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Chemicalstructureofcyperotundicacidfrom
rhizomesofCyperusrotundus
XUHongbo,GENGChangan,ZHANGXuemei,MAYunbao,HUANGXiaoyan,CHENJijun
(StateKeyLaboratoryofPhytochemistryandPlantResourcesinWestChina,KunmingInstituteof
Botany,ChineseAcademyofSciences,Kunming650201,China)
[Abstract] ThirteencompoundswereisolatedfromtheethylacetateextractoftherhizomesofCyperusrotundus(Xiangfu)bymeans
ofvariouschromatographictechniques(silicagel,Al2O3,SephadexLH20,MCIGELCHP20PandHPLC),andtheirstructureswere
identifiedascyperotundicacid(1),(4S,5E,10R)7oxotrinoreudesm5en4βol(2),4hydroxy4,7dimethyl1tetralone(3),tar
axerone(4),dammaradienylacetate(5),zeorin(6),sarmentine(7),guineensine(8),pelitorine(9),caprolactam(10),lirioden
drin(11),3hydroxy1(4hydroxy3,5dimethoxyphenyl)2[4(3hydroxy1(E)propenyl)2,6dimethoxyphenoxy]propylβD
glucopyranoside(12)and1(3,4methylenedioxyphenyl)1Etetradecene(13)byextensivespectroscopicanalyses(IR,MS,1Dand
2DNMR)Compound1wasanewrearangedsesquiterpeneandnamedascyperotundicacid,whichdidnotobeytheisoprene
ruleCompounds213wereobtainedfromthegenusCyperusforthefirsttime
[Keywords] Cyperusrotundus;cyperotundicacid;sesquiterpene;amide
doi:10.4268/cjcmm20160615
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Vol41,No.6 March,2016
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[
yg?z
]
[1]
$%,m
.
[1
[S].2010:241.
[2] RaoBS,PanickerPB,SudboroughJJ.EssentialoilofCyperus
rotundus[J].JIndianInstSci,1925,8A:39.
[3] HegdeBJ,RaoBS.EssentialoilfromtherhizomesofCyperus
rotundus,Linn[J].JSocChemInd(London),1935,54:387.
[4] BradfieldAE,HedgeBH,RaoBS,etal.Alphacyperone,a
sesquiterpeneketonefromtheoilofCyperusrotundus[J].J
ChemSoc,doi:101039/JR9360000667.
[5]
²
,
Àö
,
&
,
ö
.
[\_
[J].
$
%(1-.
,2010,16(11):214.
[6]
Ëù©
,
+%Ý
.
[\_,
[J].
$
,Ê
,2003,26(1):65.
[7] XuHB,MaYB,HuangXY,etal.Bioactivityguidedisola
tionofantihepatitisBvirusactivesesquiterpenoidsfromthetra
ditionalChinesemedicine:rhizomesofCyperusrotundus[J].J
Ethnopharmacol,2015,171:131.
[8] GuoChiZ,HatanoM,IshitsukaMO,etal.Novelsecoand
seconorsesquiterpeneshavingacyclopropaneringfromtheoki
nawanactiniaAnthopleurapacificaUchida[J].TetrahedronLet,
1990,31(18):2617.
[9] ChengSY,WangS,WenZH,etal.Threeneweudesmanoids
fromtheFormosansoftcoralNephtheaerecta[J].JAsianNat
ProdRes,2009,11(11):967.
[10] MulholandDA,McfarlandK,RandrianarivelojosiaM.Sesquit
erpenoidderivativesfromCipadesaboiviniana(Meliaceae)[J].
BiochemSystEcol,2006,34(4):365.
[11]
±¬
,
ÍR7
,
Í9
,
ö
.
Ó¢£Ý_
[J].
9
,2007,29(5):586.
[12] GrandeM,ToresP,PieraF,etal.TriterpenoidsfromDitrichia
viscosa[J].Phytochemistry,1992,31(5):1826.
[13] FengJ,YangXW,SuSD,etal.Studiesonchemicalconstitu
entsfromherbsofUsnealongisima[J].ChinaJChinMate
Med,2009,34(6):708.
[14] LikhitwitayawuidK,RuangrungsiN,LangeGL,etal.Structur
alelucidationandsynthesisofnewcomponentsisolatedfromPiper
sarmentosum(Piperaceae)[J].Tetrahedron,1987,43(16):
3689.
[15] LeeSA,HwangJS,HanXH,etal.Methylpiperatederivatives
fromPiperlongumandtheirinhibitionofmonoamineoxidase[J].
ArchPharmacalRes,2008,31(6):679.
[16] LeitoCunhaEV,OliveiraChavesMC.TwoamidesfromPiper
tuberculatumfruits[J].Fitoterapia,2001,72(2):197.
[17]
Ùý
,
±:Ý
,
Í4¹
,
ö
.
¤¥V$s©_=
Vv
[J].
$%,_-.
,2009,19(5):368.
[18]
¹+{
,
À¦
,
OOE
,
ö
.
§¨þ_
[J].
$
%,-.
,2005,40(9):653.
[19] TakaraK,MatsuiD,WadaK,etal.Newantioxidativephenolic
glycosidesisolatedfromKokutononcentrifugedcanesugar[J].
BiosciBiotechnolBiochem,2002,66(1):29.
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