Three new secolignan glycosides from Urtica fissa E. Pritz

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Three new secolignan glycosides from Urtica fissa E. Pritz

JNatMed(2012)66:562–565DOI10.1007/s11418-011-0615-x

NOTE

ThreenewsecolignanglycosidesfromUrtica?ssaE.Pritz

Bao-minFeng?Hai-hongQin?Hui-guoWangLi-yingShi?Da-yongYu?Bao-quanJi?QiZhao?Yong-qiWang

Received:28August2011/Accepted:11November2011/Publishedonline:29November2011ÓTheJapaneseSocietyofPharmacognosyandSpringer2011

AbstractThreenewsecolignanglycosides{3,4-trans-4-[bis(3,4-dimethoxyphenyl)methyl]-2-oxotetrahydrafuran-3-yl}methyl-O-b-glucopyranoside(1),{3,4-trans-4-[(3-methoxy-4-hydroxyphenyl)(3,4-dimethoxyphenyl)methyl]-2-oxote-trahydrafuran-3-yl}methyl-O-b-glucopyranoside(2)and{3,4-cis-4-[(3-methoxy-4-hydroxyphenyl)(3,4-dimethoxy-phenyl)methyl]-2-oxotetrahydrafuran-3-yl}methyl-O-b-glu-copyranoside(3)wereisolatedfromtherootsofUrtica?ssaE.Pritz.Theirstructureswereidenti?edbyspectralmethodsincluding1DNMR,2DNMRandHR-EI-MS.KeywordsUrtica?ssaE.PritzÁUrticaceaeÁSecolignanglycosidesÁLignans

yl)methanol,whichcanbesubstitutedbyOH/OMeatphenylgroupsorbereducedatthe2-carboxylgroup.Secolignans,whichwerefoundtoshowantivirus,antitumor,anti-in?ama-tory,etc.activities[13,14,16],arepotentnaturalproductsthatdeservedextensiveresearch.ThispaperdealswiththreenewsecolignansisolatedfromUrtica?ssaE.Pritz.TheirstructuresweredeterminedbyanalysesofNMR,HR-ESI–http://wendang.chazidian.compounds1–3possessedoneortwoextramethoxysubsti-tutionsattheC-3/4positionsofthebenzeneringtothosereportedpreviouslyinthisplant[7]andtheyalsohavedifferentglycosylationpositionscomparedwiththoseisolatedfromUrticatriangularisHand.-Mazz.[8].Experimental

Introduction

Urticaspeciesarefamousfortheirtraditionaluseinthetreat-mentofosteoarthritis,rheumatism,benignprostatehyperplasia(BPH),jointpain,etc.inmanyorientalandEuropeancountries[1–5].Duringourpreviousstudies,severalsecolignanswereisolatedfrom3typesofUrticaplants[6–8].Secolignansarerarelyreportednaturalproducts,?rstfoundinPeperomiajaponica[9].Nomorethan20secolignansandtheirglycosideshavebeenisolatedfromseveralkindsofplants,especiallyfromPeperomiaspecies,todate[10–15].Theskeletonstructureofsecolignansis(4-bisphenylmethyl-2-oxotetrahydrafuran-3-B.Feng(&)ÁH.WangÁL.ShiÁD.YuÁB.JiÁQ.ZhaoÁY.Wang

SchoolofLifeScienceandBiotechnology,DalianUniversity,Dalian116622,Chinae-mail:fengbaomin@http://wendang.chazidian.com

H.Qin

MedicalCollege,DalianUniversity,Dalian116622,China

General

MeltingpointsweremeasuredonanXT4Amicromeltingpointapparatusanduncorrected.OpticalrotationsweremeasuredwithaP3002/RSpolarimeter.NMRspectraweretakenonaBruker-ARX-500spectrometerusingstandardBrukersoftware.TheHR-EI-MSspectrawererecordedonaZabSpecmagneticmassspectrometer.Columnchromatography(CC)wascarriedonsilicagel(200–300mesh,QingdaoMarineChemicalGroup,Qingdao)andC18reverse-phasesilicagel(250mesh,Merck).TLCwasusedtomonitorthefractionsonpre-coatedsilicagelGF254plates(QingdaoMarineChemicalGroup).Thefractionswerefurtherpuri?edbyHPLC(ODScolumn,8lm,109250mm,wavelengthofdetector254nm).Plantmaterial

TherootsofUrtica?ssaE.PritzwerecollectedinAugust2004,inSichuanprovince,China.Avoucherspecimen,

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JNatMed(2012)66:562–565identi?edbyProf.ChenChen(LiaoningNormalUniver-sity),wasdepositedwithregistrationno.04026intheSchoolofLifeScienceandBiotechnologyofDalianUniversity.

Extractionandisolation

ThedriedrootspowderofUrtica?ssaE.Pritz(8kg)wereextractedwithEtOH(95%)underre?uxandthen?lteredthroughgauze.TheEtOHextractwasconcentratedbyevaporationtogivetheresidue,whichwasfurtherextractedwithpetroleumetherandEtOAcsuccessivelysuspendedinH2O.TheH2Olayerwasevaporatedandtheresiduewasseparatedintoseveralfractionsbypolyporusresin(D101),elutingwithEtOH:H2O(30:70,50:50,100:0).ThefractionelutedwithEtOH:H2O(50:50)wasseparatedintoseveralfractionsbycolumnchromatographyonsilicagel,andelutedwithCHCl3:MeOHmixtures.ThefractionelutedwithCHCl3:MeOH(6:1)wasfurtherseparatedbyHPLCtoafford1(11mg),2(7mg)and3(13mg).Resultsanddiscussion

Compound1wasobtainedaspaleyellowamorphouspow-der,m.p.120–122°C(MeOH),½a 20D-34.6(MeOHc2.45).ThemolecularformulawasdeducedtobeC28H36O12(calcd564.2207)accordingtoHR-ESI–MS,whichshowedaquasi-molecularionpeakatm/z564.2221([M]?),togetherwith1

H-NMRand13C-NMR.Inthe1H-NMRspectrum,sixaromaticprotonsatd6.88(1H,d,J=8.5),6.90(1H,d,J=8.1),6.95(1H,m),6.95(1H,d,J=1.9),6.97(1H,d,J=2.0),and6.99(1H,dd,J=8.1and1.9)belongedtotwoABXsystemswhichindicatedtwo1,2,4-trisubstitutedphenylgroups.The1H-NMRalsoshowed4methoxylsignalsatd3.79,3.82(both6H,s),twomethylenesignalsatd4.35(dd,J=8.8and8.3),3.88(1H,dd,J=8.8and7.1),3.74(dd,J=10.3and2.7),3.31(1H,dd,J=10.4and4.2),andthreemethinesignalsatd2.56(dt,J=7.4and3.3),3.68(1H,m)and3.84(1H,d,J=11.5).The13C-NMRspectra,togetherwithHSQC,showed12signalsforaromaticC-atomsatd113.2,113.4(39C),121.0,121.6,137.0,137.2,149.5(29C),150.6and150.7,twomethylenesignalsatd68.4,72.8,threemethinesignalsatd41.5,48.0,56.4,onecarbonylsignalatd180.5andfourmethoxylsignalsatd56.5,56.6,56.7and56.8.

Additionallythe1H-and13C-NMRspectrashowedsignalsforasugarmoietyatd4.12(1H,d,J=7.9),3.16(1H,m),3.21(1H,m),3.31(2H,m),3.71(1H,dd,J=11.7and5.4),3.86(1H,dd,J=11.7and2.5)and104.7,78.0(29C),75.1,71.5,62.7.BasedontheHSQC,HMBC,andNOESYdata,itwaselucidatedasb-glucopyranosylmoi-ety.Theabsolutecon?gurationofthesugar-moietyisvery

563

likelytobeD,butclear-cutexperimentalevidencewasabsent.

Thetwobenzeneringswerebothdeterminedtobe3,4-dimethoxyphenylbyHMBCcorrelationsbetweenthetwomethoxylsatd(3.79,3.82)andC-30,300/C-40,400(Fig.1),respectively.Thepresenceofabis(3,4-dimethoxy-phenyl)methylgroupwasprovedbyHMBCcross-peaksbetweenH-6andthearomaticprotonsC-10,C-100,C-20,C-200,C-60andC-600.Ac-butyrolactoneringwasdeducedfromtheHMBCcross-peaksbetweenH-3,H-4,H-5andthecarbonylC-2.Thedi(3,4-dimethoxyphenyl)methylgroupwassuggestedtobelocatedatC-4ofthec-butyro-lactoneringbyHMBCcorrelationsbetweenH-4,H-5,andC-6.

TheglycopyranosylunitwasshowntobeattachedtoC-7asdemonstratedbyboththeglycosylationshiftofdC-7from60.8inurticol(asecolignanaglyconeisolatedfromUrticamaireiLevl.)[6]to68.4incompound1andtheHMBCcorrelationbetweenH-1000oftheglucopyranosylandC-7.TheHMBCbetweenH-7andC-2,C-3suggestedthestructureof1asshowninFig.1.Ithadatranscon-?gurationatC-3/C-4byNOESYcorrelationbetweenH-3andH-6,H-4andH-7(Fig.2).Thusthestructureof1was

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564JNatMed(2012)66:562–565

determinedas{3,4-trans-4-[bis(3,4-dimethoxyphenyl)me-thyl]-2-oxotetrahydrafuran-3-yl}methyl-O-b-glucopyrano-side(1)(Fig.2).

Compound2wasalsoobtainedaspaleyellowamor-phouspowder,m.p.128–130°C(MeOH),½a 20D-32.4(MeOHc0.71).TheHR-EI-MSofcompound2gavea

molecularionpeakatm/z550.2069,inaccordancewiththemolecularformulaC27H34O12(calcd550.2050).Thedif-ferencebetweencompound2andcompound1isthatonly3methoxylgroups[3.79(3H,s),3.81(3H,s)and3.84(3H,s)]wereobservedinthe1HNMRspectrum.Likecom-pound1,two1,2,4-trisubstitutedphenylgroupswerealso

Table1The1HNMRdataofcompounds1,2and3(dppminCD3ODandJinHz)Positions3456720506

000

Compound1

2.56,1H,dt,J=7.4,3.33.68,1H,m

4.35,1H,dd,J=8.8,8.33.88,1H,dd,J=8.8,7.13.84,1H,d,J=11.53.74,1H,dd,J=10.3,2.73.31,1H,dd,J=10.4,4.26.97,1H,d,J=2.06.88,1H,d,J=8.56.95,1H,m6.95,1H,d,J=1.96.90,1H,d,J=8.16.99,1H,dd,J=8.1,1.94.12,1H,d,J=7.93.16,1H,m3.21,1H,m3.31,1H,m3.31,1H,m

3.86,1H,dd,J=11.7,2.53.71,1H,dd,J=11.7,5.43.79,both6H,s3.82,both6H,s

Compound2

2.57,1H,dt,J=7.3,3.33.66,1H,m4.35,1H,m

3.88,1H,dd,J=8.8,6.73.80,1H,d,m

3.75,1H,dd,J=10.4,2.83.35,1H,dd,J=10.3,3.86.93,1H,d,J=1.96.74,1H,d,J=8.16.84,1H,dd,J=8.1,1.96.94,1H,d,J=2.06.90,1H,d,J=8.36.99,1H,dd,J=8.3,2.04.11,1H,d,J=7.83.15,1H,m3.20,1H,m3.32,1H,m3.32,1H,m

3.87,1H,dd,J=11.7,2.33.71,1H,dd,J=11.7,5.33.84,3H,s

3.79,3.81,both3H,s

Compound3

2.75,1H,dt,J=9.2,3.13.72,1H,m

4.24,1H,dd,J=11.0,8.33.90,1H,t,J=8.33.83,1H,d,J=11.04.19,1H,dd,J=9.9,2.53.51,1H,dd,J=9.9,2.17.00,1H,d,J=1.96.78,1H,d,J=8.16.94,1H,dd,J=8.1,1.96.95,1H,d,J=1.96.84,1H,d,J=8.36.92,1H,dd,J=8.3,1.94.30,1H,d,J=7.93.24,1H,m3.24,1H,m3.30,1H,t,J=6.73.42,1H,t,J=8.93.86,1H,m,hidein-OMe3.64,1H,dd,J=12.1,5.63.85,3H,s

3.77,3.80,both3H,s

250060010002

000

3000400050006

000

30/300-OCH340,400-OCH3

Table2TheNo.23456712

CNMRdataofcompounds1,2and3(inCD3OD)

1180.548.041.572.856.468.4137.0113.2150.6149.5113.4121.056.556.7

2180.748.041.772.956.568.6135.9113.0149.2146.6116.5121.8–56.6

3181.644.242.874.556.668.9137.9113.4149.4146.4116.5121.1–56.6

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