全 文 ：Lignans from Gardneria multiflora
XIE Guang-Hui1 , MA Lei2 , ZHENG Zong-Ping2 , HU Li-Hong1 ,2＊
1 School of Pharmacy , East China University of Science &Technology , Shanghai 200237 ;
2 Shanghai Research Center for Modernization of Traditional Chinese Medicine , Shanghai Institute of Materia Medica , Shanghai 201203 ,
China
【ABSTRACT】　AIM:Lignan compounds were expected to be obtained from Gardneria multiflora.METHODS:The con-
stituents were isolated and purified by column chromatography and the structures were identified by spectral analysis.
RESULTS:Four lignans with dibenzylbutyrolactone skeleton and a dihydrobenzofuran neolignan were obtained as mutiflinoside
(1), trachelosiaside(2), (-)-arctigenin(3), matairesinoside(4), sisymbrifolin(5).CONCLUSION:All the compounds
were obtained from this plant for the first time.Lignan 1 was structurally identified to be a new compound , and a rare C-glu-
cosyl-lignan.
【KEY WORDS】　Gardneria multiflora;lignans;C-glucosy l-lignan
【CLCNumber】　R284.1　　【Document code】　A　　【Ariticle ID】　1672-3651(2007)04-0255-04
【Received on】　2007-06-15
【＊Corresponding author】　HU Li-Hong:Professor , Tel(Fax):86-21-
50272221;E-mai l:simmhulh@mail.shcnc.ac.cn
　　Alkaloids (more than 18 compounds)have been
isolated from the plants of Gardneria spp.(Loganiace-
ae).They belong to monoterpenoid indole alkaloids
possessing a sarpagine skeleton
[ 1] .But no lignans have
been isolated from this genus before.We have investi-
gated the constituents of the whole plant of Gardneria
multiflora , and resulted in the isolation of five lignans.
They are mutiflinoside (1), trachelosia-side (2) ,
(-)-arctigenin(3), matairesinoside (4)and sisymb-
rifolin(5), respectively.Mutiflinoside (1)was a new
rare C-glucosyl-lignan.In the paper , we wish to de-
scribe the isolation and structural elucidation of the
above lignans , especially the new compound , mutiflino-
side (1).
Fig 1　Chemical structure of compounds 1 and 2
1　Results and Discussion
The molecular formula of mutiflinoside(1)was de-
termined as C27H32O13 by HR-ESI-MS from the [M +
Na] + and [M-H] - signals at m z 587.174 4(positive)
and 563.176 7(negative mode), respectively.The UV
spectrum of 1 showed absorptionmaxima at 293 and 308
nm.Its IR spectrum revealed the presence of a lactone
ring (1 764 cm-1), hydroxy (3 434 cm-1)and an un-
saturated ketofunction (1 654 cm-1).The 1 H NMR
spectrum indicated two sets of tetrasubstituted aromatic
ring signals , at δ:6.58 (1H , d , J =1.5 Hz)and
6.75(1H , d , J = 1.5 Hz), and at δ:7.05 (2H ,
s).In the 1H NMR spectrum , a signal at δ:4.49
(1H , d , J =9.0 Hz)suggested a proton attached to
C-1 of a β-D-glycosyl moiety[ 2] .This proton was attri-
buted using an HMQC experiment to a carbon at δ:
78.4 , a shift found in C-glucosides[ 3] ;The HMQC and
HMBC map disclosed that all sugar carbon atoms were
due to the remained carbons in the δ:60-82 range[ 2] .
The hexose was identified as β-D-glucopyranose on the
basis of its
1
H NMR and
13
C NMR data
[ 4] .A clear
HMBC correlation between the anomeric proton of this
glucosyl and C-5 in the lignan moiety substantiated the
linkage position.Abe et al.had reported trachelosia-
side (2)isolated from Trachelospermum asiaticum[ 3] .
Comparing the carbon resonances of 1 with those of
　2007年 7月　第 5卷　第 4期 Chin J Nat Med　July 2007　Vol.5　No.4　255　
trachelosiaside (2) , the C-7′has been oxygenated ,
down-field shifting to δ:198.4 , and C-5′position was
linked to the methoxyl group.The CD curve of 1
showed a negative Cotton effect at around 336 nm , and
the optical rotation of compound 1 ([ α] 20D -2.3°, c
1.5 , MeOH )showed it was levorotatory[ 5] .Therefore ,
the absolute configuration was indicated to be 8R , 8′
R .Consequently , 1 was proved to be 5′-methoxy-7′-
oxo-trachelosiaside , named mutiflinoside. To our
knowledge , it might be the third example [ The first
compound was trachelosiaside
[ 3]
and the second com-
pound was 8′-hydrotrachelosiaside[ 6] .] of natural occur-
ring C-glucoside of lignan.
2　Experimental
2.1　General experimental procedures
UV spectra were obtained on a Shimadzu UV-
2501PC spectrophotometer.Melting points were deter-
mined using a X-4 digital micromelting point apparatus
and uncorrected.1H NMR(500 MHz)and 13C NMR
(125 MHz)spectra were recorded with Brucher ACF-
500 NMR spectrometer.ESI-MS was collected on Es-
quire 3000 plus 01005 spectrometers.All solvents
used were of analytical grade (Shanghai Chemical
Plant).Column chromatography consisted of the follow-
ing :Silica Gel(200-300mesh and thin-layer H;Qing-
dao Marine Chemical Ltd., Qingdao , China), Sepha-
dex LH-20 25-100 μm (Pharmacia Fine Chemical Co.
Ltd.), andMCI gel CHP 20P 75 ～ 150μm(Mitsubishi
Chemical Corporation).TLC was performed using a sili-
ca gel (GF254 , Yantai Huiyou Silica Gel Co.Ltd.,
Shandong).
2.2　Plant materials
Gardneria multiflora were collected in Nanchuan
County , Chongqing City , China and identified by Si-
Rong Yi(The Plant Garden of Chongqing).A voucher
specimen (2001007)was deposited in the Shanghai Re-
search Center for Modernization of Traditional Chinese
Medicine , Shanghai Institute of Materia Medica.
2.3　 Extraction and isolation
The dried and powdered (2.0 kg)plant was ex-
tracted with CH3OH three times at boiling temperature.
The residue was separated by column of silica gel with a
gradient mixture of CHCl3-MeOH to give four fractions
(A-D).Fraction B (CHCl3-MeOH , 50∶1)was sepa-
rated into subfractions by MCI-gel for six fractions ,
namely B1-B6 fractions.Fraction B2 (H2O-CH3OH ,
40:60)was separated by column of silica gel with
CHCl3 to give compound 3 (1 895 mg).Fraction D
(CHCl3-MeOH , 1:1)was separated into subfractions
by MCI-gel for six fractions , namely D1-D6 fractions.
Fraction D3 separated by column of silica gel with
CHCl3-MeOH(10∶1)to give compound 1(122 mg).
Fraction D4 separated by column of silica gel with
CHCl3-MeOH(10∶1)to give compound 2(725 mg), 5
(35 mg)and CHCl3-MeOH(15∶1)to give compound 4
(110 mg).
3　Identification
Mutiflinoside (1)　 amorphous brownish white
powder;mp 114 ～ 116 ℃(MeOH);[ α] 20D-2.3°(c
1.5 , MeOH);UV(CH3OH)λmax(logε):293(4.29),
308(4.30)nm;IRυmax(KBr)cm-1:3 423 , 1 764 , 1
654 , 1 517 , 1 459 , 1 361 , 1 024 , 750;1 H NMR
(CD3OD , 500 MHz)δ:3.84(6H , s , CH3O-3′, 5′),
3.60(3H , s , CH3O-3), 6.58(1H , d , J =1.5Hz ,
H-2), 6.75 (1H , d , J = 1.5 Hz , H-6), 2.67 ,
3.12 (2H , m , H-7), 3.46 (1H , m , H-8), 7.05
(2H , s , H-2′, 6′), 4.37(1H , dd , J =16.7 , 8.3
Hz , H-8′), 4.00(1H , t , J =8.4Hz , H-9′), 4.41
(1H , d , J = 8.5 Hz , H-9′), 4.49(1H , d , J =
9.0 Hz , H-1″), 3.45 (1H , m , H-2″), 3.42 (1H ,
m , H-3″), 3.40(1H , m , H-4″), 3.36(1H , m , H-
5″), 3.72 (1H , dd , J = 11.2 , 5.1 Hz , H-6″),
3.84(1H , d , J = 6.1 Hz , H-6″);13C NMR(CD3
OD , 125MHz)δ:57.6(q , CH3O-3′, 5′), 56.8(q ,
CH3O-3), 130.1(s , C-1), 113.7(d , C-2), 149.2
(s , C-3), 145.2 (s , C-4), 127.1 (s , C-5), 122.4
(s , C-6), 36.6(t , C-7), 47.3(d , C-8), 180.5(s ,
C-9), 128.5(s , C-1′), 108.2(s , C-2′, 6′), 149.5
(s , C-3′, 5′), 143.7 (s , C-4′), 198.4(s , C-7′),
48.9(d , C-8′), 78.4 (t , C-9′), 78.4(d , C-1″),
80.3(d , C-2″), 76.2 (d , C-3″), 72.2 (d , C-4″),
82.4 (d , C-5″), 63.5 (t , C-6″);HR-ESI-MS
(pos.):587.174 4 ([M +Na] + , C27H32NaO13 calc.
587.174 1).HR-ESI-MS (neg.):563.1767 ([ M-
H] - , C27H31O13;calc. 563.1765);CD Cotton:
[θ] 336 51415.
Trachelosiaside (2)　amorphous brownish white
powder , C26H32O11;1H NMR(300 MHz , CD3OD)δ:
256　　Chin J Nat Med　July 2007　Vol.5　No.4 　2007年 7月　第 5卷　第 4期
6.58(1H , d , J =1.8 Hz , H-2), 6.75(1H , d , J
=1.8 Hz , H-6), 2.80 , 2.79(2H , m , H-7), 2.59
(1H , m , H-8), 3.74 (6H , s , CH3O -3 , 3′), 6.59
(1H , d , J = 1.5 Hz , H-2′), 6.88 (1H , d , J =
7.8 Hz , H-5′), 6.51(1H , dd , J =7.8 , 1.5 Hz ,
H-6′), 2.51(2H , m , H-7′), 2.53(1H , m , H-8′),
4.09 , 3.85(2H , m , H-9′), 4.58(1H , d , J =8.7
Hz , H-1″), 3.49(1H , m , H-2″), 3.51(1H , m , H-
3″), 3.42 (1H , m , H-4″), 3.59 (1H , m , H-5″),
3.70 , 3.56(2H , m , H-6″);13C NMR(75.0 MHz ,
CD3OD)δ:130.3 (C , C-1), 113.2 (CH , C-2),
149.1(C , C-3), 144.9(C , C-4), 126.6(C , C-5),
122.5(CH , C-6), 35.5(CH2 , C-7), 47.9(CH , C-
8), 181.8(C=O , C-9), 131.6 (C , C-1′), 113.6
(CH , C-2′), 149.1 (C , C-3′), 146.2 (C , C-4′),
116.4(CH , C-5′), 122.4(CH , C-6′), 39.0(CH2 ,
C-7′), 42.74(CH , C-8′), 73.1(CH2 , C-9′), 77.9
(CH , C-1″), 80.2 (CH , C-2″), 75.7 (CH , C-3″),
72.0(CH , C-4″), 82.4(CH , C-5″), 63.2(CH2 , C-
6″).Identified by comparison with literature values[ 3].
(-)-arctigenin (3)　Gum , C21H24O6 , EI-MS
m z 372 [ M] +;[ α] 23D -37°(c 1.5 , EtOH);
1
H NMR(300 MHz , CDCl3)δ:6.56(1H , d , J =
1.5 Hz , H-2), 6.73 (1H , d , J =7.8 Hz , H-5),
6.53(1H , dd , J =7.8 , 1.5Hz , H-6), 2.83(2H ,
dd , J =11.1 , 6.3Hz , H-7), 2.51(1H , m , H-8),
6.40(1H , d , J =1.8 Hz , H-2′), 6.66(1H , d , J
=8.1 Hz , H-5′), 6.46 (1H , dd , J = 8.1 , 1.8
Hz , H-6′), 2.41(2H , m , H-7′), 2.46(1H , m , H-
8′), 3.78 , 4.04 (2H , m , H-9′);13 C NMR (75.0
MHz , CDCl3)δ:129.1 (s , C-1), 111.4(d , C-2),
146.5(s , C-3), 144.2(s , C-4), 114.0(d , C-5),
121.6(d , C-6), 34.1 (t , C-7), 46.1 (d , C-8),
178.6(s , C-9), 130.2(s , C-1′), 111.5(d , C-2′),
148.6(s , C-3′), 147.3 (s , C-4′), 110.9 (d , C-
5′), 120.2(d , C-6′), 37.6(t , C-7′), 40.6(d , C-
8′), 71.0(t , C-9′).Identified by comparison with lit-
erature values
[ 7] .
Matairesinoside (4)　amorphous brownish white
powder , C26H32O11;1H NMR(300 MHz , CD3OD)δ:
6.75(1H , d , J =1.8 Hz , H-2), 7.05(1H , d , J
=8.1 Hz , H-5), 6.32 (1H , dd , J = 8.1 , 1.8
Hz , H-6), 2.68 , 3.78 (2H , m , H-7), 3.78(1H ,
m , H-8), 3.88 (3H , s , OCH3), 3.77 (3H , s ,
OCH3), 6.56(1H , d , J =1.8 Hz , H-2′), 6.68
(1H , d , J =8.1 Hz , H-5′), 6.50 (1H , dd , J =
8.1 , 1.8 Hz , H-6′), 2.48 (2H , m , H-7′), 3.38
(1H , m , H-8′), 3.91 , 4.18 (2H , m , H-9′), 4.86
(1H , d , J =7.5 Hz , H-1″), 3.86(1H , m , H-2″),
3.52(1H , m , H-3″), 3.48 (1H , m , H-4″), 3.48
(1H , m , H-5″), 3.66 , 3.70 (2H , m , H-6″);13 C
NMR(75.0 MHz , CD3 OD)δ:134.3 (C , C-1),
114.9(CH , C-2), 150.7(C , C-3), 146.9 (C , C-
4), 117.9 (CH , C-5), 123.1(CH , C-6), 35.4
(CH2 , C-7), 47.9 (CH , C-8), 181.6 (C=O , C-
9), 131.5 (C , C-1′), 113.4 (CH , C-2′), 149.2
(C , C-3′), 146.5 (C , C-4′), 116.3(CH , C-5′),
122.4(CH , C-6′), 39.0 (CH2 , C-7′), 42.7 (CH ,
C-8′), 73.1(CH2 , C-9′), 103.0(CH , C-1″), 78.3
(CH , C-2″), 75.0 (CH , C-3″), 71.4 (CH , C-4″),
77.9(C-5″), 62.6 (CH2 , C-6″).Identified by com-
parison with literature values
[ 3] .
Sisymbrifolin (5)　gum , C20 H24 O8;1 H NMR
(300MHz , CD3OD)δ:6.94(1H , d , J =2.6 Hz ,
H-2), 6.82 (1H , dd , J = 8.2 , 1.7 Hz , H-6),
6.76(1H , d , J =8.1 Hz , H-5), 5.53(1H , d , J
=6.2 Hz , H-7), 6.94(1H , s , H-2′), 6.90 (1H ,
s , H-6′), 4.57 (1H , d , J = 6 Hz , H-7′), 3.87
(3H , s , OCH3), 3.81(3H , s , OCH3), 3.77 (2H ,
m , H-9), 3.70(1H , m , H-8′), 3.53 , 3.39(2H ,
m , H-9′), 3.35 (1H , m , H-8);13 C NMR (75.0
MHz , CD3OD)δ:137.1(C , C-1), 110.9(CH , C-
2), 149.4(C , C-3), 147.8(C , C-4), 116.5(CH ,
C-5), 120.0 (CH , C-6), 89.4 (CH , C-7), 55.6
(CH , C-8), 65.1 (CH2 , C-9), 139.8 (C , C-1′),
113.0(CH , C-2′), 145.5(C , C-3′), 149.2(C , C-
4′), 134.9 (C , C-5′), 116.9 (CH , C-6′), 75.7
(CH , C-7′), 77.8 (CH , C-8′), 64.6 (CH , C-9′).
Identified by comparison with literature values
[ 8].
References
[ 1] 　Aimi N , Sakai S , Ban Y.The Alkaloids[ M] .Academic Press ,
New York , 1989 , 36:1-68.
[ 2] 　Agrawal PK.NMR spect roscopy in the structural elucidation of
oligosaccharides and glycosides [ J] .Phytochemistry , 1992 , 31:
3307-3330.
[ 3] 　Abe F , Yamauchi TL.Lignans f rom Trachelospermum asiaticum
[ J] .Chem Pharm Bull , 1986 , 34:4340-4345.
[ 4] 　Mcnally DJ , Wurms KV , Labbe C , et al.Complex C-glycosyl f la-
vonoid phytoalexins from Cucumis sativus [ J] .J Nat Prod , 2003 ,
66:1280-1283.
[ 5] 　Prabhu BR , Mulchandani NB.Lignans from Piper cubeba [ J] .
　2007年 7月　第 5卷　第 4期 Chin J Nat Med　July 2007　Vol.5　No.4　257　
Phytochemistry , 1985, 24:329-331.
[ 6] 　Tan XQ , Chen HS , Liu RH.Lignans from Trachelospermum jasmi-
noides [ J] .Planta Med , 2005 , 71:93-95.
[ 7] 　Suzuki H , Lee KH , Haruna M.(+)-arctigenin , a lignan from
Wikstroemia indica [ J] .Phytochemistry .1982 , 21:1824-1825.
[ 8] 　Chakravarty AK , Mukhopadhyay S , Saha S.A neolignan and sterols
in f ruits of Solanum sisymbrifolium [ J] .Phytochemistry , 1996, 41:
935-939.
蓬莱葛中木脂体类化学成分
谢光辉1 ,马　磊2 ,郑宗平2 ,胡立宏1 , 2＊
1华东理工大学药学院 , 上海 200237;
2中国科学院上海市药物研究所上海中药现代化研究中心 ,上海 201203
【摘　要】　目的:从蓬莱葛中分离木脂体类化合物。方法:采用柱色谱进行分离纯化 , 应用波谱方法鉴定其结构。结
果:从蓬莱葛中分离得到 4 个二芳基丁内酯类木脂体和 1 个苯并二氢呋喃新木脂体类化合物。分别为:mutiflinside(1),
trachelosiaside(2), (-)-arctigenin(3), matairesinoside(4), sisymbrifolin(5)。结论:其中化合物 1为新化合物 ,而且属于自
然界比较少见的碳苷类木脂体 ,化合物 2 , 3 , 4 , 5 为首次从该属植物中分得。
【关键词】　蓬莱葛;木脂体;碳苷类木脂体
·征订启事·
欢迎订阅 2008年《医药导报》杂志
《医药导报》杂志系国家一级学会———中国药理学会等联合主办的医药专业期刊 , 是国家科技部中国科技论文
统计源期刊(中国科技核心期刊),被美国《化学文摘》(CA)、《国际药学文摘》(IPA)和俄罗斯《文摘杂志》(AJ)收录。
2006年被评为湖北省优秀期刊。是万方数据库 、中文科技期刊数据库 、中国生物医学期刊引文数据库 、中国学术期
刊综合评价数据库来源期刊 ,经国家新闻出版总署批准面向国内外公开发行。
该刊设有“特约稿” 、“药物研究” 、“药物与临床” 、“药学进展” 、“用药指南” 、“药品质量控制” 、“新药介绍” 、“药物
制剂” 、“药物不良反应” 、“药事管理” 、“作者·编者·读者”等栏目 ,每期组编某类药物或某类疾病的药物治疗专栏。读
者对象是临床医师 、药师 、医药院校师生和医药研究所 、药品检验所的科技工作者及药品监督管理 、医药工商企业经
营者。
《医药导报》创刊 27年来 , 始终坚持刊物的科学性 、实用性 、信息性 , 以普及 、运用 、服务为宗旨 ,及时报道国内外
医药研究新成果 、新技术 、新方法 ,指导临床合理用药 , 在医药科研 、生产 、经营 、使用间发挥纽带和桥梁作用。该刊
已被国家认定为发布处方药广告的宣传媒体 ,并被评为武汉市广告协会先进集体。 2006 年 ,《医药导报》被湖北省印
刷产品质量监督检验站认定为湖北省优秀产品。曾获中国科协专项基金资助。月刊 , 每月 1 日出版 , 每期 10.00 元 ,
全年 120.00 元(含邮资),欢迎广大读者到当地邮局订阅 ,如错过邮局订阅时间 , 可随时向该刊编辑部邮订。
地址:武汉市航空路 1 号 ,邮政编码:430030
网址:www.yydbzz.com 或 www.yydb.cn
E-mail:y198203@public.wh.hb.cn
电话及传真:027-83643083 , 83666619
国内总发行:湖北省邮政报刊发行局。邮发代号 38-173。全国各地邮局。国外总发行:中国国际图书贸易总公
司(北京 399 信箱), 国外代号:BM6485 或中国出版对外贸易总公司(北京 782 信箱)。
国内统一刊号:CN42-1293/ R, 国际标准出版物号:ISSN1004-0781。广告许可证:武工商 0620 号。
258　　Chin J Nat Med　July 2007　Vol.5　No.4 　2007年 7月　第 5卷　第 4期