全 文 ：　　　　 天然产物研究与开发　 　　　　　
2004　Vol.16　No.5 NATU RAL PRODUCT RESEARCH AND DEVELOPMENT　 　　　　　　　　　　
　
　
　
　
　　Received 04 January 2004;Accepted 02 February 2004
　　Foundation Item:the Natural Science Foundation of Guangxi(No.
9811009)
　＊Corresponding author　Tel:86-771-5868986;E-mail:hping1208@
hotmail.com
PHENYLPROPANOID GLYCOSIDES FROM TYPHONIUM
FLAGELLIFORME(ARACEACE)
HUANG Ping
1＊ ,GLORIA Karagianis2 ,PETER G .Waterman2
(1.Guangxi Institute of T raditional Medical and Pharmaceutical Sciences , Nanning 530022 , China;
2.Centre for Phy tochemistry , Southern Cross University , Lismore NSW 2480 , Australia)
Abstract　The roo ts of Typhonium f lagelliforme(Araceace)were ex tracted with hot 95% EtOH , Petrol , EtOAc
and n-BuOH.Then the ex tract was separated by HPLC , and three compounds have been isolated.On the basis of
spectroscopic evidence(UV , IR, 1H NM R , 1 3C NMR and 2D NMR), their structures have been elucidated as
coniferin(1), methylconiferin(2)and potassium nitrate(3).Phenylpropanoid glycosides were isolated from Typhoni-
um flagelliforme for the first time.
Key words　 Typhonium flagelliforme;Araceace;pheny lpropanoid glycoside;coniferin;methy lconiferin;po tassium
nitrate
鞭檐犁头尖中的苯丙素甙类化合物
黄　平1 　Gloria Karagianis2 　Peter G .Waterman2
(1.广西中医药研究所　南宁　530022;
2.澳大利亚南十字星大学植物化学研究中心　利斯墨　NSW 2480)
摘　要　从天南星科植物鞭檐犁头尖的根茎中分离得到 3 个化合物 , 运用波谱技术(UV , IR , 1H NMR , 13C
NMR and 2D NM R)对它们的化学结构进行解析 , 分别鉴定为松柏甙(1), 甲基松柏甙(2)和硝酸钾(3)。从鞭
檐犁头尖中分离得到苯丙素甙类化合物尚属首次。
关键词　鞭檐犁头尖;天南星科;松柏甙;甲基松柏甙;硝酸钾
Typhonium f lagelli forme(Lodd.)Blume has a wide dis-
tribution in the moist , warm , habitats of Southeast Asia ,
ranging f rom Northern Aust ralia to South India[ 1] .In
Malaysia the plant is known locally as the `rodent tuber
and is commonly used to treat various types of cancer[ 2] .
In China it is mainly used as an alternative to the t radi-
tional Chinese medicinal herb , Pinellia Tuber(Pinellia
temata)to treat colds and coughs.Crude ext racts have
been reported to produce a reduction in lymphoid cell
grow th and exhibit weak cy totoxic activity in vitro[ 3] , as
well as relieving cough , eliminating expectoration , and
showing anti-asthmatic , analgesic , and anti-inflammatory
properties in mice[ 4 , 5] .The methyl ester of 13-phenyl-
tridecanoic acid , along with several fatty acids and aliphat-
ics have been reported from the hexane ext ract of this
plant
[ 6 , 7] .We reexamined the chemical constituents of
Typhonium f lagel li forme and obtained two phenyl-
propanoid glycosides , along with potassium nitrate.In this
paper , we describe the isolation and the st ructure elucida-
tion of these compounds.
Fig.1　Structures of compound 1 and 2
Experimental
General
Column chromatography was carried out on silica gel(200
～ 300 mesh , Qingdao Marine Chemical Inc.,China).Se-
403
DOI :10.16333/j.1001-6880.2004.05.007
mi-preparative HPLC was performed on a Hewlett
Packard 1100 series HPLC using a Zorbax 250 mm ×10
mm ,5 μm C-18 reversed-phase semi-preparative column.
Purity checks of compounds were performed using an Agi-
lent 125 mm×4 mm , 5 μm C-18 reversed-phase analytical
column.IR spect ra were obtained on a Bruker Vector 33
FT-IR spectrophotometer as KBr disks.UV spectra were
recorded on a Hewlett Packard 8453 UV-visible spec-
trophotometer.NMR data was obtained using a Bruker A-
vance DRX-500 spect rometer operating at 500.13 MHz
for 1H and 125.77 MHz for 13C.Chemical shift δvalues
were referenced to CD3OD(1H 3.31 ppm;13C 49.15
ppm).MS(low resolution)were obtained using a Hewlett
Packard Agilent 1100 series LC-MSD in APCI mode and
an Agilent 6890 GC-MS system in EI mode;HRMS were
recorded on a VG Autospec-oa-TOF MS in ESI mode.
Plant material
The roo t tubers of T .f lagell iforme were collected
from Yulin City ,Guangxi ,China , in 2000 and identi-
f ied by Professor Fang Ding.A voucher specimen
(No.06939)was deposi ted in the herbarium of
Guangxi Insti tute of T raditional Medical and Pharma-
ceut ical Sciences.
Extraction and isolation
The tubers(15 kg)of T .f lagel li forme were ex tract-
ed wi th hot 95% EtOH(3×45 l , reflux).After re-
moval of the solvent by evaporation in vacuo , the
residue(2 kg)was suspended in H2O and ext racted
w ith pet rol ,EtOAc and n-BuOH successively .The n-
BuOH ex tract w as further separated by semi-prepara-
tive HPLC using a linear gradient of 80%H2O-20%
MeOH to 5%H2O-95%MeOH to give compound 1(18 mg)and 2(4 mg), respect ively .The residual w a-
ter phase w as concentrated to small volume and placed
in a refrigerator for a few day s.The needle crystals of
3(2 g)were separated out and were purified by re-
peated crystallization.
Identification
Coniferin(1)　White needle ,mp.176 ～ 178 ℃(MeOH),
UV(MeOH)λmax nm:215 , 259;IR υKBrmax cm-1:3356 ,
2925 , 2855 , 1575 , 1513 , 1415 , 1266 , 1223 , 1264 , 1223 ,
1074;APCI-MS m/ z :360(M +H+OH-] +.1H and 13C
NMR data see Table 1.[ 8 , 9] The complete assignments of
the H and C atoms were furthering confirmed by HSQC ,
1H-1H COSY ,NOESY and HMBC experiments.
Methylconiferin(2)　White needle , mp.167 ～ 169 ℃
(MeOH),UV λmax(MeOH)nm(log ε):213(4.32), 259
(4.20), 292(3.71);IR υKBrmax cm-1:3356 , 2925 , 2855 ,
1575 , 1513 , 1415 , 1266 , 1223 , 1264 1223 , 1074;APCI-
MS(probe)150 eV , m/ z(rel.int.):374[M +H+OH-] +
(3), 163(100);HR-ESI-MS:m/ z 355.1430 [ M-H]-
(calc.for C17H23O8 355.1393);1H and 13C NM R data see
T able 1[ 9] .The complete assignments of the H and C
atoms were furthering confirmed by 1H-1H COSY ,
NOESY ,HSQC and HMBC experiments.
Table 1　1H and 13C NMR spectroscopic data of compound 1
and 2 in CD3OD
Position
δC δH(J in Hz)
I II I II
1 147.9 147.8
2 150.7 150.9
3 111.3 111.5 7.07 d(1.7) 7.08 d(2.0)
4 132.7 133.6
5 120.8 120.9
6 116.9 117.9 7.11 d(8.4) 7.10 d(8.4)
1′ 129.8 133.6 6.55 d(15.7) 6.58 d(16.0)
2′ 130.4 125.5 6.28 dt(15.7 ,6.2) 6.22 dt(16.0 ,
6.2)
3′ 63.3 74.1 4.21 dd(6.2 , 1.2) 4.07 dd(6.2 ,1.3)
2-OMe 56.3 56.7 3.89 s 3.88 s
3′-OM e 57.9 3.37 s
1′ 102.7 102.8 4.89 d(7.1) 4.89 d(7.4)
2′ 75.3 75.0 3.48 m 3.48 m
3′ 78.9 78.0 3.40 m 3.45 m
4′ 71.5 71.4 3.48 m 3.34 m
5′ 79.3 78.2 3.40 m 3.34 m
6′ 62.8 62.5 3.87 m
3.69 m
3.86 m
3.69 m
Potassium nitrate(3)　White needle ,mp.:>300 ℃, IR
υKBrmax cm-1 :2401 , 1761 , 1384 , 835.The element contents
of 3 were determined by ICP , only K+ and NO3-were
measured.
Acknowledgements　The authors are grateful to thank
Larry A.Hick at the Department of Chemistry , University
of Wollongong , for technical assistance in obtaining the
HRMS data.Thanks are also made to Don Brushet t at the
Centre for Phytochemistry , Southern Cross University , for
technical assistance with the LC-MS analysis.
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404　　　　　　　　　 天然产物研究与开发 2004　Vol.16　No.5
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A NewApproach to Natural Products Discovery Exemplified by the Identification of Sulfated Nu-
cleosides in Spider Venom
Andrew E.Taggi , Jer rold Meinwald , and Frank C.Schroeder＊
Contribution from The Cornell Institute for Research in Chemical Ecology and TheDepartment of Chemistry and Chemical Biology ,
Baker Laboratory , Cornell UniVersity , I thaca , New York 14853
Abstract　Using a new approach based on the NM R spectroscopic analysis of the entire , unpurified spider venom , we identified a fam-
ily of unusual sulfated nucleoside derivatives from the venom of the hobo spider , Tegenaria agrestis.These compounds are ribonucleo-
side mono- and disulfates derived from guanosine and xanthosine , some of which are glycosylated , bearing one o r tw o D-fucose units.
The use of NMR spectroscopy to characterize the unfractionated venom was central to the discovery of this heretofore overlooked class
of venom components.
J.Am .Chem .Soc., 2004 , 126 , 10364-10369
Extraction of Mass Spectra and Chromatographic Profiles fromOverlapping GC/MS Signal with
Background
Shao Xueguang＊ ,Wang Guoqing ,Wang Sufang , and Su Qingde
Depart ment of Chemistry , University of Science and Technology of China , Hefei , Anhui , 230026 , People s Republic of China
An adaptive immune alg orithm(AIA)was proposed fo r resolution of the overlapping GC/MS signal with background.By using A IA ,
the chromato graphic profiles corresponding to the independent components(ICs)in the overlapping signal are calculated with the mass
spectra ex tracted by means of independent component analy sis(ICA).The number of the ICs in the overlapping signal is determined
by the difference between the reconstructed and the original data.Both simulated and experimental data are investigated with the pro-
po sed AIA approach.I t w as found that the mass spectra and chromatog raphic profiles o f the components in an overlapping multicom-
ponent GC/MS signal can be accurately resolved with the existence of backg round , and the results are better than that by using an in-
teractive self-modeling mix ture analy sis (SIMPLISMA)method.The AIA approach may be a promising tool for the resolution of
ov erlapping GC/MS signal.
Analy tical Chemistry
4052004　Vol.16　No.5 黄　平等:鞭檐犁头尖中的苯丙素甙类化合物