全 文 ：天然产物研究与开发 NatProdResDev2007, 19:620-622, 630
文章编号:1001-6880(2007)04-0620-04
　
　
　ReceivedSeptember13, 2006;AcceptedOctober31, 2006
＊CorespondingauthorTel:86-871-5223246;E-mail:cxchen@mail.
kib.ac.cn
角果胡椒的化学成分研究
李君竹 ,刘海洋 ,董　秋 ,陈昌祥＊
中国科学院昆明植物研究所 植物化学与西部植物资源持续利用国家重点实验室 , 昆明 650204
摘　要:从角果胡椒的乙醇提取物中分离得到 6个甾醇 , 通过波谱方法鉴定它们的结构为 5α, 8α-过氧-(22E,
24R)-麦角甾-6, 22-二烯-3β-醇(1), (22E, 24R)-麦角甾-5, 7, 22-三烯-3β-醇(2), (22E, 24R)-麦角甾-7, 22-二烯-
3β, 5α, 6β-三醇(3),豆甾醇-5, 11-二烯-3β-醇(4),豆甾醇-3, 6-二酮(5), sitoindosideΙ(6)。
关键词:角果胡椒;甾醇
中图分类号:R284.1;Q946 文献标识码:A
ChemicalConstituentsofPiperpedicelatumC.DC
LIJun-zhu, LIUHai-yang, DONGQiu, CHENChang-xiang＊
StateKeyLaboratoryofPhytochemistryandPlantResourcesinWestChina, KunmingInstitute
ofBotany, theChineseAcademyofSciences, Kunming650204 , China
Abstract:Sixsteroidswereisolatedfromthe75% EtOHofthewholeplantofPiperpedicelatumforthefirsttime.On
thebasisofthespectraldata, theywereidentifiedas5α, 8α-epidioxy-(22E, 24R)-ergosta-6, 22 -diene-3β-ol(1), (22E,
24R)-ergosta-5, 7, 22-triene-3β-ol(2), (22E, 24R)-ergosta-7, 22-diene-3β, 5α, 6β-triol(3), stigmasta-5, 11-dien-3β-
ol(4), stigmasta-3, 6-dione(5), sitoindosideΙ(6).
Keywords:Piperpedicellatum;Piperacreae;steroids
Introduction
ThegenusPiperL.iswidelydistributedthroughout
tropicalandsubtropicalregionsandcomprisesabout
2000species[ 1] .SixtyofthemaredistributedinChi-
na.About40 speciesofthisgenushavebeenfoundin
YunnanProvince.Piperspecieshavebeenusedintra-
ditionalmedicinalsystemsforthousandsofyears, inclu-
dingtheChineseandIndiansystems, aswelasinfolk-
loremedicinesofLatinAmericaandtheWestIndies.
Inpreviousreportsofthisgenus, numerousbiologicaly
activecompoundssuchasalkaloids, propenylphenols,
lignans, neolignans, terpenes, steroids, kawapyrones,
piperolides, chalcones, dihydrochalcones, flavones, and
flavanoneshavebeenisolated.Piperine, thefirstamide
secondarymetabolitetobeisolatedfromPiperspp.,
displayedseveralinterestingactivities, suchasacentral
nervoussystemdepresant[ 2] .Aduncamide, anewam-
idefromP.aduncumthatshowedantibacterialactivity
againstBacilussubtilisandMicrococcusluteus, wasalso
showntobecytotoxictowardKBnasopharyngealcarci-
nomacels[ 3] .Kadsurenone, anovelneolignanfromP.
futokadsurawasidentifiedasapotentinhibitorina
plateletactivatingfactor(PAF)bindingassay[ 4] .Con-
sideringthatPiperspecieshavealreadyyieldednumer-
oussecondarymetabolitesofpotentialtherapeuticinter-
est, thegenusPiperwouldseemtoconstitutearichpo-
tentialsourceofadditionalnovelactiveprinciples.
InChina, PiperpedicelatumC.DC.ismainlydistribu-
tedintheXishuangbannanofYunnanProvince.How-
ever, nochemicalworkhasbeendonetothisspecie.
Forseekingbioactivecompounds, weexaminedtheex-
tractsfromtheP.pedicelatum.Inthispaper, wereport
6 knownsteroids, 5α, 8α-epidioxy-(22E, 24R)-ergos-
ta-6, 22-diene-3β-ol(1), (22E, 24R)-ergosta-5, 7, 22-
triene-3β-ol(2), (22E, 24R)-ergosta-7 , 22-diene-3β,
5α, 6β-triol(3), stigmasta-5, 11-dien-3β-ol(4), stig-
masta-3, 6-dione(5), sitoindosideΙ(6).Compound1,
DOI :10.16333/j.1001-6880.2007.04.025
asa5α, 8α-epidioxysterolhasbeenreportedtheactiv-
ityofagainsttheHTLV-1 virusinvitro[ 5] .
Fig.1　Structuresofcompounds1-6
Experimental
General
1HNMR, 13CNMRspectrawererecordedonaBruker
AM-400 MHzandaDRX-500 spectrometerwithTMS
standardandCDCl3 andCD3OD-d4 assolvent, chemi-
calshiftvalueswerereportedinδ(ppm)andcoupling
constantsinHzunits;FAB-MSdatawerereportedona
VGAutospec-3000 spectrometer;EI-MS:70 eV.Col-
umnchromatography(CC):silicagel(Hand200-300
mesh;QingdaoMarineChemicalsCo., Ltd.), Sepha-
dexLH-20 gel(Amershanbiosciences, Sweden).
MPLC:BǜchipumpModuleC-605 , Bǜchipumpman-
agerC-615 , BǜchiFrctionColectorC-600.
Plantmaterial
ThewholeplantsofPiperpedicelatumwerecolected
inSeptember2003 from Xishaungbannan, Yunnan
Province, ChinaandidentifiedbyProf.TaoGuo-daat
XishuangbannanTropicalBotanicalGarden, theChi-
neseAcademyofSciences(CAS).
Extractionandisolation
Theair-driedandpowderedwholeplantsofPiperpedi-
celatum(5kg)wereextractedwith75% ethanolunder
reflux(25 L×3, each3 h).Theextractwasevaporated
invacuotogiveablack-browngum(119 g).Thegum
wassubjectedtoCC(SiO2;Petroleumether/EtOAc(0:
1※1:0)toafordtwelvefractions(Fr.1-12)asjudged
byTLC.Fr.7(10 g)wasfurtherpurifiedbyCC(SiO2;
Petroleumether/EtOAc)togive1(10mg), 2(19mg),
3(10mg), 4(24mg).Fr.10(5.2 g)wassubjectedto
CC(SiO2;Petroleumether/EtOAc)toyield5(10 mg)
and6(39 mg).
ResultsandDiscussion
5α, 8α-Epidioxy-(22E, 24R)-ergosta-6, 22-diene-
3β-ol(1)　Whiteflakycrystal, C28H44O3.EI-MSm/z
(%):428 [ M] +(3), 410 [ M-H2O] +(5), 396[ M-
32] +(18), 376(5), 363(8), 249(8), 107(31), 69
(100).1HNMR(CDCl3 , 400 MHz)δ:6.49(1H, d, J
=8.49Hz, H-7), 6.23(1H, d, J=8.47 Hz, H-6),
5.22(1H, dd, J=16 Hz, 7.38 Hz, H-23), 5.13(1H,
dd, J=16, 8 Hz, H-22), 3.96(1H, m, H-3).13 C
NMR(CDCl3 , 100 MHz)δ:34.7(t, C-1), 30.1(t, C-
2), 66.4(d, C-3), 36.9(t, C-4), 82.25(s, C-5),
135.2(d, C-6), 130.7(d, C-7), 79.42(s, C-8),
51.14(d, C-9), 36.9(s, C-10), 23.4(t, C-11), 39.3
(t, C-12), 44.5(s, C-13), 51.7(d, C-14), 20.6(t, C-
15), 28.6(t, C-16), 56.2(d, C-17), 12.8(q, C-18),
18.1(q, C-19), 39.6(d, C-20), 20.8(q, C-21),
135.4(d, C-22), 132.2(d, C-23), 42.7(d, C-24),
33.0(d, C-25), 19.9(q, C-26), 19.6(q, C-27), 17.5
(q, C-28).TheNMRdatawereinaccordancewith
thosereported[ 5].
(22E, 24R)-Ergosta-5, 7, 22- triene-3β-ol(2)　
Whiteneedles, C28H44O;EI-MSm/z(%):396 [ M] +
(5), 378 [ M-H2O] + (4), 271 [ M-sidechain] +
(13), 69(100).1HNMR(CDCl3 , 400 MHz)δ:0.61
(3H, s, Me, H-18), 1.02(3H, s, H-19), 3.61(1H, m,
H-3), 5.18(1H, d, J=7.25 Hz, H-6), 5.16(1H, d, J
=7.25 Hz, H-7), 5.54(1H, brd, J=3.35 Hz, H-
22), 5.36(1H, t, J=2.6 Hz, H-23);13C NMR
(CDCl3 , 100 MHz)δ:33.1(t, C-1), 28.2(t, C-2),
70.5(d, C-3), 32.0(t, C-4), 139.8(s, C-5), 119.6
(d, C-6), 116.3(d, C-7), 141.3(s, C-8), 54.5(d, C-
9), 37.1(s, C-10), 21.1(t, C-11), 39.1(t, C-12),
42.8(s, C-13), 46.2(d, C-14), 23.0(t, C-15), 28.2
(t, C-16), 55.7(d, C-17), 12.0(q, C-18), 16.2(q,
C-19), 40.3(d, C-20), 21.1(q, C-21), 135.5(d, C-
22), 132.0(d, C-23), 42.8(d, C-24), 32.0(d, C-
25), 19.9(q, C-26), 19.6(q, C-27), 17.5(q, C-28).
TheNMRdatawereinconsistentwiththoserepor-
ted[ 6] .
(22E, 24R)-Ergosta-7, 22-diene-3β , 5α, 6β-triol(3)
Whiteflakycrystal, C28 H46 O3.EI-MSm/z(%):430
621Vol.19 LIJun-zhuetal:ChemicalConstituentsofPiperpedicelatumC.DC
[ M] + (1), 412 [ M-H2O] + (23), 394(32), 379
(34), 376(20), 251(100), 69(89).1H NMR
(CD3OD, 400 MHz)δ:0.62(3H, s, H-18), 1.04(3H,
s, H-19), 1.02(3H, d, J=6.16 Hz, H-21), 3.97
(1H, m, H-3), 5.25(1H, m, H-7), 5.19(2H, m, H-
22 , 23);13 CNMR(CD3OD, 100 MHz)δ:31.5(t, C-
1), 33.7(t, C-2), 68.2(d, C-3), 40.5(t, C-4), 76.8
(s, C-5), 74.0(d, C-6), 118.8(d, C-7), 143.7(d, C-
8), 44.2(d, C-9), 38.0(s, C-10), 22.9(t, C-11),
40.3(t, C-12), 44.5(s, C-13), 55.7(d, C-14), 23.9
(t, C-15), 29.0(t, C-16), 57.2(d, C-17), 12.7(q, C-
18), 18.8(q, C-19), 41.6(d, C-20), 21.6(q, C-21),
136.8(d, C-22), 133.0(d, C-23), 44.1(d, C-24),
34.2(d, C-25), 20.0(q, C-26), 20.42(q, C-27),
18.1(q, C-28).TheNMRdatawereinconsistentwith
thosereported[ 7] .
Stigmasta-5, 11-dien-3β-ol(4)　 Whiteneedles,
C29H48O.EI-MSm/z(%):412 [ M] +(6), 397(30),
381(70), 369(20);1HNMR(CDCl3 , 400 MHz)δ:
0.68(3H, s, H-18), 1.01(3H, s, H-19), 3.52(1H,
m, H-3), 5.03(1H, d, J=8.0 Hz, H-12), 5.15(1H,
m, H-11), 5.34(1H, m, H-6);13CNMR(CDCl3 , 100
MHz)δ:32.7(t, C-1), 31.6(t, C-2), 71.7(d, C-3),
42.2(t, C-4), 140.7(s, C-5), 121.7(d, C-6), 24.3
(t, C-7), 50.1(d, C-8), 51.3(d, C-9), 36.5(s, C-
10), 129.2(d, C-11), 138.3(d, C-12), 42.3(s, C-
13), 56.7(d, C-14), 24.3(t, C-15), 28.3(t, C-16),
56.0(d, C-17), 12.0(q, C-18), 19.3(q, C-19), 36.1
(d, C-20), 18.7(q, C-21), 39.7(t, C-22), 26.1(t, C-
23), 45.7(d, C-24), 29.1(d, C-25), 19.8(q, C-26),
19.0(q, C-27), 23.0(q, C-28), 11.8(q, C-29).The
NMRdatawereidenticaltothosereported[ 8] .
Stigmasta-3, 6-dione(5) 　 Amorphouspower,
C29H48O2.EI-MSm/z(%):428 [ M] +(40), 413 [ M-
15] +(4), 399 [ M-28] +(17), 287(37), 259(12),
245(100), 231(36).1HNMR(CDCl3 , 500 MHz)δ:
5.31(1H, brs, H-6), 4.35(1H, d, J=7.5 Hz, H-1′),
0.96(3H, s, H-19), 0.90(3H, d, J=6.0 Hz, H-21),
0.85(3H, d, J=6.6 Hz, H-27), 0.82(3H, t, J=7.1
Hz, H-29), 0.79(3H, d, J=6.8 Hz, H-26), 0.65
(3H, s, H-18);13 CNMR(CDCl3 , 125 MHz)δ:38.1
(t, C-1), 39.4(t, C-2), 209.0(s, C-3), 37.3(t, C-
4), 57.6(s, C-5), 211.2(s, C-6), 46.6(d, C-7),
38.8(d, C-8), 53.6(d, C-9), 41.2(s, C-10), 23.1
(t, C-11), 38.8(t, C-12), 41.2(s, C-13), 56.1(d, C-
14), 26.1(t, C-15), 28.0(t, C-16), 56.8(d, C-17),
12.0(q, C-18), 19.8(q, C-19), 36.0(d, C-20), 18.7
(q, C-21), 36.0(d, C-22), 28.0(d, C-23), 45.8(d,
C-24), 29.2(d, C-25), 19.0(q, C-26), 18.7(q, C-
27), 21.7(q, C-29), 12.5(q, C-29).TheNMRdata
wereinaccordancewiththosereported[ 9] .
SitoindosideΙ(6)　Amorphouspower.C51 H90 O7.
(-)FAB-MSm/z(%):813 [ M-H] -;EI-MSm/z
(%):414 [ M-Glu-R +H2O] +(18), 396(4), 322
(17), 255(100), 161(5), 119(7), 87(13), 69(20),
57(23).1HNMR(CDCl3 , 400 MHz)δ:5.31(1H, brs,
H-6), 4.35(1H, d, J=7.5Hz, H-1′), 0.96(3H, s, H-
19), 0.90(3H, d, J=6.0 Hz, H-21), 0.85(3H, d, J
=6.6 Hz, H-27), 0.82(3H, t, J=7.1 Hz, H-29),
0.79(3H, d, J=6.8 Hz, H-26), 0.65(3H, s, H-18);
13CNMR(CDCl3 , 100MHz)δ:37.3(t, C-1), 34.3(t,
C-2), 79.7(d, C-3), 38.9(t, C-4), 140.3(s, C-5),
122.1(d, C-6), 31.9(d, C-7), 33.9(s, C-8), 50.2
(d, C-9), 36.8(s, C-10), 21.1(t, C-11), 39.8(t, C-
12), 42.3(s, C-13), 56.8(d, C-14), 24.3(t, C-15),
28.9(t, C-16), 56.2(d, C-17), 11.8(q, C-18), 19.4
(q, C-19), 36.1(d, C-20), 19.0(q, C-21), 34.3(d,
C-22), 31.8(d, C-23), 45.8(d, C-24), 29.1(d, C-
25), 19.8(q, C-27), 11.9(q, C-28), 101.3(d, C-
1′), 70.4(d, C-2′), 76.2(d, C-3′), 73.4(d, C-4′),
73.7(d, C-5′), 63.6(t, C-6′), 101.3(d, C-1′), 174.
3(C=O), 21.0-29.7(14 ×CH2), 14.1(CH3).The
NMRdatawereidenticaltothosereported[ 10] .
Reference
1　DelectisFloraeReipublicaePopularisSinicaeAgendaeAca-
demiaeSinicaeEdita, FloraReipublicaePopularisSinicae,
SciencePress, Beijing, 1982, Tomus20:67-68.
2　ParmarVS, JainSC, BishtKS, etal.Phytochemistryofthe
genusPiper.Phytochemistry, 1997, 46:597-673.
3　OrjalaJ, WrightAD, RaliT, etal.Aduncamide, acytotoxic
and antibacterialβ-phenylethylamine-derivedamidefrom
Piperaduncum.NatProdLet, 1993, 2:231-236.
4　ChangMN, HanGQ, ArisonBH, etal.NeolignansfromPiper
futokadsura.Phytochemistry, 1985, 24:2079-2082.
(下转第 630页)
622 NatProdResDev　　　　　　　　　　　　　　　　　　　　　 　Vol.19
MIC:1.54%。
3.4　绿茶提取物对两种代表性细菌的抑菌效果远
好于桑叶 ,最小抑菌浓度低 。
参考文献
1　FanLS(樊黎生).ResearchontheantimicrobialofMorus
albaL.leaves.NatProdResDev(天然产物研究与开发),
2001, 13:30-32.
2　ShenP(沈萍), FanXR(范秀蓉).ExperimentsonMicrobi-
ology(微生物学实验).Beijing:AdvancedEducationPub-
lishingHouse, 1999.64-72.
3　OrthDS.Linearregressionmethodforrapiddeterminationof
adequacyofcosmeticpreservativeefficacy.JSocCosm
Chem, 1979, 30:321-332.
4　OrthDS.Preservativeefficacytesting:areviewofvarioustes-
tingmethodsandtheirreliability.Cosmetics＆ Toiletries,
1997, (112):58-61.
5　MuscatielloMJ.CTFA′sPreservationguidelines:ahistorical
perspectiveandreview.Cosmetics＆Toiletries, 1993, 108:53-
59.
6　WangQ(王琼).Greentea.DieteticScience(饮食科学),
2003, (7):10-11.
7　QiuBY(裘炳毅).CosmeticChemistryandTechnology(化
妆品化学与技术大全), Beijing:LightIndustryPressof
China, 1997.390-391.
8　InstituteofMedicalplantDevelopment.ChineseAcademyof
MedicalScienceandPekingUnionMedicalColege.Record
ofChineseMateriaMedical(中药志).Beijing:People s
MedicalpublishingHouse, 1960.290-292.
9　JiangsuNewMedicalColege.DictionaryofChineseMateria
Medical(中药大辞典).Shanghai:ShanghaiScientificand
TechnicalPublishers, 1997.
(上接第 622页)
5　GauvinA, SmadjaJ, AkninM, etal.Isolationofbioactive
5α, 8α-epidioxysterolfromthemarinespongeLuffarielacf.
variabilis.CanJChem, 2000, 78:986-992.
6　YoshihisaT, MinoruU, TakasdhiO, etal.Glycosidesofer-
gosterolderivativesfromHericiumerinacens.Phytochemistry,
1991, 30:4117.
7　IirizziM, MinaleL, RiccioR, etal.Polarsteroidsfromthe
marinescalopPatiopectenyessoensis.JNatProd, 1988, 51:
1098-1103.
8　AlamMS, ChopraN, AliM, etal.Ursaneandsterolderives
from Pleuchenlanceolata.Phytochemistry, 1994, 37:521-
524.
9　GasparEMM, NevesHJC.Steroidalconstituentsfrommature
wheatstraw.Phytochemistry.1993, 34:523-527.
10 LuoXD, WuShH, MaYB, etal.Chemicalconstituentsfrom
Dysoxylumhainanense.ActaBotanicaYunnanica, 2001, 23:
368-372.
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