全 文 ：簇序草化学成分的研究
岳建民1　陈绍农1　杨升平1　樊成奇1　林中文2　孙汉董2
(1.中国科学院上海生命科学研究院药物研究所 , 上海 200031;2.中国科学院昆明植物研究所 , 昆明 650204)
摘要:　首次从簇序草(Craniotome furcata (Link.)O.Kuntze)的乙酸乙酯部分分离到化合物 cranioside A(1)、 cranio-
side B(2)、mussaenoside(3)和 ningpogenin(4)。利用波谱方法(1H-NMR、13C-NMR 和 ESI_MS 等)对这些化合物的结
构进行了鉴定。其中 1和 2 为新化合物。
关键词:　簇序草;唇形科;cranioside A;cranioside B;mussaenoside;ningpogenin
中图分类号:R914　　　文献标识码:A　　　文章编号:0577-7496(2001)11-1199-03
Chemical Components from Craniotome furcata
YUE Jian_Min1＊ , CHEN Shao_Nong1 , YANG Sheng_Ping1 , FAN Cheng_Qi1 ,
LIN Zhong_Wen2 , SUN Han_Dong2
(1.Institute of Materia Medica , Shanghai Institute for Biological Sciences , The Chinese Academy of Sciences , Shanghai 200031 , China;
2.Laboratory of Phytochemistry , Kunming Institute of Botany , The Chinese Academy of Sciences , Kunming 650204, China)
Abstract:　Four compounds , craniosides A (1)and B (2), mussaenoside (3)and ningpogenin (4)were
isolated from the ethyl acetate fraction of Craniotome furcata (Link.)O.Kuntze for the first time.Among
them , craniosides A(1)and B(2)were identified as new compounds.The structures of the two new com-
pounds were assigned mainly by spectral methods.
Key words:　Craniotome furcata;Labiatae;cranioside A;cranioside B;mussaenoside;ningpogenin
　　Craniotome furcata (Link.)O.Kuntze , the only
species of the genus Craniotome (Labiatae), is a herba-
ceous plant and is mainly distributed in Yunnan and
Sichuan provinces of China
[ 1] .The chemical components
of this plant have never been investigated.In an effort to
identify the compounds with important bioactivity and
chemical diversity , an initial chemical research of the
aerial parts of C.furcata collected from Lijiang of Yun-
nan Province was carried out.Four compounds , cranio-
sides A (1)and B (2), mussaenoside (3)and ning-
pogenin(4)were identified from the ethyl acetate soluble
fraction of C.furcata.The components , craniosides A(1)and B(2), were assigned to be new compounds.In
the present paper , we report the isolation and structure
elucidation of these four compounds.
1　Results and Discussion
Cranioside A (1)was isolated as white amorphous
powder.The molecular formula C16H20O7was deduced by
13
C-NMR(DEPT)and EIMS.The spectral data indicated
the presence of hydroxyl groups (IR 3 415 cm-1), a
methoxy group(1H_NMRδ3.79 , s , 3H)and one ester
group(IR 1 697 cm-1 , 13C_NMRδ166.26).1H_NMR
spectrum of 1 showed the signals for a pair of trans
olefinic protons(6.45(1H , d , J =15.9 Hz)and 7.62(1H , d , J =15.9 Hz)), a 1 , 4_disubstituted benzene
ring (6.79(2H , d , J =8.7Hz)and 7.68(2H , d , J
=8.7 Hz))and one methoxyl group 3.79(1H , s), in-
dicating the possible presence of p_methoxycinnamoyl
group.An anomeric proton(6.45(1H , d , J =4.2 Hz)
and a methyl group 1.05 (3H , d , J =6.2 Hz)in the
1H_NMR spectrum , and 13C_NMR signals at 94.1 and
17.7 suggested the presence of a rhamnose moiety.The
coupling constant of anomeric proton(J =4.2 Hz)indi-
cates a β_rhamnose.In the case of an α_rhamnose , the
coupling constant normally appears at approximately 1-2
Hz[ 2] .The down field shifted signal of anomeric proton at
6.45(1H , d , J =4.2 Hz , H_1′)and carbon signal(C_
1′)of β_rhamnose at 94.1 indicated that the C_1′of β_
rhamnose bore the p_methoxycinnamoyl group.This pro-
posal was supported by the EIMS ion peaks at m/ z 324
[ M] + andm/ z 178 [M-146(rha)] +.The structure of
cranioside A was thus elucidated to be 1.
Cranioside B (2)was isolated as white amorphous
powder.The molecular formula C21H26O14was deduced by
13
C_NMR(DEPT)and ESI_MS.The IR spectrum indi-
cated the presence of hydroxyl groups(IR 3 373 cm-1),
a carbonyl group (1 699 cm-1)and an aromatic ring
(1 637 , 1 610 and 1 520 cm-1).The 1H_NMR spectrum
of 2 showed the signals for a pair of trans olefinic protons(6.19(1H , d , J =15.9 Hz)and 7.48(1H , d , J =
15.9 Hz))and a 1 ,4_disubstituted benzene ring (6.63(2H , d , J =8.4 Hz)and 7.27 (2H , d , J =8.4
Hz)).The 13C_NMR of 2 exhibited a carbon signal at
Received:2000-09-28　Accepted:2001-04-23
植　物　学　报　2001 , 43(11):1199-1201 　 　 　 　 　 　 　
Acta Botanica Sinica
Fig.1.　Structures of compounds 1-4.
169.7 and carbon signals for a 1 ,4_disubstituted benzene
ring (Table 1).The characteristics of proton signals at
the down field of the 1H_NMR and the down field carbon
signals in the 13C_NMRwere very similar to those of cran-
ioside A(1), except for the absence of a methoxyl group.
The above_mentioned spectral data suggested the presence
of a p_coumaroyl group.Basic hydrolysis of 2 gave glu-
cose , glucuronic acid and p_coumaric acid(monitored by
TLC and PC).Positive ESI_MS only showed two ion
peaks at m/ z 503 [M +H] + and m/z 674 [ 2×(M -
C9H9O3)] +.The ESI_MS fragment at m/ z 674 corre-
sponding to a two_times_ion of the loss of a coumaroyl
group and one molecularwater [M-C9H7O2-H2O] + , a
typical feature of ESI_MS , indicated the presence of a se-
quence of two sugar units.The configuration of the
anomeric center and the sequence of sugar moiety were as-
signed to be _(β_D_glucopyranosyluronyl_(6_1)_β_D_glu_
copyranosyl)on the basis of both the chemical shift of the
Table 1　13C_NMR data of craniosides A(1)and B(2)＊
Carbons
Cranioside A(1)1) Cranioside B(2)2)
p_Methoxy-
cinnamoyl
Rha
p_
Coumaroyl
GlcUA Glc
1(1′, 1″) 166.3 94.1 170.0 94.5 98.7
2(2′, 2″) 115.6 71.7 115.4 72.2 74.3
3(3′, 3″) 144.3 68.1 147.2 75.9＊ 75.3＊
4(4′, 4″) 126.7 74.3 127.6 72.5 71.3
5(5′, 5″) 130.1 65.4 131.6 76.7 78.4
6(6′, 6″) 114.4 17.7 117.3 169.6 65.3
7 161.1 161.7
8 114.4 117.3
9 130.1 131.6
—OMe 55.3
＊ The assignments for the carbons may be interchanged.1)13C_NMR data
of cranioside A(1)were measured in DMSO_d6.2)13C_NMR data of cranio-
side B(2)were recorded in CD 3OD.
anomeric carbon and proton signals(see Table 1 and ex-
perimental)[ 3] .The C_1′signal of glucouronyl at 94.5
and the C_1 signal of coumaroyl at 169.7 indicated that
the coumaroyl group was attached to the C_1′position of
glucouronyl group[ 4] .The structure of cranioside B (2)
was therefore assigned to be 1_O_p_Coumaroyl_β_D_glu-
copyranosyluronyl_(6_1)_β_D_glucopyranoside.
Two known compounds—mussaenoside (3) and
ningpogenin(4)—were also isolated and identified from
this plant for the first time.The structures of the two
known compounds were identified on the basis of spectral
data[ 5 , 6] .
2　Experimental
2.1　General experimental procedures
IR spectrum was measured using a Nicolet Magna
750 spectrometer with KBr discus.NMR spectrum was
obtained using a Brucker Am_400 MHz spectrometer.
General 1H_NMR data were obtained at 400 MHz , and
13C_NMR was measured at 100.6 MHz.ESI_MS and
EIMS were respectively recorded with a Finnigan LCQDE-
CA mass spectrometer and a Finnigan MAT 95 mass
spectrometer.
2.2　Plant material
The whole plant of Craniotome furcata (Link.)O.
Kuntze was collected at Lijiang , Yunnan Province , Chi-
na.The plant was authenticated by Professor LIN Zhong_
Wen , Kunming Institute of Botany , The Chinese Acade-
my of Sciences , where a voucher specimen was deposited.
2.3　Extraction and separation
The air_dried and powdered whole herb of C.furca-
ta (2.5 kg)was extracted three times with 95%EtOH at
room temperature.The extract was evaporated to give
160_g dry powder under reduced pressure.The crude ex-
tract was dissolved in 300_mL methanol and decolorized
on an MCI GEL CHP20P column to obtain 147_g brown
syrup.It was then dissolved in water(2 L)and the aque-
ous suspension was extracted with ethyl acetate and
n_butanol to give fractions E (21 g)and N(56 g), re-
spectively.The aqueous solution was evaporated to dry-
ness under reduced pressure to afford fraction W (71 g).
Part E(21 g)was chromatographed on a column of
silica gel(200 g)eluting with chloroform_methanol(4∶1 ,
3∶1 , 2∶1 , 1∶1 and methanol)to give fractions 1-21.
The 3rd and 4th fractions were combined and rechro-
matographed on a C_18 silica gel column eluting with
methanol_water(8∶2)to give ningpogenin(4)(50 mg).
The fractions 8-11 were combined and chromatographed
on silica gel column to yield cranioside A (1)(1.2 g).
The fraction 15 was chromatographed on the column of C_
18 silica gel with elute MeOH_H2O (6∶4)to yield mus-
saenoside (3)(37 mg).The fractions 18 ,19 were com-
bined and chromatographed on a column of MCI GEL CHP
20P with methanol_water(7∶3)to give a major fraction ,
which was then rechromatographed on a C_18 silica gel
column eluting with methanol_water(6∶4)to afford cran-
ioside B(2)(40 mg).
1200　 植　物　学　报　　Acta Botanica Sinica 43 卷
2.4　Identification
Cranioside A (1)　C16H20O7 , white amorphous
powder.IR(cm-1):3 415 (—OH), 2 997 , 2 924 ,
1 697 (carbonyl), 1 630 , 1 605 and 1 512 (aromatic
ring and double bond).1H_NMR (DMSO_d6)δ:1.05(3H , d , J =6.2 Hz , H_6′), 3.79 (3H , s , —OMe),
3.90(1H , m , H_5′), 4.75(1H , d , J =6.8 Hz , H_
3′), 4.90 (1H , d , J =4.2 Hz , H_2′), 4.95 (1H ,
dd , J =6.8 , 6.8 Hz , H_4′), 6.45(1H , d , J =4.2
Hz , H_1′), 6.50 (1H , d , J =15.9 Hz , H_3), 6.79(2H , d , J =8.7 Hz , H_6 , 8), 7.62 (1H , d , J =
15.9 Hz , H_2), 7.68(2H , d , J =8.7 Hz , H_5 , 9).
13C_NMR data are shown in Table 1.EIMS m/ z(%):
324 [M] +(5), 178 [ M-146] +(63)and 161 [M -
163] +(100).
Cranioside B (2)　C21H26O14 , white amorphous
powder.IR (cm-1):3 373 (—OH), 2 904 , 1 699(carbonyl), 1 637 , 1 610 and 1 520(aromatic ring and
double bond).1H_NMR (CD3OD)δ:3.02(1H , m),
3.10-3.30 (7H , m), 3.38(1H , m), 3.55 (1H ,
dd), 3.84(1H , m), 4.05-4.17 (3H , m), 4.30-
4.45 (4H , m), 4.95 (1H , d , J =3.7 Hz , H_5′),
6.19(1H , d , J =15.9 Hz , H_3), 6.63(2H , d , J =
8.7 Hz , H_6 , 8), 7.27(2H , d , J =8.7 Hz , H_5 ,
9), 7.48(1H , d , J =15.9 Hz , H_2).13C_NMR data
are shown in Table 1.Positive ESI_MS m/ z (%):503
[M+H] + and 674 [ 2×(M-C9H7O2-H2O)] +.
Mussaenoside(3)　C17H26O10 , white amorphous
powder.1H_NMR(CD3OD)δ:5.30(1H , d , J =4.0
Hz , H_1), 7.23(1H , s , H_3), 3.00(1H , m , H_5),
2.10 (1H , m , H_6α), 1.25(1H , m , H_6β), 1.55(1H , m , H_7), 2.05(1H , dd , J =4.2 , 9.3 Hz , H_
9), 1.18 (3H , s , H_10), 3.55 (3H , s , —OMe),
4.25(1H , d , J =7.8 Hz , H_1′), 3.0-3.25 (3H ,
m , H_2′, 3′, 4′, 5′), 3.45(1H , m , H_6′a)and 3.72
(1H , m , H_6′b).13H-NMR(CD3OD)δ:95.8(C_1),
152.4(C_3), 113.8(C_4), 32.4(C_5), 31.2(C_6),
41.2(C_7), 80.9(C_8), 52.2(C_9), 25.1 (C_10),
169.8 (C_11), 52.7(—OMe), 100.2 (C_1′), 75.1(C_2′), 78.7(C_3′), 72.1(C_4′), 78.3(C_5′)and
63.3 (C_6′).Positive ESI_MS m/ z (%):391 [M +
H] +(100).
Ningpogenin (4)　C9H14O3 , white amorphous
powder.1H_NMR(DMSO_d6)δ:4.93(1H , br d , J =
7.3 Hz , H_1), 3.60 -3.75 (2H , m , H_3), 1.88(1H , m , H_4α), 1.75 (1H , m , H_4β), 3.00 (1H ,
m , H_5), 2.88(1H , m , H_6), 5.55(1H , s , H_8),
3.60 (2H , m , H_9)and 4.10 (2H , br s , H_10).
13C_NMR (DMSO_d6)δ:86.9 (C_1), 67.1(C_3),
28.1(C_4), 43.3(C_5), 49.0(C_6), 149.5(C_7),
126.2(C_8), 61.6 (C_9)and 60.1 (C_10).Positive
ESI_MS m/z(%):193 [M+Na] +(100)and 363 [ 2M
+Na] +.
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(责任编辑:王　葳)
11 期 岳建民等:簇序草化学成分的研究(英) 1201