全 文 ：　　　　 天然产物研究与开发　 　　　　　
Vo1.14　No.1 NATURAL PRODUCT RESEARCH AND DEVELOPMENT　 　　　
　
　
　
　A CONTRACEPTIVE CONSTITUENT FROM
ARNEBIA EUCHROMA(ROYLE)JOHNST＊.
ZHANG Hui-zhen1 , 2 ,LIAO Mao-chuan＊＊2 ,XUAN Li-jiang3 ,GUO Ji-xian1
(1.School of Pharmacy , Fudan University , Shanghai　200032 , China;
2.National Laboratory of Drugs and Devices for Family Planning ,
Shanghai Institute of Planned Parenthood Research , Shanghai　200032 , China;
3.Shanghai Institute of Materia Medica , CAS , Shanghai　200031 , China)
Abstract　F rom the roots of Arnebia euchroma(Roy le)Johnst., dipotassium rabdosiin 1 , potassium rosmari-
nate 2, sodium rosmarinate 3 and sodium ferulate 4, were isolated by means of reversed phase chromato-
g raphy.Their structures were identified by spectral analyses (UV , IR , MS , 1H NM R , 13C NMR).Com-
pound 1 exhibited conspicuous contraceptiv e effect.Compound 2 , 3 and 4 were discovered in the roots of A.
euchroma firstly.
Key words　Arnebia euchroma(Royle)Johnst.;dipo tassium rabdosiin;contraceptiv e effect
0　Introduction
The root of Arnebia euchroma is used as a traditional
Chinese medicine named ” Xinjiang Zicao” , which
shows many pharmacological activities , such as pro-
moting blood circulation , counteracting toxici ty and
facilitating eruption.In 1982 , Liu reported that the
aqueous ex tract of Arnebia euchroma could terminate
the early pregnancy of mice and rabbits [ 1].In this pa-
per , we reported the isolat ion and st ructural elucida-
tion of four phenolics:dipotassium rabdosiin 1 , potas-
sium rosmarinate 2 , sodium rosmarinate 3 and sodium
ferulate 4 f rom the roo ts of Arnebia euchroma.A-
mong them , compound 1 exhibited conspicuous con-
t raceptive effect , which could exci te the uterine
smooth muscle of mice and stimulate the necrosis of
human decidual cell.Compound 2 , 3 and 4 were dis-
covered fi rst ly f rom this plant.
收稿日期:2001-11-05　　修回日期:2001-12-29
＊The Project S upported by National Laboratory of Drugs and Devices for Family Planning.
＊＊Author to w hom correspondence should be addressed.
1
1　Results and Discussion
Compound 1 , a tan amorphous powder , was separat-
ed by MCI gel CHP20P cc of the aqueous ext ract of
the roots of Arnebia euchroma , and showed a dark-
blue colorat ion with FeCl3 reagent , indicative of its
phenolic nature.Its UV spectrum (H2O) showed
peaks at 252 , 282 , 316 (sh)and 343 nm .The IR
spectrum revealed the presence of phenolic groups
(3600 ～ 3300 cm -1), conjugated carbonyl groups
(1692 cm-1), and aromatic rings (1600 ～ 1400
cm-1).The 1H NMR (in D2O)spect rum exhibited
three one-pro ton aromatic or olefinic sing lets(δ6.52 ,
6.87 , 7.53 , s , 1 H each), tw o aliphatic methines
(δ3.90 , 4.46 , br.s , 1 H each), two oxygen-bear-
ing methines (δ4.84 , 4.98 , br.d , 1 H each), two
methylenes(δ2.65 ～ 3.12 , m , 4 H), and three cat-
echol rings.The protons at δ6.52 and 6.87 can be
at t ributed to a 1 , 2 , 4 , 5-tet rasubstituted benzene
moiety , and that at δ7.53 to the β-proton of the caf-
feoyl g roup.The 13 C NMR (in D2O) spectrum
showed signals due to four carboxy l carbons , four
aromatic rings , a double bond , two oxygen-bearing
carbons , and four aliphatic carbons.These data were
identical with those of rabdosiin [ 2]　.Compound 1 was
suggested to be a salt because of its poor solubili ty in
o rganic solvents.It w as confirmed by IR spectral da-
ta.No signals above 1720 cm -1 were detected ,
which are diagnastic to the caboxyl group.Instead ,
signals at 1586 cm
-1
and 1396 cm
-1
were showed to
be assigned to caboxylate moity.ESI-MS showed the
molecular ion peak at 795 , which w as 76 more than
that of robaosiin , indicative of two potassium ion.
Consistently , atom absorbance spectrum conf irmed
the existence these two potassium ion quantat itively.
Consequently , compound 1 w as identified as dipotas-
sium rabdasiin.
2　Experimental
2.1　General
UV was tested by Lambda 20 in H 2O.IR was
reco rded by 360FT-IR Nicolet.NMR spectra w ere
acquired on Bruker AM-400 , Bruker-DRX 400 and
Gemini-300 , with TMS as internal standard.EI-MS
data w as obtained on HP5989A.
Column chromatog raphy w as performed using MCI
gel CHP20P (75 ～ 150 μ, Mitsubishi Chemical In-
dust ries Co.Ltd.), TSK gel Toyopearl HW-40F(30
～ 60 μ, TOSO Co.Ltd.), Cosmosil 75 C18-OPN
(42 ～ 105μ, Nacalai Tesque Inc.), Sephadex LH-20
(25 ～ 100 μ, Pharmacie F ine Chemical Co.Ltd.).
T LC was conducted on precoated HSGF254 plates
(Qingdao Ocean Chemical Co.)with benzene-ethyl
acetate-formic acid(2∶7∶1).
2.2　Plant material
The dried root of Arnebia euchroma (Roy le)Johnst.
was bought f rom Shanghai Huayu Ltd.The voucher
specimen w as ident if ied by Professo r Guo Jixian and
deposi ted in the Department of Pharmacognosy ,
School of Pharmacy , Fudan University.
2.3　Extraction and Isolation
The dried roots of Arnebia euchroma (8 kg)were
ext racted wi th 70% aqueous Me2CO.The aqueous
Me2CO extract was concentrated to yield an aqueous
solution.After removal of the insolubles by filt ration ,
the filt rate w as concentrated under reduced pressure ,
and subjected to MCI gel CHP20P column chromato-
graphy w ith H2O containing an increasing amount of
MeOH to give f ive f ractions:FractionsⅠ(196 g), Ⅱ
(20.6 g), Ⅲ(22.3 g), Ⅳ(18.7 g)and Ⅴ(10.5
g).Fraction Ⅰ was subsequent ly chromatographed
over Cosmosil 75 C18-OPN [ H2O-MeOH (1∶0※3∶
7)] to furnish compound 1(1.20 g).Repeated chro-
2　　 天然产物研究与开发 Vo1.14　No.1
matog raphy of f raction Ⅱ on Sephadex LH-20 [H2O-
MeOH (1∶0※1∶1)] , Cosmosil 75 C18-OPN [ H2O-
MeOH (1∶0※3∶7)] , and TSK gel Toyopearl HW-
40F [ H2O-MeOH (1:0※3:7)] , affo rded compounds
2(1.02 g)and 3 (0.47 g).Fraction Ⅳ was chro-
matog raphed on Cosmosil 75 C18-OPN [ H2O-MeOH
(1∶0※4∶6)] and then TSK gel Toyopearl HW-40F
[H2O-MeOH (1:0 ※1:1)] to yield compound 4
(1.07 g).
2.4　Identification
2.4.1 　Compound 1 , a tan amorphous powder.
[α] 22D-113.4°[ c = 0.91 , H2O] .UV λmax(H2O)
nm:252 , 282 , 316 (sh), 343.IR(KBr)cm-1:
3600 ～ 3300 (br.), 1692 , 1586 , 1521 , 1396 ,
1242 , 1115 , 820 , 800.ESI-MS m/ z :[ M +K ] +
833 , 795 , 757. Elemental analysis found C
48.15%, H 4.46%, calculated for C36H28 O16K2·
6H2O , C 47.89%, H 4.43%.1H NMR(300 MHz ,
D2O)δ:2.65 ～ 3.12(m , H-7”), 3.90 (br.s , H-
2), 4.46 (br.s , H-1), 4.84 (br.dd , H-8”), 4.98
(br.dd , H-8”), 6.52 (s , H-8), 6.87 (s , H-5),
7.53(s , H-4), 6.85 (d , J =2 Hz , H-2”), 6.76
(d , J =2 Hz , H-2”), 6.75 (d , J =8 Hz , H-5”),
6.67(d , J =8 Hz , H-5”), 6.62 (dd , J =2 and 8
Hz , H-6”), 6.37(dd , J =2 and 8 Hz , H-6”), 6.61
(d , J =2 Hz , H-2 ), 6.64 (d , J =8 Hz , H-5 ),
6.34(dd , J =2 and 8 Hz , H-6 ).13C NMR(100
MHz , D2O)δ:46.4(C-1), 48.4(C-2), 133.4(C-
3), 142.4 (C-4), 137.8 (C-4a), 119.4 (C-5),
145.7(C-6), 149.5(C-7), 119.8(C-8),126.2(C-
8a), 123.2(C-1 ), 117.6(C-2 ), 145.3(C-3 ),
146.2(C-4 ), 118.6(C-5 ), 122.1(C-6 ), 132.7
(C-1”), 133.0 (C-1”), 118.8 (C-2”), 145.0 (C-
3”), 145.2(C-3”), 146.4(C-4”), 119.1 (C-5”),
124.1(C-6”), 124.2 (C-6”), 39.1 (C-7”), 39.3
(C-7”), 79.6 (C-8”), 79.8 (C-8”), 179.3 (C-
9”), 179.7 (C-9”), 176.4 (2-COO-), 170.7 (3-
COO-).
2.4.2　Compound 2 , a tan amorphous powder.UV
λmax(H2O)nm :197 , 220 , 284 , 324.IR (KBr)
cm-1:3400 ～ 3000 (br.), 1692 , 1598 , 1521 ,
1447 , 1401 , 1263 , 1116 , 820 , 813.EI-MS m/ z :
413 [ M-K] +.Elemental analy sis found C 48.58%,
H 4.74%, calculated for C18 H15 O8K ·3H2O , C
47.79%, H 4.65%.1H NMR(400 MHz , D2O)δ:
7.08(s , H-2), 6.87(d , J =8 Hz , H-5), 6.97(d ,
J =8 Hz , H-6), 7.46(d , J =15.9 Hz , H-7), 6.26
(d , J =16 Hz , H-8), 5.06 (dd , J =3.2 and 8.8
Hz , H-10), 3.01 (dd , J =3.2 and 14.2 Hz , H-
11), 3.13(dd , J =8.8 and 14.2 Hz , H-11), 6.91
(s , H-13), 6.87 (d , J =7.8 Hz , H-16), 6.80(d ,
J =7.8 Hz , H-17).13C NMR(100 MHz , D2O)δ:
129.5 (C-1), 117.7 (C-2), 146.7 (C-3), 149.5
(C-4), 118.8 (C-5), 125.2 (C-6), 148.6(C-7),
117.7(C-8), 171.5(C-9), 79.0(C-10), 39.5(C-
11), 132.8(C-12), 119.8(C-13), 146.4(C-14),
145.3 (C-15), 118.6 (C-16), 124.4 (C-17),
179.7(C-18).These data were ident ical wi th those
of potassium rosmarinate[ 3 ,4] .
2.4.3　Compound 3 , a white amorphous powder.
UV λmax(H2O)nm:197 , 220 , 284 , 324.IR(KBr)
cm-1:3400 ～ 3200 (br.), 1692 , 1598 , 1516 ,
1455 , 1396 , 1262 , 1115 , 820 , 800.ESI-MS m / z:
[ M + K ] + 421.Elemental analy sis found C
50.72%, H 4.88%, calculated for C18 H15 O8Na·
3H2O , C 49.54%, H 4.82%.1H NMR(300 MHz ,
D2O)δ:7.06(d , J =2 Hz , H-2), 6.87(d , J =8
Hz , H-5), 6.95(dd , J =2 and 8 Hz , H-6), 7.45
(d , J =16 Hz , H-7), 6.25(d , J =16 Hz , H-8),
5.06(dd , J =4 and 9 Hz , H-10), 3.01(dd , J =4
and 14 Hz , H-11), 3.13(dd , J =9 and 14 Hz , H-
11), 6.91 (d , J =2 Hz , H-13), 6.86 (d , J =8
Hz , H-16), 6.80(dd , J =2 and 8 Hz , H-17).13C
NMR(100 MHz , D2O)δ:129.7(C-1), 117.1(C-
2), 146.8 (C-3), 149.6 (C-4), 118.8 (C-5),
125.3(C-6), 148.6 (C-7), 117.8 (C-8), 171.6
(C-9), 79.1(C-10), 39.5(C-11), 132.9(C-12),
119.9 (C-13), 146.4 (C-14), 145.3 (C-15),
118.8(C-16), 124.5(C-17), 179.8(C-18).These
data were ident ical wi th those of sodium rosmari-
nate[ 3 ,4] .
2.4.3　Compound 4 , a white amo rphous powder.
UV λmax (H2O)nm:214 , 286 , 310.IR (KBr)
cm-1:3500 ～ 3000 (br.), 1640 , 1596 , 1514 ,
1401 , 1275 , 1123 , 980 , 852 , 818.EIMS m / z:
194 , 179 , 150 , 135.1H NMR(400 MHz , D2O)δ:
7.11(s , H-2), 7.02 (d , J =8.1 Hz , H-5), 6.84
(d , J =8.1 Hz , H-6), 7.27 (d , J =15.9 Hz , H-
3Vo1.14　No.1 张慧桢等:新疆紫草中抗生育化学成分 　　
7), 6.32 (d , J =15.9 Hz , H-8), 3.83 (s , 3-
OCH3).13C NMR(100 MHz , D2O)δ:130.7 (C-
1), 113.6 (C-2), 150.1 (C-3), 149.1 (C-4),
118.2(C-5), 124.7 (C-6), 143.8 (C-7), 124.1
(C-8), 177.9 (C-9), 58.5 (3-OCH3).These data
w ere ident ical w ith those of sodium ferulate[ 4] .
References
1　Liu F , et al.Terminating the early pregnancy activity of
Arnebia euchroma in mice and rabbits.Journal of X injiang
Medical University , 1982 , 5:199
2　Isao A , et al.A tetrameric deriv ative of caffeic acid from
Rabdosia japonica.Phytochemistry , 1989 , 28(9):2447
3　Charles JK , et al.Carbon-13 nuclear magnetic resonance of
lithospermic and rosmarinic acids J Org Chem , 1975 , 40
(12):1804
4　Charles JK , et al.isoiation and.structure de termination of
litho spermic acid.J Org Chem , 1976 , 41(3):449
新疆紫草中抗生育化学成分
张慧桢1 , 2 　廖矛川2 　宣利江3 　郭济贤1
(1.复旦大学药学院　上海　200032;
2.上海市计划生育科学研究所国家计划生育药具重点实验室　上海　200032;
3.中国科学院上海药物研究所　上海　200031)
摘　要　从新疆紫草(Arnebia euchroma(Royle)Johnst.)的根部分得四种酚类化合物 , 经波谱分析 , 确定
为 rabdosiin 二钾盐(dipo tassium rabdo siin 1), 迷迭香酸钾盐(potassium rosmarinate 2), 迷迭香酸钠盐
(sodium rosmarinate 3), 阿魏酸钠盐(sodium ferulate 4)。其中 rabdosiin 二钾盐具有显著的抗生育活性 ,
而迷迭香酸钾盐 、迷迭香酸钠盐和阿魏酸钠盐为首次从该植物中分离获得。
关键词　新疆紫草;rabdosiin二钾盐;抗生育活性
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4　　 天然产物研究与开发 Vo1.14　No.1