全 文 ：天然产物研究与开发 NatProdResDev2008, 20:66-69
文章编号:1001-6880(2008)01-0066-04
　
　
　ReceivedOctober16, 2006;AcceptedFebruary7, 2007
　FoundationItem:TheprojectwassupportedbytheScientificResearch
FoundationfortheReturnedOverseasChineseScholars, StateEduca-
tionMinistry.
＊CorespondingauthorTel:86-731-8995848;E-mail:lxq0001@hotmail.com
异柱五加叶中齐墩果烷型皂苷的研究
刘向前 1＊ ,金寅钐 2 ,陆昌洙 2 ,南相吉 2 ,李龙燮 2
1中南大学化学化工学院制药工程系 , 长沙 410083;2庆熙大学药学院生药学硏究室 ,首尔
摘　要:利用柱色谱从异柱五加 (AcanthopanaxsieboldianusformaalbeofoliumYook)叶的甲醇提取液中分离出四
个齐墩果烷型皂苷类化合物。通过波谱方法(1HNMR、13CNMR、 2DNMR和 FAB-MS)鉴定它们分别为 kalo-
panax-saponinB(1)、acanthopanaxsaponinCP3(2)、kalopanax-saponinA(3)和 sieboldianosideA(4)。
关键词:异柱五加;齐墩果烷型皂苷;Kalopanax-saponinB;AcanthopanaxsaponinCP3;SieboldianosideA;Kalopanax-
saponinA
中图分类号:R284.2 文献标识码:A
OleaneneGlycosidesfromtheLeavesofAcanthopanaxseiboldianus
formaalbeofoliumYook
LIUXiang-qian1＊ , KIMIn-seon2 , YOOKChang-soo2 , NAMSang-gil2 , LEEYong-eup2
1ColegeofChemistryandChemicalEngineering, CentralSouthUniversity, Changsha410083 , China;
2ColegeofPharmacy, KyungHeeUniversity, Hoegi-dongDongdaemun-ku
SeoulKoreaDepartmentofPharmaceuticalIndustry, Seoul, Korea
Abstract:FourknownoleananeglycosideswereisolatedforthefirsttimefromtheMeOHextractoftheleavesofAcan-
thopanaxsieboldianusformaalbeofoliumYookbyusingcolumnchromatography.Theywereidentifiedaskalopanax-sapo-
ninB(1), acanthopanaxsaponinCP3(2), kalopanax-saponinA(3)andsieboldianosideA(4)onthebasisofphysi-
cochemicalandspectroscopicdata(1HNMR, 13CNMR, 2DNMRandFAB-MS).
Keywords:AcanthopanaxsieboldianusformaalbeofoliumYook;oleananeglycoside;Kalopanax-saponinB;acanthopanax
saponinCP3;sieboldianosideA;Kalopanax-saponinA
Introduction
TheplantsofAcanthopanxgenus(Araliaceae), impor-
tantmedicinalplantsusedasatonicandasasedative
intraditionalorientalmedicine, havebeenrecentlyat-
tractedpublicatentionasacomponentofdietarysup-
plementsinKorea.Manyreportshavebeenissuedon
thechemicalconstituentsofsomeplantsbelongstothis
genus, especialy, ontriterpenoidglycosides[ 1-7] .
A.seibolidanusMakinowasimportedfromChinatoKo-
reamanyyearsago, andwascultivatedasamedicinal
gardenplantinKoreaandJapan[ 8] .A.sieboldianusfor-
maalbeofoliumYookiscloselyrelatedtoA.sieboldia-
nusandhasadistinguishablemorphologicalcharacter-
isticintheleaves.Someoleananetriterpeneshadbeen
reportedfromtherootsofA.sieboldianus[ 3] .However,
uptonow, therehasnoreportontheconstituentsofA.
sieboldianusformaalbeofoliumYook.Duringthestudy
onconstituentsofAcanthopanxgenus, thetriterpenoidal
constituentsofA.sieboldianusformaalbeofoliumYook
cultivatedinKoreawereinvestigated.Herewereport
theisolationandstructuredeterminationoffourknown
triterpenoidalglycosidesfromthisplant.Theyarekalo-
panax-saponinB(1), acanthopanaxsaponinCP3(2),
kalopanax-saponinA(3)andsieboldianosideA(4).
InourcontinuingstudyonAcanthopanaxgenus, some
oleananetriterpenoidswerefrequentlyfoundinsome
acanthopanaxspeciesincludingA.sieboldianus, A.sen-
ticosus, A.japonicusandA.spinosus.Fromthechemot-
DOI :10.16333/j.1001-6880.2008.01.027
axonomicviewofpoint, A.sieboldianusformaalbeofoli-
umispossibletobeclasifiedintoagrouppossessing
oleanane.A.senticosusandA.japonicusareahomologue
plants[ 9] .
Experimental
Instrumentsandreagents
OpticalrotationsweremeasuredusingaJASCOD-1010
polarimeter.FAB-MSwasperformedonaJEOLJMS-
700instrumentusingm-nitrobenzylalcoholasamatrix
inpositiveionmode.IRspectrawereobtainedwitha
Hitachi270-30 typespectrophotometer.NMRspectra
weremeasuredinpyridine-d5 onaVarianUI-500spec-
trometerandchemicalshiftsarequotedrelativetotet-
ramethylsilane(TMS).DiaionHP-20 (Mitsubishi
Chem.Co., Ltd.), SephadexLH-20 (PharmaciaBio-
tech), Silicagel60 (0.04-0.063mm, Merck)andLi-
ChroprepRP-18(40-63 m, Merck)wereusedforopen
columnchromatography.TLCwasperformedusingsili-
cagel60 F254 plates(Merck).GLCwasperformedon
aHP5890Agaschromatographwithflame-ionization
detector(column:HP-5 fusedsilicacapilarycolumn,
0.32mmid×30 m).
Plantmaterial
TheleavesofAcanthopanaxsieboldianusformaaleofoli-
um Yook(variegated)werecolectedinChulipo,
ChungNam, Korea, inAugust2005.Speciesidentifica-
tionwasperformedbyoneoftheauthors, Prof.Chang-
SooYookattheDepartmentofPharmacognosyin
KyungHeeUniversity.Avoucherspecimenhasbeen
depositedattheOrientalMedicineSpecimenMuseum
atKyungHeeUniversity.
Extractionandisolation
Driedleaves(250.14g)wereextractedtwicewithhot
MeOH.AfterevaporatingMeOHundervacuum, theres-
idue(45.80g)wassubjectedtoDiaionHP-20column
chromatographyusing0-100% aqueousMeOHassol-
ventstogivefractionsI-V.FractionVfromtheeluate
of100%MeOHwassubsequentlyseparatedonasilica
gelcolumnelutedgradientwithCHCl3-MeOH-H2O
(9:1:0.1※ 6:4:1)togive10 fractions(Fr.1-
Fr.10).Compound1(kalopanax-saponinB, 0.29mg,
yield0.64%)wasobtainedfromfractionFr.5 (0.29
g)separatedoversilicagelcolumnchromatography.
FractionFr.3(0.41 g)wasseparatedonasilicagel
columngradientlyelutedwithCHCl3 -MeOH-H2O(9:
1:0.1※7:3:0.2 )togive4 fractions(Fr.A-Fr.D).
Compound2 (acanthopanaxsaponinCP3 , 0.162 g,
yield0.35%)wasobtainedfromthefractionFr.B
(0.162 g)bysilicagelcolumnchromatographyre-
peatedly.
FractionFr.8 (1.04 g)wasdividedinto5 fractions
(Fr.a-Fr.e)overODScolumnelutedwithMeOH.
Compound3 (kalopanaxsaponinA, 0.595 g, yield
1.32%)wasobtainedfromfractionFr.d(0.595 g)
byusinganODScolumnchromatographyrepeatedly.
FractionFr.9 (1.25 g)wasdividedinto14 fractions
(Fr.1-Fr.14)overODScolumnelutedwithMeOH.
Compound4 (sieboldianosideA, 0.170 g, yield
0.38%)wasobtainedfromfractionFr.7 (0.170 g)
byusinganODScolumnchromatography.
Identification
Kalopanax-saponinB(1)　Yield0.64%, whitea-
morphouspowder.mp.253-256 ℃ (decomp.), [ α] 19D
+18.6°(c0.59 , inMeOH), IRυKBrmax cm-1:3430
(OH), 1695 (COOH).FAB-MSm/z:751 [ M +
H] +.1HNMRδ:1.63 (3H, d, J= 6.1 Hz, RhaH-
6), 3.29(1H, brd, J=13.6 Hz, H-18), 4.12 (1H,
m, H-3), 5.12 (1H, d, J=6.1 Hz, AraH-1), 5.51
(1H, brs, H-12), 6.23 (1H, s, RhaH-1).13CNMR
dataseeTables1and2.Itsspectraldatawereidentical
tothosereported[ 7] .
AcanthopanaxsaponinCP3 (2)　 Yield0.35%,
whiteamorphouspowder.[ α] 24D-4.9°(c0.71, in
MeOH), IRυKBrmaxcm-1:3425 (OH), 1690 (COOH).
FAB-MSm/z:867 [ M+H] +.1HNMRδ:4.93(1H,
d, J=8.0 HzAraH-1), 5.47(1H, d, J=7.7Hz, Xyl
H-1), 6.31 (1H, s, RhaH-1).13CNMRdataseeTa-
bles1 and2.
KalopanaxsaponinA(3)　Yield1.32%, whitea-
morphouspowder.[α] 21D-20.5°(c0.50inMeOH), IRυKBrmax
cm-1:3440(OH), 1730(ester).FAB-MS(negative)m/z:
1219 [ M-H] - , 1073 [ M-Rha-H] - , 749 [ M-(Glc-Glc-
Rha)-H] - , 603[ M-(Glc-Glc-Rha)-(Rha)-H] - , 471[ 749-
67Vol.20 LIUXiang-qian, etal:OleaneneGlycosidesfromtheLeavesofAcanthopanaxseiboldianusformaalbeofoliumYook
(Ara-Rha)-H] -.1HNMRδ:1.64 (3H, d, J=6.1 Hz,
RhaH-1), 1.70 (3H, d, J=6.2 Hz, RhaH-1), 5.01
(1H, d, J=7.6 Hz, GlcH-1), 5.12(1H, d, J=6.2Hz,
AraH-1), 5.86 (1H, s, RhaH-1), 6.26 (1H, s, J=8.0
Hz, esterGlcH-1), 6.66(1H, s, RhaH-1).13CNMRda-
taseeTables1and2.
SieboldianosideA(4)　Yield0.037%, whiteamor-
phouspowder.[ α] 21D -24.2°(c0.50, inMeOH),
IRυKBrmaxcm-1:3425(OH), 1730(ester).Elemetalanal-
ysisfoundC, 54.58;H, 7.75 (C64H104O30· 3H2Ore-
quires;C, 54.61;H, 7.88).FAB-MS(negative)m/z:
1351 [ M-H] - , 1219 [ M-Xyl-H] - , 1073 [ M-(Rha-
Xyl)-H] -, 881[ M-(Glc-Glc-Rha)-H] - , 749[ M-(Glc-
Glc-Rha)-(Xyl)-H] - , 603 [ M-(Glc-Glc-Rha)-(Rha-
Xyl)-H] -.1HNMRδ:5.00 (1H, d, J=7.4 Hz, Glc
H-1), 5.07(1H, d, J=6.1Hz, AraH-1), 5.35 (1H,
d, J=7.7 Hz, XylH-1), 5.85 (1H, s, RhaH-1),
6.25(1H, d, J=8.0 Hz, esterGlcH-1), 6.35 (1H,
s, RhaH-1).13CNMRdataseeTables1and2.
Thespectraldataofcompounds2, 3 and4 werecon-
sistentrespectivelywiththoseofacanthopanaxsaponin
CP3(2), kalopanax-saponinA(3)andsieboldianoside
A(4)isolatedfromA.sieboldianus[ 3] .
Table1　 13 CNMRdataforaglyconemoietiesofcom-
pounds1-4 inpyridine-d5(125 MHz)
Carbon 1 2 3 4
1 38.7 39.1 38.8 38.8
2 25.9 26.3 26 26.1
3 80.8 81.1 80.8 80.8
4 43.3 43.6 43.3 43.4
5 47.4 47.7 47.4 47.4
6 18.3 18.2 18 17.9
7 32.6 32.6 31.3 32.5
8 39.5 39.9 39.6 39.7
9 47.9 48.2 47.9 48
10 36.6 36.9 36.6 36.6
11 23.5 23.9 23.4 23.6
12 122.3 122.9 122.7 122.8
13 144.6 144.1 143.9 143.9
14 41.9 42.2 42.9 41.9
15 28.1 28.3 28 28.1
16 23.4 23.4 23.1 23.1
17 47.4 47 46.8 46.8
18 41.7 41.7 41.4 41.4
19 46.2 46.2 45.9 45.9
20 30.7 30.8 30.5 30.5
21 34 34 33.7 33.7
22 32.6 32.8 32.5 32.5
23 63.7 28.4 63.7 63.7
24 13.7 14.2 13.7 14
25 15.8 16.2 15.9 16
26 17.9 17.6 17.3 17.3
27 25.9 26.1 25.8 25.8
28 180.1 180.0 176.3 176.3
29 33 33.1 32.9 32.9
30 23.5 23.7 23.4 23.4
Table2　 13CNMRDataforsugarmoietiesofcompounds1-
4 inpyridine-d5(125 MHz)
Carbon 1 2 3 4
3-O- 104.7
Ara-1 104.3 105.2 104.5 75.8
2 75.8 75.6 75.9 75.3
3 74.8 74.5 74.7 69.6
4 69.5 69.2 69.4 66.13
5 65.6 65.5 65.7 101.4
Rha-1 101.7 101.4 101.8 71.9
2 72.5 71.9 72.4 83.1
3 72.7 83 72.6 73.1
4 74.2 73 74.3 69.8
5 69.7 69.6 69.8 18.7
6 18.7 18.4 18.6 107.6
Xyl-1 107.5 75.5
2 75.3 78.5
3 78.4 71.3
4 71.1 67.5
5 67.4
28-O- 95.6
Glc-1 95.9 73.9
2 74.3 78.4
3 78.5 70.9
4 71.0 78
5 78.3 69.2
6 69.5 104.8
Glc-1 104.9 75.3
2 75.7 76.5
3 76.8 78.9
4 79.0 77.3
5 77.4 61.4
6 61.5 102.8
Rha-1 102.9 72.8
2 72.8 72.9
3 73.0 74.0
4 74.1 70.5
5 70.6 18.6
6 18.8 104.7
68 NatProdResDev　　　　　　　　　　　　　　　　　　　　　 　Vol.20
Fig.1　Compounds1-4isolatedfromAcanthopanaxsieboldianusformaaleofolium
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