全 文 ：New C_glycosylflavones from Tetrastigma hemsleyanum (Vitaceae)
LIU Dong1 , JU Jian_Hua1 , LIN Geng1 , XU Xu_Dong1 , YANG Jun_Shan1 , TU Guang_Zhong2
(1.Institute of Medicinal Plant Development , Chinese Academy of Medical Sciences and Peking Union Medical College , Bei jing 100094 , China;
2.Beijing Institute of Microchemistry Research , Beijing 100060, China)
Abstract:　Two novel C_glycosylflavones , apigenin_6_C_α_L_arabinopyranosyl_(1_4)_α_L_rhamnopyranoside(hemsleyanoside , 1) and apigenin_8_C_α_L_arabinopyranosyl_(1_4)_α_L_rhamno_pyranoside (isohems-
leyanoside , 2), together with a known compound(apigenin_6 ,8_di_C_β_D_glucopyranoside , 3), were isolated
from the 95%EtOH extract of Tetrastigma hemsleyanum Diels et Gilg.Their structures were elucidated by
chemical evidence and spectral analysis.
Key words:　Tetrastigma hemsleyanum ;C_glycosylflavone;hemsleyoside;isohemsleyoside
　　Tetrastigma hemsleyanum Diels et Gilg.(Vitaceae), which is native to China , distributes in the
east , middle , south and southwest provinces of China.As
a Chinese folk herb medicine , the whole herb or its rhi-
zome possesses the functions of antipyretic and detoxifica-
tion , antiinflammation , improving circulation and reliev-
ing pain.It is used for the treatment of infantile febrile
convulsion , pneumonia , asthma , hepatitis , rheumatism ,
irregular menstruation and sore throat[ 1 ,2] .No phyto-
chemical investigation of this species has ever been report-
ed.During the course of studying its effective con-
stituents , two new C_glycosylflavones hemsleyanoside (1)
and isohemsleyanoside (2)were isolated from the 95%
EtOH extract of this plant together with another known
flavonoid apigenin_6 ,8_di_C_β_D_glucopyranoside(3).
1　Results and Discussion
Compound 1 was obtained as yellowish powder
(MeOH), with mp of 218-220 ℃, [ α] 20D +9.0°(c
0.022 , MeOH), and responded to the Molish and Shino-
da(Mg_HCl)tests.The UV absorption(UV λMeOHmax nm:
270 , 336;277 , 329(sh), 396(NaOAc/H3BO3))and
the IR spectrum (IRνKBrmax cm-1:3 400 , 1 650 , 1 620 ,
1 485 , 1 100 , 1 050 , 840)implied that it was a flavone
glycoside.Acid hydrolysis revealed only rhamnose.The
EI_MS spectrum gave the peaks at m/z 384 (30), 283(100), 270 (61), 165 (30).The FAB_MS spectrum
gave its quasimolecular ion at m/ z 549(M++H)as well
as the ion at m/ z 403(M++H-146)consistent with a
molecular formula of C26H28O13 , which was confirmed by
1H-NMR and 13C-NMR spectra (Table 1).
The 13C-NMR spectrum gave the signal atδ108.9
which indicated the glycosyl moiety was attached to C_6 of
the aglycone
[ 3] .All these with the 1H-NMR spectrum(Table 1)suggested that compound 1 was a double_sugar
carbon glycoside of 5 , 7 , 4′_trihydroxyl flavone (api-
genin).The 13C_NMR spectrum(Table 1)gave nine car-
bon signals between δ68 and δ76 , namely δ75.5 ,
73.9 , 72.2 , 69.5 , 68.3 , 70.4 , 70.6 , 71.5 , 70.2 as
well as δ100.7 (anomeric carbon signal of rhamnose)
andδ17.7(C_6″signal of rhamnose).All these eleven
carbon signals were due to the two sugars of which the ex-
ternal onewas a rhamnose and the internal one was a pen-
tose.The pentose was deduced as arabinose , whose
anomeric carbon signal appeared atδ73.9 due to its con-
nection with the flavone at C_6.The C_4″signal of the
arabinose appeared atδ70.6 due to its connection with
the anomeric carbon of rhamnose.This can also be sup-
ported in the HMBC spectrum where δ5.00 (1H , d ,
J =1.5 Hz , Rha_H_1)corresponded with δ68.3 (C_
5 ), 70.4 (C_3 )of rhamnose and δ70.6(C_4″)of
arabinose.
Table 1　1H-NMR and 13C_NMR data of compounds 1 and 2 (in
DMSO_d6 , 1H-NMR in 500 MHz and 13C_NMR in 125 MHz)
No. 1 2δC δH (J , Hz) δC δH (J , Hz)
2 163.6 164.1
3 102.9 6.70 s 101.8 6.80 s
4 181.9 181.9
5 159.6 160.9
6 108.9 98.1 6.24 s
7 162.7 162.2
8 94.6 6.53 s 104.4
9 156.6 155.9
10 103.8 104.1
1′ 121.2 121.0
2′ 128.5 7.88(d , J=8.5) 129.5 8.28(d, J =8.5)
3′ 116.3 6.92(d , J=8.5) 115.9 6.88(d, J =8.5)
4′ 161.1 160.6
5′ 116.1 6.92(d , J=8.5) 115.9 6.88(d, J =8.5)
6′ 128.3 7.88(d , J=8.5) 129.5 8.28(d, J =8.5)
Ara
1″ 73.9 4.60 m 73.5 4.64(d, J =10.0)
2″ 75.5 76.1
3″ 72.2 72.6
4″ 70.6 71.0
5″ 69.5 69.6
Rha
1 100.7 5.00 brs 100.5 4.99 brs
2 70.2 70.2
3 70.4 70.4
4 71.5 71.5
5 68.3 68.0
6 17.7 0.54(d , J=6.0) 17.4 0.45(d, J =6.0)
Received:2000-12-20　Accepted:2001-03-22
Supported by the Key Project of the National Natural Science Foundation of China(29732040).
植　物　学　报　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　

Acta Botanica Sinica　2002 , 44(2):227-229
　　The above evidence unambiguously allows us to es-
tablish the structure of compound 1 as apigenin_6_C_α_L_
arabinopyranosyl-(1_4)_α_L_rhamnopyranoside (Fig.1).
It is a new C_glycosyl flavone , named as hemsleyanoside.
Compound 2 was isolated as yellowish powder
(MeOH), with mp of 216-218 ℃, [ α] 20D +8.8°(c
0.019 , MeOH), positive to theMolish and Shinoda(Mg_
HCl)tests.The UV spectrum(UVλMeOHmax nm:272 , 335;
278 , 329 (sh), 398 (NaOMe);278 , 302 , 348(AlCl3);278 , 302 , 348 (AlCl3/HCl);278 , 390(NaOAc);278 , 390 (NaOAc/H3BO3)) and the IR
spectrum(IRνKBrmax cm-1:3 400 , 1 650 , 1 620 , 1 485 ,
1 100 , 1 050 , 840)implied that it was a flavone glyco-
side.The EI_MS spectrum gave the peaks at m/ z 384(30), 283(100), 270 (61), 165 (30).The FAB_MS
spectrum gave its quasimolecular ion at m/ z 549(M++
H)as well as the ion at m/ z 403(M++H-146), con-
sistent with a molecular formula of C26H28O13 , which was
confirmed by
1
H_NMR and 13C_NMR spectra (Table 1).
Acid hydrolysis revealed only a rhamnose.Comparing its
EI_MS , UV , 1H-NMR and 13C_NMR spectra with com-
pound 1 , it was found that they were very similar except
thatδ108.9 andδ94.6 of compound 1 were substituted
forδ98.1 andδ104.4 of compound 2.We can conclude
that compound 2 was an isomer of compound 1 , namely
compound 2 was a C_glycosyl flavone at C_8.Therefore ,
compound 2 was characterized as apigenin_8_C_α_L_
arabinopyranosyl(1_4)_α_L_rhamnopyranoside (Fig.1).
It is also a new C_glycosylflavone , named as isohems-
leyanoside.
Fig.1.　Structures of compounds 1 and 2.
2　Experimental
2.1　General experimental procedures
Melting points were determined with Fisher_Jones(uncorrected).Optical rotations were measured with a
Perkin_Elmer 241 polarimeter.UV spectra were measured
with a Philips PYE Unican PU8800 spectrometer.IR
spectra were measured with a Peking_Elmer 983G spec-
trometer.NMR spectra were obtained with a Bruker AM_
500MHz spectrometer (500 MHz for 1H-NMR and 125
MHz for 13C_NMR).A ZAB_HS spectrometer was used to
record FAB_MS spectra.EI_MS spectra were obtained
with a KYKY_ZSP_50 spectrometer.Silica gel and
Sephadex LH_20 were used for column chromatography.
2.2　Plant material
Tetrastigma hemsleyanum Diels et Gilg.was collect-
ed from Jiuling Mountain of Jiangxi Province in January
1998 , and identified by Professor LIAN Wen_Yan , Insti-
tute of Medicinal Plant Development , Chinese Academy of
Medical Sciences and Peking UnionMedical College.
2.3　Extraction and isolation
The plant material(5.9 kg)was extracted with hot
ethanol for three times to afford EtOH extract(640 g)that
was suspended in water , and extracted with petroleum ,
CHCl3 , ethyl acetate and n_butanol , respectively.The
ethyl acetate residue (21.2 g)was chromatographed on
silica gel with a CHCl3_MeOH gradient system repeatedly
and purified on Sephadex LH_20 with MeOH to obtain
compound 1(65 mg), 2(15 mg)and 3(34 mg).
2.4　Identification
Hemsleyanoside (1)　Yellow powder.Mp 218-
220 ℃.[ α] 20D +9.0°(c 0.022 , MeOH).UV λMeOHmax
nm:270 , 336;277 , 329(sh), 396 (NaOMe);277 ,
302 , 348(AlCl3);277 , 302 , 348 (AlCl3/HCl);278 ,
392 (NaOAc);270 , 344 (NaOAc/H3BO3).IR νKBrmax
cm-1:3 400 , 1 650 , 1 620 , 1 485 , 1 100 , 1 050 ,
840.EI_MS m/ z (%):384 (30), 283 (100), 270
(61), 165 (30).FAB_MS m/z:549(M++H), 403(M++H -146).1H-NMR and 13C_NMR(DMSO_d6)
see Table 1.
Isohemsleyanoside (2)　Yellow powder.Mp 216-218 ℃.[α] 20D +8.8°(c 0.019 , MeOH).UV λMeOHmax
nm:272 , 335;278 , 329(sh), 398 (NaOMe);278 ,
302 , 348(AlCl3);278 , 302 , 348 (AlCl3/HCl);278 ,
390 (NaOAc);278 , 390 (NaOAc/H3BO3).IR νKBrmax
cm
-1:3 400 , 1 650 , 1 620 , 1 485 , 1 100 , 1 050 ,
840.EI_MS m/ z (%):384 (30), 283 (100), 270
(61), 165 (30).FAB_MS m/z:549(M++H), 403
(M++H -146).1H-NMR and 13C_NMR(DMSO_d6)
see Table 1.
Apigenin_6 , 8_di_C_β_D_glucopyranoside (3)　
Pale powder.Mp 256 -258 ℃.Molecular formula
C27H30O15.UV λMeOHmax nm:270 , 330;278 , 322 (sh),
394(NaOMe);276 , 302 , 352(AlCl3);276 , 302 , 350(AlCl3/HCl);277 , 390(NaOAc);277 , 312(NaOAc/
H3BO3).IRνKBrmax cm-1:3 400 , 2 960 , 1 640 , 1 620 ,
1 500 , 1 360 , 1 080.EI_MS m/ z(%):384(30), 283(100), 270(61), 165(30).FAB_MS m/ z:595(M+
+H).1H-NMR (DMSO_d6)δ:6.77 (1H , s , 3_H),
8.00(2H , d , J =8.0 Hz , 2′, 6′_H), 6.90(2H , d ,
J =8.0 Hz , 3′, 5′_H), 4.65(1H , d , J =8.0Hz , H_
1 , 6_glu), 4.91 (1H , d , J =8.0 Hz , H_1 , 8_glu).
13C_NMR(DMSO_d6)δ:164.0 (C_2), 103.2 (C_3),
182.2(C_4), 158.5(C_5), 107.4(C_6), 160.9(C_
7), 105.2(C_8), 155.0(C_9), 103.8(C_10), 121.4
228　 植物学报　Acta Botanica Sinica　Vol.44　No.2　2002
(C_1′), 128.9(C_2′), 115.8(C_3′), 161.1 (C_4′),
115.7 (C_5′), 128.6 (C_6′);6_glu:74.0 (C_1″),
71.9 (C_2″), 78.8 (C_3″), 70.5 (C_4″), 81.8 (C_
5″), 61.2(C_6″);8_glu:73.2(C_1 ), 70.9(C_2 ),
77.7(C_3 ), 69.0(C_4 ), 80.8 (C_5 ), 59.7(C_
6 ).It was identified by comparison with authentic sam-
ple[ 3] .
References:[ 1] 　Jiangsu New Medical College(江苏新医学院).Dictionary
of Chinese Traditional Medicine.Shanghai:Shanghai Peo-
ples Publishing House , 1977.2123.(in Chinese)
[ 2] 　Editing Group of “ Collection of Chinese Traditional and
Herbal Drugs” (“全国中草药汇编”编写组).Collection
of Chinese Traditional and Herbal Drugs.Beijing:Peoples
Health Publishing House , 1982.31.(in Chinese)
[ 3] 　Yu D_Q(于德泉), Yang J_S (杨峻山).Handbook of
Analytical Chemistry.Vol.7.2nd ed.Beijing:Chemical
Industry Press , 1999.836-837.(in Chinese)
三叶崖爬藤中的新黄酮碳甙
刘　东1　鞠建华1　林　耕1　许旭东1　杨峻山1　涂光忠2
(1.中国协和医科大学中国医学科学院药用植物研究所 , 北京 100094;2.北京微量化学研究所 , 北京 100083)
摘要:　从三叶崖爬藤(Tetrastigma hemsleyanum Diels et Gilg.)的 95%乙醇提取物中分离得到 3 个黄酮碳甙 , 经化学
方法和光谱分析鉴定为:5 , 7 , 4′_三羟基黄酮_6_α_L_吡喃鼠李糖(1_4)_α_L_吡喃阿拉伯糖甙(1), 5 , 7 , 4′_三羟基黄酮_8_
α_L_吡喃鼠李糖(1_4)_α_L_吡喃阿拉伯糖甙(2), 5 , 7 , 4′_三羟基黄酮_6 , 8_二_C_β_D_吡喃葡萄糖甙(3), 1 和 2 为新化合
物 ,分别命名为崖爬藤甙和异崖爬藤甙。
关键词:　三叶崖爬藤;黄酮碳甙;崖爬藤甙;异崖爬藤甙
中图分类号:R914　　　文献标识码:A　　　文章编号:0577-7496(2002)02-0227-03
收稿日期:2000-12-20　接收日期:2001-03-22
基金项目:国家自然科学基金重点资助项目(29732040)。
(责任编辑:王　葳)
LIU Dong et al:The New C_glycosylflavones from Tetrastigma hemsleyanum (Vitaceae) 229