Triterpenoids from Rhaponticum uniflorum

Article abstract of DOI:10.1002/jccs.200200020

The isolation and identification of twenty-one components (including four new triterpenoid saponins and one new triterpenoid acid) from the root of Rhaponticum uniflorum (L.) DC. (Compositae) are described. Their structures were determined on the basis of

Full text of DOI:10.1002/jccs.200200020

JournaloftheChineseChemicalSociety, 2002, 49, 117-124
117
Triterpenoids from Rhaponticum uniflorum
Yong-Hong Zhang (
Li Yang (
), Jie-Kai Cheng (
) and Dong-Liang Cheng* (
),
)
DepartmentofChemistry,NationalLaboratoryofAppliedOrganicChemistry,LanzhouUniversity,
Lanzhou 730000, P. R.China
Theisolationandidentificationoftwenty-onecomponents(includingfournewtriterpenoid sapo nins and one
new triterpenoid acid) from the root of Rhaponticum uniflorum (L.) DC. (Compositae) are de scribed. Their struc-
tures were de ter mined on the ba sis of spec tral anal y sis and chem i cal trans for ma tion. The new com pounds were
iden ti fied as 3-O- -L-arabinopyranosyl-urs-12,18(19)-dien-28-oic acid -D-glucopyranosyl es ter, 3 -hy-
droxy urs-12,18(19)-dien-28-oic acid -D-glucopyranosyl es ter, 3 -hydroxyurs-12,19(29)-dien-28-oic acid
-
D-glucopyranosylester,3-O- -L-arabinopyranosyl-urs-9(11),12-dien-28-oic acid -D-glucopyranosyl es-
ter and 2 ,3 ,19 ,25-tetrahydroxyurs-12-en-23,28-dioic acid.
1
4
3
15
INTRODUCTION
Rhaponticum uniflorum (L.) DC. (Compositae) is dis-
acid (18), arc tic acid (19), (+)-catechin (20), and dau-
1
6
costerol (21) on the ba sis of their NMR and MS spec tra, and
comparisonwithauthenticsamplesandliteraturedata.Five
of them were iden ti fied as new com pounds, 3-O- -L- arab-
inopyranosyl-urs-12,18(19)-dien-28-oic acid -D- gluco-
pyranosyl es ter (10), 3 -hydroxyurs-12,18(19)-dien-28-oic
acid -D-glucopyranosyl es ter (11), 3 -hydroxyurs-12,19(29)-
dien-28-oic acid -D-glucopyranosyl es ter (12), 3-O- -L-
arabinopyranosyl-urs-9(11),12-dien-28-oic acid -D-gluco-
pyranosyl es ter (13), and 2 ,3 ,19 ,25-tetrahydroxyurs-
12-en-23,28-dioic acid (14) by var i ous NMR tech niques, in-
clud ing COSY, NOESY, HMQC and HMBC ex per i ments
and chem i cal meth ods. These five com pounds gave pos i tive
re sponse to the Liebermann-Burchard test and com pounds
10-13 alsoshowedpositivecolorationtomolishtest,indicat-
ing 10-13 to be triterpenoid saponins and 14 to be a tri-
terpene.
trib uted in north ern China. Its root is a Chi nese tra di tional
medicineandhasbeenusedforintoxicationandforthetreat-
1
mentoffever. Recently,itwasdemonstratedthatitsethylac-
e tate ex tract in hib its peroxidation of mem brane lipids and
2
posseses antiatherosclerotic ac tiv ity. Some lipophilic com-
ponentsofsulfur-containingacetylenecompoundshavebeen
3
iso lated from this plant. Many phytoecdysteroids were iso-
4
latedfromitsrootsandaerialparts. Wehaveinvestigatedthe
chem i cal con stit u ents of its root, lead ing to the iso la tion of
twenty-one com po nents in clud ing five triterpenoid ac ids,
nine triterpenoid sapo nins, three phytoecdysteroids, one phe-
nols, one thiophene, one flavonoid, and one ste roid. Of these
com po nents, four triterpenoid sapo nins and one triterpenoid
acid are new com pounds. In this pa per, we de scribe the struc-
turalelucidationofisolatedcomponents.
Com pound 10 was ob tained as an amor phous pow der,
mp 203-205 C. The IR spec trum showed the ab sorp tion for
-
1
-1
hydroxyl groups (3354 cm ), es ter car bonyl (1727 cm ) and
-
1
RESULT S AND DISCUSSION
dou ble bond (1640 cm ). Acid hy dro ly sis of10 in refluxing
5% HCl ben zene af forded D-glucose and L-arabinose, iden-
1
Separation of the methanolic extract of roots of
Rhaponticum uniflorum over sil ica gel and Sephadex LH-20
yielded twenty-one com pounds. Six teen of them were iden ti-
ti fied by PC. The HR-FABMS showed the mo lec u lar ion at
m/z 748.4392, corresponding to the molecular formula
C
41
H
64
O12. 10 had ul tra vi o let ab sorp tion max i mum at 238
5
fied as known com pounds, ursolic acid (1), 3-oxo-19 -hy-
nm,indicatingtheexistenceofaconjugateddienesystem.Its
6
7
1
droxyurs-12-en-28-oic acid (2), pomolic acid (3), ziyu
3
H NMR spec trum (400 MHz, CD OD) showed the pres ence
8
glycoside II (4), 28-O- -D-glucopyranosyl pomolic acid es-
of one vi nyl hy dro gen ( 5.37, t, J = 4.0 Hz) and one vi nyl-
6
8
ter (5), ziyu glycoside I (6), 2 ,3 ,19 -trihydroxyurs-12-
attached methyl group ( 1.73, s). These data con cluded com-
9
10
11
17
en-28-oic acid (7), rosmutin (8), sauvissimoside R
1
(9),
pound 10 to be a 12,18(19)-diene ursane type triterpene.
The H NMR spec trum showed two anomeric pro tons at
1
2
13
1
ecdysterone (15), ajugasterone C (16), ajugasterone C-
1
3
2
0,22-monoacetonide (17), 3,3 ,4-tri (O-methyl) ellagic
6.20 (d, J = 8.1 Hz, glc-1) and 4.26 (d, J = 6.9 Hz, ara-1), in-

118 J. Chin. Chem. Soc., Vol. 49, No. 1, 2002
Zhang et al.
30
2
9
R2
20 21
HO
1
2
HO
1
1
9
1
8
2
5
26
COOH
CO2R2
1
5
CO2R2
1
4
16
HO
HO
2
7
7
R1
1
R O
6
2
4
23
R1
OH
H
3
4
5
6
1 2
R =R =H
1
R1=
R =H
2
8
9
R1=CH3 R2=Glc
R1=CO2H R2=Glc
R1=Ara R2=H
R1=H R2=Glc
R1=Ara R2=Glc
2
R1=O R2=OH
CO2Glc
CO2Glc
2
CO Glc
RO
HO
AraO
1
1
0
1
R=Ara
R=H
13
12
OR3
OR2
HO
21
24
26
O
1
8
2
0
23
25
27
C
O
O
C
OH
R1
12
11
R4
1
7
R
19
CO2H
HO
H3CO
OCH3
HO
HO
1
15
9
OH
4
7
HO
H3CO
H
O
O
HOOC
7
1
R=CH3
R=CH2OH
18
4
15 R1=R2=R3=H R4=OH
1
1
6
7
R1=OH R2=R3=R4=H
R =OH R R =CMe R =H
1
2
3
2
4
OH
HO
O
OH
OH
H3C
C
C
CO2H
OH
S
S
GlcO
1
9
2
0
2
1
+
dic a tive of the pres ence of a -glucosyl and a -arabinosyl
293-295 C, m/z: 454 [M] . Many fea tures in its EI mass spec-
moiety. Onacidhydrolysis, 10 fur nished an aglycone, mp
trum in di cated that the aglycone was closely re lated in struc-

Triterpenoids from Rhaponticum uniflorum
J. Chin. Chem. Soc., Vol. 49, No. 1, 2002 119
1
3
Table 1. C NMR Spectral Data of Compounds 10~12
olefinic pro tons cor re spond ing to the aglycone groups in the
1
(
100 MHz, 10 in CD
3
5 5
OD, 11~12 in C D N)
H NMR spec trum of 11+12. The IR spec trum showed the
-
1
C
10
11
12
presence of hydroxyl groups (3433 cm ), ester carbonyl
-
1
-1
(
1723 cm ) and dou ble bond (1631 cm ).Acidhydrolysisof
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
40.23 t
27.47 t
90.66 d
40.35 s
57.20 d
19.27 t
35.85 t
40.64 s
48.58 d
37.82 s
24.23 t
127.70 d
139.54 s
45.69 s
29.24 t
27.14 t
48.36 s
134.04 s
137.53 s
35.63 d
31.61 t
35.85 t
28.66 q
17.14 q
16.70 q
18.74 q
22.35 q
176.60 s
19.79 q
18.74 q
39.36 t
28.15 t
79.08 d
39.45 s
55.96 d
18.67 t
35.11 t
39.81 s
48.32 d
37.51 s
23.48 t
126.65 d
138.75 s
44.91 s
29.05 t
26.74 t
49.90 s
133.84 s
137.51 s
34.58 d
30.97 t
35.31 t
28.79 q
16.60 q
16.31 q
18.56 q
22.11 q
174.74 s
19.53 q
18.68 q
39.05 t
28.15 t
79.32 d
39.45 s
55.96 d
18.67 t
35.11 t
39.45 s
48.10 d
37.51 s
23.85 t
128.56 d
138.75 s
42.80 s
29.05 t
25.77 t
49.80 s
52.23 d
153.45 d
37.40 s
30.63 t
37.18 t
28.79 q
16.51 q
15.77 q
18.68 q
22.11 q
176.28 s
110.37 t
19.38 q
the mix ture af forded D-glucose as the sole sugar, and HR-
FABMS(m/z 616.3969; calc.: 616.3969), in di cated that the
mo lec u lar for mula should be C36
H
56
8
O . The NMR spec trum
of 11+12 showed that 11 and12werestructuralisomers.The
1
H NMR spec trum (400 MHz, pyridine-d
5
) in di cated that 11
was closely re lated to 10, ex cept for the ab sence of arabinosyl
1
3
moi ety at C-3. The C NMR spec trum of 11+12exhibited
0
12
sig nals for two
-dou ble bond ( 126.65, 138.75; 128.56,
-dou ble bond ( 133.84, 137.51) and one
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
8(19)
1
38.75), one
terminaldoublebond[ 153.45(s), 110.37(t)].Comparison
1
3
of the C NMR and DEPT spec tral data of 11 and 12 with
those of re lated com pounds found com pound11 and 12 to
12,18 17
12,19(29)
have a con ju gated
,
and
func tions, re spec-
1
5
1
tively. The H NMR spec trum of 11+12 showed sig nals for
twoanomericprotonsofglucose( 6.32, 6.31, d,J = 8.1 Hz),
H-29 ( 1.79, 3H, s; 5.53, 5.18, 2H, br s), H-12 ( 5.75, 1H,
t; 5.65, 1H, t), and H-3 ( 3.45, 2H, dd, J = 11.1, 4.1 Hz).
Thus, 11 was elu ci dated as Ilexolic acid 28-O- -D-gluco-
pyranoside (18-dehydro-20-epiursolic acid 28-O- -D- gluco-
pyranosyl ester) and 12 was deduced as 3 -hydroxyurs-
1
2,19(29)-dien-28-oic acid -D-glucopyranosylester.
The com pound 13, platelet crys tals, mp 247-249 C,
hadamolecularformula,C 41
H
64
O12, based on the HR- FABMS
(
m/z748.4394; calc.: 748.4392). The IR spec trum (KBr) in di-
-
1
Sugar moieties
cated the pres ence of hydroxyl groups (3437 cm ), es ter car-
bonyl (1729 cm ) and dou ble bond (1645 cm ). Acid hy dro-
Glc-28
95.77 d
74.03 d
78.63 d
71.26 d
78.39 d
62.61 t
Ara-3
Glc-28
95.80 d
74.11 d
78.87 d
71.18 d
78.06 d
62.30 t
Glc-28
95.90 d
74.05 d
78.87 d
71.18 d
78.14 d
62.30 t
-1
-1
1
2
3
4
5
6
lysisof13affordedD-glucoseandL-arabinose, identifiedby
1
PC. The H NMR spec trum of13 showed the pres ence of two
trisubstituted dou ble bonds. That these two trisubstituted
dou ble bonds form a homoannular diene sys tem was ev i dent
fromitsUVabsorptionmaximumat280nmcharacteristicof
17
1
such a sys tem. The fol low ing H NMR spec tral data of 13
400 MHz, pyridine-d ) sug gested the struc tural fea tures of
1
2
3
4
5
107.09 d
72.83 d
74.33 d
69.47 d
66.32 t
(
5
an urs-9(11),12-dien-28-oic acid bioside triterpene: a broad
sin glet at 1.97 (H-18), two olefinic pro tons at 5.70 (d, J =
1
0.7 Hz, H-11) and 6.49 (d, J = 10.5 Hz, H-12), which were
con firmed by the cross peaks be tween H-11 and H-12 in the
1
1
H- H COSY spec trum, and H-29 ( 0.75, d, J = 6.4 Hz, 3H),
1
7
ture to Ilexolic acid. Thus 10 was de ter mined to be Ilexolic
acid 3-O- -L-arabinopyranosyl-28-O- -D-glucopyranoside
H-30 ( 0.97, d, J= 6.7 Hz, 3H) and two anomeric pro tons at
6.20 (d, J = 8.1 Hz, glc-1) and 4.75 (d, J = 7.0 Hz, ara-1).
1
3
(
3-O- -L-arabinopyranosyl-18-dehydro-20-epiursolic acid
The C NMR spec trum showed four olefinic car bons at
135.49 (s, C-9), 127.34 (d, C-11) and 125.99 (d, C-12),
138.25 (s, C-13), and a car boxyl car bon at 176.58 (s, C-28).
2
8-O- -D-glucopyranosylester).
Compounds11 and 12 wereisolatedasaninseparable
1
3
mix ture in a ra tio of 3:2, based on the in te gra tion of the
The as sign ments of the C NMR sig nals of 13 were made by

120 J. Chin. Chem. Soc., Vol. 49, No. 1, 2002
Zhang et al.
1
13
5 5
Table 2. H and C NMR Spectral Data of Compound 13 (400 MHz, C D N)
No.
H
C
Observed connectivities in HMBC spectrum
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
0.97 m, 1.81 m
1.91 m, 2.20 m
3.35 dd (11.8, 4.1)
38.29 t
26.54 t
88.56 d
39.64 s
55.32 d
26.61 t
32.82 t
40.86 s
135.49 s
36.65 s
127.34 d
125.99 d
138.25 s
42.48 s
32.00 t
25.68 t
47.16 s
54.67 d
27.80 d
34.67 d
32.60 t
24.99 t
27.90 q
16.66 q
18.37 q
17.00 q
21.23 q
176.58 s
19.46 q
16.42 q
H-2, H-25
H-1
H-1, H-2, Ara-1 , H-23, H-24
H-23, H-24
H-24, H-23, H-1
H-26
H-26
H-11, H-18, H-6, H-26, H-27
H-11, H-12, H-18, H-27
H-1, H-2, H-25
H-18
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
5.70 d (10.7)
6.49 d (10.5)
H-18
H-12, H-26, H-27
H-12, H-15, H-26, H-27
H-26, H-27, H-16
H-15, H-27
H-22
H-12
H-29, H-21, H-22
H-19, H-29, H-30
H-30
H-20, H-29
H-3, H-24
1.67 m, 2.15 m
1.65 m, 2.01 m
1.97
2.81 m
1.26 s
0.92 s
0.86 s
1.14 s
1.00 s
H-3, H-23
H-1
H-26
Glc-1 , H-22, H-21
H-28
0.75 d (6.4)
0.97 d (6.7)
Ara-3
1
2
3
4
4.75 d (7.0)
4.45 m
4.16 m
4.32 m
4.02 m, 3.98 m
107.47 d
72.88 d
74.58 d
69.47 d
66.70 t
5
Glc-28
1
2
3
4
5
6
6.20 d (8.1)
4.17 m
4.42 m
4.37 m
3.83 m
96.37 d
74.09 d
79.25 d
71.25 d
78.81 d
62.36 t
4.28 m, 4.24 m
1
8
-1
com par i son with those of model triterpenes and were con-
firmedbytheHMQCandHMBCspectralanalysis(seeTable
2
ab sorp tion for hydroxyl groups (3412 cm ) and a carboxylic
-
1
group (1689 cm ). The EI-MS ex hib ited sig nif i cant ions at
m/z 264, 246, 201, 187, and 146, which in di cated the pres-
ence of a ter tiary hydroxyl func tion on C-19 in the urs-12-
). On the ba sis of these data, the struc ture of 13 was elucided
as 3-O- -L-arabinopyranosyl-urs-9(11),12-dien-28-oic acid
1
3
-
D-glucopyranosylester.
en-28-oic acid skel e ton in ac cord with its C NMR spec-
1
9
1
Thecompound14, amorphouspowder, mp293-295 C,
trum. The H NMR spec trum of 14 showed sig nals for two
protonsonC-1( 1.47, 2.28, m, 2H) and two geminal pro tons
on C-25 ( 4.17, 4.22, dd, J = 13.8,1.5 Hz, 2H), which were
hasamolecularformula,C 30
46 8
H O , based on the HR-FABMS
(
m/z 534.3191; calc.: 534.3189). The IR spec trum showed the

Triterpenoids from Rhaponticum uniflorum
J. Chin. Chem. Soc., Vol. 49, No. 1, 2002 121
1
13
5 5
Table 3. H and C NMR Spectral Data of Compound 14 (400 MHz, C D N)
No.
H
C
Observed connectivities in HMBC spectrum
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
1.47 m, 2.28 m
4.23 m
4.62 d (8.4)
48.26 t
68.69 d
81.24 d
54.70 s
52.34 d
21.37 t
33.31 t
40.44 s
48.07 d
38.54 s
24.10 t
127.63 d
140.08 s
42.09 s
29.25 t
26.96 t
48.07 s
54.70 d
72.70 s
42.31 d
26.40 t
38.54 t
181.05 s
13.73 q
64.79 t
17.31 q
24.61 q
181.05 s
27.08 q
16.74 q
H-1, H-3
H-1, H-24
H-3, H-5, H-24
H-24, H-26
H-5, H-26
H-26
2.23 m
H-26, H-27
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
H-1, H-25, H-26
H-12, H-27
H-11, H-18
H-18, H-27
H-12, H-18, H-26, H-27
2.08 m, 2.23 m
5.54 m
1.16 m, 2.21 m
2.02 m, 3.10 m
H-27
H-15, H-18
H-11, H-29
H-18, H-29, H-30
H-29, H-30
H-30
3.02 br s
1.30 m
1.40 m
2.04 m
1.68 s
4.17, 4.22 dd (13.8, 1.5)
1.06 s
1.62 s
H-3, H-5
H-2
H-11
H-30
H-18
1.39 s
1.08 d (6.6)
con firmed by the cross peaks be tween H-1 and H-25 in the
car boxyl group was assigned to C-23 on the ba sis of HMBC
and NOESY dif fer ence spec tra (see Ta ble 3). Thus, 14 was
elu ci dated as 2 ,3 ,19 ,25-tetrahydroxyurs-12-en-23,28-
dioicacid.
1
1
15
H- HCOSYspectrum. Since the sig nal of C-4 was shifted
6
to lower field ( 54.70) than that of7 ( 38.67), and was very
1
1
sim i lar to that of the co-occurring known triterpene 9, the
The above twenty-one com pounds con tained seven dif-
ferentskeletons:fiveursanetypetriterpenoidacids(1, 2, 3, 7,
and 14), nine ursane type triterpenoid sapo nins (4, 5, 6, 8, 9,
1
0, 11, 12, and 13), three ecdysteroids (15, 16, and 17), one
HO
phenol(18), one thiophene (19), one flavonoid (20), and one
ste roid (21). Triterpenoid is an other ma jor prod uct in this
plant ex cept the phytoecdysones.
HOH2C
COOH
HO
HO
EXPERIMENTAL SECTION
HOOC
General Methods
Melting points were de ter mined on a Kofler micro-
melting point ap pa ra tus and are un cor rected. Op ti cal ro ta-
Fig. 1. SelectedHMBCcorrelationsof14.

122 J. Chin. Chem. Soc., Vol. 49, No. 1, 2002
Zhang et al.
O
C
H
OH
OH
O
OH
O
O
H
O
: HMBC
HO
HO
: NOESY
OH
H
OH
Fig. 2. Key HMBC and NOESY cor re la tions of13.
tions were ob tained with a JASCO-20 polarimeter. IR spec tra
were re corded on a Bio-Rad FTS spec trom e ter and UV spec-
tra on an UV-210A spec trom e ter. NMR spec tra were per-
formed on a Bruker AM-400 us ing TMS as an in ter nal stan-
dard. NMR ex per i ments in cluded H- H COSY, NOESY,
HMQC, and HMBC. HR-FABMS was mea sured on a Bruker
APEX II, and FABMS and EIMS were mea sured on a VG-
ZAB-HSmassspectrometer.
2
LH-20 and eluted with MeOH or H O-MeOH to yield 21 (36
mg), 4 (50 mg), 5 (42 mg), 11 and 12 (50 mg). Frac tion IV
was purified by repeated chromatography on Sephadex
LH-20 and eluted with a gra di ent of H O-MeOH to give8 (45
2
1
1
mg), 6 (80 mg), 10 (55 mg), 13 (56 mg), 15 (31 mg), 16 (23
mg) and 17 (25 mg).
The n-BuOH layer was con cen trated un der re duced
pres sure to leave a brown syrup (36 g) which was sub jected to
chro ma tog ra phy on sil ica gel (1.8 Kg, 200-300 mesh) and
Plant Material
eluted with a gra di ent of CHCl
(46 mg).
3
and MeOH (8:1) to af ford 9
The roots of Rhaponticum uniflorum (L.) DC. (Com-
positae) were pur chased from a com pany of Chi nese me dic i-
nal ma te ri als in Gansu Prov ince, China, and were iden ti fied
by Prof. Yin-Shou Zhou, Lanzhou Medical College. A
voucherspecimenNo.98001wasdepositedintheHerbarium
ofthePharmacyDepartment,LanzhouMedicalCollege,and
3-O- -L-Arabinopyranosyl-urs-12,18(19)-dien-28-oic acid
-D-glucopyranosyl ester (10)
2
0
Amor phous pow der (MeOH), mp 203-205 C; [ ]
D
+67.1 (MeOH; c 0.31); UV (MeOH) max (log ): 238 (3.75)
-
1
intheLaboratoryofNaturalProducts,LanzhouUniversity,P. nm; IR (KBr, cm ): 3354 (OH), 1727 (C=O), 1449, 1386,
1
R. China.
1074; H NMR (400 MHz, CD
3
OD): 3.15 (1H, dd,J = 11.1,
4
.1 Hz, H-3), 5.37 (1H, t, J = 4.0 Hz, H-12), 1.73 (3H, s,
Extraction and Isolation
H-29), 0.99 (3H, d, J = 6.4 Hz, H-30), 0.84, 0.92, 0.98, 1.04,
1.10 (each 3H, s, Me 5), 4.26 (1H, d, J = 6.9 Hz, H-Ara1),
The roots of Rhaponticum uniflorum (3 kg) were ex-
tracted with MeOH ( 6) at room tem per a ture, and con cen-
trated to give a dark brown syrup (156 g). The MeOH ex tract
was sus pended in wa ter and sub jected to se quen tial ex trac-
tion with petrol, EtOAc and n-BuOH, successively. The
EtOAc layer was con cen trated un der re duced pres sure to
leave a brown syrup (41 g) which was sub jected to chro ma-
tog ra phy on sil ica gel (2.1 Kg, 200-300 mesh) and eluted with
a gra di ent of petrol and EtOAc (9:1) to af ford five frac tions.
FractionII(16g)underwentcolumnchromatographyonsil-
ica-gel (1.6 Kg, 300-400 mesh) and eluted with n-hexane-
EtOAc(9:1)toobtain19 (25 mg), 1 (10 mg), 2 (14 mg), 3 (56
mg), 7 (41 mg), 14 (46 mg), 18 (65 mg), and 20 (45 mg), suc-
ces sively. Frac tion III was chromatographed on Sephadex
1
3
6.20 (1H, d, J = 8.1 Hz, H-Glc1); C NMR (100 MHz,
CD OD) data is listed in Ta ble 1; EIMS m/z (rel. Int.): 586
3
(M-Glc, 2.1), 454 (M-Glc-Ara, 5.3), 437 (5.6), 408 (2.4), 246
(26.6), 208 (3.6), 207 (14.7), 201 (51.6), 190 (54.8), 189
+
(50.0), 145 (35.0), 119 (48.0); FAB-MS m/z: 771 [M+Na] ,
+
749 [M+H] ; HR-FABMS m/z 748.4400, calcd for C41
H
64
12
O :
748.4392.
3 -Hydroxyurs-12,18(19)-dien-oic acid -D-
glucopyranosyl es ter (11) and 3 -hydroxyurs-
12,19(29)-dien-28-oic acid -D-glucopyranosyl es ter (12)
-
1
Amor phous pow der (MeOH). IR (KBr, cm ): 3433
1
(OH), 1723 (C=O), 1631 (C=C), 1454, 1387, 1198, 1071; H

Triterpenoids from Rhaponticum uniflorum
J. Chin. Chem. Soc., Vol. 49, No. 1, 2002 123
NMR (400 MHz, C
5
D
5
N): 3.45 (1H, dd, J = 11.0, 4.0 Hz,
to the Na tional Lab o ra tory of Ap plied Or ganic Chem is try
1
H-3), 5.69, 5.53, t, H-12; 1.79 (3H, s, H-29), 5.53, 5.18 (2H,
andAnalyticCenter,LanzhouUniversityformeasuring H,
1
3
br s, H-29 ), 1.00 (3H, d, J = 6.2 Hz, H-30), 0.91, 1.00, 1.08,
C-NMR spec tra and FAB-MS, HR-FABMS, EI-MS, re-
1
.15, 1.21 (each 3H, s, Me 5), 6.31, 6.32 (each 1H, d,J = 8.1
spec tively. This work was sup ported by the Na tional Sci-
ences Foun da tion of China (No. 29772010).
1
3
Hz, glc-1); C NMR (100 MHz, C
5 5
D N) data is listed in Ta-
ble 1; EIMS m/z (rel. Int.): 454 (M-Glc, 5.0), 408 (2.9), 246
(
(
6
27.2), 208 (4.2), 207 (16.0), 201 (53.0), 190 (56.0), 189
+
51.0), 145 (34.2), 119 (47.5); FAB-MS m/z : 639 [M+Na] ,
Received July 23, 2001.
+
17 [M+H] ; HR-FABMS m/z 616.3969, calcd for C 36
H
56
O
8
:
6
16.3969.
Key Words
Rhaponticum uniflorum; Compositae; Triterpenoid
sapo nins; Triterpenoid ac ids.
3
-O- -L-Arabinopyranosyl-urs-9(11),12-dien-28-oic acid
D-glucopyranosyl ester (13)
Platelet crys tals (MeOH), mp 247-249 C; [ ] +21
-
2
D
0
-1
REFERENCES
(
pyridine; c 0.12); IR (KBr, cm ): 3437 (OH), 1729 (C=O),
645 (C=C), 1468, 1370, 1068; UV (MeOH) max (log ): 280
1
1
13
1. Jiangsu New Med i cal Col lege. TheEncyclopediaofTradi-
tionalChineseMedicine;ShanghaiScienceandTechnology
Press: Shang hai, 1985; Vol. 2, pp 2576-2579.
. Fu, N. W.; Quan, L. P.; Xu, S. L.; Huang, T. X. Zhongcaoyao
989, 20, 25-27.
(
3.91) nm; H NMR, C NMR (400 MHz, C
5
D
5
N) data is
+
+
listed in Ta ble 2; FABMS m/z: 771 [M+Na] , 749 [M+H] ,
+
+
586 [M-Glc] , 454 [M-Glc-Ara] ; HR-FABMS m/z 748.4394,
2
3
4
calc.: 748.4392.
1
. Wei, H. X.; Gao, W. Y.; Tian, Y. J.; Guan, Y. K.; Huang, M.
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Pharma. Sin. 1991, 26, 442-446.
2
,3 ,19 ,25-Tetrahydroxyurs-12-en-23,28-dioic acid
(14)
2
D
0
Amor phous pow der (MeOH), mp 293-295 C; [ ]
-
1
+
43.6 (pyridine; c 0.21); IR (KBr, cm ): 3412 (OH), 1689
5. Kuo, Y. H.; Yeh, M. H. J. Chin. Chem. Soc. 1997, 44,
1
13
(
COOH), 1605 (C=C), 1558, 1461, 1398, 1051; H NMR, C
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17 (M+H-H O, 100), 498 (M-2H O, 13.0), 264 (3.0), 246
3.5), 201 (5.0), 187 (2.7), 146 (4.0); FABMS m/z: 534 [M] ,
379-383.
6
. Cheng, D. L.; Cao, X. P. Phytochemistry 1992, 31,
317-1320.
5
D
5
1
5
2
2
+
7. Hidaka, K.; Ito, M.; Matsuda, Y.; Kohda, H.; Yamasaki, K.;
(
+
Yamahaea, J. Phytochemistry 1987, 26, 2023-2027.
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Pharm. Bull. 1971, 19, 1700-1705.
5
17 [M+H-H
2
O] ; HR-FABMS m/z 534.3191, calcd for
8
9
30 46 8
C H O
: 534.3189.
. Takahashi, K.; Kawaguchi, S.; Nishimura, K.; Kubota, K.;
Tanabe, Y.; Takani, M. Chem. Pharm. Bull. 1974, 22, 650-
Total hydrolysis of compounds 8,9,10,11+12,13
6 6
Each com pound (20 mg), 15% HCl (20 mL) and C H
6
53.
(
20 mL) were mixed and refluxed for 10 hr. Af ter neu tral iza-
10. Du, H. Q.; Zhao, X.; Zhao, T. Z.; Wang, M. T. Acta Pharm.
Sin. 1983, 18, 314-316.
tion of the aq. layer, the soln was filtered and concd. D-
Glucose in com pounds8, 9, 10, 11+12, and 13 wasidentified
11. Gao, F.; Chen, F.; Tanaka, T.; Kasai, R.; Seto, T.; Tanaka, O.
Chem. Pharm. Bull. 1985, 33, 37-40.
by PC us ing EtOAc-pyridine-H O(12:5:4)asdevelopingsol-
2
1
1
1
1
2. Pinheiro, M. L.; Filho, W. W.; Rocha, A. I.; Por ter, B.;
Wenkert, E. Phytochemistry 1983, 22, 2320-2321.
3. Zhang, M. L.; Stout, M. J.; Kubo, I. Phytochemistry 1992,
vent. L-Arabinose in com pounds 10 and 13 was de tected by
PC.
3
1, 247-250.
4. Takuo, K.; Masami, Y.; Hitoshi, I. Chem. Pharm. Bull. 1984,
2, 4478-4481.
ACKNOWLEDGEMENT
3
5. Jia, Z. J.; Liu, X. Q.; Liu, Z. M. Phytochemistry 1993, 32,
The au thors are grate ful to Pro fes sor Yin-Suo Zhou
155-159.
(
Faculty of Pharmacy, Lanzhou Medical College, P. R.
16. Sakakibara, J.; Kaiya, T.; Fukuda, H.; Ohki, T. Phyto-
chemistry 1983, 22, 2553-2555.
China)forhishelpinidentificationoftheplantmaterial, and

124 J. Chin. Chem. Soc., Vol. 49, No. 1, 2002
Zhang et al.
1
1
7. Zhen, L. M.; Su, J. W.; Zhang, S. D. Chem. J. Chin. Univ.
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1