全 文 ：热带亚热带植物学报 2003，l 1(2)：143-147
)ourna／of Tropical and Subtrop／ca／Botany
华麻花头根中的蜕皮甾酮类成分
凌铁军 马文哲 魏孝义 ‘
(中国科学院华南植物研究所，广东 广州 510650)
擅要：从华麻花头 (&mUula chinensis S．Moore)根中分得 7种蜕皮甾酮类化合物，经光谱分析和化学方法，分别鉴定
为：20-羟基蜕皮松 (1)，podec~ysone C(2)，3一氧 ·乙酰基 —2o．羟基蜕皮松 (3)，20-羟基蜕皮松 ·20,22·缩丁醛 (4)，
shidasterone(S)，atrotosteroneC(6)和 ca]曲锄los 黝 eC7)’其中 20-羟基蜕皮松 -20,22·缩丁醛为一新的化合物。
关■词：麻花头属；华麻花头；蜕皮甾酮类化合物；20-羟基蜕皮松-20~2·缩丁醛
中圈分类号：Q946．885．9 文献标识码：A 文章编号：1005-3395(2003)02--0143--05
Ecdysteroids from the Roots of Serratala chinensis
LING Tie-jun MA Wen-zhe WEI Xiao·yi‘
(sD Ch／na Institute of Botany,the Chinese Academy of Sciences，C,uangzlmu510650，China)
Abstract： Seven ecdysteroids，20-hydroxyecdysone(1)，podecdysone C(2)，3-O-acetyl-20-hydroxyecdysone(3)，
20-hydroxyecdysone-20，22·butylidene acetal(4)，shidasterone(5)，atrotosterone C and carthamosterone ，
were isolated from the roots ofSerratu／a ch／nem／~S． Moore． All compounds except compound 1 wel~isolated
from this plant forthe first time，and compoun d4 was foundto be a new ecdysteroid．
Key words：& tram／a；Serracu／a ch／nens／s；Ecdysteroid；20·hydroxyecdysone·20，22-butylidene acetal
Se门 u2口chinensis S．Moore(Compositae)is a
perennial herbaceous plant growing mainly in South
Chinap],where its roots areused asoneofthe substi．
tutes ofthetraditional Chinesemedicine,“Sheng．Ma”
(Cimicifuga foetidaL．)翻． occuITcnce of20-hydro-
xyecdysone from the plant was previously reported[31，
but its further chemical composition was unknown．In
order to discover new bioactive compounds。 we
investigated its chemical co nstituen ts． From ethanol
extract of the roots， seven ecdys嘶 ids have been
isolated． sUucU~s ofthe compounds(Fig．1)wore
elucidated oil the basis of spectroscopic analysis and
chemi cal correlation．
1 Results and discussion
By combined analysis ofUV， H and ℃ NMR
Reeeive~ 2002-09-16 Aeeepted：2003-01-03
Foundation item： Supported by the 100-Project of Science
and Tedmology Innovation t2gJ304201st
Gn~ gdongProvince,China．
‘~onespondingauthor
spectral da ta, compo un ds l—7 were determined to be
ecdysteroids with ,qaTru~stfllctIlIaI nuclei and diferent
side chains．Six known ecAysteroids were identified to
be 20-hydroxyecdysone(1)，podecdysone C(2)，3—()I
acetyl-20-hydroxyecdysone(3),shidasterone atroto-
sterone C(6)and carthamosterone ，respectively,as
physical and spectral data were in good agreement
with those already reported in the literatures[~．
Compound 4 was obtained as co lorless
amorphous solid． ESI-M S gave a base ion pcal【at
m／z 557【M+Na】+’indicating the molecular weight of
534．By combined analysis ofESI．MS，IT NMR an d
the DEPT data, its molecular formula was suggested
as C31H507． Its H an d 3C NMR spectra were similar
to those of 20-hydroxyecdysone (1)， except the
presence of four additional c8~oon signals at 8 104．4
(d)，38．1(t)，l7．9(t)and 14．4( in the ℃ NMR
speotrum an d four additional proton signals at 6 5．09
(1It,tJ：4．8 Hz)，1．73(2 m)，1．52(2H，in)and
0．92(3H， J：7．6 I-Iz)in the H NMR spectrum．
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144 热 带亚热带植物 学报 第 1l卷
1 R1=H R2= lla．
2 R1=H R2= ，·
3 R1=Ac R2=
O
OH
6
OH
4 R1 H R2 21 ，·
． 。 5 R1=H R2= H ’ 。
OH
OH 6 R1 H R2
H 7 R1 H R
carbon signal at 8 104．4 and the proton signal
at龟5．09 suggested the presence ofanacetafic methine．
Bycare~ analysisoftheIli．1Hand ℃-IHCOSYdata,a
group of n-butylidene acetal was deduced． 1e
downfield shifts of ℃ NMR signals for C．20 and
C-22 t0 6 84．2 and 84．7， respectively, suggested that
the n-butylidene acetal group WaS connected to C一20
and C-22． This was supported by the acid hydrolysis
of compound 4 to aford 20-hydroxyecdysone (1)．
Compound 4 was thus determined to be 20-hydro-
xyecdysone20，22-butylidene aceta1．
．
To determine the stereochemistry ofthe acetalie
carbon in compo un d 4， NOESY measurement Was
carried out． In the NOESY speotrul~ofcompoun d 4．
the presence ofa strong Cross peak between H-22(8
3．87) and H．1’(8 5．09)，andthe absence ofa CROSS
peak between H．21(8 1．32)and H．1’，indicated the
H．1’Was at B orientation ig．2)．As the R and R
configuration has been assigned for C-20 and C-22 ，
respectively, the absolute configuration of C-l’in
compo un d4 couldbedeterminedas R．
ll l
H
H
Though compo un d 4 has not been reported
before， it is suppo sed to be an artifcial product from
condensation of 20-hydroxyecdysone and butanal in
n-BuOH， as the compo un d could not be detected in
EtOH extract．
Fig．2 Significant correlations forthe sidechainof
compound 4 ／-theNOESY 印e‘
H
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第 2期 凌铁军等 ：华麻花头根 中的蜕皮甾酮类成分 l45
C 1 2 3 4 5 6 7
2 Experimental
General Melting points were uncorrected．
UV spectra were obtainedusinga Perkin Elmer lambda
25 UV，、，IS spectrophotometer． IR spec lra were
recorded on a WQF-410 FT-IR spectrophotometer．
Optical rotations were measured with a Perkin Elmer
343 polarimeter． NMR spectra wore measured on a
Bruker DRX_400 instrument ( H at400 MHz： ℃ at
lo0 MH using TMS as an internal standard．ESI．MS
spectra were obtained with a MDS SCⅡⅨ API 2000
LC／MS／MS spectrometer by direct inlet using MeOH
as solven t．SilicagelforCC and silicagel 60GF~ for
preparative TLC were from Qingdao Marine Chemical
L1d ， China． N【eOH was used as the eluant in
Sc phadex LH-2O CC． HlYrLC Was performed on
precoated silicagelplates(Merck,Kieselgel60 F2
usingEtOAc-MeOH-NH3·H20(concenwated)(10：0．5：
O．2) as the developing solvent and spoted with 10％
H2SO4inEtoHfolowedby heating．
Plant m terlal The roots of ＆ chinensis
wele collec ted in Lechang COWlty, Guangdong
province，China,inAutumn 2001，andidentifiedby
Prof．Ze-xian Li at South ChinaInstitute ofBotany,the
ChineseAcademyofSciences．
Extraction and isolation 111c groun d dry
roots(4．8 kg)ofS．ch／nens／,were extractedby perco-
lationwi th 95~／,EtOHthreetimes atlOOm temperature．
The EtOH solution was concenwatedto syrup (247 g)
t)~Cl／O． This syrup Was suspen ded in H20 and the
aqueous suspension was extracted successively wi th
petroleum (500 ml x4)， CHCh (5O0 ml x5) and
n-BuOH(500ml x5)．
111e BuOH extract,upon concentration un der
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146 热带亚 热带植物 学报 第 11卷
reduced pressure， aforded 78 g oflight brown syrup．
This syrupwasfurtherfractionatedby aDiaionHP·2O
CC eluted sequentially with 20％ EtOH, 50~／0 EtOH
and97％EtOH,yieldingthlcefractions㈣ ．Fraction
Dwas subjectedto a silicagelCCusingCHCI3-MeOH
(6：1)astheeluantfolowedbyrecrystalization,yielaing
compound 1(4 258 mg)and compound 2(184 mg)．
FractionFwassubjectedto a silicagelCC elutedwith
CHCI3-MeOH (2O：1) and repeated Sephadex LH-20
CC to yield compound 3 (48O mg) and compound 4
(378mg)．
The CHCh extract, on concentration, gave a
brown syrup(15|c}．This syrupwas subjectedtoa silica
gel(10 一l20 mesh)CC，eluted with CHCIrMoOH
mixtureofincreasingpolarity【(98：2)to(9：1)】，yielding
three fractions(A—C)．FractionB，afterchromatography
over a silica gel(200-300 mesh) column using
CHCI3-MeOH (92：8) as the eluant, folowed by a
Sephadex LH-20 CC，aforded compound 5(22 mg)．
FractionCwas sequentiallychroma tographed onasilica
gel column eluted with CHC13·MeOH【9：1)mixture，a
Sephadex LH·2O column,an d a preparative t—hi—n layer
usingEtOAc·MeOH-NI-I3·H20(concentrated)(10：0．5：
O．2)asthe developing solvent，yielding compound 6
(15mg)andcompound7(50mg)．
20-hydroxyeedysone(1) C 正{．p7，colorless
needles，mp 243-245~(2(MeOH)，【Q】苗+59．3。(c O．3，
MeOl-I)；ESI-MS m／z(％)：503 ar【1Oo)；IR
V cm ：3423，2966，1655，1382，1057；Uv 入
nm(1og。)：242．3(4．O6)； HNMR(CD3OD)6：O．88，
0．96，1．18，1．189，1．194(each 3H，s，Me x5)，3．13
(1H’m，H·9)，3．83(1H’br‘lJfil1．2 Hz,H．2 Q)，3．94
(1H’br s，H-3 Q)，5．8O(1H，‘lJ=2．0 Hz，H-7)； ℃
NMR(CD3OD)：seeTabIe 1．
PodecdysoneC【2) colorlessneedles,
mp 160—165℃ (MeOH)，【Q】苗+53．0。 (c O．37，
MeoH)；ESI-MS m／z(％)：519[M+Nar(1Oo)；UV
入 urn(1og。)：241．8【4．13)； H NMR(CD3OD)6：
0．88，0．96，1．13，1．19(each 3H，s，Me×4)，3．13(1H，
m’H-9)，3．36(2H，s，H-26)，3．83(1H，br dd,J=3．6，
l1．6 H·2Q)，3．94(1H’br s，H·3Q)，5．8O(1 d，fi
2．0Hz，H-7)； 3CNMR(CD3OD)：seeTable 1．
3-0·Acetyl·20-hydroxyecdysone(3) C29H4608’
amorphous solid,【Q +51．8o(c0．114,MeOI-1)；ESI．
*
MS m／z(％)：545[M+Nar(10o)；UV 入 (1og 。)：
242．4(4．22)； H NMR(CD3OD)6：0．89，0．99，1．18，
1．191，1．196(each 3H，s’Me×5)，2．1l(3H，s，Ac)，
3．16(1H，m，H．9)，3．97(1H，br dd,Jfi3．6，l1．6 Hz’
H．2Q)5．14(1l|l br H·3 Q)5．82(1l|l d，J=2．0 I-Iz,
H．7)； ℃NMR(CDsOD)：seeTable 1．
【4)
C3lH ，colorles am orphous solid, 【Q +55．0。(c
O．1，MeOH)；ESI．1 S m／z(％)：573[M+K】 (21)，557
【M+Nar(10)，535【M+I-I] (22)；瓜 V cm ：3425,
2964，1653，1380，1057；Uv 入 一nil1(1og e)：241．8
(4．0o)； H NMR(C5D 6：O．92(3H，tJ=7．6 Hz,
H-4’)，1．04，1．O5，1．32，1．37，1．38(cach 3H，s，H．18，
H．19，H-2l，H_27，H．26)，1．52(2H，m’H-3’)，1．73
(2H，m’H-2’)，2．79(1H，m’H-17)，3．00(1I-I,dd,J=
3．2，l2．8}Iz，H-5)，3．55(1I-I,hr tJ=8．0 Hz，H·9)，
3．87(1H，br‘lJ-9．6 Hz’H·22)，4．17(1H’br dd,J=
3．6，l1．6}Iz，H·2 Q)，4．23(1H’hr s，H-3 Q)，5．o9
(1H’t =4．8Hz’H-l)，6．26(1H’‘l， =2．0Hz，H-7)；
℃ NMR(C5D ：see Table 1．
Addhydrolysisof~ompouml4 Tl1e solution
ofcompound 4 in 2 ml ofmethanolic HCl(6％) wss
refluxed for l hour． 111c reaction mixture was diluted
wi th 3 ml of water and evaporated to remove
methano1． Th e aqueous solution was extracted wi th
n-BuOH 11le BuOHlayer,afterevaporation, af orded
2O·hydroxye~dysone,whichwasidentified bythedirect
comparison onTLC wi th compo un d 1．
Shidasterone(5) C I． am orphous solid,
【Q】苗+31．4。(c 0．086，MeOI-I)；ESI-MS m／z(％)：485
[M+Nar(10o)；UV 入 nm (1og 。)：240．8【4．15)；
H NMR(CD3OD) 6：0．84，0．95，1．21，1．23，1．24
(each3H,s’Mex5)，3．13(1H’m’H．9)，3．83(1H’brdd,
-3．2’11．4Hz,H-2Q)’3 (1l|lbrd,Jfil0．0Hz,H-22g
3．94(1H’br H-3 Q)’5．80(1l|l d， ：2-0 H H-7)； ℃
NMR(CD3OD)：see Tabk 1．
A 的略te】m啦 C( colorlessnoodles,
mp 219-225~C 0V~eOh0，【Q瑶 +44．0。(c O．116，
MeOI-I)；ESI-MS m／z(％)：515[M+Na】+(1Oo)；UV
入 衄 (1og e)：242．3(4．O8)； HNMR(C5D 6：
1．O7，1．2l，1．52，1．59，1．59(each 3H，s，Mex5)，3．60
(1H，br tJ=8．8 Hz’H·9)，4．09(1H’br‘lJ=8．8 Hz
H·22)，4．18(1H，br‘l．，=l1．6 Hz’H-2 Q)，4．23(1H’
br s，H·3 Q)，5．12(1H’br s’H-28a)，5．29(1I-I,br sI
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第 2期 凌铁军等：华麻花头根中的蜕皮 甾酮类成分 147
H-28b)，6．26 (1H，‘lJ=2．0 Hz，H-7)； ℃NMR
(C5D ：seeTable 1．
Clirthalllf161~roll~ (7) c29H 8’amorphous
soUd,【a】 +46．1。(c 0．436，MeOH)；ESI-MS m／z
：541【MI+Nar(1 ；Uv nlI1(1og )：240．8
(4．14)； H NMR(C5D 6：1．07，1．22，1．34，1．4l，
1．65(each 3H，S，Mex5)，3．56(1H，br tJ=8．4 Hz，
H-9)，4．16(IH，br‘lJ=10．0 Hz，H-2 a)，4．16(1Hbr
‘lJ=10．0 Hz，H-22)，4．24(1Hbr S，H-3 a)，6．26(1H
‘l，-2．0 Hz，H-7)，6．30(1H，S，H-28)； 3C NMR
(C5D ：see Tab】e 1．
Acknowledgements： We thank Mr．R Q Cher~
Guangzhou Institute of Chemistry, the Chinese
Academy of Seiences， for NMR measurementS，and
Dr．A D Ma， First Military Medical Universit y，
for ESI measurementS．
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