anomala subsp. veitchii ( Lynch) (Hong
et al . 2001 ) is oneof the most important crude drugs
in traditional Chinese medicine, used as antiinflamma-
tory, analgesic and sedative agent . It is also frequently
used as a remedy for female diseases ( Wu, 1990 ) .
Phytochemical analysis on this plant led to isolation of
twenty-two compounds ( 1 - 22) , including a new trit-
erpenoid derivative (1) . In thispaper, wedescribethe
isolation and structural elucdation of 1 .
Results and Discussions
Paeonenolide H ( 1 ) , obtained as white amor-
phous powder, gave a quasimolecular ion peak at m?z
497 [M-H] - in the negative FABMS spectrum, corre-
sponding to themolecular formulaC31 H46 O5 determined
by the HR-FAB-MS . Considering the structuresof trit-
erpenoids previously isolated fromthe P . anomala sub-
sp. Veitchii and careful inspection of the 1 H- and 13 C-
NMR ( including DEPT) spectra (Table 1) , compound
1 should possess theskeleton of bisnortriterpenoid deri-
vative similar to paeonenolide C ( Wu et al . 2005 ) .
The prominent differences between two compoundswere
thepresence of additional three carbon signals in 1 at
δC 110 .4 (s) , 26 .8 ( q) and 26 .5 ( q) , which were
attributed toa 1 , 3-dioxolanemoiety . A careful analys-
is of the 2D NMR spectroscopic data led to the conclu-
sion that the acetal C-atomof 1 was connected withC -
4 and C - 23 through O-atoms forming a five-membered
1 , 3-dioxolane moiety instead of the six-membered 1 ,
3-dioxolanemoiety of paeonenolide C , on the basis of
云 南 植 物 研 究 2007 , 29 (2) : 259～262
Acta Botanica Yunnanica

?
?? ?Author for correspondence . E-mail : hdsun@ mail . kib. ac. cn, Tel: 0871 - 5223251
Received date: 2006 - 09 - 07 , Accepted date: 2006 - 10 - 11
作者简介 : 李鲜 ( 1974 - ) 女 , 理学博士 , 讲师 , 主要从事植物化学研究。 ?
Foundation item: Financial support of this research was provided by the Natural Science Foundation of Yunnan Province ( No . 2004C0008Z) .
Fig . 1 The selected HMBC correlations of compound 1
HMBC ( Fig . 1 ) correlations of H - 23 (δH 4 .13 and
3 .78 , d, J = 8 .4 Hz, each 1H ) and ( - 蟎Me)2 C - 2′
(δH 1 .40 and 1 .36 , s, each 3H) with the acetal C -
2′atom (δC 110 .4 ) , and the absence of the HMBC
correlation between H - 3 (δH 3 .22, dd, J = 5 .0 ,
11 .7 Hz, 1H) and the acetal C - 2′atom . The abnor-
mal downfield chemical shifts of the acetal C - 2′atom
and C - 4 were attributed to the strain effect in thefive-
membered ring . Thus, 1 was determined to be ( 3β,
4β) -3-hydroxy-4 , 23 ( isopropylidendioxy)-24 , 30-di-
norolean-12 , 20 ( 29)-dien-28-oic acid .
The known compounds were determined as oplo-
panxogenin C (2) (Adam et al . 1982) , 3β, 23-ace-
tonide-hederagenin (3 ) ( Wu et al . 2005 ) , 3β, 4β,
23-trihydroxy-24 , 30-dinor-olean-12 , 20 ( 29 )-dien-
28-oic acid ( 4 ) ( Wu et al . 2001 ) , paeonenolide F
(5) (Wu et al . 2005) , paeonenolide G ( 6 ) ( Wu et
al . 2005 ) , hederagenin ( 7 ) ( Ikuta and Itokawa,
062 云 南 植 物 研 究 29 卷
1988 ) , 3β, 23-acetonide-4β-hydroxy-24 , 30-dino-
rolean-12 , 20 ( 29)-dien-28-oic acid ( 8) ( Wu et al .
2005) , paeoniflorigenone ( 9) (Shimizu et al . 1981) ,
lactiflorin ( 10 ) ( Lang et al . 1990 ) , benzoylpaeoni-
florin ( 11 ) ( Ishida et al . 1987 ) , 6′-O-benzoyl-4″-
hydroxy-3″-methoxy-paeoniflorin ( 12 ) ( Wu et al .
2002) , gallic acid ( 13 ) , benzoic acid ( 14 ) , 3 , 4-
dimethoxybenzaldehyde ( 15 ) , 2-hydroxy-benzyl-3-
hydroxy-benzoate (16) , euglobal (17) (Kozuka et al .
1982) , twenty-two carboxylic acid (18) , 2-hydroxy-1-
linoleic acid-propaneyl ester ( 19 ) , 2-hydroxy-1-lino-
lenic acid-propaneyl ester (20) , daucosterol (21 ) , β-
sitosterol ( 22) .
Experimental Part
General Optical rotation was recordedona SEPA-300 po-
larimetre . UV spectrum was obtained on a Shimadzu double-
beam 210A spectrometer in pyridine . The MS spectra were per-
formed on a VG Autospec-3000 spectrometer with 70 eV . 1 H , 13
C NMR and 2D NMR were recorded on a Bruker AM-400 and
DRX-500 spectrometer with TMS as internal standard . The silica
gel for TLC and column chromatography were obtained from
Qingdao Marine Chemical Inc ., China .
Plant Material The root cortex of Paeonia anomala sub-
sp. Veitchii was bought fromCrude Drug Company, in Kunming,
Yunnan Province, in December 2003 . It was identified by Pro-
fessor Lin Zhong-Wen . The voucher specimen ( KIB-2003-024
Lin) was deposited in Laboratory of Phytochemistry, Kunming
Institute of Botany, Chinese Academy of Sciences .
Extraction and Isolation The dried and powdered root
cortex ( 14 .5 kg) wereextracted with 70% acetoneat roomtem-
perature for 3× 24 h . The extract was concentrated and parti-
tioned between EtOAc and H2 O . The EtOAc extract ( 1 . 14 kg)
was subjected to column chromatography over silica gel ( 100 -
200 mesh, 2 . 5 kg) elutingwith CHCl3?Me2 CO (from 1∶0 to 0∶
1) to give six fractions . Compounds 13 (1 .05 g) , 14 (15 .0 g)
15 (12 mg) , 16 (15 mg) , 19 (15 mg) , 22 ( 60 mg) were ob-
tained fromfraction Ⅰ , 2 ( 15 mg) , 4 ( 12 mg) were purified
from fraction Ⅱ , 9 ( 1 .50 g) , 20 ( 19 mg) were purified from
fractionⅢ , 3 (2 mg) , 7 (15 mg) , 8 (20 mg) , 5 ( 11 mg) , 1
(6 mg) , 6 (8 mg) , 17 (75 mg) wereachievedfromfractionⅣ ,
and 21 (15 mg) , 12 (105 mg) , 11 (25 mg) , 10 ( 25 mg) , 18
(8 mg) were achieved from fraction Ⅴ , respectively, after re-
peatedly RP-18 andSephadex LH-20 columnchromatography and
semipreparative reverse-phase HPLC .
Paeonenolide H ( 1) : white needles crystal; C31 H46 O5 ;
[α] 21D + 92.4°( c 1.46 , C5 H5 N) . UVλMeOHmax nm: 203 ( 3 .98 ) ;
IR νKBrmax cm- 1 : 3432 , 2936 , 1721 , 1697 , 1459 , 1378 ,
1194; FAB (negative) m?z: 497 [M-H ] - ; HR-FABMS ( neg-
ative) : 497.3254 ( calcd . for C31 H46 O5 : 497 .3267) ; 1 H and13
C NMR (pyridine-d5 ) data seeTable 1 .
Oplopanaxogenin C ( 2 ) : white amorphous powder; C30
H48O4 ; Mp . 270 - 273℃ ; IRνKBrmax cm- 1 : 3426 , 2942 , 1692 ,
1640 , 1452 , 1384 , 1046; [α] 20D + 8°( c 0 .4 , CHCl3 ) . NMR
data: same as the data reported in Adam et al . (1982) .
3β, 23-acetonide Hederagenin ( 3 ) : white amorphous
powder; C30 H48 O4 ; EIMS m?z: 498 [M] + , 265 , 248 ( 100 ) ,
203 . NMR data: same as the data reported in Wu et al .
(2005) .
3β, 4β, 23-trihydroxy-24 , 30-dinorolean-12 , 20 ( 29 )-
dien-28-oic acid ( 4 ) : white amorphous powder; C28 H42 O4 ;
[α]24D + 89 .3°( c 0 .252 , MeOH ) . UV λMeOHmax nm: 204 .5 ; IR
νKBrmax cm- 1 : 3421 , 2936 , 1719 , 1690 , 1663 , 1465 , 1443 ,
1382 , 1295 , 1046 , 886 . NMR data: same as the data reported
in Wu et al . ( 2001) .
Table 1 1 H and 13C NMR data of compound 1 ( in pyridine-d5 , J in Hz)
No . δH δC No . δH δC
1 ?1 .38 ( 1H , m) , 0 . 84 ( 1H , overlap) 38 .2 ( t) 17 ;46 .8 (s)
2 ?1 .66 ( 2H , overlap) 27 .6 ( t) 18 ;2 *. 71 (1H , dd, 4 2. 7 , 10 .8 ) 46 .9 ( d)
3 ?3 .22 ( 1H , dd , 5 . 0 , 11 .7 ) 71 .1 ( d) 19 ;2 *. 50 (1H , t like, 10 .8) , 2 . 15 (1H , overlap) 41 .2 (t)
4 ?85 .3 (s) 20 ;147 .8 (s)
5 ?0 .84 ( 1H , overlap) 52 .8 ( d) 21 ;2 *. 10 (1H , overlap) , 2 . 15 (1H , overlap) 30 .0 (t)
6 ?1 .61 ( 2H , m) 19 .2 ( t) 22 ;1 *. 89 (2H , m) 37 .3 (t)
7 ?1 .43 ( 1H , m) , 1 . 12 ( 1H , m) 32 .3 ( t) 23 ;4 *. 13 (1H , d, 8 . 4 ) , 3 . 78 ( 1H , d, 8 . 4) 70 .0 (t)
8 ?39 .4 (s) 25 ;0 *. 99 (3H , s, Me-25) 14 .7 ( q)
9 ?1 .52 ( 1H , dd , 7 . 4 , 10 .8 ) 46 .5 ( d) 26 ;0 *. 80 (3H , s, Me-26) 17 .0 ( q)
10 /37 ?. 4 (s) 27 ;1 *. 15 (3H , s, Me-26) 25 .9 ( q)
11 /1 ?. 76 ( 1H , overlap) 23 ?. 1 ( t) 28 ;182 .4 (s)
12 /5 ?. 35 ( 1H , d, 3 . 2) 123 ?. 2 ( d) 29 ;4 *. 62 (2H , br s) 107 .1 ( t)
13 /142 . 9 ( s) C-2 A′ 110 ?. 4 (s)
14 /42 ?. 1 (s) Me-1 W′ 1 *. 40 (3H , s) 26 .8 ( q)
15 /2 ?. 10 ( 1H , overlap) , 1 . 76 (1H , overlap) 28 ?. 4 ( t) Me-3 W′ 1 *. 36 (3H , s) 26 .5 ( q)
16 /2 ?. 10 ( 1H , overlap) , 1 . 66 (1H , overlap) 23 ?. 3 ( t)
1622 期 LI Xian et al .: Chemical Constituents from Paeonia anomala subsp. veitchii (Paeoniaceae)
Paeonenolide F (5) : whiteamorphous powder; C32 H46 O5 ;
[α] 24D + 71 .1°( c 0 .24 , CHCl3 ) ; UVλMeOHmax nm: no absorption;
IRνKBrmax cm- 1 : 2938 , 2859 , 1777 , 1466 , 1391 , 1361 , 1256 ,
1220 , 1167 , 1133 , 1114 , 1067 , 1024 , 932 , 895 , 872 ,
863; EIMS m?z: 510 [M ] + , 495 ( 100 ) , 435 , 291 , 263 ,
247 , 233 , 219 , 201 , 189 , 173 , 159 , 147 , 119 , 105 , 95 .
NMR data: sameas the data reported in Wu et al . (2005) .
Paeonenolide G ( 6 ) : white amorphous powder; C32 H46
O5 ; [α] 24D + 92 .1°( c 0 .35 , CHCl3 ) ; UVλMeOHmax nm: no absorp-
tion; IRνKBrmax cm- 1 : 3528 , 3063 , 2946 , 1775 , 1647 , 1396 ,
1365 , 1257 , 1230 , 1146 , 1079 , 1051 , 985 , 927 , 873 ; EIMS
m?z: 512 [M] + , 497 ( 100 ) , 468 , 453 , 437 , 293 , 265 ,
247 , 232 , 221 , 203 , 189 , 173 , 159 , 147 , 105 , 91 . NMR da-
ta: sameas the data reported in Wu et al . (2005 ) .
Hederagenin ( 7) : white amorphous powder ; C30 H48 O4 ;
UVλMeOHmax nm: 206 (3 .78) ; IRνKBrmax cm- 1 : 3449 , 2943 , 2577 ,
1697 , 1463 , 1386 , 1267 , 1206 , 1037 , 1013 , 653; EIMS m?
z: 472 [M] + , 454 , 426 , 248 (100) , 223 , 203 , 187 , 175 ,
119 , 107 , 95 , 81 , 69 . NMR data: sameas thedata reported in
Ikuta et al . (1988) .
3β, 23-acetonide-4β-hydroxy-24 , 30-dinorolean-12 , 20
(29 )-dien-28-oic acid (8) : C32 H48 O4 ; FABMS (negative) m?
z: 495 [M-H] - . NMR data: same as the data reported in Wu
et al . (2005) .
Paeoniflorigenone (9) : C17 H18 O6 ; UVλMeOHmax nm: 240 .5 ,
274 .5 , 282.0 ; IRνKBrmax cm- 1 : 3421 , 2971 , 1723 , 1600 , 1451 ,
1397 , 1315 , 1278 , 1102 , 1171 , 1033 , 963 , 712 . NMR data:
same as the data reported in Shimizu et al . ( 1981) .
Lactiflorin ( 10 ) : white amorphous powder; C23 H26 O10 ;
Mp . 195 - 198℃ ; [α]23D + 37 .2°( c 0 .90 , EtOH ) ; IR νKBrmax
cm- 1 : 3505 - 3460 , 1745 , 1722 , 1450 , 1380 , 1340 , 1275 ,
1230 , 1174 , 1110 , 1065 , 1025 , 968 , 892 , 850; EIMS m?z:
462 [M] + , 371 , 340 , 300 , 285 (100) , 255 , 214 , 196 , 178 ,
163 , 162 , 150 , 135 , 127 , 122 , 105 , 77 . NMR data: same as
the data reported in Lang et al . (1990) .
Benzoylpaeoniflorin ( 11) : white amorphous powder; C30
H32 O12 ; [α] 17D = - 13.97°( c= 0 .36 , MeOH) ; IRνKBrmax cm- 1 :
3450 , 2904 , 1713 , 1600 , 1554 , 1452 , 1345 , 1278 , 1177 ,
1070 , 956 , 712 . NMR data: same as the data reported in Ishida
et al . (1987) .
6′-O-benzoyl-4″-hydroxy-3″-methoxy-aeoniflorin ( 12 ) :
white amorphous powder; C31 H34 O14 ; [α] 17D - 13 .95°( c 0.43 ,
MeOH) ; UV λMeOHmax nm: 203 ( 4 .36 ) ; IR νKBrmax cm- 1 : 3430 ,
1711 , 1599 , 1514 , 1450 , 1428 , 1383 , 1345 , 1284 , 1222 ,
1179 , 1115 , 1073 , 1025 , 823 , 763 , 714 . NMR data: same as
the data reported in Wu et al . (2002) .
Gallic acid (13) : colorless needle; C7 H6 O5 ; Mp . 247 -
249℃ ; UVλMeOHmax nm: 270 ; IRνKBrmax cm- 1 : 3490 , 3060 , 2650 ,
1708 , 1623 , 1524 , 1450 , 1330 , 1246 , 1031 , 954 ; FABMS
(negative) m?z: 169 [M-H ] - .
Benzoic acid ( 14 ) : colorless needle; C7 H6 O5 ; EIMS m?
z: 122 [M] + , 105 (100 ) , 94 , 77 , 58 . The value of Rf is
consistent with that of authentic sample on TLC .
3 , 4-dimethoxybenzaldehyde ( 15 ) : colorless needle;
C9 H10 O3 ; FABMS ( negative) m?z: 165 [M-H] - . NMR data:
same as the data reported in AldrichLibrary of
13
C and
1
H NMR
spectra .
2-hydroxy-benzyl-3-hydroxy-benzoate (16 ) : yellow amor-
phous powder; C14 H12 O4 ; FABMS (negative) m?z: 243 [M-H] - .
Euglobal ( 17) : colorless needle; C10 H16 O3 ; ESIMS ( neg-
ative) m?z: 183 [M + H] + . NMR data: same as the data re-
ported in Kozuka et al . (1982) .
Twenty-two carboxylic acid ( 18 ) : C23 H46 O2 ; FABMS
(negative) m?z: 339 [M-H ] - .
2-hydroxy-1-linoleic acid-propaneyl ester ( 19) : C21 H38
O4 ; FABMS ( positive) m?z: 355 [M + H] + .
2-hydroxy-1-linolenic acid-propaneyl ester (20) : C21 H36
O4 ; FABMS ( positive) m?z: 353 [M + H] + .
Daucosterol (21) : FAB MS m?z 575 ( [M-1 ] - ) ; The
value of Rf is consistent with that of authentic sampleon TLC .
β-Sitosterol (22 ) : EI MS m?z 414 ( [M] + , 80 ) ; The
value of Rf is consistent with that of authentic sample onTLC .
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262 云 南 植 物 研 究 29 卷