[生物醫(yī)藥論文精品a]線紋香茶菜中木脂素的分離與結(jié)構(gòu)鑒定

ISOLATIONANDSTRUCTUREIDENTIFICATIONOFLIGNANSFROMRABDOSIALOPHANTHOIDESBUCHHAMEXDDONHARAFENGWEISHENG1,ZANGXINYU1,ZHENGXIAOKE2,WANGYANZHI1,LIHONGWEI1ANDLIZHEN11SCHOOLOFPHARMACY2BASICMEDICALCOLLEGE,HENANUNIVERSITYOFTRADITIONALCHINESEMEDICINE,1JINSHUIROAD,ZHENGZHOU450008,CHINAABSTRACTTOSTUDYTHECHEMICALCONSTITUENTSOFRABDOSIALOPHANTHOIDESBUCHHAMEXDDONHARAVARIOUSCOLUMNSINCLUDINGDIAIONHP20,TOYOPEARLHW40C,SEPHADEXLH20,SILICAGELWEREEMPLOYEDFORTHEISOLATIONANDPURIFICATIONOFCOMPOUNDSFROMRABDOSIALOPHANTHOIDESBUCHHAMEXDDONHARATHESTRUCTURESOFTHECOMPOUNDSWEREELUCIDATEDBYTHEIRPHYSIOCHEMICALCHARACTERISTICSANDSPECTRALDATATWONEWDIHYDROBENZOFURANLIGNANOSIDES,LOPHANTHOSIDEB1ANDAENANTIOMEROFUMBROSIDE2,ALONGWITHSEVENKNOWNLIGNANS39,WEREISOLATEDFROMRABDOSIALOPHANTHOIDESBUCHHAMEXDDONHARACOMPOUND16WASSOLATEDFROMTHISSPECIESFORTHEFIRSTTIME,ALLTHECOMPOUNDSWEREISOLATEDFROMTHISPLANTFORTHEFIRSTTIMEKEYWORDSRABDOSIALOPHANTHOIDESCHEMICALCONSITITUENTSLIGNANS線紋香茶菜中木脂素的分離與結(jié)構(gòu)鑒定A1A0A21A4A5A3A61A4A8A7A92A4A11A10A121A4A14A13A151A4A14A161A18A17A19A20A21A22,1A24A21A222A25A23A20A21A22,A26A27A28A29A30A31A321A33450008A34A35A36A37A38A39A40A41A42A43A44A45A46A47A48A49A50A51A52A53DIAIONHP20A50TOYOPEARLHW40CA50SEPHADEXLH20A50SILICAGELA54A55A56A57A58A59A60A61A49A62,A63A64A65A66A46A67A68A69A70A57A71A64A72A73A46A74A75A76A77A78A49A62A79A80A81A82A83A45A84A85A81A86A87A88A89A90A91A92,LOPHANTHOSIDEB1A93A94A95UMBROSIDEA96A97A98A992,A100A101A102A95A103A104A96A105A106A107A108A109A110A111A112A113A114A109A110A11116A115A116A117A118A119A120A121A111A114A122A123A124A125A126A96A109A110A111A127A115A116A117A118A128A129A130A131A132A114A122A123A112A133A134A135A134A135A134A135A136A136A136A137A138A139A140A141A142A143A144A145A146A142A147A148A149ISODONRABDOSIAISACOSMOPOLITANANDIMPORTANTGENUSOFTHELABIATAELAMIACEAEFAMILYABOUT150SPECIESOFUNDERSHRUBS,SUBUNDERSHRUBSORPERENNIALHERBSAREFOUNDTHROUGHOUTTHEWORLDMAINLYINTROPICALANDSUBTROPICALASIATHEUSEOFISODONSPECIESINCHINESEPOPULARFOLKMEDICINEHASALONGTRADITIONMOSTHERBSOFTHISSPECIESHAVEBEENFOUNDTOHAVEOBVIOUSBIOLOGICALACTIVITIESWITHLOWTOXICITYRABDOSIALOPHANTHOIDESBUCHHAMEXDDONHARAHASBEENUSINGFORTHETREATMENTOFACUTEICTERICHEPATITIS,ACUTECHOLECYSTITI,SPHAGITIS,GYNAECOPATHIA1,ANDSOONHOWEVER,FEWOFTHEPHYTOCHEMICALSTUDIESOFTHEPLANT,ESPECIALLYLIGNANS,HAVEBEENREPORTEDPREVIOUSLYTHEFIRSTINVESTIGATIONONISODONSPECIESCANCORRESPONDINGAUTHORTEL8637165680011,FAX8637165680011,EMAILFWSHHACTCMEDUCNOOHOH3COOCH3OHOHOOHOH3COOCH3OHOCH3OCH3HOHOHOOHHOOHOOHOHOOHOOHMEOOCOOMEOHOMEOH1234567839978OHOOOHHOOHHOOMEOOHOHOOR1MEOR3OOR2OHOOHOOHOCH3OCH3HOHOHOOHHOBETRACEBACKTO1900SDURINGTHESEYEARS,HUNDREDSOFDITERPENOIDSHAVEBEENFOUND,ANDANUMBEROFTHOSEISOLATEDDITERPENOIDSHAVEBEENFOUNDTOHAVEPOTENTANTITUMOURACTIVITIES2HOWEVER,DIHYDROBENZOFURANLIGNANSANDTHEIRGLYCOSIDES,WHICHALSOACTASANIMPORTANTBIOLOGICALACTIVITIESGROUP,HAVENEVERBEENFOUNDINISODONSPECIESBEFOREINTHISPAPER,WEREPORTTHATTWONEWDIHYDROBENZOFURANLIGNANOSIDES,LOPHANTHOSIDEB1ANDAENANTIOMEROFUMBROSIDE2,ALONGWITHFOURKNOWNLIGNANS39,THEYWEREALLISOLATEDFROM50AQUEOUSACETONEEXTRACTOFRABDOSIALOPHANTHOIDESBUCHHAMEXDDONHARATHECHEMICALSTRUCTURESOF19WEREFULLYELUCIDATEDBYEXTENSIVESPECTROSCOPICMETHODSINCLUDING1HAND13CNMR,1H,1HCOSY,HMBC,HSQC,ANDNOESYEXPERIMENTSANDHRESIMS12789RESULTSANDDISCUSSIONCOMPOUND1WASOBTAINEDASAWHITE,AMORPHOUSPOWDER,WITHTHEMOLECULARFORMULAR1R2R33HHGLU4HHH5MEGLUH6MEGLUHC34H40O15,ASDEDUCEDFROMTHEMNAPEAKATM/Z7112260BYHRESIMSIRSPECTRUMEXHIBITEDABSORPTIONOFOHGROUPS3423CM1,CARBONYL1697CM1,ANDAROMATICRINGS1612,1516CM1,THEUVSPECTRUMSHOWEDABSORPTIONMAXIMUMAT280NM,INDICATINGTHEPRESENCEOFAROMATICRINGTHE1HNMRAND13CNMRSPECTRAOF1TABLE1CLEARLYSHOWEDTHEPRESENCEOFDIHYDROBENZOFURANSKELETON,WITHONEGLUCOSEMOIETYH441D,J78HZ,1H,330M,1H,358M,1H,342M,2H,439M,1H,476M,1HC1040C1“,751C2“,756C3“,720C4“,780C5“,653C6“,ONEMETHOXYLH376S,3HC564MEOANDTHESIGNALSOFASYRINGOYLMOIETYH729S,2H,374S,6HC1210C1“1082C2“6“1492C3“5“1425C4“1681CO5672MEOTHEDIHYDROBENZOFURANSKELETONWASIDENTIFIEDBYCOMPARISONOFITSNMRSPECTRALDATAWITHTHOSEREPORTED3THESKELETALSTRUCTRUEWASESTABLISHEDBYTHEHMBCCORRELATIONSBETWEENHC6“H439,476MANDCOC1681,ANDBETWEENHC1“H441D,J78HZANDC9C727,ANDBETWEENHCMEOH376SANDC3C1492ITWASCONCLUDEDTHATTHESYRINGOYLMOIETYCOULDBELOCATEDATC6“OFTHEGLUCOSEGROUP,ANDTHEOGLUCOPYRANOSYLCOULDBELOCATEDATC9ANDTHEMETHOXYLATC3,RESPECTIVELYINADDITION,THEABSOLUTECONFIGURATIONOFC7C894ANDC8C541WASFURTHERPROVEDBYMEANSOFITSDIFFERENTCHEMICALSHIFTSIN13CNMRACCORDINGTOTHEREPORT3,4C7880895ANDC8535550WAS7R,8SC7865875ANDC8565575WAS7S,8R,ANDATRANSCONFIGURATIONBETWEENC7ANDC8WASDETERMINEDFROMTHECOUPLINGCONSTANTJ60HZ5THESEDATASUGGESTEDTHATTHEABSOLUTECONFIGURATIONOFC7ANDC8INCOMPOUND1WASRANDS,RESPECTIVELYONTHEBASISOFSPECTRALEVIDENCE,THESTRUCTUREOFCOMPOUND1WASELUCIDATEDAS7R,8S4,3,9TRIHYDROXYL3METHOXYL7,8DIHYDROBENZOFURAN1PROPYLNEOLIGNAN9O6OSYRINGOYLDGLUCOPYRANOSIDECOMPOUND2WASOBTAINEDASAWHITE,AMORPHOUSPOWDER,WITHTHEMOLECULARFORMULAC25H32O11,ASDEDUCEDFROMTHEMNAPEAKATM/Z5311841BYHRESIMSIRSPECTRUMEXHIBITEDABSORPTIONOFOHGROUPS34003500CM1ANDAROMATICRINGS1608,1510CM1,THEUVSPECTRUMSHOWEDABSORPTIONMAXIMUMAT214,233AND282NM,INDICATINGTHEPRESENCEOFAROMATICRINGTHE1HNMRAND13CNMRSPECTRAOF2TABLE1EXHIBITEDTHECHARACTERISTICPATTERNOFADIHYDROBENZOFURANSKELETON,WITHONEGLUCOSEMOIETYH501D,J75HZ,1H,332M,1H,334M,1H,340M,1H,329M,1H,365M,1H,376M,1HC1027C1“,748C2“,776C3“,713C4“,780C5“,622C6“,ANDONEMETHOXYLH376S,3HC564MEOTHESKELETALSTRUCTRUEWASESTABLISHEDBYTHEHMBCCORRELATIONSBETWEENHC1“H501D,J75HZANDC3C1424,ANDBETWEENHCMEOH380SANDC3C1491ITWASCONCLUDEDTHATTHEOGLUCOPYRANOSYLCOULDBELOCATEDATC3ANDTHEMETHOXYLATC3THESTRUCTUREOF2ISCLOSELYRELATEDTOTHATOFUMBROSIDE6,EXCEPTFORTHE1HNMRAND13CNMRDATEOFC7ANDC8THEABSOLUTECONFIGURATIONOFC7C894ANDC8C549WASPROVEDBYMEANSOFITSDIFFERENTCHEMICALSHIFTSIN13CNMRACCORDINGTOTHEREPORT3,4C7880895ANDC8535550WAS7R,8SC7865875ANDC8565575WAS7S,8R,ANDATRANSCONFIGURATIONBETWEENC7ANDC8WASDETERMINEDFROMTHECOUPLINGCONSTANTJ60HZ5THECDSPECTRAEXHIBITEDPOSITIVECOTTONEFFECTAT221NM214OFCOMPOUND2APOSITIVECOTTONEFFECTAT223NM119WASREPORTEDWITH2R,3S2,3DIHYDROY24HYDROXY3METHOXYPHENYL3HYDROXYMETHYL7METHOXY5BENZOFURANPROPANOL4ODGLUCOPYRANOSID7THESEDATASUGGESTEDTHATTHEABSOLUTECONFIGURATIONOFC7ANDC8INCOMPOUND2WASRANDS,RESPECTIVELYONTHEBASISOFSPECTRALEVIDENCE,THESTRUCTUREOFCOMPOUND2WASELUCIDATEDAS7R,8S4,9,9TRIHYDROXYL3METHOXYL7,8DIHYDROBENZOFURAN1PROPYLNEOLIGNAN3ODGLUCOPYRANOSIDE,AENANTIOMEROFUMBROSIDETABLE1HAND13CNMRDATAOF1AND2AT400AND100MHZ,RESP,INCD3ODINPPM,JINHZARBITRARYATOMNUMBERINGPOSITION12HCHC1135013422694D,J181107685D,J1711083149214914147214765669D,J801160666D,J8111626680DD,J80,181196674DD,J81,1712007554D,J58894550D,J628948359M541341DD,J121,635499399M727376M6483OME376S564380S5641136813712656BRS1168681BRS11793141914244148914735129113056656BRS1171670BRS11957251T,J80326260T,J803278177M357180M3559353T,J68623352T,J686241441D,J751040501D,J7510272330M751332M7483358M756334M7764342M720340M7135342M780329M7806476M439M653365M376M6221“12102“,6“729S10823“,5“14924“1425MEO374S567CO1681COMPOUND39WEREELUCIDATEDAS7S,8R4,9,9TRIHYDROXYL3METHOXYL7,8DIHYDROBENZOFURAN1PROPYLNEOLIGNAN3ODGLUCOPYRANOSIDE3,7S,8R3,4,9,9TETRAHYDROXYL3METHOXYL7,8DIHYDROBENZOFURAN1PROPYLNEOLIGNAN4,7S,8R4,9DIHYDROXYL3,3DIMETHOXYL7,8DIHYDROBENZOFURAN1PROPYLNEOLIGNAN9ODGLUCOPYRANOSIDE5,7S,8R4,9,9TRIHYDROXYL3,3DIMETHOXYL7,8DIHYDROBENZOFURAN1PROPYLNEOLIGNAN6,SYRINGARESINOL4ODGLUCOPYRANOSIDE7,4,4,8TRIHYDROXYL3,3DIMETHOXYLBISEPOXYLIGNAN8HYDROXYPINORESINOL8,PINORESINOL4ODGLUCOPYRANOSIDE9,RESPECTIVELY,WITHTHEHELPOFSPECTROSCOPICTECHNIQUESTHEIR1HAND13CNMRDATAWEREINAGREEMENTWITHTHEONESREPORTEDINTHELITERATUREEXPERIMENTALSECTIONMELTINGPOINTSWEREDETERMINEDONAKOFLERMICROMELTINGPOINTAPPARATUSUNCORRECTEDOPTICALROTATIONSWEREMEASUREDWITHAPERKINELMER341POLARIMETERCDSPECTRAWERERECORDEDONAJASCOJ715SPECTROPOLARIMETERUVSPECTRAWEREMEASUREDWITHASHIMADZUUVVIS2201SPECTROPHOTOMETERIRSPECTRAWEREMEASUREDWITHASHIMADZUFTIR8201PCSPECTROMETERTHE1HAND13CNMRSPECTRAWEREOBTAINEDONABRUKERDPX400SPECTROMETER400OR300MHZFOR1HNMRAND100MHZFOR13CNMRWITHTMSASINTERNALSTANDARDHRESIMSWERERECORDEDONANAPEXIISPECTROMETERCOLUMNCHROMATOGRAPHYWASPERFORMEDONDIAIONHP20MITSUBISHICHEMICALCORP,JAPAN,SILICAGEL160200MESH,QINGDAOHAIYANGCHEMICALCO,LTD,CHINA,TOYOPEARLHW40CTOSOHCORP,JAPANTLCWASCONDUCTEDONSELFMADESILICAGELGQINGDAOHAIYANGCHEMICALCO,LTD,CHINAPLATESTHECHEMICALREAGENTSWEREPURCHASEDFROMBEIJINGCHEMICALPLANTANDTIANJINNO3REAGENTPLANTEMULSINANDHESPERIDINASEWEREPURCHASEDFROMSIGMACHEMCO,ANDRANDSTRIFLUOROMETHYLPHENYLACETICACIDSMTPAWEREFROMNACALAITESQUECO,LTDPLANTMATERIALDRIEDRABDOSIALOPHANTHOIDESWERECOLLECTEDFROMJIYUANCOUNTY,HENANPROVINCEINCHINA,ANDIDENTIFIEDBYPROFDONGCHENGMINGOFHENANUNIVERSITYOFTRADITIONALCHINESEMEDICINEAVOUCHERSPECIMENNO20060609ISDEPOSITEDINTHEHERBARIUMOFHENANUNIVERSITYOFTCM,ZHENGZHOU,PEOPLESREPUBLICOFCHINAEXTRACTIONANDISOLATIONDRIEDPLANTS90KGOFRLOPHANTHOIDESWEREEXTRACTEDBY50AQUEOUSACETONETWICEATROOMTEMPERATURE,ANDCONCENTRATEDUNDERREDUCEDPRESSUREBELLOW40THEWATERSOLUTABLEPARTWASCHROMATOGRAPHEDOVERDIAIONHP20WITHH2OCONTAININGINCREASINGAMOUNTOFMEOH,THE20MEOHELUATE106GWASCHROMATOGRAPHEDONTOYOPEARLHW40COARSEGRADEDEVELOPINGWITH10MEOH50MEOHTHE20MEOHELUTE29GWASRECHROMATOGRAPHEDONTOYOPEARLHW40ANDONSILICAGELTOYIELDCOMPOUND160MGANDCOMPOUND215MGTHE30MEOHELUATE119GWASCHROMATOGRAPHEDONTOYOPEARLHW40COARSEGRADEDEVELOPINGWITH10MEOH50MEOHTHE10MEOHELUTE16GWASRECHROMATOGRAPHEDONTOYOPEARLHW40ANDONSILICAGELTOYIELDCOMPOUND350MGAND425MGTHE40MEOHELUATE93GWASCHROMATOGRAPHEDONTOYOPEARLHW40COARSEGRADEDEVELOPINGWITH10MEOH50MEOHTHE10MEOHELUTE20GWASRECHROMATOGRAPHEDONTOYOPEARLHW40ANDONSILICAGELTOYIELDCOMPOUND520MG,COMPOUND620MG,730MG,815MGAND925MGIDENTIFICATION7S,8R3,9,9TRIHYDROXYL3METHOXYL7,8DIHYDROBENZOFURAN1PROPYLNEOLIGNAN4ODGLUCOPYRANOSIDE3WHITEPOWDER,1HNMRCD3OD,400MHZ486D,J80,1H552D,J60,1H656S,1H658S,1H694DD,J84,16,1H705D,J16,1H713D,J84,1H13CNMRCD3OD,100MHZ3271C83581C75500C85665C3OME6247C96520C98817C711106C211634C211666C511794C611931C612946C113689C513862C114194C314642C414748C415088C3GLC10276C17490C27783C37132C47820C56230C6THEDATAOF1HNMRAND13CNMRWERECONSISTENTWITHTHOSEOFTHEREFERENCE87S,8R3,4,9,9TETRAHYDROXYL3METHOXYL7,8DIHYDROBENZOFURAN1PROPYLNEOLIGNAN4WHITEPOWDER,1HNMRCD32CO,400MHZ176M,2H255T,J80,2H380S,3H551D,J65,1H658S,1H662S,1H681D,J81,1H689DD,J16,81,1H704D,J16,1H13CNMRCD32CO,100MHZ3228C83573C75510C85601C3OME6162C96451C98793C711025C211542C211614C511658C611941C612964C113446C113612C514139C314580C414691C414812C3THEDATAOF1HNMRAND13CNMRWERECONSISTENTWITHTHOSEOFTHEREFERENCE97S,8R4,9DIHYDROXYL3,3DIMETHOXYL7,8DIHYDROBENZOFURAN1PROPYLNEOLIGNAN9ODGLUCOPYRANOSIDE5WHITEPOWDER,1HNMRCD32CO,400MHZ178M,2H260M,J80,2H382S,3H385S,3H441D,J76,1H553D,J64,1H673BRS,1H678D,J80,1H682BRS,1H687DD,J80,20,1H707D,J20,1H13CNMRCD32CO,100MHZ3243C73562C85230C85616C3OME5624C3OME6153C97142C98812C711062C211549C611549C511772C211927C511937C613417C113629C114471C314669C414704C414817C3GLC10376C17470C27749C37153C47786C56268C6THEDATAOF1HNMRAND13CNMRWERECONSISTENTWITHTHOSEOFTHEREFERENCE107S,8R4,9,9TRIHYDROXYL3,3DIMETHOXYL7,8DIHYDROBENZOFURAN1PROPYLNEOLIGNAN6WHITEPOWDER,1HNMRCD32CO,400MHZ179M,2H261T,2H350T,1H357M,2H376M,1H379S,3H383S,3H387M,1H551D,J64,1H672BRS,1H674BRS,1H680D,J80,1H689DD,J20,80,1H703D,J20,1H13CNMRCD32CO,100MHZ3242C73555C85474C85609C3OME5626C3OME6167C96453C98797C711035C211366C211556C511739C611929C612971C113437C113609C514462C414687C414705C314820C3THEDATAOF1HNMRAND13CNMRWERECONSISTENTWITHTHOSEOFTHEREFERENCE11SYRINGARESINOL4ODGLUCOPYRANOSIDE7WHITEPOWDER,1HNMRCD32CO,400MHZ298M,1H298M,1H366S,6H369S,6H375M,1H406D,J40,1H413M,1H455D,J43,1H461D,J67,1H655S,2H662S,2H13CNMRCD32CO,100MHZ551C8552C8565C3,5OME567C3,5OME723C97240C98660C7864C71043C2,61045C2,613300C11355C11362C41394C41485C3,51538C3,5GLC1058C1755C27749C37133C4775C56268C6THEDATAOF1HNMRAND13CNMRWERECONSISTENTWITHTHOSEOFTHEREFERENCE128HYDROXYPINORESINOL4,4,8TRIHYDROXYL3,3DIMETHOXYLBISEPOXYLIGNAN8HYDROXYPINORESINOL8WHITEPOWDER,1HNMRCD3OD,400MHZ678D,J80,1H681D,J80,1H684DD,J80,20,1H688DD,J80,20,1H707D,J19,1H709D,J19,1H13CNMRCD3OD,100MHZ5608C3,3OME6105C87171C97570C98663C78860C79255C811088C211215C211504C511540C511989C612099C612917C113390C114684C414696C414777C314818C3THEDATAOF1HNMRAND13CNMRWERECONSISTENTWITHTHOSEOFTHEREFERENCE13PINORESINOL4ODGLUCOPYRANOSIDE9WHITEPOWDER,1HNMRCD32CO,400MHZ717D,J83,1H679D,J80