全 文 ：A new p icfeltarraenone glycoside from P icria fel-terrae
ZOU Jie-m ing1* , WANG Li-sheng1, 2 , GUO Ya-jian2 , WANG Zheng1 , WANG Rui-zh i1
(1. Gu ilin Sanjin Pharm aceutica l Co. L td. , Guilin 541004 , China;
2. Institute of Ch ineseM edica, B eijing University of Traditional Ch ineseMa teriaM ed ica, B eijing 100102 , Ch ina)
Abstract:Ami 　To investigate the chem ical constituents from P icria fel-terrae Lour. M ethods
Co lumn chromatog raphy techniques w ere used to isola te the chem ica l constituents, physico-chem ica l
constan ts and spectroscop ic analysisw e re emp loyed fo r structural elucidation. Results　Tw o trite rpeno ids
named picfeltarraenone I (1) and picfeltarraenin X I (2) we re isola ted, and their struc tures w ere
estab lished to be 3 , 11, 22-trioxo-16α-hydroxy-(20S , 24)-epoxy-cucurbit-5 , 23-diene (1) and 3, 11, 22-
trioxo-16α-hydroxy-(20S , 24)-epoxy-cucurbit-5 , 23-diene-2β-O-β-D-glucopy ranoside (2), re spective ly.
Conc lusion　Compound 2 is a new compound, the 13CNMR data o f compound 1 is repo rted for the first
time.
Key words:P icria fel-terrae;triterpenoid;picfe ltarraenin
CLC number:R284. 1;R284. 2　　　Docum ent code:A　　　A rtic le ID:0513 -4870(2005)01 - 0036 -03
Received date:2004-06-05.
* Correspond ing au thor　Tel:86 -773 - 5842588,
Fax:86 - 773 - 5812547,
E-m ail:San jin@g.l gx. cn info. net
苦玄参中一个新苦玄参酮苷的分离与结构鉴定
邹节明 1* , 王力生 1, 2 , 郭亚健2 , 王　征 1 , 王睿陟 1
(1. 桂林三金药业股份有限公司 , 广西 桂林 541004;2. 北京中医药大学 中药学院 , 北京 100102)
摘要:目的　研究苦玄参的三萜类化学成分。方法　采用大孔树脂 、硅胶柱色谱纯化 ,经理化常数 、光谱学方法
鉴定结构。结果　分离得到了 2个三萜成分 ,分别鉴定为 3, 11, 22-三羰基-16α-羟基-(20S , 24)-环氧苦味素-5, 23-二
烯(1)和 3, 11, 22-三羰基-16α-羟基-(20S , 24)–环氧苦味素-5, 23-二烯-2β-O-β-D-吡喃葡糖苷(2)。结论　化合物 1
为已知化合物苦玄参酮 I,其 13CNMR数据为本文首次报导;化合物 2为新三萜皂苷。
关键词:苦玄参;三萜;苦玄参苷
Introduction
　　P icria fel-tarrae Lour. , an annua l plan t ma in ly
distributed in sou thern Ch ina, is used as a fo lk
medicine fo r the treatment of he rpes infec tions,
cancer, and inflamma tion[ 1] . M any chem ical stud ies
on this plant we re focused on its triterpeno ids
[ 2, 3]
. In
th is paper, we repo rt the struc tura l eluc idation of a new
triterpeno id, picfe ltarraenin X I (2) from P icia fel-
terrae.
Results and discussion
Compound 1　 Co lorless need les, mp 218 -
219 ℃. The EIM S show ed a molecula r ion peak a t
m /z 482[M ] +, compatible w ith themo lecu lar formula
C30H42O5 , which w as supported by 13CNMR andDEPT
spectra. The
13
CNMR spectrum o f 1 showed 30 carbon
signals, including three carbony l carbon signa ls (δ
206.7 , 212.8 and 212.8), four o lefinic carbons (δ
101.1 d, 119.8 d, 141.3 s and 195.1 s) and eigh t
methy l carbon resonances. Tw o o lefinic pro ton signals
(δ5.58 and 5.66) we re observed in the 1HNMR
spectrum. In terpre tation of the
13
CNMR and 2D NMR
spectral da ta o f 1 (Tab le 1) led to the identification o f
1 as picfeltarraenone I
[ 4]
.
Compound 2　Amorphous powder, exhibited a
quasi-mo lecu lar ion peak a tm /z 659[M -H ] - and a
characteristic fragment ion peak atm /z 497 ( loss o f
162 u) in FABM S ind ica ted that there is a
36 药学学报 A cta Pha rmaceutica Sinica 2005, 40(1):36 - 38
Tab le 1　NMR data of compounds 1 and 2a(J in
H z in parentheses)
N o.
2
1H 13C
1
13C
Aglycone
1 2. 58m 35. 2 t 25. 3 t
1. 66 overlap
2 5. 52m 78. 8 d 38. 2 t
3 212. 6 s 212. 8 s
4 51. 7 s 48. 2 s
5 140. 7 s 141. 3 s
6 5. 75 b r s 120. 4 d 119. 8 d
7 2. 31 dd (6. 0, 13. 0) 24. 2 t 24. 2 t
1. 75 overlap
8 1. 85 overlap 43. 0 d 43. 0 d
9 48. 2 s 49. 2 s
10 3. 10 b r d (12. 0) 34. 2 d 35. 9 d
11 211. 7 s 212. 8 s
12 3. 00 d (16. 0) 48. 7 t 48. 8 t
2. 52 d (16. 0)
13 48. 9 s 50. 6 s
14 50. 6 s 51. 2 s
15 1. 90 overlap 46. 4 t 46. 5 t
1. 70 b r d (12. 0)
16 4. 75 t (8. 0) 69. 7 d 69. 7 d
17 2. 95 d(8. 0) 59. 1 d 59. 2 d
18 0. 92 s 19. 9 q 19. 7 q
19 1. 15 s 20. 1 q 20. 1 q
20 91. 0 s 90. 9 s
21 1. 52 s 23. 1 q 23. 2 q
22 206. 9 s 206. 7 s
23 5. 65 s 101. 2 d 101. 1 d
24 195. 3 s 195. 1 s
25 2. 60m 30. 4 d 30. 3 d
26 1. 05 d(6. 0) 19. 7 q 19. 6 q
27 1. 08 d(6. 0) 19. 4 q 19. 4 q
28 1. 34 s 28. 6 q 28. 7 q
29 1. 36 s 21. 2 q 22. 8 q
30 1. 43 s 18. 6 q 18. 7 q
G lucosy l
1 5. 16 d(7. 8) 104. 1 d
2 4. 22 t (7. 8) 75. 9 d
3 4. 10 t (7. 8) 78. 5 d
4 4. 30 overlap 71. 3 d
5 3. 86m 77. 9 d
6 4. 50m;4. 35 m 62. 5 t
a 400MH z and 100MH z fo r 1H and 13CNMR in py rid ine-d5.
A ll 1H and 13CNM R signa ls we re assigned by m eans o f1H-1H
COSY, HMQC and HMBC expe rim ents
glucopy ranosy l mo iety in 2. Its mo lecu lar formu la,
C36H52O 11 , was determ ined by HRFABMS, m /z
659.341 2 [M -H ] - . In UV spectrum the maximum
abso rption a t261 nm (4.16) suggested the presence of
C =C -C =O functiona lity. The 13CNMR spectrum
further indicated that compound 2 was a trite rpene
g ly coside and the ag lycone was ve ry sim ilar to 1 (Table
1). The placemen t of the g lucopy ranosylmo ie ty on the
ag lycone w as determ ined by HMBC spectrum. Long-
range corre lations we re observed be tw een H-2 (δ
5.52)w ith the anome ric carbon (δ104.1) o f g lucose
unit, and the anomeric pro ton (δ5.16, d , J =7.8H z)
w ith C-2 (δ78.8), indicated that the g lucopyranose
w as loca ted a t C-2. The re lative ste reochem istry o f 2
was estab lished on the basis o f a ROESY experimen.t
The cross-peak observed betw een 10α-H and 2α-H
sugge sted that the g lucopy ranose a t C-2 is in β
configuration. A ccordingly, a ll the 1D and 2D NMR
data w ere w e ll assigned, and the struc ture of 2 was
complete ly established to be 3, 11, 22-trioxo-16α-
hydroxy-(20S , 24)-epoxy-cucurb it-5, 23-diene-2β-O-
β-D-glucopy ranoside, and assigned the triv ia l name
picfeltarraenin X I.
F igure 1　Key HMBC co rrela tions of compound 2
A rrow s point from p ro ton to carbon
Expermi ental
Melting points we re dete rm ined on a XRC-1
m icrome lting po int apparatus and w ere unco rrected.
TheM S andHRMS were ob tained on a FinniganMAT
90 instrumen.t O ptica l ro tations we re determ ined w ith
a Perkin-E lme r mode l 241 po larime te r. IR spectra
w ere run on a B io-Rad FTS-135 grating in frared
spectropho tomete r. UV spectra w ere taken on a
UV210A spectrom eter. 1D and 2D NMR spec tra w ere
recorded w ith a B ruke r AM-400 spectrome te r.
Chem ica l shifts (δ) were g iven w ith TMS as an
interna l standard. S ilica gel precoated p lates(Q ingdao
Ocean Chem ical Co. )were used in TLC and detection
w as carried ou t by spray ing w ith 10% H2 SO4 e thano l
fo llow ed by heating.
P lantM ater ial　The who le p lant o f P icria fel-
tarrae Lour. (Scrophu lariaceae) was co llected in
Wuzhou city, China, in 2001. A voucher spec imen
(PF-0101) is deposited in the herbarium o f the test
37 ZOU Jie-m ing, et a l:A new picfe ltarraenone glycoside from P icria fel-terrae
center ofGu ilin Sanjin Pha rm. Co. , China.
Extraction and Isolation　Dried and powde red
plantm aterial(10 kg)was ex tracted w ith E tOH (2×
100 L ) under ref lux. The combined filtrate w as
concentrated under reduced p ressure, then subjected to
co lumn chroma tography (CC ) on D iaion HP-20
(M itsubish i) e lu ted w ith H2O and M eOH. The
fraction e lu ted w ith M eOH was concen trated and
chromatographed on silica ge l co lumn, eluted w ith a
CHC l3-MeOH gradient( from 19∶1 to 1∶1), g iving 10
fractions. Fraction II w as sub jected to co lumn
chromatography on silica gel repeatedly. E lu tion w ith
solvent CHC l3-MeOH (9∶1) yie lded compound 1 (125
mg). F raction IV w as sub jec ted to repea ted co lumn
chromatography on silica ge l using CHC l3-MeOH
(12∶1) as e luent, resu lting in the iso lation of
compound 2 (25mg).
P icfe ltarraenone I (1)　Co lo rless need les, mp
218 - 219 ℃. UV (MeOH) λmax nm ( log ε):260
(4.10) (O =C -C =C). EIMS:m /z 482 [M ] +.
13
CNMR data (C5D5N):see table 1.
P icfe ltarraen in XI (2) 　W hite amo rphous
powder. [ α] 26D +35.9°(c 0.167, M eOH). IR(KB r)
νmax cm - 1: 3 442 (OH ), 1 690 (C =O ), 1 585
(C =C -C =O). UV(MeOH) λmax nm ( log ε):261
(4.16). FABM S(g lyce ro l):m /z 659 [M - H ] - ,
645, 629, 497 [ M - 162 - H ] -. HRFABMS:m /z
659.341 2 [ M - H ] - ( calcd fo r C36H 51O 11 ,
659.343 1). 1H and 13CNMR data (C5D5N): see
tab le 1.
A cknow ledgements:The au thors are indeb ted to P ro .f
Sun H andong, m em be r of Chine seAcademy of Sc ience, Dr. N iu
Xueme i and H an Quanbin (Kunm ing Institute o f Bo tany,
Chine se Academ y of Sc ience s, Kunm ing, Ch ina) fo r the ir help
on this paper. The au thors are a lso g ra te fu l to Zheng Yaonian,
Gu ilin Sanjin Pha rmaceutica l Co. L td. , for his iden tification of
the plan.t
References:
[ 1] H uang Y, B ruyne T, Apers S, et a l. Comp lem en t-
inh ib iting cucurb itacin g lycosides from P icria fe l-tarrae
[ J] . J Nat Prod, 1998, 61(6):757 - 761.
[ 2] Cheng GR, Jin JL, Wen YX, et a l. Studies on the
constituents of P icria fel-tarrae I. The structures of
picfe ltarraegenin I [ J] . Acta Chim S in (化学学报 ),
1982, 40(8):737 - 746.
[ 3] H u LH , Chen ZL, X ie YY. New triterpeno id saponins
from P icria fel-tarrae [ J] . J Nat Prod , 1996, 59(12):
1186 - 1188.
[ 4] Cheng GR, Jin JL, Gan LX. The structure of
picfe ltarraenone I [ J] . Acta Bot Sin (植物学报 ),
1982, 24(2):194 - 196.
38 药学学报 A cta Pha rmaceutica Sinica 2005, 40(1):36 - 38